Compound containing ascorbic acid derivative

Abstract

The present invention relates to a composition in which browning is suppressed, said composition containing an ascorbic acid 2-glucoside basic amino acid salt. The inclusion of the ascorbic acid 2-glucoside basic amino acid salt makes it possible to suppresses the browning of the composition.

Description

Ascorbic acid derivative-containing composition

[0001] The present invention relates to a composition containing ascorbic acid 2-glucosides that is inhibited from browning.

[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 in hygroscopic and alkaline conditions. Furthermore, aqueous solutions of ascorbic acid are not only highly acidic and irritating, but also easily oxidize. The Maillard reaction occurs with typical amines involved in the decomposition, causing browning and furthering the browning reaction. 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 ascorbic acid 2-glucoside. Therefore, an object of the present invention is to provide a new method for inhibiting the browning of ascorbic acid 2-glucoside, and a composition containing ascorbic acid 2-glucoside in which browning is inhibited.

[0006] Therefore, the present inventors have conducted various studies to find new means for inhibiting the browning of ascorbic acid 2-glucoside. First, the inventors focused on the fact that ascorbic acid is a sugar acid having an unsaturated lactone. Since it has been known that sugar and amino acid-containing substances are susceptible to the Maillard reaction (i.e., browning) at room temperature or when heated, various amino acids, amino acid / sugar mixtures, amino acid / amino acid ester mixtures, peptides, 2-amino-2-methyl-1-propanol, ε-aminocaproic acid, γ-aminobutyric acid, etc., were added to ascorbic acid and mixed. It was found that the addition of amino acids to ascorbic acid rapidly promoted the browning reaction. Therefore, a mixed system of ascorbic acid 2-glucoside and an amino acid was used as a test system for the browning reaction of ascorbic acid 2-glucoside, and a screening was conducted for components that inhibit the browning of ascorbic acid 2-glucoside. Surprisingly, the researchers found that converting ascorbic acid 2-glucoside into an ascorbic acid 2-glucoside basic amino acid salt significantly inhibits the browning reaction. Furthermore, the researchers found that the ascorbic acid 2-glucoside basic amino acid salt can be obtained as a powder with good storage stability, and that its aqueous solution has a pH ranging from weakly acidic to neutral, causing little skin irritation, making it an excellent ingredient for use in various compositions, such as cosmetics. Furthermore, the researchers found that the combined use of ascorbic acid 2-glucoside basic amino acid salt and ascorbic acid or a salt thereof can result in a composition that provides a good feel when used.

[0007] The present invention provides the following inventions [1] to

[10] . [1] A composition containing an ascorbic acid 2-glucoside basic amino acid salt and inhibiting browning. [2] The composition according to [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] The composition according to [1] or [2], wherein the pH of the composition is 5.0 or more and 7.5 or less. [4] The composition according to any one of [1] to [3], which is a food composition, a pharmaceutical composition, or a cosmetic composition. [5] A composition containing (a) ascorbic acid 2-glucoside basic amino acid salt and (b) ascorbic acid or a salt thereof. [6] The composition according to [5], wherein (b) ascorbic acid or a salt thereof is one or more selected from ascorbic acid, alkali metal ascorbic acid salts, amino acid salts of ascorbic acid, and amine ascorbic acid salts. [7] The composition according to [5] or [6], wherein (a) ascorbic acid 2-glucoside basic amino acid salt is 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. [8] The composition according to any one of [5] to [7], wherein the pH of the composition is 5.0 or more and 7.5 or less. [9] The composition according to any one of [5] to [8], which is a food composition, a pharmaceutical composition, or a cosmetic composition.

[10] A powder of ascorbic acid 2-glucoside basic amino acid salt.

[0008] An aqueous solution of ascorbic acid 2-glucoside basic amino acid salt exhibits significantly reduced browning and has a pH ranging from weakly acidic to neutral, thereby exhibiting the diverse functions of ascorbic acids, including a whitening effect due to the inhibition of melanin production and an anti-wrinkle effect due to the activation of collagen production, making it useful as a safe, non-irritating ingredient in foods, pharmaceuticals, or cosmetics. Furthermore, since the present invention enables the production of ascorbic acid 2-glucoside basic amino acid salt in powder form, the ingredient can be stably stored for long periods of time and can be incorporated at high concentrations into compositions such as cosmetics, foods, pharmaceuticals, and the like. By containing ascorbic acid 2-glucoside basic amino acid salt and ascorbic acid or a salt thereof, food compositions, pharmaceutical compositions, and cosmetic compositions with excellent storage stability and a pleasant feel when used can be obtained.

[0009] 1 is a diagram showing the degree of browning of L-ascorbic acid due to the addition of amino acids; 2 is a diagram showing the FT / IR spectrum of ascorbic acid 2-glucoside arginine salt powder; 3 is a diagram showing the results of evaluating the degree of browning (coloration) by measuring the absorption spectrum (wavelength 480 nm) of a test solution sampled at specified months (Example 1); 4 is a diagram showing the results of evaluating the degree of browning (coloration) by measuring the absorption spectrum (wavelength 480 nm) of a test solution sampled at specified months (Example 2).

[0010] The present inventors have found that various compositions containing ascorbic acid 2-glucoside basic amino acid salts are inhibited from browning. Accordingly, one aspect of the present invention is a composition containing ascorbic acid 2-glucoside basic amino acid salts and inhibited from browning.

[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. 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] As shown in the Examples below, ascorbic acid 2-glucoside basic amino acid salts are extremely stable and do not brown even in aqueous solution. This effect is completely unexpected, considering that browning occurs due to the Maillard reaction between ascorbic acid and ordinary amino acids. Therefore, compositions containing ascorbic acid 2-glucoside basic amino acid are useful as compositions for foods, pharmaceuticals, cosmetics, and the like, which are inhibited from browning.

[0015] 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 the browning inhibitory effect and the ability of the ascorbic acid 2-glucoside basic amino acid salt to exhibit its function as ascorbic acid.

[0016] Compositions containing ascorbic acid 2-glucoside basic amino acid 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 preparations such as tablets, granules, and syrups; transdermal 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, 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, the cosmetic of the present invention is more preferably a skin cosmetic, from the viewpoint of fully utilizing the functions of ascorbic acid 2-glucoside basic amino acid salts. The cosmetic composition is preferably in the form of an aqueous liquid cosmetic, an oil-in-water emulsion cosmetic, or a water-in-oil emulsion cosmetic.

[0017] 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 viewpoint of inhibiting browning and reducing irritation when applied to the skin.

[0018] The composition containing the ascorbic acid 2-glucoside basic amino acid salt of the present invention can be further blended with ascorbic acid or a salt thereof to provide a composition, particularly a cosmetic, with an excellent feel when used. Accordingly, another aspect of the present invention is a composition containing (a) ascorbic acid 2-glucoside basic amino acid salt and (b) ascorbic acid or a salt thereof.

[0019] The salt of ascorbic acid may be any salt of ascorbic acid and a basic substance, and may be, for example, one or more selected from alkali metal ascorbic acid salts, amino acid ascorbic acid salts, and amine ascorbic acid salts. Examples of alkali metal ascorbic acid salts include sodium, potassium, and lithium salts of ascorbic acid. Examples of amino acid ascorbic acid salts include glycine, alanine, valine, leucine, isoleucine, lysine, arginine, histidine, serine, threonine, cysteine, methionine, asparagine, glutamine, proline, phenylalanine, tyrosine, and tryptophan salts of ascorbic acid. Examples of amine salts of ascorbic acid include ammonium, alkylamine, and alkanolamine salts of ascorbic acid. Of these, alkali metal ascorbic acid salts are more preferred. The molar ratio of ascorbic acid to the basic substance in the salt of ascorbic acid is preferably 1:1.5 to 1.5:1, more preferably 1:1.2 to 1.2:1.

[0020] The molar ratio (a / b) of the components (a) and (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 browning-inhibiting effect of the composition, the effect of exhibiting the functions of ascorbic acid, and the feel upon use, such as stickiness.

[0021] From the same viewpoint as above, 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.

[0022] Compositions containing ascorbic acid 2-glucoside basic amino acid salts and ascorbic acid or its salts include food compositions, pharmaceutical compositions, and cosmetic compositions, as described above. These compositions may take 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 or its salts, 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 ascorbic acid 2-glucoside basic amino acid salt and ascorbic acid or a salt thereof, 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.

[0023] The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples.

[0024] [Preparation of Test System] The difference in browning degree (coloring degree) based on the type of amino acid was examined for reaction solutions of ascorbic acid (1%) and amino acids (0.12%) in 10 mM citrate phosphate buffer, pH 7.0. Measurement wavelength: 480 nm, measurement time: 10 days after production. The results are shown in Figure 1. As a result, it was suggested that the browning degree (coloring degree) was high when the amino acids added to ascorbic acid were glycine, histidine, lysine, and alanine, and that the browning degree was particularly remarkable and the browning rate was fast when glycine and histidine were added. Therefore, in the system in which amino acids were added to ascorbic acid, browning of ascorbic acid proceeded extremely rapidly, and it was found that the test system in which amino acids were added to ascorbic acid is suitable as a screening system for amino acid browning inhibitors.

[0025] [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 2. 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.

[0026]

[0027] [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%).

[0028]

[0029] Example 1 (Effect of Addition of Ascorbic Acid 2-Glucoside Arginine Salt on Changes in Browning Degree (Coloration Degree) of Ascorbic Acid Due to Addition of Amino Acids) 1.5% ascorbic acid (ASA) was dissolved in 100 ml of water, and the pH was adjusted to 5.0 with 1 M sodium hydroxide solution to prepare a test solution. Ascorbic acid 2-glucoside arginine salt (ASA2-G·Arg) was prepared by dissolving the product of Production Example 1 in 100 ml of water to a concentration of 1.5%. 0.2% glycine was added to each of these test solutions, which were then stored at room temperature for 20 months. This test solution was sampled at specified months, and the absorption spectrum (wavelength 480 nm) was measured to evaluate the browning degree (coloration degree). The results are shown in Figure 3.

[0030] [Evaluation] Appearance (Transparency) At zero (0), the initial state immediately after preparation was visually observed. At other specified months, measurements were taken using a spectrophotometer (absorption spectrum: wavelength 480 nm). With ascorbic acid, browning began to occur at 4 months, and the appearance of transparency was confirmed visually, and at 14 months, a noticeable light brown color appeared. On the other hand, the initial state was confirmed for the ASA2-G·Arg-added system. Furthermore, the ASA2-G·Arg-added system was visually observed at 20 months, and the initial state was observed, with an absorption spectrum of 0.01.

[0031] Example 2 Experiment 2: Changes in browning (coloring) degree of ascorbic acid and ascorbic acid 2-glucoside lysine salt (Production Example 2) with the addition of an amino acid mixture. A 4% solution of ascorbic acid (ASA) was dissolved in 200 ml of water, and the pH was adjusted to 5.0 with 1 M sodium hydroxide solution to prepare test solutions. A 4% solution of ascorbic acid 2-glucoside lysine salt (ASA2-G·Lys) (Production Example 2) was similarly dissolved to prepare test solutions. An amino acid mixture (1.5% histidine, 1.2% alanine, 2.6% leucine) was added to each test solution and stored at room temperature for 20 months. Each test solution was sampled at designated months, and the absorption spectrum (wavelength: 480 nm) was measured to evaluate the change in browning (coloring) degree. The results are shown in Figure 4.

[0032] [Evaluation] Appearance (Transparency) In this measurement, an amino acid mixture was added to the test solution. As a result, ascorbic acid (ASA) began to brown after 4 months, as in Example 1, and the browning phenomenon continued rapidly thereafter, turning brown at 20 months. ASA2-G·Lys turned a very light brown at 20 months, and the absorbance (Abs) of the absorption spectrum at this time was 0.017.

[0033] Example 3 A formulation example and a manufacturing method example for producing a beauty serum containing 10% by mass of ascorbic acid 2-glucoside arginine salt (ASA2-G·Arg) are shown below. (1) Composition (unit: mass%) 1. Water 67.98% 2. Propanediol 17.0% 3. ASA2-G・Arg 10.0% 4. Glycerin 3.9% 5. Sodium Citrate 0.5% 6. 1,3-BG 0.30% 7. Glycosphingolipid 0.15% 8. Xanthan Gum 0.12% 9. Sodium Hyaluronate 0.02% 10. Citric Acid 0.02% 11. Acetylhydroxyproline 0.01% 12. Hydrolyzed Collagen 0.001% 13. Hydrolyzed Elastin 0.00001% (2) Manufacturing Method The oil phase ingredients are mixed and heated to approximately 80°C. Next, the remaining ingredients (water-soluble ingredients) are mixed and heated to approximately 80°C. While maintaining the temperature at 80°C, gradually add the oil phase ingredients to the water-soluble ingredients while stirring with a homomixer to emulsify. Finally, cool to room temperature, add ASA2-G Ag, mix well, and homogenize to make the final product.

[0034] Example (Comparison of Stability of ASG and ASA2-G·Arg) A cosmetic serum containing 5% by mass of ASA2-G·Arg and ascorbic acid 2-glucoside (ASG) was prepared in the same manner as in the above example and used as a sample. It was filled into a transparent 30 mL glass bottle with a lid and stored at room temperature under an illumination of 30,000 lux. The absorbance at 420 nm was measured at 0, 1, 2, 3, 4, 5, and 6 months. The sample was diluted 100-fold with water at the time of measurement. Water was used as a blank.

[0035]

[0036] Browning was observed over time with the ASG-containing serum, but no browning was observed with the ASA2-G·Arg-containing serum within the six months of continued testing.

[0037] Example (Mixture of ASA2-G Arg and Sodium Ascorbate) A beauty serum (total concentration of these components: 30% by mass) containing a mixture of ASA2-G Arg and sodium ascorbate (ASNa) was prepared, and six subjects applied it to their faces. A questionnaire survey was conducted to assess the feel (stickiness) of the product after use. Scores on a five-point scale from good to bad were averaged.

[0038]

[0039] Some subjects felt that test product 1 was sticky after application. Test products 2-6 had almost the same feel when used. It was found that the feel when used was significantly improved when ASNa was blended at 20% or more. Furthermore, test products 1-5 had the same degree of browning when stored at 40°C, with no difference.

Claims

1. A composition comprising (a) an ascorbic acid 2-glucoside basic amino acid salt, and (b) ascorbic acid or a salt thereof.

2. 2. The composition according to claim 1, wherein (b) the ascorbic acid or a salt thereof is one or more selected from the group consisting of ascorbic acid, alkali metal ascorbic acid salts, amino acid salts of ascorbic acid and amine salts of ascorbic acid.

3. 3. The composition according to claim 1 or 2, wherein the (a) 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.

4. 3. The composition according to claim 1, wherein the pH of the composition is from 5.0 to 7.

5.

5. 3. The composition according to claim 1 or 2, which is a food composition, a pharmaceutical composition or a cosmetic composition.