AU1029599A - Application of halogenated triphenylmethane sulfonates for dying fibers containing keratin - Google Patents

Abstract

The invention relates to the application of halogenated triphenylmethane sulfonates of formula (I), wherein R<1>, R<2>, R<3> and R<4>, independent of one another, represent a hydrogen atom, a chlorine atom, a bromine atom or a hydroxyl group. R<5>, R<6>, R<7> and R<8> independent of one another, represent a hydrogen atom, a chlorine atom or a bromine atom. X represents a hydrogen atom, alkali atom, alkaline-earth atom or an ammonium group. The inventive halogenated triphenylmethane sulfonates are used for dying fibers containing keratin, especially human hair.

Description

1 Application of Halogenated Triphenylmethane Sulfonates for Dying Fibres Containing Keratin This invention relates to the use of halogenated triphenylmethane sulfonates for colouring keratin-containing fibres, more particularly human hair, to a composition containing triphenylmethane 5 sulfonates for colouring keratin-containing fibres and to a process for colouring keratin-containing fibres. In general, keratin-containing fibres, for example hair, wool or pelts, are dyed either with substantive dyes or with oxidation dyes which are formed by oxidative coupling of one or more primary intermediates with one another or with one or more secondary intermediates. Primary and 10 secondary intermediates are also known as oxidation dye precursors. The substantive dyes form the colour on the fibre itself by virtue of their own colouring. The colour on the fibre gradually fades or is washed out during washing. Compared with oxidation dyes, colour intensity and fastness are poorer. Although intensive colours with good fastness properties can be obtained with oxidation dyes, 15 the colour is generally developed under the influence of oxidising agents, such as H202 for example, which in some cases can result in damage to the fibres, In addition, some oxidation dye precursors or certain mixtures of oxidation dye precursors can occasionally have a sensitising effect in people with sensitive skin. Substantive dyes are applied under more moderate conditions. They are often used in 20 combination with oxidation dyes to obtain certain shades of colour. The problem addressed by the present invention was to provide colorants for keratin fibres, more especially human hair, which could be used as substantive colorants and which would be at least equivalent in quality to conventional oxidation hair colorants in regard to depth of colour, grey coverage and fastness properties. Another problem addressed by the invention was to provide 25 colorants with which a wide range of colour tones could be obtained without any staining of the skin. In addition, the colorants according to the invention would have very little, if any, sensitising potential. It has now surprisingly been found that certain halogenated triphenylmethane sulfonates are eminently suitable for colouring keratin-containing fibres. These compounds may be applied in organic, aqueous or organic-aqueous preparations and give colours with excellent brilliance and depth 30 of colour and lead to a wide variety of colour tones. The use of oxidising agents is not necessary but, in principle, is not ruled out either. Accordingly, the present invention relates to the use of halogenated triphenylmethane sulfonates corresponding to formula I: Br Br HO 0 R1 Fe R 2 R4 0OeXe R6 V R8O R R

R(I

2 in which R 1 , R 2 , R 3 and R 4 independently of one another represent a hydrogen atom, a chlorine atom, a bromine atom or a hydroxy group, R 5 , R 6 , R 7 and R 8 independently of one another represent a hydrogen atom, a chlorine atom or a bromine atom and X is a hydrogen, alkali metal or alkaline earth atom or an ammonium group, for colouring keratin-containing fibres, more particularly human hair. 5 The present invention also relates to a composition for colouring keratin-containing fibres, more particularly human hair, characterised in that it contains halogenated triphenylmethane sulfonates corresponding to formula I: Br Br HO 0 O 0 Rs S.R O . X RT in which R 1 , R 2 , R 3 and R 4 independently of one another represent a hydrogen atom, a chlorine atom, 10 a bromine atom or a hydroxy group, R 5 , R 6 , R 7 and R 8 independently of one another represent a hydrogen atom, a chlorine atom or a bromine atom and X is a hydrogen, alkali metal or alkaline earth atom or an ammonium group In the context of the invention, keratin-containing fibres are understood to include wool, pelts, feathers and, in particular, human hair. In principle, however, the colorants according to the invention 15 may also be used to colour other natural fibres such as, for example, cotton, jute, sisal, linen or silk, modified natural fibres such as, for example, regenerated cellulose, nitro, alkyl or hydroxyalkyl or acetyl cellulose and synthetic fibres such as, for example, polyamide, polyacrylonitrile, polyurethane and polyester fibres. Suitable compounds corresponding to formula I are bromopyrogallol red, bromophenol blue, 20 tetraphenol blue, bromophenol red, bromothymol blue, bromocresol green and bromocresol purple. The compounds corresponding to formula I are present in the colorant according to the invention in a quantity of preferably 0.03 to 65mmol and more preferably I to 40mmol, based on 1Og of the colorant as a whole. The variety of shades and the colour fastness of the compounds of formula I used in 25 accordance with the invention can be increased by combining these compounds with other substantive dyes and even oxidation hair dyes. In all colorants, several different colouring substances may also be used together. Several different components from the groups of compounds containing a primary or secondary amino group, nitrogen-containing heterocycles, aromatic hydroxy compounds or amino acids may also be used 30 together, as described for example in German patent application 197 17 224.5. The colorants according to the invention give a broad range of colour tones in the yellow, red, blue, blue-green and green range. Their fastness properties are excellent and their sensitising potentials very low.

3 In one preferred embodiment, the colorants according to the invention contain typical substantive dyes, for example from the group of nitrophenylenediamines, nitroaminophenols, anthraquinones, indophenols or the compounds known by the name of Arianore, in addition to the compounds present in accordance with the invention in order further to modify the colour tones. 5 Examples of substantive dyes are the compounds known under the International names or commercial names of 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 and picramic acid, 2-amino-6-chloro-4-nitrophenol, 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 6 10 nitro-1,2,3,4-tetrahydroquinoxaline, 4-N-ethyl-1,4-bis-(2'-hydroxyethylamino)-2-nitrobenzene hydrochloride and 1-methyl-3-nitro-4-(2'-hydroxyethyl)-aminobenzene. The compositions according to the invention in this embodiment contain the substantive dyes in a quantity of, preferably, 0.01 to 20wt%, based on the colorant as a whole. In addition, the compositions according to the invention may also contain naturally occurring 15 dyes such as, for example, henna red, henna neutral, henna black, camomile blossom, sandalwood, black tea, black alder bark, sage, logwood, madder root, catechu, sedre and alkanet. With regard to other typical dye components and the individual dyes components suitable for use in accordance with the invention, reference is specifically made to the series "Dermatology" (Editors: Ch. Culnan and H. Maibach) published by Marcel Dekker Inc., New York/Basel, 1986, Vol. 7, 20 Ch. Zviak's work The Science of Hair Care, Chapter 7, pages 248-250 (substantive dyes) and Chapter 8, pages 264-267 (oxidation dyes), and to the "Europsische Inventar der Kosmetik-Rohstoffe", 1996, published by the European Commission and available in diskette form from the Bundesverband Deutscher Industrie- und Handelsuntemehmen fbr Arzneimittel, Reformwaren und K6rperpflegemittel e.V., Mannheim, Germany. 25 The other substantive dyes optionally present and the oxidation dye precursors optionally present do not have to be single compounds. Instead, the hair colorants according to the invention due to the processes used for producing the individual dyes may contain small quantities of other components providing they do not adversely affect the colouring result or have to be ruled out for other reasons, for example toxicological reasons. 30 The colorants according to the invention produce intensive colours even at physiologically compatible temperatures of <450C. Accordingly, they are particularly suitable for colouring human hair. For application to human hair, the colorants are normally incorporated in a water-containing cosmetic carrier. Suitable water-containing cosmetic carriers are, for example, creams, emulsions, gels or even surfactant-containing foaming solutions, for example shampoos or other formulations 35 suitable for application to the keratin-containing fibres. If necessary, the colorants may even be incorporated in water-free carriers. The colorants according to the invention may also contain any of the known active substances, additives and auxiliaries typical of such formulations. In many cases, the colorants contain at least one surfactant, both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants being 4 suitable in principle. In many cases, however, it has been found to be of advantage to select the surfactants from anionic, zwitterionic or nonionic surfactants. Suitable anionic surfactants for the compositions according to the invention are any anionic surface-active substances suitable for use on the human body. Such substances are characterised 5 by a water-solubilising anionic group such as, for example, a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group containing around 10 to 22 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether, amide groups and hydroxy groups may also be present in the molecule. The following are examples of suitable anionic surfactants - in the form of the sodium, potassium and ammonium salts and the mono-, di- and trialkanolammonium salts containing 10 2 or 3 carbon atoms in the alkanol group: - linear fatty acids containing 10 to 22 carbon atoms (soaps), - ether carboxylic acids corresponding to the formula R-O-(CH 2

-CH

2 O)x-CH2-COOH, in which R is a linear alkyl group containing 10 to 22 carbon atoms and x = 0 or 1 to 16, - acyl sarcosides containing 10 to 18 carbon atoms in the acyl group, 15 - acyl taurides containing 10 to 18 carbon atoms in the acyl group, - acyl isethionates containing 10 to 18 carbon atoms in the acyl group, - sulfosuccinic acid mono- and dialkyl esters containing 8 to 18 carbon atoms in the alkyl group and sulfosuccinic acid monoalkyl polyoxyethyl esters containing 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups, 20 - linear alkane sulfonates containing 12 to 18 carbon atoms, - linear a-olefin sulfonates containing 12 to 18 carbon atoms, - a-sulfofatty acid methyl esters of fatty acids containing 12 to 18 carbon atoms, - alkyl sulfates and alkyl polyglycol ether sulfates corresponding to the formula R-O(CH 2

-CH

2 0)r S0 3 H, in which R is a preferably linear alkyl group containing 10 to 18 carbon atoms and x = 0 or 25 1 to 12, - mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030, - sulfated hydroxyalkyl polyethylene and/or hydroxyalkylene propylene glycol ethers according to DE-A-37 23 354, - sulfonates of unsaturated fatty acids containing 12 to 24 carbon atoms and 1 to 6 double bonds 30 according to DE-A-39 26 344, - esters of tartaric acid and citric acid with alcohols in the form of addition products of around 2 to 15 molecules of ethylene oxide and/or propylene oxide with fatty alcohols containing 8 to 22 carbon atoms. Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether 35 carboxylic acids containing 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, more particularly, unsaturated C8-22 carboxylic acids, such as oleic acid, stearic acid, isostearic acid and palmitic acid. In the context of the invention, zwitterionic surfactants are surface-active compounds which contain at least one quaternary ammonium group and at least one -COOH or -SO 3 ) group in the 40 molecule. Particularly suitable zwitterionic surfactants are the so-called betaines, such as N-alkyl- 5 N,N-dimethyl ammonium glycinates, for example coconutalkyl dimethyl ammonium glycinate, N acylaminopropyl-N,N-dimethyl ammonium glycinates, for example coconutacylaminopropyl dimethyl ammonium glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethyl imidazolines containing 8 to 18 carbon atoms in the alkyl or acyl group and coconutacylaminoethyl hydroxyethyl carboxymethyl 5 glycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known by the CTFA name of Cocamidopropyl Betaine. Ampholytic surfactants are surface-active compounds which, in addition to a Ca-1a 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 which are capable of forming inner salts. Examples of suitable ampholytic surfactants are N-alkyl 10 glycines, N-alkyl propionic acids, N-alkyl aminobutyric acids, N-alkyl iminodipropionic acids, N hydroxyethyl-N-alkyl amidopropyl glycines, N-alkyl taurines, N-alkyl sarcosines, 2-alkyl aminopropionic acids and alkyl aminoacetic acids containing around 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-coconutalkyl aminopropionate, coconutacyl aminoethyl aminopropionate and C12-18 acyl sarcosine. 15 Nonionic surfactants contain, for example, a polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether groups as the hydrophilic group. Examples of such compounds are - products of the addition of 2 to 30mol of ethylene oxide and/or 0 to 5mol of propylene oxide onto linear fatty alcohols containing 8 to 22 carbon atoms, onto fatty acids containing 12 to 22 carbon 20 atoms and onto alkylphenols containing 8 to 15 carbon atoms in the alkyl group, - C12-22 fatty acid monoesters and diesters of products of the addition of 1 to 30mol of ethylene oxide onto glycerol, - C_22 alkyl mono- and oligoglycosides and ethoxylated analogues thereof, - products of the addition of 5 to 60mol of ethylene oxide onto castor oil and hydrogenated castor 25 oil, - products of the addition of ethylene oxide onto sorbitan fatty acid esters, - products of the addition of ethylene oxide onto fatty acid alkanolamides. Examples of cationic surfactants suitable for use in the hair treatment formulations according to the invention are, in particular, quaternary ammonium compounds. Preferred quaternary ammonium 30 compounds are ammonium halides, such as alkyl trimethyl ammonium chlorides, dialkyl dimethyl ammonium chlorides and trialkyl methyl ammonium chlorides, for example cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, lauryl dimethyl ammonium chloride, lauryl dimethyl benzyl ammonium chloride and tricetyl methyl ammonium chloride. Other cationic surfactants suitable for use in accordance with the invention are the 35 quaternised protein hydrolysates. Also suitable for use in accordance with the invention are cationic silicone oils such as, for example, the commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilised trimethyl silyl amodimethicone), Dow Corning 929 Emulsion (containing a hydroxyamino-modified silicone which is also known as amodimethicone), SM-2059 (manufacturer: General Electric), SLM- 6 55067 (manufacturer: Wacker) and Abil@-Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethyl siloxanes, quaternium-80). Alkyl amidoamines, particularly fatty acid amidoamines, such as the stearyl amidopropyl dimethyl amine obtainable as Tego Amid@S 18, are distinguished not only by their favourable 5 conditioning effect, but also and in particular by their ready biodegradability. Quaternary ester compounds, so-called "esterquats", such as the methyl hydroxyalkyl dialkoyloxyalkyl ammonium methosulfates marketed under the trade name of Stepantex@, are also readily biodegradable. One example of a quaternary sugar derivative suitable for use as a cationic surfactant is the 10 commercially available product Glucquat@100 (CTFA name: Lauryl Methyl Gluceth-10 Hydroxypropyl Dimonium Chloride). The compounds containing alkyl groups used as surfactants may be single compounds. In general, however, these compounds are produced from native vegetable or animal raw materials so that mixtures with different alkyl chain lengths dependent upon the particular raw material are 15 obtained. The surfactants representing addition products of ethylene and/or propylene oxide with fatty alcohols or derivatives of these addition products may be both products with a "normal" homologue distribution and products with a narrow homologue distribution. Products with a "normal" homologue distribution are mixtures of homologues which are obtained in the reaction of fatty alcohol and 20 alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates as catalysts. By contrast, narrow homologue distributions are obtained when, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates are used as catalysts. The use of products with a narrow homologue distribution can be of advantage. Other active substances, auxiliaries and additives are, for example, 25 - nonionic polymers such as, for example, vinyl pyrrolidone/vinyl acrylate copolymers, polyvinyl pyrrolidone and vinyl pyrrolidone/vinyl acetate copolymers and polysiloxanes, - cationic polymers, such as quaternised cellulose ethers, polysiloxanes containing quaternary groups, dimethyl diallyl ammonium chloride polymers, acrylamide/dimethyl diallyl ammonium chloride copolymers, dimethyl aminoethyl methacrylate/vinyl pyrrolidone copolymers quaternised 30 with diethyl sulfate, vinyl pyrrolidone/imidazolinium methochloride copolymers and quaternised polyvinyl alcohol, - zwitterionic and amphoteric polymers such as, for example, acrylamidopropyl/trimethyl ammonium chloride/acrylate copolymers and octyl acrylamide/methyl methacrylate/tert.butyl aminoethyl methacrylate/2-hydroxypropyl methacrylate copolymers, 35 - 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/ isobomyl acrylate copolymers, methyl vinyl ether/maleic anhydride copolymers and acrylic acid/ethyl acrylate/N-tert.butyl acrylamide terpolymers, - thickeners, such as agar agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust 40 bean gum, linseed gums, dextrans, cellulose derivatives, for example methyl cellulose, 7 hydroxyalkyl cellulose and carboxymethyl cellulose, starch fractions and derivatives, such as amylose, amylopectin and dextrins, clays such as, for example, bentonite or fully synthetic hydrocolloids such as, for example, polyvinyl alcohol, - structurants, such as glucose and maleic acid, 5 - hair-conditioning compounds, such as phospholipids, for example soy lecithin, egg lecithin and kephalins, and also silicone oils, - protein hydrolysates, more particularly elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolysates, condensation products thereof with fatty acids and quaternised protein hydrolysates, 10 - perfume oils, dimethyl isosorbide and cyclodextrins, - solubilisers, such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol, - antidandruff agents, such as Piroctone Olamine and Zinc Omadine, " other substances for adjusting the pH value, 15 - active substances, such as panthenol, pantothenic acid, allantoin, pyrrolidone carboxylic acids and salts thereof, plant extracts and vitamins, - cholesterol, - UV filters, - consistency factors, such as sugar esters, polyol esters or polyol alkyl ethers, 20 - fats and waxes, such as spermaceti, 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 agents, such as glycerol, propylene glycol monoethyl ether, carbonates, 25 hydrogen carbonates, guanidines, ureas and primary, secondary and tertiary phosphates, imidazoles, tannins, pyrrole, - opacifiers, such as latex, - pearlisers, such as ethylene glycol mono- and distearate, - propellents, such as propane/butane mixtures, N 2 0, dimethyl ether, C02 and air and 30 - antioxidants. To produce the colorants according to the invention, the constituents of the water-containing carrier are used in the usual quantities for this purpose. For example, emulsifiers are used in concentrations of 0.5 to 30wt% while thickeners are used in concentrations of 0.1 to 25wt%, based on the colorant as a whole. 35 It can be of advantage to the colouring result to add ammonium or metal salts to the colorants. Suitable metal salts are, for example, formates, carbonates, halides, sulfates, butyrates, valerates, caproates, 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 aluminium, manganese, iron, cobalt, copper or zinc, 40 sodium acetate, lithium bromide, calcium bromide, calcium gluconate, zinc chloride, zinc sulfate, 8 magnesium chloride, magnesium sulfate, ammonium carbonate, chloride and acetate being preferred. These salts are preferably present in a quantity of 0.03 to 65mmol and more preferably in a quantity of 1 to 40mmol, based on 100g of the colorant as a whole. The pH of the ready-to-use colouring compositions is normally in the range from 2 to 11 and 5 preferably in the range from 5 to 9. In order to colour the keratin-containing fibres, more especially human hair, the colorants are generally applied to the hair in the form of the water-containing cosmetic carrier in a quantity of 100 g, left thereon for about 30 minutes and then rinsed out or washed out with a commercially available shampoo. 10 Examples Preparation of a colouring cream To prepare a colouring cream, 1.0g of cetearyl alcohol, 1.Og of coconut alcohol, 1.1g of sodium laureth-5-carboxylate, 0.05g of propyl paraben and 0.15g of methyl paraben were melted at 80*C, mixed with 70g of water heated to 80 0 C and emulsified with vigorous stirring. The emulsion was then 15 left to cool with gentle stirring. The colorant was dissolved in 10g of water at 500C with addition of 3.Og of ammonium sulfate and ammonia. The dye solution was added to the emulsion, adjusted to pH9 with ammonia and made up with water to 100g. The cream was then cooled while stirring to room temperature. The colouring cream obtained was then applied to a blond hair tress for 30 minutes at 30*C. 20 The coloured tress was then rinsed for 30s with luke-warm water, dried in a stream of warm air (30 400C) and then combed. The colours were visually evaluated in daylight. The particular shades and depths of colour are shown in the following Tables. The depth of colour was evaluated on the following scale: very faint, if any, colour 25 (+) : weak intensity + : medium intensity +(+) :medium to strong intensity ++ : strong intensity ++(+) :strong to very strong intensity 30 +++ : very strong intensity Table I Colorant Concentration c [wt%] Colour Intensity 3,3-Tetrabromo-m-cresol sulfonphthalein (bromocresol green) 1 Grey-turquoise ++(+) 5,5'-dibromo-o-cresol sulfonphthalein (bromocresol purple) 1 Flat green ++ Bromopyrogallol red 0.75 Bluebell-violet ++ Tetrabromophenol blue 0.18 Blue-green ++(+) |Bromophenol blue 0.5 Grey-blue +++ |Bromothymol blue, sodium salt 0.5 Yellow-brown 1+

Claims (6)

1. The use of halogenated triphenylmethane sulfonates corresponding to formula I: Br Br HO 0 O RR 2 R in which R 1 , R 2 , R 3 and R 4 independently of one another represent a hydrogen atom, a chlorine atom, 5 a bromine atom or a hydroxy group, R5, R 6 , R 7 and R 8 independently of one another represent a hydrogen atom, a chlorine atom or a bromine atom and X is a hydrogen, alkali metal or alkaline earth atom or an ammonium group, for colouring keratin-containing fibres, more particularly human hair.

2. A composition for colouring keratin-containing fibres, more particularly human hair, containing as a colouring component halogenated triphenylmethane sulfonates corresponding to 10 formula I: Br Br HO 0 O R- R 4 R R R 3 0R 5W W eex0 R 5 S 7 in which R1, R 2 , R 3 and R 4 independently of one another represent a hydrogen atom, a chlorine atom, a bromine atom or a hydroxy group, R5, R 6 , R 7 and R 8 independently of one another represent a hydrogen atom, a chlorine atom or a bromine atom and X is a hydrogen, alkali metal or alkaline earth 15 atom or an ammonium group.

3. A composition as claimed in claim 2, characterised in that the compounds corresponding to formula I are selected from bromopyrogallol red, bromophenol blue, tetraphenol blue, bromophenol red and bromothymol blue.

4. A composition as claimed in claim 2 or 3, characterised in that the compounds of formula 20 I are present in a quantity of 0.03 to 65mmol and more particularly 1 to 40mmol, based on 1 0Og of the colorant as a whole.

5. A composition as claimed in any of claims 2 to 4, characterised in that anionic, zwitterionic and/or nonionic surfactants are used.

6. A process for colouring keratin-containing fibres in which a colorant containing 25 halogenated triphenylmethane sulfonates corresponding to formula I: 10 Br Br HO 0 R 1 R4 R 5 R 2 R 3 0 R 6 R R(I in which R1, R 2 , R 3 and R 4 independently of one another represent a hydrogen atom, a chlorine atom, a bromine atom or a hydroxy group, R 5 , R 6 , R 7 and R8 independently of one another represent a hydrogen atom, a chlorine atom or a bromine atom and X is a hydrogen, alkali metal or alkaline earth 5 atom or an ammonium group and typical cosmetic ingredients is applied to the keratin-containing fibres, left thereon for a time, usually about 30 minutes, and then rinsed out again or washed out with a shampoo.