WO2005027861A1 - Agents permettant de reduire la coloration du cuir chevelu lors de processus de coloration capillaire - Google Patents

Agents permettant de reduire la coloration du cuir chevelu lors de processus de coloration capillaire Download PDF

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Publication number
WO2005027861A1
WO2005027861A1 PCT/EP2004/010005 EP2004010005W WO2005027861A1 WO 2005027861 A1 WO2005027861 A1 WO 2005027861A1 EP 2004010005 W EP2004010005 W EP 2004010005W WO 2005027861 A1 WO2005027861 A1 WO 2005027861A1
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compounds
acid
amino
hair
group
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PCT/EP2004/010005
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German (de)
English (en)
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Horst Höffkes
Barbara Horstmann
Winifried Neuhaus
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Henkel Kommanditgesellschaft Auf Aktien
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Priority to EP04764948A priority Critical patent/EP1684871A1/fr
Publication of WO2005027861A1 publication Critical patent/WO2005027861A1/fr

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/55—Phosphorus compounds
    • A61K8/553—Phospholipids, e.g. lecithin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/36—Carboxylic acids; Salts or anhydrides thereof
    • A61K8/365—Hydroxycarboxylic acids; Ketocarboxylic acids
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/41—Amines
    • A61K8/411—Aromatic amines, i.e. where the amino group is directly linked to the aromatic nucleus
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/41—Amines
    • A61K8/416—Quaternary ammonium compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/4906—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom
    • A61K8/4926—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having six membered rings
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
    • A61K8/4946—Imidazoles or their condensed derivatives, e.g. benzimidazoles
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/58—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing atoms other than carbon, hydrogen, halogen, oxygen, nitrogen, sulfur or phosphorus
    • A61K8/585—Organosilicon compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/67—Vitamins
    • A61K8/676—Ascorbic acid, i.e. vitamin C
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/10—Preparations for permanently dyeing the hair

Definitions

  • the invention relates to an agent for treating the scalp, a method for pretreating the scalp and the use of special components for pretreating the scalp before a hair coloring process.
  • It also relates to a kit that contains a scalp pretreatment agent and a hair dye in two separate packages.
  • Coloring agents or tinting agents which contain so-called direct draws as the coloring component are usually used for temporary dyeings. These are dye molecules that attach directly to the hair and do not require an oxidative process to form the color. These dyes include, for example, henna, which is known from antiquity for coloring body and hair. These dyeings are generally sensitive to shampooing, so that a frequently undesirable shift in shades or even a visible “discoloration" can occur.
  • oxidation dyes are used for permanent, intensive dyeings with appropriate fastness properties.
  • Such colorants usually contain oxidation dye precursors, so-called developer components and coupler components.
  • the developer components form the actual dyes under the influence of oxidizing agents or atmospheric oxygen with one another or under coupling with one or more coupler components.
  • the oxidation coloring agents are characterized by excellent, long-lasting coloring results.
  • another dyeing process has received great attention. In this process, precursors of the natural hair dye melanin are applied to the hair; These then form naturally analogous dyes in the hair as part of oxidative processes.
  • Such a process with 5,6-dihydroxyindoline as a dye precursor was described in EP-B 1-530 229.
  • Another way to dye keratin-containing fibers is to use dyes that are a combination of components
  • the above-mentioned components A and B are generally not themselves dyes and are therefore not suitable for dyeing keratin fibers on their own. In combination, they form dyes in a non-oxidative process.
  • Corresponding oxidation dye precursors of the developer and / or coupler type with or without the use of an oxidizing agent can, however, also be used among compounds of component B.
  • oxo dyeing This dyeing method (hereinafter called oxo dyeing) can thus be easily combined with the oxidative dyeing system.
  • Components A and B are referred to below as oxo dye precursors.
  • the oxo dyeing is described, for example, in the publications WO-A1-99 / 18916, WO-A1 -00/38638, WO-A1 -01/34106 and WO-A1 -01/47483.
  • DE-A1-100 28 723 discloses a hair dyeing method in which the scalp and the hair contour area are first treated with a water-in-oil emulsion based on an oil component and a nonionic emulsifier to reduce scalp staining. The hair dye product is then applied to the hair. After a usual exposure time for hair coloring, the hair is washed thoroughly.
  • the W / O-emulsion according to DE-A1 -10028723 also includes a volatile silicone.
  • WO-A1 -96 / 18379 discloses a cosmetic and dermatological agent which contains at least one compound from the group of the flavonoids to protect the skin and hair from oxidative stress.
  • the subject of this application is an agent for "pretreating the scalp before a hair dyeing process which, in order to reduce the color of the scalp, comprises at least one component from the group of physiologically compatible hydroxycarboxylic acids, inorganic and organic reducing agents, quaternary ammonium compounds, amphoteric or zwitterionic surfactants, non-volatile silicone compounds, Contains office scale agents and / or from mixtures of these compounds and / or from the physiologically tolerable salts of these compounds.
  • Hydroxycarboxylic acids and salts of hydroxycarboxylic acids in the context of the invention are lactic acid, mandelic acid, malic acid, tartaric acid, citric acid, salicylic acid and the salts of these acids.
  • the agents additionally have a physiologically tolerable content of aldonic acid, malonic acid, phosphonic acid, sulfonic acid, hydrochloric acid, phosphoric acid, dihydrogphosphate and oxydicarboxylic acids from monosaccharides such as glucose, mannose, galactose or the physiologically tolerable salts of these acids.
  • Physiologically acceptable salts are to be understood as alkali and alkaline earth and ammonium salts.
  • the hydroxycarboxylic acids and / or the hydroxycarboxylic acid salts are usually used in the agents according to the invention in an amount of 0.05 to 10% by weight, based on the total weight of the agent.
  • the agents contain sodium salicylate.
  • Inorganic and organic reducing agents in the context of the invention include the compounds sodium metabisulfite, sodium dithionite, sodium salts of hydroxymethanesulfonic acid, the sulfinic acid derivatives listed in documents WO 02/039965 AI, WO 02 / 030369A1 and WO 02/015855, thiols such as cysteine, N-acetylcysteine, Cysteamine, the reduced form of glutathione, ascorbic acid, isoascorbic acid, 2,3-dihydroxy-2-cyclopenten-l-one or 6-0-palmitoyl ascorbate understood.
  • thiols such as cysteine, N-acetylcysteine, Cysteamine, the reduced form of glutathione, ascorbic acid, isoascorbic acid, 2,3-dihydroxy-2-cyclopenten-l-one or 6-0-palmitoyl ascorbate understood.
  • the inorganic reducing agents are usually used in the agents according to the invention in an amount of 0.05 to 10% by weight, preferably in an amount of 1 to 5% by weight, in each case based on the total weight of the agent.
  • the agents contain ascorbic acid or isoascorbic acid.
  • Quaternary ammonium compounds in the sense of the invention can be selected from cationic polymers with quaternary ammonium group and from cationic surfactants with quaternary ammonium group.
  • Cationic polymers suitable according to the invention are those under the INCI names Polyquaternium-2, Polyquaternium-4, Polyquaternium-6, Polyquaternium-7, Polyquaternium-10, Polyquaternium-11, Polyquaternium-16, Polyquaternium-22, Polyquaternium-28, Polyquatemium-29 , Polyquaternium-32, Polyquaternium-37, Polyquaternium-44, available polymers.
  • the cationic polymers are usually used in the agents according to the invention in an amount of 0.1 to 5% by weight, preferably in an amount of 0.1-3% by weight, in each case based on the total weight of the agent.
  • Cationic surfactants suitable according to the invention are cationic surfactants of the quaternary ammonium compound, esterquat and amidoamine type.
  • Preferred quaternary ammonium compounds are ammonium halides, especially chlorides and bromides, such as alkyltriethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g. B.
  • cetyltrimethylammonium chloride stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylarmnonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylarrimonium chloride, as well as the compounds known under the INCI names Quatemium-27 and Quatemium-83 imidazolium.
  • the long alkyl chains of the above-mentioned surfactants preferably have 10 to 18 carbon atoms.
  • Ester quats are known substances which contain both at least one ester function and at least one quaternary ammonium group as a structural element.
  • Preferred ester quats are quaternized ester salts of fatty acids with triethanolamine, quaternized ester salts of fatty acids with diethanolalkylamines and quaternized ester salts of fatty acids with 1,2-dihydroxypropyldialkylamines.
  • Such products are sold, for example, under the trademarks Stepantex ® , Dehyquart ® and Armocare ® .
  • alkylamidoamines are usually produced by amidation of natural or synthetic fatty acids and fatty acid cuts with dialkylaminoamines.
  • An inventively particularly suitable compound from this group is that available under the name Tegoamid ® S 18 commercially stearamidopropyl dimethylamine.
  • Linoleamidopropyl PG-Dimonium Chloride Phosphate which is sold under the trade name Phospholipid EVA ® (Uniqema) is a preferably used in the inventive compositions cationic surfactant.
  • the agents contain linoleamidopropyl PG-dimonium chloride phosphates, alkyltrimethylammonium halides, dialkyldimethylammonium halides, trialkylmethylammonium halides or esterquats.
  • Preferred halides for the purposes of the invention are understood to mean chlorides and bromides; the chlorides are particularly preferred.
  • the cationic surfactants are preferably present in the agents according to the invention in amounts of 0.05 to 10% by weight, based on the total agent. Amounts of 0.1 to 5% by weight are particularly preferred.
  • Amphoteric or zwitterionic surfactants which are suitable according to the invention are selected from surface-active compounds which, in addition to a C 8 -C 24 -alkyl or -acyl group, contain at least one free amino group and at least one -COOH or -SOaH group in the molecule and to form internal salts are qualified.
  • ampholytic or zwitterionic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N- Alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyltaurine, N-alkylsarcosine, 2-alkylaminopropionic acid, alkylaminoacetic acids and acylaminoalkylbetaines, each with about 8 to 24 carbon atoms in the alkyl group.
  • ampholytic or zwitterionic surfactants are the N-cocoalkylaminopropionate and dipropionate, the cocoacylaminoethylamino propionate, the C 2 -Ci ⁇ -acyl sarcosine and the cocoamidopropyl betaine.
  • the agents contain cocoamphodipropionate or cocoamidopropylbetaine.
  • amphoteric or zwitterionic surfactants are preferably present in the agents according to the invention in amounts of 0.05 to 10% by weight, based on the total agent. Amounts of 0.1 to 5% by weight are particularly preferred.
  • non-volatile silicones suitable according to the invention are water-soluble surfactants based on silicone. In a preferred embodiment, these are nonionic.
  • Particularly preferred water-soluble surfactants based on silicone are selected from the group of dimethicone copolyols which are preferably alkoxylated, in particular polyethoxylated and / or polypropoxylated.
  • the water-soluble silicone surfactant is used in the compositions according to the invention in an amount of 0.01 to 10% by weight, in particular in an amount of 0.1 to 5% by weight.
  • Dimethicone copolyols are understood according to the invention to mean polyoxyalkylene-modified dimethylpolysiloxanes of the general formulas I or II: (I)
  • the radical R can represent a hydrogen atom, an alkyl group with 1 to 12 C atoms, an alkoxy group with 1 to 12 C atoms or a hydroxyl group,
  • x represents an integer from 1 to 100, preferably from 20 to 30,
  • - Y represents an integer from 1 to 20, preferably from 2 to 10, and
  • a and b are integers from 0 to 50, preferably from 10 to 30.
  • dimethicone copolyols for the purposes of the invention are, for example, the products sold commercially under the trade names SILWET (Union Carbide Corporation) and DOW CORNING (Dow).
  • Dow Corning 190 and Dow Corning 193 are particularly preferred dimethicone copolyols according to the invention.
  • Antidandruff active substances which are suitable according to the invention are, for example, elementary colloidal sulfur, zinc pyridinthione and those of the Tradenames available from Octopirox and Climbazol.
  • antidandruff agents based on natural substances for example extracts from arnica, birch, burdock root, beard lichen, poplar, nettle and walnut shells can also be used according to the invention.
  • the antidandruff active ingredients are usually used in the agents according to the invention in a concentration of 0.05-5% by weight, preferably in a concentration of 0.1-2% by weight and in particular 0.15-1% by weight.
  • the agents contain at least two components from the group of the physiologically compatible hydroxycarboxylic acids, inorganic and organic reducing agents, quaternary ammonium compounds, amphoteric or zwitterionic surfactants, non-volatile silicone compounds, antidandruff agents and / or mixtures of these compounds and / or from the physiologically tolerable salts of these compounds.
  • the agents according to the invention can preferably be formulated in an aqueous or aqueous-alcoholic base.
  • Lower alcohols such as ethanol and isopropanol are particularly suitable as alcohols.
  • Aqueous-alcoholic bases can contain water-alcohol, preferably in a ratio of 1: 5 to 5: 1.
  • a preferred aqueous-alcoholic base has an alcohol content of up to 15% by weight, based on the amount of water.
  • the agents according to the invention are therefore formulated for treating the scalp as aqueous or aqueous-alcoholic agents.
  • Thickened formulations have proven to be particularly effective for the treatment of the hair contour area, since they adhere well to the skin and thus do not get into the eyes of the user.
  • the agents according to the invention are therefore formulated as thickened agents for treating the hair contour area.
  • these consistency regulators and / or thickeners are added.
  • Suitable consistency agents are primarily fatty alcohols or hydroxyfatty alcohols with 12 to 22 and preferably 16 to 18 carbon atoms and also partial glycerides, fatty acids or hydroxyfatty acids. A combination of these substances with alkyl oligoglucosides and or fatty acid N-methylglucamides of the same chain length and / or polyglycerol poly-12-hydroxystearates is preferred.
  • Suitable thickeners are, for example, polysaccharides, in particular xanthan gum, guar guar, agar agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl cellulose, and also hearing molecules
  • surfactants such as, for example, ethoxylated fatty acid glycerides, esters of fatty acids with polyols such as, for example, pentaerythritol or trimethylolpropane with fatty alcohol narrow homolog distribution or alkyl oligoglucosides as well as electrolytes such as table salt and ammonium chloride.
  • the thickeners are usually used in a concentration of 0.1-10% by weight, preferably in a concentration of 0.2-5% by weight and in particular 0.3-2% by weight, in the agents according to the invention.
  • the agents according to the invention have a pH in the range of 0-10, preferably in the range of 0.5-7 and in particular in the range of 1-6.
  • the pretreatment of the scalp and the hair contour area with the agents according to the invention is particularly useful and necessary if the hair is to be colored with deep and intense oxidative, direct or natural dyes.
  • the agents can also be used prophylactically before each hair coloring.
  • the term dyeing process includes all processes known to the person skilled in the art, in which a dye is applied to the optionally moistened hair and either left on the hair for a period of between a few minutes and about 45 minutes and then rinsed out with water or a surfactant-containing agent or is left entirely on the hair.
  • a dye is applied to the optionally moistened hair and either left on the hair for a period of between a few minutes and about 45 minutes and then rinsed out with water or a surfactant-containing agent or is left entirely on the hair.
  • monographs e.g. Kh. Schrader, Fundamentals and Recipes of Cosmetics, 2nd edition, Hüthig Buch Verlag, Heidelberg, 1989, referring to the corresponding knowledge of the expert.
  • composition of the colorants or tints is not subject to any fundamental restrictions.
  • Oxidation dye precursors of the developer and coupler type
  • the direct dyes are usually nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols.
  • Preferred direct dyes are those with the international names or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, Acid Yellow 1, Acid Yellow 10, Acid Yellow 23, Acid Yellow 36, HC Orange 1 , Disperse Orange 3, Acid Orange 7, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, Acid Red 33, Acid Red 52, HC Red BN, Pigment Red 57: 1, HC Blue 2 , HC Blue 12, Disperse Blue 3, Acid Blue 7, Acid Green 50, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Acid Violet 43, Disperse Black 9, Acid Black 1 and Acid Black 52 known compounds as well as 1,4 -Diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1, 4-bis- (ß-hydroxyethyl) -
  • Cationic direct dyes can also be used. Particular preference is given to (a) cationic triphenylmethane dyes, such as, for example, Basic Blue 7, Basic Blue 26, Basic Violet 2 and Basic Violet 14, (b) aromatic systems which are substituted by a quaternary nitrogen group, such as, for example, Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 and Basic Brown 17, as well as (c) direct dyes which contain a heterocycle which has at least one quaternary nitrogen atom, as described, for example, in EP-A2-998 908, at this point explicit reference is made to claims 6 to 11.
  • quaternary nitrogen group such as, for example, Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 and Basic Brown 17
  • direct dyes which contain a heterocycle which has at least one quaternary nitrogen atom, as described, for example, in EP-A2-998 908, at this point explicit reference is made to claims 6 to 11.
  • Preferred cationic direct dyes of group (c) are in particular the following compounds:
  • the compounds of the formulas (DZl), (DZ3) and (DZ5) are very particularly preferred cationic direct dyes of the group (c).
  • the cationic direct dyes sold under the trademark Arianor ® are particularly preferred direct dyes according to the invention.
  • developer type oxidation dye precursors are p-phenylenediamine derivatives or one of its physiologically tolerable salts.
  • P-Phenylenediamine derivatives of the formula (E1) are particularly preferred
  • G 1 represents a hydrogen atom, a d- to C 4 -alkyl radical, a C- ⁇ - to C 4 - monohydroxyalkyl radical, a C 2 - to C 4 -polyhydroxyalkyl radical, a (C- ⁇ - to C 4 ) alkoxy - (Cr to C 4 ) alkyl, a 4'-aminophenyl or a C 1 - to C 4 alkyl which is substituted by a nitrogen-containing group, a phenyl or a 4'-aminophenyl group;
  • - G 2 represents a hydrogen atom, a C to C 4 alkyl radical, a C 1 -C 4 monohydroxyalkyl radical, a C 2 to C 4 polyhydroxyalkyl radical, a (C1 to C 4 ) alkoxy (i.e. - to C 4 ) -alkyl radical or a C to C 4 -alkyl radical which is substituted by a nitrogen-containing group;
  • G 3 represents a hydrogen atom, a halogen atom, such as a chlorine, bromine, iodine or fluorine atom, a C to C 4 alkyl radical, a C to C 4 monohydroxyalkyl radical, a C 2 to C 4 polyhydroxyalkyl radical, a Cr to C 4 hydroxyalkoxy radical, a C to C 4 acetylaminoalkoxy radical, a C to C 4 mesylaminoalkoxy radical or a C 1 to C 4 carbamoylaminoalkoxy radical;
  • a halogen atom such as a chlorine, bromine, iodine or fluorine atom
  • a C to C 4 alkyl radical such as a chlorine, bromine, iodine or fluorine atom
  • a C to C 4 alkyl radical such as a chlorine, bromine, iodine or fluorine atom
  • a C to C 4 alkyl radical such as a chlorine,
  • G 4 represents a hydrogen atom, a halogen atom or a Cr to C 4 alkyl radical or - If G 3 and G 4 are ortho to each other, they can together form a bridging ⁇ , ⁇ -alkylenedioxo group, such as an ethylenedioxy group.
  • C 1 -C 4 -alkyl radicals mentioned as substituents in the compounds according to the invention are the groups methyl, ethyl, propyl, isopropyl and butyl. Ethyl and methyl are preferred alkyl radicals.
  • Cr to C 4 alkoxy radicals preferred according to the invention are, for example, a methoxy or an ethoxy group. Further preferred examples of a Cr to C 4 - hydroxyalkyl group are a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group. A 2-hydroxyethyl group is particularly preferred.
  • a particularly preferred C 2 - to C 4 -polyhydroxyalkyl group is the 1, 2-dihydroxyethyl.
  • halogen atoms according to the invention are F, Cl or Br atoms, Cl atoms are very particularly preferred.
  • the other terms used are derived from the definitions given here.
  • nitrogen-containing groups of the formula (E1) are in particular the amino groups, Cr to C 4 monoalkylamino groups, Cr to C 4 dialkylamino groups, Cr to C 4 trialkylammonium groups, Cr to C 4 monohydroxyalkylamino groups, imidazolinium and ammonium.
  • Particularly preferred p-phenylenediamines of the formula (E1) are selected from p-phenylenediamine, p-toluenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2 , 6-diethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, N, N-dipropyl-p-phenylenediamine, 4 -Amino-3-methyl- (N, N-diethyl) aniline, N, N-bis- ( ⁇ -hydroxyethyl) -p-phenylenediamine, 4-N, N-bis- ( ⁇ -hydroxyethyl) -amino-2 -methylaniline, 4-
  • P-Phenylenediamine derivatives of the formula (E1) which are particularly preferred according to the invention are p-phenylenediamine, p-toluenediamine, 2- ( ⁇ -hydroxyethyl) -p-phenylenediamine, 2- ( ⁇ , ⁇ -dihydroxyethyl) -p-phenylenediamine and N, N -Bis- (ß-hydroxyethyl) -p-phenylenediamine.
  • developer component compounds which contain at least two aromatic nuclei which are substituted by amino and / or hydroxyl groups.
  • binuclear developer components which can be used in the coloring compositions according to the invention, one can name in particular the compounds which correspond to the following formula (E2) and their physiologically tolerable salts:
  • - Z 1 and Z 2 independently of one another represent a hydroxyl or NH 2 radical which is optionally substituted by a Cr to C 4 alkyl radical, by a C to C 4 hydroxyalkyl radical and / or by a bridging Y or which is optionally Is part of a bridging ring system, -
  • the bridge Y stands for an alkylene group with 1 to 14 carbon atoms, such as a linear or branched alkylene chain or an alkylene ring which is interrupted or terminated by one or more nitrogen-containing groups and / or one or more heteroatoms such as oxygen, sulfur or nitrogen atoms may be and may be substituted by one or more hydroxyl or C to C ⁇ alkoxy groups, or a direct bond,
  • G 5 and G 6 are each independently a hydrogen or halogen atom, a Cr to C 4 alkyl group, a Cr to C 4 - monohydroxyalkyl radical, a C 2 - to C 4 - polyhydroxyalkyl radical, a C ⁇ - C 4 - aminoalkyl radical or a direct connection to the bridging Y,
  • G 7 , G 8 , G 9 , G 10 , G 11 and G 12 independently of one another represent a hydrogen atom, a direct bond to the bridging Y or a C to C 4 alkyl radical, with the provisos that the compounds of the formula ( E2) contain only one bridge Y per molecule and the compounds of the formula (E2) contain at least one amino group which carries at least one hydrogen atom.
  • Preferred dinuclear developer components of the formula (E2) are in particular: N, N , -Bis- ( ⁇ -hydroxyethyl) -N, N'-bis- (4'-aminophenyl) -1, 3-diamino-propan-2-ol, N, N'-bis (ß-hydroxyethyl) -N, N'-bis (4'-aminophenyl) ethylenediamine, N, N'-bis (4-aminophenyl) tetramethylene diamine, N, N'-bis - (ß-hydroxyethyl) -N, N'-bis- (4-aminophenyl) tetramethylene diamine, N, N'-bis (4-methyl-aminophenyl) tetramethylene diamine, N.N'-diethyl-N.N ' bis - ⁇ '- amino-S'-methylphenyl) ethylenediamine, bis (2-hydroxy-5-aminoph
  • Very particularly preferred dinuclear developer components of the formula (E2) are N, N'-bis ( ⁇ -hydroxyethyl) -N, N , -bis- (4'-aminophenyl) -1,3-diamino-propan-2-ol, Bis (2-hydroxy-5-aminophenyl) methane, 1, 3-bis (2,5-diaminophenoxy) propan-2-ol, N, N ' -Bis (4'-aminophenyl) -1, 4-diazacycloheptane and 1, 10-bis- (2 ', 5'-diaminophenyl) -1, 4,7,10-tetraoxadecane or one of their physiologically tolerable salts.
  • P-Aminophenol derivatives of the formula (E3) are particularly preferred
  • - G 13 represents a hydrogen atom, a halogen atom, a C to C 4 alkyl radical, a C to C 4 monohydroxyalkyl radical, a C 2 to C 4 polyhydroxyalkyl radical, a (Cr to C 4 ) alkoxy (C to C) alkyl group, a Cr to C 4 aminoalkyl radical, a hydroxy (d- alkylamino-C), a Cr to C 4 -Hydroxyalkoxyrest, a Cr to C 4 - aminoalkyl hydroxyalkyl (Crbis C) or ( di- C to C 4 alkylamino) - (d-C) alkyl, and
  • G 14 represents a hydrogen or halogen atom, a Cr to C 4 alkyl radical, a d to C 4 monohydroxyalkyl radical, a C 2 to C 4 polyhydroxyalkyl radical, a (Cr to C 4 ) alkoxy (Cr to C 4 ) alkyl, a C to C 4 aminoalkyl or a C to C 4 cyanoalkyl
  • G 15 represents hydrogen, a Cr to C alkyl radical, a C to C 4 monohydroxyalkyl radical, a C 2 to C 4 polyhydroxyalkyl radical, a phenyl radical or a benzyl radical, and
  • - G 16 represents hydrogen or a halogen atom.
  • Preferred p-aminophenols of the formula (E3) are in particular p-aminophenol, N-methyl-p-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 2-hydroxymethylamino-4-aminophenol, 4 -Amino-3-hydroxymethylphenol, 4-amino- 2- (D-hydroxyethoxy) phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethyl-phenol, 4-amino -2-aminomethylphenol, 4-amino-2- (ß-hydroxyethyl-aminomethyl) phenol, 4-amino-2- ( ⁇ , ß-dihydroxyethyl) phenol, 4-amino-2-fluorophenol, 4-amino-2 -chlorophenol, 4-amino-2,6-dichlorophenol, 4-amino-2- (diethyl-aminomethyl) -phenol and their physiologically toler
  • Very particularly preferred compounds of the formula (E3) are p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- ( ⁇ , ⁇ -dihydroxyethyl) phenol and 4-amino- 2- (diethylaminomethyl) -phenol.
  • the developer component can also be selected from o-aminophenol and its derivatives, such as, for example, 2-amino-4-methylphenol, 2-amino-5-methylphenol or 2-amino-4-chlorophenol.
  • the developer component can be selected from heterocyclic developer components, such as, for example, the pyridine, pyrimidine, pyrazole, pyrazole-pyrimidine derivatives and their physiologically tolerable salts.
  • heterocyclic developer components such as, for example, the pyridine, pyrimidine, pyrazole, pyrazole-pyrimidine derivatives and their physiologically tolerable salts.
  • Preferred pyridine derivatives are, in particular, the compounds described in patents GB 1 026 978 and GB 1 153 196, such as 2,5-diamino pyridine, 2- (4'-methoxyphenyl) amino-3-amino-pyridine, 2,3-diamino-6-methoxy-pyridine, 2- ( ⁇ -methoxyethyl) amino-3-amino-6-methoxy-pyridine and 3,4-diamino-pyridine.
  • Preferred pyrimidine derivatives are, in particular, the compounds which are described in German patent DE 2 359 399, Japanese laid-open patent publication JP 02019576 A2 or in laid-open publication WO 96/15765, such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy- 2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2-dimethylamino-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6- triaminopyrimidine.
  • Preferred pyrazole derivatives are, in particular, the compounds described in patents DE 3 843 892, DE 4 133 957 and patent applications WO 94/08969, WO 94/08970, EP-740 931 and DE 195 43 988, such as 4.5 - diamino-1-methylpyrazole, 4,5-diamino-1- (ß-hydroxyethyl) -pyrazole, 3,4-
  • Preferred pyrazolopyrimidine derivatives are in particular the derivatives of pyrazolo [1, 5-a] pyrimidine of the following formula (E4) and its tautomeric forms, provided that there is a tautomeric equilibrium: in which:
  • G 17 , G 18 , G 19 and G 20 independently of one another represent a hydrogen atom, a Cr to C 4 alkyl radical, an aryl radical, a Cr to C 4 hydroxyalkyl radical, a C 2 to d polyhydroxyalkyl radical a ( d- to C4) -alkoxy- (Cr to C 4 ) - alkyl radical, a Cr to C 4 -aminoalkyl radical, which can optionally be protected by an acetyl-ureide or a sulfonyl radical, a (Cr to C 4 ) - Alkylamino- (Cr to C 4 ) -alkyl radical, a di - [(Cr to C 4 ) -alkyl] - (Cr to C 4 ) -aminoalkyl radical, the dialkyl radicals optionally being a carbon cycle or a heterocycle with 5 or 6 chain links form a Cr to C 4 - hydroxyalkyl or
  • the X radicals independently of one another represent a hydrogen atom, ad- to C 4 -alkyl radical, an aryl radical, a Cr to C 4 -hydroxyalkyl radical, a C 2 - to C 4 -polyhydroxyalkyl radical, a Cr to C 4 - Aminoalkyl radical, a (Cr to C) alkylamino (Cr to C 4 ) alkyl radical, a di - [(d to C 4 ) alkyl] - (d to C 4 ) aminoalkyl radical, the dialkyl radicals optionally a carbocycle or a heterocycle with 5 or 6 chain members, form a d- to C 4 - hydroxyalkyl or a di- (d- d-up hydroxyalky aminoalkyl group, an amino group, a d- to C 4 -alkyl- or di- (Cr to C 4 -hydroxyalkyl) amino radical, a halogen atom, a
  • - i has the value 0, 1, 2 or 3
  • - n has the value 0 or 1, with the proviso that
  • n has the value 0, and the groups NG 17 G 18 and NG 19 G 20 occupy positions (2,3); (5,6); (6,7); (3.5) or (3.7); - if p + q is 1, n is 1, and the groups NG 17 G 18 (or NG 19 G 20 ) and the group OH occupy positions (2,3); (5,6); (6,7); (3.5) or (3.7).
  • pyrazolo [1, 5-a] pyrimidines of the formula (E4) above one can mention in particular: pyrazolo [1, 5-a] pyrimidine-3,7-diamine; 2,5-dimethyl-pyrazolo [1,5-a] pyrimidine-3,7-diamine; Pyrazolo [1,5-a] pyrimidine-3,5-diamine; 2,7-dimethylpyrazolo [1,5-a] pyrimidine-3,5-diamine; 3-amino-pyrazolo [1,5-a] pyrimidin-7-ol; 3-amino-pyrazolo [1,5-a] pyrimidin-5-ol; 2- (3-amino-pyrazolo [1,5-a] pyrimidin-7-ylamino) ethanol; 2- (7-amino-pyrazolo [1,5-a] pyrimidin-3-ylamino) ethanol; 2 - [(3-amino-
  • pyrazolo [1, 5-a] pyrimidines of the above formula (E4) can be prepared as described in the literature by cyclization starting from an aminopyrazole or from hydrazine.
  • Those indoles and indolines which have at least one hydroxyl or amino group, preferably as a substituent on the six-membered ring, are preferably used as precursors of nature-analogous dyes.
  • These groups can carry further substituents, e.g. B. in the form of etherification or esterification of the hydroxy group or an alkylation of the amino group.
  • R 1 represents hydrogen, a dd-alkyl group or a dd-hydroxyalkyl group
  • R 2 stands for hydrogen or a -COOH group, where the -COOH group can also be present as a salt with a physiologically compatible cation
  • R 3 represents hydrogen or a dd-alkyl group
  • R 4 stands for hydrogen, a dd-alkyl group or a group -CO-R 6 , in which R 6 stands for a dd-alkyl group, and
  • R 5 stands for one of the groups mentioned under R 4 , as well as physiologically tolerable salts of these compounds with an organic or inorganic acid.
  • Particularly preferred derivatives of indoline are 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5 , 6-dihydroxyindoline, 5,6-dihydroxyindoline-2-carboxylic acid and the 6-hydroxyindoline, the 6-aminoindoline and the 4-aminoindoline.
  • N-methyl-5,6-dihydroxyindoline N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline and especially 5 6-Dihydroxyindolin.
  • R 1 is independently hydrogen, a dd-alkyl group or a Crd-hydroxyalkyl group
  • R 2 stands for hydrogen or a -COOH group, where the -COOH group can also be present as a salt with a physiologically compatible cation
  • R 3 represents hydrogen or a dd-alkyl group
  • R 4 stands for hydrogen, a dd-alkyl group or a group -CO-R 6 , in which R 6 stands for a dd-alkyl group, and
  • R 5 stands for one of the groups mentioned under R 4 ,
  • Particularly preferred derivatives of indole are 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl 5,6-dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid, 6-hydroxyindole, 6-aminoindole and 4-aminoindole.
  • N-methyl-5,6-dihydroxyindole N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole, and especially 5,6 -Dihydroxyindol.
  • the rndoline or indole derivative in hair colorants in combination with at least one amino acid or an oligopeptide.
  • the amino acid is advantageously an ⁇ -amino acid; very particularly preferred ⁇ -amino acids are arginine, ornithine, lysine, serine and histidine, in particular arginine.
  • Oxidation dye precursors of the coupler type which are preferred according to the invention
  • o-diamino benzene and its derivatives such as 3,4-diamino benzoic acid and 2,3-diamino-1-methylbenzene, di- or trihydroxybenzene derivatives such as resorcinol, resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5- Dimethylresorcinol, 2-chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1, 2,4-trihydroxybenzene,
  • Pyridine derivatives such as 2,6-dihydroxypyridine, 2-amino-3-hydroxypyridine, 2-amino-5-chloro-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,6-dihydroxy-3, 4-dimethylpyridine, 2,6-dihydroxy-4-methylpyridine, 2,6-diaminopyridine, 2,3-diamino-6-methoxypyridine and 3,5-diamino-2,6-dimethoxypyridine,
  • Naphthalene derivatives such as 1-naphthol, 2-methyl-1-naphthol, 2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 1, 7-dihydroxynaphthalene, 1, 8-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 2,3-dihydroxynaphthalene,
  • Morpholine derivatives such as 6-hydroxybenzomorpholine and 6-aminobenzomorpholine,
  • Quinoxaline derivatives such as 6-methyl-1, 2,3,4-tetrahydroquinoxaline, pyrazole derivatives such as 1-phenyl-3-methylpyrazol-5-one,
  • Indole derivatives such as 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole, pyrimidine derivatives such as 4,6-diaminopyrimidine, 4-amino-2,6-dihydroxypyrimidine, 2,4-diamino-6-hydroxypyrimidine, 2,4, 6-trihydroxypyrimidine, 2-amino-4-methylpyrimidine, 2-amino-4-hydroxy-6-methylpyrimidine and 4,6-dihydroxy-2-methylpyrimidine, or
  • Coupling components which are particularly preferred according to the invention are 1-naphthol, 1, 5-, 2,7- and 1, 7-dihydroxynaphthalene, 3-aminophenol, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, resorcinol, 4-chlororesorcinol , 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol and 2,6-dihydroxy-3,4-dimethylpyridine.
  • the agents according to the invention can also contain naturally occurring dyes such as those in, for example, henna red, henna neutral, henna black, Chamomile flower, sandalwood, black tea, sapwood, sage, blue wood, madder root, catechu, sedre and alkanna root are included.
  • naturally occurring dyes such as those in, for example, henna red, henna neutral, henna black, Chamomile flower, sandalwood, black tea, sapwood, sage, blue wood, madder root, catechu, sedre and alkanna root are included.
  • the oxidation dye precursors or the direct dyes each represent uniform compounds. Rather, the coloring agents used may, due to the manufacturing processes for the individual dyes, contain minor components in minor amounts, provided that these do not adversely affect the coloring result or for other reasons, e.g. toxicological, must be excluded.
  • Reactive carbonyl compounds according to the invention as an oxo dye precursor of component A have at least one carbonyl group as a reactive group, which reacts with component B to form a covalent bond.
  • compounds according to the invention can also be used as reactive carbonyl compounds in which the reactive carbonyl group is derivatized in such a way that the reactivity of the carbon atom of the derivatized carbonyl group with component B is always present.
  • These derivatives are preferably addition compounds of a) amines and their derivatives to form hinen or oximes as addition compound b) of alcohols to form acetals or ketals as addition compound to the carbon atom of the carbonyl group of the reactive carbonyl compound and c) of water to form hydrates.
  • the reactive carbonyl compound is preferably selected from compounds according to formula IV,
  • AR stands for benzene, naphthalene, pyridine, pyrimidine, pyrazine, pyridazine, carbazole, pyrrole, pyrazole, furan, thiophene, 1, 2,3-triazine, 1, 3,5-triazine, quinoline, isoquinoline, indole, indoline, Indolizine, indan, imidazole, 1, 2,4-triazole, 1, 2,3-triazole, tetrazole, benzimidazole, 1, 3-thiazole, benzothiazole, indazole, benzoxazole, quinoxaline, quinazoline, quinolizine, cinnoline, acridine, julolidine, Acenaphthene, fluorene, biphenyl, diphenylmethane, benzophenone, diphenyl ether, azobenzene, chromone, coumarin, diphen
  • R 1 represents a hydrogen atom, a dC ⁇ -alkyl, C 2 -C 6 -acyl, C 2 -d-alkenyl, Crd-perfluoroalkyl, an optionally substituted aryl or heteroaryl group,
  • R 2 , R 3 and R 4 independently of one another represent a hydrogen atom, a halogen atom, a CrC 6 -alkyl, CrC 6 -alkoxy, CrC 6 -aminoalkyl, CrC 6 - hydroxyalkyl group, a d-Ce-alkoxy- -C ö alkyloxy group, a d-C ⁇ - acyl group, an acetyl, carboxyl, carboxylato, carbamoyl, sulfo, sulfato, sulfonamide, sulfonamido, C 2 -C 6 alkenyl, an aryl, an aryl-CrC ⁇ -alkyl group, a hydroxy, a nitro, a pyrrolidino, a morpholino, a piperidino, an amino or ammonio or a 1-imidazole (in) io group, the last three groups with one or more CrC
  • Z represents a direct bond, a carbonyl, a carboxy (CrC 4 ) alkylene, an optionally substituted C 2 -C 6 alkenylene, dC ⁇ alkadienylene, furylene, thienylene, arylene, Vinylene arylene, vinylene furylene, vinyl thienylene group, where Z together with the -YR 1 group can also form an optionally substituted 5-, 6- or 7-ring, • Y stands for a group which is selected from carbonyl, a group according to formula V and a group according to formula ⁇ / ⁇
  • R 5 represents a hydrogen atom, a hydroxy group, a CrC 4 alkoxy group, a CrC 6 alkyl group, a CrC 6 hydroxyalkyl group, a C 2 -C 6 polyhydroxyalkyl group, a CrC 6 alkoxy-CrC 6 alkyl group
  • R and R independently of one another represent a CrC 6 -alkyl group, an aryl group or together with the structural element OCO of the formula IV form a 5- or 6-membered ring.
  • the reactive carbonyl compound is particularly preferably selected from the group consisting of acetophenone, propiophenone, 2-hydroxyacetophenone, 3-hydroxyacetophenone, 4-hydroxyacetophenone, 2-hydroxypropiophenone, 3-
  • Hydroxypropiophenone 4-hydroxypropiophenone, 2-hydroxybutyrophenone, 3-hydroxybutyrophenone, 4-hydroxybutyrophenone, 2,4-dihydroxyacetophenone, 2,5-dihydroxyacetophenone, 2,6-dihydroxyacetophenone, 2,3,4-trihydroxyacetophenone, 3,4,5- Trihydroxyacetophenone, 2,4,6-trihydroxyacetophenone, 2,4,6-trimethoxyacetophenone, 3,4,5-trimethoxyacetophenone, 3,4,5-trimethoxyacetophenone-diethyl ketal, 4-hydroxy-3-methoxyacetophenone, 3, 5-dimethoxy-4-hydroxyacetophenone, 4-aminoacetophenone, 4-dimethylaminoacetophenone, 4-morpholinoacetophenone, 4-piperidinoacetophenone, 4-imidazolinoacetophenone, 2-hydroxy-5-bromoacetophenone, 4-hydroxy-3-nitroacetophenone carboxylic acid,
  • Ethoxybenzaldehyde 4-hydroxy-2,3-dimethoxy-benzaldehyde, 4-hydroxy-2,5-dimethoxy-benzaldehyde, 4-hydroxy-2,6-dimethoxy-benzaldehyde, 4-hydroxy-2-methyl-benzaldehyde, 4- Hydroxy-3-methyl-benzaldehyde, 4-hydroxy-2,3-dimethyl-benzaldehyde, 4-hydroxy-2,5-dimethyl-benzaldehyde, 4-hydroxy-2,6-dimethyl-benzaldehyde, 4-hydroxy-3, 5-dimethoxy-benzaldehyde, 4-hydroxy-3,5-dimethyl-benzaldehyde, 3,5-diethoxy-4-hydroxy-benzaldehyde, 2,6-diethoxy-4-hydroxy-benzaldehyde, 3-hydroxy-4-methoxy benzaldehyde, 2-hydroxy-4-methoxy-benzaldehyde, 2-ethoxy-4-hydroxy-benzaldehyde, 3-
  • At least one further compound as a component selected from (a) CH-acidic compounds and (b) compounds with primary or secondary to the hair dye used in addition to a reactive carbonyl compound Amino or hydroxy group, selected from aromatic hydroxy compounds, primary or secondary aromatic amines and nitrogen-containing heterocyclic compounds, (c) amino acids and (d) oligopeptides composed of 2 to 9 amino acids.
  • the CH-acidic compounds (a) of the oxo dye precursors of component B are preferably selected from the group consisting of 1,3,3,3-tetramethyl-3H-indolium iodide, 1,3,3-tetramethyl-3H-indolium p-toluenesulfonate, 1,2,3,3-tetramethyl-3H ⁇ indolium methanesulfonate, 1,3,3-trimethyl-2-methylene indoline (Fischer's base), 2,3-dimethyl-benzothiazolium iodide, 2,3 -Dimethyl-benzothiazolium-p-toluenesulfonate, 2,3-dimethyl-naphtho [1,2-d] thiazolium-p-toluenesulfonate, 3-ethyl-2-methyl-naphtho [1,2-d] thiazolium -p-toluenesulfonate,
  • the primary and secondary aromatic amines (b) of the oxo dye components of component B are preferably selected from the group consisting of N, N-dirnethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, N- (2-hydroxyethyl) - N-ethyl-p-phenylenediamine, N, N-bis- (2-hydroxyethyl) -p-phenylenediamine, N- (2-methoxyethyl) -p- phenylene diamine, 2,3-dichloro-p-phenylene diamine, 2,4-dichloro-p-phenylene diamine, 2,5-dichloro-p-phenylene diamine, 2-chloro-p-phenylene diamine, 2,5-dihydroxy-4-morpholinoaniline, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminomethyl-4-aminophenol, 2-hydroxymethyl-4
  • Diaminobenzoic acid 2,5-diaminobenzoic acid, 3,4-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 3-amino-4-hydroxy-benzoic acid, 4-amino-3-hydroxy-benzoic acid, 2 -Aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4-hydroxybenzenesulfonic acid, 4-amino-3-hydroxy-naphthalene-1-sulfonic acid, 6-amino-7-hydroxynaphthalene-2-sulfonic acid, 7-amino-4 - hydroxynaphthalene-2-sulfonic acid, 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid, 3-amino-2-naphthoic acid, 3-aminophthalic acid,
  • R 10 represents a hydroxy or an amino group
  • the -C ö by -C 6 alkyl, - hydroxyalkyl, -C 6 alkoxy or -C 6 -alkoxy-C ⁇ -C 6 alkyl groups may be substituted
  • R 11 , R 12 , R 13 , R 14 and R 15 independently of one another for a hydrogen atom, a hydroxyl or an amino group, by -CC 6 alkyl, d-C ⁇ -hydroxyalkyl, CrC ⁇ -alkoxy -, D-C ⁇ -aminoalkyl or d-Ce-alkoxy-CrC ⁇ -alkyl groups can be substituted, and
  • 4,4'-diaminostilbene and its hydrochloride 4,4 * -diaminostilbene-2,2'-disulfonic acid mono- or -di-Na salt, 4-amino-4 * -dimethylaminostilbene and its hydrochloride, 4, 4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 4,4'- Diaminodiphenyl sulfoxide, 4,4'-diaminodiphenylamine, 4,4'-diaminodiphenylamine-2-sulfonic acid, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenyl ether, 3,3 ', 4,4'-tetraaminodiphenyl, 3,3 ', 4,4'-tetraamino-benzophenone, 1,3-bis (2,4-diaminophenoxy) propane, 1,
  • the nitrogen-containing heterocyclic compounds (b) of the oxo dye components of component B are preferably selected from the group consisting of 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-amino-3-hydroxy-pyridine, 2,6-diamino-pyridine, 2,5-diamino-pyridine, 2- (aminoethylammo) -5-aminopyridine, 2,3-diamino-pyridine, 2-dimethylamine-5-amino-pyridine, 2-methylamino-3-amino-6-methoxy- pyridine, 2,3-diamino-6-methoxy-pyridine, 2,6-dimethoxy-3,5-diamino-pyridine, 2,4,5-triamino-pyridine, 2,6-dihydroxy-3,4- dimethylpyridine, N- [2- (2,4-diaminophenyl) aminoethyl] -N- (5-amino-2-pyri
  • the hydroxypyrimidines disclosed in DE-Ul-299 08 573 can also be used as heterocyclic compounds.
  • the aforementioned compounds can be used both in free form and in the form of their physiologically tolerable salts, e.g. B. as salts of inorganic acids, such as hydrochloric or sulfuric acid.
  • the aromatic hydroxy compounds (b) of the oxo dye component B are preferably selected from the group consisting of 2-methylresorcinol, 4-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, resorcinol, 3-methoxyphenol, pyrocatechol, hydroquinone, pyrogallol, phloroglucinol , Hydroxyhydroquinone, 2-methoxyphenol, 3-methoxyphenol, 4-methoxyphenol, 3-dimethylaminophenol, 2- (2-hydroxyethyl) phenol, 3,4-methylenedioxyphenol, 2,4-dihydroxybenzoic acid, 3.4 Dihydroxybenzoic acid, 2,4-dihydroxyphenylacetic acid, gallic acid, 2,4,6-trihydroxybenzoic acid, acetophenone, 2-chlonesorcinol, 4-chloreesorcinol, 1-naphthol, 1,5-dihydroxy-naphthalene, 2,3
  • amino acids (c) of the oxo dye components of component B all naturally occurring and synthetic ⁇ -amino acids are preferred, e.g. obtained by hydrolysis from vegetable or animal proteins, e.g. Collagen, keratin, casein, elastm, soy protein, wheat gluten or almond protein accessible amino acids. Both acidic and alkaline amino acids can be used. Preferred amino acids are arginine, histidine, tyrosine, phenylalanine, DOPA (dihydroxyphenylalanine), omithin, proline, lysine and tryptophan. But also other amino acids, e.g. 6-aminocaproic acid and ⁇ -alanine can be used.
  • the oligopeptides (d) of the oxo dye precursors of component B can be naturally occurring or synthetic oligopeptides, but also the oligopeptides contained in polypeptide or protein hydrolyzates, provided that they have sufficient water solubility for use in the colorants according to the invention.
  • examples include glutathione or the oligopeptides contained in the hydrolyzates of collagen, keratin, casein, elastin, soy protein, wheat gluten or almond protein. Use together with compounds having a primary or secondary amino group or with aromatic hydroxy compounds is preferred.
  • the dyes which can be used in the hair dyeing and toning agents according to the invention reference is expressly made to the monograph Ch.
  • Hair dyes especially if the coloring is oxidative, be it with atmospheric oxygen or other oxidizing agents such as hydrogen peroxide, are usually weakly acidic to alkaline, i.e. H. adjusted to pH values in the range of about 5 to 11.
  • the colorants contain alkalizing agents, usually alkali or alkaline earth metal hydroxides, ammonia or organic amines.
  • Preferred alkalizing agents are monoethanolamine, monoisopropanolamine, 2-amino-2-methyl-propanol, 2-amino-2-methyl-1, 3-propanediol, 2-amino-2-ethyl-1, 3-propanediol, 2-amino -2-methylbutanol and triethanolamine as well as alkali and alkaline earth metal hydroxides.
  • Monoethanolamine, triethanolamine and 2-amino-2-methyl-propanol and 2-amino-2-methyl-1,3-propanedol are particularly preferred in this group. It is also possible to use ⁇ -amino acids such as ⁇ -aminocaproic acid as an alkalizing agent.
  • customary oxidizing agents such as in particular hydrogen peroxide or its adducts with urea, melamine or sodium borate, can be used.
  • oxidation with atmospheric oxygen as the only oxidizing agent can be preferred. It is also possible to carry out the oxidation with the aid of enzymes, the enzymes being used both for producing oxidizing per compounds and for Enhancing the effect of a small amount of oxidizing agents present, or also enzymes which transfer electrons from suitable developer components (reducing agents) to atmospheric oxygen.
  • Oxidases such as tyrosinase, ascorbate oxidase and laccase are preferred, but also glucose oxidase, uricase or pyruvate oxidase. Furthermore, the procedure should be mentioned to increase the effect of small amounts (e.g. 1% and less, based on the total agent) of hydrogen peroxide by peroxidases.
  • the preparation of the oxidizing agent is then expediently mixed with the preparation with the dye precursors immediately before dyeing the hair.
  • the resulting ready-to-use hair dye preparation should preferably have a pH in the range from 6 to 10. It is particularly preferred to use the hair dye in a weakly alkaline environment.
  • the application temperatures can be in a range between 15 and 40 ° C., preferably at the temperature of the scalp. After an exposure time of about 5 to 45, in particular 15 to 30, minutes, the hair dye is rinsed off the hair to be dyed. Washing with a shampoo is not necessary if a carrier with a high surfactant content, e.g. B. a coloring shampoo was used.
  • the scalp and hair contour area are treated with color-rich 5,6-dihydroxyindoline derivatives, in particular before the hair coloring, with the agents according to the invention.
  • the scalp and hair contour area are treated with deep-colored reactive carbonyl compounds and their derivatives with the agents according to the invention, especially before hair coloring.
  • nonionic polymers such as, for example, vinyl pyrrolidone / vinyl acrylate copolymers, polyvinyl pyrrolidone and vinyl pyrrolidone / vinyl acetate copolymers, anionic polymers, such as polyacrylic and polymethacrylic acids in the form of their copolymers with acrylic and methacrylic acid esters and amides, polyoxycarboxylic acids, such as polyketo and polyhydrocarboxylic acids and their salts, and also polymers and copolymers of crotonic acid with esters and amides of acrylic and methacrylic acid, such as vinyl acetate-crotonic acid and vinyl acetate-vinyl propionate-crotonic acid copolymers, structurants such as glucose and maleic acid, hair-conditioning compounds such as phospholipids, for example soy lecithin, egg lecithin and cephalins, perfume oils,
  • anionic polymers such as polyacrylic and polymethacrylic
  • Solubilizers such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol, diethylene glycol and ethoxylated triglycerides,
  • Active ingredients such as bisabolol, allantoin, panthenol, niacinamide, tocopherol and plant extracts,
  • Fats and waxes such as walrus, beeswax, montan wax, paraffins, esters, glycerides and fatty alcohols,
  • Swelling and penetration substances such as PCA, glycerol, propylene glycol monoethyl ether, carbonates, hydrogen carbonates, guanidines, ureas and primary, secondary and tertiary phosphates,
  • Opacifiers such as latex or styrene / acrylamide copolymers
  • Pearlizing agents such as ethylene glycol mono- and distearate or PEG-3 distearate,
  • Propellants such as propane-butane mixtures, N2O, dimethyl ether, CO2 and air,
  • the invention also relates to a method for reducing scalp staining, in which the scalp and / or the hair contours are treated before the hair coloring with an agent which quaternarily contains at least one component from the group of the physiologically compatible hydroxycarboxylic acids, inorganic and organic reducing agents
  • the method is used before oxidative hair coloring.
  • the method is applied with deep shades of color before hair coloring.
  • color-deep shades are to be understood as shades which, when colored on white hair (code Kerling, natural white), result in a ⁇ L value of more than 30.
  • a hair contour area is to be understood as the transition area from an almost hairless skin area to skin areas with pronounced hair growth.
  • the hair contour area on the head is therefore usually in the area of the hairline on the forehead, temples, over the ears and on the neck or neck, and comprises 1 to 3 cm of the hairy skin area and 1 to 3 cm of the hairless skin area.
  • this transition region is preferably treated with the agent according to the invention.
  • the hairy areas of the skin can have areas where, although there is hair growth, the skin becomes visible. This is particularly the case with a crown or in the center of a so-called vortex-shaped hair growth.
  • the agent according to the invention is preferably applied to such areas.
  • the agent according to the invention is preferably applied directly to the corresponding skin areas with the aid of applicators.
  • Applicators in the sense of the method according to the invention are particularly suitable the narrow brushes referred to as appliqués in the hairdressing sector and in particular the bottles with a narrow application tip which are customary in the home application area.
  • the agent can also reach the site of action with the help of the hands, for example by massaging. For this purpose, it can be present as a shampoo, for example.
  • Another object of the invention is the use of at least one component from the group of physiologically compatible hydroxycarboxylic acids, inorganic and organic reducing agents, quaternary
  • Another object of the invention is the use of at least one component from the group of physiologically compatible hydroxycarboxylic acids, inorganic reducing agents, quaternary ammonium compounds, amphoteric surfactants, silicone compounds and / or from mixtures of these compounds and / or from the physiologically compatible salts Reduction of scalp staining during oxidative hair coloring with deep shades.
  • Another object of the invention is a kit containing, in two separate packages, an inventive agent for pretreating the scalp and / or the hair contours as well as a hair dye.
  • the lotions were applied to the scalp with a pipette. Care was taken to ensure that the hair was wetted as little as possible. Lotions 1 to 5 as well as 11 and 12 were half-sided before hair coloring with a formulation which contained 1.5% dihydroxyindoline hydrobromide and was adjusted to a pH of 10.0 with 0.6% arginine and ammonia used. The scalp on the side that had been pretreated with the formulations according to the invention showed almost no scalp staining.
  • Lotions 6 to 10 were tested on one side with oxidation hair color formulations with shades of black and blue-black from the commercially available Poly Brillance Intensive Color Cream series. Here too, there was a significant reduction in the color of the scalp.
  • Formulations 13 to 15 for the hair contours were applied before coloring with black coloring products in the area of the hair contours. With all 3 formulations, practically no skin staining was noticeable after the dyeing process had ended and the formulations according to the invention had been removed from the hair contour area.
  • Ci 6 -i 8 fatty acid mono-di-glyceride (INCI name: Glyceryl Stearate) (manufacturer: SHC)

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Abstract

La présente invention concerne des agents de prétraitement du cuir chevelu utilisés avant un processus de coloration capillaire afin de réduire la coloration du cuir chevelu. Ces agents comprennent au moins un composant issu du groupe des acides hydroxycarboxyliques, des agents de réduction inorganiques et organiques, des composés d'ammonium quaternaires, des agents tensioactifs amphotères ou zwitterioniques, des composés de silicone non volatils, des substances actives antipelliculaires physiologiquement compatibles et/ou de mélanges de ces composés et/ou des sels de ces composés physiologiquement compatibles. Le prétraitement du cuir chevelu et/ou des contours capillaires à l'aide de ces agents assure la possibilité d'une coloration capillaire ultérieure présentant une certaine intensité de coloration et/ou une certaine profondeur de teinte, mais sans aucune coloration ou avec seulement une légère coloration du cuir chevelu et des contours capillaires.
PCT/EP2004/010005 2003-09-17 2004-09-08 Agents permettant de reduire la coloration du cuir chevelu lors de processus de coloration capillaire WO2005027861A1 (fr)

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EP04764948A EP1684871A1 (fr) 2003-09-17 2004-09-08 Agents permettant de reduire la coloration du cuir chevelu lors de processus de coloration capillaire

Applications Claiming Priority (2)

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DE10343235.3 2003-09-17
DE2003143235 DE10343235A1 (de) 2003-09-17 2003-09-17 Mittel zur Verminderung der Kopfhautanfärbung bei Haarfärbeprozessen

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1754515A1 (fr) * 2005-08-15 2007-02-21 Henkel Kommanditgesellschaft auf Aktien Kit pour la colouration et le traitement capillaire contenant des colorants et des agents pour proteger la couleur

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Publication number Priority date Publication date Assignee Title
EP0271186A1 (fr) * 1986-11-21 1988-06-15 Repligen Corporation Hydroxyindoles et leur application comme colorant
EP0475205A1 (fr) * 1990-09-11 1992-03-18 Bristol-Myers Squibb Company Méthode pour réduire la coloration du crâne
US5354870A (en) * 1988-09-12 1994-10-11 L'oreal Indole derivatives for dyeing keratin materials
US5500218A (en) * 1992-02-28 1996-03-19 Wella Aktiengesellschaft Method of preventing coloring of skin adjacent the hairline during dyeing of hair
US5518505A (en) * 1991-01-21 1996-05-21 L'oreal Compositions and methods for the dyeing of keratinous fibers with oxidation dye precursors, indole derivative couplers and oxidizing agents
DE10029384A1 (de) * 2000-06-21 2002-01-03 Henkel Kgaa Mittel zum Färben von keratinhaltigen Fasern
US20020144356A1 (en) * 2001-01-05 2002-10-10 Kao Corporation Semipermanent hair dye composition
US20020172648A1 (en) * 2001-03-09 2002-11-21 Ursula Hehner Anti-dandruff composition and method of preventing, reducing or treating dandruff formation with same
US20030163877A1 (en) * 2001-12-04 2003-09-04 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Colouring composition
EP1433470A1 (fr) * 2002-12-23 2004-06-30 Henkel Kommanditgesellschaft auf Aktien Composition de teinture des fibres kératiniques

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0271186A1 (fr) * 1986-11-21 1988-06-15 Repligen Corporation Hydroxyindoles et leur application comme colorant
US5354870A (en) * 1988-09-12 1994-10-11 L'oreal Indole derivatives for dyeing keratin materials
EP0475205A1 (fr) * 1990-09-11 1992-03-18 Bristol-Myers Squibb Company Méthode pour réduire la coloration du crâne
US5518505A (en) * 1991-01-21 1996-05-21 L'oreal Compositions and methods for the dyeing of keratinous fibers with oxidation dye precursors, indole derivative couplers and oxidizing agents
US5500218A (en) * 1992-02-28 1996-03-19 Wella Aktiengesellschaft Method of preventing coloring of skin adjacent the hairline during dyeing of hair
DE10029384A1 (de) * 2000-06-21 2002-01-03 Henkel Kgaa Mittel zum Färben von keratinhaltigen Fasern
US20020144356A1 (en) * 2001-01-05 2002-10-10 Kao Corporation Semipermanent hair dye composition
US20020172648A1 (en) * 2001-03-09 2002-11-21 Ursula Hehner Anti-dandruff composition and method of preventing, reducing or treating dandruff formation with same
US20030163877A1 (en) * 2001-12-04 2003-09-04 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Colouring composition
EP1433470A1 (fr) * 2002-12-23 2004-06-30 Henkel Kommanditgesellschaft auf Aktien Composition de teinture des fibres kératiniques

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1754515A1 (fr) * 2005-08-15 2007-02-21 Henkel Kommanditgesellschaft auf Aktien Kit pour la colouration et le traitement capillaire contenant des colorants et des agents pour proteger la couleur

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EP1684871A1 (fr) 2006-08-02

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