EP0569368A1 - 2,5-diamino phenoxy oxaalkanes and their use as initial oxidation dyes - Google Patents

2,5-diamino phenoxy oxaalkanes and their use as initial oxidation dyes

Info

Publication number
EP0569368A1
EP0569368A1 EP19920901017 EP92901017A EP0569368A1 EP 0569368 A1 EP0569368 A1 EP 0569368A1 EP 19920901017 EP19920901017 EP 19920901017 EP 92901017 A EP92901017 A EP 92901017A EP 0569368 A1 EP0569368 A1 EP 0569368A1
Authority
EP
European Patent Office
Prior art keywords
bis
formula
diaminophenoxy
hair
oxaalkanes
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP19920901017
Other languages
German (de)
French (fr)
Inventor
David Rose
Horst Höffkes
Edgar Lieske
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0569368A1 publication Critical patent/EP0569368A1/en
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • A61K8/411—Aromatic amines, i.e. where the amino group is directly linked to the aromatic nucleus
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/78—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
    • C07C217/80—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings
    • C07C217/82—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring
    • C07C217/84—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring the oxygen atom of at least one of the etherified hydroxy groups being further bound to an acyclic carbon atom

Definitions

  • the invention relates to 2,5-diaminophenoxy-oxaalkanes, their preparation and use as oxidation dye precursors for the production of oxidation dyeings, in particular for the preparation of hair dyes.
  • Oxidation dyes contain oxidation dye precursors in a suitable carrier. Developments are used as oxidation dye precursors which form intensive colorations by oxidative coupling with one another or with one or more coupler substances in the presence of atmospheric oxygen or oxidizing agents.
  • z. B primary aromatic amines with a further in para or orthoposition free or substituted hydroxy ode A ino group, further diaminopyridines, heterocyclic hydrazone derivatives 4-aminopyrazolone derivatives and tetraaminopyrimidines.
  • the dyestuff which can be obtained by self-coupling of the developer substances is usually unsatisfactory. Coupling with phenols or aromatic amines can often be used to achieve high intensity and brilliant colors.
  • Suitable so-called coupler substances are, for example, -phenylenediamines, m-aminophenols for resorcinols, naphthol and pyrazolones.
  • oxidation hair dye precursors must first of all meet the following prerequisites: b they must develop the desired color shades with sufficient intensity in the oxidative coupling. You must also have a good ability to draw on human hair without staining the scalp too much. Au The color should be applied evenly, ie the more heavily used hair tips should not be colored more than the little damaged hairline. The dyeings thus produced must have a high stability against heat, light, shampoo and the chemicals used in the permanent waving. Finally, the oxidation hair dye precursors should be harmless from a toxicological and dermatological point of view.
  • the invention relates to bis (2,5-diaminophenoxy) oxaalkanes of the general formula I
  • n »2 or 3 and x is an integer from 1 to 3.
  • the compounds of formula I are new. However, they can be prepared in a conventional manner by adding a bis (2-amino-5-nitro-phenoxy) oxaalkane of the formula II , ,
  • n 2 or 3 and x is an integer from 1 to 3 is catalytically hydrogenated to the corresponding bis- (2,5-diamino-phenoxa) -oxaalkane of the formula I.
  • the hydrogenation is carried out by known processes using hydrogen in the presence of a catalyst, preferably from the group of platinum metals, e.g. B. in finely divided form or on activated carbon or in the presence of Raney nickel.
  • a catalyst preferably from the group of platinum metals, e.g. B. in finely divided form or on activated carbon or in the presence of Raney nickel.
  • the two nitro groups are converted into amino groups.
  • the new bis- (2,5-diaminophenoxy) oxaalkanes of the formula I or their water-soluble salts are suitable as developer compounds (primary intermediate) for producing oxidation colorations.
  • the oxidation stains that can be obtained from this apply particularly well to hair and other keratin fibers.
  • a particular advantage lies in the fact that the hair coloration obtained is applied evenly to damaged hair of different degrees and has a high resistance to shampoos. Even after repeated shampooing, the hair dyed according to the invention is evenly dyed.
  • the colors which can be produced by oxidation with the new bis- (2,5-diaminophenoxy) -oxaalkanes of the formula I can be modified considerably in terms of their intensity, brilliance and nuance by joint oxidation with numerous customary coupler compounds.
  • hair colorants which contain oxidation dye precursors in a carrier, the oxidation dye precursors being at least one bis- (2,5-diaminophenoxy) oxaalkane of formula I or its water-soluble salt as developer component and at least one in oxidation hair dye
  • Common coupler components are included.
  • those from the group of resorcinols, naphthols, aminophenols or hydroxypyridines are particularly suitable for the new developers of the formula (I).
  • hair dye of the type mentioned above which contains at least one compound from the group of resorcinols, naphthols, aminophenols or hydroxypyridines as a coupler component.
  • the bis (2,5-diaminophenoxy) oxaalkanes of the formula I form salts with acids.
  • the water-soluble salts which are formed with inorganic or organic acids, for. B. hydrochlorides, sulfates, phosphates, acetates, propionates, lactates or citrates.
  • the hair colorants according to the invention can also contain other known developer compounds if this is necessary to achieve certain shades.
  • known, direct hair dyes e.g. B. nitrophenylenediamine derivatives, anthraquinone dyes or indophenols can be added.
  • the new developers of the formula I and the known developer compounds which may additionally be present are generally used in approximately molar amounts, based on the coupler substances used. Even if the molar use has proven to be expedient, a certain excess of individual oxidation dye precursors is not disadvantageous, so that developer substances and coupler substances can be contained in a molar ratio of 1: 0.5 to 1: 2.
  • the oxidation dye precursors are incorporated into a suitable cosmetic carrier.
  • suitable cosmetic carrier are e.g. B. creams, emulsions, gels or surfactant-containing, foaming solutions, eg. B. shampoos or other preparations, which are suitable for use on the hair.
  • Common components of such cosmetic preparations are e.g. B. wetting and emulsifying agents such as ' onic, nonionic, a pholytic or zwitterionic surfactants, e.g. B.
  • soaps fatty alcohol sulfates, alkane sulfonates, alpha-olefin sulfonates, fatty alcohol polyglycol ether sulfates, ethylene oxide addition products to fatty alcohols, to fatty acids and to alkylphenols, sorbitan fatty acid esters and fatty acid partial glycerides, fatty acid alkanolamides and thickeners such as, for. As methyl or hydroxyethylene cellulose, starch, fat components such as. B. fatty alcohols, paraffin oils or fatty acid esters, also perfume oils and hair care additives, such as. B. water-soluble cationic polymers, protein derivatives, pantothenic acid and cholesterol.
  • Particularly suitable as a carrier is a gel with a content of 1-20% by weight of a soap, preferably ammonium oleate or an oil-in-water emulsion with a content of 1-25% by weight of a fat component and 0, 5 to 30% by weight of an emulsifier from the group of anionic, nonionic, ampholytic or zwitterionic surfactants.
  • the oxidation dye precursors are mixed into the carrier in amounts of 0.2-5% by weight, preferably 1-3% by weight, of the total colorant.
  • the content of bis- (2,5-diaminonphenoxy) -oxaalkanes of the formula (I) in the hair colorants according to the invention can be about 0.05-10 millimoles per 100 g of the hair colorant.
  • the oxidative development of the color can basically be done with atmospheric oxygen.
  • a chemical oxidizing agent is preferably used, especially if, in addition to the coloring, a whitening effect on the hair is desired.
  • 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.
  • a preparation of the oxidizing agent is preferably mixed with the preparation of oxidation dye precursors and carrier immediately before hair coloring.
  • the resulting ready-to-use hair dye preparation should preferably have a pH in the range of 6-10. It is particularly preferred to use the hair dye in a weakly alkaline environment.
  • the application temperatures can be in a range between 15 ° C and 40 ° C.
  • the hair dye is removed from the hair to be dyed by rinsing.
  • the hair is then washed with a mild shampoo and dried. Washing with a shampoo is not necessary if a carrier with a high tenside content, e.g. B. a coloring shampoo was used.
  • Hair colorants according to the invention were produced in the form of a hair dyeing cre e-emulsion of the following composition:
  • 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 9.5 with concentrated ammonia solution, and the mixture was then made up to 100 g with water.
  • the oxidative development of the color was carried out using 3% hydrogen peroxide solution as the oxidizing agent.
  • 100 g of the emulsion were mixed with 50 g of hydrogen peroxide solution (3%) and mixed.
  • the coloring cream was applied to strands approx. 5 cm long, 90% gray, but not specially pretreated, and left there for 30 minutes at 27 ° C. After the dyeing process had ended, the hair was rinsed, washed out with a customary shampoo and then dried.
  • Example 1.1 (E1) and Example 1.2 (E2) were used as developer components.
  • the following compounds were used as coupler components
  • Example 2.19 the developer El was used instead of a coupler (thus a total of 15 mmol El).

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
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Abstract

Des bis-(2,5-diaminophénoxy)-oxaalcanes ayant la formule (I), dans laquelle n vaut 2 ou 3 et x représente un nombre entier compris entre 1 et 3, sont utiles comme développeurs générateurs de colorations par oxydation, notamment pour produire des colorants pour cheveux. Avec des copulateurs appropriés, sélectionnés de préférence parmi les résorcines, les naphtols, les aminophénols ou les hydroxypyrines, on obtient des colorations très brillantes et uniformes des cheveux, avec de bonnes propriétés de résistance.Bis (2,5-diaminophenoxy) -oxaalcanes having the formula (I), in which n is 2 or 3 and x represents an integer between 1 and 3, are useful as developers generating oxidation dyes, in particular for produce hair dyes. With suitable couplers, preferably selected from resorcins, naphthols, aminophenols or hydroxypyrins, very brilliant and uniform hair colorings are obtained, with good resistance properties.

Description

"2,5-Diaminophenoxy-oxaalkane und deren Verwendung als Oxidationsfarb- stoffVorprodukte" "2,5-diaminophenoxy-oxaalkanes and their use as oxidation dye precursors"
Die Erfindung betrifft 2,5-Diaminophenoxy-oxaalkane, deren Herstellung un Verwendung als OxidationsfarbstoffVorprodukte zur Erzeugung von Oxida tionsfärbungen, insbesondere zur Herstellung von Haarfärbemitteln.The invention relates to 2,5-diaminophenoxy-oxaalkanes, their preparation and use as oxidation dye precursors for the production of oxidation dyeings, in particular for the preparation of hair dyes.
Oxidationsfärbe ittel enthalten Oxidationsfarbstoffvorprodukte in eine geeigneten Träger. Als Oxidationsfarbstoffvorprodukte werden Entwickle substanzen eingesetzt, die durch oxidative Kupplung untereinander oder mi einer oder mehreren Kupplersubstanzen in Gegenwart von Luftsauerstoff ode Oxidationsmitteln intensive Färbungen ausbilden. Als Entwicklersubstanze eignen sich z. B. primäre aromatische Amine mit einer weiteren in Para oder Orthoposition befindlichen freien oder substituierten Hydroxy- ode A inogruppe, ferner Diaminopyridine, heterocyclische Hydrazonderivate 4-Aminopyrazolonderivate und Tetraaminopyrimidine.Oxidation dyes contain oxidation dye precursors in a suitable carrier. Developments are used as oxidation dye precursors which form intensive colorations by oxidative coupling with one another or with one or more coupler substances in the presence of atmospheric oxygen or oxidizing agents. As a developer, z. B. primary aromatic amines with a further in para or orthoposition free or substituted hydroxy ode A ino group, further diaminopyridines, heterocyclic hydrazone derivatives 4-aminopyrazolone derivatives and tetraaminopyrimidines.
Die durch Selbstkupplung der Entwicklersubstanzen erhältlichen Farbstoff sind meist unbefriedigend. Durch Kupplung mit Phenolen oder aromatische A inen lassen sich jedoch oft Färbungen von hoher Intensität und Brillan erzielen. Als sogenannte Kupplersubstanzen (auch "color modifier genann eignen sich z. B. -Phenylendiamine, m-Aminophenolef Resorcine, Naphthol und Pyrazolone.The dyestuff which can be obtained by self-coupling of the developer substances is usually unsatisfactory. Coupling with phenols or aromatic amines can often be used to achieve high intensity and brilliant colors. Suitable so-called coupler substances (also known as color modifiers) are, for example, -phenylenediamines, m-aminophenols for resorcinols, naphthol and pyrazolones.
Eines der bedeutendsten Anwendungsgebiete für Oxidationsfärbemittel i das Gebiet der Haarfärbemittel. Gute Oxidations-HaarfarbstoffVorproduk müssen in erster Linie folgende Voraussetzungen erfüllen: Sie müssen b der oxidativen Kupplung die gewünschten Farbnuancen in ausreichender I tensität ausbilden. Sie müssen ferner ein gutes Aufziehvermögen a menschlichem Haar besitzen, ohne die Kopfhaut zu stark anzufärben. Au soll der Farbaufzug gleichmäßig erfolgen, d. h. die stärker strapazierten Haarspitzen sollen nicht stärker gefärbt werden als der wenig geschädigte Haaransatz. Die damit erzeugten Färbungen müssen eine hohe Stabilität ge¬ gen Wärme, Licht, Haarwaschmittel und die bei der Dauerwellung verwendeten Chemikalien aufweisen. Schließlich sollen die OxidationshaarfarbstoffVor¬ produkte in toxikologischer und dermatologischer Hinsicht unbedenklich sein.One of the most important areas of application for oxidation dyes is the area of hair dyes. Good oxidation hair dye precursors must first of all meet the following prerequisites: b they must develop the desired color shades with sufficient intensity in the oxidative coupling. You must also have a good ability to draw on human hair without staining the scalp too much. Au The color should be applied evenly, ie the more heavily used hair tips should not be colored more than the little damaged hairline. The dyeings thus produced must have a high stability against heat, light, shampoo and the chemicals used in the permanent waving. Finally, the oxidation hair dye precursors should be harmless from a toxicological and dermatological point of view.
Aus der Europäischen Patentschrift EP 11843 Bl sind Bis-(2,5-diaminophen- oxy)-alkane und deren Eignung als Oxidationsfarbstoffvorprodukte bekannt. Die mit diesen Entwicklerverbindungen erzeugten Oxidationsfärbungen weisen bei geschädigtem Haar eine geringere Waschechtheit auf, dadurch erscheint das gefärbte Haar nach dem Waschen ungleichmäßig gefärbt und im Bereich der Haarspitzen farblich verändert.Bis- (2,5-diaminophenoxy) alkanes and their suitability as oxidation dye precursors are known from the European patent EP 11843 B1. The oxidation colorations produced with these developer compounds are less washfast when the hair is damaged, as a result of which the colored hair appears unevenly colored after washing and changes color in the area of the hair tips.
Es wurde nun gefunden, daß Bis-2,5-diaminophenoxyoxaalkane dieser im fol¬ genden näher spezifizierten Art diese Nachteile nicht aufweisen.It has now been found that bis-2,5-diaminophenoxyoxaalkanes of the type specified in more detail below do not have these disadvantages.
Gegenstand der Erfindung sind Bis-(2,5-diaminophenoxy)-oxaalkane der all¬ gemeinen Formel IThe invention relates to bis (2,5-diaminophenoxy) oxaalkanes of the general formula I
in der n » 2 oder 3 und x eine ganze Zahl von 1 - 3 ist.in which n »2 or 3 and x is an integer from 1 to 3.
Von den Verbindungen der Formel I kommt solchen, in denen n * 2 und x = 1 oder 2 ist, die größte Bedeutung zu.Of the compounds of the formula I, those in which n * 2 and x = 1 or 2 are of the greatest importance.
Die Verbindungen der Formel I sind neu. Sie lassen sich aber auf an sich üblichem Wege dadurch herstellen, daß man ein Bis-(2-amino-5-nitro-phen- oxy)-oxaalkan der Formel II, . .The compounds of formula I are new. However, they can be prepared in a conventional manner by adding a bis (2-amino-5-nitro-phenoxy) oxaalkane of the formula II , ,
in der n = 2 oder 3 und x eine ganze Zahl von 1 bis 3 ist katalytisch zum entsprechenden Bis-(2,5-diamino-phenoxa)-oxaalkan der Formel I hydriert. in which n = 2 or 3 and x is an integer from 1 to 3 is catalytically hydrogenated to the corresponding bis- (2,5-diamino-phenoxa) -oxaalkane of the formula I.
Die Hydrierung wird nach bekannten Verfahren mit Wasserstoff in Gegenwart eine Katalysators, bevorzugt aus der Gruppe der Platinmetalle, z. B. in feinverteilter Form oder auf Aktivkohle oder in Gegenwart von Raney-Nickel durchgeführt. Dabei werden die beiden Nitrogruppen in Aminogruppen über¬ führt.The hydrogenation is carried out by known processes using hydrogen in the presence of a catalyst, preferably from the group of platinum metals, e.g. B. in finely divided form or on activated carbon or in the presence of Raney nickel. The two nitro groups are converted into amino groups.
Die neuen Bis-(2,5-diaminophenoxy)-oxaa1kane der Formel I oder deren was¬ serlösliche Salze eignen sich als Entwicklerverbindungen (primary inter- mediate) zur Erzeugung von Oxidationsfärbungen. Die damit erhältlichen Oxidationsfärbungen ziehen besonders gut auf Haare und andere Keratin- fasern auf. Ein besonderer Vorteil liegt darin, daß die erzielten Haaran- färbungen auch auf unterschiedlich stark geschädigtes Haar gleichmäßig aufziehen und eine hohe Beständigkeit gegen Haarwaschmittel aufweisen. Auch nach mehrmaligem Shamponieren ist das erfindungsgemäß gefärbte Haar gleichmäßig angefärbt.The new bis- (2,5-diaminophenoxy) oxaalkanes of the formula I or their water-soluble salts are suitable as developer compounds (primary intermediate) for producing oxidation colorations. The oxidation stains that can be obtained from this apply particularly well to hair and other keratin fibers. A particular advantage lies in the fact that the hair coloration obtained is applied evenly to damaged hair of different degrees and has a high resistance to shampoos. Even after repeated shampooing, the hair dyed according to the invention is evenly dyed.
Die mit den neuen Bis-(2,5-diaminophenoxy)-oxaalkanen der Formel I durch Oxidation herstellbaren Farben lassen sich durch gemeinsame Oxidation mit zahlreichen üblichen Kupplerverbindungen in ihrer Intensität, Brillanz und in der Nuance erheblich modifizieren.The colors which can be produced by oxidation with the new bis- (2,5-diaminophenoxy) -oxaalkanes of the formula I can be modified considerably in terms of their intensity, brilliance and nuance by joint oxidation with numerous customary coupler compounds.
Ein weiterer Patentgegenstand sind daher Haarfärbemittel, die Oxidations¬ farbstoffvorprodukte in einem Träger enthalten, wobei als Oxidationsfarb¬ stoffvorprodukte wenigstens ein Bis-(2,5-diaminophenoxy)-oxaalkan der For¬ mel I oder dessen wasserlösliches Salz als Entwicklerkomponente un wenigstens eine in Oxidationshaarfärbe itteln übliche Kupplerkomponent enthalten sind. Unter den zahlreichen bekannten Kupplersubstanzen sind für die neuen Ent¬ wickler der Formel (I) besonders solche aus der Gruppe der Resorcine, Naphthole, Aminophenole oder Hydroxypyridine geeignet. Eine weitere, be¬ sonders bevorzugte Ausführung der Erfindung sind daher Haarfärbemittel der oben genannten Art, die als Kupplerkomponente wenigstens eine Verbindung aus der Gruppe der Resorcine, Naphthole, Aminophenole oder Hydroxypyridine enthalten.Another subject matter of the patent are therefore hair colorants which contain oxidation dye precursors in a carrier, the oxidation dye precursors being at least one bis- (2,5-diaminophenoxy) oxaalkane of formula I or its water-soluble salt as developer component and at least one in oxidation hair dye Common coupler components are included. Among the numerous known coupler substances, those from the group of resorcinols, naphthols, aminophenols or hydroxypyridines are particularly suitable for the new developers of the formula (I). A further, particularly preferred embodiment of the invention is therefore hair dye of the type mentioned above, which contains at least one compound from the group of resorcinols, naphthols, aminophenols or hydroxypyridines as a coupler component.
Die Bis-(2,5-diaminophenoxy)-oxaalkane der Formel I bilden mit Säuren Sal¬ ze. Bevorzugt geeignet sind die wasserlöslichen Salze, die mit anorgani¬ schen oder organischen Säuren gebildet werden, z. B. Hydrochloride, Sul¬ fate, Phosphate, Acetate, Propionate, Lactate oder Citrate.The bis (2,5-diaminophenoxy) oxaalkanes of the formula I form salts with acids. The water-soluble salts which are formed with inorganic or organic acids, for. B. hydrochlorides, sulfates, phosphates, acetates, propionates, lactates or citrates.
Die erfindungsgemäßen Haarfärbemittel können außer den neuen Bis-(2,5-di- aminophenoxy)-oxaalkanen auch andere bekannte Entwicklerverbindungen ent¬ halten, wenn dies zur Erzielung bestimmter Nuancen erforderlich ist. Wei¬ terhin können zur Modifikation der Haarfärbung auch bekannte, direktzie¬ hende Haarfarbstoffe, z. B. Nitrophenylendiaminderivate, Anthrachinonfarb- stoffe oder Indophenole zugesetzt werden.In addition to the new bis- (2,5-diaminophenoxy) -oxaalkanes, the hair colorants according to the invention can also contain other known developer compounds if this is necessary to achieve certain shades. Furthermore, known, direct hair dyes, e.g. B. nitrophenylenediamine derivatives, anthraquinone dyes or indophenols can be added.
In den erfindungsgemäßen Haarfärbemitteln werden die neuen Entwickler der Formel I und die gegebenenfalls zusätzlich vorhandenen bekannten Entwick¬ lerverbindungen im allgemeinen in etwa molaren Mengen, bezogen auf die eingesetzten Kupplersubstanzen angewendet. Wenn sich auch der molare Ein¬ satz als zweckmäßig erwiesen hat, so ist doch ein gewisser Überschuß ein¬ zelner Oxidationsfarbstoffvorprodukte nicht nachteilig, so daß Entwickler¬ substanzen und Kupplersubstanzen in einem Molverhältnis von 1 : 0,5 bis 1 : 2 enthalten sein können.In the hair colorants according to the invention, the new developers of the formula I and the known developer compounds which may additionally be present are generally used in approximately molar amounts, based on the coupler substances used. Even if the molar use has proven to be expedient, a certain excess of individual oxidation dye precursors is not disadvantageous, so that developer substances and coupler substances can be contained in a molar ratio of 1: 0.5 to 1: 2.
Es ist auch nicht erforderlich, daß die Bis-(2,5-diaminophenoxy)-oxaalkane der Formel I einheitliche chemische Verbindungen darstellen. Vielmehr kön¬ nen diese auch Gemische verschiedener Verbindungen der Formel I sein.It is also not necessary for the bis (2,5-diaminophenoxy) oxaalkanes of the formula I to be uniform chemical compounds. Rather, these can also be mixtures of different compounds of the formula I.
Zur Herstellung der erfindungsgemäßen Haarfärbemittel werden die Oxida- tionfarbstoffvorprodukte in einen geeigneten kosmetischen Träger eingear¬ beitet. Solche Träger sind z. B. Cremes, Emulsionen, Gele oder auch ten- sidhaltige, schäumende Lösungen, z. B. Shampoos oder andere Zubereitungen, die für die Anwendung auf dem Haar geeignet sind. Übliche Bestandteile solcher kosmetischer Zubereitungen sind z. B. Netz- und Emulgiermittel wie am'onische, nichtionische, a pholytische oder zwitterionische Tenside, z. B. Seifen, Fettalkoholsulfate, Alkansulfonate, alpha-Olefinsulfonate, Fettalkoholpolyglykolethersulfate, Ethylenoxidanlagerungsprodukte an Fett¬ alkohole, an Fettsäuren und an Alkylphenole, Sorbitanfettsäureester und Fettsäurepartialglyceride, Fettsäurealkanolamide sowie Verdickungsmittel wie z. B. Methyl- oder Hydroxyethylencellulose, Stärke, Fettkomponenten wie z. B. Fettalkohole, Paraffinöle oder Fettsäureester, ferner Parfümöle und haarpflegende Zusätze, wie z. B. wasserlösliche kationische Polymere, Proteinderivate, Pantothensäure und Cholesterin.To produce the hair colorants according to the invention, the oxidation dye precursors are incorporated into a suitable cosmetic carrier. Such carriers are e.g. B. creams, emulsions, gels or surfactant-containing, foaming solutions, eg. B. shampoos or other preparations, which are suitable for use on the hair. Common components of such cosmetic preparations are e.g. B. wetting and emulsifying agents such as ' onic, nonionic, a pholytic or zwitterionic surfactants, e.g. B. soaps, fatty alcohol sulfates, alkane sulfonates, alpha-olefin sulfonates, fatty alcohol polyglycol ether sulfates, ethylene oxide addition products to fatty alcohols, to fatty acids and to alkylphenols, sorbitan fatty acid esters and fatty acid partial glycerides, fatty acid alkanolamides and thickeners such as, for. As methyl or hydroxyethylene cellulose, starch, fat components such as. B. fatty alcohols, paraffin oils or fatty acid esters, also perfume oils and hair care additives, such as. B. water-soluble cationic polymers, protein derivatives, pantothenic acid and cholesterol.
Besonders geeignet als Träger ist ein Gel mit einem Gehalt von 1 - 20 Gew.-% einer Seife, bevorzugt Ammoniumoleat oder eine Öl-in-Wasser-Emul- sion mit einem Gehalt von 1 - 25 Gew.-% einer Fettkomponente und 0,5 - 30 Gew.-% eines Emulgiermittels aus der Gruppe der anionischen, nichtioni¬ schen, ampholytisehen oder zwitterionischen Tenside.Particularly suitable as a carrier is a gel with a content of 1-20% by weight of a soap, preferably ammonium oleate or an oil-in-water emulsion with a content of 1-25% by weight of a fat component and 0, 5 to 30% by weight of an emulsifier from the group of anionic, nonionic, ampholytic or zwitterionic surfactants.
Die Oxidationsfarbstoffvorprodukte werden in Mengen von 0,2 - 5 Gew.-%, vorzugsweise 1 - 3 Gew.-% des gesamten Färbemittels, in den Träger einge¬ mischt. Der Gehalt an Bis-(2,5-diaminonphenoxy)-oxaalkanen der Formel (I) kann in den erfindungsgemäßen Haarfärbemitteln etwa 0,05 - 10 Millimol pro 100 g des Haarfärbemittels betragen.The oxidation dye precursors are mixed into the carrier in amounts of 0.2-5% by weight, preferably 1-3% by weight, of the total colorant. The content of bis- (2,5-diaminonphenoxy) -oxaalkanes of the formula (I) in the hair colorants according to the invention can be about 0.05-10 millimoles per 100 g of the hair colorant.
Die oxidative Entwicklung der Färbung kann grundsätzlich mit Luftsauer stoff erfolgen. Bevorzugt wird jedoch ein chemisches Oxidationsmittel ein gesetzt, besonders dann, wenn neben der Färbung ein Aufhelleffekt am Haa gewünscht wird. Als Oxidationsmittel kommen insbesondere Wasserstoffper oxid oder dessen Anlagerungsprodukte an Harnstoff, Melamin oder Natrium borat sowie Gemische aus derartigen Wasserstoffperoxidanlagerungsprodukte mit Kaliumperoxiddisulfat in Betracht.The oxidative development of the color can basically be done with atmospheric oxygen. However, a chemical oxidizing agent is preferably used, especially if, in addition to the coloring, a whitening effect on the hair is desired. 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.
Bevorzugt wird eine Zubereitung des Oxidationsmittels unmittelbar vor de Haarefärben mit der Zubereitung aus OxidationsfarbstoffVorprodukten un Träger vermischt. Das dabei entstehende gebrauchsfertige Haarfärbepräpara sollte bevorzugt einen pH-Wert in Bereichen von 6 - 10 aufweisen. Besonders bevorzugt ist die Anwendung der Haarfärbemittel in einem schwach alkalischen Milieu. Die Aπwendungste peraturen können in einem Bereich zwischen 15°C und 40° C liegen. Nach einer Einwirkungszeit von ca. 30 Mi¬ nuten wird das Haarfärbemittel durch Ausspülen von dem zu färbenden Haar entfernt. Danach wird das Haar mit einem milden Shampoo πachgewaschen und getrocknet. Das Nachwaschen mit einem Shampoo entfällt, wenn ein stark tensidhaltiger Träger, z. B. ein Färbeshampoo verwendet wurde.A preparation of the oxidizing agent is preferably mixed with the preparation of oxidation dye precursors and carrier immediately before hair coloring. The resulting ready-to-use hair dye preparation should preferably have a pH in the range of 6-10. It is particularly preferred to use the hair dye in a weakly alkaline environment. The application temperatures can be in a range between 15 ° C and 40 ° C. After an exposure time of approximately 30 minutes, the hair dye is removed from the hair to be dyed by rinsing. The hair is then washed with a mild shampoo and dried. Washing with a shampoo is not necessary if a carrier with a high tenside content, e.g. B. a coloring shampoo was used.
Die nachfolgenden Beispiele sollen den Erfindungsgegenstand näher erläu¬ tern ohne ihn jedoch hierauf zu beschränken. The following examples are intended to explain the subject matter of the invention in more detail without, however, restricting it thereto.
B e i s p i e l eB e i s p i e l e
1. Herstellungsbeispiele1. Manufacturing examples
1.1 1.8-Bis-(2,5-diaminopheπoxy)-3.5-dioxaoctan-tetrahvdrochlorid (Formel I, n = 2, x - 2)1.1 1.8-bis (2,5-diaminopheπoxy) -3.5-dioxaoctane-tetrahvdrochloride (formula I, n = 2, x - 2)
8,0 g l,8-Bis-(5-πitro-2-aminophenoxy)-3,6-dioxaoctan, hergestell gemäß Khim Geterotsikl. Soedin 1989. (5) 677-9 (Che . Abstr. 11 (1990): 158214p), wurden in 250 ml Ethanol gelöst und nach Zugabe vo Palladium (auf Kohle) als Katalysator mit Wasserstoff (20 bar) be 50°C hydriert. Nach Beendigung der Wasserstoffaufnähme wurde der Kata lysator durch Filtration abgetrennt und das Filtrat mit verdünnte Salzsäure angesäuert. Nach dem Abdampfen des Lösungsmittels wurden al Rückstand 8,3 g (86 % d. Th) in Form grauer Kristalle mit eine Schmelzpunkt ab 201 βC (unter Zersetzung) erhalten.8.0 gl, 8-bis- (5-πitro-2-aminophenoxy) -3,6-dioxaoctane, prepared according to Khim Geterotsikl. Soedin 1989. (5) 677-9 (Che. Abstr. 11 (1990): 158214p), were dissolved in 250 ml of ethanol and, after addition of palladium (on carbon) as a catalyst, hydrogenated at 50 ° C. with hydrogen (20 bar) . After the hydrogen uptake had ended, the catalyst was removed by filtration and the filtrate was acidified with dilute hydrochloric acid. After evaporation of the solvent, 8.3 g (86% of theory) were obtained as a residue in the form of gray crystals with a melting point from 201 ° C. (with decomposition).
1.21.5-Bis-f2.5-diaminophenoxy)-3-oxapentan-tetrahvdrochlorid (Formel I n - 2, x - 1)1.21.5-bis-f2.5-diaminophenoxy) -3-oxapentane tetrahvdrochloride (formula I n - 2, x - 1)
Eine Mischung aus 23,1 g (0,15 Mol) 2-Amino-5-nitrophenol, 27,9 g (0, Mol) Kaliumcarbonat und 150 ml Dimethylfor amid wurde auf 40 °C er wärmt. Dann wurden 17,4 g (0,075 Mol) Dibrom-diethylether zugetropf und die Reaktionsmischung 6 Stunden lang auf 140 °C erhitzt. Nach de Abkühlen auf 20 °C wurde das Reaktionsgemisch unter Rühren in 1,5 Wasser gegossen. Das dabei ausfallende Reaktionsprodukt wurde abfil triert, mit Wasser gewaschen und bei 75 °C unter vermindertem Druc getrocknet. Dabei fielen 23,6 g rohes l,5-Bis-(2-amino-5-nitrophen oxy)-3-oxapentan mit einem Schmelzpunkt von 137,5 - 139 β C an.A mixture of 23.1 g (0.15 mol) of 2-amino-5-nitrophenol, 27.9 g (0, mol) of potassium carbonate and 150 ml of dimethylfor amide was heated to 40 ° C. Then 17.4 g (0.075 mol) of dibromo-diethyl ether were added dropwise and the reaction mixture was heated to 140 ° C. for 6 hours. After cooling to 20 ° C., the reaction mixture was poured into 1.5 water with stirring. The resulting reaction product was filtered off, washed with water and dried at 75 ° C. under reduced pressure. In this case were 23.6 g of crude l, 5-bis- (2-amino-5-nitrophen oxy) -3-oxapentane having a melting point 137.5 to 139 C to β.
Von diesem l,5-Bis-(2-amino-5-nitrophenoxy)-3-oxapentan wurden 20 g i 400 ml Ethanol und 40 ml Wasser gelöst, und nach Zusatz von 5 Gew.- Palladium auf Aktivkohle als Katalysator bei 50 °C mit Wasserstoff (2 bar) hydriert. Nach Beendigung der Wasserstoffaufnahme wurde der Kata lysator durch Filtration abgetrennt und das Filtrat mit verdünnte Salzsäure angesäuert. Nach dem Einengen zur Trockene wurden 23,6 rohes l,5-Bis-(2,5-diaminophenoxy)-3-oxapentan erhalten. Das Produk wurde aus 70 ml halbkonzentrierter Salzsäure umkristall siert und be 75 °C getrocknet. Es wurden 17,4 g in Form grauer Kristalle erhalten die sich oberhalb 215 °C violett verfärben und sich ab 230 °C zerset¬ zen.From this 1,5-bis- (2-amino-5-nitrophenoxy) -3-oxapentane, 20 gi 400 ml of ethanol and 40 ml of water were dissolved, and after adding 5% by weight of palladium on activated carbon as a catalyst at 50 ° C. hydrogenated with hydrogen (2 bar). After the hydrogen uptake had ended, the catalyst was separated off by filtration and the filtrate was acidified with dilute hydrochloric acid. After concentration to dryness, 23.6 crude 1,5-bis (2,5-diaminophenoxy) -3-oxapentane was obtained. The product was recrystallized from 70 ml of semi-concentrated hydrochloric acid and dried at 75 ° C. 17.4 g were obtained in the form of gray crystals which turn violet above 215 ° C and decompose above 230 ° C.
2. Anwendunαsbeispiele2. Application examples
Es wurden erfindungsgemäße Haarfärbemittel in Form einer Haarfärbe-Cre e- emulsion der folgenden Zusammensetzung hergestellt:Hair colorants according to the invention were produced in the form of a hair dyeing cre e-emulsion of the following composition:
Fettalkohol C12-C18 10 gFatty alcohol C12-C18 10 g
Fettalkohol C12-C1 + 2 EO-sulfatFatty alcohol C12-C1 + 2 EO-sulfate
Na-Salz, 28%ig 25 gNa salt, 28% 25 g
Wasser 60 gWater 60 g
Entwicklerkomponente (El, E2) 7,5 MolDeveloper component (El, E2) 7.5 mol
Kupplerkomponente (Kl - K13) 7,5 mMolCoupler component (Kl - K13) 7.5 mmol
Na2S03 (Inhibitor) 1.0 g konzentrierte Ammoniak-Lösung bis pH = 9,5Na2S03 (inhibitor) 1.0 g concentrated ammonia solution up to pH = 9.5
Wasser ad 100 gWater ad 100 g
Die Bestandteile wurden der Reihe nach miteinander vermischt. Nach Zugabe der Oxidationsfärbemittelvorprodukte und des Inhibitors wurde zunächst mit konzentrierter Ammoniak-Lösung der pH-Wert der Emulsion auf 9,5 einge¬ stellt, 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 9.5 with concentrated ammonia solution, and the mixture was then made up to 100 g with water.
Die oxidative Entwicklung der Färbung wurde mit 3%iger Wasserstoffperoxid¬ lösung als Oxidationsmittel 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 using 3% hydrogen peroxide solution as the oxidizing agent. 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 Haarwaschmittel ausgewaschen und anschließend getrocknet.The coloring cream was applied to strands approx. 5 cm long, 90% gray, but not specially pretreated, and left there for 30 minutes at 27 ° C. After the dyeing process had ended, the hair was rinsed, washed out with a customary shampoo and then dried.
Als Entwicklerkomponenten wurden die erfindungsgemäßen Verbindungen gemäß Beispiel 1.1 (El) und Beispiel 1.2 (E2) eingesetzt. Als Kupplerkomponenten wurden die folgenden Verbindungen verwendetThe compounds according to the invention according to Example 1.1 (E1) and Example 1.2 (E2) were used as developer components. The following compounds were used as coupler components
Kl Resorc nKl Resorc n
K2 4-ChlorresorcinK2 4-chlororesorcinol
K3 α-NaphtholK3 α-naphthol
K4 1,5-DihydroxynaphthalinK4 1,5-dihydroxynaphthalene
K5 -AminophenolK5 aminophenol
K6 5-Amino-2-methy1pheno1K6 5-amino-2-methylpheno1
K7 5-Amino-4-chlor-2-methylphenolK7 5-amino-4-chloro-2-methylphenol
K8 2-Chlor-3-amino-6-methylphenolK8 2-chloro-3-amino-6-methylphenol
K9 2,4-Dichlor-3-aminophenolK9 2,4-dichloro-3-aminophenol
K10 l,3-Bis-(2,4-diaminophenoxy)-propanK10 l, 3-bis (2,4-diaminophenoxy) propane
Kll l-Phenyl-3-methyl-pyrazolon-5Kll l-phenyl-3-methyl-pyrazolon-5
K12 l-Phenyl-3-amino-pyrazolon-5K12 1-phenyl-3-aminopyrazolone-5
K13 2,6-Dihydroxy-3,4-dimethylpyridinK13 2,6-dihydroxy-3,4-dimethylpyridine
K14 8-Methyl-imidazo[l,2a]pyridin-2K14 8-methyl-imidazo [1,2a] pyridine-2
Die mit diesen OxidationsfarbstoffVorprodukten in der Kombination gemä Tabelle I erhaltenen Haaranfärbungen sind der Tabelle zu entnehmen.The hair colorations obtained with these oxidation dye precursors in the combination according to Table I can be seen from the table.
In Beispiel 2.19 wurde anstelle eines Kupplers der Entwickler El einge setzt (also insgesamt 15 mMol El). In Example 2.19 the developer El was used instead of a coupler (thus a total of 15 mmol El).
Tabelle ITable I
Fortsetzung Tabelle I Continuation of table I

Claims

P a t e n t a n s p r ü c h e Patent claims
1. Bis-(2, 5-diaminophenoxy)-oxaalkane der Formel I1. bis (2,5-diaminophenoxy) oxaalkanes of the formula I.
in der n = 2 oder 3 und x eine ganze Zahl von 1 - 3 ist. in which n = 2 or 3 and x is an integer from 1 to 3.
2. Bis-(2,5-diaminophenoxy)-oxaalkane gemäß Patentanspruch 1, dadurch gekennzeichnet, daß n = 2 und x = 1 oder 2 ist.2. bis (2,5-diaminophenoxy) oxaalkanes according to claim 1, characterized in that n = 2 and x = 1 or 2.
3. Verfahren zur Herstellung von Bis-(2,5-diaminophenoxy)-oxaalkanen der Formel I gemäß Anspruch 1, dadurch gekennzeichnet, daß man ein Bis- (2-amino-5-nitrophenoxy)-oxaalkan der Formel II3. A process for the preparation of bis (2,5-diaminophenoxy) oxaalkanes of the formula I according to claim 1, characterized in that a bis (2-amino-5-nitrophenoxy) oxaalkane of the formula II
in der n = 2 oder 3 und x eine ganze Zahl von 1 - 3 ist, katalytisch zum entsprechenden Bis-(2,5-diaminophenoxy)oxaalkan der Formel I hy¬ driert. in which n = 2 or 3 and x is an integer from 1 to 3, is catalytically hydrogenated to the corresponding bis- (2,5-diaminophenoxy) oxaalkane of the formula I.
4. Verwendung von Bis-(2,5-diaminophenoxy)-oxaa1kanen der Formel I gemäß Anspruch 1 oder 2 sowie deren wasserlösliche Salze als Entwicklerver¬ bindungen zur Erzeugung von Oxidationsfärbungen.4. Use of bis- (2,5-diaminophenoxy) -oxaa1kanen of formula I according to claim 1 or 2 and their water-soluble salts as developer compounds for producing oxidation colorations.
5. Haarfärbemittel, enthaltend Oxidationsfarbstoffvorprodukte in einem Träger, dadurch gekennzeichnet, daß als Oxidationsfarbstoffvorprodukte wenigstens ein Bis-(2,5-diaminophenoxy)-oxaalkan der Formel I gemäß Anspruch 1 oder 2 oder dessen wasserlösliches Salz als Entwicklerkom¬ ponente und wenigstens eine in Oxidationshaarfärbemitteln übliche Kupperkomponente enthalten sind. 5. Hair dye containing oxidation dye precursors in a carrier, characterized in that as oxidation dye precursors at least one bis- (2,5-diaminophenoxy) -oxaalkane of the formula I according to claim 1 or 2 or its water-soluble salt as developer component and at least one in oxidation hair dye Usual coupler components are included.
6. Haarfärbemittel nach Anspruch 5, dadurch gekennzeichnet, daß al Kupplerkomponente wenigstens eine Verbindung aus der Gruppe der Re sorcine, Naphthole, Aminophenole oder Hydroxypyridine enthalten ist.6. Hair dye according to claim 5, characterized in that al coupler component contains at least one compound from the group of Re sorcine, naphthols, aminophenols or hydroxypyridines.
7. Haarfärbemittel nach Anspruch 5 oder 6, dadurch gekennzeichnet, da als Träger ein wäßriges Gel mit einem Gehalt von 1 - 20 Gew.-% eine Seife oder eine Öl-in-Wasser-Emulsion mit einem Gehalt von 1 - 2 Gew.-% einer Fettkomponente und 0,5 - 30 Gew.-% eines Emulgiermittel aus der Gruppe der oberflächenaktiven Substanzen und als Oxidations farbstoffvorprodukt wenigstens ein Bis-(2,5-diaminophenoxy)-oxaalka der Formel I in einer Menge von 0,05 - 10 Millimol pro 100 g de Haarfärbemittels enthalten ist. 7. Hair dye according to claim 5 or 6, characterized in that as a carrier an aqueous gel with a content of 1 - 20 wt .-%, a soap or an oil-in-water emulsion with a content of 1 - 2 wt .-% % of a fat component and 0.5-30% by weight of an emulsifier from the group of surface-active substances and as an oxidation dye precursor, at least one bis- (2,5-diaminophenoxy) oxaalka of the formula I in an amount of 0.05-10 Millimoles per 100 g of hair dye is included.
EP19920901017 1991-01-31 1991-12-19 2,5-diamino phenoxy oxaalkanes and their use as initial oxidation dyes Withdrawn EP0569368A1 (en)

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DE19607751A1 (en) * 1996-02-29 1997-09-04 Henkel Kgaa New aminophenol derivatives and their use
FR2767685B1 (en) † 1997-09-01 2004-12-17 Oreal COMPOSITION FOR OXIDATION DYEING OF KERATINIC FIBERS COMPRISING 2-CHLORO 6-METHYL 3-AMINOPHENOL AND AN OXIDATION BASE, AND DYEING METHOD
FR2779948B1 (en) * 1998-06-19 2004-04-23 Oreal TINCTORIAL COMPOSITION CONTAINING 1,8-BIS- (2,5-DIAMINOPHENOXY) -3,5-DIOXAOCTANE, AN ADDITIONAL OXIDATION BASE AND A COUPLER, AND DYEING METHODS
FR2799960B1 (en) * 1999-10-21 2002-12-20 Oreal KERATINIC FIBER OXIDATION DYE COMPOSITION AND DYEING METHOD USING THE SAME
FR2799962B1 (en) * 1999-10-21 2002-07-26 Oreal KERATINIC FIBER OXIDATION DYE COMPOSITION AND DYEING METHOD USING THE SAME
DE10125880A1 (en) * 2001-05-28 2002-12-05 Henkel Kgaa New developer components for oxidation hair colors
DE10128472A1 (en) * 2001-06-12 2002-12-19 Henkel Kgaa Oxidative dyeing compositions for keratin fibers contain m-phenylenediamine derivatives (some of which are novel compounds) as couplers giving red shades with conventional developers
DE10160815A1 (en) * 2001-12-11 2003-06-18 Henkel Kgaa Oxidation dye composition, useful for dyeing keratin fibers, especially human hair, comprises 2,4-dichloro-3-aminophenol and a bis-p-phenylenediamine or bis-p-aminophenol compound
DE102004045323A1 (en) * 2004-09-16 2006-03-30 Henkel Kgaa Polyalkoxylated diaminobenzenes as a developer
WO2007073562A2 (en) * 2005-12-20 2007-06-28 Invitrogen Corporation Fluorescent ion indicators for cadmium and lanthanide ion detection

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DE2852272A1 (en) * 1978-12-02 1980-06-19 Henkel Kgaa NEW DEVELOPMENT COMPONENTS FOR OXIDATION HAIR COLORS, THEIR PRODUCTION AND THEIR HAIR COLORING CONTAINERS
DE3011191A1 (en) * 1980-03-22 1981-10-01 Henkel KGaA, 4000 Düsseldorf NEW COUPLER COMPONENTS FOR OXIDATION HAIR COLORS, THEIR PRODUCTION AND USE AND THEIR HAIR COLORING CONTAINERS
DE3149330A1 (en) * 1981-12-12 1983-06-16 Henkel KGaA, 4000 Düsseldorf Hydroxyethylated bis(2,5-diaminophenoxy)alkanes and their use in hair dyes
FR2636062B1 (en) * 1988-09-06 1990-11-30 Oreal PROCESS FOR THE PREPARATION OF (ALPHA), (OMEGA) -DIAMINES ALIPHATICS, NEW COMPOUND AND ITS USE IN HAIR DYEING

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