DE2623563A1 - Oxidation hair dye compsn. - contains a hydroxy tetralin coupler and aminopyrimidine developer and dyes hair in yellow to brown shades - Google Patents

Abstract

An oxidn. hair dye compsn. contains a hydroxy-5,6,7,8-tetrahydronaphthalene of formula (I), (where R1 and R2 are each H, 1-4C alkyl or OH provided that >=1 is OH and X is H, 1-4c alkyl, 1-4C alkoxy or aryl) as the coupler and a conventional developer (II) for oxidn. dyes. (I) are special yellow couplerx with tetra-amino-pyridine (II) systems and result in intense yellow and brown dyes of improved heat stability. They also have esp. good light fastness. A chemical oxidant is not obligatory, air being sufficient.

Description

Hair coloring agents The invention relates to agents for oxidative Hair coloring based on hydroxy-5,6,7,8-tetrahydronaphtha linen as a coupler component.

The so-called oxidation colors play a role in the coloring of hair, that by oxidative coupling of a developer component with a coupler component arise because of their intense colors and very good fastness properties preferred role. Nitrogen bases are usually used as developer substances, such as p-phenylenediamine derivatives, diaminopyridines, 4-amino-pyrazolone derivatives, heterocyclic ones Hydrazones used. The so-called I-coupler components are m-phenylene-diamine derivatives, Phenols, naphthols, resorein derivatives and pyrazolones called Good oxidation hair dye components must primarily meet the following requirements: You must with the oxidative Coupling with the respective developer or coupler components the desired Develop color nuances with sufficient intensity. You must also have a sufficient to have very good absorption properties on human hair, and they should above it also be harmless from a toxicological and dermatological point of view. Farther It is important that the hair to be colored is as strong and natural as possible Hair color nuances largely corresponding shades can be obtained. This is where the intense ones play yellow and yellow-brown hues play a special role. The general one is more subtle Stability of the dyes formed and their lightfastness, washfastness and Thermostability of particular importance to avoid color shift from the original Avoid color nuances or even color changes in other shades.

There was therefore a search for useful oxidation hair dyes the task of finding suitable components, the aforementioned requirements meet in an optimal way.

It has now been found that hair dyes based on oxidation dyes with a content of hydroxy-5,6,7,8-tetrahydronaphthalenes of the general formula in which R1, R2 can represent hydrogen, an alkyl radical with 1-4 EohlenM material atoms, a hydroxyl group, with the proviso that one of the substituents R1 or R2 is a hydroxyl group and the other has the meaning also given and X is hydrogen, an alkyl radical with 1-4 carbon atoms means an alkoxy radical with 1-4 carbon atoms or an aryl radical as coupler substances and the developer components customary in oxidation hair dyes that meet the requirements to a particularly high degree.

Bci their use as coupler components provide the invention Compounds with the developer substances generally used for oxidation hair coloring very intense yellow and brown color nuances, as they are with these developer substances and the previously known couplers were not achievable and thus represent an essential Enrichment of the oxidative color of the skin.

The hydroxy-5,6,7,8-tetrahydronaphthalenes according to the invention are also notable by very good fastness properties of the dyeings achieved therewith, by a good solubility in water, good storage stability and toxicological as well as dermatological Indispensability.

Coupler components to be used according to the invention are, for example 1 hydroxy-5,6,7,8-tetrahydronaphthalene, 1-hydroxy-8-methyl-5,6,7,8-tetrahydronaphthalene, 1-hydroxy-5-phenyl-5,6,7,8-tetrahydronaphthalene, 1-hydroxy-8-butyl-5,6,7,8-tetrahydronaphthalene, 1-hydroxy-3-ethyl-5,6,7,8-tetrahydronaphthalene, 1-hydroxy-4-propyl-5,6,7,8-tetrahydronaphthalene, 1-hydroxy-4-ethoxy-5,6,7,8-tetrahydronaphthalene, 1-hydroxy-2-isopropyl-5,6,7,8-tetrahydronaphthalene, 2-hydroxy-5,6,7,8-tetrahydronaphthalene, 2-hydroxy-1-isopropyl 5,6,7,8-tetrahydronaphthalene, 2-hydroxy-3-methoxy-5,6,7,8-tetrahydronaphthalene, 2-hydroxy-6-phenyl-5,6,7,8-tetrahydronaphthalene, 2-hydroxy-8-ethyl-5,6,7,8-tetrahydronaphthalene, 2-hydroxy-7-methyl-5,6,7,8-tetrahydronaphthalene, 2-hydroxy-4-butyl-5,6,7,8-tetrahydronaphthalene, 2-hydroxy-5-ethoxy-5,6,7,8-tetrahydronaphthalene to be mentioned, the hydroxy-5 to be used as coupler components according to the invention , 6, 7, 8-tetrahydronaphthalenes can be prepared by conventional chemical synthesis processes produce and represent all compounds known from the literature. Their production can for example by hydrogenating appropriate naphthols in the presence of rhodium catalysts take place. Another way of synthesis is the ring closure reaction of optionally substituted m-penten-4-yl-phenols at elevated temperatures in a closed tube.

As examples of those to be used in the hair colorants according to the invention Developer components are primary aromatic amines with another in p-position functional group located such as p-phenylenediamine, p-tolylenediamine, p-dimethylaminoaniline, p-aminophenol, p-diaminoanisole or

other compounds of the type mentioned, which continue to be one or more functional groups such as OH groups, Ni12 groups, NIIR groups, NR2 groups where R represents an alkyl or hydroxyalkyl radical with 1-4 carbon atoms, furthermore Diaminopyridine derivatives, heterocyclic hydrazone derivatives, 4-aminopyrazolone derivatives how to list 4-amino-1-phenyl-3-carbomoyl-pyrazolon-5 $.

The hydroxy-5,6,7,8-tetrahydronaphthalenes to be used according to the invention as coupler components are of particular importance as yellow couplers in combination with tetraaminopyrimidines of the general formula in which R1 - R6 is hydrogen, an alkyl radical with 1 - 4 carbon atoms, the radical - (CH2) n - X, in which n = 1 - 4 and X is a hydroxyl group, a halogen atom, a -Mi2- -NHR '- and -NR 'R' group, where R 'and R''can be alkyl radicals with 1-4 carbon atoms or closed with the nitrogen atom to form a heterocyclic ring which can contain a further nitrogen atom or oxygen atom, furthermore R1 and R2, R3 and R4, R5 and R6 together with the respective nitrogen atom can represent a heterocyclic 5- or 6-membered ring with one or two nitrogen atoms or one nitrogen atom and one oxygen atom and their inorganic or organic salts as developer substances.

The tetraaminopyrimidines to be used as developer components can either as such or in the form of their salts with inorganic or organic Acids, e.g.

as chlorides, sulfates, phosphates, acetates, propionates, lactates, citrates can be used.

As in combination with the hydroxy-5,6'7,8-tetrahydronaphthalenes in the hair dyes according to the invention.

Tetraaminopyrimidines to be used are z, B.

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, 4,5,6Triamino-2-dimethylamino-2,4,5-triamino-6-methylamino-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-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-, 2,5,6-triamino-4-dimethylamino-, 4,5,6-triamino-2-morpholino-2,4,5-triamino-6-ß- hydroxyethylamino, 4,5,6-triamino-2-ß-amino-ethylamino-, 2,5,6-triamino-4-ß-methylamino-ethylamino-, 2,5-diamino-4,6-bis-γ-diethylamino-propylamino-, 4,5-diamino-2-methylamino-6-ß-hydroxy-ethylamino-, 5-Amino-2,4,6-triethylamino-, 2S4-bis-ß-hydroxyethylamino-6-anilino-5-aminopyrimidine to call.

The preparation of the tetraaminopyrimidines to be used as developer components is already known from the literature and can be compared to the monograph by D.J. Brown, "The Pyrimidines" in the series Heterocyclic Compounds, Interscience Publishers (1962) Volumes I and II can be removed.

For the synthesis of the compounds to be used as developer components one generally starts from 2,4,6-triaminepyrimidines from, in which introduced the 5-amino group by nitrosation and subsequent reduction will. But you can also use appropriately substituted triaminoalkyl mercaptopyrimidines go out and substitute the alkyl mercapto group with amines. The latter method is particularly suitable for introducing amino groups or substituted amino groups in the 2-, 4- or 6-position of the pyrimidine ring.

When used as developer components, the tetraaminopyrimidines provide with the coupler substances generally used for oxidation hair coloring the most varied, very intense colors. They also stand out the tetraaminopyrimidines because of their very good fastness properties Dyeings, due to good solubility in water, good storage stability and toxicological and dermatological safety.

It has now been found that the coupler components according to the invention Hydroxy-5,6,7,8-tetrahydronaphthalenes used are excellent suitable as a special yellow coupler for the tetraaminopyrimidine developer system, A particularly advantageous effect is that the thermal stability of the resulting Yellow and brown dyes versus that of one produced with other couplers Dye is significantly improved. Furthermore, with the inventive Coupler substances produced dyes due to their particularly good lightfastness. However, intensive use is also made with other developer components that have been customary up to now Hair colors obtained, which are characterized by extraordinary lightfastness and good Distinguish through coloring capacity.

The coupler components are used in the Daar coloring agents according to the invention generally ill approximately molar amounts, based on the developer substances used, used. Whenever the molar use proves to be expedient, so it is but not disadvantageous if the coupler component in a certain excess or Deficiency is used.

It is also not necessary that the developer component and the coupler substance represent uniform products, rather both the Developer component Mixtures of the developer compounds to be used according to the invention as well as the coupler substance mixtures of the hydroxy-5,6,7,8-tetrahydronaphthalenes to be used according to the invention represent.

In addition, the hair dyes according to the invention can optionally Usual direct drawing dyes contained in the mixture, if this is to achieve certain color nuances is required.

The oxidative coupling, i.e. the development of the color, can in principle As with other oxidation hair dyes, it is done by means of atmospheric oxygen. Zwecl; moderately however, chemical oxidizing agents are used.

Hydrogen peroxide or its addition products in particular come as such of urea, melamine and sodium borate and mixtures of such hydrogen peroxide addition compounds indications with italium peroxide disulfate.

The tetraaminopyrimidines have the developer component The advantage that they are fully satisfactory even with oxidative coupling by atmospheric oxygen Staining results deliver and thus a hair damage by the Oxidizing agents otherwise used for the oxidative coupling can be avoided. However, if at the same time a lightening effect is wiped on the hair in addition to the coloring, so the use of oxidizing agents is necessary.

The hair dyes according to the invention are suitable for use in cosmetic preparations such as creams, emulsions, gels or simple solutions incorporated and immediately before application on the flaar with one of the mentioned Oxidizing agents added. The concentration of such dyeing preparations of the coupler-developer combination is 0.2 to 5 percent by weight, preferably 1 to 3 percent by weight, for the production of creams, emulsions or gels the dye components with the other ingredients customary for such preparations mixed. Such additional components are e.g.

Wetting or emulsifying agents of the anionic or nonionic type such as alkylbenzenesulfonates, fatty alcohol sulfates, alkyl sulfonates, fatty acid alkanolamides, Addition products of ethylene oxide to fatty alcohols, thickeners such as methyl cellulose, Starch, higher Fcttalkeole, paraffin oil, fatty acids, furthermore perfume oils and hair care products like pantothenic acid and cholesterol. The additives mentioned are used in the amounts customary for this purpose, such as wetting and emulsifying agents in concentrations of 0.5 to 30 percent by weight and thickeners in concentrations from 0.1 to 25 percent by weight, in each case based on the total preparation.

The application of the hair colorants according to the invention can, independently whether it is a solution, an emulsion, a cream or a gel, in the weakly acidic neutral or in particular an alkaline environment at a pH of 8-10. The application temperatures vary in the range from 15 to 40 ° C. After a full exposure time of approx. 30 minutes it becomes the hair dye is removed from the all-colored hair by rinsing. After that it will Hair washed with a mild shampoo and dried. The following examples are intended to explain the subject matter of the invention in more detail, but without restricting it to this.

EXAMPLES In the following examples were given below Listed hydroxy-5,6,7,8-tetrahydronaphthalenes used as coupler components: K 1: 1-hydroxy-5,6,7,8-tetrahydronaphthalene K 2: 1-hydroxy-5,6,7,8-tetrahydronaphthalene The following compounds were used as developer components: E 1: 2,4,5,6-tetraaminopyrimidine E 2: 2-morpholino-4,5,6-triaminopyrimidine E 3: 2-methylamino-4,5,6-triaminopyrimidine E 4: 2-dimethylamino-4,5,6-triaminopyrimidine E 5: 4-piperidino-2,5,6-triaminopyrimidine E 6: p-phenylondiamine E 7: p-tolylenediamine E 8: p-aminophonel The invention Ila stains were used in the form of a cream emulsion. In an emulsion of 10 parts by weight of fatty alcohols of chain length C12-C18 10 parts by weight Fatty alcohol sulfate (sodium salt) chain length C12-C18 75 parts by weight of water each 0.01 mol of the developer substances listed in the table below and Hydroxy-5,6,7,8-tetrahydronaphthalenes incorporated. Thereafter, the pH was the Emulsion adjusted to 9.5 by means of ammonia and the emulsion made up to 100 parts by weight with water. The oxidative coupling was either with atmospheric oxygen or with 1% hydrogen peroxide solution as the oxidizing agent carried out, with 100 parts by weight of the emulsion 10 parts by weight of hydrogen peroxide solution were given.

The respective dye remnants with or without an additional oxidizing agent was applied to 90% gray not specially pretreated human hair and leave there for 30 minutes. After completing the dyeing process, the hair was Washed out with a standard shampoo and then dried. the The colorations obtained in this way are shown in Table 1 below.

Table 1 At- a) Ent- b) Kupp- Color obtained play winder with air with 1% iger oxidation of H2O2 solution 1 E 1 K 1 olive yellow-brown 2 E 2 K 1 yellow-brown 3 E 3 K 1 olive brown gray yellow 5 E 4 K 1 olive brown gray yellow 5 E 5 K 1 olive brown light brown 6 E 6 K 1 olive brown violet gray 7 E 7 K 1 olive brown - dark blue 8 E 8 K 1 olive brown yellow brown 9 E 1 K 2 gray-yellow yellow-brown 10 E 3 K 2 honey yellow gray yellow 11 E 4 K 2 gray-yellow gray-yellow # 12 E 6 K 2 olive brown red gray 13 E 7 K 2 olive brown dark brown 14 E 8 K 2 olive brown yellow brown

Claims (4)

Patent claims 1. Hair colorants based on oxidation dyes, characterized by a content of hydroxy-5,6,7,8 tetrahydronaphthalenes of the general formula in which R1, R2 can represent hydrogen, an alkyl radical with 1-4 carbon atoms, a hydroxyl group, with the proviso that one of the substituents R1 or R2 is an hydroxyl group and the other has the meaning also given and X is hydrogen, an alkyl radical with 1 - 4 carbon atoms, an alkoxy radical with 1 - 4 carbon atoms or an aryl radical means the coupler substances and the developer components customary in oxidation hair dyes. 2. Hair dye according to claim 1, characterized in that the developer component. Tetraaminopyrimidines of the general formula in which R1 - R6 is hydrogen, an alkyl radical with 1 - 4 carbon atoms, the radical - (CH2) n ~ X, in which n = 1 - 4 and X is a hydroxyl group, a halogen atom, a -NE2-, -NERt- and - NR'R "group, where R 'and R" can represent alkyl radicals with 1-4 carbon atoms or are closed with the nitrogen atom to form a heterocyclic ring which can contain a further nitrogen atom or oxygen atom, furthermore R1 and R2, R3 and R4, R5 and R6 together with the respective nitrogen atom can represent a heterocyclic 5- or 6-membered ring with one or two nitrogen atoms or one nitrogen atom and one oxygen atom and their inorganic or organic salts can be used. 3. Hair dye according to claim 1 and 2, characterized by a Content of other customary coupler substances and, where appropriate, customary direct pulling substances Dyes. 4. Hair dye according to claim 1-3, characterized by a Content of developer-coupler combinations from 0.2 to 5 percent by weight, preferably 1 to 3 percent by weight