DE20115892U1 - Hair dyes containing pyrazole and/or substituted triazine oxidation dye precursors give more brilliant and intense shades when dihydroxy acetone, alloxan, methyl glyoxal or potassium iodide is present - Google Patents

Abstract

Hair dyes containing pyrazole (or a derivative such as a water-soluble salt) and/or a substituted triazine as a water-based oxidation dye precursor also contain 0.0001-5 wt.% (based on total composition wt.) of dihydroxy acetone, alloxan, methyl glyoxal and/or potassium iodide.

Description

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; A-33/01-U

Hair dye

The present invention relates to a hair dye based on a peroxide-reacting oxidation dye system which provides permanent, intense color tones which can either be applied as such or, in combination with other developers and/or couplers, to achieve further color nuances.

The developer substances still most commonly used in hair dyes are 1,4-diaminobenzene (p-phenylenediamine) and 1-methyl-2,5-diaminobenzene (p-toluenediamine). Although the use of these substances largely meets the color-technical wishes of the users, there are still color nuances that cannot be fully achieved or intensified.

It has already been proposed to close this gap by using alternative developing substances. This is possible to a limited extent by using 2-(2,5-diaminophenyl)ethanol (cf. EP-A 7537 and EP-B 400 330); however, compromises in the color intensity of other shades must then be accepted.

A further satisfactory solution to this problem is also achieved by the use of 2-(2'-hydroxyethylamino)-5-aminotoluene or its water-soluble salts as developing substances in hair dyes, as described in EP-A 615 743.

Even so, there are still some color-related wishes that remain unfulfilled.

Pyrazole and its derivatives such as 3,4-diamino-5-hydroxypyrazole have also been suggested as components of oxidative hair dyes.
However, it has not been possible to produce dyes in all desirable shades and, above all, in the desired intensity.

The invention is therefore based on the task of creating a hair dye which is suitable for producing a large number of shades and, above all, produces a particularly intense, shiny color.

This object is achieved in that such a hair dye contains at least one oxidation dye system which reacts with peroxide and which consists of a combination of at least one pyrazole or its water-soluble salts and/or a substituted triazole and 0.0001 to 5, preferably 0.001 to 1 wt. % of dihydroxyacetone and/or alloxan and/or methylglyoxal and/or potassium iodide, calculated on the total amount of the agent, in an aqueous base.

Preferred pyrazoles are pyrazole itself and the substituted pyrazoles 1-hydroxyethyl^.S-diaminopyrazole, 3,4-diamino-5-hydroxypyrazole, 3,5-diaminopyrazole, 3,5-diaminopyrazole-i-carboxamide, 3-amino-5-hydroxypyrazole, 1-phenyl-2-methylpyrazole, 1-phenyl-3-methylpyrazol-5-one, 3,5-dimethylpyrazole, 3,5-dimethylpyrazole-1-methanol and/or 3,5-diamino-1,2,4-triazole or their water-soluble salts.

Preferably, the agent according to the invention contains at least one coupling substance, for example selected from resorcinol, 2-methylresorcinol, 4-chlororesorcinol, 2-amino-4-chlorophenol, 5-amino-4-methoxy-2-methylphenol, 2-aminophenol, 3-aminophenol, 1-methyl-2-hydroxy-4-aminobenzene, 3-N,N-dimethylaminophenol, 2,6-dihydroxy-3,5-dimethoxypyridine, 5-amino-3-methylphenol, 6-amino-3-methylphenol, 3-amino-2-methylamino-6-methoxypyridine, 2-amino-3-hydroxypyridine, 2-dimethylamino-5-aminopyridine, 2,6-diaminopyridine, 1,3-diaminobenzene, 1-amino-3-(2'-hydroxyethylamino)benzene, 1-Amino-3-[bis(2'-hydroxyethyl)amino]benzene, a-naphthol, 4,6-dichlororesorcinol, 1,3-diaminotoluene, 1-hydroxynaphthalene, 4-hydroxy-1,2-methylenedioxybenzene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,7-Dihydroxynaphthalene, 1-hydroxy-2-methylnaphthalene, 4-hydroxy-1,2-methyldioxybenzene, 2,4-diamino-3-chlorophenol and/or 1-methoxy-2-amino-4-(2'-hydroxyethylamino)benzene or their water-

soluble salts.

However, this does not mean that the addition of further developers and couplers should be excluded.

When these compositions are used on a conventional base, very expressive, intense, permanent hair colors are obtained after oxidation with peroxide, which can be varied to other color nuances by adding appropriate additional developers and couplers.
The additional use of other known developing substances is also possible.

As such, preferably 1,4-diaminobenzene and substituted p-phenylenediamines, in particular 2,5-diaminotoluene, 2-n-propyl- or 2-ethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2-(2,5-diaminophenylene)ethariol, 1-amino-4-bis-(2'-hydroxyethyl)aminobenzene, 2-(-2-hydroxyethylamino)-5-aminotoluene, 4,4'-diaminodiphenylamine, 4-aminodiphenylamine, 2-amino-5-N,N-diethylaminotoluene, 4-amino-N-ethyl-N-isopropylaniline, 2-chloro-p-phenylenediamine, 1 ß-hydroxyethyl-2,5-diamino-4-methylbenzene, 2-methoxy-p-phenylenediamine, N,N-diethyl-p-phenylenediamine, 1-amino-4-ß-methoxyethylaminobenzene, 1-dimethylamino-4-aminobenzene, 1-hydroxy-2,5-diamino-4-methylbenzene, 1-hydroxymethyl-2,5-diaminobenzene, 1,3-dimethyl-2,5-diaminobenzene, 1,4-diaminoisopropylbenzene, i-amino-4-ß-hydroxypropylaminobenzene, 2-aminophenol, 4-aminophenols and their derivatives, tetraaminopyrimidines, triaminohydroxypyrimidines, diaminodihydroxypyrimidines, 5-aminosalicylic acid and/or 1,2,4-triaminobenzene or their water-soluble salts.

The total concentration of the developing substances is usually between about 0.05 and 5%, preferably 0.1 and 4%, in particular 0.25 to 0.5% and 2.5 to 3% by weight of the total composition of the hair dye (without oxidizing agent), whereby the information in each case refers to the proportion of free base.

The preferred weight ratio of the developer substances mentioned to the other developer and coupler substances is between about 1:8 to 8:1, preferably about 1:5 to .5:1, in particular..1..: 245is2:1? · : .:

The coupler substance(s) as reaction partner of the developer substance(s) are present in the hair dyes according to the invention in approximately the same molar proportion as the developer substances, i.e. in amounts of 0.01 to 5.0%, preferably 0.05 to 4%, in particular 0.1 to 3% by weight of the total composition (without oxidizing agent), whereby the information in each case refers to the proportion of free base.

The proportion of dihydroxyacetone and/or alloxan and/or methylglyoxal and/or potassium iodide is preferably about 0.0001 to 5, in particular about 0.001 to 1 wt.% of the colorant (without oxidizing agent composition).
If desired, the compositions according to the invention can also contain so-called shading agents for fine adjustment of the desired colour tone, in particular direct dyes.

Such nuancers are, for example, nitro dyes such as 2-amino-4,6i-dinitrophenol, 2-amino-4-nitrophenol, 2-amino-6-chloro-4-nitrophenol, etc., preferably in amounts of about 0.05 to 2.5%, in particular 0.1 to 1% by weight of the color composition (without oxidizing agent).

The hair dyes according to the invention can contain the basic and additive ingredients, conditioning agents, etc. that are customary in such agents and that are known to the person skilled in the art and are described, for example, in the monograph by
K. Schrader, "Fundamentals and formulations of cosmetics", 2nd edition (Hüthig Buch Verlag, Heidelberg, 1989), pp. 782 to 815. They can be in the form of solutions, creams, gels or in the form of aerosol preparations; suitable carrier material compositions are well known from the state of the art.

For application, the oxidation dye precursor according to the invention is mixed with an oxidizing agent. The preferred oxidizing agent is hydrogen peroxide, for example in a concentration of 2 to 12 percent.
However, other peroxides such as urea peroxide and melamine peroxide can also be used.

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As an alternative to peroxide oxidation, air oxidation can also be carried out, for example by applying a composition containing an oxidation dye precursor to the hair as an aerosol foam and leaving it there for about 15 to 30 minutes.

The pH value of the ready-to-use hair dye, i.e. after mixing with peroxide, can be in the weakly acidic range, i.e. a range from 5.5 to 6.9, in the neutral range or in the alkaline range, i.e. between pH 7.1 and 11.

In the following, various examples are given to explain the
invention given.

basis 8.0 (wt.%) Stearyl alcohol 4.5 Coconut fatty acid monoethanolamide 1.3 1,2-Propanediol mono/distearate 4.0 Coconut fatty alcohol polyglycol ether 1.0 Sodium lauryl sulfate 2.0 Oleic acid 1.5 1,2-Propanediol 0.5 Na-EDTA 1.0 Sodium sulphite 0.5 Protein hydrolysate 0.2 Ascorbic acid 0.4 Perfume 1.0 Ammonia, 25% 0.5 Ammonium chloride 0.8 Panthenol 0.0001 to 0.50 Potassium iodide 0.50 to 5.0 Dihydroxyacetone and/or alloxan and/or methylglyoxal up to 100,00 Water

The oxidation dye combinations according to the invention were incorporated into this base, with a corresponding reduction in the water content.
The dyeing was carried out on wool patches and strands of bleached human hair by applying a 1:1 mixture of dye precursor and 6% hydrogen peroxide solution (pH value of the mixture: 9.8) and leaving it for 20 minutes at room temperature, followed by rinsing and drying.

The following colorings were generated: _{#: :}

-7-

1.

1 2 3 4 5 6 7 8th 9 10 11 Hydroxyethyl^.S-diamino-
pyrazole sulfate 0.54 0.54 0.54 0.27 0.54 0.54 3,4-diamino-5-hydroxypyrazole sulfate 0.48 0.24 S.S-diaminopyrazole-i-carboxamide 0.31 3-Amino-5-hydroxypyrazole 0.22 1 -Phenyl-S-methylpyrazole-S-one 0.39 3,5-Diamino-1,2,4-triazol 0.22 p-Toluenediamine sulfate 0.50 0.49 4-Amino-2-hydroxytoluene 0.27 0.13 0.27 0.27 2-Amino-4-hydroxyethyl-amino-
anisole sulfate 0.62 0.62 4-Amino-3-methylphenol 0.27 1-Naphthol 0.16 Resorcin 0.30 Dihydroxyacetone 0.50 0.40 0.25 0.25 Alloxane 0.50 0.40 0.25 0.25 0.50 Methylglyoxal 0.50 0.45 0.25 0.25 0.50 Potassium iodide 0.002 0.002 0.002 0.003 0.005 0.005

Staining results: Without additional active ingredients With active ingredient combination

Intense dark magenta

Intense red copper

Deep purple

Intense red copper

Orange white

Intense violet

Brown-grey

Intense medium blonde

Red copper

Grey-brown

Dark magenta

1 Light magenta 2 Red copper 3 Violet 4 Red copper 5 Pink white 6 Matte violet 7 Yellow grey 8th Light blonde 9 Copper Blonde 10 Light grey brown 11 Light magenta

-8th-

2.

The following oxidation dye mixture was introduced into the described base, each with and without active ingredient, and the pH value was adjusted so that when mixed with 2% aqueous H ₂ O ₂ solution in a weight ratio of 1:1, a pH value of the ready-to-use mixture of 6.8 was achieved.
The mixture was then applied to wool patches and strands of bleached human hair, washed out and dried after 15 minutes of exposure, and the color was evaluated.

The following result was achieved:
composition

number 1 No. 1a 1-Hydroxyethyl-4,5-diaminopyrazole sulfate 0.54% 0.54% 4-Amino-2-hydroxytoluene 0.27% 0.27% Methylglyoxal 0.50% Potassium iodide 0.002% coloring Intense red copper Red copper

The composition No. 1 according to the invention achieves a shiny, intense
Coloration that was significantly superior to that of composition 1a.

Claims (5)

1. Agent for dyeing human hair, containing at least one oxidation dye precursor selected from pyrazole and its derivatives or their water-soluble salts and/or a substituted triazole in an aqueous base, characterized by a content of 0.0001 to 5% by weight of dihydroxyacetone and/or alloxan and/or methylglyoxal and/or potassium iodide, calculated on the total composition of the agent. 2. Agent according to claim 1, containing as pyrazole or triazole derivative at least one compound selected from 1-hydroxyethyl-4,5-diaminopyrazole, 3,4-diamino-5-hydroxypyrazole, 3,5-diaminopyrazole, 3,5-diaminopyrazole-1-carboxamide, 3-amino-5-hydroxypyrazole, 1-phenyl-2-methylpyrazole, 1-phenyl-3-methylpyrazole-5-one, 3,5-dimethylpyrazole, 3,5-dimethylpyrazole-1-methanol and/or 3,5-diamino-1,2,4-triazole or their water-soluble salts. 3. Agent according to claim 1 and/or 2, characterized in that it additionally contains at least one coupling substance. 4. Agent according to claim 3, containing at least one coupler substance selected from resorcinol, 2-methylresorcinol, 4-chlororesorcinol, 2-amino-4-chlorophenol, 5-amino-4-methoxy-2-methylphenol, 2-aminophenol, 3- Aminophenol, 1-methyl-2-hydroxy-4-aminobenzene, 3-N,N-dimethylaminophenol, 2,6-dihydroxy-3,5-dimethoxypyridine, 5-amino-3-methylphenol, 6-amino-3-methylphenol, 3-Amino-2-methylamino-6-methoxypyridine, 2-amino-3-hydroxypyridine, 5-amino-2-methoxyphenol, 2-dimethylamino-5-aminopyridine, 2,6-diaminopyridine, 1,3-diaminobenzene, 1- Amino-3-(2'-hydroxyethylamino)benzene, 1-Amino-3-[bis(2'hydroxyethyl)amino]benzene, α-naphthol, 4,6-dichlororesorcinol, 1,3-diaminotoluene, 1-hydroxynaphthalene, 4-hydroxy-1,2-methylenedioxybenzene, 1, 5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1-hydroxy-2-methylnaphthalene, 2,4-diamino-3-chlorophenol and/or 1-methoxy-2-amino- 4-(2'-hydroxyethylamino)benzene or its water-soluble salts. 5. Agent according to one or more of claims 1 to 4, containing 0.001 to 1 wt. % of dihydroxyacetone and/or alloxan and/or methylglyoxal and/or potassium iodide, based on the total composition.