WO2024070264A1

WO2024070264A1 - Hair coloring agent

Info

Publication number: WO2024070264A1
Application number: PCT/JP2023/029101
Authority: WO
Inventors: 慶彦那波; 良太竹内
Original assignee: 一丸ファルコス株式会社
Priority date: 2022-09-26
Filing date: 2023-08-09
Publication date: 2024-04-04

Abstract

[Problem] To newly provide an agent for coloring hair to be used to hide gray hair, dye hair black after bleaching, deeply dye hair, etc., for use in humans or the like. [Solution] An agent for coloring hair that contains squid-ink-derived melanin and hemin.

Description

Hair coloring agent

Cross References

This application claims priority in Japan to Patent Application No. 2022-152169, filed on September 26, 2022, and the entire contents of that application are incorporated herein by reference in their entirety.

The present invention relates to a hair coloring agent for use in humans, for example, to hide gray hair, dye hair black after bleaching, dye hair dark, etc.

Hair plays a very important role in beauty, as it greatly affects a person's appearance. Hair is mainly composed of the cuticle that covers the surface, the cortex inside that accounts for the majority of the hair, and the medulla that exists in the center of the hair. Among them, the cuticle has a structure in which scale-like structures are piled up from the root to the tip of the hair, and plays a role in protecting the inside of the hair from the outside. In recent years, structural analysis of the cuticle has progressed, and it is known that the outermost layer of the cuticle has a structure in which a long-chain fatty acid called 18-methyleicosanoic acid is chemically bonded to hair protein. Hair is continuously damaged on a daily basis by chemical treatments such as perms, bleaching, and hair coloring, ultraviolet rays from sunlight, heat from hair dryers, brushing, etc. It has been found that when hair is damaged in this way, the long-chain fatty acids on the surface of the cuticle are released, and this damage to the surface of the cuticle reduces the smoothness and ease of running your fingers through the hair, which is one of the factors that makes the hair feel damaged (Patent Document 1).

In light of these circumstances, there is a continuing need for the development of hair colorants (e.g. temporary hair colorants) that have good color tone and hiding effect as a hair colorant, adhere well to hair, do not transfer color even when rubbed, and have a satisfying feel in terms of use such as a natural finish and a pleasant texture, while also having excellent storage stability (Patent Document 2, Non-Patent Document 1).

It is believed that when pigments such as iron oxide are used as colorants, the hiding effect is so strong that there is a large difference in color tone between the areas where the hair colorant is applied and those where it is not, and the difference in color from the natural hair is also noticeable, resulting in an unnatural finish. In addition, inorganic pigments generally have strong cohesive power, and it is said that they can make the hair feel stiff after application. On the other hand, when melanin is used as a colorant, the color tone blends well with the black color of the hair, resulting in a natural finish, but the color intensity may not be sufficient to hide gray hair. It is said that when the melanin content is increased to increase the color intensity, satisfactory results are not obtained in terms of adhesion to hair, lack of color transfer, and feel. Furthermore, colorants can cause aggregation in the formulation, and storage stability continues to be said to be an issue (Patent Document 2, Non-Patent Document 1).

Patent Publication No. 2021-113179 Patent Publication 2014-193828 Patent Publication 2014-152201

The problem that the present invention aims to solve is to provide a new agent that can continuously give hair a natural black color (for example, to enable hair to maintain its black color with a single hair coloring treatment).

The inventors of the present invention conducted extensive research and discovered that by containing melanin derived from squid ink, which has a color tone that blends well with hair and is an edible material (highly safe material), and hemin, it is possible to give hair a natural, continuous black color, and thus completed the present invention.

The present invention includes the following items.
[Item 1] An agent for coloring hair, comprising melanin and hemin derived from squid ink.
[Item 2] An agent for coloring hair, containing hemin.
[Item 3] A method for coloring hair, comprising the steps of treating the hair with an oxidation dye and, after the step, treating the hair with the agent described in [Item 2].
[Item 4] A kit for coloring hair, comprising an oxidation dye and the agent according to [Item 2], and comprising treating the hair with the oxidation dye and then treating the hair with the agent according to [Item 2].
[Item 5] An agent for coloring hair, comprising melanin derived from squid ink.
[Item 6] A composition comprising the agent according to [Item 1], the agent according to [Item 2] and/or the agent according to [Item 5].
[Item 7] The composition according to [Item 6], which is in the form of a composition for external application to the skin.

The present invention can provide agents for coloring hair, etc.

The figure shows a color space three-dimensional image of the L ^* a ^* b ^* color system used in Experimental Example 1 (the CIE1976L ^* a ^* b ^* color system is commonly used to quantify colors). L ^* is the lightness index, and chromaticity, which represents hue and saturation, is quantified with a ^* b ^* , which is the chromaticity index. a ^* indicates the red direction, -a ^* indicates the opposite green direction, b ^* indicates the yellow direction, and -b ^* indicates the blue direction. The closer to the center, the duller the color becomes, and the more outside, the more vivid the color becomes (Patent Document 3).

The following describes how to implement the present invention.

(Melanin derived from squid ink)
Squid ink-derived melanin has a natural blackness and color compatibility with hair, and is an essential component for an agent that hides gray hair and the like with a natural finish. In the present invention, any squid ink-derived melanin that is used in food, industrial, cosmetics, etc. can be suitably used without any particular restrictions. Squid ink-derived melanin is produced, for example, by washing the contents of the ink sac of a Japanese squid or the like with ethanol, deodorizing the contents, drying, and pulverizing the contents. The melanin thus obtained is a mixture of melanin pigment compounds having a yellow to brown to black color tone, and has a molecular weight of approximately tens of thousands to several million. It is available in several forms, such as a powder form or a paste form dispersed in oil or the like. In the present invention, a powder form is preferred, and a particle diameter of approximately 200 to 1000 nm is more preferred.

Because squid ink-derived melanin is an organic compound, it can eliminate problems with conventional inorganic pigments, such as poor storage stability due to strong cohesive forces caused by surface charges and a stiff feel after use. Furthermore, by increasing dispersibility using cationic surfactants, particularly two-chain cationic surfactants, it is possible to realize remarkable storage stability (Patent Document 2). Examples of squid ink-derived melanin products include AICA BLACK S (Nippon Chlorophyll Co., Ltd.) and squid ink pigment (Kamitsu Biological Science Institute Co., Ltd.).

The amount of squid ink-derived melanin contained in a composition containing the agent of the present invention is, for example, preferably 0.1% or more, more preferably 0.5% or more, and even more preferably 1% or more, in order to exert the desired effect. Also, the amount of hemin contained in a composition containing the agent of the present invention is, for example, preferably 15% or less, more preferably 12.5% or less, and even more preferably 10% or less, taking into consideration the desired toxicity, etc.

(Hemin)
The hemin contained in the composition containing the agent of the present invention is, for example, preferably 0.001% or more, more preferably 0.002% or more, and even more preferably 0.005% or more in order to exert the desired effect. Also, the hemin contained in the composition containing the agent of the present invention is, for example, preferably 5% or less, more preferably 1% or less, more preferably 0.1% or less, and even more preferably 0.05% or less in consideration of the desired toxicity.

(Coloring hair)
Hair coloring includes, for example, fashion dyeing to dye black hair lighter, hair dyeing to thoroughly cover gray hair (dyeing hair black or other colors), black dyeing after bleaching, and dark dyeing of hair (Japan Hair Color Industry Association website, URL: https://www.jhcia.org/information/1_classification.html).

(Oxidation dyes)
Oxidation dyes are dyes that develop color as oxidized polymers obtained by oxidation treatment, as described in, for example, Patent No. 7182378. Oxidation dyes are classified into "precursors" that can be oxidized alone, and "couplers" that cannot be oxidized alone but are oxidized when used in combination with a precursor.

The "oxidation polymer of an oxidation dye" may be a polymer of at least two oxidation dyes, and may be an oxidation polymer of one precursor, an oxidation copolymer of two or more precursors, or an oxidation copolymer of at least one precursor and at least one coupler. Among these, from the viewpoint of minimizing the change in dye color and dye density when the hair dye is stored for a long period of time and being easy to synthesize, an oxidation polymer of one precursor, an oxidation copolymer of two precursors, or an oxidation copolymer of one precursor and one coupler is preferred, an oxidation copolymer of two precursors, or an oxidation copolymer of one precursor and one coupler is more preferred, and an oxidation copolymer of one precursor and one coupler is even more preferred.

Examples of precursors include p-phenylenediamine, p-aminophenol, 2,5-diaminotoluene, N-phenyl-p-phenylenediamine, 4,4'-diaminodiphenylamine, p-methylaminophenol, o-phenylenediamine, toluene-3,4-diamine, o-aminophenol, nitro-p-phenylenediamine, 2-amino-5-nitrophenol, 4-amino-2-nitrophenol, m-phenylenediamine, and the like. These may be used as salts such as hydrochlorides, sulfates, acetates, or hydrates. Among these, from the viewpoints of excellent dyeing power and dyeing fastness, and of minimizing changes in dyeing color and dyeing density when the hair dye is stored for a long period of time, p-phenylenediamine, p-aminophenol, 2,5-diaminotoluene, o-aminophenol, or 4,4'-diaminodiphenylamine is preferred, and p-phenylenediamine, p-aminophenol, or 2,5-diaminotoluene is more preferred.

Examples of couplers include 5-amino-o-cresol, resorcin (m-diphenol), 2,4-diaminophenoxyethanol, m-aminophenol, 2,6-diaminopyridine, toluene-2,4-diamine, etc. These may be used as salts such as hydrochlorides, sulfates, acetates, etc., or as hydrates. Among these, 5-amino-o-cresol, resorcin, 2,4-diaminophenoxyethanol, m-aminophenol, and 2,6-diaminopyridine are preferred from the viewpoint of minimizing changes in dyed color and dyeing density when the hair dye is stored for a long period of time.

(Form of composition)
The composition according to the present invention (e.g., a composition for external application to the skin) may be in an appropriate form for use, such as ampoules, capsules, powders, granules, liquids, gels, foams, emulsions, sheets, mists, sprays, etc., and may be used as 1) medicines, 2) quasi-drugs, or 3) topical or whole body external skin preparations (for example, basic cosmetics such as lotions, milky lotions, creams, ointments, lotions, oils, and packs, face washes and skin cleansers such as solid soaps, liquid soaps, and hand washes, massage preparations, cleansing preparations, hair removal preparations, depilatories, shaving treatments, aftershave lotions, preshave lotions, shaving creams, foundations, lipsticks, blushers, and eye shadows). , eyeliner, mascara and other make-up cosmetics, perfumes, nail beautifying agents, nail beautifying enamel, nail beautifying enamel remover, poultices, plasters, tapes, sheets, patches, aerosols, etc.); 4) medicinal and/or cosmetic preparations applied to the scalp and hair (e.g. shampoos, rinses, hair treatments, pre-hair treatments, permanent solutions, hair dyes, hair styling products, hair tonics, hair growth and tonics, poultices, plasters, tapes, sheets, aerosols, etc.); 5) bath products used by being dropped into the bath; 6) other products such as underarm odor prevention agents, deodorants, antiperspirants, sanitary products, sanitary cotton, wet tissues, etc.

Furthermore, such compositions can be produced by arbitrarily selecting and combining the components and additives exemplified below as necessary, provided that the effects of the present invention are not impaired.

(Cationic Surfactant)
Cationic surfactants are excellent as dispersants for stably dispersing squid ink-derived melanin, and contribute to suppressing aggregation and caking of squid ink-derived melanin in formulations. In addition, cationic surfactants have excellent affinity and adsorption to hair, so when applied to hair, they are components that firmly adsorb squid ink-derived melanin to hair and increase adhesion.

Specific examples of suitable cationic surfactants include mono-long-chain alkyl quaternary ammonium salts, di-long-chain alkyl quaternary ammonium salts, and ethylene oxide adduct quaternary ammonium salts. In addition, cationic surfactants containing an ester group can also be used suitably, such as mono-long-chain alkyloyl quaternary ammonium salts and di-long-chain alkyloyl quaternary ammonium salts. Of these, di-long-chain alkyl quaternary ammonium salts and di-long-chain alkyloyl quaternary ammonium salts, which are two-chain cationic surfactants, are more preferred, as they are particularly excellent in dispersing squid ink-derived melanin. Commercially available examples of cationic surfactants include GENAMIN STAC (Clariant), which is monostearyl trimethyl ammonium chloride; GENAMIN KDM-P (Clariant), which is monobehenyl trimethyl ammonium chloride; Arcard 2HP Flake (Lion), which is distearyl dimethyl ammonium chloride; VARISOFT PATC (Evonik Goldschmidt), which is palmitamidopropyl trimethyl ammonium chloride; and DEHYQUART AU-56G (BASF), which is dipalmitoyl ethyl hydroxyethyl monium methosulfate, and these can also be suitably used in the present invention.

The lower and upper limits of the content of the cationic surfactant are not particularly limited, but are preferably as follows.
Lower limit: preferably 0.01% or more, more preferably 0.1% or more, and even more preferably 0.2% or more.
Upper limit: preferably 10% or less, more preferably 3% or less, and even more preferably 2% or less.
It is believed that by setting the content within the upper and lower limits, the squid ink-derived melanin can be dispersed well, and furthermore, affinity of the squid ink-derived melanin to the hair surface can be imparted, thereby increasing adsorption.

(Film-forming agent)
There are no particular limitations on the film-forming agent that can be used as long as it is a film-forming agent that is commonly used in cosmetics and that provides a finish that is free of adhesion of the squid ink-derived melanin pigment to hair, is non-sticky, and does not transfer color when the product of the present invention is applied to hair.

Specific examples of film-forming agents include cationic film-forming agents such as vinylpyrrolidone-N,N-dimethylaminoethyl methacrylic acid copolymer diethyl sulfate, acrylic acid amidopropyltrimonium chloride/acrylic acid amide copolymer, and polyquaternium-106, nonionic film-forming agents such as polyvinylpyrrolidone, (vinylpyrrolidone/methacrylamide/vinylimidazole) copolymer, and anionic film-forming agents such as (acrylates/t-butylamide) copolymer and N,N-dimethylammonium α-N-methylcarboxybetaine/butyl methacrylate copolymer. Of these, cationic film-forming agents are particularly excellent in terms of adhesion to hair and the finish that is not sticky and does not transfer color, and are therefore more suitable for use. Commercially available examples of film-forming agents include vinylpyrrolidone-N,N-dimethylaminoethyl methacrylic acid copolymer diethyl sulfate solution, available from H.C. Examples of such polymers include Polymer 2L (manufactured by Osaka Organic Chemical Industry Co., Ltd.), Salcare SC60 (manufactured by BASF Corporation), which is an (acrylamidopropyltrimonium chloride/acrylic acid amide) copolymer, Rubiscol K90 (manufactured by BASF Corporation), which is a polyvinylpyrrolidone, Rubiset Clear (manufactured by BASF Corporation), which is a (vinylpyrrolidone/methacrylamide/vinylimidazole) copolymer, Yukaformer SM (manufactured by Mitsubishi Chemical Corporation), which is an N,N-dimethylammonium α-N-methylcarboxybetaine/butyl methacrylate copolymer, and Plussize L-6330 (manufactured by Go-o Chemical Industry Co., Ltd.), which is an (alkyl acrylate/diacetone acrylamide) copolymer AMP, and these can also be suitably used in the present invention.

The amount of the film-forming agent is not particularly limited, but is preferably 0.1 to 5%, and more preferably 1 to 3%. By keeping it within this range, it is believed that when the product of the present invention is applied to hair, the squid ink-derived melanin adheres well to the hair, resulting in a non-sticky, non-transferable, excellent finish.

Other ingredients that are normally used in cosmetics, namely oily ingredients, lower alcohols, polyhydric alcohols, aqueous ingredients such as moisturizers, UV absorbers, antioxidants, beauty ingredients, preservatives, oil-soluble resins, dyes, cooling agents, pigments, fragrances, etc., can also be appropriately contained within a range that does not interfere with the effects of the present invention.

The present invention will be described in more detail below with reference to examples, but the present invention is in no way limited to these examples. In the following examples, the unit % of the numerical values showing the amount of each component added means mass %.

The following describes an embodiment of the present invention.

(Experiment 1: Dyeing test using human hair)
This test confirmed the degree of hair dyeing by applying a composition containing squid ink-derived melanin and hemin (containing an agent containing squid ink-derived melanin and hemin) to hair. Figure 1 shows an image (a color space three-dimensional image of the L ^* a ^* b ^* color system) to explain the L value, a value, and b value measured in this experiment 1.

(experimental method)
0. Preparation of solutions used in the experiment The following were prepared.
Solution 1 (solution containing squid ink-derived melanin): Aika Black S (Nippon Chlorophyll) was used as squid ink-derived melanin. Solution 1 was prepared according to the composition shown in Table 1 below.
Solution 2 (containing hemin, composition as shown on the right): 93% water, 5% ethanol, 1% hemin, 1% phenoxyethanol
- Human hair bundle (hair bundle, Beaulax, 10 cm, 1 g, black hair, BM-W-A)

The structure of hemin is shown below (Chemical formula 1).

1. Preparation of hair (hair after bleaching) used in the experiment A human hair bundle (hair bundle, Beaulax, 10 cm, 2 g, black hair) was washed with 1% SDS for 1 hour at room temperature (25°C). After washing with tap water, the hair bundle was naturally dried at room temperature.

2. Bleaching treatment After step 1, the hair bundle was immersed (treated) in 6% hydrogen peroxide water (pH adjusted to 10.4 with ammonia water) at room temperature for 1 hour. After this immersion, the hair bundle was washed with tap water. After washing with tap water, the hair bundle was naturally dried at room temperature. After this natural drying, a part of the hair bundle was sampled. This sampled hair bundle was designated as "measurement (0)".

3. Sample Treatment The hair bundle after the bleaching treatment in 2 was coated with the above-mentioned solution 1 and/or solution 2 as shown in Table 2. After coating, the hair bundle was wrapped in a commercially available wrap and left to stand at 40°C for 15 minutes. By leaving it to stand, solution 1 and/or solution 2 was allowed to blend into the hair bundle. After leaving it to stand, the wrap was removed (removed the wrapper) and washed with tap water. After washing with tap water, the hair bundle was naturally dried at room temperature. After naturally drying, a part of the hair bundle was sampled. This sample was used as the hair bundle for "measurement (1)".

4. Further sample treatment After the treatment in 3, the sample treatment in 3 (application of solution 1 and/or solution 2) was performed multiple times (2 or 4 times). The hair bundle that was sampled after performing the following treatment 2 more times was designated as "Measurement (3)", and the hair bundle that was sampled after performing the following treatment 4 more times was designated as "Measurement (5)".

5. Measurement of L value, a value, and b value Using a spectrophotometer (JASCO Corporation UV-Visible Near-Infrared Spectrophotometer V-770), the values (L value, a value, b value) of the samples of "Measurement (1)", "Measurement (3)", and "Measurement (5)" were measured in comparison with the sample of "Measurement (0)".

(Experimental result)
The results of the measurements using the spectrophotometer are shown in Table 2. Compared to the group to which only solution 2 was applied, the group to which solutions 1 and 2 were applied had a higher L value, and darker dyeing was confirmed.

(Experiment 2: Dyeing test using human hair (gray hair))
This test confirmed the degree of hair dyeing achieved by applying a hemin-containing composition (containing a hemin-containing agent) to gray hair.

(experimental method)
1. Preparation of solutions used in the experiment The following were prepared.
- Solution 2 (solution containing hemin, composition as shown on the right): 93% water, 5% ethanol, 1% hemin, 1% phenoxyethanol).
Hair bundle 1: human hair bundle (hair bundle, Beaulux, 10 cm, 1 g, white hair, BM-W-A).
Hair bundle 2: A human hair bundle (hair bundle, Beaulux, 10 cm, 1 g, white hair, BM-W-A) was immersed in a 1% SDS solution at 25°C for 1 hour and washed, then immersed in a 0.5% EDTA-2Na solution at 25°C for 3 hours and air-dried.

2. Sample Treatment Hair bundle 1 and hair bundle 2 were dyed using a commercially available hair coloring agent (Beauteen Tone Down Color Super Black, Hoyu Co., Ltd.). The labeling of the hair coloring agent states that the agent contains 2,5-diaminotoluene, p-phenylenediamine, and p-aminophenol as oxidation dyes. After dyeing, the following treatment was carried out.
The dyed hair bundle 1 was washed with 1% SDS at 25°C for 15 minutes by shaking.
The dyed hair bundle 2 was washed with 1% SDS containing 0.2% solution 2 at 25°C for 15 minutes by shaking.

After the washing, the hair was collected, washed with water, and air-dried. This was the initial hair bundle (0 min) for the fading test. Then, the following treatment was performed.
The initial hair bundle 1 was washed with 1% SDS at 25°C for 15 hours by shaking.
The initial hair bundle 2 was washed with 1% SDS containing 0.2% solution 2 at 25°C for 15 hours by shaking.

After the washing, the hair was collected, washed with water, and air-dried. This was used as the 15-hour hair bundle (15 hours) for the fading test. Then, the following treatment was performed.
Hair bundle 1 of the 15-hour hair bundle was washed with shaking at 25°C for 15 hours using 1% SDS.
Hair bundle 2 of the 15-hour hair bundle was washed with shaking at 25°C for 15 hours in 1% SDS containing 0.2% solution 2.

After washing, the hair was collected, rinsed with water, and air-dried. This was used as the 30-hour hair bundle (30 hours) for the fading test.

3. Measurement Using a spectrophotometer (JASCO Corporation, UV-Vis-NIR Spectrophotometer V-770), L* was measured for each group (initial hair bundle, 15-hour hair bundle, and 30-hour hair bundle) in accordance with the literature (Journal of the Illuminating Engineering Society of Japan, Vol. 76, No. 9, 1992, pp. 24-27, Trends in the Development of Color ^Difference Formulas). The measurement results are shown in Table 3.

The results showed that Hair Strand 2 had a smaller L ^* (i.e., the black dye was less removed) than Hair Strand 1, even in the initial hair strand, the 15-hour hair strand, and the 30-hour hair strand.

(Experiment 3: Dyeing test using human hair)
This test further confirmed the degree of hair dyeing by applying a composition containing squid ink-derived melanin and hemin (containing an agent containing squid ink-derived melanin and hemin) to hair.

(experimental method)
0. Preparation of solutions used in the experiment The following were prepared.
Solution 1 (solution containing squid ink-derived melanin): A solution having the composition described in Table 1 above.
- Solution 2 (solution containing hemin, composition as shown on the right): 93% water, 5% ethanol, 1% hemin, 1% phenoxyethanol.
- Human hair bundle (hair bundle, Beaulux, 10 cm, 1 g, white hair, BM-W-A).

1. Preparation of hair (hair after bleaching) used in the experiment The human hair bundle was washed with 1% SDS for 1 hour at room temperature (25°C). After washing, the hair bundle was washed with tap water. After washing with tap water, the hair bundle was naturally dried at room temperature.

2. Bleaching treatment After step 1, the hair bundle was immersed (treated) in 6% hydrogen peroxide solution (pH adjusted to 10.4 with ammonia water) at room temperature for 1 hour. After this immersion, the hair bundle was washed with tap water. After washing with tap water, the hair bundle was naturally dried at room temperature. After the natural drying, a part of the hair bundle was sampled as a control group.

3. Sample Treatment 2. The above-mentioned solution 1 or solution 2 was applied to the hair bundle after the bleaching treatment as shown in Table 4. After the application, the hair bundle was wrapped in a commercially available wrap and left to stand at 40°C for 15 minutes. By leaving it to stand, solution 1 or solution 2 was allowed to blend into the hair bundle. After leaving it to stand, the wrap was removed (removed the wrapper) and washed with tap water. After washing with tap water, the hair bundle was naturally dried at room temperature.

4. Measurement of L ^* , a ^* , and b ^* values Using a spectrophotometer (JASCO Corporation, UV-Vis-NIR Spectrophotometer V-770), the L ^* , a ^* , and b ^* values of the hair bundle after sample treatment were measured in the same manner as in Experiment 2.

(Measurement result)
The results of the measurements using the spectrophotometer are shown in Table 4. The results showed that the L ^* was smaller (i.e., the black staining was less removed) in the sample treatment groups with solution 1 or solution 2 compared to the control group.

(Experiment 4: Dyeing test using human hair)
The degree of dyeing of hair by applying a composition containing squid ink-derived melanin and hemin (containing an agent containing squid ink-derived melanin and hemin) to hair was further confirmed.

(experimental method)
0. Preparation of solutions used in the experiment The following were prepared.
Solution 1 (solution containing squid ink-derived melanin): A solution having the composition described in Table 1 above.
- Solution 2 (solution containing hemin, composition as shown on the right): 93% water, 5% ethanol, 1% hemin, 1% phenoxyethanol.
- Human hair bundle (bundle of hair (gray hair), Beaulux, 10 cm, 1 g, BM-WA).
Seawater minerals: Ichimaru Pharcos Co., Ltd. Contains sodium salt, magnesium salt, and potassium salt. The pH of the solution obtained by dissolving 1.0 g of this product in 10 mL of freshly boiled and cooled water is 7.0 to 10.0.

1. Preparation of hair to be used in the experiment 1-1. Preparation of normal hair A bundle of human hair was used as normal hair.

1-2. Preparation of bleached hair The human hair bundle was washed with 1% SDS for 1 hour at room temperature (25°C). After washing, the hair bundle was washed with tap water. After washing with tap water, the hair bundle was naturally dried at room temperature.

1-2-1. Bleaching Treatment After step 1, the hair bundle was immersed (treated) in 6% hydrogen peroxide water (pH adjusted to 10.4 with ammonia water) at room temperature for 1 hour. After this immersion, the hair bundle was washed with tap water. After washing with tap water, the hair bundle was naturally dried at room temperature. After the natural drying, a part of the hair bundle was sampled.

2. Sample Treatment The above-mentioned solution 1, solution 2 and/or seawater minerals were applied to the normal hair bundle (hair) of 1-1 or the bleached hair bundle (hair) of 1-2-1, as shown in Table 5. After application, the hair bundle was wrapped in a commercially available wrap and left to stand at 40°C for 15 minutes. By leaving it to stand, solution 1, solution 2 and/or seawater minerals were allowed to blend into the hair bundle. After leaving it to stand, the wrap was removed (removed the wrapper) and washed with tap water. After washing with tap water, the hair bundle was naturally dried at room temperature. After naturally drying, a part of the hair bundle was sampled.

3. Measurement of L ^* value, a ^* value, and b ^* value Using a spectrophotometer (JASCO Corporation, UV-Vis-NIR spectrophotometer V-770), the L ^* value, a ^* value, and b ^* value of the hair bundle after sample treatment were measured in the same manner as in Experiment 2.

(Measurement result)
The results of measurements using the spectrophotometer are shown in Table 5. The results showed that L ^* was smaller (i.e., the black dye was less removed) in the sample-treated group compared to the control group of normal hair bundles and the control group of bleached hair bundles.

(Experiment 5: Dyeing test using human hair, confirmation of degree of fading due to washing)
The degree of dyeing of hair by applying a composition containing squid ink-derived melanin and hemin (containing an agent containing squid ink-derived melanin and hemin) to hair was further confirmed.

(experimental method)
0. Preparation of solutions used in the experiment The following were prepared.
Solution 1 (solution containing squid ink-derived melanin): A solution having the composition described in Table 1 above.
- Solution 2 (solution containing hemin, composition as shown on the right): 93% water, 5% ethanol, 1% hemin, 1% phenoxyethanol.
- Human hair bundle (bundle of hair (gray hair), Beaulux, 10 cm, 1 g, BM-WA).
Seawater minerals: Ichimaru Pharcos Co., Ltd. Contains sodium salt, magnesium salt, and potassium salt. When 1.0 g of this product is dissolved in 10 mL of freshly boiled and cooled water, the pH of the solution is 7.0 to 10.0.
- Sample treatment solution for experiment 5: An aqueous solution made by mixing 1% solution 1, 5% solution 2, 2% seawater minerals, and 92% distilled water (DW).

2. Preparation of hair used in the experiment 1-1. Preparation of normal hair A bundle of human hair was used as normal hair.

2. Sample Treatment The sample treatment solution of Experiment 5 was applied to the normal hair bundle (hair) of 1-1 or the bleached hair bundle (hair) of 1-2-1. After application, the hair bundle was wrapped in a commercially available wrap and left to stand at 40°C for 15 minutes. By leaving it to stand, solution 1, solution 2 and/or seawater minerals were allowed to blend into the hair bundle. After leaving it to stand, the wrap was removed (removed the wrapper) and washed with tap water. After washing with tap water, the hair bundle was naturally dried at room temperature. After naturally drying, a part of the hair bundle was sampled.

3. Washing Step After the sample treatment, the hair bundle was washed with water and shampooed (including drying), i.e., the washing step was carried out a predetermined number of times (1, 3, 5, 10, 20, 30 times).

4. Measurement of L ^* value, a ^* value, and b ^* value Using a spectrophotometer (JASCO Corporation, UV-Vis-NIR Spectrophotometer V-770), the L ^* value, a ^* value, and b ^* value of the hair bundle after sample treatment and the hair bundle after washing a specified number of times were measured in the same manner as in Experiment 2.

(Measurement result)
The results of measurements using the spectrophotometer are shown in Table 6. The results showed that L ^* was smaller (i.e., the black dye was less removed) in the sample-treated group, both in the normal hair bundle and in the bleached hair bundle.

　The above describes the embodiment of the present invention (including examples) with reference to the drawings, but the specific configuration of the present invention is not limited to this, and even if there are design changes, etc., within the scope that does not deviate from the gist of the present invention, they are still included in the present invention.

According to the present invention, it is utilized as a novel agent for coloring hair, etc.

Claims

A hair coloring agent that contains squid ink-derived melanin and hemin.
A hair coloring agent that contains hemin.
A method for coloring hair, comprising the steps of treating the hair with an oxidative dye and, after the step, treating the hair with the agent according to claim 2.
A kit for coloring hair, comprising an oxidation dye and the agent according to claim 2, and comprising a step of treating the hair with the oxidation dye followed by a step of treating the hair with the agent according to claim 2.
An agent for coloring hair, containing squid ink-derived melanin.