JP2001158739A - Composition containing proanthocyanidin and vitamin b6 derivative or its salt - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition excellent in stability of proanthocyanidin, to obtain drinks, foods, cosmetics and medicines each containing the composition and to provide a method for stabilizing proanthocyanidin for preventing discoloration or the like caused by oxidative polymerization or the like. SOLUTION: This composition is obtained by including proanthocyanidin and a vitamin B6 derivative or its salt and the drinks, foods, cosmetics and medicines are obtained by including the composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a composition containing proanthocyanidin, a beverage, a food, a cosmetic and a medicine containing the composition, and a method for stabilizing proanthocyanidin.

[0002]

2. Description of the Related Art Proanthocyanidin is a substance contained in many plants and known to have a strong antioxidant action, but is unstable to oxidation, and in the presence of oxygen,
It is known that oxidative polymerization or the like occurs immediately and discolors. As a conventionally known method of stabilizing proanthocyanidins, for example, in wine, a method of blending potassium pyrosulfite, and in apple juice, a method of blending ascorbic acid has been mainly used. .

[0003] Also, JP-A-6-336420 discloses that
Disclosed are cosmetics containing sodium bisulfite, 1-hydroxyethane-1,1-disulfonic acid, diethylenetriaminepentaacetic acid or phytic acid in order to prevent the coloring of proanthocyanidins with time. Further, as a composition for stabilizing or preventing discoloration of polyphenol or for stabilizing or preventing discoloration of polyphenol, (1) JP-B-8-2819 discloses polyphenol containing a porphyrin zinc complex and an organic reducing agent. (2) JP-A-5-112441 discloses a method for preventing discoloration of
A skin cosmetic in which a polyphenol compound is blended with a higher fatty acid ester of sucrose, (3) Japanese Patent Application Laid-Open No. 5-163131 is a skin cosmetic in which an alkylglucoside is blended with a polyphenol compound, and (4) Japanese Patent No. 2744572 is a polyvalent compound. Disclosed is a method for preventing discoloration of a skin external preparation composition containing a polyphenol compound containing three or more phenolic hydroxyl groups containing alcohol or saccharide.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a composition having excellent stability of proanthocyanidin, a beverage, a food, a cosmetic and a pharmaceutical containing the composition, and a proanthocyanidin for preventing discoloration due to oxidative polymerization and the like. An object of the present invention is to provide a method for stabilizing anthocyanidins.

[0005]

The present invention provides a composition containing proanthocyanidin and a vitamin B ₆ derivative or a salt thereof, and beverages, foods, cosmetics and medicaments containing the composition. Further, the present invention provides a method for stabilizing proanthocyanidin, which comprises mixing a vitamin B ₆ derivative or a salt thereof with proanthocyanidin.

The present invention also provides a proanthocyanidin stabilizer containing a vitamin B ₆ derivative or a salt thereof.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Specific examples of vitamin B ₆ derivatives include pyridoxine, pyridoxal, pyridoxamine, and phosphates thereof, such as pyridoxal-5-phosphate. Pyridoxine, pyridoxal and pyridoxamine are compounds represented by the following general formula (I).

[0008]

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[0009] [In the formula, R ^1, CH ₂ OH (pyridoxine), CHO (pyridoxal) or CH represents a ₂ NH ₂ (pyridoxamine)] As the salts of the vitamin B ₆ derivative, hydrochloride of vitamin B ₆ derivatives Inorganic acid salts such as salts, sulfates, nitrates and phosphates, or organic acid salts such as maleates, fumarates, citrates and acetates.

The vitamin B ₆ derivative or a salt thereof may exist in the form of a hydrate or a solvate. Vitamin B ₆ derivatives or salts thereof can be prepared by known methods,
For example, it can be synthesized by the method described in the Chemical Dictionary, Edited by the Chemical Dictionary Editing Committee, Kyoritsu Shuppan Co., Ltd., Vol. 7, p. 406, August 5, 1962. You may.

Examples of proanthocyanidins include a compound group in which two or more flavan-7-ol derivatives represented by the following general formula (II) are bonded.

[0012]

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(Wherein R ³ and R ⁴ are the same or different and represent hydrogen, hydroxyl, galloyloxy or glucopyranosyloxy, and R ² , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ is the same or different and represents hydrogen or a hydroxyl group) Preferred specific examples of the flavan-7-ol derivative represented by the general formula (II) include catechin, epicatechin,
Gallocatechin, epigallocatechin, afzeletin, epiafuzeletin and the like.

In proanthocyanidins, the carbon of the flavan-7-ol derivative is different from that of the other flavan-7-ol.
The carbon is bonded to the carbon of the all derivative by a single bond or an ether bond via an oxygen atom (in the case of an ether bond, it may be via the hydroxyl group of the flavan-7-ol derivative) or the like. The carbon concerned may be any carbon that can be bonded. The structural units of the flavan-7-ol derivative may be the same or different.

Examples of the form of the bond between the flavan-7-ol derivatives in proanthocyanidins are represented by the following general formulas (III-a), (III-b) and (III-c).

[0016]

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[0017]

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[0018]

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(Wherein R^3a, R^4a, R^3b, R^4b, R^3c,
R^4c, R^3d, R^4d, R^3e, R^4e, R^3fAnd R^4fIs the same
One or different may be hydrogen, hydroxyl, galloyloxy, etc.
Or glucopyranosyloxy group;^5a, R^6a, R
^7a, R^8a, R^9a, R^2b, R^5b, R^7b, R^8b, R^9b,
R^5c, R^6c, R^7c, R^8c, R^9c, R^2d, R^5d, R^6d, R
^7d, R^8d, R^9d, R^5e, R^6e, R^7e, R^8e, R^9e,
R^2f, R^5f, R^7f, R^8fAnd R ^9fAre the same or different
Represents hydrogen or a hydroxyl group.) Proanthocyanidins include the flavan-7-O
The structural unit of the derivative is preferably 2 to 10, more preferably
Preferably, those having 2 to 4 are used.

The dimer of the flavan-7-ol derivative includes, for example, a combination of epicatechin and catechin such as epicatechin- (4β → 8) -catechin, epicatechin-
(4β → 6) -epicatechin, epicatechin- (4β →
8) -Epicatechin dimer such as epicatechin (procyanidin B-2) and catechin dimer such as catechin- (4α → 8) -catechin, etc., and trimer of flavan-7-ol derivative As a body, for example, epicatechin-
(4β → 8) -epicatechin- (4β → 8) -epicatechin, epicatechin- (4β → 8) -epicatechin-
Trimeric epicatechin such as (4β → 6) -epicatechin, catechin- (4α → 8) -catechin- (4α → 8)
Catechin trimer such as catechin, epicatechin- (4
Mixed trimers of epicatechin and catechin, such as β → 8) -epicatechin- (4β → 8) -catechin, and the like.

In the present invention, a compound in which a sugar such as gallic acid, glucose or rhamnose is added to the above-described compound is also included in the concept of proanthocyanidins. In the present invention, proanthocyanidins have various isomers such as various optical isomers, and all of them and mixtures thereof are also applicable to the present invention. Proanthocyanidins include grape, apple, barley, oyster,
Grape belonging to coconut genus, cacao genus, pine genus, lingonberry, fragaria, kidney bean, peanut, etc.,
Apples, barley, oysters, palms, cacao, pine, blueberries, strawberries, adzuki beans, peanuts, and other various fermented products, as well as fermented products of these extracts, such as wine, apple cider, and beer And by purifying them.

Extraction and purification from plants can be performed by the following known methods. After collecting the fruits, seeds, leaves, stems, roots, rhizomes, etc. of the raw materials of the plant at an appropriate time,
It is used as it is or is usually subjected to a drying step such as air drying to be used as an extraction raw material. When proanthocyanidins are extracted from the dried plants described above, a known method [Chemical and Pharmaceutical Britain (Chemical & Ph.
armaceutical Bulletin), 38 : 3218, 1990 and id., 4
0 : 889-898, 1992]. That is, after pulverizing or shredding the raw material, extraction is performed using a solvent. As the extraction solvent, a hydrophilic or lipophilic solvent such as water, alcohols such as ethanol, methanol, and isopropyl alcohol, ketones such as acetone and methyl ethyl ketone, and esters such as methyl acetate and ethyl acetate, alone or in a mixed solvent Can be used as The extraction temperature is usually 0 to 100 ° C, preferably 5 to 100 ° C.
５０50 ° C.

The extraction time is about 1 hour to about 10 days, and the amount of the solvent is usually 1 to 30 times, preferably 5 to 10 times the weight of the dry raw material. The extraction operation may be performed by stirring or immersion. The extraction operation may be repeated two or three times as necessary. The method of purifying proanthocyanidin from the extract obtained by removing the insoluble residue from the crude extract obtained by the above operation by filtration or centrifugation, or the squeezed liquid or sap of a plant (purification method A) is a known crude drug separation method. Any purification method may be used, but two-phase solvent partitioning, column chromatography,
It is preferable to use preparative high performance liquid chromatography alone or in combination. For example, as a two-phase solvent partitioning method, a method of extracting and removing oil-soluble components and dyes from the above-mentioned extract with n-hexane, petroleum ether, or the like, or partitioning the extract with a solvent such as n-butanol or methyl ethyl ketone and water. To recover the proanthocyanidin into the solvent phase. As a column chromatography method, Amberlite IR-120 is used as a carrier.
B, ion-exchange column chromatography using Amberlite IRA-402 and the like, normal-phase silica gel, reverse-phase silica gel, Diaion HP-20 as a carrier,
An adsorption column chromatography method using Sepabeads SP-207 or the like, a gel filtration method using Sephadex LH-20 or the like as a carrier, etc., can be used alone or in combination and repeated. Examples of the preparative high performance liquid chromatography method include a method using a reverse phase column using octadecyl silica or the like, a method using a normal phase column using silica gel or the like, and the like.

By the above-mentioned purification method, water-soluble ionic substances such as salts, nonionic substances such as saccharides and polysaccharides, oils, dyes, and the like are removed from the crude extract, and proanthocyanidins are purified. Also, grape seed extract proanthocyanidins are available from Acta Derm. Veneleodica (Stockholm) [Acta Derm. Venereol. (Stockh.)], 78 , 428
(1998) and the like.

As a method for producing proanthocyanidins by a synthesis method, a method for producing a dimer of epicatechin or catechin is described in Journal of Chemical Society.
Perkin Transaction I (Journal of the Chemic
al Society: Perkin Transactions I): 1535〜1543, 19
83, and various proanthocyanidins can be synthesized by the method described in the literature or according to the method.

An alcohol fermentation product of a plant extract containing proanthocyanidin can be obtained by the following known method. That is, in the case of a single fermentation type fermented liquor such as wine and apple liquor, fruit juice is produced by alcohol fermentation with yeast. For example, in the production of red wine from grape juice, grape fruit is crushed, an antioxidant is added, and then 2-5% of sake brewer is added, followed by main fermentation for 7-10 days. Then, it is squeezed to remove the pericarp and sediment, transferred to an oven with a fermentation stopper, and post-fermented at about 10 ° C. to a residual sugar of 0.2% or less. Precipitates such as tartar, tannin, protein, etc. are produced and stored and aged for several years. In the case of a double fermentation type fermented liquor such as beer, cereal starch is used as a raw material, saccharification with amylase is performed first, and then alcohol fermentation is performed. For example, in the production of beer using barley as a main raw material, wort is made from malt and water, and yeast is added for fermentation. Main fermentation is carried out at 7-10 ° C for 10 days, transferred to a storage tank and post-fermented at 0-2 ° C for 60 days. After completion of the post-fermentation, filtration or heat sterilization is performed to obtain a desired fermentation product.

As a method for purifying proanthocyanidins from the above-mentioned alcoholic fermentation products, the same method as exemplified in the above-mentioned purification method A can be mentioned. By the above-mentioned purification method, proanthocyanidins can be purified as a result of removing water-soluble ionic substances such as salts, nonionic substances such as saccharides and polysaccharides, oils, pigments and the like from alcohol fermentation products.

When proanthocyanidins are used as a component in the composition of the present invention, one kind or two or more kinds of proanthocyanidins may be mixed. Specific examples include grape seed extract proanthocyanidin, red wine extract purified product, apple-derived proanthocyanidin, pine-derived proanthocyanidin, purified proanthocyanidin oligomer, and the like.

In the composition of the present invention, the content of proanthocyanidin is not particularly limited depending on the use and the like.
For example, in a composition for use in beverages, foods, cosmetics, pharmaceuticals, and the like, it is preferably 0.01 to 20% by weight, more preferably 0.1 to 20% by weight, based on the total amount of the composition (total weight of all components of the formulation). 1 to 10% by weight. In the composition of the present invention,
The content of the vitamin B ₆ derivative or the salt thereof is not particularly limited depending on the use and the type of proanthocyanidin. For example, in a composition for use such as beverages, foods, cosmetics, and pharmaceuticals, the total amount of the composition (all the components of the formulation) 0.001 to 1% by weight, more preferably 0.005 to 0.5% by weight, and still more preferably 0.01 to 1% by weight.
~ 0.3% by weight.

The composition of the present invention may contain, for example, antioxidants such as sodium bisulfite, potassium pyrosulfite, ascorbic acid, erythorbic acid and tocopherols. Further, the composition of the present invention can be used for applications such as beverages, foods, cosmetics, and pharmaceuticals by appropriately adding additives and the like suitable for each application.

Hereinafter, the present invention containing the composition of the present invention will be described.
Explain beverages, foods, cosmetics, and pharmaceuticals. The present invention
Beverages such as fruit liquor and soft drinks
Drinks, health drinks, stamina drinks, vitamins
Drinks, fruit juice drinks and the like can be mentioned. The beverage of the present invention,
(1) Those that squeeze plant materials and eat them directly, for example,
Apple juice, grape juice, blueberry juice
(2) heat vegetable ingredients or their processed products
Drinks obtained by water extraction, for example, barley tea, green tea, oolo
Tea, black tea, kakinoha tea, wolfberry tea, etc. (3)
Drink obtained by alcoholic fermentation of plant juice
Foods, such as grape wine, apple wine, blueberry wine, etc.
Alcoholic beverages such as fruit wine, beer, low-malt beer, or
(4) Soak the fruit in alcohol and extract the extract
Beverages obtained by doing
Vitamins in beverages containing proanthocyanidins such as sake
B₆Can be obtained by blending the derivative or its salt.
Can be. Soft drinks, health drinks and
And stamina drinks are proanthocyanidins and vitamins
B ₆In addition to the derivative or its salt, if necessary,
Proteins, sugars, fats, trace elements, vitamins, emulsification
Additives, flavors, etc., and can be manufactured by standard methods
You.

The food of the present invention may be in the form of tablets, capsules, powders, pills, jellies, frozen foods, powdered foods, sheet foods, bottled foods, canned foods, retort foods, etc., as well as naturally flowing foods. Examples include processed forms such as food, semi-digestive nutritional food, component nutritional food, and the like. Food of the present invention, the proanthocyanidin and the vitamin B ₆ derivative or its salt, common ingredients used in foods, for example, proteins, sugars, fats,
It can be produced by a conventional method by adding trace elements, vitamins, emulsifiers, flavors and the like.

The food of the present invention includes, for example, products obtained by processing fruits, such as various jams and syrup-soaked products of various fruits. Examples of the form of the cosmetic of the present invention include liquid products, gel products, emulsion products, and solid products such as creams.
The cosmetic of the present invention comprises proanthocyanidin and vitamin B
₆ Derivatives or salts thereof, common raw materials used in cosmetics, for example, solid oil / semi-solid oil, liquid oil, humectant, emollient, surfactant, water-soluble polymer, oil-soluble polymer, organic Or inorganic pigments, organic powders, ultraviolet absorbers, anti-inflammatory agents, cooling agents, preservatives, antioxidants, pH adjusters (citrate buffer solution, etc.), bactericides, vitamins, crude drugs and crude drug components, skin softness It can be produced by a conventional method by adding an agent, a fragrance, a pigment, ethanol, purified water and the like.

The cosmetics of the present invention include, for example, lotion, serum, milky lotion, cream, pack, hair growth tonic,
Shampoo and the like. As the form of the pharmaceutical of the present invention, tablets, capsules, powders, pills, powders, fine granules,
Granules, syrups, troches and the like can be mentioned. The medicament of the present invention contains proanthocyanidin, a vitamin B ₆ derivative or a salt thereof, and if necessary, other medicament-active ingredients, and is usually formulated by an ordinary method using an excipient. Examples of the excipient include sorbitol, lactose, glucose, sugars such as lactose, dextrin, starch, calcium carbonate, inorganic substances such as calcium sulfate, crystalline cellulose, distilled water, sesame oil, corn oil, olive oil, cottonseed oil, and the like. Any commonly used excipient can be used. When formulating, binders, lubricants, dispersants, suspensions, emulsifiers,
Additives such as diluents, buffers, antioxidants, and bacterial inhibitors may be used.

The compositions of the present invention and the beverages, foods, cosmetics, and medicaments containing the compositions of the present invention are excellent in the stability of proanthocyanidins and have little discoloration of the proanthocyanidins with time. Further, the present invention provides a method stabilizing proanthocyanidin, which comprises blending a vitamin B ₆ derivative or its salt in proanthocyanidin, the method, the amount of the vitamin B ₆ derivative or its salt Such conditions can be implemented by setting the conditions according to the description of the composition of the present invention and the beverage, food, cosmetics, and medicine of the present invention.

Further, the present invention provides also a stabilizing agent of proanthocyanidins containing a vitamin B ₆ derivative or its salt, the conditions of the amount of each vitamin B ₆ derivative or its salt of the present invention described above It can be set according to the description in the description of the composition and the beverages, foods, cosmetics, and medicines of the present invention. Next, regarding the embodiment of the present invention,
The examples, test examples, and reference examples are specifically shown.

[0037]

In the following, (W / W) represents (weight / weight) and (V / V) represents (volume / volume). Example 1 The components shown in Table 1 below were stirred and mixed, and solids were dissolved to produce Compositions 1 to 5 of the present invention. Further, procyanidin B-2 was produced according to Reference Example 3.

[0038]

[Table 1]

Example 2 The components shown in Tables 2-1 and 2-2 below were stirred and mixed, and solids were dissolved to prepare compositions 6 to 13 of the present invention. Further, procyanidin B-2 was produced according to Reference Example 3.

[0040]

[Table 2]

[0041]

[Table 3]

Example 3 The components shown in Tables 3-1 and 3-2 below were stirred and mixed to dissolve solids, and the compositions 14 to 18 of the present invention were dissolved.
Was manufactured. Further, procyanidin B-2 is referred to in Reference Example 3.
Manufactured by

[0043]

[Table 4]

[0044]

[Table 5]

Example 4 The components shown in Table 4 below were stirred and mixed, and solids were dissolved to prepare compositions 19 to 23 of the present invention. Further, procyanidin B-2 was produced according to Reference Example 3.

[0046]

[Table 6]

Example 5 Production of Apple Juice 10 g of pyridoxine hydrochloride was added to 100 kg of the cloudy apple juice obtained in Reference Example 1 to obtain an apple juice bulk, which was filled in a paper pack container to obtain a final product.

Example 6 Production of Wine To 100 kg of the fermented liquor from the barrels obtained in Reference Example 2 was added 10 g of pyridoxine hydrochloride, and the mixture was uniformly stirred and dissolved to obtain a product. This is filled in a glass container to obtain a final product.

Example 7 Production of Blueberry Jam Blueberry 100 kg Granulated sugar 60 kg Lemon juice 1 kg Pyridoxine hydrochloride 0.03 kg (Preparation method) Granulated sugar is added to washed strawberries and heated for 30 minutes. After cooling, add lemon juice and pyridoxine hydrochloride and mix uniformly. Fill into glass containers to make products.

Example 8 Preparation of Beverage (Healthy Drink) Grape Seed Proanthocyanidin (Reference Example 4) 1.0 g Pyridoxine hydrochloride 0.1 g Sodium benzoate 1.0 g Fructose 10.0 g Flavor (fruit mix) Appropriate amount of pigment (blueberry) Dye) Appropriate amount Purified water Appropriate amount Total amount 1000g (Preparation method) The above mixture is uniformly stirred and dissolved, filled into a bottle, and then heat-treated to obtain a product.

Example 9 Preparation of lotion (oil phase component) Perfume (menthol) 0.05 g Polyoxyethylene (60 mol) hydrogenated castor oil (manufactured by Nippon Emulsion Co., Ltd.) 2.0 g 1,3-butylene glycol 0 g (aqueous phase component) Procyanidin B-2 (Reference Example 3) 0.5 g Pyridoxine hydrochloride 0.06 g Glycerin 5.0 g Methyl paraben 0.1 g Citric acid 0.1 g Sodium citrate 0.2 g Ethanol 8.0 g Purified water Appropriate oil The total amount of the phase component and the aqueous phase component 100.0 g (Preparation method) The oil phase component and the aqueous phase component are each dissolved uniformly, and the oil phase is added to the aqueous phase while stirring to prepare a lotion.

Example 10 Preparation of Emulsion (Oil Phase Component) Squalane 4.0 g Wheat Germ Oil 2.0 g Monoglyceryl stearate 1.0 g Polyoxyethylene stearyl ether (manufactured by Nippon Emulsion Co., Ltd.) 4.0 g Propyl paraben 1 g (aqueous phase component) Procyanidin B-2 (Reference Example 3) 0.5 g Pyridoxine hydrochloride 0.06 g Methyl paraben 0.1 g Propylene glycol 0.1 g Polyethylene glycol 6000 (manufactured by NOF CORPORATION) 0.2 g 1% Sodium hyaluronate 5.0 g Purified water appropriate amount Total amount of oil phase component and water phase component 100.0 g (Preparation method) Heat the oil phase component and the water phase component to 80 ° C., respectively, to make them homogeneous, and add the water phase to the oil phase with stirring. Emulsify.

Example 11 Preparation of Hair Restoration Tonic (Oil Phase Component) Ethanol 70 g dl-α-tocopherol acetate 0.2 g Pantothenyl alcohol 0.3 g Polyoxyethylene (60 mol) hydrogenated castor oil (Nippon Emulsion Co., Ltd.) 1 3.0 g Propylene glycol 3.0 g Fragrance (menthol) Trace (aqueous phase component) Procyanidin B-2 (Reference Example 3) 1.0 g Pyridoxine hydrochloride 0.06 g Biotin 0.0001 g Assembly extract 3.0 g Citric acid 0.04 g Citric acid Sodium 0.03 g Sodium bisulfite 0.1 g Purified water appropriate amount Total amount of oil phase component and aqueous phase component 100.0 g (Preparation method) Make oil phase component and aqueous phase component uniform at room temperature, respectively, and stir aqueous phase into oil phase Add to the hair growth tonic.

Example 12 Preparation of Tablets Grape Seed-derived Proanthocyanidin (Reference Example 4) 10.0 g Pyridoxine hydrochloride 1.0 g Lactose 89.0 g Dried corn starch 2.0 g Talc 1.8 g Calcium stearate 0.2 g (Preparation method) Are uniformly mixed and tableted with a single-shot tableting machine to produce tablets having a diameter of 7 mm and a weight of 250 mg.

Example 13 Preparation of Vitamin Drink Proanthocyanidin Derived from Grape Seed (Reference Example 4) 0.3 g Pyridoxine hydrochloride 0.03 g Taurine 1.0 g Thiamine 0.001 g Elleuterococ extract (Morinaga Dairy Co., Ltd.) 0.004 g Ascorbin Acid 0.1 g Citric acid 0.5 g Fructose dextrose liquid sugar (F-55: Sanmatsu Kogyo Co., Ltd.) 20 g Sodium benzoate 0.04 g Flavor (fruit mix) qs Purified water qs 100.0 g (Preparation method) After uniformly stirring and dissolving, the mixture is filled in a glass container and heat-treated to obtain a product.

Test Example 1 Measurement of Color Change of Proanthocyanidin with Time The compositions 1 to 22 obtained in Examples 1 to 4 were stored at 50 ° C. for 1 week or 4 weeks, and then the compositions 1 to 9, 14 to 22 and their control groups have a wavelength of 400 nm (optical path length: 1 c
m), compositions 10-13 and their control group have a wavelength of 5
The absorbance was measured at 00 nm (optical path length: 1 cm). Here, the composition of the control group means that vitamin B ₆
Except for the exclusion of only the derivative or its salt, it refers to a composition produced using the same components as the respective compositions.

The results are shown in Tables 5 to 8.

[0058]

[Table 7]

[0059]

[Table 8]

[0060]

[Table 9]

[0061]

[Table 10]

From the above results, it can be seen that the composition of the present invention has less coloring of proanthocyanidin with time than the composition of the control group.

Test Example 2 Stability test of proanthocyanidins Compositions 6 to 8 obtained in Example 2 and Composition 1 obtained in Example 3
4, 15, the compositions 19 to 23 obtained in Example 4 and their control group were stored at 50 ° C. for 2 weeks or 4 weeks,
Under the following analysis conditions, the content of procyanidin B-2 was measured by high performance liquid chromatography (HPLC). Here, the compositions of the control group are compositions manufactured using the same components as the respective compositions except that only the vitamin B ₆ derivative or the salt thereof was removed from the respective compositions. (HPLC analysis conditions) Column: Inertsil ODS-2 (4.6 mm in diameter) manufactured by GL Sciences
X length 250mm) Mobile phase: acetonitrile / 0.05% trifluoroacetic acid (9
/ 91: volume ratio) Detector: UV 280 nm The retention of procyanidin B-2 in the table was calculated by the following formula.

[0064]

(Equation 1)

The results of Test Example 2 are shown in Tables 9 and 10.

[0066]

[Table 11]

[0067]

[Table 12]

From the above results, it can be seen that the composition of the present invention is superior in the stability of proanthocyanidin to the composition of the control group. Reference Example 1 Production of Apple Cloudy Juice Liquid 1 ton of washed Fuji apple was placed in a crusher, and 10 kg of a 10% aqueous ascorbic acid solution was added. Next, the juice was squeezed by a press and passed through a 60-mesh sieve. Next, a sterilization operation was performed at 95 ° C. for 20 seconds using an instant sterilizer, immediately cooled, and then centrifuged to obtain a cloudy apple juice. Reference Example 2 Production of fermented liquid of grape stuffed in barrels 10 g of grape berries of Cabernet-Sauvignon were crushed, 800 g of potassium pyrosulfite was added, and then 3% of sake brewer was added. Subsequently, it was squeezed to remove the pericarp and precipitates, transferred to a kettle equipped with a fermentation stopper, and subjected to post-fermentation at 15 ° C. The product was stored and aged for 2 years while the deposits such as tartar, tannin, protein, etc. were being permeated.

Reference Example 3 Purification method of procyanidin B-2 [epicatechin- (4β → 8) -epicatechin] from apple juice 21120 kg of apple juice was equilibrated with water by Diaion HP-20 resin (Mitsubishi Chemical Corporation) Through a column (diameter 60 cm × length 88.5 cm: 250 L volume) packed with 1000 L of deionized water and 500 L of 1 L
The column was washed with a 5% (V / V) aqueous methanol solution.
Next, the target substance was eluted with 500 L of a 45% (V / V) methanol aqueous solution. The eluate was dried and 9450 g
Was obtained.

1465 g of the dried product was 25% (V /
V) Sephadex LH-20 dissolved in aqueous methanol solution and equilibrated with 25% (V / V) aqueous methanol solution
(Manufactured by Pharmacia) and passed through a column (diameter 18 cm × length 39.3 cm: 10 L volume).
5% (V / V) methanol aqueous solution, 20 L of 50% (V / V)
/ V) After sequentially washing the column with an aqueous methanol solution, 20 L
The eluted product was eluted with a 75% (V / V) methanol aqueous solution of the above, and the eluted product was dried to obtain 233 g of a dried product.

After dissolving 116 g of the dried product in deionized water, the solution was subjected to preparative high performance liquid chromatography (150 mmφ ×
1000 mm: ODS column, methanol / 0.00
(01% aqueous acetic acid solution = 12/88). Thus, 16.5 g of procyanidin B-2 [purity 94
% Or more]. ¹ H of the obtained procyanidin B-2
-NMR, ¹³ C-NMR and mass spectrum were consistent with those of the standard. The purity of procyanidin B-2 was analyzed by HPLC, and the analysis conditions were the same as those described in Test Example 2. Reference Example 4 Purification of Proanthocyanidins from Grape Seeds Acta Derm. Veneleodica (Stockholm) [Acta Derm. Venereol. (Stockh.)], 78 , 428 (19
98), proanthocyanidins are extracted and purified from Chardonnay grape seeds to obtain grape seeds having an average degree of polymerization of 3.5 and a galloylation ratio of 25% (molar ratio) per proanthocyanidin constituent monomer. The derived proanthocyanidins were obtained.

Galloylation and average degree of polymerization were determined by the method of Acta dermato veneleolodica (Stockholm) [Ac
(Stockh.)], 78 , 428 (1998).

[0073]

According to the present invention, there is provided a composition excellent in the stability of proanthocyanidins, a beverage containing the composition, a food, a cosmetic and a medicine, and a method for stabilizing proanthocyanidins for preventing discoloration due to oxidative polymerization and the like. Provided.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) A23L 2/38 A61K 7/00 K 4C088 A61K 7/00 HD 35/78 C 35/78 H J U B A61P 39/06 A61P 39/06 C12G 1/00 C12G 1/00 A23L 2/00 F (72) Inventor Minako Tajima 2nd Miyukigaoka, Tsukuba, Ibaraki Pref. Kyowa Hakko Kogyo Co., Ltd. Tsukuba Research Institute F-term (reference) 4B017 LC03 LK06 LL09 4B018 MD07 MD23 ME06 4B041 LD04 LK05 4C083 AA111 AA112 AC841 AC842 AC851 AC852 AD631 AD632 CC04 CC05 CC37 DD27 DD31 EE01 4C086 AA01 BA08 BC18 MA02 MA04 NA03 ZC24 ZC41 AB03 AB03 AB03 AB03 AB03 AB08 NA03 ZB21 ZC24

Claims (12)

[Claims] 1. A composition comprising proanthocyanidin and a vitamin B ₆ derivative or a salt thereof. 2. The composition according to claim 1, wherein the concentration of the vitamin B ₆ derivative or a salt thereof is in the range of 0.001 to 1% by weight of the whole composition. 3. The composition according to claim 1, wherein the concentration of proanthocyanidin is 0.01 to 20% by weight of the total composition. 4. The composition according to claim 1, wherein the vitamin B ₆ derivative is pyridoxine, pyridoxal, pyridoxamine or a phosphate thereof. 5. The proanthocyanidin is derived from a plant belonging to the genus grape, apple, barley, coconut, cacao, pine, lingonberry, fragaria, kidney bean or peanut. A composition as described. 6. A beverage containing the composition according to claim 1. 7. A food containing the composition according to claim 1. 8. A cosmetic comprising the composition according to claim 1. 9. A medicament comprising the composition according to claim 1. 10. The beverage according to claim 6, wherein the beverage is a fruit liquor, a fruit juice beverage, or a health drink. 11. Vitamin B _{6 is} added to proanthocyanidins.
A method for stabilizing proanthocyanidin, which comprises adding a derivative or a salt thereof. 12. A proanthocyanidin stabilizer containing a vitamin B ₆ derivative or a salt thereof.