WO1996005800A1 - Aminomethylated dihydroxybenzenes - Google Patents
Aminomethylated dihydroxybenzenes Download PDFInfo
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- WO1996005800A1 WO1996005800A1 PCT/EP1995/003156 EP9503156W WO9605800A1 WO 1996005800 A1 WO1996005800 A1 WO 1996005800A1 EP 9503156 W EP9503156 W EP 9503156W WO 9605800 A1 WO9605800 A1 WO 9605800A1
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- Prior art keywords
- hair
- bis
- components
- hydroxyethyl
- developer
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Classifications
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- 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
-
- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
- C07C215/46—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton
- C07C215/48—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton with amino groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by carbon chains not further substituted by hydroxy groups
- C07C215/50—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton with amino groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by carbon chains not further substituted by hydroxy groups with amino groups and the six-membered aromatic ring, or the condensed ring system containing that ring, bound to the same carbon atom of the carbon chain
Definitions
- the invention relates to oxidation colorants for dyeing human hair, which contain customary developer components and aminomethyl-substituted dihydroxybenzene derivatives as coupler components.
- oxidation hair colorants play a preferred role for dyeing hair because of their intense colors and good fastness properties.
- hair dyes contain oxidation dye precursors in a cosmetic carrier.
- Developer components and coupler components are used as oxidation dye precursors.
- the developer components form the actual dyes under the influence of oxidizing agents or of atmospheric oxygen with one another or under coupling with one or more coupler components.
- Special representatives are, for example, p-toluenediamine, 2,4,5,6-tetraaminopyrimidine, p-aminophenol, N, N-bis (2-hydroxyethyl) -p-phenylenediamine, 2- (2,5-diaminophenyl) - ethanol, 2- (2,5-diaminophenoxy) ethanol, l-phenyl-3-carboxyamido-4-amino-pyrazolon-5 and 4-amino-3-methylphenol, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triaminohydroxypyrimidine.
- M-Phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenols are generally used as coupler components.
- coupler substances ⁇ -naphthol, pyrogallol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, l-phenyl3-methyl- pyrazolon-5, 2,4-dichloro-3-aminophenol, l, 3-bis (2,4-diaminophenoxy) propane, 2-chloro-resorcinol, 2-chloro-6-methyl-3-aminophenol and 2-methylresorcinol.
- a certain developer component can also form very different shades of color by combination with different couplers. Nevertheless, it is often not possible to achieve the multitude of natural hair color shades with the help of a single developer component. In practice, therefore, a combination of different developer components and coupler components is usually required in order to obtain a single, natural-looking hair color. There is therefore a constant need for new, improved coupler / developer combinations.
- oxidation dye precursors must first of all meet the following requirements: they must develop the desired color shades with sufficient intensity and authenticity in the oxidative coupling. They must also have a good ability to draw on human hair, with no noticeable differences between stressed and freshly regrown hair (leveling ability). They should be resistant to light, heat and the influence of chemical reducing agents, e.g. B. against permanent wave liquids. After all, they should not stain the scalp too much, and above all they should be harmless in toxicological and dermatological terms.
- the European patent application EP 0 398 702 A2 discloses hair colorants which contain aminomethyl-substituted m-aminophenols as couplers.
- the present invention relates to oxidation hair colorants for dyeing keratin fibers, in particular human hair, containing coupler components and developer components in a water-containing carrier, characterized in that at least one conventional developer component in an amount of 0.01 to 20% by weight. %, preferably 0.5 to 5% by weight, and a dihydroxybenzene derivative of the formula I as the coupler component
- X is a hydrogen atom, a halogen atom or a Cj-C / j-alkyl group
- R * and R ⁇ independently of one another represent hydrogen, Cj-C4-alkyl group or C2-C_ ⁇ , -hydroxyalky1- groups and the unit NR ⁇ R ⁇ also a heterocyclic
- non-aromatic optionally containing an oxygen or nitrogen atom, five or six ring.
- N, N-bis- ( ⁇ -hydroxyethyl) -2,4-dioxybenzylamine or N, N-bis- ( ⁇ -hydroxyethyl) -2,4-dioxy-3-methylbenzylamine are particularly suitable as coupler components.
- Some of the dihydroxybenzene derivatives of the formula I are known from the literature and can be prepared by known synthesis methods, for example by aminomethylation according to Mannich (for further details see the example section), but in some cases they are also new, such as N, N-bis- (ß-hydroxy) - ethyl) -2,4-dioxy-3-methylbenzylamine; his synthesis is described in detail in Example 1.
- the substances already described in more detail above can be used as customary developer components which can be used in the oxidation hair colorants according to the invention.
- the developer and coupler components can be used both as free bases and in the form of their inorganic or organic salts, e.g. the hydrochloride or hydrobromide.
- the colorants according to the invention provide a broad spectrum of oxidation colors of interest in terms of application technology in the range from yellow-brown to dark brown shades of high brilliance, good leveling ability and good fastness properties.
- Preferred colorants provide shades in the red range; Such nuances can be achieved with the oxidation hair colorants according to the invention in particular when the developer component is 2,4,5,6-tetraamino-pyrimidine.
- the hair colorants according to the invention contain, in addition to the dihydroxybenzene derivatives of the formula I and the developer components, customary direct dyes, for example from the group of the nitrophenylenediamines, nitroaminophenols, anthraquinones or indophenols, such as, for example, those under the international names or, in addition to the dihydroxybenzene derivatives of the formula I and the developer components Trade names HC Yellow 2, HC Yellow 4, Methyl Yellow, Fluor Yellow, Basic Yellow 57, Disperse Orange 3, HC Red 3, HC Red BN, Cardinal Red, Red Y, Red X, Basic Red 76, HC Blue 2, Nitro Blue, Disperse Blue 3, Basis Blue 99, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9, Basis Brown 16, Picramic Acid and Rodol 9 R Connections, in an amount of 0.01 to 20 wt .-%, based on the entire oxidation hair dye.
- customary direct dyes for example from the group of the
- dihydroxybenzene derivatives of formula I the developer components or the optional direct dyes each represent uniform compounds. Rather, mixtures of various dihydroxybenzene derivatives of the formula I, developer components and substantive dyes can also be used in the hair colorants according to the invention.
- dihydroxybenzene derivatives of the formula I other conventional, above-mentioned. Coupler components may be included.
- developer components and coupler components are generally used in approximately molar amounts to one another. If the molar use has also proven to be expedient, a certain excess of individual oxidation dye precursors is not disadvantageous, so that developer components and coupler components can be present in a molar ratio of 1: 0.5 to 1: 2 .
- the oxidation dye precursors are incorporated in a suitable water-containing carrier.
- suitable water-containing carrier are e.g. Creams, emulsions, gels or also surfactant-containing foaming solutions, e.g. Sha poos, foam aerosols or other preparations that are suitable for use on the hair.
- the water-containing carrier usually contains wetting and emulsifying agents such as anionic, nonionic or ampholytic surfactants, eg fatty alcohol sulfates, alkane sulfonates, ⁇ -olefin sulfonates, fatty alcohol polyglycol ether sulfates, alkyl glycosides, ethylene oxide addition products on fatty alcohols, on fatty acids, on alkylphenols, on sorbitan fatty acid esters, on fatty acid partial glycerides and fatty acid alkanolamides; Thickeners, e.g. B.
- anionic, nonionic or ampholytic surfactants eg fatty alcohol sulfates, alkane sulfonates, ⁇ -olefin sulfonates, fatty alcohol polyglycol ether sulfates, alkyl glycosides, ethylene oxide addition products on fatty alcohols, on fatty acids, on alkylphenols, on
- fatty alcohols fatty acids, paraffin oils, fatty acid esters and other fat components in emulsified form
- water-soluble polymeric thickeners such as natural gums, e.g. B. gum arabic, karaya gum, guar gum, locust bean gum, linseed gums; biosynthetic gums, for example xanthan gums and dextrans; synthetic gums, e.g. B. agar and algin, starch fractions and derivatives such as amylose, amylopectin and Dextri ⁇ ne; modified cellulose molecules, e.g. B. methyl cellulose, hydroxyalkyl cellulose and carboxymethyl cellulose; Clays such as B.
- the constituents of the water-containing carrier are used for the production of the hair colorants according to the invention in amounts customary for this purpose;
- emulsifiers are used in concentrations of 0.5 to 30 wt .-% and thickeners in concentrations of 0.1 to 25 wt .-% of the total colorant.
- the oxidative development of the color can in principle be carried out with atmospheric oxygen.
- a chemical oxidizing agent is preferably used, especially when a lightening effect on the hair is desired in addition to the coloring.
- Particularly suitable oxidizing agents are hydrogen peroxide or its adducts with urea, melamine or sodium borate, and mixtures of such hydrogen peroxide adducts with potassium peroxide disulfate.
- the preparation of the oxidizing agent is expediently mixed with the preparation from the oxidation dye precursors immediately before hair coloring.
- 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. After an exposure time of approx. 30 minutes, the hair dye is removed from the hair to be colored by rinsing. Washing with a shampoo is not necessary if a carrier with a high tenside content, e.g. a coloring shampoo was used.
- Hair colorants according to the invention were produced in the form of a hair color cream emulsion in the following composition:
- Coupler component (K1-K2) 0.0075 mol
- the ingredients were mixed together in order. After the oxidation dye precursors and the inhibitor had been added, the pH of the emulsion was first adjusted to 10 using concentrated ammonia solution, and the mixture was then made up to 100 g with water.
- the oxidative development of the color was carried out with 3% hydrogen peroxide solution as the oxidation solution.
- 100 g of the emulsion were mixed with 50 g of hydrogen peroxide solution (3%) and mixed.
- the coloring cream was applied to approx. 5 cm long strands of standardized, 90% gray but not specially pretreated human hair and left there for 30 minutes at 27 ° C. After the dyeing process had ended, the hair was rinsed, washed with a conventional shampoo and then dried.
- the developer components were E1 to E7
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Abstract
Description
"Aminomethylierte Dihydroxybenzole" "Aminomethylated Dihydroxybenzenes"
Die Erfindung betrifft Oxidationsfärbemittel zum Färben von mensch¬ lichen Haaren, die übliche Entwicklerkomponenten und als Kupplerkom¬ ponenten aminomethylsubstituierte Dihydroxybenzolderivate enthalten.The invention relates to oxidation colorants for dyeing human hair, which contain customary developer components and aminomethyl-substituted dihydroxybenzene derivatives as coupler components.
Für das Färben von Haaren spielen die sogenannten Oxidationshaar- färbemittel wegen ihrer intensiven Farben und guten Echtheitseigen¬ schaften eine bevorzugte Rolle. Solche Haarfärbemittel enthalten Oxidationsfarbstoffvorprodukte in einem kosmetischen Träger. Als Oxidationsfarbstoffvorprodukte werden Entwicklerkomponenten und Kupplerkomponenten eingesetzt. Die Entwicklerkomponenten bilden un¬ ter dem Einfluß von Oxidations itteln oder von Luftsauerstoff unter¬ einander oder unter Kupplung mit einer oder mehreren Kupplerkompo¬ nenten die eigentlichen Farbstoffe aus.The so-called oxidation hair colorants play a preferred role for dyeing hair because of their intense colors and good fastness properties. Such hair dyes contain oxidation dye precursors in a cosmetic carrier. Developer components and coupler components are used as oxidation dye precursors. The developer components form the actual dyes under the influence of oxidizing agents or of atmospheric oxygen with one another or under coupling with one or more coupler components.
Als Entwicklerkomponenten werden üblicherweise primäre aromatische Amine mit einer weiteren, in para- oder ortho-Position befindlichen freien oder substituierten Hydroxy- oder A inogruppe, Diaminopyri- dinderivate, heterocyclische Hydrazone, 4-Aminopyrazolonderivate sowie 2,4,5,6-Tetraaminopyrimidin und dessen Derivate eingesetzt.Primary aromatic amines with a further free or substituted hydroxy or amino group in the para or ortho position, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazolone derivatives and 2,4,5,6-tetraaminopyrimidine and the like are usually used as developer components Derivatives used.
Spezielle Vertreter sind beispielsweise p-Toluylendiamin, 2,4,5,6- Tetraaminopyrimidin, p-Aminophenol, N,N-Bis-(2-hydroxyethyl)-p-phe- nylendiamin, 2-(2,5-Diaminophenyl)-ethanol, 2-(2,5-Diaminophenoxy)- ethanol, l-Phenyl-3-carboxyamido-4-amino-pyrazolon-5 und 4-Amino-3- methylphenol , 2-Hydroxy-4,5,6-triaminopyrimidin, 2,4-Dihydroxy-5,6- diaminopyrimidin und 2,5,6-Triaminohydroxypyrimidin.Special representatives are, for example, p-toluenediamine, 2,4,5,6-tetraaminopyrimidine, p-aminophenol, N, N-bis (2-hydroxyethyl) -p-phenylenediamine, 2- (2,5-diaminophenyl) - ethanol, 2- (2,5-diaminophenoxy) ethanol, l-phenyl-3-carboxyamido-4-amino-pyrazolon-5 and 4-amino-3-methylphenol, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triaminohydroxypyrimidine.
Als Kupplerkomponenten werden in der Regel m-Phenylendiaminderivate, Naphthole, Resorcin und Resorcinderivate, Pyrazolone und m-Aminophe- nole verwendet. Als Kupplersubstanzen eignen sich insbesondere α-Naphthol, Pyrogallol, 1,5-, 2,7- und 1,7-Dihydroxynaphthalin, 5- Amino-2-methylphenol , m-Aminophenol, Resorcin, Resorcinmonomethyl- ether, m-Phenylendiamin, l-Phenyl3-methyl-pyrazolon-5, 2,4-Dichlor- 3-aminophenol , l,3-Bis-(2,4-diaminophenoxy)-propan, 2-Chlor-resor- cin, 2-Chlor-6-methyl-3-aminophenol und 2-Methylresorcin.M-Phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenols are generally used as coupler components. Are particularly suitable as coupler substances α-naphthol, pyrogallol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, l-phenyl3-methyl- pyrazolon-5, 2,4-dichloro-3-aminophenol, l, 3-bis (2,4-diaminophenoxy) propane, 2-chloro-resorcinol, 2-chloro-6-methyl-3-aminophenol and 2-methylresorcinol.
Eine bestimmte Entwicklerkomponente kann durch Kombination mit un¬ terschiedlichen Kupplern auch sehr unterschiedliche Farbnuancen bil¬ den. Trotzdem gelingt es oft nicht, mit Hilfe einer einzigen Ent¬ wicklerkomponente zu der Vielzahl natürlicher Haarfarbnuancen zu kommen. In der Praxis ist daher meist eine Kombination verschiedener Entwicklerkomponenten und Kupplerkomponenten erforderlich, um eine einzige, natürlich wirkende Haarfärbung zu erhalten. Es besteht da¬ her ständig Bedarf an neuen, verbesserten Kuppler/Entwickler-Kom¬ binationen.A certain developer component can also form very different shades of color by combination with different couplers. Nevertheless, it is often not possible to achieve the multitude of natural hair color shades with the help of a single developer component. In practice, therefore, a combination of different developer components and coupler components is usually required in order to obtain a single, natural-looking hair color. There is therefore a constant need for new, improved coupler / developer combinations.
Es ist Aufgabe der vorliegenden Erfindung, neue Kupplerkomponenten aufzufinden, die die an Oxidationsfarbstoffvorprodukte zu stellenden Anforderungen in besonderem Maße erfüllen.It is an object of the present invention to find new coupler components which meet the requirements placed on oxidation dye precursors to a particular degree.
Gute Oxidationsfarbstoffvorprodukte müssen in erster Linie folgende Voraussetzungen erfüllen: Sie müssen bei der oxidativen Kupplung die gewünschten Farbnuancen in ausreichender Intensität und Echtheit ausbilden. Sie müssen ferner ein gutes Aufziehvermögen auf mensch¬ lichem Haar besitzen, wobei keine merklichen Unterschiede zwischen strapaziertem und frisch nachgewachsenem Haar bestehen dürfen (Ega¬ lisiervermögen). Sie sollen beständig sein gegen Licht, Wärme und dem Einfluß chemischer Reduktionsmittel, z. B. gegen Dauerwellflüs¬ sigkeiten. Schließlich sollen sie die Kopfhaut nicht zu sehr anfär¬ ben, und vor allem sollen sie in toxikologischer und dermatologi¬ scher Hinsicht unbedenklich sein. Die eruopäische Offenlegungsschrift EP 0 398 702 A2 offenbart Haar¬ färbemittel, die als Kuppler aminomethylsubstituierte m-Aminophenole enthalten.Good oxidation dye precursors must first of all meet the following requirements: they must develop the desired color shades with sufficient intensity and authenticity in the oxidative coupling. They must also have a good ability to draw on human hair, with no noticeable differences between stressed and freshly regrown hair (leveling ability). They should be resistant to light, heat and the influence of chemical reducing agents, e.g. B. against permanent wave liquids. After all, they should not stain the scalp too much, and above all they should be harmless in toxicological and dermatological terms. The European patent application EP 0 398 702 A2 discloses hair colorants which contain aminomethyl-substituted m-aminophenols as couplers.
Gegenstand der vorliegenden Erfindung sind Oxidationshaarfärbemittel zum Färben von Keratinfasern, insbesondere menschlichen Haaren, ent¬ haltend Kupplerkomponenten und Entwicklerkomponenten in einem was¬ serhaltigen Träger, dadurch gekennzeichnet, daß mindestens eine üb¬ liche Entwicklerkomponente in einer Menge von 0,01 bis 20 Gew.-%, vorzugsweise 0,5 bis 5 Gew.-%, und als Kupplerkomponente ein Dihy- droxybenzolderivat der Formel IThe present invention relates to oxidation hair colorants for dyeing keratin fibers, in particular human hair, containing coupler components and developer components in a water-containing carrier, characterized in that at least one conventional developer component in an amount of 0.01 to 20% by weight. %, preferably 0.5 to 5% by weight, and a dihydroxybenzene derivative of the formula I as the coupler component
oder dessen Salz in einer Menge von 0,01 bis 20 Gew.-%, vorzugsweise 0,5 bis 5 Gew.-%, jeweils bezogen auf das gesamte Oxidationshaarfär¬ bemittel, enthalten ist, wobei X für ein Wasserstoffatom, ein Halo¬ genatom oder eine Cj-C/j-Alkylgruppe steht, und R* und R^ unabhängig voneinander Wasserstoffe, Cj-C4-Alkylgruppe oder C2-C_ι,-Hydroxyalky1- gruppen bedeuten und die Einheit NR^R^ auch einen heterocycTischenor its salt is contained in an amount of 0.01 to 20% by weight, preferably 0.5 to 5% by weight, in each case based on the entire oxidation hair dyeing composition, where X is a hydrogen atom, a halogen atom or a Cj-C / j-alkyl group, and R * and R ^ independently of one another represent hydrogen, Cj-C4-alkyl group or C2-C_ι, -hydroxyalky1- groups and the unit NR ^ R ^ also a heterocyclic
nicht aromatischen, gegebenenfalls ein Sauerstoff- oder Stickstoff¬ atom enthaltenden, Fünf- oder Sechs-Ring darstellen kann.can be non-aromatic, optionally containing an oxygen or nitrogen atom, five or six ring.
Besonders eignen sich N,N-Bis-(ß-hydroxyethyl)-2,4-dioxybenzylamin oder N,N-Bis-(ß-hydroxyethyl)-2,4-dioxy-3-methylbenzylamin als Kupp¬ lerkomponenten. Die Dihydroxybenzolderivate der Formel I sind teils literaturbekannt und lassen sich nach bekannten Synthesemethoden, z.B. durch Amino- methylierung nach Mannich, herstellen (näheres siehe Beispielteil) , teils sind sie aber auch neu, wie z.B. das N,N-Bis-(ß-hydroxy- ethyl)-2,4-dioxy-3-methylbenzylamin; eine genaue Beschreibung seiner Synthese erfolgt im Beispielte l.N, N-bis- (β-hydroxyethyl) -2,4-dioxybenzylamine or N, N-bis- (β-hydroxyethyl) -2,4-dioxy-3-methylbenzylamine are particularly suitable as coupler components. Some of the dihydroxybenzene derivatives of the formula I are known from the literature and can be prepared by known synthesis methods, for example by aminomethylation according to Mannich (for further details see the example section), but in some cases they are also new, such as N, N-bis- (ß-hydroxy) - ethyl) -2,4-dioxy-3-methylbenzylamine; his synthesis is described in detail in Example 1.
Als übliche in den erfindungsgemäßen Oxidationshaarfärbemitteln ein¬ setzbaren Entwicklerkomponenten kommen die bereits oben näher be¬ schriebenen Substanzen in Frage. Die Entwickler- und Kupplerkompo¬ nenten können dabei sowohl als freie Basen als auch in Form ihrer anorganischen oder organischen Salze, z.B. der Hydrochloride oder Hydrobromide, eingesetzt werden.The substances already described in more detail above can be used as customary developer components which can be used in the oxidation hair colorants according to the invention. The developer and coupler components can be used both as free bases and in the form of their inorganic or organic salts, e.g. the hydrochloride or hydrobromide.
Die erfindungsgemäßen Färbemittel liefern ein breites Spektrum an¬ wendungstechnisch interessanter Oxidationsfarben im Bereich gelb¬ brauner bis dunkelbrauner Nuancen von hoher Brillanz, gutem Egali¬ siervermögen und guten Echtheitseigenschaften.The colorants according to the invention provide a broad spectrum of oxidation colors of interest in terms of application technology in the range from yellow-brown to dark brown shades of high brilliance, good leveling ability and good fastness properties.
Bevorzugte Färbemittel liefern Nuancen im Rot-Bereich; solche Nuan¬ cen lassen sich mit den erfindungsgemäßen Oxidationshaarfärbemitteln insbesondere dann erzielen, wenn die Entwicklerkomponente 2,4,5,6- Tetraamino-pyrimidin ist.Preferred colorants provide shades in the red range; Such nuances can be achieved with the oxidation hair colorants according to the invention in particular when the developer component is 2,4,5,6-tetraamino-pyrimidine.
In einer bevorzugten Ausführungsform enthalten die erfindungsgemäßen Haarfärbemittel zur weiteren Modifizierung der Farbnuancen neben den Dihydroxybenzolderivaten der Formel I und den Entwicklerkomponenten zusätzlich übliche direktziehende Farbstoffe, z.B. aus der Gruppe der Nitrophenylendiamine, Nitroaminophenole, Anthrachinone oder In- dophenole, wie z.B. die unter den internationalen Bezeichnungen bzw. Handelsnamen HC Yellow 2, HC Yellow 4, Methylgelb, Fluorgelb, Basic Yellow 57, Disperse Orange 3, HC Red 3, HC Red BN, Kardinalrot, Rot Y, Rot X, Basic Red 76, HC Blue 2, Nitroblau, Disperse Blue 3, Basis Blue 99, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9, Basis Brown 16, Pikraminsäure und Rodol 9 R, bekannten Ver¬ bindungen, in einer Menge von 0,01 bis 20 Gew.-%, bezogen auf das gesamte Oxidationshaarfärbemittel.In a preferred embodiment, the hair colorants according to the invention contain, in addition to the dihydroxybenzene derivatives of the formula I and the developer components, customary direct dyes, for example from the group of the nitrophenylenediamines, nitroaminophenols, anthraquinones or indophenols, such as, for example, those under the international names or, in addition to the dihydroxybenzene derivatives of the formula I and the developer components Trade names HC Yellow 2, HC Yellow 4, Methyl Yellow, Fluor Yellow, Basic Yellow 57, Disperse Orange 3, HC Red 3, HC Red BN, Cardinal Red, Red Y, Red X, Basic Red 76, HC Blue 2, Nitro Blue, Disperse Blue 3, Basis Blue 99, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9, Basis Brown 16, Picramic Acid and Rodol 9 R Connections, in an amount of 0.01 to 20 wt .-%, based on the entire oxidation hair dye.
Es ist nicht erforderlich, daß die Dihydroxybenzolderivate der For¬ mel I, die Entwicklerkomponenten oder die fakultativ enthaltenen direktziehenden Farbstoffe jeweils einheitliche Verbindungen dar¬ stellen. Vielmehr können in den erfindungsgemäßen Haarfärbemitteln auch Gemische verschiedener Dihydroxybenzolderivate der Formel I, Entwicklerkomponenten und direktziehender Farbstoffe verwendet wer¬ den. Insbesondere können neben den Dihydroxybenzolderivaten der For¬ mel I weitere übliche, o.g. Kupplerkomponenten enthalten sein.It is not necessary that the dihydroxybenzene derivatives of formula I, the developer components or the optional direct dyes each represent uniform compounds. Rather, mixtures of various dihydroxybenzene derivatives of the formula I, developer components and substantive dyes can also be used in the hair colorants according to the invention. In particular, in addition to the dihydroxybenzene derivatives of the formula I, other conventional, above-mentioned. Coupler components may be included.
In den erfindungsgemäßen Haarfärbemitteln werden Entwicklerkompo¬ nenten und Kupplerkomponenten im allgemeinen in etwa molaren Mengen zueinander eingesetzt. Wenn sich auch der molare Einsatz als zweck¬ mäßig erwiesen hat, so ist ein gewisser Überschuß einzelner Oxida¬ tionsfarbstoffvorprodukte nicht nachteilig, so daß Entwicklerkom¬ ponenten und Kupplerkomponenten in einem Mol-Verhältnis von 1 : 0,5 bis 1 : 2 enthalten sein können.In the hair colorants according to the invention, developer components and coupler components are generally used in approximately molar amounts to one another. If the molar use has also proven to be expedient, a certain excess of individual oxidation dye precursors is not disadvantageous, so that developer components and coupler components can be present in a molar ratio of 1: 0.5 to 1: 2 .
Zur Herstellung der erfindungsgemäßen Färbemittel werden die Oxida¬ tionsfarbstoffvorprodukte in einem geeigneten wasserhaltigen Träger eingearbeitet. Solche Träger sind z.B. Cremes, Emulsionen, Gele oder auch tensidhaltige schäumende Lösungen, z.B. Sha poos, Schaumaeroso¬ le oder andere Zubereitungen, die für die Anwendung auf dem Haar geeignet sind.To produce the colorants according to the invention, the oxidation dye precursors are incorporated in a suitable water-containing carrier. Such carriers are e.g. Creams, emulsions, gels or also surfactant-containing foaming solutions, e.g. Sha poos, foam aerosols or other preparations that are suitable for use on the hair.
Der wasserhaltige Träger enthält üblicherweise Netz- und Emulgier¬ mittel wie anionische, nichtionische oder ampholytische Tenside, z.B. Fettalkoholsulfate, Alkansulfonate, α-Olefinsulfonate, Fett¬ alkoholpolyglykolethersulfate, Alkylglycoside, Ethylenoxidanlage- rungsprodukte an Fettalkohole, an Fettsäuren, an Alkylphenole, an Sorbitanfettsäureester, an Fettsäurepartialglyceride und Fettsäure- alkanolamide; Verdickungsmittel , z. B. Fettalkohole, Fettsäuren, Paraffinöle, Fettsäureester und andere Fettkomponenten in emulgier- ter Form; wasserlösliche polymere Verdickungsmittel wie natürliche Gummen, z. B. Gummi arabicum, Karaya-Gummi, Guar-Gummi , Johannis¬ brotkernmehl, Leinsamengummen; biosynthetische Gummen, z.B. Xanthan- Gumrni und Dextrane; synthetische Gummen, z. B. Agar-Agar und Algin, Stärke-Fraktionen und Derivate wie Amylose, Amylopektin und Dextri¬ ne; modifizierte Cellulosemoleküle, z. B. Methylcellulose, Hydroxy- alkylcellulose und Carboxymethylcellulose; Tone wie z. B. Bentonit oder vollsynthetische Hydrokolloide, z.B. Polyvinylalkohol oder Po- lyvinylpyrrolidon; haarpflegende Zusätze, wie z. B. wasserlösliche kationische Polymere, anionische Polymere, nichtionische Polymere, amphotere oder zwitterionische Polymere, Pantothensäure, Vitamine, Pflanzenextrakte oder Cholesterin; pH-Stellmittel, Komplexbildner und Parfumöle sowie Reduktionsmittel zur Stabilisierung der Inhalts¬ stoffe, z. B. Ascorbinsäure; schließlich können auch Farbstoffe zum Einfärben der kosmetischen Zubereitungen enthalten sein. Insbeson¬ dere Johannisbrotkernmehl und Guarkernmehl sind als ideale Ver¬ dickungsmittel für nicht-quellfähige Hölzer, z. B. Sandelholz, ent¬ haltende Naturhaarfarbstoffe bekannt. Dementsprechend sind diese Verdickungsmittel bevorzugt zu verwenden, wenn die erfindungsgemäßen Oxidationshaarfärbemittel zusätzlich nicht-quellfähige Hölzer ent¬ halten.The water-containing carrier usually contains wetting and emulsifying agents such as anionic, nonionic or ampholytic surfactants, eg fatty alcohol sulfates, alkane sulfonates, α-olefin sulfonates, fatty alcohol polyglycol ether sulfates, alkyl glycosides, ethylene oxide addition products on fatty alcohols, on fatty acids, on alkylphenols, on sorbitan fatty acid esters, on fatty acid partial glycerides and fatty acid alkanolamides; Thickeners, e.g. B. fatty alcohols, fatty acids, paraffin oils, fatty acid esters and other fat components in emulsified form; water-soluble polymeric thickeners such as natural gums, e.g. B. gum arabic, karaya gum, guar gum, locust bean gum, linseed gums; biosynthetic gums, for example xanthan gums and dextrans; synthetic gums, e.g. B. agar and algin, starch fractions and derivatives such as amylose, amylopectin and Dextri¬ ne; modified cellulose molecules, e.g. B. methyl cellulose, hydroxyalkyl cellulose and carboxymethyl cellulose; Clays such as B. bentonite or fully synthetic hydrocolloids, for example polyvinyl alcohol or polyvinylpyrrolidone; hair care additives such. B. water-soluble cationic polymers, anionic polymers, nonionic polymers, amphoteric or zwitterionic polymers, pantothenic acid, vitamins, plant extracts or cholesterol; pH adjusting agents, complexing agents and perfume oils as well as reducing agents for stabilizing the ingredients, e.g. B. ascorbic acid; finally, dyes for coloring the cosmetic preparations can also be present. In particular locust bean gum and guar gum are ideal thickeners for non-swellable woods, e.g. B. sandalwood, ent¬ natural hair dyes known. Accordingly, these thickeners are to be used preferably if the oxidation hair colorants according to the invention additionally contain non-swellable woods.
Die Bestandteile des wasserhaltigen Trägers werden zur Herstellung der erfindungsgemäßen Haarfärbemittel in für diesen Zweck üblichen Mengen eingesetzt; z.B. werden Emulgiermittel in Konzentrationen von 0,5 bis 30 Gew.-% und Verdickungsmittel in Konzentrationen von 0,1 bis 25 Gew.-% des gesamten Färbemittels eingesetzt.The constituents of the water-containing carrier are used for the production of the hair colorants according to the invention in amounts customary for this purpose; For example, emulsifiers are used in concentrations of 0.5 to 30 wt .-% and thickeners in concentrations of 0.1 to 25 wt .-% of the total colorant.
Die oxidative Entwicklung der Färbung kann grundsätzlich mit Luft¬ sauerstoff erfolgen. Bevorzugt wird jedoch ein chemisches Oxidati¬ onsmittel eingesetzt, besonders dann, wenn neben der Färbung ein Aufhelleffekt am Haar gewünscht ist. Als Oxidationsmittel kommen insbesondere Wasserstoffperoxid oder dessen Anlagerungsprodukte an Harnstoff, Melamin oder Natriumborat sowie Gemische aus derartigen Wasserstoffperoxidanlagerungsprodukten mit Kaliumperoxiddisulfat in Betracht.The oxidative development of the color can in principle be carried out with atmospheric oxygen. However, a chemical oxidizing agent is preferably used, especially when a lightening effect on the hair is desired in addition to the coloring. Particularly suitable oxidizing agents are hydrogen peroxide or its adducts with urea, melamine or sodium borate, and mixtures of such hydrogen peroxide adducts with potassium peroxide disulfate.
Zweckmäßigerweise wird die Zubereitung des Oxidationsmittels unmit¬ telbar vor dem Haarefärben mit der Zubereitung aus den Oxidations- farbstoffvorprodukten vermischt. Das dabei entstehende gebrauchsfer¬ tige Haarfärbepräparat sollte bevorzugt einen pH-Wert im Bereich von 6 bis 10 aufweisen. Besonders bevorzugt ist die Anwendung der Haar¬ färbemittel in einem schwach alkalischen Milieu. Die Anwendungstem¬ peraturen können in einem Bereich zwischen 15 und 40 °C liegen. Nach einer Einwirkungszeit von ca. 30 Minuten wird das Haarfärbemittel durch Ausspülen von dem zu färbenden Haar entfernt. Das Nachwaschen mit einem Shampoo entfällt, wenn ein stark tensidhaltiger Träger, z.B. ein Färbeshampoo, verwendet wurde.The preparation of the oxidizing agent is expediently mixed with the preparation from the oxidation dye precursors immediately before hair coloring. 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. After an exposure time of approx. 30 minutes, the hair dye is removed from the hair to be colored by rinsing. Washing with a shampoo is not necessary if a carrier with a high tenside content, e.g. a coloring shampoo was used.
Die nachfolgenden Beispiele sollen den Erfindungsgegenstand näher erläutern, ohne ihn jedoch hierauf zu beschränken. B e i s p i e l eThe following examples are intended to explain the subject of the invention in more detail, but without restricting it thereto. Examples
I. HerstellungsbeispieleI. Manufacturing examples
1. Literaturzitat für N,N-Bis-(ß-hydroxyethyl)-2,4-dioxybenzylamin x HC1 (Kl) "Leder" (1950), 821. Literature citation for N, N-bis- (β-hydroxyethyl) -2,4-dioxybenzylamine x HC1 (Kl) "Leder" (1950), 82
2. Synthese von N,N-Bis-(ß-hydroxyethyl)-2,4-dioxy-3-methyl-benzylamin x HC1 (K2).2. Synthesis of N, N-bis (ß-hydroxyethyl) -2,4-dioxy-3-methyl-benzylamine x HC1 (K2).
6,2 g (0,05 Mol) 2-Methylresorcin wurden bei 45° C in 50 ml 50%iger Salzsäure gelöst. Dann wurden 5,85 g (0,05 Mol) 3-ß-Hy- droxyethyl-oxazolidin (D0S224636) zugetropft. Nach 1 Stunde bei 45°C wurde das Produkt abgesaugt, mit Ethanol nachgewaschen und i.V. bei 60°C getrocknet. Weiße Kristalle: 166°C.6.2 g (0.05 mol) of 2-methylresorcinol were dissolved in 50 ml of 50% hydrochloric acid at 45 ° C. 5.85 g (0.05 mol) of 3-β-hydroxyethyl-oxazolidine (D0S224636) were then added dropwise. After 1 hour at 45 ° C, the product was filtered off, washed with ethanol and i.V. dried at 60 ° C. White crystals: 166 ° C.
Anwendunαsbeispiele:Application examples:
Es wurden erfindungsgemäße Haarfärbemittel in Form einer Haarfärbe- cremeemulsion in der folgenden Zusammensetzung hergestellt:Hair colorants according to the invention were produced in the form of a hair color cream emulsion in the following composition:
Fettalkohol C12-C14 2,0 g,Fatty alcohol C12-C14 2.0 g,
Fettalkohol C1 -C20 8.5 g, Fettalkohol C12-C14 + 2 EO-Sulfat,Fatty alcohol C1 -C20 8.5 g, fatty alcohol C12-C14 + 2 EO sulfate,
Natriums*".*: 28 %ig 20 g, Wasser 40 g,Sodium * " . * : 28% 20 g, Water 40 g,
Entwicklerkomponente (E1-E7) 0,0075 mol,Developer component (E1-E7) 0.0075 mol,
Kupplerkomponente (K1-K2) 0,0075 mol,Coupler component (K1-K2) 0.0075 mol,
Na2Sθ3 (Inhibitor) 1,0 g,Na2Sθ3 (inhibitor) 1.0 g,
(NH4) S04 1,0 g, konzentrierte Ammoniaklösung bis pH = 10,(NH 4 ) S0 4 1.0 g, concentrated ammonia solution up to pH = 10,
Wasser ad 100 g.Water ad 100 g.
Die Bestandteile wurden der Reihe nach miteinander vermischt. Nach Zugabe der Oxidationsfarbstoffvorprodukte und des Inhibitors wurde zunächst mit konzentrierter Ammoniaklösung der pH-Wert der Emulsion auf 10 eingestellt, dann wurde mit Wasser auf 100 g aufgefüllt.The ingredients were mixed together in order. After the oxidation dye precursors and the inhibitor had been added, the pH of the emulsion was first adjusted to 10 using concentrated ammonia solution, and the mixture was then made up to 100 g with water.
Die oxidative Entwicklung der Färbung wurde mit 3 %iger Wasserstoff¬ peroxidlösung als Oxidationslösung durchgeführt. Hierzu wurden 100 g der Emulsion mit 50 g Wasserstoffperoxidlösung (3 %ig) versetzt und vermischt.The oxidative development of the color was carried out with 3% hydrogen peroxide solution as the oxidation solution. For this purpose, 100 g of the emulsion were mixed with 50 g of hydrogen peroxide solution (3%) and mixed.
Die Färbecreme wurde auf ca. 5 cm lange Strähnen standardisierten, zu 90 % ergrauten aber nicht besonders vorbehandelten Menschenhaars aufgetragen und dort 30 Minuten bei 27 °C belassen. Nach Beendigung des Färbeprozesses wurde das Haar gespült, mit einem üblichen Haar¬ waschmittel gewaschen und anschließend getrocknet.The coloring cream was applied to approx. 5 cm long strands of standardized, 90% gray but not specially pretreated human hair and left there for 30 minutes at 27 ° C. After the dyeing process had ended, the hair was rinsed, washed with a conventional shampoo and then dried.
Als Entwicklerkomponenten El bis E7 wurdenThe developer components were E1 to E7
El p-Toluylendiamin, E2 p-Aminophenol , E3 2,4,5,6-Tetraaminopyrimidin, E4 2-Dimethylamino-4,5,6-triaminopyrimidin, E5 2-Morpholino-4,5,6-triaminopyrimidin, E6 2-Piperidyl-4,5,6-triaminopyrimidin, E7 : 2-Methylamino-4,5,6-triaminopyrimidinEl p-toluenediamine, E2 p-aminophenol, E3 2,4,5,6-tetraaminopyrimidine, E4 2-dimethylamino-4,5,6-triaminopyrimidine, E5 2-morpholino-4,5,6-triaminopyrimidine, E6 2- Piperidyl-4,5,6-triaminopyrimidine, E7: 2-methylamino-4,5,6-triaminopyrimidine
eingesetzt.used.
Tabelle 1Table 1
Entwicklerkomponenten erzielte Ausfärbungen erzielte Ausfärbungen El - E7 mit Kl mit K2Developments achieved colorations achieved colorations El - E7 with Kl with K2
El schokoladenbraun dunkelbraunEl chocolate brown dark brown
E2 gelbbraun braunE2 yellow-brown brown
E3 rotgrau himbeerrotE3 red-gray raspberry red
E4 — graurotE4 - gray red
E5 — braunrotE5 - brown-red
E6 — braunrotE6 - brown-red
E7 — braunviolett E7 - brown violet
Claims
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4429344.5 | 1994-08-18 | ||
| DE19944429344 DE4429344A1 (en) | 1994-08-18 | 1994-08-18 | Aminomethylated dihydroxybenzenes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1996005800A1 true WO1996005800A1 (en) | 1996-02-29 |
Family
ID=6526024
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP1995/003156 Ceased WO1996005800A1 (en) | 1994-08-18 | 1995-08-09 | Aminomethylated dihydroxybenzenes |
Country Status (2)
| Country | Link |
|---|---|
| DE (1) | DE4429344A1 (en) |
| WO (1) | WO1996005800A1 (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1222700A (en) * | 1959-01-20 | 1960-06-13 | Oreal | New aromatic aminohydroxy derivatives usable as oxidation dyes, process for the preparation and process for the use of these derivatives |
| WO1993010744A2 (en) * | 1991-12-03 | 1993-06-10 | L'oreal | Process for dyeing keratin fibres using an acid ph alcoxymetephenylenediamine and compositions therefor |
-
1994
- 1994-08-18 DE DE19944429344 patent/DE4429344A1/en not_active Withdrawn
-
1995
- 1995-08-09 WO PCT/EP1995/003156 patent/WO1996005800A1/en not_active Ceased
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1222700A (en) * | 1959-01-20 | 1960-06-13 | Oreal | New aromatic aminohydroxy derivatives usable as oxidation dyes, process for the preparation and process for the use of these derivatives |
| WO1993010744A2 (en) * | 1991-12-03 | 1993-06-10 | L'oreal | Process for dyeing keratin fibres using an acid ph alcoxymetephenylenediamine and compositions therefor |
Also Published As
| Publication number | Publication date |
|---|---|
| DE4429344A1 (en) | 1996-02-22 |
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