WO2006061877A1 - Propolis extract with improved water dispersibility, propolis-containing beverage, and method of improving water dispersibility of propolis extract - Google Patents

Propolis extract with improved water dispersibility, propolis-containing beverage, and method of improving water dispersibility of propolis extract Download PDF

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Publication number
WO2006061877A1
WO2006061877A1 PCT/JP2004/018163 JP2004018163W WO2006061877A1 WO 2006061877 A1 WO2006061877 A1 WO 2006061877A1 JP 2004018163 W JP2004018163 W JP 2004018163W WO 2006061877 A1 WO2006061877 A1 WO 2006061877A1
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Prior art keywords
propolis
water dispersibility
propolis extract
extract
improved
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PCT/JP2004/018163
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French (fr)
Japanese (ja)
Inventor
Rindai Yamamoto
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Rindai Yamamoto
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Priority to CN2004800445476A priority Critical patent/CN101083915B/en
Priority to PCT/JP2004/018163 priority patent/WO2006061877A1/en
Priority to TW093140567A priority patent/TW200621169A/en
Publication of WO2006061877A1 publication Critical patent/WO2006061877A1/en

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    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L2/00Non-alcoholic beverages; Dry compositions or concentrates therefor; Their preparation
    • A23L2/52Adding ingredients
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L21/00Marmalades, jams, jellies or the like; Products from apiculture; Preparation or treatment thereof
    • A23L21/20Products from apiculture, e.g. royal jelly or pollen; Substitutes therefor
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L33/00Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
    • A23L33/10Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
    • A23L33/105Plant extracts, their artificial duplicates or their derivatives
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K35/00Medicinal preparations containing materials or reaction products thereof with undetermined constitution
    • A61K35/56Materials from animals other than mammals
    • A61K35/63Arthropods
    • A61K35/64Insects, e.g. bees, wasps or fleas
    • A61K35/644Beeswax; Propolis; Royal jelly; Honey

Definitions

  • the present invention relates to a propolis extract with improved dispersibility in water and a beverage containing such a propolis extract.
  • Such a propolis extract is supplied in a dropper bottle or the like in which a dropper is set in a cap as a liquid (propolis liquid) that can be mixed with ethanol or other suitable solvent and dropped with a dropper.
  • a liquid propolis liquid
  • 20-30 drops of the liquid is dropped into a suitable amount of water, hot water, milk, coffee, tea, juice, honey, drinks or alcoholic beverages, in the morning, noon and evening. Ingested orally three times a day, or in the morning, noon, candy, and 4 times a day before going to bed four times a day before going to bed, it is said to be taken orally by dropping into the beverage.
  • the water-insoluble component of the propolis extract is dissolved in the beverage. It may become “swift” and float on the surface of the beverage, or may sink and adhere to the bottom or side of the container, making it impossible to take the required amount.
  • ingredients that float on the surface of the beverage may stick to the drinker's teeth, gums, tongue, palate, or throat during drinking and may not be able to be effectively consumed, and even after drinking For some time, discomfort or irritation continues.
  • the propolis extract is so-called “bitter taste” in terms of taste, and feels “spicy” at the time of quoting, and it is generally difficult to drink because it smells too strong.
  • means such as capsules.
  • the amount of a single dose is 20-30 drops! / 50-50 and so many drops! It was suitable for drinking! /, Became large, or increased in the number of capsules to be consumed at one time.
  • Patent Document 1 proposes a technique of adding and blending milk proteins such as milk casein.
  • Patent Document 1 JP 2001-169736 A
  • the present invention improves the above-mentioned conventional problems, that is, the disadvantages of propolis having excellent characteristics without using milk protein or the like, adhesion to containers, oral cavity and throat, flavor
  • the object is to provide a method for improving the difficulty of improvement and a propolis in which these drawbacks are improved.
  • the water dispersibility-improved propolis extract of the present invention is a propolis extract by alcohol extraction as described in claim 1, and is sodium carbonate, Z, or hydrogen carbonate. Water-dispersible modified propolis extract heat-treated in the presence of sodium.
  • the propolis-containing beverage of the present invention is a propolis-containing beverage containing the water dispersibility-improved propolis extract as described above.
  • the method for improving water dispersibility of a propolis extract of the present invention is a propolis extract obtained by alcohol extraction, wherein the propolis extract has a constitution in which heat treatment is performed in the presence of sodium carbonate or Z and sodium bicarbonate. This is a method for improving the water dispersibility of products.
  • the invention's effect is a propolis extract obtained by alcohol extraction, wherein the propolis extract has a constitution in which heat treatment is performed in the presence of sodium carbonate or Z and sodium bicarbonate.
  • the water dispersibility-improved propolis extract of the present invention since there is no attachment to the container, the oral cavity or the throat, there is no wasteful part attached to the container, so that the entire amount can be ingested.
  • the container can be easily cleaned after use, and it can be used repeatedly, and it is not necessary to carry a dedicated container when going out, and the discomfort caused by attachment to the oral throat, An unpleasant taste with no unpleasantness and a long-lasting odor is prevented.
  • a beverage containing a propolis extract that is easy to clean, and can contain only a small amount of beverage that can be drunk in a single or half mouth, but can contain the necessary amount of propolis for a healthy person It can be.
  • FIG. 1 is a chromatogram obtained by high-performance liquid chromatography of a propolis solution before treatment for improving water dispersibility.
  • FIG. 2 High-performance liquid chromatogram of propolis extract (A) with improved water dispersibility.
  • a propolis extract obtained by alcohol extraction is obtained in the form of a propolis solution dissolved in ethanol.
  • the content of the propolis extract in this propolis liquid is generally 20-33% by volume, and in addition, some water (about 10-15% by volume) and ethanol (remaining amount).
  • the propolis extract contained in such a propolis liquid is subjected to a heat treatment in the presence of sodium carbonate or Z and sodium bicarbonate.
  • the amount of sodium hydrogen carbonate and the sodium carbonate water dispersibility improver varies depending on the content of the propolis extract contained in the pour-polis solution to be used. In the case of 33% by volume of propolis liquid, it is 0.5% by mass or more and 2% by mass or less. At this time, if the addition amount is less than 0.5% by mass, sufficient water dispersibility improvement effect may not be obtained. Moreover, if the added amount is close to 2% by mass, a sufficient effect of improving water dispersibility can be obtained, and even if added in excess of 2% by mass, it does not dissolve in the propolis solution, and it appears to be unreacted even after heat treatment. In some cases, it may be necessary to remove the powder by means such as filtration. In the case of a propolis liquid having a different volume content of the propolis extract, the water dispersibility improver should be converted so that it falls within the range of the ratio of the propolis extract and the water dispersibility improver in the above example. Added.
  • a preferable heat treatment temperature has a lower limit of 40 ° C. or higher, desirably 50 ° C. or higher, and an upper limit of 70 ° C. or lower, desirably 65 ° C. or lower.
  • propolis extract obtained by alcohol extraction
  • water dispersibility-improved propolis extract heat-treated in the presence of sodium carbonate, Z, or sodium bicarbonate uniformly emulsified?
  • this water dispersibility-improved propolis extract has a high ethanol content, so if it is sealed, there is no risk of spoilage.
  • each major component of quercetin, kaempferol, diterpene, and paracoumaric acid which is considered to be an active ingredient in the propolis extract, does not change before and after the treatment. There is no difference in the components or the results of high-performance liquid chromatography. In addition, no change was seen before and after the water dispersibility improvement treatment in the analysis using an absorptiometer in the ultraviolet region.
  • the water dispersibility-improved propolis extract thus obtained is excellent in water dispersibility, so that the components settle even when mixed with general soft drinks, tea, tea, etc. at various mixing ratios. There is nothing to do.
  • a propolis-containing beverage can be easily obtained by blending the water-dispersibility-improved propolis extract in the production process of these soft drinks, etc., so that masking of the odor peculiar to propolis becomes easier. Easy to drink or drink.
  • the propolis solution is an ethanol solution containing 32% by volume propolis extract (however,
  • sodium bicarbonate (NaHCO3) in the amounts shown in Tables 1 and 2 was used.
  • the pH of the water dispersibility-improved propolis extract in Tables 1 and 2 is about 6.7-6.9 compared to 5.3 for the original propolis solution. It was almost neutral.
  • Fig. 1 shows the chromatogram of the propolis solution before the water dispersibility improvement treatment
  • Fig. 2 shows the chromatogram of the water dispersibility improved provolis extract (A).
  • the water dispersibility-improved propolis extract (A) was evaluated for the degree of adhesion to the container at the same time as the evaluation with the propolis liquid without the water dispersibility improvement treatment.
  • Kenferrol and quercetin were measured under the above conditions, except that the detection wavelength was 380 nm. As a result, these components having peaks at retention times of about 25 minutes and about 52 minutes, and those components that do not change in peak height and area before and after the treatment, are also subjected to the water dispersibility improvement treatment of the present invention. It was confirmed that it was not affected.
  • the average mass of the adhered residue is 0.1 l lg, and this amount corresponds to a little over 7% as the propolis component.
  • the average amount of adhering residue in the cup is 0.002 g, indicating that there is virtually no adhering residue. confirmed. It was confirmed that the slight adhesion residue at this time can be easily removed by hand washing with running water.
  • the water dispersibility-improved propolis extract A does not impair its good water dispersibility even when dripped not only in water but also in green tea, black tea, and the like.
  • the components do not sink even if the residual alcohol content is reduced by, for example, decompression or heating after addition to beverages or water. It has been found that the water dispersibility-improved provolis extract of the present invention can also be applied to the field of non-alcoholic beverages and the like in which the above problems are problematic.
  • the disadvantages of a propolis having a number of excellent properties are the disadvantages of adhesion to containers, oral cavity and throat, and difficulty in improving flavor. It can be remarkably improved without using milk protein or the like. For this reason, the water dispersibility-improved propolis extract according to the present invention can be easily applied to the food and beverage fields, which have been difficult to apply, as well as the fields where the conventional propolis extract is used.

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  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Nutrition Science (AREA)
  • Engineering & Computer Science (AREA)
  • Food Science & Technology (AREA)
  • Polymers & Plastics (AREA)
  • Insects & Arthropods (AREA)
  • Epidemiology (AREA)
  • Animal Husbandry (AREA)
  • Botany (AREA)
  • Zoology (AREA)
  • Medicinal Chemistry (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Mycology (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Medicines Containing Material From Animals Or Micro-Organisms (AREA)
  • Jellies, Jams, And Syrups (AREA)

Abstract

[PROBLEMS] To provide a method of relieving the adhesion to container, inside of oral cavity and throat and difficulty in flavor enhancement being drawbacks of propolis with excellent performance without the use of substances having the danger of hindering the absorption of milk protein, etc., and to provide a propolis extract with improved water dispersibility wherein the above drawbacks have been relieved. [MEANS FOR SOLVING PROBLEMS] There is provided a propolis extract with improved water dispersibility, produced by heating a propolis extract obtained by alcohol extraction in the presence of sodium carbonate or/and sodium hydrogen carbonate.

Description

明 細 書  Specification
水分散性改良プロポリス抽出物、含プロポリス飲料、及び、プロポリス抽出 物の水分散性改良方法  Water dispersibility improved propolis extract, propolis-containing beverage, and method for improving water dispersibility of propolis extract
技術分野  Technical field
[0001] 本発明は、水に対する分散性を改善させたプロポリス抽出物、及び、そのようなプロ ポリス抽出物を含む飲料に関する。  [0001] The present invention relates to a propolis extract with improved dispersibility in water and a beverage containing such a propolis extract.
背景技術  Background art
[0002] 最近の健康ブームや自然派志向により、さまざまな天然健康食品が注目されて 、 る。これら天然健康食品の中でも、ミツバチによって作り出される天然の抗生物質、あ るいは、天然の細胞活性ィ匕物質とも云われるプロポリス力も抽出されたプロポリス抽 出物は、健康増進、体質改善に供するものとして、あるいは、高い抗ガン効果が期待 されるものとして特に注目されて 、る。  [0002] Due to the recent health boom and naturalism orientation, various natural health foods are attracting attention. Among these natural health foods, the natural antibiotics produced by bees or the propolis extract from which propolis power, also called natural cell-active substances, has been extracted are intended to promote health and improve health. Or, it is particularly attracting attention as a high anti-cancer effect.
[0003] このようなプロポリス抽出物はエタノール他の適当な溶媒に混合してスポイトにより 滴下可能な液 (プロポリス液)として、スポイトがキャップにセットされたスポイト瓶など に容れられて供給され、例えば、健康維持目的ではその液の 20— 30滴を適量の水 、湯、牛乳、コーヒー、紅茶、ジュース、蜂蜜、ドリンク剤あるいは酒類などの飲料に滴 下して朝、昼、及び、晩の一日 3回経口摂取し、あるいは、体調を崩したときには朝、 昼、晚、及び、就寝前の一日 4回、 50— 100滴をやはり上記飲料に滴下して経口摂 取するとされている。  [0003] Such a propolis extract is supplied in a dropper bottle or the like in which a dropper is set in a cap as a liquid (propolis liquid) that can be mixed with ethanol or other suitable solvent and dropped with a dropper. For health maintenance purposes, 20-30 drops of the liquid is dropped into a suitable amount of water, hot water, milk, coffee, tea, juice, honey, drinks or alcoholic beverages, in the morning, noon and evening. Ingested orally three times a day, or in the morning, noon, candy, and 4 times a day before going to bed four times a day before going to bed, it is said to be taken orally by dropping into the beverage.
[0004] し力しながら、エタノールに溶解したプロポリス液が上記のような飲料に滴下されると 、そのプロポリス抽出物のうち、水可溶成分は飲料に溶解するものの、水不溶性成分 はいわゆる「やに」状となり、飲料の表面に浮いたり、あるいは、沈下して容器の底や 側面に付着してしまい、所要量の摂取ができなくなるおそれがある。  [0004] However, when the propolis solution dissolved in ethanol is dropped into the beverage as described above, the water-insoluble component of the propolis extract is dissolved in the beverage. It may become “swift” and float on the surface of the beverage, or may sink and adhere to the bottom or side of the container, making it impossible to take the required amount.
[0005] このうち、飲料表面に浮いた成分は飲用の際に飲用者の歯や歯ぐき、舌、口蓋ある いはのどに付着して、有効に摂取できなくなる場合がある上に、飲用後もしばらくの 間、不快感ゃあるいは刺激感を与え続ける。  [0005] Of these, ingredients that float on the surface of the beverage may stick to the drinker's teeth, gums, tongue, palate, or throat during drinking and may not be able to be effectively consumed, and even after drinking For some time, discomfort or irritation continues.
[0006] 一方、容器の底や側面に付着した成分は、当然、飲用できないので有効に活用さ れな 、上に、通常の洗浄方法 (洗剤を用いた洗浄)では容易に除去できな ヽ(特に 漆器に付着した場合には、器を傷めずに洗浄除去することは経験上不可能である) と云った問題があった。 [0006] On the other hand, the components adhering to the bottom and side surfaces of the container cannot be drunk naturally, and thus are effectively utilized. In addition, it cannot be removed easily by ordinary cleaning methods (cleaning with a detergent) (especially if it adheres to lacquer ware, it is impossible to wash and remove without damaging the container. There was a problem that said.
[0007] さらに、プロポリス抽出物は味覚という点では、いわゆる「口苦し」であって、引用時 にのどに「辛さ」を感じ、また、においもきついため、一般に飲みにくい。ここで、カプ セルィ匕などの手段を利用することも可能ではある力 一回当たりの飲用量が上記のよ うに 20— 30滴な!/、し 50— 100滴と多!、ため、カプセルが飲用に適さな!/、大きさとな り、あるいは、一度に飲むカプセル数が多くなり、いずれも実用的でなぐ根本的な解 決が望まれていた。  [0007] Furthermore, the propolis extract is so-called “bitter taste” in terms of taste, and feels “spicy” at the time of quoting, and it is generally difficult to drink because it smells too strong. Here, it is also possible to use means such as capsules. The amount of a single dose is 20-30 drops! / 50-50 and so many drops! It was suitable for drinking! /, Became large, or increased in the number of capsules to be consumed at one time.
[0008] そこで、プロポリス液を他の飲料成分に混合して、飲みやす 、飲料とする検討が行 われていたが、上記のような容器への付着の問題が解決されておらず、付着しない 程度に配合すると配合量が少なくなり、プロポリス抽出物の充分な飲用量を確保する ための必要な飲用量が、例えば 200mLと多くなる。このとき量が多いため飲む途中 に息継ぎが必要となるが、ー且息継ぎをすると、その後継続して飲用することがため らわれて必要量が飲みきれずに残したり、あるいは、全量飲みきるのに大きな決心が 必要とされたりして、風味を改善し、飲みやすくするという点では困難があった。  [0008] Therefore, studies have been made to mix propolis liquid with other beverage components to make it easier to drink, but the above-mentioned problem of adhesion to containers has not been solved and does not adhere. When it is blended to the extent, the blending amount is reduced, and the necessary dose for securing a sufficient dose of propolis extract is increased to, for example, 200 mL. At this time, since the amount is large, breathing is necessary while drinking, but if you breathe, you will be reluctant to continue drinking afterwards, or you may not be able to drink the necessary amount, or you may drink all of the amount. However, it was difficult to improve the flavor and make it easier to drink.
[0009] ここでプロポリス抽出物の水分散性を向上させるために特開 2001— 169736号公 報 (特許文献 1)では、ミルクカゼイン等の乳蛋白質を添加配合する技術が提案され ている。  Here, in order to improve the water dispersibility of the propolis extract, Japanese Patent Laid-Open No. 2001-169736 (Patent Document 1) proposes a technique of adding and blending milk proteins such as milk casein.
[0010] し力しながら、充分に分散させるための液量はかなり多く必要で、そのためプロポリ ス抽出物の充分な飲用量を確保するための必要な飲用量も多くなると云う上記欠点 は解消されない。また、例えば、子供が洗剤等を誤飲した際に、まず第 1の処置とし て、その吸収を妨げるために牛乳を飲ませることが知られているように、乳蛋白質に は他の物質の吸収を遅らせたり、妨げたりする機能があり、上記従来技術ではプロボ リスの有効成分を体内に取り込めな 、可能性が指摘されて 、た。  [0010] However, the above-mentioned drawback that the amount of liquid required for sufficient dispersion is considerably large and therefore the amount necessary for securing a sufficient amount of the propolis extract is increased cannot be solved. . Also, for example, it is known that when a child accidentally swallows a detergent etc., milk protein is used as the first treatment to prevent the absorption of other substances in milk protein. It has the function of delaying or preventing absorption, and it has been pointed out that the above-mentioned conventional technology cannot incorporate the active ingredient of Provolis into the body.
特許文献 1:特開 2001— 169736号公報  Patent Document 1: JP 2001-169736 A
発明の開示  Disclosure of the invention
発明が解決しょうとする課題 [0011] 本発明は、上記した従来の問題点を改善する、すなわち、乳蛋白質等を用いること なぐ優れた特性を有するプロポリスが持つ欠点である、容器、口腔内やのどへの付 着、風味改善への困難性を改善する方法、および、これら欠点が改善されたプロポリ スを提供することを目的とする。 Problems to be solved by the invention [0011] The present invention improves the above-mentioned conventional problems, that is, the disadvantages of propolis having excellent characteristics without using milk protein or the like, adhesion to containers, oral cavity and throat, flavor The object is to provide a method for improving the difficulty of improvement and a propolis in which these drawbacks are improved.
課題を解決するための手段  Means for solving the problem
[0012] 本発明の水分散性改良プロポリス抽出物は上記課題を解決するため、請求項 1に 記載の通り、アルコール抽出によるプロポリス抽出物であって、炭酸ナトリウム、あるい は Z及び、炭酸水素ナトリウム存在下で加熱処理された水分散性改良プロポリス抽 出物である。  [0012] In order to solve the above-mentioned problem, the water dispersibility-improved propolis extract of the present invention is a propolis extract by alcohol extraction as described in claim 1, and is sodium carbonate, Z, or hydrogen carbonate. Water-dispersible modified propolis extract heat-treated in the presence of sodium.
[0013] また、本発明の含プロポリス飲料は上記のような水分散性改良プロポリス抽出物を 含有する含プロポリス飲料である。  [0013] The propolis-containing beverage of the present invention is a propolis-containing beverage containing the water dispersibility-improved propolis extract as described above.
[0014] さらに、本発明のプロポリス抽出物の水分散性改良方法は、アルコール抽出による プロポリス抽出物であって、炭酸ナトリウム、あるいは Z及び、炭酸水素ナトリウム存在 下で加熱処理する構成を有するプロポリス抽出物の水分散性改良方法である。 発明の効果  [0014] Further, the method for improving water dispersibility of a propolis extract of the present invention is a propolis extract obtained by alcohol extraction, wherein the propolis extract has a constitution in which heat treatment is performed in the presence of sodium carbonate or Z and sodium bicarbonate. This is a method for improving the water dispersibility of products. The invention's effect
[0015] 本発明の水分散性改良プロポリス抽出物によれば、容器や、口腔内 ·のどへの付 着がないため、容器に付着して無駄となる部分がないので全量摂取が可能であり、 使用後の容器の洗浄が容易であり、容器の繰り返し利用が可能となり、また、外出時 などに際しても専用容器を持ち運ぶことが必要でなくなり、また、口腔内'のどへの付 着による違和感、不快感がなぐ不快な味'臭いの長時間残留が防止される。  [0015] According to the water dispersibility-improved propolis extract of the present invention, since there is no attachment to the container, the oral cavity or the throat, there is no wasteful part attached to the container, so that the entire amount can be ingested. The container can be easily cleaned after use, and it can be used repeatedly, and it is not necessary to carry a dedicated container when going out, and the discomfort caused by attachment to the oral throat, An unpleasant taste with no unpleasantness and a long-lasting odor is prevented.
[0016] さらに、水に容易に分散させることができ、数週間は沈降が認められないことから、 飲みやすい香味等を有する含プロポリス飲料への加工が容易であり、そのときも、 10 一 30mL程度の、一口か半口で飲用できるごく少量の飲料でありながら、健康者の 1 日所要量のプロポリス成分を含む飲料とすることができ、かつ、容器の洗浄が容易な プロポリス抽出物含有飲料とすることができる。  [0016] Furthermore, since it can be easily dispersed in water and no sedimentation is observed for several weeks, it can be easily processed into a propolis-containing beverage having a flavor that is easy to drink. A beverage containing a propolis extract that is easy to clean, and can contain only a small amount of beverage that can be drunk in a single or half mouth, but can contain the necessary amount of propolis for a healthy person It can be.
図面の簡単な説明  Brief Description of Drawings
[0017] [図 1]水分散性改良処理前のプロポリス液の高速液体クロマトグラフィーによるクロマト グラムである。 [図 2]水分散性改良プロポリス抽出物 (A)の高速液体クロマトグラフィーによるクロマト グラムである。 [0017] FIG. 1 is a chromatogram obtained by high-performance liquid chromatography of a propolis solution before treatment for improving water dispersibility. [Fig. 2] High-performance liquid chromatogram of propolis extract (A) with improved water dispersibility.
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0018] アルコール抽出によるプロポリス抽出物は、エタノールに溶解した、プロポリス液の 形で入手される。このプロポリス液中の、プロポリス抽出物の含有量は一般に 20— 33 体積%であり、その他、若干の水(10— 15体積%程度)とエタノール (残量)である。  [0018] A propolis extract obtained by alcohol extraction is obtained in the form of a propolis solution dissolved in ethanol. The content of the propolis extract in this propolis liquid is generally 20-33% by volume, and in addition, some water (about 10-15% by volume) and ethanol (remaining amount).
[0019] 本発明では、このようなプロポリス液に含まれたプロポリス抽出物に対して、炭酸ナト リウム、あるいは Z及び、炭酸水素ナトリウム存在下で加熱処理を施す。  In the present invention, the propolis extract contained in such a propolis liquid is subjected to a heat treatment in the presence of sodium carbonate or Z and sodium bicarbonate.
[0020] 炭酸水素ナトリウムおよび炭酸ナトリウムの水分散性改良剤の添加量は、用いるプ 口ポリス液に含まれたプロポリス抽出物の含有量によっても異なる力 通常、例えばプ 口ポリス抽出物含有量が 33体積%のプロポリス液の場合、 0. 5質量%以上 2質量% 以下であり、このとき、添加量が 0. 5質量%未満では充分な水分散性改良効果が得 られない場合があり、また、添加量が 2質量%近くあれば充分な水分散性改良効果 が得られ、かつ、 2質量%を越えて添加してもプロポリス液に溶解せず、加熱処理後 においても未反応と思われる粉末が沈降するので、この粉末を濾過等の手段により 除去する必要が発生する場合がある。なお、プロポリス抽出物の体積含有率が異な るプロポリス液の場合には、換算して上記例のプロポリス抽出物と水分散性改良剤と の比の範囲内となるように水分散性改良剤を添加する。  [0020] The amount of sodium hydrogen carbonate and the sodium carbonate water dispersibility improver varies depending on the content of the propolis extract contained in the pour-polis solution to be used. In the case of 33% by volume of propolis liquid, it is 0.5% by mass or more and 2% by mass or less. At this time, if the addition amount is less than 0.5% by mass, sufficient water dispersibility improvement effect may not be obtained. Moreover, if the added amount is close to 2% by mass, a sufficient effect of improving water dispersibility can be obtained, and even if added in excess of 2% by mass, it does not dissolve in the propolis solution, and it appears to be unreacted even after heat treatment. In some cases, it may be necessary to remove the powder by means such as filtration. In the case of a propolis liquid having a different volume content of the propolis extract, the water dispersibility improver should be converted so that it falls within the range of the ratio of the propolis extract and the water dispersibility improver in the above example. Added.
[0021] なお、本発明の水分散性改良プロポリス抽出物の製造方法では、水分散性改良剤 として炭酸水素ナトリウムあるいは炭酸ナトリウムを用いる必要がある。クェン酸等の 可食酸を用いたり、あるいは水酸ィ匕ナトリウムをプロポリス液が中性になるように添カロ した後に加熱処理を行うなどしても、充分な水分散性改良効果は得られな 、。  [0021] In the method for producing a water dispersibility-improving propolis extract of the present invention, it is necessary to use sodium hydrogen carbonate or sodium carbonate as the water dispersibility improver. Even if edible acid such as citrate is used or heat treatment is performed after sodium hydroxide is added so that the propolis solution becomes neutral, sufficient water dispersibility improvement effect can be obtained. Nah ...
[0022] このようにプロポリス液に対して炭酸ナトリウム、ある!/、は Z及び、炭酸水素ナトリウ ムを添加した後、加熱処理を行う。  [0022] In this way, after adding sodium carbonate, certain! /, Z and sodium hydrogen carbonate to the propolis solution, heat treatment is performed.
[0023] 好ましい加熱処理温度としては、下限が 40°C以上、望ましくは 50°C以上、上限は 7 0°C以下で望ましくは 65°C以下である。  A preferable heat treatment temperature has a lower limit of 40 ° C. or higher, desirably 50 ° C. or higher, and an upper limit of 70 ° C. or lower, desirably 65 ° C. or lower.
[0024] 加熱処理は加熱による発泡が完了するまで続ける(通常、 15— 30分程度)力 40 °C以下の場合、 30分を越えて加熱処理を行っても発泡が終了せず、また、このとき、 充分な水分散性改良効果が得られない場合がある。一方、 70°Cを越えた温度では 処理後のプロポリス液が赤く変色する場合があり、また、飲用時での「辛味」やのどへ の刺激等が増加する場合がある。 [0024] The heat treatment continues until foaming by heating is completed (usually about 15-30 minutes). When the force is 40 ° C or less, foaming does not end even if the heat treatment is performed for more than 30 minutes. At this time, A sufficient water dispersibility improvement effect may not be obtained. On the other hand, if the temperature exceeds 70 ° C, the treated propolis solution may turn red, and “pungency” or irritation to the throat during drinking may increase.
[0025] このようにアルコール抽出によるプロポリス抽出物であって、炭酸ナトリウム、あるい は Z及び、炭酸水素ナトリウム存在下で加熱処理された水分散性改良プロポリス抽 出物は均一に乳化しているかの状態となるが、安定で数週間経っても沈降しない。さ らにこの水分散性改良プロポリス抽出物はエタノール含有量が高 、ため密栓さえして おけば腐敗等の恐れはな 、。  [0025] As described above, is a propolis extract obtained by alcohol extraction, and is the water dispersibility-improved propolis extract heat-treated in the presence of sodium carbonate, Z, or sodium bicarbonate uniformly emulsified? However, it does not settle even after several weeks. Furthermore, this water dispersibility-improved propolis extract has a high ethanol content, so if it is sealed, there is no risk of spoilage.
[0026] また、成分についてもプロポリス抽出物中の有効成分と目されるケルセチン、ケンフ エロール、ジテルペン、パラクマル酸の各主要成分の含有量についても、処理の前 後で変化はなぐまた、その他の成分についても高速液体クロマトグラフィーによる分 祈の結果でも差異は見られない。また、紫外域での吸光光度計による分析でも水分 散性改良処理の前後で変化が見られな 、。  [0026] In addition, the content of each major component of quercetin, kaempferol, diterpene, and paracoumaric acid, which is considered to be an active ingredient in the propolis extract, does not change before and after the treatment. There is no difference in the components or the results of high-performance liquid chromatography. In addition, no change was seen before and after the water dispersibility improvement treatment in the analysis using an absorptiometer in the ultraviolet region.
[0027] このようにして得られた水分散性改良プロポリス抽出物は水分散性に優れているた め、一般の清涼飲料やお茶、紅茶等に、様々な混合比で混ぜても成分が沈降するこ とがない。  [0027] The water dispersibility-improved propolis extract thus obtained is excellent in water dispersibility, so that the components settle even when mixed with general soft drinks, tea, tea, etc. at various mixing ratios. There is nothing to do.
[0028] このため、これら清涼飲料等の製造過程で水分散性改良プロポリス抽出物を配合 することで、容易に含プロポリス飲料を得ることができるので、プロポリス特有の匂いの マスキングが容易となり、より飲みやす 、飲料とすることができる。  [0028] Therefore, a propolis-containing beverage can be easily obtained by blending the water-dispersibility-improved propolis extract in the production process of these soft drinks, etc., so that masking of the odor peculiar to propolis becomes easier. Easy to drink or drink.
実施例  Example
[0029] 以下に本発明の水分散性改良プロポリス抽出物の実施例について具体的に説明 する。  [0029] Examples of the water dispersibility-improved propolis extract of the present invention will be specifically described below.
[0030] <処理条件の影響についての検討 >  [0030] <Examination of effects of processing conditions>
プロポリス液としては、 32体積%のプロポリス抽出物を含むエタノール溶液 (ただし The propolis solution is an ethanol solution containing 32% by volume propolis extract (however,
、若干の水を含む)を用いた。 , Containing some water).
[0031] これらプロポリス液に対して、表 1及び表 2に示す量で炭酸水素ナトリウム (NaHCO [0031] To these propolis solutions, sodium bicarbonate (NaHCO3) in the amounts shown in Tables 1 and 2 was used.
)または炭酸ナトリウム (Na CO )を添加し、次いで、やはり表 1に示す温度で加熱 ) Or sodium carbonate (Na 2 CO 3) and then heating at the temperatures shown in Table 1
3 2 3 3 2 3
処理を、発泡が終了するまで(15— 25分程度)行った。 [0032] このとき、容器内の液面に膜が発生したかどうか、また、他の容器への移し替えを行 つたときに元の容器の壁面、底面に付着物があるかどうかを目視で調べた他、実際 に飲用し、官能試験も行った。このときの結果を表 1に併せて記載する。 The treatment was carried out until foaming was completed (about 15-25 minutes). [0032] At this time, whether or not a film has formed on the liquid level in the container, and whether or not there are deposits on the wall surface and bottom surface of the original container when transferred to another container are visually observed. In addition to the investigation, it was actually consumed and a sensory test was conducted. The results are shown in Table 1.
[0033] [表 1]  [0033] [Table 1]
Figure imgf000007_0001
Figure imgf000007_0001
[0034] [表 2] [0034] [Table 2]
添加量 (質量 ¾) 加熱処理 膜の 容器へ 目視検査、 官能試験での特記事項Amount added (mass ¾) Heat treatment Membrane container Special instructions for visual inspection and sensory test
NaHCO Na 2C03 温度 (°C) 形成 の付着 NaHCO Na 2 C0 3 temperature (° C) formation adhesion
0 3 . 0 4 5 なし 微量に 粉末状の沈殿あり、 濾過除去後は完全 あり に均一分散  0 3. 0 4 5 None Slightly powdered precipitate, completely dispersed after filtration removed, evenly dispersed
0 1 . 0 4 5 なし 微量に 完全に均一分散  0 1 .0 4 5 None
あり  Yes
0 1 . 5 5 0 なし 微量に 完全に均一分散  0 1 .5 5 0 None
あり  Yes
0 1 . 5 6 0 なし なし 完全に均一分散  0 1 .5 6 0 None None Completely uniform dispersion
0 3 . 0 7 0 なし なし 粉末状の沈殿あり、 濾過除去後は完全 に均一分散、 変色 (赤) が認められ る、 濾過後飲用時に、 のどへの刺激が 強い  0 3. 0 7 0 None None Precipitate in powder form, completely uniform dispersion after removal by filtration, discoloration (red), strong irritation to throat when drinking after filtration
1 . 0 1 , 5 6 0 なし なし 完全に均一分散  1.0 1, 5 6 0 None None Completely uniform dispersion
[0035] 表 1及び表 2によれば、プロポリス液に対する炭酸水素ナトリウム及び炭酸ナトリウム の総添加量が 2質量%以上の系ではこれらの残留物と思われる粉末状の沈殿が見ら れたが、総添加量が 2質量%以下の系では分散性が向上したことが判る。なお、上 記表 1及び表 2において、均一分散状態が得られたサンプルについて、密閉条件で 室温下 3週間の放置テストを行ったが、沈殿の発生はなぐ均一分散状態が保たれ た。 [0035] According to Tables 1 and 2, in the system in which the total amount of sodium hydrogen carbonate and sodium carbonate added to the propolis liquid was 2% by mass or more, a powdery precipitate that was thought to be a residue was observed. It can be seen that the dispersibility was improved in the system with a total addition amount of 2% by mass or less. In Tables 1 and 2 above, samples that were uniformly dispersed were subjected to a standing test at room temperature for 3 weeks under sealed conditions, but the uniform dispersion state was maintained with no precipitation.
[0036] なお、表 1及び表 2での水分散性改良プロポリス抽出物の pHは、元のプロポリス液 の pHが 5. 3であったのに対して、 6. 7-6. 9程度とほぼ中性域となっていた。なお、 未処理のプロポリス液に pHが 6. 8になるように水酸ィ匕ナトリウム水溶液を添カ卩し、次 いで 60°Cで 25分間の加熱処理を行った力 この場合には分散性の向上は見られな かった。  [0036] The pH of the water dispersibility-improved propolis extract in Tables 1 and 2 is about 6.7-6.9 compared to 5.3 for the original propolis solution. It was almost neutral. In addition, the power of adding sodium hydroxide aqueous solution to untreated propolis solution to pH 6.8, followed by heat treatment at 60 ° C for 25 minutes. There was no improvement.
[0037] また、これら水分散性改良プロポリス抽出物のうち、容器への付着がなしとされたサ ンプルについては、実際の官能検査のときにも、唇や歯茎などへの付着残留感を与 えることが全くなぐまた、容器への付着が微量とされたサンプルについてもこれら付 着残留感を殆どないことが確認され、また、これら両者において、未処理のプロポリス 液を用いた場合にしばしば生じる、飲用後 30分一 1時間程度継続するの、のどへの 刺激感も 5分以内に解消することが確認された。  [0037] Among these water dispersibility-improved propolis extracts, the samples that were not attached to the container gave a residual feeling of adhesion to the lips and gums even during the actual sensory test. In addition, it was confirmed that there was almost no sticking to these samples even when the amount of adhesion to the container was very small. In both cases, it often occurred when untreated propolis solution was used. It was confirmed that the irritation to the throat was resolved within 5 minutes.
[0038] <水分散性改良処理のプロポリスの成分への影響につ!、て > ここで、炭酸水素ナトリウムを 2質量%添加し、 60°Cで加熱処理を行った水分散性 改良プロポリス抽出物 (A)について、水分散性改良処理の処理前後の、その成分の 変化の有無の検討を高速液体クロマトグラフィーにより行った。 [0038] <Influence of Propolis on Water Dispersibility Improvement Treatment!> Here, with regard to the water dispersibility improved propolis extract (A) added with 2% by weight of sodium hydrogencarbonate and heat-treated at 60 ° C, the presence or absence of changes in its components before and after the water dispersibility improvement treatment Were examined by high performance liquid chromatography.
[0039] 分析は、装置として島津製作所製 HPLC Class Lc 10、カラムとして島津テクノ リサーチ社 ODS— II (4. 6mm φ、 150mm)、移動相として、メタノール、水酢及び酢 酸混合液 (それぞれ体積比で 70、 30及び 1)、検出器としてフォトダイオードアレイ検 出器をそれぞれ用い、流量を 1. 2mLZ分、カラム温度を 50°Cとし、測定波長 275η mで行った。 [0039] The analysis was performed using HPLC Class Lc 10 manufactured by Shimadzu Corporation as the instrument, Shimadzu Techno Research Co., Ltd. ODS-II (4.6 mm φ, 150 mm) as the column, and methanol, water vinegar and acetic acid mixed solution (volumes respectively) as the mobile phase. The ratio was 70, 30 and 1), and a photodiode array detector was used as the detector, the flow rate was 1.2 mLZ, the column temperature was 50 ° C, and the measurement wavelength was 275 ηm.
[0040] 水分散性改良処理前のプロポリス液のクロマトグラムを図 1に、水分散性改良プロボ リス抽出物 (A)のクロマトグラムを図 2にそれぞれ示す。  [0040] Fig. 1 shows the chromatogram of the propolis solution before the water dispersibility improvement treatment, and Fig. 2 shows the chromatogram of the water dispersibility improved provolis extract (A).
[0041] また、さらに、水分散性改良プロポリス抽出物 (A)について容器への付着程度の評 価を、水分散性改良処理を行なわな 、プロポリス液での評価と同時に行った。 [0041] Furthermore, the water dispersibility-improved propolis extract (A) was evaluated for the degree of adhesion to the container at the same time as the evaluation with the propolis liquid without the water dispersibility improvement treatment.
[0042] 図 1及び図 2において、保持時間が約 3分(2. 95-2. 97分)のところに現れたピー クがパラクマル酸である力 その他の成分にっ 、ても水分散性改良処理の処理前後 で変化が見られないこと、及び、水分散性改良処理によって、新たな成分が発生しな いことが判る。 [0042] In Fig. 1 and Fig. 2, the force that the peak appearing at the retention time of about 3 minutes (2. 95-2. 97 minutes) is paracoumaric acid, and other components, even water dispersibility It can be seen that there is no change before and after the improvement treatment and that no new components are generated by the water dispersibility improvement treatment.
[0043] なお、ケンフエロール及びケルセチンにっ 、ては、上記条件で、ただし、検出波長 を 380nmとして測定をした。その結果、保持時間が約 25分及び約 52分の箇所にピ ークを有するこれら物質の、処理前後でのピーク高さ及び面積に変化がなぐこれら 成分も本発明の水分散性改良処理の影響を受けないことが確認された。  [0043] Kenferrol and quercetin were measured under the above conditions, except that the detection wavelength was 380 nm. As a result, these components having peaks at retention times of about 25 minutes and about 52 minutes, and those components that do not change in peak height and area before and after the treatment, are also subjected to the water dispersibility improvement treatment of the present invention. It was confirmed that it was not affected.
[0044] <飲用容器への付着の検討 >  [0044] <Examination of adhesion to drinking containers>
予め質量を測定した透明なプラスチック製コップ 12個にそれぞれ水道水を lOOmL 入れ、これらのうち 6個に水分散性改良処理前のプロポリス液 (プロポリス成分含有量 32質量%: 0. 48)を、他の 6個に上記水分散性改良プロポリス抽出物 A (プロポリス 成分含有量 32% : 0. 48g (添加した炭酸水素ナトリウムは全量反応したとし、かつ、 添加した炭酸水素ナトリウム由来のナトリウム成分質量は微量であるとして無視した) をそれぞれ 1. 5g (約 60滴分であり、健康維持に充分であるとされている 1日量に相 当する)ずつ滴下した。 [0045] これら容器を軽く振って攪拌した後、内容液を捨て、その後自然乾燥によって容器 を乾燥させた後、各々の容器の質量変化を調べ、付着物質量を測定し、それぞれ平 均した。 LOOmL of tap water was put in 12 transparent plastic cups whose masses were measured in advance, and 6 of these were pre-polish solution (propolis component content 32% by mass: 0.48) before water dispersibility improvement treatment. In the other six, the above-described water dispersibility-improved propolis extract A (propolis component content 32%: 0.48 g (the added sodium hydrogen carbonate was reacted in its entirety, and the added sodium hydrogen carbonate-derived sodium component mass was 1.5 g (about 60 drops, equivalent to the daily dose that is considered sufficient for maintaining health) was added dropwise. [0045] After these containers were shaken lightly and stirred, the liquid contents were discarded, and then the containers were dried by natural drying. Then, the change in mass of each container was examined, and the amount of adhered substances was measured and averaged.
[0046] その結果、水分散性改良処理前のプロポリス液の場合には、付着残留物の平均質 量は 0. l lgであり、この量はプロポリス成分として 7%強に相当する。  As a result, in the case of the propolis liquid before the water dispersibility improving treatment, the average mass of the adhered residue is 0.1 l lg, and this amount corresponds to a little over 7% as the propolis component.
[0047] これに対して、本発明に係る水分散性改良プロポリス抽出物 Aの場合にはコップの 付着残留物質量の平均は 0. 002gと、付着残留物が事実上ない状態であることが確 認された。なお、このときのわずかな付着残留物は流水で手洗浄することにより、容 易に除去可能であることが確認された。  [0047] On the other hand, in the case of propolis extract A with improved water dispersibility according to the present invention, the average amount of adhering residue in the cup is 0.002 g, indicating that there is virtually no adhering residue. confirmed. It was confirmed that the slight adhesion residue at this time can be easily removed by hand washing with running water.
[0048] これら結果により、本発明に係る水分散性改良プロポリス抽出物は容器に付着する ことがないので、全量を確実に飲用できること判る。  [0048] From these results, it can be seen that the water dispersibility-improved propolis extract according to the present invention does not adhere to the container, so that the entire amount can be surely consumed.
[0049] また、水分散性改良プロポリス抽出物 Aは水のみならず、緑茶、紅茶などに滴下し てもその良好な水分散性が損なわれないことが確認された。また、水分散性が良好 であるため、例えば飲料や水に添加した後、減圧や加熱などにより残留アルコール 分を減少させても成分が沈下することはないことも確認され、これらより、アルコール 分が問題となるような非アルコール飲料等の分野にも本発明の水分散性改良プロボ リス抽出物が応用可能であることが判った。  [0049] In addition, it was confirmed that the water dispersibility-improved propolis extract A does not impair its good water dispersibility even when dripped not only in water but also in green tea, black tea, and the like. In addition, because of its good water dispersibility, it was also confirmed that the components do not sink even if the residual alcohol content is reduced by, for example, decompression or heating after addition to beverages or water. It has been found that the water dispersibility-improved provolis extract of the present invention can also be applied to the field of non-alcoholic beverages and the like in which the above problems are problematic.
産業上の利用可能性  Industrial applicability
[0050] 本発明に係るプロポリス液の水分散性改良方法によれば、数多くの優れた特性を 有するプロポリスが持つ欠点である、容器、口腔内やのどへの付着、風味改善への 困難性を、乳蛋白質等を用いることなく著しく改善することができる。このため、本発 明に係る水分散性改良プロポリス抽出物は従来のプロポリス抽出物が用いられてい た分野は勿論、応用が困難であったような食品、飲料分野への応用が容易になる。 [0050] According to the method for improving the water dispersibility of a propolis liquid according to the present invention, the disadvantages of a propolis having a number of excellent properties are the disadvantages of adhesion to containers, oral cavity and throat, and difficulty in improving flavor. It can be remarkably improved without using milk protein or the like. For this reason, the water dispersibility-improved propolis extract according to the present invention can be easily applied to the food and beverage fields, which have been difficult to apply, as well as the fields where the conventional propolis extract is used.

Claims

請求の範囲 The scope of the claims
[1] アルコール抽出によるプロポリス抽出物であって、炭酸ナトリウム、あるいは Z及び、 炭酸水素ナトリウム存在下で加熱処理されたことを特徴とする水分散性改良プロポリ ス抽出物。  [1] A propolis extract obtained by alcohol extraction, which is heat-dispersed in the presence of sodium carbonate or Z and sodium bicarbonate, and is improved in water dispersibility.
[2] 上記加熱処理力 0°C以上 70°C以下で行なわれたことを特徴とする請求項 1に記 載の水分散性改良プロポリス抽出物。  [2] The water dispersibility-improved propolis extract according to claim 1, wherein the heat treatment power is 0 ° C or higher and 70 ° C or lower.
[3] 請求項 1または請求項 2に記載の水分散性改良プロポリス抽出物を含有することを 特徴とする含プロポリス飲料。 [3] A propolis-containing beverage comprising the water-dispersibility-improved propolis extract according to claim 1 or 2.
[4] アルコール抽出によるプロポリス抽出物であって、炭酸ナトリウム、あるいは Z及び、 炭酸水素ナトリウム存在下で加熱処理することを特徴とするプロポリス抽出物の水分 散性改良方法。 [4] A method for improving water dispersibility of a propolis extract, which is a propolis extract obtained by alcohol extraction, wherein the extract is heated in the presence of sodium carbonate or Z and sodium bicarbonate.
[5] 上記加熱処理力 0°C以上 70°C未満で行うことを特徴とする請求項 2に記載のプロ ポリス抽出物の水分散性改良方法。  [5] The method for improving water dispersibility of a propolis extract according to claim 2, wherein the heat treatment is performed at a temperature of 0 ° C or higher and lower than 70 ° C.
PCT/JP2004/018163 2004-12-06 2004-12-06 Propolis extract with improved water dispersibility, propolis-containing beverage, and method of improving water dispersibility of propolis extract WO2006061877A1 (en)

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GR20170100541A (en) * 2017-11-30 2019-06-20 Γεωργιος Χαραλαμπου Βλαχοπουλος Propolis dilution in grape marc distilate

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CN105560295A (en) * 2015-04-08 2016-05-11 王晓丽 Propolis composition capable of restraining fungi
CN107198188A (en) * 2017-06-13 2017-09-26 重庆市畜牧科学院 The preparation method of water-soluble bee glue
CN114306390A (en) * 2022-01-23 2022-04-12 吉林蜂道馆健康产业有限公司 Preparation method of bee therapy product for reducing blood sugar

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JP2014198687A (en) * 2013-03-29 2014-10-23 ユーハ味覚糖株式会社 Propolis- and quercetin-containing composition with enhanced anti-inflammatory activity
GR20170100541A (en) * 2017-11-30 2019-06-20 Γεωργιος Χαραλαμπου Βλαχοπουλος Propolis dilution in grape marc distilate
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