JPH0662383B2 - Method for manufacturing cosmetic raw materials - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for producing a cosmetic raw material containing, as a main component, a mucopolysaccharide-free acidic polysaccharide obtained from shellfish meat.

[Conventional technology]

Cosmetic raw materials based on acidic mucopolysaccharides are widely used. For example, hyaluronic acid and chondroitin are used.

However, as a result of an experiment conducted by the present inventor, hyaluronic acid, chondroitin, chondroitin-4-
Mucopolysaccharides such as sulfuric acid, chondroitin-6-sulfate, dermatan sulfate, heparin and heparin sulfate were not contained.

However, although the structure could not be clarified, it was discovered that acidic polysaccharides other than these mucopolysaccharides are contained and that they are promising as raw materials for cosmetics.

The method for extracting the acidic polysaccharide is generally the method described in Japanese Patent Publication No. 51-11178.

Recently, shred shellfish or animal ointment, or add freeze-dried alkaline solution containing neutral salt to extract mucus from tissue and neutralize it with acid solution. , A method of removing protein to obtain a mucopolysaccharide has been proposed.

Since this method is extraction with an alkaline liquid such as NaOH or Ca (OH) ₂ , there is a possibility that sulfate groups will be released. Further, in this extraction method, all of the saccharides are extracted and other substances are also included, which is not preferable in terms of purification.

[Problems to be solved by the invention]

When the acidic polysaccharide is extracted with an alkaline liquid, the sulfate group may be released. There is a need for an extraction method that eliminates the risk of the elimination of sulfate groups.

On the other hand, the pearl oysters used for pearl farming have no choice but to discard the flesh other than the scallops after collecting the pearls, which causes marine pollution and makes it difficult to dispose of them.

It is an object of the present invention to develop a method for extracting acidic polysaccharides from shellfish meat that is free from the fear of leaving sulfate groups, and to provide a method for producing cosmetic raw materials and solving problems such as marine pollution.

[Means for Solving the Problems]

The present inventor has completed the present invention as a result of intensive studies to solve the above problems.

That is, according to the present invention, after degrading shellfish with a protease, complete deproteinization is performed to remove low-molecular substances,
A method for producing a cosmetic raw material containing an acidic polysaccharide as a main component, which comprises adding a secondary ammonium salt to precipitate and separate the acidic polysaccharide.

For complete deproteinization, 10% of trichloroacetic acid or perchloric acid
Use solution or Sevag method. The Sevag method is also called the chloroform method and was devised by MG Sevag in 1934. When chloroform is added to an aqueous solution containing protein and shaken vigorously, protein molecules are denatured and adsorbed at the water-chloroform interface. Since the adsorbed denatured protein is insoluble, it can be easily removed. This method is very sensitive.

To remove low molecular weight substances, dialysis, gel filtration, ultrafiltration, or an organic solvent that precipitates acidic polysaccharides is used.

Further, in order to purify the acidic polysaccharide separated and precipitated by the quaternary ammonium salt, an aqueous solution of an inorganic salt is added to the precipitate and dissolved therein, followed by reprecipitation with an aqueous alcohol solution, or by repeating this method. It can be purified.

The method of the present invention will be described in detail.

In the first step, shellfish meat from which shells have been removed is decomposed by a protease. In order to facilitate this treatment, it is preferable to heat and denature and then pulverize with a mixer or the like. When pearl oysters are used, mucus associated with the flesh is also used as a raw material, and only mucus may be used. At this time, it can be used regardless of taking out pearls unlike the case of using shellfish, the raw material can be easily collected, and the crushing step is not necessary.

The proteolytic enzyme is not particularly limited, but one that has no substrate specificity and strong decomposing power is preferable. For example, it is decomposed using one kind or a mixture of two or more kinds such as papain, actiners, samoase and denazyme.

In the second step, deproteinization is performed to remove undegraded proteins, nucleic acids and enzymes. The method for deproteinization is not particularly limited, but generally trichloroacetic acid or perchloric acid is used at a concentration of 10% or the Sevag method is used.

In the third step, low molecular weight substances such as deproteinizing agents, amino acids, peptides and salts are removed. As a removing means, there are a dialysis method, gel filtration, ultrafiltration, and a method of adding an organic solvent in which an acidic polysaccharide is precipitated, and the dialysis method is preferable.

In the fourth step, neutral polysaccharides and glycoproteins that are present together with acidic polysaccharides are separated. As a removing means, an aqueous solution of a quaternary ammonium salt is added. Since the acidic polysaccharide binds to quaternary ammonium and precipitates, it is separated by decantation or centrifugation.

As the quaternary ammonium salt, one in which one of the alkyl groups has 12 or more carbon atoms may be used. Also in the pyridinium type, it is sufficient that the alkyl group bonded to nitrogen has 12 or more carbon atoms. For example, lauryl trimethyl ammonium salt, stearyl trimethyl ammonium salt, cetyl pyridinium chloride, etc. can be illustrated.

Up to the 4th stage, acidic polysaccharides can be obtained, but since this precipitate contains quaternary ammonium salts and other salts, further purification is preferable.

For purification, an inorganic salt aqueous solution is added to this precipitate to dissolve it, and the complex is dissociated and dissolved, and then alcohol is added to reprecipitate the acidic polysaccharide and the quaternary ammonium salt is separated into the liquid. Remove. This precipitate is dissolved in purified water, added to an alcohol concentration of 80%, stirred, allowed to stand and then centrifuged to obtain a precipitate. It is preferable to repeat this step 2-3 times.

Any inorganic salt can be used as long as it dissociates and dissolves the complex of the quaternary ammonium salt of acidic polysaccharide. Examples thereof include sodium chloride and potassium chloride.

The salt form used here determines the salt form of the final product.
For example, with sodium chloride, the final product will be the sodium salt.

The inorganic salt and the concentration are such that the complex pair is dissociated, and sodium chloride needs to be 1.5 M or more. There is no particular upper limit, but if the concentration is too high, the desalting operation will take time, waste of reagents will occur, and the limit is about 4M. Further, when it is desired to remove the remaining proteins and pigments, Lloyd's reagent and kaolin are added to an aqueous solution obtained by dissolving the precipitate in water to adsorb and remove the pigments and proteins. After removing the adsorbent by centrifugation and filtration, the acidic polysaccharide is freeze-dried.

When the acidic polysaccharide obtained in this manner is incorporated into cosmetics, the result is that it has high water retention and moisturizing properties similar to hyaluronic acid, etc., so as to moisturize the skin and hair and prevent drying, Due to its excellent penetrability and tissue affinity, it showed a unique lubricity effect.

In addition, increasing the viscosity of the cosmetics themselves to improve stability and usability is one of the important effects.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1 a. 100 kg of pearl oysters from which the shells were removed were heated, denatured, and then pulverized with a mixer.

b. Add 100g of actinase E to this, 45 ℃
The mixture was left to stand for 24 hours while being stirred.

c. 10 kg of trichloroacetic acid was added, and the mixture was stirred, allowed to stand for 1 hour and then centrifuged to remove the precipitate, and deproteinized.

Further, dialysis was performed for 48 hours using a cellophane tube to remove low molecular weight substances.

d. Thereafter, 1 kg of cetylpyridinium chloride was added, and the mixture was stirred, allowed to stand for 1 hour, and then centrifuged to obtain a precipitate of cetylpyridinium salt of acidic polysaccharide.

e. 2M sodium chloride was added to this precipitate to dissolve the precipitate. Ethyl alcohol (3 times) is added thereto, and the mixture is stirred, left standing for 1 hour and then centrifuged to obtain a precipitate.

f. A small amount of purified water was added to this precipitate to dissolve the precipitate,
Ethyl alcohol is added to a concentration of 80%, the mixture is stirred, left for 1 hour and then centrifuged to obtain a precipitate.

g. f was repeated 3 times.

The yield was 512 g.

Example 2 a. 100 kg of pearl oysters from which the shells were removed were heated, denatured, and then pulverized with a mixer.

b. After adjusting this to pH 6-6.5, 100 g of Samoases and 500 g of Denazyme were added, and the mixture was left standing for 100 minutes with stirring at 60 ° C.

c. Centrifuge to remove insoluble matter, add 10 kg of trichloroacetic acid, stir, leave for 1 hour, centrifuge,
After removing the precipitate, low molecular weight substances were removed by ultrafiltration with a molecular weight of 10,000.

d. To this, 10 kg of purified water was added and dissolved, then 1 kg of cetylpyridinium chloride was added and stirred, and the mixture was left standing for 1 hour and then centrifuged to separate the precipitate.

e. 2M potassium chloride was added to this precipitate to dissolve the precipitate. Add 3 times ethyl alcohol to this and stir,
After standing for 1 hour, the mixture was centrifuged to obtain a precipitate of acidic polysaccharide.

f. A small amount of purified water was added to this precipitate to dissolve the precipitate,
Ethyl alcohol was added to a concentration of 80%, and the mixture was stirred, allowed to stand for 1 hour and then centrifuged to obtain a precipitate.

g. f was repeated 3 times.

h. To this, 10 kg of purified water was added and dissolved, 500 g of kaolin was added and stirred, and the precipitate was removed by centrifugation, filtered through a 5 micron filter, and freeze-dried.

The yield was 485 g.

(Formulation Example 1) ... Emollient cream (% by weight) Liquid paraffin 25.0 Beeswax 5.0 Jojoba oil 7.0 Stearyl alcohol 2.0 Stearate monoglyceride 2.0 Sorbitan monostearate 3.5 Polyoxyethylene sorbitan monostea Rate (60 E.O.) 4.0 Purified water 45.6 Propylene glycol 5.0 Acidic polysaccharide powder 0.5 Methyl paraoxybenzoate 0.2 Perfume 0.2 (Prescription example 2) ... Lotion Squalane 1. 0 Fragrance 0.2 Polyoxyethylene hydrogenated Himan oil (60 E.O.) 2.5 Purified water 78.1 1,3 Butylene glycol 5.0 Glycerin 3.0 5% Aqueous polysaccharide aqueous solution 10.0 Paraoxybenzoic acid Methyl 0.2 (Formulation Example 3) ... Shampoo Sodium alkyl ether sulfate 16.0 Dier lauric acid Tanolamide 5.0 Purified water 73.0 Propylene glycol 5.0 Acidic polysaccharide powder 1.0 Methyl paraoxybenzoate 0.2 Perfume 0.2 The comparative example is more than the formulation example, acidic polysaccharide powder or acidic polysaccharide aqueous solution. Is replaced by purified water, Comparative Example 1 corresponds to Formulation Example 1, Comparative Example 2 corresponds to Formulation Example 2, and Comparative Example 3 corresponds to Formulation Example 3.

(Usage test) A questionnaire survey was conducted by having 15 panels use the panel. The results are shown in Tables 1 and 2.

(The numerical value is the average value of the evaluation points of 15 people) (Humidity test) A sample was applied to the inside of the forearm of 10 panelists.

The water content of the part to be coated is measured by IBS Moisture Analyzer SC-1
It was measured at 0.

Next, the sample was applied, and after 20 minutes, 40 minutes, 60 minutes, and 80 minutes, the water content of the applied site was measured.

Indoor temperature 25 ± 2 ° C, humidity 65 ± 10% The results are shown in Table 3.

[Effect of the invention] According to the method for producing a cosmetic raw material of the present invention, since an alkaline liquid is not used in the extraction of acidic polysaccharides from shellfish meat, it is considered that sulfuric acid is bound to the acidic polysaccharides. The acidic polysaccharide contained as it is can be extracted without the risk of leaving the group.

As is clear from Examples and Formulation Examples, the acidic polysaccharide produced by the method of the present invention has excellent water retention and moisturizing properties, so that it moisturizes the skin and hair, prevents drying, and has excellent permeability and tissue affinity. From the sex, it showed a unique activity effect.

In addition, it greatly contributes to increase the viscosity of the cosmetic itself and improve stability and usability.

Claims (2)

[Claims] 1. A method of degrading shellfish meat with a proteolytic enzyme, followed by complete deproteinization to remove low-molecular substances, and then adding a quaternary ammonium salt to precipitate and separate the acidic polysaccharide. The manufacturing method of the cosmetic raw material which has an acidic polysaccharide as a main component. 2. After decomposing shellfish meat with a protease,
Use a 10% concentration solution of trichloroacetic acid or perchloric acid, or perform complete deproteinization by the Sevag method, perform dialysis, and then add a quaternary ammonium salt to precipitate and separate the acidic polysaccharides. The method for producing a cosmetic raw material according to claim 1, wherein an inorganic salt aqueous solution is added and dissolved, and then an alcohol aqueous solution is added to reprecipitate and purify.