EP1879661A1 - 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
EP1879661A1
EP1879661A1 EP06723691A EP06723691A EP1879661A1 EP 1879661 A1 EP1879661 A1 EP 1879661A1 EP 06723691 A EP06723691 A EP 06723691A EP 06723691 A EP06723691 A EP 06723691A EP 1879661 A1 EP1879661 A1 EP 1879661A1
Authority
EP
European Patent Office
Prior art keywords
group
hydroxy
formyl
alkyl group
dihydro
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Withdrawn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
EP06723691A
Other languages
German (de)
English (en)
Inventor
Wibke Gross
Horst Höffkes
Doris Oberkobusch
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 EP1879661A1 publication Critical patent/EP1879661A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/10—Preparations for permanently dyeing the hair
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—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
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/37—Esters of carboxylic acids
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/42—Amides
    • 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
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/42—Colour properties
    • A61K2800/43—Pigments; Dyes
    • A61K2800/432—Direct dyes
    • A61K2800/4324—Direct dyes in preparations for permanently dyeing the hair

Definitions

  • the invention relates to an agent for dyeing keratin-containing fibers, in particular human hair, containing selected benzoic acids functionalized with at least one formyl group and at least one hydroxyl group and / or its derivatives in combination with CH-acidic compounds, the use of this combination in dyeing agents of keratin-containing fibers, for color refreshment or nuancing of already dyed keratin-containing 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 derivatives are generally used.
  • 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-methylaminopyridine and 3,5-diamino-2,6-dimethoxypyridine.
  • 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. 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.
  • Object of the present invention is to provide colorants for keratin fibers, especially human hair, which in terms of color depth and the Fastness properties, such as light, friction and wash fastness and welding and cold wave fastness, qualitatively the usual oxidation hair dyes are at least equivalent, but without necessarily on oxidizing agents such. B. H 2 O 2 instructed to be.
  • the colorants must have no or only a very low sensitizing potential and may under no circumstances be mutagenic.
  • Colorants containing compounds of the formula I below in combination with CH-acidic compounds, and the use of this combination for dyeing keratin-containing fibers or for color refreshing or shading already dyed keratin fibers are not yet known.
  • 2-dihydropyrimidinium derivatives are known, which are suitable in combination with reactive carbonyl compounds, in particular benzaldehyde derivatives, for coloring keratin-containing fibers.
  • the disclosed benzaldehyde derivatives may generally bear a carboxy group (-COOH) or a carbamoyl group (-CO-NH 2 ) as well as a hydroxy group.
  • Benzaldehydes with the substitution pattern of the compounds of the invention according to the following formula I are not mentioned therein.
  • 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, wherein
  • 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 ( ⁇ VC alkoxy group, a C 1 -C 6 - hydroxyalkyl group, a C 2 -C 6 polyhydroxyalkyl group, a hydroxy (C r C 6) alkyloxy group, a carboxy group, a (CrC 6) alkoxycarbonyl, hydroxy (C 2 -C 6) alkyloxycarbonyl group, a C 2 -C 6 - Acyl group, a formyl group, a nitro group, a group -C (O) - NR 4 R 5 , or a group
  • R 4 , R 5 , R 6 and R 7 are independently a hydrogen atom, a C r C 6 alkyl group or a C 2 -C 6 hydroxyalkyl group and n is a is an integer from 0 to 6, where R1 and R2 can form a 5- or 6-membered aromatic or heteroaromatic ring,
  • Y stands for a group -OR 1 or -NR 11 R 1 'wherein R 1, R 11 and R 1 "independently represent hydrogen atom, a Ci-C 6 alkyl, C 2 -C 6 alkenyl group, a C 2 -C 6 -, P ⁇ ydroxyalkyl distr, a C 2 -C 6 polyhydroxyalkyl group, a -C (6 Ci-C) alkyl group 6 alkoxy, an aryl group, a heteroaryl group, an aryl alkyl group (CrC 6) a group - (CH 2 ) m NR 6a R 7a , wherein R 6a and R 7a are independently a hydrogen atom, a C r C 6 alkyl group or a C 2 -C 6 hydroxyalkyl group and m is an integer from 1 to 6 stands, along with
  • 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 CrC 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 r C 6 ) alkoxy group is the 2-hydroxyethoxy group.
  • Preferred hydroxy (C 2 -C 6 ) alkyloxycarbonyl groups are the 2-
  • halogen atoms are F, Cl, Br or I atoms, with Br, 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-dimethylaminocarbonyl, N, N-diethylaminocarbonyl, N, N-bis (2-hydroxyethyl) aminocarbonyl and the carbamoyl group are exemplary groups
  • Preferred arylCrC 6 -alkyl groups are benzyl and 2-phenylethyl.
  • Preferred aryl groups are phenyl, naphthyl and biphenyl.
  • heteroaryl group examples include pyrrolidyl, 2-furyl, 2-thienyl, 4-pyridyl, 3
  • radicals R1, R2 and R3 independently represent a hydrogen atom, a halogen atom, a C r C 6 alkyl group or a C 1 -C koxy devis 6 -alkyl in compounds are ,
  • the agent according to the invention preferably contains at least one compound of the formula (I) which carries a hydrogen atom as substituent R 2 and R 3.
  • radical R 1 a hydrogen atom, a C r C 6 -alkyl group (in particular a methyl group), a C r C 6 -alkoxy group (in particular a methoxy group) or carry a halogen atom. It is in this embodiment in turn, particularly preferred when the radicals R2 and R3 are a hydrogen atom.
  • Y in formula (I) and its abovementioned embodiments preferably represents a group -OR 1 or -NR 11 R 1 ", in which R 1 , R 11 and R 1 " independently of one another represent a hydrogen atom, a C 1 -C 6 -alkyl group (in particular Methyl or ethyl), a C 2 -C 6 -hydroxyalkyl group (especially 2-hydroxyethyl), a C 2 -C 6 -polyhydroxyalkyl group, a C 1 -C 6 -alkoxy- (C 1 -C 6 ) -alkyl group (especially a 2-methoxyethyl group) ,
  • those compounds according to the invention are also suitable as component A according to formula (I) in which the carbonyl group of the -CHO group in formula (I) is derivatized or masked such that the reactivity of the carbon atom of the derivatized carbonyl group towards the CH-acid Compounds of component B is always present.
  • 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 of component B 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 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-CrC 6 - alkyl group, a CrC 6- hydroxyalkyl group, a C 2 -C 6 polyhydroxyalkyl group, a d-Ce-alkoxy-CrCe-alkyl group, a group R IV R V N- (CH 2 ) P -, wherein R ⁇ v and R v independently represent a Hydrogen atom, a C r C 4 alkyl group, a C r C 4 -hydroxyalkyl group or an aryl-Ci-C 6 alkyl group, wherein R IV and R v together with the nitrogen atom, a 5-, 6- or 7-membered ring can form and p stands for a number 2, 3, 4, 5 or 6,
  • R 10 and R 12 independently of one another represent a hydrogen atom or a C 1 -C 6 -alkyl group, where at least one of the radicals R 10 and R 12 denotes a C 1 -C 6 -alkyl group,
  • R 11 stands for a hydrogen atom, a CrC 6 alkyl group, a C 1 -C 6 - hydroxyalkyl group, a C 2 -C 6 polyhydroxyalkyl group, a C r C 6 alkoxy group, a C r C 6 -hydroxyalkoxy group, a group R vl R vll N- (CH 2 ) q-, where R v ⁇ and R v "independently of one another represent a hydrogen atom, a C r C 6 -alkyl group, a d-Ce Hydroxyalkyl group or an arylC 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 is a 5- or 6- membered aromatic ring may form optionally substituted by a halogen atom, a Ci-C 6 alkyl group, a -C 6 - hydroxyalkyl group, a
  • Y 1 represents an oxygen atom, a sulfur atom or a group NR X, where R x is a hydrogen atom, an aryl group, a heteroaryl group, a -C 6 - alkyl group or a -C 6 -arylalkyl group,
  • 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 necessarily stands for 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 1 is an oxygen or a sulfur atom, more preferably an oxygen atom.
  • the radical R 8 is preferably selected from a (C r 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 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 1 is an oxygen or sulfur atom
  • the radical R 8 is selected from a (C r 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.
  • 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 compatible counterion X ' , which is formed from salts of
  • the anions chloride, bromide, iodide, hydrogen sulfate or p-toluenesulfonate are particularly preferably 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 of one another 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, a cyanomethyl group, a cyanomethylcarbonyl group, a optionally substituted heteroaryl group, an arylCrCe 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 r C 6 alkoxycarbonyl group, a C 1 -C 6 -alkoxy-C 2 -C 6 - alkyl group, CrC a- 6 sulfoalkyl, a Ci-C 6 carboxyalkyl group, a group R x R xl "N- (CH 2)
  • 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 CrC ⁇ -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 arylC r C 6 alkyl group, a C 1 -C 6 hydroxyalkyl group, a C 2 -C 6 polyhydroxyalkyl group, a C r C 6 alkoxy group, a C r C 6 alkoxycarbonyl group, a C 1 -C 6 alkoxy C 2 -C 6 alkyl group, a C 1 -C 6 sulfoalkyl group, a C r C 6 carboxyalkyl group and a group R
  • X 4 is an oxygen atom, a sulfur atom, a vinyl group or an NH group, where the last two groups independently optionally mjt a linear or cyclic Ci-C 6 alkyl group, a C 2 -C 6 - alkenyl group, an optionally substituted Aryl group, one optionally substituted heteroaryl group, an arylC r C 6 alkyl group, a C 2 -C 6 hydroxyalkyl group, a C 2 -C 6 polyhydroxyalkyl group, a C 1 -C 6 alkoxy C 2 -C 6 alkyl group, a C 1 -C 6 -sulfoalkyl group, a C r C 6 -carboxyalkyl group, a group R XIII R XIV N- (CH 2 ) U -, in which R xl "and R x ⁇ v independently of one another represent a hydrogen atom, a linear or cyclic C 6 alkyl group, a C 2
  • 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) -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-Dimethylpyrrole-3-oyl) -acetonitrile, 2-
  • the inventive compositions 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 with respect to the CH-acidic compounds of component B is always present.
  • 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 or ketals as addition compound c) of water. Formation of 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 1 -C 6 dialkylamino group, a di (C 2 -C 6 - hydroxyalkyl) amino group, a DKCrCe-alkoxy-CRCE-alkyOaminoguppe, a C 1 - C 6 -Hydroxyalkyloxy distr, 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,
  • 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 benzaldehydes, naphthaldehydes or cinnamaldehydes of the reactive carbonyl compound according to component C are particularly preferably selected from at least one compound of the group 4-hydroxy-3-methoxybenzaldehyde, 3,5-dimethoxy-4-hydroxybenzaldehyde, 4-hydroxy-1-naphthaldehyde , 4-hydroxy-2-methoxybenzaldehyde, 3,4-dihydroxy-5-methoxybenzaldehyde, 3,4,5-
  • Trihydroxybenzaldehyde 4-dimethylaminobenzaldehyde, 4-diethylaminobenzaldehyde, A-dimethylamino-2-hydroxybenzaldehyde, 4-pyrrolidinobenzaldehyde, A-
  • the colorant additionally comprises at least one reaction product (hereinafter referred to as reaction product RP) from a A compound of formula I and a compound of component B as a 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. It is also possible to use the reaction products analogously to the literature procedure in Gadella et al., Bulletin of the National Research Center (Egypt), 1993, 18 (3), 151-162 or H. Baumann et al, J. Liebigs Ann. Chem., 1968, 717, 124-136.
  • 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 / or (VII),
  • R 12 is a hydrogen atom or a C 1 -C 6 -alkyl group (preferred for a hydrogen atom or a methyl group), whereby it is again particularly preferred if R 11 stands for a hydrogen atom.
  • the above-mentioned compounds of the formula I 1, the compounds of component B, component C and the reaction products RP are, when they are used, in each case preferably in an amount of 0.03 to 65 mmol, in particular from 1 to 40 mmol to 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 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 radical (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 ,
  • 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
  • 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:
  • Z and Z independently represent a hydroxyl or NH 2 -ReSt, the optionally substituted by a C 1 - to C 4 -alkyl radical, by a C 1 - to C 4 -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 may be interrupted or terminated by one or more nitrogen-containing groups and / or one or more heteroatoms such as oxygen, sulfur or nitrogen atoms and possibly by one or more hydroxyl or C 1 - to C 8 - alkoxy may be substituted, 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 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 bridging 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 - (ß-hydroxyethyl) -N, N'-bis (4-aminophenyl) - tetramethylenediamine, N, N'-bis (4-methyl-aminophenyl) tetramethylenediamine, N 1 N'-diethyl-N, N 1 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-diaminopropan-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 monohydroxyalkyl radical d- 4 to C, 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 r to C 4 ) aminoalkyl or a (di-C 1 - to C 4 alkylamino) - (C r to C 4 ) alkyl, 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 ) - Alkoxy (C r 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-methyl-phenol, 4-amino-3-fluorophenol, 2-hydroxymethylamino-4-aminophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2- ( ⁇ -hydroxyethoxy) -phenol, 4- Amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethyl-phenol, 4-amino-2-aminomethylphenol, 4-amino-2- ( ⁇ -hydroxyethyl-aminomethyl) -phenol, 4- Amino-2- ( ⁇ , ⁇ -dihydroxyethyl) phenol, 4-amino-2-fluorophenol, 4-amino-2-chlorophenol, 4-amino-2,6-dichlorophenol, 4-amino-2-fluorophenol, 4-amino-2-chlorophenol, 4-amin
  • 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 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-ajpyrimidine 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 Polyhydroxyalkylrest a (C 1 - to C 4 J-AIkOXy- (C 1 - to C 4 ) -alkyl radical, a C 1 - to C 4 -Aminoalkylrest, which may be protected by an acetyl-ureide or a sulfonyl radical may be a (C 1 to C 4 ) alkylamino (C r to C 4 ) alkyl radical, a di-J (C 1 to C 4 ) alkyl] - (C r to C 4 ) aminoalkyl radical, where the dialkyl radicals optionally form a carbon cycle or a heterocycle with 5 or 6 chain members, a C 1 -
  • the pyrazolol, 5-a] pyrimidines of the above formula (E4) can be prepared as described in the literature by cyclization from an aminopyrazole or hydrazine.
  • the colorants according to the invention contain at least one coupler component.
  • coupler components are usually m-phenylenediamine derivatives, naphthols, Resorcinol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives.
  • 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-4-chloro
  • 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,
  • o-diaminobenzene and its derivatives such as 3,4-diaminobenzoic acid and 2,3-diamino-1-methylbenzene,
  • 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-hydroxy
  • 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-methyl resorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol and 2,6-dihydroxy-3,4-dimethylpyridine.
  • 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 C 1 -C 4 -alkyl group or a group -CO-G 26 in which
  • G% 26 represents a C 1 -C 4 -alkyl group
  • 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, a C 1 -C 4 -alkyl group or a C 1 -C 4 -hydroxyalkyl group,
  • 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 1 -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 stands for 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 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 .-%.
  • oxidizing agents for. B. H 2 O 2
  • 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 .
  • 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. Examples are salts, chelate complexes or oxides of iron, ruthenium, manganese and copper.
  • oxidation catalysts 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'
  • 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 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 of other components may be included, as far as they do not adversely affect the staining or other reasons, eg, 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 are usually incorporated into an aqueous cosmetic carrier.
  • Suitable hydrous cosmetic carriers are for.
  • As creams, emulsions, gels or surfactant-containing foaming solutions such.
  • the colorants according to the invention may be composed according to known colorants or contain the usual ingredients for them. Examples of further suitable and inventively preferred ingredients are given below.
  • 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 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. 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.
  • Zwitterionic surfactants are those surface-active compounds which carry in the molecule at least one quaternary ammonium group and at least one -COO W or -SO ⁇ group.
  • 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-imidazolines having in each case 8 to 18 carbon atoms in the alkyl or acyl group and the cocoacylaminoethylhydroxyethylcarboxymethyl glycinate.
  • a preferred zwitterionic surfactant is the fatty acid amide derivative known by the CTFA name Coca
  • 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-co kosalkylaminopropionat, cocoacylaminoethyl aminopropionate and C 12 - 18 - s
  • 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; diquatemmaschinee 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 generally preferred to use native plant or animal raw materials in the production of these substances, so that substance mixtures having different alkyl chain lengths depending on the particular raw material are obtained.
  • 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. Polyvinyl alcohol, structurants such as glucose and maleic acid, hair-conditioning compounds such as phospholipids, for example soya lecithin, egg lecithin and cephalins, and also 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, glycerine 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.
  • emulsifiers in concentrations of 0.5 to 30 wt .-%
  • thickening agents in concentrations of 0.1 to 25 wt .-% of the total colorant used.
  • ammonium or metal salts are, for.
  • 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 g of the total ready colorant.
  • 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 of the formula I 1
  • 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.
  • at least one 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, R3 and Y 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 input may be provided by an external heat source, e.g. warm air of a hot air blower, as well as, especially when a hair color on living subjects, done 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 thereby the compounds be added with the 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 optionally mentioned derivatives of indole or indoline is applied to the fiber and after a reaction time optionally with the addition of aforementioned suitable oxidizing agents on the hair for 5-45 minutes leave the keratin fiber. Thereafter, the hair is rinsed.
  • existing oxidation dyeings can be given a new shade of shade. If you choose the color shade of the invention
  • 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 preferred to formulate these as a solid, in particular in the form of a preferably multilayer molded article, for example as a tablet. 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. In the separate storage, the reactive components are intimately mixed with each other just before use. In dry storage, a defined amount of warm (3O 0 C to 80 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 1
  • R1, R2, R3 and Y 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,
  • 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 compound of the invention (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, then was 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.

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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 des acides benzoïques fonctionnalisés avec au moins un groupe formyle et au moins un groupe hydroxy 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, ainsi qu'un procédé pour colorer des fibres à base de kératine, notamment des cheveux humains.
EP06723691A 2005-05-12 2006-03-24 Agent pour colorer des fibres a base de keratine Withdrawn EP1879661A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE200510022789 DE102005022789A1 (de) 2005-05-12 2005-05-12 Mittel zum Färben von keratinhaltigen Fasern
PCT/EP2006/002709 WO2006119821A1 (fr) 2005-05-12 2006-03-24 Agent pour colorer des fibres a base de keratine

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EP1879661A1 true EP1879661A1 (fr) 2008-01-23

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EP (1) EP1879661A1 (fr)
DE (1) DE102005022789A1 (fr)
WO (1) WO2006119821A1 (fr)

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09328622A (ja) * 1996-04-11 1997-12-22 Konica Corp 新規色素及び電子写真用トナー
FR2787705B1 (fr) * 1998-12-23 2002-06-14 Oreal Procede de teinture mettant en oeuvre une amine cationique aliphatique et un compose choisi parmi un aldehyde, une cetone, une quinone et un derive de la di-imino-isoindoline ou de la 3-amino-isoindolone
DE10148843A1 (de) * 2001-10-04 2003-04-10 Henkel Kgaa Mittel zum Färben von keratinhaltigen Fasern mit Isophthalaldehyden
DE10241076A1 (de) * 2002-09-05 2004-03-11 Henkel Kgaa Mittel zum Färben von keratinhaltigen Fasern

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2006119821A1 *

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DE102005022789A1 (de) 2006-11-16
WO2006119821A1 (fr) 2006-11-16

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