DE19717224A1 - Use of unsaturated aldehydes for dyeing keratin fibers - Google Patents

Abstract

The invention relates to the use of unsaturated aldehydes of formulae (Ia) or (Ib), wherein R<1>, R<2>, R<3> and R<4> independently mean hydrogen, halogen, a C1-C4-alkoxy, C1-C4-alkyl, aryl radical or a C1-C4-alkoxy-C1-C4-aryl radical and n stands for 1 or 2, wherein R<1> and R<2>, R<1> and R<3>, R<2> and R<3> and R<2> and R<4> can form together with a residual molecule a ring with 5 to 7 units when n equals 1, in addition to the corresponding mono, bis or omega -alkoxy acetals, for the dying of fibers containing keratin, specially human hair.

Description

The invention relates to the use of unsaturated aldehydes for coloring keratin containing fibers, especially human hair.

For dyeing keratin fibers, e.g. B. hair, wool or furs come in all mean either direct dyes or oxidation dyes by oxidative Coupling one or more developer components with each other or with one or several coupler components are created for use. Coupler and developer compo nenten are also referred to as oxidation dye precursors.

Primary aromatic amines with a white are usually used as developer components teren, in the para or ortho position free or substituted hydroxy or ami nogroup, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazolone derivatives as well as 2,4,5,6-tetraaminopyrimidine and its derivatives.

Special 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-diamino phenyl) ethanol, 2- (2,5-diaminophenoxy) ethanol, 1-phenyl-3-carboxyamido-4-amino-pyrazo lon-5, 4-amino-3-methylphenol, 2-aminomethyl-4-aminophenol, 2-hydroxymethyl-4-amino phenol, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-tri amino-4-hydroxypyrimidine.

Usually m-phenylenediamine derivatives, naphthols, resor are used as coupler components cin and resorcinol derivatives, pyrazolones and m-aminophenols are used. As a coupler substance zen are particularly suitable for α-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino 2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 2,4-diaminophenoxyethanol, 1-phenyl-3-methyl-pyrazolon-5, 2,4-dichloro-3-aminophenol, 1,3- Bis- (2,4-diaminophenoxy) propane, 2-chlororesorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3-ami nophenol, 2-methylresorcinol and 5-methylresorcinol.  

With regard to other conventional dye components, the Colipa list is explicitly mentioned issued by the Industrial Association for Personal Care and Detergent, Frankfurt, reference genom men.

With oxidation dyes intensive dyeings can be achieved with good fastness properties, but the development of the color is generally done under the influence of oxidizing agents such as. B. H ₂ O ₂ . which in some cases can damage the fiber. Furthermore, some oxidation dye precursors or certain mixtures of oxidation dye precursors can sometimes have a sensitizing effect on people with sensitive skin. Direct dyes are applied under gentler conditions, but their disadvantage is that the dyeings often have inadequate fastness properties.

German patent application DE 28 30 497 discloses hair dyes which contain salicylaldehyde in combination with oxidation dye precursors, e.g. B. 2,5-diaminotoluene, 4-amino phenol or 2,4-diaminotoluene, which, however (in combination with the additionally contained hydrogen peroxide) can have a more or less great sensitization potential. Oils German Auslegeschrift DE 29 32 489 also discloses H ₂ O ₂ -containing hair dye medium, the benzaldehydes, for. B. 2-hydroxy-3-methoxybenzaldehyde or 4-hydroxy-3-methoxy benzaldehyde, in combination with oxidation dye precursors. The patent specifications US 5,034,014 and US 5,199,954 describe hair dye formulation examples, the p-dimethylaminobenzaldehyde or p-dimethylaminocinnamaldehyde z. B. in combination with the sen sensitizing p-phenylenediamine.

The patent US 4,391,603 has the object of oxidizing agent-free hair colorants contain substituted benzaldehydes. The hair dyes disclosed there are direct hair dyes with which there are no color shades, depths and color fastness units of hair dyes containing oxidation precursors.

The use of the aromatic aldehydes described in more detail below for dyeing Fibers containing keratin are not yet known.

The object of the present invention is to provide colorants for keratin fibers, in particular human hair, which are qualitatively at least equivalent to the usual oxidation hair colorants in terms of color depth, gray coverage and fastness properties, but without necessarily relying on oxidizing agents such as e.g. B. H ₂ O _{2 to be} instructed. In addition, the colorants may have little or no potential for sensitization.

The invention relates to the use of unsaturated aldehydes described by the tautomeric limit formulas Ia and Ib,

in which R ¹ , R ² , R ³ and R ⁴ independently of one another are hydrogen, halogen, a C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkyl, aryl or C ₁ -C ₄ alkoxy -C ₁ -C ₄ alkyl and n stand for the numbers 1 or 2, where R ¹ and R ² , R ¹ and R ³ , R ² and R ³ and R ² and R ⁴ each together with the rest of the molecule is a 5th - Can form 7-membered ring when n is 1, and the corresponding mono-, bis- or ω-alkoxyacetals for dyeing keratin fibers, especially human hair.

Surprisingly, it was found that the alde shown in the formulas Ia and Ib hyde is excellent for coloring ke even in the absence of oxidizing agents fibers containing ratin are suitable. They result in colorations with excellent brilliance and Depth of color and lead to diverse color shades. The use of oxidizing agents is said to However, they are not excluded in principle.

Among keratin fibers are wool, furs, feathers and especially human hair to understand. In principle, however, the colorants according to the invention can also be used for dyeing other natural fibers, such as. B. cotton, jute, sisal, linen or silk, modified nature 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 be used.

The unsaturated aldehydes of the formulas Ia and Ib are preferably selected from the Group glutaconaldehyde, 1-formyl-3-hydroxymethylene-1-cyclohexene, 1-formyl-3-hydroxyme thylene-1-cycloheptene and 7-hydroxy-2,4,6-heptatrienal and their substituted derivatives so such as the physiologically acceptable salts thereof, especially the alkali and ammonium  salt, the tetrabutylammonium salts and Na salts and mixtures thereof being particularly preferred are preferred.

The substances according to formulas Ia and Ib are known from the literature or are commercially available Lich.

The aldehydes of the formulas Ia and Ib are preferably present in the colorants in an amount from 0.03 to 65, in particular 1 to 40 mmol, in each case based on 100 g of the total ten colorant. A single compound with the formula Ia or Ib or a mixture of several compounds can be used. You can as direct Coloring agents or in the presence of compounds that invent the coloring effect of the aldehydes used in accordance with the invention, such as oxidation dye precursors be set.

Coloring agents which alone contain aldehydes of the formulas Ia or Ib as the coloring component, are preferred for coloring in the yellow and red range. Colorings with increased ter brilliance and further improved fastness properties, especially in the yellow-orange, Brown and black areas as well as in the red and blue areas are achieved if the Al dehydes of the formulas Ia or Ib together with compounds with primary or secondary Amino group, e.g. B. aniline derivatives, with nitrogen-containing heterocyclic compounds gene, e.g. B. primary heteroaromatic amines, aromatic hydroxy compounds or CH-active compounds are used. On the one hand, these are connections that stand for themselves Only stain keratin fibers only weakly and only together with the aldehydes Formulas Ia and Ib give brilliant colors. On the other hand, Ver bonds that are already used as oxidation dye precursors.

Another object of the present invention is an agent for dyeing keratin fibers, in particular human hair, the
A at least one unsaturated aldehyde with the formula Ia or Ib and
B at least one compound having a primary or secondary amino group or hydroxy group, selected from primary or secondary aliphatic or aromatic amines, nitrogen-containing heterocyclic compounds, amino acids, oligopeptides and aromatic hydroxy compounds composed of 2 to 9 amino acids, and / or at least one CH-active compound,
contains.

The above-mentioned compounds of component B can be used in an amount of in each case 0.03 to 65, in particular 1 to 40 mmol, in each case based on 100 g of the total Colorant can be used.

Several different aldehydes of the formulas Ia or Ib can also be used in all colorants are used together; several different connections can also be used Component B can be used together. This embodiment is included also the use of such substances, the reaction products of unsaturated Represent aldehydes of the formula I with the compounds B mentioned.

Suitable compounds with primary or secondary amino groups are e.g. B. primary aromatic amines such as N, N-dimethyl, N, N-diethyl, N- (2-hydroxyethyl) -N-ethyl, N, N-bis (2-hydroxyethyl) -, N- ( 2-methoxyethyl-), 2,3-, 2,4-, 2,5-dichloro-p-phenylenediamine, 2-chloro-p-phenylene diamine, 2,5-dihydroxy-4-morpholinoaniline dihydrobromide, 2-, 3-, 4-aminophenol, 2-aminomethyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol o-, m-, p-phenylenediamine, o-, m-toluenediamine, 2,5-diaminotoluene, -phenol, - phenethol, 4-amino-3-methylphenol, 2- (2,5-diaminophenyl) ethanol, 2,4-diaminophenoxyethanol, 2- (2,5-diaminophenoxy) ethanol, 4-methylamine, 3-amino -4- (2'-hydroxyethyloxy) -, 3,4-methylenediamino-, 3,4-methylenedioxyaniline, 3-amino-2,4-dichloro-, 4-methylamino-, 2-methyl-5-amino-, 3rd -Methyl-4-amino-, 2-methyl-5- (2-hydroxyethylamino) -, 6-methyl-3-amino-2-chloro, 2-methyl-5-amino-4-chloro, 5- ( 2-hydroxyethylamino) -4-methoxy-2-methylphenol, 1,3-diamino-2,4-dimethoxybenzene, 2-, 3-, 4-amino benzoic acid, -phenylacetic acid, 2,3-, 2,4 -, 2,5-, 3,4-, 3,5-diaminobenzoic acid, 4-, 5- Amino salicylic acid, 3-amino-4-hydroxy-, 4-amino-3-hydroxy-benzoic acid, 2-, 3-, 4-aminobenzene sulfonic acid, 3-amino-4-hydroxybenzenesulfonic acid, 4-amino-3-hydroxynaphthalene-1 -sulfonic acid, 6-amino-7-hydroxynaphthalene-2-sulfonic acid, 7-amino-4-hydroxynaphthalene-2-sulfonic acid, 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid, 3-amino-2-naphthoic acid , 3-amino phthalic acid, 5-aminoisophthalic acid, 1,3,5-, 1,2,4-triaminobenzene, 1,2,4,5-tetraaminobenzene, 2,4,5-triaminophenol, pentaaminobenzene, hexaaminobenzene, 2,4 , 6 triaminoresorcinol, 4,5-diamino-catechol, 4,6-diaminopyrogallol, 3,5-diamino-4-hydroxy-catechol, aromatic cal anilines or phenols with a further aromatic radical, as shown in formula II

in the R ⁵ for a hydroxy or an amino group, which is substituted by C _1-4 alkyl, C _1-4 hydroxyalkyl, C _1-4 alkoxy or C _1-4 alkoxyC _1-4 alkyl groups can be substituted,
R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ^{10 represent} hydrogen, a hydroxy or an amino group which can be substituted by C _1-4 -alkyl-, C _1-4 -hydroxyalkyl-, C _1-4 -alkoxy-, C _1-4 aminoalkyl or C _1-4 alkoxyC _1-4 alkyl groups may be substituted, or represent a sulfonic acid group, and
X for a direct bond, a saturated or unsaturated carbon chain with 1 to 4 carbon atoms, optionally substituted by hydroxyl groups, a carbonyl, sulfonyl or imino group, an oxygen or sulfur atom, or a group with the formula III

Z- (CH ₂ -Q-CH ₂ -Z ') _o (III)

in which Q denotes a direct bond, a CH ₂ or CHOH group,
Z and Z 'independently of one another for an oxygen atom, an NR ¹¹ group, wherein
R ¹¹ denotes hydrogen, a C _1-4 alkyl or a hydroxy C _1-4 alkyl group,
the group O- (CH ₂ ) _p -NH or NH- (CH ₂ ) _{p '} -O, where p and p' are 2 or 3, and
o means a number from 1 to 4,
such as 4,4'-diaminostilbene, 4,4'-diaminostilbene-2,2'-disulfonic acid mono- or di-sodium salt, 4,4'-diaminodiphenylmethane, sulfide, sulfoxide, amine, 4 , 4'-diaminodiphenylamine-2-sulfonic acid, 4,4'-diaminobenzophenone, -diphenyl ether, 3,3 ', 4,4'-tetraaminodiphenyl, 3,3', 4,4'-tetrnamino-benzophenone, 1,3- Bis- (2,4-diaminophenoxy) propane, 1,8-bis (2,5-diaminophenoxy) -3,6-dioxaoctane, 1,3-bis (4-aminophenylamino) propane, -2- propanol, 1,3-bis- [N- (4-aminophenyl) -2-hydroxyethylamino] -2-propanol, N, N-bis- [2- (4-aminophenoxy) ethyl] methylamine, N-phenyl -1,4-phenylenediamine.

The aforementioned compounds can be used both in free form and in the form of their physio logically compatible salts, in particular as salts of inorganic acids, such as salt or Sulfuric acid.

Suitable nitrogen-containing heterocyclic compounds are e.g. B. 2-, 3-, 4-amino-, 2-amino- 3-hydroxy, 2,6-diamino, 2,5-diamino, 2,3-diamino, 2-dimethylamino-5-amino, 2-methyl mino-3-amino-6-methoxy-, 2,3-diamino-6-methoxy-, 2,6-dimethoxy-3,5-diamino-, 2,4,5-tria mino-, 2,6-dihydroxy-3,4-dimethylpyridine, 2,4-dihydroxy-5,6-diamino-, 4,5,6-triamino-, 4-Hy droxy-2,5,6-triamino, 2-hydroxy-4,5,6-triamino-, 2,4,5,6-tetraamino-, 2-methylamino-4,5,6- triamino-, 2,4-, 4,5-diamino-, 2-amino-4-methoxy-6-methyl-pyrimidine, 3,5-diaminopyrazole, -1,2,4-triazole, 3-amino, 3-amino-5-hydroxypyrazole, 2-, 3-, 8-aminoquinoline, 4-amino-quinaldine 2-, 6-aminonicotinic acid, 5-aminoisoquinoline, 5-, 6-aminoindazole, 5-, 7-amino-benzimidazole,  -benzothiazole, 2,5-dihydroxy-4-morpholinoaniline as well as indole and indoline derivatives, such as 4-, 5-, 6-, 7-aminoindole, 5,6-dihydroxyindole, 5,6-dihydroxyindoline and 4-hydroxyindoline. The featured named compounds can be used both in free form and in the form of their physiological compatible salts, e.g. B. as salts of inorganic acids, such as hydrochloric or sulfuric acid, be used.

All naturally occurring and synthetic amino acids come in as amino acids Question, e.g. B. by hydrolysis of vegetable or animal proteins, e.g. B. collagen, Ke ratin, casein, elastin, soy protein, wheat gluten or almond protein, accessible amino acids. Both acidic and alkaline amino acids can be used will. Preferred amino acids are arginine, histidine, tyrosine, phenylalanine, DOPA (Dihydroxyphenylalanine), omithine, lysine and tryptophan.

The oligopeptides can be naturally occurring or synthetic oligopeptides, however the oligopeptides contained in polypeptide or protein hydrolyzates, if they are about sufficient water for use in the colorants of the invention dispose of solubility. As examples are e.g. B. glutathione or in the hydrolysates of Kolla gene containing keratin, casein, elastin, soy protein, wheat gluten or almond protein to call gopeptides. Use together with compounds is preferred primary or secondary amino group or with aromatic hydroxy compounds.

Suitable aromatic hydroxy compounds are e.g. B. 2-, 4-, 5-methylresorcinol, 2,5-dimethyl resorcin, resorcinol, 3-methoxyphenol, pyrocatechol, hydroquinone, pyrogallol, phloroglucin, Hydroxyhydroquinone, 2-, 3-, 4-methoxy, 3-dimethylamino, 2- (2-hydroxyethyl) -, 3,4-methy lendioxyphenol, 2,4-, 3,4-dihydroxybenzoic acid, phenylacetic acid, gallic acid, 2,4,6- Trihydroxybenzoic acid, acetophenone, 2-, 4-chlororesorcinol, 1-naphthol, 1,5-, 2,3-, 2,7- Dihydroxynaphthalene, 6-dimethylamino-4-hydroxy-2-naphthalenesulfonic acid, 3,6-dihydroxy- 2,7-naphthalenesulfonic acid.

1,2,3,3-Tetramethyl-3H-in can be mentioned as examples of CH-active compounds dolium iodide, 1,2,3,3-tetramethylindolium p-toluenesulfonate, 1,2,3,3-tetramethyl-3H-indolium methanesulfonate, 2,3-dimethyl-benzothiazolium iodide, 2,3-dimethyl-benzothiazolium-p-toluene sulfonate, rhodanine, rhodanine-3-acetic acid, 1-ethyl-2-quinal dinium iodide, 1-methyl-2-quinaldi nium iodide barbituric acid, thiobarbituric acid, 1,3-dimethylthiobarbituric acid, diethylthiobarbitur acid, oxindole, 3-indoxy acetate, coumaranone and 1-methyl-3-phenyl-2-pyrazolinone.  

The compounds of component B are particularly preferably selected from the Group consisting of N- (2-hydroxyethyl) -N-ethyl-, 2-chloro-p-phenylenediamine, N, N-bis (2-Hy droxyethyl) -p-phenylenediamine, 4-aminophenol, p-phenylenediamine, 2- (2,5-diaminophenyl) - ethanol, 2,5-diaminotoluene, 3,4-methylenedioxyaniline, 3-amino-2,4-dichloro-, 2-methyl-5-amino-, 3-methyl-4-amino, 2-methyl-5- (2-hydroxyethylamino) -, 2-methyl-5-amino-4-chloro, 6-methyl-3- amino-2-chloro, 2-aminomethyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol, 3,4-methyl lendioxyphenol, 3,4-diaminobenzoic acid, 2,5-diamino-, 2-dimethylamino-5-amino-, 3-A- mino-2-methylamino-6-methoxy-, 2,3-diamino-6-methoxy-, 3,5-diamino-2,6-dimethoxy-, 2,6-di hydroxy-3,4-dimethylpyridine, 2-hydroxy-4,5,6-triamino-, 4-hydroxy-2,5,6-triamino-, 2,4,5,6-Te traamino-, 2-methylamino-4,5,6-triamino-pyrimidine, 3,5-diaminopyrazole, 3-amino-5- hydroxypyrazole, 5,6-dihydroxyindole and 5,6-dihydroxyindoline and preferably with them inorganic acids formed physiologically acceptable salts.

On the presence of oxidizing agents, e.g. B. H ₂ O ₂ , can be omitted. However, it can It may be desirable to add hydrogen peroxide or other oxidizing agents to the agents according to the invention for obtaining nuances which are lighter than the keratin-containing fiber to be colored. Oxidizing agents are generally used in an amount of 0.01 to 6% by weight, based on the application solution. A preferred oxidizing agent for human hair is H ₂ O ₂ .

The colorants according to the invention result in a wide range of color shades in the range from yellow-orange to brown-black; the fastness properties are excellent, the sen potential for sensitization very low.

In a preferred embodiment, the colorants according to the invention contain white teren modification of the color shades in addition to the compounds contained according to the invention gene and possibly other oxidation dye precursors additionally conventional direct Dyes, e.g. B. from the group of nitrophenylenediamines, nitroaminophenols, anthrachi none or indophenols, e.g. B. the under the international names or Han The names HC Yellow 2, HC Yellow 4, Basic Yellow 57, Disperse Orange 3, HC Red 3, HC Red BN, Basic Red 76, HC Blue 2, Disperse Blue 3, Basic Blue 99, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9, Basic Brown 16, Picramic Acid and Rodol 9 R known compounds, and 4-N-ethyl-1,4-bis (2'-hydroxyethylamino) -2-nitrobenzene, 1- (2'-hydroxyethylamino) -4-methyl-2-nitro-benzene, 1-amino-2-nitro-4- (2'-hydroxyethylamino) -5- chlorobenzene, 4-amino-2-nitro-diphenylamine-2'-carboxylic acid and / or 6-nitro-1,2,3,4-tetrahy droquinoxaline in an amount of 0.01 to 20 wt .-%, based on the total oxide hair dye.  

It is not necessary that the compounds of component B and possibly further oxidation dye precursors or the optional direct dyes represent uniform connections. Rather, in the colorants according to the invention, due to the manufacturing process for the individual dyes, in subordinate Amounts of other components may be included, provided that these do not affect the coloring result adversely affect or for other reasons, e.g. B. toxicological, excluded Need to become.

The colorants according to the invention already result at a physiologically compatible temperature temperatures of less than 45 ° C intense coloring. They are therefore particularly suitable for dyeing of human hair. The dye can be used on human hair agents are usually incorporated into a water-containing cosmetic carrier. Ge Suitable water-containing cosmetic carriers are e.g. B. creams, emulsions, gels or surfactant-containing foaming solutions such as B. shampoos or other preparations for the application on the keratin fibers are suitable. If necessary, it is too possible to incorporate the colorants in anhydrous carriers.

Furthermore, the colorants according to the invention can all be in such preparations known active ingredients, additives and auxiliary substances. In many cases, the colorants contain at least one surfactant, in principle both anionic and zwitterionic, ampho lytic, nonionic and cationic surfactants are suitable. In many cases it has but proved to be advantageous, the surfactants from anionic, zwitterionic or select nonionic surfactants.

Suitable anionic surfactants in preparations according to the invention are all anionic surface-active substances suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such as. B. a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group with about 10 to 22 carbon atoms. In addition, 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 having 10 to 22 carbon atoms and x = 0 or 1 to 16,
• Acyl sarcosides with 10 to 18 carbon atoms in the acyl group,
• Acyl taurides with 10 to 18 carbon atoms in the acyl group,
• Acyl isethionates with 10 to 18 carbon atoms in the acyl group,
• - Monosulfonic succinate 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 esters 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 carbon atoms and x = 0 or 1 to 12,
• Mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030,
• - Sulphated hydroxyalkyl polyethylene and / or hydroxyalkylene propylene glycol ether according to DE-A-37 23354,
• - Sulfonates of unsaturated fatty acids with 12 to 24 carbon atoms and 1 to 6 double bonds gene according to DE-A-39 26 344,
• - esters of tartaric acid and citric acid with alcohols, the addition products of about 2-15 molecules of ethylene oxide and / or propylene oxide on fatty alcohols with 8 to 22 carbon atoms represent.

Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids 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 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 (⁻) - 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 cocoalkyl-dimethylammonium glycinate, N-acyl-aminopropyl-N, N-dimethylammonium glycinate, for example the cocoacylaminopropyl-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 zwitter ionic surfactant is the fatty acid amide derivative known under the CTFA name Cocamidopropyl Betaine.

Ampholytic surfactants are those surface-active compounds which, in addition to a C _8-18 alkyl or acyl group, contain at least one free amino group and at least one -COOH or -SO ₃ H group in the molecule and are capable of forming internal salts are. Examples of suitable ampholytic surfactants are N-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N-alkyliminodipropionic acid, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyltaurine, N-alkyl sarcosine, 2-alkylaminopropionic acid and alkylaminoacetic acid each with about 8 up to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C _12-18 acyl sarcosine.

Nonionic surfactants contain z as a hydrophilic group. B. a polyol group, a poly alkylene glycol ether group or a combination of polyol and polyglycol ether group. Such connections are, for example

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

Examples of the cationi which can be used in the hair treatment compositions according to the invention In particular, surfactants are quaternary ammonium compounds. Ammo are preferred nium halides such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and Trialkylmethylammoniumchloride, e.g. B. Cetyltrimethylammonium chloride, stearyltrimethylam monium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryl dimethylbenzylammonium chloride and tricetylmethylammonium chloride. More fiction The quaternized protein hydrolyzates represent usable cationic surfactants.

Also suitable according to the invention are cationic silicone oils such as those in the Commercially available products Q2-7224 (manufacturer: Dow Coming; a stabilized trimethyl silylamodimethicone), Dow Corning 929 emulsion (containing a hydroxylamino modified  Silicon, which is also called Amodimethicone), SM-2059 (Manufacturer: General Elec tric), SLM-55067 (manufacturer: Wacker) and Abil®-Quat 3270 and 3272 (manufacturer: Th. Gold schmidt; diquaternary polydimethylsiloxanes, Quaternium-80).

Alkylamidoamines, especially fatty acid amidoamines such as that under the name Tego Amear®S 18 available stearylamidopropyldimethylamine, stand out apart from a good one conditioning effect especially due to its good biodegradability.

Quaternary ester compounds are also very readily biodegradable "Esterquats", such as the dialkylammonium sold under the trademark Stepantex® methosulfates and methyl-hydroxyalkyldialkoyloxyalkyl-ammonium methosulfates.

This is an example of a quaternary sugar derivative that can be used as a cationic surfactant 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 in each case be act uniform substances. However, it is usually preferred in the manufacture these substances from natural vegetable or animal raw materials, so that one Mixtures of substances with different alkyl chains depending on the respective raw material lengths received.

In the case of surfactants, the addition products of ethylene and / or propylene oxide with fatty alcohol hole or derivatives of these investment products, both products with a "normal" homolog distribution as well as those with a narrow homolog distribution be used. Under "normal" homolog distribution, mixtures of Homologues understood that one under the implementation of fatty alcohol and alkylene oxide Use of alkali metals, alkali metal hydroxides or alkali metal alcoholates as kata lysators receives. On the other hand, narrow homolog distributions are obtained if at for example hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates can be used as catalysts. The use of pro Products with a narrow homolog distribution can be preferred.

Other active ingredients, auxiliaries and additives are, for example

• non-ionic polymers such as, for example, vinyl pyrrolidone / vinyl acrylate copolymers, Polyvinyl pyrrolidone and vinyl pyrrolidone / vinyl acetate copolymers and polysiloxanes,  
• - cationic polymers such as quaternized cellulose ethers, polysiloxanes with quaternary Groups, dimethyldiallylammonium chloride polymers, acrylamide-dimethyldiallylammoni umchloride copolymers, dimethylaminoethyl methacrylate quaternized with diethyl sulfate Vinyl pyrrolidone copolymers, vinyl pyrrolidone imidazolinium methochloride copolymers and quaternized polyvinyl alcohol,
• - zwitterionic and amphoteric polymers such as acrylamidopropyl trimethyl ammonium chloride / acrylate copolymers and octylacrylamide / methyl methacrylate / tert-butyl aminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers,
• anionic polymers such as polyacrylic acids, crosslinked polyacrylic acids, Vinyl acetate / crotonic acid copolymers, vinyl pyrrolidone / vinyl acrylate copolymers, vinylace tat / butyl maleate / isobomylacrylate copolymers, methyl vinyl ether / maleic anhydride co polymers and acrylic acid / ethyl acrylate / N-tert-butylacrylamide terpolymers,
• - Thickeners such as agar agar, guar gum, alginates, xanthan gum, gum arabic Karaya gum, locust bean gum, linseed gums, dextrans, cellulose deri vate, e.g. B. methyl cellulose, hydroxyalkyl cellulose and carboxymethyl cellulose, starch ke fractions and derivatives such as amylose, amylopectin and dextrins, clays such. B. bentonite or fully synthetic hydrocolloids such. B. polyvinyl alcohol,
• Structurants such as glucose and maleic acid,
• - Hair conditioning compounds such as phospholipids, for example soy lecithin, Ei-Le citin and kephaline, as well as silicone oils,
• - Protein hydrolyzates, especially elastin, collagen, keratin, milk protein, soy protein and Wheat protein hydrolyzates, their condensation products with fatty acids and qua ternized 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 Zink Omadine, other substances for adjusting the pH value,
• - Active ingredients such as panthenol, pantothenic acid, allantoin, pyrrolidonecarboxylic 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 phos phate, imidazole, 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 and
• - antioxidants.

The constituents of the water-containing carrier are used to produce the inventive Colorants used in amounts customary for this purpose; e.g. B. are emulsifiers in Concentrations of 0.5 to 30% by weight and thickeners in concentrations of 0.1 up to 25 wt .-% of the total colorant used.

For the coloring result it can be advantageous to use ammonium or metal as coloring agents add salts. Suitable metal salts are e.g. B. formates, carbonates, halides, sulfates, Butyrate, Valeriate, Capronate, Acetate, Lactate, Glycolate, Tartrate, Citrate, Gluconate, Pro pionates, phosphates and phosphonates of alkaline earth metals, such as potassium, sodium or Lithium, alkaline earth metals, such as magnesium, calcium, strontium or barium, or from Alumi nium, manganese, iron, cobalt, copper or zinc, whereby sodium acetate, lithium bromide, calci umbromide, calcium gluconate, zinc chloride, zinc sulfate, magnesium chloride, magnesium sulfate Ammonium carbonate, chloride and acetate are preferred. These salts are preferably in an amount of 0.03 to 65, in particular from 1 to 40 mmol, based on 100 g of the ge whole colorant.

The pH value of the ready-to-use coloring preparations is usually between 2 and 11, preferably between 5 and 9.

For dyeing keratin fibers, especially for dyeing human hair ren, the colorants are usually in the form of the aqueous cosmetic carrier applied to the hair in an amount of 100 g, left there for about 30 minutes and turned on finally rinsed out or washed out with a commercially available hair shampoo.

The aldehydes of the formulas Ia and Ib and the compounds of component B can be ent neither be applied to the hair at the same time, but also one after the other, taking it it is irrelevant which of the two components is applied first. The optional ent holding ammonium or metal salts can be the first or the second compo be added. Between the application of the first and second components  can be up to 30 minutes apart. Pretreatment of the fibers with the Saline solution is possible.

The aldehydes of the formulas Ia and Ib and the compounds of component B can either stored separately or together, either in a liquid to pasty Preparation (aqueous or anhydrous) or as a dry powder. Are the components in a liquid preparation stored together, so this should reduce Re action of the components must be largely free of water. In the case of separate storage the reactive components are intimately mixed only immediately before use. In dry storage, a defined amount is usually used before use warm (50 to 80 ° C) water added and a homogeneous mixture is made.

Examples Preparation of a coloring solution

A slurry of 10 mmol of an aldehyde with the formula Ia or Ib, 10 mmol of a reactant, 10 mmol of sodium acetate and a drop of 20% fatty alkyl prepares ether sulfate solution in 100 ml of water. The slurry was briefly raised to approximately 80 ° C heated and filtered after cooling, the pH was then adjusted to 6.

A streak of 90% was not grayed in this dyeing solution at 30 ° C. for 30 minutes pretreated human hair introduced. The colored streak then turned 30 Rinsed with lukewarm water, dried in a warm (30-40 ° C) air stream and turned on combed out. Then the colorations are assessed visually in daylight.

The respective color shades and color depths are shown in Table 1 below ben.

The color depth was rated on the following scale:
-: no or very pale color
(+): weak intensity
+: medium intensity
+ (+): medium to strong intensity
++: strong intensity
++ (+): strong to very strong intensity
+++: very strong intensity

Colorings with 2-chloro-1-formyl-3-hydroxymethylene-cyclohexene

Colorings with 2-chloro-1-formyl-3-hydroxymethylene-cyclohexene

Colorings with glutaconaldehyde tetrabutylammoium salt

Colorings with glutaconaldehyde tetrabutylammoium salt

Colorings with glutaconaldehyde sodium salt

Colorings with glutaconaldehyde sodium salt

Claims (13)

1. Use of unsaturated aldehydes with the formulas Ia and Ib
independently in which R ^1, R ^2, R ³ and R ⁴ represent hydrogen, halogen, a C ₁ - C ₄ alkoxy, C ₁ -C ₄ alkyl, aryl or C ₁ -C ₄ alkoxy C ₁ -C ₄ alkyl and n represent the numbers 1 or 2, where R ¹ and R ² , R ¹ and R ³ , R ² and R ³ as well as R ² and R ^{4 together} with the rest of the molecule form a 5- can form a 7-membered ring if n is 1, and the corresponding mono-, bis- or ω-alkoxyacetals for dyeing keratin fibers, in particular human hair. 2. Use according to claim 1, characterized in that the aldehydes of For meln Ia or Ib in an amount of 0.03 to 65, in particular 1 to 40 mmol, based on 100 g of the total colorant. 3. Use according to claim 1 or 2, characterized in that the aldehydes of the formulas Ia and Ib are selected from glutaconaldehyde, 1-formyl-3-hydroxymes ethylene-1-cyclohexene, 1-formyl-3-hydroxymethylene-1-cycloheptene and 7-hydroxy- 2,4,6-heptatrienal, its substituted derivatives and the salts thereof. 4. Use according to one of claims 1 to 3, characterized in that additionally at least one compound with primary or secondary amino group or Hydroxy group selected from primary or secondary aliphatic or aroma table amines, nitrogen-containing heterocyclic compounds, amino acids 2 to 9 amino acids built oligopeptides and aromatic hydroxyverbin dungen, and / or at least one CH-active compound is used. 5. Use according to one of claims 1 to 4, characterized in that oxi dationsmittel in an amount of 0.01 to 6 wt .-%, based on the application sol solution.   6. Use according to claim 5, characterized in that H ₂ O _{2 is} used as the oxidizing agent. 7. Use according to one of claims 1 to 6, characterized in that anionic, zwitterionic and / or nonionic surfactants are used. 8. Containing compositions for dyeing keratin fibers, in particular human hair
A at least one unsaturated aldehyde of the formula Ia or Ib
in which R ¹ , R ² , R ³ and R ⁴ independently of one another are hydrogen, halogen, a C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkyl, aryl or C ₁ -C ₄ alkoxy C ₁ -C ₄ alkyl radical and n represent the numbers 1 or 2, where R ¹ and R ² , R ¹ and R ³ , R ² and R ³ and R ² and R ⁴ each together with the rest of the molecule form a 5 to Can form 7-membered ring when n is 1, and the corresponding mono-, bis- or ω-alkoxyacetals and
B at least one compound having a primary or secondary amino group or hydroxy group, selected from primary or secondary aliphatic or aromatic amines, nitrogen-containing heterocyclic compounds, amino acids, oligopeptides composed of 2 to 9 amino acids and aromatic hydroxy compounds, and / or at least one CH-active compound . 9. Composition according to claim 8, characterized in that component B is selected from
primary or secondary amines selected from the group consisting of N- (2-hydroxyethyl) -N-ethyl-, N- (2-methoxyethyl-), 2,3-, 2,4-, 2,5-dichloro-p -phenylene diamine, 2-chloro-p-phenylene diamine, N, N-bis- (2-hydroxyethyl) -p-phenylene diamine, 2,5-dihydroxy-4-morpholinoaniline dihydrobromide, 2-, 3-, 4-aminophenol, o -, m-, p-Phenylenediamine, 2,4-diaminophenoxyethanol, 2- (2,5-diaminophenyl) ethanol, 2,5-diaminotoluene, -phenol, -phenethol, 4-ethylamino-, 3-amino-4 - (2'-hydroxyethyloxy) -, 3,4-methylenediamino-, 3,4-methylenedioxyaniline, 3-amino-2,4-dichloro-, 4-methylamino-, 2-methyl-5-amino-, 3- Methyl-4-amino-, 2-methyl-5- (2-hydroxyethylamino) -, 2-methyl-5-amino-4-chloro, 6-methyl-3-amino-2-chloro, 5- (2nd -Hydroxyethylamino) -4-methoxy-2-methyl-, 4-amino-2-aminomethyl-phenol, 4-amino-2-hydroxymethyl-phenol, 1,3-diamino-2,4-di methoxybenzene, 2-, 3rd -, 4-aminobenzoic acid, phenylacetic acid, 2,3-, 2,4-, 2,5-, 3,4-, 3,5-diaminobenzoic acid, 4-, 5-aminosalicylic acid, 3-amino-4-hydroxy- , 4-amino-3-hydro xy-benzoic acid, 2-, 3-, 4-aminobenzenesulfonic acid, 3-amino-4-hydroxybenzenesulfonic acid, 4-amino-3-hydroxynaphthalene-sulfonic acid, 6-amino-7-hydroxynaphthalene-2-sulfonic acid, 7-amino-4 -hydroxynaphthalene-2-sulfonic acid, 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid, 3-amino-2-naphthoic acid, 3-aminophthalic acid, 5-aminoisophthalic acid, 1,3,5-, 1,2, 4-triaminobenzene, 1,2,4,5-tetraaminobenzene tetrahydrochloride, 2,4,5-triaminophenol trihydrochloride, pentaaminobenzene pentahydrochloride, hexaami nobenzol hexahydrochloride, 2,4,6-triaminoresorcinol trihydrochloride, 4,5-diaminobenzene catechol sulfate, 4,6-diaminopyrogallol dihydrochloride, 3,5-diamino-4-hydroxybrenzcate chin sulfate, aromatic anilines or phenols with a further aromatic radical such as 4,4'-diaminostilbene dihydrochloride, 4,4, -diaminostilbene 2,2'-disulfonic acid, Na salt, 4,4'-diaminodiphenylmethane, sulfide, sulfoxide, amine, 4,4'-diaminodiphenylamine 2-sulfonic acid, 4,4'-diaminobenzophenone, diphenyl ether, 3, 3 ', 4,4'-tetraaminod iphe nyl-tetrahydrochloride, 3,3 ', 4,4'-tetraamino-benzophenone, 1,3-bis (2,4-diaminophen oxy) propane tetrahydrochloride, 1,8-bis (2,5-diaminophenoxy ) -3,6-dioxaoctane-tetrahyrochloride, 1,3-bis- (4-aminophenylamino) propane, -2-propanol, 1,3-bis- [N- (4-aminophenyl) -2-hydroxyethylamino] -2-propanol, N, N-bis- [2- (4-aminophenoxy) ethyl] methyl amine trihydrochloride,
from nitrogen-containing heterocyclic compounds selected from the group consisting of 2-, 3-, 4-amino, 2-amino-3-hydroxy, 2,6-diamino, 2,5-diamino, 2,3-di amino-, 2-dimethylamino-5-amino-, 3-amino-2-methylamino-6-methoxy-, 2,3-diamino no-6-methoxy-, 3,5-diamino-2,6-dimethoxy-, 2,4,5-triamino-, 2,6-dihydroxy-3,4-dimethylpyridine, 4,5,6-triamino-, 2-hydroxy-4,5,6-triamino-, 4-hydroxy-2, 5,6-triamino-, 2,4,5,6-tetraamino-, 2-methylamino-4,5,6-triamino-, 2,4-, 4,5-diamino-, 2-amino-4-methoxy -6-methyl-pyrimidine, 2,3,4-trimethylpyrrole, 2,4-dimethyl-3-ethyl-pyrrole, 3,5-diaminopyrazole, -1,2,4-triazole, 3-amino, 3-amino -5-hydroxypyrazole, 2-, 3-, 8-aminoquinoline, 4-aminoquininaldine, 2-, 6-aminonicotinic acid, 5-aminoisoquinoline, 5-, 6-aminoin dazol, 5-, 7-amino-benzimidazole, -benzothiazole, 2,5-dihydroxy-4-morpholinoaniline as well as indole and indolinden derivatives such as 4-, 5-, 6-, 7-aminoindole, 4-, 5-, 6-, 7-hydroxyindole, 5,6- Dihydroxyindole, 5,6-dihydroxyindoline and 4-hydroxyindoline, and jew quickly from the physiologically tolerable salts of these compounds, preferably formed with organic acids,
aromatic hydroxy compounds selected from the group consisting of 2-, 4-, 5-methylresorcinol, 2,5-dimethylresorcinol, resorcinol, 3-methoxyphenol, pyrocatechin, hydroquinone, pyrogallol, phloroglucinol, hydroxyhydroquinone, 2-, 3-, 4- Methoxy-, 3-dimethylamino-, 2- (2-hydroxyethyl) -, 3,4-methylenedioxyphenol, 2,4-, 3,4-dihydroxy benzoic acid, -phenylacetic acid, gallic acid, 2,4,6-trihydroxybenzoic acid, -aceto phenone, 2-, 4-chlororesorcinol, 1-naphthol, 1,5-, 2,3-, 2,7-dihydroxynaphthalene, 6-dimethylamino-4-hydroxy-2-naphthalenesulfonic acid, 3,6-dihydroxy-2 , 7-naphthalenesulfonic acid, and
CH-active compounds selected from the group consisting of 1,2,3,3-tetra methyl-3H-indolinium iodide, 1,2,3,5-teframethylindolinium p-toluenesulfonate, 1,2,3,5-tetramethylindolinium methanesulfonate, 2,3-dimethyl-benzothiazolium iodide, 2,3-dimethyl-benzothiazolium-p-toluenesulfonate, rhodanine, rhodanine-3-acetic acid, 1-ethyl (methyl) -2-quinaldinium iodide, barbituric acid, thiobarbituric acid, 1,3- Dimethyl- (ethyl) thiobarbituric acid, oxindole, coumaranone and 1-methyl-3-phenyl-2-pyrazolinone. 10. Composition according to claim 9, characterized in that the connection of the compo nente B is selected from the group consisting of N- (2-hydroxyethyl) -N-ethyl-, 2-chloro-p-phenylenediamine, N, N-bis (2-hydroxyethyl) -p-phenylenediamine, 4-aminophe nol, p-phenylenediamine, 2- (2,5-diaminophenyl) ethanol, 2,5-diaminotoluene, 3,4-methy lendioxyaniline, 3-amino-2,4-dichloro, 2-methyl-5-amino, 3-methyl-4-amino, 2-methyl 5- (2-hydroxyethylamino) -, 2-methyl-5-amino-4-chloro, 6-methyl-3-amino-2- chloro, 2-aminomethyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol 3,4-methylene dioxyphenol, 3,4-diaminobenzoic acid, 2,5-diamino-, 2-dimethylamino-5-amino-, 3- Amino-2-methylamino-6-methoxy-, 2,3-diamino-6-methoxy-, 3,5-diamino-2,6-dimeth oxy-, 2,6-dihydroxy-3,4-dimethylpyridine, 2-hydroxy-4,5,6-triamino-, 4-hydroxy-2,5,6- triamino-, 2,4,5,6-tetraamino, 2-methylamino-4,5,6-triamino-pyrimidine, 3,5-diamino pyrazole, 3-amino-5-hydroxypyrazole, 5,6-dihydroxyindole and 5,6-dihydroxyindoline so as in each case from the physiologically preferably formed with inorganic acids compatible salts of these compounds. 11. Agent according to one of claims 8 to 10, characterized in that direct pull dyes from the group of nitrophenylenediamines, nitroaminophenols, An thrachinones or indophenols can be used.   12. Composition according to one of claims 8 to 11, characterized in that Ammo nium or metal salts selected from the group of formates, carbonates, halogens nides, sulfates, butyrutes, valerates, capronates, acetates, lactates, glycolates, tartrates, Citrates, gluconates, propionates, phosphates and phosphonates of alkaline earth metals, such as potassium, sodium or lithium, alkaline earth metals such as magnesium, calcium, stron tium or barium, or of aluminum, manganese, iron, cobalt, copper or zinc be admitted. 13. A process for dyeing keratin-containing fibers, which contains a colorant
A at least one unsaturated aldehyde of the formula Ia or Ib
in which R ¹ , R ² , R ³ and R ⁴ independently of one another are hydrogen, halogen, a C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkyl, aryl or C ₁ -C ₄ alkoxy C ₁ -C ₄ alkyl radical and n represent the numbers 1 or 2, where R ¹ and R ² , R ¹ and R ³ , R ² and R ³ and R ² and R ⁴ each together with the rest of the molecule form a 5 to Can form 7-membered ring when n is 1, and the corresponding mono-, bis- or ω-alkoxyacetals and
B at least one compound having a primary or secondary amino group or hydroxy group, selected from primary or secondary aliphatic or aromatic amines, nitrogen-containing heterocyclic compounds, amino acids, oligopeptides composed of 2 to 9 amino acids and aromatic hydroxy compounds, and / or at least one CH-active compound ,
and the usual cosmetic ingredients are applied to the keratin fibers, left on the fibers for some time, usually about 30 minutes, and then rinsed out or washed out with a shampoo.