DE20115884U1 - Oxidative dye precursors for human hair contain 1,4-diaminobenzene or a substituted p-phenylenediamine or their salts, together with dihydroxyacetone, alloxane, methyl glyoxal and/or potassium iodide - Google Patents

Abstract

A dye for human hair containing, as oxidation precursor, 1,4-diaminobenzene or a substituted p-phenylenediamine or their salts in an aqueous base, also contains 0.0001-5 wt.% dihydroxyacetone, alloxane, methyl glyoxal and/or (potassium, in disclosure but not claims) iodide.

Description

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Hair dye

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

The developer substances 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.

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

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This object is achieved in that such a hair dye contains at least one oxidation dye precursor which reacts with peroxide and which is selected from 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-diaminophenyl)ethanol, 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-chlorobenzene, 1-ß-hydroxyethyl-2,5-diamino-4-methylbenzene, 2-methoxy-p-phenylenediamine, N,N-di-ethyl-p-phenylenediamine, 1-amino-4-ß-methoxyethylaminobenzene, i-dimethylamino-4-aminobenzene, 1 -hydroxy^.S-diamino^-methylbenzene, 1 -hydroxymethyl^.S-diaminobenzene, 1,3-dimethyl-2,5-diaminobenzene, 1,4-diaminoisopropylbenzene and/or 1-amino-4-ß-hydroxypropylaminobenzene or their water-soluble salts, in an aqueous base, and 0.0001 to 5 wt.% dihydroxyacetone and/or alloxan and/or methylglyoxal and/or potassium iodide, calculated on the total composition of the agent.

Preferably, the agent according to the invention contains at least one coupling substance which can be 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, S-amino^-methylamino-e-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,

cc-naphthol, 4,6-dichlororesorcinol, 1,3-diamino-toluene, 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, 5-Amino-2-methoxy-

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phenol 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, in particular pyrazole and its derivatives such as 1-hydroxyethyl-4,5-diaminopyrazole, 3,4-diamino-5hydroxypyrazole, 3,5-diaminopyrazole, SS-diaminopyrazole-i-carboxamide, 3-amino-5-hydroxypyrazole, 1-phenyl-2-methylpyrazole, 1-phenyl-3-methylpyrazole-5-one, 3,5-dimethylpyrazole, 3,5-dimethylpyrazole-1-methanol, 3,5-diamino-1,2,4,-triazole, 2-aminophenol, 4-aminophenol and its derivatives such as 4-amino-3-methylphenol, 2-chloro-4-aminophenol, 2,6-dichloro-4-aminophenol, 2,4-diaminophenol, 2,6-dibromo-4-aminophenol, hydroxyindoles and -indolines as well as Tetraaminopyrimidines, triaminohydroxypyrimidines, aminodihydroxypyrimidines, amino-substituted triazines, 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 1:2 to 2:1.
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 ratio as the

developing 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 refers in each case 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, especially 0.025 to 2.5, in particular about 0.001 to 1% by weight of the colorant (without oxidizing agent composition).

If desired, the compositions according to the invention can also contain so-called shading agents for fine-tuning the desired color tone, in particular direct dyes.

Such nuancers are, for example, nitro dyes such as 2-amino-4,6-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 either in the weakly acidic range, e.g. a range of 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 embodiments are given to explain the invention.

basis

Stearyl alcohol 8.0 (wt.%)

Coconut fatty acid monoethanolamide 4.5

1,2-propanediol mono/distearate 1,3

Coconut fat alcohol polyglycol ether 4.0

Sodium lauryl sulfate 1.0

Oleic acid 2.0

1,2-Propanediol 1,5

Na-EDTA 0.5

Sodium sulphite 1.0

Protein hydrolysate 0.5

Ascorbic acid 0.2

Perfume 0.4

Ammonia, 25% 1.0

Ammonium chloride 0.5

Panthenol 0.8 Potassium iodide 0.0001 to 0.500 Dihydroxyacetone and/or Alloxan and/or 0.05 to 5.00 Methylglyoxal
Water ad 100,00

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The oxidation dye combinations according to the invention and dihydroxyacetone and/or alloxan and/or methylglyoxal and/or potassium iodide 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 colorations were achieved:

1 2 3 4 5 6 7 8th G 10 11 p-Phenylenediamine 0.24% p-Toluenediamine sulfate 1.01 0.54 0.88 Hydroxyethyl-p-
phenylenediamine sulfate 0.56 N,N-Bis-Hydroxyethyl-p-
phenylenediamine sulfate 0.66 2-(2'-Hydroxyethylamino)-
5-aminotoluenesulfate 0.71 2-Amino-5-diethylamino-
toluene hydrochloride 0.48 4-Amino-N-ethyl-N-iso-
propylaniline 0.48 0.48 1-ß-Hydroxyethyl-2,5-di-
amino-4-methylbenzene 0.60 Resorcin 0.21 0.03 0.25 0.25 m-Aminophenol 0.23 0.11 0.13 m-Phenylenediamine 0.24 4-Amino-2-hydroxytoluene 0.55 0.04 0.30 2-Amino-4-hydroxyethyl-
aminoanisole sulfate 0.63 2-Amino-3-hydroxypyridine 0.25% 0.2 0.25 1-Naphthol 0.16 0.16 Alloxane 0.50 0.40 0.25 025 0.50 Methylglyoxal 0.50 0.45 0.25 0.25 0.50 Dihydroxyacetone 0.50 0.40 0.25 0.25 Potassium iodide 0.002 0.002 0.002 0.005 0.003 0.005

Coloring results: Without additional active ingredients With active ingredient combination

1 Red Brown Intense Red Brown

2 Violet Deep violet

3 Medium Blonde Intense Medium Blonde

4 Mahogany Intense Mahogany

5 Red Brown Intense Red Brown

6 Azure Dark Azure

7 Navy Blue Dark Navy Blue

Matt red -8th- Grey-brown 8th Turquoise Dark turquoise 9 Matt red Grey-brown 10 Violet Deep purple 11

2,

The following oxidation dye mixtures, each with and without 0.5% by weight of dihydroxyacetone and 0.005% by weight of potassium iodide, were introduced into the described base 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 mixtures were then applied to wool patches and strands of bleached human hair, washed out and dried after 15 minutes of exposure, and the coloring was evaluated.
The following result was achieved:

No. 1 1a 2 2a 3 3a Violet p-Toluenediamine sulfate 1.40 1.40 0.45 0.45 1.17 1.17 Resorcin 0.60 0.60 0.10 0.10 — — 3-Aminophenol 0.10 0.10 0.07 0.07 — — 2-Amino-4-hydroxyethylaminoanisole sulfate 0.02 0.02 — — — — 4-Amino-2-hydroxytoluene — — 0.01 0.01 0.60 0.60 1-Naphthol — — — — 0.15 0.15 2,5,6-triamino-4-hydroxypyrimidine sulfate — — 0.01 0.01 — — Dihydroxyacetone 0.50 — 0.50 — 0.50 — Potassium iodide 0.005 — 0.005 — 0.005 — coloring Light brown Medium blonde

Compositions Nos. 1, 2 and 3 according to the invention all achieved shiny, intense colorations which were clearly superior to those of compositions 1a, 2a and 3a.

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3,

A colour foam aerosol with the following composition was prepared:

p-Toluenediamine sulfate pH 0.60 (wt.%) ad 0.20 N,N-Bis(hydroxyethyl)-p-phenylenediamine sulfate 0.20 Resorcin 0.15 3-Aminophenol 0.05 1-Naphthol 0.10 Sodium sulphite 0.10 Ascorbic acid 0.15 Cocamide MEA 0.13 Stearamide MEA 0.15 Perfume 0.30 Hydroxyethylcellulose 0.25 Ammonium chloride 2.00 Cocoamidopropyl betaine 1.00 Oleth-5 0.70 Cetearyl alcohol 0.10 Preservatives 0.10 EDTA 8.5 Ethanolamine 100.00 Water

100 parts by weight of this composition were filled into an aerosol can equipped with a foam valve with 6 parts by weight of a commercially available propellant mixture of propane/butane.

To a portion of the composition, 0.7 wt% dihydroxyacetone and 0.25 wt% alloxan were added.

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In a half-side test, the composition without dihydroxyacetone and alloxan was evenly applied to the wet hair of one half of the head and the composition with dihydroxyacetone and alloxan was evenly applied to the other half of the head.

After 15 minutes of exposure, the hair was rinsed, dried and both halves of the hair were compared.

The half of the hair treated with the composition according to the invention containing dihydroxyacetone and alloxan had a shiny medium blonde color, while the half of the hair treated with the composition according to the prior art showed a significantly paler light blonde color.

Claims (5)

1. Agent for dyeing human hair, containing at least one oxidation dye precursor selected from 1,4-diaminobenzene and substituted p-phenylenediamines or their water-soluble salts 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 iodide calculated on the total composition of the agent. 2. Agent according to claim 1, containing as substituted p-phenylenediamines 2,5-diaminotoluene, 2-n-propyl- or 2-ethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2-(2,5-diaminophenyl)ethanol, 1-amino-4-bis-(2'-hydroxyethyl)-aminobenzene, 2-(2-hydroxyethylamino)-5-aminotoiuoi, 4,4'-diaminodiphenylamine, 4-aminodiphenylamine, 2-amino-5-N,N-diethylaminotoluene, 4-amino-N-ethyl-nisopropylaniline, 2-chloro-p-phenylenediamine, 1-β-hydroxyethyl-2,5-diamino-4-chlorobenzene, 1-β-hydroxyethyl-2,5-diamino-4-methylbenzene, 2-methoxy-p-phenylenediamine, N,N-diethyl-p-phenylenediamine, 1-amino-4-β-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 and/or 1-amino-4-β-hydroxypropylaminobenzoi 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 coupling 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, 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, 4-hydroxy-1,2-methylenedioxybenzene, 2,4-diamino-3-chlorophenol, 5-amino-2-methoxyphenol and/or 1-methoxy-2-amino-4-(2'-hydroxyethylamino)benzene or their water-soluble salts. 5. Agent according to one or more of claims 1 to 4, containing 0.001 to 1 wt.% dihydroxyacetone, based on the total composition.