JP7004682B2 - Hair color method - Google Patents

Description

The present invention relates to a hair coloring method, and in particular, a hair coloring using a mixture of a hair cosmetic composition and a hair coloring agent composition, which is less likely to damage the hair and can reduce skin disorders and has excellent color retention and penetrating dyeing power. Regarding the method.

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, the hair coloring composition containing para-phenylenediamine (oxidation dye) 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 No. 11-501947

However, as in the prior art including Patent Document 1, those containing para-phenylenediamine (oxidation dye) have a large amount of diamine-based compound in the case of a dark black color as described above. , Skin disorders caused by a substance called para-phenylenediamine (oxidative dye) have been reported.

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, it is difficult for the practitioner to apply it to the very limit of the hairline, and the dyeing is worse than the hair color for the practitioner's skill, so it is a hair dye that is often avoided in salons and beauty salons. It has become.

On the other hand, the above-mentioned hair color can dye cortex (fur quality, inside of hair) firmly, but in general hair color treatment, cuticle (hair cuticle) and cortex near the hair surface are dyed. In some cases, it was not possible to achieve a hair color with sufficient color retention.

Therefore, an object of the present invention is to provide a hair coloring method that has better color retention, is para-phenylenediamine-free, is less likely to damage the hair, and can reduce skin disorders in hair dyeing.

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

That is, the hair coloring method of the present invention comprises (A) thioglycolic acid , 3-mercapto-1,2-propanediol, cysteamine, and at least one selected from the group consisting of salts thereof , sodium hydroxymethanesulfinate, and the like. A hair coloring agent containing at least a basic dye, an HC dye, a second amino acid, a first cationic surfactant, a thickener, an oil agent, a first pH adjuster, and a wetting agent, and the hair coloring agent. The pH of the agent is a hair coloring agent having a pH of 6.8 to 10 , and
(B) Hair cosmetics containing at least an alkaline agent, a first amino acid, higher alcohols having 12 to 22 carbon atoms, a surfactant, and a thickener.
And the process of applying a mixture of
It is characterized by including a step of providing a predetermined time after the coating.

Further, in a preferred embodiment of the present invention, the content of the sodium hydroxymethanesulfinate is 0.01 to 10.0% by weight or less based on the total amount of the hair coloring agent.

Further, in a preferred embodiment of the hair coloring method of the present invention, a step of applying the cuticle care agent after the application is further included.

Further, in a preferred embodiment of the hair coloring method of the present invention, the cuticle care agent includes at least one selected from sodium bromate and hydrogen peroxide, a second cationic surfactant, and a second pH adjustment. It is characterized by containing an agent.

Further, a preferred embodiment of the hair coloring method of the present invention is characterized by comprising a step of leaving the cuticle care agent for a certain period of time after application.

Further, in a preferred embodiment of the hair coloring method of the present invention, the blending ratio of the (A) hair coloring agent and the (B) hair cosmetic is (A) / (B) = 1 to 20. It is characterized by that.

Further, in a preferred embodiment of the hair coloring method of the present invention, the alkaline agent is at least one selected from aqueous ammonia, ammonium carbonate, sodium carbonate, ethanolamines, and ammonium hydrogen carbonate.

Further, in a preferred embodiment of the hair coloring method of the present invention, the first or second 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 method of the present invention, at least one of the hair coloring agent, the hair cosmetics, and the cuticle care agent contains an antibody production inhibitor.

Further, in a preferred embodiment of the hair coloring method of the present invention, the hair is heated in a step of providing a predetermined time after the application.

According to the hair coloring method of the present invention, by not containing para-phenylenediamine, in addition to reducing the risk of scalp and contact dermatitis, it is difficult to damage the hair even when the hair coloring is used for a long period of time. However, it has a good color retention and has an advantageous effect that the practitioner can provide hair coloring to the new part without worrying about adhesion to the scalp.

Further, according to the hair coloring method of the present invention, the use of a specific component has an advantageous effect that the permeability is good and the amount of 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. 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 method of the present invention comprises (A) thioglycolic acid, cysteine, 3-mercapto-1,2-propanediol, cysteamine, and at least one selected from the group consisting of derivatives and salts thereof, hydroxymethanesulfinic acid. A hair coloring agent containing at least sodium, a basic dye, an HC dye, a second amino acid, a first cationic surfactant, a thickener, an oil agent, a first pH adjuster, and a wetting agent. The pH of the hair coloring agent is that of a coloring agent having a pH of 3.5 or higher.
(B) Hair cosmetics containing at least an alkaline agent, a first amino acid, higher alcohols having 12 to 22 carbon atoms, a surfactant, and a thickener.
And the process of applying a mixture of
It is characterized by including a step of providing a predetermined time after the coating. The hair coloring agent is at least one selected from the group consisting of thioglycolic acid, cysteine, 3-mercapto-1,2-propanediol, cysteamine, and derivatives and salts thereof, sodium hydroxymethanesulfinate, and a base. It contains a sex dye, an HC dye, a second amino acid, a first cationic surfactant, a thickener, an oil agent, a first pH adjuster, and a wetting agent, and has a pH. Is 3.5 or more, and the hair cosmetic contains an alkaline agent, a first amino acid, higher alcohols having 12 to 22 carbon atoms, a surfactant, and a thickener. Is preferable. This is done by adding thioglycerin (scientific name: 3-mercapto-1,2-propanediol), etc. to raise the pH without adding thioglycerin, etc., without raising the pH or heating. This is because the present inventors have found that the hair dyeing is better than that of the hair dyed by warming.

First, a hair coloring agent composition and a hair coloring agent applicable to the present invention will be described below.

The hair coloring composition applicable to 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 hydroxy. A hair coloring composition containing sodium methanesulfinate, a basic dye, an HC dye, an amino acid, a cationic surfactant, a thickener, an oil agent, a pH adjuster, and a wetting agent. When the pH of the hair coloring agent composition is mixed with thioglycerin, sodium hydroxymethanesulfinate, or the like, it is possible to dye hair having good robustness without raising the pH or heating. From the viewpoint, the pH is 3.5 or higher. Further, in the hair coloring composition applicable to the present invention, by setting the pH to 6.8 or higher, the cuticle can be easily opened, and at the same time, basicity such as L-arginine, L-lysine, L-histidine, and salts thereof. It is a product that can be colored while repairing basic amino acids that have flowed out of the hair in the past (as damage to the hair) by sending amino acids into the hair. That is, when the hair colorant composition of the present invention is applied, the cuticle can be opened, and a hair color having a good color can be achieved, which is an advantageous effect.

Further, in the present invention, 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 / or sodium hydroxymethanesulfinate can be used.

Further, the present invention does not require an alkaline agent and has an excellent effect of promoting the penetration of the dye into the hair even in the neutral region. However, in a preferred embodiment of the hair coloring agent composition applicable to the present invention, the cuticle From the viewpoint of making it easier to open and adjusting the pH to a value higher than the desired value, the pH adjuster includes citric acid, phosphoric acid, lactic acid, malic acid, aqueous ammonia, ammonium hydrogencarbonate, ammonium carbonate, potassium hydroxide and hydroxide. At least one selected from sodium, monoethanolamine, ammonium phosphate, sodium citrate, ammonium citrate, sodium lactate, potassium phosphate and sodium phosphate 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.

In a preferred embodiment of the invention, the content of at least one component selected from the group consisting of thioglycolic acid, cystine, 3-mercapto-1,2-propanediol, cysteamine, and derivatives and salts thereof, and / Alternatively, the content of sodium hydroxymethanesulfinate is 0.01 to 10.0 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% by weight, preferably 0.05 to 5.0% by weight, and more preferably 0.1 to 3.0% by weight.

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 3.5 or more, more preferably 5 to 11, and even more preferably. It can be adjusted to 6.8 to 10.

Further, in a preferred embodiment of the hair coloring composition applicable to the present invention, the amino acid is characterized by being at least one selected from cysteine, arginine, lysine, or 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 0.5% by mass, based on the total amount of the composition, from the viewpoint of maintaining the moisturizing and softness of the hair. , 0.01 to 0.3% by mass, more preferably 0.02 to 0.2% by mass.

Further, in a preferred embodiment of the hair coloring composition applicable to the present invention, the basic dye is a basic blue 3 (basic) under the name INCI (International Nomenclature of Cosmetic Ingredient). Blue 3), 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) 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) It is characterized by being at least one selected from yellow 57), basic purple 2 (basic violet 2), basic tea 16 (basic brown 16), and 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 applicable to the present invention, the HC dye is HC blue 2 (HC blue 2), HC blue 12 (HC blue 12), HC blue 14 (HC blue 12) in the INCI name. 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), HC Yellow 4 (HC Yellow 4), It is characterized by being at least one selected from 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). .. 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 applicable to the present invention, the cationic surfactant is a quaternary ammonium salt and / or a tertiary amine from the viewpoint of further improving the feel given to the hair. It is characterized by being. 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, the tertiary amine is characterized by being stearic acid dimethylaminopropylamide, stearic acid diethylaminoethylamide, or behenamide propyldimethylamine. The amount of the cationic surfactant is not particularly limited, but is 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 preferably 0.1 to 5% by mass, more preferably 1 to 3% by mass.

In addition, the hair coloring agent composition applicable to 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, with respect to the total amount of the composition from the viewpoint of improving the stability of the product. It can be 1 to 0.5% by mass, 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, with respect to the total amount of the composition from the viewpoint of ease of application of the product. It can be 5 to 10% by mass, 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 stability of the product. Can be 3 to 15% by mass.

Further, the hair coloring agent applicable to the present invention is characterized by containing the above-mentioned hair coloring agent composition applicable to the present invention. If desired, or depending on the use of the hair coloring agent, the hair coloring agent can appropriately contain a hair coloring agent composition applicable to the present invention.

In addition, an example of a hair cosmetic composition and a hair cosmetic applicable to the present invention is as follows.

The hair cosmetic composition applicable to the present invention is characterized by containing an alkaline agent, an amino acid, higher alcohols having 12 to 22 carbon atoms, a surfactant, and a thickener. It is not essential to add an alkaline agent, but it is possible to open the cuticle by adding an alkaline agent. That is, in the conventional hair coloring or the like, the cuticle (hair cutlet) and the cortex near the hair surface may be dyed, and it may not be possible to achieve a hair color having a sufficiently long-lasting color. It is possible to open the cuticle, and by extension, it has the advantageous effect of achieving a hair color with good color.

That is, conventionally, for dyeing cuticles and cortex near the surface, basic dyes and HC dyes are basic to the deeper part of the hair by using the hair cosmetic composition (swelling agent). It has been found by the present inventors that it is possible to dye with a dye and an HC dye.

Further, from the viewpoint that the cuticle can be opened efficiently and the swelling effect can be satisfactorily exhibited, the pH value of the hair cosmetic composition is preferably 3.5 or more, more preferably 5 to 11, and even more preferably. It can be adjusted to 6.8 to 10. The amount of the alkaline agent is not particularly limited, but is preferably 0.1 to 3% by mass with respect to the total amount of the composition from the viewpoint of efficiently opening the cuticle and exhibiting a good swelling effect. can do.

The amount of amino acids is not particularly limited, but is preferably 0.01 to 0.5% by mass, more preferably 0.01 to 0.5% by mass, based on the total amount of the composition, from the viewpoint of maintaining the moisturizing and softness of the hair. , 0.01 to 0.3% by mass, more preferably 0.02 to 0.2% by mass.

In the hair cosmetic composition applicable to the present invention, the higher alcohol having 12 to 22 carbon atoms is not particularly limited, but from the viewpoint of imparting smoothness to the hair, improving the emulsification stability and adjusting the viscosity, for example. , Cetyl alcohol, lauryl alcohol, myristyl alcohol, cetostearyl alcohol, stearyl alcohol, behenyl alcohol and the like.

The amount of higher alcohols having 12 to 22 carbon atoms is not particularly limited, but is based on the total amount of the composition from the viewpoint of imparting smoothness to the hair, improving emulsion stability and adjusting the viscosity. It can be preferably 0.1 to 5.0% by mass, more preferably 0.1 to 3.0% by mass, and even more preferably 0.2 to 2.0% by mass.

In a preferred embodiment, the alkaline agent is not particularly limited, and examples thereof include at least one selected from aqueous ammonia, ammonium carbonate, sodium carbonate, ethanolamines, ammonium hydrogencarbonate, and arginine. Further, in a preferred embodiment of the hair cosmetic composition applicable to the present invention, the ethanolamines are monoethanolamine, diethanolamine, and / or triethanolamine. Ethanolamines such as monoethanolamine have little odor because they are non-volatile, but they remain in the hair and may damage the hair. In addition, arginine has a high affinity for hair, but its action as an alkaline agent is weak and its reaction is mild. Ammonia water has a pungent odor because it is volatile, but it is characterized by a small amount of residue on the hair and a quick reaction. From this point of view, the alkaline agent is preferably ammonia water.

Also, in a preferred embodiment, the amino acid may include at least one selected from cysteine, arginine, lysine, and / or histidine, and salts thereof. It has been reported that arginine and histidine inside the hair decrease with aging, but in the present invention, arginine, histidine hydrochloride and lysine contained in the hair cosmetic composition (swelling agent) of the present invention have been reported. It is possible for the hydrochloride salt to penetrate the hair and exert a hair repair effect.

The hair cosmetic composition applicable to the present invention may contain a surfactant and a thickener. The surfactants and thickeners are not particularly limited as long as they do not deviate from the effects of the present invention, and known ones can be used.

Further, in a preferred embodiment, in the hair cosmetic composition applicable to the present invention, the alkaline agent contained in the hair cosmetic composition can open the cuticle.

It is also possible to apply, for example, a cuticle care agent containing sodium bromate, for example, in order to tighten the cuticle after hair coloring containing the hair cosmetic composition applicable to the present invention. It is also possible to delay the discoloration by dyeing the inside of the hair with an HC dye that easily discolors.

Further, the hair cosmetics applicable to the present invention are characterized by containing the hair cosmetic composition.

The above is an explanation of an example of a hair cosmetic and a hair coloring agent.

In the present invention, a mixture of these hair coloring agents and hair cosmetics in a predetermined ratio can be applied. The reason why the two are mixed is that the present inventors have found that when the two are mixed and used as compared with these single uses, the dyeing is deeper and the color retention is improved. It is sufficient to mix the two, and the predetermined ratio is not particularly limited, but in a preferred embodiment, the blending ratio of the (A) hair coloring agent and the (B) hair cosmetic is the mixing ratio of (A) / (. B) = 1 to 20. That is, from the viewpoint of hair dyeing ability, the blending ratio of the hair coloring agent and the hair cosmetic is preferably a mass ratio of 1 to 20: 1, more preferably 5 to 15: 1, and even more preferably 8. The mass ratio can be ~ 12: 1.

Further, in the present invention, a predetermined time can be provided after the application from the viewpoint that the cuticle can be efficiently opened, the swelling effect can be satisfactorily exhibited, and the dyeing can proceed. Further, in a preferred embodiment of the hair coloring method of the present invention, the hair is heated from the viewpoint of enhancing the osmotic dyeing power in the step of providing a predetermined time after the application. The heating time is also not particularly limited as desired, but can be 1 to 60 minutes, preferably 5 to 40 minutes from the viewpoint of efficient hair dyeing. From the viewpoint of the treatment process time, the temperature may be raised to about 40 ° C. in about 10 minutes to (about 10 minutes or more), and the temperature may be maintained for about 30 minutes. Further, in a preferred embodiment of the hair coloring method of the present invention, the coated portion may be covered with a wrap and heated using a hair dryer heat cap during the time of leaving the hair with the coating.

Further, in the present invention, the step of applying the cuticle care agent after the predetermined time can be included. Further, in a preferred embodiment of the hair coloring method of the present invention, after the cuticle care agent is applied, the cuticle (hair cuticle) opened is tightened and the HC dye is left to stand for a certain period of time from the viewpoint of dyeing the inside of the hair. Can include steps. The leaving time is not particularly limited, but for example, the leaving time can be 1 to 20 minutes, preferably 1 to 10 minutes.

Further, in a preferred embodiment of the hair coloring method of the present invention, a step of applying a cuticle care agent may be further included. For example, in a preferred embodiment, after the hair cosmetic and the hair coloring agent are mixed and applied, at least one selected from sodium bromate and hydrogen peroxide and a second cationic surfactant are added. , A step of applying a cuticle care agent containing a second pH adjuster and the like may be included. As the second pH adjuster, a pH adjuster on the acidic side can be blended. From the viewpoint of returning to a healthy hair state (isoelectric band pH 4.5 to 5.5), the pH adjuster includes organic acids such as citric acid, phosphoric acid, phytic acid, lactic acid and malic acid, and glutamic acid. Such as acidic amino acids and the like can be mentioned.

Further, in a preferred embodiment of the hair coloring method of the present invention, the alkaline agent is at least one selected from aqueous ammonia, ammonium carbonate, sodium carbonate, ethanolamines, ammonium hydrogencarbonate and arginine. do. For the alkaline agent, the above description in the hair cosmetics and the like applicable to the present invention can be referred to.

Further, in a preferred embodiment of the hair coloring method of the present invention, the first or second amino acid is characterized by being at least one selected from cysteine, arginine, lysine, or histidine and salts thereof. .. For the first or second amino acid, the above description in the hair cosmetics and hair coloring agents applicable to the present invention can be referred to.

Further, in a preferred embodiment of the hair coloring method of the present invention, application of a shampoo agent may be further included. When the shampoo agent is applied to hair, it may be applied before hair cosmetics from the viewpoint of removing inhibitory factors such as hair styling products and sebum. In this case, as the shampoo agent, preferably, estrone shampoo, estrone black, apple cell shampoo premium, nanosupplement cleansing shampoo and the like (manufacturers and distributors of these products: Sunny Place Co., Ltd.) can be used.

Further, the shampoo agent may be applied after coloring. In this case, the pH of the shampoo is preferably weakly acidic. Further, as the shampoo agent, preferably, estrone shampoo or Aplusel shampoo premium (manufacturer / distributor: Sunny Place shampoo agent) can be used.

Further, in a preferred embodiment of the hair coloring method of the present invention, at least one of the hair coloring agent, the hair cosmetics, and the cuticle care agent can further contain an antibody production inhibitor. 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.

An example of the hair coloring method of the present invention 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, examples of a hair coloring agent and a cuticle care agent suitable for the hair coloring method of the present invention will be described, but the present invention is not construed as being limited to the following examples.

First, a hair coloring agent applicable to the present invention was prepared.

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 drops below 43 ° C, preservatives, 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 carried out 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 applicable to 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. In contrast to conventional hair coloring agents, the hair coloring agent applied to the present invention not only makes it easier for the base color to penetrate, but also does not contain acid dyes, so it does not care about adhesion to the scalp and from the new part to the tip of the hair. It turned out that it can be applied up to.

As described above, the hair coloring agent and the like applied to 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 higher hair strength. There is no problem that the hair becomes thinner, loses elasticity, and becomes thinner (conventional hair color), 2) if the scalp is irritated, the irritated part is dyed and it is quite difficult to remove (conventional hair manicure). It has been found to provide hair cosmetics with better color retention and penetrating power. That is, it was also found that the present invention has safety as well as color retention.

Next, a hair cosmetic product applicable to the present invention was prepared.

As the alkaline agent, aqueous ammonia, ammonium carbonate, sodium carbonate, mono, ethanolamines such as triethanolamine, ammonium hydrogencarbonate, arginine and the like can be considered. However, ethanolamines such as monoethanolamine have a low odor because they are non-volatile, but they have a high residual content on the hair and may damage the hair. In addition, arginine has a high affinity for hair, but its action as an alkaline agent is weak and its reaction is mild. Ammonia water has a pungent odor because it is volatile, but it has a property that it does not remain on the hair and reacts quickly.

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 of the hair due to damage, and basic amino acids and their salts 0.01 to 0.5. It turned out that% by mass was preferable.

Table 2 shows an example of the components of the hair cosmetic composition according to one embodiment of the present invention.

Table 3 shows an example of adjustment regarding an example of a component of a hair cosmetic according to an embodiment of the present invention.

The adjustment method is as follows.
1. 1. After confirming the dissolution of the amino acid group in the purified water of phase A in Table 3, the alkaline agent is uniformly mixed.
2. 2. Then, while stirring the A phase of Table 3, the B phase of Table 3 is added and mixed uniformly.
3. 3. Add the C phase shown in Table 3 with moderate stirring, and stir until uniform.

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.)

Table 4 shows an example of the components of the cuticle care agent according to one embodiment of the present invention. The cuticle care agent includes an action of improving the condition of the cuticle, such as preparing and tightening the cuticle. In other words, it is not limited to the action of adjusting and tightening.

Table 5 shows an example of a method for preparing a cuticle care agent applicable to the present invention in one embodiment of the present invention.

本発明に適用可能なキューティクルケア剤の調整方法は以下の通りである。
調整方法：
１．表５のＡ相の精製水に残りの成分を均一に混合する。
２．表５のＡ相を撹拌しながら表５のＢ相を加えて均一に混合する。
３．適度に撹拌しながら表５のＣ相を加え、均一になるまで撹拌する。

The method for adjusting the cuticle care agent applicable to the present invention is as follows.
Adjustment method:
1. 1. The remaining components are uniformly mixed with the purified water of phase A in Table 5.
2. 2. While stirring the A phase of Table 5, the B phase of Table 5 is added and mixed uniformly.
3. 3. Add the C phase shown in Table 5 with moderate stirring, and stir until uniform.

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.)

Next, an example based on the present invention will be described.
Example 1
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 2
Using the dyes of Basic Brown 16 and Basic Blue 77, which had good penetration in Example 1, 100% untreated hair on the market (product number: BS-C, manufactured by Bureaux) 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. 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 3
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-glutamate triethanolamine solution (product number: Aminosurfact ACMT-L, manufactured by Asahi Kasei Finechem Co., Ltd.) was used as the cleaning solution. Table 7 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８に示す。表８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８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 8 shows the colors (L *, a *, b *) of the number of washings of each formulation. Table 8 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 8, L * is the lightness, 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 4
Using the dyes of Basic Brown 16 and Basic Blue 77, which had good penetration in Example 1, 100% untreated hair on the market (product number: BS-C, manufactured by Burax Co., Ltd.) was prepared in the following formulation example (Table 9). The hair was dyed dark brown by leaving it for 30 minutes in a constant temperature bath at 40 ° C. Table 9 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. 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 5
Using the dyes of Basic Brown 16 and Basic Blue 77, which had good penetration in Example 1, 100% untreated hair on the market (product number: BS-C, manufactured by Burax Co., Ltd.) was prepared in the following formulation example (Table 10). The hair was dyed dark brown by leaving it for 30 minutes in a constant temperature bath at 40 ° C. Table 10 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 hydroxymethanesulfinate 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 washing liquid as in Example 3 was prepared and washed with sodium hydroxymethanesulfinate in the same manner, a spectrocolorimeter (Nippon Denki) was used to quantify the discoloration due to the number of hair washings. It was measured by Kogyo Co., Ltd., device name: SD6000). Table 11 shows the colors (L *, a *, b *) of the number of washings of each formulation.

表１１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１１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 11 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 11, L * is the lightness, 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, when thioglycerin or the like is blended, a step of providing a predetermined time after application is necessary, but it is possible to dye hair having good robustness without raising the pH or heating. It turned out to be. It was also found that it is more effective to add thioglycerin or 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 addition of thioglycerin in the coloring of hair and the like makes it easier for the dye to enter the hair.

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 applicability.

Claims (10)

(A) At least one selected from the group consisting of thioglycolic acid , 3-mercapto-1,2-propanediol, cysteamine, and salts thereof , sodium hydroxymethanesulfinate, basic dye, HC dye, second. A hair coloring agent containing at least an amino acid, a first cationic surfactant, a thickener, an oil agent, a first pH adjusting agent, and a wetting agent, and the pH of the hair coloring agent is pH 6.8 to 10 . With a hair colorant that is
(B) Hair cosmetics containing at least an alkaline agent, a first amino acid, higher alcohols having 12 to 22 carbon atoms, a surfactant, and a thickener.
And the process of applying a mixture of
A hair coloring method comprising a step of providing a predetermined time after the application. The hair coloring method according to claim 1, wherein the content of the sodium hydroxymethanesulfinate is 0.01 to 10.0% by weight with respect to the total amount of the hair coloring agent. The hair coloring method according to claim 1 or 2, further comprising a step of applying the cuticle care agent after the application. The method according to claim 3, wherein the cuticle care agent comprises at least one selected from sodium bromate and hydrogen peroxide, a second cationic surfactant, and a second pH adjuster. The method according to claim 3 or 4, which comprises a step of leaving the cuticle care agent for a certain period of time after application. The blending ratio of the (A) hair coloring agent and the (B) hair cosmetic to be mixed is (A) / (B) = 1 to 20, according to any one of claims 1 to 5. Method. The method according to any one of claims 1 to 6, wherein the alkaline agent is at least one selected from aqueous ammonia, ammonium carbonate, sodium carbonate, ethanolamines, and ammonium hydrogen carbonate. The method according to any one of claims 1 to 7, wherein the first or second amino acid is at least one selected from cysteine, arginine, lysine, histidine, and salts thereof. The method according to claim 3 , wherein at least one of the hair coloring agent, the hair cosmetic, and the cuticle care agent contains an antibody production inhibitor. The method according to any one of claims 1 to 9, wherein the hair is heated in the step of providing a predetermined time after the application.

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