EP1893165A1 - Mehrkomponentenmittel zum färben keratinischer fasern - Google Patents
Mehrkomponentenmittel zum färben keratinischer fasernInfo
- Publication number
- EP1893165A1 EP1893165A1 EP06707642A EP06707642A EP1893165A1 EP 1893165 A1 EP1893165 A1 EP 1893165A1 EP 06707642 A EP06707642 A EP 06707642A EP 06707642 A EP06707642 A EP 06707642A EP 1893165 A1 EP1893165 A1 EP 1893165A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- group
- amino
- preparation
- hydroxy
- alkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- 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
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
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- 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
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
- A61K8/4906—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom
- A61K8/4913—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having five membered rings, e.g. pyrrolidone carboxylic acid
- A61K8/492—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having five membered rings, e.g. pyrrolidone carboxylic acid having condensed rings, e.g. indol
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
- A61K8/4906—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom
- A61K8/4926—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having six membered rings
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
- A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
- A61K8/4953—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom containing pyrimidine ring derivatives, e.g. minoxidil
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- 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
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/80—Process related aspects concerning the preparation of the cosmetic composition or the storage or application thereof
- A61K2800/88—Two- or multipart kits
Definitions
- the present invention relates to a multi-component agent for coloring keratinic fibers, which is packaged in a multi-chamber tube, a corresponding Mehrschtube and a method for coloring keratinic fibers using this agent.
- Human hair is today treated in a variety of ways with hair cosmetic preparations. These include, for example, the cleansing of hair with shampoos, the care and regeneration with rinses and cures and the bleaching, dyeing and shaping of the hair with dyes, tinting agents, waving agents and styling preparations. In this case, means for changing or nuancing the color of the head hair play a prominent role.
- dyeing or tinting agents which contain so-called direct drawers as a coloring component. These are dye molecules that attach directly to the hair and do not require an oxidative process to form the paint. These dyes include, for example, the henna already known from antiquity for coloring body and hair. These dyeings are generally much more sensitive to shampooing than the oxidative dyeings, so that a much more undesirable nuance shift or even a visible "discoloration" occurs much more quickly.
- oxidation colorants For permanent, intensive colorations with corresponding fastness properties, so-called oxidation colorants are used. Such colorants usually contain oxidation dye precursors, so-called developer components and coupler components. The developer components form under the influence of oxidizing agents or of atmospheric oxygen with one another or with coupling with one or more coupler components, the actual dyes.
- the oxidation stains are characterized by excellent, long lasting staining results.
- intensive dyeings with good fastness properties can be obtained with oxidation dyes, the development of the color is generally carried out under the influence of oxidizing agents such. H 2 O 2 , which in some cases may result in damage to the fiber.
- some oxidation dye precursors or certain mixtures of oxidation dye precursors can sometimes have a sensitizing effect in persons with sensitive skin.
- a first subject of the present invention are therefore agents for coloring keratinous fibers, comprising a multicomponent agent and a multichamber tube, wherein the multicomponent agent comprises a first preparation (A) containing at least one reactive carbonyl compound and a second preparation (B) at least one compound selected from (a) CH-acidic compounds and (b) compounds having a primary amino group selected from primary aromatic amines and primary heteroaromatic amines, and the two preparations are packaged separately in the chambers of the multi-chamber tube.
- the multicomponent agent comprises a first preparation (A) containing at least one reactive carbonyl compound and a second preparation (B) at least one compound selected from (a) CH-acidic compounds and (b) compounds having a primary amino group selected from primary aromatic amines and primary heteroaromatic amines, and the two preparations are packaged separately in the chambers of the multi-chamber tube.
- compositions of the invention are characterized by excellent care and dyeing performance and high stability. In addition, it is ensured that the consumer applies the components in the mixing ratio planned by the manufacturer. In this way, on the one hand, product safety is increased and, on the other hand, it is ensured that the product provides the desired performance. Also, a separate mixing process can be dispensed with, since the individual dye components in the region of the outlet opening of the multi-chamber tube can sufficiently contact each other.
- the multicomponent agents according to the invention are two- or three-component agents.
- Preparation (A) contains at least one reactive carbonyl compound.
- Reactive carbonyl compounds in the context of the invention have at least one carbonyl group as a reactive group which reacts with a CH-acidic compound to form a carbon-carbon bond or with a compound having a primary amino group to form a Schiff base.
- Preferred reactive carbonyl compounds are aldehydes and ketones, especially aromatic aldehydes.
- those compounds which can be used as reactive carbonyl compounds in which the reactive carbonyl group is derivatized or masked such that the reactivity of the carbon atom of the dehvated carbonyl group with the CH-acidic compounds or primary amines are always present.
- These derivatives are preferably addition compounds a) of amines and derivatives thereof to form imines or oximes as addition compound b) of alcohols to form acetals or ketals as addition compound c) of water to form hydrates as an addition compound (the reactive carbonyl compound is derived in this case c) from an aldehyde) to the carbon atom of the carbonyl group of the reactive carbonyl compound.
- the reactive carbonyl compound is preferably selected from compounds of the formula (Ca-1),
- AR is 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, diphenylamine
- R 1 represents a hydrogen atom, a CrC 6 alkyl, C 2 -C 6 alkenyl, C r C alkyl 4 -Perfluor-, an optionally substituted aryl or heteroaryl group,
- R 2 , R 3 and R 4 independently represent a hydrogen atom, a halogen atom, a C r C 6 alkyl, CrC 6 alkoxy, C r C 6 aminoalkyl, C r C 6 hydroxyalkyl group, a CrCe-alkoxy-d-C ⁇ -alkyloxy group, a C 2 -C acyl group, an acetyl, carboxyl, carboxylato, carbamoyl, sulfo, sulfato, sulfonamide, sulfonamido, C 2 -C 6 alkenyl -, an aryl, an aryl-Ci-C 6 alkyl group, a hydroxy, a nitro, a pyrrolidino, a morpholino, a piperidino, an amino or ammonio or a 1-imidazole (in ) iooli which latter three groups with one or more -C 6 alkyl, -
- • 2 represents a direct bond, a carbonyl, a carboxy (C r C 4 ) alkylene, an optionally substituted C 2 -C 6 alkenylene, C 4 -C 6 alkadienylene, furylene, thienylene , Arylen-, Vinylenarylen-, Vinylenfurfurylen-, vinylenthienylene group, wherein Z together with the -YR 1 group can also form an optionally substituted 5-, 6- or 7-ring,
- Y is a group which is selected from carbonyl, a group according to formula (Ca-2) and a group according to formula (Ca-3),
- R 5 represents a hydrogen atom, a hydroxy group, a -C 4 alkoxy group, a C r C 6 alkyl group, a Ci-C 6 hydroxyalkyl group, a C 2 -C 6 alkyl group -Polyhydroxy-, a CRCE-alkoxy-CRCE alkyl group,
- R 6 and R 7 independently of one another represent a hydrogen atom, a C 1 -C 6 -alkyl group, an aryl group or together with the structural element OC-O of the formula (Ca-3) form a 5- or 6-membered ring.
- Ethylcarbazole-3-aldehyde 2-formylmethylene-1,3,3-trimethylindoline (Fischer's aldehyde or tribasic aldehyde),
- the reactive carbonyl compound such that the group Y of formula (Ca-1) is not a carbonyl group. In this case, it may be preferable to select the reactive carbonyl compound from one or more of the following group
- Y of formula (Ca-1) represents formula (Ca-2) in which R 5 represents 2-hydroxyethyl
- Y of the formula (Ca-1) represents formula (Ca-3) in which R 6 and R 7 signify an ethyl group
- Y of the formula (Ca-1) represents formula (Ca-3) in which R 6 and R 7 represent a hydrogen atom
- benzaldehyde, cinnamaldehyde and naphthaldehyde derivatives listed above particular preference is given to benzaldehyde, cinnamaldehyde and naphthaldehyde in the compositions according to the invention and, in particular, their derivatives with one or more Hydroxy, alkoxy or amino substituents.
- the compounds according to formula (Ca-4) are preferred,
- R 1, R 2 and R 3 are independently a hydrogen atom, a halogen atom, a CrC 6 alkyl group, a hydroxy group, a C r C 6 alkoxy group, a CrC ⁇ -dialkylamino group, a di (C 2 ⁇ C 6 - hydroxyalkyl) amino group, di (C 1 -C 6 alkoxyC r C 6 alkyl) amino group, d-C ⁇ hydroxyalkyloxy group, sulfonyl group, carboxyl group, sulfonic acid group, sulfonamido group, sulfonamide group, carbamoyl group , a C 2 -C 6 acyl group, an acetyl group or a nitro group,
- Z ' is a direct bond or a vinylene group
- R 4 and R 5 represent a hydrogen atom or together form, together with the remainder of the molecule, a 5- or 6-membered aromatic or aliphatic ring.
- Very particularly preferred reactive carbonyl compounds are selected from the group consisting of 4-hydroxy-3-methoxybenzaldehyde (vanillin), 3,5-dimethoxy-4-hydroxybenzaldehyde, 4-hydroxy-1-naphthaldehyde, 4-hydroxy-2-methoxybenzaldehyde, 3 , 4-dihydroxy-5-methoxybenzaldehyde, 3,4,5-trihydroxybenzaldehyde, 3,5-dibromo-4-hydroxybenzaldehyde, 4-hydroxy-3-nitrobenzaldehyde, 3-bromo-4-hydroxybenzaldehyde, A-hydroxy-3-methylbenzaldehyde , 3,5-dimethyl-4-hydroxybenzaldehyde, 5-bromo-4-hydroxy-3-methoxybenzaldehyde, 4-diethylamino-2-hydroxybenzaldehyde, 4-dimethylamino-2-methoxybenzaldehyde, 2-methoxybenzaldehyde, 3-methoxybenzaldehy
- Trihydroxybenzaldehyde 4-dimethylaminobenzaldehyde, 4-diethylaminobenzaldehyde, A-dimethylamino-2-hydroxybenzaldehyde, 4-pyrrolidinobenzaldehyde, A-
- reactive carbonyl compounds which are selected from the group consisting of vanillin, 4-hydroxy-3,5-dimethoxybenzaldehyde, 4-hydroxy-3,5-dimethylbenzaldehyde, 2,4 Dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, 4-hydroxy-2-methoxybenzaldehyde, 4-hydroxy-1-naphthaldehyde, 4-dimethylamino-2-methoxybenzaldehyde, 3,5-dibromo-4-hydroxybenzaldehyde , 3,5-dichloro-4-hydroxybenzaldehyde, 4-hydroxy-3,5-diiodobenzaldehyde, 3-chloro-4-hydroxybenzaldehyde, 3-bromo-4-hydroxybenzaldehyde, 5-chloro-3,4-dihydroxybenzaldehyde, 5 -Brom-3,4-dihydroxybenzaldehyde
- the agents of the invention preferably contain the reactive carbonyl compounds in an amount of 0.03 to 65 mmol, more preferably 1 to 40 mmol per 100 g of the total multicomponent agent.
- Preparation (B) of the multi-component agent of the invention contains at least one compound selected from (a) CH-acidic compounds and (b) primary amino group compounds selected from primary aromatic amines and primary heteroaromatic amines.
- CH-acidic compounds are generally considered to carry a bound to an aliphatic carbon atom hydrogen atom, wherein due to electron-withdrawing substituents, activation of the corresponding carbon-hydrogen bond is effected.
- the CH-acidic compounds are preferably selected from compounds according to one of the formulas (C1) to (C23): M 1 - CH 2 - M 2 (C1)
- M 2 has the same meaning as M 1 or is a cyano group, a substituted or unsubstituted aryl group or aryl-CrC 4 -allyl group, a substituted or unsubstituted, saturated or unsaturated heterocycle,
- M 5 is a cyano group, a substituted or unsubstituted aryl group or an arylC r C 4 alkyl group, a substituted or unsubstituted, saturated or unsaturated heterocycle or a group -COM 7 or COOM 7 , wherein M 7 represents a hydrogen atom or a C r is C 6 -alkyl group,
- M 6 is a substituted or unsubstituted C r C 6 alkyl group, an acetyloxy group, a C 3 -C 6 cycloalkyl group, a substituted or unsubstituted aryl group or aryl C 1 -C 4 alkyl group, a substituted or unsubstituted aminoaryl group, a substituted or unsubstituted, saturated or unsaturated heterocycle,
- M 8 is a cyano group, a substituted or unsubstituted aryl group or arylCroC 4 alkyl group, a substituted or unsubstituted, saturated or unsaturated heterocycle or a group -COM 10 or COOM 10 , wherein M 10 is a hydrogen atom or a C r C 6- Alkylgru ⁇ pe stands,
- M 9 is a substituted or unsubstituted aryl group or arylC r C 4 alkyl group, a substituted or unsubstituted aminoaryl group, a substituted or unsubstituted, saturated or unsaturated heterocycle,
- M 11 and M 12 are independently a substituted or unsubstituted C r Ce alkyl group, an acetyloxy group, a C 3 -C 6 cycloalkyl group, a substituted or unsubstituted aryl group or arylC r C 4 alkyl group, a substituted or unsubstituted aminoaryl group , a substituted or unsubstituted, saturated or unsaturated heterocycle, M 13 is a hydrogen atom or a substituted or unsubstituted C 1 -C 6 -alkyl group,
- M 14 and M 15 are independently a -C 6 alkyl group, a C 2 -C 6 - alkenyl group, a Cs-Ce cycloalkyl group, an aryl Ci-C 4 alkyl group, a substituted or unsubstituted aryl group, or a Bicyclic compound bound via the radicals M 14 or M 15 ,
- X is an oxygen or a sulfur atom
- 16 is a substituted or unsubstituted C r C 6 alkyl group or substituted or unsubstituted aryl group,
- M 17 is a hydrogen atom, a substituted or unsubstituted C r C 6 alkyl group or a substituted or unsubstituted aryl group,
- M 18 represents a hydrogen atom, a cyano group, a substituted or unsubstituted C r C 6 -alkyl group, a group COOM 19 , in which M 19 denotes a hydrogen atom or a substituted or unsubstituted C r C 6 -alkyl group,
- A represents an oxygen atom, a sulfur atom, a sulfoxyl group, a sulfonyl group or a group NM 20a
- M 20a represents a hydrogen atom, a substituted or unsubstituted C 1 -C 6 alkylene group
- M 20 and M 21 independently represent a hydrogen atom Chlorine, bromine, hydroxy, nitro, C 1 -C 6 alkyl, C r C 6 alkoxy, carboxamide, sulfonamide, carboxyl, C 1 -C 4 acyl, cyano or an amino group -NM 22 M 23, where M 22 and M 23 are independently 6 alkyl group for a hydrogen atom or a C r C,
- a ' represents an oxygen atom, a sulfur atom or a group NM 25 , in which M 25 denotes a hydrogen atom or a substituted or unsubstituted C 1 -C 6 -alkyl group,
- M 24 is a hydrogen, a chlorine, a bromine atom, a hydroxy group, a nitro group, a -C 6 alkyl, a C r C 6 alkoxy, a carboxamide, a sulfonamide, a carboxyl, a C r C 4 acyl, a cyano group or an amino group NM 26 M 27, where M 26 and M 27 independently represent hydrogen and 6 alkyl group, a C r C,
- M 28 is a hydrogen atom, a hydroxy group, a substituted or unsubstituted C r C 6 alkyl group or a substituted or unsubstituted aryl or C 1 -C 6 alkylaryl group;
- M 29 is a hydrogen atom or a C 1 -C 4 -alkyl group
- M 30 is a hydrogen, a chlorine, a bromine atom, a nitro, a C 1 -C 6 -AIKyI-, a C r C 6 alkoxy, a carboxamide, a sulfonamide or a cyano group,
- Z represents an oxygen atom or a group NM 32, where M is 32 a hydrogen atom or a C r C 6 alkyl group,
- Z ' is a sulfur atom or a group NM 33, where M is 33 a hydrogen atom or a C r C 6 alkyl group, M 31 is a hydrogen atom, a C r C 6 -alkyl group or a C r C 4 -carboxy-alkyl group,
- M 34 and M 35 independently represent a hydrogen, a chlorine, a bromine atom, a hydroxy group, a nitro group, a -C 6 alkyl, a C 1 -C 6 - alkoxy, carboxamide, sulfonamide -, a carboxyl, a CrC 4 -acyl 1 a cyano group or an amino group -NM 36 M 37, where M 36 and M 37 are independently hydrogen or a C r C 6 alkyl group,
- M 38 and M 39 independently represent a hydrogen, a chlorine, a bromine atom, a hydroxy group, a nitro group, a -C 6 alkyl, a C 1 -C 6 - alkoxy, carboxamide, sulfonamide a carboxyl, a C 1 -C 4 -acyl, a cyano group or an amino group -NM 41 M 42 , in which M 41 and M 42 independently of one another represent a hydrogen atom or a C 1 -C 6 -alkyl group,
- M 40 is a hydrogen atom or a C r C 6 -alkyl group
- M 43 and M 44 independently of one another represent a hydrogen, a chlorine, a bromine atom, a hydroxy group, a nitro group, a C r C ⁇ alkyl, a C 1 -C 6 alkoxy, a carboxamide, a sulfonamide, a carboxyl, a C 1 -C 4 acyl, a cyano group or an amino group -NM 45 M 46 , in which M 45 and M 46 independently of one another represent a hydrogen atom or a C 1 -C 6 -alkyl group,
- D 1 is a fused aromatic or heteroaromatic ring
- D 2 is a carbonyl group
- a group C CD 1 D 11 or a group CD 1 D ", in which D 1 or D" is in each case a substituent with a Hammett constant between 0.4 and 2.0 or both substituents in the sum has a Hammett constant between 0.4 and 2.0;
- M 49 and M 50 independently of one another are a hydrogen atom or a substituted or unsubstituted C 1 -C 6 -alkyl group
- E 1 is an oxygen, a sulfur atom or a group NH
- E 2 represents a group NH or an oxygen atom
- E 3 is an amino group or a hydroxy group
- M 51 and M 52 are independently a hydrogen atom, a halogen atom, a hydroxy group, a -C 4 -hydroxyalkyl group, a C 1 -C 6 - Aminoaikyl distr, a CrC 4 dialkylamino-C r C 4 alkyl group, a linear or branched dC 6 alkyl group, a C 2 -C 6 alkenyl group, an optionally substituted aryl group, a sulfonic acid group, a carboxyl group, a formyl group, a nitro group, a cyano group or a group -NM 54 M 55 , wherein M 54 and M 55 stand independently represent a hydrogen atom, a C 1 - C 6 alkyl group, a C 2 -C 6 alkenyl group, an aryl-C r C 4 alkyl group or a C 1 - C 4 -hydroxyalkyl group, where M 51 and M 52 together membered 6-
- M 53 represents a hydrogen atom, a C 1 -C 4 -hydroxyalkyl group, a C 1 -C 6 -aminoalkyl group, a C 1 -C 4 -dialkylamino-C 1 -C 4 -alkyl group, a linear or branched C 1 -C 6 -alkyl group, a C 2 -C 6 Alkenyl group, an optionally substituted aryl group, a Ci-C 4 -Sulfonylalkyl distr, a C r C 4 - carboxyalkyl group or a C 2 -C 6 polyhydroxyalkyl group, Y is an oxygen atom, a sulfur atom, an optionally substituted methylene group or a group NM 60 , where M 6Q can stand for the same groups defined under M 55 ,
- a ' is a chloride, bromide, iodide, hexafluorophosphate, tetrachlorozincate, tetrafluoroborate, trifluoromethylsulfonate, methylsulfonate or p-toluenesulfonate,
- M 51 , M 52 , M 53 and A ' are selected from the groups defined under compound C19,
- R 1 and R 2 are independently a linear or cyclic C 1 -C 6 - alkyl group, a C 2 -C 6 alkenyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, an aryl-CrC 6 - alkyl group, a C r C 6 hydroxyalkyl group, a C 2 -C 6 polyhydroxyalkyl group, a C 1 -C 6 alkoxyCrCe alkyl group, a group R l R ll N- (CH 2 ) m - 1 where R 1 and R "are each independently a hydrogen atom, a C 1 -C 4 -alkyl group, a C 1 -C 4 -hydroxyalkyl group or an aryl-C 1 -C 6 -alkyl group, wherein R 1 and R "together with the nitrogen atom are a 5-, 6- or 7-membered Ring can form and m stands for a number 2, 3, 4, 5 or
- R 3 and R 4 independently represent a hydrogen atom or a C r C 3 - alkyl group, wherein at least one of the radicals R 3 and R 4 is a Ci-C 6 alkyl group,
- R 5 represents a hydrogen atom, a ⁇ dC alkyl group, a group dC 6 hydroxyalkyl, a C 2 -C 6 polyhydroxyalkyl group, a C r C 6 alkoxy group, a C r C 6 - hydroxyalkoxy group, a group R '"R lv N- (CH 2) q - wherein R 1" and R IV are independently a hydrogen atom, a C r C 6 alkyl group, a d-Ce-hydroxyalkyl group or an aryl-dC 6 alkyl group and q stands for a number 1, 2, 3, 4, 5 or 6, where the radical R 5 together with one of the radicals R 3 or R 4 can form a 5- or 6-membered aromatic ring which is optionally substituted by a halogen atom, a C r C 6 alkyl group, a d-C ⁇ -hydroxyalkyl group, a C 2 - r C 6 -polyhydroxyalky
- Y represents an oxygen atom, a sulfur atom or a group NR V ", wherein R v" stands for a hydrogen atom, an aryl group, a heteroaryl group, a dC 6 - alkyl group or a C r C 6 arylalkyl group,
- X is halide, benzenesulfonate, p-toluenesulfonate, C r C 4 -alkanesulfonate, trifluoromethanesulfonate, perchlorate, 0.5 sulfate, hydrogensulfate, tetrafluoroborate, hexafluorophosphate or tetrachlorozincate,
- Het is an optionally substituted heteroaromatic
- X 1 is a direct bond or a carbonyl group
- the radical Het according to formula (C23) preferably represents the molecule fragment of the formula (I),
- R 1 and R 2 are independently a hydrogen atom, a hydroxy group, a halogen atom, a nitro group, a linear or cyclic C r C group 6 alkyl, a C 2 -C 6 alkenyl group, an optionally substituted Aryl group, a cyanomethyl group, a cyanomethylcarbonyl group, an optionally substituted heteroaryl group, an arylCrC 6 -alkyl group, a C r C 6 -hydroxyalkyl group, a C 2 -C 6 polyhydroxyalkyl group, a C r C 6 alkoxy group, a C r C 6 alkoxycarbonyl group, a -C 6 -alkoxy-C 2 -C 6 alkyl group, a C 1 -C 6 alkyl group -SuIfO-, a CrC ⁇ -carboxyalkyl group, a group R'R "N- (CH 2) m - in which R 1 and R "
- X 2 and X 3 are independently of each other a nitrogen atom or a group
- R 3 is C 2 -C 6 alkenyl group, an optionally substituted aryl group, a cyanomethyl group, a cyanomethylcarbonyl a hydrogen atom, a hydroxy group, a halogen atom, a nitro group, a linear or cyclic -C 6 alkyl group, a C, a optionally substituted heteroaryl group, an aryl-alkyl group -C 6, a C 1 -Ce- hydroxyalkyl group, a C 2 -C 6 polyhydroxyalkyl group, a CrC ⁇ -alkoxy group, a C r C 6 alkoxycarbonyl group, a C r C 6 alkoxy C 2 -C 6 alkyl group, a C 1 -C 6 sulfoalkyl group, a C r C 6 carboxyalkyl group and a group R 111 R 17 N- ( CH 2 ) H -, wherein R 1 "and R l
- X 4 is an oxygen atom, a sulfur atom, a vinyl group or an NH group, which latter two groups are independently optionally substituted with a linear or cyclic -C 6 alkyl group, a C 2 -C 6 - alkenyl group, an optionally substituted aryl group an optionally substituted heteroaryl group, an aryl-CrC 6 -alkyl group, a C 2 -C 6 -hydroxyalkyl group, a C 2 -C 6 -polyhydroxyalkyl group, a C r C 6 -alkoxy-C 2 -C 6 -alkyl group , a C r C 6 sulfoalkyl group, a Ci-C 6 -Carboxyalkyl distr, a group R V R VI N- (CH 2 ) P -, wherein R v and R v ⁇ independently represent a hydrogen atom, a linear or cyclic C t -C 6 -alkyl group,
- CH-acidic compounds also include enamines which are formed from quaternized N-heterocycles with an CH acidic alkyl group in conjugation with the quaternary nitrogen by alkaline treatment.
- enamines which are formed from quaternized N-heterocycles with an CH acidic alkyl group in conjugation with the quaternary nitrogen by alkaline treatment.
- suitable enamines compounds having the general formula (C24) can be mentioned,
- M 61 is an aromatic radical, in particular an optionally with a C r C 4 alkyl, C r C 4 hydroxyalkyl, hydroxy, methoxy or halogen group-substituted 5-membered or 6-membered aryl group, preferably a Phenyl radical, or a 5-membered or 6-membered, fused, aliphatic or aromatic, carbocyclic or heterocyclic ring, preferably a phenyl radical, a quinoline or pyridyl radical,
- M 62 represents a hydrogen atom, a linear or branched d-Ca-alkyl, a linear or branched C r C 8 -hydroxyalkyl or a C r C 8 -alkoxyalkyl group, wherein between the C atoms of the alkyl chain an oxygen atom can sit, and
- M 63 is a linear or branched C r -C 8 alkyl group, a C 1 -C 6 -alkoxy-C 1 - C 6 alkyl group, a Ci-Ce-alkylamino-CRCE-alkyl group, a C r C 6 - alkylmercapto C r C 6 alkyl group, a Ci-C 6 -alkoxy-C r C 6 alkylene group, a C r C 6 alkylamino -C 6 alkylene group, a C r C 6 -alkylmercapto-C r C 6 - alkylene group, with the proviso that the radicals M 61 and M 63 form a straight chain or branched C r C 8 alkylene group, or an oxygen atom, a nitrogen atom or a sulfur atom together with the nitrogen atom and the carbon atom of the enamine structure a cyclic compound, if M 63 is equal to a linear or
- the CH-acidic compounds are selected from the group consisting of physiologically compatible anions, in particular p-toluenesulfonates, methanesulfonates, hydrogensulfates, tetrafluoroborates and halides, such as the chlorides, bromides and iodides, formed salts of 1, 4- Dimethylquinolinium, 1-ethyl-4-methyl-quinolinium, 1-ethyl-2-methylquinolinium, 1, 2,3,3-tetramethyl-3H-indolium, 2,3-dimethylbenzothiazolium, 2,3-dimethylnaphtho [ 1,2-d] thiazoliums, 3-ethyl-2-methyl-naphtho [1,2-d] thiazoliums, 3-ethyl-2-methylbenzoxazoliums, 1,2,3-trimethylquinoxaliniurns, 3-ethyl-2- Methyl-benzothiazolium,
- Ndan-1-one, 2-amino-4-imino-1, 3-thiazoline hydrochloride Benzoylacetonitrile, 3-dicyanomethylenedan-1-one, 2- (2-furanoyl) acetonitrile, 2- (2-theonyl) acetonitrile, 2- (cyanomethyl) benzimidazole, 2- (cyanomethyl) benzothiazole and 2- (2.5 dimethyl-3-furanoyl) acetonitrile.
- the agents according to the invention preferably contain the CH-acidic compounds in an amount of 0.03 to 65 mmol, more preferably 1 to 40 mmol per 100 g of the total multicomponent agent.
- the primary amino group compounds which the preparation (B) may contain are preferably benzene derivatives having at least one primary amino group.
- those benzene derivatives are preferred which carry in ortho, metha or para position to the primary amino group at least one group which is selected from: a hydroxyl group, a primary amino group, a secondary amino group and a tertiary amino group
- These primary aromatic amines are preferably selected from the compounds of formula (Am1),
- G 1 represents a hydrogen atom, a C 1 - to C 4 -alkyl radical, a Cr to C 4 -mono- hydroxyalkyl radical, a C 2 - to C 4 polyhydroxyalkyl radical, a (C 1 - to C 4) alkoxy (C 1 - to C 4 ) -alkyl radical, a 4'-aminophenyl radical or a C 1 - to C 4 -alkyl radical which is substituted by a nitrogen-containing group, a phenyl or a 4'-aminophenyl radical;
- G 2 represents a hydrogen atom, a C r to C 4 alkyl radical, a C 1 - to C 4 -mono hydroxyalkyl radical, a C 2 - to C 4 -polyhydroxyalkyl radical, a (C 1 - to C 4 ) -alkoxy - (C 1 - to C 4 ) -alkyl radical or a C 1 - to C 4 -alkyl radical which is substituted by a nitrogen-containing group;
- G 3 represents a hydrogen atom, a halogen atom, such as a chlorine, bromine, iodine or fluorine atom, a C 1 - to C 4 -alkyl radical, a C 1 - to C 4 -monohydroxyalkyl radical, a C 2 - to C 4 -polyhydroxyalkyl, C 1 - to C 4 -hydroxyalkoxy, C 1 - to C 4 -acetylaminoalkoxy, C 1 - to C 4 -mesylaminoalkoxy or C 1 - to C 4 -carbamoylaminoalkoxy;
- a halogen atom such as a chlorine, bromine, iodine or fluorine atom
- a C 1 - to C 4 -alkyl radical such as a chlorine, bromine, iodine or fluorine atom
- a C 1 - to C 4 -alkyl radical such as a chlorine, bromine
- G 4 represents a hydrogen atom, a halogen atom or a C 1 - to C 4 -alkyl radical or
- G 3 and G 4 when G 3 and G 4 are ortho to each other, they may together form a bridging ⁇ , ⁇ -alkylenedioxy group, such as, for example, an ethylenedioxy group.
- nitrogen-containing groups of the formula (Am-1) are, in particular, the amino groups, 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.
- C 1 - to C 4 -alkyl radicals mentioned as substituents are the groups methyl, ethyl, propyl, isopropyl and butyl. Ethyl and methyl are preferred alkyl radicals.
- C 1 -C 4 -alkoxy radicals which are preferred according to the invention are, for example, a methoxy radical. or an ethoxy group.
- a C 1 to C 4 hydroxyalkyl group there may be mentioned a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group. A 2-hydroxyethyl group is particularly preferred.
- a particularly preferred C 2 to C 4 polyhydroxyalkyl group is the 1, 2-dihydroxyethyl group.
- halogen atoms are according to the invention F, Cl or Br atoms, Cl atoms are very particularly preferred.
- the other terms used are derived according to the invention from the definitions given here.
- Particularly preferred primary aromatic amines of formula (Am-1) 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 1 N-BiS- ( ⁇ -hydroxyethyl) -p-phenylenediamine, 4-N, N-bis- ( ⁇ -) hydroxyethyl) amino-2-methylaniline, 4-N, N-bis (
- p-phenylenediamine derivatives of the formula (Am-1) are p-toluenediamine, 2- (ß-hydroxyethyl) -p-pheny! Endiamin and N, N-bis (.beta.-hydroxyethyl) -p-phenylenediamine.
- aromatic primary amines which contain at least two aromatic nuclei.
- Z 1 and Z 2 independently of one another represent a hydroxyl or NH 2 radical which is optionally substituted by a C 1 - to C 4 -alkyl radical, by a C 1 - to C 4 -hydroxyalkyl radical and / or by a bridge Y is substituted or optionally
- the bridge Y is an alkylene group having 1 to 14 carbon atoms, such as a linear or branched alkylene chain or an alkylene ring, of one or more nitrogen-containing groups and / or one or more
- Heteroatoms such as oxygen, sulfur or nitrogen atoms may be interrupted or terminated and possibly by one or more hydroxyl or d-bis
- C 8 alkoxy may be substituted, or a direct bond
- G 5 and G 6 are each independently a hydrogen or halogen atom, a C 1 - to C 4 -alkyl radical, a d- to C 4 monohydroxyalkyl radical, a C 2 - to C 4 -
- Polyhydroxyalkyl radical a C 1 - to C 4 -aminoalkyl radical or a direct compound for bridging Y,
- G 7 , G 8 , G 9 , G 10 , G 11 and G 12 are each independently
- Hydrogen atom a direct bond to the bridging Y or a C 1 - to C 4 -
- Preferred binuclear compounds of the formula (Am-2) are in particular: N, N'-bis ( ⁇ -hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diamino-propane-2 ol, N, N'-bis- ( ⁇ -hydroxy- ethyl) -N, N'-bis (4'-aminophenyl) ethylenediamine, N, N'-bis (4-aminophenyl) tetramethylene diamine, N, N'-bis ( ⁇ -hydroxyethyl) -N , N'-bis (4-aminophenyl) tetramethylenediamine, N 1 N'-bis (4-methyl-aminophenyl) tetramethylenediamine, N, N'-diethyl-N, N'-bis- (4'-amino 3'-methylphenyl) ethylenediamine, bis (2-hydroxy-5-aminophenyl)
- a p-aminophenol derivative or one of its physiologically acceptable salts as the primary aromatic amine.
- Particularly preferred are p-aminophenol derivatives of the formula (Am-3)
- G 13 represents a hydrogen atom, a halogen atom, a C 1 to C 4 alkyl radical, a C 1 to C 4 monohydroxyalkyl radical, a C 2 to C 4 polyhydroxyalkyl radical, a (C 1 to C 4 ) , alkyl alkoxy (C r to C 4) a C 1 - to C 4 aminoalkyl radical, a hydroxy (C 1 - to C 4) alkylamino group, a C 1 - to C 4 -Hydroxyalkoxyrest, C 1 - to C 4 - hydroxyalkyl (C r to C 4 ) aminoalkyl or a (di-C 1 - to C 4 alkylamino) - (C r to C 4 ) alkyl, and
- G 14 is a hydrogen or halogen atom, a C 1 - to C 4 -alkyl radical, a C 1 - to C 4 -monohydroxyalkyl radical, a C 2 - to C 4 -polyhydroxyalkyl radical, a (C 1 - to C 4 ) - Alkoxy (C r to C 4 ) -alkyl radical, a C 1 - to C 4 -aminoalkyl radical or a C 1 - to C 4 -cyanoalkyl radical, G 15 represents a hydrogen atom and
- G 16 is hydrogen or a halogen atom.
- Particularly preferred p-aminophenols of the formula (Am-3) are p-aminophenol, A-amino-3-methylphenol, 4-amino-3-fluorophenol, 2-hydroxymethylamino-4-arninophenol, 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 and their physiologically acceptable salts.
- Very particularly preferred compounds of the formula (Am-3) are p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- ( ⁇ , ⁇ -dihydroxyethyl) phenol and amino-2- (diethylaminomethyl) -phenol.
- the primary aromatic amines present in the agents according to the invention are furthermore preferably selected from o-aminophenol and its derivatives, for example 2-amino-4-methylphenol, 2-amino-5-methylphenol or 2-amino-4-chlorophenol,
- Diaminobenzene and its derivatives such as 3,4-diaminobenzoic acid and 2,3-diamino-1-methylbenzene.
- heteroaromatic primary amines according to the invention are selected, for example, from the pyridine, pyrimidine, pyrazole, pyrazolopyrimidine derivatives having at least one primary amino group 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-amino-pyridine , 2,3-diamino-6-methoxy-pyridine, 2- ( ⁇ -methoxy-ethyl) -amino-3-amino-6-methoxypyridine and 3,4-diamino-pyridine, but also 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-diamino-pyridine, 2,3-diamino-6-methoxypyridine and 3,5-diamino-2,6-dimethoxypyr
- Particularly preferred pyridine derivatives are 2-amino-3-hydroxypyridine, 2-amino-5-chloro-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine and 3,5-diamino-2,6-di- methoxypyridine.
- Preferred pyrimidine derivatives are, in particular, the compounds described in German Patent DE 2 359 399, Japanese Laid-Open Patent Publication JP 02019576 A2 or in the published patent application WO 96/15765, such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy- 2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2-dimethylamino-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6- Triaminopyrimidine, but also 4,6-diaminopyrimidine, 4-amino-2,6-dihydroxypyrimidine, 2,4-diamino-6-hydroxypyrimidine, 2-amino-4-methylpyrimidine and 2-amino-4-hydroxy-6-methylpyrimidine.
- Particularly preferred pyrimidine derivatives are 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine and 2-hydroxy-4,5,6-triaminopyrimidine.
- Preferred pyrazole derivatives are, in particular, the compounds described in patents DE 3 843 892, DE 4 133 957 and patent applications WO 94/08969, WO 94/08970, EP-740 931 and DE 195 43 988, such as 4,5 -Diamino-1-methylpyrazole, 4,5- Diamino-1- ( ⁇ -hydroxyethyl) pyrazole, 3,4-diaminopyrazole, 4,5-diamino-1- (4'-chlorobenzyl) pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4.5 Diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazinopyrazole, 1-benzyl-4,5-diamino-3 -methylpyrazole, 4,5-diamino-3-tert-butyl
- a particularly preferred pyrazole derivative is 4,5-diamino-1- ( ⁇ -hydroxyethyl) pyrazole.
- Preferred pyrazolo-pyrimidine derivatives are, in particular, the derivatives of the pyrazolo [1,5-a] pyrimidine of the following formula (Am-4) and its tautomeric forms, provided that a tautomeric equilibrium exists:
- G 17 , G 18 , G 19 and G 20 independently of one another represent a hydrogen atom, a C 1 - to C 4 -alkyl radical, an aryl radical, a C 1 - to C 4 -hydroxyalkyl radical, a C 2 - to C 4 polyhydroxyalkyl a (C 1 - to C 4) alkoxy, alkyl (C r to C 4) a C 1 - to C 4 -aminoalkyl radical, which may be optionally protected by an acetyl ureide or a sulfonyl radical , a (C 1 - to C 4 ) -alkylamino- (C r to C 4 ) -alkyl radical, a di-C (C 1 - to C 4 ) -alkyl] - (C 1 -C 4 ) -aminoalkyl radical where the dialkyl radicals optionally form a carbon cycle or a heterocycle having 5 or 6 chain members,
- the X radicals independently of one another represent a hydrogen atom, a C 1 - to C 4 -alkyl radical, an aryl radical, a C 1 - to C 4 -hydroxyalkyl radical, a C 2 - bis C 4 - Polyhydroxyalkyl group, a C 1 - to C 4 aminoalkyl radical, a (C 1 - to C 4) alkylamino (C 1 - to C 4) alkyl group a di - [(C r to C 4) alkyl] - ( C 1 - to C 4 ) -aminoalkyl radical, where the dialkyl radicals optionally form a carbon cycle or a heterocycle having 5 or 6 chain members, a C 1 - to C 4 -hydroxyalkyl- or a di- (C 1 - to C 4 - hydroxyalkyl) aminoalkyl radical, an amino radical, a C 1 - to C 4 -alkyl or di- (C 1 - to C
- pyrazolo [1, 5-a] pyrimidines of the above formula (Am-4) can be prepared as described in the literature by cyclization from an aminopyrazole or from hydrazine.
- the agents according to the invention preferably contain the compound with primary amino group in an amount of 0.03 to 65 mmol, preferably 1 to 40 mmol per 100 g of the total multicomponent agent.
- Formulation (A) and / or preparation (B) may further contain one or more substantive dyes for shade.
- Direct dyes are usually nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols.
- Preferred substantive dyes are those having the international designations or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, Acid Yellow 1, Acid Yellow 10, Acid Yellow 23, Acid Yellow 36, HC Orange Disperse Orange 3, Acid Orange 7, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, Acid Red 33, Acid Red 52, HC Red BN, Pigment Red 57: 1, HC Blue 2, HC Blue 11, HC Blue 12, Disperse Blue 3, Acid Blue 7, Acid Green 50, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Acid Violet 43, Disperse Black 9, Acid Black 1, and Acid Black 52 known compounds as well as 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis ( ⁇ -hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- ( ⁇ -hydroxyethyl) aminophenol, 2- (2'-hydroxyethyl) amino-4,6-dinitrophenol, 1- (2'-hydroxyethyl) amino-4-
- cationic compounds are preferably used as substantive dyes. Particularly preferred are
- aromatic systems substituted with a quaternary nitrogen group such as Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 and Basic Brown 17, as well as
- Preferred cationic substantive dyes of group (c) are in particular the following compounds:
- the compounds of the formulas (DZ1), (DZ3) and (DZ5) which are also known by the names Basic Yellow 87, Basic Orange 31 and Basic Red 51, are very particularly preferred cationic substantive dyes of group (c).
- the cationic direct dyes which are sold under the trademark Arianor ® are, according to the invention also very particularly preferred cationic direct dyes.
- compositions according to the invention according to this embodiment preferably contain the substantive dyes in an amount of from 0.01 to 20% by weight, based on the total multicomponent agent.
- the preparations of the invention may also naturally occurring dyes such as henna red, henna neutral, henna black, chamomile, sandalwood, black tea, buckthorn bark, sage, bluewood, madder root, Catechu, Sedre and alkano root are included.
- the agent according to the invention may optionally contain one or more oxidation dye precursors, so-called coupler and developer components. It is important to ensure that the selection and preparation of the oxidation dye precursors carried out so that it does not come before the application of the agent on the fiber to be dyed to an undesirable reaction with the other dye precursors.
- oxidation dye precursors which carry a primary amino group, they must not be added to the preparation (A), for example, in order to prevent premature reaction with the reactive carbonyl component. Usually, the oxidation dye precursors are therefore added to the preparation (B) or formulated separately from preparation (A) and (B) in a separate chamber of the multi-chamber tube.
- the developer components are usually primary aromatic amines having a further, in the para or ortho position, free or substituted hydroxy or amino group, diaminopyridine derivatives, heterocyclic hydrazones, 4-amino pyrazole derivatives and 2,4,5,6-tetraaminopyrimidine and its Derivatives used.
- the preferred developer components correspond to the compounds already described above as primary amino group compounds.
- Suitable coupler substances for use in the multicomponent agents according to the invention are, in particular, 1-naphthol, 1, 5, 2,7- and 1, 7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, Phenylenediamine, 1-phenyl-3-methyl-pyrazolone-5, 2,4-dichloro-3-aminophenol, 1,3-bis (2 ', 4'-diaminophenoxy) -propane, 2-chloro resorcinol, 4-chloro-resorcinol, 2-chloro-6-methyl-3-aminophenol, 2-amino-3-hydroxypyridine, 2-methylresorcinol
- Preferred coupler components according to the invention are m-aminophenol and its derivatives such as, for example, 5-amino-2-methylphenol, N-cyclopentyl-3-aminophenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-amino phenoxyethanol, 2,6-dimethyl-3-aminophenol, 3-trifluoroacetylamino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol,
- Resorcinol monomethyl ether 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol,
- Pyridine derivatives such as 2,6-dihydroxypyridine, 2-amino-3-hydroxypyridine,
- Naphthalene derivatives such as 1-naphthol, 2-methyl-1-naphthol, 2-hydroxy-methyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1, 5-dihydroxynaphthalene, 1, 6
- Morpholine derivatives such as 6-hydroxybenzomorpholine and 6-aminobenzomorpholine,
- Indole derivatives such as 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole,
- Pyrimidine derivatives such as 4,6-diaminopyrimidine, 4-amino-2,6-dihydroxypyrimidine, 2,4-diamino-6-hydroxypyrimidine, 2,4,6-trihydroxypyrimidine, 2-
- Methylenedioxybenzene derivatives such as 1-hydroxy-3,4-methylenedioxybenzene, 1-amino-3,4-methylenedioxybenzene and 1- (2'-hydroxyethyl) -amino-3,4-methylenedioxybenzene.
- coupler components according to the invention are 1-naphthol, 1, 5, 2,7- and 1, 7-dihydroxynaphthalene, 3-aminophenol, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, resorcinol, 4-chlororesorcinol , 2-chloro-6-methyl-3-aminophenol, 2-methyl resorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol and 2,6-dihydroxy-3,4-dimethylpyridine.
- the agent according to the invention comprises at least one developer component selected from p-phenylenediamine, p-toluenediamine, p-aminophenol, N, N-bis (2-hydroxyethyl) -p-phenylenediamine, 1 - (2-hydroxyethyl) -2,5-diaminobenzene, 3-methyl-4-aminophenol, bis (2-hydroxy-5-aminophenyl) methane, 2,4,5,6-tetraaminopyrimidine and 1- (2-hydroxyethyl ) - 4,5-diaminopyrazole, and / or at least one further coupler component selected from 2- (2,4-diaminophenoxy) ethanol, 1, 3-bis (2,4-diaminophenoxy) -propane, 5-amino-2 - methylphenol, 2-amino-3-hydroxypyridine, resorcinol, 2-methylresorcino
- the developer components and the coupler components are contained in the multi-component agents according to the invention preferably in an amount of 0.005 to 20 wt .-%, preferably 0.1 to 5 wt .-%, each based on the total multi-component agent.
- developer components and coupler components are generally used in approximately molar amounts to each other.
- a certain excess of individual oxidation dye precursors is not disadvantageous, so that developer components and coupler components in a molar ratio of 1: 0.5 to 1: 3, in particular 1: 1 to 1 : 2, may be included.
- the agent according to the invention may contain a precursor of a naturally-analogous dye.
- precursors of naturally-analogous dyes such indoles and indolines are preferably used which have at least one hydroxy or amino group, preferably as a substituent on the six-membered ring. These groups may carry further substituents, e.g. In the form of an etherification or esterification of the hydroxy group or an alkylation of the amino group.
- Particularly suitable precursors of natural-analogous hair dyes are derivatives of 5,6-dihydroxyindoline of the formula (Ia),
- R 1 is hydrogen, a C r C 4 -alkyl group or a C r C 4 -hydroxy-alkyl group
- R 2 is hydrogen or a -COOH group, where the -COOH group may also be present as a salt with a physiologically compatible cation,
- R 3 is hydrogen or a C 1 -C 4 -alkyl group
- R 4 is hydrogen, a C r C 4 alkyl group or a group -CO-R 6 , in which
- R 6 is a C 1 -C 4 -alkyl group
- R 5 is one of the groups mentioned under R 4 , as well as physiologically acceptable salts of these compounds with an organic or inorganic acid.
- Particularly preferred derivatives of indoline are 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6 dihydroxyindoline, 5,6-dihydroxyindoline-2-carboxylic acid and 6-hydroxyindoline, 6-aminoindoline and 4-aminoindoline.
- N-methyl-5,6-dihydroxyindoline N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline and especially 5, 6-Dihydroxyindolin.
- R 1 is hydrogen, a C r C 4 -alkyl group or a C r C 4 -hydroxyalkyl group
- R 2 is hydrogen or a -COOH group, where the -COOH group may also be present as a salt with a physiologically compatible cation,
- R 3 is hydrogen or a C 1 -C 4 -alkyl group
- R 4 is hydrogen, a C r C 4 alkyl group or a group -CO-R 6 , in which
- R 6 is a C 1 -C 4 -alkyl group
- R 5 represents one of the groups mentioned under R 4 ,
- Particularly preferred derivatives of indole are 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5, 6-dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid, 6-hydroxyindole, 6-aminoindole and 4-aminoindole.
- N-methyl-5,6-dihydroxyindole N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole, and especially the 5,6 -Dihydroxyindol.
- the indoline and indole derivatives can be used in the inventive compositions both as free bases and in the form of their physiologically acceptable salts with inorganic or organic acids, for.
- hydrochlorides sulfates and hydrobromides are used.
- the indole or indoline derivatives are contained in these usually in amounts of 0.05-10 wt .-%, preferably 0.2-5 wt .-%, each based on the total multicomponent agent.
- the indoline or indole derivative in hair dyes in combination with at least one amino acid or an oligopeptide.
- the amino acid is advantageous an ⁇ -amino acid;
- Very particularly preferred ⁇ -amino acids are arginine, ornithine, lysine, serine and histidine, in particular arginine.
- oxidation dye precursors or the direct dyes it is not necessary for the oxidation dye precursors or the direct dyes to be in each case homogeneous compounds. Rather, in the hair colorants according to the invention, due to the production process for the individual dyes, in minor amounts, further components may be included, as far as they do not adversely affect the dyeing result or for other reasons, e.g. toxicological, must be excluded.
- oxidizing agents for. B. H 2 O 2
- oxidizing agents can be dispensed with without problems in such a case. However, it may u. It may be desirable to add hydrogen peroxide or other oxidizing agents to the compositions of the invention for achieving the shades that are lighter than the keratin-containing fiber to be dyed.
- oxidizing agent chemical oxidizing agents can be used.
- Hydrogen peroxide is a very particularly preferred chemical oxidizing agent according to the invention.
- the agent according to the invention can also be at least one oxidizing agent
- the behavior described under (i) typically has oxidases that react with their respective substrate to form hydrogen peroxide.
- oxidases that react with their respective substrate to form hydrogen peroxide.
- examples of such enzymes are glucose oxidase (EC No. 1.1.3.4), alcohol oxidase (EC No. 1.1.3.13), oxidase for secondary alcohols (EC No. 1.1.3.18), oxidase for long-chain alcohols (US Pat. EC No. 1.1.3.20), glycerol-3-phosphate oxidase (EC No. 1.1.3.21), glycolate oxidase (EC No. 1.1.3.15), methanol oxidase (EC No. 1.1.3.31 ), Vanillyl alcohol oxidase (EC No.
- oxidases are uricase, glucose oxidase and choline oxidase.
- Uricase is a very particularly preferred class (i) enzyme.
- the compositions according to the invention must always contain the corresponding substrates in a sufficient amount.
- Enzymes which directly oxidize the dye precursors by means of atmospheric oxygen are, for example, the laccases (EC No. 1.10.3.2), the tyrosinases (EC No. 1.10.3.1), ascorbate oxidase (EC No. 1.10 .3.3), bilirubin oxidases (EC No. 1.3.3.5) and phenol oxidases of the type Acremonia, Stachybotrys or Pleurotus.
- the laccases are according to the invention very particularly preferred enzymes of class (ii).
- Category (iii) of the enzymes preferred according to the invention includes the peroxidases (EC No. 1.11.1.7). These allow dyeings even with small amounts of hydrogen peroxide. It is immaterial whether small amounts of hydrogen peroxide are incorporated into the formulation or whether this is formed in situ by the enumerated under (i) enzymes.
- Particularly preferred according to the invention is the peroxidase, which can be obtained from horseradish.
- the enzyme is preferably used in an amount of 0.0001 - 1 wt .-%, based on the protein amount of the enzyme and the entire multicomponent agent.
- Oxidizing agents which can furthermore be used are oxidation catalysts, for example metal ions, iodides or quinones. These catalysts usually accelerate the oxidation of the dye precursors by atmospheric oxygen. But it is also conceivable that the catalysts accelerate the oxidation by a present chemical oxidant. In the context of this latter embodiment, on the one hand, the reaction rate can be increased or, on the other hand, the concentration of the chemical oxidants used can be reduced.
- Suitable metal ions are, for example, Zn 2+ , Cu 2+ , Fe 2+ , Fe 3+ , Mn 2+ , Mn 4+ , Li + , Mg 2+ , Ca 2+ and Al 3+ . Particularly suitable are Zn 2+ , Cu 2+ and Mn 2+ .
- the metal ions can in principle 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.
- the agent according to the invention preferably contains no oxidizing agent, since in this case a particularly gentle coloring agent results.
- the addition of care substances can further reduce any possible stress or damage to the fiber to be dyed during the dyeing process.
- the preparation (A) and / or the preparation (B) therefore preferably also contains at least one care component.
- a care component for example, cationic surfactants can be used. Preference is given to cationic surfactants of the quaternary ammonium compounds, esterquats and amidoamines type.
- Preferred quaternary ammonium compounds are ammonium halides, in particular chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, eg.
- alkyltrimethylammonium chlorides dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, eg.
- cetyltrimethylammonium chloride stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethyl ammonium chloride, Lauryldirnethylbenzylammoniumchlorid and Tricetylmethylammonium- chloride, as well as known under the INCI names Quatemium-27 and Quatemium-83 imidazolium compounds.
- the long alkyl chains of the above-mentioned surfactants preferably have 10 to 18 carbon atoms.
- Esterquats 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 marketed under the trade names Stepantex® ®, ® and Dehyquart® Armocare® ®.
- the products Armocare® ® VGH-70, an N, N-bis (2-Palmitoyloxy- ethyl) dimethy! Ammonium chloride, and Dehyquart® ® F-75, Dehyquart® ® C-4046, Dehyquart® ® L80 and Dehyquart® ® AU-35 are examples of such esterquats.
- the alkylamidoamines are usually prepared by amidation of natural or synthetic fatty acids and fatty acid cuts with dialkylaminoamines.
- An inventively particularly suitable compound from this group of substances that available under the name Tegoamid ® S 18 commercially stearamidopropyldimethylamine is dimethylamine.
- the cationic surfactants are contained in the multicomponent agents according to the invention preferably in amounts of from 0.05 to 10% by weight, based on the total application preparation. Amounts of 0.1 to 5 wt .-% are particularly preferred. Also suitable as a care component are nourishing polymers, for example cationic polymers, which have a group in the main and / or side chain which may be "temporary" or “permanent” cationic.
- "permanently cationic” refers to those polymers which have a cationic group, irrespective of the pH of the agent. These are usually polymers containing a quaternary nitrogen atom, for example in the form of an ammonium group. Preferred cationic groups are quaternary ammonium groups. In particular, those polymers in which the quaternary ammonium group is bonded via a C 1- 4 hydrocarbon group to a synthesized from acrylic acid, methacrylic acid or derivatives thereof, polymer backbone have been found to be particularly suitable.
- copolymers of vinylpyrrolidone such as the commercial products Copolymer 845 (manufactured by ISP), Gaffix ® VC 713 (manufactured by ISP), Gafquat ® ASCP 1011, Gafquat ® HS 110, Luviquat ® 8155 and Luviquat ® MS 370 available are.
- erfindungsi employable cationic polymers are the so-called "temporary cationic" polymers. These polymers usually contain an amino group which, at certain pH values, is present as quaternary ammonium group and thus cationic.
- temporary cationic polymers usually contain an amino group which, at certain pH values, is present as quaternary ammonium group and thus cationic.
- chitosan and its derivatives, such as 101 are freely available commercially, for example under the trade names Hydagen CMF ®, Hydagen HCMF ®, Kytamer ® PC and Chitolam ® NB /.
- cationic polymers are cationic cellulose derivatives and chitosan and its derivatives, in particular the commercial products Polymer ® JR 400, Hydagen ® HCMF and Kytamer ® PC, cationic guar derivatives, cationic honey derivatives, in particular the commercial product Honeyquat ® 50, cationic Alkylpolyglycodside according to DE-PS 44 13 686 and polymers of the type Polyquaternium-37.
- cationized protein hydrolysates are to be counted among the cationic polymers, wherein the underlying protein hydrolyzate from the animal, for example from collagen, milk or keratin, from the plant, for example from wheat, corn, rice, potatoes, soy or almonds, marine life forms, for example from fish collagen or algae, or biotechnologically derived protein hydrolysates.
- the agents according to the invention preferably contain the caring polymers in an amount of from 0.01 to 5% by weight, in particular in an amount of from 0.1 to 2% by weight, in each case based on the total application preparation.
- care component it is also possible to add at least one vitamin, one provitamin, one vitamin precursor and / or one of its derivatives.
- vitamins, pro-vitamins and vitamin precursors are preferred, which are usually assigned to groups A, B, C, E, F and H.
- the two-component agents according to the invention particularly preferably contain vitamins, provitamins and vitamin precursors from groups A, B, C, E and H.
- Panthenol, pantolactone, pyridoxine and its derivatives as well as nicotinamide and biotin are very particularly preferred.
- extracts are produced by extraction of the whole plant. However, in individual cases it may also be preferred to prepare the extracts exclusively from flowers and / or leaves of the plant.
- the extracts of green tea, oak bark, nettle, witch hazel, hops, henna, chamomile, burdock root horsetail, Hawthorn, lime blossom, almond, aloe vera, spruce needle, horse chestnut, sandalwood, juniper, coconut, mango, apricot, lime, wheat, kiwi, melon, orange, grapefruit, sage, rosemary, birch, mallow, meadowfoam, quenelle, yarrow, thyme , Balm, toadstool, coltsfoot, marshmallow, meristem, ginseng and ginger root are preferred.
- compositions according to the invention may furthermore contain as care component at least one protein hydrolyzate and / or one of its derivatives.
- Protein hydrolysates are product mixtures obtained by acid, alkaline or enzymatically catalyzed degradation of proteins (proteins).
- the term protein hydrolyzates also means total hydrolyzates as well as individual amino acids and their derivatives as well as mixtures of different amino acids.
- polymers made up of amino acids and amino acid derivatives are understood by the term protein hydrolyzates. The latter include, for example, polyalanine, polyasparagine, polyserine, etc.
- Further examples of compounds which can be used according to the invention are L-alanyl-L-proline, polyglycine, glycyl-L-glutamine or D / L-methionine-S-methylsulfonium chloride.
- ⁇ -amino acids and their derivatives such as ⁇ -alanine, anthranilic acid or hippuric acid can also be used.
- the molecular weight of the protein hydrolysates which can be used according to the invention is between 75, the molecular weight for glycine, and 200,000, preferably the molecular weight is 75 to 50,000 and very particularly preferably 75 to 20,000 daltons.
- protein hydrolysates of both vegetable and animal or marine or synthetic origin can be used.
- compositions according to the invention can also be used as care component, for example UV stabilizers, for example TiO 2 , which can also be used as whitening agent, carboxylic acids, ectoine or ectoine derivatives, allantoin, taurine and / or bisabolol, mono- or oligosaccharides, silicone oil and / or silicone gum, lipids, oily bodies, enzymes and pearl extracts.
- preparations (A) and (B) may furthermore contain all active ingredients, additives and auxiliaries known for such preparations.
- the colorants contain at least one surfactant, wherein in principle both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants are suitable. In many cases, however, it has proved to be advantageous to select the surfactants from anionic, zwitterionic or nonionic surfactants.
- Suitable anionic surfactants in preparations according to the invention are all anionic surfactants suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such. Example, a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group having about 10 to 22 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups may be present in the molecule.
- anionic surfactants are, in each case in the form of the sodium, potassium and ammonium and the mono-, di- and Trialkanolammoniumsalze with 2 or 3 C atoms in the alkanol group, linear fatty acids having 10 to 22 carbon atoms (soaps )
- 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 having 8 to 22 carbon atoms.
- Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids having 10 to 18 C atoms in the alkyl group and up to 12 glycol ether groups in the molecule, and in particular salts of saturated and in particular unsaturated C 8 -C 22 carboxylic acids, such as oleic acid, stearic acid , Isostearic acid and palmitic acid.
- Nonionic surfactants contain as hydrophilic group z.
- a polyol group for example, a polyalkylene glycol ether or a combination of polyol and Polyglykolether- group.
- Such compounds are, for example
- Preferred nonionic surfactants are alkyl polyglycosides of the general formula R 1 O- (Z) x . These connections are identified by the following parameters.
- the alkyl radical R 1 contains 6 to 22 carbon atoms and may be both linear and branched. Preference is given to primary linear and 2-methyl-branched aliphatic see leftovers.
- Such alkyl radicals are, for example, 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-stearyl. Particularly preferred are 1-octyl, 1-decyl, 1-lauryl, 1-myristyl.
- oxo-alcohols 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 one particular alkyl radical R 1 .
- these compounds are prepared starting from natural fats and oils or mineral oils.
- the alkyl radicals R are mixtures corresponding to the starting compounds or corresponding to the particular work-up of these compounds.
- C 10 alkyl groups mainly of C 12 - - and C 4 alkyl groups, essentially of C 8 - to C 16 -alkyl groups or C essentially of alkyl polyglycosides are those in which R 1 consists essentially of C 8 are particularly preferred 12 - to C 16 alkyl groups.
- sugar building block Z it is possible to use any desired mono- or oligosaccharides.
- sugars with 5 or 6 carbon atoms and the corresponding oligosaccharides are used.
- Such sugars are, for example, glucose, fructose, galactose, arabinose, ribose, xylose, lyxose, allose, altrose, mannose, gulose, idose, talose and sucrose.
- Preferred sugar building blocks are glucose, fructose, galactose, arabinose and sucrose; Glucose is particularly preferred.
- alkyl polyglycosides which can be used according to the invention contain on average from 1.1 to 5 sugar units. Alkyl polyglycosides having x values of 1.1 to 1.6 are preferred. Very particular preference is given to alkyl glycosides in which x is 1: 1 to 1, 4.
- the alkyl glycosides can also serve to improve the fixation of fragrance components on the hair.
- This substance class as a further constituent of the preparations according to the invention in the event that an effect of the perfume oil on the hair which exceeds the duration of the hair treatment is desired.
- the alkoxylated homologs of said alkyl polyglycosides can also be used according to the invention. These homologs may contain on average up to 10 ethylene oxide and / or propylene oxide units per alkyl glycoside unit.
- zwitterionic surfactants can be used, in particular as cosurfactants.
- Zwitterionic surfactants are surface-active compounds which carry at least one quaternary ammonium group and at least one -COO H or -SO 3 H group in the molecule.
- Particularly suitable zwitterionic surfactants are the so-called betaines such as N-alkyl-N, N-dimethylammonium glycinates, for example cocoalkyldimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinates, for example cocoacylaminopropyldimethylammonium monium glycinate, and 2-alkyl-3-carboxylmethyl-3-hydroxyethyl-imidazolines having in each case 8 to 18 C atoms in the alkyl or acyl group, and the cocoacylaminoethylhydroxy-ethylcarboxymethylglycinate.
- a preferred zwitterionic surfactant is the fatty acid amide derivative known by the INCI name Cocamidopropyl Betaine.
- ampholytic surfactants are also particularly suitable as co-surfactants.
- am- pholytica surfactants are surface-active compounds which, apart from a C 8 -C S alkyl or acyl group in the molecule at least one free amino group and contain at least one -COOH or -SO 3 H group and to form internal Salts are capable.
- ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each having about 8 to 18 C atoms in the alkyl group.
- Particularly preferred ampholytic surfactants are N-cocoalkyl aminopropionate, cocoacylaminoethyl aminopropionate and C 2- i8 acyl sarcosine.
- cationic surfactants in particular the compounds of the type of quaternary ammonium compounds, the esterquats and the amidoamines can be used, which are also used as a care component.
- cationic silicone oils such as 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 GIu- Ceth-10 hydroxypropyl dimonium chloride".
- the compounds used as surfactant with alkyl groups may 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 having different alkyl chain lengths depending on the respective raw material are obtained.
- both products with a "normal” homolog distribution and those with a narrow homolog distribution can be used.
- normal homolog distribution are meant mixtures of homologs obtained in the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates as catalysts. Narrowed homolog distributions, on the other hand, are obtained when, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates are used as catalysts.
- the use of products with narrow homolog distribution may be preferred.
- colorants according to the invention can be further active, auxiliary and
- Additives such as nonionic polymers such as vinylpyrrolidone / vinyl acrylate copolymers, polyvinylpyrrolidone and vinylpyrrolidone / inylacetate copolymers and polysiloxanes, cationic polymers such as quaternized cellulose ethers, polysiloxanes with quaternary groups, dimethyldiallylammonium chloride polymers, acrylamide-dimethyldiallylammonium chloride copolymers, quaternized with diethyl sulfate Dimethylaminoethylmethacrylate-vinylpyrrolidone copolymers, vinylpyrrolidone-imidazolinium methochloride copolymers and quaternized polyvinyl alcohol, zwitterionic and amphoteric polymers such as, for example, acrylamidopropyltrimethylammonium chloride / acrylate copolymers and octylacrylamide / methyl me
- Thickeners such as agar-agar, guar gum, alginates, xanthan gum, gum arabicum, karaya gum, locust bean gum, linseed gums, dextrans, celulose derivatives, e.g. For example, methyl cellulose, hydroxyalkyl cellulose and carboxymethylcellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such. 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 soya lecithin, egg lecithin and cephalins,
- Protein hydrolysates in particular elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolysates, their condensation products with fatty acids and quaternized protein hydrolysates, perfume oils, dimethyl isosorbide and cyclodextrins,
- Solvents and mediators such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol, fiber-structure-improving agents, especially mono-, di- and oligosaccharides such as glucose, galactose, fructose, fructose and lactose, quaternized amines such as methyl-1-alkylamidoethyl 2-alkylimidazolinium methosulfate defoamers such as silicones, dyes for staining the agent,
- Antidandruff active ingredients 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 conventional acids, in particular edible acids and bases,
- Active ingredients such as allantoin, pyrrolidonecarboxylic acids and their salts, and also bisabolol, cholesterol, bodying agents such as sugar esters, polyol esters or polyol alkyl ethers, Fats and waxes such as spermaceti, beeswax, montan wax and paraffins, fatty acid alkanolamides,
- - swelling and penetrating substances such as glycerol, propylene glycol monoethyl ether, carbonates, bicarbonates, guanidines, ureas and primary, secondary and tertiary phosphates,
- Opacifiers such as latex, styrene / PVP and styrene / acrylamide copolymers, pearlescing agents such as ethylene glycol mono- and distearate and PEG-3-distearate, preservatives,
- Propellants such as propane-butane mixtures, N 2 O, dimethyl ether, CO 2 and air,
- the preparations (A) and (B) preferably contain the components essential to the invention in a suitable aqueous, alcoholic or aqueous-alcoholic carrier.
- a suitable aqueous, alcoholic or aqueous-alcoholic carrier for the purpose of hair coloring
- hair coloring such carriers are for example creams, emulsions, gels or surfactant-containing foaming solutions, such as shampoos or other preparations which are suitable for use on the hair.
- aqueous-alcoholic solutions are to be understood as meaning aqueous solutions containing from 3 to 70% by weight of a C 1 -C 4 -alkoHO, in particular ethanol or isopropanol.
- the compositions of the invention may additionally contain other organic solvents, such as methoxybutanol, benzyl alcohol, ethyl diglycol or 1, 2-propylene glycol. Preference is given to all water-soluble organic solvents.
- the agents according to the invention may contain a reducing agent.
- reducing agents which are preferred according to the invention are sodium sulfite, Ascorbic acid, thioglycolic acid and its derivatives, sodium thionite, alkali metal citrate salts and N-acetyl-L-cysteine
- Very particularly preferred reducing agents are alkali metal citrate salts, especially sodium citrate, and N-acetyl-L-cysteine.
- N-acetyl-L-cysteine is a particularly preferred reducing agent.
- the agents according to the invention may contain alkalizing agents, usually alkali metal or alkaline earth metal hydroxides, ammonia or organic amines.
- alkalizing agents are monoethanolamine, monoisopropanolamine, 2-amino-2-methyl-propanol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, 2-amino-2 -methylbutanol and triethanolamine and alkali and alkaline earth metal hydroxides.
- monoethanolamine, triethanolamine and 2-amino-2-methyl-propanol and 2-amino-2-methyl-1, 3-propanediol are preferred within the scope of this group.
- ⁇ -amino acids such as ⁇ -aminocaproic acid as an alkalizing agent is also possible.
- compositions according to the invention in the preparation (A) and / or the preparation (B) for coloring may contain pearlescent pigments.
- Pearlescent pigments which are preferred according to the invention are natural pearlescent pigments, such as e.g. Fish silver (guanine / hypoxanthine mixed crystals from fish scale) or mother-of-pearl (from ground mussel shells), monocrystalline pearlescent pigments, such as Bismuth oxychloride, and pearlescent pigments based on mica or mica / metal oxide.
- the latter pearlescent pigments are provided with a metal oxide coating.
- the use of the pearlescent pigments achieves gloss and optionally additionally color effects in the multicomponent agents according to the invention.
- the coloring by the pearlescent pigments used in the multicomponent agents does not influence the color result of the dyeing of the keratin fibers.
- Mica-based and mica / metal oxide-based pearlescent pigments are likewise preferred according to the invention.
- Mica belongs to the layer silicates. The most important representatives of these silicates are muscovite, phlogopite, paragonite, biotite, lepidolite and margarite.
- the mica predominantly muscovite or phlogopite, is coated with a metal oxide. Suitable metal oxides include TiO 2 , Cr 2 O 3 and Fe 2 O 3 .
- interference pigments and color luster pigments are prepared as pearlescent pigments according to the invention. obtained pigments. In addition to a glittering optical effect, these pearlescent pigment types also have color effects.
- the pearlescent pigments which can be used according to the invention can furthermore contain a color pigment which does not derive from a metal oxide.
- the grain size of the pearlescent pigments preferably used is preferably between 1.0 and 100 .mu.m, particularly preferably between 5.0 and 60.0 .mu.m.
- Particularly preferred pearlescent pigments are marketed by Merck under the trade names Colorona ®, wherein the pigments Colorona ® red- brown (47-57 wt.% Muscovite mica (KH 2 (AISiO 4) S) 1 43-50 wt .% Fe 2 O 3 (INCI: Iron oxide Cl 77491), ⁇ 3 weight% TiO 2 (INCI: Titanium Dioxide CI 77891).., Colorona ® Blue Black Star (39-47% by weight of muscovite mica (KH 2 (AISi0 4 .) 3), 53-61% by weight of Fe 3 O 4 (INCI:.
- Colorona ® Red Black Star 39-47% by weight of muscovite mica (KH 2 (AISi0 4 .) 3
- Fe 3 O 4 INCI:.
- Iron oxide Cl 77499) Colorona ® Fine Siena (35-45% by weight of muscovite mica (KH 2 (AISi0 4) 3), 55-65 .% by weight of Fe 2 O 3 (INCI: Iron oxide Cl 77491)), Colorona ® Abrare Amber (50-62% by weight of muscovite mica (KH 2 (AISi0 4). 3), 36-44% by weight of Fe 3 O 4.
- pearlescent pigments which can be used in the compositions according to the invention, reference is expressly made to the monographs Inorganic Pigments, Chemical Technology Review No. 166, 1980, pages 161-173 (ISBN 0-8155-0811-5) and Industrial Inorganic Pigments, 2nd edition, Weinheim , VCH, 1998, pages 211-231.
- a multi-component agent is packaged in different chambers of a multi-chamber tube.
- the preparation (B) contains a compound with primary amino group selected from primary aromatic amines and primary heteroaromatic amines
- it is preferably in the multi-chamber tube to a two-chamber tube, wherein a first chamber, the preparation (A) and a second Chamber receives the preparation (B).
- the Preparation (B) contains a CH-acidic compound
- it is preferably in the multi-chamber tube to a three-chamber tube, wherein a first chamber, the preparation (A), a second chamber, the preparation (B) and a third chamber, a preparation containing an alkalizing agent , picks up.
- preparation (A) and / or preparation (B) can be distributed to several chambers of the multi-chamber tube, whereby, of course, care must be taken that in a certain chamber only preparation (A) or preparation (B) is located.
- preparation (A) and preparation (B) each occupy only one chamber, with the remaining chambers being provided for further components, for example a preparation containing an oxidizing agent and / or an alkalizing agent.
- Two-chamber tubes are in principle already known in the art.
- the tubes have two separate chambers, which are designed as nested hoses. These define the inner and outer chambers and terminate in the common head or exit region.
- the head area is designed so that the two preparations emerge together from the tube as soon as pressure is exerted on the tube.
- the design of the head region determines in which striped pattern the preparations emerge from the tube. Problems often arise in the two-chamber tubes commonly used in that the individual chambers in the head area are not completely separated from each other.
- the constituents of the separately formulated phases can thus diffuse into one another, especially during prolonged storage, which in the case of the multicomponent agents according to the invention leads to undesired conversion of the constituents into finished dyes already in the tube.
- this can be prevented by the special configuration of the head region of the multi-chamber tube used, in particular by reinforcement of the shoulder region.
- the multicomponent agents according to the invention are preferably packaged in a multichamber tube which has an inner and an outer chamber, both of which end in a common head region (outlet region).
- the head area is designed so that the two preparations emerge together from the tube as soon as pressure is exerted on the tube.
- the design of this head area determines in which pattern the preparations emerge from the tube.
- the choice of the volumes of the individual chambers depends on the desired ratio of the volumes of preparation (A), preparation (B) and optionally further phases present in the multicomponent agent.
- the preferred multi-chamber tube is characterized in particular by a special design of the outlet area. This reflects the ratio of the chamber volumes in the cross sections of the paths defined for the partial flows. It should be noted that the partial stream of a preparation may have multiple parallel branch streams. Thus, separating means can divide the cross-section of the passage channel at least almost in proportion to the ratio in two or more partial flows. It should be noted that it is advantageous for the function of the multi-chamber tubes if the various components present in the respective tube chambers each have approximately the same viscosity.
- the invention should in principle not be restricted in any way with regard to the pattern with which the preparations emerge from the tube, it may be preferred according to the invention if the first preparation emerges as the main strand and the second preparation forms a plurality of strips running along this main strand. Also with regard to the number of strips, the invention should not be limited. However, a number of 2 to 4 strips according to the invention may be particularly preferred for application reasons. In this case, in a first embodiment, the preparation (A) form the strips, while the preparation (B) forms the main strand and in a second embodiment, the preparation (B) form the strips, while the preparation (A) forms the main strand.
- the two preparations may also be preferred for the two preparations to form the main strand proportionally together next to one another.
- the outlet strand can consist of an inner region, formed from a first preparation, and an outer region, formed from the second preparation, wherein the preparations also form the outlet strand according to their arrangement in the tube.
- the amount ratio of the preparation (A) to the amount of the preparation (B) according to the invention is preferably in a range of 1: 3 to 3: 1, a range of 1: 1, 5 to 1, 5: 1 is particularly preferred according to the invention.
- the present invention is intended to include any distribution of the chambers within the tube.
- the two individual chambers may be arranged side by side in an outer shell.
- the multi-chamber tube consists of an inner tube which is completely surrounded by an outer tube. This embodiment is characterized by an optimally constant dosage of the two preparations.
- every distribution of the preparations to the chambers of the tube should be encompassed according to the invention, it can be particularly preferred if the preparation (A) is in the outer tube and the preparation (B) is in the inner tube.
- the multi-chamber tube is preferably made of a material suitable for packaging tinting and coloring agents of this type.
- laminated aluminum has proved itself both for the outer walls and for the inner walls.
- tubes made of plastic laminate (PE, PET, PP) or plastic coextrudates (PE, PET, PP) are also conceivable.
- the material of the inner tube can be selected independently of the material of the outer tube.
- the inner tube made of aluminum laminate, which is optionally still protected with a paint
- the outer tube is made either of aluminum laminate or plastic laminate.
- Under aluminum laminate is understood according to the invention a coated with plastic aluminum layer.
- the shoulder region of the outer tube is reinforced with blanks which have particularly good barrier properties. It is advantageous to incorporate aluminum in the material of the blanks.
- the actual colorant is obtained by mixing the two exits from the tube preparations (A) and (B).
- This mixing of the separately emerging from the tube preparations (A) and (B) can be carried out both before the application to the fibers in a separate step as well as a side effect in the incorporation of the exit strand into the fibers.
- the resulting ready-to-use hair dye preparation should preferably have a pH in the range of 6 to 12.
- the pH value in the context of the present disclosure is to be understood as the pH at 25 ° C.
- Particularly preferred is the use of the hair dye in an alkaline environment.
- the application temperatures can be in a range between 15 and 40 0 C.
- the hair dye is removed by rinsing of the hair to be dyed.
- the washing with a shampoo is omitted if a strong surfactant-containing carrier, such as a dyeing shampoo was used.
- the formulations (A) and (B) according to the invention preferably have viscosities in the range of 2000 (rpm Brookfield viscometer, spindle no. 4, 20, 2O 0 C) to 200 000 mPas, particularly 5000 to 50000 mPas on. In this way it is ensured that the multicomponent agent has a good miscibility and yet the exit pattern has a sufficient stability.
- the present invention further provides a multi-chamber tube, preferably a two-chamber tube, comprising in a first chamber a preparation (A) containing at least one reactive carbonyl compound, and in a second chamber a preparation (B) containing at least one compound selected from (a) CH-acidic compound; and (b) primary amino group compounds selected from primary aromatic amines and primary heteroaromatic amines.
- A a preparation containing at least one reactive carbonyl compound
- B containing at least one compound selected from (a) CH-acidic compound
- primary amino group compounds selected from primary aromatic amines and primary heteroaromatic amines.
- the multi-chamber tube is designed so that the preparations in a ratio of (A) :( B) corresponding to 1: 2 to 2: 1 emerge from the tube.
- Another object of the present invention is a method for coloring keratinic fibers, in particular human hair, wherein a multi-component agent according to the invention is squeezed out of the tube, the resulting application preparation is applied to the fibers and rinsed again after a contact time.
- the creams A1 to A5 were each packaged in a ratio of 1: 1 with the creams B1 to B6 in a two-chamber tube. Likewise, the preparation of the creams A'1 to A'5 and B'1 to B'6 in the ratio 1: 1.
- the two-component agent from the two-chamber tube was applied directly to human hair (Kerling natural white), massaged there, allowed to act at room temperature for 30 minutes and then rinsed out. After drying the hair intensive copper, red or brown nuances were achieved.
- Dehyton ® CN N-dimethyl-N- (C 8- i B -kokosamidopropyl) ammoniumaceto- betaine (30% active substance; INCI name: Aqua (Water), Cocamidopropyl Betaine) (Cognis)
- Ci 6 -ia fatty alcohol (INCI name: Cetearyl alcohol)
- Lamesoft ® PO65 alkyl polyglucoside oleic acid monoglyceride mixture (about 65-70% solids, INCI name: Coco-Glucoside, Glyceryl Oleate, Aqua (Water)) (Cognis)
- Phopholipid ® EFA (INCI name: Linoleamidopropyl PG-Dimonium
- Chloride Phosphate (Uniqema) Plantacare® ® 2000 C 12-1s fatty alcohol-1.4-glucoside (about 50-53%
- Texapon ® K 14 S 70 C Laurylmyristylethersulfat sodium salt (ca. 68% to 73% active substance content '; INCI name: Sodium Myreth Sulfate) (Cognis)
- Rewoteric ® AM BU 185 Undecylenamidopropyl-dimethyl-glycine (INCI name: Undecylenamidopropyl Betaine) (Degussa) Turpinal ® SL 1-hydroxyethane-1, (1-diphosphonic acid, about 58-61% active substance content; INCI name: Etidronic Acid, Aqua (Water)) (Solutia)
- Varisoft ® BT 85 Docosantrimethylammonium chloride (INCI name: Behentrimonium Chloride) (Degussa) Gluadin ® Almond protein hydrolyzate from sweet almond flour (INCI name: Hydrolyzed Sweet Almond Protein) (Cognis) Herbalia ® Green Tea extract from the leaves of Camellia Sinensis (INCI - Name: Camellia Sinensis Leaf Extract) (Cognis) Quaternium 80 dimethylsiloxane / dimethyl silicone terminated with 3 - (- 3 - ((3-cocoamidopropyl) dimethylammonium) -2-hydroxypropyl) - propyl acetate groups (INCI name: Quaternium-80) (Degussa)
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- 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)
- Emergency Medicine (AREA)
- Cosmetics (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE200510026545 DE102005026545A1 (de) | 2005-06-08 | 2005-06-08 | Mehrkomponentenmittel zum Färben keratinischer Fasern |
PCT/EP2006/002710 WO2006131163A1 (de) | 2005-06-08 | 2006-03-24 | Mehrkomponentenmittel zum färben keratinischer fasern |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1893165A1 true EP1893165A1 (de) | 2008-03-05 |
Family
ID=36499226
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP06707642A Ceased EP1893165A1 (de) | 2005-06-08 | 2006-03-24 | Mehrkomponentenmittel zum färben keratinischer fasern |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP1893165A1 (de) |
DE (1) | DE102005026545A1 (de) |
WO (1) | WO2006131163A1 (de) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102007028266A1 (de) * | 2007-06-15 | 2008-12-18 | Henkel Ag & Co. Kgaa | Kit zur Bereitstellung von lagerstabilen Formulierungen |
FR2920778B1 (fr) | 2007-09-11 | 2009-10-30 | Oreal | Composes quinoliniums azoiques a motif disulfure/thiol, compositions les comprenant, procede de coloration de fibres keratiniques et dispositif. |
FR2921382B1 (fr) | 2007-09-21 | 2009-10-30 | Oreal | Colorant derive de phenyl-pyridol[1,2-a]indolium thiol-disulfure, composition tinctoriale comprenant ce colorant, procede d'eclaircissement des matieres keratiniques a partir de ce colorant |
FR2921258A1 (fr) * | 2007-09-24 | 2009-03-27 | Oreal | Composition tinctoriale comprenant au moins un precurseur incolore disulfures/thiol, proced de coloration a partir de la composition |
DE102007058032A1 (de) * | 2007-11-30 | 2009-06-04 | Henkel Ag & Co. Kgaa | Mittel zur Hautbräunung |
DE102008061857A1 (de) * | 2008-10-22 | 2010-04-29 | Henkel Ag & Co. Kgaa | Färbemittel auf Basis von CH-aciden Verbindungen |
DE102008061855A1 (de) * | 2008-10-22 | 2010-04-29 | Henkel Ag & Co. Kgaa | Mittel zum Färben von keratinhaltigen Fasern |
CN103249455B (zh) | 2010-12-20 | 2017-04-19 | 莱雅公司 | 在热存在下使用羟基苯甲醛衍生物、氧化剂和碱化剂对角蛋白纤维进行染色的方法 |
DE102014017032A1 (de) * | 2014-11-19 | 2016-05-19 | Henkel Ag & Co. Kgaa | Abgabevorrichtung sowie zugehöriger Spender für fließfähige Produktzusammensetzungen |
DE102016004698A1 (de) | 2016-04-20 | 2017-10-26 | Wind Plus Sonne Gmbh | Flambierpasten |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2787708B1 (fr) * | 1998-12-23 | 2002-09-13 | Oreal | Procede de teinture mettant en oeuvre un compose a methylene actif et un compose choisi parmi un aldehyde, une cetone, une quinone et un derive de la di-imino-isoindoline ou de la 3-amino-isoindolone |
DE19951134A1 (de) * | 1999-10-23 | 2001-04-26 | Henkel Kgaa | Mittel zum Färben von keratinhaltigen Fasern |
DE19962875A1 (de) * | 1999-12-24 | 2001-06-28 | Henkel Kgaa | Verwendung von Methylchinolinium-Verbindungen zum Färben von keratinhaltigen Fasern |
DE10022743A1 (de) * | 2000-05-10 | 2001-11-22 | Wella Ag | Mittel zur Färbung von Fasern |
CA2449214C (en) * | 2001-07-11 | 2009-03-10 | The Procter & Gamble Company | Multi-chambered tube comprising a flow regulating element for uniform dispensing of fluids |
MXPA04000234A (es) * | 2001-07-11 | 2005-03-07 | Procter & Gamble | Tubo de camaras multiples para despachar uniformemente. |
DE10163722A1 (de) * | 2001-12-21 | 2003-07-03 | Maegerle Karl Lizenz | Mehrkammertube |
DE10359557A1 (de) * | 2003-12-17 | 2005-07-14 | Hans Schwarzkopf & Henkel Gmbh & Co. Kg | Oxidationsfärbemittel in Tube |
DE10359538A1 (de) * | 2003-12-17 | 2005-07-14 | Hans Schwarzkopf & Henkel Gmbh & Co. Kg | Tönungsmittel in Tuben |
-
2005
- 2005-06-08 DE DE200510026545 patent/DE102005026545A1/de not_active Withdrawn
-
2006
- 2006-03-24 EP EP06707642A patent/EP1893165A1/de not_active Ceased
- 2006-03-24 WO PCT/EP2006/002710 patent/WO2006131163A1/de not_active Application Discontinuation
Non-Patent Citations (1)
Title |
---|
See references of WO2006131163A1 * |
Also Published As
Publication number | Publication date |
---|---|
DE102005026545A1 (de) | 2006-12-21 |
WO2006131163A1 (de) | 2006-12-14 |
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