DE3638227A1 - Hair dyes - Google Patents

Abstract

Oxidation hair dyes based on known developer components, e.g. p-phenylenediamine derivatives, p-aminophenols or 2,4,5,6-tetraaminopyrimidine, contain as coupler 2,4-dichloro-3-acetylaminophenol. The shades generated thereby are predominantly in the blue range and display good fastness properties.

Description

The invention relates to hair dyes based on Oxidation dyes. Such hair dyes contain oxidation dye precursors in a cosmetic carrier. As oxidation dye precursors become developer substances and Coupler substances used under the influence of oxidizing agents or form dyes from atmospheric oxygen. As serve cosmetic carriers for the oxidation dye precursors Creams, emulsions, gels, shampoos, aerosols or others Preparations that are suitable for use on the hair are.

So-called oxidation colors play a role in dyeing hair, by oxidative coupling of one or more developer components with each other or with one or more Coupler components are created because of their intense colors and good fastness properties play a preferred role. As Developer substances are usually primary, aromatic Amine with another in para or orthoposition free or substituted hydroxy or amino group, further Diaminopyridine derivatives, heterocyclic hydrazone derivatives, 4- Aminopyrazolone derivatives and tetraaminopyrimidines used. As so-called coupler substances are m-phenylenediamine derivatives, Napthols, resorcinol derivatives and pyrazolones are used.

Good oxidation hair dye precursors are essential in the first place meet the following requirements: You have to use the oxidative Coupling the desired color shades in sufficient intensity form. You must also have good wind-up ability  possess human hair without staining the scalp too much. The dyeings produced with it must be very stable against heat, light and those used in permanent hair Chemicals. Finally, the oxidation dye precursors in toxicological and dermatological Be harmless.

From DE-PS 25 09 096 2,4-dichloro- and 4,6-dichloro-3-aminophenol Known as a coupler for oxidation hair dye. Out DE-AS 24 29 967 is already a 6-chloro-3-acetylaminophenol as a coupler, however, not in terms of light fastness and Fastness against permanent wave treatment of the hair staining achieved with it.

It has now surprisingly been found that 2,4-dichloro-3-acetylaminophenol has very good coupler properties and with usual Developing substances for hair coloring of special high intensity and authenticity. This is especially in view very surprisingly that the corresponding 4,6-dichloro-3- acetylaminophenol practically no useful coupler properties owns.

The invention therefore relates to hair dyes containing Oxidation dye precursors in a cosmetic carrier, thereby characterized in that as oxidation dye precursors 2,4-dichloro-3-acetylaminophenol as a coupler component and the in Oxidation colorants contain usual developer substances are. The 2,4-dichloro-3-acetylaminophenol is not known from the literature, but it is from the 2,4-dichloro-3-aminophenol Acetylation with acetic anhydride by the usual method producible. 2,4-dichloro-3-acetylaminophenol is suitable as Coupler connection for a variety of known developer substances for the formation of oxidation stains of high intensity  and authenticity, with predominantly shades in the blue range will.

All known compounds can be used as developers will. Such developer substances are, for example p-phenylene diamine, p-tolylene diamine, N, N-diethyl-2-methyl-p-phenyl diamine, N-ethyl-N- (2-hydroxyethyl) -p-phenylenediamine, Chloro-p-phenylenediamine, N, N-bis (2-hydroxylethyl) -p-phenylenediamine, N, N-dimethyl-p-phenylenediamine, methoxy-p-phenylenediamine, 2,6-dichloro-p-phenylenediamine, 2-chloro-6-bromo-p-phenylenediamine, 2-chloro-6-methyl-p-phenylenediamine. 6-methoxy-3-methyl p-phenylenediamine, 2,5-diaminoanisole, N- (2-hydroxypropyl) -p-phenylenediamine, N-2-methoxyethyl-p-phenylenediamine, N-butyl-N-sulfobutyl- p-phenylenediamine and other compounds of the above Kind that further one or more NH₂ groups, NHR groups, May contain NR₂ groups, where R is an alkyl radical 1-4 or a hydroxyl alkyl group with 2-4 carbon atoms represents, also p-aminophenols, diaminopyridine derivatives and especially tetraaminopyrimidines such as 2,4,5,6-tetraaminopyrimidine, 4,5-diamino-2,6-bis-methylaminopyrimidine, 2,5-diamino-4-diethylamino 6-methylamino-pyrimidine, 2,4,5-triamino-6-piperidino-pyrimidine, 2,4,5-triamino-6-anilino-pyrimidine, 2,4,5-triamino-6- morpholinopyrimidine, 2,4,5-triamino-6- (2-hydroxyethyl) aminopyrimidine.

The hair dye according to the invention can in addition to the invention 2,4-dichloro-3-acetylaminophenol to be used also contain other known coupler substances for modification the color nuance and to create natural tones required are. Such usual coupler connections are e.g. B. other m-phenylenediamines, e.g. B. 2,4-diaminophenyl-2-hydroxyethyl ether and 2,4-diaminoanisole and phenols, naphthols, resorcinol derivatives, e.g. B. 2-methylresorcinol or pyrazolones.  

If necessary, direct dyes can also be used be used to further modify the color shades. Such substantive dyes are e.g. B. nitrophenylenediamines, Nitro-aminophenols, anthraquinone dyes or indophenols.

In the hair colorants according to the invention, the 2,4-dichloro- 3-acetylaminophenol and any additional ones Coupler substances generally in about molar amounts, based used on the developer substances used. If Molar use has also proven to be expedient however, it does not adversely affect a certain excess of individuals Bring oxidation dye precursors to use, where Developer substances and coupler substances in a molar ratio from 1: 0.5 to 1: 2 can be included.

The oxidative development of the color can in principle Atmospheric oxygen. However, a chemical one is preferred Oxidizing agents are used, especially if in addition to the coloring a lightening effect on the hair is desired. As an oxidizing agent come in particular hydrogen peroxide or its addition products of urea, melamine or sodium borate and Mixtures of such hydrogen peroxide addition products with potassium peroxide disulfate.

To produce the hair dye according to the invention the oxidation dye precursors in a suitable cosmetic Carrier incorporated. Such carriers are for example Creams, emulsions, gels or surfactant-containing, foaming Solutions, e.g. B. shampoos or other preparations that are suitable for use on the hair. Common ingredients such cosmetic preparations are such. B. network and emulsifiers such as anionic, nonionic or ampholytic Surfactants, e.g. B. soaps, fatty alcohol sulfates, alkane sulfonates, alpha-olefin sulfonates, fatty alcohol polyglycol ether sulfates, ethylene oxide addition products  of fatty alcohols, fatty acids and alkylphenols, Sorbitan fatty acid esters and fatty acid partial glycerides, Fatty acid alkanolamides and thickeners such as. B. methyl or hydroxyethyl cellulose, starch, fatty alcohols, paraffin oils, Fatty acids, also perfume oils and hair care additives, such as. B. water-soluble cationic polymers, protein derivatives, pantothenic acid and cholesterol.

The components of the cosmetic carrier are used in the manufacture of the hair dye according to the invention in the usual for these purposes Amounts used, e.g. B. become emulsifiers in concentrations of 0.5-30% by weight and thickeners in concentrations of 0.1-25 wt .-% of the total colorant used. The oxidation dye precursors are in quantities of 0.2-5% by weight, preferably 1 to 3% by weight of the total colorant mixed into the carrier. The content of 2,4-dichloro-3-acetylaminophenol can in the hair dye according to the invention be about 0.05-10 millimoles per 100 grams of hair dye.

The application of the hair dye according to the invention can be done independently on the type of cosmetic preparation, e.g. B. as a cream, gel or shampoo in weakly acidic, neutral or alkaline environment. It is preferred to use the Hair dye in a pH range of 8-10. The application temperatures can range between 15 ° C and 40 ° C lie. After an exposure time of approx. 30 minutes it will Hair dye removed by rinsing from the hair to be dyed. The hair is then washed with a mild shampoo and dried. There is no need to wash with a shampoo, if a high tenside carrier, e.g. B. a coloring shampoo has been used.

The dyeings achievable with the hair dye compositions according to the invention have high brilliance as well as good heat, light,  Wash and rub fastness properties as well as high stability against perm treatments.

The following examples are intended to illustrate the subject matter of the invention explain, but without restricting him to this.

Examples 1. Preparation of 2,4-dichloro-3-acetylaminophenol

A mixture of 20 g (0.09 mol) of 2,4-dichloro-3-aminophenol hydrochloride, 8.4 g (0.1 mol) of sodium acetate, 9.4 g (0.09 mol) of acetic anhydride and 40 ml of glacial acetic acid was refluxed for 4 hours heated to boiling. After cooling, the white one Filtered precipitate and discarded. The filtrate became Evaporated to dryness and the residue from aqueous ethanol recrystallized. The product was in the form of colorless Obtained crystals with a melting point of 77 to 79 ° C.

2. Hair dye attempts

There were hair colorants according to the invention in the form of a hair dye cream emulsion of the following composition:

Fatty alcohol C₁₂ _- ₁₄10 g fatty alcohol C₁₂ _- ₁₄ + EO-sulfate,
Na salt, 28% 25 g water 60 g coupler substance 0.0075 mol developer substance 0.0075 mol Na₂SO₃ (inhibitor) 1.0 g concentrated ammonia solution up to pH = 9.5 water 100 g

The ingredients were mixed together in order. After adding the oxidation dye precursors and the inhibitor was first the with concentrated ammonia solution pH of the emulsion was adjusted to 9.5, then was with water made up to 100 g.  

The oxidative development of the color was with 3% hydrogen peroxide solution performed as an oxidizing agent. For this 100 g of the emulsion were mixed with 50 g of hydrogen peroxide solution (3%) offset and mixed.

The coloring cream was standardized on approx. 5 cm long strands, 90% gray, but not specially pretreated Apply human hair and leave it there for 30 minutes at 27 ° C. After the dyeing process was finished, the hair was rinsed, washed out with a normal shampoo and then dried.

The following compound was used as the coupler substance:

K = 2,4-dichloro-3-acetylaminophenol

The following compounds were used as developer substance:

E 1 p-toluenediamine
E 2 N, N-bis ( β- hydroxyethyl) -p-phenylenediamine
E 3 p-aminophenol
E 4 p-phenylenediamine
E 5 2-chloro-p-phenylenediamine
E 6 N, N-dimethyl-p-phenylenediamine
E 7 2,5-diamino anisole
E 8 2,4,5,6-tetraaminopyrimidine

In Table I the results of the hair dye tests are shown with the coupler according to the invention and the developer substances E 1 to E 8 listed.  

Table I

Developer shade of dyed hair

E 1 black blue E 2 blue black E 3somali E 4 blue black E 5graumagenta E 6 blue black E 7 blue black E 8 storm blue

3. Comparative experiments

There were hair dyes of the same composition under Use of the developer substances E 1 to E 3 and the DE-OS 24 29 967 known coupler substance 6-chloro-3-acetyl aminophenol (KV). These hair dyes were made in dyed in the same way on strands of hair and lightfastness of hair coloring in the following way:

Lightfastness test

The lightfastness of the colored strands of hair was analogous to DIN 54 004 (April 1966), section 7.5.2. The method is there essentially in that the colored strands of hair next to Textile samples graded with 6 blue, lightfast Type staining of the light fastness scale with a xenon arc lamp exposed with a color temperature of 5500 to 6500 ° K.  will. For this, the highlights and textile samples are placed side by side attached to a cardboard and the marginal zones of the Highlights and textile samples parallel to the long edge of the sample holder covered. The exposure is under frequent control by removing the template until type 3 of the light fastness scale between the exposed and the unexposed part a clearly noticeable difference shows. Then you determine whether the samples show changes and evaluates them against the changes if necessary types 1, 2 and 3 of the light fastness scale. Then Exposure continues until type 4 of the light fastness scale the now exposed and the unexposed part shows a just perceptible color difference. Then swap one out the cover plate by a larger one, which is about 1/2 the covers previously exposed area parallel to the longitudinal edge. The Exposure continues until Type 6 of the scale is even noticeable color difference shows. The determination of light fastness is done by comparing the contrasts on the hair strands with the contrasts on the type colorations of the light fastness scale.

The results of the tests are summarized in Table II.  

Table II

From Table II it follows that the hair stains with the couplers according to the invention always have a higher light fastness rating exhibit.

Claims (2)

1. Hair dye containing oxidation dye precursors in a cosmetic carrier, characterized in that 2,4-dichloro-3-acetylaminophenol is present as the oxidation dye precursors as a coupler component and the developer substances customary in oxidation colorants. 2. Hair dye according to claim 1, characterized in that additionally contain other known coupler substances are that developer substances and coupler substances in molar ratio 1: 0.5 to 1: 2 are included, that the content of Oxidation dye precursors 0.2 to 5.0 wt .-% of the hair dye and the content of 2,4-dichloro-3-acetylaminophenol 0.05 to 10 millimoles per 100 g of hair dye.