JPH0660089B2 - Hair dye cosmetics - Google Patents

Description

TECHNICAL FIELD The present invention relates to a hair dye cosmetic containing an iridoid glycoside or a secoiridoid glycoside obtained from a plant as an active ingredient.

(B) Conventional technology Various hair dye cosmetics are used for the purpose of dyeing white hair, white beard, or changing the color of hair, but at present, permanent hair dyeing is mostly done by oxidation dyes. . This is because a low molecular weight colorless dye intermediate (hair dye) such as paraphenylenediamine, N-phenylparaphenylenediamine, toluene-2,5-diamine, and paraaminophenyl penetrates into the fur and then peroxidizes. This is based on the principle that an oxidant such as hydrogen is oxidatively polymerized to make it insoluble and develop color. Due to this reaction, a dye having a large molecular weight is formed, and the formed dye also reacts with amino groups and guanidyl groups in the hair, so it is difficult to seep out of the hair,
The dyeing effect lasts. However, hair dyes are often toxic because they easily bind to proteins, and allergic humans are prone to allergic contact dermatitis.The oxidizing agents used also tend to damage the skin. Requires careful attention and meticulous dyeing technique in terms of safety for human body. In this respect, there has been a demand for a permanent hair dye cosmetic that can be easily applied with a small amount. In addition, in order to compensate for this drawback, a method of reacting tannic acid and a metal to dye the tannin salt to dye it,
It has the drawback of being relatively weak in dyeing properties such as washing hair with detergent and accompanied by metallic luster peculiar to metal salts. Further, as a solvent-type dyeing method, there is a method of dissolving an acid dye in a solvent and dyeing, but the dyeing is not permanent as compared with the oxidation dyeing method.
It has the disadvantage that it must be decolorized in 4 weeks and that a solvent that is not compatible with the skin such as ventil alcohol must be used.

Geniposide, which is contained in the genus Chino of the family Akane, and iridoid glycosides and secoiridoid glycosides, which are contained in plants such as aucvin, which is contained in the Aoki of the Mizuki family, react with primary amines in the presence of β-glucoxidase. However, it is known that it develops a color and forms a pigment, and the pigment formed is safe and is used as a pigment in the fields of food and medicine. (Tetrahedron Letters, pp. 2347-2350 (196
9), JP-A-52-53934, JP-B-61-19234] However, the use of these iridoid glycosides and secoiridoid glycosides for permanent dyeing of hair has not been known at all.

(C) Problems to be Solved by the Invention That is, the inventors of the present invention have hydrolyzed iridoid glycosides and secoiridoid glycosides that exist as components in highly safe natural plants, and the glycosides. The present inventors have found that when they are mixed with a degradable enzyme and applied to human or animal hair having a primary amino group present in the peptide, they exhibit excellent hair dyeing properties, and arrived at the present invention. It is considered that this dyeing property is due to the fact that the glycoside is converted to aglycone by the action of an enzyme to remove a sugar component, which is bound to an amino group of hair to develop a color, which causes hair dyeing.

(D) Means for Solving the Problems Thus, the present invention provides a composition (A) containing at least one of an iridoid glycoside and a secoiridoid glycoside as an active ingredient, and hydrolyzing the glycoside. The present invention provides a hair dye cosmetic composition which comprises a combination with a composition (B) containing an active enzyme as an active ingredient.

The present invention also provides a composition (A) containing at least one of an iridoid glycoside and a secoiridoid glycoside as an active ingredient, and a composition containing an enzyme capable of hydrolyzing the glycoside as an active ingredient. (B) is mixed in advance and applied to the hair, or the composition (A) is applied to the hair and then the composition (B) is applied to dye the hair. It is a thing.

The active ingredient iridoid glycoside used in the present invention is
It is a compound in which one or more sugars (mainly glucose) are bound to a monoterpene having a 1-isopropyl-2,3-dimethylcyclopentane skeleton having a structure such as the formula (1).

The secoiridoid glycoside is an analogue of the iridoid glycoside and has a slightly different cyclic structure, and is a glycoside having a structure such as the formula (2). The main ones of these glycosides are as follows.

(Iridoid glycoside) Aucubin (Aucubin C ₁₅ H ₂₂ O ₉ mp 182 ° C containing plants:
Dogwood family Aoki, plantain family plantain, etc.) Geniposide (Geniposide C ₁₇ H ₂₄ O ₁₀ , mp.163 ° C-containing plants; gardenia gardenia, dogwood family sanshyu, dogwood, etc.) Catalposide (Catalposide C ₂₂ H ₂₆ O ₁₂ , mp 215 ° C.-containing plant: Acalyptaceae, Catalpa family, Rubiaceae gardenia etc.) Loganin (Loganin C ₁₇ H ₂₆ O ₁₀ , mp 222 ° C.-containing plant:
Gentianaceae Mitsuwagashiku, Machinidae Homika etc.) Asperuloside (Asperuloside C ₁₈ H ₂₂ O ₁₁ , mp.129-130)
℃, Containing plants: Rubiaceae, Jaitobana, Yamegara, etc.) Methyldeacetyl Asperulosidate
asperuloside C ₁₇ H ₂₄ O ₁₁ · H ₂ O, mp.129-131 ℃, Containing plant: Gardenia gardenia Geniposidic acid C ₁₆ H ₂₂ O ₁₀ , Rubiaceae Yaitobana Yuzuriha, etc. Gardenoside (Gardenoside C ₁₇ H) Plants containing ₂₄ O ₁₁ :
Gardenia of Rubiaceae, Yuzuriha of Euphorbiaceae, etc.) Pederoside (Paederoside C ₁₈ H ₂₂ O ₁₀ S, Rubiaceae, Yaitobana, etc.) (Sequoiridoid glycoside) Gentiopicroside C ₁₆ H ₂₀ O ₉ , mp 1
Plants containing 91 ℃: Gentianaceae, Gentian, Gentiana, etc. Swertiamarin C ₁₆ H ₂₂ O ₁₂ , mp 110
Plants containing ~ 112 ° C: Gentianaceae, senburi, murasakisen, etc.) These iridoid glycosides or secoiridoid glycosides can be extracted by, for example, extracting plants containing them with water or a hydrophilic organic solvent, and using a known separation method. For example, it can be obtained by separation and purification by a method such as filtration, concentration, chromatography, fractional recrystallization, high performance liquid chromatography, countercurrent partition extraction and the like.

The hair dye cosmetic in the present invention means a cosmetic used for dyeing or discoloring hair such as head hair, beard and body hair.

The hair dye cosmetic composition of the present invention may be in the form of liquid, semi-solid or solid. As liquid cosmetics, hair liquids, permanent wave liquids, hair tonics, hair styling, hair sprays and the like, and bases and additives used therefor can be used. As a semi-solid cosmetic, a hair cream-like form and bases and additives used therefor can be used. As the solid cosmetic, a hair stick-like form and bases and additives used therefor can be used.

The hair dye cosmetic composition of the present invention comprises a composition (A) containing a glycoside as an active ingredient and a composition (B) containing an enzyme as an active ingredient. These two compositions are compatible with each other or It is desirable to have good miscibility. For example, it is preferable that the composition (A) is liquid and the composition (B) is also liquid. However, the composition (A) is made into a solid form such as a tablet or capsule,
It is also possible to make the composition (B) liquid. (However, when this is used for hair, it is used as a solution or suspension by previously mixing both compositions as described below).

A preferred form of the hair dye cosmetic of the present invention is the composition (A).
And the composition (B) are both liquid. In particular, for liquid compositions, the base is water and water-miscible organic solvents (ethanol, propanol, cetyl alcohol, glycerin, ethylene glycol, propylene glycol, pyriethylene glycol, ethylene glycol methyl (or ethyl)). Ether, dimethyl sulfoxide, etc.). In addition, polyvinyl alcohol and carboxymethyl cellulose can also be used as a part of the base material.

As additives, preservatives (butyl p-hydroxybenzoate, butyl p-hydroxybenzoate, dehydroacetic acid, sorbic acid, etc.), fragrances (natural or artificial fragrances), coloring agents, hair restorers (hormones, vitamins, Amino acids, etc., Hair growth agents (Acetylcholine chloride, Pilocarpine chloride, Cantharis tincture, etc.), Moisturizers (glycerin, sorbit), Microbicides (hinokitiol), Cationic surfactants, Oils (olive oil, liquid paraffin, squalane, silicone oil) , Lanolin, etc.) and the like. In addition, in the cosmetic of the present invention, calcium thioglycolate, 1-dodecylazacycloheptan-2-one, hexamethylene lauramide, N-methyl-2-pyrrolidone, sucrose fatty acid ester (particularly palmitic acid or laurin). Acid ester), dimethylsulfoxide, and a nonionic surfactant (polyoxyethylene glycol oleate, sorbitan monostearate, etc.) are preferably added. It is considered that these compounds act to promote absorption of glycosides into the hair, which is the active ingredient of the present invention. The amount used is 0.05 to 10% (weight) in the total cosmetics. In addition, small amounts of proteolytic enzymes (e.g.
Addition of 05 to 3% (by weight) is effective in promoting hair dyeing and increasing color depth.

The content of the iridoid glycoside or the secoiridoid glycoside in the composition (A) is generally 0.05 to 8% (weight), for example, 1% in consideration of the desired color, color contrast, and the like.
2%, 3%, 4% or 5%.

On the other hand, the composition (B) contains an enzyme capable of hydrolyzing the glycoside. Examples of the enzyme include its β-glucosidase. The origin of β-glycosidase is not particularly limited. Typical examples include β-glycosidase type 2 manufactured by Sigma and liquid β-glycosidase (Maltozyme L, manufactured by Nagase Biochemical Co., Ltd.). The compounding agent is not particularly limited, but it is desirable to determine the compounding amount per unit volume in consideration of the concentration of the glycoside in the composition (A) and the like. Since the enzyme is originally for catalytic hydrolysis of glycosides, it is added in an amount sufficient to hydrolyze the existing amount of glycosides (in vitro or in vivo).

Next, the composition (A) and the composition (B) according to the present invention are
It is generally preferable to mix them at the time of use and use them on the hair. However, if you mix it for a long time (for example, several days) before using it,
The aglycone produced by hydrolyzing the active ingredient in the composition (A) is unstable to light, heat, etc., so that the coloring power may decrease. Therefore, the mixture more than one day before use,
Not preferable. If mixed, it is desirable to store at low temperature in the dark.

On the other hand, after applying the composition (A) of the present invention to hair,
The composition (B) may be applied.

It is also possible to mix aglycone generated by hydrolysis of iridoid glycoside and dye hair as a cosmetic. Moreover, as described above, aglycones are generally unstable, and it is not preferable to formulate them as cosmetics in advance.

The composition of this invention can be used to change the color of hair in various colors. For example, black, black purple, purple, red purple, blue purple, blue, light blue, green, yellow green, gold, orange, brown, black brown, light brown, reddish brown,
Gives gray etc. This coloring varies depending on the type and concentration of iridoid glycoside and the coloring time.For example, geniposide is dark blue purple, aukbin is black purple, geniposide acid is red purple, gartenoside is light blue purple, methyl deacetyl asperoside is yellow. Is mainly presented.

The hair colored by these hair dyes has a strong fastness to washing with a liquid agent and does not show fading for a long time. Thus, according to the present invention, permanent fast hair dyeing can be performed and the hair is derived from natural plant ingredients, so that the skin, which has been a problem in conventional hair dyeing cosmetics, is easily rashed, and allergic contact dermatitis and hair are caused. There are almost no side effects such as damage, and an ideal hair dye cosmetic can be provided.

(E) Example Production Example 1 Production of aukbin 1 kg of Aoki fruit was shredded and extracted 3 times with 5 parts of methanol, and the extract was concentrated under reduced pressure.
And the insoluble matter is filtered off. The filtrate was washed with 500 m of water, and the washing and filtrate were combined and concentrated under reduced pressure to about 1, and the concentrate was poured into an activated carbon column [activated carbon 300 g, Celite 300 g] to be adsorbed, and water (5), 20% methanol ( Three
), 100% methanol (10) in this order, and elute 1
The 00% methanol fraction was concentrated under reduced pressure, and the obtained residue was purified by silica gel column chromatography using a chloroform-methanol system developing solvent to obtain 15.6 g of pale yellow crystals of aukvin. Its properties were as follows.

Production Example 2 Production of Zeniposide 1.5 kg of dried dye (Yamasako) was extracted 3 times with 6 times each of methanol, the extract was concentrated under reduced pressure, water 5 was added to the concentrated distillate, and the insoluble matter was filtered off. Then, the mixture is washed with water 1, the filtrate and the washings are combined, and concentrated again under reduced pressure to obtain an aqueous solution 2.5. The aqueous solution was washed with 1.5 times of ethyl acetate by shaking,
The aqueous layer is further concentrated under reduced pressure to 1. Activated carbon column [activated carbon (purified Shirasagi) 300g, Celite 300g]
Then, the following elution is carried out while successively increasing the methanol concentration with water and a water-methanol mixed solvent. Water (5.
7), 5% methanol (2.0), 10% methanol (2.0) 20% methanol (2.0), 30% methanol (6.0), 40% methanol (12.0), 50% methanol (6.0), 70% methanol (7.0) ， 100
% Methanol (16.0) Concentrate the 70 to 100% methanol eluate of the above activated carbon column to dryness and recrystallize the residue from ethanol to give mp 163.5.
33.0 g of colorless needles of geniposide at ℃ are obtained. The properties of this product are as follows.

[Α] _D ²⁴ ; + 7.09 ° C. (C = 2.54, methanol). Dyeing test Test example 1 Hair dyeing test using aukbin Aqueous solution containing 0.1%, 1%, 3% and 5% 3
Β-Glucosidase Type 2 at 0 m (5.9U / mg manufactured by Sigma)
Add 100mg of each to dissolve and add 10g of human gray hair to this.
Dip each one and let it stand at room temperature of 25 ° C for 48 hours, air dry the hair, and visually judge the dyeing condition of the hair (No. 1).
table).

Further, after washing the dyed hair with shampoo, the degree of color loss was dyed by an oxidative dyeing method in which the dyed hair was dipped in a 1% N-phenylenediamine solution for 1 hour and then dipped in 5% hydrogen peroxide for 30 minutes. A comparison was made with 10 human white hair dyed by the tannin hair dyeing method, which is immersed in a ferric chloride solution for 30 minutes. The results are shown in Table 2.

(Note 1 U = 1.0 μmol glucose from salicin to pH 5.3
Ability to release for 1 minute at 7 ° C. Table 1 Dyeing state Aukbin concentration (%) Hair color tone 0.1% Dark green-blue green 1.0% Blue black 3.0% Blue black 5.0% Black As described above, hair dyeing using aukbin and β-glucosidase has a deep hair color tone and is excellent in color fastness as compared with other hair dyeing methods.

Test Example 2 Hair dyeing test using geniposide Aqueous solution containing geniposide 0.1%, 1%, 3%, 5% 3
Β-Glucosidase Type 2 at 0 m (5.9U / mg manufactured by Sigma)
Add 100mg of each to dissolve and add 10g of human gray hair to this.
Each book was dipped and allowed to stand at room temperature of 25 ° C. for 48 hours, and the hair was air-dried to visually judge the dyeing state of the hair (Table 3).

Further, after washing the dyed hair with shampoo, the degree of color loss was dyed by an oxidative dyeing method in which the dyed hair was dipped in a 1% N-phenylenediamine solution for 1 hour and then dipped in 5% hydrogen peroxide for 30 minutes. 48 in a book and 5% tannic acid solution
A comparison was made with 10 human white hair dyed by the tannin hair dyeing method, which was dipped in the solution for 5 hours and dipped in a 5% ferric chloride solution for 30 minutes. The results are shown in Table 4.

Results Table 3 Dyeing state Geniposide concentration (%) Hair color 0.1% Dark green-blue green 1.0% Blue black 3.0% Blue black 5.0% Black As described above, hair dyeing using geniposide and β-glucosidase has a deep hair color tone and is excellent in color fastness as compared with other hair dyeing methods.

Formulation 1 Hair dye A liquid Aucubin 5.0% Fragrance 0.05% Methylparaben 0.1% Purified water 94.85% Liquid B Maltoteam L [Nagase Seikagaku Corp. β-glucosidase 2000AuN / m-containing liquid enzyme] 99.05% Methylparapen 0.05% At the time of use: Mix B liquid 1 with A liquid 9 and apply to hair.

Formulation 2 Hair dye (A liquid) Aucubin 5.0% Methylbaraben 0.1% Dimethyl sulfoxide 2.0% Carboxyvinyl polymer 1.2% Propylene glycol 5.0% Perfume 0.05% Purified water 96.65% (B liquid) Maltozyme L 98.9% Polyvinyl Alcohol 1.0% Methylparaben 0.05% When using A liquid 9 mix B liquid 1 and apply to hair.

Formulation Example 3 Hair liquid A liquid Geniposide 5.0% Fragrance 0.05% Methylparaben 0.1% Purified water 94.85% B liquid Maltozyme L 99.05% Methylparaben 0.05% When using A liquid 9 and B liquid 1 are applied.

Formulation 4 Hair Liquid (Solution A) Genipon 5.0% Methylparaben 0.1% Hexamethylenelauramide 2.0% Propylene glycol 15.0% Perfume 0.05% Purified water 77.85% (Solution B) Maltozyme L 98.95% Carboxyvinyl polymer 1.00% Methylparaben 0.05% At the time of use: Mix B liquid 1 with A liquid 9 and apply to hair.

Formulation 5 Hair liquid (Solution A) Aucubin 5.0% Polyoxypropylene (40 mol) Butyl ether 25.0% Lanolin derivative 1.0% Ethyl alcohol 10.0% Propylene glycol 5.0% Fragrance 1.0% Methylparaben 0.1% Purified water 57.9% (Solution B) Maltozyme L 99.05% Methylparaben 0.05% When (A) 9 is used, (B) 1 is mixed to make a liquid.

Formulation 6 Hair Liquid (Solution A) Geniposide 5.0% Polyoxypropylene (40 mol) Butyl ether 20.0% Polyoxyethylene oleyl alcohol ether 2.0% Propylene glycol 5.0% Ethyl alcohol 5.0% Methylparaben 0.1% Perfume 1.0% Purified water 66.9% (B Powder) β-Glycosidase Type 2 (manufactured by Sigma) 99.0% Polyvinyl alcohol 1.0% When used (Liquid A) 99 (B) Powder 1 is mixed and dissolved to produce a liquid. Formulation 7 Hair emulsion (A liquid) Aucubin 5.0% Cetyl alcohol 8.0% Stearic acid 10.0% Lanolin 2.0% Glycerin monostearate 8.0% Polyoxyethylene sorbitan monostearate 2.0% Fragrance 0.3% Ethylparaben 0.3% Purified water 64.4% (Solution B) Maltozyme L 96.8% Glycerin 3.0% Camaxoxy vinyl polymer 0.2% When (A) 9 is used, (B) 1 is mixed and applied to the hair.

(F) Effects of the Invention According to the present invention, it is possible to easily dye hair of each color with high fastness, and since the active ingredient is a natural product, it is possible to prevent skin irritation like conventional hair dyes. There are no side effects.

Claims (2)

[Claims] 1. A composition (A) containing at least one of an iridoid glycoside and a secoiridoid glycoside as an active ingredient, and a composition containing an enzyme capable of hydrolyzing the glycoside as an active ingredient. A hair dye cosmetic in combination with (B). 2. A composition (A) containing at least one of an iridoid glycoside and a secoiridoid glycoside as an active ingredient, and a composition containing an enzyme capable of hydrolyzing the glycoside as an active ingredient. A method for dyeing hair, characterized in that (B) is mixed in advance and applied to hair, or the composition (A) is applied to hair and then the composition (B) is applied to dye hair.