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
  • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
  • A61K8/41—Amines
  • A61K8/415—Aminophenols
• • 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
  • A61K8/41—Amines
  • A61K8/411—Aromatic amines, i.e. where the amino group is directly linked to the aromatic nucleus
• • 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
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
  • C07C217/78—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
  • C07C217/80—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings
  • C07C217/82—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring
  • C07C217/84—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring the oxygen atom of at least one of the etherified hydroxy groups being further bound to an acyclic carbon atom
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
  • C07C271/06—Esters of carbamic acids
  • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
  • C07C271/26—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring
  • C07C271/28—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring to a carbon atom of a non-condensed six-membered aromatic ring
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
  • C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
  • C07D261/04—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
  • D06P3/02—Material containing basic nitrogen
  • D06P3/04—Material containing basic nitrogen containing amide groups
  • D06P3/08—Material containing basic nitrogen containing amide groups using oxidation dyes

Definitions

• the present invention relates to agents for dyeing keratinic fibers, which contain, especially m-phenylenediamine derivatives, a method for dyeing hair with these agents, as well as some of these m-phenylenediamine derivatives themselves and intermediate products, which are formed during the synthesis of these compounds.
• oxidation dyes play an important role in dyeing keratin fibers, especially human hair.
• dyeing agents contain oxidation dye precursors, so-called developer components and coupling components. Under the influence of oxidizing agents or of oxygen from the air, the developer components form the actual dyes with one another or by coupling with one or more coupling components.
• Special representatives are, for example, p-phenylenediamine, p-toluylenediamine, 2,4,5,6-tetraminopyrimidine, p-aminophenol, N,N-bis(2-hydroxyethyl)-p-phenylenediamine, 2-(2,5-diaminophenyl)-ethanol, 2-(2,5-diaminophenoxy)-ethanol, 1-phenyl-3-carboxyamido-4-amino-pyrazolone-5,4-amino-3-methylphenol, 2-aminomethyl-4-aminophenol, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triamino-4-hydroxypyrimidine and 1,3-N,N′-bis(2-hydroxyethyl)-N,N′-bis(4-aminophenyl)-diamino-propane-2-ol.
• m-phenylenediamine derivatives, napthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenols are used as coupling components.
• 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethylether, m-phenylenediamine, 1-phenyl-3-methyl-pyrazolone-5, 2,4-dichloro-3-aminophenol, 1,3-bis-(2,4-diaminophenoxy)-propane, 2-chlororesorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol and 2-methyl-4-chloro-5-aminophenol are suitable as coupling substances.
• Good oxidation dye precursors should primarily fulfill the following prerequisites. During oxidative coupling, they must form the desired color nuances in a sufficient intensity and fastness. Furthermore, they must have a good affinity for the fibers. Especially in the case of human hair, there must be no noticeable differences between stressed and freshly washed hair (leveling capability). They should be resistant to the effects of light, heat, perspiration, friction and the effects of chemical reducing agents, such as permanent waving liquids. Finally, if they are to be used as hair-dyeing agents, they should not dye the scalp too much and, above all, they should be safe from a toxicological and dermatological point of view. Finally, it should be easily possible to remove the dyeing achieved from the hair by bleaching in the event that it does not meet the individual requirements of the particular person involved and is to be undone.
• Another aspect of the present invention is the use of the m-phenylenediamine derivatives for dyeing keratinic fibers according to the invention.
• Yet another aspect of the present invention is a method for dyeing keratinic fibers, for which the hair-dyeing agent according to the invention is applied on the fibers and, after a period of action, rinsed off once again.
• a further aspect of the present invention are m-phenylenediamine derivatives of Formula (I)
• Still another aspect of the present invention are the first intermediate stages of the synthesis of the m-phenylenediamines according to the invention, selected from the group formed by bis(2-chloroethyl)(2-methoxy-5-methyl-1,3-phenylene) biscarbamate and bis(2-chloroethyl)(2-methoxy-1,3-phenylene) biscarbamate.
• An even further aspect of the present invention are the second intermediate stages of the synthesis of the m-phenylenediamines according to the invention, selected from the group formed by 3,3′-(2-methoxy-5-methyl-1,3-phenylene)bis(1,3-oxazolidine-2-one) and 3,3′-(2-methoxy-1,3-phenylene)bis(1,3-oxazolidine-2-one).
• keratinic fibers are understood to be fur, wool, feathers and, in particular, human hair.
• the oxidation dyes according to the invention are primarily suitable for dyeing keratinic fibers, there is, in principle, no reason why they cannot also be used in other fields, especially in color photography.
• the known acid addition salts can be prepared in the normal way from these. All statements in this publication and, accordingly, the claimed scope of protection therefore relates to the compounds present in free form as well as to their water-soluble, physiologically acceptable salts. Examples of such salts are hydrochlorides, hydrobromides, sulfates, phosphates, acetates, propionates, citrates and lactates. Moreover, the hydrochlorides and sulfates are particularly preferred.
• Methyl, ethyl, propyl, isopropyl, butyl, pentyl and hexyl are examples of C 1 to C 6 alkyl groups, named as substituents in the compounds according to the invention, ethyl and methyl being preferred.
• Hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl or 4-hydroxybutyl are named as preferred C 1 to C 6 monohydroxyalkyl groups, a 2-hydroxyethyl group being particularly preferred.
• m-phenylenediamine derivatives of Formula (I) can be synthesized with the help of conventional organic methods.
• m-phenylenediamine derivatives of Formula (I) are preferred, for which the substituents R 3 and R 4 are identical.
• the substituents R 3 and R 4 represent a 2-hydroxyethyl group or a 3-hydroxypropyl group. A 2-hydroxyethyl group is most particularly preferred.
• the m-phenylenediamine derivatives of Formula (I), in which the R 1 substituent represents a C 1 to C 4 alkyl group are preferred pursuant to the invention.
• m-phenylenediamine derivatives of Formula (I), in which R 2 represents a methyl group may be preferred pursuant to the invention.
• the dyes according to the invention furthermore may contain at least one developer component.
• developer component primary aromatic amines with a further free or substituted hydroxy or amino group in the para or ortho position, diaminopyridine derivatives, heterocyclic hydrazones, 4-amino-pyrazole derivatives, such as 2,4,5,6-tetraminopyrimdine and its derivatives, are usually used.
• a p-phenylenediamine derivate or one of its physiologically acceptable salts may be preferred.
• Particularly preferred are p-phenylenediamine derivates of Formula (E1) in which
• Examples of the C 1 to C 4 alkyl groups are the methyl, ethyl, propyl, isopropyl and butyl groups, ethyl and methyl groups being preferred alkyl groups.
• methoxy or ethoxy groups are C 1 to C 4 alkoxy groups, which are preferred pursuant to the invention.
• a hydroxymethyl group, a 2-hydroxyethyl group, a 3-hydroxypropyl group or a 4-hydroxybutyl group may be named as a preferred example of a C 1 to C 4 hydroxyalkyl group, a 2-hydroxyethyl group being particularly preferred.
• the 1,2-dihydroxyethyl group is a particularly preferred C 2 to C 4 polyhydroxyalkyl group.
• F, Cl or Br atoms are examples of halogen atoms pursuant to the invention, Cl atoms being particularly preferred.
• the further concepts used can be derived from the definitions given here.
• Especially the amino group, C 1 to C 4 monoalkylamino groups, C 1 to C 4 dialkylamino groups, C 1 to C 4 trialkylammonium groups, C 1 to C 4 monohydroxyalkylamino groups, imidazolinium and ammonium are examples of nitrogen-containing groups of Formula (E1).
• Especially preferred p-phenylenediamines of Formula (E1) are selected from p-phenylenediamine, p-toluylenediamine, 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-
• p-phenylenediamine, p-toluylenediamine, 2-( ⁇ -hydroxyethyl)-p-phenylenediamine, 2-( ⁇ , ⁇ -dihydroxyethyl)-p-phenylenediamine and N,N-bis-( ⁇ -hydroxyethyl)-p-phenylenediamine are particularly preferred p-phenylenediamine derivatives of Formula (E1).
• the two-ring developer components which may be used in the dye compositions according to the invention, include, in particular, those corresponding to the following Formula (E2) as well as their physiologically tolerated salts in which
• Preferred, two-ring developer compounds of 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)-tetramethylenediamine, N,N′-diethyl-N,N′-bis-(4′-amino-3′-methylphenyl)-ethylenediamine, bis-(2-hydroxy-5-a
• Particularly preferred two-ring developer components of 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 their physiologically acceptable salts.
• Bis-(2-hydroxy-5-aminophenyl)-methane is a particularly preferred two-ring developer component of Formula (E2).
• p-aminophenol derivative or one of its physiologically salts may be preferred pursuant to the invention.
• Particularly preferred are p-aminophenol derivatives of Formula (E3) in which:
• Preferred p-aminophenol of 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-(diethyl-aminomethyl)-phenol as well as their physiologically acceptable salts.
• p-Aminophenol 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2-( ⁇ , ⁇ -dihydroxyethyl)-phenol and 4-amino-2-(diethyl-aminomethyl)-phenol are especially preferred compounds of Formula (E3).
• the developer component can 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 pyridine, pyrimidine, pyrazole, pyrazole-pyrimidine derivatives and their physiologically acceptable salts.
• heterocyclic developer components such as pyridine, pyrimidine, pyrazole, pyrazole-pyrimidine derivatives and their physiologically acceptable salts.
• Preferred pyridine derivatives are, in particular, the compounds, which are described in the British patents 1,026,978 and 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, which are described in the German patent DE 2 359 399, the Japanese publication JP 02019576 A2 or in the Offenlegungsschrift WO 96/15765, such as 2,4,5,6-tetraminopyrimidine, 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, which are described in the German patents 3 843 892 and 4 133 957 and in the 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-di
• Preferred pyrazole pyrimidine derivatives are, in particular, the derivatives of pyrazole-(1,5-a)-pyrimidine of the following Formula (E4) and its tautomeric forms, provided that there is a tautomeric equilibrium: in which:
• the pyrazole-(1,5-a)-pyrimidines of the above formula may be synthesized by cyclizing starting out from an amino pyrazole or from hydrazine.
• the dyeing agent according to the invention contain at least one further coupling component.
• m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives are used as coupling components.
• Coupling components preferred pursuant to the invention, are
• the hair-dyeing agents according to the invention contain the developer components as well as the coupling components preferably in an amount of 0.005 to 20% by weight and especially 0.1 to 5% by weight, based in each case on the total oxidative dyeing agent. Moreover, developer components and coupling components generally are used in the equal molar amounts. Even though the molar use has proven to be appropriate, a certain excess of individual oxidation dye precursors is not disadvantageous, so that the developer component and coupler component may be contained a molar ratio of 1:0.5 to 1:3 and especially of 1:1 to 1:2.
• the dyeing agents may contain at least one precursor of a dye similar to a natural product.
• precursor of dyes similar to natural products, those indoles and indolines are used, which have at least one hydroxy or amino group, preferably as a substituent in the six-membered ring. These groups may carry further substituents, for example, in the form of an etherification or an esterification of the hydroxy group or an alkylation of the amino group.
• the dyeing agents contain at least one indole derivative and/or indoline derivative.
• Derivatives of 5,6-dihydroxyindolines of Formula (IIa), are particularly suitable as precursors of hair dyes, similar to natural products, in which, independently of one another
• N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline and especially 5,6-dihydroxyindoline are to be emphasized especially.
• derivatives of 5,6-dihydroxyindole of Formula (IIB) are outstandingly suitable as precursors of dyes, similar to natural products, in which, independently of one another,
• N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole and especially 5,6-dihydroxyindole are to be emphasized.
• the indole derivatives and the indoline derivatives may be used as the free bases as well as in the form of their physiologically acceptable salts with organic or inorganic acid, such as the hydrochlorides, the sulfates and hydrobromides.
• the indole derivatives or indoline derivatives are usually contained in these in amounts of 0.05 to 10% by weight and preferably of 0.2 to 5% by weight.
• the indoline derivatives or indole derivatives in dyeing agents in combination with at least one amino acid or one oligopeptide.
• the amino acid advantageously is an ⁇ -amino acid and particularly preferred ⁇ -amino acids are arginine, ornithine, lysine, serine and histidine, especially arginine.
• the dyeing agents according to the invention may contain, in addition to the m-phenylenediamine derivatives of Formula (I) according to the invention, one or more substantive dyes for nuancing.
• substantive dyes are nitrophenylenediamines, nitroaminophenoles, azo dyes, anthraquinone or indophenole.
• Preferred substantive dyes are the compounds known under the international names or trade names as 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 1, 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, as well as 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis-( ⁇ -hydroxyethyl)-amino-2-nitrobenzene, 3-nitro-4-( ⁇ -hydroxyethyl)-aminophenol, 2-(2′-hydroxyethyl)amino-4,6-dinitrophenol, 1-(2′-hydroxy
• agents according to the invention may contain a cationic substantive dye. Particularly preferred in this connection are
• the compounds of Formulas (DZ1), (DZ3) and (DZ5) which are also known under the names Basic Yellow 87, Basic Orange 31 and Basic Red 51, are particularly preferred cationic substantive dyes of group (c).
• the cationic substantive dyes which are sold under the trade name Arianor® are, pursuant to the invention, also particularly preferred cationic substantive dyes.
• the agents of this embodiment according to the invention contain the substantive dyes in amounts of 0.01 to 20% by weight based on the whole of the dyeing agent.
• preparations according to the invention may also be contained in naturally occurring dyes such as, in particular, henna red, henna natural, henna black, chamomile flowers, sandalwood, black tea, buckthorn bark, sage, dogwood, madder root, catechu, sedre and alkanet.
• naturally occurring dyes such as, in particular, henna red, henna natural, henna black, chamomile flowers, sandalwood, black tea, buckthorn bark, sage, dogwood, madder root, catechu, sedre and alkanet.
• the oxidation dye precursors or the substantive dyes in each represent uniform compounds.
• other components may be contained in subordinate amounts in the hair-dyeing agents according to the invention, provided that they do not have a negative effect on the dyeing result or are precluded for other reasons, such as toxicological reasons.
• the dyeing agents according to the invention furthermore may contain all active ingredients, additives and auxiliary materials, which are known for such preparations.
• the dyeing agents contain at least one surfactant, anionic as well as zwitterionic, ampholytic, nonionic and cationic surfactants, in principle, being suitable.
• anionic, surface-active materials suitable for use on the human body, are suitable as anionic surfactants in the preparation according to the invention. They are characterized, by a water-solubilizing, anionic group, such as a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group with about 10 to 22 carbon atoms.
• anionic group such as a carboxylate, sulfate, sulfonate or phosphate group
• a lipophilic alkyl group with about 10 to 22 carbon atoms.
• glycol ether groups or polyglycol ether groups, ester, ether and amide groups, as well as hydroxyl groups may be contained in the molecule.
• suitable anionic surfactants always in the form of the sodium, potassium and ammonium salts, as well as the mono-, di- and trialkylanol ammonium salts with 2 or 3 carbon atoms in the alkanol group, are
• nonionic surfactants contain, for example, a polyol group, a polyalkylene glycol ether group or a combination of a polyol ether and a polyglycol ether group.
• a polyol group a polyalkylene glycol ether group or a combination of a polyol ether and a polyglycol ether group.
• Such compounds are, for example,
• Alkyl polyglycosides of the general formula R 1 O-(Z) x are preferred nonionic surfactants. These compounds are characterized by the following parameters.
• the R 1 alkyl group contains 6 to 22 carbon atoms and may be linear as well as branched. Primary linear aliphatic groups and aliphatic groups, which are methyl-branched in the 2 position, are preferred. Such alkyl groups are, for example, 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-stearyl, 1-octyl, 1-decyl, 1-lauryl, 1-myristyl being particularly preferred. When so-called “oxo alcohols” are used as starting materials, compounds with an odd number of carbon atoms in the alkyl chain predominate.
• Alkylpolyglycosides which can be used pursuant to the invention, may, for example, have only one particular R 1 alkyl group.
• these compounds are synthesized starting from natural fats or oils or mineral oils. In this case, mixtures, corresponding to the starting compounds or to the respective working up of these compounds, are present as R alkyl groups.
• alkylpolyglycosides are those, in which R 1 consists essentially of
• Any monosaccharides or oligosaccharides can be used as the Z sugar component.
• sugars with 5 to 6 carbon atoms and the corresponding oligosaccharides are used.
• sugars are glucose, fructose, galactose, arabinose, ribose, xylose, lyxose, allose, altrose, mannose, glucose, idose, talose and sucrose, glucose, fructose, galactose, arabinose and sucrose being preferred and glucose being particularly preferred.
• Alkyl polyglycosides which can be used pursuant to the invention, contain, on the average 1.1 to 5 sugar units. Alkyl polyglycosides, in which x has values of 1.1 to 1.6, are preferred. Alkylglycosides, in which x has a value from 1.1 to 1.4, are particularly preferred.
• the alkyl glycoside can also improve the fixation of a fragrance component on the hair.
• the effect of a perfume oil is to go beyond the duration of the hair treatment, someone of ordinary skill in the art will therefore preferably resort to this class of substances as a further component of the preparation according to the invention.
• alkoxylated homologs of said alkylpolyglycosides can also be used pursuant to the invention. These homologs may, on the average, contain up to 10 ethylene oxide and/or propylene units per alkyl glycoside units.
• Zwitterionic surfactants in particular may be used as co-surfactants.
• Zwitterionic surfactants are those surface-active compounds, which contain, in the molecule at least one quaternary ammonium group and at least one —COO ( ⁇ ) - or —SO 3 ( ⁇ ) group.
• Particularly suitable as zwitterionic surfactants are the so-called betaines, such as the N-alkyl-N,N-dimethylammonium glycinates, for example, the coconut alkyl-dimethylammonium glycinate, N-acyl-aminopropyl-N,N-dimethylammonium glycinates, for example, the coconut acylaminopropyl-dimethylammonium glycinate, and 2-alkyl-3-carboxylmethyl-3-hydroxyethyl imidazolines with, in each case 8 to 18 carbon atoms in the alkyl or acyl group, as well as the coconut acylaminoethyl hydroxyethylcarboxymethyl glycinate.
• the fatty acid amide derivative known under the INCI name as cocoamidopropyl betaine, is a preferred zwitterionic surfactant.
• Ampholytic surfactants are likewise especially suitable as co-surfactants.
• Ampholytic surfactants are understood to be surface-active compounds, which contain, aside from a C 8 -C 18 alkyl or acyl group, at least one free amino group and at least one —COOH— or —SO 3 H group in the molecule and are capable of forming internal salts.
• Suitable ampholytic surfactants are, for example, N-alkyl glycines, N-alkylpropionic acids, N-alkylamino butyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropyl glycines, N-alkyl taurines, N-alkyl sarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids with, in each case, 8 to 18 carbon atoms in the alkyl group.
• the N-coconut alkyl amino propionate, the coconut acylamino ethylamino propionate and the C 12-18 acyl sarcosine are particularly preferred ampholytic surfactant.
• surfactants especially of the quaternary ammonium compounds, esterquats and the amidoamines type, are used as cationic surfactant.
• Ammonium halides are preferred quaternary ammonium compounds. They include, in particular, the chlorides and bromides, such as the alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, such as, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride, as well as the imidazolium compounds, known under the INCI name as Quaternium 27 and Quaternium 83.
• the long alkyl chains of the surfactants named above have 10 to 18 carbon atoms.
• Esterquats are known materials, which contain at least one ester function and at least one quaternary ammonium group as structural element. Quaternized ester salts of fatty acids with triethanolamine, quaternized ester salts of fatty acids with diethanolalkylamines and quaternized ester salts of fatty acids with 1,2-dihydroxypropyldialkylamines are preferred esterquats. Such products are sold, for example, under the trade names of Stepanex®, Dehyquart® and Armocare®.
• Armocare® VGH-70 and N,N-bis(2-palmitoyloxyethyl)dimethylammonium chloride, as well as Dehyquart® F-75 and Dehyquart® AU-35 are examples of such esterquats.
• the aklyamidoamines usually are synthesized by amidation of natural or synthetic fatty acids and fatty acid fractions with dialkylaminoamines.
• the stearamidopropyl dimethylamine obtainable commercially under the name Tegoamide® 18, is a compound of this group of substances, which is particularly suitable pursuant to the invention.
• the quaternized protein hydrolysates represent further cationic surfactants, which may be used pursuant to the invention.
• Cationic silicone oils such as the commercially available 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) as well as Abil®-Quat 3270 and 3272 (Manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, Quaternium-80), are also suitable pursuant to the invention.
• the commercial product Glucquat®100 which, according to INCI name, is a “Lauryl Methyl Gluceth-10 Hydroxypropyl Dimonium Chloride”, represents an example of a quaternary sugar derivative, which can be used as a cationic surfactant.
• the compounds with alkyl groups, used as surfactants may be uniform substances. As a rule, however, during the production of these materials, it is usually preferred to start out from natural vegetable or animal raw materials, so that substance mixtures with different alkyl chains, the lengths of which depend on the respective raw materials, are obtained.
• homologs of a “normal” distribution are understood to be mixtures of homologs, which are obtained from the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates as catalysts.
• homologs of a narrowed distribution are obtained when, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids or alkaline earth metal oxides, hydroxides or alcoholates are used as catalysts. The use of products with a narrowed distribution of homologs may be preferred.
• the dyeing agent according to the invention may contain further active ingredients, auxiliary materials and additives, such as
• the agents according to the invention contain the dyeing agent precursors preferably in a suitable aqueous, alcoholic or aqueous-alcoholic carrier.
• a suitable aqueous, alcoholic or aqueous-alcoholic carrier for the purpose of dyeing hair, such carriers are, for example, creams, emulsions, gels or also surfactant-containing foaming solutions, such as shampoos, foaming aerosols or other preparations, which are suitable for application on the hair.
• a suitable aqueous, alcoholic or aqueous-alcoholic carrier are, for example, creams, emulsions, gels or also surfactant-containing foaming solutions, such as shampoos, foaming aerosols or other preparations, which are suitable for application on the hair.
• surfactant-containing foaming solutions such as shampoos, foaming aerosols or other preparations, which are suitable for application on the hair.
• aqueous-alcoholic solutions are aqueous solutions containing 3 to 70% by weight of a C 1 -C 4 alcohol, especially ethanol or isopropanol.
• the agents according to the invention may contain further organic solvents, such as methoxybutanol, benzyl alcohol, ethyl diglycol or 1,2-propylene glycol. In this connection, all water-soluble organic solvents are preferred.
• the actual oxidative dyeing of the fibers can basically take place with oxygen from the air.
• a chemical oxidizing agent is used, especially when human hair is to be brightened as well as dyed.
• Persulfates, chlorites and, in particular, hydrogen peroxide or its addition products with urea, melamin and sodium borates come into consideration as oxidizing agents.
• the oxidation dyeing agent can also be applied on the hair together with a catalyst, which activates the oxidation of the dye precursors, for example, with oxygen from the air.
• Metal ions, iodides, quinones or certain enzymes are such catalysts.
• Zn 2+ , Cu 2+ , Fe 2+ , Fe 3+ , Mn 2+ , Mn 4+ , Li + , Mg 2+ , Ca 2+ and Al 3+ , for example, are suitable metal ions, Zn 2+ , Cu 2+ , Mn 2+ being particularly suitable.
• the metal ions may be used in the form of any physiologically acceptable salts or in the form of a complex compound. Acetates, sulfates, halides, lactates and tartrates are preferred salts. The use of these metal salts can accelerate the coloration and selectively influence the color shade.
• Suitable enzymes are, for example, peroxidases, which can clearly intensify the action of small amounts of hydrogen peroxide. Furthermore, those enzymes are suitable pursuant to the invention, which oxidize the oxidation dye precursor directly with the help of oxygen from the air, such as the laccases, or produce hydrogen peroxide in situ in small amounts and, in this way, activate the oxidation of dye precursors biocatalytically.
• Particularly suitable catalysts for the oxidation of the dye precursors are the so-called 2-electron oxidoreductases in combination with the substrates specific for this purpose, such as
• the actual hair-dyeing agent is prepared advisably immediately before use by mixing the preparation of the oxidizing agent with the preparation containing the dye precursors.
• the thereby resulting, ready-for-use hair-dyeing preparation preferably should have a pH ranging from 6 to 12.
• the use of the hair-dyeing agents in a weakly alkaline medium is particularly preferred.
• the application temperatures may range from 150 and 40° C. After a period of action of 5 to 45 minutes, the hair-dyeing agent is removed by rinsing from the hair, which is to be dyed. Subsequent washing with a shampoo may be omitted if a carrier, containing a surfactant in an appropriate amount, such as a dyeing shampoo, was used.
• the preparation with the dye precursor may also be applied on the hair without previously being mixed with the oxidizing component. After a period of action of 20 to 30 minutes, optionally after an intermediate rinsing, the oxidizing component is applied. After a further period of action of 10 to 20 minutes, the hair is then rinsed and, if desired, shampooed.
• the corresponding agent is adjusted to a pH of about 4 to 7.
• oxidation by air is aimed for at first, the agent applied preferably having a pH of 7 to 10.
• the use of acidically adjusted peroxidisulfate solutions as oxidizing agent may be preferred.
• 2,6-Dinitro-4-methylanisole 100 g
• 1.35 L of methanol, 150 mL of water and 1 g of Pd/C (5%) were placed in an autoclave and hydrogenated for 12 hours at 50° C. with hydrogen at a pressure of 50 bar.
• the autoclave was allowed to cool down and the formulation was poured into 1.0 L of half concentrated HCl.
• the catalyst was filtered off and the filtrate was evaporated to dryness in a rotary evaporator and dried under vacuum overnight.
• 2,6-Diamino-4-methylanisole dihydrochloride 56 g
• 134 g of calcium carbonate 134 g
• 80 g of 2-chloroethyl chloroformate were added and the formulation was stirred for a further 4 hours at this temperature and then allowed to cool down, the mineral salts being filtered off.
• the filtrate was poured into ice water and the resulting light brown crystals were filtered off and dried under vacuum.
• 2,6-Dinitro-4-chloroanisole (23.3 g), 450 mL of ethanol, 50 mL of water, 9.8 g of potassium acetate and 0.1 g of Pd/C (5%) were added to an autoclave and hydrogenated for 12 hours at 50° C. with hydrogen under a pressure of 50 bar. Subsequently, the autoclave was allowed to cool down, the catalyst was filtered was off and the filtrate evaporated to dryness in a rotary evaporator. The residue was subsequently distilled in a Kugelrohr.
• a cream base For preparing the dyeing cream, 50 g of a cream base were weighed into a 250 mL beaker and melted at 80° C.
• the cream base used had the following formulation: Hydrenol ® D 1 17.0% by weight Lorol ® tech. 2 4.0% by weight Texapon ® NSO 3 40.0% by weight Dehyton ® K 4 25.0% by weight Eumulgin ® B2 5 1.5% by weight water 12.5% by weight 1 C 16-18 Fatty alcohol (INCI name: Cetearyl alcohol) (Cognis) 2 C 12-18 Fatty alcohol (INCI name: Coconut alcohol) (Cognis) 3 Sodium salt of lauryl ether sulfate (approx.
• the dissolved dye precursors were incorporated consecutively into the hot cream. Subsequently, distilled water was added to a total weight of 97 g and the pH was adjusted with ammonium hydroxide to a value of 9.5. After adding distilled water to 100 g, the formulation was stirred until cool (below 30° C.), a homogeneous cream being formed.
• a hair strand (turned 80% grey; 330 mg to 370 mg in weight) was added to each of the mixtures so obtained. Subsequently, the mixtures and the hair strands were added to a clock glass and the hair strands were embedded in the dyeing cream. After a 30 minute ( ⁇ 1 minute) period of action at room temperature, the hair strands were removed and washed with aqueous Texapon® EVR solutions 9 , until the excess dye had been removed. The hair strands were dried in air and their color shade was determined under a daylight lamp (color testing device HE240A) and noted (Taschenlexikon der Weg Kon of Colors), A. Kornerup and J. H.
• Formulations 1 to 8 were mixed with the above-described oxidizing agent (item 2.1) and the resulting application preparation was applied on strands (Kerling, natural white). After a period of action of 30 minutes at room temperature, the fibers were thoroughly rinsed with water, dried with a blower and the colorations were evaluated. The following results were obtained: Formulation Number Color Results 1 intensive wine red 2 intensive violet 3 intensive orange red 4 blackish red 5 dark violet 6 dark ruby 7 dark aubergine 8 luminous orange red

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