JP2746527B2 - Slow-dyeing hair dye composition and method for producing the same - Google Patents

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, has an effect of gradually coloring hair without dyeing the hands during use, can be manufactured stably, and has storage stability and skin safety. The present invention relates to an aerosol foam-like slow-dyeing hair dye composition having excellent properties.

[0002]

2. Description of the Related Art Conventionally, in the field of hair dyes, a two-part oxidative hair dye comprising a first agent mainly containing paraphenylenediamine or toluene-2,5-diamine and a second agent mainly containing an oxidizing agent. Agents are 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 firstly used just before use.
It is necessary to uniformly mix the agent and the second agent, and the operation of the hair dyeing treatment is very complicated, and the irritation is so high that it cannot be applied particularly to allergic persons. Furthermore, it is immediately recognized that a third party has dyed the hair because the hair color is rapidly changed, which causes an uncomfortable feeling. In recent years, rinse-type hair dyes using acid dyes characterized by gradually dyeing hair have been put on the market, but hair dyes using this acid dye have very little hand or scalp. It has a problem that it is easily dyed and does not easily fall once dyed. Therefore, the hair color gradually changes to the natural color naturally without a sudden change in color, and it can be easily dyed without complicated operations, and furthermore, it is safe to dye hands and scalp etc. Tall ones are strongly desired.

[0003] Japanese Patent Laid-Open No.
Japanese Patent No. 308215 proposes a method using an acid dye and a quaternary ammonium salt. However, an anionic acid dye and a cationic quaternary ammonium salt form an insoluble salt, and a sufficient There is a problem that dyeing power cannot be obtained and that skin is more easily dyed than hair. Japanese Patent Application Laid-Open No. 61-78714 proposes a gray hair coloring agent for cumulative hair dyeing using an oxidation dye such as paraphenylenediamine, but the operation is complicated and the hair is damaged. There is. Also, Japanese Patent Application Laid-Open No. 2-53
715, JP-in JP 6 2 -126114, JP-
Attempts have been made to develop one-part hair dyes using 2,4-diaminophenol, but these methods require a hair dyeing time of 10 minutes or more, are inconvenient, and have low safety to the skin. The composition was insufficient, and discoloration and the like occurred during the production, and the stability of the composition was poor, so that practical use was impossible.

[0004]

DISCLOSURE OF THE INVENTION In view of the above circumstances, the present inventors have intensively studied to develop a hair dye composition which has improved the problems and disadvantages of the prior art. 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. The two types of aerosol stock solution and the aerosol propellant are contained, and the pH at the time of mixing the aerosol stock solution is 6.5-8. The slow-dyeing hair dye composition is characterized in that it has an effect of gradually coloring hair without dyeing hands at the time of use, can be manufactured stably, and has good storage stability and skin safety. It was found that they were excellent, and the present invention was completed.

That is, the present invention comprises an aerosol stock solution prepared separately in the following (A) and (B) and (C), and the pH of the aerosol stock solution of (A) and (B) at the time of mixing is 6.5. It is a slow dyeing hair dye composition characterized by being -8.0. (A) 2,4-diaminophenol or a salt thereof, ascorbic acid and a salt thereof, a sulfite, a bisulfite
Sulfate, thiosulfate, thioglycolic acid and salts thereof, L
-Cysteine and its salt, N-acetyl-L-cysteine
And its salts, thiolactic acid and its salts.
P containing at least one or more antioxidants
Aerosol stock solution of H2.0～6.0 (B) an aerosol stock solution containing an alkali agent and a foaming agent (C) an aerosol propellant invention further an aerosol stock solution was prepared by dividing into (A) and (B) Store individually until just before filling, after filling and mixing in an aerosol pressure vessel , or after mixing just before filling
After filling into an aerosol pressure container, further (C) Air
A method for producing a slow-dyeing hair dye composition, which is filled in a sol pressure container .

Hereinafter, the present invention will be described in detail. The 2,4-diaminophenol in the aerosol stock solution (A) in the present invention is a known compound, and any of a free compound or a salt compound may be used.
Considering the implementation of the present invention, it is preferable to use sulfates, hydrochlorides, acetates and the like in terms of stability during the production process. The amount 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. If it is less than 0.1% by weight, a satisfactory hair dyeing effect is hardly obtained, and if it is more than 5% by weight, there are problems in safety and stability, which is not preferable.

[0007] Antioxidants of aerosol stock solution of (A) in the present invention is for stabilizing the dye in the aerosol stock solution, is an antioxidant, ascorbic acid and its salts, sulfites, Bisulfite, thiosulfate, thioglycolic acid and its salts, L-cysteine and its salts,
N-acetyl-L-cysteine and its salts, thiolactic acid and its salts , and these can be applied in combination. The amount of the stabilizer is usually 0.05 to 1% by weight based on the total amount of the composition. If the amount is less than 0.05% by weight, it is impossible to sufficiently stabilize the dye stock solution. If the amount is more than 1% by weight, the dye undergoes a reducing action, causing a problem in color development or irritation to the skin. It is not preferable.

[0008] The pH of the aerosol stock solution of (A) of the present invention is adjusted to 2.0 to 6.0, preferably 3.0 to 5.0.
5 If the pH is less than 2.0, the filling device and the storage container (particularly, made of stainless steel) are corroded during production filling or storage, which is not preferable in terms of stability of the stock solution. Further, when the pH is 6.
If it exceeds 0, the stock solution itself develops color and 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 aerosol stock solutions (A)
The method for adjusting H can be achieved without adding an acid by using an acid salt such as hydrochloride, sulfate and acetate for 2,4-diaminophenol and other compound dyes.
Furthermore, it can be achieved by blending organic acids such as citric acid, tartaric acid, malic acid and salts thereof, inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid and salts thereof.

The aerosol stock 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 anionic, nonionic, amphoteric, and cationic surfactants may be used. 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, from the viewpoint of the stability of the stock solution, a water-soluble one is preferable. A preferred amount is 0.01% to 5.0% by weight 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, , 3-
Butylene glycol, polyethylene glycol, hexylene glycol, ethanol, isopropyl alcohol, benzyl alcohol, N-methylpyrrolidone, methylcellosolve, ethylcellosolve, and the preferred compounding amount is 1 to 30 based on the total amount of the composition. % By weight.

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

Specific examples of the alkaline agent in the aerosol stock solution (B) in the present invention include monoethanolamine, diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine,
Examples thereof include organic alkalis such as aminomethylpropanol 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, corrosion of the aerosol pressure container and the like should be taken into consideration. For example, one that corrodes a resin and an aluminum can, such as ammonia, is generally not preferable. The amount of the alkaline agent is 0.1 to 1 based on the total amount of the composition.
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 aerosol stock solution.
In the range of H6.5 to 8.0, any type may be used as long as it is stable and has sufficient foaming properties. Specific examples of the anionic foaming agent include sodium lauryl sulfate and lauryl. Higher alkyl sulfates such as ammonium sulfate, polyoxyethylene alkyl sulfates such as sodium POE lauryl ether sulfate, disodium lauryl sulfosuccinate, sulfosuccinates such as sodium dioctyl sulfosuccinate, and higher grades such as sodium N-lauryl-N-methyltaurine Fatty acid amide sulfonate, triethanolamine lauryl phosphate, phosphate ester such as POE alkyl ether phosphate, sulfonate such as dodecylbenzene sulfonate, N-acyl sarcosine salt such as sodium lauroyl sarcosine, N
N-acyl amino acid salts such as -lauroyl glutamate and N-lauroyl aspartate. In addition, fatty acid soaps such as alkyl carboxylate and oleic acid soap have foaming properties in a high pH range, and cannot be set to a target pH range, which is not preferable.

Specific examples of nonionic surfactant foaming agents include sorbitan fatty acid esters such as sorbitan monostearate, glycerin fatty acid esters such as glyceryl monostearate, polyglycerin fatty acid esters such as decaglycerin monolaurate, and POE sorbitan. Polyoxyethylene sorbitan fatty acid esters such as stearates, polyoxyethylene glycerin fatty acid esters such as POE glycerin stearate, polyethylene glycol fatty acid esters such as POE monolaurate, POE
Polyoxyethylene alkyl ethers such as cetyl ether, polyoxyethylene polyoxypropylene alkyl ethers such as POE / POP cetyl ether, polyoxyethylene alkyl phenyl ethers such as POE nonyl phenyl ether, and polyoxyethylene cured casters 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, aminocarboxylates such as sodium N-coconut oil alkyl-β-aminopropionate, sulfobetaine, and aminobetaine. I can do it.

Specific examples of the foaming agent for the cationic surfactant include lauryltrimethylammonium chloride, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, behenyltrimethylammonium chloride, palmityltrimethylammonium chloride, cocoyltrimethylammonium chloride and eicosyltrimethyl. Mono-long chain alkyl quaternary ammonium salts such as ammonium chloride, dipalmityl dimethyl ammonium chloride, distearyl dimethyl ammonium chloride, di-hydrogenated tallow alkyl dimethyl ammonium chloride, di-hydrogenated tallow alkyl dimethyl ammonium diethyl sulfate, etc. Long-chain alkyl quaternary ammonium salt, stearyl pentaethoxy ammonium chloride, ethyl sulfate Lanolin fatty acid aminopropyl ethyl dimethyl ammonium, benzalkonium chloride, and benzethonium chloride.

The 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 amount is less than 0.3% by weight, it is difficult to obtain a sufficient foaming property, and the dyeing on the skin such as hands and scalp becomes remarkable. When the content is 30% by weight or more, the foam is hard to be crushed, the hair dyeing property is reduced, and skin irritation such as Kayumi and rash is caused.

The pH of the aerosol stock solution (B) of the present invention is usually adjusted to 6.5 to 12.0, preferably 7.0.
１10.0. If the pH is less than 6.5, it is difficult to adjust the pH of the final composition to the pH range (pH 6.5 to 8.0). If the pH exceeds 12.0, the foaming agent deteriorates and deteriorates during storage. And the like, and high heat of neutralization is generated when mixed immediately before filling.

In the present invention, the pH of the stock aerosol solutions (A) and (B) at the time of mixing is in the range of 6.5 to 8.0, preferably 6.8 to 7.8. pH 6.5
If it is less than 10 minutes, no color is formed in a short time of several minutes, and the hair dyeing property is poor. In addition, the dye monomer remains on the scalp, causing Kayumi and rash, which is not preferable in terms of safety. If the pH exceeds 8.0, the coloring property is too fast, and the dye does not penetrate into the hair, so that an excellent dyeing effect is not exhibited. Further, it is not preferable because skin such as hands and scalp is remarkably stained.

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

The aerosol propellant of the component (C) in the present invention is one or more selected from liquefied petroleum gas, dimethyl ether, carbon dioxide, and inert gas such as nitrogen. The amount which can produce sufficient foaming properties and can be ejected in a foam state is preferably 1 to 10% by weight. If the amount is less than 1% by weight, the foaming property is weak and does not form a foam, and if the foaming is weak, it is undesirably dyed on the skin such as hands and scalp. On the other hand, when the content exceeds 10% by weight, the contents are scattered, which is not preferable.

The dosage form of the slow-dyeing hair dye composition of the present invention is provided in the form of an aerosol foam. In order to obtain such a dosage form, in addition to the above-mentioned components, emulsifiers, solubilizers, wetting agents, thickeners, feel improvers, and protective agents usually used in the cosmetics field as long as the effects of the present invention are not impaired. Agents, oils and fats, waxes, ester oils, sequestering agents, fragrances and the like may be added.

The method for producing the sustained-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 mixing them immediately before filling. You. In the production method of the present invention, the aerosol stock solutions (A) and (B) are individually stored until filling,
It means a method in which each is mixed in an aerosol pressure-resistant container at the time of filling or mixed immediately before filling and then filled. When the aerosol stock solutions (A) and (B) are mixed before filling, the mixed solution begins to develop color in a short time with oxygen in the air, discoloration occurs during the production of the aerosol stock solution, and a period of 2 to 3 days It is difficult to store, and it is not preferable because discoloration occurs during the filling operation. After the filling, a valve is attached and then the aerosol propellant (C) is filled according to a conventional method of a manufacturing process of an aerosol product to manufacture the product. For more stable production, it is preferable to reduce the pressure at the time of mounting the valve to remove air in the head space portion, or to produce the head space portion at a filling rate of 70% or more so as to minimize the air space.

The method of using the sustained-dyeing hair dye composition of the present invention comprises applying foam sprayed from an aerosol pressure-resistant container to hair. Before or after shampooing, apply evenly to hair, leave for 1 to 5 minutes,
Rinse lightly. By repeating this operation three to five times, the gray hair can be made inconspicuous without any strange feeling.

[0025]

EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples. Before describing each example, test methods used will be described. The contents of the products shown in the following formulations and tables are% by weight.

(1) Production stability test The 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 undiluted aerosol solution into an aerosol pressure-resistant container, crimping and filling with a propellant were carried out, and changes in foam (discoloration and deterioration) were compared with a sample that was immediately filled without standing for a certain period of time. Evaluation was based on criteria.

[0027]

[Table 1]

(2) Hair coloring effect test 5 g of a hair bundle (a bundle of white hair) was washed with a commercially available shampoo for 2 minutes, rinsed with warm water for 1 minute, applied with 2 g of a test sample, and left for 3 minutes. Thereafter, it was washed with water and air-dried. This series of operations was performed five times. Next, the color of the sample test hair bundle before and after the test sample treatment was measured using a high-speed colorimeter (CMS-1000, manufactured by Murakami Color Materials Co., Ltd.), and the X, Y, and Change the Z value to Hunter's L,
After conversion to the a and b color system, the color difference (ΔE) before and after the processing was obtained and evaluated using Equation 1. The larger the ΔE, the more 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 skin on the back of a test animal (rabbit), 1.0 g of each test sample was applied, washed 5 minutes later, and this operation was repeated once a day. For five days. Next, each test site was visually observed by a skilled appraiser and evaluated according to the criteria shown in Table 2, and the average of scores of 10 test animals was calculated and evaluated.

[0031]

[Table 2]

(4) Practical test: Dyeability on hands and scalp,
Hair Coloring Property The hair dye composition in each example was converted to a white hair-mixed panel 20.
The name was used five times, and the coloring properties on the hands and scalp and the hair dyeing effect on the hair were evaluated based on the criteria shown in Table 3 based on the gray hair hiding effect.

[0033]

[Table 3]

EXAMPLE 1 Aerosol stock solutions (A) and (B) of a hair dye composition having the following composition were prepared by a conventional method, and were prepared in a closed container for 1 day and 3 days.
After standing for a day, the aerosol pressure container was simultaneously filled, and after crimping, the propellant (C) was filled, and the above-mentioned tests were performed. 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 of (A) and (B) in Example 1 were mixed, allowed to stand 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 excellent hair coloring effect without dyeing the skin such as hands and scalp when used, can be manufactured stably, and has good storage stability and skin stability. Excellent safety. Comparative Example 1 prepared without dividing the aerosol stock solution is extremely inferior in production stability, discoloration and alteration of the composition occurs, hair coloring property is reduced, and dyeing on the skin such as hands and scalp becomes easy.

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 sealed in a closed container. After leaving for 1 day and 3 days, the aerosol pressure container was filled, the propellant (C) was filled according to a conventional method, and the above-mentioned tests were performed. The results are shown in Table 5. (A) 2,4-diaminophenol hydrochloride 1.8% by weight monoethanolamine thioglycolate 0.2 PG 10.0 Triethanolamine Appropriate amount Purified water The total amount is adjusted to 50.0. (B) Stearyl trimethylammonium 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 excellent hair coloring effects without dyeing hands and scalp skin during use, can be manufactured stably, and have good storage stability and Excellent skin safety. In comparison, Comparative Examples 2 to 5 did not provide a sufficient effect on 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, subjected to the above-mentioned tests, 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 excellent hair coloring effects without staining hands, scalp and skin at the time of use, can be manufactured stably, and have good storage stability and Excellent skin safety.

[0044]

As described above, the present invention has an excellent hair coloring effect without staining the hands and scalp skin when used.
It is apparent that the present invention provides a sustained-dyeing hair dye composition which can be stably manufactured, has excellent storage stability and skin safety, and a method for manufacturing the same.

Claims (3)

(57) [Claims] 1. An aerosol stock solution prepared separately in the following (A) and (B) and (C) are contained, and the pH of the aerosol stock solution of (A) and (B) at the time of mixing is 6.5 to 8.0. A slow-dyeing hair dye composition, characterized in that: (A) 2,4-diaminophenol or a salt thereof, ascorbic acid and its salt
Salts, sulfites, bisulfites, thiosulfates, thioglycosides
Acid and its salt, L-cysteine and its salt,
Cetyl-L-cysteine and its salts, thiolactic acid and its salts
PH2.0~6.0 aerosol stock solution containing at least one or more antioxidants selected from the group consisting of a salt (B) an aerosol stock solution containing an alkali agent and a foaming agent (C) an aerosol propellant 2. An aerosol stock solution prepared separately in the following (A) and (B) and (C), and the pH of the aerosol stock solution of (A) and (B) at the time of mixing is 6.5 to 8.0. A slow-dyeing hair dye composition, characterized in that: (A) 2,4-di-aminophenol or a salt thereof, Ass
Corbic acid and its salts, sulfites, bisulfites, thio
Sulfate, thioglycolic acid and salts thereof, L-cysteine
And a salt thereof, N-acetyl-L-cysteine and a salt thereof.
Salt, thiolactic acid and its salts
PH 2.0 or more containing at least one or more antioxidants
6.0 aerosol stock solution (B) monoethanolamine, diethanolamine,
Liethanolamine, diisopropanolamine, tri
Isopropanolamine, aminomethylpropanol,
Ammonium bicarbonate and salts thereof, sodium hydroxide
, Potassium hydroxide, calcium hydroxide
Aerosol stock solution containing an alkali agent and a foaming agent selected (C) an aerosol propellant 3. The aerosol pressure solution according to claim 1 or 2, wherein the prepared aerosol stock solutions (A) and (B) are individually stored until just before filling, and after filling and mixing in an aerosol pressure container , or after mixing just before filling. A method for producing a slow-dyeing hair dye composition, which further comprises filling (C) into an aerosol pressure-resistant container after filling the container .