DK148011B - HAIR PAINTING BASIS OF OXIDATION COLORS - Google Patents

Abstract

1. Hair dyes based on oxidation dyes, characterized by a content of N-(2-hydroxypropyl)-p-phenylene diamine and its inorganic or organic salts as developer substance and the coupler substances normally used in oxidation hair dyes.

Description

in 148011

The present invention relates to oxidation dye-based hair colorants having a hydroxyalkyl-substituted p-phenylenediamine type developing component as well as the usual coupling compounds of the oxidizing dyes.

For dyeing hair, the so-called oxidation dyes, which are formed by the oxidative coupling of a developer component with a coupling component, play a prominent role because of their intense colors and very good authenticity properties. Nitrogen bases such as p-phenylenediamine derivatives, diaminopyridines, 4-amino-pyrazolone derivatives and heterocyclic hydrazones are usually used as the developing compounds. As so-called coupling components may be mentioned m-phenylenediamine derivatives, phenols, naphthols, resorcinol derivatives and pyrazolones.

Good oxidation hair dye components must primarily fulfill the following conditions:

They must, by the oxidative coupling with the relevant developer or coupling components, form the desired shades of color with sufficient intensity. In addition, they must have a sufficient to excellent application ability on human hair, and in addition they must be toxic, in terms of toxicology and dermatology.

The compound class usually used as a class of compounds comprising the substituted or unsubstituted p-phenylenediamines has the disadvantage of causing hypersensitivity in a number of persons and consequently severe allergies. The developer compounds proposed for the elimination of these dermatological features recently have not always been fully satisfactory in terms of their technical properties.

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Therefore, in the search for usable oxidation hair dyes, it was the task of finding suitable components which do not suffer from the aforementioned disadvantages and which fulfill the aforementioned conditions optimally.

The hair dyes of the invention are characterized in that they which induce contain N- (2-hydroxypropyl) -p-phenylenediamine or inorganic or organic salts thereof.

It has been found that such hair colorants meet the requirements of a hair colorant to a very high degree.

N- (2-hydroxypropyl) -p-phenylenediamine can be obtained by the usual methods of organic synthesis. A suitable method of manufacture is given in the specific part of the specification.

When used as a developing component, N- (2-hydroxypropyl) -p-phenylenediamine, together with the commonly used oxidation hair dye, results in a wide range of very intense color shades that could not be obtained with these coupling compounds and the known developers. Accordingly, hair dyes with a content of N- (2-hydroxypropyl) -p-phenylene = diamine present a significant enrichment of the possibilities of oxidative hair dye. In addition, the stains obtained with this compound are distinguished by superior authenticity properties.

Furthermore, N- (2-hydroxypropyl) -p-phenylenediamine and its salts are toxicologically and dermatologically harmless and have good water solubility as well as good storage stability.

In the hair colorants of the invention, N- (2-hydroxypropyl) -p-phenylenediamine can be used either as such or in the form of salts thereof with inorganic or organic acids, e.g. such as chloride, sulfate, phosphate, acetate, propionate, lactate or citrate.

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As additional dye components, they are usually used as coupling compounds, contained in the hair dyes of the invention. Examples of such coupling components are; α-naphthol, o-cresol, m-cresol, 1,6-dimethylphenol, 2,5-dimethylphenol, pyro-catechol, pyrogallol, 1,5- or 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m -aminophenol, 2,4-diaminoanisole, m-toluylenediamine, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 1-phenyl-3-methylpyrazolone-5,1-amino-3-acetylacetamino-4-nitrobenzene or 1-amino-3-cyanoacetyl = amino-4-nitrobenzene, 2-methylresorcinol, 2,4-diaminophenol, 3,5-diamino-2-methoxybenzene, 1-ethoxy-2-bis- (β-hydroxyethyl) amino-4-aminobenzene, 2.4 -dichloro-3-aminophenol, 1-phenyl-3-ethylureidopyrazolone-5, 1,3-bis- (2,4-diaminophenoxy) propane and 4-chloro resorcinol.

In the hair dye compositions of the invention, the developer components are generally used in approximately molar amounts, relative to the coupling compounds used.

However, although the molar application has proved appropriate, there is no disadvantage when the developer component is present in a certain excess or deficit.

It is not necessary that the developer component and the coupling compound be present as single compounds, on the contrary, both the developer component and the coupling agent can be present as mixtures of the above-mentioned compounds.

In addition, the hair dye compositions of the invention may contain other known and usual developer components as well as optionally also conventional dyes for direct application to the blend, if this is necessary to obtain certain shades of color.

The oxidative coupling, i.e. in principle, as in the case of other oxidation hair dyes, it can also be effected by the oxygen of the air.

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Conveniently, however, chemical oxidants are used. As such, especially hydrogen peroxide or its preparation products for urea, melamine and sodium laboratory and mixtures of such hydrogen peroxide preparation compounds with potassium peroxodisulfate are considered.

The hair dyes of the invention are incorporated into suitable cosmetic compositions, such as creams, emulsions, gels or simple solutions for the purpose of application, and added to one of said oxidizing agents immediately prior to application to the hair. The concentration of coupling agent-developer combination of such staining compositions is 0.2-5% by weight, preferably 1-3% by weight. For the preparation of creams, emulsions or gels, the dye components are mixed with the usual additional ingredients for such preparations. As such additional ingredients may be mentioned, for example, wetting or emulsifying agents of anionic or nonionic type, such as alkylbenzene sulfonates, fatty alcohol sulfates, alkyl sulfonates, fatty acid alkanolamides, ethylene oxide fatty alcohol adjuvants, thickening agents, such as methyl cellulose, thickeners such as methyl cellulose, in addition, perfume oils and hair care products such as pantothenic acid and cholesterol.

Said additives are used in the usual amounts for these purposes, such as, for example, wetting and emulsifying agents at concentrations of 0.5-30% by weight and thickening agents at concentrations of 0.1-25% by weight, relative to the total composition.

The use of the hair colorants of the invention, regardless of whether it is a solution, an emulsion, a cream or a gel, can be carried out in a slightly acidic, neutral or especially alkaline environment at a pH of 8-10. temperatures range from 15 to 40 ° C. After an impact time of approx. For 30 minutes, the hair dye is removed from the hair to be stained by rinsing. Then the hair is washed with a mild shampoo and dried.

The color tones obtainable with the hair dyes of the invention, using various developer and coupling components, exhibit an extremely wide range of options ranging from dark brown to ruby red, black blue and violet. The obtained color tones have good light, wash and rub properties and can easily be removed again by means of reducing agents.

The use of N-hydroxyalkyl-substituted p-phenylenediamines as components of oxidation hair dyes is known from U.S.A. Patent Specification No. 1,932,901 and from German Patent Specification No. 2,240,495. N- (2-hydroxypropyl) -p-phenylene = diamine, however, is not mentioned in either of the two printouts as a single chemical or special case. Accordingly, there is also no reference to the surprising and excellent light-fastening properties of the stains obtainable with N- (2-hydroxypropyl) -p-phenylenediamine as the developing component in oxidation dyes.

From usa. In addition, patent specification 3,970,423 is known to p-phenylenediamine derivatives, which differ, however, more from the developing component used in the hair dyes according to the invention than is the case for the comparative compounds mentioned in the comparative test for light fastness described in the following. Those from U.S.A. The p-phenylenediamine derivatives known in the patent carry at least two substituents on the benzene nucleus, at least two of the substituents R, R, R and R being other than hydrogen. For example, the compound disclosed in Example 11 (4-amino-2-methyl-N- (2-hydroxyethyl) -aniline) has an additional substituent on the benzene core, and the compound disclosed in Example 16 (N-ethyl-N-hydroxyethyl) p-phenylenediamine) has an additional substituent attached to the nitrogen atom.

The following examples further illustrate the invention.

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The N- (2-hydroxypropyl) -p-phenylenediamine determined for use in the following hair dye compositions of the invention was prepared as dihydrochloride by the usual methods of organic synthesis. The preparation selected is briefly described below: A) N- (2-hydroxypropylamino) -4-nitrobenzene.

A mixture of 21.2 g (0.15 mole) of 4-fluoro-nitrobenzene, 15 g (0.2 mole) of 1-amino-2-propanol and 10.4 g of potassium carbonate was heated for 2 hours to reflux in 25 ml. dimethylformamide. After cooling, the reaction mixture was poured into ice water and the precipitate was filtered off.

By recrystallization from toluene, yellow crystals were obtained, mp 79 ° C.

B) N- (2-hydroxypropyl) -p-phenylenediamine dihydrochloride.

15 g of N- (2-hydroxypropylamino) -4-nitrobenzene was hydrogenated in 100 ml of ethanol in the presence of 5 wt% palladium on carbon at 25 ° C and a hydrogen pressure of 2 bar. After completion of hydrogen uptake, the catalyst was filtered off and the filtrate was acidified with dilute hydrochloric acid and evaporated to dryness. Gray crystals were obtained, mp 230 ° C.

In the following examples, N- (2-hydroxypropyl) -p-phenylene = diamine hydrochloride was used in combination with the compounds listed below as coupling agents: 7 148011 K 1: α-naphthol, Κ 2: 1,7-dihydroxynaphthalene, Κ 3: Resorcinol, Κ 4: 2-methylresorcinol, Κ 5: m-aminophenol, Κ 6: 5-amino-2-methylphenol, Κ 7: 2,4-dichloro-3-aminophenol, Κ 8: 1-phenyl-3 -methylureido-pyrazolone.

The hair dyes of the invention were used in the form of a cream emulsion. To this end, in an emulsion of 10 parts by weight of fatty alcohols of the chain length 10 parts by weight of fatty alcohol sulphate (sodium salt) with the chain length C 2 - ("18 ° 9 75 parts by weight of water) 0.01 mol of N- (2-hydroxypropyl) -p-phenylenediamine was incorporated. -dihydrochloride as the developing compound and 0.01 mole of the coupling agents listed in the following table, then the pH of the emulsion was adjusted to 9.5 by means of ammonia and the emulsion was brought to 100 parts by weight with water. with a 1% hydrogen peroxide solution as the oxidizing agent, adding 100 parts by weight of the emulsion to 10 parts by weight hydrogen peroxide solution. The color creams with the addition of oxidizing agents were applied to 90% gray, not very pretreated human hair and left there for 30 minutes. For example, the hair was washed out with a conventional hair washing agent and then dried, and the resulting stains are shown in the following Table 1.

TABLE 1.

With 1% I ^ Oj solution

Example Coupling agent obtained tint 1 K Black Blue 2 K 2 Black Blue 3 K 3 Brown black 4 K 4 Brown gray 5 K 5 Black violet 6 K 6 Dark violet 7 K 7 Violet black 8 K 8 Dark ruby red

Comparison experiments on light fastness.

The light fastness properties were assessed according to DIN 54 004. To prepare the dyes, dyes were prepared with the following coupling agents:

K1: a-naphthol, K3: Resorcinol, K6: 5-amino-2-methylphenol, K9: 1-phenyl-3-acetamidopyrazolone.

The following p-phenylene = diamines were used as developer components: E 1: N- (2-hydroxypropyl) -p-phenylenediamine, E 2: N- (2-hydroxy-2-methylpropyl-2) -p-phenylenediamine, E 3: N- (6-hydroxyhexyl) -p-phenylenediamine, of which E 2 and E 3 represent comparative compounds.

The results obtained in the assessment according to DIN 54 004 are listed in the following Table 2.