WO2007051527A1 - Washing-active pit emulsions - Google Patents

Washing-active pit emulsions Download PDF

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Publication number
WO2007051527A1
WO2007051527A1 PCT/EP2006/010079 EP2006010079W WO2007051527A1 WO 2007051527 A1 WO2007051527 A1 WO 2007051527A1 EP 2006010079 W EP2006010079 W EP 2006010079W WO 2007051527 A1 WO2007051527 A1 WO 2007051527A1
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WIPO (PCT)
Prior art keywords
alkyl
amino
acid
carbon atoms
alcohols
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PCT/EP2006/010079
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German (de)
French (fr)
Inventor
Martina Seiler
Konstantin Goutsis
Detlef Hollenberg
Original Assignee
Henkel Ag & Co. Kgaa
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Publication date
Application filed by Henkel Ag & Co. Kgaa filed Critical Henkel Ag & Co. Kgaa
Priority to EP06806389A priority Critical patent/EP1945180A1/en
Publication of WO2007051527A1 publication Critical patent/WO2007051527A1/en

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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
    • A61Q5/02—Preparations for cleaning the hair
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04—Dispersions; Emulsions
    • A61K8/06—Emulsions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/39—Derivatives containing from 2 to 10 oxyalkylene groups
    • 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
    • A61K8/60—Sugars; Derivatives thereof
    • A61K8/604—Alkylpolyglycosides; Derivatives thereof, e.g. esters
    • 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
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/86—Polyethers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/10—Washing or bathing preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/59—Mixtures
    • A61K2800/596—Mixtures of surface active compounds

Definitions

  • the invention relates to stable, wash-active PIT emulsions containing as detergent substance at least one anionic alkyl or Alkenyloligoglykosid derivative, and a production process.
  • phase inversion temperature emulsions For the preparation of finely divided emulsions via the phase inversion temperature method, mixtures of different emulsifiers in combination with oil bodies are usually used.
  • An overview of phase inversion temperature emulsions can be found in A. Wadle et al. in Parf.Kosm. 72, 250 (1996); Representative of the extensive state of the art, reference is made to the publications DE-A1 3819193, DE-A1 4010393, DE-A1 4140562, DE-A1 4318171 and DE-A1 4337041.
  • EP-A2-1 321 132 describes stable dyeing emulsions in which oxidation dye precursors are incorporated in a PIT emulsion. If the washing with a shampoo is to be omitted, according to this document a washing-active surfactant can be added to obtain a dyeing shampoo. However, the problem arises here for the skilled person that the PIT emulsion loses stability in the presence of washing-active surfactants.
  • the object of the invention is to provide stable PIT emulsions which contain a washing-active surfactant and develop a cleaning action when applied to the skin and / or the hair.
  • the PIT emulsions should in particular at basic pH be stable and allow the penetration of an active substance such as a dye or more dye precursors into the substrate.
  • the invention relates to an emulsion prepared by the phase inversion temperature method comprising
  • the emulsifiers are preferably present in amounts of 0.5 to 20, preferably 1 to 10 wt .-% - based on the weight of the emulsions - in the emulsions according to the invention.
  • the emulsifier used is preferably at least one nonionic surfactant, more preferably at least one nonionic surfactant from at least one of the following groups:
  • glycerol mono- or diesters (partial glycerides) as well as sorbitan mono- and diesters, each of saturated and / or unsaturated fatty acids having 6 to 22 carbon atoms and their ethylene oxide addition products;
  • alkyl mono- and oligoglycosides having 8 to 22 carbon atoms in the alkyl group and their ethoxylated analogs; in particular alkyl or alkenyl, mono- or oligoglycosides of the formula
  • R ' is a C 6-22 alkyl or C 6-22 alkenyl group
  • Gl is a glycoside unit derived from a sugar having 5 or 6 carbon atoms and m is a number from 1 to 10.
  • the alkyl and / or Alkenyloligoglykoside are derived from aldoses or ketoses with 5 or 6 carbon atoms (remainder Gl), preferably glucose.
  • the preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides.
  • the index number m in the general formula (I) indicates the degree of oligomerization (DP), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10.
  • oligoglycoside and "polyglycoside” are used in the context of the application used synonymously according to this definition.
  • the alkyl or alkenyl radical R ' can be derived from primary alcohols having 4 to 11, preferably 8 to 10 carbon atoms. Typical examples are butanol, caproic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and technical mixtures thereof, as obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the hydrogenation of aldehydes from Roelen's oxo synthesis.
  • the alkyl or alkenyl radical R 'can also be derived from primary alcohols having 12 to 22, preferably 12 to 14 carbon atoms.
  • Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol and technical mixtures thereof which can be obtained as described above.
  • Preference is given to alkyl oligoglucosides based on hydrogenated C 12 / n cocoalcohol having a DP of 1 to 3;
  • polystyrene resin e.g. Polyglycerol polyricinoleate, polyglycerol poly-12-hydroxy stearate or polyglycerol dimerate. Also suitable are mixtures of compounds of several of these classes of substances;
  • the addition products of ethylene oxide and / or of propylene oxide to fatty alcohols, fatty acids, alkylphenols, glycerol mono- and diesters and sorbitan mono- and diesters of fatty acids or to castor oil are known, commercially available products. These are homolog mixtures, whose average degree of alkoxylation corresponds to the ratio of the molar amounts of ethylene oxide and / or propylene oxide and substrate with which the addition reaction is carried out. 12 C / i 8 fatty acid monoesters and diesters of addition products of ethylene oxide onto glycerol are known from DE-PS 20 24 051. as refatting agents for cosmetic preparations.
  • zwitterionic surfactants can be used as emulsifiers.
  • Zwitterionic surfactants are those surface-active compounds which carry at least one quaternary ammonium group and at least one carboxylate and one sulfonate 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-acylamino-propyl-N, N-dimethylammonium glycinates, for example cocoacylaminopropyldimethylammonium glycinate, and 2-alkyl-3-carboxylmethyl 3-hydroxyethylimidazolines having in each case 8 to 18 carbon atoms in the alkyl or acyl group, and the Kokosacylaminoethyl- hydroxyethylcarboxymethylglycinat.
  • betaines such as N-alkyl-N, N-dimethylammonium glycinates, for example cocoalkyldimethylammonium glycinate, N-acylamino-propyl-N, N-dimethylammonium gly
  • fatty acid amide derivative known under the CTFA name Cocamidopropyl Betaine.
  • emulsifiers are ampholytic surfactants.
  • phobic surfactants are surface-active compounds which, apart from a C 8 i 8 alkyl or acyl group in the molecule at least one free amino group and at least one -COOH or -SO / 3 H group and are capable of forming inner salts are.
  • 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 carbon atoms in the alkyl group.
  • Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C 12/18 acylsarcosine.
  • quaternary emulsifiers are also suitable, with those of the esterquat type, preferably methyl-quaternized difatty acid triethanolamine ester salts, being particularly preferred.
  • the emulsions comprise at least one emulsifier selected from the group formed by alkyl monoglycosides, alkyl oligoglycosides, alkenyl monoglycosides, alkenyl oligoglycosides and the ethoxylated analogs of all the representatives, the alkyl or alkenyl groups being from 6 to 22 Possess carbon atoms.
  • the emulsifiers of the formula (I) listed under (4) are preferred (vide supra).
  • the addition products of ethylene oxide and / or of propylene oxide according to (1) are preferably fatty alcohol ethoxylates and more preferably follow the formula (II)
  • R 1 is a linear or branched alkyl radical having 12 to 22 carbon atoms and n is a number from 5 to 50 and preferably 15 to 35.
  • Typical examples are adducts of 10 to 30 moles of ethylene oxide with lauryl alcohol, isotridecyl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, linolyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachidyl alcohol, gadolyl alcohol or behenyl alcohol and their technical mixtures, for example in US Pat the pressure fission of natural fats and oils or in the reduction of aldehydes from Roelen's oxo synthesis incurred.
  • adducts of 20 to 30 moles of ethylene oxide with fatty alcohols having 16 to 18 carbon atoms are used. These are very particularly preferably contained as emul
  • Partial glycerides which are suitable as emulsifier, preferably follow the formula (III),
  • R 2 CO stands for a linear or branched acyl radical having 12 to 22 carbon atoms and x, y and z in total for 0 or for numbers from 1 to 50, preferably 15 to 35.
  • R 2 CO stands for a linear or branched acyl radical having 12 to 22 carbon atoms and x, y and z in total for 0 or for numbers from 1 to 50, preferably 15 to 35.
  • typical Examples of partial glycerides suitable for the purposes of the invention are lauric acid monoglyceride, coconut fatty acid mono-glyceride, palmitic acid monoglyceride, stearic acid monoglyceride,
  • monoglycerides or technical mono / Diglyceridgemische with predominantly Monoglyceridanteil of formula (III) are used, in which R 2 CO is a linear acyl radical having 16 to 18 carbon atoms.
  • the emulsions contain at least one of emulsifiers
  • the emulsions according to the invention are free of emulsifiers which contain at least one ester bond -C (O) -O- as structural element. This is especially true at a pH of the emulsion of pH> 7.
  • the emulsifiers or mixtures thereof cause a phase inversion temperature of the emulsion according to the invention for the preparation of -5 ° C to 45 0 C, in particular from 1O 0 C to 30 0 C.
  • PIT emulsions are in the document DE-A1-102 56 507, the contents of which are expressly and fully incorporated by reference.
  • the oil body is preferably at least one member selected from the group consisting of Guerbet alcohols based on fatty alcohols having 6 to 18 carbon atoms, esters of linear C 6 -C 2 o fatty acids with linear C 6 -C 2 o-fatty alcohols, esters of branched C6-C13-carboxylic acids with linear C6-C20-fatty alcohols, esters of linear C6-C18-fatty acids with branched alcohols, in particular with 2-ethylhexanol,
  • Esters of linear and / or branched fatty acids with polyhydric alcohols and / or Guerbet alcohols such as dimerdiol or trimer triol
  • triglycerides based on C6-C10 fatty acids vegetable oils, branched primary alcohols, substituted cyclohexanes, Guerbet carbonates, dialkyl ethers and / or aliphatic or naphthenic hydrocarbons (eg paraffin oil) in question.
  • Preferred oil bodies are at least one member of the group formed from Guerbet alcohols based on fatty alcohols having 6 to 18, preferably 8 to 10 carbon atoms, vegetable oils, branched primary alcohols, substituted cyclohexanes, Guerbet carbonates, (C 6 to C 22 ) dialkyl ethers (especially dioctyl ether (Cetiol OE ® of the company. Cognis)) and aliphatic or naphthenic hydrocarbons (such as paraffin oil).
  • Guerbet alcohols based on fatty alcohols having 6 to 18, preferably 8 to 10 carbon atoms, vegetable oils, branched primary alcohols, substituted cyclohexanes, Guerbet carbonates, (C 6 to C 22 ) dialkyl ethers (especially dioctyl ether (Cetiol OE ® of the company. Cognis)) and aliphatic or naphthenic hydrocarbons (such as paraffin oil).
  • the emulsions according to the invention are particularly preferably free from those oil bodies which contain at least one ester bond -C (O) -O- as structural element. This is especially true at a pH of the emulsion of pH> 7.
  • the oily bodies are preferably present in an amount of from 1 to 50% by weight, more preferably from 5 to 20% by weight, based in each case on the weight of the emulsion.
  • anionic alkyl oligoglycoside or anionic alkenyl oligoglycoside derivatives (iii) contained in the emulsions according to the invention are preferably selected from alkyl and / or alkenyl oligoglycoside carboxylates, sulfates, phosphates and / or isethionates derived from alkyl and / or alkenyl oligoglycosides derive the general formula (IV),
  • G glycoside unit derived from a sugar with 5 or 6 carbon atoms, p number from 1 to 10.
  • the alkyl / alkenyl radical R of the formula (IV) is preferably derived from primary alcohols having 6 to 22, preferably 12 to 18 carbon atoms.
  • Typical examples are caproic alcohol, caprylic alcohol, capric alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol and behenyl alcohol, as well as technical fractions which, in addition to the saturated alcohols mentioned, may also contain portions of unsaturated alcohols and those based on natural fats and oils, for example palm oil, palm kernel oil, coconut oil or beef tallow. The use of technical coconut oil is particularly preferred here.
  • radical R according to formula (IV) can also be derived from synthetic primary alcohols having 6 to 22 carbon atoms, in particular the so-called oxo alcohols, which have a proportion of 5 to 40% by weight of branched isomers.
  • Particularly preferred alkyl radicals R of the formula (IV) are those having 8/10, 12/14, 8 to 16, 12 to 16 or 16 to 18 C atoms. Mixtures of the alkyl radicals result in a preparation starting from natural fats and oils or mineral oils.
  • Alkyl oligoglycoside carboxylates, sulfates, phosphates and / or isethionates, particularly preferably alkyl oligoglycoside carboxylates or phosphates, in particular alkyl glycoside carboxylates, are preferably used according to the invention.
  • hydroxyl groups of the glucoside can also be etherified, for example.
  • alkyl oligoglycoside carboxylate in which the alkyl radical R of the formula (IV) is a lauryl radical.
  • R of the formula (IV) is a lauryl radical.
  • alkyl glycosides having an average degree of oligomerization p of 1.1 to 3.0 are used. Especially Preferred are those alkyl glycosides whose degree of oligomerization is less than 1.5, and in particular between 1.1 and 1.4.
  • the glycoside units G are preferably derived from aldoses or ketoses.
  • the aldoses used are particularly suitable for their easy accessibility and technical availability.
  • the alkylglycosides which are particularly preferably used as starting materials are therefore the alkylglucosides.
  • the alkyl or alkenyl oligoglycoside carboxylates, phosphates, sulfates or isethionates used according to the invention can be prepared by known processes.
  • the carboxylates are prepared, for example, by reacting the alkyloligoglycosides with salts of chlorocarboxylic acids in the presence of bases. For example, it is possible to react with 2-chloroacetic acid sodium salt in the presence of NaOH. In the reaction, both the hydroxyl groups in the ring as well as the
  • the alkyl oligoglycosides are reacted at least on the -CH 2 -OH group, optionally with an agent capable of reacting one or more of the hydroxyl groups on the ring.
  • the preparation of the isethionates is described, for example, in WO 94/26857. It also states that the products can be used for hair and body care.
  • aqueous detergent mixtures are described which contain alkyloligoglycoside isethionates and, for example, further anionic surfactants.
  • sulfates The preparation of the sulfates is described, for example, in WO 93/10208 and WO 91/15192. In the latter document are also mixtures of APG sulfates with, inter alia, alkyl sulfates or Alkyl ether sulfates and other ingredients described. It is stated that the surfactant mixtures can be used in products that are used for washing, dyeing, rippling or rinsing hair.
  • the preparation of the sulfates can also be carried out as described in EP-A-0 186 242.
  • the corresponding alkyl glycoside can be reacted with gaseous sulfur trioxide or with sulfuric acid followed by neutralization.
  • DE-A-195 01 185 describes detergent mixtures of alkyl oligoglycoside sulfates and alkyl ether phosphates which can be used, for example, in hair rinses, hair dyes or hair waving agents.
  • emulsions according to the invention comprise at least one alkyl and / or alkenyl oligoglycoside carboxylate, sulfate, phosphate and / or isethionate, preferably in an amount of 0.2 to 15% by weight, particularly preferably 0.5 to 10% by weight. -%.
  • the agent in addition to the inventive component (iii) contains no further anionic surfactants.
  • phase inversion The preparation of an emulsion by the phase inversion method is known per se to the person skilled in the art.
  • a preferred method of preparation is to produce so-called PIT emulsions in which the oil bodies and the emulsifiers are heated to the production temperature and mixed with the amount of water which is likewise heated to the production temperature.
  • the production temperature must be above the phase inversion temperature.
  • the phase inversion temperature see A. Domsch, The Cosmetic Preparations, 4th Edition, Volume III, Verlag für ehem. Industrie, H. Ziolkowsky, Augsburg 1994, page 109.
  • the phase inversion takes place within a temperature range.
  • the phase inversion temperature range should therefore first be determined on the basis of a test application. All components of the emulsion, including the water, are heated, the temperature range being determined by means of a conductivity meter, at which the conductivity decreases sharply as a result of phase inversion.
  • the determination of the temperature range of the phase inversion is carried out according to DE-A1-102 56 507 [0011] to [0013]. It is preferred according to the invention to add the anionic surfactants of component (iii) of the emulsion according to the invention to the oil body (i) heated to the production temperature. This can be done together with, before or after the addition of the emulsifier component (ii), preferably after the addition of the emulsifier component (ii). Subsequently, the mixture of all components (i) to (iv) is brought together to the ambient temperature.
  • the PIT emulsions according to the invention preferably have a droplet size of from 10 nm to 500 nm, in particular from 10 nm to 200 nm.
  • the pH of the emulsion according to the invention is preferably from pH 5 to pH 12, more preferably the pH is between pH 7 and pH 12, in particular in a range from pH 7.5 to pH 10.
  • the wash-active PIT emulsions of the invention can be used for a variety of applications, but preferably for the production of skin and hair care products, such as hair shampoos, hair dyes, hair lotions, bubble baths, creams, lotions or ointments.
  • the emulsions preferably additionally contain at least one active substance as the active ingredient. These may include UV filters, coloring components and care substances.
  • the active ingredient is preferably added to the finished PIT emulsion base, preferably in the form of an aqueous solution.
  • the PIT emulsion base according to the invention preferably has a temperature below the phase inversion temperature, particularly preferably from 10 to 35 ° C., very particularly preferably room temperature.
  • the emulsions according to the invention comprise as colorants keratin-containing fibers, in particular human hair, as additional active substance at least one coloring component.
  • Keratin fibers are wool, furs, feathers and especially human hair to understand.
  • the colorants of the invention can in principle but also for dyeing other natural fibers such.
  • As polyamide, polyacrylonitrile, polyurethane and polyester fibers are used.
  • the emulsions according to the invention preferably contain (A) at least one oxidation dye precursor of the developer component type and optionally additionally at least one coupler component and / or
  • developer components are usually primary aromatic amines with another, in the para or ortho position, free or substituted hydroxy or amino group, diaminopyridine, heterocyclic hydrazones, 4-aminopyrazole derivatives and 2,4,5,6-tetraaminopyrimidine and its derivatives used ,
  • p-phenylenediamine derivatives of the formula (Ent1) it may be preferred according to the invention to use as the developer component a p-phenylenediamine derivative or one of its physiologically acceptable salts. Particular preference is given to p-phenylenediamine derivatives of the formula (Ent1)
  • G 1 represents a hydrogen atom, a Ci to C 4 alkyl, C 1 - to C 4 - monohydroxyalkyl radical, a C 2 - to C 4 polyhydroxyalkyl radical, a (C 1 - to C 4 ⁇ AIkOXy- (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 is a hydrogen atom, a alkyl alkoxy (d- to C 4) C 1 - to C 4 alkyl, C 1 - to C 4 - monohydroxyalkyl radical, a C 2 - - to C 4 polyhydroxyalkyl radical, a (C 4 to C 1) or a C 1 to C 4 alkyl radical substituted with 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;
  • G 4 represents a hydrogen atom, a halogen atom or a C 1 - to C 4 -alkyl radical or when G 3 and G 4 are ortho to each other, they may together form a bridging ⁇ , ⁇ -alkylenedioxy group, such as, for example, an ethylenedioxy group.
  • C 1 - to C 4 -alkyl radicals mentioned as substituents in the compounds according to the invention are the groups methyl, ethyl, propyl, isopropyl and butyl. Ethyl and methyl are preferred alkyl radicals.
  • C 1 -C 4 -alkoxy radicals which are preferred according to the invention are, for example, a methoxy or an ethoxy group.
  • a C 1 - to C 4 -hydroxyalkyl group a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group may be mentioned.
  • a 2-hydroxyethyl group is particularly preferred.
  • a particularly preferred C 2 to C 4 polyhydroxyalkyl group is the 1, 2-dihydroxyethyl group.
  • halogen atoms are according to the invention F, Cl or Br atoms, Cl atoms are very particularly preferred.
  • the other terms used are derived according to the invention from the definitions given here.
  • nitrogen-containing groups of the formula (Ent1) 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.
  • Particularly preferred p-phenylenediamines of the formula (Ent1) are selected from p-phenylenediamine, p-toluenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2 , 6-diethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, N, N-dipropyl-p-phenylenediamine, 4 -Amino-3-methyl- (N, N-diethyl) -aniline, N, N-bis- ( ⁇ -hydroxyethyl) -p-phenylenediamine, 4-N, N-bis- ( ⁇ -hydroxyethyl) amino-2- methylaniline, 4-N,
  • Very particular preferred p-phenylenediamine derivatives of the formula (Ent1) according to the invention are p-phenylenediamine, p-toluenediamine, 2- ( ⁇ -hydroxyethyl) -p-phenylenediamine, 2- ( ⁇ , ⁇ -dihydroxyethyl) -p-phenylenediamine and N, N bis (.beta.-hydroxyethyl) -p-phenylenediamine. It may further be preferred according to the invention to use as developer component compounds which contain at least two aromatic nuclei which are substituted by amino and / or hydroxyl groups.
  • binuclear developer components that can be used in the compositions according to the invention, mention may be made in particular of the compounds which correspond to the following formula (Ent2) and their physiologically tolerated salts:
  • 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.
  • the bridge Y is an alkylene group having 1 to 14 carbon atoms, such as a linear or branched alkylene chain or an alkylene ring, which is one or more nitrogen-containing groups and / or one or more heteroatoms such as oxygen , Sulfur or nitrogen atoms may be interrupted or terminated and may possibly be substituted by one or more hydroxyl or C 1 - to C 8 -alkoxy radicals, or a direct bond,
  • G 5 and G 6 independently of one another represent a hydrogen or halogen atom, a C 1 - to C 4 -alkyl radical, a C 1 - to C 4 -monohydroxyalkyl radical, a C 2 - to C 4 -hydroxyalkyl radical, a C 1 - to C 4 -aminoalkyl radical or a direct compound for bridging Y,
  • G 7 , G 8 , G 9 , G 10 , G 11 and G 12 independently represent a hydrogen atom, a direct bond to the bridge Y or a C 1 - to C 4 -alkyl radical, with the provisos that the compounds of the formula (Ent2) contain only one bridge Y per molecule and the compounds of the formula (Ent2) contain at least one amino group which carries at least one hydrogen atom.
  • the substituents used in formula (Ent2) are inventively defined analogous to the above statements.
  • Preferred binuclear developer components of the formula (Ent2) are in particular: N, N'-bis ( ⁇ -hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diamino-propan-2-ol, N, N'-bis ( ⁇ -hydroxyethyl) -N, N'-bis (4'-aminophenyl) ethylenediamine, N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis - (.beta.-hydroxyethyl) -N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis (4-methylaminophenyl) tetramethylenediamine, N, N'-diethyl-N, N ' bis- (4'-amino-3-dimethylphenyl) ethylenediamine, bis (2-hydroxy-5-aminophenyl
  • Very particularly preferred binuclear developer components of the formula (Ent2) are N, N'-bis ( ⁇ -hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diamino-propan-2-ol, Bis (2-hydroxy-5-aminophenyl) methane, 1, 3-bis (2,5-diaminophenoxy) -propan-2-ol, N, N'-bis (4'-aminophenyl) -1, 4-diazacycloheptane and 1, 10-bis (2 ', 5'-diaminophenyl) -1,4,7,10-tetraoxadecan or one of its physiologically acceptable salts.
  • p-aminophenol derivatives of the formula (Ent3) it may be preferred according to the invention to use as the developer component a p-aminophenol derivative or one of its physiologically tolerable salts. Particular preference is given to p-aminophenol derivatives of the formula (Ent3)
  • G 13 represents a hydrogen atom, a halogen atom, a C 1 - to C 4 -alkyl radical, a C 1 - to C 4 -monohydroxyalkyl radical, a C 2 - to C 4 -polyhydroxyalkyl radical, a (C 1 - to C 4 ) -alkoxy - (C 1 - to C 4) alkyl group a C 1 - to C 4 aminoalkyl radical, a hydroxy (d- to C 4) - alkylamino, C 1 - to C 4 -Hydroxyalkoxyrest, a C 1 - to C 4 hydroxyalkyl (C 4 to C!) - aminoalkyl radical or a (di-C 1 - to C 4 -alkylamino) - alkyl (C r to C 4), and G 14 represents a hydrogen or halogen atom, a C 1 - to C 4 alkyl, C 1 - to C 4 -
  • G 15 is hydrogen, C 1 - to C 4 -alkyl, C 1 - to C 4 -monohydroxyalkyl, C 2 - to C 4 -polyhydroxyalkyl, phenyl or benzyl, and
  • G 16 is hydrogen or a halogen atom.
  • Preferred p-aminophenols of the formula (Ent3) are, in particular, p-aminophenol, N-methyl-p-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 2-hydroxymethylamino-4-aminophenol, 4 -Amino-3-hydroxymethylphenol, 4-amino-2- ( ⁇ -hydroxyethoxy) -phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 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 physiological
  • Very particularly preferred compounds of the formula (Ent3) are p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- ( ⁇ , ⁇ -dihydroxyethyl) -phenol and 4-amino 2- (diethylaminomethyl) -phenol.
  • the developer component may be selected from o-aminophenol and its derivatives such as 2-amino-4-methylphenol, 2-amino-5-methylphenol or 2-amino-4-chlorophenol.
  • the developer component may be selected from heterocyclic developer components, such as the pyridine, pyrimidine, pyrazole, pyrazole pyrimidine derivatives and their physiologically acceptable salts.
  • Preferred pyridine derivatives are, in particular, the compounds described in the patents GB 1 026 978 and GB 1 153 196, such as 2,5-diamino-pyridine, 2- (4'-methoxyphenyl) amino-3-amino-pyridine, 2,3-diamino-6-methoxy-pyridine, 2- ( ⁇ -methoxyethyl) amino-3-amino-6-methoxy-pyridine and 3,4-diamino-pyridine.
  • Preferred pyrimidine derivatives are, in particular, the compounds described in German Patent DE 2 359 399, Japanese Laid-Open Patent Publication JP 02019576 A2 or in Laid-Open Publication WO 96/15765, such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2-dimethylamino-4,5, 6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triaminopyrimidine.
  • Preferred pyrazole derivatives are, in particular, the compounds described in patents DE 3 843 892, DE 4 133 957 and patent applications WO 94/08969, WO 94/08970, EP-740 931 and DE 195 43 988, such as 4,5 Diamino-1-methylpyrazole, 4,5-diamino-1- ( ⁇ -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-1
  • Triaminopyrazole 1-methyl-3,4,5-triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole and 3,5-diamino-4- ( ⁇ -hydroxyethyl) amino-1-methylpyrazole.
  • Preferred pyrazolopyrimidine derivatives are, in particular, the derivatives of the pyrazolo [1,5-a] opyrimidine of the following formula (Ent4) and their tautomeric forms, if a tautomeric equilibrium exists:
  • G 17, G 18, G 19 and G 20 are independently a hydrogen atom, a C 1 - to C 4 -alkyl radical, an aryl radical, a Ci to C 4 -hydroxyalkyl group, a C 2 - to C 4 - Polyhydroxyalkylrest a (C 1 - to C 4 J-AIkOXy- (C 1 - to C 4 ) -alkyl radical, a C 1 - to C 4 - aminoalkyl radical which may optionally be protected by an acetyl-ureide or a sulfonyl radical , a (C 1 to C 4 ) alkylamino (C 1 to C 4 ) alkyl radical, a DK (C 1 to C 4 ) alkyl] (C r to C 4 ) aminoalkyl radical, wherein the Dialkyl radicals optionally form a carbon cycle or a heterocycle with 5 or 6 chain members, a C 1 - to C 4 -hydroxyalkyl or
  • Group OH occupy the positions (2,3); (5,6); (6,7); (3,5) or (3,7);
  • pyrazolo [1, 5-a] pyrimidines of the above formula (Ent4) can be prepared as described in the literature by cyclization from an aminopyrazole or hydrazine.
  • m-phenylenediamine derivatives naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives and heterocyclic compounds are generally used.
  • Coupler components preferred according to the invention are m-aminophenol and its derivatives, such as, for example, 5-amino-2-methylphenol, N-
  • Cyclopentyl-3-aminophenol 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 2,6-dimethyl-3-aminophenol, 3-TNfluoroacetylamino-2-chloro-6-methylphenol, 5- Amino-4-chloro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol, 5- (2'-
  • Resorcinol monomethyl ether 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2-
  • Naphthalene derivatives such as 1-naphthol, 2-methyl-1-naphthol, 2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 1, 7-dihydroxynaphthalene, 1 , 8-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 2,3-dihydroxynaphthalene,
  • Morpholine derivatives such as 6-hydroxybenzomorpholine and 6-aminobenzomorpholine,
  • Quinoxaline derivatives such as 6-methyl-1,2,3,4-tetrahydroquinoxaline, pyrazole derivatives such as 1-phenyl-3-methylpyrazol-5-one, indole derivatives such as 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole, pyrimidine derivatives such as For example, 4,6-diaminopyrimidine, 4-amino-2,6-dihydroxypyrimidine, 2,4-diamino-6-hydroxypyrimidine, 2,4,6-trihydroxypyrimidine, 2-amino-4-methylpyrimidine, 2-amino-4-hydroxy 6-methylpyrimidine and 4,6-dihydroxy-2-methylpyrimidine, or methylenedioxybenzene derivatives such as, for example, 1-hydroxy-3,4-methylenedioxybenzene, 1-amino-3,4-methylenedioxybenzene and 1- (2'-hydroxyethyl) -amino 3,4-methylenedioxybenzene and their physiologically
  • coupler components according to the invention are 1-naphthol, 1, 5, 2,7- and 1, 7-dihydroxynaphthalene, 3-aminophenol, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, resorcinol, 4-chlororesorcinol , 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol and 2,6-dihydroxy-3,4-dimethylpyridine and the physiologically acceptable salts of the aforementioned compounds.
  • the agents according to the invention preferably contain the developer components in an amount of from 0.005 to 10% by weight, preferably from 0.1 to 5% by weight, in each case based on the total agent.
  • the agents of the invention preferably contain the coupler components in an amount of 0.005 to 10 wt .-%, preferably from 0.1 to 5 wt .-%, each based on the total agent.
  • composition according to the invention can be used as a coloring component in the form of the oxo dye precursors at least one combination of at least one compound of the component
  • Compounds according to the invention having a reactive carbonyl group have at least one carbonyl group as reactive group which reacts with the compounds of component 2 to form a chemical bond linking both components. Further, according to the invention, those compounds are also included as component 1 in which the reactive carbonyl group is derivatized or masked in such a way that the reactivity of the carbon atom of the derivatized or masked carbonyl group with respect to the component 2 is always present.
  • These derivatives are preferably condensation compounds of reactive carbonyl compounds with a) amines and their derivatives to form imines or oximes as a condensation compound b) alcohols to form acetals or ketals as a condensation compound c) water to form hydrates as a condensation compound of aldehydes.
  • Component 1 is preferably selected from the group formed from acetophenone, propiophenone, 2-hydroxyacetophenone, 3-hydroxyacetophenone, 4-hydroxyacetophenone, 2-hydroxypropiophenone, 3-hydroxypropiophenone, 4-hydroxypropiophenone, 2-hydroxybutyrophenone, 3 Hydroxybutyrophenone, 4-hydroxybutyrophenone, 2,4-dihydroxyacetophenone, 2,5-dihydroxyacetophenone, 2,6-dihydroxyacetophenone, 2,3,4-trihydroxyacetophenone, 3,4,5-trihydroxyacetophenone, 2,4,6-dihydroxyacetophenone Trihydroxyacetophenone, 2,4,6-trimethoxyacetophenone, 3,4,5-trimethoxyacetophenone, 3,4,5-trimethoxyacetophenone diethyl ketal, 4-hydroxy-3-methoxy-acetophenone, 3,5-dimethoxy-4- hydroxyacetophenone, 4-aminoacetophenone, 4-dimethylamino
  • 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.
  • CH-acidic compounds also include enamines which are formed by alkaline treatment of quaternized N-heterocycles with a CH-acidic alkyl group in conjugation with the quaternary nitrogen.
  • the CH-acidic compounds of component 2 are preferably selected from the group consisting of 1, 2,3,3-tetramethyl-3H-indolium iodide, 1, 2,3,3-tetramethyl-3H-indolium p-toluenesulfonate, 1, 2,3,3-tetramethyl-3H-indolium methanesulfonate, 1,3,3-trimethyl-2-methylenindoline (Fischer's base), 2,3-dimethylbenzothiazolium iodide, 2,3-dimethylbenzothiazolium-p-toluenesulfonate Fonate, 2,3-dimethyl-naphtho [1,2-d] thiazolium p-toluenesulfonate, 3-ethyl-2-methyl-naphtho [1,2-d] thiazolium p-toluenesulfonate, rhodanine, rhodanine-3
  • Preferred primary or secondary aromatic amines of component B are selected from N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, N- (2-hydroxyethyl) -N-ethyl-p-phenylenediamine, N, N-bis (2-hydroxyethyl) -p-phenylenediamine, N- (2-methoxyethyl) -p-phenylenediamine, 2,3-dichloro-p-phenylenediamine, 2,4-dichloro-p-phenylenediamine, 2.5- Dichloro-p-phenylenediamine, 2-chloro-p-phenylenediamine, 2,5-dihydroxy-4-morpholinoaniline, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminomethyl-4-aminophenol, 2-hydroxymethyl-4- aminophenol, o-phenylenediamine, m-phen
  • R 7 represents a hydroxy or amino group represented by C 1-4 alkyl, C 1-4 hydroxyalkyl, C 1-4 alkoxy or R 8 , R 9 , R 10 , R 11 and R 12 independently represent a hydrogen atom, a hydroxy or an amino group represented by C 1 -C 4 alkyl, C 1 -C 8 hydroxyalkyl, C 1 -AIkOXy- -C 4, C 1 -C 4 - aminoalkyl or C 1 -C 4 -alkoxy-C 1 -C 4 alkyl groups may be substituted, stand, and P is a direct bond, a saturated or unsaturated, optionally hydroxy-substituted carbon chain of 1 to 4 carbon atoms, a carbonyl, sulfoxy, sulfonyl or imino group, an oxygen or sulfur atom, or a group of formula VI
  • Q signifies a direct bond, a CH 2 or CHOH group
  • Q 'and Q independently represent an oxygen atom, an NR 13 group in which R 13 represents a hydrogen atom, a C 1-4 alkyl or a hydroxyC 1-4 alkyl group, both of which together with the remainder of the molecule 5-, 6- or 7-membered ring, means the group O- (CH 2 ) P -NH or NH- (CH 2 ) P -O, wherein p and p 1 are 2 or 3, and
  • O is a number from 1 to 4,
  • 4,4'-diaminostilbene and its hydrochloride 4,4'-diaminostilbene-2,2'-disulfonic acid mono- or di-Na salt, 4-amino-4'-dimethylaminostilbene and its hydrochloride, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfoxide, 4,4'-diaminodiphenylamine, 4,4'-diaminodiphenylamine-2-sulfonic acid, 4,4'-diaminobenzophenone, 4,4 ' - Diaminodiphenylether, 3,3 ', 4,4'-tetraaminodiphenyl, 3,3', 4,4'-tetraamino-benzophenone, 1, 3-bis (2,4-diaminophenoxy) -propane, 1, 8-bis
  • Suitable nitrogen-containing heterocyclic compounds are, for. B. 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-amino-3-hydroxy-pyridine, 2,6-diamino-pyridine, 2,5-diamino-pyridine, 2- (aminoethylamino) -5-aminopyridine, 2,3-diamino-pyridine, 2-dimethylamino-5-amino-pyridine, 2-methylamino-3-amino-6-methoxy-pyridine, 2,3-diamino-6-methoxy-pyridine, 2,6-dimethoxy 3,5-diamino-pyridine, 2,4,5-triamino-pyridine, 2,6-dihydroxy-3,4-dimethyl-pyridine, N- [2- (2,4-diaminophenyl) aminoethyl] -N- (5- amino-2-pyridyl) amine, N- [2- (4-aminopheny
  • heterocyclic compounds the hydroxypyrimidines disclosed in DE-U 1-299 08 573 can be used according to the invention.
  • the aforementioned compounds can be used both in free form and in the form of their physiologically acceptable salts, for. B. as salts of inorganic acids, such as hydrochloric or sulfuric acid, are used.
  • Suitable aromatic hydroxy compounds are, for. 2-methylresorcinol, 4-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, resorcinol, 3-methoxyphenol, pyrocatechol, hydroquinone, pyrogallol, phloroglucinol, hydroxyhydroquinone, 2-methoxyphenol, 3-methoxyphenol, 4-methoxyphenol, 3 Dimethylaminophenol, 2- (2-hydroxyethyl) phenol, 3,4-methylenedioxyphenol, 2,4-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 2,4-dihydroxy-phenylacetic acid, 3,4-dihydroxyphenylacetic acid, gallic acid, 2,4 , 6-trihydroxybenzoic acid, 2,4,6-trihydroxyace- tophenone, 2-chlororesorcinol, 4-chlororesorcinol, 1-naphthol, 1, 5-dihydroxynaphthalene, 2,3-
  • the compounds of component A and the compounds of component B are preferably used in the shading agents according to the invention in each case in an amount of 0.03 to 65 mmol, in particular from 1 to 40 mmol, based on 100 g of the total Nuancierstoffs used.
  • the molar ratio of the compound of component A and the compound of component B may range from 0.5 to 2.0, preferably using equimolar amounts.
  • the actual Nuancierstoff is prepared with separate storage of components A and B immediately before use by mixing.
  • indoles and indolines which have at least one hydroxy or amino group, preferably as a substituent on the six-membered ring.
  • these groups may carry further substituents, e.g. Example in the form of etherification or esterification of the hydroxy group or alkylation of the amino group.
  • the colorants contain at least one indole and / or indoline derivative.
  • Particularly suitable precursors of naturally-analogous dyes are derivatives of 5,6-dihydroxyindoline of the formula (VIIa),
  • G 19 is hydrogen, a C 1 -C 4 -alkyl group or a C 1 -C -hydroxyalkyl group,
  • G 20 is hydrogen or a -COOH group, where the -COOH group may also be present as a salt with a physiologically compatible cation,
  • G 2 i is hydrogen or a C 1 -C 4 -alkyl group
  • G 22 is hydrogen, a CVCU alkyl group or a group -CO-G 24 in which G 24 is a C 1 -C 4 alkyl group, and
  • G 23 stands for one of the groups mentioned under G 22 , as well as physiologically tolerable salts of these compounds with an organic or inorganic acid.
  • Particularly preferred derivatives of indoline are 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6 dihydroxyindoline, 5,6-dihydroxyindoline-2-carboxylic acid and 6-hydroxyindoline, 6-aminoindoline and 4-aminoindoline.
  • N-methyl-5,6-dihydroxyindoline N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline and especially 5, 6-Dihydroxyindolin.
  • G 25 is hydrogen, a C 1 -C 4 -alkyl group or a C 1 -C 4 -hydroxyalkyl group,
  • G 26 is hydrogen or a -COOH group, where the -COOH group may also be present as a salt with a physiologically compatible cation,
  • G 27 is hydrogen or a C r C 4 -alkyl group
  • G 28 is hydrogen, a C 1 -C 4 -alkyl group or a group -CO-G 30 in which G 30 is a C 1 -C 4 -alkyl group, and
  • G 29 is one of the groups mentioned under G 28 , as well as physiologically acceptable salts of these compounds with an organic or inorganic acid.
  • Particularly preferred derivatives of indole are 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6- dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid, 6-hydroxyindole, 6-aminoindole and 4-aminoindole.
  • N-methyl-5,6-dihydroxyindole N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole, and especially the 5,6 -Dihydroxyindol.
  • the indoline and indole derivatives can be used in the emulsions of the invention 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 usually contained in these in amounts of 0.05 to 10 wt .-%, preferably 0.2 to 5 wt .-%.
  • the amino acid is advantageously an ⁇ -amino acid; Very particularly preferred ⁇ -amino acids are arginine, ornithine, lysine, serine and histidine, in particular arginine.
  • Preferred substantive dyes which are used in the compositions according to the invention as a coloring component are 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 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
  • agents according to the invention may contain a cationic substantive dye. 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 preferably contain the substantive dyes in an amount of from 0.01 to 20% by weight, based on the ready-to-use agent.
  • 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 oxidation dye precursors or the direct dyes are in each case homogeneous compounds. Rather, in the inventive Compositions, due to the production process for the individual dyes, be contained in minor amounts of other components, as far as they do not adversely affect the color result or other reasons, such as toxicological, must be excluded.
  • the emulsion according to the invention contains oxidation dye precursors or in particular precursors of a nature-analogous dye based on indole or indoline
  • the actual oxidative dyeing of the fibers can in principle be carried out with atmospheric oxygen.
  • the presence of oxidation dye precursors is therefore not a mandatory requirement for the use of chemical oxidants in the emulsions according to the invention.
  • a chemical oxidizing agent is in particular hydrogen peroxide and / or at least one addition product thereof, in particular to inorganic or organic compounds such as sodium perborate, sodium percarbonate, magnesium percarbonate,
  • the actual colorant is prepared by separate storage of dye precursors in the emulsion of the invention and the oxidizing agent immediately before use by mixing.
  • the emulsion may also be applied to the hair together with a catalyst which promotes the oxidation of the dye precursors, e.g. by atmospheric oxygen, activated.
  • catalysts are e.g. Metal ions, iodides, quinones or certain enzymes.
  • Suitable metal ions are, for example, Zn 2+ , Cu 2+ , Fe 2+ , Fe 3+ , Mn 2+ , Mn 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.
  • Suitable enzymes include peroxidases, which can significantly enhance the effect of small amounts of hydrogen peroxide. Furthermore, such enzymes are according to the invention suitable, which directly oxidize the oxidation dye precursors with the aid of atmospheric oxygen, such as the laccases, or in situ produce small amounts of hydrogen peroxide and thus biocatalytically activate the oxidation of the dye precursors. Particularly suitable catalysts for the oxidation of the dye precursors are the so-called 2-electron oxidoreductases in combination with the specific substrates, eg
  • Lactate oxidase and lactic acid and their salts Lactate oxidase and lactic acid and their salts
  • the actual colorant is conveniently prepared immediately prior to use by mixing the preparation of the chemical oxidant (oxidation component) with the emulsion of the invention containing the coloring components.
  • the application temperatures can be in a range between 15 and 40 0 C. After a contact time of 5 to 45 minutes, the hair dye is removed by rinsing of the hair to be dyed. The washing with a shampoo is eliminated.
  • an emulsion according to the invention may optionally be applied to the hair with additional dye precursors but also without prior mixing with the oxidation component.
  • the chemical oxidant is applied.
  • a further exposure time of 10 to 20 minutes is then rinsed and nachshampooniert if desired.
  • the corresponding agent is adjusted to a pH of about 4 to 7.
  • an air oxidation is initially desired, wherein the applied agent preferably has a pH of 7 to 10.
  • the ready-to-use colorants preferably contain the chemical oxidizing agents in an amount of from 0.5 to 12.0% by weight, in particular from 6 to 12% by weight, based in each case on the weight of the ready-to-use colorant.
  • the emulsions according to the invention may contain, as further auxiliaries and additives, surfactants, in particular cationic surfactants, superfatting agents, stabilizers, waxes, consistency regulators, thickeners, cationic polymers, silicone compounds, biogenic agents, antidandruff agents, film formers, preservatives, hydrotropes, solubilizers, fragrances and the like ,
  • surfactants in particular cationic surfactants, superfatting agents, stabilizers, waxes, consistency regulators, thickeners, cationic polymers, silicone compounds, biogenic agents, antidandruff agents, film formers, preservatives, hydrotropes, solubilizers, fragrances and the like ,
  • Surfactants which may be present are nonionic, anionic, cationic and / or amphoteric or amphoteric surfactants, the proportion of which in the compositions is usually from about 50 to 99 and preferably from 70 to 90% by weight.
  • anionic surfactants are soaps, alkylbenzenesulfonates, alkanesulfonates, olefinsulfonates, alkyl ether sulfonates, glycerol ether sulfonates, ⁇ -methyl ester sulfonates, fatty acid fatty acids, alkyl sulfates, fatty alcohol ether sulfates, glycerol ether sulfates, hydroxy mixed ether sulfates, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, mono- and dialkyl sulfosuccinates, mono- and dialkylsulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, N-acylamino acids
  • the agents according to the invention preferably contain no anionic surfactant which is different from the component (iii) of the emulsion according to the invention.
  • Cationic surfactants in particular as a care substance, of the quaternary ammonium compound type, the esterquats and / or the amidoamines, may likewise be present in the emulsions according to the invention.
  • Preferred quaternary ammonium compounds are ammonium halides, in particular chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, eg.
  • cetyltrimethylammonium chloride stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride, as well as the imidazolium compounds known under the INCI names Quaternium-27 and Quaternium-83.
  • 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® ®.
  • 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 is that available under the name Tegoamid ® S 18 commercially stearamidopropyl dimethylamine.
  • the cationic surfactants can be present in the emulsions according to the invention in amounts of from 0.05 to 10% by weight, based on the weight of the emulsion. Amounts of 0.1 to 5 wt .-% are preferred.
  • Superfatting agents which can be used are substances such as lanolin and lecithin, as well as polyethoxylated or acylated lanolin and lecithin derivatives, polyol fatty acid esters and fatty acid alkanolamides, the latter also serving as foam stabilizers.
  • consistency factors are primarily fatty alcohols having 12 to 22 and preferably 16 to 18 carbon atoms into consideration.
  • alkyl oligoglucosides and / or fatty acid N-methyl glucamides of the same chain length and / or polyglycerol poly-12-hydroxy stearates is preferred.
  • Suitable thickening agents are, for example, polysaccharides, in particular xanthan gum, guar guar, agar agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl cellulose, and also higher molecular weight
  • surfactants such as ethoxylated fatty acid glycerides, esters of fatty acids with polyols such as pentaerythritol or trimethylolpropane, fatty alcohol ethoxylates with narrow homolog distribution or Alkyloligoglucoside and electrolyte such as sodium chloride and ammonium chloride.
  • Suitable cationic polymers are, for example, cationic cellulose derivatives, cationic starch, copolymers of diallylammonium salts and acrylamides, quaternized vinylpyrrolidone / vinylimidazole polymers such as Luviquat® (BASF AG, Ludwigshafen / FRG), condensation products of polyglycols and amines, quaternized collagen polypeptides such as lauryldimonium hydroxypropyl hydrolyzed collagen (Lamequat®L, Grünau GmbH), quaternized wheat polypeptides, polyethylenimine, cationic silicone polymers such as amidomethicones or Dow Corning, Dow Corning Co./US, copolymers of adipic acid and Dimethylaminohydroxypropyldiethylentrimamin (Cartaretine®, Sandoz / CH), polyaminopolyamides such as described in FR-A 22 52 840 and their crosslinked water
  • emulsions according to the invention act as a carrier for oxidation dye precursors
  • An oxidant-containing preparation is packaged in a storage container 2.
  • At least one of the storage containers 1 or 2 preferably provides for the addition of one of the two components to the other.
  • both storage containers for example, by plugging or screwing, are connected to each other, being created by this process, a spatial connection of the two storage containers and a transition of the components is made possible from one to the other storage container.
  • a mixture is prepared by shaking.
  • Both storage containers can also be spatially separate chambers in a multi-chamber vessel, wherein before, during or after the removal mix the separately assembled components.
  • the two components can also be given from the respective storage containers for mixing in a mixing bowl.
  • a second object of the invention is a process for the preparation of the emulsion according to the invention of the first subject of the invention, in which
  • At least one oil body is heated to a temperature above the phase inversion temperature and at least one emulsifier is added,
  • At least one active substance preferably in dissolved form, is added wherein during at least one of the preceding steps or in between at least one anionic alkyl oligoglucoside derivative and / or at least one anionic alkenyl oligoglucoside derivative is added.
  • the anionic alkyl oligoglucoside derivative or anionic alkenyl oligoglucoside derivative may preferably be added between steps (1) and (2), between steps (2) and (3), in step (3), between step (3) and (4 ), in step (4) and / or after step (4).
  • a third object of the invention is the use of the emulsion of the first subject of the invention as a cleanser for skin and / or hair.
  • a fourth subject of the invention is the use of the emulsion of the first subject of the invention additionally containing at least one coloring component as a cleaning and color-changing agent for keratin-containing fibers, in particular human hair.
  • the following inventive emulsion was prepared by the PIT method.
  • Emulgade PL 68/50 ® 1 is 4.4
  • cetylstearyl alcohol with approx. 20 EO units (INCI name: Ceteareth-20) (Cognis)
  • Emulsion according to Table 1 40.00 p-toluenediamine 1, 43
  • the dye precursor support of Table 2 of the invention is stable, low viscosity, and therefore, is excellently suited for use in a two component system.
  • 50.0 g of the dye precursor carrier were mixed with 50.0 g of the developer dispersion according to Table 3 in a shaking container. The mixture of components proceeded quickly and easily by shaking.
  • the resulting application mixture was applied to a test hair strand (Kerling, natural white). After 30 minutes exposure time at 32 0 C, the hair was rinsed, washed with a conventional shampoo and then dried.

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Abstract

Emulsions which are prepared by the phase inversion temperature method and comprise (i) at least one emulsifier, (ii) at least one oil body, (iii) at least one anionic alkyl oligoglucoside derivative and/or at least one anionic alkenyl oligoglucoside derivative and (iv) water are storage-stable and washing-active. They can be used particularly well as carriers of active ingredients for washing-active skin and/or washing-active hair care compositions.

Description

„Waschaktive PIT-Emulsionen""Washing active PIT emulsions"
Die Erfindung betrifft stabile, waschaktive PIT-Emulsionen, die als waschaktive Substanz mindestens ein anionisches Alkyl- bzw. Alkenyloligoglykosid-Derivat enthalten, sowie ein Herstellungsverfahren.The invention relates to stable, wash-active PIT emulsions containing as detergent substance at least one anionic alkyl or Alkenyloligoglykosid derivative, and a production process.
Zur Herstellung feinteiliger Emulsionen über die Phaseninversionstemperatur-Methode werden üblicherweise Mischungen aus verschiedenen Emulgatoren in Kombination mit ölkörpern eingesetzt. Eine Übersicht zu Phaseninversionstemperatur-Emulsionen (PIT-Emulsionen) findet sich von A. Wadle et al. in Parf.Kosm. 72, 250 (1996); stellvertretend für den umfangreichen Stand der Technik sei auf die Druckschriften DE-A1 3819193, DE-A1 4010393, DE-A1 4140562, DE-A1 4318171 und DE-A1 4337041 verwiesen.For the preparation of finely divided emulsions via the phase inversion temperature method, mixtures of different emulsifiers in combination with oil bodies are usually used. An overview of phase inversion temperature emulsions (PIT emulsions) can be found in A. Wadle et al. in Parf.Kosm. 72, 250 (1996); Representative of the extensive state of the art, reference is made to the publications DE-A1 3819193, DE-A1 4010393, DE-A1 4140562, DE-A1 4318171 and DE-A1 4337041.
Aus der Druckschrift W0-A1 -98/51267 ist ein Verfahren zu Herstellung von Haarfärbemitteln bekannt, in welchem unter Verwendung von ölkörpern und Emulgatoren aus der Gruppe Alkyl- und/oder Alkenyloligoglykoside, Polyolpoly-12-hydroxystearaten, Fettalkoholen und Fettalkoholpotyethylenglykolethern, eine wässrige Zubereitung in Form einer PIT-Emulsion oder Mikroemulsion hergestellt wird und anschließend in einem Kaltprozeß die Farbstoffe bzw. deren Vorprodukte eingerührt werden.From the document W0-A1 -98 / 51267 a process for the production of hair colorants is known, in which using oil bodies and emulsifiers from the group alkyl and / or Alkenyloligoglykoside, Polyolpoly-12-hydroxystearaten, fatty alcohols and Fettalkoholpotyethylenglykolethern, an aqueous preparation is prepared in the form of a PIT emulsion or microemulsion and then the dyes or their precursors are stirred in a cold process.
Die Druckschrift EP-A2-1 321 132 beschreibt stabile Färbeemulsionen, in denen Oxidationsfarbstoffvorprodukte in eine PIT-Emulsion eingearbeitet sind. Wenn das Nachwaschen mit einem Shampoo entfallen soll, könne gemäß dieser Druckschrift ein waschaktives Tensid unter Erhalt eines Färbeshampoos zugesetzt werden. Allerdings ergibt sich hierbei für den Fachmann das Problem, dass in Gegenwart waschaktiver Tenside die PIT-Emulsion an Stabilität verliert.The document EP-A2-1 321 132 describes stable dyeing emulsions in which oxidation dye precursors are incorporated in a PIT emulsion. If the washing with a shampoo is to be omitted, according to this document a washing-active surfactant can be added to obtain a dyeing shampoo. However, the problem arises here for the skilled person that the PIT emulsion loses stability in the presence of washing-active surfactants.
Die Aufgabe der Erfindung besteht darin, stabile PIT-Emulsionen bereitzustellen, die ein waschaktives Tensid enthalten und eine Reinigungswirkung bei Anwendung auf der Haut und/oder dem Haar entfalten. Zusätzlich sollen die PIT-Emulsionen insbesondere bei basischem pH-Wert stabil sein und die Penetration eines Wirkstoffs wie z.B. eines Farbstoffs bzw. mehrerer Farbstoffvorprodukte in das Substrat ermöglichen.The object of the invention is to provide stable PIT emulsions which contain a washing-active surfactant and develop a cleaning action when applied to the skin and / or the hair. In addition, the PIT emulsions should in particular at basic pH be stable and allow the penetration of an active substance such as a dye or more dye precursors into the substrate.
Gegenstand der Erfindung ist eine Emulsion, die nach der Phaseninversionstemperatur-Methode hergestellt wurde, enthaltendThe invention relates to an emulsion prepared by the phase inversion temperature method comprising
(i) mindestens einen Emulgator,(i) at least one emulsifier,
(ii) mindestens einen ölkörper,(ii) at least one oily body,
(iii) mindestens ein anionisches Alkyloligoglucosid-Derivat und/oder mindestens ein anionisches Alkenyloligoglucosid-Derivat und (iv) Wasser.(iii) at least one anionic alkyl oligoglucoside derivative and / or at least one anionic alkenyl oligoglucoside derivative and (iv) water.
Die Emulgatoren sind bevorzugt in Mengen von 0,5 bis 20, vorzugsweise 1 bis 10 Gew.-% - bezogen auf das Gewicht der Emulsionen - in den erfindungsgemäßen Emulsionen enthalten.The emulsifiers are preferably present in amounts of 0.5 to 20, preferably 1 to 10 wt .-% - based on the weight of the emulsions - in the emulsions according to the invention.
Als Emulgator kommt bevorzugt mindestens ein nichtionogenes Tensid, besonders bevorzugt mindestens ein nichtionogenes Tensid aus wenigstens einer der folgenden Gruppen in Frage:The emulsifier used is preferably at least one nonionic surfactant, more preferably at least one nonionic surfactant from at least one of the following groups:
(1) Anlagerungsprodukte von 2 bis 30 Mol Ethylenoxid und/ oder 0 bis 5 Mol Propylenoxid an lineare Fettalkohole mit 8 bis 22 C-Atomen, an Fettsäuren mit 12 bis 22 C-Atomen und an Alkylphenole mit 8 bis 15 C-Atomen in der Alkylgruppe;(1) addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear fatty alcohols having 8 to 22 carbon atoms, to fatty acids having 12 to 22 carbon atoms and to alkylphenols having 8 to 15 carbon atoms in the alkyl group;
(2) C12/i8-Fettsäuremono- und -diester von Anlagerungsprodukten von 1 bis 30 Mol Ethylenoxid an Glycerin;(2) C 12 / i 8 fatty acid monoesters and diesters of addition products of 1 to 30 mol ethylene oxide onto glycerol;
(3) Glycerinmono- bzw. -diester (Partialglyceride) sowie Sorbitanmono- und -diester, jeweils von gesättigten und/oder ungesättigten Fettsäuren mit 6 bis 22 Kohlenstoffatomen und deren Ethylenoxidanlagerungsprodukte;(3) glycerol mono- or diesters (partial glycerides) as well as sorbitan mono- and diesters, each of saturated and / or unsaturated fatty acids having 6 to 22 carbon atoms and their ethylene oxide addition products;
(4) Alkylmono- und -oligoglykoside mit 8 bis 22 Kohlenstoffatomen im Alkylrest und deren ethoxylierte Analoga; insbesondere Alkyl- bzw. Alkenyl-, Mono- bzw. Oligoglykoside der Formel(4) alkyl mono- and oligoglycosides having 8 to 22 carbon atoms in the alkyl group and their ethoxylated analogs; in particular alkyl or alkenyl, mono- or oligoglycosides of the formula
R'-O-(GI)m, (I) worinR'-O- (GI) m , (I) wherein
R' eine C6-22-Alkyl- oder C6-22-Alkenylgruppe,R 'is a C 6-22 alkyl or C 6-22 alkenyl group,
Gl eine Glykosideinheit, die sich von einem Zucker mit 5 oder 6 Kohlenstoffatomen ableitet und m eine Zahl von 1 bis 10 bedeutet. Die Alkyl- und/oder Alkenyloligoglykoside leiten sich von Aldosen bzw. Ketosen mit 5 oder 6 Kohlen-stoffatomen (Rest Gl), vorzugsweise der Glucose ab. Die bevorzugten Alkyl- und/oder Alkenyloligoglykoside sind somit Alkyl- und/oder Alkenyloligoglucoside. Die Indexzahl m in der allgemeinen Formel (I) gibt den Oligomerisierungsgrad (DP), d. h. die Verteilung von Mono- und Oligoglykosiden an und steht für eine Zahl zwischen 1 und 10. Die Begriffe „Oligoglykosid" und „Polyglykosid" werden im Rahmen der Anmeldung synonym nach dieser Definition verwendet.Gl is a glycoside unit derived from a sugar having 5 or 6 carbon atoms and m is a number from 1 to 10. The alkyl and / or Alkenyloligoglykoside are derived from aldoses or ketoses with 5 or 6 carbon atoms (remainder Gl), preferably glucose. The preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides. The index number m in the general formula (I) indicates the degree of oligomerization (DP), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10. The terms "oligoglycoside" and "polyglycoside" are used in the context of the application used synonymously according to this definition.
Wahrend m in einer gegebenen Verbindung stets ganzzahlig sein muß und hier vor allem die Werte m = 1 bis 6 annehmen kann, ist der Wert m für ein bestimmtes Alkyloligoglykosid eine analytisch ermittelte rechnerische Größe, die meistens eine gebrochene Zahl darstellt. Vorzugsweise werden Alkyl- und/oder Alkenyloligoglykoside mit einem mittleren Oligomerisierungsgrad m von 1 ,1 bis 3,0 eingesetzt. Aus anwendungstechnischer Sicht sind solche Alkyl- und/oder Alkenyloligoglykoside bevorzugt, deren Oligomerisierungsgrad kleiner als 1 ,7 ist und insbesondere zwischen 1 ,2 und 1 ,4 liegt. Der Alkyl- bzw. Alkenylrest R' kann sich von primären Alkoholen mit 4 bis 11 , vorzugsweise 8 bis 10 Kohlenstoffatomen ableiten. Typische Beispiele sind Butanol, Capronalkohol, Caprylalkohol, Caprinalkohol und Undecylalkohol sowie deren technische Mischungen, wie sie beispielsweise bei der Hydrierung von technischen Fettsäuremethylestern oder im Verlauf der Hydrierung von Aldehyden aus der Roelen'schen Oxosynthese erhalten werden. Bevorzugt sind Alkyloligo- glucoside der Kettenlänge C8-C10 (DP = 1 bis 3), die als Vorlauf bei der destillativen Auftrennung von technischem C8-C18-Kokosfettalkohol anfallen und mit einem Anteil von weniger als 6 Gew.-% C12-Alkohol verunreinigt sein können sowie Alkyloligoglucoside auf Basis technischer C9/11-Oxoalkohole (DP = 1 bis 3). Der Alkyl- bzw. Alkenylrest R' kann sich ferner auch von primären Alkoholen mit 12 bis 22, vorzugsweise 12 bis 14 Kohlenstoffatomen ableiten. Typische Beispiele sind Laurylalkohol, Myristylalkohol, Cetylalkohol, Palmoleylalkohol, Stearylalkohol, Isostearylalkohol, Oleylalkohol, Elaidylalkohol, Petro- selinylalkohol, Arachylalkohol, Gadoleylalkohol, Behenylalkohol, Erucylalkohol, Brassidylalkohol sowie deren technische Gemische, die wie oben beschrieben erhalten werden können. Bevorzugt sind Alkyloligoglucoside auf Basis von gehärtetem C12/n- Kokosalkohol mit einem DP von 1 bis 3;Whereas m always has to be an integer in a given compound, and above all the values m = 1 to 6, the value m for a given alkyloligoglycoside is an analytically determined arithmetic variable, which usually represents a fractional number. Preference is given to using alkyl and / or alkenyl oligoglycosides having a mean degree of oligomerization m of from 1.1 to 3.0. From an application point of view, those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4 are preferred. The alkyl or alkenyl radical R 'can be derived from primary alcohols having 4 to 11, preferably 8 to 10 carbon atoms. Typical examples are butanol, caproic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and technical mixtures thereof, as obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the hydrogenation of aldehydes from Roelen's oxo synthesis. Preference is given to alkyl oligoglucosides of chain length C 8 -C 10 (DP = 1 to 3), which are obtained as a feedstock in the distillative separation of technical C 8 -C 18 coconut fatty alcohol and in a proportion of less than 6% by weight C 12 alcohol may be contaminated as well as alkyl oligoglucosides based on technical C 9/11 oxo alcohols (DP = 1 to 3). The alkyl or alkenyl radical R 'can also be derived from primary alcohols having 12 to 22, preferably 12 to 14 carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol and technical mixtures thereof which can be obtained as described above. Preference is given to alkyl oligoglucosides based on hydrogenated C 12 / n cocoalcohol having a DP of 1 to 3;
(5) Anlagerungsprodukte von 15 bis 60 Mol Ethylenoxid an Ricinusöl und/oder gehärtetes Ricinusöl;(5) addition products of 15 to 60 moles of ethylene oxide with castor oil and / or hydrogenated castor oil;
(6) Polyol- und insbesondere Polyglycerinester, wie z.B. Polyglycerinpolyricinoleat, Polyglycerinpoly-12-hydroxystearat oder Polyglycerindimerat. Ebenfalls geeignet sind Gemische von Verbindungen aus mehreren dieser Substanzklassen;(6) polyol and especially polyglycerol esters, e.g. Polyglycerol polyricinoleate, polyglycerol poly-12-hydroxy stearate or polyglycerol dimerate. Also suitable are mixtures of compounds of several of these classes of substances;
(7) Anlagerungsprodukte von 2 bis 15 Mol Ethylenoxid an Ricinusöl und/oder gehärtetes Ricinusöl; (8) Partialester auf Basis linearer, verzweigter, ungesättigter bzw. gesättigter C6/22-Fettsäuren, Ricinolsäure sowie 12-Hydroxystearinsäure und Glycerin, Polyglycerin, Pentaerythrit, Dipenta-erythrit, Zuckeralkohole (z.B. Sorbit), Alkylglucoside (z.B. Methylglucosid, Butylglucosid, Lauryl-glucosid) sowie Polyglucoside (z.B. Cellulose);(7) addition products of 2 to 15 moles of ethylene oxide with castor oil and / or hydrogenated castor oil; (8) partial esters based on linear, branched, unsaturated or saturated C 6/22 fatty acids, ricinoleic acid and 12-hydroxystearic acid and glycerol, polyglycerol, pentaerythritol, dipentaerythritol, sugar alcohols (eg sorbitol), alkyl glucosides (eg methyl glucoside, butyl glucoside, Lauryl glucoside) as well as polyglucosides (eg cellulose);
(9) Trialkylphosphate sowie Mono-, Di- und/oder Tri-PEG-alkylphosphate;(9) trialkyl phosphates and mono-, di- and / or tri-PEG-alkyl phosphates;
(10) Wollwachsalkohole;(10) wool wax alcohols;
(11) Polysiloxan-Polyalkyl-Polyether-Copolymere bzw. entsprechende Derivate;(11) polysiloxane-polyalkyl-polyether copolymers or corresponding derivatives;
(12) Mischester aus Pentaerythrit, Fettsäuren, Citronensäure und Fettalkohol gemäß DE-PS 1165574 und/oder Mischester von Fettsäuren mit 6 bis 22 Kohlenstoffatomen, Methylglucose und Polyolen, vorzugsweise Glycerin sowie(12) mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohol according to DE-PS 1165574 and / or mixed esters of fatty acids having 6 to 22 carbon atoms, methyl glucose and polyols, preferably glycerol and
(13) Polyalkylenglycole.(13) Polyalkylene glycols.
Die Anlagerungsprodukte von Ethylenoxid und/oder von Propylenoxid an Fettalkohole, Fettsäuren, Alkylphenole, Glycerinmono- und -diester sowie Sorbitanmono- und -diester von Fettsäuren oder an Ricinusöl stellen bekannte, im Handel erhältliche Produkte dar. Es handelt sich dabei um Homologen-gemische, deren mittlerer Alkoxylierungsgrad dem Verhältnis der Stoffmengen von Ethylenoxid und/ oder Propylenoxid und Substrat, mit denen die Anlagerungsreaktion durchgeführt wird, entspricht. C12/i8-Fettsäuremono- und -diester von Anlagerungsprodukten von Ethylenoxid an Glycerin sind aus DE-PS 20 24 051 als Rückfettungsmittel für kosmetische Zubereitungen bekannt.The addition products of ethylene oxide and / or of propylene oxide to fatty alcohols, fatty acids, alkylphenols, glycerol mono- and diesters and sorbitan mono- and diesters of fatty acids or to castor oil are known, commercially available products. These are homolog mixtures, whose average degree of alkoxylation corresponds to the ratio of the molar amounts of ethylene oxide and / or propylene oxide and substrate with which the addition reaction is carried out. 12 C / i 8 fatty acid monoesters and diesters of addition products of ethylene oxide onto glycerol are known from DE-PS 20 24 051. as refatting agents for cosmetic preparations.
Weiterhin können als Emulgatoren zwitterionische Tenside verwendet werden. Als zwitterionische Tenside werden solche oberflächenaktiven Verbindungen bezeichnet, die im Molekül mindestens eine quartäre Ammoniumgruppe und mindestens eine Carboxylat- und eine Sulfonatgruppe tragen. Besonders geeignete zwitterionische Tenside sind die sogenannten Betaine wie die N-Alkyl- N,N-dimethylammoniumglycinate, beispielsweise das Kokosalkyldimethylammoniumglycinat, N- Acylamino-propyl-N.N-dimethylammoniumglycinate, beispielsweise das Kokosacyl- aminopropyldimethylammonium-glycinat, und 2-Alkyl-3-carboxylmethyl-3-hydroxyethylimidazoline mit jeweils 8 bis 18 C-Atomen in der Alkyl- oder Acylgruppe sowie das Kokosacylaminoethyl- hydroxyethylcarboxymethylglycinat. Besonders bevorzugt ist das unter der CTFA-Bezeichnung Cocamidopropyl Betaine bekannte Fettsäureamid-Derivat. Ebenfalls geeignete Emulgatoren sind ampholytische Tenside. Unter am phobischen Tensiden werden solche oberflächenaktiven Verbindungen verstanden, die außer einer C8/i8-Alkyl- oder -Acylgruppe im Molekül mindestens eine freie Aminogruppe und mindestens eine -COOH- oder -SO3H-Gruppe enthalten und zur Ausbildung innerer Salze befähigt sind. Beispiele für geeignete ampholytische Tenside sind N- Alkylglycine, N-Alkylpropionsäuren, N-Alkylaminobuttersäuren, N-Alkyliminodipropionsäuren, N- Hydroxyethyl-N-alkylamidopropylglycine, N-Alkyltaurine, N-Alkylsarcosine, 2-Alkylaminopropion- säuren und Alkylaminoessigsäuren mit jeweils etwa 8 bis 18 C-Atomen in der Alkylgruppe. Besonders bevorzugte ampholytische Tenside sind das N-Kokosalkylaminopropionat, das Kokosacylaminoethylaminopropionat und das C12/18-Acylsarcosin. Neben den ampholytischen kommen auch quartäre Emulgatoren in Betracht, wobei solche vom Typ der Esterquats, vorzugsweise methylquaternierte Difettsäuretriethanolaminester-Salze, besonders bevorzugt sind.Furthermore, zwitterionic surfactants can be used as emulsifiers. Zwitterionic surfactants are those surface-active compounds which carry at least one quaternary ammonium group and at least one carboxylate and one sulfonate 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-acylamino-propyl-N, N-dimethylammonium glycinates, for example cocoacylaminopropyldimethylammonium glycinate, and 2-alkyl-3-carboxylmethyl 3-hydroxyethylimidazolines having in each case 8 to 18 carbon atoms in the alkyl or acyl group, and the Kokosacylaminoethyl- hydroxyethylcarboxymethylglycinat. Particularly preferred is the fatty acid amide derivative known under the CTFA name Cocamidopropyl Betaine. Also suitable emulsifiers are ampholytic surfactants. Among the phobic surfactants are surface-active compounds which, apart from a C 8 i 8 alkyl or acyl group in the molecule at least one free amino group and at least one -COOH or -SO / 3 H group and are capable of forming inner salts are. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each having about 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C 12/18 acylsarcosine. In addition to the ampholytic, quaternary emulsifiers are also suitable, with those of the esterquat type, preferably methyl-quaternized difatty acid triethanolamine ester salts, being particularly preferred.
Es ist erfindungsgemäß ganz besonders bevorzugt, wenn die Emulsionen mindestens einen Emulgator enthalten, der ausgewählt wird aus der Gruppe, die gebildet wird aus Alkylmonoglykosiden, Alkyloligoglykosiden, Alkenylmonoglykosiden, Alkenyloligoglykosiden sowie den ethoxylierten Analoga aller Vertreter, wobei die Alkyl- bzw. Alkenylgruppen 6 bis 22 Kohlenstoffatome besitzen. Die unter (4) gelisteten Emulgatoren mit der Formel (I) sind dabei bevorzugt (vide supra).It is very particularly preferred according to the invention if the emulsions comprise at least one emulsifier selected from the group formed by alkyl monoglycosides, alkyl oligoglycosides, alkenyl monoglycosides, alkenyl oligoglycosides and the ethoxylated analogs of all the representatives, the alkyl or alkenyl groups being from 6 to 22 Possess carbon atoms. The emulsifiers of the formula (I) listed under (4) are preferred (vide supra).
Die Anlagerungsprodukte von Ethylenoxid und/oder von Propylenoxid gemäß (1) sind vorzugsweise Fettalkoholethoxylate und folgen besonders bevorzugt der Formel (II),The addition products of ethylene oxide and / or of propylene oxide according to (1) are preferably fatty alcohol ethoxylates and more preferably follow the formula (II)
R1(OCH2CH2)nOH (II)R 1 (OCH 2 CH 2 ) n OH (II)
in der R1 für einen linearen oder verzweigten Alkylrest mit 12 bis 22 Kohlenstoffatomen und n für Zahlen von 5 bis 50 und vorzugsweise 15 bis 35 steht. Typische Beispiele sind Anlagerungsprodukte von 10 bis 30 Mol Ethylenoxid an Laurylalkohol, Isotridecylalkohol, My- ristylalkohol, Palmitylalkohol, Stearylalkohol, Isostearylalkohol, Oleylalkohol, Elaidylalkohol, Li- nolylalkohol, Linolenylalkohol, Elaeostearylalkohol, Arachidylalkohol, Gadolylalkohol oder Behenylalkohol sowie deren technische Mischungen, die z.B. bei der Druckspaltung von natürlichen Fetten und ölen oder bei der Reduktion von Aldehyden aus der Roelen'schen Oxosynthese anfallen. Vorzugsweise werden Anlagerungsprodukte von 20 bis 30 Mol Ethylenoxid an Fettalkohole mit 16 bis 18 Kohlenstoffatomen eingesetzt. Diese sind ganz besonders bevorzugt als Emulgator in den erfindungsgemäßen Emulsionen enthalten.in which R 1 is a linear or branched alkyl radical having 12 to 22 carbon atoms and n is a number from 5 to 50 and preferably 15 to 35. Typical examples are adducts of 10 to 30 moles of ethylene oxide with lauryl alcohol, isotridecyl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, linolyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachidyl alcohol, gadolyl alcohol or behenyl alcohol and their technical mixtures, for example in US Pat the pressure fission of natural fats and oils or in the reduction of aldehydes from Roelen's oxo synthesis incurred. Preferably, adducts of 20 to 30 moles of ethylene oxide with fatty alcohols having 16 to 18 carbon atoms are used. These are very particularly preferably contained as emulsifier in the emulsions according to the invention.
Partialglyceride, die als Emulgator in Betracht kommen, folgen vorzugsweise der Formel (III),Partial glycerides, which are suitable as emulsifier, preferably follow the formula (III),
CH2O(CH2CH2O)x-COR2 ICH 2 O (CH 2 CH 2 O) x -COR 2 I
CH-O(CH2CH2O)yH (III)CH-O (CH 2 CH 2 O) y H (III)
II
CH2O(CH2CH2O)Z-HCH 2 O (CH 2 CH 2 O) Z -H
in der R2CO für einen linearen oder verzweigten Acylrest mit 12 bis 22 Kohlenstoffatomen und x, y und z in Summe für 0 oder für Zahlen von 1 bis 50, vorzugsweise 15 bis 35 steht. Typische Beispiele für im Sinne der Erfindung geeignete Partialglyceride sind Laurinsäuremonoglycerid, Kokosfettsäuremono-glycerid, Palmitinsäuremonoglycerid, Stearinsäuremonoglycerid,in which R 2 CO stands for a linear or branched acyl radical having 12 to 22 carbon atoms and x, y and z in total for 0 or for numbers from 1 to 50, preferably 15 to 35. typical Examples of partial glycerides suitable for the purposes of the invention are lauric acid monoglyceride, coconut fatty acid mono-glyceride, palmitic acid monoglyceride, stearic acid monoglyceride,
Isostearinsäuremonoglycerid, ölsäure-monoglycerid und Talgfettsäuremonoglycerid sowie deren Addukte mit 5 bis 50 und vorzugsweise 20 bis 30 Mol Ethylenoxid. Vorzugsweise werden Monoglyceride bzw. technische Mono/Diglyceridgemische mit überwiegendem Monoglyceridanteil der Formel (III) eingesetzt, in der R2CO für einen linearen Acylrest mit 16 bis 18 Kohlenstoffatomen steht.Isostearic acid monoglyceride, oleic acid monoglyceride and tallow fatty acid monoglyceride and their adducts with 5 to 50 and preferably 20 to 30 moles of ethylene oxide. Preferably, monoglycerides or technical mono / Diglyceridgemische with predominantly Monoglyceridanteil of formula (III) are used, in which R 2 CO is a linear acyl radical having 16 to 18 carbon atoms.
Ganz besonders bevorzugt enthalten die Emulsionen als Emulgatoren mindestens eineWith very particular preference the emulsions contain at least one of emulsifiers
Kombination auscombination of
(M) mindestens einem Fettalkoholethoxylat als Anlagerungsprodukt von 2 bis 30 Mol(M) at least one fatty alcohol ethoxylate as an adduct of 2 to 30 mol
Ethylenoxid und/ oder 0 bis 5 Mol Propylenoxid an lineare Fettalkohole mit 8 bis 22 C-Ethylene oxide and / or 0 to 5 moles of propylene oxide with linear fatty alcohols having 8 to 22 C
Atomen, insbesondere solche der obenstehenden Formel (II), mit (i2) mindestens einem Alkyl- und/oder Alkenyloligoglykosid, insbesondere der obenstehendenAtoms, in particular those of the above formula (II), with (i2) at least one alkyl and / or Alkenyloligoglykosid, in particular the above
Formel (I).Formula (I).
Ganz besonders bevorzugt sind die erfindungsgemäßen Emulsionen frei von Emulgatoren, die als Strukturelement mindestens eine Esterbindung -C(O)-O- enthalten. Dies gilt insbesondere bei einem pH-Wert der Emulsion von pH > 7.Most preferably, the emulsions according to the invention are free of emulsifiers which contain at least one ester bond -C (O) -O- as structural element. This is especially true at a pH of the emulsion of pH> 7.
Besonders bevorzugt bewirken die Emulgatoren bzw. deren Mischungen eine Phaseninversionstemperatur zur Herstellung der erfindungsgemäßen Emulsion von -5°C bis 450C, insbesondere von 1O0C bis 300C. Solche PIT-Emulsionen werden in der Druckschrift DE-A1-102 56 507 beschrieben, auf deren Inhalt ausdrücklich und vollinhaltlich Bezug genommen wird.Particularly preferred are the emulsifiers or mixtures thereof cause a phase inversion temperature of the emulsion according to the invention for the preparation of -5 ° C to 45 0 C, in particular from 1O 0 C to 30 0 C. Such PIT emulsions are in the document DE-A1-102 56 507, the contents of which are expressly and fully incorporated by reference.
Als ölkörper kommt bevorzugt mindestens ein Vertreter aus der Gruppe, bestehend aus Guerbetalkoholen auf Basis von Fettalkoholen mit 6 bis 18 Kohlenstoffatomen, Estern von linearen C6-C2o-Fettsäuren mit linearen C6-C2o-Fett-alkoholen, Estern von verzweigten C6-C13-Carbonsäuren mit linearen C6-C20-Fettalkoholen, Estern von linearen C6-C18-Fettsäuren mit verzweigten Alkoholen, insbesondere mit 2- Ethylhexanol,As the oil body is preferably at least one member selected from the group consisting of Guerbet alcohols based on fatty alcohols having 6 to 18 carbon atoms, esters of linear C 6 -C 2 o fatty acids with linear C 6 -C 2 o-fatty alcohols, esters of branched C6-C13-carboxylic acids with linear C6-C20-fatty alcohols, esters of linear C6-C18-fatty acids with branched alcohols, in particular with 2-ethylhexanol,
Estern von linearen und/oder verzweigten Fettsäuren mit mehrwertigen Alkoholen und/ oder Guerbetalkoholen (wie z.B. Dimerdiol oder Trimertriol), Triglyceriden auf Basis von C6-C10-Fettsäuren, pflanzlichen ölen, verzweigten primären Alkoholen, substituierten Cyclohexanen, Guerbetcarbonaten, Dialkylethern und/oder aliphatischen bzw. naphthenischen Kohlenwasserstoffen (z.B. Paraffinöl) in Frage.Esters of linear and / or branched fatty acids with polyhydric alcohols and / or Guerbet alcohols (such as dimerdiol or trimer triol), triglycerides based on C6-C10 fatty acids, vegetable oils, branched primary alcohols, substituted cyclohexanes, Guerbet carbonates, dialkyl ethers and / or aliphatic or naphthenic hydrocarbons (eg paraffin oil) in question.
Bevorzugte ölkörper sind mindestens ein Vertreter der Gruppe, gebildet aus Guerbetalkoholen auf Basis von Fettalkoholen mit 6 bis 18, vorzugsweise 8 bis 10 Kohlenstoffatomen, pflanzlichen ölen, verzweigten primären Alkoholen, substituierten Cyclohexanen, Guerbetcarbonaten, (C6-bis C22)- Dialkylethern (insbesondere Dioctylether (Cetiol® OE der Fa. Cognis)) und aliphatischen bzw. naphthenischen Kohlenwasserstoffen (wie beispielsweise Paraffinöl).Preferred oil bodies are at least one member of the group formed from Guerbet alcohols based on fatty alcohols having 6 to 18, preferably 8 to 10 carbon atoms, vegetable oils, branched primary alcohols, substituted cyclohexanes, Guerbet carbonates, (C 6 to C 22 ) dialkyl ethers ( especially dioctyl ether (Cetiol OE ® of the company. Cognis)) and aliphatic or naphthenic hydrocarbons (such as paraffin oil).
Besonders bevorzugt sind die erfindungsgemäßen Emulsionen frei von solchen ölkörpern, die als Strukturelement mindestens eine Esterbindung -C(O)-O- enthalten. Dies gilt insbesondere bei einem pH-Wert der Emulsion von pH > 7.The emulsions according to the invention are particularly preferably free from those oil bodies which contain at least one ester bond -C (O) -O- as structural element. This is especially true at a pH of the emulsion of pH> 7.
Die ölkörper sind bevorzugt in einer Menge von 1 bis 50 Gew.-%, besonders bevorzugt von 5 bis 20 Gew.-%, jeweils bezogen auf das Gewicht der Emulsion, enthalten.The oily bodies are preferably present in an amount of from 1 to 50% by weight, more preferably from 5 to 20% by weight, based in each case on the weight of the emulsion.
Bevorzugt werden die in den erfindungsgemäßen Emulsionen enthaltenen anionischen Alkyloligoglykosid bzw. anionischen Alkenyloligoglykosid-Derivate (iii) ausgewählt aus Alkyl- und/oder Alkenyl-Oligoglykosidcarboxylaten, -sulfaten, -phosphaten und/oder -isethionaten, die sich von Alkyl- und/oder Alkenyloligoglykosiden der allgemeinen Formel (IV) ableiten,The anionic alkyl oligoglycoside or anionic alkenyl oligoglycoside derivatives (iii) contained in the emulsions according to the invention are preferably selected from alkyl and / or alkenyl oligoglycoside carboxylates, sulfates, phosphates and / or isethionates derived from alkyl and / or alkenyl oligoglycosides derive the general formula (IV),
R-O-(G)p (IV)R-O- (G) p (IV)
mit der Bedeutungwith the meaning
R C6-22-Alkyl oder Ce-^-Alkenyl,RC 6-22 alkyl or Ce - ^ - alkenyl,
G Glykosideinheit, die sich von einem Zucker mit 5 oder 6 Kohlenstoffatomen ableitet, p Zahl von 1 bis 10.G glycoside unit derived from a sugar with 5 or 6 carbon atoms, p number from 1 to 10.
Der Alkyl-/Alkenylrest R der Formel (IV) leitet sich bevorzugt von primären Alkoholen mit 6 bis 22, vorzugsweise 12 bis 18 Kohlenstoffatomen ab. Typische Beispiele sind Capronalkohol, Caprylalkohol, Caprinalkohol, Laurylalkohol, Myristylalkohol, Cetylalkohol, Stearylalkohol und Behenylakohol sowie technische Fraktionen, die neben den genannten gesättigten Alkoholen auch Anteile an ungesättigten Alkoholen enthalten können und die auf Basis von natürlichen Fetten und ölen, beispielsweise Palmöl, Palmkernöl, Kokosöl oder Rindertalg gewonnen werden. Der Einsatz von technischem Kokosalkohol ist hierbei besonders bevorzugt.The alkyl / alkenyl radical R of the formula (IV) is preferably derived from primary alcohols having 6 to 22, preferably 12 to 18 carbon atoms. Typical examples are caproic alcohol, caprylic alcohol, capric alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol and behenyl alcohol, as well as technical fractions which, in addition to the saturated alcohols mentioned, may also contain portions of unsaturated alcohols and those based on natural fats and oils, for example palm oil, palm kernel oil, coconut oil or beef tallow. The use of technical coconut oil is particularly preferred here.
Neben den genannten Fettalkoholen kann sich der Rest R gemäß Formel (IV) auch von synthetischen primären Alkoholen mit 6 bis 22 Kohlenstoffatomen, insbesondere den sogenannten Oxoalkoholen ableiten, die einen Anteil von 5 bis 40 Gew.-% verzweigter Isomeren aufweisen.In addition to the fatty alcohols mentioned, the radical R according to formula (IV) can also be derived from synthetic primary alcohols having 6 to 22 carbon atoms, in particular the so-called oxo alcohols, which have a proportion of 5 to 40% by weight of branched isomers.
Besonders bevorzugte Alkylreste R der Formel (IV) sind solche mit 8/10, 12/14, 8 bis 16, 12 bis 16 oder 16 bis 18 C-Atomen. Mischungen der Alkylreste ergeben sich bei einer Herstellung ausgehend von natürlichen Fetten und ölen oder Mineralölen.Particularly preferred alkyl radicals R of the formula (IV) are those having 8/10, 12/14, 8 to 16, 12 to 16 or 16 to 18 C atoms. Mixtures of the alkyl radicals result in a preparation starting from natural fats and oils or mineral oils.
Erfindungsgemäß werden bevorzugt Alkyloligoglykosidcarboxylate, -sulfate, -phosphate und/oder - isethionate, besonders bevorzugt Alkyloligoglykosidcarboxylate oder -phosphate, insbesondere Alkylglykosidcarboxylate eingesetzt.Alkyl oligoglycoside carboxylates, sulfates, phosphates and / or isethionates, particularly preferably alkyl oligoglycoside carboxylates or phosphates, in particular alkyl glycoside carboxylates, are preferably used according to the invention.
In den Alkyl- und/oder Alkenyl-Oligoglykosiden ist vorzugsweise in mindestens einem der Reste G der Formel (IV) mindestens eine Hydroxylgruppe durch -O-C^^-Alkenyl-COOM, -O(CH2-)nCOOM, -OSO3M1 -OP(O)(OM)2 oder -0-CH2-CH2-SO3M mit M = H, Alkalimetall oder NH4 ersetzt.In the alkyl and / or alkenyl oligoglycosides at least one hydroxyl group is preferably in at least one of the radicals G of the formula (IV) by -OC ^^ - alkenyl-COOM, -O (CH 2 -) n COOM, -OSO 3 M 1 -OP (O) (OM) 2 or -O-CH 2 -CH 2 -SO 3 M with M = H, alkali metal or NH 4 replaced.
Dabei wird besonders bevorzugt ein Alkyloligoglykosid-Carboxylat eingesetzt, in dem mindestens eine Hydroxylgruppe des Rests G in Formel (IV) durch -O-C2-i2-Alkenylen-COOM oder -0(CH2- JnCOOM mit M = H, Na oder K und n = 1 bis 3 ersetzt ist. Besonders bevorzugt ist der Rest -O- CH2-COOM, insbesondere mit M = Na.In this case, particularly preferably an alkyl oligoglycoside carboxylate is applied, in which at least one hydroxyl group of the residue G in formula (IV) -O-C 2 i 2 -alkenylene-COOM or -0 (CH 2 - J n COOM with M = H, Na or K and n = 1 to 3. Particularly preferably, the radical is -O-CH 2 -COOM, in particular with M = Na.
Weitere Hydroxylgruppen des Glukosids können beispielsweise auch verethert sein.Further hydroxyl groups of the glucoside can also be etherified, for example.
Besonders bevorzugt wird ein Alkyloligoglykosidcarboxylat eingesetzt, in dem der Alkylrest R der Formel (IV) ein Laurylrest ist. Speziell bevorzugt ist ein Laurylglucosidcarboxylat, wie es als Plantapon® LGC von Cognis Deutschland erhältlich ist.Particular preference is given to using an alkyl oligoglycoside carboxylate in which the alkyl radical R of the formula (IV) is a lauryl radical. A Laurylglucosidcarboxylat as available as ® Plantapon LGC from Cognis Germany being especially preferred.
Die Indexzahl p in der allgemeinen Formel (IV) gibt den Oligo- bzw. Polymerisierungsgrad, d.h. die Verteilung von Mono- und Oligoglykosiden an und steht für eine Zahl zwischen 1 und 10. Während p in einer gegebenen Verbindung stets ganzzahlig sein muss und hier vor allem die Werte p = 1 bis 6 annehmen kann, ist der Wert p für ein bestimmtes Alkylglykosid eine analytische ermittelte rechnerische Größe, die meistens eine gebrochene Zahl darstellt. Vorzugsweise werden Alkylglykoside mit einem mittleren Oligomerisierungsgrad p von 1 ,1 bis 3,0 verwendet. Besonders bevorzugt sind solche Alkylglykoside, deren Oligomerisierungsgrad kleiner als 1 ,5 ist und insbesondere zwischen 1 ,1 , und 1 ,4 liegt.The index number p in the general formula (IV) indicates the degree of oligo- or polymerization, ie the distribution of monoglycerides and oligoglycosides, and stands for a number between 1 and 10. While p in a given compound must always be integer and here before For all given values p = 1 to 6, the value p for a given alkyl glycoside is an analytic calculated arithmetic quantity, which is usually a fractional number. Preferably, alkyl glycosides having an average degree of oligomerization p of 1.1 to 3.0 are used. Especially Preferred are those alkyl glycosides whose degree of oligomerization is less than 1.5, and in particular between 1.1 and 1.4.
In den Alkylglykosiden der allgemeinen Formel (IV) leiten sich die Glykosid-Einheiten G vorzugsweise von Aldosen bzw. Ketosen ab.In the alkyl glycosides of the general formula (IV), the glycoside units G are preferably derived from aldoses or ketoses.
Vorzugsweise werden wegen der besseren Reaktionsfähigkeit als Rest G der Formel (IV) die reduzierend wirkenden Saccharide, die Aldosen, verwendet. Unter den Aldosen kommt wegen ihrer leichten Zugänglichkeit und technischen Verfügbarkeit insbesondere die Glucose in Betracht. Die als Ausgangsstoffe besonders bevorzugt eingesetzten Alkylgykoside sind daher die Alkylglucoside.Preferably, because of the better reactivity than the radical G of formula (IV), the reducing saccharides, the aldoses used. Among the aldoses, glucose is particularly suitable for their easy accessibility and technical availability. The alkylglycosides which are particularly preferably used as starting materials are therefore the alkylglucosides.
Verfahren zur Herstellung der entsprechenden Alkyl- bzw. Alkenyloligoglykoside als Ausgangsstoff sind beispielsweise in den amerikanischen Patentschriften US 3,547,828 und US 3,839,318 sowie der deutschen Patentanmeldung DE-A-37 23 826 beschrieben. Für Alkylpolyglykoside an sich kann beispielsweise auf die DE-A-100 27 975, DE-A-101 38 094 und DE-A-100 31 014 verwiesen werden. Für eine weitere Diskussion der Alkyloligo-/Alkylpolyglykoside (APG) kann auf WO 03/013450 verwiesen werden.Processes for preparing the corresponding alkyl or alkenyl oligoglycosides as starting material are described, for example, in US Pat. Nos. 3,547,828 and 3,839,318 and German Patent Application DE-A-37 23 826. For alkyl polyglycosides per se, reference may be made, for example, to DE-A-100 27 975, DE-A-101 38 094 and DE-A-100 31 014. For a further discussion of the alkyloligo- / alkyl polyglycosides (APG), reference may be made to WO 03/013450.
Die Herstellung der erfindungsgemäß eingesetzten Alkyl- oder Alkenyl-Oligoglykosidcarboxylate, - Phosphate, -sulfate oder -isethionate kann nach bekannten Verfahren erfolgen. Die Herstellung der Carboxylate erfolgt beispielsweise durch Umsetzung der Alkyloligoglykoside mit Salzen von Chlorcarbonsäuren in Gegenwart von Basen. Beispielsweise kann mit 2-Chloressigsäure- Natriumsalz in Gegenwart von NaOH umgesetzt werden. Bei der Umsetzung können sowohl die Hydroxylgruppen im Ring wie auch dieThe alkyl or alkenyl oligoglycoside carboxylates, phosphates, sulfates or isethionates used according to the invention can be prepared by known processes. The carboxylates are prepared, for example, by reacting the alkyloligoglycosides with salts of chlorocarboxylic acids in the presence of bases. For example, it is possible to react with 2-chloroacetic acid sodium salt in the presence of NaOH. In the reaction, both the hydroxyl groups in the ring as well as the
-CH2-OH-Gruppe umgesetzt werden. Der Umsetzungsgrad ist u.a. abhängig von der Stöchiometrie der Einsatzprodukte. Vorzugsweise werden die Alkyloligoglykoside zumindest an der -CH2-OH-Gruppe umgesetzt, wobei optional ein Mittel eine oder mehreren der am Ring befindlichen Hydroxylgruppen umgesetzt werden können.-CH 2 -OH group are reacted. The degree of conversion depends inter alia on the stoichiometry of the feedstock. Preferably, the alkyl oligoglycosides are reacted at least on the -CH 2 -OH group, optionally with an agent capable of reacting one or more of the hydroxyl groups on the ring.
Die Herstellung der Isethionate ist beispielsweise in der WO 94/26857 beschrieben. Dort ist ferner angegeben, dass die Produkte zur Haar- und Körperpflege eingesetzt werden können. Es werden insbesondere wässrige Detergenzgemische beschrieben, die Alkyloligoglykosidisethionate und beispielsweise weitere anionische Tenside enthalten.The preparation of the isethionates is described, for example, in WO 94/26857. It also states that the products can be used for hair and body care. In particular, aqueous detergent mixtures are described which contain alkyloligoglycoside isethionates and, for example, further anionic surfactants.
Die Herstellung der Sulfate ist beispielsweise in der WO 93/10208 und WO 91/15192 beschrieben. In letzterer Schrift sind auch Gemische der APG-Sulfate mit u.a. Alkylsulfaten oder Alkylethersulfaten sowie weiteren Inhaltsstoffen beschrieben. Es ist angegeben, dass die Tensidmischungen in Produkten eingesetzt werden können, die zum Waschen, Färben, Wellen oder zur Spülung von Haaren dienen.The preparation of the sulfates is described, for example, in WO 93/10208 and WO 91/15192. In the latter document are also mixtures of APG sulfates with, inter alia, alkyl sulfates or Alkyl ether sulfates and other ingredients described. It is stated that the surfactant mixtures can be used in products that are used for washing, dyeing, rippling or rinsing hair.
Die Herstellung der Sulfate kann zudem wie in EP-A-O 186 242 beschrieben erfolgen. Beispielsweise kann das entsprechende Alkylglykosid mit gasförmigem Schwefeltrioxid oder mit Schwefelsäure, gefolgt von Neutralisierung, umgesetzt werden.The preparation of the sulfates can also be carried out as described in EP-A-0 186 242. For example, the corresponding alkyl glycoside can be reacted with gaseous sulfur trioxide or with sulfuric acid followed by neutralization.
Weiterhin kann auf die DE-A-195 00 780 hingewiesen werden, in der kosmetische und pharmazeutische Zubereitungen beschrieben sind, die Alkyloligoglykosidsulfate enthalten.Furthermore, reference may be made to DE-A-195 00 780, in which cosmetic and pharmaceutical preparations containing alkyloligoglycoside sulfates are described.
In der DE-A-195 01 185 sind Detergenzgemische aus Alkyloligoglykosidsulfaten und Alkyletherphosphaten beschrieben, die beispielsweise in Haarspülungen, Haarfärbemitteln oder Haarwellmitteln eingesetzt werden können.DE-A-195 01 185 describes detergent mixtures of alkyl oligoglycoside sulfates and alkyl ether phosphates which can be used, for example, in hair rinses, hair dyes or hair waving agents.
Diese erfindungsgemäßen Emulsionen enthalten mindestens ein Alkyl- und/oder Alkenyl- Oligoglykosidcarboxylat, -sulfat, -phosphat und/oder -isethionat, vorzugsweise in einer Menge von 0,2 bis 15 Gew.-%, besonders bevorzugt 0,5 bis 10 Gew.-%.These emulsions according to the invention comprise at least one alkyl and / or alkenyl oligoglycoside carboxylate, sulfate, phosphate and / or isethionate, preferably in an amount of 0.2 to 15% by weight, particularly preferably 0.5 to 10% by weight. -%.
Es ist erfindungsgemäß bevorzugt, wenn das Mittel neben der erfindungsgemäßen Komponente (iii) keine weiteren Aniontenside enthält.It is inventively preferred if the agent in addition to the inventive component (iii) contains no further anionic surfactants.
Die Herstellung einer Emulsion nach der Phaseninversionsmethode ist dem Fachmann per se bekannt. Eine bevorzugte Herstellmethode besteht darin, sogenannte PIT-Emulsionen herzustellen, in dem man die ölkörper und die Emulgatoren auf die Herstelltemperatur aufheizt und mit der ebenfalls auf Herstelltemperatur aufgeheizten benötigten Menge Wasser mischt. Die Herstelltemperatur muß oberhalb der Phaseninversionstemperatur liegen. Zur Definition der Phaseninversionstemperatur siehe A. Domsch, Die kosmetischen Präparate, 4. Auflage, Band III, Verlag für ehem. Industrie, H. Ziolkowsky, Augsburg 1994, Seite 109. Die Phaseninversion findet innerhalb eines Temperaturbereichs stattfindet.The preparation of an emulsion by the phase inversion method is known per se to the person skilled in the art. A preferred method of preparation is to produce so-called PIT emulsions in which the oil bodies and the emulsifiers are heated to the production temperature and mixed with the amount of water which is likewise heated to the production temperature. The production temperature must be above the phase inversion temperature. For the definition of the phase inversion temperature, see A. Domsch, The Cosmetic Preparations, 4th Edition, Volume III, Verlag für ehem. Industrie, H. Ziolkowsky, Augsburg 1994, page 109. The phase inversion takes place within a temperature range.
Den Phaseninversionstemperaturbereich sollte man daher zunächst anhand eines Probeansatzes ermitteln. Dabei werden alle Komponenten der Emulsion, einschließlich des Wassers erhitzt, wobei man mit Hilfe eines Leitfähigkeitsmeßgerätes den Temperaturbereich bestimmt, bei dem - infolge Phasenumkehr - die Leitfähigkeit stark abnimmt. Die Bestimmung des Temperaturbereichs der Phaseninversion wird gemäß DE-A1-102 56 507 [0011] bis [0013] durchgeführt. Es ist erfindungsgemäß bevorzugt die anionischen Tenside der Komponente (iii) der erfindungsgemäßen Emulsion in die auf die Herstelltemperatur aufgeheizten ölkörper (i) zu geben. Dies kann gemeinsam mit, vor oder nach der Zugabe der Emulgatorkomponente (ii), bevorzugt nach der Zugabe der Emulgatorkomponente (ii) erfolgen. Anschließend wird das Gemisch aller Komponenten (i) bis (iv) gemeinsam auf die Umgebungstemperatur gebracht.The phase inversion temperature range should therefore first be determined on the basis of a test application. All components of the emulsion, including the water, are heated, the temperature range being determined by means of a conductivity meter, at which the conductivity decreases sharply as a result of phase inversion. The determination of the temperature range of the phase inversion is carried out according to DE-A1-102 56 507 [0011] to [0013]. It is preferred according to the invention to add the anionic surfactants of component (iii) of the emulsion according to the invention to the oil body (i) heated to the production temperature. This can be done together with, before or after the addition of the emulsifier component (ii), preferably after the addition of the emulsifier component (ii). Subsequently, the mixture of all components (i) to (iv) is brought together to the ambient temperature.
Die erfindungsgemäßen PIT-Emulsionen besitzen bevorzugt eine Tröpfchengröße von 10 nm bis 500 nm, insbesondere von 10 nm bis 200 nm.The PIT emulsions according to the invention preferably have a droplet size of from 10 nm to 500 nm, in particular from 10 nm to 200 nm.
Der pH-Wert der erfindungsgemäßen Emulsion beträgt bevorzugt pH 5 bis pH 12, besonders bevorzugt liegt der pH-Wert zwischen pH 7 und pH 12, insbesondere in einem Bereich von pH 7,5 bis pH 10.The pH of the emulsion according to the invention is preferably from pH 5 to pH 12, more preferably the pH is between pH 7 and pH 12, in particular in a range from pH 7.5 to pH 10.
Die erfindungsgemäßen waschaktiven PIT-Emulsionen können für eine Vielzahl von Anwendungszwecken, vorzugsweise aber für die Herstellung von Haut- und Haarpflegemittel eingesetzt werden, wie beispielsweise Haarshampoos, Haarfärbemittel, Haarlotionen, Schaumbäder, Cremes, Lotionen oder Salben. Zu diesem Zweck enthalten die Emulsionen bevorzugt zusätzlich mindestens eine Aktivsubstanz als Wirkstoff. Dies können unter anderem UV-Filter, farbgebende Komponenten sowie Pflegestoffe sein. Zur Zubereitung der Emulsionen mit mindestens einer zusätzlichen Aktivsubstanz mischt man bevorzugt der fertigen PIT- Emulsionsbasis den Wirkstoff, bevorzugt in Form einer wässrigen Lösung, zu. Während der Zugabe der Aktivsubstanzen besitzt die erfindungsgemäße PIT-Emulsionsbasis bevorzugt eine Temperatur unterhalb der Phaseninversionstemperatur, besonders bevorzugt von 10 bis 350C, ganz besonders bevorzugt Raumtemperatur.The wash-active PIT emulsions of the invention can be used for a variety of applications, but preferably for the production of skin and hair care products, such as hair shampoos, hair dyes, hair lotions, bubble baths, creams, lotions or ointments. For this purpose, the emulsions preferably additionally contain at least one active substance as the active ingredient. These may include UV filters, coloring components and care substances. To prepare the emulsions with at least one additional active substance, the active ingredient is preferably added to the finished PIT emulsion base, preferably in the form of an aqueous solution. During the addition of the active substances, the PIT emulsion base according to the invention preferably has a temperature below the phase inversion temperature, particularly preferably from 10 to 35 ° C., very particularly preferably room temperature.
Die erfindungsgemäßen Emulsionen enthalten in einer bevorzugten Ausführungsform als Färbemittel keratinhaltiger Fasern, insbesondere menschlicher Haare, als zusätzliche Aktivsubstanz mindestens eine farbgebende Komponente.In a preferred embodiment, the emulsions according to the invention comprise as colorants keratin-containing fibers, in particular human hair, as additional active substance at least one coloring component.
Unter keratinhaltigen Fasern sind Wolle, Pelze, Federn und insbesondere menschliche Haare zu verstehen. Die erfindungsgemäßen Färbemittel können prinzipiell aber auch zum Färben anderer Naturfasern, wie z. B. Baumwolle, Jute, Sisal, Leinen oder Seide, modifizierter Naturfasern, wie z. B. Regeneratcellulose, Nitro-, Alkyl- oder Hydroxyalkyl- oder Acetylcellulose und synthetischer Fasern, wie z. B. Polyamid-, Polyacrylnitril-, Polyurethan- und Polyesterfasern verwendet werden.Keratin fibers are wool, furs, feathers and especially human hair to understand. The colorants of the invention can in principle but also for dyeing other natural fibers such. As cotton, jute, sisal, linen or silk, modified natural fibers such. As regenerated cellulose, nitro, alkyl or hydroxyalkyl or acetyl cellulose and synthetic fibers, such as. As polyamide, polyacrylonitrile, polyurethane and polyester fibers are used.
Als farbgebende Komponente enthalten die erfindungsgemäßen Emulsionen bevorzugt (a) mindestens ein Oxidationsfarbstoffvorprodukt vom Typ der Entwicklerkomponenten und gegebenenfalls zusatzlich mindestens eine Kupplerkomponente und/oderAs coloring component, the emulsions according to the invention preferably contain (A) at least one oxidation dye precursor of the developer component type and optionally additionally at least one coupler component and / or
(b) mindestens ein Oxofarbstoffvorprodukt und/oder(B) at least one Oxofarbstoffvorprodukt and / or
(c) mindestens einen direktziehenden Farbstoff und/oder(c) at least one substantive dye and / or
(d) mindestens eine Vorstufe naturanaloger Farbstoffe.(d) at least one precursor of naturally-colored dyes.
Als Entwicklerkomponenten werden üblicherweise primäre aromatische Amine mit einer weiteren, in para- oder ortho-Position befindlichen, freien oder substituierten Hydroxy- oder Aminogruppe, Diaminopyridinderivate, heterozyklische Hydrazone, 4-Aminopyrazolderivate sowie 2,4,5,6- Tetraaminopyrimidin und dessen Derivate eingesetzt.As developer components are usually primary aromatic amines with another, in the para or ortho position, free or substituted hydroxy or amino group, diaminopyridine, heterocyclic hydrazones, 4-aminopyrazole derivatives and 2,4,5,6-tetraaminopyrimidine and its derivatives used ,
Es kann erfindungsgemäß bevorzugt sein, als Entwicklerkomponente ein p-Phenylendiaminderivat oder eines seiner physiologisch verträglichen Salze einzusetzen. Besonders bevorzugt sind p- Phenylendiaminderivate der Formel (Ent1)It may be preferred according to the invention to use as the developer component a p-phenylenediamine derivative or one of its physiologically acceptable salts. Particular preference is given to p-phenylenediamine derivatives of the formula (Ent1)
Figure imgf000013_0001
wobei
Figure imgf000013_0001
in which
G1 steht für ein Wasserstoffatom, einen Ci- bis C4-Alkylrest, einen C1- bis C4- Monohydroxyalkylrest, einen C2- bis C4-Polyhydroxyalkylrest, einen (C1- bis C4^AIkOXy-(C1- bis C4)-alkylrest, einen 4'-Aminophenylrest oder einen C1- bis C4-Alkylrest, der mit einer stickstoffhaltigen Gruppe, einem Phenyl- oder einem 4'-Aminophenylrest substituiert ist; G2 steht für ein Wasserstoffatom, einen C1- bis C4-Alkylrest, einen C1- bis C4- Monohydroxyalkylrest, einen C2- bis C4-Polyhydroxyalkylrest, einen (C1- bis C4)-Alkoxy-(d- bis C4)-alkylrest oder einen C1- bis C4-Alkylrest, der mit einer stickstoffhaltigen Gruppe substituiert ist;G 1 represents a hydrogen atom, a Ci to C 4 alkyl, C 1 - to C 4 - monohydroxyalkyl radical, a C 2 - to C 4 polyhydroxyalkyl radical, a (C 1 - to C 4 ^ AIkOXy- (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 is a hydrogen atom, a alkyl alkoxy (d- to C 4) C 1 - to C 4 alkyl, C 1 - to C 4 - monohydroxyalkyl radical, a C 2 - - to C 4 polyhydroxyalkyl radical, a (C 4 to C 1) or a C 1 to C 4 alkyl radical substituted with a nitrogen-containing group;
G3 steht für ein Wasserstoffatom, ein Halogenatom, wie ein Chlor-, Brom-, lod- oder Fluoratom, einen C1- bis C4-Alkylrest, einen C1- bis C4-Monohydroxyalkylrest, einen C2- bis C4-Polyhydroxyalkylrest, einen C1- bis C4-Hydroxyalkoxyrest, einen C1- bis C4- Acetylaminoalkoxyrest, einen C1- bis C4- Mesylaminoalkoxyrest oder einen C1- bis C4- Carbamoylaminoalkoxyrest; G4 steht für ein Wasserstoffatom, ein Halogenatom oder einen C1- bis C4-Alkylrest oder wenn G3 und G4 in ortho-Stellung zueinander stehen, können sie gemeinsam eine verbrückende α,ω-Alkylendioxogruppe, wie beispielsweise eine Ethylendioxygruppe bilden.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; G 4 represents a hydrogen atom, a halogen atom or a C 1 - to C 4 -alkyl radical or when G 3 and G 4 are ortho to each other, they may together form a bridging α, ω-alkylenedioxy group, such as, for example, an ethylenedioxy group.
Beispiele für die als Substituenten in den erfindungsgemäßen Verbindungen genannten C1- bis C4- Alkylreste sind die Gruppen Methyl, Ethyl, Propyl, Isopropyl und Butyl. Ethyl und Methyl sind bevorzugte Alkylreste. Erfindungsgemäß bevorzugte C1- bis C4-Al koxyreste sind beispielsweise eine Methoxy- oder eine Ethoxygruppe. Weiterhin können als bevorzugte Beispiele für eine C1- bis C4-Hydroxyalkylgruppe eine Hydroxymethyl-, eine 2-Hydroxyethyl-, eine 3-Hydroxypropyl- oder eine 4-Hydroxybutylgruppe genannt werden. Eine 2-Hydroxyethylgruppe ist besonders bevorzugt. Eine besonders bevorzugte C2- bis C4-Polyhydroxyalkylgruppe ist die 1 ,2-Dihydroxyethylgruppe. Beispiele für Halogenatome sind erfindungsgemäß F-, Cl- oder Br-Atome, Cl-Atome sind ganz besonders bevorzugt. Die weiteren verwendeten Begriffe leiten sich erfindungsgemäß von den hier gegebenen Definitionen ab. Beispiele für stickstoffhaltige Gruppen der Formel (Ent1) sind insbesondere die Aminogruppen, C1- bis C4-Monoalkylaminogruppen, C1- bis C4- Dialkylaminogruppen, C1- bis C4-Trialkylammoniumgruppen, C1- bis C4- Monohydroxyalkylaminogruppen, Imidazolinium und Ammonium.Examples of the C 1 - to C 4 -alkyl radicals mentioned as substituents in the compounds according to the invention are the groups methyl, ethyl, propyl, isopropyl and butyl. Ethyl and methyl are preferred alkyl radicals. C 1 -C 4 -alkoxy radicals which are preferred according to the invention are, for example, a methoxy or an ethoxy group. Furthermore, as preferred examples of a C 1 - to C 4 -hydroxyalkyl group, a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group may be mentioned. A 2-hydroxyethyl group is particularly preferred. A particularly preferred C 2 to C 4 polyhydroxyalkyl group is the 1, 2-dihydroxyethyl group. Examples of halogen atoms 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. Examples of nitrogen-containing groups of the formula (Ent1) 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.
Besonders bevorzugte p-Phenylendiamine der Formel (Ent1) sind ausgewählt aus p- Phenylendiamin, p-Toluylendiamin, 2-Chlor-p-phenylendiamin, 2,3-Dimethyl-p-phenylendiamin, 2,6-Dimethyl-p-phenylendiamin, 2,6-Diethyl-p-phenylendiamin, 2,5-Dimethyl-p-phenylendiamin, N,N-Dimethyl-p-phenylendiamin, N,N-Diethyl-p-phenylendiamin, N,N-Dipropyl-p-phenylendiamin, 4-Amino-3-methyl-(N,N-diethyl)-anilin, N,N-Bis-(ß-hydroxyethyl)-p-phenylendiamin, 4-N,N-Bis-(ß- hydroxyethyl)amino-2-methylanilin, 4-N,N-Bis-(ß-hydroxyethyl)amino-2-chloranilin, 2-(ß-Particularly preferred p-phenylenediamines of the formula (Ent1) are selected from p-phenylenediamine, p-toluenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2 , 6-diethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, N, N-dipropyl-p-phenylenediamine, 4 -Amino-3-methyl- (N, N-diethyl) -aniline, N, N-bis- (β-hydroxyethyl) -p-phenylenediamine, 4-N, N-bis- (β-hydroxyethyl) amino-2- methylaniline, 4-N, N-bis- (β-hydroxyethyl) amino-2-chloroaniline, 2- (β-
Hydroxyethyl)-p-phenylendiamin, 2-(α,ß-Dihydroxyethyl)-p-phenylendiamin, 2-Fluor-p- phenylendiamin, 2-lsopropyl-p-phenylendiamin, N-(ß-Hydroxypropyl)-p-phenylendiamin, 2- Hydroxymethyl-p-phenylendiamin, N,N-Dimethyl-3-methyl-p-phenylendiamin, N,N-(Ethyl,ß- hydroxyethyl)-p-phenylendiamin, N-(ß,γ-Dihydroxypropyl)-p-phenylendiamin, N-(4'-Aminophenyl)-p- phenylendiamin, N-Phenyl-p-phenylendiamin, 2-(ß-Hydroxyethyloxy)-p-phenylendiamin, 2-(ß- Acetylaminoethyloxy)-p-phenylendiamin, N-(ß-Methoxyethyl)-p-phenylendiamin und 5,8- Diaminobenzo-1 ,4-dioxan sowie ihren physiologisch verträglichen Salzen.Hydroxyethyl) -p-phenylenediamine, 2- (α, β-dihydroxyethyl) -p-phenylenediamine, 2-fluoro-p-phenylenediamine, 2-isopropyl-p-phenylenediamine, N- (β-hydroxypropyl) -p-phenylenediamine, 2 Hydroxymethyl-p-phenylenediamine, N, N-dimethyl-3-methyl-p-phenylenediamine, N, N- (ethyl, β-hydroxyethyl) -p-phenylenediamine, N- (β, γ-dihydroxypropyl) -p-phenylenediamine , N- (4'-aminophenyl) -p-phenylenediamine, N-phenyl-p-phenylenediamine, 2- (β-hydroxyethyloxy) -p-phenylenediamine, 2- (β-acetylaminoethyloxy) -p-phenylenediamine, N- (β -Methoxyethyl) -p-phenylenediamine and 5,8-diaminobenzo-1, 4-dioxane and their physiologically acceptable salts.
Erfindungsgemäß ganz besonders bevorzugte p-Phenylendiaminderivate der Formel (Ent1) sind p-Phenylendiamin, p-Toluylendiamin, 2-(ß-Hydroxyethyl)-p-phenylendiamin, 2-(α,ß- Dihydroxyethyl)-p-phenylendiamin und N,N-Bis-(ß-hydroxyethyl)-p-phenylendiamin. Es kann erfindungsgemäß weiterhin bevorzugt sein, als Entwicklerkomponente Verbindungen einzusetzen, die mindestens zwei aromatische Kerne enthalten, die mit Amino- und/oder Hydroxylgruppen substituiert sind.Very particular preferred p-phenylenediamine derivatives of the formula (Ent1) according to the invention are p-phenylenediamine, p-toluenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (α, β-dihydroxyethyl) -p-phenylenediamine and N, N bis (.beta.-hydroxyethyl) -p-phenylenediamine. It may further be preferred according to the invention to use as developer component compounds which contain at least two aromatic nuclei which are substituted by amino and / or hydroxyl groups.
Unter den zweikernigen Entwicklerkomponenten, die in den Mitteln gemäß der Erfindung verwendet werden können, kann man insbesondere die Verbindungen nennen, die der folgenden Formel (Ent2) entsprechen, sowie ihre physiologisch verträglichen Salze:Among the binuclear developer components that can be used in the compositions according to the invention, mention may be made in particular of the compounds which correspond to the following formula (Ent2) and their physiologically tolerated salts:
Figure imgf000015_0001
wobei:
Figure imgf000015_0001
in which:
Z1 und Z2 stehen unabhängig voneinander für einen Hydroxyl- oder NH2-ReSt, der gegebenenfalls durch einen C1- bis C4-Alkylrest, durch einen C1- bis C4-Hydroxyalkylrest und/oder durch eine Verbrückung Y substituiert ist oder der gegebenenfalls Teil eines verbrückenden Ringsystems ist, die Verbrückung Y steht für eine Alkylengruppe mit 1 bis 14 Kohlenstoffatomen, wie beispielsweise eine lineare oder verzweigte Alkylenkette oder einen Alkylenring, die von einer oder mehreren stickstoffhaltigen Gruppen und/oder einem oder mehreren Heteroatomen wie Sauerstoff-, Schwefel- oder Stickstoffatomen unterbrochen oder beendet sein kann und eventuell durch einen oder mehrere Hydroxyl- oder C1- bis C8-Alkoxyreste substituiert sein kann, oder eine direkte Bindung,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. or which is optionally part of a bridging ring system, the bridge Y is an alkylene group having 1 to 14 carbon atoms, such as a linear or branched alkylene chain or an alkylene ring, which is one or more nitrogen-containing groups and / or one or more heteroatoms such as oxygen , Sulfur or nitrogen atoms may be interrupted or terminated and may possibly be substituted by one or more hydroxyl or C 1 - to C 8 -alkoxy radicals, or a direct bond,
G5 und G6 stehen unabhängig voneinander für ein Wasserstoff- oder Halogenatom, einen C1- bis C4-Alkylrest, einen C1- bis C4-Monohydroxyalkylrest, einen C2- bis C4- Polyhydroxyalkylrest, einen C1- bis C4-Aminoalkylrest oder eine direkte Verbindung zur Verbrückung Y,G 5 and G 6 independently of one another represent a hydrogen or halogen atom, a C 1 - to C 4 -alkyl radical, a C 1 - to C 4 -monohydroxyalkyl radical, a C 2 - to C 4 -hydroxyalkyl radical, a C 1 - to C 4 -aminoalkyl radical or a direct compound for bridging Y,
G7, G8, G9, G10, G11 und G12 stehen unabhängig voneinander für ein Wasserstoffatom, eine direkte Bindung zur Verbrückung Y oder einen C1- bis C4-Alkylrest, mit den Maßgaben, dass die Verbindungen der Formel (Ent2) nur eine Verbrückung Y pro Molekül enthalten und die Verbindungen der Formel (Ent2) mindestens eine Aminogruppe enthalten, die mindestens ein Wasserstoffatom trägt. Die in Formel (Ent2) verwendeten Substituenten sind erfindungsgemäß analog zu den obigen Ausführungen definiert.G 7 , G 8 , G 9 , G 10 , G 11 and G 12 independently represent a hydrogen atom, a direct bond to the bridge Y or a C 1 - to C 4 -alkyl radical, with the provisos that the compounds of the formula (Ent2) contain only one bridge Y per molecule and the compounds of the formula (Ent2) contain at least one amino group which carries at least one hydrogen atom. The substituents used in formula (Ent2) are inventively defined analogous to the above statements.
Bevorzugte zweikernige Entwicklerkomponenten der Formel (Ent2) sind insbesondere: N,N'-Bis- (ß-hydroxyethyl)-N,N'-bis-(4'-aminophenyl)-1 ,3-diamino-propan-2-ol, N,N'-Bis-(ß-hydroxyethyl)- N,N'-bis-(4'-aminophenyl)-ethylendiamin, N,N'-Bis-(4-aminophenyl)-tetramethylendiamin, N,N'-Bis- (ß-hydroxyethyl)-N,N'-bis-(4-aminophenyl)-tetramethylendiamin, N,N'-Bis-(4-methyl-aminophenyl)- tetramethylendiamin, N,N'-Diethyl-N,N'-bis-(4'-amino-3Vnethylphenyl)-ethylendiamin, Bis-(2- hydroxy-5-aminophenyl)-methan, 1 ,3-Bis-(2,5-diaminophenoxy)-propan-2-ol, N,N'-Bis-(4'- aminophenyl)-1 ,4-diazacycloheptan, N,N'-Bis-(2-hydroxy-5-aminobenzyl)-piperazin, N-(4'- Aminophenyl)-p-phenylendiamin und 1 ,10-Bis-(2',5'-diaminophenyl)-1 ,4,7,10-tetraoxadecan und ihre physiologisch vertraglichen Salze.Preferred binuclear developer components of the formula (Ent2) are in particular: N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diamino-propan-2-ol, N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) ethylenediamine, N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis - (.beta.-hydroxyethyl) -N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis (4-methylaminophenyl) tetramethylenediamine, N, N'-diethyl-N, N ' bis- (4'-amino-3-dimethylphenyl) ethylenediamine, bis (2-hydroxy-5-aminophenyl) -methane, 1, 3-bis- (2,5-diaminophenoxy) -propan-2-ol, N, N'-bis (4'-aminophenyl) -1, 4-diazacycloheptane, N, N'-bis (2-hydroxy-5-aminobenzyl) piperazine, N- (4'-aminophenyl) -p-phenylenediamine and 1, 10-bis- (2 ', 5'-diaminophenyl) -1, 4,7,10-tetraoxadecane and their physiologically acceptable salts.
Ganz besonders bevorzugte zweikernige Entwicklerkomponenten der Formel (Ent2) sind N,N'-Bis- (ß-hydroxyethyl)-N,N'-bis-(4'-aminophenyl)-1 ,3-diamino-propan-2-ol, Bis-(2-hydroxy-5- aminophenyl)-methan, 1 ,3-Bis-(2,5-diaminophenoxy)-propan-2-ol, N,N'-Bis-(4'-aminophenyl)-1 ,4- diazacycloheptan und 1 ,10-Bis-(2',5'-diaminophenyl)-1,4,7,10-tetraoxadecan oder eines ihrer physiologisch verträglichen Salze.Very particularly preferred binuclear developer components of the formula (Ent2) are N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diamino-propan-2-ol, Bis (2-hydroxy-5-aminophenyl) methane, 1, 3-bis (2,5-diaminophenoxy) -propan-2-ol, N, N'-bis (4'-aminophenyl) -1, 4-diazacycloheptane and 1, 10-bis (2 ', 5'-diaminophenyl) -1,4,7,10-tetraoxadecan or one of its physiologically acceptable salts.
Weiterhin kann es erfindungsgemäß bevorzugt sein, als Entwicklerkomponente ein p- Aminophenolderivat oder eines seiner physiologisch verträglichen Salze einzusetzen. Besonders bevorzugt sind p-Aminophenolderivate der Formel (Ent3)Furthermore, it may be preferred according to the invention to use as the developer component a p-aminophenol derivative or one of its physiologically tolerable salts. Particular preference is given to p-aminophenol derivatives of the formula (Ent3)
Figure imgf000016_0001
wobei:
Figure imgf000016_0001
in which:
G13 steht für ein Wasserstoffatom, ein Halogenatom, einen C1- bis C4-Alkylrest, einen C1- bis C4-Monohydroxyalkylrest, einen C2- bis C4-Polyhydroxyalkylrest, einen (Ci- bis C4)-Alkoxy- (C1- bis C4)-alkylrest, einen C1- bis C4-Aminoalkylrest, einen Hydroxy-(d- bis C4)- alkylaminorest, einen C1- bis C4-Hydroxyalkoxyrest, einen C1- bis C4-Hydroxyalkyl-(C!-bis C4)- aminoalkylrest oder einen (Di-C1- bis C4-Alkylamino)-(Cr bis C4)-alkylrest, und G14 steht für ein Wasserstoff- oder Halogenatom, einen C1- bis C4-Alkylrest, einen C1- bis C4- Monohydroxyalkylrest, einen C2- bis C4-Polyhydroxyalkylrest, einen (C1- bis C4)-Alkoxy-(Cr bis C4)-alkylrest, einen C1- bis C4-Aminoalkylrest oder einen C1- bis C4-Cyanoalkylrest,G 13 represents a hydrogen atom, a halogen atom, a C 1 - to C 4 -alkyl radical, a C 1 - to C 4 -monohydroxyalkyl radical, a C 2 - to C 4 -polyhydroxyalkyl radical, a (C 1 - to C 4 ) -alkoxy - (C 1 - to C 4) alkyl group a C 1 - to C 4 aminoalkyl radical, a hydroxy (d- to C 4) - alkylamino, C 1 - to C 4 -Hydroxyalkoxyrest, a C 1 - to C 4 hydroxyalkyl (C 4 to C!) - aminoalkyl radical or a (di-C 1 - to C 4 -alkylamino) - alkyl (C r to C 4), and G 14 represents a hydrogen or halogen atom, a C 1 - to C 4 alkyl, C 1 - to C 4 - monohydroxyalkyl radical, a C 2 - to C 4 polyhydroxyalkyl radical, a (C 1 - to C 4) - Alkoxy (C r to C 4 ) -alkyl radical, a C 1 - to C 4 -aminoalkyl radical or a C 1 - to C 4 -cyanoalkyl radical,
G15 steht für Wasserstoff, einen C1- bis C4-Alkylrest, einen C1- bis C4-Monohydroxyalkylrest, einen C2- bis C4-Polyhydroxyalkylrest, einen Phenylrest oder einen Benzylrest, undG 15 is hydrogen, C 1 - to C 4 -alkyl, C 1 - to C 4 -monohydroxyalkyl, C 2 - to C 4 -polyhydroxyalkyl, phenyl or benzyl, and
G16 steht für Wasserstoff oder ein Halogenatom.G 16 is hydrogen or a halogen atom.
Die in Formel (Ent3) verwendeten Substituenten sind erfindungsgemäß analog zu den obigen Ausführungen definiert.The substituents used in formula (Ent3) are defined according to the invention analogously to the above statements.
Bevorzugte p-Aminophenole der Formel (Ent3) sind insbesondere p-Aminophenol, N-Methyl-p- aminophenol, 4-Amino-3-methyl-phenol, 4-Amino-3-fluorphenol, 2-Hydroxymethylamino-4- aminophenol, 4-Amino-3-hydroxymethylphenol, 4-Amino-2-(ß-hydroxyethoxy)-phenol, 4-Amino-2- methylphenol, 4-Amino-2-hydroxymethylphenol, 4-Amino-2-methoxymethyl-phenol, 4-Amino-2- aminomethylphenol, 4-Amino-2-(ß-hydroxyethyl-aminomethyl)-phenol, 4-Amino-2-(α,ß- dihydroxyethyl)-phenol, 4-Amino-2-fluorphenol, 4-Amino-2-chlorphenol, 4-Amino-2,6- dichlorphenol, 4-Amino-2-(diethyl-aminomethyl)-phenol sowie ihre physiologisch verträglichen Salze.Preferred p-aminophenols of the formula (Ent3) are, in particular, p-aminophenol, N-methyl-p-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 2-hydroxymethylamino-4-aminophenol, 4 -Amino-3-hydroxymethylphenol, 4-amino-2- (β-hydroxyethoxy) -phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethyl-phenol, 4-amino -2-aminomethylphenol, 4-amino-2- (β-hydroxyethyl-aminomethyl) phenol, 4-amino-2- (α, β-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.
Ganz besonders bevorzugte Verbindungen der Formel (Ent3) sind p-Aminophenol, 4-Amino-3- methylphenol, 4-Amino-2-aminomethylphenol, 4-Amino-2-(α,ß-dihydroxyethyl)-phenol und 4- Amino-2-(diethyl-aminomethyl)-phenol.Very particularly preferred compounds of the formula (Ent3) are p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (α, β-dihydroxyethyl) -phenol and 4-amino 2- (diethylaminomethyl) -phenol.
Ferner kann die Entwicklerkomponente ausgewählt sein aus o-Aminophenol und seinen Derivaten, wie beispielsweise 2-Amino-4-methylphenol, 2-Amino-5-methylphenol oder 2-Amino-4- chlorphenol.Further, the developer component may be selected from o-aminophenol and its derivatives such as 2-amino-4-methylphenol, 2-amino-5-methylphenol or 2-amino-4-chlorophenol.
Weiterhin kann die Entwicklerkomponente ausgewählt sein aus heterozyklischen Entwicklerkomponenten, wie beispielsweise den Pyridin-, Pyrimidin-, Pyrazol-, Pyrazol-Pyrimidin- Derivaten und ihren physiologisch verträglichen Salzen.Further, the developer component may be selected from heterocyclic developer components, such as the pyridine, pyrimidine, pyrazole, pyrazole pyrimidine derivatives and their physiologically acceptable salts.
Bevorzugte Pyridin-Derivate sind insbesondere die Verbindungen, die in den Patenten GB 1 026 978 und GB 1 153 196 beschrieben werden, wie 2,5-Diamino-pyridin, 2-(4'-Methoxyphenyl)amino- 3-amino-pyridin, 2,3-Diamino-6-methoxy-pyridin, 2-(ß-Methoxyethyl)amino-3-amino-6-methoxy- pyridin und 3,4-Diamino-pyridin.Preferred pyridine derivatives are, in particular, the compounds described in the patents GB 1 026 978 and GB 1 153 196, such as 2,5-diamino-pyridine, 2- (4'-methoxyphenyl) amino-3-amino-pyridine, 2,3-diamino-6-methoxy-pyridine, 2- (β-methoxyethyl) amino-3-amino-6-methoxy-pyridine and 3,4-diamino-pyridine.
Bevorzugte Pyrimidin-Derivate sind insbesondere die Verbindungen, die im deutschen Patent DE 2 359 399, der japanischen Offenlegungsschrift JP 02019576 A2 oder in der Offenlegungsschrift WO 96/15765 beschrieben werden, wie 2,4,5,6-Tetraaminopyrimidin, 4-Hydroxy-2,5,6- triaminopyrimidin, 2-Hydroxy-4,5,6-triaminopyrimidin, 2-Dimethylamino-4,5,6-triaminopyrimidin, 2,4-Dihydroxy-5,6-diaminopyrimidin und 2,5,6-Triaminopyrimidin.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 Laid-Open Publication WO 96/15765, such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2-dimethylamino-4,5, 6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triaminopyrimidine.
Bevorzugte Pyrazol-Derivate sind insbesondere die Verbindungen, die in den Patenten DE 3 843 892, DE 4 133 957 und Patentanmeldungen WO 94/08969, WO 94/08970, EP-740 931 und DE 195 43 988 beschrieben werden, wie 4,5-Diamino-1-methylpyrazol, 4,5-Diamino-1-(ß- hydroxyethyl)-pyrazol, 3,4-Diaminopyrazol, 4,5-Diamino-1-(4'-chlorbenzyl)-pyrazol, 4,5-Diamino- 1 ,3-dimethylpyrazol, 4,5-Diamino-3-methyl-1-phenylpyrazol, 4,5-Diamino-1-methyl-3- phenylpyrazol, 4-Amino-1 ,3-dimethyl-5-hydrazinopyrazol, 1-Benzyl-4,5-diamino-3-methylpyrazol, 4,5-Diamino-3-tert.-butyl-1-methylpyrazol, 4,5-Diamino-1-tert.-butyl-3-methylpyrazol, 4,5-Diamino- 1-(ß-hydroxyethyl)-3-methylpyrazol, 4,5-Diamino-1-ethyl-3-methylpyrazol, 4,5-Diamino-1-ethyl-3- (4'-methoxyphenyl)-pyrazol, 4,5-Diamino-1 -ethyl-3-hydroxymethylpyrazol, 4,5-Diamino-3- hydroxymethyl-1-methylpyrazol, 4,5-Diamino-3-hydroxymethyl-1-isopropylpyrazol, 4,5-Diamino-3- methyl-1 -isopropylpyrazol, 4-Amino-5-(2-aminoethyl)amino-1 ,3-dimethylpyrazol, 3,4,5-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- (β-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-1-methylpyrazole, 4,5-diamino-1-tert-butyl-3-methylpyrazole, 4, 5-diamino-1- (β-hydroxyethyl) -3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3- (4'-methoxyphenyl) pyrazole , 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3 methyl-1-isopropylpyrazole, 4-amino-5- (2-aminoethyl) amino-1,3-dimethylpyrazole, 3,4,5-
Triaminopyrazol, 1-Methyl-3,4,5-triaminopyrazol, 3,5-Diamino-1-methyl-4-methylaminopyrazol und 3,5-Diamino-4-(ß-hydroxyethyl)amino-1-methylpyrazol.Triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole and 3,5-diamino-4- (β-hydroxyethyl) amino-1-methylpyrazole.
Bevorzugte Pyrazolopyrimidin-Derivate sind insbesondere die Derivate des Pyrazolo[1 ,5- a]opyrimidin der folgenden Formel (Ent4) und dessen tautomeren Formen, sofern ein tautomeres Gleichgewicht besteht:Preferred pyrazolopyrimidine derivatives are, in particular, the derivatives of the pyrazolo [1,5-a] opyrimidine of the following formula (Ent4) and their tautomeric forms, if a tautomeric equilibrium exists:
Figure imgf000018_0001
wobei:
Figure imgf000018_0001
in which:
G17, G18, G19 und G20 unabhängig voneinander stehen für ein Wasserstoffatom, einen C1- bis C4-Alkylrest, einen Aryl-Rest, einen Ci- bis C4-Hydroxyalkylrest, einen C2- bis C4- Polyhydroxyalkylrest einen (C1- bis C4J-AIkOXy-(C1- bis C4)-alkylrest, einen C1- bis C4- Aminoalkylrest, der gegebenenfalls durch ein Acetyl-Ureid- oder einen Sulfonyl-Rest geschützt sein kann, einen (C1- bis C4)-Alkylamino-(C1- bis C4)-alkylrest, einen DK(C1- bis C4)-alkyl]-(Cr bis C4)-aminoalkylrest, wobei die Dialkyl-Reste gegebenenfalls einen Kohlenstoffzyklus oder einen Heterozyklus mit 5 oder 6 Kettengliedern bilden, einen C1- bis C4-Hydroxyalkyl- oder einen Di-(C1- bis C^-tHydroxyalkylHd- bis C4)-aminoalkylrest, die X-Reste stehen unabhängig voneinander für ein Wasserstoffatom, einen C1- bis C4- Alkylrest, einen Aryl-Rest, einen C1- bis C4-Hydroxyalkylrest, einen C2- bis C4- Polyhydroxyalkylrest, einen C1- bis C4-Aminoalkylrest, einen (C1- bis C^-Alkylamino^Cr bis C4)-alkylrest, einen DK(C1- bis C4)alkyl]- (C1- bis C4)-aminoalkylrest, wobei die Dialkyl-Reste gegebenenfalls einen Kohlenstoffzyklus oder einen Heterozyklus mit 5 oder 6 Kettengliedern bilden, einen C1- bis C4-Hydroxyalkyl- oder einen Di-(C1- bis C4-hydroxyalkyl)aminoalkylrest, einen Aminorest, einen C1- bis C4-Alkyl- oder Di-(C1- bis C4-hydroxyalkyl)aminorest, ein Halogenatom, eine Carboxylsäuregruppe oder eine Sulfonsäuregruppe, i hat den Wert 0, 1 , 2 oder 3, p hat den Wert 0 oder 1 , q hat den Wert 0 oder 1 und n hat den Wert 0 oder 1 , mit der Maßgabe, dass die Summe aus p + q ungleich 0 ist, wenn p + q gleich 2 ist, n den Wert 0 hat, und die Gruppen NG17G18 und NG19G20 belegen dieG 17, G 18, G 19 and G 20 are independently a hydrogen atom, a C 1 - to C 4 -alkyl radical, an aryl radical, a Ci to C 4 -hydroxyalkyl group, a C 2 - to C 4 - Polyhydroxyalkylrest a (C 1 - to C 4 J-AIkOXy- (C 1 - to C 4 ) -alkyl radical, a C 1 - to C 4 - aminoalkyl radical which may optionally be protected by an acetyl-ureide or a sulfonyl radical , a (C 1 to C 4 ) alkylamino (C 1 to C 4 ) alkyl radical, a DK (C 1 to C 4 ) alkyl] (C r to C 4 ) aminoalkyl radical, wherein the Dialkyl radicals optionally form a carbon cycle or a heterocycle with 5 or 6 chain members, a C 1 - to C 4 -hydroxyalkyl or a di- (C 1 - to C ^ -tHydroxyalkylHd- to C 4 ) aminoalkyl radical, the X- radicals are each independently a hydrogen atom, a C 1 - to C 4 - alkyl radical, an aryl radical, a C 1 - to C 4 -hydroxyalkyl group, a C 2 - to C 4 - polyhydroxyalkyl radical, a C 1 - to C 4 Aminoalkyl radical, a ( C 1 - to C ^ -alkylamino ^ Cr bis C 4 ) -alkyl radical, a DK (C 1 - 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 group, an amino group, a C 1 - to C 4 -alkyl- or di- (C 1 - to C 4 hydroxyalkyl) amino, a halogen atom, a carboxylic acid group or a sulfonic acid group, i has the value 0, 1, 2 or 3, p has the value 0 or 1, q has the value 0 or 1 and n has the value 0 or 1, with the proviso in that the sum of p + q is not equal to 0 when p + q is 2, n is 0, and the groups NG 17 G 18 and NG 19 G 20 occupy the
Positionen (2,3); (5,6); (6,7); (3,5) oder (3,7); wweennnn pp ++ qq gglleeiicchh 11 iisstt,, nn ddeenn WWeerrtt 11 hhaatt,, uurnd die Gruppen NG17G18 (oder NG19G20) und diePositions (2,3); (5,6); (6,7); (3,5) or (3,7); wweennnn pp ++ qq gglleeiicchh 11 uisstt ,, nn ddeenn WWeerrtt 11 hhaatt ,, about the groups NG 17 G 18 (or NG 19 G 20 ) and the
Gruppe OH belegen die Positionen (2,3); (5,6); (6,7); (3,5) oder (3,7);Group OH occupy the positions (2,3); (5,6); (6,7); (3,5) or (3,7);
Die in Formel (Ent4) verwendeten Substituenten sind erfindungsgemäß analog zu den obigen Ausführungen definiert.The substituents used in formula (Ent4) are defined according to the invention analogously to the above statements.
Wenn das Pyrazolo[1 ,5-a]pyrimidin der obenstehenden Formel (Ent4) eine Hydroxygruppe an einer der Positionen 2, 5 oder 7 des Ringsystems enthält, besteht ein tautomeres Gleichgewicht, das zum Beispiel im folgenden Schema dargestellt wird:When the pyrazolo [1,5-a] pyrimidine of the above formula (Ent4) contains a hydroxy group at one of the 2, 5 or 7 positions of the ring system, there is a tautomeric equilibrium which is shown, for example, in the following scheme:
Figure imgf000019_0001
Figure imgf000019_0001
Unter den Pyrazolo[1 ,5-a]pyrimidinen der obenstehenden Formel (Ent4) kann man insbesondere nennen:Among the pyrazolo [1, 5-a] pyrimidines of the above formula (Ent4) may be mentioned in particular:
Pyrazolo[1 ,5-a]pyrimidin-3,7-diamin;Pyrazolo [1,5-a] pyrimidine-3,7-diamine;
2,5-Dimethyl-pyrazolo[1 ,5-a]pyrimidin-3,7-diamin;2,5-dimethyl-pyrazolo [1,5-a] pyrimidine-3,7-diamine;
Pyrazolo[1 ,5-a]pyrimidin-3,5-diamin;Pyrazolo [1,5-a] pyrimidine-3,5-diamine;
2,7-Dimethyl-pyrazolo[1,5-a]pyrimidin-3,5-diamin;2,7-dimethyl-pyrazolo [1,5-a] pyrimidine-3,5-diamine;
3-Aminopyrazolo[1 ,5-a]pyrimidin-7-ol;3-aminopyrazolo [1,5-a] pyrimidin-7-ol;
3-Aminopyrazolo[1 ,5-a]pyrimidin-5-ol; 2-(3-Aminopyrazolo[1 ,5-a]pyrimidin-7-ylamino)-ethanol; 2-(7-Aminopyrazolo[1 ,5-a]pyrimidin-3-ylamino)-ethanol; 2-[(3-Aminopyrazolo[1 ,5-a]pyrimidin-7-yl)-(2-hydroxy-ethyl)amino]-ethanol; 2-[(7-Aminopyrazolo[1 ,5-a]pyrimidin-3-yl)-(2-hydroxy-ethyl)amino]-ethanol; 5,6-Dimethylpyrazolo[1 ,5-a]pyrimidin-3,7-diamin; 2,6-Dimethylpyrazolo[1 ,5-a]pyrimidin-3,7-diamin; 3-Amino-7-dimethylamino-2,5-dimethylpyrazolo[1 ,5-a]pyrimidin; sowie ihre physiologisch verträglichen Salze und ihre tautomeren Formen, wenn ein tautomeres Gleichgewicht vorhanden ist.3-aminopyrazolo [1,5-a] pyrimidin-5-ol; 2- (3-aminopyrazolo [1,5-a] pyrimidin-7-ylamino) ethanol; 2- (7-aminopyrazolo [1,5-a] pyrimidin-3-ylamino) ethanol; 2 - [(3-aminopyrazolo [1,5-a] pyrimidin-7-yl) - (2-hydroxy-ethyl) -amino] -ethanol; 2 - [(7-aminopyrazolo [1,5-a] pyrimidin-3-yl) - (2-hydroxy-ethyl) -amino] -ethanol; 5,6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine; 2,6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine; 3-amino-7-dimethylamino-2,5-dimethylpyrazolo [1,5-a] pyrimidine; and their physiologically acceptable salts and their tautomeric forms when tautomeric equilibrium is present.
Die Pyrazolo[1 ,5-a]pyrimidine der obenstehenden Formel (Ent4) können wie in der Literatur beschrieben durch Zyklisierung ausgehend von einem Aminopyrazol oder von Hydrazin hergestellt werden.The pyrazolo [1, 5-a] pyrimidines of the above formula (Ent4) can be prepared as described in the literature by cyclization from an aminopyrazole or hydrazine.
Als Kupplerkomponenten werden in der Regel m-Phenylendiaminderivate, Naphthole, Resorcin und Resorcinderivate, Pyrazolone und m-Aminophenolderivate sowie heterozyklische Verbindungen verwendet.As coupler components m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives and heterocyclic compounds are generally used.
Erfindungsgemäß bevorzugte Kupplerkomponenten sind m-Aminophenol und dessen Derivate wie beispielsweise 5-Amino-2-methylphenol, N-Coupler components preferred 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-chlor-6-methylphenol, 2-Hydroxy-4- aminophenoxyethanol, 2,6-Dimethyl-3-aminophenol, 3-TNfluoroacetylamino-2-chlor-6- methylphenol, 5-Amino-4-chlor-2-methylphenol, 5-Amino-4-methoxy-2-methylphenol, 5-(2'-Cyclopentyl-3-aminophenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 2,6-dimethyl-3-aminophenol, 3-TNfluoroacetylamino-2-chloro-6-methylphenol, 5- Amino-4-chloro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol, 5- (2'-
Hydroxyethyl)-amino-2-methylphenol, 3-(Diethylamino)-phenol, N-Cyclopentyl-3-aminophenol,Hydroxyethyl) -amino-2-methylphenol, 3- (diethylamino) -phenol, N-cyclopentyl-3-aminophenol,
1,3-Dihydroxy-5-(methylamino)-benzol, 3-Ethylamino-4-methylphenol und 2,4-Dichlor-3- aminophenol, o-Aminophenol und dessen Derivate, m-Diaminobenzol und dessen Derivate wie beispielsweise 2,4-Diaminophenoxy-ethanol, 1 ,3-1,3-dihydroxy-5- (methylamino) -benzene, 3-ethylamino-4-methylphenol and 2,4-dichloro-3-aminophenol, o-aminophenol and its derivatives, m-diaminobenzene and its derivatives such as 2,4 -Diaminophenoxyethanol, 1, 3
Bis-(21,4'-diaminophenoxy)-propan, 1-Methoxy-2-amino-4-(2'-hydroxyethylamino)benzol, 1 ,3-Bis (2 1, 4'-diaminophenoxy) -propane, 1-methoxy-2-amino-4- (2'-hydroxyethylamino) benzene, 1, 3-
Bis-(2',4'-diaminophenyl)-propan, 2,6-Bis-(2'-hydroxyethylamino)-1-methylbenzol, 2-({3-[(2-Bis- (2 ', 4'-diaminophenyl) -propane, 2,6-bis- (2'-hydroxyethylamino) -1-methylbenzene, 2 - ({3 - [(2-
Hydroxyethyl)amino]-4-methoxy-5-methylphenyl}amino)ethanol, 2-({3-[(2-Hydroxyethyl)amino]-Hydroxyethyl) amino] -4-methoxy-5-methylphenyl} amino) ethanol, 2 - ({3 - [(2-hydroxyethyl) amino] -
2-methoxy-5-methylphenyl}amino)ethanol, 2-({3-[(2-Hydroxyethyl)amino]-4,5-dimethylphenyl}- amino)ethanol, 2-[3-Morpholin-4-ylphenyl)amino]ethanol, 3-Amino-4-(2-methoxyethoxy)-5- methylphenylamin und 1-Amino-3-bis-(2'-hydroxyethyl)-aminobenzol, o-Diaminobenzol und dessen Derivate wie beispielsweise 3,4-Diaminobenzoesäure und 2,3-2-methoxy-5-methylphenyl} amino) ethanol, 2- ({3 - [(2-hydroxyethyl) amino] -4,5-dimethylphenyl} -amino) ethanol, 2- [3-morpholin-4-yl-phenyl) -amino ] ethanol, 3-amino-4- (2-methoxyethoxy) -5-methylphenylamine and 1-amino-3-bis (2'-hydroxyethyl) aminobenzene, o-diaminobenzene and its derivatives such as 3,4-diaminobenzoic acid and 2,3
Diamino-1-methylbenzol,Diamino-1-methylbenzene,
Di- beziehungsweise Trihydroxybenzolderivate wie beispielsweise Resorcin,Di- or trihydroxybenzene derivatives such as resorcinol,
Resorcinmonomethylether, 2-Methylresorcin, 5-Methylresorcin, 2,5-Dimethylresorcin, 2-Resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2-
Chlorresorcin, 4-Chlorresorcin, Pyrogallol und 1 ,2,4-Trihydroxybenzol, Pyridinderivate wie beispielsweise 2,6-Dihydroxypyridin, 2-Amino-3-hydroxypyridin, 2-Amino-5- chlor-3-hydroxypyridin, 3-Amino-2-methylamino-6-methoxypyridin, 2,6-Dihydroxy-3,4- dimethylpyridin, 2,6-Dihydroxy-4-methylpyridin, 2,6-Diaminopyridin, 2,3-Diamino-6- methoxypyridin und 3,5-Diamino-2,6-dimethoxypyridin,Chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1,2,4-trihydroxybenzene, Pyridine derivatives such as 2,6-dihydroxypyridine, 2-amino-3-hydroxypyridine, 2-amino-5-chloro-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,6-dihydroxy-3,4 dimethylpyridine, 2,6-dihydroxy-4-methylpyridine, 2,6-diaminopyridine, 2,3-diamino-6-methoxypyridine and 3,5-diamino-2,6-dimethoxypyridine,
Naphthalinderivate wie beispielsweise 1-Naphthol, 2-Methyl-1-naphthol, 2-Hydroxymethyl-1- naphthol, 2-Hydroxyethyl-1-naphthol, 1 ,5-Dihydroxynaphthalin, 1 ,6-Dihydroxynaphthalin, 1 ,7- Dihydroxynaphthalin, 1 ,8-Dihydroxynaphthalin, 2,7-Dihydroxynaphthalin und 2,3- Dihydroxynaphthalin,Naphthalene derivatives such as 1-naphthol, 2-methyl-1-naphthol, 2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 1, 7-dihydroxynaphthalene, 1 , 8-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 2,3-dihydroxynaphthalene,
Morpholinderivate wie beispielsweise 6-Hydroxybenzomorpholin und 6-Amino- benzomorpholin,Morpholine derivatives such as 6-hydroxybenzomorpholine and 6-aminobenzomorpholine,
Chinoxalinderivate wie beispielsweise 6-Methyl-1 ,2,3,4-tetrahydrochinoxalin, Pyrazolderivate wie beispielsweise 1-Phenyl-3-methylpyrazol-5-on, Indolderivate wie beispielsweise 4-Hydroxyindol, 6-Hydroxyindol und 7-Hydroxyindol, Pyrimidinderivate, wie beispielsweise 4,6-Diaminopyrimidin, 4-Amino-2,6-dihydroxypyrimidin, 2,4-Diamino-6-hydroxypyrimidin, 2,4,6-Trihydroxypyrimidin, 2-Amino-4-methylpyrimidin, 2- Amino-4-hydroxy-6-methylpyrimidin und 4,6-Dihydroxy-2-methylpyrimidin, oder Methylendioxybenzolderivate wie beispielsweise 1-Hydroxy-3,4-methylendioxybenzol, 1- Amino-3,4-methylendioxybenzol und 1-(2'-Hydroxyethyl)-amino-3,4-methylendioxybenzol sowie deren physiologisch verträglichen Salze.Quinoxaline derivatives such as 6-methyl-1,2,3,4-tetrahydroquinoxaline, pyrazole derivatives such as 1-phenyl-3-methylpyrazol-5-one, indole derivatives such as 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole, pyrimidine derivatives such as For example, 4,6-diaminopyrimidine, 4-amino-2,6-dihydroxypyrimidine, 2,4-diamino-6-hydroxypyrimidine, 2,4,6-trihydroxypyrimidine, 2-amino-4-methylpyrimidine, 2-amino-4-hydroxy 6-methylpyrimidine and 4,6-dihydroxy-2-methylpyrimidine, or methylenedioxybenzene derivatives such as, for example, 1-hydroxy-3,4-methylenedioxybenzene, 1-amino-3,4-methylenedioxybenzene and 1- (2'-hydroxyethyl) -amino 3,4-methylenedioxybenzene and their physiologically acceptable salts.
Erfindungsgemäß besonders bevorzugte Kupplerkomponenten sind 1-Naphthol, 1 ,5-, 2,7- und 1 ,7-Dihydroxynaphthalin, 3-Aminophenol, 5-Amino-2-methylphenol, 2-Amino-3-hydroxypyridin, Resorcin, 4-Chlorresorcin, 2-Chlor-6-methyl-3-aminophenol, 2-Methylresorcin, 5-Methylresorcin, 2,5-Dimethylresorcin und 2,6-Dihydroxy-3,4-dimethylpyridin und die physiologisch verträglichen Salzen der vorgenannten Verbindungen.Particularly preferred coupler components according to the invention are 1-naphthol, 1, 5, 2,7- and 1, 7-dihydroxynaphthalene, 3-aminophenol, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, resorcinol, 4-chlororesorcinol , 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol and 2,6-dihydroxy-3,4-dimethylpyridine and the physiologically acceptable salts of the aforementioned compounds.
Die erfindungsgemäßen Mittel enthalten die Entwicklerkomponenten bevorzugt in einer Menge von 0,005 bis 10 Gew.-%, vorzugsweise von 0,1 bis 5 Gew.-%, jeweils bezogen auf das gesamte Mittel.The agents according to the invention preferably contain the developer components in an amount of from 0.005 to 10% by weight, preferably from 0.1 to 5% by weight, in each case based on the total agent.
Die erfindungsgemäßen Mittel enthalten die Kupplerkomponenten bevorzugt in einer Menge von 0,005 bis 10 Gew.-%, vorzugsweise von 0,1 bis 5 Gew.-%, jeweils bezogen auf das gesamte Mittel.The agents of the invention preferably contain the coupler components in an amount of 0.005 to 10 wt .-%, preferably from 0.1 to 5 wt .-%, each based on the total agent.
Das erfindungsgemäße Mittel kann als farbgebende Komponente in Form der Oxofarbstoffvorprodukte mindestens eine Kombination, aus mindestens einer Verbindung der KomponenteThe composition according to the invention can be used as a coloring component in the form of the oxo dye precursors at least one combination of at least one compound of the component
1 Verbindungen, die eine reaktive Carbonylgruppe enthalten mit mindestens einer Verbindung der Komponente 2 Verbindungen, ausgewählt aus (a) CH-aciden Verbindungen, (b) Verbindungen mit primärer oder sekundärer Aminogruppe oder Hydroxygruppe, ausgewählt aus primären oder sekundären aromatischen Aminen, stickstoffhaltigen heterozyklischen Verbindungen und aromatischen Hydroxyverbindungen enthalten.1 compounds containing a reactive carbonyl group with at least one compound of the component 2 compounds selected from (a) CH-acidic compounds, (b) compounds containing primary or secondary amino group or hydroxy group selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds.
Erfindungsgemäße Verbindungen mit einer reaktiven Carbonylgruppe (im Folgenden auch reaktive Carbonylverbindungen oder Komponente 1 genannt) besitzen mindestens eine Carbonylgruppe als reaktive Gruppe, welche mit den Verbindungen der Komponente 2 unter Ausbildung einer beide Komponenten verknüpfenden chemischen Bindung reagiert. Ferner sind erfindungsgemäß auch solche Verbindungen als Komponente 1 umfaßt, in denen die reaktive Carbonylgruppe derart derivatisiert bzw. maskiert ist, daß die Reaktivität des Kohlenstoffatoms der derivatisierten bzw. maskierten Carbonylgruppe gegenüber der Komponente 2 stets vorhanden ist. Diese Derivate sind bevorzugt Kondensationsverbindungen von reaktiven Carbonylverbindungen mit a) Aminen und deren Derivate unter Bildung von Iminen oder Oximen als Kondensationsverbindung b) Alkoholen unter Bildung von Acetalen oder Ketalen als Kondensationsverbindung c) Wasser unter Bildung von Hydraten als Kondensationsverbindung von Aldehyden.Compounds according to the invention having a reactive carbonyl group (also referred to below as reactive carbonyl compounds or component 1) have at least one carbonyl group as reactive group which reacts with the compounds of component 2 to form a chemical bond linking both components. Further, according to the invention, those compounds are also included as component 1 in which the reactive carbonyl group is derivatized or masked in such a way that the reactivity of the carbon atom of the derivatized or masked carbonyl group with respect to the component 2 is always present. These derivatives are preferably condensation compounds of reactive carbonyl compounds with a) amines and their derivatives to form imines or oximes as a condensation compound b) alcohols to form acetals or ketals as a condensation compound c) water to form hydrates as a condensation compound of aldehydes.
Die Komponente 1 wird bevorzugt ausgewählt aus der Gruppe, die gebildet wird aus Acetophenon, Propiophenon, 2-Hydroxyacetophenon, 3-Hydroxyacetophenon, 4-Hydroxy- acetophenon, 2-Hydroxypropiophenon, 3-Hydroxypropiophenon, 4-Hydroxypropiophenon, 2- Hydroxybutyrophenon, 3-Hydroxybutyrophenon, 4-Hydroxybutyrophenon, 2,4-Dihydroxy- acetophenon, 2,5-Dihydroxyacetophenon, 2,6-Dihydroxyacetophenon, 2,3,4-Trihydroxy- acetophenon, 3,4,5-Trihydroxyacetophenon, 2,4,6-Trihydroxyacetophenon, 2,4,6-Trimeth- oxyacetophenon, 3,4,5-Trimethoxyacetophenon, 3,4,5-Trimethoxy-acetophenon-diethylketal, 4- Hydroxy-3-methoxy-acetophenon, 3,5-Dimethoxy-4-hydroxyacetophenon, 4-Aminoacetophenon, 4-Dimethylaminoacetophenon, 4-Morpholinoacetophenon, 4-Piperidinoacetophenon, 4- Imidazolinoacetophenon, 2-Hydroxy-5-brom-acetophenon, 4-Hydroxy-3-nitroacetophenon, Acetophenon-2-carbonsäure, Acetophenon-4-carbonsäure, Benzophenon, 4-Component 1 is preferably selected from the group formed from acetophenone, propiophenone, 2-hydroxyacetophenone, 3-hydroxyacetophenone, 4-hydroxyacetophenone, 2-hydroxypropiophenone, 3-hydroxypropiophenone, 4-hydroxypropiophenone, 2-hydroxybutyrophenone, 3 Hydroxybutyrophenone, 4-hydroxybutyrophenone, 2,4-dihydroxyacetophenone, 2,5-dihydroxyacetophenone, 2,6-dihydroxyacetophenone, 2,3,4-trihydroxyacetophenone, 3,4,5-trihydroxyacetophenone, 2,4,6-dihydroxyacetophenone Trihydroxyacetophenone, 2,4,6-trimethoxyacetophenone, 3,4,5-trimethoxyacetophenone, 3,4,5-trimethoxyacetophenone diethyl ketal, 4-hydroxy-3-methoxy-acetophenone, 3,5-dimethoxy-4- hydroxyacetophenone, 4-aminoacetophenone, 4-dimethylaminoacetophenone, 4-morpholinoacetophenone, 4-piperidinoacetophenone, 4-imidazolinoacetophenone, 2-hydroxy-5-bromo-acetophenone, 4-hydroxy-3-nitroacetophenone, acetophenone-2-carboxylic acid, acetophenone-4 carboxylic acid, benzophenone, 4-
Hydroxybenzophenon, 2-Aminobenzophenon, 4,4'-Dihydroxybenzophenon, 2,4-Dihydroxy- benzophenon, 2,4,4'-Trihydroxybenzophenon, 2,3,4-Trihydroxybenzophenon, 2-Hydroxy-1- acetonaphthon, 1-Hydroxy-2-acetonaphthon, Chromon, Chromon-2-carbonsäure, Flavon, 3- Hydroxyflavon, 3,5,7-Trihydroxyflavon, 4',5,7-Trihydroxyflavon, 5,6,7-Trihydroxyflavon, Quercetin, 1-lndanon, 9-Fluorenon, 3-Hydroxyfluorenon, Anthron, 1 ,8-Dihydroxyanthron, Vanillin, Coniferylaldehyd, 2-Methoxybenzaldehyd, 3-Methoxybenzaldehyd, 4-Methoxybenzaldehyd, 2- Ethoxybenzaldehyd, 3-Ethoxybenzaldehyd, 4-Ethoxybenzaldehyd, 4-Hydroxy-2,3-dimethoxy- benzaldehyd, 4-Hydroxy-2,5-dimethoxy-benzaldehyd, 4-Hydroxy-2,6-dimethoxy-benzaldehyd, A- Hydroxy-2-methyl-benzaldehyd, 4-Hydroxy-3-methyl-benzaldehyd, 4-Hydroxy-2,3-dimethyl- benzaldehyd, 4-Hydroxy-2,5-dimethyl-benzaldehyd, 4-Hydroxy-2,6-dimethyl-benzaldehyd, A- Hydroxy-3,5-dimethoxy-benzaldehyd, 4-Hydroxy-3,5-dimethyl-benzaldehyd, 3,5-Diethoxy-4- hydroxy-benzaldehyd, 2,6-Diethoxy-4-hydroxy-benzaldehyd, 3-Hydroxy-4-methoxy-benzaldehyd, 2-Hydroxy-4-methoxy-benzaldehyd, 2-Ethoxy-4-hydroxy-benzaldehyd, 3-Ethoxy-4-hydroxy- benzaldehyd, 4-Ethoxy-2-hydroxy-benzaldehyd, 4-Ethoxy-3-hydroxy-benzaldehyd, 2,3- Dimethoxybenzaldehyd, 2,4-Dimethoxybenzaldehyd, 2,5-Dimethoxybenzaldehyd, 2,6- Dimethoxybenzaldehyd, 3,4-Dimethoxybenzaldehyd, 3,5-Dimethoxybenzaldehyd, 2,3,4- Trimethoxybenzaldehyd, 2,3,5-Trimethoxybenzaldehyd, 2,3,6-Trimethoxybenzaldehyd, 2,4,6- Trimethoxybenzaldehyd, 2,4,5-Trimethoxybenzaldehyd, 2,5,6-Trimethoxybenzaldehyd, 2- Hydroxybenzaldehyd, 3-Hydroxybenzaldehyd, 4-Hydroxybenzaldehyd, 2,3-Dihydroxybenzaldehyd, 2,4-Dihydroxybenzaldehyd, 2,5-Dihydroxybenzaldehyd, 2,6-Dihydroxybenzaldehyd, 3,4- Dihydroxybenzaldehyd, 3,5-Dihydroxybenzaldehyd, 2,3,4-Trihydroxybenzaldehyd, 2,3,5- Trihydroxybenzaldehyd, 2,3,6-Trihydroxybenzaldehyd, 2,4,6-Trihydroxybenzaldehyd, 2,4,5- Trihydroxybenzaldehyd, 2,5,6-Trihydroxybenzaldehyd, 4-Hydroxy-2-methoxybenzaldehyd, 4-Dime- thylaminobenzaldehyd, 4-Diethylaminobenzaldehyd, 4-Dimethylamino-2-hydroxybenzaldehyd, A- Diethylamino-2-hydroxybenzaldehyd, 4-Pyrrolidinobenzaldehyd, 4-Morpholinobenzaldehyd, 2-Mor- pholinobenzaldehyd, 4-Piperidinobenzaldehyd, 2-Methoxy-1-naphthaldehyd, 4-Methoxy-1- naphthaldehyd, 2-Hydroxy-i-naphthaldehyd, 2,4-Dihydroxy-i-napthaldehyd, 4-Hydroxy-3-methoxy- 1-naphthaldehyd, 2-Hydroxy-4-methoxy-1-naphthaldehyd, 3-Hydroxy-4-methoxy-1-naphthaldehyd, 2,4-Dimethoxy-1-naphthaldehyd, 3,4-Dimethoxy-1-naphthaldehyd, 4-Hydroxy-1-naphthaldehyd, A- Dimethylamino-1-naphthaldehyd, 2-Methoxy-zimtaldehyd, 4-Methoxy-zimtaldehyd, 4-Hydroxy-3- methoxy-zimtaldehyd, 3,5-Dimethoxy-4-hydroxy-zimtaldehyd, 4-Dimethylaminozimtaldehyd, 2- Dimethylaminobenzaldehyd, 2-Chlor-4-dimethylaminobenzaldehyd, 4-Dimethylamino-2- methylbenzaldehyd, 4-Diethylamino-zimtaldehyd, 4-Dibutylamino-benzaldehyd, 4-Dipheny!amino- benzaldehyd, 4-Dimethylamino-2-methoxybenzaldehyd, 4-(1-lmidazolyl)-benzaldehyd, Piperonal, 2,3,6,7-Tetrahydro-1 H,5H-benzo[ij]chinolizin-9-carboxaldehyd, 2,3,6,7-Tetrahydro-8-hydroxy- 1 H,5H-benzo[ij]chinolizin-9-carboxaldehyd, N-Ethylcarbazol-3-aldehyd, 2-Formylmethylen-1 ,3,3- trimethylindolin (Fischers Aldehyd oder Tribasen Aldehyd), 2-lndolaldehyd, 3-lndolaldehyd, 1- Methylindol-3-aldehyd, 2-Methylindol-3-aldehyd, 1-Acetylindol-3-aldehyd, 3-Acetylindol, 1-Methyl-3- acetylindol, 2-(1'l3',3'-Trimethyl-2-indolinyliden)-acetaldehyd, 1-Methylpyrrol-2-aldehyd, 1-Methyl-2- acetylpyrrol, 4-Pyridinaldehyd, 2-Pyridinaldehyd, 3-Pyridinaldehyd, 4-Acetylpyridin, 2-Acetylpyridin, 3-Acetylpyridin, Pyridoxal, Chinolin-3-aldehyd, Chinolin-4-aldehyd, Antipyrin-4-aldehyd, Furfural, 5- Nitrofurfural, 2-Thenoyl-trifluor-aceton, Chromon-3-aldehyd, 3-(5'-Nitro-2'-furyl)-acrolein, 3-(2'- Furyl)-acrolein und lmidazol-2-aldehyd, 1 ,3-Diacetylbenzol, 1 ,4-Diacetylbenzol, 1 ,3,5- Triacetylbenzol, 2-Benzoyl-acetophenon, 2-(4'-Methoxybenzoyl)-acetophenon, 2-(2'-Furoyl)- acetophenon, 2-(2'-Pyridoyl)-acetophenon und 2-(3'-Pyridoyl)-acetophenon, Benzylidenaceton, 4- Hydroxybenzylidenaceton, 2-Hydroxybenzylidenaceton, 4-Methoxybenzylidenaceton, 4-Hydroxy-3- methoxybenzylidenaceton, 4-Dimethylaminobenzylidenaceton, 3,4-Me- thylendioxybenzylidenaceton, 4-Pyrrolidinobenzylidenaceton, 4-Piperidinobenzylidenaceton, 4-Mor- pholinobenzylidenaceton, 4-Diethylaminobenzylidenaceton, 3-Benzyliden-2,4-pentandion, 3-(4'- Hydroxybenzyliden)-2,4-pentandion, 3-(4'-Dimethylaminobenzyliden)-2,4-pentandion, 2- Benzylidencyclohexanon, 2-(4'-Hydroxybenzyliden)-cyclohexanon, 2-(4'-Dimethylaminobenzy- liden)-cyclohexanon, 2-Benzyliden-1 ,3-cyclohexandion, 2-(4'-Hydroxybenzyliden)-1 ,3-cyclohexan- dion, 3-(4'-Dimethylaminobenzyliden)-1 ,3-cyclohexandion, 2-Benzyliden-5,5-dimethyl-1 ,3-cyclohexandion, 2-(4'-Hydroxybenzyliden)-5,5-dimethyl-1 ,3-cyclohexandion, 2-(4'-Hydroxy-3-meth- oxybenzyliden)-5,5-dimethyl-1 ,3-cyclohexandion, 2-(4'-Dimethylaminobenzyliden)-5,5-dimethyl- 1 ,3-cyclohexandion, 2-Benzylidencyclopentanon, 2'-(4-Hydroxybenzyliden)-cyclopentanon, 2-(4'- Dimethylaminobenzyliden)-cyclopentanon, 5-(4-Dimethylaminophenyl)penta-2,4-dienal, 5-(4- Diethylaminophenyl)penta-2,4-dienal, 5-(4-Methoxyphenyl)penta-2,4-dienal, 5-(3,4-Hydroxybenzophenone, 2-aminobenzophenone, 4,4'-dihydroxybenzophenone, 2,4-dihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2-hydroxy-1-acetonaphthone, 1-hydroxybenzophenone 2-acetonaphthone, chromone, chromone-2-carboxylic acid, flavone, 3-hydroxyflavone, 3,5,7-trihydroxyflavone, 4 ', 5,7-trihydroxyflavone, 5,6,7-trihydroxyflavone, quercetin, 1-indanone, 9 Fluorenone, 3-hydroxyfluorenone, anthrone, 1,8-dihydroxyanthrone, vanillin, coniferylaldehyde, 2-methoxybenzaldehyde, 3-methoxybenzaldehyde, 4-methoxybenzaldehyde, 2- Ethoxybenzaldehyde, 3-ethoxybenzaldehyde, 4-ethoxybenzaldehyde, 4-hydroxy-2,3-dimethoxybenzaldehyde, 4-hydroxy-2,5-dimethoxy-benzaldehyde, 4-hydroxy-2,6-dimethoxy-benzaldehyde, A-hydroxy 2-methylbenzaldehyde, 4-hydroxy-3-methylbenzaldehyde, 4-hydroxy-2,3-dimethylbenzaldehyde, 4-hydroxy-2,5-dimethylbenzaldehyde, 4-hydroxy-2,6-dimethyl- benzaldehyde, A-hydroxy-3,5-dimethoxybenzaldehyde, 4-hydroxy-3,5-dimethylbenzaldehyde, 3,5-diethoxy-4-hydroxybenzaldehyde, 2,6-diethoxy-4-hydroxybenzaldehyde, 3-hydroxy-4-methoxybenzaldehyde, 2-hydroxy-4-methoxybenzaldehyde, 2-ethoxy-4-hydroxybenzaldehyde, 3-ethoxy-4-hydroxybenzaldehyde, 4-ethoxy-2-hydroxybenzaldehyde, 4-ethoxy-3-hydroxybenzaldehyde, 2,3-dimethoxybenzaldehyde, 2,4-dimethoxybenzaldehyde, 2,5-dimethoxybenzaldehyde, 2,6-dimethoxybenzaldehyde, 3,4-dimethoxybenzaldehyde, 3,5-dimethoxybenzaldehyde, 2,3, 4-trimethoxybenzaldehyde, 2,3,5-trimethoxybenzaldehyde, 2,3,6-trimethoxybenzaldehyde, 2,4,6-trimethoxybenzaldehyde, 2,4,5-trimethoxybenzaldehyde, 2,5,6- Trimethoxybenzaldehyde, 2-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 2,3-dihydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 2,5-dihydroxybenzaldehyde, 2,6-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, 3,5-dihydroxybenzaldehyde, 2,3,4-trihydroxybenzaldehyde, 2,3,5-trihydroxybenzaldehyde, 2,3,6-trihydroxybenzaldehyde, 2,4,6-trihydroxybenzaldehyde, 2,4,5-trihydroxybenzaldehyde, 2,5,6-trihydroxybenzaldehyde, 4- Hydroxy-2-methoxybenzaldehyde, 4-dimethylaminobenzaldehyde, 4-diethylaminobenzaldehyde, 4-dimethylamino-2-hydroxybenzaldehyde, A-diethylamino-2-hydroxybenzaldehyde, 4-pyrrolidinobenzaldehyde, 4-morpholinobenzaldehyde, 2-morpholinobenzaldehyde, 4-piperidinobenzaldehyde, 2-methoxy-1-naphthaldehyde, 4-methoxy-1-naphthaldehyde, 2-hydroxy-i-naphthaldehyde, 2,4-dihydroxy-i-naphthaldehyde, 4-hydroxy-3-methoxy-1-naphthaldehyde, 2-hydroxy 4-methoxy-1-naphthaldehyde, 3-hydroxy-4-methoxy-1-naphthaldehyde, 2,4-dimethoxy-1-naphthaldehyde, 3,4-dimethoxy-1-naphthaldehyde, 4-hydroxy-1-naphthaldeh yd, A-dimethylamino-1-naphthaldehyde, 2-methoxycinnamaldehyde, 4-methoxycinnamaldehyde, 4-hydroxy-3-methoxycinnamaldehyde, 3,5-dimethoxy-4-hydroxy-cinnamaldehyde, 4-dimethylaminocinnamaldehyde, 2- Dimethylaminobenzaldehyde, 2-chloro-4-dimethylaminobenzaldehyde, 4-dimethylamino-2-methylbenzaldehyde, 4-diethylamino-cinnamaldehyde, 4-dibutylaminobenzaldehyde, 4-diphenylaminobenzaldehyde, 4-dimethylamino-2-methoxybenzaldehyde, 4- (1 -lmidazolyl) -benzaldehyde, piperonal, 2,3,6,7-tetrahydro-1H, 5H-benzo [ij] quinolizine-9-carboxaldehyde, 2,3,6,7-tetrahydro-8-hydroxy-1H, 5H-benzo [ij] quinolizine-9-carboxaldehyde, N-ethylcarbazole-3-aldehyde, 2-formylmethylene-1,3,3-trimethylindoline (Fischer's aldehyde or tribasic aldehyde), 2-indolaldehyde, 3-indolaldehyde, 1-methylindole 3-aldehyde, 2-methylindole-3-aldehyde, 1-acetylindole-3-aldehyde, 3-acetylindole, 1-methyl-3-acetylindole, 2- (1 ' l 3', 3'-trimethyl-2-indolinylidene ) -acetaldehyde, 1-methylpyrrole-2-aldehyde, 1-methyl-2-acetylpyrrole, 4-pyridine aldehyde, 2-pyridine aldehyde, 3-pyridine dehyde, 4-acetylpyridine, 2-acetylpyridine, 3-acetylpyridine, pyridoxal, quinoline-3-aldehyde, quinoline-4-aldehyde, antipyrine-4-aldehyde, furfural, 5-nitrofurfural, 2-thenoyl-trifluoro-acetone, chromone 3-aldehyde, 3- (5'-nitro-2'-furyl) acrolein, 3- (2'-furyl) -acrolein and imidazole-2-aldehyde, 1, 3-diacetylbenzene, 1, 4-diacetylbenzene, 1 , 3,5- Triacetylbenzene, 2-benzoyl-acetophenone, 2- (4'-methoxybenzoyl) -acetophenone, 2- (2'-furoyl) -acetophenone, 2- (2'-pyridoyl) -acetophenone and 2- (3'-pyridoyl) - acetophenone, benzylideneacetone, 4-hydroxybenzylideneacetone, 2-hydroxybenzylideneacetone, 4-methoxybenzylideneacetone, 4-hydroxy-3-methoxybenzylideneacetone, 4-dimethylaminobenzylideneacetone, 3,4-methylenedioxybenzylideneacetone, 4-pyrrolidinobenzylideneacetone, 4-piperidinobenzylideneacetone, 4-morpholinobenzylideneacetone, 4-diethylaminobenzylideneacetone, 3-benzylidene-2,4-pentanedione, 3- (4'-hydroxybenzylidene) -2,4-pentanedione, 3- (4'-dimethylaminobenzylidene) -2,4-pentanedione, 2-benzylidenecyclohexanone, 2 (4'-hydroxybenzylidene) cyclohexanone, 2- (4'-dimethylaminobenzylidene) cyclohexanone, 2-benzylidene-1, 3-cyclohexanedione, 2- (4'-hydroxybenzylidene) -1,3-cyclohexanedione, 3 - (4'-dimethylaminobenzylidene) -1,3-cyclohexanedione, 2-benzylidene-5,5-dimethyl-1,3-cyclohexanedione, 2- (4'-hydroxybenzylidene) -5,5-dimethyl-1,3-cyclohexanedione , 2- (4'-Hydroxy-3-methoxybenzyli den-5,5-dimethyl-1,3-cyclohexanedione, 2- (4'-dimethylaminobenzylidene) -5,5-dimethyl-1,3-cyclohexanedione, 2-benzylidenecyclopentanone, 2 '- (4-hydroxybenzylidene) -cyclopentanone , 2- (4'-Dimethylaminobenzylidene) cyclopentanone, 5- (4-dimethylaminophenyl) penta-2,4-dienal, 5- (4-diethylaminophenyl) penta-2,4-dienal, 5- (4-methoxyphenyl) penta -2,4-dienal, 5- (3,4-
Dimethoxyphenyl)penta-2,4-dienal, 5-(2,4-Dimethoxyphenyl)penta-2,4-dienal, 5-(4-Dimethoxyphenyl) penta-2,4-dienal, 5- (2,4-dimethoxyphenyl) penta-2,4-dienal, 5- (4-
Piperidinophenyl)penta-2,4-dienal, 5-(4-Morpholinophenyl)penta-2,4-dienal, 5-(4-Piperidinophenyl) penta-2,4-dienal, 5- (4-morpholinophenyl) -penta-2,4-dienal, 5- (4-
Pyrrolidinophenyl)penta-2,4-dienal, 6-(4-Dimethylaminophenyl)hexa-3,5-dien-2-on, 6-(4- Diethylaminophenyl)hexa-3,5-dien-2-on, 6-(4-Methoxyphenyl)hexa-3,5-dien-2-on, 6-(3,4- Dimethoxyphenyl)hexa-3,5-dien-2-on, 6-(2,4-Dimethoxyphenyl)hexa-3,5-dien-2-on, 6-(4- Piperidinophenyl)hexa-3,5-dien-2-on, 6-(4-Morpholinophenyl)hexa-3,5-dien-2-on, 6-(4-Pyrrolidinophenyl) penta-2,4-dienal, 6- (4-dimethylaminophenyl) hexa-3,5-dien-2-one, 6- (4-diethylaminophenyl) hexa-3,5-dien-2-one, 6- (4-methoxyphenyl) hexa-3,5-dien-2-one, 6- (3,4-dimethoxyphenyl) hexa-3,5-dien-2-one, 6- (2,4-dimethoxyphenyl) hexa-3 , 5-dien-2-one, 6- (4-piperidinophenyl) hexa-3,5-dien-2-one, 6- (4-morpholinophenyl) hexa-3,5-dien-2-one, 6- ( 4
Pyrrolidinophenyl)hexa-3,5-dien-2-on, 5-(4-Dimethylamino-1-naphthyl)penta-3,5-dienal, 2- Nitrobenzaldehyd, 3-Nitrobenzaldehyd, 4-Nitrobenzaldehyd, 4-Methyl-3-nitrobenzaldehyd, 3- Hydroxy-4-nitrobenzaldehyd, 4-Hydroxy-3-nitrobenzaldehyd, 5-Hydroxy-2-nitrobenzaldehyd, 2- Hydroxy-5-nitrobenzaldehyd, 2-Hydroxy-3-nitrobenzaldehyd, 2-Fluor-3-nitrobenzaldehyd, 3- Methoxy-2-nitrobenzaldehyd, 4-Chlor-3-nitrobenzaldehyd, 2-Chlor-6-nitrobenzaldehyd, 5-Chlor-2- nitrobenzaldehyd, 4-Chlor-2-nitrobenzaldehyd, 2,4-Dinitrobenzaldehyd, 2,6-Dinitrobenzaldehyd, 2- Hydroxy-3-methoxy-5-nitrobenzaldehyd, 4,5-Dimethoxy-2-nitrobenzaldehyd, 6-Nitropiperonal, 2- Nitropiperonal, 5-Nitrovanillin, 2,5-Dinitrosalicylaldehyd, 5-Brom-3-nitrosalicylaldehyd, 3-Nitro-4- formylbenzolsulfonsäure, 4-Nitro-1-naphthaldehyd, 2-Nitrozimtaldehyd, 3-Nitrozimtaldehyd, 4- Nitrozimtaldehyd, 9-Methyl-3-carbazolaldehyd, 9-Ethyl-3-carbazolaldehyd, 3-Acetylcarbazol, 3,6- Diacetyl-9-ethylcarbazol, 3-Acetyl-9-methylcarbazol, 1 ,4-Dimethyl-3-carbazolaldehyd, 1 ,4,9- Trimethyl-3-carbazolaldehyd, 4-Formyl-1-methylpyridinium-, 2-Formyl-i-methylpyridinium-, A- Formyl-1-ethylpyridinium-, 2-Formyl-1-ethylpyridinium-, 4-Formyl-i-benzylpyridinium-, 2-Formyl-1- benzylpyridinium-, 4-Formyl-1 ,2-dimethylpyridinium-, 4-Formyl-1 ,3-dimethylpyridinium-, 4-Formyl- 1-methylchinolinium-, 2-Formyl-1-methylchinolinium-, 4-Acetyl-1-methylpyridinium-, 2-Acetyl-1-me- thylpyridinium-, 4-Acetyl-1-methylchinolinium-, 5-Formyl-1-methylchinolinium-, 6-Formyl-1- methylchinolinium-, 7-Formyl-i-methylchinolinium-, 8-Formyl-i-methylchinolinium, 5-Formyl-1- ethylchinolinium-, 6-Formyl-i-ethylchinolinium-, 7-Formyl-i-ethylchinolinium-, 8-Formyl-1- ethylchinolinium, 5-Formyl-i-benzylchinolinium-, 6-Formyl-i-benzylchinolinium-, 7-Formyl-1- benzylchinolinium-, 8-Formyl-i-benzylchinolinium, 5-Formyl-i-allylchinolinium-, 6-Formyl-1- allylchinolinium-, 7-Formyl-i-allylchinolinium- und 8-Formyl-i-allylchinolinium-, 5-Acetyl-1- methylchinolinium-, 6-Acetyl-1 -methylchinolinium-, 7-Acetyl-1 -methylchinolinium-, 8-Acetyl-1- methylchinolinium, 5-Acetyl-1-ethylchinolinium-, 6-Acetyl-1-ethylchinolinium-, 7-Acetyl-1- ethylchinolinium-, 8-Acetyl-1-ethylchinolinium, 5-Acetyl-1-benzylchinolinium-, 6-Acetyl-1- benzylchinolinium-, 7-Acetyl-1-benzylchinolinium-, 8-Acetyl-1-benzylchinolinium, 5-Acetyl-1- allylchinolinium-, 6-Acetyl-1 -allylchinolinium-, 7-Acetyl-1-allylchinolinium- und 8-Acetyl-1- allylchinolinium, 9-Formyl-10-methylacridinium-, 4-(2'-Formylvinyl)-1-methylpyridinium-, 1 ,3- Dimethyl-2-(4'-formylphenyl)-benzimidazolium-, 1 ,3-Dimethyl-2-(4'-formylphenyl)-imidazolium-, 2- (4'-Formylphenyl)-3-methylbenzothiazolium-, 2-(4'-Acetylphenyl)-3-methylbenzothiazolium-, 2-(4'- Formylphenyl)-3-methylbenzoxazolium-, 2-(5'-Formyl-2'-furyl)-3-methylbenzothiazolium-, 2-(5'- Formyl-2'-furyl)-3-methylbenzothiazolium-, 2-(5'-Formyl-2'-thienyl)-3-methylbenzothiazolium-, 2-(3'- Formylphenyl)-3-methylbenzothiazolium-, 2-(4'-Formyl-1 -naphthyl)-3-methylbenzothiazolium-, 5- Chlor-2-(4'-formylphenyl)-3-methylbenzothiazolium-, 2-(4'-Formylphenyl)-3,5-dimethyl- benzothiazolium-Salze, bevorzugt mit Benzolsulfonat, p-Toluolsulfonat, Methansulfonat, Perchlorat, Sulfat, Chlorid, Bromid, lodid, Tetrachlorozinkat, Methylsulfat, Trifluormethansulfonat oder Tetrafluoroborat als Gegenion, lsatin, 1-Methyl-isatin, 1-Allyl-isatin, 1-Hydroxymethyl-isatin, 5- Chlor-isatin, 5-Methoxy-isatin, 5-Nitroisatin, 6-Nitro-isatin, 5-Sulfo-isatin, 5-Carboxy-isatin, Chinisatin, 1-Methylchinisatin, sowie beliebigen Gemischen der voranstehenden Verbindungen.Pyrrolidinophenyl) hexa-3,5-dien-2-one, 5- (4-dimethylamino-1-naphthyl) penta-3,5-dienal, 2-nitrobenzaldehyde, 3-nitrobenzaldehyde, 4-nitrobenzaldehyde, 4-methyl-3 -nitrobenzaldehyde, 3-hydroxy-4-nitrobenzaldehyde, 4-hydroxy-3-nitrobenzaldehyde, 5-hydroxy-2-nitrobenzaldehyde, 2-hydroxy-5-nitrobenzaldehyde, 2-hydroxy-3-nitrobenzaldehyde, 2-fluoro-3-nitrobenzaldehyde , 3-methoxy-2-nitrobenzaldehyde, 4-chloro-3-nitrobenzaldehyde, 2-chloro-6-nitrobenzaldehyde, 5-chloro-2-nitrobenzaldehyde, 4-chloro-2-nitrobenzaldehyde, 2,4-dinitrobenzaldehyde, 2.6 Dinitrobenzaldehyde, 2-hydroxy-3-methoxy-5-nitrobenzaldehyde, 4,5-dimethoxy-2-nitrobenzaldehyde, 6-nitropiperonal, 2-nitropiperonal, 5-nitrovanillin, 2,5-dinitrosalicylaldehyde, 5-bromo-3-nitrosalicylaldehyde , 3-nitro-4-formylbenzenesulfonic acid, 4-nitro-1-naphthaldehyde, 2-nitrocinnamaldehyde, 3-nitrocinnamaldehyde, 4-nitrocinnamaldehyde, 9-methyl-3-carbazolaldehyde, 9-ethyl-3-carbazolaldehyde, 3-acetylcarbazole, 3 , 6-Diacetyl-9-ethylcarbazole, 3-acetyl-9-methylcarbazole, 1, 4-dimethyl l-3-carbazolaldehyde, 1, 4,9-trimethyl-3-carbazolaldehyde, 4-formyl-1-methylpyridinium, 2-formyl-i-methylpyridinium, A-formyl-1-ethylpyridinium, 2-formyl-1 -ethylpyridinium, 4-formyl-i-benzylpyridinium, 2-formyl-1-benzylpyridinium, 4-formyl-1,2-dimethylpyridinium, 4-formyl-1,3-dimethylpyridinium, 4-formyl-1 methylquinolinium, 2-formyl-1-methylquinolinium, 4-acetyl-1-methylpyridinium, 2-acetyl-1-methylpyridinium, 4-acetyl-1-methylquinolinium, 5-formyl-1-methylquinolinium, 6-formyl-1- methylquinolinium, 7-formyl-i-methylquinolinium, 8-formyl-i-methylquinolinium, 5-formyl-1-ethylquinolinium, 6-formyl-1-ethylquinolinium, 7-formyl-1-ethylquinolinium, 8-formyl 1-ethylquinolinium, 5-formyl-1-benzylquinolinium, 6-formyl-1-benzylquinolinium, 7-formyl-1-benzylquinolinium, 8-formyl-1-benzylquinolinium, 5-formyl-1-allylquinolinium, 6 -Formyl-1-allylquinolinium, 7-formyl-i-allylquinolinium and 8-formyl-i-allylquinolinium, 5-acetyl-1-methylquinolinium, 6-acetyl-1-methylquinolinium, 7-acetyl-1 - methylquinolinium, 8-acetyl-1-methylquinolinium, 5-acetyl-1-ethylquinolinium, 6-acetyl-1-ethylquinolinium, 7-acetyl-1-ethylquinolinium, 8-acetyl-1-ethylquinolinium, 5-acetyl 1-benzylquinolinium, 6-acetyl-1-benzylquinolinium, 7-acetyl-1-benzylquinolinium, 8-acetyl-1-benzylquinolinium, 5-acetyl-1-allylquinolinium, 6-acetyl-1-allylquinolinium, 7 Acetyl-1-allylquinolinium and 8-acetyl-1-allylquinolinium, 9-formyl-10-methylacridinium, 4- (2'-formylvinyl) -1-me thylpyridinium, 1,3-dimethyl-2- (4'-formylphenyl) benzimidazolium, 1,3-dimethyl-2- (4'-formylphenyl) imidazolium, 2- (4'-formylphenyl) -3- methylbenzothiazolium, 2- (4'-acetylphenyl) -3-methylbenzothiazolium, 2- (4'-formylphenyl) -3-methylbenzoxazolium, 2- (5'-formyl-2'-furyl) -3-methylbenzothiazolium, 2- (5'-formyl-2'-furyl) -3-methylbenzothiazolium, 2- (5'-formyl-2'-thienyl) -3-methylbenzothiazolium, 2- (3'-formylphenyl) -3-methylbenzothiazolium -, 2- (4'-Formyl-1-naphthyl) -3-methylbenzothiazolium, 5-chloro-2- (4'-formylphenyl) -3-methylbenzothiazolium, 2- (4'-formylphenyl) -3.5 dimethylbenzothiazolium salts, preferably with benzenesulfonate, p-toluenesulfonate, methanesulfonate, perchlorate, sulfate, chloride, bromide, iodide, tetrachlorozincate, methylsulfate, trifluoromethanesulfonate or tetrafluoroborate as counterion, isatin, 1-methyl-isatin, 1-allyl-isatin , 1-hydroxymethyl-isatin, 5-chloro-isatin, 5-methoxy-isatin, 5-nitro-isatin, 6-nitro-isatin, 5-sulfo-isatin, 5-carboxy-isatin, quinisatin, 1-meth ylchinisatin, as well as any mixtures of the above compounds.
Als CH-acide werden im allgemeinen solche Verbindungen angesehen, die ein an ein aliphatisches Kohlenstoffatom gebundenes Wasserstoffatom tragen, wobei aufgrund von elektronenziehenden Substituenten eine Aktivierung der entsprechenden Kohlenstoff-Wasserstoff- Bindung bewirkt wird. Unter CH-acide Verbindungen fallen erfindungsgemäß auch Enamine, die durch alkalische Behandlung von quaternierten N-Heterozyklen mit einer in Konjugation zum quartären Stickstoff stehenden CH-aciden Alkylgruppe entstehen.As 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. According to the invention, CH-acidic compounds also include enamines which are formed by alkaline treatment of quaternized N-heterocycles with a CH-acidic alkyl group in conjugation with the quaternary nitrogen.
Die CH-aciden Verbindungen der Komponente 2 sind bevorzugt ausgewählt aus der Gruppe bestehend aus 1 ,2,3,3-Tetramethyl-3H-indoliumiodid, 1 ,2,3,3-Tetramethyl-3H-indolium-p- toluolsulfonat, 1 ,2,3,3-Tetramethyl-3H-indolium-methansulfonat, 1 ,3,3-Trimethyl-2-methylenindolin (Fischersche Base), 2,3-Dimethyl-benzothiazoliumiodid, 2,3-Dimethyl-benzothiazolium-p-toluolsul- fonat, 2,3-Dimethyl-naphtho[1 ,2-d]thiazolium-p-toluolsulfonat, 3-Ethyl-2-methyl-naphtho[1 ,2- d]thiazolium-p-toluolsulfonat, Rhodanin, Rhodanin-3-essigsäure, 1 ,4-Dimethylchinolinium-iodid, 1 ,2-Dimethylchinolinium-iodid, Barbitursäure, Thiobarbitursäure, 1 ,3-Dimethylthiobarbitursäure, 1 ,3-Diethylthiobarbitursäure, 1 ,3-Diethylbarbitursäure, Oxindol, 3-lndoxylacetat, 2-Cumaranon, 5- Hydroxy-2-cumaranon, 6-Hydroxy-2-cumaranon, 3-Methyl-1-phenyl-pyrazolin-5-on, lndan-1 ,2-dion, lndan-1 ,3-dion, lndan-1-on, Benzoylacetonitril, 3-Dicyanmethylenindan-1-on, 2-Amino-4-imino-1 ,3- thiazolin-hydrochlorid, 5,5-Dimethylcyclohexan-1 ,3-dion, 2H-1 ,4-Benzoxazin-4H-3-on, 3-Ethyl-2- methyl-benzoxazoliumiodid, 3-Ethyl-2-methyl-benzothiazoliumiodid, 1-Ethyl-4-methyl- chinoliniumiodid, 1-Ethyl-2-methylchinoliniumiodid, 1 ,2,3-Trimethylchinoxaliniumiodid, 3-Ethyl-2- methyl-benzoxazolium-p-toluolsulfonat, 3-Ethyl-2-methyl-benzothiazolium-p-toluolsulfonat, 1-Ethyl- 4-methyl-chinolinium-p-toluolsulfonat, 1 -Ethyl-2-methylchinolinium-p-toluolsulfonat, und 1 ,2,3- Trimethylchinoxalinium-p-toluolsulfonat.The CH-acidic compounds of component 2 are preferably selected from the group consisting of 1, 2,3,3-tetramethyl-3H-indolium iodide, 1, 2,3,3-tetramethyl-3H-indolium p-toluenesulfonate, 1, 2,3,3-tetramethyl-3H-indolium methanesulfonate, 1,3,3-trimethyl-2-methylenindoline (Fischer's base), 2,3-dimethylbenzothiazolium iodide, 2,3-dimethylbenzothiazolium-p-toluenesulfonate Fonate, 2,3-dimethyl-naphtho [1,2-d] thiazolium p-toluenesulfonate, 3-ethyl-2-methyl-naphtho [1,2-d] thiazolium p-toluenesulfonate, rhodanine, rhodanine-3 acetic acid, 1, 4-dimethylquinolinium iodide, 1, 2-dimethylquinolinium iodide, barbituric acid, thiobarbituric acid, 1, 3-dimethylthiobarbituric acid, 1,3-diethylthiobarbituric acid, 1,3-diethylbarbituric acid, oxindole, 3-indoxylacetate, 2-coumaranone, 5-hydroxy-2-cumaranone, 6-hydroxy-2-cumaranone, 3-methyl-1-phenyl-pyrazolin-5 on, indan-1, 2-dione, indane-1, 3-dione, indan-1-one, benzoylacetonitrile, 3-dicyanomethylenedan-1-one, 2-amino-4-imino-1,3-thiazoline hydrochloride, 5,5-dimethylcyclohexane-1,3-dione, 2H-1,4-benzoxazin-4H-3-one, 3-ethyl-2-methylbenzoxazolium iodide, 3-ethyl-2-methyl-benzothiazolium iodide, 1-ethyl 4-methylquinolinium iodide, 1-ethyl-2-methylquinolinium iodide, 1, 2,3-trimethylquinoxaluminum iodide, 3-ethyl-2-methylbenzoxazolium p-toluenesulfonate, 3-ethyl-2-methylbenzothiazolium p-toluenesulfonate, 1-ethyl-4-methyl-quinolinium p-toluenesulfonate, 1-ethyl-2-methylquinolinium p-toluenesulfonate, and 1,2,3-trimethylquinoxaluminum p-toluenesulfonate.
Bevorzugte primäre oder sekundäre aromatische Amine der Komponente B sind ausgewählt aus N,N-Dimethyl-p-phenylendiamin, N,N-Diethyl-p-phenylendiamin, N-(2-Hydroxyethyl)-N-ethyl-p- phenylendiamin, N,N-Bis-(2-hydroxyethyl)-p-phenylendiamin, N-(2-Methoxyethyl)-p- phenylendiamin, 2,3-Dichlor-p-phenylendiamin, 2,4-Dichlor-p-phenylendiamin, 2,5-Dichlor-p- phenylendiamin, 2-Chlor-p-phenylendiamin, 2,5-Dihydroxy-4-morpholinoanilin, 2-Aminophenol, 3- Aminophenol, 4-Aminophenol, 2-Aminomethyl-4-aminophenol, 2-Hydroxymethyl-4-aminophenol, o-Phenylendiamin, m-Phenylendiamin, p-Phenylendiamin, 2,5-Diaminotoluol, 2,5,-Diaminophenol, 2,5-Diaminoanisol, 2,5,Diaminophenethol, 4-Amino-3-methylphenol, 2-(2,5-Diaminophenyl)-etha- nol, 2,4-Diaminophenoxyethanol, 2-(2,5-Diaminophenoxy)-ethanol, 3-Amino-4-(2-hydroxy- ethyloxy)phenol, 3,4-Methylendioxyphenol, 3,4-Methylendioxyanilin, 3-Amino-2,4-dichlorphenol, 4- Methylaminophenol, 2-Methyl-5-aminophenol, 3-Methyl-4-aminophenol, 2-Methyl-5-(2-hydro- xyethylamino)phenol, 3-Amino-2-chlor-6-methylphenol, 2-Methyl-5-amino-4-chlorphenol, 5-(2- Hydroxyethylamino)-4-methoxy-2-methylphenol, 4-Amino-2-hydroxymethylphenol, 2-Preferred primary or secondary aromatic amines of component B are selected from N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, N- (2-hydroxyethyl) -N-ethyl-p-phenylenediamine, N, N-bis (2-hydroxyethyl) -p-phenylenediamine, N- (2-methoxyethyl) -p-phenylenediamine, 2,3-dichloro-p-phenylenediamine, 2,4-dichloro-p-phenylenediamine, 2.5- Dichloro-p-phenylenediamine, 2-chloro-p-phenylenediamine, 2,5-dihydroxy-4-morpholinoaniline, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminomethyl-4-aminophenol, 2-hydroxymethyl-4- aminophenol, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,5-diaminotoluene, 2,5-diaminophenol, 2,5-diaminoanisole, 2,5, diaminophenethol, 4-amino-3-methylphenol, 2- 2,5-diaminophenyl) ethanol, 2,4-diaminophenoxyethanol, 2- (2,5-diaminophenoxy) ethanol, 3-amino-4- (2-hydroxyethyloxy) phenol, 3,4-methylenedioxyphenol, 3,4-methylenedioxyaniline, 3-amino-2,4-dichlorophenol, 4-methylaminophenol, 2-methyl-5-aminophenol, 3-methyl-4-aminophenol, 2-methyl-5- (2-hydroxyethyl) lamino) phenol, 3-amino-2-chloro-6-methylphenol, 2-methyl-5-amino-4-chlorophenol, 5- (2-hydroxyethylamino) -4-methoxy-2-methylphenol, 4-amino-2- hydroxymethylphenol, 2-
(Diethylaminomethyl)-4-aminophenol, 4-Amino-1-hydroxy-2-(2-hydroxyethylaminomethyl)-benzol, 1-Hydroxy-2-amino-5-methyl-benzol, 1-Hydroxy-2-amino-6-methyl-benzol, 2-Amino-5-acetamido- phenol, 1,3-Dimethyl-2,5-diaminobenzol, 5-(3-Hydroxypropylamino-)2-methylphenol, 5-Amino-4- methoxy-2-methylphenol, N,N-Dimethyl-3-aminophenol, N-Cyclopentyl-3-aminophenol, 5-Amino-4- fluor-2-methylphenol, 2,4-Diamino-5-fluortoluol, 2,4-Diamino-5-(2-hydroxyethoxy)-toluol, 2,4- Diamino-5-methylphenetol, 3,5-Diamino-2-methoxy-1-methylbenzol, 2-Amino-4-(2- hydroxyethylamino)-anisol, 2,6-Bis-(2-hydroxyethylamino)-1-methylbenzol, 1 ,3-Diamino-2,4-di- methoxybenzol, 3,5-Diamino-2-methoxy-toluol, 2-Aminobenzoesäure, 3-Aminobenzoesäure, A- Aminobenzoesäure, 2-Aminophenylessigsäure, 3-Aminophenylessigsäure, 4-Amino- phenylessigsäure, 2,3-Diaminobenzoesäure, 2,4-Diaminobenzoesäure, 2,5-Diaminobenzoesäure, 3,4-Diaminobenzoesäure 3,5-Diaminobenzoesäure, 4-Aminosalicylsäure, 5-Aminosalicylsäure, 3- Amino-4-hydroxy-benzoesäure, 4-Amino-3-hydroxy-benzoesäure, 2-Aminobenzolsulfonsäure, 3- Aminobenzolsulfonsäure, 4-Aminobenzolsulfonsäure, 3-Amino-4-hydroxybenzolsulfonsäure, 4- Amino-3-hydroxynaphthalin-1-sulfonsäure, 6-Amino-7-hydroxynaphthalin-2-sulfonsäure, 7-Amino- 4-hydroxynaphthalin-2-sulfonsäure, 4-Amino-5-hydroxynaphthalin-2,7-disulfonsäure, 3-Amino-2- naphthoesäure, 3-Aminophthalsäure, 5-Aminoisophthalsäure, 1 ,3,5-Triaminobenzol, 1 ,2,4- Triaminobenzol, 1 ,2,4,5-Tetraaminobenzol, 2,4,5-Triaminophenol, Pentaaminobenzol, Hexaamino- benzol, 2,4,6-Triaminoresorcin, 4,5-Diaminobrenzcatechin, 4,6-Diaminopyrogallol, 1-(2-Hydroxy-5- aminobenzyl)-2-imidazolidinon, 4-Amino-2-((4-[(5-amino-2-hydroxyphenyl)methyl]- piperazinyl)methyl)phenol, 3,5-Diamino-4-hydroxybrenzcatechin, 1 ,4-Bis-(4-aminophenyl)-1 ,4- diazacycloheptan, aromatische Nitrile, wie 2-Amino-4-hydroxybenzonitril, 4-Amino-2- hydroxybenzonitril, 4-Aminobenzonitril, 2,4-Diaminobenzonitril, Nitrogruppen-haltige Aminoverbindungen, wie 3-Amino-6-methylamino-2-nitro-pyridin, Pikraminsaure, [8-[(4-Amino-2- nitrophenyl)-azo]-7-hydroxy-naphth-2-yl]-trimethylammoniumchlorid, [8-((4-Amino-3-nitrophenyl)- azo)-7-hydroxy-naphth-2-yl]-trimethylammoniumchlorid (Basic Brown 17), 1-Hydroxy-2-amino-4,6- dinitrobenzol, 1-Amino-2-nitro-4-[bis-(2-hydroxyethyl)amino]-benzol, 1-Amino-2-[(2- hydroxyethyl)amino]-5-nitrobenzol (HC Yellow Nr. 5), 1-Amino-2-nitro-4-[(2-hydroxyethyl)amino]- benzol (HC Red Nr. 7), 2-Chlor-5-nitro-N-2-hydroxyethyl-1 ,4-phenylendiamin, 1-[(2- Hydroxyethyl)amino]-2-nitro-4-amino-benzol (HC Red Nr. 3), 4-Amino-3-nitrophenol, 4-Amino-2- nitrophenol, 6-Nitro-o-toluidin, 1-Amino-3-methyl-4-[(2-hydroxyethyl)amino]-6-nitrobenzol (HC Violet Nr. 1), 1-Amino-2-nitro-4-[(2,3-dihydroxypropyl)amino]-5-chlor-benzol (HC Red Nr. 10), 2-(4- Amino-2-nitroani!ino)-benzoesaure, 6-Nitro-2,5-diaminopyridin, 2-Amino-6-chlor-4-nitrophenol, 1- Amino-2-(3-nitrophenylazo)-7-phenylazo-8-naphthol-3,6-disulfonsaure Dinatriumsalz (Acid blue Nr. 29), 1 -Amino-2-(2-hydroxy-4-nitrophenylazo)-8-naphthol-3,6-disulfonsaure Dinatriumsalz (Palatinchrome green), 1 -Amino-2-(3-chlor-2-hydroxy-5-nitrophenylazo)-8-naphthol-3,6- disulfonsäure Dinatriumsalz (Gallion), 4-Amino-4'-nitrostilben-2,2'-disulfonsäure Dinatriumsalz, 2,4-Diamino-3',5'-dinitro-2'-hydroxy-5-methyl-azobenzol (Mordant brown 4), 4'-Amino-4- nitrodiphenylamin-2-sulfonsäure, 4'-Amino-3'-nitrobenzophenon-2-carbonsäure, 1-Amino-4-nitro- 2-(2-nitrobenzylidenamino)-benzol, 2-[2-(Diethylamino)ethylamino]-5-nitroanilin, 3-Amino-4-hydro- xy-5-nitrobenzolsulfonsäure, 3-Amino-3'-nitrobiphenyl, 3-Amino-4-nitro-acenaphthen, 2-Amino-1- nitronaphthalin, 5-Amino-6-nitrobenzo-1 ,3-dioxol, Aniline, insbesondere Nitrogruppen-haltige Aniline, wie 4-Nitroanilin, 2-Nitroanilin, 1 ,4-Diamino-2-nitrobenzol, 1 ,2-Diamino-4-nitrobenzol, 1- Amino-2-methyl-6-nitrobenzol, 4-Nitro-1 ,3-phenylendiamin, 2-Nitro-4-amino-1 -(2-hy- droxyethylamino)-benzol, 2-Nitro-1-amino-4-[bis-(2-hydroxyethyl)-amino]-benzol, 4-Amino-2- nitrodiphenylamin-2'-carbonsäure, 1-Amino-5-chlor-4-(2-hydroyethylamino)-2-nitrobenzol, aromatische Aniline bzw. Phenole mit einem weiteren aromatischen Rest, wie sie in der Formel V dargestellt sind
Figure imgf000028_0001
in der(Diethylaminomethyl) -4-aminophenol, 4-amino-1-hydroxy-2- (2-hydroxyethylaminomethyl) benzene, 1-hydroxy-2-amino-5-methylbenzene, 1-hydroxy-2-amino-6- methylbenzene, 2-amino-5-acetamidophenol, 1,3-dimethyl-2,5-diaminobenzene, 5- (3-hydroxypropylamino) -2-methylphenol, 5-amino-4-methoxy-2-methylphenol, N, N-dimethyl-3-aminophenol, N-cyclopentyl-3-aminophenol, 5-amino-4-fluoro-2-methylphenol, 2,4-diamino-5-fluorotoluene, 2,4-diamino-5- (2 -hydroxyethoxy) -toluene, 2,4-diamino-5-methylphenol, 3,5-diamino-2-methoxy-1-methylbenzene, 2-amino-4- (2-hydroxyethylamino) -anisole, 2,6-bis- (2-hydroxyethylamino) -1-methylbenzene, 1, 3-diamino-2,4-dimethoxybenzene, 3,5-diamino-2-methoxy-toluene, 2-aminobenzoic acid, 3-aminobenzoic acid, A-aminobenzoic acid, 2- Aminophenylacetic acid, 3-aminophenylacetic acid, 4-aminophenylacetic acid, 2,3-diaminobenzoic acid, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,4-diaminobenzoic acid 3,5-diaminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 3 - Amino-4 -hydroxybenzoic acid, 4-amino-3-hydroxy-benzoic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4-hydroxybenzenesulfonic acid, 4-amino-3-hydroxynaphthalene-1-sulfonic acid, 6-amino 7-hydroxynaphthalene-2-sulfonic acid, 7-amino 4-hydroxynaphthalene-2-sulfonic acid, 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid, 3-amino-2-naphthoic acid, 3-aminophthalic acid, 5-aminoisophthalic acid, 1, 3,5-triaminobenzene, 1, 2, 4-triaminobenzene, 1, 2,4,5-tetraaminobenzene, 2,4,5-triaminophenol, pentaaminobenzene, hexaaminobenzene, 2,4,6-triaminoresorcinol, 4,5-diaminobrcatechol, 4,6-diaminopyrogallol, 1 (2-Hydroxy-5-aminobenzyl) -2-imidazolidinone, 4-amino-2 - ((4 - [(5-amino-2-hydroxyphenyl) methyl] -piperazinyl) -methyl) -phenol, 3,5-diamino-4 -hydroxy catechol, 1,4-bis (4-aminophenyl) -1,4-diazacycloheptane, aromatic nitriles such as 2-amino-4-hydroxybenzonitrile, 4-amino-2-hydroxybenzonitrile, 4-aminobenzonitrile, 2,4-diaminobenzonitrile Nitro-containing amino compounds such as 3-amino-6-methylamino-2-nitro-pyridine, picramic acid, [8 - [(4-amino-2-nitrophenyl) -azo] -7-hydroxy-naphth-2-yl] trimethylammonium chloride, [8 - ((4-amino-3-nitrophenyl) azo) -7-hydroxy-naphth-2-yl] -trimethylammonium chloride (Basic Brown 17), 1-hydroxy-2-amino-4 , 6-dinitrobenzene, 1-amino-2-nitro-4- [bis (2-hydroxyethyl) amino] benzene, 1-amino-2 - [(2-hydroxyethyl) amino] -5-nitrobenzene (HC Yellow No 5), 1-amino-2-nitro-4 - [(2-hydroxyethyl) amino] benzene (HC Red No. 7), 2-chloro-5-nitro-N-2-hydroxyethyl-1, 4- phenylenediamine, 1 - [(2-hydroxyethyl) amino] -2-nitro-4-aminobenzene (HC Red No. 3), 4-amino-3-nitrophenol, 4-amino-2-nitrophenol, 6-nitro o-toluidine, 1-amino-3-methyl-4 - [(2-hydroxyethyl) amino] -6-nitrobenzene (HC Violet No. 1), 1-amino-2-nitro-4 - [(2,3- dihydroxypropyl) amino] -5-chloro-benzene (HC Red No. 10), 2- (4-amino-2-nitroani! ino) benzoic acid, 6-nitro-2,5-diaminopyridine, 2-amino-6- Chloro-4-nitrophenol, 1-amino-2- (3-nitrophenylazo) -7-phenylazo-8-naphthol-3,6-disulfonic acid disodium salt (Acid blue No. 29), 1-amino-2- (2-hydroxy 4-nitrophenylazo) -8-naphthol-3,6-disulfonic acid disodium salt (Palatinchrome green), 1-amino-2- (3-chloro-2-hydroxy-5-nitrophenylazo) -8-naphthol-3,6-disulfonic acid Disodium salt (gallium), 4-amino-4'-nitrostilbene-2,2'-disulfo acidic disodium salt, 2,4-diamino-3 ', 5'-dinitro-2'-hydroxy-5-methylazobenzene (Mordant brown 4), 4'-amino-4-nitrodiphenylamine-2-sulfonic acid, 4'-amino 3'-nitrobenzophenone-2-carboxylic acid, 1-amino-4-nitro-2- (2-nitrobenzylideneamino) -benzene, 2- [2- (diethylamino) ethylamino] -5-nitroaniline, 3-amino-4-hydro xy-5-nitrobenzenesulfonic acid, 3-amino-3'-nitrobiphenyl, 3-amino-4-nitro-acenaphthene, 2-amino-1-nitronaphthalene, 5-amino-6-nitrobenzo-1,3-dioxole, aniline, in particular nitro groups-containing anilines, such as 4-nitroaniline, 2-nitroaniline, 1, 4-diamino-2-nitrobenzene, 1, 2-diamino-4-nitrobenzene, 1-amino-2-methyl-6-nitrobenzene, 4-nitro -1, 3-phenylenediamine, 2-nitro-4-amino-1- (2-hydroxyethylamino) -benzene, 2-nitro-1-amino-4- [bis (2-hydroxyethyl) amino] benzene , 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 1-amino-5-chloro-4- (2-hydroxyethylamino) -2-nitrobenzene, aromatic anilines or phenols with a further aromatic radical, as shown in the formula V are shown
Figure imgf000028_0001
in the
R7 für eine Hydroxy- oder eine Aminogruppe, die durch C1-4-Alkyl-, C1-4-Hydroxyalkyl-, C1-4- Alkoxy- oder
Figure imgf000028_0002
substituiert sein kann, steht, R8, R9, R10, R11 und R12 unabhängig voneinander für ein Wasserstoffatom, eine Hydroxy- oder eine Aminogruppe, die durch C1-C4-AIKyI-, CrC-Hydroxyalkyl, C1-C4-AIkOXy-, C1-C4- Aminoalkyl- oder C1-C4-Alkoxy-C1-C4-alkylgruppen substituiert sein kann, stehen, und P für eine direkte Bindung, eine gesättigte oder ungesättigte, ggf. durch Hydroxygruppen substituierte Kohlenstoffkette mit 1 bis 4 Kohlenstoffatomen, eine Carbonyl-, Sulfoxy-, Sulfonyl- oder Iminogruppe, ein Sauerstoff- oder Schwefelatom, oder eine Gruppe mit der Formel VIR 7 represents a hydroxy or amino group represented by C 1-4 alkyl, C 1-4 hydroxyalkyl, C 1-4 alkoxy or
Figure imgf000028_0002
R 8 , R 9 , R 10 , R 11 and R 12 independently represent a hydrogen atom, a hydroxy or an amino group represented by C 1 -C 4 alkyl, C 1 -C 8 hydroxyalkyl, C 1 -AIkOXy- -C 4, C 1 -C 4 - aminoalkyl or C 1 -C 4 -alkoxy-C 1 -C 4 alkyl groups may be substituted, stand, and P is a direct bond, a saturated or unsaturated, optionally hydroxy-substituted carbon chain of 1 to 4 carbon atoms, a carbonyl, sulfoxy, sulfonyl or imino group, an oxygen or sulfur atom, or a group of formula VI
-Q'-(CH2-Q-CH2-Q")O- (VI)-Q '- (CH 2 -Q-CH 2 -Q ") O - (VI)
in derin the
• Q eine direkte Bindung, eine CH2- oder CHOH-Gruppe bedeutet,Q signifies a direct bond, a CH 2 or CHOH group,
• Q' und Q" unabhängig voneinander für ein Sauerstoffatom, eine NR13-Gruppe, worin R13 ein Wasserstoffatom, eine C^-Alkyl- oder eine Hydroxy-C1-4-alkylgruppe, wobei auch beide Gruppen zusammen mit dem Restmolekül einen 5-, 6- oder 7-Ring bilden können, bedeutet, die Gruppe O-(CH2)P-NH oder NH-(CH2)P-O, worin p und p1 2 oder 3 sind, stehen und• Q 'and Q "independently represent an oxygen atom, an NR 13 group in which R 13 represents a hydrogen atom, a C 1-4 alkyl or a hydroxyC 1-4 alkyl group, both of which together with the remainder of the molecule 5-, 6- or 7-membered ring, means the group O- (CH 2 ) P -NH or NH- (CH 2 ) P -O, wherein p and p 1 are 2 or 3, and
• o eine Zahl von 1 bis 4 bedeutet,O is a number from 1 to 4,
wie beispielsweise 4,4'-Diaminostilben und dessen Hydrochlorid, 4,4'-Diaminostilben-2,2'-disulfon- säure-mono- oder -di-Na-Salz, 4-Amino-4'-dimethylaminostilben und dessen Hydrochlorid, 4,4'- Diaminodiphenylmethan, 4,4'-Diaminodiphenylsulfid, 4,4'-Diaminodiphenylsulfoxid, 4,4'- Diaminodiphenylamin, 4,4'-Diaminodiphenylamin-2-sulfonsäure, 4,4'-Diaminobenzophenon, 4,4'- Diaminodiphenylether, 3,3',4,4'-Tetraaminodiphenyl, 3,3',4,4'-Tetraamino-benzophenon, 1 ,3-Bis- (2,4-diaminophenoxy)-propan, 1 ,8-Bis-(2,5-diaminophenoxy)-3,6-dioxaoctan, 1 ,3-Bis-(4-amino- phenylamino)propan, , 1 ,3-Bis-(4-aminophenylamino)-2-propanol, 1 ,3-Bis-[N-(4-aminophenyl)-2- hydroxyethylamino]-2-propanol, N,N-Bis-[2-(4-aminophenoxy)-ethyl]-methylamin, N-Phenyl-1 ,4- phenylendiamin und Bis-(5-amino-2-hydroxyphenyl)-methan. Die vorgenannten Verbindungen können sowohl in freier Form als auch in Form ihrer physiologisch vertraglichen Salze, insbesondere als Salze anorganischer Sauren, wie Salz- oder Schwefelsäure, eingesetzt werden.such as 4,4'-diaminostilbene and its hydrochloride, 4,4'-diaminostilbene-2,2'-disulfonic acid mono- or di-Na salt, 4-amino-4'-dimethylaminostilbene and its hydrochloride, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfoxide, 4,4'-diaminodiphenylamine, 4,4'-diaminodiphenylamine-2-sulfonic acid, 4,4'-diaminobenzophenone, 4,4 ' - Diaminodiphenylether, 3,3 ', 4,4'-tetraaminodiphenyl, 3,3', 4,4'-tetraamino-benzophenone, 1, 3-bis (2,4-diaminophenoxy) -propane, 1, 8-bis - (2,5-diaminophenoxy) -3,6-dioxaoctane, 1,3-bis (4-aminophenylamino) propane, 1,1,3-bis (4-aminophenylamino) -2-propanol, 1, 3 Bis- [N- (4-aminophenyl) -2-hydroxyethylamino] -2-propanol, N, N-bis [2- (4-aminophenoxy) ethyl] methylamine, N-phenyl-1,4-phenylenediamine and bis (5-amino-2-hydroxyphenyl) methane. The abovementioned compounds can be used both in free form and in the form of their physiologically compatible salts, in particular as salts of inorganic acids, such as hydrochloric or sulfuric acid.
Geeignete stickstoffhaltige heterocyclische Verbindungen sind z. B. 2-Aminopyridin, 3- Aminopyridin, 4-Aminopyridin, 2-Amino-3-hydroxy-pyridin, 2,6-Diamino-pyridin, 2,5-Diamino- pyridin, 2-(Aminoethylamino)-5-aminopyridin, 2,3-Diamino-pyridin, 2-Dimethylamino-5-amino- pyridin, 2-Methylamino-3-amino-6-methoxy-pyridin, 2,3-Diamino-6-methoxy-pyridin, 2,6- Dimethoxy-3,5-diamino-pyridin, 2,4,5-Triamino-pyridin, 2,6-Dihydroxy-3,4-dimethylpyridin, N-[2- (2,4-Diaminophenyl)aminoethyl]-N-(5-amino-2-pyridyl)-amin, N-[2-(4-Aminophenyl)aminoethyl]-N- (5-amino-2-pyridyl)-amin, 2,4-Dihydroxy-5,6-diaminopyrimidin, 4,5,6-Triaminopyrimidin, 4-Hydroxy- 2,5,6-triaminopyrimidin, 2-Hydroxy-4,5,6-triaminopyrimidin, 2,4,5,6-Tetraaminopyrimidin, 2-Me- thylamino-4,5,6-triaminopyrimidin, 2,4-Diaminopyrimidin, 4,5-Diaminopyrimidin, 2-Amino-4- methoxy-6-methyl-pyrimidin, 3,5-Diaminopyrazol, 3,5-Diamino-1 ,2,4-triazol, 3-Aminopyrazol, 3- Amino-5-hydroxypyrazol, 1-Phenyl-4,5-diaminopyrazol, 1-(2-Hydroxyethyl)-4,5-diaminopyrazol, 1- Phenyl-3-methyl-4,5-diaminopyrazol, 4-Amino-2,3-dimethyl-1-phenyl-3-pyrazolin-5-on (4- Aminoantipyrin), 1-Phenyl-3-methylpyrazol-5-on, 2-Aminochinolin, 3-Aminochinolin, 8-Amino- chinolin, 4-Aminochinaldin, 2-Aminonicotinsaure, 6-Aminonicotinsaure, 5-Aminoisochinolin, 5- Aminoindazol, 6-Aminoindazol, 5-Aminobenzimidazol, 7-Aminobenzimidazol, 5-Aminobenzo- thiazol, 7-Aminobenzothiazol, 2,5-Dihydroxy-4-morpholino-anilin sowie Indol- und Indolinderivaten, wie 4-Aminoindol, 5-Aminoindol, 6-Aminoindol, 7-Aminoindol, 5,6-Dihydroxyindol, 5,6-Dihy- droxyindolin und 4-Hydroxyindolin. Weiterhin als heterocyclische Verbindungen können erfindungsgemäß die in der DE-U 1-299 08 573 offenbarten Hydroxypyrimidine eingesetzt werden. Die vorgenannten Verbindungen können sowohl in freier Form als auch in Form ihrer physiologisch verträglichen Salze, z. B. als Salze anorganischer Säuren, wie Salz- oder Schwefelsaure, eingesetzt werden.Suitable nitrogen-containing heterocyclic compounds are, for. B. 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-amino-3-hydroxy-pyridine, 2,6-diamino-pyridine, 2,5-diamino-pyridine, 2- (aminoethylamino) -5-aminopyridine, 2,3-diamino-pyridine, 2-dimethylamino-5-amino-pyridine, 2-methylamino-3-amino-6-methoxy-pyridine, 2,3-diamino-6-methoxy-pyridine, 2,6-dimethoxy 3,5-diamino-pyridine, 2,4,5-triamino-pyridine, 2,6-dihydroxy-3,4-dimethyl-pyridine, N- [2- (2,4-diaminophenyl) aminoethyl] -N- (5- amino-2-pyridyl) amine, N- [2- (4-aminophenyl) aminoethyl] -N- (5-amino-2-pyridyl) amine, 2,4-dihydroxy-5,6-diaminopyrimidine, 4, 5,6-triaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4,5,6-tetraaminopyrimidine, 2-methylamino-4,5, 6-triaminopyrimidine, 2,4-diaminopyrimidine, 4,5-diaminopyrimidine, 2-amino-4-methoxy-6-methyl-pyrimidine, 3,5-diaminopyrazole, 3,5-diamino-1,2,4-triazole, 3-aminopyrazole, 3-amino-5-hydroxypyrazole, 1-phenyl-4,5-diaminopyrazole, 1- (2-hydroxyethyl) -4,5-diaminopyrazole, 1-phenyl-3-methyl-4,5-diaminopyrazole, 4-amino-2,3 -dimethyl-1-phenyl-3-pyrazolin-5-one (4-aminoantipyrine), 1-phenyl-3-methylpyrazol-5-one, 2-aminoquinoline, 3-aminoquinoline, 8-aminoquinoline, 4-aminoquinaldine, 2-aminonicotric acid, 6-aminonicotric acid, 5-aminoisoquinoline, 5-aminoindazole, 6-aminoindazole, 5-aminobenzimidazole, 7-aminobenzimidazole, 5-aminobenzothiazole, 7-aminobenzothiazole, 2,5-dihydroxy-4-morpholino-aniline, and the like Indole and indoline derivatives, such as 4-aminoindole, 5-aminoindole, 6-aminoindole, 7-aminoindole, 5,6-dihydroxyindole, 5,6-dihydroxyindoline and 4-hydroxyindoline. Furthermore, as heterocyclic compounds, the hydroxypyrimidines disclosed in DE-U 1-299 08 573 can be used according to the invention. The aforementioned compounds can be used both in free form and in the form of their physiologically acceptable salts, for. B. as salts of inorganic acids, such as hydrochloric or sulfuric acid, are used.
Geeignete aromatische Hydroxyverbindungen sind z. B. 2-Methylresorcin, 4-Methylresorcin, 5- Methylresorcin, 2,5-Dimethylresorcin, Resorcin, 3-Methoxyphenol, Brenzkatechin, Hydrochinon, Pyrogallol, Phloroglucin, Hydroxyhydrochinon, 2-Methoxyphenol, 3-Methoxyphenol, 4- Methoxyphenol, 3-Dimethylaminophenol, 2-(2-Hydroxyethyl)phenol, 3,4-Methylendioxyphenol, 2,4- Dihydroxybenzoesaure, 3,4-Dihydroxybenzoesäure, 2,4-Dihydroxy-phenylessigsäure, 3,4- Dihydroxy-phenylessigsäure, Gallussäure, 2,4,6-Trihydroxybenzoesäure, 2,4,6-Trihydroxyace- tophenon, 2-Chlorresorcin, 4-Chlorresorcin, 1-Naphthol, 1 ,5-Dihydroxynaphthalin, 2,3- Dihydroxynaphthalin, 2,7-Dihydroxynaphthalin, 6-Dimethylamino-4-hydroxy-2-naphthalinsulfon- säure und 3,6-Dihydroxy-2,7-naphthalinsulfonsäure.Suitable aromatic hydroxy compounds are, for. 2-methylresorcinol, 4-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, resorcinol, 3-methoxyphenol, pyrocatechol, hydroquinone, pyrogallol, phloroglucinol, hydroxyhydroquinone, 2-methoxyphenol, 3-methoxyphenol, 4-methoxyphenol, 3 Dimethylaminophenol, 2- (2-hydroxyethyl) phenol, 3,4-methylenedioxyphenol, 2,4-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 2,4-dihydroxy-phenylacetic acid, 3,4-dihydroxyphenylacetic acid, gallic acid, 2,4 , 6-trihydroxybenzoic acid, 2,4,6-trihydroxyace- tophenone, 2-chlororesorcinol, 4-chlororesorcinol, 1-naphthol, 1, 5-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 6-dimethylamino-4 -hydroxy-2-naphthalenesulfonic acid and 3,6-dihydroxy-2,7-naphthalenesulfonic acid.
Die Verbindungen der Komponente A und die Verbindungen der Komponente B werden vorzugsweise in den erfindungsgemäßen Nuanciermitteln jeweils in einer Menge von 0,03 bis 65 mmol, insbesondere von 1 bis 40 mmol, bezogen auf 100 g des gesamten Nuanciermittels, verwendet. Das molare Verhältnis von der Verbindung der Komponente A und der Verbindung der Komponente B kann im Bereich von 0,5 bis 2,0 liegen, wobei vorzugsweise äquimolare Mengen eingesetzt werden. Das eigentliche Nuanciermittel wird bei getrennter Lagerung der Komponenten A und B unmittelbar vor der Anwendung durch Mischen hergestellt.The compounds of component A and the compounds of component B are preferably used in the shading agents according to the invention in each case in an amount of 0.03 to 65 mmol, in particular from 1 to 40 mmol, based on 100 g of the total Nuanciermittels used. The molar ratio of the compound of component A and the compound of component B may range from 0.5 to 2.0, preferably using equimolar amounts. The actual Nuanciermittel is prepared with separate storage of components A and B immediately before use by mixing.
Als Vorstufen naturanaloger Farbstoffe werden bevorzugt solche Indole und Indoline eingesetzt, die mindestens eine Hydroxy- oder Aminogruppe, bevorzugt als Substituent am Sechsring, aufweisen. Diese Gruppen können weitere Substituenten tragen, z. B. in Form einer Veretherung oder Veresterung der Hydroxygruppe oder eine Alkylierung der Aminogruppe. In einer zweiten bevorzugten Ausführungsform enthalten die Färbemittel mindestens ein Indol- und/oder Indolinderivat.As 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. Example in the form of etherification or esterification of the hydroxy group or alkylation of the amino group. In a second preferred embodiment, the colorants contain at least one indole and / or indoline derivative.
Besonders gut als Vorstufen naturanaloger Farbstoffe geeignet sind Derivate des 5,6- Dihydroxyindolins der Formel (VIIa),Particularly suitable precursors of naturally-analogous dyes are derivatives of 5,6-dihydroxyindoline of the formula (VIIa),
Figure imgf000030_0001
in der unabhängig voneinander
Figure imgf000030_0001
in the independently of each other
G19 steht für Wasserstoff, eine d-C4-Alkylgruppe oder eine Ci-Cj-Hydroxy-alkylgruppe,G 19 is hydrogen, a C 1 -C 4 -alkyl group or a C 1 -C -hydroxyalkyl group,
G20 steht für Wasserstoff oder eine -COOH-Gruppe, wobei die -COOH-Gruppe auch als Salz mit einem physiologisch verträglichen Kation vorliegen kann,G 20 is hydrogen or a -COOH group, where the -COOH group may also be present as a salt with a physiologically compatible cation,
G2i steht für Wasserstoff oder eine Ci-C4-Alkylgruppe,G 2 i is hydrogen or a C 1 -C 4 -alkyl group,
G22 steht für Wasserstoff, eine CVCU-Alkylgruppe oder eine Gruppe -CO-G24, in der G24 steht für eine CrC^Alkylgruppe, undG 22 is hydrogen, a CVCU alkyl group or a group -CO-G 24 in which G 24 is a C 1 -C 4 alkyl group, and
G23 steht für eine der unter G22 genannten Gruppen, sowie physiologisch verträgliche Salze dieser Verbindungen mit einer organischen oder anorganischen Säure.G 23 stands for one of the groups mentioned under G 22 , as well as physiologically tolerable salts of these compounds with an organic or inorganic acid.
Besonders bevorzugte Derivate des Indolins sind das 5,6-Dihydroxyindolin, N-Methyl-5,6- dihydroxyindolin, N-Ethyl-5,6-dihydroxyindolin, N-Propyl-5,6-dihydroxyindolin, N-Butyl-5,6- dihydroxyindolin, 5,6-Dihydroxyindolin-2-carbon-säure sowie das 6-Hydroxyindolin, das 6- Aminoindolin und das 4-Aminoindolin. Besonders hervorzuheben sind innerhalb dieser Gruppe N-Methyl-5,6-dihydroxyindolin, N-Ethyl- 5,6-dihydroxyindolin, N-Propyl-5,6-dihydroxyindolin, N-Butyl-5,6-dihydroxyindolin und insbesondere das 5,6-Dihydroxyindolin.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. Particularly noteworthy within this group are 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.
Als Vorstufen naturanaloger Farbstoffe hervorragend geeignet sind weiterhin Derivate des 5,6- Dihydroxyindols der Formel (VIIb),Also suitable as precursors of naturally-analogous dyes are derivatives of the 5,6-dihydroxyindole of the formula (VIIb),
Figure imgf000031_0001
Figure imgf000031_0001
in der unabhängig voneinanderin the independently of each other
G25 steht für Wasserstoff, eine Ci-C4-Alkylgruppe oder eine d-C^Hydroxyalkylgruppe,G 25 is hydrogen, a C 1 -C 4 -alkyl group or a C 1 -C 4 -hydroxyalkyl group,
G26 steht für Wasserstoff oder eine -COOH-Gruppe, wobei die -COOH-Gruppe auch als Salz mit einem physiologisch vertraglichen Kation vorliegen kann,G 26 is hydrogen or a -COOH group, where the -COOH group may also be present as a salt with a physiologically compatible cation,
G27 steht für Wasserstoff oder eine CrC4-Alkylgruppe,G 27 is hydrogen or a C r C 4 -alkyl group,
G28 steht für Wasserstoff, eine Ci-C4-Alkylgruppe oder eine Gruppe -CO-G30, in der G30 steht für eine Ci-C4-Alkylgruppe, undG 28 is hydrogen, a C 1 -C 4 -alkyl group or a group -CO-G 30 in which G 30 is a C 1 -C 4 -alkyl group, and
G29 steht für eine der unter G28 genannten Gruppen, sowie physiologisch verträgliche Salze dieser Verbindungen mit einer organischen oder anorganischen Säure.G 29 is one of the groups mentioned under G 28 , as well as physiologically acceptable salts of these compounds with an organic or inorganic acid.
Besonders bevorzugte Derivate des Indols sind 5,6-Dihydroxyindol, N-Methyl-5,6-dihydroxyindol, N-Ethyl-5,6-dihydroxyindol, N-Propyl-5,6-dihydroxyindol, N-Butyl-5,6-dihydroxyindol, 5,6- Dihydroxyindol-2-carbonsäure, 6-Hydroxyindol, 6-Aminoindol und 4-Aminoindol.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.
Innerhalb dieser Gruppe hervorzuheben sind N-Methyl-5,6-dihydroxyindol, N-Ethyl-5,6- dihydroxyindol, N-Propyl-5,6-dihydroxyindol, N-Butyl-5,6-dihydroxyindol sowie insbesondere das 5,6-Dihydroxyindol.Emphasized within this group are 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.
Die Indolin- und Indol-Derivate können in den erfindungsgemäßen Emulsionen sowohl als freie Basen als auch in Form ihrer physiologisch verträglichen Salze mit anorganischen oder organischen Säuren, z. B. der Hydrochloride, der Sulfate und Hydrobromide, eingesetzt werden. Die Indol- oder Indolin-Derivate sind in diesen üblicherweise in Mengen von 0,05 bis 10 Gew.-%, vorzugsweise 0,2 bis 5 Gew.-% enthalten. In einer weiteren Ausführungsform kann es erfindungsgemäß bevorzugt sein, das Indolin- oder Indolderivat in Färbemitteln in Kombination mit mindestens einer Aminosäure oder einem Oligopeptid einzusetzen. Die Aminosäure ist vorteilhafterweise eine α-Aminosäure; ganz besonders bevorzugte α-Aminosäuren sind Arginin, Ornithin, Lysin, Serin und Histidin, insbesondere Arginin.The indoline and indole derivatives can be used in the emulsions of the invention both as free bases and in the form of their physiologically acceptable salts with inorganic or organic acids, for. As the hydrochlorides, sulfates and hydrobromides are used. The indole or indoline derivatives are usually contained in these in amounts of 0.05 to 10 wt .-%, preferably 0.2 to 5 wt .-%. In a further embodiment, it may be preferred according to the invention to use the indoline or indole derivative in colorants in combination with at least one amino acid or an oligopeptide. The amino acid is advantageously an α-amino acid; Very particularly preferred α-amino acids are arginine, ornithine, lysine, serine and histidine, in particular arginine.
Bevorzugte direktziehende Farbstoffe, die in den erfindungsgemäßen Mitteln als farbgebende Komponente Verwendung finden, sind Nitrophenylendiamine, Nitroaminophenole, Azofarbstoffe, Anthrachinone oder Indophenole. Bevorzugte direktziehende Farbstoffe sind die unter den internationalen Bezeichnungen bzw. Handelsnamen HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, Acid Yellow 1 , Acid Yellow 10, Acid Yellow 23, Acid Yellow 36, HC Orange 1 , Disperse Orange 3, Acid Orange 7, HC Red 1, HC Red 3, HC Red 10, HC Red 11 , HC Red 13, Acid Red 33, Acid Red 52, HC Red BN, Pigment Red 57:1 , HC Blue 2, HC Blue 12, Disperse Blue 3, Acid Blue 7, Acid Green 50, HC Violet 1 , Disperse Violet 1 , Disperse Violet 4, Acid Violet 43, Disperse Black 9, Acid Black 1 , und Acid Black 52 bekannten Verbindungen sowie 1 ,4-Diamino-2-nitrobenzol, 2-Amino-4-nitrophenol, 1 ,4-Bis-(ß-hydroxyethyl)amino-2-nitrobenzol, 3- Nitro-4-(ß-hydroxyethyl)aminophenol, 2-(2'-Hydroxyethyl)amino-4,6-dinitrophenol, 1-(2'-Preferred substantive dyes which are used in the compositions according to the invention as a coloring component are 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 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 (β-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (β-hydroxyethyl) aminophenol, 2- 2'-hydroxyethyl) amino-4,6-dinitrophenol, 1- (2'-
Hydroxyethyl)amino-4-methyl-2-nitrobenzol, 1-Amino-4-(2'-hydroxyethyl)amino-5-chlor-2- nitrobenzol, 4-Amino-3-nitrophenol, 1-(2'-Ureidoethyl)amino-4-nitrobenzol, 4-Amino-2-nitrodiphe- nylamin-2'-carbonsäure, 6-Nitro-1 ,2,3,4-tetrahydrochinoxalin, 2-Hydroxy-1 ,4-naphthochinon, Pikraminsäure und deren Salze, 2-Amino-6-chloro-4-nitrophenol, 4-Ethylamino-3- nitrobenzoesäure und 2-Chloro-6-ethylamino-1-hydroxy-4-nitrobenzol.Hydroxyethyl) amino-4-methyl-2-nitrobenzene, 1-amino-4- (2'-hydroxyethyl) amino-5-chloro-2-nitrobenzene, 4-amino-3-nitrophenol, 1- (2'-ureidoethyl) amino-4-nitrobenzene, 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone, picramic acid and its salts, 2-Amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene.
Ferner können die erfindungsgemäßen Mittel einen kationischen direktziehenden Farbstoff enthalten. Besonders bevorzugt sind dabeiFurthermore, the agents according to the invention may contain a cationic substantive dye. Particularly preferred are
(a) kationische Triphenylmethanfarbstoffe, wie beispielsweise Basic Blue 7, Basic Blue 26, Basic Violet 2 und Basic Violet 14,(a) cationic triphenylmethane dyes such as Basic Blue 7, Basic Blue 26, Basic Violet 2 and Basic Violet 14,
(b) aromatischen Systeme, die mit einer quaternären Stickstoffgruppe substituiert sind, wie beispielsweise Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 und Basic Brown 17, sowie(b) 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
(c) direktziehende Farbstoffe, die einen Heterozyklus enthalten, der mindestens ein quaternäres Stickstoffatom aufweist, wie sie beispielsweise in der EP-A2-998 908, auf die an dieser Stelle explizit Bezug genommen wird, in den Ansprüchen 6 bis 11 genannt werden.(c) substantive dyes containing a heterocycle having at least one quaternary nitrogen atom, as mentioned, for example, in EP-A2-998 908, which is incorporated herein by reference, in claims 6 to 11.
Bevorzugte kationische direktziehende Farbstoffe der Gruppe (c) sind insbesondere die folgenden Verbindungen:
Figure imgf000033_0001
Preferred cationic substantive dyes of group (c) are in particular the following compounds:
Figure imgf000033_0001
CH3SO4 ' CH 3 SO 4 '
Figure imgf000033_0002
Figure imgf000033_0002
Cl" Cl "
Figure imgf000033_0003
Figure imgf000034_0001
Figure imgf000033_0003
Figure imgf000034_0001
Die Verbindungen der Formeln (DZ1), (DZ3) und (DZ5), die auch unter den Bezeichnungen Basic Yellow 87, Basic Orange 31 und Basic Red 51 bekannt sind, sind ganz besonders bevorzugte kationische direktziehende Farbstoffe der Gruppe (c).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).
Die kationischen direktziehenden Farbstoffe, die unter dem Warenzeichen Arianor® vertrieben werden, sind erfindungsgemäß ebenfalls ganz besonders bevorzugte kationische direktziehende Farbstoffe.The cationic direct dyes, which are sold under the trademark Arianor ® are, according to the invention also very particularly preferred cationic direct dyes.
Die erfindungsgemäßen Zusammensetzungen enthalten die direktziehenden Farbstoffe bevorzugt in einer Menge von 0,01 bis 20 Gew.-%, bezogen auf das anwendungsbereite Mittel.The compositions according to the invention preferably contain the substantive dyes in an amount of from 0.01 to 20% by weight, based on the ready-to-use agent.
Weiterhin können die erfindungsgemäßen Zubereitungen auch in der Natur vorkommende Farbstoffe wie sie beispielsweise in Henna rot, Henna neutral, Henna schwarz, Kamillenblüte, Sandelholz, schwarzem Tee, Faulbaumrinde, Salbei, Blauholz, Krappwurzel, Catechu, Sedre und Alkannawurzel enthalten sind, enthalten.Furthermore, 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.
Es ist nicht erforderlich, dass die Oxidationsfarbstoffvorprodukte oder die direktziehenden Farbstoffe jeweils einheitliche Verbindungen darstellen. Vielmehr können in den erfindungsgemäßen Zusammensetzungen, bedingt durch die Herstellungsverfahren für die einzelnen Farbstoffe, in untergeordneten Mengen noch weitere Komponenten enthalten sein, soweit diese nicht das Farbeergebnis nachteilig beeinflussen oder aus anderen Gründen, z.B. toxikologischen, ausgeschlossen werden müssen.It is not necessary for the oxidation dye precursors or the direct dyes to be in each case homogeneous compounds. Rather, in the inventive Compositions, due to the production process for the individual dyes, be contained in minor amounts of other components, as far as they do not adversely affect the color result or other reasons, such as toxicological, must be excluded.
Bezüglich weiterer fakultativer Komponenten sowie die eingesetzten Mengen dieser Komponenten wird ausdrücklich auf die dem Fachmann bekannten einschlägigen Handbücher, z. B. Kh. Schrader, Grundlagen und Rezepturen der Kosmetika, 2. Auflage, Hüthig Buch Verlag, Heidelberg, 1989, verwiesen.With regard to further optional components as well as the amounts of these components used, reference is expressly made to the relevant manuals known to the person skilled in the art, eg. B. Kh. Schrader, bases and formulations of cosmetics, 2nd edition, Hüthig book publisher, Heidelberg, 1989, referenced.
Wenn die erfindungsgemäße Emulsion Oxidationsfarbstoffvorprodukte oder insbesondere Vorstufen eines naturanalogen Farbstoffs auf Indol- bzw. Indolin-Basis, enthält, kann die eigentliche oxidative Färbung der Fasern grundsätzlich mit Luftsauerstoff erfolgen. Bevorzugt wird jedoch ein von Luft verschiedenes chemisches Oxidationsmittel eingesetzt, besonders dann, wenn neben der Färbung ein Aufhelleffekt der natürlichen Pigmente des menschlichen Haars gewünscht ist. Dieser Aufhelleffekt kann unabhängig von der Färbemethode gewünscht sein. Die Gegenwart von Oxidationsfarbstoffvorprodukten ist demnach keine zwingende Voraussetzung für einen Einsatz von chemischen Oxidationsmitteln in den erfindungsgemäßen Emulsionen. Als chemisches Oxidationsmittel kommt insbesondere Wasserstoffperoxid und/oder mindestens ein Anlagerungsprodukt davon, insbesondere an anorganische oder organische Verbindungen, wie beispielsweise Natriumperborat, Natriumpercarbonat, Magnesiumpercarbonat,If the emulsion according to the invention contains oxidation dye precursors or in particular precursors of a nature-analogous dye based on indole or indoline, the actual oxidative dyeing of the fibers can in principle be carried out with atmospheric oxygen. However, preference is given to using a chemical oxidizing agent other than air, especially when, in addition to the coloring, a whitening effect of the natural pigments of the human hair is desired. This lightening effect may be desired regardless of the staining method. The presence of oxidation dye precursors is therefore not a mandatory requirement for the use of chemical oxidants in the emulsions according to the invention. As a chemical oxidizing agent is in particular hydrogen peroxide and / or at least one addition product thereof, in particular to inorganic or organic compounds such as sodium perborate, sodium percarbonate, magnesium percarbonate,
Natriumpercarbamid, Polyvinylpyrrolidon n H2O2 (n ist eine positive ganze Zahl größer 0), Harnstoffperoxid und Melaminperoxid, dem Nuanciermittel zugesetzt, in Frage. Das eigentliche Färbemittel wird bei getrennter Lagerung der Farbstoffvorprodukte in der erfindungsgemäßen Emulsion und des Oxidationsmittels unmittelbar vor der Anwendung durch Mischen hergestellt.Sodium percarbamide, polyvinylpyrrolidone n H 2 O 2 (n is a positive integer greater than 0), urea peroxide and melamine peroxide added to the shading agent in question. The actual colorant is prepared by separate storage of dye precursors in the emulsion of the invention and the oxidizing agent immediately before use by mixing.
Erfindungsgemäß kann aber die Emulsion auch zusammen mit einem Katalysator auf das Haar aufgebracht werden, der die Oxidation der Farbstoffvorprodukte, z.B. durch Luftsauerstoff, aktiviert. Solche Katalysatoren sind z.B. Metallionen, lodide, Chinone oder bestimmte Enzyme.However, according to the invention, the emulsion may also be applied to the hair together with a catalyst which promotes the oxidation of the dye precursors, e.g. by atmospheric oxygen, activated. Such catalysts are e.g. Metal ions, iodides, quinones or certain enzymes.
Geeignete Metallionen sind beispielsweise Zn2+, Cu2+, Fe2+, Fe3+, Mn2+, Mn4+, Li+, Mg2+, Ca2+ und Al3+. Besonders geeignet sind dabei Zn2+, Cu2+ und Mn2+. Die Metallionen können prinzipiell in der Form eines beliebigen, physiologisch verträglichen Salzes oder in Form einer Komplexverbindung eingesetzt werden. Bevorzugte Salze sind die Acetate, Sulfate, Halogenide, Lactate und Tartrate. Durch Verwendung dieser Metallsalze kann sowohl die Ausbildung der Färbung beschleunigt als auch die Farbnuance gezielt beeinflusst werden.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. By using these metal salts, both the formation of the dyeing can be accelerated and the color shade can be specifically influenced.
Geeignete Enzyme sind z.B. Peroxidasen, die die Wirkung geringer Mengen an Wasserstoffperoxid deutlich verstärken können. Weiterhin sind solche Enzyme erfindungsgemäß geeignet, die mit Hilfe von Luftsauerstoff die Oxidationsfarbstoffvorprodukte direkt oxidieren, wie beispielsweise die Laccasen, oder in situ geringe Mengen Wasserstoffperoxid erzeugen und auf diese Weise die Oxidation der Farbstoffvorprodukte biokatalytisch aktivieren. Besonders geeignete Katalysatoren für die Oxidation der Farbstoffvorläufer sind die sogenannten 2- Elektronen-Oxidoreduktasen in Kombination mit den dafür spezifischen Substraten, z.B.Suitable enzymes include peroxidases, which can significantly enhance the effect of small amounts of hydrogen peroxide. Furthermore, such enzymes are according to the invention suitable, which directly oxidize the oxidation dye precursors with the aid of atmospheric oxygen, such as the laccases, or in situ produce small amounts of hydrogen peroxide and thus biocatalytically activate the oxidation of the dye precursors. Particularly suitable catalysts for the oxidation of the dye precursors are the so-called 2-electron oxidoreductases in combination with the specific substrates, eg
Pyranose-Oxidase und z.B. D-Glucose oder Galactose,Pyranose oxidase and e.g. D-glucose or galactose,
Glucose-Oxidase und D-Glucose,Glucose oxidase and D-glucose,
Glycerin-Oxidase und Glycerin,Glycerol oxidase and glycerin,
Pyruvat-Oxidase und Benztraubensäure oder deren Salze, - Alkohol-Oxidase und Alkohol (MeOH, EtOH),Pyruvate oxidase and pyruvic acid or its salts, - alcohol oxidase and alcohol (MeOH, EtOH),
Lactat-Oxidase und Milchsäure und deren Salze,Lactate oxidase and lactic acid and their salts,
Tyrosinase-Oxidase und Tyrosin,Tyrosinase oxidase and tyrosine,
Uricase und Harnsäure oder deren Salze,Uricase and uric acid or their salts,
Cholinoxidase und Cholin,Choline oxidase and choline,
Aminosäure-Oxidase und Aminosäuren.Amino acid oxidase and amino acids.
Bei einer Anwendung von chemischen Oxidationsmitteln wird das eigentliche Färbemittel zweckmäßigerweise unmittelbar vor der Anwendung durch Mischung der Zubereitung des chemischen Oxidationsmittels (Oxidationskomponente) mit der erfindungsgemäßen Emulsion, enthaltend die farbgebenden Komponenten, hergestellt.In an application of chemical oxidants, the actual colorant is conveniently prepared immediately prior to use by mixing the preparation of the chemical oxidant (oxidation component) with the emulsion of the invention containing the coloring components.
Die Anwendungstemperaturen können in einem Bereich zwischen 15 und 40 0C liegen. Nach einer Einwirkungszeit von 5 bis 45 Minuten wird das Haarfärbemittel durch Ausspülen von dem zu färbenden Haar entfernt. Das Nachwaschen mit einem Shampoo entfällt.The application temperatures can be in a range between 15 and 40 0 C. After a contact time of 5 to 45 minutes, the hair dye is removed by rinsing of the hair to be dyed. The washing with a shampoo is eliminated.
Insbesondere bei schwer färbbarem Haar kann eine erfindungsgemäße Emulsion gegebenenfalls mit zusätzlichen Farbstoffvorprodukten aber auch ohne vorherige Vermischung mit der Oxidationskomponente auf das Haar aufgebracht werden. Nach einer Einwirkdauer von 20 bis 30 Minuten wird dann - gegebenenfalls nach einer Zwischenspülung - das chemische Oxidationsmittel aufgebracht. Nach einer weiteren Einwirkdauer von 10 bis 20 Minuten wird dann gespült und gewünschtenfalls nachshampooniert. Bei dieser Ausführungsform wird gemäß einer ersten Variante, bei der das vorherige Aufbringen der Farbstoffvorprodukte eine bessere Penetration in das Haar bewirken soll, das entsprechende Mittel auf einen pH-Wert von etwa 4 bis 7 eingestellt. Gemäß einer zweiten Variante wird zunächst eine Luftoxidation angestrebt, wobei das aufgebrachte Mittel bevorzugt einen pH-Wert von 7 bis 10 aufweist. Bei der anschließenden beschleunigten Nachoxidation kann die Verwendung von sauer eingestellten Peroxidisulfat- Lösungen als Oxidationsmittel bevorzugt sein. Die gebrauchsfertigen Färbemittel enthalten die chemischen Oxidationsmittel bevorzugt in einer Menge von 0,5 bis 12,0 Gew.%, insbesondere 6 bis 12 Gew.-%, jeweils bezogen auf das Gewicht des anwendungsbereiten Färbemittels.In particular, in the case of hair which is difficult to dye, an emulsion according to the invention may optionally be applied to the hair with additional dye precursors but also without prior mixing with the oxidation component. After an exposure time of 20 to 30 minutes then - optionally after an intermediate rinse - the chemical oxidant is applied. After a further exposure time of 10 to 20 minutes is then rinsed and nachshampooniert if desired. In this embodiment, according to a first variant, in which the previous application of the dye precursors is intended to effect a better penetration into the hair, the corresponding agent is adjusted to a pH of about 4 to 7. According to a second variant, an air oxidation is initially desired, wherein the applied agent preferably has a pH of 7 to 10. In the subsequent accelerated post-oxidation, the use of acidified Peroxidisulfat- solutions may be preferred as the oxidizing agent. The ready-to-use colorants preferably contain the chemical oxidizing agents in an amount of from 0.5 to 12.0% by weight, in particular from 6 to 12% by weight, based in each case on the weight of the ready-to-use colorant.
Ferner können die erfindungsgemäßen Emulsionen als weitere Hilfs- und Zusatzstoffe Tenside, insbesondere kationische Tenside, Überfettungsmittel, Stabilisatoren, Wachse, Konsistenzgeber, Verdickungsmittel, Kationpolymere, Siliconverbindungen, biogene Wirkstoffe, Antischuppenmittel, Film-bildner, Konservierungsmittel, Hydrotrope, Solubilisatoren, Duftstoffe und dergleichen enthalten.Furthermore, the emulsions according to the invention may contain, as further auxiliaries and additives, surfactants, in particular cationic surfactants, superfatting agents, stabilizers, waxes, consistency regulators, thickeners, cationic polymers, silicone compounds, biogenic agents, antidandruff agents, film formers, preservatives, hydrotropes, solubilizers, fragrances and the like ,
Als oberflächenaktive Stoffe können nichtionische, anionische, kationische und/oder amphotere bzw. amphotere Tenside enthalten sein, deren Anteil an den Mitteln üblicherweise bei etwa 50 bis 99 und vorzugsweise 70 bis 90 Gew.-% beträgt.Surfactants which may be present are nonionic, anionic, cationic and / or amphoteric or amphoteric surfactants, the proportion of which in the compositions is usually from about 50 to 99 and preferably from 70 to 90% by weight.
Typische Beispiele für anionische Tenside sind Seifen, Alkylbenzolsulfonate, Alkansulfonate, Olefinsulfonate, Alkylethersulfonate, Glycerinethersulfonate, α-Methylestersulfonate, SuI- fofettsäuren, Alkylsulfate, Fettalkoholethersulfate, Glycerinethersulfate, Hydroxymischethersulfate, Monoglycerid(ether)sulfate, Fettsäureamid(ether)sulfate, Mono- und Dialkyl-sulfosuccinate, Mono- und Dialkylsulfosuccinamate, Sulfotriglyceride, Amidseifen, Ethercarbonsäuren und deren Salze, Fettsäureisethionate, Fettsäuresarcosinate, Fettsäuretauride, N-Acylaminosäuren, wie beispielsweise Acyllactylate, Acyltartrate, Acylglutamate und Acylaspartate, Alkyloligogluco- sidsulfate, Proteinfettsäurekondensate (insbesondere pflanzliche Produkte auf Weizenbasis) und Alkyl(ether)phosphate. Sofern die anionischen Tenside Polyglycoletherketten enthalten, können diese eine konventionelle, vorzugsweise jedoch eine eingeengte Homologenverteilung aufweisen. Gemäß der zuvor erwähnten Ausführungsform enthalten die erfindungsgemäßen Mittel jedoch bevorzugt kein anionisches Tensid, welches von der Komponente (iii) der erfindungsgemäßen Emulsion verschieden ist.Typical examples of anionic surfactants are soaps, alkylbenzenesulfonates, alkanesulfonates, olefinsulfonates, alkyl ether sulfonates, glycerol ether sulfonates, α-methyl ester sulfonates, fatty acid fatty acids, alkyl sulfates, fatty alcohol ether sulfates, glycerol ether sulfates, hydroxy mixed ether sulfates, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, mono- and dialkyl sulfosuccinates, mono- and dialkylsulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, N-acylamino acids such as acyl lactylates, acyl tartrates, acyl glutamates and acylaspartates, alkyl oligoglucoside sulfates, protein fatty acid condensates (especially wheat-based vegetable products) and alkyl (ether) phosphates. If the anionic surfactants contain polyglycol ether chains, these may have a conventional, but preferably a narrow homolog distribution. However, according to the aforementioned embodiment, the agents according to the invention preferably contain no anionic surfactant which is different from the component (iii) of the emulsion according to the invention.
Erfindungsgemäß können ebenfalls kationische Tenside, insbesondere als Pflegestoff, vom Typ der quartären Ammoniumverbindungen, der Esterquats und/oder der Amidoamine in den erfindungsgemäßen Emulsionen enthalten sein. Bevorzugte quaternäre Ammoniumverbindungen sind Ammoniumhalogenide, insbesondere Chloride und Bromide, wie Alkyltrimethylammonium- chloride, Dialkyldimethylammoniumchloride und Trialkylmethylammoniumchloride, z. B. Cetyltri- methylammoniumchlorid, Stearyltrimethylammoniumchlorid, Distearyldimethylammoniumchlorid, Lauryldimethylammoniumchlorid, Lauryldimethylbenzylammoniumchlorid und Tricetylmethyl- ammoniumchlorid, sowie die unter den INCI-Bezeichnungen Quaternium-27 und Quaternium-83 bekannten Imidazolium-Verbindungen. Die langen Alkylketten der oben genannten Tenside weisen bevorzugt 10 bis 18 Kohlenstoffatome auf. Bei Esterquats handelt es sich um bekannte Stoffe, die sowohl mindestens eine Esterfunktion als auch mindestens eine quartäre Ammoniumgruppe als Strukturelement enthalten. Bevorzugte Esterquats sind quaternierte Estersalze von Fettsäuren mit Triethanolamin, quaternierte Estersalze von Fettsäuren mit Diethanolalkylaminen und quaternierten Estersalzen von Fettsäuren mit 1 ,2-Dihydroxypropyldialkylaminen. Solche Produkte werden beispielsweise unter den Warenzeichen Stepantex®, Dehyquart® und Armocare® vertrieben. Die Produkte Armocare® VGH- 70, ein N,N-Bis(2-Palmitoyloxyethyl)dimethylammoniumchlorid, sowie Dehyquart® F-75, Dehyquart® C-4046, Dehyquart® L80 und Dehyquart® AU-35 sind Beispiele für solche Esterquats.Cationic surfactants, in particular as a care substance, of the quaternary ammonium compound type, the esterquats and / or the amidoamines, may likewise be present in the emulsions according to the invention. Preferred quaternary ammonium compounds are ammonium halides, in particular chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, eg. For example, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride, as well as the imidazolium compounds known under the INCI names Quaternium-27 and Quaternium-83. 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, a N, N-bis (2-palmitoyloxyethyl) dimethylammonium chloride, as well as Dehyquart ® F-75, Dehyquart ® C-4046, Dehyquart ® L80 and Dehyquart ® AU-35 are examples of such esterquats.
Die Alkylamidoamine werden üblicherweise durch Amidierung natürlicher oder synthetischer Fettsäuren und Fettsäureschnitte mit Dialkylaminoaminen hergestellt. Eine erfindungsgemäß besonders geeignete Verbindung aus dieser Substanzgruppe stellt das unter der Bezeichnung Tegoamid® S 18 im Handel erhältliche Stearamidopropyl-dimethylamin dar.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 is that available under the name Tegoamid ® S 18 commercially stearamidopropyl dimethylamine.
Die kationischen Tenside können in den erfindungsgemäßen Emulsionen in Mengen von 0,05 bis 10 Gew.-%, bezogen auf das Gewicht der Emulsion, enthalten sein. Mengen von 0,1 bis 5 Gew.-% sind dabei bevorzugt.The cationic surfactants can be present in the emulsions according to the invention in amounts of from 0.05 to 10% by weight, based on the weight of the emulsion. Amounts of 0.1 to 5 wt .-% are preferred.
Als Überfettungsmittel können Substanzen wie beispielsweise Lanolin und Lecithin sowie polyethoxylierte oder acylierte Lanolin- und Lecithinderivate, Polyolfettsäureester und Fettsäure- alkanolamide verwendet werden, wobei die letzteren gleichzeitig als Schaumstabilisatoren dienen. Als Konsistenzgeber kommen in erster Linie Fettalkohole mit 12 bis 22 und vorzugsweise 16 bis 18 Kohlenstoffatomen in Betracht. Bevorzugt ist eine Kombination dieser Stoffe mit Alkyloligoglucosiden und/oder Fettsäure-N-methyl-glucamiden gleicher Kettenlänge und/oder Polyglycerinpoly-12-hydroxy-stearaten. Geeignete Verdickungsmittel sind beispielsweise Polysaccharide, insbesondere Xanthan-Gum, Guar-Guar, Agar-Agar, Alginate und Tylosen, Carboxymethylcellulose und Hydroxyethylcellulose, ferner höhermolekulareSuperfatting agents which can be used are substances such as lanolin and lecithin, as well as polyethoxylated or acylated lanolin and lecithin derivatives, polyol fatty acid esters and fatty acid alkanolamides, the latter also serving as foam stabilizers. As consistency factors are primarily fatty alcohols having 12 to 22 and preferably 16 to 18 carbon atoms into consideration. A combination of these substances with alkyl oligoglucosides and / or fatty acid N-methyl glucamides of the same chain length and / or polyglycerol poly-12-hydroxy stearates is preferred. Suitable thickening agents are, for example, polysaccharides, in particular xanthan gum, guar guar, agar agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl cellulose, and also higher molecular weight
Polyethylenglycolmono- und -diester von Fettsäuren, Polyacrylate, Polyvinylalkohol und Polyvi- nylpyrrolidon, Tenside wie beispielsweise ethoxylierte Fettsäureglyceride, Ester von Fettsäuren mit Polyolen wie beispielsweise Pentaerythrit oder Trimethylolpropan, Fettalkoholethoxylate mit eingeengter Homologenverteilung oder Alkyloligoglucoside sowie Elektrolyt^ wie Kochsalz und Ammoniumchlorid.Polyethylene glycol mono- and diesters of fatty acids, polyacrylates, polyvinyl alcohol and polyvinylpyrrolidone, surfactants such as ethoxylated fatty acid glycerides, esters of fatty acids with polyols such as pentaerythritol or trimethylolpropane, fatty alcohol ethoxylates with narrow homolog distribution or Alkyloligoglucoside and electrolyte such as sodium chloride and ammonium chloride.
Geeignete kationische Polymere, insbesondere als Pflegestoffe, sind beispielsweise kationische Cellulosederivate, kationische Stärke, Copolymere von Diallylammoniumsalzen und Acrylamiden, quaternierte Vinylpyrrolidon/Vinylimidazol-Polymere wie z.B. Luviquat® (BASF AG, Ludwigshafen/ FRG), Kondensationsprodukte von Polyglycolen und Aminen, quaternierte Kollagenpolypeptide wie beispielsweise Lauryldimonium hydroxypropyl hydrolyzed collagen (Lamequat®L, Grünau GmbH), quaternierte Weizenpolypeptide, Polyethylenimin, kationische Siliconpolymere wie z.B. Amidomethicone oder Dow Corning, Dow Corning Co./US, Copolymere der Adipinsäure und Dimethylaminohydroxypropyldiethylentrimamin (Cartaretine®, Sandoz/CH), Polyaminopolyamide wie z.B. beschrieben in der FR-A 22 52 840 sowie deren vernetzte wasserlöslichen Polymere, kationische Chitinderivate wie beispielsweise quaterniertes Chitosan, gegebenenfalls mikrokristallin verteilt, Kondensationsprodukte aus Dihalogenalkylen wie z.B. Dibrombutan mit Bisdialkylaminen wie z.B. Bis-Dimethylamino-1 ,3-propan, kationischer Guar-Gum wie z.B. Jaguar® CBS, Jaguar® C-17, Jaguar® C-16 der Celanese/US, quaternierte Ammoniumsalz- Polymere wie z.B. Mirapol® A-15, Mirapol® AD-1 , Mirapol® AZ-1 der Miranol/US.Suitable cationic polymers, in particular as care substances, are, for example, cationic cellulose derivatives, cationic starch, copolymers of diallylammonium salts and acrylamides, quaternized vinylpyrrolidone / vinylimidazole polymers such as Luviquat® (BASF AG, Ludwigshafen / FRG), condensation products of polyglycols and amines, quaternized collagen polypeptides such as lauryldimonium hydroxypropyl hydrolyzed collagen (Lamequat®L, Grünau GmbH), quaternized wheat polypeptides, polyethylenimine, cationic silicone polymers such as amidomethicones or Dow Corning, Dow Corning Co./US, copolymers of adipic acid and Dimethylaminohydroxypropyldiethylentrimamin (Cartaretine®, Sandoz / CH), polyaminopolyamides such as described in FR-A 22 52 840 and their crosslinked water-soluble polymers, cationic chitin derivatives such as quaternized chitosan, optionally microcrystalline distributed, condensation products of Dihalogenalkylen such as dibromobutane with bis-dialkylamines such as Bis-dimethylamino-1,3-propane, cationic guar gum such as Jaguar® CBS, Jaguar® C-17, Jaguar® C-16 from Celanese / US, quaternized ammonium salt polymers such as Mirapol® A-15, Mirapol® AD-1, Mirapol® AZ-1 from Miranol / US.
Wenn die erfindungsgemäßen Emulsionen als Träger für Oxidationsfarbstoffvorprodukte fungiert, ist es im Rahmen eines 2-Komponentensystems bevorzugt, die erfindungsgemäße Emulsion in einem Vorratsbehältnis 1 zu konfektionieren. Eine oxidationsmittelhaltige Zubereitung wird in einem Vorratsbehältnis 2 konfektioniert.When the emulsions according to the invention act as a carrier for oxidation dye precursors, it is preferred in the context of a 2-component system to prepare the emulsion according to the invention in a storage container 1. An oxidant-containing preparation is packaged in a storage container 2.
Bevorzugt sieht mindestens eines der Vorratsbehältnisse 1 bzw. 2 die Zugabe einer der beiden Komponenten zu der jeweils anderen vor. Zu diesem Zweck können beide Vorratsbehältnisse, beispielsweise durch stecken oder schrauben, miteinander verbunden werden, wobei durch diesen Vorgang eine räumliche Verbindung beider Vorratsbehältnisse geschaffen und ein Übergang der Komponenten von einem in das andere Vorratsbehältnis ermöglicht wird. Nach Zusammenbringen beider Komponenten im geeigneten Vorratsbehältnis wird eine Mischung durch Schütteln hergestellt.At least one of the storage containers 1 or 2 preferably provides for the addition of one of the two components to the other. For this purpose, both storage containers, for example, by plugging or screwing, are connected to each other, being created by this process, a spatial connection of the two storage containers and a transition of the components is made possible from one to the other storage container. After combining both components in a suitable storage container, a mixture is prepared by shaking.
Beide Vorratsbehältnisse können auch räumlich getrennte Kammern in einem Mehrkammergefäß sein, wobei sich vor, während oder nach der Entnahme die getrennt konfektionierten Komponenten mischen.Both storage containers can also be spatially separate chambers in a multi-chamber vessel, wherein before, during or after the removal mix the separately assembled components.
Die beiden Komponenten können jedoch ebenso aus den jeweiligen Vorratsbehältnissen zur Mischung in eine Anmischschale gegeben werden.However, the two components can also be given from the respective storage containers for mixing in a mixing bowl.
Gleiches gilt für 2-Komponentensysteme des Oxofärbesystems. Hier wird bevorzugt eine Zusammensetzung, enthaltend mindestens ein Oxofarbstoffvorprodukt der Komponente 1 im Vorratsbehältnis 1 , sowie eine Zusammensetzung, enthaltend mindestens ein Oxofarbstoffvorprodukt der Komponente 2 im Vorratsbehältnis 2 konfektioniert. Ein zweiter Gegenstand der Erfindung ist ein Verfahren zur Herstellung der erfindungsgemäßen Emulsion des ersten Erfindungsgegenstandes, in demThe same applies to 2-component systems of the oxo dyeing system. Here, preferably, a composition comprising at least one Oxofarbstoffvorprodukt of component 1 in the storage container 1, and a composition containing at least one Oxofarbstoffvorprodukt the component 2 in the storage container 2 made up. A second object of the invention is a process for the preparation of the emulsion according to the invention of the first subject of the invention, in which
(1) in einem ersten Schritt mindestens ein ölkörper auf eine Temperatur oberhalb der Phaseninversionstemperatur erwärmt wird und mindestens ein Emulgator zugegeben wird,(1) in a first step, at least one oil body is heated to a temperature above the phase inversion temperature and at least one emulsifier is added,
(2) diese Mischung wird unter Rühren in einem zweiten Schritt in Wasser gegeben, wobei das Wasser ebenfalls oberhalb der Phaseninversionstemperatur temperiert ist,(2) this mixture is added with stirring in a second step in water, wherein the water is also heated above the phase inversion temperature,
(3) die Mischung des zweiten Schritts in einem dritten Schritt auf eine Temperatur unterhalb der Phaseninversionstemperatur abgekühlt wird,(3) the mixture of the second step is cooled in a third step to a temperature below the phase inversion temperature,
(4) gegebenenfalls in einem vierten Schritt mindestens eine Aktivsubstanz, bevorzugt in gelöster Form, zugegeben wird wobei während mindestens eines der vorangegangenen Schritte oder dazwischen mindestens ein anionisches Alkyloligoglucosid-Derivat und/oder mindestens ein anionisches Alkenyloligoglucosid-Derivat zugegeben wird.(4) optionally in a fourth step, at least one active substance, preferably in dissolved form, is added wherein during at least one of the preceding steps or in between at least one anionic alkyl oligoglucoside derivative and / or at least one anionic alkenyl oligoglucoside derivative is added.
Das anionische Alkyloligoglucosid-Derivat bzw. anionische Alkenyloligoglucosid-Derivat kann dabei bevorzugt zwischen den Schritten (1 ) und (2), zwischen den Schritten (2) und (3), in Schritt (3), zwischen Schritt (3) und (4), in Schritt (4) und/oder nach Schritt (4) zugegeben werden. Erfindungsgemäß besonders bevorzugt ist es, mindestens ein anionisches Alkyloligoglucosid- Derivat und/oder mindestens ein anionisches Alkenyloligoglucosid-Derivat zwischen den Schritten (1) und (2), zwischen den Schritten (2) und (3) und/oder in Schritt (3) zuzugeben.The anionic alkyl oligoglucoside derivative or anionic alkenyl oligoglucoside derivative may preferably be added between steps (1) and (2), between steps (2) and (3), in step (3), between step (3) and (4 ), in step (4) and / or after step (4). According to the invention, it is particularly preferred to use at least one anionic alkyl oligoglucoside derivative and / or at least one anionic alkenyl oligoglucoside derivative between steps (1) and (2), between steps (2) and (3) and / or in step (3). admit.
Ein dritter Gegenstand der Erfindung ist die Verwendung der Emulsion des ersten Erfindungsgegenstandes als Reinigungsmittel für Haut und/oder Haare.A third object of the invention is the use of the emulsion of the first subject of the invention as a cleanser for skin and / or hair.
Ein vierter Gegenstand der Erfindung ist die Verwendung der Emulsion des ersten Erfindungsgegenstandes enthaltend zusätzlich mindestens eine farbgebende Komponente als Reinigungs- und Farbveränderungsmittel für keratinhaltige Fasern, insbesondere menschliche Haare.A fourth subject of the invention is the use of the emulsion of the first subject of the invention additionally containing at least one coloring component as a cleaning and color-changing agent for keratin-containing fibers, in particular human hair.
Für die Ausführungsformen der Emulsionen der Erfindungsgegenstände zwei bis vier gilt mutatis mutandis das im ersten Erfindungsgegenstand Gesagte. B e i s p i e l eFor the embodiments of the emulsions of the subject invention two to four applies mutatis mutandis what is said in the first subject of the invention. Examples
Es wurde folgende erfindungsgemäße Emulsion nach der PIT-Methode hergestellt.The following inventive emulsion was prepared by the PIT method.
Tabelle 1 :Table 1 :
Gew.-%Wt .-%
Emulgade® PL 68/50 1 4,4Emulgade PL 68/50 ® 1 4.4
Eumulgin® B2 2 2,1Eumulgin B2 2 ® 2.1
Eumulgin® BA 10 3 1 ,5Eumulgin ® BA 10 3 1 5
Cetiol® OE 4 10,0Cetiol ® OE 4 10.0
Plantapon® LGC UP 5 5,0Plantapon ® LGC UP 5 5.0
Paraffinöl, dünnflüssig 9,0Paraffin oil, fluid 9.0
Parfüm 1 ,0Perfume 1, 0
Wasser ad 100Water ad 100
1 Mischung aus C16- bis C18-Alkyloligoglucosid und C16- bis C18-Fettalkohol im Gewichtsverhältnis von 1 :1 (enthält 1 Gew.-% Glucose und 10 Gew.-% einer Mischung von Ethanol und Wasser im Verhältnis von 1 zu 2) (INCI-Bezeichnung: Cetearyl Glucoside, Cetearyl Alkohol) (Cognis) 1 mixture of C 16 - to C 18 -Alkyloligoglucosid and C 16 - to C 18 fatty alcohol in a weight ratio of 1: 1 (contains 1 wt .-% glucose and 10 wt .-% of a mixture of ethanol and water in the ratio of 1 to 2) (INCI name: Cetearyl Glucoside, Cetearyl Alcohol) (Cognis)
2 Cetylstearylalkohol mit ca. 20 EO-Einheiten (INCI-Bezeichnung: Ceteareth-20) (Cognis) 2 cetylstearyl alcohol with approx. 20 EO units (INCI name: Ceteareth-20) (Cognis)
3 ethoxylierter Behenylalkohol (INCI-Bezeichnung: Beheneth-10) (Cognis) 3 ethoxylated behenyl alcohol (INCI name: Beheneth-10) (Cognis)
4 Dioctylether (INCI-Bezeichnung: Dicaprylylether) (Cognis) 4 dioctyl ether (INCI name: dicaprylyl ether) (Cognis)
5 Alkylpolyglucosid-Carboxylat Natriumsalz; 30 %-ige wässrige Lösung (Cognis) 5 alkyl polyglucoside carboxylate sodium salt; 30% aqueous solution (Cognis)
Zu 40 g der erfindungsgemäßen Emulsion gemäß Tabelle 1 wurden bei Raumtemperatur Oxidationsfarbstoffvorprodukte, Ascorbinsäure, Natriumsulfit, Turpinal® SL und Monoethanolamin gemäß Tabelle 2 gegeben. Man erhielt die in Tabelle 2 aufgeführte Zusammensetzung. To 40 g of the emulsion according to the invention in accordance with Table 1 oxidation dye precursors, ascorbic acid, sodium sulfite, Turpinal SL ® and monoethanolamine were added according to Table 2 at room temperature. The composition listed in Table 2 was obtained.
Tabelle 2: FarbstoffvorproduktträgerTable 2: Dye precursor carrier
Gew.-%Wt .-%
Emulsion gemäß Tabelle 1 40,00 p-Toluylendiamin 1 ,43Emulsion according to Table 1 40.00 p-toluenediamine 1, 43
Resorcin 0,55 m-Aminophenol 0,15Resorcinol 0.55 m-aminophenol 0.15
3-Amino-2-methylamino-6-methoxypyridin 0,043-Amino-2-methylamino-6-methoxypyridine 0.04
Ascorbinsäure 0,50Ascorbic acid 0.50
Natrium sulfit 0,50Sodium sulfite 0.50
Turpinal® SL 6 0,20Turpinal SL ® 6 0.20
Monoethanolamin 8,00Monoethanolamine 8,00
Wasser ad 100Water ad 100
6 1-Hydroxyethan-1 ,1-diphosphonsäure (INCI-Bezeichnung: Etidronic Acid, Aqua (Water)) 6 1-Hydroxyethane-1, 1-diphosphonic acid (INCI name: Etidronic Acid, Aqua (Water))
(Solutia)(Solutia)
Der erfindungsgemäße Farbstoffvorproduktträger der Tabelle 2 ist stabil, dünnflüssig und eignet sich daher hervorragend zur Verwendung in einem Zwei-Komponenten-System. Dazu wurden 50.0 g des Farbstoffvorproduktträgers mit 50.0 g der Entwicklerdispersion gemäß Tabelle 3 in einem Schüttelbehältnis vermischt. Die Mischung der Komponenten verlief schnell und einfach durch schütteln.The dye precursor support of Table 2 of the invention is stable, low viscosity, and therefore, is excellently suited for use in a two component system. For this purpose, 50.0 g of the dye precursor carrier were mixed with 50.0 g of the developer dispersion according to Table 3 in a shaking container. The mixture of components proceeded quickly and easily by shaking.
Tabelle 3: EntwicklerdispersionTable 3: Developer dispersion
Gew.-%Wt .-%
Dipicolinsäure 0,62Dipicolinic acid 0.62
Natriumpyrophosphat 0,03Sodium pyrophosphate 0.03
Turpinal® SL 1,50Turpinal® ® SL 1.50
Texapon® NSO 7 2,00Texapon.RTM ® NSO 7 2.00
Dow Corning DB 110 A 8 0,07Dow Corning DB 110 A 8 0.07
Aculyn® 33 A 9 12,00Aculyn ® 33 A 9 12.00
Wasserstoffperoxid (50 %ige wässrige Lösung) 12,0Hydrogen peroxide (50% aqueous solution) 12.0
Wasser ad 100Water ad 100
Natriumlaurylethersulfat (27 % Aktivsubstanz INCI: Sodium Laureth Sulfate) (Cognis) nniicchhttiioonnooggeennee SSiilliikkoonneemmuullssion (10 Gew.-% Aktivsubstanz) (INCI-Bezeichnung: Dimethicone) (Dow Corning) 9 30 Gew.-% Aktivsubstanz in Wasser (INCI-Bezeichnung: Acrylates Copolymer) (Rohm &Sodium lauryl ether sulfate (27% active ingredient INCI: Sodium Laureth Sulfate) (Cognis) nniicchhttiioonnooggeennee SSiilliikkoonneemmuullssion (10 wt .-% active ingredient) (INCI name: Dimethicone) (Dow Corning) 9 30% by weight of active substance in water (INCI name: Acrylates Copolymer) (Rohm & Co.)
Haas)Haas)
Die resultierende Anwendungsmischung wurde auf eine Testhaarsträhne (Kerling, Naturweiß) aufgetragen. Nach 30 Minuten Einwirkungszeit bei 32 0C wurde das Haar gespült, mit einem üblichen Haarwaschmittel ausgewaschen und anschließend getrocknet. The resulting application mixture was applied to a test hair strand (Kerling, natural white). After 30 minutes exposure time at 32 0 C, the hair was rinsed, washed with a conventional shampoo and then dried.

Claims

P a t e n t a n s p r ü c h e Patent claims
1. Emulsion, die nach der Phaseninversionstemperatur-Methode hergestellt wurde, enthaltend1. An emulsion prepared by the phase inversion temperature method comprising
(i) mindestens einen Emulgator,(i) at least one emulsifier,
(ii) mindestens einen ölkörper,(ii) at least one oily body,
(iii) mindestens ein anionisches Alkyloligoglucosid-Derivat und/oder mindestens ein anionisches Alkenyloligoglucosid-Derivat und (iv) Wasser.(iii) at least one anionic alkyl oligoglucoside derivative and / or at least one anionic alkenyl oligoglucoside derivative and (iv) water.
2. Emulsion nach Anspruch 1 , dadurch gekennzeichnet, daß sie als Emulgator (i) mindestens ein nichtionogenes Tensid enthält.2. Emulsion according to claim 1, characterized in that it contains as emulsifier (i) at least one nonionic surfactant.
3. Emulsion nach einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, daß sie als Emulgator (i) mindestens ein nichtionogenes Tensid aus wenigstens einer der folgenden Gruppen enthält:3. Emulsion according to one of claims 1 or 2, characterized in that it contains as emulsifier (i) at least one nonionic surfactant from at least one of the following groups:
(1) Anlagerungsprodukte von 2 bis 30 Mol Ethylenoxid und/ oder 0 bis 5 Mol Propylenoxid an lineare Fettalkohole mit 8 bis 22 C-Atomen, an Fettsäuren mit 12 bis 22 C-Atomen und an Alkylphenole mit 8 bis 15 C-Atomen in der Alkylgruppe;(1) addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear fatty alcohols having 8 to 22 carbon atoms, to fatty acids having 12 to 22 carbon atoms and to alkylphenols having 8 to 15 carbon atoms in the alkyl group;
(2) C12/18-Fettsäuremono- und -diester von Anlagerungsprodukten von 1 bis 30 Mol Ethylenoxid an Glycerin;(2) C 12/18 fatty acid mono- and diesters of addition products of 1 to 30 moles of ethylene oxide with glycerol;
(3) Glycerinmono- bzw. -diester (Partialglyceride) sowie Sorbitanmono- und -diester, jeweils von gesättigten und/oder ungesättigten Fettsäuren mit 6 bis 22 Kohlenstoffatomen und deren Ethylenoxidanlagerungsprodukte;(3) glycerol mono- or diesters (partial glycerides) as well as sorbitan mono- and diesters, each of saturated and / or unsaturated fatty acids having 6 to 22 carbon atoms and their ethylene oxide addition products;
(4) Alkylmono- und -oligoglykoside mit 8 bis 22 Kohlenstoffatomen im Alkylrest und deren ethoxylierte Analoga; insbesondere Alkyl- bzw. Alkenyl-, Mono- bzw. Oligoglykoside der Formel(4) alkyl mono- and oligoglycosides having 8 to 22 carbon atoms in the alkyl group and their ethoxylated analogs; in particular alkyl or alkenyl, mono- or oligoglycosides of the formula
(5) Anlagerungsprodukte von 15 bis 60 Mol Ethylenoxid an Ricinusöl und/oder gehärtetes Ricinusöl;(5) addition products of 15 to 60 moles of ethylene oxide with castor oil and / or hydrogenated castor oil;
(6) Polyol- und insbesondere Polyglycerinester, wie z.B. Polyglycerinpolyricinoleat, Polyglycerinpoly-12-hydroxystearat oder Polyglycerindimerat. Ebenfalls geeignet sind Gemische von Verbindungen aus mehreren dieser Substanzklassen;(6) polyol and especially polyglycerol esters, e.g. Polyglycerol polyricinoleate, polyglycerol poly-12-hydroxy stearate or polyglycerol dimerate. Also suitable are mixtures of compounds of several of these classes of substances;
(7) Anlagerungsprodukte von 2 bis 15 Mol Ethylenoxid an Ricinusöl und/oder gehärtetes Ricinusöl;(7) addition products of 2 to 15 moles of ethylene oxide with castor oil and / or hydrogenated castor oil;
(8) Partialester auf Basis linearer, verzweigter, ungesättigter bzw. gesättigter C6^- Fettsäuren, Ricinolsäure sowie 12-Hydroxystearinsäure und Glycerin, Polyglycerin, Pentaerythrit, Dipenta-erythrit, Zuckeralkohole (z.B. Sorbit), Alkylglucoside (z.B. Methylglucosid, Butylglucosid, Lauryl-glucosid) sowie Polyglucoside (z.B. Cellulose);(8) partial esters based on linear, branched, unsaturated or saturated C 6 - fatty acids, ricinoleic acid and 12-hydroxystearic acid and glycerol, polyglycerol, Pentaerythritol, dipentaerythritol, sugar alcohols (eg sorbitol), alkyl glucosides (eg methyl glucoside, butyl glucoside, lauryl glucoside) and polyglucosides (eg cellulose);
(9) Trialkylphosphate sowie Mono-, Di- und/oder Tri-PEG-alkylphosphate;(9) trialkyl phosphates and mono-, di- and / or tri-PEG-alkyl phosphates;
(10) Wollwachsalkohole;(10) wool wax alcohols;
(11) Polysiloxan-Polyalkyl-Polyether-Copolymere bzw. entsprechende Derivate;(11) polysiloxane-polyalkyl-polyether copolymers or corresponding derivatives;
(12) Mischester aus Pentaerythrit, Fettsäuren, Citronensäure und Fettalkohol gemäß DE- PS 1165574 und/oder Mischester von Fettsäuren mit 6 bis 22 Kohlenstoffatomen, Methylglucose und Polyolen, vorzugsweise Glycerin sowie(12) mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohol according to DE-PS 1165574 and / or mixed esters of fatty acids having 6 to 22 carbon atoms, methyl glucose and polyols, preferably glycerol and
(13) Polyalkylenglycole.(13) Polyalkylene glycols.
4. Emulsion nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß sie als Emulgator (i) mindestens einen Emulgator der Formel (I)4. Emulsion according to one of claims 1 to 3, characterized in that it comprises as emulsifier (i) at least one emulsifier of the formula (I)
R'-O-(GI)m, (I)R'-O- (GI) m , (I)
enthält, in dercontains, in the
R' eine C6-22-Alkyl- oder C6-22-Alkenylgruppe,R 'is a C 6-22 alkyl or C 6-22 alkenyl group,
Gl eine Glykosideinheit, die sich von einem Zucker mit 5 oder 6 Kohlenstoffatomen ableitet und m eine Zahl von 1 bis 10 bedeuten.Gl is a glycoside unit derived from a sugar having 5 or 6 carbon atoms and m is a number from 1 to 10.
5. Emulsion nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß sie als Emulgator (i) mindestens ein Fettalkoholethoxylat der Formel (II) enthält,5. Emulsion according to one of claims 1 to 4, characterized in that it contains as emulsifier (i) at least one fatty alcohol ethoxylate of the formula (II),
R1(OCH2CH2)nOH (II)R 1 (OCH 2 CH 2 ) n OH (II)
in der R1 für einen linearen oder verzweigten Alkylrest mit 12 bis 22 Kohlenstoffatomen und n für Zahlen von 5 bis 50 steht.in which R 1 is a linear or branched alkyl radical having 12 to 22 carbon atoms and n is a number from 5 to 50.
6. Emulsion nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß sie als Emulgator (i) eine Kombination aus6. Emulsion according to one of claims 1 to 5, characterized in that it comprises as emulsifier (i) a combination of
(11) mindestens einem Fettalkoholethoxylat als Anlagerungsprodukt von 2 bis 30 Mol Ethylenoxid und/ oder 0 bis 5 Mol Propylenoxid an lineare Fettalkohole mit 8 bis 22 C- Atomen, mit(11) at least one fatty alcohol ethoxylate as an adduct of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide with linear fatty alcohols having 8 to 22 carbon atoms, with
(12) mindestens einem Alkyl- und/oder Alkenyloligoglykosid enthält. (12) contains at least one alkyl and / or Alkenyloligoglykosid.
7. Emulsion nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß der ölkörper (ii) ausgewählt wird aus mindestens einem Vertreter aus der Gruppe, bestehend aus7. Emulsion according to one of claims 1 to 6, characterized in that the oil body (ii) is selected from at least one member selected from the group consisting of
Guerbetalkoholen auf Basis von Fettalkoholen mit 6 bis 18 Kohlenstoffatomen,Guerbet alcohols based on fatty alcohols having 6 to 18 carbon atoms,
Estern von linearen C6-C20-Fettsäuren mit linearen C6-C20-Fett-alkoholen,Esters of linear C6-C20 fatty acids with linear C6-C20 fatty alcohols,
Estern von verzweigten C6-C13-Carbonsäuren mit linearen C6-C20-Fettalkoholen,Esters of branched C6-C13 carboxylic acids with linear C6-C20 fatty alcohols,
Estern von linearen C6-C18-Fettsäuren mit verzweigten Alkoholen,Esters of linear C6-C18 fatty acids with branched alcohols,
Estern von linearen und/oder verzweigten Fettsauren mit mehrwertigen Alkoholen und/ oder Guerbetalkoholen,Esters of linear and / or branched fatty acids with polyhydric alcohols and / or Guerbet alcohols,
Triglyceriden auf Basis von C6-C10-Fettsäuren, pflanzlichen ölen, verzweigten primären Alkoholen, substituierten Cyclohexanen,Triglycerides based on C6-C10 fatty acids, vegetable oils, branched primary alcohols, substituted cyclohexanes,
Guerbetcarbonaten,Guerbet,
Dialkylethern und/oder aliphatischen bzw. naph-thenischen Kohlenwasserstoffen.Dialkyl ethers and / or aliphatic or naphthenic hydrocarbons.
8. Emulsion nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß die anionischen Alkyloligoglykosid bzw. anionischen Alkenyloligoglykosid-Derivate (iii) ausgewählt aus Alkyl- und/oder Alkenyl-Oligoglykosidcarboxylaten, -Sulfaten, -phosphaten und/oder -isethionaten, sich von Alkyl- und/oder Alkenyloligoglykosiden der allgemeinen Formel (IV) ableiten,8. Emulsion according to one of claims 1 to 7, characterized in that the anionic alkyloligoglycoside or anionic Alkenyloligoglykosid derivatives (iii) selected from alkyl and / or alkenyl Oligoglykosidcarboxylaten, sulfates, phosphates and / or -isethionaten, itself of alkyl and / or alkenyl oligoglycosides of the general formula (IV),
R-O-(G)P (IV)RO- (G) P (IV)
mit der Bedeutungwith the meaning
R C6-22-Alkyl oder C^-Alkenyl,RC 6-22 alkyl or C ^ alkenyl,
G Glykosideinheit, die sich von einem Zucker mit 5 oder 6 Kohlenstoffatomen ableitet, p Zahl von 1 bis 10.G glycoside unit derived from a sugar with 5 or 6 carbon atoms, p number from 1 to 10.
9. Emulsion nach Anspruch 8, dadurch gekennzeichnet, daß die anionischen Alkyl- und/oder Alkenyl-Oligoglykoside in mindestens einem der Reste G der Formel (IV) mindestens eine Hydroxylgruppe durch9. Emulsion according to claim 8, characterized in that the anionic alkyl and / or alkenyl oligoglycosides in at least one of the radicals G of the formula (IV) at least one hydroxyl group
-O-C2-i2-Alkenylen-COOM,-OC 2 -i 2 -alkenylene COOM,
-O(CH2-)nCOOM,-O (CH 2 -) n COOM,
-OSO3M, -OP(O)(OM)2 oder -0-CH2-CH2-SO3M mit M = H, Alkalimetall oder NH4 ersetzt ist.-OSO 3 M, -OP (O) (OM) 2 or -O-CH 2 -CH 2 -SO 3 M with M = H, alkali metal or NH 4 is replaced.
10. Emulsion nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß sie einen pH- Wert von pH 5 bis pH 12, insbesondere zwischen pH 7 und pH 12, besitzt.10. An emulsion according to any one of claims 1 to 9, characterized in that it has a pH of pH 5 to pH 12, in particular between pH 7 and pH 12.
11. Emulsion nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, daß sie zusätzlich als farbgebende Komponente11. An emulsion according to any one of claims 1 to 10, characterized in that they additionally as a coloring component
(a) mindestens ein Oxidationsfarbstoffvorprodukt vom Typ der Entwicklerkomponenten und gegebenenfalls zusätzlich mindestens eine Kupplerkomponente und/oder(A) at least one oxidation dye precursor of the developer component type and optionally additionally at least one coupler component and / or
(b) mindestens ein Oxofarbstoffvorprodukt und/oder(B) at least one Oxofarbstoffvorprodukt and / or
(c) mindestens einen direktziehenden Farbstoff und/oder(c) at least one substantive dye and / or
(d) mindestens eine Vorstufe naturanaloger Farbstoffe enthält.(D) contains at least one precursor of natural dyes.
12. Verfahren zur Herstellung einer Emulsion gemäß Anspruch 1 , dadurch gekennzeichnet, daß12. A process for the preparation of an emulsion according to claim 1, characterized in that
(1) in einem ersten Schritt mindestens ein ölkörper auf eine Temperatur oberhalb der Phaseninversionstemperatur erwärmt wird und mindestens ein Emulgator zugegeben wird,(1) in a first step, at least one oil body is heated to a temperature above the phase inversion temperature and at least one emulsifier is added,
(2) diese Mischung unter Rühren in einem zweiten Schritt in Wasser gegeben wird, wobei das Wasser ebenfalls oberhalb der Phaseninversionstemperatur temperiert ist,(2) this mixture is added with stirring in a second step in water, wherein the water is also heated above the phase inversion temperature,
(3) die Mischung des zweiten Schritts in einem dritten Schritt auf eine Temperatur unterhalb der Phaseninversionstemperatur abgekühlt wird,(3) the mixture of the second step is cooled in a third step to a temperature below the phase inversion temperature,
(4) gegebenenfalls in einem vierten Schritt mindestens eine Aktivsubstanz, bevorzugt in gelöster Form, zugegeben wird wobei während mindestens eines der vorangegangenen Schritte oder dazwischen mindestens ein anionisches Alkyloligoglucosid-Derivat und/oder mindestens ein anionisches Alkenyloligoglucosid-Derivat zugegeben wird.(4) optionally in a fourth step, at least one active substance, preferably in dissolved form, is added wherein during at least one of the preceding steps or in between at least one anionic alkyl oligoglucoside derivative and / or at least one anionic alkenyl oligoglucoside derivative is added.
13. Verwendung einer Emulsion nach einem der Ansprüche 1 bis 10 als Reinigungsmittel für Haut und/oder Haare. 13. Use of an emulsion according to any one of claims 1 to 10 as a cleanser for skin and / or hair.
14. Verwendung einer Emulsion nach Anspruch 11 als Reinigungs- und Farbveränderungsmittel für keratinhaltige Fasern, insbesondere menschliche Haare. 14. Use of an emulsion according to claim 11 as a cleaning and color-changing agent for keratin-containing fibers, in particular human hair.
PCT/EP2006/010079 2005-11-07 2006-10-19 Washing-active pit emulsions WO2007051527A1 (en)

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