JP2006008580A - Production method of non-polymer catechins composition - Google Patents

Production method of non-polymer catechins composition Download PDF

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JP2006008580A
JP2006008580A JP2004187340A JP2004187340A JP2006008580A JP 2006008580 A JP2006008580 A JP 2006008580A JP 2004187340 A JP2004187340 A JP 2004187340A JP 2004187340 A JP2004187340 A JP 2004187340A JP 2006008580 A JP2006008580 A JP 2006008580A
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green tea
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JP4773696B2 (en
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Masahiro Fukuda
昌弘 福田
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Kao Corp
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a production method of a purified non-polymer catechins composition by reducing the amount of caffeine in a water-soluble composition obtained by extracting tea leaves with water without affecting the composition of non-polymer catechins prior to purification. <P>SOLUTION: In the production method of the non-polymer catechins composition, the water-soluble composition, obtained by extracting tea leaves with water, is passed through a column filled with a synthetic adsorbent at a flow rate SV (space velocity) of 0.5-5 [h<SP>-1</SP>] to be adsorbed in an amount corresponding to 0.5-10 times the volume of the synthetic adsorbent and subsequently desorbed by a two-step desorption process wherein a 10-14 (v/v)% aqueous ethanol solution and a 15-19 (v/v)% aqueous ethanol solution in amounts corresponding to 0.5-10 times the volume of the synthetic adsorbent are successively passed through the column. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

本発明は緑茶葉から水を用いて抽出した水溶性組成物を非重合体カテキン類の精製処理前の組成を損うことなくカフェイン量を低減し、精製処理された非重合体カテキン類組成物の製造法に関する。   The present invention reduces the amount of caffeine in a water-soluble composition extracted from green tea leaves using water without impairing the composition before purification of the non-polymer catechins, and the composition of the purified non-polymer catechins The present invention relates to a manufacturing method of goods.

カテキン類の効果としてはαアミラーゼ活性阻害作用などが報告されている（例えば、特許文献１参照）。このような生理効果を発現させるためには、成人一日あたり４〜５杯のお茶を飲むことが必要であることから、より簡便に大量のカテキン類を摂取するため、飲料にカテキン類を高濃度配合する技術が望まれていた。   As an effect of catechins, an α-amylase activity inhibitory action and the like have been reported (for example, see Patent Document 1). In order to express such a physiological effect, it is necessary to drink 4 to 5 cups of tea per day for an adult. Therefore, in order to ingest a large amount of catechins more easily, catechins are increased in the beverage. A technique for blending concentrations has been desired.

この方法の一つとして、緑茶抽出物の濃縮物などの水溶性組成物を利用して、カテキン類を飲料に溶解状態で添加する方法が用いられている。しかしながら、カテキン類を高濃度に配合する対象となる飲料の種類によっては、例えば紅茶抽出液や炭酸飲料にカテキン類を添加する場合など、カフェイン及び緑茶由来の風味の残存が飲料の商品価値を大きく損ねることがわかっている。
そこでこの課題を解決する為に高純度に精製された非重合体カテキン類組成物を添加する方法を用いることとなるが、従来の精製法のいずれもが水溶性組成物の精製前後における非重合体カテキン類の組成維持に対しての考慮がなされておらず、精製前の水溶性組成物で検証された生理効果が精製による組成変化後においては保証できないという問題があった。またカフェイン低減においてもクロロホルム処理などの更なる処理が必要となる問題があった。 As one of the methods, a method of adding catechins to a beverage in a dissolved state using a water-soluble composition such as a concentrate of green tea extract is used. However, depending on the type of beverage for which catechins are to be blended at a high concentration, for example, when catechins are added to black tea extracts or carbonated beverages, the remaining caffeine and green tea-derived flavors may increase the commercial value of the beverage. It is known that it will greatly damage.
Therefore, in order to solve this problem, a method of adding a high-purity purified non-polymer catechin composition is used. However, all of the conventional purification methods are non-heavy before and after purification of the water-soluble composition. No consideration has been given to maintaining the composition of the combined catechins, and the physiological effect verified with the water-soluble composition before purification cannot be guaranteed after the composition change due to purification. In addition, there is a problem that further treatment such as chloroform treatment is necessary for reducing caffeine.

このような背景の中、従来の精製法の中でも、緑茶葉から水を用いて抽出した水溶性組成物を、吸着剤に一旦吸着させ、その後溶剤等で脱着回収するという従来技術は多数試みられている（例えば、特許文献２〜６参照）。しかしながら、特許文献２は、ハイドロキシルプロピル化デキストランゲル又は親水性ビニルポリマーゲルを用いて精製する方法であるが、脱着に使用される有機溶媒濃度が常に２０％以上と高い為に、精製後のカフェイン量が多くなるという問題があった。また特許文献３は、スチレン−ジビニルベンゼン或いはメタアクリル酸エステルを用いて精製する方法であるが脱着に使用される有機溶媒濃度が最終的に６０％程度である為に、カラム処理後に別途クロロホルム処理による脱カフェイン処理を行う必要があった。同様に特許文献３、４及び５においても３０％、４０％以上あるいは５０％以上の濃度の有機溶媒である為に同様の精製状態となっていた。   Against this background, among conventional purification methods, many conventional techniques have been attempted in which a water-soluble composition extracted from green tea leaves using water is once adsorbed on an adsorbent and then desorbed and recovered with a solvent or the like. (For example, see Patent Documents 2 to 6). However, Patent Document 2 is a method of purification using a hydroxypropylated dextran gel or a hydrophilic vinyl polymer gel. However, since the concentration of the organic solvent used for desorption is always as high as 20% or more, There was a problem that the amount of caffeine increased. Patent Document 3 is a method of purification using styrene-divinylbenzene or methacrylic acid ester. However, since the concentration of the organic solvent used for desorption is finally about 60%, a separate chloroform treatment is performed after the column treatment. It was necessary to carry out a decaffeination treatment. Similarly, in Patent Documents 3, 4 and 5, since the organic solvent has a concentration of 30%, 40% or more, or 50% or more, the same purified state was obtained.

またこれらのいずれの方法においても処理前後の組成維持という概念は見受けられない。
特開平３−１３３９２８号公報 特開平１−１７５９７８号公報 特開平２−３１１４７４号公報 特開平１０−６７７７１号公報 特開平４−１８２４７９号公報 特開平６−９６０７号公報 In any of these methods, the concept of maintaining the composition before and after the treatment is not found.
JP-A-3-133828 JP-A-1-175978 Japanese Patent Laid-Open No. 2-311474 Japanese Patent Laid-Open No. 10-67771 JP-A-4-182479 JP-A-6-9607

本発明の課題は緑茶葉から水を用いて抽出した水溶性組成物を非重合体カテキン類の精製処理前の組成を損うことなくカフェイン量を低減し、精製処理された非重合体カテキン類組成物の製造法を提供することにある。   An object of the present invention is to reduce the amount of caffeine in a water-soluble composition extracted from green tea leaves using water without impairing the composition before the purification treatment of non-polymer catechins, and to obtain a purified non-polymer catechin It is in providing the manufacturing method of a kind composition.

本発明者は、緑茶葉から水を用いて抽出した水溶性組成物を非重合体カテキン類の精製処理前の組成を損うことなくカフェイン量を低減すべく検討した結果、特定の合成吸着剤に非重合体カテキン類を吸着・脱着させる工程において、使用するエタノール水溶液のエタノール濃度を制御することにより、従来よりもカフェイン含量が低く、処理前後での組成変化の小さい、緑茶風味の低減された非重合体カテキン類組成物を高収率で得られることを見出した。   As a result of examining the water-soluble composition extracted from green tea leaves using water to reduce the amount of caffeine without impairing the composition before the purification treatment of non-polymer catechins, a specific synthetic adsorption In the process of adsorbing and desorbing non-polymer catechins to the agent, the ethanol concentration of the aqueous ethanol solution used is controlled to lower the caffeine content and reduce the composition of the green tea flavor before and after treatment. It was found that the obtained non-polymer catechin composition can be obtained in high yield.

本発明は、緑茶葉から水を用いて抽出した水溶性組成物を、合成吸着剤を充填したカラムに、ＳＶ(空間速度)＝０．５〜５[ｈ-1]の通液速度で、合成吸着剤に対する通液倍数として０．５〜１０[ｖ／ｖ] 吸着させ、次いで１０〜１４（ｖ／ｖ）％エタノール水溶液を合成吸着剤の充填体積量当り０．５〜１０倍量通液し、さらにに１５〜１９（ｖ／ｖ）％エタノール水溶液を合成吸着剤の充填体積量当り０．５〜１０倍量通液させる二段階の脱着工程により脱着させる非重合体カテキン類組成物の製造方法を提供するものである。
また、本発明は、（Ａ）カフェイン／非重合体カテキン類（重量比）が０．０４未満であり、（Ｂ）緑茶葉から水を用いて抽出した水溶性組成物の非重合体カテキン類中の非重合体カテキンガレート体類率を１とした時のカテキンガレート体類率が８０〜１２０％、（Ｃ）緑茶葉から水を用いて抽出した水溶性組成物の非重合体カテキン類中の非重合体ガロ体類率を１とした時の非重合体カテキン類中の非重合体ガロ体類率が８５〜１１５％である非重合体カテキン類組成物を提供するものである。 In the present invention, a water-soluble composition extracted from green tea leaves using water is passed through a column packed with a synthetic adsorbent at a flow rate of SV (space velocity) = 0.5 to 5 [h −1 ], 0.5 to 10 [v / v] is adsorbed as the passing ratio of the synthetic adsorbent, and then 10 to 14 (v / v)% aqueous ethanol solution is passed through the synthetic adsorbent in an amount of 0.5 to 10 times per filled volume. A non-polymer catechin composition that is further desorbed by a two-stage desorption step in which a 15 to 19 (v / v)% aqueous ethanol solution is passed through the synthetic adsorbent in an amount of 0.5 to 10 times the filled volume of the synthetic adsorbent. The manufacturing method of this is provided.
The present invention also provides (A) a non-polymer catechin of a water-soluble composition extracted from green tea leaves with water, wherein (A) caffeine / non-polymer catechins (weight ratio) is less than 0.04. Non-polymer catechins of water-soluble compositions extracted from green tea leaves using water, with a catechin gallate ratio of 80 to 120% when the ratio of non-polymer catechin gallates in the class is 1 The present invention provides a non-polymer catechin composition having a non-polymer gallo-form ratio in the non-polymer catechin of 85 to 115% when the non-polymer gallo-form ratio is 1.

本発明により、従来よりもカフェイン含量が低く、処理前後での組成変化の小さい、緑茶風味の低減された非重合体カテキン類組成物を高収率で得ることができる。   According to the present invention, a non-polymer catechin composition having a lower caffeine content and a smaller compositional change before and after the treatment and a reduced green tea flavor can be obtained in a high yield.

本発明で非重合体カテキン類とは、カテキン、ガロカテキン、カテキンガレート、ガロカテキンガレートなどの非エピ体カテキン類及びエピカテキン、エピガロカテキン、エピカテキンガレート、エピガロカテキンガレートなどのエピ体カテキン類をあわせての総称である。   Non-polymer catechins in the present invention are non-epimeric catechins such as catechin, gallocatechin, catechin gallate, and gallocatechin gallate, and epicatechins such as epicatechin, epigallocatechin, epicatechin gallate, and epigallocatechin gallate. Is a collective term.

本発明で非重合体カテキンガレート体類とは、カテキンガレート、ガロカテキンガレート、エピカテキンガレート、エピガロカテキンガレートなどをあわせての総称である。また非重合体ガロ体類とは、ガロカテキン、ガロカテキンガレート、エピガロカテキン、エピガロカテキンガレートなどをあわせての総称である。   The non-polymer catechin gallate body in the present invention is a general term including catechin gallate, gallocatechin gallate, epicatechin gallate, epigallocatechin gallate and the like. The non-polymer gallo form is a general term including gallocatechin, gallocatechin gallate, epigallocatechin, epigallocatechin gallate and the like.

本発明に使用する緑茶葉としては、Camellia属、例えばC. sinensis、C. assamica及びやぶきた種、又はそれらの雑種から得られる茶葉から製茶された茶葉が挙げられる。例えば、蒸し製茶葉では普通煎茶、深蒸し煎茶、玉露、かぶせ茶、玉緑茶、番茶などが好ましい。また釜炒り製では玉緑茶や中国緑茶が特に好ましい。   Examples of the green tea leaves used in the present invention include tea leaves made from tea leaves obtained from the genus Camellia, such as C. sinensis, C. assamica and Yabuki species, or hybrids thereof. For example, for steamed tea leaves, ordinary sencha, deep steamed sencha, gyokuro, kabusecha, tama green tea, bancha and the like are preferred. In the case of making the kettle, particularly preferred are green tea and Chinese green tea.

本発明で使用する水溶性組成物は通常の緑茶抽出条件で製造される。緑茶葉からの抽出時の温度は非重合体カテキン類の抽出効率を高くする観点から７０℃〜沸騰水、さらに好ましくは８０℃〜沸騰水を使っても差し支えない。緑茶葉からの抽出時の水の量は、緑茶葉に対して５〜６０重量倍、特に５〜４０重量倍が好ましい。緑茶葉からの抽出時間は１〜６０分が好ましく、より好ましくは１〜４０分、さらに好ましくは１〜３０分である。抽出時間は短すぎると非重合体カテキン類の溶出が不十分であり、長すぎると非重合体カテキン類の熱変性異性化反応が進行してしまう。   The water-soluble composition used in the present invention is produced under normal green tea extraction conditions. From the viewpoint of increasing the extraction efficiency of non-polymer catechins, the temperature at the time of extraction from green tea leaves may be 70 ° C to boiling water, more preferably 80 ° C to boiling water. The amount of water at the time of extraction from green tea leaves is preferably 5 to 60 times by weight, particularly 5 to 40 times by weight, relative to the green tea leaves. The extraction time from green tea leaves is preferably 1 to 60 minutes, more preferably 1 to 40 minutes, and further preferably 1 to 30 minutes. If the extraction time is too short, elution of the non-polymer catechins is insufficient, and if it is too long, the heat-denaturing isomerization reaction of the non-polymer catechins proceeds.

本発明に用いる水溶性組成物は、いわゆる緑茶抽出物を濃縮したものであって、特開昭５９−２１９３８４号公報、特開平４−２０５８９号公報、特開平５−２６０９０７号公報、特開平５−３０６２７９号公報、特願２００２−１１４３５５、特願２００２−０２０４１５などに詳細に例示されている方法で調製したものを使用しても良い。市販品としては、三井農林（株）「ポリフェノン」、伊藤園（株）「テアフラン」、太陽化学（株）「サンフェノン」などが挙げられる。そのほか、カラム精製品及び化学合成品でも使用できる。ここでいう茶抽出物の濃縮物の形態としては、固体、水溶液、スラリー状など種々のものが挙げられるが、本発明の処理においては事前に水溶液の状態に調整する。   The water-soluble composition used in the present invention is a concentrate of a so-called green tea extract, which is disclosed in JP 59-219384, JP 4-20589, JP 5-260907, and JP 5-5. -306279 gazette, Japanese Patent Application No. 2002-114355, Japanese Patent Application No. 2002-020415, and the like may be used. Examples of commercially available products include “Polyphenone”, Mitsui Norin Co., Ltd., “Theafranc”, ITO EN Co., Ltd., and “Sunphenon”, Taiyo Kagaku Co., Ltd. In addition, it can also be used in column purified products and chemically synthesized products. The form of the concentrate of the tea extract here includes various forms such as a solid, an aqueous solution, and a slurry.

本発明で用いる水溶性組成物のＢrixは２〜２５、好ましくは３〜２５、更に好ましくは３〜２０の範囲にすることで、非重合体カテキン類の回収率が高まり、脱カフェイン効率も改善される。ここで前記緑茶抽出物の濃縮物を使用する場合、そのBrixは１０〜２５、さらに１５〜２５が好ましい。   The Brix of the water-soluble composition used in the present invention is 2 to 25, preferably 3 to 25, more preferably 3 to 20, thereby increasing the recovery rate of non-polymer catechins and improving the decaffeination efficiency. Improved. Here, when using the concentrate of the said green tea extract, the Brix is 10-25, Furthermore, 15-25 are preferable.

本発明に用いる合成吸着剤としては、スチレン−ジビニルベンゼン、修飾スチレン−ジビニルベンゼン又はメタクリル酸メチルを母体とするものが挙げられる。スチレン−ジビニルベンゼン系の合成吸着剤の例としては、三菱化学社製の商品名ダイヤイオンＨＰ−２０、ＨＰ−２１、セパビーズＳＰ７０、ＳＰ７００、ＳＰ８２５、ＳＰ−８２５やオルガノ社（供給元：米国ローム＆ハース社）のアンバーライトＸＡＤ４、ＸＡＤ１６ＨＰ、ＸＡＤ１１８０、ＸＡＤ２０００、住友化学（供給元：米国ローム＆ハース社）のデュオライトＳ８７４、Ｓ８７６等が挙げられる。臭素原子を核置換して吸着力を強めた修飾スチレン−ジビニルベンゼン系の合成吸着剤の例としては、三菱化学社製の商品名セパビーズＳＰ２０５、ＳＰ２０６、ＳＰ２０７等が挙げられる。メタクリル酸メチル系の合成吸着剤の例としては、三菱化学社製のセパビーズＨＰ１ＭＧ、ＨＰ２ＭＧやオルガノ社のＸＡＤ７ＨＰ、住友化学のデュオライトＳ８７７等が挙げられる。
合成吸着剤の中でも特に、特に修飾ポリスチレン系合成吸着剤及びメタクリル酸メチル系合成吸着剤が好ましい。前者はポリスチレン系合成吸着剤に比べ吸着容量が高く、また高比重である為に精製プロセスの中でアップフロー通液が可能となって好ましい。また後者は吸着量は少ないものの高極性有機物の吸着に有利な点が挙げられる。 Examples of the synthetic adsorbent used in the present invention include those based on styrene-divinylbenzene, modified styrene-divinylbenzene, or methyl methacrylate. Examples of synthetic adsorbents based on styrene-divinylbenzene include Mitsubishi Chemical's trade names Diaion HP-20, HP-21, Sepabeads SP70, SP700, SP825, SP-825, and Organo (supplier: ROHM, USA) And Amberlite XAD4, XAD16HP, XAD1180, XAD2000, and Duolite S874, S876 (supplied by Rohm & Haas, USA). Examples of modified styrene-divinylbenzene-based synthetic adsorbents that have a bromine atom substituted into the nucleus to enhance the adsorptive power include trade name products SP205, SP206, and SP207 manufactured by Mitsubishi Chemical Corporation. Examples of methyl methacrylate-based synthetic adsorbents include Sepabeads HP1MG and HP2MG manufactured by Mitsubishi Chemical Corporation, XAD7HP manufactured by Organo Corporation, and Duolite S877 manufactured by Sumitomo Chemical.
Among the synthetic adsorbents, a modified polystyrene synthetic adsorbent and a methyl methacrylate synthetic adsorbent are particularly preferable. The former is preferable because it has a higher adsorption capacity and higher specific gravity than the polystyrene-based synthetic adsorbent, and allows upflow through the purification process. The latter is advantageous in adsorbing highly polar organic substances although the amount of adsorption is small.

本発明に用いる合成吸着剤は具体的には、ＳＰ２０７などの修飾ポリスチレン系合成吸着剤（三菱化学社製）、ＨＰ２ＭＧなどのメタクリル系合成吸着剤（三菱化学社製）が挙げられるが、前述の理由からＳＰ２０７、ＨＰ２ＭＧが好ましく、ＳＰ２０７がより好ましい。   Specific examples of the synthetic adsorbent used in the present invention include a modified polystyrene synthetic adsorbent such as SP207 (manufactured by Mitsubishi Chemical Corporation) and a methacrylic synthetic adsorbent such as HP2MG (manufactured by Mitsubishi Chemical Corporation). For reasons, SP207 and HP2MG are preferable, and SP207 is more preferable.

本発明においては、まず水溶性組成物を合成吸着剤を充填したカラムに通液するが、予めＳＶ(空間速度)＝１〜５[ｈ-1]、合成吸着剤に対する通液倍数として２〜５[ｖ／ｖ] の通液条件で９５（ｖ／ｖ）％エタノール水溶液で洗浄を行い、合成吸着剤の原料モノマーや原料モノマー中の不純物等を除去するのが良い。そして、その後ＳＶ(空間速度)＝１〜５[ｈ-1]、合成吸着剤に対する通液倍数として１〜４[ｖ／ｖ] の通液条件により水洗し、エタノールを除去して合成吸着剤の含液を水系に置換する方法が選択できる。 In the present invention, first, the water-soluble composition is passed through a column packed with a synthetic adsorbent, and SV (space velocity) = 1 to 5 [h −1 ] is preliminarily set to 2 to 2 as a passage ratio for the synthetic adsorbent. It is preferable to remove the raw material monomer of the synthetic adsorbent and impurities in the raw material monomer by washing with a 95 (v / v)% aqueous ethanol solution under a flow rate of 5 [v / v]. Then, after washing with water under conditions of SV (space velocity) = 1 to 5 [h −1 ] and a passage ratio of 1 to 4 [v / v] as a passage ratio for the synthetic adsorbent, ethanol is removed and the synthetic adsorbent is removed. A method of substituting the liquid-containing solution with an aqueous system can be selected.

水溶性組成物を、合成吸着剤を充填したカラムに通液する条件としては、ＳＶ(空間速度)＝０．５〜５[ｈ-1]の通液速度で、合成吸着剤に対する通液倍数として０．５〜１０[ｖ／ｖ] で通液するのが好ましい。さらに、ＳＶ＝１〜５[ｈ-1]の通液速度で、合成吸着剤に対する通液倍数として１〜８[ｖ／ｖ] で通液するのがより好ましい。 The conditions for passing the water-soluble composition through the column filled with the synthetic adsorbent were SV (space velocity) = 0.5 to 5 [h −1 ] and the liquid passing rate with respect to the synthetic adsorbent. It is preferable to pass through at 0.5 to 10 [v / v]. Further, it is more preferable that the liquid is passed at 1 to 8 [v / v] as a liquid passing rate with respect to the synthetic adsorbent at a liquid passing speed of SV = 1 to 5 [h −1 ].

水溶性組成物をカラムに吸着後、エタノール水溶液によって脱着する条件としては、まず１０〜１４（ｖ／ｖ）％エタノール水溶液を合成吸着剤の充填体積当り０．５〜１０倍量通液し、次いで１５〜１９（ｖ／ｖ）％エタノール水溶液を合成吸着剤の充填体積量当り０．５〜１０倍量通液する二段階のグラディエント方式を採用することが非重合体カテキン類の効率的な溶出及び精製ができる点で好ましい。
ここで、１０（ｖ／ｖ）％未満のエタノール水溶液で溶出する場合、カフェイン／非重合体カテキン類比率は下がるものの、合成吸着剤に対する通液倍数が１５[ｖ／ｖ]超となり、多量の溶出液を要しかつ非重合体カテキン類の回収率が低くなってしまう。一方、２０（ｖ／ｖ）％以上のエタノール水溶液で溶出する場合、カフェインと非重合体カテキン類の分離が悪くなる。 As conditions for adsorbing the water-soluble composition to the column and then desorbing with an aqueous ethanol solution, first, a 10 to 14 (v / v)% aqueous ethanol solution was passed through the synthetic adsorbent in an amount of 0.5 to 10 times the packed volume, Next, it is effective for non-polymer catechins to adopt a two-stage gradient system in which a 15 to 19 (v / v)% aqueous ethanol solution is passed through the synthetic adsorbent in an amount of 0.5 to 10 times the filling volume. This is preferable in that it can be eluted and purified.
Here, when elution is performed with an aqueous ethanol solution of less than 10 (v / v)%, the ratio of caffeine / non-polymer catechins decreases, but the ratio of liquid passage to the synthetic adsorbent is over 15 [v / v] And the recovery rate of non-polymer catechins is low. On the other hand, when elution is performed with an ethanol aqueous solution of 20 (v / v)% or more, the separation of caffeine and non-polymer catechins becomes worse.

本発明で使用される合成吸着剤は精製処理後に所定の方法を用いることにより再使用できる。具体的には、９０〜９９．５（ｖ／ｖ）％エタノール水溶液を通液し吸着剤上に残存する水溶液組成物成分をすべて脱着させる。   The synthetic adsorbent used in the present invention can be reused by using a predetermined method after the purification treatment. Specifically, a 90 to 99.5 (v / v)% ethanol aqueous solution is passed through to desorb all aqueous solution composition components remaining on the adsorbent.

本発明により得られる非重合体カテキン類組成物は、（Ａ）カフェイン／非重合体カテキン類（重量比）が０．０４未満であり、カフェイン含量が低い。また、本発明方法によれば、水溶性組成物からの（Ｂ）非重合体カテキン類の回収率が７５重量％以上、（Ｃ）非重合体カテキン類中の非重合体カテキンガレート体類率の濃度変化が２０％未満、（Ｄ）非重合体カテキン類中の非重合体ガロ体類率の濃度変化が１５％未満であり、処理前後の組成変化が極めて少ない。   The non-polymer catechin composition obtained by the present invention has (A) caffeine / non-polymer catechin (weight ratio) of less than 0.04 and a low caffeine content. Further, according to the method of the present invention, the recovery rate of (B) non-polymer catechins from the water-soluble composition is 75% by weight or more, and (C) the rate of non-polymer catechin gallates in the non-polymer catechins The change in the concentration of the non-polymer galactols in the non-polymer catechins is less than 15%, and the composition change before and after the treatment is extremely small.

本発明で得られた非重合体カテキン類組成物はそのままで使用しても良く、減圧濃縮、薄膜濃縮などの方法によりエタノールを除去してもよい。通常飲料への配合に使用する場合、エタノールを完全に除去した方が好ましい。また非重合体カテキン類組成物の製品形態として粉体が望ましい場合は、噴霧乾燥や凍結乾燥等の方法によって粉体化できる。   The non-polymer catechin composition obtained in the present invention may be used as it is, or ethanol may be removed by a method such as vacuum concentration or thin film concentration. When used for blending into a normal beverage, it is preferable to completely remove ethanol. In addition, when a powder is desirable as a product form of the non-polymer catechin composition, it can be pulverized by a method such as spray drying or freeze drying.

本発明で得られた非重合体カテキン類組成物は容器詰飲料に配合できる。使用される容器は一般の飲料と同様にポリエチレンテレフタレートを主成分とする成形容器（いわゆるＰＥＴボトル）、金属缶、金属箔やプラスチックフィルムと複合された紙容器、瓶などの通常の形態で提供することができる。ここでいう容器詰飲料とは希釈せずに飲用できるものをいう。   The non-polymer catechin composition obtained in the present invention can be blended in a packaged beverage. Containers to be used are provided in ordinary forms such as molded containers (so-called PET bottles) mainly composed of polyethylene terephthalate, metal cans, paper containers combined with metal foil and plastic film, bottles, etc., as with general beverages. be able to. The container-packed drink here means a drink that can be taken without dilution.

また上記の容器詰飲料は、例えば、金属缶のように容器に充填後、加熱殺菌できる場合にあっては食品衛生法に定められた殺菌条件で製造される。ＰＥＴボトル、紙容器のようにレトルト殺菌できないものについては、あらかじめ上記と同等の殺菌条件、例えばプレート式熱交換器などで高温短時間殺菌後、一定の温度迄冷却して容器に充填する等の方法が採用される。また無菌下で、充填された容器に別の成分を配合して充填してもよい。   Moreover, said container-packed drink is manufactured on the sterilization conditions prescribed | regulated to the food hygiene law, for example, when it can heat-sterilize after filling a container like a metal can. For PET bottles and paper containers that cannot be sterilized by retort, sterilize under the same conditions as above, for example, after sterilizing at high temperature and short time with a plate heat exchanger, etc. The method is adopted. Moreover, you may mix | blend another component with the filled container under aseptic conditions.

（カテキン類の測定法）
フィルター（０．８μｍ）で濾過し、次いで蒸留水で希釈した容器詰めされた飲料を、島津製作所製、高速液体クロマトグラフ（型式ＳＣＬ-１０ＡＶＰ）を用い、オクタデシル基導入液体クロマトグラフ用パックドカラム Ｌ−カラムＴＭ ＯＤＳ（４．６ｍｍφ×２５０ｍｍ：財団法人 化学物質評価研究機構製）を装着し、カラム温度３５℃でグラジエント法により行った。移動相Ａ液は酢酸を０．１ｍｏｌ／Ｌ含有の蒸留水溶液、Ｂ液は酢酸を０．１ｍｏｌ／Ｌ含有のアセトニトリル溶液とし、試料注入量は２０μＬ、ＵＶ検出器波長は２８０ｎｍの条件で行った。 (Measurement method of catechins)
Packed column for liquid chromatography with octadecyl group introduction, using a high-performance liquid chromatograph (model SCL-10AVP), manufactured by Shimadzu Corporation, for the beverage packed in a container after filtering with a filter (0.8 μm) and then diluting with distilled water L -Column TM ODS (4.6 mmφ x 250 mm: manufactured by Chemical Substance Evaluation Research Organization) was attached, and the gradient was performed at a column temperature of 35 ° C. The mobile phase A solution was a distilled aqueous solution containing 0.1 mol / L of acetic acid, the B solution was an acetonitrile solution containing 0.1 mol / L of acetic acid, the sample injection amount was 20 μL, and the UV detector wavelength was 280 nm. .

（Ｂrixの測定法）
測定試料をイオン交換水によってゼロ点調節したＢrix計（ＲＸ−５０００α（ＡＴＡＧＯ社製））により、測定を行った。 (Measurement method of Brix)
The measurement was performed with a Brix meter (RX-5000α (manufactured by ATAGO)) whose zero point was adjusted with ion-exchanged water.

（殺菌後の風味評価）
各実施例で得られた非重合体カテキン類組成物をカテキン含有率が０．１７５％[ｗ／ｖ]となるように脱イオン水で希釈し、その４０ｍＬを５０ｍＬの耐圧製ガラス容器に入れた。そこにアスコルビン酸Ｎａを０．１重量％添加し、５％重炭酸Ｎａ水溶液でｐＨを６．４に調整し、窒素置換を行い、オートクレーブで１２１℃、１０分間加熱滅菌した。その後、評価パネラー５名によって緑茶由来の異味・異臭が感じられないか確認を行った。 (Flavor evaluation after sterilization)
The non-polymer catechin composition obtained in each example was diluted with deionized water so that the catechin content was 0.175% [w / v], and 40 mL thereof was placed in a 50 mL pressure-resistant glass container. It was. Thereto was added 0.1% by weight of sodium ascorbate, the pH was adjusted to 6.4 with a 5% aqueous sodium bicarbonate solution, nitrogen substitution was performed, and the mixture was sterilized by heating at 121 ° C. for 10 minutes in an autoclave. Then, it was confirmed by the evaluation panelists whether or not the taste and odor derived from green tea were felt.

（沈殿の評価方法）
耐圧製ガラス容器に入っている評価サンプルを、５５℃の恒温槽に入れて、濁りの発生状況を確認した。イルミネーター上で内容物の状態を観察し、澱の観察された時点を澱生成日とした。 (Evaluation method of precipitation)
The evaluation sample contained in the pressure-resistant glass container was placed in a constant temperature bath at 55 ° C., and the occurrence of turbidity was confirmed. The state of the contents was observed on an illuminator, and the time when starch was observed was defined as the starch production date.

実施例１
宮崎産緑茶２番茶１００ｇを８５℃の脱イオン水１，５００gで３０分間抽出、冷却、搾汁後、２号ろ紙によりろ過し、Brix３．４の抽出液１，２００ｇを得た。次いで、ガラスカラム（内径４０ｍｍ×高さ４００ｍｍ）に充填した合成吸着剤セパビーズＳＰ−２０７（三菱化学（株）製）３００ｍＬを、予めＳＶ＝３（ｈ-1）で９５％（ｖ／ｖ）エタノール９００ｍＬによる洗浄を行い、ＳＶ＝３（ｈ-1)で６００ｍＬの水で洗浄した。その後、得られた抽出液１，２００ｇをＳＶ＝３（ｈ-1）で通液し、通過液は廃棄した。茶抽出液を吸着後、カラム内のＳＰ−２０７に１２％（ｖ／ｖ）エタノール水をＳＶ＝３（ｈ-1）で１，８００ｍＬ通液した後、１７％（ｖ／ｖ）エタノール水をＳＶ＝３（ｈ-1）で１，２００ｍＬ通液した。得られた溶出液をロータリーエバポレーターによりBrix２０まで減圧濃縮して非重合体カテキン類組成物１００．１ｇを得た。 Example 1
100 g of 2nd green tea from Miyazaki green tea was extracted with 1,500 g of deionized water at 85 ° C. for 30 minutes, cooled and squeezed, and then filtered through No. 2 filter paper to obtain 1,200 g of Brix 3.4 extract. Next, 300 mL of a synthetic adsorbent Sepabead SP-207 (manufactured by Mitsubishi Chemical Corporation) packed in a glass column (inner diameter 40 mm × height 400 mm) was previously 95% (v / v) at SV = 3 (h −1 ). Washing was performed with 900 ml of ethanol, and washing with 600 ml of water at SV = 3 (h −1 ). Thereafter, 1,200 g of the obtained extract was passed at SV = 3 (h −1 ), and the passed solution was discarded. After adsorbing the tea extract, 1,800 mL of 12% (v / v) ethanol water was passed through SP-207 in the column at SV = 3 (h −1 ), and then 17% (v / v) ethanol water. Was passed through 1,200 mL at SV = 3 (h −1 ). The obtained eluate was concentrated under reduced pressure to Brix 20 by a rotary evaporator to obtain 100.1 g of a non-polymer catechin composition.

実施例２
合成吸着剤にセパビーズＳＰ−７０（三菱化学（株）製）を使用した以外は実施例１と全く同様にして非重合体カテキン類組成物108.6gを得た。 Example 2
A non-polymer catechin composition 108.6 g was obtained in the same manner as in Example 1 except that Sepabead SP-70 (manufactured by Mitsubishi Chemical Corporation) was used as the synthetic adsorbent.

実施例３
合成吸着剤にセパビーズＨＰ２ＭＧ（三菱化学（株）製）を使用した以外は実施例１と全く同様にして非重合体カテキン類組成物１０６．８ｇを得た。 Example 3
Except for using Sepabeads HP2MG (manufactured by Mitsubishi Chemical Corporation) as a synthetic adsorbent, 106.8 g of a non-polymer catechin composition was obtained in the same manner as in Example 1.

実施例４
実施例１と同様に抽出した抽出液をロータリーエバポレーターによりＢrix２０まで減圧濃縮して濃縮液１０３．５ｇを得た。その後、実施例１と同様にガラスカラム（内径４０ｍｍ×高さ４００ｍｍ）に充填した合成吸着剤セパビーズＳＰ−２０７（三菱化学（株）製）３００ｍＬに通液させ、非重合体カテキン類組成物１０５ｇを得た。 Example 4
The extract extracted in the same manner as in Example 1 was concentrated under reduced pressure to Brix 20 using a rotary evaporator to obtain 103.5 g of a concentrated solution. Thereafter, the solution was passed through 300 mL of a synthetic adsorbent Sepabead SP-207 (Mitsubishi Chemical Corporation) packed in a glass column (inner diameter 40 mm × height 400 mm) in the same manner as in Example 1, and 105 g of the non-polymer catechin composition Got.

参考例１
宮崎産緑茶２番茶１００ｇを８５℃の脱イオン水１，５００gで３０分間抽出、冷却、搾汁後、２号ろ紙によりろ過し、Brix３．４の抽出液１，２００ｇを得た。 Reference example 1
100 g of 2nd green tea from Miyazaki green tea was extracted with 1,500 g of deionized water at 85 ° C. for 30 minutes, cooled and squeezed, and then filtered through No. 2 filter paper to obtain 1,200 g of Brix 3.4 extract.

比較例１
実施例１の１２％（ｖ／ｖ）エタノール水及び１７％（ｖ／ｖ）エタノール水を通液する代わりに、５％（ｖ／ｖ）エタノール水をＳＶ＝３（ｈ-1）で３，０００ｍＬ通液した以外は全く同様にして行った。得られた非重合体カテキン類組成物は１１０．２ｇであった。 Comparative Example 1
Instead of passing 12% (v / v) ethanol water and 17% (v / v) ethanol water of Example 1, 5% (v / v) ethanol water was changed to 3 at SV = 3 (h −1 ). , Except that 1,000 mL was passed. The obtained non-polymer catechin composition was 110.2 g.

比較例２
実施例１の１２％（ｖ／ｖ）エタノール水及び１７％（ｖ／ｖ）エタノール水を通液する代わりに、３０％（ｖ／ｖ）エタノール水をＳＶ＝３（ｈ-1）で９００ｍＬを通液した以外は全く同様にして行った。得られた非重合体カテキン類組成物は１０５．３ｇであった。 Comparative Example 2
Instead of passing 12% (v / v) ethanol water and 17% (v / v) ethanol water of Example 1, 900 mL of 30% (v / v) ethanol water at SV = 3 (h −1 ). The procedure was exactly the same except that the solution was passed through. The obtained non-polymer catechin composition was 105.3 g.

比較例３
実施例１の１２％（ｖ／ｖ）エタノール水及び１７％（ｖ／ｖ）エタノール水を通液する代わりに、２０％（ｖ／ｖ）エタノール水をＳＶ＝３（ｈ-1）で９００ｍＬを通液した以外は全く同様にして行った。 Comparative Example 3
Instead of passing 12% (v / v) ethanol water and 17% (v / v) ethanol water of Example 1, 900 mL of 20% (v / v) ethanol water at SV = 3 (h −1 ). The procedure was exactly the same except that the solution was passed through.

比較例４
宮崎産緑茶２番茶１０００ｇを８５℃の脱イオン水１０Lで１０分間抽出、冷却、搾汁後、２号ろ紙によりろ過し、その後、減圧濃縮してBrix２１．３の茶抽出液１，５００ｇを得た。次いで、ガラスカラム（内径４０ｍｍ×高さ４００ｍｍ）に充填した合成吸着剤デュオライトＳ−８７６（デュオライトインターナショナルINC社製）３００ｍＬを、予めＳＶ＝３（ｈ-1）で６０％（ｖ／ｖ）アセトン水溶液９００ｍＬによる洗浄を行い、ＳＶ＝３（ｈ-1)で６００ｍＬの水で洗浄した。その後、得られた茶抽出液１，５００ｇをＳＶ＝３（ｈ-1）で通液し、通過液は廃棄した。茶抽出液を吸着後、カラム内のＳ−８７６に１０％（ｖ／ｖ）アセトン水溶液をＳＶ＝３（ｈ-1）で１，８００ｍＬ通液した後、６０％（ｖ／ｖ）アセトン水溶液をＳＶ＝３（ｈ-1）で１，２００ｍＬ通液した。得られた溶出液をロータリーエバポレーターによりBrix２０まで減圧濃縮して非重合体カテキン類組成物１０６．３ｇを得た。 Comparative Example 4
Extract 1000g of Miyazaki green tea No. 2 tea with 10L of deionized water at 85 ° C for 10 minutes, cool, squeeze, filter with No. 2 filter paper, and then concentrate under reduced pressure to obtain 1,500 g of Brix21.3 tea extract It was. Next, 300 mL of a synthetic adsorbent Duolite S-876 (manufactured by Duolite International Inc.) packed in a glass column (inner diameter 40 mm × height 400 mm) was preliminarily set to 60% (v / v) at SV = 3 (h −1 ). ) Washing was performed with 900 mL of an aqueous acetone solution and then with 600 mL of water at SV = 3 (h −1 ). Thereafter, 1,500 g of the obtained tea extract was passed at SV = 3 (h −1 ), and the passing solution was discarded. After adsorbing the tea extract, 1,800 mL of 10% (v / v) acetone aqueous solution was passed through S-876 in the column at SV = 3 (h −1 ), and then 60% (v / v) acetone aqueous solution. Was passed through 1,200 mL at SV = 3 (h −1 ). The obtained eluate was concentrated under reduced pressure to Brix 20 using a rotary evaporator to obtain 106.3 g of a non-polymer catechin composition.

表１に分析並びに評価結果を示す。   Table 1 shows the analysis and evaluation results.

Figure 2006008580
Figure 2006008580

実施例１〜４のいずれにおいても処理前後におけるカテキン類組成の変化を極力抑えるとともに回収率が高く、カフェイン濃度の低い非重合体カテキン類組成物を得ることができた。また容器詰飲料をモデル系とした殺菌後の風味評価において緑茶由来の異味・異臭が感じられず、５５℃保存後の澱生成もみられなかった。   In any of Examples 1 to 4, it was possible to obtain a non-polymer catechin composition having a low caffeine concentration and a high recovery rate while minimizing a change in the catechin composition before and after the treatment. In addition, in the flavor evaluation after sterilization using a packaged beverage as a model system, no off-flavor and off-flavor derived from green tea was felt, and no starch was produced after storage at 55 ° C.

Claims (4)

緑茶葉から水を用いて抽出した水溶性組成物を、合成吸着剤を充填したカラムに、ＳＶ(空間速度)＝０．５〜５[ｈ-1]の通液速度で、合成吸着剤に対する通液倍数として０．５〜１０[ｖ／ｖ] 吸着させ、次いで１０〜１４（ｖ／ｖ）％エタノール水溶液を合成吸着剤の充填体積量当り０．５〜１０倍量通液し、さらに１５〜１９（ｖ／ｖ）％エタノール水溶液を合成吸着剤の充填体積量当り０．５〜１０倍量通液させる二段階の脱着工程により脱着させる非重合体カテキン類組成物の製造方法。 A water-soluble composition extracted from green tea leaves using water is passed through a column packed with a synthetic adsorbent at a liquid passing speed of SV (space velocity) = 0.5 to 5 [h −1 ] with respect to the synthetic adsorbent. 0.5 to 10 [v / v] is adsorbed as the passing ratio, and then 10 to 14 (v / v)% aqueous ethanol solution is passed through the synthetic adsorbent in an amount of 0.5 to 10 times per filled volume. A method for producing a non-polymer catechin composition in which a 15 to 19 (v / v)% aqueous ethanol solution is desorbed by a two-stage desorption process in which 0.5 to 10 times the amount of the synthetic adsorbent is filled. （Ａ）カフェイン／非重合体カテキン類（重量比）が０．０４未満であり、（Ｂ）緑茶葉から水を用いて抽出した水溶性組成物の非重合体カテキン類中の非重合体カテキンガレート体類率を１とした時のカテキンガレート体類率が８０〜１２０％、（Ｃ）緑茶葉から水を用いて抽出した水溶性組成物の非重合体カテキン類中の非重合体ガロ体類率を１として時の非重合体カテキン類中の非重合体ガロ体類率が８５〜１１５％である請求項１記載の非重合体カテキン類組成物の製造方法。   (A) Caffeine / non-polymer catechins (weight ratio) is less than 0.04, (B) non-polymer in non-polymer catechins of water-soluble composition extracted from green tea leaves using water Non-polymer galloins in non-polymer catechins of water-soluble compositions extracted from green tea leaves with water, with a catechin gallate ratio of 80 to 120% when the catechin gallate ratio is 1. The method for producing a non-polymer catechin composition according to claim 1, wherein the ratio of the non-polymer galchins in the non-polymer catechins is 85 to 115% when the body rate is 1. 緑茶葉から水を用いて抽出した水溶性組成物のＢrixが２〜２５である請求項１又は２記載の非重合体カテキン類組成物の製造方法。   The method for producing a non-polymer catechin composition according to claim 1 or 2, wherein Brix of the water-soluble composition extracted from green tea leaves using water is 2 to 25. （Ａ）カフェイン／非重合体カテキン類（重量比）が０．０４未満であり、（Ｂ）緑茶葉から水を用いて抽出した水溶性組成物の非重合体カテキン類中の非重合体カテキンガレート体類率を１とした時のカテキンガレート体類率が８０〜１２０％、（Ｃ）緑茶葉から水を用いて抽出した水溶性組成物の非重合体カテキン類中の非重合体ガロ体類率を１とした時の非重合体カテキン類中の非重合体ガロ体類率が８５〜１１５％である非重合体カテキン類組成物。   (A) Caffeine / non-polymer catechins (weight ratio) is less than 0.04, (B) non-polymer in non-polymer catechins of water-soluble composition extracted from green tea leaves using water When the catechin gallate product rate is 1, the catechin gallate product rate is 80 to 120%. (C) Non-polymer galloins in non-polymer catechins of water-soluble compositions extracted from green tea leaves using water A non-polymer catechin composition having a non-polymer gallo-form ratio in the non-polymer catechins of 85 to 115% when the body ratio is 1.
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