JPH0246004B2 - - Google Patents

Description

[Detailed description of the invention]

FIELD OF THE INVENTION The present invention provides a gray hair dye, and more particularly a two-part hair dye using an oxidative dye that does not react or bind with iron ions, which is stable, hypoallergenic, and non-damaging to the hair. This invention relates to a hair dye that dyes only human gray hair. BACKGROUND OF THE INVENTION Conventionally, it consists of two dosage forms, the first part containing an oxidation dye and the second part containing hydrogen peroxide, and when used, the first part and the second part are mixed and applied to the hair.
Hair dyes are known that penetrate oxidative dye molecules into the hair, bleach the hair with nascent oxygen that generates hydrogen peroxide, and oxidatively polymerize the oxidative dye to develop color, thereby coloring the hair. ing. However, the bleaching effect of hydrogen peroxide is very strong, causing hair damage, and when dyeing gray hair, it bleaches even black hair, leaving the entire hair in a faded state. Further, for convenience of use, it is desired to form an aerosol, but there is also the problem that it is difficult to stabilize hydrogen peroxide, making it impossible to form an aerosol. In addition, since such hair dyes generally dye the hair strongly all at once, the appearance of the hair changes too rapidly, causing an unnatural feeling, which is particularly problematic when dyeing gray hair. The present inventors solved the problems with two-part hair dyes using oxidation dyes and hydrogen peroxide, and
We conducted extensive research in order to create a hair dye that is highly effective for dyeing gray hair. As a result, it was surprisingly discovered that the object could be achieved by using bromate and iron ions instead of hydrogen peroxide and combining them with an oxidation dye that does not react with or bind to iron ions. I've come to the point where I can complete it. Summary of the Invention The present invention is a two-part system consisting of a first part that contains an oxidation dye that does not react or bond with iron ions as an essential component, and a second part that does not contain hydrogen peroxide and has a bromate as an essential component. Another object of the present invention is to provide a hair dye for gray hair, characterized in that iron ions are blended into at least either the first agent or the second agent. Bromate is also an oxidizing agent similar to hydrogen peroxide, but its oxidizing power is very weak, and even if it is combined with an oxidative dye, the oxidative dye will not polymerize or develop color, and hair will not be dyed. However, according to the present invention, by coexisting iron ions with these, the oxidized dye develops color, and a good, gentle hair dyeing effect can be obtained. Furthermore, as mentioned above, the oxidizing power of bromate is weak, and little oxygen is produced during the nascent period, so there is no damage to hair or bleaching of black hair, and therefore only gray hair is dyed. Moreover, bromate and iron systems are stable and can be made into aerosol forms.
In addition, conventionally, such hair dyes generally swell the hair to facilitate the penetration of dye molecules into the interior of the hair, as well as to promote the generation of nascent oxygen from hydrogen peroxide. So-called alkaline agents such as ammonia and mono-, di- or trialkanolamines are added to the
In the present invention, an alkaline agent is not necessarily required, and the problems of irritation and hair damage caused by alkaline agents can be avoided. Detailed Description of the Invention The first agent of the hair dye of the present invention contains an oxidative dye as an essential component. The oxidative dye is not particularly limited, and any dye that does not react or bond with iron ions and is used for dyeing gray hair may be used. For example, 2-amino-4
-Nitrophenol, 2-amino-5-nitrophenol, 1-amino-4-methylaminoanthraquinone, 3,3'-iminodiphenol, 2,4-diaminophenol hydrochloride, N-phenyl paraphenylene diamine acetate, 1,5-dihydroxynaphthalenediamine, N-phenylparaphenylenediamine hydrochloride, metaphenylenediamine hydrochloride,
Orthoaminophenol, 1,4-diaminoanthraquinone, 2,6-diaminopyridine, diphenylamine, toluene-2,5-diamine, toluene-3,4-diamine, nitroparaphenylenediamine, paraaminoorthocresol, paraaminophenyl sulfate Amic acid, para-aminophenol, para-nitro-orthophenylene diamine, para-phenylene diamine, para-methylaminophenol, picramic acid, picric acid, hydroquinone, N-phenyl para-phenylene diamine, phloroglucin, hydroxyflazylene, meta-aminophenol, Metaphenylenediamine, orthochlorparaphenylenediamine sulfate, 4,4'- sulfate
Diaminodiphenylamine, para-nitrometaphenylenediamine sulfate, 2-amino-5-nitrophenol sulfate, ortho-aminophenol sulfate, toluene-2,5-diamine sulfate, nitro-paraphenylenediamine sulfate, para-aminophenol sulfate, para-sulfate nitroorthophenylenediamine,
Paraphenylenediamine sulfate, paramethylaminophenol sulfate, metaphenylenediamine sulfate,
Examples include meta-aminophenol sulfate, para-amino orthocresol sulfate, catechol, resorcinol, and their salts.
Two or more types can also be used in combination. The amount of oxidation dye can be selected as appropriate, but generally it is 0.1 to 5% (wt%) based on the total amount of the first agent.
(the same applies below). The second agent of the hair dye of the present invention contains bromate as an essential component. The bromate used is sodium bromate,
Potassium bromate, zinc bromate, aluminum bromate, ammonium bromate are listed, and they have hair dyeing effects,
From the point of view of economic efficiency, etc., 0.1 to 20% based on the total amount of the second agent,
Preferably, it is blended in an amount of 1 to 5%. Further, in the present invention, iron ions are blended into either the first agent or the second agent, or both. The iron ion may be either divalent or trivalent ion, and the combination of iron ions may be, for example, ferrous sulfate, ferric sulfate, ferrous chloride, ferric chloride,
Ferrous compounds such as ammonium ferrous citrate, ferrous nitrate, ferric nitrate, ferrous hydroxide, ferric hydroxide, ferrous phosphate, ferric phosphate, potassium ferrocyanide, potassium ferricyanide, etc. This can be done by addition. The concentration of iron ions to be blended is 10 ^-4 to 5%, preferably 10 ^-2 to 1% as iron content, based on the total amount of the first or second agent. If the iron ion concentration is too high, the oxidation dye will develop color faster, but the dyeability will weaken and the preparation itself will become brownish.On the other hand, if the iron ion concentration is too low, the oxidation dye will not be able to develop color, so it is recommended that the oxidation dye develop color quickly. do. As is clear from the experiments described below, the hair dyeing effect of the hair dye of the present invention is specific to the oxidative dye monobromate-iron ion system; A combination of oxidation dyes and iron ions alone does not produce any hair dyeing effect, and good hair dyeing effects cannot be obtained even when other metal ions are used in place of iron ions. Thus, both the first agent and the second agent of the hair dye of the present invention can be made into a dosage form such as an aqueous solution, emulsion, cream, paste, or gel according to a conventional method. Unlike bromate, bromate is stable even when made into an aerosol form, and can be made into an aerosol form according to conventional methods, and can be used as hair dyes such as shampoo type, treatment type, and pre-treatment type. can. Other ingredients are not particularly limited,
Various solubilizers, emulsifiers, solvents, wetting agents, chelating agents, foaming agents, foaming aid oils and fats, waxes, hydrocarbons, fatty acids, alcohols, polyhydric alcohols, ester oils, fragrances, etc. are appropriately combined and blended. be able to. Also, like conventional hair dyes, ammonia,
Although an alkaline agent such as mono-, di-, or trialkanolamine may be blended, the hair dye of the present invention provides good hair dyeing effects even without the use of such an alkaline agent. Although not particularly limited, in the hair dye of the present invention, it is preferable to adjust the pH to 6 to 8 from the viewpoint of preventing hair damage. At this time, when the pH is higher than 6, iron ions tend to precipitate as iron hydroxide, so use chelating agents such as EDTA salt, sodium tripolyphosphate, phytic acid, sorbitol, and 1-hydroxyethane-1,1-diphosphoric acid. Based on the total amount of the first or second agent, 0.1 to 2
It is preferable to mix about %. Furthermore, in the hair dye of the present invention, it has been found that when a cationic surfactant is used in combination, the hair dyeing properties are improved. Such cationic surfactants include:
Examples include monoalkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, alkylpyridinium salts, etc.
It is preferable to mix it in an amount of about 0.1 to 5% based on the total amount of the agent. The hair dye of the present invention can be used in the same manner as conventional two-dose hair dyes, for example, when used, the first
The agent and the second agent are mixed in a weight ratio of 1:4 to 4:1, applied uniformly to the hair, left for 1 to 30 minutes, then rinsed lightly and shampooed as usual. The hair dye of the present invention replaces conventional hydrogen peroxide with
It uses a combination of hydrobromide and iron, which has a mild reaction, and can prevent hair damage and dye gray hair well and gently. Experiment (1) Color development test of oxidation dyes using a combination of bromate and iron ions The first agent (liquid) of the following formulation and the second agent of bromate, iron ion, or a combination of them as shown in Table 1. Hair dyeability was evaluated using the agent (liquid). First agent prescription ingredients % Paraphenylene diamine 1.5 N-phenylparaphenylene diamine 0.7 Isopropyl alcohol 10.0 Propylene glycol 5.0 Sodium lauryl sulfate 1.0 Anhydrous sodium sulfite 0.2 Purified water Remainder First and second agents in a weight ratio of 1: Mix with 1,
The product was applied to untreated blonde hair, dyed at 25-27°C for 5 minutes, washed with water, and visually evaluated for hair dyeability according to the following criteria. ○: Good (hair dye color...black gray to black blue) △: Slightly good ×: Bad results are shown in Table 1.

【table】

[Table] *: The remainder is purified water **: As iron As is clear from the results in Table 1, oxidation dyes,
A specifically good hair dyeing effect is obtained only when bromate and iron ions are combined and is independent of PH. Also, bromate is 0.1-20%, iron ion is
A good hair dyeing effect can be obtained at 10 ^-4 to 5%. (2) Hair dyeability of various metal ions The hair dyeability of various metal ions was evaluated in the same manner as the test in (1) above, except that the formulation of the second agent was changed as shown in Table 2. The results are shown in Table 2.

【table】

[Table] *The remainder is purified water As shown in Table 2, a good hair dyeing effect can be obtained only when iron ions are used, and the iron ions may be divalent or trivalent. Examples Next, the present invention will be explained in more detail with reference to examples. Example 1 A gray hair dye having a cream as the first agent and a liquid as the second agent was obtained according to the following formulation in accordance with a conventional method. First agent prescription ingredients % Liquid paraffin 10.0 Cetyl alcohol 5.0 Polyoxyethylene (4) stearyl 1.5 Ether polyoxyethylene (12) cetyl 0.7 Ether propylene glycol 5.0 Thioglycolic acid 0.01 EDTA・2Na 0.2 Paraphenylene diamine 0.5 Resorcinol 0.5 Meta Aminophenol 0.7 Methyl paraoxybenzoate 0.1 Fragrance 0.5 28% aqueous ammonia 5.0 Purified water Remaining ingredients for the second agent % Sodium bromate 5.0 Ferrous sulfate 0.5 Citric acid 0.1 Purified water Remaining Example 2 Accordingly, a gray hair dye was obtained in which the first part was a shampoo liquid and the second part was a cream. First agent prescription ingredients % Ammonium lauryl sulfate 15.0 Coconut oil fatty acid diethanolamide 5.0 Polyoxyethylene (5) nonyl 5.0 Phenyl ether 1,3-butylene glycol
10.0 EDTA・2Na 0.1 Anhydrous sodium sulfite 0.3 Ferric chloride 1.0 Metaphenylenediamine 0.5 Metaaminophenol 0.5 Toluene-2,5-diamine sulfate 0.7 Purified water Remainder Second agent prescription ingredients % Sodium bromate 1.0 Second phosphate Sodium hydrogen 0.1 Sodium hydroxide 0.01 Setanol 3.0 Stearyltrimethylammonium chloride 2.0 Purified water Remaining Example 3 Two-dose gray hair dyes, each of which is a treatment type, were obtained according to the conventional method using the following formulation. First agent prescription ingredients % Distearyldimethylammonium chloride 2.5 Stearyl alcohol 1.0 Isopropyl myristate 1.0 Polyethylene glycol 400 5.5 95% ethanol 5.0 Sorbitan monooleate 1.0 Polyoxyethylene (20) Sorbitan monooleate 1.0 Sodium laurylamine dipropionate 1.5 Sorbitol 2.0 Cysteine 0.03 Triethanolamine 2.0 Paraphenylenediamine 0.5 N-phenylparaphenylenediamine 0.3 2,6-diaminopyridine 0.6 Orthoaminophenol 0.2 Purified water Remainder Second agent prescription ingredients % Sodium bromate 0.5 Cetostearyl Alcohol 1.5 Glyceryl monostearate 1.5 Jojoba oil 0.2 1-Hydroxyethane-1,1-diphosphoric acid 0.5 Stearyldimethylamine oxide 1.0 Lauryldimethylamine oxide 3.0 Iron ammonium citrate 2.0 Glycerin 3.0 95% ethanol 8.0 Purified water Remaining Example 4 Implementation Filling an aerosol container with the first agent obtained in Example 3 at a weight ratio of 96:4 and the second agent together with LPG gas at a weight ratio of 94:6,
A two-dose gray hair dye in the form of an aerosol foam was obtained. Example 5 A two-dose gray hair dye consisting of a shampoo as the first part and a cream as the second part was obtained according to the following formulation according to a conventional method. First agent prescription ingredients % Oleic acid 5.0 Oleyl alcohol 5.0 N-lauryl-N,N-dimethylacetic acid sodium betaine 8.5 Lauric acid diethanolamide 3.0 Polyoxyethylene (40) stearyl ether
1.5 N-methylpyrrolidone 7.0 Propylene glycol 3.0 Anhydrous sodium sulfite 0.8 Ferric phosphate 0.7 Phytic acid 0.5 Paraphenylenediamine 1.2 Metaaminophenol 0.3 Metaphenylenediamine 0.6 Resorcinol 0.5 Fragrance 0.3 28% aqueous ammonia 10.0 Purified water Balance 2nd Prescription ingredients % Potassium bromate 3.0 Sodium lauroylmethyltaurate 5.0 Behenyl alcohol 0.5 Glyceryl monostearate 2.0 EDTA・2Na 0.1 Purified water Balance

Claims (1)

[Scope of Claims] 1. A first agent that contains an oxidation dye that does not react with or bind to iron ions as an essential component, and a second agent that does not contain hydrogen peroxide and has a bromate as an essential component. 2.
1. A hair dye for gray hair, which is a hair dye containing iron ions in at least one of the first part and the second part. 2 0.1 to 20% by weight of bromate based on the total amount of the second agent, and iron ions based on the total amount of the first or second agent.
10 ⁻⁴ to 5% by weight of the hair dye according to item 1 above. 3. The hair dye according to item 1 or 2 above, wherein the first agent and the second agent have a pH of 6 to 8. 4. The hair dye according to any one of Items 1 to 3 above, which contains a chelating agent. 5 Item 1 above containing a cationic surfactant
Any one hair dye of item 4. 6. Item 1 above which is an aerosol foam dosage form.
Any one hair dye of item 5.