TW201808980A - 2-O-[alpha]-D-glycosyl-L-ascorbic acid metal salts, their uses as an antioxidant and a manufacturing method of the metal salts powder - Google Patents

Abstract

The present invention provides a metal salt of 2-O-[alpha]-D-glycosyl-L-ascorbic acid represented by general formula (1), and amorphous powder there of and (wherein, n represents an integer above 1.) Further, the present invention provides an antioxidant comprising the metal salt of 2-O-[alpha]-D-glycosyl-L-ascorbic acid.

Description

2-O-α-D-glycosyl-L-ascorbic acid metal salt, its use as an antioxidant, and method for producing powder of the metal salt

The present invention relates to a method for producing 2-O-α-D-glycosyl-L-ascorbic acid metal salt with excellent stability, its use as an antioxidant, and an amorphous powdery solid of the metal salt.

2-O-α-D-glucopyranosyl-L-ascorbic acid, which is a typical 2-O-α-D-glycosyl-L-ascorbic acid, has a chemical structure represented by the following chemical formula (2), and L-ascorbic acid and D-glucose are produced by hydrolysis:

Compared with L-ascorbic acid, it is known that 2-O-α-D-glucopyranosyl-L-ascorbic acid is not easily oxidized and has excellent stability. On the other hand, it is easily hydrolyzed in the body to have the same level as L-ascorbic acid The physiological activity (Patent Documents 1 and 2) is expected to be widely used in cosmetics, foods, and pharmaceuticals. In addition, it is known that 2-O-α-D-glucopyranosyl-L-ascorbic acid based on crystals is particularly excellent in stability (Patent Document 1). However, the stability in the solution of 2-O-α-D-glucopyranosyl-L-ascorbic acid is problematic, and it is insufficient in terms of the moisturizing property required for skin external preparations such as cosmetics. In addition, aluminum salts and zinc salts of 2-O-α-D-glucopyranosyl-L-ascorbic acid (Patent Document 3), and alkali metal salts such as sodium and potassium are known (Patent Document 4).

[Prior technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 03-135992

[Patent Document 2] Japanese Patent Laid-Open No. 03-183492

[Patent Document 3] Japanese Unexamined Patent Publication No. 06-220081

[Patent Document 4] Japanese Patent Laid-Open No. 2002-088095

The subject is to provide 2-O-α-D-glycosyl-L-ascorbic acid metal salt and 2-O-α-D-glycosyl-L-ascorbic acid metal salt with high stability and excellent moisture retention as antioxidants. use.

As a result of intensive research by the present inventors, they found that salts of Group 2 elements of 2-O-α-D-glycosyl-L-ascorbic acid and salts of a combination of Group 2 elements and other metals are particularly stable and moisturizing. Excellent, and the metal salt of 2-O-α-D-glycosyl-L-ascorbic acid is useful as an antioxidant, thereby completing the present invention.

An embodiment of the present invention is exemplified as follows.

(1) A metal salt of 2-O-α-D-glycosyl-L-ascorbic acid, which is a metal salt of 2-O-α-D-glycosyl-L-ascorbic acid represented by the following general formula (1) :

(Where n is an integer from 1 to 8)

The metal ion contains at least one metal ion of a second group element.

(2) The 2-O-α-D-glycosyl-L-ascorbic acid metal salt according to (1), which is a 2-O-α-D-glycosyl-L-ascorbic acid metal salt, and the metal ion is more Contains metal ions of Group I elements.

(3) The 2-O-α-D-glycosyl-L-ascorbic acid metal salt according to (1) or (2), wherein the metal ion of the second group element is a 2-O-α-D-sugar The molar ratio of the base-L-ascorbic acid ranges from 0.01 to 0.50, 0.05 to 0.30, 0.10 to 0.20, or 0.01 to 0.20.

(4) The 2-O-α-D-glycosyl-L-ascorbic acid metal salt according to any one of (1) to (3), wherein the metal ion of the second group element is a magnesium ion.

(5) The 2-O-α-D-glycosyl-L-ascorbic acid metal salt according to any one of (1) to (4), wherein the magnesium ion pairs 2-O-α-D-glycosyl The molar ratio of -L-ascorbic acid is in the range of 0.01 to 0.50, 0.05 to 0.30, 0.10 to 0.20, or 0.01 to 0.20.

(6) The 2-O-α-D-glycosyl-L-ascorbic acid metal salt according to any one of (1) to (5), wherein the 2-O-α-D-glycosyl-L- Ascorbic acid contains 2-O-α-D-glucopyranosyl-L-ascorbic acid.

(7) The 2-O-α-D-glycosyl-L-ascorbic acid metal salt according to (6), wherein the 2-O-α-D-glycosyl-L-ascorbic acid further contains a member selected from 2-O -α-D-maltosyl-L-ascorbic acid, 2-O-α-D-maltotriosyl-L-ascorbic acid, or a mixture thereof.

(8) An amorphous powder of the 2-O-α-D-glycosyl-L-ascorbic acid metal salt according to any one of (1) to (7).

(9) A skin external preparation containing the amorphous powder according to (8) Become.

(10) A method for producing an amorphous powder of 2-O-α-D-glycosyl-L-ascorbic acid metal salt, which comprises: (1) to ((1) to ( 7) The step of the 2-O-α-D-glycosyl-L-ascorbic acid metal salt solution according to any one of the above; spraying the solution to dry the 2-O-α-D-glycosyl-L- The step of ascorbic acid metal salt is an amorphous powder.

(11) An antioxidant comprising a metal salt of 2-O-α-D-glycosyl-L-ascorbic acid represented by the following general formula (1):

(Where n is an integer from 1 to 8).

(12) The antioxidant according to (11), wherein the 2-O-α-D-glycosyl-L-ascorbic acid is 2-O-α-D-glucopyranosyl-L-ascorbic acid.

(13) The antioxidant according to (11) or (12), wherein the metal salt of 2-O-α-D-glycosyl-L-ascorbic acid is a salt of a group 1 metal ion or a group 2 metal ion .

(14) The antioxidant according to any one of (11) to (13), wherein The metal salt of 2-O-α-D-glycosyl-L-ascorbic acid is a potassium salt or a magnesium salt.

(15) The antioxidant according to any one of (11) to (14), wherein the metal salt of 2-O-α-D-glycosyl-L-ascorbic acid is an amorphous powder.

(16) A skin external preparation containing the 2-O-α-D-glycosyl-L-ascorbic acid metal salt according to any one of (1) to (7) or (11) to (15) Any one of the antioxidants described above.

(17) A food containing the 2-O-α-D-glycosyl-L-ascorbic acid metal salt according to any one of (1) to (7) or any one of (11) to (15) The antioxidants described in the item.

(18) An antioxidant-containing composition comprising the antioxidant according to any one of (11) to (15) and a component to be prevented from oxidation, wherein the antioxidant is The ratio of the component to be prevented from being oxidized is 0.1% by weight to 30% by weight.

One embodiment of the present invention provides 2-O-α-D-glycosyl-L-ascorbic acid metal salt, which has high stability and excellent moisturizing property in any of solid state and liquid state.

Furthermore, one embodiment of the present invention provides an antioxidant containing a 2-O-α-D-glycosyl-L-ascorbic acid metal salt.

FIG. 1 is a powder X-ray diffraction pattern of 2-O-α-D-glucopyranosyl-L-ascorbic acid metal salt (K, Mg) (Example 1).

Figure 2 is 2-O-α-D-glucopyranosyl-L-ascorbic acid metal salt (K) A powder X-ray diffraction pattern of (Example 10).

Fig. 3 is a powder X-ray diffraction pattern of 2-O-α-D-glucopyranosyl-L-ascorbic acid (Comparative Example 1).

The present invention includes a plurality of embodiments. The terms used and / or defined in one embodiment are considered to have the same meaning in all other embodiments unless otherwise defined.

<2-O-α-D-glycosyl-L-ascorbic acid>

In one embodiment of the present invention, 2-O-α-D-glycosyl-L-ascorbic acid refers to 2-O-α-D-glycosyl-L-ascorbic acid represented by the following general formula (1): Species or mixtures of:

(In the formula, n is an integer of 1 or more.)

The n in the aforementioned general formula (1) means that the number of sugars (glucose) bonded to the α-position of a glucose residue at the 2-position of L-ascorbic acid is an integer of 1 or more, preferably 1 to 8 or 1 to 3, Super Best Line 1. The present invention may be 2-O-α-D-glucopyranosyl-L-ascorbic acid (n = 1), 2-O-α-D-maltosyl-L-ascorbic acid (n = 2), 2- O-α-D-maltotriosyl-L-ascorbic acid (n = 3), 2-O-α-D-maltotetraosyl-L-ascorbic acid (n = 4), 2-O-α- D-maltopentosyl-L-ascorbic acid (n = 5), 2-O-α-D-maltohexaosyl-L-ascorbic acid (n = 6), 2-O-α-D-malt Either heptosyl-L-ascorbic acid (n = 7) or 2-O-α-D-maltooctacosyl-L-ascorbic acid (n = 8) or a mixture of these, but preferably Contains at least 2-O-α-D-glucopyranosyl-L-ascorbic acid represented by the following chemical formula (2):

From the viewpoint of more excellent moisturizing properties, 2-O-α-D-glycosyl-L-ascorbic acid is preferred, and in addition to 2-O-α-D-glucopyranosyl-L-ascorbic acid, It further contains 2-O-α-D-maltosyl-L-ascorbic acid and / or 2-O-α-D-maltotriosyl-L-ascorbic acid.

The 2-O-α-D-glycosyl-L-ascorbic acid can be produced by a known method, for example, the method described in Patent Document 1. A method for producing 2-O-α-D-glucopyranosyl-L-ascorbic acid is described below as an example.

(1) In a solution containing L-ascorbic acid and an α-glucosyl sugar compound, the glycosyltransferase acts, and then the glucoamylase acts to prepare As a solution containing 2-O-α-D-glucopyranosyl-L-ascorbic acid.

(2) Refining a solution containing 2-O-α-D-glucopyranosyl-L-ascorbic acid using an ion exchange resin or the like to produce 2-O-α-D-glucopyranose with high purity -L-ascorbic acid solution.

(3) Crystallizing 2-O-α-D-glucopyranosyl-L-ascorbic acid to obtain 2-O-α-D-glucopyranosyl-L-ascorbic acid.

In the present invention, a metal salt can be directly produced using a solution containing 2-O-α-D-glucopyranosyl-L-ascorbic acid (2).

<2-O-α-D-glycosyl-L-ascorbic acid metal salt>

The 2-O-α-D-glycosyl-L-ascorbic acid metal salt can be produced by reacting 2-O-α-D-glycosyl-L-ascorbic acid with a metal salt.

In one embodiment of the present invention, the metal ion of the 2-O-α-D-glycosyl-L-ascorbic acid metal salt may be a metal ion selected from Group I elements such as sodium ion and potassium ion; for example, magnesium ion Metal ions of Group 2 elements such as calcium ions; transition metal ions such as iron ions and copper ions; and metal ions or a combination thereof composed of other metal ions such as zinc ions and aluminum ions.

In one embodiment of the present invention, the metal ion of the 2-O-α-D-glycosyl-L-ascorbic acid metal salt contains at least one metal ion of a second group element. Preferably, it contains magnesium ion. In this embodiment, the molar ratio of the metal ion of the second group element of the 2-O-α-D-glycosyl-L-ascorbic acid metal salt to the 2-O-α-D-glycosyl-L-ascorbic acid may be 0.01 or more, 0.05 or more, or 0.10 or more, and may be 0.50 or less, 0.30 or less, or 0.20 or less, preferably in the range of 0.01 to 0.20. When the 2-O-α-D-glycosyl-L-ascorbic acid metal salt contains magnesium ions, the magnesium ions are resistant to 2-O-α-D-glycosyl-L- The molar ratio of blood acid may be 0.01 or more, 0.05 or more, or 0.10 or more, and may be 0.50 or less, 0.30 or less, or 0.20 or less, preferably in the range of 0.01 to 0.20.

Examples of metal salts that react with 2-O-α-D-glycosyl-L-ascorbic acid include magnesium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium chloride, sodium chloride, potassium chloride, and chlorine. Calcium, magnesium sulfate, sodium sulfate, potassium sulfate, sodium nitrate, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium phosphate, etc. Since the by-product of the reaction is water, particularly preferred are metal hydroxides such as magnesium hydroxide, sodium hydroxide, potassium hydroxide, and calcium hydroxide.

<Method for manufacturing 2-O-α-D-glycosyl-L-ascorbic acid metal powder>

An amorphous powder of 2-O-α-D-glycosyl-L-ascorbic acid metal salt can be produced by a method including the following steps: making the 2-O-α-D-glycosyl group dissolved in a solvent -A step of a solution of the metal salt of L-ascorbic acid; and a step of spray-drying the aforementioned solution to make the 2-O-α-D-glycosyl-L-ascorbic acid metal salt an amorphous powder.

The solvent may be any known solvent as long as it dissolves 2-O-α-D-glycosyl-L-ascorbic acid metal salt, but water and / or alcohol is preferred, and water is particularly preferred. The alcohol is preferably ethanol.

The spray drying can be performed using, for example, a spray dryer. Spray drying is preferably performed when the inlet temperature of the spray dryer is 140 to 180 ° C. When the temperature is lower than 140 ° C, the solvent may not be sufficiently evaporated, so there is a possibility that a dry powder cannot be obtained. On the other hand, when the temperature is higher than 180 ° C, there will be 6-fluorenyl-2-O-α-D-glycosyl-L-ascorbic acid in the step. And 2-O-α-D-glycosyl-L-ascorbic acid may be decomposed or volatile. Moreover, it is preferable to carry out when the exit temperature of a spray dryer is 50-100 degreeC.

In one embodiment of the present invention, the 2-O-α-D-glycosyl-L-ascorbic acid metal salt system not only stabilizes itself but also has the effect of stabilizing other components. That is, a 2-O-α-D-glycosyl-L-ascorbic acid metal salt system is useful as a stabilizer.

The stabilizer refers to an additive added to prevent decomposition, deterioration, deterioration, and the like of other components due to heat, light, and oxygen. The stabilizer may be an antioxidant used to prevent a compound having weak oxidation resistance from being oxidized and decomposed.

In one embodiment of the present invention, the ingredients for preventing oxidation by antioxidants are not particularly limited, and examples thereof include vitamins such as vitamin A, vitamin C, and vitamin E; chlorogenic acids, tannins, catechins, and quercetin Polyphenols, such as carotene; carotenoids, such as carotene and lutein.

In one embodiment of the present invention, in order to obtain a sufficient stabilization effect, it is preferable to add a stabilizer to the component to be stabilized by 0.1% by weight or more, 1% by weight or more, 2% by weight or more, 5% by weight or more, or 10% by weight or more. 2-O-α-D-glycosyl-L-ascorbic acid metal salt has a high stabilization effect even in a slight amount, so it can be 30% by weight or less and 20% by weight relative to the component to be stabilized as desired. Use below 10% by weight, below 5% by weight, below 2% by weight.

In one embodiment of the present invention, the 2-O-α-D-glycosyl-L-ascorbic acid metal salt is not harmful to animals such as humans, and can be added to foods, skin external preparations, and the like. 2-O-α-D-glycosyl-L-ascorbic acid metal salt can be used alone or in combination with other ingredients as food or drink, skin external preparation, etc. use.

The external preparation for skin means a composition applied to the outer skin, and includes, for example, cosmetics, pharmaceuticals, and quasi-drugs. The outer skin contains hair and nails.

The external preparation for skin can be appropriately selected and applied in accordance with the purpose of use, the characteristics of the preparation, and the use form, and known bases, carriers, and the like that are generally used in the preparation of external preparations for skin. In addition, other ingredients may be used in combination, such as a surfactant, a skin absorption enhancer, an antioxidant, a supplement, an ultraviolet absorber, a thickener, an extender, a stabilizer, a coloring agent, a fragrance attaching agent, and a preservative. Agents, mold inhibitors, etc.

The external preparations for the skin can be appropriately selected and prepared as an ointment, cream, spray, lotion, powder, gel, sol, aerosol, lozenge, patch, etc. according to the intended use and the use form. Agents, lotions, lotions, lotions, beauty liquids, masks, base makeup, foundations and other dosage forms.

In one embodiment of the present invention, the skin external preparation contains 0.001 to 50% by weight, or 0.01 to 20% by weight, and preferably 2-O-α- D-glycosyl-L-ascorbic acid metal salt.

(Example)

In the following examples, the present invention will be described in more detail, but the present invention is not limited thereto.

Other terms and concepts in the present invention are based on the meanings of terms commonly used in the field. Various technologies used in order to implement the present invention. Except for the technology that clearly indicates the source, as long as it is a person in the technical field, it can be based on well-known documents. It is easy and reliable to implement. Also, various analysis It is carried out by the methods described in the operating instructions, catalogues, etc. of the analysis equipment or reagents used, the kits.

In addition, the contents described in the prior art documents, patent publications, and patent application specifications cited in this specification are the contents of the present invention by reference.

(Example 1)

2-O-α-D-glucopyranosyl-L-ascorbic acid metal salt (K, Mg)

(1) Synthesis of 2-O-α-D-glucopyranosyl-L-ascorbic acid

To 1000 g of water, 125 g of liquefied starch and 50 g of L-ascorbic acid were added and dissolved, and the pH was adjusted to 5.0. 20 g of a cyclomaltodextrin dextran transferase enzyme preparation (Toruzyme 3.0L, manufactured by Novozymes) was added thereto, and the mixture was reacted at 50 ° C. for 48 hours to obtain 2-O-α-D-glucopyranosyl- L-ascorbic acid, 2-O-α-maltosyl-L-ascorbic acid, 2-O-α-maltotriosyl-L-ascorbic acid, 2-O-α-maltotetraosyl-L-ascorbic acid, etc. 2 -O-α-D-glycosyl-L-ascorbic acid reaction solution.

After heating the obtained reaction solution to deactivate the enzyme and stop the reaction, 1.5 g of a glucoamylase enzyme preparation (GLUCZYME AF6, manufactured by Amano Enzyme Co., Ltd.) was added and reacted at 50 ° C for 16 hours to obtain 2-O -α-D-glucopyranosyl-L-ascorbic acid reaction solution. After the reaction, the enzyme is heated to deactivate the enzyme and stop the reaction.

(2) Purification of 2-O-α-D-glucopyranosyl-L-ascorbic acid

Heating the obtained reaction solution to deactivate the enzyme and stop the reaction After that, activated carbon was added, decolorized, and filtered. The filtrate was passed through a column filled with an H-type cation exchange resin to remove metal ions, and then passed through a column filled with an OH-type anion exchange resin to pass 2-O-α-D-glucopyranosyl- L-ascorbic acid adsorption. After washing the anion exchange resin to which 2-O-α-D-glucopyranosyl-L-ascorbic acid has been adsorbed to remove unreacted saccharides, 0.1N sodium hydroxide is passed through the liquid to precipitate 2-O-α- D-glucopyranosyl-L-ascorbic acid. Further, the eluate was passed through a column filled with an H-type cation exchange resin to obtain a purified solution of 2-O-α-D-glucopyranosyl-L-ascorbic acid from which metal ions were removed.

(3) Synthesis of 2-O-α-D-glucopyranosyl-L-ascorbic acid metal salt

Add 0.05 mol equivalent of magnesium hydroxide and 0.90 mol equivalent of potassium hydroxide to 2-O-α-D-glucopyranosyl-L-ascorbic acid contained in the purified solution, and stir at 40 ° C for 1 hour. To obtain an aqueous solution of 2-O-α-D-glucopyranosyl-L-ascorbic acid metal salt (K, Mg).

(4) Spray drying of 2-O-α-D-glucopyranosyl-L-ascorbic acid metal salt

The 2-O-α-D-glucopyranosyl-L-ascorbic acid metal salt solution was heated under reduced pressure and concentrated to about 15% solid content, and then activated carbon was added to decolorize and refine it, and then filtered. The filtrate was spray-dried using a spray dryer (manufactured by BUCHI Corporation, B-290) at an inlet temperature of 160 ° C and an outlet temperature of 75 ° C to obtain 2-O-α-D-glucopyranosyl-L-ascorbic acid metal 48g of salt (K, Mg) powder.

(Example 2)

2-O-α-D-glucopyranosyl-L-ascorbic acid metal salt (K, Mg)

Except that 0.01 mol equivalent of magnesium hydroxide and 0.98 mol equivalent of potassium hydroxide are used in place of the 0.05 mol equivalent of magnesium hydroxide and 0.90 mol equivalent of potassium hydroxide described in Example 1 (3). In the same manner as in Example 1, a powder of 2-O-α-D-glucopyranosyl-L-ascorbic acid metal salt (K, Mg) was obtained.

(Example 3)

2-O-α-D-glucopyranosyl-L-ascorbic acid metal salt (K, Mg)

Except that 0.10 mol equivalent of magnesium hydroxide and 0.80 mol equivalent of potassium hydroxide are used in place of the 0.05 mol equivalent of magnesium hydroxide and 0.90 mol equivalent of potassium hydroxide described in Example 1 (3). In the same manner as in Example 1, a powder of 2-O-α-D-glucopyranosyl-L-ascorbic acid metal salt (K, Mg) was obtained.

(Example 4)

2-O-α-D-glucopyranosyl-L-ascorbic acid metal salt (K, Mg)

Except using 0.20 mol equivalent of magnesium hydroxide and 0.60 mol equivalent of potassium hydroxide instead of 0.05 mol equivalent of magnesium hydroxide and 0.90 mol equivalent of potassium hydroxide described in Example 1 (3), and In the same manner as in Example 1, a powder of 2-O-α-D-glucopyranosyl-L-ascorbic acid metal salt (K, Mg) was obtained.

(Example 5)

2-O-α-D-glucopyranosyl-L-ascorbic acid metal salt (K, Mg)

Instead of using 0.30 mol equivalent of magnesium hydroxide and 0.40 mol equivalent of potassium hydroxide instead of the 0.05 mol equivalent of magnesium hydroxide described in Example 1 (3) A powder of 2-O-α-D-glucopyranosyl-L-ascorbic acid metal salt (K, Mg) was obtained in the same manner as in Example 1 except for 0.90 mol equivalent of potassium hydroxide.

(Example 6)

2-O-α-D-glucopyranosyl-L-ascorbic acid metal salt (Mg)

2-O was obtained in the same manner as in Example 1 except that 0.50 mol equivalent of magnesium hydroxide was used instead of 0.05 mol equivalent of magnesium hydroxide and 0.90 mol equivalent of sodium hydroxide described in Example 1 (3). -α-D-glucopyranosyl-L-ascorbic acid metal salt (Mg) powder.

(Example 7)

2-O-α-D-glucopyranosyl-L-ascorbic acid metal salt (Na, Mg)

Except using 0.05 mol equivalent of magnesium hydroxide and 0.90 mol equivalent of sodium hydroxide instead of 0.05 mol equivalent of magnesium hydroxide and 0.90 mol equivalent of potassium hydroxide described in Example 1 (3), and In the same manner as in Example 1, 50 g of a powder of 2-O-α-D-glucopyranosyl-L-ascorbic acid metal salt (Na, Mg) was obtained.

(Example 8)

2-O-α-D-glucopyranosyl-L-ascorbic acid metal salt (Ca, Mg)

Except using 0.05 mol equivalent of magnesium hydroxide and 0.45 mol equivalent of calcium hydroxide instead of the 0.05 mol equivalent of magnesium hydroxide and 0.90 mol equivalent of potassium hydroxide described in Example 1 (3), and In the same manner as in Example 1, 52 g of powder of 2-O-α-D-glucopyranosyl-L-ascorbic acid metal salt (Ca, Mg) was obtained.

(Example 9)

2-O-α-D-glucopyranosyl-L-ascorbic acid metal salt (Na)

2-O was obtained in the same manner as in Example 1 except that 1 mol equivalent of sodium hydroxide was used instead of the 0.05 mol equivalent of magnesium hydroxide and 0.90 mol equivalent of potassium hydroxide described in Example 1 (3). 46g of -α-D-glucopyranosyl-L-ascorbic acid metal salt (Na).

(Example 10)

2-O-α-D-glucopyranosyl-L-ascorbic acid metal salt (K)

2-O was obtained in the same manner as in Example 1 except that 1 mol equivalent of potassium hydroxide was used instead of the 0.05 mol equivalent of magnesium hydroxide and 0.90 mol equivalent of potassium hydroxide described in Example 1 (3). 47g of -α-D-glucopyranosyl-L-ascorbic acid metal salt (K) powder.

(Comparative example 1)

2-O-α-D-glucopyranosyl-L-ascorbic acid

The purified solution obtained in the same manner as in Example 1 (2) was concentrated under heating and reduced pressure at 50 ° C, and concentrated to about 60% of the solid content, and then the aqueous solution was cooled to 10 ° C to precipitate crystals. The precipitate was collected by filtration and washed with a small amount of water. The precipitate was dried under reduced pressure to obtain 17 g of 2-O-α-D-glucopyranosyl-L-ascorbic acid crystalline powder.

(Comparative example 2)

2-O-α-D-glucopyranosyl-L-ascorbic acid amorphous powder

The purified solution obtained in the same manner as in step (2) of Example 1 was concentrated under heating and reduced pressure at 50 ° C., and concentrated to about 15% of solid content, and then activated carbon was added for decolorization and purification, and filtered. The filtrate was spray-dried (manufactured by BUCHI, Japan, B-290) at an inlet temperature of 160 ° C, The mouth temperature was 75 ° C and spray-dried to obtain 41 g of 2-O-α-D-glucopyranosyl-L-ascorbic acid amorphous powder.

<Assessment of preservation stability>

Stability of powder

The 2-O-α-D-glucopyranosyl-L-ascorbic acid metal salt or 2-O-α-D-glucopyranosyl-L-ascorbic acid obtained in Examples 1 to 10 and Comparative Example 1, respectively 5 g of the crystal powder was placed in a closed container and stored in a 40 ° C environment for 250 hours to perform a stability test. The stability is determined by quantitatively analyzing the powder after the test by a high-performance liquid chromatography (HPLC) method under the following conditions, and calculating the residual rate. The results are shown in Table 1. The HPLC method uses a high-performance liquid chromatography device manufactured by Waters, and the column system uses Shodex Asahipak NH2P-50 4E 4.6 × 250 mm. (Column temperature: 40 ° C, mobile phase: acetonitrile / 0.1% phosphate buffer = 60/40, flow rate: 0.7mL / min, wavelength: 254nm)

Stability of aqueous solution

The 2-O-α-D-glucopyranosyl-L-ascorbic acid metal salt or 2-O-α-D-glucopyranosyl-L-ascorbic acid obtained in Examples 1 to 10 and Comparative Example 1 were respectively used. 1 g was dissolved in 20 g of water to form an aqueous solution. This aqueous solution was placed in a closed container and stored in a 40 ° C. environment for 250 hours to perform a stability test. The stability is evaluated by quantitative analysis of the aqueous solution after the test by HPLC, and calculating the residual rate. The results are shown in Table 1.

<Evaluation method of moisturizing property>

Adjust the 30% by weight aqueous solution of each product, and put 10g of the aqueous solution in A 45mm glass plate was placed in a thermostat / humidifier at a temperature of 25 ° C and a humidity of 35% and held for 24 hours. The weight of each product after the retention was measured, and the weight residual ratio (%) was calculated. The results are shown in Table 1. The higher the weight residual rate, the higher the moisturizing power.

<Powder X-ray Diffraction Device>

A powder X-ray diffraction device (RINT2200, manufactured by Rigaku Electric Co., Ltd.) using CuK α rays as an X-ray source was used, with a tube voltage of 40 kV, a tube current of 20 mA, a scanning range (2 θ) of 5 ° to 40 °, and divergence. The measurement was performed under conditions of a slit of 1/2 °, a scattering slit of 1/2 °, a light receiving slit of 0.15 mm, a sampling width of 0.02 °, and a scanning speed of 4 ° / minute. The peak of 2-O-α-D-glucopyranosyl-L-ascorbic acid metal salt (K, Mg) in Example 1 is shown in FIG. 1, The peak of 2-O-α-D-glucopyranosyl-L-ascorbic acid metal salt (K) in Example 10 is shown in FIG. 2, and the 2-O-α-D-glucopyridine in Comparative Example 1 is shown in FIG. 2. The peak of glycosyl-L-ascorbic acid is shown in FIG. 3.

The peaks of powder X-ray diffraction show that 2-O-α-D-glucopyranosyl-L-ascorbic acid metal salts of Examples 1 and 10 are amorphous, while that of Comparative Example 1 2-O-α- D-glucopyranosyl-L-ascorbic acid is crystalline. It is recognized that the solids of Examples 2 to 9 and Comparative Example 2 which were powdered in the same manner as in Examples 1 and 10 were also amorphous.

Surprisingly, the 2-O-α-D-glucopyranosyl-L-ascorbic acid metal salt of Examples 1 to 8 still showed 2-O- with crystallinity even though it was amorphous in the solid state. Alpha-D-glucopyranosyl-L-ascorbic acid is equally stable. In addition, although 2-O-α-D-glucopyranosyl-L-ascorbic acid metal salt exhibits high stability and excellent moisturizing property when the metal ion contains a metal ion of a second group element, it is unexpectedly associated with metal Compared with the case where the ions are only metal ions of the second group element, the metal ions having the second group element and other metal ions have a more excellent effect.

<Preparation of mixed preparations>

(Modulation example 1)

0.5 g of each powder prepared in Examples 6, 10 and Comparative Examples 1 and 2 and 5 g of powder of L-ascorbic acid were put into a 110 ml sample bottle, and the powder was mixed with a mixing rotator to prepare an L-ascorbic acid mixed preparation.

(Modulation example 2)

In addition to replacing L-ascorbic acid in Preparation Example 1 with epigallocatechin-3-gallate (EGCG) (Sunphenon EGCG-OP, Sun Chemical Co., Ltd. has Co., Ltd.) was manufactured in the same manner to prepare a mixed preparation containing EGCG.

(Modulation example 3)

Except changing L-ascorbic acid in Preparation Example 1 to α-tocopherol (Vitacoat E-70 α: α-tocopherol content rate of 70%, manufactured by Yokohama Oils and Fats Industry Co., Ltd.), the same procedure was performed to produce α-tocopherol. Mixed formulation of phenol.

(Modulation example 4)

A mixed preparation containing quercetin was prepared in the same manner except that L-ascorbic acid in Preparation Example 1 was replaced with quercetin.

(Modulation example 5)

0.1 g, 0.25 g, 0.5 g, 1.0 g, 1.5 g, 2.5 g, and 5.0 g of the powder prepared in Example 10 were mixed with 5 g of the powder of L-ascorbic acid in the same manner as in Preparation Example 1 to prepare each powder. Composition of L-ascorbic acid mixed preparation.

(Modulation example 6)

A mixed preparation containing EGCG of each composition was prepared in the same manner except that L-ascorbic acid in Preparation Example 5 was replaced with EGCG.

<Assessment of preservation stability>

5 g of various mixed preparations obtained in each of the preparation examples were put into a container, and stored in a 60 ° C. environment for 500 hours to perform a stability test. The stability was evaluated by quantitatively analyzing L-ascorbic acid, EGCG, α-tocopherol, and quercetin contained in the powder by a high-performance liquid chromatography (HPLC) method under the following conditions, and calculating the residual rate. In addition, 5 g of L-ascorbic acid, EGCG, α-tocopherol, and quercetin were put into a container, and a stability test was performed in the same manner as an example of no stabilizer. The results of the residual rate after 500 hours are shown in Table 1 below. And Table 2. The HPLC method uses a high-performance liquid chromatography device manufactured by Waters, and the column system uses COSMOSIL 5C18-MS-II 4.6 × 250mm. The measurement is performed for each composition under the following conditions.

L-ascorbic acid (column temperature: 40 ° C, mobile phase: 0.3% acetic acid aqueous solution, flow rate: 1 mL / min, measurement wavelength: 230 nm)

EGCG (column temperature: 40 ° C, mobile phase: acetonitrile / 0.1% acetic acid aqueous solution = 10/90, flow rate: 1mL / min, measurement wavelength 230nm)

α-Tocopherol (column temperature: 30 ° C, mobile phase: methanol / water = 90/10, flow rate 1mL / min, measurement wavelength 295nm)

Quercetin (column temperature: 40 ° C, mobile phase: acetonitrile / 0.01% acetic acid aqueous solution = 20/80, flow rate 0.5mL / min, measurement wavelength: 254nm)

The 2-O-α-D-glucosyl-L-ascorbic acid metal salt of Examples 6 and 10 showed a high stabilization effect on any of L-ascorbic acid, EGCG, α-tocopherol, and quercetin. It is known from the adjustment examples 5 and 6 that the 2-O-α-D-glucosyl-L-ascorbic acid metal salt shows a high stabilization effect even if only a small amount of 2% by weight is stabilized, 5 to 10% by weight A sufficient stabilization effect can be obtained. As a result, it was surprising that the stabilization effect of the 2-O-α-D-glucosyl-L-ascorbic acid metal salt exceeded the effect expected from the effect of decomposing by replacing other components.

(Industrial availability)

The 2-O-α-D-glucopyranosyl-L-ascorbic acid metal salt of the present invention is particularly useful for external skin preparations such as cosmetics.

Claims (15)

A 2-O-α-D-glycosyl-L-ascorbic acid metal salt, which is a metal salt of 2-O-α-D-glycosyl-L-ascorbic acid represented by the following general formula (1): In the formula, n is an integer of 1 to 8; and the metal ion contains at least one metal ion of a second group element. The 2-O-α-D-glycosyl-L-ascorbic acid metal salt as described in item 1 of the scope of patent application, which is a 2-O-α-D-glycosyl-L-ascorbic acid metal salt, and the metal ion is more Contains metal ions of Group I elements. The 2-O-α-D-glycosyl-L-ascorbic acid metal salt according to item 1 or item 2 of the scope of the patent application, wherein the metal ion of the aforementioned second group element is magnesium ion. The 2-O-α-D-glycosyl-L-ascorbic acid metal salt according to any one of claims 1 to 3, wherein the metal ion of the second group element is a 2-O-α The molar ratio of -D-glycosyl-L-ascorbic acid is 0.01 to 0.20. 2-O- as described in any one of claims 1 to 4 α-D-glycosyl-L-ascorbic acid metal salt, wherein 2-O-α-D-glycosyl-L-ascorbic acid contains 2-O-α-D-glucopyranosyl-L-ascorbic acid. An amorphous powder composed of a 2-O-α-D-glycosyl-L-ascorbic acid metal salt as described in any one of claims 1 to 5 of the scope of patent application. A method for manufacturing an amorphous powder of 2-O-α-D-glycosyl-L-ascorbic acid metal salt, which comprises the following steps: preparing the first to the first patent application scope dissolved in a solvent of water and / or alcohol The step of a 2-O-α-D-glycosyl-L-ascorbic acid metal salt solution according to any one of 5 items; and spray-drying the aforementioned solution to make 2-O-α-D-glycosyl-L -The step of powdering ascorbic acid metal salt. An antioxidant comprising a metal salt of 2-O-α-D-glycosyl-L-ascorbic acid represented by the following general formula (1): In the formula, n is an integer of 1 to 8. The antioxidant according to item 8 of the scope of the patent application, wherein the metal salt of 2-O-α-D-glycosyl-L-ascorbic acid is a salt of a group 1 metal ion or a group 2 metal ion. The antioxidant according to claim 8 or claim 9, wherein the metal salt of 2-O-α-D-glycosyl-L-ascorbic acid is a potassium salt or a magnesium salt. The antioxidant according to any one of items 8 to 10 in the scope of patent application, wherein the metal salt of 2-O-α-D-glycosyl-L-ascorbic acid is the items 1 to 5 in the scope of patent application The 2-O-α-D-glycosyl-L-ascorbic acid metal salt according to any one of the items. The antioxidant according to any one of claims 8 to 11, in which the metal salt of 2-O-α-D-glycosyl-L-ascorbic acid is an amorphous powder. An antioxidant-containing composition is a composition containing the antioxidant described in any one of claims 8 to 12 and a component to be prevented from oxidizing, wherein the antioxidant is The ratio of the component to be prevented from being oxidized is 0.1% by weight to 30% by weight. A skin external preparation containing the 2-O-α-D-glycosyl-L-ascorbic acid metal salt according to any one of claims 1 to 5 of the scope of patent application or the scope of claims 8 to 8 of the scope of patent application The antioxidant according to any one of 12 items. A food product containing 2-O-α-D-glycosyl-L-ascorbic acid metal salt as described in any one of claims 1 to 5 of the scope of patent application or claims 8 to 12 of the scope of patent application The antioxidant according to any one of the above.