SE447338B - SHARPING AGENTS BASED ON THE OXIDATION SUBSTANCES - Google Patents

Description

'447 saa # 3 baits of the formed dyes as well as their lightfastness, washability and thermostability are of great importance in avoiding color shifts from the original color shades or even color changes to other color tones.

Thus, when searching for useful oxidative hair dyes, one tried to find suitable components which optimally met the above conditions.

It has now been found that hair dyes based on oxidation dyes with a content of aminonaphthol monosulfonic acids and / or aminonaphthol disulfonic acids as coupling substances and the developing components customary in oxidation hair dyes correspond to a particularly high degree to the requirements.

When used as coupling components, the compounds according to the invention with the developing substances generally used for oxidative hair coloring give very intense yellow, red and brown color shades and thus provide a substantial enrichment of the oxidative hair coloring possibilities. In addition, the aminonaphthol sulfonic acids according to the invention are distinguished for giving very good authenticity properties of the dyes thus obtained, as well as for good solubility in water, good storage stability and for being toxicologically and pharmacologically risk-free.

The aminonaphthol sulfonic acids used according to the invention constitute compounds known from the literature.

The coupling components to be used according to the invention are, for example, 1-amino-8-naphthol-2,4-disulfonic acid, 1-amino-8-naphthol-3,6-disulfonic acid, 1-amino-8-naphthol-4,6-disulfonic acid , 2-amino-5-naphthol-1,7-disulfonic acid, 2-amino-8-naphthol-3,6-disulfonic acid, 1-amino-5-naphthol-7-sulfonic acid, 2-amino-S-naphthol-7 -sulfonic acid, 2-amino-8-naphthol-6-sulfonic acid, 1-amino-8-naphthol-6-sulfonic acid, 1-amino-8-naphthol-4-sulfonic acid.

As examples of the developing dyes used in the hair dyes according to the invention, primary aromatic amines have a further functional group present in the p-position such as p-phenylenediamine, p-toluylenediamine, p-dimethylaminoaniline, p-aminophenol, p-diaminoanisole resp. other compounds of the type mentioned, which may further contain one or more functional groups such as OH groups, NH2 groups, NHR groups, NR2 groups, wherein R represents an alkyl or a hydroxyalkyl group having 1-4 carbon atoms, in addition diaminopyridine radicals. heterocyclic hydrazone derivatives, 4-aminopyrazolone derivatives such as 4-amino-1-phenyl-3-carbamoyl-pyrazolone-5. e ..... \ .., ...-.._...........__..._....__., ....._ e _. Of particular importance are the aminonaphthol sulfonic acids used in combination with the tetraaminopyrimidines of the general formula R5 \ / R6 N NH 2 'ïÅ RARR / \ R 2 h' as components of the invention as cooling components. R 6 represents hydrogen, an alkyl radical having 1-4 carbon atoms, the radical ~ (CH 2) n ~ X, wherein n = 1-4 and X is a hydroxyl group, a halogen atom, an -NH-, -NHR'-alkyl; -NR'R "group, wherein R 'and R" represent alkyl groups having 1-4 carbon atoms, or R1 and R2, R3 and R4, R5 and R6 together with the nitrogen atom in question represent a heterocyclic 5- or 6- articulated ring with one or two nitrogen atoms or a nitrogen atom and an oxygen atom and their inorganic or organic salts as developing substances.

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

The tetraaminopyrimidines which can be used in combination with the aminonaphthol sulfonic acids in the hair dyes of the invention are, for example, 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-dimethylamino-6-ethylamino-, 4,5-diamino-2-dimethylamino-6-isopropylamino-, 4,5-diamino-2- dimethylamino-6-methylamino-, 4,5-diamino-6-dimethylamino-2-methylamino-, 4,5-diamino-2-dimethylamino-6-propylamino-, 2,4,5-triamino-6-dimethylamino-, 4,5,6-triamino-2-dimethylamino-, 2,4,5-triamino-6-methylamino-, 4,5,6-triamino-2-methylamino-, 4,5-diamino-2-dimethylamino-6 -piperidino-, 447 3%. 4,5-diamino-6-motylamino-2-piperidino-, 2,4,5-triamino-6-piperidino-, 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-, 2,4,5-triamino -6-di-n-propylamino-, 2,4,5-triamino-6-morpholino-, 2,6,6-triamino-4-dimethylamino-, 4,5,6-triamino-2-morpholino-, 2,4 , 5-triamipo-6-β-hydroxyethylamino-, 4,5,5-triamino-2-β-amino-ethylamino-, 2,5,6-triamino-4-3-methylamino-ethylamino-, 2,5- diamino-4,6-bis-fa-diethylamino-propylamino-, 4,5-diamino-2-methylamino-6-β-hydroxy-ethylamino-, 5-amino-2,4,6-triethylamino-, 2,4 -bis-β-hydroxyethylamino-6-anilino-5-amino-pyrimidine.

When the tetraaminopyrimidines are used as developing components, they give different, very intense color tones with the coupling substances generally used for oxidative hair dyeing. In addition, the tetraaminopyrimidines are distinguished by very good authenticity properties of the dyes thus obtained, by a good solubility in water, good storage stability and by being toxicologically and dermatologically risk-free.

It has now been found that the aminonaphthol sulfonic acids used according to the invention as coupling components are excellently suitable as special yellow, red and brown couplers for the tetraaminopyrimidine developing system. It is particularly advantageous that the intensity of the yellow, red and brown dyes formed is significantly improved in comparison with the dyes generated with another coupling component. In addition, the colors obtained with the coupling substances according to the invention are distinguished by a particularly good lightfastness.

Although intense hair dyes have also been obtained with other hitherto usual developing components, they are distinguished by excellent lightfastness and good through-dyeing ability.

In the hair dyes according to the invention, the coupling components are generally used in approximately molar amounts, calculated on the developing substance used. Although molar amounts have been found to be suitable, it is not inappropriate, however, if the coupling component is used in p. 447 338 a certain surplus or deficit.

It is also not necessary that the developing component and the coupling substance constitute uniform products, but the developing component may constitute mixtures of the developing compounds used according to the invention and the coupling component may constitute mixtures of the aminonaphthol sulfonic acids used according to the invention.

In addition, the hair dyes according to the invention may optionally contain customary direct pulling dyes in admixture if this is required to obtain a certain color shade.

The oxidative coupling, ie. the development of the dye, can in principle, as with other oxidative hair dyes, also take place with atmospheric oxygen.

Suitably, however, chemical oxidizing agents are used. As such, hydrogen peroxide or its storage products for urea, melamine and sodium borate and mixtures of such hydrogen peroxide storage compounds with potassium peroxide disulfate are particularly relevant.

As developing components, the tetraaminopyrimidines have the advantage that they already give a completely satisfactory color result during oxidative coupling with atmospheric oxygen and thus hair damage through the oxidizing agents otherwise used for oxidative coupling can be avoided. If, however, it is desired to obtain a bleaching effect on the hair at the same time as the color, it is necessary to also use oxidizing agents.

The hair dyes according to the invention are incorporated for use in corresponding cosmetic preparations such as creams, emulsions, gels or even simple solutions and are applied immediately before use to the hair with one of the mentioned oxidizing agents. The concentration of such coloring compounds of coupling-developing combination is 0.2-5% by weight, preferably 1-3% by weight. To prepare creams, emulsions or gels, the dye components are mixed with the additional ingredients customary for such preparations. As such additional constituents, for example, hydrogen or emulsifier of anionic or nonionic type such as alkylbenzene sulfonates, fatty alcohol sulfates, alkyl sulfates, fatty acid alkanolamides, ethylene oxide storage products to fatty alcohols, thickeners such as methylcellulose, paraffin oil, starch oil, perfume oil and hair care products such as pantothenic acids and carbonic acid are mentioned. The above-mentioned additives are used in the amounts suitable for these purposes, such as, for example, wetting and emulsifying models in concentrations of 0.5-30% by weight and thickening model concentrations of 0.1 to 25% by weight, calculated on each occasion on the total preparation. 447 3-53 6 The use of the hair dyes according to the invention can, regardless of whether it is a solution, an emulsion, a cream or a gel, be used in a slightly acidic, neutral or preferably alkaline environment at a pH value of 8- l0. The operating temperature then ranges in the range of 15-40 ° C. After an effect time of about 30 minutes, the hair dye is removed from the hair to be dyed, by rinsing. Then wash the hair with a mild shampoo and dry.

The invention is further illustrated by the following examples, in which the temperatures refer to degrees Celsius. The following examples were used as coupling components: 1: 2-amino-5-naphthol-7-sulfonic acid 2: 1-amino-5-naphthol-7-sulfonic acid 3: 2-amino-8-naphthol-3,6-disulfonic acid 4: 1-amino-8-naphthol-4,6-disulfonic acid: 2-amino-5-naphthol-1,7-disulfonic acid: 2-amino-8-naphthol-6-sulfonic acid 7: 1-amino-8-naphthol -6-sulfonic acid x vr w vv xv: w> <'w sf 5 6 7: 1-amino-8-naphthol-3,6-disulfonic acid 8 9: 1-amino-8-naphthol-4-sulfonic acid K10: 1 -amino-8-naphthol-2,4-disulfonic acid The following compounds were used as developing components: 1: 2,4,5,6-tetraaminopyrimidine 2: 2-dimethylamino-4,5,6-triaminopyrimidine 3: 4-piperidino-2, 5,6-triaminopyrimidine 4: 2-morpholino-4,5,6-triaminopyrimidine 5: 2-piperidino-4,5,6-triaminopyrimidine 6: 2-methylamino-4,5,6-triaminopyrimidine: r. 7: 4-Morpholino-2,5,6-triaminopyrimidine 8: ip-toluylenediamine Bibi 9: p-aminophenol The hair dyes according to the invention are used in the form of a cream emulsion; Thereby, in an emulsion of 10 parts by weight of fatty alcohol with the chain length C12-C18, 10 parts by weight of fatty alcohol sulphate (sodium salt), chain length C12-C18, 75 parts by weight of water were in each case 0.01 mol of the developing substance sulfonic acid sulfonic acid sulfonic acid listed in the table below. Then the pH of the emulsion with ammonia was adjusted to 9.5 and the emulsion was filled with water to 100 parts by weight. The oxidative coupling was carried out either with atmospheric oxygen or with 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 color cream in question with or without additional oxidizing agent was applied to 90% granular, not very pre-treated human hair and allowed to remain there for 30 minutes. After the coloring process was completed, the hair was washed with a conventional hair detergent and then dried. The colors obtained are shown in Table 1 below. 447 Table 1 Obtained color tone 'flour in air oxidation with m-ig Hzoz solution; 1 E 1 K 1 olive brown yellow 2 E 2 K 1 yellow-brown light brown 3 E 3 K 1 gray-yellow gray-yellow Eel E 5 K 1 light brown light brown 5 E 6 K 1 light brown brown 6 “E 4 K 1 yellow-brown: yellow-brown 7 13 1 K 2 ' yellow-brown yellow-brown 8 E 2 K 2 brown-orange brown-orange 9 E 3 K g brown-gray gray-brown 1o E 9 1: 2 brown yellow 11 E 1 K 3 yellow yellow 12 E 2 K 3 beige beige 13 E 8 K 3 brown olive brown 11! E 9 K 3 brunorfzngjca yellow 15 E 1 K lt gray-brown gray-brown 16 13 2 1ç L; reddish brown brown-orange 17 E s K L; brown chocolate brown 18 E 9 K Eel- gray gray 19 E 1 K 5 9111 light yellow 20 E 2 K 5 reddish brown yellow PJ E 8 K 5 olive chocolate brown 22 E 9 Ii 5 brown brown 23 E 1 K 6 brown orange orange zh r: s 1 : 6 gray cnoklaabrun 25 E 2 K 6 Or fi n fi íe reddish brown 26 IB 9 K 6 brown brown 27 B 1 K 7 brown orange orange 28 ESK 7 olive brown dark brown 9 Éabell 1 cont. 447 338 Yärhfxllelx fiüfqtfgn EX fl UP0l: íêïä: ššn.;: Fi ë: åånS vid luftoxidation nud 1 -í fi Hzoz-lësninq 29 E 9 K 7 kamelbrun brun 30 E 2 I. 7 rød rødolfansl fl 31 E 1 K 2 rødbrun 32 run gray brown 33 E 7 K 8 olive yellow 34 E 5 K 3 red maroon 35 13 6 1; g reddish brown qrish brown 36 in E 3 K 3 Stone gray earth brown 37 E 9 K 8 brown brown 38 E 1 K 9 brown light brown 39 E 2 1; 9 * reddish brown 'red _' ÅO E 5 K 9 brown red reddish brown H1 E 6 K 9 gray-brown reddish brown M2 E 8 K 10 gray-brown olive brown # 3 E 9 K 10 hair brown yellow-brown A4 E 1 K 10 yellow red-orange A5 E 3 K 19 red beige . , 4, ... .... rww ».

Claims (4)

_; _ V z: i: ll447 i A PATENTKRAV 1. Hair dyes based on oxidation dyes, characterized by a content of aminonaphthol monosulphonic acids and / or aminonaphthol disulphonic acids as coupling substances and in oxidation dyes customary developing components, the content of fi frame-calling-5-coupling combination being 0. Cent. A hair dye according to claim 1, k n n e t e c k- n a t thereof; that the tetraaminopyrimidines of the general formula used are the developing component: R5 \) R6 m2 * WR RßN / KN / N '3 / \ R 112 u' wherein R1-R6 represents hydrogen, an alkyl radical having 1 to 4 carbon atoms, the residue - ( CH 2) n X, wherein n is 1-4 and X is a hydroxyl group, a halogen atom, an -NH-, -NHR'- or -NR'R "group, wherein R 'and R" are alkyl radicals having 1-4 carbon atoms or R1 and R2, R3 and R4 and R6 and R6 nitrogen atom form a heterocyclic 5- or 6-membered ring with one or together with the two nitrogen atoms or a nitrogen atom and an oxygen atom, and their inorganic or organic salts. Hair dye according to Claim 1 or 2, characterized in that it contains additional customary coupling substances and, if appropriate, customary direct-acting dyes. 4. A hair dye according to claims 1-3, characterized in that the content of developing-coupling combination is 1-3% by weight.