JP7111365B2 - hair color method - Google Patents

Description

TECHNICAL FIELD The present invention relates to a hair coloring method, and more particularly, to a hair coloring method using a mixture of a hair cosmetic composition and a hair coloring agent composition which are less likely to damage hair, can reduce skin disorders, and can be colored in a design.

Hair coloring mainly includes hair coloring, which is a quasi-drug permanent hair dye, and hair manicure and hair color treatment, which are semi-permanent hair dyes of cosmetics. In particular, most permanent hair dyes contain a substance called paraphenylenediamine (oxidation dye). Caution is required.

For example, hair coloring compositions containing paraphenylenediamine (oxidative dye) selected from (a) water-soluble peroxygen bleach, (b) organic peroxyacid bleach precursors and/or preformed organic peroxyacids. A hair coloring composition comprising a bleaching aid and (c) one or more hair coloring agents is known (Patent Document 1).

Japanese Patent Publication No. 11-501947

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

In addition, semi-permanent hair manicures are characterized by the pigment (acid dye) penetrating into the hair with one use and the color lasting for 2 to 3 weeks, but if it adheres to the scalp and is left for a long time, it will last longer. Indeed, it is difficult to remove the dyed pigment, and it is difficult for the practitioner to apply it to the very last minute of the hairline. It has become.

On the other hand, with the above hair colors, the cortex (cortex, the inside of the hair) can be thoroughly dyed, but with general hair color treatments, the cuticle (hair cuticle) and the cortex near the surface of the hair are dyed. However, in some cases, a sufficiently long-lasting hair color could not be achieved.

In recent years, there has also been a demand for “design colors” and “fashionable dyeing” for healthy hair with raised color tones. Making points is desired.

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a hair coloring method that provides longer lasting color, is paraphenylenediamine-free, less likely to damage hair, and capable of reducing skin disorders in dyeing hair.

In order to achieve the above object, the present inventors have made intensive studies on hair coloring methods, and as a result, have found the present invention.

That is, the hair coloring method of the present invention includes a step of bleaching before the step of applying (A) a hair coloring agent and (B) a hair cosmetic,
(A) thioglycolic acid , 3-mercapto-1,2-propanediol, cysteamine, and at least one selected from the group consisting of 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 oily agent, a first pH adjusting agent, and a wetting agent, wherein the hair coloring agent has a pH of 6.8 to 10 . a hair coloring agent that is
(B) a hair cosmetic containing at least an alkaline agent, a first amino acid, a higher alcohol having 12 to 22 carbon atoms, a surfactant, and a thickener;
A step of applying a mixture of at a predetermined ratio;
and a step of providing a predetermined time after the coating.

Further, in a preferred embodiment of the hair coloring method of the present invention, the blending amount of the basic dye or HC dye is 0.5% by weight or less with respect to the total amount of the hair coloring agent.

A preferred embodiment of the hair coloring method of the present invention is characterized by further comprising the step of applying a cuticle care agent after the application.

In a preferred embodiment of the hair coloring method of the present invention, the cuticle care agent comprises at least one selected from sodium bromate and hydrogen peroxide, a second cationic surfactant, and a second pH adjuster. and an agent.

In a preferred embodiment of the hair coloring method of the present invention, it is characterized by including the step of leaving for a certain period of time after applying the cuticle care agent.

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

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.

In a preferred embodiment of the hair coloring method of the present invention, the first or second amino acid is at least one selected from cysteine, arginine, lysine, histidine, and salts thereof. .

Moreover, in a preferred embodiment of the hair coloring method of the present invention, at least one of the hair coloring agent, the hair cosmetic, and the cuticle care agent contains an antibody production inhibitor.

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

According to the hair coloring method of the present invention, by not containing paraphenylenediamine, in addition to reducing the risk of rashes and contact dermatitis, even when the hair coloring is used for a long time, it is difficult to damage the hair. Also, the color lasts well, and the operator can provide hair coloring even to the nascent part without worrying about adhesion to the scalp.

In addition, according to the post-bleaching hair color composition of the present invention, the use of the specific component has good permeability, and even with a small amount of dye, etc., it is possible to realize a design color, etc. There is an advantageous effect that it is.

FIG. 1 shows the results of optical microscope observation of cross-section samples of hair treated with 0%, 1% and 3% solutions of 3-mercapto-1,2-propanediol when using various dyes. .

The hair coloring method of the present invention includes a step of bleaching before the step of applying (A) a hair coloring agent and (B) a hair cosmetic,
(A) at least one selected from the group consisting of thioglycolic acid, cysteine, 3-mercapto-1,2-propanediol, cysteamine, and derivatives and salts thereof, a basic dye, an HC dye, a second amino acid, A hair coloring agent containing at least a first cationic surfactant, a thickening agent, an oil agent, a first pH adjusting agent, and a wetting agent, wherein the hair coloring agent has a pH of 3.5 or higher. a coloring agent;
(B) a hair cosmetic containing at least an alkaline agent, a first amino acid, a higher alcohol having 12 to 22 carbon atoms, a surfactant, and a thickener;
A step of applying a mixture of at a predetermined ratio;
and a step of providing a predetermined time after the coating. The hair color agent comprises at least one selected from the group consisting of thioglycolic acid, cysteine, 3-mercapto-1,2-propanediol, cysteamine, and derivatives and salts thereof, a basic dye, an HC dye, containing a second amino acid, a first cationic surfactant, a thickener, an oil agent, a first pH adjuster, and a wetting agent, and having a pH of 3.5 or higher The hair cosmetic composition preferably contains an alkaline agent, a first amino acid, higher alcohols having 12 to 22 carbon atoms, a surfactant, and a thickener. The hair coloring agent can also preferably contain sodium hydroxymethanesulfinate.

This can be achieved by adding thioglycerin (scientific name: 3-mercapto-1,2-propanediol) or the like without raising the pH or heating. The inventors of the present invention have found that the hair is dyed better than that dyed by heating.

The reason why the decolorization process is adopted this time is because it is specified that the hair coloring agent or the like is applied after the so-called decolorization process. That is, unless it has undergone a bleaching treatment, the above-mentioned hair penetrating agents such as thioglycolic acid, cysteine, 3-mercapto-1,2-propanediol, cysteamine, etc. are used to directly apply hair color to healthy hair. This is because even if the agent composition is applied, there is almost no change in the black hair, and the design color may not be enjoyed. Therefore, the present invention can be more effectively exhibited on hair that has undergone bleaching treatment once.

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

The hair coloring agent composition applicable to the present invention includes at least one selected from the group consisting of thioglycolic acid, cysteine, 3-mercapto-1,2-propanediol, cysteamine, and derivatives and salts thereof; A hair coloring agent 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 thioglycerin, sodium hydroxymethanesulfinate, or the like is added to the hair coloring agent composition, it is said that it is possible to dye hair with good fastness properties without raising the pH or heating. From the point of view, the pH is 3.5 or higher. In addition, in the hair coloring agent composition applicable to the present invention, the pH of 6.8 or higher facilitates the opening of the cuticle, and at the same time, L-arginine, L-lysine, L-histidine, or a basic ingredient such as L-arginine, L-lysine, L-histidine or salts thereof. It is a product that delivers amino acids to the inside of the hair and can be colored while supplementing and repairing the basic amino acids that have flowed out of the hair in the past (as damage to the hair). That is, when the hair coloring agent composition of the present invention is applied, it is possible to open the cuticle, and it is possible to achieve a long-lasting hair coloring, which is an advantageous effect.

Further, in a preferred embodiment of the present invention, from the viewpoint of design color, the blending amount of the basic dye or HC dye is 0.5% by mass or less with respect to the total amount of the composition. From the viewpoint of design color, it is preferably 0.005 to 0.5 mass %, more preferably 0.01 to 0.45 mass %, still more preferably 0.005 to 0.5 mass %, more preferably 0.01 to 0.45 mass %, based on the total amount of the composition. 05 to 0.4% by mass. If the blending amount of the basic dye or HC dye is more than 0.5% by mass, the brightness may decrease, and it may be difficult to achieve the desired effect. For the gray hair dyeing, the gray hair was dyed darkly and the brightness was set to about 4 to 5 on the scale level. In addition, the 6th to 7th level of lightness is a hair color that looks black under healthy hair and under lighting, but it looks a little brown when the sun hits it, and the atmosphere is softer than jet black hair color. It is said that it can be seen, and it is considered to be the brightness of judgment standards in the workplace such as banks, hotels, and Japanese airlines. The level called fashionable dyeing of the present invention is aimed at 8 to 10 levels with further increased brightness, and the brightness of 11 levels or higher is in the oxidative hair dye range as a permanent hair dye. Therefore, in the examples described later, a hair coloring level scale sold by the Japan Hair Color Association (JHCA) was purchased, and hair was measured using a spectral colorimeter (manufactured by Nippon Denshoku Industries Co., Ltd., model number: SD 6000). The brightness of the bundle was measured and quantified. In addition, when two colors of blue and red scarlet are dyed on each bleached hair bundle and measured using a spectrocolorimeter, the measured value of lightness (L*) is 0.8% with a scarlet dye content of 0.8% It was found to be 19.79, with a blue dye loading of 0.8% and a lightness (L*) measurement of 19.12, corresponding to 9 levels. From this point of view, the desired amount can be determined for the final desired lightness.

In the past, gray hair was dyed exclusively by darkening the pigment with a composition containing 1 to 3% by weight of a basic dye. In other words, there is no such thing as black in basic dyes, and blackish finish is achieved by deepening brown or deepening blue. This time, as a result of examining whether basic dyes can be applied to healthy hair as well, we found that by blending sodium hydroxymethanesulfinate and thioglycerin (3-mercapto-1,2-propanediol), the dye can be applied to the inside of the hair. can be penetrated and finished with a deeper blackness, and surprisingly, even if the amount of the existing pigment is reduced to 30 to 50 times less than 0.5% by mass, The present inventors have found that the design color and the like can be enjoyed by going through the decolorization process.

For example, since the amount of pigment added is reduced, only the gray hair part is dyed and the dyeing result is uneven for those who have more than 10% gray hair. The present invention can preferably be used for healthy hair, and using a destaining agent (lightener or powder bleaching agent) on healthy hair, for example, the hair coloring level scale sold by the Japan Hair Color Association It is possible to have the effect of enjoying "design color" and "fashionable dyeing" by making the hair with a color tone raised to 9 to 11 levels.

In the present invention, at least one selected from the group consisting of thioglycolic acid, cysteine, 3-mercapto-1,2-propanediol, cysteamine, derivatives and salts thereof, and/or sodium hydroxymethanesulfinate The reason for this is that by containing these components, it is possible to deeply penetrate the components such as dyes into the hair, so that even a small amount of dye can sufficiently achieve hair color, and the dye can be used for a long time. This is because it is possible to maintain the effect. In the present invention, among thioglycolic acid, cysteine, 3-mercapto-1,2-propanediol, cysteamine, derivatives and salts thereof, and/or sodium hydroxymethanesulfinate, from the viewpoint of odor and crystal precipitation, Preferably 3-mercapto-1,2-propanediol and/or sodium hydroxymethanesulfinate can be used.

In addition, in the present invention, an alkali agent is not essential, and even in a neutral region, there is an excellent effect of promoting dye penetration into the hair. From the viewpoint of facilitating the opening of the cuticle and adjusting the pH to a desired value or more, the pH adjuster includes citric acid, phosphoric acid, lactic acid, malic acid, aqueous ammonia, ammonium hydrogen carbonate, ammonium carbonate, potassium hydroxide, water. At least one selected from sodium oxide, monoethanolamine, ammonium phosphate, sodium citrate, ammonium citrate, sodium lactate, potassium phosphate, and sodium phosphate can be used. From the standpoint of being weakly alkaline and less likely to remain on the hair, preferred examples of the pH adjuster include ammonium hydrogencarbonate and sodium hydrogencarbonate.

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

From the standpoint 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 5 to 11. 6. Can be adjusted from 8 to 10.

In a preferred embodiment of the hair coloring agent composition applicable to the present invention, the amino acid is at least one selected from cysteine, arginine, lysine, histidine and salts thereof. In addition, the amount of the amino acid is not particularly limited, but from the viewpoint of maintaining the moisture retention and flexibility of the hair, it 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. , 0.01 to 0.3 mass %, more preferably 0.02 to 0.2 mass %.

In a preferred embodiment of the hair coloring agent composition applicable to the present invention, the basic dye is a basic blue 3 (basic blue 3) 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), 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 brown 16 (basic brown 16), or basic brown 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). In addition, the amount of the basic dye is not particularly limited, but from the viewpoint of the design color, it is 0.005 to 0.5% by mass, more preferably 0.01 to 0.5% by mass, based on the total amount of the composition. 0.45 mass %, more preferably 0.05 to 0.4 mass %.

In a preferred embodiment of the hair coloring agent composition applicable to the present invention, the HC dyes have the INCI name of HC blue 2 (HC blue 2), HC 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), 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). . The amount of the HC dye is not particularly limited, but from the viewpoint of the design color, it is preferably 0.005 to 0.5% by mass, more preferably 0.01, based on the total amount of the composition. It can be up to 0.45% by mass, more preferably 0.05 to 0.4% by mass.

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 of the hair. characterized by being In a preferred embodiment of the hair coloring agent composition of the present invention, the quaternary ammonium salt is a liquid alkyltrimethylammonium chloride, stearyltrimethylammonium chloride, or stearyltrimethylammonium bromide. In a preferred embodiment, the tertiary amine is stearic acid dimethylaminopropylamide, stearic acid diethylaminoethylamide, or behenamidopropyldimethylamine. In addition, the amount of the cationic surfactant is not particularly limited, but from the viewpoint of improving the hair dyeing power of the basic dye, it is preferably 0.01 to 10% by mass, based on the total amount of the composition. It is 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 thickening agents, wetting agents, oil agents, 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 thickening agents include hydroxyethyl cellulose, xanthan gum, polyethylene glycol, and the like, from the viewpoint of product stability. In addition, the amount of the thickening agent is not particularly limited, but from the viewpoint of improving the stability of the product, it is preferably 0.05 to 0.8% by mass, more preferably 0 .1 to 0.5% by mass, more preferably 0.2 to 0.4% by mass.

Wetting agents include glycerin, diglycerin, and 1,3-butylene glycol. Although the amount of the wetting agent is not particularly limited, it is preferably 0.1 to 15 mass %, more preferably 0.1 to 15 mass %, more preferably 0.1 to 15 mass %, based on 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 oil agents include fats and oils, waxes, hydrocarbons, alkylglyceryl ethers, esters, silicones, and higher alcohols. In addition, the amount of the oil agent is not particularly limited, but from the viewpoint of preventing drying during the application standing time and the stability of the product, it is preferably 1 to 30% by mass, more preferably 2 to 20% by mass, further preferably 2 to 20% by mass. can be 3 to 15% by mass.

Moreover, the hair coloring agent applicable to the present invention is characterized by including the hair coloring agent composition applicable to the present invention described above. If desired or depending on the use of the hair coloring agent, the hair coloring agent composition applicable to the present invention can be appropriately included in the hair coloring agent.

Examples of hair cosmetic compositions and hair cosmetics applicable to the present invention are as follows.

A hair cosmetic composition applicable to the present invention is characterized by containing an alkaline agent, an amino acid, a higher alcohol having 12 to 22 carbon atoms, a surfactant, and a thickener. The addition of an alkaline agent is not essential, but it is possible to open the cuticle by adding an alkaline agent. That is, in conventional hair coloring, etc., the cuticle and the cortex near the surface of the hair are dyed, and in some cases it is not possible to achieve sufficiently long-lasting hair color. , it is possible to open the cuticle, and thus it has the advantageous effect of achieving a long-lasting hair color.

That is, conventionally, basic dyes and HC dyes are used to dye cuticles and cortex near the surface. It has been found by the inventors that it is possible to dye with dyes and HC dyes.

From the viewpoint of efficiently opening the cuticle and satisfactorily exhibiting the swelling effect, the pH value of the hair cosmetic composition is preferably 3.5 or higher, more preferably 5 to 11, and still more preferably. 6. Can be adjusted from 8 to 10. Although the amount of the alkali agent is not particularly limited, it is preferably 0.1 to 3% by mass based on the total amount of the composition from the viewpoint of efficiently opening the cuticle and satisfactorily exhibiting the swelling effect. can do.

In addition, the amount of the amino acid is not particularly limited, but from the viewpoint of maintaining the moisture retention and flexibility of the hair, it 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. , 0.01 to 0.3 mass %, more preferably 0.02 to 0.2 mass %.

In the hair cosmetic composition applicable to the present invention, the higher alcohol having 12 to 22 carbon atoms is not particularly limited. , cetyl alcohol, lauryl alcohol, myristyl alcohol, cetostearyl alcohol, stearyl alcohol, behenyl alcohol and the like.

In addition, the amount of higher alcohols having 12 to 22 carbon atoms is not particularly limited, but from the viewpoint of imparting smoothness to hair, improving emulsification stability and adjusting viscosity, the total amount of the composition is It is preferably 0.1 to 5.0% by mass, more preferably 0.1 to 3.0% by mass, still more preferably 0.2 to 2.0% by mass.

In a preferred embodiment, the alkaline agent is not particularly limited, but includes, for example, at least one selected from aqueous ammonia, ammonium carbonate, sodium carbonate, ethanolamines, ammonium hydrogencarbonate, and arginine. 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 are non-volatile and have little odor, but may leave a large amount of residue on the hair and damage the hair. Also, arginine has a high affinity with hair, but its action as an alkaline agent is weak and its reaction is mild. Ammonia water is volatile and has a pungent odor, but it is characterized by a short reaction time and little residue on the hair. From this point of view, the alkaline agent is preferably aqueous ammonia.

In a preferred embodiment, the amino acid is at least one selected from cysteine, arginine, lysine, and/or histidine, and salts thereof. It has been reported that arginine and histidine in the interior of hair decrease with aging. It is possible for the hydrochloride to permeate the hair and exert a hair repair effect.

A hair cosmetic composition applicable to the present invention may contain a surfactant and a thickener. These 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.

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 cuticles.

After hair coloring containing the hair cosmetic composition applicable to the present invention, it is also possible to apply a cuticle care agent containing sodium bromate, for example, in order to tighten cuticles. It is also possible to delay the color fading by dyeing the HC dye, which easily loses color, inside the hair.

Moreover, the hair cosmetics applicable to this invention are characterized by including the said hair cosmetics composition.

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

In the present invention, a bleaching step is carried out before the following step of applying (A) a hair coloring agent and (B) a hair cosmetic. That is, as described above, unless the hair coloring agent composition is applied directly to healthy hair using thioglycolic acid or the like, which has the above-described hair penetrating action, unless it has been subjected to a bleaching treatment, the hair color will be black. This is because there is little change in the hair of the user, and there is a possibility that the design color cannot be enjoyed. Regarding the step of decolorizing, it is possible to decolorize by leaving it at room temperature for about 5 to 30 minutes while checking the degree of decolorization using a cream type or powder type decolorant. Thereafter, the chemical solution can be removed with water or lukewarm water, and then dried using shampoo and towel dry or a hair dryer.

In the present invention, it is possible to apply a mixture of the above-mentioned hair coloring agents and hair cosmetics in a predetermined ratio. The reason why the two are mixed is that the present inventors have found that the use of a mixture of the two results in a deeper dyeing and a longer lasting color compared to the use of the two alone. It is sufficient to mix both, and the predetermined ratio is not particularly limited, but in a preferred embodiment, the blending ratio for mixing the (A) hair coloring agent and the (B) hair cosmetic is B)=1 to 20. That is, from the viewpoint of hair dyeing power, the blending ratio of the hair coloring agent and the hair cosmetic is preferably 1 to 20:1 by weight, more preferably 5 to 15:1 by weight, and still more preferably 8. A weight ratio of ˜12:1 can be achieved.

Further, in the present invention, a predetermined time can be provided after the application from the viewpoint of efficiently opening the cuticle, satisfactorily exhibiting the swelling effect, and allowing the dyeing to proceed. In a preferred embodiment of the hair coloring method of the present invention, in the step of providing a predetermined time after application, the hair is heated from the viewpoint of enhancing penetration dyeing power. The heating time is also not particularly limited as desired, but from the viewpoint of efficient hair dyeing, it can be 1 to 60 minutes, preferably 5 to 40 minutes. From the viewpoint of treatment process time, the temperature may be raised to around 40° C. in about 10 minutes (about 10 minutes or longer) and maintained for about 30 minutes. Also, in a preferred embodiment of the hair coloring method of the present invention, the application area may be covered with plastic wrap and warmed using a hair dryer heat cap between application and the time the hair is left on.

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

A preferred embodiment of the hair coloring method of the present invention may further include a step of applying a cuticle care agent. For example, in a preferred embodiment, after mixing and applying the hair cosmetic and the hair coloring agent, at least one selected from sodium bromate and hydrogen peroxide, and a second cationic surfactant. , a second pH adjuster, and a step of applying a cuticle care agent. As the second pH adjuster, an acidic pH adjuster can be blended. In addition, from the viewpoint of restoring healthy hair (isoelectric pH 4.5 to 5.5), pH adjusters include organic acids such as citric acid, phosphoric acid, phytic acid, lactic acid, and malic acid, and glutamic acid. and acidic amino acids such as

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. As for the alkaline agent, the description of the hair cosmetic and the like applicable to the present invention can be referred to.

In a preferred embodiment of the hair coloring method of the present invention, the first or second amino acid is at least one selected from cysteine, arginine, lysine, histidine and salts thereof. . As for the first or second amino acid, the description of the hair cosmetic, hair coloring agent, etc. applicable to the present invention can be referred to.

Moreover, in a preferred embodiment of the hair coloring method of the present invention, further application of a shampoo may be included. When a shampoo is applied to the hair, it may be applied before hair cosmetics from the viewpoint of removing hindrance factors such as hair styling agents and sebum. In this case, as the shampoo agent, it is preferable to use Brilliant Shampoo, Brilliant Black, Applecell Shampoo Premium, Nano Supplement Cleansing Shampoo, etc. (manufacturer of these products: Sunny Place Co., Ltd.).

A shampoo may also be applied after coloring. In this case, the pH of the shampoo is preferably weakly acidic. As the shampoo agent, it is preferable to use Shining Shampoo or Applecell Shampoo Premium (manufactured and sold by Sunny Place Co., Ltd. shampoo agent).

In a preferred embodiment of the hair coloring method of the present invention, at least one of the hair coloring agent, the hair cosmetic, and the cuticle care agent may further contain an antibody production inhibitor. Antibody production inhibitors include pomegranate seed extracts, mushrooms belonging to the genus Agaricus, extracts of willow mint, edelweiss, etc., from the viewpoint of prevention and improvement of allergic diseases.

For example, the case where pomegranate seed extract is used as an antibody production inhibitor is explained as follows. Pomegranate seed extract is an extract derived from pomegranate seeds. The pomegranate seed extract applicable to the present invention includes all pomegranate seed extracts as long as they are derived from pomegranate seeds.

In a preferred embodiment, the pomegranate seed extract contains punicic acid or ellagic acid. A pomegranate seed extract can be obtained, for example, by the following method. First, a pulverized material obtained by pulverizing 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. Characterized by the obtained For example, shake extraction can be performed. In the shaking extraction, for example, extraction can be performed in a low temperature room such as about 4° C. while being set in a rotator and rotated.

More specifically, first prepare the pomegranate seeds. Pomegranate seeds are washed and dried as needed. Thorough drying is preferred. This is for the purpose of uniform pulverization later.

Then crush the pomegranate seeds. The method of pulverization is not particularly limited, and known pulverizers such as ball mills, hammer mills, roller mills, rod mills, sample mills, stamp mills, disintegrators, mortars, and blenders with cooling devices can be used. Since it is possible that the pomegranate seed composition is decomposed due to the heat generated during the pulverization, the pulverization can be repeated several times for several seconds.

Next, after pulverizing the pomegranate seeds to obtain a pulverized product, the pulverized product is immersed in various solvents. The solvent in this case is not particularly limited, and a suitable solvent can be selected according to the desired effect. A preferred embodiment of the method for producing a pomegranate seed extract of the present invention is characterized in that the solvent is at least one selected from the group consisting of ethanol, methanol, hexane and water. Examples of solvents include polar and nonpolar solvents such as ethanol, methanol, water, hexane, ethyl acetate, chloroform, and acetone. Methanol, ethanol, water and the like can be mentioned preferably.

Immersion can be performed under gentle agitation. Various solutions are obtained by immersing the pulverized material in various solvents. Various solutions may be stirred depending on the state of the solution, and depending on the situation, the solution may be left as it is. Stirring is not particularly limited, but can be continued for 10 hours to 48 hours, preferably about one day (24 hours).

After that, the pomegranate seed extract can be obtained by fractionating the supernatant. If necessary, evaporate the supernatant to dryness. Evaporation to dryness can be carried out using an evaporator on a warm 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 properties by extracting the pomegranate seeds with solvents having different polarities. Therefore, the types and contents 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 agents and dirt.
2) Perform decolorization by a conventional method. This bleaching step facilitates the application of the post-bleaching hair coloring agent, making it possible to achieve a design color.
3) A mixture of a post-bleaching hair coloring agent (containing a hair dyeing component) and a hair cosmetic (containing a basic cuticle swelling agent) applicable to the present invention is mixed at a predetermined ratio and applied to the hair with a brush.
4) Cover the applied hair with plastic wrap, heat with a hair dryer or heat cap, and leave for about 30 minutes.
5) After 4), if necessary, apply a sufficient amount of cuticle care agent to the hair and leave it on for about 6 minutes.
6) After 5), wash your hair with warm water and shampoo.
7) After towel drying, dry the hair with a hair dryer.

As described above, conventionally, a relatively large amount of a hair coloring agent composition + a hair cosmetic containing an alkaline agent or the like is mixed with a subject with gray hair, applied, and then heated or left unheated. After that, if necessary, a cuticle care agent was applied, and the hair was washed and finished (leave for about 10 to 30 minutes).

On the other hand, this time, in the present invention, for subjects with black healthy hair, after lightening the hair in the bleaching process, hair cosmetics containing about 1/30 of the conventional amount of the composition + alkaline agent etc. are applied. After mixing, applying, and leaving with or without heating, if necessary, apply a cuticle care agent, wash and finish the hair (leave for about 10 to 30 minutes) to apply the design color. With a small amount of dye, it became possible to enjoy.

Examples of hair coloring agents and cuticle care agents suitable for the hair coloring method of the present invention are described below, but the present invention should not be construed as being limited to the following examples.

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

As for the alkaline agent (pH adjuster), in the present example, ammonium hydrogen carbonate was used as an example and tested from the viewpoint that it is weakly alkaline and does not easily cause skin irritation.

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 abundantly contained in the hair, and L-cysteine and its salts keep the hair moisturized and flexible. I tried blending for the purpose. Representative basic amino acids include L-arginine, L-lysine, and L-histidine, and these are known to flow out when damaged. % has been found to be preferable.

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

The adjustment method is as follows.

Adjustment method:
1. Warm the aqueous phase of Table 1 to 75-77° C. with stirring.
2. Stir while heating the oil phase in Table 1 to 75-79° C. to homogenize.
3. Add the dye to the water phase heated to 75-77°C and homogenize, add the oil phase to emulsify, and stir until uniform.
4. The contents are slowly cooled, and when the temperature reaches 43°C or below, the antiseptic, refreshing ingredients, anti-inflammatory ingredients, and amino acids are added, stirred until uniform, and cooled to 32°C or below.

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

Further, in Table 1, the same test was conducted when "thioglycerin" was changed to "sodium oxymethylene sulfoxylate" (manufacturer: Tokyo Kasei Kogyo Co., Ltd., 0.5% of the compounding amount).

In this way, a hair coloring agent applicable to the present invention was prepared, and a color fading test was performed on hair tresses.

Conventionally, when a hair coloring agent that does not contain paraphenylenediamine is applied and left to stand, the base color is a basic dye or HC dye, which is said to be safer than an oxidation dye, but the hair is dyed. However, it has a drawback that the color does not last long after dyeing and that the color tends to fade due to repeated shampooing. In contrast to conventional hair coloring agents, the hair coloring agent applied to the present invention not only facilitates the penetration of the base color, but also does not contain acid dyes, so there is no need to worry about adhesion to the scalp from the nascent part to the tip of the hair. It was found that up to

As described above, the hair coloring agent, etc., applied to the present invention can be compared with conventional hair coloring and hair manicures in performing hair dyeing. 2) When a rash occurs on the scalp, the rash is dyed and is difficult to remove (conventional hair manicure). It was found to provide a hair cosmetic having better color retention and penetration and dyeing power. In other words, it was found that the present invention also provided safety in addition to color durability.

Next, hair cosmetics applicable to the present invention were prepared.

As for the alkaline agent, ammonia water, ammonium carbonate, sodium carbonate, ethanolamines such as mono-, di-, and tri-ethanolamine, ammonium hydrogencarbonate, arginine, and the like can be considered. However, since ethanolamines such as monoethanolamine are non-volatile, they have little odor, but they remain highly on the hair and may damage the hair. Also, arginine has a high affinity with hair, but its action as an alkaline agent is weak and its reaction is mild. Ammonia water is volatile and has a pungent odor, but 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 abundantly contained in the hair, and L-cysteine and its salts keep the hair moisturized and flexible. I tried blending for the purpose. Representative basic amino acids include L-arginine, L-lysine, and L-histidine, and these are known to flow out of hair upon damage. % by weight has been found to be preferred.

Table 2 shows examples of ingredients of the hair cosmetic composition in one embodiment of the present invention.

Table 3 shows adjustment examples regarding component examples of hair cosmetics in one embodiment of the present invention.

The adjustment method is as follows.
1. After confirming that the amino acids are dissolved in the purified water of phase A in Table 3, the alkaline agent is uniformly mixed.
2. Next, while stirring Phase A in Table 3, Phase B in Table 3 is added and mixed uniformly.
3. Add Phase C of 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.)
pH meter electrode: Model 9615 (Horiba, Ltd.)

Table 4 shows examples of ingredients of the cuticle care agent in one embodiment of the present invention. A cuticle care agent includes an action to improve the state of the cuticle, such as trimming and tightening the cuticle. In other words, it is not limited to a trimming or tightening action.

Table 5 shows an example of a method for adjusting 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。

A method for preparing a cuticle care agent applicable to the present invention is as follows.
Adjustment method:
1. The remaining ingredients are uniformly mixed with the purified water of Phase A in Table 5.
2. While stirring Phase A of Table 5, Phase B of Table 5 is added and mixed uniformly.
3. Add Phase C of 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.)
pH meter electrode: Model 9615 (Horiba, Ltd.)

Next, examples based on the present invention will be described.
Example 1
The penetration of main basic dyes applicable to the present invention was compared. Commercially available 100% untreated gray hair (product number: BS-C, manufactured by Beaulux) of 30 cm in length was divided into three equal parts and used as hair samples to be dyed. Basic Red 51, Basic Brown 16 and 17 were obtained by dissolving 0.2% of the dye in purified water, adjusting the pH to alkaline using 25% ammonia water (manufactured by Wako Pure Chemical Industries, Ltd.), and converting 3-mercapto thioglycerin. 0%, 1% and 3% solutions of -1,2-propanediol (manufactured by Wako Pure Chemical Industries, Ltd.) were 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 may precipitate in the solution if the pH is too high. For Basic Blue 75, 77, 99, Basic Violet 2, and Basic Yellow 57, an amidobetaine-type double-sided active agent, coconut oil fatty acid amidopropylbetaine liquid (product number: Softazolin CPB-R, Kawaken Fine Chemicals Co., Ltd.) is added to increase the solubility of the dye. 0.7% of the dye is dissolved in 5.0% (manufactured by Co., Ltd.), purified water is added, and the pH is adjusted to alkaline using 25% ammonia water (manufactured by Wako Pure Chemical Industries, Ltd.), and 3-mercapto-1 0%, 1% and 3% solutions of ,2-propanediol were prepared. A hair sample obtained by dividing one white hair into three equal parts is immersed in 0%, 1%, and 3% solutions of 3-mercapto-1,2-propanediol of each dye, and left for 30 minutes using a 40°C constant temperature bath. dyed. After the above hair sample was freeze-embedded using PVA resin, 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, 3-mercapto-1,2-propanediol at 3% penetrates the dye into the hair sample most deeply (range from the outer circumference of the cross section where the color is darker). is the largest). Especially in the case of the Basic Brown 16 and Basic Blue 77 dyes, the good penetration was more evident.

Example 2
Using the dyes of Basic Brown 16 and Basic Blue 77, which had good permeation, 100% untreated hair (product number: BS-C, manufactured by Beaulux Co., Ltd.) was treated at a constant temperature of 40 ° C according to the following formulation example (Table 6). The hair was dyed dark brown by leaving it for 30 minutes using a bath. Table 6 shows component examples and formulation examples.

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結果、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良好な観察結果が得られた。すなわち、ヒドロキシメタンスルフィン酸ナトリウムを用いた場合、チオグリセリンのように染色力が上がるという効果は低いものの、配合しないときよりも配合した方が洗浄回数による色落ちが防げることが判明した。

After the above hair sample was freeze-embedded using PVA resin, a hair cross-section sample (section thickness: 10 μm) was prepared using a microtome. Then, as a sample for microscopic observation, it was placed on a slide glass and compared with a microscope. , 1%, 3%, 5%, 7% and 10% solutions were obtained with good optical microscopy. That is, when sodium hydroxymethanesulfinate is used, although the effect of increasing the dyeing power is low as compared to thioglycerin, it was found that the addition of sodium hydroxymethanesulfinate prevents discoloration due to the number of washes compared to when it is not added.

Example 3
Next, regarding the coefficient of friction, the lower the value, the smoother it is, and the gloss is how much the light irradiated at an angle of 85° is reflected and returned, and the higher the value, the higher the gloss. Effects of the post-bleaching hair color composition and the like of the present invention were investigated.

First, the following bleached hair tresses were prepared using commercially available 100% untreated human black hair tresses (product number: BS-B-A, manufactured by Beaulux) with a length of 10 cm and a weight of 1 g. In addition, 1) a decolorizing agent with a trial formulation, 2) a commercially available cream-type decolorizing agent, and 3) a commercially available powder-type decolorizing agent were used.

1) Prototype decolorizing agent
Agent I:
Strong ammonia water (25%) 9.20%
Ammonium bicarbonate 8.00%
EDTA-4Na 0.10%
Purified water remaining 82.7%

Agent II:
Hydrogen peroxide solution (30%) 20.00%
Purified water remaining 80%

Soak a bundle of 100% commercially available human black hair untreated hair in a 1:1 mixture of agent I and agent II, leave it at 25°C for 30 minutes, remove the chemicals with lukewarm water, and dry with shampoo and a hair dryer. Created bleached hair. It showed 9 levels in the hair coloring level scale sold by the Japan Hair Color Association.

2) Cream-type commercially available decolorizer
Agent I: "Fijore BL Color Lightener (manufactured and sold by Shisei Chemical Co., Ltd.)" and Agent II: 6% hydrogen peroxide on the market were mixed at a ratio of 1:1. It was applied to a bundle and allowed to stand at 25°C for 30 minutes, after which the chemical solution was removed with lukewarm water and dried with shampoo and a hair dryer. This process was repeated 5 times to produce bleached hair. It showed 11 levels in the hair coloring level scale sold by the Japan Hair Color Association.

3) Powder type commercially available decolorizer
Agent I: "Number 3 BP (manufacturer: Number 3 Co., Ltd.)" and Agent II: 6% hydrogen peroxide on the market were mixed at a ratio of 1:3. After applying the product and leaving it at 25°C for 30 minutes, the chemical solution was removed with lukewarm water, and the bleached hair was prepared by shampooing and drying with a hair dryer, showing a level of 10 on the hair coloring level scale sold by the Japan Hair Coloring Association.

For these three types of hair tresses, the hair color agent composition for the fashionable dyeing prescription in Table 1 etc. described above and "Illumina Color TWI-6" (manufactured and sold by Procter & Gamble, Inc.), which is an oxidation hair dye for fashionable dyeing, were applied. Japan Co., Ltd.”, “Nondiamine Helper DF/P-08 Manufacturing and Sales Agency: Estate Chemical Co., Ltd.”, and the dyed hair bundle is subjected to a friction tester (Kato Tech Co., Ltd.), hair gloss meter (Nippon Denshoku Industries Co., Ltd.), and hair damage using a constant temperature dryer (Sanshosha Co., Ltd.). measured by

Sensory evaluation such as "stroking" the texture of hair was measured (average value) as "smoothness" as a coefficient of friction using "KES-SE friction tester (manufactured by Kato Tech Co., Ltd.)". The measurement was performed in a constant temperature and humidity room, and the environmental temperature and humidity for measurement was 20°C/61%RH. Table 7 shows the evaluation results for the coefficient of friction.

Therefore, even after any one of the bleaching steps 1) to 3), the post-bleaching hair color composition and hair coloring agent of the present invention exhibited low values and excellent smoothness. did.

Example 4
Next, the same hair bundle as in Example 3 was measured using a glossiness meter (VG7000) manufactured by Nippon Denshoku Industries Co., Ltd., and the measured values (average values) at an incident angle of 85° are shown below. Table 8 shows the results.

Therefore, the post-bleaching hair color composition and hair coloring agent of the present invention show high numerical values and, in turn, good gloss even after undergoing any one of the bleaching steps 1) to 3). found.

Example 5
The same hair bundle as in Example 3 was heated at 65°C for 40 minutes using a constant temperature dryer (SDN27P) manufactured by Sanshosha. The values (average values) obtained by heating at 180°C for 30 minutes are shown below. Specifically, the moisture content of the hair was measured using an electronic moisture meter (EB-340MOC; manufactured by Shimadzu Corporation) in accordance with the moisture loss measurement method. Table 9 shows the results.

As a result of Table 9, the primary evaporated water is assumed to be at the temperature of the hair dryer. It can be seen from the fact that the product of the present invention provides more moisture to the hair than the other two products.

In general, fashionable hair colors are based on oxidation hair dyes that develop colors with oxidation dyes and oxidizing agents such as hydrogen peroxide, but the present invention uses basic dyes that do not need to be reacted with oxidizing agents, etc. When hair is dyed in a two-step process of adjusting the amount of pigment, bleaching and dyeing, it is called "design color". It has become possible to change the brightness of a part to create a three-dimensional effect, or to dye a part to create a point.

Moreover, from the above results, it was found that when thioglycerin or the like is blended, it is possible to dye hair with good fastness properties without raising the pH or heating. It was also found that adding thioglycerin or the like and increasing the temperature and pH are more effective. In the case of the dyes Basic Blue 99 and Basic Brown 16, hair dyeing with better fastness properties is possible as the pH is increased to around pH 10, while in the case of Basic Blue 77, the pH is increased to 8 or more. It was found that when the dye was raised, the pigment was destroyed, the color changed, and the hair tended to be weakly dyed.

As described above, it has been found that the addition of thioglycerin or the like in the coloring of hair or the like facilitates the penetration of the dye into the hair.

According to the present invention, a coloring method that hardly damages hair, can reduce skin disorders, and allows dyes to easily enter the hair is easy to spread and has high industrial utility value.

Claims (10)

A step of bleaching before the step of applying the following (A) hair coloring agent and (B) hair cosmetic;
(A) thioglycolic acid , 3-mercapto-1,2-propanediol, cysteamine, and at least one selected from the group consisting of 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 oily agent, a first pH adjusting agent, and a wetting agent, wherein the hair coloring agent has a pH of 6.8 to 10 . a hair coloring agent that is
(B) a hair cosmetic containing at least an alkaline agent, a first amino acid, a higher alcohol having 12 to 22 carbon atoms, a surfactant, and a thickener;
A step of applying a mixture of at a predetermined ratio;
and providing a predetermined time after the application. 2. The hair coloring method according to claim 1, wherein the blending amount of said basic dye or HC dye is 0.5% by weight or less with respect to the total amount of said hair coloring agent. 3. The hair coloring method according to claim 1, further comprising the step of applying a cuticle care agent after said application. 4. 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. 5. The method according to claim 3 or 4, comprising the step of leaving the cuticle care agent to stand for a certain period of time after applying the cuticle care agent. The composition according to any one of claims 1 to 5, wherein (A) the hair coloring agent and (B) the hair cosmetic are mixed at a mixing ratio of (A)/(B) = 1 to 20. 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 said first or second amino acid is at least one selected from cysteine, arginine, lysine, histidine, and salts thereof. 4. The method according to claim 3 , wherein at least one of said hair coloring agent, said hair cosmetic, and said 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 application.

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