EP1879660A1 - Agent pour colorer des fibres a base de keratine - Google Patents

Agent pour colorer des fibres a base de keratine

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Publication number
EP1879660A1
EP1879660A1 EP06723689A EP06723689A EP1879660A1 EP 1879660 A1 EP1879660 A1 EP 1879660A1 EP 06723689 A EP06723689 A EP 06723689A EP 06723689 A EP06723689 A EP 06723689A EP 1879660 A1 EP1879660 A1 EP 1879660A1
Authority
EP
European Patent Office
Prior art keywords
group
hydroxy
dihydro
hydroxybenzaldehyde
pyrimidinium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP06723689A
Other languages
German (de)
English (en)
Inventor
Wibke Gross
Horst Höffkes
Doris Oberkobusch
Helmut Müller
Carsten Brake
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP1879660A1 publication Critical patent/EP1879660A1/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Withdrawn legal-status Critical Current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
    • A61K8/494—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
    • A61K8/4946—Imidazoles or their condensed derivatives, e.g. benzimidazoles
    • 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
    • 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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/35—Ketones, e.g. benzophenone
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • 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
    • A61K8/36—Carboxylic acids; Salts or anhydrides thereof
    • A61K8/368—Carboxylic acids; Salts or anhydrides thereof with carboxyl groups directly bound to carbon atoms of aromatic 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
    • A61K8/49—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
    • A61K8/494—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
    • A61Q5/06—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 invention relates to an agent for dyeing keratin-containing fibers, in particular human hair, containing 3-allyl-4-hydroxybenzaldehyde and / or its derivatives in combination with CH-acidic compounds, the use of this combination in agents for dyeing keratin fibers, for Color refreshing or shading of already colored keratin-containing fibers and a process 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 derivatives are generally used.
  • Suitable coupling agents 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-methylpyrazol-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 -dimethoxy
  • 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.
  • the object of the present invention is to provide colorants for keratin-containing fibers, in particular human hair, which are at least equivalent in terms of color depth and fastness properties, such as light fastness, rubfastness and washfastness, as well as perspiration and cold wave fastness, to the usual oxidation hair colorants
  • colorants for keratin-containing fibers, in particular human hair
  • fastness properties such as light fastness, rubfastness and washfastness, as well as perspiration and cold wave fastness
  • the compounds represented in formula I in combination with CH-acidic compounds are outstandingly suitable for dyeing keratin-containing fibers, even in the absence of oxidizing agents. They result in colorations with excellent brilliance and color depth and lead to a variety of color nuances.
  • dyeings having improved fastness properties are obtained over a range of shades from yellow through orange, brown-orange, brown, red, red-violet to blue-violet and dark blue.
  • oxidizing agents should not be ruled out in principle.
  • the benzaldehyde derivatives according to the invention are distinguished by an increased physiological compatibility.
  • a first subject of the invention is an agent for dyeing keratin-containing fibers, in particular human hair, comprising, in a cosmetic carrier, as component A at least one compound according to formula I,
  • R1, R2 and R3 are independently a hydrogen atom, a halogen atom, a C r C 6 alkyl group, a C 2 -C 6 alkenyl group, a hydroxy group, a C r C 6 alkoxy group, a C r C 6 - , hydroxyalkyl group, a C 2 -C 6 polyhydroxyalkyl group, a hydroxy alkyloxy group (Cr C 6), a sulfonyl group, a carboxy group, a (C 1 - C 6) alkoxycarbonyl group, a hydroxy (C 2 -C 6) alkyloxycarbonyl a Suifonklad, a Sulfonamido group, a sulfonamide group, a C 2 -C 6 acyl group, a formyl group, a nitro group, a carbamoyl group
  • R 4 , R 5 , R 6 and R 7 independently represent a hydrogen atom, a CrC 6 - alkyl group or a C 2 -C 6 -hydroxyalkyl group and n is an integer from 0 to 6, where R 1 and R 2 can form a 5- or 6-membered aromatic or heteroaromatic ring,
  • At least one CH-acidic compound as component B At least one CH-acidic compound as component B.
  • 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.
  • C r 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
  • Examples of preferred C 2 -C 6 -alkenyl radicals are vinyl and allyl.
  • Examples of a C 2 -C 6 -polyhydroxyalkyl group are the 2,3-dihydroxypropyl group,
  • C r -C 6 -alkoxy groups which are preferred according to the invention are, for example, a methoxy or an ethoxy group.
  • Butoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, n-pentyloxycarbonyl and n-hexyloxycarbonyl are examples of C r C 6 alkoxycarbonyl groups;
  • Methoxycarbonyl and the ethoxycarbonyl group are particularly preferred.
  • acetyl, n-propanoyl, n-butanoyl group and n-hexanoyl group are examples of one
  • Methoxyhexyl group are examples of inventive C 1 -C 6 -Akoxy-C 2 -C 6 - alkyl groups.
  • a preferred hydroxy (C 1 -C 6 ) alkoxy group is the 2-hydroxyethoxy group.
  • a preferred hydroxy (C 2 -C 6 ) alkoxycarbonyl group is the 2-
  • halogen atoms are F, Cl, Br or I atoms, with Cl atoms being particularly preferred.
  • Piperidinomethyl, pyrrolidinomethyl, morpholinomethyl, bis (2-hydroxyethyl) amino and the amino group are examples of a group R 6 R 7 N- (CH 2 ) n -, wherein the
  • Amino group are particularly preferred.
  • N, N-dimethylcarbamoyl, N, N -diethylcarbamoyl, N, N-bis (2-hydroxyethyl) carbamoyl and the carbamoyl group are exemplary carbamoyl groups R 4 R 5 NC (O) -.
  • the agent according to the invention comprises at least one compound of the formula (I) which carries a hydrogen atom as substituent R 2 and R 3.
  • the remainder R1 is a hydrogen atom, a C r C 6 alkyl group, a C 2 -C 6 alkenyl group (particularly, a. Allyl group), a C r C 6 alkoxy group (especially a methoxy group), a formyl group, a hydroxy group, a halogen atom, a carboxy group or a nitro group.
  • the radicals R 2 and R 3 it is again particularly preferred for the radicals R 2 and R 3 to stand for a hydrogen atom.
  • Formula (I) is contained in the agent according to the invention:
  • compositions according to the invention at least one
  • those compounds according to the invention as component A according to formula (I) can be used in which the reactive carbonyl group is derivatized or masked such that the reactivity of the carbon atom of the derivatized carbonyl group is always present against the CH-acidic compounds of component B.
  • These derivatives are preferably addition compounds a) of amines and their derivatives to form imines or oximes as addition compound b) of alcohols to form acetals as addition compound c) of water to form hydrates as addition compound to the carbon atom of the formyl group -CHO in compounds according to Formula (I).
  • CH-acidic compounds are generally considered those compounds which 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 there are no limits to the choice of CH-acidic compounds as long as a compound which is visibly colored visibly to the human eye is obtained after the aldol condensation with the benzaldehyde derivatives of the formula (I) according to the invention. It is inventively preferred and such CH-acidic compounds containing an aromatic and / or a heterocyclic radical.
  • the heterocyclic radical may again be aliphatic or aromatic.
  • the 3-allyl-4-hydroxybenzaldehyde compounds of formula (I) are combined with at least one CH-acidic compound selected from formulas (II) and / or (III)
  • R 8 and R 9 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 CiC 6 - alkyl group, a C R is C 6 hydroxyalkyl, C 2 -C 6 polyhydroxyalkyl, C 1 -C 6 alkoxyCrC ⁇ alkyl, R 1 R 11 N- (CH 2 ) In -, where R 1 and R 11 are independently for a hydrogen atom, a C r C 4 alkyl group, a CrC 4 -hydroxyalkyl group or an aryl-C- ⁇ -C 6 alkyl group, wherein R 1 and R 11 together with the nitrogen atom is a 5-, 6- or 7-membered Ring can form and m stands for a number 2, 3, 4, 5 or 6,
  • R 10 and R 12 independently represent a hydrogen atom or a C1 - Ce alkyl group, wherein at least one of the radicals R 10 and R 12 is a C 1 -C 6 - alkyl group,
  • R 11 stands for 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 Ci-C 6 alkoxy group, a C r C 6 -hydroxyalkoxy group, a group R 111 R 17 N- (CH 2) Q -, in which R 1 "and R IV are independently a hydrogen atom, a CrC 6 alkyl group, a C r C 6 hydroxyalkyl group, or an aryl-C r C 6 -alkyl group and q is a number 1, 2, 3, 4, 5 or 6, wherein the radical R 11 together with one of the radicals R 10 or R 12 can form a 5- or 6-membered aromatic ring, optionally with a halogen atom, a C r C 6 alkyl group, a C 1 -C 6 hydroxyalkyl group, a C 2 -C 6 polyhydroxyalkyl group,
  • Y represents an oxygen atom, a sulfur atom or a group NR V ", wherein R v" stands for a hydrogen atom, an aryl group, a heteroaryl group, a C 1 -C 6 - alkyl group or a C r 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.
  • At least one group R 10 or R 12 according to formula II is necessarily a C 1 -C 6 -alkyl group.
  • This alkyl group preferably carries at least two hydrogen atoms on its ⁇ -carbon atom.
  • Particularly preferred alkyl groups are the methyl, ethyl, propyl, n-butyl, iso-butyl, n-pentyl, neo-pentyl, n-hexyl group.
  • R 10 and R 12 are each independently hydrogen or a methyl group, wherein at least one group R 10 or R 12 is a methyl group.
  • Y is an oxygen or a sulfur atom, particularly preferably an oxygen atom.
  • the radical R 8 is preferably selected from a (C 1 -C 6 ) -alkyl group (particularly preferably a methyl group), a C 2 -C 6 -alkenyl group (in particular an allyl group), a hydroxy (C 2 - to C 6 ) -alkyl group or an optionally substituted benzyl group.
  • R 11 is preferably a hydrogen atom.
  • the radicals R 9 , R 10 and R 12 are a methyl group
  • the radical R 11 is a hydrogen atom
  • Y is an oxygen or sulfur atom
  • the radical R 8 is selected - from a (CrC 6 ) alkyl group (particularly preferably one Methyl group), a C 2 -C 6 alkenyl group (particularly an allyl group), a hydroxy (C 2 - to C 6 alkyl group) or an optionally substituted benzyl group.
  • the compounds of formula II are selected from one or more compounds of the group of salts with physiologically acceptable
  • Counterion X " which is formed from salts of the
  • Very particularly preferred compounds according to formula II are selected from one or more compounds of the group of salts with physiologically acceptable counterion X " , which is formed from salts of
  • X " in formula (II) and in the above lists preferably represents halide, benzenesulfonate, p-toluenesulfonate, C r C 4 -alkanesulfonate, trifluoromethanesulfonate, perchlorate, 0.5 sulfate, hydrogensulfate, tetrafluoroborate, hexafluorophosphate or tetrachlorozincate , Bromide, iodide, hydrogen sulfate or p-toluenesulfonate used as X " .
  • the radical Het according to formula (III) is preferably the molecule fragment of the formula (IV)
  • R 13 and R 14 independently represent a hydrogen atom, a hydroxy group, a halogen atom, a nitro group, a linear or cyclic C 1 - C 6 alkyl group, a C 2 -C 6 alkenyl group, an optionally substituted aryl group, an cyanomethyl group, a cyanomethylcarbonyl, an optionally substituted heteroaryl group, an aryl-CrC 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 Ci-C 6 alkoxycarbonyl group, a C 1 -C 6 -alkoxy-C 2 -C 6 - alkyl group, a -C 6 sulfoalkyl, a Ci-C 6 carboxyalkyl group, a group R ⁇ r VIII R lx N- (CH 2) wherein R vl "
  • X 2 and X 3 independently of one another represent a nitrogen atom or a group CR 15 , where R 15 is a hydrogen atom, a hydroxy group, a halogen atom, a nitro group, a linear or cyclic C r C 6 alkyl group, a C 2 C 6 alkenyl group, an optionally substituted aryl group, a cyanomethyl group, a cyanomethylcarbonyl group, an optionally substituted heteroaryl group, an arylCrC 6 alkyl group, a C 1 -C 6 hydroxyalkyl group, a C 2 -C 6 polyhydroxyalkyl group, a C r is C 6 alkoxy, C r C 6 alkoxycarbonyl, C r C 6 alkoxy C 2 -C 6 alkyl, C 1 -C 6 sulfoalkyl, CrCe carboxyalkyl and R x R xl N- (CH 2 ) n -, in which
  • X 4 is an oxygen atom, a sulfur atom, a vinyl group or an NH group, which latter two groups are independently optionally substituted with a linear or cyclic C- ⁇ -C6 alkyl group, a C 2 -C 6 - alkenyl group, a optionally substituted aryl group, an optionally substituted heteroaryl group, an aryl-C 1 -C 6 -alkyl group, a C 2 -C 6 -hydroxyalkyl group, a C 2 -C 6 -polyhydroxyalkyl group, a C r C 6 -alkoxy-C 2 -C 6 -alkyl group, a C r C 6 -Sulfoalkyl distr, a C r C 6 -Carboxyalkyl distr, a group R XII R XIII N- (CH 2 ) P -, wherein R x "and R x ⁇ " independently represent a hydrogen atom , a linear or cycl
  • R 13 or R 14 form the bond to the molecular fragment -X 1 --CH 2 -C ⁇ N when X 4 is an oxygen atom or a sulfur atom and X 2 and X 3 represent a nitrogen atom.
  • the radical Het according to formula (IV) is particularly preferably derived from the heteroaromatics 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, benzothiazole , Phenazine, benzocinnoline, benzoquinazoline, benzoquinox
  • the compounds according to formula (III) are selected from 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) -acetonitrii, 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-Dimethylpyrrole-3-oyl) -acetonitrile
  • the color spectrum may be advantageous for extending the color spectrum to add at least one further compound as component C in addition to at least one compound of formula (I) as component A and at least one compound of component B.
  • the compound of component C is selected from at least one reactive carbonyl compound, which are different from compounds of formula (I).
  • Reactive carbonyl compounds as component C according to the invention have at least one carbonyl group as a reactive group which reacts with the CH-acidic compound of component B to form a carbon-carbon bond.
  • Preferred reactive carbonyl compounds are aldehydes and ketones, especially aromatic aldehydes.
  • those compounds are also usable as component C, in which the reactive carbonyl group is derivatized or masked such that the reactivity of the carbon atom of the derivatized carbonyl group over the CH-acidic compounds of component B is always present.
  • These derivatives are preferably addition compounds a) of amines and derivatives thereof to form imines or oximes as addition compound b) of alcohols to form acetals or ketals as addition compound c) of water to form hydrates as addition compound (component C is derived in this case c) from an aldehyde) to the carbon atom of the carbonyl group of the reactive carbonyl compound.
  • Preferred reactive carbonyl compounds of component C are selected from the group consisting of benzaldehyde and its derivatives, naphthaldehyde and its derivatives, cinnamaldehyde and its derivatives, 2,3,6,7-tetrahydro-1H, 5H-benzo [ij] quinolizine-9 carboxaldehyde, 2,3,6,7-tetrahydro-8-hydroxy-1H, 5H-benzo [ij] quinolizine-9-carboxaldehyde, N-ethylcarbazole-3-aldehyde, 2-formylmethylene-1,3,3-trimethylindoline (Fischer's aldehyde or tribasic aldehyde),
  • Benzaldehyde, cinnamaldehyde and naphthaldehyde and their derivatives, in particular with one or more hydroxyl, alkoxy or amino substituents, are used with particular preference as the reactive carbonyl compound of component C in the agents according to the invention.
  • the compounds according to formula (Ca-1) are preferred,
  • 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 C r C 6 dialkylamino group group, a di (C 2 -C 6 - hydroxyalkyl) amino group, a di (C r C 6 -alkoxy-CrC 6 alkyl) aminoguppe, a C 1 - Ce-hydroxyalkyloxy group, a sulfonyl group, a carboxy group, a sulfonic acid group, a sulfonamido group , a sulfonamide group, a 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 derivatives of the benzaldehydes, naphthaldehydes or cinnamaldehydes of the reactive carbonyl compound according to component C are particularly preferably selected from 4-hydroxy-3-methoxybenzaldehyde, 3,5-dimethoxy-4-hydroxybenzaldehyde, A-hydroxy-1-naphthaldehyde, 4-hydroxybenzaldehyde 2-methoxybenzaldehyde, 3,4-dihydroxy-5-methoxybenzaldehyde, 3,4,5-trihydroxybenzaldehyde, 3,5-dibromo-4-hydroxybenzaldehyde, 4-hydroxy-3-nitrobenzaldehyde, 3-bromo-4-hydroxybenzaldehyde, 4- Hydroxy-3-methylbenzaldehyde, 3,5-dimethyl-4-hydroxybenzaldehyde, 5-bromo-4-hydroxy-3-methoxybenzaldehyde, 4-diethylamino-2-hydroxybenzaldehyde, 4-dimethylamino
  • the colorant additionally contains at least one reaction product (hereinafter referred to as reaction product RP) of a compound of formula I and a compound of component B as direct dye.
  • reaction product RP can z.
  • Example be obtained by heating the two reactants in an aqueous neutral to slightly alkaline medium, wherein the reaction products RP precipitate either as a solid from the solution or isolated by evaporation of the solution thereof.
  • Possibility to represent the reaction products analogously to the literature procedure in H. Mauchle et al., Pharmacy, 1999, 54 (4), 269-279.
  • molar ratios of component B to the compound according to formula I may be useful.
  • reaction products RP are selected from compounds of the formulas (V), (VI) and (VII),
  • R12 most preferably represents a hydrogen atom.
  • the compounds of the formulas (V) and (VI) are preferred reaction products RP according to the invention.
  • the above-mentioned compounds of the formula I, the compounds of the component B, component C and the reaction products RP 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.
  • agents according to the invention may comprise 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 represents a hydrogen atom, a C r 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 ) -alkoxy- (C 1 - 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 C 1 - to C 4 alkyl, C 1 - to C 4 - monohydroxyalkyl radical, a C 2 - to C 4 polyhydroxyalkyl radical, a (C 1 - to C 4) alkoxy (C 1 - to C 4 ) -alkyl radical or a C 1 - to C 4 -alkyl radical which is substituted by a nitrogen-containing group;
  • 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 -Monohydroxyalkylrest, a C 2 - to C 4 polyhydroxyalkyl, C 1 - to C 4 -hydroxyalkoxy, C 1 - to C 4 - acetylaminoalkoxy, C 1 - to C 4 - mesylaminoalkoxy or C 1 - to C 4 - carbamoylaminoalkoxy;
  • a halogen atom such as a chlorine, bromine, iodine or fluorine atom
  • a C 1 - to C 4 alkyl radical such as a chlorine, bromine, iodine or fluorine atom
  • a C 1 - to C 4 alkyl radical such as a chlorine, bromine, iodine or flu
  • 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 one another, they may together form a bridging ⁇ , ⁇ -alkylenedioxy group, 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 particularly preferred.
  • 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, in particular, the amino groups, C 1 - to CrMonoalkylamino phenomenon, C 1 - to C 4 dialkylamino, C 1 - 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 particularly preferred p-phenylenediamine derivatives of the formula (E1) according to the invention are p-phenylenediamine, p-toluenediamine, 2- ( ⁇ -hydroxyethyl) -p-phenylenediamine, 2- ( ⁇ , ⁇ -dihydroxyethyl) -p-phenylenediamine 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.
  • 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: in which:
  • 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, of 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 optionally be substituted by one or more hydroxyl or C 1 to C 8 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 C 4 -hydroxyalkyl radical, a C 1 - to C 4 -aminoalkyl radical or a direct compound for bridging Y,
  • 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 proviso that the compounds of the Formula (E2) contain only one bridge Y per molecule.
  • 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-methyl-aminophenyl) -tetramethylendiannin, N 1 N'-diethyl-N, N'-bis- (4'- amino-3'-methylphenyl) ethylenediamine, bis (2-hydroxy-5-aminophenyl) methane
  • 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, 1, 3-bis (2,5-diaminophenoxy) -propan-2-ol, 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 C 1 - to C 4 -monohydroxyalkyl radical, a C 2 - to C 4 -polyhydroxyalkyl radical, a (C 1 - to C 4 ) - Alkoxy (C r to C 4 ) alkyl, a C 1 - to C 4 -Aminoalkylrest, a hydroxy (C r to C 4 ) alkylamino, a C 1 - to C 4 -hydroxyalkoxy, a C 1 - C 4 - hydroxyalkyl- (C 1 -C 4 ) -aminoalkyl or (C 1 -C 4 -alkylamino) - (C 1 to C 4 ) -alkyl, and
  • G 14 represents a hydrogen or halogen atom, a C r to C 4 alkyl radical, a C 1 - to C 4 -monohydroxyalkyl radical, a C 2 - to C 4 -polyhydroxyalkyl radical, a (C 1 - bis C 4 ) -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 r 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, A-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, A-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 the 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- ( ⁇ -
  • 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 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- triaminopyrimidine.
  • 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-diaminopyrazole, 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-hydrazinopyrazole, 1-Benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-buty
  • Preferred pyrazolopyrimidine derivatives are, in particular, the derivatives of the pyrazolo [1,5-a] pyrimidine of the following formula (E4) and their tautomeric forms, if a tautomeric equilibrium exists:
  • G% 1 1 7 ', 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 -Polyhydroxyaikylrest a (C 1 - to C 4) alkoxy (C r to C 4) alkyl group, a C 1 - to C 4 aminoalkyl, optionally substituted by an acetyl ureide or a sulfonyl -Rest, a (C 1 - to C 4 ) -alkylamino (C r to C 4 ) -alkyl radical, a di - [(C r to C 4 ) -alkyl] - (C r to C 4 ) aminoalkyl radical, wherein the dialkyl radicals optionally form a carbon cycle or a heterocycle with 5 or 6 chain
  • the pyrazolo1, 5-a] pyrimidines of the above formula (E4) can be used as in the literature described by cyclization starting from an aminopyrazole or hydrazine.
  • the colorants according to the invention 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, resorcinomonomethylether, 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 and 2-methyl
  • Preferred coupler components according to the invention are 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-diaminobenzene and its derivative
  • Di- or trihydroxybenzene derivatives 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-diamino-2,6-dimethoxypyridine, naphthalene derivatives such as 1-naphthol, 2-methyl-1-naphthol, 2- Hydr
  • Morpholine derivatives such as 6-hydroxybenzomorpholine and 6-aminobenzomorpholine,
  • Quinoxaline derivatives such as 6-methyl-1,2,3,4-tetrahydroquinoxaline, pyrazole derivatives such as 1-phenyl-3-methylpyrazol-5-one, indole derivatives such as 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole, pyrimidine derivatives such as For example, 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 1-hydroxy-3,4-methylenedioxybenzene, 1-amino-3,4-methylenedioxybenzene and 1 - (2'-hydroxyethyl) amino-3,4-methylenedioxybenzene and their physiologically acceptable salts.
  • 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.
  • indoles and indolines in the Agents of the invention which have at least one hydroxy 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 natural-analogous hair dyes are derivatives of the 5,6-dihydroxyindoline of the formula Villa,
  • G 21 is hydrogen, a C r C 4 -alkyl group or a C r 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 an alkyl group 4 C r C,
  • G 24 is hydrogen, a CrC 4 alkyl group or a group -CO-G 26 wherein G 26 represents a C r C 4 alkyl group, and
  • G 25 is 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, group 4 hydroxyalkyl, a C r C 4 alkyl group or a CrC,
  • 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 r C 4 alkyl group, and
  • G 31 is one of the groups mentioned under G 30 , 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 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 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 .-%.
  • 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 complex ⁇ 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.
  • Suitable catalysts for the oxidation of the dye precursors are the so-called 2-electron oxidoreductases in combination with the specific substrates, eg
  • Lactate oxidase and lactic acid and their salts Lactate oxidase and lactic acid and their salts
  • 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 Nitrophenylendiamine, Nitroaminophenole, 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'
  • aromatic systems substituted with a quaternary nitrogen group such as Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 and Basic Brown 17, as well as
  • 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 of the invention may also naturally occurring dyes, such as those contained in henna red, henna neutral, henna black, chamomile flower, sandalwood, black tea, buckthorn bark, sage, bluewood, madder root, Catechu, Sedre and alkanel.
  • 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, minor amounts may contain other components, as far as they are not Dyeing result adversely affect or other reasons, eg. As toxicological, must be excluded.
  • compositions according to the invention may additionally contain color enhancers.
  • the color enhancers 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, 4-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 10% by weight, in particular 0.5 to 5% by weight, in each case based on 100 g of the ready-to-use colorant.
  • the agents according to the invention may have a pH of from pH 4 to 12, preferably from pH 5 to 10.
  • 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 or surfactant-containing foaming solutions such.
  • it is also possible to incorporate the colorants in anhydrous carrier. Examples of further suitable and inventively preferred ingredients are given below.
  • a cosmetic carrier in particular an otherwise customary carrier of agents for dyeing human hair is used.
  • the colorants according to the invention can be composed in accordance with known colorants or are conventional for these Contain ingredients. Examples of further suitable and inventively preferred ingredients are given below.
  • the agents according to the invention contain the compounds of the formula (I) and the compounds of component B preferably in a suitable aqueous, alcoholic or aqueous-alcoholic carrier.
  • a suitable aqueous, alcoholic or aqueous-alcoholic carrier for the purpose of hair coloring such carriers 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.
  • hair coloring such carriers 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.
  • the dye precursors in a powdered or tablet-shaped formulation.
  • aqueous-alcoholic solutions are to be understood as meaning aqueous solutions containing 3 to 70% by weight of a C 1 -C 4 -alkoxy, 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.
  • the colorants contain at least one surfactant, wherein in principle both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants are suitable. 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.
  • 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, linear fatty acids with 10 to 22 carbon atoms (soaps),
  • 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 have at least one quaternary ammonium group in the molecule and at least one -COO H - or -SO 3 ⁇ -GrUpPe wear.
  • 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
  • Ampholytic surfactants are surface-active compounds which, in the 3 H-group in addition to a C 8- i 8 alkyl or acyl group in the molecule at least one free amino group and at least one -COOH or -SO and which are capable of forming inner salts
  • suitable 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, cocoacylaminoethylaminopropionate and C 12 -i ⁇ -acy
  • Nonionic surfactants contain as hydrophilic group z.
  • Such compounds are, for example
  • ammonium halides such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, eg. 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 base these materials on natural plant or animal raw materials, so as to obtain mixtures of substances with different, depending on the particular raw 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, on the other hand, are obtained when, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates are used as catalysts.
  • the use of products with narrow homolog distribution may be preferred.
  • auxiliaries and additives are, for example, nonionic polymers such as vinylpyrrolidone / inylacrylate copolymers, polyvinylpyrrolidone and vinylpyrrolidone / inylacetate 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, celiac gums lulose derivatives, e.g. 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.
  • 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,
  • Antidandruff active ingredients such as Piroctone Olamine and Zinc Omadine, other pH-adjusting agents such as ammonia, monoethanolamine, basic amino acids and citric acid active ingredients 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 water-containing carrier are used to prepare the colorants 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.
  • Suitable metal salts are, for. As formates, carbonates, halides, sulfates, butyrates, valerates, capronates, acetates, lactates, glycolates, tartrates, citrates, gluconates, propionates, phosphates and phosphonates of alkali metals such as potassium, sodium or lithium, alkaline earth metals such as magnesium, calcium, Strontium or barium, or of aluminum, manganese, iron, cobalt, copper or zinc, sodium acetate, lithium bromide, calcium bromide, calcium gluconate, zinc chloride, zinc sulfate, magnesium chloride, magnesium sulfate, ammonium carbonate, chloride and acetate being preferred. These salts are preferably contained in an amount of 0.03 to 10 wt .-%, in particular from 0.5 to 5 wt .-%, based on 100
  • the pH of the ready-to-use dyeing preparations is usually between 2 and 11, preferably between 5 and 10.
  • a second subject of the present invention relates to the use of at least one compound according to formula I,
  • R1, R2 and R3 are as defined in the first subject of the invention, together with at least one CH-acidic compound as component B as a coloring component in hair dyes.
  • those compounds of the formula I are used as the coloring component in hair colorants, which are selected from the preferred and particularly preferred representatives mentioned in the first subject of the invention.
  • reaction product RP from a compound according to formula I and a representative of component B as coloring components in hair dyes.
  • a third object of the present invention relates to a process for dyeing keratin-containing fibers, in particular human hair, wherein a colorant contained in a cosmetic carrier
  • R1, R2 and R3 are as defined in the first subject of the invention, together with
  • At least one CH-acidic compound as component B 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 supply can be done by an external heat source, such as warm air of a hot air blower, as well as, especially in a hair dye on living subjects, by the body temperature of the subject. In the latter case, usually the part to be dyed is covered with a hood.
  • the compounds of the formula I and the compounds of component B can be applied as coloring components either simultaneously to the hair or else sequentially, ie in a multi-stage process, wherein it is irrelevant which of the components is applied first.
  • the optionally contained ammonium or metal salts can be added to the compounds of formula I or the compounds of component B. 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, e.g. a peroxodisulfate 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, if appropriate, the abovementioned derivatives of indole or indoline are applied to the fiber and, after an exposure time, optionally with the addition of above-mentioned suitable oxidizing agents, left on the hair for 5-45 minutes on the keratin 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 hair dye is preferably in a pH range of pH 7 to pH 11, particularly preferably pH 8 to pH 10.
  • the oxidizing agent may be mixed with the hair dye immediately prior to application and the mixture applied to the hair. If the compounds of the formula I and the component B are applied to the hair in a two-stage process, the oxidizing agent must be used in one of the two 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 of formula I and the compounds of component B can be stored either in separate containers or together in a container, either in a liquid to pasty preparation (aqueous or anhydrous) or as a solid, for example as a dry powder. If the components are stored together in a liquid preparation, it should be substantially anhydrous to reduce a reaction of the components and have an acidic pH. If the components are stored together, it is preferable to use these as Solid, in particular in the form of a preferably multilayer shaped body, for example, as a tablet to assemble. In the case of the multilayer molded bodies, the component A is incorporated in one layer and the component B in another layer, wherein between these layers is preferably a further layer as a release layer. The separating layer is free of compounds of components A and B.
  • the reactive components are intimately mixed with each other just before use.
  • dry storage a defined amount of warm (3O 0 C to 8O 0 C) water is usually added prior to application and made a homogeneous mixture.
  • a fourth subject of the invention is the use of at least one compound according to formula I,
  • R1, R2 and R3 are as defined in the first subject of the invention, together with
  • a fifth object of the invention is the use of at least one compound according to formula I,
  • R1, R2 and R3 are as defined in the first subject of the invention, together with
  • the dyeings of keratin-containing fibers are known to be exposed to environmental influences, such as light, friction or washes, and may thereby lose brilliance and color depth. In the worst case, if necessary, a nuance shift of the coloring sets in.
  • Such aged dyeings of keratinous fibers if desired by the user, may be restored to the color state by color refreshment as presented immediately after the initial dyeing. It is according to the invention to use a combination of at least one compound of the formula I and at least one compound of the component B for such a color refreshment.
  • the aromatic aldehyde (component A) was dissolved or suspended in a little water. To increase the solubility was alkalized if necessary with a few drops of 50% sodium hydroxide solution. The mixture was then made up to 98 g with water and stirred until complete dissolution of the aldehyde (partially with gentle warming to about 40 0 C). Natrosol was then added with stirring and the swelling process was awaited.
  • the C, H-acidic compound (component B) was first dissolved with stirring in a little water, then made up to 98 g with water. While stirring, the Natrosol was added and the swelling process was awaited.
  • the two aqueous gel formulations (gel 1 and gel 2) were mixed in a ratio of 1: 1, then the pH was adjusted with ammonia or tartaric acid.
  • B2 1-AlII-1,2-dihydro-3,4,6-trimethyl-2-oxopyrimidinium bromide
  • B3 2-Dihyclro-1- (2-hydroxyethyl) -3,4 J 6-trimethyl-2-oxopyrimidinium p-toluenesulfonate
  • B4 2- (cyanomethyl) benzimidazole

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Abstract

L'invention concerne un agent permettant de colorer des fibres à base de kératine, notamment des cheveux humains, qui contient du 3-allyle-4-hydroxybenzaldéhyde et/ou ses dérivés, en combinaison avec des composés CH-acides. L'invention concerne également l'utilisation de cette combinaison dans des agents pour colorer des fibres à base de kératine, pour raviver la couleur de fibres à base de kératine d'ores et déjà colorées ou les nuancer, ainsi qu'un procédé pour colorer des fibres à base de kératine, notamment des cheveux humains.
EP06723689A 2005-05-12 2006-03-24 Agent pour colorer des fibres a base de keratine Withdrawn EP1879660A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005022790A DE102005022790A1 (de) 2005-05-12 2005-05-12 Mittel zum Färben von keratinhaltigen Fasern
PCT/EP2006/002707 WO2006119819A1 (fr) 2005-05-12 2006-03-24 Agent pour colorer des fibres à base de kératine

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EP1879660A1 true EP1879660A1 (fr) 2008-01-23

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EP06723689A Withdrawn EP1879660A1 (fr) 2005-05-12 2006-03-24 Agent pour colorer des fibres a base de keratine

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US (1) US7393367B2 (fr)
EP (1) EP1879660A1 (fr)
AU (1) AU2006246134A1 (fr)
DE (1) DE102005022790A1 (fr)
WO (1) WO2006119819A1 (fr)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004028599A1 (de) * 2004-06-12 2005-12-29 Henkel Kgaa Milde Bleichmittel mit erhöhter Aufhellleistung
DE102005062834A1 (de) * 2005-12-27 2007-06-28 Henkel Kgaa Reversibel schaltbare Haarfärbung
DE102006060150A1 (de) * 2006-12-18 2008-06-19 Henkel Kgaa Mittel zum Färben von keratinhaltigen Fasern
DE102007040314A1 (de) * 2007-08-24 2009-02-26 Henkel Ag & Co. Kgaa Kit zur Bereitstellung von Färbemitteln
DE102008052618A1 (de) 2008-10-21 2010-04-22 Henkel Ag & Co. Kgaa Tricyclische Aldehyde und C,H-acide Verbindungen
DE102008061863A1 (de) * 2008-10-22 2010-04-29 Henkel Ag & Co. Kgaa Verfahren zur Kaschierung grauer Haare
DE102008061855A1 (de) * 2008-10-22 2010-04-29 Henkel Ag & Co. Kgaa Mittel zum Färben von keratinhaltigen Fasern
DE102008061862A1 (de) 2008-12-15 2010-06-17 Henkel Ag & Co. Kgaa Färbemittel, enthaltend spezielle halogensubstituierte Brenzcatechinaldehyde und spezielle CH-acide Verbindungen
WO2015044944A2 (fr) * 2013-09-26 2015-04-02 Coloright Ltd. Lecteur de cheveux, dispositif distributeur et systèmes et procédés associés
US10799440B2 (en) 2016-04-22 2020-10-13 Innospec Limited Methods, compositions and uses relating thereto
CN109310594A (zh) 2016-04-22 2019-02-05 因诺斯佩克有限公司 方法、组合物及其相关用途

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE626050A (fr) 1962-03-30
DE1492175A1 (de) 1965-07-07 1970-02-12 Schwarzkopf Gmbh Hans Verfahren zum Faerben von lebenden Haaren
DE2359399C3 (de) 1973-11-29 1979-01-25 Henkel Kgaa, 4000 Duesseldorf Haarfärbemittel
DE3723354A1 (de) * 1987-07-15 1989-01-26 Henkel Kgaa Sulfatierte hydroxy-mischether, verfahren zu ihrer herstellung und ihre verwendung
DE3725030A1 (de) 1987-07-29 1989-02-09 Henkel Kgaa Oberflaechenaktive hydroxysulfonate
JP2526099B2 (ja) 1988-07-07 1996-08-21 花王株式会社 角質繊維染色組成物
DE3843892A1 (de) 1988-12-24 1990-06-28 Wella Ag Oxidationshaarfaerbemittel mit einem gehalt an diaminopyrazolderivaten und neue diaminopyrazolderivate
FR2642967B1 (fr) * 1989-02-15 1991-06-07 Oreal Utilisation en cosmetique de diorganopolysiloxanes a fonction benzalmalonate et nouvelles compositions cosmetiques contenant ces composes, destinees a la protection de la peau et des cheveux
DE3926344A1 (de) 1989-08-09 1991-02-28 Henkel Kgaa Verfahren zur herstellung von hellfarbigen oelsaeuresulfonaten
DE4133957A1 (de) 1991-10-14 1993-04-15 Wella Ag Haarfaerbemittel mit einem gehalt an aminopyrazolderivaten sowie neue pyrazolderivate
DE4234887A1 (de) * 1992-10-16 1994-04-21 Wella Ag Oxidationshaarfärbemittel mit einem Gehalt an 4,5-Diaminopyrazolderivaten sowie neue 4,5-Diaminopyrazolderivate und Verfahren zu ihrer Herstellung
DE4234885A1 (de) 1992-10-16 1994-04-21 Wella Ag Verfahren zur Herstellung von 4,5-Diaminopyrazol-Derivaten, deren Verwendung zum Färben von Haaren sowie neue Pyrazol-Derivate
DE4440957A1 (de) * 1994-11-17 1996-05-23 Henkel Kgaa Oxidationsfärbemittel
FR2733749B1 (fr) 1995-05-05 1997-06-13 Oreal Compositions pour la teinture des fibres keratiniques contenant des diamino pyrazoles, procede de teinture, nouveaux diamino pyrazoles et leur procede de preparation
DE19543988A1 (de) 1995-11-25 1997-05-28 Wella Ag Oxidationshaarfärbemittel mit einem Gehalt an 3,4,5-Triaminopyrazolderivaten sowie neue 3,4,5-Triaminopyrazolderivate
DE19843290A1 (de) 1998-09-22 2000-03-23 Km Europa Metal Ag Verfahren zur Lokalisierung von Elementkonzentrationen in einem Gußstrang und Vorrichtung des Verfahrens
DE10241076A1 (de) * 2002-09-05 2004-03-11 Henkel Kgaa Mittel zum Färben von keratinhaltigen Fasern
DE102004044231A1 (de) * 2004-09-14 2006-03-16 Henkel Kgaa Mittel zum Färben von keratinhaltigen Fasern

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2006119819A1 *

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DE102005022790A1 (de) 2006-11-16
WO2006119819A1 (fr) 2006-11-16
US7393367B2 (en) 2008-07-01
AU2006246134A1 (en) 2006-11-16
US20080104772A1 (en) 2008-05-08

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