JPH0662395B2 - Oxidative hair dye comprising liquid colorant and emulsified oxidant-containing composition, and oxidative hair dyeing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a liquid color former and an emulsified composition containing at least 2.5 to 12 weight percent of a C ₁₀ to C ₂₄ natural or synthetic aliphatic alcohol and an oxidizing agent. , 1: 1.5 to 11: 4, respectively,
The present invention relates to an oxidative dyeing agent for hair obtained by mixing, and an oxidative dyeing method.

Oxidative hair dyes are still very important constituents in the field of hair treatment as they are today. It has two components. These components are mixed just before use and applied to the treated hair.

The first component, that is, the color former contains a substance having a color forming action. It is provided in liquid, gel or emulsion form. The second component contains a suitable oxidant,
It is provided in the form of an aqueous solution, cream or powder.

In this case, dyeing is carried out by reacting a specific developing component and a specific coupling component in the presence of a suitable oxidizing agent such as hydrogen peroxide. Mainly as a color development component,
4-diaminobenzene, 2,5-diaminotoluene, 2,5-diaminophenylethanol, 4-aminophenol and 4-
Amino-3-methylphenol is used. For the coupling component, for example, resorcin, 4-chlorresorcin, sesame oil, 2-methylresorcin, 3-aminophenol, 4- (2'-hydroxyethyl) amino-1,2-
Methylenedioxybenzene and 2-amino-4- (2'-hydroxyethylamino) -anisole are commonly used.

Color formers are used in some countries, for example in the United States,
Liquids are mainly used. Liquid color formers are given considerable importance in publications. This has the advantage that the raw material contained therein is easily available in terms of price and that the liquid material is technically easy to manufacture.

In carrying out dyeing, the liquid color former is usually mixed with an aqueous hydrogen peroxide solution at a ratio of 1: 1 or 1: 2, for example. The mixture of the color former and the aqueous hydrogen peroxide solution is produced, for example, by pouring it into a bottle for application, and is applied to the hair to be dyed immediately after the production.

However, liquid color formers have a major drawback. That is, when the liquid color former is mixed with the hydrogen peroxide solution, it immediately becomes dark. Also, the hair coated with this oxidative hair dye is very slowly dyed while in contact with the hair dye. However, because the oxidative hair dye is already blackened, the hair dye tends to be washed out too early, resulting in too short an action time on the hair,
The defect occurs that it is not dyed to the desired density.

Furthermore, the commonly used liquid color formers also have the disadvantage that they release an ammonia content very easily and thus suffer from an unpleasant odor. In addition, liquid hair dyes, especially those with a light color, are known to cause unwanted irritation to the scalp. Therefore, the present invention provides an oxidative hair dye based on a liquid colorant which does not exhibit the above-mentioned drawbacks of known liquid colorants in the oxidative dyeing of hair, and a hair produced by the oxidative hair dye. The challenge was to provide an oxidation dyeing method.

And here, the oxidative hair dye obtained by mixing the oxidant-containing emulsified composition with the liquid color developer has no problem on the scalp, and adversely affects the dyeing result at an early stage after mixing the oxidant. It has been found that no such darkening is exhibited, and the unpleasant odor caused by released ammonia is significantly less than that of known hair dyes.

That is, the present invention relates to component (A), that is, a liquid color former having a viscosity of 100 mPa.s or less at 30 degrees Celsius, and component (B), that is, at least one of C ₁₀ to C ₂₄ natural or synthetic aliphatic alcohols. .5 to 1
An emulsified composition containing 2 weight percent and an oxidizer,
Ingredient (A): Ingredient (B) = 1: 1.5 to 1: 4 by weight ratio is intended for an oxidation dyeing agent for hair obtained by mixing.

A particularly preferred embodiment of the dyeing agent according to the invention is that the weight ratio of component (A): component (B) is from 1: 2 to 1: 3. The viscosity of the liquid color former is measured using a Haake viscometer (Rod II, 5 grams) at 30 degrees Celsius.

The natural or synthetic aliphatic alcohol contained in the emulsified oxidant-containing component (B) is preferably a C ₁₄ to C ₂₀ aliphatic alcohol. Examples of the aliphatic alcohol that can be contained in the component (B) include cetyl alcohol and stearyl alcohol and mixtures thereof.

Component (B) contains 1 to 18 weight percent oxidizer, particularly preferably 4 to 14 weight percent. As oxidizing agents for the color development of hair dyes there may be mentioned in particular hydrogen peroxide or its addition compounds to urea, melanin and sodium borate. Ingredient (B)
In particular, it is desirable to contain hydrogen peroxide in an amount of 1 to 18% by weight.

Component (A) comprises 2 to 30% by weight, particularly preferably 8 to 16% by weight, of natural or synthetic C ₁₀ to C ₂₄ , particularly preferably C ₁₆ to C _22.
Saturated or unsaturated fatty acid of 1) is contained alone or in mixture. Such fatty acids that may be included in component (A) include, for example, erucic acid, myristic acid, ricinoleic acid, lauric acid, palmitic acid, and oleic acid. These fatty acids are preferably dissolved in the hair dye according to the invention in the form of ammonium salts by adding ammonia. However, instead of ammonia it is also possible to use aliphatic amines, for example monoethanolamine.

Component (A) may be a low molecular weight C ₁ to C ₄ alcohol, C ₂ to C ₆ glycol such as ethanol, propanol, isopropanol, ethylene glycol, 1,2-propylene glycol or butyl glycol, or 2 to 30 of these mixtures
It may contain weight percent, desirably 12 to 28 weight percent.

In addition to this, the component (A) further contains a nonionic emulsifier in an amount of 0.1.
To 25 weight percent. Particularly preferably, the hair dye of the present invention contains 10 to 2 nonionic emulsifiers.
Contains 0 weight percent. Nonionic emulsifiers that can be used include, in particular, oxyethylated C ₁₀ to C ₂₀ aliphatic alcohols or oxyethylated alkylphenols having C ₆ to C ₁₄ alkyl groups or mixtures thereof. Ingredient (A)
The fatty alcohols and alkylphenols contained therein are oxyethylated with 1 to 8, preferably 1 to 6, ethylene oxide units.

Component (A) contains at least one coupling component and at least one color-developing component, and optionally a dye precursor pair which can be supplementarily self-coupled and a dye which can be dyed directly on the hair. . The coupling component and the color-developing component may be contained in the hair dye as it is or in the form of a salt with an inorganic acid or an organic acid which does not cause a physiological problem, for example, chloride, sulfate, phosphate or acetate. , Propionate, lactate, or citrate.

The coupling component is usually used in an approximately equimolar amount with respect to the color developing component. It is obviously the purpose to use equimolar amounts, but there is no problem even if the coupling component is excessive or excessive to some extent. Further, the coupling component and the color developing component need not be a single product, and the color developing component may be a mixture of known color developing components, and the coupling component may be a mixture of known coupling components. .

The liquid color former, that is, the component (A) is, for example, among known coupling components, particularly 1-naphthol, 4-methoxy-1-naphthol, resorcin, 4-chlorresorcin,
4,6-dichlororesorcin, 2-methylresorcin, 3-aminophenol, 4-hydroxy-1,2-methylenedioxybenzene, 4-amino-1,2-methylenedioxybenzene, 4-
(Β-Hydroxyethylamino) -1,2-methylenedioxybenzene, 4-hydroxyindole, 5-hydroxy-
Benzodiosisols- (1,3), 5-amino-benzodioxole- (1,3), 5-((2-hydroxyethyl) amino) benzodioxole- (1,3), and 5 -amino-
Contains 2-methylphenol alone or in combination. Other suitable coupling components include, for example, 2,4-dihydroxyanisole and 2,4-dihydroxyphenol ethers such as 2,4-dihydroxyphenoxyethanol.

Among the known color developing components, as the hair dye component of the present invention, particularly 1,4-diaminobenzene, 2,5-diaminotoluene, 2,5-
Diaminoanisole, 2,5-diaminobenzyl alcohol, 3-methyl-4-aminophenol, 2- (β-hydroxyethyl) -1,4-diaminobenzene, tetraaminopyrimidine, 2- (2 ′, 5′- Mention may be made of diaminophenyl) -ethanol and 4-aminophenol.

Among known oxidants for hair dyeing, those which can be applied to the component (A) are particularly preferably E.I. Zagarin's book "Cosmetics, Science and Technology", Intescience Publisher, Inc., New York (195
7), pages 503-504, and those described by H. Janistin's author "Cosmetics and Fragrances Hanbook" (1973), pages 338-339.

The total amount of the color-developing component and the coupling component contained in the component (A) is 0.01 to 12.0% by weight, particularly preferably 0.2 to 4.0% by weight.

In addition to the above, more commonly used direct dyes for obtaining the desired shade, such as diamond fuchsin (CI42 510) and leather ruby HF (CI42 52
0) triphenylmethane dyes, 2-amino-4,6-
Dinitro-phenol, 2-nitro-4- (β-hydroxyethylamino) aniline, 2-N-β-dihydroxypropylamino-5- (N-methyl, N-hydroxyethyl) amino
-Aromatic nitro dyes such as nitrobenzene and 2-amino-4-nitrophenol, Acid Brown 4 (C.
I.14 805) and Acid Blue 135 (CI13 385)
Azo dyes like Disperse Violet 4 (C.
I.61 105), Disperse Blue 1 (CI64 500),
Disperse Red 15 (CI60 710), Disperse Violet 1 (CI61 100) and anthraquinone dyes such as 1,4,5,8-tetraaminoanthraquinone and 1,4-diaminoanthraquinone as ingredients ( It can be used by adding it to A). Component (A) is also a dye precursor that can be further self-coupled, such as 2-amino-.
5-methylphenol, 2-amino-6-methylphenol,
It may contain 2-amino-5-ethoxyphenol, as well as 2-propylamino-5-aminopyridine. The total amount of direct dyes and self-coupling dyes in component (A) is 0.01 to 7.0 weight percent, preferably 0.
2 to 4.0 weight percent.

Further, the component (A) contains an antioxidant such as ascorbic acid, resorcin or sodium sulfite, and a complex compound-forming substance with respect to a heavy metal such as ethylenediaminetetraacetate or nitriloacetic acid in a proportion of 0.5% by weight or less. Can be done. Perfume oils may be contained in the hair dye according to the invention in an amount of up to 1% by weight. In addition, the component (A) may contain a wetting agent, an emulsifying agent, a protective agent, a cationic resin, and commonly used additives.

The weight percent amounts used here are not the numerical values in the finished product but the numerical values relating to the component (A) or the component (B), respectively.

The finished product obtained by mixing the components (A) and (B) in the mixing ratio according to the present invention can be adjusted to be acidic, neutral or alkaline in the oxidation dyeing of hair. In applying the oxidative dyeing of hair, the PH value of the agent according to the present invention is preferably in the range of 7.5 to 12.0.

The oxidative hair dyes mentioned above are used according to the method of the invention. That is, first, immediately before use, the liquid color former (component A) and the hydrogen peroxide emulsion (component B) are mixed in a weight mixing ratio according to the present invention, that is, a ratio of 1: 1.5 to 1: 4,
Then, a sufficient amount of this mixture is applied to the hair to be dyed, usually 90 to 160 g depending on the amount of the hair. The mixture is about 5 at 15 to 50 degrees Celsius for hair
Approximately 60 minutes, preferably 30 minutes. Then rinse with water, shampoo and rinse as needed, and dry.

The subject of the invention will now be described in more detail with reference to examples.

Examples Example 1: Oxidative hair dye for light color dyeing Immediately before use, 40 g of the above liquid color former and 80 g of hydrogen peroxide emulsion are mixed (in this case, the mixing ratio is 1: 2). 120 g of this mixture is applied to medium brown human hair and left to act for 20 minutes at room temperature. The hair dye is then rinsed with water and dried. By this treatment, the hair is uniformly dyed in a light brown color from the root to the tip. The oxidation dyeing agent for hair according to the present invention hardly darkens even after mixing two components, has a slight ammonia odor, and shows no problem to the skin.

Example 2: Oxidative hair dye Immediately before use, 40 g of the above liquid color former and 80 g of hydrogen peroxide emulsion are mixed (in this case, the mixing ratio is 1: 2). 120 g of this mixture is applied to gray human hair and left to act for 20 minutes at room temperature. The hair dye is then rinsed with water and the hair is dried. The hair oxidative dyeing agent according to the present invention exhibits almost no ammonia odor,
Moreover, even after mixing with the oxidizing agent, almost no darkening is shown, and there is no problem on the skin. The above treatment uniformly dyes the hair in dark brown.

Example 3: Oxidative hair dye Immediately before use, 40 g of the above liquid color former is mixed with 80 g of the hydrogen peroxide emulsion (component B) described in Example 2 (in this case, the mixing ratio is 1: 2). 120 g of this mixture is applied to gray human hair and left to act for 20 minutes at room temperature.
The hair dye is then rinsed with water and the hair is dried. The agent for oxidative dyeing of hair according to the present invention shows almost no ammonia odor, shows almost no darkness even after mixing with an oxidant, and has no problem on the skin at all. The above treatment uniformly dyes gray hair to a light blond color.

Comparative Experiment A: Effect on Skin in Light Color Dyeing An experiment was conducted to compare the effect on skin of the oxidative hair dye according to the present invention and a conventionally known oxidative hair dye. First, 20 g of the liquid color former described in Example 1 and 40 g of a hydrogen peroxide composition having the following composition, which is generally used, are mixed with the hair of the left head of each of 10 subjects having medium brown hair. A conventional oxidative hair dye known in the art is applied.

Commonly used hydrogen peroxide composition Next, for each of the above test subject's right head hair,
Oxidative hair dye 60 according to the invention obtained according to Example 1
g. Here both drugs are allowed to act on the hair or scalp for 20 minutes at room temperature. The drug is then rinsed with water, the hair is shampooed, rinsed and dried.

The effect of both oxidative hair dyes The mesothelizers felt a much stronger pain on the skin of the left head as compared to the skin of the right head treated with the hair dye according to the invention.

After washing both oxidative hair dyes with water, it was confirmed that 30% of the subjects had very reddish left head and abnormalities. None of the subjects had their scalp reddened by the drug according to the present invention.

As a result of the comparative experiment, it was confirmed that the oxidative hair dye according to the present invention had no problem on the skin and was very excellent.

Comparative experiment B: Ammonia odor of drug To compare the discomfort due to the ammonia odor caused by the oxidative hair dye according to the present invention with the ammonia odor caused by the conventionally used oxidative hair dye, a comparative experiment. I went.

First, 20 g of the liquid color-forming agent described in Example 2 is mixed with 40 g of a hydrogen peroxide composition having the following composition that has been commonly used in the past to produce an oxidative hair dye that has been conventionally used.

Commonly used hydrogen peroxide composition 60 g of this oxidative hair dye is applied to the left head of each of 10 test subjects who have gray hair.

For comparison, 60 g of the oxidative hair dye according to the present invention obtained according to Example 2 is applied to the right head of each of the above subjects.

Then act for 20 minutes. During this period of action, the ammonia odor of both drugs is evaluated.

The barbers who performed the experiment all evaluated the same.
That is, the right head treated with the oxidative hair dye of the present invention had almost no ammonia odor, while the left head had a very strong irritating odor due to the released ammonia.

Comparative Experiment C: Darkening by Mixing Two Components Furthermore, in the oxidative hair dye obtained in Example 3 according to the present invention and the oxidative hair dye conventionally used,
A comparative experiment was conducted on the darkening of the drug after mixing the two components.

First, 20 g of the liquid color-forming agent described in Example 3 is mixed with 40 g of a hydrogen peroxide composition having the following composition that is conventionally used, to produce an oxidation hair dye that is conventionally used.

Commonly used hydrogen peroxide composition 60 g of the above mixture is applied to the left head of each of the 10 subjects with white hair. On the other hand, 60 g of the oxidation hair dye according to the present invention obtained in Example 3 is applied to the right head. There is then a 20 minute action time at room temperature. During this time, the barber will evaluate the darkening of both drugs.

As a result of the comparative experiment, unlike the conventionally used oxidative hair dye applied to the left head, the oxidative hair dye according to the present invention applied to the right head showed substantially no darkening. Thus, the oxidative hair dye according to the present invention shows almost no darkening, so that the desired dyeing result can be obtained with certainty. On the other hand, in the case of the conventionally used oxidative hair dye, darkening occurs rapidly after mixing the two components, so that the determination of the degree of progress of dyeing is incorrect, and the desired dyeing density cannot be obtained. Was often.
With the drug according to the invention, such mistakes can be avoided.

All percentages mentioned herein are weight percentages.

Claims (12)

[Claims] 1. Component (A), a liquid color former having a viscosity of 100 mPa.s or less at 30 degrees Celsius, and component (B), ie, at least one C ₁₀ to C ₂₄ natural or synthetic aliphatic alcohol. Hair obtained by mixing an emulsified composition containing 0.5 to 12% by weight and an oxidizing agent in a weight ratio of component (A): component (B) = 1: 1.5 to 1: 4. For oxidative dyeing. 2. The weight ratio of component (A) and component (B) is 1 :.
The drug according to claim 1, characterized in that it is 2 to 1: 3. 3. The drug according to claim 1, wherein the component (A) contains 2 to 30% by weight of a C ₁₀ to C ₂₄ saturated fatty acid or an unsaturated fatty acid or a mixture thereof. 4. Component according to claim 1, characterized in that component (A) contains 2 to 30% by weight of a C ₁ to C ₄ alcohol, a C ₂ to C ₆ glycol, or a mixture thereof. The drug according to item 1. 5. The agent according to claim 1, wherein the component (A) contains 0.1 to 25% by weight of a nonionic emulsifier. 6. A nonionic emulsifier which is oxyethylated C
The drug according to claim 5, which is a ₁₀ to C ₂₀ aliphatic alcohol, an oxyethylated alkylphenol having a C ₆ to C ₁₄ alkyl group, or a mixture thereof. 7. An oxyethylated aliphatic alcohol and an oxyethylated alkylphenol are 1 to 8.
7. Drug according to claim 6, characterized in that it is oxyethylated by ethylene oxide units. 8. The agent according to claim 1, wherein the component (A) contains 0.01 to 12.0 weight% of the total amount of the color-developing component and the coupling component. . 9. Component (A) according to claim 1, characterized in that it contains 0.01 to 7.0% by weight of direct dyes and self-coupling dye precursors. Drug. 10. The agent according to claim 1, wherein the component (B) contains 1 to 18% by weight of an oxidizing agent. 11. The component (B) comprises hydrogen peroxide of 1 to 18
11. Content by weight percent.
The drug according to. 12. The method according to claim 1, wherein the aliphatic alcohol contained in the component (B) is a C ₁₄ to C ₂₀ natural or synthetic aliphatic alcohol.
The drug according to item.