WO2023008455A1

WO2023008455A1 - Agent for suppressing epimerization of non-polymerized catechin, container-filling beverage containing epimeric non-polymerized catechin, and method for producing same

Info

Publication number: WO2023008455A1
Application number: PCT/JP2022/028857
Authority: WO
Inventors: 貴嗣土屋; 亮太宮成; 将士伊藤
Original assignee: サントリーホールディングス株式会社
Priority date: 2021-07-27
Filing date: 2022-07-27
Publication date: 2023-02-02
Also published as: JPWO2023008455A1

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

Epimerization inhibitor for unpolymerized catechins, packaged beverage containing epimerized unpolymerized catechins, and method for producing the same

The present invention relates to an epimerization inhibitor for non-polymerized catechins. The present invention also relates to a packaged beverage containing epi-unpolymerized catechin. The present invention also relates to a method for producing a packaged beverage containing epi-unpolymerized catechin.

Non-polymerized catechins are a kind of polyphenols and are known to have various physiological effects. For example, epi-unpolymerized catechins such as epicatechin gallate and epigallocatechin gallate are known to have antioxidant and antiviral effects. Health foods that are expected to have the functionality and health effects of non-polymerized catechins are also on the market.

In Patent Document 1, (A) 0.06 to 0.5% by mass of non-polymer catechins, (B) L-isoleucine, L-leucine, L-valine, L-threonine, DL-methionine, L- 0.01 to 5.0% by mass of one or more amino acids or salts thereof selected from methionine, L-histidine, L-phenylalanine, L-lysine and L-tryptophan, and (C) a sweetener of 0.0001 to It describes a packaged beverage containing 20% by mass, having a (G) non-polymer catechin gallate ratio of 5 to 55% by mass, and having a pH of 2.5 to 5.1.

JP 2008-178395 A

Beverages containing non-polymerized catechins as active ingredients are useful as functional beverages that contribute to the maintenance and promotion of health. However, for example, in beverages containing epi-unpolymerized catechins, part of the epi-non-polymerized catechins undergoes epimerization to become non-epi-unpolymerized catechins during production or storage after production. As a result, the content of epi-unpolymerized catechins in the beverage is reduced. It is important to enhance the stability of active ingredients in anticipation of functional beverages exhibiting their functionality, and a method capable of suppressing epimerization of non-polymerized catechins is desired. Patent Document 1 does not discuss a method for suppressing epimerization of non-polymerized catechins.

An object of the present invention is to provide an epimerization inhibitor for non-polymerized catechins. Another object of the present invention is to provide a packaged beverage containing epi-unpolymerized catechin in which epimerization of epi-non-polymerized catechin is suppressed, and a method for producing the same.

The present inventors have investigated techniques for suppressing epimerization of non-polymerized catechins and found that specific amino acids, dipeptides and salts thereof have the effect of suppressing epimerization of non-polymerized catechins.

That is, although not limited thereto, the present invention provides the following epimerization inhibitor for non-polymerized catechins, a packaged beverage containing epi-unpolymerized catechins, and a method for producing packaged beverages containing non-polymerized epi-catechins. contain.
[1] A non-polymerized catechin containing, as an active ingredient, at least one compound (A) selected from the group consisting of aromatic amino acids, cysteine, aromatic amino acids and/or cysteine-containing dipeptides, and salts thereof. Epimerization inhibitor.
[2] The compound (A) is at least one selected from the group consisting of an aromatic amino acid, a dipeptide containing an aromatic amino acid, and a salt thereof. [1] suppresses epimerization of non-polymerized catechins. agent.
[3] Epimerization of non-polymerized 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. inhibitor.
[4] Any one of [1] to [3] above, wherein the compound (A) is at least one selected from the group consisting of histidine, methylhistidine, histidine or a dipeptide containing methylhistidine and salts thereof. Epimerization inhibitor of non-polymerized catechins as described.
[5] The epimerization inhibitor of non-polymerized catechins according to any one of [1] to [4] above, wherein the compound (A) is histidine and/or a salt thereof.
[6] Compound (A) is at least one selected from the group consisting of carnosine, anserine and salts thereof, suppressing epimerization of non-polymerized catechins according to any one of [1] to [4] above agent.
[7] The compound (A) is at least one selected from the group consisting of cysteine, cysteine-containing dipeptides, and salts thereof.
[8] to suppress epimerization of at least one non-polymerized 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-polymerized catechins according to any one of [1] to [7], which is used in the above.
[9] The above [1], which is used to suppress epimerization of at least one epimerized unpolymerized catechin selected from the group consisting of epicatechin, epigallocatechin, epicatechin gallate and epigallocatechin gallate. The epimerization inhibitor for non-polymerized catechins according to any one of [8].
[10] containing histidine and/or a salt thereof (A1) and an epi-unpolymerized catechin (B1), having a pH of more than 4.5 and not more than 7.9, wherein the histidine and/or salt thereof (A1 ) has a histidine-equivalent concentration of 0.015 to 3 w/v% and a Brix of 3.0% or less.
[11] The epi-isomer 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. A packaged beverage containing non-polymerized catechins.
[12] The epi-unpolymerized catechin (B1) contains epigallocatechin gallate and/or epicatechin gallate, and the epigallocatechin gallate concentration in the beverage is 2400 µg/mL or less, and/or the epicatechin gallate concentration The packaged beverage containing epi-unpolymerized catechins according to [10] or [11] above, wherein the is 2400 μg/mL or less.
[13] Any one of [10] to [12] above, wherein the epi-unpolymerized catechin (B1) contains epigallocatechin gallate, and the concentration of epigallocatechin gallate in the beverage is 400 μg/mL or less. A packaged beverage containing epi-unpolymerized catechins.
[14] The packaged beverage containing epi-unpolymerized catechins according to any one of [10] to [13] above, which has a Brix of 1.4% or less.
[15] The packaged beverage containing epi-unpolymerized catechins according to any one of [10] to [14] above, wherein the beverage is a tea beverage.
[16] containing histidine and/or a salt thereof (A1), an epi-unpolymerized catechin (B1), and an aqueous medium containing water (C), wherein the histidine and/or salt thereof (A1) is converted to histidine The concentration of 0.015 to 3 w / v%, the pH is more than 4.5 and 8.0 or less, and the Brix is 3.0% or less, and a step of heat-treating at 100 ° C. or higher A method for producing a packaged beverage containing epi-unpolymerized catechin, comprising:
[17] The production method according to [16] above, wherein the epi-unpolymerized catechin (B1) is at least one selected from the group consisting of epicatechin, epigallocatechin, epicatechin gallate and epigallocatechin gallate. .
[18] The epi-unpolymerized catechin (B1) contains epigallocatechin gallate and/or epicatechin gallate, and the concentration of epigallocatechin gallate in the mixture is 2400 μg/mL or less, and/or epicatechin gallate The production method according to [16] or [17] above, wherein the concentration is 2400 μg/mL or less.
[19] Any one of [16] to [18] above, wherein the epi-unpolymerized catechin (B1) contains epigallocatechin gallate, and the concentration of epigallocatechin gallate in the mixture is 400 μg/mL or less. Method of manufacture as described.
[20] The production method according to any one of [16] to [19] above, wherein the mixture has a Brix of 1.4% or less.
[21] 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, for suppressing epimerization of non-polymerized catechins use.

According to the present invention, an epimerization inhibitor for non-polymerized catechins can be provided. Moreover, according to the present invention, it is possible to provide a packaged beverage containing epi-non-polymerized catechin in which epimerization of epi-non-polymerized catechin is suppressed, and a method for producing the same.

<Epimerization inhibitor for non-polymerized catechin>
The epimerization inhibitor of non-polymerized catechins of the present invention comprises 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 suppressing epimerization of non-polymerized catechins. Compound (A) may be a single compound or a combination of two or more compounds. The aromatic amino acid, cysteine, is a free amino acid.
Epimerization of non-polymerized catechin means that non-polymerized catechin changes to its epimer. Epimerization of non-polymerized catechin is that epi-non-polymerized catechin changes to non-epi-non-polymerized catechin (epimerization of epi-non-polymerized catechin). Including changing (epimerization of non-epi unpolymerized catechins). The conversion of epi-nonpolymerized catechin to non-epi-nonpolymerized catechin is also called non-epimerization or non-epimerization. The conversion of non-epi-unpolymerized catechins to epi-catechins is also referred to as epimerization.

In the present invention, non-polymerized catechins include epicatechin, epigallocatechin, epicatechin gallate, epigallocatechin gallate and other epi-non-polymerized catechins; is a generic term for The non-polymerized catechin may be one of the above compounds, or may be a combination of two or more compounds.
When the above compound (A) is used, epimerization of epi-nonpolymerized catechin to non-epi-nonpolymerized catechin (for example, from epicatechin to catechin, from epigallocatechin to gallocatechin, from epicatechin gallate to catechin gallate, or from epigallocatechin) epimerization of catechin gallate to gallocatechin gallate), epimerization of non-epi non-polymerized catechins to epi non-polymerized catechins (e.g., catechin to epicatechin, gallocatechin to epigallocatechin, catechin gallate to epicatechin gallate, or , epimerization of gallocatechin gallate to epigallocatechin gallate) can be effectively inhibited. For example, epimerization of non-epi-polymerized catechins by heat, pH, etc., into non-epi-non-polymerized catechins can be effectively inhibited by using the compound (A).

In one embodiment, the non-polymerized catechin epimerization inhibitor of the present invention is selected from the group consisting of epicatechin, epigallocatechin, epicatechin gallate, epigallocatechin gallate, catechin, gallocatechin, catechin gallate and gallocatechin gallate. It is preferably used for suppressing epimerization of at least one non-polymerized catechin. The epimerization inhibitor of unpolymerized catechins of the present invention inhibits the epimerization of at least one epimerized unpolymerized catechin selected from the group consisting of epicatechin, epigallocatechin, epicatechin gallate and epigallocatechin gallate. and more preferably for suppressing epimerization of epicatechin gallate and/or epigallocatechin gallate. In one aspect, the epimerization inhibitor of non-polymerized catechins of the present invention is suitably used for suppressing the epimerization of epi-non-polymerized catechins to non-epi-non-polymerized catechins. Unpolymerized catechins contained in natural products such as plants are mainly epi-unpolymerized catechins. The epimerization inhibitor of non-polymerized catechins of the present invention is useful, for example, for inhibiting epimerization of non-polymerized catechins derived from natural products such as plants.

In one aspect, the compound (A) is preferably 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. At least one amino acid selected from the group consisting of histidine, methylhistidine, phenylalanine, tryptophan and tyrosine is preferable as the aromatic amino acid in the present invention. Among them, histidine and methylhistidine are more preferable, and histidine is even more preferable, since they are highly effective in suppressing epimerization of non-polymerized catechins.

Dipeptides containing histidine or methylhistidine are preferred as dipeptides containing aromatic amino acids. As dipeptides containing histidine or methylhistidine, carnosine and anserine are preferred. In one aspect, compound (A) is preferably at least one selected from the group consisting of carnosine, anserine and salts thereof.

In one aspect of the present invention, compound (A) is preferably at least one selected from the group consisting of histidine, methylhistidine, dipeptides containing histidine or methylhistidine, and salts thereof. and salts thereof, more preferably at least one selected from the group consisting of these, more preferably histidine and/or salts thereof, and particularly preferably histidine.
In one aspect, when epimerization of epi-unpolymerized catechin to non-epi-unpolymerized catechin is suppressed, the compound (A) is preferably histidine and/or a salt thereof, more preferably histidine.

In another aspect of the present invention, the compound (A) is preferably at least one selected from the group consisting of cysteine, dipeptides containing cysteine, and salts thereof. Cysteine-containing dipeptides include, for example, γ-glutamylcysteine.

In the present invention, the amino acid may be L-form, D-form, or a mixture thereof (DL-form).
Salts of the above amino acids or dipeptides are not particularly limited, but salts acceptable for food and drink or pharmacologically acceptable salts are preferable. The above amino acid or dipeptide salts may be either acid salts or basic salts. Acid salts include, for example, inorganic salts such as hydrochlorides, sulfates, nitrates, phosphates; Examples include organic acid salts such as acid salts and propionate salts. Examples of basic salts include alkali metal salts such as sodium salts and potassium salts; alkaline earth metal salts such as calcium salts and magnesium salts; Among them, acid salts are preferred, inorganic acid salts are preferred, and hydrochlorides are more preferred.

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

The total content of compound (A) in the epimerization inhibitor of unpolymerized catechins of the present invention may be, for example, 0.01 to 95 w/v%. The epimerization inhibitor for unpolymerized catechins of the present invention may contain components (for example, additives) other than the compound (A).

Addition of the compound (A) to the 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 the compound (A). Even if the non-polymerized catechin-containing composition contains the compound (A), the epimerization of non-polymerized catechins can be effectively suppressed by adding the epimerization inhibitor of non-polymerized catechins of the present invention. It becomes possible. The epimerization inhibitor of non-polymerized catechins of the present invention can be used in various compositions such as foods and drinks containing non-polymerized catechins, pharmaceuticals, quasi-drugs, cosmetics, feeds, and raw materials thereof. can be used to suppress the epimerization of

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, particle, etc.). but preferably in liquid form. The epimerization inhibitor of non-polymerized catechins is preferably used by being added to the non-polymerized catechin-containing liquid composition. Epimerization of non-polymerized catechins usually proceeds in a solution of non-polymerized catechins. Therefore, when the non-polymerized catechin epimerization inhibitor of the present invention is used in a non-polymerized catechin-containing liquid composition, the effect of the present invention can be particularly greatly obtained. The epimerization inhibitor for non-polymerized catechins of the present invention is an epimerized non-polymerized catechin or a non-epi non-polymerized catechin in a composition containing non-polymerized catechins in which epi-non-polymerized catechins and non-epi non-polymerized catechins are not in equilibrium. is preferably used to suppress the epimerization of

The origin and production method of the non-polymerized catechin are not particularly limited. Non-polymerized catechins may be derived from, for example, natural materials or chemically synthesized products. For example, non-polymerized catechins can be blended into the composition using natural materials containing non-polymerized catechins, extracts obtained by extracting the natural materials, and the like. Plant materials containing epi-unpolymerized catechins include leaves (tea leaves) of Camellia sinensis belonging to the genus Camellia of the family Theaceae. Examples of non-polymerized catechin-containing compositions include tea leaf extracts and liquid compositions such as beverages containing the same.

The non-polymerized catechin-containing composition is preferably a beverage containing non-polymerized catechin, more preferably a packaged beverage containing non-polymerized catechin, still more preferably a packaged beverage containing epi-unpolymerized catechin, particularly Packaged tea beverages containing epi-unpolymerized catechins are preferred. In one aspect, the epimerization inhibitor of unpolymerized catechins of the present invention can be suitably used as an epimerization inhibitor of unpolymerized catechins for packaged beverages.
In packaged beverages containing non-polymerized catechins, for example, beverages containing epi-unpolymerized catechins, the epi-unpolymerized catechins undergo epimerization over time during and after production. When at least one compound (A) is added to a packaged beverage containing epi-unpolymerized catechin, epimerization of the epi-unpolymerized catechin in the beverage can be suppressed. The epimerization inhibitor for non-polymerized catechins of the present invention may be added to raw materials during production of the non-polymerized catechin-containing composition, or may be added to the non-polymerized catechin-containing composition.

When the non-polymerized catechin-containing composition is liquid, the composition preferably has a pH of 3.0 to 8.0, more preferably 3.0 to 7.9. When the pH of the non-polymerized catechin-containing composition is within the above range, epimerization of non-polymerized catechins can be effectively suppressed when the epimerization inhibitor of non-polymerized catechins of the present invention is used. As used herein, pH is the pH at 25°C. pH can be measured with a commercially available pH meter.

In one aspect, when suppressing epimerization of the epi-unpolymerized catechin, the non-polymerized catechin-containing composition preferably has an epi-isomer ratio of the unpolymerized catechin of 45% or more, more preferably 50% or more. It is preferably 55% or more, even more preferably 60% or more, particularly preferably 63% or more, and most preferably 65% or more. In addition, the epi-body rate 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 non-polymerized catechin epimer ratio is preferably 45 to 100%, more preferably 50 to 100%, 55 to 100%, 60 to 100%, or 60 to 95%. , more preferably 60 to 92%, still more preferably 60 to 90%, particularly preferably 63 to 90%, most preferably 65 to 90%. When the epimerization inhibitor of non-polymerized catechins of the present invention is added to a composition containing non-polymerized catechins having an epi-isomer ratio within the above range, the epimerization of non-polymerized epi-isomers of catechins can be effectively suppressed. In the present invention, it is preferable that the epi-isomer rate of each epi-isomer unpolymerized catechin such as epigallocatechin gallate and epigallocatechin gallate contained in the non-polymerized catechin-containing composition is within the above range. For example, when the non-polymerized catechin-containing composition contains epigallocatechin gallate, the epimerization rate of epigallocatechin gallate is preferably within the above range, and when the composition contains epicatechin gallate, epicatechin gallate It is preferable that the volume ratio is within the above range. When the non-polymerized catechin-containing composition contains epicatechin, it is preferable that the epi-isomer rate of epicatechin is within the above range, and when it contains epigallocatechin, the epi-isomer rate of epigallocatechin is within the above range. is preferred.
In another aspect, when suppressing epimerization of non-epi non-polymerized catechins, the composition containing non-polymerized catechins preferably has a non-epi catechin rate of 45% or more, preferably 50% or more. is more preferably 55% or more, even more preferably 60% or more, particularly preferably 63% or more, and most preferably 65% or more. In addition, the non-epiform ratio may be 100% or less, 95% or less, 92% or less, or 90% or less. In one embodiment, the non-epi isomer ratio of non-polymerized catechin is preferably 45-100%, more preferably 50-100%, 55-100%, 60-100% or 60-95%, still more preferably 60-92%. %, still more preferably 60-90%, particularly preferably 63-90%, most preferably 65-90%. When the epimerization inhibitor of non-polymerized catechins of the present invention is added to a composition containing non-polymerized catechins having a non-epi isomer ratio within the above range, the epimerization of non-epi non-polymerized catechins can be effectively suppressed. . It is preferable that the non-epi isomer ratio of each non-epi catechin contained in the non-polymerized catechin-containing composition is within the above range.
The epi- and non-epi catechin ratios of the non-polymerized catechins are calculated from the content (concentration) (μg/mL) of the epi-non-polymerized catechins and the non-epi-non-polymerized catechins according to the following equations.
Ratio of epi isomer (%) = 100 x concentration of non-polymerized epi catechin/total concentration of non-polymerized epi catechin and non-polymerized catechin of non-epi catechin Ratio of non-epi catechin (%) = 100 x concentration of non-polymerized non-epi catechin /Total concentration of epi-non-polymerized catechin and non-epi-non-polymerized catechin

The amount of the epimerization inhibitor for non-polymerized catechins to be used is not particularly limited, and may be appropriately set according to, for example, the type of compound (A) and the composition containing non-polymerized catechins. The amount of the epimerization inhibitor for non-polymerized catechins used may be, for example, an amount such that the content of compound (A) in the composition containing non-polymerized catechins is 0.001 w/v% or more, and the compound ( The content of A) may be 20 w/v% or less. For example, when the compound (A) is histidine and / or a salt thereof, the content of histidine and / or a salt thereof in terms of histidine 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, still more preferably 0.016 w/v% or more or 0.017 w/v% or more, still more preferably 0.018 w/v% or more, particularly preferably 0.019 w/v % or more, most preferably 0.020 w/v % or more. On the other hand, when the content of histidine and/or its salt in the non-polymerized catechin-containing composition is high, the flavor derived from histidine and/or its salt becomes strong, which may be undesirable from the viewpoint of flavor. In one aspect, histidine and/or a salt thereof has a histidine-equivalent content in the non-polymerized catechin-containing composition, preferably 3 w/v% or less, more preferably 2 w/v% or less, even more preferably 1 w/v%. 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, most preferably 0.05w /v% or less is preferably used. In one aspect, when the compound (A) is histidine and/or a salt thereof, the amount of the epimerization inhibitor of non-polymerized catechin used is such that the content of histidine and/or a salt thereof in terms of histidine contains non-polymerized catechin In the composition, 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%, 0.015 to 1 w/v%. 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%, more preferably 0.020 to 0.2 w/v%, still more preferably 0.020 to 0.1 w/v%, particularly preferably 0.020 to 0.06 w/v%, most preferably 0 An amount of 0.020 to 0.05 w/v% is preferred. In one aspect, it is preferable to add an epimerization inhibitor of non-polymerized catechins so that the content of histidine and/or a salt thereof in terms of histidine in the non-polymerized catechin-containing composition falls within the above range. In a preferred embodiment of the present invention, non-polymerized catechins are epimerized such that the content of histidine and/or salts thereof in terms of histidine in beverages (preferably tea beverages) containing non-polymerized catechins falls within the above range. An inhibitor is preferably added to the beverage.

By adding the compound (A) to the 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 the compound (A) to the non-polymerized catechin-containing composition, epimerization of the non-polymerized catechin during storage can be suppressed, for example.

<Contained beverage containing epi-unpolymerized catechin>
The packaged beverage containing epi-unpolymerized catechin of the present invention contains histidine and/or a salt thereof (A1) and epi-unpolymerized catechin (B1), and has a pH of more than 4.5 and 7.9 or less. The histidine and/or salt thereof (A1) has a histidine-equivalent concentration of 0.015 to 3 w/v% and a Brix of 3.0% or less.
The packaged beverage containing epi-unpolymerized catechin of the present invention (hereinafter sometimes referred to as the packaged beverage of the present invention) is a packaged beverage in which a beverage containing epi-unpolymerized catechin is filled in a container.

Examples of histidine salts include the same amino acid or dipeptide salts as described above. The salt of histidine is preferably an acid salt of histidine, more preferably an inorganic acid salt of histidine, and still more preferably a hydrochloride of histidine.
In one aspect, histidine and/or histidine hydrochloride are preferable as histidine and/or its salt (A1), and histidine is more preferable.
The epi-unpolymerized catechin (B1) is preferably at least one selected from the group consisting of epicatechin, epigallocatechin, epicatechin gallate and epigallocatechin gallate. The epi-unpolymerized catechin (B1) more preferably contains epicatechin gallate and/or epigallocatechin gallate, and more preferably epigallocatechin gallate and/or epicatechin gallate.

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. In the packaged beverage containing the epi-unpolymerized catechin (B1), the epi-unpolymerized catechin in the beverage is epimerized over time and converted into the non-epi-unpolymerized catechin. When the histidine-equivalent concentration of histidine and/or a salt thereof (A) is within the above range, epimerization (non-epimerization) of the epi-unpolymerized catechin (B1) in the beverage over time is effectively suppressed. be able to. For this reason, it is effective to reduce the concentration of epi-unpolymerized catechins over time in packaged beverages (decrease in epi-unpolymerized catechins) and the ratio of epi-unpolymerized catechins in unpolymerized catechins (epi catechin ratio). can be suppressed to The concentration of histidine and/or its salt (A1) in the beverage, in terms of histidine, is preferably 0.016 w/v% or more, more preferably 0.017 w/v% or more, and still more preferably It is 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, when the concentration of histidine and/or its salt is high, it may not be preferable from the viewpoint of the flavor of the beverage. The concentration of histidine and/or salts thereof in the beverage is preferably 2 w/v% or less, more preferably 1 w/v% or less or 0.5 w/v% or less, still more preferably 0.2 w/v in terms of histidine. % or less, still 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 one embodiment, the histidine-equivalent concentration of histidine and/or a salt thereof 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 0.019 to 0.2 w/v%, 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% %, most preferably 0.020-0.05 w/v %. The concentration of histidine and/or its salt (A1) can be measured by a known method such as fluorescence method. Histidine and/or its salt (A1) is preferably dissolved and/or dispersed in the beverage.

The concentration of the epi-unpolymerized catechin (B1) in the beverage is not particularly limited. The total concentration of the epi-unpolymerized catechin (B1) in the beverage is, for example, preferably 50 μg/mL or more, more preferably 100 μg/mL or more, and preferably 5000 μg/mL or less, It is more preferably 4800 µg/mL or less, and even more preferably 2400 µg/mL or less. In the packaged beverage of the present invention, if the total concentration of the epi-unpolymerized catechins (B1) is within the above range, epimerization of the epi-unpolymerized catechins can be more effectively suppressed, which is preferable.
The beverage of the present invention preferably contains epigallocatechin gallate and/or epicatechin gallate. In this case, it is preferable that the epigallocatechin gallate concentration in the beverage is 2400 μg/mL or less and/or the epicatechin gallate concentration is 2400 μg/mL or less. When the concentration of epigallocatechin gallate in the beverage is within the above range, epimerization of epigallocatechin gallate to gallocatechin gallate can be further suppressed. Moreover, when the concentration of epicatechin gallate is within the above range, epimerization of epicatechin gallate to catechin gallate can be further suppressed.
In one aspect, the beverage contains epigallocatechin gallate and/or epicatechin gallate, the epigallocatechin gallate concentration in the beverage is 2400 μg/mL or less, and the epicatechin gallate concentration is 2400 μg/mL or less. Preferably. When the beverage contains epigallocatechin gallate, the concentration of epigallocatechin gallate in the beverage is preferably 50 μg/mL or more, more preferably 100 μg/mL or more, and 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, more preferably 200 μg/mL or less, even more preferably 160 μg/mL or less, and 150 μg/mL or less. It is particularly preferred to be no more than mL, most preferably no more than 140 μg/mL. When 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, and is 1200 μg/mL or less, 800 μg/mL. 600 μg/mL or less, 400 μg/mL or 300 μg/mL or less, more preferably 200 μg/mL or less, even more preferably 160 μg/mL or less, and 150 μg/mL or less is particularly preferred, and 140 μg/mL or less is most preferred. The epi-unpolymerized catechin (B1) is preferably dissolved and/or dispersed in the beverage.
The concentration of epi-unpolymerized catechin (B1) can be measured by a high performance liquid chromatography (HPLC) method. As the measurement conditions, the conditions described in Examples can be used.

In the present invention, the pH of the beverage is preferably more than 4.5 and 7.0 or less, more preferably more than 4.5 and 6.5 or less, 4.7 to 6.5 more preferably 4.9 to 6.5, even more preferably 5.0 to 6.5, particularly preferably 5.0 to 6.2, 5 .0 to 6.0 is most preferred.

The packaged beverage of the present invention has a Brix of 3.0% or less. The beverage preferably has a Brix of 1.8% or less. When the Brix of the beverage of the present invention is within the above range, epimerization of non-epi-polymerized catechin to non-epi-polymerized catechin can be more effectively suppressed. The beverage of the present invention preferably has a Brix of 1.4% or less, more preferably 1.2% or less, even more preferably 1.0% or less, and 0.9% or less. Alternatively, it is particularly preferably 0.8% or less, most preferably 0.7% or less. Brix of the beverage may be 0.01% or more, preferably 0.05% or more, more preferably 0.1% or more, further preferably 0.15% or more, particularly preferably 0.2% or more, 0.3% or more is most preferable. In one aspect, the beverage preferably has a Brix of 0.01 to 1.4%, 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%, more preferably 0.2 to 0.8% is more preferred, 0.2 to 0.7% is particularly preferred, and 0.3 to 0.7% is most preferred. It is also preferred that the Brix of the beverage is between 0.3 and 0.8%. It is preferable from the viewpoint of flavor that the Brix is within the above range. Brix can be evaluated by a Brix value obtained using a saccharimeter or a refractometer. The Brix value is a value obtained by converting the refractive index measured at 20° C. into mass/mass percent of the sucrose solution based on the conversion table of ICUMSA (International Commission for the Analysis of Sugar). The unit is "°Bx", "%" or "degree". Brix can be measured, for example, with a digital saccharimeter manufactured by ATAGO, model number: PR-101α.

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 one extracted from a plant material, one produced by a fermentation method, or a chemically synthesized product. The epi-unpolymerized catechin (B1) may be extracted from a plant containing epi-unpolymerized catechin. Plant materials containing epi-unpolymerized catechin include, for example, leaves of Camellia sinensis belonging to the genus Camellia of the family Theaceae. 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 non-polymerized catechin (B2). The packaged beverage of the present invention preferably has an epi-isomer rate of non-polymerized catechin of 45% or more, more preferably 50% or more, even more preferably 55% or more, and 60% or more. is even more preferred, 63% or more is particularly preferred, and 65% or more is most preferred. In addition, the epi-body rate may be 100% or less, 95% or less, 92% or less, or 90% or less. In one embodiment, the non-polymerized catechin epimer ratio in the beverage is preferably 45 to 100%, more preferably 50 to 100%, 55 to 100%, 60 to 100% or 60 to 95%, more preferably 60-92%, even more preferably 60-90%, particularly preferably 63-90%, most preferably 65-90%. It is preferable that the epi-isomer rate of each non-polymerized catechin such as epigallocatechin gallate and epigallocatechin gallate contained in the beverage is within the above range. For example, when the beverage contains epigallocatechin gallate, the epi-percentage of epigallocatechin gallate is preferably within the above range. When the beverage contains epicatechin gallate, the epicatechin gallate ratio is preferably within the above range. When the beverage contains epicatechin, the epicatechin ratio is preferably within the above range, and when it contains epigallocatechin, the epigallocatechin epibody ratio is preferably within the above range. In one aspect, the beverage of the present invention can also be produced by blending an extract of tea tree containing epi-unpolymerized catechins.

The beverage (liquid for internal use) in the packaged beverage of the present invention is liquid and contains water. The form of the beverage may be a straight beverage or a concentrated beverage, but a straight beverage is preferred. A straight drink means a drink that can be drunk as it is without dilution. Concentrated beverages refer to beverages that are diluted with a drinking solvent such as water. Beverages in the present invention may be non-alcoholic beverages or alcoholic beverages, but non-alcoholic beverages are preferred. In one aspect, the packaged beverage of the present invention is preferably a beverage other than a beer-taste alcoholic beverage (including beer), and more preferably a non-alcoholic beverage. Non-alcoholic beverages refer to beverages with an ethanol concentration of less than 1 v/v%. Examples of non-alcoholic beverages include, but are not limited to, tea beverages, non-alcoholic beer-taste beverages, and the like. In one aspect, the non-alcoholic beverage is preferably a non-alcoholic beverage other than a non-alcoholic beer-taste beverage. Alcoholic beverages include, but are not limited to, beer, beer-taste beverages, red wine, white wine, whiskey, and the like.

A tea beverage refers to a beverage containing a plant extract as a tea raw material. The raw material plant (plant-derived raw material) of the plant extract is not particularly limited, but includes leaves (tea leaves) of Camellia sinensis belonging to the family Camellia family Camellia sinensis, cereals, and leaves, stems, and roots of plants other than tea. .
Examples of tea leaves include tea leaves such as green tea, oolong tea (Tieguanyin, Irotane, Ogonkatsura, Wuyi rock tea, etc.), and black tea. One type of tea leaves may be used, or two or more types 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.
Grains include, for example, wheat such as barley, wheat, dove, and rye; rice such as brown rice; and millet such as beans such as soybeans and black soybeans. Grains can be used singly or in combination of two or more. Wheat is preferably barley or pigeon barley. Stems, leaves, or roots of plants other than tea tree include, for example, leaves of sagebrush.
The beverage of the present invention may contain one or more of tea extracts such as green tea extracts, oolong tea extracts, black tea extracts, and cereal extracts. The beverages of the present invention are preferably tea beverages such as green tea beverages, oolong tea beverages, black tea beverages, barley tea beverages, and blended tea beverages. A green tea beverage refers to a beverage containing 50% by weight or more of green tea leaves relative to the total amount of raw material plants used in the production of the beverage. A black tea beverage refers to a beverage in which black tea leaves are used in an amount of 50% by weight or more based on the total amount of raw material plants used in the production of the beverage. Oolong tea beverage refers to a beverage containing 50% by weight or more of oolong tea leaves based on the total amount of raw material plants used for the production of the beverage. A barley tea beverage is a beverage containing 50% by weight or more of barley (preferably barley and/or pigeon barley) relative to the total amount of raw material plants used in the production of the beverage. Blended tea beverages use multiple types of raw material plants, and the amount of green tea leaves, black tea leaves, oolong tea leaves, and barley used is less than 50% by weight of the total amount of raw material plants used in the manufacture of the beverage. Refers to a certain tea drink.

The packaged beverage of the present invention contains, for example, additives that can be used in beverages (e.g., antioxidants, flavors, vitamins, pigments, acidulants, emulsifiers, preservatives, seasonings, extracts, pH adjusters, quality additives such as stabilizers) may be contained in one or more.

In the packaged beverage of the present invention, the shape of the container is not particularly limited, and examples thereof include metal containers such as cans, bottles, retort pouches, PET bottles, paper packs, aluminum pouches, and vinyl pouches.
The method for producing the packaged beverage of the present invention is not particularly limited. For example, it can be produced by the following method for producing a packaged beverage containing epi-unpolymerized catechin.

In the packaged beverage of the present invention, epimerization of the epi-unpolymerized catechin is suppressed. By suppressing the epimerization of the epimerized non-polymerized catechin, for example, it is possible to suppress the decrease in the concentration of the epi-unpolymerized catechin over time during storage of the packaged beverage (decrease in the epi-unpolymerized catechin). . In addition, it is possible to suppress a decrease in the ratio of epi-unpolymerized catechin in non-polymerized catechin during storage (epi-isomer ratio).

<Method for producing packaged beverage containing epi-nonpolymerized catechin>
The present invention also includes the following method for producing a packaged beverage.
Contains histidine and/or a salt thereof (A1), an epi-unpolymerized catechin (B1), and an aqueous medium containing water (C), wherein the concentration of histidine and/or salt thereof (A1) in terms of histidine is 0.015 to 3 w/v%, a pH of more than 4.5 and 8.0 or less, and a Brix of 3.0% or less, including a step of heat-treating the mixture at 100 ° C. or higher. A method for producing a packaged beverage containing polyunpolymerized catechins.

In the production method of the present invention, a mixture containing histidine and/or a salt thereof (A), an epi-unpolymerized catechin (B1), and an aqueous medium containing water (C) is heated to 100°C or higher. A process (also called a heating process) is included. The mixture subjected to the heating step is a liquid mixture (liquid composition).

Preferred aspects of histidine and/or its salt (A1) are the same as in the case of the beverage described above, and histidine and/or histidine hydrochloride are preferred, and histidine is preferred.
The concentration of histidine and/or a salt thereof (A1) in the mixture, in terms of histidine, is preferably 0.016 w/v% or more, more preferably 0.017 w/v% or more, and still 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. Moreover, when the concentration of histidine and/or its salt is high, it may not be preferable from the viewpoint of the flavor of the resulting beverage. The concentration of histidine and/or a salt thereof (A1) in the mixture, in terms of histidine, is preferably 2 w/v% or less, more preferably 1 w/v% or less or 0.5 w/v% or less, still more preferably is 0.2 w/v % or less, still 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 one aspect, the concentration of histidine and/or a salt thereof (A1) in the mixture is preferably 0.015 to 2 w/v%, more preferably 0.015 to 1 w/v%, in terms of histidine, 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 to 0.2 w/v%, more preferably 0.020 to 0.2 w/v%, even more preferably 0.020 to 0.1 w/v%, particularly preferably 0.020 to 0.1 w/v%. 020-0.06 w/v%, most preferably 0.020-0.05 w/v%. The concentration of histidine and/or its salt (A1) in the mixture before heat treatment is preferably within the above range.
In the above mixture, histidine and/or its salt (A1) is preferably dissolved and/or dispersed in the aqueous medium (C).

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) includes epicatechin gallate and/or epigallocatechin gallate. In the above mixture, the epi-unpolymerized catechin (B1) is preferably dissolved and/or dispersed in the aqueous medium (C).

When the 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, epimerization of epigallocatechin gallate to gallocatechin gallate during heat treatment can be further suppressed. When the 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, epimerization of epicatechin gallate to catechin gallate during heat treatment can be further suppressed. In one aspect, the mixture contains 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. It is preferably 2400 μg/mL or less, and more preferably, the concentrations of both epigallocatechin gallate and epicatechin gallate are 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, and is 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, more preferably 200 μg/mL or less, even more preferably 160 μg/mL or less, particularly preferably 150 μg/mL or less, and 140 μg /mL or less is most preferred. When the 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, and 1200 μg/mL or less, 800 μg/mL or less. mL or less, 600 μg/mL or less, 400 μg/mL or less, or 300 μg/mL or less, more preferably 200 μg/mL or less, even more preferably 160 μg/mL or less, and 150 μg/mL is particularly preferably 140 μg/mL or less, most preferably 140 μg/mL or less. The concentration of epigallocatechin gallate and/or the concentration of epicatechin gallate in the mixture before heat treatment is preferably within the above range.

The aqueous medium (C) contains water, but may contain solvents other than water. Solvents other than water include alcohols (eg, ethanol), and one or more of these can be used. The content of the aqueous medium (C) in the above mixture is preferably 85% by weight or more, more preferably 97.0% by weight or more, still more preferably 98.2% by weight or more, and particularly preferably 98.2 to 99% by weight. 9% by weight. The water content in the aqueous medium (C) is preferably 99% by weight or more, more preferably 99.9 to 100% by weight. In one aspect, the aqueous medium (C) preferably has an alcohol concentration of less than 1 v/v %, more preferably an ethanol concentration of less than 1 v/v %.

In the production method of the present invention, a mixture having a pH of more than 4.5 and less than or equal to 8.0 is heat-treated. The pH of the mixture before the heat treatment should be within the above range. When the mixture contains histidine and/or a salt thereof at the above concentration and has a pH of more than 4.5 and not more than 8.0, the epimerization of the epi-unpolymerized catechin during heat treatment can be effectively suppressed. can be done. Also, by heating the above mixture, a beverage having a pH exceeding 4.5 and not exceeding 7.9 can be produced. The pH of the mixture before heat treatment is preferably more than 4.5 and 7.0 or less, more preferably more than 4.5 and 6.5 or less, and 4.7 to 6.5 more preferably 4.9 to 6.5, even more preferably 5.0 to 6.5, particularly preferably 5.0 to 6.2, 5 .0 to 6.0 is most preferred.

The mixture may contain components other than histidine and/or its salt (A1), epi-unpolymerized catechin (B1) and aqueous medium (C). The mixture may contain, for example, additives that can be used in beverages. The mixture may contain non-epi non-polymerized catechin (B2). The above mixture preferably has an epi-isomer rate of non-polymerized epi-isomer catechin of 45% or more, more preferably 50% or more, even more preferably 55% or more, and 60% or more. is even more preferred, 63% or more is particularly preferred, and 65% or more is most preferred. In addition, the epi-body rate may be 100% or less, 95% or less, 92% or less, or 90% or less. In one aspect, in the above mixture, the epi-isomer ratio of non-polymerized catechin is preferably 45 to 100%, more preferably 50 to 100%, 55 to 100%, 60 to 100% or 60 to 95%, further preferably 60-92%, even more preferably 60-90%, particularly preferably 63-90%, most preferably 65-90%. It is preferable that the epi-isomer rate of each non-polymerized catechin such as epigallocatechin gallate and epigallocatechin gallate contained in the mixture is within the above range. For example, when the mixture contains epigallocatechin gallate, the epi-percentage of epigallocatechin gallate is preferably within the above range. When the mixture contains epicatechin gallate, the epicatechin gallate ratio is preferably within the above range. When the mixture contains epicatechin, the ratio of epi-isomer of epicatechin is preferably within the above range, and when the mixture contains epigallocatechin, the ratio of epi-isomer of epigallocatechin is preferably within the above range. The epi-isomer ratio of the mixture before heat treatment is preferably within the above range. The mixture contains one or more of plant extracts used in the above tea beverages, such as tea extracts such as green tea extracts, oolong tea extracts and black tea extracts, grain extracts, and the like. good too. The origin and production method of histidine and/or its salt (A1) and epi-unpolymerized 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. The epi-unpolymerized catechin (B1) may be blended into the mixture, for example, in the form of a plant extract containing it. In one aspect, the mixture is preferably a raw material liquid for tea beverages (green tea beverages, oolong tea beverages, black tea beverages, barley tea beverages, blended tea beverages, etc.).

The above mixture has a Brix of 3.0% or less before heat treatment. The mixture preferably has a Brix of 1.5% or less, more preferably 1.4% or less, since epimerization of the epimerized non-polymerized catechins during heat treatment can be further suppressed. % or less, more preferably 1.0% or less, particularly preferably 0.9% or less or 0.8% or less, most preferably 0.7% or less . The Brix may be 0.01% or more, more preferably 0.05% or more, still more preferably 0.1% or more, even more preferably 0.15% or more, and particularly preferably 0.2% or more , 0.3% or more is most preferred. In one aspect, the mixture preferably has a Brix of 0.01 to 1.5% or 0.01 to 1.4%, 0.01 to 1.2%, 0.01 to 1.0%, More preferably 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% , more preferably 0.2 to 0.8%, particularly preferably 0.2 to 0.7%, and most preferably 0.3 to 0.7%. Brix is also preferably between 0.3 and 0.8%. It is preferable from the viewpoint of the flavor of the obtained beverage that the Brix of the mixture before heat treatment is within the above range. The method of adjusting Brix is not particularly limited. For example, a method of diluting with water or the like, a method of adjusting the composition of the mixture, or the like can be employed.

In the heat treatment, the mixture is heated to the above temperature. Epimerization of epi-unpolymerized catechins tends to progress at higher temperatures. In the production method of the present invention, epimerization of epi-unpolymerized catechins during heat treatment can be suppressed.
The temperature of the heat treatment is preferably 115° C. or higher and preferably 150° C. or lower from the viewpoint of effectively suppressing the epimerization of the epi-unpolymerized catechin. A heating means is not particularly limited. Heat treatment can be performed using a known device.
The heat treatment time is preferably 30 seconds to 400 minutes, more preferably 30 seconds to 240 minutes, still more preferably 30 seconds to 14 minutes, and particularly preferably 30 seconds to 5 minutes.
The heat treatment may be performed after the mixture is filled in the container or before the mixture is filled in the container. Heating in the heat treatment may be heating for sterilization. Heating for sterilization may be performed with a UHT (Ultra High Temperature) sterilizer or a retort sterilizer such as an autoclave.
By the above heat treatment, a beverage containing histidine and/or a salt thereof (A), an epi-unpolymerized catechin (B1) and an aqueous medium containing water (C) is obtained. Preferred embodiments of the epi-nonpolymerized catechin-containing beverage include the above preferred embodiments of the packaged beverage of the present invention.

The production 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 beverage containing epi-non-polymerized catechin obtained by the heat treatment to preferably 23° C. or lower, more preferably 15° C. or lower.
The production method of the present invention comprises, for example, histidine and/or a salt thereof (A1), an epi-unpolymerized catechin (B1), and an aqueous medium (C), and the pH exceeds 4.5 to 8.5. A step of preparing a mixture having a Brix of 0 or less and a Brix of 3.0% or less, a step of filling a container with the mixture (or a heat-treated mixture (beverage)), a step of replacing the air in the container with nitrogen, etc. may include one or more steps of Examples of the container include the same containers as those used for the above-mentioned packaged beverages.
The method for preparing the above mixture is not particularly limited. For example, histidine and / or a salt thereof (A1), an aqueous medium (C) containing epi-unpolymerized catechin (B1) and water, and if necessary, other components may be mixed, and pH and Brix may be adjusted to produce. can. The mixture may contain, for example, a plant extract such as the tea extract described above. In one embodiment, the epi-unpolymerized catechin (B1) may be formulated using a tea extract containing it. The method for adjusting the pH of the mixture is not particularly limited, and for example, a pH adjuster such as an acid used for adjusting the pH of beverages can be used. Further, for example, by using a histidine salt such as histidine hydrochloride in the preparation of the mixture, the pH of the mixture can be adjusted. The pH and Brix of the mixture may be adjusted during mixing of the components, or after mixing the components. Moreover, if necessary, a step of adjusting the Brix of the beverage containing epi-non-polymerized catechin obtained by the heat treatment may be carried out.

According to the production method of the present invention, a packaged beverage containing epi-unpolymerized catechin in which epimerization of epi-unpolymerized catechin is suppressed can be obtained. In one aspect, the packaged beverage is preferably a packaged tea beverage (green tea beverage, oolong tea beverage, black tea beverage, barley tea beverage, blended tea beverage, etc.).

<Method for Suppressing Epimerization of Non-Polymerized Catechin>
The present invention provides a composition containing 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, and non-polymerized catechins. A method for suppressing epimerization of non-polymerized catechins, which is added to the product, is also included.
The present invention provides at least one compound (compound (A)) selected from the group consisting of aromatic amino acids, cysteine, aromatic amino acids and/or cysteine-containing dipeptides, and salts thereof, of non-polymerized catechins. Also included is use for inhibiting epimerization.
In the method and use described above, the compound (A), the non-polymerized catechins, the non-polymerized catechin-containing composition and preferred embodiments thereof are the same as those in the epimerization inhibitor of the non-polymerized catechins described above.

For clarity, numerical ranges expressed herein by lower and upper values, ie, "lower to upper", include those lower and upper values. For example, a range represented by "1-2" means from 1 to 2 and includes 1 and 2. In this specification, the upper limit and the lower limit may be any combination of ranges.

EXAMPLES The present invention will be described in more detail below with reference to examples, but the scope of the present invention is not limited by these examples.

<Method for measuring epi-unpolymerized catechin>
The concentration of epi-unpolymerized catechin was measured by high performance liquid chromatography.
(Measurement condition)
The sample diluted 2-fold with 100% methanol was then centrifuged (13,500 rpm x 5 minutes) to collect the supernatant, and the octadecyl group was analyzed using a high-performance liquid chromatograph (model Vanquish) manufactured by Thermo Fisher Scientific. Introduction A packed column for liquid chromatography Unison UK-C18HT (3 mmφ×100 mm: Imtakt) was mounted, and measurement was performed at a column temperature of 40° C. by a gradient method. Mobile phase solution A is a distilled aqueous solution containing 0.1% formic acid, solution B is an acetonitrile solution containing 0.1% formic acid, the sample injection volume is 2 μL, the flow rate is 1.0 mL/min, and the UV detector wavelength is 280 nm. was performed under the conditions of
Gradient conditions (v/v%)
0 min B liquid 2%, 3 min B liquid 20%, 4.2 min B liquid 23%, 4.5 min B liquid 80%, 4.6 min B liquid 80%, 4.7 min B liquid 2%
Standard substances include (-)-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 Industry Co., Ltd.), (-)-gallocatechin (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.), (-)-epicatechin (manufactured by Tokyo Chemical Industry Co., Ltd.) and (+)-catechin (manufactured by Tokyo Chemical Industry Co., Ltd.) were used.

<Method for measuring histidine>
Histidine was quantified using a histidine quantification kit (MicroMolar Histidine Assay Kit, manufactured by ProFoldin) according to the kit's instructions. With this kit, histidine is measured by a fluorescence method (detection method: fluorescence, measurement wavelength: excitation 485 nm, fluorescence 535 nm).

<pH>
The pH (25° C.) was measured with a pH meter (manufactured by HORIBA, model number: LAQUA F71).

<Heat treatment>
The heat treatment was performed using an autoclave (model: HV-50IILB) manufactured by Hirayama Seisakusho.

<Epi body rate and non-epi body rate>
In the examples, the epi-isomer rate was obtained by calculating from the concentration (μg/mL) of the epi non-polymerized catechin and the non-epi non-polymerized catechin using the following formula.
Percentage of epi isomer (%)=100×concentration of non-polymerized epi catechin/total concentration of non-polymerized epi catechin and non-epi catechin Non-epi catechin was calculated by the following formula.
Non-epi catechin ratio (%) = 100 x concentration of non-epi non-polymerized catechin/total concentration of non-epi non-polymerized catechin and non-epi non-polymerized catechin

Amino acids used are in the L configuration unless otherwise specified. L-histidine is manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd. (hereinafter abbreviated as histidine), carnosine is manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd., anserine is manufactured by Combi-Blocks, and 1-methylhistidine is manufactured by Cosmo Bio. 3-methylhistidine manufactured by Sigma-Aldrich, and D-histidine manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd. was used. L-histidine hydrochloride monohydrate manufactured by Fuji Film Wako Pure Chemical Industries, Ltd. was used as the L-histidine hydrochloride reagent. L-histidine raw material (food additive with L-histidine content of 98.0% or more) and histidine hydrochloride raw material (food additive with L-histidine hydrochloride content of 98.0% or more) are Ajinomoto Healthy Supply Co., Ltd. product was used. Amino acids other than those described above were manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.

As propylene glycol, a food additive raw material manufactured by Lucas Guitar Co., Ltd. was used.
Epigallocatechin gallate raw material (hereinafter referred to as EGCg raw material) contains powdered raw material extracted and refined from green tea (epigallocatechin gallate (EGCg) content is 95.3% by weight, gallocatechin gallate (GCg) content is detected 100% epi-body rate) was used. The epicatechin gallate raw material (hereinafter referred to as ECg raw material) is a powdered raw material extracted and refined from green tea (epicatechin gallate (ECg) content of 93.3% by weight, catechin gallate (Cg) content of less than the detection limit, 100% epibody ratio) was used. As epigallocatechin (EGC), epigallocatechin (purity of 98% or more) manufactured by Tokyo Chemical Industry Co., Ltd. was used. As epicatechin (EC), epicatechin (purity of 97% or more) manufactured by Tokyo Kasei Kogyo Co., Ltd. was used. (+)-catechin manufactured by Tokyo Kasei Kogyo Co., Ltd. was used as catechin (C). As catechin gallate (Cg), (-)-catechin gallate manufactured by Nagara Science Co., Ltd. was used. As gallocatechin (GC), (−)-gallocatechin manufactured by Fuji Film Wako Pure Chemical Industries, Ltd. was used. As gallocatechin gallate (GCg), (−)-gallocatechin gallate manufactured by Fuji Film Wako Pure Chemical Industries, Ltd. was used.

For the preparation of the sample and the control sample, a commercially available soft drink blended tea (from barley, pigeon barley, roasted rice, soybean, habu tea) (hereinafter abbreviated as blended tea A), a commercially available soft drink A certain blended tea (derived from green tea, barley, roasted rice, and Japanese black tea) (hereinafter abbreviated as blended tea B) and a commercially available soft drink green tea (hereinafter abbreviated as green tea beverage C) were used.

pH of blended teas A to B and green tea beverage C, 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, epimerization rate and histidine concentration are described below. Histidine contained in the beverages below was all L-histidine. 1 μg/mL is 0.0001 w/v% when converted to weight volume concentration (w/v%).
(Blended tea A)
pH 5.3, EGCg concentration: below detection limit, GCg 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: detection Below the limit, GC concentration: below the detection limit, histidine concentration: 0.0033 w / v%
(Blended tea B)
pH 5.8, EGCg concentration: 25 μg/mL, GCg concentration: 26 μg/mL, ECg concentration: 11 μg/mL, Cg concentration: 9 μg/mL, EC concentration: below detection limit, C concentration: below detection limit, EGC concentration: 26 μg /mL, GC concentration: 20 μg / mL, EGCg epibody rate: 48.8%, ECg epibody rate: 55.0%, EGC epibody rate: 57.0%, Histidine concentration: 0.0037 w / v%
(Green tea drink C)
pH 6.3, EGCg concentration: 109 μg/mL, GCg concentration: 130 μg/mL, ECg concentration: 33 μg/mL, Cg concentration: 28 μg/mL, EC concentration: 40 μg/mL, C concentration: 39 μg/mL, EGC concentration: 83 μg /mL, GC concentration: 84 μg / mL, EGCg epibody rate: 45.8%, ECg epibody rate: 54.2%, EC epibody rate: 50.4%, EGC epibody rate: 49.6%, Histidine concentration: 0.0076 w/v%

In Examples 1 to 15 and 18 below, attention was paid to epigallocatechin gallate (EGCg), and the epimerization-suppressing effect of compounds such as amino acids on EGCg was investigated.

<Example 1>
Green tea beverage C was used as the base beverage. A base liquid was obtained by dissolving the EGCg raw material in the 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 baking soda (manufactured by Marugo Corporation) (hereinafter abbreviated as baking soda), and control samples 1 to 3 ( pH 4.4-5.8) was prepared.
In addition, according to the formulation 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. Samples 1 to 16 (pH 4.9 to 5.2) ) was prepared. The compounding recipe shown in the table is the compounding amount of each component (raw material). For example, no histidine was added to control sample 1, but the sample contained 0.0076 w/v% histidine from the base beverage (green tea beverage C).
Control samples and samples were filled into glass vials and heated in an autoclave at 115° C. for 5 minutes. After this heating, it was cooled to room temperature and the pH and the concentrations of EGCg and GCg were measured.

The EGCg ratio (%) was calculated from the sum of the EGCg concentration and the GCg concentration by the formula of 100×EGCg concentration/(EGCg concentration+GCg concentration), and this was taken as the epimer ratio (EGCg/(EGCg+GCg)). Epi-body rate (%) in Examples 2-12, 14, and 18 was also calculated in the same manner as in Example 1.

In the examples, the epimerization reaction rate (k) and the pH-corrected epimerization reaction rate ratio were obtained by the following methods unless otherwise specified. By using the pH-corrected epimerization reaction rate ratio, it is possible to correct and compare the effects of the difference in pH between samples. The calculations were made assuming that the non-polymerized catechin epi-isomer ratio in the equilibrium state was 45% and the non-epi-isomer ratio was 55%.
The epimerization reaction rate (k) is the heating time (t), the value (X) obtained by subtracting 45% as the epi-form ratio in the equilibrium state of EGCg and GCg from the epi-form ratio after heating, and the epi-form ratio before heating. It was calculated by the following formula (1), which is represented by the value (X ₀ ) obtained by subtracting 45% as the epi-form ratio in the equilibrium state of EGCg and GCg.
Formula (1) Log(X/X ₀ )=k×t

In addition, since the epimerization rate is related to pH, pH-corrected epimerization reaction rate ratios were also calculated (Examples 1 to 4, 6 to 7, 9, 14 to 15). As a calculation method, first, from X and X ₀ of three control samples with different pH (for example, control samples 1 to 3 in Example 1), the horizontal axis is the pH after heating, and the vertical axis is X / X ₀ . , a regression equation of X/X ₀ against pH was determined for the control sample. This regression equation is represented by the following equation ( ₂ ) with pH, X and X0. In the following formula (2), b represents the slope and A represents the intercept.
Formula (2) X/X ₀ =b×[pH]+A
By substituting the pH after heating of the sample to be evaluated in the above formula (2), the pH correction X/X ₀ of the control sample (X/X ₀ of the control sample having the same pH as the sample to be evaluated) is obtained. . The pH correction rate of the control sample ( _k _{Control sample} ) is calculated. The ratio (k _{control sample} /k _sample ) between this and the epimerization reaction rate (k _sample ) calculated from the epimerization rate of the sample was calculated and used as the pH-corrected epimerization reaction rate ratio.
A larger value of this pH-corrected epimerization reaction rate ratio means that the epimerization (non-epimerization) suppression rate from the epi-form to the non-epi-form is high.

In Examples 5, 8, 10 to 13, and 16 to 18, epimerization reaction rate ratios without pH correction were determined. The non-pH-corrected epimerization kinetic ratio (hereafter, epimerization kinetic ratio) indicates the kinetic ratio of a sample (k _sample and k _{control sample} ) compared to a control sample of similar pH (after heating). there is This epimerization reaction rate ratio is obtained by obtaining the epimerization reaction rate (k _sample and k _{control sample} ) from formula (1) by the above method for each of the sample and the control sample, and comparing the epimerization reaction rate of the sample to the sample and Calculated as the ratio of epimerization kinetics of control samples of similar pH (k _{control samples} /k _samples ).
A larger number of this epimerization reaction rate ratio means that the epimerization from epimerization to non-epimerization (non-epimerization) suppression rate is higher.

Table 1 shows the pH before and after heating, the concentration of EGCg and GCg, the epimerization ratio (EGCg/(EGCg+GCg)), and the epimerization reaction rate ratio (value corrected for pH or value not corrected for pH). show.

<Example 2>
A base liquid was obtained by dissolving the EGCg raw material in the blended tea A according to the formulation (w/v%) shown in Table 2. The pH of this base solution was adjusted using VC and sodium bicarbonate to prepare control samples 4-6 (pH 5.0-5.6).
In addition, according to the formulation shown in Table 2, the EGCg raw material and amino acids were dissolved and/or suspended in blended tea A, and the pH was adjusted with VC and sodium bicarbonate to prepare samples 17 to 20 (pH 5.3).
The control sample and sample were heated and cooled in the same manner 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.

<Example 3>
A base liquid was obtained by dissolving the EGCg raw material in the green tea beverage C according to the formulation (w/v%) shown in Table 3. The pH of this base solution was adjusted using VC and sodium bicarbonate to prepare control samples 7-9 (pH 4.5-5.6).
Further, according to the compounding recipe shown in Table 3, the EGCg raw material and amino acids were dissolved in green tea beverage C, and the pH was adjusted with VC and sodium bicarbonate to prepare samples 21 and 22.
The control sample and sample were heated and cooled in the same manner 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.

As shown in Tables 1 to 3, it was found that aromatic amino acids (histidine, phenylalanine, tryptophan, tyrosine) and cysteine are highly effective in suppressing the epimerization of non-epi-polymerized catechins into non-epi-polymerized catechins. . Among them, histidine showed an excellent effect of suppressing epimerization.

<Example 4>
A base liquid was obtained by dissolving the EGCg raw material in the blended tea B according to the formulation (w/v%) shown in Table 4. The pH of this base solution was adjusted using VC and sodium bicarbonate to prepare control samples 10-12 (pH 5.0-5.5).
Further, according to the formulation shown in Table 4, the EGCg raw material and histidine, carnosine, anserine, 3-methylhistidine or 4-methylhistidine were dissolved in blended tea B, and the pH was adjusted with VC and sodium bicarbonate. (pH 5.1-5.5) was prepared.
Control samples and samples were filled into glass vials, heated in an autoclave at 120° C. for 5 minutes, and 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.

As shown in Table 4, it was found that histidine, carnosine, anserine, 3-methylhistidine and 1-methylhistidine are highly effective in suppressing the epimerization of non-epi-polymerized epi-polymerized catechins to non-epi-polymerized catechins. These results suggest that aromatic amino acids, dipeptides containing them, and related compounds have an effect of suppressing epimerization of non-polymerized catechins.

<Example 5>
The EGCg raw material was dissolved in the blended tea A according to the formulation (w/v%) shown in Table 5 to obtain a base liquid. The pH of this base solution was adjusted using VC and sodium bicarbonate to prepare control sample 13 (pH 5.7).
Further, according to the formulation shown in Table 5, the EGCg raw material and histidine were dissolved in blended tea A, and the pH was adjusted with VC and sodium bicarbonate to prepare samples 28 to 33 (pH 5.8).
Control samples and samples were filled into glass vials, heated in an autoclave at 130° C. for 1 minute, and 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 kinetics, the ratio of the kinetics of each sample to the control sample 13 was calculated.

<Example 6>
An EGCg raw material was dissolved in green tea beverage C according to the formulation (w/v%) shown in Table 6 to obtain a base liquid. Control samples 14 to 16 (pH 4.5 to 5.6) were prepared by using VC and sodium bicarbonate to adjust the pH of this base solution.
Further, according to 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 to 42 (pH 5.1).
Control samples and samples were filled into glass vials, heated in an autoclave at 115° C. for 5 minutes, and 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.

<Example 7>
The EGCg raw material was dissolved in the blended tea A according to the formulation (w/v%) shown in Table 7 to obtain a base liquid. The pH of this base solution was adjusted using VC and sodium bicarbonate to prepare control samples 17-19 (pH 3.8-5.2).
Further, according to the formulation shown in Table 7, the EGCg raw material and histidine were dissolved in blended tea A, and the pH was adjusted with VC and sodium bicarbonate to prepare samples 43 to 45 (pH 5.1 to 5.3).
Control samples and samples were filled into glass vials, heated in an autoclave at 130° C. for 1 minute, and 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.

As shown in Tables 5 to 7, the epimerization inhibitory effect was confirmed by the addition of histidine.

<Example 8>
A base liquid was obtained by dissolving the EGCg raw material in the blended tea A according to the formulation (w/v%) shown in Table 8. Control samples 20 to 25 (pH 2.6 to 5.2) were prepared by using VC and sodium bicarbonate to adjust the pH of this base solution.
Further, according to the formulation shown in Table 8, the EGCg raw material and histidine were dissolved in blended tea A, and the pH was adjusted with VC and sodium bicarbonate to prepare samples 46 to 51 (pH 2.6 to 5.1).
Control samples and samples were filled into glass vials, heated in an autoclave at 130° C. for 1 minute, and 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 kinetic ratios, sample 46 to control 20, sample 47 to control 21, sample 48 to control 22, sample 49 to control 23, and control 24. The ratio of reaction rate of sample 51 to sample 50, control sample 25 was calculated.

<Example 9>
A base liquid was obtained by dissolving the EGCg raw material in the blended tea A according to the formulation (w/v%) shown in Table 9. The pH of this base solution was adjusted using VC and sodium bicarbonate to prepare control samples 26-28 (pH 6.0-8.0).
Also, according to the formulation shown in Table 9, the EGCg raw material and histidine were dissolved in blended tea A, and the pH was adjusted with VC and sodium bicarbonate to prepare samples 52 to 54 (pH 6.0 to 8.0).
Control samples and samples were filled 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 kinetic ratios, the ratio of the kinetics of sample 52 to control 26, sample 53 to control 27, and sample 54 to control 28 was calculated.

As shown in Tables 8 and 9, the epimerization inhibitory effect of histidine was observed at any pH of 2 to 8.

<Example 10>
A base liquid was obtained by dissolving the EGCg raw material in the blended tea A according to the formulation (w/v%) shown in Table 10. The pH of this base solution was adjusted using VC and sodium bicarbonate to prepare control samples 29-37 (pH 5.3).
Also, according to the formulation shown in Table 10, the EGCg raw material and histidine were dissolved in blended tea A, and the pH was adjusted with VC and sodium bicarbonate to prepare samples 55 to 63 (pH 5.3).
Control samples and samples 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 kinetic ratios, sample 55 versus control 29, sample 56 versus control 30, sample 57 versus control 31, sample 58 versus control 32, and control 33. The ratios of the reaction rates of sample 59, sample 60 to control 34, sample 61 to control 35, sample 62 to control 36, and sample 63 to control 37 were calculated.

As shown in Table 10, the effect of suppressing epimerization was confirmed at any concentration of epi-unpolymerized catechin. A particularly high epimerization inhibitory effect was obtained when the concentration of epi-unpolymerized catechin was in the range of 50 to 2400 μg/mL.

<Example 11>
A base liquid was obtained by dissolving the EGCg raw material in green tea beverage C according to the formulation (w/v%) shown in Table 11. The pH of this base solution was adjusted using VC and sodium bicarbonate to prepare control samples 38-42 (pH 5.7).
In addition, according to the formulation shown in Table 11, the 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 to 68 (pH 5.7).
The control sample and sample were heat treated using a heat exchanger (model: MINI UHT P-20) manufactured by Power Point International, Inc. at the temperatures and times shown in Table 11, and cooled to room temperature. Table 11 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 kinetic ratios, sample 64 to control 38, sample 65 to control 39, sample 66 to control 40, sample 67 to control 41, and control 42. A ratio of reaction rates for sample 68 was calculated.

<Example 12>
A base liquid was obtained by dissolving the ECg raw material in the blended tea A according to the formulation (w/v%) shown in Table 12. The pH of this base liquid was adjusted using VC and sodium bicarbonate to prepare control sample 43 (pH 4.9).
Further, according to the formulation shown in Table 12, the EGCg raw material and histidine were dissolved in blended tea A, and the pH was adjusted with VC and sodium bicarbonate to prepare samples 69 to 72 (pH 4.9).
A control sample and a sample were placed in a 1.5 mL tube, and a block incubator (model: MG-3100, manufactured by EYELA) was used. Heat at 100° C. for 15-240 minutes and cool 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 kinetic ratio, the ratio of the kinetics of samples 69-72 to control sample 43 was calculated.

<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 the blended tea A according to the formulation (w/v%) shown in Table 13. The pH of this ECg-containing beverage was adjusted using VC and baking soda to prepare control sample 44 (pH 5.7).
Further, according to the formulation shown in Table 13, the ECg solution and histidine were dissolved in blended tea A, and the pH was adjusted with VC and sodium bicarbonate to prepare sample 73 (pH 5.6).
Control samples and samples were filter sterilized and sealed in 50 mL glass vials. It was stored at the temperature shown in Table 13 for 3 weeks using an incubator (product name: Heratherm 100, manufactured by Thermo Fisher Scientific). After storage, pH and concentrations of ECg and catechin gallate (Cg) were measured. Table 13 shows pH after storage, concentrations of ECg and Cg, epimerization rate (ECg/(ECg+Cg)), and epimerization reaction rate ratio. In Example 13, the epi-isomer ratio (ECg/(ECg+Cg)) was obtained from the concentration of non-polymerized catechin (w/v%) by the following formula.
Epibody rate (%) = 100 x concentration of ECg/(total concentration of ECg and Cg)
The epimerization reaction rate (k) is the heating time (t), the value (X) obtained by subtracting 45% as the epimerization rate in the equilibrium state from the epimerization rate after heating, and the epimerization rate in the equilibrium state from the epimerization rate before heating. It was calculated by the following formula (3), which is represented by the value (X ₀ ) obtained by subtracting 45% as the bulk ratio.
Formula (3) Log(X/X ₀ )=k×t
For the epimerization kinetic ratio, the ratio of the kinetics of sample 73 to control sample 44 was calculated.

As shown in Tables 11 to 13, the epimerization inhibitory effect of histidine was confirmed in any temperature range from 23°C to 145°C. Epimerization proceeded at higher temperature, but epimerization was effectively inhibited by histidine.

<Example 14>
An EGCg raw material was dissolved in green tea beverage C according to the formulation (w/v%) shown in Table 14 to obtain a base liquid. The pH of this base solution was adjusted using VC and sodium bicarbonate to prepare control samples 45-47 (pH 4.5-5.6).
In addition, EGCg raw material and histidine or a salt thereof were dissolved in green tea beverage C according to the formulation shown in Table 14 to prepare samples 74 to 77 (pH 5.1). As histidine or a salt thereof, histidine, L-histidine hydrochloride reagent, L-histidine raw material or L-histidine hydrochloride raw material was used.
Control samples and samples were filled into glass vials, heated in an autoclave at 115° C. for 5 minutes, and 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.

As shown in Table 14, epimerization-suppressing effects were confirmed regardless of whether the reagent, raw material histidine, or histidine salt was used.

<Example 15>
A base liquid was obtained by dissolving the EGCg raw material in the blended tea beverage A according to the formulation (w/v%) shown in Table 15. The pH of this base solution was adjusted using VC and sodium bicarbonate to prepare control samples 48-50 (pH 4.6-5.6).
In addition, samples 78 to 83 (pH 5.0 to 5.2) were prepared by dissolving the EGCg raw material and histidine in a commercially available blended tea beverage A according to the formulation shown in Table 15. L-histidine (histidine) or D-histidine was used.
Control samples and samples were filled into glass vials, heated in an autoclave at 115° C. for 5 minutes, and 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.

<Example 16>
In the blending recipe (w / v%) shown in Table 16, blended tea A (concentration of each non-polymerized catechin: below the detection limit) was added to epi-non-polymerized catechin (EGCg raw material, ECg raw material, epigallocatechin (EGC) or epi Catechin (EC)) was dissolved and/or suspended to obtain a liquid containing epi-unpolymerized catechin. Control samples 51 to 62 (pH 4.5 to 5.5) were prepared by adjusting the pH of the resulting solution containing epi-unpolymerized catechin.
In addition, according to the formulation shown in Table 16, epi-unpolymerized catechin (EGCg raw material, ECg raw material, EGC or EC) and histidine were dissolved and/or suspended in blended tea A, and samples 84 to 87 (pH 5.0) were prepared. 0) was prepared.
Control samples and samples were filled into glass vials and heated in an autoclave at 130° C. for 1 minute. After cooling, pH and epi-nonpolymerized catechins (EGCg, ECg, EGC, EC) and non-epi-nonpolymerized catechins (gallocatechin gallate (GCg), catechin gallate (Cg), gallocatechin (GC), catechin (C)) was measured. Table 16 shows the pH after heating, the concentration of non-polymerized catechin, the epimerization rate (epimer/(epimer+non-epimer)), and the pH-corrected epimerization reaction rate ratio. A "-" indicates that the concentration was below the detection limit.

The epimerization reaction rate (k) is the heating time (t), the value (X) obtained by subtracting 45% as the epimerization rate in the equilibrium state from the epimerization rate after heating, and the epimerization rate in the equilibrium state from the epimerization rate before heating. It was calculated by the above formula (3), which is represented by the value (X ₀ ) obtained by subtracting 45% as the bulk ratio.
The pH-corrected epimerization reaction rate ratio was calculated in the same manner as in Example 1. The above regression equation (formula (2)) is for EGCg (control samples 51 to 53), ECg (control samples 54 to 56), EGC (control samples 57 to 59), and EC (control samples 60 to 62). created each.

<Example 17>
In the formulation (w / v%) shown in Table 17, blended tea A (concentration of each non-polymerized catechin: below the detection limit), non-epi non-polymerized catechins (gallocatechin gallate (GCg), catechin gallate (Cg), Gallocatechin (GC) or catechin (C)) was dissolved and/or suspended to obtain a non-epi-nonpolymerized catechin-containing liquid. Control samples 63 to 66 (pH 6.0) were prepared by adjusting the pH of the resulting non-epi-non-polymerized catechin-containing liquid.
In addition, according to the formulation shown in Table 17, non-epi-nonpolymerized catechin (GCg, Cg, GC or C) and histidine were dissolved and/or suspended in blended tea A, the pH was adjusted, and sample 88 ~91 (pH 6.0) was prepared.
Control samples and samples were placed in 1.5 mL tubes, heated to 100° C. for 15 minutes in a block incubator, and cooled to room temperature. The pH and the concentrations of epi-nonpolymerized catechins (EGCg, ECg, EGC, EC) and non-epi-nonpolymerized catechins (GCg, Cg, GC, C) were measured. Table 17 shows the pH after heating, the concentration of non-polymerized catechins, the ratio of non-epi isomers (non-epi isomers/(epi isomers + non-epi isomers)), and the epimerization reaction rate ratio.

The epimerization reaction rate (k) is the heating time (t), the value (X) obtained by subtracting 55% as the non-epi isomer ratio in the equilibrium state from the non-epi isomer ratio after heating, and the non-epi isomer ratio before heating to the equilibrium It was calculated by the following formula (4), which is represented by the value (X ₀ ) obtained by subtracting 55% as the non-epi body ratio of the state.
Formula (4) Log(X/X ₀ )=k×t
For the epimerization kinetic ratios, the ratio of the kinetics of sample 88 to control 63, sample 89 to control 64, sample 90 to control 65, and sample 91 to control 66 was calculated. In Example 17, the higher the number of this epimerization reaction rate ratio, the higher the epimerization (epimerization) suppression rate from the non-epimeter to the epimerization.

As shown in Tables 16 and 17, epimerization-suppressing effects by histidine were confirmed for both epi- and non-epi-nonpolymerized catechins.

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

As shown in Table 18, any Brix of 0.1 to 3.1% inhibited the epimerization of epimerized unpolymerized catechin by histidine.

Claims

Aromatic amino acids, cysteine, dipeptides containing aromatic amino acids and / or cysteine, and at least one compound (A) selected from the group consisting of salts thereof as an active ingredient for suppressing epimerization of non-polymerized catechins agent.
2. The inhibitor of epimerization of non-polymerized catechins according to claim 1, 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. The epimerization inhibitor of unpolymerized catechins according to claim 1 or 2, wherein the aromatic amino acid is at least one amino acid selected from the group consisting of histidine, methylhistidine, phenylalanine, tryptophan and tyrosine.
Compound (A) is at least one selected from the group consisting of histidine, methylhistidine, dipeptides containing histidine or methylhistidine and salts thereof, nonpolymerization according to any one of claims 1 to 3 Catechin epimerization inhibitor.
The epimerization inhibitor of non-polymerized catechins according to any one of claims 1 to 4, wherein the compound (A) is histidine and/or a salt thereof.
The epimerization inhibitor of non-polymerized catechins according to any one of claims 1 to 4, wherein the compound (A) is at least one selected from the group consisting of carnosine, anserine and salts thereof.
2. The epimerization inhibitor of non-polymerized catechins according to claim 1, wherein the compound (A) is at least one selected from the group consisting of cysteine, cysteine-containing dipeptides, and salts thereof.
Epicatechin, epigallocatechin, epicatechin gallate, epigallocatechin gallate, catechin, gallocatechin, catechin gallate and gallocatechin gallate are used to suppress epimerization of at least one non-polymerized catechin. The epimerization inhibitor for non-polymerized catechins according to any one of claims 1 to 7.
9. The composition according to any one of claims 1 to 8, which is used for suppressing epimerization of at least one epi-unpolymerized catechin selected from the group consisting of epicatechin, epigallocatechin, epicatechin gallate and epigallocatechin gallate. 3. The epimerization inhibitor for non-polymerized catechins according to claim 1.
Containing histidine and/or a salt thereof (A1) and an epi-unpolymerized catechin (B1),
The pH is more than 4.5 and 7.9 or less, the histidine and/or salt thereof (A1) concentration in terms of histidine is 0.015 to 3 w/v%, and the Brix is 3.0% or less. A packaged beverage containing an epi-unpolymerized catechin.
The epi-unpolymerized catechin-containing according to claim 10, wherein the epi-unpolymerized catechin (B1) is at least one selected from the group consisting of epicatechin, epigallocatechin, epicatechin gallate and epigallocatechin gallate. packaged beverages.
The epi-unpolymerized catechin (B1) contains epigallocatechin gallate and/or epicatechin gallate, and the epigallocatechin gallate concentration in the beverage is 2400 μg/mL or less, and/or the epicatechin gallate concentration is 2400 μg/ml. 12. The packaged beverage containing epi-unpolymerized catechin according to claim 10 or 11, which is mL or less.
The epi-unpolymerized catechin (B1) comprises epigallocatechin gallate, and the concentration of epigallocatechin gallate in the beverage is 400 μg/mL or less, the epi-unpolymerized catechin according to any one of claims 10 to 12. A packaged beverage containing polymerized catechins.
The packaged beverage containing epi-unpolymerized catechins according to any one of claims 10 to 13, having a Brix of 1.4% or less.
The packaged beverage containing epi-unpolymerized catechins according to any one of claims 10 to 14, wherein the beverage is a tea beverage.
Containing histidine and/or a salt thereof (A1), an epi-unpolymerized catechin (B1), and an aqueous medium containing water (C),
The histidine and/or salt thereof (A1) has a histidine-equivalent concentration of 0.015 to 3 w/v%, a pH exceeding 4.5 and 8.0 or less, and a Brix of 3.0% or less. A method for producing a packaged beverage containing epi-unpolymerized catechins, comprising the step of heat-treating a certain mixture at 100°C or higher.
17. The production method according to claim 16, wherein the epi-unpolymerized catechin (B1) is at least one selected from the group consisting of epicatechin, epigallocatechin, epicatechin gallate and epigallocatechin gallate.
The epi-unpolymerized catechin (B1) contains epigallocatechin gallate and/or epicatechin gallate, and the epigallocatechin gallate concentration in the mixture is 2400 μg/mL or less and/or the epicatechin gallate concentration is 2400 μg. /mL or less, the production method according to claim 16 or 17.
The production method according to any one of claims 16 to 18, wherein the epi-unpolymerized catechin (B1) contains epigallocatechin gallate, and the concentration of epigallocatechin gallate in the mixture is 400 µg/mL or less. .
The production method according to any one of claims 16 to 19, wherein the mixture has a Brix of 1.4% or less.
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, for suppressing epimerization of non-polymerized catechins.