JP4542621B1 - Photosensitive hair dye and method for producing the same - Google Patents

Abstract

The photosensitive hair coloring material of the present invention is a photosensitive hair coloring material in which a silver salt is mixed with a substrate material having moisture so that gray hair is dyed black even if the light irradiation time is short and does not easily fall off by washing the hair. , 0.3 to 9% alkanolamines with respect to the total amount of photosensitive hair dye in the substrate material, and 0.3 to 2.0% of the silver salt with respect to the total amount, silver sulfate, silver acetate, It includes one selected from silver lactate, silver oxide and the like.
[Selection] Figure 4

Description

  The present invention relates to a photosensitive hair dye that can be easily dyed and a method for producing the same, and in particular, to a photosensitive hair dye that can be dyed even by irradiation with light for a short time and a method for producing the same.

  Photosensitive hair dyes containing silver sulfate and citric acid that have recently been put into practical use are gradually dyed in about two days when exposed to sunlight. Just as with normal hair care products, hair can be applied simply by applying it. Since the hair is dyed and there is no irritation or allergies, the number of customers who use it tends to increase gradually. This photosensitive hair dye was completed by the development of the present inventor, and a hair dye disclosed in Japanese Patent No. 3881688 is known as a prior art document.

In the hair dye of the above-mentioned patented invention, the hair dye contains a silver salt that is reduced by irradiation with ultraviolet rays or the like to precipitate metallic silver in a water-soluble state made acidic with citric acid. In addition, hair can be dyed just by applying hair dye to the hair, and since it is made into an acidic region using citric acid, oxidation by dark reaction is suppressed, and silver sulfate is stably dissolved Can be obtained.
The principle that the above-mentioned hair coloring dyes gray hair by sunlight is that silver ions contained in hair cream and the like contained in 0.5% to 1.0% are reduced to metallic silver fine particles by light, and it adheres uniformly to the hair. The gray hair appears to be dyed black. Hair dyes for dyeing gray hair using this principle have the effect of protecting the hair from UV rays and chemicals as silver fine particles are coated on the hair surface. Once dyed, it is easy to wash the hair. It has a characteristic that does not fall.

  On the other hand, in recent years, women who try to protect their skin by avoiding ultraviolet rays by reducing parasols or going out to avoid the cause of spots and freckles due to the deposition of melanin due to the trend of whitening skin, or women who rarely go out Due to the increase, the above-mentioned hair dye is gradually dyed in a short period of time when exposed to sunlight, and the white hair is dyed black, but the period until dyeing is extended to 3 to 4 days, and there is a problem that it is difficult to dye. ing. In addition, it has been pointed out that in the case of a woman with a lot of hair, the root of the hair that is difficult to receive light is difficult to dye. And once the hair dye has been dyed, it does not easily fall off even if the hair is washed, but a user who points out that the white hair is not easily dyed black also points out that it is easily dropped by washing the hair.

  As another prior art document, a hair dye composed of a silver ethanolamine compound and a reducing agent that reduces this to release silver has been proposed (see Patent Document 2). In Example 1 of Patent Document 2, silver nitrate is dissolved in distilled water, a monoethanolamine aqueous solution is added thereto, then methylcellulose is dissolved to form a viscous liquid, and monoethanolamine is used as a silver salt stabilizer. To prepare a monoethanolamine additive aqueous solution, and after applying this solution to the hair, it is dyed black over time when exposed to sunlight, etc., and the hair dyes of other Examples 2 to 4 However, a specific range of monoethanolamine concentration is not necessary when hair is dyed using a reducing agent. The present inventors have found that when the alkanolamine concentration is higher than the silver salt concentration, a complete form of alkanolamine silver complex is formed and stabilized so that it cannot be reduced by light. Accordingly, it is presumed that the hair dyes of Examples 2 to 4 of Patent Document 2 are not reduced by light because a complete alkanolamine silver complex is formed.

Japanese Patent No. 3881688 Japanese Patent Laid-Open No. 48-18438

  The photosensitive hair dyes have a long period of 3 to 4 days until the white hair is dyed in black for women who have little needs for whitening skin and have little opportunities to go out in recent years. In this case, there is a problem that the root of the hair is difficult to be dyed because light is difficult to hit, that is, a problem that the time until white hair is dyed black when the light irradiation time is short, and a problem that it is easily dropped by washing the hair. It has been pointed out.

In addition, Patent Document 2 describes that, after the monoethanolamine additive aqueous solution, which is the hair dye of Example 1, is applied to hair, it is dyed black over time when exposed to sunlight or the like. In order to stain black with sunlight, etc., a complete form of alkanolamine silver complex is not formed.Therefore, there is an appropriate range of monoethanolamine concentration with respect to silver sulfate concentration. Not listed.

  Therefore, an object of the present invention is to provide a photosensitive hair dye having an alkanolamine concentration that does not form a complete form of an alkanolamine silver complex salt, and even if the irradiation time of light is short, white hair is dyed black and does not easily fall off by washing the hair. It is to be.

As a result of diligent research aimed at solving this problem, the present inventors have found that 0.3 to 9% by weight of alkanolamines and 0.3 to 2.0% by weight of silver salt are added to the substrate material having moisture. As a result, it was found that the complete form of the alkanolamine silver complex salt was not formed, and as a result, the dyeing and dyeing properties were remarkably improved even when the light irradiation time was short, and the present invention was completed. Is.
In order to solve the above-described problem, the photosensitive hair dye according to claim 1 is prepared by mixing silver sulfate and alkanolamines with a substrate material having moisture, and silver ions are reduced to metallic silver fine particles by light. that a photosensitive hair dye, the weight ratio of the amount of the silver sulfate salt and alkanolamines, relative to sulfuric acid silver salt 1, a alkanolamines 1 to 4.5, to said substrate material, said the sulfuric acid silver salt of 0.3 to 2.0 wt% with respect to the photosensitive hair dye total amount, formed by a 0.3 to 9.0% by weight of alkanolamines, silver ions and alkanolamine silver complex only contains, characterized in that the silver ions are reduced by light.
Similarly, the photosensitive hair dye according to claim 2 is characterized in that the substrate material is an emulsion in which an oil component is emulsified in a water-soluble component.
The photosensitive hair dye according to claim 3 is characterized in that the substrate material is a gel in which a polymer material is dispersed and dissolved in a predetermined dispersion and dissolution medium.
The photosensitive hair dye according to claim 4 is characterized in that the substrate material is an aqueous solution.
The photosensitive hair dye according to claim 5 is characterized in that the photosensitive hair dye contains 0.1 to 1.4% by weight of copper sulfate as a stabilizer relative to the total amount.
A method for producing a photosensitive hair dye according to claim 6, wherein the substrate material having water contains silver sulfate and alkanolamines , wherein silver ions are reduced to fine metal silver particles by light. And the weight ratio of the compounding quantity of the said silver sulfate salt and alkanolamines is alkanolamines 1-4.5 with respect to the silver sulfate 1, and is 0.00 with respect to the said photosensitive hair dye whole quantity. Silver ions and alkanolamine silver complex salts are formed by adding 0.3 to 2.0% by weight of silver sulfate to an aqueous solution in which 3 to 9.0% by weight of alkanolamine is dissolved. It is characterized by doing.

  The photosensitive hair dye of the present invention has a dyeing / dyeing property that, compared with the conventionally used photosensitive hair dyes, even when the light irradiation time is short, the gray hair is dyed black, and even if the hair is washed after coloring, the hair dyes. Are better. Unlike oxidative hair dyes that contain dyes, paraphenylenediamine derivatives, oxidants, etc., they are highly safe hair dyes that do not cause allergies or rashes. In addition, it can be used as a hair cream, hair liquid, lotion, gel or mousse, and has the advantage that it can be easily dyed black because it does not need to be washed away immediately. And merchandise stability improves by adding copper sulfate as a stabilizer to the photosensitive hair dye of this invention.

It is the figure which compared the dyeing | staining and dyeing property of the gray hair of Example 1 and Comparative Example 1. It is the figure which compared the dyeing | staining property of the white hair for every irradiation time of the light of Example 2 and Comparative Example 2. It is the figure which left the white hair of Example 1 and Comparative Example 1 in the shade for 60 minutes to compare the dyeing / dyeing properties. It is the figure which compared the dyeing / dyeing property of 9 kinds of samples and the gray hair for every silver sulfate concentration.

Embodiments of the present invention will be described below. In addition, “%” shown below indicates a ratio to the total amount of the photosensitive hair dye.
In the photosensitive hair dye, what is usually present as silver ions is used as a silver complex salt with an alkanolamine, and the silver salt reacts with the alkanolamine to form a silver ion with the alkanolamine silver complex. . The alkanolamine silver complex salt does not form a complete silver complex salt, that is, in order to form silver ions with the alkanolamine silver complex salt, the alkanolamines are 0.3% based on the total amount of the photosensitive hair dye in the substrate material. -9% is contained, and the silver sulfate is contained 0.3-2.0%.

The substrate material may be an aqueous solution containing water, may be an emulsion in which an oil component is emulsified in a water-soluble component, or may be a gel in which a polymer material is dissolved in a predetermined dissolution medium.
The blending amount of the silver salt and the alkanolamines is preferably a weight ratio of alkanolamines 1 to 4.5 with respect to the silver salt 1. Since silver salts are used up to 0.3-2%, alkanolamines are in the range of 0.3-9%. In addition, silver sulfate dissolves only 0.8% in water, but dissolves 5% or more in the presence of alkanolamines.
For example, it has been found that when 4.8% or more of monoethanolamine is blended with 1.0% of silver sulfate, no hair is dyed even when exposed to sunlight.
Examples will be described below.

Example 1
In a 100 kg vacuum emulsifier, 1 kg of polyoxyethylene (15 mol) cetyl ether, 5 kg of cetanol, 10 kg of liquid paraffin, 1.0 kg of stearic acid, 1.0 kg of silicon oil, and 0.1 kg of stearyl glycyrrhetinate are dissolved at 80 ° C. ( Oil phase). In another kettle, 0.5 kg of monoethanolamine and 70.0 kg of water are placed and heated to 80 ° C. (water phase). While stirring the oil phase vigorously, the aqueous phase is added little by little to emulsify. When emulsified sufficiently, gently stir and cool to 45 ° C. Weigh out 10.15 kg of water in another kettle and add 0.5 kg of silver sulfate and 0.75 kg of monoethanolamine to make a clear aqueous solution at room temperature (phase A). Stirring was continued while the A phase was added dropwise little by little in the emulsion cooled to 45 ° C., and the mixture was cooled to room temperature to obtain 98.8 kg of white cream. All operations were performed with care to avoid exposure to light.

(Example 2)
In a 100 kg vacuum emulsifier, 1 kg of polyoxyethylene (15 mol) cetyl ether, 4 kg of cetanol, 10 kg of silicon oil, 1.0 kg of stearic acid and 1.0 kg of squalane are dissolved at 80 ° C. (oil phase). In another kettle, 0.5 kg of monoethanolamine and 70.0 kg of water are placed and heated to 80 ° C. (water phase). The water phase is added little by little while emulsifying the oil phase and emulsified. Stir gently after emulsification and cool to 45 ° C. Take 9.8 kg of water in another kettle, add 0.7 kg of silver sulfate, 1.5 kg of monoethanolamine, and 0.5 kg of copper sulfate pentahydrate and stir well to obtain a clear aqueous solution at room temperature (phase A) ). Phase A was slowly dropped into the emulsion cooled to 45 ° C., and stirring was continued, followed by cooling to room temperature to obtain 99 kg of a blue emulsion.

(Light irradiation test 1)
The photosensitive hair dye cream (0.5% silver sulfate) prepared in Example 1 and the conventional photosensitive hair dye cream (monoethanolamine) of Comparative Example 1 containing only silver sulfate (0.8%). 1g white hair bundle is divided into two bundles, 0.5g each is applied, exposed to direct sunlight for 30 minutes, washed with detergent, and compared with dyeing and dyeing properties of white hair by visual sensory test did. As used herein, the term “dyeing / dyeing property” means a state in which white hair coated with cream or the like is dyed black even when washed with detergent after being dyed black by light irradiation.
FIG. 1 is a diagram comparing the dyeing / dyeing properties of gray hair in Example 1 and Comparative Example 1.
In Example 1 on the right, the cream contains only 0.5% silver sulfate, but compared with Comparative Example 1 on the left containing 0.8% silver sulfate, irradiation with direct sunlight for 30 minutes. It turned out that it is excellent in dyeing | staining and dyeing property even if it is time (refer FIG. 1).

(Light irradiation test 2)
Photosensitive hair dye cream produced in Example 2 (0.7% silver sulfate) and Comparative hair dye silver cream (0.7%) only in Comparative Example 2 (without monoethanolamine) Divide 1g white hair bundle into 2 bundles, apply 0.5g each, expose to direct sunlight for 5, 10, 20, 30, 120 minutes, wash with detergent and dye white hair Wearability was compared by visual sensory test.
FIG. 2 is a diagram comparing the dyeing and dyeing properties of gray hair for each light irradiation time of Example 2 and Comparative Example 2.
Example 2 on the right has the same silver sulfate concentration as that of Comparative Example 2, but the cream containing monoethanolamine is irradiated with direct sunlight for 5 minutes, 10 minutes, 20 minutes, 30 minutes, and 120 minutes. On the other hand, it is clear from this figure that the dyeing and dyeing properties are excellent at any irradiation time.

(Light irradiation test 3)
The photosensitive hair dye cream (0.5% silver sulfate) prepared in Example 1 and the conventional photosensitive hair dye cream (monoethanolamine) of Comparative Example 1 containing only silver sulfate (0.8%). 1g white hair bundle is divided into two bundles, 0.5g each is applied, left in the shade 1m away from the window for 60 minutes, washed with detergent and the hair dyed and dyed visually Comparison was made by sensory test.
FIG. 3 is a diagram comparing the dyeing / dyeing properties of the white hair of Example 1 and Comparative Example 1 when left in the shade for 60 minutes.
It was found that Example 1 on the right side was excellent in dyeing / dyeing property even with weak light as compared with Comparative Example 1 on the left side (see FIG. 3).

(Light irradiation test 4)
A test was conducted to examine the relationship between the concentration of silver sulfate aqueous solution and the dyeing / dyeing properties.
1.7 (weight) of monoethanolamine is added to 1 (weight) of silver sulfate, and 0.1, 0.3, 0.5, 0.7, 1.0, 2.0, and 3.0, respectively. Samples of nine types of 4.0 and 5.0% silver sulfate aqueous solutions were prepared. 0.5 g of this solution was applied to 1 g of gray human hair, irradiated with a blue light emitting diode / lamp for 10 minutes, washed thoroughly, and dyeing / dyeing property was examined by visual sensory inspection. The relationship between the sample number and the silver sulfate concentration (%) is as shown in Table 1.

[Table 1]
As Comparative Example 3, a silver sulfate 0.8% solution containing citric acid 0.1 instead of monoethanolamine was applied to 1 g of white hair human hair, irradiated with a blue light emitting diode lamp for 10 minutes, and washed thoroughly. Then, the dyeing and dyeing properties were examined by visual sensory inspection.
FIG. 4 is a diagram comparing the dyeing / dyeing properties of 9 different samples and the gray hair for each silver sulfate concentration. Sample number 10 represents Comparative Example 3.

  Sample numbers 1 to 6 in FIG. 4 indicate that the dyeing and dyeing properties are improved and excellent as the silver sulfate concentration increases. At 0.1%, the dyeing / dyeing property is not good, but when it is 0.2% or more, it becomes better as the concentration increases, and the tendency continues to 2.0%, but it becomes 2.0% or more. This shows that the improvement in dyeing / dyeing property is in an equilibrium state, and Comparative Example 3 of sample number 10 is slightly inferior to the dyeing / dyeing property of sample number 2. From this, short-time light irradiation, which is irradiation for 10 minutes using a blue light emitting diode lamp (wavelength: 450 nm), is more dyeable / stainable than Comparative Example 3 if the silver sulfate concentration is 0.2% or more. This shows that the dyeing / dyeing property is improved to 2.0% as the concentration increases.

  From the results of the above light irradiation tests 1 to 4, compared to conventional hair dyes, even if the irradiation time of light is short, white hair is dyed black, and is excellent in dyeing / dyeing properties that do not fall even after washing after coloring. I found out.

Claims (6)

A photosensitive hair coloring material in which silver sulfate and alkanolamines are mixed in a substrate material having moisture, wherein silver ions are reduced to fine particles of metallic silver by light ,
0 weight ratio of the amount of the silver sulfate salt and alkanolamines, relative to sulfuric acid silver salt 1, a alkanolamines 1 to 4.5, the matrix material, relative to the photosensitive hair dye total amount .3～2.0% by weight of the sulfuric acid silver salt, formed by a 0.3 to 9.0% by weight of alkanolamines, looking containing silver ions and alkanolamine silver complex, silver ions light A photosensitive hair dye characterized by being reduced by the following .   The photosensitive hair dye according to claim 1, wherein the substrate material is an emulsion in which an oil component is emulsified in a water-soluble component.   The photosensitive hair dye according to claim 1, wherein the substrate material is a gel in which a polymer material is dissolved in a predetermined dissolution medium.   The photosensitive hair dye according to claim 1, wherein the substrate material is an aqueous solution. The photosensitive hair dye according to claim 1, wherein the photosensitive hair dye contains 0.1 to 1.4% by weight of copper sulfate as a stabilizer relative to the total amount. A method for producing a photosensitive hair dye, wherein the substrate material having moisture contains silver sulfate and alkanolamines , wherein silver ions are reduced to fine particles of metallic silver by light ,
The weight ratio of the blended amount of the silver sulfate and alkanolamine is 1 to 4.5 alkanolamine with respect to silver sulfate 1, and 0.3 to 9.9 with respect to the total amount of the photosensitive hair dye. A silver ion and an alkanolamine silver complex salt are formed by adding 0.3 to 2.0% by weight of silver sulfate to an aqueous solution in which 0% by weight of alkanolamine is dissolved. A method for producing a photosensitive hair dye.