DD294632A5 - Oxidation hair - Google Patents

Abstract

Agent for oxidative dyeing of hair containing a combination of a developer substance and at least one coupler substance which contains as developer substance * or its physiologically acceptable water-soluble salt and the coupler substance is selected from resorcinol, 2-methylresorcinol, 4-chlororesorcinol, 3,4 -Methylendioxyphenol, 3-aminophenol and * or their physiologically acceptable water-soluble salts. The agents have good faerberic properties and are not mutagenic and non-sensitizing. {Oxidative staining; Hair; Developing agent; Coupling substance; * Resorcinol; 2-methylresorcinol; 4-chlororesorcinol; 3,4-methylenedioxyphenol; 3-aminophenol; *}

Description

Field of application of the invention

The invention relates to means for the oxidative dyeing of hair containing a non-sensitizing non-mutagenic developing agent-coupler substance combination, wherein 2- (2,5-diaminophenyl) ethanol is used as a developer in combination with certain coupler substances.

Characteristic of the known state of the art

In the field of hair coloring oxidation dyes have acquired a significant importance. The color is formed by reaction of certain developer substances with certain Kuppiersubstanzen in the presence of an oxidizing agent. The presently preferably used developers are 2,5-diaminotoluene, p-phenylenediamine, 4-aminophenol and 4-amino-3-methylphenol, while as couplers a variety of compounds such. B. resorcinol, 2-methylresorcinol, 4-chlororesorcinol, 2-chlororesorcinol, 4,6-dichlororesorcinol, 2-amino-4- (2-hydroxyethyl) aminoanisole, 2- (2,4-diaminophenoxy) ethanol, 1-naphthol, m-phenylenediamine, 5-amino-2-methylphenol, S-amino-1-chloro-e-methylphenol, 3-amino-2-methylphenol, 2- (4-amino-2-hydroxyphenoxylethanol, 4-amino-1,2-methylenedioxybenzene , 2,4-diamino · 5 · ethoxytoluene, 4 · hydoxy-indole, 3-amino-5-hydroxy-2,6-dimethoxypyridine, 3,5-diamino-2,6-dimethoxypyridine, 3-amino-6-methoxy-2 -methylaminopyridine, thymol, 2- (2-hydroxyethyl) -5-methylphenol, 2-hydroxymethyl-5-methylphenol, 3-aminophenol and N- (2-hydrox yethyl) -3,4-methylenedioxyaniline.

There are many special requirements for oxidation dyes that are to be used for coloring human hair. The dyes must be harmless in toxicological and dermatological terms and allow dyeings of the desired intensity. Furthermore, a good light, permanent wave, acid and rubbing fastness is required for the hair dyeings achieved.

In any case, such hair dyeings must remain stable for a period of at least four to six weeks without exposure to light, friction and chemical agents. In addition, it is necessary that a wide range of different color shades can be produced by combining suitable developer and coupler components. Bedenkon has recently been raised with respect to its physiological compatibility with the currently used mainly p-phenylenediamine, 2,5-diaminotoluene and 4-aminophenol. One problem is the sensitization of certain persons to p-phenylenediamine derivatives of (parallalgic). This group of people has so far not been able to color their hair with hair dye based on p-phenylenediamine derivatives. Furthermore, not only the sensitizing effect of the pure developer substances, but also of the mixtures with coupler substances and the dyes formed therefrom must be considered.

Although the provision of pyrimidine derivatives as developing agents has alleviated the toxicological problems, these compounds are not entirely satisfactory from a dyeing point of view. ·

Object of the invention

The aim of the invention is to enable a toxicologically and dermatologically harmless hair coloring of different shades, which is stable to light, friction and chemical agents over a longer period of time.

Presentation of the Wesuns of the invention

It is therefore an object to provide oxidation hair dyes based on a well-colored, but not sensitizing and non-mutagenic developer-coupler substance combination available.

For this purpose, it has now surprisingly found that by a means for oxidative dyeing of hair containing a combination of 2- (2,5-diaminophenyl) ethanol as the developer and at least one coupler substance selected from resorcinol, 2-methylresorcinol, 4-chlororesorcinol, 3 , 4-Methylendioxyphenol, 3-aminophenol and N- (2-hydroxyethyl) -3,4-methylenedioxyanilin the task is achieved in an excellent manner.

The 2- (2,5-diaminophenyl) ethanol has been mentioned for some time as a component of oxidation hair dyes in the patent literature. As a possible component of Oxidationshaarfärbemitteln it is listed, for example, in the separate European patent application 0 166155 and in the own German patents 3625916,3627398 and 3706565 and also in DE-OS 3545371. Further, the 2- (2,5-diaminophenyl) ethanol falls under a general formula for 1-hydroxyalkyl-2,5-diaminobenzene compound, which are recommended as oxidation hair dye developing agents in European Published Patent Application 0007537. However, the compound 1-hydroxymethyl-2,5-diaminobenzene (2,5-diaminobenzyl alcohol) which has been mentioned several times there has proven to be sensitizing. The excellent suitability of the developing agent 2- (2,5-diaminophonyl) ethanol in combination with the aforementioned coupler substances to solve the problem has not been recognized. Accordingly, the developer substance-coupler substance combinations according to the invention are not described in any of these publications.

The concrete representation of the 2- (2,5-diaminophenyl) ethanois has also neither been described, nor has this developer substance found its way into hair dyeing practice. Because of the sensitizing properties of the homologous compound 2,5-diaminobenzyl alcohol known from European published patent application 0007537, a synthesis of this compound did not appear to be worthwhile either.

The use of the compound 2- (2,5-diaminophenyl) ethanol as the developer shows no difference with respect to the achievable colorations compared to the commonly used developer substances 2,5-diaminotoluene and p-phenylenediamine and the 2,5-diaminobenzyl alcohol. With dyn coupling substances according to the invention the expected hues are obtained. The fastnesses and the stability of the dyeings are comparable to the fastnesses achieved with the use of 2,5-diaminobenzyl alcohol. With regard to the intensities of the dyeings obtained, even a slightly worse result can be observed.

The great and surprising technical progress that can be achieved with the use of 2- (2,5-diaminophenyl) ethanol with the above-mentioned coupler substances is due rather to the physiological properties.

Thus shows the 2- (2,5-diaminophenyl) ethanol in the mutagenicity test according to Arnes both in the presence and in the absence of hydrogen peroxide, in the chromosome aberration test on CHO cells in vitro (CA test), in the Mouse Lymphoma test (point mutation in vitro) and in the Sister Chromatide Exchange (SCE) test, no mutagenicity, while the developing agent 2,5-diaminobenzyl alcohol has a potential in some of these assays.

Another advantage of the developing agent-coupler substance combination of the invention becomes apparent when the developer substance-coupler substance combination in hair dye mixtures under use conditions or when colored hair strands in the Ames test are tested for mutagenic activity.

The comparison of hair dyeing solutions containing the developing agent p-phenylenediamine, 2,5-diaminotoluene or 2- (2,5-diaminophenyl) ethanol, under oxidative conditions in the Amestest shows that the commonly used developer substances show a mutagenic potential, while the inventive Developer substance 2- (2,5-diaminophenyl) ethanol is not mutagenic.

Another surprising advantage for the developer substance-coupler substance combination according to the invention results from the comparison of dyed hair tresses in the Amestest. Haarsträhnchen were used for this experiment, on the one hand dyed with a mixture of p-phenylenediamine or 2,5-diaminotoluene as a developer and various coupler substances and on the other hand with a mixture of the novel 2- (2,5-diaminophenyl) ethanol and the same hair color couplers had been.

The results of these experiments are shown in Table 1 below:

Table 1

Amesteste of dyed strands of hair

Coupler substance Developer substance

2,5-diaminotoluene p-phenylenediamine 2- (2,5-diamino-

phenyljethanol

without coupler substance + + -

Resorcinol + (+) -

2-Meth''resorcinol + + -

3,4-MeI'onodioxyphenol + + -

3-aminopnenol (+) (+) + mutagenic (+ (weakly mutagenic - not mutagenic)

Test conditions: Hair tresses of 30-50 hair are impregnated with an agent according to Example 1, in which the coupler substance, in each case in an equimolar ratio to the developer substance, was contained. The tresses were then stored for 30 minutes at 40 ⁰ C in the cabinet, then rinsed thoroughly with water and finally dried. The dyed hair was then cut into 2.5 cm pieces and tested according to the method of BN Arnes on Salmonella typhimurium strains TA97, TA98 and TA 100 in the presence of S9 mix.

As the results show, in contrast to combinations of 2,5-diaminotoluene or p-phenylenediamine and the aforementioned coupler substances, no mutagenic potential of the hair tresses colored with the combination according to the invention is present.

Further, the developer-coupler substance combination of the present invention shows no sensitizing effect in a sensitization test according to the OECD Guidelines in both topical and intradermal treatment.

This surprising finding makes it possible for the first time to provide hair colorants for people with para-allergies. With the prior art developer substance-coupler substance combinations, however, the production of high-quality non-mutagenic and non-sonsibilizing hair dye is not possible.

The subject of the present application therefore relates to an agent for the oxidative coloring of hair containing a developer substance-coupler substance combination, characterized in that it contains as developing agent 2- (2,5-diaminophenyl) ethanol or its physiologically acceptable, water-soluble salt and the coupler substance is selected from resorcinol, 2-methylresorcinol, 4-chlororesorcinol, 3,4-methylenedioxyphenol, 3-aminophenol and N- (2-hydroxyethyl) -3,4-methylenedioxyaniline or their physiologically acceptable water-soluble salts.

The developer substances and coupler substances should be present therein as such or in the form of the physiologically tolerable salts, for example the hydrochlorides or the sulfates.

The hair dyes according to the invention are said to be 2- (2,5-diaminophenyl) ethanol or its physiologically acceptable salts in an amount sufficient for hair coloring from 0.01 to 4.0 wt .-%, preferably 0.1 to 3.0 wt. %, the total amount of the coupler substances should also be 0.01 to 4.0% by weight, preferably 0.1 to 3.0.

Owing to the advantageous properties of the 2- (2,5-diaminophenyl) ethanol according to the invention, this compound should preferably be present as sole developing agent in the compositions. However, if the compositions contain other developing agents, it must be ensured that they are also not mutagenic or sensitizing.

In addition to the abovementioned coupler substances used according to the invention, further coupler substances may optionally additionally be present in lesser amounts to achieve certain color shades, provided that no mutagone or sensitizing effect of the agent thereby occurs. However, the agent preferably contains only one or more of the aforementioned coupler substances. The coupler substances may be contained in the hair colorant individually or in gomic with each other. The total amount of the developer and coupler substances contained in the hair dye described herein should be 0.01 to 8.0 wt%, preferably 0.5 to 6.0 wt%.

The developer substances are generally used in approximately equimolar amounts, based on the coupler substances.

However, it is not disadvantageous if the developer substance is present in a certain excess or deficiency.

Furthermore, the hair dye of this application may additionally contain other non-sensitizing and non-mutagenic direct dyeing color components, for example 4- (N-ethyl, N-2'-hydroxyethyl) amino-1- (2 "-hydroxyethyl) amino-2-nitrobenzene and 1- (2'-Ureidoethyl-amino) -4-nitrobenzene, wherein the amount of these dyes is about 0.1 to 4.0 wt .-%.

Of course, the coupler and developer substances and the other color components, if they are bases, in the form of the cosmetically acceptable acid addition salts, for example as hydrochloride or as sulfate orsofern tis are compounds with phenolic or acid groups in the form of salts with bases , For example, as Alkalip.ienolate used.

The ertindungsgemäße developer substance 2- (2,5-diaminophenyl) ethanol can be prepared starting from 2- {2-aminophenyl) ethanol. In this case, the diacetyl compound obtainable from 2- (2-aminophenyl) ethanol and acetic anhydride is nitrated. The resulting mixture of N-acetyl-2- (2-acetoxyethyl) -4-nitroaniline and N-acetyl-2- (2-acetoxyethyl) -5-nitroaniline is saponified with hydrochloric acid. The desired 2- (2-amino-5-nitrophenyl) ethanol can be separated therefrom by partial hydrolysis of the hydrochlorides. The 2- (2,5-diaminophenyl) ethanol is obtained therefrom by catalytic hydrogenation.

Ausführungsbelsplele

In the following examples, the object of the invention will be explained in more detail, without limiting it to the examples.

Examples of hair dyes

Example 1 Hair dyeing solution

0.91 g of 2- (2,5-diaminophenyl) ethanol 0.66 g of resorcinol

10.00 g sodium lauryl alcohol diglycol ether sulfate, 28% aqueous solution 10.00 g ammonia, 25% aqueous solution 78.43 g water demineralized 100.00 g

Shortly before use, 10 g of the above hair dye is mixed with 10 ml of hydrogen peroxide solution (6%) and allowed to act for 30 minutes at 4O ⁰ C on gray natural hair. Then the hair is rinsed with water. The hair is dyed in a natural-brown color.

Example 2

Hair dye in cream form 3,0g2- (2,5-diaminophenyl) ethanol sulfate 0,6g resorcinol 0,6g 3-aminophenol 0,6gN- (2-hydroxyethyl) -3,4-methylenedioxyaniline hydrochloride 15.0g cetyl alcohol 0, 3 g sodium sulfite, anhydrous 3.5 g sodium lauryl alcohol diglycol ether sulfate, 26% aqueous solution

3.0 g ammonia, 25% aqueous solution 73.4 g water 100.0 g

50g of this hair dye are mixed shortly before use with 50g hydrogen peroxide solution (6%). Subsequently, the mixture contributes to graying hair of people who are sensitized to p-phenylenediamine and p-toluene diamine, and leave it for 30 minutes at 4O ⁰ C act. It is then rinsed with water and dried. The hair is dyed black. The subjects (para-allergic) do not react allergically during and after the staining.

Example 3 Hair Dyes in Gel Form 0.64 g 2- (2,5-diaminophenyl) ethanol 0.27 g resorcinol 0.30 g ascorbic acid 15.00 g oleic acid 7.00 g isopropanol 10.00 g ammonia, 22% aqueous solution 66.79 g water 100, 00 g

Shortly before use, 50 g of the above hair dye is mixed with 50 g of hydrogen peroxide solution (6%) and allowed to act on white natural hair for 30 minutes. Thereafter, the hair is rinsed with water and dried. The hair has adopted a natural, dark blonde color.

Example 4 Hair dyeing solution

1.25 g of 2- (2,5-diaminophenyl) ethanol sulfate 1.10 g of N- (2-hydroxyethyl) -3,4-methylenedioxyaniline hydrochloride 10.00 g of sodium lauryl alcohol diglycol ether sulfate, 28% aqueous solution 10.00 g of ammonia, 22% Aqueous solution 77.65 g of water 100.00 g

Shortly before use 10 g of the above hair dye mixed with 10 g of hydrogen peroxide solution (6%) and allowed to act for 30 minutes at 40 ° C on blonde natural hair. After rinsing with water and drying, the hair is dyed in a greenish ashy natural tone.

Claims (7)

1. A composition for the oxidative coloring of hair containing a developer substance-coupler substance combination, characterized in that it contains as developer substance (2- (2,5-DiaminophenyOethanol or its physiologically acceptable, water-soluble salt, and the coupler substance is selected from Resorcinol, 2-methylresorcinol, 4-chlororesorcinol, 3,4-methylenedioxyphenol, 3-aminophenol and N- (2-hydroxyethyl) -3,4-methylenedioxyaniline or their physiologically acceptable water-soluble salts. 2. Composition according to claim 1, characterized in that the coupler substance is selected from resorcinol, 4-chlororesorcinol, 2-methylresorcinol and 3-aminophencl. 3. Composition according to claim 1 and 2, characterized in that the developer substance / coupler substance combination in an amount of 0.01 to 8.0 wt .-%, preferably 0.5 to 6.0 wt .-%, is included. 4. Composition according to claim 1 to 3, characterized in that it contains a color component which is selected from 4- (N-ethyl, N-2'-hydroxyethyl) amino-1- (2 "-hydroxyethyl) amino-2-nitrobenzene and 1- (2'-ureidoethyl-amino) -4-nitrobenzene. 5. Composition according to claim 1 to 4, characterized in that it contains as antioxidants ascorbic acid, thioglycolic acid or sodium sulfite. 6. Composition according to claim 1 to 5, characterized in that it has a pH of 8.0 to 11.0. 7. Composition according to claim 1 to 6, characterized in that it is used for coloring the hair of para-allergic people.