AT393219B - Colorant for keratin fibres, in particular for hair, and method for colouring keratin fibres, in particular hair - Google Patents

Abstract

The invention relates to a colorant for keratin fibres, in particular for hair, which contains in a cosmetic carrier material besides water at least one oxidation base selected from p-phenylenediamines, p-aminophenols and heterocyclic bases, and, where appropriate, other cosmetic adjuvants. The composition according to the invention is characterized in that it contains as coupler at least one m-phenylenediamine of the general formula (I) in which the substituents have the meaning stated in Claim 1. The invention additionally relates to a method for colouring keratin fibres, in particular hair, using this composition. <IMAGE>

Description

AT 393 219 B

The present invention relates to a colorant for keratin fibers, in particular for hair, and a method for dyeing keratin fibers, in particular hair.

The m-phenylenediamines have been known to play an important role in dyeing keratin fibers such as hair or furs for a long time. They are part of the class of compounds commonly called couplers. These couplers, together with p-phenylenediamines or p-aminophenols, which are called oxidation bases, give colored indamines, indoanilines or indophenols in an alkaline, oxidizing medium.

If m-phenylenediamines are reacted with p-phenylenediamines in an alkaline, oxidizing medium, in particular in the presence of hydrogen peroxide, indamines are obtained which give the keratin fibers very strong blue colorations. In addition, the m-phenylenediamines together with p-aminophenols in an alkaline, oxidizing medium give indoanilines, which give the keratin fibers more or less purple red colorations. The m-phenylenediamines thus play a double role as couplers in hair coloring, they bring blue and red, which are two essential basic colors, in order to obtain not only black or gray, but also chestnut-colored tones with an ash or copper shimmer.

Despite its important role, this type of coupler is limited in practice to a very limited number of connections. This is explained by the fact that only compounds can be used for the coloring of keratin fibers, which give dyeings of very good quality, i. H. that do not change over time, especially as a result of light or weather. When it comes to hair coloring, the couplers used must also be completely harmless and may be used, especially in the Ames test with Salmonella Thyphimurium (TA 1538, TA 98, TA 100, TA 1537 and TA 1535, in the absence or presence of "S9 MIX "activated with" Arochlor 1254 ") practically does not react mutagenically.

DE-OS 27 37 138 of the applicant describes as couplers for colorants which contain oxidation bases, hydroxyalkyl derivatives of 2,4-diaminophenol, which, in contrast to the couplers used according to the present invention, are only monohydroxy compounds.

The present invention thus relates to a colorant for keratin fibers, in particular for hair, in the form of a cosmetic preparation, for. B. in the form of a liquid, a cream, a gel or an aerosol, consisting of a cosmetic carrier material which, in addition to water, has at least one oxidation base selected from p-phenylenediamines, p-aminophenols and heterocyclic bases, and optionally further cosmetic adjuvants, such as alkalizing agents Acidifying agents, surface-active agents, organic solvents, thickeners, antioxidants, penetrants, film-forming agents, foaming agents, sequestering agents, care agents and fragrances, which is characterized in that it is a coupler of 0.001-2.85% by weight, based on the Total weight of the agent, at least one m-phenylenediamine of the general formula

OZ

in which Z is either a polyhydroxyalkyl group whose alkyl group contains 3 to 6 C atoms, which polyhydroxyalkyl group has 2 or 3 hydroxyl groups, or an alkyl group with 4 to 8 C atoms which is interrupted by at least one oxygen atom and has at least one hydroxyl group , wherein this hydroxyl group (s) is (are) bonded to a carbon atom which has no further oxygen bond, or at least one of its acid addition salts and moreover optionally at least one further coupler, optionally at least one compound selected from o-diphenol, o -Phenylenediamine or o-aminophenol, which can optionally be substituted on the ring or the amine functions, and also optionally contains at least one dye precursor from the benzene or naphthalene series, furthermore optionally at least one direct dye and further optionally at least one indoanuine, indophenol or indamine leuco derivative andhas a pH of 8 to 11.5. In particular, the agent according to the invention contains at least one m-phenylenediamine of the general formula (I), in which 1 Z denotes an alkyl group which is interrupted by at least one oxygen atom or at least one acid addition salts. -2-

AT393 219 B

The agent according to the invention is further characterized in that it contains at least one m-phenylenediamine of the general formula (I), in which Zessen ß- (ß'-Hydroxyäthoxy) ethyl or aß - [(ß'-Hydroxyäthoxy) -äthoxy] ethyl radical or represents a ß, γ-dihydroxypropyl or a 3 '- (ß-hydroxyethoxy) -2'-hydroxypropyl radical or contains at least one of its acid addition salts. According to a particular embodiment, the m-phenylenediamine is e.g. B. in an amount of 0.001 - 2.5 wt .-%, based on the total weight of the agent.

The oxidation bases contained in the colorant according to the invention are in particular the following: A) p-phenylenediamines of the general formula

in which R j, R2 and R3 are identical or different and are hydrogen, an alkyl radical having 1 to 4 carbon atoms or an alkoxy radical having 1 to 2 carbon atoms, R4 and R5 are identical or different and hydrogen, an alkyl radical, a hydroxyalkyl radical , an alkoxyalkyl radical in which the alkoxy group has 1 to 2 carbon atoms, a carbamylalkyl, mesylaminoalkyl, acetylaminoalkyl, ureidoalkyl, carbäthoxyaminoalkyl, aminoalkyl, monoalkylaminoalkyl, di-alkylaminoalkyl, piperidinoalkyl, morpholinoalkyl radical, where the alkyl groups in the radicals R4 and R ^ have 1 to 4 carbon atoms, or R4 or R5 together with the nitrogen atom to which they are attached form a piperidine or morpholine radical, where Rj and R3 are hydrogen, in the case that R4 and R5 are not hydrogen, or their acid addition salts; B) p-aminophenols of the general formula

OH, (ΠΙ) * 6 NH2 wherein Rg is hydrogen, an alkyl radical having 1 to 4 carbon atoms or a halogen atom, for example chlorine or bromine, or their acid addition salts; C) heterocyclic bases such as 2,5-diamino-pyridine, 3-methyl-7-aminobenzomorpholine and 5-aminoindole.

It has been found that by using the m-phenylenediamines of the general formula (I) together with at least one oxidation base specified under A, B and C, colorants can be obtained which give the hair good color tones, which are particularly washable.

In general, with the couplers contained in the colorant according to the invention, together with the p-phenylenediamines, blue colorations can be achieved which are more or less rich in shades of green or purple, while red colors are achieved with the p-aminophenols. The colorant according to the invention can thus advantageously contain both p-phenylenediamines and p-aminophenols at the same time.

It was also found that among the compounds of general formula (I) or the acid addition salts with the (2,4-diamino) phenyl-β- (β'-hydroxyethoxy) ethyl ether, in particular in the form of the dihydrochloride and / or the (2,4-diamino) phenyl-β, y-dihydroxypropyl ether, particularly in the form of the dihydrochloride, particularly good results can be achieved.

In addition to the coupler (s) of the general formula (I) and the -3-

AT 393 219 B

Oxidation base (s), alone or in combination, contain the following products: 1) Other known couplers, for example resorcinol, 2-methylresorcinol, m-aminophenol, 2-methyl-5-aminophenol, 2-methyl-N- (β-hydroxyethyl) -5 -aminophenol, 6-hydroxybenzomorpholine, 2,6-dimethyl-3-5 acetylaminophenol, 2-methyl-5-carbäthoxyaminophenol, 2-methoxy-5-carbäthoxyaminophenol, 2-methyl-5-ureidophenol and l-phenyl-3-methyl- 5-pyrazolone; 2) o-phenylenediamines and o-aminophenols, which may have substituents on the core or on the amine function, and o-diphenol, these products being able to lead to new colored compounds through complex oxidation mechanisms, by self-cyclization or by reaction with the p-phenylenediamines ; 3) Dye precursors of the benzene series with at least three substituents on the core, selected from hydroxyl, methoxy or amino, for example dichlorohydrate from 2,6-diaminohydroquinone, trichlorohydrate from 2,6-diamino-N, N-bis-4- (ethyl) aminophenol, dichlorohydrate of 2,4-diaminophenol, 2,3,5-trihydroxytoluene, 15 4-methoxy-2-amino-N- (β-hydroxyethyl) aniline or 1,2,4-trihydroxybenzene; 4) Naphthalene series dye precursors such as 2-hydroxy-l, 4-naphthoquinone and 5-hydroxy-l, 4-naphthoquinone; 5) Leuco derivatives of indoanilines or indophenols, for example 4,4'-dihydroxy-2-amino-5-methyldiphenylamine, 4,4'-dihydroxy-N- (β-hydroxyethyl) -2-amino-5-methyl-2 ' -chlorodiphenylamine, 2,4, -diamino-4-hydroxy-5-methyldiphenylamine, 2,4-dihydroxy-N- (ß-methoxyethyl) -4, -ammodiphenylamine, 2,4-dihydroxy-5-methyl-N- ( β-methoxyethyl) 4'-aminodiphenylamine; 25 6) direct dyes, selected from nitrated dyes of the benzene series, for example N, N-bis (ß-

Hydroxyethyl) -l-amino-3-nitro-N'-4-methylaminobenzene, N, N - (methyl.ß-hydroxyethyl) -l-amino-3-nitro-N, - (ß-hydroxyethyl) -4-aminobenzene , N, N- (methyl, ß-hydroxyethyl> l-amino-3-nitro-N, -methyl-4-aminobenzene, 3-nitro-N- (ß-hydroxyethyl) -4-aminoanisole, 3-nitro-N - (ß-Hydroxyethyl) -4-aminophenol, (3-nitro-4-amino) -phenoxyethanol, (3-nitro-N-4-methylamino) -phenoxyethanol, N- (ß-hydroxyethyl) -2-amino-5 -nitioanisoL 30

The pH of the colorant according to the invention is basic and is, for example, between 8 and 11.5. As usable alkalizing agents, ammonia, alkylamines such as ethylamine or triethylamine, alkanolamines such as mono-, di- or triethanolamine, alkylalkanolamines such as methyldiethanolamine, sodium or potassium hydroxides, sodium, potassium or ammonium carbonates can be mentioned. As acidifiers that can be used, there can be mentioned 3 5 lactic acid, acetic acid, tartaric acid and phosphoric acid.

Water-soluble anionic, cationic, non-ionic or amphoteric surface-active agents or mixtures thereof can also be added to the agent according to the invention. Of these, in particular alkylbenzenesulfonates, alkylnaphthalenesulfonates, sulfates, ether sulfates and sulfonates of fatty alcohols, quaternary ammonium salts, e.g. As trimethylcetylammonium bromide, cetylpyridinium bromide, fatty acid diethanoiamide, 40 polyoxäthylenierte or with glycerol polycondensed acids and alcohols and polyoxäthylenierte or polycondensed with glycerol to name alkylphenols. The amount of surface-active agents contained in the agent according to the invention is preferably 0.5-55% by weight, in particular 4-40% by weight, based on the total weight of the agent.

Organic solvents can also be added to the agent according to the invention in order to dissolve the compounds which are not sufficiently water-soluble. As a solvent that can be used advantageously, for example, ethanol, isopropanol, glycerol, glycols and their ether such. B. 2-butoxyethanol, ethylene glycol, propylene glycol, diethylene glycol monoethyl ether and monomethyl ether and similar solvents. The solvents can be contained in the agent in a concentration of 1-40% by weight, preferably 5-30% by weight, based on the total weight of the agent. 50 The thickening agents which can be added to the agent according to the invention are preferably selected from sodium alginate, gum arabic, cellulose derivatives, e.g. Methyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, the sodium salt of carboxymethyl cellulose and acrylic acid polymers. Mineral thickeners, such as bentonite, can also be used. The concentration of thickener is preferably between 0.5 and 5% by weight, in particular between 0.5 and 3% by weight, based on the total weight of the agent.

Antioxidants which can be added to the agent according to the invention are preferably selected from sodium sulfite, thioglycolic acid, mercapto-succinic acid, sodium bisulfite, ascorbic acid and hydroquinone. -4-

AT 393 219 B

These antioxidants can be present in the agent according to the invention in a concentration of 0.05 to 1.5% by weight, based on the total weight of the agent.

The colorant according to the invention is mixed at the time of use with an oxidizing agent, such as hydrogen peroxide, urea peroxide or persalts, such as ammonium persulfate.

The colorant according to the invention can be in the form of a liquid, a cream, a gel, an aerosol or in any other form suitable for coloring keratin fibers.

The present invention further relates to a process for dyeing keratin fibers, in particular hair, using the agent according to the invention, which is characterized in that this agent is mixed with the oxidizing agent, such as hydrogen peroxide, urea peroxide or persalts, immediately before use, the mixture thus obtained applied to the fibers or hair and allowed to act for a period of 5 to 45 minutes, then rinsed, optionally shampooed and rinsed again and then the fibers or hair dried

The present invention is explained in more detail below, preceded by rules of haste for the active connections, using exemplary embodiments, which, however, do not constitute a restriction.

Procedure 1: Preparation of (2,4-diaminnl-rtop.nyl-ß (ß'-hydroxyethoxy) ethyl ether dihydrochloride of the following formula:

First stage: OH

NHCOCH, NO Second stage: OK

KOH

OK

NHCOCH, NO "

o-ch2-ch2-o-ch2-ch2-oh ^ W-NHCOCHj + ci-ch2-ch2-o-ch2-ch2-oh no2

NO.

Third stage: o-ch2-ch2-o-ch2-ch2-oh

Reduction U. HCl NH, nhcoch.

Fourth stage:

acid hydrolysis

-5-

AT 393 219 B

First stage: Preparation of the 2-acetylamino-4-nitrophenol potassium salt 2150 ml of ethanol, which contains 133 g (1.89 mol) of 80% potassium hydroxide, are cooled to -10 ° C. and gradually 371 g with stirring (1.89 mol) 2-acetylamino-4-nitrophenol added while keeping the temperature below 5 ° C. The potassium salt Mt out; the product is filtered off, washed with ethanol and dried in vacuo at 50 ° C.

Mass (determined by potentiometry): 226, theoretically. Value: 234

Second stage: preparation of (2-acetylamino-4-nitro) phenyl-β- (β'-hydroxyethoxy) ethyl ether 117 g (0.5 mol) of the potassium salt of 2-acetylamino-4-nitrophenol are introduced into 500 ml of dimethylformamide and then 64 ml (0.6 mol) of diethylene glycol monochlorohydrin was added with stirring. The mixture is kept under stirring at a temperature of about 100 ° C. for 8 hours and then poured into 21 ice water. The crude product is filtered off, washed with water, then with cold 1N sodium hydroxide solution and finally again with water. After drying in vacuo and recrystallization from ethanol, the expected product melts at 152 ° C.

Analysis for Ci2Hi6 ^ 2 ^ 6: C H N O calculated: 50.70 5.67 9.86 33.77% found: 50.88 5.64 9.74 33.90%

Third stage: Preparation of the monochlorohydrate of (2-acetylammo-4-ammo) -phenyl-ß- (ß'-hydroxyethoxy) ethyl ether 400 ml of ethanol (96% by volume), the 75 ml of water, 10 g of ammonium chloride and 200 g Zinc powder are added, the mixture is heated under reflux and then little by little 91 g (0.32 mol) (2-acetylamino-4-nitro) phenyl-β- (β'-hydroxyethoxy) ethyl ether is added with further stirring. After each addition, the reaction medium decolors very quickly. After the addition of the nitroderivative has ended, the mixture is heated for a further 10 minutes and then the reaction mixture is filtered off, the filtrate in 30 ml of ethanol (96% by volume), which is mixed with 34 ml of hydrochloric acid (36%) and with the aid of a dry ice / ethanol mixture beforehand had been cooled is ingested. The desired product crystallizes out in the form of the chlorohydrate. It is filtered off, washed with a little absolute ethanol, which had previously been cooled to -10 ° C, and then dried in vacuo at 55 ° C; Mp (decomposition): 190-192 ° C.

Analysis for C ^ Hig ^ O ^ HCl: C H N O CI calculated: 49.57 638 9.63 22.01 12.19% found: 49.56 630 9.48 21.83 1230%

Fourth stage: Preparation of the dichlorohydrate of (2,4-diamino) -phenyl- (ß'-hydroxyethoxy) ethyl ether 70.9 g (0.25 mol) (2-acetylamino-4-amino) -phenyl-ß- ( ß4iydroxyäthoxy) ethyl ether monohydrochloride in 210 ml of absolute ethanol saturated with hydrogen chloride gas are heated under reflux with stirring. After heating for 10 minutes, the dissolution is complete; the desired dichlorohydrate then begins to fail after about 1/2 hour. The mixture is heated for a total of 1 h and then the reaction medium is cooled to 0 ° C. The dichlorohydrate is filtered off, washed with a little absolute ethanol at 0 ° C and dried in vacuo at 55 ° C. It melts between 180 and 185 ° C with decomposition.

Analysis for C ^ Hig ^ Oj ^ HCl: CHNO CI calculated: 42.12 6.36 9.82 16.83 24.87% found: 42.24 6.39 9.73 17.07 24.90 - 24, 94% -6

AT393 219 B

Regulation2; Production of (, 2,4-DiaminQVphenyl-ß.y-dihvdroxvpropvläthCTdichlodivdiat of the following formula:

First stage: OKNHCOCH-

N02 Second stage:

+ cich2-choh-ch2oh

Reduction 0-CH2-CH0H-CH20Hj ^ pNHCOCHj # HC1 INH «

Third step:

acid hydrolysis - &gt;

First stage: Preparation of (2-acetylamino-4-nitro) -phenyl-ß, y-dihydroxypropyl ether In 100 ml of l-chloro-2,3-propanediol, to which 20 ml of water have been added, 46.8 g (0, 2 mol) 2-acetylamino-4-nitro-phenyl potassium salt entered. The mixture is then heated in a boiling water bath for 10 hours. 13.8 g (0.1 mol) of potassium carbonate are added and the mixture is heated for a further 6 h. After cooling, the mineral salts are removed by filtration. 250 ml of ethanol (96% by volume) are added to the filtrate and the mixture is cooled to 0 ° C. overnight. The desired product crystallizes out; it is suctioned off, washed with ethanol, then with 1N sodium hydroxide solution and then with water. After recrystallizing twice from ethanol and drying in vacuo at 55 ° C, the product melts at 142 ° C. -7-

AT 393 219 B

Analysis for Cj jH ^ NjOg: C H N O calculated: 48.89 5.22 1037 3532% found: 48.77 5.15 10.44 3532 - 35.46%

Second stage: Preparation of the chlorohydrate of (2-acetylamino4-amino) -phenyl-β, y-dihydroxypropyl ether 17 ml of ethanol (96% by volume) mixed with 2.5 ml of water, 0.4 g of ammonium chloride and 8 g of zinc powder are stirred on Heated to reflux. Then 1.33 × 10 * ^ mol (3.6 g) (2-acetylamino-4-nitro) phenyl-β, Y-dihydroxypropyl ether are added little by little with further stirring. When the addition is complete, the reaction mixture is decolorized; it is filtered off and the filtrate is taken up in 1.5 ml of ethanol (96% by volume) to which 1.5 ml of hydrochloric acid (36%) have been added, cooling using an ethanol / dry ice mixture. The desired product crystallizes in the form of the chlorohydrate in the cooled filtrate. It is suctioned off, washed with a little absolute ethanol, which has previously been cooled, and then dried at 55 ° C. in vacuo; Mp (decomposition): 228-230 ° C.

Analysis for CuHjg ^ O ^ HCl: C H N O CI calculated: 47.74 6.19 10.12 23.13 12.81% found: 47.86 636 10.16 23.08 12.90%

Third stage: Preparation of the dichlorohydrate of (2,4-diamino) phenyl-ß, y-dihydroxypropyl ether 54 g (0.195 mol) of the chlorohydrate of (2-acetylamino-4-amino) -phenyl-ß, y-dihydroxypropyl ether are in 270 ml of absolute ethanol, which had previously been saturated with hydrogen chloride gas and 54 ml of a 12N hydrochloric acid solution had been added. The reaction mixture is often heated to about 100 ° C with stirring 1. The desired dichlorohydrate, which is insoluble in the hot reaction mixture, is then suctioned off. The product is then washed with a little absolute ethanol saturated with hydrogen chloride gas and then with acetone. After drying in vacuo at 55 ° C, it melts with decomposition at 210 to 215 ° C.

Analysis for C ^ H J4N2O3.2HCI: C H N O CI calculated: 39.86 5.95 10.33 17.70 26.15% found: 39.96 6.04 1038 17.64 2633%

Regulation 3: Preparation of the dichlorohydrate of (2,4-diamino) -phenyl-ß - [(ß'-hydroxyethoxy) ethoxy] ethyl ether of the following formula: OCHCHOCH CHOCHCH OH | 2 2 2 2 2 2 -NH, [M *. 2HC1 NH,

First stage:

NHCOCHj NO,

KOH

OK NHCOCHj

NO 2 -8-

AT 393 219 B

Second stage: OK

+ cich2ch2och2ch2och2ch2oh - &gt;

Third stage: och2ch2och2ch2och2ch2oh

NHCOCH-NO. o OC ^ CHgOCHgCHgOCHgCHgOH NH-

+ Pd / C

NH-, 2HC1 HCl / XthanoX 2

First stage: Preparation of the potassium salt of 2-aminoacetyl-4-nitrophenol 2150 ml of ethanol, which contains 1.89 mol (133 g) of 80% potassium hydroxide dissolved, are cooled to -10 ° C. Then, while stirring, 1.89 mol (371 g) of 2-acetylamino-4-nitrophenol are added gradually, the temperature being kept below 5 ° C. The potassium salt precipitates. The product is filtered off, washed with ethanol and dried in vacuo at 50 ° C;

Mass (potentiometry): 226, theoretical. Value: 234.

Second step: Preparation of (2-acetylamino-4-nitro) phenyl-ß - [(ß'-hydroxyethoxy) ethoxy] ethyl ether 0.2 mol (46.85 g) of the potassium salt of 2-acetylamino-4-nitrophenol are added to 200 ml of dimethylformamide. 0.24 mol (40.5 g) of triethylene glycol monochlorohydrin (bp = 256-258 ° C.) are then added with stirring. The mixture is kept under stirring at a temperature of about 100 ° C. for 8 hours and then poured into 800 ml of ice water. The crude product is dried, washed with water, then with an ice-cooled n-soda solution and finally again with water. After drying in vacuo and recrystallization from ethanol, the expected product melts at 104 ° C.

Analysis for C14H20O7N2: C H N O calculated: 51.21 6.14 8.53 34.11% found: 51.33 6.19 8.49 33.96%

Third stage: Preparation of the dichlorohydrate of (2,4-diamino) -phenyl-ß - [(ß'-hydroxyethoxy) ethoxy) ethyl ether

16.4 g of 10% palladium-carbon and then 0.65 mol (66 ml) of cyclohexene are introduced into 160 ml of ethanol (96% by volume). With vigorous stirring, a suspension of 0.1 mol (32.83 g) of 2-acetylamino-4-nitro-phenyl-β- [ß'-hydroxy-ethoxy) -ethoxy] ethyl ether and 60 ml of ethanol (96% by volume) added. The mixture is heated under reflux under nitrogen for 2 h. The boiling reaction mixture is filtered and then 50 ml of 32% ethanolic hydrochloric acid are added to the filtrate. The dichlorohydrate formed is filtered off. Salt formation is accomplished by refluxing the 15.2 g of crude dichlorohydrate in 150 ml of 32% ethanolic hydrochloric acid for 3 hours. It is allowed to cool and then the salt is precipitated with 500 ml of ethyl ether -9-

AT 393 219 B

The product is filtered off, washed several times with ethyl ether and dried in vacuo at about 50 ° C; 7.8 g of this product are obtained with an mp = 156 ° C. (Kofler).

Analysis for ^ 2 ^ 22¾¾¾1 C H N O calculated: 43.78 6.73 8.51 19.44% found: 43.05 6.58 8.29 19.97%

Regulation 4: Preparation of the dichlorohydrate of (2,4-diamino) phenyl-3 '- (β-hydroxyethoxy) -2'-hydroxypropyl ether of the following formula:

• 2KC1

OK

NHCOCH, NO,

KOH

OH 1 ^ -NHCOCH,

First stage: ly N0o ·

Second stage: OK JL NHCOCH, V NOo

+ C1CH2CH0HCH20CH2CH20H - »HJ

0CH2CH0HCH20CH2CH20H NHCOCH, N02

Third step:

First stage: Preparation of the potassium salt of 2-acetylamino-4-nitrophenol 2150 ml of ethanol, which contains 1.89 mol (133 g) of 80% potassium hydroxide, are cooled to -10 ° C .; then 1.89 moles (371 g) of 2-acetylamino-4-nitro-phenol are gradually added with stirring, the temperature being kept below 5 ° C. The potassium salt precipitates. The product is filtered off, washed with ethanol and dried in vacuo at 50 ° C; -10-

AT 393 219 B

Mass (potentiometry): 226, theoretical. Value: 234.

Second Substance: Production of (2-acetylamino-4-mtro) -phenyl-3 '- (ß-hydroxyethoxy) -2'-hydroxypropyl ether 0.2 mol (46.85 g) of the potassium salt of 2-acetylamino4-nitrophenol are in 200 ml of dimethylformamide and 0.24 mol of 2-hydroxy-3-chloropropyl-2'-hydroxyethyl ether (bp = 110 oC / 0.53 mbar) (Ref .: Pretrow, Stephenson, J. Pharm. Pharmacol. 7 (1955), 198,200).

The mixture is kept under stirring at a temperature of about 100 ° C. for 8 hours and then poured into 800 ml of ice water. The precipitate is dried, washed with water, then with an ice-cooled n-soda solution and finally again with water. After drying in vacuo and recrystallization from acetonitrile, the expected product melts at 65 ° C.

Analysis calculated for C H N O: 49.68 5.77 8.91 35.63% found: 49.59 5.76 8.94 35.57%

Third stage: Production of the dichlorohydrate of (2,4-diamino) phenyl-3 '- (ß-hydroxyethoxy) -2’-hydroxy-propyl ether

3.2 g of 10% palladium-carbon and then 0.13 mol (13.2 ml) of cyclohexene are added to 32 ml of ethanol (96% by volume). A suspension of 0.02 mol (6.28 g) of 2-acetylamino-4-nitro-phenyl-3 '- (β-hydroxyethoxy) -2'-hydroxypropyl ether and 12 ml of ethanol is added with vigorous stirring. The mixture is heated under reflux for 3 h and then the boiling reaction mixture is filtered. The ethanolic filtrate is then mixed with 150 ml of ethanol and 17.4 ml of 32% ethanolic hydrochloric acid. The mixture is heated under reflux for 3 h, then concentrated to a volume of 75 ml and then precipitated with ethyl ether. The precipitate is dried and washed again with ethyl ether. The mixture is then dried in vacuo at room temperature for 48 h. A beige product with an mp = 207-210 ° C. (Kofler) is obtained.

Analysis for C j C H N O calculated: 41.92 6.39 8.89 22.50% found: 41.32 6.45 8.80 22.20%

Example 1:

A colorant of the following composition is produced:

Compound according to protocol 1 2.85 g p-phenylenediamine 1.08 g

Nonylphenol ethylenated with 4 moles of ethylene oxide 21 g

Nonylphenol ethylenated with 9 moles of ethylene oxide 24 g oleic acid 4 g 2-butoxyethanol 3 g ethanol (96% by volume) 10 g

Pentasodium salt of diethylenetriaminepentaacetic acid 2.5 g

Thioglycolic acid 0.6 g

Ammonia (d = 1.18 g / cnr) 10 g

Make up to 100 g with water

The pH of this product is 9.7.

At the time of application, 100 g of 6% hydrogen peroxide are added. This mixture is applied to 90% naturally blond hair and left to act for 25 min at 28 ° C. After rinsing and shampooing, a blue-black color is obtained. -11-

AT 393 219 B

Example 2:

A colorant of the following composition is produced:

Compound according to regulation 2 0.0067 g p-phenylenediamine 0.0027 g 2-butoxyethanol 8 g

Carboxymethyl cellulose 2 g

Ammonium lauryl sulfate 5 g

Ammonium acetate 1 g

Propylene glycol 8 g

Pentasodium salt of diethylene triamine pentaacetic acid 2 g

Thioglycolic acid 0.4 g

Ammonia (d = 1.18 g / cm ^) 5 g

Make up to 100 g with water

The pH of this product is 10.1.

At the time of application, 50 g of 6% hydrogen peroxide are added. This mixture is applied to decolorized hair and left to act at 28 ° C for 30 min. After rinsing and shampooing, you get a light silver tint with a blue shimmer.

Example 3:

A colorant of the following composition is produced:

Compound according to protocol 2 0.542 g p-aminophenol 0.218 g

Acrylic acid polymer (molecular weight 2 to 3 million) 14 g of ethanol 11 g of 2-butoxyethanol 5 g

Trimethylcetylammonium bromide 1 g of ethylenediaminetetraacetic acid 0.1 g

Ammonia (d = 1.18 g / cm ^) 10 g

Thioglycolic acid 0.2 g

Make up to 100 g with water

The pH of this agent is 10.2.

At the time of application, 80 g of 6% hydrogen peroxide are added. This mixture is applied to 90% naturally white hair and left to act at 28 ° C for 25 min. After rinsing and shampooing, a dark red color is obtained.

Example 4:

A colorant of the following composition is produced:

Compound according to instructions 1. 1.42 g p-aminophenol 045 g 2-butoxyethanol 8 g propylene glycol 8 g carboxymethyl cellulose 2 g ammonium lauryl sulfate 5 g pentasodium salt of diethylenetriaminepentaacetic acid 2 g thioglycolic acid 0.4 g ammonia (d = 1.18 g / cm ^) 10 g Make up to 100 g with water

The pH of this product is 10.

At the time of application, 100 g of 6% hydrogen peroxide are added. This mixture is applied to 90% naturally white hair and left to act at 25 ° C for 30 min. After rinsing and shampooing, a copper-red color is obtained. -12-

AT 393 219 B

Example 5:

A colorant of the following composition is produced;

Compound according to protocol 2 0.271 g of 4-N-β-methoxyethylamino-aniline dihydrocidoride 0.239 g of nonylphenol oxyethylenated with 4 moles of ethylene oxide 12 g of nonylphenol oxydized with 9 moles of ethylene oxide 15 g of oleyl oxide oxyethylenated with 2 moles of ethylene oxide U g with 4 moles of ethylene oxide g propylene glycol 6 g ethylenediaminetetraacetic acid 0.12 g ammonia (d = 1.18 gjm?) 11 g thioglycolic acid 0.6 g Make up to 100 g with water

The pH of this product is 10.4.

At the time of application, 100 g of 6% hydrogen peroxide are added. This mixture is applied to 90% naturally white hair and left to act at 25 ° C for 20 min. After rinsing and shampooing, you get a fresh, blue color.

Example 6:

A colorant of the following composition is produced:

Compound according to instructions 1 0.285 g of 2,6-dimethyl-p-phenylenediamine dihydrochloride 0.209 g of oleyl alcohol ethylenated with 2 moles of ethylene oxide 4.5 g of oleyl alcohol oxied with 4 moles of ethylene oxide 4.5 g of oleic acid amide oxidized with 12 moles of ethylene oxide 4.5 g of co-fatty acid diethanolamide 9 g propylene glycol 4 g 2-butoxyethanol 8 g ethanol (96% by volume) 6 g pentasodium salt of diethylenetriaminepentaacetic acid 2 g hydroquinone 0.15 g sodium bisulfite solution (d = 1.32 yaw?) U g ammonia (d = 1.18 yeast? ) 5 g Make up to 100 g with water

The pH of this product is 10.

At the time of application, 100 g of 6% hydrogen peroxide are added. This mixture is applied to previously discolored hair and left to act at 28 ° C for 30 min. After rinsing and shampooing, you get an intense blue color with a slight purple tinge.

Peispigl 7;

A colorant of the following composition is produced:

Compound according to instructions 1 0.012 g p-phenylenediamine 0.108 g 2,6-dimethyl-p-phenylenediamine dihydrochloride 0.0502 g p-aminophenol 0.155 g 2-methylresorcinol 0.19 g m-aminophenol 0.12 g 1-phenyl-3 -methyl-5-pyrazolone 0.09 g (3-N-methylamino-4-nitro) -phenoxyethanol 0.2 g with 4 mol of ethylene oxide nonylphenol 12 g with 9 mol of ethylene oxide nonylphenol 15 g with 2 mol of ethylene oxide oleylated with 2 mol of ethylene oxide g -13-

AT393 219 B 14 g 6 g 0.12 g 11 g 0.2 g 00 g

Oleyl alcohol ethylenated with 4 moles of ethylene oxide

Propylene glycol ethylenediaminetetraacetic acid

Ammonia (d = 1.18 g / cm ^)

Mercaptosuccinic acid

Fill up with water

The pH of this product is 10.4.

At the time of application, 75 g of 6% hydrogen peroxide are added. This mixture is applied to previously decolorized hair and left to act at 30 ° C for 25 min. After rinsing and shampooing, you get a golden-sand-colored tint.

Example 8:

A colorant of the following composition is produced: g g g g g g g g g g g g g g g g g g g g

Compound according to protocol 2 0.065 p-phenylenediamine 0.2 p-aminophenol 0.4 N-methyl-p-aminophenol sulfate 0.31 2-methylresorcinol 0.3 m-aminophenol 0.405 2-methyl-5-N-β-hydroxyethylamino -phenol 0.08 (3-N-methylamino-4-nitro) -phenoxyethanol 0.5

Oleyl alcohol 4.5 ethylenated with 2 moles of ethylene oxide

Oleyl alcohol 4.5, ethylenated with 4 moles of ethylene oxide

Oleylamine 4.5 ethylenated with 2 moles of ethylene oxide

Coconut fatty acid diethanoiamide 9

Propylene glycol 4 2-butoxyethanol 8 ethanol (96% by volume) 6

Pentasodium salt of diethylenetriaminepentaacetic acid 2

Hydroquinone 0.15

Sodium bisulfite solution (d = 1.32 g / crr?) 1.3

Ammonia (d = 1.18 g / cnP) 8

Make up to 100 with water

The pH of this agent is 10.5.

At the time of application, 80 g of 6% hydrogen peroxide are added. This mixture is applied to previously straw-blonde hair and left to act for 35 minutes. After rinsing and shampooing, you get a medium maroon color with copper shimmer.

Example 9:

A colorant of the following composition is produced:

Compound according to instructions 1,042 g p-phenylenediamine 0.6 g p-aminophenol 0.8 g 4-N, N-di-β-hydroxyethylamino-aniline dihydrochloride 1 g m-aminophenol 0.5 g resorcinol 144 g 3-itro -4-amino-phenol 0.6 g oleylated with 2 moles of ethylene oxide oleyl alcohol 4.5 g with oleylated with 4 moles of ethylene oxide oleyl alcohol 44 g with oleylamine oxied with 12 moles of ethylene oxide 44 g coconut fatty acid diethylamine 9 g propylene glycol 4 g 2-butoxyethanol 8 g -14-

AT 393 219 B ethanol (96% by volume) 6 g pentasodium salt of diethylenetriaminepentaacetic acid 2 g thioglycolic acid 03 g ammonia (d = 1.18 g / cm ^) 10 g Make up to 100 g with water

The pH of this product is 10.3.

At the time of application, 100 g of 6% hydrogen peroxide are added. This mixture is applied to dark blonde discolored hair and left to act at 28 ° C for 30 min. After rinsing and shampooing, a brown color is obtained.

Example 10:

A colorant of the following composition is produced:

/

Compound according to regulation 2 0.04 g p-phenylenediamine 0.955 g o-aminophenol 0.375 g resorcinol 0.09 g m-aminophenol 0.155 g 2-methyl-5-N-β-hydroxyethylaminophenol 1.12 g cetylstearyl alcohol 19 g 2-octyl dodecanol 43 g cetylstearyl alcohol ethylenated with 15 moles of ethylene oxide 23 g ammonium lauryl sulfate (30% active substance) 12 g

Polymer consisting of recurring units of the formula: 4 g 2 g 11 g 1 g 13 g 100 g

Benzyl alcohol

Ammonia (d = 1.18 g / cm ^) ethylenediaminetetraacetic acid

Sodium bisulfite solution (d = 1.32 g / cm ^)

Fill up with water

The pH of this agent is 10.2.

At the time of application, 100 g of 6% hydrogen peroxide are added. This mixture is applied to straw-colored hair and left to act for 20 minutes at 25 ° C. After rinsing and shampooing, a dark purple color is obtained.

Example 11:

A colorant of the following composition is produced:

Compound according to instructions 1 0.1 g p-phenylenediamine 031 g -15 AT393 219 B p-aminophenol 0.4 g 4-N-methylaminophenol sulfate 0.4 g resorcinol 0.5 g m-aminophenol 03 g 2 -Methyl-5-N-ß-hydroxyethylamino-phenol 0.41 g 2-isopropyl-6-nitro-aniline 0.81 g cetylstearyl alcohol 8 g sodium cetylstearyl sulfate 03 g oxyethylenated castor oil 1 g oleic acid diethyl amide 13 g pentasodium salt of diethylenetriamine pentamino pentamino pentadiol 03 g hydroquinone 0.15 g ammonia (d = 1.18 g / cm ^) 11 g make up to 100 g with water. The pH of this product is 10.4.

100 g of 6% hydrogen peroxide are added at the time of application. This mixture is applied to decolorized hair and left to act for 30 minutes at 30 ° C. After rinsing and shampooing, you get a medium brown color with a copper sheen.

Example 12:

A colorant of the following composition is produced: 0.0143 g 0.0120 g 13 g 11 g 5 g 1 g 0.1 g 10 g 03 g 100 g

Compound according to instructions 1 4-N-ß-methoxyethylamino-aniline dihydrochloride acrylic acid polymer (molecular weight 2 to 3 million) ethanol (96% by volume) 2-butoxyethanol

Trimethylcetylammonium bromide ethylenediaminetetraacetic acid ammonia (d = 1.18 g / cm ^)

Thioglycolic acid Make up to water The pH of this product is 10.2.

At the time of application, 20 g of 6% hydrogen peroxide are added. This mixture is applied to decolorized hair and left to act for 30 minutes at 30 ° C. After rinsing and shampooing, you get a turquoise blue color with silver shimmer.

Example 13:

A colorant of the following composition is produced: 0.055 g 0.058 g 03 g 0.4 g 0.103 g 0.05 g 031 g 12 g 15 g 13 g 13 g 6 g 13 g 0.12 g

Compound according to regulation 1 p-phenylenediamine p-aminophenol

Resorcinol m-aminophenol 2-methyl-5-N-ß-hydroxyethylamino-phenol 3-nitro-4-N-methylamino-N, N-di-ß-hydroxy-äthylanilin Oxygenated nonylphenol with 4 moles of ethylene oxide Oxygenated nonylphenol with 9 moles of ethylene oxide Oleylated with 2 moles of ethylene oxide oleylated with 4 moles of ethylene oxide propylene glycol

Sodium bisulfite solution (d = 132 g / cnr) ethylenediaminetetraacetic acid -16-

AT393 219 B

Triethanolamine until a pH of 8.5 is reached

Make up to 100 g with water

At the time of application, 70 g of 6% hydrogen peroxide are added. This mixture is applied to decolorized hair and left to act at 28 ° C. for 25 minutes. After rinsing and shampooing, a hazelnut brown color is obtained.

Example 14:

A colorant of the following composition is produced: 1.3 g 1.81 g 0.8 g 0.2 g 0.803 g 0.81 g 0.9 g 21 g 24 g 4 g 3 g 10 g 2.5 g 0, 6 g 10 g 100 g

Compound according to instructions 1 p-phenylenediamine p-aminophenol (2,4-diamino) -phenoxyethanol dihydrochloride 2-methyl-5-N-ß-hydroxyethylamino-phenol resorcinol m-aminophenol

Nonylphenol ethylenated with 4 moles of ethylene oxide Nonylphenol oxied with 9 moles of ethylene oxide oleic acid 2-butoxyethanol ethanol (96% by volume)

Pentasodium salt of diethylenetriaminepentaacetic acid thioglycolic acid ammonia (d = 1.18 g / cm3)

Top up with water. The pH of this product is 9.5.

At the time of application, 120 g of 6% hydrogen peroxide are added. This mixture is applied to straw-colored hair and left to act at 28 ° C for 25 min. After rinsing and shampooing, a raven black color is obtained.

Example 15:

A colorant of the following composition is produced:

Compound according to instructions 1 0.252 g 4-N-β-methoxyethylamino-anihn-dihydrochloride 0.6 g 2,6-dimethyl-p-phenylenediamine dihydrochloride 02 g p-aminophenol 0.6 g resorcinol 0.905 g m-aminophenol 0.435 g 2 -Methyl-5-N-ß-hydroxyethylamino-phenol 0.2 g 6-hydroxy-benzomorphoUn 0.435 g 2-methyl-4-amino-5-nitro-phenol 0.703 g nonylphenol 12 g with 4 moles of ethylene oxide with 9 moles of ethylene oxide oxyethylenated nonylphenol 15 g with 2 moles of ethylene oxide oleylated with oleyl alcohol 14 g with 4 moles of ethylene oxide with oleylated with oleylene oxide 14 g propylene glycol 6 g ethylenediaminetetraacetic acid 0.12 g ammonia (d = 1.18 g / cm3) 11 g thiglycolic acid 0.6 g Make up with water 100 g

The pH of this product is 9.9. -17-

AT 393 219 B

At the time of application, 100 g of 6% hydrogen peroxide are added. This mixture is applied to 90% naturally white hair and left at 30 ° C for 30 minutes. After rinsing and shampooing, you get a light chestnut brown with a copper sheen.

Example 16:

A colorant of the following composition is produced:

Compound according to instructions 1,0306 g of p-phenylenediamine 0307 g of 4-N-β-methoxyethylamino-aniline dihydrochloride 0.15 g of 2-methyl-resorcinol 0.405 g of 2-methyl-5-N-β-hydroxyethylamino-phenol 0.115 g (2nd , 4-diamino) -phenoxyethanol-dihydrochloride 0.106 g 2-amino-3-nitro-phenol 0303 g cetylstearyl alcohol 8 g sodium cetylstearyl sulfate 03 g oxyethylenated castor oil 1 g oleic acid diethanoiamide 13 g pentasodium salt of diethylenetriamine pentanoic acid thioglythanoic acid thioglyne acetic acid (d = 1.18 g / cm ^) 11 g Make up to 100 g with water

The pH of this product is 103-

At the time of application, 90 g of 6% hydrogen peroxide are added. This mixture is applied to 90% naturally white hair and left to act at 25 ° C for 25 min. After rinsing and shampooing, an anthracite gray color is obtained.

Example 17:

A colorant of the following composition is produced:

Compound according to regulation 2 13 g Compound according to regulation 1 0.42 g p-phenylenediamine 0.62 g 4-NN-di-ß-hydroxyethylamino-aniline dihydrochloride 0.42 g p-aminophenol 0.705 g resorcinol 0.81 g 2- Methyl 5-N-ß-hydroxyethylamino-phenol 031 g 2-amino-3-nitro-phenol 0.61 g cetylstearyl alcohol 8 g sodium cetylstearyl sulfate 03 g oxyethylenated castor oil 1 g oleic acid diethyl amide 13 g pentasodium salt of diethylene triamine pentacetic acid 23 g 15 g ammonia (d = 1.18 g / cnr *) 11 g Make up to 100 g with water

The pH of this product is 10.1.

At the time of application, 100 g of 6% hydrogen peroxide are added. This mixture is applied to 90% naturally white hair and left to act at 28 ° C for 20 min. After rinsing and shampooing, you get a very dark brown color. -18-

Claims (8)

AT393 219 B Example 18: A colorant of the following composition is prepared: Compound according to specification 3 0.496 g p-aminophenol 0.218 g butyl glycol 5 g 5 g ammonia oxyethylenated with 10.5 mol ethylene oxide (d = 1.18 g / cm ^) 6 g Make up to 100 g with water. The pH of this product is 10.3. At the time of application, 25 g of 6% hydrogen peroxide are added. This mixture is applied to 90% naturally white hair and left to act at 25 ° C for 15 min. After rinsing and shampooing, a rosewood-colored color is obtained. Example 19: A colorant of the following composition is produced: Compound according to instruction 4 1.57 g p-aminophenol 0.55 g 2. Composition according to claim 1, characterized in that it as a coupler at least one m-phenylenediamine of the general formula (I) of the general definition given in claim 1, in which Z represents an alkyl group which is interrupted by at least one oxygen atom, or at least contains one of its acid addition salts 2-butoxyethanol 8 g propylene glycol 8 g carboxymethyl cellulose 2 g ammonium lauryl sulfate 5 g pentasodium salt of diethylenetriaminepentaacetic acid 2 g thioglycolic acid 0.4 g ammonia (d = 1.18 g / cnr) 10 g Make up to 100 g with water The pH of this product is 9.8. At the time of application, 100 g of 6% hydrogen peroxide are added. This mixture is applied to 90% naturally white hair and left to act for 30 minutes at room temperature. After rinsing and shampooing, a durable rosewood coloration is obtained. PATENT CLAIMS 1. Colorants for keratin fibers, especially for hair, in the form of a cosmetic preparation, e.g. B. in the form of a liquid, a cream, a gel or an aerosol, consisting of a cosmetic carrier material which, in addition to water, has at least one oxidation base selected from p-phenylenediamines, p-aminophenols and heterocyclic bases and, if appropriate, further cosmetic adjuvants, such as alkalizing agents Acidifying agents, surfactants, organic solvents, thickeners, antioxidants, penetrants, film-forming agents, foaming agents, sequestering agents, care agents and fragrances, characterized in that it contains 0.001 to 2.85% by weight, based on the total weight of the agent, as a coupler at least one m-phenylenediamine of the general formula OZ, (D nh2 nh2 -19- AT 393 219 B in which Z is either a polyhydroxyalkyl group whose alkyl group contains 3 to 6 carbon atoms, this polyhydroxyalkyl group having 2 hydroxyl groups, or an alkyl group with 4 represents up to 8 carbon atoms, which are defined by mi at least one oxygen atom is interrupted and has at least one hydroxyl group, said hydroxyl group (s) being (are) bound to a carbon atom which has no further oxygen bond, or at least one of its addition salts and, if appropriate, at least one further coupler, optionally at least one compound selected from o-diphenol, o-phenylenediamine or o-aminophenol, which can optionally be substituted on the ring or the amine functions, and also optionally at least one dye precursor of the benzene or naphthalene series, further optionally at least one direct dye and further optionally contains at least one indoaniline, indophenol or indamine leuco derivative and has a pH of 8 to 11.5. 3. Composition according to claim 1, characterized in that it as a coupler at least one m-phenylenediamine of the general formula (I) of the general definition given in claim 1, in which Z is a ß- (ß'-hydroxyethoxy) -ethyl- or one ß - [(ß'-Hydroxyäthoxy) -ethoxy] -ethyl means or contains at least one of its acid addition salts. 4. Composition according to claim 1, characterized in that it as a coupler at least one m-phenylenediamine of the general formula (I) of the general definition given in claim 1, in which Z is a β, γ-dihydroxypropyl or a 3 '- (ß -Hydroxyäthoxy) -2'-hydroxypropylrest means or contains at least one of its acid addition salts 5. Composition according to one of claims 1 to 4, characterized in that the m-phenylenediamine of the general formula (I) of the general definition given in claim 1 in an amount of 0.001 to 2.5 wt .-%, based on the total weight of the agent is included. 6. Composition according to one of claims 1 to 5, characterized in that the further coupler optionally present is selected from the following: resorcinol, 2-methylresorcinol, m-aminophenol, 2-methyl-5-amino-phenol, 2-methyl N- (ß-hydroxyethyl) -5-amino-phenol, 6-hydroxybenzomorpholine, 2,6-dimethyl-3-acetyl-amino-phenol, 2-methyl-5-carbäthoxyamino-phenol, 2-methoxy-carbäthoxy-5- aminophenol, 2-methyl-5-ureidophenol and l-phenyl-3-methyl-5-pyrazolone. 7. Agent according to one of claims 1 to 6, characterized in that the dye precursor of the benzene series optionally present on the ring is substituted by at least three substituents selected from hydroxyl, methoxy or amino groups. 8. A process for dyeing keratin fibers, in particular hair, using an agent according to any one of claims 1 to 7, characterized in that this agent is mixed with the oxidizing agent such as hydrogen peroxide, urea peroxide or persalts immediately before use, the mixture thus obtained brings on the fibers or hair, and allows to act for a period of 5 to 45 min, then rinsed, optionally shampooed and rinsed again and then the fibers or hair dries. -20-