JPH0782121A - Slowly dyeing hair-dye composition and its production - Google Patents

Abstract

PURPOSE:To provide a stably producible hair-dye composition effective for slowly coloring the hair without staining the hand and having excellent storage stability and safety to the skin. CONSTITUTION:This slowly dyeing hair-dye composition contains (A) an aerosol stock liquid composed of 2,4-diaminophenol or its salt and an antioxidant, (B) an aerosol stock liquid composed of an alkaline agent and a foaming agent and (C) an aerosol propellant. The pH of the mixture obtained by mixing A with B is 6.5-8.0.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hair dye composition, and more particularly, it has an effect of gradually coloring hair without dyeing on the hands during use, can be stably produced, and has storage stability and skin safety. TECHNICAL FIELD The present invention relates to an aerosol foam-type slow-dyeing hair dye composition.

[0002]

2. Description of the Related Art Conventionally, in the field of hair dyes, a two-component oxidative hair dye consisting of a first agent containing paraphenylenediamine or toluene-2,5-diamine as a main agent and a second agent containing an oxidizing agent as a main agent. The agent is widely applied. This type of hair dye has various color tones and is excellent in hair dyeing power and fastness. However, these hair dyes are first
It is necessary to uniformly mix the second agent with the second agent, and the hair dyeing operation is very complicated, and since the irritation is very high, there is a drawback that it cannot be applied especially to people with an allergic constitution. Furthermore, it is immediately recognized that the hair is dyed by a third party due to a rapid change in the hair color, which causes a feeling of strangeness. In addition, in recent years, a rinse-type hair dye using an acid dye, which is characterized by gradually dyeing hair, has been put on the market, but a hair dye using this acid dye has a very high hand, scalp, etc. It has a problem that it is easily dyed and cannot be easily removed once dyed. Therefore, the hair color changes gradually and naturally without abrupt color change, and it can be easily dyed without requiring complicated operations, and it is safe and does not stain hands or scalp. High ones are strongly desired.

As a means for achieving these things, Japanese Patent Laid-Open No. 1-1999
In JP-A-308215, a method using an acid dye and a quaternary ammonium salt is proposed, but an acid dye that is anionic and a quaternary ammonium salt that is cationic form an insoluble salt, which is sufficient. There is a problem that the dyeing power cannot be obtained and that the skin is dyed more easily than the hair. JP-A-61-78714 proposes a gray hair dye for cumulative hair dyeing using an oxidation dye such as paraphenylenediamine, but the operation is complicated and the hair is damaged. There is. In addition, JP-A-2-53
In Japanese Patent Laid-Open No. 715 and Japanese Patent Laid-Open No. 60-126114,
Attempts have been made to develop a one-pack type hair dye using 2,4-diaminophenol, but these methods require a hair dyeing time of 10 minutes or more, lack convenience, and are safe for the skin. Insufficient, and discoloration and the like occurred during production, resulting in poor stability of the composition and impractical application.

[0004]

DISCLOSURE OF THE INVENTION In view of the above problems, the inventors of the present invention have earnestly studied to develop a hair dye composition in which the above problems and drawbacks of the prior art are improved. As a result, the aerosol stock solution was adjusted to pH 2.0 to 6.0 containing 2,4-diaminophenol and an antioxidant.
And an aerosol stock solution containing an alkali agent and a foaming agent, and these two types of aerosol stock solutions and an aerosol propellant are contained, and the pH of the aerosol stock solution is 6.5 to 8 when mixed. A slow-dyeing hair dye composition having a color density of 0.0 has an effect of gradually coloring hair without dyeing hands at the time of use, can be stably produced, and has storage stability and skin safety. They have found that they are excellent and completed the present invention.

That is, the present invention contains an aerosol stock solution and (C) separately prepared in the following (A) and (B) and has a pH of 6.5 when the aerosol stock solutions of (A) and (B) are mixed. It is a slow-dyeing hair dye composition characterized by being -8.0. (A) Aerosol stock solution containing 2,4-diaminophenol and a salt thereof and an antioxidant and having a pH of 2.0 to 6.0 (B) Aerosol stock solution containing an alkali agent and a foaming agent (C) Aerosol propellant Further, according to the present invention, the aerosol undiluted solutions prepared separately in (A) and (B) are individually stored until just before filling, and mixed in the aerosol pressure-resistant container or mixed just before filling and then filled in the aerosol pressure-resistant container. And a method for producing a slow-dyeing hair dye composition, which further comprises filling (C).

The present invention will be described in detail below. The 2,4-diaminophenol in the aerosol stock solution (A) in the present invention is a known compound, and either a free compound or a salt compound may be used,
Considering the practice of the present invention, it is preferable to use sulfates, hydrochlorides, acetates, etc. in terms of stability in the production process. The content of these 2,4-diaminophenols is usually 0.1 to 5% by weight, preferably 0.3 to 3% by weight, based on the total amount of the composition. When it is less than 0.1% by weight, it is difficult to obtain a satisfactory hair dyeing effect, and when it is 5% by weight or more, there is a problem in safety and stability, which is not preferable.

The antioxidant (A) in the undiluted aerosol solution of the present invention stabilizes the dye in the undiluted aerosol solution. Specific examples of the antioxidant include ascorbic acid and its salts and sulfites. , Bisulfite, thiosulfate, thioglycolic acid and its salt, L-cysteine and its salt, N-acetyl-L-cysteine and its salt, thiolactic acid and its salt, etc., and these are applied in combination. You can also The stabilizer is usually added in an amount of 0.05 to 1% by weight based on the total amount of the composition. If it is less than 0.05% by weight, it is impossible to sufficiently stabilize the stock solution of dye, and if it exceeds 1% by weight, the dye is subjected to a reducing action to cause a problem in color developability or irritation to the skin. Is not desirable.

The pH of the aerosol stock solution (A) of the present invention is adjusted to 2.0 to 6.0, preferably 3.0 to 5.
It is 5. When the pH is less than 2.0, the filling device and the storage container (particularly made of stainless steel) are corroded at the time of manufacturing, filling or storing, which is not preferable in terms of stability of the stock solution. Further, the pH is 6.
When it exceeds 0, color development of the undiluted solution itself occurs, it cannot be stored for a long time before filling, and discoloration or the like occurs during the filling manufacturing process, which is not preferable. P of these (A) aerosol stock solutions
As a method for adjusting H, for 2,4-diaminophenol and other compounded dyes, it can be achieved without adding an acid by using an acid salt such as hydrochloride, sulfate and acetate.
Further, it is also achieved by blending an organic acid such as citric acid, tartaric acid, malic acid and the salts thereof, an inorganic acid such as hydrochloric acid, sulfuric acid, phosphoric acid and the salts thereof.

The undiluted aerosol solution (A) of the present invention can be further stabilized by adding a small amount of a surfactant, and the binding or reaction between dye molecules can be suppressed. As the surfactant that can be added, any of known anion, nonion, amphoteric and cationic surfactants may be used, and preferably the same surfactant as the foaming agent in the aerosol stock solution of (B), Alternatively, it is a surfactant that does not form an ion complex. Further, in view of stability of the stock solution, a water-soluble one is preferable. The preferable blending amount is 0.01 wt% to 5.0 wt% based on the total amount of the composition.

The aerosol stock solution of (A) of the present invention can be further stabilized by adding various solvents. Specific examples of the solvent include propylene glycol, dipropylene glycol, glycerin, and 1 , 3-
Butylene glycol, polyethylene glycol, hexylene glycol, ethanol, isopropyl alcohol, benzyl alcohol, N-methylpyrrolidone, methyl cellosolve, ethyl cellosolve are mentioned, and the preferable compounding amount is 1 to 30 based on the total amount of the composition. % By weight.

In the aerosol stock solution (A) of the present invention,
Further known coupling substances can be used if necessary for delicate color control. Specific examples of such coupling substances include phenylenediamines such as p-phenylenediamine and m-phenylenediamine, toluylenediamines such as toluene-2,5-diamine, p-aminophenol, o-aminophenol, and the like.
Aminophenols such as m-aminophenol, aminonitrophenols, diphenylamines, diaminophenylamines, N-phenylphenylenediamines,
Examples thereof include diaminopyridines, resorcinol, pyrogallol, hydroxybenzenes such as catechol, and one or more of salts thereof.

Specific examples of the alkaline agent in the aerosol stock solution (B) of the present invention include monoethanolamine, diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine,
Examples thereof include organic alkalis such as aminomethyl propanol and ammonium bicarbonate and salts thereof, and inorganic alkalis such as sodium hydroxide, potassium hydroxide and calcium hydroxide and salts thereof. In selecting the alkaline agent, the corrosion of the aerosol pressure-resistant container should be taken into consideration. For example, those that corrode the resin and the aluminum can, such as ammonia, are usually not preferable. The blending amount of these alkaline agents is 0.1 to 1 based on the total amount of the composition.
It is 0% by weight, preferably 0.3 to 5% by weight.

The foaming agent in the aerosol stock solution (B) in the present invention is one or a mixture of two or more selected from anionic, nonionic, amphoteric and cationic surfactants. The foaming agent to be blended is p after mixing the undiluted aerosol solution.
Any type may be used as long as it is stable and has sufficient foamability in the H6.5 to 8.0 range. Specific examples of the anionic foaming agent include sodium lauryl sulfate and lauryl. Higher alkyl sulfate such as ammonium sulfate, polyoxyethylene alkyl sulfate such as POE sodium lauryl ether sulfate, disodium lauryl sulfosuccinate, sulfosuccinate such as dioctyl sodium sulfosuccinate, higher N-lauryl-N-methyltaurine sodium Fatty acid amide sulfonates, triethanolamine lauryl phosphate, phosphate esters such as POE alkyl ether phosphates, sulfonates such as dodecylbenzene sulfonate, N-acyl sarcosinates such as sodium lauroyl sarcosine, N
Examples include N-acyl amino acid salts such as -lauroyl glutamate and N-lauroyl aspartate. In addition, fatty acid soaps such as alkylcarboxylic acid salts and oleic acid soaps have foaming properties in a high pH range, and it is not possible to set them in a target pH range, which is not preferable.

Specific examples of the nonionic surfactant blowing agent include sorbitan monostearate and other sorbitan fatty acid esters, glyceryl monostearate and other glycerin fatty acid esters, decaglycerin monolaurate and other polyglycerin fatty acid esters, and POE sorbitan. Polyoxyethylene sorbitan fatty acid ester such as stearate, POE glycerin stearate or other polyoxyethylene glycerin fatty acid ester, polyethylene glycol fatty acid ester such as POE monolaurate, POE
Polyoxyethylene alkyl ethers such as cetyl ether, polyoxyethylene polyoxypropylene alkyl ethers such as POE / POP cetyl ether, polyoxyethylene alkylphenyl ethers such as POE nonylphenyl ether, and polyoxyethylene cured castor such as POE hydrogenated castor oil Oil, polyoxyethylene lanolin
Examples thereof include lanolin alcohol, alkanolamides such as coconut oil fatty acid diethanolamide, and alkylamine oxides.

Specific examples of the amphoteric surfactant foaming agent include carboxybetaines such as N, N-dimethyl-N-lauryl-N-carboxymethylammonium betaine,
Examples thereof include imidazoline derivatives such as 2-lauryl-N-carboxyethyl-N-hydroxyethylimidazolium betaine, aminocarboxylic acid salts such as sodium N-coconut oil alkyl-β-aminopropionate, sulfobetaines, aminobetaines and the like. I can.

Specific examples of the foaming agent of the cationic surfactant include lauryltrimethylammonium chloride, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, behenyltrimethylammonium chloride, palmityltrimethylammonium chloride, cocoyltrimethylammonium chloride and eicosyltrimethyl chloride. Mono-long-chain alkyl quaternary ammonium salts such as ammonium chloride, dipalmityldimethylammonium chloride, distearyldimethylammonium chloride, di-hydrogenated tallow alkyldimethylammonium chloride, di-hydrogenated tallow alkyldimethylammoniumdiethylsulfate Long-chain alkyl quaternary ammonium salt, stearyl pentaethoxyammonium chloride, ethyl sulphate Lanolin fatty acid aminopropyl ethyl dimethyl ammonium, benzalkonium chloride, and benzethonium chloride.

The blending amount of these foaming agents is 0.3 to 30% by weight, preferably 0.5 to 10% by weight, based on the total amount of the composition. If the blending amount is less than 0.3% by weight, it is difficult to obtain sufficient foaming properties, and the dyeing on the skin such as the hands and the scalp becomes remarkable. When it is 30% by weight or more, the foam is less likely to be crushed, the hair dyeing property is deteriorated, and it causes skin irritation such as itchiness and rash, which is not preferable.

The pH of the aerosol stock solution of (B) of the present invention is usually adjusted to 6.5 to 12.0, preferably 7.0.
~ 10.0. When the pH is less than 6.5, it is difficult to adjust the pH range of the final composition (pH 6.5 to 8.0), and when the pH exceeds 12.0, the foaming agent deteriorates or deteriorates during storage. And the like, or a high heat of neutralization is generated when mixing immediately before filling, which is not preferable.

In the present invention, the pH of the aerosol stock solutions (A) and (B) when mixed is in the range of 6.5 to 8.0, preferably 6.8 to 7.8. pH 6.5
When the amount is less than the above, the color is not developed in a short time of several minutes and the hair dyeing property is poor. Further, the dye monomer remains on the scalp, causing itchiness and rash, which is not preferable in terms of safety. When the pH exceeds 8.0, the color developability is too fast, the dye does not penetrate into the hair, and the excellent dyeing effect is not exhibited. In addition, it is not preferable because it stains the skin of hands and scalp.

Regarding the mixing ratio of the aerosol stock solutions of (A) and (B) in the present invention, if one of the aerosol stock solutions is extremely small, it is considered that the dispersion of the filling is widened during the production and the pH of the final composition varies. Therefore, it is preferable that it is in the range of 5/95 to 95/5 in consideration of the filling variation at the time of manufacturing. .

The aerosol propellant as the component (C) in the present invention is one or more selected from inert gases such as liquefied petroleum gas, dimethyl ether, carbon dioxide and nitrogen. The amount is preferably 1 to 10% by weight, which gives sufficient foamability and can be ejected in a foam state. When the amount is less than 1% by weight, the foaming property is weak and the foam state is not obtained, and when the foaming is weak, the skin such as hands and scalp is dyed, which is not preferable. On the other hand, if it exceeds 10% by weight, scattering of the contents occurs, which is not preferable.

The dosage form of the sustained-release hair dye composition of the present invention is provided as an aerosol type foam-like dosage form. In order to obtain such a dosage form, in addition to the above components, an emulsifier, a solubilizer, a humectant, a thickener, a texture improver, and a protective agent that are usually used in the field of cosmetics, in a range not impairing the effects of the present invention. Agents, oils and fats, waxes, ester oils, sequestering agents, perfumes and the like may be added.

The method for producing the slow-dyeing hair dye composition of the present invention is produced by mixing the prepared aerosol stock solutions (A) and (B) in an aerosol pressure resistant container or immediately before filling. It In the production method of the present invention, the aerosol stock solutions (A) and (B) are individually stored before filling,
It means a method of mixing each in an aerosol pressure resistant container at the time of filling, or after mixing immediately before filling and then filling. When the aerosol stock solutions (A) and (B) are mixed before filling, the mixed solution begins to develop color with oxygen in the air in a short time, and discoloration also occurs during the production of the aerosol stock solution, which is a period of 2 to 3 days. It is difficult to store, and discoloration occurs during the filling operation, which is not preferable. After the filling, a valve is attached and then the aerosol propellant of (C) is filled by a conventional method in the manufacturing process of the aerosol product. Further, for more stable production, it is preferable to reduce the pressure when the valve is attached to remove the air in the head space portion, or to produce the head space portion with a filling rate of 70% or more so as to be as small as possible.

The method of using the slow-dyeing hair dye composition of the present invention comprises applying the foam ejected from the aerosol pressure resistant container to the hair. Before or after shampoo, apply evenly on hair, leave for 1 to 5 minutes, then
Rinse gently. By repeating this operation 3 to 5 times, it is possible to make the gray hair inconspicuous without feeling strange.

[0025]

EXAMPLES The present invention will be described in more detail below with reference to examples, but the test methods used will be described prior to the description of each example. In addition, the content of each product shown in the following formulations and tables is% by weight.

(1) Manufacturing Stability Test An aerosol stock solution prepared by a conventional method was filled in a closed container and left at room temperature for 1 day and 3 days. After filling the aerosol undiluted solution into the aerosol pressure resistant container, crimping and propellant filling were performed, and changes in foam (discoloration, deterioration) were compared with a sample immediately filled without leaving for a certain period of time. It was evaluated according to the standard.

[0027]

[Table 1]

(2) Hair Coloring Effect Test 5 g of a hair bundle (a bundle of white hair) was washed with a commercial shampoo for 2 minutes, rinsed with warm water for 1 minute, and then 2 g of the test sample was applied and left for 3 minutes. Then, it was washed with water and air-dried. This series of operations was repeated 5 times. Next, the sample test hair bundles before and after the test sample treatment were subjected to color measurement using a high-speed colorimeter (CMS-1000 type manufactured by Murakami Coloring Materials Co., Ltd.), and X, Y, and Z value is Hunter's L,
After conversion into the a and b color systems, the color difference (ΔE) before and after the treatment was obtained and evaluated by Formula 1. The larger ΔE indicates that the hair was colored.

[0029]

[Equation 1] ΔE = {(L−L ₀ ) ² + (a−a ₀ ) ² +
(B−b ₀ ) ² } ^1/2 L ₀ , a ₀ , b ₀ : L, a, b values of sample hair before treatment L, a, b: L, a, b values of sample hair after treatment

(3) Skin irritation Using the back skin of a test animal (rabbit), 1.0 g of each test sample was applied and washed 5 minutes later, and this operation was continued once a day. I went for 5 days. Next, each test site was visually observed by a skilled appraiser and evaluated according to the criteria in Table 2, and the average value of the scores of 10 test animals was calculated and evaluated.

[0031]

[Table 2]

(4) Practical test: dyeability to hands and scalp,
Hair dyeing properties The hair dye composition in each example is used as a panelist 20 with white hair.
The name was used 5 times, and the coloring properties on the hands and scalp and the hair dyeing effect on the hair were evaluated according to the criteria shown in Table 3 by the effect of hiding the gray hair.

[0033]

[Table 3]

Example 1 An aerosol stock solution of (A) and (B) of a hair dye composition having the following composition was prepared by a conventional method and stored in a closed container for 1 day and 3 days.
After standing for a day, the aerosol pressure resistant container was filled at the same time, after crimping, the propellant of (C) was filled, and the above-mentioned various tests were carried out. The results are shown in Table 4. (A) 2,4-diaminophenol hydrochloride 1.8% by weight ammonium thioglycolate 0.2 edetate 0.1 PG 10.0 purified water 37.9 (B) sodium lauryl sulfate 2.0 triethanolamine 2.7 Purified water 41.3 (C) Liquefied petroleum gas 5.0

Comparative Example 1 Same as Example 1 except that the aerosol stock solutions (A) and (B) in Example 1 were mixed and then left in a sealed container for 1 day and 3 days and filled in an aerosol pressure resistant container. The results are shown in Table 4.

[0036]

[Table 4]

As is clear from Table 4, the composition of Example 1 of the present invention has an excellent hair coloring effect without being dyed on the skin of the hands, scalp and the like at the time of use, can be stably produced, and has storage stability and skin. It was excellent in safety. Comparative Example 1, which was prepared without dividing the aerosol stock solution, was extremely inferior in production stability, and the composition was discolored or deteriorated to deteriorate the hair coloring property, and the skin such as hands or scalp was easily dyed.

Examples 2 to 7 and Comparative Examples 2 to 5 The aerosol stock solutions (A) and (B) of the hair dye compositions having the following compositions were adjusted to a predetermined pH with triethanolamine and then stored in a closed container. After standing for 1 day and 3 days, it was filled in an aerosol pressure resistant container, filled with a propellant (C) according to a conventional method, and the above-mentioned various tests were carried out. The results are shown in Table 5. (A) 2,4-diaminophenol hydrochloride 1.8% by weight thioglycolic acid monoethanolamine 0.2 PG 10.0 triethanolamine proper amount purified water The total amount is 50.0 (B) stearyltrimethylammonium chloride 1 0.0 Triethanolamine Appropriate amount Purified water Total amount is 45.0 (C) Liquefied petroleum gas 5.0

[0039]

[Table 5]

As is clear from Table 5, the compositions of Examples 2 to 7 of the present invention have an excellent hair coloring effect without being dyed on the skin of the hands and scalp skin during use, can be stably manufactured, and have storage stability and storage stability. It was excellent in skin safety. In comparison, in Comparative Examples 2 to 5, sufficient effects were not obtained for any of the evaluation items.

Examples 8 to 13 and Comparative Examples 6 to 9 Hair dye compositions having the composition shown in Table 6 were prepared according to a conventional method, the above-mentioned tests were conducted, and the results are shown in the same table.

[0042]

[Table 6]

As is clear from Table 6, the compositions of Examples 8 to 13 of the present invention have an excellent hair coloring effect without being dyed on the skin of the hands or scalp skin during use, can be stably produced, and have storage stability and storage stability. It was excellent in skin safety.

[0044]

EFFECTS OF THE INVENTION As described above, the present invention is excellent in hair coloring effect without staining hands or scalp skin when used,
It is apparent that the present invention provides a slow-dyeing hair dye composition which can be stably produced and is excellent in storage stability and skin safety, and a method for producing the same.

Claims (2)

[Claims] 1. An aerosol undiluted solution prepared separately according to the following (A) and (B) and (C) are contained, and when the undiluted aerosol solutions of (A) and (B) are mixed, the pH is 6.5 to 8.0. A slow-dissolving hair dye composition. (A) 2,4-diaminophenol or its salt, and an undiluted aerosol solution having a pH of 2.0 to 6.0 containing an antioxidant (B) An undiluted aerosol solution containing an alkali agent and a foaming agent (C) An aerosol propellant 2. The prepared aerosol stock solutions (A) and (B) according to claim 1, which are individually stored until just before filling, and mixed or filled just before filling in an aerosol pressure-resistant container, and then (C). ) Is filled, The manufacturing method of the slow dyeing hair dye composition characterized by the above-mentioned.