DE19951009A1 - Composition used for dyeing keratin containing fibers, especially human hair, contains p-aminophenol derivative and 1,4-diazacyclopentane derivative as developer - Google Patents

Abstract

Composition (A) contains: (a) at least one p-aminophenol derivative (I), and (b) at least one 1,4-diazacyclopentane derivative (II). Composition (A) contains: (a) at least one p-aminophenol derivative of formula (I) or its salts, and (b) at least one 1,4-diazacyclopentane derivative of formula (II) or its salts. R1-R4 = 1-4C alkyl, 1-4C alkoxy, 1-4C monohydroxyalkyl, 3-4C dihydroxyalkyl, -CaH2aOCbH2b+1, allyl, allyloxy, CH=CH-COOX or halo; X = H or inorganic or organic cation; a, b = 1-3; one of R3, R4 = 1-4C alkoxy, 1-4C alkyl, 1-4C hydroxyalkyl (preferably terminally hydroxylated) or halo, and the other is allyloxy, CH=CH-COOX, or an aminophenol derivative of formula (i) or (ii); A = (CH2)x, O(CH2)yO, O(CnH2n-z(OH)z)O, O(C2H4O)u or O(C3H6O)v; u, v, x, y = 1-4; n = 1-10; z = 1, or may also be 2 if n = at least 3; R5-R7 = as R1, R2; R8-R11 = H, 1-4C alkyl, 1-4C hydroxyalkyl or 2-4C dihydroxyalkyl; Y, Z' = H, Cl, F, 1-4C alkyl, 1-4C hydroxyalkyl, 1-4C aminoalkyl, 1-4C alkoxy, 2-4C dihydroxyalkyl or allyl, and R12, R13 = H or 1-4C alkyl. An Independent claim is included for a method of dyeing keratin containing fibers, involving applying a dyeing composition (A) containing (a) and (b) (or their reaction product) and conventional components to the fibers, leaving (A) in contact with the fibers for a suitable time (generally 30 minutes) and rinsing or washing with shampoo.

Description

The invention relates to means for dyeing keratinous fibers, which is a combination of at least one p-aminophenol derivative and at least one 1,4- Containing diazacycloheptane derivative, and a method of coloring keratin-containing Fibers.

For the dyeing of keratin fibers, especially human hair, play the so-called oxidation dyes because of their intense colors and good fastness egg a preferred role. Such colorants include oxidation dye products, so-called developer components and coupler components. The Ent Wicklerkomponenten form under the influence of oxidizing agents or air oxygen with each other or under coupling with one or more Kupplerkompo nents the actual dyes.

Good oxidation dye precursors must meet the following requirements in the first place You must: In the oxidative coupling you have the desired color shades in form sufficient intensity and authenticity. You also need a good upgrade have toe on the fiber, especially in human hair no noticeable differences between strained and newly regrown hair may exist (leveling ability). They should be resistant to light, heat and the influence of chemical reducing agents, eg. B. against perming fluids. After all should they - if used as a hair dye used - the scalp not too much and, above all, they should be toxicological and dermatological be harmless.  

As developer components are usually primary aromatic amines with a further, in the para or ortho position free or substituted hydroxy or Amino group, Diaminopyridinderivate and 2,4,5,6-tetraaminopyrimidine and its Derivatives used.

Specific representatives are, for example, p-phenylenediamine, p-toluenediamine, 2,4,5,6-tetra aminopyrimidine, p-aminophenol, N, N-bis- (2'-hydroxyethyl) -p-phenylenediamine, 2- (2,5-di aminophenyl) 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.

As coupler components usually m-phenylenediamine derivatives, naphthols, Re sorcin and resorcinol derivatives, pyrazolones and m-aminophenol derivatives. When Coupler substances are particularly suitable 1-naphthol, 1,5-, 2,7- and 1,7- Dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol mono 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-methylre sorciri and 2-methyl-4-chloro-5-aminophenol.

With regard to further customary dye components, express reference is made to the series "Der Matology ", edited by Ch. Culnan, H. Maibach, published by Marcel Dekker Inc., New York, Basel, 1986, vol. 7, Ch. Zviak, The Science of Hair Care, ch. 7, pages 248-250 (Direct dyes), and Chap. 8, pages 264-267 (oxidation dyes), and the "European Inventory of Cosmetic Raw Materials", 1996, published by the Euro European Commission, available in disk form from the Federal Association of German Industrial and commercial enterprise for pharmaceuticals, health products and personal care products e.V., Mannheim.

In DE 196 07 751 A1, the use of special aminophenol derivatives solely as a developer component in oxidation dyes for dyeing keratin fibers  described. In DE 197 07 545 A1 1,4-diazacycloheptane derivatives and their Use as a developer component in oxidation dyes disclosed.

With a developer component or a specific coupler / developer Combination usually does not succeed, a naturally acting on the hair To get color nuance. In practice, therefore, usually combinations various developer components and coupler components used. It exists Therefore, there is a constant need for new, improved dye combinations.

It was therefore the object of the present invention to provide combinations of components find that are suitable to be used in colorants, and in particular meet the requirements to be placed on oxidation dyes in particular. It has now been found that combinations of certain aminophenol derivatives and 1,4-diazacycloheptane derivatives excellently as coloring component in agents for Dyeing keratin fibers are suitable and meet the requirements. Thus, using these developer components with the most known Coupler components have brilliant color shades, especially in the brown, blue and violet Area, which are extremely light and washfast. Continue to stand out the colors obtained by extraordinary cold-wave fastness and thermal stability, as well as by an excellent equalization.

An object of the present invention are therefore agents for dyeing keratin-containing fibers containing a combination of

• A) at least one aminophenol derivative of the formula I or one of the water-soluble, physiologically acceptable salts
  wherein
  the radicals R ¹ and R ² 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 _3-4 -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 R ³ and R ⁴ is
  Hydrogen,
  a C _1-4 alkoxy group,
  a C _1-4 alkyl group,
  a C _1-4 hydroxyalkyl group, preferably hydroxy-terminated, or
  a halogen atom,
  and the other radical R ³ or R ⁴ is one of the groups:
  -O-CH ₂ -CH = CH ₂ ,
  -CH = CH-COOX, where X is hydrogen or a physiologically compatible inorganic or organic cation,
  for a group
  or
  for a group
  where -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- where n = 1-10 and z = 1 or when 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 are each independently
  Hydrogen,
  a C _1-4 alkyl group,
  a C _1-4 alkoxy group,
  a C _1-4 monohydroxyalkyl group,
  a C _3-4 -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 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.

Since all substances of the formulas I and II are amino compounds, can be prepared from these in the usual way, the known acid addition salts. All statements of this document and accordingly the claimed scope Therefore, both the present in free form compounds of formula (I) and Formula (II) as well as their water-soluble, physiologically acceptable salts. Examples for such salts are the hydrochlorides, the hydrobromides, the sulfates, the phosphates, the Acetates, Propionates, Citrates and Lactates.

Among keratin-containing fibers are wool, furs, feathers and especially human To understand hair. The inventive compositions can in principle but also for Dyeing other natural fibers, such. Cotton, jute, sisal, linen or silk, modified natural fibers, such as. Regenerated cellulose, nitro, alkyl or hydroxyalkyl or acetyl cellulose and synthetic fibers, such as. As polyamide, polyacrylonitrile, poly urethane and polyester fibers are used. Although the compositions of the invention in are primarily suitable for dyeing keratin fibers, is in principle a Verwen also in other areas, especially in color photography.  

Examples of the C ₁ -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. Further, as preferred examples of a C ₁ to C ₄ hydroxyalkyl group, there may be mentioned a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group, a 2-hydroxyethyl group is particularly preferable. A preferred C ₁ - to C ₄ -alkoxy group 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. The other terms used are derived according to the invention from the definitions given here.

The compounds described as component A are for example from DE 196 06 751 A1 discloses and can be prepared by known organic synthesis methods put. The compounds of component B are described, for example, in DE 197 07 545 A1 disclosed and can also be obtained by known synthesis methods, unless they are commercially available. The compounds of component A and the Component B is preferably in a molar ratio of 1:20 to 20: 1 used.

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

Likewise 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.

Among the binuclear p-aminophenol derivatives are the symmetrically substituted Compounds preferred according to the invention.

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

Finally, among the compounds which are hydroxyalkyl diethers are those preferred in which n is a number from 1 to 6, in particular from 1 to 3, and the have a hydroxy group on the aliphatic chain (z = 1).

Particularly excellent in the sense of Gesamtterfindung suitable substances of Component A are bis (5-amino-2-hydroxyphenyl) -methane, bis (5-amino-3-methyl-2-) hydroxyphenyl) methane, 3-hydroxy-6-aminoallyloxybenzene, 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) propan-2-ol.

Preferably used substances of component B are 1,4-diazacycloheptane derivatives according to formula (II), in which both radicals R ¹² and R ¹³ on the 1,4-diazacycloheptane ring are hydrogen.

Likewise 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-diazacycloheptane 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 proved to be very particularly advantageous groups Y and Z.

Preferred for the purposes of the invention are 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-methyl phenyl) -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 particularly preferred.

The agents according to the invention are particularly suitable as so-called An oxidation. In Oxidationsfärbemitteln the combination of the invention acts from the compounds of formulas I and II as developing components. It can if desired, further developer components and coupler components be included. With respect to the other developer and coupler components is on the referenced at the beginning of the description, the preferred further Represent dye components.

Developer components preferred according to the invention are p-phenylenediamine, p-toluene lendiamine, p-aminophenol, o-aminophenol, 1- (2'-hydroxyethyl) -2,5-diaminobenzene, N, N- Bis (2'-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-amino-phenol, 4,4'-diaminodiphenylamine, 4-amino-3-fluorophenol, 2-aminomethyl-4-amino-phenol, 2-diethylaminomethyl-4- aminophenol, 2-hydroxymethyl-4-aminophenol, bis (2-hydroxy-5-aminophenyl) -methane, 1,4-Bis- (4-aminophenyl) -diazacycloheptane, 1,3-bis (N (2-hydroxyethyl) -N- (4-aminophenyl amino)) - 2-propanol, 4-amino-2- (2-hydroxyethoxy) -phenol and 4,5-diaminopyrazole Derivatives according to EP 0 740 931 or WO 94/08970 such. B. 4,5-diamino-1- (2'-hydroxyethyl) - pyrazole.

Very particularly preferred further developer components are 2,4,5,6-tetraaminopy rimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 1- (2-hydroxyethyl) -2,5-diaminobenzene, p- Phenylenediamine, p-toluenediamine, N, N-bis- (2'-hydroxyethyl) -p-phenylenediamine, p-amino phenol, 3-methyl-p-aminophenol, 2-aminomethyl-p-aminophenol, 2-diethylaminomethyl-4- aminophenol and 1,3-N, N'-bis (2'-hydroxyethyl) -N, N'-bis (4'-amino-phenyl) -diamino-1,3- propane-2-ol.  

Preferred coupler components 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-dichloro-3-aminophenol, 1,3-bis- (2,4-diaminophenoxy) -propane, 4-chlororesorcinol, 2- Chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2,6-dihydroxypyridine, 2,6-diaminopyridine, 2-amino-3-hydroxypyridine, 2,6-dihydroxy-3,4- diaminopyridine, 3-amino-2-methylamino-6-methoxypyridine, 4-amino-2-hydroxytoluene, 2,6- Bis (2'-hydroxyethylamino) toluene, 2,4-diaminophenoxyethanol, 1-methoxy-2-amino-4- (2-bis) hydroxyethylamino) benzene, 2-methyl-4-chloro-5-amino-phenol, 6-methyl-1,2,3,4-tetrahydro quinoxaline, 3,4-methylenedioxyphenol, 3,4-methylenedioxyaniline, 2,6-dimethyl-3-amino phenol, 3-amino-6-methoxy-2-methylaminophenol, 2-hydroxy-4-aminophenoxyethanol, 2- Methyl 5- (2-hydroxyethylamino) phenol and 2,6-dihydroxy-3,4-dimethylpyridine.

Particularly preferred coupler components are 1-naphthol, resorcinol, 1,3-bis (2,4-diami nophenoxy) 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-2-methylphenol, 2-methyl-5 (2-hydroxy ethylamino) -phenol and 3-amino-2-methylamino-6-methoxy-pyridine.

These further developer and coupler components are usually in free form used. For substances with amino groups, it may be preferable to use them in Salt form, especially in the form of hydrochlorides and sulfates, use.

The agents according to the invention contain both the developer components of Components A and B as well as the optionally present coupler components preferably in an amount of 0.005 to 20% by weight, preferably 0.1 to 5% by weight, each based on the total oxidation colorant. Thereby developing compo nenten and coupler components generally in about molar amounts to each other set. Although the molar use has proved to be useful, so is a certain excess of individual oxidation dye precursors not disadvantageous, so that Developer components and coupler components in a molar ratio of 1: 0.5 to 1: 3, in particular 1: 1 to 1: 2, may be included.  

In a preferred embodiment, the inventive compositions for further modification of the color shades in addition to the oxidation dye precursors in addition usual substantive dyes. Direct dyes are common Nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophe nole. Preferred substantive dyes are those under the international name 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 1,4-bis- (β-hydroxyethyl) -amino-2-nitrobenzene, 4-amino-2-nitrodiphenylamine-2'- carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, hydroxyethyl-2-nitro-toluidine, picramine 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 according to this Embodiment, the substantive dyes preferably contain in an amount of 0.01 to 20 wt .-%, based on the total colorant.

Furthermore, the preparations according to the invention can also occur in nature Dyes such as henna red, henna neutral, henna black, chamomile flower, Sandalwood, black tea, buckthorn bark, sage, bluewood, madder root, catechu, Sedre and alcano root included.

It is not necessary that the oxidation dye precursors or the optional direct-acting dyes contained in each case represent uniform compounds. Rather, in the compositions of the invention, due to the Production process for the individual dyes, in minor amounts still may contain other components, as far as these are not detrimental to the dyeing result influence or for other reasons, eg. As toxicological, are excluded have to.

Further dye components contained in the agents according to the invention can also Indoles and indolines, and their physiologically acceptable salts, be. preferred  Examples are 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihy droxyindole, 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 compositions of the invention give already at physiologically tolerable Tempe temperatures below 45 ° C. They are therefore particularly suitable for Dyeing of human hair. For use on human hair can the agents are usually incorporated into an aqueous cosmetic carrier become. Suitable hydrous cosmetic carriers are for. As creams, emulsions, Gels or surfactant-containing foaming solutions such. As shampoos or others Preparations suitable for use on the keratin-containing fibers. If it is also possible to incorporate the agents in anhydrous carriers.

Furthermore, the agents according to the invention can all be known in such preparations Active substances, additives and auxiliary substances. In many cases, the funds contain at least one Surfactant, whereby in principle both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants are suitable. In many cases, however, it has proved to be proved to be advantageous, the surfactants from anionic, zwitterionic or nonionic Select surfactants.

Suitable anionic surfactants in preparations according to the invention are all anionic surfactants suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such as. Example, a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group having about 10 to 22 carbon atoms. In addition, glycol or poly glycol 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 C 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 having 10 to 22 C atoms and x = 0 or 1 to 16,
• Acylsarcosides having 10 to 18 C atoms in the acyl group,
• Acyltaurides having 10 to 18 C atoms in the acyl group,
• Acyl isethionates having 10 to 18 C atoms in the acyl group,
• - Sulfobernsteinsäuremono- and -dialkylester having 8 to 18 carbon atoms in the alkyl group and sulfosuccinic acid mono-alkyl polyoxyethyl esters having 8 to 18 carbon atoms in the Alkyl group and 1 to 6 oxyethyl groups,
• Linear alkanesulfonates having 12 to 18 C atoms,
• - linear alpha-olefin sulfonates having 12 to 18 C atoms,
• Alpha-sulfofatty acid methyl esters of fatty acids containing 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 having 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 Hydroxyalkylpolyethylen- and / or Hydroxyalkylenpropylenglykolether according to DE-A-37 23 354,
• - Sulfonates of unsaturated fatty acids having 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 with fatty alcohols with 8 bis Represent 22 C atoms.

Preferred anionic surfactants are alkyl sulfates, Alkylpolyglykolethersulfate and Ethercar bonsäuren having 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 especially 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 in the molecule at least one quaternary ammonium group and at least one -COO ^(-) or -SO ₃ ^(-) group. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammoniumglycinate, for example the cocoalkyl dimethylammoniumglycinat, N-acyl-aminopropyl-N, N-dimethylam moniumglycinate, for example Kokosacylaminopropyl-dimethylammoniumglycinat, and 2-alkyl 3-carboxymethyl-3-hydroxyethyl-imidazolines having in each case 8 to 18 carbon atoms in the alkyl or acyl group and the Kokosacylaminoethylhydroxyethylcarboxymethyl glycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known by the CTFA name Cocamidopropyl Betaine.

Ampholytic surfactants are understood to mean those surface-active compounds which, apart from 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 which are capable of forming internal salts are. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylamino-propionic acids and alkylaminoacetic acids each having about 8 to 18 C atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C _12-18 acylsarcosine.

Nonionic surfactants contain as hydrophilic group z. As a polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether group. Such compounds are, for example

• - Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear fatty alcohols having 8 to 22 C atoms, to fatty acids having 12 to 22 C atoms and to alkylphenols having 8 to 15 C atoms in the alkyl group,
• C _12-22 fatty acid mono- and diesters of addition products of 1 to 30 moles of ethylene oxide with glycerol,
• C _{8-22 alkyl} mono- and oligoglycosides and their ethoxylated analogs,
• - Addition products of 5 to 60 moles 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 to fatty acid alkanolamides.

Examples of the usable in the hair treatment compositions according to the invention kat ionic surfactants are especially quaternary ammonium compounds. Preferred are Ammonium halides such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and Trialkylmethylammoniumchloride, z. Cetyltrimethylammonium chloride, stea ryltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethyl ammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride. Further cationic surfactants which can be used according to the invention are the quaterni siert protein hydrolysates.

Likewise suitable according to the invention are cationic silicone oils, such as those described in US Pat Commercially available products Q2-7224 (manufactured by Dow Corning; a stabilized Tri methylsilylamodimethicone), Dowing Coming 929 emulsion (containing a hydroxylamino modified silicone, also referred to as amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil® Quat 3270 and 3272 (Manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, quaternium-80).

Alkylamidoamines, especially fatty acid amidoamines such as that under the name Tego Amid®S 18 available stearylamidopropyldimethylamine, stand out next to one good conditioning effect especially by their good biodegradability.

Also very readily biodegradable are quaternary ester compounds, so-called "Esterquats" such as methylhydroxy marketed under the trademark Stepantex alkyldialkoyloxyalkylammoniummethosulfate.

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

The compounds used as surfactants with alkyl groups may be in each case act uniform substances. However, it is usually preferred in the production These substances are based on native plant or animal raw materials, so that one  Substance mixtures with different alkyl chains depending on the respective raw material length receives.

In the case of the surfactants, the addition products of ethylene oxide and / or propylene oxide Fatty alcohols or derivatives of these addition products, both Pro products with a "normal" distribution of homologs as well as those with a narrower Homolog distribution can be used. Under "normal" homolog distribution understood mixtures of homologues, which in the implementation of Fettal khol and alkylene oxide using alkali metals, alkali metal hydroxides or Alkali metal alcoholates obtained as catalysts. Narrow homolog distributions who obtained, however, if, for example, hydrotalcites, alkaline earth metal salts of Ethercarbonsäuren, alkaline earth metal oxides, hydroxides or alkoxides as catalysts be used. The use of products with narrow homolog distribution may be preferred.

Other active ingredients, auxiliaries and additives are, for example

• Nonionic polymers such as vinyl pyrrolidone / vinyl acrylate copolymers, Polyvinylpyrrolidone and vinylpyrrolidone / vinyl acetate copolymers and polysiloxanes,
• Cationic polymers such as quaternized cellulose ethers, polysiloxanes with quaternary Groups, dimethyldiallylammonium chloride polymers, acrylamide-dimethyldiallyl ammonium chloride copolymers, diethyl sulfate quaternized dimethylaminoethyl methacrylate-vinylpyrrolidone copolymers, vinylpyrrolidone-imidazolinium methochloride Copolymers and quaternized polyvinyl alcohol,
• Zwitterionic and amphoteric polymers such as acrylamidopropyl tri methylammonium chloride / acrylate copolymers and octylacrylamide / methylmethacrylate lat / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers,
• Anionic polymers such as, for example, polyacrylic acids, crosslinked polyacrylic acids, Vinyl acetate / crotonic acid copolymers, vinyl pyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride tride copolymers and acrylic acid / ethyl acrylate / N-tert-butylacrylamide terpolymers,
• - Thickeners such as agar-agar, guar gum, alginates, xanthan gum, gum ara bicum, karaya gum, locust bean gum, linseed gums, dextrans, cel  lulose derivatives, e.g. Methylcellulose, hydroxyalkylcellulose and carboxymethylcel cellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such as As bentonite or fully synthetic hydrocolloids such. For example, polyvinyl alcohol,
• - structurants such as glucose and maleic acid,
• Hair conditioning compounds such as phospholipids, for example soya lecithin, Egg lecithin and cephalins, as well as silicone oils,
• - Protein hydrolysates, especially elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolysates, their condensation products with fatty acids and quaternized protein hydrolysates,
• Perfume oils, dimethylisosorbide and cyclodextrins,
• - Solubilizers such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol,
• Anti-dandruff agents such as Piroctone Olamine and Zinc Omadine,
• - other substances for adjusting the pH,
• - Active substances such as panthenol, pantothenic acid, allantoin, pyrrolidonecarboxylic acids and their salts, plant extracts and vitamins,
• - cholesterol,
• - light stabilizers,
• Bodying agents such as sugar esters, polyol esters or polyol alkyl ethers,
• - Fats and waxes such as spermaceti, beeswax, montan wax, paraffins, fatty alcohols and fatty acid esters,
• - fatty acid,
• - complexing agents such as EDTA, NTA and phosphonic acids,
• - Swelling and penetration substances such as glycerol, propylene glycol monoethyl ether, Carbo nate, bicarbonates, guanidines, ureas and primary, secondary and ter tiary phosphates, imidazoles, tannins, pyrrole,
• Opacifiers such as latex,
• Pearlescing agents such as ethylene glycol mono- and distearate,
• - Propellants such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air and
• - antioxidants.

The constituents of the water-containing carrier are used to prepare the erfindungsge means are used in quantities customary for this purpose; z. B. become emulsifiers in concentrations of 0.5 to 30% by weight and thickeners in concentrations of 0.1 to 25 wt .-% of the total agent used.

For the dyeing result, it may be advantageous to the means ammonium or metal salts admit. Suitable metal salts are, for. 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 minium, 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 are preferred. These salts are preferred in an amount of 0.03 to 65, in particular from 1 to 40, mmol based on 100 g of the entire agent.

To prepare the agents according to the invention, the oxidation dye precursors incorporated into a suitable aqueous carrier. For the purpose of hair coloring are such carrier z. As creams, emulsions, gels or surfactant foaming Solutions, eg. As shampoos, foam aerosols or other preparations for the Application on the hair are suitable.

Another object of the present invention relates to a process for dyeing keratin-containing fibers, in particular human hair, wherein a colorant ent holding a combination of

• A) at least one aminophenol derivative of the formula I or one of the water-soluble, physiologically acceptable salts
  wherein
  the radicals R ¹ and R ² 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 _3-4 -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 R ³ and R ⁴ is
  Hydrogen,
  a C _1-4 alkoxy group,
  a C _1-4 alkyl group,
  a C _1-4 hydroxyalkyl group, preferably hydroxy-terminated, or
  a halogen atom,
  and the other radical R ³ or R ⁴ is one of the groups:
  -O-CH ₂ -CH = CH ₂ ,
  -CH = CH-COOX, where X is hydrogen or a physiologically compatible inorganic or organic cation,
  for a group
  or
  for a group
  where -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- where n = 1-10 and z = 1 or when 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 are each independently
  Hydrogen,
  a C _1-4 alkyl group,
  a C _1-4 alkoxy group,
  a C _1-4 monohydroxyalkyl group,
  a C _3-4 -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 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 of these compounds as well as usual cosmetic ones Ingredients, applied to the keratin fibers, some time, usually about 30 Minutes, left on the fiber and then rinsed out again or with a Shampoo is washed out.

The oxidative development of the dyeing can in principle be carried out with atmospheric oxygen. Preferably, however, a chemical oxidizing agent is used, especially when in addition to the coloring, a lightening effect on human hair is desired. As oxidation Persulfates, chlorites and in particular hydrogen peroxide or its derivatives are used Addition products of urea, melamine and sodium borate in question. It continues possible to carry out the oxidation with the aid of enzymes. The enzymes can for transferring atmospheric oxygen to the developer component or for reinforcement serve the effect of small amounts of existing oxidizing agents. An example of one enzymatic process represents the procedure, the effect of small amounts (eg 1% and less, based on total agent) of hydrogen peroxide by peroxidases strengthen.  

Conveniently, the preparation of the oxidizing agent immediately before Hair dyeing mixed with the preparation of the oxidation dye precursors. The The resulting ready-to-use hair dye preparation should preferably have a pH in the Range of 2 to 11, in particular from 5 to 10, have. Particularly preferred is the Application of the agent in a weakly alkaline medium. The application temperatures can range between 15 and 40 ° C. After an exposure time of About 30 minutes, the agent is removed by rinsing of the hair to be dyed. The Washing with a shampoo is eliminated if a strong surfactant-containing carrier, eg. B. a Dyeing shampoo, was used.

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

Examples colorations

A cream base of the following composition was first prepared [all statements are in g], unless stated otherwise:

tallow 17.0 Lorol®techn. ¹ 4.0 Texapon®N 28 ² 40.0 Dehyton®K ³ 25.0 Eumulgin®B 2 ⁴ 1.5 distilled water 12.5 ¹ C _12-18 fatty alcohol (HENKEL) @ ² Sodium lauryl ether sulfate (about 28% active substance, CTFA name: Sodium Laureth Sulfate) (HENKEL) @ ³ fatty acid amide derivative having a betaine structure of the formula R-CONH (CH ₂ ) ₃ N ⁺ (CH ₃ ) ₂ CH ₂ COO- (about 30% active substance, CTFA name cocoamidopropyl betaine) (HENKEL) @ ⁴ cetylstearyl alcohol with approx. 20 mol EO (CTFA name: Ceteareth-20) (HENKEL)

cream base 50.0 Developer Component A 7.5 mmol Developer component B 7.5 mmol Kupplerkomponente 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

Based on this cream, the following hair dye cream emulsion was then prepared:  

The ingredients were mixed together in order. After adding the Oxidation dye precursors and the inhibitor was initially concentrated with Ammonia solution adjusted the pH of the emulsion to 10, then it was watered up 100 g filled.

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

The staining cream was standardized to about 5 cm long strands, 90% gray, but not particularly pre-treated human hair applied and there 30 minutes left at 32 ° C. After completion of the dyeing process, the hair was rinsed with a conventional shampoo and then dried.

For the colorations, the developer components bis (5-amino-2-hydroxyphenyl) - methane (component A) and N, N'-bis (4-aminophenyl) -1,4-diazacycloheptane (Component B) used.

The coupler components used as well as the staining results are as follows Table shown.

The following colorations were found:

Claims (17)

1. An agent for dyeing keratin-containing fibers, containing a combination of

• A) at least one aminophenol derivative of the formula I or one of the water-soluble, physiologically acceptable salts
  wherein
  the radicals R ¹ and R ² 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 _3-4 -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 R ³ and R ⁴ is
  Hydrogen,
  a C _1-4 alkoxy group,
  a C _1-4 alkyl group,
  a C _1-4 hydroxyalkyl group, preferably hydroxy-terminated, or
  a halogen atom,
  and the other radical R ³ or R ⁴ is one of the groups:
  -O-CH ₂ -CH = CH ₂ ,
  -CH = CH-COOX, where X is hydrogen or a physiologically compatible inorganic or organic cation,
  for a group
  or
  for a group
  where -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- where n = 1-10 and z = 1 or when 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 are each independently
  Hydrogen,
  a C _1-4 alkyl group,
  a C _1-4 alkoxy group,
  a C _1-4 monohydroxyalkyl group,
  a C _3-4 -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 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.

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. Composition according to one of claims 1 to 3, characterized in that X for Hydrogen stands. 6. Composition according to one of claims 1 to 5, characterized in that in the compound of the formula II both radicals R ¹² and R ^{13 are} hydrogen. 5. Composition according to one of claims 1 to 3, characterized in that n = 1-6, especially 1-3, and z = 1. 7. Composition according to one of claims 1 to 6, characterized in that in the compound of formula II at least three of the groups R ⁸ , R ⁹ , R ¹⁰ and R ^{11 are} hydrogen. 8. Composition according to one of claims 1 to 7, characterized in that in the compound of formula II Y and Z are independently 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 of formula II from N, N'-bis (4-aminophenyl) -1,4-diazacycloheptane and N, N'-bis (4-amino-3-methylphenyl) -1,4-diazacycloheptane are selected. 10. Composition according to one of claims 1 to 9, characterized in that Compounds of the formula I and of the formula II in total in an amount of 0.005 to 20 wt .-%, preferably 0.1 to 5 wt .-% are included. 11. Composition according to one of claims 1 to 9 characterized gekennzeichet that there is a Oxidation hair dye is. 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- (2-hydroxyethyl) -2,5-diaminobenzene, p-phenylenediamine, p-toluenediamine, N, N-bis- (2'-hydroxyethyl) -p-phenylenediamine, p-aminophenol, 3- Methyl p-aminophenol, 2-aminomethyl-p-aminophenol, 2-diethylaminomethyl-4- aminophenol and 1,3-N, N'-bis (2'-hydroxyethyl) -N, N'-bis (4'-amino-phenyl) -diamino 1,3-propan-2-ol are included.   13. Composition according to one of claims 1 to 12, characterized in that it 1- Naphthol, resorcinol, 1,3-bis (2,4-diaminophenoxy) propane, 4-chlororesorcinol, 2,4-diami nophenoxyethanol, 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-2-methylphenol, 2-methyl-5 (2-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 agent, are included. 15. Composition according to one of claims 1 to 14, characterized in that further at least one substantive dye is included. 16. A process for dyeing keratin-containing fibers, in particular human hair, wherein a colorant containing a combination of

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

wherein
the radicals R ¹ and R ² 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 _1-4 -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 R ³ and R ⁴ is
Hydrogen,
a C _1-4 alkoxy group,
a C _1-4 alkyl group,
a C _1-4 hydroxyalkyl group, preferably hydroxy-terminated, or
a halogen atom,
and the other radical R ³ or R ⁴ is one of the groups:
-O-CH ₂ -CH = CH ₂ ,
-CH = CH-COOX, where X is hydrogen or a physiologically compatible inorganic or organic cation,
for a group
or
for a group
where -A- each represents one of the groups
- (CH ₂ ) _x with x = 1-4,
-O- (CH ₂ ) YO- with y = 1-4,
-O- (C _n H _2n-z (OH) _z ) -O- where n = 1-10 and z = 1 or when 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 are each independently
Hydrogen,
a C _1-4 alkyl group,
a C _1-4 alkoxy group,
a C _1-4 monohydroxyalkyl group,
a C _3-4 -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

• 1.
• 2. 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 of these compounds and conventional kosme tables ingredients applied to the keratin fibers, some time, usually about 30 minutes, left on the fiber and then rinsed again or washed out with a shampoo.