DK149051B - METHOD AND PROCEDURE FOR OXIDATIVE DYING OF HAIR - Google Patents

Description

149051

The present invention relates to an agent for oxidative dyeing of hair containing a combination of p-phenylenediamine or a derivative thereof as a carcinogen and a coupling agent, and optionally direct-dye, antioxidants and usual adjuvants. Furthermore, the invention relates to a method of oxidative dyeing of hair using said agent.

For dyeing hair, dyes based on oxidation dyes have gained great importance. The staining occurs in the way that certain developer substances react with certain coupling agents in the presence of a suitable oxidizing agent.

In particular, 2,5-diamino-toluene, 1,4-diaminobenzene, p-aminophenol and 3-methyl-4-15 aminophenol are used as the developing substances. Preferred coupling agents are α-naphthol, resorcin, 4-chloro resorcin, m-aminophenol and derivatives of m-phenylenediamine such as m-toluylenediamine and 2,4-diaminoanisole. These derivatives as well as the m-phenyl diamine itself, because of their ability to produce blue shades by oxidative coupling 20 with 1,4-diaminobenzene or 1,4-diaminobenzene derivatives, have become important as so-called blue coupling agents.

Many special requirements are made for oxidizing agents which are used for dyeing human hair.

25 Thus, they must be non-toxic in terms of toxicity and dermatology and enable the attainment of stains of the desired intensity. Furthermore, it is necessary that by combining suitable developer and coupling components a wide range of different color nuances can be provided. Furthermore, for the attainable hair dyes, good light, permanent, acid and abrasion resistance are required. In any case, such hair dyes must remain stable over a period of at least 4-6 weeks without the effects of light, chemicals and abrasion.

The mb-phenylenediamine and its derivatives m-toluylenediamine and 2,4-diaminoanisole, commonly used as a blue-coupling agent in hair dyes, as well as the recently recommended blue-coupling agents such as 1-hydroxy-3-amino-6-chlorobenzene and 2,4-diaminophenoxyethanol, may not satisfactorily meet the above requirements.

Danish Patent Application 3705/77 discloses an agent for oxidative dyeing of hair which, in addition to "oxidation bases" such as p-phenylenediamines, contains at least one coupling substance of the general formula: ίτ · NHR 'wherein R' is a hydrogen atom or an alkyl - or hydroxyalkyl group having 1-3 C atoms and Z is a hydroxyalkyl, (C1-C2) alkoxyalkyl, mesylaminoalkyl, acetylaminoalkyl, ureidoaminoalkyl or carbethoxyaminoalkyl group, the alkyl groups of group Z has 2 or 3 C atoms, or acid salts thereof. In particular, 2,4-diaminophenoxyethanol can be used as the coupling agent.

Dyestuffs having a coupling substance content of the above general formula, when combined with the majority of the p-phenylenediamines, result in blue hair dyes that are more or less rich in green and purple tones.

25 However, with blue tones containing red or violet hues, it is impossible or very difficult to dye hair in ascetones. Said coupling agents are therefore unsuitable as the blue coupling agents necessary for obtaining ascetones.

30. The agent of the present invention for oxy-dot dyeing of hair, which is of the type initially described, is characterized in that it contains as a coupling substance at least one 1- (β-hydroxyalkyl) -2,4-diamihobenzene of the general formula: 3 149051

R

H-C-OH

CH2 -'NH2

T

10 nh 2 where R is a hydrogen atom, a CH 2 or C 2 H 5 group, optionally in the form of inorganic or organic salts thereof, and optionally further known coupling substances.

The above - 1- ((3-hydroxyalkyl) -2,4-diamino benzenes of formula I, as coupling agents in combination with the inducing substances 1,4-diaminobenzene and 1,4-diaminobenzene derivatives give relatively cold, very intense blue tones without the content of red, which has not been obtained with the above-mentioned blue-dyeing agents commonly used in hair dyeing agents.The agent according to the invention therefore makes it possible to color hair in ashy natural colors without any further additional characteristics of the agent according to the invention are discussed below.

The 1- (β-hydroxyalkyl) -2,4-diaminobenzene compounds of the formula I, which are coupling agents in the hair dyes, are well soluble in water, the solubility of which can be further increased by the addition of alkalis such as sodium hydroxide, and they further show an excellent shelf life, particularly as a component of the hair dye in question.

In the hair dyes, said coupling agents, of which 1- (β-hydroxyethyl) -2,4-diaminobenzene is preferred, must be contained at a concentration of about 0.01 to 4.0% by weight, preferably 0.02-2.0% by weight.

149051 4

In addition, as the further known coupling agents, the hair dyeing agent may contain in particular at least one of the coupling agents α-naphthol, 3,4-diaminobenzoic acid, resorcin, 4-chloro resorcin, m-aminophenol and 3-amino-6-5 methylphenol. 4-oxy-1,2-methylenedioxybenzene can also be used as a coupling agent.

Among the known developing substances, especially component 1,4-diaminobenzene and 2,5-diaminotoluene are considered as constituents of the hair dye in question.

Furthermore, as suitable developing substance, 2,5-diaminobenzyl alcohol can also be used.

Both the 1- (β-hydroxyalkyl) -2,4-diamino benzenes of the general formula I as well as the known coupling agents and developer substances may be contained in the hair-dyeing agents alone or in admixture with one another.

The total amount of the hair-dye-agent-coupling-substance combination contained in the hair dyeing agents described herein should amount to approx. 0.1-5.0% by weight, preferably 0.5-3.0% by weight.

The developer substances are generally used in approximately equimolar amounts, based on the coupling components. However, it is not a matter of whether the developer component in this respect is present in a certain excess or deficit.

Furthermore, the hair dye mites in question may additionally contain other color components, such as in particular 6-amino-3-methylphenol, which is particularly suitable as a nuance dye to obtain natural tones, modern tones and especially matte color tones. As any direct coloring dyes, e.g. such as triphenylmethane dyes, such as Diamond Fuchsin (C.I.

42 510) and Leather Ruby HF (CI 42 520), aromatic nitro dyes such as 2-nitro-1,4-diaminobenzene and 2-amino-4-nitrophenol, azo dyes such as Acid Brown 4 35 (cI 14 805) and Acid Blue 135 (CI 13 385), anthraqui non-dyes, such as Disperse Red 15 (CI 60 710) and 5 149051

Disperse Violet 1 (C.I. 61,100), and additionally 1,4,5,8-tetraamino-anthraquinone and 1,4-diamino-anthraquinone.

Furthermore, in the hair colorants, there may also be usual cosmetic additives, e.g. antioxidants such as ascorbic acid or sodium sulfite, perfume oils, complexing agents, wetting agents, emulsifiers, thickening agents and care products.

The condition may be a solution, preferably a cream, gel or emulsion. The composition of the composition is a mixture of the dye components with the usual ingredients for such compositions. As usual constituents of creams, emulsions or gels, for example, wetting agents or emulsifiers come from the class of anionic, cationic or nonionic surfactants, such as fatty alcohol sulfates, alkyl sulfonates, alkylbenzenesulfonates, alkyltrimethylammonylatedene, ethoxylated salts, ethoxylated fatty acid alkanolamides, further thickeners such as higher fatty alcohols, starches, cellulose derivatives, paraffin oil and fatty acids, as well as care products such as lanolin derivatives, cholesterol and pantothenic acid in consideration. Said components are used in the usual amounts for such purposes, e.g. wetting agents and emulsifiers in concentrations of approx. 0.5 to 30% by weight, while thickeners may be contained in the compositions in an amount of approx. 0.1-25% by weight.

Depending on the composition, the coloring agents in question may react slightly acidic, neutral or alkaline.

In particular, they exhibit a pH in the alkaline range 30 between 8.0 and 11.5, the setting being preferably with ammonia. However, organic amines such as monoethanolamine or triethanolamine can also be used.

The present method for oxidative dyeing of hair is of the kind specified in the preamble of the process claim 35 and is characterized by the characterizing part of the process claim. As the oxidizing agent in the hair dye comes mainly hydrogen peroxide, for example as 6% aqueous solution or addition compound 149051.

6 considers thereof with urea, melamine or sodium borate. The action time of the agent is preferably 30 minutes. For rinsing, e.g. a weak organic acid such as citric or tartaric acid is used.

5 For the preparation of the 1- (3-hydroxyalkyl) -2,4-diaminobenzzenes contained in the hair dyeing agents described, various synthetic routes are known in the literature. Thus, for example, in the preparation of 1- (β-hydroxyethyl) -2,4-diaminobenzene, β-phenylethyl alcohol 10 can be used as starting material. The β-phenylethyl alcohol is first acetylated to protect the OH group and then nitrated. By catalytic hydrogenation of the 2,4-di-nitro compound formed and subsequent deacetylation, 1- (β-hydroxyethyl) -2,4-diaminobenzene can be recovered in high yield.

Also of particular importance is the advancement in toxicological and dermatological terms obtained by using the 1-tho-hydroxyalkyl) -2,4-diaminobenzzenes of the formula I disclosed in the hair dyeing agents described herein, e.g. . compared with the known blue coupling agents 2,4-diaminotoluene, 2,4-diaminoanisole and 1,3-diamino-benzene, which progress is due to the hydroxyalkyl group attached to the substituted benzene nucleus and the associated decrease in lipoid solubility.

In addition to the already mentioned ability to dye hair in ash-like natural colors, the color-superior properties of the hair dye in accordance with the invention furthermore show that 1- (g-hydroxyalkyl) -2,4- diaminobenzene 30 may also produce dark natural tones, in particular a black.

Finally, it is also possible with this hair dye to stain gray, chemically unprepared hair without any problems and while obtaining a previously unavailable covering ability.

The invention is further described by the following examples.

7 149051

Example 1 Hair dye in gel form: 0.5 g of 1- (β-hydroxyethyl) -2,4-diaminobenzene dihydrochloride 0.5 g of 2,5-diaminotoluene sulfate 0.3 g of ascorbic acid 1.0 g of hydroxyethyl cellulose, high viscosity 5.0 g lauryl alcohol diglycol ether sulfate, sodium salt (28% aqueous solution) 10.0 g ammonia, 22% 82.7 g water 15 g

Shortly before use, 50 g of this hair dye was mixed with 50 ml of hydrogen peroxide solution (6%). and the mixture was allowed to interact for 30 minutes at 40 ° C on blond human hair. Then it was rinsed with water and dried. The hair had been intensely bluish.

Example 2 Hair dye in gel form: 0.5 g of 1- (β-hydroxyethyl) -2,4-diaminobenzene dihydrochloride 1.0 g 1,4-diaminobenzene 0.5 g resorcin 0.2 g m-aminophenol 0.3 15.0 g oleic acid 7.0 g isopropanol 10.0 g ammonia, 22% 65.5 g water 100 g

Claims (8)

Of this hair dye, 50 g shortly before use was mixed with 50 ml of hydrogen peroxide solution (6%) and then the mixture was applied to human blonde hair. After a 30 minute action at 40 ° C, 5 was rinsed with water and dried. The hair was colored in a deep blue-black tone. All percentages given indicate weight percentages. 10 15 20 PATENT REQUIREMENTS An agent for oxidative dyeing of hair, which contains a combination of p-phenylenediamine or a derivative thereof as a developing substance and a coupling substance 25 as well as any direct coloring dyes, antioxidants and usual adjuvants, characterized in that it contains as a coupling substance. at least one 1- (β-hydroxyalkyl) -2,4-diaminobenzene of the general formula: 149051 R1 HC-OH CH2 An agent according to claim 1, characterized in that it contains as a coupling substance 1- (ω-hydroxyethyl) -2,4-diaminobenzene, optionally in the form of inorganic or organic salts thereof. An agent according to claim 1 or 2, characterized in that it contains the present coupling substances at a concentration of approx. 0.01-4.0% by weight, preferably 0.02-2.0% by weight. An agent according to any one of claims 1-3, characterized in that it contains at least one of the developing substances 1,4-diaminobenzene, 2,5-diaminooluene and 2,5-diaminobenzyl alcohol. An agent according to any one of claims 1-4, characterized in that, as a further known coupling agent, it contains at least one of the coupling substances α-naphthol, 3,4-diaminobenzoic acid, resorcin, 4-chloro resorcin, m-aminophenol, 4 -oxy-1,2-methylenedioxybenzene and 3-amino-6-methylphenol. Wherein R is a hydrogen atom, a CH 2 or C 2 H 9 group, optionally in the form of inorganic or organic salts thereof, and optionally further known coupling agents. An agent according to any one of claims 1-5, characterized in that the total amount of the developer-substance coupling substance contained contains 0.1-5.0% by weight, preferably 0.5-3.0 weight percent. 149051 Agent according to any one of claims 1-6, characterized in that it further contains as a color component 6-amino-3-methylphenol. A method of oxidative dyeing of hair using an agent containing a combination of p-phenylenediamine or a derivative thereof as a developing substance and a coupling agent, and optionally direct-dye, antioxidants and usual adjuvants, characterized in that agent according to any one of claims 1-7, containing, as a coupling agent, a 1- ((3-hydroxyalkyl) -2,4-diami-nobenzene of the general formula: R HC-OH CH2 9 wherein R is a hydrogen atom, a CH 2 or group, optionally in the form of salts thereof with inorganic or organic acids, and optionally additional known coupling agents, after the addition of an oxidizing agent, preferably hydrogen peroxide, is applied to the hair, where it is allowed to act for about 10-45 minutes at a temperature of 15-50 ° C, 30 after which the hair is rinsed, optionally washed and rinsed, and then dried. Langkjær Kobenhavn