Epimerization inhibitor for non-polymerized catechins, packaged beverage containing epi-non-polymerized catechin, and method for producing the same.

Abstract

The purpose of the present invention is to provide: an agent for suppressing epimerization of a non-polymerized catechin; a container-filling beverage containing an epimeric non-polymerized catechin, the container-filling beverage being such that epimerization of the epimeric non-polymerized catechin is suppressed; and a method for producing the same. The present invention relates to, inter alia, an agent for suppressing epimerization of a non-polymerized catechin, the agent containing, as an active ingredient, at least one compound (A) selected from the group consisting of aromatic amino acids, cysteine, dipeptides containing aromatic amino acids and / or cysteine, and salts of these.

Description

[Technical Field]

[0001] This invention relates to an inhibitor of epimerization of non-polymerized catechins. Furthermore, this invention relates to a packaged beverage containing epi-non-polymerized catechins. Finally, this invention relates to a method for producing a packaged beverage containing epi-non-polymerized catechins. [Background technology]

[0002] Non-polymerized catechins are a type of polyphenol and are known to have various physiological effects. For example, epi-form non-polymerized catechins such as epicatechin gallate and epigallocatechin gallate are known to have antioxidant and antiviral effects. Health foods that utilize the functionality and health benefits of non-polymerized catechins are also on the market.

[0003] Patent Document 1 describes a packaged beverage containing (A) 0.06 to 0.5% by mass of nonpolymerized catechins, (B) 0.01 to 5.0% by mass of one or more amino acids selected from L-isoleucine, L-leucine, L-valine, L-threonine, DL-methionine, L-methionine, L-histidine, L-phenylalanine, L-lysine, and L-tryptophan, or a salt thereof, and (C) 0.0001 to 20% by mass of a sweetener, (G) a gallate content of nonpolymerized catechins of 5 to 55% by mass, and a pH of 2.5 to 5.1. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2008-178395 [Overview of the project] [Problems that the invention aims to solve]

[0005] Beverages containing non-polymerized catechins as active ingredients are useful as functional beverages that contribute to maintaining and improving health. However, in beverages containing, for example, epi-non-polymerized catechins, some of the epi-non-polymerized catechins undergo epimerization during manufacturing or storage after manufacturing, becoming non-epi-non-polymerized catechins. As a result, the amount of epi-non-polymerized catechins in the beverage decreases. In order to expect functional beverages to exhibit their functionality, it is important to improve the stability of the active ingredient, and there is a need for a method that can suppress the epimerization of non-polymerized catechins. Patent Document 1 does not examine a method for suppressing the epimerization of non-polymerized catechins.

[0006] The present invention aims to provide an agent for inhibiting the epimerization of non-polymerized catechins. Furthermore, the present invention aims to provide a packaged beverage containing epi-non-polymerized catechins in which epimerization of epi-non-polymerized catechins is suppressed, and a method for producing the same. [Means for solving the problem]

[0007] The inventors investigated techniques to suppress the epimerization of non-polymerized catechins and found that specific amino acids, dipeptides, and their salts have the effect of suppressing the epimerization of non-polymerized catechins.

[0008] In other words, although not limited thereto, the present invention includes the following: an inhibitor of epimerization of non-polymerized catechins, a packaged beverage containing epi-non-polymerized catechins, and a method for producing a packaged beverage containing epi-non-polymerized catechins. [1] An epimerization inhibitor of nonpolymerized catechins, comprising as an active ingredient at least one compound (A) selected from the group consisting of aromatic amino acids, cysteine, dipeptides containing aromatic amino acids and / or cysteine, and salts thereof. [2] The epimerization inhibitor of non-polymerized catechins according to [1] above, wherein compound (A) is at least one selected from the group consisting of aromatic amino acids, dipeptides containing aromatic amino acids, and salts thereof. [3] An epimerization inhibitor of nonpolymerized catechins according to [1] or [2] above, wherein the aromatic amino acid is at least one amino acid selected from the group consisting of histidine, methylhistidine, phenylalanine, tryptophan, and tyrosine. [4] An epimerization inhibitor of nonpolymerized catechin according to any one of [1] to [3] above, wherein compound (A) is at least one selected from the group consisting of histidine, methylhistidine, histidine or methylhistidine-containing dipeptides and salts thereof. [5] An epimerization inhibitor of non-polymerized catechins according to any one of [1] to [4] above, wherein compound (A) is histidine and / or a salt thereof. [6] An epimerization inhibitor of nonpolymerized catechins according to any one of [1] to [4] above, wherein compound (A) is at least one selected from the group consisting of carnosine, anserine, and salts thereof. [7] The epimerization inhibitor of nonpolymerized catechins according to [1] above, wherein compound (A) is at least one selected from the group consisting of cysteine, cysteine-containing dipeptides, and salts thereof. [8] An epimerization inhibitor for nonpolymerized catechins according to any one of [1] to [7] above, used to suppress the epimerization of at least one nonpolymerized catechin selected from the group consisting of epicatechin, epigallocatechin, epicatechin gallate, epigallocatechin gallate, catechin, gallocatechin, catechin gallate, and gallocatechin gallate. [9] An epimerization inhibitor for non-polymerized catechins according to any one of [1] to [8] above, used to suppress the epimerization of at least one non-polymerized epicatechin selected from the group consisting of epicatechin, epigallocatechin, epicatechin gallate, and epigallocatechin gallate.

[10] A packaged beverage containing epi-unpolymerized catechin, comprising histidine and / or a salt thereof (A1) and epi-unpolymerized catechin (B1), having a pH greater than 4.5 and less than or equal to 7.9, a histidine-equivalent concentration of the above histidine and / or salt thereof (A1) of 0.015 to 3 w / v%, and a Brix of 3.0% or less.

[11] The epi-unpolymerized catechin-containing packaged beverage according to

[10] above, wherein the epi-unpolymerized catechin (B1) is at least one selected from the group consisting of epicatechin, epigallocatechin, epicatechin gallate, and epigallocatechin gallate.

[12] The epi-nonpolymerized catechin-containing packaged beverage according to

[10] or

[11] above, wherein the epi-nonpolymerized catechin (B1) contains epigallocatechin gallate and / or epicatechin gallate, and the concentration of epigallocatechin gallate in the beverage is 2400 μg / mL or less, and / or the concentration of epicatechin gallate is 2400 μg / mL or less.

[13] A packaged beverage containing epigallocatechin (B1) as described in any of

[10] to

[12] above, wherein the epigallocatechin (B1) contains epigallocatechin gallate, and the concentration of epigallocatechin gallate in the beverage is 400 μg / mL or less.

[14] A packaged beverage containing epi-nonpolymerized catechin as described in any of

[10] to

[13] above, wherein the Brix is ​​1.4% or less.

[15] A packaged beverage containing epi-nonpolymerized catechin as described in any of

[10] to

[14] above, wherein the beverage is a tea beverage.

[16] A method for producing a packaged beverage containing epitidine nonpolymerized catechin, comprising the step of heating a mixture containing histidine and / or a salt thereof (A1), epitidine nonpolymerized catechin (B1), and an aqueous medium (C) containing water, wherein the histidine-based concentration of the histidine and / or salt thereof (A1) is 0.015 to 3 w / v%, the pH is greater than 4.5 and 8.0 or less, and the Brix is ​​3.0% or less, to 100°C or higher.

[17] The method for producing the epi-nonpolymerized catechin (B1) according to

[16] above, wherein the epi-molten catechin (B1) is at least one selected from the group consisting of epicatechin, epigallocatechin, epicatechin gallate, and epigallocatechin gallate.

[18] The method for producing the epicatechin (B1) described in

[16] or

[17] above, wherein the nonpolymerized epicatechin (B1) comprises epigallocatechin gallate and / or epicatechin gallate, and the concentration of epigallocatechin gallate in the mixture is 2400 μg / mL or less, and / or the concentration of epicatechin gallate is 2400 μg / mL or less.

[19] The method for producing epigallocatechin (B1) according to any one of

[16] to

[18] , wherein the epigallocatechin (B1) contains epigallocatechin gallate, and the concentration of epigallocatechin gallate in the mixture is 400 μg / mL or less.

[20] The manufacturing method according to any one of

[16] to

[19] above, wherein the Brix of the above mixture is 1.4% or less.

[21] Use of at least one compound selected from the group consisting of aromatic amino acids, cysteine, dipeptides containing aromatic amino acids and / or cysteine, and salts thereof, to suppress epimerization of nonpolymerized catechins. [Effects of the Invention]

[0009] According to the present invention, an agent for inhibiting the epimerization of non-polymerized catechins can be provided. Furthermore, according to the present invention, a packaged beverage containing epi-non-polymerized catechins in which the epimerization of epi-non-polymerized catechins is suppressed, and a method for producing the same can be provided. [Modes for carrying out the invention]

[0010] <An inhibitor of epimerization of non-polymerized catechins> The present invention provides an epimerization inhibitor for non-polymerized catechins, comprising at least one compound (A) selected from the group consisting of aromatic amino acids, cysteine, dipeptides containing aromatic amino acids and / or cysteine, and salts thereof, as an active ingredient. Compound (A) has the effect of inhibiting the epimerization of non-polymerized catechins. Compound (A) may be a single compound or a combination of two or more compounds. The aromatic amino acid and cysteine ​​mentioned above are free amino acids. Epimerization of non-polymerized catechins refers to the change of non-polymerized catechins into their epimers. Epimerization of non-polymerized catechins includes the change of epimeric non-polymerized catechins into non-epimeric non-polymerized catechins (epimerization of epimeric non-polymerized catechins), and the change of non-epimeric non-polymerized catechins into epimeric non-polymerized catechins (epimerization of non-epimeric non-polymerized catechins). The change of epimeric non-polymerized catechins into non-epimeric non-polymerized catechins is also referred to as non-epimerization or de-epimerization. The change of non-epimeric non-polymerized catechins into epimeric catechins is also referred to as epimerization.

[0011] In the present invention, non-polymerized catechins are a general term for epimeric non-polymerized catechins such as epicatechin, epigallocatechin, epicatechin gallate, and epigallocatechin gallate; and non-epimeric non-polymerized catechins such as catechin, gallocatechin, catechin gallate, and gallocatechin gallate. The non-polymerized catechins may be one kind of the above compounds, or a combination of two or more kinds of compounds. When using the above compound (A), epimerization of epimeric non-polymerized catechins into non-epimeric non-polymerized catechins (for example, epimerization from epicatechin to catechin, from epigallocatechin to gallocatechin, from epicatechin gallate to catechin gallate, or from epigallocatechin gallate to gallocatechin gallate), and epimerization of non-epimeric non-polymerized catechins into epimeric non-polymerized catechins (for example, epimerization from catechin to epicatechin, from gallocatechin to epigallocatechin, from catechin gallate to epicatechin gallate, or from gallocatechin gallate to epigallocatechin gallate) can be effectively suppressed. For example, epimeric non-polymerized catechins epimerize into non-epimeric non-polymerized catechins due to heat, pH, etc., but when using the above compound (A), such epimerization can be effectively suppressed.

[0012] In one aspect, the epimerization inhibitor of non-polymeric catechins of the present invention is preferably used for suppressing the epimerization of at least one non-polymeric catechin selected from the group consisting of epicatechin, epigallocatechin, epicatechin gallate, epigallocatechin gallate, catechin, gallocatechin, catechin gallate, and gallocatechin gallate. The epimerization inhibitor of non-polymeric catechins of the present invention is more preferably used for suppressing the epimerization of at least one epimeric non-polymeric catechin selected from the group consisting of epicatechin, epigallocatechin, epicatechin gallate, and epigallocatechin gallate, and even more preferably used for suppressing the epimerization of epicatechin gallate and / or epigallocatechin gallate. In one aspect, the epimerization inhibitor of non-polymeric catechins of the present invention is preferably used for suppressing the epimerization of epimeric non-polymeric catechins to non-epimeric non-polymeric catechins. Non-polymeric catechins contained in natural products such as plants are mainly epimeric non-polymeric catechins. The epimerization inhibitor of non-polymeric catechins of the present invention is useful, for example, for suppressing the epimerization of non-polymeric catechins derived from natural products such as plants.

[0013] In one aspect, it is preferable that the above compound (A) is at least one selected from the group consisting of aromatic amino acids, dipeptides containing aromatic amino acids, and salts thereof. The aromatic amino acid may be any amino acid having an aromatic group. As the aromatic amino acid in the present invention, at least one amino acid selected from the group consisting of histidine, methylhistidine, phenylalanine, tryptophan, and tyrosine is preferable. Among them, histidine and methylhistidine are more preferable, and histidine is even more preferable because of its high epimerization inhibitory effect on non-polymeric catechins.

[0014] As the dipeptide containing an aromatic amino acid, a dipeptide containing histidine or methylhistidine is preferable. As the dipeptide containing histidine or methylhistidine, carnosine and anserine are preferable. In one aspect, it is preferable that the compound (A) is at least one selected from the group consisting of carnosine, anserine, and salts thereof.

[0015] In one embodiment of the present invention, compound (A) is preferably at least one selected from the group consisting of histidine, methylhistidine, histidine, or dipeptides containing methylhistidine and salts thereof, more preferably at least one selected from the group consisting of histidine, methylhistidine and salts thereof, even more preferably histidine and / or a salt thereof, and particularly preferably histidine. In one embodiment, when suppressing the epimerization of epi-nonpolymerized catechin to non-epi-nonpolymerized catechin, histidine and / or a salt thereof is preferred as compound (A), and histidine is more preferred.

[0016] In another embodiment of the present invention, compound (A) is preferably at least one selected from the group consisting of cysteine, cysteine-containing dipeptides, and salts thereof. Examples of cysteine-containing dipeptides include γ-glutamylcysteine.

[0017] In the present invention, the amino acid may be the L-form, the D-form, or a mixture thereof (DL-form). The above-mentioned salts of amino acids or dipeptides are not particularly limited, but salts that are acceptable in food and beverages or pharmacologically acceptable are preferred. The above-mentioned salts of amino acids or dipeptides may be either acidic salts or basic salts. Examples of acidic salts include inorganic acid salts such as hydrochloride, sulfate, nitrate, and phosphate; and organic acid salts such as acetate, citrate, maleate, malate, oxalate, lactate, succinate, fumarate, and propionate. Examples of basic salts include alkali metal salts such as sodium salt and potassium salt; and alkaline earth metal salts such as calcium salt and magnesium salt. Among these, acidic salts are preferred, inorganic acid salts are preferred, and hydrochloride salts are more preferred.

[0018] In the present invention, the origin and method of production of compound (A) are not particularly limited. Compound (A) may be derived from natural materials, produced by fermentation, or chemically synthesized. Compound (A) may, for example, be extracted from a plant containing the compound.

[0019] The total content of compound (A) in the non-polymerized catechin epimerization inhibitor of the present invention may be, for example, 0.01 to 95 w / v%. The non-polymerized catechin epimerization inhibitor of the present invention may also contain components other than compound (A) (for example, additives, etc.).

[0020] Adding compound (A) to a non-polymerized catechin-containing composition can suppress the epimerization of the non-polymerized catechin. The non-polymerized catechin-containing composition may or may not contain compound (A). Even if the non-polymerized catechin-containing composition contains compound (A), adding the non-polymerized catechin epimerization inhibitor of the present invention can effectively suppress the epimerization of the non-polymerized catechin. The non-polymerized catechin epimerization inhibitor of the present invention can be used to suppress the epimerization of non-polymerized catechin in various compositions, such as foods and beverages, pharmaceuticals, quasi-drugs, cosmetics, animal feed, and their raw materials, for example, that contain non-polymerized catechin.

[0021] The form of the non-polymerized catechin-containing composition is not particularly limited and may be liquid (e.g., liquid (including suspension, emulsion), gel, etc.) or solid (e.g., powder, particulate, etc.), but is preferably liquid. The non-polymerized catechin epimerization inhibitor is preferably used by being added to the non-polymerized catechin-containing liquid composition. Epimerization of non-polymerized catechin usually proceeds in the solution of non-polymerized catechin. Therefore, by using the non-polymerized catechin epimerization inhibitor of the present invention in the non-polymerized catechin-containing liquid composition, the effects of the present invention can be particularly greatly enjoyed. The non-polymerized catechin epimerization inhibitor of the present invention is preferably used to suppress epimerization of epi-nonpolymerized catechin or non-epi-nonpolymerized catechin in a non-polymerized catechin-containing composition in which epi-nonpolymerized catechin and non-epi-nonpolymerized catechin are not in equilibrium.

[0022] The origin and manufacturing method of non-polymerized catechins are not particularly limited. Non-polymerized catechins may be derived from natural materials, for example, or they may be chemically synthesized. For example, non-polymerized catechins can be incorporated into a composition using natural materials containing non-polymerized catechins, or extracts obtained by extracting such natural materials. An example of a plant material containing epi-non-polymerized catechins is the leaves (tea leaves) of the tea plant (Camellia sinensis) of the Camellia genus in the Theaceae family. An example of a composition containing non-polymerized catechins is an extract of tea leaves, or a liquid composition such as a beverage containing the same.

[0023] The non-polymerized catechin-containing composition is preferably a beverage containing non-polymerized catechin, more preferably a packaged beverage containing non-polymerized catechin, even more preferably a packaged beverage containing epi-non-polymerized catechin, and particularly preferably a packaged tea beverage containing epi-non-polymerized catechin. In one embodiment, the non-polymerized catechin epimerization inhibitor of the present invention can be suitably used as a non-polymerized catechin epimerization inhibitor for packaged beverages. In containerized beverages containing non-polymerized catechins, such as beverages containing epi-non-polymerized catechins, epimerization of the epi-non-polymerized catechin occurs over time during and after manufacturing. Adding at least one of the above-mentioned compound (A) to a containerized beverage containing epi-non-polymerized catechins can suppress the epimerization of the epi-non-polymerized catechin in the beverage. The non-polymerized catechin epimerization inhibitor of the present invention may be added to the raw materials during the manufacture of the non-polymerized catechin-containing composition, or it may be added to the non-polymerized catechin-containing composition.

[0024] When the non-polymerized catechin-containing composition is in liquid form, the pH of the composition is preferably 3.0 to 8.0, and more preferably 3.0 to 7.9. When the pH of the non-polymerized catechin-containing composition is within the above range, the epimerization of non-polymerized catechin can be effectively suppressed when the non-polymerized catechin epimerization inhibitor of the present invention is used. In this specification, pH refers to the pH at 25°C. pH can be measured using a commercially available pH meter.

[0025] In one embodiment, when suppressing the epimerization of non-polymerized epicatechins, the non-polymerized catechin-containing composition preferably has an epimerization ratio of 45% or more, more preferably 50% or more, even more preferably 55% or more, even more preferably 60% or more, particularly preferably 63% or more, and most preferably 65% ​​or more. Furthermore, the epimerization ratio may be 100% or less, 95% or less, 92% or less, or 90% or less. In one embodiment, in the non-polymerized catechin-containing composition, the epimerization ratio of non-polymerized catechin is preferably 45-100%, more preferably 50-100%, 55-100%, 60-100%, or 60-95%, even more preferably 60-92%, even more preferably 60-90%, particularly preferably 63-90%, and most preferably 65-90%. When the non-polymerized catechin epimerization inhibitor of the present invention is added to a non-polymerized catechin-containing composition having an epimerization ratio within the above range, the epimerization of the epi non-polymerized catechin can be effectively suppressed. In the present invention, it is preferable that the epimerization ratio of each epi non-polymerized catechin, such as epigallocatechin gallate and epigallocatechin gallate, contained in the non-polymerized catechin-containing composition is within the above range. For example, if the non-polymerized catechin-containing composition contains epigallocatechin gallate, it is preferable that the epimerization ratio of epigallocatechin gallate is within the above range, and if the composition contains epicatechin gallate, it is preferable that the epimerization ratio of epicatechin gallate is within the above range. If the non-polymerized catechin-containing composition contains epicatechin, it is preferable that the epimerization ratio of epicatechin is within the above range, and if it contains epigallocatechin, it is preferable that the epimerization ratio of epigallocatechin is within the above range. In another embodiment, when suppressing epimerization of non-epi non-polymerized catechins, the non-epi ratio of non-polymerized catechins in the non-polymerized catechin-containing composition is preferably 45% or more, more preferably 50% or more, even more preferably 55% or more, even more preferably 60% or more, particularly preferably 63% or more, and most preferably 65% ​​or more. Furthermore, the non-epi ratio may be 100% or less, 95% or less, 92% or less, or 90% or less. In one embodiment, the non-epi ratio of non-polymerized catechins is preferably 45-100%, more preferably 50-100%, 55-100%, 60-100%, or 60-95%, even more preferably 60-92%, even more preferably 60-90%, particularly preferably 63-90%, and most preferably 65-90%. When the non-epimerization inhibitor of the present invention is added to a non-polymerized catechin-containing composition in which the non-epimerization ratio is within the above range, the epimerization of the non-epi non-polymerized catechin can be effectively suppressed. It is preferable that the non-epimerization ratio of each non-epi non-polymerized catechin contained in the non-polymerized catechin-containing composition is within the above range. The epi and non-epi fractions of non-polymerized catechins can be calculated from the content (concentration) (μg / mL) of epi and non-epi non-polymerized catechins using the following formula. Epi-molecule percentage (%) = 100 × concentration of non-epi-molecule catechin / total concentration of non-epi-molecule catechin and non-epi-molecule catechin Non-epi form percentage (%) = 100 × concentration of non-epi form unpolymerized catechin / total concentration of epi form unpolymerized catechin and non-epi form unpolymerized catechin

[0026] The amount of the non-polymerized catechin epimerization inhibitor used is not particularly limited and may be set appropriately depending on the type of compound (A) and the non-polymerized catechin-containing composition. The amount of the non-polymerized catechin epimerization inhibitor used may be, for example, an amount such that the content of compound (A) in the non-polymerized catechin-containing composition is 0.001 w / v% or more, or an amount such that the content of compound (A) is 20 w / v% or less. For example, if compound (A) is histidine and / or a salt thereof, an amount can be used such that the histidine-equivalent content of histidine and / or a salt thereof in the non-polymerized catechin-containing composition is 0.003 w / v% or more, 0.008 w / v% or more, 0.01 w / v% or more, 0.011 w / v% or more, or 0.012 w / v% or more, preferably 0.013 w / v% or more, more preferably 0.015 w / v% or more, even more preferably 0.016 w / v% or more or 0.017 w / v% or more, even more preferably 0.018 w / v% or more, particularly preferably 0.019 w / v% or more, and most preferably 0.020 w / v% or more. On the other hand, if the histidine and / or salt content in the non-polymerized catechin-containing composition is high, the flavor derived from histidine and / or a salt becomes strong, which may be undesirable from the viewpoint of flavor. In one embodiment, it is preferable to use histidine and / or its salt in such an amount that the histidine-based content in the non-polymerized catechin-containing composition is preferably 3 w / v% or less, more preferably 2 w / v% or less, even more preferably 1 w / v% or less or 0.5 w / v% or less, even more preferably 0.2 w / v% or less or 0.1 w / v% or less, particularly preferably 0.06 w / v% or less, and most preferably 0.05 w / v% or less.In one embodiment, when compound (A) is histidine and / or a salt thereof, the amount of the non-polymerized catechin epimerization inhibitor used is such that the histidine content of histidine and / or a salt thereof in the non-polymerized catechin-containing composition is preferably 0.015 to 3 w / v% or 0.015 to 2 w / v%, more preferably 0.015 to 1 w / v%, 0.015 to 0.5 w / v%, or 0.015 A quantity of ~0.2 w / v%, 0.016~0.2 w / v%, 0.017~0.2 w / v%, 0.018~0.2 w / v%, or 0.019~0.2 w / v%, more preferably 0.020~0.2 w / v%, even more preferably 0.020~0.1 w / v%, particularly preferably 0.020~0.06 w / v%, and most preferably 0.020~0.05 w / v% is preferred. In one embodiment, it is preferable to add an epimerization inhibitor of non-polymerized catechin so that the histidine-equivalent content of histidine and / or its salt in the non-polymerized catechin-containing composition falls within the above range. In a preferred embodiment of the present invention, it is preferable to add an epimerization inhibitor for non-polymerized catechins to a beverage (preferably a tea beverage) containing non-polymerized catechins such that the histidine-based content of histidine and / or its salts in the beverage is within the above range.

[0027] By adding compound (A) to a non-polymerized catechin-containing composition, a non-polymerized catechin-containing composition in which epimerization of the non-polymerized catechin is suppressed can be obtained. By adding compound (A) to a non-polymerized catechin-containing composition, epimerization of the non-polymerized catechin can be suppressed, for example, during storage.

[0028] <Container-packaged beverage containing non-polymerized epiform catechins> The present invention provides a packaged beverage containing epi-unpolymerized catechin, comprising histidine and / or its salt (A1) and epi-unpolymerized catechin (B1), having a pH greater than 4.5 and 7.9 or less, a histidine-based concentration of the histidine and / or its salt (A1) of 0.015 to 3 w / v%, and a Brix of 3.0% or less. The present invention's packaged beverage containing epi-nonpolymerized catechin (hereinafter sometimes referred to as the "packaged beverage of the present invention") is a packaged beverage in which a beverage containing epi-nonpolymerized catechin is filled into a container.

[0029] Examples of histidine salts include the same salts as those of the amino acids or dipeptides mentioned above. Preferably, the histidine salt is an acidic salt of histidine, more preferably an inorganic salt of histidine, and even more preferably a hydrochloride salt of histidine. In one embodiment, histidine and / or histidine hydrochloride are preferred as histidine and / or its salt (A1), and histidine is more preferred. The non-polymerized epicatechin (B1) is preferably at least one selected from the group consisting of epicatechin, epigallocatechin, epicatechin gallate, and epigallocatechin gallate. The non-polymerized epicatechin (B1) is more preferably epicatechin gallate and / or epigallocatechin gallate, and even more preferably epigallocatechin gallate and / or epicatechin gallate.

[0030] In the packaged beverage of the present invention, the concentration of histidine and / or its salt (A1) is 0.015 to 3 w / v% in terms of histidine equivalent. In a packaged beverage containing epi-unpolymerized catechin (B1), the epi-unpolymerized catechin in the beverage undergoes epimerization over time and is converted to non-epi-unpolymerized catechin. When the histidine equivalent concentration of histidine and / or its salt (A) is within the above range, the epimerization (non-epimerization) of epi-unpolymerized catechin (B1) in the beverage over time can be effectively suppressed. Therefore, the decrease in the concentration of epi-unpolymerized catechin over time (decrease in epi-unpolymerized catechin) and the decrease in the ratio of epi-unpolymerized catechin in non-polymerized catechin (epi ratio) in the packaged beverage can be effectively suppressed. The concentration of histidine and / or its salt (A1) in the beverage is preferably 0.016 w / v% or higher, more preferably 0.017 w / v% or higher, even more preferably 0.018 w / v% or higher, particularly preferably 0.019 w / v% or higher, and most preferably 0.020 w / v% or higher, in terms of histidine equivalent. On the other hand, a high concentration of histidine and / or its salt may be undesirable from the viewpoint of the flavor of the beverage. The concentration of histidine and / or its salt in the beverage is preferably 2 w / v% or less, more preferably 1 w / v% or less or 0.5 w / v% or less, even more preferably 0.2 w / v% or less, even more preferably 0.1 w / v% or less, particularly preferably 0.06 w / v% or less, and most preferably 0.05 w / v% or less, in terms of histidine equivalent. In one embodiment, the histidine-based concentration of histidine and / or its salt in the beverage is preferably 0.015-2 w / v%, more preferably 0.015-1 w / v%, 0.015-0.5 w / v%, 0.015-0.2 w / v%, 0.016-0.2 w / v%, 0.017-0.2 w / v%, 0.018-0.2 w / v%, or 0.019-0.2 w / v%, even more preferably 0.020-0.2 w / v%, even more preferably 0.020-0.1 w / v%, particularly preferably 0.020-0.06 w / v%, and most preferably 0.020-0.05 w / v%. The concentration of histidine and / or its salt (A1) can be measured by known methods, such as fluorescence methods.Histidine and / or its salt (A1) are preferably dissolved and / or dispersed in the beverage.

[0031] The concentration of epi-unpolymerized catechin (B1) in the beverage is not particularly limited. The total concentration of epi-unpolymerized catechin (B1) in the beverage is preferably, for example, 50 μg / mL or more, more preferably 100 μg / mL or more, preferably 5000 μg / mL or less, more preferably 4800 μg / mL or less, and even more preferably 2400 μg / mL or less. In the packaged beverage of the present invention, it is preferable that the total concentration of epi-unpolymerized catechin (B1) is within the above range because it can more effectively suppress the epimerization of epi-unpolymerized catechin. The beverage of the present invention preferably contains epigallocatechin gallate and / or epicatechin gallate. In this case, it is preferable that the concentration of epigallocatechin gallate in the beverage is 2400 μg / mL or less, and / or the concentration of epicatechin gallate is 2400 μg / mL or less. When the concentration of epigallocatechin gallate in the beverage is within the above range, the epimerization of epigallocatechin gallate to gallocatechin gallate can be further suppressed. Also, when the concentration of epicatechin gallate is within the above range, the epimerization of epicatechin gallate to catechin gallate can be further suppressed. In one embodiment, it is preferable that the beverage contains epigallocatechin gallate and / or epicatechin gallate, with the concentration of epigallocatechin gallate in the beverage being 2400 μg / mL or less, and the concentration of epicatechin gallate being 2400 μg / mL or less. When the beverage contains epigallocatechin gallate, it is preferable that the concentration of epigallocatechin gallate in the beverage be 50 μg / mL or more, more preferably 100 μg / mL or more, more preferably 1200 μg / mL or less, 800 μg / mL or less, 600 μg / mL or less, 400 μg / mL or less, or 300 μg / mL or less, even more preferably 200 μg / mL or less, even more preferably 160 μg / mL or less, particularly preferably 150 μg / mL or less, and most preferably 140 μg / mL or less. If the beverage contains epicatechin gallate, the concentration of epicatechin gallate in the beverage is preferably 50 μg / mL or more, more preferably 100 μg / mL or more, more preferably 1200 μg / mL or less, 800 μg / mL or less, 600 μg / mL or less, 400 μg / mL or 300 μg / mL or less, even more preferably 200 μg / mL or less, even more preferably 160 μg / mL or less, particularly preferably 150 μg / mL or less, and most preferably 140 μg / mL or less. The non-polymerized epicatechin (B1) is preferably dissolved and / or dispersed in the beverage. The concentration of epi-unpolymerized catechin (B1) can be measured by high-performance liquid chromatography (HPLC). The measurement conditions described in the examples can be used.

[0032] In the present invention, the pH of the beverage is preferably greater than 4.5 and 7.0 or less, more preferably greater than 4.5 and 6.5 or less, more preferably between 4.7 and 6.5, even more preferably between 4.9 and 6.5, even more preferably between 5.0 and 6.5, particularly preferably between 5.0 and 6.2, and most preferably between 5.0 and 6.0.

[0033] The packaged beverage of the present invention has a Brix of 3.0% or less. Preferably, the beverage has a Brix of 1.8% or less. When the Brix of the beverage of the present invention is within the above range, the epimerization of non-polymerized epicatechin to non-polymerized epicatechin can be more effectively suppressed. The beverage of the present invention is more preferably 1.4% or less, even more preferably 1.2% or less, even more preferably 1.0% or less, particularly preferably 0.9% or less or 0.8% or less, and most preferably 0.7% or less. The Brix of the beverage may be 0.01% or more, preferably 0.05% or more, more preferably 0.1% or more, even more preferably 0.15% or more, particularly preferably 0.2% or more, and most preferably 0.3% or more. In one embodiment, the beverage preferably has a Brix of 0.01 to 1.4%, more preferably 0.01 to 1.2%, 0.01 to 1.0%, 0.01 to 0.9%, 0.01 to 0.8%, 0.05 to 0.8%, 0.1 to 0.8%, or 0.15 to 0.8%, even more preferably 0.2 to 0.8%, particularly preferably 0.2 to 0.7%, and most preferably 0.3 to 0.7%. The Brix of the beverage may also preferably be 0.3 to 0.8%. A Brix within the above range is also preferable from the viewpoint of flavor. Brix can be evaluated by the Brix value obtained using a sugar meter or refractometer. The Brix value is the value obtained by converting the refractive index measured at 20°C into mass / mass percent of the sucrose solution based on the ICUMSA (International Commission for Uniform Sugar Analysis) conversion table. The unit is expressed as "°Bx", "%", or "degrees". Brix can be measured, for example, using an ATAGO digital refractometer, model number PR-101α.

[0034] The origin and production method of histidine and / or its salt (A) and epi-unpolymerized catechin (B1) are not particularly limited. For example, histidine and / or its salt (A1) may be extracted from plant material, produced by fermentation, or chemically synthesized. Epi-unpolymerized catechin (B1) may be extracted from a plant containing epi-unpolymerized catechin. Examples of plant material containing epi-unpolymerized catechin include the leaves of the tea plant (Camellia sinensis) of the Camellia genus in the Theaceae family. The beverage of the present invention may contain components other than histidine and / or its salt (A1) and epi-unpolymerized catechin (B1). The packaged beverage of the present invention may contain, for example, non-epi-unpolymerized catechin (B2). The packaged beverage of the present invention preferably has an epi-isomer ratio of 45% or more of non-polymerized catechin, more preferably 50% or more, even more preferably 55% or more, even more preferably 60% or more, particularly preferably 63% or more, and most preferably 65% ​​or more. Furthermore, the above epi-isomer ratio may be 100% or less, 95% or less, 92% or less, or 90% or less. In one embodiment, the epi-isomer ratio of non-polymerized catechin in the beverage is preferably 45-100%, more preferably 50-100%, 55-100%, 60-100%, or 60-95%, even more preferably 60-92%, even more preferably 60-90%, particularly preferably 63-90%, and most preferably 65-90%. It is preferable that the epi-isomer ratio of each non-polymerized catechin, such as epigallocatechin gallate, epigallocatechin gallate, etc., contained in the beverage is within the above range. For example, if the beverage contains epigallocatechin gallate, it is preferable that the epi isomer ratio of epigallocatechin gallate is within the above range. If the beverage contains epicatechin gallate, it is preferable that the epi isomer ratio of epicatechin gallate is within the above range. If the beverage contains epicatechin, it is preferable that the epi isomer ratio of epicatechin is within the above range, and if it contains epigallocatechin, it is preferable that the epi isomer ratio of epigallocatechin is within the above range. In one embodiment, the beverage of the present invention can also be produced by incorporating an extract of tea plant containing non-polymerized epi catechin.

[0035] The beverage (contents) in the packaged beverage of the present invention is liquid and contains water. The beverage may be in the form of a straight beverage or a concentrated beverage, but a straight beverage is preferred. A straight beverage is one that can be drunk as is without dilution. A concentrated beverage is one that is diluted with a drinking solvent such as water before drinking. The beverage in the present invention may be a non-alcoholic beverage or an alcoholic beverage, but a non-alcoholic beverage is preferred. In one embodiment, the packaged beverage of the present invention is preferably a beverage other than a beer-flavored alcoholic beverage (including beer), and more preferably a non-alcoholic beverage. A non-alcoholic beverage is a beverage with an ethanol concentration of less than 1 v / v%. Examples of non-alcoholic beverages include, but are not limited to, tea beverages and non-alcoholic beer-flavored beverages. In one embodiment, the non-alcoholic beverage is preferably a non-alcoholic beverage other than a non-alcoholic beer-flavored beverage. Examples of alcoholic beverages include, but are not limited to, beer, beer-flavored beverages, red wine, white wine, and whiskey.

[0036] Tea beverages refer to beverages that contain plant extracts as tea ingredients. There are no particular limitations on the plant sources (plant-derived ingredients) used for the plant extracts, but examples include the leaves (tea leaves) of the tea plant (Camellia sinensis) of the Camellia genus in the Theaceae family, grains, and the leaves, stems, and roots of plants other than the tea plant. Examples of tea leaves include green tea, oolong tea (such as Tieguanyin, Sezhong, Huangjin Gui, and Wuyi rock tea), and black tea. One type of tea leaf may be used, or two or more may be used. Green tea is a type of unfermented tea, oolong tea is a type of semi-fermented tea, and black tea is a type of fermented tea. Examples of grains include barley, wheat, adlay, rye, and other grains; brown rice and other rice varieties; and soybeans, black soybeans, and other grains. One or more types of grains can be used. Barley and adlay are preferred. Examples of stems, leaves, or roots of plants other than tea plants include the leaves of Cassia obtusifolia. The beverage of the present invention may contain one or more tea extracts such as green tea extract, oolong tea extract, and black tea extract, and grain extracts. Preferably, the beverage of the present invention is a tea beverage such as a green tea beverage, oolong tea beverage, black tea beverage, barley tea beverage, or blended tea beverage. A green tea beverage is a beverage in which green tea leaves are used at a rate of 50% by weight or more of the total amount of raw plant material used in the production of the beverage. A black tea beverage is a beverage in which black tea leaves are used at a rate of 50% by weight or more of the total amount of raw plant material used in the production of the beverage. An oolong tea beverage is a beverage in which oolong tea leaves are used at a rate of 50% by weight or more of the total amount of raw plant material used in the production of the beverage. A barley tea beverage is a beverage in which barley (preferably barley and / or adlay) is used at a rate of 50% by weight or more of the total amount of raw plant material used in the production of the beverage. A blended tea beverage is a tea beverage in which multiple types of raw plant material are used, and the amount of green tea leaves, black tea leaves, oolong tea leaves, and barley used is each less than 50% by weight of the total amount of raw plant material used in the production of the beverage.

[0037] The packaged beverage of the present invention may contain, for example, one or more additives that can be used in beverages (for example, antioxidants, flavorings, vitamins, colorants, acidulants, emulsifiers, preservatives, seasonings, extracts, pH adjusters, quality stabilizers, etc.).

[0038] In the packaged beverage of the present invention, the form of the container is not particularly limited and includes metal containers such as cans, bottles, retort pouches, PET bottles, paper cartons, aluminum pouches, vinyl pouches, and the like. The method for producing the packaged beverage of the present invention is not particularly limited. For example, it can be produced by the method for producing a packaged beverage containing epi-nonpolymerized catechin described below.

[0039] In the packaged beverage of the present invention, the epimerization of epi nonpolymerized catechins is suppressed. By suppressing the epimerization of epi nonpolymerized catechins, for example, it is possible to suppress the decrease in the concentration of epi nonpolymerized catechins over time during storage of the packaged beverage (decrease in epi nonpolymerized catechins). Furthermore, it is possible to suppress the decrease in the ratio of epi nonpolymerized catechins to nonpolymerized catechins (epi ratio) during storage.

[0040] <Method for producing a packaged beverage containing non-polymerized epiform catechins> The present invention also includes the following methods for producing packaged beverages. A method for producing a packaged beverage containing epitidine nonpolymerized catechin, comprising the step of heating a mixture containing histidine and / or a salt thereof (A1), epitidine nonpolymerized catechin (B1), and an aqueous medium (C) containing water, wherein the histidine concentration of the histidine and / or salt thereof (A1) is 0.015 to 3 w / v%, the pH is greater than 4.5 and 8.0 or less, and the Brix is ​​3.0% or less, to 100°C or higher.

[0041] The present invention provides a manufacturing method comprising a step of heating a mixture containing histidine and / or a salt thereof (A), an epitidine nonpolymerized catechin (B1), and an aqueous medium containing water (C) to 100°C or higher (also referred to as the heating step). The mixture subjected to the heating step is a liquid mixture (liquid composition).

[0042] The preferred embodiment of histidine and / or its salt (A1) is the same as in the case of the beverage described above, with histidine and / or histidine hydrochloride being preferred, and histidine being preferred. The concentration of histidine and / or its salt (A1) in the above mixture is preferably 0.016 w / v% or higher, more preferably 0.017 w / v% or higher, even more preferably 0.018 w / v% or higher, particularly preferably 0.019 w / v% or higher, and most preferably 0.020 w / v% or higher, in terms of histidine equivalent. Furthermore, a high concentration of histidine and / or its salt may be undesirable from the viewpoint of the flavor of the resulting beverage. The concentration of histidine and / or its salt (A1) in the above mixture is preferably 2 w / v% or less, more preferably 1 w / v% or less or 0.5 w / v% or less, even more preferably 0.2 w / v% or less, even more preferably 0.1 w / v% or less, particularly preferably 0.06 w / v% or less, and most preferably 0.05 w / v% or less, in terms of histidine equivalent. In one embodiment, the concentration of histidine and / or its salt (A1) in the above mixture is preferably 0.015 to 2 w / v%, more preferably 0.015 to 1 w / v%, 0.015 to 0.5 w / v%, 0.015 to 0.2 w / v%, 0.016 to 0.2 w / v%, 0.017 to 0.2 w / v%, 0.018 to 0.2 w / v%, or 0.019 to 0.2 w / v%, even more preferably 0.020 to 0.2 w / v%, even more preferably 0.020 to 0.1 w / v%, particularly preferably 0.020 to 0.06 w / v%, and most preferably 0.020 to 0.05 w / v%. It is preferable that the concentration of histidine and / or its salt (A1) in the above mixture before heat treatment is within the above range. In the above mixture, it is preferable that histidine and / or its salt (A1) are dissolved and / or dispersed in the aqueous medium (C).

[0043] The epi-unpolymerized catechin (B1) is preferably at least one selected from the group consisting of epicatechin, epigallocatechin, epicatechin gallate, and epigallocatechin gallate. More preferably, the epi-unpolymerized catechin (B1) contains epicatechin gallate and / or epigallocatechin gallate. In the above mixture, the epi-unpolymerized catechin (B1) is preferably dissolved and / or dispersed in an aqueous medium (C).

[0044] If the above mixture contains epigallocatechin gallate, the concentration of epigallocatechin gallate in the mixture is preferably 2400 μg / mL or less. When the concentration of epigallocatechin gallate in the mixture is 2400 μg / mL or less, the epimerization of epigallocatechin gallate to gallocatechin gallate during heat treatment can be further suppressed. If the above mixture contains epicatechin gallate, the concentration of epicatechin gallate in the mixture is preferably 2400 μg / mL or less. When the concentration of epicatechin gallate in the mixture is 2400 μg / mL or less, the epimerization of epicatechin gallate to catechin gallate during heat treatment can be further suppressed. In one embodiment, the above mixture preferably contains epigallocatechin gallate and / or epicatechin gallate, with the concentration of epigallocatechin gallate in the mixture being 2400 μg / mL or less, and / or the concentration of epicatechin gallate being 2400 μg / mL or less, and more preferably the concentrations of both epigallocatechin gallate and epicatechin gallate being 2400 μg / mL or less. The concentration of epigallocatechin gallate in the mixture is preferably 50 μg / mL or more, more preferably 100 μg / mL or more, more preferably 1200 μg / mL or less, 800 μg / mL or less, 600 μg / mL or less, 400 μg / mL or less, or 300 μg / mL or less, even more preferably 200 μg / mL or less, even more preferably 160 μg / mL or less, particularly preferably 150 μg / mL or less, and most preferably 140 μg / mL or less. If the above mixture contains epicatechin gallate, the concentration of epicatechin gallate in the mixture is preferably 50 μg / mL or more, more preferably 100 μg / mL or more, more preferably 1200 μg / mL or less, 800 μg / mL or less, 600 μg / mL or less, 400 μg / mL or less, or 300 μg / mL or less, even more preferably 200 μg / mL or less, even more preferably 160 μg / mL or less, particularly preferably 150 μg / mL or less, and most preferably 140 μg / mL or less. It is preferable that the concentration of epigallocatechin gallate and / or epicatechin gallate in the above mixture before heat treatment be within the above range.

[0045] The aqueous medium (C) contains water, but may also contain a solvent other than water. Examples of solvents other than water include alcohols (e.g., ethanol), and one or more of these can be used. The content of aqueous medium (C) in the above mixture is preferably 85% by weight or more, more preferably 97.0% by weight or more, even more preferably 98.2% by weight or more, and particularly preferably 98.2 to 99.9% by weight. The water content in aqueous medium (C) is preferably 99% by weight or more, more preferably 99.9 to 100% by weight. In one embodiment, the alcohol concentration of aqueous medium (C) is preferably less than 1 v / v%, and the ethanol concentration is preferably less than 1 v / v%.

[0046] In the manufacturing method of the present invention, a mixture having a pH greater than 4.5 and 8.0 or less is heat-treated. The pH of the mixture before heat treatment may be within the above range. If the mixture contains histidine and / or its salt at the above concentrations and has a pH greater than 4.5 and 8.0 or less, the epimerization of non-polymerized epicatechin during heat treatment can be effectively suppressed. Furthermore, by heating the above mixture, a beverage with a pH greater than 4.5 and 7.9 or less can be produced. The pH of the mixture before heat treatment is preferably greater than 4.5 and 7.0 or less, more preferably greater than 4.5 and 6.5 or less, even more preferably between 4.7 and 6.5, still more preferably between 4.9 and 6.5, still more preferably between 5.0 and 6.5, particularly preferably between 5.0 and 6.2, and most preferably between 5.0 and 6.0.

[0047] The above mixture may contain components other than histidine and / or its salt (A1), epi-unpolymerized catechin (B1), and an aqueous medium (C). The above mixture may contain, for example, additives that can be used in beverages. The mixture may contain non-epi-unpolymerized catechin (B2). The above mixture preferably has an epi-isomer ratio of 45% or more, more preferably 50% or more, even more preferably 55% or more, even more preferably 60% or more, particularly preferably 63% or more, and most preferably 65% ​​or more. Furthermore, the epi-isomer ratio may be 100% or less, 95% or less, 92% or less, or 90% or less. In one embodiment, in the above mixture, the epi isomer ratio of non-polymerized catechins is preferably 45-100%, more preferably 50-100%, 55-100%, 60-100%, or 60-95%, even more preferably 60-92%, even more preferably 60-90%, particularly preferably 63-90%, and most preferably 65-90%. It is preferable that the epi isomer ratios of each non-polymerized catechin, such as epigallocatechin gallate, contained in the mixture are within the above ranges. For example, if the mixture contains epigallocatechin gallate, it is preferable that the epi isomer ratio of epigallocatechin gallate is within the above ranges. If the mixture contains epicatechin gallate, it is preferable that the epi isomer ratio of epicatechin gallate is within the above ranges. If the mixture contains epicatechin, it is preferable that the epi isomer ratio of epicatechin be within the above range, and if it contains epigallocatechin, it is preferable that the epi isomer ratio of epigallocatechin be within the above range. The epi isomer ratio of the mixture before heat treatment is preferably within the above range. The mixture may contain one or more plant extracts used in the above tea beverage, such as green tea extract, oolong tea extract, black tea extract, and grain extracts. The origin and production method of histidine and / or its salt (A1) and epi nonpolymerized catechin (B1) are not particularly limited. Histidine and / or its salt (A1) may be incorporated into the mixture, for example, in the form of a plant extract containing it. Epi nonpolymerized catechin (B1) may be incorporated into the mixture, for example, in the form of a plant extract containing it.In one embodiment, the above mixture is preferably a raw material liquid for a tea beverage (green tea beverage, oolong tea beverage, black tea beverage, barley tea beverage, blended tea beverage, etc.).

[0048] The above mixture has a Brix of 3.0% or less before heat treatment. Since the epimerization of non-polymerized epicatechin during heat treatment can be further suppressed, the above mixture preferably has a Brix of 1.5% or less, more preferably 1.4% or less, even more preferably 1.2% or less, even more preferably 1.0% or less, particularly preferably 0.9% or less or 0.8% or less, and most preferably 0.7% or less. The above Brix may be 0.01% or more, more preferably 0.05% or more, even more preferably 0.1% or more, even more preferably 0.15% or more, particularly preferably 0.2% or more, and most preferably 0.3% or more. In one embodiment, the mixture preferably has a Brix of 0.01 to 1.5% or 0.01 to 1.4%, more preferably 0.01 to 1.2%, 0.01 to 1.0%, 0.01 to 0.9%, 0.01 to 0.8%, 0.05 to 0.8%, 0.1 to 0.8%, or 0.15 to 0.8%, even more preferably 0.2 to 0.8%, particularly preferably 0.2 to 0.7%, and most preferably 0.3 to 0.7%. A Brix of 0.3 to 0.8% is also preferable. A Brix of the mixture before heat treatment being within the above range is also preferable from the viewpoint of the flavor of the resulting beverage. The method of adjusting the Brix is ​​not particularly limited. For example, methods such as dilution with water or adjusting the proportions of the mixture can be employed.

[0049] In the heat treatment, the mixture is heated to the above temperature. Epimerization of the epiteran nonpolymerized catechin tends to proceed at higher temperatures. In the production method of the present invention, epimerization of the epiteran nonpolymerized catechin during heat treatment can be suppressed. The heat treatment temperature is preferably 115°C or higher, and preferably 150°C or lower, from the viewpoint of effectively suppressing the epimerization of the non-polymerized epicatechin. The means of heating are not particularly limited. The heat treatment can be carried out using known apparatus. The heating time is preferably 30 seconds to 400 minutes, more preferably 30 seconds to 240 minutes, even more preferably 30 seconds to 14 minutes, and particularly preferably 30 seconds to 5 minutes. The heat treatment may be performed after filling the above mixture into containers, or before filling the mixture into containers. The heat treatment may be for sterilization purposes. Sterilization may be performed using a UHT (Ultra High Temperature) sterilizer or a retort sterilizer such as an autoclave. The above heat treatment yields an epi-nonpolymerized catechin-containing beverage containing histidine and / or its salt (A), epi-nonpolymerized catechin (B1), and an aqueous medium (C) containing water. A preferred embodiment of the epi-nonpolymerized catechin-containing beverage is the containerized beverage of the present invention described above.

[0050] The manufacturing method of the present invention may include steps other than the heating step. After the heat treatment, it is preferable to perform a step of cooling the epi-nonpolymerized catechin-containing beverage obtained from the heat treatment to a temperature of preferably 23°C or lower, more preferably 15°C or lower. The manufacturing method of the present invention may include, for example, one or more steps such as: preparing a mixture containing histidine and / or a salt thereof (A1), epitionic unpolymerized catechin (B1), and an aqueous medium (C), having a pH greater than 4.5 and 8.0 or less, and a Brix of 3.0% or less; filling the mixture (or the mixture after heat treatment (beverage)) into a container; and purging the air in the container with nitrogen. Examples of containers include those used for the above-mentioned packaged beverages. The method for preparing the above mixture is not particularly limited. For example, it can be prepared by mixing histidine and / or its salt (A1), epi-unpolymerized catechin (B1), and water in an aqueous medium (C), and optionally other components, and adjusting the pH and Brix. The mixture may contain, for example, plant extracts such as the above-mentioned tea extract. In one embodiment, the epi-unpolymerized catechin (B1) may be prepared using a tea extract containing it. The method for adjusting the pH of the mixture is not particularly limited; for example, pH adjusting agents such as acids used to adjust the pH of beverages can be used. Alternatively, for example, the pH of the mixture can be adjusted by using a histidine salt such as histidine hydrochloride in the preparation of the mixture. The pH and Brix of the mixture may be adjusted during or after mixing the components. Additionally, if necessary, a step may be taken to adjust the Brix of the epi-unpolymerized catechin-containing beverage obtained by heat treatment.

[0051] According to the manufacturing method of the present invention, a packaged beverage containing epimerization of epimerization of non-polymerized

[0052] <Method for suppressing epimerization of non-polymerized catechins> The present invention also includes a method for suppressing epimerization of non-polymerized catechins, which involves adding at least one compound (A) selected from the group consisting of aromatic amino acids, cysteine, dipeptides containing aromatic amino acids and / or cysteine, and salts thereof, to a composition containing non-polymerized catechins. The present invention also includes the use of at least one compound (compound (A)) selected from the group consisting of aromatic amino acids, cysteine, dipeptides containing aromatic amino acids and / or cysteine, and salts thereof, to suppress the epimerization of nonpolymerized catechins. In the above method and use, compound (A), non-polymerized catechin, non-polymerized catechin-containing composition, and preferred embodiments thereof are the same as those in the non-polymerized catechin epimerization inhibitor described above.

[0053] For clarification, the numerical range expressed by a lower limit and an upper limit in this specification, i.e., "lower limit to upper limit," includes those lower and upper limits. For example, the range expressed by "1 to 2" means 1 or more and 2 or less, including 1 and 2. In this specification, the upper and lower limits may be any combination of ranges. [Examples]

[0054] The present invention will be described in more detail below with reference to examples, but this will not limit the scope of the present invention.

[0055] <Method for measuring epi-nonpolymerized catechins> The concentration of non-polymerized epicatechin was measured by high-performance liquid chromatography. (Measurement conditions) The sample was diluted 2-fold with 100% methanol, then centrifuged (13,500 rpm × 5 min) to collect the supernatant. A Thermo Fisher Scientific high-performance liquid chromatograph (model Vanquish) was used, fitted with a Unison UK-C18HT (3 mmφ × 100 mm: Imtakt) packed column for octadecyl group-introduced liquid chromatography, and measured by gradient method at a column temperature of 40°C. Mobile phase A was a distilled aqueous solution containing 0.1% formic acid, and mobile phase B was an acetonitrile solution containing 0.1% formic acid. The sample injection volume was 2 μL, the flow rate was 1.0 mL / min, and the UV detector wavelength was 280 nm. Gradient condition (v / v%) 0min B liquid 2%, 3min B liquid 20%, 4.2min B liquid 23%, 4.5min B liquid 80%, 4.6min B liquid 80%, 4.7min B liquid 2% The following standard substances were used: (-)-epigallocatechin gallate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), (-)-gallocatechin gallate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), (-)-epicatechin gallate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), (-)-catechin gallate (manufactured by Nagara Science Co., Ltd.), (-)-epigallocatechin (manufactured by Tokyo Chemical Industries, Ltd.), (-)-gallocatechin (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), (-)-epicatechin (manufactured by Tokyo Chemical Industries, Ltd.), and (+)-catechin (manufactured by Tokyo Chemical Industries, Ltd.).

[0056] <Method for measuring histidine> Histidine was quantified using a histidine quantification kit (MicroMolar Histidine Assay Kit, ProFoldin) according to the kit's instructions. This kit measures histidine using fluorescence (detection method: fluorescence, measurement wavelength: excitation 485 nm, fluorescence 535 nm).

[0057] <ph> pH (25°C) was measured using a pH meter (HORIBA, model number: LAQUA F71).

[0058] <Heat treatment> For the heat treatment, an autoclave manufactured by Hirayama Seisakusho Co., Ltd. (model: HV-50IILB) was used.

[0059] <Epiphyseal rate and non-epiphyseal rate> In the examples, the epi group ratio was calculated from the concentrations (μg / mL) of epi nonpolymerized catechin and non-epi nonpolymerized catechin using the following formula. Epi-molecule percentage (%) = 100 × concentration of non-epi-molecule catechin / total concentration of non-epi-molecule catechin and non-epi-molecule catechin The non-epiphyseal fraction was calculated using the following formula. Non-epi form percentage (%) = 100 × concentration of non-epi form unpolymerized catechin / total concentration of epi form unpolymerized catechin and non-epi form unpolymerized catechin

[0060] Unless otherwise specified, the amino acids used were L-isomers. L-histidine was manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. (hereinafter abbreviated as histidine), carnosine was manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., anserine was manufactured by Combi-Blocks, 1-methylhistidine was manufactured by Cosmo Bio Inc., 3-methylhistidine was manufactured by Sigma-Aldrich, and D-histidine was manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. For the L-histidine hydrochloride reagent, L-histidine hydrochloride monohydrate manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. The L-histidine raw material (food additive with an L-histidine content of 98.0% or more) and histidine hydrochloride raw material (food additive with an L-histidine hydrochloride content of 98.0% or more) were manufactured by Ajinomoto Healthy Supply Co., Ltd. For amino acids other than those listed above, we used amino acids manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.

[0061] The propylene glycol used was a food additive ingredient manufactured by Lucas Guitars. For the epigallocatechin gallate raw material (hereinafter referred to as EGCg raw material), a powdered raw material extracted and purified from green tea was used (the epigallocatechin gallate (EGCg) content was 95.3% by weight, the gallocatechin gallate (GCg) content was below the detection limit, and the epi isomer ratio was 100%). For the epicatechin gallate raw material (hereinafter referred to as ECg raw material), a powdered raw material extracted and purified from green tea was used (the epicatechin gallate (ECg) content was 93.3% by weight, the catechin gallate (Cg) content was below the detection limit, and the epi isomer ratio was 100%). For epigallocatechin (EGC), epigallocatechin (purity 98% or higher) manufactured by Tokyo Chemical Industry Co., Ltd. was used. For epicatechin (EC), epicatechin (purity 97% or higher) manufactured by Tokyo Chemical Industry Co., Ltd. was used. For catechin (C), we used (+)-catechin manufactured by Tokyo Chemical Industry Co., Ltd. For catechin gallate (Cg), we used (-)-catechin gallate manufactured by Nagara Science Co., Ltd. For gallocatechin (GC), we used (-)-gallocatechin manufactured by Fujifilm Wako Pure Chemical Corporation. For gallocatechin gallate (GCg), we used (-)-gallocatechin gallate manufactured by Fujifilm Wako Pure Chemical Corporation.

[0062] For the preparation of the samples and control samples, commercially available soft drinks were used: Blended Tea (derived from barley, Job's tears, roasted rice, soybeans, and senna tea) (hereinafter abbreviated as Blended Tea A), Blended Tea (derived from green tea, barley, roasted rice, and Japanese black tea) (hereinafter abbreviated as Blended Tea B), and Green Tea (hereinafter abbreviated as Green Tea Beverage C).

[0063] The pH, epigallocatechin gallate (EGCg) concentration, gallocatechin gallate (GCg) concentration, epicatechin gallate (ECg) concentration, catechin gallate (Cg) concentration, epicatechin (EC) concentration, catechin (C) concentration, epigallocatechin (EGC) concentration, gallocatechin (GC) concentration, epi-isomer ratio, and histidine concentration of blended teas A-B and green tea beverage C are listed below. All histidine contained in the beverages listed below was L-histidine. 1 μg / mL is equivalent to 0.0001 w / v% when converted to weight-to-volume concentration (w / v%). (Blended Tea A) pH 5.3, EGCg concentration: below detection limit, GCGg concentration: below detection limit, ECg concentration: below detection limit, Cg concentration: below detection limit, EC concentration: below detection limit, C concentration: below detection limit, EGC concentration: below detection limit, GC concentration: below detection limit, histidine concentration: 0.0033 w / v% (Blended Tea B) pH5.8, EGCg concentration: 25μg / mL, GCg concentration: 26μg / mL, ECg concentration: 11μg / mL, Cg concentration: 9μg / mL, EC concentration: below detection limit, C concentration: below detection limit, EG C concentration: 26 μg / mL, GC concentration: 20 μg / mL, EGCg epi form rate: 48.8%, ECg epi form rate: 55.0%, EGC epi form rate: 57.0%, histidine concentration: 0.0037w / v% (Green tea drink C) pH6.3, EGCg concentration: 109μg / mL, GCg concentration: 130μg / mL, ECg concentration: 33μg / mL, Cg concentration: 28μg / mL, EC concentration: 40μg / mL, C concentration: 39μg / mL, EGC concentration: 83 μg / mL, GC concentration: 84 μg / mL, EGCg epi form rate: 45.8%, ECg epi form rate: 54.2%, EC epi form rate: 50.4%, EGC epi form rate: 49.6%, histidine concentration: 0.0076w / v%

[0064] In Examples 1-15 and 18 below, we focused on epigallocatechin gallate (EGCg) and investigated the effect of compounds such as amino acids on inhibiting the epimerization of EGCg.

[0065] <Example 1> Green tea beverage C was used as the base beverage. A base solution was obtained by dissolving EGCg raw material in green tea beverage C according to the formulation (w / v%) shown in Table 1. The pH of this base solution was adjusted using ascorbic acid (manufactured by Marugo Corporation) (hereinafter abbreviated as VC) and sodium bicarbonate (manufactured by Marugo Corporation) (hereinafter abbreviated as sodium bicarbonate) to prepare control samples 1-3 (pH 4.4-5.8). Furthermore, using the formulations shown in Table 1, EGCg raw materials and amino acids were dissolved and / or suspended in green tea beverage C, and the pH was adjusted with VC and sodium bicarbonate to prepare samples 1-16 (pH 4.9-5.2). The formulations shown in the table represent the amounts of each component (raw material). For example, although no histidine was added to control sample 1, this sample contains 0.0076 w / v% histidine derived from the base beverage (green tea beverage C). The control sample and the sample were filled into glass vials and heated in an autoclave at 115°C for 5 minutes. After heating, they were cooled to room temperature, and the pH and concentrations of EGCg and GCG were measured.

[0066] The EGCg ratio (%) was calculated from the sum of the EGCg and GCG concentrations using the formula 100 × EGCg concentration / (EGCg concentration + GCG concentration), and this was defined as the epitaminophen ratio (EGCg / (EGCg + GCG)). The epitaminophen ratio (%) in Examples 2-12, 14, and 18 was calculated using the same method as in Example 1.

[0067] In the examples, the epimerization reaction rate (k) and the pH-corrected epimerization reaction rate ratio were determined by the method described below unless otherwise specified. Using the pH-corrected epimerization reaction rate ratio allows for comparison while correcting for the effects of pH differences between samples. The calculations were performed assuming an epimerization ratio of 45% and a non-epimerization ratio of 55% for non-polymerized catechins at equilibrium. The epimerization reaction rate (k) was calculated using the following formula (1), which is expressed by the heating time (t), the value obtained by subtracting 45% of the epimerization rate at the equilibrium state of EGCg and GCG from the epimerization rate after heating (X), and the value obtained by subtracting 45% of the epimerization rate at the equilibrium state of EGCg and GCG from the epimerization rate before heating (X0). Equation (1) Log(X / X0)=k×t

[0068] In addition, since the epimer ratio is related to pH, the epimerization reaction rate ratio corrected for pH was also calculated (Examples 1 to 4, 6 to 7, 9, 14 to 15). As the calculation method, first, from X and X0 of three control samples with different pHs (for example, Control Samples 1 to 3 in Example 1), with the pH after heating on the horizontal axis and X / X0 on the vertical axis, a regression equation of X / X0 with respect to pH was obtained for the control samples. This regression equation is represented by the following formula (2) depending on pH, X, and X0. In the following formula (2), b represents the slope and A represents the intercept. Formula (2) X / X0 = b × [pH] + A By substituting the pH after heating of the sample to be evaluated into the above formula (2), the pH-corrected X / X0 of the control sample (X / X0 of the control sample having the same pH as the sample to be evaluated) is obtained. From the pH-corrected X / X0 of the control sample obtained by substituting pH into this formula (2), and further from the above-mentioned epimerization reaction rate calculation formula (the above formula (1)), the pH-corrected rate (k 対照試料 ) of the control sample is calculated. The ratio (k 試料 ) of this to the epimerization reaction rate (k 対照試料 / k 試料 ) calculated from the epimer ratio of the sample is calculated and taken as the epimerization reaction rate ratio corrected for pH. The larger the number of this epimerization reaction rate ratio corrected for pH, the higher the suppression rate of epimerization (non-epimerization) from the epimer to the non-epimer.

[0069] In Examples 5, 8, 10 to 13, 16 to 18, the epimerization reaction rate ratio without pH correction was determined. The epimerization reaction rate ratio without pH correction (hereinafter referred to as the epimerization reaction rate ratio) indicates the reaction rate ratio (k 試料 and k 対照試料 ) of the sample compared with the control sample having the same pH (after heating). This epimerization reaction rate ratio is obtained by calculating the epimerization reaction rates (k 試料 and k 対照試料 ) from formula (1) for each of the sample and the control sample by the above method, and taking the ratio (k 対照試料 / k 試料 ) of the epimerization reaction rate of the control sample having the same pH as the sample to the epimerization reaction rate of the sample. A higher epimerization reaction rate ratio indicates a higher inhibition rate of epimerization (de-epimerization) from the epimerized isomer to the non-epimerized isomer.

[0070] Table 1 shows the pH before and after heating, the concentrations of EGCg and GCG, the epimerization ratio (EGCg / (EGCg+GCg)), and the epimerization reaction rate ratio (pH-corrected or uncorrected).

[0071] [Table 1]

[0072] <Example 2> Using the formulations (w / v%) shown in Table 2, EGCg raw material was dissolved in Blend Tea A to obtain a base solution. The pH of this base solution was adjusted using VC and sodium bicarbonate to prepare control samples 4-6 (pH 5.0-5.6). Furthermore, using the formulation shown in Table 2, EGCg raw materials and amino acids were dissolved and / or suspended in Blend Tea A, and the pH was adjusted with VC and sodium bicarbonate to prepare samples 17-20 (pH 5.3). The control sample and the sample were heated and cooled using the same method as in Example 1. Table 2 shows the pH before and after heating, the concentrations of EGCg and GCg, the epimerization rate (EGCg / (EGCg+GCg)), and the pH-corrected epimerization reaction rate ratio.

[0073] [Table 2]

[0074] <Example 3> Using the formulations (w / v%) shown in Table 3, EGCg raw material was dissolved in green tea beverage C to obtain a base solution. The pH of this base solution was adjusted using VC and sodium bicarbonate to prepare control samples 7-9 (pH 4.5-5.6). Furthermore, using the formulation shown in Table 3, samples 21-22 were prepared by dissolving EGCg raw materials and amino acids in green tea beverage C, and adjusting the pH with VC and sodium bicarbonate. The control sample and the sample were heated and cooled using the same method as in Example 1. Table 3 shows the pH before and after heating, the concentrations of EGCg and GCg, the epimerization rate (EGCg / (EGCg+GCg)), and the pH-corrected epimerization reaction rate ratio.

[0075] [Table 3]

[0076] As shown in Tables 1-3, aromatic amino acids (histidine, phenylalanine, tryptophan, tyrosine) and cysteine ​​were found to be highly effective in suppressing the epimerization of non-epimeric catechins to non-epimeric polymerized catechins. Among these, histidine showed particularly excellent epimerization inhibitory activity.

[0077] <Example 4> Using the formulations (w / v%) shown in Table 4, EGCg raw material was dissolved in Blend Tea B to obtain a base solution. The pH of this base solution was adjusted using VC and sodium bicarbonate to prepare control samples 10-12 (pH 5.0-5.5). Furthermore, using the formulation shown in Table 4, EGCg raw material and histidine, carnosine, anserine, 3-methylhistidine, or 4-methylhistidine were dissolved in Blend Tea B, and the pH was adjusted with VC and sodium bicarbonate to prepare samples 23-27 (pH 5.1-5.5). The control sample and the sample were packed into glass vials, heated in an autoclave at 120°C for 5 minutes, and then cooled to room temperature. Table 4 shows the pH before and after heating, the concentrations of EGCg and GCG, the epimerization rate (EGCg / (EGCg+GCg)), and the pH-corrected epimerization reaction rate ratio.

[0078] [Table 4]

[0079] As shown in Table 4, histidine, carnosine, anserine, 3-methylhistidine, and 1-methylhistidine were found to be highly effective in suppressing the epimerization of non-epimeric catechins to non-epimeric polymerized catechins. These results suggest that aromatic amino acids, dipeptides containing them, and related compounds have an inhibitory effect on the epimerization of non-epimeric catechins.

[0080] <Example 5> Using the formulations (w / v%) shown in Table 5, EGCg raw material was dissolved in Blend Tea A to obtain a base solution. The pH of this base solution was adjusted using VC and sodium bicarbonate to prepare control sample 13 (pH 5.7). Furthermore, using the formulation shown in Table 5, EGCg raw material and histidine were dissolved in Blend Tea A, and the pH was adjusted with VC and sodium bicarbonate to prepare samples 28-33 (pH 5.8). The control sample and the sample were packed into glass vials, heated in an autoclave at 130°C for 1 minute, and then cooled to room temperature. Table 5 shows the pH before and after heating, the concentrations of EGCg and GCG, the epimerization ratio (EGCg / (EGCg+GCg)), and the epimerization reaction rate ratio. For the epimerization reaction rate, the ratio of the reaction rate of each sample to the control sample 13 was calculated.

[0081] [Table 5]

[0082] <Example 6> Using the formulations (w / v%) shown in Table 6, EGCg raw material was dissolved in green tea beverage C to obtain a base solution. The pH of this base solution was adjusted using VC and sodium bicarbonate to prepare control samples 14-16 (pH 4.5-5.6). Furthermore, using the formulation shown in Table 6, EGCg raw material and histidine were dissolved in green tea beverage C, and the pH was adjusted with VC and sodium bicarbonate to prepare samples 34-42 (pH 5.1). The control sample and the sample were packed into glass vials, heated in an autoclave at 115°C for 5 minutes, and then cooled to room temperature. Table 6 shows the pH before and after heating, the concentrations of EGCg and GCG, the epimerization rate (EGCg / (EGCg+GCg)), and the pH-corrected epimerization reaction rate ratio.

[0083] [Table 6]

[0084] <Example 7> Using the formulations (w / v%) shown in Table 7, EGCg raw material was dissolved in Blend Tea A to obtain a base solution. The pH of this base solution was adjusted using VC and sodium bicarbonate to prepare control samples 17-19 (pH 3.8-5.2). Furthermore, using the formulation shown in Table 7, EGCg raw material and histidine were dissolved in Blend Tea A, and the pH was adjusted with VC and sodium bicarbonate to prepare samples 43-45 (pH 5.1-5.3). The control sample and the sample were packed into glass vials, heated in an autoclave at 130°C for 1 minute, and then cooled to room temperature. Table 7 shows the pH before and after heating, the concentrations of EGCg and GCG, the epimerization rate (EGCg / (EGCg+GCg)), and the pH-corrected epimerization reaction rate ratio.

[0085] [Table 7]

[0086] As shown in Tables 5-7, the addition of histidine was confirmed to have an inhibitory effect on epimerization.

[0087] <Example 8> Using the formulations (w / v%) shown in Table 8, EGCg raw material was dissolved in Blend Tea A to obtain a base solution. The pH of this base solution was adjusted using VC and sodium bicarbonate to prepare control samples 20-25 (pH 2.6-5.2). Furthermore, using the formulation shown in Table 8, EGCg raw material and histidine were dissolved in Blend Tea A, and the pH was adjusted with VC and sodium bicarbonate to prepare samples 46-51 (pH 2.6-5.1). The control sample and the sample were packed into glass vials, heated in an autoclave at 130°C for 1 minute, and then cooled to room temperature. Table 8 shows the pH before and after heating, the concentrations of EGCg and GCG, the epimerization rate (EGCg / (EGCg+GCg)), and the epimerization reaction rate ratio. For the epimerization reaction rate ratio, the ratio of the reaction rates of sample 46 to control sample 20, sample 47 to control sample 21, sample 48 to control sample 22, sample 49 to control sample 23, sample 50 to control sample 24, and sample 51 to control sample 25 were calculated.

[0088] [Table 8]

[0089] <Example 9> Using the formulations (w / v%) shown in Table 9, EGCg raw material was dissolved in Blend Tea A to obtain a base solution. The pH of this base solution was adjusted using VC and sodium bicarbonate to prepare control samples 26-28 (pH 6.0-8.0). Furthermore, using the formulation shown in Table 9, EGCg raw material and histidine were dissolved in Blend Tea A, and the pH was adjusted with VC and sodium bicarbonate to prepare samples 52-54 (pH 6.0-8.0). The control sample and the sample were packed into glass vials, heated in an autoclave at 105°C for 1 minute, and cooled to room temperature. Table 9 shows the pH before and after heating, the concentrations of EGCg and GCG, the epimerization rate (EGCg / (EGCg+GCg)), and the epimerization reaction rate ratio. For the epimerization reaction rate ratio, the ratio of the reaction rates of sample 52 to control sample 26, sample 53 to control sample 27, and sample 54 to control sample 28 was calculated.

[0090] [Table 9]

[0091] As shown in Tables 8-9, the histidine-induced inhibition of epimerization was observed at all pH levels from 2 to 8.

[0092] <Example 10> Using the formulations (w / v%) shown in Table 10, EGCg raw material was dissolved in Blend Tea A to obtain a base solution. The pH of this base solution was adjusted using VC and sodium bicarbonate to prepare control samples 29-37 (pH 5.3). Furthermore, using the formulation shown in Table 10, EGCg raw material and histidine were dissolved in Blend Tea A, and the pH was adjusted with VC and sodium bicarbonate to prepare samples 55-63 (pH 5.3). The control sample and the sample were filled into glass vials, heated in an autoclave at 130°C for 1 minute, and cooled to room temperature. Table 10 shows the pH before and after heating, the concentrations of EGCg and GCG, the epimerization rate (EGCg / (EGCg+GCg)), and the epimerization reaction rate ratio. For the epimerization reaction rate ratio, the ratio of the reaction rates of sample 55 to control sample 29, sample 56 to control sample 30, sample 57 to control sample 31, sample 58 to control sample 32, sample 59 to control sample 33, sample 60 to control sample 34, sample 61 to control sample 35, sample 62 to control sample 36, and sample 63 to control sample 37.

[0093] [Table 10]

[0094] As shown in Table 10, an epimerization inhibitory effect was confirmed at all concentrations of non-polymerized epimeric catechins. Particularly high epimerization inhibitory effects were obtained in the range of 50 to 2400 μg / mL for non-polymerized epimeric catechin concentrations.

[0095] <Example 11> Using the formulations (w / v%) shown in Table 11, EGCg raw material was dissolved in green tea beverage C to obtain a base solution. The pH of this base solution was adjusted using VC and sodium bicarbonate to prepare control samples 38-42 (pH 5.7). Furthermore, using the formulation shown in Table 11, EGCg raw material and histidine were dissolved in green tea beverage C, and the pH was adjusted with VC and sodium bicarbonate to prepare samples 64-68 (pH 5.7). The control sample and the sample were heat-treated at the temperatures and times shown in Table 11 using a heat exchanger (model: MINI UHT P-20) manufactured by PowerPoint International Co., Ltd., and then cooled to room temperature. Table 11 shows the pH before and after heating, the concentrations of EGCg and GCG, the epimerization fraction (EGCg / (EGCg+GCg)), and the epimerization reaction rate ratio. For the epimerization reaction rate ratio, the ratio of the reaction rates of sample 64 to control sample 38, sample 65 to control sample 39, sample 66 to control sample 40, sample 67 to control sample 41, and sample 68 to control sample 42 were calculated.

[0096] [Table 11]

[0097] <Example 12> A base solution was obtained by dissolving the ECg raw material in blended tea A according to the formulation (w / v%) shown in Table 12. The pH of this base solution was adjusted using VC and sodium bicarbonate to prepare control sample 43 (pH 4.9). Furthermore, using the formulation shown in Table 12, EGCg raw material and histidine were dissolved in Blend Tea A, and the pH was adjusted with VC and sodium bicarbonate to prepare samples 69-72 (pH 4.9). The control sample and the sample were placed in 1.5 mL tubes and used in a block incubator (model: MG-3100, EYELA). They were heated at 100°C for 15 to 240 minutes and then cooled to room temperature. Table 12 shows the pH before heating, the concentrations of EGCg and GCG before and after heating, the epimerization rate (EGCg / (EGCg+GCg)), and the epimerization reaction rate ratio. For the epimerization reaction rate ratio, the ratio of the reaction rates of samples 69-72 to control sample 43 was calculated.

[0098] [Table 12]

[0099] <Example 13> An ECg raw material was dissolved in propylene glycol at 80°C to prepare a 20 w / v% ECg solution (hereinafter referred to as ECg solution) dissolved in propylene glycol. An ECg-containing beverage was obtained by dissolving the ECg solution in blended tea A according to the formulation (w / v%) shown in Table 13. The pH of this ECg-containing beverage was adjusted using vitamin C and sodium bicarbonate to prepare control sample 44 (pH 5.7). Furthermore, using the formulation shown in Table 13, ECg solution and histidine were dissolved in Blend Tea A, and the pH was adjusted with VC and sodium bicarbonate to prepare Sample 73 (pH 5.6). The control sample and the sample were filter-sterilized and sealed in 50 mL glass vials. These were stored for 3 weeks in an incubator (product name: Heratherm 100, Thermo Fisher Scientific) at the temperatures shown in Table 13. After storage, the pH and the concentrations of ECg and catechin gallate (Cg) were measured. Table 13 shows the pH, concentrations of ECg and Cg, epimerization ratio (ECg / (ECg+Cg)), and epimerization reaction rate ratio after storage. In Example 13, the epimerization ratio (ECg / (ECg+Cg)) was calculated from the concentration of non-polymerized catechin (w / v%) using the following formula. Epiphyseal percentage (%) = 100 × concentration of ECg / (total concentration of ECg and Cg) The epimerization reaction rate (k) was calculated using the following formula (3), which is expressed by the heating time (t), the value obtained by subtracting 45% of the epimerization rate at equilibrium from the epimerization rate after heating (X), and the value obtained by subtracting 45% of the epimerization rate at equilibrium from the epimerization rate before heating (X0). Equation (3) Log(X / X0)=k×t The epimerization reaction rate ratio was calculated by determining the ratio of the reaction rate of sample 73 to that of control sample 44.

[0100] [Table 13]

[0101] As shown in Tables 11-13, the histidine-mediated effect of inhibiting epimerization was confirmed in all temperature ranges from 23°C to 145°C. Epimerization progressed at higher temperatures, but histidine effectively suppressed it.

[0102] <Example 14> Using the formulations (w / v%) shown in Table 14, EGCg raw material was dissolved in green tea beverage C to obtain a base solution. The pH of this base solution was adjusted using VC and sodium bicarbonate to prepare control samples 45-47 (pH 4.5-5.6). Furthermore, samples 74-77 (pH 5.1) were prepared by dissolving EGCg raw material and histidine or its salt in green tea beverage C using the formulation shown in Table 14. Histidine, L-histidine hydrochloride reagent, L-histidine raw material, or L-histidine hydrochloride raw material were used as the histidine or its salt. The control sample and the sample were packed into glass vials, heated in an autoclave at 115°C for 5 minutes, and then cooled to room temperature. Table 14 shows the pH before and after heating, the concentrations of EGCg and GCG, the epimerization rate (EGCg / (EGCg+GCg)), and the pH-corrected epimerization reaction rate ratio.

[0103] [Table 14]

[0104] As shown in Table 14, an epimerization inhibitory effect was confirmed regardless of whether the reagent or raw material histidine or histidine salt was used.

[0105] <Example 15> Using the formulations (w / v%) shown in Table 15, EGCg raw material was dissolved in blended tea beverage A to obtain a base solution. The pH of this base solution was adjusted using VC and sodium bicarbonate to prepare control samples 48-50 (pH 4.6-5.6). Furthermore, samples 78-83 (pH 5.0-5.2) were prepared by dissolving EGCg raw material and histidine in commercially available blended tea beverage A using the formulation shown in Table 15. L-histidine (histidine) or D-histidine was used. The control sample and the sample were packed into glass vials, heated in an autoclave at 115°C for 5 minutes, and then cooled to room temperature. Table 15 shows the pH before and after heating, the concentrations of EGCg and GCG, the epimerization rate (EGCg / (EGCg+GCg)), and the pH-corrected epimerization reaction rate ratio.

[0106] [Table 15]

[0107] <Example 16> Using the formulations (w / v%) shown in Table 16, epi-nonpolymerized catechins (EGCg raw material, ECg raw material, epigallocatechin (EGC) or epicatechin (EC)) were dissolved and / or suspended in Blend Tea A (concentration of each nonpolymerized catechin: below the detection limit) to obtain a solution containing epi-nonpolymerized catechins. The pH of the obtained epi-nonpolymerized catechin-containing solution was adjusted to prepare control samples 51-62 (pH 4.5-5.5). Furthermore, samples 84-87 (pH 5.0) were prepared by dissolving and / or suspending epi-nonpolymerized catechins (EGCg raw material, ECg raw material, EGC or EC) and histidine in blended tea A using the formulation shown in Table 16. The control sample and the sample were filled into glass vials and heated in an autoclave at 130°C for 1 minute. After cooling, the pH and the concentrations of epitropic unpolymerized catechins (EGCg, ECg, EGC, EC) and non-epitropic unpolymerized catechins (gallocatechin gallate (GCg), catechin gallate (Cg), gallocatechin (GC), catechin (C)) were measured. Table 16 shows the pH after heating, the concentration of nonpolymerized catechins, the epitropic ratio (epitropic / (epitropic + non-epitropic)), and the pH-corrected epimerization reaction rate ratio. "-" indicates that the concentration was below the detection limit.

[0108] The epimerization reaction rate (k) was calculated using the above formula (3), which is expressed by the heating time (t), the value obtained by subtracting 45% of the epimerization rate at equilibrium from the epimerization rate after heating (X), and the value obtained by subtracting 45% of the epimerization rate at equilibrium from the epimerization rate before heating (X0). The pH-corrected epimerization reaction rate ratio was calculated using the same method as in Example 1. The regression equation (Equation (2)) above was prepared for EGCg (control samples 51-53), ECg (control samples 54-56), EGC (control samples 57-59), and EC (control samples 60-62), respectively.

[0109] [Table 16]

[0110] <Example 17> Using the formulations shown in Table 17 (w / v%), non-epi non-polymerized catechins (gallocatechin gallate (GCg), catechin gallate (Cg), gallocatechin (GC), or catechin (C)) were dissolved and / or suspended in Blend Tea A (concentration of each non-polymerized catechin: below the detection limit) to obtain a non-epi non-polymerized catechin-containing solution. The pH of the obtained non-epi non-polymerized catechin-containing solution was adjusted to prepare control samples 63-66 (pH 6.0). Furthermore, using the formulation shown in Table 17, non-epi non-polymerized catechins (GCg, Cg, GC, or C) and histidine were dissolved and / or suspended in Blend Tea A, and the pH was adjusted to prepare samples 88-91 (pH 6.0). The control sample and the sample were placed in 1.5 mL tubes, heated in a block incubator at 100°C for 15 minutes, and then cooled to room temperature. The pH and the concentrations of epi-unpolymerized catechins (EGCg, ECg, EGC, EC) and non-epi-unpolymerized catechins (GCg, Cg, GC, C) were measured. Table 17 shows the pH after heating, the concentration of non-polymerized catechins, the non-epi ratio (non-epi / (epi + non-epi)), and the epimerization reaction rate ratio.

[0111] The epimerization reaction rate (k) was calculated using the following formula (4), which is expressed by the heating time (t), the value obtained by subtracting 55% of the non-epi component percentage at equilibrium from the non-epi component percentage after heating (X), and the value obtained by subtracting 55% of the non-epi component percentage at equilibrium from the non-epi component percentage before heating (X0). Equation (4) Log(X / X0)=k×t The epimerization reaction rate ratio was calculated by comparing the reaction rates of sample 88 to control sample 63, sample 89 to control sample 64, sample 90 to control sample 65, and sample 91 to control sample 66. In Example 17, a larger number in this epimerization reaction rate ratio indicates a higher suppression rate of epimerization (epiformation) from the non-epiform to the epiform.

[0112] [Table 17]

[0113] As shown in Tables 16-17, the histidine-mediated inhibitory effect on epimerization was confirmed in both epimeric and non-epimeric non-polymerized catechins.

[0114] <Example 18> Blend tea A (concentration of each non-polymerized catechin: below the detection limit) was diluted with deionized water according to the formulation (w / v%) shown in Table 18, or white sugar (manufactured by Nisshin Sugar Refining Co., Ltd.) was added and dissolved to adjust the Brix, and the EGCg raw material was dissolved to obtain a base solution. The pH of this base solution was adjusted using VC and sodium bicarbonate to prepare control samples 67-74 (pH 5.5). Brix (25°C) was measured using an ATAGO digital refractometer, model number: PR-101α. Furthermore, using the formulation shown in Table 18, blended tea A was diluted with deionized water, or white sugar (manufactured by Nisshin Sugar Refining Co., Ltd.) was added and dissolved to adjust the Brix level. EGCg raw material and histidine were then dissolved, and the pH was adjusted with VC and sodium bicarbonate to prepare samples 92-99 (pH 5.5). The control sample and the sample were filled into glass vials, heated in an autoclave at 130°C for 1 minute, and cooled to room temperature. Table 18 shows the pH before and after heating, the concentrations of EGCg and GCG, the epimerization ratio (EGCg / (EGCg+GCg)), the epimerization reaction rate ratio, and Brix. For the epimerization reaction rate ratio, the ratio of the reaction rates of sample 92 to control sample 67, sample 93 to control sample 68, sample 94 to control sample 69, sample 95 to control sample 70, sample 96 to control sample 71, sample 97 to control sample 72, sample 98 to control sample 73, and sample 99 to control sample 74.

[0115] [Table 18]

[0116] As shown in Table 18, epimerization of non-polymerized epithelial catechins by histidine was suppressed in all Brix concentrations from 0.1% to 3.1%.< / ph>

Claims

1. An epimerization inhibitor for non-polymerized catechins, comprising at least one compound (A) selected from the group consisting of histidine, methylhistidine, phenylalanine, tryptophan, tyrosine, carnosine, anserine, and salts thereof, as an active ingredient.

2. The epimerization inhibitor of nonpolymerized catechins according to claim 1, wherein compound (A) is at least one selected from the group consisting of histidine, methylhistidine, histidine or methylhistidine-containing dipeptides and salts thereof.

3. The epimerization inhibitor of nonpolymerized catechins according to claim 1 or 2, wherein compound (A) is histidine and / or a salt thereof.

4. The epimerization inhibitor for non-polymerized catechins according to claim 1 or 2, wherein compound (A) is at least one selected from the group consisting of carnosine, anserine, and salts thereof.

5. An epimerization inhibitor of nonpolymerized catechins according to claim 1 or 2, used to suppress the epimerization of at least one nonpolymerized catechin selected from the group consisting of epicatechin, epigallocatechin, epicatechin gallate, epigallocatechin gallate, catechin, gallocatechin, catechin gallate, and gallocatechin gallate.

6. An epimerization inhibitor of non-polymerized catechins according to claim 1 or 2, used to suppress epimerization of at least one non-polymerized epicatechin selected from the group consisting of epicatechin, epigallocatechin, epicatechin gallate, and epigallocatechin gallate.

7. It comprises histidine and / or a salt thereof (A1) and epi-unpolymerized catechin (B1), A packaged beverage containing epi-unpolymerized catechin, wherein the pH is greater than 4.5 and less than or equal to 7.9, the histidine-equivalent concentration of histidine and / or its salt (A1) is 0.015 to 3 w / v%, the concentration of epi-unpolymerized catechin (B1) is 50 μg / mL to 5000 μg / mL, and the Brix is ​​3.0% or less.

8. The epi-unpolymerized catechin (B1) is at least one selected from the group consisting of epicatechin, epigallocatechin, epicatechin gallate, and epigallocatechin gallate, as described in claim 7.

9. The epi-nonpolymerized catechin-containing packaged beverage according to claim 7 or 8, wherein the epi-nonpolymerized catechin (B1) contains epigallocatechin gallate and / or epicatechin gallate, and the concentration of epigallocatechin gallate in the beverage is 2400 μg / mL or less, and / or the concentration of epicatechin gallate is 2400 μg / mL or less.

10. The epi-nonpolymerized catechin-containing packaged beverage according to claim 7 or 8, wherein the epi-nonpolymerized catechin (B1) contains epigallocatechin gallate, and the concentration of epigallocatechin gallate in the beverage is 400 μg / mL or less.

11. A packaged beverage containing epi-nonpolymerized catechin according to claim 7 or 8, wherein Brix is ​​1.4% or less.

12. The containerized beverage containing epi-nonpolymerized catechin according to claim 7 or 8, wherein the beverage is a tea beverage.

13. It contains histidine and / or a salt thereof (A1), epi-nonpolymerized catechin (B1), and an aqueous medium (C) containing water. A method for producing a packaged beverage containing epi-nonpolymerized catechin, comprising the step of heating a mixture having a histidine-based concentration of histidine and / or its salt (A1) of 0.015 to 3 w / v%, a pH greater than 4.5 and 8.0 or less, a concentration of epi-nonpolymerized catechin (B1) of 50 μg / mL to 5000 μg / mL, and a Brix of 3.0% or less, to 100°C or higher.

14. The method for producing the epi-nonpolymerized catechin (B1) according to claim 13, wherein the epi-molten catechin (B1) is at least one selected from the group consisting of epicatechin, epigallocatechin, epicatechin gallate, and epigallocatechin gallate.

15. The method for producing the product according to claim 13 or 14, wherein the nonpolymerized epicatechin (B1) comprises epigallocatechin gallate and / or epicatechin gallate, and the concentration of epigallocatechin gallate in the mixture is 2400 μg / mL or less, and / or the concentration of epicatechin gallate is 2400 μg / mL or less.

16. The production method according to claim 13 or 14, wherein the nonpolymerized epicatechin (B1) contains epigallocatechin gallate, and the concentration of epigallocatechin gallate in the mixture is 400 μg / mL or less.

17. The manufacturing method according to claim 13 or 14, wherein the Brix of the mixture is 1.4% or less.

18. Use of at least one compound selected from the group consisting of histidine, methylhistidine, phenylalanine, tryptophan, tyrosine, carnosine, anserine, and salts thereof, for inhibiting the epimerization of nonpolymerized catechins.

Images