EP1965754A1 - Agent de coloration capillaire - Google Patents

Agent de coloration capillaire

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Publication number
EP1965754A1
EP1965754A1 EP06829813A EP06829813A EP1965754A1 EP 1965754 A1 EP1965754 A1 EP 1965754A1 EP 06829813 A EP06829813 A EP 06829813A EP 06829813 A EP06829813 A EP 06829813A EP 1965754 A1 EP1965754 A1 EP 1965754A1
Authority
EP
European Patent Office
Prior art keywords
group
sub
alkyl group
alkyl
aryl
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.)
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Application number
EP06829813A
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German (de)
English (en)
Inventor
Wibke Gross
Doris Oberkobusch
Horst Höffkes
Melanie Moch
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP1965754A1 publication Critical patent/EP1965754A1/fr
Withdrawn legal-status Critical Current

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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
    • A61K8/4906—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom
    • A61K8/4926—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having six membered rings
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/34—Alcohols
    • A61K8/347—Phenols
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
    • A61K8/4953—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom containing pyrimidine ring derivatives, e.g. minoxidil
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/10—Preparations for permanently dyeing the hair

Definitions

  • the invention relates to an agent for dyeing keratin-containing fibers, in particular human hair, containing specific formyl-substituted quinolinium derivatives in combination with heterocyclic, CH-acidic compounds and aromatic aldehyde derivatives, the use of this combination for dyeing keratin inconveniencer fibers, and a method for dyeing keratin-containing fibers, in particular human hair.
  • Coupler and developer components are also referred to as oxidation dye precursors.
  • the developer components are usually primary aromatic amines having a further free or substituted hydroxy or amino group in para or ortho position, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazolone derivatives and 2,4,5,6-tetraaminopyrimidine and derivatives thereof used.
  • m-phenylenediamine derivatives naphthols, resorcinol and resorcinol derivatives, pyrazolones, m-aminophenols and substituted pyridine are generally used. used derivatives.
  • Suitable coupler substances are in particular ⁇ -naphthol, 1, 5, 2,7- and 1, 7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 2,4-diaminophenoxyethanol , 2-amino-4- (2-hydroxyethylamino) -anisole (Lehmann's Blue), 1-phenyl-3-methyl-pyrazol-5-one, 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, 3-amino-6-methoxy-2 -methylamino-pyridine and 3,5-diamino-2,6-dimeth
  • oxidation dyes Although intensive dyeings with good fastness properties can be obtained with oxidation dyes, the development of the color is generally carried out under the influence of oxidizing agents such. H 2 O 2 , which in some cases may result in damage to the fiber. Still problematic is the provision of oxidation hair dyeings in the red region with sufficient fastness properties, in particular with very good washing and rubbing fastnesses. Furthermore, some oxidation dye precursors or certain mixtures of oxidation dye precursors can sometimes have a sensitizing effect on persons with sensitive skin. Direct dyes are applied under gentler conditions, but their disadvantage lies in the fact that the dyes often have only insufficient fastness properties.
  • component B compounds selected from (a) CH-acidic compounds and (b) compounds having a primary or secondary amino group or hydroxy group selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds.
  • the corresponding dyeing method (referred to below as oxo dyeing) is described, for example, in the publications WO-A1-99 / 18916, WO-A1 -00 / 38638, WO-A1-01 / 34106 and WO-A1-01/47483.
  • the resulting dyeings have partially color fastness on the keratin-containing fiber, which are comparable to those of the oxidation dyeing.
  • the Nuancenspektrum achievable with the gentle oxo staining is very broad and the color obtained often has an acceptable brilliance and color depth.
  • the aforementioned components A and B hereinafter referred to as Oxofarbstoffvor area, are generally not themselves dyes, and are therefore each alone taken not for coloring keratin-containing fibers. In combination, they form dyes in a non-oxidative process.
  • the oxo staining method can be readily combined with the oxidative staining system.
  • German patent application DE-A1-2047431 describes cationic methine dyes for dyeing anionically modified fibers, such as acid-modified polyesters or acrylonitrile polymers.
  • anionically modified fibers such as acid-modified polyesters or acrylonitrile polymers.
  • cationic methine dyes inter alia, 3,4-dihydro-3-methyl-4-methylene-quinazol-2-one and 1, 3,6-trimethyl-4-methylene-pyrimidin-2-one and mandatory terephthalaldehyde are used.
  • German patent application DE-A1-2165913 describes a process for producing bleaching images using photosensitive dyes proposed.
  • the claimed photosensitive dyes belong to the class of pyrimidone and thiopyrimidone dyes, respectively.
  • German Patent Application DE-A1-102 41 076 proposes 1,2-dihydro-2-oxopyrimidinium derivatives in combination with reactive carbonyl compounds as agents for coloring keratin fibers.
  • these means are still in need of improvement with regard to the authenticity of the dyeings obtained therewith, in particular light and wash fastness.
  • a first subject of the invention are therefore agents for dyeing keratin-containing fibers, in particular human hair, containing in a cosmetic carrier a combination of (A) at least one compound according to formula (I) or its hydrate wherein R 1 represents a (d-CeJ-alkyl group, (C 2 -C 6 ) -alkenyl group, aryl group, aryl (C r C 6 ) -alkyl group or heteroaryl (C r C 6 ) -alkyl group,
  • R 2 and R 3 each independently represent a hydrogen atom, a halogen atom, a (C 1 -C 6 ) alkyl group, a (C 1 -C 4 alkoxy group, hydroxy (C 1 -C 6 ) alkoxy group, hydroxy group, nitro group, aryl group, trifluoromethyl group, amino group, and the like by (CrCeJ-alkyl groups may be substituted, or (Ci-C 6 ) acyl group and
  • a ⁇ means a physiologically acceptable anion
  • the compounds of the formula (I) are present in aqueous carriers in chemical equilibrium with the hydrates of the formula (Ia). This is exemplified below:
  • the hydrates can be isolated and are also suitable for use in the colorants of the invention.
  • Preferred compounds according to formula I are those in which the formyl group -CHO is bonded in the 2- or 4-position.
  • A is according to formula I preferably halide, benzenesulfonate, p-toluenesulfonate, methanesulfonate, trifluoromethanesulfonate, perchlorate, sulfate, hydrogensulfate, tetrachlorozincate or N-oxide of quinoline, particularly preferably a p-toluenesulfonate, methanesulfonate, trifluoromethanesulfonate, methylsulfate or benzenesulfonate ion.
  • the preferred anion is the p-toluenesulfonate ion.
  • R 1 according to formula I is preferably a (C 1 -C 6 ) -alkyl group.
  • the compounds of the formula I are particularly preferably selected from the group consisting of the benzenesulfonates, p-toluenesulfonates, methanesulfonates, trifluoromethanesulfonates, perchlorates, sulfates, chlorides, bromides, iodides and / or tetrachlorozincates of 4-formyl-1-methylquinolinium and 2-formyl 1-methylquinolinium.
  • CH-acidic compounds are generally considered to carry a bound to an aliphatic carbon atom hydrogen atom, wherein due to electron-withdrawing substituents activation of the corresponding carbon-hydrogen bond is effected.
  • CH-acidic compounds also include enamines which are formed by alkaline treatment of quaternized N-heterocycles with a CH-acidic alkyl group in conjugation with the quaternary nitrogen.
  • the heterocyclic, CH-acidic compound is selected from at least one compound of the formula (II) and / or (III) and / or (IV) wherein
  • R 4 and R 5 are independently a linear or cyclic C 1 -C 6 - alkyl group, a C 2 -C 6 alkenyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, an aryl-CrC 6 - alkyl group, a CrC 6- hydroxyalkyl group, a C 2 -C 6 -polyhydroxyalkyl group, a C 1 -C 6 -alkoxy-C 1 -C 6 -alkyl group, a group R 1 R 11 N- (CH 2 ) P -, wherein R 1 and R 11 independently represent a hydrogen atom a C r C 4 alkyl group, a d ⁇ -hydroxyalkyl group or an aryl-C r C 6 alkyl group, wherein R 1 and R "together with the nitrogen atom can form a 5-, 6- or 7-membered ring and p stands for a number 2, 3, 4, 5 or 6,
  • R 6 and R 7 independently of one another represent a hydrogen atom or a C 1 -C 6 -alkyl group, where at least one of the radicals R 6 or R 7 denotes a C 1 -C 6 -alkyl group,
  • R 8 represents a hydrogen atom, a C r C 6 alkyl group, a C 1 -C 6 hydroxyalkyl group, a C 2 -C 6 polyhydroxyalkyl group, a C 1 -C 6 alkoxy group, a C 1 -Ce hydroxyalkoxy group, a group R 1, R 1 v N- (CH 2) q - wherein R 1 "and R IV are independently a hydrogen atom, an alkyl group CrC 6 alkyl group, a C r C 6 hydroxyalkyl group, or an aryl-C r C 6 and q is a number 1, 2, 3, 4, 5 or 6, wherein the radical R 8 together with one of the radicals R 6 or R 7 can form a 5- or 6-membered aromatic ring which optionally substituted with a halogen atom, a CrC 6 alkyl group, a Ci-C 6 - hydroxyalkyl group, a C 2 -C 6 polyhydroxyalkyl group, a C 1
  • Y 1 represents an oxygen atom, a sulfur atom or a group NR V ", in which R v " represents a hydrogen atom, an aryl group, a heteroaryl group, a C 1 -C 6 -alkyl group or a C 1 -C 6 -arylalkyl group,
  • X " is a physiologically acceptable anion
  • Het is an optionally substituted heteroaromatic
  • X 1 represents a direct bond or a carbonyl group.
  • R 9 and R 10 either together with the nitrogen atom form a saturated or unsaturated 5- or 6-membered ring or independently represent a (C 1 -C 4 ) alkyl group, a (C 2 -C 6 ) -alkenyl group, an aryl group, a Aryl (C r Ce) alkyl group, a (C 2 -C 6 ) hydroxyalkyl group, a (C 2 -C 6 ) polyhydroxyalkyl group or a group R 1 R 11 N- (CH 2 ) n, -, wherein R 1 and R 11 independently represent a hydrogen atom, a (C r C 6 ) alkyl group, a (CrC 6 ) alkenyl group or an arylC r C 6 alkyl group, wherein R 1 and R 11 together with the nitrogen atom can form a 5-, 6- or 7-membered ring and m is a number 2, 3, 4, 5 or 6, and
  • R 11 is a hydrogen atom, a (C r C6) alkyl, one alkyl group (C 2 -C 6) alkenyl group, an aryl group, an aryl (CrC 6) a (C 2 -C 6) - Hydroxyalkyl group, a (C 2 -C 6 ) -polyhydroxyalkyl group or a group R '' R lv N- (CH 2 ) n -, wherein R 1 "and R IV independently of one another represent a hydrogen atom, a (C 1 -C 6 ) - alkyl group, a (C 1 -C 6 ) alkenyl group or an aryl-CrC 6 alkyl group, wherein R MI and R ⁇ v together with the nitrogen atom can form a 5-, 6- or 7-membered ring and n is a number 2, 3, 4, 5 or 6.
  • C 1 -C 6 -alkyl radicals are the groups methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl and tert-butyl, n-pentyl and n-hexyl.
  • Propyl, ethyl and methyl are preferred alkyl radicals.
  • Examples of corresponding cyclic alkyl groups are cyclopentyl and cyclohexyl.
  • examples for preferred C 2 -C 6 alkenyl radicals are vinyl and allyl.
  • C 1 -C 6 -alkoxy radicals preferred according to the invention are, for example, a methoxy or an ethoxy group.
  • the methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, sec-butoxycarbonyl and tert-butoxycarbonyl groups are examples of CrC-alkoxycarbonyl groups; the methoxycarbonyl and ethoxycarbonyl groups are particularly preferred.
  • a C 1 -C 6 -hydroxyalkyl group there may be mentioned hydroxymethyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl, 5-hydroxypentyl and 6-hydroxyethyl to be named.
  • a 2-hydroxyethyl group is particularly preferred.
  • the methoxyethyl, ethoxyethyl, methoxypropyl, methoxybutyl, ethoxybutyl and methoxyhexyl groups are examples of C 1 -C 6 -alkoxy C 1 -C 6 -alkyl groups according to the invention.
  • Examples of a C 2 -C 6 polyhydroxyalkyl group are the 2,3-dihydroxypropyl group, 3,4-dihydroxybutyl group and the 2,4-dihydroxybutyl group.
  • a preferred hydroxyC r C 6 alkoxy group is the 2-hydroxyethoxy group.
  • Preferred aryl groups are phenyl, naphthyl and biphenyl. Examples of halogen atoms are F, Cl, Br or I atoms, with Cl atoms being particularly preferred.
  • Preferred C r C 6 aminoalkyl groups are the aminomethyl, aminoethyl and aminopropyl groups.
  • Preferred aryl-C 1 -C 6 -alkyl groups are benzyl and 2-phenylethyl.
  • aminomethyl, 2-aminoethyl, 3-aminopropyl, 2-dimethylaminoethyl, diethylaminomethyl, dimethylaminomethyl, 2-methylaminoethyl, dimethylamino, piperidinomethyl, pyrrolidinomethyl, morpholinomethyl and amino groups are examples of a group R'R "N- (CH 2 ) n-, with the diethylaminomethyl, piperidinomethyl, 2-dimethylaminoethyl, dimethylamino and amino groups being particularly preferred.”
  • a heteroaryl group are pyrrolidyl, 2-furyl, 2-thienyl, 4-pyridyl.
  • the 4- carboxypropylene group is the 3-carboxypropyl group
  • the groups 1-carboxypropylene and 1-carboxyethylene are b Preferred carboxy (C 1 -C 4 ) alkyl
  • Counterion X " which is formed from salts of the
  • the physiologically acceptable anions X " according to formula (II) may not only carry a negative charge, but may also have a charge number greater than 1. In the latter case, the anions X " of the salt form are preserved to maintain electroneutrality by formulating a stoichiometric coefficient of less than 1 described before the name of the anion.
  • the physiologically acceptable anions are preferably selected from halide, 0.5 sulfate, hydrogen sulfate, 0.5 carbonate, bicarbonate, 1/3 phosphate, 0.5 hydrogen phosphate, dihydrogen phosphate, Carboxylate, such as lactate, citrate or tartrate.
  • the compounds of formula II according to the invention are CH-acidic compounds. They are in chemical equilibrium with their corresponding enamine form. With the aid of a base, the corresponding enamines can be specifically prepared from the compounds of the said formulas by deprotonation on the carbon atom of the activated methyl groups in the 4- or 6-position. As an example, this deprotonation is illustrated below.
  • Compounds according to formula IIa are examples of the enamine forms according to the invention of the compounds of the formula (II) which are included in the scope of protection.
  • compounds of the formula (III) are particularly suitable for those in which the radical Het according to formula III is derived from one of the heteroaromatic compounds furan, thiophene, pyrrole, isoxazole, isothiazole, imidazole, oxazole, thiazole, pyridine, pyridazine, pyrimidine, pyrazine , 1, 2,3-triazine, 1, 2,4-triazine, 1, 3,5-triazine, benzopyrrole, benzofuran, benzothiophene, benzimidazole, benzoxazole, indazole, benzoisoxazole, benzoisothiazole, indole, quinoline, isoquinoline, cinnoline, phthalazine , Quinazoline, quinoxaline, acridine, benzoquinoline, benzoisoquinoline, phenazine, benzocinnoline, benzoqui
  • the compounds of formula III are selected from at least one member of the group consisting of 2- (2-furoyl) -acetonitrile, 2- (5-bromo-2-furoyl) -acetonitrile, 2- (5-methyl-2-trifluoromethyl 3-furoyl) -acetonitrile, 3- (2,5-dimethyl-3-furyl) -3-oxopropanitrile, 2- (2-thenoyl) -acetonitrile, 2- (3-thenoyl) -acetonitrile, 2- (5 Fluoro-2-thenoyl) - acetonitrile, 2- (5-chloro-2-thenoyl) -acetonitrile, 2- (5-bromo-2-thenoyl) -acetonitrile, 2- (5-methyl-2-thenoyl) - acetonitrile, 2- (2,5-dimethylpyrrol-3-oyl) -acetonitrile, 2-
  • the known salts can be prepared as acid addition salts in many cases from these in a customary manner. All statements of this document and, accordingly, the scope claimed cover both the compounds present in free form and their water-soluble, physiologically tolerated salts. Examples of such salts are the hydrochlorides, hydrobromides, sulfates, phosphates, acetates, propionates, citrates and lactates. The hydrochlorides and the sulfates are particularly preferred. The same applies to the amino-containing compounds of the formula (IV).
  • Preferred compounds of the formula (IV) are selected from the representatives in which the radicals R 6 and R 7 according to formula (IV) together with the nitrogen atom form a saturated 5- or 6-membered ring.
  • This ring in turn may optionally contain an oxygen atom and / or optionally a plurality of nitrogen atoms in the skeleton.
  • Particularly preferred examples of such rings are piperidinyl, morpholinyl and pyrrolidinyl.
  • heterocyclic, CH-acidic compounds is selected from at least one compound of the group consisting of
  • aromatic aldehyde derivative is preferably selected according to the invention from compounds of the formula (V)
  • R 1 * , R 2 * and R 3 * independently represent a hydrogen atom, a halogen atom, a C r C 6 alkyl group, a hydroxy group, a C 1 -C 6 alkoxy group, a CrC ⁇ dialkylamino group, a di (C 2 -C 6 - hydroxyalkyl) amino group, a DKCrCe-alkoxy-CRCE-alkylJaminoguppe, a CrC 6 -Hydroxyalkyloxy distr, a C 1 -C 6 -AIkOXy- (C 2 -C 6) - alkyloxy group, a sulfonyl group, a carboxy group , a sulfonic acid group, a sulfonamido group, a sulfonamide group, carbamoyl group, a C 2 -C 6 acyl group or a nitro group,
  • Z ' is a direct bond or a vinylene group
  • R 4 * and R 5 * represent a hydrogen atom or together form, together with the remainder of the molecule, a 5- or 6-membered aromatic or aliphatic ring.
  • the radicals R 1 * , R 2 * and R 3 * according to formula (V) are preferably, independently of one another, a hydrogen atom, a halogen atom, a C 1 -C 6 -alkyl group, a hydroxy group, a C 1 -C 6 -alkoxy group, a C 1 -C 6 -alkoxy ⁇ CrCeJ-alkyloxy group, a C 1 -C 6 - dialkylamino group, a di (C 2 -C 6 -hydroxyalkyl) amino group, a di (C 1 -C 6 -BIkOXy-C 1 - C 6 alkyl) or a C aminoguppe r C 6 -hydroxyalkyloxy group.
  • the radical R 1 * according to formula (V) is preferably a hydroxy group.
  • the group Z 'according to formula (V) is preferably a direct bond.
  • aromatic aldehyde derivatives are particularly preferably selected from at least one compound selected from the group consisting of
  • the colorants according to the invention give intensive dyeings even at physiologically compatible temperatures of below 45.degree. They are therefore particularly suitable for dyeing human hair.
  • the colorants can usually be incorporated into an aqueous cosmetic carrier.
  • Suitable hydrous cosmetic carriers are for.
  • As creams, emulsions, gels, foam aerosols or surfactant-containing foaming solutions such.
  • shampoos or other preparations which are suitable for use on the keratin fibers.
  • the cosmetic carriers are especially aqueous or aqueous-alcoholic.
  • aqueous cosmetic carrier contains at least 50% by weight of water.
  • aqueous-alcoholic cosmetic carriers are to be understood as meaning aqueous solutions containing from 3 to 70% by weight of a C 1 -C 4 -alkyl alcohol, in particular ethanol or isopropanol.
  • the compositions of the invention may additionally contain other organic solvents, such as methoxybutanol, benzyl alcohol, ethyl diglycol or 1, 2-propylene glycol. Preference is given to all water-soluble organic solvents.
  • Keratin fibers are wool, furs, feathers and especially human hair to understand.
  • the colorants of the invention can in principle but also for dyeing other natural fibers such.
  • As regenerated cellulose, nitro, alkyl or hydroxyalkyl or acetyl cellulose can be used.
  • the above-mentioned compounds of the formula I, the heterocyclic, CH-acidic compounds, and the aromatic aldehyde derivatives are each preferably in an amount of 0.03 to 65 mmol, in particular from 1 to 40 mmol, based on 100 g of the total colorant, used.
  • the agents according to the invention may additionally contain at least one developer component and optionally at least one coupler component as oxidation dye precursors.
  • p-phenylenediamine derivatives of the formula (E1) 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 (E1)
  • G 1 is a hydrogen atom, a C 1 - to C 4 -alkyl radical, a C 1 - to C 4 -
  • Monohydroxyalkyl radical a C 2 - to C 4 -polyhydroxyalkyl radical, a (C 1 - to C 4 ) -
  • G 2 is a hydrogen atom, a C 1 - to C 4 -alkyl radical, a C 1 - to C 4 -
  • Monohydroxyalkyl radical a C 2 - to C 4 -polyhydroxyalkyl radical, a (C 1 - to C 4 ) -
  • G 3 represents a hydrogen atom, a halogen atom such as a chlorine, bromine, iodine or
  • Fluorine atom a C 1 to C 4 alkyl radical, a C 1 to C 4 monohydroxyalkyl radical, a
  • G 4 represents a hydrogen atom, a halogen atom or a C 1 - to C 4 -alkyl radical or when G 3 and G 4 are ortho to each other, they may together form a bridging ⁇ , ⁇ -alkylenedioxy group, such as, for example, an ethylenedioxy group.
  • C 1 - to C 4 -alkyl radicals mentioned as substituents in the compounds according to the invention are the groups methyl, ethyl, propyl, isopropyl and butyl. Ethyl and methyl are preferred alkyl radicals.
  • C 1 -C 4 -alkoxy radicals which are preferred according to the invention are, for example, a methoxy or an ethoxy group.
  • a C 1 to C 4 hydroxyalkyl group there may be mentioned a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group. A 2-hydroxyethyl group is especially prefers.
  • a particularly preferred C 2 to C 4 polyhydroxyalkyl group is the 1, 2-dihydroxyethyl group.
  • halogen atoms are according to the invention F, Cl or Br atoms, Cl atoms are very particularly preferred.
  • the other terms used are derived according to the invention from the definitions given here.
  • nitrogen-containing groups of the formula (E1) are especially the amino groups, d- to C 4 monoalkylamino, C 1 - to C 4 dialkylamino, C r to C 4 - trialkylammonium groups, C 1 - to C 4 -Monohydroxyalkylamino phenomenon, imidazolinium and Ammonium.
  • Particularly preferred p-phenylenediamines of the formula (E1) are selected from p-phenylenediamine, p-toluenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2 , 6-diethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, N, N-dipropyl-p-phenylenediamine, 4-amino 3-methyl- (N, N-diethyl) -aniline, N, N-bis- ( ⁇ -hydroxyethyl) -p-phenylenediamine, 4-N, N-bis ( ⁇ -hydroxyethyl) amino-2-methylaniline , 4-N, N-bis (
  • Very particular preferred p-phenylenediamine derivatives of the formula (E1) according to the invention are p-phenylenediamine, p-toluenediamine, 2- ( ⁇ -hydroxyethyl) -p-phenylenediamine, 2- ( ⁇ , ⁇ -dihydroxyethyl) -p-phenylenediarine and N, N bis (.beta.-hydroxyethyl) -p-phenylenediamine.
  • developer component compounds which contain at least two aromatic nuclei which are substituted by amino and / or hydroxyl groups.
  • Z 1 and Z 2 independently of one another, are a hydroxyl or NH 2 radical, which is optionally substituted by a C 1 - to C 4 -alkyl radical, by a C to C 4 - substituted hydroxyalkyl radical and / or by a bridge Y, or which is optionally part of a bridging ring system
  • the bridge Y is an alkylene group having 1 to 14 carbon atoms, such as a linear or branched alkylene chain or an alkylene ring, which is one or more nitrogen-containing groups and / or one or more heteroatoms such as oxygen, Sulfur or nitrogen atoms may be interrupted or terminated and may be optionally substituted by one or more hydroxyl or C 1 - to C 8 -Al koxyreste, or a direct bond
  • G 5 and G 6 are independently a hydrogen or halogen atom , a C 1 - to C 4 -alkyl radical, a C 1 - to C 4 -monohydroxy
  • G 7 , G 8 , G 9 , G 10 , G 11 and G 12 independently of one another represent a hydrogen atom, a direct bond to the bridge Y or a C 1 - to C 4 -alkyl radical, with the provisos that
  • the compounds of formula (E2) contain only one bridge Y per molecule and the compounds of formula (E2) contain at least one amino group which carries at least one hydrogen atom.
  • Preferred binuclear developer components of the formula (E2) are in particular: N, N'-bis ( ⁇ -hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diamino-propan-2-ol, N, N'-bis ( ⁇ -hydroxyethyl) -N, N'-bis (4'-aminophenyl) ethylenediamine, N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis - ( ⁇ -hydroxyethyl) -N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis (4-methylaminophenyl) tetramethylenediamine, N, N 1 -diethyl-N, N ' bis (4'-amino-3'-methylphenyl)
  • Very particularly preferred binuclear developer components of the formula (E2) are N, N'-bis ( ⁇ -hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diamino-propan-2-ol, Bis (2-hydroxy-5-aminophenyl) methane, N, N'-bis (4'-aminophenyl) -1, 4-diazacycloheptane and 1, 10-bis- (2 ', 5'-diaminophenyl) - 1, 4,7,10-tetraoxadecane or one of its physiologically acceptable salts.
  • 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 C 1 - to C 4 -alkyl radical, a d- to C 4 monohydroxyalkyl radical, a C 2 - to C 4 polyhydroxyalkyl radical, a (Cr to C4) alkoxy (C r to C 4) alkyl, d- a to C 4 aminoalkyl radical, a hydroxy (C r to C 4) alkylamino group, a C 1 - to C 4 -Hydroxyalkoxyrest, a C 1 - to C 4 - Hydroxyalkyl (C 1 -C 4 ) -aminoalkyl radical or a (C 1 -C 4 -alkylamino) (C 1 -C 4 ) -alkyl radical, and
  • G 14 is 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 C 4 -polyhydroxyalkyl radical, a (C 1 - to C 4 J-alkoxy- (C 1 - to C 4 ) -alkyl radical, a C 1 - to C 4 -aminoalkyl radical or a C 1 - to C 4 -cyanoalkyl radical,
  • G 15 is hydrogen, a C 1 - to C 4 -alkyl radical, a C 1 - to C 4 -
  • 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-methylphenol, 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 chlorophenol, 4-amino-2,6-dichlorophenol, 4-amino-2- (diethylaminomethyl) phenol and their physiologically acceptable salts.
  • 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 developer components such as the pyridine, pyrimidine, pyrazole, pyrazole pyrimidine derivatives and their physiologically acceptable salts.
  • Preferred pyridine derivatives are, in particular, the compounds described in patents GB 1 026 978 and GB 1 153 196, such as 2,5-diamino-pyridine, 2- (4'-methoxyphenyl) -amino-3-amino-pyridine , 2,3-diamino-6-methoxy-pyridine, 2- (ß-
  • Methoxyethyl) amino-3-amino-6-methoxy-pyridine and 3,4-diamino-pyridine Preferred pyrimidine derivatives are, in particular, the compounds described in German Patent DE 2 359 399, Japanese Patent Publication JP 02019576 A2 or in the 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 -Triaminopyrimidin.
  • 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 I 3,4-diaminopyrazole, 4,5-diamino-1- (4'-chlorobenzyl) -pyrazole, 4.5- Diamino-i, 3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazinopyrazole, 1-Benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-but
  • Preferred pyrazole-pyrimidine derivatives are, in particular, the derivatives of pyrazolo [1,5-a] pyrimidine of the following formula (E4) and their tautomeric forms, provided that a tautomeric equilibrium exists:
  • G 17 , G 18 , G 19 and G 20 independently of one another represent a hydrogen atom, a C 1 - to C 4 -alkyl radical, an aryl radical, a C 1 - to C 4 -hydroxyalkyl radical, a C 2 - to C 4 polyhydroxyalkyl radical is a (C r to C 4) alkoxy (Cr to C4) alkyl, a
  • Sulfonyl radical may be protected, a (C 1 - to C 4) alkylamino (Ci to C 4) - alkyl group, a di - [(C r to C 4) alkyl] - (Cr to C 4) aminoalkyl radical, where the dialkyl
  • Radicals optionally have a carbon cycle or a 5 or 6 heterocycle
  • C 4 alkyl radical an aryl radical, a C 1 - to C 4 -hydroxyalkyl radical, a C 2 - to C 4 -
  • (C 1 - to C 4 ) -alkyl radical a di-E (C 1 - to C 4 ) alkyl] - (C 1 - to C 4 ) -aminoalkyl radical
  • dialkyl radicals optionally have a carbon cycle or a heterocycle with 5 or 6 chain members, form a C 1 - to C 4 hydroxyalkyl or a di- (C 1 - to C 4 hydroxyalkyl) aminoalkyl group, an amino group, a C 1 - to C 4 -alkyl- or
  • the pyrazolo [1, 5-a] -pyrimidines of the above formula (E4) can be prepared as described in the literature by cyclization from an aminopyrazole or from hydrazine.
  • the coupler components optionally contained in the agents according to the invention are preferably selected from m-aminophenol and its derivatives such as, 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-trifluoroacetylamino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4-methoxy-2- methylphenol, 5- (2'-hydroxyethyl) amino-2-methylphenol, 3- (diethylamino) -phenol, N-cyclopentyl-3-aminophenol, 1, 3-dihydroxy-5- (methylamino) -benzene, 3-ethylamino-4-methylphenol and 2,4-dichloro-3-aminophenol, - o-aminophenol and its derivatives, m- Dia
  • Resorcinol monomethyl ether 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol,
  • Pyridine derivatives such as 2,6-dihydroxypyridine, 2-amino-3-hydroxypyridine,
  • Naphthalene derivatives such as 1-naphthol, 2-methyl-1-naphthol, 2-
  • Morpholine derivatives such as 6-hydroxybenzomorpholine and 6-aminobenzomorpholine,
  • 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-
  • Methylenedioxybenzene derivatives such as 1-hydroxy-3,4-methylenedioxybenzene
  • 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 Methyl resorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol and 2,6-dihydroxy-3,4-dimethylpyridine.
  • indoles and indolines in the agents according to the invention which have at least one hydroxyl or amino group, preferably as a substituent on the six-membered ring.
  • These groups may carry further substituents, e.g. Example in the form of etherification or esterification of the hydroxy group or alkylation of the amino group.
  • the colorants contain at least one indole and / or indoline derivative.
  • Particularly suitable precursors of naturally-analogous hair dyes are derivatives of 5,6-dihydroxyindoline of the formula (IN-1),
  • G 21 is hydrogen, a C 1 -C 4 -alkyl group or a C 1 -C 4 -hydroxy-alkyl group,
  • G 22 is hydrogen or a -COOH group, where the -COOH group may also be in the form of a salt with a physiologically compatible cation,
  • - G 23 is hydrogen or a
  • G 24 is hydrogen, a C r C 4 alkyl group or a group -CO-G 26 , in which G 26 is a CrC ⁇ alkyl group, and
  • G 25 represents one of the groups mentioned under G 24 , 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-dihydroxyindoline and especially 5, 6-Dihydroxyindolin.
  • - G 27 is hydrogen, 4 alkyl group or a C group is a C r C 1 -C 4 hydroxyalkyl
  • G 28 is hydrogen or a -COOH group, where the -COOH group may also be present as a salt with a physiologically compatible cation,
  • - G 29 is hydrogen or an alkyl group 4 C r C,
  • G 30 is hydrogen, a C r C 4 alkyl group or a group -CO-G 32 , in which G 32 is a C 1 -C 4 alkyl group, and
  • G 31 stands for one of the groups mentioned in G 30 ,
  • Particularly preferred derivatives of indole are 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5, 6-dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid, 6-hydroxyindole, 6-aminoindole and 4-aminoindole.
  • N-methyl-5,6-dihydroxyindole N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole, and especially the 5,6 -Dihydroxyindol.
  • 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 inorganic or organic acids, for.
  • the hydrochlorides the sulfates and hydrobromides, are used.
  • the indole or indoline derivatives are contained therein usually in amounts of 0.05-10 wt .-%, preferably 0.2-5 wt .-%.
  • the colorants according to the invention for further modifying the color shades in addition to the compounds according to the invention additionally contain conventional substantive dyes, such as nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols.
  • Preferred substantive dyes are those having the international designations or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, Acid Yellow 1, Acid Yellow 10, Acid Yellow 23, Acid Yellow 36, HC Orange Disperse Orange 3, Acid Orange 7, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, Acid Red 33, Acid Red 52, HC Red BN, Pigment Red 57: 1, HC Blue 2, HC Blue 12, Disperse Blue 3, Acid Blue 7, Acid Green 50, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Acid Violet 43, Disperse Black 9, Acid Black 1, and Acid Black 52 known compounds as well as 1 , 4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis (.beta.-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (.beta.-hydroxyethyl) -aminophenol, 2 - (2'-hydroxyethyl) amino-4,6-dinitrophenol, 1- (2'
  • agents according to the invention may preferably contain a cationic substantive dye. Particularly preferred are
  • Preferred cationic substantive dyes of group (c) are in particular the following compounds:
  • the compounds of the formulas (DZ1), (DZ3) and (DZ5) are very particularly preferred cationic substantive dyes of group (c).
  • the cationic direct dyes, which are sold under the trademark Arianor ® are, according to the invention particularly preferred substantive dyes.
  • the agents according to the invention according to this embodiment preferably contain the substantive dyes in an amount of from 0.01 to 20% by weight, based on the total colorant.
  • preparations according to the invention may also contain naturally occurring dyes such as those found in henna red, henna neutral, henna black, chamomile flower, sandalwood, black tea, buckthorn bark, sage, sawnwood, madder root, catechu, seder and alkano root.
  • naturally occurring dyes such as those found in henna red, henna neutral, henna black, chamomile flower, sandalwood, black tea, buckthorn bark, sage, sawnwood, madder root, catechu, seder and alkano root.
  • the optionally contained substantive dyes each represent uniform compounds. Rather, in the colorants according to the invention, due to the production process for the individual dyes, in minor amounts, other components may be included, as far as they do not adversely affect the dyeing result or for other reasons, eg. As toxicological, must be excluded.
  • compositions according to the invention may additionally contain color enhancers.
  • the color intensifiers are preferably selected from the group consisting of piperidine, piperidine-2-carboxylic acid, piperidine-3-carboxylic acid, piperidine-4-carboxylic acid, pyridine, 2-hydroxypyridine, 3-hydroxypyridine, A- Hydroxypyridine, imidazole, 1-methylimidazole, arginine, histidine, pyrrolidine, proline, pyrrolidone, pyrrolidone-5-carboxylic acid, pyrazole, 1, 2,4-triazole, piperazidine, their derivatives and their physiologically acceptable salts.
  • the color intensifiers mentioned above can be used in an amount of 0.03 to 65 mmol, in particular 1 to 40 mmol, in each case based on 100 g of the total colorant.
  • Oxidizing agents for. B. H 2 O 2 , can be dispensed with, especially if the agent according to the invention contains no oxidation dye precursors. If the agent according to the invention contains air-oxidizable oxidation dye precursors or indole or indoline derivatives, oxidizing agent can be dispensed with without problems in such a case. However, it may u. It may be desirable to add hydrogen peroxide or other oxidizing agents to the compositions of the invention for achieving the shades that are lighter than the keratin-containing fiber to be dyed. Oxidizing agents are generally used in an amount of 0.01 to 6 wt .-%, based on the application solution.
  • a preferred oxidizing agent for human hair is H 2 O 2 .
  • Mixtures of several oxidizing agents such as a combination of hydrogen peroxide and peroxodisulfates of the alkali and alkaline earth metals or from iodide ion sources, such as alkali metal iodides and hydrogen peroxide or the aforementioned peroxodisulfates, can be used.
  • the oxidizing agent or the oxidizing agent combination can be used according to the invention in conjunction with oxidation catalysts in the hair dye.
  • Oxidation catalysts are, for example, metal salts, metal chelate complexes or metal oxides, which allow a slight change between two oxidation states of the metal ions.
  • oxidation catalysts examples are enzymes.
  • suitable enzymes are peroxidases, which can markedly increase the effect of small amounts of hydrogen peroxide.
  • 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.
  • catalysts for the oxidation of the dye precursors are the so-called 2-electron oxidoreductases in combination with the specific substrates, eg Pyranose oxidase and eg D-glucose or galactose,
  • Lactate oxidase and lactic acid and their salts Lactate oxidase and lactic acid and their salts
  • compositions according to the invention may contain all known in such preparations active ingredients, additives and excipients.
  • the colorants contain at least one surfactant, with both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants being suitable in principle. In many cases, however, it has proved to be advantageous to select the surfactants from anionic, zwitterionic or nonionic surfactants.
  • 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 as. 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. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium as well as the mono-, di- and trialkanolammonium salts with 2 or 3 C atoms in the alkanol group,
  • Ethercarbon Acid the formula RO- (CH 2 -CH 2 O) x -CH 2 -COOH, in which R is a linear
  • Esters of tartaric acid and citric acid with alcohols which are adducts of about 2 to 15 molecules of ethylene oxide and / or propylene oxide with fatty alcohols having 8 to 22 carbon atoms.
  • Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids having 10 to 18 C 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 8 -C 22 carboxylic acids, such as oleic acid, stearic acid , Isostearic acid and palmitic acid.
  • Zwitterionic surfactants are those surface-active compounds which carry at least one quaternary ammonium group and at least one -COO H or -SO 3 H group in the molecule.
  • Particularly suitable zwitterionic surfactants are the so-called betaines such as N-alkyl-N, N-dimethylammonium glycinates, for example cocoalkyldimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinates, for example cocoacylaminopropyldimethylammonium glycinate, and Alkyl-3-carboxymethyl-3-hydroxyethyl-imidazoline having in each case 8 to 18 carbon atoms in the alkyl or acyl group and the Kokosacylaminoethylhydroxyethylcarboxymethyl- glycinate.
  • a preferred zwitterionic surfactant is the fatty acid amide derivative known by the CTFA name Cocamidopropyl Betaine.
  • Ampholytic surfactants are understood as meaning those surface-active compounds which, apart from a C 8-18 -alkyl or -acyl group in the molecule, contain at least one free amino group and at least one -COOH or -SO 3 H group and are capable of forming internal salts.
  • 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-co kosalkylaminopropionat, cocoacylaminoethyl aminopropionate and C 2- I8- sarcosine.
  • Nonionic surfactants contain as hydrophilic group z.
  • Such compounds are, for example
  • ammonium halides such as Alkyltrimethylarnmoniumchloride, Dialkyldimethylammoniumchloride and Trialkylmethylammoniumchloride, z. Cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride.
  • Further cationic surfactants which can be used according to the invention are the quaternized protein hydrolysates.
  • cationic silicone oils such as, for example, the commercially available products Q2-7224 (manufacturer: Dow Corning, a stabilized trimethylsilylamodimethicone), Dow Corning 929 emulsion (containing a hydroxylamino-modified silicone, which is also referred to as amodimethicone) , SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ® quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, quaternium-80).
  • Alkylamidoamines in particular fatty acid amidoamines, such as the stearylamidopropyldimethylamine obtainable under the name Tego Amid® S 18, are distinguished not only by a good conditioning action but also by their good biodegradability.
  • a suitable cationic surfactant quaternary sugar derivative is the commercial product Glucquat 100 ®, according to CTFA nomenclature a "lauryl methyl Gluceth-10 Hydroxypropyl Dimonium Chloride”.
  • the compounds containing alkyl groups used as surfactants may each be uniform substances. However, it is usually preferred to start from the production of these substances from native plant or animal raw materials, so as to obtain substance mixtures with different, depending on the particular raw material alkyl chain lengths.
  • both products with a "normal” homolog distribution and those with a narrow homolog distribution can be used.
  • "normal” homolog distribution are meant mixtures of homologs obtained in the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates as catalysts. Narrowed homolog distributions are obtained when, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alkoxides as catalysts be used. The use of products with narrow homolog distribution may be preferred.
  • the pH of the composition according to the invention is usually between 2 and 11, preferably between 8 and 10.
  • auxiliaries and additives are, 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 dimethylaminoethyl methacrylate-vinylpyrrolidone copolymers, vinylpyrrolidone-imidazolinium methochloride copolymers and quaternized polyvinyl alcohol, zwitterionic and amphoteric polymers such as acrylamidopropyltrimethylammonium chloride / acrylate copolymers and octylacrylamide
  • Thickeners such as agar-agar, guar gum, alginates, xanthan gum, gum arabicum, karaya gum, locust bean gum, linseed gums, dextrans, celulose derivatives, eg. For example, methyl cellulose, hydroxyalkyl cellulose and carboxymethylcellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such. As bentonite or fully synthetic hydrocolloids such. For example, polyvinyl alcohol,
  • Structureants such as glucose and maleic acid, hair conditioning compounds such as phospholipids, for example soya lecithin, egg lecithin and cephalins, and silicone oils,
  • 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, perfume oils, dimethyl isosorbide and cyclodextrins, Solubilizers such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol,
  • Anti-dandruff agents such as Piroctone Olamine and Zinc Omadine, other pH adjusters,
  • Active substances such as panthenol, pantothenic acid, allantoin, pyrrolidonecarboxylic acids and their salts, plant extracts and vitamins, cholesterol, light stabilizers,
  • Bodying agents such as sugar esters, polyol esters or polyol alkyl ethers, fats and waxes such as spermaceti, beeswax, montan wax, paraffins, fatty alcohols and fatty acid esters, fatty acid alkanolamides,
  • Swelling and penetration substances such as glycerol, propylene glycol monoethyl ether, carbonates, bicarbonates, guanidines, ureas and primary, secondary and tertiary phosphates, imidazoles, tannins, pyrrole, opacifiers such as latex,
  • Propellants such as propane-butane mixtures, N 2 O, dimethyl ether, CO 2 and air and antioxidants.
  • the constituents of the cosmetic carrier are used to prepare the compositions of the packaging unit according to the invention in amounts customary for this purpose; z. B. emulsifiers in concentrations of 0.5 to 30 wt .-% and thickening agents in concentrations of 0.1 to 25 wt .-% of the total colorant used.
  • a second subject of the present invention relates to a process for dyeing keratin-containing fibers, in particular human hair, wherein an agent of the first subject of the invention applied to the keratin fibers, left on the fiber for some time, usually about 15-30 minutes, and then rinsed again or washed out with a shampoo.
  • an agent of the first subject of the invention applied to the keratin fibers, left on the fiber for some time, usually about 15-30 minutes, and then rinsed again or washed out with a shampoo.
  • the heat can be through an external heat source, such as warm air of a hot air blower, as well as, especially when a hair coloring on live subjects, by the body temperature of the subject done. In the latter case, usually the part to be dyed is covered with a hood.
  • the optionally contained ammonium or metal salts can be added to the compounds of the formula I or the other components according to the invention. Between the application of the individual components can be up to 30 minutes time interval. Pre-treatment of the fibers with the saline solution is also possible.
  • the agent according to the invention Before applying the agent according to the invention in the process according to the invention, it may be desirable to subject the keratin-containing fiber to be dyed to a pretreatment.
  • the time sequence of the pretreatment step required for this purpose and the application of the agent according to the invention need not be in immediate succession, but there may be a period of up to a maximum of two weeks between the pretreatment step and the application of the agent according to the invention.
  • several pre-treatment methods are suitable.
  • the fiber is preferred
  • the keratin-containing fiber is treated with a bleaching agent.
  • the bleaching agent contains, in addition to an oxidizing agent, such as usually hydrogen peroxide, preferably at least one inorganic persalt effective as an oxidation and bleach booster, such as a peroxydisulfate of sodium, potassium or ammonium. Dyes according to the method according to the invention obtained by the pre-treatment V1 a special brilliance and color depth.
  • an agent containing the aforementioned oxidation dye precursors as developer and optionally coupler components and optionally mentioned derivatives of indole or indoline is applied to the fiber and after a contact time optionally with the addition of aforementioned suitable oxidizing agents on the hair for 5-45 minutes leave the core fiber. Thereafter, the hair is rinsed.
  • existing oxidation dyeings can be given a new shade of shade. If the color shade of the agent according to the invention is selected in the same shade of the oxidative dyeing, then the dyeing of existing oxidation dyeings can be refreshed by the process according to the invention. It turns out that the color refreshing or shading according to the method of the invention is superior to color refreshing or shading alone with conventional substantive dyes in the color brilliance and color depth.
  • the pH of the hydrogen peroxide-containing hair colorant is preferably in a pH range from pH 7 to pH 11, particularly preferably pH 8 to pH 10.
  • the oxidizing agent can be used immediately before use mixed with the hair dye and the mixture applied to the hair. If the compounds of the formula I 1 are applied to the hair in the heterocyclic, CH-acidic compounds and the aromatic aldehyde derivatives in a two- to multistage process, the oxidizing agent must be used in one of the process stages together with the corresponding coloring component. For this purpose, it may be preferable to formulate the oxidizing agent with one of the coloring components in a container.
  • the compounds according to formula I, the heterocyclic, CH-acidic compounds and the aromatic aldehyde derivatives can either be stored separately or together, either in a liquid to pasty preparation (aqueous or anhydrous) or as a dry powder. If the components are stored together in a liquid preparation, it should be substantially anhydrous to reduce the reaction of the components. In the separate storage, the reactive components are intimately mixed with each other just before use. At the troc During storage, a defined amount of warm (3O 0 C to 8O 0 C) water is usually added before use and a homogeneous mixture is produced.
  • a third subject of the invention is the use of a composition of the first subject of the invention for dyeing keratin-containing fibers, in particular human hair.
  • cetylstearyl alcohol with approx. 20 EO units (INCI name: Ceteareth-20) (Cognis)
  • Hydroxyethylcellulose (INCI name: Hydroxyethylcellulose) (Hercules)
  • Ciz.ie fatty alcohol i ⁇ glucoside (about 50-53% active ingredient content; INCI name: Lauryl Glucoside, Aqua (Water)) (Cognis)
  • alkylpolyglucoside monoglyceride mixture about 65-70% solids; INCI name: Coco-Glucoside, Glyceryl Oleate, Aqua (Water)) (Cognis) 18 Polymer ® W 37194ca. 20% by weight of active substance content in water; INCI name: Acrylamidopropyltrimonium Chloride / Acrylates Copolymer (Stockhausen)
  • the recipe ingredients Nos. 1 to 4 were successively weighed into a beaker, melted at 80 0 C and mixed together. From components A and B, a separate mixture was prepared together with the recipe components No. 7 and No. 8. This mixture was incorporated into the still hot cream. Subsequently, the still missing recipe ingredients Nos. 9 to 13 were added in order, and made up to 100% with distilled water. The batch was stirred cold, forming a homogeneous cream.
  • the C, H-acidic compound (component B) was first dissolved with stirring in 20 wt .-% water. With stirring, the Natrosol was added and made up to 100 wt .-% with water. The swelling process was awaited and the resulting gel was stirred well again.
  • Leveling strands are made by setting off 18 cm strands with 80% gray content (Kerling) in the middle and bleaching in the upper part once with Poly Blonde Ultra (Schwarzkopf & Henkel), in the lower part 2x alternating with Poil Lock normal Welle (Schwarzkopf & Henkel) permed and bleached with Poly Blonde Ultra (Schwarzkopf & Henkel).
  • Poly Blonde Ultra Korean Biolated
  • the leveling strands were measured colorimetrically using a Datacolor Spectraflash 450 colorimeter. On each tress, 6 measurements were made at the top and 6 measurements at the bottom of the tress, and the readings per tress part per tress were averaged. To simulate the washing process, the hair strands were placed for 15 minutes in an ultrasonic bath from Elma (type T 790 / H, level 5), which was filled with a 1% Texapon NSO-UP solution. After drying, a new colorimetric measurement was carried out in the upper and in the lower part of the hair strand.
  • dE [(Li-L 0 ) 2 + (a, -a 0 ) 2 + (b, -b 0 )] 1 ' 2
  • L 0 , a 0 and b 0 are the colorimetric values in the upper, hardly damaged part of the
  • the dE value indicates the color difference that exists between the less damaged portion of the hair strand and the severely damaged portion of the hair strand.
  • the leveling power is the worse, the greater the dE value.
  • the dE values were determined both directly after the dyeing process and after 6 hair washes. Dyeing results and dE values are summarized in Table 4.
  • the two-component colorants F1 to F9 each consist of a cream component and a gel component. 50.0 g of the cream component was mixed with 50.0 g of the corresponding gel component.
  • the two-component colorants F10 to F19 each consist of a cream component and a dispersion component. 50.0 g of the cream component was mixed with 50.0 g of the corresponding dispersion component.

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Abstract

L’invention concerne un agent de coloration de fibres contenant de la kératine, notamment de cheveux humains, ledit agent contenant dans un véhicule cosmétique un mélange de (A) au moins un composé selon la formule (I) ou son hydrate, R1 représentant un groupement alkyle en C1 à C6, un groupement alcényle en C2 à C6, un groupement aryle, un groupement aryle-alkyle en C1 à C6 ou un groupement hétéroaryle-alkyle en C1 à C6, R2 et R3 représentant indépendamment l’un de l’autre un atome d’hydrogène, un atome d’halogène, un groupement alkyle en C1 à C6, un groupement alcoxy en C1-C8, un groupement hydroxy-alcoxy en C1 à C6, un groupement hydroxy, un groupement nitro, un groupement aryle, un groupement trifluorméthyle, un groupement amino pouvant être substitué par un groupement alkyle en C1 à C6, ou un groupement acyle en C1 à C6 et A? représentant un anion physiologiquement compatible, de (B) au moins un composé hétérocyclique à liaisons CH acides et de (C) au moins un dérivé d'aldéhyde aromatique différent des composés de formule (I), ledit agent de coloration pouvant notamment être utilisé pour entretenir une coloration intense. Cet agent permet notamment d’obtenir une coloration uniforme sur un substrat nmhomogène, comme une fibre capillaire abîmée de manière non uniforme, avec une excellente authenticité.
EP06829813A 2005-12-27 2006-12-21 Agent de coloration capillaire Withdrawn EP1965754A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE200510062833 DE102005062833A1 (de) 2005-12-27 2005-12-27 Haarfärbemittel
PCT/EP2006/012380 WO2007073923A1 (fr) 2005-12-27 2006-12-21 Agent de coloration capillaire

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EP1965754A1 true EP1965754A1 (fr) 2008-09-10

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EP06829813A Withdrawn EP1965754A1 (fr) 2005-12-27 2006-12-21 Agent de coloration capillaire

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EP (1) EP1965754A1 (fr)
DE (1) DE102005062833A1 (fr)
WO (1) WO2007073923A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102007058032A1 (de) * 2007-11-30 2009-06-04 Henkel Ag & Co. Kgaa Mittel zur Hautbräunung
FR2945744B1 (fr) * 2009-05-19 2011-06-10 Oreal Composition tinctoriale comprenant une base d'oxydation para-phenylene diamine secondaire et un sel de 4-formyl-1-methylquinolinium

Family Cites Families (4)

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Publication number Priority date Publication date Assignee Title
DE19745356A1 (de) * 1997-10-14 1999-04-15 Henkel Kgaa Verwendung von Oniumaldehyden und -ketonen zum Färben von keratinhaltigen Fasern
DE19962875A1 (de) * 1999-12-24 2001-06-28 Henkel Kgaa Verwendung von Methylchinolinium-Verbindungen zum Färben von keratinhaltigen Fasern
DE10211413A1 (de) * 2002-03-15 2003-09-25 Wella Ag Quinolinium-Salze enthaltende Färbemittel
DE102004025273A1 (de) * 2004-05-19 2005-12-08 Henkel Kgaa Verwendung von speziellen formylierten Chinoliniumderivaten in Komination mit 2-Amino-6-chlor-4-nitrophenol und mindestens einem weiteren primären oder sekundären, aromatischen Amin

Non-Patent Citations (1)

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Title
See references of WO2007073923A1 *

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DE102005062833A1 (de) 2007-06-28
WO2007073923A1 (fr) 2007-07-05

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