JP6757567B2 - Hair dye - Google Patents

Description

The present invention relates to a non-oxidizing hair dye and a hair dyeing method using the same.

Permanent hair dyes are hair dyes that give the hair a permanent dyeing result. As the permanent hair dye, an oxidation type that conventionally uses a first agent containing an oxidizing dye such as para-phenylenediamine and an alkaline agent and a second agent containing an oxidizing agent such as hydrogen peroxide solution in a mixed manner. Hair dyes are generally widely used. However, the oxidized hair dye may damage the hair due to the action of the alkaline agent and the hydrogen peroxide solution. In addition, some oxidative dyes may cause a strong allergic reaction.

In recent years, various types of non-oxidizing hair dyes have been proposed in order to solve the problems that may occur in such oxidized hair dyes. For example, reaction between polyhydric phenols and metal salts. There are known hair dyes that dye hair using the above (see Patent Documents 1 to 7). In addition, photobleaching includes a combination of a substance that develops color by reacting with iron such as tannic acid, gallic acid and derivatives thereof, a first agent containing an ultraviolet absorber, and a second agent containing an iron salt. A non-oxidizing hair dye having a preventive effect has also been proposed (Patent Document 8). Further, the hair dye consisting of a first agent containing a color former that develops color by reacting with metal ions and a second agent containing a metal salt is selected from the group consisting of HC dyes, basic dyes and direct dyes. A hair dye containing a dye has been proposed (Patent Document 9).

Tokukousho 48-31902 Japanese Unexamined Patent Publication No. 53-52633 Japanese Unexamined Patent Publication No. 55-154912 Japanese Unexamined Patent Publication No. 62-33113 Japanese Unexamined Patent Publication No. 64-90117 Japanese Unexamined Patent Publication No. 4-164017 Japanese Unexamined Patent Publication No. 5-170629 Japanese Unexamined Patent Publication No. 2011-126845 Japanese Unexamined Patent Publication No. 2013-95734

However, all of the conventional non-oxidizing hair dyes as disclosed in the patent documents require a long time to dye the hair or repeatedly dye the hair, and the hair dyeing effect thereof. The color tone and gray hair hiding effect were not always satisfactory. In particular, when tannic acid, gallic acid and their derivatives and iron salts are mixed, the bluish color of the hair after dyeing tends to become stronger when the color is darkened in order to sufficiently dye the gray hair, which is natural for the hair. It was difficult to give a good finish color tone.

An object of the present invention is a non-oxidizing hair dye capable of adjusting the hair after dyeing to a natural hair color and giving a natural color finish while having an excellent hair dyeing effect and a gray hair hiding effect. Is to provide.

The present inventors have repeated detailed studies in order to solve the above problems, and have completed the present invention. That is, the present invention includes the following preferred embodiments.
[1] A hair dye comprising at least the first agent, the second agent and the third agent.
The first agent comprises at least one selected from the group consisting of gallic acid, tannic acid and derivatives thereof.
The second agent contains an iron salt and contains
The third agent contains at least one selected from salicylic acid and its derivatives.
A hair dye in which the third agent is applied to the hair after the first and second agents.
[2] The hair dye according to the above [1], further comprising a fourth agent containing an iron salt.
[3] The hair dye according to the above [1] or [2], which comprises applying the first agent and the second agent to the hair in this order or at the same time, and then applying the third agent. Hair dyeing method.

According to the present invention, a non-oxidizing hair dye capable of adjusting the hair after dyeing to a natural hair color and giving a natural color finish while having an excellent hair dyeing effect and a gray hair hiding effect. Can be provided.

Hereinafter, embodiments of the present invention will be described in detail. The scope of the present invention is not limited to the embodiments described here, and various modifications can be made without impairing the gist of the present invention.

The hair dye of the present invention is composed of at least a first agent, a second agent and a third agent. The first agent contained in the hair dye of the present invention contains at least one selected from the group consisting of gallic acid, tannic acid and derivatives thereof. Gallic acid, tannic acid and their derivatives are components that develop color by reacting with iron, and in the hair dye of the present invention, gallic acid, tannic acid and / or their derivatives contained in the first agent at the time of hair dyeing. And the iron salt contained in the second agent react with each other to produce a hair dyeing effect.

Examples of tannic acid include hydrolyzable tannins and condensed tannins. Examples of hydrolyzed tannins include tannins obtained from quintuplets, gall nuts, smacks, cod, chestnuts, myrobalan, oak, dividibi, algarovia, geranium thunbergii and the like. Examples of condensed tannins include tannins obtained from Gambia, Gebracho, Mimosa, Mangrove, Hemlock, Spruce, Burmakatch, Kashiwa bark, and persimmon astringent.

Derivatives of gallic acid include, for example, alkyl esters of gallic acid. Examples of the alkyl ester of gallic acid include an ester of gallic acid and a linear or branched alkyl having 1 to 10 carbon atoms, preferably 2 to 5 carbon atoms. Examples of such an alkyl ester include ethyl gallate, propyl gallate, and isoamyl gallate. The gallic acid or a derivative thereof may be chemically synthesized by a known method or may be isolated from a plant. It may be isolated from a plant and further chemically synthesized. Further, an extract obtained from a plant containing gallic acid or a derivative thereof may be used as it is. For example, gallic acid derived from the legume cod, gallic acid derived from quintuplet generated in Rhus chinensis, or an extract containing them can be used. Derivatives obtained by chemically esterifying these gallic acids can also be used.

These gallic acid, tannic acid and their derivatives may be used alone or in combination of two or more. It is preferable that the first agent contains gallic acid because the hair dyeing effect and the gray hair hiding effect can be further enhanced by containing gallic acid.

The content of at least one selected from the group consisting of gallic acid, tannic acid and derivatives thereof in the first agent is preferably 0.1 to 10% by mass with respect to the total amount of the first agent. More preferably, it is 0.5 to 6% by mass. When a plurality of types of gallic acid, tannic acid and derivatives thereof are contained, the total amount thereof is preferably within the above range. When the content of at least one selected from the group consisting of gallic acid, tannic acid and derivatives thereof is within the above range, a good hair dyeing effect and a gray hair hiding effect can be obtained.

In the present invention, the first agent is at least one selected from the group consisting of gallic acid, tannic acid and derivatives thereof, at least one organic compound that develops color by reacting with iron, and / or the organic. It may contain at least one plant extract containing the compound. Such organic compounds and plant extracts include, for example, quintuple, pyrogallol, logwood, hematein, catechin, salicylic acid and its derivatives, phthalic acid, eugenol, isoeugenol, nicotinic acid amide, dehydroacetic acid, pyridoxin, ellagic acid, Kodiic acid, maltor, ferulic acid, hinokithiol, turmeric extract, curcumin, ginger extract, onion extract, quercetin, rutin, hesperetin, hesperidin, raw coffee bean extract, caffeic acid, chlorogenic acid, cha extract, catechin, epicatechin, sikon extract, Examples thereof include perilla extract, sisonin, grape leaf extract, butou extract, enocianine, lacic acid, lac, cochineal, carmic acid, elderberry, red cabbage, purple potato, tamarind, coulyan, apigeninidin, and luteolinidin. Among them, salicylic acid and its derivatives are preferable as the organic compound and the plant extract from the viewpoint of enhancing the hair dyeing effect.

The first agent comprises at least one selected from the group consisting of gallic acid, tannic acid and derivatives thereof, as well as at least one organic compound that reacts with iron to develop color and / or the organic compound. When at least one type of plant extract is contained, the content thereof is preferably 0.1 to 5% by mass, more preferably 0.2 to 3% by mass, based on the total amount of the first agent. ..

The first agent in the hair dye of the present invention may contain urea. When the first agent contains urea, the content thereof is preferably 1% by mass or more, more preferably 3% by mass or more, based on the total amount of the first agent. When the first agent contains 1% by mass or more of urea, a hair dye having a higher hair dyeing effect and a gray hair hiding effect can be obtained. The upper limit of the urea content is preferably 20% by mass or less, and more preferably 10% by mass or less, from the viewpoint of the stability of the first agent.

In the hair dye of the present invention, the pH of the first agent is preferably 6 to 10 and more preferably 7 to 9 from the viewpoint of hair dyeing effect and stability of the agent.

The second agent contained in the hair dye of the present invention contains an iron salt. The iron salt reacts with at least one selected from the group consisting of gallic acid, tannic acid and derivatives thereof contained in the first agent to develop a color and can fix the pigment on the hair.

Examples of iron salts include ferrous sulfate, ferrous chloride, ferrous acetate, ferrous phosphate, ferrous oxalate, ferric sulfate, ferric chloride, ferric acetate and the like. Can be mentioned. From the viewpoint of hair dyeing effect, the second agent is at least one iron salt selected from the group consisting of ferrous sulfate, ferrous chloride, ferrous acetate, ferric sulfate and ferric chloride. It is preferably contained, and more preferably it contains at least one iron salt selected from the group consisting of ferrous sulfate, ferrous chloride and ferrous acetate. One of these iron salts may be used alone, or a plurality of types may be used in combination.

The content of the iron salt in the second agent may be appropriately determined within the range in which the effect of the present invention is exhibited, but from the viewpoint of the stability of the agent and the hair dyeing effect, it is preferably 0 based on the total amount of the second agent. .5 to 10% by mass, more preferably 1 to 6% by mass.

In the hair dye of the present invention, the pH of the second agent is preferably 2 to 6, more preferably 3 to 5, from the viewpoint of the hair dyeing effect and the stability of the agent.

The third agent contained in the hair dye of the present invention contains at least one selected from salicylic acid and its derivatives. When the third agent contains at least one selected from salicylic acid and its derivatives, a high gray hair hiding effect can be obtained. Further, where the conventional non-oxidizing hair dye tends to increase the bluish color of the hair after dyeing, the first agent and the second agent contain at least one selected from salicylic acid and its derivatives. By using the third agent, it is possible to adjust the color tone of the hair after dyeing to a natural color tone with less bluish appearance.

Derivatives of salicylic acid include, for example, esters and salts of salicylic acid. Examples of the salt of salicylic acid include alkali metal salts of salicylic acid, and specific examples thereof include sodium salicylate. Examples of the salicylic acid ester include linear or branched alkyl esters and phenyl esters having 1 to 10 carbon atoms, and specific examples thereof include octyl salicylate, phenyl salicylate, and methyl salicylate. Of these, salicylic acid and sodium salicylate are preferable because a high gray hair hiding effect can be obtained. When the first agent contained in the hair dye of the present invention contains one selected from salicylic acid and its derivatives, at least one selected from salicylic acid and its derivatives contained in the third agent is the first agent. It may be the same as or different from salicylic acid and its derivatives.

The content of at least one selected from salicylic acid and its derivatives in the third agent is preferably 0.1 to 3% by mass, more preferably 0.2 to 2.5% by mass, based on the total amount of the third agent. %. By including at least one selected from salicylic acid and its derivatives in the above range, a high gray hair hiding effect and a natural color tone with suppressed bluish color can be obtained.

The third agent contained in the hair dye of the present invention is an oil agent from the viewpoint of stably blending at least one selected from salicylic acid and its derivatives in the third agent to enhance the hair dyeing effect and the gray hair hiding effect. It is preferable to contain it. Examples of the oil agent include ester oil, hydrocarbon oil, silicone oil, animal and vegetable oil, higher alcohol liquid at room temperature, higher fatty acid liquid at room temperature, and the like. From the viewpoint of the stability of the third agent, it is more preferable to contain at least one selected from the group consisting of hydrocarbon oil, ester oil, higher alcohol liquid at room temperature and silicone oil as the oil agent, and the hydrocarbon oil and It is more preferable to contain at least one selected from the group consisting of ester oils. From the viewpoint of stably blending at least one selected from salicylic acid and its derivatives in the third agent, it is more preferable to contain a hydrocarbon oil. Examples of the hydrocarbon oil include liquid paraffin, dioctylcyclohexane, α-olefin oligomer, light isoparaffin, light liquid isoparaffin, squalane, polybutene, and liquid isoparaffin.

When the third agent contains an oil agent, the content of the oil agent is preferably 1% by mass or more, more preferably 3% by mass or more, based on the total amount of the third agent, from the viewpoint of the stability of the preparation. .. Further, from the viewpoint of usability, it is preferably 30% by mass or less, more preferably 15% by mass or less.

Furthermore, the third agent in the hair dye of the present invention may contain urea. When the third agent contains urea, the content thereof is preferably 1% by mass or more, more preferably 3% by mass or more, based on the total amount of the third agent. When the first agent contains 1% by mass or more of urea, a hair dye having a higher hair dyeing effect and a gray hair hiding effect can be obtained. The upper limit of the urea content is preferably 20% by mass or less, and more preferably 10% by mass or less, from the viewpoint of the stability of the first agent.

In the hair dye of the present invention, the pH of the third agent is preferably 6 to 10, and more preferably 7 to 9 from the viewpoint of hair dyeing effect and stability of the agent.

The hair dye of the present invention may further contain a fourth agent containing an iron salt in addition to the first agent, the second agent and the third agent. By including the fourth agent containing an iron salt in addition to the first agent, the second agent and the third agent, the hair dyeing agent consisting of only the first agent, the second agent and the third agent is compared. It is a hair dye that can obtain a higher hair dyeing effect and a gray hair hiding effect, and can give a natural color tone with less bluish tint. In the hair dye of the present invention, the fourth agent is preferably used after the third agent or at the same time as the third agent.

Examples of the iron salt contained in the fourth agent include the same iron salts as those exemplified as the iron salt in the second agent, and one type may be used alone as the iron salt, or a plurality of types may be used in combination. You may. The iron salt content in the fourth agent may be appropriately determined within the range in which the effect of the present invention is exhibited, but is preferable based on the total amount of the fourth agent from the viewpoint of the stability of the agent and the hair dyeing effect. Is 0.5 to 10% by mass, more preferably 1 to 6% by mass.

In the hair dye of the present invention, the pH of the fourth agent is preferably 2 to 6, more preferably 3 to 5, from the viewpoint of hair dyeing effect and stability of the agent.

In the hair dye of the present invention, the fourth agent may be the same agent as the second agent, and is different from the second agent in, for example, the type and amount of iron salt, other components, and the like. May be good.

In the hair dye of the present invention, the first agent, the second agent, the third agent and the fourth agent contain, in addition to the above-mentioned essential components and optional components, other components usually used in the hair dye, respectively. It may be contained in an amount within the range in which the effect of the present invention is exhibited. Such ingredients include, for example, bases, surfactants, fats and oils, solvents, thickeners, organic acids, preservatives, antioxidants, pH regulators, wetting agents, fragrances, masking agents for metallic odors, etc. Coloring agents, UV absorbers, hair growth and nourishing agents, antiseptic agents, antibacterial agents, fabric softeners, moisturizers, active oxygen removers, antioxidants, antimicrobial agents, silicones, minerals, hydrolyzed proteins, peptides, amino acids, etc. Can be mentioned.

Examples of the base include higher alcohols, hydrocarbons, fatty acid esters, vegetable oils, fatty acids and the like. In particular, from the viewpoint of the stability of the preparation, the first agent and the third agent preferably contain a higher alcohol, and at least one higher grade selected from the group consisting of setostearyl alcohol, cetyl alcohol, stearyl alcohol and behenyl alcohol. It is more preferable to contain alcohol. The content of the higher alcohol in the first agent and the third agent is preferably 1% by mass or more, more preferably 3 based on the total amount of each of the first agent or the third agent from the viewpoint of the stability of the preparation. It is mass% or more. Further, from the viewpoint of usability, it is preferably 20% by mass or less, and more preferably 10% by mass or less.

Examples of the surfactant include anionic surfactants, nonionic surfactants, amphoteric surfactants, cationic surfactants and the like. Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, glycerin fatty acid ester, polyglycerin fatty acid ester, polyethylene glycol fatty acid ester, alkyl glucoside and the like. Examples of the anionic surfactant include polyoxyethylene alkyl ether phosphoric acid and salts thereof, N-acylamino acid salt, alkyl ether carboxylate, alkyl sulfate, polyoxyethylene alkyl ether sulfate, sulfonate and the like. Can be mentioned. Examples of the cationic surfactant include an alkylammonium salt and the like. Examples of the amphoteric surfactant include alkylamide propyl betaine and the like.

In particular, in the hair dye of the present invention, from the viewpoint of the stability of the preparation, the first agent and the third agent preferably contain at least one nonionic surfactant, and contain a polyoxyethylene alkyl ether. It is more preferable to do so. In that case, the content of the nonionic surfactant is preferably 0.1 to 10% by mass, more preferably 1 to 7% by mass, based on the total amount of each of the first agent and the third agent. ..

Examples of the antioxidant include ascorbic acid and its derivatives, sodium sulfite and the like.

Examples of the pH adjuster include citrate, phosphoric acid, ammonia, ammonium hydrogencarbonate, ammonium carbonate, potassium hydroxide, sodium hydroxide, monoethanolamine, isopropanolamine, ammonium phosphate, diammonium monohydrogen phosphate, and citrate. Examples thereof include sodium acid, ammonium citrate, potassium phosphate, sodium phosphate and the like.

Examples of the wetting agent include 1,3-butylene glycol, propylene glycol, glycerin, sorbitol, sodium pyrrolidone carboxylate, amino acids, vegetable oils and the like.

Examples of the thickener include xanthan gum, polyethylene glycol, hydroxyethyl cellulose and the like.

Examples of the solvent include water, ethanol, isopropyl alcohol, 1,3-butylene glycol, 1,2-pentanediol, 2-methyl-2,4-pentanediol, glycerin, diglycerin, propylene glycol, dipropylene glycol, and the like. Benzyl alcohol and the like can be mentioned.

The dosage forms of the first agent, the second agent, the third agent and the fourth agent contained in the hair dye of the present invention are not particularly limited, and are, for example, creams, liquids, gels, emulsions, sprays and aerosols. It can be a dosage form such as a mold. All agents may be of the same type or different types. From the viewpoint of usability and stability, the first agent and the third agent are preferably creams or gels. Further, from the viewpoint of usability, the second agent and the fourth agent are preferably creams or gels.

The method for preparing the first agent, the second agent, the third agent and the fourth agent contained in the hair dye of the present invention is not particularly limited, and can be produced by a usual method.

Hair can be dyed by applying the first agent, the second agent and the third agent contained in the hair dye of the present invention, and, if included, the fourth agent to the hair.
The hair dye of the present invention first applies a first agent containing gallic acid, tannic acid or a derivative thereof, and a second agent containing an iron salt to the hair, and then at least selected from salicylic acid and its derivatives. By applying the third agent containing one type, it is possible to exhibit a high hair dyeing effect and a gray hair hiding effect, and to give the hair after dyeing a natural color tone with suppressed bluishness. As a method of applying the first agent and the second agent to the hair, for example, (i) first apply the first agent to the hair, leave it for a certain period of time, and then apply the second agent without washing away the first agent. Then, the method of leaving the hair for a certain period of time, (ii) the method of applying the first agent and the second agent to the hair at the same time and leaving the hair for a certain period of time, and (iii) the first agent and the second agent were mixed and obtained. Examples thereof include a method in which the composition is applied to the hair and left for a certain period of time. From the viewpoint of the hair dyeing effect, the method (i) described above is preferable as the method of applying the first agent and the second agent to the hair.

In the present invention, the ratio of the first agent to the second agent used is preferably 1st agent: 2nd agent = 1: 0.5 to 1: 2 in terms of mass ratio from the viewpoint of usability, and more preferably. First agent: Second agent = 1: 0.8 to 1: 1.2, more preferably 1: 1.

The first agent and the second agent are applied by the method as described above, and the third agent is applied to the hair. The third agent can be applied without washing away the first agent and / or the second agent, but since the hair dyeing effect and the gray hair hiding effect are enhanced, the first agent and / or the first agent and / / Alternatively, it is preferable to wash away the second agent. Hair can be dyed by leaving it for a certain period of time after applying the third agent. The washing of each agent may be carried out with shampoo or only with running water.

When the hair dye of the present invention contains a fourth agent, (iv) the third agent is applied and then left for a certain period of time, the fourth agent is applied without washing away the third agent, and the third agent is left for a certain period of time. After that, the agent was washed away, (v) the third agent and the fourth agent were applied to the hair at the same time, and the agent was washed away after being left for a certain period of time, and (vi) the third agent and the fourth agent were mixed and obtained. Examples thereof include a method in which the above composition is applied to hair, left for a certain period of time, and then the agent is washed away. From the viewpoint of hair dyeing effect, the method ( iv ) described above is preferable as the method of applying the third agent and the fourth agent to the hair.

The leaving time after application to the hair is appropriately adjusted according to the amount of application to the hair, the desired degree of dyeing, and the like. In any of the above methods, the leaving time after application to the hair may be, for example, 1 to 60 minutes, preferably 5 to 40 minutes, respectively, in the state where each agent is applied.

The amount of the first agent, the second agent, the third agent, and the fourth agent applied to the hair is appropriately adjusted according to the amount and length of the hair, the desired degree of dyeing, and the like. From the viewpoint of usability, each agent preferably weighs about 30 to 70 g, more preferably about 40 to 60 g, for hair having a length of about 20 cm. In one aspect of the present invention, 50 g of each of the first agent, the second agent, the third agent and the fourth agent may be applied to hair having a length of about 20 cm. From the viewpoint of burden on the hair and the human body, the temperature at the time of application to the hair is usually preferably 15 to 45 ° C.

Hereinafter, the present invention will be described in more detail with reference to Examples. The scope of the present invention is not limited to the contents of the following examples.

1. 1. Preparation of Formulations Containing Gallic Acid, Tannic Acid or Derivatives thereof According to the composition shown in Table 1, the preparations of Formulation Examples 1 to 12 were prepared as follows.
(1) Preparation of Preparations of Formulation Examples 1 to 3 Liquid paraffin, cetostearyl alcohol and polyoxyethylene setostearyl ether 30EO were mixed as oil phase components and sufficiently heated and dissolved. As the aqueous phase component, components other than the oil phase component excluding potassium hydroxide and urea were mixed and sufficiently heated and dissolved. Then, the aqueous phase component was added to the oil phase component that was heated and dissolved while stirring, and the mixture was emulsified. The obtained emulsion was cooled, and potassium hydroxide having an pH of 8 and urea dissolved in water were added to obtain each of Formulation Examples 1 to 3.

(2) Preparation of Formulation of Formulation Example 12 The preparation of Formulation Example 12 was prepared in the same manner as in Formulation Example 1 and the like of (1) above, except that urea was not added.

2. 2. According to the formulation shown in preparation Table 2 of salicylic acid or formulation containing the induction body in the following manner, it was prepared formulations of Formulation Example 4-11.
Liquid paraffin, setostearyl alcohol and polyoxyethylene setostearyl ether 30EO were mixed as oil phase components and sufficiently heated and dissolved. As the aqueous phase component, components other than the oil phase component excluding potassium hydroxide and urea were mixed and sufficiently heated and dissolved. Then, the aqueous phase component was added to the oil phase component that was heated and dissolved while stirring, and the mixture was emulsified. The obtained emulsion was cooled, and potassium hydroxide having an pH of 8 and urea dissolved in water were added to obtain the respective preparations of Formulation Examples 4 to 11.

3. 3. Preparation of Formulations Containing Iron Salts Formulations A to C were prepared as follows according to the formulations shown in Table 3.
(1) Preparation of Formulation Examples A and B As aqueous phase components, ferrous sulfate or ferrous chloride was added to purified water at room temperature, and ascorbic acid was further added and mixed. As an oil phase component, setostearyl alcohol and polyoxyethylene setostearyl ether were mixed and sufficiently heated and dissolved. Then, the aqueous phase component was added to the oil phase component with stirring and emulsified to obtain the preparations of Formulation Examples A and B. The pH of each of the obtained preparations was about 3.
(2) Preparation of Formulation of Formulation Example C Ferrous sulfate was added to purified water at room temperature, and ascorbic acid was further added and dissolved by stirring to obtain a preparation of Formulation Example C. The pH of each of the obtained preparations was about 3.

4. Hair Dye Evaluation The following hair dyes of Examples 1 to 16 and Comparative Examples 1 to 6 in which the combinations of the formulations of Formulation Examples 1 to 12 and A to C were changed according to the hair dye formulations shown in Table 4. According to the method, the hair dyeing effect, the gray hair hiding effect, and the color tone after hair dyeing were evaluated.

(1) Evaluation of Hair Dyeing Effect and Color Tone 2 g of the first agent was applied to 1 g of shampoo and rinsed hair bundle (white hair ratio 100%), and left at 30 ° C. and 65% relative humidity for 15 minutes. Then, 2 g of the second agent was applied and left again at 30 ° C. and 65% relative humidity for 15 minutes. The hair bundles were then shampooed and rinsed and dried with a dryer. Then, 2 g of the third agent was applied and left at 30 ° C. and a relative humidity of 65% for 15 minutes. Then, 2 g of the fourth agent was applied and left again at 30 ° C. and 65% relative humidity for 15 minutes. The hair bundles were then shampooed and rinsed and dried with a dryer.
In Example 12 not containing the fourth agent, after leaving the third agent in the above treatment method, the hair bundle was shampooed and rinsed, dried with a dryer, and evaluated. Similarly, in Comparative Examples 2, 5 and 6 containing no third agent and fourth agent, after leaving the second agent, the hair bundle was shampooed and rinsed, dried with a dryer, and evaluated.

Using the dried hair bundle, the hair dyeing effect and the color tone of the hair after dyeing were evaluated as follows.

(Hair dyeing effect)
The hair dyeing effect was evaluated with the naked eye by five specialized panelists according to the criteria shown below. If the evaluations of the five panelists were divided into two, the higher evaluation was adopted, and if the evaluations were divided into three or more, the evaluations were repeated until the evaluations of the five people matched or were divided into two. ..
Evaluation Criteria for Hair Dyeing Effect ◎: The hair was dyed deeply.
◯: Hair was dyed clearly.
Δ: The hair was slightly dyed.
X: Hair was not dyed.

(Color tone)
The color (strength of reddish brownness) was evaluated with the naked eye by five specialized panelists according to the criteria shown below. When the evaluation of the five panelists was divided into two or three or more, the evaluation was performed in the same manner as above. By feeling the reddish brown taste, the bluish color developed by the reaction between gallic acid, tannic acid or a derivative thereof and an iron salt can be softened, so that the bluish color is naturally suppressed.
Evaluation criteria for hair color ◎: Feel reddish brown 〇: Feel reddish brown slightly △: Do not feel reddish brown so much ×: No reddish brown

(2) Evaluation of Gray Hair Hiding Effect 4 g of the first agent was applied to 2 g of shampoo and rinsed hair bundles (gray hair ratio 20%), and left at 30 ° C. and 65% relative humidity for 15 minutes. Then, 4 g of the second agent was applied and left again at 30 ° C. and 65% relative humidity for 15 minutes. The hair bundles were then shampooed and rinsed and dried with a dryer. Then, 2 g of the third agent was applied and left at 30 ° C. and a relative humidity of 65% for 15 minutes. Then, 2 g of the fourth agent was applied and left again at 30 ° C. and 65% relative humidity for 15 minutes. The hair bundles were then shampooed and rinsed and dried with a dryer.
In Example 12 not containing the fourth agent, after leaving the third agent in the above treatment method, the hair bundle was shampooed and rinsed, dried with a dryer, and evaluated. Similarly, in Comparative Examples 2, 5 and 6 containing no third agent and fourth agent, after leaving the second agent, the hair bundle was shampooed and rinsed, dried with a dryer, and evaluated.

Using the dried hair bundle, the gray hair hiding effect was evaluated as follows.

(Gray hair hiding effect)
According to the criteria shown below, the gray hair hiding effect was evaluated with the naked eye by five specialized panelists. When the evaluation of the five panelists was divided into two or three or more, the evaluation was performed in the same manner as above.
Evaluation criteria for gray hair hiding effect ◎: Gray hair is not noticeable ○: Gray hair is slightly noticeable △: Gray hair is noticeable ×: Gray hair is not dyed

The first agent contains gallic acid, tannic acid or a derivative thereof, the second agent contains an iron salt, the third agent contains salicylic acid or a derivative thereof, and after the first agent and the second agent. It was confirmed that the hair dye of the present invention to which the third agent is applied has a high hair dyeing effect and a gray hair hiding effect, and gives the hair after dyeing a natural color tone with suppressed bluish tint. In addition, the hair dye containing the fourth agent containing an iron salt has a higher hair dyeing effect, gray hair hiding effect, and hair color tone than the hair dye containing only the first agent, the second agent, and the third agent. It was excellent. On the other hand, when the agent containing salicylic acid or a derivative thereof was not applied after the agent containing gallic acid and the agent containing iron salt (Comparative Examples 1 and 2), the hair after dyeing had no reddish brown taste. It became an unnatural color tone with a strong bluish appearance. This tendency was the same in the hair dye (Comparative Example 3) in which the agent containing sodium salicylate was applied before the agent containing gallic acid. In addition, when an agent containing gallic acid, tannic acid or a derivative thereof was not applied (Comparative Examples 4 and 5), the gray hair hiding effect was low, and a sufficient effect was not obtained in terms of color tone. Further, a hair dye containing gallic acid and sodium salicylate in one agent (first agent), and not applying an agent containing salicylic acid or a derivative thereof after the first agent and a second agent containing an iron salt (comparison). Even in Example 6), a sufficient effect was not obtained in terms of color tone.

Claims (4)

A hair dye composed of at least the first agent, the second agent and the third agent.
The first agent comprises at least one selected from the group consisting of gallic acid, tannic acid and derivatives thereof.
The second agent contains an iron salt and contains
The third agent contains at least one selected from salicylic acid and its derivatives.
A hair dye in which the third agent is applied to the hair after the first and second agents. Claim 1 in which the content of at least one selected from the group consisting of gallic acid, tannic acid and derivatives thereof in the first agent is 0.1 to 10% by mass with respect to the total amount of the first agent. The hair dye described in. The hair dye according to claim 1 or 2, further comprising a fourth agent containing an iron salt. After or simultaneously applied to the hair the second agent and the first agent in this order, seen including applying a third agent, if a fourth agent, and a third agent and fourth agent in this order or including a simultaneously applied to the hair, hair method using a hair dye according to any one of claims 1 to 3.