JP2003104837A - Emulsified composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for safely producing an emulsified substance effective for the skin. SOLUTION: The highly effective and emulsified substance is obtained by reacting a sugar with highly effective and highly safe marine collagen without using a harmful catalyst.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an emulsified composition containing a carbonyl reaction product of a marine organism-derived collagen and a saccharide.

[0002]

BACKGROUND OF THE INVENTION Collagen is a major protein forming animal skin such as cowhide, pig skin, and fish skin. Collagen is an important connective tissue protein that occupies 70% of the dermis and is involved in the generation of firmness and wrinkles of the skin, and also has a high moisturizing property and also affects the freshness of the skin. However, it is damaged by aging and sunlight. In order to prevent this, it has been used in large amounts as a raw material for cosmetics. Further, they are also used in medicines and medical devices because they have excellent biocompatibility. Furthermore, in recent years, it has attracted attention as a food material. Collagen that has been used so far was mainly derived from cowhide and pig skin, but in recent years, due to the influence of viruses contained in them, collagen has a different structure depending on its origin, and collagen of various origins has been developed. ing. Moreover, regarding shellfish meat, the pearl oysters used for cultivating scallops and pearls had a problem in treating the shellfish as waste except for the scallops. Already, patent registration Nos. 1853341, 1805187, 192981
The patents used in each of the publications of No. 5 are open to the public, but at present, many parts are discarded as waste.

On the other hand, a protein-polysaccharide complex is a substance having an emulsifying activity or an antibacterial property and is disclosed in JP-A-3-215498.
It is known in Japanese Patent Publication No. From the viewpoint of safety, various studies have been made on the emulsifier in order to suppress the amount used, and a substance which is a natural product and has an emulsifying property has been demanded.

DISCLOSURE OF THE INVENTION The present inventors have investigated a method for safely producing a substance that is emulsifying and effective on the skin.

[0004]

[Means for Solving the Problems] By utilizing marine collagen, which is highly effective and highly safe, by reacting it with sugars without using a dangerous catalyst, it is highly effective and emulsifiable. Was successfully obtained.

Examples of marine collagens include skins of yellowfin tuna, salmon, cod, shark, sole, saury, eel and the like. A known method may be adopted as the collecting method. As an example, a method for collecting shellfish collagen of pearl oysters will be described below. When pearls are cultivated for pearl oysters and pearls are taken out, scallops collect shell meat after removing the scallops. Water is added to this and stirred to collect insoluble matter. The method may be a known method. That is, for example, a method of adding water and then stirring and then separating with a centrifuge or a method of leaving the supernatant after leaving it still may be selected. To further remove impurities from this insoluble matter, salt solutions such as sodium chloride, potassium chloride, sodium acetate, sodium citrate, sodium hydrogen phosphate, sodium hydroxide, potassium hydroxide, calcium hydroxide,
A basic solution such as aqueous ammonia or a chelating agent such as ethylenediaminetetraacetate is added and stirred to collect insoluble matter. After further removing impurities with a water-soluble organic solvent such as ethanol, collagen is obtained by acid extraction with acetic acid, citric acid, lactic acid, hydrochloric acid, phosphoric acid or the like. The concentration varies depending on the type of acid and various conditions, but is 0.
It is carried out at a concentration of 01 to 2 molar. It is extracted by adding this solution and stirring for 2 to 48 hours. The temperature is 30 ° C or lower, preferably 2 to 10 ° C. In addition, the enzyme may be used, and then extraction may be performed by a known method such as an acid extraction method.
Further, depending on the application, it may be better to further purify, and it is purified using a hydrophilic organic solvent, a salting-out method or the like.

[0006] Commercially available marine collagens include extracts from yellowfin tuna skin, shark-derived extracts, and sole's soles, and these can also be used.

Sugar is reacted with the above-mentioned marine collagen. As a result of studies conducted by the present inventors, it was found that glycogen, dextrin, and glucose were most suitable for use in the present invention. In particular, glucose is highly reactive, and as a result, a substance having a good emulsifying property is obtained. In addition, the glycogen derived from pearl oyster disclosed in JP 2001-97845 A has a high function as a skin external preparation,
It is suitable as a saccharide used in the present invention.

The above-mentioned marine collagen and saccharide are reacted to obtain a carbonyl reaction product, but it is not necessary to use a special catalyst or condition. The reaction occurs when both are mixed and allowed to stand, but in order to enhance the reaction, the solid state is better and the reaction is better when the water content is smaller. The relative humidity is preferably 30 to 70%, and the reaction proceeds better when heated, but the desired carbonyl compound cannot be obtained if heated too much, so 100 ° C or lower is appropriate. The reaction time varies greatly depending on conditions such as temperature and humidity, but as a result of examination by the present inventors, when the relative humidity is 65% and the temperature is 80 ° C., the reaction time is 6 to 30.
The time was right. Also, the mixing ratio of marine collagen and saccharides does not pose any problem even if it remains as an unreacted product, so it can be set arbitrarily, but if there is too much difference between the two, the amount of the required carbonyl reactant will be obtained. Therefore, the mixing ratio of marine collagen and saccharides is preferably about 0.2 to 3 with marine collagen as 1 and saccharides. (The following ratios and percentages are weight ratios unless otherwise specified)

This is compounded in an emulsified composition. The dosage form is not particularly limited as long as it is an emulsified composition, so lotions, emulsions,
Select any form of creams, ointments, packs,
Further, the mixing ratio is arbitrary, but 0.0001 to 10
Blend in the range of%. To formulate these dosage forms, natural animal and vegetable oils and fats such as olive oil, mink oil, castor oil, palm oil, evening primrose oil, coconut oil, castor oil, cocoa oil, macadamia nut oil and the like; waxes such as jojoba oil, beeswax , Lanolin, carnauba wax, candelilla wax and the like; higher alcohols such as lauryl alcohol, stearyl alcohol, cetyl alcohol, oleyl alcohol and the like; higher fatty acids such as lauric acid, palmitic acid, stearic acid, oleic acid, behenic acid and lanolin fatty acid; Higher aliphatic hydrocarbons such as liquid paraffin, solid paraffin, squalane, petrolatum, ceresin, microcrystalline wax, etc .; synthetic ester oils such as butyl stearate, hexyl laurate, diisopropyl adipate, diisopropyl sebum Door,
Octyldodecyl myristate, isopropyl myristate, isopropyl palmitate isopropyl myristate, cetyl isooctanoate, neopentyl glycol dicaprate; Silicone derivatives Silicone oils such as methyl silicone and methyl phenyl silicone

For the purpose of the present invention, the surfactant should not be blended or should be kept in a small amount, but when blended, the surfactant may be an anionic surfactant such as an alkyl sulfate or a fatty acid. Salt, alkyl phosphate,
Phosphates and sulfates of polyoxyethylene alkyl ether; nonionic surfactants such as glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkyl ether, sorbitan fatty acid ester, polyoxyethylene hydrogenated castor oil, Polyglycerin fatty acid ester, etc .; Double-sided activator, for example, alkyl betaine, phosphobetaine, phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidylglycerol, phosphatidylinositol and their lyso forms, as well as phosphofatidic acid and its salts

Polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol,
Further polyethylene glycols, propylene glycol, dipropylene glycol, further polypropylene glycols, 1,3-butylene glycol,
Butylene glycols such as 1,4-butylene glycol, glycerin, diglycerin, and more polyglycerins, sorbitol, mannitol, xylitol,
Maltitol and other sugar alcohols, glycerin ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO) adduct, sugar alcohols E
O, PO adducts, saccharides such as galactose, glucose and fructose and their EO and PO adducts, maltose,
Polysaccharides such as lactose and polyhydric alcohols such as EO and PO adducts

As drugs, tocopherol, tocopherol acetate, vitamin C, allantoin, elastin, arbutin, collagen, triclosan, trichlorocarbane, dipotassium glycyrrhizinate, methylparaben, butylparaben.

The production examples, examples, etc., which are the practical use methods of the present invention, will be described below.
It is not limited to the examples. Production Example 1 2 g of pearl oyster collagen and 1 g of dextrin (trade name dextrin manufactured by Wako Pure Chemical Industries, Ltd.) were mixed and allowed to stand at 80 ° C. for 12 hours while maintaining a relative humidity of 65%.

The pearl oyster collagen was prepared by the following method. 30 880g of pearl oyster collagen pearl oyster excluding shells and pearls
After washing with g salt to remove slimy skin, 0.6
An aqueous solution of potassium chloride N was added to 1200 ml and stirred for 1 hour. Then, the mixture was stirred with 1200 ml of 0.45 M sodium chloride for 1 hour, and the collected shellfish was washed with water, then washed with 0.1
The mixture was stirred in 500 ml of an aqueous M acetic acid solution for 12 hours. The obtained suspension was centrifuged at 3000 xg for 20 minutes, and the precipitate was collected. This was added to 600 ml of 0.01 N hydrochloric acid aqueous solution, then 1.0 g of pepsin was added, and the mixture was stirred at 37 ° C. for 12 hours. The obtained suspension was centrifuged at 9500 × g for 2 hours, the supernatant was applied to a dialysis membrane (molecular weight 10000), and the solution was left standing for 12 hours in purified water. The dialyzed solution was freeze-dried. The yield was 3.0 g.

Production Example 2 The same procedure as in Production Example 1 except that the dextrin in Production Example 1 was replaced with pearl oyster-derived glycogen.

The pearl oyster-derived glycogen was prepared as follows. Glycogen derived from pearl oysters was obtained by the following method. Mucus of the pearl oyster was removed on a wire net, and 1500 g of the flesh was homogenized with a Waring blender for 2 minutes. Add 2500 ml of distilled water to this, and add 3 in boiling water.
Heated for 0 minutes with stirring. The mixture was centrifuged at 350 G for 20 minutes, 1000 ml of distilled water was added to the residue, and the mixture was likewise heated several times until no opalescence was observed. The glycogen extracts were combined to form Toyo Filter Paper No. Suction filtered with 1,
The filtrate was concentrated under reduced pressure to 3750 ml, trichloroacetic acid was added so that the final concentration was 5% by volume, and the mixture was allowed to stand at 4 ° C. for 12 hours. Centrifuge at 4500G for 60 minutes to remove proteins, and then add 3 volumes of ethanol to the supernatant to give a final concentration of 75
It was brought to volume% and precipitated to give crude glycogen. This was dissolved in 400 ml of distilled water and then 1600 ml of ethanol was added to collect the precipitate. This operation was repeated 3 times to wash glycogen. At this time, 1-2 drops of a saturated calcium chloride solution were added in order to completely form a precipitate. The obtained precipitate was dissolved in a small amount of cold distilled water, dialyzed against the same solution, centrifuged at 2500 G for 10 minutes, and the supernatant was lyophilized to obtain pearl oyster-derived glycogen.

Production Example 3 The dextrin of Production Example 1 was replaced with glucose, and the others were produced in the same manner.

Production Example 4 The pearl pearl oyster collagen of Production Example 1 was replaced with yellowfin tuna collagen (trade name Marine Pure Collagen manufactured by Katakura Chikkarin Co., Ltd.) and the others were prepared in the same manner.

Production Example 5 The pearl pearl oyster collagen of Production Example 1 was replaced with cod collagen (trade name marine collagen manufactured by Yaizu Suisan Co., Ltd.), and other preparations were made in the same manner.

Example 1 A (gel) Production Example 1 1.0 Glycerin 23.5 Squalane 0.48 Vitamin E (RIKEN Vitamin E700) 0.02 B A (gel) 3.0 1,3 Butylene glycol 20.0 Purified water 77.0 The method of preparation is to prepare a gel according to the conventional method with component A, and then
Using this gel, an emulsion was prepared at a ratio like B according to a conventional method.

Example 2 Mineral oil 5.0 Beeswax 1.0 Production example 2 3.0 Behenyl alcohol 0.5 Macadamia nut oil 6.0 Silicone 0.2 Vitamin E 0.1 Purified water 63.75 Glycerin 15.0 1. 2 Pentanediol 5.0 Sodium hydroxide 0.05 Carboxyvinyl polymer 0.3 Sodium hyaluronate 0.1 The method of preparation is to homogenize an aqueous component and an oily component to obtain an emulsion, and then add a water-soluble polymer phase. Then, an emulsion was obtained.

[0022] Example 3 Mineral oil 2.0 Production Example 3 2.0 Purified water 45.8 Glycerin 40.0 Methyl paraoxybenzoate 0.2 An emulsion was prepared according to a conventional method.

Example 4 The example 2 was prepared in the same manner as the example 2 except that the example 2 of the example 2 was replaced with the example 4.

Example 5 Example 3 was prepared in the same manner as in Example 3 except that Production Example 3 was replaced with Production Example 5.

As a comparative example, the following cream was prepared. Comparative Example 1 Manufactured in the same manner as in Example 1 except that Production Example 1 of Example 1 was replaced with 0.67% of pearl oyster collagen and 0.33% of dextrin.

Comparative Example 2 Preparation was carried out in the same manner as in Example 1 except that Production Example 2 of Example 2 was replaced with pearl oyster collagen 2.0% and pearl oyster derived glycogen 1.0%.

The following experiments were conducted to confirm the effectiveness. Experiment 1 Example 1 and Comparative Example 1 were stored in a thermostatic chamber at 25 ° C. and 50 ° C., and the absorbance at 750 nm was measured as one index of emulsifying property. The results are shown below. As described above, the emulsifiability after preparation is good, and the emulsifiability is better than that of the comparative example even when left at 50 ° C.

As a result of measuring the particle size, the results are as follows.

Experiment 3 When 10 women evaluated the oily feeling, the following results were obtained. As described above, since the particle size of Example 2 is smaller than that of Comparative Example 2, oiliness is less likely to be felt, which is due to the small particle size.

As described above, marine collagen, which is highly effective and safe, is used to react with sugars without using a dangerous catalyst, so that it is highly effective and has an emulsifying property. Succeeded in obtaining the substance.

【effect】

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Nobuhide Tsuji             34, 9 Hommachi, Ise City, Mie Prefecture F-term (reference) 4C083 AA071 AA072 AA082 AA162                       AB032 AB052 AC022 AC072                       AC122 AC482 AD092 AD152                       AD332 AD431 AD432 AD662                       CC05 DD31 EE10

Claims (3)

[Claims] 1. An emulsified composition comprising a carbonyl reaction product of a marine organism-derived collagen and a saccharide. 2. The emulsified composition according to claim 1, wherein the marine organism-derived collagen is collagen obtained from shellfish meat. 3. The emulsion composition according to claim 1, wherein the saccharide is glucose, glycogen or dextrin.