EP1229891A1

EP1229891A1 - Agent for colouring keratin containing fibres

Info

Publication number: EP1229891A1
Application number: EP00969497A
Authority: EP
Inventors: David Rose; Horst Höffkes; Bernd Meinigke
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1999-10-22
Filing date: 2000-10-13
Publication date: 2002-08-14
Also published as: DE19951009A1; WO2001034105A1; AU7919000A

Abstract

An agent for colouring keratin containing fibres is disclosed, which is particularly suitable as an oxidative colouring agent and comprises a combination of: A) at least one aminophenol derivative of formula (I), or a water-soluble, physiologically acceptable salt thereof and B) at least one 1,4-diazacycloheptane derivative of formula (II).

Description

"Means for dyeing fibers containing keratin"

The invention relates to agents for dyeing keratin-containing fibers which contain a combination of at least one p-aminophenol derivative and at least one 1,4-diazacycloheptane derivative, and to a process for dyeing keratin-containing 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 hydroxy 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-diethylaminomethyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol , 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triamino-4-hydroxypyrimidine.

M-Phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives are generally used as coupler components. Particularly suitable coupler substances are 1-naphthol, 1, 5-, 2,7- and 1, 7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinomino methyl ether, 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-methylresorcinol, 5-methylresorcinol and 2-methyl-4-chloro-5-aminophenol.

With regard to further customary dye components, reference is expressly made to the “Dermatology” series, edited by Ch. Cuinan, H. Maibach, publisher 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 Industrial and Commercial Enterprises for Medicines, Health Care Products and Personal Care Products, Mannheim ,

DE 196 07 751 A1 describes the use of special aminophenol derivatives alone as a developer component in oxidation colorants for dyeing keratin fibers. DE 197 07 545 A1 discloses 1,4-diazacycloheptane derivatives and their use as developer components in oxidation colorants.

With a developer component or a special coupler / developer combination alone, it is usually not possible to obtain a color shade that looks natural on the hair. In practice, therefore, combinations are usually used various developer components and coupler components. There is therefore a constant need for new, improved dye combinations.

It was therefore the object of the present invention to find combinations of components which are suitable for use in colorants and which, in particular, particularly meet the requirements for oxidation colorants.

It has now been found that combinations of certain aminophenol derivatives and 1,4-diazacycloheptane derivatives are outstandingly suitable as a coloring component in agents for dyeing keratin-containing fibers and also meet the requirements. Thus, using these developer components with most known coupler components, brilliant color shades are obtained, particularly in the brown, blue 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 agents for dyeing fibers containing keratin, comprising a combination of

A) at least one aminophenol derivative of the formula I or one of the water-soluble, physiologically tolerable salts

wherein the radicals R ¹ and R ^{2 are} independently

Hydrogen, a C _1-4 -alkyl group, a C _M -alkoxy group, a C _1-4 -monohydroxyalkyl group, a C ^ -dihydroxyalkyl group, a -C _a H _2a OC _b H _{2b + 1} group with a = 1 - 3 and b = 1 - 3, an allyl group, - -O-CH ₂ -CH = CH ₂ ,

-CH = CH-COOX with X = H or a physiologically compatible inorganic or organic cation, or a halogen atom, and one of the radicals R ³ and R ⁴ stands for

Hydrogen is a C _1-4 alkoxy group, a C _1-4 alkyl group, a C ^ hydroxyalkyl group, preferably with a terminal

Hydroxy group, or a halogen atom, and the other R ³ or R "represents one of the groups:

-O-CH ₂ -CH = CH _2,

-CH = CH-COOX, where X stands for hydrogen or a physiologically compatible inorganic or organic cation, for a group

or for a group

in which -A- stands for «sine of the groups

- (CH ₂ ) _X - with x = 1 - 4,

-O- (CH ₂ ) _y -O- with y = 1 * - 4, -O- (C _n H _2n . ₂ (OH) _z ) -O- with n = 1 - 10 and z = 1 or if n is greater than or equal to 3, Z = 2, -O- (C ₂ H ₄ - O) _u - with u = 1 - 4 and

--O- (C ₃ H ₆ -O) _v - with v = 1 - 4, and in which the radicals R ⁵ , R ⁶ and R ⁷ independently of one another represent hydrogen, a C 1-4 alkyl group, a C _{1- 4} -alkoxy group, a C _1-4 -monohydroxyalkyl group, a C ^ -dihydroxyalkyl group, a -C _a H _2a OC _b H _{2b +} ι group with a = 1-3 and b = 1-3, an allyl group,

- -O-CH ₂ -CH = CH ₂ ,

-CH = CH-COOX with X = H or a physiologically compatible inorganic or organic cation, or a halogen atom, and at least one 1,4-diazacycloheptane derivative of the formula II

in the

R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ independently represent hydrogen, a C _1-4 -

Alkyl or hydroxyalkyl group or a C _2-4 -dihydroxyalkyl group,

Y and Z independently represent hydrogen, chlorine, fluorine, one

C _M -alkyl, -hydroxyalkyl, -aminoalkyl or -alkoxy group, a C _2-4 -

Dihydroxyalkyl group or an allyl group and

R ¹² and R ¹³ independently of one another represent hydrogen or a C _1-4 -

Alkyl group. Since all substances with the formulas I and II are amino compounds, the known acid addition salts can be prepared from them in the usual way. All statements in this document and accordingly the claimed scope of protection therefore relate both to the compounds according to formula (I) and formula (II) present in free form and to their water-soluble, physiologically tolerable salts. Examples of such salts are the hydrochlorides, the hydrobromides, the sulfates, the phosphates, the acetates, the propionates, the citrates and the lactates.

Keratin-containing fibers are wool, furs, feathers and in particular human hair. In principle, however, the agents according to the invention can also be used for dyeing other natural fibers, such as, for. As cotton, jute, sisal, linen or silk, modified natural fibers, such as. B. regenerated cellulose, nitro, alkyl or hydroxyalkyl or acetyl cellulose and synthetic fibers such as. B. polyamide, polyacrylonitrile, polyurethane and polyester fibers can be used. 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.

Examples of the C _r to C ₄ alkyl groups mentioned as substituents in the compounds according to the invention are the groups methyl, ethyl, propyl, isopropyl and butyl. Ethyl and methyl are preferred alkyl groups. Furthermore, a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group can be mentioned as preferred examples of a Cr to C ₄ -hydroxyalkyl group, a 2-hydroxyethyl group is particularly preferred. A C to C ₄ alkoxy group preferred according to the invention is, for example, a methoxy or an ethoxy group. Examples of a halogen atom are, according to the invention, an F, a Cl or a Br atom, a Cl atom is particularly preferred. According to the invention, the other designations used are derived from the definitions given here.

The compounds described as component A are known, for example, from DE 196 06 751 A1 and can be prepared using known organic synthesis methods. The compounds of component B are disclosed, for example, in DE 197 07 545 A1 and can also be obtained by known synthesis methods, provided that they are not commercially available. The compounds of component A and Component B is preferably used in a molar ratio of 1:20 to 20: 1.

The compounds of component A which are particularly suitable according to the invention have proven to be the aminophenol derivatives of the formula (I) in which both R ¹ and R ^{2 are} hydrogen.

Also preferred according to the invention are those compounds of the formula (I) in which one of the two radicals R ³ or R ^{4 is} hydrogen.

According to the dinuclear p-aminophenol derivatives, the symmetrically substituted compounds are preferred according to the invention.

Among the compounds of formula (I) derived from cinnamic acid, the free acids (X = H) are preferred. However, the alkali metal, alkaline earth metal, aluminum, ammonium and the mono-, di- and tri-C _1-4 -hydroxyalkylammonium salts can also be used according to the invention.

Among the compounds which represent hydroxyalkyl diethers, preference is given to those in which n is a number from 1 to 6, in particular from 1 to 3, and which have a hydroxyl group on the aliphatic chain (z = 1).

Substances of component A which are particularly outstanding in the sense of the overall invention are bis- (5-amino-2-hydroxyphenyl) methane, bis- (5-amino-3-methyl-2-hydroxyphenyl) methane, 3-hydroxy-6- amino-allyloxybenzene, 2-hydroxy-5-amino-allyloxybenzene, 5-amino-2-hydroxycinnamic acid, bis- [2- (2'-hydroxy-5'-aminophenoxy) ethyl] ether, 1, 8-bis [ 2'-hydroxy-5'-aminophenoxy] -3,6-dioxaoctane, 1,3-bis (2'-hydroxy-5'-aminophenoxy) propane and 1,3-bis (2'-hydroxy-5 ' -aminophenoxy) propane-2-ol.

Substances of component B which are preferably used are 1,4-diazacycloheptane derivatives of the formula (II) in which both radicals R ¹² and R ¹³ on the 1,4-diazacycloheptane ring are hydrogen. Also preferred according to the invention are those compounds of the formula (II) in which at least three, in particular all four, groups R ⁸ , R ⁹ , R ¹⁰ and R ^{11 are} hydrogen.

Finally, those 1,4-diazacycioheptane derivatives according to formula (II) have also proven to be particularly suitable according to the invention in which the two substituents Y and Z on the two aromatic rings independently of one another represent hydrogen, fluorine, chlorine or a C _{1- 4} alkyl group. Hydrogen and methyl groups have proven to be particularly advantageous groups Y and Z.

For the purposes of the invention, preference is given to N, N'-bis (4'-aminophenyl) -1, 4-diazacycloheptane, N, N'-bis (4'-amino-2'-methylphenyl) -1, 4-diazacycloheptane and N, N'-bis (4'-amino-3'-methylphenyl) -1, 4-diazacycloheptane. Among these compounds, N, N'-bis (4'-aminophenyl) -1, 4-diazacycloheptane and N, N'-bis (4'-amino-3'-methylphenyl) -1, 4-diazacycloheptane are particularly special prefers.

The compositions according to the invention are particularly suitable as so-called oxidation colorants. In oxidation colorants, the combination of the compounds of the formulas I and II according to the invention acts as developer components. If desired, further developer components and coupler components can also be included. With regard to the further developer and coupler components, reference is made to the substances listed at the beginning of the description, which are preferred further dye components.

Preferred developer components according to the invention are p-phenylenediamine, p-toluylenediamine, p-aminophenol, o-aminophenol, 1- (β-hydroxyethyl) -2,5-diaminobenzene, N, N-bis (β-hydroxyethyl) -p- phenylenediamine, 2- (2 ', 5'-diaminophenoxy) ethanol, 4-amino-3-methylphenol, 2,4,5, 6-tetraaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 4-hydroxy- 2,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2-dimethylamino-4,5,6-triaminopyrimidine, 2-hydroxyethylaminomethyl-4-aminophenol, 4,4'-

Diaminodiphenylamine, 4-amino-3-fluorophenol, 2-aminomethyl-4-aminophenol, 2-diethylaminomethyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol, N, N'-bis (ß-hydroxyethyl) -N , N'-bis- (4'-aminophenyl) -1, 3-diamino-propan-2-ol, 4-amino-2- (ß- hydroxyethoxy) phenol and 4,5-diminopyrazole derivatives according to EP 0 740 931 or WO 94/08970 such as 4,5-dimin-1- (β-hydroxyethyl) pyrazole

Very particularly preferred further developer components are 2,4,5,6-tetraamine-πmidine, 4-hydroxy-2,5,6-trionamine-pyramide, 1- (β-hydroxyethyl) -2,5-diminobenzene, p-phenylenediamine, p- Toluene diamine, N, N-Bιs- (ß-hydroxyethyl) -p-phenylenedιamιn, p-aminophenol, 3-methyl-p-aminophenol, 2-aminomethyl-p-aminophenol, 2-

Dιethylamιnomethyl-4-amιnophenol and N, N'-Bιs- (ß-hydroxyethyl) -N, N'-bιs (4'-amιno-phenyl) -1, 3-dιamιno-propan-2-ol

Coupler components preferred according to the invention are 1-naphthol, pyrogallol, 1, 5-, 2,7- and 1,7-dihydroxynaphthalene, o-aminophenol, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m- Phenylenediamine, 1-phenyl-3-methyl-pyrazolone-5, 2,4-dιchlor-3-aminophenol, 1, 3-bιs- (2 ', 4'-dιamιnophenoxy) propane, 4-chloro-resorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcin, 5-methylresorcin, 2,5-dimethyresorcinol, 2,6-dihydroxypyridin, 2,6-diminopyridin, 2-aminon-3-hydroxypyridin, 2, 6- dihydroxy-3,4-diminopyπdιn, 3-amino-2-methylamine-6-methoxypyride, 4-amino-2-hy-hydroxytoluene, 2,6-bis (β-hydroxyethylamino) toluene, 2 4-diminophenoxyethanol , 1-methoxy-2-amino-4- (ß-hydroxyethylamine) -benzene, 2-methyl-4-chloro-5-amino-phenol, 6-methyl-1, 2,3,4-tetrahydro-chlorooxaline , 3,4-methylenedoxoxyphenol, 3,4-methylenedoxoxynol, 2,6-dimethyl-3-amino-phenol, 3-amino-6-methoxy-2-methylaminophenol, 2-hydroxy-4-aminophenoxyethanol , 2-methyl-5- (ß-hydroxyethylamιno) phenol and 2,6-dihydroxy-3,4-dimethylpyndine

Particularly preferred coupler components are 1-naphthol, resorcinol, 1, 3-Bιs (2 ', 4'-dι- amlnophenoxy) propane, 4-chloro-resorcinol, 2,4-Dιamιnophenoxyethanol, 2-methyl-resorcιn, 2-Amιno-3- hydroxypyrιdιn, 2-amino-5-chloro-3-hydroxypyπdιn, 5-amino-2-methylpenol, 3-amino-2-chloro-6-methylphenol, 5-amino-3-chloro-2-methylphenol, 2-methyl 5- (ß-hydroxy-ethylamιno) phenol and 3-amιno-2-methylamιno-6-methoxy-pyrιdιn

These further developer and coupler components are usually used in free form. For substances with amino groups, however, it may be preferred to use them in salt form, in particular in the form of the hydrochloride and sulfates The agents according to the invention contain both the developer components of components A and B and the optional coupler components, preferably in an amount of 0.005 to 20% by weight, preferably 0.1 to 5% by weight, based in each case on the entire oxidation colorant. Developer components and coupler components are generally used in approximately molar amounts to one another. If the 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 are present in a molar ratio of 1: 0.5 to 1: 3, in particular 1: 1 to 1: 2 could be.

In a preferred embodiment, the agents according to the invention contain, in addition to the oxidation dye precursors, customary direct dyes for further modification of the color shades. Direct dyes are usually nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols. Preferred direct dyes are those with the international names or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, 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- (ß-hydroxyethyl ) -Amino-2-nitrobenzene, 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 6-nitro-1, 2,3,4-tetrahydroquinoxaline, hydroxyethyl-2-nitro-toluidine, picramic acid, 2-amino -6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethyiamino-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, sapwood, 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 can be contained in minor amounts, provided that these do not adversely affect the coloring result or have to be excluded for other reasons, for example toxicological ones.

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 one lipophilic alkyl group with about 10 to 22 carbon atoms. In addition, the molecule can contain glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups. 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, acyl taurides with 10 to 18 C atoms in the acyl group, acyl isethionates with 10 to 18 C atoms in the acyl group,

Sulfosuccinic acid 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 surface-active compounds that contain at least one quaternary ammonium group and at least one -COO ^w - or -SO ₃ ⁽⁾ group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinate, for example the coconut alkyl dimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinate, for example the 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 understood to mean those surface-active compounds which, in addition to a C ₈ . ₁₈ -alkyl or -acyl group in the molecule contain at least one free amino group and at least one -COOH or -SO ₃ H group and are capable of forming internal 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 alkylaminoacetic acids each with about 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocosalkylaminopropionate, cocoacylaminoethylaminopropionate and C _12-18 acylsarcosine.

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 of ethylene oxide and / or 0 to 5 mol of propylene oxide with linear fatty alcohols with 8 to 22 C atoms, with fatty acids with 12 to 22 C atoms and with alkylphenols with 8 to 15 C atoms in the alkyl group , C ₁₂ . ₂₂ fatty acid monoesters and diesters of adducts of 1 to 30 mol of ethylene oxide with glycerol, C ₈ . ₂₂ alkyl mono- and oligoglycosides and their ethoxylated analogs, Addition products of 5 to 60 mol of ethylene oxide with castor oil and hardened

Castor oil,

Addition products of ethylene oxide onto 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 trialkylmethylammonium chlorides, for. B. cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride. The quaternized protein hydrolyzates 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 trimethylsilyiamodimethicone), Dow Corning 929 emulsion (containing a hydroxylamino-modified silicone, which is also referred to as amodimethicone) , SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ^® -Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, Quatemium-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", alkyldialkoyloxyalkylammoniummethosulfate such as those sold under the trademark Stepantex ^® methylhydroxy-.

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 homologues which are obtained as catalysts when fatty alcohol and alkylene oxide are reacted 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 acrylamide groups, dimethyldiallydiallyl, dimethyldiallyl diiallyl - ammonium chloride copolymers, dimethylaminoethyl methacrylate-vinylpyrrolidone copolymers quaternized with diethyl sulfate, vinylpyrrolidone-

Imidazolinium methochloride copolymers and quaternized polyvinyl alcohol, zwitterionic and amphoteric polymers such as, for example, acrylamidopropyl-trimethylammonium chloride / acrylate copolymers and octylacrylamide / methyl methacrylate / tert.-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers, for example polyacrylic acids, polyacrylic acids, such as anionic polymers, anionic polymers such as anionic polymers , Vinyl acetate / crotonic acid copolymers, vinylpyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and acrylic acid / ethyl acrylate / N-tert.-butylacrylamide polymers, Thickeners such as agar agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives, e.g. As methyl cellulose, hydroxyalkyl cellulose and carboxymethyl cellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such as. 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 such as 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 as 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, with sodium acetate, lithium bromide, calcium bromide, calcium gluconate, zinc chloride, zinc sulfate, magnesium chloride, magnesium sulfate, ammonium carbonate, chloride and acetate being 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.

To produce the agents according to the invention, the oxidation dye precursors are incorporated into a suitable water-containing carrier. For the purpose of hair coloring, such carriers are e.g. Creams, emulsions, gels or also surfactant-containing foaming solutions, e.g. Shampoos, aerosols or other preparations that are suitable for use on the hair.

The present invention further relates to a method for dyeing keratin-containing fibers, in particular human hair, in which a colorant comprising a combination of

wherein the radicals R ¹ and R ^{2 are} independently

Hydrogen, a C _1-4 alkyl group, a C _1-4 alkoxy group, a C _1-4 monohydroxyalkyl group, a Cs ^ -dihydroxyalkyl group, a -C _a H _2a OC _b H _{2b + 1} group with a = 1 - 3 and b = 1-3, an allyl group, - -O-CH ₂ -CH = CH ₂ ,

Hydrogen is a C _1-4 alkoxy group, a C _1-4 alkyl group, a C _1-4 hydroxyalkyl group, preferably with a terminal

Hydroxy group, or a halogen atom, and the other R ³ or R ⁴ represents one of the groups:

-O-CH ₂ -CH = CH _2,

or for a group in which -A- each represents one of the groups - (CH ₂ ) _X - with x = 1 - 4,

- -O- (CH ₂ ) _y -O- with y = 1 - 4,

-O- (C _n H _2n . _Z (OH) _z ) -O- with n = 1 - 10 and z = 1 or if n is greater than or equal to 3, Z = 2, -O- (C ₂ H ₄ - O) _u - with u = 1 - 4 and

- -O- (C ₃ H ₆ -O) _v - with v = 1 - 4, and in which the radicals R ⁵ , R ⁶ and R ⁷ independently of one another represent hydrogen, a C _1-4 alkyl group, a C _1-4 alkoxy group, a C _1-4 monohydroxyalkyl group, a C ^ dihydroxyalkyl group, a -C _a H _2a OC _b H _{2b + 1} group with a = 1-3 and b = 1-3, an allyl group,

- -O-CH ₂ -CH = CH ₂ ,

-CH = CH-COOX with X = H or a physiologically compatible inorganic or organic cation, or a halogen atom, and B) at least one 1,4-diazacycloheptane derivative of the formula II

in the R ⁸ , R ⁹ , R ¹⁰ and R ¹ independently of one another stand for hydrogen, a C _1-4 alkyl or hydroxyalkyl group or a C _1-4 dihydroxyalkyl group, Y and Z independently of one another stand for hydrogen, chlorine, fluorine, a C _{1 -4} - alkyl, hydroxyalkyl, aminoalkyl or alkoxy group, a C _2-4 dihydroxyalkyl group or an allyl group and

R ¹² and R ¹³ independently of one another represent hydrogen or a C _1-4 alkyl group, and / or of reaction products from these compounds and conventional cosmetic ingredients, applied to the fibers containing keratin, for some time, usually about 30 minutes, on the fiber leave and then rinsed out 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 their 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 is the procedure to increase the effect of small amounts (e.g. 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 coloring. The resulting ready-to-use hair dye preparation should preferably have a pH in the range from 2 to 11, in particular from 5 to 10. The use of the agents in a weakly alkaline environment is particularly preferred. 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, such as a coloring shampoo, has been used. The following examples are intended to explain the subject of the invention in more detail.

B e i s p i e l e

colorations

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. ¹ 4.0

Texapon.RTM ^® N 28 * 40.0

Dehyton ^® K ³ 25.0

Eumulgin ^® B 2 1, 5 distilled water 12.5

1

^ 12-18 ^" ' ^{=: e} ^ ^a "^<0' ^no '(HENKEL)

Sodium lauryl ether sulfate (approx. 28% active substance; CTFA name: Sodium Laureth Sulfate) (HENKEL)

Fatty acid amide derivative with betaine structure of the formula

R-CONH (CH) N ⁺ (CH) CH COO ^" (approx. 30% active substance; CTFA designation-

2 3 3 2 2 cocoamidopropyl betaine) (HENKEL)

Cetylstearyl alcohol with approx. 20 mol EO (CTFA name: Ceteareth-20) (HENKEL)

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

Cream base 50.0

Developer component A 7.5 mmol

Developing component B 7.5 mmol

Coupler component 7.5 mmol

Na _∑ SO (inhibitor) 1.0 (NH) SO 1.0

4 2 4 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, the pH of the emulsion was first adjusted to 10 using concentrated ammonia solution, and the mixture was then made up to 100 g with water.

For the oxidative development of the coloring, 100 g of the emulsion were mixed with 50 g of hydrogen peroxide solution (concentration see table) and mixed.

The coloring cream was applied to approx. 5 cm long strands of 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.

Bis- (5-amino-2-hydroxyphenyl) methane (component A) and N, N'-bis (4-aminophenyl) -1, 4-diazacycioheptane (component B) were used as developer components for the colorations.

The coupler components used and the coloring results are shown in the following table.

The following colors were found:

Coupler component shade of colored hair

Air oxidation 1% H ₂ O ₂ 9% H ₂ O ₂ 1, 3-bis- (2 ', 4'-diaminophenoxy) propane black blue black blue black blue

2,6-dimethyl-3-aminophenol fawn brown violet brown dark magenta

3,4-methylenedioxyphenol light blonde beaver brown beaver brown

2-chloro-6-methyl-3-aminopenol brown gray dark violet dark violet

4-chloro-6-methyl-3-aminopenol violet gray violet matt violet 1-Naphthol cafe au lait dark purple dark purple

2-methylamino-3-amino-6-methoxypyridine olive dark blue dark blue 2-methyl-5-aminophenol fawn brown violet brown dark magenta

3-aminophenol olive-brown smoke-colored smoke-colored 2,4-diaminophenoxyethanol black-blue black-blue black-blue 1, 5-dihydroxynaphthalene gray-brown dark violet plum-colored

Claims

P a t e n t a n s r u c h e

Agent for dyeing keratin fibers, containing a combination of A) at least one aminophenol derivative of the formula I or one of the water-soluble, physiologically tolerable salts

wherein the radicals R ¹ and R ^{2 are} independently

Hydrogen, a C _1-4 alkyl group, a C _1-4 alkoxy group, a C _1-4 monohydroxyalkyl group, a Ca ^ dihydroxyalkyl group, a -C _a H _2a OC _b H _{2b + 1} group with a = 1 - 3 and b = 1-3, an allyl group, - -O-CH ₂ -CH = CH ₂ ,

Hydrogen is a C alkoxy group a C ^ alkyl group, a C _1-4 hydroxyalkyl group, preferably with a terminal

-O-CH ₂ -CH = CH _2, -CH = CH-COOX, where X stands for hydrogen or a physiologically compatible inorganic or organic cation, for a group

or for a group

in which -A- stands for one of the groups

- - (CH ₂ ) _X - with x = 1 - 4,

- -O- (CH ₂ ) _y -O- with y = 1 - 4,

-O- (C _n H _2n . ₂ (OH) _z ) -O- with n = 1 - 10 and z = 1 or if n is greater than or equal to 3, Z = 2, -O- (C ₂ H ₄ - O) _u - with u = 1 - 4 and

--O- (C ₃ H ₆ -O) _v - with v = 1 - 4, and in which the radicals R ⁵ , R ⁸ and R ⁷ independently of one another represent hydrogen, a C _1-4 alkyl group, a C. _1-4 alkoxy group, a C _1-4 monohydroxyalkyl group, a C ₃ ^ dihydroxyalkyl group, a -C _a H _2a OC _b H _{2b + 1} group with a = 1-3 and b = 1-3, an allyl group .

- -O-CH ₂ -CH = CH ₂ ,

-CH = CH-COOX with X = H or a physiologically acceptable inorganic or organic cation, or a halogen atom, and B) at least one 1,4-diazacycloheptane derivative of the formula II

in the

R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ independently represent hydrogen, a C 1-4

Alkyl or hydroxyalkyl group or a C _2-4 -dihydroxyalkyl group,

Y and Z independently represent hydrogen, chlorine, fluorine, one

C ^ -alkyl, -hydroxyalkyl, -aminoalkyl or -alkoxy group, a C _2- -

Dihydroxyalkyl group or an allyl group and

R ¹² and R ¹³ independently of one another represent hydrogen or a C _1-4 -

Alkyl group.

2. Composition according to claim 1, characterized in that both radicals R ¹ and R ^{2 are} hydrogen.

3. Composition according to claim 1 or 2, characterized in that R ³ or R ^{4 is} hydrogen.

4. Agent according to one of claims 1 to 3, characterized in that X represents hydrogen.

5. Agent according to one of claims 1 to 3, characterized in that n = 1-6, in particular 1-3, and z = 1.

6. Composition according to one of claims 1 to 5, characterized in that both radicals R ¹² and R ^{13 are} hydrogen in the compound of formula II.

7. Composition according to one of claims 1 to 6, characterized in that in connection with formula II at least three of the groups R ⁸ , R ⁹ , R ¹⁰ and R ^{1 are} hydrogen.

8. Composition according to one of claims 1 to 7, characterized in that in the compound having the formula II Y and Z independently of one another represent hydrogen, fluorine, chlorine or a C _1-4 alkyl, in particular methyl, group.

9. Composition according to one of claims 1 to 8, characterized in that the compounds having the formula II from N, N'-bis (4'-aminophenyl) -1, 4-diazacycloheptane and N, N'-bis (4 ' -amino-3'-methyl-phenyl) -1, 4-diazacycloheptane are selected.

10. Composition according to one of claims 1 to 9, characterized in that compounds with the formula I and with the formula II are contained in a total amount of 0.005 to 20 wt .-%, preferably 0.1 to 5 wt .-% ,

11. Agent according to one of claims 1 to 9, characterized in that it is an oxidation hair dye.

12. Composition according to one of claims 1 to 11, characterized in that further developer components selected from 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 1- (β-hydroxyethyl) -2,5-diaminobenzene, p-phenylenediamine, p-toluenediamine, N, N-bis (ß-hydroxyethyl) -p-phenylenediamine, p-aminophenol, 3-methyl-p-aminophenol, 2-aminomethyl-p-aminophenol , 2-Diethylaminomethyl-4-aminophenol and N, N'-bis (ß-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1, 3-diamino-propan-2-ol are included.

13. Composition according to one of claims 1 to 12, characterized in that it is 1-naphthol, resorcinol, 1, 3-bis (2 ', 4'-diaminophenoxy) propane, 4-chlororesorcinol, 2,4-diaminophenoxyethanol, 2- Methylresorcinol, 2-amino-3-hydroxypyridine, 2-amino-5-chloro-3-hydroxypyridine, 5-amino-2-methylpenol, 3-amino-2-chloro-6-methylphenol, 5-amino-3-chloro Contains 2-methylphenol, 2-methyl-5 (ß-hydroxyethylamino) phenol, 3-amino-2-methylamino-6-methoxy-pyridine as a coupler component.

14. Composition according to one of claims 12 or 13, characterized in that the further developer and coupler components each in an amount of 0.005 to 20 wt .-%, preferably 0.1 to 5 wt .-%, each based on the total Means included.

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

16. A method for dyeing keratin fibers, in particular human hair, in which a colorant containing a combination of

wherein the radicals R ¹ and R ^{2 are} independently

Hydrogen, a C _1-4 alkyl group, a C _1-4 alkoxy group, a C _M monohydroxyalkyl group, a C ₃ ^ dihydroxyalkyl group, a -C _a H _2a OC _b H _{2b + 1} group with a = 1 - 3 and b = 1-3, an allyl group, - -O-CH ₂ -CH = CH ₂ ,

hydrogen a C _1-4 alkoxy group a C _1-4 alkyl group, a C _M hydroxyalkyl group, preferably with a terminal hydroxyl group, or a halogen atom, and the other R ³ or R ⁴ represents one of the groups: -O-CH ₂ - CH = CH ₂

or for a group

in which -A- stands for one of the groups

- - (CH ₂ ) _X - with x = 1 - 4,

- -O- (CH ₂ ) _y -O- with y = 1 - 4,

-O- (C _π H _2n-z (OH) ₂ ) -O- with n = 1 - 10 and z = 1 or if n is greater than or equal to 3, Z = 2, -O- (C ₂ H ₄ - O) _u - with u = 1 - 4 and

--O- (C ₃ H ₆ -O) _v - with v = 1 - 4, and in which the radicals R ⁵ , R ⁶ and R ⁷ independently of one another represent hydrogen, a C _1-4 alkyl group, a C. _1-4 alkoxy group, a C _1-4 monohydroxyalkyl group, a C ₃ ^ -dihydroxyalkyl group, a -C _a H _2a OC _b H _{2b + 1} group with a = 1-3 and b = 1-3, an allyl group,

-O-CH ₂ -CH = CH ₂ ,

-CH = CH-COOX with X = H or a physiologically acceptable inorganic or organic cation, or a halogen atom, and

B) at least one 1,4-diazacycloheptane derivative of the formula II

in the

R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ independently of one another represent hydrogen, a C 1-4 alkyl or hydroxyalkyl group or a C _2-4 dihydroxyalkyl group, Y and Z independently of one another represent hydrogen, chlorine, fluorine, a C _{1 -4} -alkyl, -hydroxyalkyl, -aminoalkyl or -alkoxy group, a C _2-4 - dihydroxyalkyl group or an allyl group and

R ¹² and R ¹³ independently of one another represent hydrogen or a C _1-4 alkyl group, and / or reaction products from these compounds and customary cosmetic ingredients, applied to the fibers containing keratin, left on the fiber for some time, usually about 30 minutes and then rinsed out or washed out with a shampoo.