JP2747587B2 - Melanin production inhibitor consisting of brown algae extract - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] The present invention relates to a water-soluble, non-gel-forming, phenolic compound obtained from seaweeds, particularly brown algae: Phaeophyta, which has no gel-forming ability. The present invention relates to a melanin production inhibitor comprising an acidic extract.

"Industrial application field" The melanin production inhibitor according to the present invention has an effect of suppressing the production of black melanin pigment (melanin polymer: hereinafter simply referred to as melanin for convenience) obtained by acting tyrosine on tyrosine. .

Therefore, its application fields include, for example, cosmetics,
Agents used in external application and rubbing forms: They can be used as they are in pharmaceuticals, quasi-drugs, etc. (hereinafter simply referred to as cosmetics for convenience), or blended in their formulations.

The melanin production inhibitor according to the present invention may be used in sunlight (ultraviolet)
Deterioration of skin and hair by irradiation: Helps prevent and alleviate sunburn.

"Conventional technology" (1) Broad classification of seaweeds and history of application Seaweeds can be broadly classified into brown algae, red algae, and green algae according to botanical classification. In Japan, some of these algae are also referred to as sea vegetables and have been used for a long time as edible foods. For example, they are used as cooking soup (seasoning) for celebrations and rituals, and in general households. Is
It has been used in the form of miso soup, sashimi ingredients (knobs), boiled in tsukudani, etc.

On the other hand, seaweed alga bodies are equivalent to the leaves and stems of above-ground plants, and are treated with acids, alkalis, enzymes, etc. based on the tissue fibers constituting this part, and the mucous polysaccharide: alginic acid , Carrageenan, agar, fungi, etc., are also used as a paste, binder, bulking agent, emulsion stabilizer, and humectant in the food field, pharmaceuticals, cosmetics, etc. These polysaccharides resemble the properties of pectin and hyaluronic acid sugars, and usually have the property of increasing their concentration and forming a gel (jelly-like) even if they are soluble in a small amount in an aqueous system.

(2) Water-soluble components in seaweed The water-soluble components contained in seaweed include such polysaccharides, low-molecular-weight sugars such as amino acids and mannitol, various mineral components, iodine, and phenolic substances. Have been.

In the step of obtaining a polysaccharide as described above as a seaweed component, treatment such as decolorization and desalting is performed, and water-soluble components other than the polysaccharide are usually purified and removed as unnecessary by-products, or It was only used as a salted seasoning or amino acid seasoning.

On the other hand, in Europe, aqueous extracts of brown alga Hibamata have been used as a folk medicine for cellulitis of the skin, but amino acids, low-molecular-weight sugars, and various minerals are used for skin and hair. It has been postulated that it enhances function and its effect on cellulitis is due to iodine and minerals.

(3) Use as a melanin production inhibitor There is no known publication that found a melanin production inhibitor from seaweed. However, in cosmetics, components such as vitamin C lighten skin spots and blacken them. It is used for the purpose of preventing aging.

"Problems to be solved by the invention" The present inventors have considered the history of application of seaweeds described above,
Brown algae: Research has begun on whether the water-soluble component can be used more effectively based on the kelp, kelp, alana, serrata, and serrata.

The solution eluted from the brown algae into the water system without gel formation gradually changes from green-brown to brown to black-brown when left to stand, and changes to a black-brown state due to concentration. Therefore, we tried to separate the solution mainly composed of the changed pigment component from the colorless solution, and performed various studies on each of them. And started applying it as a melanin production inhibitor.

`` Constitution of the invention''The present invention is a brown algae: extracted based on Phaeophyta,
It is composed of a melanin production inhibitor consisting essentially of a water-soluble extract containing a phenolic compound derived from brown algae and having no gel-forming ability.

"Means for Solving the Problems" The evaluation method of the melanin production inhibitor according to the present invention is as shown in the following section. In this test, a method of measuring the absorbance of the dopa quinone at the production stage is usually adopted.
This means is not preferred because the sample exhibits a similar color tone (black-brown). Therefore, in this test, a method for evaluating the effect of inhibiting the formation of melanin (precipitate) generated by further autoxidation was performed.

[Melanin production inhibitory effect test] (1) Preparation of reagent L-Tyrosine solution: L-Tyrosine is dissolved in purified water to a concentration of 0.3 mg / mL and stored in a cool, dark place.

Mcllvain buffer: Adjust to pH 6.8 with 0.1 M citric acid and 0.2 M disodium hydrogen phosphate.

Tyrosinase solution: Sigma mushroom-derived T
1 mg of yrosinase (2,750 unit / mg) is weighed and 3 mL of Mcllvai
Dissolve in n buffer and adjust as needed.

(2) Preparation of sample solution Eight small test tubes are arranged in a line, and 1 mL of purified water is dispensed into test tubes No. 2 to No. 8. Next, take 2 mL of the test solution in the first test tube (No. 1), withdraw 1 mL from the No. 1 test tube, dilute sequentially (from No. 2 to No. 8) 2-fold, and perform the final test. Discard 1 mL from the tube (No. 8). This series is 1, 1: 1, 1:
It is a dilution of 2, 1: 4, 1: 8, 1:16, 1:32, 1:64.

(3) Operation method 1 mL of L-Tyrosine solution, 1 mL of Mcllvain buffer and 0.9 mL of each dilution series test solution were placed in a test tube, and allowed to stand in a thermostat at 37 ° C. for 10 minutes, and then 0.1 mL of Tyrosinase solution was added. Mix well and leave for 1 hour. Next, it is taken out of the thermostat and left at room temperature overnight to make a judgment.

(4) Judgment method When observing the test tube with a blank sheet in the background or at the bottom,
When melanin (black crystalline precipitate) is recognized, it is +, and when it is not recognized, it is-.

"Examples" The present inventors adopted the above-mentioned evaluation method, and the manufacturing method was simple, there was no waste in the eluted component, and as its use, it could be immediately used in cosmetics, Various production (extraction) trial productions were performed under conditions that could be easily achieved.

As a result, it was found that, for example, the target melanin production inhibitor could be obtained by the following method.

(Selection of Raw Materials) In the present invention, brown algae: Phaeophyta are used, but red algae: Phodophyceae can also be used. However, red algae has a weak melanin production inhibitory effect and is poorer in persistence than brown algae.

When a brown algae that belongs to the family Hirata is used as a raw material, it has a strong melanin production inhibitory effect and a good yield. However, the use of seaweeds is not limited to this, and brown algae used for the production of alginic acid: extraction having a sufficient action by using algal bodies belonging to the family Hibamata, Kombuaceae, and Hondawaraaceae Things are obtained.

Separately, red algae used for carrageenan, furceleran, and agar: Algae such as Acrophoridae, Ogonoriaceae, Echinaceae, Noriaceae, Obaxaceae, Simiidae, and Suzukabeniidae can also be used.

(Manufacturing method: Extraction method-A) Brown algae: Drying of alga bodies (parts corresponding to leaves and stems of above-ground plants) harvested in winter (cold season), any of hibamata, kombu, kurome, alana, and hondawara After washing 1 kg of the product in running water in advance, it is placed in a container containing 5 to 10 L of water and heated (40 to 100 ° C.) and immersed for 1 to 10 hours (preferably 3 to 6 hours).

As a result, most of the water-soluble components contained in the brown algal body migrate into the water, and the liquid changes from green-brown to brown. In this process, if the time required for heating and immersion is long, sufficient care must be taken because some polysaccharides constituting the algal bed may be eluted. In particular, this tendency is exhibited when red algae is used as a raw material.

In addition, 5 kg of water per 1 kg of washed alga bodies (in terms of dry matter)
The elution of polysaccharide can be prevented by immersing in cold water at about 10 ° C (± 10 ° C) using 0L. In this case, the time required for immersion in cold water is preferably about 6 hours to one day and night.

Also in cold water immersion and warm water immersion, transfer of water-soluble components into water is promoted by occasionally or gently stirring.

After immersion in the above process, the aqueous layer was separated and
The solution is allowed to stand at about 10 ° C. (± 10 ° C.) for about 3 to 15 days, and filtered to obtain a crude liquid. The crude liquid is concentrated to about the weight of the starting material, or further concentrated to dryness, and then (1) a mixture of ethanol and water at a ratio of 50:50 to 70:30, or (2) a polyol solvent. As, for example, the ratio of glycerin, propylene glycol, 1,3-butylene glycol, etc. and water is 50:
A mixed solution having a ratio of 50 to 70:30, or (3) a mixed solution in which the ratio of ethanol and the polyol solvent is not limited,
(4) A mixture of three types of ethanol, polyol-based solvent and water, the mixing ratio of which is not limited, is added to 1 to 10 L of a mixed solution, dissolved under stirring, and then cooled again in a cold place. Let stand for ~ 10 days. Thereafter, the solution is filtered and the filtrate is collected to obtain a melanin production inhibitor. Hereinafter, what is obtained here is referred to as extract A for convenience.

(Production method: Extraction method-B) As in Production method-A, brown alga was used as a raw material, and fresh algae (undried) were thoroughly washed with water and then dehydrated. 10 kg
Using a mixture of 10 to 40 L (preferably about 20 L) of a mixture of a polyol solvent and water at a ratio of 40:60 to 80:20 to 20 ° C. (± 20
C.) for 3 to 15 days with occasional stirring, and the immersion liquid is collected by centrifugation.

The residue separated in this step is immersed again in 10 to 40 L (preferably about 20 L) of an aqueous solution containing 20% of a polyol solvent, and the immersion liquid is mixed with the immersion liquid of the destination, followed by filtration. I do. At that time, the concentration of the polyol solvent used in the system was adjusted to 10 to 50% (preferably about 45%), and the mixture was aged for 7 to 45 days (stationary), and then treated with a melanin production inhibitor. I do. This is referred to as extract B for convenience.

(Confirmation of action: influence by heating) Both the extract A or B obtained by the above-mentioned production method has a melanin production inhibitory action. The following table "Table 1" shows the results obtained by further heating and heating the extracts A and B and evaluating the same effect. That is, the extracts A and B according to the present invention
Both are hardly affected by the heating treatment, the melanin production inhibitory action is maintained, and heating, it can be blended in the production of known cosmetics such as creams and emulsions accompanied by the heating treatment. The effect was assessed as sustained.

In the case of the extracts A and B, some solvents and their combinations were shown in the production, but this was examined in terms of the melanin production inhibitory action and the formation of the precipitate in the extract. Although this is shown based on the results obtained, there are also reasons to be described later.

"Confirmation of Components or Indicator Values" What is the active ingredient of the melanin production inhibitor according to the present invention has been of interest to the present inventors.
It goes without saying that the elution residue remaining at the time of obtaining the extract A or B can be further used as a raw material for extracting alginic acid. That is, in order to obtain a polysaccharide from brown algae or the like, water washing has been conventionally well performed, and water-soluble substances other than the polysaccharide have been removed in advance.

By the way, on the main subject, the extracts A and B according to the present invention include:
It is characteristic that such a polysaccharide is hardly contained. That is, if a polysaccharide is present, the extract is in the presence of a polyol-based solvent to promote gel formation, or the extract is a colloidal solution having a viscous solution without a clear feeling. And B have no gel formation or colloidal shape, and exhibit a slightly slippery viscosity.

This is due to the relatively low molecular weight saccharides such as mannitol contained and the polyol solvent used. And, since these polysaccharides and saccharides do not have melanin production-inhibiting ability, it is considered that the leading role substance is another component.

Therefore, confirmation tests have been continued using various qualitative and quantitative methods, but as a result, it was considered to be a phenolic compound from the viewpoint of dissolution in the solvent used.

The following table (Table 2) shows the numerical values or indication values in the minimum confirmation test for quality standard control used for cosmetics, in relation to the melanin production inhibitory ability when extracted based on the examples. Things. According to the production method as shown in the extraction methods -A and -B, a phenolic compound was confirmed regardless of the type of brown algae used as the raw material, and the resulting extract contained in the extract (Table 1) ), The effect of suppressing the production of melanin is confirmed.

However, in the case of red algae, even if a phenolic compound can be confirmed, a melanin production inhibitory action cannot be confirmed, or the content of the phenolic compound may be extremely small. In such a case, even if the final concentration is adjusted by controlling the amount of the solvent used in the production process, or an operation such as concentration is performed, there are some which do not have the melanin production inhibitory ability as in the present invention.

In other words, using red algae as a raw material is inefficient and has a weak effect. As a result, it is thought that phenolic compounds contained in seaweed include those that have the property of inhibiting melanin production and those that do not, and have specific effects in brown algae. It was determined that a phenolic compound was contained. Therefore, when using red algae as a raw material, it is important to first check the amount of total phenol contained in the raw material before using it.

On the other hand, about 3 to 8% is contained in brown algae (undried matter), and the alga bodies belonging to the family Hibamatidae are always contained stably in a large amount. In other brown algae, it is in the range of 1-4% on average. Regarding the melanin production inhibitory ability, it was confirmed that all of those obtained from these brown algae exhibited an effect, and among them, it was confirmed that the extract from Hibamata had a strong effect in proportion to its content.

"Effect of the Invention" The present invention is a melanin production inhibitor based on a water-soluble component obtained from brown algae and having no gel-forming ability, and it is greatly used in cosmetics. The effect is.

Further, according to the present invention, it is possible to use alginic acid obtained from brown algae or the like with by-products thereof. In other words, since the production of polysaccharide: alginic acid requires the removal of water-soluble components other than the target substance, it is possible to effectively use brown alga without waste by combining this step with the above step.

One of the great features of the present invention is that it contains a phenolic compound contained in brown algae, and the present invention opens up a new field in the effective use of components contained in seaweed. The effect is great.

In the present invention, the production method as a form easily used in cosmetics as a melanin production inhibitor was shown. Here, the main substance showing melanin production inhibitory ability is derived from a phenolic component. For extraction into water, immersion in water, alcohols, or a mixture of alcohol and ether makes it possible to remove pigments and the like, and to obtain purified products.

 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-62-286907 (JP, A) JP-A-64-16713 (JP, A) JP-A 1-186813 (JP, A)

Claims (1)

(57) [Claims] 1. A melanin production inhibitor comprising a water-soluble extract of a brown algae, which essentially contains a phenolic compound derived from a brown algae and has no gel-forming ability.