JP6348392B2 - Method for producing purified chlorogenic acid-containing composition - Google Patents
Method for producing purified chlorogenic acid-containing composition Download PDFInfo
- Publication number
- JP6348392B2 JP6348392B2 JP2014200016A JP2014200016A JP6348392B2 JP 6348392 B2 JP6348392 B2 JP 6348392B2 JP 2014200016 A JP2014200016 A JP 2014200016A JP 2014200016 A JP2014200016 A JP 2014200016A JP 6348392 B2 JP6348392 B2 JP 6348392B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- containing composition
- exchange resin
- chlorogenic acid
- mass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 235000001368 chlorogenic acid Nutrition 0.000 title claims description 130
- PZIRUHCJZBGLDY-UHFFFAOYSA-N Caffeoylquinic acid Natural products CC(CCC(=O)C(C)C1C(=O)CC2C3CC(O)C4CC(O)CCC4(C)C3CCC12C)C(=O)O PZIRUHCJZBGLDY-UHFFFAOYSA-N 0.000 title claims description 91
- CWVRJTMFETXNAD-JUHZACGLSA-N chlorogenic acid Chemical compound O[C@@H]1[C@H](O)C[C@@](O)(C(O)=O)C[C@H]1OC(=O)\C=C\C1=CC=C(O)C(O)=C1 CWVRJTMFETXNAD-JUHZACGLSA-N 0.000 title claims description 90
- CWVRJTMFETXNAD-FWCWNIRPSA-N 3-O-Caffeoylquinic acid Natural products O[C@H]1[C@@H](O)C[C@@](O)(C(O)=O)C[C@H]1OC(=O)\C=C\C1=CC=C(O)C(O)=C1 CWVRJTMFETXNAD-FWCWNIRPSA-N 0.000 title claims description 87
- CWVRJTMFETXNAD-KLZCAUPSSA-N Neochlorogenin-saeure Natural products O[C@H]1C[C@@](O)(C[C@@H](OC(=O)C=Cc2ccc(O)c(O)c2)[C@@H]1O)C(=O)O CWVRJTMFETXNAD-KLZCAUPSSA-N 0.000 title claims description 87
- 229940074393 chlorogenic acid Drugs 0.000 title claims description 87
- FFQSDFBBSXGVKF-KHSQJDLVSA-N chlorogenic acid Natural products O[C@@H]1C[C@](O)(C[C@@H](CC(=O)C=Cc2ccc(O)c(O)c2)[C@@H]1O)C(=O)O FFQSDFBBSXGVKF-KHSQJDLVSA-N 0.000 title claims description 87
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- 239000000203 mixture Substances 0.000 title claims description 81
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- UFCLZKMFXSILNL-PSEXTPKNSA-N Isochlorogenic acid b Chemical compound O([C@@H]1C[C@@](O)(C[C@H]([C@H]1OC(=O)\C=C\C=1C=C(O)C(O)=CC=1)O)C(O)=O)C(=O)\C=C\C1=CC=C(O)C(O)=C1 UFCLZKMFXSILNL-PSEXTPKNSA-N 0.000 description 4
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- 239000004925 Acrylic resin Substances 0.000 description 3
- GYFFKZTYYAFCTR-ZNEHSRBWSA-N Cryptochlorogensaeure Natural products O[C@@H]1C[C@@](O)(C[C@@H](O)[C@@H]1OC(=O)C=Cc2ccc(O)c(O)c2)C(=O)O GYFFKZTYYAFCTR-ZNEHSRBWSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
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Landscapes
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Description
本発明は、精製クロロゲン酸類含有組成物の製造方法に関する。 The present invention relates to a method for producing a purified chlorogenic acid-containing composition.
クロロゲン酸類は、優れた血圧降下作用を有するという報告がなされており、サプリメントや飲食品への応用が期待されている。クロロゲン酸類を多く含有する素材としてコーヒー豆が挙げられるが、コーヒー豆中にはカフェインが含まれている。このため、カフェインを含有するクロロゲン酸類含有組成物から、カフェインを選択的に除去する方法が検討されてきた。 It has been reported that chlorogenic acids have an excellent blood pressure lowering effect, and application to supplements and foods and drinks is expected. Coffee beans can be mentioned as a material containing a large amount of chlorogenic acids, and caffeine is contained in the coffee beans. For this reason, methods for selectively removing caffeine from chlorogenic acid-containing compositions containing caffeine have been studied.
例えば、生コーヒー豆の水性溶媒抽出物を強酸性陽イオン交換樹脂と接触させる方法(特許文献1)、コーヒー豆抽出物のpHを0.5〜4.0に調整した後、固液分離した液を合成吸着剤に接触させ、アルカリ性水溶液を通液してクロロゲン酸類を溶出させる方法(特許文献2)等が知られている。また、クロロゲン酸類含有組成物を陽イオン交換樹脂に接触させ、次いでその処理液を陰イオン交換樹脂に接触させ、次いで陰イオン交換樹脂に脱離液を接触させる方法も提案されている(特許文献3) For example, a method in which an aqueous solvent extract of green coffee beans is brought into contact with a strongly acidic cation exchange resin (Patent Document 1), and after adjusting the pH of the coffee bean extract to 0.5 to 4.0, solid-liquid separation is performed. A method is known in which a liquid is brought into contact with a synthetic adsorbent, and an alkaline aqueous solution is passed through to elute chlorogenic acids (Patent Document 2). In addition, a method is also proposed in which a chlorogenic acid-containing composition is brought into contact with a cation exchange resin, then the treatment liquid is brought into contact with an anion exchange resin, and then the desorption liquid is brought into contact with the anion exchange resin (Patent Document). 3)
本発明の課題は、クロロゲン酸類を損なうことなく、カフェインを効率的に低減可能な精製クロロゲン酸類含有組成物の製造方法を提供することにある。 The subject of this invention is providing the manufacturing method of the refinement | purification chlorogenic acid containing composition which can reduce caffeine efficiently, without impairing chlorogenic acids.
そこで、本発明者らは、上記課題に鑑み種々検討した結果、原料クロロゲン酸類含有組成物を陽イオン交換樹脂に接触させ、次いでその処理液を陰イオン交換樹脂に接触させた後、特定の温度以上の水で陰イオン交換樹脂を洗浄し、次いで陰イオン交換樹脂に特定の脱離液を接触させることにより、クロロゲン酸類を損なうことなく、カフェインがより一層低減された精製クロロゲン酸類含有組成物を収率よく得られることを見出した。 Therefore, as a result of various investigations in view of the above problems, the present inventors brought the raw material chlorogenic acid-containing composition into contact with the cation exchange resin, and then brought the treatment liquid into contact with the anion exchange resin, and then a specific temperature. Purified chlorogenic acid-containing composition in which caffeine is further reduced without damaging chlorogenic acids by washing the anion exchange resin with the above water and then bringing the specific anion exchange resin into contact with the anion exchange resin. Was found to be obtained in good yield.
すなわち、本発明は、原料クロロゲン酸類含有組成物を陽イオン交換樹脂に接触させる工程Aと、
工程Aにより得られた液を弱塩基性陰イオン交換樹脂に接触させる工程Bと、
工程B後の弱塩基性陰イオン交換樹脂に35℃以上の水を接触させる工程Cと、
工程C後の弱塩基性陰イオン交換樹脂に酸性水溶液、又はアルカリ性水溶液を接触させる工程D
を備える、精製クロロゲン酸類含有組成物の製造方法を提供するものである。
That is, the present invention includes a step A in which a raw material chlorogenic acid-containing composition is contacted with a cation exchange resin;
Contacting the liquid obtained in step A with a weakly basic anion exchange resin; and
Step C in which water at 35 ° C. or higher is brought into contact with the weakly basic anion exchange resin after Step B;
Step D in which an acidic aqueous solution or an alkaline aqueous solution is brought into contact with the weakly basic anion exchange resin after Step C
A method for producing a purified chlorogenic acid-containing composition is provided.
本発明によれば、クロロゲン酸類を損なうことなく、カフェインがより一層低減された精製クロロゲン酸類含有組成物を簡便な操作で製造することができる。 According to the present invention, a purified chlorogenic acid-containing composition in which caffeine is further reduced can be produced by a simple operation without impairing chlorogenic acids.
本発明の精製クロロゲン酸類含有組成物の製造方法は、工程A、工程B、工程C及び工程Dを備えるものである。以下、各工程について詳細に説明する。 The method for producing a purified chlorogenic acid-containing composition of the present invention comprises Step A, Step B, Step C and Step D. Hereinafter, each step will be described in detail.
(工程A)
本発明に係る工程Aは、原料クロロゲン酸類含有組成物を陽イオン交換樹脂に接触させる工程である。
(Process A)
Step A according to the present invention is a step of bringing the raw material chlorogenic acid-containing composition into contact with a cation exchange resin.
原料クロロゲン酸類含有組成物としては、クロロゲン酸類が含まれていれば特に限定されないが、クロロゲン酸類を含む植物の抽出物を用いることができる。このような植物抽出物としては、例えば、ヒマワリ種子、リンゴ未熟果、コーヒー豆、シモン葉、マツ科植物の球果、マツ科植物の種子殻、サトウキビ、南天の葉、ゴボウ、ナスの皮、ウメの果実、フキタンポポ、ブドウ科植物等から抽出されたものが挙げられる。なお、抽出方法及び抽出条件は特に限定されず、公知の方法及び条件を採用することができる。 Although it will not specifically limit as a raw material chlorogenic acid containing composition if chlorogenic acids are contained, The extract of the plant containing chlorogenic acids can be used. Examples of such plant extracts include sunflower seeds, apple immature fruits, coffee beans, Simon leaves, pine cones, pine seed shells, sugar cane, southern leaves, burdock, eggplant skin, Examples include those extracted from ume fruit, dandelion, and vines. In addition, an extraction method and extraction conditions are not specifically limited, A well-known method and conditions are employable.
これらの中でも、原料クロロゲン酸類含有組成物としては、クロロゲン酸類含量等の点から、コーヒー豆の抽出物が好ましい。また、抽出に使用するコーヒー豆は、生コーヒー豆でも、焙煎コーヒー豆でもよく、これらを併用することも可能であるが、クロロゲン酸類の含量等の点から、生コーヒー豆及び浅焙煎コーヒー豆から選ばれる1種以上が好ましく、生コーヒー豆が更に好ましい。浅焙煎コーヒー豆のL値は、クロロゲン酸類の含量の点から、27以上が好ましく、29以上が更に好ましく、また風味の点から、62未満が好ましく、60以下がより好ましく、55以下が更に好ましい。浅焙煎コーヒー豆のL値の範囲としては、好ましくは27以上62未満、より好ましくは29〜60、更に好ましくは29〜55である。ここで、本明細書において「L値」とは、黒をL値0とし、また白をL値100として、焙煎コーヒー豆の明度を色差計で測定したものである。 Among these, as the raw material chlorogenic acid-containing composition, an extract of coffee beans is preferable from the viewpoint of chlorogenic acid content and the like. Further, the coffee beans used for extraction may be raw coffee beans or roasted coffee beans, and these can be used in combination. However, from the viewpoint of the content of chlorogenic acids, etc., raw coffee beans and shallow roasted coffee beans can be used. One or more selected from beans are preferred, and green coffee beans are more preferred. The L value of the lightly roasted coffee beans is preferably 27 or more, more preferably 29 or more, and more preferably less than 62, more preferably 60 or less, and even more preferably 55 or less from the viewpoint of the content of chlorogenic acids. preferable. The range of the L value of the shallow roasted coffee beans is preferably 27 or more and less than 62, more preferably 29 to 60, and still more preferably 29 to 55. Here, “L value” in this specification is a value obtained by measuring the brightness of roasted coffee beans with a color difference meter, with black as L value 0 and white as L value 100.
コーヒーの木の種類としては、アラビカ種、ロブスタ種、リベリカ種及びアラブスタ種のいずれでもよい。また、コーヒー豆の産地は特に限定されないが、例えば、ブラジル、コロンビア、タンザニア、モカ、キリマンジャロ、マンデリン、ブルーマウンテン、グアテマラ、ベトナム、インドネシア等が挙げられる。抽出方法及び抽出条件は特に限定されないが、例えば、特開昭58−138347号公報、特開昭59−51763号公報、特開昭62−111671号公報、特開平5−236918号公報等に記載の方法を採用することができる。なお、抽出溶媒として、水に代えて、エタノール又はエタノール及び水の混合溶媒を用いることも可能であり、混合溶媒中のエタノール濃度は適宜選択することができる。 The type of coffee tree may be any of Arabica, Robusta, Revelica and Arabsta. Moreover, although the production region of coffee beans is not particularly limited, examples include Brazil, Colombia, Tanzania, Mocha, Kilimanjaro, Mandelin, Blue Mountain, Guatemala, Vietnam, Indonesia, and the like. The extraction method and extraction conditions are not particularly limited, but are described in, for example, JP-A-58-138347, JP-A-59-51763, JP-A-62-111671, JP-A-5-236918, and the like. This method can be adopted. In addition, it is also possible to use ethanol or a mixed solvent of ethanol and water instead of water as the extraction solvent, and the ethanol concentration in the mixed solvent can be appropriately selected.
また、原料クロロゲン酸類含有組成物として市販のクロロゲン酸類含有製剤を使用してもよく、例えば、フレーバーホルダーRC(長谷川香料株式会社製)が挙げられる。なお、原料クロロゲン酸類含有組成物の形態としては、例えば、液体、スラリー、半固体、固体等の種々のものが挙げられる。 Moreover, you may use a commercially available chlorogenic acid containing formulation as a raw material chlorogenic acid containing composition, for example, flavor holder RC (made by Hasegawa Incense Co., Ltd.) is mentioned. In addition, as a form of raw material chlorogenic acid containing composition, various things, such as a liquid, a slurry, a semi-solid, a solid, are mentioned, for example.
陽イオン交換樹脂に接触させる際の原料クロロゲン酸類含有組成物は、水溶液の形態であることが好ましい。水溶液の形態の原料クロロゲン酸類含有組成物は、例えば、クロロゲン酸類を含有する植物から水を用いて抽出された抽出液を、必要により希釈又は濃縮して用いてもよい。また、得られた抽出液から水及びエタノールから選ばれる抽出溶媒を除去した乾燥物を、再び水に溶解した液を用いてもよい。 It is preferable that the raw material chlorogenic acid-containing composition to be brought into contact with the cation exchange resin is in the form of an aqueous solution. The raw material chlorogenic acid-containing composition in the form of an aqueous solution may be used, for example, by diluting or concentrating, if necessary, an extract extracted with water from a plant containing chlorogenic acids. Moreover, you may use the liquid which melt | dissolved the dry substance which removed the extraction solvent chosen from water and ethanol from the obtained extract again in water.
原料クロロゲン酸類含有組成物を溶解させた水溶液中のクロロゲン酸類含有量は適宜選択可能であるが、精製効率の観点から、0.1質量%以上が好ましく、0.5質量%以上がより好ましく、1質量%以上が更に好ましく、そして20質量%以下が好ましく、10質量%以下がより好ましく、5質量%以下が更に好ましい。かかるクロロゲン酸類の含有量の範囲としては、好ましくは0.1〜20質量%、より好ましくは0.5〜20質量%、更に好ましくは0.5〜10質量%、より更に好ましくは1〜5質量%である。ここで、本明細書における「クロロゲン酸類」とは、3−カフェオイルキナ酸、4−カフェオイルキナ酸及び5−カフェオイルキナ酸のモノカフェオイルキナ酸と、3−フェルラキナ酸、4−フェルラキナ酸及び5−フェルラキナ酸のモノフェルラキナ酸と、3,4−ジカフェオイルキナ酸、3,5−ジカフェオイルキナ酸及び4,5−ジカフェオイルキナ酸のジカフェオイルキナ酸を併せての総称であり、本発明においては上記9種のうち少なくとも1種を含有すればよい。なお、クロロゲン酸類の含有量は上記9種の合計量に基づいて定義される。 The chlorogenic acid content in the aqueous solution in which the raw material chlorogenic acid-containing composition is dissolved can be appropriately selected, but from the viewpoint of purification efficiency, 0.1% by mass or more is preferable, 0.5% by mass or more is more preferable, 1 mass% or more is still more preferable, 20 mass% or less is preferable, 10 mass% or less is more preferable, and 5 mass% or less is still more preferable. The range of the content of such chlorogenic acids is preferably 0.1 to 20% by mass, more preferably 0.5 to 20% by mass, still more preferably 0.5 to 10% by mass, and still more preferably 1 to 5%. % By mass. Here, “chlorogenic acids” in the present specification means 3-caffeoylquinic acid, 4-caffeoylquinic acid and monocaffeoylquinic acid of 5-caffeoylquinic acid, 3-ferlaquinic acid and 4-ferlaquina. Acid and 5-ferlaquinic acid monoferlaquinic acid and 3,4-dicaffeoylquinic acid, 3,5-dicaffeoylquinic acid and 4,5-dicaffeoylquinic acid dicaffeoylquinic acid In the present invention, at least one of the above nine types may be contained. The content of chlorogenic acids is defined based on the total amount of the nine types.
陽イオン交換樹脂としては、強酸性陽イオン交換樹脂及び弱酸性陽イオン交換樹脂のいずれも用いることができる。陽イオン交換樹脂の樹脂母体としては、例えば、スチレン系樹脂、アクリル酸系樹脂、メタクリル酸系樹脂等が挙げられる。中でも、スチレン系樹脂が好ましく、スチレン−ジビニルベンゼン共重合体が更に好ましい。また、陽イオン交換樹脂の樹脂構造としては、例えば、ゲル型、ポーラス型が挙げられる。ここで、本明細書において「ゲル型」とは、膨潤によって生じる細孔であるミクロポアのみを有するものをいい、また「ポーラス型」とは、ミクロポアの他に、乾燥状態でも消滅しない物理的細孔であるマクロポアを有するものをいう。陽イオン交換樹脂の官能基としては、例えば、スルホン酸基、カルボキシル基、リン酸基等が挙げられ、中でも、スルホン酸基が好ましい。 As the cation exchange resin, both strong acid cation exchange resins and weak acid cation exchange resins can be used. Examples of the resin matrix of the cation exchange resin include a styrene resin, an acrylic acid resin, and a methacrylic acid resin. Of these, styrene resins are preferable, and styrene-divinylbenzene copolymers are more preferable. Examples of the resin structure of the cation exchange resin include a gel type and a porous type. As used herein, the term “gel type” refers to those having only micropores that are pores generated by swelling, and the “porous type” refers to physical fines that do not disappear even in a dry state in addition to micropores. It has a macropore which is a hole. Examples of the functional group of the cation exchange resin include a sulfonic acid group, a carboxyl group, and a phosphoric acid group. Among them, a sulfonic acid group is preferable.
このような陽イオン交換樹脂として市販品を使用してもよく、強酸性陽イオン交換樹脂としては、例えば、ダイヤイオンSK1B、SK1BH、SK102、SK116、PK208、PK212(三菱化学社製)、アンバーライト200CT、IR118、IR120B、IR124(ダウ・ケミカル社製)等を挙げることができる。また、弱酸性陽イオン交換樹脂としては、例えば、ダイヤイオンWK10、WK40L(三菱化学社製)、アンバーライトIRC76(ダウ・ケミカル社製)等が挙げられる。 Commercially available products may be used as such cation exchange resins. Examples of strongly acidic cation exchange resins include Diaion SK1B, SK1BH, SK102, SK116, PK208, PK212 (Mitsubishi Chemical Corporation), Amberlite. 200CT, IR118, IR120B, IR124 (manufactured by Dow Chemical Company) and the like can be mentioned. Examples of the weakly acidic cation exchange resin include Diaion WK10, WK40L (manufactured by Mitsubishi Chemical Corporation), Amberlite IRC76 (manufactured by Dow Chemical Company), and the like.
中でも、本工程で用いる陽イオン交換樹脂としては、夾雑物の除去の点から、強酸性陽イオン交換樹脂が好ましく、H型陽イオン交換樹脂が更に好ましい。H型陽イオン交換樹脂としては、Na型の陽イオン交換樹脂をH型に置換した陽イオン交換樹脂が挙げられ、市販品として、例えば、ダイヤイオンSK1BHを挙げることができる。なお、陽イオン交換樹脂は、予め水で洗浄し、陽イオン交換樹脂の原料モノマーや原料モノマー中の不純物を除去しておくことが好ましい。 Especially, as a cation exchange resin used at this process, a strong acidic cation exchange resin is preferable and the H-type cation exchange resin is still more preferable from the point of removal of a foreign material. Examples of the H-type cation exchange resin include a cation exchange resin obtained by substituting an Na-type cation exchange resin with an H-type, and examples of commercially available products include Diaion SK1BH. The cation exchange resin is preferably washed with water in advance to remove the cation exchange resin raw material monomer and impurities in the raw material monomer.
陽イオン交換樹脂との接触方法としては、バッチ式でもカラム式でもよいが、精製効率の点から、カラム式が好ましい。カラム式の場合、陽イオン交換樹脂を充填したカラムに、原料クロロゲン酸類含有組成物を溶解させた水溶液を通液すればよい。 The contact method with the cation exchange resin may be a batch method or a column method, but the column method is preferred from the viewpoint of purification efficiency. In the case of the column type, an aqueous solution in which the raw material chlorogenic acid-containing composition is dissolved may be passed through a column filled with a cation exchange resin.
カラム式で接触させる場合、原料クロロゲン酸類含有組成物の通液速度は適宜選択することが可能であるが、空間速度(SV)として、0.1[hr-1]以上が好ましく、0.2[hr-1]以上がより好ましく、0.5[hr-1]以上が更に好ましく、そして50[hr-1]以下が好ましく、10[hr-1]以下がより好ましく、8[hr-1]以下が更に好ましく、5[hr-1]以下がより更に好ましい。かかる空間速度(SV)の範囲としては、好ましくは0.1〜50[hr-1]、より好ましくは0.1〜10[hr-1]、更に好ましくは0.2〜8[hr-1]、より更に好ましくは0.5〜5[hr-1]である。
また、原料クロロゲン酸類含有組成物の通液量も適宜選択可能であるが、陽イオン交換樹脂の充填容量に対する通液倍数(BV)として、0.5(mL/mL)以上が好ましく、1(mL/mL)以上がより好ましく、5(mL/mL)以上が更に好ましく、10(mL/mL)以上がより更に好ましく、そして100(mL/mL)以下が好ましく、80(mL/mL)以下がより好ましく、60(mL/mL)以下が更に好ましく、40(mL/mL)以下がより更に好ましい。かかる通液倍数の範囲としては、好ましくは0.5〜100(mL/mL)、より好ましくは1〜80(mL/mL)、更に好ましくは5〜60(mL/mL)、より更に好ましくは10〜40(mL/mL)である。
In the case of contacting by a column type, the liquid flow rate of the raw material chlorogenic acid-containing composition can be appropriately selected, but the space velocity (SV) is preferably 0.1 [hr −1 ] or more, 0.2 [Hr -1 ] or more is more preferable, 0.5 [hr -1 ] or more is more preferable, 50 [hr -1 ] or less is preferable, 10 [hr -1 ] or less is more preferable, and 8 [hr -1 ] is more preferable. The following is more preferable, and 5 [hr −1 ] or less is more preferable. The scope of such a space velocity (SV), preferably 0.1~50 [hr -1], and more preferably 0.1~10 [hr -1], and more preferably 0.2 to 8 [hr -1 ], More preferably, it is 0.5-5 [hr < -1 >].
In addition, the flow rate of the raw material chlorogenic acid-containing composition can be appropriately selected, but the flow rate multiple (BV) with respect to the filling capacity of the cation exchange resin is preferably 0.5 (mL / mL) or more. more preferably 5 (mL / mL) or more, more preferably 10 (mL / mL) or more, and more preferably 100 (mL / mL) or less, and 80 (mL / mL) or less. Is more preferable, 60 (mL / mL) or less is still more preferable, and 40 (mL / mL) or less is still more preferable. As a range of such liquid passing multiples, preferably 0.5 to 100 (mL / mL), more preferably 1 to 80 (mL / mL), still more preferably 5 to 60 (mL / mL), and still more preferably. 10 to 40 (mL / mL).
また、バッチ式で接触させる場合、陽イオン交換樹脂1質量部に対する原料クロロゲン酸類含有組成物の使用量は、原料クロロゲン酸類含有組成物の固形分質量として、好ましくは0.021〜4.3質量部、より好ましくは0.042〜3.5質量部、更に好ましくは0.21〜2.6質量部、より更に好ましくは0.42〜1.8質量部である。 Moreover, when making it contact in a batch type, the usage-amount of the raw material chlorogenic acid containing composition with respect to 1 mass part of cation exchange resins, as a solid content mass of a raw material chlorogenic acid containing composition, Preferably it is 0.021-4.3 mass. Parts, more preferably 0.042 to 3.5 parts by mass, still more preferably 0.21 to 2.6 parts by mass, and still more preferably 0.42 to 1.8 parts by mass.
工程Aにより得られた液のpH(20℃)は、カフェインの低減、精製クロロゲン酸類含有組成物の収率、クロロゲン酸類の純度の観点から、4未満が好ましく、3.5以下がより好ましく、3以下が更に好ましく、そして0.5以上が好ましく、1以上が更に好ましい。当該液のpHの範囲としては、好ましくは0.5以上4未満、より好ましくは0.5以上3.5以下、更に好ましくは1以上3以下である。ここで、本明細書において「工程Aにより得られた液」とは、バッチ式の場合は原料クロロゲン酸類含有組成物を陽イオン交換樹脂と接触させた後の液であり、カラム式の場合は陽イオン交換樹脂を充填したカラムに原料クロロゲン酸類含有組成物を通液して得られる液である。 The pH (20 ° C.) of the liquid obtained in step A is preferably less than 4 and more preferably 3.5 or less from the viewpoints of caffeine reduction, the yield of the purified chlorogenic acid-containing composition, and the purity of chlorogenic acids. 3 or less is more preferable, 0.5 or more is preferable, and 1 or more is more preferable. The pH range of the liquid is preferably 0.5 or more and less than 4, more preferably 0.5 or more and 3.5 or less, and still more preferably 1 or more and 3 or less. Here, in the present specification, the “liquid obtained by step A” is a liquid after the raw material chlorogenic acid-containing composition is brought into contact with a cation exchange resin in the case of a batch type, and in the case of a column type. This is a liquid obtained by passing a raw material chlorogenic acid-containing composition through a column filled with a cation exchange resin.
(工程B)
本発明に係る工程Bは、工程Aにより得られた液を弱塩基性陰イオン交換樹脂に接触させる工程である。これにより、クロロゲン酸類の純度及び収率を高めることができる。
(Process B)
Step B according to the present invention is a step of bringing the liquid obtained in Step A into contact with a weakly basic anion exchange resin. Thereby, the purity and yield of chlorogenic acids can be increased.
弱塩基性陰イオン交換樹脂の樹脂母体としては、例えば、スチレン系樹脂、アクリル酸系樹脂、メタクリル酸系樹脂が挙げられ、中でも、アクリル酸系樹脂が好ましい。弱塩基性陰イオン交換樹脂の樹脂構造としては、例えば、ゲル型、ポーラス型が挙げられる。弱塩基性陰イオン交換樹脂の官能基としては、例えば、一級アミノ基、二級アミノ基、三級アミノ基等を挙げることができる。一級アミノ基としては、例えばメチルアミノ基等が挙げられ、二級アミノ基としては、例えばジメチルアミノ基等が挙げられ、三級アミノ基としては、例えばジメチルアミノメチル基等が挙げられる。
このような弱塩基性陰イオン交換樹脂として市販品を使用してもよく、例えば、ダイヤイオンWA10、WA20、WA21J、WA30(三菱化学社製)、アンバーライトIRA67、IRA743、IRA96SB、XE583、XT6050RF(ダウ・ケミカル社製)等が挙げられる。なお、弱塩基性陰イオン交換樹脂は、予め水で洗浄し、吸着剤の原料モノマーや原料モノマー中の不純物を除去しておくことが好ましい。
Examples of the resin base of the weakly basic anion exchange resin include styrene resins, acrylic resins, and methacrylic resins, and among them, acrylic resins are preferable. Examples of the resin structure of the weakly basic anion exchange resin include a gel type and a porous type. Examples of the functional group of the weakly basic anion exchange resin include a primary amino group, a secondary amino group, and a tertiary amino group. Examples of the primary amino group include a methylamino group. Examples of the secondary amino group include a dimethylamino group. Examples of the tertiary amino group include a dimethylaminomethyl group.
Commercially available products may be used as such a weakly basic anion exchange resin. For example, Diaion WA10, WA20, WA21J, WA30 (manufactured by Mitsubishi Chemical Corporation), Amberlite IRA67, IRA743, IRA96SB, XE583, XT6050RF ( Dow Chemical Co.). The weakly basic anion exchange resin is preferably washed with water in advance to remove the raw material monomer of the adsorbent and impurities in the raw material monomer.
弱塩基性陰イオン交換樹脂との接触方法は、バッチ式でもカラム式でもよいが、精製効率の点から、カラム式が好ましい。カラム式の場合には、弱塩基性陰イオン交換樹脂を充填したカラムに、工程Aにより得られた液を通液すればよい。 The contact method with the weakly basic anion exchange resin may be a batch method or a column method, but the column method is preferable from the viewpoint of purification efficiency. In the case of the column type, the liquid obtained in step A may be passed through a column filled with a weakly basic anion exchange resin.
また、カラム式で行う場合、陽イオン交換樹脂を充填したカラムと、弱塩基性陰イオン交換樹脂を充填したカラムを連結し、工程Aと工程Bを連続して行ってもよい。 Moreover, when performing by a column type, the column filled with the cation exchange resin and the column filled with the weak basic anion exchange resin may be connected, and the process A and the process B may be performed continuously.
カラム式で行う場合、工程Aにより得られた液の通液速度は、空間速度(SV)として、0.1[hr-1]以上が好ましく、0.2[hr-1]以上がより好ましく、0.5[hr-1]が更に好ましく、そして50[hr-1]以下が好ましく、10[hr-1]以下がより好ましく、8[hr-1]以下が更に好ましく、5[hr-1]以下がより更に好ましい。かかる空間速度(SV)の範囲としては、好ましくは0.1〜50[hr-1]、より好ましくは0.1〜10[hr-1]、更に好ましくは0.2〜8[hr-1]、より更に好ましくは0.5〜5[hr-1]である。
また、工程Aにより得られた液の通液量は、弱塩基性陰イオン交換樹脂の充填容量に対する通液倍数(BV)として、0.5(mL/mL)以上が好ましく、1(mL/mL)以上がより好ましく、5(mL/mL)以上が更に好ましく、10(mL/mL)以上がより更に好ましく、そして100(mL/mL)以下が好ましく、60(mL/mL)以下がより好ましく、45(mL/mL)以下が更に好ましく、30(mL/mL)以下がより更に好ましい。かかる通液倍数の範囲としては、好ましくは0.5〜100(mL/mL)、より好ましくは1〜60(mL/mL)、更に好ましくは5〜45(mL/mL)、より更に好ましくは10〜30(mL/mL)である。
When the column method is used, the flow rate of the liquid obtained in step A is preferably 0.1 [hr −1 ] or more, more preferably 0.2 [hr −1 ] or more as the space velocity (SV). 0.5 [hr −1 ], more preferably 50 [hr −1 ] or less, more preferably 10 [hr −1 ] or less, further preferably 8 [hr −1 ] or less, 5 [hr − 1 ] The following is more preferable. The scope of such a space velocity (SV), preferably 0.1~50 [hr -1], and more preferably 0.1~10 [hr -1], and more preferably 0.2 to 8 [hr -1 ], More preferably, it is 0.5-5 [hr < -1 >].
Further, the flow rate of the liquid obtained in the step A is preferably 0.5 (mL / mL) or more as a flow rate multiple (BV) with respect to the filling capacity of the weakly basic anion exchange resin, and preferably 1 (mL / mL). mL (mL / mL) or more, more preferably 5 (mL / mL) or more, still more preferably 10 (mL / mL) or more, and preferably 100 (mL / mL) or less, more preferably 60 (mL / mL) or less. Preferably, 45 (mL / mL) or less is more preferable, and 30 (mL / mL) or less is still more preferable. As a range of such liquid passing multiples, preferably 0.5 to 100 (mL / mL), more preferably 1 to 60 (mL / mL), still more preferably 5 to 45 (mL / mL), and still more preferably. 10-30 (mL / mL).
また、バッチ式で接触させる場合、弱塩基性陰イオン交換樹脂に対する工程Aにより得られた液の使用量は適宜選択することが可能であるが、例えば、弱塩基性陰イオン交換樹脂1質量部に対する工程Aにより得られた液の使用量は、好ましくは0.82〜160質量部、より好ましくは1.6〜98質量部、更に好ましくは8.2〜74質量部、より更に好ましくは16〜50質量部である。 Moreover, when making it contact by a batch type, although the usage-amount of the liquid obtained by the process A with respect to weak basic anion exchange resin can be selected suitably, for example, 1 mass part of weak basic anion exchange resin The amount of the liquid obtained by the process A is preferably 0.82 to 160 parts by mass, more preferably 1.6 to 98 parts by mass, still more preferably 8.2 to 74 parts by mass, and still more preferably 16 -50 mass parts.
(工程C)
本発明に係る工程Cは、工程B後の弱塩基性陰イオン交換樹脂に35℃以上の水を接触させる工程である。弱塩基性陰イオン交換樹脂を35℃以上の水で洗浄することにより、水で洗浄しない場合、あるいは25℃程度の水で洗浄する場合に比して、カフェインをより一層低減することができる。
(Process C)
Step C according to the present invention is a step of bringing water at 35 ° C. or higher into contact with the weakly basic anion exchange resin after Step B. By washing the weakly basic anion exchange resin with water of 35 ° C. or higher, caffeine can be further reduced as compared with the case of not washing with water or washing with water of about 25 ° C. .
洗浄に使用する水としては、例えば、水道水、蒸留水、イオン交換水、天然水等を適宜選択することができる。
水の温度は35℃以上であるが、40℃以上が好ましく、45℃以上がより好ましく、55℃以上が更に好ましく、65℃以上がより更に好ましく、70℃以上が殊更に好ましく、そして100℃以下が好ましく、99℃以下がより好ましく、98℃以下が更に好ましく、97℃以下がより更に好ましい。かかる水の温度の範囲としては、好ましくは40〜100℃、より好ましくは45〜100℃、更に好ましくは55〜99℃、より更に好ましくは65〜98℃、殊更に好ましくは70〜97℃である。
As water used for washing, for example, tap water, distilled water, ion-exchanged water, natural water and the like can be appropriately selected.
The temperature of the water is 35 ° C or higher, preferably 40 ° C or higher, more preferably 45 ° C or higher, still more preferably 55 ° C or higher, still more preferably 65 ° C or higher, even more preferably 70 ° C or higher, and 100 ° C. The following is preferable, 99 ° C. or lower is more preferable, 98 ° C. or lower is further preferable, and 97 ° C. or lower is still more preferable. The temperature range of such water is preferably 40 to 100 ° C, more preferably 45 to 100 ° C, still more preferably 55 to 99 ° C, still more preferably 65 to 98 ° C, and even more preferably 70 to 97 ° C. is there.
工程Cをカラム式で行った場合、水の通液速度は、空間速度(SV)として、0.5[hr-1]以上が好ましく、1[hr-1]以上がより好ましく、2[hr-1]が更に好ましく、そして50[hr-1]以下が好ましく、30[hr-1]以下がより好ましく、20[hr-1]以下が更に好ましく、10[hr-1]以下がより更に好ましい。かかる空間速度(SV)の範囲としては、好ましくは0.5〜50[hr-1]、より好ましくは1〜30[hr-1]、更に好ましくは2〜20[hr-1]、より更に好ましくは2〜10[hr-1]である。
また、水の通液量は、弱塩基性陰イオン交換樹脂の充填容量に対する通液倍数(BV)として、0.5(mL/mL)以上が好ましく、1(mL/mL)以上がより好ましく、5(mL/mL)以上が更に好ましく、10(mL/mL)以上がより更に好ましく、そして100(mL/mL)以下が好ましく、60(mL/mL)以下がより好ましく、45(mL/mL)以下が更に好ましく、30(mL/mL)以下がより更に好ましい。かかる通液倍数の範囲としては、好ましくは0.5〜100(mL/mL)、より好ましくは1〜60(mL/mL)、更に好ましくは5〜45(mL/mL)、より更に好ましくは10〜30(mL/mL)である。
When Step C is performed by a column system, the water flow rate is preferably 0.5 [hr −1 ] or more, more preferably 1 [hr −1 ] or more, as the space velocity (SV), 2 [hr]. -1 ] is more preferred, and 50 [hr -1 ] or less is preferred, 30 [hr -1 ] or less is more preferred, 20 [hr -1 ] or less is more preferred, and 10 [hr -1 ] or less is even more preferred. preferable. The range of the space velocity (SV) is preferably 0.5 to 50 [hr −1 ], more preferably 1 to 30 [hr −1 ], still more preferably 2 to 20 [hr −1 ], and still more. Preferably it is 2-10 [hr < -1 >].
In addition, the water flow rate is preferably 0.5 (mL / mL) or more, more preferably 1 (mL / mL) or more, as the flow rate (BV) with respect to the filling capacity of the weakly basic anion exchange resin. 5 (mL / mL) or more is more preferable, 10 (mL / mL) or more is more preferable, 100 (mL / mL) or less is preferable, 60 (mL / mL) or less is more preferable, 45 (mL / mL) mL) or less, more preferably 30 (mL / mL) or less. As a range of such liquid passing multiples, preferably 0.5 to 100 (mL / mL), more preferably 1 to 60 (mL / mL), still more preferably 5 to 45 (mL / mL), and still more preferably. 10-30 (mL / mL).
また、バッチ式で洗浄する場合、水の使用量は適宜選択することが可能であるが、弱塩基性陰イオン交換樹脂1質量部に対する水の使用量は、好ましくは0.82〜160質量部、より好ましくは1.6〜98質量部、更に好ましくは8.2〜74質量部、より更に好ましくは16〜50質量部である。 In the case of washing with a batch method, the amount of water used can be appropriately selected. The amount of water used is preferably 0.82 to 160 parts by mass with respect to 1 part by mass of the weakly basic anion exchange resin. More preferably, it is 1.6-98 mass parts, More preferably, it is 8.2-74 mass parts, More preferably, it is 16-50 mass parts.
(工程D)
本発明に係る工程Dは、工程C後の弱塩基性陰イオン交換樹脂に酸水溶液又はアルカリ水溶液を接触させる工程である。工程Dにより、クロロゲン酸類を含む脱離液として、本発明の精製クロロゲン酸類含有組成物を得ることができる。
(Process D)
The process D according to the present invention is a process in which the weakly basic anion exchange resin after the process C is brought into contact with an acid aqueous solution or an alkali aqueous solution. By the process D, the purified chlorogenic acid-containing composition of the present invention can be obtained as a detachment liquid containing chlorogenic acids.
本工程に用いる酸水溶液は、酸を水に溶解して調製したものを適宜使用することが可能である。酸としては、有機酸でも無機酸でもよく、それらの塩であってよい。塩としては、例えば、アルカリ金属塩が挙げられ、その具体例として、カリウム塩、ナトリウム塩等を挙げることができる。酸は、1種又は2種以上を適宜選択することが可能であり、また酸性水溶液を調製する際に使用する水は、例えば、水道水、蒸留水、イオン交換水、天然水等を適宜選択することができる。
有機酸は、一塩基酸でも、多塩基酸でもよく、例えば、ギ酸、酢酸、プロピオン酸、酪酸、吉草酸、シュウ酸、マロン酸、フマル酸、イタコン酸、フタル酸、イソフタル酸、テレフタル酸、グルタミン酸、アスパラギン酸、グリコール酸、リンゴ酸、ピルビン酸、酒石酸、クエン酸、乳酸、コハク酸、マレイン酸、グルタル酸、コウジ酸、ジピコリン酸、アコニット酸、レブリン酸、ヒドロキシアクリル酸、α−オキシ酪酸、グリセリン酸、タルトロン酸、サリチル酸、没食子酸、トロパ酸、アスコルビン酸、グルコン酸等を挙げることができる。また、無機酸としては、例えば、塩酸、リン酸、硫酸、亜硫酸、スルファミン酸等を挙げることができる。中でも、酸としては、pH調整の容易さ、クロロゲン酸類の純度及び収率、食品への使用等の観点から、塩酸が好ましい。
As the acid aqueous solution used in this step, one prepared by dissolving an acid in water can be appropriately used. The acid may be an organic acid or an inorganic acid, or a salt thereof. Examples of the salt include alkali metal salts, and specific examples thereof include potassium salts and sodium salts. One or more acids can be selected as appropriate, and the water used when preparing the acidic aqueous solution is, for example, tap water, distilled water, ion-exchanged water, natural water, etc. can do.
The organic acid may be a monobasic acid or a polybasic acid, such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, oxalic acid, malonic acid, fumaric acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, Glutamic acid, aspartic acid, glycolic acid, malic acid, pyruvic acid, tartaric acid, citric acid, lactic acid, succinic acid, maleic acid, glutaric acid, kojic acid, dipicolinic acid, aconitic acid, levulinic acid, hydroxyacrylic acid, α-oxybutyric acid Glyceric acid, tartronic acid, salicylic acid, gallic acid, tropic acid, ascorbic acid, gluconic acid and the like. Examples of inorganic acids include hydrochloric acid, phosphoric acid, sulfuric acid, sulfurous acid, sulfamic acid, and the like. Among these, hydrochloric acid is preferable as the acid from the viewpoints of ease of pH adjustment, purity and yield of chlorogenic acids, use in foods, and the like.
酸水溶液の濃度は、クロロゲン酸類の純度及び収率の観点から、0.5質量%以上が好ましく、1質量%以上がより好ましく、そして15質量%以下が好ましく、10質量%以下がより好ましく、5質量%以下が更に好ましい。かかる酸水溶液の濃度範囲としては、好ましくは0.5〜15質量%、より好ましくは1〜10質量%、更に好ましくは1〜5質量%である。
酸水溶液のpH(20℃)は、強酸性であることが好ましく、より具体的には、4以下が好ましく、3以下が更に好ましく、そして0.5以上が好ましい。かかるpHの範囲としては、好ましくは0.5〜4、更に好ましくは0.5〜3である。
The concentration of the acid aqueous solution is preferably 0.5% by mass or more, more preferably 1% by mass or more, and preferably 15% by mass or less, more preferably 10% by mass or less, from the viewpoints of purity and yield of chlorogenic acids. 5 mass% or less is still more preferable. The concentration range of the acid aqueous solution is preferably 0.5 to 15% by mass, more preferably 1 to 10% by mass, and further preferably 1 to 5% by mass.
The pH (20 ° C.) of the aqueous acid solution is preferably strongly acidic, more specifically, preferably 4 or less, more preferably 3 or less, and preferably 0.5 or more. The pH range is preferably 0.5-4, more preferably 0.5-3.
また、本工程に用いるアルカリ水溶液は、アルカリを水に溶解して調製したものを適宜使用することが可能である。アルカリとしては、例えば、水酸化ナトリウム、水酸化カリウム等のアルカリ金属の水酸化物、水酸化マグネシウム、水酸化カルシウム、水酸化バリウム等のアルカリ土類金属の水酸化物、炭酸ナトリウム、炭酸カリウム等のアルカリ金属の炭酸塩、炭酸マグネシウム、炭酸カルシウム、炭酸バリウム等のアルカリ土類金属の炭酸塩、炭酸水素ナトリウム、炭酸水素カリウム等のアルカリ金属の炭酸水素塩、炭酸水素マグネシウム、炭酸水素カルシウム、炭酸水素バリウム等のアルカリ土類金属の炭酸水素塩、炭酸アンモニウム、炭酸水素アンモニウム、アンモニア、水酸化テトラアルキルアンモニウム、ヒドラジン等を挙げることができる。なお、アルカリは、1種又は2種以上組わせて用いることが可能である。中でも、アルカリとしては、pH調整の容易さ、クロロゲン酸類の純度及び収率の観点から、アルカリ金属の水酸化物が好ましく、水酸化ナトリウムが更に好ましい。なお、アルカリ水溶液を調製する際に使用する水は、例えば、水道水、蒸留水、イオン交換水、天然水等を適宜選択することができる。 Moreover, the aqueous alkali solution used for this process can use suitably what prepared by melt | dissolving an alkali in water. Examples of the alkali include hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide, hydroxides of alkaline earth metals such as magnesium hydroxide, calcium hydroxide and barium hydroxide, sodium carbonate and potassium carbonate. Alkali metal carbonates, Magnesium carbonate, Calcium carbonate, Barium carbonate and other alkaline earth metal carbonates, Sodium bicarbonate, Potassium bicarbonate alkali metal bicarbonates, Magnesium bicarbonate, Calcium bicarbonate, Carbonate Examples include alkaline earth metal hydrogen carbonates such as barium hydrogen, ammonium carbonate, ammonium hydrogen carbonate, ammonia, tetraalkylammonium hydroxide, and hydrazine. In addition, an alkali can be used 1 type or in combination of 2 or more types. Among these, alkali is preferably an alkali metal hydroxide, more preferably sodium hydroxide, from the viewpoints of ease of pH adjustment, purity and yield of chlorogenic acids. In addition, the water used when preparing alkaline aqueous solution can select suitably tap water, distilled water, ion-exchange water, natural water etc., for example.
アルカリ水溶液の濃度は、クロロゲン酸類の純度及び収率の観点から、0.1質量%以上が好ましく、0.3質量%以上がより好ましく、そして5質量%以下が好ましく、3質量%以下が更に好ましい。かかるアルカリ水溶液の濃度範囲としては、好ましくは0.1〜5質量%、更に好ましくは0.2〜3質量%である。
アルカリ水溶液のpH(20℃)は、10以上が好ましく、11以上が更に好ましく、そして13.5以下が好ましく、13以下が更に好ましい。かかるpHの範囲としては、好ましくは10〜13.5、更に好ましくは11〜13である。
The concentration of the alkaline aqueous solution is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and preferably 5% by mass or less, and more preferably 3% by mass or less, from the viewpoints of purity and yield of chlorogenic acids. preferable. The concentration range of the alkaline aqueous solution is preferably 0.1 to 5% by mass, and more preferably 0.2 to 3% by mass.
The pH (20 ° C.) of the alkaline aqueous solution is preferably 10 or more, more preferably 11 or more, and preferably 13.5 or less, more preferably 13 or less. The pH range is preferably 10 to 13.5, and more preferably 11 to 13.
工程Dをカラム式で行った場合、酸水溶液又はアルカリ水溶液の通液速度は、空間速度(SV)として、0.5[hr-1]以上が好ましく、1[hr-1]以上がより好ましく、2[hr-1]が更に好ましく、そして50[hr-1]以下が好ましく、30[hr-1]以下がより好ましく、20[hr-1]以下が更に好ましく、10[hr-1]以下がより更に好ましい。かかる空間速度(SV)の範囲としては、好ましくは0.5〜50[hr-1]、より好ましくは1〜30[hr-1]、更に好ましくは2〜20[hr-1]、より更に好ましくは2〜10[hr-1]である。
また、酸水溶液又はアルカリ水溶液の通液量は、弱塩基性陰イオン交換樹脂に対する通液倍数(BV)として、0.5(mL/mL)以上が好ましく、1(mL/mL)以上がより好ましく、5(mL/mL)以上が更に好ましく、10(mL/mL)以上がより更に好ましく、そして100(mL/mL)以下が好ましく、70(mL/mL)以下がより好ましく、50(mL/mL)以下が更に好ましく、40(mL/mL)以下がより更に好ましい。かかる通液倍数の範囲としては、好ましくは0.5〜100(mL/mL)、より好ましくは1〜70(mL/mL)、更に好ましくは5〜50(mL/mL)、より更に好ましくは10〜40(mL/mL)である。
When Step D is performed by a column system, the flow rate of the aqueous acid solution or aqueous alkali solution is preferably 0.5 [hr −1 ] or more, more preferably 1 [hr −1 ] or more, as the space velocity (SV). 2 [hr -1 ] is more preferred, and 50 [hr -1 ] or less is preferred, 30 [hr -1 ] or less is more preferred, 20 [hr -1 ] or less is more preferred, and 10 [hr -1 ] is preferred. The following is even more preferable. The range of the space velocity (SV) is preferably 0.5 to 50 [hr −1 ], more preferably 1 to 30 [hr −1 ], still more preferably 2 to 20 [hr −1 ], and still more. Preferably it is 2-10 [hr < -1 >].
In addition, the passing amount of the aqueous acid solution or aqueous alkali solution is preferably 0.5 (mL / mL) or more, more preferably 1 (mL / mL) or more, as the passing ratio (BV) to the weakly basic anion exchange resin. Preferably, 5 (mL / mL) or more is more preferable, 10 (mL / mL) or more is more preferable, 100 (mL / mL) or less is preferable, 70 (mL / mL) or less is more preferable, 50 (mL / ML) or less, more preferably 40 (mL / mL) or less. As a range of such a flow rate multiple, it becomes like this. Preferably it is 0.5-100 (mL / mL), More preferably, it is 1-70 (mL / mL), More preferably, it is 5-50 (mL / mL), More preferably 10 to 40 (mL / mL).
また、バッチ式で接触させる場合には、弱塩基性陽イオン交換樹脂1質量部に対する酸水溶液又はアルカリ水溶液の使用量は、好ましくは0.82〜160質量部、より好ましくは1.6〜110質量部、更に好ましくは8.2〜82質量部、より更に好ましくは16〜65質量部である。 Moreover, when making it contact in a batch type, the usage-amount of the acid aqueous solution or alkali aqueous solution with respect to 1 mass part of weak basic cation exchange resins becomes like this. Preferably it is 0.82-160 mass part, More preferably, it is 1.6-110. It is a mass part, More preferably, it is 8.2-82 mass part, More preferably, it is 16-65 mass part.
工程D後、精製クロロゲン酸類含有組成物の安定性の観点から、得られた精製クロロゲン酸類含有組成物のpHを調整してもよい。pH調整方法としては、例えば、
1)酸、又はアルカリによる調整、
2)電気透析によるアルカリ金属イオン、又は酸の除去、
3)陽イオン交換樹脂によるアルカリ金属イオンの除去、
4)減圧濃縮による酸の留去
等を挙げることができる。中でも、工程Dにおいて脱離液としてアルカリ水溶液を使用した場合には、プロセスの簡便性から、陽イオン交換樹脂により調整することが好ましい。陽イオン交換樹脂としては、工程Aと同様のものを用いることができる。一方、工程Dにおいて脱離液として酸性水溶液を使用した場合には、プロセスの簡便性から、減圧濃縮による酸の留去が好ましい。なお、pH調整後の精製クロロゲン酸類含有組成物のpH(20℃)は2以上が好ましく、そして7以下が好ましく、5以下がより好ましく、4以下が更に好ましい。かかるpHの範囲としては、好ましくは2〜7、より好ましくは2〜5、更に好ましくは2〜4である。
After Step D, the pH of the obtained purified chlorogenic acid-containing composition may be adjusted from the viewpoint of the stability of the purified chlorogenic acid-containing composition. As a pH adjustment method, for example,
1) Adjustment with acid or alkali,
2) Removal of alkali metal ions or acid by electrodialysis,
3) Removal of alkali metal ions by cation exchange resin
4) The acid can be distilled off by concentration under reduced pressure. Among these, when an alkaline aqueous solution is used as the desorbing liquid in Step D, it is preferable to adjust with a cation exchange resin from the simplicity of the process. As the cation exchange resin, the same cation exchange resin as in step A can be used. On the other hand, when an acidic aqueous solution is used as the desorbing liquid in the step D, it is preferable to distill off the acid by concentration under reduced pressure for the convenience of the process. The pH (20 ° C.) of the purified chlorogenic acid-containing composition after pH adjustment is preferably 2 or more, preferably 7 or less, more preferably 5 or less, and still more preferably 4 or less. The pH range is preferably 2 to 7, more preferably 2 to 5, and still more preferably 2 to 4.
本発明の製造方法により得られた精製クロロゲン酸類含有組成物は、下記の特性(i)〜(v)を具備することができる。
(i)精製クロロゲン酸類含有組成物は、原料クロロゲン酸類含有組成物を基準として、クロロゲン酸類を、好ましくは80質量%以上、より好ましくは85質量%以上、更に好ましくは90質量%以上の収率で回収することができる。
(ii)精製クロロゲン酸類含有組成物は、該精製クロロゲン酸類含有組成物中のクロロゲン酸類の純度が、好ましくは60質量%以上、より好ましくは65質量%以上、更に好ましくは70質量%以上である。
(iii)精製クロロゲン酸類含有組成物は、カフェインの含有量が、該精製クロロゲン酸類含有組成物の固形分中に、好ましくは1.8質量%以下、より好ましくは1.5質量%以下、更に好ましくは1.2質量%以下である。なお、かかるカフェインの含有量は、精製クロロゲン酸類含有組成物中の固形分中に、0質量%であってもよいが、生産効率の観点から、0.01質量%以上が好ましい。
(iv)精製クロロゲン酸類含有組成物は、クロロゲン酸類の含有量が、該精製クロロゲン酸類含有組成物の固形分中に、好ましくは60質量%以上、より好ましくは65質量%以上、更に好ましくは70質量%以上である
(v)精製クロロゲン酸類含有組成物は、カフェイン/クロロゲン酸類の質量比が、好ましくは0.03以下、より好ましくは0.025以下、更に好ましくは0.02以下である。なお、カフェイン/クロロゲン酸類の質量比は0であってもよいが、生産効率の観点から、0.0001以上が好ましい。
The purified chlorogenic acid-containing composition obtained by the production method of the present invention can have the following characteristics (i) to (v).
(I) The purified chlorogenic acid-containing composition is based on the raw material chlorogenic acid-containing composition, and the yield of chlorogenic acids is preferably 80% by mass or more, more preferably 85% by mass or more, and still more preferably 90% by mass or more. Can be recovered.
(Ii) In the purified chlorogenic acid-containing composition, the purity of the chlorogenic acids in the purified chlorogenic acid-containing composition is preferably 60% by mass or more, more preferably 65% by mass or more, and further preferably 70% by mass or more. .
(Iii) In the purified chlorogenic acid-containing composition, the content of caffeine is preferably 1.8% by mass or less, more preferably 1.5% by mass or less, in the solid content of the purified chlorogenic acid-containing composition. More preferably, it is 1.2 mass% or less. The content of caffeine may be 0% by mass in the solid content of the purified chlorogenic acid-containing composition, but is preferably 0.01% by mass or more from the viewpoint of production efficiency.
(Iv) In the purified chlorogenic acid-containing composition, the content of chlorogenic acid is preferably 60% by mass or more, more preferably 65% by mass or more, and still more preferably 70% in the solid content of the purified chlorogenic acid-containing composition. The mass ratio of caffeine / chlorogenic acids in the composition containing (v) purified chlorogenic acids that is at least% by mass is preferably 0.03 or less, more preferably 0.025 or less, still more preferably 0.02 or less. . The mass ratio of caffeine / chlorogenic acids may be 0, but is preferably 0.0001 or more from the viewpoint of production efficiency.
1.クロロゲン酸類及びカフェインの分析
(分析機器)
HPLC(日立製作所(株)製)を使用した。装置の構成ユニットの型番は次の通りである。
・送液ユニット(デガッサ内蔵):L−2130
・オートサンプラ(クーラー付):L−2200
・カラムオーブン:L−2300
・分離カラム:Cadenza CD−C18、Size:4.6mm i.d.×150mm、3μm(インタクト株式会社)
・検出器(紫外可視吸光光度計):L−2420
1. Analysis of chlorogenic acids and caffeine (analytical instrument)
HPLC (manufactured by Hitachi, Ltd.) was used. The model numbers of the constituent units of the apparatus are as follows.
・ Liquid feeding unit (built-in degasser): L-2130
・ Autosampler (with cooler): L-2200
-Column oven: L-2300
Separation column: Cadenza CD-C18, Size: 4.6 mm i. d. × 150mm, 3μm (Intact Corporation)
Detector (ultraviolet visible absorption photometer): L-2420
(分析条件)
・サンプル注入量:10μL
・流量:1.0mL/min
・紫外線吸光光度計検出波長:325nm(クロロゲン酸類)、270nm(カフェイン)
・溶離液A:0.05mol/L酢酸、0.01mol/L酢酸ナトリウム、及び0.1mmol/L HEDPO(1−ヒドロキシエタン−1,1−ジホスホン酸)を含有する5%アセトニトリル
・溶離液B:アセトニトリル
(Analysis conditions)
Sample injection volume: 10 μL
・ Flow rate: 1.0 mL / min
-UV absorption photometer detection wavelength: 325nm (chlorogenic acids), 270nm (caffeine)
Eluent A: 5% acetonitrile containing 0.05 mol / L acetic acid, 0.01 mol / L sodium acetate, and 0.1 mmol / L HEDPO (1-hydroxyethane-1,1-diphosphonic acid) Eluent B : Acetonitrile
濃度勾配条件
時間 溶離液A 溶離液B
(分) (体積%) (体積%)
0.0 100 0
10.0 100 0
15.0 95 5
20.0 95 5
22.0 92 8
50.0 92 8
52.0 10 90
60.0 10 90
60.1 100 0
70.0 100 0
Concentration gradient condition Time Eluent A Eluent B
(Min) (volume%) (volume%)
0.0 100 0
10.0 100 0
15.0 95 5
20.0 95 5
22.0 92 8
50.0 92 8
52.0 10 90
60.0 10 90
60.1 100 0
70.0 100 0
(クロロゲン酸類のリテンションタイム)
・3−カフェオイルキナ酸(3−CQA):5.2min
・5−カフェオイルキナ酸(5−CQA):8.7min
・4−カフェオイルキナ酸(4−CQA):11.2min
・3−フェルラキナ酸(3−FQA):12.6min
・5−フェルラキナ酸(5−FQA):19.1min
・4−フェルラキナ酸(4−FQA):20.9min
・3,5−ジカフェオイルキナ酸(3,5−diCQA):37.0min
・3,4−ジカフェオイルキナ酸(3,4−diCQA):37.5min
・4,5−ジカフェオイルキナ酸(4,5−diCQA):44.8min
ここで求めた面積百分率から5−CQAを標準物質とし、クロロゲン酸類を定量した。
(Retention time of chlorogenic acids)
・ 3-Caffeoylquinic acid (3-CQA): 5.2 min
・ 5-Caffeoylquinic acid (5-CQA): 8.7 min
4-Caffeoylquinic acid (4-CQA): 11.2 min
3-Ferlaquinic acid (3-FQA): 12.6 min
5-Ferlaquinic acid (5-FQA): 19.1 min
4-Ferlaquinic acid (4-FQA): 20.9 min
3,5-dicaffeoylquinic acid (3,5-diCQA): 37.0 min
3,4-dicaffeoylquinic acid (3,4-diCQA): 37.5 min
・ 4,5-dicaffeoylquinic acid (4,5-diCQA): 44.8 min
From the area percentage obtained here, chlorogenic acids were quantified using 5-CQA as a standard substance.
(カフェインのリテンションタイム)
18.8min
ここで求めた面積百分率から試薬カフェインを標準物質とし、カフェインを定量した。
(Caffeine retention time)
18.8min
Caffeine was quantified from the area percentage determined here using the reagent caffeine as a standard substance.
2.クロロゲン酸類の収率
クロロゲン酸類の収率は、各実施例、比較例で得られた精製クロロゲン酸類含有組成物に含まれるクロロゲン酸類量を、原料クロロゲン酸類含有組成物に含まれるクロロゲン酸類量で除することにより求めた。
2. Yield of chlorogenic acids The yield of chlorogenic acids was calculated by dividing the amount of chlorogenic acids contained in the purified chlorogenic acid-containing compositions obtained in each Example and Comparative Example by the amount of chlorogenic acids contained in the raw material chlorogenic acids-containing composition. Was determined by
3.カフェイン含有率
カフェイン含有率は、各実施例、比較例で得られた精製クロロゲン酸類含有組成物に含まれるカフェイン量を、各実施例、比較例で得られた精製クロロゲン酸類含有組成物の全質量で除することにより求めた。
3. Caffeine content The caffeine content is the amount of caffeine contained in the purified chlorogenic acid-containing composition obtained in each Example and Comparative Example, and the purified chlorogenic acid-containing composition obtained in each Example and Comparative Example. Was obtained by dividing by the total mass of.
4.クロロゲン酸類含有率
クロロゲン酸類含有率は、各実施例、比較例で得られた精製クロロゲン酸類含有組成物に含まれるクロロゲン酸類量を、各実施例、比較例で得られた精製クロロゲン酸類含有組成物の全質量で除することにより求めた。
4). Chlorogenic acid content rate Chlorogenic acid content rate is the amount of chlorogenic acid contained in the purified chlorogenic acid-containing composition obtained in each example and comparative example, and the purified chlorogenic acid-containing composition obtained in each example and comparative example. Was obtained by dividing by the total mass of.
5.カフェイン/クロロゲン酸類の質量比
カフェイン/クロロゲン酸類の質量比は、各実施例、比較例で得られた精製クロロゲン酸類含有組成物に含まれるカフェイン量を、各実施例、比較例で得られた精製クロロゲン酸類含有組成物に含まれるクロロゲン酸類量で除することにより求めた。
5. Mass ratio of caffeine / chlorogenic acids The mass ratio of caffeine / chlorogenic acids is determined by the amount of caffeine contained in the purified chlorogenic acid-containing composition obtained in each example and comparative example. It calculated | required by remove | dividing by the amount of chlorogenic acids contained in the refine | purified chlorogenic acid containing composition obtained.
6.クロロゲン酸類の純度
クロロゲン酸類の純度は、精製クロロゲン酸類含有組成物の固形分中に含まれるクロロゲン酸類質量を、精製クロロゲン酸類含有組成物の固形分質量で除することにより求めた。
ここで、本明細書において「固形分」とは、試料を105℃の電気恒温乾燥機で3時間乾燥して揮発物質を除いた残分をいう。
6). Purity of chlorogenic acids The purity of chlorogenic acids was determined by dividing the mass of chlorogenic acids contained in the solid content of the purified chlorogenic acid-containing composition by the solid content mass of the purified chlorogenic acid-containing composition.
As used herein, “solid content” refers to a residue obtained by drying a sample for 3 hours with an electric thermostatic dryer at 105 ° C. to remove volatile substances.
7.L値の測定
試料を、色差計(スペクトロフォトメーター SE2000、日本電色社製)を用いて測定した。
7). Measurement of L value The sample was measured using a color difference meter (Spectrophotometer SE2000, manufactured by Nippon Denshoku).
調製例1
ロブスタ種の生コーヒー豆を熱水にて抽出し、乾燥して粉末状の原料クロロゲン酸類含有組成物を得た。原料クロロゲン酸類含有組成物は、クロロゲン酸類含量が38.2質量%、カフェイン含量が9.93質量%、カフェイン/クロロゲン酸類の質量比が0.26であった。次に、原料クロロゲン酸類含有組成物をクロロゲン酸類含有量が1.2質量%となるようにイオン交換水に溶解して「溶液A」を調製した。この溶液のpHは5.7であった。
Preparation Example 1
Robusta-type raw coffee beans were extracted with hot water and dried to obtain a powdery raw material chlorogenic acid-containing composition. The raw material chlorogenic acid-containing composition had a chlorogenic acid content of 38.2% by mass, a caffeine content of 9.93% by mass, and a mass ratio of caffeine / chlorogenic acids of 0.26. Next, the raw material chlorogenic acid-containing composition was dissolved in ion-exchanged water so that the chlorogenic acid content was 1.2% by mass to prepare “Solution A”. The pH of this solution was 5.7.
実施例1
(工程A)
調製例1によって得られた溶液Aを、H型陽イオン交換樹脂(三菱化学社製、商品名SK1BH)の充填されたカラムに、25℃、SV=1[hr-1]の空間速度にて樹脂の充填容量に対して20(mL/mL)通液させた。通液後の溶液のpHは2.3であった。
(工程B)
工程Aで得られた液を弱塩基性陰イオン交換樹脂(ダウ・ケミカル社製、商品名IRA67)の充填されたカラムに、25℃、SV=1[hr-1]の空間速度にて樹脂の充填容量に対して15(mL/mL)通液させた。
(工程C)
工程B後の弱塩基性陰イオン交換樹脂に、90℃の洗浄水をSV=5[hr-1]の空間速度にて樹脂の充填容量に対して15(mL/mL)通液させた。
(工程D)
工程C後の弱塩基性陰イオン交換樹脂に、アルカリ水溶液(0.5質量%NaOH水溶液、pH12.4)を、25℃、SV=5[hr-1]の空間速度にて樹脂の充填容量に対して25(mL/mL)通液させた。
工程Dで得られた液をH型陽イオン交換樹脂(三菱化学社製、商品名SK1BH)の充填されたカラムに通液させてpHを3.1に調整し、「精製クロロゲン酸類含有組成物」を得た。なお、ここで使用したH型陽イオン交換樹脂は、弱塩基性陰イオン交換樹脂の充填容量に対して1.2(mL/mL)であった。次いで、精製クロロゲン酸類含有組成物について分析を行った。その結果を表1に示す。
Example 1
(Process A)
Solution A obtained in Preparation Example 1 was placed in a column packed with an H-type cation exchange resin (trade name: SK1BH, manufactured by Mitsubishi Chemical Corporation) at a space velocity of 25 ° C. and SV = 1 [hr −1 ]. 20 (mL / mL) was passed through the filling volume of the resin. The pH of the solution after passing through was 2.3.
(Process B)
The liquid obtained in step A was applied to a column filled with a weakly basic anion exchange resin (trade name IRA67, manufactured by Dow Chemical Co., Ltd.) at 25 ° C. and a space velocity of SV = 1 [hr −1 ]. 15 (mL / mL) was passed through to the filling volume.
(Process C)
Washing water at 90 ° C. was passed through the weakly basic anion exchange resin after Step B at a space velocity of SV = 5 [hr −1 ] by 15 (mL / mL) with respect to the resin filling capacity.
(Process D)
The weakly basic anion exchange resin after Step C is charged with an alkaline aqueous solution (0.5 mass% NaOH aqueous solution, pH 12.4) at 25 ° C. and a space velocity of SV = 5 [hr −1 ]. Liquid (25 mL / mL).
The liquid obtained in step D was passed through a column packed with an H-type cation exchange resin (trade name: SK1BH, manufactured by Mitsubishi Chemical Corporation) to adjust the pH to 3.1, and “Purified chlorogenic acid-containing composition” " The H-type cation exchange resin used here was 1.2 (mL / mL) with respect to the filling capacity of the weakly basic anion exchange resin. Subsequently, the purified chlorogenic acid-containing composition was analyzed. The results are shown in Table 1.
実施例2〜4
工程Cにおいて表1に示す温度の洗浄水を使用したこと以外は、実施例1と同様の操作により精製クロロゲン酸類含有組成物を得た。次いで、精製クロロゲン酸類含有組成物について分析を行った。その結果を表1に示す。
Examples 2-4
A purified chlorogenic acid-containing composition was obtained in the same manner as in Example 1 except that the washing water having the temperature shown in Table 1 was used in Step C. Subsequently, the purified chlorogenic acid-containing composition was analyzed. The results are shown in Table 1.
実施例5
工程Cにおいて表1に示す通液倍数の洗浄水を使用したこと以外は、実施例1と同様の操作により精製クロロゲン酸類含有組成物を得た。次いで、精製クロロゲン酸類含有組成物について分析を行った。その結果を表1に示す。
Example 5
A purified chlorogenic acid-containing composition was obtained in the same manner as in Example 1 except that the washing water having a flow rate as shown in Table 1 was used in Step C. Subsequently, the purified chlorogenic acid-containing composition was analyzed. The results are shown in Table 1.
実施例6
(工程A)
調製例1によって得られた溶液Aを、H型陽イオン交換樹脂(三菱化学社製、商品名SK1BH)の充填されたカラムにSV=1[hr-1]の空間速度にて樹脂の充填容量に対して20(mL/mL)通液させた。通液後の溶液のpHは2.3であった。
(工程B)
工程Aで得られた液を弱塩基性陰イオン交換樹脂(ダウ・ケミカル社製、商品名IRA67)の充填されたカラムに、SV=1[hr-1]の空間速度にて樹脂の充填容量に対して15(mL/mL)通液させた。
(工程C)
工程B後の弱塩基性陰イオン交換樹脂に、90℃の洗浄水をSV=5[hr-1]の空間速度にて樹脂の充填容量に対して15(mL/mL)通液させた。
(工程D)
工程C後の弱塩基性陰イオン交換樹脂に、酸水溶液(1.8質量%HCl水溶液、pH0.5)をカラムにSV=5[hr-1]の空間速度にて樹脂の充填容量に対して25(mL/mL)通液させた。
工程Dで得られた液を20torrの減圧下で濃縮し、溶液に残存したHClを留去し、「精製クロロゲン酸類含有組成物」を得た。次いで、精製クロロゲン酸類含有組成物について分析を行った。その結果を表1に示す。
Example 6
(Process A)
The solution A obtained in Preparation Example 1 was charged into a column packed with an H-type cation exchange resin (trade name SK1BH, manufactured by Mitsubishi Chemical Corporation) at a space velocity of SV = 1 [hr −1 ]. 20 (mL / mL) was passed through. The pH of the solution after passing through was 2.3.
(Process B)
The liquid obtained in step A is packed in a column filled with a weakly basic anion exchange resin (trade name IRA67, manufactured by Dow Chemical Co., Ltd.) at a space velocity of SV = 1 [hr −1 ]. 15 (mL / mL) was passed through.
(Process C)
Washing water at 90 ° C. was passed through the weakly basic anion exchange resin after Step B at a space velocity of SV = 5 [hr −1 ] by 15 (mL / mL) with respect to the resin filling capacity.
(Process D)
To the weakly basic anion exchange resin after Step C, an acid aqueous solution (1.8 mass% HCl aqueous solution, pH 0.5) is applied to the column at a space velocity of SV = 5 [hr −1 ] with respect to the resin packing capacity. 25 (mL / mL).
The liquid obtained in Step D was concentrated under a reduced pressure of 20 torr, and HCl remaining in the solution was distilled off to obtain a “purified chlorogenic acid-containing composition”. Subsequently, the purified chlorogenic acid-containing composition was analyzed. The results are shown in Table 1.
比較例1
工程Cにおいて25℃の洗浄水を用いたこと以外は、実施例1と同様の操作にて「精製クロロゲン酸類含有組成物」を得た。次いで、精製クロロゲン酸類含有組成物について分析を行った。その結果を表1に示す。
Comparative Example 1
A “purified chlorogenic acid-containing composition” was obtained in the same manner as in Example 1, except that 25 ° C. washing water was used in Step C. Subsequently, the purified chlorogenic acid-containing composition was analyzed. The results are shown in Table 1.
比較例2
工程Cを行わなかったこと以外は、実施例1と同様の操作にて「精製クロロゲン酸類含有組成物」を得た。次いで、精製クロロゲン酸類含有組成物について分析を行った。その結果を表1に示す。
Comparative Example 2
A “purified chlorogenic acid-containing composition” was obtained in the same manner as in Example 1 except that Step C was not performed. Subsequently, the purified chlorogenic acid-containing composition was analyzed. The results are shown in Table 1.
比較例3
工程Bにおいて強塩基性陰イオン交換樹脂を用いたこと以外は、実施例1と同様の操作にて「精製クロロゲン酸類含有組成物」を得た。次いで、精製クロロゲン酸類含有組成物について分析を行った。その結果を表1に示す。
Comparative Example 3
A “purified chlorogenic acid-containing composition” was obtained in the same manner as in Example 1, except that a strongly basic anion exchange resin was used in Step B. Subsequently, the purified chlorogenic acid-containing composition was analyzed. The results are shown in Table 1.
表1から、原料クロロゲン酸類含有組成物を陽イオン交換樹脂、弱塩基性陰イオン交換樹脂に順次接触させ、更に弱塩基性陰イオン交換樹脂に35℃以上の水を接触させた後、酸水溶液又はアルカリ水溶液で溶出させることにより、クロロゲン酸類を損なうことなく、カフェインがより一層低減された精製クロロゲン酸類含有組成物が得られることがわかる。 From Table 1, the raw material chlorogenic acid-containing composition was sequentially brought into contact with a cation exchange resin and a weakly basic anion exchange resin, and further contacted with a weakly basic anion exchange resin with water at 35 ° C. or higher, followed by an acid aqueous solution. Alternatively, it can be seen that by eluting with an alkaline aqueous solution, a purified chlorogenic acid-containing composition in which caffeine is further reduced can be obtained without impairing the chlorogenic acids.
Claims (7)
工程Aにより得られた液を弱塩基性陰イオン交換樹脂に接触させる工程Bと、
工程B後の弱塩基性陰イオン交換樹脂に35℃以上の水を接触させる工程Cと、
工程C後の弱塩基性陰イオン交換樹脂に酸水溶液を接触させる工程D
を備える、精製クロロゲン酸類含有組成物の製造方法。 Contacting the raw material chlorogenic acid-containing composition with a cation exchange resin; and
Contacting the liquid obtained in step A with a weakly basic anion exchange resin; and
Step C in which water at 35 ° C. or higher is brought into contact with the weakly basic anion exchange resin after Step B;
Step D of contacting the acid aqueous solution to a weakly basic anion exchange resin after step C
A method for producing a purified chlorogenic acid-containing composition.
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