JPH05186319A - Oxidative hair dye - Google Patents

Abstract

PURPOSE: To obtain an oxidative hair dye capable of dyeing the hair fast with natural dense color without any problems in terms of both toxicology and dermatology by the use of an inexpensive dye. CONSTITUTION: This oxidative hair dye contains (A) 2,5-diaminotoluene as color developing ingredient and, as coupling agent, at least one kind of compound selected from (B) 2,6-diaminopyridine, (C) resorcinol and (D) compounds of the formula (R<1> is H, F, Cl, Br or I; R<2> is H, a 1-4C hydroxyalkyl, or 2-4C dihydroxyalkyl).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention uses 2, 5 as a color developing component.
-Diaminotoluene and 2,6 as coupling component
-For oxidative hair dyes, characterized in that they use a combination of diaminopyridine, resorcin and a specific aminophenol derivative.

[0002]

2. Description of the Related Art Oxidation dyeing methods have been widely used in the field of dyeing hair, particularly for producing dark shades. In this dyeing method, a hair dye is produced by oxidative coupling of an appropriate color-developing component and a coupling component in the hair shaft. It has the properties of exhibiting a very dark color and being very robust. Furthermore, various colors can be expressed in a wide range of colors by combining various color-developing components and coupling components. In dyeing human hair, various conditions are imposed on the oxidative dye. First, the dye must be toxicologically and dermatologically problem-free and must be able to be dyed to the desired concentration. The resulting color is then required to be robust to light, perm treatment, acid and abrasion. Moreover, the color obtained in this case must be robust for at least 4 to 6 weeks without being exposed to light, rubbing or chemical agents.

To produce black or light gray,
In most cases a blue coupling component should be used. As blue coupling components, for example 1,3-diaminobenzene and 2,4-diaminoanisole are known and have been used for a long time. In addition to this, a specific pyridine derivative such as 2,6-diaminopyridine is described in the literature as a blue coupling component. However, there are problems in using the m-phenylenediamine derivative as described above for a hair dye.
That is, the concentration of the color obtained with 1,3-diaminobenzene is not sufficient, while the use of 2,4-diaminoanisole has been prohibited for toxicological and dermatological reasons.

2,6-Diaminopyridine is a DE-AS
1142045 describes that it is used in combination with the color-developing component 2,5-diaminotoluene as a blue coupling component, and is subsequently listed in various publications as a component of oxidative hair dyes. ..
In addition, 2,6-diaminopyridine is commercially available at a relatively reasonable price. Nevertheless, 2,6-diaminopyridine is actually not used in hair dyes, or very rare, if at all. This is because 2,6-diaminopyridine is a color developing component p.
-Due to being able to display only a purplish blue color of insufficient concentration when combined with phenylenediamine. On the other hand, when it is combined with the color-developing component 2,5-diaminotoluene, a pale, unnatural greenish blue color is exhibited. Therefore, to express dark tones, especially black, 2, 6-
Diaminopyridine is totally unsuitable.

[0005]

DISCLOSURE OF THE INVENTION The present invention is capable of avoiding the above-mentioned problems relating to the density or physiology of the color obtained in such an oxidative hair dye, and is also desirable in terms of cost, Further, it is an object to provide an oxidative hair dye capable of expressing particularly dark color tone and black color.

[0006]

SUMMARY OF THE INVENTION In the present invention, surprisingly, in an oxidative hair dye based on a combination of a color developing component and a coupling component, A) 2, Oxidized hair dye containing 5-diaminotoluene as a coupling component, B) 2,6-diaminopyridine, C) resorcin, and D) at least one compound represented by the following general formula (I). It has been found that the agent can solve the above problems very well.

[0007]

[Chemical 2]

(Here, R ¹ represents H, F, Cl, Br, or I group, and R ² represents H, C ₁ -C ₄ hydroxyalkyl or C ₂ -C ₄ dihydroxyalkyl group.)

The combination of the color-developing component and the coupling component according to the invention makes the hair more natural, darker, bluish and especially darker than the combination of 2,5-diaminotoluene and 1,3-diaminobenzene alone. It has the characteristic that it can be dyed in shades and shades of black and that the color obtained thereby is fast. This new hair dye is clearly superior to hair dyes containing 1,3-diaminobenzene.

For the production of dark and black shade hair dyes, the dye concentration generally has to be high, so that
Inevitably, the final product price of the dye will be high. However, in the case of the combination of the color-developing component and the coupling component according to the present invention, since only inexpensive dyes are used, the cost is greatly reduced as compared with the conventional hair dye.

In the hair dye according to the invention, component A) is
0.5 to 8 weight percent, preferably 1 to 7 weight percent, component B) 0.01 to 3 weight percent, preferably 0.02 to 2 weight percent, component C) 0.1 to 3 weight percent, Desirably 0.4 to 3 weight percent, and component D) is included from 0.01 to 2 weight percent, preferably 0.01 to 1 weight percent.

Of the compounds represented by the general formula (I), a compound having a methyl group at a position para to the NHR ² group and a R ¹ group at a position para to the OH group, and N
Particularly preferred are compounds having a methyl group in the para position to the HR ² group, an OH group and an R ¹ group in the ortho position to the NHR ² group.

Among the compounds represented by the general formula (I), the compound in which R ¹ group and / or R ² group is hydrogen is
It is particularly suitable for the hair dye according to the invention.

Examples of the compound represented by the general formula (I) include the following compounds. 5-amino-2-methylphenol, 5-((2'-hydroxyethyl)-
Amino) -2-methylphenol, 5-((3′-hydroxypropyl) -amino) -2-methylphenol,
5-amino-4-chloro-2-methylphenol, 5-
Amino-4-fluoro-2-methylphenol, and 3-amino-2-chloro-6-methylphenol.

Of these compounds, 5-amino-2-methylphenol and 5-((2'-hydroxyethyl)-
Amino) -2-methylphenol, and 5-((3 '
-Hydroxypropyl) -amino) -2-methylphenol is preferable, and 5-amino-2-methylphenol is particularly preferable.

In order to express a particular color shade, the hair dye according to the invention may contain other known color-developing components and coupling components, preferably in an amount of 0.1 to 4% by weight. ..

Among known color-developing components, 1,4-diaminobenzene and 2- (2 ', 5'-diaminophenyl) are particularly preferable.
-Ethanol, 4-aminophenol and 4-amino-3-methylphenol can be used in combination with component A) as a constituent of the hair dye according to the invention. These known color developing components can be used alone or in combination. Among known coupling components as the coupling component, 4-chlororesorcin, 3-aminophenol, 5-hydroxy-1,3-benzodioxole, 5-amino-1,3-benzodioxole and 5-((2'-hydroxyethyl) -amino) -1,3
-Benzodioxoles can be used.

Such a material commonly used for dyeing hair is described by E. Sagarin in "Cosmetics, Science and Technology", Interscience Publishers Inc., New York (19).
57) 503 pages or less, and H. Janistyn's book "Cosmetics and Fragrance Handbook" (revised edition 3, 1978, ISBN 3-7785-
0423-1) pp. 454 et seq.

The color-developing component is usually used in approximately equal amounts with respect to the coupling component. However, there is no problem even if the developer component is used too little or too much with respect to the coupling component.

In addition to the above, the hair dye according to the present invention is a self-coupling dye precursor such as 2-amino-5-.
It can contain methylphenol, 2-amino-6-methylphenol or 2-amino-5-ethoxyphenol.

In order to obtain a specific color shade, the hair dye according to the invention can also be used in addition to the commonly used direct dyes, for example Diamond Fuchsin (CI. 42510) or Basic Blue 26 (CI. (44045)
Triphenylmethane dyes such as, picramic acid or 2-((2'-hydroxyethyl) -amino) -4,
Aromatic nitro dyes such as 6-dinitrophenol or 4-((2'-hydroxyethyl) -amino) -2-nitroaniline, Acid Brown 4 (C.I.
4805) or Acid Blue 135 (C.I.
Azo dyes such as 13385) or anthraquinone dyes such as Violet 1 (C.I. 61100) can be included in amounts of 0.01 to 4 weight percent. In addition to this, a direct dye useful for hair,
For example, JC Johnson's book "Hye Dye" Noyes Data
Corp. Park Ridge USA (1973).

Obviously, the color-developing component, the coupling component and the other dye component are in the form of physiologically problem-free acid addition salts when they are bases, such as hydrochloride or sulfate. It can be used in the form and also in the form of salts with inorganic salts, if they contain aromatic hydroxyl groups, for example in the form of alkali phenol salts.

Particularly, in the case of an amino compound which is easily oxidized, it is advantageous to employ a salt form at the time of producing the hair dye. For example, 2,5-diaminotoluene is preferably used in the form of sulfate. It is desirable to use 2,6-diaminopyridine in the form of the free base obtained on a large scale, or in the form of its monohydrochloride or hemisulfate, since it may be easily oxidized.

The total amount of the color-developing component, the coupling component, the dye precursor capable of self-coupling and the direct dye or salts thereof used in the hair dye according to the present invention is
It is about 0.1 to 10.0 weight percent, preferably 3.0 to 8.0 weight percent.

In addition to the hair dye according to the present invention,
Commonly used cosmetic additives, for example antioxidants such as ascorbic acid or sodium sulfite,
It may contain perfume oils, complexing agents, wetting agents, emulsifying agents, thickening agents, protective agents and the like.

The formulation may take the form of, for example, a solution, especially an aqueous solution or a water-alcohol solution. However, the preferred formulation is in the form of a cream, gel or emulsion. In this case, the constituents are a mixture of dye constituents and the additives customarily used for such formulations.

Typical additives to solutions, creams, gels or emulsions are solvents such as water and lower aliphatic alcohols such as ethanol, propanol or isopropanol, glycols such as propylene glycol or polyols such as glycerin, or Glycol ether and the like, further wetting agents or emulsifiers such as aliphatic alcohol sulfates, alkyl sulfonates, alkylbenzene sulfonates, alkyl trimethylane magnesium salts, alkyl betaines, oxyethylated aliphatic alcohols, oxyethylated nonylphenols, fatty acid alcohol amines, or Anionic, cationic, amphoteric or nonionic surfactants such as oxyethylated fatty acid ester, higher aliphatic alcohol, starch, Cellulose derivatives, petrolatum, thickeners, and lanolin derivatives such as paraffin oils or fatty acids, co Listerine, a protective agent such as pantothenic acid or betaine.

The above-listed components are used in the amounts generally used, depending on the purpose. For example, wetting agents and emulsifiers are used at about 0.5 to 30 weight percent, thickeners at about 0.1 to 25 weight percent, and protectants at about 0.1 to 5 weight percent.

The hair dye according to the present invention is adjusted to be weakly acidic, neutral or alkaline after preparation. In particular, it is desirable that the pH value is in the alkaline range of 8.0 to 11.5, and in that case, it is desirable that the pH adjustment is performed using ammonia. However, it is also possible to use organic amines such as monoethanolamine and triethanolamine and inorganic bases such as sodium hydroxide and potassium hydroxide.

To oxidatively dye hair, the above-mentioned hair dye is mixed with an oxidizing agent immediately before use, and this mixture is applied to the hair in an amount sufficient for the amount of hair, usually about 60 to 200 g.

Hydrogen peroxide or its addition compound to urea, melamine or sodium borate is mainly used as an oxidizing agent in the form of an aqueous solution of 3 to 12%, preferably 6%.

When using a 6% aqueous hydrogen peroxide solution as the oxidant, the weight ratio of hair dye to oxidant is 5: 1 to 1: 2, preferably 1: 1. When the concentration of the dye in the hair dye is high or at the same time the hair is strongly bleached, a large amount of the oxidizing agent is used.

After application, the mixture is left to act on the hair at 15 to 50 ° C. for about 10 to 45 minutes, preferably 30 minutes, then the hair is rinsed with water and dried. If necessary, shampooing is carried out after this washing, and optionally further rinsing with a weak organic acid such as citric acid or tartaric acid, and finally the hair is dried.

By using the hair dyes according to the invention, very fast dyeing results can be obtained which are very fast, in particular against light, washing and rubbing. This dyeing can be restored again with a reducing agent. The hair dye according to the present invention, by selecting its type and formulation ingredients,
A wide range of tones can be displayed for various colors. The dyeing density and clarity of the dyeings obtained are also noteworthy. Furthermore, according to the hair dye of the present invention,
Gray hair can also be dyed very well without any problems without chemical pretreatment. In that case, even if the condition of the hair is not uniform, the hair can be dyed very well and uniformly without being affected by it. The subject of the invention will now be described in more detail on the basis of examples.

[0035]

【Example】

Examples for hair dyes Example 1: Cream hair dye 2,5-diaminotoluene sulphate 3.8g 2,6-diaminopyridine 0.6g resorcin 0.8g 5-amino-2-methylphenol 0.1g. Anhydrous sodium sulfite 0.3g Lauryl alcohol-diglycol ether Sulfuric acid ester-28% aqueous solution of sodium salt 3.5g Cetyl alcohol 15.0g 25% aqueous solution of ammonia 4.0g Completely demineralized water 71.9g 100.0g Immediately before use 50 g of the above hair dye is mixed with 50 g of a 6% aqueous hydrogen peroxide solution and applied to bleached hair. After working for 30 minutes at 40 ° C., the hair is rinsed with water, shampooed and dried. The hair is dyed a deep black color.

Example 2: Solution hair dye 2,5-diaminotoluene sulfate 1.8 g 2,6-diaminopyridine 0.7 g resorcin 0.4 g 5-((2'-hydroxyethyl) -amino)- 2-Methylphenol 0.1 g Lauryl alcohol-diglycol ether sulfuric acid ester-28% aqueous solution of sodium salt 10.0 g Isopropanol 10.0 g Ascorbic acid 0.3 g Ammonia 25% aqueous solution 10.0 g Completely demineralized water 66.7 g 100. 0 g Immediately before use, 50 g of the above hair dye solution is mixed with 50 g of 6% hydrogen peroxide solution and applied to bleached hair. 40 ° C
At room temperature for 30 minutes, rinse hair with water,
Shamp and dry. This dyes the hair dark brown.

Example 3 Gel Hair Dye 2,5-Diaminotoluene Sulfate 5.0 g 2,6-Diaminopyridine Sulfate (2: 1) 1.5 g 5-Amino-2-methylphenol 0.2 g Resorcin 2.5g Ascorbic acid 0.3g Oleic acid 15.0g Isopropanol 7.0g 25% aqueous ammonia solution 9.0g Completely demineralized water 59.5g 100.0g Immediately before use, 50g of the above gel hair dye was added to 6%. Mix with 50 g of hydrogen peroxide solution and apply to bleached hair. Four
After working for 30 minutes at 0 ° C., the hair is rinsed with water, shampooed and dried. This dyes the hair a deep black color.

Example 4: Cream hair dye 2,5-diaminotoluene sulphate 3.8 g 2,6-diaminopyridine monohydrochloride 0.8 g 5-amino-2-methylphenol 0.1 g resorcin 0.1. 8 g 3-aminophenol 1.2 g 2-((2'-hydroxyethyl) -amino) -4,6-dinitrophenol 0.2 g anhydrous sodium sulfite 0.3 g lauryl alcohol-diglycol ether sulfate ester-sodium salt 28 % Aqueous solution 3.5 g cetyl alcohol 15.0 g 25% aqueous ammonia solution 4.0 g complete demineralized water 70.3 g 100.0 g Immediately before use, 50 g of the above hair dye is mixed with 50 g of 6% hydrogen peroxide aqueous solution to bleach. Apply to hair that has been made. After working for 30 minutes at 40 ° C., the hair is rinsed with water, shampooed and dried. This dyes the hair dark brown.

Example 5: Solution hair dye 2,5-diaminotoluene sulfate 1.8 g 2,6-diaminopyridine 0.7 g resorcin 0.4 g 5-((3'-hydroxypropyl) -amino)- 2-Methylphenol 0.1 g Lauryl alcohol-diglycol ether sulfuric acid ester-28% aqueous solution of sodium salt 10.0 g Isopropanol 10.0 g Ascorbic acid 0.3 g Ammonia 25% aqueous solution 10.0 g Completely demineralized water 66.7 g 100. 0 g Immediately before use, 50 g of the above hair dye is mixed with 50 g of a 6% aqueous hydrogen peroxide solution and applied to bleached hair. After working for 30 minutes at 40 ° C., the hair is rinsed with water, shampooed and dried. This dyes the hair dark brown.

Example 6 Gel Hair Dye 2,5-Diaminotoluene Sulfate 1.20 g 2,6-Diaminopyridine 0.02 g 5-Amino-2-methylphenol 0.01 g 3-Aminophenol 0.08 g Picramic acid 0.04 g Resorcin 0.40 g Sodium sulfite 0.30 g Oleic acid 15.00 g Isopropanol 7.00 g 25% aqueous ammonia solution 9.00 g Completely demineralized water 66.95 g 100.00 g The above hair dye 50 g just before use Mix with 50 g of 6% aqueous hydrogen peroxide and apply to bleached hair. After working for 30 minutes at 40 ° C., the hair is rinsed with water, shampooed and dried. This causes the hair to be dyed a medium light gray color.

Example 7: Gel hair dye 2,5-diaminotoluene sulfate 6.0 g 2,6-diaminopyridine 0.8 g 5-amino-4-chloro-2-methylphenol 0.3 g resorcin 2. 5g Ascorbic acid 0.3g Oleic acid 15.0g Isopropanol 7.0g Aqueous solution of 25% ammonia 9.0g Completely demineralized water 59.1g 100.0g Immediately before use, 50g of the above hair dye is added to 50g of 6% hydrogen peroxide solution Mix with and apply to bleached hair. After working for 30 minutes at 40 ° C., the hair is rinsed with water, shampooed and dried. This dyes the hair a deep black color.

Example 8: Creamy hair dye 2,5-diaminotoluenesulfate 3.8 g 2,6-diaminopyridine monohydrochloride 0.8 g 5-amino-4-fluoro-2-methyl-phenol. 1 g resorcin 0.8 g 3-aminophenol 1.2 g 2-((2'-hydroxyethyl) -amino) -4,6-dinitrophenol 0.2 g anhydrous sodium sulfite 0.3 g lauryl alcohol-diglycol ether sulfate- 28% aqueous solution of sodium salt 3.5 g Cetyl alcohol 15.0 g 25% aqueous solution of ammonia 4.0 g Complete desalting 70.3 g 100.0 g Immediately before use, 50 g of the above hair dye was added to 50 g of 6% aqueous hydrogen peroxide solution. Mix and apply to bleached hair. After working for 30 minutes at 40 ° C., the hair is rinsed with water, shampooed and dried. This dyes the hair dark brown.

Preparation Example Example 9: Preparation of 2,6-diaminopyridine hemisulfate 2,6-diaminopyridine was added at 150 ° C. and 0.05 mbar.
And purified by distillation, and 19.0 g (0.17 mol) of this purified product is dissolved in 250 ml of ethanol. The solution is filtered and cooled to 0 ° C. 10 ml of concentrated sulfuric acid in the above solution
Is dripped. The white precipitate is filtered off with suction, washed with ethanol and dried in a desiccator over calcium chloride. This gave 22.0 g (0.
14 mol) is obtained. It decomposes at 274 ° C.

CHNS microanalysis C ₅ H ₈ N ₃ O ₂ S _0.5 C% H% N% S% Calculated 37.97 5.10 26.57 10.13 Measured 37.96 5.23 26.65 10.09

Example 10: Preparation of 5-((3'-hydroxypropyl) -amino) -2-methylphenol First step N- (3-hydroxy-4-methylphenyl) carbamic acid- (3-chloropropyl) )ester

[0046]

[Chemical 3]

5-amino-2-methylphenol 13.8
g (0.6 mol), 100.1 g of calcium carbonate (0.33 mol) and 300 ml of dioxane are heated to 90 ° C. under a stream of nitrogen. Chloroformic acid- (3-
103.6 g (0.66 mol) of chloropropyl) ester are added dropwise over 1 hour. The mixture is subsequently heated at 90 ° C. for a further 3 hours. The insoluble constituents are then filtered off through diatomaceous earth and the filter residue is rewashed with 150 ml of warm dioxane. Collect the filtrate and pour onto 1.2 l of ice water. The resulting precipitate (143.7 g) was added to toluene 9
Recrystallize with 00 ml. This gives 125.4 g (0.51 mol) of a beige, microcrystalline product. It melts in the range 103-105 ° C. The yield is 86% of theory.

CHN microanalysis C ₁₁ H ₁₄ ClNO ₃ C% H% N% Calculated 54.28 5.79 5.74 Measured 54.35 5.74 5.74

Second stage 5-((3'-hydroxypropyl) -amino) -2-
Methylphenol

[0050]

[Chemical 4]

In a nitrogen atmosphere, at 45 ° C., 250 ml of a caustic soda solution was added with 48.8 g (0.2 mol) of N- (3-hydroxy-4-methylphenyl) carbamic acid- (3-chloropropyl) ester over 30 minutes. Drop it. The mixture is stirred at 45 ° C. for a further 30 minutes. Then, after adding 300 g of ice, the mixture was mixed with concentrated hydrochloric acid 60
Adjust the pH value to about 6 with ml. The aqueous phase is extracted with diethyl ether (3 x 200 ml). The diethyl ether extract is dried over magnesium sulfate, filtered and the diethyl ether is evaporated. As a result, 15.6 g (0.08) of oily product was obtained.
6 mol) is obtained. This is gradually crystallized. The yield is 43% of theory. The above crude product can be recrystallized using warm water. This gives a beige powder. It melts in the temperature range 72-75 ° C.

CHN microanalysis C ₁₀ H ₁₅ NO ₂ C% H% N% Calculated 66.27 8.34 7.73 Measured 66.32 8.37 7.48

Claims (12)

[Claims] 1. An oxidative hair dye based on a combination of a color developing component and a coupling component, wherein A) 2,5-diaminotoluene is used as the color developing component and B) 2,6-diaminopyridine is used as the coupling component. , C) resorcin, and D) at least one compound represented by the following general formula (I): (Wherein R ¹ represents H, F, Cl, Br, or I group, and R ² represents H, C ₁ -C ₄ hydroxyalkyl or C ₂ -C ₄ dihydroxyalkyl group). An oxidative hair dye. 2. In the general formula (I), there is a methyl group at a position para to the NHR ² group and an R ¹ group at a position para to the OH group. The described hair dye. 3. A methyl group at a position para to the NHR ² group in the general formula (I), an OH group and an NHR ² group.
Hair dye according to claim 1, characterized in that there is an R ¹ group in the ortho position relative to the group. 4. The R ¹ group is hydrogen,
The oxidative hair dye according to any one of claims 1 to 3. 5. The R ² group is hydrogen,
The oxidative hair dye according to any one of claims 1 to 4. 6. A compound represented by the general formula (I):
5-amino-2-methylphenol, 5-((2'-hydroxyethyl) -amino) -2-methylphenol, 5
-((3'-hydroxypropyl) -amino) -2-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4-fluoro-2-methylphenol, and 3-amino-2 An oxidative hair dye according to claim 1, characterized in that it is selected from chloro-6-methylphenol. 7. A compound represented by the general formula (I) is
5-amino-2-methylphenol, 5-((2'-hydroxyethyl) -amino) -2-methylphenol, and 5-((3'-hydroxypropyl) -amino) -2
-Oxidative hair dye according to claim 1, characterized in that it is selected from methylphenol. 8. The compound represented by the general formula (I) is 5
An oxidative hair dye according to claim 1, which is -amino-2-methylphenol. 9. Supplementary 1,4-diaminobenzene, 2
-(2 ', 5'-diaminophenyl) -ethanol, 4
The oxidative hair dye according to any one of claims 1 to 8, which contains at least one developer component selected from the group consisting of -aminophenol and 4-amino-3-methylphenol. 10. Supplementary 4-chlororesorcinol, 3-aminophenol, 5-hydroxy-1--3-benzodioxole, 5-amino-1,3-benzodioxole and 5-((2 ' -Hydroxyethyl) -amino)-
10. The oxidative hair dye according to any one of claims 1 to 9, which contains at least one coupling component selected from the group consisting of 1,3-benzodioxole. 11. A self-coupling dye precursor which is at least one selected from the group consisting of 2-amino-5-methylphenol, 2-amino-6-methylphenol and 2-amino-5-ethoxyphenol. The oxidative hair dye according to any one of claims 1 to 10, which comprises a body. 12. A diamond fuchsin (C.
I. 42510), Basic Blue 26 (C.I.
44045), piclamic acid, 2-((2'-hydroxyethyl) -amino) -4,6-dinitrophenol,
4-((2'-hydroxyethyl) -amino) -2-nitroaniline, Acid Brown 4 (C.I. 148
05), Acid Blue 135 (C.I. 1338)
5), Disperse Violet 4 (C.I. 611
05), Disperse Red 15 (CI.6071)
0) and Disperse Violet 1 (C.I. 6)
1100) containing at least one direct dye selected from the group consisting of 1100).
1. The oxidative hair dye according to any one of 1.