United States Patent (19) (11) 4,208,183 Grollier et al. (45) Jun. 17, 1980

54 PROCESS FOR IMPROVING THE STORAGE Attorney, Agent, or Firm-Fleit & Jacobson STABILITY OF INDOLE DYESTUFFS 57 ABSTRACT 75 Inventors: Jean F. Grollier; Chantal Fourcadier, The invention relates to storage-stable dyestuff solu both of Paris, France tions which can be mixed at the time of use with appro 73) Assignee: L'Oreal, Paris, France priate carriers. These solutions comprise at least one dihydroxyindole 21 Appl. No.: 904,309 of the formula: 22 Filed: May 9, 1978 (30) Foreign Application Priority Data HO May 10, 1977 (FR) France ...... 77 14254 51) Int. Cl...... A61K 7/13 HO ICJ'N R 52 U.S. Cl...... 8/409; 8/609; 8/611 58 Field of Search ...... 8/10, 10.1, 10.2, 11, in which R1 and R2 independently of one another de 8/32, 93 note hydrogen or methyl, or a cosmetically acceptable (56) References Cited salt thereof, in an anhydrous solvent chosen from U.S. PATENT DOCUMENTS amongst ethyl, isopropyl and tert-butyl alcohol, ethyl ene glycol monomethyl, monoethyl and monobutyl 3,194,734 7/1965 Seenuller et al...... 8/10.2 ethers and the acetate of ethylene glycol monoethyl 4,03,404 3/1977 Parent et al...... 8/10.2 X ether. Primary Examiner-Howard T. Mars Assistant Examiner-Vera C. Clarke 10 Claims, No Drawings 4,208, 183 1. 2 a substantially longer time than was possible to when PRO (CESS FOR IMPROVING THE STORAGE this same dyestuff was stored in dyeing compositions STABILITY OF INDOLE DYESTUFFS which were ready to be applied to the hair. The present invention also provides a process for the The present invention relates to solutions of indole 5 preparation of a dyeing composition intended to be dyestuffs. The invention more particularly relates to a applied directly to the hair which comprises introduc process for preserving these dyestuffs in a liquid me ing a dyestuff solution of this invention into a cosmeti dium before they are introduced into dyeing composi cally acceptable carrier usually employed in hair dye tions used for dyeing keratin fibres and, in particular, 1ng. human hair. O The cosmetic carriers which can be used according The dyestuffs of the indole family, and in particular to the invention can be in the form of creams, thickened the 5,6-dihydroxyindoles, are well-known and have gels or liquids, emulsions or simple lotions. formed the subject of French Pat. Nos. 1,264,707, When these carriers are in the form of a cream, they 1,133,594 and 1,166,172. However, it has been found generally comprise soaps or fatty alcohols in the pres that the commercial exploitation of these dyestuffs for 15 hair dyeing presents numerous problems, especially ence of emulsifiers. because of their lack of stability during storage in the The soaps are typically formed from natural or syn aqueous dyeing compositions usually employed for thetic fatty acids having 12 to 18 carbon atoms, such as dyeing the hair. lauric acid, myristic acid, palmitic acid and stearic acid, Storage stability is known to be of great importance 20 suitably at concentrations from 10 to 30% by weight from the commercial point of view, mainly because it is with alkalizing agents such as sodium hydroxide, potas sometimes necessary for the dyeing compositions to be sium hydroxide, ammonia, monoethanolamine, diethan stored for long periods of time and frequently under olamine or triethanolamine. high ambient temperature conditions. These creams can contain, in addition to the soaps, It has been suggested that the dyestuff can be pre 25 adjuvants such as fatty amides and fatty alcohols. served in the form of a powder which would only be Typical fatty amides include the mono- or di mixed with the cosmetic carrier at the time of use, but ethanolamides of acids derived from copra, of lauric the dyestuff gradually loses its solubility and its dyeing acid, of oleic acid or of stearic acid, and are preferably capacity if it is not preserved under very strict condi used at concentrations of up to 10% by weight. tions. 30 Amongst the fatty alcohols, oleyl, myristyl, cetyl, We have now discovered that, in certain well-defined stearyl and isostearyl alcohols can be used, in particular solvents, the 5,6-dihydroxyindoles preserve their dye at concentrations of up to 10% by weight. ing capacity during storage. The creams can also be formulated from natural or The solutions which contain one or more 5,6-dihy synthetic alcohols having 12 to 18 carbon atoms, which droxyindoles correspond to the general formula: 35 are mixed with emulsifiers. Typical alcohols include lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, cetyl/stearyl HO alcohol and hydroxystearyl alcohol, generally used in an amount from 3 to 25% by weight. The emulsifiers may be, for example, polyoxye HO thyleneated or polyglycerolated fatty alcohols such as a polyoxyethyleneated oleyl alcohol containing from 10 to 30 mols of ethylene oxide, stearyl alcohol containing in which R1 and R2, which are identical or different, 10 to 15 or 20 mols of ethylene oxide, polyglycerolated denote a hydrogen atom or a methyl group, or a cos 45 oleyl alcohol containing 4 mols of glycerol and polyox metically acceptable salt thereof, such as a halide and, in particular, the hydrobromide, in one or more anhydrous yethyleneated synthetic C9-C15 fatty alcohols contain solvents chosen from ethyl alcohol, isopropyl alcohol ing 5 to 10 mols of ethylene oxide. These "non-ionic' and tert-butyl alcohol, ethylene glycol monomethyl, emulsifiers are generally present in an amount of 5 to monoethyl and monobutyl ethers and the acetate of 50 25% by weight. ethylene glycol monoethyl ether. Other emulsifiers which can be used include alkyl Amongst these solutions, those in ethyl alcohol, eth sulphates, which may or may not be oxyethyleneated, ylene glycol monoethyl ether, ethylene glycol monobu such as sodium lauryl-sulphate, ammonium lauryl-sul tyl ether and the acetate of ethylene glycol monoethyl phate, sodium cetyl-/stearyl-sulphate, triethanolamine ether are particularly preferred. 55 cetyl-/stearyl-sulphate, mono- or tri-ethanolamine lau The dyestuff as defined above is suitably present in ryl-sulphate, the sodium salt of the sulphate half-ester of the solution in an amount from 0.1 to 80%, and prefera lauryl alcohol which has been polyoxyethyleneated bly from 5 to 50%, by weight. The concentration can be (with, for example, 2.2 mols of ethylene oxide) and the adjusted, according to the shades which it is desired to monoethanolamine salt of the sulphate half-ester of obtain, when the solution is used in the preparation of a lauryl alcohol which has been oxyethyleneated (with, composition intended for coloring the hair. for example, 2.2 mols of ethylene oxide). These constit The present invention also provides a process for uents are generally present at concentrations of 3 to preserving a dyestuff of formula (I) which consists in 15% by weight. storing the dyestuff, immediately after it has been syn When the cosmetic carriers used according to the thesized, in one or more of the solvents defined above, 65 invention are in the form of thickened gels or liquids, preferably in the above-mentioned amounts. they either contain thickeners, which may or may not Thus, it has been found that the dyestuff stored in the be in the presence of organic solvents, or they contain above-mentioned solvents retains its dyeing capacity for polyoxyethyleneated or polyglycerolated non-ionic 4,208, 183 3 4. compounds which may or may not be mixed with sol 734, having a molecular weight of 100,000, and GAF. Vents. QUAT 755, having a molecular weight of 1,000,000, by Typical thickeners include sodium alginate or gum Messrs. GENERAL ANILINE, quaternary derivatives arabic, or cellulose derivatives such as methylcellulose, of cellulose ether such as those sold under the name JR hydroxymethylcellulose, hydroxyethylcellulose, hy 125, JR 400 and JR 30 M by Messrs. UNION CAR droxypropylcellulose, hydroxypropylmethylcellulose BIDE, the quaternized polymers described in French or carboxymethylcellulose, or carboxyvinyl polymers Patent Applications Nos. 75/15162 and 76/20261, and such as the Carbopols. The lotions can also be thickened soluble crosslinked polyamino-amides such as those using a mixture of polyethylene glycols and stearates or described in French Patent Application No. 2,252,840 distearates of polyethylene glycols, or a mixture of 10 or in French Patent No. 1,583,363. amides and phosphoric acid esters. The polymer concentrations are generally 0.1 to 5% The concentration of thickener is generally from 0.5 and preferably 0.1 to 3%, by weight. to 30%, and preferably from 0.5 to 15%, by weight. The solvents can be low molecular weight alcohols They can also contain a surface-active agent in order having 1 to 4 carbon atoms or glycols such as those to impart foaming and detergent properties to these 15 mentioned above. The solvent concentrations are gen carriers. erally up to 50% by weight. The carriers which are in the form of a gel can con All these carriers can contain additives which are tain oxyethyleneated or polyglycerolated non-ionic usually employed in hair cosmetics, such as sunlight compounds, typically at concentrations of 1 to 60% by filters, optical brighteners, antioxidants, sequestering or weight optionally mixed with up to 30% by weight of 20 complexing agents and perfumes. solvent. The following may be mentioned by way of example: Amongst the polyoxyethyleneated or poly benzylidene-camphor as sunlight filter, sodium bisul glycerolated non-ionic compounds, there may be men phite and thioglycolic or thiolactic acids and their salts tioned, in particular, polyoxyethyleneated nonylphenol as antioxidants, ethylenediaminetetraacetic acid or di containing 4 or 9 mols of ethylene oxide, poly 25 ethylenetriaminepentaacetic acid and their salts as com glycerolated oleyl alcohol containing 2 or 4 mols of plexing agent. glycerol, polyglycerolated cetyl/stearyl alcohol con The pH can be adjusted with alkaline agents such as taining 2 or 6 mols of glycerol and polyoxyethyleneated mono- or tri-ethanolamine, ammonia, ammonium car synthetic fatty alcohols having 11 to 15 carbon atoms bonate, potassium carbonate or sodium carbonate or and containing from 3 to 10 mols of ethylene oxide. The 30 sodium hydroxide, or with acidifying agents such as gels can also be obtained from soaps of liquid fatty acids phosphoric, hydrochloric, tartaric, acetic, lactic or cit such as oleic or isostearic acid. ric acid. It is generally from 3 to 12 and preferably from Amongst the solvents which can be used in this type 5 to 10. of carrier, there may be mentioned, in particular, lower The amount of dyestuff solution containing dyestuffs (i.e. of 1 to 6 carbon atoms) aliphatic alcohols such as 35 relative to the cosmetic carrier is generally 1 to 80%, ethyl alcohol or propyl or isopropyl alcohol, and gly and preferably 3 to 50%, by weight. cols such as propylene glycol, butylglycol or ethyl The storage and subsequent mixing can be carried out glycol. in various ways using known devices, such as devices These carriers can also contain adjuvants such as possessing two compartments, one of which contains fatty amides. The latter can be the same as those listed the dyestuff solution and the other of which contains above for the creams. the cosmetic carrier. When the carriers are in the form of emulsions, they A preferred method of carrying out the invention can be non-ionic or anionic. The non-ionic emulsions consists in using an aerosol device with a double com are formed from a mixture of oils and/or waxes, fatty partment, the solvent phase containing the said dye alcohols, and polyoxyethyleneated fatty alcohols such 45 stuffs and the aqueous phase forming the carrier being as polyoxyethyleneated stearyl or cetyl/stearyl alco mixed by means of the valve. The propellants used in hols. Cations can be added to these compositions. the said aerosols can be, in particular, carbon dioxide The anionic emulsions are usually formed from soaps; gas, nitrogen, nitrous oxide, volatile hydrocarbons such examples include the emulsion comprising self-emulsi as butane, isobutane and propane, and halogenohydro fying glycerol stearate and sold under the name IMWI 50 carbons such as methylene chloride or, preferably, TOR 960 K by Messrs. DYNAMIT NOBEL, and the fluorohydrocarbons (sold under the name Freon by emulsions comprising a combination of glycerol mono Messrs. DU PONT DE NEMOURS), in particular stearate with citric acid esters or with fatty alcohols and fluorochlorohydrocarbons such as dichlorodifluoro lipopeptides or with alkali metal stearates and sold methane (Freon 12), dichlorotetrafluoroethane (Freon under the names Lameform ZEM, LPM and NSM, 55 14) and trichloromonofluoromethane (Freon 11), chlo respectively, by Messrs. GRUNAU. rodifluoromethane (Freon 22), 1-chloro-1,1-difluoroe When the carriers are in the form of lotions, they thane (Freon 142 B) and 1-monochloro-2,2,2-trifluoroe generally comprise water or aqueous solutions to which thane (Freon 133A). These propellants can be used by solvents and/or treatment products of cationic charac themselves or in combination; a mixture of Freon ter, such as cations or cationic polymers which are 114/12, in proportions varying from 40:60 to 80:20, can usually employed in hair cosmetics, are optionally be used in particular. added. Suitable devices which can be used include those Quaternary ammonium salts such as trimethyl described in, inter alia, French Pat. No. 1,557,740, and cetylammonium bromide and cetylpyridinium bromide French Patent Application Nos. 73/46537, 71/08902, can be used as cations. 65 72/02321 and 76/05827. There may be mentioned, in The following may be mentioned as typical cationic particular, the plugs having a cavity of the sliding cap polymers: quaternary vinylpyrrolidone copolymers type containing the solution which is to be mixed with such as the polymers sold under the name GAFOUAT the carrier inside the flask carrying the plug, or an un 4,208, 83 5 6 pressurized container possessing at least one dispensing Oxidizing agents which decompose in water should orifice in its outer casing, the said outer casing being either be used in powder form or dissolved at the time elongate and made of deformable flexible material and of use. enclosing at least one closed, brittle, rigid tube, the The concentrations of oxidizing agent is generally cosmetic carrier being situated outside the above-men from 0.1 to 6% by weight. tioned brittle tube and inside the flexible envelope and The compositions of this invention can be applied to the dyestuff solution according to the invention being any type of hair, that is to say natural hair, permed hair situated inside the rigid brittle tube. or hair which has been more or less bleached. A further example of a device which makes it possible The following Examples further illustrate the present to carry out the invention is a flask containing the cos 10 invention. metic carrier and possessing a chamber having a dia Tables I to Villustrate compositions according to the phragm, which chamber is located inside the neck of the invention and their method of use. flask and contains the dyestuff solution. In this case, Initially, dyestuff solutions indicated in Table I are mixing is carried out when a trocar, which is held by a prepared by mixing the dyestuff and the solvent which rim against the extreme outer edge of the neck of the 15 is substantially anhydrous, this Table showing the na said flask, slides and perforates the diaphragm and the ture and amount of the dyestuff, the solvent and the botton of the chamber. amount of solvent. The compositions prepared by introducing dyestuff When it has been prepared, the solution is stored for solutions according to the present invention into the the lengths of time shown in Table I and is then mixed cosmetic carriers can be used for dyeing the hair essen with the various cosmetic carriers shown in Table I and tially in accordance with two processes using either explained in Table II. development of the coloration due to the effect of the When it has been prepared, the dyeing composition is air or development by means of an oxidizing agent. applied to the head of hair, the initial color of which is In the dyeing process using development in air, the indicated in Tables III and IV. dyestuff solution mixed with the carrier is applied to the 25 Unless an oxidizing solution is indicated in the Tables, hair for, say, 5 to 30 minutes and is then rinsed out; the the coloration is developed by oxidation in air. coloration is developed by oxidation in the air. Table III relates to a process of application in a single In the dyeing process using development by means of stage which consists in introducing an oxidizing solu an oxidizing agent, an oxidizing agent, as a powder or in tion, in the amounts shown in Table III, into the dyeing solution, is mixed with the carrier to which the dye 30 compositions shown in Table I, and applying the com stuffs solution defined above has been added, and the position thus prepared to the hair for the periods of time composition is applied to the hair by following the indicated. This Table indicates the color of the hair above procedure. The oxidizing agent, as a powder or which has been treated and the shades obtained. in solution, can also be applied in a second stage after Table IV relates to a two-stage dyeing process which application to the hair of the dyeing composition pre 35 consists in applying the dyeing compositions defined in pared as indicated above, and after rinsing. Table I for the periods of time shown, and applying, Suitable oxidizing agents are hydrogen peroxide, urea after rinsing, an oxidizing solution of the type, and in the peroxide, persalts such as ammonium persulphate, so amounts, shown in Table IV with reference to the par dium persulphate or potassium persulphate, barium ticulars given in Table V. peroxide and silver carbonate. The shades obtained are observed after rinsing, sham Stabilized oxidizing solutions can be in various forms, pooing if desired, and drying. for example creams, thickened gels or liquids, emulsions The reference S indicates that the hair has been sham or simple lotions. pooed and the reference R indicates that it has only been rinsed. TABLE I PREPARATION OF THE DYENG COMPOSITIONS Dyestuff solution Cosmetic carrier Preparation Storage Amount Amount Examples Dyestuffs g % Solvent time used (g) Nature (g) S1 5,6-Dihydroxyindole 16.5 Ethylglycol 8 2.5 A 37.5 qSp 100 months 2,3-Dimethyl-5,6-dihydroxy indole hydrobromide 2 S2 5,6-Dihydroxyindole- 28.6 Ethylglycol 50 6 2.8 B 17.2 Butylglycol months Sp 100 S3 2,3-Dimethyl-5,6-dihydroxy- Ethylglycol 10 2 8 C 32 indole 5 Ethylglycol months acetate qsp 00 S4 2,3-Dimethyl-5,6-dihydroxy- Butylglycol 35 6 5 D 5 indole hydrobromide 30 Ethanol qsp 100 months S5 5,6-Dihydroxyindole 50 Butylglycol 40 6 1.6 38.4 months Ethanol qsp 100 Sg 5,6-Dihydroxyindole 30 Ethylglycol 20 10 25 F 18.75 2,3-Dimethyl-5,6-dihydroxy- 2 Ethanol qsp 100 months indole S. 2-Methyl-5,6-dihydroxy- 10 Ethylglycol 30 6 2.5 G 17.5 indole months 2,3-Dimethyl-5,6-dihydroxy- 30 Ethanol qsp OO indole hydrobromide 4,208, 183 7 TABLE I-continued PREPARATION OF THE DYEING COMPOSITIONS Dyestuff Solution Cosmetic carrier - Preparation- Storage Amount Annount " Examples Dyestuffs g % Soivent time used (g) Nature (g) S3 5,6-Diihydroxyindole 25.5 Ethylglycol 35 2.75 A 37.25 year 2-Methyl-5,6-dihydroxy- .5 Ethanol asp 100 indole S9 5,6-Dihydroxyindole 1) 2,3-Dimethyl-5,6- Ethylglycol OO 4,4 H 35.6 dihydroxyindole asp year Slo 5,6-Dihydroxyindole 20 Butylglycol 00 24 4. H 36 asp hours S11 5,6-Dihydroxyindole 10 2,3-Dimethyl-5,6- 2.5 Ethylglycol E00 4. 4. 36 dihydroxyindole hydro- asp months bromide S12 5,6-Dihydroxyindole 5 Butylglycol 30 32 25 J 38.2 Ethanol asp 100 months S13 5,6-Dihydroxyindole 19 Butylglycol OO 8 4. K 36 asp months Si4 5,6-Dihydroxyindole 20 Ethylglycol 00 M 8 sp months

TABLE II EXAMPLES OF CARRIERS Constituents Carrier A Carrier B Carrier C Copra diethanolamide sold under the maine "COMPERLAN KD" by Messrs. DEHYDAG 5.3 g 1.6 g. 5g Hydroxymethylpropylcellulose sold under the name “METHOCEL F4 M' by Messrs. DOW CHEMICAL i. 1 g 2.3 g .5g Sodium lauryl-sulphate containing 2 mols of ethylene oxide, sold under the name “DELF 8533' by Messrs. ASTRA CALVE 10 g Sodium bisulphite | cc Urea 7.5 g Monoethanoianine g Triethanolamine 7 g Water usp 100 g gsp 100 g qsp 100 g Constituents Carrier D Carrier L Polyoxyethyleneated nonylphenol containing 4 mois of ethylene oxide, sold under the name "REMCOPAL 334" by Messrs. GUERLAND 40 g 22g Polyoxyethyleneated nonylphenol containing 9 mols of ethylene oxide, sold under the name "REMCOPAL 349" by Messrs. GUERLAND 13.5g 22 g EDTA sold under the name "DISSOLVINE Z" by Messrs. NOURY FRANCE 0.4 g Butylglycol 3 g Propylene glycol 3 g 40% Strength solution of DTPA in water, sold under the name "MASQUOL DTPA" by Messrs. PROTEX 5.5 g Sodium bisulphite | cc 22 Baume strength ammonia solution -0.5 cc 10 cc Water sp 100 g qsp 100 g Constituents Carrier E Carrier F Carrier G Carrier K 50/50 Cetyl/stearyl alcohol sold under the name "LANETTE WAX 0" by Messrs. DEHYDAG g 6 g 16 g 8g Oley alcohol 35 g 2.7 g ... g. 1.35 g Tertiary fatty amine sold under the name "CEMULCAT OS 12" by Messrs. RHONE POULENC Industries 1.6 g 3.2 g 3.2 g 1.6 g Ammonium lauryl-sulphate containing 20% of fatty acid, sold under the name “SIPON LA 30" by Messrs. HENKEL 5.5g | g | g 5.5g 40% Strength solution of DTPA in water, sold under the name "MASQUOL DTPA" by Messrs. PROTEX (.4g 4.4 g lig Sodium bisulphite cc Monoethanolamine 2.9 g Triethanolamine 5g 3g 22 Baume strength ammonia solution 2.5 cc Water qsp 100 g qSp 100 g qsp 100 g qsp 100 g Constituents Carrier H Carrier

4,208, 183 TABLE II-continued EXAMPLES OF CARRIERS 16% Strength hydroxyethylcellulose sold under the name "CELLOSIZE WP 3" by Messrs. CARBIDE & CARBONI 34g 34g 40% Strength solution of DTPA in water, sold under the name of "MASQUOL DTPA" by Messrs. PROTEX 1.1 g Sodium bisulphite 1 cc Pure lactic acid qsp. pH 6 Water qsp 100 g qsp 100 g Constituents Carrier J Partially oxyethyleneated self-emulsifying non-ionic wax sold under the name "SINNOWAXOD" by Messrs. SINNOVA 2g Cocoa monoethanolamide 0.6 g. Trimethylcetylammonium bromide 0.1 g Triethanolamine 2.9 g Water qsp 100 g Carrier M Quaternized vinylpyrrolidone copolymer having a molecular weight of 1,000,000, marketed under the name GAFOUAT 755 by Messrs. GENERAL ANELINE 0.5g Quaternized cellulose sold under the name JR 400 by Messrs. UNION CARBOE 0.5g Quaternized polymer having the formula: 0.3 c. CH3C- CH3Cl- w -- -(CH)-N' -(CH2)6 CH3 CH3 r Water q.s.p. 100 g pH adjusted to 6.

TABLE III APPLICATION TO HARDYEING - Application Oxidizing solution Time (of Dyeing introduced into the applica- Post composi- dyeing composition tion) treat Examples tion Nature g minutes ment Head of hair Shades obtained 1 S1 15 S Light chestnut Lightgrey con containing a high cealing white percentage of hair white hair 2 S2 hydrogen peroxide 20 20 R Blond containing Uniform blond of 10 volumes 80% of white strength hair 3 S2 urea peroxide 1. 20 R Blond containing Very luminous (powder) 80% of white blond hair 4. S3 20 S Light chestnut Golden containing a high chestnut percentage of white hair 5 S4 hydrogen peroxide 20 30 S Blond containing Natural blond of 4 volumes a high percentage strength of white hair 6 S5 20 S White Light chestnut 7 Sis hydrogen peroxide 20 20 S Deep chestnut Chestnut of 2 volumes containing 60% strength of white hair and bleached beforehand 8 S7 hydrogen peroxide 20 30 S Blond hair con- Deep blond with of 4 volumes taining a high a red sheen strength percentage of white hair

TABLE IV TWO-STAGEDYEING PROCESS Oxidizing solution applied to the head of hair Time (of 4,208,183 11 12 TABLE IV-continued Dyeing Applica- applica- Post composi- ition time tion) treat Examples tion minutes Head of hair treated Nature minutes ment Shades obtained 9 S1 15 Light chestnut con- O 5 S Uniform light taining a high per- chestnut with a centage of white golden sheen hair 10 S8 5 Chestnut containing O1 5 R Chestnut with an a high percentage auburn sheen of white hair and bleached beforehand 11 S9 15 White O3 0. S Ashen deep grey 15 S Golden grey 12 S10 20 Deep blond containing O2 0 S Ashen deep blond 90% of white hair 13 S11 15 Chestnut containing iO4 10 S Natural deep blond a high percentage of with a good white hair and covering of white bleached beforehand hair in two tones Oxidizing solution applied to the head of hair Dyeing Applica- Post composi- tion time Time treat Examples tion minutes Head of hair treated Nature minutes ment Shades obtained 4. Si2 15 Chestnut with a high O 5 S Luminous copper percentage of white chestnut with a hair good covering of white hair 15 S13 20 White hair permed O2 5 to S Natural blond to beforehand 25 natural chestnut 16 S15 5 Blond containing a hydro- 5 R Uniform ashen high percentage of ger blond white hair per oxide of 10 "volumes strength

EXAMPLE 1.7 TABLE V-continued A dyestuff solution is prepared by mixing 9 g of 5,6- OXIDIZING SOLUTIONS dihydroxyindole with ethanol which is present in a Constituents O O2 O3 O4 sufficient amount to make up 100 g. under the name "MASQUOL 1 g 1 g After storing the said solution for 8 months, 4 g of this R E. PROTEX 5 solution ae mixed, at the time of use, with4-l. 36 g of the 21OOC2Oate Baume strength 2.9 cc 5 cc 5 cc cosmeticThis dyeing carrier composition K defined inis appliedTable II. for 20 minutes to 45 ammoniaWater q.s.p. solution 100 g 100 g 100 g 100 g a light chestnut head of hair containing a high percent age of white hair and is then rinsed out. We claim: 40 g of the composition obtained by mixing, weight 1. A process for improving the storage stability of for weight, the carrier L defined in Table II and an 50 either a dye having the formula: oxidizing solution indicated in Tables III to V are then applied for 15 minutes. After rinsing, shampooing and drying, the following HO colorations are obtained, depending on the oxidizing solution chosen: very natural chestnut, using hydrogen 55 peroxide of 2 volumes strength as the oxidizing solution, HO and restrained ashen chestnut, using a 1% strength by weight solution of ammonium persulphate. TABLE V in which R1 and R2, identical or different, are hydrogen OXIDIZING SOLUTIONS or methyl, or a cosmetically acceptable salt of said dye Constituents O O2 O3 O4 comprising the steps of dissolving at least one of said Silver carbonate 0.3g dye or salt thereof in at least one substantially anhy Hydrogen peroxide of 20 15 g 5g drous hydroxylic solvent selected from the group con volumes strength sisting of ethyl alcohol, isopropyl alcohol, tert-butyl Powdered barium peroxide g 65 alcohol, ethylene glycol monomethyl ether, ethylene Olein 2g Ethanol 4g glycol monoethyl ether, ethylene glycol monobutyl 40% strength solution of ether, and the acetate of ethylene glycol monoethyl DTPA in Water, sold ether, wherein the dye or salt thereof is present in an 4,208, 183 3 14 6. The process of claim 1, wherein the dye is 2,3- amount from about 0.1 to 80% by weight, and maintain dimethyl-5,6-dihydroxyindole. ing said dye in the presence of said anhydrous solvent 7. The process of claim 1, wherein the anhydrous during storage. solvent is ethyl alcohol. 2. The process of claim 1, wherein the dye is in the 8. The process of claim 1, wherein the dye is present in an amount from 0.5 to 50% by weight. form of a halide. 9. The process of claim 1, wherein the dye is 2-meth 3. The process of claim 1, wherein the dye is in the yl-5,6-dihydroxyindole. form of a hydrobromide. 10. The process of claim 1, wherein the anhydrous 10 solvent is selected from the group consisting of ethylene 4. The process of claim 1, wherein the dye is 5,6-dihy glycol monoethyl ether, ethylene glycol monobutyl droxyindole. ether and the acetate of ethylene glycol monoethyl 5. The process of claim 3, wherein the dye is 2,3- ether. dimethyl-5,6-dihydroxyindole hydrobromide. st 5

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