JP2005263632A - Method for producing composition containing high concentration of chlorogenic acid - Google Patents
Method for producing composition containing high concentration of chlorogenic acid Download PDFInfo
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本発明は、食品添加物、化粧品などの抗酸化剤、紫外線吸収剤、食品、健康食品などに有用なクロロゲン酸類を高濃度に含有する組成物の製造方法に関する。 The present invention relates to a method for producing a composition containing a high concentration of chlorogenic acids useful for food additives, antioxidants such as cosmetics, ultraviolet absorbers, foods, health foods and the like.
コーヒー生豆には、主成分としての下式（Ｉ）に示すクロロゲン酸（キナ酸の５位のヒドロキシル基にコーヒー酸がエステル結合した５−カフェロイルキナ酸，以下、「クロロゲン酸（Ｉ）」と記す）や、３−カフェロイルキナ酸、４−カフェロイルキナ酸、３−ｐ−クマロイルキナ酸、５−フェルロイルキナ酸、３，４−ジカフェロイルキナ酸、３，５−ジカフェロイルキナ酸、４，５−ジカフェロイルキナ酸、３−カフェロイル−４−フェルロイルキナ酸（３−フェルロイル−４−カフェロイルキナ酸）、３−カフェロイル−５−フェルロイルキナ酸（３−フェルロイル−５−カフェロイルキナ酸）、４−カフェロイル−５−フェルロイルキナ酸（４−フェルロイル−５−カフェロイルキナ酸）などクロロゲン酸同族体からなるクロロゲン酸類をはじめカフェインなどの有用な成分が含まれている。 In green coffee beans, chlorogenic acid represented by the following formula (I) as a main component (5-caffeoylquinic acid in which caffeic acid is ester-bonded to the hydroxyl group at 5-position of quinic acid, hereinafter referred to as “chlorogenic acid (I)” 3) -caffeoylquinic acid, 4-caffeoylquinic acid, 3-p-coumaroylquinic acid, 5-feruloylquinic acid, 3,4-dicaffeoylquinic acid, 3,5-dicaffee. Roylquinic acid, 4,5-dicaffeoylquinic acid, 3-caferoyl-4-feruloylquinic acid (3-feruloyl-4-caffeoylquinic acid), 3-caferoyl-5-feruloylquinic acid (3- Chlorogenic acid homologues such as feruloyl-5-caffeoylquinic acid) and 4-caffeoyl-5-feruloylquinic acid (4-feruloyl-5-caffeoylquinic acid). It contains useful components, such as the beginning caffeine acids.
そして、上記のようなクロロゲン酸類は、いずれも抗酸化性や生理活性を示すことが知られている（たとえば、非特許文献１参照）。
ところで、上記のようなクロロゲン酸類をコーヒー生豆から抽出する手法として、コーヒー生豆の粉砕物から水やアルコール水溶液を用いて抽出する方法が一般的に知られている。
And it is known that all the above chlorogenic acids show antioxidant property and physiological activity (for example, refer nonpatent literature 1).
By the way, as a method for extracting the chlorogenic acids as described above from green coffee beans, a method of extracting from ground coffee beans using water or an aqueous alcohol solution is generally known.
しかしながら、従来の抽出法で得られた抽出液中には糖分、蛋白質等の水に可溶な成分などの多くの夾雑物が含まれている。このため、抽出液を乾燥することで得られた組成物中に含まれるクロロゲン酸類の含有量は２０〜３０重量％程度の極めて低いものであった。
そこで、これを解決するために、上記のようにしてコーヒー生豆からアルコール水溶液で抽出したクロロゲン酸類を含む抽出液をスチレン・ジビニルベンゼン系又はメタクリル酸エステル系多孔質性重合樹脂と接触処理し、次いで該多孔質性重合樹脂を希アルカリ水溶液で処理してクロロゲン酸類を選択的に溶離採取する方法（たとえば、特許文献１参照）が既に提案されている。
However, the extract obtained by the conventional extraction method contains many impurities such as components soluble in water such as sugar and protein. For this reason, the content of chlorogenic acids contained in the composition obtained by drying the extract was extremely low, about 20 to 30% by weight.
Therefore, in order to solve this, an extract containing chlorogenic acids extracted from green coffee beans with an aqueous alcohol solution as described above is contact-treated with a styrene / divinylbenzene-based or methacrylate-based porous polymer resin, Next, a method of treating the porous polymer resin with a dilute alkaline aqueous solution to selectively elute and collect chlorogenic acids (for example, see Patent Document 1) has already been proposed.
ところで、一般にコーヒー生豆からクロロゲン酸類を抽出させるには、上記のようにアルコール水溶液が用いられる。したがって、抽出液中にアルコールが含まれるため、抽出液を多孔性重合樹脂で直接処理しようとしても、アルコールの存在が問題となり、その存在により十分な吸着が望めない。このため、抽出液から蒸留などにより完全にアルコールを留去する必要があるが、完全に留去することは難しい。
そこで、上記特許文献１の方法の場合、抽出液に食塩を添加し、その塩析効果によりクロロゲン酸類の多孔性重合樹脂への吸着性を高めることで、アルコールを含む抽出液をそのまま使用できるようにする工夫がなされている。さらに、多孔性重合樹脂に吸着させたクロロゲン酸類を効率よく溶出させるために、炭酸ナトリウムなどのアルカリ水溶液を用いる方法が提案されている。
By the way, generally, in order to extract chlorogenic acids from green coffee beans, an alcohol aqueous solution is used as described above. Therefore, since alcohol is contained in the extract, even if the extract is to be directly treated with the porous polymer resin, the presence of alcohol becomes a problem, and sufficient adsorption cannot be expected due to the presence. For this reason, it is necessary to completely distill off alcohol from the extract by distillation or the like, but it is difficult to distill off completely.
Therefore, in the case of the method of Patent Document 1 described above, by adding sodium chloride to the extract and enhancing the adsorptivity of chlorogenic acids to the porous polymer resin by the salting-out effect, the extract containing alcohol can be used as it is. The idea to make is made. Furthermore, a method using an aqueous alkali solution such as sodium carbonate has been proposed in order to efficiently elute chlorogenic acids adsorbed on the porous polymer resin.
しかし、クロロゲン酸類はキナ酸にカフェー酸やフェルラ酸がエステル結合した化合物であるため、アルカリや酸の添加はエステル結合の加水分解を進行させる。このため、これらの使用は好ましくない。特に、アルカリ性水溶液の添加はフェノール性水酸基を解離させるとともに、酸化反応を促進させクロロゲン酸類を黒色に変化させる。したがって、上記特許文献１の方法の場合、イオン交換樹脂などを用いて添加した食塩やアルカリ性成分を除去する工程が後処理として不可欠となっており、作業がどうしても煩雑とならざるを得ない。しかも、高価な多孔質性重合樹脂を用いなければならないため、製造コストにも問題がある。 However, since chlorogenic acids are compounds in which caffeic acid or ferulic acid is ester-bonded to quinic acid, the addition of alkali or acid causes hydrolysis of the ester bond to proceed. For this reason, their use is not preferred. In particular, the addition of an alkaline aqueous solution dissociates the phenolic hydroxyl group and accelerates the oxidation reaction to change the chlorogenic acids to black. Therefore, in the case of the method described in Patent Document 1, a step of removing salt and alkaline components added using an ion exchange resin or the like is indispensable as a post-treatment, and the work is inevitably complicated. Moreover, since an expensive porous polymer resin must be used, there is a problem in manufacturing cost.
本発明は、上記事情に鑑みて、アルコール等の溶媒を含有する水溶液を抽出液として用いる高濃度クロロゲン酸類含有組成物の製造において、抽出液からのアルコール等の溶媒成分の留去や食塩の添加、さらに溶出時のアルカリ性水溶液の使用といった煩雑な工程を経ることなく、単純な工程でクロロゲン酸類を高濃度で含有する組成物を製造する方法を提供することを目的としている。 In view of the above circumstances, in the production of a high-concentration chlorogenic acid-containing composition using an aqueous solution containing a solvent such as alcohol as an extract, in the present invention, distillation of solvent components such as alcohol from the extract or addition of sodium chloride Another object of the present invention is to provide a method for producing a composition containing chlorogenic acids at a high concentration in a simple process without going through complicated processes such as the use of an alkaline aqueous solution during elution.
上記目的を達成するために、本発明にかかる高濃度のクロロゲン酸類を含む組成物の製造方法は、植物から得られるクロロゲン酸類を含む水溶性抽出物を活性炭処理後、活性炭に吸着した吸着物を有機溶媒あるいはそれらを含む水溶液で溶離させる工程を備えることを特徴とする。 In order to achieve the above-mentioned object, the method for producing a composition containing a high concentration of chlorogenic acids according to the present invention comprises treating the water-soluble extract containing chlorogenic acids obtained from plants with activated carbon, and then adsorbing the adsorbed material adsorbed on the activated carbon. And elution with an organic solvent or an aqueous solution containing them.
また、原料となる植物としては、特に限定されないが、たとえば、コーヒー生豆、ヨモギ類、ジャガイモ、サツマイモ等が挙げられ、中でもコーヒー生豆が好適に使用される。 Moreover, it does not specifically limit as a plant used as a raw material, For example, a coffee raw bean, mugworts, a potato, a sweet potato etc. are mentioned, Especially, a coffee raw bean is used suitably.
本発明に用いる活性炭は、工業用に利用される粉末、顆粒、カラム用各種活性炭を用いることができる。また、活性炭による吸着方法としては、カラム充填による流通式あるいは回分式で行うことができる。回分式およびカラム充填による流通式で用いる場合には、顆粒状の活性炭を用いることが好ましい。用いる活性炭の種類については、ヤシ殻、石炭、木質などを原料とした活性炭を用いることができる。しかし、酸やアルカリ等で処理した活性炭はクロロゲン酸の吸脱着を著しく阻害するため使用するには不適である。また、酸処理等で精製した活性炭などを使用する必要はなく、むしろこれらはクロロゲン酸の強い吸着を招き、溶離が困難となり、使用するには不適である。さらに、活性炭の水浸液のｐＨがアルカリ性を示す場合、クロロゲン酸類のフェノール性水酸基を解離させ、酸化反応を促進させるため、クロロゲン酸類の黒色変化を招く。このため、使用する活性炭の水浸液のｐＨは、中性から弱酸性（ｐＨ７−４）が好ましい。 As the activated carbon used in the present invention, powders, granules, and various activated carbons for columns used for industrial use can be used. Moreover, as an adsorption method using activated carbon, it can be carried out by a flow system by column packing or a batch system. In the case of using the batch type and the flow type by column packing, it is preferable to use granular activated carbon. About the kind of activated carbon to be used, activated carbon made from coconut shell, coal, wood, or the like can be used. However, activated carbon treated with acid, alkali or the like is unsuitable for use because it significantly inhibits adsorption and desorption of chlorogenic acid. Moreover, it is not necessary to use activated carbon or the like purified by acid treatment or the like. Rather, these cause strong adsorption of chlorogenic acid, making elution difficult, and are not suitable for use. Further, when the pH of the activated carbon immersion liquid shows alkalinity, the phenolic hydroxyl groups of chlorogenic acids are dissociated and the oxidation reaction is promoted, resulting in a black change in chlorogenic acids. For this reason, the pH of the immersion liquid of activated carbon used is preferably neutral to weakly acidic (pH 7-4).
活性炭の使用量は、コーヒー生豆抽出物の場合、抽出物に対して１／１０〜１０倍であるが、高濃度のクロロゲン酸類を吸着するためには１／２倍以上の使用が好ましい。活性炭に吸着させる温度は室温から６０℃で行えるが、いずれの温度においても大きな差異はない。本発明における精製処理の大きな特徴の一つとしては、コーヒー生豆等の植物から抽出された抽出液あるいはその濃縮液を酸やアルカリ、食塩などのその他の添加物を加える処理をすることなく、そのままで活性炭処理に引き続き溶離処理をすることで高濃度のクロロゲン酸類を含む組成物を得ることができることである。
活性炭処理する際の抽出液あるいはその濃縮液は水溶液である必要はなく、汎用されるエタノール、メタノールなどのアルコールやその他の有機溶媒を３０容量％以下（好ましくは１０容量％以下）程度含まれていてもそのまま活性炭で処理することができる。
In the case of green coffee bean extract, the amount of activated carbon used is 1/10 to 10 times that of the extract, but in order to adsorb high-concentration chlorogenic acids, use of 1/2 times or more is preferable. The temperature to be adsorbed on the activated carbon can be from room temperature to 60 ° C., but there is no significant difference at any temperature. One of the major features of the purification treatment in the present invention is that the extract extracted from plants such as green coffee beans or the concentrated solution thereof is not subjected to a treatment of adding other additives such as acid, alkali, and salt, A composition containing a high concentration of chlorogenic acids can be obtained by subjecting the activated carbon treatment to the elution treatment as it is.
The extract or the concentrated solution for the activated carbon treatment does not have to be an aqueous solution, and contains about 30% by volume or less (preferably 10% by volume or less) of alcohol and other organic solvents such as ethanol and methanol which are widely used. However, it can be directly treated with activated carbon.
活性炭に吸着したクロロゲン酸類を溶離させる溶媒としては、メタノール、エタノール、イソプロピルアルコール、アセトン、アセトニトリルおよびそれらの水溶液が用いることができるが、これらの溶媒に限定するものではない。また、溶媒は、水溶液の状態でも用いることができるが、水溶液の状態で用いる場合は、５０容量％以上の濃度で用いることが好ましい。すなわち、５０容量％未満の濃度では、溶媒によっては溶離が不十分となる恐れがある。 As a solvent for eluting the chlorogenic acids adsorbed on the activated carbon, methanol, ethanol, isopropyl alcohol, acetone, acetonitrile, and an aqueous solution thereof can be used, but are not limited to these solvents. The solvent can also be used in the form of an aqueous solution, but when used in the form of an aqueous solution, it is preferably used at a concentration of 50% by volume or more. That is, at a concentration of less than 50% by volume, the elution may be insufficient depending on the solvent.
本発明にかかる高濃度のクロロゲン酸類を含む組成物の製造方法は、以上のように、植物から抽出される水溶性抽出物を、安価な活性炭による吸脱着を利用して高濃度にクロロゲン酸類を含む組成物を得るようにしたので、製造コストが低減できる。即ち、活性炭は通常、水に溶けにくい疎水性の分子をよく吸着する性質があり排水中や化成品中の微量着色成分や不純物の除去に用いられている。また、活性炭は合成高分子と異なり、吸着サイトとして有する細孔分布が広範囲に渡り、その吸着性能は極めて強いといえる。このことは、水溶性であるクロロゲン酸類を効率よく吸着するのに適した構造を有しているものと考えられる。
また、活性炭を吸着剤として用いる方法であれば、有機溶媒を含む抽出液であっても有機溶媒が３０容量％以下程度の濃度であれば、食塩等の添加による塩析効果を利用しなくてクロロゲン酸類吸着できる。そして、高濃度の溶媒を含む抽出液に活性炭を曝せば、吸着したクロロゲン酸類が簡単に溶離する。したがって、食塩やアルカリ成分を除去するためにイオン交換樹脂などで後処理する必要もなくなり、製造工程が簡略化できる。
As described above, the method for producing a composition containing a high concentration of chlorogenic acids according to the present invention can be applied to a water-soluble extract extracted from a plant by using adsorption / desorption by cheap activated carbon to a high concentration of chlorogenic acids. Since the composition containing it is obtained, the manufacturing cost can be reduced. That is, activated carbon usually has a property of adsorbing hydrophobic molecules that are hardly soluble in water, and is used to remove trace coloring components and impurities in wastewater and chemical products. Moreover, unlike synthetic polymers, activated carbon has a wide distribution of pores as adsorption sites, and it can be said that its adsorption performance is extremely strong. This is considered to have a structure suitable for efficiently adsorbing water-soluble chlorogenic acids.
Moreover, if the method uses activated carbon as an adsorbent, even if it is an extract containing an organic solvent, if the organic solvent has a concentration of about 30% by volume or less, the salting-out effect due to the addition of salt or the like need not be used. Can adsorb chlorogenic acids. And if activated carbon is exposed to the extract containing a high concentration solvent, the adsorbed chlorogenic acids are easily eluted. Therefore, it is not necessary to perform post-treatment with an ion exchange resin or the like in order to remove salt and alkali components, and the manufacturing process can be simplified.
以下に、本発明を、その実施の形態を詳しく説明する。
本発明の高濃度クロロゲン酸類を含む組成物の製造方法は、まず、コーヒー生豆等のクロロゲン酸類を含む植物からメタノール、エタノール、イソプロピルアルコール、アセトン、アセトニトリルあるいはそれらの水溶液を用いて、クロロゲン酸類の抽出液を得る。
Hereinafter, embodiments of the present invention will be described in detail.
The method for producing a composition containing high-concentration chlorogenic acids according to the present invention is as follows. First, from a plant containing chlorogenic acids such as green coffee beans, methanol, ethanol, isopropyl alcohol, acetone, acetonitrile or an aqueous solution thereof is used. Obtain an extract.
つぎに、抽出液から溶媒を留去するか抽出液を水で希釈して溶媒が３０容量％以下のクロロゲン酸類を含む水溶液とする。
そして、このクロロゲン酸類を含む水溶液を酸処理やアルカリ処理等を施していない活性炭と接触させ、一旦クロロゲン酸類を活性炭に吸着させる。
Next, the solvent is distilled off from the extract or the extract is diluted with water to obtain an aqueous solution containing chlorogenic acids whose solvent is 30% by volume or less.
Then, the aqueous solution containing the chlorogenic acids is brought into contact with activated carbon that has not been subjected to acid treatment or alkali treatment, and the chlorogenic acids are once adsorbed on the activated carbon.
そののち、クロロゲン酸類を吸着させた活性炭を水で洗浄し、必要に応じて吸引脱水等を行う。次に、クロロゲン酸類が吸着した活性炭を、５０容量％以上の濃度の溶媒を含む水溶液に曝し、溶媒中に活性炭に吸着したクロロゲン酸類を活性炭から溶離させる。
そして、溶出液を濃縮、噴霧乾燥することによって高濃度にクロロゲン酸類を含む組成物を得る。
After that, the activated carbon on which chlorogenic acids are adsorbed is washed with water, and suction dehydration or the like is performed as necessary. Next, the activated carbon on which chlorogenic acids are adsorbed is exposed to an aqueous solution containing a solvent having a concentration of 50% by volume or more, and the chlorogenic acids adsorbed on the activated carbon in the solvent are eluted from the activated carbon.
Then, the eluate is concentrated and spray-dried to obtain a composition containing chlorogenic acids at a high concentration.
以下に、本発明を実施例によって具体的に説明するが、本発明の範囲はこれらの実施例に限定されるものではない。 EXAMPLES The present invention will be specifically described below with reference to examples, but the scope of the present invention is not limited to these examples.
（実施例１）
粉砕したコーヒー生豆（アラビカ種）を６０容量％エタノール水溶液で抽出し、噴霧乾燥したコーヒー抽出物１ｇ(クロロゲン酸(I)の含有量１９重量％、総クロロゲン酸含有量３０重量％、カフェイン５重量％)を蒸留水１０ｍＬに溶解し、直径１．５ｃｍのガラスカラムにクロマト用活性炭（和光純薬工業社製）３ｇを充填したカラムに通液した。水（１５０ｍＬ）およびメタノール水溶液（１０〜５０容量％）を１００ｍＬずつ順に通液し、溶出するクロロゲン酸の濃度を高速液体クロマトグラフ装置(HPLC)により調べ、その結果を図１に示した。
(Example 1)
Ground coffee beans (Arabica) extracted with 60% ethanol aqueous solution and spray-dried coffee extract 1g (chlorogenic acid (I) content 19% by weight, total
図１に示すように、３０容量％以下のメタノール水溶液でクロロゲン酸の溶出は認められず、５０容量％以上のメタノール水溶液で溶出することが確認できた。
すなわち、図１から、活性炭を用いる吸着処理においては、３０容量％以下のアルコールを含有する抽出物ではクロロゲン酸類の溶出は認められず、５０容量％以上のアルコール水溶液で初めて溶出させることが可能となること、さらに、活性炭に吸着処理されたクロロゲン酸類を５０容量％以上のアルコール水溶液で溶出処理して濃縮、噴霧乾燥などにより乾燥させるだけで高濃度にクロロゲン酸類を含む抽出物を製造できることがよくわかる。
As shown in FIG. 1, elution of chlorogenic acid was not observed in 30% by volume or less of methanol aqueous solution, and it was confirmed that it was eluted in 50% by volume or more of methanol aqueous solution.
That is, from FIG. 1, in the adsorption treatment using activated carbon, elution of chlorogenic acids is not observed in an extract containing 30% by volume or less of alcohol, and it can be eluted for the first time in an aqueous solution of 50% or more by volume of alcohol. Furthermore, it is often possible to produce an extract containing chlorogenic acids at a high concentration simply by eluting chlorogenic acids adsorbed on activated carbon with an aqueous alcohol solution of 50% by volume or more and drying them by concentration, spray drying or the like. Understand.
（比較例１）
粉砕したコーヒー生豆（アラビカ種）を６０容量％エタノール水溶液で抽出し、噴霧乾燥したコーヒー抽出物１ｇ(クロロゲン酸（Ｉ）の含有量１９重量％、総クロロゲン酸含有量３０重量％、カフェイン５重量％)を蒸留水１０ｍＬに溶解し、直径１．５ｃｍのガラスカラムに合成吸着剤アンバーライトXAD7HD（オルガノ社製）３０ｍＬを充填したカラムに通液した。その後、水１５０ｍＬおよび１０容量％メタノール水溶液１００ｍＬ２０容量％メタノール水溶液１００ｍＬ，５０容量％メタノール水溶液２００ｍＬを順に通液し、溶出するクロロゲン酸の濃度を高速液体クロマトグラフ装置(HPLC)により調べその結果を図２に示した。
(Comparative Example 1)
Ground coffee beans (Arabica varieties) extracted with 60 vol% ethanol aqueous solution and spray-dried 1 g coffee extract (chlorogenic acid (I) content 19% by weight, total
（比較例２）
合成高分子吸着剤にアンバーライトXAD2（オルガノ社製）を用いた以外は比較例１と同様の操作で行った。その結果を図３に示した。
(Comparative Example 2)
The same operation as in Comparative Example 1 was performed except that Amberlite XAD2 (manufactured by Organo) was used as the synthetic polymer adsorbent. The results are shown in FIG.
（実施例２）
実施例１で用いたクロロゲン酸含有量１９％のコーヒー生豆抽出物１ｇを蒸留水２０ｍＬに溶解し、以下の表1に示す使用量で粒状活性炭（日本エンバイロケミカルズ社製白鷺ＫＬ）をそれぞれ添加し、真空脱気を３回繰り返し１時間室温で撹拌した。その後活性炭を吸引濾過し、活性炭を１００ｍＬの蒸留水で洗浄した。この活性炭をビーカーに移し、２０ｍＬの６０容量％エタノール水溶液を加え、１０分間撹拌した。これを吸引濾過し、活性炭吸着物を溶出させた。この操作を３回繰り返し、約６０ｍＬのエタノール水溶液を得た。溶出液をロータリーエバポレーターで蒸発、真空乾燥する淡黄色粉末組成物が得られた。得られた淡黄色粉末組成物中に含まれるクロロゲン酸およびカフェインの含有量をそれぞれ測定し、その結果を表１に合わせて示した。なお、クロロゲン酸とカフェインの含有量はＨＰＬＣで定量した（化粧品種別配合成分規格（追補Ｉ）（日本化粧品連合工業会）コーヒーエキス項定量法に従った）。なお、表１中、（）内に示した百分率はすべて重量％である。
(Example 2)
1 g of coffee bean extract having a chlorogenic acid content of 19% used in Example 1 was dissolved in 20 mL of distilled water, and granular activated carbon (Shirakaba KL manufactured by Nippon Environmental Chemicals Co., Ltd.) was added in the amounts shown in Table 1 below. Then, vacuum degassing was repeated 3 times and stirred at room temperature for 1 hour. Thereafter, the activated carbon was filtered by suction, and the activated carbon was washed with 100 mL of distilled water. The activated carbon was transferred to a beaker, 20 mL of a 60 vol% ethanol aqueous solution was added, and the mixture was stirred for 10 minutes. This was suction filtered to elute the activated carbon adsorbate. This operation was repeated three times to obtain about 60 mL of an ethanol aqueous solution. A light yellow powder composition was obtained by evaporating the eluate with a rotary evaporator and vacuum drying. The contents of chlorogenic acid and caffeine contained in the obtained pale yellow powder composition were measured, and the results are shown in Table 1. In addition, the content of chlorogenic acid and caffeine was quantified by HPLC (according to the method for determining the amount of ingredients for cosmetic varieties (Appendix I) (Japan Cosmetics Association)). In Table 1, all percentages shown in parentheses are% by weight.
上記表１から、コーヒー生豆抽出物に対して１から１．５倍量の活性炭の使用量が好ましいことがわかる。 From Table 1 above, it can be seen that the amount of activated carbon used is preferably 1 to 1.5 times the amount of green coffee bean extract.
（実施例３）
実施例１で用いたクロロゲン酸含有量１９％のコーヒー生豆抽出物３ｇを蒸留水３０ｍＬに溶解し、表２に示す活性炭３ｇを添加し１時間撹拌した。その後活性炭を吸引濾過し、活性炭を約１００ｍＬの蒸留水で洗浄した。その後、表２に示す抽出溶剤を用いて活性炭をそれぞれ吸引洗浄し、吸着物を溶出させた。溶出液をロータリーエバポレーターで蒸発、真空乾燥すると淡黄色粉末抽出物がそれぞれ得られた。得られた淡黄色粉末組成物中に含まれるクロロゲン酸およびカフェインの含有量をそれぞれ測定し、その結果を表１に合わせて示した。なお、クロロゲン酸とカフェインの含有量はＨＰＬＣで定量した（化粧品種別配合成分規格（追補Ｉ）（日本化粧品連合工業会）コーヒーエキス項定量法に従った）。総クロロゲン酸量は、非特許文献1（M.Murata, H.Okada, S. Homma, ASIC,16 Colloque, Kyoto, pp199-207, 1995）に従って、ＨＰＬＣで分析した。また、表２中、（）内に示した百分率は、抽出溶剤の濃度のみ容量％、それ以外は重量％である。
(Example 3)
3 g of green coffee bean extract having a chlorogenic acid content of 19% used in Example 1 was dissolved in 30 mL of distilled water, 3 g of activated carbon shown in Table 2 was added, and the mixture was stirred for 1 hour. Thereafter, the activated carbon was filtered by suction, and the activated carbon was washed with about 100 mL of distilled water. Thereafter, the activated carbon was suction-washed using the extraction solvent shown in Table 2 to elute the adsorbate. The eluate was evaporated with a rotary evaporator and dried under vacuum to obtain a pale yellow powder extract. The contents of chlorogenic acid and caffeine contained in the obtained pale yellow powder composition were measured, and the results are shown in Table 1. In addition, the content of chlorogenic acid and caffeine was quantified by HPLC (according to the method for determining the amount of ingredients for cosmetic varieties (Appendix I) (Japan Cosmetics Association)). The total amount of chlorogenic acid was analyzed by HPLC according to Non-Patent Document 1 (M. Murata, H. Okada, S. Homma, ASIC, 16 Colloque, Kyoto, pp199-207, 1995). In Table 2, the percentages shown in parentheses are% by volume only for the concentration of the extraction solvent, and% by weight otherwise.
上記表２から抽出溶媒として６０容量％〜８０容量％の有機溶媒を含む水溶液を用いること、あるいは、活性炭として工業用よりクロマト用のものを用いる方がより高濃度クロロゲン酸類を含む組成物を得られることがよくわかる。 From Table 2 above, a composition containing a higher concentration of chlorogenic acids is obtained by using an aqueous solution containing an organic solvent of 60 vol% to 80 vol% as an extraction solvent, or by using a chromatographic active carbon as an activated carbon. You can see well.
（実施例４）
実施例１で用いたクロロゲン酸含有量１９重量％のコーヒー生豆抽出物３ｇを蒸留水３０ｍＬに溶解し、顆粒状活性炭（二村化学社製太閤ＳＧ）５ｇをウエット状態で充填した直径２ｃｍのガラスカラムに通液した。さらに、蒸留水３００ｍＬを流し活性炭を洗浄した後、３００ｍＬの６０容量％メタノール水を通液し、溶出液を得た。この水溶液の溶媒を留去し、乾燥すると６２３ｍｇの淡黄色粉末が得られた。これに含まれるクロロゲン酸は１９５ｍｇ（３１重量％）でクロロゲン酸類を含めると３０５ｍｇ（４９重量％）の含有量の高い純度でクロロゲン酸類を含む組成物が得られた。カフェインの含有は２５ｍｇ（４重量％）であった。
Example 4
A glass having a diameter of 2 cm, in which 3 g of green coffee bean extract having a chlorogenic acid content of 19% by weight used in Example 1 was dissolved in 30 mL of distilled water and 5 g of granular activated carbon (Taiko SG manufactured by Nimura Chemical Co., Ltd.) was filled in a wet state. The solution was passed through the column. Further, 300 mL of distilled water was poured to wash the activated carbon, and then 300 mL of 60% by volume methanol water was passed through to obtain an eluate. The solvent of this aqueous solution was distilled off and dried to obtain 623 mg of a pale yellow powder. The chlorogenic acid contained therein was 195 mg (31 wt%), and when chlorogenic acids were included, a composition containing chlorogenic acids with a high content of 305 mg (49 wt%) was obtained. The caffeine content was 25 mg (4% by weight).
（実施例５）
実施例１で用いたクロロゲン酸含有量１９％のコーヒー生豆抽出物３ｇを蒸留水３０ｍＬに溶解し、顆粒状活性炭（二村化学社製太閤ＳＧＰ）５ｇを添加して真空脱気を３回繰り返しその後１時間撹拌した。その後活性炭を吸引濾過し、活性炭を約３００ｍＬの蒸留水でそのまま吸引洗浄した。この活性炭をビーカーに移し、１００ｍＬの６０容量％エタノール水溶液を加え、１０分間撹拌した。これを吸引濾過し、活性炭吸着物を溶出させた。この操作を２回繰り返し、約２００ｍＬのエタノール水溶液を得た。この水溶液の溶媒を留去し、乾燥すると８６０ｍｇの淡黄色粉末が得られた。これに含まれるクロロゲン酸は３４４ｍｇ（４０重量％）でクロロゲン酸類を含めると５０７ｍｇ（５９重量％）の含有量の高い純度でクロロゲン酸類を含む組成物が得られた。カフェインの含有は２６ｍｇ（３重量％）であった。
(Example 5)
3 g of green coffee bean extract having a chlorogenic acid content of 19% used in Example 1 was dissolved in 30 mL of distilled water, 5 g of granular activated carbon (Nimura Chemical Co., Ltd., Taiho SGP) was added, and vacuum degassing was repeated three times. The mixture was then stirred for 1 hour. Thereafter, the activated carbon was subjected to suction filtration, and the activated carbon was suction-washed with about 300 mL of distilled water. The activated carbon was transferred to a beaker, 100 mL of a 60 vol% ethanol aqueous solution was added, and the mixture was stirred for 10 minutes. This was suction filtered to elute the activated carbon adsorbate. This operation was repeated twice to obtain about 200 mL of an aqueous ethanol solution. When the solvent of this aqueous solution was distilled off and dried, 860 mg of a pale yellow powder was obtained. The chlorogenic acid contained therein was 344 mg (40 wt%), and when chlorogenic acids were included, a composition containing chlorogenic acids with a high content of 507 mg (59 wt%) was obtained. The caffeine content was 26 mg (3% by weight).
（実施例６）
実施例１で用いたクロロゲン酸含有量１９％のコーヒー生豆抽出物３ｇを蒸留水３０ｍＬに溶解し、顆粒状活性炭（二村化学社製太閤ＳＧ）５ｇを添加して真空脱気を３回繰り返しその後１時間撹拌した。その後活性炭を吸引濾過し、活性炭を約３００ｍＬの蒸留水でそのまま吸引洗浄した。この活性炭をビーカーに移し、５０ｍＬの６０容量％エタノール水溶液を加え、１０分間撹拌した。これを吸引濾過し、活性炭吸着物を溶出させた。この操作を３回繰り返し、１５０ｍＬのエタノール水溶液を得た。この水溶液を６０ｍＬの強酸性イオン交換カラム（アンバーライト２００ＣＴ）にＳＶ４で通液し、全量約２００ｍＬの処理液を得た。この処理液の溶媒を留去し、乾燥すると５９０ｍｇの白色粉末が得られた。これに含まれるクロロゲン酸は２４８ｍｇ（４２重量％）でクロロゲン酸類を含めると３９５ｍｇ（６７重量％）の含有量の高い純度でクロロゲン酸類を含む組成物が得られた。カフェインの含有は３ｍｇ（０．５重量％）と極めて低かった。
(Example 6)
3 g of raw coffee bean extract having a chlorogenic acid content of 19% used in Example 1 was dissolved in 30 mL of distilled water, 5 g of granular activated carbon (Taiko SG manufactured by Nimura Chemical Co., Ltd.) was added, and vacuum deaeration was repeated three times. The mixture was then stirred for 1 hour. Thereafter, the activated carbon was subjected to suction filtration, and the activated carbon was suction-washed with about 300 mL of distilled water. The activated carbon was transferred to a beaker, 50 mL of a 60 vol% ethanol aqueous solution was added, and the mixture was stirred for 10 minutes. This was suction filtered to elute the activated carbon adsorbate. This operation was repeated three times to obtain 150 mL of an aqueous ethanol solution. This aqueous solution was passed through a 60 mL strongly acidic ion exchange column (Amberlite 200CT) with SV4 to obtain a total treatment solution of about 200 mL. The solvent of this treatment solution was distilled off and dried to obtain 590 mg of white powder. The chlorogenic acid contained therein was 248 mg (42% by weight), and when chlorogenic acids were included, a composition containing chlorogenic acids with a high content of 395 mg (67% by weight) was obtained. The caffeine content was very low at 3 mg (0.5% by weight).
（実施例７）
粉砕したコーヒー生豆（アラビカ種）１５ｇを６０容量％エタノール水溶液５０ｍＬに添加し、５０℃で１時間撹拌抽出、固形物をろ別し、エタノール水抽出液を得た。さらに６０容量％エタノール水溶液５０ｍＬを用いてろ別した固形物から同様に抽出操作を行った後、あわせたエタノール水抽出液約１００ｍＬを約２０ｍＬまで減圧濃縮した。この濃縮抽出液に水を加え５０ｍＬとし、顆粒状活性炭（二村化学社製太閤ＳＧ）５ｇを添加してその後１時間撹拌した。その後活性炭を吸引濾過し、活性炭を約１５０ｍＬの蒸留水でそのまま吸引洗浄した。この活性炭をビーカーに移し、６０容量％エタノール水溶液５０ｍＬを加え、１０分間撹拌した。これを吸引濾過し、活性炭吸着物を溶出させた。この操作を２回繰り返し、約１００ｍＬのエタノール水溶液を得た。この水溶液を６０ｍＬの強酸性イオン交換カラム（アンバーライト２００ＣＴ）にＳＶ４で通液し、全量約１５０ｍＬの処理液を得た。この処理液の溶媒を留去し、乾燥すると３４５ｍｇの白色粉末が得られた。これに含まれるクロロゲン酸は１３１ｍｇ（３８重量％）でクロロゲン酸類を含めると１７９ｍｇ（５２重量％）の含有量を示すとともに、カフェインの含有は１ｍｇ（０．３重量％）と極めて低く、高い純度でクロロゲン酸類を含む組成物が得られた。
(Example 7)
15 g of crushed green coffee beans (Arabica seed) was added to 50 mL of a 60% by volume ethanol aqueous solution, stirred and extracted at 50 ° C. for 1 hour, and solids were separated by filtration to obtain an ethanol water extract. Furthermore, after performing extraction operation similarly from the solid substance filtered off using 50 mL of 60 volume% ethanol aqueous solution, about 100 mL of combined ethanol water extract was concentrate | evaporated under reduced pressure to about 20 mL. Water was added to this concentrated extract to make 50 mL, and 5 g of granular activated carbon (Nimura SG, Nimura Chemical Co., Ltd.) was added, followed by stirring for 1 hour. Thereafter, the activated carbon was subjected to suction filtration, and the activated carbon was suction-washed with about 150 mL of distilled water. This activated carbon was transferred to a beaker, and 50 mL of a 60% by volume ethanol aqueous solution was added, followed by stirring for 10 minutes. This was suction filtered to elute the activated carbon adsorbate. This operation was repeated twice to obtain about 100 mL of an aqueous ethanol solution. This aqueous solution was passed through a 60 mL strongly acidic ion exchange column (Amberlite 200CT) with SV4 to obtain a treatment solution of about 150 mL in total. The solvent of this treatment solution was distilled off and dried to obtain 345 mg of white powder. Chlorogenic acid contained in this is 131 mg (38% by weight), and when chlorogenic acids are included, it shows a content of 179 mg (52% by weight), and the content of caffeine is extremely low, 1 mg (0.3% by weight). A composition containing chlorogenic acids in purity was obtained.
本発明にかかる高濃度のクロロゲン酸類を含む組成物の製造方法で得られる組成物は、クロロゲン酸類を高濃度で含んでおり、抗酸化剤として食品添加物、化粧品および食品、健康食品などに広く用いられることが期待される。 The composition obtained by the method for producing a composition containing a high concentration of chlorogenic acids according to the present invention contains a high concentration of chlorogenic acids and is widely used as an antioxidant in food additives, cosmetics and foods, health foods and the like. Expected to be used.
Claims (4)
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