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WO1996022077A1 - Aryl ketones for colouring keratin-containing fibres - Google Patents

Aryl ketones for colouring keratin-containing fibres Download PDF

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Publication number
WO1996022077A1
WO1996022077A1 PCT/EP1996/000062 EP9600062W WO9622077A1 WO 1996022077 A1 WO1996022077 A1 WO 1996022077A1 EP 9600062 W EP9600062 W EP 9600062W WO 9622077 A1 WO9622077 A1 WO 9622077A1
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WIPO (PCT)
Prior art keywords
groups
amino
formula
alkyl
group
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Application number
PCT/EP1996/000062
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German (de)
French (fr)
Inventor
Hinrich Möller
Horst Höffkes
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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Publication of WO1996022077A1 publication Critical patent/WO1996022077A1/en

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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
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/35—Ketones, e.g. benzophenone
    • 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
    • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
    • A61Q5/065—Preparations for temporary colouring the hair, e.g. direct dyes

Definitions

  • the invention relates to the use of certain aryl ketones for dyeing keratin-containing fibers, in particular human hair.
  • keratin fibers e.g. B. hair, wool or furs
  • direct dyes or oxidation dyes which are formed by oxidative coupling of one or more developer components with each other or with one or more coupler components
  • oxidation dyes intensive dyeings with good fastness properties can be achieved, but the development of the color takes place under the influence of oxidizing agents such as. B. H2Ü2, which often results in damage to the fiber.
  • Direct dyes are applied under gentler conditions, but their disadvantage is that the dyeings often have inadequate fastness properties.
  • keratin fibers e.g. Wool, furs, skins and human hair are considered.
  • the aryl ketones described below can also be used to dye other natural fibers, e.g. Cotton, jute, sisal, linen or silk, modified natural fibers, e.g. Regenerated cellulose, nitro, alkyl or hydroxyalkyl or acetyl cellulose and synthetic fibers such as e.g. Polyamide, polyacrylonitrile, polyurethane and polyester fibers can be used.
  • the invention relates to the use of aryl ketones of the formula I
  • R represents a C 1 -C 4 -alkyl group or an aryl group and R * also a C 1 -C 4 -alkylene group which is connected to the aromatic radical of the formula I or an N, S or O-containing isoelectronic group , optionally benzo-fused
  • R ⁇ , R and R 4 independently of one another for hydrogen, halogen atoms, hydroxy groups, -C-C _ ⁇ - alkoxy groups, -C-C4-alkyl groups, C2 ⁇ C4-hydroxyalkyl groups, amino (-C-C4) alkyl groups, -C-C4-alkoxy- (C ⁇ -C.4) - alkyl groups, nitro, carboxy or sulfo groups or groups NR5R6, where R5 and R & C ⁇ -C4 ⁇ alkyl groups or C2 ⁇ C4- Hydroxyalkyl groups mean and together with the N atom can also represent a 5-, 6- or 7-membere
  • aryl ketones or their ketals to be used according to the invention are: acetophenone, propiophenone, 2-, 3-, 4-hydroxyacetophenone, -propiophenone, -butyrophenone, 2,4-, 2,5-, 2,6-dihydroxyacetophenone , 2,3,4-, 3,4,5-, 2,4,5-trihydroxy, 2,4,6-, 3,4,5-trimethoxy-acetophenone, 3,4,5-trimethoxy-acetophenone diethyl ketal, 4-hydroxy-3-methoxy, 3,5-dimethoxy-4-hydroxy, 4-amino, 4-dimethylamino, 4-morpholino, 4-piperidino, 4-imidazolino, 2-hydroxy-5-bromo, 4-hydroxy-3-nitroacetophenone, acetophenone-2-, -4-carboxylic acid, benzophenone, 4-hydroxy, 2-amino, 4,4'-, 2,4-dihy - Hydroxy-, 2,4,4'--hydroxy
  • Acetophenone, 2-hydroxyacetophenone, 4-hydroxyacetophenone, 2,4-dihydroxyacetophenone, 2,5-dihydroxyacetophenone, 2,6-dihydroxyacetophenone, 2,4,6-trihydroxyacetophenone, 2,3,4-trihydroxyacetophenone and quercetin are preferably used and (+) - usnic acid.
  • the aryl ketones of formula I alone only weakly stain keratin fibers. Brilliant colorations in the orange, brown, red-brown, blue-black and black range with good fastness properties (fastness to light, fastness to washing, fastness to rubbing) are achieved if the aryl ketones of the formula I together with compounds having a primary or secondary amino group, for example aniline derivatives , with a nitrogen-containing heterocytic compound, eg primary heteroaro a- table amines, or an aromatic hydroxy compound can be used. On the one hand, these are compounds which also only weakly dye hair on their own and only give brilliant colorations together with the aryl ketones of the formula I.
  • Suitable compounds with a primary or secondary amino group are, for example, primary aromatic amines such as N- (2-hydroxyethyl) -N-ethyl-, N, N-bis- (2-hydroxyethyl) -, N- (2-methoxyethyl-), 2 , 3-, 2,4-, 2,5-dichloro-p-phenylene diamine, 2-chloro-p-phenylene diamine, 2,5-dihydroxy-4-morpholinoaniline dihydrobromide, 2-, 3-, 4- Aminophenol, o-, m-, p-phenylene diamine, 2,5-diaminotoluene, phenol, anisole, phenethole, 2-chloro-p-phenylene diamine, 4-methylamino, 3-, 4-dimethylamino , 3,4-methylene-dioxyaniline, 3-amino-2,4-dichloro, 4-methylamino, 2-methyl-5-amino, 3-methyl
  • Suitable nitrogen-containing heterocycles are e.g. 2-, 3-, 4-amino, 2-amino-3-hydroxy, 2,6-diamino, 2,5-diamino, 2,3-diamino, 2-dimethylamino-5-amino -, 3-amino-2-methylamino-6-methoxy-, 2,3-diamino-6-methoxy-, 3,5-diamino-2,5-dimethoxy-, 2,4,5-triamino-, 2,6-di-hydroxy-3,4-dimethylpyridine, 4,5,6-triamino-, 4-hydroxy-2,5,6-tri-amino-, 2,4,5,6-tetraamino-, 2nd -Methylamino-4,5,6-triamino-, 2,4-, 4,5-diamino-, 2-amino-4-methoxy-6-methyl-pyrimidine, 3,5-diamino-pyrazole, -1.2
  • Suitable aromatic hydroxy compounds are, for example, 2-, 4-, 5-methylresorcinol, resorcinol, 3-methoxyphenol, pyrocatechol, hydroquinone, pyrogallol, phloroglucinol, hydroxyhydroquinone, 2-, 3-, 4-methoxy-, 3-dimethylamino-, 2 - (2-hydroxyethyl) -, 3,4-methylenedioxyphenol, 2,4-, 3,4-dihydroxybenzoic acid, -phenylacetic acid, gallic acid, 2,4,6-trihydroxybenzoic acid, -acetophenone, 2-, 4-methyl-, 2-, 4-chlororesorcinol, 1-, 2-naphthol, 1 , 5-, 2,3-, 2,7-dihydroxynaphthalene, 6-dimethylamino-4-hydroxy-2-naphthalenesulfonic acid, 3,6-dihydroxy-2,7-naphthalenesulfonic acid.
  • Amino acids or oligopeptides composed of 2 to 9 amino acids are also suitable. All naturally occurring and synthetic amino acids are suitable as amino acids, e.g. which by hydrolysis from vegetable or animal proteins, e.g. Collagen, keratin, casein, elastin, soy protein, wheat gluten or almond protein accessible amino acids. Both acidic and alkaline amino acids can be used. Suitable 01igopeptides are all oligopeptides made up of naturally occurring and synthetic amino acids.
  • the oligopeptides can be naturally occurring or synthetic oligopeptides, but also the oligopeptides contained in polypeptide or protein hydrolyzates, provided they have sufficient water solubility for use in the colorants according to the invention. Examples are e.g. Glutathione or the oligopeptides contained in the hydrolyzates of collagen, keratin, casein, elastin, soy protein, wheat gluten or almond protein.
  • aryl ketones of the formula I can also be used together in all colorants; Likewise, several different components from the groups of compounds having a primary or secondary amino group, nitrogen-containing heterocycles, aromatic hydroxy compounds or amino acids can also be used together.
  • the colorants produce intensive colorations even at physiologically tolerable temperatures of below 45 ° C. They are therefore particularly suitable for dyeing human hair.
  • the colorants can be incorporated into a water-containing cosmetic carrier. Suitable water-containing cosmetic carriers are, for example, creams, emulsions, gels or also surfactant-containing foaming solutions such as shampoos or other preparations which are suitable for use on the hair.
  • the water-containing cosmetic carrier usually contains wetting and emulsifying agents such as anionic, nonionic or apholytic surfactants, for example fatty alcohol sulfates, alkane sulfonates, ⁇ -olefin sulfonates, fatty alcohol polyglycol ether sulfates, alkyl glycosides, ethylene oxide addition products with fatty alcohols, with fatty acids, with sorbitan fatty acids, with sorbitan fatty acids, with alkyl phenols Fatty acid partial glycerides and fatty acid alkanolamides; Thickeners, e.g. B.
  • anionic, nonionic or apholytic surfactants for example fatty alcohol sulfates, alkane sulfonates, ⁇ -olefin sulfonates, fatty alcohol polyglycol ether sulfates, alkyl glycosides, ethylene oxide addition products with fatty alcohols, with fatty acids, with
  • 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 and pectin, biosynthetic gums, such as xanthan gum and Dextra ⁇ e, synthetic gums, z.
  • bentonite or fully synthetic hydrocolloids such as polyvinyl alcohol or polyvinylpyrrolidone
  • hair care additives such as 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 oil Reducing agents to stabilize the ingredients, e.g. B. ascorbic acid, finally can also contain dyes for coloring the cosmetic preparations.
  • solubilizers such as ethylene, 1,3-propylene, 1,2-propylene, 1,2-butylene glycol, glycerol, ethanol, tert. Butanol, 2-propanol or phenethol in amounts of 2-50% may be useful.
  • water-free carriers are also suitable if the substrate to be colored is moistened with water.
  • Suitable water-free carriers are e.g. Oils combined with anhydrous emulsifiers such as paraffin oils or silicone oils of low to medium viscosity.
  • the aryl ketones of the formula I and the compounds having a primary or secondary amino group, the amino acids or oligopeptides composed of 2 to 9 amino acids, the nitrogen-containing heterocycles or the aromatic hydroxy compounds are in each case in an amount of 0.3 to 65, preferably 6 to 20 mmol, based in each case on 100 g of the total colorant.
  • Suitable metal salts are, for example, the formates, carbonates, halides, sulfates, butyrates, valerates, capronates, acetates, lactates, glycolates, tartrates, citrates, gluconates, propionates, phosphates and phosphonates of potassium, sodium, lithium, magnesium, calcium , Strontiums, bariums, manganese, iron, cobalt, copper, zinc; sodium acetate, lithium bromide, calcium bromide, calcium gluconate, zinc chloride, zinc sulfate, magnesium chloride, magnesium sulfate, ammonium carbonate, chloride and acetate are preferred, which in the given case are present in an amount of 0.3 to 65, preferably 6 to 20 mmol, based on 100 g of the total colorant, are contained.
  • the pH of the ready-to-use coloring preparations is between 2 and 11, preferably
  • the colorants are applied to the hair in the form of the water-containing, or else the water-free, cosmetic carrier in an amount of 50-100 g, left there for about 30 minutes and then rinsed out or washed out with a commercially available hair shampoo.
  • the two reactive components can either be applied to the hair at the same time or else one after the other, regardless of which of the two components is applied first; the ammonium or metal salts can be added to the first or second component. There may be a time interval of up to 30 minutes between the application of the first and the second component. Pretreatment of the hair with the saline solution is also possible.
  • the two reactive components can be stored together and separately either without water or already in the finished formulation. When stored separately, the reactive components are only intimately mixed with one another immediately before use.
  • the water-free storage can take place either in powder form or in water-free gels or dispersions. When stored as a powder, a defined amount of 50-80 ° C warm water is added to the mixture and a homogeneous mixture is produced. If an anhydrous gel is used, it can be mixed with water or applied directly to damp hair.
  • a slurry of 10 mmoles of an aryl ketone of formula I and 10 mmoles of a reactant, 10 mmoles of sodium acetate and a drop of a 20% fatty alkyl ether sulfate solution in 100 ml of water was prepared.
  • the slurry was etched to boiling temperature and filtered after cooling, the pH was then adjusted to 6.
  • the color depth was rated on the following scale:

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Abstract

The object of the invention is the use of aryl ketones of the formula (I) and for their ketals for colouring Keratin-containing fibres, especially human hair. In formula (I) R1 is a C¿1?-C4-alkyl group or an aryl group and R?1¿ may also be a C¿1?-C4-alkylene group bonded with the aromatic radical of formula (I) or an isoelectronic, N, S or O-containing, possibly benzoannellised group and R?2, R3 and R4¿ are mutually independently hydrogens, halogen atoms, hydroxy groups, C¿1?-C4-alkoxy groups, C1-C4-alkyl groups, C2-C4-hydroxyalkyl groups, amino-(C1-C4)-alkyl groups, C1-C4-alkoxy-(C1-C4)-alkyl groups nitro, carboxy or sulpho groups or NR?5R6¿ groups, in which R?5 and R6¿ are C¿1?-C4-alkyl groups or C2-C4-hydroxyalkyl groups, and together with the N atom can represent a 5, 6 or 7 member ring or the aromatic system represents an usnic acid radical.

Description

"Arylketone zum Färben keratinhaltiger Fasern" "Aryl ketones for dyeing keratin fibers"
Gegenstand der Erfindung ist die Verwendung von bestimmten Arylketo- nen zum Färben von keratinhaltigen Fasern, insbesondere menschlichen Haaren.The invention relates to the use of certain aryl ketones for dyeing keratin-containing fibers, in particular human hair.
Für das Färben von keratinhaltigen Fasern, z. B. Haaren, Wolle oder Pelzen, kommen im allgemeinen entweder direktziehende Farbstoffe oder Oxidationsfarbstoffe, die durch oxidative Kupplung einer oder mehrerer Entwicklerkomponeπten untereinander oder mit einer oder mehreren Kupplerkomponenten entstehen, zur Anwendung. Mit Oxidati- onsfarbstoffen lassen sich zwar intensive Färbungen mit guten Echt¬ heitseigenschaften erzielen, die Entwicklung der Farbe geschieht jedoch unter dem Einfluß von Oxidationsmitteln wie z. B. H2Ü2, was häufig Schädigungen der Faser zur Folge hat. Direktziehende Farb¬ stoffe werden unter schonenderen Bedingungen appliziert, ihr Nach¬ teil liegt jedoch darin, daß die Färbungen häufig nur über unzurei¬ chende Echtheitseigenschaften verfügen.For dyeing keratin fibers, e.g. B. hair, wool or furs, generally either direct dyes or oxidation dyes, which are formed by oxidative coupling of one or more developer components with each other or with one or more coupler components, are used. With oxidation dyes intensive dyeings with good fastness properties can be achieved, but the development of the color takes place under the influence of oxidizing agents such as. B. H2Ü2, which often results in damage to the fiber. Direct dyes are applied under gentler conditions, but their disadvantage is that the dyeings often have inadequate fastness properties.
Überraschenderweise wurde nun gefunden, daß sich bestimmte Arylke¬ tone auch in Abwesenheit von oxidierenden Agentien hervorragend zum Färben von keratinhaltigen Fasern eignen. Der Einsatz von oxidieren¬ den Agentien soll dabei jedoch keineswegs prinzipiell ausgeschlossen werden. Die Verwendung der unten näher beschriebenen Arylketone zum Färben von keratinhaltigen Fasern ist bislang nicht bekannt.Surprisingly, it has now been found that certain aryl ketones are outstandingly suitable for dyeing keratin-containing fibers even in the absence of oxidizing agents. The use of oxidizing agents should in no way be excluded in principle. The use of the aryl ketones described below for dyeing keratin fibers is not yet known.
Als keratinhaltige Fasern kommen z.B. Wolle, Pelze, Felle und menschliche Haare in Betracht. Die unten näher bezeichneten Arylke- tonen können prinzipiell aber auch zum Färben anderer Naturfasern, wie z.B. Baumwolle, Jute, Sisal, Leinen oder Seide, modifizierter Naturfasern, wie z.B. Regeneratcellulose, Nitro-, Alkyl- oder Hy- droxyalkyl- oder Acetylcellulose und synthetischer Fasern, wie z.B. Polyamid-, Polyacrylnitril ,-, Polyurethan- und Polyesterfasern ver¬ wendet werden.As keratin fibers, e.g. Wool, furs, skins and human hair are considered. In principle, the aryl ketones described below can also be used to dye other natural fibers, e.g. Cotton, jute, sisal, linen or silk, modified natural fibers, e.g. Regenerated cellulose, nitro, alkyl or hydroxyalkyl or acetyl cellulose and synthetic fibers such as e.g. Polyamide, polyacrylonitrile, polyurethane and polyester fibers can be used.
Gegenstand der Erfindung ist die Verwendung von Arylketonen der For¬ mel IThe invention relates to the use of aryl ketones of the formula I
Figure imgf000004_0001
Figure imgf000004_0001
in der R für eine Cι-C.4-Alkylgruppe oder eine Arylgruppe steht und R* auch eine mit dem aromatischen Rest der Formel I verbundene C\- C4~Alkylengruppe oder eine dazu isoelektronische N-, S- oder O-hal¬ tige, gegebenenfalls benzoannellierte, Gruppe sein kann, und R^, R und R4 unabhängig voneinander für Wasserstoffe, Halogenatome, Hy- droxygruppen, Cι-C_}-Alkoxygruppen, Cι-C4-Alkylgruppen, C2~C4-Hy- droxyalkylgruppen, Amino-(Cι-C4)-alkylgruppen, Cι-C4-Alkoxy-(Cι-C.4)- alkylgruppen, Nitro-, Carboxy- oder Sulfogruppen oder Gruppen NR5R6 stehen, worin R5 und R& Cι-C4~Alkylgruppen oder C2~C4-Hydroxyalkyl- gruppen bedeuten und gemeinsam mit dem N-Atom auch einen 5-, 6- oder 7-gliedrigen Ring darstellen können oder das aromatische System einen Usninsäurerest darstellt sowie deren Ketale, zum Färben von keratinhaltigen Fasern, insbesondere menschlichen Haaren.in which R represents a C 1 -C 4 -alkyl group or an aryl group and R * also a C 1 -C 4 -alkylene group which is connected to the aromatic radical of the formula I or an N, S or O-containing isoelectronic group , optionally benzo-fused, and R ^, R and R 4 independently of one another for hydrogen, halogen atoms, hydroxy groups, -C-C _} - alkoxy groups, -C-C4-alkyl groups, C2 ~ C4-hydroxyalkyl groups, amino (-C-C4) alkyl groups, -C-C4-alkoxy- (Cι-C.4) - alkyl groups, nitro, carboxy or sulfo groups or groups NR5R6, where R5 and R & Cι-C4 ~ alkyl groups or C2 ~ C4- Hydroxyalkyl groups mean and together with the N atom can also represent a 5-, 6- or 7-membered ring or the aromatic system represents a usnic acid residue and their ketals for dyeing keratin fibers, in particular human hair.
Als Beispiele für die erfindungsgemäß einzusetzenden Arylketone bzw. deren Ketale können genannt werden: Acetophenon, Propiophenon, 2-, 3-, 4-Hydroxyacetophenon, -propiophenon, -butyrophenon, 2,4-, 2,5-, 2,6-Dihydroxyacetophenon, 2,3,4-, 3,4,5-, 2,4,5-Trihydroxy-, 2,4,6-, 3,4,5-Trimethoxy-acetophenon, 3,4,5-Trimethoxy-acetophenon-diethyl- ketal, 4-Hydroxy-3-methoxy-, 3,5-Dimethoxy-4-hydroxy-, 4-Amino-, 4-Dimethylamino-, 4-Morpholino-, 4-Piperidino-, 4-Imidazolino-, 2- Hydroxy-5-brom-, 4-Hydroxy-3-nitroacetophenon, Acetophenon-2-, -4- carbonsäure, Benzophenon, 4-Hydroxy-, 2-Amino-, 4,4'-, 2,4-Dihy- droxy-, 2,4,4'-, 2,3,4-Trihydroxybenzophenon, 2-Hydroxy-l-, 1-Hydro- xy-2-acetonaphthon, Chromon, Chromon-2-carbonsäure, Flavon, 3-Hydro- xy-, 3,5,7-, 4',5,7-, 5,6,7-Trihydroxyflavon, Quercetin, Tannin, Rutin, Indanon, 9-Fluorenon, 3-Hydroxyfluorenon, Anthron, 1,8-Di- hydroxyanthron.Examples of the aryl ketones or their ketals to be used according to the invention are: acetophenone, propiophenone, 2-, 3-, 4-hydroxyacetophenone, -propiophenone, -butyrophenone, 2,4-, 2,5-, 2,6-dihydroxyacetophenone , 2,3,4-, 3,4,5-, 2,4,5-trihydroxy, 2,4,6-, 3,4,5-trimethoxy-acetophenone, 3,4,5-trimethoxy-acetophenone diethyl ketal, 4-hydroxy-3-methoxy, 3,5-dimethoxy-4-hydroxy, 4-amino, 4-dimethylamino, 4-morpholino, 4-piperidino, 4-imidazolino, 2-hydroxy-5-bromo, 4-hydroxy-3-nitroacetophenone, acetophenone-2-, -4-carboxylic acid, benzophenone, 4-hydroxy, 2-amino, 4,4'-, 2,4-dihy - Hydroxy-, 2,4,4'-, 2,3,4-trihydroxybenzophenone, 2-hydroxy-1, 1-hydroxy-2-acetonaphthone, chromone, chromone-2-carboxylic acid, flavone, 3-hydro - xy-, 3,5,7-, 4 ', 5,7-, 5,6,7-trihydroxyflavon, quercetin, tannin, rutin, indanon, 9-fluorenone, 3-hydroxyfluorenone, anthrone, 1,8-di - hydroxyanthrone.
Bevorzugte Verwendung finden Acetophenon, 2-Hydroxyacetophenon, 4- Hydroxyacetophenon, 2,4-Dihydroxyacetophenon, 2,5-Dihydroxyaceto- phenon, 2,6-Dihydroxyacetophenon, 2,4,6-Trihydroxyacetophenon, 2,3,4-Trihydroxyacetophenon und Quercetin sowie (+)-Usninsäure.Acetophenone, 2-hydroxyacetophenone, 4-hydroxyacetophenone, 2,4-dihydroxyacetophenone, 2,5-dihydroxyacetophenone, 2,6-dihydroxyacetophenone, 2,4,6-trihydroxyacetophenone, 2,3,4-trihydroxyacetophenone and quercetin are preferably used and (+) - usnic acid.
Diese Substanzen sind i.a. literaturbekannt oder im Chemikalienhan¬ del erhältlich.These substances are generally Known from the literature or available in chemicals trade.
Die Arylketone der Formel I alleine färben Keratinfasern nur schwach. Brillante Färbungen im Orange-, Braun-, Rotbraun-, Blau¬ schwarz- und Schwarzbereich mit guten Echtheitseigenschaften (Licht¬ echtheit, Waschechtheit, Reibechtheit) werden erzielt, wenn die Arylketone der Formel I gemeinsam mit Verbindungen mit primärer oder sekundärer Aminogruppe, z.B. Anilinderivaten, mit einer Stickstoff enthaltenden heterocycTischen Verbindung, z.B. primären heteroaro a- tischen Aminen, oder einer aromatischen Hydroxyverbindung verwendet werden. Dies sind einerseits Verbindungen, die für sich alleine Haare ebenfalls nur schwach färben und erst gemeinsam mit den Aryl- ketonen der Formel I brillante Färbungen ergeben. Andererseits sind darunter aber auch Verbindungen, die als Oxidationsfarbstoffvorpro- dukte Verwendung finden und für sich allein zum Haarefärben geeignet sind; in Gegenwart der Arylketone der Formel I jedoch werden noch kräftigere, brillantere Nuancen mit noch besseren Echtheitseigen¬ schaften erzielt.The aryl ketones of formula I alone only weakly stain keratin fibers. Brilliant colorations in the orange, brown, red-brown, blue-black and black range with good fastness properties (fastness to light, fastness to washing, fastness to rubbing) are achieved if the aryl ketones of the formula I together with compounds having a primary or secondary amino group, for example aniline derivatives , with a nitrogen-containing heterocytic compound, eg primary heteroaro a- table amines, or an aromatic hydroxy compound can be used. On the one hand, these are compounds which also only weakly dye hair on their own and only give brilliant colorations together with the aryl ketones of the formula I. On the other hand, however, there are also compounds which are used as oxidation dye precursors and which are suitable for dyeing hair on their own; in the presence of the aryl ketones of the formula I, however, even stronger, more brilliant shades with even better fastness properties are achieved.
Geeignete Verbindungen mit primärer oder sekundärer Aminogruppe sind z.B. primäre aromatische A ine wie N-(2-Hydroxyethyl)-N-ethyl-, N,N- Bis-(2-hydroxyethyl)-, N-(2-Methoxyethyl-) , 2,3-, 2,4-, 2,5-Dichlor- p-phenylendiamin, 2-C lor-p-phenylendiamin, 2,5-Dihydroxy-4-morpho- linoanilin-dihydrobromid, 2-, 3-, 4-Aminophenol , o-, m-, p-Phenylen- dia in, 2,5-Diaminotoluol, -phenol, -anisol, -phenethol, 2-Chlor-p- phenylendiamin, 4-Methylamino-, 3-, 4-Dimethylamino-, 3,4-Methylen- dioxyanilin, 3-Amino-2,4-dichlor-, 4-Methylamino-, 2-Methyl-5-ami- no-, 3-Methyl-4-amino-, 2-Methyl-5-(2-hydroxyethylamino)-, 2-Me- thyl-5-amino-6-chlor-, 2-Methyl-5-amino-4-chlor-, 2-Methyl-5-amino- 6-chlor-, 5-(2-Hydroxyethylamino)-4-methoxy-2-methyl-, 4-Amino-2- a inomethyl-phenol , l,3-Diamino-2,4-dimethoxybenzol , 2-, 3-, 4-Ami- nobenzoesäure, -phenylessigsäure, 2,3-, 2,4-, 2,5-, 3,4-, 3,5-Di- aminobenzoesäure, 4-, 5-Aminosalicylsäure, 3-Amino-4-hydroxy-, 4- Amino-3-hydroxy-benzoesäure, 2-, 3-, 4-Aminobenzolsulfonsäure, 3- Amino-4-hydroxybenzolsulfonsäure, 4-Amino-3-hydroxynaphthalin-l- sulfonsäure, 6-Amino-7-hydroxynaphthalin-2-sulfonsäure, 7-Amino-4- hydroxynaphthalin-2-sulfonsäure, 4-Amino-5-hydroxynaphthalin-2,7-di- sulfonsäure, 3-Amino-2-naphthoesäure, 3-Aminophthalsäure, 5-Amino- isophthalsäure, 1,3,5-, 1,2,4-Triaminobenzol, 1,2,4,5-Tetraaminoben- zol-tetrahydrochlorid, 2,4,5-Tπ'aminophenol-trihydrochlorid, Penta- aminobenzol-pentahydrochlorid, Hexaaminobenzol-hexahydrochlorid, 2,4,6-Triaminoresorcin-trihydrochlorid, 4,5-Diaminobrenzcatechin- sulfat, 4,6-Diaminopyrogallol-dihydrochlorid, 3,5-Diaπrino-4-hydroxy- brenzcatechin-sulfat, aromatische Aniline bzw. Phenole mit einem weiteren aromatischen Rest wie 4,4'-Diaminostilben-dihydrochlorid, 4,4'-Diaminostilben-2,2'-disulfonsäure, Na-Salz, 4,4'-Diaminodiphe- nyl ethan, -sulfid, -sulfoxid, -amin, 4,4'-Diaminodiphenylamin-2- sulfonsäure, 4,4'-Diaminobenzophenon, -diphenylether, 3,3' ,4,4'-Te- traaminodiphenyl-tetrahydrochlorid, 3,3' ,4,4'-Tetraamino-benzophe- non, l,3-Bis-(2,4-diaminophenoxy)-propan-tetrahydrochlorid, 1,8-Bis- (2,5-diaminophenoxy)-3,6-dioxaoctan-tetrahydrochlorid, l,3-Bis-(4- aminophenylamino)-propan, -2-propanol , l,3-Bis-[N-(4-aminophenyl)-2- hydroxyethylamino]-2-propanol , N,N-Bis-[2-(4-aminophenoxy)-ethyl]- methylamin-trihydrochlo id.Suitable compounds with a primary or secondary amino group are, for example, primary aromatic amines such as N- (2-hydroxyethyl) -N-ethyl-, N, N-bis- (2-hydroxyethyl) -, N- (2-methoxyethyl-), 2 , 3-, 2,4-, 2,5-dichloro-p-phenylene diamine, 2-chloro-p-phenylene diamine, 2,5-dihydroxy-4-morpholinoaniline dihydrobromide, 2-, 3-, 4- Aminophenol, o-, m-, p-phenylene diamine, 2,5-diaminotoluene, phenol, anisole, phenethole, 2-chloro-p-phenylene diamine, 4-methylamino, 3-, 4-dimethylamino , 3,4-methylene-dioxyaniline, 3-amino-2,4-dichloro, 4-methylamino, 2-methyl-5-amino, 3-methyl-4-amino, 2-methyl-5 - (2-hydroxyethylamino) -, 2-methyl-5-amino-6-chloro, 2-methyl-5-amino-4-chloro, 2-methyl-5-amino-6-chloro, 5th - (2-Hydroxyethylamino) -4-methoxy-2-methyl-, 4-amino-2- a inomethyl-phenol, l, 3-diamino-2,4-dimethoxybenzene, 2-, 3-, 4-aminobenzoic acid , -phenylacetic acid, 2,3-, 2,4-, 2,5-, 3,4-, 3,5-diaminobenzoic acid, 4-, 5-aminosalicylic acid, 3-amino-4-hydroxy-, 4- Amino-3-hydroxy-benzoic acid, 2-, 3-, 4-amino benzenesulfonic acid, 3-amino-4-hydroxybenzenesulfonic acid, 4-amino-3-hydroxynaphthalene-l-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, 5-aminoisophthalic acid, 1,3,5-, 1,2,4-triaminobenzene, 1,2,4 , 5-tetraaminobenzene tetrahydrochloride, 2,4,5-Tπ ' aminophenol trihydrochloride, pentaaminobenzene pentahydrochloride, hexaaminobenzene hexahydrochloride, 2,4,6-triaminoresorcinol trihydrochloride, 4,5-diaminobenzene catechol sulfate, 4,6-diaminopyrogallol dihydrochloride, 3,5-diaπrino-4-hydroxy-catechol sulfate, aromatic anilines or phenols with a further aromatic radical such as 4,4'-diaminostilbene dihydrochloride, 4,4'-diaminostilbene -2,2'-disulfonic acid, Na salt, 4,4'-diaminodiphenyl ethane, sulfide, sulfoxide, amine, 4,4'-diaminodiphenylamine-2-sulfonic acid, 4,4'-diaminobenzophenone, diphenyl ether, 3,3 ', 4,4'-tetraaminodiphenyl tetrahydrochloride, 3,3', 4,4'-tetraamino-benzophenone, 1,3-bis (2,4-diaminophenoxy) propane- tetrahydrochloride, 1,8-bis- (2,5-diaminophenoxy) -3,6-dioxaoctane-tetrahydrochloride, 1,3-bis- (4-aminophenylamino) propane, -2-propanol, 1,3-bis- [ N- (4-aminophenyl) -2-hydroxyethylamino] -2-propanol, N, N-bis- [2- (4-aminophenoxy) ethyl] methylamine-trihydrochloride.
Geeignete stickstoffhaltige Heterocyclen sind z.B. 2-, 3-, 4-Amino-, 2-Amino-3-hydroxy-, 2,6-Diamino-, 2,5-Diamino-, 2,3-Diamino-, 2-Di- methylamino-5-amino-, 3-Amino-2-methylamino-6-methoxy-, 2,3-Diami- no-6-methoxy-, 3,5-Diamino-2,5-dimethoxy-, 2,4,5-Triamino-, 2,6-Di- hydroxy-3,4-dimethylpyridin, 4,5,6-Triamino-, 4-Hydroxy-2,5,6-tri- amino-, 2,4,5,6-Tetraamino-, 2-Methylamino-4,5,6-triamino-, 2,4-, 4,5-Diamino-, 2-Amino-4-methoxy-6-methyl-pyrimidin, 3,5-Diamino- pyrazol, -1,2,4-triazol , 3-Amino-, 3-Amino-5-hydroxypyrazol, 2-,3-, 8-Aminochinolin, 4-Amino-chinaldin, 2-, 6-Aminonicotinsäure, 5-Ami- noisochinolin, 4-, 5-, 6-, 7-Aminoindol , 5-, 6-Aminoindazol , 5-, 7-Amino-benzimidazol, -benzothiazol, 2,5-Dihydroxy-4-morpholinoani- lin sowie Indol- und Indolinderivate, z.B. 5,6-Dihydroxyindol , 5,6- Dihydroxyindolin und 4-Hydroxyindolin, sowie deren mit vorzugsweise anorganischen Säuren wie z. B. Salz- oder Schwefelsäure gebildeten Salze.Suitable nitrogen-containing heterocycles are e.g. 2-, 3-, 4-amino, 2-amino-3-hydroxy, 2,6-diamino, 2,5-diamino, 2,3-diamino, 2-dimethylamino-5-amino -, 3-amino-2-methylamino-6-methoxy-, 2,3-diamino-6-methoxy-, 3,5-diamino-2,5-dimethoxy-, 2,4,5-triamino-, 2,6-di-hydroxy-3,4-dimethylpyridine, 4,5,6-triamino-, 4-hydroxy-2,5,6-tri-amino-, 2,4,5,6-tetraamino-, 2nd -Methylamino-4,5,6-triamino-, 2,4-, 4,5-diamino-, 2-amino-4-methoxy-6-methyl-pyrimidine, 3,5-diamino-pyrazole, -1.2 , 4-triazole, 3-amino-, 3-amino-5-hydroxypyrazole, 2-, 3-, 8-aminoquinoline, 4-aminoquininaldine, 2-, 6-aminonicotinic acid, 5-aminoisoquinoline, 4-, 5-, 6-, 7-aminoindole, 5-, 6-aminoindazole, 5-, 7-amino-benzimidazole, -benzothiazole, 2,5-dihydroxy-4-morpholinoaniline as well as indole and indoline derivatives, eg 5,6-dihydroxyindole, 5,6-dihydroxyindoline and 4-hydroxyindoline, as well as their preferably inorganic acids such as. B. hydrochloric or sulfuric acid salts formed.
Geeignete aromatische Hydroxyverbindungen sind z.B. 2-, 4-, 5-Me- thylresorcin, Resorcin, 3-Methoxyphenol, Brenzkatechin, Hydrochinon, Pyrogallol, Phloroglucin, Hydroxyhydrochinon, 2-, 3-, 4-Methoxy-, 3-Dimethylamino-, 2-(2-Hydroxyethyl)-, 3,4-Methylendioxyphenol, 2,4-, 3,4-Dihydroxybenzoesäure, -phenylessigsäure, Gallussäure, 2,4,6-Trihydroxybenzoesäure, -acetophenon, 2-, 4-Methyl-, 2-, 4- Chlorresorcin, 1-, 2-Naphthol, 1,5-, 2,3-, 2,7-Dihydroxynaphthalin, 6-Dimethylamino-4-hydroxy-2-naphthalinsulfonsäure, 3,6-Dihydroxy- 2,7-naphthalinsulfonsäure.Suitable aromatic hydroxy compounds are, for example, 2-, 4-, 5-methylresorcinol, resorcinol, 3-methoxyphenol, pyrocatechol, hydroquinone, pyrogallol, phloroglucinol, hydroxyhydroquinone, 2-, 3-, 4-methoxy-, 3-dimethylamino-, 2 - (2-hydroxyethyl) -, 3,4-methylenedioxyphenol, 2,4-, 3,4-dihydroxybenzoic acid, -phenylacetic acid, gallic acid, 2,4,6-trihydroxybenzoic acid, -acetophenone, 2-, 4-methyl-, 2-, 4-chlororesorcinol, 1-, 2-naphthol, 1 , 5-, 2,3-, 2,7-dihydroxynaphthalene, 6-dimethylamino-4-hydroxy-2-naphthalenesulfonic acid, 3,6-dihydroxy-2,7-naphthalenesulfonic acid.
Auch Aminosäuren oder aus 2 bis 9 Aminosäuren aufgebaute Oligopep- tide sind geeignet. Als Aminosäuren kommen alle natürlich vorkom¬ menden und synthetischen Aminosäuren in Frage, z.B. die durch Hy¬ drolyse aus pflanzlichen oder tierischen Proteinen, z.B. Kollagen, Keratin, Casein, Elastin, Sojaprotein, Weizengluten oder Mandelpro¬ tein zugänglichen Aminosäuren. Dabei können sowohl sauer als auch alkalisch reagierende Aminosäuren eingesetzt werden. Geeignete 01 i- gopeptide sind alle aus natürlich vorkommenden und synthetischen Aminosäuren aufgebauten Oligopeptide.Amino acids or oligopeptides composed of 2 to 9 amino acids are also suitable. All naturally occurring and synthetic amino acids are suitable as amino acids, e.g. which by hydrolysis from vegetable or animal proteins, e.g. Collagen, keratin, casein, elastin, soy protein, wheat gluten or almond protein accessible amino acids. Both acidic and alkaline amino acids can be used. Suitable 01igopeptides are all oligopeptides made up of naturally occurring and synthetic amino acids.
Die Oligopeptide können dabei natürlich vorkommende oder syntheti¬ sche Oligopeptide, aber auch die in Polypeptid- oder Proteinhydro- lysaten enthaltenen Oligopeptide sein, sofern sie über eine für die Anwendung in den erfindungsgemäßen Färbemitteln ausreichende Was¬ serlöslichkeit verfügen. Als Beispiele sind z.B. Glutathion oder die in den Hydrolysaten von Kollagen, Keratin, Casein, Elastin, Sojapro¬ tein, Weizengluten oder Mandelprotein enthaltenen Oligopeptide zu nennen.The oligopeptides can be naturally occurring or synthetic oligopeptides, but also the oligopeptides contained in polypeptide or protein hydrolyzates, provided they have sufficient water solubility for use in the colorants according to the invention. Examples are e.g. Glutathione or the oligopeptides contained in the hydrolyzates of collagen, keratin, casein, elastin, soy protein, wheat gluten or almond protein.
In allen Färbemitteln können auch mehrere verschiedene Arylketone der Formel I gemeinsam zum Einsatz kommen; ebenso können auch meh¬ rere verschiedene Komponenten aus den Gruppen von Verbindungen mit primärer oder sekundärer Aminogruppe, von stickstoffhaltigen Hetero- cyclen, aromatischen Hydroxyverbindungen oder Aminosäuren gemeinsam verwendet werden. Die Färbemittel ergeben bereits bei physiologisch verträglichen Temperaturen von unter 45°C intensive Färbungen. Sie eignen sich deshalb besonders zum Färben von menschlichen Haaren. Zur Anwendung auf dem menschlichen Haar können die Färbemittel in einen wasser¬ haltigen kosmetischen Träger eingearbeitet werden. Geeignete was¬ serhaltige kosmetische Träger sind z.B. Cremes, Emulsionen, Gele oder auch tensidhaltige schäumende Lösungen wie z.B. Shampoos oder andere Zubereitungen, die für die Anwendung auf dem Haar geeignet sind.Several different aryl ketones of the formula I can also be used together in all colorants; Likewise, several different components from the groups of compounds having a primary or secondary amino group, nitrogen-containing heterocycles, aromatic hydroxy compounds or amino acids can also be used together. The colorants produce intensive colorations even at physiologically tolerable temperatures of below 45 ° C. They are therefore particularly suitable for dyeing human hair. For use on human hair, the colorants can be incorporated into a water-containing cosmetic carrier. Suitable water-containing cosmetic carriers are, for example, creams, emulsions, gels or also surfactant-containing foaming solutions such as shampoos or other preparations which are suitable for use on the hair.
Der wasserhaltige kosmetische Träger enthält üblicherweise Netz- und Emulgiermittel wie anionische, nichtionische oder a pholytische Ten- side, z.B. Fettalkoholsulfate, Alkansulfonate, α-Olefinsulfonate, Fettalkoholpolyglykolethersulfate, Alkylglycoside, Ethylenoxidanla- gerungsprodukte 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 und Pektin, biosynthetische Gummen, z.B. Xanthan-Gummi und Dextraπe, synthetische Gummen, z. B. Agar- Agar und Algin, Stärke-Fraktionen und Derivate wie Amylose, Amylo- pektin und Dextrine, modifizierte Cellulosemoleküle, z. B. Methyl- cellulose, Hydroxyalkylcellulose und Carboxymethylcellulose, Tone wie z. B. Bentonit oder vollsynthetische Hydrokolloide, z.B. Poly- vinylalkohol oder Polyvinylpyrrolidon, 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 Inhaltsstoffe, z. B. Ascorbinsäure, schließlich können auch Farbstoffe zum Einfärben der kosmetischen Zubereitungen enthalten sein.The water-containing cosmetic carrier usually contains wetting and emulsifying agents such as anionic, nonionic or apholytic surfactants, for example fatty alcohol sulfates, alkane sulfonates, α-olefin sulfonates, fatty alcohol polyglycol ether sulfates, alkyl glycosides, ethylene oxide addition products with fatty alcohols, with fatty acids, with sorbitan fatty acids, with sorbitan fatty acids, with alkyl phenols 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 and pectin, biosynthetic gums, such as xanthan gum and Dextraπe, synthetic gums, z. B. agar-agar and algin, starch fractions and derivatives such as amylose, amylopectin and dextrins, modified cellulose molecules, eg. As methyl cellulose, hydroxyalkyl cellulose and carboxymethyl cellulose, clays such as. B. bentonite or fully synthetic hydrocolloids, such as polyvinyl alcohol or polyvinylpyrrolidone, hair care additives such as 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 oil Reducing agents to stabilize the ingredients, e.g. B. ascorbic acid, finally can also contain dyes for coloring the cosmetic preparations.
Außerdem kann der Zusatz von Lösungsvermittlern wie Ethylen-, 1,3- Propylen-, 1,2-Propylen-, 1,2-Butylenglykol, Glycerin, Ethanol, tert. Butanol, 2-Propanol oder Phenethol in Mengen von 2 - 50 % nützlich sein.In addition, the addition of solubilizers such as ethylene, 1,3-propylene, 1,2-propylene, 1,2-butylene glycol, glycerol, ethanol, tert. Butanol, 2-propanol or phenethol in amounts of 2-50% may be useful.
Auch die Anwendung aus wasserfreien Trägern ist geeignet, wenn das zu färbende Substrat mit Wasser angefeuchtet ist. Als wasserfreie Träger eignen sich z.B. mit wasserfreien Emulgatoren kombinierte Öle wie Paraffinöle oder Silikonöle niedriger bis mittlerer Viskosität.The use of water-free carriers is also suitable if the substrate to be colored is moistened with water. Suitable water-free carriers are e.g. Oils combined with anhydrous emulsifiers such as paraffin oils or silicone oils of low to medium viscosity.
Die Arylketone der Formel I sowie die Verbindungen mit primärer oder sekundärer Aminogruppe, die Aminosäuren oder aus 2 bis 9 Aminosäuren aufgebaute Oligopeptide, die stickstoffhaltigen Heterocyclen bzw. die aromatischen Hydroxyverbindungen sind dabei in einer Menge von jeweils 0,3 bis 65, vorzugsweise 6 bis 20 mMol, jeweils bezogen auf 100 g des gesamten Färbemittels, enthalten.The aryl ketones of the formula I and the compounds having a primary or secondary amino group, the amino acids or oligopeptides composed of 2 to 9 amino acids, the nitrogen-containing heterocycles or the aromatic hydroxy compounds are in each case in an amount of 0.3 to 65, preferably 6 to 20 mmol, based in each case on 100 g of the total colorant.
Für das Färbeergebnis kann es vorteilhaft sein, den Färbemitteln Ammonium- oder Metallsalze zuzugeben. Geeignete Metallsalze sind z.B. die Formiate, Carbonate, Halogenide, Sulfate, Butyrate, Vale- riate, Capronate, Acetate, Lactate, Glykolate, Tartrate, Citrate, Gluconate, Propionate, Phosphate und Phosphonate des Kaliums, Na¬ triums, Lithiums, Magnesiums, Calciums, Strontiums, Bariums, Man¬ gans, Eisens, Kobalts, Kupfers, Zinks; bevorzugt sind Natriu acetat, Lithiumbromid, Calciumbro id, Calciu gluconat, Zinkchlorid, Zink¬ sulfat, Magnesiumchlorid, Magnesiumsulfat, Ammoniumcarbonat, -Chlo¬ rid und -acetat, die im gegebenen Falle in einer Menge von 0,3 bis 65, vorzugsweise 6 bis 20 mMol, bezogen auf 100 g des gesamten Fär¬ bemittels, enthalten sind. Der pH-Wert der gebrauchsfertigen Färbezubereitungen liegt zwischen 2 und 11, vorzugsweise zwischen 5 und 9.For the coloring result it can be advantageous to add ammonium or metal salts to the coloring agents. Suitable metal salts are, for example, the formates, carbonates, halides, sulfates, butyrates, valerates, capronates, acetates, lactates, glycolates, tartrates, citrates, gluconates, propionates, phosphates and phosphonates of potassium, sodium, lithium, magnesium, calcium , Strontiums, bariums, manganese, iron, cobalt, copper, zinc; sodium acetate, lithium bromide, calcium bromide, calcium gluconate, zinc chloride, zinc sulfate, magnesium chloride, magnesium sulfate, ammonium carbonate, chloride and acetate are preferred, which in the given case are present in an amount of 0.3 to 65, preferably 6 to 20 mmol, based on 100 g of the total colorant, are contained. The pH of the ready-to-use coloring preparations is between 2 and 11, preferably between 5 and 9.
Zum Haarefärben werden die Färbemittel in Form des wasserhaltigen, - oder auch des wasserfreien - kosmetischen Trägers in einer Menge von 50 - 100 g auf das Haar aufgebracht, ca. 30 Minuten dort belassen und dann ausgespült oder mit einem handelsüblichen Haarshampoo aus¬ gewaschen.For hair dyeing, the colorants are applied to the hair in the form of the water-containing, or else the water-free, cosmetic carrier in an amount of 50-100 g, left there for about 30 minutes and then rinsed out or washed out with a commercially available hair shampoo.
Die beiden reaktiven Komponenten können entweder gleichzeitig auf das Haar aufgebracht werden oder aber auch nacheinander, wobei es keine Rolle spielt, welche der beiden Komponenten zuerst aufgetragen wird; die Ammonium- oder Metallsalze können dabei der ersten oder zweiten Komponente zugesetzt werden. Zwischen dem Auftragen der ersten und der zweiten Komponente können bis zu 30 Minuten Zeitab¬ stand liegen. Auch eine Vorbehandlung der Haare mit der Salzlösung ist möglich.The two reactive components can either be applied to the hair at the same time or else one after the other, regardless of which of the two components is applied first; the ammonium or metal salts can be added to the first or second component. There may be a time interval of up to 30 minutes between the application of the first and the second component. Pretreatment of the hair with the saline solution is also possible.
Die beiden reaktiven Komponenten können zusammen und getrennt entwe¬ der wasserfrei oder bereits in der fertigen Formulierung gelagert werden. Bei der getrennten Lagerung werden die reaktiven Komponenten erst unmittelbar vor der Anwendung miteinander innig vermischt. Die wasserfreie Lagerung kann entweder in Pulverform oder in wasserfrei¬ en Gelen oder Dispersionen erfolgen. Bei der Lagerung als Pulver wird dem Gemisch eine definierte Menge 50 - 80°C warmen Wassers hin¬ zugefügt und eine homogene Mischung hergestellt. Bei Verwendung eines wasserfreien Gels kann mit Wasser gemischt werden oder eine direkte Applikation auf dem feuchten Haar erfolgen.The two reactive components can be stored together and separately either without water or already in the finished formulation. When stored separately, the reactive components are only intimately mixed with one another immediately before use. The water-free storage can take place either in powder form or in water-free gels or dispersions. When stored as a powder, a defined amount of 50-80 ° C warm water is added to the mixture and a homogeneous mixture is produced. If an anhydrous gel is used, it can be mixed with water or applied directly to damp hair.
Die folgenden Beispiele sollen den Erfindungsgegenstand näher erläu¬ tern, ohne ihn jedoch hierauf zu beschränken. B e i s p i e l eThe following examples are intended to explain the subject matter of the invention in more detail, but without restricting it thereto. Examples
Herstellung einer Färbelösung:Preparation of a coloring solution:
Es wurde eine Aufschlämmung von 10 mMol eines Arylketons der Formel I und 10 mMol eines Reaktants, 10 mMol Natriumacetat und einem Tropfen einer 20 %igen Fettalkylethersulfat-Lösung in 100 ml Wasser bereitet. Die Aufschlämmung wurde auf Siedetemperatur e- -tzt und nach dem Abkühlen filtriert, der pH-Wert wurde anschließend auf 6 eingestellt.A slurry of 10 mmoles of an aryl ketone of formula I and 10 mmoles of a reactant, 10 mmoles of sodium acetate and a drop of a 20% fatty alkyl ether sulfate solution in 100 ml of water was prepared. The slurry was etched to boiling temperature and filtered after cooling, the pH was then adjusted to 6.
In diese Färbelösung wurden bei 30°C 30 Minuten lang zu 90 % ergrau¬ te, nicht vorbehandelte Menschenhaare eingebracht. Die jeweiligen Färbetemperaturen, Färbedauern, Farbnuancen und Farbtiefen sind der Tabelle 1 zu entnehmen.90% gray, untreated human hair was introduced into this coloring solution at 30 ° C. for 30 minutes. The respective dyeing temperatures, dyeing times, shades and depths of color are shown in Table 1.
Die Farbtiefe wurde dabei nach folgender Skala bewertet:The color depth was rated on the following scale:
keine oder eine sehr blasse Ausfärbungno or very pale color
(♦) schwache Intensität( ♦ ) weak intensity
+ mittlere Intensität+ medium intensity
♦(+) mittlere bis starke Intensität ♦ (+) medium to strong intensity
++ starke Intensität++ strong intensity
+♦(+) starke bis sehr starke Intensität+ ♦ (+) strong to very strong intensity
+++ sehr starke Intensität +++ very strong intensity
Figure imgf000013_0001
Figure imgf000013_0001
Figure imgf000014_0001
Figure imgf000014_0001
Figure imgf000015_0001
Figure imgf000015_0001
Figure imgf000016_0001
Figure imgf000016_0001
Figure imgf000017_0001
Figure imgf000017_0001
Figure imgf000018_0001
Figure imgf000018_0001
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Figure imgf000019_0001
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Figure imgf000023_0001
Figure imgf000023_0001

Claims

Patentansprüche claims
1. Verwendung von Arylketonen der Formel I1. Use of aryl ketones of the formula I.
Figure imgf000024_0001
Figure imgf000024_0001
in der R^ für eine Cj-C4-Alkylgruppe oder eine Arylgruppe steht und R* auch eine mit dem aromatischen Rest der Formel I verbun¬ dene Cι-C4~Alkylidengruppe oder eine dazu isoelektronische N-, S- oder O-haltige, gegebenenfalls benzoannellierte Gruppe sein kann, und R^, R3 und R4 unabhängig voneinander für Wasserstoffe, Halogenatome, Hydroxygruppen, Cj-C4-Alkoxygruppen, Cj-C4-Alkyl- gruppen, C2~C4-Hydroxyalkylgruppen, Amino-(Cι-C4)-alkylgruppen, Cι-C4-Alkoxy-(Cι-C4)-alkylgruppen, Nitro-, Carboxy- oder Sulfo- gruppen oder Gruppen R^RÖ stehen, worin R5 und R^ Cι-C4-Alkyl- gruppen oder C2~C4-Hydroxyalkylgruppen bedeuten und gemeinsam mit dem N-Atom auch einen 5-, 6- oder 7-gliedrigen Ring dar¬ stellen können oder das aromatische System einen Usninsäurerest darstellt sowie deren Ketale, zum Färben von keratinhaltigen Fasern, insbesondere menschlichen Haaren. Verwendung nach Anspruch 1, dadurch gekennzeichnet, daß das Arylketon der Formel I ausgewählt ist aus Acetophenon, 2-Hydro- xyacetophenon, 4-Hydroxyacetophenon, 2,4-Dihydroxyacetophenon, 2,5-Dihydroxyacetophenon, 2,6-Dihydroxyacetophenon, 2,4,6-Tri- hydroxyacetophenon, 2,3,4-Trihydroxyacetophenon, Quercetin und (+)-Usninsäure. in which R 4 represents a C 1 -C 4 -alkyl group or an aryl group and R * also a C 1 -C 4 -alkylidene group or an isoelectronic N-, S- or O-containing, optionally connected to the aromatic radical of the formula I can be benzo-fused group, and R ^, R3 and R 4 independently of one another for hydrogen, halogen atoms, hydroxyl groups, C j -C4-alkoxy groups, C j -C4-alkyl groups, C2 ~ C4-hydroxyalkyl groups, amino ((-C-C4 ) -alkyl groups, -C-C4-alkoxy- (-C-C4) -alkyl groups, nitro, carboxy or sulfo groups or groups R ^ RÖ, where R5 and R ^ Cι-C4-alkyl groups or C2 ~ C4 -Hydroxyalkyl groups and together with the N atom can also represent a 5-, 6- or 7-membered ring or the aromatic system is a usnic acid residue and their ketals for dyeing keratin fibers, in particular human hair. Use according to claim 1, characterized in that the aryl ketone of formula I is selected from acetophenone, 2-hydroxyacetophenone, 4-hydroxyacetophenone, 2,4-dihydroxyacetophenone, 2,5-dihydroxyacetophenone, 2,6-dihydroxyacetophenone, 2,4 , 6-tri-hydroxyacetophenone, 2,3,4-trihydroxyacetophenone, quercetin and (+) - usnic acid.
PCT/EP1996/000062 1995-01-18 1996-01-09 Aryl ketones for colouring keratin-containing fibres WO1996022077A1 (en)

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Cited By (3)

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Publication number Priority date Publication date Assignee Title
WO2000015183A1 (en) * 1998-09-15 2000-03-23 Henkel Kommanditgesellschaft Auf Aktien Agents for dyeing fibres containing keratin
US7179912B2 (en) 2000-09-01 2007-02-20 Icos Corporation Materials and methods to potentiate cancer treatment
US8404681B2 (en) 2003-03-24 2013-03-26 Luitpold Pharmaceuticals, Inc. Xanthones, thioxanthones and acridinones as DNA-PK inhibitors

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US6291442B1 (en) 1998-02-03 2001-09-18 The General Hospital Corporation Pharmacological modulators of voltage-gated potassium ion channels
EP2072083B1 (en) 2007-12-19 2012-02-15 Symrise AG Utilisation of 2.4'-dimethyl-propiophenon as an aroma

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DE1492195A1 (en) * 1964-09-02 1969-12-04 Therachemie Chem Therapeut Process and means for facilitating the coloring of hair with anion-active substantive dyes
DE1492196A1 (en) * 1964-09-02 1969-12-04 Therachemie Chem Therapeut Process and means for facilitating the coloring of hair with cationic substantive dyes
DE2717041A1 (en) * 1977-04-18 1978-10-26 Henkel Kgaa Oxidn. dye-based hair-dyeing compsns. yielding brown shades - contain tetra:amino- pyrimidine developer and resorcinol deriv. coupler
FR2400359A1 (en) * 1977-08-19 1979-03-16 Oreal TINCTORIAL COMPOSITIONS BASED ON DIRECT DYES CONTAINING A (2,5-DIHYDROXYPHENYL) CARBOXYL ACID OR ONE OF ITS SALTS
FR2543434A1 (en) * 1983-04-01 1984-10-05 Muller International Sarl Alba COMPOSITION AND METHOD FOR DYEING THE PILED SYSTEM.
EP0335403A2 (en) * 1988-03-30 1989-10-04 Sansho Seiyaku Co., Ltd. Hair-dyeing composition
JPH02138114A (en) * 1988-11-18 1990-05-28 Kashiwa Kagaku Kogyo:Kk Hair dye
EP0498707A1 (en) * 1991-02-04 1992-08-12 L'oreal Process of dyeing keratinous fibers with a mono- or di-hydroxyindole and a non-oxidative aromatic carbonyl derivative and dyeing agent
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DE1492196A1 (en) * 1964-09-02 1969-12-04 Therachemie Chem Therapeut Process and means for facilitating the coloring of hair with cationic substantive dyes
DE2717041A1 (en) * 1977-04-18 1978-10-26 Henkel Kgaa Oxidn. dye-based hair-dyeing compsns. yielding brown shades - contain tetra:amino- pyrimidine developer and resorcinol deriv. coupler
FR2400359A1 (en) * 1977-08-19 1979-03-16 Oreal TINCTORIAL COMPOSITIONS BASED ON DIRECT DYES CONTAINING A (2,5-DIHYDROXYPHENYL) CARBOXYL ACID OR ONE OF ITS SALTS
FR2543434A1 (en) * 1983-04-01 1984-10-05 Muller International Sarl Alba COMPOSITION AND METHOD FOR DYEING THE PILED SYSTEM.
EP0335403A2 (en) * 1988-03-30 1989-10-04 Sansho Seiyaku Co., Ltd. Hair-dyeing composition
JPH02138114A (en) * 1988-11-18 1990-05-28 Kashiwa Kagaku Kogyo:Kk Hair dye
EP0498707A1 (en) * 1991-02-04 1992-08-12 L'oreal Process of dyeing keratinous fibers with a mono- or di-hydroxyindole and a non-oxidative aromatic carbonyl derivative and dyeing agent
WO1993009758A1 (en) * 1991-11-18 1993-05-27 Henkel Kommanditgesellschaft Auf Aktien Hair-tinting agents

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000015183A1 (en) * 1998-09-15 2000-03-23 Henkel Kommanditgesellschaft Auf Aktien Agents for dyeing fibres containing keratin
US7179912B2 (en) 2000-09-01 2007-02-20 Icos Corporation Materials and methods to potentiate cancer treatment
US8242115B2 (en) 2000-09-01 2012-08-14 Luitpold Pharmaceuticals, Inc. Materials and methods to potentiate cancer treatment
US8404681B2 (en) 2003-03-24 2013-03-26 Luitpold Pharmaceuticals, Inc. Xanthones, thioxanthones and acridinones as DNA-PK inhibitors

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