WO2026013296A1

WO2026013296A1 - Oxidative dyeing composition, dyeing product, method, and use

Info

Publication number: WO2026013296A1
Application number: PCT/EP2025/070003
Authority: WO
Inventors: Tamara PLATZ
Original assignee: Kao Germany GmbH
Current assignee: Kao Germany GmbH
Priority date: 2024-07-12
Filing date: 2025-07-11
Publication date: 2026-01-15
Anticipated expiration: 2027-01-12

Abstract

The present invention is directed to an oxidative dyeing composition A for keratin fibers, preferably for human keratin fibers, more preferably for human hair, comprising a) one or more oxidative hair dye(s), b) one or more inorganic pigment(s), c) one or more alkalizing agent(s), wherein the weight ratio of one or more compound(s) according to group b) to compound(s) according to group a) is 1 or more.

Description

OXIDATIVE DYEING COMPOSITION, DYEING PRODUCT, METHOD, AND USE

Field of the invention

The present invention is directed to an oxidative dyeing composition, dyeing product, and method for keratin fibers.

Background of the invention

Consumers and professional users alike demand long-lasting high-performance products for perfectly covering gray hair. Such products typically comprise oxidative hair dyes. However, directly upon dyeing the hair, users may be surprised by the amount of color bleeding with the first shampooing. Moreover, this color bleeding may result in a hair color different to the initial one directly upon dyeing.

Inorganic pigments are commonly used in temporary hair dyeing, as the pigments cannot penetrate into the hair fiber due to their particle sizes and will only reside at the hair surface. Thus, any dyeing achieved with inorganic pigments is temporary and usually lasts until the next hair wash.

Typically, such color bleeding of oxidative dyes is undesired for all users. Therefore, there is a need for products being able to reduce the color bleeding of oxidative dyes.

Summary of the invention

The first object of the present invention is an oxidative dyeing composition A for keratin fibers, preferably for human keratin fibers, more preferably for human hair, comprising: a) one or more oxidative hair dye(s), b) one or more inorganic pigment(s), c) one or more alkalizing agent(s), wherein the weight ratio of the one or more compound(s) according to group b) to the compound(s) according to group a) is 1 or more.

The second object of the present invention is an aqueous oxidative dyeing composition A for keratin fibers, preferably human keratin fibers, more preferably human hair, having a pH in the range of 6 to 12 according to any of the preceding claims comprising: a) p-toluene diamine, 1-naphtol, and/or their salt(s), and/or their mixtures, at a total concentration in the range of 0.01% to 10% by weight, calculated to the total weight of composition A, b) one or more ultramarine(s) pigment(s), c) ammonia and/or its salts and/or one or more organic alkalizing agent(s) and/or its/their salt(s), wherein the weight ratio of one or more compound(s) according to group b) to compound(s) according to group a) is 2 or more.

The third object of the present invention is an oxidative dyeing product for keratin fibers, preferably human keratin fibers, more preferably human hair, comprising the composition A as defined above and an acidic composition B comprising one or more oxidizing agent(s), preferably hydrogen peroxide.

The fourth object of the present invention is a method for oxidative dyeing of keratin fibers, preferably human keratin fibers, more preferably human hair, comprising the steps of: a) mixing the composition A as defined above with a composition B as defined above to yield a ready-to-use composition having a pH in the range of 7 to 12, then b) applying the ready-to-use composition onto keratin fibers and leaving it for a time period of 1 to 60 min, then c) rinsing off the keratin fibers and optionally shampooing the keratin fibers.

The fifth object of the present invention is a use of one or more compound(s) according to group c) as defined above for reducing the bleeding of oxidative hair dyes during the first washing of the keratin fibers, preferably human keratin fibers, more preferably human hair, upon dyeing.

Detailed description of the invention

The inventors of the present invention have surprisingly and unexpectedly found that compositions, kits, methods, and use according to the claims of the present invention decreased the bleeding of oxidative dyes during the first shampooing after dyeing, thereby minimizing the change of color with respect to the freshly colored keratin fibers. In addition, the washout of the oxidative dyes from the fibers as well as the damage to the fibers were minimal.

Oxidative dyeing composition A

The present invention is directed to an oxidative dyeing composition A for keratin fibers, preferably for human keratin fibers, more preferably for human hair, comprising: a) one or more oxidative hair dye(s), b) one or more inorganic pigment(s), c) one or more alkalizing agent(s), wherein the weight ratio of the one or more compound(s) according to group b) to the compound(s) according to group a) is 1 or more.

Preferably, the one or more compound(s) according to group a) is/are one or more p- phenylene diamine(s), one or more p-aminophenol(s), one or more diamino pyrazol(s), one or more resorcinol(s), one or more m-aminophenols, one or more m- phenylene diamine(s), one or more pyridine(s), one or more naphtol(s), and/or their salt(s), and/or their mixtures.

Suitably, the one or more compound(s) according to group a) are p-toluene diamine,

1.4-diamino-2-methoxymethyl-benzene, 5-amino-2-methylphenol, 2-methyl-5- hydroxyethylaminophenol, 2, 4, -diaminophenoxyethanol, 2-amino-4- hydroxyethylaminoanisol, 2-methyl-5-amino-6-chlorphenol, 1 ,3-bis-(2,4- diam inophenoxy)-propane, 2-bis(2-hydroxyethyl)-am inotoluene, 2-am ino-5- methylphenol, resorcinol, 2-methylresorcinol, 4-chlororesorcinol, 2-amino-4- chlorophenol, 5-amino-4-methoxy-2-methylphenol, 2-aminophenol, 3-amino-phenol, 1-methyl-2-hydroxy-4-aminobenzene, 3-N,N-dimethyl aminophenol, 2,6-dihydroxy-

3.5-dimethoxypyridine, 5-amino-3-methylphenol, 6-amino-3-methylphenol, 1 ,3- diamino- benzene, 1-amino-3-(2’-hydroxyethylamino)benzene, 1-amino-3-[bis(2’- hydroxy-ethyl) amino]benzene, 1 -naphthol, 4,6-dichlororesorcinol, 1 ,3-diamino- toluene, 4-hydroxy-1 ,2-methylenedioxy benzene, 1 ,5-dihydroxy naphthalene, 1 ,6- dihydroxy naphthalene, 1 ,7-dihydroxy naphthalene, 2,7-dihydroxy naphthalene, 1- hydroxy-2-methyl naphthalene, 4-hydroxy-1 ,2-methyldioxy benzene, 2,4-diamino-3- chlorophenol, 5-amino-2-methoxyphenol and/or 1 -methoxy-2-amino-4-(2’- hydroxyethyl amino)-benzene, 2,4,5,6-tetraaminopyrimidine, 2,5,6-triamino-5- pyrim idinol, and/or their salt(s), and/or their mixtures.

More preferably, the one or more compound(s) according to group a) are p-toluene diamine, 1 -naphtol, p-phenylene diamine, 1 ,4-diamino-2-methoxymethyl-benzene, and/or their salt(s), and/or their mixtures, still more preferably the one or more compound(s) according to group a) is p-toluene diamine, 1 -naphtol, and/or their salt(s), and/or their mixtures.

It is preferred from the viewpoint of dyeing intensity and cometic safety that the total concentration of the one or more compound(s) according to group a) is in the range of 0.01 % to 10% by weight, preferably in the range of 0.025% to 5% by weight, more preferably in the range of 0.05% to 3% by weight, still more preferably in the range of 0.075% to 1 % by weight, calculated to the total weight of the composition A.

Preferably, the one or more compound(s) according to group b) are ultramarine(s) such as ultramarine blue, ultramarine green, ultramarine red, ultramarine violet, and/or ferric blue, Prussian blue, Persian blue, cobalt blue, han blue, azurite, and manganese blue, iron oxides, chrome green, viridian, cobalt green, malachite, cupric acetate, and green earth, carbon black, graphite, fullerene, carbon nanotubes, carbon megatubes, charcoal, soot, titanium black, and/or their mixtures.

The term 'ultramarine(s)’ relates to inorganic pigments with various colors according to the Color index (Cl). Such pigments are, for example, Ultramarine blue as Pigment Blue 29 (Cl 77007), Ultramarine green as Pigment Green 24 (Cl 77013), and Pigment Green 55 (Cl 77007), Ultramarine red as Pigment Red 259, Ultramarine violet as Pigment Violet 15.

In the group of ultramarines, the ultramarine blue (Cl Pigment Blue 29 (77007)) with a molar mass from 916 bis 1026 g/mol and the Cl Pigment Violet 15 (77007) with a molar mass of 874 to 918 g/mol is preferred. Suitable examples are Ultramarine blue light: Na6Al6SieO24S2, Ultramarine blue medium: Na?Al6Si6O24S3, Ultramarine blue dark: NasAl6Si6O24S4, Cl Pigment Violet 15 (77007) with a molar mass of 874 to 918 g/mol are Ultramarine pink: H2Na4Al6SieO24S2 and Ultramarine pink: H2Na6Al6SieO24S2. It is further preferred that the one or more compound(s) according to group b) have a particle size in the range of 1 pm to 1 ,000 pm, more preferably in the range of 5 pm to 500 pm, still more preferably in the range of 10 pm to 250 pm, the particles sizes being average diameters as measured by light microscopy.

It is preferred that the total concentration of the one or more compound(s) according to group b) is in the range of 0.01 % to 10% by weight, preferably in the range of 0.025% to 5% by weight, more preferably in the range of 0.05% to 3% by weight, still more preferably in the range of 0.075% to 1 % by weight, calculated to the total weight of the composition A.

It is further preferred that the total concentration of the ultramarine(s) as the one or more compound(s) according to group b) is in the range of 0.01 % to 10% by weight, preferably in the range of 0.025% to 5% by weight, more preferably in the range of 0.05% to 3% by weight, still more preferably in the range of 0.075% to 1% by weight, calculated to the total weight of the composition A.

It is further preferred that the weight ratio of the one or more compound(s) according to group b) to the one or more compound(s) according to group a) in composition A is 1.2 or more, preferably 1 .5 or more, still more preferably 2 or more.

It is further preferred from the viewpoint of gray hair coverage as well as dyeing intensity that the weight ratio of the one or more compound(s) according to group b) to the one or more compound(s) according to group a) in composition A is 10 or less, preferably 8 or less, still more preferably 5 or less.

For attaining the above-mentioned effects, it is preferred that the weight ratio of the one or more compound(s) according to group b) to the one or more compound(s) according to group a) in composition A is in the range of 1 .2 to 10, preferably in the range of 1 .5 to 8, still more preferably in the range of 2 to 5.

It is further preferred from the viewpoint of alkalinity that the one or more compound(s) according to group c) in composition A are ammonia and/or its salts, one or more metal hydroxide(s), one or more organic alkalizing agent(s) and/or its/their salt(s), preferably the one or more compound(s) according to group c) are selected from ammonia and/or its salt(s), sodium and/or potassium hydroxide, and/or organic alkyl and/or alkanol amines and/or their salt(s) according to the following general structure: wherein Ri , R2, and R3 are independently selected from H, linear Ci-Ce alkyl which may be substituted with one hydroxyl group, or branched C3-C12 alkyl or alkanol, wherein at least one of R1, R2, or R3 is different from H, and/or their salts, and/or their mixtures, more preferably the one or more compound(s) according to group c) are selected from ammonia and/or its salts or monoethanolamine, diethanolamine, monoethanol methylamine, monoethanol dimethylamine, diethanolmethylamine, monoethanolethylamine, monoethanoldiethylamine, diethanolethylamine, monoethanolpropylamine, monoethanoldipropylamine, diethanolpropylamine, monoethanolbutylamine, diethanolbutylamine, trimethylamine, triethylamine, 2- amino-2-methylpropanol, tris-(hydroxymethyl)-aminomethane and/or its/their salt(s), and/or their mixtures, still more preferably the one or more compound(s) according to group c) are selected from ammonia and/or its salt(s), sodium hydroxide, potassium hydroxide, monoethanolamine, 2-amino-2-methylpropanol, tris-(hydroxymethyl)- aminomethane, and/or its/their salt(s).

It is further preferred that the total concentration of the one or more compound(s) according to group c) in composition A is in the range of 0.1 % to 40% by weight, preferably in the range of 0.25% to 30% by weight, more preferably in the range of 0.4% to 25% by weight, still more preferably in the range of 1 % to 20% by weight, still further more preferably in the range of 2% to 10% by weight, calculated to the total weight of composition A.

Product forms of composition A

Preferably, composition A is an aqueous composition comprising water at 50% by weight or more, calculated to the total weight of the composition, and preferably the composition A has a pH in the range of 6 to 12, more preferably it has a pH in the range of 7 to 11 , still more preferably it has a pH in the range of 8 to 10.5. The present invention is also directed to an aqueous oxidative dyeing composition A for keratin fibers, preferably human keratin fibers, more preferably human hair, having a pH in the range of 6 to 12 according to any of the preceding claims comprising: a) p-toluene diamine, 1-naphtol, and/or their salt(s), and/or their mixtures, at a total concentration in the range of 0.01% to 10% by weight, calculated to the total weight of composition A, b) one or more ultramarine(s) pigment(s), c) one or more metal hydroxide(s), preferably sodium hydroxide or potassium hydroxide, wherein the weight ratio of one or more compound(s) according to group b) to compound(s) according to group a) is 2 or more.

Alternatively, the composition A may be a solid composition at 25°C and atmospheric pressure, preferably a hair dyeing powder composition, and more preferably the composition A comprises water at 10% by weight or less, more preferably the composition A comprises water at 1 % by weight or less, still more preferably the composition A comprises water at 0.1 % by weight or less, calculated to the total weight of the composition A, still more preferably the composition A is anhydrous.

Oxidizing agents

In one aspect of the present invention, the composition A further comprises one or more oxidizing agents, preferably hydrogen peroxide.

Suitably, the total concentration of oxidizing agents, preferably the total concentration of hydrogen peroxide, in composition A is in the range of 1 % to 20% by weight, more preferably in the range of 2% to 15% by weight, still more preferably in the range of 3% to 12% by weight, calculated to the total weight of composition A.

The person skilled in the art recognizes that this aspect relates to the composition A being a ready-to-use composition, being preferably prepared directly upon application onto keratin fibers. For this aspect, it is further preferred that the pH of the composition A comprising one or more oxidizing agent(s), preferably hydrogen peroxide, is in the range of 6 to 8, more preferably in the range of 6.5 to 7.5, still more preferably in the range of 6.7 to 7.3.

Lipophilic compounds and surfactants

It is preferred from the viewpoint of user convenience and viscosity that the composition A of the present invention comprises one or more lipophilic compound, said compound(s) being preferably selected from from C12 to C22 fatty alcohols, esters of C3 to C22 alcohols with C12 to C22 fatty acids, Cs to C22 fatty acids, vegetable oils, and/or silicones, and/or hydrocarbon-based products, and/or their mixtures.

Suitable C12 to C22 fatty acohols are linear or branched, saturated or unsaturated fatty alcohols with C12 to C22 substituted with hydroxy or unsubstituted alkyl or alkylene group, preferably they are lauryl alcohol, tridecyl alcohol, myristyl alcohol, pentadecyl alcohol, cetyl alcohol, palmitoleyl alcohol, heptadecyl alcohol, stearyl alcohol, nonadecyl alcohol, arachidyl alcohol, behenyl alcohol, and/or their mixtures.

Suitable fatty acids are saturated or unsaturated fatty acids with or without a hydroxyl group. Suitable are myristoleic acid, palmitoleic acid, oleic acidlinoleic acid, arachidonic acid, and/or their mixtures.

Suitable esters of C3 to C22 alcohols with C12 to C22 fatty acids are isopropyl palmitate, isopropyl myristate, octyl palmitate, isocetyl palmitate, octyl stearate, oleyl oleate, ethylhexyl hydroxystearate, myristyl myristate, behenyl behenate, and/or their mixtures.

Suitable vegetable oils are jojoba oil, avocado oil, sunflower seed oil, walnut oil, peanut oil, olive oil, rapeseed oil, cottonseed oil, palm oil, sesame oil, soybean oil, coconut oil, safflower oil, almond oil, macadamia nut oil, grapefruit seed oil, lemon kernel oil, orange kernel oil, apricot kernel oil, castor oil, and/or their mixtures.

Suitable petrolatum-based products are liquid paraffins, especially paraffinum perliquidum and paraffinum subliquidum, polydecenes, and mineral oil, in particular white mineral oil, and/or their mixtures. Suitable silicones are dimethylpolysiloxanes, and modified silicones (for example, amino-modified silicones, fluorine-modified silicones, alcohol-modified silicones, polyether-modified silicones, epoxy-modified silicones, or alkyl-modified silicones), but dimethylpolysiloxane, polyether-modified silicones and amino-modified silicones are preferred. Amino-modified silicones are commonly known under their CTFA name amodimethicone.

Specific examples of suitable commercially available amodimethicone oils such as SF8452C, SS-3551 (all by Dow Coming Toray Co., Ltd.), KF-8004, KF-867S, and KF-8015 (all by Shin-Etsu Chemical Co. , Ltd.), and amodimethicone emulsions such as SM8704C, SM8904, BY22-079, FZ-4671 , and FZ-4672 (all by Dow coming Toray Co., Ltd.).

The amino-modified silicone may be any silicone having an amino group or a quaternary ammonium group, and examples thereof include amine-modified silicone oil having all or a part of the terminal hydroxyl groups capped with a methyl group for example, and an amodimethicone which does not have the terminals capped.

The most preferred lipophilic compound is cetearyl alcohol.

Suitably, the total concentration of one or more lipophilic compound(s) in composition A, preferably the total concentration of C12 to C22 fatty alcohols, esters of C3 to C22 alcohols with C12 to C22 fatty acids, Cs to C22 fatty acids, vegetable oils, and/or silicones, and/or hydrocarbon-based products, and/or their mixtures, is in the range from 0.1 % to 25% by weight, preferably in the range of 0.25% to 20% by weight, more preferably in the range of 0.5% to 15% by weight, still more preferably in the range of 1 % to 10% by weight, calculated to the total weight of the composition A.

Preferably, the composition A according to the present invention comprises one or more surfactant(s), preferably one or more non-ionic, anionic, cationic or amphoteric/zwitterionic surfactant surfactant(s), and/or their salt(s), and/or their mixtures.

Anionic surfactants suitable are in principle known from the cleansing compositions. These are anionic surfactants of the sulfate, sulfonate, carboxylate and alkyl phosphate type, for example, the known Cio-C -alkyl sulfates, and in particular the respective ether sulfates, for example, Ci2-Ci4-alkyl ether sulfate, lauryl ether sulfate, especially with 1 to 4 ethylene oxide groups in the molecule, monoglyceride (ether) sulfates, fatty acid amide sulfates obtained by ethoxylation and subsequent sulfatation of fatty acid alkanolamides, and the alkali salts thereof, as well as the salts of long-chain mono- and dialkyl phosphates. Preferred anionic surfactants are alkyl sulphate surfactants especially lauryl sulfate, cetearyl sulfate, and/or its/their salts.

Suitable amphoteric/zwitterionic surfactants are in particular the various known betaines such as alkyl betaines, fatty acid amidoalkyl betaines and sulfobetaines, for example, lauryl hydroxysulfobetaine; long-chain alkyl amino acids, such as cocoaminoacetate, cocoaminopropionate and sodium cocoamphopropionate and - acetate are also suitable.

Typical cationic surfactants are cetyl trimethyl ammonium chloride, stearyl trimonium chloride, dipalmitoyl dimonium chloride, distearyl dimethyl ammonium chloride, stearamidopropyl trimonuim chloride, dioleoylethyl dimethyl ammonium methosulfate, dioleoylethyl hydroxyethylmonium methosulfate.

Suitably, composition A comprises nonionic surfactants. Non-limiting examples are long-chain fatty acid mono- and dialkanolamides, such as coco fatty acid mono- or diethanolamide and myristic fatty acid mono or diethanolamide, stearic acid mono or diethanolamide, alkyl polyglucosides with an alkyl group of 8 to 18 carbon atoms, and with 1 to 5 glucoside units, sorbitan esters, such as polyethylene glycol sorbitan stearic, palmitic, myristic and lauric acid esters, fatty acid polyglycol esters or polycondensates of ethyleneoxide and propyleneoxide, as they are on the market, for example, under the trade name "Pluronics^R", as well as ethoxylated fatty alcohols, C -C22-fatty alcohol ethoxylates, known by the generic terms "Laureth", "Myristeth", "Oleth", "Ceteth", "Deceth", "Steareth" and "Ceteareth" according to the CTFA nomenclature, including addition of the number of ethylene oxide molecules, e.g., "Laureth-16": The average degree of ethoxylation thereby ranges between about 2.5 and about 100, preferably about 10 and about 30.

Preferably, the one or more non-ionic surfactant(s) are selected from alkyl polyglycosides, ethoxylated triglycerides, ethoxylated fatty alcohols, ethoxylated fatty acid esters, and/or their mixtures, still more preferably said compound(s) are selected from ethoxylated C10-C22 fatty alcohols.

The preferred surfactants for composition A are anionic surfactants. It is further preferred that the concentration one or more surfactants, preferably the total concentration of anionic surfactant(s), is in the range from 0.1 % to 25% by weight, preferably in the range of 0.25% to 20% by weight, more preferably in the range of 0.5% to 15% by weight, still more preferably in the range of 1 % to 10% by weight, calculated to the total weight of the composition A.

In a further preferred aspect, the composition of the present invention is an emulsion, preferably an oil-in-water emulsion. Suitably, the lipophilic compounds and surfactants as disclosed above are present.

Oxidative dyeing product

The present invention is also directed to an oxidative dyeing product for keratin fibers, preferably human keratin fibers, more preferably human hair, comprising the composition A as defined above and an acidic composition B comprising one or more oxidizing agent(s), preferably hydrogen peroxide.

Preferably, the compositions A and B are kept separate directly prior to application onto keratin fibers. Further preferably, the pH of the ready-to-use composition prepared by mixing the compositions A and B directly prior to application onto keratin fibers is in the range of 6.5 to 8.0, more preferably in the range of 6.5 to 7.5, still more preferably in the range of 6.5 to 7.2.

It is further preferred that the composition B is an aqueous composition. The term ‘aqueous’ has the same denotation as disclosed further above.

In one aspect of the present invention, the composition B is an aqueous composition, and the composition A is not. It is preferred from the viewpoint of stability, that the total concentration of water in the compositions A is 10% by weight or less, preferably 1% by weight or less, more preferably 0.1 % by weight or less, calculated to the total weight of compositions A, more preferably compositions A is an anhydrous composition.

Suitably, composition A is a powder composition.

It is preferred from the viewpoint of performance that the composition of the present invention is obtainable by mixing/dissolving/dispersing the compositions A and B of the oxidative dyeing product directly prior to the application onto keratin fibers. Dyeing method

The present invention is also directed to a method for oxidative dyeing of keratin fibers, preferably human keratin fibers, more preferably human hair, comprising the steps of: a) mixing the composition A as defined above with a composition B as defined above to yield a ready-to-use composition having a pH in the range of 6 to 12, then b) applying the ready-to-use composition onto keratin fibers and leaving it for a time period of 1 to 60 min, then c) rinsing off the keratin fibers and optionally shampooing the keratin fibers.

The preferred application time if step b) is in the range of 2 min to 45 min, more preferably it is in the range of 5 min to 35 min, still more preferably it is in the range of 5 min to 25 min.

It is further preferred that the pH of the ready-to-use composition of step a) is in the range of 6.5 to 8.0, more preferably in the range of 6.5 to 7.5, still more preferably in the range of 6.5 to 7.2.

Furthermore, it is preferred that the mixing ratio by weight of composition A to composition B in step a) is in the range of 0.3 to 3, preferably in the range of 0.5 to 2.5, still more preferably it is 0.5.

It is preferred in step c) that the keratin fibers are not shampooed.

Use

The present invention is also directed to the use of one or more compound(s) according to group c) as defined above for reducing the bleeding of oxidative hair dyes during the first washing of the keratin fibers, preferably human keratin fibers, more preferably human hair, upon dyeing.

The following examples are to illustrate the present invention and not to limit it. EXAMPLES

Table 1

Methods

The compositions A of table 1 were mixed with an oxidizing composition B comprising hydrogen peroxide at 2% by weight in a weight ratio of 1 :2 to prepare a ready-to-use composition having a pH of 6.8 ± 0.1. Yak hair streaks (11 cm long, 2 g per bundle) were dyed for 30 min at 40°C, then the streaks were rinsed-off with water and blow dried.

L*i, a*i, b*i values of Yak hair streaks (11 cm long, 2 g per bundle) were measured with a Datacolor 45 spectrometer (rinsed-off once + dried)

The hair streaks were then immersed in a shaking bath comprising 5% by weight of sodium laureth sulfate for 5 min, rinsed-off with water, and blow-dried. L*2, a*2, b*2 (1^st wash + dried) values were measured with a Datacolor 45 spectrometer. AE*was calculated as follows:

Claims

1. An oxidative dyeing composition A for keratin fibers, preferably for human keratin fibers, more preferably for human hair, comprising: a) one or more oxidative hair dye(s), b) one or more inorganic pigment(s), c) one or more alkalizing agent(s), wherein the weight ratio of the one or more compound(s) according to group b) to the compound(s) according to group a) is 1 or more.

2. The composition according to claim 1 characterized in that the one or more compound(s) according to group a) is one or more p-phenylene diamine(s), one or more p-aminophenol(s), one or more diamino pyrazol(s), one or more resorcinol(s), one or more m-aminophenols, one or more m-phenylene diamine(s), one or more pyridine(s), one or more naphtol(s), and/or their salt(s), and/or their mixtures, preferably the one or more compound(s) according to group a) are p-toluene diamine, 1 ,4-diamino-2-methoxymethyl-benzene, 5-amino-2-methylphenol, 2-methyl- 5-hydroxyethylaminophenol, 2, 4, -diaminophenoxyethanol, 2-amino-4- hydroxyethylaminoanisol, 2-methyl-5-amino-6-chlorphenol, 1 ,3-bis-(2,4- diam inophenoxy)-propane, 2-bis(2-hydroxyethyl)-am inotoluene, 2-am ino-5- methylphenol, resorcinol, 2-methylresorcinol, 4-chlororesorcinol, 2-amino-4- chlorophenol, 5-amino-4-methoxy-2-methylphenol, 2-aminophenol, 3-amino-phenol, 1-methyl-2-hydroxy-4-aminobenzene, 3-N,N-dimethyl aminophenol, 2,6-dihydroxy- 3,5-dimethoxypyridine, 5-amino-3-methylphenol, 6-amino-3-methylphenol, 1 ,3- diamino- benzene, 1-amino-3-(2’-hydroxyethylamino)benzene, 1-amino-3-[bis(2’- hydroxy-ethyl) amino]benzene, 1 -naphthol, 4,6-dichlororesorcinol, 1 ,3-diamino- toluene, 4-hydroxy-1 ,2-methylenedioxy benzene, 1 ,5-dihydroxy naphthalene, 1 ,6- dihydroxy naphthalene, 1 ,7-dihydroxy naphthalene, 2,7-dihydroxy naphthalene, 1- hydroxy-2-methyl naphthalene, 4-hydroxy-1 ,2-methyldioxy benzene, 2,4-diamino-3- chlorophenol, 5-amino-2-methoxyphenol and/or 1-methoxy-2-amino-4-(2’- hydroxyethyl amino)-benzene, 2,4,5,6-tetraaminopyrimidine, 2,5,6-triamino-5- pyrim idinol, and/or their salt(s), and/or their mixtures, more preferably the one or more compound(s) according to group a) is p-toluene diamine, 1-naphtol, p- phenylene diamine, 1 ,4-diamino-2-methoxymethyl-benzene, and/or their salt(s), and/or their mixtures, still more preferably the one or more compound(s) according to group a) is p-toluene diamine, 1-naphtol, and/or their salt(s), and/or their mixtures.

3. The composition according to any of the preceding claims characterized in that the total concentration of the one or more compound(s) according to group a) is in the range of 0.01 % to 10% by weight, preferably in the range of 0.025% to 5% by weight, more preferably in the range of 0.05% to 3% by weight, still more preferably in the range of 0.075% to 1 % by weight, calculated to the total weight of the composition A.

4. The composition according to any of the preceding claims characterized in that the one or more compound(s) according to group b) are ultramarine(s) such as ultramarine blue, ultramarine green, ultramarine red, ultramarine violet, and/or, ferric blue, Prussian blue, Persian blue, cobalt blue, han blue, azurite, and manganese blue, iron oxides, chrome green, viridian, cobalt green, malachite, cupric acetate, and green earth, carbon black, graphite, fullerene, carbon nanotubes, carbon megatubes, charcoal, soot, titanium black, and/or their mixtures, preferably the one or more compound(s) according to group b) are ultramarines such as ultramarine blue, ultramarine green, ultramarine red, ultramarine violet, and/or their mixtures.

5. The composition according to any of the preceding claims characterized in that the total concentration of the one or more compound(s) according to group b) is in the range of 0.01 % to 10% by weight, preferably in the range of 0.025% to 5% by weight, more preferably in the range of 0.05% to 3% by weight, still more preferably in the range of 0.075% to 1 % by weight, calculated to the total weight of the composition A.

6. The composition according to any of the preceding claims characterized in that the weight ratio of the one or more compound(s) according to group b) to the one or more compound(s) according to group a) is 1 .2 or more, preferably 1 .5 or more, still more preferably 2 or more.

7. The composition according to any of the preceding claims characterized in that the one or more compound(s) according to group c) are ammonia and/or its salts, one or more metal hydroxide(s), one or more organic alkalizing agent(s) and/or its/their salt(s), preferably the one or more compound(s) according to group c) are selected from ammonia and/or its salt(s), sodium and/or potassium hydroxide, and/or organic alkyl and/or alkanol amines and/or their salt(s) according to the following general structure: wherein Ri , R2, and R3 are independently selected from H, linear Ci-Ce alkyl which may be substituted with one hydroxyl group, or branched C3-C12 alkyl or alkanol, wherein at least one of R1, R2, or R3 is different from H, and/or their salts, and/or their mixtures, more preferably the one or more compound(s) according to group c) are selected from ammonia and/or its salts, sodium hydroxide, potassium hydroxide, monoethanolamine, diethanolamine, monoethanol methylamine, monoethanol dimethylamine, diethanolmethylamine, monoethanolethylamine, monoethanoldiethylamine, diethanolethylamine, monoethanolpropylamine, monoethanoldipropylamine, diethanolpropylamine, monoethanolbutylamine, diethanolbutylamine, trimethylamine, triethylamine, 2-amino-2-methylpropanol, tris- (hydroxymethyl)-aminomethane and/or its/their salt(s), and/or their mixtures, still more preferably the one or more compound(s) according to group c) are selected from ammonia and/or its salt(s), sodium hydroxide, potassium hydroxide, and/or monoethanolamine, 2-amino-2-methylpropanol, tris-(hydroxymethyl)-aminomethane, and/or its/their salt(s).

8. The composition according to any of the preceding claims characterized in that the total concentration of one or more compound(s) according to group c) is in the range of 0.1 % to 40% by weight, preferably in the range of 0.25% to 30% by weight, more preferably in the range of 0.4% to 25% by weight, still more preferably in the range of 1 % to 20% by weight, still further more preferably in the range of 2% to 10% by weight, calculated to the total weight of composition A.

9. The composition according to any of the preceding claims characterized in that the composition is an aqueous composition comprising water at 50% by weight or more, calculated to the total weight of the composition, and preferably the composition has a pH in the range of 6 to 12, more preferably it has a pH in the range of 7 to 11 , still more preferably it has a pH in the range of 8 to 10.5.

10. The composition according to any of the claims 1 to 8 characterized in that the composition is a solid composition at 25°C and atmospheric pressure, preferably a hair dyeing powder composition, and more preferably the composition comprises water at 10% by weight or less, more preferably the composition comprises water at 1% by weight or less, still more preferably the composition comprises water at 0.1 % by weight or less, calculated to the total weight of the composition A, still more preferably the composition is anhydrous.

11 . The composition according to any of the preceding claims characterized in that the composition A further comprises one or more oxidizing agents, preferably hydrogen peroxide.

12. An aqueous oxidative dyeing composition A for keratin fibers, preferably human keratin fibers, more preferably human hair, having a pH in the range of 7 to 12 according to any of the preceding claims comprising: a) p-toluene diamine, 1-naphtol, and/or their salt(s), and/or their mixtures, at a total concentration in the range of 0.01% to 10% by weight, calculated to the total weight of composition A, b) one or more ultramarine(s) pigment(s), c) ammonia and/or its salts and/or one or more organic alkalizing agent(s) and/or its/their salt(s), wherein the weight ratio of one or more compound(s) according to group b) to compound(s) according to group a) is 2 or more.

13. An oxidative dyeing product for keratin fibers, preferably human keratin fibers, more preferably human hair, comprising the composition A as defined in any of the claims 1 to 12 and an acidic composition B comprising one or more oxidizing agent(s), preferably hydrogen peroxide.

14. A method for oxidative dyeing of keratin fibers, preferably human keratin fibers, more preferably human hair, comprising the steps of: a) mixing the composition A as defined in any of the claims 1 to 12 with a composition B as defined in claim 13 to yield a ready-to-use composition having a pH in the range of 6 to 12, then b) applying the ready-to-use composition onto keratin fibers and leaving it for a time period of 1 to 60 min, then c) rinsing off the keratin fibers and optionally shampooing the keratin fibers.

15. Use of one or more compound(s) according to group c) as defined in any of the claims 1 to 12 for reducing the bleeding of oxidative hair dyes during the first washing of the keratin fibers, preferably human keratin fibers, more preferably human hair, upon dyeing.