JP4589858B2 - Method for producing polyphenol-containing material and food and drink - Google Patents

Description

  The present invention relates to a method for producing a polyphenol-containing material that is used by being added to foods and beverages, pharmaceuticals, and the like, and food and beverages containing the material. More specifically, the present invention relates to a method for producing a polyphenol-containing material containing a citrus-derived polyphenol and a food or drink containing the polyphenol-containing material.

  Citrus juice, pericarp, pericarp-containing materials and / or pomace contain antioxidant substances such as eriocitrin, 6,8-di-C-glucosyl diosmin, 6-C-glucosyl diosmin. These antioxidant substances are produced by extracting with water, an organic solvent or a mixture thereof, and performing the obtained extract in combination with a purification treatment such as reverse phase resin treatment or liquid chromatography (for example, patents). References 1 and 2).

On the other hand, Patent Document 3 discloses a method for producing a high-concentration eriocitrin-containing food material containing eriocitrin at a high concentration. In this method, at least one of citrus fruit juice, pericarp, and juice squeezed juice is extracted with a polar solvent, and the extract is applied to a synthetic adsorption resin to adsorb eriocitrin and then synthesized with water or warm water. The adsorbent resin is washed and the food material is separated and recovered using an organic solvent.
JP 9-48969 A Japanese Patent Laid-Open No. 10-245552 JP 2000-217560 A

  However, in the polyphenol-containing material produced by the production methods described in Patent Documents 1 and 2, when the ingestion is taken orally, unpleasant bitterness and miscellaneous taste are felt, and those bitterness and miscellaneous taste are unpleasant aftertaste. Had a problem of remaining for a long time. Furthermore, these polyphenol-containing materials also have a problem of making them feel a unique odor like traditional Chinese medicine because heat is applied during each process when extracting, concentrating and purifying. In addition, with these polyphenol-containing materials, it was difficult to maintain a high quality for a long period of time because odors and browning were likely to occur over time. Moreover, in patent document 3, in order to reduce bitterness, although the resin which adsorb | sucked the polyphenol containing material is wash | cleaned with warm water, when a polyphenol containing material is added to a foodstuff at high concentration, bitterness and miscellaneous taste are still felt. There is a current situation.

  The present invention has been made paying attention to such problems existing in the prior art. The object is to provide a method for producing a polyphenol-containing material that can easily reduce the content of components that degrade the quality while containing a high concentration of citrus-derived polyphenols. Another object is to provide food and drink with high quality while containing citrus-derived polyphenols.

In order to achieve the above object, the invention described in claim 1 is a method for producing a material containing at least one polyphenol selected from citrus-derived eriocitrin, hesperidin, and naringin , the method comprising: , An extraction step of immersing the citrus fruit or its constituents in an extraction solvent to obtain an aqueous solution containing the extract containing the polyphenol as a main component, and water containing the extract as a main component and a processing step of bentonite processing to the aqueous solution, in the processing step, after allowed to coexist with the addition of bentonite in water solution containing water as a main component with containing the extract, removing the bentonite from the solution The gist is that the operation is performed.

The method for producing a polyphenol-containing material according to claim 2 is characterized in that, in the invention according to claim 1, pectinase is added to the extraction solvent in the extraction step.
In the method for producing a polyphenol-containing material according to claim 3, in the invention according to claim 1 or claim 2, in the treatment step, an ingredient exhibiting an unpleasant odor, bitterness and miscellaneous taste contained in the extract. The gist is that they are adsorbed by the bentonite and that their components are removed from the solution together with the bentonite.

  The method for producing a polyphenol-containing material according to claim 4 is the invention according to any one of claims 1 to 3, wherein in the treatment step, yellowness and redness of the solution containing the extract are reduced. The gist is that

  The method for producing a polyphenol-containing material according to claim 5 is the invention according to any one of claims 1 to 4, wherein the method further includes a purification step after the treatment step, and the purification step. Then, an adsorption treatment for adsorbing the treatment liquid after the treatment step to an adsorption resin, a washing treatment for washing the adsorption resin after the adsorption treatment with water or a 20% by volume or less hydrous alcohol, and the washing treatment after the washing treatment The gist is that an elution treatment for eluting the polyphenol from the adsorption resin is performed.

  The food and drink according to claim 6 includes the polyphenol-containing material produced by the method for producing a polyphenol-containing material according to any one of claims 1 to 5.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the polyphenol containing raw material which can reduce easily content of the component which reduces quality, while containing polyphenol derived from citrus fruits at a high density | concentration can be provided. Moreover, according to this invention, the food / beverage products provided with high quality can be provided, containing the citrus origin polyphenol.

Hereinafter, one embodiment which materialized the manufacturing method and food-drinks of the polyphenol content material of the present invention is described.
The polyphenol-containing material of the present embodiment contains a citrus-derived polyphenol at a high concentration, and is mainly used by being added to foods and drinks, pharmaceuticals, and the like. This polyphenol-containing material may be either liquid or powder. The polyphenol-containing material preferably contains polyphenol as a main component. The above-mentioned polyphenol as a main component means that the content of polyphenol among soluble solids in the polyphenol-containing material is higher than any other component, and the polyphenol is preferably 30% by weight or more, more preferably 50% by weight. % Or more.

  Examples of citrus fruits include citrus citrus fruits such as lemon, lime, shikwasa, sudachi, yuzu, daidai, kabosu, grapefruit, navel orange, valencia orange, sour orange, hassaku, mandarin orange, ikankan, ponkan, sweet summer, bungtan, etc. It is done. The polyphenol-containing material of the present embodiment contains a polyphenol derived from one or more kinds of citrus fruits among these citrus fruits. Moreover, you may contain the polyphenol derived from the hybrid | sebration kind of these enumerated multiple types of citrus. Examples of polyphenols contained in these citrus fruits include eriocitrin, hesperidin, 6,8-di-C-glucosyl diosmine, 6-C-glucosyl diosmine, naringin and the like. Since these polyphenols have various physiological effects useful for living bodies, including an antioxidant action, they have high value as active ingredients in health foods and pharmaceuticals.

  These polyphenols are contained in large amounts in the citrus peel. By the way, citrus fruits are provided with pericarp, fruit juice, scabbard, saury and seeds. In addition to the above polyphenols, citrus peels have an unpleasant odor component of Chinese herbal medicine, an unpleasant bitterness, a taste component that makes a bitter taste, a visual turbidity, or a loss of freshness. Ingredients such as coloring components are also included. These odor components, taste components, and coloring components are generally easily extracted from the citrus peel along with the polyphenol by a polar solvent such as water or alcohol.

  The polyphenol-containing material of the present embodiment makes it difficult to feel an unpleasant odor of traditional Chinese medicine caused by heat applied in processing steps such as extraction, concentration, and purification, and can reduce the occurrence of unpleasant change odor over time. Therefore, it is suitable for use in foods and drinks, or pharmaceutical products having oral or nasal dosage forms. Furthermore, the polyphenol-containing material of the present embodiment has a taste characteristic that it is difficult to feel unpleasant bitterness and miscellaneous taste when taken orally, and it is difficult to maintain an unpleasant aftertaste caused by the bitter taste or miscellaneous taste. Since it has, it is suitable for the utilization to the pharmaceutical which has the dosage form of food-drinks or an oral preparation.

  In general, when the brown content of the polyphenol-containing material is large, the food / beverage product itself is likely to be colored when it is added to the food / beverage product, but the appearance is impaired, but the polyphenol-containing material of this embodiment affects the color tone of the appearance. There is also a visual characteristic that a good color tone can be easily obtained and the color tone can be maintained for a long period of time. For this reason, the polyphenol-containing material is suitable for use in beverages, liquid foods or pharmaceuticals, particularly foods and beverages or pharmaceuticals with a low degree of transparency or coloring. Since the deterioration of the color tone is deeply related to browning, it can be evaluated by, for example, the strength of yellowing and the strength of redness. The strength of yellowness and the strength of redness can be quantitatively evaluated by measuring the absorbance at wavelengths near 420 nm and 520 nm for a solution containing a polyphenol-containing material.

Next, the manufacturing method of the polyphenol containing raw material of this embodiment is demonstrated.
The method for producing a polyphenol-containing material according to the present embodiment includes an extraction step of immersing a raw material composed of citrus fruits or its constituents in an extraction solvent to obtain an extract (extract), and an extract after the extraction step And a bentonite treatment process. In the extraction step, an extract containing the odor component, taste component, coloring component and the like together with polyphenol is obtained. In the treatment step, the odor component, taste component, and color component are selectively removed from the extract. Therefore, a high-quality polyphenol-containing material containing polyphenol at a high concentration is produced. In addition, a process process may be implemented in multiple times as needed.

  In the extraction step, the polyphenol contained in the raw material is transferred into the extraction solvent by immersing the raw material in the extraction solvent. At this time, in order to increase the extraction rate of polyphenol, the extraction solvent may be stirred. Further, in this extraction step, after sufficiently transferring the polyphenol into the extraction solvent, solid-liquid separation is performed to separate the solid (raw material) and the extraction solvent (extract). By this solid-liquid separation, an extract obtained by dissolving an extract such as polyphenol in an extraction solvent is obtained. Incidentally, the extract after the solid-liquid separation contains polyphenols and other extracts such as odor components, taste components and coloring components as soluble solids.

  As the raw material, citrus fruits or their constituent components are used. Examples of the constituent components of fruits include fruit skin, fruit juice, scabbard, potato and seeds. Among these constituent components, since it is easy to obtain a large amount of polyphenol, a fruit skin or a juice residue is preferably used. The squeezed residue is a residue after squeezing the fruit juice from the fruit, and includes a fruit skin, a fungus membrane, a part of the sage, seeds, and a very small amount of fruit juice that could not be squeezed. Incidentally, when using the squeezed residue in the extraction step, it is preferable that the fruit skin (flavedo) is removed by peeling.

  As an extraction solvent, an organic solvent such as methanol, ethanol, butanol, propanol, isopropanol, glycerin, glacial acetic acid, hexane, ethyl acetate, or water is used, and water or ethanol is used when a polyphenol-containing material is added to a food or drink. Is preferably used, and water is particularly preferably used because it is inexpensive. These extraction solvents may be used alone or in combination of two or more. Moreover, when using water, you may adjust pH suitably with an alkali and an acid. In addition, it is preferable that the extraction time in an extraction process is 30 minutes or more in order to fully transfer a polyphenol in an extraction solvent. Incidentally, since citrus fruits or their constituents contain a lot of water, the extract after the extraction step tends to be an aqueous solution containing water as a main component.

  For the solid-liquid separation, a known separation method such as centrifugation or membrane separation can be employed. However, since it is simple, centrifugation is preferably employed. In centrifugation, the conditions under which solids such as fruit skin and the extract can be separated may be selected as appropriate. In addition, as a pretreatment for centrifugation or membrane separation, it is preferable to remove in advance large solids such as pericarp by mesh filtration or decantation as necessary. The extract after the solid-liquid separation is subjected to a treatment step after being concentrated or diluted with water as necessary. For concentration of the extract, known vacuum concentration, membrane concentration, freeze concentration and the like can be employed.

  In the extraction process of this embodiment, pectinase treatment is simultaneously performed by adding pectinase to the extraction solvent in order to increase the extraction rate of polyphenol and increase the clarity of the resulting extract to make it transparent. It is particularly preferable to do this. Pectinase breaks down the pectin contained in the raw material and facilitates the transfer of polyphenols from the lump (solid matter) of the peel or juice residue into the extraction solvent. In addition, when adding pectinase to the extraction solvent, the extraction solvent is preferably water or a buffer solution in order to make it difficult to reduce pectinase activity, but lower alcohol, glycerin, glacial acetic acid are used at low concentrations. Etc. may be contained. Moreover, it is preferable that the extraction temperature in an extraction process exists in the range of the optimal temperature of pectinase activity.

  In the treatment step, the bentonite treatment is performed by adding bentonite to the solution containing the extract extracted in the extraction step, particularly preferably an aqueous solution containing the extract and allowing to stand for a predetermined time, and then after the bentonite treatment. A removal operation for removing bentonite from the solution (aqueous solution) is performed. That is, in this treatment step, the extract and bentonite are allowed to coexist in the solution (aqueous solution) to selectively adsorb the odor component, taste component, and coloring component on the bentonite, and then the components. Are removed from the solution (aqueous solution) together with bentonite. At this time, since polyphenol is hardly adsorbed to bentonite in the solution (aqueous solution), a high-quality treatment liquid containing polyphenol in a high ratio is recovered after the treatment step.

  The solution containing the extract may be any solvent such as methanol, ethanol, butanol, propanol, isopropanol, glycerin, glacial acetic acid, hexane, ethyl acetate, water, or a mixed solvent thereof. Refers to those dissolved in On the other hand, as the aqueous solution containing the extract, when an extraction solvent mainly composed of water is used in the extraction step, it is most convenient to use the extract after the extraction step as it is. However, when the content of water in the extract is low enough that the odor component, taste component, and coloring component are not easily absorbed by bentonite, the extract is diluted with water, or the extract is concentrated. Thus, a product obtained by selectively volatilizing a lower alcohol or the like is used. The content of water in the aqueous solution containing the extract is preferably 50% by volume or more, more preferably 60% by volume or more, in order to efficiently adsorb the odor component, taste component and coloring component to bentonite. Preferably it is 70 volume% or more.

  Bentonite is a basic claystone produced by contact of volcanic ash with seawater or tuffing by hydrothermal alteration. Montmorillonite as the main component, quartz, calcite, α-cristobalite, opal, feldspar , And associated minerals such as mica. Bentonite exhibits swelling properties, thickening properties and thickening properties, and has a feature of having high adsorption performance for cationic substances, and is used in water-based paints, cosmetics, pharmaceuticals, toothpastes, foods and the like.

  The bentonite treatment is carried out by adding bentonite suspended (swelled) in the solvent of the solution to the solution containing the extract in order to rapidly proceed with the treatment. In addition, it is especially preferable that the bentonite treatment of the present embodiment is performed by adding bentonite suspended (swelled) in water to the aqueous solution containing the extract. In this bentonite treatment, in order to sufficiently adsorb the odor component, taste component and coloring component to bentonite, the bentonite is added to a solution (aqueous solution) containing the extract, and then the extract and bentonite are mixed for 30 minutes or more. It is preferable to coexist (react). In addition, in the bentonite process of this embodiment, it is also possible to add the montmorillonite which is a main component of a bentonite with respect to the solution (aqueous solution) containing an extract instead of adding a bentonite.

  In the removal operation, a known separation method such as centrifugation or membrane separation can be employed. However, since it is simple, centrifugation is preferably employed. In centrifugation, the conditions which can isolate | separate bentonite from the solution (aqueous solution) containing an extract and bentonite should just be employ | adopted suitably. The treatment liquid after the removal operation can be used as it is as a polyphenol-containing material, and can also be used as a polyphenol-containing material after being concentrated or diluted with water as necessary. For the concentration of the treatment liquid, known vacuum concentration, membrane concentration, freeze concentration and the like can be employed.

  In addition, in the manufacturing method of this embodiment, it is preferable that the process liquid after removal operation is used for the refinement | purification process for removing a contaminant and raising content of polyphenol. Contaminants refer to components other than polyphenols contained in the extract, and specifically include other components such as pectin in addition to the odor component, taste component, and coloring component. Although the purification method employ | adopted at a refinement | purification process is not specifically limited, It is especially preferable to employ | adopt the purification method using adsorption resin. In the purification step using the adsorption resin, it is most simple to carry out using the treatment liquid after the treatment step as it is.

  As the adsorption resin, a resin capable of adsorbing polyphenol is used. Examples of the material of the adsorption resin include styrene synthetic resins and acrylic synthetic resins. Specifically, Amberlite XAD-16 manufactured by Rohm and Haas, or SP700 series or SP800 series manufactured by Mitsubishi Chemical Corporation is preferably used. When carrying out a purification process using such an adsorbent resin, first, after applying an adsorption treatment in which the treatment liquid after the treatment process is applied to the adsorbent resin to adsorb polyphenol to the adsorbent resin, the adsorbent resin is washed. A washing process is performed, followed by an elution process for eluting the polyphenol from the adsorption resin.

  The adsorption treatment is performed to apply the treatment liquid to the adsorption resin packed in the column and adsorb the polyphenol in the treatment liquid to the adsorption resin. In order to make it easy to adsorb and hold the polyphenol in the treatment liquid on the adsorption resin, the treatment liquid is preferably an aqueous solution containing 70% by volume or more, more preferably 90% by volume or more of water.

  The washing process is a process of washing the adsorption resin by flowing a washing solvent through the column after the adsorption treatment, and is performed to remove many impurities other than the polyphenol from the adsorption resin. As the washing solvent, a solvent capable of maintaining the adsorption state of polyphenol with respect to the adsorption resin is used, but the above polar solvent is preferably used, and more preferably water or hydrous alcohol having an alcohol concentration of 20% by volume or less is used. More preferably, warm water or hydrous ethanol having an alcohol concentration of 20% by volume or less is used. In this washing treatment, the adsorbability of some impurities to the adsorbent resin in the presence of the washing solvent is lower than the adsorbability of polyphenol, so that the impurities are easily eluted and the polyphenol is likely to remain in the adsorbent resin. Is used. Further, when the washing solvent is water, it may be allowed to flow through the column in an unheated state, but in order to efficiently remove impurities other than polyphenol, the column is heated to 40 to 100 ° C. It is preferable to be washed away. In addition, when the cleaning solvent is a hydrous alcohol, if the alcohol concentration in the solvent exceeds 20% by volume, polyphenol is easily eluted from the adsorption resin, so that there is a high possibility that the final recovery rate is lowered. .

  The elution process is a process for eluting the polyphenol adsorbed on the adsorption resin by flowing an elution solvent through the column after the washing process, and is performed to recover the polyphenol from the column. By this elution treatment, an eluate obtained by dissolving polyphenol in the elution solvent is obtained. As elution solvents, alcohols such as ethanol, organic solvents such as acetone, hexane, chloroform, glycerin, glacial acetic acid, and water can be used. When polyphenols are included in foods and drinks, the alcohol concentration exceeds 20% by volume. Water-containing ethanol, preferably water-containing ethanol having an alcohol concentration of 30% by volume or more is preferably used. These enumerated solvents may be used alone or in combination of two or more. Incidentally, when water-containing ethanol is used as an elution solvent, it is difficult to elute polyphenol from the adsorption resin when the alcohol concentration in the solvent is 20% by volume or less. Moreover, when using water-containing ethanol as an elution solvent, the upper limit value of the alcohol concentration of water-containing ethanol may be set as appropriate based on the improvement in combination with bentonite treatment and the amount of polyphenol that is finally obtained.

  The eluate obtained by the purification process (elution treatment) can be used as it is as a polyphenol-containing material, and can also be used as a polyphenol-containing material in a state of being concentrated, dried or diluted with water as necessary. It is. For concentration and drying of the eluate, known vacuum concentration, membrane concentration, freeze concentration, vacuum drying or freeze drying can be employed.

  The food / beverage products of this embodiment contain the polyphenol containing material manufactured by the manufacturing method mentioned above. As food and drinks, supplements such as health foods are included in addition to beverages such as drinks and foods such as cookies. It is preferable that content of the polyphenol in food-drinks is 0.05 to 50 weight%. If the content of polyphenols contained in foods and drinks is less than 0.05% by weight, it is difficult to sufficiently exert useful physiological effects such as antioxidant action, and conversely, if it exceeds 50% by weight, it is not economical. It is. It is preferable that food and drink be taken orally continuously every day. Moreover, it is preferable to take it orally by dividing into several times a day. In foods and drinks, the intake of polyphenols varies depending on age, weight, etc., but is preferably 0.05 to 300 g, more preferably 0.1 to 50 g per day for an adult. If the intake amount of polyphenol per day is less than 0.05 g, it is difficult to sufficiently exert the useful physiological action, and conversely, if it exceeds 300 g, it is uneconomical. In the case of a dwarf, half the amount for an adult is a guide.

The effects exhibited by the embodiment will be described below.
-The manufacturing method of the polyphenol containing raw material of this embodiment is equipped with the extraction process and the process process of carrying out the bentonite process with respect to the extract extracted by this extraction process. In the extraction step, unpleasant odor components, taste components and coloring components derived from citrus peels and the like are extracted at the same time with polyphenols, but these unpleasant components are selectively removed by the bentonite treatment, It becomes possible to produce a high-quality polyphenol-containing material that contains polyphenol at a high concentration. Therefore, according to the production method of the present embodiment, while containing a polyphenol derived from citrus fruits at a high concentration, while maintaining a low brownness color tone that does not affect the addition to other food and drink, It is extremely easy to provide a polyphenol-containing material with high quality that does not exhibit a bad smell and bitterness.

  In particular, in the production method of the present embodiment, the extraction step is performed using water as an extraction solvent, bentonite is added as it is to the water extract after the extraction step, the bentonite treatment is performed, and then the removal operation is performed by centrifugation. Implementation is most efficient. In addition, by adding pectinase to the extraction solvent in the extraction step, the extraction rate of polyphenol can be increased, and a clear extract with little turbidity can be easily obtained.

  -The food / beverage products of this embodiment contain the high quality polyphenol containing material manufactured through the bentonite process. For this reason, in this food / beverage product, even when polyphenol derived from citrus fruits is contained at a high concentration, it tends to have high quality with respect to odor, taste and color tone. Therefore, it becomes easy to take food and drink easily and easily every day.

<Manufacture of polyphenol-containing material 1>
(Comparative Example 1)
After adding 1 L of water and 500 mg of pectinase (pectinase PL manufactured by Amano Enzyme Co., Ltd.) to 200 g of lemon fruit juice residue and stirring, the extraction step was carried out by allowing to stand at room temperature for 30 minutes. The water extract after the extraction step was subjected to mesh filtration (mesh size: 500 μm / 32 mesh), and then centrifuged at 9000 rpm for 20 minutes. The supernatant after centrifugation was subjected to ultrafiltration with a molecular weight cut-off of 20000 to obtain a transparent filtrate. The soluble solid concentration of this filtrate (water extract) was Brix 2.2.

(Test Example 1)
According to the method of Comparative Example 1, a filtrate (water extract) having a soluble solid content concentration of Brix 2.2 was obtained. Next, with respect to 900 mL of the obtained filtrate (water extract), 100 mL of a 2% bentonite (Hogel Co., Ltd. Bengel series) suspension previously swollen with water was added and stirred well, and then at room temperature for 30 minutes. The bentonite process was implemented by leaving still. The soluble solid content concentration at this time was Brix 2.0. Next, the liquid after bentonite treatment was centrifuged at 9000 rpm for 10 minutes to obtain a supernatant liquid (polyphenol-containing material of Test Example 1). The soluble solid content concentration of the supernatant was Brix 2.0.

(Test Example 2)
A polyphenol-containing material was obtained according to the method of Test Example 1. Next, after adding 100 mL of 2% bentonite suspension previously swollen with water to the resulting supernatant liquid (polyphenol-containing material) and stirring well, the mixture is allowed to stand at room temperature for 30 minutes, whereby the second The second bentonite treatment was performed. The liquid after the second bentonite treatment was centrifuged at 9000 rpm for 10 minutes to obtain a supernatant (polyphenol-containing material of Test Example 2).

<Evaluation of color tone of polyphenol-containing material>
For each sample of Test Examples 1 and 2 and Comparative Example 1, the absorbance at 420 nm and 520 nm was measured using a spectrophotometer (Hitachi Double Beam Spectrophotometer Model U-2000). The measurement results for each sample were corrected to match the soluble solids concentration to Brix 2.0 for comparison. The results are shown in Table 1.

色調の悪化は、褐変と深い関わりを持っているため、黄みの強さ（４２０ｎｍにおける吸光度）と、赤みの強さ（５２０ｎｍにおける吸光度）とによって評価可能である。表１より、試験例１では、ベントナイト処理により、黄み及び赤みがともに低下した。よって、試験例１は、比較例１よりも、色調に関して高い品質を有していることが示された。さらに、ベントナイト処理を２回実施した試験例２では、１回実施した試験例１よりも色調が改善されていることも示された。よって、ベントナイト処理により、色調を改善することができた。

Since the deterioration of the color tone has a deep connection with browning, it can be evaluated by the intensity of yellowing (absorbance at 420 nm) and the intensity of redness (absorbance at 520 nm). From Table 1, in Test Example 1, both yellowishness and redness were reduced by the bentonite treatment. Therefore, it was shown that Test Example 1 has higher quality with respect to the color tone than Comparative Example 1. Furthermore, in Test Example 2 in which the bentonite treatment was performed twice, it was also shown that the color tone was improved over Test Example 1 in which the bentonite treatment was performed once. Therefore, the color tone could be improved by the bentonite treatment.

<Manufacture of lemon-style beverages containing polyphenol-containing materials>
(Comparative Example 2)
After adding 10 L of water and 5 g of pectinase PL to 2 kg of lemon fruit squeezed residue and stirring, the extraction step was carried out by allowing to stand at room temperature for 30 minutes. The water extract after the extraction step was subjected to mesh filtration (mesh size: 500 μm / 32 mesh), and then centrifuged at 9000 rpm for 20 minutes. The supernatant after centrifugation was subjected to ultrafiltration with a molecular weight cut-off of 20000 to obtain a transparent filtrate. The soluble solid content concentration of this filtrate was Brix 2.2.

  Next, the obtained filtrate was passed through a column packed with 200 mL of an adsorption resin (Amberlite XAD-16 manufactured by Rohm and Haas), and the column was washed with 1 L of 10% by volume of water-containing ethanol. Subsequently, 1 L of 30% by volume aqueous ethanol was passed through the column to obtain an eluate, and the obtained eluate was concentrated under reduced pressure. The concentrated eluate was analyzed by high performance liquid chromatography (HPLC; Shimadzu LC-10A) to quantify the concentration of eriocitrin contained in the eluate. As HPLC analysis conditions, 10 μL of the eluate passed through a 0.45 μm filter was injected (injected) into an ODS column (column temperature; 40 ° C.), and the mobile phase (methanol: 5% acetic acid = 30: 70). ) At a flow rate of 1 mL / min, followed by peak separation, followed by detection at 280 nm. As a result, the concentrated eluate (the water extract of Comparative Example 2) contained about 18000 ppm of eriocitrin.

  Next, after adding 64 g of sucrose, 9.1 g of anhydrous citric acid, and 0.6 g of ascorbic acid to 100 g of the obtained eluate (water extract of Comparative Example 2), 1 L of lemon-style beverage was added with water. Was made. This lemon-like beverage was sterilized at 95 ° C. for 30 seconds, and then 100 mL each was hot-packed into the bottle. The lemon-like beverage of Comparative Example 2 has a soluble solid content concentration of Brix 7.2, an acidity of 0.93 (citric acid acidity; w / v%), and contains 1800 ppm equivalent of eriocitrin.

(Test Example 3)
After adding 10 L of water and 5 g of pectinase PL to 2 kg of lemon fruit squeezed residue and stirring, the extraction step was carried out by allowing to stand at room temperature for 30 minutes. The aqueous extract after the extraction step was filtered and then centrifuged at 9000 rpm for 20 minutes. The supernatant after centrifugation was subjected to ultrafiltration with a molecular weight cut-off of 20000 to obtain a transparent filtrate. The soluble solid content concentration of this filtrate was Brix 2.2.

  Next, 1 L of a 2% bentonite suspension previously swollen with water was added to 9 L of the obtained filtrate, and the mixture was well stirred, and then allowed to stand at room temperature for 30 minutes to perform bentonite treatment. The liquid after the bentonite treatment was centrifuged at 9000 rpm for 10 minutes to obtain a supernatant.

  Next, the obtained supernatant was passed through a column filled with 200 mL of an adsorption resin (Amberlite XAD-16), and the column was washed with 1 L of 10% aqueous ethanol. Subsequently, 1 L of 30% aqueous ethanol was passed through the column to obtain an eluate, and the obtained eluate was concentrated under reduced pressure. By analyzing the concentrated eluate by HPLC, the concentration of eriocitrin contained in the eluate was quantified. As a result, about 18000 ppm of eriocitrin was contained in the eluate after concentration (the polyphenol-containing material of Test Example 3).

  Next, after adding 64 g of sucrose, 9.1 g of anhydrous citric acid and 0.6 g of ascorbic acid to 100 g of the obtained eluate (polyphenol-containing material of Test Example 3), 1 L of a lemon-style beverage is added with water. Was made. This lemon-like beverage was sterilized at 95 ° C. for 30 seconds, and then 100 mL each was hot-packed into the bottle. The lemon-like beverage of Test Example 3 has a soluble solid content concentration of Brix 7.2, an acidity of 0.93 (citric acid acidity; w / v%), and contains 1800 ppm equivalent of eriocitrin.

<Evaluation of the color tone of lemon-style beverages>
An acceleration aging test was performed by allowing the lemon-like beverages of Test Example 3 and Comparative Example 2 to stand at 60 ° C. for 3 days. About each lemon-like drink, the light absorbency in 420 nm and 520 nm of the thing immediately after manufacture (non-aging product) and the thing left still at 60 degreeC (aging product) was measured using the spectrophotometer, respectively. The results are shown in Table 2.

表２より、未経時品同士を比較すると、試験例３は、比較例２よりも色調に関して高い品質を有していることが示された。さらに、試験例３の経時品は、比較例２の未経時品よりも色調に関して高い品質を有していることも示された。よって、ベントナイト処理により、色調に関する品質を長期に亘って持続することができた。

From Table 2, when the unaged products were compared with each other, it was shown that Test Example 3 had a higher quality with respect to the color tone than Comparative Example 2. Furthermore, it was also shown that the time-lapse product of Test Example 3 has higher quality in terms of color than the non-time-lapse product of Comparative Example 2. Therefore, the quality regarding a color tone was able to be maintained over a long period of time by bentonite treatment.

<Evaluation of smell and taste of lemon-style beverage>
Ten expert panelists were allowed to drink each of the lemon-style beverages of Test Example 3 and Comparative Example 2, and each evaluation item shown in Table 3 was evaluated according to the evaluation criteria shown in the same table, with a 7-level evaluation and each evaluation. A comprehensive evaluation was performed based on the results. In each evaluation, the untimed product of Comparative Example 2 was defined as a standard product (ie, evaluation score 0). Table 3 shows the average value of the evaluation points.

表３に示す各評価項目においては、いずれも小さい数値である方が高い品質を有していることを示している。一方、総合評価においては、大きい数値であるほうが高い品質を有していることを示している。表３より、試験例３のレモン風飲料は、比較例２よりも臭い及び呈味に優れていることが示された。よって、ベントナイト処理により、臭い及び呈味に関する品質が改善されるとともに、該品質を長期に亘って高く維持することが可能であることが示された。

In each evaluation item shown in Table 3, it is shown that the smaller the numerical value, the higher the quality. On the other hand, in the comprehensive evaluation, a larger numerical value indicates higher quality. From Table 3, it was shown that the lemon-like beverage of Test Example 3 is superior in odor and taste to Comparative Example 2. Therefore, it was shown that the quality related to odor and taste can be improved by the bentonite treatment, and that the quality can be maintained high over a long period of time.

<Examination of Bentonite Treatment Conditions 1> Examination of Bentonite Amount in Water Extraction In order to optimize the conditions of the bentonite treatment, a relative quantitative ratio between the amount of polyphenol and the amount of bentonite in the treatment was examined. First, the water extract of Comparative Example 1 (Brix 2.2) was concentrated to Brix 10 by concentration under reduced pressure, and then various water extracts diluted to the soluble solids concentration shown in Table 4 when the bentonite swelling liquid was added. Prepared each. Next, bentonite was added to each aqueous extract so as to have a final concentration of 0.5% and stirred well, and then allowed to stand at room temperature for 30 minutes, thereby performing bentonite treatment. Each solution after the bentonite treatment was centrifuged at 9000 rpm for 10 minutes to obtain a supernatant.

  About each supernatant liquid and the water extract of the comparative example 1, after diluting with water so that it might become Brix2.0, the light absorbency in 420 nm and 520 nm was measured using the spectrophotometer, respectively. Furthermore, each supernatant liquid and the water extract of Comparative Example 1 were each diluted with water to give Brix 2.0, and then subjected to HPLC analysis to determine the eriocitrin concentration. Using the obtained eriocitrin concentration, the recovery rate (%) of eriocitrin recovered in each supernatant was determined. These results are shown in Table 4.

表４より、水抽出液の可溶性固形分濃度（ポリフェノール量）に対して、ベントナイト量を相対的に多く設定してベントナイト処理を実施することにより、色調に関する品質の高いポリフェノール含有素材が得られることが示された。

From Table 4, it is possible to obtain a high-quality polyphenol-containing material related to color tone by performing a bentonite treatment with a relatively large amount of bentonite with respect to the soluble solid content concentration (polyphenol amount) of the water extract. It has been shown.

  Furthermore, in this test, when the bentonite treatment was performed with a large amount of bentonite set relative to the soluble solid content concentration (polyphenol amount) of the water extract, and when the bentonite treatment was performed with a small amount of bentonite set, Surprisingly, the recovery rate of eriocitrin was almost the same value. That is, in the bentonite treatment, it was shown that many components that degrade the quality in proportion to the amount of bentonite used can be removed, while polyphenols can be recovered at a high rate. Therefore, it has been shown that the bentonite treatment is a treatment for selectively removing components that degrade the quality while keeping the polyphenol recovery loss small.

<Reference example 1> Examination of relative quantitative ratio of polyphenol and activated carbon in activated carbon treatment For reference, a test for removing components that deteriorate the quality from the aqueous extract of Comparative Example 1 was performed using activated carbon. First, the water extract (Brix 2.2) of Comparative Example 1 was concentrated to a soluble solid content concentration of Brix 8. Next, the amount shown in Table 5 was added to the concentrated liquid of Comparative Example 1 in the amount of activated carbon (Taiko FC manufactured by Phutamura Chemical Co., Ltd.) and allowed to stand at room temperature for 1 hour. Then, after removing activated carbon by filtration, it diluted with water so that it might become the soluble solid content concentration of Brix4.

  About each diluted solution after dilution, the light absorbency in 420 nm and 520 nm was each measured using the spectrophotometer. Moreover, the ratio of the absorbance of each sample when the absorbance obtained with the sample to which no activated carbon was added was taken as 100% was also determined. Furthermore, the eriocitrin concentration was quantified by HPLC analysis of each diluted solution. Using the obtained eriocitrin concentration, the recovery amount (mg) and recovery rate (%) of eriocitrin recovered in each dilution were determined. These results are shown in Table 5.

表５より、水抽出液の可溶性固形分濃度（ポリフェノール量）に対して、活性炭の添加量を相対的に多く設定して活性炭処理することにより、色調が改善されることが示された。しかしながら、色調の改善に反比例して、エリオシトリンの回収率が低下することも示された。従って、活性炭処理は、品質を低下させる成分及びポリフェノールの両方を非選択的に除去する処理であることが示された。以上の結果を踏まえると、活性炭処理によっても色調に関する品質の向上は可能ではあるが、ポリフェノールの精製という観点からは、品質を低下させる成分を選択的に除去できるベントナイト処理がより有効な処理方法であると言える。

From Table 5, it was shown that the color tone is improved by setting the amount of activated carbon to be relatively large with respect to the soluble solid content concentration (polyphenol amount) of the water extract and treating with activated carbon. However, it was also shown that the recovery rate of eriocitrin decreased in inverse proportion to the improvement in color tone. Thus, the activated carbon treatment was shown to be a treatment that non-selectively removes both the quality-degrading component and the polyphenol. Based on the above results, it is possible to improve the color quality by activated carbon treatment, but from the viewpoint of polyphenol purification, bentonite treatment that can selectively remove components that degrade quality is a more effective treatment method. It can be said that there is.

<Examination of Bentonite Treatment Conditions 2> Examination of Polyphenol Concentration and Bentonite Concentration In order to optimize the bentonite treatment conditions, the polyphenol concentration and the bentonite concentration in the water extract were examined. The test was carried out in exactly the same manner as in Example 3 except that bentonite was added to each water extract so as to have the final concentration shown in Table 6 and the bentonite treatment was performed. The results are shown in Table 6.

表６より、可溶性固形分濃度（ポリフェノール濃度）及びベントナイト濃度が低い程、色調の改善及びエリオシトリンの回収率がともに高められる傾向が見られた。

From Table 6, it was found that the lower the soluble solid content concentration (polyphenol concentration) and the bentonite concentration, the higher the color tone and the higher the recovery rate of eriocitrin.

<Examination of Bentonite Treatment Conditions 3> Examination of Bentonite Treatment Time After concentrating the water extract (Brix 2.2) of Comparative Example 1 to approximately Brix 8 (see Table 7 for details), the final concentrations shown in Table 7 Bentonite was added so that the bentonite treatment was started at room temperature. After 0.5 hours, 3 hours, and 5 hours from the start of the bentonite treatment, a small amount of the treatment solution was collected and centrifuged at 9000 rpm for 10 minutes to obtain a supernatant. About each obtained supernatant liquid, the light absorbency in 420 nm and 520 nm was measured using the spectrophotometer, respectively. The results are shown in Table 7.

表７より、ベントナイト処理を０．５時間以上実施すれば、色調が十分に改善されることが示された。また、水抽出液の可溶性固形分濃度（ポリフェノール量）に対して、ベントナイト量を相対的に多く設定してベントナイト処理を実施することにより、色調に関する品質の高いポリフェノール含有素材が得られることが再確認された。

From Table 7, it was shown that if the bentonite treatment is carried out for 0.5 hour or longer, the color tone is sufficiently improved. In addition, by setting the amount of bentonite to a relatively large amount of soluble solid content (polyphenol amount) in the water extract and carrying out the bentonite treatment, it is possible to obtain a high-quality polyphenol-containing material related to color tone. confirmed.

<Examination of Bentonite Treatment Conditions 4> Examination of Bentonite Treatment Frequency After concentrating the aqueous extract (Brix 2.2) of Comparative Example 1 to approximately Brix 8, add bentonite so that the final concentration is 0.5%. After thoroughly stirring, the first bentonite treatment was carried out by standing at room temperature for 30 minutes. The liquid after the first bentonite treatment was centrifuged at 9000 rpm for 10 minutes to obtain a supernatant.

  Next, the bentonite was added to the supernatant obtained so that the final concentration was 0.5% and stirred well, and then allowed to stand at room temperature for 30 minutes, whereby the second bentonite treatment was performed. . The liquid after the second bentonite treatment was centrifuged at 9000 rpm for 10 minutes to obtain a supernatant. Thus, the bentonite process was implemented to the 4th time.

  The supernatant obtained in each bentonite treatment and the water extract (Brix8) of Comparative Example 1 were each measured for absorbance at 420 nm and 520 nm using a spectrophotometer, and diluted with water to give Brix2. Thereafter, the eriocitrin concentration was quantified by HPLC analysis. Using the obtained eriocitrin concentration, the recovery rate (%) of eriocitrin recovered in each supernatant was determined. These results are shown in Table 8.

表８より、ベントナイト処理回数が増える程、色調が改善されることが示された。しかしながら、ベントナイト処理回収が増えると、最終的なエリオシトリンの回収量が減少するとともに、製造にかかる手間及び時間が増大することから、ベントナイト処理は２回までが適当であると考えられる。

Table 8 shows that the color tone improves as the number of bentonite treatments increases. However, when the recovery of bentonite treatment increases, the final recovery amount of eriocitrin decreases and the labor and time required for production increase. Therefore, it is considered that the bentonite treatment is suitable up to twice.

<Manufacture of polyphenol-containing materials derived from citrus other than lemon>
(Test Example 4)
Grapefruits, sweeties, buntans, hassakus, etc. are known as citrus fruits belonging to the citrus subfamily genus Citrus subgenus Bungtan. Among these citrus fruits belonging to Bungtan District, a polyphenol-containing material was produced from grapefruit (star ruby species) which is a typical citrus fruit.

  First, 1 L of water and 500 mg of pectinase PL were added to 200 g of grapefruit juice residue, stirred, and then allowed to stand at room temperature for 30 minutes to carry out the extraction step. The water extract after the extraction step was filtered through a mesh (500 μm / 32 mesh, the same in the following test examples and comparative examples), and then centrifuged at 9000 rpm for 20 minutes to obtain a supernatant. Next, 100 mL of a 2% bentonite suspension previously swollen with water was added to 900 mL of the obtained supernatant, and the mixture was stirred well, and then allowed to stand at room temperature for 30 minutes to perform bentonite treatment. After the bentonite-treated liquid was centrifuged at 9000 rpm for 20 minutes to obtain a supernatant, the supernatant was subjected to ultrafiltration with a molecular weight cut off of 20000 to obtain a transparent filtrate. The obtained filtrate was diluted with pure water so as to be Brix2, whereby the polyphenol-containing material of Test Example 4 was obtained.

(Comparative Example 3)
After adding 1 L of water and 500 mg of pectinase PL to 200 g of grapefruit juice residue and stirring, the extraction step was carried out by allowing to stand at room temperature for 30 minutes. The water extract after the extraction step was mesh filtered, and then centrifuged at 9000 rpm for 20 minutes to obtain a supernatant. Next, the obtained supernatant was subjected to ultrafiltration with a molecular weight cut-off of 20000 to obtain a transparent filtrate. The obtained filtrate was diluted with pure water so as to be Brix2, thereby obtaining the water extract of Comparative Example 3.

(Test Example 5)
Lime, bergat, etc. are known as citrus fruits belonging to the citrus subgenus Lime District of the Citrus genus. Among the citrus fruits belonging to these lime zones, a polyphenol-containing material was produced from lime, which is a typical citrus fruit. That is, a transparent filtrate was obtained in the same manner as in Example 4 above, using 200 g of lime juice residue instead of 200 g of grape fruit juice residue in Test Example 4. The obtained filtrate was diluted with pure water so as to be Brix 1.4, so that the polyphenol-containing material of Test Example 5 was obtained.

(Comparative Example 4)
A transparent filtrate was obtained in the same manner as in Comparative Example 3 using 200 g of lime juice residue instead of 200 g of grape fruit juice residue in Comparative Example 3 above. The obtained filtrate was diluted with pure water so as to be Brix 1.4 to obtain an aqueous extract of Comparative Example 4.

(Test Example 6)
Orange, Daidai, Iyokan, etc. are known as citrus fruits belonging to the dairy genus Citrus subgenus Daidai. Among these citrus fruits belonging to Daidai, a polyphenol-containing material was produced from orange (navel) which is a typical citrus fruit. That is, a transparent filtrate was obtained in the same manner as in Example 4 using 200 g of orange juice residue instead of 200 g of grapefruit juice residue in Test Example 4. The obtained filtrate was diluted with pure water so as to be Brix1.4, whereby the polyphenol-containing material of Test Example 6 was obtained.

(Comparative Example 5)
A transparent filtrate was obtained in the same manner as in Comparative Example 3 above, using 200 g of orange juice residue instead of 200 g of grapefruit juice residue in Comparative Example 3 above. The obtained filtrate was diluted with pure water so as to be Brix 1.4 to obtain an aqueous extract of Comparative Example 5.

(Test Example 7)
Citrus species of the citrus family Citrus subgenus Citrus subgenus Citrus citrus are known as Wenzhou mandarin orange, Sikhwasa, Mandarin, Ponkan and the like. Among the citrus fruits belonging to these mandarin oranges, in this test example, a polyphenol-containing material was produced from the citrus fruits of Wenzhou. That is, a transparent filtrate was obtained in the same manner as in Example 4 above, using 200 g of squeezed residue of citrus mandarin orange instead of 200 g of squeezed residue of grapefruit in Test Example 4. The obtained filtrate was diluted with pure water so as to be Brix 2.5 to obtain a polyphenol-containing material of Test Example 7.

(Comparative Example 6)
A transparent filtrate was obtained in the same manner as in Comparative Example 3 above, using 200 g of squeezed mandarin orange juice instead of 200 g of grapefruit squeezed residue in Comparative Example 3 above. The obtained filtrate was diluted with pure water so as to be Brix 2.5 to obtain an aqueous extract of Comparative Example 6.

(Test Example 8)
Among the citrus fruits belonging to the mandarin orange group, in this test example, a polyphenol-containing material was produced from Sikhwasa, which is a typical citrus fruit. That is, a transparent filtrate was obtained in the same manner as in Example 4 above, using 200 g of squeezed juice residue instead of 200 g of grapefruit juice residue in Test Example 4. The obtained filtrate was diluted with pure water so as to be Brix 1.2, whereby the polyphenol-containing material of Test Example 8 was obtained.

(Comparative Example 7)
A transparent filtrate was obtained in the same manner as in Comparative Example 3 above, using 200 g of squeezed juice residue instead of 200 g of grapefruit juice residue in Comparative Example 3 above. The obtained filtrate was diluted with pure water so as to have Brix 1.2, whereby a water extract of Comparative Example 7 was obtained.

(Test Example 9)
Citrus species belonging to the citrus family Citrus subgenus Citrus subgenus Yuzu-ku are known as Yuzu, Sudachi, Kabosu, and Hyuga Summer. Of these citrus fruits belonging to Yuzu Ward, polyphenol-containing materials were produced from Yuzu, which is a typical citrus. That is, a transparent filtrate was obtained in the same manner as in Example 4 above, using 200 g of yuzu juice residue instead of 200 g of grapefruit juice residue in Test Example 4. The obtained filtrate was diluted with pure water so as to be Brix 1.7, whereby the polyphenol-containing material of Test Example 9 was obtained.

(Comparative Example 8)
A transparent filtrate was obtained in the same manner as in Comparative Example 3 above, using 200 g of yuzu juice residue instead of 200 g of grapefruit juice residue in Comparative Example 3 above. The obtained filtrate was diluted with pure water so as to be Brix 1.7, thereby obtaining a water extract of Comparative Example 8.

<Evaluation 1 of polyphenol-containing material>
About each sample of Test Examples 4-9 and Comparative Examples 3-8, the quality regarding a color tone was evaluated by measuring the light absorbency in 420 nm and 520 nm, respectively. Next, each sample was subjected to HPLC analysis under the above analysis conditions, and the concentration of each polyphenol in each sample was determined from the peak area of each polyphenol. And about each sample, the amount of polyphenol (mg) contained in 180 g of liquids before a bentonite process was calculated | required using each obtained polyphenol density | concentration. Subsequently, each sample was evaluated for flavor and taste (sensory evaluation regarding bitterness and miscellaneous taste) by an experienced panelist. These results are shown in Table 9. In addition, the ratio (decrease rate) to which each polyphenol amount and each absorbance value were changed by the bentonite treatment is also shown in the same table.

表９に示すように、レモン以外の他の区に属する柑橘類でも、レモンの場合と全く同様の結果が得られた。従って、本実施形態のポリフェノール含有素材の製造方法は、柑橘類全般に関して、該柑橘類由来のポリフェノールを高い濃度で含有しつつ品質を低下させる成分の含有量を低減させることが可能であることが確認された。なお、表９には、ポリフェノール量の減少率がマイナスで表示されているケースが見られるが、これらはいずれもポリフェノールの含有量が微量であるための分析誤差に起因するものである。

As shown in Table 9, the same results as in the case of lemon were obtained with citrus fruits belonging to other sections than lemon. Therefore, it has been confirmed that the method for producing a polyphenol-containing material of the present embodiment can reduce the content of components that lower the quality while containing the citrus-derived polyphenol at a high concentration with respect to citrus fruits in general. It was. In Table 9, there are cases where the decrease rate of the amount of polyphenol is displayed as a negative value, and these are all caused by an analysis error due to a very small amount of polyphenol.

In this example, various conditions for optimizing the method for producing a polyphenol-containing material were examined.
<Influence of peeling>
(Comparative Example 9)
After removing the flavedo portion from the lemon fruit by peeling, the juice was squeezed out with an inline squeezer to obtain a squeezed residue. Next, after adding 1 L of water and 500 mg of pectinase PL to 200 g of the obtained juice residue and stirring, the extraction step was carried out by allowing to stand at room temperature for 30 minutes. The water extract after the extraction step was mesh filtered, and then centrifuged at 9000 rpm for 20 minutes to obtain a supernatant. The obtained supernatant was subjected to ultrafiltration with a molecular weight cut-off of 20000 to obtain a transparent filtrate. The obtained filtrate was diluted with pure water so as to be Brix1.8, thereby obtaining a water extract of Comparative Example 9.

(Test Example 10)
After removing the flavedo portion from the lemon fruit by peeling, the juice was squeezed out with an inline squeezer to obtain a squeezed residue. Next, after adding 1 L of water and 500 mg of pectinase PL to 200 g of the obtained juice residue and stirring, the extraction step was carried out by allowing to stand at room temperature for 30 minutes. The water extract after the extraction step was mesh filtered, and then centrifuged at 9000 rpm for 20 minutes to obtain a supernatant.

  After adding 100 mL of 2% bentonite suspension swollen with water in advance to 900 mL of the obtained supernatant liquid and stirring well, the bentonite treatment was carried out by allowing to stand at room temperature for 30 minutes. After the bentonite-treated liquid was centrifuged at 9000 rpm for 20 minutes to obtain a supernatant, the supernatant was subjected to ultrafiltration with a molecular weight cut off of 20000 to obtain a transparent filtrate. The obtained filtrate was diluted with pure water so as to be Brix1.8, thereby obtaining the polyphenol-containing material of Test Example 10.

(Comparative Example 10)
Using the whole lemon fruit from which the flavedo portion was not removed, the juice was squeezed with an in-line squeezing machine to obtain a squeezed residue. A water extract was produced in the same manner as in Comparative Example 9 using 200 g of the obtained juice residue. That is, in Comparative Example 9, instead of lemon squeezed residue 200 g after removal of the flavedo portion, 200 g of lemon squeezed residue from which the flavedo portion of this comparative example was not removed was used in the same manner as in Comparative Example 9 above. A clear filtrate was obtained. The obtained filtrate was diluted with pure water so as to be Brix1.8, thereby obtaining a water extract of Comparative Example 10.

(Test Example 11)
Using the whole lemon fruit from which the flavedo portion was not removed, the juice was squeezed with an in-line squeezing machine to obtain a squeezed residue. A polyphenol-containing material was produced in the same manner as in Test Example 10 using 200 g of the obtained juice residue. That is, in Test Example 10, instead of 200 g of lemon juice residue after removal of the flavedo portion, 200 g of lemon juice residue from which the flavedo portion of this test example was not removed was used in the same manner as in Test Example 10 above. A clear filtrate was obtained. The obtained filtrate was diluted with pure water so as to be Brix1.8, thereby obtaining the polyphenol-containing material of Test Example 11.

<Evaluation 2 of polyphenol-containing materials>
The samples of Test Examples 10 and 11 and Comparative Examples 9 and 10 were evaluated in the same manner as in <Evaluation 1 of polyphenol-containing material> in Example 7 above. The results are shown in Table 10.

表１０に示すように、フラベド部を除去した果実の搾汁残渣から製造されたポリフェノール含有素材では、フラベド部を除去していない果実の搾汁残渣から製造されたポリフェノール含有素材よりも、色調及び苦味・雑味における品質が高いことが示された。さらに、剥皮によるフラベド部の除去と、ベントナイト処理とを併用することにより、ポリフェノール含有素材の品質がより一層高められることも確認された。

As shown in Table 10, in the polyphenol-containing material produced from the fruit juice residue from which the flavedo portion was removed, the color tone and the polyphenol-containing material produced from the fruit juice residue from which the flavedo portion was not removed. It was shown that the quality in bitterness and miscellaneous taste was high. Furthermore, it was also confirmed that the quality of the polyphenol-containing material can be further improved by using the removal of the flavedo portion by peeling and the bentonite treatment in combination.

<Influence of pectinase treatment>
(Reference Example 2)
Juice residue was obtained by squeezing fruit juice from lemon fruit with an in-line squeezer. Next, after adding and stirring 500 g of pure water at room temperature (27 ° C.) to 100 g of the obtained juice residue, the extraction step was carried out by allowing to stand at room temperature (27 ° C.) for 30 minutes. The water extract after the extraction step was mesh filtered, and then centrifuged at 9000 rpm for 20 minutes to obtain a supernatant. The obtained supernatant was subjected to ultrafiltration with a molecular weight cut-off of 20000 to obtain 475.7 g of a transparent filtrate (water extract of Reference Example 2). The soluble solid content concentration of the obtained filtrate was Brix 1.0.

(Reference Example 3)
Juice residue was obtained by squeezing fruit juice from lemon fruit with an in-line squeezer. Next, after adding 500 g of pure water of 45 ° C. to 100 g of the obtained juice residue and stirring, the extraction step was carried out by standing at 45 ° C. for 30 minutes. The water extract after the extraction step was mesh filtered, and then centrifuged at 9000 rpm for 20 minutes to obtain a supernatant. The obtained supernatant was subjected to ultrafiltration with a molecular weight cut-off of 20000 to obtain 479.7 g of a transparent filtrate (water extract of Reference Example 3). The soluble solid concentration of the obtained filtrate was Brix 1.1.

(Reference Example 4)
Juice residue was obtained by squeezing fruit juice from lemon fruit with an in-line squeezer. Next, after adding 500 g of pure water at 45 ° C. and 250 mg of pectinase PL to 100 g of the obtained juice residue and stirring, the extraction step was carried out by allowing to stand at 45 ° C. for 30 minutes. The water extract after the extraction step was mesh filtered, and then centrifuged at 9000 rpm for 20 minutes to obtain a supernatant. The obtained supernatant was subjected to ultrafiltration with a molecular weight cut-off of 20000 to obtain 480.2 g of a transparent filtrate (water extract of Reference Example 4). The soluble solid concentration of the obtained filtrate was Brix 1.2.

(Reference Example 5)
Juice residue was obtained by squeezing fruit juice from lemon fruit with an in-line squeezer. Next, after adding 500 g of pure water of 45 ° C. and 500 mg of pectinase PL to 100 g of the obtained squeezed residue and stirring, the extraction step was carried out by allowing to stand at 45 ° C. for 30 minutes. The water extract after the extraction step was mesh filtered, and then centrifuged at 9000 rpm for 20 minutes to obtain a supernatant. The obtained supernatant was subjected to ultrafiltration with a molecular weight cut-off of 20000, thereby obtaining 484.4 g of a transparent filtrate (water extract of Reference Example 5). The soluble solid content concentration of the obtained filtrate was Brix 1.3.

<Evaluation 3 of polyphenol-containing material>
Each sample of Reference Examples 2 to 5 was evaluated in the same manner as in <Evaluation 1 of polyphenol-containing material> in Example 7 above. The results are shown in Table 11.

表１１に示すように、抽出工程でペクチナーゼを添加することにより、ポリフェノールを多量に抽出できることが示された。なおこの場合、苦味・雑味も同時に多量に抽出されるが、本実施形態のベントナイト処理を実施することにより、苦味・雑味を効果的に低減可能であることは容易に推察される。

As shown in Table 11, it was shown that polyphenols can be extracted in large amounts by adding pectinase in the extraction step. In this case, although bitterness and miscellaneous taste are also extracted in large quantities at the same time, it is easily guessed that bitterness and miscellaneous taste can be effectively reduced by performing the bentonite treatment of this embodiment.

<Optimization of purification process>
After adding 10 L of water and 5 g of pectinase PL to 2 kg of lemon juice residue and stirring, the extraction step was carried out by allowing to stand at room temperature for 30 minutes. The water extract after the extraction step was mesh filtered, and then centrifuged at 9000 rpm for 20 minutes to obtain a supernatant. Next, the obtained supernatant was subjected to ultrafiltration with a molecular weight cut-off of 20000 to obtain a transparent filtrate (water extract). The soluble solid concentration of the obtained filtrate was Brix2. The obtained filtrate was divided into six sections, and samples of Comparative Examples 11 to 13 and Test Examples 12 to 14 described below were prepared.

(Comparative Example 11)
The aqueous extract was subjected to adsorption treatment by passing through a column packed with 200 mL of Amberlite XAD-16, and then the column was washed with 1 L of pure water at room temperature (27 ° C.). The cleaning treatment was performed by flowing 1 L of pure water (27 ° C.). Next, elution was performed by flowing 30% by volume of water-containing ethanol through the column. The obtained eluate was concentrated under reduced pressure, and then the concentrated solution was subjected to HPLC analysis to quantify the concentration of eriocitrin. As a result, the concentrated solution of Comparative Example 11 contained about 18000 ppm of eriocitrin.

(Test Example 12)
After adding 10 parts by weight of a 2% bentonite suspension previously swollen with water to 90 parts by weight of the water extract and stirring well, the bentonite treatment was carried out by allowing to stand at room temperature for 30 minutes. The liquid after the bentonite treatment was centrifuged at 9000 rpm for 10 minutes to obtain a supernatant.

  Next, the resulting supernatant was subjected to an adsorption treatment by passing through a column packed with 200 mL of Amberlite XAD-16, and then the column was washed with 1 L of pure water at room temperature (27 ° C.) Washing was performed by flowing 1 L of pure water at room temperature (27 ° C.) through the column. Next, elution was performed by flowing 30% by volume of water-containing ethanol through the column. The obtained eluate was concentrated under reduced pressure, and then the concentrated solution was subjected to HPLC analysis to quantify the concentration of eriocitrin. As a result, the concentrated solution of Test Example 12 contained about 18000 ppm of eriocitrin.

(Comparative Example 12)
Adsorption treatment was performed by passing the water extract through a column filled with 200 mL of Amberlite XAD-16, and then the column was washed with 1 L of pure water at 70 ° C., and then the column was cooled to room temperature (27 ° C.). Washing was performed by flowing 1 L of pure water. Next, elution was performed by flowing 30% by volume of water-containing ethanol through the column. The obtained eluate was concentrated under reduced pressure, and then the concentrated solution was subjected to HPLC analysis to quantify the concentration of eriocitrin. As a result, the concentrated solution of Comparative Example 12 contained about 18000 ppm of eriocitrin.

(Test Example 13)
After adding 10 parts by weight of a 2% bentonite suspension previously swollen with water to 90 parts by weight of the water extract and stirring well, the bentonite treatment was carried out by allowing to stand at room temperature for 30 minutes. The liquid after the bentonite treatment was centrifuged at 9000 rpm for 10 minutes to obtain a supernatant.

  Next, after the obtained supernatant was passed through a column packed with 200 mL of Amberlite XAD-16, the column was washed with 1 L of pure water at 70 ° C. Washing was performed by flowing 1 L of pure water (27 ° C.). Next, elution was performed by flowing 30% by volume of water-containing ethanol through the column. The obtained eluate was concentrated under reduced pressure, and then the concentrated solution was subjected to HPLC analysis to quantify the concentration of eriocitrin. As a result, the concentrated solution of Test Example 13 contained about 18000 ppm of eriocitrin.

(Comparative Example 13)
Adsorption treatment was performed by passing the aqueous extract through a column packed with 200 mL of Amberlite XAD-16, and then the column was washed with 1 L of 10 vol% aqueous ethanol at room temperature (27 ° C.). A washing treatment was performed by flowing 1 L of pure water at room temperature (27 ° C.). Next, elution was performed by flowing 30% by volume of water-containing ethanol through the column. The obtained eluate was concentrated under reduced pressure, and then the concentrated solution was subjected to HPLC analysis to quantify the concentration of eriocitrin. As a result, the concentrated solution of Comparative Example 13 contained about 18000 ppm of eriocitrin.

(Test Example 14)
After adding 10 parts by weight of a 2% bentonite suspension previously swollen with water to 90 parts by weight of the water extract and stirring well, the bentonite treatment was carried out by allowing to stand at room temperature for 30 minutes. The liquid after the bentonite treatment was centrifuged at 9000 rpm for 10 minutes to obtain a supernatant.

  Next, the resulting supernatant was subjected to an adsorption treatment by passing it through a column packed with 200 mL of Amberlite XAD-16, and then the column was washed with 1 L of 10 volume% aqueous ethanol at room temperature (27 ° C.). Further, the column was washed by flowing 1 L of normal water (27 ° C.) through the column. Next, elution was performed by flowing 30% by volume of water-containing ethanol through the column. The obtained eluate was concentrated under reduced pressure, and then the concentrated solution was subjected to HPLC analysis to quantify the concentration of eriocitrin. As a result, the concentrated solution of Test Example 14 contained about 18000 ppm of eriocitrin.

<Manufacture and evaluation of lemon-style beverages>
After adding 64 g of sucrose, 9.1 g of anhydrous citric acid and 0.6 g of ascorbic acid to 100 g of each sample (concentrated liquid) of Comparative Examples 11 to 13 and Test Examples 12 to 14, 1 L of lemon-style Each beverage was prepared. Each lemon-like beverage was sterilized at 95 ° C. for 30 seconds, and then 100 mL each was hot-packed into the bottle. Each lemon-like beverage has a soluble solid content concentration of Brix 7.2, an acidity of 0.93 (citric acid acidity; w / v%), and contains eriocitrin equivalent to 1800 ppm.

  Next, an acceleration aging test was performed by allowing each lemon-style beverage to stand at 60 ° C. for 3 days. About each lemon-like drink, the light absorbency in 420 nm and 520 nm of the thing immediately after manufacture (non-aging product) and the thing left still at 60 degreeC (aging product) was measured using the spectrophotometer, respectively. Furthermore, the flavor evaluation in <Evaluation 1 of a polyphenol containing material> of the said Example 7 was implemented about each lemon-like drink. The results are shown in Table 12.

表１２に示すように、精製工程において、洗浄処理に用いる洗浄用溶媒として、常温よりも高い温度の水（温水）又は１０容量％の含水エタノールを用いることにより、常温の水を用いる場合よりも、苦味・雑味の少ないポリフェノール含有素材を製造可能であることが示された。また、ベントナイト処理により、褐変及び苦味・雑味の少ないポリフェノール含有素材を容易に製造できることも再確認された。

As shown in Table 12, in the purification process, by using water (warm water) having a temperature higher than room temperature or 10% by volume of water-containing ethanol as a solvent for washing used in the washing treatment, water at room temperature is used. It was shown that it is possible to produce a polyphenol-containing material with little bitterness and miscibility. It was also reconfirmed that the bentonite treatment can easily produce a polyphenol-containing material with less browning and less bitterness and miscellaneous taste.

Further, the technical idea that can be grasped from the embodiment will be described below.
In the treatment step, the concentration of the polyphenol contained in the solution containing the extract is small, and the content of components exhibiting odor, bitterness, and miscellaneous taste is greatly reduced. Item 3. A method for producing a polyphenol-containing material according to Item 2.

-The polyphenol containing material manufactured by the manufacturing method of the polyphenol containing material as described in any one of Claims 1-5.
A method for producing a material containing a citrus-derived polyphenol, the method comprising immersing the citrus fruit or its constituents in an extraction solvent to obtain an extract containing the polyphenol, and the extraction A bentonite treatment step on the product, wherein the bentonite is added to the aqueous solution containing the extract and allowed to coexist, and then the bentonite is removed from the aqueous solution. A method for producing a polyphenol-containing material.

  A method for producing a material containing a citrus-derived polyphenol, the method comprising immersing the citrus fruit or its constituents in water to obtain an aqueous extract containing the polyphenol, and the water A treatment step of treating the extract with bentonite, and in the treatment step, after adding bentonite to the water extract and causing it to coexist, an operation of removing the bentonite from the water extract is performed. A method for producing a characteristic polyphenol-containing material.

Claims (6)

A method for producing a material containing at least one polyphenol selected from citrus-derived eriocitrin, hesperidin, and naringin ,
The method includes an extraction step to obtain an aqueous solution containing water as a main component containing said citrus fruits or component thereof is immersed in the extraction solvent extract containing the polyphenol, water containing extract primarily And a treatment step of performing a bentonite treatment on an aqueous solution as a component ,
In the processing step, polyphenol-containing material, characterized in that after being coexistent with the addition of bentonite in water solution containing water as a main component with containing the extract, the operation of removing the bentonite from the solution is carried out Manufacturing method.   In the said extraction process, pectinase is added to the said extraction solvent, The manufacturing method of the polyphenol containing material of Claim 1 characterized by the above-mentioned.   In the treatment step, components exhibiting unpleasant odor, bitterness and miscellaneous taste contained in the extract are adsorbed on the bentonite, and these components are removed from the solution together with the bentonite. The manufacturing method of the polyphenol containing raw material of Claim 1 or Claim 2.   4. The method for producing a polyphenol-containing material according to claim 1, wherein yellowishness and redness of a solution containing the extract are reduced in the treatment step. 5. The method further includes a purification step after the treatment step,
In the purification step, an adsorption treatment for adsorbing the treatment liquid after the treatment step onto an adsorption resin, a washing treatment for washing the adsorption resin after the adsorption treatment with water or a 20% by volume or less hydrous alcohol, and the washing treatment The method for producing a polyphenol-containing material according to any one of claims 1 to 4, wherein an elution treatment for eluting the polyphenol from the adsorbing resin later is performed.   Food-drinks containing the polyphenol containing material manufactured by the manufacturing method of the polyphenol containing material as described in any one of Claims 1-5.