JP4242908B2 - Method for producing purified tea extract - Google Patents

Description

  The present invention relates to a method for producing a purified tea extract.

  As an effect of catechin, an α-amylase activity inhibitory action and the like have been reported (for example, see Patent Document 1). In order to express such a physiological effect, in order to ingest a large amount of catechin, a technique for blending a high concentration of catechin into a beverage has been desired.

  As one of the methods, a method of adding a catechin to a beverage in a dissolved state using a tea extract such as a concentrate of a green tea extract is used. However, depending on the type of beverage for which catechin is blended at a high concentration, for example, when adding catechin to tea-based beverages, non-tea-based beverages such as carbonated beverages, etc., bitterness derived from caffeine and green tea It has been found that remaining and coloring greatly impairs the commercial value of beverages.

Adsorption methods (Patent Documents 2 to 4), extraction methods (Patent Documents 5 to 6), and the like are known as methods for removing impurities such as caffeine from tea extracts.
In the above method, when increasing the content of non-polymer catechins in the tea extract, it is necessary to use an organic solvent. However, when viewed industrially, there is a problem that the recovery rate is low. .
As a method for improving the color tone of the tea extract, an adjustment method of an antibacterial deodorant obtained by causing activated carbon to act on the tea extract in the presence of cyclodextrin and adsorbing and removing the coloring components on the activated carbon (Patent Document 7) However, its use in beverage catechin preparations has been difficult.
JP-A-3-133828 JP-A-5-153910 JP-A-8-109178 JP 2002-335911 A JP-A-1-289447 JP 59-219384 A JP 2001-299887 A

  An object of the present invention is to provide a method for producing a purified tea extract having a high recovery rate of non-polymer catechins, a low caffeine content, a good color tone, and an improved taste.

  The present inventor has a first step of selectively eluting non-polymer catechins with an organic solvent aqueous solution or a basic aqueous solution after adsorbing the tea extract to the synthetic adsorbent, and further the organic solvent aqueous solution as the eluent. By performing the second step in which the activated carbon is brought into contact, non-polymer catechins can be recovered in a high yield, a good color tone, a reduced caffeine content, and a purified product with improved taste can be obtained. I found out.

In the present invention, first, after a tea extract is adsorbed on a synthetic adsorbent, the synthetic adsorbent is washed with an organic solvent aqueous solution having an organic solvent concentration of 0 to 5% by mass, and the synthetic adsorbent has an organic solvent concentration of 8 to 8. A method for producing a purified tea extract comprising contacting a 60% by mass organic solvent aqueous solution to elute non-polymer catechins, and then contacting the eluate with activated carbon in an organic solvent aqueous solution having an organic solvent concentration of 1 to 80% by mass. It is to provide.
Second, after the tea extract is adsorbed on the synthetic adsorbent, the synthetic adsorbent is washed with an organic solvent aqueous solution having an organic solvent concentration of 0 to 5% by mass, and the basic adsorbent is brought into contact with the synthetic adsorbent so Provided is a method for producing a purified tea extract in which coalescent catechins are eluted, and then the eluate is contacted with activated carbon in an organic solvent aqueous solution having an organic solvent concentration of 1 to 80% by mass .
In the present invention, the non-polymer catechins in the solid content are 25 to 95% by mass, the gallate content in the non-polymer catechins is 0 to 70% by mass, and the ratio of gallic acid to non-polymer catechins is 0. 0.1 to 0, the color tone at 450 nm when the ratio of caffeine to non-polymer catechins is 0 to 0.2 and the concentration of non-polymer catechins is 1% by mass is 0 or more and 0 The present invention provides a purified tea extract that is .8 or less.

  According to the present invention, a purified tea extract having a high recovery rate of non-polymer catechins, a low caffeine content, a good color tone and an improved taste can be obtained.

  In the present invention, the non-polymer catechins include non-epi catechins such as catechin, gallocatechin, catechin gallate and gallocatechin gallate and epi-catechins such as epicatechin, epigallocatechin, epicatechin gallate and epigallocatechin gallate. It is a general term.

In the present invention, the non-polymer catechin gallate body is a general term including catechin gallate, gallocatechin gallate, epicatechin gallate, epigallocatechin gallate and the like.
The percentage of gallate body in non-polymer catechins is a weight ratio of the non-polymer catechin gallate body to the total amount of non-polymer catechins.

Examples of the tea extract used in the present invention include an extract obtained from tea leaves. A mixture of a caffeine-containing extract such as coffee and a tea extract derived from other caffeine-containing plants can also be used. More specifically, the tea leaves used include tea leaves made from tea leaves obtained from the genus Camellia, for example, C. sinensis, C. assamica, and camellia seeds or hybrids thereof. The tea leaves produced include green teas such as sencha, bancha, gyokuro, tencha, roasted tea, semi-fermented tea typified by oolong tea, and fermented tea typified by black tea. Moreover, you may use the tea leaf which gave the carbon dioxide contact process of the supercritical state. The tea extract used in the present invention is preferably a green tea extract from the viewpoint of the content of non-polymer catechins.
About the method of extracting tea, it carries out by conventional methods, such as stirring extraction and drip extraction. Moreover, you may add organic acids or organic acid salts, such as sodium ascorbate, to the water at the time of extraction beforehand. Moreover, you may use together the method of extracting in so-called non-oxidative atmosphere, ventilating boil degassing and inert gas, such as nitrogen gas, and removing dissolved oxygen. The extract thus obtained can be used in the present invention as it is, even if it is dried and concentrated. Examples of the tea extract include liquid, slurry, semi-solid, and solid state.

For the tea extract used in the present invention, instead of using an extract extracted from tea leaves, a concentrate of tea extract dissolved or diluted in water or an organic solvent may be used. You may use together with the concentrate of a tea extract.
Here, the concentrate of tea extract is obtained by concentrating an extract extracted from tea leaves with hot water or an organic solvent aqueous solution. For example, JP-A-59-219384 and JP-A-4-20589. This refers to those prepared by the methods described in JP-A-5-260907, JP-A-5-306279, and the like. Specifically, as a tea extract, a commercially available crude catechin preparation such as “Polyphenone” manufactured by Tokyo Food Techno Co., “Theafuran” manufactured by ITO EN, or “Sunphenon” manufactured by Taiyo Kagaku Co., Ltd. it can.

  As the synthetic adsorbent, generally an insoluble three-dimensional crosslinked structure polymer which does not substantially have a functional group such as an ion exchange group, and preferably has an ion exchange capacity of less than 1 meq / g. . The matrix of the synthetic adsorbent is preferably styrene, methacrylic, acrylic or polyvinyl, and styrene is particularly preferred from the viewpoint of separability between catechin and caffeine. As specific synthetic adsorbents, the matrix is styrene, such as Amberlite XAD4, XAD16HP, XAD1180, XAD2000 (supplier: Rohm & Haas, USA), Diaion HP20, HP21 (Mitsubishi Chemical), Sepabeads SP850, SP825, SP700, SP70 (manufactured by Mitsubishi Chemical Corporation), VPOC1062 (manufactured by Bayer Corporation); modified styrene series in which the bromine atom is replaced with a nucleus to enhance the adsorptive power, for example, Sepabeads SP205, SP206, SP207 (manufactured by Mitsubishi Chemical Corporation) Methacrylic, for example Diaion HP1MG, HP2MG (Mitsubishi Chemical); phenolic, for example Amberlite XAD761 (Rohm and Haas); acrylic, for example Amberlite XAD7HP (Rohm and Haas); polyvinyl For example TOYOPEARL, HW-40C (manufactured by Tosoh Corporation); dextran based, for example SEPHADEX, LH-20 (Pharmacia) or the like can be used.

  As a means for adsorbing the tea extract to the synthetic adsorbent, the synthetic adsorbent is added to the tea extract and its aqueous solution, stirred, adsorbed, and then packed with a batch method or synthetic adsorbent that collects the synthetic adsorbent by filtration. A column method in which adsorption treatment is performed by continuous treatment using a column is employed, but a continuous treatment method using a column is preferable from the viewpoint of productivity.

The column packed with the synthetic adsorbent is preliminarily SV (space velocity) = 0.5 to 10 [h ⁻¹ ], and 95 vol under a liquid passing condition of 2 to 10 [v / v] as the liquid passing ratio with respect to the synthetic adsorbent. It is preferable to remove the raw material monomer of the synthetic adsorbent, impurities in the raw material monomer, etc. by washing with a% ethanol aqueous solution. Then, SV = 0.5 to 10 [h ⁻¹ ], and a water passage condition of 1 to 60 [v / v] as a liquid passage ratio with respect to the synthetic adsorbent is performed to remove ethanol and remove the synthetic adsorbent. The ability to adsorb non-polymer catechins is improved by replacing the liquid-containing solution with an aqueous system.

  As conditions for passing the tea extract through the column, when adsorbing to the synthetic adsorbent, the concentration of non-polymer catechins in the tea extract is preferably 0.1 to 22% by mass, more preferably 0.1 to 15% by mass, particularly preferably 0.5 to 10% by mass, particularly preferably 0.5 to 3% by mass is preferable from the viewpoint of the adsorption efficiency to the synthetic adsorbent.

The condition for passing the tea extract through the column filled with the synthetic adsorbent is SV (space velocity) = 0.5 to 10 [h ⁻¹ ], and the flow rate of the synthetic adsorbent is as a multiple. It is preferable to pass the liquid at 0.5 to 20 [v / v]. If the non-polymer catechins are not sufficiently adsorbed at a flow rate of 10 [h ^-1 ] or higher, or if the non-polymer catechins are not stably adsorbed if the flow rate is 20 [v / v] or higher. There is.

  After adsorbing the tea extract, the synthetic adsorbent is preferably washed with water or an organic solvent aqueous solution. The aqueous solution used for washing the synthetic adsorbent is preferably water having a pH of 7 or less from the viewpoint of catechin recovery, and can also be used in a mixed system with an organic solvent. Examples of the organic solvent include acetone, methanol, ethanol and the like, and ethanol is preferable from the viewpoint of use in foods. The concentration of the organic solvent to be contained is preferably 0 to less than 5% by mass, preferably 0 to 2% by mass, and more preferably 0 to 1% by mass from the viewpoint of catechin recovery.

In this washing step, SV (space velocity) = 0.5 to 10 [h ⁻¹ ], and 1 to 10 [v / v] as a solution passage ratio with respect to the synthetic adsorbent, It is preferable to remove adhering impurities. Further, it is possible to wash at a flow rate of SV = 0.5 to 5 [h ⁻¹ ] and a flow rate of 1 to 5 [v / v] to remove impurities and to recover non-polymer catechins. From the point of view, it is preferable.

When the organic solvent aqueous solution of the first invention is used as an eluent, the organic solvent used for elution of non-polymer catechins is preferably a water-soluble organic solvent, and includes acetone, methanol, ethanol, etc. From the viewpoint of use, ethanol is preferable. Such an organic solvent is preferably used as an aqueous solution from the viewpoint that the yield of non-polymer catechins is large and the amount of impurities is reduced. The concentration of the organic solvent is 8 to 60% by mass , particularly 10 to 40 %. It is preferably used as a mass% aqueous solution.
Non-polymer catechins can be eluted at a flow rate of SV (space velocity) = 0.5 to 5 [h ⁻¹ ] and a flow rate of 1 to 15 [v / v] with respect to the synthetic adsorbent. preferable. Furthermore, it is preferable from the viewpoint of productivity and the recovery rate of non-polymer catechins to elute at a liquid flow rate of SV = 1 to 3 [h ⁻¹ ] and a liquid flow rate of 2 to 10 [v / v].
When an organic solvent aqueous solution is used as an eluent used for elution of non-polymer catechins, it is preferable from the viewpoint of simplification of the process and purification cost.

  In the elution step, two or more organic solvent aqueous solutions having different concentrations are used as the organic solvent aqueous solution used for elution, and these organic solvent aqueous solutions can be brought into contact with the synthetic adsorbent in the order of decreasing concentration. Different non-polymer catechins and other components can be desorbed in each concentration category.

  The eluate containing non-polymer catechins is concentrated or hydrated to precipitate the precipitate, and solid-liquid separation is performed to remove the precipitate (turbidity removing step). It is preferable for improving the performance.

To precipitate a precipitate, the eluate is concentrated or added with water. The ethanol concentration is adjusted by operation to precipitate impurities. The concentration of ethanol after concentration or addition is preferably 0.01 to 40% by mass, more preferably 0.1 to 30% by mass, and still more preferably 0.2% from the viewpoint of taste and separability of precipitated impurities. ˜20 mass%. The concentration of the non-polymer catechins in the eluate is preferably from 0.1 to 60% by mass, more preferably from 0.8 to 30% by mass, from the viewpoint of taste and separability of precipitated impurities. 0-15 mass% is still more preferable.
The aging time for depositing the turbid component is not particularly limited. For example, it is preferably 2 minutes to 50 hours, more preferably 2 minutes to 24 hours, and particularly preferably 5 minutes to 6 hours. Moreover, the precipitation temperature of a turbid component is -5-40 degreeC from the point which lowers the solubility of a precipitate, and after the turbid component is deposited, from the point of the taste and the separability of the deposited foreign substance, and also 5-25 degreeC. Is preferred.

  Specific operations for solid-liquid separation include filtration and / or centrifugation. The turbidity of the tea extract aqueous solution, which is a water-soluble part obtained by solid-liquid separation of the tea extract aqueous solution, is 0.1 to 100 NTU, more preferably 0.5 to 70 NTU, still more preferably 1 to 50 NTU. From the viewpoint of taste and stability of the beverage. Turbidity is measured with 2100P type (manufactured by Hack Co., Ltd.), and the value [unit: NTU] obtained here can be used as an index of separation clarity.

As a solid-liquid separation method, a method that can be used in the food industry can be applied. For example, as membrane filtration conditions when performing solid-liquid separation by membrane filtration, the temperature is preferably 5 to 70 ° C, and more preferably 10 to 40 ° C. The membrane pore size is preferably 0.1 to 10 μm from the viewpoint of a predetermined turbidity, more preferably 0.1 to 5 μm, and particularly 0.1 to 2 μm is the time required for filtration and the separability of turbid components. It is preferable from the point. Examples of the method for measuring the membrane pore diameter include general measurement methods using a mercury intrusion method, a bubble point test, a bacterial filtration method, and the like, but it is preferable to use a value obtained by a bubble point test. As the material of the membrane used in the membrane filtration, a polymer membrane, a ceramic membrane, a stainless membrane or the like can be used.
The centrifuge is preferably a general device such as a separation plate type, a cylindrical type, or a decanter type. As the centrifugation conditions, the temperature is preferably 5 to 70 ° C., more preferably 10 to 40 ° C., and the rotation speed and time are preferably adjusted so as to have a predetermined turbidity. For example, in the case of a separator plate type, it is 3000 to 10000 r / min, further 5000 to 10000 r / min, particularly 6000 to 10000 r / min, 0.2 to 30 minutes, further 0.2 to 20 minutes, particularly 0.2 to 15 minutes. Is preferred.

  When the basic aqueous solution of the second invention is used, the basic aqueous solution used for elution of the non-polymer catechins is an alkaline aqueous solution such as an alkali metal salt or alkaline earth metal salt, preferably sodium or potassium alkaline An aqueous solution such as an aqueous sodium hydroxide solution or an aqueous sodium carbonate solution can be suitably used. The pH of the alkaline aqueous solution is preferably in the range of 7 to 14, and preferably 9 to 13.8, particularly preferably 10 to 13.5, from the viewpoint of the recovery rate of non-polymer catechins. Examples of the sodium-based aqueous solution having a pH of 7 to 14 include a 4% or less sodium hydroxide aqueous solution and a 1N-sodium carbonate aqueous solution. You may mix and use basic aqueous solution and an organic solvent. As a density | concentration of an organic solvent, the range of 0-90 mass% is preferable from the point of the separability of caffeine and catechin, 0-50 mass% is more preferable, 0-20 mass% is still more preferable.

  In the elution step, two or more basic aqueous solutions having different pH values are used as the basic aqueous solution used for elution, and these basic aqueous solutions can be brought into contact with the synthetic adsorbent in order of decreasing pH. Different non-polymer catechins and other components can be desorbed in each pH category.

It is preferable to elute non-polymer catechins at a flow rate of SV (space velocity) = 2 to 10 [h ⁻¹ ] and a flow rate of 1 to 30 [v / v] with respect to the synthetic adsorbent. Furthermore, it is preferable from the viewpoint of productivity and the recovery rate of non-polymer catechins to elute at a liquid passing rate of SV = 3 to 7 [h ⁻¹ ] and a liquid passing ratio of 3 to 15 [v / v].
When a basic aqueous solution is used as an eluent used for elution of non-polymer catechins, it is preferable from the viewpoint of the color tone of the purified tea extract and the recovery rate in the activated carbon treatment.

  When eluted with a basic aqueous solution, the eluate of non-polymer catechins is basic. From the viewpoint of the stability of the non-polymer catechins, the pH of the eluate is preferably 7 or less, more preferably the pH. It is adjusted to 1 to 6, more preferably 1 to 5, particularly preferably 2 to 4. Specifically, neutralization with an acid, removal of alkali metal ions by electrodialysis, or removal of alkali metal ions by an ion exchange resin can be used. As the ion exchange resin, it is particularly preferable to use an H-type cation exchange resin. From the simplicity of the process, pH adjustment with an ion exchange resin is preferred. Specifically, Amberlite 200CT, IR120B, IR124, IR118, Diaion SK1B, SK1BH, SK102, PK208, PK212, etc. can be used as the cation exchange resin.

  In the case of elution with a basic aqueous solution, it is preferable to concentrate the eluate after neutralization and remove the precipitated impurities by solid-liquid separation for improving taste and product stability. Concentration can be performed by vacuum distillation, thin film distillation, membrane concentration, or the like. The concentration factor is preferably 2 to 500 times, more preferably 2 to 250 times, and particularly preferably 2 to 125 times from the viewpoint of taste and separability of precipitated impurities. The concentration of the non-polymer catechins after the concentration is 0.1 to 60% by mass, more preferably 0.2 to 30% by mass, and particularly 0.5 to 15% by mass from the viewpoint of taste and separability of the deposited impurities. Is preferred. Specific operations for solid-liquid separation include filtration and / or centrifugation. The turbidity of the tea extract aqueous solution, which is a water-soluble part obtained by solid-liquid separation of the tea extract aqueous solution, is 0.1 to 100 NTU, more preferably 0.5 to 70 NTU, still more preferably 1 to 50 NTU. From the viewpoint of taste and stability of the beverage. Turbidity is measured with 2100P type (manufactured by Hack Co., Ltd.), and the value [unit: NTU] obtained here can be used as an index of separation clarity.

  As the solid-liquid separation method, a method that can be used in the food industry can be applied as in the case of the first invention.

The eluate is brought into contact with activated carbon in an organic solvent aqueous solution. Examples of the activated carbon material include coconut shell, wood, and coal, but wood is preferred. Examples of the activated carbon activation method include a steam activation method, a gas activation method, and a chemical activation method, and the chemical activation method is preferable.
For example, ZN-50, Y-10S, GS-1, GS-B (manufactured by Ajinomoto Fine Techno), Kuraray Coal GLC, Kuraray Coal PK-D, Kuraray Coal PW-D, Kuraray Coal GW, Kuraray Coal GA, Kuraray Coal GA-D, Kuraray Coal RP-15 (manufactured by Kuraray Chemical Co., Ltd.), white birch AW50, white birch A, white birch P, white birch KL, white birch M, white birch C, carborafine, WH2C (manufactured by Nippon Envirochemicals), GM130A, CW130A, CW130AR , CW350AR, GL130A, SG, SGA, SGP (manufactured by Phutamura Chemical), coconut, MAS mark, plum bee mark, plum bee F mark (manufactured by Taihei Chemical Sangyo), CPG, CAL, S80A (manufactured by Mitsubishi Chemical Calgon), etc. Product can be used.

From the viewpoint of improving the color tone of the product, reducing the amount of activated carbon used, and improving the recovery rate, the following are preferable as the activated carbon. The average pore diameter is preferably 0.5 to 10 nm (nanometer), more preferably 1.0 to 9.0 nm (nanometer), and particularly preferably 2.0 to 8.0 nm (nanometer). The pore volume is preferably 0.01 to 2.5 mL / g, more preferably 0.1 to 2.0 mL / g, and particularly preferably 0.5 to 1.7 mL / g. The specific surface area is 800~2000m ² / g, further 900~1600m ² / g, particularly preferably in the range of 1000~1500m ² / g. These physical property values are values based on the nitrogen adsorption method.

  Activated carbon is added in an amount of 1 to 200 parts by weight, more preferably 5 to 100 parts by weight, particularly 10 to 80 parts by weight with respect to 100 parts by weight of non-polymer catechins in the eluate, thereby improving the purification effect and the recovery rate. It is preferable at a point with the small cake resistance in a filtration process.

Examples of the organic solvent used when contacting with activated carbon include acetone, methanol, ethanol and the like, and ethanol is preferable from the viewpoint of use in foods. Such an organic solvent is used as an aqueous solution from the viewpoints of a good product color tone, a high yield of non-polymer catechins, and a small amount of impurities. The organic solvent concentration is preferably 1 to 80% by weight, more preferably 2 to 70% by weight, particularly 5 to 50% by weight, particularly 7 to 40% by weight.
When contacting with activated carbon, the concentration of non-polymer catechins in the organic solvent aqueous solution is 0.5 to 20% by mass, more preferably 1 to 15% by mass, particularly 2 to 8% from the viewpoint of improving the purification effect and the recovery rate. Mass% is preferred.
When contacting with activated carbon, the eluate from the synthetic adsorbent is adjusted to a prescribed concentration of solvent and non-polymer catechins by adding water or organic solvent aqueous solution, vacuum concentration, membrane concentration, desolvation, etc. It is preferable.

  As a means for bringing the activated carbon into contact, an activated tank is added to the eluate, stirred and adsorbed, and then a stirring tank method for collecting the activated carbon by filtration operation or a column method for contacting by continuous treatment using a column filled with activated carbon is adopted. However, the continuous processing method by the column method is preferable from the viewpoint of productivity.

  The purified tea extract obtained by the present invention contains 25 to 95% by mass of non-polymer catechins in the solid content, but is 40 to 95% by mass, more preferably 50 to 90% by mass, particularly 60 to 85% by mass. % Content is preferable for blending into beverages.

  In the purified tea extract obtained by the present invention, the proportion of gallate bodies composed of catechin gallate, epicatechin gallate, gallocatechin gallate and epigallocatechin gallate in all non-polymer catechins is 0 to 70% by mass. Further, 1 to 60% by mass, particularly 2 to 40% by mass, particularly 10 to 35% by mass is preferable from the viewpoint of the effectiveness of physiological effects of non-polymer catechins and the reduction of bitterness.

  The concentration of caffeine in the purified tea extract obtained in the present invention is caffeine / non-polymer catechins (mass ratio) = 0 to 0.2, more preferably 0 to 0.15 with respect to non-polymer catechins. In particular, it is preferably 0 to 0.1, more preferably 0 to 0.05, and particularly preferably 0 to 0.035 from the viewpoint of improving taste.

  The ratio (mass ratio) of gallic acid and non-polymer catechins in the purified tea extract obtained in the present invention is 0 to 0.1, more preferably 0 to 0.07, and particularly 0 to 0.05. Is preferable in terms of taste improvement and color tone.

  As for the color tone of the purified tea extract obtained in the present invention, the color tone (/ cm) at 450 nm when the concentration of the non-polymer catechins is 1% by mass is 0 to 0.8, and further 0.01 It is preferable that it is -0.75, especially 0.1-0.6, especially 0.2-0.5 from the point of the color tone when mix | blending with a drink, and the point of refinement | purification cost.

The tea extract can be hydrolyzed when it is desired to further reduce the bitterness. The hydrolysis treatment is preferably performed before the resin treatment of the present invention. As the hydrolysis treatment, treatment with an enzyme having tannase activity is preferred. From the viewpoint of taste, it is preferable to perform an enzyme treatment before adsorbing to the synthetic adsorbent.
Specifically, pectinase PL Amano (manufactured by Amano Enzyme), hemicellulase amano 90 (manufactured by Amano Enzyme), tannase KTFH (manufactured by Kikkoman), etc. can be used as commercially available enzymes having tannase activity. Of these, tannase is preferred. For example, tannase obtained by culturing tannase-producing bacteria belonging to the genus Aspergillus, Penicillium or Rhizopus. Of these, those derived from Aspergillus oryzae are preferred.
The enzyme treatment having tannase activity performed in the present invention, that is, the enzyme reaction, is preferably performed by tannin acylhydrase EC 3.1.1.20 or the like. As a commercial item, brand name "Tannase" product made by Kikkoman Co., Ltd., tannase "Sankyo" product made by Sankyo Co., Ltd., etc. are mentioned.
The enzyme having tannase activity to be used in the present invention preferably has an enzyme activity of 500 to 100,000 U / g. If it is 500 U / g or less, a large amount is required for treatment within an industrially limited time. The enzyme reaction rate is too high when it is 100,000 U / g or more, and it becomes difficult to control the reaction system. Here, 1 Unit represents the amount of enzyme that hydrolyzes 1 micromole of an ester bond contained in tannic acid in water at 30 ° C. Here, having tannase activity has activity of degrading tannin, and any enzyme can be used as long as it has this activity.

The non-polymer catechin concentration during the treatment with an enzyme having tannase activity is preferably 0.1 to 22% by mass, more preferably 0.1 to 15% by mass, particularly preferably 0.5 to 10% by mass, and even more preferably. Is 0.5-3 mass%. If the amount is less than 0.1% by mass, the amount of adsorption decreases during the subsequent adsorption to the synthetic adsorbent. If the amount exceeds 22% by mass, the hydrolysis process takes a long time, and productivity and the taste of the tea extract are required. Is not preferable.
Enzymes having tannase activity for non-polymer catechins in tea extract are preferably 1-300 Unit / g-non-polymer catechin, more preferably 3-200 Unit / g-non-polymer catechin, particularly preferably Add 5-150 Unit / g-non-polymer catechin.
The temperature of the enzyme treatment is preferably from 0 to 70 ° C., more preferably from 0 to 60 ° C., particularly preferably from 5 to 50 ° C. at which the optimum enzyme activity can be obtained.

In order to terminate the enzyme reaction, it is necessary to deactivate the enzyme activity. The enzyme deactivation temperature is preferably 70 to 100 ° C.
The enzyme can be deactivated by heating in a continuous manner such as a batch type or a plate type heat exchanger. In addition, after inactivation of tannase, the tea extract can be cleaned by an operation such as centrifugation.

  The purified tea extract obtained in the present invention can be used as a beverage as it is. Further, the solvent may be removed by a method such as vacuum concentration or thin film concentration. When powder is desirable as the product form of the purified tea extract, it can be pulverized by a method such as spray drying or freeze drying.

  The concentration of non-polymer catechins in a packaged beverage using the purified tea extract of the present invention is 0.05 to 0.5% by mass, preferably 0.06 to 0.5% by mass, and further 0.08 to 0. When adjusted to 5% by mass, more preferably 0.092 to 0.4% by mass, even more preferably 0.11 to 0.3% by mass, particularly preferably 0.12 to 0.3% by mass, This is preferable in that a packaged beverage having a good flavor can be obtained.

  The ratio of the generic gallate body consisting of catechin gallate, epicatechin gallate, gallocatechin gallate and epigallocatechin gallate in the non-polymer catechins in the packaged beverage is 0 to 70% by mass, and further 1 to 60%. The mass%, particularly 2 to 40 mass%, particularly 10 to 35 mass% is preferable in terms of the effectiveness of the physiological effects of taste and non-polymer catechins.

  In addition, the gallic acid content in the packaged beverage of the present invention is preferably less than 10 mg / 100 mL from the viewpoint of bitterness, sourness-reducing effect, and storage stability of flavor and color.

  The packaged beverage of the present invention can be used as a tea-based beverage and a non-tea beverage. Specific examples of non-tea beverages include acidic beverages containing sweeteners and fruit flavors, and sports beverages or isotonic beverages.

As the sweetener used in the packaged beverage of the present invention, artificial sweeteners, carbohydrates, and glycerol (for example, glycerin) are used.
Fruit flavors include fruit juice and fragrance. In general, fruit juice is called fruit juice, and flavor is called flavor. Natural or synthetic flavors and fruit juice containing these can be used in the present invention.

When the packaged beverage of the present invention is a sports drink or an isotonic beverage, it is preferable to contain sodium ions and / or potassium ions.
Furthermore, if necessary, the beverage of the present invention may contain a sour agent. Examples of acidulants include edible acids such as malic acid, citric acid, tartaric acid, fumaric acid and the like. A sour agent may be used to adjust the pH of the beverage of the present invention.

  The container-packed beverage of the present invention is preferably mixed with a bitter and astringent taste suppressant because it is easy to drink. The bitter and astringent taste inhibitor to be used is not particularly limited, but cyclodextrin is preferred. As the cyclodextrin, α-, β-, γ-cyclodextrin and branched α-, β-, γ-cyclodextrin can be used. The cyclodextrin is preferably contained in the beverage in an amount of 0.005 to 0.5 mass%, more preferably 0.01 to 0.3 mass%. The packaged beverage of the present invention includes antioxidants, various esters, inorganic salts, pigments, emulsifiers, preservatives, seasonings, sweeteners, sour agents, gums, emulsifiers, oils, vitamins, amino acids, vegetable extracts. , Nectar extracts, pH adjusters, quality stabilizers and the like can be added alone or in combination.

  The pH of the packaged beverage of the present invention is preferably 2 to 7, preferably 2 to 6.5 at 25 ° C. from the viewpoint of taste and stability of non-polymer catechins.

  In the packaged beverage of the present invention, from the viewpoint of securing the necessary daily intake for obtaining the physiological effect of catechin, 300 mg or more, preferably 450 mg or more, per one packaged beverage (350 to 500 mL) of the present invention, More preferably, the amount is 500 mg or more.

  Moreover, said container-packed drink is manufactured on the sterilization conditions prescribed | regulated to the food hygiene law, for example, when it can heat-sterilize after filling a container like a metal can. For PET bottles and paper containers that cannot be sterilized by retort, sterilize under the same conditions as above, for example, after sterilizing at high temperature and short time with a plate heat exchanger, etc. The method is adopted. Moreover, you may mix | blend another component with the filled container under aseptic conditions.

(1) Measurement sample solutions of catechins, caffeine and gallic acid are filtered through a filter (0.45 μm), and used for high performance liquid chromatograph (model SCL-10AVP) manufactured by Shimadzu Corporation for liquid chromatography with octadecyl group introduction A packed column L-column TM ODS (4.6 mmφ × 250 mm: manufactured by Chemical Substances Evaluation and Research Institute) was attached and analyzed by a gradient method at a column temperature of 35 ° C. The mobile phase A solution was a distilled aqueous solution containing 0.1 mol / L of acetic acid, the B solution was an acetonitrile solution containing 0.1 mol / L of acetic acid, the sample injection amount was 20 μL, and the UV detector wavelength was 280 nm. .

(2) Evaluation of taste of purified tea extract The purified green tea extract obtained in each example was deionized water so that the non-polymer catechin content was 0.175% [w / v]. Dilute and place 40 mL in a 50 mL pressure-resistant glass container. Thereto was added 0.1% by mass of Na ascorbate, the pH was adjusted to 6.4 with a 5% aqueous sodium bicarbonate solution, nitrogen substitution was performed, and the mixture was sterilized by heating in an autoclave at 121 ° C. for 10 minutes. Then, bitterness was evaluated about the taste and aftertaste by five evaluation panelists. The bitterness was determined by the quinine sulfate method. Moreover, regarding Example 10, evaluation about miscellaneous taste was performed by five evaluation panelists.

(3) Evaluation of bitterness by quinine sulfate method (equivalent concentration test method) Quinine sulfate dihydrate was adjusted to a concentration corresponding to the bitterness intensity described in the table. After tasting the evaluation sample, it was determined which sample of the standard bitterness solution had the same bitterness intensity. The bitterness intensity was confirmed by five evaluation panelists. (Reference: New edition Sensory Test Handbook, Nikkatsu Rensen Sensory Test Committee p448-449, Perception & Psychophysics, 5, 1696, 347-351)

(4) Color tone measurement Using a HITACHI spectrophotometer (model U-2001 type), dilute the glass cell with ion-exchanged water so that the concentration of the non-polymer catechins in the sample is 1% by mass. Measured. The measurement wavelength of the spectrophotometer at the time of analysis was set to 450 nm.

Example 1
Add 45 kg of 88 ° C hot water to 3 kg of green tea leaves (from Kenya, large-leaf seeds), extract with stirring for 60 minutes, perform coarse filtration through a 100 mesh wire mesh, and then centrifuge to remove fines in the extract To obtain 37.2 kg (pH 5.4) of “green tea extract” (non-polymer catechin concentration in green tea extract = 0.89 mass%, gallate body ratio of green tea extract = 52.3 mass) %, Caffeine 0.17% by mass). This green tea extract was kept at a temperature of 15 ° C., tannase (Kikkoman Tannase KTFH, 500 U / g) was added at a concentration of 430 ppm with respect to the green tea extract, kept for 55 minutes, and the gallate body fraction was 30. When it reached 5% by mass, the solution was heated to 90 ° C. and held for 2 minutes to inactivate the enzyme to stop the reaction (pH 5.1). Subsequently, concentration treatment was performed under reduced pressure concentration to a Brix concentration of 20% under conditions of 70 ° C. and 6.7 kpa, and further spray-dried to obtain 0.9 kg of a powdered “tannase-treated green tea extract”. The resulting green tea extract had a non-polymer catechin content of 27.8% by mass, a non-polymer catechin gallate content of 30.3% by mass, a caffeine content of 6.74% by mass, and a gallic acid of 3.58% by mass. Met. 285 g of “tannase-treated green tea extract” was dissolved in 8550 g of deionized water with stirring at 25 ° C. for 30 minutes (tannase treatment solution).

Next, 2209 mL of a synthetic adsorbent SP-70 (manufactured by Mitsubishi Chemical Corporation) was packed in a stainless steel column 1 (inner diameter 110 mm × height 230 mm, volume 2185 mL). Stainless steel column 2 (inner diameter 38 mm × height 770 mm, 877.4 volume mL) was charged with 852 mL of ion exchange resin SK1BH (manufactured by Mitsubishi Chemical Corporation). In both columns, SV = 5 (h ⁻¹ ) and 95% (v / v) ethanol through 4 times volume (vs. packed resin), and then 10 times volume (vs. filled resin) of water. Washed. Thereafter, 8835 g of the tannase treatment solution (4 volumes vs. synthetic adsorbent) was passed through the column 1 at SV = 1 (h ⁻¹ ), and the permeate was discarded. It was then washed with 2209 mL (1 volume vs. synthetic adsorbent) of water at SV = 2 (h ⁻¹ ). After washing with water, 13256 mL of 0.1 mass% sodium hydroxide aqueous solution (pH 12.4) was passed through at SV = 5 (h ⁻¹ ) (6 times volume vs. synthetic adsorbent). The eluate was continuously passed through the column 2 for deionization to obtain 13080 g (pH 3.3) of a non-polymer catechin composition. This extract contained 0.38% by mass of non-polymer catechins, and the gallate content of the non-polymer catechins composition was 28.6% by mass. The amount of caffeine was 0% by mass and the amount of gallic acid was 0.002% by mass. The non-polymer catechins in the solid content of the tea extract was 69.0% by mass. Furthermore, it concentrated under reduced pressure on 40 degreeC and 2.6 kPa conditions, and concentrated to non-polymer catechin density | concentration 6% (turbidity 208NTU). Next, it was passed through a 0.8 μm cellulose acetate membrane (ADVANTEC: C080A090C), and was subjected to solid-liquid separation from the suspension to obtain “resin-treated product 1” (turbidity 1.5 NTU). Next, 6.5 g of granular activated carbon Taiho SGP (Futamura Chemical Co., Ltd.) was packed in a stainless steel column 3 (inner diameter 22 mm × height 145 mm, volume 55.1 mL). “Resin-treated product 1” was prepared so as to have a non-polymer catechin concentration of 4% and an ethanol concentration of 20% by mass, and 267 g of the solution was passed through column 3 with SV = 2 (h ⁻¹ ) (active carbon The amount is 0.6) relative to the amount of non-polymer catechins. Subsequently, filtration was performed with a 0.2 μm membrane filter. Finally, 50 g of ion-exchanged water was added, ethanol was distilled off under the conditions of 40 ° C. and 2.7 kPa, and then the water content was adjusted to obtain “activated carbon product 1” (2.1 NTU). This extract contained 13.7% by mass of non-polymer catechins, and the gallate content of the non-polymer catechins composition was 23.5% by mass. The amount of caffeine was 0% by mass and the amount of gallic acid was 0.054% by mass. The non-polymer catechins in the solid content was 79.6% by mass.

Comparative Example 1
“Resin-treated product 1” in Example 1.

Example 2
A stainless steel column 4 (inner diameter 110 mm × height 230 mm, volume 2185 mL) was filled with 2048 mL of synthetic adsorbent SP-70 (manufactured by Mitsubishi Chemical Corporation). The column was previously washed in the same manner as in Example 1. Thereafter, 8191 g of the tannase treatment solution obtained in Example 1 (4 times volume vs. synthetic adsorbent) was passed through the column 4 at SV = 1 (h ⁻¹ ), and the permeate was discarded. It was then washed with 2048 mL (1 volume vs. synthetic adsorbent) of water at SV = 2 (h ⁻¹ ). After washing with water, a 20 mass% ethanol aqueous solution was passed through 12287 mL (6 times volume to synthetic adsorbent) at SV = 2 (h ⁻¹ ) to obtain 12090 g (pH 2.1) of a non-polymer catechin composition. This extract contained 0.51% by mass of non-polymer catechins, and the gallate content of the non-polymer catechins composition was 27.4% by mass. The amount of caffeine was 0.075% by mass and the amount of gallic acid was 0.002% by mass. The non-polymer catechins in the solid content of the tea extract was 62.5% by mass. Further, ethanol was distilled off at 40 ° C. and 2.7 kPa by concentration under reduced pressure, and then the water content was adjusted to obtain “resin-treated product 2”. Next, contact treatment with activated carbon was performed in the same manner as in Example 1 (the amount of activated carbon was 0.6 relative to the amount of non-polymer catechins) to obtain “activated carbon product 2” (1.7 NTU). This extract contained 15.0% by mass of non-polymer catechins, and the gallate content of the non-polymer catechins composition was 20.9% by mass. The amount of caffeine was 0.264% by mass and the amount of gallic acid was 0.057% by mass. The non-polymer catechins in the solid content was 72.8% by mass.

Comparative Example 2
“Resin-treated product 2” in Example 2.

  Table 2 shows the results of comparison between Example 1 and Comparative Example 1, and Example 2 and Comparative Example 2.

  As is clear from Table 2, after adsorbing the tea extract to the synthetic adsorbent, it is eluted with an organic solvent aqueous solution or a basic aqueous solution, and then activated carbon treatment in the organic solvent aqueous solution reduces caffeine, A refined tea extract with reduced aftertaste bitterness and improved color tone could be obtained. Therefore, this extract is useful not only for tea-based beverages but also for non-tea-based beverages.

Examples 3-6
By the operation according to Example 1, no hydrolysis treatment and hydrolysis treatment until the gallate body ratio is about 3.5%, the concentration of the organic solvent aqueous solution at the time of contact with activated carbon is 20 mass% and 60 mass% The operation was performed (the amount of activated carbon was 0.6 relative to the amount of non-polymer catechins). The results are shown in Table 3.

  From Table 3, when the concentration of the organic solvent aqueous solution at the time of contact with activated carbon is 20% by mass and 60% by mass, 20% by mass is preferable in terms of color tone. In terms of the recovery rate, 60% by mass is preferable.

Examples 7-9, Comparative Examples 3-4
By the operation according to Example 1 and Example 2, the organic solvent aqueous solution density | concentration at the time of activated carbon contact was made into 0 mass%, 7.5 mass%, and 20 mass%, and contact operation with activated carbon was performed by the stirring tank method (activated carbon Is 0.6) relative to the amount of non-polymer catechins. The results are shown in Table 4.

  As is clear from Table 4, the organic solvent aqueous solution concentration at the time of activated carbon contact is 7.5% by mass, compared with the case where the organic solvent aqueous solution concentration at the time of activated carbon contact is 0 mass% (when water is used as a solvent). When it is 20% by mass, the color tone is better and the recovery rate is better.

Example 10
A stainless steel column 5 (inner diameter 36 mm × height 330 mm, volume 1310 mL) was filled with 1186 mL of a synthetic adsorbent SP-70 (manufactured by Mitsubishi Chemical Corporation). The column was previously washed in the same manner as in Example 1. Thereafter, 4744 g of the tannase treatment solution obtained in Example 1 (4 volumes vs. synthetic adsorbent) was passed through the column 5 at SV = 1 (h ⁻¹ ), and the permeate was discarded. It was then washed with 1779 mL (1.5 volumes vs. synthetic adsorbent) of water at SV = 1 (h ⁻¹ ). After washing with water, 1483 mL (1.25-fold volume vs. synthetic adsorbent) of 50 mass% ethanol aqueous solution was passed at SV = 1 (h ⁻¹ ), and fractions 0 to 1.25 BV were fractionated “resin-treated product” 3 "(33.4 NTU) was obtained. To this desorbed solution, 444 g of water (0.38 times volume vs. synthetic adsorbent) was added and stirred for 2 hours to precipitate a precipitate. The turbidity at that time was 122 NTU. This solution was precipitated with a centrifuge at 6000 rpm for 10 min to obtain 40.9 g (pH 4.7) of a non-polymer catechin composition as a supernatant “centrifugal turbid product 1” (3.8 NTU). This extract contained 1.78% by mass of non-polymer catechins, and the gallate content of the non-polymer catechins composition was 35% by mass. The amount of caffeine was 0.51% by mass and the amount of gallic acid was 0.001% by mass. The non-polymer catechins in the solid content of the tea extract was 61.0% by mass.

Next, 27.9 g of granular activated carbon Taiho SGP (manufactured by Futamura Chemical Co., Ltd.) was packed in a stainless steel column 6 (inner diameter 22 mm × height 145 mm, volume 55.1 mL). “Centrifuged turbid product 1” was passed through column 6 at SV = 0.75 (h ⁻¹ ) (the amount of activated carbon was 0.6 relative to the amount of non-polymer catechins). Subsequently, filtration was performed with a 0.2 μm membrane filter.

  Ethanol was distilled off under conditions of 40 ° C. and 2.7 kPa, and then the water content was adjusted to obtain “activated carbon product 3”. This extract contained 1.1% by mass of non-polymer catechins, and the gallate content of the non-polymer catechins composition was 31% by mass. The non-polymer catechins in the solid content were 82% by mass.

Comparative Example 5
“Resin-treated product 3” in Example 10.

  In Example 10, a purified tea extract having a high recovery rate of non-polymer catechins before and after the treatment, a reduced caffeine concentration and hue, a reduced miscellaneous taste, and an improved taste was obtained. Since the comparative example 5 did not have a turbidity removal process and there was no activated carbon treatment, caffeine was contained, and the color tone and taste were also bad.

Example 11
Using the “activated carbon product 1” of Example 1, the packaged beverages shown in Table 6 were prepared. A sterilization treatment and hot pack filling based on the Food Sanitation Law were performed to obtain a container-packed beverage.

  The produced packaged beverage was stored at 37 ° C. for 30 days and then evaluated. Appearance and taste stability were good.

Claims (8)

After the tea extract is adsorbed on the synthetic adsorbent, the synthetic adsorbent is washed with an organic solvent aqueous solution having an organic solvent concentration of 0 to 5% by mass, and an organic solvent aqueous solution having an organic solvent concentration of 8 to 60% by mass is applied to the synthetic adsorbent. A method for producing a purified tea extract, wherein non-polymer catechins are eluted by contact, and then the eluate is contacted with activated carbon in an organic solvent aqueous solution having an organic solvent concentration of 1 to 80% by mass . After the tea extract is adsorbed on the synthetic adsorbent, the synthetic adsorbent is washed with an organic solvent aqueous solution having an organic solvent concentration of 0 to 5% by mass, and a basic aqueous solution is brought into contact with the synthetic adsorbent to remove non-polymer catechins. A method for producing a purified tea extract , which is eluted and then the eluate is contacted with activated carbon in an organic solvent aqueous solution having an organic solvent concentration of 1 to 80% by mass . The method for producing a purified tea extract according to claim 1 or 2, wherein the non-polymer catechins in the solid content of the purified tea extract are 50 to 95% by mass . The method for producing a purified tea extract according to any one of claims 1 to 3 , wherein the tea extract is obtained by hydrolysis treatment. The method for producing a purified tea extract according to any one of claims 1 to 4 , wherein the organic solvent is ethanol. The method for producing a purified tea extract according to any one of claims 2 to 5 , wherein the eluate is adjusted to pH 7 or less after contacting a basic aqueous solution with the synthetic adsorbent to elute non-polymer catechins. After the precipitated solid-liquid separation caused by concentration or hydrolysis of eluate, any one of claim 1 to 6 is contacted with activated carbon eluate with an organic solvent concentration is from 1 to 80% by weight of the organic solvent in the aqueous solution A method for producing the purified tea extract as described. Non-polymer catechins in solid content of 25-95% by mass, gallate content in non-polymer catechins of 0-70% by mass, ratio of gallic acid to non-polymer catechins of 0-0.1, cafe Purification in which the color tone at 450 nm is from 0 to 0.8 when the ratio of in to non-polymer catechins is 0 to 0.2 and the concentration of non-polymer catechins is 1% by mass. Tea extract.