DE10061990A1 - Agent for dyeing keratinous fibers - Google Patents

Abstract

The invention relates to an agent for dyeing keratin containing fibers, especially human hair. The inventive agent contains as the dyeing component compounds of formula (I): A-CH=B-CH=A', wherein =B- represents a group =CR<1>- or a group (1), A is selected from the groups (A1), (A2), (A3), (A4) and A' is selected from the groups (A11), (A12), (A13), (A14), wherein X and Y independently represent a sulfur atom, an oxygen atom, or a group NR', wherein R' represents a C1-C4 alkyl group that is optionally substituted with an SO3<-> group, R<1> represents hydrogen, a C1-C4 alkyl group or a group NH2, R<2> represents hydrogen or a halogen atom, especially a chlorine atom, R<5> and R<23> independently represent a C1-C4 alkyl group that is optionally substituted with one or more hydroxy group(s) or an acid or acid anion group, especially an SO3<-> group, R<8>, R<17>, R<25> and R<26> independently represent hydrogen, a C1-C4 alkyl group, a C1-C4 alkoxy group, a phenyl group, an SO2CF3 group or a carboxy group that is esterified with a C1-C4 alkyl group, and the remaining rests independently represent hydrogen, a halogen atom, a C1-C4 alkyl group or a C1-C4 alkoxy group that are optionally substituted by one or more hydroxy groups or halogen atoms. The positive charge in the groups used can be compensated for by a negative charge in one of the rests or by an acid anion. The inventive agents are especially useful for dyeing keratin containing fibers, particularly in the absence of oxidizing agents.

Description

The invention relates to an agent for dyeing keratin-containing fibers, in particular human hair that contains special coloring component, the use of this special components as a coloring component in hair dyes and a Verfah ren for dyeing keratin-containing fibers, in particular human hair.

For the dyeing of keratin-containing fibers, for example hair, wool or furs, In general, either direct dyes or oxidation dyes, the by oxidative coupling of one or more developer components with each other or arise with one or more coupler components, for use. Coupler and Developer components are also referred to as oxidation dye precursors.

As developer components are usually primary aromatic amines with a further, in the para or ortho position free or substituted hydroxy or Amino group, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazole probe and 2,4,5,6-tetraaminopyrimidine and derivatives thereof.

Specific representatives are, for example, p-phenylenediamine, p-toluenediamine, 2,4,5,6-Te traaminopyrimidine, p-aminophenol, N, N-bis- (2'-hydroxyethyl) -p-phenylenediamine, 2- (2 ', 5'-diaminophenyl) ethanol, 2- (2', 5'-diaminophenoxy) ethanol, 1-phenyl-3-carboxy amido-4-amino-pyrazolone-5, 4-amino-3-methylphenol, 2-aminomethyl-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 are usually m-phenylenediamine derivatives, naphthols, Resorcinol and resorcinol derivatives, pyrazolones, m-aminophenols and substituted pyridine used. Particularly suitable as coupler substances are α-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, Resorcinol monomethyl ether, m-phenylenediamine, 2,4-diaminophenoxyethanol, 2-amino-4 (2'-hydroxyethylamino) -anisole, 1-phenyl-3-methyl-pyrazolone-5, 2,4-dichloro-3-aminophe nol, 1,3-bis (2 ', 4'-diaminophenoxy) -propane, 2-chlororesorcinol, 4-chlororesorcinol, 2-chloro-6- methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 3-amino-6-methoxy-2- methylamino-pyridine and 3,5-diamino-2,6-dimethoxypyridine.

With regard to 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), as well the "European Inventory of Cosmetic Raw Materials", 1996, published by the Euro European grain mission, available in disk form from the Federal Association of German In industrial and commercial enterprise for pharmaceuticals, health products and personal care products e. V., Mannheim.

Although intensive dyeings with good fastness properties can be achieved with oxidation dyes, the development of the color generally takes place under the influence of oxidizing agents such as H ₂ O ₂ , which may in some cases result in damage to the fiber. Furthermore, some oxidation dye precursors or certain mixtures of oxidation dye precursors can sometimes have a sensitizing effect on persons with sensitive skin. Direct dyes which applied to the gentler conditions, but their disadvantage is that the dyeings often have only insufficient fastness properties.

The use of the special components for dyeing keratin-containing fibers is 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, without, however, necessarily pointing to oxidizing agents such as H ₂ O ₂ his. In addition, the colorants must have no or only a very small sensitizing potential.

Surprisingly, it has now been found that the verbin shown in the formula I. even in the absence of oxidizing agents are excellent for dyeing of keratin-containing fibers are suitable. They give colorations with excellent brilliance and color depth and lead to diverse color nuances. The use of oxidizing agents However, zien should not be excluded in principle.

The invention relates to an agent for dyeing keratin-containing fibers, in particular human hair, containing as coloring component compounds of the formula I,

A-CH = B-CH = A '(I)

in which = B- stands for a group = CR ¹ - or a group

A is selected from the groups

and A 'is selected from the groups

in which
X and Y independently of one another represent a sulfur atom, an oxygen atom, or a group NR ', where R' is a C ₁ - to C ₄ -alkyl group which is optionally substituted by an SO ₃ ^- group,
R ¹ is hydrogen, a C ₁ - to C ₄ -alkyl group or a group NH ₂ ,
R ² is hydrogen or a halogen atom, in particular a chlorine atom,
R ⁵ and R ²³ independently of one another represent a C ₁ - to C ₄ -alkyl group which is optionally substituted by one or more hydroxyl group (s) or an acid or acid anion group, in particular an SO ₃ ^- group,
R ⁸ , R ¹⁷ , R ²⁵ and R ²⁶ independently of one another represent hydrogen, a C ₁ - to C ₄ -alkyl group, a C ₁ - to C ₄ -alkoxy group, a phenyl group, an SO ₂ CF ₃ group or a carboxy group esterified with a C ₁ to C ₄ alkyl group, and
the remaining radicals are independently of one another hydrogen, a halogen atom, a C ₁ - to C ₄ -alkyl group or a C ₁ - to C ₄ -alkoxy group which are optionally substituted by one or more hydroxyl groups or halogen atoms,
wherein the positive charge can be balanced by a negative charge in one of the residues or by an acid anion.

Among keratin-containing fibers are wool, furs, feathers and especially human To understand hair. In principle, however, the colorants according to the invention can also be used for Dyeing other natural fibers, such as 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 poly amide, polyacrylonitrile, polyurethane and polyester fibers are used.

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. C ₁ -C ₄ -alkoxy radicals which are preferred according to the invention are, for example, a methoxy or an ethoxy group. Furthermore, as preferred examples of a C ₁ - to C ₄ -hydroxyalkyl group, a hydroxy methyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group may be mentioned. A 2-hydroxyethyl group is particularly preferred. Examples of halo genatome according to the invention F, Cl or Br atoms, Cl atoms are very particularly preferred. The other terms used are derived according to the invention from the definitions given here.

According to the invention compounds are particularly preferred of the formula I wherein R ⁵ and R ²³ are independently a methyl group, an ethyl group, a 2- hydroxyethyl group or a 2-Sulfonatpropylgruppe.

Particular preference is furthermore given to compounds of the formula I in which R ⁸ , R ¹⁷ , R ²⁵ and R ²⁶ independently of one another represent hydrogen, a methyl group, an ethyl group, a methoxy group, a phenyl group, an SO ₂ CF ₃ group or a carboxyethyl group.

In a particularly preferred embodiment of the present invention are as Compounds of the formula I, one or more of the compounds mentioned in Table 1 used, wherein the substituents not defined in the table are hydrogen.  

Preferred acid anions to balance the positive charge are acid anion group within the compounds of formula I itself or free anions, in particular Benzenesulfonate, p-toluenesulfonate, methanesulfonate, ethanesulfonate, propanesulfonate, Perchlo sulfate, chloride, bromide, iodide, tetrachlorozincate, methylsulfates, trifluoromethanesul fonate, hexafluorophosphate and / or tetrafluoroborate.

Some of the compounds of the formula I are known from the literature, commercially available or can be prepared by known synthesis methods.

The above-mentioned compounds of the formula I are preferably used in the agents according to the invention each in an amount of 0.03 to 65 mmol, in particular from 1 to 40 mmol, based on 100 g of the total colorant used.

The compounds of the formula I used according to the invention can be used as direktzie or in the presence of conventional oxidation dye precursors, such as conventional coupler and developer components already described in the introductory part of Be were used.

Colorants, the only coloring component, the compounds of the invention are preferably used for colorations of yellow, orange to red.

To obtain further and more intense colorations, the inventive Agent additionally color enhancers included. The color enhancers are preferably out selected from the group consisting of piperidine, piperidine-2-carboxylic acid, piperidine-3-car bonsäure, piperidine-4-carboxylic acid, pyridine, 2-hydroxypyridine, 3-hydroxypyridine, 4- Hydroxypyridine, imidazole, 1-methylimidazole, histidine, pyrrolidine, proline, pyrrolidone, Pyrrolidone-5-carboxylic acid, pyrazole, 1,2,4-triazole, piperazine, their derivatives and their physiologically acceptable salts.

The color enhancers mentioned above may be in an amount of 0.03 to 65, in particular 1 to 40 mmol, in each case based on 100 g of the total colorant, be used.  

In all colorants also several different compounds of the formula I can are used; as well as several different oxidation dye vor products and / or color intensifiers are used together.

The presence of oxidizing agents, such as H ₂ O ₂ , can be dispensed with. However, it may be desirable under some circumstances, the erfindungsge MAESSEN means to achieve the nuances that are brighter than the keratin-containing Fa ser to be dyed, hydrogen peroxide or other oxidizing agents add. Oxidizing agents are usually used in an amount of 0.01 to 6 wt .-%, based on the appli cation solution. A preferred oxidizing agent for human hair is H ₂ O ₂ .

In a preferred embodiment, the inventive colorants for further modification of the shades in addition to the invention contained verbin In addition, customary substantive dyes, for example from the group of Ni trophenylenediamines, nitroaminophenols, anthraquinones or indophenols, such as example, under the international names or trade names HC Yellow 2, HC Yellow 4, HC Yellow 6, 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 and Basic Brown 17 Known Ver compounds and picramic acid 2-amino-6-chloro-4-nitrophenol, 4-amino-2-nitrodiphe nylamine-2'-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 4-N-ethyl-1,4-bis (2'-hy droxyethylamino) -2-nitrobenzene hydrochloride and 1-methyl-3-nitro-4- (2'-hydroxyethyl) - aminobenzene. The agents according to the invention according to this embodiment contain the substantive dyes preferably in an amount of 0.01 to 20 wt .-%, based on the entire 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 alkano root included.  

It is not necessary that the compounds according to the invention of the formula I or the optional oxidation dye precursors, color enhancers and directly drawing dyes each represent uniform compounds. Rather, in the colorants according to the invention, due to the production process for the one individual dyes, minor amounts of other components, as far as these do not adversely affect the staining result or for other reasons, For example, toxicological, must be excluded.

The colorants according to the invention give already at physiologically tolerable Tem temperatures of less than 45 ° C. They are therefore particularly suitable for Dyeing of human hair. For use on human hair, the Colorants usually incorporated in an aqueous cosmetic carrier who the. Suitable hydrous cosmetic carriers are, for example, creams, emulsions, Gels or surfactant-containing foaming solutions such as shampoos or on preparations suitable for use on the keratin-containing fibers. If necessary, it is also possible to incorporate the colorants in anhydrous carrier.

Furthermore, the colorants of the invention may be all in such preparations be knew active ingredients, additives and excipients included. In many cases, the colorants contain at least one surfactant, wherein in principle both anionic and zwitterionic, am phytic, nonionic and cationic surfactants are suitable. In many cases it has However, 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 surfactants suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such as a carboxylate, sulfate, sulfonate or phosphate group and a lipo philic alkyl group having about 10 to 22 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups may be present in the molecule. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium as well as the mono-, di- and trialkanolammonium salts having 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-alkylpolyoxyethylester 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 ether carboxylic acids having 10 to 18 carbon atoms in the alkyl group and up to 12 Glykolethergrup 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 N-alkyl-N, N-dimethylammonium glycinates, for example cocoalkyl dimethylammonium glycinate, N-acylaminopropyl N, N-dimethylammoniumglycinates, for example cocoacylaminopropyl-dimethylammonium glycinate, and Alkyl-3-carboxymethyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and Kokosacylaminoethylhydroxyethylcarboxy methylglycinat. A preferred zwitterionic surfactant is the fatty acid amide derivative known under the CTFA designation 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-alkylaminopropionic 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, for example, a polyol group, a polyalkylene glycol ether 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 containing 8 to 22 carbon atoms, to fatty acids containing 12 to 22 carbon atoms Atoms and 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 hydrogenated Rizi nusöl,
• - Addition products of ethylene oxide to 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, dialkyldimethylammoni Rechlorides and Trialkylmethylammoniumchloride, for example Cetyltrimethylammoni chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, Lau Ryldimethylammoniumchlorid, Lauryldimethylbenzylammoniumchlorid and Tricetylme methylammonium. Further cationic surfactants which can be used according to the invention the quaternized protein hydrolysates.

Likewise suitable according to the invention are cationic silicone oils, such as those described in US Pat Commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trim thylsilylamodimethicone), Dow Corning 929 emulsion (containing a hydroxyl-amino-mo 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 methylhydroxyal sold under the trademark Stepantex® kyldialkoyloxyalkylammoniummethosulfate.

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, depending on the particular raw material alkyl chain lengths receives.

For the surfactants, the adducts of ethylene and / or propylene oxide to fat Alcohols or derivatives of these addition products may represent both products with a "normal" homolog distribution as well as with a restricted homo logen distribution be used. Under "normal" homolog distribution are thereby Mixtures of homologues understood in the reaction of fatty alcohol and Alkylene oxide using alkali metals, alkali metal hydroxides or alkali obtained metal alkoxides as catalysts. Narrow homolog distributions are there when, for example, hydrotalcites, alkaline earth metal salts of ethercarbon acids, alkaline earth metal oxides, hydroxides or alcoholates used as catalysts become. The use of products with restricted homolog distribution can be be preferred.

Other active ingredients, auxiliaries and additives are, for example

• Nonionic polymers such as vinyl pyrrolidone / vinyl acrylate copo polymers, polyvinylpyrrolidone and vinylpyrrolidone / vinyl acetate copolymers and poly siloxanes,
• 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 methochlo Rid copolymers and quaternized polyvinyl alcohol,
• Zwitterionic and amphoteric polymers such as acrylamidopropyl tri methyl ammonium chloride / acrylate copolymers and octylacrylamide methyl methacrylate 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 acid anhydride 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, dextran, cellu lose derivatives, for example methylcellulose, hydroxyalkylcellulose and carboxy methylcellulose, starch fractions and derivatives such as amylose, amylopectin and Dextrins, clays such as bentonite or fully synthetic hydrocolloids such as 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 colorants are used in amounts customary for this purpose; for example, who the emulsifier in concentrations of 0.5 to 30 wt .-% and thickener in Concentrations of 0.1 to 25 wt .-% of the total colorant used.

For the dyeing result, it may be advantageous to the colorants ammonium or metal Add salts. Suitable metal salts are, for example, formates, carbonates, halo genides, sulphates, butyrates, valerates, capronates, acetates, lactates, glycolates, tartrates, Citrates, gluconates, propionates, phosphates and phosphonates of alkali metals, such as Potassium, sodium or lithium, alkaline earth metals such as magnesium, calcium, strontium or barium, or of aluminum, manganese, iron, cobalt, copper or zinc, wherein Sodium acetate, lithium bromide, calcium bromide, calcium gluconate, zinc chloride, zinc sulfate, Magnesium chloride, magnesium sulfate, ammonium carbonate, chloride and acetate are. These salts are preferably in an amount of 0.03 to 65 mmol, in particular from 1 to 40 mmol, based on 100 g of the total colorant. The pH the ready-to-use dyeing preparations is usually between 2 and 12, preferably between 4 and 10.

A second object of the present invention relates to the use of the verbin formulations of the formula I for coloring keratinic fibers.

A third object of the present invention relates to a process for dyeing keratin-containing fibers, in particular human hair, in which a colorant enthal at least one compound of the formula I and customary cosmetic ingredients The keratin fibers applied, some time, usually about 30 minutes, on the Leave fiber and then rinsed again or out with a shampoo will wash.  

The compounds of the formula I and the oxidation dye which may be present Precursors, color enhancers and direct dyes can be used either simultaneously be applied to the hair or even sequentially, where it is irrelevant which of the two components is applied first. The facultative Am Mono or metal salts may be added to the first or the second component become. Between the application of the first and the second component can be up to 30 minutes interval. Also a pretreatment of the fibers with the saline solution is possible.

The compounds of the formula I and the oxidation dye which may be present precursors, color enhancers and direct dyes can be either separated or be stored together, either in a liquid to pasty preparation (aqueous or anhydrous) or as a dry powder. In the separate storage, the Kom components are intimately mixed immediately before use. At the troc kenen storage is usually a defined amount of warm (30 to 80 ° C) added water and made a homogeneous mixture.  

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 (Cognis)
² sodium lauryl ether sulfate (about 28% active, CTFA name: Sodium Laureth Sulfate) (Cognis)
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 designation Cocoamidopropyl Betaine) (Cognis)
⁴ cetylstearyl alcohol with about 20 moles of EO (CTFA designation: ceteareth-20) (Cognis) @@@

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

cream base 50.0 coloring component 7.5 mmol Na ₂ SO ₃ (inhibitor) 1.0 (NH ₄ ) ₂ SO ₄ 1.0 conc. ammonia solution ad pH 10 water ad 100

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

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

The coloring components used and the dyeing results are in the following Ta belle shown.

coloring component hue Compound 1 according to Table 1 Kalypsorot Compound 2 according to Table 1 melon Orange Compound 3 according to Table 1 lemon Compound 4 according to Table 1 cream Compound 5 according to Table 1 Red orange Compound 6 according to Table 1 red

Claims (11)

1. A composition for dyeing keratin-containing fibers, in particular human hair, ent holding as a coloring component compounds of the formula I,
A-CH = B-CH = A '(I)
where = B- stands for a group = CR 'or a group
A is selected from the groups
and A 'is selected from the groups
in which
X and Y independently of one another represent a sulfur atom, an oxygen atom, or a group NR ', where R' is a C ₁ - to C ₄ -alkyl group which is optionally substituted by an SO ₃ ^- group,
R ¹ is hydrogen, a C ₁ - to C ₄ -alkyl group or a group NH ₂ ,
R ² is hydrogen or a halogen atom, in particular a chlorine atom,
R ⁵ and R ²³ independently of one another represent a C ₁ - to C ₄ -alkyl group which is optionally substituted by one or more hydroxy group (s) or an acid or acid anion group, in particular an SO ₃ ^- group,
R ^8, R ^17, R ²⁵ and R ²⁶ are independently hydrogen, a C ₁ - to C ₄ - alkyl group, a C ₁ - to C ₄ alkoxy group, a phenyl group, an SO ₂ CF ₃ - group or a with a C ₁ - to C ₄ alkyl group esterified carboxy group, and
the remaining radicals are independently of one another hydrogen, a halogen atom, a C ₁ - to C ₄ -alkyl group or a C ₁ - to C ₄ -alkoxy group which, if appropriate, are substituted by one or more hydroxyl groups or halogen atoms,
wherein the positive charge can be balanced by a negative charge in one of the residues or by an acid anion. 2. Composition according to claim 1, characterized in that R ⁵ and R ²³ independently of one another represent a methyl group, an ethyl group, a hydroxyethyl group or a 2-sulfonatopropyl group. 3. Composition according to one of claims 1 or 2, characterized in that R ⁸ , R ¹⁷ , R ²⁵ and R ²⁶ are each independently hydrogen, a methyl group, an ethyl group, a methoxy group, a phenyl group, a SO ₂ CF ₃ - Group or a carboxyethyl group. 4. Composition according to one of claims 1 to 3, characterized in that as Verbindun conditions with the formula I one of the compounds mentioned in Table 1 is used, wherein the substituents not defined in the table represent hydrogen. 5. Composition according to one of claims 1 to 4, characterized in that it color enhancers ker selected from the group consisting of piperidine, piperidine-2-carboxylic acid, Piperidine-3-carboxylic acid, piperidine-4-carboxylic acid, pyridine, 2-hydroxypyridine, 3-Hy droxypyridine, 4-hydroxypyridine, imidazole, 1-methylimidazole, histidine, pyrrolidine, Proline, pyrrolidone, pyrrolidone-5-carboxylic acid, pyrazole, 1,2,4-triazole, piperazidine or containing any mixtures thereof. 6. Composition according to one of claims 1 to 5, characterized in that it direktzie The following dyes from the group of Nitrophenylendiamine, Nitroaminophenole, An thraquinones or indophenols, preferably in an amount of from 0.01 to 20% by weight, based on the total colorant contains. 7. Composition according to one of claims 1 to 6, characterized in that ammonium or metal salts selected from the group of formates, carbonates, halides, Sul fate, butyrates, valerates, capronates, acetates, lactates, glycolates, tartrates, citrates, glu conates, propionates, phosphates and phosphonates of alkali metals, such as potassium, Na trium or lithium, alkaline earth metals such as magnesium, calcium, strontium or Ba or aluminum, manganese, iron, cobalt, copper or zinc the. 8. Composition according to one of claims 1 to 7, characterized in that it contains oxidizing agent, in particular H ₂ O ₂ , in an amount of 0.01 to 6 wt .-%, based on the appli cation solution. 9. Composition according to one of claims 1 to 8, characterized in that it anionic, contains zwitterionic or nonionic surfactants. 10. Use of compounds of the formula I as a coloring component in Agents for dyeing keratinous fibers. 11. A method for dyeing keratin-containing fibers, in particular human hair, wherein a colorant containing at least one compound of the formula I and usual cosmetic ingredients, applied to the keratin fibers, some  Time, usually about 30 minutes, left on the fiber and then again rinsed or washed out with a shampoo.