FI65909C - HAORFAERGNINGSMEDEL - Google Patents

Description

65909 desired color tones with a sufficiently high intensity. In addition, they must have a sufficiently good or, preferably, a very good adhesion to human hair, in addition to which they must be completely harmless in toxicological and dermatological terms. In addition, it is of great importance that the hair to be dyed can have the strongest and most natural color tones that correspond to the desired color tones. In addition to this, it is important that the toners are stable and resistant to washing and the effects of light and heat, so that changes in color from the original color tone or even color changes are avoided.

Thus, in the search for useful hair oxidizing dyes, it is necessary to find components that meet the above requirements in the best possible way.

U.S. Patent No. 2,468,277 describes azo dyes obtained by diazonation of 6-amino-1,3-benzodioxane and coupling at azo switch pressure. Also in Melliand Textilberichte 40, (1959), no. 4, pp. 417-419 discloses benzo-1,4-dioxane azo dyes. However, in terms of their composition, coloring properties and use, these dyes differ so thoroughly from oxidizing dyes that it is not possible to deduce anything about the suitability of the starting materials for their preparation for the production of hair oxidizing dyes.

It has now been found that a hair dye based on oxidative dyes and containing benzodioxole or benzodioxane derivatives of the general formula R satisfies the above requirements very well.

R, - <, —x Τ '(CXY) .401 i

R 1 in which the formula R 1 -R 4 are independently hydrogen, an alkyl group having 1 to 4 carbon atoms, a hydroxy group or an amino group, in which case at least one of R 1 -R 65 659 is hydrogen and at least one other . the groups have a hydroxy group or an amino group, in which case there may be no more than two hydroxy groups, and in which X and Y may be the same or different and may represent hydrogen, an alkyl group having 1 to 4 carbon atoms, or an aryl group, and m represents a numerical value O or 1 and n denote the numerical value 1 or 2, or in the case of amino derivatives, their inorganic or organic salts as coupling agents and, in the case of oxidation dyes, the customary developer components.

When added as coupling components, the compounds of the invention generally impart very intense yellow to dark blue colorants to the oxidative hair dye developers and thus substantially improve the use of oxidative hair dye. In addition, the benzodioxole and benzodioxane derivatives of the present invention are characterized by the fact that the dyes applied to them give a very authentic impression, in addition to which they are very soluble in water, very stable in storage and completely harmless in toxicological and dermatological terms.

According to the invention, the benzodioxole and bentodioxane derivatives used as coupling components can be added to the mixture, either as such or, in the case of amino derivatives, also in the form of their salts with inorganic or organic acids, such as chlorides, sulphates, phosphates, acetates, lactates, propionates, propionates.

The benzodioxo-li and benzodioxane derivatives used as coupling components according to the invention are known compounds and can be prepared using known methods for benzodioxole derivatives in DT-OS 2,221,706 and for benzodioxane derivatives in F.D. Chattaway and K. Irving, J. Chem.Soc. 1931, pp. 2494, W. Borsche and A.D. Berkhout, Ann. 330 (1903), pp. 99, P.M. Heertjes, A.A. Knape, H. Talsma, J. Chem. Soc. 1954, b. 1869, P.M. Heertjes, H.C. van Beek, J. Chem. Soc. 1961, s, 2149 M. Ando, S. Emoto, Bull. Chem. Soc. Jap. 46 (1973) pp. 2903, von W. Hensel, H. Hoyer, Zeitschr. f. Naturforschung B (1963) 65909 18 B and CH. M. Bowman, R. J. Wikholm, J. Boler, C.B. Bogentoft, K. Folkers, J. Med. Chem. 16 (1973) pp. 990.

Among the coupling components used according to the invention are 5-amino, 5-hydroxy, 5-amino-2-methyl, 5-hydroxy-2,2-dimethyl, 5-hydroxy-2-ethyl, 5-hydroxy-2 -butyl, 5-hydroxy-2-phenyl, 5,6-dihydroxy, 4,7-dihydroxy, 4,7-diamino-2-methyl, 5,6-diamino-2,2- diphenyl, 4,5,7-triamino, 5-hydroxy-7-methyl-2,2-diethyl-1,3-benzodioxole, 5-amino, 5-hydroxy, 6,8-diamino, 6 , 8-diamino-7-methyl, 5,7-diamino-2-methyl, 5-hydroxy-2,2-dimethyl, 6,7-dihydroxy-4-methyl, 6,7-diamino-2-phenyl -, 5,8-dihydroxy-2,2-dimethyl-1,3-benzodioxane, 5-hydroxy-, 6,7-diamino-, 5,7-diamino-, 5-hydroxy-2-methyl-, 5-hydroxy- 3-methyl-, 5,7-diamino-2-ethyl-, 6-7-dihydroxy-3-butyl, 6-7-diamino-2-phenyl-, 6,8-diamino-7-methyl-, 5- hydroxy-8-methyl-2,2-dimethyl-1,4-benzodioxans.

Examples of developer components to be added to hair dyes according to the invention are primary aromatic amines which additionally have a functional group in the p-position, such as p-phenylenediamine, p-toluenediamine, mono-chloro-p-phenylenediamine, p-dimethylamino-pine, p-dimethylaminoaniline, -diaminoananizes as well as other such compounds further having one or more functional groups such as OH groups, NH 4 groups, NHR groups, NR 4 groups, wherein R is an alkyl-C 1-4 hydroxyalkyl group having 1 -4 carbon atoms, in addition to diaminopyridine derivatives, heterocyclic hydrazone derivatives, 4-aminopyrazolone derivatives such as 4-amino-1-phenyl-3-carbamoyl-pyrazolone-5.

Another important group of developer components are tetraaminopyrimidines of the general formula τ'Λγ, Η * R 2 ^ * 4 6 5909 wherein R 1 -R 8 may be hydrogen, an alkyl group having 1 to 4 carbon atoms, a group - (CH 2) n X wherein n is 1-4 and X is a hydroxyl group, a halogen atom, an -NH 2 -N NMR 'or -NR'R' 'group, wherein R' and H 1 'may represent alkyl groups having 1 to 4 carbon atom or which form a heterocyclic ring with a nitrogen atom, which may further contain another nitrogen atom, and in which R 1 or R 2 and R 4 or R 4 and R 2 may form a heterocyclic 5- or 6-membered ring with one nitrogen atom having one or two nitrogen atoms or one nitrogen atom and one oxygen atom, and their inorganic or organic salts.

The tetraaminopyrimidines used as developer components can be added either as such or in the form of their salts with inorganic or organic acids, such as, for example, chlorides, sulfates, phosphates, acetates, propionates, lactates, and citrates.

Examples of tetraaminopyrimidines which can be used in combination with benzodioxole or benzodioxane derivatives in the hair dye according to the invention are: 2,4,5,6-tetraamino, 4,5-diamino-2,6-bismethylamino, 2,5-diamino-4,6-bismethylamino, 4,5-diamino-6-butylamino-2-dimethylamino, 2,5-diamino-4-diethylamino-6-methylamino, 4,5-diamino-6-diethylamino-2-dimethylamino, 4,5-diamino-2-diethylamino-6-methylamino -, 4,5-diamino-2-diroethylamino-6-ethylamino, 4,5-diamino-2-dimethylamino-6-isopropylamino, 4,5 "diamino-2-diraethylamino-6-methylamino, 4,5-diamino-6- dimethylamino-2-methylamino, 4,5-diamino-2-dimethylamino-6-propylamino, 2,4,5-triaraino-6-dimethylamino, 4.5,6-triamino-2-diraethylamino, 2.4.5-triamino— 6-methylethylamino, 4,5,6-triamino-2-methylamino, 4,5-diamino-2-dimethylamino-6-piperidino, 4,5-diamino-6-methylamino-2-piperidino, 2,4,5-triamino-6- piperidiono-, 6 65909 2.4.5-triamino-6-anilino-, 2.4. 5-triamino-6-benzylamino, 2,4,5-triamino-6-benzylideneamino, 4,5,6-triamino-2-piperidino, 2,4,6-trismethylamino-5-amino, triamino-6-di-n-propylamino, 2.4.5-triamino-6-morpholino, 2.5.6-triamino-4-dimethylamino, 4.5.6-triamino-2-morpholino, 2.4.5-triamino- 6- [3-hydroxyethylamino-, 4,5,6-triamino-2- [3-amino] ethylamino, 2,5,6-triamino-4- [N-diethylamino] ethylamino], 2,5-diaraino-4,6-bis -p-Diethylamino-propylamino-, 4,5-diaraino-2-methyl-amino-6- [3-hydroxy-ethylamino-, 5-amino-2,4,6-triethylamino-, 2,4-bis-γ (? -hydroksietyyliamino-6-anilino-5-amino-pyrimidine.

Coupling components are generally added to the hair dyes of this invention in approximately molar amounts based on the developers used. However, even if a molar addition amount proves to be appropriate, it is not detrimental if the coupling components are used in some excess or underscore.

Furthermore, it is not necessary that the developer components and the coupling components form homogeneous products, but rather mixtures of the developer compounds used according to the invention and mixtures of benzodioxole or benzodioxane derivatives used according to the invention can be used as developer components.

In addition, the hair dyes according to the invention may, if necessary, also contain the usual direct coloring dyes in mixtures, if this is necessary for the purposes of the invention in order to obtain certain color tones.

Oxidative coupling reaction, i.e. the development of coloring can, in principle, take place in the same way as with the use of other antioxidant hair dyes, i.e. under the influence of oxygen in the air. However, it is appropriate to use chemical oxidants, 65909, which are added to the mixture. Suitable such substances are, in particular, hydrogen peroxide or its reaction products with urea, melamine and sodium borate, or mixtures of such reaction products with potassium peroxide disulphate.

The tetraaminopyrimidines then have the advantage, as developer components, that they provide a completely satisfactory coloring result in oxygen-coupled air, as a result of which damage to the hair by the oxidizing coupling agents can be avoided. However, if, in addition to coloring, it is desired to achieve hair bleaching at the same time, it is necessary that oxidizing agents are also used.

The hair dyes according to the invention are mixed in a similar manner as cosmetic preparations, such as creams, emulsions, gels or also as simple solutions, and are immediately mixed with one of the abovementioned oxidizing agents immediately before use. Such dyeing preparations have a content of the coupling developer combination of 0.2 to 5% by weight, preferably 1 to 3% by weight. In preparing creams, emulsions or gels, the dye components are mixed with the ingredients commonly used in such preparations. Such ingredients include, for example, wetting or emulsifying agents of either the anionic or nonionic type, such as alkylbenzenesulfonates, fatty alcohol sulfates, alkyl sulfonates, fatty acid alkanolamides, ethylene oxide and fatty alcohol fusion products, thickening agents such as methyl -alcohols, paraffin oil, fatty acids and in addition perfume oils and hair conditioners such as pantothenic acid and cholesterol. Said additives are then used to achieve these purposes in conventional amounts, such as, for example, wetting and emulsifying agents, in concentrations of 0.5 to 30% by weight and thickeners are used in concentrations of 0.1 to 25% by weight, the percentages being calculated on the total weight of the preparation.

The hair dye according to the invention can be used, whether it is a solution, emulsion, cream or gel, in a slightly acidic, neutral and especially alkaline environment with a pH of 8-10. The operating temperatures are then in the range 15-40 ° C. After a treatment time of about 30 minutes, the hair dye is removed from the hair to be dyed by rinsing. The hair is then post-washed using a mildly active shampoo, followed by drying.

The following examples further illustrate the subject matter of the invention without limiting the scope of the invention in any way.

In the following examples, the benzodioxyl or benzodioxane derivatives to be added as coupling components are either commercially available products or are prepared by the preparation methods described in the above-mentioned literature references.

The following compounds were used as developer components in the examples: E 1 2,4,5,6-tetraolinopyrimidine, E 2 p-twilylenediamine, E 3 p-phenyldiamine, E 4 p-amylophenol, E 5 4-amino-N, N-dimethylaniline dihydrochloride, E 6 2-morpholino-4,5,6-triamiopyrimidine.

The following compounds were used as coupling components: K 15 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 65909 K 8 A mixture of 5,7-diamino-1,4-benzodioxane dihydrochloride K 9 with 2-methyl and 3-methyl-5-hyuroxy-1,4- benzodioxane K 10% -hydroxy-1,4-benzodioxane.

The hair dyes according to the invention were used as a cream emulsion. An emulsion having the following composition was prepared.

10 parts by weight of a fatty alcohol having a chain length of c12 to C18 by weight of a fatty alcohol sulfate (sodium salt) having a carbon chain length of C1 to C10. to 75 parts by weight of water, to which were added in each case 0.01 mol of the developing agents and benzodioxole or benzodioxane derivatives shown in the following table. The pH of the emulsion was then adjusted to 9.5 using ammonia, and water was added to the emulsion so that the total amount of the emulsion became one hundred parts by weight. The oxidative coupling reaction was performed using either oxygen-free or 1% hydrogen peroxide solution as the oxidizing agent, with 10 parts by weight of hydrogen peroxide solution being added to one hundred parts by weight of the emulsion. Each prepared coloring cream, with or without added oxidizing agent, was applied to 90% grayed but not specifically pretreated human hair and the cream was left in place for 30 minutes. After completing the coloring process, the hair was washed using a conventional hair wash sponge, after which the hair was dried. The stains obtained in this case are shown in Table 1 below.

10 65909

table 1

Example a) frame- b) switch-Achieved color tone _ tin material using air using 1- oxidized $ Η? 0 ~ -li buy 1 E 1 K 1 gray-brown gray-brown 2 E 2 K 1 olive brown earth brown 3 E 1 K 2 reddish brown reddish brown 4 E 2 K 2 olive brown gray-brown 5 E 1 K 3 olive brown brown-orange 6 E 2 K 3 olive brown gray-brown 7 E 1 K 4 yellow-brown yellow-brown 8 E 2 K 4 gray-brown gray-brown 9 E 1 K 5 brass-yellow brown-yellow 11 E 1 K 6 gray-yellow gray-yellow yellow 12 E 2 K 6 gray-brown gray-brown 13 E 1 K 7 yellow-brown yellow-brown 14 E 2 K 7 olive brown olive brown 15 E 1 K 8 deep green olive 16 E 2 K 8 dark blue dark blue 17 E 2 9 E 1 K 10 light gray olive gray 19 K 2 K 10 light gray dark blue 20 E 3 K 10 blue-gray purple-gray 21 E 4 K 10 brown-orange gray-brown 22 E 5 K 10 fur gray dark blue 23 E 6 K 10 brown-gray aa brown-gray ____. l_I_

Claims (3)

65909 11 Hair dye based on oxidative dyes, characterized in that it contains benzodioxole or benzodioxane derivatives of the general formula * 4 R 5 -, C 1 -C 5) in which R 1 -R 2 may independently be hydrogen, an alkyl group having 1 -4 carbon atoms, a hydroxy group, or an amino group, wherein in this context at least one of the groups R 1 -R 2 is hydrogen and at least one other is the groups have a hydroxy group or an amino group, in which case there may be no more than two hydroxy groups, and in which X and Y may be the same or different and may represent hydrogen, an alkyl group having 1 to 4 carbon atoms, or an aryl group, and m represents a numerical value O or 1 and n denote the numerical value 1 or 2, or in the case of amino derivatives, their inorganic or organic salts as coupling agents and, in the case of oxidation dyes, the customary developer components. Hair dye according to Claim 1, characterized in that it also contains customary coupling agents and, if appropriate, also customary direct coloring dyes. Hair dye according to Claim 1 or 2, characterized in that it has a developer composition with a concentration of 0.2 to 5% by weight, preferably 1 to 3% by weight.