JPH0656638A - Hair dye and hair dyeing method - Google Patents

Abstract

PURPOSE:To provide an ylidoid hair-dye having excellent hair-dyeing property and safety, enabling the dyeing of hair in a short time and causing remarkably suppressed tinting of skin. CONSTITUTION:The two-pack hair-dye is composed of the 1st agent consisting of an ylidoid compound and the 2nd agent consisting of an ylidoid-amino acid- reactional product. The ylidoid compound is an ylidoid glycoside or its aglycon and the compounds may be natural substance obtained from the plant of the family Rubiaceae, Euphorbiaceae, Gentianaceae, etc., or synthetic substance. Examples of the natural substance are asperuloside, geniposide, geniposidic acid and aucubin and examples of the aglycon of the ylidoid glycoside of the natural substance are genipin which is the non-sugar part of geniposide, aucubigenin of aucubin and eucommiol. Hair is dyed by applying the ylidoid compound to the hair and then applying the ylidoid-amino acid-reactional product.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hair dye and a hair dyeing method, and more specifically, it has been known in the prior art that the compound contains an iridoid compound and an iridoid-amino acid reaction product. The present invention relates to a hair dye and a hair dyeing method capable of dramatically improving the hair dyeing effect of the hair dye by an iridoid compound and significantly reducing the skin coloring at the time of hair dyeing.

[0002]

2. Description of the Related Art For dyeing gray hair, that is, for dyeing hair,
Henna, chamomile, walnut in Europe,
In Asia, plant dyeing and mineral hair dyeing such as sumi lotus are well known. Since Monnet and others commercialized a completed product called hair dye in the 1880s,
In recent years, along with the diversification of fashion, various types of hair dyes have been required according to the purpose, such as fashionable dyeing for dyeing hair in a desired color tone, and easy and acidic hair dyeing with less damage to hair.

Known hair dyeing substances are plant components such as (naphtho) quinones and (polyhydric) phenols, mineral dyes, tar dyes and oxidative dyes of phenylene amines. Depending on the degree of hair dyeing, temporary, semi-permanent, permanent or hair dye, hair dye, acid hair or powder, liquid, cream, one-part formula, depending on the formulation, 2
It is classified into various types such as drug formulas, pharmaceuticals, and quasi-drugs.

In Japan, since the introduction of oxidative dyes in the late Meiji era, hair dyeing has often been an oxidative dye. Oxidative dyes have been accepted by many people because they have less hair coloring compared to other hair dyeing substances and have excellent fastness. However, it is a well-known fact that the safety of imine compounds generated during the oxidation process of phenylene amines has been questioned for a long time. Regarding the fear of skin sensitization, irritation, carcinogenicity, etc. of phenylene amines, although the rapid subsequent reaction of imine intermediates and the removal method have been devised and improved, it is basically safe. It is hard to say that it is a hair dyeing substance.

Oxidative polymerization of phenylene amines is indispensable for the hair dyeing mechanism, and damage and decolorization of hair and skin by an oxidizing agent added to accelerate this oxidation process are
Along with the danger of phenylene amines, it can be said that oxidation hair dye has a major drawback. In recent years, safety, damage to hair and skin, odor, etc. have been improved to a level unprecedented by using dosage forms, treatment methods, devising oxidants, and non-alkali treatment. However, as I have said many times, the current oxidation dyes cannot avoid the formation of imines due to natural dyeing due to the hair coloring mechanism that is caused by the oxidative polymerization of phenylene amines. It also leads to a great decrease in the property, and in the end, it is recognized that safety and hair dyeing are in conflict with each other, and they are incompatible.

[0006] Further, including the washing of hair takes about 20 minutes, and the laboriousness of the operation, in which attention must be paid to coloring of the clothes, is not keeping up with the modern lifestyle. Therefore, it is well known that a hair dyeing method using a simple treatment such as tar dye has recently been highlighted again. However, tar-based hair dyes
Compared with oxidative dyes, it has a remarkably lacking hair dyeing property, and also has a drawback that it is more colored than the hair and the skin is poor in fastness. Under such circumstances surrounding hair dyes, very recently, hair dyes completely different from the conventional hair dyeing mechanism have been proposed (Japanese Patent Laid-Open No. HEI 3).
-220115, JP-A-3-227913).

[0007] This focuses on the fact that iridoid, which is abundant in plants such as gardenia, reacts with primary amines to develop color, which is an epoch-making hair dyeing attempt to chemically bond hair with a hair dyeing substance. It is an agent. Gardenia is referred to as the crude drug name sansisi in Chinese medicine, and has been widely used in fields such as food as a sedative, anti-inflammatory, antipyretic, choleretic agent, and crocin in gardenia as a natural plant pigment. Hair dyeing with this iridoid is excellent in safety and has a remarkable effect on hair dyeability, especially fastness, as can be inferred from the chemical reaction mechanism.

[0008]

Problems to be Solved by the Invention As described above, the iridoid hair dye is far superior in safety and hair dyeing property to conventional hair dyes (materials) and is a hair dye that can be expected in the future. .
However, iridoid hair dye is a primary amine (free amino acid, N-terminal lysine, etc.) that can react with iridoid in hair.
Due to the low degree of freedom between the iridoid and the iridoid-amino acid reaction product in which the amino acid in the hair is bonded to the hair in a 1: 1 relationship with the iridoid and the hair, the hair does not polymerize easily at low temperatures, and it is difficult to dye hair. There was still room for improvement, such as skin coloring due to the inability to selectively dye. Against this background, a hair dyeing method has been proposed which utilizes the good permeability of an oxidative dye into hair and the reaction color development of iridoid with a primary amine (JP-A-3-219003).

That is, first, the phenylene amines are quickly attached to the hair and penetrated, and then the iridoid is applied to the hair so that the iridoid and the oxidative dye are reacted and colored. As a result, iridoid reacts with phenyleneamines, which are more reactive than amino acids in hair, and as a result, hair dyeability is improved. According to this method, hair can be dyed without oxidation of phenylene amines (formation of imine form), which is significantly safer than conventional oxidative hair dyes, and the previously proposed iridoid hair dye. Compared with this, it has excellent hair dyeing properties.

However, the fact is that phenylene amine is used, and the adverse effect of natural oxidation cannot be completely wiped out even if the phenylene amines are not artificially oxidized. Although the iridoid hair dye was intended to wipe away conventional hair dyes (materials) such as oxidative hair dyes, it had both a hair dyeing property and safety, but further shortening of hair dyeing time and dyeing There has been a demand for reducing skin coloration when hair is applied.

[0011]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a hair dye and a hair dyeing method, which are excellent in hair dyeing property and safety, can be dyed in a short time, and the problem of skin coloring is significantly suppressed. To do.

[0012]

[Means for Solving the Problems] The inventors of the present invention have conducted extensive studies to solve the problems of the iridoid hair dye, and as a result, applied iridoid to hair and, after binding, used an iridoid-amino acid reaction product in combination. By doing so, a means for improving the hair dyeability while maintaining the safety of the conventional iridoid hair dye without using phenyleneamines was found, and the present invention was completed. That is, according to the present invention, there is provided a two-component hair dye comprising one agent comprising an iridoid compound and two agents comprising an iridoid-amino acid reaction product.
Further, according to the present invention, there is provided a hair dyeing method, which comprises applying an iridoid compound to hair in advance and then applying an iridoid-amino acid reaction product.

[0013]

DETAILED DESCRIPTION OF THE INVENTION The technical feature of the present invention is that a low amount of iridoid compound is applied to hair in advance to react with the amino acid in the hair, and then the iridoid-amino acid reaction product is newly added. The reaction coloring mechanism of iridoid and amino acid is described in, for example, JP-B-57-14781,
As known from Japanese Patent Publication No. 63-12499,
It is a compound in which the nitrogen (2) -position of the iridoid is substituted with the nitrogen of the primary amine (monomers) to sequentially polymerize to develop a color. In this case, in the one-to-one reaction (monomer) stage of iridoid and amino acid, the macroscopic color tone is a light color with absorption in the short wavelength region of yellow to red and the monomer is unstable and polymerizes quickly. Will end up.

By polymerizing, the conjugated system is extended and the macroscopic color tone becomes blueish, which has absorption in the long wavelength region and is stabilized. The polymer (polymer) which has undergone the polymerization is proposed as a natural pigment in, for example, Japanese Patent Publication No. 54-13451. Replacing this in the case of hair, it means that the iridoids bonded to the amino acids in the hair in a one-to-one manner are polymerized on the hair to develop color. However, as described above, the degree of freedom of the iridoid bound to the amino acid in the hair is small, and water is indispensable for the polymerization, so that it is difficult to polymerize with the adjacent iridoid bound to the hair amino acid.

That is, in the solution, the iridoids bound to the hair amino acids are easily polymerized and colored, but the iridoids, even if bound to the hair, develop color (hair dyeing) only by applying the iridoid to the hair. It is difficult. Therefore, in the present invention, after applying and binding iridoid to hair, a free iridoid-amino acid reaction product that can freely move without being bound by hair protein chains is separately added together with water, and iridoid bound to hair is added. It is intended to react and develop color.

The iridoid-amino acid reaction product used here is a low polymer such as a monomer or trimer, and is not a polymer conventionally proposed as a colorant or the like. Iridoids do not react with primary amines in a ratio of 1: 1 or more, and for example, the above-mentioned monomers and polymers once have a 1: 1 ratio with amine acids.
The iridoid reacted in (1) never reacts with the amino acid in the hair. That is, the known iridoid-amino acid compound alone is hair or amino acid, for example,
No chemical bond reaction due to replacement of oxygen and nitrogen,
Even if it is used as a hair coloring substance, dyeing on hair, like tar dyes, is ionic electrical with the amino acid of hair,
Only physical dyeing.

However, in the present invention, the iridoid is bound to the hair (amino acid) in advance, and the iridoid-amino acid reaction product is newly added to chemically bond the iridoid to the hair to cause coloration. . That is, in the present invention, it is essential that iridoid is bound to hair in advance.

According to the above method, the hair proposed by the previously proposed iridoid can be dyed more quickly, the iridoid-amino acid reaction product does not react with the skin (amino acid), and the iridoid first applied to the hair is conventionally Law 3
Skin coloring can also be significantly reduced because the concentration is reduced to one-tenth or less.

The iridoid referred to here is Japanese Patent Laid-Open No. 3-22.
As described in Japanese Patent No. 7913, iridoid glycosides or aglycones thereof are applicable. The iridoid glycoside is a compound in which one or more sugar residues are ether-bonded to a monoterpene (iridoid) having a 1-isopropyl-2,3-dimethylcyclopentane skeleton. These compounds may be, for example, natural products obtained from plants such as Akaneaceae, dairy family, ginger family, or may be synthetic products.

Examples of natural products include asperloside, geniposide, geniposide acid, aucbin and the like. Examples of the aglycone include those obtained by hydrolyzing the above-mentioned iridoid glycosides in the plant with an enzyme (for example, β-glucosidase), acid or alkali, and synthetic products derived from mevalonic acid, tryptophan, and the like. Examples of aglycones of iridoid glycosides of natural products include genipin, which is a non-sugar portion of geniposide, and aukubigenin and yukomiol of aukvin.

Examples of the actual hair dyeing method include, but are not limited to, the following methods. However, it is essential to first apply the iridoid compound as one agent to the hair, and then apply the iridoid-amino acid reactant or iridoid and amino acid.

Aglycon on hair once or twice a day,
After application for several days to several weeks, aglycone and amino acid in separate containers are applied once or twice a day for several days to several weeks. A method of applying aglycone to hair in the same manner, and then applying aglycone and an amino acid reaction product in the same manner. A method in which the iridoid glycoside and the enzyme are similarly applied to the hair, and then the aglycone and the amino acid are similarly applied. A method in which aglycone is similarly applied to hair, and then an iridoid glycoside, an enzyme and an amino acid are applied. Although the hair dyeing effect is not inferior or superior, it can be said that the method is preferable in terms of handiness and stability of dosage form.

It is the time to apply two agents after applying one agent.
For example, to apply two agents several hours after applying one agent once a day
This may be repeated several times to several months, or one agent may be applied once to several times a day, and this may be repeated for several days to several weeks, and then two agents may be applied one to several times a day for several days to several times. May be repeated for several weeks. As described above, the method for applying the one agent and the two agents is not limited, but one agent, that is, aglycone (or a glycoside and one having hydrolyzing ability thereof),
It is essential to first apply it to the hair.

The term "amino acid" as used herein refers to a single amino acid compound, a complex thereof, a protein, a protein hydrolyzate, or the like having a primary amine capable of reacting with iridoid, alone or in a mixture. -The enzyme means an enzyme group capable of hydrolyzing a β-linked sugar such as β-glucosidase, or an extract or a culture solution containing them. The (iridoid) aglycone and the amino acid reaction product are those in which the aglycone and the amino acid are bonded in a one-to-one relationship (monomers) or low polymers thereof, and may be purified compounds or include them. It may be an iridoid-amino acid reaction solution (object). The iridoid glycoside and the aglycone may be purified single compounds alone, a mixture, or a plant extract containing them.

The concentration of the iridoid and amino acid in the actual formulation is not particularly limited, but in the formulation of a single iridoid compound alone, a mixture or a plant extract containing them, the iridoid aglycone and the glycoside are included. It is desirable to add 0.05 to 5% as the total amount. In the case of glycoside, the hydrolase is, for example, β-glucosidase (from almonds), the amount of β-glucosidase in the purified product or the contained extract or the culture solution is 0.001 as compared with that of glycoside. It is desirable to add 0.1 to 0.1%. The amount of amino acid is also not particularly limited, and the amino acids can be used alone or in a mixture as long as they do not hinder the formulation stability and use.

[0026]

[Test example]

Hair dyeing and skin coloring test Add about 1% sodium alginate to the following solution, stir it, and apply it to a human head with gray hair to get a viscosity of several poise. (Coloring) Color tone and degree were visually evaluated.

Example 1: 0.5% Genipin (25%
EtOH solution) applied once a day and left as it is.
After repeating for 30 days, 0.5% genipin-3% glycine ethyl ester hydrochloride was reacted at 40 ° C. for 30 minutes (25% EtO 3
H solution) is applied once a day in the same manner and left standing for 7 days. * After the second day, wash the head with warm water and shampoo before applying, and lightly wipe with a towel to apply the test solution. Comparative Example 1: 0.5% Genipin (25% EtOH solution)
Is applied once a day and left for 14 days, which is repeated as in Example 1. Comparative Example 2: 0.5% Genipin-3% Glycine Ethyl Ester Hydrochloride 40 ° C., 30 minutes Reaction solution (25% EtOH solution) was applied once a day and left for 14 days, the same as Example 1. Repeat. (Comparative Example) 3: 0.5% genipin-3% glycine ethyl ester hydrochloride at 40 ° C for 24 hours, reaction solution (25% EtOH
The solution) is applied once a day and left standing for 14 days, which is repeated as in Example 1. (Comparative Example) 4: 0.5% Genipin (25% EtOH solution)
Was applied once a day and left standing for 7 days in the same manner as in Example 1, and then 0.5% genipin-3% glycine ethyl ester hydrochloride at 40 ° C. for 24 hours, and the reaction solution (25% EtOH solution) was added. Application once a day and leaving for 7 days are repeated as in Example 1. (Comparative example) 5: 0.5% genipin (25% EtOH solution) and 0.5% glycine ethyl ester hydrochloride (25% EtOH solution), which were placed in separate containers, were applied simultaneously once a day and left. Is repeated for 14 days as in Example 1. (Comparative Example) 6: 0.5% genipin-3% glycine ethyl ester hydrochloride 40 ° C, 30 minutes reaction solution (25% EtOH solution) was applied once a day and left for 7 days, the same as Example 1. And then 0.5% genipin (25% EtOH solution)
Is applied once a day and left standing for 7 days, which is repeated in the same manner as in Example 1. (Comparative Example) 7: 0.5% Genipin (25% EtOH solution)
Is applied once a day and left for 42 days, which is repeated in the same manner as in Example 1.

[0028]

【result】

When the 1st agent (genipin) and the 2nd agent (genipin-glycine ethyl ester hydrochloride reaction solution) of Example 1 were used in reverse (Comparative Example 6), the hair dyeing property was remarkably lowered. Further, in the conventionally known iridoid hair dyeing method (Comparative Examples 1 and 7), in order to obtain the hair dyeing effect similar to that in Example 1, it is necessary to triple the hair dyeing period, and the conventional method causes skin coloring. Remarkable.

<Prescription example> In the prescription example, the "appropriate amount" means an amount of 100% by weight as a whole. (1) Solvent weight (%) 1 agent Genipin 0.50 Glycerin 5.00 Sorbitol 4.00 Polyoxyl stearate 40 1.55 Ethanol 30.00 Purified water Appropriate amount Mix and stir each component to dissolve them Make solvent. 2 agents Genipin 0.50 Glycine ethyl ester hydrochloride 1.50 Glycerin 5.00 Sorbitol 4.00 Polyoxyl stearate 40 1.55 Ethanol 20.00 Purified water Suitable amount After stirring at 45 ° C for 30 minutes, add ascorbic acid pH
Adjust to 3.5 to 4.0, enclose in a container filled with nitrogen and store at 10 ° C or below

(2) Solvent 1 Agent-1 Geniboside 1.00 Ethanol 35.00 Purified water Appropriate amount Each component is mixed and stirred, and these are dissolved to prepare a solvent. 1 agent-2 β-glucosidase (from almonds) 0.01 Purified water Appropriate amount Each component is mixed and stirred, and these are dissolved to prepare a solvent. 2 agents Genipin 0.50 Glycine ethyl ester hydrochloride 1.50 Glycerin 5.00 Sorbitol 4.00 Polyoxyl stearate 40 1.55 Ethanol 20.00 Purified water Suitable amount After stirring at 45 ° C for 30 minutes, add ascorbic acid pH
Adjust to 3.5 to 4.0, enclose in a container filled with nitrogen and store at 10 ° C or below

(3) Emulsion 1 agent A. 1,3-butylene glycol 4.00 purified water suitable amount B.I. Aukbigenin 0.50 Ethanol 10.00 Polyethylene glycol 400 6.00 Purified water 20.00 A and B are heated and A is added to B to prepare an emulsion. Two agents A. 1,3-butylene glycol 4.00 glycine 0.50 L-arginine 0.50 purified water proper amount B.I. Aukbigenin 0.50 Ethanol 10.00 Polyethylene glycol 400 6.00 Purified water 20.00 A and B are heated to 80 ° C., A is added to B to prepare an emulsion, and immediately thereafter, it is sealed in a container filled with nitrogen, Degassed to 10 ° C
Save below

(4) Emulsion 1 agent A. White petrolatum 2.50 Silicone oil 0.50 Stearyl alcohol 2.20 Sucrose fatty acid ester 5.00 Octyldodecanol 2.20 Squalane 6.30 Jojoba oil 0.20 Polyoxyl stearate 40 2.50 Paratoluenediamine 0.10 B. Purified water Appropriate amount Genipin 0.20 Dipropylene glycol 3.00 Propylene glycol alginate 0.30 Xanthan gum 0.05 A and B are heated and dissolved. A is added to B to produce an emulsion. Two agents A. White petrolatum 2.50 Silicone oil 0.50 Stearyl alcohol 2.20 Sucrose fatty acid ester 5.00 Octyldodecanol 2.20 Squalane 6.30 Jojoba oil 0.20 Polyoxyl stearate 40 2.50 Paratoluenediamine 0.10 B. Purified water qs Genipin 0.20 Cystine 0.20 L-proline 0.30 Dipropylene glycol 3.00 Propylene glycol alginate 0.30 Xanthan gum 0.05 A and B are heated to 80 ° C. and B is added to A. Immediately after making the milky lotion, put it in a container filled with nitrogen and degas it to 10 ° C.
Save below

(5) One Cream A. Purified water proper amount 1,3-butylene glycol 3.00 sorbitol 7.00 genipin 0.10 dl-PCA sodium (50%) 3.00 B.I. Polysorbate 60 2.50 Monostearic acid glyceride 1.50 Cetanol 3.00 Vaseline 5.00 Octyldodecyl myristate 5.00 Octimedodecanol 6.00 Squalane 15.00 A and B are dissolved by heating and A is added to B. In addition, an emulsifying cream is produced. Two agents A. Purified water Appropriate amount Genipin 0.10 Lysine 0.01 Chitosan 0.01 1,3-Butylene glycol 3.00 Sorbitol 7.00 dl-PCA sodium (50%) 3.00 B.I. Polysorbate 60 2.50 Monostearic acid glyceride 1.50 Cetanol 3.00 Vaseline 5.00 Octyldodecyl myristate 5.00 Octimedodecanol 6.00 Squalane 15.00 A and B are heated to 80 ° C., and B is added. Immediately after adding the cream to A to make a cream, put it in a container filled with nitrogen and degas it.
Store below 0 ℃

Claims (2)

[Claims] 1. A two-part hair dye comprising one part consisting of an iridoid compound and two parts consisting of an iridoid-amino acid reaction product. 2. A hair dyeing method comprising applying an iridoid compound to hair in advance and then applying an iridoid-amino acid reaction product.