Composition for coloring keratin material with oxidative coupler dyes

Abstract

The object of the present invention is to provide a novel composition for coloring or dyeing keratinous substances that does not require the use of an oxidation precursor or base. [Solution] The present invention provides, (a) At least one oxidative coupler dye that generates at least one autocoupling oxidative dye precursor by oxidation, (b) At least one oxidation catalyst selected from (b1) enzymes and (b2) inorganic catalysts The present invention relates to a composition containing [a certain substance]. The composition according to the present invention is very preferred for coloring and / or dyeing keratinic substances.

Description

Technical Field

[0001] The present invention relates to a composition for coloring or dyeing keratinous substances, preferably a cosmetic composition, comprising at least one oxidative coupler dye that produces at least one auto-coupling oxidative dye precursor by oxidation. The present invention also relates to a beauty method for coloring or dyeing keratinous substances using the same.

Background Art

[0002] It is known to dye keratin fibers, particularly human hair, with dyeing compositions containing oxidative coloring precursors and couplers generally called oxidative bases. These bases and these couplers are colorless or lightly colored compounds and can provide colored compounds through an oxidative condensation process in combination with an oxidizing agent product.

[0003] In addition to oxidative bases and couplers, oxidative catalysts that enhance oxidative coloring of hair are widely used. For example, WO2001 / 172272, EP0642783A, JP2014-114264A, JP2003-119115A, JP2003-055175A, EP1297817A, and EP1325733A disclose the use of oxidative catalysts such as metals alone or their salts, metals with ligands (acids, hexacyanoferrates), or chelating agents (EDTA), enzymes of the peroxidase family (lactoperoxidase, horseradish peroxidase), or laccase or tyrosinase, and halogen oxidative catalysts (iodine).

[0004] Most oxidative precursors or bases for hair coloring are evaluated within strict regulatory limits due to their high risks regarding human safety and environmental footprint. Furthermore, there are also concerns about the safety of some catalysts used to enhance oxidative coloring for humans and the environment. Therefore, there is a need to develop new methods for coloring or dyeing keratinous substances with less impact on human safety and the environment.

Prior Art Documents

[0005]

Patent Document 1

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Non-licensed literature

[0006]

Non-Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0007] An object of the present invention is to provide a new composition for coloring or dyeing keratin substances without the need to use an oxidation precursor or a base.

Means for Solving the Problems

[0008] [[ID=Z23]]The above object of the present invention is (a) at least one oxidation coupler dye that generates at least one auto-coupling oxidation dye precursor by oxidation, and (b) at least one oxidation catalyst selected from (b1) an enzyme and (b2) an inorganic catalyst can be achieved by a composition comprising.

[0009] (a) The oxidation coupler dye may be selected from 1-naphthol and 6-hydroxyindole.

[0010] The composition according to the present invention may comprise at least one enzyme selected from (b1) peroxidase, particularly non-specific peroxidase.

[0011] The composition according to the present invention may comprise at least one inorganic catalyst selected from (b2) a metal catalyst.

[0012] The metal catalyst may be selected from a metal organic framework (MOF), a mesoporous structure in which a metal such as zeolite is doped inside, and a metal organic complex.

[0013] The metal in the metal catalyst is selected from copper, iron, titanium, magnesium, zinc, cobalt, platinum, cerium, nickel, silver, zirconium, chromium, molybdenum, tungsten, gold, vanadium, and combinations thereof, and is preferably selected from copper(II), iron(II) or (III), titanium(IV), magnesium(II), and combinations thereof, particularly copper(II).

[0014] Metal-organic frameworks (MOFs) or mesoporous structures doped with metal may have a mesoporous or microporous structure.

[0015] The mesoporous or microporous structure of a metal-organic framework (MOF) or a metal-doped mesoporous structure may have pore diameters in the range of 3 to 30 angstroms, preferably 5 to 25 angstroms, and more preferably 7 to 20 angstroms.

[0016] The metal-organic complex includes organic ligands that can be selected from porphyrin ligands, chlorin ligands, such as chlorophyllin, bacteriochlorin ligands, β-diketone ligands, and combinations thereof.

[0017] The metal-organic complex can be selected from metal acetylacetonates, metal chlorophyllins, and metal phthalocyanines.

[0018] The amount of (a) oxide coupler dye in the composition may be in the range of 0.05% to 3% by mass, preferably 0.075% to 1% by mass, and more preferably 0.1% to 0.5% by mass, relative to the total mass of the composition.

[0019] The amount of enzyme (b1) in the composition may be in the range of 0.005% to 0.3% by mass, preferably 0.01% to 0.2% by mass, and more preferably 0.015% to 0.1% by mass, relative to the total mass of the composition.

[0020] The amount of (b2) inorganic catalyst in the composition is in the range of 0.05% to 1% by mass, preferably 0.1% to 0.75% by mass, and more preferably 0.2% to 0.5% by mass, relative to the total mass of the composition.

[0021] The present invention also, (a) At least one oxidative coupler dye that generates at least one autocoupling oxidative dye precursor by oxidation, and (b) At least one oxidation catalyst selected from (b1) enzymes and (b2) inorganic catalysts A first compartment containing a first composition including, A second compartment comprising a second composition containing at least one oxidizing agent and Regarding a kit that includes the following:

[0022] The present invention also relates to a method for coloring or dyeing a keratin substance, preferably hair, (1) A step of mixing the first composition and the second composition to prepare a mixture, The first composition is (a) At least one oxidative coupler dye that generates at least one autocoupling oxidative dye precursor by oxidation, and (b) At least one oxidation catalyst selected from (b1) enzymes and (b2) inorganic catalysts Includes, The second composition comprises at least one oxidizing agent, and the process is as follows: (2) A step of applying the mixture to a keratin substance and This includes methods. [Modes for carrying out the invention]

[0023] As a result of diligent research, the inventors have discovered that a composition comprising at least one oxidation catalyst selected from (b)(b1) enzymes and (b2) inorganic catalysts can produce improved coloring properties even without using conventional oxidation dyes, by using a specific type of (a) at least one oxidation coupler dye as a starting material, thereby completing the present invention.

[0024] Therefore, the present invention is (a) At least one oxidative coupler dye that generates at least one autocoupling oxidative dye precursor by oxidation, (b) At least one oxidation catalyst selected from (b1) enzymes and (b2) inorganic catalysts This relates to a composition containing the following:

[0025] The compositions according to the present invention are highly preferable for coloring or dyeing keratinous substances, such as hair, because they can provide improved coloring properties without using traditional oxidative dyes, most of which are known to pose high risks to human safety and the environment.

[0026] The compositions and methods according to the present invention will be described in more detail below.

[0027] [Composition] The composition according to the present invention is (a) At least one oxidative coupler dye that generates at least one autocoupling oxidative dye precursor by oxidation, (b) At least one oxidation catalyst selected from (b1) enzymes and (b2) inorganic catalysts Includes.

[0028] The compositions according to the present invention are intended for use in coloring or dyeing keratinous substances. Therefore, the compositions according to the present invention may be topical cosmetic compositions intended for application on keratinous substances. For the purposes of the present invention, the term "keratinous substance" includes substances containing keratin as a main component, preferably hair.

[0029] The composition according to the present invention can color keratin fibers. In a preferred embodiment, the composition according to the present invention is for coloring or dyeing keratin, particularly hair. Therefore, the present invention may be a hair coloring composition.

[0030] In a preferred embodiment, the composition according to the present invention can be used for hair coloring. Therefore, the composition may be a hair coloring product.

[0031] The composition according to the present invention can produce an oxidation dye by a two-step reaction. First, (a) the oxidation coupler dye of the present invention is oxidized by the action of (b) an oxidation catalyst to produce an autocoupling oxidation dye precursor. Then, the produced autocoupling oxidation dye precursor self-couples to produce an oxidation dye. Therefore, the composition according to the present invention can produce an oxidation dye without using traditional oxidation precursors / bases that are unsafe for human health to color keratinous materials. Thus, the present invention can provide coloring or dyeing of keratinous materials with minimal impact on human safety and the environment.

[0032] The compositions according to the present invention can take various forms, such as solutions, gels, lotions, serums, suspensions, dispersions, fluids, milks, pastes, creams, foams, emulsions (O / W or W / O form), and multiple (e.g., W / O / W, polyol / O / W, and O / W / O) emulsions.

[0033] The components of the composition are described in detail below.

[0034] (Oxide coupler dye) The composition according to the present invention comprises (a) at least one oxide coupler dye. A single type of (a) oxide coupler dye may be used, or two or more different types of (a) oxide coupler dyes may be used in combination.

[0035] (a) The oxidative coupler dye of the present invention produces at least one autocoupling oxidative dye precursor by oxidation. For the purposes of the present invention, the term “autocoupling oxidative dye precursor” means a precursor that produces an oxidative dye by a self-coupling reaction. For the purposes of the present invention, the term “self-coupling” describes a molecule that can couple to itself in a standard oxidizing environment (oxygen in the air) to form new molecules, such as dimers, trimers, and polymers.

[0036] In particular, (a) the oxidation dye precursor is selected from 1-naphthol and 6-hydroxyindole. 1-naphthol and 6-hydroxyindole are 1,8-dihydroxynaphthalene and 5,6-dihydroxyindole, and it is known that these readily self-couple to form oxidation dyes of melanin derivatives of allomelanin and eumelanin, respectively. Allomelanin and eumelanin are known as colorants and can impart color to keratinic substances.

[0037] It is known that 1-naphthol and 6-hydroxyindole have lower human safety and environmental impact than most conventional oxidation precursors and couplers used for hair coloring, while it is also known that their coloring properties are limited or nonexistent.

[0038] Specifically, 1-naphthol and 6-hydroxyindole can be oxidized in situ by the action of the oxidation catalyst of the present invention (b), which will be described later, to form 1,8-dihydroxynaphthalene and 5,6-dihydroxyindole, respectively.

[0039] [ka]

[0040] Subsequently, the generated 1,8-dihydroxynaphthalene and 5,6-dihydroxyindole are spontaneously converted to allomelanin and eumelanin, respectively. The generated allomelanin and eumelanin can diffuse into the keratinous substance, preferably the interior of the hair, to color the keratinous substance. Thus, 1-naphthol and 6-hydroxyindole can be said to be autocoupling oxidative dye precursors, meaning that these compounds are starting materials for the autocoupling of oxidative dyes, resulting in an autocoloring system. 1,8-dihydroxynaphthalene and 5,6-dihydroxyindole autocouple under atmospheric oxygen, and indeed 1-naphthol and 6-hydroxyindole become autocoupling oxidative dye precursors. Because 1,8-dihydroxynaphthalene and 5,6-dihydroxyindole autocouple, the present invention has the advantage that it does not require, and is not essential, the use of coupling 1-naphthol or 6-hydroxyindole with traditional oxidative precursors / bases that are not safe with respect to human health.

[0041] The amount of (a) an oxide coupler dye, preferably 1-naphthol and / or 6-hydroxyindole, in the composition according to the present invention may be 0.05% by mass or more, preferably 0.075% by mass or more, and more preferably 0.1% by mass or more, based on the total mass of the composition.

[0042] The amount of (a) an oxide coupler dye, preferably 1-naphthol and / or 6-hydroxyindole, in the composition according to the present invention may be 3% by mass or less, preferably 1% by mass or less, and more preferably 0.5% by mass or less, based on the total mass of the composition.

[0043] The amount of (a) an oxide coupler dye, preferably 1-naphthol and / or 6-hydroxyindole, in the composition according to the present invention may be in the range of 0.05% to 3% by mass, preferably 0.075% to 1% by mass, and more preferably 0.1% to 0.5% by mass, based on the total mass of the composition.

[0044] In the context of this specification, any combination of the above upper and lower limits may represent a preferred range of quantities.

[0045] (Oxidation catalyst) The compositions according to the present invention include at least one oxidation catalyst selected from (b)(b1) enzymes and (b2) inorganic catalysts. A single type of (b) oxidation catalyst may be used, or two or more different types of (b) oxidation catalysts may be used in combination.

[0046] The (b) oxidation catalyst of the present invention is selected from (b1) an enzyme and (b2) an inorganic catalyst. Each of (b1) the enzyme and (b2) the inorganic catalyst can be used alone, or each of (b1) the enzyme and (b2) the inorganic catalyst can be used in combination.

[0047] As explained above, (b) the oxidation catalyst catalyzes the hydroxylation reaction of (a) 1-naphthol and / or 6-hydroxyindole to produce 1,8-dihydroxynaphthalene and / or 5,6-dihydroxyindole, respectively.

[0048] (b) Examples of substrates for the oxidation catalyst include oxidizing agents such as hydrogen peroxide and peroxide salts such as sodium peroxygenated, potassium peroxide, and calcium peroxide. Preferably, the substrate for the oxidation catalyst is hydrogen peroxide (H2O2).

[0049] (b1) Enzymes and (b2) Inorganic catalysts are described in detail below.

[0050] (b1) Enzyme A single type of (b1) enzyme may be used, or a combination of two or more different types of (b1) enzymes may be used.

[0051] (b1) The enzyme is a biocatalyst well known in the art, and therefore, it can be said that (b1) is a biocatalytic enzyme.

[0052] (b1) The enzyme is not limited as long as it can catalyze the hydroxylation reaction of (a) 1-naphthol and 6-hydroxyindole.

[0053] In a preferred embodiment of the present invention, (b1) the enzyme is selected from peroxygenases (EC1.1.1 and 1.1.2), particularly nonspecific peroxygenases (UPO, EC1.11.2.1). Nonspecific peroxygenases are used in the following reactions: RH + H2O2 ⇔ ROH + H2O (In the formula, R may represent a monovalent organic group, in particular a monovalent hydrocarbon group.) It catalyzes [the process]. Therefore, nonspecific peroxygenases use hydrogen peroxide as a substrate. Consequently, peroxygenases can be used in combination with hydrogen peroxide as an oxidizing agent.

[0054] The use of peroxygenase has the advantage that peroxygenase is more stable than conventional enzymes such as peroxidase, laccase, and tyrosinase, and maintains its activity under ambient conditions.

[0055] (b1) As for commercially available enzymes, one example is nonspecific peroxygenase under the name UPO (nonspecific peroxygenase) provided by Aminoverse.

[0056] If the composition according to the present invention contains (b) at least one (b1) enzyme as an oxidation catalyst, the amount of enzyme (b1) in the composition may be 0.005% by mass or more, preferably 0.01% by mass or more, and more preferably 0.015% by mass or more, based on the total mass of the composition.

[0057] If the composition according to the present invention contains (b) at least one (b1) enzyme as an oxidation catalyst, the amount of enzyme (b1) in the composition may be 0.3% by mass or less, preferably 0.2% by mass or less, and more preferably 0.1% by mass or less, based on the total mass of the composition.

[0058] If the composition according to the present invention contains (b) at least one (b1) enzyme as an oxidation catalyst, the amount of enzyme (b1) in the composition may be in the range of 0.005% to 0.3% by mass, preferably 0.01% to 0.2% by mass, and more preferably 0.015% to 0.1% by mass, relative to the total mass of the composition.

[0059] (b2) Inorganic catalyst A single type of (b2) inorganic catalyst may be used, or a combination of two or more different types of (b2) inorganic catalysts may be used.

[0060] (b2) The inorganic catalyst is not limited as long as it can catalyze the hydroxylation reaction of (a) 1-naphthol and 6-hydroxyindole.

[0061] (b2) The inorganic catalyst is preferably selected from metal catalysts.

[0062] (b2) The inorganic catalyst metal can be selected from, but is not limited to, copper, iron, titanium, magnesium, zinc, cobalt, platinum, cerium, nickel, silver, zirconium, chromium, molybdenum, tungsten, gold, vanadium, and combinations thereof. Preferably, (b2) the inorganic catalyst metal is selected from copper(II), iron(II) or (III), titanium(IV), magnesium(II), and combinations thereof, in particular copper(II).

[0063] The metal catalyst is preferably selected from metal-organic frameworks (MOFs), metal-doped mesoporous structures such as zeolites, metal-organic complexes, and combinations thereof.

[0064] Metal-organic structures (MOFs) may include metal ions and organic ligands having two or more sites capable of coordinating with the metal within the molecule. Examples of organic ligands in MOFs include, for example, dicarboxylic acids and their derivatives, tricarboxylic acids and their derivatives, tetracarboxylic acids and their derivatives, imidazoles and their derivatives, pyrazoles and their derivatives, triazoles and their derivatives, tetraazoles and their derivatives, pyridines and their derivatives, pyrimidines and their derivatives, triazines and their derivatives, and combinations thereof. As a preferred example, the organic ligand of a metal-organic structure (MOF) is selected from tricarboxylic acids and their derivatives.

[0065] A metal-doped mesoporous structure has a mesoporous structure made of an inorganic material. Preferably, a metal-doped mesoporous structure has a mesoporous structure made of a metal oxide. The metal oxide may be an aluminosilicate, preferably a crystalline aluminosilicate. In one preferred embodiment, the metal oxide may be an aluminosilicate material selected from zeolites and zeotype materials. The zeolite framework may be selected from MFI, BEA, MOR, AEL, CHA, ERI, TON, and FER, in particular from BEA and MFI.

[0066] (b2) Metal-organic frameworks (MOFs) as inorganic catalysts and metal-doped mesoporous structures may have a mesoporous or microporous structure. In this embodiment, the pore diameter of the mesoporous or microporous structure may be in the range of 3 to 30 angstroms, preferably 5 to 25 angstroms, and more preferably 7 to 20 angstroms. For the purposes of the present invention, the pore diameter here may mean the diameter of the most abundant pores in the microporous structure. The pore diameter can be measured by any means common in the art, for example, by a pore size distribution plot obtained from nitrogen adsorption-desorption isotherms and by a porosity analyzer.

[0067] (b2) As a commercially available metal-organic framework (MOF) for use as an inorganic catalyst, we can mention the metal-organic framework sold by BASF under the name Basolite F300, which has a tricarboxylic acid-iron network with a pore size of 12 angstroms to 20 angstroms.

[0068] Metal-organic frameworks (MOFs) and (b2) mesoporous structures doped with metal as an inorganic catalyst are typically solid under ambient conditions (25°C, 1 atm). In one embodiment of the present invention, the metal-organic frameworks (MOFs) and the mesoporous structures doped with metal are in the form of particles. In this embodiment, the average (primary) particle diameter may be in the range of 1 nm to 200 nm, preferably 5 nm to 150 nm, and more preferably 10 nm to 100 nm. As used herein, average (primary) particle size or average (primary) particle diameter is the arithmetic mean diameter. As used herein, the term "average primary particle size" may refer to the volume-average size mean diameter given by the statistical particle size distribution for half of the population, D 50 This is referred to as [a specific term]. For example, the volume-average particle size can be measured using a laser diffraction particle size distribution analyzer, such as the Mastersizer 2000 from Malvern Corp.

[0069] Metal-organic frameworks (MOFs) and metal-doped mesoporous structures may have a mesoporous or microporous structure. Metal-organic frameworks (MOFs) and metal-doped mesoporous structures may have a thickness of 25-500 m 2 / g, preferably 50-400m 2 / g, more preferably 70-300m 2The specific surface area (SW) per unit mass can be expressed in the range of / g. The specific surface area per unit mass can be determined by the nitrogen absorption method known as the BET (Brunauer-Emmett-Teller) method, which is described in The Journal of the American Chemical Society, Vol. 60, p. 309, February 1938, and corresponds to the international standard ISO 5794 / 1 (Addendum D). The BET specific surface area corresponds to the total specific surface area of ​​the particle under consideration.

[0070] (b2) Commercially available mesoporous structures doped with metal as inorganic catalysts include: - Zeolite beta-BEA with a pore diameter of 7 angstroms, doped with iron(II), iron(III), or copper(II), supplied by Clariant under the names FeCZB 30, FeCZB 25, and CuCZB 30, respectively, and - Zeolite pentasil MFI with a pore diameter of 5.6 angstroms, doped with iron(II), iron(III), copper(II), or titanium silicate, sold by Clariant under the names FeCZP 30, FeCZP 27, CuCZP 30, and [Ti]CZP, respectively. We can list some examples.

[0071] In a preferred embodiment of the present invention, (b2) the metal-doped mesoporous structure as an inorganic catalyst is selected from zeolite betacopper(II), zeolite pentasylcopper(II), zeolite betairon(II), zeolite betairon(III), zeolite betairon(II), and combinations thereof.

[0072] Metal-organic complexes may contain metal ions and organic ligands that coordinate to the metal ions. The organic ligands of metal-organic complexes can be selected from porphyrin ligands, chlorin ligands, such as chlorophyllin, bacteriochlorin ligands, β-diketone ligands, and combinations thereof. Examples of β-diketone ligands include, but are not limited to, acetylacetonate, dipivaloylmethane, and combinations thereof, with acetylacetonate being preferred. Metal-organic complexes differ from metal-organic structures (MOFs) in that they do not contain porous structures.

[0073] The metal-organic complex is preferably selected from metal acetylacetonates, metal chlorophyllins, and metal phthalocyanines.

[0074] (b2) As for commercially available metal-organic complexes as inorganic catalysts, - Products of metal acetylacetonates, for example, bis(2,4-pentanedione)copper(II) and tris(2,4-pentanedione)iron(III), - Products of metal chlorophyllin, such as sensitive nature col green and chlorophyllin copper complexes, and - Products containing metal phthalocyanines, e.g., copper phthalocyanine and pigment blue 15 We can list some examples.

[0075] In one preferred embodiment of the present invention, (b2) the metal-organic complex as the inorganic catalyst is selected from copper(II) sulfate, iron(II) sulfate, iron(III) sulfate, copper(II) acetacetonate, iron(III) acetacetonate, copper(II) phthalocyanine, copper(II) acetacetonate, iron(III) acetacetonate, and combinations thereof.

[0076] Free metal ions leached from catalysts can be problematic for human health and the environment, but the use of the inorganic catalyst (b2) of the present invention has the advantage of not generating them. In particular, free metal ions can penetrate deep into keratinous materials, which can lead to the breakdown and destruction of protein structures. Since the size of the inorganic catalyst (b2) and enzyme (b1) of the present invention is not small enough to penetrate keratinous materials, these problems are not caused by the use of these oxidation catalysts.

[0077] If the composition according to the present invention contains (b) at least one (b2) inorganic catalyst as an oxidation catalyst, the amount of the (b2) inorganic catalyst in the composition may be 0.05% by mass or more, preferably 0.1% by mass or more, and more preferably 0.2% by mass or more, based on the total mass of the composition.

[0078] If the composition according to the present invention contains (b) at least one (b2) inorganic catalyst as an oxidation catalyst, the amount of the (b2) inorganic catalyst in the composition may be 1% by mass or less, preferably 0.75% by mass or less, and more preferably 0.5% by mass or less, based on the total mass of the composition.

[0079] If the composition according to the present invention contains (b) at least one (b2) inorganic catalyst as an oxidation catalyst, the amount of the (b2) inorganic catalyst in the composition may be in the range of 0.05% to 1% by mass, preferably 0.1% to 0.75% by mass, and more preferably 0.2% to 0.5% by mass, based on the total mass of the composition.

[0080] (Optional components) - Oxidizing agent The compositions according to the present invention can be combined with at least one oxidizing agent immediately before use for coloring or dyeing keratinous substances.

[0081] One type of oxidizing agent may be used alone, or two or more types of oxidizing agents may be used in combination.

[0082] The oxidizing agent can be selected from hydrogen peroxide, peroxygenated salts, and compounds capable of producing hydrogen peroxide by hydrolysis, i.e., from hydrogen peroxide production systems. For example, the oxidizing agent can be selected from aqueous hydrogen peroxide solutions, urea peroxide, alkali metal bromates and ferricyanides, and perates of alkali metals or alkaline earth metals, such as perborates, persulfates, peracids and percarbonates. At least one oxidase enzyme selected from, for example, laccase, peroxidase and 2-electron oxidoreductase, such as uricase, can also be used as an oxidizing agent if appropriate in the presence of their respective donors or cofactors.

[0083] In one preferred embodiment of the present invention, the oxidizing agent is hydrogen peroxide, such as an aqueous solution of hydrogen peroxide.

[0084] If the composition according to the present invention contains at least one oxidizing agent, the amount of the oxidizing agent in the composition may be 0.5% by mass or more, preferably 0.75% by mass or more, and more preferably 1% by mass or more, based on the total mass of the composition.

[0085] If the composition according to the present invention contains at least one oxidizing agent, the amount of the oxidizing agent in the composition may be 20% by mass or less, preferably 15% by mass or less, and more preferably 12.5% ​​by mass or less, based on the total mass of the composition.

[0086] If the composition according to the present invention contains at least one oxidizing agent, the amount of the oxidizing agent in the composition may be in the range of 0.5% to 20% by mass, preferably 0.75% to 15% by mass, and more preferably 1% to 12.5% ​​by mass, based on the total mass of the composition.

[0087] In one embodiment of the present invention, the composition according to the present invention is mixed with an oxidizing composition containing at least one oxidizing agent immediately before being applied to a keratin substance. The mixing ratio of the composition according to the present invention and the oxidizing composition may be 1:3 to 3:1 by mass, preferably 1:2 to 2:1, and more preferably 1:1.5 to 1.5:1.

[0088] If the composition according to the present invention contains at least one oxidizing agent after being mixed with the oxidizing composition, the amount of (a) 1-naphthol or 6-hydroxyindole in the composition may be 0.01% by mass or more, preferably 0.025% by mass or more, and more preferably 0.05% by mass or more, based on the total mass of the composition.

[0089] If the composition according to the present invention contains at least one oxidizing agent after being mixed with the oxidizing composition, the amount of (a) 1-naphthol or 6-hydroxyindole in the composition may be 20% by mass or less, preferably 15% by mass or less, and more preferably 12.5% ​​by mass or less, based on the total mass of the composition.

[0090] If the composition according to the present invention contains at least one oxidizing agent after being mixed with the oxidizing composition, the amount of (a) 1-naphthol or 6-hydroxyindole in the composition may be in the range of 0.01% to 20% by mass, preferably 0.025% to 15% by mass, and more preferably 0.05% to 12.5% ​​by mass, based on the total mass of the composition.

[0091] If the composition according to the present invention contains at least one oxidizing agent after being mixed with the oxidizing composition, the amount of (b) enzyme as an oxidation catalyst in the composition may be 0.0025% by mass or more, preferably 0.005% by mass or more, and more preferably 0.0075% by mass or more, based on the total mass of the composition.

[0092] If the composition according to the present invention contains at least one oxidizing agent after being mixed with the oxidizing composition, the amount of (b) enzyme as an oxidation catalyst in the composition may be 0.2% by mass or less, preferably 0.1% by mass or less, and more preferably 0.05% by mass or less, relative to the total mass of the composition.

[0093] If the composition according to the present invention contains at least one oxidizing agent after being mixed with the oxidizing composition, the amount of (b) enzyme as an oxidation catalyst in the composition may be in the range of 0.0025% to 0.2% by mass, preferably 0.005% to 0.1% by mass, and more preferably 0.0075% to 0.05% by mass, relative to the total mass of the composition.

[0094] If the composition according to the present invention contains at least one oxidizing agent after being mixed with the oxidizing composition, the amount of (b1) enzyme in the composition may be 0.0025% by mass or more, preferably 0.005% by mass or more, and more preferably 0.01% by mass or more, based on the total mass of the composition.

[0095] If the composition according to the present invention contains at least one oxidizing agent after being mixed with the oxidizing composition, the amount of (b1) enzyme in the composition may be 0.2% by mass or less, preferably 0.1% by mass or less, and more preferably 0.05% by mass or less, based on the total mass of the composition.

[0096] If the composition according to the present invention contains at least one oxidizing agent after being mixed with the oxidizing composition, the amount of (b1) enzyme in the composition may be in the range of 0.0025% to 0.2% by mass, preferably 0.005% to 0.1% by mass, and more preferably 0.01% to 0.05% by mass, based on the total mass of the composition.

[0097] If the composition according to the present invention contains at least one oxidizing agent after being mixed with the oxidizing composition, the amount of (b2) inorganic catalyst in the composition may be 0.025% by mass or more, preferably 0.05% by mass or more, and more preferably 0.1% by mass or more, based on the total mass of the composition.

[0098] If the composition according to the present invention contains at least one oxidizing agent after being mixed with the oxidizing composition, the amount of (b2) inorganic catalyst in the composition may be 0.75% by mass or less, preferably 0.5% by mass or less, and more preferably 0.25% by mass or less, based on the total mass of the composition.

[0099] If the composition according to the present invention contains at least one oxidizing agent after being mixed with the oxidizing composition, the amount of (b2) inorganic catalyst in the composition may be in the range of 0.025% to 0.75% by mass, preferably 0.05% to 0.5% by mass, and more preferably 0.1% to 0.25% by mass, based on the total mass of the composition.

[0100] - water The composition typically contains water.

[0101] The amount of water in the composition may be 50% by mass or more, preferably 60% by mass or more, and more preferably 70% by mass or more, based on the total mass of the composition.

[0102] The amount of water in the composition may be 98% by mass or less, preferably 95% by mass or less, and more preferably 90% by mass or less, relative to the total mass of the composition.

[0103] The amount of water in the composition may be in the range of 50% to 98% by mass, preferably 60% to 95% by mass, and more preferably 70% to 90% by mass, relative to the total mass of the composition.

[0104] - Hydrophilic organic solvents acceptable as cosmetics The cosmetic composition according to the present invention may contain at least one hydrophilic organic solvent that is acceptable as a cosmetic. Two or more hydrophilic organic solvents that are acceptable as cosmetic may be used in combination. Therefore, a single hydrophilic organic solvent that is acceptable as a cosmetic, or a combination of different hydrophilic organic solvents that are acceptable as cosmetic may be used.

[0105] Examples of hydrophilic organic solvents acceptable as cosmetics include substantially linear or branched lower monoalcohols having 1 to 8 carbon atoms, such as ethanol, propanol, butanol, isopropanol, and isobutanol; aromatic alcohols, such as benzyl alcohol and phenylethyl alcohol; polyols or polyol ethers, such as propylene glycol, dipropylene glycol, isoprene glycol, butylene glycol, pentylene glycol, glycerin, propanediol, sorbitol, ethylene glycol monomethyl, monoethyl, and monobutyl ethers; propylene glycol ethers, such as propylene glycol monomethyl ether; diethylene glycol alkyl ethers, such as diethylene glycol monoethyl ether or monobutyl ether; polyethylene glycols, such as PEG-4, PEG-6, and PEG-8, and their derivatives, and combinations thereof.

[0106] In a preferred embodiment, the cosmetic composition comprises a linear lower monoalcohol having 1 to 8 carbon atoms, particularly 1 to 4 carbon atoms, especially ethanol, and a hydrophilic organic solvent acceptable as a cosmetic, selected from polyols, particularly diols, particularly propylene glycol, butylene glycol, pentylene glycol, and combinations thereof, to a minimum.

[0107] Hydrophilic organic solvents acceptable as cosmetics may be present in the cosmetic composition in an amount of 3% by mass or more, preferably 5% by mass or more, and more preferably 10% by mass or more, based on the total mass of the composition.

[0108] Hydrophilic organic solvents acceptable as cosmetics may be present in the composition in an amount of 35% by mass or less, preferably 30% by mass or less, and more preferably 25% by mass or less, based on the total mass of the composition.

[0109] Hydrophilic organic solvents acceptable as cosmetics may be present in amounts ranging from 3% to 35% by mass, preferably 5% to 30% by mass, and more preferably 10% to 25% by mass, based on the total mass of the composition.

[0110] - dye The compositions according to the present invention may, without departing from the scope of the present invention, include (a) at least one dye different from the oxidative coupler dye. If two or more dyes are used, they may be the same or different.

[0111] The dye is preferably selected from oxidation dyes.

[0112] Oxidative dyes can be selected from oxidation precursors / bases.

[0113] The oxidation base can be selected from those conventionally known in oxidative staining, preferably from ortho- and para-phenylenediamine, double base, ortho- and para-aminophenol, heterocyclic base, and their acid addition salts.

[0114] especially, - (I) The following equation (I):

[0115] [ka]

[0116] (In the formula, R1 represents a hydrogen atom, a C1-C4 alkyl group, a monohydroxy(C1-C4 alkyl) group, a polyhydroxy(C2-C4 alkyl) group, a (C1-C4) alkoxy(C1-C4) alkyl group, a C1-C4 alkyl group substituted with a nitrogen-containing group, a phenyl group, or a 4'-aminophenyl group. R2 represents a hydrogen atom, a C1-C4 alkyl group, a monohydroxy(C1-C4 alkyl) group, a polyhydroxy(C2-C4 alkyl) group, a (C1-C4)alkoxy(C1-C4)alkyl group, or a C1-C4 alkyl group substituted with a nitrogen-containing group. R1 and R2 may also, together with the nitrogen atom having them, form a 5-membered or 6-membered nitrogen-containing heterocycle which is optionally substituted with one or more alkyl, hydroxyl, or ureido groups. R3 represents a hydrogen atom, a halogen atom such as a chlorine atom, a C1-C4 alkyl group, a sulfo group, a carboxyl group, a monohydroxy(C1-C4 alkyl) group, a hydroxy(C1-C4 alkoxy) group, an acetylamino(C1-C4 alkoxy) group, a mesylamino(C1-C4 alkoxy) group, or a carbamoylamino(C1-C4 alkoxy) group. R4 represents a hydrogen atom, a halogen atom, or a C1-C4 alkyl group. Examples include para-phenylenediamine and their acid addition salts.

[0117] Among the nitrogen-containing groups of formula (I) above, examples include amino, mono(C1-C4)alkylamino, (C1-C4)dialkylamino, (C1-C4)trialkylamino, monohydroxy(C1-C4)alkylamino, di(monohydroxy(C1-C4)alkyl)amino, imidazolinium, and ammonium groups.

[0118] Among the para-phenylenediamines of formula (I) above, more specifically, para-phenylenediamine, para-tolylenediamine, 2-chloro-paraphenylenediamine, 2,3-dimethyl-paraphenylenediamine, 2,6-dimethyl-paraphenylenediamine, 2,6-diethyl-paraphenylenediamine, 2,5-dimethyl-paraphenylenediamine, N,N-dimethylparaphenylenediamine, N,N-diethyl-paraphenylenediamine, N,N-dipropyl-paraphenylenediamine, 4-amino-N,N-diethyl-3-methylaniline, N,N-bis(β-hydroxyethyl)-paraphenylenediamine, 4-N,N-bis(β-hydroxyethyl)amino-2-methylaniline, 4-N,N-bis(β-hydroxyethyl)amino-2-chloroaniline, 2-β-hydroxyethyl-paraphenylenediamine, 2-fluoro-paraphenylenediamine, 2-isopropyl-paraphenylenediamine Examples include amine, N-(β-hydroxypropyl)-paraphenylenediamine, 2-hydroxymethyl-paraphenylenediamine, N,N-dimethyl-3-methylparaphenylenediamine, N,N-(ethyl-β-hydroxyethyl)-paraphenylenediamine, N-(β,γ-dihydroxypropyl)-paraphenylenediamine, N-(4'-aminophenyl)-paraphenylenediamine, N-phenyl-paraphenylenediamine, 2-β-hydroxyethyloxy-paraphenylenediamine, 2-β-acetylaminoethyloxy-paraphenylenediamine, N-(β-methoxyethyl)-paraphenylenediamine, 2-methyl-1-N-β-hydroxyethyl-paraphenylenediamine, N-(4-aminophenyl)-3-hydroxypyrrolidine, 2-[{2-[(4-aminophenyl)amino]ethyl}(2-hydroxyethyl)amino]ethanol, and their acid addition salts.

[0119] Among the para-phenylenediamines of formula (I) above, para-phenylenediamine, para-tolylenediamine, 2-isopropyl-para-phenylenediamine, 2-β-hydroxyethyl-para-phenylenediamine, 2-β-hydroxyethyloxy-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, N,N-bis(β-hydroxyethyl)-para-phenylenediamine, 2-chloro-para-phenylenediamine, and their acid addition salts are most particularly preferred.

[0120] - (II) According to the present invention, “double base” is understood to mean a compound containing at least two aromatic rings having amino and / or hydroxyl groups.

[0121] Among the dual bases, more specifically, examples include N,N'-bis(β-hydroxyethyl)-N,N'-bis(4'-aminophenyl)-1,3-diaminopropanol, N,N'-bis(β-hydroxyethyl)-N,N'-bis(4'-aminophenyl)ethylenediamine, N,N'-bis(4-aminophenyl)-tetramethylenediamine, N,N'-bis(β-hydroxyethyl)-N,N'-bis(4-aminophenyl)tetramethylenediamine, N,N'-bis(4-methylaminophenyl)tetramethylenediamine, N,N'-bis(ethyl)-N,N'-bis(4'-amino-3'-methylphenyl)ethylenediamine, 1,8-bis(2,5-diaminophenoxy)-3,5-dioxaoctane, and their acid addition salts. N,N'-bis(β-hydroxyethyl)-N,N'-bis(4'-aminophenyl)-1,3-diaminopropanol, 1,8-bis(2,5-diaminophenoxy)-3,5-dioxaoctane, or one of the acid addition salts thereof is particularly preferred.

[0122] Among the para-aminophenols, more specifically, we can list para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2-(β-hydroxyethylaminomethyl)phenol, and their acid addition salts.

[0123] - (IV) Ortho-aminophenols that can be used as an oxidation base in the context of the present invention are selected in particular from 2-aminophenol, 2-amino-1-hydroxy-5-methylbenzene, 2-amino-1-hydroxy-6-methylbenzene, 5-acetamide-2-aminophenol, and their acid addition salts.

[0124] - (V) Among the heterocyclic bases that can be used as an oxidation base in the dyeing composition according to the present invention, more specifically, pyridine derivatives, pyrimidine derivatives, pyrazole derivatives, and their acid addition salts can be mentioned.

[0125] Among pyridine derivatives, more specifically, examples include compounds described in patents GB1,026,978 and GB1,153,196, such as 2,5-diaminopyridine, 2-(4-methoxyphenyl)amino-3-aminopyridine, 2,3-diamino-6-methoxypyridine, 2-(β-methoxyethyl)amino-3-amino-6-methoxypyridine, 3,4-diaminopyridine, and their acid addition salts.

[0126] Among pyrimidine derivatives, more specifically, compounds described in, for example, patents DE2359399, JP88-169571 and JP91-10659, or patent application WO96 / 15765, such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine, and pyrazolopyrimidine. Zin derivatives, for example, those listed in patent application FR-A-2750048, include pyrazolo[1,5-a]-pyrimidine-3,7-diamine, 2,5-dimethyl-pyrazolo[1,5-a]-pyrimidine-3,7-diamine, pyrazolo[1,5-a]pyrimidine-3,5-diamine, 2,7-dimethylpyrazolo[1,5-a]pyrimidine-3,5-diamine, 3-aminopyrazolo[1,5-a]pyrimidine-7-ol, 3-aminopyrazolo[ 1,5-a]pyrimidine-5-ol, 2-(3-amino-pyrazolo-[1,5-a]pyrimidine-7-ylamino)ethanol, 2-(7-aminopyrazolo[1,5-a]pyrimidine-3-ylamino)ethanol, 2-[(3-amino-pyrazolo[1,5-a]pyrimidine-7-yl)-(2-hydroxyethyl)amino]ethanol, 2-[(7-aminopyrazolo[1,5-a]-pyrimidine-3-yl)-(2-hydroxyethyl)amino]ethanol, 5,6 Examples include dimethylpyrazolo-[1,5-a]pyrimidine-3,7-diamine, 2,6-dimethylpyrazolo-[1,5-a]pyrimidine-3,7-diamine, 2,5,N7,N7-tetramethylpyrazolo[1,5-a]pyrimidine-3,7-diamine, 3-amino-5-methyl-7-imidazolylpropyl-aminopyrazolo[1,5-a]-pyrimidine, their addition salts, and, if tautomeral equilibrium exists, their tautomerized forms, as well as their acid addition salts.

[0127] Among pyrazole derivatives, more specifically, compounds described in patents DE3843892 and DE4133957, and patent applications WO94 / 08969, WO94 / 08970, FR-A-2733749 and DE19543988, such as 4,5-diamino-1-methylpyrazole, 3,4-diaminopyrazole, 4,5-diamino-1-(4'-chlorobenzyl)-pyrazole, and 4,5-diamino-1,3-dimethylpyrazole. Lu, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino-1-tert-butyl-3-methylpyrazole, 4,5-diamino-1-(β-hydroxyethyl)- Examples include 3-methylpyrazole, 4,5-diamino-1-(β-hydroxyethyl)pyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3-(4'-methoxyphenyl)pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3-methyl-1-isopropylpyrazole, 4-amino-5-(2'-aminoethyl)amino-1,3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole, 3,5-diamino-4-(β-hydroxyethyl)amino-1-methylpyrazole, and their acid addition salts.

[0128] Among the heterocyclic bases that can be used as oxidation bases, more specifically, diaminopyrazolopyrazolone, and in particular 2,3-diamino-6,7-dihydro-1H5H-[pyrazolo1,2,a]pyrazole-1-one, and the acid addition salts of these diaminopyrazolopyrazolones are mentioned.

[0129] Generally, oxidation-based acid addition salts are selected from hydrochlorides, hydrobroms, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfons, phosphates, and acetates.

[0130] The composition according to the present invention may contain at least one autocoupling dye. Examples of autocoupling dyes include all derivatives of dihydroxyindole, e.g., 5,6-dihydroxyindole, 5,6-dihydroxyindolecarboxylic acid and dihydroxyindoline; all derivatives of DOPA, dopaquinone, and dihydroxynaphthalene, e.g., 1,8-dihydroxynaphthalene, trihydroxybenzene, e.g., pyrogallol, hydroxyquinol and phloroglucinol; polyphenols, e.g., tannic acid, tannin, gallic acid, flavonoids (flavones, flavonols, flavonones, isoflavones, anthocyanins, anthocyanidins, catechins, hesperetin and cyanidins); catechol-containing molecules, e.g., caffeic acid, quercetin, epinephrine and norepinephrine; and molecular derivatives of hydroquinone, e.g., lawsone and naphthalezaline.

[0131] The amount of dye in the composition according to the present invention can be in any range, for example, 0.005% to 20% by mass, preferably 0.01% to 10% or more by mass, relative to the total mass of the composition.

[0132] - Adjuvant The composition may contain, or may not contain, any adjuvants typically used in cosmetics, within limits that do not impair the effects of the present invention, such as inorganic or organic powders; anionic, nonionic, amphoteric or zwitter polymers, or mixtures thereof; anionic, cationic and amphoteric surfactants; thickeners; fragrances; antioxidants; pH adjusters, preservatives; chelating agents or sequestering agents; and emulsions.

[0133] The total amount of adjuvant in the composition may be in the range of 0.01% to 30% by mass, preferably 0.1% to 20% by mass, and more preferably 0.5% to 10% by mass, relative to the total mass of the composition.

[0134] The composition can be prepared by mixing the above-mentioned essential and optional components according to any method well known to those skilled in the art.

[0135] According to a preferred embodiment, the composition according to the present invention is, with respect to the total mass of the composition, (a) an oxidative coupler dye in an amount of 0.05% to 3% by mass that generates at least one autocoupling oxidative dye precursor by oxidation, and (b) At least one (b1) enzyme in an amount of 0.005% to 0.3% by mass, or 0.05% to 1% by mass of at least one (b2) inorganic catalyst Includes.

[0136] According to another preferred embodiment, the composition according to the present invention is, with respect to the total mass of the composition, (a) 0.075% to 1% by mass of 1-naphthol or 6-hydroxyindole, (b) 0.01% to 0.2% by mass of at least one (b1) enzyme selected from peroxygenases, Alternatively, at least one (b2) inorganic catalyst selected from metal-organic frameworks (MOFs), metal-doped mesoporous frameworks, and metal-organic complexes, in an amount of 0.1% to 0.75% by mass, wherein the metal is copper, iron, titanium, magnesium, zinc, cobalt, platinum, cerium, nickel, silver, zirconium, chromium, molybdenum, tungsten, gold, vanadium, and combinations thereof, and Includes.

[0137] In another preferred embodiment, the composition according to the present invention is, with respect to the total mass of the composition, (a) 0.1% to 0.5% by mass of 1-naphthol or 6-hydroxyindole, (b) 0.015% to 0.1% by mass of at least one (b1) enzyme selected from nonspecific peroxygenases, Alternatively, at least one (b2) inorganic catalyst comprising 0.2% to 0.5% by mass of a metal-organic structure (MOF) and a mesoporous structure having a mesoporous or microporous structure in which metal is doped internally, wherein the pore diameter is in the range of 3 angstroms to 30 angstroms, preferably 5 angstroms to 25 angstroms, more preferably 7 angstroms to 20 angstroms, the metal-organic complex is selected from metal acetylacetonate, metal chlorophyllin, and metal phthalocyanine, and the metal is selected from copper(II), iron(II) or (III), titanium(IV), magnesium(II), and combinations thereof, and at least one (b2) inorganic catalyst. Includes.

[0138] [kit] The present invention also relates to a kit, preferably a cosmetic kit, more preferably a keratin substance, preferably keratin fibers, and in particular a cosmetic kit for coloring or dyeing hair. (a) Oxidation coupler dyes that produce at least one autocoupling oxidation dye precursor by oxidation, and (b) At least one oxidation catalyst selected from (b1) enzymes and (b2) inorganic catalysts A first compartment containing a first composition including, A second compartment comprising a second composition containing at least one oxidizing agent and Regarding a kit that includes the following:

[0139] The first composition in the kit of the present invention corresponds to the composition according to the present invention as described above.

[0140] The first composition may further contain any of the optional components described above.

[0141] The second composition in the kit of the present invention corresponds to the oxidizing composition described above. Therefore, the oxidizing agent in the second composition is the same as that described in the composition according to the present invention.

[0142] For example, the kit can be used by dispensing or dispensing a first composition from a first compartment and a second composition from a second compartment, and then treating a keratinous substance, preferably keratinous fibers, such as hair, with a mixture of the first and second compositions.

[0143] A mixture of the first composition and the second composition can be considered a ready-to-use composition.

[0144] The mixing ratio of the first composition and the second composition is not limited. The mixing ratio may be 1:3 to 3:1, preferably 1:2 to 2:1, and more preferably 1:1.5 to 1.5:1, as their mass ratio.

[0145] [method] The present invention also relates to a method, preferably a cosmetic method, more preferably a keratin substance, preferably a keratin fiber, and in particular a cosmetic method for coloring or dyeing hair. (1) A step of mixing the first composition and the second composition to prepare a mixture, The first composition is (a) Oxidation coupler dyes that produce at least one autocoupling oxidation dye precursor by oxidation, and (b) At least one oxidation catalyst selected from (b1) enzymes and (b2) inorganic catalysts Includes, The second composition comprises at least one oxidizing agent, and the process is as follows: (2) A step of applying the mixture to a keratin substance and This includes methods.

[0146] The first composition in the kit of the present invention corresponds to the composition according to the present invention as described above.

[0147] The first composition may further contain any of the optional components described above.

[0148] The second composition in the kit of the present invention corresponds to the oxidizing composition described above. Therefore, the oxidizing agent in the second composition is the same as that described in the composition according to the present invention.

[0149] The mixing ratio of the first composition and the second composition is not limited. The mixing ratio may be 1:3 to 3:1, preferably 1:2 to 2:1, and more preferably 1:1.5 to 1.5:1, as their mass ratio.

[0150] The method according to the present invention preferably further includes, with or without drying, a step of washing the keratinous material, such as hair, before and / or after the step of applying a mixture of the first composition and the second composition as a ready-to-use composition to the keratinous material.

[0151] The step of applying the prepared composition onto the keratin material can be carried out using conventional application tools such as brushes, or by hand.

[0152] The keratin material to which the prepared composition has been applied can be left under ambient conditions for an appropriate amount of time required to process the keratin material. The length of the processing time is not limited, but it can be from 1 minute to 24 hours, preferably from 1 minute to 12 hours. For example, the time for dyeing keratin fibers can be from 1 to 120 minutes, preferably from 5 to 60 minutes. [Examples]

[0153] The present invention will be described in more detail by reference to examples. However, these examples should not be construed as limiting the scope of the present invention. The following examples are presented as non-limiting illustrations in the art of the present invention.

[0154] [Composition] Each of the compositions from Examples 1 to 15 (Ex.1 to Ex.15) and Comparative Examples 1 and 2 (Comp.Ex.1 and Comp.Ex.2) was prepared by mixing the components listed in Tables 1 to 4 below. All numerical values ​​regarding the amount of components are based on the "mass%" of the active raw materials.

[0155] [evaluation] For each of the compositions from Examples 1 to 3, 12.5 g of each composition was mixed (in a mass ratio of 1:1) with 12.5 g of an oxidation composition containing 0.04% or 0.4% hydrogen peroxide to prepare the final composition. The formulations of these compositions are shown in Table 1. Therefore, the final composition contained 0.072% by mass of 1-naphthol or 6-hydroxyindole, 0.01% by mass of peroxygenase, and 0.02% by mass (Ex.1) or 0.2% by mass (Ex.2) of hydrogen peroxide.

[0156] For each of the compositions from Examples 3 to 15 and Comparative Examples 1 and 2, 12.5 g of each composition was mixed (mass ratio 1:1) with 12.5 g of an oxidation composition containing 2.7% hydrogen peroxide to prepare the final composition. Therefore, the final composition contained 0.072% by mass of 1-naphthol or 6-hydroxyindole, 0.2% by mass of an inorganic catalyst, and 1.35% by mass of hydrogen peroxide. The formulations of each of the compositions from Examples 3 to 15 and Comparative Examples 1 and 2 are shown in Tables 2 to 4.

[0157] The color of each component in the final composition was evaluated by visual observation (bulk color).

[0158] The following evaluations were performed using the final composition obtained as described above. Two hair swatch samples (1 g, 20 cm) were prepared: one from natural white hair (BN) and the other from pre-sensitized and permed white hair (BP). The hair swatches were completely immersed in the prepared final composition at 25°C for 24 hours. The hair swatches were then rinsed with tap water for 1 minute and dried.

[0159] The color of the colored swatches was evaluated by visual observation. Furthermore, the color was evaluated by measuring colorimetric analysis values ​​(L*, a*, b*, lightness / green-red / blue-yellow) using a Konica Minolta Spectrophotometer CM-3600A. ΔE * The ΔE ratio (between swatches before and after coloring) was calculated. * The larger the value, the better the color characteristics.

[0160] The results are shown in Tables 1 to 4.

[0161] [Table 1]

[0162] [Table 2]

[0163] [Table 3]

[0164] [Table 4]

[0165] As shown in Table 1, the compositions according to Examples 1 and 2, which contain (b1) enzyme as the (b) oxidation catalyst of the present invention, were able to exhibit hair color change properties when combined with (a) oxidation coupler dyes of 1-naphthol or 6-hydroxyindole. When used in combination with at least one peroxygenase, Examples 1 and 2 have a better effect on coloring properties as the concentration of hydrogen peroxide decreases.

[0166] As shown in Tables 2 to 4, the compositions of Examples 3 to 15, which include an inorganic catalyst (b2) as the (b) oxidation catalyst of the present invention, showed improved coloring properties when combined with a (a) oxidation coupler dye of 1-naphthol or 6-hydroxyindole, compared to the compositions of Comparative Examples 1 and 2, which use conventionally used ammonia catalysts.

[0167] Furthermore, the compositions produced by Examples 1 to 15 were able to produce various colors such as brown, yellow, blue, and green, depending on the type of oxidation catalyst used. The present invention can be said to be very useful as a product for coloring or dyeing keratin materials.

[0168] Therefore, it can be concluded that the compositions according to the present invention are very preferable for coloring and / or dyeing keratinous substances.

Claims

1. (a) At least one oxidative coupler dye that generates at least one autocoupling oxidative dye precursor by oxidation, (b) At least one oxidation catalyst selected from (b1) enzymes and (b2) inorganic catalysts A composition containing the following:

2. (a) The composition according to claim 1, wherein the oxidation coupler dye is selected from 1-naphthol and 6-hydroxyindole.

3. (b1) The composition according to claim 1 or 2, comprising at least one enzyme selected from peroxygenases, particularly nonspecific peroxygenases.

4. (b) The composition according to any one of claims 1 to 3, comprising at least one inorganic catalyst selected from metal catalysts.

5. The composition according to claim 4, wherein the metal catalyst is selected from metal-organic frameworks (MOFs), metal-doped mesoporous structures, and metal-organic complexes.

6. The composition according to claim 4 or 5, wherein the metal is selected from copper, iron, titanium, magnesium, zinc, cobalt, platinum, cerium, nickel, silver, zirconium, chromium, molybdenum, tungsten, gold, vanadium, and combinations thereof, preferably selected from copper(II), iron(II) or (III), titanium(IV), magnesium(II), and combinations thereof, particularly copper(II).

7. The composition according to any one of claims 4 to 6, comprising a metal-organic structure (MOF) or a metal-doped mesoporous structure having a mesoporous or microporous structure.

8. The composition according to claim 7, wherein the mesoporous or microporous structure of the metal-organic framework (MOF) or a metal-doped mesoporous structure has pore diameters in the range of 3 angstroms to 30 angstroms, preferably 5 angstroms to 25 angstroms, and more preferably 7 angstroms to 20 angstroms.

9. The composition according to claim 5 or 6, wherein the metal-organic complex comprises an organic ligand selected from porphyrin ligands, chlorin ligands, such as chlorophyllin, bacteriochlorin ligands, β-diketone ligands, and combinations thereof.

10. The composition according to claim 9, wherein the metal-organic complex is selected from metal acetylacetonate, metal chlorophyllin, and metal phthalocyanine.

11. The composition according to any one of claims 1 to 10, wherein the amount of (a) oxide coupler dye in the composition is in the range of 0.05% to 3% by mass, preferably 0.075% to 1% by mass, and more preferably 0.1% to 0.5% by mass, based on the total mass of the composition.

12. The composition according to any one of claims 1 to 3 and 11, wherein the amount of enzyme (b1) in the composition is in the range of 0.005% to 0.3% by mass, preferably 0.01% to 0.2% by mass, and more preferably 0.015% to 0.1% by mass, based on the total mass of the composition.

13. The composition according to any one of claims 1, 2, and 4 to 11, wherein the amount of (b2) inorganic catalyst in the composition is in the range of 0.05% to 1% by mass, preferably 0.1% to 0.75% by mass, and more preferably 0.2% to 0.5% by mass, relative to the total mass of the composition.

14. (a) At least one oxidative coupler dye that generates at least one autocoupling oxidative dye precursor by oxidation, and (b) At least one oxidation catalyst selected from (b1) enzymes and (b2) inorganic catalysts A first compartment containing a first composition including, A second compartment comprising a second composition containing at least one oxidizing agent and A kit that includes the following:

15. A method for coloring or dyeing keratin substances, preferably hair, (1) A step of mixing the first composition and the second composition to prepare a mixture, The first composition is (a) At least one oxidative coupler dye that generates at least one autocoupling oxidative dye precursor by oxidation, and (b) At least one oxidation catalyst selected from (b1) enzymes and (b2) inorganic catalysts Includes, The second composition comprises at least one oxidizing agent. The process, (2) A step of applying the mixture to a keratin substance and Methods that include...

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