WO2006105853A1

WO2006105853A1 - Thickening of cosmetics having a high electrolyte content

Info

Publication number: WO2006105853A1
Application number: PCT/EP2006/002308
Authority: WO
Inventors: Claudia Brockmann; Horst Höffkes
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 2005-04-06
Filing date: 2006-03-14
Publication date: 2006-10-12
Also published as: DE102005015895A1

Abstract

The invention relates to thickened compositions having a pH value higher than 6 and an increased electrolyte content. According to the invention, the compositions are thickened very effectively by a thickener system containing at least one polymer based on unsaturated carboxylic acids and at least one cationic surfactant. The thickening effect obtained is stable and renders said compositions easy to handle, inter alia, during the application thereof, especially to fibres containing keratin, and increases the durability of the agent when it is applied to pre-determined regions of the fibre.

Description

"Thickening of cosmetics with high electrolyte content"

The invention relates to thickened compositions containing a thickener system containing at least one polymer based on unsaturated carboxylic acids and at least one cationic surfactant, have a pH greater than 6 and have an increased content of electrolyte, and the use of the thickener combination according to the invention for thickening of compositions with a pH greater than pH 6 and an increased electrolyte content.

Basic compositions having an increased electrolyte content can be found to thicken unsatisfactorily with acrylic acid-based polymers. If the respective basic compositions contain, as electrolytes, strong oxidizing agents in the form of inorganic persalts, the thickening effect of the polymers based on unsaturated carboxylic acids is additionally reduced. The rheology of these thickened compositions is still in need of improvement in view of the effectiveness of the thickening and on the stability of the thickening effect. The compositions when applied at selected locations, e.g. different places of a fiber, not lost.

It is therefore an object of the present invention to improve the rheology or the thickening of compositions with increased electrolyte content.

The Applicant has now surprisingly found that compositions with increased electrolyte content can be thickened excellently by a thickener system comprising at least one acrylate-based polymer and at least one cationic surfactant. The thickening is effective and stable over a long period of time. The thickening achieved gives the compositions in use, in particular on keratin-containing fibers, among others, easy handling and increases the fate of the agent when applied to predetermined locations of the fiber. A first subject of the invention is therefore a composition having a pH greater than pH 6 and an electrolyte content of at least 0.01 v / 100 g, preferably at least 0.05 v / 100 g, particularly preferably at least 0.1 v / v, containing! (a) at least one polymer which comprises at least one monomer unit of a

'unsaturated carboxylic acid is formed, and (b)' at least one cationic surfactant.

The electrolyte content is expressed as the product of the valency of the electrolyte (charge number) multiplied by the molar amount in moles of the electrolyte per 100 g of the agent according to the invention. If several electrolytes are contained in the agent according to the invention, the sum. all amounts of electrolyte calculated in the manner previously described over all ¹ electrolytes formed. This electrolyte content carries the unit VaI. It is thus defined that electrolytes are contained in an amount of at least 0.01 VaI, in particular of at least 0.05 VaI, particularly preferably of at least 0.1 VaI, in each case based on 100 g of the composition according to the invention.

By definition, the electrolytes present in the compositions according to the invention are salts of inorganic or organic compounds, which are preferably formed by reaction of an inorganic or organic acid with an inorganic or organic base. According to the invention, a salt is understood as meaning a heteropolar compound in whose crystal lattice at least one type of cation different from hydrogen ions (protons) or at least one type of anion other than hydroxide ions is involved. In this case, strong electrolytes are preferred according to the invention. These are formed from weak bases with strong acids, or strong bases with weak acids. It is particularly preferred if the electrolytes are selected from the group consisting of inorganic salts such as sodium chloride, sodium sulfate, peroxodisulfates of ammonium, sodium or potassium, ammonium sulfate, sodium sulfite and calcium chloride,

Salts which are formed by reaction of organic compounds with organic or inorganic acids, in particular inorganic acids, such as, for example, p-toluenediamino ₂ S0 ₄ , 2,4,5,6-tetraaminopyrimidine-2 H ₂ SO ₄ According to the invention, the electrolytes according to the invention have no surfactant character and no emulsifier properties. In addition, the electrolytes preferably have a molar mass of less than 1000 g / mol.

The polymer present in the composition according to the invention, which is formed as a monomer from at least one unsaturated carboxylic acid, is preferably an anionic polymer. The carboxyl groups of the unsaturated carboxylic acid monomer remain as a side chain after polymerization in the polymer. The polymer according to the invention may be homopolymers or copolymers which are crosslinked or linear. The copolymers can also be present as random, block or graft polymers.

The monomer unit of an unsaturated carboxylic acid is preferably selected from a group consisting of acrylic acid, methacrylic acid, itaconic acid, crotonic acid and maleic acid. The acidic groups may be wholly or partly present as sodium, potassium, ammonium, mono- or triethanolammonium salt. Particularly preferred polymers are selected from the group consisting of carbomer, acrylamide / sodium acrylate copolymer, acrylates / acetoacetoxyethyl methacrylate copolymer, acrylates / beheneth-25 methacrylate copolymer, acrylates / C 10-30 alkyl acrylate crosspolymer, acrylates / ceteth-20 Itaconate Copolymer, Acrylates / Ceteth-20 Methacrylate Copolymer, Acrylates / Laureth-25 Methacrylate Copolymer, Acrylates / Palmeth-25 Acrylate Copolymer, Acrylates / Palmeth-25 Itaconate Copolymer, Acrylates / Steareth-50 Acrylate Copolymer, Acrylates / Steareth-20 Itaconate Copolymer , Acrylates / Steareth-20 Methacrylate Copolymer, Acrylates / Stearyl Methacrylate Copolymer, Acrylates / Vinyl Isodecanoate Crosspolymer, Acrylic Acid / Acrylonitrogen Copolymer, Ammonium Acrylates / Acrylonitrogens Copolymer, Ammonium Acrylates Copolymer, Calcium Potassium Carbomer, DMAPA Acrylates / Acrylic Acid / Acrylonitrogens Copolymer, Ethylene / Sodium Acrylate Copolymer, Octadecenes / MA Copolymer, Sodium Acrylates / Acryloyldim ethyl Taurate Copolymer, Sodium Acrylates / Acrolein Copolymer, Sodium Acrylates / Acrylonitrogen Copolymer, Sodium Acrylates Copolymer, Sodium Acrylates / Vinyl Isodecanoate Crosspolymer, Sodium Acrylate / Vinyl Alcohol Copolymer, Sodium Carbomer, Sodium Isooctylene / MA Copolymer, Sodium Polyacrylate, Sodium Polymethacrylate, Sodium Styrene / Acrylates Copolymer, Sodium Tauride Acrylates / Acrylic Acid / Acrylonitrogens Copolymer and Starch / Acrylates / Acryiamide Copolymer. Very particularly preferred polymers selected from the group consisting of carbomer, acrylamide / sodium acrylate copolymer, acrylates / beheneth-25 methyl acrylate copolymer, acrylates / C 10-30 alkyl acrylate crosspolymer, acrylates / ceteth-20 itaconate copolymer, acrylates / ceteth-20 methacrylate copolymer , Acrylates / Laureth-25 Methacrylate Copolymer, Acrylates / Palmeth-25 Acrylate Copolymer, Acrylates / Palmeth-25 Itaconate Copolymer, Acrylates / Steareth-50 Acrylate Copolymer, Acrylates / Steareth-20 Itaconate 'Copolymer and Acrylates / Steareth-20 Methacrylate Copolymer.

All particularly preferred and most preferred polymers are defined by their INCI names.

The inventive polymers according to feature (a) are preferably present in an amount of from 0.1 to 10% by weight, more preferably from 1 to 5% by weight, based in each case on the weight of the composition, of the compositions according to the invention.

Quaternary ammonium compounds are particularly preferred as the cationic surfactant according to the invention. The cationic surfactant is preferably selected from the group of ammonium halides, in particular chlorides or bromides, which is particularly preferably formed from N- (C ₈ - to C ₃₀ ) -alkylpyridinium halide, benzyltrimethylammonium halide, benzyl- (C ₈ - bis C ₃₀ ) -α | alkyldimethylammonium halide, benzyl-di (C ₈ - to C ₃₀ ) -alkylmethylammonium halide, (C ₈ - to C ₃₀ ) -alkyltrimethylammonium halide, (C ₈ - to C ₃₀ ) -dialkyldimethylammonium halide and (C ₈ - to C ₃₀ ) -trialkylmethylammonium halide. Preferred (C ₈ - to C ₃₀ ) -alkyl groups are myristyl, cetyl, lauryl, stearyl and behenyl. Representatives of these cationic surfactants are z. N-cetyl pyridinium chloride, cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, lauryl dimethyl ammonium chloride, lauryl dimethyl benzyl ammonium chloride and tricetylmethyl ammonium chloride.

Also, as a cationic surfactant according to the invention preferably suitable are quaternary Esterverbindungen, so-called "esterquats", such as those sold under the trademark Stepantex ^® Methylhydroxyalkyldialkoyloxyalkyl-ammonium methosulfate as well as the products marketed under the trade name Dehyquart ^® products such as Dehyquart ^® AU-46th Further cationic surfactants which can be used according to the invention are the quaternized protein hydrolysates.

Also suitable as cationic surfactant according to the invention are cationic silicone oils such as, for example, the commercially available products Q2-7224 (manufacturer: Dow Coming, a stabilized trimethylsilylamodimethicone), Dow Corning 929 emulsion (containing a hydroxylamino-modified silicone, which is also referred to as amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ^® quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary poly dimethyl siloxanes, quaternium-80).

The inventive cationic surfactants according to feature (b) are preferably in an amount of 0.1 to 10 wt.%, Particularly preferably from 0.5 to 5 wt.%, Based on the weight of the composition in the. Contain compositions of the invention.

The polymers of feature (a) and the cationic surfactants of feature (b) are used according to the invention preferably in a weight ratio of from 20 to 1 to 1 to 20, particularly preferably from 10 to 1 to 1 to 10, in the thickening compositions according to the invention.

The polymers of feature (a) and electrolytes according to the invention are preferably present in a weight ratio of 10: 1 to 1: 10, more preferably 5: 1 to 1: 5, in the compositions according to the invention.

The compositions according to the invention are preferably used as aqueous carrier or aqueous-alcoholic carrier for cosmetic active substances. An aqueous carrier, according to the invention, contains at least 10% by weight of water. Anhydrous refers to systems containing less than 10% by weight of water. For the purposes of the present invention, aqueous alcoholic carriers are aqueous systems containing from 3 to 70% by weight of an optionally substituted C 1 -C ₄ -alcohol having at least one hydroxyl group, for example methoxybutanol, benzyl alcohol, ethyldiglycol or 1,2-propylene glycol, glycerol and, in particular, ethanol or Isopropanol, to understand. It is (according to the invention preferred if the means have a pH of greater than pH 7.

The usable alkalizing agents for adjusting the pH are not subject to any restrictions. Ammonia, basic amino acids (eg arginine, lysine), alkanolamines (eg monoethanolamine), ammonium, alkali metal and alkaline earth metal hydroxides, carbonates, bicarbonates, hydroxycarbonates, carbamides, silicates, in particular metasilicates and alkali metal phosphates can advantageously be used become.

In addition, saturated or unsaturated, linear or branched alcohols having 8 to 36 carbon atoms may be present in the compositions according to the invention. These are preferably fatty alcohols and / or Guerbet alcohols.

Fatty alcohols are to be understood as meaning primary aliphatic alcohols of the formula (I)

R ⁷ OH (I)

in which R is an aliphatic, linear or branched hydrocarbon radical having 8 to 22 carbon atoms, which is saturated or may contain up to 3 double bonds.

Typical examples are 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, olenyl alcohol, elaeostearyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol, and technical mixtures thereof For example, in the high pressure hydrogenation of technical methyl esters based on fats and oils or aldehydes from the Roelen oxo synthesis and as a monomer fraction in the dimerization of unsaturated fatty alcohols incurred. Preference is given to technical fatty alcohol mixtures having 12 to 18 carbon atoms, for example coconut, palm, palm kernel or tallow fatty alcohol, in particular coconut and / or tallow fatty alcohol.

Guerbet alcohols are alcohols which are prepared by alkaline condensation of alcohols to higher molecular weight, branched Isό alcohols. This implementation was first published by Guerbet in 1899. Machemer presented 1952 essential steps of the reaction (Angewandte Chemie 64 (1952) 213-20): In addition to the dehydrogenation to ketone, in which hydrogen is split off, and the aldol condensation is the crotonization, in which water is split off, an important step in the reaction process , The prior art is a reaction at atmospheric pressure and a reaction temperature of 240 to 260 ⁰ C. The branched alcohols thus obtained are referred to as Guerbet alcohols. In the meantime, a large number of other processes are known from the prior art according to which Guerbet alcohols can be obtained.

As additional surfactants anionic, amphoteric, zwitterionic and nonionic surfactants may be included in the compositions of the invention.

Suitable anionic surfactants in preparations according to the invention are all anionic surfactants suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such. Example, a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group having about 10 to 22 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups may be present in the molecule. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium and the mono-, di- and Trialkanolammoniumsalze with 2 or 3 C-atoms in the Aikanolgruppe, linear fatty acids having 10 to 22 carbon atoms (soaps )

Ethercarbonsäuren the formula RO- (CH ₂ -CH ₂ O) _x -CH ₂ -COOH, in the R ine linear

Alkyl group having 10 to 22 C atoms and x = 0 or 1 to 16,

Acylsarcosides having 10 to 18 C atoms in the acyl group,

Acyltaurides having 10 to 18 C atoms in the acyl group,

Acyl isethionates having 10 to 18 C atoms in the acyl group, ; ₍ ^' Sulfobemsteinsäuremono- and dialkyl esters having 8 to 18 carbon atoms in the alkyl

I,:, and sulfosuccinic acid mono-alkyl polyoxyethyl esters having 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups, linear alkanesulfonates having 12 to 18 carbon atoms, linear alpha-olefin sulfonates having 12 to 18 carbon atoms, ', alpha -Sulfofettsäuremethylester of fatty acids having 12 to 18 carbon atoms, ¹ alkyl sulfates and Alkylpolyglykolethersulfate of the formula RO (CH ₂ -CH ₂ O) _x -SO ₃ H, in ¹ the R is a preferably linear alkyl group having 10 to 18 carbon atoms and x = 0 or 1 to 12, ^' '

Blends of surface-active hydroxysulfonates according to DE-A-37 25 030, sulfated hydroxyalkylpolyethylene and / or hydroxyalkylene-propylene glycol ethers according to DE-A-37 23 354,

Sulfonates of unsaturated fatty acids having 12 to 24 carbon atoms and 1 to 6 Doppelbin _^ fertilize according to DE-A-39 26 344,

Esters of tartaric acid and citric acid with alcohols, the adducts of about 2-15 molecules of ethylene oxide and / or propylene oxide with fatty alcohols having 8 to 22

Represent C atoms.

Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids having 10 to 18 C atoms in the alkyl group and up to 12 glycol ether groups in the molecule, and in particular salts of saturated and in particular unsaturated C ₈ -C ₂₂ carboxylic acids, such as oleic acid, stearic acid , Isostearic acid and palmitic acid.

Zwitterionic surfactants are surface-active compounds which have at least one quaternary ammonium group and at least one -COO ^(" 'or -SO ₃ ^H group in the molecule." Particularly suitable zwitterionic surfactants are the so-called betaines, such as N-alkyl-N. N-dimethylammonium glycinates, for example the cocoalkyl dimethylammonium glycinate, N-acylaminopropyl N, N-dimethylammonium glycinates, for example Kokosacylaminopropyl- dimethylammoniumglycinat, and 2-alkyl-3-carboxymethyl-3-hydroxyethyl-imidazoline with 8 to 18 C in each case A preferred zwitterionic surfactant is the fatty acid amide derivative known under the INCI name cocamidopropyl betaine, in the alkyl or acyl group and the cocoacylaminoethyl- hydroxyethylcarboxymethylglycinate. Ampholytic surfactants are surface-active compounds which, in the ₃ H-group in addition to a C _8- i ₈ alkyl or acyl group in the molecule at least one free amino group and at least one -COOH or -SO and which are capable of forming inner salts , 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 alkylarήinoacetic acids each having about 8 to 18 C Atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethyl aminopropionate and C ₁₂ - ₁₈ lsarcosin -Acy.

Nonionic surfactants contain as hydrophilic group z. B. a polyol group, a polyalkylenglykolethergruppe or a combination of polyol and Polyglykolether- group. Such compounds are, for example

- Addition products of 2 to 100 mol, preferably 2 to 50 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 C atoms in the alkyl group,

- C ₁₂ . _22- fatty acid mono- and diesters of addition products of 1 to 30 moles of ethylene oxide with glycerol,

C _{8-22 alkyl} mono- and oligoglycosides and their ethoxylated analogs,

Adducts of 5 to 60 moles of ethylene oxide with castor oil and hydrogenated castor oil,

- Addition products of ethylene oxide to sorbitan fatty acid esters

- Addition products of ethylene oxide to fatty acid alkanolamides.

Suitable adducts of 2 to 100 moles of ethylene oxide with a linear fatty alcohol containing 12 to 22 carbon atoms are all adducts obtainable by the known technical ethoxylation processes. Preference is given to the addition products which contain only a small amount of free fatty alcohol and have a narrow homolog distribution (so-called narrow-rank ethoxylates), as described, for example, in US Pat. are accessible according to the method described in DE 38 43 713 A1.

In addition, the agents of the invention may contain addition products of from 1 to 4 moles of ethylene oxide onto a fatty alkylamine. As addition products of 1 to 4 mol JΞ ^ ethylene oxide with a linear fatty alkylamine having 12 to 22 carbon atoms are all suitable adducts obtainable by known industrial processes, which are also commercially available.Especially suitable is the adduct of 2 moles of ethylene oxide to a C ^ -

■ Cr] ß-cocoalkylamine.

Arriphothere surfactants for the purposes of the present invention are, for example, N- • fatty alkyl-dimethyl-glycine or N-fatty-acylaminopropionic acid and / or zwitterionic surfactants, e.g. N-fatty alkyl-dimethylammonium glycinate or N-fatty acylaminopropyl dimethylglycinate.

Furthermore, proteins and / or derivatives of plant or animal origin such as, for example, pea, soybean, wheat and almond protein hydrolyzate or acacia protein and also collagen or keratin hydrolyzate can be present in the compositions according to the invention.

In addition, hair cosmetic auxiliaries may be contained, in particular bisabolol, plant extracts, vitamins such as preferably niacinamide, tocopherol _j vitamin, A, biotin and vitamin D.

In a preferred embodiment, the composition according to the invention is present as oxidative coloring agent for keratin-containing fibers, in particular for human hair, and additionally contains at least one oxidation dye precursor of the developer type (developer component) and / or coupler type (coupler component). For permanent, intensive dyeings of fibers, in particular keratin-containing fibers, with corresponding fastness properties, these oxidation dyes are used. Such colorants usually contain oxidation dye precursors, so-called developer components and coupler components. The developer components form under the influence of the oxidizing agent added before the application with each other or under coupling with one or more coupler components, the actual dyes. The oxidation stains are characterized by excellent, long lasting staining results.

Temporary dyeings are achieved on a fiber when so-called substantive dyes are used in colorants. Direct dyes are on -sich colored and require no oxidizing agent for color formation. However, the substantive dyes can also be used together with oxidative colorants to specifically influence the shade.

In the context of this application, nucleated fibers are understood to mean furs, wool, feathers and, in particular, human hair.

The developer components can be in the form of a salt and thus serve as the electrolyte according to the invention. The oxidation dye precursors, in particular p-toluenediamine, are preferably used in the form of their physiologically acceptable salts. These are formed by reacting the oxidation dye precursor with an inorganic or organic acid. As developer components are usually primary aromatic amines with another, located in the para or ortho position, free or substituted hydroxy or amino group, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazole derivatives and 2,4,5,6-tetraaminopyrimidine and its derivatives used ,

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)

in which

G ¹ represents a hydrogen atom, a C ₁ - to C ₄ alkyl, C ₁ - to C ₄ - monohydroxyalkyl radical, a C ₂ - to C ₄ polyhydroxyalkyl radical, a (C ₁ - to C ₄₎ - AIkOXy- ( C ₁ to C ₄ ) alkyl, a 4'-aminophenyl radical or a C _{1 to} C ₄ alkyl radical substituted with a nitrogen-containing group, a phenyl or a 4'-aminophenyl radical;

G ² represents a hydrogen atom, a C ₁ - to C ₄ alkyl, C ₁ - to C ₄ - monohydroxyalkyl radical, a C ₂ - to C ₄ polyhydroxyalkyl radical, a (C ₁ - to C ₄₎ - ", AIkOXy- (C ₁ - to C ₄ ) -alkyl radical or a C ₁ - to C ₄ -alkyl radical which is substituted by a,,, 'nitrogen-containing group;

- '; G ³ represents a hydrogen atom, a halogen atom such as a chlorine, bromine, iodine or

, Fluorine atom, a C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ -monohydroxyalkyl radical, a C ₂ - to C ₄ -polyhydroxyalkyl radical, a C ₁ - to C ₄ -hydroxyalkoxy radical, a C ₁ - to ! C ₄ -acetylaminoalkoxy radical, a C ₁ - to C ₄ -mesylaminoalkoxy radical or a C ₁ -

\ to C ₄ carbamoylaminoalkoxy radical;

4 G ⁴ represents a hydrogen atom, a halogen atom or a C ₁ - to C ₄ -alkyl radical or ■ ^' ' when G ³ and G ⁴ are ortho to one another, they may together form a bridging α, ω-alkylenedioxo group, such as for example, form an ethylene endoxy group.

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.

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 (f3-hydroxyethyl) amino-2- methylaniline, 4-N, N-bis (β-hydroxyethyl) amino-2-chloroanine, 2- (β-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 ,

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 (β-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.

Among the binuclear developer components which can be used in the colorants 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:

in which:

Z ¹ and Z ² independently of one another represent a hydroxyl or NH ₂ -ReSt, which is optionally substituted by a C ₁ - to C ₄ -alkyl radical, by a C ₁ - to C ₄ - "\ Hydroxyalkyl radical and / or is substituted by a bridge Y or the j ^{1 is} optionally part of a bridging ring system,

- ", the bridge Y is an alkylene group having 1 to 14 carbon atoms, such as

I is for example a linear or branched alkylene chain or an alkylene ring interrupted by one or more nitrogen-containing groups and / or one or more heteroatoms such as oxygen, sulfur or nitrogen atoms or

\ may be terminated and possibly by one or more hydroxyl or Cr bis

' _: Cβ-alkoxy may be substituted, or a direct bond,

G ⁵ and G ⁶ independently of one another are a hydrogen or halogen atom, a C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ -monohydroxyalkyl radical, a C ₂ - to C ₄ -

Polyhydroxyalkyl radical, a C ₁ - to C ₄ -aminoalkyl radical or a direct compound for bridging Y,

G ⁷ , G ⁸ , G ⁹ , G ¹⁰ , G ¹¹ and G ¹² are each independently

Hydrogen atom, a direct bond to the bridging Y or a C ₁ - to C ₄ -

Alkyl radical, with the provisos that the compounds of formula (Ent2) contain only one bridge Y per molecule and ^{• • • ■} . ' ^•

- The compounds of 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 (β-hydroxyethyl) -N, N- ^l 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 - (ß-hydroxyethyl) -N, N'-bis (4-aminophenyl) - tetramethylenediamine, ^• N, N'-bis (4-methyl-aminophenyl) -tetramethylendiarnin, N ₁ N'-diethyl-N, N 'bis (4'-amino-3'-methylphenyl) ethylenediamine, bis (2-hydroxy-5-aminophenyl) methane, 1, 3-bis (2,5-diaminophenoxy) -propan-2-one 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. Very particularly preferred binuclear developer components of the formula (Ent 2) are N, N ¹ -Bis (β-hydroxyethyl) -N, N'-bis (4 ¹ -aminophenyl) -1,3-diamino-propan-2-ol, Bis (2-hydroxy-5-aminophenyl) methane, 1, 3-bis (2,5-diaminophenoxy) -propan-2-ol, N, N'-bis (4'-aminophenyl) -1, 4-diazacycloheptane and 1, 10-bis (2 ', 5'-diaminophenyl) -1, 4,7,10-tetraoxadecane or one of its physiologically acceptable salts.

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)

in which:

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, C ₁ to C ₄ aminoalkyl, a

Hydroxy (C _r to C ₄ ) -alkylamino, a C ₁ - to C ₄ -hydroxyalkoxy, a C ₁ - to C ₄ -hydroxyalkyl (C _r to C ₄ ) aminoalkyl or a (di-C ₁ - bis C ₄ -alkylamino) -

(C ₁ - to C ₄ ) -alkyl radical, and

G ¹⁴ represents a hydrogen or halogen atom, a C ₁ - to C ₄ -alkyl radical, a

C ₁ - to C ₄ monohydroxyalkyl radical, a C ₂ - to C ₄ polyhydroxyalkyl radical, a (C ₁ - to C ₄₎ alkoxy (C _r to C ₄₎ alkyl group, a C ₁ - to C ₄ -aminoalkyl or a C ₁ to C ₄ cyanoalkyl radical,

G ¹⁵ is hydrogen, a C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ -

Monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a phenyl radical or a benzyl radical, and

G ¹⁶ is hydrogen or a halogen atom.

The substituents used in formula (Ent3) are defined according to the invention analogously to the above statements. >'Preferred p-aminophenols of the formula (Ent3) are in particular p-aminophenol, N-

\ ^" Methyl p-aminophenol, 4-amino-3-methyl-phenol, 4-amino-3-fluorophenol, 2-

, Hy, droxymethylamino-4-aminophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2- (D-

₍ hydroxyethoxy) phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, A-

Arr) ino-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- (diethylaminomethyl) -pheηol and their physiologically acceptable salts.

Very particularly preferred compounds of the formula (Ent3) are p-aminophenol, A-amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (α, β-dihydroxyethyl) phenol and 4-amino 2- (diethylaminomethyl) -pheno !.

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.

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.

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.

Preferred pyrimidine derivatives are, in particular, the compounds described in German Patent DE 2 359 399, Japanese Laid-Open Patent Publication JP 02019576 A2 or in the published patent application WO 96/15765, such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy- 2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2-dimethylamino-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6- triaminopyrimidine:

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-A 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- (D-aminoethyl) amino-1,3-dimethylpyrazole, 3,4,5-

Triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole and 3,5-diamino-4- (β-hydroxyethyl) amino-1-methylpyrazole.

Preferred pyrazolopyrimidine derivatives are in particular the derivatives of pyrazolo [1,5-a] opyrimidine of the following formula (Ent4) and its tautomeric forms, provided that a tautomeric equilibrium exists:

in which:

G ¹⁷ , G ¹⁸ , G ¹⁹ and G ²⁰ independently of one another represent a hydrogen atom, a C ₁ - to C ₄ -alkyl radical, an aryl radical, a C ₁ - to C ₄ -hydroxyalkyl radical, a C ₂ - to C ₄ -Polyhydroxyalkylrest a (C ₁ - to C ₄ J-AIkOXy- (C ₁ - to C ₄ ) -alkyl radical, a C ₁ - to C ₄ -Aminoalkylrest, optionally protected by an acetyl-ureide or a sulfonyl radical may be a (C ₁ - to C ₄₎ alkylamino (Cr to C ₄₎ - alkyl group, a di-e (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 ₄ ) - [hydroxyalkyl] - (C _r to C ₄ ) -aminoalkyl radical, the X radicals independently of one another represent a hydrogen atom, a C ₁ - to C ₄ -alkyl radical, an aryl radical, a C ₁ - to C ₄ -hydroxyalkyl radical, a C ₂ - to C ₄ - Polyhydroxyalkyl, a C ₁ - to C ₄ -Aminoalkylrest , a (C ₁ - to C ₄ ) -alkylamino », (C ₁ - to C ₄ ) -alkyl radical, a di-KC ₁ - to C ₄ ) alkyl] - (C ₁ - to C ₄ ) -aminoalkyl radical, wherein

^Ji: the dialkyl radicals are optionally substituted an carbon cycle or a heterocycle

"form with 5 or 6 chain members, a C ₁ - to C ₄ -hydroxyalkyl- or a di- (C ₁ -

, to C ₄ -hydroxyalkyl) aminoalkyl radical, an amino radical, a C ₁ - to C ₄ -alkyl or di-

(C ₁ - to C ₄ -hydroxyalkyl) amino, a halogen atom, a carboxylic acid group or a sulfonic acid group, - i has the value 0, 1, 2 or 3, rp has the value 0 or 1, - q has the value 0 or 1 and n has the value 0 or 1, with the proviso that the sum of p + '' q is not 0, if p + q is 2, n is 0, and the groups NG ¹⁷ G ¹⁸ and NG ¹⁹ G ²⁰ occupy the positions (2, 3); (5,6); (6,7); (3,5) or (3,7); when p + q is 1, n is 1, and the groups NG ¹⁷ G ¹⁸ (or NG ¹⁹ G ²⁰ ) and the group OH occupy the positions (2, 3); (5,6); (6,7); (3,5) or (3,7);

The substituents used in formula (Ent4) according to the invention, defined analogously to the above statements.

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, for example as shown in the scheme:

^88th

Among the pyrazolo [1, 5-a] pyrimidines of the above formula (Ent4) may be mentioned in particular:

Pyrazolo [1,5-a] pyrimidine-3,7-diamine;

2,5-dimethyl-pyrazolo [1,5-a] pyrimidine-3,7-diamine; Pyrazolo [1,5-a] pyrimidine-3,5-diamine;

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-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.

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.

As precursors of naturally-analogous dyes, preference is given to using, as oxidizing dye precursor of the developer type, 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. In a second preferred embodiment, the colorants contain at least one indole and / or indoline derivative.

Particularly suitable precursors of naturally-analogous hair dyes are derivatives of 5,6-dihydroxyindoline of the formula (IIIa),

(purple) in the independently of each other

R ¹ is hydrogen, a C ₁ -C ₄ -AikyIgPUPPe or a CiC ₄ -hydroxy-alkyl

", group,

R ² is hydrogen or a -COOH group, where the -COOH group may also be in the form of a salt with a physiologically compatible cation,

R ³ is hydrogen or a C 1 -C ₄ -alkyl group,

■ IR ⁴ is hydrogen, a C _r C ₄ alkyl group or a group -CO-R ⁶ , in which '. R ⁶ is a C _r C ₄ alkyl group, and

- R ⁵ is one of the groups mentioned under R ⁴ , as well as physiologically acceptable salts of these compounds with an organic or inorganic acid.

Particularly preferred derivatives of indoline are 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6 dihydroxyindoline, 5,6-dihydroxyindoline-2-carboxylic acid and 6-hydroxyindoline, 6-aminoindoline and 4-aminoindoline.

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.

Also suitable as precursors of naturally-analogous hair dyes are derivatives of the 5,6-dihydroxyindole of the formula (IIIb),

in the independently of each other

R ¹ is hydrogen, a C _r C ₄ -alkyl group or a C 1 -C ₄ -hydroxyalkyl group,

R ² is hydrogen or a -COOH group, where the -COOH group may also be present as a salt with a physiologically compatible cation,

R ³ is hydrogen or a C _r C ₄ -alkyl group, R ⁴ is hydrogen, a C 1 -C ₄ -alkyl group or a group -CO-R ⁶ , in which R ⁶ is a C 1 -C ₄ -alkyl group, and

R ⁵ represents one of the groups mentioned under R ⁴ ,

- As well as physiologically acceptable salts of these compounds with an organic or inorganic acid.

Particularly preferred derivatives of 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.

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.

In a further preferred embodiment, the colorants according to the invention contain at least one coupler component.

As coupler components m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives are generally used. Suitable coupler substances are in particular 1-naphthol, 1, 5, 2,7- and 1, 7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinomonomethylether, m-phenylenediamine, 1-phenyl 3-methyl-pyrazolone-5, 2,4-dichloro-3-aminophenol, 1, 3-bis (2 ', 4'-diaminophenoxy) -propane, 2-chloro-resorcinol, 4-chloro-resorcinol, 2 Chloro-6-methyl-3-aminophenol, 2-amino-3-hydroxypyridine, 2-methyl resorcinol, 5-methylresorcinol and 2-methyl-4-chloro-5-aminophenol.

When the composition according to the invention contains a coupler component as the colorant component, the preferred coupler components according to the invention are:

- M-aminophenol and its derivatives such as 5-amino-2-methylphenol, N-cyclopentyl-3-aminophenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 2,6-dimethyl 3-aminophenol, 3-trifluoroacetylamino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol, 5- (2'-hydroxyethyl) - amino-2-methylphenol, 3- (diethylamino) -phenol, ", N-cyclopentyl-3-aminophenol, 1, 3-dihydroxy-5- (methylamino) -benzene, 3-ethylamino

¹ V 4-methylphenol and 2,4-dichloro-3-aminophenol,

1. o-aminophenol and its derivatives,

, '- ₍ m-Diaminobenzene and its derivatives such as 2,4-diaminophenoxy- ¹ ethanol, 1, 3-bis (2 ^l , 4'-diaminophenoxy) propane, 1-methoxy-2-amino-4- ( 2 '

', hydroxyethylamino) benzene, 1,3-bis- (2', 4'-diaminophenyl) -propane, 2,6-bis- (2'-)

'^' hydroxyethylamino) -1-methylbenzene, 2 - ({3 - [(2-hydroxyethyl) amino] -4-methoxy-5-

: 'methyl-phenyl} -amino) -ethanol,, 2 - ({3 - [(2-hydroxyethyl) -amino] -2-methoxy-5-methyl-phenyl} -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-methylbenzene,

Di- or trihydroxybenzene derivatives such as, for example, resorcinol, resorcinomonomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2-chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1,2,4-trihydroxybenzene,

Pyridine derivatives such as, for example, 2,6-dihydroxypyridine, 2-amino-3-hydroxypyridine, 2-amino-5-chloro-3-hydroxypyridine, 3-aminb-2-methyl-amino-6-methoxypyridine, 2,6-dihydroxy-3, 4-dimethylpyridine, 2,6-dihydroxy-4-methylpyridine, 2,6-diaminopyridine, 2,3-diamino-6-methoxypyridine and 3,5-diamino-2,6-dimethoxypyridine,

Naphthalene derivatives such as, for example, 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 4,6-diaminopyrimidine, 4-amino-2,6-dihydroxypyrimidine, 2,4-diamino-6-hydroxypyrimidine, 2,4,6-trihydroxypyrimidine, 2-amino-4-methylpyrimidine, 2-amino 4-hydroxy-6-methylpyrimidine and 4,6-dihydroxy-2-methylpyrimidine, or Methylenedioxybenzene derivatives such as 1-hydroxy-3,4-methylenedioxybenzene, 1-amino-3,4-methylendioxybenΣol and 1- (2'-hydroxyethyl) amino-3,4-methylenedioxybenzene and their physiologically acceptable salts.

Coupler components which are particularly preferred according to the invention are 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 3-aminophenol, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, resorcinol, 4-chlororesorcinol , 2-chloro-6-methyl-3-aminophenol, 2-methyl resorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol and 2,6-dihydroxy-3,4-dimethylpyridine.

Preferred substantive dyes which are used in the compositions according to the invention 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-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.

Furthermore, the agents according to the invention may contain a cationic substantive dye. Particularly preferred are

(a) cationic triphenylmethane dyes such as Basic Blue 7, Basic Blue 26, Basic Violet 2 and Basic Violet 14,

(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). 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.

Preferred cationic substantive dyes of group (c) are in particular the following compounds:

CH ₃ SO ₄ ^"

Cf

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). ^l Diö, cationic direct dyes, which are sold under the trademark Arianor ^®, are also very particularly preferred according to the invention

'cationic substantive dyes.

Diö compositions of the invention contain this embodiment according to 'the direct dyes preferably in an amount of 0.01 to 20 wt .-%, bezo- ^■ gön on the total colorant.

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.

It is not necessary for the oxidation dye precursors or the direct dyes to be in each case homogeneous compounds. Rather, in the compositions according to the invention, due to the production process for the individual dyes, minor amounts of other components may be included, as far as they do not adversely affect the dyeing result or for other reasons, e.g. toxicological, must be excluded.

If the composition according to the invention is present as an oxidative colorant, oxidation dye precursors or direct dyes can be admixed immediately before use. It is preferred if the composition according to the invention of this embodiment is formulated in such a way that at least oxidation dye precursors in a mixture with the composition according to the invention are stored in a container.

With regard to the dyes which can be used in the compositions according to the invention, reference is expressly made to the monograph Ch. Zviak, The Science of Hair Care, Chapter 7 (pages 248-250, direct dyes) and Chapter 8, pages 264-267; Oxidation dye precursors), published as volume 7 of the series "Dermatology"<Hrg .: Ch., Culnan and H. Maibach), published by Marcel Dekker Inc., New York, Basel, 1986, as well as the "European Inventory of Cosmetic Raw Materials", published by the European Community, available in disk form from the Federal Association of German industrial and commercial enterprises for pharmaceuticals, health products and personal care registered association, Mannheim, reference is made.

If the composition according to the invention contains oxidation dye precursors, the actual oxidative dyeing of the fibers can in principle be carried out with atmospheric oxygen. Preferably, however, a chemical oxidizing agent is used, especially if, in addition to the coloring, a lightening effect on human hair is desired. Suitable oxidizing agents are persulfates, chlorites and in particular hydrogen peroxide or its addition products of urea, melamine and sodium borate. However, according to the invention, the oxidation colorant can also be applied to the hair together with a catalyst which promotes the oxidation of the dye precursors, e.g. by Luftsaüerstoff, activated. Such 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. By using these metal salts, both the formation of the dyeing can be accelerated and the color shade can be specifically influenced.

Suitable enzymes are e.g. Peroxidases that can significantly increase the effect of small amounts of hydrogen peroxide. Furthermore, such enzymes are suitable according to the invention which directly oxidize the oxidation dye precursors with the aid of atmospheric oxygen, such as, for example, the laccases, or generate small amounts of hydrogen peroxide in situ and thus biocatalytically activate the oxidation of the dye precursors. Particularly suitable catalysts for the oxidation of the dye precursors are the so-called 2-electron oxidoreductases in combination with the specific substrates, e.g.

Pyranose oxidase and e.g. D-glucose or galactose,

Glucose oxidase and D-glucose,

Glycerol oxidase and glycerin,

Pyruvate oxidase and pyruvic acid or its salts, Alcohol oxidase and alcohol (MeOH, EtOH), - lactate oxidase and lactic acid and their salts,

Tyrosinase oxidase and tyrosine, uricase and uric acid or their salts, choline oxidase and choline, amino acid oxidase and amino acids.

If the agents according to the invention are formulated as oxidative hair dyes, they preferably have a pH of from 7.5 to 11, in particular from 8 to 10.

In a further preferred embodiment of the invention, the composition according to the invention is present as an agent for lightening or bleaching keratin-containing fibers, in particular human hair. In this embodiment, the composition additionally contains hydrogen peroxide and, as electrolyte, at least one persalt.

The hydrogen peroxide is according to the invention as, or solution, in the form of a ¹ solid addition compound of hydrogen peroxide with inorganic or organic compounds, such as sodium perborate, sodium percarbonate

Magnesium percarbonate, sodium percarbamide, polyvinylpyrrolidone-n H ₂ O ₂ (n is a positive integer greater than 0), urea peroxide and melamine peroxide used.

The selection of the persalts preferably present as the electrolyte in the composition according to the invention is subject in principle to no restrictions; common persalts known to those skilled in the art are, for example, (i) peroxodisulfates, persulfates and peroxodiphosphates such as ammonium peroxodisulfate, potassium peroxodisulfate, sodium peroxodisulfate, ammonium persulfate, potassium persulfate, sodium persulfate, potassium peroxodiphosphate, and further (ii) peroxides of alkali and alkaline earth metals such as magnesium and barium peroxides and (iii) physiologically acceptable salts of peroxycarboxylic acids, such as magnesium perphthalate. Among these persalts, which can also be used in combination, according to the invention, the inorganic compounds are preferred. Particularly preferred are the peroxodisulfates, in particular ammonium peroxodisulfate. The persalts are preferably present in the compositions of this embodiment in amounts of 1 to 40 wt .-%, in particular in amounts of 2 to 20 wt .-%, each based on the weight of the composition according to the invention. In the dosage of persalts in the form of electrolytes, the requirement of the electrolyte content must always be met.

Preferably, the composition according to the invention, when present as a bleaching agent, contains as alkalizing agent at least one metasilicate of ammonium or of the alkali metals or alkaline earth metals as alkalizing agent. Very particularly preferred metasilicates according to the invention are water glasses which are formed from an aqueous solution of a silicate of the formula (SiO ₂ ) n (Na ₂ O) _m (K ₂ O) p, where n is a positive rational number and m and p are independent of one another for a positive rational number or for 0, with the provisos that at least one of the parameters m or p is different from 0 and the ratio between n and the sum of m and p is between 1: 4 and 4: 1.

The efficiency of the present invention as bleaching agents for keratin fibers is greatest at a basic pH (pH> 7), especially at a pH of 8 to 12.

A second aspect of the invention is the use of a combination of at least one polymer which is formed from at least one monomer unit of an unsaturated carboxylic acid and at least one cationic surfactant for thickening compositions having an electrolyte content of at least 0.01 equivalent / 100 g and a pH Value greater than pH 6.

The preferred parameters of the embodiments according to the first article also apply to the second subject of this invention.

The following examples are intended to explain the subject matter of the invention in more detail: Examples

All amounts are, unless otherwise indicated, weight percent of the individual components based on the weight of the corresponding composition. The following raw materials were used:

Stenol 1618 ^® C ₁₆ -C ₁₈ fatty alcohol (INCI name: Cetearyl alcohol)

(Cognis Germany)

Kokoslorol ^® Ci ₂ -C ₁₈ C ₁₂ -Ci ₈ fatty alcohol (INCI name: Coconut Alcohol)

(Cognis Germany)

Texapon ^® NSO. Sodium Lauryl Ether Sulfate (27% Active Ingredient INCI: Sodium

Laureth Sulfate) (Cognis Germany)

Eumulgin ^® B2 Cetylstearylalkohol with about 20 EO units (INCI

Name: Ceteareth-20) (Cognis Germany)

Aculyn ^® 33A 30 wt .-% of active substance in water (INCI name:

Acrylate copolymer) (Rohm & Haas)

Turpinal ^® SL 1-hydroxyethane-1, 1-diphosphonic acid (INCI name:

Etidronic Acid, Aqua (Water)) (Solutia)

Dehyquart® ^® A-CA trimethylhexadecylammonium, 25% active ingredient

(INCI name: Aqua (Water), Cetrimonium Chloride) (Cognis Germany)

1.0 alkaline bleaching agent (pH 9.4) with and without persalt

First, a bleaching cream according to item 1.1 and an oxidizing agent-containing composition according to item 1.2 were provided using known manufacturing methods.

To prepare the bleaching agent, the amount of blonding cream is initially introduced and all other ingredients (Dehyquart A-CA, ammonium peroxydisulfate) are added. Finally, the recipe is added 0x1 or 0x2 in the specified amount with stirring and the pH adjusted. Subsequently, the viscosity is measured (Brookfield rotational viscometer, spindle 5, 4upm, 2O ⁰ C). The compositions of the finished bleaching agents and the viscosities are shown in Table 2 of item 1.3. 1.1 Blondiercreme

Raw material weight%

Stenol ^® 1618 11 0

Kokoslorol® C ₁₂ -C ₁₈ 2,2

Texapon® NSO 26.5

Ammonium sulfate 1.0

Sodium water glass 40/42 0,5

Ammonia, 25% to pH 9.5-10.0

Water ad 100

1.2 Oxidant-containing Composition Table 1:

1.3 Mixtures Table 2:

1 Dje'.EIektrolytkonzentration in the example formulations 3 to 10 is greater than 0.1 Val / 100g. The formulations 4 and 8 are according to the invention. f ''

2.0 mild alkaline blonding agent (pH 7.2)

First, a bleaching cream according to point 2.1 and an oxidant-containing composition according to point 2.2 were provided using known manufacturing methods. '

To prepare the bleaching agent, the developer is initially introduced with Dehyquart A and all other constituents (bleaching cream, ammonium persulfate) admixed. Finally, the recipe Ox1 or 0x2 in the specified amount with stirring added and the pH adjusted. Subsequently, the viscosity is measured (Brookfield rotational viscometer, spindle 5, 4upm, 2O ⁰ C). The compositions of the finished bleaching agents and the viscosities are shown in Table 3 of item 2.3. '

2.1 Blondiercreme

Raw material weight%

Steno) ^® 1618 15.0

Coconut oil ^® C ₁₂ -C ₁₈ 2,4

Texapon.RTM ^® NSO 26.5

PHB propyl ester 0.2

EDTA disodium salt 0.1

Ammonium sulfate 1.0

Imidazole 3.0

Sodium water glass 40/42 0,5

Phenoxyethanol 0.4

Citric acid, 50% 0.5

Water ad 100

2.2 Oxidant-containing composition

see formulas from point 1.2 2.3 mixtures

Table 3:

The electrolyte concentration in the example formulations 11 to 17 is greater than 0.1 Val / 100g.

The formulations 12 and 13 are according to the invention.

The inventive formulation 12 with polymer and with 3.0 g of cationic surfactant has a higher viscosity than all comparative formulations:

Formulation 11 with inventive polymer / without cationic surfactant

Formulation 16 without inventive polymer / with 3.0 g of cationic surfactant

Formulation 15 without polymer according to the invention / without cationic surfactant.

The inventive formulation 13 with polymer and with 5.0 g of cationic surfactant has a higher viscosity than all comparative formulations:

Formulation 11 with inventive polymer / without cationic surfactant

Formulation 17 without inventive polymer / with 5.0 g of cationic surfactant

Formulation 15 without polymer according to the invention / without cationic surfactant. 3 ^ 0 thickening of an alkaline blonding agent without persalt (pH 9.7)

)

First, a bleaching cream according to item 3.1 and an oxidizing agent-containing composition according to item 3.2 were provided using known manufacturing methods.

To prepare the bleaching agent, the developer is initially introduced with Dehyquart A and all other constituents (bleaching cream, Ammoniümpersulfat) admixed. Finally, the recipe is added 0x1 or 0x2 in the specified amount with stirring and the pH adjusted. The viscosity is then measured (Brookfield F ^ otationsviskosimeter, spindle 5, 4upm, 2O ⁰ C) .. The compositions of the final bleaching and the viscosities are given in Table 3 of the point 3.3.

3.1 Blondiercreme

Raw material ^' wt .-% ^■'

Stenol ^® 1618 10.0

Kokoslorol ^® C ₁₂ -C ₁₈ 3.0

Eumulgin ^® B2 3.0

Ammonium sulfate 1, 0

Turpinal SL ^® 0.2

Sodium water glass 40/42 0,5

Ammonia to pH 9.5-10.0

Water ad 100

3.2 Developer

identical to formulas under point 1.2 3.3 mixtures

Table 4:

The electrolyte concentration in example formulations 18 to 22 is 0.013 V / 100 g.

The recipe 19 is according to the invention. It has a viscosity more than twice as high as the comparative formulations

with inventive polymer / without cationic surfactant (formulation 18)

without inventive polymer / without cationic surfactant (formulation 20) and

without inventive polymer / with cationic surfactant (formulations 21 and 22).

Claims

». ^"; • '36th

pH 6 and with one

, Electrolyte content of at least 0.01 v / 100 g, preferably at least 0.05 v / 100 g, more preferably at least 0.1 v / 100 g, characterized in that ', they, a combination of

^] (a) at least one polymer, which is formed from at least one monomer unit ', ^{' of} an unsaturated carboxylic acid, and

(B) contains at least one cationic surfactant.

2. Composition according to claim 1, characterized in that the polymer is an anionic polymer.

3. A composition according to any one of claims 1 or 2, characterized in that the monomer unit of an unsaturated carboxylic acid is selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, crotonic acid and maleic acid. '

4. The composition according to any one of claims 1 to 3, characterized in that the polymer is selected from carbomer, acrylamide / sodium acrylate copolymer, acrylates / acetoacetoxyethyl methacrylate copolymer, acrylates / beheneth-25 methacrylate copolymer, acrylates / C 10-30 alkyl Acrylate Crosspolymer, Acrylates / Ceteth-20 Itaconate Copolymer, Acrylates / Ceteth-20 Methacrylate Copolymer, Acrylates / Laureth-25 Methacrylate Copolymer, Acrylates / Palmeth-25 Acrylate Copolymer, Acrylates / Palmeth-25 Itaconate Copolymer, Acrylates / Steareth-50 Acrylate Copolymer , Acrylates / Steareth-20 Itaconate Copolymer, Acrylates / Steareth-20 Methacrylate Copolymer, Acrylates / Stearyl Methacrylate Copolymer, Acrylates / Vinyl Isodecanoate Crosspolymer, Acrylic Acid / Acrylonitrogen Copolymer, Ammonium Acrylates / Acrylonitrogens Copolymer, Ammonium Acrylates Copolymer, Calcium Potassium Carbomer, DMAPA Acrylates / Acrylic Acid / Acrylonitrogen Copolymer, Ethylene / Sodium Acrylate Copolymer, Octadecenes / MA Copolymer, Sodium Acrylate / Acryloyldimethyl Taurate Copolymer, Sodium Acrylate / Acrolein Copolymer, Sodium Acrylate / Acrylonitrogen Copolymer, Sodium Acrylate Copolymer, Sodium Acrylate / Vinyl Isodecanoate Crosspolymer, Sodium Acrylates / Viny! Alcohol Copolymer, Sodium Carbomer, Sodium Isooctylene / MA Copolymer, Sodium Polyacrylate, Sodium Polymethacrylate, Sodium Styrene / Acrylate Copolymer, Sodium Tauride Acrylate / Acrylic Acid / Acrylonitrogen Copolymer and Starch / Acrylate / Acrylamide Copolymer,

Composition according to any one of Claims 1 to 4, characterized in that the cationic surfactant is chosen from the group constituted by N- (C ₈ - to C ₃₀ ) -alkylpyridinium halide, benzyltrimethylammonium halide, benzyl- (C ₈ - to C ₃₀ -alkyldimethylammoniumhalogenid) benzyl-di (C ₈ - C ₃₀₎ alkyl methylammonium halide, (C ₈ - to C ₃ o) -Alkyltrimethylammoniumhalogenid, (Cs to _C30) -Dialkyldimethylammoniumhalogenid and (C ₈ - to C ₃₀ ) -Trialkyl- methylammonium halide.

6. A composition according to any one of claims 1 to 5, characterized in that the polymer is contained in an amount of 0.1 to 10% by weight, based on the weight of the composition.

7. A composition according to any one of claims 1 to 6; characterized in that the cationic surfactant is contained in an amount of 0.1 to 10% by weight based on the weight of the composition.

8. Composition according to one of claims 1 to 7, characterized in that the polymers (a) and the cationic surfactants (b) in a weight ratio of 20 to 1 to 1 to 20, in particular from 10 to 1 to 1 to 10, contain are.

9. Composition according to one of claims 1 to 8, characterized in that the polymers (a) and electrolytes in a weight ratio of 10 to 1 to 1 to 10, in particular from 5 to 1 to 1 to 5, are included.

Composition according to any one of Claims 1 to 9, characterized in that it additionally contains at least one developer type oxidation dye precursor and / or at least one coupler type oxidation dye precursor.

11. A composition according to any one of claims 1 to 10, characterized in that it contains at least one persalt as the electrolyte. according to any one of claims 1 to 11, characterized "in that it additionally contains j ^'• 12-' composition, hydrogen peroxide.

)

13. ' Composition according to any one of Claims 1 to 12, characterized in that the pH is greater than pH 7.

14. ^' Using a combination of

(A) at least one polymer which is formed from at least one Moriomereinheit of an unsaturated carboxylic acid, and

(B) at least one cationic surfactant for thickening of compositions having an electrolyte content of 0.01 Val / 100g and a pH greater than pH 6.