Improvement of wash fastness of pigment-containing colorants by application of oxidative pretreatment agents.

Abstract

The present invention relates to a method for dyeing keratinous materials, particularly human hair, comprising the steps of applying a pretreatment agent (V) to the keratinous material and applying a colorant (F) to the keratinous material, wherein the pretreatment agent contains (V-1) at least one oxidizing agent in a cosmetic carrier, and the colorant contains (F-1) at least one amino-functionalized silicone polymer and (F-2) at least one pigment.

Description

Technical Field

[0001] The subject of the present application is a method for the cosmetic coloring of keratinous substances, in particular human hair, which comprises the application of at least two different agents (V) and (F). Agent (V) represents a pretreatment agent containing at least one oxidizing agent in a cosmetic carrier. The coloring agent (F) consists of at least one amino-functionalized silicone polymer (F-1) and at least one pigment (F-2) in a cosmetic carrier.

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

[0003] A third subject of the present application is the use of said coloring agent (F) for coloring oxidatively pretreated human hair.

Background Art

[0004] Changing the shape and color of keratin fibers, in particular human hair, is an important area of modern cosmetics. To change the color of hair, experts know various coloring systems according to the coloring requirements. For long-lasting strong coloring with good fastness and good gray hair coverage, oxidative dyes are usually used. Such coloring agents contain oxidative dye precursors (so-called developing components) and coloring components, which, under the influence of an oxidizing agent such as hydrogen peroxide, produce the actual coloring agent with each other. Oxidative dyes are characterized by a very long-lasting staining result.

[0005] When using direct dyes, the already prepared coloring agent diffuses from the coloring agent into the hair fibers. Compared to oxidative hair dyeing, the dyed product obtained using direct dyes has a shorter color retention time and more rapid washability. Dyeing with direct dyes usually remains on the hair during 5 to 20 washings.

[0006] The use of coloring pigments is known to temporarily alter the color of hair and / or skin. Coloring pigments are generally understood to be insoluble coloring substances. They exist as small particles in the coloring composition, undissolved, and adhere exclusively to the surface of hair fibers and / or skin from the outside. Therefore, coloring pigments can usually be removed without residue by washing several times with a detergent containing a surfactant. Various products of this type are commercially available under the name "hair mascara."

[0007] Previously, if users desired particularly long-lasting color, oxidative dyes were the only option. However, despite numerous optimizations, oxidative hair dyes cannot completely avoid the unpleasant odor of ammonia or amines. Furthermore, the hair damage associated with the use of oxidative dyes negatively impacts the user's hair. Therefore, the search for alternative, high-performance dyeing methods remains an ongoing challenge. One possible alternative coloring system that has recently been gaining increasing attention is based on the use of coloring pigments.

[0008] Pigment-based coloring offers several significant advantages. Because the pigments only adhere to the keratinous substance, particularly the hair fibers, unwanted coloring can be quickly and easily removed without leaving any residue, allowing users to instantly return to their original hair color without any hassle. Therefore, this coloring process is especially appealing to consumers who do not want to permanently recolor their hair.

[0009] Recent research has addressed the issue of the low durability of this dyeing system. In this regard, it has been found that the wash fastness of coloring results obtained using pigments can be significantly improved by combining the pigments with certain amino-functionalized silicone polymers. Furthermore, by selecting pigments and pigment concentrations particularly suitable for dark-colored hair, lighter coloring results could be achieved, making it even possible to lighten hair with this dyeing system. This was previously only possible with oxidative hair treatments (bleachers or blonding agents).

[0010] However, in addition to these many advantages, pigment-based coloring systems also have some drawbacks, stemming from the shallow penetration depth of the pigments into the keratinous material. Since the pigments do not diffuse into the keratinous material or keratinous fibers but merely deposit on the outside of the keratinous material as a shell or film, the wash fastness of the dyes produced by this system still needs improvement. Even though good improvements in wash fastness have already been achieved by selecting particularly suitable pigments or aminosilicones, this is still not optimal. [Overview of the project] [Problems that the invention aims to solve]

[0011] Therefore, the object of this application is to find a pigment-based dyeing method that can achieve strong dyeing with improved fastness to washing. In this regard, keratinous substances, especially hair, dyed by this method should be precisely colored to the shade and intensity that the user expects after reading the relevant package information or instructions for use, regardless of the hair type and other cosmetics already used. Even after a long time and several hair washes, there should be no undesirable changes in the nuances of the dyed hair. [Means for solving the problem]

[0012] Surprisingly, it was found that subjecting keratinous substances, particularly hair, to oxidative pretreatment before the actual dyeing process significantly improved the wash fastness of the pigment dyeing system.

[0013] The first object of the present invention is, • A step of applying a pretreatment agent (V) to a keratin substance, and • A step of applying a coloring agent (F) to the keratin substance. A method for coloring keratinous substances, particularly human hair, including, The pretreatment agent in the cosmetic carrier contains (V-1) at least one oxidizing agent, The colorants present in the cosmetic carrier contain (F-1) at least one amino-functionalized silicone polymer and (F-2) at least one pigment. It is a method. [Effects of the Invention]

[0014] In the investigations leading to the present invention, it was found that applying two agents (V) and (F) in succession to color the hair yielded a particularly strong and wash-fast coloring result. Even after several hair washes, no undesirable or unattractive changes in nuance occurred. [Modes for carrying out the invention]

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

[0016] Preferably, the keratinous substance is understood to be human hair, human skin, and human nails (especially fingernails and toenails). The keratinous substance is understood to be, in particular, human hair.

[0017] Coloring agents In this specification, the term “colorant” is used for colorants of keratinous substances, particularly hair, which are brought about using pigments. In this coloring process, the pigment is deposited as a coloring compound on the surface of the keratinous substance in a particularly uniform, homogeneous, and smooth film.

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

[0019] Pretreatment agent (V) Cosmetic carrier The pretreatment agent (V) is characterized in that it contains at least one oxidizing agent (V-1) in the cosmetic carrier.

[0020] For pretreatment agent (V), suitable aqueous, alcoholic, or aqueous-alcoholic carriers can be used, for example. In the case of hair dyeing, such carriers are, for example, surfactant-containing foaming liquids such as creams, emulsions, gels, pastes, or shampoos, foam aerosols, foam compositions, or other preparations suitable for application to hair.

[0021] When the pretreatment agent (V) contains an oxidizing agent in aqueous solution or a water-containing carrier, the pretreatment agent (V) preferably has an average water content. Based on the total weight of the pretreatment agent (V), a pretreatment agent (V) containing 30.0 to 80.0% by weight, preferably 35.0 to 80.0% by weight, more preferably 40.0 to 70.0% by weight, and very preferably 45.0 to 60.0% by weight of water was found to be particularly suitable for use in the method of the present invention.

[0022] In one embodiment, the method of the present invention is characterized in that the pretreatment agent (V) contains 30.0 to 80.0% by weight, preferably 35.0 to 80.0% by weight, more preferably 40.0 to 70.0% by weight, and very preferably 45.0 to 60.0% by weight of water, based on the total weight of the pretreatment agent (V).

[0023] Oxidizing agent (V-1) or (V-2) in pretreatment agent (V) An oxidizing agent is a substance that has an oxidizing effect. In particular, the oxidizing agent in this invention can oxidatively modify keratin substances or human hair. Unlike oxygen in the atmosphere, the oxidizing agent in the sense of this invention has the ability to establish disulfide crosslinks within the hair keratin protein and within the natural pigment melanin, or between the hair keratin protein and the natural pigment melanin, which are oxidatively lightened.

[0024] In one embodiment, particularly preferred oxidizing agents are hydrogen peroxide and / or at least one adduct thereof (especially to inorganic or organic compounds), such as sodium perborate, sodium percarbonate, magnesium percarbonate, sodium percarbamide, polyvinylpyrrolidone, nH2O2 (where n is a positive integer greater than 0), urea peroxide, and melamine peroxide.

[0025] In another embodiment, persulfates and / or salts thereof can also be used as oxidizing agents in pretreatment agent (V). Particular preference is the use of one or more persulfates selected from the group consisting of ammonium peroxodisulfate, potassium peroxodisulfate, and sodium peroxodisulfate.

[0026] Ammonium peroxodisulfate, also known as ammonium persulfate, is understood to refer to a persulfate with the empirical formula (NH4)2S2O8.

[0027] Potassium peroxodisulfate, also known as potassium persulfate, is understood to refer to a persulfate with the empirical formula K2S2O8.

[0028] Sodium peroxodisulfate, also known as sodium persulfate, is understood to refer to a persulfate with the empirical formula: Na2S2O8.

[0029] In a particularly preferred embodiment, the method of the present invention is characterized in that the pretreatment agent (V) comprises at least one oxidizing agent (V-1) selected from the group consisting of hydrogen peroxide, ammonium peroxodisulfate, potassium peroxodisulfate, and sodium peroxodisulfate.

[0030] In carrying out tests leading to the present invention, it was found that, in the method of the present invention, particularly when a pretreatment agent (V) containing a combination of different oxidizing agents is used, a strong and effective improvement in cleaning robustness can be achieved. Particularly good results were obtained when a pretreatment agent (V) containing a combination of hydrogen peroxide (V-1) and at least one persulfate (V-2) selected from the group consisting of ammonium peroxodisulfate, potassium peroxodisulfate, and sodium peroxodisulfate was used.

[0031] In another very particularly preferred embodiment, the method of the present invention is characterized in that the pretreatment agent (V) comprises hydrogen peroxide (V-1) and at least one persulfate (V-2) selected from the group consisting of ammonium peroxodisulfate, potassium peroxodisulfate, and sodium peroxodisulfate.

[0032] In another very particular embodiment, the method of the present invention is characterized in that the pretreatment agent (V) comprises (V-1) hydrogen peroxide and (V-2) ammonium peroxodisulfate.

[0033] In another very particular embodiment, the method of the present invention is characterized in that the pretreatment agent (V) comprises (V-1) hydrogen peroxide and (V-2) potassium peroxodisulfate.

[0034] In another very particular embodiment, the method of the present invention is characterized in that the pretreatment agent (V) comprises (V-1) hydrogen peroxide and (V-2) sodium peroxodisulfate.

[0035] In another very particularly preferred embodiment, the method of the present invention is characterized in that the pretreatment agent (V) comprises (V-1) hydrogen peroxide and (V-2) ammonium peroxodisulfate and potassium peroxodisulfate.

[0036] In another very particularly preferred embodiment, the method of the present invention is characterized in that the pretreatment agent (V) comprises (V-1) hydrogen peroxide and (V-2) ammonium peroxodisulfate and sodium peroxodisulfate.

[0037] In another very particularly preferred embodiment, the method of the present invention is characterized in that the pretreatment agent (V) comprises (V-1) hydrogen peroxide and (V-2) potassium peroxodisulfate and sodium peroxodisulfate.

[0038] In another very particularly preferred embodiment, the method of the present invention is characterized in that the pretreatment agent (V) comprises (V-1) hydrogen peroxide and (V-2) ammonium peroxodisulfate and potassium peroxodisulfate and sodium peroxodisulfate.

[0039] In the present invention, the oxidative cosmetic pretreatment agent may additionally contain at least one catalyst as an optional component, which activates the oxidation of substances such as melanin present in keratinous substances. Such catalysts include metal ions, iodides, quinones, or certain enzymes.

[0040] Suitable metal ions are, for example, Zn 2+ , Cu 2+ , Fe 2+ , Fe 3+ , Mn 2+ , Mn 4+ , Li + , Mg 2+ , Ca 2+ and Al 3+ . Zn 2+ , Cu 2+ and Mn 2+ are particularly suitable. In principle, the metal ions can be used in the form of physiologically acceptable salts or complex compounds. Preferred salts are acetates, sulfates, halides, lactates and tartrates.

[0041] Suitable enzymes include peroxidases, which can significantly enhance the effect of small amounts of hydrogen peroxide. Also suitable in this invention are enzymes that generate small amounts of hydrogen peroxide in situ with the help of atmospheric oxygen, thereby biocatalyzing the oxidation of dye precursors. Catalysts particularly suitable for the oxidation of dye precursors are so-called 2-electron oxidoreductases combined with specific substrates for this purpose, examples of which are given below: • Pyranose oxidase and, for example, D-glucose or galactose, • Glucose oxidase and D-glucose, Glycerol oxidase and glycerol, • Pyruvate oxidase and benzopropic acid or salts thereof, • Alcohol oxidase and alcohols (MeOH, EtOH) Lactate oxidase and lactic acid and their salts, • Tyrosinase oxidase and tyrosine, • Uricase and uric acid or their salts, • Choline oxidase and choline, • Amino acid oxidase and amino acids.

[0042] By selecting an appropriate quantitative range of oxidizing agent (V-1) [or (V-1) and (V-2)] in the pretreatment agent (V), the magnitude of the effect of the pretreatment agent (V) on the wash fastness of the subsequently applied colorant (F) can be particularly controlled. In this regard, it has been found that the greater the amount of oxidizing agent used in the pretreatment agent (V), the better the wash fastness. However, on the other hand, damage to keratin substances or keratin fibers / hair also increases with increasing amounts of oxidizing agent used. To find the optimal balance between these two effects, it has been found that it is particularly preferable to use the oxidizing agent in a very specific quantitative range in the pretreatment agent.

[0043] Preferably, the pretreatment agent in the present invention contains 0.1 to 12.0% by weight, more preferably 0.5 to 10.0% by weight, even more preferably 1.5 to 8.0% by weight, and very preferably 3.0 to 6.0% by weight of hydrogen peroxide (V-1), based on the total weight of the pretreatment agent.

[0044] In another very particularly preferred embodiment, the method of the present invention is characterized in that the pretreatment agent (V) contains 0.1 to 12.0% by weight, preferably 0.5 to 10.0% by weight, more preferably 1.5 to 8.0% by weight, and very particularly preferably 3.0 to 6.0% by weight of hydrogen peroxide (V-1), based on the total weight of the pretreatment agent.

[0045] Preferably, the pretreatment agent (V) in the present invention contains, based on the total weight of the pretreatment agent, one or more persulfates (V-2) selected from the group consisting of ammonium peroxodisulfate, potassium peroxodisulfate, and sodium peroxodisulfate in a total amount of 5.0 to 30.0% by weight, more preferably 8.0 to 27.0% by weight, even more preferably 11.0 to 24.0% by weight, and very particularly 14.0 to 21.0% by weight.

[0046] In another particularly preferred embodiment, the method of the present invention is characterized in that the pretreatment agent (V) contains, based on the total weight of the pretreatment agent, one or more persulfates (V-2) selected from the group consisting of ammonium peroxodisulfate, potassium peroxodisulfate, and sodium peroxodisulfate in a total amount of 5.0 to 30.0% by weight, preferably 8.0 to 27.0% by weight, more preferably 11.0 to 24.0% by weight, and most preferably 14.0 to 21.0% by weight.

[0047] Coloring agent (F) In the method of the present invention, a coloring agent (F) is applied to the keratin substance following the application of a pretreatment agent (V).

[0048] Cosmetic carrier for colorant (F) The coloring agent (F) comprises at least one amino-functionalized silicone polymer (F-1) and at least one pigment (F-2) in a cosmetic carrier.

[0049] For example, a suitable aqueous, alcoholic, or aqueous-alcoholic carrier can be used as a cosmetic carrier for the colorant (F). For hair dyeing purposes, such carriers may be, for example, a surfactant-containing foaming liquid, foam aerosol, foam composition, or other preparation suitable for application to hair, such as a cream, emulsion, gel, paste, or shampoo.

[0050] When the colorant (F) contains an amino-functionalized silicone polymer (F-1) and a pigment (F-2) in an aqueous or water-containing carrier, the colorant (F) preferably has a high water content. Based on the total weight of the pretreatment agent (V), a colorant (F) containing 50.0 to 99.0% by weight, preferably 60.0 to 99.0% by weight, more preferably 70.0 to 99.0% by weight, and very preferably 80.0 to 99.0% by weight of water has been found to be particularly suitable for use in the method of the present invention.

[0051] In one embodiment, the method of the present invention is characterized in that the coloring agent (F) contains 50.0 to 99.0% by weight, preferably 60.0 to 99.0% by weight, more preferably 70.0 to 99.0% by weight, and very preferably 80.0 to 99.0% by weight of water, based on the total weight of the coloring agent (F).

[0052] 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. The amino-functionalized silicone polymer may also be referred to as aminosilicone or amodimethicone.

[0053] Silicone polymers generally have 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, and are macromolecules containing repeating organic units.

[0054] The maximum molecular weight of a silicone polymer depends on the degree of polymerization (number of monomers polymerized) and batch size, and is in part determined by the polymerization method. For the purposes of this invention, the maximum molecular weight of the silicone polymer is 10 7 g / mol or less, preferably 10 6 g / mol or less, particularly preferably 10 5 It is preferable that the concentration is g / mol or less.

[0055] Silicone polymers contain many Si-O repeating units, and the Si atoms may have organic residues, such as alkyl groups or substituted alkyl groups. Therefore, silicone polymers are also called polydimethylsiloxanes or their derivatives.

[0056] Silicone polymers, corresponding to their high molecular weight, are 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.

[0057] An amino-functionalized silicone polymer is understood to be a functionalized silicone containing at least one structural unit having an amino group. Preferably, the amino-functionalized silicone polymer has multiple structural units, each having at least one amino group. The amino group is understood to mean a primary amino group, a secondary amino group, and a tertiary amino group. All of these amino groups may be protonated in an acidic environment and exist in a cationic form.

[0058] In principle, good effects were obtained with the amino-functionalized silicone polymer (F-1) when it had at least one primary amino group, at least one secondary amino group, and / or at least one tertiary amino group. However, in the case of dye (F), the most wash-fast staining was observed when an amino-functionalized silicone polymer (F-1) having at least one secondary amino group was used.

[0059] In a particularly preferred embodiment, the method of the present 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.

[0060] One or more secondary amino groups can be present at various positions in amino-functionalized silicone polymers. Formula (Si-amino): Particularly good effects were observed when using an amino-functionalized silicone polymer (F-1) having at least one, preferably more, structural units represented by TIFF0007840863000001.tif7674.

[0061] In the structural unit represented by the formula (Si-amino), the abbreviations ALK1 and ALK2 independently represent a linear or branched divalent C1-C group. 20 Represents an alkylene group.

[0062] In another very particular embodiment, the method of the present invention uses a colorant (F) of the formula (Si-amino): TIFF0007840863000002.tif7674[In the formula, ALK1 and ALK2 are independently divalent C1-C12 or divalent C1-C12. 20 [Represents an alkylene group] The present invention is characterized by comprising at least one amino-functionalized silicone polymer (F-1) containing at least one structural unit represented by .

[0063] The positions indicated by the asterisk (*) represent bonding to other structural units of the silicone polymer. For example, a silicon atom adjacent to an asterisk may bond to another oxygen atom, and an oxygen atom adjacent to an asterisk may bond to another silicon atom or even a C1-C6 alkyl group.

[0064] Alternatively, divalent C1~C 20 The alkylene group is a divalent C1-C 20 These are sometimes referred to as alkylene groups, which means that each ALK1 and ALK2 group can form two bonds.

[0065] In the case of ALK1, one bond is formed from the silicon atom to the ALK1 group, and a second bond exists between ALK1 and the secondary amino group.

[0066] In the case of ALK2, there is one bond from the secondary amino group to the ALK2 group, and a second bond exists between ALK2 and the primary amino group.

[0067] Linear divalent C1~C 20 Examples of alkylene groups include methylene (-CH2-), ethylene (-CH2-CH2-), propylene (-CH2-CH2-CH2-), and butylene (-CH2-CH2-CH2-CH2-). Propylene (-CH2-CH2-CH2-) is particularly preferred. The divalent alkylene group may be branched from the chain length of three carbon atoms. Branched chain divalent C3~C 20 Examples of alkylene groups are (-CH2-CH(CH3)-) and (-CH2-CH(CH3)-CH2-).

[0068] In another particularly preferred embodiment, the structural unit represented by formula (Si-amino) represents a repeating unit in the amino-functionalized silicone polymer (F-1), so the silicone polymer contains multiple structural units represented by formula (Si-amino).

[0069] The following are particularly suitable amino-functionalized silicone polymers (F-1) having at least one secondary amino group.

[0070] In the method of the present invention, structural units represented by formula (Si-I) and structural units represented by formula (Si-II): When at least one dyeing agent (F) containing at least one amino-functionalized silicone polymer (F-1) including TIFF0007840863000003.tif80142 was applied to a keratinous substance, a dye with very good wash fastness was obtained.

[0071] In another very particular embodiment, the method of the present invention provides a colorant (F) with structural units represented by formula (Si-I) and formula (Si-II): It is characterized by containing at least one amino-functionalized silicone polymer (F-1) including TIFF0007840863000004.tif80142.

[0072] Corresponding amino-functionalized silicone polymers having structural units represented by formula (Si-I) and formula (Si-II) are, for example, the commercially available DC 2-8566 or Dowsil 2-8566 Amino Fluid, which is commercially available from Dow Chemical Company and has the name "Siloxane and Silicone, 3-[(2-aminoethyl)amino]-2-methylpropyl Me, Di-Me-siloxane" and CAS number 106842-44-8. Another particularly preferred commercial product is Dowsil AP-8658 Amino Fluid, also commercially available from Dow Chemical Company.

[0073] In another preferred embodiment, the method of the present invention is represented by formula (Si-III): TIFF0007840863000005.tif51111[In the formula, -m and n are numbers selected such that the sum (n+m) is in the range of 1 to 1000. -n is a number in the range of 0 to 999, and m is a number in the range of 1 to 1000. -R1, R2, and R3 are the same or different, and each has a hydroxyl group or C1~4 Represents an alkoxy group, -Here, at least one of R1 to R3 represents a hydroxyl group. The method is characterized by applying a coloring agent (F) comprising at least one amino-functional silicone polymer (F-1) as shown in the formula to a keratin substance.

[0074] Another preferred method of the present invention is formula (Si-IV): TIFF0007840863000006.tif48111[in formula -p and q are numbers selected such that the sum (p+q) is in the range of 1 to 1000. -p is a number in the range of 0 to 999, and 1 is a number in the range of 1 to 1000. -R1 and R2 are different, and are either hydroxyl groups or C 1~4 [Represents an alkoxy group, and at least one of R1 to R2 represents a hydroxyl group.] The method is characterized by applying a coloring agent (F) comprising at least one amino-functional silicone polymer (F-1) as shown in the formula to a keratin substance.

[0075] The silicone represented by formula (Si-III) and the silicone represented by formula (Si-IV) differ in the group of the Si atom containing the nitrogen group. In formula (Si-III), R2 is either a hydroxyl group or C 1~4 The alkoxy group is represented, while the group in formula (Si-IV) is a methyl group. The individual Si groups indicated by the subscripts m and n or p and q do not necessarily exist as blocks; rather, the individual units may exist in a statistically distributed manner. That is, in formulas (Si-III) and (Si-IV), not all R1-Si(CH3)2 groups are necessarily bonded to the -[O-Si(CH3)2] group.

[0076] Also, equation (Si-V): TIFF0007840863000007.tif4696[in the formula, A represents the group -OH, -O-Si(CH3)3, -O-Si(CH3)2OH, -O-Si(CH3)2OCH3, D represents the groups -H, -Si(CH3)3, -Si(CH3)2OH, and -Si(CH3)2OCH3. b, n, and c represent integers from 0 to 1000. For more details -n>0 and b+c>0 -At least one of the following conditions is met: A = -OH or D = -H] It has also been found that the present invention, which involves applying a colorant (F) containing at least one amino-functional silicone polymer (F-1) as shown in the formula to keratin fibers, is particularly effective with respect to the desired effect.

[0077] In the above formula (Si-V), the individual siloxane units having subscripts b, c, and n are statistically distributed; that is, they do not necessarily have to be block copolymers.

[0078] The coloring agent (F) is given by formula (Si-VI): M(R a Q b SiO (4-a-b) / 2 ) x (R c SiO (4-c) / 2 ) y M (Si-VI) [In the formula, R is a hydrocarbon or a hydrocarbon group having 1 to about 6 carbon atoms, and Q is a hydrocarbon of the general formula -R 1 HZ [here, R 1[where Z is a polar group represented by , where Z is a divalent linking group to which a hydrogen atom is bonded, consisting of a carbon and hydrogen atom, a carbon, hydrogen and oxygen atom, or a carbon, hydrogen and nitrogen atom, and Z is an organic amino functional group containing at least one amino functional group; a is a value in the range of about 0 to about 2, b is a value in the range of about 1 to about 3, a+b is 3 or less, c is a number in the range of about 1 to about 3, x is a number in the range of 1 to about 2000, preferably about 3 to about 50, most preferably about 3 to about 25, y is a number in the range of about 20 to about 10,000, preferably about 125 to about 10,000, most preferably about 150 to about 1,000, and M is a suitable silicone end group known in the art, preferably trimethylsiloxy] It may further contain one or more different amino-functionalized silicone polymers represented by .

[0079] Non-limiting examples of the group 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 1 to about 6 carbon atoms, and most preferably, R is methyl. 1 Examples include methylene, ethylene, propylene, hexamethylene, decamethylene, -CH2CH(CH3)CH2-, phenylene, naphthylene, -CH2CH2SCH2CH2-, -CH2CH2OCH2-, -OCH2CH2-, -OCH2CH2CH2-, -CH2CH(CH3)C(O)OCH2-, -(CH2)3CC(O)OCH2CH2-, -C6H4C6H4-, -C6H4CH2C6H4-; and -(CH2)3C(O)SCH2CH2-.

[0080] Z is an organic amino functional group containing at least one amino functional group. One possible formula for Z is NH(CH2) z NH2 [where z is greater than or equal to 1]. Another possible expression for Z is -NH(CH2) z (CH2) zz NH [wherein 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 -NHCH2CH2NH2 group. Another possible formula for Z is -N(CH2) z (CH2) zz NX2 or -NX2 [wherein each X in X2 is independently hydrogen and C] 1~12 [Selected from the group consisting of alkyl groups, and zz is 0]

[0081] Q is most preferably a polar amino functional group represented by the formula -CH2CH2CH2NHCH2CH2NH2, where a takes a value in the range of about 0 to about 2, b takes a value in the range of about 2 to about 3, a+b is less than or equal to 3, and c takes a value in the range of about 1 to about 3. a Q b SiO (4-a-b) / 2 Units and R c SiO (4-c) / 2 The molar ratio to the unit is in the range of approximately 1:2 to 1:65, preferably in the range of approximately 1:5 to 1:65, and most preferably in the range of approximately 1:15 to 1:20. When using one or more silicones represented by the above formula, the various variable substituents in the above formula may differ for the various silicone components present in the silicone mixture.

[0082] In a particularly preferred embodiment, the method of the present invention uses a colorant (F) of formula (Si-VII): R' a G 3-a -Si(OSiG2) n -(OSiG b R' 2-b ) m -O-SiG 3-a -R' a (Si-VII) [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 their sum (m+n) is between 1 and 2000, preferably between 50 and 150, where n is preferably between 0 and 1999, particularly between 49 and 149, and m is preferably between 1 and 2000, particularly 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-, -CH(CH3)CH2CH2-, R'' represents -H, -phenyl, -benzyl, -CH2-CH(CH3)Ph, C 1-20 This represents the same or different groups selected from the group consisting of alkyl, preferably -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -CH2CH2CH2H3, -CH2CH(CH3)2, -CH(CH3)CH2CH3, and -C(CH3)3. A represents an anion preferably selected from chloride, bromide, iodide, or methosulfate. [A monovalent group selected from] The method is characterized by applying a coloring agent (F), which is an amino-functional silicone polymer represented by [formula], to a keratin substance.

[0083] In another preferred embodiment, the method of the present invention is represented by formula (Si-VIIa): TIFF0007840863000008.tif21123[In the formula, m and n are numbers such that the sum (m+n) is between 1 and 2000, preferably between 50 and 150, where n is preferably between 0 and 1999, particularly between 49 and 149, and m is preferably between 1 and 2000, particularly between 1 and 10] The method is characterized by applying a coloring agent (F) comprising at least one amino-functional silicone polymer (F-1) as shown in the formula to a keratin substance.

[0084] In INCI terminology, these silicones are called trimethylsilylamodimethicone.

[0085] In another preferred embodiment, the method of the present invention is represented by formula (Si-VIIb): TIFF0007840863000009.tif21111[In the formula, R represents a -OH, -O-CH3 or -CH3 group, m, n1, and n2 are numbers such that their sum (m + n1 + n2) is between 1 and 2000, preferably between 50 and 150, where the sum (n1 + n2) is preferably between 0 and 1999, particularly between 49 and 149, and m is preferably between 1 and 2000, particularly between 1 and 10. The method is characterized by applying a coloring agent (F) comprising at least one amino-functional silicone polymer represented by [formula] to a keratin substance.

[0086] In INCI terminology, these amino-functionalized silicone polymers are called amodimethicone.

[0087] Regardless of which amino-functional silicone is used, the colorant (F) according to the present invention is preferred, which contains an amino-functional silicone polymer having an amine value greater than 0.25 meq / g, preferably greater than 0.3 meq / g, and more preferably greater 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 can also be expressed in mg KOH / g units.

[0088] Furthermore, a colorant (F) containing a specific 4-morpholinomethyl-substituted silicone polymer (F-1) is also suitable for use in the method of the present invention. This amino-functionalized silicone polymer contains structural units represented by formula (Si-VIII) and formula (Si-IX). TIFF0007840863000010.tif49139

[0089] The following are examples of suitable 4-morpholinomethyl-substituted silicone polymers. The corresponding amino-functionalized silicone polymer is known as amodimethicone / morpholinomethylsilsesquioxane copolymer and is commercially available from Wacker in the form of the raw material Belsil ADM 8301 E.

[0090] Examples of 4-morpholinomethyl-substituted silicones include those of formulas (Si-VIII), (Si-IX), and (Si-X): TIFF0007840863000011.tif63145[In the formula, R1 is -CH3, -OH, -OCH3, -O-CH2CH3, -O-CH2CH2CH3, or -O-CH(CH3)2. R2 is -CH3, -OH, or -OCH3. Silicone having the structural units shown can be used.

[0091] A particularly preferred colorant (F) in the present invention is of formula (Si-XI): TIFF0007840863000012.tif69161[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 groups -H, -Si(CH3)3, -Si(CH3)2OH, and -Si(CH3)2OCH3. a, b, and c independently represent integers between 0 and 1000, given the condition a+b+c>0. m and n are independent integers from 1 to 1000. however, • At least one of the conditions B = -OH or D = -H is satisfied. • The units a, b, c, m, and n are either statistically distributed or block-like in the molecule. It contains at least one 4-morpholinomethyl-substituted silicone as shown in [the formula].

[0092] In structural formula (Si-XI), it is intended to show that the siloxane groups n and m do not necessarily have to be directly bonded to 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., terminal groups B or D are preferably bonded to a dimethylsiloxy group. Furthermore, in formula (Si-VI), the siloxane units a, b, c, m and n are preferably statistically distributed.

[0093] The silicone used in accordance with the present invention and represented by formula (Si-VI) 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: 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 are selected from among the following. These silicones result in a significant improvement in the hair properties of hair treated with the agent of the present invention, and significantly improved protection in oxidation treatment.

[0094] It has been found that the colorant in the present invention is particularly advantageous when it contains one or more amino-functionalized silicone polymers (F-1) within a certain quantitative range. Particularly favorable results were obtained when the colorant contained 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 most preferably 0.4 to 2.5% by weight, relative to the total weight of the colorant.

[0095] In another particularly preferred embodiment, the device is according to the present invention. The method is characterized in that the colorant (F) contains 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.

[0096] Pigment (F-2) in coloring agent (F) As a second essential component of the present invention, the colorant (F) used in the method of the present invention contains at least one pigment.

[0097] In the sense of the present invention, a pigment is a coloring compound having a solubility in water at 25°C of less than 0.5 g / L, preferably less than 0.1 g / L, and more preferably less than 0.05 g / L. Solubility in water can be measured, for example, by the following method: Weigh 0.5 g of pigment into a beaker. Add a glass beaker. Then add 1 L of distilled water. Heat this mixture 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, possibly due to the high intensity of finely dispersed pigment, filter the mixture. If undissolved pigment remains on the filter paper, the solubility of that pigment is less than 0.5 g / L.

[0098] The appropriate coloring pigment may be of inorganic and / or organic origin.

[0099] In a preferred embodiment, the colorant (F) in the present invention is characterized by comprising at least one coloring compound (F-2) selected from the group consisting of inorganic pigments and / or organic pigments.

[0100] In a preferred embodiment, the colorant (F) in the present invention is characterized by comprising at least one inorganic pigment and / or organic pigment (F-2).

[0101] Preferred coloring pigments are selected from synthetic or natural inorganic pigments. Naturally derived inorganic coloring pigments can be prepared, for example, from chalk, ochre, amber, green earth, calcined terra di Siena, or graphite. In addition, black pigments such as black iron oxide, colored pigments such as ultramarine or red iron oxide, and fluorescent or phosphorescent pigments can be used as inorganic coloring pigments.

[0102] Colored metal oxides, metal hydroxides and metal oxide hydrates, mixed-phase pigments, sulfur-containing silicates, silicates, metal sulfides, complex metal cyanides, metal sulfates, chromates and / or molybdates are particularly suitable. Particularly preferred coloring 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 (ferric ferrocyanide, CI 77510) and / or carmine (cochineal).

[0103] In this invention, colored pearlescent pigments are also particularly preferred coloring pigments. These are typically mica and / or mica-based and may be coated with one or more metal oxides. Mica belongs to the layered silicate group. The most important representative examples of these silicates are muscovite, phlogopite, soda mica, biotite, scallop mica, and margareite. To produce pearlescent pigments in combination with metal oxides, mica, mainly muscovite or phlogopite, is coated with a metal oxide.

[0104] As a substitute for natural mica, synthetic mica coated with one or more metal oxides can be used as a pearlescent pigment. Particularly preferred pearlescent pigments are those based on natural or synthetic mica, coated with one or more of the aforementioned metal oxides. By changing the thickness of the metal oxide layer, the color of each pigment can be changed.

[0105] In another preferred embodiment, the method of the present invention is characterized in that the colorant (F) comprises at least an inorganic pigment (F-2) preferably selected from the group consisting of colored metal oxides, metal hydroxides, metal oxide hydrates, silicates, metal sulfides, complex metal cyanides, metal sulfates, and bronze pigments, and / or colored mica or mica-based pigments coated with at least one metal oxide and / or metal acid chloride.

[0106] In another preferred embodiment, the method of the present invention is characterized in that the colorant (F) comprises at least one pigment 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 oxide (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).

[0107] Examples of particularly suitable coloring pigments are available from Merck under the trade names Rona®, Colorona®, Xiron®, 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®.

[0108] Particularly preferred coloring pigments with the product name Colorona (registered trademark) include the following: Colorona Copper, Merck, Mica, CI 77491 (Iron Oxide) Colorona Passion Orange, Merck, Mica, CI 77491 (Iron Oxide), Alumina Colorona Patina Silver, Merck, Mica, CI 77499 (Iron Oxide), 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 Oxide) Colorona Dark Blue, Merck, Mica, Titanium Dioxide, Ferrocyanide Colorona Chameleon, Merck, CI 77491 (iron oxide), mica Colorona Aborigine Amber, Merck, Mica, CI 77499 (Iron Oxide), 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 (Iron Ferrocyanide) Colorona Red Brown, Merck, Mica, CI 77491 (Iron Oxide), 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), Iron Ferrocyanide (CI 77510) Colorona Red Gold, Merck, Mica, CI 77891 (Titanium Dioxide), CI 77491 (Iron Oxide) 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 Oxide) 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 Oxides, Mica, CI 77891, CI 77491 (EU) Colorona Mica Black, Merck, CI 77499 (Iron Oxide), 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 Oxide)

[0109] Other particularly preferred coloring pigments with the trade name Xirona® include, for example: Xirona Golden Sky, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide Xirona Caribbean Blue, Merck, Mica, CI 77891 (Titanium Dioxide), Silica, Tin Oxide Xirona Kiwi Rose, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide Xirona Magic Mauve, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide

[0110] Furthermore, particularly preferred coloring pigments with the product name Unipure (registered trademark) include the following: Unipure Red LC 381 EM, Sensient CI 77491 (Iron Oxide), Silica Unipure Black LC 989 EM, Sensient, CI 77499 (Iron Oxide), Silica Unipure Yellow LC 182 EM, Sensient, CI 77492 (Iron Oxide), Silica

[0111] In another embodiment, the pretreatment agent (V) according to the present invention may also include one or more organic pigments.

[0112] The organic pigment in the present invention may be selected from the group consisting of, for example, nitroso, nitro-azo, xanthene, anthraquinone, isoindolinone, isoindolinone, quinacridone, perinone, perylene, diketo-pyrrolopyrrole, indigo, thioindigo, dioxazine, and / or triarylmethane compounds, and is a moderately insoluble organic dye or color lacquer.

[0113] Examples of particularly suitable organic pigments include carmine, quinacridone, phthalocyanine, sorghum, blue pigments with color indices of Cl 42090, CI 69800, CI 69825, CI 73000, CI 74100, CI 74160, yellow pigments with color indices of CI 11680, CI 11710, CI 15985, CI 19140, CI 20040, CI 21100, CI 21108, CI 47000, CI 47005, green pigments with color indices of CI 61565, CI 61570, CI 74260, orange pigments with color indices of CI 11725, CI 15510, CI 45370, CI 71105, and CI 12085, CI 12120, CI 74260. 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 red pigments.

[0114] In another particularly preferred embodiment, the method of the present invention uses a colorant (F) of carmine, quinacridone, phthalocyanine, sorghum, a blue pigment with color indexes of Cl 42090, CI 69800, CI 69825, CI 73000, CI 74100, CI 74160, a yellow pigment with color indexes of CI 11680, CI 11710, CI 15985, CI 19140, CI 20040, CI 21100, CI 21108, CI 47000, CI 47005, a green pigment with color indexes of CI 61565, CI 61570, CI 74260, an orange pigment with color indexes of CI 11725, CI 15510, CI 45370, CI 71105, and a colorant (F) of CI 12085, CI The present invention is characterized by comprising at least one organic pigment (F-2) preferably selected from the group consisting of red pigments 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.

[0115] The organic pigment may also be a color paint. In the sense of the present invention, the term "color lacquer" means particles comprising a layer of absorbed dye, where the particle and dye units are insoluble under the above conditions. The particles may be, for example, an inorganic substrate, which may be aluminum, silica, calcium borosilicate, calcium aluminum borosilicate, or aluminum.

[0116] For example, Alizarin color varnish can be used.

[0117] Due to their excellent resistance to light and temperature, it is particularly preferable to use the above-mentioned pigment in the colorant (F) of the method of the present invention. Furthermore, it is preferable that the pigment used has a specific particle size. Accordingly, 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, preferably 10 to 40 μm, and particularly 14 to 30 μm. 50 Having is advantageous. Average particle size D 50 This can be measured, for example, using dynamic light scattering (DLS).

[0118] Pigment (F-2) constitutes the second essential component of the colorant (F) in the present invention and is preferably used in the agent within a certain quantitative range. Particularly good results were obtained when the colorant contained 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.

[0119] In another very particularly preferred embodiment, the method of the present invention is characterized in that the colorant (F) 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 very particularly preferably 0.25 to 1.5% by weight, based on the total weight of the colorant.

[0120] Direct dyes in colorants (F) In principle, the colorant (F) used in the method of the present invention may contain one or more direct colorants as optional components. Direct-acting dyes are dyes that act directly on hair and do not require an oxidation step to form color. Direct dyes are typically nitrophenylenediamine, nitroaminophenol, azo dyes, anthraquinones, triarylmethane dyes, or indophenol.

[0121] Direct dyes in the sense of the present invention have a solubility in water at 25°C greater than 0.5 g / L (760 mmHg) and are therefore not treated as pigments. Preferably, direct dyes in the sense of the present invention have a solubility in water at 25°C greater than 1.0 g / L (760 mmHg).

[0122] However, the essential advantage of the method of the present invention is that the coloring obtained with the pigment-based colorant (F) is, on the one hand, very washable, and on the other hand, has very high hue stability. This means that if fading occurs to the extent that it decreases after several washes of the keratin material, the fading occurs while maintaining the nuance of the color without any visible change in color. This hue stability is also observed when the colorant (F) contains a mixture of pigments (F-2) of different colors.

[0123] While not bound by this theory, in this invention, the reason for the high stability of the color is thought to be that all pigments are deposited as a film on the surface of the keratin material. Unlike direct dyes, pigments cannot diffuse into the keratin material. Also, unlike direct dyes, the size or structure of the pigment cannot affect the depth of penetration into the keratin material.

[0124] When a mixture of different colored direct dyes is applied to a keratinous substance, these different dyes are typically based on different color-developing structures and molecules of different dimensions. Due to these structural differences, these different dyes can diffuse into the keratinous substance to different depths and are washed away from the keratinous substance to different degrees during washing. In particular, when dyeing with natural shades produced by, for example, a mixture of yellow, red, and blue direct dyes, a change from brown to a yellowish, reddish, or bluish color may be observed during the process of several washes or shampoos.

[0125] The coloring produced by the method of the present invention is based on a pigment-silicone film localized on the surface of a keratinous substance. Washing tests showed that repeated washing slightly reduced the color intensity, but no change in hue occurred. Thus, the dissolution of different colored pigments from the film during hair washing is fairly uniform.

[0126] The fact that this color shift does not occur when using the method of the present invention is a significant advantage over dyeing systems based on direct dyes. For this reason, it is particularly preferable that the colorant (F) contains no direct dye or only a small amount of direct dye.

[0127] In another very particularly preferred embodiment, the method of the present invention is characterized in that the total amount of direct dye contained in the colorant (F) is less than 0.1% by weight, preferably less than 0.05% by weight, more preferably less than 0.01% by weight, and very particularly preferably less than 0.001% by weight, based on the total weight of the colorant (F).

[0128] In other words, in another particularly preferred embodiment, the method of the present invention is characterized in that the total amount of direct dye contained in the colorant (F) is less than 0.1% by weight, preferably less than 0.05% by weight, more preferably less than 0.01% by weight, and very particularly preferably less than 0.001% by weight, based on the total weight of the colorant (F), and the direct dye has a solubility in water at 25°C (760 mmHg) greater than 0.5 g / L.

[0129] In another very particular embodiment, the method of the present invention is characterized in that the colorant (F) does not contain a direct dye.

[0130] Direct dyes can be classified into anionic, cationic, and nonionic types.

[0131] Cationic direct dyes include, for example, Basic Blue 7, Basic Blue 26, HC Blue 16, Basic Violet 2 and Basic Violet 14, Basic Yellow 57, Basic Red 76, Basic Blue 16, Basic Blue 347 (Cationic Blue 347 / Dystar), HC Blue No. 16, Basic Blue 99, Basic Brown 16, Basic Brown 17, Basic Yellow 57, Basic Yellow 87, Basic Orange 31, Basic Red 51, and Basic Red 76.

[0132] Examples of nonionic direct dyes include nitro dyes, quinone dyes, and neutral azo dyes. Other examples of nonionic direct dyes include 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, and Disperse Black. 9, and 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 These are known by the international names or trade names of -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.

[0133] Anionic direct dyes are also called acid dyes. Acid dyes are direct dyes having at least one carboxylic acid group (-COOH) and / or at least one sulfonic acid group (-SO3H). Depending on the pH value, the protonated form (-COOH, -SO3H) of the carboxylic acid group or sulfonic acid group becomes their deprotonated form (-COOH). - , -SO3 -It exhibits an equilibrium relationship with (the presence of). The proportion of the protonated form increases with decreasing pH. When the direct dye is used as its salt, the carboxylic acid group or sulfonic acid group exists in a deprotonated form and is 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 in the sense of the present invention have a solubility in water at 25°C greater than 0.5 g / L (760 mmHg) and are therefore not treated as pigments. Preferably, acid dyes in the sense of the present invention have a solubility in water at 25°C greater than 1.0 g / L (760 mmHg).

[0135] Alkaline earth salts (e.g., calcium and magnesium salts) or aluminum salts of acid dyes often have lower solubility than their 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 characteristic of acid dyes is their ability to form anionic charges, and the carboxylic acid or sulfonic acid groups involved are typically bonded to various color-developing systems. Suitable color-developing systems are found, for example, in the structures of nitrophenylenediamine, nitroaminophenol, azo dyes, anthraquinone dyes, triarylmethane dyes, xanthan gum dyes, rhodamine dyes, oxazine dyes, and / or indophenol dyes.

[0137] Examples of acid dyes include: Acid Yellow 1 (D&C Yellow 7, Citronin A, Ext. D&C Yellow No. 7, Japan Yellow 403, CI 10316, COLIPA n°B001), Acid Yellow 3 (COLIPA n°54, D&C Yellow N°10, Quinoline Yellow, E104, Food Yellow 13), Acid Yellow 9 (CI 13015), Acid Yellow 17 (CI 18965), Acid Yellow 23 (COLIPA n°29, Covacap Jaune W 1100 (LCW), Sicovit Tartrazine 85 E 102 (BASF), Tartrazine, Food Yellow 4, Japan Yellow 4, FD&C Yellow No. 5), Acid Yellow 36 (CI 13065), Acid Yellow 121 (CI Acid Orange 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; KATSU201; 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, Red 18; CI 16255), Acid Red 27(E 123, CI 16185, C-Rot 46, Real red D, FD&C Red Nr.2、Food Red 9、Naphthol red S)、Acid Red 33(Red 33、Fuchsia Red、D&C Red 33、CI 17200)、Acid Red 35(CI C.I.18065)、Acid Red 51(CI 45430、Pyrosin B、Tetraiodfluorescein、Eosin J、Iodeosin)、Acid Red 52(CI 45100、Food Red 106、Solar Rhodamine B、Acid Rhodamine B、Red n°106 Pontacyl Brilliant Pink)、Acid Red 73(CI 27290)、Acid Red 87(Eosin、CI 45380)、Acid Red 92(COLIPA n℃53、CI 45410)、Acid Red 95(CI 45425、Erythtosine,Simacid Erythrosine Y)、Acid Red 184(CI 15685)、Acid Red 195、Acid Violet 43(Jarocol Violet 43、Ext. D&C Violet n°2、C.I. 60730、COLIPA n°C063)、Acid Violet 49(CI 42640)、Acid Violet 50(CI 50325)、Acid Blue 1(Patent Blue、CI 42045)、Acid Blue 3(Patent Blue V、CI 42051)、Acid Blue 7(CI 42080)、Acid Blue 104(CI 42735)、Acid Blue 9(E 133、Patent blue AE、Amido blue AE、Erioglaucin A、CI 42090、C.I. Food Blue 2)、Acid Blue 62(CI 62045)、Acid Blue 74(E 132、CI 73015)、Acid Blue 80(CI 61585)、Acid Green 3(CI 42085、Foodgreen1)、Acid Green 5(CI 42095)、Acid Green 9(C.I.42100)、Acid Green 22(C.I.42170), Acid Green 25 (CI 61570, Japan Green 201, D&C Green No. 5), Acid Green 50 (Brilliant Acid Green BS, CI 44090, Acid Brilliant Green BS, E 142), Acid Black 1 (Black n°401, Naphthalene Black 10B, Amido Black 10B, CI 20 470, COLIPA n°B15), Acid Black 52(CI 15711), Food Yellow 8(CI 14270), Food Blue 5, D&C Yellow 8, D&C Green 5, D&C Orange 10, D&C Orange 11, D&C Red 21, D&C Red 27, D&C Red 33, D&C Violet 2 and / or D&C Brown 1. .

[0138] For example, the water solubility of anionic direct dyes can be measured by the following method: 0.1 g of anionic direct dye is placed in a beaker. A stirrer is added. Then 100 mL of water is added. This mixture is heated to 25°C while stirring on a magnetic stirrer. Stirring is continued for 60 minutes. The aqueous mixture is then visually evaluated. If undissolved residue is still present, the amount of water is increased, for example, in 10 mL increments. Water is added until the amount of dye used is completely dissolved. If the dye-water mixture cannot be visually evaluated due to the high intensity of the dye, the mixture is filtered. If undissolved dye remains on the filter paper, the solubility test is repeated using more water. When 0.1 g of anionic direct dye is dissolved in 100 mL of water at 25°C, the solubility of the dye is 1.0 g / L.

[0139] Acid Yellow 1 is referred to as 8-hydroxy-5,7-dinitro-2-naphthalenesulfonic acid disodium salt and has a solubility of at least 40 g / L in water (at 25°C). Acid Yellow 3 is a mixture of the monosulfonic and disulfonic sodium salts of 2-(2-quinolyl)-1H-indene-1,3(2H)-dione, with a solubility of 20 g / L in water (at 25°C). 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 (at 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, which 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 (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 more 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-oxoxanthene-9-yl)benzoic acid, and its solubility in water is indicated as 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-cyclohexadiene-1-ylidene}methyl)-benzenesulfonate and has a solubility in water greater than 20% by weight (at 25°C).

[0140] Further optional components in agent (V) and / or (F) In addition to the components essential to the present invention as already described, the pretreatment agent (V) and / or coloring agent (F) may also include other optional components.

[0141] The agent may also contain other active ingredients, auxiliary agents, and additives, such as solvents; C8~C 30 Fatty alcohols, C8~C 30 Fatty acid triglycerides, C8~C 30 Fatty acid monoglycerides, C8~C 30Fatty components such as fatty acid diglycerides and / or hydrocarbons; polymers; structuralants, e.g., glucose, maleic acid and lactic acid; hair conditioning compounds, e.g., phospholipids, e.g., lecithin and kephalin; fragrance oils, dimethyl isosorbide and cyclodextrin; fiber structure improving active ingredients, especially monosaccharides, disaccharides and oligosaccharides, e.g., glucose, galactose, fructose, fructose and lactose; dyes for coloring products; anti-dandruff active ingredients, e.g., piroctone olamine, zinc omazine and crimbazole; amino acids and oligopeptides; animal and / or plant protein hydrolysates, as well as protein hydrolysates in the form of fatty acid condensates or optionally anionic or cationic modified derivatives; vegetable oils; light stabilizers and UV blockers; active ingredients, e.g., panthenol, pantothenic acid, pantolactone, allantoin, pyrrolidinone carboxylic acid and its salts, bisabolol; polyphenols, especially hydroxycinnamic acid, 6,7-dihydroxycoumarin, hydroxybenzoic acid, catechin, tannin, leucoanthocyanidin, anthocyanidin, flavanone, flavone and flavonol; ceramide or pseudoceramide; vitamins, provitamins and vitamin precursors; plant extracts; fats and waxes, e.g., fatty alcohols, beeswax, montan wax and kerosene; swelling agents and penetrating agents, e.g., glycerol, propylene glycol monoethyl ether, carbonate, bicarbonate, guanidine, urea, primary, secondary and tertiary phosphates; opacifying agents, e.g., latex, styrene / PVP and styrene / acrylamide copolymers; pearlescent agents, e.g., ethylene glycol mono- and distearate and PEG-3 distearate; and foaming agents, e.g., propane-butane mixtures, N2O, dimethyl ether, CO2 and air.

[0142] The selection of these other substances is made by those skilled in the art, depending on the desired properties of the agent. Other optional components and the amounts to be used are specified in relevant manuals known to those skilled in the art. 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, particularly 0.0005 to 15% by weight, based on the total weight of each agent.

[0143] pH value of pretreatment agent (V) and / or coloring agent (F) The pH values ​​of agents (V) and (F) in the present invention can be adjusted to a slightly acidic to alkaline pH.

[0144] In one embodiment, the pretreatment agent (V) has a pH of 6.0 to 12.0, preferably 7.0 to 11.5, more preferably 7.5 to 11.0, and most preferably 9.0 to 11.0. When a pretreatment agent (V) having these pH values ​​was used in the method of the present invention, a color with particularly good colorfastness was obtained.

[0145] In another embodiment, the method of the present invention is characterized in that the pretreatment agent (V) has a pH of 6.0 to 12.0, preferably 7.0 to 11.5, more preferably 7.5 to 11.0, and most preferably 9.0 to 11.0.

[0146] The pH value of the coloring agent (F) in the present invention can be adjusted to a slightly acidic to alkaline pH. Very preferably, the coloring agent (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.

[0147] The desired pH values ​​can be set using alkalizing and acidifying agents known to those skilled in the art. The pH value for the purposes of this invention is the pH value measured at a temperature of 22°C.

[0148] As an alkalizing agent, the agent may include, for example, ammonia, alkanolamines, and / or basic amino acids.

[0149] The alkanolamines that can be used in the agents of the present invention can preferably be selected from primary amines having a C2-C6 alkyl base with at least one hydroxyl group. Preferred alkanolamines are selected from the group formed from 2-aminoethane-1-ol (monoethanolamine), 3-aminopropane-1-ol, 4-aminobutan-1-ol, 5-aminopentan-1-ol, 1-aminopropane-2-ol, 1-aminobutan-2-ol, 1-aminopentan-2-ol, 1-aminopentan-3-ol, 1-aminopentan-4-ol, 3-amino-2-methylpropane-1-ol, 1-amino-2-methylpropane-2-ol, 3-aminopropane-1,2-diol, and 2-amino-2-methylpropane-1,3-diol.

[0150] In the present invention, particularly preferred alkanolamines are selected from 2-aminoethane-1-ol and / or 2-amino-2-methylpropane-1-ol. Accordingly, a particularly preferred embodiment is characterized in that the agent in the present invention comprises an alkanolamine selected from 2-aminoethane-1-ol and / or 2-amino-2-methylpropane-1-ol as an alkalizing agent.

[0151] For the purposes of the present invention, an amino acid is an organic compound whose structure contains at least one protic amino group and at least one -COOH group or at least one -SO3H group. Preferred amino acids are aminocarboxylic acids, particularly α-(alpha)-aminocarboxylic acids and ω-aminocarboxylic acids, in which case α-aminocarboxylic acids are particularly preferred.

[0152] In this invention, a basic amino acid is an amino acid having an isoelectric point pI greater than 7.0.

[0153] Basic α-aminocarboxylic acids contain at least one chiral carbon atom. In the present invention, both enantiomers can be used equally as specific compounds or mixtures thereof, particularly as racemates. However, it is particularly preferable to use the isomer form that is typically L-configuration and is therefore necessarily preferred.

[0154] The basic amino acid is preferably selected from the group consisting of arginine, lysine, ornithine, and histidine, and particularly preferably arginine and lysine. Accordingly, in another particularly preferred embodiment, the agent of the present invention is characterized in that the alkalizing agent is a basic amino acid selected from the group consisting of arginine, lysine, ornithine, and / or histidine.

[0155] Furthermore, the product may contain other alkalizing agents, particularly inorganic alkalizing agents. The inorganic alkalizing agents used in the present invention are preferably selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium phosphate, potassium phosphate, sodium silicate, sodium metasilicate, potassium silicate, sodium carbonate, and potassium carbonate.

[0156] In this invention, the desired pH value can also be adjusted by a buffer system. A buffer or buffer system is generally understood to be a mixture of a weak or moderately strong acid (e.g., acetic acid) and a substantially completely dissociated neutral salt of the same acid (e.g., sodium acetate). Adding a small amount of base or acid will hardly change the pH value (buffering). The effect of the buffering substance contained in the buffer solution is based on the scavenging reaction of hydrogen ions or hydroxide ions, which involves the formation of a weak acid or weak base due to dissociation equilibrium. A buffer system can be formed from a mixture of an inorganic or organic acid and its corresponding salt. 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 acids (which completely dissociate into ions) can be buffered, for example, by the addition of sodium acetate. Equilibrium below: According to TIFF0007840863000013.tif8106, hydrochloric acid is converted to weak acetic acid by sodium acetate, forming sodium chloride. Sodium chloride dissociates only slightly in the presence of excess sodium acetate. A buffer effective for both acids and bases is a mixture of a weak acid and its salt.

[0157] Examples of buffer systems known from the literature include acetate / sodium acetate, boric acid / sodium borate, phosphoric acid / sodium phosphate, and bicarbonate / sodium.

[0158] The pH of the agent in this invention can be adjusted, for example, by adding an inorganic or organic buffer system. For the purposes of this invention, the inorganic buffer system is understood to be a mixture of an inorganic acid and its corresponding conjugated inorganic base.

[0159] For the purposes of this invention, an organic buffer system is understood to be a mixture of an organic acid and its corresponding conjugate base. Due to the organic acid group, the corresponding conjugate base of the organic acid is also organic. Here, the cation present to neutralize the charge of the acidic anion may be inorganic or organic.

[0160] Examples of inorganic acids include sulfuric acid, hydrochloric acid, and phosphoric acid (H3PO4). Phosphoric acid is a particularly preferred medium-strength acid.

[0161] Potassium dihydrogen phosphate is a particularly suitable inorganic acid. 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 readily soluble in water (222 g / L at 20°C) and is acidic in water. A 5% aqueous solution of potassium dihydrogen phosphate has a pH of 4.4.

[0162] Another particularly suitable 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 to acidity in aqueous solution.

[0163] A particularly preferred corresponding salt for the two acids mentioned above is dipotassium hydrogen phosphate. Dipotassium hydrogen phosphate has the molecular formula K2HPO4 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 with alkaline solutions in aqueous solution.

[0164] Disodium hydrogen phosphate is also particularly preferred as the corresponding salt of the two acids mentioned above. Disodium hydrogen phosphate has the molecular formula: Na2HPO4 and has 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 alkalinely in aqueous solution.

[0165] Examples of organic acids include citric acid, succinic acid, tartaric acid, lactic acid, acetic acid, malic acid, malonic acid, and maleic acid.

[0166] Examples of the corresponding salts of these organic acids include the sodium and potassium salts of citric acid, succinic acid, tartaric acid, lactic acid, acetic acid, malic acid, malonic acid, and maleic acid.

[0167] Method and sequence of steps As mentioned earlier, the pretreatment agent (V) is applied before the coloring agent (F). In this regard, it was found that the application of the pretreatment agent (V) to the keratin substance is particularly preferable. The pretreatment agent (V) is allowed to act for a certain period of time, and then rinsed off with water again.

[0168] Therefore, for another target, the following steps: (1) A step of applying a pretreatment agent (V) as disclosed in detail in the description of the first subject of the invention to keratin fibers, (2) A step of applying the pretreatment agent applied in step (1) to the keratin fibers for 2 to 45 minutes, preferably 2 to 30 minutes, and particularly preferably 2 to 20 minutes. (3) A step of rinsing off the pretreatment agent with water, (4) A step of applying a colorant (F) as disclosed in detail in the description of the first subject of the invention to keratin fibers, (5) A step of allowing the coloring agent applied in step (4) to act on the keratin fibers for 15 seconds to 45 minutes, preferably 30 seconds to 30 minutes, more preferably 1 to 15 minutes. (6) The process of rinsing off the dye with water. This is a method for coloring keratin fibers, particularly human hair, by including them in this order.

[0169] In step (1) of the method according to the present invention, a pretreatment agent (V) containing at least one oxidizing agent in a water-containing carrier is applied to the hair.

[0170] In the subsequent step, the previously applied pretreatment agent (V) is applied to the keratin fibers. Various exposure times are possible for this, ranging from 2 to 45 minutes, preferably 2 to 30 minutes, and particularly preferably 2 to 20 minutes.

[0171] Following the action of the pretreatment agent (V) on the keratin fibers, in step (3), they are finally rinsed with water. In this case, the pretreatment agent (V) can be washed away with water alone, i.e., without using shampoo, or the rinsing process can be assisted by the application of shampoo.

[0172] In principle, users are free to choose the time between applying the two agents (V) and (F).

[0173] However, it may be preferable not to apply other products such as other conditioners or styling products between the application of the two products (V) and (F). Thus, the maximum time between the application of the two products (V) and (F) is preferably limited to a maximum of 24 hours.

[0174] It was found that it is preferable to have a time interval of 24 hours or less, preferably 12 hours or less, more preferably 6 hours or less, and very preferably 3 hours or less between rinsing the pretreatment agent (V) with water and applying the coloring agent (F) to the keratin fibers.

[0175] In another preferred embodiment, the method of the present invention is characterized in that there is a time interval of 24 hours or less, preferably 12 hours or less, more preferably 6 hours or less, and very preferably 3 hours or less between steps (3) and (4).

[0176] In another preferred embodiment, the method of the present invention is characterized by performing step (4) immediately after step (3). Step (4) is used for the application of a colorant.

[0177] The action of the coloring agent (F) on the keratin fibers in step (5) may be for a period of time ranging from 15 seconds to 30 minutes, for example, preferably in the range of 30 seconds to 15 minutes, and more preferably in the range of 1 to 15 minutes.

[0178] Subsequently, in step (6), the coloring agent (F) is finally rinsed with water. In a preferred embodiment, the coloring agent (F) is washed away with water alone, that is, without using any post-treatment agents or shampoos that do not conform to the present invention.

[0179] Multi-component packaging unit To enhance user convenience, users may preferably obtain all essential ingredients in the form of a multi-component packaging unit (kit of parts).

[0180] Therefore, another subject of the present invention is a separately prepared, A first container containing a pretreatment agent (V) as disclosed in detail in the description of the first subject of the invention, and • A second container containing a colorant (F) as disclosed in detail in the description of the first subject of the invention. It is a multi-component packaging unit (kit of parts) for staining keratinous materials, comprising [the specified components].

[0181] With regard to another preferred embodiment of the multi-component packaging unit in the present invention, the methods described in the present invention apply with necessary modifications.

[0182] Use of dyeing mixture (F) for dyeing oxidatively pretreated hair As mentioned earlier, by sequentially applying the pretreatment agent (V) and the dyeing agent (F), the wash fastness was significantly improved, and dyeing with very good color stability was obtained. This oxidative pretreatment is considered to be the factor in the improved durability of the coloring agent (F). In other words, it is thought that the structural change of the keratin substance caused by the action of the oxidizing agent (V-1) results in a film formed by the coloring agent (F) with improved adhesion to the surface of the keratin substance (or hair fibers).

[0183] Therefore, the first method of the present invention is extremely suitable for producing a stable dye after washing hair. However, there is still the possibility that users who have already subjected their hair to an oxidative treatment such as hair bleaching or decolorization may subsequently want to change the color of their bleached hair again. As described above, the colorant (F) of the present invention is also very suitable for this group of people.

[0184] Accordingly, another subject of the present invention is the use of the colorant (F), which is disclosed in detail in the description of the first subject of the invention, for coloring oxidatively pretreated human hair.

[0185] Oxidative pretreatment of hair refers to the treatment of hair with an oxidizing agent, and commercially available bleaches or bleaches can usually be used for this purpose. These commercially available bleaches, which are well known to those skilled in the art, generally contain, as an oxidizing agent, at least one oxidizing agent selected from the group consisting of hydrogen peroxide, ammonium peroxodisulfate, potassium peroxodisulfate, and sodium peroxodisulfate.

[0186] With regard to another preferred embodiment of use in the present invention, the methods described in the present invention will apply with necessary modifications. [Examples]

[0187] Examples 1. Composition The following ready-to-use pretreatment agent (V) was prepared (all data are shown in weight percent unless otherwise specified). TIFF0007840863000014.tif136154

[0188] The following coloring agent (F) was prepared (all data are shown in weight percent unless otherwise specified). TIFF0007840863000015.tif90154

[0189] 2. Application to bundles First, pretreatment agent (V) was applied to hair bundles (Kerling company). For this purpose, 0.2g of pretreatment agent (V) per gram of hair was applied to each bundle, massaged in, and left at room temperature for 30 minutes. Next, the hair bundles were rinsed with water. Immediately afterward, colorant (F) was applied to the still-damp hair. For this purpose, 0.2g of colorant (F) per gram of hair bundle was massaged in, left for 1 minute, then rinsed again with water and dried.

[0190] The reference hair bundle was treated directly with colorant (F) without the application of pretreatment agent (V). Before applying colorant (F), the reference hair bundle was moistened with water only, and then the colorant was applied according to the procedure described above.

[0191] Dry hair strands were color-measured using a Datacolor Spectraflash 450 type colorimeter.

[0192] Next, each colored hair bundle was manually washed six times. After each wash, the hair bundle was moistened, and then a commercially available shampoo (Schwarzkopf, Schauma 7 herbs) was massaged into the hair bundle for 25 seconds (0.25g of shampoo per gram of hair). The hair bundle was then rinsed with lukewarm tap water for 30 seconds and dried.

[0193] After six hair washes were completed, each hair bundle was color-analyzed again.

[0194] The dE value used to evaluate wash fastness is derived from the measured L*a*b* colorimetric values, as follows: dE = [(L i - L0) 2 + (a i - a0) 2 + (b i - b0)] 1 / 2 L0, a0, and b0 are measurements of colored hair bundles before washing. L i a i and b i This is a measurement of colored hair bundles after six hair washes.

[0195] TIFF0007840863000016.tif29161

[0196] Example 1 is a comparative example in which the coloring agent (F) was applied without any pretreatment.

[0197] Example 2 is an example of the present invention in which the pretreatment agent (V) and the coloring agent (F) are applied consecutively.

[0198] When the method of the present invention is applied, a significantly reduced dE value is observed, and therefore, a significantly improved cleaning fastness is observed.

Claims

1. The following steps: - A step of applying a pretreatment agent (V) to a keratin substance, and - Process of applying coloring agent (F) to keratin material A method for staining keratinous substances, including, The pretreatment agent in the cosmetic carrier contains, based on the total weight of the pretreatment agent, 3.0 to 6.0% by weight of (V-1) hydrogen peroxide and 14.0 to 21.0% by weight of at least one persulfate selected from the group consisting of (V-2) ammonium peroxodisulfate, potassium peroxodisulfate, and sodium peroxodisulfate. The colorant present in the cosmetic carrier contains (F-1) at least one amino-functionalized silicone polymer and (F-2) at least one pigment, wherein the at least one amino-functionalized silicone polymer comprises structural units represented by formula (Si-I) and structural units represented by formula (Si-II): The polymer comprises at least one amino-functionalized silicone polymer (F-1) including the following: method.

2. The method according to claim 1, characterized in that the coloring agent (F) contains one or more amino-functionalized silicone polymers (F-1) in a total amount of 0.1 to 8.0% by weight based on the total weight of the coloring agent.

3. The method according to claim 1 or 2, characterized in that the coloring agent (F) comprises at least an inorganic pigment (F-2) selected from the group consisting of colored metal oxides, metal hydroxides, metal oxide hydrates, silicates, metal sulfides, complex metal cyanides, metal sulfates, and bronze pigments, and / or colored mica or mica-based pigments coated with at least one metal oxide and / or metal acid chloride.

4. The colorants (F) are carmine, quinacridone, phthalocyanine, sorghum, blue pigments with color indices Cl 42090, CI 69800, CI 69825, CI 73000, CI 74100, CI 74160, yellow pigments with color indices CI 11680, CI 11710, CI 15985, CI 19140, CI 20040, CI 21100, CI 21108, CI 47000, CI 47005, green pigments with color indices CI 61565, CI 61570, CI 74260, orange pigments with color indices CI 11725, CI 15510, CI 45370, CI 71105, and CI 12085, CI 12120, CI The method according to any one of claims 1 to 3, characterized in that it comprises at least one organic pigment (F-2) selected from the group consisting of red pigments 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.

5. The method according to any one of claims 1 to 4, characterized in that the coloring agent (F) contains one or more pigments (F-2) in a total amount of 0.01 to 10.0% by weight based on the total weight of the coloring agent.

6. The method according to any one of claims 1 to 5, characterized in that the total amount of direct dye contained in the coloring agent (F) is less than 0.1% by weight, based on the total weight of the coloring agent (F).

7. The following steps: (1) A step of applying the pretreatment agent (V) described in claim 1 to keratin fibers, (2) A step of applying the pretreatment agent applied in step (1) to the keratin fibers for 2 to 45 minutes. (3) A step of rinsing off the pretreatment agent with water, (4) A step of applying the coloring agent (F) according to any one of claims 1 to 6 to keratin fibers, (5) A step of allowing the coloring agent applied in step (4) to act on the keratin fibers for 15 seconds to 45 minutes, and (6) Rinsing off the coloring agent with water A method for coloring keratin fibers, comprising the following in this order.

8. The method according to claim 7, characterized in that there is a time interval of 24 hours or less between steps (3) and (4).

9. Individually packaged, - A first container containing the pretreatment agent (V) described in claim 1, and - A second container containing the coloring agent (F) according to any one of claims 1 to 6. A kit of parts for staining keratinous materials, comprising [the specified components].

10. Use of a coloring agent (F) according to any one of claims 1 to 6 for coloring human hair that has been oxidatively pretreated with a pretreatment agent (V) comprising (V-1) hydrogen peroxide and (V-2) at least one persulfate selected from the group consisting of ammonium peroxodisulfate, potassium peroxodisulfate, and sodium peroxodisulfate.

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