JP7065518B2 - Hair coloring composition - Google Patents

Description

The present invention relates to a hair coloring agent composition, and more particularly to a hair coloring agent composition capable of reducing skin disorders.

Hair coloring mainly includes hair coloring, which is a permanent hair dye for quasi-drugs, and hair manicure and hair color treatment, which are semi-permanent hair dyes for cosmetics. In particular, the hair color of permanent hair dyes mainly contains a substance called para-phenylenediamine (oxidative dye), but in the case of dark black colors, the amount of diamine compounds is large, so it is even more important. Attention is needed.

For example, as a hair coloring composition containing para-phenylenediamine (oxidation dye), it was selected from (a) water-soluble peroxygen bleach; (b) organic peroxyic acid bleach precursor and / or preformed organic peroxy acid. A hair coloring composition characterized by containing a bleaching aid; and (c) one or more hair coloring agents is known (Patent Document 1).

Special table 11-501947

However, in the prior art including the above Patent Document 1, those containing para-phenylenediamine (oxidation dye) are further noted because the amount of the diamine-based compound is large in the case of a dark black color as described above. In recent years, skin disorders have been reported due to a substance called para-phenylenediamine (oxidative dye).

In addition, hair manicure, which is a semi-permanent hair dye, is characterized by the fact that the pigment (acid dye) penetrates into the inside of the hair with a single use and has a color retention of 2 to 3 weeks. It is difficult to remove the dyed pigment, and it is difficult for the practitioner to apply it to the very limit of the hairline. It has become.

Therefore, an object of the present invention is to provide a para-phenylenediamine-free hair coloring agent capable of reducing skin disorders.

In order to achieve the above object, the present inventors have found the present invention as a result of diligent studies on hair color treatment.

That is, the hair coloring agent composition of the present invention contains at least one selected from the group consisting of thioglycolic acid , 3-mercapto-1,2-propanediol, cysteamine, and salts thereof , and sodium hydroxymethanesulfinate. A hair coloring composition containing a basic dye, an HC dye, an amino acid, a cationic surfactant, a thickening agent, an oil agent, a pH adjusting agent, and a wetting agent. The pH of the composition is 6.8 to 10 .

Further, in a preferred embodiment of the hair coloring agent composition of the present invention, the pH adjusting agent is citric acid, phosphoric acid, lactic acid, malic acid, aqueous ammonia, ammonium hydrogencarbonate, ammonium carbonate, potassium hydroxide, sodium hydroxide. , Monoethanolamine, ammonium phosphate, sodium citrate, ammonium citrate, sodium lactate, potassium phosphate, sodium phosphate.

Further, in a preferred embodiment of the hair coloring agent composition of the present invention, the amino acid is characterized by being at least one selected from cysteine, arginine, lysine, histidine and salts thereof.

Further, in a preferred embodiment of the hair coloring agent composition of the present invention, the basic dye is a basic blue 3 (basic blue 3) under the name INCI (International Nomenclature of Cosmetic Ingredient). , Basic Blue 7 (Basic Blue 7), Basic Blue 9 (Basic Blue 9), Basic Blue 26 (Basic Blue 26), Basic Blue 75 (Basic Blue 75), Basic Blue 77 (Basic Blue 77) , Basic Blue 99 (Basic Blue 99), Basic Blue 124 (Basic Blue 124), Basic Red 51 (Basic Red 51), Basic Red 76 (Basic Red 76), Basic Yellow 57 (Basic Yellow 57) , Basic purple 2 (basic violet 2), basic tea 16 (basic brown 16), or basic tea 17 (basic brown 17).

Further, in a preferred embodiment of the hair coloring agent composition of the present invention, the HC dye is referred to as HC Blue 2 (HC Blue 2), HC under the name INCI (International Nomenclature of Cosmetic Ingredient). Blue 12 (HC Blue 12), HC Blue 14 (HC Blue 14), HC Blue 15 (HC Blue 15), HC Blue 16 (HC Blue 16), HC Blue 18 (HC Blue 18), HC Yellow 2 (HC Yellow) 2), select from HC Yellow 4 (HC Yellow 4), HC Yellow 5 (HC Yellow 5), HC Red 1 (HC Red 1), HC Red 3 (HC Red 3), or HC Orange 1 (HC Orange 1). It is characterized by being at least one species.

Further, in a preferred embodiment of the hair coloring agent composition of the present invention, the cationic surfactant is a quaternary ammonium salt and / or a tertiary amine.

Further, in a preferred embodiment of the hair coloring agent composition of the present invention, the quaternary ammonium salt is characterized by being an alkyltrimethylammonium chloride solution, stearyltrimethylammonium chloride, or stearyltrimethylammonium bromide.

Further, in a preferred embodiment of the hair coloring agent composition of the present invention, the tertiary amine is characterized by being dimethylaminopropylamide stearate, diethyl aminoethyl amide stearate, or behenamide propyl dimethylamine.

Further, the hair coloring agent of the present invention is characterized by containing the hair coloring agent composition of the present invention.

According to the hair coloring composition of the present invention, it does not contain para-phenylenediamine and is suitable for those who are suffering from scalp or who are worried about contact dermatitis, and the hair coloring is used for a long period of time due to aging. It has the advantage of being able to provide a hair color product that can be used with peace of mind because it has the potential to become a hair color product that can be applied to new areas without worrying about adhesion to the scalp. It works.

Further, according to the hair coloring agent composition of the present invention, the use of a specific component has an advantageous effect that the permeability is good and the amount of a dyeing agent or the like can be reduced.

FIG. 1 is a diagram showing the observation results of a hair cross-section sample treated in a 0%, 1%, and 3% solution of 3-mercapto-1,2-propanediol using various dyes with an optical microscope. .. FIG. 2 shows treatment in a 0%, 0.5%, 1%, 3% solution of 3-mercapto-1,2-propanediol when Basic Brown 16 0.2% and Basic Blue 77 0.2% were mixed to make a dark brown color. It is a figure which shows the observation result by the optical microscope of the hair cross-section sample. FIG. 3 shows 0%, 0.5%, 1%, 3%, 4% of 3-mercapto-1,2-propanediol when Basic Brown 16 0.2% and Basic Blue 77 0.2% were mixed to make a dark brown color. It is a figure which shows the observation result by the optical microscope of the hair cross-section sample treated in 5% and 10% solutions. (To be on the safe side, additional data of the PCT filed the other day is inserted. Please check.) FIG. 4 shows 0%, 0.5%, 1%, 3%, 5%, 7%, and 10% of sodium hydroxymethanesulfate when Basic Brown 16 0.2% and Basic Blue 77 0.2% are mixed to make a dark brown color. It is a figure which shows the observation result by the optical microscope of the hair cross section sample treated in the solution.

The hair coloring composition of the present invention comprises at least one selected from the group consisting of thioglycolic acid, cysteine, 3-mercapto-1,2-propanediol, cysteamine, and derivatives and salts thereof, and hydroxymethanesulfinic acid. A hair coloring composition comprising sodium, a basic dye, an HC dye, an amino acid, a cationic surfactant, a thickener, an oil agent, a pH adjusting agent, and a wetting agent. The pH of the colorant composition is characterized by a pH of 3.5 or higher. This can be done by blending thioglycerin (scientific name: 3-mercapto-1,2-propanediol) and / or sodium hydroxymethanesulfinate, etc. without raising the pH or heating. This is because the present inventors have found that the hair dyeing is better than the hair dyeing by raising the pH and heating the hair without blending the above. Further, in the hair coloring composition of the present invention, it was found that the cuticle can be easily opened by setting the pH to 6.8 or higher, and at the same time, bases such as L-arginine, L-lysine, L-histidine, and salts thereof. It was found that it is a product that can perform color treatment while sending sex amino acids into the hair and supplementing and repairing the basic amino acids that have flowed out due to pain. That is, in hair color treatments and the like, cuticles (hair follicles) and cortex near the surface of the hair are dyed, and in some cases it is not possible to achieve a hair color having a sufficiently long-lasting color. By applying an object, it is possible to open the cuticle, which in turn has the advantageous effect of achieving a hair color with good color retention.

Further, in the present invention, with at least one selected from the group consisting of thioglycolic acid, cystine, 3-mercapto-1,2-propanediol, cysteamine, and derivatives and salts thereof, and / or sodium hydroxymethanesulfinate. By including these components, it is possible to penetrate the components such as dyes deeply into the hair, and even a small amount of dye can sufficiently realize hair color, and moreover, the dye can be used for a long period of time. This is because it is possible to maintain the effect. In the present invention, among thioglycolic acid, cystine, 3-mercapto-1,2-propanediol, cysteamine, derivatives and salts thereof, and / or sodium hydroxymethanesulfinate, from the viewpoint of odor and crystal precipitation, etc. Preferably, 3-mercapto-1,2-propanediol and sodium hydroxymethanesulfinate can be used.

In a preferred embodiment of the present invention, at least one component selected from the group consisting of thioglycolic acid, cystine, 3-mercapto-1,2-propanediol, cysteamine, and derivatives and salts thereof, or hydroxymethanesulfinic acid. The content of sodium is 0.01 to 10.0% by weight, preferably 0.01 to 10.0% by weight, from the viewpoint of a composition that is hypoallergenic to the total amount of the hair coloring agent and has an excellent effect of promoting penetration into hair. It may be 0.05 to 5.0% by weight, more preferably 0.1 to 3.0% by weight.

Further, in a preferred embodiment of the hair coloring agent composition of the present invention, the pH adjusting agent is citric acid, phosphoric acid, lactic acid, or apple acid from the viewpoint of facilitating the opening of the cuticle and adjusting the pH to a desired value or higher. , Ammonia water, ammonium hydrogen carbonate, ammonium carbonate, potassium hydroxide, sodium hydroxide, monoethanolamine, ammonium phosphate, sodium citrate, ammonium citrate, sodium lactate, potassium phosphate, sodium phosphate at least One kind can be mentioned. From the viewpoint of being weakly alkaline and having a small amount of residue on the hair, preferably, the pH adjusting agent includes ammonium hydrogencarbonate, sodium hydrogencarbonate and the like.

From the viewpoint of efficiently opening the cuticle and exhibiting good color retention, the pH value of the hair coloring agent composition of the present invention is preferably pH 3.5 or higher, more preferably pH 5 to 11, and even more preferably. Can be adjusted to pH 6.8-10.

Further, in a preferred embodiment of the hair coloring agent composition of the present invention, the amino acid is characterized by being at least one selected from cysteine, arginine, lysine, histidine and salts thereof. The amount of amino acids is not particularly limited, but is preferably 0.01 to 0.5% by mass, more preferably 0.01 to 0.3, based on the total amount of the composition, from the viewpoint of maintaining the moisturizing and softness of the hair. It can be% by mass, more preferably 0.02 to 0.2% by mass.

Further, in a preferred embodiment of the hair coloring agent composition of the present invention, the basic dye is a basic blue 3 (basic blue 3) under the name INCI (International Nomenclature of Cosmetic Ingredient). , Basic Blue 7 (Basic Blue 7), Basic Blue 9 (Basic Blue 9), Basic Blue 26 (Basic Blue 26), Basic Blue 75 (Basic Blue 75), Basic Blue 77 (Basic Blue 77) , Basic Blue 99 (Basic Blue 99), Basic Blue 124 (Basic Blue 124), Basic Red 51 (Basic Red 51), Basic Red 76 (Basic Red 76), Basic Yellow 57 (Basic Yellow 57) , Basic purple 2 (basic violet 2), basic tea 16 (basic brown 16), or basic tea 17 (basic brown 17). INCI (INCI: International Nomenclature of Cosmetic Ingredient) is an international labeling name for cosmetic ingredients created by the International Nomenclature Committee (INC). The amount of the basic dye is not particularly limited, but is preferably 0.0005 to 5% by mass, based on the total amount of the composition, from the viewpoint that the dyeing power is not strong but the damage to the hair is small. It can be preferably 0.01 to 3% by mass, more preferably 0.1 to 1% by mass.

Further, in a preferred embodiment of the hair coloring agent composition of the present invention, the HC dye is referred to as HC Blue 2 (HC Blue 2), HC under the name INCI (International Nomenclature of Cosmetic Ingredient). Blue 12 (HC Blue 12), HC Blue 14 (HC Blue 14), HC Blue 15 (HC Blue 15), HC Blue 16 (HC Blue 16), HC Blue 18 (HC Blue 18), HC Yellow 2 (HC Yellow) 2), select from HC Yellow 4 (HC Yellow 4), HC Yellow 5 (HC Yellow 5), HC Red 1 (HC Red 1), HC Red 3 (HC Red 3), or HC Orange 1 (HC Orange 1). It is characterized by being at least one species. INCI (INCI: International Nomenclature of Cosmetic Ingredient) is an international labeling name for cosmetic ingredients created by the International Nomenclature Committee (INC). The amount of the HC dye is not particularly limited, but since the HC dye dyes the inside of the hair, it is preferably 0.0005 to the total amount of the composition from the viewpoint of exhibiting a deeper color. It can be 5% by mass, more preferably 0.01 to 3% by mass, and even more preferably 0.1 to 1.5% by mass.

Further, in a preferred embodiment of the hair coloring agent composition of the present invention, the cationic surfactant is a quaternary ammonium salt and / or a tertiary amine from the viewpoint of further improving the feel on the hair. It is a feature. Further, in a preferred embodiment of the hair coloring agent composition of the present invention, the quaternary ammonium salt is characterized by being an alkyltrimethylammonium chloride solution, stearyltrimethylammonium chloride, or stearyltrimethylammonium bromide. Further, in a preferred embodiment of the hair coloring agent composition of the present invention, the tertiary amine is characterized by being dimethylaminopropylamide stearate, diethyl aminoethyl amide stearate, or behenamide propyl dimethylamine. The amount of the cationic surfactant is not particularly limited, but is preferably 0.01 to 10% by mass, more preferably 0.01 to 10% by mass, based on the total amount of the composition, from the viewpoint of improving the hair dyeing ability of the basic dye. It can be 0.1 to 5% by mass, more preferably 1 to 3% by mass.

In addition, the hair coloring agent composition of the present invention may contain a thickener, a wetting agent, an oil agent and the like. In the present invention, these thickeners and the like are not particularly limited as long as they do not deviate from the effects of the present invention, and known ones can be used. Examples of the thickener include hydroxyethyl cellulose, xanthan gum, polyethylene glycol and the like from the viewpoint of product stability. The amount of the thickener is not particularly limited, but is preferably 0.05 to 0.8% by mass, more preferably 0.1 to 0.5% by mass, based on the total amount of the composition from the viewpoint of improving the stability of the product. , More preferably 0.2 to 0.4% by mass.

Examples of the wetting agent include glycerin, diglycerin, and 1,3-butylene glycol. The amount of the wetting agent is not particularly limited, but is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass, based on the total amount of the composition, from the viewpoint of ease of application of the product. %, More preferably 1 to 5% by mass.

Examples of the oil agent include fats and oils, waxes, hydrocarbons, alkylglyceryl ethers, esters, silicones, higher alcohols and the like. The amount of the oil is not particularly limited, but is preferably 1 to 30% by mass, more preferably 2 to 20% by mass, still more preferably, from the viewpoint of preventing drying for a long time of application and product stability. Can be 3 to 15% by mass.

Further, the hair coloring agent of the present invention is characterized by containing the hair coloring agent composition of the present invention. If desired, or depending on the use of the hair coloring agent, the hair coloring agent composition of the present invention can be appropriately included in the hair coloring agent.

Further, in a preferred embodiment of the hair coloring agent composition of the present invention, an antibody production inhibitor can be further contained. Examples of the antibody production inhibitor include pomegranate seed extract, mushrooms belonging to the genus Agaricus, and extracts such as yanagihakka and edelweiss from the viewpoint of prevention and improvement of allergic diseases.

For example, the case where a pomegranate seed extract is used as an antibody production inhibitor will be described as an example. Pomegranate seed extract is an extract derived from pomegranate seeds. The pomegranate seed extract applied to the present invention covers all pomegranate seed extracts as long as they are derived from pomegranate seeds.

Further, in a preferred embodiment, the pomegranate seed extract is characterized by containing punicic acid or ellagic acid. The pomegranate seed extract can be obtained, for example, by the following method. First, the pulverized product obtained by crushing pomegranate seeds is immersed in at least one solvent selected from the group consisting of ethanol, methanol, water and hexane, and the supernatant is separated to obtain the pomegranate seed extract. It is characterized by the fact that it was obtained. For example, it can be shaken and extracted. In the shaking extraction, for example, it can be extracted while being set in a rotator and rotated in a low temperature chamber such as about 4 ° C.

More specifically, first, pomegranate seeds are prepared. Pomegranate seeds are washed and dried as needed. It is preferable that the drying is sufficiently performed. This is to perform the subsequent pulverization uniformly.

Next, the pomegranate seeds are crushed. The crushing method is not particularly limited, and a known crusher such as a ball mill, a hammer mill, a roller mill, a rod mill, a sample mill, a stamp mill, a disintegrator, a mortar, and a blender with a cooling device can be used. Since it is conceivable that the pomegranate seed composition may be decomposed due to the heat generated during crushing, the crushing time may be set to several seconds and the process can be repeated a dozen times.

Next, the pomegranate seeds are crushed to obtain a pulverized product, and then the pulverized product is immersed in various solvents. The solvent in this case is not particularly limited, and the solvent can be appropriately set according to the desired effect. Further, in a preferred embodiment of the method for producing a pomegranate seed extract of the present invention, the solvent is at least one selected from the group consisting of ethanol, methanol, hexane and water. Examples of the solvent include polar and non-polar solvents such as ethanol, methanol, water, hexane, ethyl acetate, chloroform and acetone. Preferably, methanol, ethanol, water and the like can be mentioned.

The dipping can be performed under gentle stirring. The pulverized product is immersed in various solvents to obtain various solutions. Various solutions may be stirred according to the state of the solution, and the solution may be left as it is in some cases. In the case of stirring, the stirring is not particularly limited, but can be sustained for 10 hours to 48 hours, preferably about 1 day (24 hours).

Then, the pomegranate seed extract can be obtained by separating the supernatant. If necessary, the supernatant is evaporated to dryness. Evaporation to dryness can be carried out using an evaporator on a hot bath at 20 ° C to 60 ° C, preferably 37 ° C to 40 ° C. By evaporating to dryness, the pomegranate seed extract can be stored for a long period of time.

The components contained in the pomegranate seeds are sorted according to their physical characteristics by extracting the pomegranate seeds with solvents having different polarities. Therefore, the type and content of the components of the pomegranate seed extract differ depending on the solvent used.

In the present invention, an example of the hair coloring method will be described below.

1) Pre-shampoo as appropriate to remove hair styling products and stains.
2) A mixture of a hair coloring agent (containing a hair dye component) and a hair cosmetic (containing a basic cuticle swelling agent) applicable to the present invention is applied to the hair by a brush.
3) Cover the applied hair with a wrap, heat it with a hair dryer or heat cap, and leave it for about 30 minutes.
4) After 3), if necessary, apply the cuticle care agent sufficiently to the hair and leave it for about 6 minutes.
5) After 4), wash your hair with hot water and shampoo.
6) After towel drying, dry the hair with a hair dryer.

Hereinafter, an embodiment of the present invention will be described, but the present invention is not construed as being limited to the following examples.

Example 1
Regarding the alkaline agent (pH adjuster), from the viewpoint of being weakly alkaline and less likely to cause skin irritation, in this example, ammonium hydrogencarbonate was used as an example for the test.

In addition, about 80% of human hair is composed of keratin protein derived from amino acids, L-cysteine is an amino acid that is also abundant in the hair, and L-cysteine and its salts keep the hair moisturized and soft. I tried to mix it for the purpose. Typical basic amino acids include L-arginine, L-lysine, and L-histidine, but these are known to flow out when damaged, and 0.01 to 0.5 mass of basic amino acids and their salts are used. % Was found to be preferable.

Table 1 shows component examples of the hair coloring agent composition in one embodiment of the present invention.

The adjustment method is as follows.

Adjustment method:
1. 1. The aqueous phase in Table 1 is heated with stirring to 75 to 77 ° C.
2. 2. The oil phase in Table 1 is stirred while heating to 75 to 79 ° C. to make it uniform.
A dye is added to the aqueous phase heated to 3.75 to 77 ° C. to make it uniform, the oil phase is added to emulsify, and the mixture is stirred until uniform.
4. The contents are slowly cooled, and when the temperature becomes 43 ° C or lower, a preservative, a cooling component, an anti-inflammatory component, and an amino acid group are added, and the mixture is stirred until uniform, and cooled to 32 ° C or lower.

The following models and electrodes were used for pH measurement.
Model of pH meter: F-71 (HORIBA, Ltd.)
Electrode of pH meter: Type 9615 (HORIBA, Ltd.)

Further, in Table 1, the same test was conducted when "thioglycerin" was changed to "Na oxymethylene sulfoxylate" (manufacturer: Tokyo Chemical Industry Co., Ltd., 0.5% of the blending amount).

In this way, when the hair coloring agent of the present invention was adjusted and a color fading test was performed on the hair bundle, it was found to be extremely excellent in color fading.

Conventionally, when a hair coloring agent containing no para-phenylenediamine is applied and left unattended, the base color is a basic dye and an HC dye, which are considered to be safer than the oxidation dye, but because they are dyed on the hair. There was a drawback that the color retention after dyeing was poor and the color was easily discolored by repeated shampooing. Compared to conventional hair coloring agents, the hair coloring agent of the present invention not only makes it easier for the base color to penetrate, but also does not contain acid dyes, so it can be applied from the new part to the tips of the hair without worrying about adhesion to the scalp. It turned out that it could be done.

As described above, the hair coloring agent and the like of the present invention are compared with conventional hair coloring and hair manicure in performing hair dyeing, and 1) those who have damaged hair due to repeated dyeing have lower hair strength. , The elasticity is lost and the hair becomes thinner (conventional hair color), 2) If the scalp is irritated, the irritated part is dyed and it is difficult to remove it (conventional hair manicure). It has been found to provide hair cosmetics with good longevity and penetrating power. That is, it was also found that the present invention has safety as well as color retention.

Example 2
The penetrations of the main basic dyes applicable to the present invention were compared. Hair Commercially available 100% untreated white hair (product number: BS-C, manufactured by Burax Co., Ltd.) A length of 30 cm was divided into three equal parts to prepare a hair sample to be dyed. For Basic Red 51, Basic Brown 16 and 17, the dye is dissolved in purified water by 0.2%, and the pH is adjusted to alkaline using 25% ammonia water (manufactured by Wako Pure Chemical Industries, Ltd.), and 3-mercapto as thioglycerin. A 0%, 1% and 3% solution of -1,2-propanediol (manufactured by Wako Pure Chemical Industries, Ltd.) was prepared. The optimum value of alkalinity is around pH 7.5 to 10.0, but there are differences depending on the dye, and some dyes cause precipitation in the solution if the pH is raised too much. In addition, Basic Blue 75, 77, 99, Basic Violet 2, and Basic Yellow 57 are amide betaine-type double-sided activators, coconut oil fatty acid amide propyl betaine solution (product number: Softazoline CPB-R, Kawaken Fine Chemicals) to improve the solubility of dyes. (Manufactured by Wako Co., Ltd.) Dissolve 0.7% of dye in 5.0%, add purified water, and use 25% ammonia water (manufactured by Wako Pure Chemical Industries, Ltd.) to adjust the pH to alkaline, and 3-mercapto-1. , 2-Propanediol 0%, 1%, 3% solutions were prepared. A hair sample obtained by dividing one white hair into three equal parts is immersed in a 0%, 1%, 3% solution of 3-mercapto-1,2-propanediol of each dye, and left for 30 minutes in a constant temperature bath at 40 ° C. Stained. The hair sample was freeze-embedded with PVA resin, and then a hair cross-section sample (section thickness: 10 μm) was prepared using a microtome. Then, they were placed on a slide glass as a sample for microscopic observation and compared with a microscope (Fig. 1).

As shown in FIG. 1, the degree of penetration of the dye into the hair sample is the deepest in all the dyes when 3-mercapto-1,2-propanediol is 3% (the range where the color from the outer periphery of the cross section is dark). Is the largest). In particular, it was more clear that the dyes of Basic Brown 16 and Basic Blue 77 had good penetration.

Example 3
Using the dyes of Basic Brown 16 and Basic Blue 77, which had good penetration in Example 2, 100% untreated hair on the market (product number: BS-C, manufactured by Burax Co., Ltd.) was prepared in the following formulation example (Table 2). The hair was dyed dark brown by leaving it for 30 minutes in a constant temperature bath at 40 ° C. Table 2 shows an example of ingredients and an example of prescription at this time. The hair sample was freeze-embedded with PVA resin, and then a hair cross-section sample (section thickness: 10 μm) was prepared using a microtome. Then, they were placed on a slide glass as a sample for microscopic observation and compared with a microscope (Fig. 2).

Example 4
Hair Commercially available 100% untreated white hair (product number: BM-WA, manufactured by Bulux Co., Ltd.) Weighs 1 g and has a length of 10 cm. The hair bundle was washed with the washing liquid for 5 minutes. An amino acid-based anionic surfactant N-coconut oil fatty acid acyl-L-glutamic acid triethanolamine solution (product number: Aminosurfact ACMT-L, manufactured by Asahi Kasei Finechem Co., Ltd.) was used as the cleaning solution. Table 3 shows the components of the cleaning liquid.

次に、毛髪洗浄回数による色落ちを数値化するために分光色彩計（日本電色工業株式会社製、装置名：ＳＤ６０００）で測定した。各処方の洗浄回数の色彩（Ｌ＊，a＊，b＊）を表４に示す。表４は、毛髪洗浄回数による色落ちに関する結果を示す。洗髪回数による色味違いについて明度（L＊）等を用いて測定した。表４中、L*は明度で、明るい色と暗い色が数値化され、数値が小さければ小さいほど黒っぽいことになることを示す。a*は数値が大きくなればなるほど赤方向に進み、数値が小さければ緑方向に進むことを示す。また、b*は数値が大きければ黄方向に、数値が小さければ青方向に進むことを示す。

Next, in order to quantify the color fading due to the number of times the hair was washed, it was measured with a spectrocolorimeter (manufactured by Nippon Denshoku Industries Co., Ltd., device name: SD6000). Table 4 shows the colors (L *, a *, b *) of the number of washings of each formulation. Table 4 shows the results regarding discoloration due to the number of hair washes. The difference in color due to the number of times the hair was washed was measured using lightness (L *) or the like. In Table 4, L * is the brightness, and light and dark colors are quantified, and the smaller the value, the darker the color. a * indicates that the larger the value, the more red the direction, and the smaller the value, the greener the direction. In addition, b * indicates that if the numerical value is large, it advances in the yellow direction, and if the numerical value is small, it advances in the blue direction.

Therefore, when thioglycerin is 0%, the values of L *, a * and b * are increased by washing 20 times, so the blackness is reduced and the red and yellow are stronger, so the color is closer to brown. You can see that it is. On the contrary, in the case of 3%, it is shown that there is almost no change even after 20 washes because the values of L *, a *, and b * hardly move. The closer the value of L * is to 0, the darker the value. From these results, it can be seen that according to the present invention, there is little decrease in lightness and very little discoloration due to washing hair.

Example 5
Using the dyes of Basic Brown 16 and Basic Blue 77, which had good penetration in Example 2, 100% untreated hair on the market (product number: BS-C, manufactured by Burax Co., Ltd.) was prepared in the following formulation example (Table 5). The hair was dyed dark brown by leaving it for 30 minutes in a constant temperature bath at 40 ° C. Table 5 shows examples of ingredients and prescriptions at this time. The hair sample was freeze-embedded with PVA resin, and then a hair cross-section sample (section thickness: 10 μm) was prepared using a microtome. Then, they were placed on a slide glass as a sample for microscopic observation and compared with a microscope (Fig. 3). FIG. 3 shows 0%, 0.5%, 1%, 3%, 4% of 3-mercapto-1,2-propanediol when Basic Brown 16 0.2% and Basic Blue 77 0.2% were mixed to make a dark brown color. It is a figure which shows the observation result by the optical microscope of the hair cross-section sample treated in 5% and 10% solutions.

Example 6
Using the dyes of Basic Brown 16 and Basic Blue 77, which had good penetration in Example 2, 100% untreated hair on the market (product number: BS-C, manufactured by Burax Co., Ltd.) was prepared in the following formulation example (Table 6). The hair was dyed dark brown by leaving it for 30 minutes in a constant temperature bath at 40 ° C. Table 6 shows examples of ingredients and formulations.

上記毛髪試料を、ＰＶＡ樹脂を用いて凍結包埋した後、ミクロトームを用いて、毛髪断面試料（切片厚：１０μｍ）を作製した。そして、顕微鏡観察用試料としてスライドガラス上に載せて顕微鏡で比較した（図４）。図４は、Basic Brown16 0.2%とBasic Blue77 0.2%を混ぜて黒褐色にした場合の、ヒドロキシメタンスルフィン酸ナトリウムの０％、０．５％、１％、３％、５％、７％及び１０％溶液中で処理した毛髪断面試料の光学顕微鏡による観察結果を示す図である。

The hair sample was freeze-embedded with PVA resin, and then a hair cross-section sample (section thickness: 10 μm) was prepared using a microtome. Then, they were placed on a slide glass as a sample for microscopic observation and compared with a microscope (FIG. 4). FIG. 4 shows 0%, 0.5%, 1%, 3%, 5%, 7% and 10% of sodium hydroxymethanesulfate when Basic Brown 16 0.2% and Basic Blue 77 0.2% are mixed to make a dark brown color. It is a figure which shows the observation result by the optical microscope of the hair cross section sample treated in the solution.

Next, when the same cleaning solution as in Example 4 was prepared and washed with sodium hydroxymethanesulfinate in the same manner, a spectrocolorimeter (Nippon Denshoku) was used to quantify the discoloration due to the number of hair washes. It was measured by Kogyo Co., Ltd., device name: SD6000). Table 7 shows the colors (L *, a *, b *) of the number of washings of each formulation.

表７は、毛髪洗浄回数による色落ちに関する結果を示す。洗髪回数による色味違いについて明度（L＊）等を用いて測定した。表７中、L*は明度で、明るい色と暗い色が数値化され、数値が小さければ小さいほど黒っぽいことになることを示す。a*は数値が大きくなればなるほど赤方向に進み、数値が小さければ緑方向に進むことを示す。また、b*は数値が大きければ黄方向に、数値が小さければ青方向に進むことを示す。

Table 7 shows the results regarding discoloration due to the number of hair washes. The difference in color due to the number of times the hair was washed was measured using lightness (L *) or the like. In Table 7, L * is the brightness, and light and dark colors are quantified, and the smaller the value, the darker the color. a * indicates that the larger the value, the more red the direction, and the smaller the value, the greener the direction. In addition, b * indicates that if the numerical value is large, it advances in the yellow direction, and if the numerical value is small, it advances in the blue direction.

Therefore, it was found that when sodium hydroxymethanesulfinate was used, the effect of increasing the dyeing power was low as in the case of thioglycerin, but the color fading due to the number of washings could be prevented by adding it than when not adding it.

From the above results, it was found that when thioglycerin or the like is blended, it is possible to dye hair having good robustness without raising the pH or heating. It was also found that it is more effective to add thioglycerin and the like, and to increase the heating and pH. In the case of the dyes Basic Blue 99 and Basic Tea 16, the higher the pH is, the more the hair dyeing with better robustness is possible, while in the case of Basic Blue 77, the pH is 8 or higher. It was found that when raised, the pigment was broken and the color changed, resulting in weak hair dyeing.

From the above, it was found that the dye can easily enter the hair by adding thioglycerin or the like in the coloring of the hair or the like.

According to the present invention, a coloring method that does not easily damage hair, can reduce skin disorders, and easily allows dye to enter hair is easy to spread and has high industrial utility value.

Claims (9)

At least one selected from the group consisting of thioglycolic acid, 3-mercapto-1,2-propanediol, cysteamine, and salts thereof, sodium hydroxymethanesulfate, basic dyes, HC dyes, amino acids, and the like. A hair coloring agent composition containing a cationic surfactant, a thickener, an oil agent, a pH adjusting agent, and a wetting agent, wherein the pH of the hair coloring agent composition is pH 6.8 to 10. A hair coloring composition. The pH adjuster includes citric acid, phosphoric acid, lactic acid, malic acid, aqueous ammonia, ammonium hydrogencarbonate, ammonium carbonate, potassium hydroxide, sodium hydroxide, monoethanolamine, ammonium phosphate, sodium citrate, and ammonium citrate. The hair coloring composition according to claim 1, wherein the hair coloring agent composition is at least one selected from sodium lactate, potassium phosphate, and sodium phosphate. The hair coloring composition according to claim 1 or 2, wherein the amino acid is at least one selected from cysteine, arginine, lysine, histidine and salts thereof. The basic dyes are, under the INCI (International Nomenclature of Cosmetic Ingredient) name, Basic Blue 3 (Basic Blue 3), Basic Blue 7 (Basic Blue 7), and Basic Blue 9 (Basic Blue 7). Basic Blue 9), Basic Blue 26 (Basic Blue 26), Basic Blue 75 (Basic Blue 75), Basic Blue 77 (Basic Blue 77), Basic Blue 99 (Basic Blue 99), Basic Blue 124 (Basic Blue 99) Basic Blue 124), Basic Red 51 (Basic Red 51), Basic Red 76 (Basic Red 76), Basic Yellow 57 (Basic Yellow 57), Basic Purple 2 (Basic Violet 2), Basic Brown 16 (Basic Brown 16) The hair coloring agent composition according to any one of claims 1 to 3, wherein the hair coloring agent composition is at least one selected from basic brown 16) or basic brown 17 (basic brown 17). The HC dyes are HC blue 2 (HC blue 2), HC blue 12 (HC blue 12), and HC blue 14 (HC blue 14) in the INCI (International Nomenclature of Cosmetic Ingredient) name. , HC Blue 15 (HC Blue 15), HC Blue 16 (HC Blue 16), HC Blue 18 (HC Blue 18), HC Yellow 2 (HC Yellow 2), HC Yellow 4 (HC Yellow 4), HC Yellow 5 (HC Yellow 4) Claims 1 to 1, characterized in that it is at least one selected from HC yellow 5), HC red 1 (HC red 1), HC red 3 (HC red 3), or HC orange 1 (HC orange 1). 4. The hair coloring agent composition according to any one of 4. The hair coloring composition according to any one of claims 1 to 5, wherein the cationic surfactant is a quaternary ammonium salt and / or a tertiary amine. The hair coloring composition according to claim 6, wherein the quaternary ammonium salt is an alkyltrimethylammonium chloride solution, stearyltrimethylammonium chloride, or stearyltrimethylammonium bromide. The hair coloring composition according to claim 6 , wherein the tertiary amine is stearic acid dimethylaminopropylamide, stearic acid diethylaminoethylamide, or behenamide propyldimethylamine. A hair coloring agent containing the hair coloring agent composition according to any one of claims 1 to 8.

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