JP4637198B2 - Propolis composition and method for producing the same - Google Patents

Description

  INDUSTRIAL APPLICABILITY The present invention can stably dissolve, as an aqueous solution, a soluble component obtained using a propolis composition and a method for producing the same, in particular, a propolis bulk material or the like as a raw material for extraction and a solvent whose main component is a hydrophilic organic solvent. The present invention relates to a propolis composition and a method for producing the same.

  Propolis is a glue-like or wax-like substance made by mixing saliva with plant exudates, shoots, and resins collected by bees for the purpose of defense and reinforcement of the nest. This propolis contains various components because bees are produced by collecting various plants around the nest box as raw materials.

  Since it is difficult to ingest the propolis bulk as it is, useful components contained in the propolis bulk have been conventionally extracted by the method disclosed in Patent Document 1, for example. Specifically, an extraction method using water or a hydrophilic organic solvent or a supercritical extraction method is used.

Among these, a soluble component obtained using a solvent whose main component is a hydrophilic organic solvent as an extraction solvent is difficult to dissolve in water, and therefore cannot be easily applied to beverages provided in the form of an aqueous solution, for example. There was a problem. Therefore, conventionally, a method for solubilizing a propolis extract disclosed in Patent Document 2 in water is known. Patent Document 2 discloses a method for solubilizing in water in which a basic amino acid is added to a propolis extract.
JP 2003-61593 A JP 2006-25790 A

  However, the method for solubilizing the propolis extract in water disclosed in Patent Document 2 has a problem that the solubility and the stability of the solution are lowered depending on the pH of the aqueous solution. Such a decrease in solubility may cause a decrease in absorption rate due to ingestion of the active ingredient in the propolis extract.

  In the propolis extract obtained by using a solvent whose main component is a hydrophilic organic solvent as an extraction solvent from a propolis bulk or the like, the present invention provides solubility in water by blending an amino acid and an alkaline agent. It is based on the discovery that it can be improved.

  The object of the present invention is to provide a propolis composition capable of improving the solubility in water in a propolis extract obtained using a solvent whose main component is a hydrophilic organic solvent from a propolis bulk or the like, and It is in providing the manufacturing method.

In order to achieve the above object, the propolis composition of the invention according to claim 1 is a raw material for extracting a propolis bulk, a supercritical extraction residue from the propolis bulk, or an extraction residue of a solvent whose main component is water. As a main component, it contains at least one selected from an extraction component of a solvent whose main component is a hydrophilic organic solvent, an alkaline agent, and an amino acid and an amino acid derivative, and the amino acid or amino acid derivative includes glycine, serine, alanine, valine, leucine, isoleucine, methionine, phenylalanine, proline, threonine, asparagine, is at least one glutamine, arginine, lysine, histidine, selected data Gaulin, and Betai down or al, the alkali agent include sodium hydroxide, potassium hydroxide , Sodium bicarbonate, potassium bicarbonate, sodium carbonate Potassium carbonate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, trisodium phosphate, tripotassium phosphate, tetrasodium pyrophosphate, tetrapotassium pyrophosphate, pyrolin It is at least one selected from sodium dihydrogen acid and potassium dihydrogen pyrophosphate.

The invention according to claim 2 is characterized in that the propolis composition according to claim 1 further contains water and is prepared as an aqueous solution.
The invention described in claim 3 is the propolis composition according to claim 1 or claim 2, wherein the aqueous solution is characterized that you have been prepared as an acidic solution.

The invention according to claim 4 is the propolis composition according to any one of claims 1 to 3 , wherein the alkaline agent is contained in an amount of 1 to 20% by mass relative to the solid matter of the propolis composition. It is characterized by that.

The method for producing a propolis composition of the invention according to claim 5 is characterized in that the main component is a propolis raw mass, or a supercritical extraction residue from the propolis raw mass or an extraction residue of a solvent whose main component is water. In the method for producing a propolis composition in which at least one selected from an extraction component of a solvent that is a hydrophilic organic solvent, an alkaline agent, and an amino acid and an amino acid derivative is dissolved in water, the amino acid or amino acid derivative includes glycine, serine, alanine, valine, leucine, is at least one isoleucine, methionine, phenylalanine, proline, threonine, asparagine, glutamine, arginine, lysine, histidine, selected data Gaulin, and Betai down or al, the alkali agent is sodium hydroxide , Potassium hydroxide, sodium bicarbonate, charcoal Potassium hydrogen carbonate, sodium carbonate, potassium carbonate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, trisodium phosphate, tripotassium phosphate, tetrasodium pyrophosphate, pyrophosphoric acid It is at least one selected from tetrapotassium, sodium dihydrogen pyrophosphate, and potassium dihydrogen pyrophosphate.

  ADVANTAGE OF THE INVENTION According to this invention, the solubility to water can be improved in the propolis extract obtained by using the solvent whose main component is a hydrophilic organic solvent from the propolis bulk.

Hereinafter, the embodiment which actualized the propolis composition of the present invention is described.
The propolis composition of this embodiment uses propolis as an extraction raw material, a soluble component (propolis extract) obtained using a solvent whose main component is a hydrophilic organic solvent as an extraction solvent, an alkaline agent, and amino acids, amino acid derivatives, And at least one selected from protein hydrolysates. The propolis composition of the present embodiment may be configured in a solid form such as a powder containing each component, may further contain water, and may be prepared as an aqueous solution.

The propolis that is an extraction raw material is a propolis bulk, or a supercritical extraction residue from the propolis bulk or a solvent extraction residue (hereinafter, referred to as “propolis bulk”). Propolis is a gelatinous or waxy substance made by mixing saliva with plant exudates, shoots and resins collected by bees such as honeybees for the purpose of defense and reinforcement of the nest. The production area of propolis used in this embodiment is not particularly limited, but includes South American countries such as Japan, China, Brazil, Argentina and Uruguay, Europe such as Hungary and Bulgaria, North America such as Canada, Oceania such as Australia and New Zealand, etc. Can be used.

  The propolis bulk can be used as an extraction raw material for a solvent in which the main component is a hydrophilic organic solvent as it is. Insoluble residue (supercritical extraction residue) after supercritical extraction of the propolis bulk can also be used as an extraction raw material. Further, an insoluble fraction (solvent extraction residue) in a solvent whose main component of the propolis bulk is water can be used as an extraction raw material. Here, the main component means that the existing ratio (volume%) in the solvent is the highest. The content of water in the solvent is preferably 50% by volume or more. The solvent whose main component is water may contain, for example, a hydrophilic organic solvent described later as another component.

  When obtaining an insoluble fraction in a solvent in which the main component of the propolis bulk is water, the temperature of the solvent is not particularly limited. In addition, what is necessary is just to perform extraction operation for about several hours, stirring at predetermined temperature. And after extracting a solvent melt | dissolution component, the insoluble fraction with respect to the solvent whose main component is water can be obtained from a propolis original lump by applying well-known solid-liquid separation methods, such as filtration and centrifugation.

  The supercritical extraction method can be carried out by using a known supercritical fluid extraction apparatus. A predetermined component is extracted from the extraction raw material by bringing the supercritical fluid into a supercritical state under the conditions of the critical temperature or higher and the critical pressure or higher and the extraction raw material. When carbon dioxide is used as a supercritical fluid, dissolved components are extracted from the extraction raw material by carbon dioxide that has become a supercritical fluid state at a critical temperature of 31.1 ° C. or higher and a critical pressure of 72.8 atm (7.4 MPa) or higher. Extracted and insoluble components remain as a residue. As the supercritical fluid, ethane, propane, carbon dioxide, nitrous oxide and the like can be used in addition to carbon dioxide, but it is most preferable to use carbon dioxide.

  In this embodiment, the main component used for the extraction treatment of propolis bulk is a hydrophilic organic solvent, such as ethanol, methanol, isopropanol and other lower alcohols having the property of dissolving in water, acetone, methyl ethyl ketone, etc. These ketones can be appropriately selected and used. These hydrophilic organic solvents can be used alone or in combination of two or more. Among these, ethanol or a mixture of ethanol and water is most preferable in view of finally ingestion. When methanol other than ethanol is used as the solvent, it is preferable to completely remove the solvent in the post-treatment step. Here, the main component means that the existing ratio (volume%) in the solvent is the highest. It means that the content of the organic solvent in the solvent is preferably 50% by volume or more. The solvent whose main component is an organic solvent contains, for example, water as another component, and may be applied as a hydrous hydrophilic organic solvent.

  When hydrous ethanol is used as the hydrous hydrophilic organic solvent, for example, the ethanol concentration in the extraction solvent is preferably 50 to 99% by volume, more preferably 60 to 90% by volume, and most preferably 65 to 80% by volume. In the case of using an organic solvent other than ethanol in the hydrous hydrophilic organic solvent, this range can be applied to the concentration of the organic solvent. The addition amount of these extraction solvents is preferably 1 to 10 parts by mass, more preferably 2 to 8 parts by mass with respect to 1 part by mass of the propolis bulk in terms of extraction efficiency. These extraction solvents are mixed and stirred together with the propolis bulk.

  When a mixture with ethanol or water is used as the solvent, the extraction temperature is preferably 5 to 40 ° C. When the extraction temperature is less than 5 ° C., the separation efficiency of the dissolved component and the insoluble component is lowered, which is not preferable. Conversely, when the extraction temperature exceeds 40 ° C., the extraction solvent (ethanol) evaporates, leading to a reduction in extraction efficiency. The extraction time is not particularly limited, but is preferably about 4 to 48 hours, for example. The obtained extract is composed of a solvent-soluble fraction and an insoluble fraction consisting of a precipitate. These soluble and insoluble fractions can be easily separated by using known methods such as filtration and centrifugation.

  The solvent extractable component (propolis extract), which is the obtained soluble component, may be mixed with other components (amino acid, alkali agent) in the extracted state (liquid), and powdered by performing a known drying treatment Etc., it may be mixed with other components. The propolis extract may be further subjected to separation / purification treatment using known chromatography, such as gas chromatography, liquid chromatography, supercritical fluid chromatography, and thin layer chromatography.

  The amino acid, amino acid derivative and protein hydrolyzate contained in the propolis composition are blended to improve the solubility in water without reducing the active ingredient of the propolis extract. Examples of amino acids or amino acid derivatives include glycine, serine, alanine, valine, leucine, isoleucine, methionine, phenylalanine, tyrosine, tryptophan, proline, threonine, cysteine, asparagine, glutamine, aspartic acid, glutamic acid, arginine, lysine, histidine, ornithine , Theanine, citrulline, γ-aminobutyric acid (GABA), taurine, betaine, carnitine, creatine, pantothenic acid, and carnosine. These amino acids or derivatives thereof can be used alone or in combination of two or more. Among these, alanine, valine, leucine, isoleucine, methionine, phenylalanine, tyrosine, tryptophan, proline, threonine, cysteine, asparagine, glutamine, aspartic acid, glutamic acid, taurine, betaine, carnitine, creatine, pantothenic acid, and carnosine preferable. Alanine, valine, leucine, isoleucine, methionine, phenylalanine, proline, threonine, asparagine, glutamine, taurine and betaine are more preferred. The protein hydrolyzate is not particularly limited as long as it is a soluble protein hydrolyzate containing the amino acid or amino acid derivative, and any size such as oligopeptide and polypeptide can be used. . As a method for hydrolyzing proteins, known methods can be appropriately employed. Examples thereof include hydrolysis treatment using various proteases, acid / alkali treatment, and heat treatment.

  The content of amino acids, amino acid derivatives and protein hydrolysates contained in the propolis composition is appropriately set depending on the components extracted from the propolis bulk and the like and the types of amino acids. From the viewpoint of the solubility and stability of the extract, in the case of an amino acid or an amino acid derivative, it is preferably 0.1 to 30% by mass, more preferably 1 to 20% by mass in the solid matter of the propolis composition.

  An alkaline agent is mix | blended in order to improve the solubility with respect to water about a propolis extract. Examples of the alkali agent include ammonia, organic amines, inorganic alkalis, and organic alkalis. Examples of the inorganic alkali include sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, and potassium carbonate. Examples of the organic alkali include sodium dihydrogen phosphate, potassium dihydrogen phosphate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, trisodium phosphate, tripotassium phosphate, tetrasodium pyrophosphate, and tetrapotassium pyrophosphate. , Sodium dihydrogen pyrophosphate, potassium dihydrogen pyrophosphate, sodium polyphosphate, sodium metaphosphate, and potassium metaphosphate. These alkaline agents can be used alone or in combination of two or more. Among these, phosphates as inorganic alkalis and organic alkalis are preferably used.

  The content of the alkaline agent contained in the propolis composition is appropriately set depending on the components extracted from the propolis bulk and the like, the type of the alkaline agent, etc. It is 20 mass%, More preferably, it is 5-10 mass%. Moreover, the blending ratio of at least one selected from amino acids, amino acid derivatives and protein hydrolysates contained in the propolis composition and the alkali agent is not particularly limited, and is appropriately set according to the components. For example, the mass ratio is preferably defined in the range of 0.1 to 20, more preferably 0.3 to 10, with respect to the alkali agent 1.

  The propolis composition further contains water and may be prepared as an aqueous solution. Furthermore, an emulsifier or the like may be included. The blending amount of water is appropriately set according to the purpose and the solubility of the blending components. The method for preparing the aqueous solution is not particularly limited, and each component may be prepared as an aqueous solution and then mixed to prepare a propolis composition as an aqueous solution. After mixing the solid components, A propolis composition as an aqueous solution may be prepared by adding water. When each solid component is added to water, the order of adding each component is not particularly limited. The pH of the aqueous solution is not particularly limited, and can be applied to any of an acidic solution, a neutral solution, and an alkaline solution. The propolis composition of the present embodiment improves the solubility in water without reducing the active ingredient of the propolis extract even if it is an acidic solution containing, for example, carbonated water or an organic acid such as citric acid. Can do. Therefore, it is preferably applied as an aqueous solution in an acidic region (for example, pH 1 to 6, preferably pH 2.5 to 4.5, more preferably pH 3 to 4).

  The field of application of the propolis composition of the present embodiment is not particularly limited. For example, for food and drink such as health food, pharmaceuticals (including quasi-drugs), and cosmetics that are finally used in the form of an aqueous solution. Applied. For example, when used in health foods, various additives such as gelling agents, thickeners, sweeteners, emulsifiers, flavoring agents, pigments, pH adjusters, etc., within a range that does not impair the physiological activity of the components. May be blended. As an application form, it is preferably used as a liquid product such as a drink or tincture as it is. The propolis composition prepared as an aqueous solution may be powdered by hot air drying, freeze drying, and spray drying. When powdered, excipients such as starch and dextrin may be added as additives. The powdered propolis composition can be applied to various uses by being redissolved in water.

According to the propolis composition of the present embodiment, the following effects can be obtained.
(1) In the propolis composition of the present embodiment, a propolis bulk or the like as an extraction raw material, a soluble component (solvent extraction component) in a solvent whose main component is a hydrophilic organic solvent, an alkaline agent, and amino acids, amino acid derivatives, and proteins Contains at least one selected from hydrolysates. Therefore, the solubility in water of the propolis extract obtained by using a propolis bulk as an extraction raw material and using a solvent whose main component is a hydrophilic organic solvent is improved.

  (2) The propolis composition of this embodiment can improve the solubility of the propolis extract in water. Therefore, it can be preferably applied to various fields such as foods and drinks, cosmetics and pharmaceuticals finally used in the form of an aqueous solution, and long-term storage stability can be improved in the form of an aqueous solution.

  (3) The propolis composition of this embodiment preferably contains water and is prepared as an aqueous solution. The propolis composition of this embodiment can improve the solubility with respect to water, without reducing the content of the active ingredient of a propolis extract. In particular, it can be stably dissolved in an aqueous solution even under acidic conditions where the solubility of the propolis extract is likely to decrease.

  (4) The propolis composition of the present embodiment is preferably a glycine, serine, alanine, valine, leucine, isoleucine, methionine, phenylalanine, tyrosine, tryptophan, proline, threonine, cysteine, asparagine, glutamine as an amino acid or amino acid derivative. , Aspartic acid, glutamic acid, arginine, lysine, histidine, ornithine, theanine, citrulline, γ-aminobutyric acid, taurine, betaine, carnitine, creatine, pantothenic acid, and carnosine are applied. Therefore, the solubility in water can be further improved without reducing the active ingredients of the propolis extract.

  (5) The propolis composition of the present embodiment is preferably an alkali agent, preferably sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, sodium dihydrogen phosphate, dihydrogen phosphate At least selected from potassium, disodium hydrogen phosphate, dipotassium hydrogen phosphate, trisodium phosphate, tripotassium phosphate, tetrasodium pyrophosphate, tetrapotassium pyrophosphate, sodium dihydrogen pyrophosphate, and potassium dihydrogen pyrophosphate A kind is used. Therefore, the solubility in water can be further improved without reducing the active ingredients of the propolis extract.

In addition, you may change the said embodiment as follows.
-The propolis composition in the above embodiment may be applied not only to foods and drinks, cosmetics and pharmaceuticals applied to humans, but also to foods and drinks such as supplements and nutritional supplements for domestic animals such as livestock, cosmetics, and pharmaceuticals. Good.

  -When performing an extraction process from a propolis bulk, it is preferable to remove and pulverize foreign substances such as dust mixed during propolis collection.

Examples and Comparative Examples are given below to describe the above embodiments more specifically, but the present invention is not limited to these.
<Test Example 1: Production and evaluation of propolis composition>
Example 1
To 400 g of the propolis bulk, 1000 mL of a 70% by volume ethanol solution was added, followed by stirring and extraction at room temperature overnight to obtain a propolis extract (about 700 mL) having a solid content of 20.5%. 16 mL of a mixture of 3.0 M glycine (300 mL) and 3.0 M sodium hydroxide (273 mL) was added to 60.0 mL of the propolis extract (glycine content: 1.884 g, sodium hydroxide content: 0.915 g). After stirring for hours, the mixture was concentrated under reduced pressure. This was lyophilized to obtain 14.0 g of a powder propolis composition of Example 1 (solid content derived from propolis: 80.1%, glycine: 13.5% by mass, sodium hydroxide: 6.5% by mass).

(Comparative Example 1)
To 60.0 mL of the propolis extract described in Example 1, 5 g of L-arginine was added and stirred for 2 hours, followed by concentration under reduced pressure. This was freeze-dried to obtain 16.1 g of powder propolis composition of Comparative Example 1 (solid content 68.8% derived from propolis).

(Comparative Example 2)
16 mL of water in which 0.915 g of sodium hydroxide was dissolved in 60.0 mL was added to the propolis extract described in Example 1, and the mixture was stirred for 2 hours and concentrated under reduced pressure. This was lyophilized to obtain 12.6 g of a powder propolis composition of Comparative Example 2 (92.7% solid content derived from propolis).

(Verification of solubility)
2 g of the powder propolis composition of each example was sampled and 8 mL of water was added and dissolved. Thereafter, the precipitate obtained by centrifugation was dried, and the solubility was calculated by measuring the remaining dissolution. The results are shown in Table 1.

(Confirmation of stability under acidic conditions (acid resistance))
In each case, 100 μL of the supernatant after confirmation of solubility was collected and dissolved in 9.9 mL of water. Then, considering using it for acidic soft drink use, the solution was adjusted to around pH 3.5 using citric acid. And the precipitation amount after standing at room temperature for 10 days was evaluated. For the measurement of the amount of precipitation, each liquid was put into a 10 mL measuring pipette, and the amount of the precipitate was measured as the height from the bottom of the measuring pipette. The height of the precipitate is 0 mm (no precipitate): very good A, more than 0 mm and less than 2 mm: good B, 2 mm or more and less than 5 mm: normal C, 5 mm or more and less than 10 mm: bad D, 10 mm or more: very It was evaluated as a bad E.

(Measurement of active ingredients)
About the powder propolis composition of each example, it measured by the analysis method of the propolis food specification standard of Japan Health and Nutrition Food Association. HPLC analysis conditions: column (Shim-pack CLC-ODS 6.0 mm ID × 150 mm), mobile phase (70% methanol containing 1% acetic acid), conditions (50 ° C., 30 minutes measurement). In addition to p-coumaric acid, which is a representative active ingredient of propolis, as the measurement component, as a cinnamic acid derivative, durpanine, artepilin C, and baccaline were measured, and the total amount thereof was measured. The results are shown in Table 1. The total content of active ingredients is 2.1 g or more A, 2.0 g or more and less than 2.1 g B, 1.9 g or more and less than 2.0 g C, 1.8 g or more and less than 1.9 g D , Less than 1.8 g was evaluated as E.

溶解度は、各例において大きな差は認められなかった。実施例１のプロポリス組成物の水に対する溶解性は特に良好であることが確認された。

There was no significant difference in solubility in each case. It was confirmed that the solubility of the propolis composition of Example 1 in water was particularly good.

  In the acid resistance evaluation, the evaluation of the powder of Comparative Example 1 was E, and it did not have stability under an acidic solution. The evaluation of the powder of Comparative Example 2 was B. Although the powders of Example 1 and Comparative Example 2 were clouded, the suspended state could be maintained for a long time. On the other hand, the powder of Comparative Example 1 was not able to maintain a suspended state at pH 3.5, and immediately aggregated to form a precipitate. Therefore, it is thought that the use to a drink formulation is unsuitable.

  Regarding the content of the active ingredient, Example 1 had the highest content of the active ingredient. In Comparative Example 2, the content of the active ingredient was lower than that in Example 1. This is considered that the active ingredient decomposed | disassembled with the mix | blended alkaline agent. From the above, it can be considered that the powder of Example 1 can be preferably applied to uses for acidic drink preparations and the like from the viewpoint of solubility, acid resistance, and evaluation of the content of active ingredients.

<Test Example 2: Examination of blending amounts of amino acid (glycine) and alkali agent (sodium hydroxide)>
(Example 2)
16 mL of a mixture of 1.5 M glycine 300 mL and 3.0 M sodium hydroxide 273 mL was added to 60.0 mL of the propolis extract described in Example 1 (glycine content: 0.942 g, sodium hydroxide content: 0.915 g) After stirring for 2 hours, the mixture was concentrated under reduced pressure. This was lyophilized to obtain 13.0 g of powdery propolis composition of Example 2 (7.2% by mass of glycine, 7.0% by mass of sodium hydroxide). About the obtained propolis composition, the solubility, acid resistance, and content of active ingredients were measured in the same manner as in Example 1.

(Example 3)
To the propolis extract described in Example 1, 16 mL of a mixture of 6.0 M glycine 300 mL and 3.0 M sodium hydroxide 273 mL was added to 60.0 mL (glycine content: 3.768 g, sodium hydroxide content: 0.915 g) After stirring for 2 hours, the mixture was concentrated under reduced pressure. This was freeze-dried to obtain 14.0 g of a powdered propolis composition of Example 3 (glycine 26.9% by mass, sodium hydroxide 6.5% by mass). About the obtained propolis composition, the solubility, acid resistance, and content of active ingredients were measured in the same manner as in Example 1.

Example 4
To the propolis extract described in Example 1, 160.0 mL of a solution obtained by mixing 300 mL of 3.0 M glycine and 273 mL of 6.0 M sodium hydroxide was added to 60.0 mL (glycine content: 1.84 g, sodium hydroxide content) : 1.830 g) After stirring for 2 hours, the mixture was concentrated under reduced pressure. This was freeze-dried to obtain 14.9 g (glycine 12.6% by mass, sodium hydroxide 12.3% by mass) of the powdery propolis composition of Example 4. About the obtained propolis composition, the solubility, acid resistance, and content of active ingredients were measured in the same manner as in Example 1. The results are shown in Table 2.

グリシン濃度が７．２質量％のプロポリス組成物の溶解度、耐酸性及び有効成分の含有量の評価は、比較的良好であることが確認された。一方、グリシン濃度が２６．９質量％のプロポリス組成物の溶解度は、実施例１の粉末よりやや低下した。以上により、グリシンの添加量は減らしても溶解度に影響はないが、グリシンの添加量を増やすと溶解度が低くなる傾向があることが確認された。

It was confirmed that the evaluation of the solubility, acid resistance and content of the active ingredient of the propolis composition having a glycine concentration of 7.2% by mass was relatively good. On the other hand, the solubility of the propolis composition having a glycine concentration of 26.9% by mass was slightly lower than that of the powder of Example 1. From the above, it was confirmed that the solubility does not affect even if the amount of glycine added is decreased, but the solubility tends to decrease when the amount of glycine added is increased.

  It was confirmed that the solubility of the propolis composition having a sodium hydroxide concentration of 12.3% by mass was substantially the same as in Example 1. It was also confirmed that the acid resistance and the evaluation of the content of the active ingredient were relatively good.

<Test Example 3: Examination of type of alkali agent>
(Example 5)
To the propolis extract described in Example 1, 16 mL of a solution obtained by mixing 100 mL of 3.0 M glycine and 90 mL of 3.0 M potassium hydroxide was added to 60.0 mL (glycine content: 1.894 g, potassium hydroxide content: 1.276 g) After stirring for 2 hours, the mixture was concentrated under reduced pressure. This was lyophilized to obtain 13.1 g (propolis solid content: 75.8%) of the powdery propolis composition of Example 5. About the obtained propolis composition (glycine 14.5 mass%, sodium hydroxide 9.7 mass%), the solubility, acid resistance, and content of the active ingredient were measured in the same manner as in Example 1. The results are shown in Table 3.

以上により、水酸化ナトリウム以外のアルカリ剤を用いても、問題なく水溶性のプロポリスエキスや粉末を得ることができた。また、このことより水酸化ナトリウム及び水酸化カリウム以外に炭酸水素ナトリウム、炭酸水素カリウム、炭酸ナトリウム、炭酸カリウム、リン酸二水素ナトリウム、リン酸二水素カリウム、リン酸水素二ナトリウム、リン酸水素二カリウム、リン酸三ナトリウム、リン酸三カリウム、ピロリン酸四ナトリウム、ピロリン酸四カリウム、ピロリン酸二水素ナトリウム、及びピロリン酸二水素カリウム等に置き換えても同様の効果が得られると思料される。

As described above, a water-soluble propolis extract or powder could be obtained without problems even when an alkaline agent other than sodium hydroxide was used. In addition to this, in addition to sodium hydroxide and potassium hydroxide, sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, disodium hydrogen phosphate, dihydrogen phosphate It is thought that the same effect can be obtained by replacing with potassium, trisodium phosphate, tripotassium phosphate, tetrasodium pyrophosphate, tetrapotassium pyrophosphate, sodium dihydrogen pyrophosphate, potassium dihydrogen pyrophosphate, and the like.

<Test Example 4: Examination of types such as amino acids>
To 60.0 mL of the propolis extract described in Example 1, a predetermined amount of each amino acid, amino acid derivative and organic acid shown in Table 4 below and each liquid amount containing 0.992 g of sodium hydroxide were added. After stirring for 2 hours, the mixture was concentrated under reduced pressure. This was freeze-dried to obtain a powdery propolis composition containing various amino acids and the like. About the obtained propolis composition, solubility, acid resistance, and active ingredients were measured in the same manner as in Example 1. The solubility was evaluated as A: 99% or more, B: 95% or more and less than 99%, C: 90% or more and less than 95%, D: 50% or more and less than 90%, and E: less than 50%. did. The results are shown in Table 4.

表４に示したように、グリシン以外のアミノ酸又はアミノ酸誘導体を用いた場合でも、溶解性及び耐酸性で良好な結果を得ることができた。尚、溶解性の低い疎水性アミノ酸を用いた場合、液量の増加を招くため、溶解性の高いアミノ酸等を使用することが好ましい。一方、有機酸を使用した各例は、溶解性を向上させることができなかった。また、アミノ酸を２種類以上組み合わせて用いても、プロポリス組成物の溶解性を向上できることが確認された。

As shown in Table 4, even when amino acids or amino acid derivatives other than glycine were used, good results were obtained with solubility and acid resistance. In addition, when a hydrophobic amino acid with low solubility is used, an increase in the amount of liquid is caused. Therefore, it is preferable to use an amino acid with high solubility. On the other hand, each example using an organic acid could not improve the solubility. It was also confirmed that the solubility of the propolis composition can be improved even when two or more amino acids are used in combination.

<Test Example 5: Examination with materials containing amino acids>
To 60.0 mL of the propolis extract described in Example 1, 130 mL of a solution obtained by mixing 100 mL of a protease treatment product of a protein derived from 20% by weight royal jelly and 30 mL of 0.8 M sodium hydroxide was added (sodium hydroxide content: 0). 960 g) After stirring for 2 hours, the mixture was concentrated under reduced pressure. This was freeze-dried to obtain 31.9 g of a powdered propolis composition. About the obtained propolis composition, solubility, acid resistance, and content of active ingredients were measured in the same manner as in Example 1 (data not shown). As a result, it was confirmed that the same evaluation results as in Example 1 were obtained. Moreover, it was confirmed that the solubility of the propolis composition can be improved even if it is replaced with a material containing a protein hydrolyzate as a containing material such as amino acid.

Claims (5)

A propolis bulk, or a supercritical extraction residue from the propolis bulk or an extraction residue of a solvent whose main component is water as an extraction raw material, an extraction component of a solvent whose main component is a hydrophilic organic solvent, an alkaline agent, and an amino acid And at least one selected from amino acid derivatives,
Wherein the amino acid or amino acid derivative, glycine, serine, alanine, selected valine, leucine, isoleucine, methionine, phenylalanine, proline, threonine, asparagine, glutamine, arginine, lysine, histidine, data Gaulin, and Betai down or al At least one kind,
The alkaline agent is sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, disodium hydrogen phosphate, dipotassium hydrogen phosphate A propolis composition comprising at least one selected from trisodium phosphate, tripotassium phosphate, tetrasodium pyrophosphate, tetrapotassium pyrophosphate, sodium dihydrogen pyrophosphate, and potassium dihydrogen pyrophosphate.   The propolis composition according to claim 1, further comprising water and prepared as an aqueous solution.   The propolis composition according to claim 2, wherein the aqueous solution is prepared as an acidic solution.   The propolis composition according to any one of claims 1 to 3, wherein the alkali agent is contained in an amount of 1 to 20 mass% with respect to the solid matter of the propolis composition. A propolis bulk, or a supercritical extraction residue from the propolis bulk or an extraction residue of a solvent whose main component is water as an extraction raw material, an extraction component of a solvent whose main component is a hydrophilic organic solvent, an alkaline agent, and an amino acid And a method for producing a propolis composition in which at least one selected from amino acid derivatives is dissolved in water,
Wherein the amino acid or amino acid derivative, glycine, serine, alanine, selected valine, leucine, isoleucine, methionine, phenylalanine, proline, threonine, asparagine, glutamine, arginine, lysine, histidine, data Gaulin, and Betai down or al At least one kind,
The alkaline agent is sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, disodium hydrogen phosphate, dipotassium hydrogen phosphate A propolis composition comprising at least one selected from trisodium phosphate, tripotassium phosphate, tetrasodium pyrophosphate, tetrapotassium pyrophosphate, sodium dihydrogen pyrophosphate, and potassium dihydrogen pyrophosphate Method.