JP5752656B2 - How to use photosensitive hair dye containing silver ions - Google Patents

Description

  The present invention relates to a method for using a silver ion-containing photosensitive hair dye, in which a silver ion-containing photosensitive hair dye is applied to the hair, washed immediately, and then dyed with light.

  Conventionally, as hair dyes, there are oxidative hair dyes called permanent hair dyes that develop color by oxidizing a phenylenediamine derivative with hydrogen peroxide, and hair manicure type semi-permanent hair dyes that combine various dyes with penetration enhancers such as benzyl alcohol. Recently, silver ion-containing photosensitive hair dyes that dye hair with light are also known and are beginning to spread. This photosensitive hair dye utilizes a reaction in which silver ions dissolved in water are reduced by light and change from ions to water-insoluble metallic silver fine particles. At that time, metallic silver breaks out using the hair surface as a carrier. So silver particles firmly adhere to the hair surface and appear dark brown. Once dyed, it is one of the features that the hair dyeing state lasts for a long time even after repeated washing (see Patent Document 1).

Commercially available photosensitive hair dyes use silver sulfate, silver oxalate, and silver lactate to give silver ions. Hydroxy organic acids such as citric acid, malic acid, glycolic acid, and tartaric acid are used to stabilize the system. In general, the pH is kept at 4.0 or lower. Various forms of hair dyes can be made, such as cream, emulsion, gel, lotion and foam, and it has the advantage of not affecting the human body and damaging the hair due to alkali and oxidation. So it continues to spread in the market.
However, conventional photosensitive hair dyes are used in such a way that they are washed on the hair after being applied to the hair and sufficiently colored by light. Therefore, the photosensitive hair dye can only be used in a non-washing-out type of hair dye used on the hair, such as hair cream, hair liquid, hair mousse and hair gel.

Japanese Patent No. 3881688

As described above, since all of the conventional photosensitive hair dyes are used while applied to the hair, depending on the dosage form, a state unfavorable to the user may occur. For example, in the case of a cream-type photosensitive hair dye, a woman with long hair feels very heavy when a required amount of cream is applied to the tip of the hair, and when dried, the hair becomes hard and solidified, and the desired smooth state is not obtained. Further, if a gel-like photosensitive hair dye is used, it is good for the gel to harden and maintain a certain hairstyle, but the hairstyle cannot be freely changed at any time. Also, there is a problem that the odor of the base material will remain forever, and if the hair touches clothes and other things until the hair is dry after applying the photosensitive hair dye, the hair dye will adhere and develop and stain after several hours. was there.
Therefore, the present invention uses a silver ion-containing photosensitive hair dye that solves all the conventional problems even if the dosage form of the photosensitive hair dye is a type of hair rinse, shampoo, washable treatment, etc. A method is provided.

The method of using the silver ion-containing photosensitive hair dye of the present invention has been developed by the following process.
When a human hair of a photosensitive hair dye was applied to the human hair of the sample and an experiment was attempted to measure the time until color development by applying a certain amount of light, the sample that had not yet developed color was washed with a detergent. Human hair was not dyed at all. The sample was stored in a dark place for a long time and it was confirmed that no color was developed. Various experiments were repeated to investigate the reason for the color development, and the following was found. Silver ions dissolved in water strongly adsorb to hard keratin (eukeratin) such as hair or nails, but not so much to skin that is soft keratin (pseudokeratin). The silver ions adsorbed on the human hair of the sample are not colored, but when light is applied to the silver ions adsorbed on the human hair, the silver ions are photoreduced and converted into metallic silver, and light is generated between the generated silver particles. Because it is absorbed, it looks dark. The amount of silver ions adsorbed on the human hair is more than expected, and the amount is sufficient to color with only the adsorbed silver. After applying to the human hair of the sample and leaving it to wash for 3 minutes or more, It was found that silver ions were photoreduced and converted to metallic silver. Based on this fact, it has been devised a method of use in which hair is dyed even if a photosensitive hair dye is applied to the hair and immediately washed away.

Therefore, the method for using the first silver ion-containing photosensitive hair dye is a method for using a silver ion-containing photosensitive hair dye (excluding those containing alkanolamines) used for hair . After applying the silver ion-containing photosensitive hair dye to the hair, the hair is left for 3 to 10 minutes , and then the hair is washed, dried and dyed with light.
The second method for using a photosensitive hair dye containing silver ions is characterized in that the photosensitive hair dye is any one of a hair rinse, a shampoo, a washable treatment, and a hair manicure.

  Conventional photosensitive hair dyes are dyed without being washed for several hours or more by being exposed to light while being applied to the hair. In the method of the present invention, the photosensitive hair dye applied to the hair is passed for 3 minutes or more. Since it is a method of washing and dyeing hair, it can be applied to dosage forms such as hair rinses, shampoos, and washable treatments where photosensitive hair dyes are washed away. Finished with a washed finish. In particular, even if shampooed, the photosensitivity effect is sufficient, so that it appears that no photosensitive hair dye is attached after washing the hair. After that, you don't have to put anything on your hair, and you can use your favorite hair styling, so it solves all the problems of fragrance, hair stickiness, and hair hardening. It is an excellent usage method. In addition, after washing, hair does not get dirty even if it touches clothes or objects.

FIG. 1 shows that 1 g of white hair human hair is used as a test piece, and this is added to a 0.8% by weight silver sulfate aqueous solution for 10 seconds, 20 seconds, 30 seconds, 40 seconds, 50 seconds, 1 minute, 2 minutes, 3 minutes, It is a photograph in which each sample was exposed to direct sunlight for 1 hour after being dipped for 4 minutes, 5 minutes and 10 minutes, then washed with hot water at 40 ° C. and then dried. It is the photograph which selected and rearranged the sample immersed for 10 seconds, 20 seconds, 40 seconds, 1 minute, 3 minutes, 5 minutes, and 10 minutes from the sample of FIG. It is the photograph which exposed the sample wash | cleaned with 3 types of hair washing methods to direct sunlight for 1 hour. It is the photograph of the sample for changing the density | concentration of silver sulfate aqueous solution and comparing the degree of adsorption | suction of silver ion by a sensory test.

Embodiments of the present invention will be described below.
(Photosensitive hair dye)
A method for producing a photosensitive hair dye used in the method of using the silver ion-containing photosensitive hair dye (hereinafter referred to as “photosensitive hair dye”) of the present invention will be described.
Photosensitive hair dye is a substrate made acidic with citric acid by bringing a predetermined substrate material having moisture into an acidic state with citric acid and mixing (adding) silver sulfate which is a water-soluble silver salt to this substrate material. In this case, silver sulfate is dissolved in the material. The substrate material may be an emulsion in which an oil component is emulsified in a water-soluble component. The substrate material may be a gel in which a polymer material is dispersed in a predetermined dispersion medium, or an aqueous solution containing alcohol.

  When photosensitive hair dye is applied to the hair and irradiated with light such as ultraviolet rays or visible light, silver ions dissolved in the photosensitive hair dye are reduced to metallic silver, and reduced metallic silver fine particles Deposits and adheres to the hair surface and develops color. In the hair dyed in this way, no change is confirmed in the hair dyeing state in normal hair washing. The metallic silver deposited by the light irradiation and adhering to the surface of the hair is considered to be strong enough not to be detached from the surface of the hair when washing the hair.

Silver sulfate (Ag ₂ SO ₄ ) is a white solid with a molecular weight of 311.79, has low solubility in water, is 0.8% by weight at 20 ° C., and slightly soluble due to the acidified state and the presence of alcohol. improves. For example, the solubility is improved to about 0.9% by weight in an acidic state. When the concentration of the dissolved silver salt is as low as about 0.4 to 0.6%, the hair becomes colored with redness. For example, when applied to gray hair, when the silver salt concentration is about 0.4 to 0.6%, the hair is dyed from pink to reddish brown, and not so dark brown. However, when the subject of hair dyeing is a woman, light brown may be preferred, and the color tone may be adjusted to some extent by the silver salt concentration.

In order to obtain an acidic state, an acid may be added. For example, strong acids such as sulfuric acid and nitric acid are not suitable for photosensitive hair dyes used in the human body. Also, hydrochloric acid cannot be used because it produces silver chloride.
In contrast to the strong acid described above, the weak acid has no influence on the human body and does not form a salt, so it is suitable as a material to be added to make it acidic. However, for example, acetic acid has a strong odor and is not suitable as a material to be added to the photosensitive hair dye.
In contrast to the above findings, citric acid, malic acid, lactic acid, glycolic acid, tartaric acid and the like do not cause the above-described problems as materials for making them acidic.

  Among these, when citric acid was used for the acidic region, a state in which silver sulfate was dissolved in a stable state was obtained without causing coloring. In addition, when citric acid is used, the solubility of silver sulfate can be increased to 0.9%. Here, it goes without saying that sodium citrate may be used as a buffering agent. In addition, the silver salt aqueous solution is very unstable, but as described above, by adding citric acid to make it an acidic region, a stable state can be obtained and the dark reaction of blackening by standing can be suppressed. become.

  When citric acid is not used, blackening gradually proceeds even when stored in a dark place, and the ability and fastness to adhere to the hair decrease. On the other hand, in the photosensitive hair dye in this Embodiment, since it was set as pH 4.0 or less by citric acid, the oxidation of the silver salt which melt | dissolved is suppressed and the production | generation of black silver oxide can be suppressed. . For example, even if the photosensitive hair dye is stored at a high temperature of 40 ° C. or higher, coloring (dark reaction) does not occur. However, it is necessary to add silver sulfate in a state where citric acid has been added in advance. Even if citric acid is added after silver sulfate is dissolved, no effect is obtained.

  On the other hand, when it is not made acidic by citric acid and is in the alkaline region, silver ions are gradually oxidized when left at room temperature (for example, 20 to 25 ° C.) even if light is blocked. As a result, silver oxide is formed and gradually becomes black. In this case, when sulfur is added as a reducing agent, the dark reaction can be suppressed even in the alkaline region. However, when sulfur is added in the alkaline region, the reactivity (sensitivity) to light is lowered.

  In addition, even if silver sulfate is about 0.5-0.9% of dissolution amount, if it is aqueous solution, the hair dyeing state mentioned above will be obtained. However, in a state where silver ions are hardly generated, for example, in a state where silver sulfate is dispersed in an oil component, the reaction by light is very slow, and the above-described hair dyeing effect cannot be obtained.

Next, the manufacturing method of the photosensitive hair dye mentioned above is demonstrated.
First, the product A is prepared using the following components.
In a vacuum emulsification pot, add 81.4 kg of purified water and heat to 90 ° C., add citric acid to make it acidic, add 0.6 kg of silver sulfate, and stir to add silver sulfate. Dissolve to make Product A. Here, an equivalent amount of sodium citrate may be added as a buffering agent.

Next, the following components are mixed to prepare a product B.
In an oil tank kettle, 12 kg of silicone oil, 4 kg of cetanol, 1.5 kg of sorbitan stearate, 0.3 kg of stearyldimethylammonium chloride, and 0.1 kg of methylparaben are stored and heated to 80 ° C. to dissolve each product B And

  Next, the product A stored in the vacuum emulsification kettle is kept at 80 ° C., and this is vigorously stirred. The product B is gradually added to the stirred state. Next, after all the product B is added to the product A, the vacuum emulsification pot is sealed to create a reduced pressure environment. After the reduced pressure environment, the contents of the vacuum emulsification pot are stirred for 8 minutes with a 3000 rpm homomixer, and then the temperature of the contents is cooled to 35 ° C. while the stirring speed is reduced.

  Finally, the emulsion obtained by mixing the product A and the product B as described above is filtered through a 20-mesh filter to obtain 98 kg of white cream (photosensitive hair dye). These preparations are performed in a state where light is almost blocked so that there is no precipitation of metallic silver due to reduction.

  The resulting white / creamy photosensitive hair dye has a pH of about 4. When this photosensitive hair dye is allowed to stand at room temperature while blocking light, it is stable without being blackened for more than 10 months. Moreover, even if this photosensitive hair dye is left in a state of 40 ° C. while blocking light, it is stable without being blackened for 6 months or more.

Next, the hair dyeing action of the photosensitive hair dye described above will be described in more detail.
The photosensitive hair dye is obtained, for example, by mixing a water-soluble silver salt of silver sulfate with a substrate material having moisture such as a hair cream. When such a photosensitive hair dye is applied to the hair, and the hair is exposed to sunlight (ultraviolet rays) in this state, the silver ions in the photosensitive hair dye are reduced by light and metal silver is precipitated, and the precipitated metal silver Adheres to the hair. Thus, the metal silver is deposited and adhered to the hair, so that the hair is dyed. Part of the metallic silver deposited on the hair reacts with sulfur in the hair and changes to black silver sulfide, or is gradually oxidized by oxygen in the air and changes to black silver oxide. Is also expected.

  The photosensitive hair dye was prepared by mixing silver, which is a dye for hair, as a silver salt and applied to the hair in a state dissolved in water, that is, in the form of water-soluble silver ions. As a result, according to the photosensitive hair dye, the silver is easily penetrated into the hair, and since the metallic silver fine particles are deposited in the state of contact with the hair surface or inside the hair, the color is fixed. It is easy. Moreover, since it does not contain diamine or lead, it does not cause allergic reactions or harm health. Furthermore, according to the photosensitive hair dye, it can be expected that the metallic silver coats the hair surface, so that the hair is protected, and of course, the hair is not damaged.

According to the photosensitive hair dye, the hair at the stage where the photosensitive hair dye is applied is not in a dyed state, but silver ions in the photosensitive hair dye are deposited as reduced metallic silver. At the stage, the hair is dyed.
By the way, in the manufacturing method mentioned above, although the silver sulfate was dissolved in the substrate material made into the emulsion to make a photosensitive hair dye, it is not limited to this. For example, silver sulfate may be dissolved in a matrix material in which a polymer material is dispersed in a predetermined dispersion medium to form a photosensitive hair dye.

  For example, 0.6 kg of silver sulfate is dissolved in 82.1 kg of purified water, 0.1 kg of citric acid and 0.1 kg of sodium citrate, and 0.5 kg of carboxyvinyl polymer and 0.5 kg of polyvinyl pyrrolidone derivative quaternary ammonium salt are added thereto. , 0.8 kg of triisopropanolamine, 14.0 kg of ethanol, 0.8 kg of polyoxyethylene lauryl ether (23E · O) and 0.5 kg of ethyl paraben may be added to obtain a transparent gel, which may be used as a photosensitive hair dye. . Of course, the production of the photosensitive hair dye is performed in a state where light is substantially blocked so that the metallic silver is not precipitated by the reduction.

An aqueous solution in which a predetermined fragrance is dissolved may be used as the substrate material.
When a milky liquid is used as the substrate material, it is generally referred to as a hair cream, and when a gel is used as the substrate material, it is generally referred to as a hair gel. In addition, when an aqueous solution is used as the substrate material, it is referred to as a hair lotion, and when a highly viscous emulsion is used as the substrate material, it is referred to as a hair wax. Moreover, these photosensitive hair dyes can be provided as, for example, a so-called hair mousse (registered trademark) in the form of a cream filled in a spray can.
As described above, the photosensitive hair dye can be used in the form of cream, emulsion, or foam for hair.

(How to use photosensitive hair dye)
After the photosensitive hair dye is applied to the hair and applied by hand so that the photosensitive hair dye reaches the inside of the hair, the hair is left for 3 minutes or more, preferably for 5 minutes or more. Thereafter, the hair is washed, dried and dyed with light.
As a hair washing method, the hair may be washed using water, hot water, or shampoo. To dry the hair, either towel drying or a hair dryer may be used, or both may be used.

  As described above, since silver ions are generally easy to dissolve in water, the present inventor shampoos hair coated with a photosensitive hair dye before silver ions are reduced to metallic silver by light. I thought that water washed away the photosensitive hair dye and it was not dyed even when irradiated with light. However, depending on the results of the silver ion adsorption test described below, even if the hair is washed with water, shampoo, or hot water, the hair will be washed if the photosensitive dye is immersed in the hair for 3 minutes, preferably after 5 minutes. Can be dyed blackish brown.

(Silver ion adsorption test on hair)
The degree of adsorption of silver ions on the hair was tested. First, it was examined how fast silver ions adsorb to the hair.
FIG. 1 shows that 1 g of white hair human hair is used as a test piece, and this is added to a 0.8% by weight silver sulfate aqueous solution for 10 seconds, 20 seconds, 30 seconds, 40 seconds, 50 seconds, 1 minute, 2 minutes, 3 minutes, It is a photograph in which each sample was exposed to direct sunlight for 1 hour after being dipped for 4 minutes, 5 minutes and 10 minutes, then washed with hot water at 40 ° C. and then dried.
When the dark brown color of the hair is compared by visual sensory test, the photograph in FIG. 1 shows that the dark brown color of the sample gradually becomes darker up to the sample of 5 minutes as the immersion time increases, and the brownish brown color at 5 minutes and 10 minutes. It turns out that the colors are the same.

Therefore, in order to easily identify the difference between the dark brown color of the hair, select samples immersed in 10 seconds, 20 seconds, 40 seconds, 1 minute, 3 minutes, 5 minutes and 10 minutes from the sample in FIG. Fig. 2 shows the rearranged photos. When comparing the dark brown color of the sample soaked for 1 minute with the sample soaked for 3 minutes, it was found that the sample soaked for 3 minutes had a slightly darker brown color.
A comparison between the sample immersed for 3 minutes and the dark brown color of the sample immersed for 5 minutes revealed that the sample immersed for 5 minutes had a slightly darker brown color. Accordingly, it has been found that if the photosensitive hair dye is immersed in the hair for 3 minutes, preferably 5 minutes or more and then washed, the hair can be dyed dark brown. Moreover, since adsorption | suction to hair arises even if it soaks for only 10 seconds, it turned out that adsorption | suction speed | velocity is quite quick.

FIG. 3 is a photograph of a sample washed with three types of hair washing methods exposed to direct sunlight for 1 hour.
The sample of FIG. 3 was immersed in a 0.8 wt% silver sulfate aqueous solution for 3 minutes, then washed with three different hair washing methods, water, shampoo or hot water and then exposed for 1 hour. The left sample in FIG. 3 was washed with 25 ° C. water, the center sample was shampooed and washed with 40 ° C. hot water, and the right sample was washed with 40 ° C. hot water.
In the photograph of FIG. 3, the dark brown color of the hair was compared by visual sensory test, and it was found that the black-brown state of the three types of samples was the same regardless of the hair washing method. Since it does not decolorize even if it is washed with a shampoo having a detergency, it is presumed that the adsorptive power to silver hair is quite strong.

FIG. 4 is a photograph of a sample for comparing the degree of adsorption of silver ions by a sensory test while changing the concentration of the aqueous silver sulfate solution. When the immersion time is fixed at 5 minutes, the concentration of the silver sulfate aqueous solution is 0.004, 0.006, 0.008, 0.01, 0.1, 0.3, 0.6, 0.8% by weight. It can be seen that the amount of adsorption increases as the concentration increases. In particular, since it is clearly dyed at a concentration of 0.1% by weight or more of silver sulfate, the concentration of the aqueous silver sulfate solution at the time of actual use in which it is allowed to stand for 5 minutes or more is suitably from 0.1% to 0.8%.
In addition, although the photographs of FIGS. 1 to 4 are displayed with black and white shading of the hair, the actual hair color is blackish brown.

Since silver ions are generally easy to dissolve in water, washing the coated hair before the silver ions are reduced to metallic silver by light will wash away the photosensitive hair dye coated with water from the hair. The result of the adsorption test of silver ions on the hair was that if the photosensitive hair dye was immersed for 3 minutes, preferably 5 minutes and then washed, the silver ions in the photosensitive hair dye adhered to the hair. It has been shown. This is presumed that cationic silver ions are adsorbed on anionic hair by ionic bonds if a photosensitive hair dye is applied to the hair for 3 minutes or longer. Since the ion-bonded silver ions are firmly attached to the hair, even if the hair is washed, the silver ions are adsorbed without flowing out into the water, so that the hair can be dyed in an excellent black-brown color by light irradiation. It turns out that you can.
(Example)

Example 1
<Photosensitive hair rinse>
Add 80 kg of water to the mixing tank (A), dissolve 0.8 kg of silver sulfate and 0.5 kg of citric acid, and keep at 80 ° C while stirring. In a separate container (B) take 0.5 kg glyceryl monostearate, 0.5 kg polyethylene glycol monostearate, 0.3 kg polyoxyethylene cetostearyl ether, 1 kg cetanol, 3 kg cyclic silicon, 1 kg methylpolysiloxane, 70 Dissolve and mix at 0 ° C. The container (B) mixture is slowly poured into the container (A) while emulating the homomixer and emulsified. While the emulsion is slowly stirred, the temperature is lowered to 60 ° C., and 1 kg of 1.3 butylene glycol and 1.5 kg of (PEG-240 / decyltetradeceth-20 / HDI) copolymer dissolved in 9.9 kg of water are stirred. Add and cool to 30 ° C. A 99.5 kg photosensitive hair rinse was obtained through a 20 mesh filter.
0.8 g of this photosensitive hair rinse was uniformly applied to 1 g of gray hair test piece, left for 5 minutes, rinsed with hot water, towel-dried and then exposed to direct sunlight for 1 hour, and dyed dark brown.

(Example 2)
<Photosensitive hair treatment>
Phase A 1. Water 75.00kg
2. Silver sulfate 0.80kg
3. Citric acid 0.10kg
Phase B 1. Glyceryl stearate 0.8kg
2. Polyoxyethylene cetostearyl ether 0.8kg
3. Cetostearyl alcohol 0.5kg
4. Hydrogenated polyisobutene 8.0kg
5. Methylpolysiloxane 3.0kg
Phase C 1. Water 8.7kg
2. (Acryloyldimethyltaurate ammonium / VP) copolymer 1.3kg
3. Glycerin 1.0kg
Add Phase A to the mixing tank and dissolve the silver sulfate while stirring at 80 ° C. Take Phase B in a container and dissolve at 70 ° C.
Add phase B to phase A little by little and stir vigorously with a homomixer to emulsify. After cooling to 60 ° C, slowly add Phase C and cool to 30 ° C with stirring. 100.0 kg of creamy hair treatment was obtained.

  One male and one female with conspicuous gray hair were selected and used. In the evening, I washed my hair with shampoo in the bathroom, then towel-dried, applied the photosensitive hair treatment evenly on my hair, waited for 5 minutes, and then washed off the hair treatment with hot water. I left it overnight without doing anything on my hair. The next day, I spent the usual day as usual and examined the morning hair the day after. If you look closely, the gray hair part is colored dark brown, and the black hair part remains as it is.

Conventional photosensitive hair dyes have been used in such a way that they are washed on the hair after being applied to the hair and sufficiently colored. Therefore, as a photosensitive hair dye, only a dosage form that does not wash away, such as hair creams, hair liquids, hair mousses, hair gels, etc. that are used while applied to the hair can be obtained.
The method of using the photosensitive hair dye of the present invention makes it possible to immediately wash out and use it, so that the photosensitive hair dye can also be used in washing-type hair rinses, shampoos, washable treatments, etc. The range has expanded. Furthermore, the present invention can be applied to hair nail polish in which a dye and a permeation accelerator are added to a photosensitive hair dye and washed off.
Therefore, the method for using the photosensitive hair dye of the present invention includes not only a colorless photosensitive hair dye but also a colored photosensitive hair dye containing a dye.

Claims (2)

A method of using a photosensitive hair dye containing silver ions (excluding those containing alkanolamines and shampoo ) used for hair,
The silver ion-containing photosensitivity characterized in that after the photosensitive hair dye containing silver ions is applied to the hair, the hair is left for 3 to 10 minutes, and then the hair is washed, dried and dyed with light. How to use hair dye. The method for using a silver ion-containing photosensitive hair dye according to claim 1, wherein the silver ion-containing photosensitive hair dye is any one of a hair rinse , a washable treat, and a hair nail polish.