NO149759B - HAARFARGEMIDDEL - Google Patents

Description

The object of the invention is a means for oxidative coloring of hair on the basis of benzodioxole or benzodioxane derivatives as coupling components.

For coloring hair, the so-called oxidation dyes, which occur by oxidative coupling of a developer component with a coupling component, play a preferred role due to their intense colors and very good authenticity properties. Nitrogen bases such as p-phenylene-diamine derivatives, diaminopyridines, 4-amino-pyrazolone derivatives, heterocyclic hydrazones are usually used as developers. Phenols, naphthols, resorcin derivatives and pyrazolones are mentioned as so-called coupling components.

Good oxidation hair dye components must first of all fulfill the following requirements: They must in the oxidative connection with the possible developer or coupler component form the desired color shades in sufficient intensity. They must also have a sufficient to very good ability to attract human hair and they should also be harmless from a toxicological and dermatological point of view. Furthermore, it is important that on the hair to be dyed, the strongest possible shades are obtained and strongly correspond to the natural hair color shades. Furthermore, the general stability of the dyes formed as well as their lightfastness, washing fastness and thermostability are of particular importance in order to avoid color shifts from the original color shade or even color changes in other shades.

When searching for usable, oxidation hair dyes, it was therefore the task of finding suitable components that fulfill the above-mentioned prerequisites to an optimal degree.

The invention relates to a hair dye agent based on oxidation dyes and with a content of additional common coupling agents as well as possibly common direct coloring dyes and a developer-coupler combination content of 0.2-5% by weight, preferably of 1-3% by weight , and the developer components common in oxidation dyes, as the hair dye is characterized by a content of benzodioxole or benzodioxane derivatives of the general formula

in which to R4 independently of each other means hydrogen, an alkyl residue with 1-4 carbon atoms, a hydroxy or amino group with the precaution that at least one of the residues R, to R^ must be hydrogen and at least one other a hydroxy or amino group and the number of hydroxy groups does not exceed 2, the residues X and Y can be the same or different and mean hydrogen, alkyl residues with 1-4 carbon atoms or phenyl residues and m has the values 0 or 1, and n the values 1 or 2, since n cannot be 2, when m means 1, as well as in the case of amino derivatives, their inorganic or organic salts as coupling agents.

When used as coupling components, the compound according to formula I with the developer substances usually used for oxidative hair dyeing produces very intense color shades that range from yellow to dark blue and is thus a significant enrichment of the oxidative hair dyeing possibilities. In addition, benzodioxol- resp. the benzodioxane derivatives in the hair dyes according to the invention are characterized by very good authenticity properties of the colorings thus obtained, by good solubility in water, good storage stability and toxicological and dermatological harmlessness.

The benzodioxol usable as coupling components

respectively benzodioxane derivatives can either be used as such or in the case of amino derivatives also in

form of their salts with inorganic or organic acids, such as e.g. such as chlorides, sulphates, phosphates, acetates, propionates, lactates, citrates.

The benzodioxole or benzodioxane derivatives in the hair dyes according to the invention are known compounds or can be prepared according to known methods such as, for example for the benzodioxole derivatives is mentioned in DE-OS 2,221,706 and for the benzodioxane derivatives by F.D. Chattaway and H. Irving in J. Chem. Soc. 19 31, p. 2494, by W. Borsche and A.D. Berkhout in Ann. 330 (1930),

p. 99, by P.M. Heertjes, A.A. Knape, H. Talsma in J. Chem. Soc. 1954, p. 1869, by P.M. Heertjes, H.C. van Beek in J. Chem. Soc. 1961, p. 2149, by M. Ando, S. Emoto in Bull. Chem. Soc. Yap. 46 (1973) p 2903, by W. Hensel, H. Hoyer in Zeitschr. f. Naturforschung B (1963) 18B and CH.M. Bowman, R.J. Wikholm, J. Boler, C.B. Bogentoft, K. Folkers in J.

With. Chem. 16 (1973) p. 990.

The use of heterocyclic ring systems as couplers for oxidation dyes is known from Harry<1>'s Cosmetology,

7th edition (1982), p. 535. From German Offenlegungsschrift

19 40 085, the use of benzo-morpholine derivatives as coupling components in oxidation hair dyes is also already known. However, this relates to structurally completely different compounds, so that no conclusions can be drawn from this to the subject of the invention.

Examples of developer components that can be used in the hair dyes according to the invention include primary aromatic amines with an additional functional group in the p-position such as p-phenylenediamine, p-toluylenediamine, monochloro-p-phenylenediamine, p-dimethylaminoaniline, p-aminophenol , p-diaminoanisole resp. other compounds of the aforementioned types which further form one or more functional groups such as OH groups, NH2~ groups, NHR groups, NR2~ groups, where R means an alkyl or hydroxyalkyl residue with 1-4 carbon atoms, further diaminopyridine derivatives , heterocyclic hydrazone derivatives, 4-aminopyrazolone derivatives as well as 4-amino-1-phenyl-3-carbamoyl-pyrazolone-5.

A further important group of developer components formed the tetraaminopyrimidines of the general formula

in which R,-R., means hydrogen, an alkyl residue with 1-4 carbon atoms, the residue.-(CH2)n~X, in which n = 1-4 and X. means a hydroxyl group, a halogen atom, a -NH2_, -NHR <1-> and -NR<1>R" group, wherein R' and R" can mean alkyl residues with 1-4 carbon atoms or are closed with the nitrogen atom of a heterocyclic ring which can contain a further nitrogen atom or oxygen atom. R-^ and R2, resp. R^ and R^, resp. R^ and R^ can with the possible nitrogen atom form a heterocyclic 5- or 6-membered ring with one or two nitrogen atoms or a nitrogen atom and an oxygen atom and their inorganic or organic salts.

The tetraaminopyrimidines usable 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, sulphates, phosphates, acetates, propionates, lactates, citrates.

They in combination with benzodioxole or the benzodioxane derivatives in the hair dyes according to the invention usable tetraaminopyrimidines are e.g. mentioned in DE-PS 2359399.

In the hair dyes according to the invention, the coupling components are usually used in approximately molar amounts, with reference to the developer used. Although the molar application also proves appropriate, it is not unfortunate if the coupling components are used in a certain surplus or deficit.

Furthermore, it is not necessary for the developer component and the coupling agent to form uniform products, thus the developer component can also form mixtures of usable developer compounds that the coupling substance also forms mixtures of usable benzodioxole or benzodioxane derivatives.

In addition, the hair dyes according to the invention may optionally contain ordinary direct coloring dyes in the mixture, if this is necessary to achieve certain color shades.

The oxidative coupling, i.e. development of the coloring can in principle take place as with other oxidation hair dyes also with atmospheric oxygen. However, chemical oxidizing agents are used appropriately. As such, hydrogen peroxide or its addition products to urea, melamine and sodium borate as well as mixtures of such hydrogen peroxide addition compounds with potassium peroxide disulphate are particularly relevant.

As the developer components, the tetraaminopyrimidine has the advantage that already upon oxidative coupling with atmospheric oxygen they give completely satisfactory color results and thus hair damage due to the oxidizing agent otherwise used for the oxidative coupling can be avoided. However, if a lightening effect is desired at the same time as the colouring, then the co-use of an oxidizing agent is necessary.

The hair dyes according to the invention are incorporated for use in corresponding cosmetic preparations such as creams, emulsions, gels or also simple solutions and are mixed immediately before application to the hair with one of the aforementioned oxidizing agents. The concentration of such color preparations of the coupler-developer combination amounts to 0.2-5% by weight, preferably 1-3% by weight. For the production of creams, emulsions or gels, the dye components are mixed with the additional components usual for such preparations.

As such additional components, there are e.g. to mention wetting or emulsifying agents of anionic or non-ionic type such as alkylbenzene 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 alcohols, paraffin oil, fatty acids, further perfume oils and hair care agents such as pantothenic acid and cholesterol. The aforementioned additives are thereby used in the usual amounts for these purposes, such as e.g. wetting and emulsifying agents in concentrations of 0.5-30% by weight and thickening agents in concentrations of 0.1-25% by weight, each time referring to the overall preparation.

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 jelly, take place in a slightly acidic, neutral or particularly alkaline environment with a pH value of 8-10. The application temperatures thereby move in the range

from 15-40°C. After an impact time 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.

The invention shall be explained by means of some examples.

Examples

In the following examples, benzodioxole or benzodioxane derivatives are either commercial products or they are produced in accordance with the specifications given in the above-mentioned literature citations.

The following compounds were used as the developer components in the following examples:

E 1 2,4,5,6-tetraaminopyrimidine,

E 2 p-toluylenediamine,

E 3 p-phenylenediamine,

E 4 p-aminophenol,

E 5 4-amino-N,N-dimethylaniline dihydrochloride, E 6 2-morpholino-4,5,6-triaminopyrimidine.

The following compounds served as coupling components:

K 1 5-amino-1,3-benzodioxole,

K 2 5-hydroxy-1,3-benzodioxole,

K 3 5-hydroxy-2,2-dimethyl-1,3-benzodioxole, K 4 6,8-diamino-1,3-benzodioxane dihydrochloride, K 5 6,8-diamino-7-methyl-1,3- benzodioxane dihydrochloride,

K 6 5-amino-1,3-benzodioxane,

K 7 6,7-diamino-1,4-benzodioxane dihydrochloride, K 8 5,7-diamino-1,4-benzodioxane dihydrochloride, K 9 Mixture of 2-methyl- and 3-methyl-5-hydroxy-1 ,4-benzodioxane,

K 10 5-hydroxy-1,4-benzodioxane.

The hair dyes according to the invention were used in the form of a cream emulsion. Thereby, in an emulsion of 10 parts by weight of fatty alcohols of chain length C±2~ C18', 10 parts by weight of fatty alcohol sulphate (sodium salt) of chain length C^2~<C>18'

75 parts by weight water,

each time incorporated 0.01 mol of the developing substances listed in the following table and benzodioxole or benzo-

dioxane derivatives. The pH value of the emulsion was then set to 9.5 using ammonia and the emulsion filled with water to 100 parts by weight. The oxidative coupling was either carried out with atmospheric oxygen or 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. The possible color cream with or without extra-oxidizing agent was applied to 90% gray, not specially pre-treated human hair, and left there for 30 minutes. After finishing the coloring process, the hair was washed out with

a regular hair detergent and then dried. The resulting colors are shown in table 1.'

Claims (1)

Hair dye based on oxidation dyes and with a content of additional common coupling agents as well as possibly common direct coloring dyes and a content of developer-coupler combinations of 0.2-5% by weight, preferably of 1-3% by weight, and the developer components common in oxidation dyes , characterized by a content of benzodioxole or benzodioxane derivatives with the general formula in which R^-R^ independently of each other means hydrogen, an alkyl residue with 1-4 carbon atoms, a hydroxy or amino group with the precaution that at least one of the residues R-^-R^ must be hydrogen and at least one another a hydroxy or amino group and the number of hydroxy groups does not exceed 2, the residues X and Y are the same or different and mean hydrogen, alkyl residues with 1-4 carbon atoms or phenyl residues and m has the value 0 or 1, and n the value 1 or 2 , where n cannot be 2, when m means 1, as well as in the case of amino derivatives, their inorganic or organic salts as coupling agents.