WO2002009662A2

WO2002009662A2 - Agent for dyeing keratin containing fibers

Info

Publication number: WO2002009662A2
Application number: PCT/EP2001/008656
Authority: WO
Inventors: David Rose; Frank Naumann; Bernd Meinigke; Horst Höffkes
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 2000-08-02
Filing date: 2001-07-26
Publication date: 2002-02-07
Also published as: DE10038029A1; EP1304995A2; WO2002009662A3; AU2002212116A1

Abstract

The invention relates to an agent for dyeing keratin containing fibers which comprises as the developer at least one compound of the general formula (I), wherein R1 and R2 are the same or different and represent hydrogen, C1-4 alkyl or C1-4 hydroxyalkyl, and R3 represents a group of the formula (II), wherein R4 represents a piperazinyl group or a group -NR7(CH2)n-NR7, wherein R7 represents hydrogen or C1-4 alkyl and n is an integer of from 1 to 4, R5 and R6 are the same or different and represent hydrogen, C1-4 alkyl or C1-4 hydroxyalkyl, or else R3 represents a group (III), or a group (IV), wherein R9 represents hydrogen, C1-4 alkyl or C1-4 hydroxyalkyl, Y represents a direct bond or a straight-chain or branched C1-5 alkylene group, and A represents a saturated or unsaturated 5-, 6- or 7-membered ring optionally containing one or more heteroatoms, a group -CO-NH2, a C1-4 alkoxy group or a C1-4 dialkylamino group, wherein A may be linked with any carbon atom of the alkylene group Y.

Description

"Means for dyeing fibers containing keratin"

The invention relates to a new agent for dyeing keratin-containing fibers, which contains oxidation dye precursors, and a method for dyeing keratin fibers.

For the coloring of keratin fibers, especially human hair, the so-called oxidation coloring agents play a preferred role because of their intense colors and good fastness properties. Such colorants contain oxidation dye precursors, so-called developer components and coupler components. The developer components form the actual dyes under the influence of oxidizing agents or atmospheric oxygen with one another or under coupling with one or more coupler components.

Good oxidation dye precursors must first of all meet the following requirements: they must develop the desired color shades with sufficient intensity and authenticity in the oxidative coupling. They must also have a good ability to draw onto the fiber, with no noticeable differences between stressed and freshly regrown hair, especially with human hair (leveling ability). They should be resistant to light, heat and the influence of chemical reducing agents, e.g. B. against perm fluids. After all, if they are used as a hair dye, they should not stain the scalp too much, and above all they should be harmless from a toxicological and dermatological point of view.

Primary aromatic amines with a further free or substituted hydroxyl or amino group in the para or ortho position, diaminopyridine derivatives and 2,4,5,6-tetraaminopyrimidine and its derivatives are usually used as developer components. Specific representatives are, for example, p-phenylenediamine, p-toluenediamine, 2,4,5,6-tetraaminopyrimidine, p-aminophenol, N, N-bis (2'-hydroxyethyl) -p-phenylenediamine, 2- (2 ', 5'-diaminophenyl) ethanol, 2- (2,5-diaminophenoxy) ethanol, 4-amino-3-methylphenol, 2-aminomethyl-4-aminophenol, 2-hydroxy-4,5,6- triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triamino-4-hydroxypyrimidine and 1,3-N, N'-bis (2'-hydroxyethyl) -N, N'-bis ( 4'-aminophenyl) diamino-propan-2-ol.

M-Phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones, m-aminophenols and substituted pyridine derivatives are generally used as coupler components. Suitable coupler substances are, in particular, α-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 2,4 -Diaminophenoxyethanol, 2-amino-4- (2'-hydroxyethylamino) anisole, 1-phenyl-3-methyl-pyrazolon-5, 2,4-dichloro-3-aminophenol, 1, 3-bis- (2nd ', 4'-diaminophenoxy) propane, 2-chlororesorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 3-amino-6-methoxy-2- methylamino-pyridine and 3,5-diamino-2,6-dimethoxypyridine.

With regard to other customary dye components, reference is expressly made to the “Dermatology” series, edited by Ch. Culnan, H. Maibach, Verlag Marcel Dekker Inc., New York, Basel, 1986, Vol. 7, Ch. Zviak, The Science of Hair Care, chap. 7, pages 248 - 250 (direct dyes), and chap. 8, pages 264 - 267 (oxidation dyes), as well as the "European Inventory of Cosmetic Raw Materials", 1996, published by the European Commission, available in disk form from the Federal Association of German Industry and Trade Companies for Medicines, Health Products and Personal Care Products, Mannheim, reference taken.

Often it is not possible with the known coloring agents to obtain a color shade that looks natural on the hair. There is therefore a constant need for new, improved dye components. It was therefore the object of the present invention to find new components which are suitable for use in colorants and which in particular meet the requirements to be placed on oxidation dye precursors to a particular degree.

It has been found that certain pyrazole derivatives are outstandingly suitable as a coloring component in agents for dyeing keratin-containing fibers, and also that of developer component requirements to a particularly high degree. Thus, using these developer components with most known coupler components, brilliant color shades are obtained, particularly in the red and violet range, which are extraordinarily lightfast and washable. Furthermore, the dyeings are characterized by extraordinary cold wave fastness and heat stability, as well as by an excellent leveling.

The present invention therefore relates to compositions for dyeing keratin-containing fibers containing oxidation dye precursors, characterized in that at least one compound of the general formula I is present as developer components

in the

R1 and R2 can be the same or different and represent hydrogen, C _1-4 alkyl or C _1-4 -

Hydroxyalkyl stand and

R3 stands for a group with the formula II, (II),

in which R4 represents a piperazinyl radical or a group -NR7 (CH ₂ ) _n -NR7, in which R7 is hydrogen or C _1-4 -alkyl and n can be an integer from 1 to 4, R5 and R6 are identical or different can be hydrogen, C _1-4 alkyl or C _1-4 hydroxyalkyl,

for a group or

for a group

in which R9 is hydrogen, C _1-4 -alkyl or C _1- -hydroxyalkyl, Y represents a direct bond or a straight-chain or branched Cι _-5 - alkylene group and

A stands for a saturated or unsaturated, optionally containing one or more heteroatoms 5-, 6- or 7-ring, a group -CO-NH ₂ , a -C _-4 - alkoxy group or a C _1-4 -dialkylamino group, where A with can be linked to any carbon atom of the alkylene group Y.

Fibers, wool, feathers and in particular human hair are to be understood as fibers containing keratin. Although the compositions according to the invention are primarily suitable for dyeing keratin fibers, there is in principle nothing to prevent them from being used in other areas, in particular in color photography.

The physiologically tolerable salts can also be prepared in a manner known per se. Examples of such salts are the hydrochlorides, the hydrobromides, the sulfates, the phosphates, the acetates, the propionates, the citrates and the lactates.

In a preferred embodiment of the present invention, R3 stands for a group of the formula II. In this embodiment, those compounds have proven to be particularly suitable in which R1 and R6 and R2 and R5 are each the same. Examples of preferred compounds which fall under this embodiment are (1,3-dimethyl-4-aminopyrazol-5-yl) - (2 - ((1,3-dimethyl-4-aminopyrazol-5-yl) amino) ethyl) amine and 1,4-bis (1,3-dimethyl-4-aminopyrazol-5-yl) piperazine and their physiologically tolerable salts.

In a further preferred embodiment, compounds of the formula I are preferred in which the group A represents one of the groups piperidyl-, morpholin-4-yl-, imidazolyl-, cyclopentyl-, piperazinyl-, pyrazolyl- or phenyl-. The compounds of the formula I in which Y represents an ethylene or a propylene group are also preferred. Compounds of the formula I in which the substituent -YA represents a 2-piperidylethyl radical, a 2- (morpholin-4'-yl) ethyl radical, a 3- (morpholin-4'-yl) propyl radical, a 3- imidazolylpropyl, a (N, N-diethylamino) pentyl, a cyclopentyl, a 2-piperazinylethyl, a 2-phenylethyl or a 3-ethoxypropyl. Examples of such preferred compounds of the formula I are (1, 3-dimethyl-4-aminopyrazol-5-yl) - (2-piperidylethyl) amine, (1, 3-dimethyl-4-aminopyrazol-5-yl) - (2- (morpholin-4'-yl) ethyl) amine, (1, 3-dimethyl-4-aminopyrazol-5-yl) - (3- (morpholin-4'-yl) propyl) amine, 1 , 3-dimethyl-4-amino-5-pyrazolylpyrazol, (1, 3-dimethyl-4-aminopyrazole-5-yl) - (3-imidazolylpropyl) - amine, N- (4 - ^((1, 3 '-Dimethyl-4'-aminopyrazol-5'-yl) -amino) pentyl) -N, N-diethyl-amine, (1, 3-dimethyl-4-aminopyrazol-5-yl) - (cyclopentyl) - amine, (1, 3-dimethyl-4-aminopyrazol-5-yl) - (2-piperazinylethyl) amine, (1, 3-dimethyl-4-aminopyrazol-5-yl) - (2-phenylethyl) - amine, 2 - ((4'-amino-1 ', 3'-dimethylpyrazol-5'-yl) amino) acetamide, (4-amino-1, 3-dimethylpyrazol-5-yl) - (3rd -ethoxy-propyl) -amine and their physiologically tolerable salts.

Any mixtures of compounds with the formula I and, if appropriate, further dye precursors can also be used.

The agents according to the invention are particularly well suited as so-called oxidation coloring agents. In oxidation colorants, the compound of formula I used according to the invention acts as a developer component. If desired, further developer components as well as one or more coupler components can be included.

Primary aromatic amines with a further free or substituted hydroxy or amino group in the para or ortho position, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazole derivatives and 2,4,5,6-tetraaminopyrimidine and. Are usually further developer components its derivatives used. Specific representatives are, for example, p-phenylenediamine, p-toluenediamine, 2,4,5,6-tetraaminopyrimidine, p-aminophenol, N, N-bis (2'-hydroxyethyl) -p-phenylenediamine, 2- (2 ', 5' -Diaminophenyl) - ethanol, 2- (2 ', 5'-diaminophenoxy) -ethanol, 4-amino-3-methylphenol, 2-aminomethyl-4-aminophenol, 4-amino-2-diethylaminomethylphenol, 2-hydroxy-4, 5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triamino-4-hydroxypyrimidine and 1,3-N, N'-bis (2'-hydroxyethyl) -N, N '-bis (4'-aminophenyl) -diamino-propan-2-ol.

Very particularly preferred further developer components are p-phenylenediamine, p-toluenediamine, N, N-bis (2'-hydroxyethyl) -p-phenylenediamine, 2,4,5,6-tetraminopyrimidine, 1- (2'-hydroxyethyl) - 2,5-diaminobenzene, 3-methyl-4-aminophenol, o-aminophenol, 2-aminomethyl and 2-hydroxymethyl-4-aminophenol. In a preferred embodiment, the agent according to the invention contains at least one coupler component.

M-Phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives are generally used as coupler components.

Coupler components preferred according to the invention are m-aminophenol and its derivatives such as 5-amino-2-methylphenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 2,6-dimethyl-3-ami- nophenol, 3-trifluoroacetylamino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol, 5- (2'-hydroxyethyl) amino -2-methylphenol, 3- (diethylamino) phenol, N-cyclopentyl-3-aminophenol, 1, 3-dihydroxy-5- (methylamino) benzene, 3- (ethylamino) -4-methylphenol and 2,4-dichloro -3-aminophenol,

o-aminophenol and its derivatives, m-diaminobenzene and its derivatives such as 2,4-diaminophenoxyethanol,

1,3-bis (2,4-diaminophenoxy) propane, 1-methoxy-2-amino-4- (2'-hydroxyethylamino) benzene, 1,3-bis (2,4-diaminophenyl) - propane, 2,6-bis (2-hydroxyethylamino) -1-methylbenzene 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 resorcinol, resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2-chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1, 2,4-trihydroxybenzene,

Pyridine derivatives such as 2,6-dihydroxypyridine, 2-amino-3-hydroxypyhdin, 2-

Amino-5-chloro-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 2,6-dihydroxy-4-methylpyridine, 2,6- Diaminopyridine, 2,3-diamino-6-methoxypyridine and 3,5-diamino-2,6-dimethoxypyridine,

Naphthalene derivatives such as 1-naphthol, 2-methyl-1-naphthol, 2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1, 5-dihydroxynaphthalene, 1, 6-dihydroxy-naphthalene, 1, 7-dihydroxynaphthalene, 1, 8-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 2,3-dihydroxynaphthalene,

Morpholine derivatives such as 6-hydroxybenzomorpholine and 6-amino-benzomorpholine,

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-methylenedioxybenzene and 1 - (2'-hydroxyethyl) amino-3,4-methylenedioxybenzene.

Particularly preferred coupler components 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.

These further developer and coupler components are usually used in free form. For substances with amino groups, however, it can be preferred to use them in salt form, in particular in the form of the hydrochlorides and sulfates.

The agents according to the invention preferably contain the compounds of formula I and any coupler components present in an amount of 0.005 to 20% by weight, preferably 0.1 to 5% by weight, each based on the total agent. The individual components are preferably used in approximately molar amounts to one another. If molar use has also proven to be expedient, a certain excess of individual oxidation dye precursors is not disadvantageous, so that developer components and coupler components in a molar ratio of 1: 0.5 to 1: 3, in particular 1: 1 to 1: 2 , can be included.

In a preferred embodiment, the agents according to the invention contain, in addition to the compounds contained according to the invention, customary direct dyes, e.g. B. from the group of nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols. Preferred direct dyes are those with the international names or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, Basic Yellow 57, Disperse Orange 3, HC Red 3, HC Red BN, Basic Red 76, HC Blue 2, HC Blue 12, Disperse Blue 3, Basic Blue 99, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9, Basic Brown 16 and Basic Brown 17 known compounds as well as 1,4-bis- (2'- hydroxyethyl) - amino-2-nitrobenzene, 3-nitro-4- (2'-hydroxyethyl) aminophenol, 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 6-nitro-1, 2,3,4-tetrahydroquinoxaline, 2- Hydroxy-1, 4-naphthoquinone, hydroxyethyl-2-nitro-toluidine, picraminic acid, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1- hydroxy-4-nitrobenzene. The agents according to the invention in accordance with this embodiment preferably contain the substantive dyes in an amount of 0.01 to 20% by weight, based on the total colorant.

Furthermore, the preparations according to the invention can also contain naturally occurring dyes such as, for example, henna red, henna neutral, henna black, chamomile flowers, sandalwood, black tea, rotten tree bark, sage, blue wood, madder root, catechu, sedre and alkanna root.

It is not necessary that the oxidation dye precursors or the optional direct dyes each represent uniform compounds. Rather, in the agents according to the invention, due to the manufacturing process for the individual dyes, further components may be contained in minor amounts, provided that these do not adversely affect the coloring result or for other reasons, e.g. B. toxicological, must be excluded.

Further dye components contained in the agents according to the invention can also be indoles and indolines, as well as their physiologically tolerable salts. Preferred examples are 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole, 6 -Hydroxyindole, 6-aminoindole and 4-aminoindole. Also preferred are 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline, 6 - hydroxyindoline, 6-aminoindoline and 4-aminoindoline.

The agents according to the invention produce intensive colorations even at physiologically compatible temperatures of below 45 ° C. They are therefore particularly suitable for dyeing human hair. For use on human hair, the agents can usually be incorporated into a water-containing cosmetic carrier. Suitable water-containing cosmetic carriers are e.g. B. creams, emulsions, gels or surfactant-containing foaming solutions such. B. shampoos or other preparations that are suitable for use on the keratin fibers. If necessary, it is also possible to incorporate the agents into anhydrous carriers. Furthermore, the agents according to the invention can contain all active ingredients, additives and auxiliaries known in such preparations. In many cases, the agents contain at least one surfactant, and in principle both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants are suitable. In many cases, however, it has proven advantageous to select the surfactants from anionic, zwitterionic or nonionic surfactants.

Suitable anionic surfactants in preparations according to the invention are all anionic surface-active substances suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such as. B. a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group with about 10 to 22 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups can be contained in the molecule. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium as well as the mono-, di- and trialkanolammonium salts with 2 or 3 carbon atoms in the alkanol group,

linear fatty acids with 10 to 22 carbon atoms (soaps),

Ether carboxylic acids of the formula RO- (CH ₂ -CH ₂ O) _x -CH ₂ -COOH, in which R is a linear alkyl group with 10 to 22 C atoms and x = 0 or 1 to 16, acyl sarcosides with 10 to 18 C atoms in the acyl group, Acyltauhde with 10 to 18 C atoms in the acyl group, Acyl isethionates with 10 to 18 C atoms in the acyl group,

Sulfosuccinic acid mono- and dialkyl esters with 8 to 18 carbon atoms in the alkyl group and sulfosuccinic acid mono-alkyl polyoxyethyl esters with 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups, linear alkanesulfonates with 12 to 18 carbon atoms, linear alpha-olefin sulfonates with 12 to 18 carbon atoms, alpha-sulfofatty acid methyl ester of fatty acids with 12 to 18 carbon atoms, alkyl sulfates and alkyl polyglycol ether sulfates of the formula RO (CH ₂ -CH ₂ O) _x -SO ₃ H, in which R is a preferably linear alkyl group with 10 to 18 C atoms and x = 0 or 1 to 12, mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030, sulfated hydroxyalkyl polyethylene and / or hydroxyalkylene propylene glycol ethers according to DE-A-37 23 354,

Sulfonates of unsaturated fatty acids with 12 to 24 carbon atoms and 1 to 6 double bonds according to DE-A-39 26 344,

Esters of tartaric acid and citric acid with alcohols, the addition products of about 2 to 15 molecules of ethylene oxide and / or propylene oxide to fatty alcohols with 8 to 22 carbon atoms.

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

Zwitterionic surfactants are those surface-active compounds which carry at least one quaternary ammonium group and at least one -COO ^(_) - or -Sθ ₃ ^H group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinate, for example coconut alkyl dimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinate, for example coconut acylaminopropyl dimethylammonium glycinate, and 2 -Alkyl-3-carboxymethyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and the cocoacylaminoethylhydroxyethylcarboxymethylglycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known under the CTFA name Cocamidopropyl Betaine.

Ampholytic surfactants are surface-active compounds which, in addition to a C _8-18 alkyl or acyl group, contain at least one free amino group and at least one -COOH or -SO ₃ H group in the molecule and are capable of forming internal salts are. Examples of suitable ampholytic surfactants are N-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N-alkyliminodipropionic acid, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyltaurine, N-alkyl sarcosine, 2-alkylaminopropionic acid and alkylaminoacetic acid each about 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-Kokosalkylaminopropio- nat, cocoacylaminoethyl aminopropionate and C _12- ι ₈ acyl sarcosine. Nonionic surfactants contain z as a hydrophilic group. B. a polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether group. Such connections are, for example

Addition products of 2 to 30 mol ethylene oxide and / or 0 to 5 mol propylene oxide with linear fatty alcohols with 8 to 22 carbon atoms, with fatty acids with 12 to 22 carbon atoms and with alkylphenols with 8 to 15 carbon atoms in the alkyl group, C _12-22 fatty acid monoesters and diesters of adducts of 1 to 30 moles of ethylene oxide with glycerol,

C _{8-22 alkyl} mono- and oligoglycosides and their ethoxylated analogues, addition products of 5 to 60 mol ethylene oxide onto castor oil and hardened castor oil,

Addition products of ethylene oxide with sorbitan fatty acid esters Addition products of ethylene oxide with fatty acid alkanolamides.

Examples of the cationic surfactants which can be used in the hair treatment compositions according to the invention are, in particular, quaternary ammonium compounds. Ammonium halides such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylam onium chlorides, e.g. B. cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride. The quaternized protein hydrolysates are further cationic surfactants which can be used according to the invention.

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

In addition to a good conditioning effect, alkylamidoamines, especially fatty acid amidoamines such as the ^{stearylamidopropyldimethylamine} available under the name Tego Amid ^® S 18, are notable for their good biodegradability. Also very good biodegradability are quaternary Esterverbindungen, so-called "esterquats", dialkoyloxyalkylammoniummethosulfate such as those sold under the trademark Stepantex ^® methyl hydroxyalkyl.

An example of a suitable cationic surfactant quaternary sugar derivative is the commercial product Glucquat ^® 100, according to CTFA nomenclature a "lauryl methyl Gluceth-10 Hydroxypropyl Dimonium Chloride".

The compounds with alkyl groups used as surfactants can each be uniform substances. However, it is generally preferred to start from natural vegetable or animal raw materials in the production of these substances, so that substance mixtures with different alkyl chain lengths depending on the respective raw material are obtained.

In the case of the surfactants, which are addition products of ethylene and / or propylene oxide onto fatty alcohols or derivatives of these addition products, both products with a "normal" homolog distribution and those with a narrowed homolog distribution can be used. “Normal” homolog distribution is understood to mean mixtures of homologs which are obtained as catalysts from the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates. In contrast, narrow homolog distributions are obtained if, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates are used as catalysts. The use of products with a narrow homolog distribution can be preferred.

Other active ingredients, auxiliaries and additives are, for example, nonionic polymers such as, for example, vinylpyrrolidone / vinyl acrylate copolymers, polyvinylpyrrolidone and vinylpyrrolidone / vinyl acetate copolymers and polysiloxanes, cationic polymers such as quaternized cellulose ethers, polysiloxanes with quaternary groups, dimethyldioxylammonylammonylammonylammonylammonylammonyl amide Copolymers, dimethylaminoethyl methacrylate quaternized with diethyl sulfate, vinyl pyrrolidone copolymers, vinyl pyrrolidone imidazolinium methochloride copolymers and quaternized polyvinyl alcohol, zwitterionic and amphoteric polymers such as acrylamidopropyl-trimethylammonium chloride / acrylate copolymers and octylacrylamide / methyl methacrylate / tert.-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers, anionic polymers such as polyacrylic acids, cross-linked polyacrylic acids, vinyl acetate / crotonic acid / vinyl acrylate / crononic acid / vinyl alcohol Copolymers, vinyl acetate / butyl maleate / isobomylacrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and acrylic acid / ethyl acrylate / N-tert-butylacrylamide terpolymers, thickeners such as agar agar, guar gum, alginates, xanthan gum, rubber arabic cum, karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives, e.g. B. methyl cellulose, hydroxyalkyl cellulose and carboxymethyl cellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such. B. bentonite or fully synthetic hydrocolloids such. B. polyvinyl alcohol, structurants such as glucose and maleic acid, hair conditioning compounds such as phospholipids, for example soy lecithin, egg lecithin and cephalins, and silicone oils,

Protein hydrolyzates, in particular elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolyzates, their condensation products with fatty acids and quaternized protein hydrolyzates, perfume oils, dimethyl isosorbide and cyclodextrins,

Solubilizers such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerin and diethylene glycol,

Anti-dandruff agents such as piroctone olamine and zinc omadine, other substances for adjusting the pH value,

Active ingredients such as panthenol, pantothenic acid, allantoin, pyrrolidone carboxylic acids and their salts, plant extracts and vitamins, cholesterol, light stabilizers,

Consistency enhancers such as sugar esters, polyol esters or polyol alkyl ethers, fats and waxes such as walrus, beeswax, montan wax, paraffins, fatty alcohols and fatty acid esters, fatty acid alkanolamides,

Complexing agents such as EDTA, NTA and phosphonic acids,

Swelling and penetration substances such as glycerol, propylene glycol monoethyl ether, carbonates, hydrogen carbonates, guanidines, ureas and primary, secondary and tertiary phosphates, imidazoles, tannins, pyrrole, Opacifiers like latex,

Pearlescent agents such as ethylene glycol mono- and distearate,

Blowing agents such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air as well

Antioxidants.

The constituents of the water-containing carrier are used for the preparation of the agents according to the invention in amounts customary for this purpose; z. For example, emulsifiers are used in concentrations of 0.5 to 30% by weight and thickeners in concentrations of 0.1 to 25% by weight of the total agent.

For the coloring result it can be advantageous to add ammonium or metal salts to the agents. Suitable metal salts are e.g. B. formates, carbonates, halides, sulfates, butyrates, valerates, capronates, acetates, lactates, glycolates, tartrates, citrates, gluconates, propionates, phosphates and phosphonates of alkali metals, such as potassium, sodium or lithium, alkaline earth metals, such as Magnesium, calcium, strontium or barium, or of aluminum, manganese, iron, cobalt, copper or zinc, whereby sodium acetate, lithium bromide, calcium bromide, calcium gluconate, zinc chloride, zinc sulfate, magnesium chloride, magnesium sulfate, ammonium carbonate, chloride and acetate are preferred. These salts are preferably present in an amount of 0.03 to 65, in particular 1 to 40, mmol based on 100 g of the total composition.

Another object of the present invention is a process for dyeing keratin-containing fibers, in particular human hair, in which a colorant according to the invention, containing customary cosmetic ingredients, is applied to the keratin-containing fibers, left on the fiber for some time, usually about 30 minutes, and then rinsed out again or washed out with a shampoo.

In principle, the oxidative development of the coloring can take place with atmospheric oxygen. However, a chemical oxidizing agent is preferably used, especially if, in addition to the coloring, a lightening effect on human hair is desired. Persulfates, chlorites and in particular hydrogen peroxide or its adducts with urea, melamine and sodium borate are suitable as oxidizing agents. It is also possible to carry out the oxidation with the aid of enzymes. The enzymes can be used to transfer atmospheric oxygen to the developer component or to enhance the effect of small amounts of oxidizing agents present. An example of an enzymatic Process represents the procedure to increase the effect of small amounts (eg 1% and less, based on the total agent) of hydrogen peroxide by peroxidases.

The preparation of the oxidizing agent is expediently mixed with the preparation from the oxidation dye precursors immediately before hair dyeing. The resulting ready-to-use hair dye preparation should preferably have a pH in the range between 2 and 11, preferably between 5 and 10. It is particularly preferred to use the hair products in a weakly alkaline environment. The application temperatures can range between 15 and 40 ° C. After an exposure time of approx. 30 minutes, the agent is removed from the hair to be colored by rinsing. Washing with a shampoo is not necessary if a carrier with a high tenside content, e.g. a coloring shampoo was used.

Yet another object of the present invention relates to the use of compounds of the formula (I) for dyeing fibers containing keratin.

The following examples are intended to explain the subject of the invention in more detail.

B e i s p i e l e

Preparation Example 1

Step 1: (4-nitro-1,3-dimethylpyrazol-5-yl) - (2 - ((4-nitro-1,3-dimethylpyrazol-5-yl) amino) ethyl) -amir To a mixture of 4, 4 g (0.025 mol) of 5-chloro-1, 3-dimethyl-4-nitropyrazole, 1.7 g (0.125 mol) of K ₂ CO ₃ and 0.1 g of Cu powder in 100 ml of 1-butanol were at 80 ° C. A solution of 0.75 g (0.0125 mol) of 1,2-diaminoethane in 25 ml of 1-butanol was added dropwise. After refluxing for 13 hours, the hot solution was filtered off, after cooling the product was filtered off with suction. Yellow crystals with a melting point of 237 ° C. were obtained

Level 2:

The product from stage 1 was hydrogenated in 200 ml of ethanol and 0.1 g of Pd / C at 78 ° C. and 25 atm. After the H ₂ uptake had ended, the catalyst was filtered off. The solution was acidified with dilute HCl and evaporated to dryness. There was (4-amino-1, 3-dimethylpyrazol-5-yl) - (2 - ((4-amino-1, 3-dimethylpyrazol-5-yl) amino) ethyl) amine x 4HCI in the form of brown crystals with obtained a melting point of 220 ° C.

Production Example 2

Stage 1: Stage 1 from preparation example 1 was repeated, using 1.1 g (0.0125 mol) of piperazine instead of 1,2-diaminoethane.

Stage 2: analogous to stage 2 from preparation example 1. 1,4-bis- (1,3-dimethyl-4-nitro-pyrazol-5-yl) -piperazine x 4 HCl was obtained in the form of orange crystals with a melting point above 206 ° C obtained (decomposition).

Production Example 3

Step 1: A mixture of 7 g (0.04 mol) of 5-chloro-1, 3-dimethyl-4-nitropyrazole, 10.3 g (0.08 mol) of 1- (2-aminoethyl) piperidine and 4 g (0.048 mol) NaHCO ₃ in 60 ml dimethyl sulfoxide was stirred at 90 ° C for 4 hours. The reaction mixture was poured onto 500 g of ice and the precipitate was filtered off with suction. Yellow crystals with a melting point of 124 ° C. were obtained. Stage 2: 9 g of the product obtained in stage 1 were hydrogenated in 400 ml of ethanol with 0.6 g of Pd / C at room temperature and 1 atm. After the H ₂ uptake had ended, the catalyst was filtered off. The solution was acidified with dilute HCl and evaporated to dryness. (4-Amino-1,3-dimethylpyrazol-5-yl) - (2-piperidyethyl) amine was obtained in the form of beige crystals with a melting point of 123 ° C. (decomposition).

Production Example 4

Step 1: Step 1 from preparation example 3 was repeated, using 10.4 g (0.08 mol) of N- (2-aminoethyl) morpholine instead of 1- (2-aminoethyl) piperidine. Yellow crystals with a melting point of 112-114 ° C. were obtained.

Step 2: analogous to step 2 from preparation example 3. It was (4-amino-1, 3-dimethylpyrazol-5-yl) - (2-morpholin-4-yl-ethyl) amine x 3HCI in the form of yellow crystals with obtained a melting point of 105 ° C.

Production Example 5

Step 1: Step 1 from preparation example 3 was repeated, using 11.5 g (0.08 mol) of N- (3-aminopropyl) morpholine instead of 1- (2-aminoethyl) piperidine. Yellow crystals with a melting point of 87-89 ° C. were obtained.

Step 2: analogous to step 2 from preparation example 3. It was (4-amino-1, 3-dimethylpyrazol-5-yl) -3-morpholin-4-yl-propyl) amine x 3HCI in the form of yellow crystals with a Obtained melting point of 104 ° C.

Production Example 6

Step 1: To a solution of 5 g (0.028 mol) of 5-hydrazino-1, 3-dimethyl-4-nitro-1H-pyrazole and 4.68 g (0.028 mol) of tetramethoxypropane in 80 ml of ethanol were 19. Given 8 ml of 10% HCI. The mixture was boiled under reflux for 2 hours, then 3 g (0.028 mol) of Na ₂ CO ₃ in 10 ml of H ₂ O were added and the solution became dry evaporated. The residue was extracted with ethanol. After concentration, the residue was recrystallized from EtOH. Bright orange crystals with a melting point of 75 ° C. were obtained.

Stage 2: analogous to stage 2 from preparation example 3. This gave (1,3-dimethyl-5-pyrazolyl-pyrazo-4-amine x 3HCI in the form of orange crystals and a melting point> 150 ° C. (decomposition).

Production Example 7

Step 1: Step 1 from preparation example 3 was repeated, using 10.09 g (0.08 mol) of 1- (3-aminopropyl) imidazole instead of 1- (2-aminoethyl) piperidine. A yellow oil was obtained.

Step 2: analogous to step 2 from preparation example 3. (4-Amino-1,3-dimethylpyrazol-5-yl) - (3-imidazolylpropyl) amine x 3HCI was obtained in the form of a brown oil.

Production Example 8

Step 1: Step 1 from preparation example 3 was repeated, using 12.7 g (0.08 mol) of 2-amino-5- (diethylamino) pentane instead of 1- (2-aminoethyl) piperidine. A yellow oil was obtained.

Step 2: analogous to step 2 from preparation example 3. (4-Amino - ((1, 3-dimethyl-4-aminopyrazol-5-yl) -amino) pentyl) -diethylamine x 3HCI was obtained in the form of a brown oil.

Production Example 9

Step 1: Step 1 from preparation example 3 was repeated, using 5.9 g (0.08 mol) of glycinamide instead of 1- (2-aminoethyl) piperidine. Orange crystals with a melting point above 250 ° C. were obtained.

Step 2: analogous to step 2 from preparation example 3. 2 - ((4-Aιmino-1, 3-dimethylpyrazol-5-yl) -amino) -acetamide x 2HCI in the form of a beige powder with a melting point of 220 ° C. ( Decomposition).

Production Example 10

Step 1: Step 1 from preparation example 3 was repeated, using 6.8 g (0.08 mol) of cyclopentylamine instead of 1- (2-aminoethyl) piperidine. Yellow crystals with a melting point of 76-80 ° C. were obtained.

Step 2: analogous to step 2 from preparation example 3. 4-Amino-1,3-dimethylpyrazol-5-yl-cyclopentylamine x 2HCI was obtained in the form of beige powder with a melting point of 147 ° C.

Production Example 11

Step 1: Step 1 from preparation example 3 was repeated, using 10.3 g (0.08 mol) of 1- (2-aminoethyl) piperazine instead of 1 - (2-aminoethyl) piperidine. Yellow crystals with a melting point of 124 ° C. were obtained.

Stage 2: analogous to stage 2 from preparation example 3. (1, 3-dimethyl-4-amino-5-yl) - (2-piperazinylethylamine) x 4HCI was obtained in the form of brown crystals with a melting point above 108 ° C. (decomposition) , Production Example 12

Step 1: Step 1 from preparation example 3 was repeated, using 8.3 g (0.08 mol) of 3-ethoxypropylamine instead of 1- (2-aminoethyl) piperidine. Yellow crystals with a melting point of 44 ° C. were obtained.

Stage 2: analogous to stage 2 from preparation example 3. 4-Amino-1,3-dimethylpyrazol-5-yl) - (3-ethoxypropyl) amine x 3HCI was obtained in the form of orange-colored hygroscopic crystals.

Production Example 13

Step 1: Step 1 from preparation example 3 was repeated, 9.7 g (0.08 mol) of 2-phenylethylamine being used instead of 1- (2-aminoethyl) piperidine. Yellow crystals with a melting point of 99-101 ° C. were obtained.

Stage 2: analogous to stage 2 from preparation example 3. It became (4-amino-1,3-dimethylpyrazol-5-yl) - (2-phenylethyl) amine x 2HCI in the form of gray-blue crystals with a melting point of 85-90 ° C received.

Production Example 14

Step 1: 7.9 g (0.045 mol) of 5-chloro-1,3-dimethyl-4-nitropyrazole were placed in 60 ml of dimethyl sulfoxide with stirring in a nitrogen atmosphere. A solution of 5 g (0.045 mol) glycinamide hydrochloride, 7.5 g potassium carbonate (0.054 mol) and 20 ml water was added. The mixture was then stirred at 70 ° C. for 22 h. The reaction mixture was cooled and poured onto ice. The yellow / orange precipitate was suction filtered, washed with water, slurried in 50 ml of cold dimethylformamide, suction filtered again and washed with water. The reaction product was dried at 50 ° C in a vacuum and had a melting point above 250 ° C.

Step 2: 3 g (0.014 mol) of 2 - ((1 ', 3'-dimethyl-4'-nitropyrazol-5'-yl) amino) -acetamide were dissolved in 150 ml of ethanol and 50 ml of water with 0.65 g of a Pd catalyst ( 5% Pd on C) at Room temperature hydrogenated. 20 ml of a 20% HCl solution were then added, the reaction mixture was filtered under nitrogen and evaporated to dryness. 2 - ((1 ', 3'-Dimethyl-4 ^, -aminopyrazol-5'-yl) amino) -acetamide dihydrochloride was obtained, which decomposed at 220 ° C.

Production Example 15

Step 1: 8.0 g (0.046 mol) of 5-chloro-1, 3-dimethyl-4-nitropyrazole, 3.6 g (0.042 mol) of cyclopentylamine and 4.4 g (0.052 mol) of sodium hydrogen carbonate were in 50 ml of dimethyl sulfoxide for 22 h at 75 to 80 ° C stirred. The reaction mixture was cooled and poured onto ice. The yellow precipitate was filtered off and recrystallized from 500 ml of water at 50 to 60 ° C. The reaction product was dried at 50 ° C in a vacuum and had a melting point of 76 to 80 ° C with decomposition.

Step 2: 6.1g (0.027 mol) (1,3-dimethyl-4-nitropyrazol-5-yl) cyclopentylamine were dissolved in 75ml ethanol and 25ml water with 0.53g Pd catalyst (5% Pd on C) at 50 ° C and 20bar hydrogenated for 24h in an autoclave. 20 ml of a 20% HCl solution were then added, the reaction mixture was filtered under nitrogen and evaporated to dryness. (1, 3-Dimethyl-4-aminopyrazol-5-yl) cyclopentylamine was obtained, which decomposed at 147 ° C.

Coloring examples 1 to 30

First, a cream base of the following composition was produced [unless otherwise stated, all data are in g]:

Taig fatty alcohol 17.0

Lorol ^® techn. 4.0

Texapon ^® N 28 ² 40.0

Dehyton ^ K 25.0

Eumulgin ^® B 2 1, 5 distilled water 12.5

C ₁₂ ιs fatty alcohol (Cognis)

Sodium lauryl ether sulfate (approx. 28% active substance; INCI name: Sodium

Laureth Sulfate) (Cognis)

Fatty acid amide derivative with betaine structure of the formula

R-CONH (CH ₂ ) ₃ N ⁺ (CH ₃ ) ₂ CH ₂ COO- (approx. 30% active substance; INCI name Co-coamidopropyl betaine) (Cognis)

Cetylstearyl alcohol with approx. 20 EO units (INCI name: Ceteareth-

20) (Cognis)

The following hair dye cream emulsion was then produced on the basis of this cream:

Cream base 50.0

Developer component 7.5 mmol

Coupler component 7.5 mmol

Na ₂ SO ₃ (inhibitor) 1.0

(NH ₄ ) ₂ SO ₄ 1.0 conc. Ammonia solution ad pH 10

Water ad 100

The ingredients were mixed together in order. After the oxidation dye precursors and the inhibitor had been added, concentrated ammonia solution, the pH of the emulsion was adjusted to 10, then the mixture was made up to 100 g with water.

The oxidative development of the color was carried out with atmospheric oxygen or 1% hydrogen peroxide solution as the oxidation solution. For this purpose, the emulsion for air oxidation was left as it was, for oxidation with H ₂ O ₂ , 100 g of the emulsion were mixed with 50 g of hydrogen peroxide solution (1%) and mixed.

The resulting application preparation was applied in each case to strands of approximately 5 cm long, standardized, 90% gray, but not specially pretreated human hair and left there at 32 ° C. for 30 minutes. After the dyeing process was completed, the hair was rinsed, washed with a conventional shampoo and then dried. The following developer and coupler components were used for the colorations:

Developer components (according to the invention)

E1 (1, 3-Dimethyl-4-aminopyrazol-5-yl) - (2 - ((1 ', 3'-dimethyl-4'-aminopyrazol-5'-yl) amino) ethyl) amine x 4HCI

E2 1, 4-bis (1 ', 3'-dimethyl-4'-aminopyrazol-5-yl) piperazine x 4 HCl

E3 (1, 3-dimethyl-4-aminopyrazol-5-yl) - (2-piperazinylethyl) amine

E4 (1, 3-Dimethyl-4-aminopyrazol-5-yl) - (2- (morpholin-4'-yl) ethyl) amine x 3HCI

E5 (1, 3-Dimethyl-4-aminopyrazol-5-yl) - (3- (morpholin-4'-yl) propyl) amine x 3HCI

E6 1 - (1 ', 3'-Dimethyl-4'-aminopyrazol-5'-yl) pyrazole x 3HCI

E7 (1, 3-Dimethyl-4-aminopyrazol-5-yl) - (3-imidazolylpropyl) amine x 3HCI

E8 (4-amino - ((1,3-dimethyl-4-aminopyrazol-5-yl) amino) pentyl) diethylamine x 3HCI

E9 2 - ((1 ', 3'-Dimethyl-4'-aminopyrazol-5'-yl) amino) acetamide x 2HCI

E10 (1, 3-dimethyl-4-aminopyrazol-5-yl) - (cyclopentyl) amine x 2HCI

E11 (1, 3-Dimethyl-4-aminopyrazol-5-yl) - (2-piperazinylethyl) amine x 4HCI x 2H ₂ O

E12 (1, 3-Dimethyl-4-aminopyrazol-5-yl) - (3-ethoxypropyl) amine x 2HCI

E13 (1,3-dimethyl-4-aminopyrazol-5-yl) - (2-phenylethyl) amine x 2HCI

Coupler components K

K1 2-methyl-5-aminophenol

K2 2-chloro-6-methyl-3-aminophenol K3 1-naphthol

K4 1,3-bis (2 ', 4'-diamino-phenoxy) propane

K5 m-aminophenol

K6 2,4-diaminophenoxyethanol

K7 resorcinol

the following colors were found:

Coloring example 31

The following coloring cream and the following oxidizing agent preparation were produced:

C ₁₂ ι fatty alcohol with approx. 2 EO units (INCI name: Laureth-2) (Cognis)

C ι _12- ₈ fatty alcohol (INCI name: Coconut Alcohol) (Cognis)

Oleic acid (INCI name: Oleic Acid) (Cognis)

Lauryl ether sulfate sodium salt (approx. 26.5 to 27.5% active substance content; INCI name: Sodium Laureth Sulfate) (Cognis)

Wheat protein hydrolyzate (approx. 40% solids; INCI name: Aqua (Water), Hydrolyzed Wheat Protein, Sodium Benzoate, Phenoxyethanol, Methylparaben, Propylparaben) (Cognis)

10

1-Hydroxyethane-1, 1-diphosphonic acid (approx. 58 to 61% active substance; INCI name: Etidronic Acid, Aqua (Water)) (Cognis)

11 methacrylic acid (stearyl alcohol + 20-EO-ester) -acrylic acid copolymer (approx. 30% active substance; INCI name: Acrylates / Steareth-20 methacrylate copolymer) (Rohm & Haas)

12 hydrogen peroxide (approx. 50% active substance content; INCI name: hydrogen peroxide) (Degussa)

2 g of the coloring cream were mixed with 2 g of the oxidizing agent preparation and applied to 5 to 6 cm long strands of hair (Kerling, 80% gray). After 30 min. Exposure time at 32 ° C, the hair was rinsed, washed out with a normal shampoo and then dried. The hair was purple in color.

Coloring example 32

13

C ₆ -i8 fatty alcohol (INCI name: Cetearyl Alcohol) (Cognis) 14

2-Octyldodecyl alcohol (INCI name: Octyldodecanol) (Cognis) 15

C ₁₆ -i8 fatty alcohol with approx. 12 EO units (INCI name: Ceteareth-12) (Cognis) 16

Lauryl myristyl ether sulfate sodium salt (approx. 68 to 73% active substance content; INCI name: Sodium Myreth Sulfate) (Cognis)

17

C _12-16 -alkyl-1,4-glucoside (approx. 50 to 53% active substance content; INCI name: Lauryl Glucoside) (Cognis) 18

Lauryl alcohol-4.5-EO-acetic acid sodium salt (at least 21% active substance content; INCI name: Sodium Laureth-6 carboxylate) (Chem-Y)

19

Acrylic acid-sodium salt-acrylamidopropyltrimethylammonium chloride copolymer preserved with Phenonip (approx. 19 to 21% active substance content; INCI name: Acrylamidopropyltrimonium Chloride / Acrylates Copolymer) (Stockhausen)

20 silicone emulsion, non-ionic (approx. 10% active substance content; INCI name: Dimethicone) (Dow Corning)

2 g of the coloring cream were mixed with 2 g of the oxidizing agent preparation and applied to 5 to 6 cm long strands of hair (Kerling, 80% gray). After 30 min. Exposure time at 32 ° C, the hair was rinsed, washed out with a normal shampoo and then dried. The hair was brown in color.

Claims

Patent claims

1. Means for dyeing keratin-containing fibers containing oxidation dye precursors, characterized in that at least one compound of the general formula I is contained as developer component

in the

R1 and R2 may be the same or different and represent hydrogen, C _1-4 alkyl or C _1-4 hydroxyalkyl and R3 represents

• for a group with the formula II,

in which R4 represents a piperazinyl radical or a group -NR7 (CH ₂ ) _n -NR7, in which R7 is hydrogen or C _1-4 -alkyl and n can be an integer from 1 to 4,

R5 and R6 may be the same or different and are hydrogen, C ₁ alkyl or C-ι mean _-4 hydroxyalkyl,

for a group ° the

• for a group

in which R9 is hydrogen, C _1-4 -alkyl or C _1- -hydroxyalkyl,

Y stands for a direct bond or a straight-chain or branched C _1-5 -

Alkylene group and A stands for a saturated or unsaturated, optionally containing one or more heteroatoms 5-, 6- or 7-ring, a group -CO-NH ₂ , a C _1- alkoxy group or a C _1- dialkylamino group, A with each any carbon atom of the alkylene group Y can be linked.

2. Composition according to claim 1, characterized in that in the formula I R3 represents a group with the formula II.

3. Means according to claim 2, characterized in that R1 and R6 and R2 and R5 are each the same.

4. Composition according to one of claims 2 or 3, characterized in that the compound of formula I is selected from (1, 3-dimethyl-4-amino-pyrazol-5-yl) - (2- ((1 ', 3rd '-dimethyl-4'-aminopyrazol-5 ^, -yl) amino) ethyl) amine and 1,4-bis (1', 3'-dimethyl-4'-aminopyrazol-5'-yl) piperazine or their salts.

5. Composition according to claim 1, characterized in that the group A represents one of the groups piperidyl, morpholin-4-yl, imidazolyl, cyclopentyl, piperazinyl, pyrazolyl or phenyl.

6. Composition according to claim 1 or 5, characterized in that the group Y represents an ethylene or a propylene group.

7. Composition according to one of claims 1, 5 or 6, characterized in that the substituent -YA stands for a 2-piperidylethyl radical, a 2- (morpholin-4-yl) ethyl radical, a 3- (morpholin-4-yl) propyl, 3-imidazolylpropyl, (N, N-diethylamino) pentyl, cyclopentyl, 2-piperazinylethyl, 2-phenylethyl or 3-ethoxypropyl.

8. Agent according to one of claims 1 or 5 to 7, characterized in that the compound of formula I is selected from (1, 3-dimethyl-4-aminopyrazol-5-yl) - (2-piperidylethyl) amine, (1,3-Dimethyl-4-aminopyrazol-5-yl) - (2- (morpholin-4'-yl) ethyl) amine, (1,3-dimethyl-4-aminopyrazol-5-yl) - (3rd - (Morpholin-4'-yl) propyl) amine, 1,3-dimethyl-4-amino-5-pyrazolylpyrazole, (1,3-dimethyl-4-aminopyrazol-5-yl) - (3-imidazolylpro - propyl) amine, N- (4 - ^((1, 3'-dimethyl-4 ^* -aminopyrazol-5'-yl) amino) pentyl) -N, N-diethyl-amine, (1,3-dimethyl-4-aminopyrazol-5-yl) - (cyclopentyl) amine, (1,3-dimethyl-4-aminopyrazol-5-yl) - (2-piperazinylethyl) amine, (1,3 dimethyl-4-aminopyrazole-5-yl) - (2-phenylethyl) - amine, 2 - ^{((4'-amino-1,} 3'-dimethylpyrazol-5'-yl) amino) -acetamide, (4 -Amino-1, 3-dimethyl-pyrazol-5-yl) - (3-ethoxypropyl) amine and their physiologically tolerable salts and any mixtures of the foregoing.

9. Composition according to one of claims 1 to 8, characterized in that the compound with the formula I is contained in total in an amount of 0.005 to 20 wt .-%, preferably 0.1 to 5 wt .-%.

10. Agent according to one of claims 1 to 9, characterized in that further developer components selected from primary aromatic amines with a further, 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 are used.

11. Agent according to claim 10, characterized in that the further developer components are selected from p-phenylenediamine, p-toluenediamine, 2,4,5,6-tetraaminopyrimidine, p-aminophenol, N, N-bis (2'-hydroxyethyl) -p-phenylenediamine, 2- (2 ', 5'-diaminophenyl) ethanol, 2- (2', 5'-diaminophenoxy) ethanol, 4-amino-3-methylphenol, 2-aminomethyl-4-aminophenol , 4-amino-2-diethylaminomethylphenol, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triamino-4-hydroxypyrimidine and 1, 3-N , N'-bis (2'-hydroxyethyl) -N, N'-bis (4'-aminophenyl) diamino-propan-2-ol are contained.

12. Composition according to one of claims 1 to 11, characterized in that it contains at least one coupler component.

13. Composition according to claim 12, characterized in that the coupler component is selected from 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.

14. Composition according to one of claims 1 to 13, characterized in that the developer and coupler components in each case in an amount of 0.005 to 20 wt .-%, preferably 0.1 to 5 wt .-%, each based on the entire oxidation colorant , are included.

15. Agent according to one of claims 1 to 14, characterized in that it also contains at least one substantive dye.

16. A process for dyeing keratin-containing fibers, in particular human hair, wherein a colorant as claimed in any one of claims 1 to 15, containing customary cosmetic ingredients, is applied to the keratin-containing fibers for some time, usually about 30 minutes, and then rinsed out again or washed out with a shampoo.

17. Use of compounds of formula (I) for dyeing keratin fibers.