Compound containing ascorbic acid derivative

Abstract

The present invention relates to a food composition, a cosmetic composition, or a drug composition that contains an ascorbic acid 2-glucoside basic amino acid salt and an ascorbic acid 2-glucoside alkali metal salt. A composition according to the present invention is stable and imparts a good sensation when applied to the skin.

Description

Ascorbic acid derivative-containing composition

[0001] The present invention relates to a stable composition containing ascorbic acid 2-glucosides.

[0002] Ascorbic acid acts as a reducing agent, collagen synthesis promoter, and antioxidant. In particular, its excellent antioxidant effect inhibits melanin production in the skin, making it a known ingredient for preventing pigmentation such as age spots and freckles. It is widely used in pharmaceuticals, foods, cosmetics, and other products. However, as a bulk powder, ascorbic acid is unstable under hygroscopic or alkaline conditions. Furthermore, aqueous solutions of ascorbic acid are not only highly acidic and irritating, but also easily oxidize, causing browning through the Maillard reaction with typical amines involved in decomposition. As a result, cosmetics containing ascorbic acid and products containing water are prone to developing unpleasant odors due to browning, which reduces their value as a product and limits the amount of ascorbic acid that can be added to the product, affecting its effectiveness (Non-Patent Document 1). From this perspective, techniques have been reported that combine ascorbic acid with flavonoid glycosides to inhibit browning (Patent Documents 1 and 2). The use of ascorbic acid 2-glucoside instead of ascorbic acid has also been reported. However, aqueous solutions of ascorbic acid 2-glucoside have a low pH, and although their stability is slightly improved, they still suffer from the drawback of browning. Therefore, techniques have been reported in which strong basic substances, lecithin, ether compounds, ester compounds, citric acid, etc. are blended with ascorbic acid 2-glucoside (Patent Documents 3 to 6).

[0003] Japanese Patent Laid-Open No. 04-099771 Japanese Patent Laid-Open No. 04-099730 Japanese Patent Laid-Open No. 2001-199863 Japanese Patent Laid-Open No. 2002-265344 Japanese Patent Laid-Open No. 2005-220029 Japanese Patent Laid-Open No. 2012-246248

[0004] Journal of the Japanese Society for Food and Nutrition Studies, Vol. 26, No. 1, 7-10 (2015)

[0005] However, none of these methods have been able to sufficiently inhibit the browning reaction of ascorbic acid 2-glucoside, and have been able to sufficiently inhibit browning while maintaining the excellent effects of compositions such as cosmetics containing the same. The present inventors then produced and isolated a basic amino acid salt of ascorbic acid 2-glucoside and found that this substance was more stable and did not brown compared to conventional ascorbic acid or ascorbic acid 2-glucoside. However, there is room for further improvement in its stability, and there is also room for improvement in the feel when applied to the skin. Therefore, an object of the present invention is to provide a composition containing ascorbic acid 2-glucosides that is stable and has a good feel when applied.

[0006] Therefore, the present inventors have compounded various ingredients with ascorbic acid 2-glucoside basic amino acid salts and investigated their stability and the sensation of use when applied to the skin. As a result, they have found that the combined use of ascorbic acid 2-glucoside basic amino acid salts and ascorbic acid 2-glucoside alkali metal salts improves the stability and the sensation of use when applied to the skin, and have thus completed the present invention.

[0007] The present invention provides the following inventions [1] to [6]. [1] A food composition, cosmetic composition, or pharmaceutical composition containing an ascorbic acid 2-glucoside basic amino acid salt and an ascorbic acid 2-glucoside alkali metal salt. [2] The composition according to [1], wherein the ascorbic acid 2-glucoside basic amino acid salt is one or more salts selected from ascorbic acid 2-glucoside lysine salt, ascorbic acid 2-glucoside arginine salt, ascorbic acid 2-glucoside histidine salt, and ascorbic acid 2-glucoside tryptophan salt. [3] The composition according to [1] or [2], wherein the ascorbic acid 2-glucoside alkali metal salt is one or two salts selected from ascorbic acid 2-glucoside sodium salt and ascorbic acid 2-glucoside potassium salt. [4] The composition according to any one of [1] to [3], wherein the pH of the composition is 5.0 or more and 7.5 or less. [5] The composition according to any one of [1] to [4], wherein the ascorbic acid 2-glucoside basic amino acid salt is ascorbic acid 2-glucoside arginine salt. [6] The composition according to any one of [1] to [5], wherein the ascorbic acid 2-glucoside alkali metal salt is ascorbic acid 2-glucoside sodium salt.

[0008] An aqueous solution containing ascorbic acid 2-glucoside basic amino acid salt and ascorbic acid 2-glucoside alkali metal salt is significantly inhibited from discoloring and has a pH ranging from weakly acidic to neutral. Therefore, the aqueous solution has various functions of ascorbic acids, such as a whitening effect due to the inhibition of melanin production and a wrinkle-reducing effect due to the activation of collagen production, and is useful as a safe, non-irritating ingredient for foods, medicines, or cosmetics.

[0009] FIG. 1 shows the FT / IR spectrum of ascorbic acid 2-glucoside arginine salt powder.

[0010] One aspect of the present invention is a composition containing ascorbic acid 2-glucoside basic amino acid salt and ascorbic acid 2-glucoside alkali metal salt, which is particularly useful as a food composition, cosmetic composition, or pharmaceutical composition.

[0011] Ascorbic acid in the present invention is a compound whose IUPAC name is (R)-3,4-dihydroxy-5-((S)-1,2-dihydroxyethyl)furan-2(5H)-one, and is also known as vitamin C or L-ascorbic acid. As mentioned above, ascorbic acid acts as a reducing agent, a collagen synthesis promoter, and an antioxidant. In particular, the excellent antioxidant effect of ascorbic acid inhibits melanin production in the skin, and it is known as a component that prevents pigmentation such as age spots and freckles, and is widely used in pharmaceuticals, foods, and cosmetics.

[0012] Ascorbic acid 2-glucoside is a substance in which glucose is bound to the carbon atom at position 2 of ascorbic acid. It is metabolized in vivo to form ascorbic acid, and is therefore considered a provitamin of ascorbic acid. The ascorbic acid 2-glucoside basic amino acid salt used in the present invention is a basic amino acid salt of ascorbic acid 2-glucoside. Examples of the ascorbic acid 2-glucoside basic amino acid include one or more selected from ascorbic acid 2-glucoside lysine salt, ascorbic acid 2-glucoside arginine salt, ascorbic acid 2-glucoside histidine salt, and ascorbic acid 2-glucoside tryptophan salt. Of these, ascorbic acid 2-glucoside lysine salt and ascorbic acid 2-glucoside arginine salt are more preferred, and ascorbic acid 2-glucoside arginine salt is even more preferred. The molar ratio of ascorbic acid 2-glucoside to basic amino acid in the basic amino acid salt of ascorbic acid 2-glucoside is preferably 1:1.5 to 1.5:1, more preferably 1:1.2 to 1.2:1.

[0013] Ascorbic acid 2-glucoside basic amino acid salts can be produced by reacting ascorbic acid 2-glucoside with a basic amino acid. Specifically, ascorbic acid 2-glucoside and a basic amino acid are added to ion-exchanged water in which the dissolved oxygen concentration has been reduced by ultrasonication or other methods, and the reaction is carried out by adjusting the amount of basic amino acid added and adjusting the pH to 5.22 to 5.55 at 40 to 60°C. After completion of the reaction, the ascorbic acid 2-glucoside basic amino acid salt can be isolated as a powder by freeze-drying, spray-drying, or other methods. The resulting ascorbic acid 2-glucoside basic amino acid salt powder is stable for long periods of time and does not brown, making it useful as a raw material for incorporating into cosmetics and pharmaceutical compositions at high concentrations. In solutions, the upper concentration limit is inevitably limited due to the need to mix with other bases. Storing raw materials in a liquid state requires the addition of preservatives, sterilization by passing the liquid through a filter, filling into sterile containers, or storage at low temperatures. However, by powdering the raw materials, they can be stored stably and compactly at room temperature without adding any other ingredients.

[0014] The content of the ascorbic acid 2-glucoside basic amino acid salt in the composition of the present invention is preferably 1 to 40% by mass, more preferably 2 to 35% by mass, and even more preferably 5 to 30% by mass, from the viewpoints of stability, usability, and the ability of the ascorbic acid 2-glucoside basic amino acid salt to exhibit its function as ascorbic acid.

[0015] Examples of alkali metal ascorbic acid 2-glucoside salts include sodium ascorbic acid 2-glucoside, potassium ascorbic acid 2-glucoside, and lithium ascorbic acid 2-glucoside. Of these, sodium ascorbic acid 2-glucoside and potassium ascorbic acid 2-glucoside are preferred, with sodium ascorbic acid 2-glucoside being more preferred. The molar ratio of ascorbic acid 2-glucoside to the alkali metal in the alkali metal ascorbic acid 2-glucoside salt is preferably 1:1.5 to 1.5:1, and more preferably 1:1.2 to 1.2:1.

[0016] Ascorbic acid 2-glucoside alkali metal salts can be produced by methods described in, for example, Japanese Patent Publication No. 2002-88095 and Japanese Patent No. 6895436. For example, ascorbic acid 2-glucoside may be reacted with an alkali metal salt such as sodium hydroxide, sodium carbonate, or sodium bicarbonate. Specifically, ascorbic acid 2-glucoside and an alkali metal salt are added to ion-exchanged water in which the dissolved oxygen concentration has been reduced by sonication or other methods at 40 to 60°C, and the pH is adjusted to 6.0 to 6.5, adjusting the amount of alkali metal salt added to allow the reaction to proceed. After completion of the reaction, ascorbic acid 2-glucoside alkali metal salts can be isolated as powders by freeze-drying, spray-drying, or other methods. While ascorbic acid 2-glucoside alkali metal salts are known to have physiological activities similar to those of ascorbic acid, it is not known that their stability and usability are improved by their combined use with ascorbic acid 2-glucoside basic amino acid salts.

[0017] The content of the alkali metal ascorbic acid 2-glucoside in the composition of the present invention is preferably 1 to 50% by mass, more preferably 2 to 45% by mass, and even more preferably 5 to 40% by mass, from the viewpoints of stability, usability, and the ability of the alkali metal ascorbic acid 2-glucoside to exhibit its function as ascorbic acid.

[0018] The molar ratio (a / b) of the ascorbic acid 2-glucoside basic amino acid salt (a) to the ascorbic acid 2-glucoside alkali metal salt (b) in the composition of the present invention is preferably 0.2 to 5.0, more preferably 0.3 to 3.0, and even more preferably 0.5 to 2.0, from the viewpoints of the effect of preventing discoloration of the composition, the effect of exhibiting the functions of ascorbic acid, and the feel upon use, such as stickiness.

[0019] The pH of the composition of the present invention is preferably 5.0 to 7.5, more preferably 5.0 to 6.5, and even more preferably 5.0 to 6.0, from the viewpoints of preventing discoloration and reducing irritation when applied to the skin.

[0020] Compositions containing ascorbic acid 2-glucoside basic amino acid salts and ascorbic acid 2-glucoside alkali metal salts include food compositions, pharmaceutical compositions, and cosmetic compositions. These compositions may be in the form of liquid compositions, emulsion compositions, powder compositions, or solid compositions. Examples of food compositions include functional foods and foods for specified health uses. Examples of pharmaceutical compositions include oral administration preparations such as tablets, granules, and syrups; transdermal administration preparations such as creams, ointments, and liquids; eye drops; and injections. Cosmetic compositions may be liquid cosmetics, emulsion cosmetics, powder cosmetics, solid cosmetics, or the like. These cosmetics preferably contain, in addition to ascorbic acid 2-glucoside basic amino acid salts and ascorbic acid 2-glucoside alkali metal salts, ascorbic acid or a salt thereof, water, oils, surfactants, moisturizing ingredients, alcohols, polyols, UV absorbers, UV protection agents, various powders, various cosmetic ingredients, antioxidants, antibacterial agents, fragrances, and the like. Furthermore, from the viewpoint of fully obtaining the functions of the ascorbic acid 2-glucoside basic amino acid salt and the ascorbic acid 2-glucoside alkali metal salt, the cosmetic of the present invention is more preferably a skin cosmetic, and is preferably in the form of an aqueous liquid cosmetic, an oil-in-water emulsion cosmetic, or a water-in-oil emulsion cosmetic.

[0021] The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples.

[0022] [Production Example 1] Ion-exchanged water was degassed using ultrasound at 0.5 kW to 1.0 kW output. The degassing was performed for 20-40 minutes at a power setting of 0.8 kW. Degassing was confirmed by measuring with a dissolved oxygen concentration meter until the dissolved oxygen concentration reached 0.5 ppm or less, yielding ion-exchanged water. 50 ml of this water was heated to 45-60°C, preferably 50°C ± 0.5°C. 5.0 g of ascorbic acid 2-glucoside was dissolved by stirring, and then 14.464 mmol of arginine was added. The pH was preferably adjusted to 5.22-5.55, more preferably 5.35. The molar concentration of arginine added was finely adjusted by adjusting the pH. This solution was lyophilized to obtain a powder of ascorbic acid 2-glucoside arginine salt (7.55 g, 90.03%). The FT / IR spectrum of the resulting powder of ascorbic acid 2-glucoside arginine salt is shown in Figure 1. The spectrum result is 1720 cm -1 (non-ionic COOH, antisymmetric stretching vibration) and characteristic band 1400 cm -1 was observed, confirming the introduction of arginine ionic bonds.

[0023]

[0024] [Production Example 2] The ion-exchanged water treatment method used for dissolution was the same as in Production Example 1. 100 ml of this ion-exchanged water was set to 50°C ± 0.5°C, and 5.0 g of ascorbic acid 2-glucoside was added and dissolved by stirring. 17.97 mmol of lysine was then added. The pH was 5.1-5.6, but the molar concentration was finely adjusted to pH 5.3. This solution was lyophilized to obtain a powder of ascorbic acid 2-glucoside lysine salt (7.62 g, 98.42%).

[0025] Example 1 (Mixture of ascorbic acid 2-glucoside arginine salt (ASA2-G·Arg) and ascorbic acid 2-glucoside sodium salt (ASA2-G·Na)) The solubility of ASA2-G is 879 g / L (25°C), or 46.8% by weight. ASA2-G·Arg and ASA2-G·Na have improved solubility in water and could be dissolved in water at a high concentration of 70% by weight or more. Furthermore, ASA2-G·Arg and ASA2-G·Na could be dissolved in water simultaneously, making it possible to increase the combined concentration of the ascorbic acid 2-glucoside derivatives. A beauty serum containing a mixture of ASA2-G·Arg and ASA2-G·Na (total concentration of these components: 40% by weight) was prepared and applied to the faces of six subjects. A questionnaire survey on the feel (stickiness) of the product was conducted. Scores ranging from good to bad (higher scores are better) were averaged. Four weight ratios of ASA2-G·Arg:ASA2-G·Na (Test Products 2-5) were used: 100:0, 80:20, 60:40, 40:60, 20:80, and 0:100. These were compared with Test Product 1, in which ASA2-G·Arg was dissolved alone. Furthermore, Test Products 1-5 were filled into transparent glass containers and stored at 40°C for two weeks, and the change in color was visually observed. The results are shown in Table 1.

[0026]

[0027] With test product 1, some subjects felt sticky after application. Test products 2-5 had almost the same feel when used, and none of the subjects felt sticky. It was found that the feel when used was significantly improved when ASA2-G Na was blended in a ratio of 1 / 4 or more to ASA2-G Arg. Furthermore, test products 2-5 showed similar levels of browning when stored at 40°C for two weeks, with no difference.

[0028] Example 2 The following is an example of the formulation and manufacturing method for producing a beauty serum by blending 5% by mass of ascorbic acid 2-glucoside arginine salt (ASA2-G·Arg) and 5% by mass of ascorbic acid 2-glucoside sodium salt (ASA2-G·Na): (1) Composition (unit: mass %) 1. Water 67.98% 2. Propanediol 17.0% 3. ASA2-G·Arg 5.0% 4. ASA2-G·Na 5.0% 5. Glycerin 3.9% 6. Sodium citrate 0.5% 7. 1,3-BG 0.30% 8. Glycosphingolipid 0.15% 9. Xanthan gum 0.12% 10. Sodium hyaluronate 0.02% 11. 1. Citric acid 0.02% 2. Acetyl hydroxyproline 0.01% 3. Hydrolyzed collagen 0.001% 4. Hydrolyzed elastin 0.00001% (2) Manufacturing method The oil phase components are mixed and heated to approximately 80°C. Next, the remaining raw materials (water-soluble components) are mixed and heated to approximately 80°C. While maintaining the temperature at 80°C, the oil phase components are gradually added to the water-soluble components while stirring with a homomixer to emulsify. Finally, the temperature is cooled to room temperature, and then ASA2-G·Arg and ASA2-GNa are added, mixed well, and homogenized to form the final product.

Claims

1. A food composition, cosmetic composition or pharmaceutical composition containing a basic amino acid salt of ascorbic acid 2-glucoside and an alkali metal salt of ascorbic acid 2-glucoside.

2. 2. The composition according to claim 1, wherein the ascorbic acid 2-glucoside basic amino acid salt is one or more selected from the group consisting of ascorbic acid 2-glucoside lysine salt, ascorbic acid 2-glucoside arginine salt, ascorbic acid 2-glucoside histidine salt, and ascorbic acid 2-glucoside tryptophan salt.

3. 3. The composition according to claim 1, wherein the alkali metal ascorbic acid 2-glucoside salt is one or two selected from the group consisting of sodium ascorbic acid 2-glucoside and potassium ascorbic acid 2-glucoside.

4. 3. The composition according to claim 1, wherein the pH of the composition is 5.0 or more and 7.5 or less.

5. 3. The composition according to claim 1, wherein the ascorbic acid 2-glucoside basic amino acid salt is ascorbic acid 2-glucoside arginine salt.

6. 3. The composition according to claim 1, wherein the alkali metal ascorbic acid 2-glucoside is sodium ascorbic acid 2-glucoside.