Hair color using oxidation dye precursors containing pyrazole primaries and couplers in combination with solubilized vat dyes for improved wash fastness

Abstract

A method and composition for coloring keratinous materials such as mammalian hair, particularly human hair, employs oxidation dye precursors comprising a pyrazole primary and a coupler, and a solubilized vat dye. The method and composition improve the washfastness of hair color produced with oxidation dyes, where one or more oxidation dyes are derived from an oxidation dye precursor comprising a pyrazole primary and a coupler.

Description

[Technical field]

[0001] Background technology Treatments for mammalian or synthetic keratin fibres are known. Mammalian keratin fibres (natural hair) have a structure consisting of a cuticle or outer layer, an inner middle layer, the cortex, which contains melanin or colour bodies and keratin bundles, and a central part called the medulla. Typical dyeing treatments focus on modifying the cortex. Of particular note are cortex treatments, which alter the appearance of the hair, for example by changing the colour or reflective properties of the hair. This can be achieved by treating the hair cortex with a preparation containing dye molecules (so-called direct dyes) which diffuse or are absorbed into the cuticle of the hair fibre. Over time, the colour imparted to the hair is removed during washing, whereas in the case of direct dyes, the colour fade is usually fast. Thus, direct dyes usually result in a short-term change in the appearance of the hair, and the colour imparted to the hair by direct dyes usually lasts only for a few washings.

[0002]

[0002] The most common technique currently used to produce permanent or semi-permanent color changes in hair involves so-called oxidation dyes, where dye precursors (primaries and intermediates called couplers) diffuse into the cortex and then react to form color species in the hair cortex. In many cases, oxidation dyes are designed to lighten the hair and bleach some of the melanin in the cortex, allowing a wider range of colors to be achieved. The color imparted to the hair by the oxidation dye is also removed during washing, but oxidation dyes can last much longer than direct dyes, and in fact, the color is difficult to remove completely, even after a significant number of washes. When the oxidation dye is finally washed off and removed, the melanin has also been bleached, so it does not revert to its original color but reverts to a lighter color, leaving a trace of color in the hair.

[0003]

[0003] Another approach to achieve long-lasting hair color changes involves so-called vat dyes. For example, vat dye pigments (insoluble in aqueous media) can be converted to the corresponding leucobat dye sulfonates by reduction in alkaline media to give the leuco form, which can then be made soluble by treatment with chlorosulfonic acid or simply sulfur trioxide. Leucobat dye sulfonates and their preparation methods are disclosed, for example, in DE 1117242 B. Conversely, leucobat dye sulfonates can be rapidly cleaved to form the classical leuco form of the corresponding vat dye. Subsequent oxidation precipitates the insoluble vat dye as a pigment. The terms "solubilized vat dye", "leucobat dye sulfonates" and "sulfonates of vat dyes" are used interchangeably in this disclosure.

[0004]

[0004] U.S. Patent No. 5,364,415 (Lewis et al.) discloses a hair coloring method based on a mild oxidative hair color system including primary intermediates and couplers, which contemplates the additional application of one of seven selected solubilized vat dyes to the hair as a special color-lightening ingredient to obtain brighter red and yellow colors than can be obtained with typical oxidative colorants alone.

[0005] DE102004014764A1 (Javet et al.) discloses a hair coloring agent comprising a vat dye and a reducing agent which forms enediol under alkaline conditions, which converts the vat dye to the leuco form under alkaline conditions. The document discloses stabilizing the leuco form by suitable packaging, protective gas blankets, the addition of stabilizing and / or protective substances (e.g. polymers, tensides, cationic compounds such as metal ions) or by esterification. DE102004014763A1 (Javet et al.) discloses a similar hair coloring agent in which the vat dye is an indigoid vat dye, which composition also comprises a reducing agent which forms enediol under alkaline conditions and further comprises a cationic compound.

[0006]

[0006] US Patent Application Publication No. 2003 / 0074745 (Vainshalboim et al.) discloses a method and system for dyeing hair without the use of chemical oxidants. The dyes used are solubilized indigoid vat dyes and anthraquinone vat dyes.

[0007]

[0007] U.S. Patent Application Publication No. 2011 / 0189116 (Gauche et al.) discloses a method for coloring a material that includes applying to the material a composition that includes a sulfur-containing nucleophile and applying to the material a composition that includes a dye compound other than a reactive dye.

[0008]

[0008] Solubilized vat dyes are versatile in hair coloring and offer properties comparable to those of oxidative dyes with respect to lightfastness and washfastness, but have not achieved the same commercial importance in hair coloring as oxidative dye systems.

[0009]

[0009] With the advent of pyrazole primaries in the mid-1990s, a new color space became available for fashion hair color, and pyrazole primaries revolutionized hair color, especially in red shades, such as the shade known today as "Vibrant Red." There is extensive literature on pyrazole primaries and their effect on orange-to-red hued hair color, as exemplified by the following patents and patent applications:

[0010]

[0010] EP 0 375 977 discloses oxidation dyes for hair colouring based on precursors such as 3,5-diaminopyrazole and 4,5-diaminopyrazole to produce vibrant hair colours with high colour depth.

[0011] DE 4234885 A1 discloses a process for preparing 4,5-diaminopyrazoles for use as dye precursors in oxidation hair coloring.

[0012]

[0012] US Pat. No. 5,380,340 discloses pyrazole derivatives such as 7-amino-2,3-dihydro-1H-imidazo[1,2-b]pyrazole, 3-nitro-4,5,6,7-tetrahydropyrazolo[1,5-a]pyrimidine or 3-amino-4,5,6,7-tetrahydropyrazolo[1,5-a]pyrimidine for oxidation hair dyeing.

[0013]

[0013] WO 02 / 051372 discloses a composition for the oxidation dyeing of keratin fibres, which comprises at least 4,5- or 3,4-diaminopyrazole or triaminopyrazole and at least certain cellulose compounds.

[0014]

[0014] EP 1 488 783 discloses a dyeing composition comprising 4,5-diamino-1-(beta-hydroxyethyl)-1H-pyrazole or 4,5-diamino-1-(beta-methoxyethyl)-1H-pyrazole as oxidation base and 2,6-dihydroxy-3,4-dimethylpyridine as coupling agent.

[0015]

[0015] EP-A-2 628 731 discloses a composition for the oxidative dyeing of keratinous fibres, in particular human keratinous fibres, which comprises 1-hexyl-1H-pyrazole-4,5-diamine hemisulfate as a primary intermediate.

[0016]

[0016] One of the major drawbacks of known oxidation-based technologies in this field is that the overall washfastness of the coloring experience is not consistent across all shades, including natural shades, fashion shades (such as Vibrant Red), and blonde tones. Even under mildly oxidizing conditions at moderately alkaline pH (such as pH=9), the washfastness of various shades is not consistent. That is, fashionable red tones always tend to wash out at a higher rate than darker natural tones.

[0017]

[0017] Such poor wash fastness of the hair colors produced, especially red fashion shades (i.e. shades produced using diaminopyrazole as primary), has been well known in the art for more than 10 years. For example, US Patent Application Publication No. 2020 / 019728 relates to an oxidative dyeing agent for keratin fibers, which comprises, in a cosmetic carrier, 3-alkyl-4,5-diaminopyrazole, iminodisuccinic acid or a salt thereof, and at least one oxidizing agent other than atmospheric oxygen. The document specifically acknowledges that "many attempts have been made to optimize the color strength and fastness properties of fashion shades. However, despite the many optimization experiments already carried out, there is still a need for improvement in the color fastness properties of oxidatively dyed keratin fibers, especially in terms of fastness properties when dyeing fashion shades in the red range."

[0018]

[0018] Thus, there exists a need for hair coloring compositions and methods that address the aforementioned shortcomings of the known art. Now, surprisingly, with the invention presented herein, a solution has been found that can address and finally resolve all of the shortcomings of conventional oxidative hair colorants as described above at an exceptionally high professional level.

[0019]

[0019] Solubilized vat dyes, particularly those from the broader family of indanthrene dyes (e.g., those characterized by anthraquinone, acridine, perylene, naphthalene, and violanthrone skeletons), when applied in combination with known oxidation primaries and couplers in mild oxidizing media (e.g., hydrogen peroxide levels in the range of 1-12%) have been demonstrated to improve the wash fastness of conventional oxidation hair colors obtained with pyrazole primaries and couplers alone, or with combinations of pyrazole primaries and couplers with direct dyes.

[0020] The color results achieved according to the concept of the present invention show significantly improved color durability, along with exceptional washfastness and lightfastness properties, starting from mild oxidizing conditions with hydrogen peroxide levels below 2% up to higher hydrogen peroxide levels such as 9% or 12%. This concept significantly improves the durability of all shades (natural shades, fashion shades, blonde shades) and provides flexibility and artistic freedom to stylists to create any possible shade. Summary of the Invention

[0021] The present invention addresses the well-known washfastness shortcomings of oxidation dyeing systems using oxidation dye precursors comprising a pyrazole primary and a coupler. According to one aspect, the subject of the present invention is a method for coloring keratinous materials comprising: a1 applying a composition A to the keratinous material, the composition A comprising an aqueous medium and an oxidation dye precursor dissolved in the aqueous medium, the oxidation dye precursor comprising a pyrazole primary and a coupler, the pyrazole primary comprising 4,5-diaminopyrazole, aminopyrazolopyridine, ring-fused 4,5-diaminopyrazolone or a combination thereof; a2 applying composition B to said keratinous material, said composition B comprising an aqueous medium and a solubilized vat dye dissolved in said aqueous medium; b. after step a2, applying a composition C to said keratinous material, said composition C comprising an oxidizing agent; Includes.

[0022]

[0022] According to another aspect, a further subject of the present invention is a ready-to-use hair color formulation, which is obtainable by mixing composition A and composition B, said composition A comprising an aqueous medium and an oxidative dye precursor dissolved in said aqueous medium, said oxidative dye precursor comprising a pyrazole primary and a coupler, said pyrazole primary comprising 4,5-diaminopyrazole, aminopyrazolopyridine, ring-fused 4,5-diaminopyrazolone or a combination thereof, and said composition B comprising an aqueous medium and a solubilized vat dye dissolved in said aqueous medium.

[0023] According to yet another aspect, a further subject of the invention is a kit for dyeing hair. This kit comprises: a compartment A comprising a composition A comprising an aqueous medium and an oxidation dye precursor dissolved in the aqueous medium, the oxidation dye precursor comprising a pyrazole primary and a coupler, the pyrazole primary comprising a 4,5-diaminopyrazole, an aminopyrazolopyridine, a ring-fused 4,5-diaminopyrazolone, or a combination thereof; Compartment B comprising composition B, said composition B comprising an aqueous medium and a solubilized vat dye dissolved in said aqueous medium; and, in separate compartments.

[0024]

[0024] According to yet another aspect, a further subject of the present invention is a hair coloring composition. The hair coloring composition may have a creamy gel-like consistency. Such a gel-like hair coloring composition may comprise one or more solubilized vat dyes, 10.0 to 30.0% by weight of one or more saturated or unsaturated fatty acids, and 50 to 89.50% by weight of water, each of which is based on the weight of the component. Alternatively, the hair coloring composition may have the consistency of a shampoo containing composition. Such shampoo-like hair color compositions may comprise one or more solubilized vat dyes each having a concentration of 0.50 to 2.0% by weight, 2.0 to 40.0% by weight of an anionic surfactant, 2.0 to 20.0% by weight of an amphoteric surfactant, 0 to 10.0% by weight of an optional humectant, and 50.0 to 95.50% by weight of water, where each weight percentage is based on the weight of that component.

[0025] A further subject of the present invention is the use of a hair colouring composition according to the present invention to improve the wash fastness of a hair colour produced with oxidative dyes, the one or more oxidative dyes being derived from an oxidative dye precursor comprising a pyrazole primary and a coupler.A further subject of the present invention is the use of a solubilised vat dye to improve the wash fastness of a hair colour produced with oxidative dyes, the one or more oxidative dyes being derived from an oxidative dye precursor comprising a pyrazole primary and a coupler.

[0026] definition

[0026] As used in this disclosure and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise.

[0027]

[0027] In the context of this application, the term "may" means "is permitted to" or "is able to" and is synonymous with the term "can." As used herein, the term "may" does not imply possibility or likelihood.

[0028]

[0028] In the context of this application, the term "and / or" means one or the other, or both. For example, an aqueous solution of A and / or B means an aqueous solution of A alone, an aqueous solution of B alone, and an aqueous solution of A and B in combination.

[0029]

[0029] The term "about" is understood to mean ±10 percent of a stated numerical value or range of values. According to an embodiment, the term "about" is understood to mean ±2 percent of a stated numerical value or range of values.

[0030]

[0030] The term "about 0% by weight" is understood to mean that the substance, compound or material referred to by zero (0) is not present or is present in negligible but detectable amounts, assuming detectability is on a ppm (parts per million) basis.

[0031]

[0031] When a feature or aspect of the invention is described in a Markush group, one skilled in the art will understand that the invention is also described with any individual element or subgroup of elements of the Markush group. For example, if X is described as being selected from the group consisting of methyl, ethyl, or propyl, a claim in which X is methyl and a claim in which X is methyl and ethyl are fully recited. Furthermore, when a feature or aspect of the invention is described in a Markush group, one skilled in the art will understand that the invention is also described with any individual element or subgroup of elements of the Markush group. Thus, for example, if X is described as being selected from the group consisting of bromine, chlorine, and iodine, and Y is described as being selected from the group consisting of methyl, ethyl, and propyl, a claim in which X is bromine and Y is methyl are fully recited.

[0032]

[0032] When the value of a variable that is necessarily an integer, such as the number of carbon atoms in an alkyl group or the number of substituents on a ring, is described as a range, for example 0 to 4, what is meant is that the value can be any integer between 0 and 4 (including the boundaries), i.e., 0, 1, 2, 3, or 4. Similarly, values ​​expressed in range format are to be interpreted flexibly to include not only the numerical values ​​explicitly stated as boundaries of the range, but also all individual numerical values ​​or subranges encompassed within the range, as if each numerical value and subrange were expressly stated. For example, the range "about 0.1% to about 5%" or "about 0.1% to about 5%" is to be interpreted to include not only about 0.1% to about 5%, but also the individual values ​​(e.g., 1%, 2%, 3%, 4%) and subranges within the stated range (e.g., 0.1% to 0.5%, 1.1% to 2.2%, 3.3% to 4.4%).

[0033]

[0033] As used herein, the term "keratinous materials" refers to natural or synthetic materials made from or containing keratin. In particular, the term "keratinous materials" encompasses natural and synthetic keratinous fibers. Preferred keratinous materials are natural keratinous fibers. Natural keratinous fibers include fibers from and / or of mammals, including humans, primates, ruminants, camelids, equines, rodents, and minks. These animals include, but are not limited to, cattle, sheep, deer, goats, buffalo, llamas, alpacas, camels, guanacos, vicuñas, horses, antelopes, moose, elks, rats, mice, beavers, rabbits, minks, monkeys, apes, and similar species. Natural keratinous fibers include hair, fur, or nails. Particularly preferred keratinous materials in the present disclosure are mammalian keratinous fibers, particularly human hair, and more particularly human scalp hair. In this specification, the term "keratinous fibers" is used interchangeably with the terms "hair" or "hair strands", unless the context indicates otherwise.

[0034]

[0034] As used herein, the term "optionally" means that the corresponding substituent or entity may or may not be present. It includes both possibilities.

[0035]

[0035] As used herein, the term "water soluble" refers to a solubility at 25°C of at least 1.0 wt%, in particular at least 5.0 wt%, for example at least 10.0 wt%, such as at least 25.0 wt%.

[0036]

[0036] The term "composition" as used herein refers to a mixture or blend containing at least two components. A typical composition contains at least one functional component (e.g., leukobat dye sulfonate ester, pH adjuster, oxidizing or reducing agent, etc.) and at least one solvent component (e.g., water or alcohol). The composition may be in any suitable physical form, e.g., liquids of various viscosities, gels, foams, creams, etc. The term "formulation" as used herein refers to a ready-to-use composition, unless the context indicates otherwise. "Ready-to-use" refers to the form in which the composition / formulation is actually applied to keratinous material such as mammalian body hair, particularly human (scalp) hair.

[0037]

[0037] The term "alkalinizing agent" as used herein refers to any compound suitable for adjusting the pH of a composition to an alkaline range. Typical alkalizing agents include bases such as NaOH, ammonia, urea, pyridine, aminomethylpropanol (AMP), monoethanolamine, 2-amino-1-propanol, and DBU (diazabicyclo-undecane). Pyridine and DBU are less preferred because they may cause safety issues.

[0038]

[0038] The term "essentially free" of a particular component means that the amount of each component in the entity is less than 1.0% by weight, based on the total weight of the entity, such as a composition. In particular, the term "essentially free" means that the amount of each component in the entity is less than 0.5% by weight, such as less than 0.1% by weight, such as less than 0.01% by weight. The term "free" of a particular component means an amount below the detection limit, assuming detectability on a ppm (parts per million) basis.

[0039]

[0039] The terms "oxidation dye precursor" or simply "dye precursor" or "color precursor" refer to compounds that can be used in the compositions of the present invention to impart color to keratinous materials and that act as primary intermediates, couplers, or both.

[0040]

[0040] The term "dye" as used herein refers to the reaction product of the "oxidation dye precursor" and the oxidized, insoluble form of the final vat dye. Although the leuco form of the vat dye may be referred to herein as "dye", such leuco form is usually uncolored or has insufficient color depth. As used herein, the term "dye" means at least one absorption maximum in the visible range (400-700 nm) of at least 0.001 AU / g / l, preferably at least 0.01 AU / g / l (absorption units per gram per liter). Furthermore, as used herein, the term "dye" excludes direct dyes. Direct dyes are excluded from the present invention because they have poor washfastness and oxidize under the conditions used in the present invention. Finally, as used herein, the term "dye" does not include inorganic pigments. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0041] The subject of the present invention is a novel and highly versatile concept for dyeing keratinous fibers, in particular mammalian body hair, more particularly human hair. The concept of the present invention is to combine the oxidative hair coloring technology using pyrazole primaries with the vat dye technology for fashion shades. The combination of the two technologies unexpectedly improves the durability or washfastness of the color imparted by the oxidative coloring system, together with the known excellent durability or washfastness of the color imparted by the vat dye.

[0042] Briefly, the present invention involves compositions A and B applied sequentially, simultaneously, or in a mixture to keratinous material such as human hair. Composition A provides an oxidative hair color technology comprising a dye precursor, the oxidative dye precursor comprising one or more pyrazole primaries and one or more couplers. Composition B provides a vat dye technology comprising one or more solubilized vat dyes.

[0043] 1. Composition A and oxidation dye precursor The present invention uses a composition (designated Composition A) with oxidative dye chemistry, which uses an oxidative dye precursor comprising a pyrazole primary (also called a primary intermediate or developer) and a coupler (also called a secondary intermediate). One or more couplers can be used with one or more primaries to obtain different shades. The primaries used may include one or more conventional primaries in addition to the pyrazole primary. Shades contemplated by the present invention include so-called fashion shades, such as shades in the color space including orange, reddish orange, copper, mahogany red, mahogany brownish, and vibrant red, among others.

[0044]

[0044] The oxidative dye precursors suitable for use herein, insofar as they are bases, may be used as free bases or in the form of cosmetically acceptable salts obtained with corresponding organic or inorganic acids, such as hydrochloric acid, hydrobromic acid, citric acid, acetic acid, lactic acid, succinic acid, tartaric acid or sulfonic acid, or, insofar as they have an aromatic hydroxyl group, may be used in the form of cosmetically acceptable salts obtained with corresponding bases, such as alkali phenolates.

[0045] Oxidative dye precursors are known in the art and include aromatic diamines, aminophenols, aromatic diols, and derivatives thereof (a representative list of oxidative dye precursors is provided, but not limited to, in Sagarin, “Cosmetic Science and Technology, Interscience, Special Edn. Vol. 2, pp. 308-310). Suitable oxidative dye precursors are also disclosed in Canadian Patent Application No. 2,576,189, in particular dye combination numbers 1-2394 in Table 1, pages 49-238, which are incorporated herein by reference. The one or more primary intermediates and one or more couplers (collectively referred to as oxidative dye precursors) detailed below are illustrative only and are not intended to limit the invention. The one or more primary intermediates and one or more couplers may be used in the form of any cosmetically acceptable salt, such as a sulfate salt.

[0046] Composition A comprises a pyrazole primary and a coupler, the pyrazole primary comprising a 4,5-diaminopyrazole, an aminopyrazolopyridine, a ring-fused 4,5-diaminopyrazolone, or a combination thereof.

[0047] According to a preferred embodiment, composition A comprises a 4,5-diaminopyrazole according to formula (1): JPEG2025505213000001.jpg37170

[0048] In the above formula, R1 is a linear or branched C1-C6 (hydroxy) alkyl, and R2 is H or a linear or branched C1-C6 (hydroxy) alkyl. Examples of 4,5-diaminopyrazoles according to formula (1) include 1-hydroxyethyl 4,5-diaminopyrazole, 4,5-diamino-1-methylpyrazole, 4,5-diamino-1-ethylpyrazole, 4,5-diamino-1-(iso)propylpyrazole, 4,5-diamino-1-butylpyrazole, 4,5-diamino-1-pentylpyrazole, 4,5-diamino-3-methylpyrazole, and 4,5-diamino-1-hexylpyrazole.

[0048]

[0049] According to certain embodiments, the pyrazole primary in Composition A comprises a 4,5-diaminopyrazole selected from 4,5-diamino-1-methylpyrazole, 4,5-diamino-1-ethylpyrazole, 4,5-diamino-1-hexylpyrazole, 4,5-diamino-1-hydroxyethylpyrazole, 4,5-diamino-3-methylpyrazole, or combinations thereof.

[0049]

[0050] According to an embodiment, composition A comprises an aminopyrazole pyridine according to formula (2): JPEG2025505213000002.jpg29170In the above formula, R3 is (2-hydroxyethyl)oxy or 4,4-dimethylpiperazinium, or a combination thereof.

[0050]

[0051] According to an embodiment, composition A comprises a ring-fused 4,5-diaminopyrazolone according to formula (3): JPEG2025505213000003.jpg34170In the above formula, R4 is methylene, ethylene, propylene, or a combination thereof.

[0051]

[0052] Examples of pyrazole primaries suitable for the present invention but not falling within formula (1) include 4,5-diamino-1-heptylpyrazole, 4,5-diamino-1-benzylpyrazole, 2,3-diamino-6,7-dihydropyrazolo[1,2-a]pyrazol-1(5H)-one.

[0052]

[0053] According to a preferred embodiment, Composition A comprises a pyrazole primary selected from 4,5-diamino-1-methylpyrazole, 4,5-diamino-1-ethylpyrazole, 4,5-diamino-1-hexylpyrazole, 4,5-diamino-1-hydroxyethylpyrazole, 4,5-diamino-3-methylpyrazole, 2,3-diaminodihydropyrazolopyrazolone (CAS#857035-94-0), dimethylpiperazinium aminopyrazolopyridine (CAS#1256553-33-9), 3-amino-2-((2-hydroxyethyl)oxy)-pyrazolo[1,5-a]pyridine (CAS#1079221-49-0) or combinations thereof. According to an even more specific embodiment, Composition A comprises a pyrazole primary selected from 4,5-diamino-1-methylpyrazole, 4,5-diamino-1-ethylpyrazole, 4,5-diamino-1-hexylpyrazole, 4,5-diamino-1-hydroxyethylpyrazole, or combinations thereof.

[0053]

[0054] Examples of conventional primaries that are not pyrazole primaries and that may be present in Composition A in addition to one or more pyrazole primaries include toluene-2,5-diamine, p-phenylenediamine, N-phenyl-p-phenylenediamine, N,N-bis(2-hydroxyethyl)-p-phenylenediamine, 2-hydroxyethyl-p-phenylenediamine, hydroxypropyl-bis-(N-hydroxyethyl-p-phenylenediamine), 3-hydroxypropyl-p-phenylenediamine, 2-methyl-p-phenylenediamine, 2-methoxymethyl-p-phenylenediamine, 2-(1,2-dihydroxyethyl)-p-phenylenediamine, 2,2'-( 2-(4-aminophenylamino)ethylazanediyl)diethanol, 2-(2,5-diamino-4-methoxyphenyl)propane-1,3-diol, 2-(7-amino-2H-benzo[b][1,4]oxazin-4(3H)-yl)ethanol, 2-chloro-p-phenylenediamine, p-aminophenol, p-(methylamino)phenol, 4-amino-m-cresol, 6-amino-m-cresol, 5-ethyl-o-aminophenol, 2-methoxy-p-phenylenediamine, 2,2'-methylenebis-4-aminophenol, 2,4,5,6-tetraaminopyrimidine, 2,5,6-triamino-4-pyrimidinol, and combinations thereof.

[0054]

[0055] According to certain embodiments, conventional primary intermediates optionally present in Composition A may include N,N-bis(2-hydroxyethyl)-p-phenylenediamine, 4-aminophenol, p-phenylenediamine, 3-hydroxypropyl-p-phenylenediamine, 2-methyl-p-phenylenediamine, 2-methoxymethyl-p-phenylenediamine, or combinations thereof.

[0055]

[0056] The one or more couplers may be a compound containing at least one phenyl ring substituted with at least one hydroxyl group. The one or more couplers may be resorcinol, 4-chlororesorcinol, 2-chlororesorcinol, 2-methylresorcinol, 4,6-dichlorobenzene-1,3-diol, 2,4-dimethylbenzene-1,3-diol, m-aminophenol, 4-amino-2-hydroxytoluene, 2-methyl-5-hydroxyethylaminophenol, 3-amino-2,6-dimethylphenol, 3-amino-2,4-dichlorophenol, 5-amino-6-chloro-o-cresol, 5-amino-4 ... -Cresol, 6-hydroxybenzomorpholine, 2-amino-5-ethylphenol, 2-amino-5-phenylphenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol, 2-amino-5-ethoxyphenol, 5-methyl-2-(methylamino)phenol, 2,4-diaminophenoxyethanol, 2-amino-4-hydroxyethylaminoanisole, 1,3-bis-(2,4-diaminophenoxy)-propane, 2,2'-(2-methyl-1,3-phenylene)bis(aza 2,2'-(4,6-diamino-1,3-phenylene)bis(oxy)diethanol, 3-(pyrrolidin-1-yl)aniline, 1-(3-(dimethylamino)phenyl)urea, 1-(3-aminophenyl)urea, 1-naphthol, 2-methyl-1-naphthol, 1,5-naphthalenediol, 2,7-naphthalenediol, 1-acetoxy-2-methylnaphthalene, 4-chloro-2-methylnaphthalene-1-ol, 4-methoxy-2-methylnaphthalene -1-ol, 2,6-dihydroxy-3,4-dimethylpyridine, 2,6-dimethoxy-3,5-pyridinediamine, 3-amino-2-methylamino-6-methoxypyridine, 2-amino-3-hydroxypyridine, 2,6-diaminopyridine, pyridine-2,6-diol, 5,6-dihydroxyindole, 6-hydroxyindole, 5,6-dihydroxyindoline, 3-methyl-1-phenyl-1H-pyrazol-5(4H)-one, 1,2,4-trihydroxybenzene, 2-(benzo[d][1,3]dioxol-5-ylamino)ethanol (also known as hydroxyethyl-3,4-methylenedioxyaniline), phenylmethylpyrazolone, 6-methoxy-2-methylamino-3-aminopyridine, and combinations thereof.

[0056]

[0057] According to certain embodiments, the coupler may include resorcinol, 2-methylresorcinol, hydroxyethyl-3,4-methylenedioxyaniline, m-aminophenol, 1-naphthol, 2-amino-4-hydroxyethylaminoanisole, 4-amino-2-hydroxytoluene, 2-methyl-5-hydroxyethylaminophenol, phenylmethylpyrazolone, 6-hydroxy-benzomorpholine, 6-methoxy-2-methylamino-3-aminopyridine, or combinations thereof.

[0057]

[0058] According to an embodiment, composition A comprises each of the primaries in a concentration of 0.005 to 6.0% by weight, in particular 0.01 to 3.0% by weight, for example 0.2 to 2.0% by weight, relative to the weight of composition A. According to an embodiment, composition A comprises each of the couplers in a concentration of 0.005 to 6.0% by weight, in particular 0.01 to 3.0% by weight, for example 0.2 to 2.0% by weight, relative to the weight of composition A.

[0058]

[0059] Typically, Composition A comprises a total amount of oxidation dye precursors, i.e., one or more couplers, one or more pyrazole primaries, and one or more optional conventional primary intermediates, up to 12.0 wt. %, or from 0.1 to 12.0 wt. %, or from 0.2 to 10.0 wt. %, or from 0.5 to 8.0 wt. %, based on the total weight of Composition A.

[0059] 2. Composition B and solubilized vat dye

[0060] Vat dyes are typically used and known for decades as powerful dyes and pigments for textile dyeing. In particular, those of the indanthrene family show excellent properties in terms of lightfastness, washfastness, are stable to any oxidation events and are extremely weather resistant. Furthermore, they show excellent melting points above 100°C, indicating high chemical stability. The only option to chemically modify them is to apply a reduction process so that they appear in a soluble and therefore processable form. A typical scheme of the conversion options is as follows (Scheme 1):

[0060]

[0061] Scheme 1: JPEG2025505213000004.jpg40170

[0061]

[0062] Vat dyes typically require strong alkaline conditions to be reduced to the corresponding leuco form, which has the ability to penetrate into fibers as a soluble dye. As such conditions (pH>13) cannot be applied to human hair, bypassing via unstable sulfonate esters is the method of choice. As already mentioned, this reactive and soluble form of vat dye pigments is of much less commercial importance than the vat dyes themselves, but was developed to color sensitive fibers (e.g. natural fibers such as silk).

[0062]

[0063] Sulfonate ester vat dyes are perfect candidates, since this structural element opens the space for many chromophores that can be modified in this way. Therefore, this ideal chromophore candidate must have at least two carbonyl groups, to which reduction and oxidation steps can be applied according to Scheme 1 above. When combined with an extended aromatic π-system, typical chromophores are formed, such as the highly stable indanthrene family of chromophores. These solubilized sulfonate ester vat dyes show a totally unexpected ability to penetrate deep into the hair cortex under weakly alkaline conditions (pH=9) in the presence of swelling promoters such as urea, mono-ethanolamine, 2-amino-1-propanol or ammonia. This observation is not trivial, given the size and bulky structure of the chromophores. In comparison with other similarly bulky direct dyes with anionic or cationic charge known in the literature (e.g. azo dyes, anthraquinone dyes), this observed penetration into the hair cortex is very moderate to low, and these conventional direct dyes can only be fixed on the outer surface of the hair, which can be evidenced by cutting the hair diameter under a microscope. This property is therefore remarkable and makes solubilized vat dyes superior to other chromophores for use as permanent hair colorants. After the completion of the penetration stage under alkaline conditions, the cleavage of the unstable sulfonate ester group is forced, usually by lowering the pH value to somewhat weakly acidic conditions (pH = 3.5), to obtain the pure reduced leuco form, which is then rapidly oxidized in the presence of oxygen in the air, hydrogen peroxide, and / or bleaching components such as persulfates. However, even without the acidification step, the cleavage of the sulfonate ester group appears to a considerable extent due to the main instability of the esters in aqueous media, especially when reducing agents such as citric acid or ascorbic acid are present in the formulation. Once the reoxidation is complete, and the vat dye pigments have precipitated in the hair cortex, a very long-lasting hair coloration is achieved due to the absolute insolubility of the pigments formed.

[0063]

[0064] Hair colorants are of high interest to toxicologists and are subject to safety confirmation by authorities before these compounds are used in commercial hair color formulations. Therefore, a careful selection of the appropriate chromophore structure is essential to provide a selection of vat dyes that can be transferred to commercial applications. Our intention is to propose a variety of dedicated vat dyes that are likely to meet all the criteria of toxicological prerequisites. The most important question is whether these dyes have the ability to penetrate the skin. Most of all previously published dyes used for hair coloring show a significant tendency to penetrate, simply caused by their water solubility as hydrophilic, anionic or cationic dyes, which is a mandatory requirement for their processing on the hair fiber, whether applied under non-oxidative or oxidative conditions. Therefore, advanced and costly toxicological evaluations are required to obtain a confirmation of safety by authorities. If penetration into the skin could be eliminated in principle, it would be an important improvement compared to the prior art. It is common sense that pigments such as the final precipitated vat dyes are completely insoluble and not bioavailable and therefore are not subject to further toxicological evaluations. Thus, the focus here is clearly on the solubilized vat dyes as intermediates applied to the hair fiber to process the penetration into the hair cortex. Thus, to obtain an acceptable safety assessment, only chromophores with large extended π-electron systems are considered. Indigoid vat dyes are excluded because their molecular weight is considered too low and they may easily penetrate the skin. On the other hand, the vat dyes and solubilized vat dyes mentioned earlier each exhibit high molecular weights and the chromophore design is characterized by a uniform, extended, bulky polycyclic aromatic hydrocarbon surface. This bulky structure exhibits great hydrophobicity and steric hindrance, significantly reducing the probability of skin penetration. This is also evident from the relatively moderate LogP values ​​of the solubilized vat dyes with significantly less hydrophilicity (see some of the solubilized vat dye LogP values ​​in Scheme 2), if the solubilized vat dyes have a very high solubility in water due to the presence of at least two sulfonate ester groups (see LogWS values).

[0064]

[0065] Scheme 2: TIFF2025505213000005.tif84170

[0065]

[0066] The dyes are selected from the general dye family "indanthrene" dyes, which is a synonym for particularly stable dyes with excellent fastness properties, rather than referring to a dedicated chemical class. Nevertheless, most of the preferred chromophores claimed in this invention are selected from dyes based on naphthalene, perylene, anthraquinone and violanthrone skeletons. As already mentioned, what they all have in common is that they do not have aromatic amine functionality, but at least two carbonyl groups that are modified into solubilized sulfonate ester intermediates that are considered as reactive color components of this oxidation hair dye system.

[0066]

[0067] These commercial dyes are prepared according to standard procedures from commercially available Vat dye pigments (see DE1117242). Reduction is carried out in alkaline medium using n-methylacetamide, potassium boronate or sodium dithionite, followed by sulfation in the presence of sulfur trioxide and dichloroethane as solvent. Alternatively, the reaction can be carried out with chlorosulfonic acid in pyridine as alkalizing agent to give the sulfonate ester. This is illustrated for solubilized Vat Green 1 in Scheme 3.

[0067]

[0068] Scheme 3: JPEG2025505213000006.jpg63170

[0068]

[0069] According to the present invention, Composition B comprises an aqueous medium and a solubilized vat dye dissolved in said aqueous medium. According to an embodiment, Composition B comprises two or more solubilized vat dyes. Typically, the solubilized vat dye in Composition B is a leucobat dye sulfonate ester or a combination of leucobat dye sulfonate esters.

[0069]

[0070] Preferred solubilized Vat dyes for use in the present invention are solubilized Vat Violet 1 (CAS#1324-57-8), solubilized Vat Yellow 4 (CAS#3564-70-3), solubilized Vat Green 1 (CAS#2538-84-3), solubilized Vat Yellow 1 (CAS#6487-09-8), solubilized Vat Red 34 (CAS#12226-70-9), solubilized Vat Red 10 (CAS#10126-90-6), solubilized Vat Orange 9 (CAS#70356-06-8), solubilized Vat Orange 3 (CAS#10290-03-6), solubilized Vat Yellow 7 (CAS#3956-62-5), which conform to the following structure in Scheme 4.

[0070]

[0071] Scheme 4:

[0072] JPEG2025505213000007.jpg69170

[0073] JPEG2025505213000008.jpg70170

[0074] JPEG2025505213000009.jpg74170

[0075] JPEG2025505213000010.jpg81170

[0076] JPEG2025505213000011.jpg60170

[0077] JPEG2025505213000012.jpg59170

[0078] JPEG2025505213000013.jpg70170

[0079] JPEG2025505213000014.jpg77170

[0080] JPEG2025505213000015.jpg63170

[0071]

[0081] According to certain embodiments, Composition B comprises a solubilized vat dye selected from solubilized Vat Yellow 4 (CAS#3564-70-3), solubilized Vat Yellow 1 (CAS#6487-09-8), solubilized Vat Orange 3 (CAS#10290-03-6), solubilized Vat Orange 9 (CAS#70356-06-8), or combinations thereof.

[0072]

[0082] According to an embodiment, composition B comprises each solubilized vat dye in a concentration of 0.50 to 2.0% by weight, in particular in a concentration of 0.6 to 1.5% by weight, for example in a concentration of 0.75 to 1.0% by weight, relative to the weight of composition B. Typically, composition B comprises a total amount of solubilized vat dyes of up to 8.0% by weight, or of 0.5 to 6.0% by weight, or of 1.0 to 5.0% by weight, or of 1.5 to 4.0% by weight, relative to the total weight of composition B.

[0073] 3. Improved washing fastness

[0083] The present invention discloses a highly versatile hair color system based on the combination of oxidative hair color technology using pyrazole primaries and vat dye technology for fashion shades. However, the gist of the present invention is not the combination of oxidative hair color technology and vat dye technology. Instead, the gist of the present invention is the unexpected discovery that the combination of these two technologies results in improved wash fastness of the resulting colors. That is, the superior durability or wash fastness of the colors imparted by the vat dyes is extended to the colors imparted by the oxidative dyes. While such an improvement is believed to be obtainable in essentially all shades (including natural and blonde shades), the effect is most noticeable and clearly visible in the fashion shades (including, for example, "Vibrant Red"). These fashion shades are obtainable with oxidative dye systems containing pyrazole primaries including 4,5-diaminopyrazole, and thus form the starting point of the present invention.

[0074]

[0084] As mentioned at the beginning, U.S. Patent No. 5,364,415 (Lewis et al.) proposed the introduction of solubilized vat dyes as a special color-lightening ingredient in addition to the common oxidation process of applying primaries and couplers to overcome the shortage of oxidative colorants and provide bright fashionable shades. However, back in 1994, pyrazoles (e.g., hydroxyethyl-4,5-diaminopyrazole or hexyl-4,5-diaminopyrazole), the current world standard as primaries to achieve truly intense and brilliant red shades, were not yet in use and were not the subject of this publication. Thus, Lewis et al. focus on the color-lightening effect of mixing solubilized vat dyes with oxidative primaries and couplers to achieve lighter shades. At the time U.S. Patent No. 5,364,415 was filed, this pyrazole blockbuster for creating today's fashion shades was not yet available, and the washfastness issues associated with the use of pyrazole primaries were not yet known. In particular, US Pat. No. 5,364,415 makes no mention whatsoever of washing fastness.

[0075]

[0085] Once the reoxidation is complete, when the vat dye pigments are precipitated in the hair cortex, a very long-lasting hair coloration is achieved due to the absolute insolubility of the pigments formed. This type of coloration therefore provides a high and long-lasting coloration that exhibits superior wash fastness compared to conventional direct dyes added to conventional oxidative hair colorants using primaries and couplers. Even after more than 15 shampoo washes, the hair thus treated remains completely unchanged and without any trace of loss of the entire dye (oxidative coupling product and vat dye, respectively). This observation is noteworthy, since the addition of solubilized vat dye not only adds additional brilliance to conventional oxidative coloration or opens up a whole new color space that is only directly accessible using conventional oxidative hair colorants, but also results in significantly improved wash fastness. This is all the more surprising, especially since it is recognized in the industry that Vibrant Red shades containing pyrazole derivatives known from the literature (e.g., hydroxyethyl-4,5-diamino-pyrazole sulfate or hexyl-4,5-diamino-pyrazole) have a lack of wash fastness and fast fading compared to other shades, which are known issues. Without wishing to be bound by theory, a plausible explanation is apparently that the polyaromatic structure of the indanthrene-related vat dyes acts like a door that closes during precipitation in the hair cortex. The vat dyes are able to find steric space between the protein-based keratin chains and form a complex-type configuration with the keratin. This makes it impossible for other water-soluble and therefore flexible and mobile molecules, such as the coupling products formed by the reaction of the primary with the coupler in conventional oxidation hair colors, to migrate out of the hair, and thus the color shows improved resistance to shampooing. This proposed mechanism appears to be supported by known literature observations.DE10259033 (Langhals, Behrens, Bauer, Speckbacher) describes the placement of water-soluble perylene dyes with very similar polyaromatic ring structures, like solubilized vat dyes, between multiple inorganic layer structures through chromophore intercalation while forming a herringbone pattern at a purpose-specific 45° angle to the layers. Such placement has been verified by X-ray analysis. This proposed concept seems to be further supported by the observation that washing fastness properties are improved when conventional oxidation dyes are applied before or simultaneously with the vat dye. If the solubilized vat dye is applied first and then treated with a conventional oxidation hair color, the color results produced by the addition of the conventional oxidation hair color are only very moderate, and these washing fastnesses are very poor and significantly reduced compared to applications without any treatment of the solubilized vat dye. This observation explains that when the vat dye is applied first, there is not enough space left for the conventional oxidation dye to penetrate into the hair cortex, since the available positions are already effectively blocked by the precipitated vat dye. When proceeding in reverse, ie, when a conventional oxidation dye is applied prior to or simultaneously with the application of the solubilized vat dye, the positive effect of improved washfastness is predictably observed.

[0076]

[0086] Another observation made by the inventors is that the structure and size of the (solubilized) polyaromatic structure of the vat dye influences the washfastness or enhancement obtained. With regard to structure, the best results were obtained with vat dyes having a flatbed polyaromatic structure as opposed to structures with a "kink" such as Vat Blue 4 (CAS#2747-19-5) or Vat Blue 6 (CAS#2519-28-0).

[0077]

[0087] Scheme 5:

[0088] JPEG2025505213000016.jpg73170

[0089] JPEG2025505213000017.jpg57170

[0090] With regard to the size of the planar polyaromatic structure, the inventors have found that a series of aromatic rings such as anthracene or its higher derivatives tetracene or pentacene do not provide optimal results. Rather, to obtain optimal results, a polyaromatic planar chromophore structure consisting of four or more polycondensed rings is required, which planar chromophore structure may optionally contain one or more nitrogen atoms and is understood to include a pyrene structural element according to the following formula (4): JPEG2025505213000018.jpg32170

[0078]

[0091] As an upper limit to achieve optimal results, a polycyclic aromatic planar chromophore structure consisting of up to eight polycondensed rings is required, which may optionally contain one or more nitrogen atoms, and which planar chromophore structure may optionally contain one or more nitrogen atoms, and which is understood to include a pyranthrene structural element according to formula (5) below. JPEG2025505213000019.jpg42170

[0079]

[0092] Optimal results are believed to be achieved with polycyclic aromatic planar chromophore structures consisting of six polycondensed rings, optionally containing one or more nitrogen atoms, said planar chromophore structures comprising a dibenzo-pyrene structural element according to formula (6): JPEG2025505213000020.jpg32170

[0080]

[0093] According to a particular embodiment, composition B comprises a solubilized vat dye selected from solubilized Vat Yellow 4 (CAS#3564-70-3), solubilized Vat Yellow 1 (CAS#6487-09-8), solubilized Vat Orange 3 (CAS#10290-03-6), solubilized Vat Orange 9 (CAS#70356-06-8) or a combination thereof. Vat Yellow 1 and Vat Orange 9 exhibit a polyaromatic tabular chromophore structure of eight polycondensed rings according to formula (5) below. Vat Yellow 4 and Vat Orange 3 exhibit a polyaromatic tabular chromophore structure of six polycondensed rings according to formula (6) below, which is currently believed to be the optimal size of the tabular structure for improved washfastness.

[0081]

[0094] The improved wash fastness achieved according to the teachings of the present invention is evaluated by determining the "as obtained" resultant hair color, i.e. before any washing, and the resultant hair color after 15 standard washing cycles, and determining the color difference. By comparing the difference between the pre-wash color obtained after coloring the hair with the oxidation dye system alone and the color after 15 washing cycles, and the difference between the pre-wash color obtained after coloring the hair with the oxidation dye system plus vat dye, and the color after 15 washing cycles, a factor may be obtained that indicates the improved wash fastness obtained.

[0082]

[0095] It should be noted that since this evaluation involves the comparison of two different shades (one with and one without color imparted by a vat dye), the coefficients obtained are only approximations that indicate the relative improvement in wash fastness. Therefore, this evaluation does not give exact results and the coefficients obtained are qualitative and not quantitative indicators. In order to eliminate the influence of the original hair color (before coloring), the evaluation is carried out using natural white hair.

[0083]

[0096] In other words, the wash fastness improvement can be described as the ratio ΔE(OXID) / ΔE(OXID+VAT), where: ΔE(OXID) is the color difference [(L2-L1) 2+(a2-a1) 2 +(b2-b1) 2 ] 1 / 2 and ΔE(OXID+VAT) is the color difference [(L4-L3) 2 +(a4-a3) 2 +(b4-b3) 2 ] 1 / 2 and L1, a1 and b1 are the CIELAB L*a*b colour coordinates determined on natural grey hair coloured with composition A alone before washing; L2, a2 ​​and b2 are the CIELAB L*a*b colour coordinates determined on natural grey hair coloured with composition A only after 15 standard wash cycles; L3, a3 and b3 are the CIELAB L*a*b colour coordinates determined on natural grey hair coloured with compositions A and B before washing; L4, a4 ​​and b4 are the CIELAB L*a*b colour coordinates determined on natural grey hair coloured with compositions A and B after 15 standard washing cycles.

[0084]

[0097] According to the invention, the ratio ΔE(OXID) / ΔE(OXID+VAT) is preferably greater than or equal to 1.5. According to an embodiment, this ratio is greater than or equal to 2.0, or even greater than or equal to 5.0.

[0085]

[0098] A standard wash cycle is defined as rinsing the colored hair tresses with lukewarm water (25°C) for 10 seconds. Approximately 10 g of commercial shampoo (e.g. SP Color Save Shampoo) is applied to the wet hair tresses and gently rubbed for 30 seconds, followed by rinsing with lukewarm water for another 30 seconds. The tresses are then gently dried with a towel, followed by drying with a hair dryer for 2 minutes. This procedure is then repeated 14 times to achieve a total of 15 wash cycles.

[0086]

[0099] To determine CIELAB L*a*b color coordinates, color is measured using a suitable spectrophotometer, for example a Konica Minolta portable spectrophotometer CM-26D.

[0087]

[0100] The colors produced by the present invention fall within a color space selected from orange, reddish orange, copper, mahogany red, mahogany brownish, or vibrant red.

[0088] 4. Methods for coloring keratinous substances

[0101] The subject of the present invention is a method for coloring keratinous materials. According to an embodiment, the keratinous materials are mammalian body hair, and in particular human hair, such as human head hair. The method comprises the steps of: a1 applying a composition A to the keratinous material, the composition A comprising an aqueous medium and an oxidation dye precursor dissolved in the aqueous medium, the oxidation dye precursor comprising a pyrazole primary and a coupler, the pyrazole primary comprising 4,5-diaminopyrazole, aminopyrazolopyridine, ring-fused 4,5-diaminopyrazolone or a combination thereof; a2 applying composition B to said keratinous material, said composition B comprising an aqueous medium and a solubilized vat dye dissolved in said aqueous medium; b. after step a2, applying a composition C to said keratinous material, said composition C comprising an oxidizing agent; Includes.

[0089]

[0102] As discussed above, Composition A includes an oxidation dye system comprising an oxidation dye precursor comprising a pyrazole primary and a coupler, the pyrazole primary comprising a 4,5-diaminopyrazole, an aminopyrazolopyridine, a ring-fused 4,5-diaminopyrazolone, or a combination thereof, while Composition B includes one or more solubilized vat dyes.

[0090]

[0103] The preferred order of application is to apply composition A to the keratinous material first, followed by composition B, or to apply compositions A and B simultaneously to the keratinous material. If desired, compositions A and B may be mixed before application to the keratinous material and the mixture applied to the keratinous material. The reverse order, i.e., applying composition B to the keratinous material first, followed by composition A, is of course technically possible but is not preferred. If the above-mentioned reverse order of application is used, the intended improvement in wash fastness is not observed.

[0091]

[0104] Composition A preferably exhibits a pH in the weakly alkaline range, i.e. in the range of 8.0 to 11.0, in particular in the range of 8.5 to 9.5, for example a pH of about 9.0, which is the usual pH range used for oxidation dyeing with oxidation colorants using primary and couplers. Similarly, composition B preferably exhibits a pH in the range of 8.0 to 1.0, in particular in the range of 8.5 to 9.5, for example a pH of about 9.0, which is particularly suitable for swelling keratinous materials and allows the pH to be maintained within the range established for the absorption of oxidation dyes.

[0092]

[0105] This makes it particularly suitable for swelling the keratinous material and allows the pH to be maintained within the range established for the absorption of oxidation dyes. This stage is also called the "penetration stage" in this specification. To do this, compositions A and B are kept on the keratinous material for a sufficient time, preferably at least 20 minutes, in particular 20 to 40 minutes. Longer penetration stages are technically of course feasible, but are subject to consumer compliance in beauty salons. A short penetration stage may result in incomplete penetration of the oxidation dye precursors and / or solubilized vat dyes into the keratinous material. The penetration stage usually involves a temperature of 20 to 40°C, in particular 35 to 40°C. The pH during penetration is usually in the range of 8.0 to 11.0, in particular in the range of 8.5 to 9.5, for example a pH of about 9.0.

[0093]

[0106] Optionally, a penetration enhancer can be incorporated into Composition A, Composition B, or both to enhance the penetration of the oxidative dye precursors and solubilized vat dye into the cortex of keratinous materials (such as human hair). Of course, the penetration enhancer can be incorporated separately rather than being a component of Composition A or B. According to embodiments, the penetration enhancer is selected from ammonia, urea, monoethanolamine, 2-amino-1-propanol, or combinations thereof.

[0094]

[0107] During the penetration stage, it is important to keep the sulfonate ester structure intact to avoid, or at least keep within acceptable limits, premature oxidation of the solubilized vat dye, which may interfere with the penetration process and lead to insufficient consumption of the amount of dye applied, and thus to unsatisfactory color results. At that point, a reducing agent may be added to the coloring mixture (especially composition B) to prevent insetting oxidation of the solubilized vat dye. Examples of suitable reducing agents include sodium sulfite, citric acid, ascorbic acid, and similar mild reducing agents, used alone or in combination.

[0095]

[0108] The penetration of the oxidation dye precursors and the solubilized vat dye into the cortex of the keratinous material can be further promoted by applying a heat treatment (during or after) the penetration step. Such a heat treatment may in particular involve treating the keratinous material with a fire having a temperature of 80-230° C. Typical durations of the heat treatment are up to 30 seconds, in particular 2-20 seconds. It is possible to extend the duration of the heat treatment (if any), but care must be taken to avoid (or at least limit) potential damage to keratinous material such as human hair.

[0096]

[0109] As mentioned above, the oxidation dye precursors and solubilized vat dyes can penetrate the cortex of keratinous materials (especially human hair) during the penetration step. It has been observed that lowering the alkaline pH, for example to pH=6, prevents the solubilized vat dyes from penetrating and, in so doing, reduces the swelling of keratinous fibers, which requires slightly alkaline conditions. Furthermore, it is not necessary to force the cleavage of sulfonate esters by lowering the pH to mildly acidic conditions. Rather, it has been observed that the bulky aromatic chromophore system flows deep into the swollen hair cortex without an acidification step, since the cleavage of the sulfonate ester group is likely due to the instability of the sulfonate esters in the aqueous medium itself.

[0097]

[0110] Following the penetration step and optional heat treatment, the oxidative dye precursor and the leukobat dye are oxidized to the oxidative dye and the vat dye, respectively, by applying composition C containing an oxidizing agent to the keratinous material. Any oxidation treatment can be applied. This includes very mild conditions, for example using hydrogen peroxide in a volume of 1.0 to 12.0%. Typical concentrations in the hair coloring industry are: 1.9, 6.0, 9.0 or 12.0% by volume. Composition C typically has a pH in the range of 2.0 to 4.0, in particular in the range of 2.5 to 3.5. However, the pH of composition C does not result in acidification. When compositions A and B are mixed, the overall pH is maintained in the range of 7.0 to 10.0, typically in the range of 8.0 to 10.0, for example in the range of 8.5 to 9.5. Composition C is preferably left on the keratinous material for less than 30 minutes, in particular for 10 to 20 minutes, at a temperature of 20 to 40° C., in particular 35 to 40° C., and at a pH of 8.0 to 11.0.

[0098]

[0111] It is further preferred that the colouring process does not include any acidification step, so that during the application step, the impregnation step, the optional heat treatment and the oxidation treatment, the pH is preferably maintained in the range of 7.0 to 10.0, typically in the range of 8.0 to 10.0, for example in the range of 8.5 to 9.5.

[0099]

[0112] The method may further include conventional post-treatment steps. For example, the keratinous material is typically rinsed after the oxidation step is completed, typically with lukewarm water or water at a temperature of about to slightly above 37° C. Optional further post-treatments include, for example, shampooing, conditioning, drying the keratinous material, or a combination thereof.

[0100]

[0113] Any of Compositions A, B, C may further comprise conventional additives such as pH adjusters, chelating agents, fragrances, care ingredients, texture ingredients, vehicle agents, solvents, surfactants, or combinations thereof.

[0101] 4.1 Oxidation dye precursor in composition A

[0114] Composition A comprises an oxidative dye system as described above. All of the above embodiments, examples and additional information in Chapter 1 apply equally to Composition A used in the method of the present invention. For completeness, the information is repeated below.

[0102]

[0115] Composition A comprises a pyrazole primary and a coupler, the pyrazole primary comprising a 4,5-diaminopyrazole, an aminopyrazolopyridine, a ring-fused 4,5-diaminopyrazolone, or a combination thereof.

[0103]

[0116] According to a preferred embodiment, composition A comprises a 4,5-diaminopyrazole according to formula (1): JPEG2025505213000021.jpg36170

[0117] In the above formula, R1 is linear or branched C1 to C6 (hydroxy)alkyl, and R2 is H or linear or branched C1 to C6 (hydroxy)alkyl.

[0104]

[0118] According to certain embodiments, the pyrazole primary in Composition A comprises a 4,5-diaminopyrazole selected from 4,5-diamino-1-methylpyrazole, 4,5-diamino-1-ethylpyrazole, 4,5-diamino-1-hexylpyrazole, 4,5-diamino-1-hydroxyethylpyrazole, 4,5-diamino-3-methylpyrazole, or combinations thereof.

[0105]

[0119] According to an embodiment, composition A comprises an aminopyrazole pyridine according to formula (2): JPEG2025505213000022.jpg29170In the above formula, R3 is (2-hydroxyethyl)oxy or 4,4-dimethylpiperazinium, or a combination thereof.

[0106]

[0120] According to an embodiment, composition A comprises a ring-fused 4,5-diaminopyrazolone according to formula (3): JPEG2025505213000023.jpg34170In the above formula, R4 is methylene, ethylene, propylene, or a combination thereof.

[0107]

[0121] According to a preferred embodiment, Composition A comprises a pyrazole primary selected from 4,5-diamino-1-methylpyrazole, 4,5-diamino-1-ethylpyrazole, 4,5-diamino-1-hexylpyrazole, 4,5-diamino-1-hydroxyethylpyrazole, 4,5-diamino-3-methylpyrazole, 2,3-diaminodihydropyrazolopyrazolone (CAS#857035-94-0), dimethylpiperazinium aminopyrazolopyridine (CAS#1256553-33-9), 3-amino-2-((2-hydroxyethyl)oxy)-pyrazolo[1,5-a]pyridine (CAS#1079221-49-0) or combinations thereof. According to an even more specific embodiment, Composition A comprises a pyrazole primary selected from 4,5-diamino-1-methylpyrazole, 4,5-diamino-1-ethylpyrazole, 4,5-diamino-1-hexylpyrazole, 4,5-diamino-1-hydroxyethylpyrazole, or combinations thereof.

[0108]

[0122] Typically, Composition A includes one or more conventional primaries in addition to the pyrazole primary. According to certain embodiments, the conventional primary intermediates optionally present in Composition A may include N,N-bis(2-hydroxyethyl)-p-phenylenediamine, 4-aminophenol, p-phenylenediamine, 3-hydroxypropyl-p-phenylenediamine, 2-methyl-p-phenylenediamine, 2-methoxymethyl-p-phenylenediamine, or combinations thereof.

[0109]

[0123] According to certain embodiments, Composition A comprises one or more couplers selected from resorcinol, 2-methylresorcinol, hydroxyethyl-3,4-methylenedioxyaniline, m-aminophenol, 1-naphthol, 2-amino-4-hydroxyethylaminoanisole, 4-amino-2-hydroxytoluene, 2-methyl-5-hydroxyethylaminophenol, phenylmethylpyrazolone, 6-hydroxy-benzomorpholine, 6-methoxy-2-methylamino-3-aminopyridine, or combinations thereof.

[0110]

[0124] According to an embodiment, composition A comprises each of the primaries in a concentration of 0.005 to 6.0% by weight, in particular 0.01 to 3.0% by weight, for example 0.2 to 2.0% by weight, relative to the weight of composition A. According to an embodiment, composition A comprises each of the couplers in a concentration of 0.005 to 6.0% by weight, in particular 0.01 to 3.0% by weight, for example 0.2 to 2.0% by weight, relative to the weight of composition A.

[0111]

[0125] Typically, Composition A comprises a total amount of oxidation dye precursors, i.e., one or more couplers, one or more pyrazole primaries, and one or more optional conventional primary intermediates, up to 12.0 wt. %, or from 0.1 to 12.0 wt. %, or from 0.2 to 10.0 wt. %, or from 0.5 to 8.0 wt. %, based on the total weight of Composition A.

[0112] 4.2 Solubilized vat dye in composition B

[0126] Composition B comprises one or more solubilized vat dyes as described above. All of the above embodiments, examples and additional information in Sections 2 and 3 apply equally to Composition B used in the method of the present invention. For completeness, the information is repeated below.

[0113]

[0127] According to the present invention, Composition B comprises an aqueous medium and a solubilized vat dye dissolved in said aqueous medium. According to an embodiment, Composition B comprises two or more solubilized vat dyes, for example, three or four solubilized vat dyes. Typically, the solubilized vat dye in Composition B is a leucobat dye sulfonate ester or a combination of two or more leucobat dye sulfonate esters.

[0114]

[0128] According to an embodiment, composition B comprises a solubilized vat dye selected from solubilized Vat Violet 1 (CAS#1324-57-8), solubilized Vat Yellow 4 (CAS#3564-70-3), solubilized Vat Green 1 (CAS#2538-84-3), solubilized Vat Yellow 1 (CAS#6487-09-8), solubilized Vat Red 34 (CAS#12226-70-9), solubilized Vat Red 10 (CAS#10126-90-6), solubilized Vat Orange 9 (CAS#70356-06-8), solubilized Vat Orange 3 (CAS#10290-03-6), solubilized Vat Yellow 7 (CAS#3956-62-5) or combinations thereof.

[0115]

[0129] According to certain embodiments, Composition B comprises a solubilized vat dye selected from solubilized Vat Yellow 4 (CAS#3564-70-3), solubilized Vat Yellow 1 (CAS#6487-09-8), solubilized Vat Orange 3 (CAS#10290-03-6), solubilized Vat Orange 9 (CAS#70356-06-8), or combinations thereof.

[0116]

[0130] According to an embodiment, composition B comprises each solubilized vat dye in a concentration of 0.50 to 2.0% by weight, in particular in a concentration of 0.6 to 1.5% by weight, for example in a concentration of 0.75 to 1.0% by weight, relative to the weight of composition B. Typically, composition B comprises a total amount of solubilized vat dyes of up to 8.0%, or 0.5 to 6.0%, or 1.0 to 5.0%, or 1.5 to 4.0%, relative to the total weight of composition B.

[0117]

[0131] According to a preferred embodiment, at least one of the solubilized vat dyes in Composition B exhibits a polyaromatic tabular chromophore structure according to formulas (4), (5) and / or (6), as described above in Chapter 3.

[0118]

[0132] The improvement in washfastness achieved by these solubilized vat dyes in Composition B preferably satisfies the ratio ΔE(OXID) / ΔE(OXID+VAT) described in Chapter 3, which ratio is greater than or equal to 1.5.

[0119] 4.3 Composition A - Formulation Details

[0133] Composition A is suitable for delivering oxidative dye precursors to the hair, is compatible with composition B and preferably has a rheology and viscosity that allows it to be used by professional hairdressers. Suitable formulations include so-called gel network systems, such as those described in EP-A-2 308 564, and oil-based compositions, such as those described in EP-A-2 338 572. According to an embodiment, composition A is preferably free of inorganic pigments, parabens, silicones or combinations thereof.

[0120] 4.3.1 Gel network system

[0134] A gel network thickener system is defined as a thickening system that includes a third component system. The system includes a first anionic surfactant component selected from C14-C30 alkyl phosphates, C14-C30 alkyl ether phosphates, and mixtures thereof, a second component selected from C14-C30 fatty alcohols, and a third nonionic surfactant component selected from polyoxyethylene C14-C30 alkyl ethers. Those skilled in the art will appreciate that gel network thickener systems typically have a complex structure of reticulated lamellar bilayers and / or vesicles, and sometimes crystals. These systems are particularly preferred because they typically have a creamy appearance and feel.

[0121]

[0135] The first anionic surfactant component of the gel network thickener system is selected from C8-C30, preferably C14-C18 alkyl phosphates, C8-C30, preferably C14-C18 alkyl ether phosphates or mixtures thereof. Preferably, the alkyl ether phosphates have an average of 1-20, preferably 1-10, most preferably 1-3 ethylene oxide units. According to an embodiment, composition A comprises at least 1.0%, preferably 1.0-3.0%, more preferably 1.2-2.0% of said first surfactant component by weight of composition A. The first surfactant component aids in the formation of the gel network and is preferably used at the above levels to aid in maintaining the desired rheological range, especially at the upper limit to prevent excessive tackiness.

[0122]

[0136] The gel network system further comprises as a second component a linear or branched C14-C30 fatty alcohol. Most preferably, the second component is selected from cetyl, stearyl, cetostearyl or behenyl alcohol or mixtures thereof. Composition A may comprise 2.0-8.0%, preferably 4.0-6.0%, of said fatty alcohol by weight of Composition A. This second component helps to stabilize the gel network system and also helps to maintain the desired rheological range, especially at the upper end, and prevents excessive stickiness.

[0123]

[0137] The third surfactant component of the gel network thickener system is preferably a non-ionic surfactant selected from polyoxyethylene C14-C30 alkyl ethers containing one or more polyethylene oxide chains having at least about 25, preferably about 50-200, and most preferably about 100-200 ethylene oxide units. Suitable surfactants include ceteareth-25, steareth-100, steareth-150, steareth-200, and mixtures thereof. The third surfactant component acts as a co-emulsifier and stabilizer for the gel network system. Additionally, the third surfactant aids in the formation of a smooth, soft composition. The third surfactant component of the gel network thickener system may be present in an amount of 0.1-5.0% by weight of Composition A.

[0124]

[0138] Two or more of each of the above identified classes of surfactants or components may be used in the gel network. Composition A, when formulated as a gel network system, may comprise a total amount of said first surfactant component, said second surfactant component and said third surfactant component of at least 3.0%, preferably at least 4.0%, more preferably at least 5.0%, by weight of Composition A.

[0125] 4.3.2 Oily compositions

[0139] When formulated as an oily composition, composition A may contain a semi-solid mixture of hydrocarbons (mainly those with a carbon number greater than 25) and fatty alcohols. The hydrocarbons, such as preferably liquid petrolatum, are present in an amount of 10.0-65.0% by weight, preferably 15.0-60.0% by weight. One or more C12-C34 fatty alcohols, such as lauryl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, are preferably present in an amount of 5.0-30.0% by weight, preferably 8.0-20.0% by weight. Fatty alcohols containing C16-C30 linear alkyl chains are preferred.

[0126]

[0140] When formulated as an oil-based composition, Composition A preferably further comprises one or more non-ionic surfactants. Examples of suitable non-ionic surfactants include POE / POP / POE (Poloxamer 184) or oxyethylated C8-C30 alcohols (such as oleyl alcohol (100E)) and mixtures thereof in the range of 5.0-15.0% by weight, preferably 7.0-10.0% by weight.

[0127]

[0141] The viscosity modifier, especially in the form of an organic derivative of hectorite clay, such as distearyldimethylammonium modified hectorite, may be present in an amount of 0.5 to 6.0% by weight, preferably 1.0 to 3.0% by weight.

[0128]

[0142] Solvents such as propylene glycol, ethanol, hexylene glycol, dipropylene glycol or combinations thereof may be present in an amount typically between 2.0 and 15.0% by weight, preferably between 3.0 and 8.0% by weight. Antioxidants such as ascorbic acid may be present in an amount typically between 0.1 and 0.7% by weight.

[0129]

[0143] The optional chelating agents may be the same or different and are typically selected from diethylenetriamine-N,N',N''-polyacid, diethylenetriaminepentaacetic acid (DTPA), diethylenetriaminepenta(methylenephosphonic acid) (DTPMP), ethylenediaminetri(methylenephosphonate), hexamethylenediaminetetra(methylenephosphonate), ethylenediaminedisuccinic acid (EDDS), salts thereof, derivatives thereof, and mixtures thereof. The total amount of chelating agent is usually at least 0.01% by weight, preferably in the range of 0.01 to 5% by weight, more preferably 0.25 to 3% by weight, and even more preferably 0.5 to 2% by weight.

[0130]

[0144] Alkalizing agents such as monoethanolamine or ammonium, sodium hydroxide may typically be present in the range of 2.0-12.0% by weight. Suitable pH adjusters and / or buffers may include, but are not limited to, ammonia, acidulants (such as inorganic acids including phosphoric acid, acetic acid, ascorbic acid, citric acid or tartaric acid, hydrochloric acid, and inorganic acids); alkanolamines (monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, dipropanolamine, tripropanolamine, 2-amino-2-methyl-1-propanol, 2-amino-1-propanol, and 2-amino-2-hydroxymethyl-1,3,-propanediol); guanidinium salts; alkali metals such as sodium hydroxide, tetrasodium pyrophosphate, or ammonium hydroxide and carbonates; and mixtures thereof.

[0131] 4.4 Composition B - Formulation Details

[0145] Composition B is suitable for delivering solubilized vat dye to hair, is compatible with Composition A, and preferably has a rheology and viscosity that is accessible to a professional beauty salon. Suitable formulations include gel-like and shampoo-like systems. According to an embodiment, Composition B is preferably free of inorganic pigments, parabens, silicones, or combinations thereof.

[0132] 4.4.1 Gel-like compositions

[0146] When formulated as a gel-like composition, composition B comprises 10.0-30.0% by weight of one or more saturated or unsaturated fatty acids. According to an embodiment, composition B comprises 12.0-25.0% by weight, in particular 15.0-20.0% by weight, of said one or more saturated or unsaturated fatty acids. Fatty acids suitable for formulating composition B as a gel-like composition preferably exhibit a linear carbon chain length of C12 or more, in particular a linear carbon chain length of C16-C30. Examples of fatty acids include palmitic acid (C16:0), stearic acid (C18:0), palmitoleic acid (C16:1), oleic acid (C18:1), linoleic acid (C18:2), linolenic acid (C18:3) or combinations thereof.

[0133]

[0147] The gel-like composition preferably further comprises 2.0-20.0 wt. % of a rheological agent, in particular the rheological agent is selected from ammonia, monoethanolamine or a combination thereof. According to a preferred embodiment, the gel-like composition exhibits a creamy consistency.

[0134] 4.4.2 Shampoo-like compositions

[0148] Composition B, when formulated as a shampoo-like composition, comprises 2.0 to 40.0% by weight of an anionic surfactant, 2.0 to 20.0% by weight of an amphoteric surfactant, and 0 to 10.0% by weight of an optional humectant.

[0135]

[0149] According to an embodiment, composition B, when formulated as a shampoo-like composition, comprises 4.0 to 25.0 wt. %, in particular 6.0 to 15.0 wt. %, of an anionic surfactant, 3.0 to 15.0 wt. %, in particular 4.0 to 10.0 wt. %, of an amphoteric surfactant, and 1.0 to 8.0 wt. % of a humectant.

[0136]

[0150] According to an embodiment, the anionic surfactant is selected from alkyl sulfates, alkyl ether sulfates, alkyl amido ether sulfates, monoglyceride sulfates, a-olefin sulfonates, paraffin sulfonates, alkyl phosphates, alkyl sulfoacetates, acyl isethionates, alkyl ether phosphates, alkyl phenyl ether sulfonates, N-cocoyl fatty acyl glutamates, N-lauroyl glutamates, N-acyl amino acid salts, N-coconut fatty acyl glycines, N-coconut fatty acyl alanines, salts of alkyl sulfosuccinic acids, and combinations thereof.

[0137]

[0151] According to an embodiment, the amphoteric surfactant is selected from betaines, in particular alkylamidobetaines, alkylbetaines, amidosulfobetaines, carboxybetaine type betaines, sulfobetaine type betaines, hydroxysulfobetaine betaines, phospobetaine type betaines, and combinations thereof.

[0138]

[0152] According to embodiments, the optional humectant is selected from glycerol, glycerol esters, propylene glycol, isopentyl diol, and combinations thereof.

[0139]

[0153] As a specific example of Composition B when formulated as a shampoo-like composition, Composition B may comprise 6.0 to 10.0% by weight sodium laureth sulfate, 4.0 to 6.0% by weight cocoamidopropyl betaine, and 2.0 to 4.0% by weight glycerin.

[0140] 4.5 Composition C - Formulation Details

[0154] Composition C comprises an oxidizing agent. In particular, composition C may comprise hydrogen peroxide, typically in a concentration of 1.0 to 12.0% by volume. Composition C preferably has a pH in the range of 2.0 to 4.0, in particular in the range of 2.5 to 3.5. Composition C may further comprise, as required, a pH adjuster, a chelating agent, a fragrance, a care ingredient, a texture ingredient, a vehicle agent, a solvent, a surfactant. According to an embodiment, composition C preferably does not comprise inorganic pigments, parabens, silicones or combinations thereof. Composition C may be, for example, a commercially available hydrogen peroxide solution, such as the composition sold under the trade name WELLOXON Perfect by Wella.

[0141] 5 Ready-to-use hair color preparations

[0155] A further subject of the present invention is a ready-to-use hair color formulation. The ready-to-use hair color formulation is obtained by mixing composition A as described above with composition B as described above. Composition A comprises an aqueous medium and an oxidation dye precursor dissolved in said aqueous medium, said oxidation dye precursor comprising a pyrazole primary and a coupler, said pyrazole primary comprising 4,5-diaminopyrazole, aminopyrazolopyridine, ring-fused 4,5-diaminopyrazolone or a combination thereof. Composition B comprises an aqueous medium and a solubilized vat dye dissolved in said aqueous medium.

[0142]

[0156] The ready-to-use hair colour preparation preferably exhibits a pH in the weakly alkaline range, ie in the range of from 8.0 to 1.0, in particular in the range of from 8.5 to 9.5, for example a pH of about 9.0.

[0143]

[0157] The ready-to-use hair color formulation may also include a penetration enhancer, especially a penetration enhancer selected from ammonia, urea, monoethanolamine, 2-amino-1-propanol, or combinations thereof.

[0144]

[0158] The oxidation dye precursors, particularly the pyrazole primaries, in the ready-to-use hair color formulations are derived from composition A. Thus, the oxidation dye system is as described above, particularly in Chapter 1. The solubilized vat dyes in the ready-to-use hair color formulations are derived from composition B. Thus, the solubilized vat dye system is as described above, particularly in Chapters 2 and 3.

[0145]

[0159] With respect to the amounts of oxidation dye precursors and solubilized vat dyes, the ready-to-use hair color formulation preferably comprises each primary at a concentration of 0.0025-3.0% by weight, each coupler at a concentration of 0.0025-3.0% by weight, and each solubilized vat dye at a concentration of 0.25-1.0% by weight, all weight % ranges being based on the total weight of the formulation. According to an embodiment, the ready-to-use hair color formulation may comprise each primary at a concentration of 0.005-1.5% by weight, each coupler at a concentration of 0.005-1.5% by weight, and each solubilized vat dye at a concentration of 0.3-0.75% by weight, all weight % ranges being based on the total weight of the formulation. The ready-to-use hair color formulation may comprise a total amount of oxidation dye precursors (couplers, pyrazole primaries and conventional primaries) up to 6.0% by weight, and a total amount of solubilized vat dyes up to 4.0% by weight, all weight % ranges being based on the total weight of the formulation.

[0146]

[0160] The above weight ranges of the oxidative dye precursor and solubilized vat dye mean that to obtain a ready-to-use hair color formulation, composition A and composition B are mixed in similar or equal amounts, i.e. in a weight ratio of about 1:1. However, the ratio of compositions a and B is not critical and it is also possible to mix compositions a and B in a deviating weight ratio, for example A:B in the range of 1:5 to 5:1, to obtain a ready-to-use hair color formulation. However, when compositions A and B are used in a weight ratio other than 1:1, the amounts of oxidative dye precursor and solubilized vat dye in compositions A and B are preferably configured to meet the weight limits above.

[0147] 6 Hair dye kits

[0161] A further subject of the invention is a kit for dyeing hair. The kit comprises in one compartment (or container) composition A as described in chapter 1 above and in a separate compartment (or container) composition B as described in chapters 2-3 above. Composition A comprises an aqueous medium and an oxidative dye precursor dissolved in said aqueous medium, said oxidative dye precursor comprising a pyrazole primary and a coupler, said pyrazole primary comprising 4,5-diaminopyrazole, aminopyrazolopyridine, ring-fused 4,5-diaminopyrazolone or a combination thereof. Compartment B comprises composition B, which comprises an aqueous medium and a solubilized vat dye dissolved in said aqueous medium.

[0148]

[0162] According to an embodiment, the kit may further comprise another separate compartment (or container), which comprises composition C as described above. Composition C comprises an oxidizing agent, in particular hydrogen peroxide, typically in a concentration of 1.0 to 12.0% by volume. Composition C may be, for example, a commercially available hydrogen peroxide solution, such as the composition sold by Wella under the trade name WELLOXON Perfect.

[0149] 7 Hair Color Ingredients

[0163] A further subject of the present invention is a hair coloring composition which is intended for use with commercially available hair coloring and oxidizing solutions, such as the commercially available cream hair color sold under the trade name KOLESTON Perfect by Wella and the commercially available hydrogen peroxide solution sold under the trade name WELLOXON Perfect by Wella.

[0150] 7.1 Gel-like hair color ingredients

[0164] The gel-like hair color composition according to the present invention comprises one or more solubilized vat dyes each having a concentration of 0.50 to 2.0% by weight, one or more saturated or unsaturated fatty acids having a concentration of 10.0 to 30.0% by weight, and water having a concentration of 50 to 89.50% by weight, where each weight percentage is based on the weight of that component.

[0151]

[0165] The solubilized vat dyes are as described above in Chapters 2-3. The gel-like hair color component comprises each solubilized vat dye at a concentration of 0.50-2.0% by weight, particularly at a concentration of 0.6-1.5% by weight, for example 0.75-1.0% by weight, based on the weight of the gel-like hair color component. Typically, the gel-like hair color component comprises a total amount of solubilized vat dyes of up to 8.0% by weight, or 0.5-6.0% by weight, or 1.0-5.0% by weight, or 1.5-4.0% by weight, based on the total weight of the gel-like hair color component.

[0152]

[0166] According to an embodiment, the gel-like hair color component comprises 12.0 to 25.0% by weight, in particular 15.0 to 20.0% by weight, of said one or more saturated or unsaturated fatty acids. Suitable fatty acids preferably exhibit a linear carbon chain length of C12 or more, in particular a linear carbon chain length of C16 to C30. Examples of fatty acids include palmitic acid (C16:0), stearic acid (C18:0), palmitoleic acid (C16:1), oleic acid (C18:1), linoleic acid (C18:2), linolenic acid (C18:3) or combinations thereof.

[0153]

[0167] According to an embodiment, the gel-like hair color component preferably further comprises 2.0 to 20.0 wt. % of a rheological agent selected from ammonia, monoethanolamine, or a combination thereof. According to a preferred embodiment, the gel-like hair color component exhibits a creamy consistency.

[0154]

[0168] The gel-like hair color component may further comprise a penetration enhancer, particularly a penetration enhancer selected from ammonia, urea, monoethanolamine, 2-amino-1-propanol, or combinations thereof (if not already present as the rheological agent).

[0155]

[0169] The gel-like hair color composition may further comprise a reducing agent, particularly sodium sulfite, citric acid, ascorbic acid, or combinations thereof.

[0156]

[0170] The gel-like hair color composition may further comprise one or more ingredients selected from pH adjusters, chelating agents, fragrances, care ingredients, texture ingredients, vehicle agents, solvents, and non-ionic surfactants.

[0157] 7.2 Shampoo-like hair color ingredients

[0171] The shampoo-like hair color composition according to the present invention comprises one or more solubilized vat dyes each having a concentration of 0.50 to 2.0% by weight, 2.0 to 40.0% by weight of an anionic surfactant, 2.0 to 20.0% by weight of an amphoteric surfactant, 0 to 10.0% by weight of an optional humectant, and 50.0 to 95.50% by weight of water, where each weight percentage is based on the weight of that component.

[0158]

[0172] The solubilized vat dyes are as described in Chapters 2-3 above. The shampoo-like hair color composition comprises each solubilized vat dye at a concentration of 0.50-2.0% by weight, particularly at a concentration of 0.6-1.5% by weight, for example 0.75-1.0% by weight, based on the weight of the gel-like hair color component. Typically, the shampoo-like hair color composition comprises a total amount of solubilized vat dyes up to 8.0% by weight, or 0.5-6.0% by weight, or 1.0-5.0% by weight, or 1.5-4.0% by weight, based on the total weight of the shampoo-like hair color component.

[0159]

[0173] According to an embodiment, the shampoo-like hair color composition comprises 4.0 to 25.0 wt. %, particularly 6.0 to 15.0 wt. %, of an anionic surfactant, 3.0 to 15.0 wt. %, particularly 4.0 to 10.0 wt. %, of an amphoteric surfactant, and 1.0 to 8.0 wt. % of a humectant.

[0160]

[0174] According to an embodiment, the anionic surfactant is selected from alkyl sulfates, alkyl ether sulfates, alkyl amido ether sulfates, monoglyceride sulfates, a-olefin sulfonates, paraffin sulfonates, alkyl phosphates, alkyl sulfoacetates, acyl isethionates, alkyl ether phosphates, alkyl phenyl ether sulfonates, N-cocoyl fatty acyl glutamates, N-lauroyl glutamates, N-acyl amino acid salts, N-coconut fatty acyl glycines, N-coconut fatty acyl alanines, salts of alkyl sulfosuccinic acids, and combinations thereof.

[0161]

[0175] According to an embodiment, the amphoteric surfactant is selected from betaines, in particular alkylamidobetaines, alkylbetaines, amidosulfobetaines, carboxybetaine type betaines, sulfobetaine type betaines, hydroxysulfobetaine betaines, phosphobetaine type betaines, and combinations thereof.

[0162]

[0176] According to embodiments, the optional humectant is selected from glycerol, glycerol esters, propylene glycol, isopentyl diol, and combinations thereof.

[0163]

[0177] Specific examples of shampoo-like hair color ingredients include 6.0 to 10.0% by weight sodium laureth sulfate, 4.0 to 6.0% by weight cocoamidopropyl betaine, and 2.0 to 4.0% by weight glycerin.

[0164]

[0178] The shampoo-like hair color composition may also include a penetration enhancer, particularly a penetration enhancer selected from ammonia, urea, monoethanolamine, 2-amino-1-propanol, or combinations thereof.

[0165]

[0179] The shampoo-like hair color composition may further comprise a reducing agent, particularly sodium sulfite, citric acid, ascorbic acid, or combinations thereof.

[0166]

[0180] The shampoo-like hair color composition may further comprise one or more ingredients selected from pH adjusters, chelating agents, fragrances, care ingredients, texture ingredients, vehicle agents, solvents, non-ionic surfactants.

[0167] 8. Use of vat dyes and / or hair color ingredients to improve the wash fastness of hair colors produced by oxidation dyes

[0181] A further subject of the present invention is the use of a solubilized vat dye, essentially as described above, or a hair color component, respectively, as described above in chapter 7, for improving the wash fastness of a hair color produced by an oxidation dye. According to an embodiment, the one or more oxidation dyes are derived from an oxidation dye precursor comprising a pyrazole primary and a coupler, as described above, especially in chapter 1. The solubilized vat dye is as described above, especially in chapters 2-3.

[0168]

[0182] The uses contemplated by the present invention particularly relate to hair colours in the orange, reddish orange, copper, mahogany red, mahogany brownish or vibrant red colour spaces.

[0169]

[0183] The wash fastness improvement can be described as the ratio ΔE(OXID) / ΔE(OXID+VAT), where: ΔE(OXID) is the color difference [(L2-L1) 2 +(a2-a1) 2 +(b2-b1) 2 ] 1 / 2 and ΔE(OXID+VAT) is the color difference [(L4-L3) 2 +(a4-a3) 2 +(b4-b3) 2 ] 1 / 2 and L1, a1 and b1 are the CIELAB L*a*b colour coordinates determined on natural grey hair coloured with composition A alone before washing; L2, a2 ​​and b2 are the CIELAB L*a*b colour coordinates determined on natural grey hair coloured with composition A only after 15 standard wash cycles; L3, a3 and b3 are the CIELAB L*a*b colour coordinates determined on natural grey hair coloured with compositions A and B before washing; L4, a4 ​​and b4 are the CIELAB L*a*b colour coordinates determined on natural grey hair coloured with compositions A and B after 15 standard washing cycles.

[0170]

[0184] According to the invention, the ratio ΔE(OXID) / ΔE(OXID+VAT) is preferably greater than or equal to 1.5. According to an embodiment, this ratio is greater than or equal to 2.0, or even greater than or equal to 5.0.

[0171]

[0185] A standard wash cycle is defined as rinsing the colored hair tresses with lukewarm water (approximately 25°C) for 10 seconds. Approximately 10 g of commercial shampoo (e.g. SP Color Save Shampoo) is applied to the wet hair tresses and gently rubbed for 30 seconds, followed by rinsing with lukewarm water for another 30 seconds. The tresses are then gently dried with a towel, followed by drying with a hair dryer for 2 minutes. This procedure is then repeated 14 times to achieve a total of 15 wash cycles.

[0172]

[0186] To determine CIELAB L*a*b color coordinates, color is measured using a suitable spectrophotometer, for example a Konica Minolta portable spectrophotometer CM-26D. EXAMPLES

[0173]

[0187] The oxidation dyeing process, which uses solubilized vat dyes in combination with traditional oxidation hair dyes, essentially consists of two steps.

[0174] A. Penetration of solubilized vat dye into hair cortex

[0188] This occurs under slightly alkaline conditions at pH=9 in the presence of ammonia, monoethanolamine, 2-amino-1-propanol, or other penetration enhancers (urea, benzyl alcohol, etc.). Oxidized primaries and couplers are optionally added already at this stage, which saves valuable time for the hair stylist when considering the overall application time. Indeed, the first penetration step can be optionally performed without the addition of oxidized primaries and couplers, but these can be added after the penetration time is completed. However, the inventors have realized that there is no merit in doing so. Therefore, it is categorically recommended to apply the mixture (solubilized vat dye and conventional oxidized hair color with primaries and couplers) together, as the obvious advantage of saving valuable application time is clearly beneficial to the present invention. At this point, it is important to keep the sulfonate ester structure intact to avoid premature oxidation of the solubilized vat dye, which would hinder the penetration process and lead to insufficient consumption of the amount of dye applied, which would then result in unsatisfactory color results. To prevent the solubilized vat dye from starting to oxidize at that point, sodium sulfite, citric acid, ascorbic acid, etc. are added to the coloring mixture as reducing agents. In contrast to U.S. Pat. No. 5,364,415 (Lewis et al.), the color result is significantly more intense and vivid if the penetration time is kept between 20 and 30 minutes at pH=9 and 40°C. Furthermore, adding sodium metabisulfite to lower the alkaline pH imparted by the addition of ammonia or urea to pH=6, as described in U.S. Pat. No. 5,364,415 (Lewis et al.), is not beneficial as it prevents the penetration of the solubilized vat dye and reduces the swelling of keratin fibers, which require weakly alkaline conditions. As mentioned above, there is also no need to forcibly cleave the sulfonate esters while lowering the pH to mildly acidic conditions. It has been observed that the bulky aromatic chromophore systems flow deep into the swollen hair cortex without an acidification step, since the cleavage of the sulfonate ester group is believed to be largely due to the instability of the sulfonate esters in the aqueous medium itself. This observation is of great benefit as it dramatically simplifies the actual application in the beauty salon.

[0175] B. Oxidation to precipitate insoluble pigments into the hair cortex

[0189] Once the penetration stage is over, an optional oxidation step can be performed. This includes very mild conditions using 1-12% hydrogen peroxide by volume. The following typical concentrations are common in the hair color industry: 1.9, 6, 9 or 12% by volume. The oxidation process to form the vat dye pigment from the leuco form and the simultaneous lift-up process (while the oxidizing agent continues to also oxidize the natural melanin in the hair) are usually completed within 20 minutes. Thus, the total processing time is less than an hour, which is sufficient for current oxidation hair color applications without increasing the processing complexity. A major advantage is that the use of organic solvents and alcohols (such as ethanol or iso-propyl alcohol) can be completely omitted. In addition, due to the fact that all solubilized vat dyes behave absolutely equally in terms of uniform dye uptake and general fastness properties, all solubilized vat dyes can be easily blended with each other in combination with various pre-formulated shades derived from conventional oxidation hair colorants including primaries and couplers, so that not only formulators and hairstylists but also retail users have the artistic freedom to create any kind of natural and fashionable shades without boundaries.

[0176] General Procedure

[0190] One exemplary color carrier mass of 5 g in the form of a gel and dye mixture, containing oleic acid and / or oleate, has a pH value of 7 to 12.0.Furthermore, this carrier mass contains antioxidants ascorbic acid or sodium sulfite, thickeners xanthan gum or diutan gum, polysaccharides such as glucans, modified and unmodified starches, amylose, amylopectin, glycogen, dextran, cellulose and its derivatives (methylcellulose, hydroxyalkylcellulose, ethylhydroxyethylcellulose and carboxymethylcellulose), complexing agents ethylenediaminetetraacetic acid (EDTA) or / and ethylenediamine-N,N'-disuccinic acid (EDDS), alkalizing agents ammonium or alkanolamines such as monoethanolamine (MEA) or aminomethylpropanol (AMP), care ingredients (amino acids, cationic cellulose, polyquaterniums), perfume oils.

[0177]

[0191] The carrier color mass in the form of a foamable liquid contains anionic surfactants, examples of which include alkyl sulfates, polyoxyethylene alkyl ether sulfates, alkyl phosphates, alkyl phenyl ether sulfonates, N-cocoyl fatty acyl glutamates, N-lauroyl glutamates, N-acyl amino acid salts, N-coconut fatty acyl glycines, N-coconut fatty acyl alanines, and salts of alkyl sulfosuccinic acids, as well as amphoteric surfactants amidosulfobetaines, carbobetaines, sulfobetaines, hydroxysulfobetaines, and phospobetaines. The foamable liquid contains humectants (glycerin, propylene glycol), and the composition contains humectants (glycerin, propylene glycol), thickeners, and preservatives (propylparaben, methylparaben, sodium benzoate). A selected mixture (not limited to examples thereof) according to the following tables (Schemes 6-7) is homogeneously blended with 5 g of a commercial oxidative dye cream (e.g., Koleston Perfect by Wella Professionals © Wella Corporation) that is not pre-formulated with the selected shade.

[0178]

[0192] Scheme 6: Gel-like composition / / Hair color component TIFF2025505213000024.tif70170

[0179]

[0193] Scheme 7: Shampoo-like composition / / Hair color ingredient TIFF2025505213000025.tif77170

[0180]

[0194] The hair strands are then placed on a plate, treated with this mixture and kept for 20 minutes at 35-40 ° C. This infiltration step is carried out at pH = 9, since an alkaline medium is the best for swelling the hair and is established as the world standard for oxidative dye uptake. The hair strands are then placed in an oxidation bath at 35-40 ° C, containing a standard commercial product containing hydrogen peroxide, the so-called color developer, kept at pH = 9 to allow an optimal lift level. Typical contents are 1.9, 6, 9, 12% by volume. The developer can be chosen absolutely freely depending on the grade of lift desired. After 20 minutes, the hair strands are removed and rinsed with lukewarm water to completely remove any traces of oxidizing agents, powder particles, etc., before being washed with shampoo, after-treated with a commercial conditioner and dried with a hair dryer. This aftercare treatment ensures that the hair cortex is closed again and that the hair is transformed so that it returns to its original state with a closed healthy surface. The same process can be applied to the head as described above.

[0181]

[0195] In principle, all common additional components which are typical components of oxidative hair dye mixtures in addition to the above-mentioned components, although not detailed in the exemplary formulations disclosed above, can likewise be applied without exception and without adversely affecting the coloring result. This includes the following common groups of ingredients: colorants (solubilized vat dyes), penetration enhancers / alkalinizing agents (e.g. ammonia, ethanolamine, 2-amino-1-propanol, benzyl alcohol, urea, etc.), reducing agents / radical scavengers (e.g. sodium sulfite, citric acid, ascorbic acid, etc.), chelating agents (e.g. EDTA, EDDS, etidronic acid, etc.), fragrances, care ingredients (e.g. hydrolyzed keratin, dimethicone, polyquaternium types, etc. texture ingredients (e.g. dinutan gum, carbomer, cocoamide, hydroxyethylcellulose, etc.), vehicle agents (e.g. oleic acid, cetearyl alcohol, lanolin alcohol, glyceryl stearate, propylene glycol, etc.), and surfactants (e.g. lauryl ether sulfate, lauryl sulfoacetate, etc.).

[0182]

[0196] The following table (Scheme 8) describes the color obtained using the oxidation dye system alone or in combination with one solubilized vat dye, both immediately after coloring and after 15 standard wash cycles. The oxidation dye system is Wella's brand name Koleston Perfect. The oxidation level is 6% hydrogen peroxide. This lift level is the most common in commercial oxidation permanent hair dyes. All experiments are performed using "natural gray hair" and at a pH of about 9.0.

[0183]

[0197] Scheme 8: TIFF2025505213000026.tif255170TIFF2025505213000027.tif38170

[0184]

[0198] The following table (Scheme 9) describes the coloration obtained using the oxidation dye system alone or in combination with one solubilized vat dye, both immediately after coloring and after 15 standard wash cycles. The oxidation dye system is Wella's brand name Koleston Perfect. The solubilized vat dyes are a combination of "Yellow 4" and "Violet 1" in a 1:1 weight ratio ("Y4 / V1") or a combination of "Yellow 4" and "Green 1" in a 2:1 weight ratio ("Y4 / G1"). The oxidation level is 6% hydrogen peroxide. This lift level is the most common in commercial oxidation permanent hair dyes. All experiments are performed on "natural gray hair" at a pH of about 9.0.

[0185]

[0199] Scheme 9: TIFF2025505213000028.tif188170

[0186]

[0200] The following table (Scheme 10) lists the coloration differences ΔL, Δa and Δb obtained by comparing the L*a*b values ​​of Schemes 8 and 9 above, obtained immediately after coloring, with the L*a*b values ​​obtained after 15 standard washing cycles.

[0187]

[0201] Scheme 10: TIFF2025505213000029.tif225170

[0188]

[0202] Scheme 10 above demonstrates that the improvement in washfastness achieved with vat dyes is significant, with the ratio ΔE(OXID) / ΔE(OXID+VAT) often exceeding 2.0 and in some cases exceeding 10.0.

[0189]

[0203] The following table (Scheme 11) lists the pyrazole primaries, conventional primaries, and couplers present in the Koleston Perfect shades used in the examples above.

[0190]

[0204] Scheme 11: TIFF2025505213000030.tif156170

[0191] The following description further illustrates the invention. 1. A method for coloring keratinous materials, comprising the steps of: a1 applying a composition A to the keratinous material, the composition A comprising an aqueous medium and an oxidation dye precursor dissolved in the aqueous medium, the oxidation dye precursor comprising a pyrazole primary and a coupler, the pyrazole primary comprising 4,5-diaminopyrazole, aminopyrazolopyridine, ring-fused 4,5-diaminopyrazolone or a combination thereof; a2 applying composition B to said keratinous material, said composition B comprising an aqueous medium and a solubilized vat dye dissolved in said aqueous medium; b. after step a2, applying a composition C to said keratinous material, said composition C comprising an oxidizing agent; Includes. 2. The method of claim 1, wherein composition B is applied to said keratinous material simultaneously with or subsequent to application of composition A to said keratinous material. 3. The method of claim 1 or 2, wherein compositions A and B are mixed prior to applying them to said keratinous material. 4. The method of any one of statements 1 to 3, wherein the oxidizing agent comprises hydrogen peroxide, and in particular, the oxidizing agent is hydrogen peroxide at a concentration of 1.0 to 12.0% by volume relative to the volume of composition C. 5. The method of any of statements 1 to 4, wherein composition A has a pH in the range of 8.0 to 11.0, in particular in the range of 8.5 to 9.5, for example a pH of about 9.0. 6. The method according to any one of statements 1 to 5, wherein composition B has a pH in the range of 8.0 to 11.0, in particular in the range of 8.5 to 9.5, for example a pH of about 9.0. 7. The method according to any one of statements 1 to 6, wherein composition C has a pH in the range of 2.0 to 4.0, in particular in the range of 2.5 to 3.5. 8. The method according to any of statements 1 to 7, wherein prior to step b, compositions A and B are maintained on the keratinous material for at least 20 minutes, in particular 20 to 40 minutes, at a temperature of 20 to 40°C, in particular 35 to 40°C, and at a pH of 8.0 to 11.0. 9. The method according to claim 8, further comprising applying a temperature of 80-230° C. to the keratinous material using a fire ignition for up to 30 seconds, in particular for 2-20 seconds, prior to step b. 10. The method according to any of statements 1 to 9, wherein during step b, composition C is maintained on the keratinous material for less than 30 minutes, in particular for 10 to 20 minutes, at a temperature of 20 to 40°C, in particular 35 to 40°C, and at a pH of 8.0 to 11.0. 11. The method of any of statements 1 to 10, wherein during steps a and b the pH is maintained within the range of 8.0 to 10.0, such as within the range of 8.5 to 9.5. 12. The method of any of statements 1 to 11, wherein composition A, B or both further comprises a penetration enhancer. 13. The method of claim 12, wherein the penetration enhancer is selected from ammonia, urea, monoethanolamine, 2-amino-1-propanol, or a combination thereof. 14 Composition A is a compound represented by the formula (1): JPEG2025505213000031.jpg36170, containing 4,5-diaminopyrazole, 14. The method of any of statements 1 to 13, wherein R1 is a linear or branched C1-C6 (hydroxy)alkyl and R2 is H or a linear or branched C1-C6 (hydroxy)alkyl. 15. The method of any one of statements 1 to 14, wherein the 4,5-diaminopyrazole is selected from 4,5-diamino-1-methylpyrazole, 4,5-diamino-1-ethylpyrazole, 4,5-diamino-1-hexylpyrazole, 4,5-diamino-1-hydroxyethylpyrazole, 4,5-diamino-3-methylpyrazole, or a combination thereof. 16 Composition A is a compound represented by the formula (2): JPEG2025505213000032.jpg28170, 16. The method of any one of statements 1 to 15, wherein R3 is (2-hydroxyethyl)oxy or 4,4-dimethylpiperazinium, or a combination thereof. 17 Composition A is a compound represented by formula (3): JPEG2025505213000033.jpg34170, including ring-fused 4,5-diaminopyrazolone, 17. The method of any one of statements 1 to 16, wherein R4 is methylene, ethylene, propylene, or a combination thereof. 18. The method of any of statements 1 to 17, wherein composition A further comprises a conventional primary selected from N,N-bis(2-hydroxyethyl)-p-phenylenediamine, 4-aminophenol, p-phenylenediamine, 3-hydroxypropyl-p-phenylenediamine, 2-methyl-p-phenylenediamine, 2-methoxymethyl-p-phenylenediamine, or a combination thereof. 19. The method of any of statements 1 to 18, wherein composition A comprises each primary in a concentration of 0.005 to 6.0% by weight or 0.01 to 3.0% by weight, based on the weight of composition A. 20. The method of any of statements 1 to 19, wherein composition A comprises a coupler selected from resorcinol, 2-methylresorcinol, hydroxyethyl-3,4-methylenedioxyaniline, m-aminophenol, 1-naphthol, 2-amino-4-hydroxyethylaminoanisole, 4-amino-2-hydroxytoluene, 2-methyl-5-hydroxyethylaminophenol, phenylmethylpyrazolone, 6-hydroxy-benzomorpholine, 6-methoxy-2-methylamino-3-aminopyridine, or a combination thereof. 21. The method of any of statements 1 to 20, wherein composition A comprises each coupler in a concentration of 0.005 to 6.0 wt % or 0.01 to 3.0 wt %, based on the weight of composition A. 22. The method of any of statements 1 to 21, wherein composition B comprises two or more solubilized vat dyes. 23. The method of any of statements 1 to 22, wherein the solubilized vat dye in composition B is a leucovat dye sulfonate ester or a combination of leucovat dye sulfonate esters. 24. The method of any of statements 1 to 23, wherein composition B comprises a solubilized vat dye selected from solubilized Vat Violet 1 (CAS#1324-57-8), solubilized Vat Yellow 4 (CAS#3564-70-3), solubilized Vat Green 1 (CAS#2538-84-3), solubilized Vat Yellow 1 (CAS#6487-09-8), solubilized Vat Red 34 (CAS#12226-70-9), solubilized Vat Red 10 (CAS#10126-90-6), solubilized Vat Orange 9 (CAS#70356-06-8), solubilized Vat Orange 3 (CAS#10290-03-6), solubilized Vat Yellow 7 (CAS#3956-62-5), or a combination thereof. 25 Composition B comprises a solubilized vat dye comprising a polycyclic aromatic tabular chromophore structure consisting of four or more polycondensed rings, optionally containing one or more nitrogen atoms, the tabular chromophore structure being represented by formula (4): 25. A method according to any of claims 1 to 24, comprising a pyrene structural element according to JPEG2025505213000034.jpg32170. 26 The solubilized vat dye comprises a polycyclic aromatic tabular chromophore structure of up to eight polycondensed rings, optionally containing one or more nitrogen atoms, the tabular chromophore structure being represented by formula (5): The method described in claim 25, comprising a pyranthrene structural element according to JPEG2025505213000035.jpg39170. 27 The solubilized vat dye comprises a polycyclic aromatic tabular chromophore structure consisting of six polycondensed rings, optionally containing one or more nitrogen atoms, the tabular chromophore structure being represented by formula (6): The method according to any one of claims 25 to 26, comprising a dibenzopyrene structural element according to JPEG2025505213000036.jpg33170. 28. The method of any of statements 1 to 27, wherein composition B comprises a solubilized vat dye selected from solubilized Vat Yellow 4 (CAS#3564-70-3), solubilized Vat Yellow 1 (CAS#6487-09-8), solubilized Vat Orange 3 (CAS#10290-03-6), solubilized Vat Orange 9 (CAS#70356-06-8), or a combination thereof. 29. The method of any of statements 1 to 28, wherein composition B comprises a reducing agent, in particular sodium sulfite, citric acid, ascorbic acid or a combination thereof. 30. The method of any of statements 1 to 29, wherein composition B comprises each solubilized vat dye at a concentration of 0.50 to 2.0 weight percent, based on the weight of composition B. 31. The method of any of statements 1 to 30, wherein one or more of compositions A, B, C further comprises one or more ingredients selected from pH adjusters, chelating agents, fragrances, care ingredients, texture ingredients, vehicle agents, solvents, surfactants. 32. The method of any of statements 1 to 31, wherein composition A comprises at least 1.0 wt.% of one or more anionic surfactants, at least 2.0 wt.% of one or more linear or branched C14 to C30 fatty alcohols, and at least 0.1 wt.% of one or more nonionic surfactants. 33. The method of any of statements 1 to 31, wherein composition A comprises at least 10% by weight of one or more hydrocarbons and at least 5.0% by weight of one or more fatty alcohols. 34. The method of any of statements 1 to 33, wherein composition B comprises 10.0 to 30.0 wt. of one or more fatty acids. 35. The method of claim 34, wherein composition B comprises 2.0-20.0 wt. % of a rheological agent selected from ammonia, monoethanolamine, or a combination thereof. 36. The method of any of statements 1 to 33, wherein composition B comprises 2.0 to 40.0 wt. % anionic surfactant, 2.0 to 20.0 wt. % amphoteric surfactant, and 0 to 10.0 wt. % optional humectant. 37. The method of any of statements 1 to 36, wherein one or more of compositions A, B, C is essentially free of pigments, parabens, silicones, or combinations thereof. 38. The method of any of statements 1 to 37, wherein the color produced is within a color space selected from orange, reddish orange, copper, mahogany red, mahogany brownish, or vibrant red. 39 The resulting improvement in washing fastness ΔE(OXID) / ΔE(OXID+VAT) is 1.5 or more, ΔE(OXID) is the color difference [(L2-L1) 2 +(a2-a1) 2 +(b2-b1) 2 ] 1 / 2 and ΔE(OXID+VAT) is the color difference [(L4-L3) 2 +(a4-a3) 2 +(b4-b3) 2 ] 1 / 2 and L1, a1 and b1 are the CIELAB L*a*b colour coordinates determined on natural grey hair coloured with composition A alone before washing; L2, a2 ​​and b2 are the CIELAB L*a*b colour coordinates determined on natural grey hair coloured with composition A only after 15 standard wash cycles; L3, a3 and b3 are the CIELAB L*a*b colour coordinates determined on natural grey hair coloured with compositions A and B before washing; L4, a4 ​​and b4 are the CIELAB L*a*b colour coordinates determined on natural grey hair coloured with compositions A and B after 15 standard washing cycles; 39. The method of any one of statements 1 to 38. 40. The method of any of statements 1 to 39, further comprising rinsing the keratinous material following step b, and optionally further comprising a post-treatment comprising shampooing, conditioning, drying the keratinous material, or a combination thereof. 41. A method according to any of statements 1 to 40, wherein the keratinous material is mammalian hair, in particular human hair. 42. A ready-to-use hair color formulation, the hair color formulation being obtainable by mixing composition A and composition B, the composition A comprising an aqueous medium and an oxidative dye precursor dissolved in the aqueous medium, the oxidative dye precursor comprising a pyrazole primary and a coupler, the pyrazole primary comprising 4,5-diaminopyrazole, aminopyrazolopyridine, ring-fused 4,5-diaminopyrazolone or a combination thereof, and the composition B comprising an aqueous medium and a solubilized vat dye dissolved in the aqueous medium. 43. A formulation according to statement 42, having a pH in the range of 8.0 to 11.0, in particular in the range of 8.5 to 9.5, for example a pH of about 9.0. 44. The formulation of statement 42 or 43, further comprising a penetration enhancer. 45. The formulation of statement 44, wherein the penetration enhancer is selected from ammonia, urea, monoethanolamine, 2-amino-1-propanol, or combinations thereof. 46 Formula (1): JPEG2025505213000037.jpg36170, containing 4,5-diaminopyrazole, 46. ​​A formulation according to any of statements 42 to 45, wherein R1 is linear or branched C1-C6 (hydroxy)alkyl and R2 is H or linear or branched C1-C6 (hydroxy)alkyl. 47. A formulation according to any of statements 42 to 46, wherein the 4,5-diaminopyrazole is selected from 4,5-diamino-1-methylpyrazole, 4,5-diamino-1-ethylpyrazole, 4,5-diamino-1-hexylpyrazole, 4,5-diamino-1-hydroxyethylpyrazole, 4,5-diamino-3-methylpyrazole, or a combination thereof. 48 Formula (2): JPEG2025505213000038.jpg28170, In the above formula, R3 is (2-hydroxyethyl)oxy or 4,4-dimethylpiperazinium, or a combination thereof; 48. A formulation according to any of statements 42 to 47. 49 Formula (3): JPEG2025505213000039.jpg34170, including ring-fused 4,5-diaminopyrazolone, In the above formula, R4 is methylene, ethylene, propylene, or a combination thereof. 49. The formulation of any of statements 42 to 48. 50. A formulation according to any of statements 42 to 49, further comprising a conventional primary selected from N,N-bis(2-hydroxyethyl)-p-phenylenediamine, 4-aminophenol, p-phenylenediamine, 3-hydroxypropyl-p-phenylenediamine, 2-methyl-p-phenylenediamine, 2-methoxymethyl-p-phenylenediamine or a combination thereof. 51. A formulation according to any of statements 42 to 50, comprising each primary in a concentration of 0.0025 to 3.0% by weight or 0.005 to 1.5% by weight relative to the total weight of the formulation. 52. A formulation according to any of statements 42 to 51, comprising a coupler comprising resorcinol, 2-methylresorcinol, hydroxyethyl-3,4-methylenedioxyaniline, m-aminophenol, 1-naphthol, 2-amino-4-hydroxyethylaminoanisole, 4-amino-2-hydroxytoluene, 2-methyl-5-hydroxyethylaminophenol, phenylmethylpyrazolone, 6-hydroxy-benzomorpholine, 6-methoxy-2-methylamino-3-aminopyridine or a combination thereof. 53. A formulation according to any of statements 42 to 52, comprising each coupler in a concentration of 0.0025 to 3.0% by weight or 0.005 to 1.5% by weight relative to the total weight of the formulation. 54. A formulation according to any of statements 42 to 53, comprising two or more solubilized vat dyes. 55. A formulation according to any of statements 42 to 54, wherein the solubilized vat dye is a leucovat dye sulfonate ester or a combination of leucovat dye sulfonate esters. 56. The formulation of any of statements 42 to 55, comprising a solubilized vat dye selected from solubilized Vat Violet 1 (CAS#1324-57-8), solubilized Vat Yellow 4 (CAS#3564-70-3), solubilized Vat Green 1 (CAS#2538-84-3), solubilized Vat Yellow 1 (CAS#6487-09-8), solubilized Vat Red 34 (CAS#12226-70-9), solubilized Vat Red 10 (CAS#10126-90-6), solubilized Vat Orange 9 (CAS#70356-06-8), solubilized Vat Orange 3 (CAS#10290-03-6), solubilized Vat Yellow 7 (CAS#3956-62-5), or a combination thereof. 57 includes a solubilized vat dye comprising a polycyclic aromatic tabular chromophore structure consisting of four or more polycondensed rings, optionally containing one or more nitrogen atoms, the tabular chromophore structure being represented by the formula (4): 57. A formulation according to any of statements 42 to 56, comprising a pyrene structural element according to JPEG2025505213000040.jpg31170. 58 The solubilized vat dye comprises a polycyclic aromatic tabular chromophore structure of up to eight polycondensed rings, optionally containing one or more nitrogen atoms, the tabular chromophore structure being represented by formula (5): 58. The formulation of claim 57, comprising a pyranthrene structural element according to JPEG2025505213000041.jpg39170. 59 The solubilized vat dye comprises a polycyclic aromatic tabular chromophore structure consisting of six polycondensed rings, optionally containing one or more nitrogen atoms, the tabular chromophore structure being represented by formula (6): A formulation according to any one of claims 57 to 58, comprising a dibenzopyrene structural element according to JPEG2025505213000042.jpg30170. 60. The formulation of any of statements 42 to 59 comprising a solubilized vat dye selected from solubilized Vat Yellow 4 (CAS#3564-70-3), solubilized Vat Yellow 1 (CAS#6487-09-8), solubilized Vat Orange 3 (CAS#10290-03-6), solubilized Vat Orange 9 (CAS#70356-06-8) or combinations thereof. 61. A formulation according to any of statements 42 to 60, comprising a reducing agent, in particular sodium sulfite, citric acid, ascorbic acid or a combination thereof. 62. A formulation according to any of statements 42 to 61, comprising each solubilized vat dye in a concentration of 0.25 to 1.0% by weight based on the total weight of the formulation. 63. A formulation according to any of statements 42 to 62, further comprising one or more ingredients selected from pH adjusters, chelating agents, fragrances, care ingredients, texture ingredients, vehicle agents, solvents, surfactants.

[0192] 64. A formulation according to any of statements 42 to 63, wherein composition A comprises at least 1.0% by weight of one or more anionic surfactants, at least 2.0% by weight of one or more linear or branched C14 to C30 fatty alcohols, and at least 0.1% by weight of one or more nonionic surfactants. 65. A formulation according to any of statements 42-63, wherein prior to mixing, composition A comprises at least 10% by weight of one or more hydrocarbons and at least 5.0% by weight of one or more fatty alcohols. 66. A formulation according to any of statements 42 to 65, wherein prior to mixing, composition B comprises 10.0 to 30.0 wt. of one or more fatty acids. 67. The formulation of statement 66, wherein composition B comprises 2.0-20.0% by weight of a rheological agent selected from ammonia, monoethanolamine, or a combination thereof. 68. A formulation according to any of statements 42 to 65, wherein composition B prior to mixing comprises 2.0 to 40.0% by weight of an anionic surfactant, 2.0 to 20.0% by weight of an amphoteric surfactant, and 0 to 10.0% by weight of an optional moisturizer. 69. A formulation according to any of statements 42 to 68, which is essentially free of pigments, parabens, silicones or combinations thereof. 70. A formulation according to any of statements 42 to 69, configured to produce a color within a color space selected from orange, reddish orange, copper, mahogany red, mahogany brownish or vibrant red. 71 It is configured to provide a wash fastness improvement ΔE(OXID) / ΔE(OXID+VAT) of 1.5 or more, ΔE(OXID) is the color difference [(L2-L1) 2 +(a2-a1) 2 +(b2-b1) 2 ] 1 / 2 and ΔE(OXID+VAT) is the color difference [(L4-L3) 2 +(a4-a3) 2 +(b4-b3) 2 ] 1 / 2 and L1, a1 and b1 are the CIELAB L*a*b colour coordinates determined on natural grey hair coloured with composition A alone before washing, L2, a2 ​​and b2 are the CIELAB L*a*b colour coordinates determined on natural grey hair coloured with composition A only after 15 standard wash cycles, L3, a3 and b3 are the CIELAB L*a*b colour coordinates determined on natural grey hair coloured with compositions A and B before washing, L4, a4 ​​and b4 are the CIELAB L*a*b colour coordinates determined on natural grey hair coloured with compositions A and B after 15 standard washing cycles, 71. A formulation according to any one of statements 42 to 70. 72 A hair dyeing kit comprising: a compartment A comprising a composition A, said composition A comprising an aqueous medium and an oxidative dye precursor dissolved in said aqueous medium, said oxidative dye precursor comprising a pyrazole primary and a coupler, said pyrazole primary comprising a 4,5-diaminopyrazole, an aminopyrazolopyridine, a ring-fused 4,5-diaminopyrazolone, or a combination thereof; a compartment B containing a composition B, said composition B comprising an aqueous medium and a solubilized vat dye dissolved in said aqueous medium; A kit comprising, in a separate compartment. 73. The kit of statement 72, further comprising a compartment C comprising composition C, said composition C comprising an oxidizing agent. 74. The kit of claim 73, wherein the oxidizing agent comprises hydrogen peroxide, and in particular, the oxidizing agent is hydrogen peroxide at a concentration of 1.0 to 12.0% by volume relative to the volume of composition C. 75. A kit according to statement 73 or 74, wherein composition C has a pH in the range of 2.0 to 4.0, in particular in the range of 2.5 to 3.5. 76. A kit according to any of statements 72 to 75, wherein composition A has a pH in the range of 8.0 to 11.0, in particular in the range of 8.5 to 9.5, for example a pH of about 9.0. 77. A kit according to any of statements 72 to 76, wherein composition B has a pH in the range of 8.0 to 11.0, in particular in the range of 8.5 to 9.5, for example a pH of about 9.0. 78. The kit of any of statements 72 to 77, wherein composition A, B or both further comprises a penetration enhancer. 79. The kit of statement 78, wherein the penetration enhancer is selected from ammonia, urea, monoethanolamine, 2-amino-1-propanol, or a combination thereof. 80 Composition A is a compound represented by the formula (1): JPEG2025505213000043.jpg35170, containing 4,5-diaminopyrazole, 80. The kit of any of statements 72 to 79, wherein R1 is linear or branched C1-C6 (hydroxy)alkyl and R2 is H or linear or branched C1-C6 (hydroxy)alkyl. 81. The kit of any of statements 72 to 80, wherein the 4,5-diaminopyrazole is selected from 4,5-diamino-1-methylpyrazole, 4,5-diamino-1-ethylpyrazole, 4,5-diamino-1-hexylpyrazole, 4,5-diamino-1-hydroxyethylpyrazole, 4,5-diamino-3-methylpyrazole, or a combination thereof. 82 Composition A is a compound represented by the formula (2): JPEG2025505213000044.jpg28170, In the above formula, R3 is (2-hydroxyethyl)oxy or 4,4-dimethylpiperazinium, or a combination thereof; 81. The kit of any of statements 72 to 80. 83 Composition A is a compound represented by the formula (3): JPEG2025505213000045.jpg34170, including ring-fused 4,5-diaminopyrazolone, In the above formula, R4 is methylene, ethylene, propylene, or a combination thereof. 83. The kit of any of statements 72 to 82. 84. The kit of any of statements 72 to 83, further comprising a conventional primary selected from N,N-bis(2-hydroxyethyl)-p-phenylenediamine, 4-aminophenol, p-phenylenediamine, 3-hydroxypropyl-p-phenylenediamine, 2-methyl-p-phenylenediamine, 2-methoxymethyl-p-phenylenediamine, or a combination thereof. 85. A kit according to any of statements 72 to 84, wherein composition A contains each primary at a concentration of 0.005 to 6.0% by weight or 0.01 to 3.0% by weight, based on the weight of composition A. 86. The kit of any of statements 72 to 85, wherein composition A comprises a coupler comprising resorcinol, 2-methylresorcinol, hydroxyethyl-3,4-methylenedioxyaniline, m-aminophenol, 1-naphthol, 2-amino-4-hydroxyethylaminoanisole, 4-amino-2-hydroxytoluene, 2-methyl-5-hydroxyethylaminophenol, phenylmethylpyrazolone, 6-hydroxy-benzomorpholine, 6-methoxy-2-methylamino-3-aminopyridine, or a combination thereof. 87. A kit according to any of statements 72 to 86, wherein composition A contains each coupler in a concentration of 0.005 to 6.0% by weight or 0.01 to 3.0% by weight, based on the weight of composition A. 88. The kit of any of statements 72 to 87, wherein composition B comprises two or more solubilized vat dyes. 89. The kit of any of statements 72 to 88, wherein the solubilized vat dye in composition B is a leucovat dye sulfonate ester or a combination of leucovat dye sulfonate esters. 90. The kit of any of statements 72 to 89, wherein composition B comprises a solubilized vat dye selected from solubilized Vat Violet 1 (CAS#1324-57-8), solubilized Vat Yellow 4 (CAS#3564-70-3), solubilized Vat Green 1 (CAS#2538-84-3), solubilized Vat Yellow 1 (CAS#6487-09-8), solubilized Vat Red 34 (CAS#12226-70-9), solubilized Vat Red 10 (CAS#10126-90-6), solubilized Vat Orange 9 (CAS#70356-06-8), solubilized Vat Orange 3 (CAS#10290-03-6), solubilized Vat Yellow 7 (CAS#3956-62-5), or a combination thereof. 91 Composition B comprises a solubilized vat dye comprising a polycyclic aromatic tabular chromophore structure consisting of four or more polycondensed rings, optionally containing one or more nitrogen atoms, the tabular chromophore structure being represented by formula (4): A kit according to any of statements 72 to 90, comprising a pyrene structural element according to JPEG2025505213000046.jpg31170. 92 The solubilized vat dye comprises a polycyclic aromatic tabular chromophore structure of up to eight polycondensed rings, optionally containing one or more nitrogen atoms, the tabular chromophore structure being represented by formula (5): The kit described in description 91, comprising a pyranthrene structural element according to JPEG2025505213000047.jpg40170. 93 The solubilized vat dye comprises a polycyclic aromatic tabular chromophore structure consisting of six polycondensed rings, optionally containing one or more nitrogen atoms, the tabular chromophore structure being represented by formula (6): A kit according to description 91 or 92, comprising a dibenzopyrene structural element according to JPEG2025505213000048.jpg32170. 94. The kit of any of statements 72 to 93, wherein composition B comprises a solubilized vat dye selected from solubilized vat yellow 4 (CAS# 3564-70-3), solubilized vat yellow 1 (CAS# 6487-09-8), solubilized vat orange 3 (CAS# 10290-03-6), solubilized vat orange 9 (CAS# 70356-06-8), or a combination thereof. 95. The kit according to any of statements 72 to 94, wherein composition B comprises a reducing agent, in particular sodium sulfite, citric acid, ascorbic acid or a combination thereof. 96. A kit according to any of statements 72 to 95, wherein composition B comprises each solubilized vat dye in a concentration of 0.50 to 2.0% by weight based on the weight of composition B. 97. The kit of any of statements 72 to 96, wherein one or more of compositions A, B, C further comprises one or more ingredients selected from a pH adjuster, a chelating agent, a fragrance, a care ingredient, a texture ingredient, a vehicle agent, a solvent, a surfactant. 98. The kit of any of statements 72 to 97, wherein composition A comprises at least 1.0% by weight of one or more anionic surfactants, at least 2.0% by weight of one or more linear or branched C14 to C30 fatty alcohols, and at least 0.1% by weight of one or more nonionic surfactants. 99. The kit of any of statements 72 to 97, wherein composition A comprises at least 10% by weight of one or more hydrocarbons and at least 5.0% by weight of one or more fatty alcohols. 100. The kit of any of statements 72 to 99, wherein composition B comprises 10.0 to 30.0 wt. of one or more fatty acids. 101. The kit of statement 100, wherein composition B comprises 2.0-20.0% by weight of a rheological agent selected from ammonia, monoethanolamine, or a combination thereof. 102. The kit of any of statements 72 to 99, wherein composition B comprises 2.0 to 40.0% by weight of an anionic surfactant, 2.0 to 20.0% by weight of an amphoteric surfactant, and 0 to 10.0% by weight of an optional moisturizer. 103. The kit of any of statements 72 to 102, wherein one or more of compositions A, B, C is essentially free of pigments, parabens, silicones, or combinations thereof. 104. The manufacturing kit of any of statements 72 to 103, configured to produce a color within a color space selected from orange, reddish orange, copper, mahogany red, mahogany brownish, or vibrant red. 105. The kit of any of claims 72 to 104, configured such that the resulting washfastness improvement ΔE(OXID) / ΔE(OXID+VAT) is 1.5 or greater, ΔE(OXID) is the color difference [(L2-L1) 2 +(a2-a1) 2 +(b2-b1) 2 ] 1 / 2 and ΔE(OXID+VAT) is the color difference [(L4-L3) 2 +(a4-a3) 2 +(b4-b3) 2 ] 1 / 2 and L1, a1 and b1 are the CIELAB L*a*b colour coordinates determined on natural grey hair coloured with composition A alone before washing; L2, a2 ​​and b2 are the CIELAB L*a*b colour coordinates determined on natural grey hair coloured with composition A only after 15 standard wash cycles; L3, a3 and b3 are the CIELAB L*a*b colour coordinates determined on natural grey hair coloured with compositions A and B before washing; L4, a4 ​​and b4 are the CIELAB L*a*b colour coordinates determined on natural grey hair coloured with compositions A and B after 15 standard wash cycles. ,kit. 106. A gel-like hair coloring composition comprising one or more solubilized vat dyes, each having a concentration of 0.50 to 2.0% by weight, 10.0 to 30.0% by weight of one or more saturated or unsaturated fatty acids, and 50 to 89.50% by weight of water, each weight percentage being based on the weight of that component. 107 A gel-like haircolor composition according to statement 106, comprising 12.0 to 25.0% by weight, in particular 15.0 to 20.0% by weight, of said one or more saturated or unsaturated fatty acids. 108. A gel-like hair color component according to statement 106 or 107, wherein the one or more saturated or unsaturated fatty acids have a linear carbon chain length of from C16 to C30. 109. A gel-like haircolor composition according to any of statements 106 to 108, wherein the one or more saturated or unsaturated fatty acids comprise palmitic acid (C16:0), stearic acid (C18:0), palmitoleic acid (C16:1), oleic acid (C18:1), linoleic acid (C18:2), linolenic acid (C18:3), or a combination thereof. 110. A gel-like hair color composition according to any of statements 106 to 109, comprising 2.0 to 20.0% by weight of a rheology agent selected from ammonia, monoethanolamine, or a combination thereof. 111 A shampoo-like hair coloring composition comprising one or more solubilized vat dyes, each in a concentration of 0.50 to 2.0% by weight, 2.0 to 40.0% by weight of an anionic surfactant, 2.0 to 20.0% by weight of an amphoteric surfactant, 0 to 10.0% by weight of an optional humectant, and 50.0 to 95.50% by weight of water, each weight percentage being based on the weight of that component. 112. A shampoo-like haircolor composition according to statement 111, comprising 4.0 to 25.0% by weight, particularly 6.0 to 15.0% by weight, of an anionic surfactant, 3.0 to 15.0% by weight, particularly 4.0 to 10.0% by weight, of an amphoteric surfactant, and 1.0 to 8.0% by weight of a humectant. 113. The shampoo-like haircolor composition of claim 111 or 112, wherein the anionic surfactant is selected from alkyl sulfates, alkyl ether sulfates, alkyl amido ether sulfates, monoglyceride sulfates, a-olefin sulfonates, paraffin sulfonates, alkyl phosphates, alkyl sulfoacetates, acyl isethionates, alkyl ether phosphates, alkyl phenyl ether sulfonates, N-cocoyl fatty acyl glutamates, N-lauroyl glutamates, N-acyl amino acid salts, N-cocoyl fatty acyl glycines, N-cocoyl fatty acyl alanines, salts of alkyl sulfosuccinic acids, and combinations thereof. 114. A shampoo-like haircolor composition according to any of statements 111 to 113, wherein the amphoteric surfactant is selected from betaines, in particular alkyl amido betaines, alkyl betaines, amido sulfo betaines, carboxy betaine type betaines, sulfo betaine type betaines, hydroxy sulfo betaine betaines, phospho betaine type betaines, and combinations thereof. 115. A shampoo-like haircolor composition according to any of statements 111 to 114, wherein the humectant is selected from glycerol, glycerol esters, propylene glycol, isopentyl diol, and combinations thereof. 116. A shampoo-like haircolor composition according to any of statements 111 to 115, comprising 6.0 to 10.0% by weight sodium laureth sulfate, 4.0 to 6.0% by weight cocoamidopropyl betaine, and 2.0 to 4.0% by weight glycerin. 117. A hair coloring composition according to any of statements 106 to 116, further comprising a penetration enhancer, particularly a penetration enhancer selected from ammonia, urea, monoethanolamine, 2-amino-1-propanol, or combinations thereof. 118. A haircoloring composition according to any of statements 106 to 117, further comprising a reducing agent, particularly sodium sulfite, citric acid, ascorbic acid, or a combination thereof. 119. A haircolor composition according to any of statements 106 to 118, further comprising one or more ingredients selected from a pH adjuster, a chelating agent, a fragrance, a care ingredient, a texture ingredient, a vehicle agent, a solvent, and a non-ionic surfactant. 120. A hair coloring composition according to any of statements 106 to 119, wherein the solubilized vat dye is a leucovat dye sulfonate ester or a combination of leucovat dye sulfonate esters. 121. A hair coloring composition according to any of statements 106 to 120, comprising a solubilized vat dye selected from solubilized Vat Violet 1 (CAS#1324-57-8), solubilized Vat Yellow 4 (CAS#3564-70-3), solubilized Vat Green 1 (CAS#2538-84-3), solubilized Vat Yellow 1 (CAS#6487-09-8), solubilized Vat Red 34 (CAS#12226-70-9), solubilized Vat Red 10 (CAS#10126-90-6), solubilized Vat Orange 9 (CAS#70356-06-8), solubilized Vat Orange 3 (CAS#10290-03-6), solubilized Vat Yellow 7 (CAS#3956-62-5), or a combination thereof. 122 includes a solubilized vat dye comprising a polycyclic aromatic tabular chromophore structure consisting of four or more polycondensed rings, optionally containing one or more nitrogen atoms, the tabular chromophore structure having the formula (4): A hair color component according to any of statements 106 to 120, comprising a pyrene structural element according to JPEG2025505213000049.jpg30170. 123 The solubilized vat dye comprises a polycyclic aromatic tabular chromophore structure of up to eight polycondensed rings, optionally containing one or more nitrogen atoms, the tabular chromophore structure being represented by formula (5): A hair coloring composition according to statement 122, comprising a pyranthrene structural element according to JPEG2025505213000050.jpg38170. 124 The solubilized vat dye comprises a polycyclic aromatic tabular chromophore structure consisting of six polycondensed rings, optionally containing one or more nitrogen atoms, the tabular chromophore structure being represented by formula (6): A hair color component according to description 122 or 123, comprising a dibenzopyrene structural element according to JPEG2025505213000051.jpg30170. 125. A hair coloring composition according to any of statements 106 to 124, comprising a solubilized vat dye selected from solubilized Vat Yellow 4 (CAS#3564-70-3), solubilized Vat Yellow 1 (CAS#6487-09-8), solubilized Vat Orange 3 (CAS#10290-03-6), solubilized Vat Orange 9 (CAS#70356-06-8), or combinations thereof. 126. Use of a hair coloring composition according to any of statements 106 to 125 to improve the washfastness of a hair color produced by an oxidation dye, wherein the one or more oxidation dyes are derived from an oxidation dye precursor comprising a pyrazole primary and a coupler. 127. The use of statement 126, wherein the one or more oxidation dyes are derived from an oxidation dye precursor comprising a pyrazole primary comprising a 4,5-diaminopyrazole, an aminopyrazolopyridine, a ring-fused 4,5-diaminopyrazolone, or a combination thereof. 128 One or more oxidation dyes are represented by the formula (1): JPEG2025505213000052.jpg36170, comprising a 4,5-diaminopyrazole-containing oxidation dye precursor according to the present invention, 128. The use according to statement 126 or 127, wherein R1 is linear or branched C1-C6 (hydroxy)alkyl and R2 is H or linear or branched C1-C6 (hydroxy)alkyl. 129. The use according to any of statements 126 to 128, wherein the 4,5-diaminopyrazole is selected from 4,5-diamino-1-methylpyrazole, 4,5-diamino-1-ethylpyrazole, 4,5-diamino-1-hexylpyrazole, 4,5-diamino-1-hydroxyethylpyrazole, 4,5-diamino-3-methylpyrazole, or a combination thereof. 130 One or more oxidation dyes are represented by the formula (2): JPEG2025505213000053.jpg28170, derived from an oxidation dye precursor comprising a pyrazole primary comprising an aminopyrazolopyridine, In the above formula, R3 is (2-hydroxyethyl)oxy or 4,4-dimethylpiperazinium, or a combination thereof; 130. The use according to any of statements 126 to 129. 131 One or more oxidation dyes are represented by the formula (3): JPEG2025505213000054.jpg33170, comprising a pyrazole primary comprising a ring-fused 4,5-diaminopyrazolone according to the present invention, In the above formula, R4 is methylene, ethylene, propylene, or a combination thereof. 131. The use according to any of statements 126 to 130. 132. The use according to any of statements 126 to 131, wherein the resulting hair color is in the color space of orange, reddish orange, copper, mahogany red, mahogany brownish or vibrant red. 133 The resulting improvement in washing fastness ΔE(OXID) / ΔE(OXID+VAT) is 1.5 or more, ΔE(OXID) is the color difference [(L2-L1) 2 +(a2-a1) 2 +(b2-b1) 2 ]1 / 2 and ΔE(OXID+VAT) is the color difference [(L4-L3) 2 +(a4-a3) 2 +(b4-b3) 2 ] 1 / 2 and L1, a1 and b1 are the CIELAB L*a*b colour coordinates determined on natural grey hair coloured with composition A alone before washing; L2, a2 ​​and b2 are the CIELAB L*a*b colour coordinates determined on natural grey hair coloured with composition A only after 15 standard wash cycles; L3, a3 and b3 are the CIELAB L*a*b colour coordinates determined on natural grey hair coloured with compositions A and B before washing; L4, a4 ​​and b4 are the CIELAB L*a*b colour coordinates determined on natural grey hair coloured with compositions A and B after 15 standard washing cycles; 133. The use according to any of statements 126 to 132. 134. Use of a solubilized vat dye to improve the washfastness of hair color produced with oxidation dyes, wherein one or more oxidation dyes are derived from an oxidation dye precursor comprising a pyrazole primary and a coupler. 135. The use of statement 134, wherein the one or more oxidation dyes are derived from an oxidation dye precursor comprising a pyrazole primary comprising a 4,5-diaminopyrazole, an aminopyrazolopyridine, a ring-fused 4,5-diaminopyrazolone, or a combination thereof. 136 One or more oxidation dyes are represented by the formula (1): JPEG2025505213000055.jpg37170, comprising a 4,5-diaminopyrazole-containing oxidation dye precursor according to the present invention, 136. The use according to statement 134 or 135, wherein R1 is linear or branched C1-C6 (hydroxy)alkyl and R2 is H or linear or branched C1-C6 (hydroxy)alkyl. 137. The use according to any of statements 134 to 136, wherein the 4,5-diaminopyrazole is selected from 4,5-diamino-1-methylpyrazole, 4,5-diamino-1-ethylpyrazole, 4,5-diamino-1-hexylpyrazole, 4,5-diamino-1-hydroxyethylpyrazole, 4,5-diamino-3-methylpyrazole or a combination thereof. 138 One or more oxidation dyes are represented by the formula (2): JPEG2025505213000056.jpg29170, derived from an oxidation dye precursor comprising a pyrazole primary comprising an aminopyrazolopyridine, In the above formula, R3 is (2-hydroxyethyl)oxy or 4,4-dimethylpiperazinium, or a combination thereof; 138. The use according to any of statements 134 to 137. 139 One or more oxidation dyes are represented by the formula (3): JPEG2025505213000057.jpg34170, comprising a pyrazole primary comprising a ring-fused 4,5-diaminopyrazolone according to the present invention, In the above formula, R4 is methylene, ethylene, propylene, or a combination thereof. 19. The use according to any of statements 134 to 138. 140. Use according to any of statements 134 to 139, wherein the solubilized vat dye is a leucovat dye sulfonate ester or a combination of leucovat dye sulfonate esters. 141 A solubilized vat dye comprising a polycyclic aromatic tabular chromophore structure comprising four or more polycondensed rings, optionally containing one or more nitrogen atoms, the tabular chromophore structure being represented by the formula (4): 140. The use according to any of descriptions 134 to 140, comprising a pyrene structural element according to JPEG2025505213000058.jpg30170. 142 The solubilized vat dye comprises a polycyclic aromatic tabular chromophore structure of up to eight polycondensed rings, optionally containing one or more nitrogen atoms, the tabular chromophore structure being represented by formula (5): The use according to description 141, comprising a pyranthrene structural element according to JPEG2025505213000059.jpg38170. 143 The solubilized vat dye comprises a polycyclic aromatic tabular chromophore structure consisting of six polycondensed rings, optionally containing one or more nitrogen atoms, the tabular chromophore structure having the formula (6): 143. Use according to claim 141 or 142, comprising a dibenzopyrene structural element according to JPEG2025505213000060.jpg30170. 144. The use of any of statements 134 to 143, wherein the solubilized vat dye is selected from solubilized vat yellow 4 (CAS#3564-70-3), solubilized vat yellow 1 (CAS#6487-09-8), solubilized vat orange 3 (CAS#10290-03-6), solubilized vat orange 9 (CAS#70356-06-8) or a combination thereof. 145. The use according to any of statements 134 to 144, wherein the resulting hair color is in the color space of orange, reddish orange, copper, mahogany red, mahogany brownish or vibrant red. 146 The resulting improvement in washing fastness ΔE(OXID) / ΔE(OXID+VAT) is 1.5 or more, ΔE(OXID) is the color difference [(L2-L1) 2 +(a2-a1) 2 +(b2-b1) 2 ] 1 / 2 and ΔE(OXID+VAT) is the color difference [(L4-L3) 2 +(a4-a3) 2 +(b4-b3) 2 ] 1 / 2 and L1, a1 and b1 are the CIELAB L*a*b colour coordinates determined on natural grey hair coloured with composition A alone before washing; L2, a2 ​​and b2 are the CIELAB L*a*b colour coordinates determined on natural grey hair coloured with composition A only after 15 standard wash cycles; L3, a3 and b3 are the CIELAB L*a*b colour coordinates determined on natural grey hair coloured with compositions A and B before washing; L4, a4 ​​and b4 are the CIELAB L*a*b colour coordinates determined on natural grey hair coloured with compositions A and B after 15 standard washing cycles; 146. The use according to any of statements 134 to 145.

Claims

1. 1. A method for coloring keratinous materials, comprising the steps of: a1 applying a composition A to the keratinous material, the composition A comprising an aqueous medium and an oxidative dye precursor dissolved in the aqueous medium, the oxidative dye precursor comprising a pyrazole primary and a coupler, the pyrazole primary comprising a 4,5-diaminopyrazole, an aminopyrazolopyridine, a ring-fused 4,5-diaminopyrazolone, or a combination thereof; a2. applying composition B to said keratinous material, said composition B comprising an aqueous medium and a solubilized vat dye dissolved in said aqueous medium, said solubilized vat dye being a leucobat dye sulfonate ester; b. after step a2, applying a composition C to the keratinous material, the composition C comprising an oxidizing agent. A method comprising:

2. 2. The method of claim 1, wherein composition B is applied to said keratinous material simultaneously with or subsequent to application of composition A to said keratinous material.

3. 3. The method according to claim 1 or 2, wherein compositions A and B are mixed before applying them to the keratinous material.

4. 4. The method according to claim 1, wherein the oxidizing agent comprises hydrogen peroxide, in particular the oxidizing agent is hydrogen peroxide in a concentration of 1.0 to 12.0% by volume relative to the volume of composition C.

5. 5. The method according to any one of claims 1 to 4, wherein composition A, B or both have a pH in the range of 8.0 to 11.0, in particular in the range of 8.5 to 9.5, for example a pH of about 9.

0.

6. 6. The method according to claim 1, wherein, prior to step b, compositions A and B are maintained on the keratinous material for at least 20 minutes, in particular for 20 to 40 minutes, at a temperature of 20 to 40° C., in particular at a temperature of 35 to 40° C., and at a pH of 8.0 to 11.

0.

7. 7. The method according to any one of claims 1 to 6, wherein in steps a and b the pH is maintained in the range of 8.0 to 10.0, such as in the range of 8.5 to 9.

5.

8. 8. The method of any one of claims 1 to 7, wherein composition A, B or both further comprises a penetration enhancer, in particular a penetration enhancer selected from ammonia, urea, monoethanolamine, 2-amino-1-propanol or a combination thereof.

9. Composition A is a compound represented by formula (1): containing a 4,5-diaminopyrazole according to 9. The method according to any one of claims 1 to 8, wherein R1 is a linear or branched C1-C6 (hydroxy)alkyl and R2 is H or a linear or branched C1-C6 (hydroxy)alkyl.

10. 10. The method of any one of claims 1 to 9, wherein the 4,5-diaminopyrazole is selected from 4,5-diamino-1-methylpyrazole, 4,5-diamino-1-ethylpyrazole, 4,5-diamino-1-hexylpyrazole, 4,5-diamino-1-hydroxyethylpyrazole, 4,5-diamino-3-methylpyrazole, or a combination thereof.

11. Composition A is a compound represented by formula (2): and In the above formula, R3 is (2-hydroxyethyl)oxy or 4,4-dimethylpiperazinium, or a combination thereof.

11. The method according to any one of claims 1 to 10.

12. Composition A is a compound represented by formula (3): ring-fused 4,5-diaminopyrazolones according to In the above formula, R4 is methylene, ethylene, propylene, or a combination thereof; 12. The method according to any one of claims 1 to 11.

13. 13. The method of any one of claims 1 to 12, wherein composition A further comprises a conventional primary selected from N,N-bis(2-hydroxyethyl)-p-phenylenediamine, 4-aminophenol, p-phenylenediamine, 3-hydroxypropyl-p-phenylenediamine, 2-methyl-p-phenylenediamine, 2-methoxymethyl-p-phenylenediamine, or combinations thereof.

14. 14. The method of any one of claims 1 to 13, wherein composition A comprises each primary in a concentration of from 0.005 to 6.0% by weight, or from 0.01 to 3.0% by weight, relative to the weight of composition A.

15. 15. The method of any one of claims 1 to 14, wherein Composition A comprises a coupler selected from resorcinol, 2-methylresorcinol, hydroxyethyl-3,4-methylenedioxyaniline, m-aminophenol, 1-naphthol, 2-amino-4-hydroxyethylaminoanisole, 4-amino-2-hydroxytoluene, 2-methyl-5-hydroxyethylaminophenol, phenylmethylpyrazolone, 6-hydroxy-benzomorpholine, 6-methoxy-2-methylamino-3-aminopyridine, or combinations thereof.

16. 16. The method according to any one of claims 1 to 15, wherein composition A comprises each coupler in a concentration of from 0.005 to 6.0% by weight or from 0.01 to 3.0% by weight relative to the weight of composition A.

17. 17. The method of any one of claims 1 to 16, wherein the Leukovat dye sulfonate ester in composition B is a combination of Leukovat dye sulfonate esters.

18. 18. The method of any one of claims 1 to 17, wherein composition B comprises a Leucobat dye sulfonate ester selected from solubilized Vat Yellow 4 (CAS# 3564-70-3), solubilized Vat Yellow 1 (CAS# 6487-09-8), solubilized Vat Orange 3 (CAS# 10290-03-6), solubilized Vat Orange 9 (CAS# 70356-06-8), or combinations thereof.

19. 19. The method according to any one of claims 1 to 18, wherein composition B comprises a reducing agent, in particular sodium sulfite, citric acid, ascorbic acid or a combination thereof.

20. 20. The method of any one of claims 1 to 19, wherein composition B comprises each Leukobat dye sulfonate ester in a concentration of 0.50 to 2.0% by weight, based on the weight of composition B.

21. 21. The method according to any one of claims 1 to 20, wherein one or more of compositions A, B, C further comprises one or more ingredients selected from pH adjusters, chelating agents, fragrances, care ingredients, texture ingredients, vehicle agents, solvents, surfactants.

22. 22. The method of any one of claims 1 to 21, further comprising rinsing the keratinous material following step b, and optionally further comprising a post-treatment comprising shampooing, conditioning, drying the keratinous material or a combination thereof.

23. 23. The method according to any one of claims 1 to 22, wherein the keratinous material is mammalian hair, in particular human hair.

24. 1. A ready-to-use hair color formulation, the hair color formulation being obtainable by mixing composition A and composition B, wherein composition A comprises an aqueous medium and an oxidative dye precursor dissolved in the aqueous medium, the oxidative dye precursor comprising a pyrazole primary and a coupler, the pyrazole primary comprising 4,5-diaminopyrazole, aminopyrazolopyridine, ring-fused 4,5-diaminopyrazolone or a combination thereof, and wherein composition B comprises an aqueous medium and a solubilized vat dye dissolved in the aqueous medium, the solubilized vat dye being a leucobat dye sulfonate ester.

25. 25. The formulation according to claim 24, having a pH in the range of 8.0 to 11.0, in particular in the range of 8.5 to 9.5, for example a pH of about 9.

0.

26. 26. The formulation of claim 24 or 25, further comprising a penetration enhancer, in particular a penetration enhancer selected from ammonia, urea, monoethanolamine, 2-amino-1-propanol or combinations thereof.

27. Formula (1): containing a 4,5-diaminopyrazole according to 27. The formulation of any one of claims 24 to 26, wherein R1 is linear or branched C1-C6 (hydroxy)alkyl and R2 is H or linear or branched C1-C6 (hydroxy)alkyl.

28. 28. The formulation of any one of claims 24 to 27, wherein the 4,5-diaminopyrazole is selected from 4,5-diamino-1-methylpyrazole, 4,5-diamino-1-ethylpyrazole, 4,5-diamino-1-hexylpyrazole, 4,5-diamino-1-hydroxyethylpyrazole, 4,5-diamino-3-methylpyrazole, or combinations thereof.

29. Formula (2): and In the above formula, R3 is (2-hydroxyethyl)oxy or 4,4-dimethylpiperazinium, or a combination thereof.

29. A formulation according to any one of claims 24 to 28.

30. Formula (3): ring-fused 4,5-diaminopyrazolones according to In the above formula, R4 is methylene, ethylene, propylene, or a combination thereof; 30. A formulation according to any one of claims 24 to 29.

31. 31. The formulation of any one of claims 24 to 30, further comprising a conventional primary selected from N,N-bis(2-hydroxyethyl)-p-phenylenediamine, 4-aminophenol, p-phenylenediamine, 3-hydroxypropyl-p-phenylenediamine, 2-methyl-p-phenylenediamine, 2-methoxymethyl-p-phenylenediamine, or combinations thereof.

32. 32. A formulation according to any one of claims 24 to 31, comprising each primary in a concentration of 0.0025 to 3.0% by weight or 0.005 to 1.5% by weight relative to the total weight of the formulation.

33. 33. The formulation of any one of claims 24 to 32, comprising a coupler comprising resorcinol, 2-methylresorcinol, hydroxyethyl-3,4-methylenedioxyaniline, m-aminophenol, 1-naphthol, 2-amino-4-hydroxyethylaminoanisole, 4-amino-2-hydroxytoluene, 2-methyl-5-hydroxyethylaminophenol, phenylmethylpyrazolone, 6-hydroxy-benzomorpholine, 6-methoxy-2-methylamino-3-aminopyridine or combinations thereof.

34. 34. A formulation according to any one of claims 24 to 33, comprising each coupler in a concentration of 0.0025 to 3.0% by weight or 0.005 to 1.5% by weight relative to the total weight of the formulation.

35. 35. A formulation according to any one of claims 24 to 34, wherein the Leucobat dye sulfonate ester in composition B is a combination of Leucobat dye sulfonate esters.

36. 36. The formulation of any one of claims 24 to 35, comprising a Leucobat dye sulfonate ester selected from solubilized Vat Yellow 4 (CAS# 3564-70-3), solubilized Vat Yellow 1 (CAS# 6487-09-8), solubilized Vat Orange 3 (CAS# 10290-03-6), solubilized Vat Orange 9 (CAS# 70356-06-8), or combinations thereof.

37. 37. The formulation according to any one of claims 24 to 36, comprising a reducing agent, in particular sodium sulfite, citric acid, ascorbic acid or a combination thereof.

38. 38. A formulation according to any one of claims 24 to 37, comprising each Leukobat dye sulfonate ester in a concentration of 0.25 to 1.0% by weight relative to the total weight of the formulation.

39. 39. A formulation according to any one of claims 24 to 38, further comprising one or more ingredients selected from pH adjusters, chelating agents, fragrances, care ingredients, texture ingredients, vehicle agents, solvents, surfactants.

40. A hair dye kit comprising: a compartment A comprising a composition A, said composition A comprising an aqueous medium and an oxidative dye precursor dissolved in said aqueous medium, said oxidative dye precursor comprising a pyrazole primary and a coupler, said pyrazole primary comprising a 4,5-diaminopyrazole, an aminopyrazolopyridine, a ring-fused 4,5-diaminopyrazolone, or a combination thereof; Compartment B comprising composition B, said composition B comprising an aqueous medium and a solubilized vat dye dissolved in said aqueous medium, said solubilized vat dye being a leucobat dye sulfonate ester; A kit comprising:

41. 41. The kit of claim 40, further comprising a compartment C comprising a composition C, said composition C comprising an oxidizing agent.

42. 42. The kit of claim 41, wherein the oxidizing agent comprises hydrogen peroxide, in particular, the oxidizing agent is hydrogen peroxide at a concentration of 1.0 to 12.0% by volume relative to the volume of composition C.

43. The kit according to claim 41 or 42, wherein composition C has a pH in the range of 2.0 to 4.0, in particular in the range of 2.5 to 3.

5.

44. 44. The kit according to any one of claims 40 to 43, wherein composition A, composition B or both have a pH in the range of 8.0 to 11.0, in particular in the range of 8.5 to 9.5, for example a pH of about 9.

0.

45. 45. The kit according to any one of claims 40 to 44, wherein composition A, B or both further comprises a penetration enhancer, in particular a penetration enhancer selected from ammonia, urea, monoethanolamine, 2-amino-1-propanol or a combination thereof.

46. Composition A is a compound represented by formula (1): containing a 4,5-diaminopyrazole according to In the above formula, R1 is a linear or branched C1-C6 (hydroxy) alkyl, and R2 is H or a linear or branched C1-C6 (hydroxy) alkyl. The kit of any one of claims 40 to 45.

47. 47. The kit of any one of claims 40 to 46, wherein the 4,5-diaminopyrazole is selected from 4,5-diamino-1-methylpyrazole, 4,5-diamino-1-ethylpyrazole, 4,5-diamino-1-hexylpyrazole, 4,5-diamino-1-hydroxyethylpyrazole, 4,5-diamino-3-methylpyrazole, or a combination thereof.

48. Composition A is a compound represented by formula (2): and In the above formula, R3 is (2-hydroxyethyl)oxy or 4,4-dimethylpiperazinium, or a combination thereof.

48. A kit according to any one of claims 40 to 47.

49. Composition A is a compound represented by formula (3): ring-fused 4,5-diaminopyrazolones according to In the above formula, R4 is methylene, ethylene, propylene, or a combination thereof; 49. The kit of any one of claims 40 to 48.

50. 50. The kit of any one of claims 40 to 49, further comprising a conventional primary selected from N,N-bis(2-hydroxyethyl)-p-phenylenediamine, 4-aminophenol, p-phenylenediamine, 3-hydroxypropyl-p-phenylenediamine, 2-methyl-p-phenylenediamine, 2-methoxymethyl-p-phenylenediamine, or combinations thereof.

51. 51. A kit according to any one of claims 40 to 50, wherein composition A comprises each primary in a concentration of 0.005 to 6.0% by weight or 0.01 to 3.0% by weight relative to the weight of composition A.

52. 52. The kit of any one of claims 40 to 51, wherein Composition A comprises a coupler comprising resorcinol, 2-methylresorcinol, hydroxyethyl-3,4-methylenedioxyaniline, m-aminophenol, 1-naphthol, 2-amino-4-hydroxyethylaminoanisole, 4-amino-2-hydroxytoluene, 2-methyl-5-hydroxyethylaminophenol, phenylmethylpyrazolone, 6-hydroxy-benzomorpholine, 6-methoxy-2-methylamino-3-aminopyridine, or a combination thereof.

53. 53. The kit according to any one of claims 40 to 52, wherein composition A comprises each coupler in a concentration of 0.005 to 6.0% by weight or 0.01 to 3.0% by weight relative to the weight of composition A.

54. 54. The kit of any one of claims 40 to 53, wherein the Leucobat dye sulfonate ester in composition B is a combination of Leucobat dye sulfonate esters.

55. 55. The kit of any one of claims 40 to 54, wherein composition B comprises a Leucobat dye sulfonate ester selected from solubilized Vat Yellow 4 (CAS# 3564-70-3), solubilized Vat Yellow 1 (CAS# 6487-09-8), solubilized Vat Orange 3 (CAS# 10290-03-6), solubilized Vat Orange 9 (CAS# 70356-06-8), or combinations thereof.

56. 56. The kit according to any one of claims 40 to 55, wherein composition B comprises a reducing agent, in particular sodium sulfite, citric acid, ascorbic acid or a combination thereof.

57. 57. The kit of any one of claims 40 to 56, wherein composition B comprises each Leukobat dye sulfonate ester in a concentration of 0.50 to 2.0% by weight, based on the weight of composition B.

58. 58. A kit according to any one of claims 40 to 57, wherein one or more of compositions A, B, C further comprises one or more ingredients selected from pH adjusters, chelating agents, fragrances, care ingredients, texture ingredients, vehicle agents, solvents, surfactants.

59. 1. A gel-like hair color composition comprising one or more leucobat dye sulfonate esters, each in a concentration of 0.50 to 2.0 wt. %, one or more saturated or unsaturated fatty acids, 10.0 to 30.0 wt. %, and water, 50 to 89.50 wt. %, each wt. % being based on the weight of said components.

60. 60. The gel-like hair color composition of claim 59, comprising 2.0 to 20.0% by weight of a rheology agent selected from ammonia, monoethanolamine, or combinations thereof.

61. 1. A shampoo-like hair coloring composition comprising one or more leucobat dye sulfonate esters, each in a concentration of 0.50 to 2.0% by weight, 2.0 to 40.0% by weight of an anionic surfactant, 2.0 to 20.0% by weight of an amphoteric surfactant, 0 to 10.0% by weight of an optional humectant, and 50.0 to 95.50% by weight of water, each weight percentage being based on the weight of said components.

62. 62. The hair color composition of claim 61, further comprising a penetration enhancer, particularly a penetration enhancer selected from ammonia, urea, monoethanolamine, 2-amino-1-propanol, or combinations thereof.

63. 63. A hair colour composition according to any one of claims 59 to 62, further comprising a reducing agent, in particular sodium sulfite, citric acid, ascorbic acid or a combination thereof.

64. 64. A hair color composition according to any one of claims 59 to 63, further comprising one or more ingredients selected from pH adjusters, chelating agents, fragrances, care ingredients, texture ingredients, vehicle reagents, solvents, non-ionic surfactants.

65. 65. The hair coloring composition of any one of claims 59 to 64, comprising a leucobat dye sulfonate ester selected from solubilized Vat Violet 1 (CAS# 1324-57-8), solubilized Vat Yellow 4 (CAS# 3564-70-3), solubilized Vat Green 1 (CAS# 2538-84-3), solubilized Vat Yellow 1 (CAS# 6487-09-8), solubilized Vat Red 34 (CAS# 12226-70-9), solubilized Vat Red 10 (CAS# 10126-90-6), solubilized Vat Orange 9 (CAS# 70356-06-8), solubilized Vat Orange 3 (CAS# 10290-03-6), solubilized Vat Yellow 7 (CAS# 3956-62-5), or combinations thereof.

66. 66. Use of the hair coloring composition according to any one of claims 59 to 65 to improve the wash fastness of a hair color produced by an oxidative dye, wherein the one or more oxidative dyes are derived from an oxidative dye precursor comprising a pyrazole primary and a coupler.

67. 67. The use according to claim 66, wherein the one or more oxidation dyes are derived from an oxidation dye precursor comprising a pyrazole primary comprising 4,5-diaminopyrazole, an aminopyrazolopyridine, a ring-fused 4,5-diaminopyrazolone or a combination thereof.

68. 68. The use according to claim 66 or 67, wherein the one or more oxidation dyes are represented by the formula (1): derived from an oxidation dye precursor containing a pyrazole primary including a 4,5-diaminopyrazole according to In the above formula, R1 is a linear or branched C1-C6 (hydroxy)alkyl, and R2 is H or a linear or branched C1-C6 (hydroxy)alkyl.

69. 69. The use according to any one of claims 66 to 68, wherein the one or more oxidative dyes are represented by formula (2): Derived from an oxidation dye precursor containing a pyrazole primary containing an aminopyrazolone pyridine according to In the above formula, R3 is (2-hydroxyethyl)oxy or 4,4-dimethylpiperazinium, or a combination thereof. use.

70. 70. The use according to any one of claims 66 to 69, wherein the one or more oxidative dyes are represented by formula (3): derived from an oxidation dye precursor containing a pyrazole primary containing a ring-fused 4,5-diaminopyrazolone according to In the above formula, R4 is methylene, ethylene, propylene, or a combination thereof; use.

71. 1. Use of a leucobat dye sulfonate ester to improve the washfastness of hair color produced with oxidation dyes, wherein one or more oxidation dyes are derived from an oxidation dye precursor comprising a pyrazole primary and a coupler.

72. 72. The use according to claim 71, wherein the one or more oxidation dyes are derived from an oxidation dye precursor comprising a pyrazole primary comprising 4,5-diaminopyrazole, an aminopyrazolopyridine, a ring-fused 4,5-diaminopyrazolone or a combination thereof.

73. 73. The use according to claim 71 or 72, wherein the one or more oxidation dyes are represented by the formula (1): derived from an oxidation dye precursor containing a pyrazole primary including a 4,5-diaminopyrazole according to In the above formula, R1 is a linear or branched C1-C6 (hydroxy)alkyl, and R2 is H or a linear or branched C1-C6 (hydroxy)alkyl.

74. 74. The use according to any one of claims 71 to 73, wherein the one or more oxidative dyes are represented by formula (2): Derived from an oxidation dye precursor containing a pyrazole primary containing an aminopyrazolopyridine according to In the above formula, R3 is (2-hydroxyethyl)oxy or 4,4-dimethylpiperazinium, or a combination thereof. use.

75. 75. The use according to any one of claims 71 to 74, wherein the one or more oxidative dyes are represented by formula (3): derived from an oxidation dye precursor containing a pyrazole primary containing a ring-fused 4,5-diaminopyrazolone according to In the above formula, R4 is methylene, ethylene, propylene, or a combination thereof; use.

76. 76. Use according to any one of claims 71 to 75, wherein the Leucobat dye sulfonate ester is a combination of Leucobat dye sulfonate esters.

77. 77. The use of any one of claims 71 to 76, wherein the Leucobat dye sulfonate ester is selected from solubilized Vat Yellow 4 (CAS# 3564-70-3), solubilized Vat Yellow 1 (CAS# 6487-09-8), solubilized Vat Orange 3 (CAS# 10290-03-6), solubilized Vat Orange 9 (CAS# 70356-06-8), or combinations thereof.

Images