EP1542982A1 - Produits de coloration capillaire contenant des derives de m-phenylenediamine en tant que composants copulants - Google Patents

Produits de coloration capillaire contenant des derives de m-phenylenediamine en tant que composants copulants

Info

Publication number
EP1542982A1
EP1542982A1 EP03750569A EP03750569A EP1542982A1 EP 1542982 A1 EP1542982 A1 EP 1542982A1 EP 03750569 A EP03750569 A EP 03750569A EP 03750569 A EP03750569 A EP 03750569A EP 1542982 A1 EP1542982 A1 EP 1542982A1
Authority
EP
European Patent Office
Prior art keywords
group
amino
ylphenyl
alkyl group
formula
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Withdrawn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
EP03750569A
Other languages
German (de)
English (en)
Inventor
Georg KNÜBEL
Bernd Meinigke
Horst Höffkes
Ralph Nemitz
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 EP1542982A1 publication Critical patent/EP1542982A1/fr
Withdrawn legal-status Critical Current

Links

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
    • A61K8/411—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

Definitions

  • the present invention relates to agents for dyeing keratin fibers which contain special m-phenylenediamine derivatives in which one of the two nitrogen atoms is part of a saturated heterocycle, a process for dyeing hair using these agents, and some of these m-phenylenediamine derivatives themselves and intermediates which arise in the manufacture of these connections.
  • oxidation dyes For dyeing keratin fibers, especially human hair, the so-called oxidation dyes play a preferred role because of their intense colors and good fastness properties.
  • colorants contain oxidation dye precursors, so-called developer components and
  • the developer components form the actual dyes under the influence of oxidizing agents or of atmospheric oxygen with one another or under coupling with one or more coupler components.
  • M-Phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenols are generally used as coupler components.
  • Particularly suitable coupler substances are 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resor- cinmonomethyl ether, m-phenylenediamine, 1-phenyl-3-methyl-pyrazolon-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.
  • Good oxidation dye precursors should primarily fulfill the following prerequisites: they must develop the desired color shades with sufficient intensity and authenticity in the oxidative coupling. You must also have a good ability to draw on the fiber, especially in the case of human hair, there must be no noticeable differences between damaged and newly grown hair (leveling ability). They should be resistant to light, heat, sweat, friction and the influence of chemical reducing agents, e.g. Perm liquids. After all, if they are used as hair dye, they should not stain the scalp too much, and above all they should be harmless from a toxicological and dermatological point of view. Furthermore, the coloring achieved should be easily removed from the hair again by bleaching, if it does not correspond to the individual wishes of the individual and is to be reversed.
  • Oligoaminopyrimidine derivatives intense brilliant shades with very good fastness properties.
  • the present invention therefore firstly relates to agents for dyeing keratin fibers, in particular human hair, containing at least one m-phenylenediamine derivative of the formula (I) or one of its physiologically tolerable salts in a cosmetically acceptable carrier as a coupler component
  • R 1 represents a hydrogen atom, a halogen atom, a d to C 4 alkyl group, a d to C 4 monohydroxyalkyl group, a C 2 to C 4 polyhydroxyalkyl group, a Ci to C 4 aminoalkyl group, a d - to C -alkoxy- (d- to C 4 ) -alkyl group or ad- to C 4 -dialkylamino- (Cr to C 4 ) -alkyl group,
  • R 2 and R 3 are independently a hydrogen atom, a C to C 4 - alkyl group, a C 2 - to C 4 -monohydroxyalkyl group, a C 3 - to C - polyhydroxyalkyl group, a C to C alkoxy (C to C) alkyl group or a C r to C 4 aminoalkyl group and
  • X stands for a saturated, 5-, 6- or 7-membered heterocycle which has at least one nitrogen atom and optionally another heteroatom selected from oxygen, sulfur or nitrogen, the heterocycle being bonded to the aromatic ring system via a nitrogen atom , and the heterocycle can optionally carry up to two substituents other than hydrogen, which are selected from a halogen atom, a C to C 4 alkyl group, a d to C 4 monohydroxyalkyl group, a C 2 to C 4 polyhydroxyalkyl group, one Ci to C 4 aminoalkyl group, ad to C 4 alkoxy (C to C 4 ) alkyl group or ad to C 4 dialkylamino (d to C 4 ) alkyl group.
  • Keratinic fibers are to be understood according to the invention to mean furs, wool, feathers and in particular human hair.
  • Oxidation dyes are primarily suitable for dyeing keratin fibers, in principle there is nothing to prevent them from being used in other areas, particularly in color photography.
  • the known acid addition salts can be prepared from them in the usual way. All statements in this document and accordingly the claimed scope of protection therefore relate both to the compounds present in free form and to their water-soluble, physiologically tolerable salts. Examples of such salts are the hydrochlorides, the hydrobromides, the sulfates, the phosphates, the acetates, the propionates, the citrates and the lactates. The hydrochlorides and the sulfates are particularly preferred.
  • Examples of the d- to d-alkyl groups mentioned as substituents in the compounds according to the invention are the groups methyl, ethyl, propyl, isopropyl and butyl. Ethyl and methyl are preferred alkyl groups.
  • Preferred d- to C 4 -alkoxy groups are the methoxy and ethoxy groups.
  • Further preferred examples of a - to C 4 -monohydroxyalkyl group are a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group.
  • a 2-hydroxyethyl group is particularly preferred.
  • a particularly preferred C 2 - to C 4 - polyhydroxyalkyl group is the 1,2-dihydroxyethyl group.
  • Examples of halogen atoms according to the invention are F, CI or Br atoms, Cl atoms are very particularly preferred. The other terms used are derived from the definitions given here.
  • the m-phenylenediamine derivatives of the formula (I) can be prepared using conventional organic methods. As an example, reference is made to the experimental procedures in the context of the exemplary embodiments.
  • the base body of the m-phenylenediamine derivatives of the formula (I) can be synthesized, for example, by reacting 3-fluoronitrobenzene with the corresponding saturated nitrogen-containing heterocycles.
  • the m-phenylenediamine derivatives of the formula (I) can therefore be preferred, the base structure of which can be prepared by reacting 3-fluomitrobenzene with one of the following compounds, which are characterized here with the aid of their chemical abstract number: CA no .: 100158-62-1, CA no .: 1003-28-7, CA no.102308-48-5, CA no.104-89-2, CA no.1064678 -13-9, CA No.:109-05-7, CA No.:109967-01-3, CA No.:110-89-4, CA No.:111- 49-9, CA.
  • CA No.: 110-85-0 CA No.:110-91-8, CA No.:116143-27-2, CA No.:122894-56-8, CA No.:123-57-9 , CA no .: 128454-20-6, CA no .: 130861-85-7, CA no .: 13961-37-0, CA no .: 141-91-3, CA no .: 142-63-2, CA No.:142-64-3, CA No.:171351-20- 5, CA No.:21655-48-1, CA No. : 25154-38-5, CA no. : 2815-34-1, CA no .: 28631-79-0, CA no .: 393781-72-1, CA no.
  • CA no .: 4554-26-1 CA no .: 6091-62-9, CA no. : 6284-84-0, CA No.:6485- 55-8, CA No. : 74879-18-8, CA no .: 75336-85-5, CA no. : 75336-86-6, CA no. : 75336-89-9 and CA no. : 84477-72-5.
  • m-phenylenediamine derivatives of the formula (I) are already known from the prior art. However, there is no indication in the literature that these can be used as coupler components in hair dyes. Structurally distantly related m-phenylenediamine derivatives are already known from DE-A1-26 22 451. There, bis-substituted benzenes are described symmetrically with secondary amines, including 1,3-bis (piperidin-1-yl) benzene.
  • this application of the prior art gives the person skilled in the art no suggestion whatsoever of using the m-phenylenediamine derivatives now claimed as coupler components. Rather, the synthesis strategy given there does not permit the production of the m-phenylenediamine derivatives now claimed and thus leads away from the subject matter of the present application.
  • the m-phenylenediamine derivatives of the formula (I) in which R 1 represents a hydrogen atom, a halogen atom, a C to C 4 alkyl group or a d to C 4 monohydroxyalkyl group can be preferred.
  • R 1 particularly preferably represents a hydrogen atom, a chlorine atom, a methyl group or a 2-hydroxyethyl group.
  • M-Phenylenediamine derivatives of the formula (I) in which R 1 represents a hydrogen atom are very particularly preferred.
  • the m-phenylenediamine derivatives of the formula (I) can furthermore be preferred in which R 2 and R 3 independently of one another represent a hydrogen atom, a d- to C -alkyl group or a d- to C 4 -monohydroxyalkyl group.
  • the substituents R 2 and R 3 are particularly preferably independently of one another a hydrogen atom, a methyl group or a 2-hydroxyethyl group.
  • R 2 and R 3 each represent a methyl group, one of the radicals R 2 or R 3 represents a 2-hydroxyethyl group and the other of the
  • R 2 or R 3 are hydrogen or both R 2 and R 3 are each hydrogen.
  • m-phenylenediamine derivatives of the formula (I) may be preferred in which X represents a pyrrolidin-1-yl group, an imidazolidin-1-yl group, a piperidin-1-yl group, a piperazin-1-yl group, a morpholine group 4-yl group, a hexahydroazepin-1-yl group or a hexahydro-1,4-oxazepin-4-yl group.
  • their derivatives substituted with an alkyl group, in particular a methyl group may also be preferred according to the invention. If the heterocycle has a second nitrogen atom, the substituted derivatives in which the substituent is bonded to the second nitrogen atom can be particularly preferred.
  • M-Phenylenediamine derivatives of the formula (I) which are particularly preferred according to the invention are selected from the group formed by 3-pyrrolidin-1-ylaniline, 3-piperidin-1-ylaniline, 3-morpholin-4-ylaniline, 3- (4- Methylpiperazin-1-yl) aniline, N, N-dimethyl-3- (pyrrolidin-1-yl) aniline, 2 - [(3-morpholin-4-ylphenyl) amino] ethan-1-ol, 2 - [(3rd -Piperidin-1-ylphenyl) amino] ethan-1-ol and 2 - [(3-pyrrolidin-1-ylphenyl) amino] -ethan-1-ol.
  • the colorants according to the invention can also contain at least one developer component.
  • G 1 represents a hydrogen atom, a d- to C 4 alkyl, a d- to C 4 - monohydroxyalkyl radical, a C 2 - to C 4 polyhydroxyalkyl radical, a (d-C) alkoxy (C 4 to C ) alkyl radical, a 4'-aminophenyl radical or ad- 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, ad to C 4 alkyl, ad to C monohydroxyalkyl, C 2 to C polyhydroxyalkyl, (d to C) alkoxy (d to C 4 ) alkyl radical or ad- 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, ad- to C -alkyl radical, a Ci- to C 4 -monohydroxyalkyl radical, a C 2 - to C -polyhydroxyalkyl radical, one d- to C -hydroxyalkoxy, a C to C - acetylaminoalkoxy, a C r to C 4 - mesylaminoalkoxy or a d to C 4 - carbamoylaminoalkoxy;
  • a halogen atom such as a chlorine, bromine, iodine or fluorine atom
  • G 4 represents a hydrogen atom, a halogen atom or a d- to C 4 -alkyl radical or if G 3 and G 4 are in the ortho position to one another, they can together form a bridging ⁇ , ⁇ -alkylenedioxo group, such as, for example, an ethylenedioxy group.
  • Ci to C alkyl radicals mentioned as substituents in the compounds according to the invention are the groups methyl, ethyl, propyl, isopropyl and butyl. Ethyl and methyl are preferred alkyl radicals.
  • C to C 4 alkoxy radicals preferred according to the invention are, for example, a methoxy or an ethoxy group.
  • a C to C -hydroxyalkyl group a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group can be mentioned.
  • a 2-hydroxyethyl group is particularly preferred.
  • a particularly preferred C 2 - to C 4 polyhydroxyalkyl group containing 1, 2- dihydroxyethyl is.
  • halogen atoms are F, CI or Br atoms, Cl atoms are very particularly preferred. According to the invention, the other terms used are derived from the definitions given here.
  • nitrogen-containing groups of the formula (E1) are especially the amino groups, monoalkylamino groups d- to C, D to C 4 dialkylamino, d- to C - trialkylammonium, C 4 to C -Monohydroxyalkylamino phenomenon, imidazolinium and ammonium.
  • Particularly preferred p-phenylenediamines of the formula (E1) are selected from p-phenylenediamine, p-toluenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2 , 6-diethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, N, N-dipropyl-p-phenylenediamine, 4 -Amino-3-methyl- (N, N-diethyl) aniline, N, N-bis- ( ⁇ -hydroxyethyl) -p-phenylenediamine, 4-N, N-bis- ( ⁇ -hydroxyethyl) -amino-2 - methylaniline,
  • p-phenylenediamine derivatives of the formula (E1) which are particularly preferred are p-phenylenediamine, p-toluenediamine, 2- ( ⁇ -hydroxyethyl) -p-phenylenediamine, 2- ( ⁇ , ⁇ -dihydroxyethyl) -p-phenylenediamine and N, N bis (.beta.-hydroxyethyl) -p-phenylenediamine.
  • binuclear 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 coloring compositions according to the invention, one can name in particular the compounds which correspond to the following formula (E2) and their physiologically tolerable salts:
  • Z 1 and Z 2 independently of one another represent a hydroxyl or NH 2 radical, which is optionally substituted by a d- to C -alkyl radical, by a d- to C -hydroxyalkyl radical and / or by a bridging Y or the optional part of a bridging ring system
  • the bridging Y represents an alkylene group having 1 to 14 carbon atoms, such as, for example, a linear or branched alkylene chain or an alkylene ring, which is formed by one or more nitrogen-containing groups and / or one or more heteroatoms such as oxygen, sulfur or Nitrogen atoms may be interrupted or terminated and may be substituted by one or more hydroxyl or C 1 -C 8 -alkoxy radicals, or a direct bond,
  • G 5 and G 6 independently of one another represent a hydrogen or halogen atom, a d- to C -alkyl radical, a C to C -monohydroxyalkyl radical, a C 2 - to C -polyhydroxyalkyl radical, a d- to C 4 -aminoalkyl radical or a direct one Connection to bridge Y,
  • G 7 , G 8 , G 9 , G 10 , G 11 and G 12 independently of one another represent a hydrogen atom, a direct bond to bridge Y or a d- to C 4 -alkyl radical, with the provisos that the compounds of the formula ( E2) contain only one bridge Y per molecule and - the compounds of the formula (E2) contain at least one amino group which carries at least one hydrogen atom.
  • the substituents used in formula (E2) are defined analogously to the above statements.
  • Preferred dinuclear developer components of the formula (E2) are in particular: N, N'-bis (ß-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1, 3-diamino-propan-2-ol, N, N'-bis (ß-hydroxyethyl) -N, N'-bis (4'-aminophenyl) ethylenediamine, N, N'-bis (4-aminophenyl) tetramethylene diamine, N, N'-bis - (ß-hydroxyethyl) -N, N'-bis (4-aminophenyl) tetramethylene diamine, N, N'-bis (4-methylaminophenyl) tetramethylene diamine, N, N'-diethyl-N, N ' bis (4'-amino-3'-methylphenyl) ethylenediamine, bis (2-hydroxy-5-aminophenyl) methane, 1, 3-
  • Very particularly preferred dual-core developer components of the formula (E2) are N, N'-bis ( ⁇ -hydroxyethyl) -N, N'-bis- (4'-aminophenyl) -1, 3-diamino-propan-2-ol, Bis (2-hydroxy-5-aminophenyl) methane, 1,3-bis (2,5-diaminophenoxy) propan-2-ol, N, N'-bis (4'-aminophenyl) -1, 4-diazacycloheptane and 1,10-bis- (2 ', 5'-diaminophenyl) -1,4,7,10-tetraoxadecane or one of their physiologically acceptable salts.
  • P-Aminophenol derivatives of the formula (E3) are particularly preferred
  • G 13 represents a hydrogen atom, a halogen atom, a C to C 4 alkyl radical, a d to C 4 monohydroxyalkyl radical, a C 2 to d polyhydroxyalkyl radical, a (d to C) alkoxy- (d- to C 4 ) -alkyl radical, ad- to C -aminoalkyl radical, a hydroxy- (C to C 4 ) -alkylamino radical, a C r to C -hydroxyalkoxy radical, a C to C 4 - Hydroxyalkyl- (d-to C 4 ) -aminoalkyl or a (di-C to C 4 -alkylamino) - (C to C 4 ) -alkyl, and
  • G 14 represents a hydrogen or halogen atom, a C to C 4 alkyl radical, a Cr to C 4 monohydroxyalkyl radical, a C 2 to C polyhydroxyalkyl radical, a (C to C 4 ) alkoxy (d to C) 4 ) -alkyl radical, a C to C 4 -aminoalkyl radical or ad- to C-cyanoalkyl radical,
  • G 15 represents hydrogen, ad to C 4 alkyl, ad to C 4 monohydroxyalkyl, C 2 to C 4 polyhydroxyalkyl, phenyl or benzyl, and
  • G 16 represents hydrogen or a halogen atom.
  • Preferred p-aminophenols of the formula (E3) are in particular p-aminophenol, N-methyl-p-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 2-hydroxymethylamino-4-aminophenol, 4 -Amino-3-hydroxymethylphenol, 4-amino-2- (ß-hydroxyethoxy) phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethyl-phenol, 4-amino -2-aminomethylphenol, 4-amino-2- (ß-hydroxyethyl-aminomethyl) phenol, 4-amino-2- ( ⁇ , ß-dihydroxyethyl) phenol, 4-amino-2-fluorophenol, 4-amino-2 -chlorophenol, 4-amino-2,6-dichlorophenol, 4-amino-2- (diethylaminomethyl) phenol and their physiologically tolerable salts
  • Very particularly preferred compounds of the formula (E3) are p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- ( ⁇ , ⁇ -dihydroxyethyl) phenol and 4-amino- 2- (diethylaminomethyl) -phenol.
  • the developer component can be selected from o-aminophenol and its derivatives, such as, for example, 2-amino-4-methylphenol, 2-amino-5-methylphenol or 2-amino-4-chlorophenol.
  • the developer component can be selected from heterocyclic developer components, such as, for example, the pyridine, pyrimidine, pyrazole, pyrazole-pyrimidine derivatives and their physiologically tolerable salts.
  • Preferred pyridine derivatives are, in particular, the compounds described in patents GB 1 026 978 and GB 1 153 196, such as 2,5-diamino-pyridine, 2- (4'-methoxyphenyl) amino-3-aminopyridine , 2,3-diamino-6-methoxy-pyridine, 2- (ß-
  • Methoxyethyl amino-3-amino-6-methoxy-pyridine and 3,4-diamino-pyridine.
  • Preferred pyrimidine derivatives are, in particular, the compounds which are described in German patent DE 2 359 399, Japanese laid-open patent publication JP 02019576 A2 or in laid-open publication 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- (ß-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
  • Triaminopyrazole 1-methyl-3,4,5-triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole and 3,5-diamino-4- ( ⁇ -hydroxyethyl) amino-1-methylpyrazole.
  • 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 there is a tautomeric equilibrium:
  • G 17 , G 18 , G 19 and G 20 independently represent a hydrogen atom, ad- to C 4 -alkyl residue, an aryl residue, ad- to C -hydroxyalkyl residue, a C 2 - to C -polyhydroxyalkyl residue a ( C to C 4 ) -alkoxy- (d- to C) -alkyl radical, a C to C 4 -aminoalkyl radical which can optionally be protected by an acetyl-ureide or a sulfonyl radical, a (Cr to C 4 ) - Alkylamino (C to C) alkyl, a di - [(d to C 4 ) alkyl] - (C to C 4 ) aminoalkyl, the dialkyl radicals optionally being a carbon cycle or a heterocycle with 5 or 6 chain links form a d- to d-hydroxyalkyl or a di- (d- to C) - [
  • the pyrazole [1, 5-a] pyrimidines of the above formula (E4) can be prepared as described in the literature by cyclization starting from an aminopyrazole or from hydrazine.
  • the colorants according to the invention contain at least one further coupler component.
  • M-Phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives are generally used as coupler components.
  • Particularly suitable coupler substances are 1-naphthol, 1,5-, 2,7- and 1, 7- Dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 1-phenyl-3-methyl-pyrazolon-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-ch
  • Coupler components preferred according to the invention are m-aminophenol and its derivatives such as 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 -Dichlor-3-aminophenol, o-aminophenol and its derivatives, m-diaminobenzene and its derivatives such as, for example, 2,4
  • o-diamino benzene and its derivatives such as 3,4-diamino benzoic 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,
  • Morpholine derivatives such as, for example, 6-hydroxybenzomorpholine and 6-amino-benzomo holin, Quinoxaline derivatives such as 6-methyl-1, 2,3,4-tetrahydroquinoxaline,
  • Indole derivatives such as 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole,
  • Pyrimidine derivatives such as 4,6-diaminopyrimidine, 4-amino-2,6-dihydroxypyrimidine, 2,4-diamino-6-hydroxypyrimidine, 2,4,6-trihydroxypyrimidine, 2-
  • Methylenedioxybenzene derivatives such as 1-hydroxy-3,4-methylenedioxybenzene, 1-amino-3,4-methylenedioxybenzene and 1- (2'-hydroxyethyl) - amino-3,4-methylenedioxybenzene.
  • Coupler components which are particularly preferred according to the invention are 1-naphthol, 1, 5-, 2,7- and 1, 7-dihydroxynaphthalene, 3-aminophenol, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, resorcinol, 4-chlororesorcinol , 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol and 2,6-dihydroxy-3,4-dimethylpyridine.
  • Couplers / developer combinations proved:
  • the colorants can contain at least one precursor of a nature-analog dye.
  • Indoles and indolines which have at least one hydroxyl or amino group, preferably as a substituent on the six-membered ring, are preferably used as precursors of nature-analogous dyes. exhibit. These groups can carry further substituents, e.g. B. in the form of etherification or esterification of the hydroxy group or an alkylation of the amino group.
  • the colorants contain at least one indole and / or indoline derivative.
  • R 1 represents hydrogen, a dC 4 -alkyl group or a CC -hydroxy-alkyl group
  • R 2 stands for hydrogen or a -COOH group, where the -COOH group can also be present as a salt with a physiologically compatible cation
  • R 3 represents hydrogen or a dd-alkyl group
  • R 4 stands for hydrogen, a dC 4 alkyl group or a group -CO-R 6 , in which R 6 stands for a CrC 4 alkyl group, and
  • R 5 stands for one of the groups mentioned under R 4 , as well as physiologically tolerable 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 the 5 6-Dihydroxyindolin.
  • R 1 represents hydrogen, a CrC -alkyl group or a dC -hydroxyalkyl- group
  • R 2 stands for hydrogen or a -COOH group, where the -COOH group can also be present as a salt with a physiologically compatible cation
  • R 3 represents hydrogen or a dd-alkyl group
  • R 4 stands for hydrogen, a dC -alkyl group or a group -CO-R 6 , in which R 6 stands for a CrC -alkyl group, and
  • R 5 stands for one of the groups mentioned under R 4 , as well as physiologically tolerable salts of these compounds with an organic or inorganic acid.
  • Particularly preferred derivatives of indole are 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5, 6-dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid, 6-hydroxyindole, 6-aminoindole and 4-aminoindole.
  • N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole and in particular 5.6 are to be emphasized -Dihydroxyindol.
  • the indoline and indole derivatives can be used in the colorants according to the invention both as free bases and in the form of their physiologically tolerable salts with inorganic or organic acids, for.
  • the indole or indoline derivatives are usually contained in these in amounts of 0.05-10% by weight, preferably 0.2-5% by weight.
  • the indoline or indole derivative in colorants in combination with at least one To use amino acid or an oligopeptide.
  • the amino acid is advantageously an ⁇ -amino acid; very particularly preferred ⁇ -amino acids are arginine, omithin, lysine, serine and histidine, in particular arginine.
  • the colorants according to the invention can contain one or more direct dyes for shading.
  • Direct dyes are usually nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols.
  • Preferred direct dyes are those with the international names 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 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 known compounds and 1 , 4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1, 4-bis (ß-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (ß-hydroxyethyl) aminophenol, 2 - (2'-Hydroxyethyl) amino-4,6-dinitrophenol, 1- (2'-hydroxyethyl) amino-4-methyl
  • agents according to the invention can contain a cationic direct dye.
  • a cationic direct dye is particularly preferred.
  • aromatic systems which are substituted with a quaternary nitrogen group, such as, for example, Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 and Basic Brown 17, and
  • Preferred cationic direct dyes of group (c) are in particular the following compounds:
  • the compounds of the formulas (DZ1), (DZ3) and (DZ5) which are also known by the names Basic Yellow 87, Basic Orange 31 and Basic Red 51, are very particularly preferred cationic direct dyes of group (c).
  • the cationic direct dyes, which are sold under the trademark Arianor ® are, according to the invention also very particularly preferred cationic direct dyes.
  • the agents according to the invention in accordance with this embodiment preferably contain the substantive dyes in an amount of 0.01 to 20% by weight, based on the total colorant.
  • preparations according to the invention can also contain naturally occurring dyes, such as those contained in henna red, henna neutral, henna black, chamomile flowers, sandalwood, black tea, sapwood, sage, blue wood, madder root, catechu, sedre and alkanna root.
  • naturally occurring dyes such as those contained in henna red, henna neutral, henna black, chamomile flowers, sandalwood, black tea, sapwood, sage, blue wood, madder root, catechu, sedre and alkanna root.
  • the hair colorants according to the invention may also contain minor components in minor amounts, provided that these do not adversely affect the coloring result or for other reasons, e.g. toxicological, must be excluded.
  • Another possibility for dyeing keratin-containing fibers is offered by the use of colorants which, in addition to the m-phenylenediamine derivatives of the formula (I) according to the invention, contain reactive carbonyl compounds, i.e. Compounds containing at least one reactive carbonyl group and / or CH-acidic compounds.
  • the abovementioned compounds are generally not themselves dyes and are therefore not suitable for dyeing keratin fibers on their own. In combination, they form dyes in a non-oxidative process.
  • This process also called oxo dyeing, is described, for example, in the publications WO-A1 -99/18916, WO-A1 -00/38638, WO-A1-01 / 34106 and WO-A 1-01 / 47483.
  • Reactive carbonyl compounds according to the invention have at least one carbonyl group as the reactive group, which reacts to form a covalent bond. Furthermore, according to the invention, such compounds are also reactive Carbonyl compound can be used in which the reactive carbonyl group is derivatized in such a way that the reactivity of the carbon atom of the derivatized carbonyl group with respect to the coupler components according to the invention and / or the CH-acidic compounds is always present.
  • These derivatives are preferably addition compounds of a) amines and their derivatives to form imines or oximes as addition compound b) of alcohols to form acetals or ketals as addition compound to the carbon atom of the carbonyl group of the reactive carbonyl compound and c) of water to form hydrates.
  • the reactive carbonyl compound is preferably selected from compounds of the formula (01)
  • AR stands for benzene, naphthalene, pyridine, pyrimidine, pyrazine, pyridazine, carbazole, pyrrole, pyrazole, furan, thiophene, 1,2,3-triazine, 1,3,5-triazine, quinoline, isoquinoline, indole, indoline, Indolizine, indan, imidazole, 1,2,4-triazole, 1,2,3-triazole, tetrazole, benzimidazole, 1, 3-thiazole, benzothiazole, indazole, benzoxazole, quinoxaline, quinazoline, quinolizine, cinnoline, acridine, julolidine, Acenaphthene, fluorene, biphenyl, diphenylmethane, benzophenone, diphenyl ether, azobenzene, chromone, coumarin, diphen
  • R 1 represents a hydrogen atom, a dC 6 -alkyl, C 2 -C 6 -acyl, C 2 -C 4 -alkenyl, CC t -perfluoroalkyl, an optionally substituted aryl or heteroaryl group,
  • R 2 R 3 and R 4 independently represent a hydrogen atom, a halogen atom, a dC 6 alkyl, -C 6 alkoxy, -C 6 aminoalkyl, C ⁇ -C 6 - hydroxyalkyl group, a C ⁇ -C 6 -Alkoxy-CrC 6 -alkyloxy group, a C 2 -C 6 -acyl group, an acetyl, carboxyl, carboxylato, carbamoyl, sulfo-, sulfato, sulfonamide, sulfonamido, C 2 -C 6 -alkenyl- , an aryl, an aryl -CC 6 alkyl group, a hydroxy, a nitro, a pyrrolidino, a morpholino, a piperidino, a Amino or ammonio or a 1-imidazole (in) io group, the last three groups with one or more
  • Z stands for a direct bond, a carbonyl, a carboxy (CrC) alkylene, an optionally substituted C 2 -C 6 alkenylene, C 4 -C 6 alkadienylene, furylene, thienylene, arylene -, vinylene arylene, vinylene furylene, vinyl thienylene group, where Z together with the -YR 1 group can also form an optionally substituted 5-, 6- or 7-ring,
  • Y represents a group which is selected from carbonyl, a group according to formula (02) and a group according to formula (03),
  • R s stands for a hydrogen atom, a hydroxyl group, a CrC alkoxy group, a C 6 alkyl group, a CrC 6 hydroxyalkyl group, a C 2 -C 6 polyhydroxyalkyl group, a CrC 6 alkoxy CrC 6 alkyl group,
  • R 6 and R 7 independently of one another represent a CrC 6 alkyl group, an aryl group or together with the structural element OCO of the formula (01) form a 5- or 6-membered ring.
  • the reactive carbonyl compound is particularly preferably selected from the group consisting of acetophenone, propiophenone, 2-hydroxyacetophenone, 3-hydroxyacetophenone, 4-hydroxyacetophenone, 2-hydroxypropiophenone, 3-hydroxypropiophenone, 4-hydroxypropiophenone, 2-hydroxybutyrophenone, 3-hydroxybutyrophenone Hydroxybutyrophenone, 2,4-dihydroxyacetophenone, 2,5-dihydroxyacetophenone, 2,6-dihydroxyacetophenone, 2,3,4-trihydroxyacetophenone, 3,4,5- Trihydroxyacetophenone, 2,4,6-trihydroxyacetophenone, 2,4,6-trimethoxyacetophenone, 3,4,5-trimethoxyacetophenone, 3,4,5-trimethoxyacetophenone-diethyl ketal, 4-hydroxy-3-methoxyacetophenone, 3, 5-dimethoxy-4-hydroxyacetophenone, 4-aminoacetophenone, 4-dimethylaminoacetophenone,
  • Trihydroxybenzaldehyde 4-hydroxy-2-methoxybenzaldehyde, 4-dimethylaminobenzaldehyde, 4-diethylaminobenzaldehyde, 4-dimethylamino-2-hydroxybenzaldehyde, 4-diethylamino-2-hydroxybenzaldehyde, 4-pyrrolidinobenzaldehyde, 4-
  • the CH-acidic compounds are preferably selected from the group consisting of 1, 2,3,3-tetramethyl-3H-indolium iodide, 1, 2,3,3-tetramethyl-3H-indolium-p-toluenesulfonate, 1, 2,3 , 3-tetramethyl-3H-indolium methanesulfonate, 1, 3,3-trimethyl-2-methylene indoline
  • the colorants according to the invention can furthermore contain all active substances, additives and auxiliaries known for such preparations.
  • the colorants contain at least one surfactant, with both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants being suitable in principle.
  • Suitable anionic surfactants in preparations according to the invention are all anionic surface-active substances suitable for use on the human body. These are characterized by a water-solubilizing, anionic Group such as B. a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group with about 10 to 22 carbon atoms.
  • anionic Group such as B. a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group with about 10 to 22 carbon atoms.
  • glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups can be contained in the molecule.
  • anionic surfactants are, in each case in the form of the sodium, potassium and ammonium and the mono-, di- and trialkanolammonium salts with 2 or 3 carbon atoms in the alkanol group, linear fatty acids with 10 to 22 carbon atoms (soaps )
  • Ether carboxylic acids of the formula RO- (CH 2 -CH 2 O) x -CH 2 -COOH, in which R is a linear alkyl group with 10 to 22 C atoms and x 0 or 1 to 16, acyl sarcosides with 10 to 18 C- Atoms in the acyl group, acyl taurides with 10 to 18 C atoms in the acyl group, acyl isethionates with 10 to 18 C atoms in the acyl group, sulfosuccinic acid and dialkyl esters with 8 to 18 C atoms in the alkyl group and sulfosuccinic acid mono-alkyl polyoxyethyl esters with 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups, linear alkane sulfonates with 12 to 18 carbon atoms, linear alpha-olefin sulfonates with 12 to 18 carbon atoms, methyl alpha
  • Esters of tartaric acid and citric acid with alcohols which are adducts of about 2-15 molecules of ethylene oxide and / or propylene oxide with fatty alcohols with 8 to 22 carbon atoms.
  • Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids with 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule, and in particular salts of saturated and in particular unsaturated Cs-d ⁇ carboxylic acids, such as oleic acid, stearic acid, isostearic acid and palmitic acid.
  • Non-ionic surfactants contain z.
  • Such connections are, for example
  • Preferred nonionic surfactants are alkyl polyglycosides of the general formula R O- (Z) ⁇ . These connections are characterized by the following parameters.
  • the alkyl radical R 1 contains 6 to 22 carbon atoms and can be either linear or branched. Primary linear and methyl-branched aliphatic radicals in the 2-position are preferred. Examples of such alkyl radicals are 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-stearyl. 1-Octyl, 1-decyl, 1-lauryl, 1-myristyl are particularly preferred. When using so-called "oxo alcohols" as starting materials, compounds with an odd number of carbon atoms in the alkyl chain predominate.
  • the alkyl polyglycosides which can be used according to the invention can contain, for example, only a certain alkyl radical R 1 .
  • these compounds are made from natural fats and oils or mineral oils.
  • the alkyl radicals R are mixtures corresponding to the starting compounds or corresponding to the respective working up of these compounds.
  • R 1 consists essentially of C 8 and C 0 alkyl groups, essentially C 12 and C 4 alkyl groups, essentially C 8 to C 6 alkyl groups or essentially C 12 - Until C ⁇ 6 alkyl groups.
  • Any mono- or oligosaccharides can be used as the sugar building block Z.
  • Sugar with 5 or 6 carbon atoms and the corresponding oligosaccharides are usually used. Examples of such sugars are glucose, fructose, galactose, arabinose, ribose, xylose, lyxose, allose, old rose, mannose, gulose, idose, talose and sucrose.
  • Preferred sugar components are glucose, fructose, galactose, arabinose and sucrose; Glucose is particularly preferred.
  • alkyl polyglycosides which can be used according to the invention contain on average 1.1 to 5 sugar units. Alkyl polyglycosides with x values from 1.1 to 1.6 are preferred. Alkyl glycosides in which x is 1.1 to 1.4 are very particularly preferred.
  • the alkyl glycosides can also serve to improve the fixation of fragrance components on the hair.
  • the person skilled in the art will preferably resort to this substance class as a further ingredient of the preparations according to the invention.
  • alkoxylated homologs of the alkyl polyglycosides mentioned can also be used according to the invention. These homologues can contain an average of up to 10 ethylene oxide and / or propylene oxide units per alkyl glycoside unit.
  • zwitterionic surfactants can be used, in particular as co-surfactants.
  • Zwitterionic surfactants are surface-active compounds that contain at least one quaternary ammonium group and at least one -COO (_) - or -SOa ⁇ group in the molecule.
  • Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinate, for example the cocoalkyl-dimethylammonium glycinate, N-acyl-aminopropyl-N, N-dimethylammonium glycinate, for example the cocoacylaminopropyl-dimethylammonium glycinate, and 2-alkyl-3-carboxylmethyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and the cocoacylaminoethyl-hydroxyethylcarboxymethylglycinate.
  • a preferred zwitterionic surfactant is the fatty acid amide derivative known under the INCI name Cocamidopropyl Betaine.
  • Ampholytic surfactants are also particularly suitable as co-surfactants.
  • Ampholytic surfactants are understood to mean those surface-active compounds which contain in addition to a C 8 -C 8 alkyl or acyl group in the molecule at least one free amino group and at least one -COOH or -SO 3 H group and are capable of forming internal salts.
  • ampholytic surfactants are N-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N-alkyliminodipropionic acid, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyltaurine, N-alkylsarcosine, 2-alkylaminopropionic acid and alkylaminoacetic acid, each with about 8 to 18 carbon atoms in the alkyl group.
  • Particularly preferred ampholytic surfactants are the N-coconut alkyl aminopropionate, the coconut acylaminoethyl aminopropionate and the C 1 -C 8 -acyl sarcosine.
  • the cationic surfactants used are, in particular, those of the quaternary ammonium compound, esterquat and amidoamine type.
  • Preferred quaternary ammonium compounds are ammonium halides, in particular chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g. B. cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride, as well as the imidazolium compounds known under the INCI names Quatemium-27 and Quaternium-83.
  • the long alkyl chains of the above-mentioned surfactants preferably have 10 to 18 carbon atoms.
  • Ester quats are known substances which contain both at least one ester function and at least one quaternary ammonium group as a structural element.
  • Preferred ester quats are quaternized ester salts of fatty acids with triethanolamine, quaternized ester salts of fatty acids with diethanolalkylamines and quaternized ester salts of fatty acids with 1,2-dihydroxypropyldialkylamines.
  • Such products are sold, for example, under the trademarks Stepantex ® , Dehyquart ® and Armocare ® .
  • alkylamidoamines are usually produced by amidation of natural or synthetic fatty acids and fatty acid cuts with dialkylaminoamines.
  • a compound from this group of substances which is particularly suitable according to the invention is that commercially available stearamidopropyldimethylamine under the name Tegoamid ® S 18.
  • the quaternized protein hydrolyzates are further cationic surfactants which can be used according to the invention.
  • cationic silicone oils such as, for example, the commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethylsilylamodimethicone), Dow Corning 929 emulsion (containing a hydroxylamino-modified silicone, which is also referred to as amodimethicone), SM-2059 (Manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ® - Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, Quaternium-80).
  • a suitable cationic surfactant quaternary sugar derivative is the commercial product Glucquat ® 100, according to INCI nomenclature a "lauryl methyl Gluceth-10 Hydroxypropyl Dimonium Chloride”.
  • the compounds with alkyl groups used as surfactant can each be uniform substances. However, it is generally preferred to use native vegetable or animal raw materials in the production of these substances, so that substance mixtures with different alkyl chain lengths depending on the respective raw material are obtained.
  • both products with a "normal” homolog distribution and those with a narrowed homolog distribution can be used.
  • “Normal” homolog distribution is understood to mean mixtures of homologs which are obtained as catalysts from the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates.
  • narrow homolog distributions are obtained if, for example, hydrotaicites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates are used as catalysts.
  • the use of products with a narrow homolog distribution can be preferred.
  • the colorants according to the invention can contain other active ingredients, auxiliaries and
  • Additives such as for example, nonionic polymers such as vinylpyrrolidone / vinyl acrylate copolymers, polyvinylpyrrolidone and vinylpyrrolidone / vinyl acetate copolymers and polysiloxanes, cationic polymers such as quaternized cellulose ethers, polysiloxanes having quaternary groups, dimethyldiallylammonium chloride polymers, acrylamide-dimethyl diallyl ammonium chloride copolymers, with diethyl sulfate quaternized Dimethylamino-ethyl methacrylate-vinylpyrrolidone copolymers, vinylpyrrolidone-imidazolinium methochloride copolymers and quaternized polyvinyl alcohol, zwitterionic and amphoteric polymers such as, for example, acrylamidopropyl-trimethylammonium chloride / acrylate copolymers and octylacrylamide
  • Thickeners such as agar agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives, e.g. B. methyl cellulose, hydroxyalkyl cellulose and carboxymethyl cellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such.
  • B. bentonite or fully synthetic hydrocolloids such as e.g. Polyvinyl alcohol, structurants such as maleic acid and lactic acid, hair-conditioning compounds such as phospholipids, for example soy lecithin, egg lecithin and cephalins,
  • Protein hydrolyzates in particular elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolyzates, their condensation products with fatty acids and quaternized protein hydrolyzates, perfume oils, dimethyl isosorbide and cyclodextrins,
  • Solvents and intermediates such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol, active substances which improve the fiber structure, in particular mono-, di- and oligosaccharides such as, for example, glucose, galactose, fructose, fructose and lactose,
  • Quaternized amines such as methyl 1-alkylamidoethyl-2-alkylimidazolinium methosulfate Defoamers such as silicones, dyes for coloring the agent,
  • Anti-dandruff agents such as piroctone olamine, zinc omadine and climbazole, light stabilizers, in particular derivatized benzophenones, cinnamic acid derivatives and triazines,
  • Substances for adjusting the pH such as customary acids, in particular edible acids and bases,
  • Active ingredients such as allantoin, pyrrolidone carboxylic acids and their salts as well as bisabolol, vitamins, provitamins and vitamin precursors, in particular those of groups A, B 3 , B 5 , B 6 , C, E, F and H,
  • Plant extracts such as the extracts from green tea, oak bark, nettle, witch hazel, hops, chamomile, burdock root, horsetail, hawthorn, linden flowers, almond, aloe vera, spruce needle, horse chestnut, sandalwood, juniper, coconut, mango, apricot, lime, wheat, kiwi , Melon, orange, grapefruit, sage, rosemary, birch, mallow, cuckoo flower, quendel, yarrow, thyme, lemon balm, squirrel, coltsfoot, marshmallow, meristem, ginseng and ginger root.
  • Cholesterol Cholesterol
  • Consistency agents such as sugar esters, polyol esters or polyol alkyl ethers, fats and waxes such as walrus, beeswax, montan wax and paraffins, fatty acid alkanolamides,
  • Complexing agents such as EDTA, NTA, ß-alaninediacetic acid and phosphonic acids, swelling and penetration substances such as glycerol, propylene glycol monoethyl ether, carbonates, hydrogen carbonates, guanidines, ureas and primary, secondary and tertiary phosphates,
  • Opacifiers such as latex, styrene / PVP and styrene / acrylamide copolymers pearlescent agents such as ethylene glycol mono- and distearate and PEG-3 distearate, pigments,
  • Stabilizing agents for hydrogen peroxide and other oxidizing agents blowing agents such as propane-butane mixtures, N 2 O, dimethyl ether, CO 2 and air, antioxidants, contain
  • the agents according to the invention preferably contain the dye precursors in a suitable aqueous, alcoholic or aqueous-alcoholic carrier.
  • a suitable aqueous, alcoholic or aqueous-alcoholic carrier are, for example, creams, emulsions, gels or also surfactant-containing foaming solutions, such as shampoos, foam aerosols or other preparations which are suitable for use on the hair.
  • surfactant-containing foaming solutions such as shampoos, foam aerosols or other preparations which are suitable for use on the hair.
  • aqueous-alcoholic solutions are to be understood as meaning aqueous solutions containing 3 to 70% by weight of a d-C alcohol, in particular ethanol or isopropanol.
  • the agents according to the invention can additionally contain other organic solvents, such as methoxybutanol, benzyl alcohol, ethyl diglycol or 1,2-propylene glycol. All water-soluble organic solvents are preferred.
  • the actual oxidative coloring of the fibers can basically be done with atmospheric oxygen.
  • a chemical oxidizing agent is preferably used, especially if, in addition to the coloring, a lightening effect on human hair is desired.
  • Persulfates, chlorites and in particular hydrogen peroxide or their adducts with urea, melamine and sodium borate are suitable as oxidizing agents.
  • the oxidation coloring agent can also be applied to the hair together with a catalyst which oxidizes the dye precursors, e.g. activated by atmospheric oxygen.
  • catalysts are e.g. Metal ions, iodides, quinones or certain enzymes.
  • Suitable metal ions are, for example, Zn 2+ , Cu 2+ , Fe 2+ , Fe 3+ , Mn 2+ , Mn + , Li + , Mg 2+ , Ca 2+ and Al 3+ .
  • Zn 2+ , Cu 2+ and Mn 2+ are particularly suitable.
  • the metal ions can be used in the form of any physiologically acceptable salt or in the form of a complex compound.
  • Preferred salts are the acetates, sulfates, halides, lactates and tartrates.
  • Suitable enzymes are, for example, peroxidases, which can significantly intensify the expression of small amounts of hydrogen peroxide. Furthermore, such enzymes are suitable according to the invention which directly oxidize the oxidation dye precursors with the help of atmospheric oxygen, such as for example the laccases, or generate small amounts of hydrogen peroxide in situ and in this way activate the oxidation of the 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, for example
  • Lactate oxidase and lactic acid and their salts Lactate oxidase and lactic acid and their salts
  • the actual hair dye is expediently prepared immediately before use by mixing the preparation of the oxidizing agent with the preparation containing the dye precursors.
  • the resulting ready-to-use hair dye preparation should preferably have a pH in the range from 6 to 12. It is particularly preferred to use the hair dye in a weakly alkaline environment. Application temperatures can range between 15 and 40 ° C. After an exposure time of 5 to 45 minutes, the hair dye is rinsed off from the hair to be colored. Washing with a shampoo is not necessary if a carrier with a high tenside content, e.g. a coloring shampoo was used.
  • the preparation with the dye precursors can also be applied to the hair without prior mixing with the oxidation component.
  • the oxidation component is then applied, if necessary after an intermediate rinse.
  • the skin is rinsed and, if necessary, re-shampooed.
  • the corresponding agent is adjusted to a pH of about 4 to 7.
  • air oxidation is initially aimed for, the agent applied preferably having a pH of 7 to 10.
  • the use of acidified peroxidisulfate solutions as the oxidizing agent can be preferred.
  • a second subject of the present application is the use of the m-phenylediamine derivatives according to the invention for dyeing keratin fibers.
  • a third object of the present invention is a process for dyeing keratin fibers, in which a hair dye according to the invention is applied to the fibers and rinsed off again after an exposure time.
  • a fourth object of the present invention are m-phenylenediamine derivatives selected from the group formed by N, N-dimethyl-3- (pyrrolidin-1-yl) aniline, 2 - [(3-morpholin-4-ylphenyl) amino] ethan-1-ol, 2 - [(3-piperidin-1-ylphenyl) amino] ethan-1-ol and 2 - [(3-pyrrolidin-1-ylphenyl) amino] ethan-1-ol.
  • a fifth object of the present invention are the first intermediates in the synthesis of the m-phenylenediamines according to the invention, selected from the group formed by (2-chloroethoxy) -N- (3-morpholin-4-ylphenyl) carboxamide, (2- Chloroethoxy) -N- (3-piperidin-1-ylphenyl) carboxamide and (2-chloroethoxy) -N- (3-pyrrolidin-1-ylphenyl) carboxamide.
  • a sixth object of the present application are the second intermediates in the synthesis of the m-phenylenediamine derivatives according to the invention, selected from the group formed by 3- (3-morpholin-4-ylphenyl) -1, 3-oxazolidin-2-one, 3 - (3-Piperidin-1-ylphenyl) -1, 3-oxazolidin-2-one and 3- (3-pyrrolidin-1-ylphenyl) -1, 3-oxazolidin-2-one.
  • the cream base used had the following composition:
  • Ci 2 - ⁇ 8 fatty alcohol (INCI name: Coconut alcohol) (Cognis)
  • the dissolved dye precursors were worked into the hot cream one after the other.
  • the mixture was then made up to 97 g with distilled water and the pH was adjusted to 9.5 with ammonia. After filling up to 100 g with distilled water, the mixture was stirred cold ( ⁇ 30 ° C.), a homogeneous cream being formed. Unless otherwise noted, 25 g of coloring cream were mixed with 25 g of the following oxidizing agent preparation for the colorations.
  • a strand of hair (80% gray; 330 mg to 370 mg in weight) was added to each of the mixtures thus obtained.
  • the mixtures and the strands of hair were then each placed on a watch glass and the strands of hair were well embedded in the coloring creams. After 30 minutes ( ⁇ 1 minute) Reaction time at room temperature were removed and the strands of hair so washed many times, until the color was removed with an excess of an aqueous solution Texapon ® EVR. 9
  • the strands of hair were air-dried and their shade determined and noted under the daylight lamp (color testing device HE240A) (Taschenlexikon der Weg Weg, A. Komerup and JH Wanscher, 3rd unchanged edition 1981, MUSTER-SCHMIDT Verlag; Zurich, Göttingen).
  • Lauryl ether sulfate sodium salt with special additives (approx. 34 to 37% active substance content; INCI name: Sodium Lauryl Sulfate, Sodium Laureth Sulfate, Lauramide MIPA, Cocamide MEA, Glycol Stearate, Laureth-10) (Cognis)
  • Active substance (Cognis Corporation (Emery)) 8 Lauryl alcohol-4.5-EO-Acetic acid sodium salt (at least 21% active substance content; INCI name: Sodium Laureth-6 carboxylate) (Chem-Y) 9 2-Octyldodecyl alcohol (INCI- Name: octyldodecanol) (Cognis) 0 approx. 20% by weight active substance content in water; INCI name: Acrylamidopropyltrimonium Chloride / Acrylates Copolymer (Stockhausen) Guar hydroxypropyltrimethylammonium chloride (at least 93% solids; INCI name: guar hydroxypropyltrimonium chloride) (Cognis CorporationCosmedia)
  • Dimethyldiallylammonium chloride acrylamide copolymer (approx.8.1-9.1% active substance in water; INCI name: Polyquaternium-7) (Ondeo-Nalco)
  • Vinylimidazolium methochloride-vinylpyrrolidone copolymer (30:70) (38-42% solids in water; INCI name: Polyquatemium-16) (BASF)
  • Acrylic acid copolymer (approx. 35 active substance in water; INCI name: Polyquaternium-22) (Ondeo-Nalco)
  • Oleic acid (INCI name: Oleic Acid) (Cognis Deutschland GmbH (Caldic))
  • Ci 2 - ⁇ fatty alcohol with approx. 2-EO units (INCI name: Laureth-2) (Cognis Deutschland GmbH)
  • Silk protein (approx. 99% protein; INCI name: Silk, Serica (Linne)) (Ikeda Bussan Kaisha)
  • Acid-containing, cross-linked acrylic copolymer (INCI name: Acrylates Copolymer, approx. 28% active substance) (Rohm & Haas) 3.12 discoloration
  • the dye product preparations 1 to 10 were mixed immediately before use in a 1: 1 ratio with a 6% hydrogen peroxide preparation (see point 3.11).
  • the resulting application preparation was on natural white strands

Landscapes

  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Cosmetics (AREA)

Abstract

L'invention concerne des produits de coloration pour fibres kératiniques, en particulier pour des cheveux humains. Ces produits contiennent, dans un véhicule cosmétiquement acceptable, en tant que composant copulant au moins un dérivé de m-phénylènediamine de formule (I) ou un de ses sels physiologiquement acceptables. Dans cette formule (I) : R1 représente un atome d'hydrogène, un atome d'halogène, un groupe alkyle en C1-C4, un groupe monohydroxyalkyle en C1-C4, un groupe polyhydroxyalkyle en C2-C4, un groupe aminoalkyle en C1-C4, un groupe alcoxy(C1-C4)-alkyle(C1-C4) ou un groupe dialkylamino(C1-C4)-alkyle(C1-C4) ; R2 et R3 représentent indépendemment l'un de l'autre un atome d'hydrogène, un groupe alkyle en C1-C4, un groupe monohydroxyalkyle en C2-C4, un groupe polyhydroxyalkyle en C3-C4, un groupe alcoxy(C1-C4)-alkyle(C1-C4), ou un groupe aminoalkyle en C1-C4 ; X représente un hétérocycle saturé à 5, 6 ou 7 chaînons comportant au moins un atome d'azote et éventuellement un autre hétéroatome, sélectionné entre oxygène, soufre ou azote, cet hétérocycle étant relié au système cyclique aromatique par l'intermédiaire d'un atome d'azote et pouvant éventuellement comprendre jusqu'à deux substituents différents de l'hydrogène, sélectionnés entre un atome d'halogène, un groupe alkyle en C1-C4, un groupe monohydroxyalkyle en C1-C4, un groupe polyhydroxyalkyle en C2-C4, un groupe aminoalkyle en C1-C4, un groupe alcoxy(C1-C4)-alkyle(C1-C4) ou un groupe dialkylamino(C1-C4)-alkyle(C1-C4). Lorsqu'ils sont combinés à des dérivés de p-phénylènediamine, à des dérivés de diaminopyrazole ainsi qu'à des dérivés d'oligoaminopyrimidine, les composants copulants selon l'invention peuvent conférer aux cheveux des nuances brillantes intenses très résistantes.
EP03750569A 2002-09-27 2003-09-18 Produits de coloration capillaire contenant des derives de m-phenylenediamine en tant que composants copulants Withdrawn EP1542982A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10245426 2002-09-27
DE2002145426 DE10245426A1 (de) 2002-09-27 2002-09-27 Neue Kupplerkomponenten
PCT/EP2003/010371 WO2004031164A1 (fr) 2002-09-27 2003-09-18 Produits de coloration capillaire contenant des derives de m-phenylenediamine en tant que composants copulants

Publications (1)

Publication Number Publication Date
EP1542982A1 true EP1542982A1 (fr) 2005-06-22

Family

ID=31984230

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03750569A Withdrawn EP1542982A1 (fr) 2002-09-27 2003-09-18 Produits de coloration capillaire contenant des derives de m-phenylenediamine en tant que composants copulants

Country Status (4)

Country Link
EP (1) EP1542982A1 (fr)
AU (1) AU2003270217A1 (fr)
DE (1) DE10245426A1 (fr)
WO (1) WO2004031164A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7303592B2 (en) * 2002-03-04 2007-12-04 The Procter & Gamble Company Hair coloring compositions for use in oxidative hair dyeing
DE10260880A1 (de) * 2002-12-23 2004-07-01 Henkel Kgaa Färbetablette
JP6081078B2 (ja) * 2012-03-19 2017-02-15 株式会社ミルボン 酸化染毛剤

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2622451A1 (de) * 1976-05-20 1977-12-08 Henkel Kgaa Haarfaerbemittel
DE2924089A1 (de) * 1979-06-15 1981-01-08 Henkel Kgaa Neue kupplerkomponenten fuer oxidationshaarfarben, deren herstellung sowie diese enthaltende haarfaerbemittel
LU86904A1 (fr) * 1987-05-29 1989-01-19 Oreal Nouvelles chlorometaphenylenediamines,leur utilisation en tanque coupleurs en teinture d'oxydation des fibres keratiniques,compositions tinctoriales pour cheveux contenant ces composes et procede de teinture utilisant lesdites compositions
WO1998001106A2 (fr) * 1996-07-03 1998-01-15 Hans Schwarzkopf Gmbh & Co. Kg Colorants d'oxydation

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2004031164A1 *

Also Published As

Publication number Publication date
WO2004031164A1 (fr) 2004-04-15
DE10245426A1 (de) 2004-04-08
AU2003270217A1 (en) 2004-04-23

Similar Documents

Publication Publication Date Title
EP1771145B1 (fr) Agents éffectuant en même temps la coloration et l'éclaircissement des fibres kératiniques
EP1726289A2 (fr) Composition de teinture pour les fibres kératiniques contenant un réducteur
EP1534227A1 (fr) Produits pour la teinture de fibres keratiniques
EP1714634A1 (fr) Kit pour le soin capillaire avec des agents chélatants
DE102005052139A1 (de) Haarfärbe- und/oder -aufhellverfahren mit verbesserter Wirksamkeit
EP1779894A1 (fr) Compositions de coloration capillaire
DE102005038073A1 (de) Mittel zum Aufhellen und/oder Färben von keratinhaltigen Fasern mit beschichtetem Alkalisierungsmittel
DE10359831A1 (de) Mittel zum Färben von keratinhaltigen Fasern
EP1776984A2 (fr) Méthode pour prolonger les cycles de recoloration
EP1542982A1 (fr) Produits de coloration capillaire contenant des derives de m-phenylenediamine en tant que composants copulants
EP1430874A2 (fr) Derivates de 4-N, N-bis-(monohydroxyalkyl)amino-3-nitrophenol dans des compositions de teinture pour des fibres kératiniques
WO2006018089A1 (fr) Colorants oxydatifs contenant des derives diaminobenzol
EP1433468A1 (fr) Imines des sels du N-methylquinoline utilisés pour la teinture des fibres keratiniques
WO2006045454A1 (fr) Agent a teneur en carbonate et/ou carbamate de silyle, servant a colorer et eclaircir simultanement des fibres keratiniques
EP1433469B1 (fr) Composition de teinture des fibres kératiniques
DE10260881A1 (de) Mittel zum Färben von keratinhaltigen Fasern
EP1909913A1 (fr) Procede pour dissimuler rapidement des racines capillaires resultant de la pousse de cheveux colores
DE102005042052A1 (de) Oxidationsfärbemittel mit 2,6-Diamino-4-methylanisol und mindestens einem speziellen Entwickler
DE102004045686A1 (de) Haarfärbemittel mit 2-((4-(Di(2-hydroxyethyl)amino)phenyl)amino)-5-((2-hydroxyethyl)-amino)-2,5-cyclohexadien-1,4-dion
DE102004029124A1 (de) Mittel zum Färben von keratinhaltigen Fasern
DE102005015329A1 (de) Mittel zum Färben von keratinhaltigen Fasern
DE102005015330A1 (de) Mittel zum Färben von keratinhaltigen Fasern
WO2007009530A1 (fr) Necessaire de traitement capillaire renfermant des agents de coloration et une bande adhesive utilisee en tant que protection contre la couleur
DE102005011924A1 (de) Neue Farbstoffe und Färbemittel mit speziellen Carbonylverbindungen

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20050107

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR

17Q First examination report despatched

Effective date: 20071114

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: HENKEL AG & CO. KGAA

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20080527