EP1771150A1 - Composes azoiques cationiques utilises comme colorations directes destinees a colorer des fibres keratiniques - Google Patents

Composes azoiques cationiques utilises comme colorations directes destinees a colorer des fibres keratiniques

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Publication number
EP1771150A1
EP1771150A1 EP05773921A EP05773921A EP1771150A1 EP 1771150 A1 EP1771150 A1 EP 1771150A1 EP 05773921 A EP05773921 A EP 05773921A EP 05773921 A EP05773921 A EP 05773921A EP 1771150 A1 EP1771150 A1 EP 1771150A1
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EP
European Patent Office
Prior art keywords
alkyl
amino
general formula
substituted
azo compounds
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.)
Ceased
Application number
EP05773921A
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German (de)
English (en)
Inventor
Georg KNÜBEL
Horst Höffkes
Helmut Giesa
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication of EP1771150A1 publication Critical patent/EP1771150A1/fr
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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/4906—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom
    • A61K8/4913—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having five membered rings, e.g. pyrrolidone carboxylic acid
    • A61K8/492—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having five membered rings, e.g. pyrrolidone carboxylic acid having condensed rings, e.g. indol
    • 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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/10—Preparations for permanently dyeing the hair

Definitions

  • the present invention relates to agents for coloring keratinic fibers containing specific cationic azo compounds, to processes for dyeing fibers, in particular hair with these agents, and to the use of the cationic azo compounds for this purpose.
  • oxidation colorants play a preferred role because of their intense colors and good fastness properties.
  • colorants contain oxidation dye precursors, so-called developer components and coupler components.
  • developer components form under the influence of oxidizing agents or of atmospheric oxygen with one another or with coupling with one or more coupler components, the actual dyes.
  • the developer components are usually primary aromatic amines having a further, in the para or ortho position, free or substituted hydroxy or amino group, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazolone derivatives and 2,4,5,6-tetraaminopyrimidine and its derivatives ⁇ sets.
  • N N-bis (2-hydroxyethyl) -p-phenylenediamine, 2- (2,5-diaminophenyl) ethanol, 2- (2,5-diaminophenoxy) ethanol, 1-phenyl-3-carboxyamido-4-amino-pyrazolone-5 , 4-amino-3-methylphenol, 2-aminomethyl-4-aminophenol, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triamino-4- hydroxypyrimidine and 1,3-N, N'-bis (2-hydroxyethyl) -N, N'-bis (4-amino-phenyl) -diaminopropan-2-ol.
  • coupler components m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenols are generally used.
  • Suitable coupler substances are, in particular, 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinomonomethyl ether, m-phenylenediamine, 1-phenyl 3-methyl-pyrazolone-5, 2,4-dichloro-3-aminophenol, 1,3-bis (2,4-diaminophenoxy) -propane, 2-chlororesorcinol, 4-chlororesorcinol, 2-chloro-6-methyl 3-aminophenol, 2-methylresorcinol, 5-methylresorcinol and 2-methyl-4-chloro-5-aminophenol.
  • direct dyes are of great importance for the dyeing of keratin fibers.
  • cationic dyes can be used, which are applied directly to them in a dyeing agent for keratinous fibers.
  • WO 95/01772 relates to a process for coloring keratinous fibers in which cationic dyes are used.
  • azo dyes can be used which have an indole radical and a thiazole radical or oxazole radical, see structures (1) and (9) of WO 95/01772.
  • the 2-position according to this document can not be substituted by groups containing aromatic nuclei.
  • the described cationic substantive dyes are used only as a combination of different substantive dyes for dyeing hair.
  • EP-A-0 875 620 relates to a process for coloring melamine fibers.
  • melamine-formaldehyde fibers are dyed, which are needed in flame retardant applications. It is described that also articles made of melamine fibers in combination with protein fibers can be used for flame retardancy.
  • mixtures of melamine fibers with protein fibers or animal fibers can be used. Examples include wool, silk, cashmere, mohair and rabbit hair. The coloring of human hair is not discussed.
  • the used Dyes are selected from direct dyes, non-metallated acid dyes, metalated acid dyes, disperse disperse dyes, and mixtures thereof.
  • Example IA is a mixture of melamine fibers and p-aramid fibers with CI. Colored in Direct Red 79. According to Example HC CI Basic Red 29 is used. On combinations of these dyes with other dyes is not discussed in the document.
  • Direct dyes can be an alternative to oxidation dyes or complement their property profile.
  • Good oxidation dye precursors are to form the desired color shades in sufficient intensity and fastness in the oxidative coupling. They should also have a good AufziehFab on the fiber, in particular in human hair no significant differences between strained and freshly regrown hair should exist (leveling). They should be resistant to light, heat, sweat, friction and the influence of chemical reducing agents, e.g. Perm liquids.
  • they should not stain the scalp too much and above all they should be safe in terms of toxicology and dermatology.
  • the coloring achieved by bleaching should be easily removed from the hair, if it does not meet the individual wishes of each person and should be reversed.
  • the object of the present invention was therefore to provide direct dyes, in particular for dyeing human hair, which are particularly useful in human hair dyeing Combined with oxidation dye precursors meet the requirements placed on these systems, including in terms of toxicological and dermatological properties, and allow colorations in a wide range of colors with good fastness properties.
  • substantive dyes are to be provided for dyeing human hair, which cause a red color.
  • specific cationic azo compounds satisfy the requirements imposed on substantive dyes for dyeing human hair to a high degree. They are particularly advantageously used in agents for oxidative dyeing of keratinic fibers, in particular human hair, since they can be advantageously combined with oxidation dye precursors.
  • R 1 is H, halogen, NO 2 , C 6 -i2-aryl, C7.13-ara.kyl. C 7 .i 3 alkaryl, Ci -6 -
  • Alkyl which are optionally substituted by: -OH, halogen, -CN, -NO 2, optionally OH-substituted Ci -4 - alkoxy, -NH 2, -NHR, -NR 2 are each independently optionally substituted with R OH-substituted Ci-4-alkyl,
  • R 3 C 6 i2-aryl, C7 .i 3 aralkyl or C 7 "i 3 alkaryl, which are optionally substituted by -OH, halogen, -CN, -NO 2, optionally OH-substituted Ci- 4 - alkoxy, -NH 2, -NHR, -NR 2 are each independently optionally substituted with R OH-substituted Ci -4 - alkyl,
  • R 2, R 4, R 5 are independently H, Ci -6 alkyl, Ci- 6 hydroxyalkyl, C 2 - 6 - alkoxyalkyl, Ci. 6 aminoalkyl, C 2 i 0 alkylaminoalkyl, C3-I2 -. Dialkylaminoalkyl, C 6] 2 aryl, C 7 .i 3 aralkyl or C 7 i 3 alkaryl,
  • a further subject is the use of cationic azo compounds of the general formula (Ia)
  • R 1 is H, halogen, NO 2 , C 6 -i 2 -aryl, C 7 .13 -ra.-alkyl. C7. 1 3-A.kary., C ,. 6 -
  • Alkyl which are optionally substituted by: -OH, halogen, -CN, -NO 2 , optionally OH-substituted C M - alkoxy, -NH 2 , -NHR, -NR 2 with R each independently of one another optionally OH-substituted C M alkyl,
  • R 3 H Ci. 6- alkyl, Cj- ⁇ -hydroxyalkyl, C 2 . 6 alkoxyalkyl, C -6 -
  • R 2, R 4, R 5 are independently H, Ci -6 alkyl; C I-6 -Hy droxyalkyl, C 2 - 6 - alkoxyalkyl, Ci-6-aminoalkyl, C i 0 2- alkylaminoalkyl, C. 3 12 - dialkylaminoalkyl, C6 "i 2 aryl, C 7- ⁇ 3 -aralkyl or C 7 .i 3 alkaryl,
  • the definition of the cationic azo compounds of the general formulas (I) and (Ia) differ in the breadth of the definition of the radical R 3 .
  • the cationic azo compounds of the formulas (I) and (Ia) are particularly advantageously used as substantive dyes in agents for the oxidative dyeing of keratinic fibers, in particular human hair.
  • the invention also relates to agents for dyeing human hair, which contain in a cosmetically acceptable carrier as substantive dye at least one cationic azo compound of the general formula (I).
  • the invention relates to agents for the oxidative coloring of keratinic fibers, in particular human hair, in a cosmetically acceptable carrier Oxidation dye precursors and at least one cationic azo compound of the general formula (Ia).
  • keratinic fibers are understood to mean furs, wool, feathers and, in particular, human hair.
  • oxidation dyes according to the invention are primarily suitable for dyeing keratin fibers, in principle, there is nothing to prevent their use in other fields, in particular in color photography.
  • C 1 -C 6 -alkyl groups which are mentioned as substituents in the compounds used according to the invention, preferably C 1 -C 4 -alkyl groups which may be linear or branched, are the groups methyl, ethyl, propyl, isopropyl, butyl, pentyl and hexyl , Ethyl and methyl are preferred alkyl groups.
  • a preferred Cj to C 6 - (mono) hydroxyalkyl group a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group may be mentioned.
  • a 2-hydroxyethyl group is particularly preferred.
  • C 2 - 6 -Alkoxyalklyreste have a total of 2 to 6 carbon atoms, which are spread on the alkoxy and the alkyl radical. It can thus be present in the alkoxy or alkyl radical in each case up to 5 carbon atoms. It is preferably a c 1-3 -alkoxy-C 1-3 -alkyl radical, particularly preferably C 1-2 -alkoxy-C 1-2 -alkyl radical. Both the alkoxy and the alkyl moiety may be linear or branched. They are preferably linear.
  • Ci -6 -Aminoalkylreste preferably Ci.
  • C 2 -i ö -Alkylaminoalkylreste preferably C 2 . 6- Alkylaminoalkylreste and C 3 .12 Dialkylaminoalkylreste, preferably C 3 .Q-Dialkylaminoalkylreste can each have linear or branched alkyl radicals.
  • Each individual alkyl group preferably has 1 to 3 carbon atoms.
  • the alkyl radicals present in the respective groups are preferably as defined above for the pure alkyl radicals.
  • radicals are optionally substituted, depending on the number of carbon atoms in the alkyl or alkoxy radical, preferably 1 to 3, particularly preferably 1 or 2, in particular a substituent, may be present. Substituents may be present for R 1 and R 3 , some of which may in turn be substituted by -OH. Preferably, only one of these further OH substituents is present.
  • C M -alkyl radicals and Cj -4 - Alkoxy radicals are in turn linear or branched, preferably linear, and particularly preferably ethyl or methyl. If one of the radicals R 2 to R 5 contains a hydroxyl group bonded to an alkylene radical, the hydroxyl group is preferably terminal, and the alkylene radical is linear. A hydroxyethyl radical is thus preferably a 2-hydroxyethyl radical.
  • Aryl radicals are preferably phenyl radicals.
  • Aralkyl radicals are an alkyl radical substituted by an aryl radical.
  • Alkaryl radicals contain an aryl radical which is substituted by an alkyl radical.
  • the aryl radical is also preferably a phenyl or phenylene radical.
  • a preferred aralkyl radical is a benzyl radical.
  • a preferred alkaryl radical is a tolyl radical.
  • the cationic azo compounds of the general formulas (I) and (Ia) are usually present as a salt with corresponding counterions, in particular physiologically acceptable anions.
  • the counterions may be halide ions, in particular chloride or sulfate, phosphate, nitrate, acetate, hydrogen sulfate, hydrogen phosphate, dihydrogen phosphate.
  • Halogen is generally F, Br, Cl or I, preferably Cl or Br.
  • an azo compound of the general formulas (I) or (Ia) has a total of not more than four OH groups, preferably not more than two OH groups. There are in the azo compound of the general formulas (I) or (Ia) preferably at most four nitrogen atoms, more preferably at most two nitrogen atoms in the radicals R 1 - R 5 before. Overall, apart from the hydroxyl groups, in the azo compound of the general formula (I) are preferably a maximum of two further oxygen atoms.
  • R 1 is hydrogen or C
  • Y is CR 5 where R 5 is hydrogen or C) - 4 alkyl.
  • R 5 is particularly preferably hydrogen.
  • R 2 and R 4 denote Ci -4 alkyl, particularly preferably methyl.
  • R 3 is phenyl, benzyl or tolyl, in particular phenyl.
  • X is particularly preferably sulfur.
  • Basic Red 29 is particularly preferably used.
  • This substantive dye corresponds to the formulas (I) and (Ia) with the meanings R 1 is hydrogen, X is sulfur, Y is CH, R 2 , R 4 is methyl, R 3 is phenyl, where the counterion is a chloride ion.
  • Human hair dyeing compositions according to the invention contain, in a cosmetically acceptable carrier as substantive dye, at least one cationic azo compound of the general formula (I) as defined above.
  • a cosmetically acceptable carrier as substantive dye
  • at least one cationic azo compound of the general formula (I) as defined above Preferred agents of this type are described, for example, in DE-A-102 59 849.
  • an agent for the oxidative dyeing of keratinic fibers, in particular human hair which contains oxidation dye precursors and at least one cationic azo compound of the general formulas (I) or (Ia) in a cosmetically acceptable carrier.
  • the agent contains at least one developer component and at least one coupler component, as exemplified below.
  • composition of the invention may contain one or more, for example at least two different azo compounds of the general formulas (I) or (Ia).
  • the azo compounds of the formulas (I) or (Ia) can be prepared by conventional organic methods.
  • compositions according to the invention for coloring keratinic fibers or human hair contain the at least one azo compound of the general formulas (I). or (Ia) preferably in an amount of 0.02 to 5 wt .-%, particularly preferably 0.1 to 2 wt .-%, based on the finished composition.
  • the agent for coloring keratinous fibers can be selected from any suitable agents that are particularly suitable for dyeing human hair.
  • a cosmetically acceptable carrier used is in particular an otherwise customary carrier of agents for dyeing human hair.
  • the colorants according to the invention may be composed according to known colorants or contain the usual ingredients for them. Examples of further suitable and inventively preferred ingredients are given below.
  • compositions according to the invention may contain the following ingredients as indicated
  • Suitable colorant compositions are described, for example, in DE-U 1-29911819, DE-A-011 25 451, DE-Ul-201 114036, Kosmetik, ed. W. Umbach, 2nd ed. 1995, G. " Thieme Verlag Stuttgart, New York described.
  • the colorants according to the invention may further comprise at least one developer component.
  • the developer components are usually primary aromatic amines having a further, in the para or ortho position, free or substituted hydroxy or amino group, diaminopyridine derivatives, heterocyclic hydrazones, 4-amino pyrazole derivatives and 2,4,5,6-tetraaminopyrimidine and its Derivatives used.
  • p-phenylenediamine derivatives of the formula (II) it may be preferred according to the invention to use as the developer component a p-phenylenediamine derivative or one of its physiologically acceptable salts. Particular preference is given to p-phenylenediamine derivatives of the formula (II)
  • G 1 represents a hydrogen atom, a Cr to C 4 alkyl group, a Cr to C 4 - monohydroxyalkyl radical, a C 2 - to C 4 polyhydroxyalkyl radical, a (Ci to C 4) - alkoxy (C) - to C 4 ) -alkyl radical, a 4'-aminophenyl radical or a C 1 to C 4 alkyl radical which is substituted by a nitrogen-containing group, a phenyl or a 4'-aminophenyl radical;
  • G 2 represents a 'hydrogen atom, a Cr to C 4 alkyl group, a Cr to C 4 - monohydroxyalkyl radical, a C 2 - to C 4 polyhydroxyalkyl s a (Cr to C 4) - Alkoxy (C 1 to C 4 ) alkyl or C 1 to C 4 alkyl substituted with a nitrogen-containing group;
  • G 3 represents a hydrogen atom, a halogen atom, such as a chlorine, bromine, iodine or fluorine atom, a C r to C 4 alkyl radical, a Cr bis - C 4 -
  • Monohydroxyalkyl radical a C 2 - to C 4 -polyhydroxyalkyl radical, a C 1 - to C 4 -
  • G is a hydrogen atom, a halogen atom or a Cj- to C 4 -
  • Examples of the Cp to C 4 -alkyl radicals mentioned as substituents in the compounds are the groups methyl, ethyl, propyl, isopropyl and butyl. Ethyl and methyl are preferred alkyl radicals.
  • Preferred C 1 -C 4 -alkoxy radicals are, for example, a methoxy or an ethoxy group.
  • a Cr to C 4 -Hy droxyalkyl distr a hydroxym ethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group may be mentioned.
  • a 2-hydroxyethyl group is particularly preferred.
  • a particularly preferred C 2 to C 4 polyhydroxyalkyl group is the 1, 2-dihydroxyethyl group.
  • halogen atoms are F, Cl or Br atoms, Cl atoms are very particularly preferred.
  • the other terms used are derived from the definitions given here.
  • nitrogen-containing groups of formula (El) are especially the amino groups, Ci to CrMonoalkylamino phenomenon, Ci to C 4 dialkylamino, C) - to C 4 - trialkylammonium, Cr to C 4 -Monohydroxyalkylamino phenomenon, imidazolinium and ammonium.
  • Particularly preferred p-phenylenediamines of the formula (III) are selected from p-phenylenediamine, p-toluenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2.6 Diethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine.
  • N N-dimethyl-p-phenylenediamine.
  • NN-diethyl-p- phenylenediamine N, N-dipropyl-p-phenylenediamine, 4-amino-3-methyl- (N, N-diethyl) -aniline, N, N-bis ( ⁇ -hydroxyethyl) -p-phenylenediamine, 4-N, N-bis ( ⁇ -hydroxyethyl) amino-2-methylaniline, 4-N, N-bis ( ⁇ -hydroxyethyl) amino-2-chloroaniline, 2- ( ⁇ -hydroxyethyl) -p-phenylenediamine, 2- ( ⁇ , ⁇ -dihydroxyethyl) -p-phenylenediamine, 2-fluoro-p-phenylenediamine, 2-isopropyl-p-phenylenediamine, N- ( ⁇ -hydroxypropyl) -p-phenylenediamine, 2-
  • P-phenylenediamine derivatives of the formula (II) which are very particularly preferably used according to the invention are p-phenylenediamine, p-toluenediamine, 2- ( ⁇ -hydroxyethyl) -p-phenylenediamine, 2- ( ⁇ , ⁇ -dihydroxyethyl) -p-phenylenediamine and N, N-bis- ( ⁇ -hydroxyethyl) -p-phenylenediamine.
  • developer component compounds which contain at least two aromatic nuclei which are substituted by amino and / or hydroxyl groups.
  • binuclear developer components which can be used in the dyeing compositions according to the invention, mention may be made in particular of the compounds corresponding to the following formula (E2) and their physiologically tolerated salts:
  • Z 1 and Z 2 independently of one another represent a hydroxyl or NH 2 -ReSt 5 which is optionally substituted by a C 1 - to C 4 -alkyl radical, by a C 1 - to C 4 -
  • the bridge Y is an alkylene group having 1 to 14 carbon atoms, such as a linear or branched alkylene chain or a
  • Alkylene ring containing one or more nitrogen-containing groups and / or one or more heteroatoms. like ' oxygen, sulfur or
  • Nitrogen atoms can be interrupted or terminated and may be substituted by one or more hydroxyl or C 1 to C 5 alkoxy radicals, or a direct bond,
  • G 5 and G 6 independently of one another represent a hydrogen or halogen atom, a C 1 - to C 4 -alkyl radical, a C 1 - to C 4 -monohydroxyalkyl radical, a C 2 - to
  • G 7 , G 8 , G 9 , G 10 , G "and G 12 are each independently
  • Preferred binuclear developer components of the formula (E2) are in particular: N, N'-bis ( ⁇ -hydroxyethyl) -N, N'-bis (4'-amino-phenyl) -1,3-diamino-propan-2-ol, N, N'-bis ( ⁇ -hydroxyethyl) -N, N'-bis (4'-aminophenyl) ethylenediamine, N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis - (.beta.-hydroxyethyl) -N, N'-bis (4-aminophenyD-tetramethylenediamine, N, N'-bis (4-methylaminophenyl) tetramethylenediamine, N, N'-diethyl-N, N'- bis (4 t -amino-3'-methylphenyl) ethylenediamine, bis (2-hydroxy-5-aminophenyl
  • p-aminophenol derivatives of the formula (E3) it may be preferred according to the invention to use as the developer component a p-aminophenol derivative or one of its physiologically tolerable salts. Particular preference is given to p-aminophenol derivatives of the formula (E3)
  • G 13 represents a hydrogen atom, a halogen atom, a Ci to C 4 alkyl radical, a Ci to C 4 monohydroxyalkyl radical, a C 2 - to C 4 polyhydroxyalkyl radical, a (C r to C 4) alkoxy ( C r to C 4) alkyl, a Ci to C 4 alkylamino aminoalkyl group, a hydroxy (Ci to C4), a C] - to C 4 -Hydroxyalkoxyrest, a Ci to C 4 hydroxyalkyl (C r to C 4 ) aminoalkyl or a (di-Ci- bis
  • G 14 represents a hydrogen or halogen atom, a C 1 to C 4 alkyl radical, a
  • Monohydroxyalkyl radical a C 2 to C 4 polyhydroxyalkyl radical, a phenyl radical or a benzyl radical, and
  • G 16 is hydrogen or a halogen atom.
  • Preferred p-aminophenols of the formula (E3) are in particular p-aminophenol, N-methyl-p-aminophenol ? 4-amino-3-methyl-phenol > 4-amino-3-fluorophenol, 2-hydroxymethylamino-4-aminophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2- ( ⁇ -hydroxyethoxy) -phenol, 4- Amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethyl-phenol, 4-amino-2-aminomethylphenol, 4-amino-2- ( ⁇ -hydroxyethyl-aminomethyl) -phenol, 4- Amino-2- ( ⁇ , ⁇ -dihydroxyethyl) -phenol, 4-amino-2-fluorophenol, 4-amino-2-chloro-phenol, 4-amino-2,6-dichloro-phenol, 4-amino-2- (diethylaminomethyl ) -phenol and their physiologically
  • Very particularly preferred compounds of the formula (E3) are p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- ( ⁇ , ⁇ -dihydroxyethyl) -phenol and 4-amino 2- (diethylaminomethyl) -phenol.
  • the developer component may be selected from o-aminophenol and its derivatives such as 2-amino-4-methylphenol, 2-amino-5-methylphenol or 2-amino-4-chlorophenol.
  • the developer component may be selected from heterocyclic developing components such as the pyridine, pyrimidine, pyrazole, pyrazole pyrimidine derivatives and their physiologically acceptable salts.
  • Preferred pyrimidine derivatives are, in particular, the compounds described in German patent DE 2 359 399, Japanese laid-open specification JP 02019576 A2 or in published patent application WO 96/15765, such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy 2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2-dimethylamino-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6- Triamino ⁇ yrimidin.
  • Preferred pyrazole derivatives are, in particular, the compounds described in patents DE 3 843 892, DE 4 133 957 and patent applications WO 94/08969, WO 94/08970, EP-740 931 and DE 195 43 988, such as 4,5 Diamino-1-methylpyrazole, 4,5-diamino-1- ( ⁇ -hydroxyethyl) pyrazole, 3,4-diamino-pyrazole, 4,5-diamino-1- (4'-chlorobenzyl) -pyrazole, 4,5- Diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazino-pyrazole, 1-Benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-
  • Preferred pyrazole-pyrimidine derivatives are, in particular, the derivatives of pyrazole [1,5-a] pyrimidine of the following formula (E4) and its tautomeric forms; if a tautomeric equilibrium exists:
  • G 17, G 18, G 19 and G 20 are independently a hydrogen atom, a CJ to C 4 alkyl radical, an aryl radical, a Ci to C 4 -hydroxyalkyl group, a C 2 - to C 4 polyhydroxyalkyl a (C 1 -C 4 ) -alkoxy- (C 1 -C 4 ) -alkyl radical, a C 1 -C 4 -aminoalkyl radical which may optionally be protected by an acetyl-ureide or a sulfonyl radical, a , alkylamino alkyl (Ci to C 4) a Di - - Ci- to C 4) [(Ci to C4) alkyl] - (Ci.r ...
  • the pyrazolo [l, 5-a] -pyrimidines of the above formula (E4) can be prepared as described in the literature by cyclization from an aminopyrazole or hydrazine.
  • the inventive colorants contain at least one coupler component.
  • coupler components m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives are generally used.
  • Suitable coupler substances are, in particular, 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinomonomethyl ether, m-phenylenediamine, 1-phenyl 3-methyl-pyrazolone-5, 2,4-dichloro-3-aminophenol, 1,3-bis (2 ', 4'-diaminophenoxy) -propane, 2-chloro-resorcinol, 4-chloro-resorcinol, 2 Chloro-6-methyl-3-aminophenol, 2-amino-3-hydroxypyridine, 2-methylresorcinol, 5-methylresorcinol
  • Coupler components according to the invention are m-aminophenol and its derivatives, for example 5-amino-2-methylphenol, N-cyclopentyl-3-aminophenol. 3-Amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 2,6-dimethyl-3-aminophenol, 3
  • Di- or Trihydroxybenzolderivate such as resorcinol, resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol. 2,5-dimethylresorcinol, 2-chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1,2,4-trihydroxybenzene,
  • Pyridine derivatives such as 2,6-dihydroxypyridine, 2-amino-3-hydroxypyridine, 2-amino-5-chloro-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,6-dihydroxy-3 , 4-dimethylpyridine, 2,6-dihydroxy-4-methylpyridine, 2,6-diaminopyridine, 2,3-diamino-6-methoxypyridine and 3,5-diammo-2,6-dimethoxypyridine,
  • Naphthalene derivatives such as, for example, 1-naphthol, 2-methyl-1-naphthol, 2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1, 5
  • Pyrazole derivatives such as, for example, 1-phenyl-3-methylpyrazol-5-one,
  • Indole derivatives such as 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole,
  • Pyrimidine derivatives such as 4,6-diaminopyrimidine, 4-amino-2,6-dihydroxypyrimidine, 2,4-diamino-6-hydroxypyrimidine, 2,4,6-trihydroxypyrimidine, 2-amino-4-methylpyrimidine, 2- Amino-4-hydroxy-6-methylpyrimidine and 4,6-dihydroxy-2-methylpyrimidine, or methylenedioxybenzene derivatives such as, for example, 1-hydroxy-3,4-methylenedioxybenzene, 1-amino-3,4-methylenedioxybenzene and 1 (2 ') hydroxyethyl) -arnino-3,4-methylenedioxybenzene.
  • Particularly preferred further coupler components according to the invention are 1-naphthol, 1,5-, 2,7- and 1, 7-dihydroxynaphthalene, 3-aminophenol, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, resorcinol, 4- Chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol and 2,6-dihydroxy-3,4-dimethylpyridine.
  • the colorants may contain at least one precursor of a naturally-analogous dye.
  • precursors of naturally-analogous dyes such indoles and indolines are preferably used, the at least one hydroxy or amino group. preferably as a substituent on the six-membered ring. These groups may carry further substituents, e.g. B. in the form of a Etherification or esterification of the hydroxy group or alkylation of the amino group.
  • the colorants contain at least one indole derivative and / or indoline derivative.
  • Particularly suitable precursors of natural-analogous hair dyes are derivatives of 5,6-dihydroxyindoline of the formula (IIa),
  • - R ! stands for hydrogen, a C] -C 4 alkyl group or a Cj-C / t-alkyl hydroxy group
  • R 2 is hydrogen or a -COOH group, where the -COOH group may also be present as a salt with a physiologically compatible cation,
  • R 3 is hydrogen or a C 1 -C 4 -alkyl group
  • R 4 is hydrogen, a C 1 -C 4 -alkyl group or a group -CO-R 6 , in which R 6 is a C 1 -C 4 -alkyl group, and
  • R 5 is one of the groups mentioned under R 4 , as well as physiologically acceptable salts of these compounds with an organic or inorganic acid.
  • Particularly preferred derivatives of indoline are 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6 dihydroxyindoline, 5,6-dihydroxyindoline-2-carboxylic acid and 6-hydroxyindoline, 6-aminoindoline and 4-aminoindoline.
  • N-methyl-5,6-dihydroxyindoline N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxy-indoline and in particular the 5,6-Dihydroxyindolin.
  • derivatives of the 5,6-dihydroxyindole of the formula (IIb) are also suitable as precursors of naturally-analogous hair dyes.
  • R 1 represents hydrogen, a Ci-C 4 alkyl group or C) -C 4 hydroxyalkyl group
  • R 2 is hydrogen or a -COOH group, where the -COOH group may also be present as a salt with a physiologically compatible cation,
  • R J is hydrogen or a C 1 -C 4 -alkyl group
  • R 4 is hydrogen, a C JC 4 -AlkVl group or a group -CO-R 6 , in which R 6 is a C) -C 4 alkyl group, and
  • R 5 is one of the groups mentioned under R 4 , as well as physiologically acceptable salts of these compounds with an organic or inorganic acid.
  • Particularly preferred derivatives of indole are 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5, 6-dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid, 6-hydroxyindole, 6-aminoindole and 4-aminoindole.
  • N-methyl-5,6-dihydroxyindole N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole and in particular the 5 , 6-dihydroxyindole.
  • the indoline and indole derivatives can be used in the colorants of the invention both as free bases and in the form of their physiologically acceptable salts with anorga ⁇ African or organic acids, eg. Hydrochlorides, sulfates and hydroxides. mide.
  • the indole or indoline derivatives are contained therein usually in amounts of 0.05-10 wt .-%, preferably 0.2-5 wt .-%.
  • the indoline or indole derivative in colorants in combination with at least one amino acid or an oligopeptide.
  • the amino acid is advantageously an ⁇ -amino acid;
  • Very particularly preferred ⁇ -amino acids are arginine, ornithine, lysine, serine and histidine, in particular arginine.
  • the colorants according to the invention may, in a further preferred embodiment of the present invention, for shading one or more further substantive
  • Dyes contain. Such other substantive dyes are common
  • Preferred further substantive dyes are those under the international designations or trade names HC Yellow 2, HC Yellow 4, HC
  • Acid black 1, and acid black 52 known compounds as well as 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis ( ⁇ -hydroxyethyl) amino-2-nitrobenzene, 3
  • compositions of the invention may contain a further cationic substantive dye. Particularly preferred are
  • Preferred cationic substantive dyes of group (c) are in particular the following compounds:
  • the compounds of the formulas (DZI), (DZ3) and (DZ5) which are also known by the names Basic Yellow 87, Basic Orange 31 and Basic Red 51, are very particularly preferred cationic substantive dyes of group (c).
  • the cationic direct dyes which are sold under the brand Arianor® ® are, according to the invention also very particularly preferred cationic direct dyes.
  • compositions according to the invention according to this embodiment preferably contain the entire substantive dyes in an amount of from 0.01 to 20% by weight, based on the total colorant.
  • preparations of the invention may also naturally occurring dyes such as henna red, henna neutral, henna black, chamomile, sandalwood, black tea, buckthorn bark, sage, bluewood, madder root, Catechu, Sedre and alkano root are included.
  • oxidation dye precursors or the direct dyes it is not necessary for the oxidation dye precursors or the direct dyes to be in each case homogeneous compounds. Rather, in the hair colorants according to the invention, due to the production process for the individual dyes, in minor amounts, further components may be included, as far as these are not detrimental to the dyeing result or for other reasons, such as toxicological, must be excluded.
  • the colorants according to the invention may furthermore contain all active ingredients, additives and auxiliaries known for such preparations.
  • the colorants contain at least one surfactant, wherein in principle both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants are suitable.
  • Suitable anionic surfactants in preparations according to the invention are all anionic surfactants suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such. Example, a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group having about 10 to 22 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups may be present in the molecule.
  • anionic surfactants are, in each case in the form of Natri ⁇ um-, potassium and ammonium and mono-, di- and Trialkanolammoniumsalze with 2 or 3 C atoms in the alkanol group, linear fatty acids having 10 to 22 carbon atoms (Soap),
  • Acylsarcosides having 10 to 18 C atoms in the acyl group, acyl taurides having 10 to 18 C atoms in the acyl group, acyl isethionates having 10 to 18 C atoms in the acyl group, sulfosuccinic acid mono- and dialkyl esters having 8 to 18 C atoms in the acyl group Alkyl group and sulfosuccinic acid mono-alkylpolyoxyethyl esters having 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups, linear alkane sulfonates having
  • Esters of tartaric acid and citric acid with alcohols which are addition products of about 2-15 molecules of ethylene oxide and / or propylene oxide onto fatty alcohols having 8 to 22 C atoms.
  • Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids having 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule and in particular salts of saturated and in particular unsaturated C 12 -C 22 -carboxylic acids, such as oleic acid, stearic acid, Isostearic acid and palmitic acid.
  • Nonionic surfactants contain as hydrophilic group z.
  • Such compounds are, for example
  • Preferred nonionic surfactants are alkyl polyglycosides of the general formula R 1 O- (Z) x . These connections are identified by the following parameters.
  • the alkyl radical R 1 contains 6 to 22 carbon atoms and may be both linear and branched. Preference is given to primary linear and methyl-branched in the 2-position aliphatic radicals.
  • Such alkyl radicals are, for example, 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-stearyl. Particularly preferred are 1-octyl, 1-decyl, 1-lauryl, 1-myristyl.
  • oxo alcohols When so-called "oxo alcohols" are used as starting materials, compounds having an odd number of carbon atoms in the alkyl chain predominate.
  • the alkyl polyglycosides which can be used according to the invention can contain, for example, only one particular alkyl radical R 1 .
  • these compounds are prepared starting from natural fats and oils or mineral oils.
  • the alkyl radicals R are mixtures corresponding to the starting compounds or corresponding to the particular work-up of these compounds.
  • R 1 consists essentially of C 1 - and C -alkyl groups, essentially of C 1 - and C 1 -alkyl groups, essentially of C 8 - to C 6 -alkyl groups or essentially of C n - to C 6 - Alkyl groups.
  • sugar building block Z it is possible to use any desired mono- or oligosaccharides. Usually, sugars with 5 or 6 carbon atoms and the corresponding oligosaccharides are used.
  • Such sugars are, for example, glucose, fructose, galactose, arabinose, ribose, xylose, lyxose, allose, altrose, mannose, gulose, idose, talose and sucrose.
  • Preferred sugar building blocks are glucose, fructose, galactose, arabinose and sucrose; Glucose is particularly preferred.
  • alkyl polyglycosides which can be used according to the invention contain on average from 1.1 to 5 sugar units. Alkyl polyglycosides having x values of 1.1 to 1.6 are preferred. Very particular preference is given to alkyl glycosides in which x is 1.1 to 1.4.
  • the alkyl glycosides can also serve to improve the fixation of fragrance components on the hair.
  • This substance class as a further constituent of the preparations according to the invention in the event that an action of the Parrumöl on the hair beyond the duration of the hair treatment is desired.
  • alkoxylated homologs of said alkyl polyglycosides can also be used according to the invention. These homologs may contain on average up to 10 ethylene oxide and / or propylene oxide units per alkyl glycoside unit.
  • zwitterionic surfactants can be used, in particular as cosurfactants.
  • Zwitterionic surfactants are surface-active compounds are distinguished be ⁇ , a -COO ⁇ in the molecule at least one quaternary ammonium group and at least - or -S ⁇ 3 ( "-).
  • Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl N, N-dimethylammonium glycinates, for example cocoalkyldimethylammonium glycinate, N-acylaminopropyl N, N-dimethylammonium glycinates, for example cocoacylaminopropyldimethylammonium glycinate, and 2-alkyl-3-carboxylmethyl-3-hydroxyethyl Iridazolines having in each case 8 to 18 C atoms in the alkyl or acyl group and the cocoacylaminoethylhydroxyethylcarboxymethylglycinate
  • a preferred zwitterionic surfactant is the fatty acid amide derivative known by the INCI name Cocamidopropyl Betaine.
  • ampholytic surfactants are understood as meaning those surface-active compounds which contain, in addition to a C 1 -C 6 -alkyl or acyl group in the molecule, at least one free arrino group and at least one -COOH or -SO 3 H group and which makes it possible to form internal salts are.
  • ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each having about 8 to 18 C atoms in the alkyl group.
  • Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethyl aminopropionate and C] 2- 18 acyl sarcosine.
  • the cationic surfactants used may in particular be those of the type of the quaternary ammonium compounds, the esterquats and the amidoamines.
  • Preferred quaternary ammonium compounds are ammonium halides, in particular chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, eg. Cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride, as well as the imidazolium compounds known under the INCI names Quaternium-27 and Quaternium-83.
  • the long alkyl chains of the above-mentioned surfactants preferably have 10 to 18 carbon atoms.
  • Esterquats are known substances which contain both at least one ester function and at least one quaternary ammonium group as structural element.
  • Preferred esterquats are quaternized ester salts of fatty acids with triethanolamine, quaternized ester salts of fatty acids with diethanolalkylamines and quaternized ester salts of fatty acids with 1,2-dihydroxypropyldialkylamines.
  • Such products are marketed under the brands Stepantex® ®, ® and Dehyquart® Armocare® ®.
  • the alkylamidoamines are usually prepared by amidation of natural or synthetic fatty acids and fatty acid cuts with dialkylaminoamines.
  • a erfm- dung as particularly suitable compound from this group of substances that available under the brand Tegoamid ® S 18 commercially stearamidopropyl dimethylamine.
  • Further inventively usable cationic surfactants are the quaternized protein hydrolysates.
  • cationic silicone oils such as the commercially available products Q2-7224 (manufactured by Dow Corning, a stabilized trimethylsilylamodine ethicone), Dow Corning 929 emulsion (containing a hydroxylamino-modified silicone, also referred to as amodimethicones), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ® - Quat 3270 and 3272 (manufacturer: Th Goldschmidt; diquaternary polydimethylsiloxanes, quaternium-80.).
  • a suitable cationic surfactant quaternary sugar derivative is the commercial product Glucquat ® 100, according to INCI nomenclature a "lauryl methyl Gluceth-10 Hydroxypropyl Dimonium Chloride”.
  • the compounds used as surfactant with alkyl groups may each be uniform substances. However, it is generally preferred to use native vegetable or animal raw materials in the production of these substances, so that substance mixtures having different alkyl chain lengths depending on the respective raw material are obtained.
  • colorants according to the invention may contain further active compounds, auxiliaries and additives such as, for example, nonionic polymers such as vinylpyrrolidone / vinyl acrylate copolymers, polyvinylpyrrolidone and vinylpyrrolidone / vinyl acetate copolymers and polysiloxanes, cationic polymers such as quaternized cellulose ethers, polysiloxanes with quaternary groups Dimethyldiallylammonium chloride polymers, acrylamide-dimethyldiallyl-ammonium chloride copolymers, diethyl sulfate-quaternized dimethylamino-ethyl methacrylate-vinylpyrrolidone copolymers, vinylpyrrolidone-imidazolinium methochloride copolymers and quaternized polyvinyl alcohol, zwitterionic and amphoteric polymers such as acrylamidopropyltrimethylammonium chloride / acrylate Copo
  • Thickeners such as agar-agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives, e.g. For example, methylcellulose, hydroxyalkylcellulose and carboxymethylcellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such.
  • B. bentonite or fully synthetic hydrocolloids such as polyvinyl alcohol, Structural agents such as maleic acid and lactic acid, hair conditioning compounds such as phospholipids, for example soya lecithin, egg lecithin and cephalins,
  • Protein hydrolysates in particular elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolysates, their condensation products with fatty acids and quaternized protein hydrolysates, parrum oils, dimethyl isosorbide and cyclodextrins,
  • Solvents and mediators such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol, fiber-structure-improving agents, especially mono-, di- and oligosaccharides such as glucose, galactose, fructose, fructose and lactose, quaternized amines such as methyl-l-alkylamidoethyl -2-alkylimidazolinium methosulfate
  • Defoamers such as silicones, dyes for coloring the agent,
  • Antidandruff active ingredients such as Piroctone oil amines, zinc Omadine and climbazole, light stabilizers, in particular derivatized benzophenones, cinnamic acid derivatives and triazines,
  • Substances for adjusting the pH such as, for example, customary acids, in particular edible acids and bases,
  • Active ingredients such as allantoin, pyrrolidonecarboxylic acids and their salts, and bisabolol,
  • Vitamins, provitamins and vitamin precursors in particular those of groups A, B 3 , B 5 , B 6 , C, E, F and H,
  • Plant extracts such as extracts of green tea, oak bark, nettle, witch hazel, hops, chamomile, burdock root, horsetail, hawthorn, lime blossom, almond, aloe vera, spruce needle, horse chestnut, sandalwood, juniper, coconut, mango, apricot, lime, wheat , Kiwi, melon, orange. Grapefruit, sage, rosemary, birch, mallow, meadowfoam, quenelle, yarrow, thyme, lemon balm. Toadstool, coltsfoot, marshmallow. Meristem, ginseng and ginger root ,. - cholesterol,
  • Bodying agents such as sugar esters, polyol esters or polyol alkyl ethers, fats and waxes such as spermaceti, beeswax, montan wax and paraffins,
  • - swelling and penetrating substances such as glycerol, propylene glycol monoethyl ether, carbonates, bicarbonates, guanidines, ureas and primary, secondary and tertiary phosphates,
  • Opacifiers such as latex, styrene / PVP and styrene / acrylamide copolymers
  • Pearlescing agents such as ethylene glycol mono- and distearate and PEG-3-distearate,
  • Stabilizing agent for Wassserstoffperoxid and other oxidizing agents such as propane-butane mixtures, N 2 O, dimethyl ether, CO2 and air,
  • Antioxidants included.
  • the agents according to the invention preferably contain the dye precursors in a suitable aqueous, alcoholic or aqueous-alcoholic carrier.
  • a suitable aqueous, alcoholic or aqueous-alcoholic carrier are, for example, creams, emulsions, gels or surfactant-containing foaming solutions, such as shampoos, foam aerosols or other preparations which are suitable for use on the hair.
  • surfactant-containing foaming solutions such as shampoos, foam aerosols or other preparations which are suitable for use on the hair.
  • aqueous-alcoholic solutions are to be understood as meaning aqueous solutions containing from 3 to 70% by weight of a C 1 -C 4 -alcohol, in particular ethanol or isopropano].
  • the agents according to the invention can additionally other organic solvents, such as methoxybutanol, benzyl alcohol, ethyl diglycol or 1, 2-propylene glycol. Preference is given to all water-soluble organic solvents.
  • the actual oxidative dyeing of the fibers can be carried out in principle with atmospheric oxygen.
  • preference is given to using a chemical oxidizing agent especially if, in addition to the dyeing, a lightening effect on human hair is desired.
  • Suitable oxidizing agents are persulfates, chlorites and in particular hydrogen peroxide or its addition products of urea, melamine and sodium borate.
  • the oxidation colorant can also be applied to the hair together with a catalyst which promotes the oxidation of the dye precursors, e.g. by atmospheric oxygen, activated.
  • catalysts are e.g. Metal ions, iodides, quinones or certain enzymes.
  • Suitable metal ions are, for example, Zn 2+ , Cu 2+ , Fe 2+ , Fe 3+ , Mn 2+ , Mn 4+ , Li + , Mg 2+ , Ca 2+ and Al 3+ . Particularly suitable are Zn 2+ , Cu 2+ and Mn 2+ .
  • the metal ions can be used in principle in the form of any physiologically acceptable salt or in the form of a complex compound.
  • Preferred salts are the acetates, sulfates, halides, lactates and tartrates.
  • Suitable enzymes are e.g. Peroxidases that can significantly increase the effect of small amounts of hydrogen peroxide. Furthermore, such enzymes are suitable according to the invention which directly oxidize the oxidation dye precursors with the aid of atmospheric oxygen, such as, for example, the laccases, or generate small amounts of hydrogen peroxide in situ and thus biocatalytically activate the oxidation of the dye precursors. Particularly suitable catalysts for the oxidation of the dye precursors are the so-called 2-electron oxidoreductases in combination with the specific substrates, e.g.
  • Glycerol oxidase and glycerin Pyruvate oxidase and pyruvic acid or its salts, alcohol oxidase and alcohol (MeOH, EtOH), lactate oxidase and lactic acid and its salts, tyrosinase oxidase and tyrosine, uricase and uric acid or their salts, choline oxidase and choline, amino acid oxidase and Amino acids.
  • the actual hair dye is expediently prepared immediately before use by mixing the preparation of the oxidizing agent with the preparation containing the dye precursors.
  • the resulting ready-to-use hair dye preparation should preferably have a pH in the range from 6 to 12. Particularly preferred is the use of the hair dye in a weakly alkaline environment.
  • the application temperatures can range between 15 and 40 ° C.
  • the hair dye is removed by rinsing of the hair to be dyed.
  • the washing with a shampoo is omitted if a strong surfactant-containing carrier, e.g. a dyeing shampoo was used.
  • the preparation with the dye precursors may also be applied to the hair without prior mixing with the oxidation component.
  • the oxidation component is then applied, if appropriate after an intermediate rinse.
  • the product is then rinsed and, if desired, shampooed again.
  • the corresponding agent is adjusted to a pH of about 4 to 7.
  • an air oxidation is initially desired, wherein the applied agent preferably has a pH of 7 to 10.
  • a third object of the present invention is a process for dyeing keratinic fibers, in particular human hair, in which a hair colorant according to the invention is applied to the fibers and rinsed off again after a contact time.
  • Eumulgin ® RO 40 ethoxylated castor oil (INCI name: PEG-40
  • Dehyquart ® A trimethylhexadecylammonium chloride, approx. 27% active ingredient (INCI name: Aqua (Water), Cetrimonium Chloride) (Cognis Germany)
  • Methyltriethanolammoniummethylsulfat- dialkyl mixture (INCI name: distearoyl ethyl Hydroxyethylmonium methosulfate, Cetearyl Alcohol) (Cognis Germany)
  • AMinor A 15 C 13-15 -Alkylethercarboxylatmonoethanolamid (INCI name: Trideceth-2 Carboxamide MEA) (KAO)
  • Methacrylate Copolymer (Rohm & Haas) Aculyn ® 33 (INCI name: Acrylates Copolymer) (Rohm & Haas) Merquat ® 280 dimethyldiallylammonium chloride-acrylic acid copolymer (INCI name: Polyquaternium-22) (Nalco)
  • Gluadin ⁇ AGP KL wheat protein hydrolyzate (INCI name:
  • Silkair 100 silk protein (INCI name: SiIk Serica (Linne)) (Ikeda Bussan Kaisha)
  • foam toning agents according to Table 1 were prepared and formulated in a pressure-release container with a propane-butane mixture as blowing agent.
  • tint lotions according to Tables 2 and 3 were prepared:
  • Powder hair colors are prepared in the form of a fine powder (sieve fraction 0.05-1.0 nm) according to Table 5:
  • a coloring cream according to Table 6 was mixed with the oxidizing agent preparation according to Table 7 in a weight ratio of 1: 1.
  • X g of this mixture was left on Y g of a human hair strand (Kerling natural white) for 30 minutes at 32 ° C on the hair and then rinsed. The strand of hair was dried and the color result was assessed.

Abstract

L'invention concerne des composés azoïques cationiques de formule (I), dans laquelle X représente O, S ; Y représente N, CR5 ; R1 représente par exemple H ; R3 représente par exemple aryle C6-12, aralkyle C7-13 ou alkaryle C7-13 ; R2, R4, R5 représentent par exemple H. Lesdits composés sont utilisés comme colorations directes destinées à colorer les cheveux humains.
EP05773921A 2004-07-28 2005-07-26 Composes azoiques cationiques utilises comme colorations directes destinees a colorer des fibres keratiniques Ceased EP1771150A1 (fr)

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DE200410036688 DE102004036688A1 (de) 2004-07-28 2004-07-28 Kationische Azoverbindungen als direktziehende Farbstoffe zur Färbung keratinischer Fasern
PCT/EP2005/008085 WO2006013036A1 (fr) 2004-07-28 2005-07-26 Composes azoiques cationiques utilises comme colorations directes destinees a colorer des fibres keratiniques

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DE102006032666A1 (de) * 2006-07-13 2008-01-17 Beiersdorf Ag Tensidhaltige kosmetische Zubereitungen mit besonderen Proteinhydrolysaten
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DE102015204471A1 (de) 2015-03-12 2016-09-15 Henkel Ag & Co. Kgaa Färbemittel für keratinische Fasern mit ausgewähltem Farbstoff und Polyol
FR3051361B1 (fr) 2016-05-18 2018-05-18 L'oreal Composition cosmetique comprenant des tensioactifs anioniques, des tensioactifs amphoteres, des polymeres cationiques et des corps gras liquides choisis parmi les alcools gras et les esters gras, et procede de traitement cosmetique

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DE2114747A1 (de) * 1970-03-26 1971-10-14 Sumitomo Chemical Co Ltd , Osaka (Japan) Kanonische Farbstoffe und Ver fahren zu deren Herstellung
DE2228147A1 (de) * 1972-06-09 1973-12-20 Bayer Ag Kationische diazacyaninfarbstoffe
TW311089B (fr) * 1993-07-05 1997-07-21 Ciba Sc Holding Ag
DE102004008607A1 (de) * 2004-02-21 2005-09-08 Wella Ag Indolylthiazoliumazofarbstoffe enthaltende Färbemittel für Keratinfasern
DE102004008606A1 (de) * 2004-02-21 2005-09-08 Wella Ag Aufhellendes Färbemittel mit Indolylthiazoliumazofarbstoffen

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