NO151570B

NO151570B - HAARFARGEMIDDEL.

Info

Publication number: NO151570B
Application number: NO813882A
Authority: NO
Inventors: David Rose; Norbert Maak
Original assignee: Henkel Kgaa
Priority date: 1980-12-13
Filing date: 1981-11-16
Publication date: 1985-01-21
Also published as: FI71875B; DK506081A; NO151570C; FI813621L; EP0055386A2; NO813882L; EP0055386A3; EP0055386B1; ATE9545T1; DE3166359D1; FI71875C; JPS57126411A; DE3047105A1

Abstract

1. Claims (for the Contracting States : BE, CH, DE, FR, GB, IT, LI, LU, NL, SE) Hair dyes based on oxidation dyes, characterized by a content of hydroxyalkylated alkylamino-p-phenylene diamines corresponding to the following general formula see diagramm : EP0055386,P6,F2 in which n is a number of from 2 to 4, R1 and R2 represent hydrogen or a C2 -C6 mono- or polyhydroxyalkyl radical with the proviso that at least one of the radicals R1 or R2 is a mono- or polyhydroxyalkyl radical, and inorganic or organic salts thereof as developer components and the coupler substances normally used in oxidation hair dyes. 1. Claims (for the Contracting State AT) Hair dyes based on oxidation dyes, characterized by a content of hydroxyalkylated alkylamino-p-phenylene diamines corresponding to the following general formula see diagramm : EP0055386,P7,F1 in which n is a number of from 2 to 4, R1 and R2 represent hydrogen or a C2 -C6 mono- or polyhydroxyalkyl radical, with the proviso that at least one of the radicals R1 or R2 is a mono- or polyhydroxyalkyl radical, and inorganic or organic salts thereof as developer components and the coupler substances normally used in oxidation hair dyes.

Description

Oppfinnelsens gjenstand er middel til oksydativ fargning av hår på basis av hydroksyalkylert alkylamino-p-fenylendiaminer som fremkallérkomponenter. The object of the invention is a means for oxidative coloring of hair based on hydroxyalkylated alkylamino-p-phenylenediamines as developer components.

For farging av hår spiller de såkalte oksydasjonsfarger som oppstår ved oksydativ kopling av en fremkallerkomponent med en koplingskomponent en foretrukket rolle pga. deres intense farger og meget gode ekthetsegenskaper. Som fremkallerstoffer anvendes vanligvis nitrogenbaser som p-fenylendiaminderivater, diaminpyridiner, 4-amino-pyrazolon-derivater, heterocykliske hydrazoner. Som såkalte koplerkomponenter nevnes m-fenylen-diamin-derivater, fenoler, naftoler, resorcinderivater og pyrazoloner. For coloring hair, the so-called oxidation colors that arise from oxidative coupling of a developer component with a coupling component play a preferred role because their intense colors and very good authenticity properties. Nitrogen bases such as p-phenylenediamine derivatives, diaminepyridines, 4-amino-pyrazolone derivatives, heterocyclic hydrazones are usually used as developers. As so-called coupling components, m-phenylene-diamine derivatives, phenols, naphthols, resorcin derivatives and pyrazolones are mentioned.

I US-patent 3.726.635 omtales nitro-p-fenylendiaminderivater. Disse stoffer er direkt-fargende fargestoffer som frembringer fargninger på hår uten oksydativ fremkalling. De adskiller seg såvel ved deres struktur som også deres fargetekniske egenskaper betraktelig fra de ikke med nitrogruppe substi-tuerte fremkallerstoffer ifølge oppfinnelsen. US patent 3,726,635 mentions nitro-p-phenylenediamine derivatives. These substances are direct-dyeing dyes that produce coloring on hair without oxidative development. They differ considerably in terms of their structure as well as their color technical properties from the developer substances according to the invention which are not substituted with a nitro group.

Fra DAS 19 45 451 er det kjent N-(«>-ureidoalkyl)-p-f enylen-diaminderivater. Fra dette utlegningsskrift kan det ikke trekkes slutninger til egenskapen av N-(p-aminofenyl)-N•,N<1->bis(g-hydroksyetyl)-1,3-diaminopropan som fremkaller for hår-fargemidler. From DAS 19 45 451 N-(«>-ureidoalkyl)-p-phenylene diamine derivatives are known. No conclusions can be drawn from this explanatory document as to the property of N-(p-aminophenyl)-N•,N<1->bis(g-hydroxyethyl)-1,3-diaminopropane as a developer for hair dyes.

Gode oksydasjonshårfargestoffkomponenter må i første rekke oppfylle følgende forutsetninger: De må ved den oksydative kopling med den eventuelle fremkaller- resp. koplerkomponent danne de ønskede farge- Good oxidation hair dye components must primarily fulfill the following requirements: They must, by the oxidative coupling with the possible developer or coupler component form the desired color-

nyanser i tilstrekkelig intensitet. De må videre ha en tilstrekkelig til meget god opptrekningsevne på menneskelig hår, og de skal dessuten i toksikologisk og dermatologisk henseende være ufarlige. shades of sufficient intensity. They must also have a sufficient to very good ability to attract human hair, and they must also be harmless from a toxicological and dermatological point of view.

De vanligvis anvendte forbindelseskiasser av de substitu- The commonly used compound types of the substituted

erte resp. usubstituerte p-fenylendiaminer som fremkallerstoffer, har den ulempe at de ved en rekke av personer frembringer sensibiliseringer. og som resultat herav, sterke aller-gier. De for unngåelse av disse dermatologiske ulemper i nyere tid foreslåtte fremkallerstoffer, har ikke fullt til-fredsstillende anvendelsestekniske egenskaper. teasing or unsubstituted p-phenylenediamines as developing substances have the disadvantage that they produce sensitizations in a number of people. and as a result, severe allergies. The developer substances proposed in recent times to avoid these dermatological disadvantages do not have fully satisfactory application technical properties.

Det besto derfor ved søkning etter brukbare oksydasjons-hårfargestoffer den oppgave å finne egnede komponenter som oppfyller overnevnte forutsetninger på optimal måte. Therefore, when searching for usable oxidation hair dyes, the task was to find suitable components that fulfill the above-mentioned prerequisites in an optimal way.

Oppfinnelsen vedrører hårfargemiddel på basis av oksydasjonsfargestoffer med et innhold av fremkallerkomponent, og de i oksydasjonshårfarger vanlige koblerstoffer, samt eventuelt vanlige direktfargende fargestoffer, karakterisert ved et innhold av N-(p-aminofenyl)-N<1>,N<1->bis-(B-hydroksyetyl)-1,3-di-aminpropan, og dets uorganiske eller organiske salter som fremkallerkomponenter. The invention relates to hair dyes based on oxidation dyes with a developer component content, and the coupling agents common in oxidation hair dyes, as well as possibly common direct coloring dyes, characterized by a content of N-(p-aminophenyl)-N<1>,N<1->bis -(B-hydroxyethyl)-1,3-di-aminopropane, and its inorganic or organic salts as developer components.

Ved deres anvendelse som fremkallerkomponenter kombinert med de for oksydasjonshårfargdnger vanligvis anvendte koplerstoffer fåes de forskjelligste meget intense fargetoner og er således en vesentlig berikelse av den oksydative hårfargemulighet. Dessuten utmerker de hydroksyalkylerte alkylamino-p-fenylendiaminer seg ved meget gode ekthetsegenskaper av de hermed oppnådde fargninger, og utmerker seg ved en god opp-løselighet i vann, en god lagringsstabilitet og toksikologisk samt dermatologisk ufarlighet. When they are used as developer components combined with the coupling substances usually used for oxidative hair dyes, a wide variety of very intense color tones are obtained and are thus a significant enrichment of the oxidative hair dye option. In addition, the hydroxyalkylated alkylamino-p-phenylenediamines are distinguished by very good authenticity properties of the colorings obtained thereby, and are distinguished by good solubility in water, good storage stability and toxicological and dermatological harmlessness.

De som fremkallerkomponenter anvendbare hydroksyalkylert alkylamino-p-fenylendiaminer kan enten anvendes som sådanne eller i form av deres salter med uorganiske eller organiske syrer, som f. eks. som klorider, sulfater, acetater, propionater, lactater, citrater. The hydroxyalkylated alkylamino-p-phenylenediamines that can be used as developer components can either be used as such or in the form of their salts with inorganic or organic acids, such as e.g. such as chlorides, sulfates, acetates, propionates, lactates, citrates.

Fremstillingen av de i hårfargemidlene ifølge oppfinnelsen The production of those in the hair dyes according to the invention

som fremkallerkomponenter anvendte hydroksyalkylerte alkyl-ert alkylamino-p-fenylendiaminer kan foregå etter generelt kjente fremgangsmåter for organisk syntese. I første trinn omsettes et N-acetylert alkylendiamin med den generelle formel hydroxyalkylated alkylated alkylamino-p-phenylenediamines used as developer components can proceed according to generally known methods for organic synthesis. In the first step, an N-acetylated alkylenediamine with the general formula is reacted

hvori n har overnevnte betydning med et brom-hydroksyalkan. Etter avspaltning av acetylgruppen fra omsetningsproduktet med saltsyre omsettes det dannede hydroksyalkylerte alkylendiamin med p-fluor- nitrobenzen til N-(p-nitrofenyl)-N<1->hydroksyalkylaminoalkan som deretter hydrogeneres til hydroksyalkylert alkylamino-p-fenylendiamin katalytisk. Fremstillingen foregår derved eksempelvis etter følgende skjema, idet n og R, har overnevnte betydning. wherein n has the above meaning with a bromo-hydroxyalkane. After cleavage of the acetyl group from the reaction product with hydrochloric acid, the hydroxyalkylated alkylenediamine formed is converted with p-fluoronitrobenzene to N-(p-nitrophenyl)-N<1->hydroxyalkylaminoalkane which is then catalytically hydrogenated to hydroxyalkylated alkylamino-p-phenylenediamine. The production thereby takes place, for example, according to the following scheme, with n and R having the above meaning.

Som utgangsmateriale for første trinn kan det tjene følgende acetylerte diaminer: etylendiamin, 1,3-diaminopropan, 1,4-diaminobutan. Som eksempel for brom-hydroksyalkaner som kan omsettes med de acetylerte alkylendiaminer er det å nevne l-brometariol-2, l-brompropanol-3, l-brombutanol-2, 3-brom-buta-nol-2, 4-brompentanol-l, 3-bromheksanol-2, 2-brompropan-diol-1,2, 4-brom-2-metyl-butandiol-2,3, 2-metyl-2-brometyl-propandiol-1,3. The following acetylated diamines can serve as starting material for the first step: ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane. Examples of bromo-hydroxyalkanes that can be reacted with the acetylated alkylenediamines are l-bromometariol-2, l-bromopropanol-3, l-bromobutanol-2, 3-bromo-butanol-2, 4-bromopentanol-1 , 3-bromohexanol-2, 2-bromopropane-diol-1,2, 4-bromo-2-methyl-butanediol-2,3, 2-methyl-2-bromomethyl-propanediol-1,3.

Som hårfargemidlene ifølge oppfinnelsen anvendbare hydroksyalkylerte alkylamino-p-fenylendiaminer er det eksempelvis å anføre N-(p-aminofenyl)-N'-(B-hydroksyetyl)-1,2-diaminoetan, N *,N'-bis-(B-hydroksyetyl)-1,2, -diaminoetan, -N1 - (B - hydroksyetyl)-1,3-diaminopropan, -N',N'-bis (B-hydroksyetyl)-1,3-diaminopropan, -N'-(B-hydroksyetyl)-1,4-diaminobutan, -N<1>,N<*->bis-(B-hydroksyetyl)-1,4-diaminobutan, -N1 -(3-hydroksy-propyl)-1,2-diaminoetan,-N<1>,N<1->bis-(3-hydroksypropyl)-1,2-diaminoetan, -N<*->(3-hydroksypropyl)-1,3-diaminopropan, -N',N'-bis-(3-hydroksypropyl)-1,3-diaminopropan, -N' ,N'-bis-(3-hydroksypropyl)-1,4-diaminobutan, -N<*>,N'-bis-(hydroksybutyl)-1,2-diaminoetan, -N'-(2-hydroksybutyl)-1,3-diaminopropan, -N'-(1,2-dihydroksypropy1)-1,2-diaminoetan, -N',N<1->bis-(1,2-di-hydroksypropyl)-1,2-diaminoetan, -N',N<*->bis-(1,2-dihydroksy-propyl)-1,3-diaminopropan, -N',N'-bis-(2-metyl-2,3-dihydroksy-butyl)-1,2-diaminoetan, -N',N'-bis-(2-metyl-2,3-dihydroksy-butyl)-1,3-diaminopropan. As the hair dye agents according to the invention usable hydroxyalkylated alkylamino-p-phenylenediamines, examples include N-(p-aminophenyl)-N'-(B-hydroxyethyl)-1,2-diaminoethane, N *,N'-bis-(B- hydroxyethyl)-1,2, -diaminoethane, -N1 - (B - hydroxyethyl)-1,3-diaminopropane, -N',N'-bis (B-hydroxyethyl)-1,3-diaminopropane, -N'-( B-hydroxyethyl)-1,4-diaminobutane, -N<1>,N<*->bis-(B-hydroxyethyl)-1,4-diaminobutane, -N1 -(3-hydroxy-propyl)-1,2 -diaminoethane,-N<1>,N<1->bis-(3-hydroxypropyl)-1,2-diaminoethane, -N<*->(3-hydroxypropyl)-1,3-diaminopropane, -N', N'-bis-(3-hydroxypropyl)-1,3-diaminopropane, -N' ,N'-bis-(3-hydroxypropyl)-1,4-diaminobutane, -N<*>,N'-bis-( hydroxybutyl)-1,2-diaminoethane, -N'-(2-hydroxybutyl)-1,3-diaminopropane, -N'-(1,2-dihydroxypropyl)-1,2-diaminoethane, -N',N<1 ->bis-(1,2-dihydroxypropyl)-1,2-diaminoethane, -N',N<*->bis-(1,2-dihydroxypropyl)-1,3-diaminopropane, -N' ,N'-bis-(2-methyl-2,3-dihydroxy-butyl)-1,2-diaminoethane, -N',N'-bis-(2-methyl-2,3-dihydroxy-butyl)-1 ,3-diaminopropane .

Blant de i hårfargemidlene ifølge oppfinnelsen som frem-kal lerkomponenter tilkommer N-(p-aminofenyl)-N•,N'-bis-(B - hydroksyetyl)-1,3-diaminopropan den største betydning såvel for den fagmessige kvalitet som også deres øvrige anvendelsestekniske egenskap. Among the developing components in the hair dyes according to the invention, N-(p-aminophenyl)-N•,N'-bis-(B-hydroxyethyl)-1,3-diaminopropane has the greatest importance both for the professional quality and also for their other application technical properties.

Som eksempler for i hårfargemidlene ifølge oppfinnelsen anvendte koplerkomponenter er det å anføre a-naftol, o-kresol, m-kresol, 2,6-dimetylfenol, 2,5-dimetylfenol, 3,4-dimetylfenol, 3,4-dimetylfenol, 3,5-dimetylfenol, pyrocatechin, pyrogallol, 1,5-resp. 1,7-dihydroksy-naftalin, 5-amino-3- metylfenol, hydrokinon, 2,4-diamino-anisol, m-toluylen-diamin, 4-aminofenol, resorcin, resorcinmonometyleter, m-fenylendiamin, 1-fenyl-3-metyl-pyrazolon-5, l-fenyl-3-amino-pyrazolon-5, 1-fenyl-3,5-diketo-pyrazolidin, l-metyl-7-dimetyl-amino-4-hydroksykinolon-2, l-amino-3-acetyl-acetamino-4- nitro-benzen eller l-amino-3-cyanacetyl-l-amino-4-nitrobenzen. Examples of coupling components used in the hair dyes according to the invention are a-naphthol, o-cresol, m-cresol, 2,6-dimethylphenol, 2,5-dimethylphenol, 3,4-dimethylphenol, 3,4-dimethylphenol, 3 ,5-dimethylphenol, pyrocatechin, pyrogallol, 1,5-resp. 1,7-dihydroxy-naphthalene, 5-amino-3-methylphenol, hydroquinone, 2,4-diamino-anisole, m-toluylene-diamine, 4-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 1-phenyl-3- methyl-pyrazolone-5, l-phenyl-3-amino-pyrazolone-5, 1-phenyl-3,5-diketo-pyrazolidine, l-methyl-7-dimethyl-amino-4-hydroxyquinolone-2, l-amino- 3-acetyl-acetamino-4-nitro-benzene or 1-amino-3-cyanoacetyl-1-amino-4-nitrobenzene.

I hårfargemidlene ifølge oppfinnelsen anvendes fremkallerkomponentene vanligvis i omtrent molare mengder referert til de anvendte koplerstoffer. Selvom den molare anvendelse viser seg hensiktsmessig så er det imidlertid ikke uheldig når frem-kal ler komponentene kommer til anvendelse i et visst over eller underskudd. In the hair dyes according to the invention, the developer components are usually used in approximately molar amounts with reference to the couplers used. Although the molar application proves appropriate, it is not unfortunate when the developer components are used in a certain excess or deficit.

Det er videre ikke nødvendig at fremkallerkomponentene og koplerstoffene er enhetlig produkter, men såvel fremkallerkomponentene kan være blandinger av de hydroksyalkylerte alkylamino-p-fenylendiaminer som også koplerstoffet kan være blandinger av overnevnte koplerkomponenter. Furthermore, it is not necessary that the developer components and the coupling substances are uniform products, but the developer components can also be mixtures of the hydroxyalkylated alkylamino-p-phenylenediamines, and the coupling substance can also be mixtures of the above-mentioned coupling components.

Dessuten kan hårfargemidlene ifølge oppfinnelsen inneholde In addition, the hair dyes according to the invention may contain

andre kjente og vanlige fremkallerkomponenter samt også eventuelt vanlige direktfargende fargestoffer i blanding, other known and common developer components as well as possibly also common direct coloring dyes in a mixture,

hvis dette er nødvendig til oppnåelse av visse fargenyanser. if this is necessary to achieve certain color shades.

Den oksydative kopling, dvs. fremkallingen av fargningen The oxidative coupling, i.e. the development of the colouration

kan prinsipielt foregå som ved andre oksydasjonshårfarge-midler, også ved hjelp av luftoksygen. Hensiktsmessig anvendes imidlertid kjemiske oksydasjonsmidler. Som slike kommer det spesielt på tale hydrogenperokfeyd eller dets tilleiringsprodukter til urinstoff, melamin eller natriumborat, samt blandinger av slike hydrogenperoksydtilleiringsforbindel-ser med kaliijmperoksyddisulfåt. can in principle take place as with other oxidation hair dyes, also with the help of atmospheric oxygen. However, chemical oxidizing agents are used appropriately. As such, hydrogen peroxide or its addition products to urea, melamine or sodium borate, as well as mixtures of such hydrogen peroxide addition compounds with potassium peroxide disulphate are particularly relevant.

Hårfargemidlene ifølge oppfinnelsen innarbeides for anvend- The hair dyes according to the invention are incorporated for use

else i tilsvarende kosmetiske tilberedninger som kremer, emulsjoner, geler eller også enkle oppløsninger og blandes umiddelbart før anvendelse på håret med et av de nevnte oksydasjonsmidler. Konsentrasjonen av slike fargetilbered-ninger av kopler-fremkallerkombinasjoner utgjør 0,2 til 5 vekt-%, fortrinnsvis 1—3 vekt-%. For fremstilling av kremer, else in corresponding cosmetic preparations such as creams, emulsions, gels or also simple solutions and mixed immediately before application to the hair with one of the aforementioned oxidizing agents. The concentration of such color preparations of coupler-developer combinations amounts to 0.2 to 5% by weight, preferably 1-3% by weight. For the production of creams,

emulsjoner eller geler blandes fargestoffkomponentene med de for slike preparater vanlige ytterligere bestanddeler. emulsions or gels, the dye components are mixed with the additional components usual for such preparations.

Som slike ekstra bestanddeler er det f. eks. å nevne fukte-eller emulgeringsmidler av anionisk eller ikke-ionogen type som alkalibenzylsulfonater, fettalkoholsulfater, alkyl-sulfonater, fettsyrealkanolamider, tilleiringsprodukter av etylenoksyd til fettalkoholer, fortykningsmidler som metyl-cellulose, stivelse, høyere fettalkohol, parafinolje, fett-syrer, videre parfymeolje og hårpleiemidler, som pantoten- As such additional components, there are e.g. to mention wetting or emulsifying agents of anionic or non-ionic type such as alkali benzyl sulphonates, fatty alcohol sulphates, alkyl sulphonates, fatty acid alkanolamides, addition products of ethylene oxide to fatty alcohols, thickeners such as methyl cellulose, starch, higher fatty alcohol, paraffin oil, fatty acids, further perfume oil and hair care products, such as pantothenic

syre og kolestrol. De nevnte tilsetningsstoffer anvendes derved i de for disse formål vanlige mengder, som f. eks. acid and cholesterol. The aforementioned additives are thereby used in the usual amounts for these purposes, such as e.g.

fukte- og emulgeringsmidler i konsentrasjoner på 0,5 - 30 vekt-% og fortykningsmiddel i konsentrasjoner på 0,1 til 25 vekt-%, hver gang referert til den samlede tilberedning. wetting and emulsifying agents in concentrations of 0.5 - 30% by weight and thickening agents in concentrations of 0.1 to 25% by weight, each time referring to the overall preparation.

Anvendelsen av hårfargemidlene ifølge oppfinnelsen kan uav-hengig av om det dreier seg om en oppløsning eller en emulsjon, en krem- eller en gel, foregå i svakt surt, nøytralt eller spesielt alkalisk miljø med en pH-verdi på 8 - 10. Anvendelsestemperaturene beveger seg derved i området fra 15 - 4 0°C. Etter en innvirkningsvarighet på ca. 30 minutter fjernes hårfargemiddelet fra håret som skal farges ved skylling. Deretter ettervaskes håret med en mild shampoo og tørkes. The use of the hair dyes according to the invention can, regardless of whether it is a solution or an emulsion, a cream or a gel, take place in a slightly acidic, neutral or particularly alkaline environment with a pH value of 8 - 10. The application temperatures vary thereby in the range from 15 - 4 0°C. After an impact duration of approx. After 30 minutes, the hair dye is removed from the hair to be dyed by rinsing. The hair is then washed with a mild shampoo and dried.

De med hårfargemidlene ifølge oppfinnelsen oppnådde fargetoner viser under anvendelse av forskjellige fremkaller- og koplerkomponenter en stor variasjonsmulighet som strekker seg fra brunt til svartblå og fører som nyanseringskomponenter til spesielt intense naturlige fargetoner. De oppnådde farger har gode lys-, vaske- og friksjonsekthetsegenskaper og lar The color tones obtained with the hair dyes according to the invention show, using different developer and coupler components, a great variety of possibilities that extend from brown to black-blue and lead to especially intense natural color tones as tinting components. The obtained colors have good light, washing and friction fastness properties and allow

seg lett igjen fjerne med reduksjonsmidler. easily removed again with reducing agents.

Oppfinnelsens gjenstand skal forklares nærmere ved hjelp av noen eksempler. The object of the invention shall be explained in more detail with the help of some examples.

Eksempler Examples

I første rekke omtales fremstillingen av det i de følgende eksempler som fremkallerkomponent anvendte N-(p-aminofenyl)-N<1>,N'-bis-(3-hydroksyetyl)-1,3-diaminopropan som ikke er In the first place, the preparation of the N-(p-aminophenyl)-N<1>,N'-bis-(3-hydroxyethyl)-1,3-diaminopropane used as developer component in the following examples is mentioned, which is not

kjent fra litteraturen. known from the literature.

1. trinn: Fremstilling av N-(p-nitrofenyl)-N",N'-bis- ( B-. hydroksyetyl)- 1, 3- diaminopropan. 1st step: Preparation of N-(p-nitrophenyl)-N",N'-bis- ( B-. hydroxyethyl)- 1, 3- diaminopropane.

En blanding av 14,1 g (0,1 mol) p-fluornitrobenzen, 16,2 g A mixture of 14.1 g (0.1 mol) of p-fluoronitrobenzene, 16.2 g

(0,1 mol) N-(3-aminopropyl)-dietanolamin og 10,4 g (0,075 (0.1 mol) N-(3-aminopropyl)-diethanolamine and 10.4 g (0.075

mol) kaliumkarbonat ble oppvarmet i 20 ml etanol pluss 5 ml vann i 6 timer i en autoklav ved 150°C. Etter avkjøling ble det helt i isvann og den dannede utfelling ekstrahert med eddikester. Etter tørkning med natriumsulfat ble det inndampet til tørrhet. Det ble dannet 16 g N-(p-nitrofenyl)-N<*>,N'-bis-(B-hydroksyetyl)-l,3-diaminopropan i form av gule krystaller og med sm.p. 52 - 54°C. 2. trinn: N-(p-aminofenyl)-N',N<1->bis-(B-hydroksyetyl)-1, 3- diaminopropan- tiahydroklorid- trihydrat. mol) of potassium carbonate was heated in 20 ml of ethanol plus 5 ml of water for 6 hours in an autoclave at 150°C. After cooling, it was poured into ice water and the precipitate formed was extracted with vinegar. After drying with sodium sulfate, it was evaporated to dryness. 16 g of N-(p-nitrophenyl)-N<*>,N'-bis-(B-hydroxyethyl)-1,3-diaminopropane were formed in the form of yellow crystals and with m.p. 52 - 54°C. 2nd step: N-(p-aminophenyl)-N',N<1->bis-(B-hydroxyethyl)-1, 3-diaminopropane-thia hydrochloride trihydrate.

15,8 g av N-(p-nitrofenyl)-N',N'-bis-(B-hydroksyetyl)-1,3-diaminopropan ble hydrogenert i 200 ml etanol i nærvær av 5 % palladium på kull ved 25°C i lato. Etter avsluttet hydrogenopptak ble det filtrert fra katalysator, surgjort med fortynnet saltsyre og inndampet. Forbindelsen ble dannet som lysebrun olje med et utbytte på 20 g. 15.8 g of N-(p-nitrophenyl)-N',N'-bis-(B-hydroxyethyl)-1,3-diaminopropane was hydrogenated in 200 ml of ethanol in the presence of 5% palladium on charcoal at 25°C in lato. After completion of hydrogen uptake, it was filtered from the catalyst, acidified with dilute hydrochloric acid and evaporated. The compound was formed as a light brown oil in a yield of 20 g.

IR-spektrum (cm<-1>): 1630, 1585, 1510, 1465, 1320, 1195, IR spectrum (cm<-1>): 1630, 1585, 1510, 1465, 1320, 1195,

1070, 1020, 900, 825, 755. 1070, 1020, 900, 825, 755.

Hårfargemiddelet ifølge oppfinnelsen ble anvendt i form av en krememulsjon. Derved ble det i en emulsjon av The hair dye according to the invention was used in the form of a cream emulsion. Thereby it was in an emulsion of

10 vektdeler fettalkoholer av kjedelengde ci2~<C>18 10 parts by weight fatty alcohols of chain length ci2~<C>18

10 vektdeler fettalkoholsulfat (natriumsalt) 10 parts by weight fatty alcohol sulfate (sodium salt)

kjedelengde C2. 2~ C18 chain length C2. 2~ C18

75 vektdeler vann 75 parts by weight water

hver gang innarbeidet 0,01 mol N-(p-aminofenyl)-N',N'-bis-(g-hydroksyetyl)-1,3-diaminopropan-trihydroklorid-trihydrat og de nedenfor oppførte koplerstoffer. Deretter ble emul-sjonens pH-verdi ved hjelp av ammoniakk innstilt på 9,5 og emulsjonen oppfylt med vann til 100 vektdeler. Den oksydative kopling ble gjennomført med 1 %-ig hydrogenperoksyd-oppløsning som oksydasjonsmiddel, -idet det til 100 vektdeler av emulsjonen ble satt 10 vektdeler hydrogenperoksyd-oppløsning. Den eventuelle fargekrem med ekstra oksydasjonsmiddel ble påført på til 90 % grånet, ikke spesielt forbe-handlet menneskehår og henlatt der i 30 minutter. Etter av-slutning av fargeprosessen ble håret vasket, med et vanlig hårvaskemiddel og deretter tørket. De derved dannede fargninger fremgår av nedenstående tabell 1. each time incorporated 0.01 mol of N-(p-aminophenyl)-N',N'-bis-(g-hydroxyethyl)-1,3-diaminopropane trihydrochloride trihydrate and the coupling substances listed below. The emulsion's pH value was then adjusted to 9.5 using ammonia and the emulsion filled with water to 100 parts by weight. The oxidative coupling was carried out with a 1% hydrogen peroxide solution as oxidizing agent, 10 parts by weight of hydrogen peroxide solution being added to 100 parts by weight of the emulsion. Any color cream with additional oxidizing agent was applied to 90% greyed, not specially pre-treated human hair and left there for 30 minutes. After finishing the coloring process, the hair was washed with a normal hair detergent and then dried. The resulting colors are shown in table 1 below.

Som koplerstoffer tjente følgende forbindelser: The following compounds served as coupling agents:

K 1 : m-aminofenol K 1 : m-aminophenol

K 2 : 3-isopropylidenamino-2,4-diklorfenol K 2 : 3-isopropylideneamino-2,4-dichlorophenol

K 3 : 2-klor-6-metyl-3-aminofenyl K 3 : 2-chloro-6-methyl-3-aminophenyl

K 4 : resorcinmonometyleter K 4 : resorcin monomethyl ether

K 5 : 2,7-dihydroksynaftalin K 5 : 2,7-dihydroxynaphthalene

K 6 : 2,4-diklor-3-aminofenol K 6 : 2,4-dichloro-3-aminophenol

K 7 : 1,3-bis-(2,4-diaminofenoksy)-propan K 7 : 1,3-bis-(2,4-diaminophenoxy)-propane

K 8 : 2-klorresorcin K 8 : 2-chlororesorcinol

K 9 : 2-metylresorcin K 9 : 2-methylresorcinol

K 10: 2,4-diaminofenol K 10: 2,4-diaminophenol

K 11: 5-amino-2-metylfenol K 11: 5-amino-2-methylphenol

K 12 : 1,5-dihydroksynaftalin K 12 : 1,5-dihydroxynaphthalene

K 13 : resorcin K 13 : resorcinol

K 14 : a-naftol K 14 : α-naphthol

K 15 : l-fenyl-3-acetamido-pyrazolon-5 K 15 : 1-phenyl-3-acetamido-pyrazolone-5

Claims

1. Hair dye on the basis of oxidation dyes with a developer component, and the coupling agents common in oxidation hair dyes, as well as possibly common direct-dye dyes, characterized by a content of N-(p-aminophenyl)-N',N<*->bis -(3-hydroxyethyl)-1,3-diaminepropane, and its inorganic or organic salts as developer components.