AU2097700A - Agent for dying keratin fibers - Google Patents

Abstract

The invention relates to an agent for dying keratin fibers, especially human hair. The inventive agent contains a naphthyl-azo compound with formula (I), in which R<1> represents hydrogen, halogen, hydroxy, nitro, a C1-C4-alkyl group, a C1-C4-alkoxy group, sulfo group or carboxy group; R<2> represents a 1- or 2-naphthyl group which comprises at least one hydroxy group and, as additional substituents, can comprise hydroxy groups, sulfo groups, carboxy groups, nitro groups or halogen atoms, or represents a 1-aryl-5-hydroxy-4-pyrazolyl radical which can be substituted in position 3 by a C1-C4-group; M represents hydrogen, an alkali metal or 1/2 alkaline earth metal, 1/3 Al(III), 1/2 Zn(II), 1/4 Ti(IV), 1/4 Zr(IV), 1/3 Cr(III), 1/2 Co(II), 1/2 Fe(II), 1/3 Mo(III) or 1/6 Mo(VI), 1/3 W(III) or 1/6 W(VI) or ammonium.

Description

WO 00/38637 1 PCT/EP99/09999 Agent for Dying Keratin Fibers This invention relates to a composition containing certain naphthylazo compounds for coloring keratin-containing fibers, more particularly human hair, to the use of these compounds as a coloring component in hair coloring compositions and to a process for coloring 5 keratin-containing fibers, more particularly human hair. In general, keratin-containing fibers, 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 primary intermediates normally used are primary aromatic amines containing another free or substituted hydroxy or amino group in the para or ortho position, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazolone derivatives and 2,4,5,6-tetraamino 15 pyrimidine and derivatives thereof. Special representatives are, for example, p-phenylenediamine, p toluylenediamine, 2,4,5,6-tetraaminopyrimidine, p-aminophenol, N,N-bis-(2 hydroxyethyl)-p-phenylenediamine, 2-(2,5-diaminophenyl)-ethanol, 2-(2,5 diaminophenoxy)-ethanol, 1 -phenyl-3-carboxyamido-4-amino-5-pyrazolone, 20 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. The secondary intermediates used are generally m-phenylene diamine derivatives, naphthols, resorcinol and resorcinol derivatives, 25 pyrazolones, m-aminophenols and substituted pyridine derivatives. Particularly suitable secondary intermediates are a-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, WO 00/38637 2 PCT/EP99/09999 resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 2,4 diaminophenoxyethanol, 2 -amino-4-(2-hydroxyethylamino)-anisole (Lehmanns Blue), 1 -phenyl-3-methyl-5-pyrazolone, 2,4-dichloro-3 aminophenol, 1, 3 -bis-(2,4-diaminophenoxy)-propane, 2-chlororesorcinol, 4 5 chlororesorcinol, 2 -chloro-6-methyl-3-aminophenol, 2-methyl resorcinol, 5 methyl resorcinol, 3 -amin-6-methoxy-2-methylaminopyridine and 3,5 diamino-2,6-dimethoxypyridine. With regard to other typical dye components, reference is specifically made to the series entitled "Dermatology" (Editors: Ch. Culnan 10 and H. Maibach), Marcel Dekker Inc., New York/Basel, 1986, Vol. 7, Ch. Zviak, The Science of Hair Care, Chapter 7 (pages 248-250; Substantive Dyes) and Chapter 8 (pages 264-267; Oxidation Dye Precursors) and to the "Europaische Inventar der Kosmetik-Rohstoffe" published by the European Commission and available on disc from the Bundesverband 15 Deutscher Industrie- und Handelsunternehmen fOr Arzneimittel, Reformwaren und K6rperpflegemittel e.V., Mannheim, Germany. Although intensive colors with good fastness properties can be obtained with oxidation dyes, the color is generally developed under the influence of oxidizing agents, such as H 2 0 2 for example, which in some 20 cases can result in damage to the fibers. In addition, some oxidation dye precursors or certain mixtures of oxidation dye precursors can occasionally have a sensitizing effect in people with sensitive skin. Although substantive dyes are applied under more moderate conditions, their disadvantage is that, in many cases, the colors obtained often have inadequate fastness 25 properties. The use of the combination of 2-hydroxy-4-sulfo-1-naphthylazo compounds with special metal salts of the 2nd or 3rd main group of the periodic system and/or salts of the transition metals, as described in more detail hereinafter, for coloring keratin-containing fibers was hitherto 30 unknown.

WO 00/38637 3 PCT/EP99/09999 The problem addressed by the present invention was to provide colorants for keratin fibers, more especially human hair, which would be at least equivalent in quality to conventional oxidation hair dyes in regard to depth of color, grey coverage and fastness properties, but which would not 5 necessarily have to contain oxidizing agents, such as H 2 0 2 for example. In addition, the colorants according to the invention would have very little, if any, sensitizing potential. It has surprisingly been found that the 2-hydroxy-4-sulfo-1 naphthylazo compounds corresponding to formula (I) below, both on their 10 own and in combination with certain metal salts, are eminently suitable for coloring keratin-containing fibers, even in the absence of oxidizing agents. They give colors with excellent brilliance and depth of color and lead to a wide variety of shades. In principle, however, oxidizing agents may be present. 15 The present invention relates to a composition for coloring keratin containing fibers, more particularly human hair, containing naphthylazo compounds corresponding to formula (1): R2 N R1OH 0~-. =O M + 20 in which

R

1 is hydrogen, halogen, hydroxy, nitro, a C1.4 alkyl group, a C1.4 alkoxy group, sulfo group or carboxy group,

R

2 is a 1- or 2-naphthyl group which bears at least one hydroxy group and 25 may carry hydroxy, sulfo, carboxy, nitro groups or halogen atoms as further substituents or a 1-aryl-5-hydroxy-4-pyrazolyl group which may be WO 00/38637 4 PCT/EP99/09999 substituted in the 3-position by a C14 group, M is hydrogen, an alkali metal or 1/2 alkaline earth metal, 1/3 A(Il), 1/2 Zn(II), 1/4 Ti(IV), 1/4 Zr(IV), 1/3 Cr(Ill), 1/2 Co(II), 1/2 Fe(ll), 1/3 Mo(lll) or 1/6 Mo(VI), 1/3 W(lll) or 1/6 W(VI) or ammonium. 5 In the context of the invention, keratin-containing fibers are understood to include wool, pelts, feathers and, in particular, human hair. In principle, however, the colorants according to the invention may also be used to color other natural fibers such as, for example, cotton, jute, sisal, linen or silk, modified natural fibers such as, for example, regenerated 10 cellulose, nitro, alkyl or hydroxyalkyl or acetyl cellulose and synthetic fibers such as, for example, polyamide, polyacrylonitrile, polyurethane and polyester fibers. The compounds corresponding to formula I are preferably selected from the group of following azo compounds: Eriochromblauschwarz R, 15 Eriochromschwarz A, Eriochromschwarz T, Hydroxynaphtholblau, Acid Blue 158, Eriochromrot B, Eriochromrot R and Acid Red 186. These compounds are known from the literature or are commercially obtainable. The above-mentioned azo compounds corresponding to formula 1 20 are used in the compositions according to the invention in quantities of normally 0.03 to 65 mmol and preferably 1 to 40 mmol, based on 100 g of the colorant as a whole. They may be used as substantive colorants or in the presence of other components. 25 Colorants which contain the azo compound corresponding to formula I on its own are preferably used for colors in the red, red-violet, blue-violet and red-brown range. The range of shades can be extended and intensity can be improved if the azo compounds corresponding to formula I are used in 30 combination with metal salts of the 2nd and 3rd main group of the periodic WO 00/38637 5 PCT/EP99/09999 system and/or salts of the transition metals. In this embodiment, the compounds corresponding to formula I and the metal salts are preferably used in a molar ratio of 0.5:1 to 2:1. The metal salts preferably used are preferably selected from the 5 chlorides, sulfates, acetates, lactates and nitrates of Ca, Mg, AI(lll), Zn(II), Ti(IV), Zr(IV), Cr(Ill), Co(II), Fe(II), Mo(Ill,VI), W(Ill, VI). Oxidizing agents, for example H 2 0 2 , need not present. However, it may be desirable in some cases to add hydrogen peroxide or other oxidizing agents to the compositions according to the invention to obtain 10 shades which are lighter than the keratin-containing fibers to be colored. Oxidizing agents are generally used in a quantity of 0.01 to 6% by weight, based on the solution applied. A preferred oxidizing agent for human hair is H 2 0 2 . In one preferred embodiment, the colorants according to the 15 invention also contain typical oxidation dye precursors, more particularly selected from the compounds mentioned above, and/or substantive dyes, for example from the group of nitrophenylenediamines, nitroaminophenols, anthraquinones or indophenols, in addition to the compounds present in accordance with the invention in order further to modify the color tones. 20 Examples of suitable 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 25 Basic Brown 17 and also picramic acid, 2-amino-6-chloro-4-nitrophenol, 4 amino-2-nitrodiphenylamine-2'-carboxylic acid, 6-nitro-1,2,3,4-tetrahydro quinoxaline, 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 30 substantive dyes in a quantity of, preferably, 0.01 to 20% by weight, based WO 00/38637 6 PCT/EP99/09999 on the colorant as a whole. The preparations according to the invention may also contain naturally occurring dyes such as, for example, henna red, henna neutral, henna black, camomile blossom, sandalwood, black tea, black alder bark, 5 sage, logwood, madder root, catechu, sedre and alkanet. The components used 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 coloring result 10 or have to be ruled out for other reasons, for example toxicological reasons. The colorants according to the invention produce intensive colors even at physiologically compatible temperatures of <450C. Accordingly, they are particularly suitable for coloring human hair. For application to 15 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 preparations suitable for application to the keratin-containing fibers. If necessary, the colorants may 20 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 preparations. In many cases, the colorants contain at least one surfactant, both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants 25 being 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 30 human body. Such substances are characterized by a water-solubilizing WO 00/38637 7 PCT/EP99/09999 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 hydroxyl groups may also be present in the molecule. 5 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 2 or 3 carbon atoms in the alkanol group: - linear fatty acids containing 10 to 22 carbon atoms (soaps), 10 - ether carboxylic acids corresponding to the formula R-O-(CH 2 -CH20)x

CH

2 -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, - acyl taurides containing 10 to 18 carbon atoms in the acyl group, 15 - 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 x-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 25 formula R-O(CH 2

-CH

2 0)x-SO3H, in which R is a preferably linear alkyl group containing 10 to 18 carbon atoms and x = 0 or 1 to 12, - mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030, - sulfated hydroxyalkyl polyethylene and/or hydroxyalkylene propylene 30 glycol ethers according to DE-A-37 23 354, WO 00/38637 8 PCT/EP99/09999 - sulfonates of unsaturated fatty acids containing 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 in the form of addition products of around 2 to 15 molecules of ethylene oxide and/or 5 propylene oxide with fatty alcohols containing 8 to 22 carbon atoms. Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether 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

C

8

-

2 2 10 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 -COO(- or -SO 3 (- group in the molecule. Particularly 15 suitable zwitterionic surfactants are the so-called betaines, such as N-alkyl N,N-dimethyl ammonium glycinates, for example cocoalkyl dimethyl am monium glycinate, N-acylaminopropyl-N,N-dimethyl ammonium glycinates, for example cocoacylaminopropyl dimethyl ammonium glycinate, and 2 alkyl-3-carboxymethyl-3-hydroxyethy imidazolines containing 8 to 18 car 20 bon atoms in the alkyl or acyl group and cocoacylaminoethyl hydroxyethyl carboxymethyl 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 C 8

-

18 alkyl or acyl group, contain at least one free amino group 25 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 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 30 aminoacetic acids containing around 8 to 18 carbon atoms in the alkyl WO 00/38637 9 PCT/EP99/09999 group. Particularly preferred ampholytic surfactants are N-cocoalkyl amino propionate, cocoacyl aminoethyl aminopropionate and C12-18 acyl sarcosine. Nonionic surfactants contain, for example, a polyol group, a poly 5 alkylene 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 30 moles of ethylene oxide and/or 0 to 5 moles of propylene oxide onto linear fatty alcohols containing 8 to 22 carbon atoms, onto fatty acids containing 12 to 22 carbon atoms and 10 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 30 moles of ethylene oxide onto glycerol, - C8-22 alkyl mono- and oligoglycosides and ethoxylated analogs thereof, - products of the addition of 5 to 60 moles of ethylene oxide onto castor 15 oil and hydrogenated castor 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 compositions according to the invention are, in particular, 20 quaternary ammonium compounds. Preferred quaternary ammonium 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 25 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 quaternized protein hydrolyzates. Also suitable for use in accordance with the invention are cationic 30 silicone oils such as, for example, the commercially available products Q2- WO 00/38637 10 PCT/EP99/09999 7224 (manufacturer: Dow Corning; a stabilized trimethyl silyl amodimethi cone), Dow Corning 929 Emulsion (containing a hydroxylamino-modified silicone which is also known as amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil@-Quat 5 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 favorable conditioning effect, but also and in 10 particular by their ready biodegradability. Quaternary ester compounds, so-called "esterquats", such as the the methyl hydroxyalkyl dialkoyloxyalkyl ammonium methosulfates marketed under the trade name of Stepantex@, are also readily biodegradable. 15 One example of a quaternary sugar derivative suitable for use as a cationic surfactant is the commercially available product Glucquat@100 (CTFA name: Lauryl Methyl Gluceth-10 Hydroxypropyl Dimonium Chloride). The compounds containing alkyl groups used as surfactants may be 20 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 obtained. The surfactants representing addition products of ethylene and/or 25 propylene oxide with fatty alcohols or derivatives of these addition products may be both products with a "normal" homolog distribution and products with a narrow homolog distribution. Products with a "normal" homolog distribution are mixtures of homologs which are obtained in the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides 30 or alkali metal alcoholates as catalysts. By contrast, narrow homolog WO 00/38637 11 PCT/EP99/09999 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 homolog distribution can be of advantage. 5 Other active substances, auxiliaries and additives are, for example, - 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 quaternized cellulose ethers, polysiloxanes 10 containing quaternary groups, dimethyl diallyl ammonium chloride polymers, acrylamide/dimethyl diallyl ammonium chloride copolymers, dimethyl aminoethyl methacrylate/vinyl pyrrolidone copolymers quater nized with diethyl sulfate, vinyl pyrrolidone/imidazolinium methochloride copolymers and quaternized polyvinyl alcohol, 15 - zwitterionic and amphoteric polymers such as, for example, acrylamido propyl/trimethyl ammonium chloride/acrylate copolymers and octyl acrylamide/methyl methacrylate/tert.butyl aminoethyl methacrylate/2 hydroxypropyl methacrylate copolymers, - anionic polymers such as, for example, polyacrylic acids, crosslinked 20 polyacrylic acids, vinyl acetate/crotonic acid copolymers, vinyl pyrrolidone/vinyl acrylate copolymers, vinyl acetate/butyl maleate/iso bornyl acrylate copolymers, methyl vinyl ether/maleic anhydride co polymers and acrylic acid/ethyl acrylate/N-tert.butyl acrylamide ter polymers, 25 - thickeners, such as agar agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives, for example methyl cellulose, hydroxyalkyl cellulose and carboxymethyl cellulose, starch fractions and derivatives, such as amylose, amylopectin and dextrins, clays such as, for example, 30 bentonite or fully synthetic hydrocolloids such as, for example, polyvinyl WO 00/38637 12 PCT/EP99/09999 alcohol, - structurants, such as glucose and maleic acid, - hair-conditioning compounds, such as phospholipids, for example soya lecithin, egg lecithin and kephalins, and also silicone oils, 5 - protein hydrolyzates, more particularly elastin, collagen, keratin, milk protein, soya protein and wheat protein hydrolyzates, condensation products thereof with fatty acids and quaternized protein hydrolyzates, - perfume oils, dimethyl isosorbide and cyclodextrins, - solubilizers, such as ethanol, isopropanol, ethylene glycol, propylene 10 glycol, glycerol and diethylene glycol, - antidandruff agents, such as Piroctone Olamine and Zinc Omadine, - other substances for adjusting the pH value, - active substances, such as panthenol, pantothenic acid, allantoin, pyrrolidone carboxylic acids and salts thereof, plant extracts and 15 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 25 monoethyl ether, carbonates, hydrogen carbonates, guanidines, ureas and primary, secondary and tertiary phosphates, imidazoles, tannins, pyrrole, - opacifiers, such as latex, - pearlizers, such as ethylene glycol mono- and distearate, 30 - propellents, such as propane/butane mixtures, N 2 0, dimethyl ether, WO 00/38637 13 PCT/EP99/09999

CO

2 and air and - antioxidants. To produce the colorants according to the invention, the constituents of the water-containing carrier are used in the usual quantities for this 5 purpose. For example, emulsifiers are used in concentrations of 0.5 to 30% by weight while thickeners are used in concentrations of 0.1 to 25% by weight, based on the colorant as a whole. It can be of advantage to the coloring result to add ammonium or alkali metal salts to the colorants. Suitable metal salts are, for example, 10 formates, carbonates, halides, sulfates, butyrates, valerates, caproates, acetates, lactates, glycolates, tartrates, citrates, gluconates, propionates, phosphates and phosphonates of NH 4 *, potassium, sodium or lithium, sodium acetate, lithium bromide, ammonium carbonate, chloride and acetate being preferred. These salts are preferably present in a quantity of 15 0.03 to 65 mmol and more preferably in a quantity of 1 to 40 mmol, based on 100 g of the colorant as a whole. The pH value of the ready-to-use coloring preparations is normally in the range from 2 to 11 and preferably in the range from 5 to 9. The present invention also relates to the use of naphthylazo 20 compounds corresponding to formula (1): R2 N OH RI o= =o M + O (I) in which 25 R 1 is hydrogen, halogen, hydroxy, nitro, a C 1

.

4 alkyl group, a C1.4 alkoxy group, sulfo group or carboxy group, WO 00/38637 14 PCT/EP99/09999

R

2 is a 1- or 2-naphthyl group which bears at least one hydroxy group and may carry hydroxy, sulfo, carboxy, nitro groups or halogen atoms as further substituents or a 1-aryl-5-hydroxy-4-pyrazolyl group which may be substituted in the 3-position by a C14 group, 5 M is hydrogen, an alkali metal or 1/2 alkaline earth metal, 1/3 Al(Ill), 1/2 Zn(Il), 1/4 Ti(IV), 1/4 Zr(IV), 1/3 Cr(Ill), 1/2 Co(l), 1/2 Fe(ll), 1/3 Mo(Ill) or 1/6 Mo(VI), 1/3 W(Ill) or 1/6 W(VI) or ammonium. as a coloring component in oxidation hair colorants. The present invention also relates to a process for coloring keratin 10 containing fibers, more particularly human hair, in which a colorant containing naphthylazo compounds corresponding to formula (1): R2 RII NN R1 oH o=- =0 M + 0() 15 in which

R

1 is hydrogen, halogen, hydroxy, nitro, a C14 alkyl group, a C14 alkoxy group, sulfo group or carboxy group,

R

2 is a 1- or 2-naphthyl group which bears at least one hydroxy group and may carry hydroxy, sulfo, carboxy, nitro groups or halogen atoms as further 20 substituents or a 1-aryl-5-hydroxy-4-pyrazolyl group which may be substituted in the 3-position by a C14 group, M is hydrogen, an alkali metal or 1/2 alkaline earth metal, 1/3 Al(Ill), 1/2 Zn(II), 1/4 Ti(IV), 1/4 Zr(IV), 1/3 Cr(lll), 1/2 Co(l), 1/2 Fe(II), 1/3 Mo(Ill) or 1/6 Mo(VI), 1/3 W(lll) or 1/6 W(VI) or ammonium. 25 and typical cosmetic ingredients is applied to the keratin-containing fibers, left thereon for a while, normally for about 30 minutes, and then rinsed out WO 00/38637 15 PCT/EP99/09999 again or washed out with a shampoo. The naphthylazo compounds and the other components may be applied to the hair either simultaneously or successively; in the latter case, it does not matter which of the components is applied first. A period of up 5 to 30 minutes may elapse between application of the individual components. The fibers may even be pretreated with a salt solution. Examples 10 Preparation of a coloring solution: 0.01 molar solutions of the compounds corresponding to formula I were prepared. Sodium acetate and optionally another salt were added in equimolar quantities, followed by the addition of one drop of a 20% fatty alkyl ether sulfate solution. The solution was adjusted to pH 6 with dilute 15 sodium hydroxide solution or hydrochloric acid. A tress of 90% grey, non-pretreated human hair was placed in this coloring solution for 30 minutes at 300C. The tress was then rinsed for 30 seconds with luke-warm water, dried with warm air and then combed out. The particular shades and depths of color are shown in Table 1 20 below. The depth of color was evaluated on the following scale: - : very faint, if any, color (+) :weak intensity + medium intensity 25 +(+) : medium to strong intensity ++ : strong intensity ++(+) :strong to very strong intensity +++ : very strong intensity WO 00/38637 16 PCT/EP99/09999 Table 1. Coloring with Eriochromrot B Metal salt Shade Intensity - Light brown +(+) Aluminium lactate Light brown + Aluminium lactate* Brown-orange ++ Magnesium chloride Light brown + Magnesium chloride* Mid-brown ++ Zinc chloride Light brown +(+) Zinc chloride* Orange-brown ++ * In these cases, the hair tresses were first placed in the 1 % metal salt solution for 10 minutes at 300C and then dabbed with absorbent paper. The tresses were then placed in a solution containing the remaining constituents. Table 2. Coloring with Eriochromblauschwarz R Metal salt Shade Intensity Brown-violet +(+) Aluminium lactate* Violet ++ Aluminium lactate Violet ++ Magnesium chloride* Violet ++ Magnesium chloride Violet-brown ++ Zinc chloride* Violet ++ Zinc chloride Brown-violet ++ Application Examples All quantities are expressed in parts by weight.

WO 00/38637 17 PCT/EP99/09999 1. Coloring cream Hydrenol@ D' 1.0 Lorol@ techn.

2 1.0 5 Akypo@ Soft RLM 45N 3 1.1 p-Hydroxybenzoic acid propyl ester 0.05 p-Hydroxybenzoic acid methyl ester 0.15 Ammonium sulfate 1.0 Eriochromblauschwarz R 0.5 10 Ammonia (25% in water) to pH 9 Water to 100 1 C 16

.

1 8 fatty alcohol (INCI name: Cetearyl Alcohol) (COGNIS) 2 C12-18 fatty alcohol (INCI name: Coconut Alcohol) (COGNIS) 15 3 Lauryl alcohol + 4.5 ethylene oxide acetic acid sodium salt (ca. 82% active substance in water; INCI name: Sodium Laureth-6 Carboxylate) (KAO) After treatment with this coloring cream, blond hair (Kerling) was 20 gray-magenta in color. 2. Coloring cream Hydrenol@ D 1.0 Lorol@ techn. 1.0 25 Akypo@ Soft RLM 45 N 1.1 p-Hydroxybenzoic acid propyl ester 0.05 p-Hydroxybenzoic acid methyl ester 0.15 Ammonium sulfate 1.0 Eriochromblauschwarz R 0.2 30 HC Blue No. 2 0.5 WO 00/38637 18 PCT/EP99/09999 Ammonia (25% in water) to pH 9 Water to 100 After treatment with this coloring cream, blond hair (Kerling) was 5 parmalilac in color. 3. Coloring cream Hydrenol@ D 1.0 Lorol@ techn. 1.0 10 Akypo@ Soft RLM 45 N 1.1 p-Hydroxybenzoic acid propyl ester 0.05 p-Hydroxybenzoic acid methyl ester 0.15 Ammonium sulfate 1.0 Eriochromblauschwarz R 0.15 15 HC Blue No. 2 0.15 HC Red No. 3 0.05 N,N'-bis-(2-hydroxyethyl)-2-nitro-p-phenylene diamine 0.45 Ammonia (25% in water) to pH 9 20 Water to 100 After treatment with this coloring cream, blond hair (Kerling) was dark purple in color. 25 4. Coloring cream Hydrenol@ D 6.0 Lorol@ techn. 2.0 Cremophor@ A25 4 1.1 Ammonium sulfate 1.0 30 Eriochromblauschwarz R 0.15 WO 00/38637 19 PCT/EP99/09999 HC Blue No. 2 0.15 HC Red No. 3 0.05 N,N'-bis-(2-hydroxyethyl)-2-nitro-p-phenylene diamine 0.45 5 Ammonia (25% in water) to pH 7 Water to 100 4 Tallow alcohol + 25 ethylene oxide (INCI name: Ceteareth-25) (BASF) 10 After treatment with this coloring cream, blond hair (Kerling) was gray-violet in color. 5. Coloring cream Stenol@ 16185 8.1 15 Paraffin oil perliqu. 8.1 Foryl@ 1006 0.6 Dehyquart@ A 7 5.0 Eriochromblauschwarz R 0.5 Ammonia (25% in water) to pH9 20 Water to 100 5 C16-18 fatty alcohol (INCI name: Cetearyl Alcohol (COGNIS) 6 C 12

-

18 fatty alcohol + 9 ethylene oxide (INCI name: Laureth-10) (COGNIS) 25 7 Trimethyl hexadecyl ammonium chloride (ca. 25% active substance in water; INCI name: Cetrimonium Chloride) (COGNIS) After treatment with this coloring cream, blond hair (Kerling) was gray-pink in color. 30

Claims (10)

1. A composition for coloring keratin-containing fibers, more particularly human hair, characterized in that it contains as a coloring component at least one naphthylazo compound corresponding to formula 5 (1): R2 RII NON R1 OH q- =0 M + 0() in which 10 R 1 is hydrogen, halogen, hydroxy, nitro, a C14 alkyl group, a C1.4 alkoxy group, sulfo group or carboxy group, R 2 is a 1- or 2-naphthyl group which bears at least one hydroxy group and may carry hydroxy, sulfo, carboxy, nitro groups or halogen atoms as further substituents or a 1-aryl-5-hydroxy-4-pyrazolyl group which may be 15 substituted in the 3-position by a C14 group, M is hydrogen, an alkali metal or 1/2 alkaline earth metal, 1/3 Al(Ill), 1/2 Zn(ll), 1/4 Ti(IV), 1/4 Zr(IV), 1/3 Cr(Ill), 1/2 Co(II), 1/2 Fe(ll), 1/3 Mo(Ill) or 1/6 Mo(VI), 1/3 W(Ill) or 1/6 W(VI) or ammonium.

2. A composition as claimed in claim 1, characterized in that 20 Eriochromblauschwarz R, Eriochromschwarz A, Eriochromschwarz T, Hydroxynaphtholblau, Acid Blue 158, Eriochromrot B, Eriochromrot R and Acid Red 186 or mixtures thereof are used as the compounds of formula 1.

3. A composition as claimed in claim 1 or 2, characterized in that the naphthylazo compounds corresponding to formula I are used in a quantity 25 of 0.03 to 65 mmol and more particularly in a quantity of 1 to 40 mmol, based on 100 g of the colorant as a whole. WO 00/38637 21 PCT/EP99/09999

4. A composition as claimed in any of claims 1 to 3, characterized in that it additionally contains one or more metal salts of the 2nd or 3rd main group of the periodic system and/or one or more salts of transition metals.

5. A composition as claimed in claim 4, characterized in that the metal 5 salts are selected from the group of chlorides, sulfates, acetates, lactates and nitrates of Ca, Mg, Al(Ill), Zn(ll), Ti(IV), Zr(IV), Cr(lll), Co(ll), Fe(ll), Mo(IlIlVI), W(Ill, VI).

6. A composition as claimed in any of claims 1 to 7, characterized in that it additionally contains oxidation dye precursors and/or substantive 10 dyes from the group of nitrophenylenediamines, nitroaminophenols, anthraquinones or indophenols, preferably in a quantity of 0.01 to 20% by weight, based on the colorant as a whole.

7. A composition as claimed in any of claims 1 to 8, characterized in that it contains oxidizing agents, more particularly H 2 0 2 , in a quantity of 15 0.01 to 6% by weight, based on the solution applied.

8. A composition as claimed in any of claims 1 to 9, characterized in that it contains anionic, zwitterionic or nonionic surfactants.

9. The use of naphthylazo compounds corresponding to formula I: R2 RII eN R1 -q OH O: M + 20 0() in which R 1 is hydrogen, halogen, hydroxy, nitro, a C14 alkyl group, a C1.4 alkoxy group, sulfo group or carboxy group, 25 R 2 is a 1- or 2-naphthyl group which bears at least one hydroxy group and may carry hydroxy, sulfo, carboxy, nitro groups or halogen atoms as further WO 00/38637 22 PCT/EP99/09999 substituents or a 1-aryl-5-hydroxy-4-pyrazolyl group which may be substituted in the 3-position by a C1.4 group, M is hydrogen, an alkali metal or 1/2 alkaline earth metal, 1/3 Al(Ill), 1/2 Zn(ll), 1/4 Ti(IV), 1/4 Zr(IV), 1/3 Cr(Ill), 1/2 Co(II), 1/2 Fe(ll), 1/3 Mo(lll) or 5 1/6 Mo(VI), 1/3 W(Ill) or 1/6 W(VI) or ammonium. as a coloring component in oxidation hair colorants.

10. A process for coloring keratin-containing fibers, more particularly human hair, in which a colorant containing a naphthylazo compound corresponding to formula (1): 10 R2 NN OH RI 0= M + in which R 1 is hydrogen, halogen, hydroxy, nitro, a C14 alkyl group, a C14 alkoxy 15 group, sulfo group or carboxy group, R 2 is a 1- or 2-naphthyl group which bears at least one hydroxy group and may carry hydroxy, sulfo, carboxy, nitro groups or halogen atoms as further substituents or a 1-aryl-5-hydroxy-4-pyrazolyl group which may be substituted in the 3-position by a C14 group, 20 M is hydrogen, an alkali metal or 1/2 alkaline earth metal, 1/3 Al(Ill), 1/2 Zn(ll), 1/4 Ti(IV), 1/4 Zr(IV), 1/3 Cr(Ill), 1/2 Co(II), 1/2 Fe(II), 1/3 Mo(Ill) or 1/6 Mo(VI), 1/3 W(llI) or 1/6 W(VI) or ammonium, and typical cosmetic ingredients is applied to the keratin-containing fibers, left thereon for a while, normally for about 30 minutes, and then rinsed out 25 again or washed out with a shampoo.