WO2017141509A1

WO2017141509A1 - Photosensitive hair dye

Info

Publication number: WO2017141509A1
Application number: PCT/JP2016/083914
Authority: WO
Inventors: 哲雄慶野; 謙二井坂
Original assignee: 株式会社アウラ
Priority date: 2016-02-17
Filing date: 2016-11-16
Publication date: 2017-08-24
Also published as: CN108697605B; KR20180044357A; TWI658838B; JP6164543B1; JP2017145212A; CN108697605A; TW201729792A

Abstract

The present invention addresses the problem of providing a photosensitive hair dye which has excellent stability and can be stored for a long period of time. Provided, as a means for solving the problem, is a photosensitive hair dye which includes an aqueous solution having a silver salt and N-acetylmethionine dissolved therein, wherein the molar ratio of N-acetylmethionine to silver atoms (N-acetylmethionine/silver) dissolved in the aqueous solution is less than 4.5 mol.

Description

Photosensitive hair dye

The present invention relates to a photosensitive hair dye.

The photosensitive hair dye develops color when silver ions are reduced by light and the precipitated fine particles of metallic silver are adsorbed on the hair surface. Photosensitive hair dyes can be made into various dosage forms such as creams, gels and lotions, can be easily dyed just by applying them on the hair and exposed to sunlight, etc. It is accepted by the market because it does not contain diamine derivatives that cause damage.

Photosensitive hair dyes are colored by metallic silver fine particles generated by photoreduction of silver ions. Therefore, the photosensitive hair dye needs an aqueous silver salt solution in which the silver salt is dissolved in water to form silver ions. Silver nitrate is known as a silver salt that dissolves well in water. Since silver nitrate is a raw material for pharmaceuticals, it cannot be used for cosmetics in Japan. As silver salts that can be used as cosmetic raw materials, silver sulfate, silver lactate, silver citrate, and silver oxide are known.
Patent Document 1 proposes a hair dye containing (a) one or more silver salts selected from the group consisting of silver sulfate, silver lactate, and silver citrate, and (b) a chelating agent. Yes. Further, the inventors of the present invention have photosensitive hair dyes (Patent Document 2) excellent in colorability combining silver sulfate and citric acid, and photosensitive hair dyes mixed with silver sulfate and alkanolamines (Patent Document 3). ), A photosensitive hair dye containing silver oxide and an amino acid (Patent Document 4).

The photosensitive hair dye needs to expose the hair to which the photosensitive hair dye has been applied to light to convert silver ions into silver particles by a photoreduction reaction. In order to shorten the light exposure time, it is sufficient to increase the reactivity of silver ions. However, a high reactivity means that the stability is low. Therefore, if the reactivity of silver ions is increased, the reduction reaction may proceed even in a light-shielding tube where no light is applied, and the photosensitive hair dye may become black and the hair dyeability may be lowered. It is also possible to increase the silver ion concentration in order to shorten the light exposure time, but silver sulfate, silver lactate, and silver citrate are sparingly soluble and silver oxide is insoluble, and dissolved in water at a high concentration. I can't. Further, when the silver salt is dissolved up to the vicinity of the upper limit of solubility, the stability is lowered, silver is precipitated, the photosensitive hair dye is blackened, and the hair dyeability may be lowered.

In addition, the conventional photosensitive hair dye can darken the color by repeating the hair dyeing, but it is dyed in a reddish brown color. Since the reddish color tone is avoided, it is adjusted to a darker color tone with reduced redness by incorporating sulfur powder (colloidal sulfur) into the photosensitive hair dye. However, there is a problem that the smell of sulfur at the time of use is strong and the sulfur smell on the hair cannot be removed even after repeated washing.

JP 2011-116708 A Japanese Patent No. 3881688 Japanese Patent No. 4542621 Japanese Patent No. 5486106

An object of the present invention is to provide a photosensitive hair dye having excellent stability that can be stored for a long period of time.

1. Containing an aqueous solution in which silver salt and N-acetylmethionine are dissolved,
A photosensitive hair dye, wherein a molar ratio of N-acetylmethionine dissolved in the aqueous solution to silver atoms (N-acetylmethionine / silver) is less than 4.5 mol.
2. The silver salt is any one of silver sulfate, silver lactate, silver citrate, silver oxide, or two or more thereof. The photosensitive hair dye described in 1.
3. 1. The silver salt concentration in the aqueous solution is 1.6 wt% or more. Or 2. The photosensitive hair dye described in 1.
4). 1. The dosage form is one of lotion, tonic, gel, cream, emulsion, mousse, hair treatment, rinse, shampoo. ~ 3. The photosensitive hair dye as described in any of 1.

The photosensitive hair dye of the present invention forms a complex in which silver ions are stable, and can be stored for a long time in a light shielding tube or the like, and the hair dyeability does not deteriorate even after storage. In particular, the photosensitive hair dye of the present invention using silver sulfate as a silver salt is excellent in storage stability even at low and high temperatures.
Compared with conventional photosensitive hair dyes, the photosensitive hair dye of the present invention can control the concentration of silver salt in a wide range. Depending on the concentration of silver salt, the time applied to the hair and the light exposure time can be controlled. Can be adjusted. A photosensitive hair dye having a high silver salt concentration can shorten the time to be applied to the hair and the light exposure time, reduce the burden on the user, and can be used conveniently. By repeatedly using a photosensitive hair dye having a low silver salt concentration, the color tone of the hair can be gradually increased, and the change in impression due to the hair dye can be suppressed.

The photosensitive hair dye of the present invention can be used for hair dyeing while being applied to the hair or after being applied to the hair and washed, and then exposed to sunlight or light from lighting equipment while living daily life. Therefore, the photosensitive hair dye of the present invention can be used daily as a hair cream, rinse, shampoo or the like without taking any special action. By using the photosensitive hair dye of the present invention every day or every few days, the newly grown part can be gradually dyed, so that the vicinity of the base of the hair does not become white and natural. Can maintain the black hair.
The photosensitive hair dye of the present invention can be dyed to brown without redness without blending sulfur. Photosensitive hair dyes that do not contain sulfur do not have a sulfur odor and are easily scented with a fragrance.

In Experiment 1, the photograph which shows the result of having dyed human white hair using the photosensitive hair dye from which the density | concentration of silver sulfate differs. In Experiment 1, the photograph which shows the result of having dyed human white hair using the photosensitive hair dye from which the density | concentration of silver sulfate differs. In Experiment 2, the photograph which shows the result of having dyed white human hair using the photosensitive hair dye from which the molar ratio of N-acetylmethionine and the silver atom in silver sulfate differs.

The photosensitive hair dye of the present invention contains an aqueous solution in which a silver salt and N-acetylmethionine are dissolved.
The silver salt itself is hardly soluble or insoluble and has low solubility in water. By dissolving the silver salt together with N-acetylmethionine, the silver atom and N-acetylmethionine form a water-soluble complex, and the silver concentration in the aqueous solution can be increased.

As the silver salt, any of silver sulfate, silver lactate, silver citrate, silver oxide, or two or more kinds can be used. Silver sulfate is preferred because it is particularly excellent in storage stability. The lower limit of the silver salt concentration in the aqueous solution is 0.01 wt% or more, preferably 0.1 wt% or more, more preferably 1.0 wt% or more, further preferably 1.6 wt% or more, and 2.0 wt% or more. Most preferred. The higher the silver salt concentration, the more the hair can be dyed even if the application time and light exposure time are short. The upper limit of the silver salt concentration in the aqueous solution varies depending on the type of silver salt, but can be dissolved up to a saturation concentration at which a complex is formed and dissolved.

N-acetylmethionine has optical isomers of L-form and D-form. As N-acetylmethionine, any of N-acetyl-L-methionine, N-acetyl-D-methionine and a mixture of N-acetyl-DL-methionine can be used. The concentration of N-acetylmethionine in the aqueous solution is 0.01 wt% or more and 50 wt% or less. By increasing the amount of N-acetylmethionine, the dissolution time of the silver salt can be shortened. Even when N-acetylmethionine is added in an amount of more than 50 wt%, the dissolution time of the silver salt hardly changes, and the solubility of N-acetylmethionine in water is exceeded. End up.

The molar ratio of N-acetylmethionine to silver atoms (N-acetylmethionine / silver) in the aqueous solution is preferably in the range of 0.05 or more and less than 4.5 mol. When N-acetylmethionine is less than 0.05 mol per mol of silver atom, no complex is formed and the silver salt is hardly dissolved. By increasing the amount of N-acetylmethionine, the dissolution time of the silver salt can be shortened, but when N-acetylmethionine is 4.5 mol or more per 1 mol of silver atoms, the hair dyeing property is lowered. To do. This is a phenomenon common to silver sulfate, silver lactate, silver citrate, and silver oxide.

A complex composed of silver and N-acetylmethionine can be prepared by simply adding a silver salt and N-acetylmethionine to water and stirring them to dissolve. Stirring can be carried out at room temperature, but if the silver salt is difficult to dissolve, it is heated to about 40-80 ° C. At this time, even if insoluble matter remains, it can be used as a photosensitive hair dye as long as the liquid component is present. From the viewpoint of hair dyeing properties, the silver salt and N-acetylmethionine are completely used. It is preferable to dissolve.
The complex composed of silver and N-acetylmethionine is stable in the aqueous solution, and even when the aqueous solution in which the complex is dissolved is irradiated with light, the complex does not collapse and silver particles do not precipitate. Moreover, even if this aqueous solution is applied onto plastic and irradiated with light, the color does not change immediately. However, when this aqueous solution is applied to the hair and irradiated with light, silver particles immediately deposit and develop color. That is, the photosensitive hair dye of the present invention containing an aqueous solution in which silver salt and N-acetylmethionine are dissolved is stably stored in a container such as plastic, and quickly develops color when applied to hair and exposed to light. It has extremely excellent properties as a photosensitive hair dye.

The reason why the photosensitive hair dye of the present invention containing a complex composed of silver and N-acetylmethionine is excellent in preservability and hair dyeability is presumed as follows.
Silver ion complexes are stable to light. For example, silver particles do not precipitate when an aqueous solution in which a silver ammine complex or a complex of silver and sodium thiosulfate is dissolved, and the aqueous solution is black. Do not turn. A complex composed of silver and N-acetylmethionine does not darken even when the aqueous solution is irradiated with light. However, since N-acetylmethionine is coordinated by forming a weak interaction with silver ions in the complex, when a strong negative charge approaches the hair surface, silver ions (Ag ⁺ ) in the complex Is attracted to the hair surface, the complex disintegrates, and silver ions are adsorbed on the hair surface. Since silver ions adsorbed on the hair do not form a complex and have low stability, they are easily reduced by light and develop color.

Therefore, the photosensitive hair dye of the present invention can be stably stored in a container having a weak charge or no charge such as plastic, and can be dyed when applied to hair and exposed to light. Excellent in hairiness and hair coloring.
It should be noted that the concentration of N-acetylmethionine is largely involved in the stabilization of a complex composed of silver and N-acetylmethionine. When the molar ratio of N-acetylmethionine to silver atom (N-acetylmethionine / silver) is 4.5 mol or more, the complex is stabilized and does not easily disintegrate even when exposed to light on the hair, and is hair-dyeing. Decreases.

The photosensitive hair dye of the present invention is applied not only to the method of exposing sunlight or illumination light while being applied to the hair, but also applied to the hair and washed, and the photosensitive hair dye is washed away and then exposed to sunlight or the like. Hair can also be dyed by the method. This is because the adsorbing power of silver ions on the hair is strong and a sufficient amount of silver ions adheres to the hair surface after normal hair washing.
The method of applying a photosensitive hair dye to the hair and washing it after exposure to sunlight, etc. is short because the time spent in the state applied to the hair is short, so it can be used easily and the burden on the user is small. Further, it is possible to reduce the reduction of the photosensitive hair coloring material attached to the clothing or the like and coloring the clothing or the like.

The photosensitive hair dye of the present invention can control the silver salt concentration in a wide concentration range, and can dye hair with a deep color tone as the silver salt concentration increases. The photosensitive hair dye of the present invention having a silver salt concentration of 1.6 wt% or more can be dyed to brown without redness substantially without containing sulfur. Here, substantially not containing sulfur means that the sulfur content is 0.1 wt% or less.

The photosensitive hair dye of the present invention can shorten the time applied to the hair and the light exposure time as the silver salt concentration in the aqueous solution increases. Since the photosensitive hair dye of the present invention having a high silver salt concentration has a short application time and light exposure time, the burden on the user is small. The photosensitive hair dye of the present invention having a low silver salt concentration does not dye a deep color tone when used once, but can be applied to a plurality of times to gradually dye the hair to a dark color tone. Moreover, the change of the impression by dyeing hair can be suppressed because hair becomes a deep color tone gradually.

The photosensitive hair dye of the present invention is a surfactant, oil agent, thickener, moisturizing agent, and the like, which are generally used as cosmetic and hair dye ingredients, as long as the complex of silver and N-acetylmethionine is not destroyed. Agents, preservatives, antioxidants, pH adjusters, fragrances, colorants, other cosmetic ingredients, medicinal ingredients, and the like can be appropriately blended. These are preferably mixed after the silver salt and N-acetylmethionine are dissolved in water to form a complex.
The photosensitive hair dye of the present invention contains an aqueous solution in which a silver salt and N-acetylmethionine are dissolved, and is an aqueous cosmetic, or a W / O emulsion, an O / W emulsion, a W / O / It can be set as the emulsification type cosmetics which are a W type emulsion and an O / W / O type emulsion.

The photosensitive hair dye of the present invention can be made into dosage forms such as lotions, tonics, gels, creams, emulsions, mousses, hair treatments, rinses and shampoos. By using the photosensitive hair dye of the present invention as the above-mentioned dosage form about once a week from every day, newly grown parts can be gradually dyed. By using it regularly, it does not become white only near the base of the hair, so it is difficult to understand that the hair is dyed, and natural black hair can be maintained.

The photosensitive hair dye of the present invention can be applied to hair on a daily basis and can also be applied to rinses or shampoos that can be easily washed away. The photosensitive hair dye of the present invention is excellent in stability, and silver particles are deposited even when left in a bathroom where the temperature fluctuates from about 20 ° C. to 40 ° C. in a bottle or the like. The hair dyeability does not decrease.

Next, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

“Experiment 1”
A silver salt and N-acetylmethionine were mixed in the composition shown in Table 1 below to prepare an aqueous solution. The value of the blending ratio shown in Table 1 is mass%. Further, since it is difficult to analyze the composition of the insoluble matter, the molar ratio (N-acetylmethionine / silver) was calculated from the blending ratio. The solubility, color tone, and dyeing time of the obtained aqueous solution were evaluated. Note that N-acetyl-DL-methionine was used as N-acetylmethionine.

(Solubility)
Very good: soluble in room temperature water.
Good: Dissolves in water at 80 ° C.
Insoluble: Not completely dissolved in water at 80 ° C. and insoluble matter remains.
Solidification: Insoluble matter solidifies and no liquid is present.
(Color tone)
Each aqueous solution was uniformly applied to human white hair, exposed to sunlight for 15 minutes under fine weather, and visually checked for color tone after washing with running water. For the solidified product, the same operation was performed except that the solidified product was adhered to gray human hair. 1 and 2 show the results of dyeing gray human hair in an example using silver sulfate.
(Dyeing time)
Each aqueous solution was uniformly applied to gray human hair, exposed to sunlight under fine weather, and the time until hair was dyed in a uniform color with no unevenness was measured.

Each silver salt showed different solubility. Silver sulfate and silver lactate were excellent in solubility and could be dissolved by 20 wt%. It was possible to dissolve 8 wt% of silver citrate and 6 wt% of silver oxide. At a concentration higher than this, the silver salt was saturated and insoluble matter remained.
In any silver salt, as the silver salt concentration increased from 0.1 wt% to 2 wt%, the hair was dyed in a deeper color. In addition, as long as no insoluble matter remained, hair was dyed in almost the same color at a silver salt concentration of 2 wt% or more, and in particular, no difference in color tone was observed at a silver salt concentration of 4 wt% or more. Even if the insoluble matter remained, the silver salt in the solution was adsorbed on the hair, so that the hair could be dyed, but the dyeability deteriorated. In addition, the solidified product could not be dyed even when it was attached to the hair.
The dyeing time was also shortened as it increased from 0.1 wt% to 2 wt%. When the silver salt concentration was 2 wt% or more, hair could be uniformly dyed in 1/5 light irradiation time as compared with 1.0 wt% silver salt concentration. The insoluble matter remained for longer dyeing time.
The effect on the color tone and dyeing time by the type of silver salt was hardly recognized.

"Experiment 2"
In the same manner as in Experiment 1, an aqueous solution was prepared by mixing with the composition shown in Table 2 below, and the solubility, color tone, and dyeing time of the obtained aqueous solution were evaluated. The value of the blending ratio shown in Table 2 is mass%. FIG. 3 shows the result of dyeing gray human hair in an example using silver sulfate. Note that N-acetyl-DL-methionine was used as N-acetylmethionine.

All compositions were excellent in solubility, and an aqueous solution free from insolubles was obtained.
In any of the silver salts, hairs having a molar ratio of about 1 or about 4 could be dyed. Particularly, when the molar ratio was about 1, hair could be dyed in a deep color tone. In contrast, at a molar ratio of 4.5, hair could not be dyed despite the aqueous solution in which the silver salt and N-acetylmethionine were completely dissolved.

“Experiment 3”
As Examples 1 to 4 and Comparative Examples 1 to 3, hair creams having the compositions shown in Table 3 below were prepared. The value of the blending ratio shown in Table 3 is mass%. The preparation procedure is as follows. Note that N-acetyl-DL-methionine was used as N-acetylmethionine.
A silver salt and N-acetylmethionine or L-methionine are added to purified water and dissolved by stirring. Next, all the remaining components are added, heated to 70 ° C., stirred until uniform, and then cooled to room temperature.

Evaluation of photosensitive hair dye The prepared hair cream was evaluated according to the following criteria. The results are shown in Table 3.
(1) Hair dyeing Using white hair human hair, apply 0.5 g of the prepared hair cream uniformly once and then expose to sunlight under fine weather for 15 minutes. Thereafter, the hair dyeability was evaluated by the color tone after washing for 1 minute.
◎: Very dark brown ○: Dark brown △: Light brown

(2) Appearance and shape About 75 g of the prepared hair cream was packed in a light-shielding ointment container (manufactured by Umano Chemical Container Co., Ltd., 125 ml) and allowed to stand at room temperature. Once a day, the lid was opened, and the off-flavor, discoloration, and viscosity change were visually observed for 60 days.
A: Almost no change for 60 days. Δ: No significant change in off-flavor, viscosity, cream color, but some sweet and sour smell peculiar to amino acids is felt. X: Offensive odor, discoloration, change in viscosity are observed (3) Stability The prepared hair cream was filled with about 75 g in a light-shielding ointment container (manufactured by Umano Chemical Container Co., Ltd., 125 ml) and left in a thermostatic bath set at 5 ° C. and 45 ° C. Once a day, the lid was opened, and the off-flavor, discoloration, and viscosity change were visually observed for 60 days.
◎: Almost no change for 60 days ○: Odor and discoloration are not observed, but a slight viscosity change is observed compared with storage at room temperature , Viscosity change is observed ×: Odor, discoloration, viscosity change is observed

Examples 1 to 4 which are photosensitive hair dyes of the present invention were excellent in hair dyeing properties. Moreover, even if it was left to stand for 60 days at room temperature, the change was hardly observed. In particular, in Example 1 using silver sulfate, no change was observed even when left at 5 ° C. and 45 ° C. for 60 days.
Comparative Examples 1 to 3 using L-methionine had hair dyeing properties immediately after preparation, but deteriorated at any of room temperature, 5 ° C. and 45 ° C., and were inferior in storage stability. It was. In Comparative Example 2 in which silver lactate was used, the odor of methionine and the sweet and sour odor of lactic acid were generated, and the cream turned slightly gray. In Comparative Example 3 using silver citrate, the odor of methionine was generated and the cream was also turned black. Comparative Example 1 using silver sulfate was superior to Comparative Examples 2 and 3 in preservability, but had a odor of methionine.

Claims

Containing an aqueous solution in which silver salt and N-acetylmethionine are dissolved,
A photosensitive hair dye, wherein a molar ratio of N-acetylmethionine dissolved in the aqueous solution to silver atoms (N-acetylmethionine / silver) is less than 4.5 mol.
The photosensitive hair dye according to claim 1, wherein the silver salt is any one of silver sulfate, silver lactate, silver citrate, and silver oxide, or two or more thereof.
The photosensitive hair dye according to claim 1 or 2, wherein a silver salt concentration in the aqueous solution is 1.6 wt% or more.
4. The photosensitive hair dye according to claim 1, wherein the dosage form is any one of lotion, tonic, gel, cream, milky lotion, mousse, hair treatment, rinse and shampoo.