JPS6289772A - Treatment of shikonin and cosmetics containing the resultant product - Google Patents

Abstract

PURPOSE:To eliminate the development of contact allergic effect on the skin caused by shikonin, by mixing treatment of shikonin with specific metallic ion in a water-soluble solvent solution containing protein and/or peptide. CONSTITUTION:Shikonin or its derivative is brought to mixing treatment with a solution of one kind of metallic ion selected from aluminum, iron, magnesium, zinc and copper ions in a water-soluble solvent solution containing protein and/or peptide. The resulting treated product is incorporated in cosmetics to put to practical use.

Description

Detailed Description of the Invention [A] Purpose of the Invention The present invention aims to reduce the contact allergic effect of shikonins on the skin when using shikonins or their derivatives (shikonins) as colorants or pigments in skin cosmetics. The present invention relates to highly safe cosmetics that eliminate the expression of

(Industrial Application Field) The shikonin or its derivative according to the present invention does not exhibit contact allergic effects even if it is directly attached to the skin.
Therefore, it can be frequently used as a coloring agent or pigment in cosmetics in general.

In addition, the means adopted for eliminating contact allergy to shikonin or shikonin IL1 according to the present invention is to use a specific metal ion together with proteins or peptides, and to mix and stir the treated product or composition. However, if this method is used, it will be possible to remove various other synthetic pigments or colorants, or other drugs used as raw materials for cosmetic formulations that are known to induce contact allergies. It can be used as an effective pretreatment means for protecting substances in cosmetic formulations.

"Table 1, Main shikonin derivatives (shikonins) (prior art) Shikonin or shikonin derivatives are known as one of the pigment components contained in the roots of purple grass, and have pharmacological effects such as anti-inflammatory and sedative effects. It is known for its antibacterial and entrapment formation promoting effects.

On the other hand, the rhizomes of Murasaki have a long history of being used as dyes for clothing IaFa, and extracts containing the pigment as a main ingredient are incorporated into cosmetics.

When using Shikonin extract in cosmetics, its purpose can be roughly divided into two categories: one is to expect the pharmacological effects of Shikonin, etc. mentioned above, and the other is to use it as a coloring agent or pigment. It was used as a.

(Public Publications) Known publications regarding shikonin, shikonin derivatives, or rhizomes of purple violet (hereinafter referred to as shikon in accordance with the Chinese herbal name) include, for example, the following publication published by the Japan Patent Office. .

(1) Published Patent Publication Showa 5O-49409(k) (2)
Published Patent Publication 1972-94432 (*) (3)
tt Showa 59-10507 (*) (4) /
/ Showa 6O-58909 (5) n
Showa 6O-58910 (6) tt Showa 6O-
58911 (7) tt 1982-2827
9(8) tt Among the publications published in 1982-28278, (1 to 3) are by the present inventors.

Conventionally, in cosmetics, liquids of Ciconix extract have been mainly used as colorants or pigments, such as the product shown in the above-mentioned Japanese Patent Publication No. 1 (1) (Siconics Liquid: - manufactured by Maru Falcos). In this case, 0.2 to 0.5% is used as an appropriate amount, and at this amount, the pharmacological effect is mild, and there are no problems when used as a coloring agent for cosmetics.

(Problems to be Solved by the Invention) Shikonins can now be produced by the tissue culture method of Shikonins, as shown in the above-mentioned publications (7-8), and based on this, mass production (extraction M separation) is possible. ) became possible.

Isolated shikonin or shikonin derivatives have strong pharmacological activity, unlike conventional shikonin extracts, and if they are incorporated into cosmetics as colorants or pigments, they may conflict with the pharmacological effects of shikonin. As a side effect, consideration must be given to the induction of contact allergic effects on the skin, but this point has not been well known in the past.

When Shikonin is used as a colorant or pigment in cosmetics, no means have been disclosed so far to prevent the induction of contact allergy.

The present inventors began research to solve this problem while conducting re-evaluation tests regarding pharmacological effects and their safety, and finally completed the present invention.

[Mouth] Structure of the Invention The present invention provides a method for preventing the induction of contact allergies by mixing shikonin or a shikonin derivative in a solution of specified metal ions and proteins or peptides, and then applying the mixture to cosmetics. It is added to.

(Means for solving the problem) "Example-1 Nonoconin bulk powder or shikonin derivatives (shown in Table 1), or a mixture thereof, was dissolved in ethanol or a mixture of methanol and water. Add 2% aluminum chloride methanol solution, 1% ferric chloride ethanol solution, zinc (Zn°゛) solution, magnesium (Mg") to the solution.
) 1 @ 1 solution, steel (Cu44) solution, any one type of metal ion solution, water-soluble protein, water-soluble peptide, or a mixture of water-soluble protein and water-soluble peptide. Examples include, but are not limited to, vegetable wheat gluten, soybean protein (soy milk), animal albumin, serum, casein, gelatin, placenta extract, or placenta, collagen, elastin, keratin, and fibroin. Next, an aqueous solution of a water-soluble low-molecular protein or peptide obtained by hydrolysis or enzymatic decomposition of sericin, etc. is mixed and stirred. A rapid precipitate is formed by adding IN sodium hydroxide solution and adjusting the pH of the mixed stirring solution to 7-8. Therefore, this precipitate is removed, thoroughly washed with water, and then incorporated into various known cosmetics. In addition, the precipitate may be washed thoroughly with water, dried, and stored as a powder, and may be used by blending it into cosmetics if necessary.Also, after washing the precipitate well with water, After dissolving in 0.2N sodium hydroxide solution, it is further neutralized using 2N hydrochloric acid solution, and dissolved in polyol solvents such as PEG (polyethylene glycol), propylene glycol, budelene glycol, water, ethanol, or water. It may also be used by mixing it in a polyol-based solvent together with alcohol or ethanol and then blending it into cosmetics.

"Example-2 Powder material mainly composed of water-insoluble protein, e.g.
Animal-derived proteins such as water-insoluble protein derived from vegetable soybeans, silk powder, fibroin, sericin, collagen, elastin, and keratin are combined with a 5% aluminum acetate aqueous solution, iron (F, ***), and zinc. (Zn”), Magnesium (Mg”), Copper (Cu**)
Add to one type of metal ion solution, stir, disperse, leave overnight, filter, wash with water, and separate the precipitate. Next, shikonin or its derivatives (shown in Table 1)
Or, the precipitate obtained earlier is added to the mixture of ethanol or methanol and water and dissolved therein, and the mixture is stirred occasionally in a hot bath at 60 to 70"C. , perform heating for about 90 minutes, after heating, leave to stand, separate the precipitate, dehydrate, wash with water, immerse in ethanol, collect the precipitate, air dry, 80 ± 5 This powder, which is dried under reduced pressure at °C and made into a powder, is blended into any cosmetic.

[C] Effects of the invention Shikonin or its derivatives treated in Example 1 or 2 in the preceding section, or a mixture thereof exhibits a red, reddish-purple, or bluish-purple color and does not exhibit a contact allergic effect on the skin. Ideal for use as a colorant or pigment in cosmetics.

The effectiveness of the present invention was determined in accordance with the maximizator method (document source: New Toxicity Test and Safety Evaluation, published by Soft Science), and in addition to the high tide method (document source: Fragrance Journal No.).

14 Fragrance Journal Co., Ltd., 1975), guinea pigs were used as the test animals, and the sensitization method was to use shikonin by intradermal injection, and after administering it to the neck, The precipitate after the treatment was used as a specimen, and this was mixed into a parent wood ointment and applied. The test was conducted using five animals per group. The sixth table (Table 2) shows the results of the precipitate treated with shikonin according to Example 1 or 2. As shown in Table 2, no skin contact allergic effects were observed.

Considering the effect on this treatment from the perspective of the structure of shikonin, the active group that has pharmacological action is found in -OH and 10, according to the structural formula of shikonin as shown below. It is assumed that -OH and 10 were one of the triggers for the development of skin contact allergy, irritating the skin. In other words, -OH and 10 were in a state where they easily acted on (easily bonded to) the proteins that make up the skin. Therefore, Example 1
In 2, by using various proteins and peptides in place of biological skin constituent proteins and reacting with them, contact allergies will not occur even when applied directly to the skin. I'm guessing.

Further, in Example 1 or 2, iron, aluminum, or the like was used as the specified metal ion solution, but even if iron or aluminum is not used, the desired contact allergy effect will not be exhibited. However, when it is added to cosmetics and subjected to heating treatment, for example, in the case of emulsions and creams, or when it is mixed in large quantities, it is sometimes necessary to conduct tests using the creams or emulsions. May cause skin contact allergy. However, when specific metal ions were used as in Examples 1 and 2, this was not observed.

If we consider this point further, we will probably find that -OH and 10, iron and aluminum, etc.
It was presumed that it acts on the inactivation of the active groups 1OH and 10 by effectively bonding with the histidine groups of other proteins and peptides.

It has been found that the treatment method according to the present invention can also be used as a means for suppressing skin contact allergies to other quinone pigments.

(shikonin)

Claims (1)

[Claims] In shikonins, aluminum, iron,
A method for treating shikonins, comprising mixing a solution of one of magnesium, zinc, and copper with a protein or peptide, or a mixture of protein and peptide in an aqueous solvent solution. (2) Shikonins contain aluminum, iron, and metal ions as metal ions.
The shikonins according to claim 1, wherein a mixing treatment is performed in an aqueous solvent solution of a solution of one of magnesium, zinc, and copper and a protein or a peptide, or a mixture of a protein and a peptide. A cosmetic product characterized by containing a treated product obtained by the treatment method.