JPH06113872A - New manufacturing method of chlorophyll composition - Google Patents
New manufacturing method of chlorophyll compositionInfo
- Publication number
- JPH06113872A JPH06113872A JP4287096A JP28709692A JPH06113872A JP H06113872 A JPH06113872 A JP H06113872A JP 4287096 A JP4287096 A JP 4287096A JP 28709692 A JP28709692 A JP 28709692A JP H06113872 A JPH06113872 A JP H06113872A
- Authority
- JP
- Japan
- Prior art keywords
- chlorophyll
- compound
- present
- algae
- composition
- 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.)
- Granted
Links
Landscapes
- Coloring Foods And Improving Nutritive Qualities (AREA)
- Edible Seaweed (AREA)
- Meat, Egg Or Seafood Products (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
(57)【要約】
【構成】 褐藻類、緑藻類、紅藻類の中から選ばれる藻
類を塩蔵した後、クロロフィル類を抽出することを特徴
とするクロロフィル類組成物の新規製造法であり、抽出
されるクロロフィル類が一般式（Ａ）で表される化合物
（１）［一般式（Ａ）でＲ1 がＯＨ基、Ｒ2 がＣＯＯＣ
Ｈ3 基の場合］及び化合物（２）［一般式（Ａ）でＲ1
がＣＯＯＣＨ3 、Ｒ2 がＯＨ基の場合］を主成分として
含有する。
【化１】
【効果】 天然の藻類中の不安定なChl a を安定な化合
物（１）及び化合物（２）に変化させることが可能にな
り、且つ、それから該物質を抽出することによって、比
較的安定なクロロフィル類組成物が、従来の化学的合成
法による場合よりも遥かに経済的に提供され、天然系色
素であるクロロフィル類組成物の食品等各種用途向け緑
色色素としての使用が可能になる。(57) [Summary] [Structure] A novel method for producing a chlorophyll composition characterized by extracting chlorophyll after salting an alga selected from brown algae, green algae, and red algae. A compound (1) in which chlorophylls represented by the general formula (A) [in the general formula (A), R 1 is an OH group and R 2 is COOC.
H 3 group] and compound (2) [in the general formula (A), R 1
Is COOCH 3 and R 2 is an OH group] as a main component. [Chemical 1] [Effect] Unstable Chla in natural algae can be converted into stable compound (1) and compound (2), and by extracting the substance therefrom, relatively stable chlorophyll can be obtained. The similar composition is provided much more economically than the conventional chemical synthesis method, and the chlorophyll composition, which is a natural pigment, can be used as a green pigment for various applications such as foods.
Description
【０００１】[0001]
【０００２】本発明は、天然系緑色色素として有用なク
ロロフィル類組成物の新規製造法に関する。The present invention relates to a novel method for producing a chlorophyll composition which is useful as a natural green pigment.
【０００３】[0003]
【０００４】クロロフィル類はマグネシウムを含む緑色
色素として知られており、広く植物に含有されていて含
有量が最も多いのがクロロフィルａ（Chl a ということ
がある）であるが、この物質やその類縁体は光や温度、
化学物質等に対して極めて不安定なものが多く、更に、
水に対する溶解性も低いこと等から製造及びその利用に
困難を伴うとされてきた。Chlorophyll is known as a green pigment containing magnesium, and it is widely contained in plants, and the highest content is chlorophyll a (sometimes called Chla). Body is light and temperature,
Many are extremely unstable to chemical substances, etc.
It has been considered to be difficult to manufacture and use because of low solubility in water.
【０００５】実際に、マグネシウムに代えて銅を用いた
類縁体が一部のガム等の食品に使用されている他は、食
品向け色素としては殆ど実用化されていない。Actually, except that an analog using copper instead of magnesium is used in some foods such as gums, it has hardly been put into practical use as a dye for foods.
【０００６】一方、クロロフィル類の中の化合物（１）
［下記一般式（Ａ）でＲ1 がＯＨ基、Ｒ2 がＣＯＯＣＨ
3 基の場合］及び化合物（２）［下記一般式（Ａ）でＲ
1 がＣＯＯＣＨ3 、Ｒ2 がＯＨ基の場合］は比較的安定
であり、その化学合成法［Ｐ．Ｍ．Ｓｃｈａｂｅｒら、
ジャーナル・オブ・クロマトグラフィー（Ｊｏｕｒｎａ
ｌ ｏｆ Ｃｈｒｏｍａｔｏｇｒａｐｈｙ），３１６
（１９８４）ｐ２５］は知られているが、藻類からの発
見例や製造例は未だ報告されていない。On the other hand, the compound (1) among chlorophylls
[In the general formula (A) below, R 1 is an OH group and R 2 is COOCH.
In the case of 3 groups] and compound (2) [R in the following general formula (A)]
1 is COOCH 3 and R 2 is an OH group] is relatively stable, and its chemical synthesis method [P. M. Schaber et al.
Journal of Chromatography (Journa
l of Chromatography), 316
(1984) p25] is known, but no discovery example or production example from algae has been reported yet.
【０００７】[0007]
【化２】 [Chemical 2]
【０００８】つまり、天然系色素であるクロロフィル類
を食品向け緑色色素として実用化することが望まれてお
り、数多く知られているクロロフィル類の中でも、光や
化学物質に対する安定性及び水に対する溶解性の優れた
クロロフィル類が要望されていた。That is, it is desired to put chlorophylls, which are natural pigments, into practical use as green pigments for foods, and among many known chlorophylls, stability to light and chemical substances, and solubility to water. The excellent chlorophylls have been demanded.
【０００９】[0009]
【００１０】しかしながら、比較的安定な化合物（１）
や化合物（２）は天然物中に見い出されておらず、従来
の化学的合成法では、あまりにも高価になってしまい実
用性に難点が残るので、クロロフィル類を食品等の用途
の緑色色素として実用化するには、経済的な天然物原料
から優れた性質のクロロフィル類を製造する方法の開発
が課題とされていたのである。However, the relatively stable compound (1)
Neither compound nor compound (2) has been found in natural products, and conventional chemical synthesis methods are too expensive and have problems in practicality. Therefore, chlorophylls are used as green pigments for applications such as foods. In order to put it into practical use, the development of a method for producing chlorophylls having excellent properties from economical natural raw materials had been a challenge.
【００１１】[0011]
【００１２】本発明者等は、上記課題を解決するため
に、鋭意研究を重ねた結果、塩蔵したコンブ及びワカメ
中にChl a よりも安定性及び水に対する溶解性が優れた
クロロフィル類組成物、即ち化合物（１）及び化合物
（２）が多く生成することを発見し、その抽出、精製に
成功し、更に、各種藻類の処理条件及び抽出条件を検討
した結果、本発明を完成するに至った。The inventors of the present invention have conducted extensive studies in order to solve the above-mentioned problems, and as a result, a chlorophyll composition which is more stable and more soluble in water than Chla in salted kelp and seaweed, That is, it was discovered that a large amount of compound (1) and compound (2) were produced, the extraction and purification thereof were successful, and the treatment conditions and extraction conditions of various algae were examined. As a result, the present invention was completed. .
【００１３】以下に本発明の内容を詳細に説明する。The contents of the present invention will be described in detail below.
【００１４】即ち、第一の本発明は、褐藻類、緑藻類、
紅藻類の中から選ばれる藻類を塩蔵した後、クロロフィ
ル類を抽出することを特徴とするクロロフィル類組成物
の新規製造法である。That is, the first aspect of the present invention is to provide brown algae, green algae,
It is a novel method for producing a chlorophyll composition, which comprises extracting an chlorophyll after salting an alga selected from red algae.
【００１５】第二の本発明は、抽出されるクロロフィル
類が一般式（Ａ）で表される化合物（１）［一般式
（Ａ）でＲ1 がＯＨ基、Ｒ2 がＣＯＯＣＨ3 基の場合］
及び化合物（２）［一般式（Ａ）でＲ1 がＣＯＯＣＨ
3 、Ｒ2 がＯＨ基の場合］を主成分として含有する前記
第一記載のクロロフィル類組成物の新規製造法である。In the second aspect of the present invention, the chlorophylls to be extracted are compounds (1) represented by the general formula (A) [in the general formula (A), R 1 is an OH group and R 2 is a COOCH 3 group. ]
And compound (2) [in the general formula (A), R 1 is COOCH
3 , when R 2 is an OH group] as a main component.
【００１６】[0016]
【化３】 [Chemical 3]
【００１７】本発明の原料である藻類は、褐藻類、緑藻
類、紅藻類の中から選ばれるが、具体的に好ましい藻類
は、コンブ目（Laminariales）に属するマコンブ（Lami
naria japonica Areschoug）、ミツイシコンブ（Lamina
ria angustata Kjellman）、ナガコンブ（Laminaria an
gustata var. longissima Miyabe）、オニコンブ（Lami
naria diabolica Miyabe）等、アナメ属（Agarum）、ス
ジメ属（Costaria）、アラメ属（Eisenia ）、ワカメ属
（Undaria ）、ホンダワラ属（Sargassum ）、ヒジキ属
（Hijikia ）等に属する各種褐藻類、アオサ目（Ulvale
s ）に属するアナアオサ（Ulva pertusa）、ヒトエグサ
（Monostroma nitidum Wittrock ）、ヒロハノヒトエグ
サ（Monostroma Latissimum ）、エゾヒトエグサ（Mono
stroma angicava ）等の各種緑藻類、アサクサノリ（Po
rphyra tenera ）等のチノリモ属（Porphyridium）に属
する各種紅藻類が挙げられる。The algae used as the raw material of the present invention is selected from brown algae, green algae and red algae, and specifically preferred algae are mackerels (Lamiriales) belonging to the order Laminariales.
naria japonica Areschoug), Mitsuishikonbu (Lamina)
ria angustata Kjellman), Nagakonbu (Laminaria an)
gustata var. longissima Miyabe), onikonbu (Lami
naria diabolica Miyabe, etc., various brown algae belonging to the genus Agarum, the genus Costaria, the genus Eisenia, the genus Wakame, the genus Undaria, the genus Sargassum, the genus Hijikia, etc. (Ulvale
s), Ulva pertusa, Monostroma nitidum Wittrock, Monostroma Latissimum, and Ezohito
Stroma angicava) and other green algae, Asakusanori (Po
Rphyra tenera) and various red algae belonging to the genus Porphyridium.
【００１８】一方、ホウレンソウ等の野菜や各種牧草、
木の葉等の陸上植物を本発明に記載された方法で処理す
ることもできるが、それらは一般に、セルロースやヘミ
セルロース、リグニンを成分とする強固な膜の中にクロ
ロフィル類が存在するので、本発明に必須の操作の他に
充分な抽出率を得るための操作を追加することが必要な
場合が多い。On the other hand, vegetables such as spinach and various grasses,
Although land plants such as leaves can be treated by the method described in the present invention, they are generally present in the present invention because chlorophylls are present in a strong membrane composed of cellulose, hemicellulose, and lignin. It is often necessary to add an operation for obtaining a sufficient extraction rate in addition to the essential operation.
【００１９】前記各種藻類に含有されている天然色素
は、殆どがChl a を主成分とするものであり、仮にこの
ものを抽出したとしても極めて不安定であり、到底各種
用途の緑色色素として用いることができない。Most of the natural pigments contained in the various algae have Chla as a main component, and even if they are extracted, they are extremely unstable and are used as green pigments for various purposes. I can't.
【００２０】本発明を実施することにより得られる化合
物（１）及び化合物（２）は、それに較べて安定であ
り、本発明の工程の一部である塩蔵操作により初めて生
成する。The compounds (1) and (2) obtained by carrying out the present invention are comparatively stable, and are first produced by the salting operation which is a part of the process of the present invention.
【００２１】その塩蔵操作は、藻類の種類等によって条
件を加減する必要があるが、例えば、コンブを例に取る
と、陸揚げした藻類を５０〜１００℃程度の湯を用いて
短時間湯通しし、水洗した後、生の藻体１ｋｇに対して
１００〜５００ｇ程度の塩を加えて暗所、例えばタンク
等の中に好ましくは８時間〜３０日程度、更に好ましく
は２４時間〜７日程度貯蔵することによって実施され
る。For the salting operation, it is necessary to adjust the conditions depending on the type of algae. For example, taking kelp as an example, landed algae are boiled for a short time using hot water at about 50 to 100 ° C., After washing with water, 100 to 500 g of salt is added to 1 kg of raw algal cells and stored in a dark place, for example, a tank or the like, preferably for 8 hours to 30 days, more preferably for 24 hours to 7 days. It is carried out by
【００２２】本発明において、クロロフィル類組成物の
抽出に有利に用いられる有機溶剤としては、エタノー
ル、メタノール、アセトン、ヘキサン、ジエチルエーテ
ル、酢酸エチルエステル等が挙げられるが、抽出の効率
やクロロフィル類の収率、更には、精製する際に除去し
やすいことや人体に対する安全性が比較的高いこと等か
ら、中でも好ましい溶剤は、エタノール及びアセトンで
ある。In the present invention, examples of the organic solvent advantageously used for extracting the chlorophyll composition include ethanol, methanol, acetone, hexane, diethyl ether, acetic acid ethyl ester, and the like. Among them, ethanol and acetone are preferable solvents because of their yield, ease of removal during purification, and relatively high safety to the human body.
【００２３】本発明を実施する際の好ましい抽出温度
は、５〜６０℃、更に好ましくは１５〜３０℃であり、
好ましい抽出時間は１〜７２時間、更に好ましくは８〜
２４時間である。The preferred extraction temperature for carrying out the present invention is 5 to 60 ° C, more preferably 15 to 30 ° C.
The preferable extraction time is 1 to 72 hours, more preferably 8 to
24 hours.
【００２４】抽出温度が５℃未満の場合には抽出に時間
がかかったり抽出されるクロロフィル類の量が少なかっ
たりすることがあるので好ましくなく、６０℃を超える
場合には目的物であるクロロフィル類の構造が変化した
り分解することがあるので好ましくない。When the extraction temperature is lower than 5 ° C., it may take a long time to extract or the amount of chlorophylls extracted may be small, which is not preferable, and when it exceeds 60 ° C., the target chlorophylls may be obtained. It is not preferable because the structure of the may change or decompose.
【００２５】また、抽出時間が１時間未満の場合にはク
ロロフィル類が充分に抽出されないことが多いので好ま
しくなく、７２時間を超える場合には抽出時間を長くし
ても抽出されるクロロフィル類の量が殆ど増加しないの
で経済的に意味が無い。When the extraction time is less than 1 hour, chlorophylls are often not sufficiently extracted, which is not preferable. When the extraction time exceeds 72 hours, the amount of chlorophylls extracted even if the extraction time is lengthened. Is almost meaningless because it hardly increases.
【００２６】以上の操作の後、溶媒に溶けた状態でのク
ロロフィル類組成物を得ることができ、この物をそのま
ま各種用途に使用することも可能であるが、更に、公知
の方法、例えば、濃縮、乾燥等の操作で溶媒を除去した
後粉末状のクロロフィル類組成物とすることもできる。After the above operation, a chlorophyll composition in a state of being dissolved in a solvent can be obtained, and this composition can be used as it is for various purposes. Further, known methods such as, for example, The solvent may be removed by operations such as concentration and drying to obtain a powdery chlorophyll composition.
【００２７】また、必要に応じて、抽出により得られた
クロロフィル類組成物を、それ自体は公知の方法、例え
ばゼオライトやアルミナやシリカゲルを用いたクロマト
分離操作等によって更に精製することも可能である。If necessary, the chlorophyll composition obtained by extraction can be further purified by a method known per se, for example, a chromatographic separation operation using zeolite, alumina or silica gel. .
【００２８】その精製操作の際には、目的物の分解を避
ける意味から、できる限り加熱しないか又は加熱条件を
温和にすることが好ましく、使用する溶媒も、目的物の
溶解性が良好で、目的物の構造や性質に悪影響を与えな
い等の意味から、ヘキサン、アセトン、ジエチルエーテ
ル、酢酸エチルエステル、エタノール、メタノールから
選ばれる１種又は２種以上のものが好ましく、中でも最
も好ましいのはヘキサンとアセトンとの混合溶媒であ
る。During the purification operation, it is preferable not to heat or to moderate the heating condition as much as possible in order to avoid decomposition of the target substance. The solvent used also has good solubility of the target substance, One or two or more selected from hexane, acetone, diethyl ether, acetic acid ethyl ester, ethanol, and methanol are preferable because they do not adversely affect the structure and properties of the target substance, and most preferable are hexane. And a mixed solvent of acetone.
【００２９】以上に説明したように、本発明を実施する
ことにより、天然の藻類中の不安定なChl a を安定な化
合物（１）及び化合物（２）に変化させることが可能に
なり、且つ、それから該物質を抽出することによって、
比較的安定なクロロフィル類組成物が、従来の化学的合
成法による場合よりも遥かに経済的に提供される。As explained above, by carrying out the present invention, it becomes possible to change unstable Chla in natural algae into stable compounds (1) and (2), and , And then by extracting the substance,
Relatively stable chlorophyll compositions are provided much more economically than by conventional chemical synthetic methods.
【００３０】本発明により得られた緑色色素化合物
（１）及び化合物（２）並びにそれらの含有物であるク
ロロフィル類組成物は、液状、粉末、顆粒、成形物等の
何れの形態での製品化も自由であり、その用途にも格別
の制約は無い。The green pigment compound (1) and the compound (2) obtained by the present invention, and the chlorophyll composition containing them are commercialized in any form such as liquid, powder, granules and molded products. Is also free, and there are no particular restrictions on its use.
【００３１】用途の一例を挙げれば、コンブエキス、ダ
シの素、麺つゆ、ドレッシング、マヨネーズ、卓上甘味
料、みりん、等の調味料や甘味料、ガム、チョコレー
ト、ビスケット、クッキー、キャラメル、キャンデー、
煎餅、あられ、かりん糖、餅類、饅頭、求肥、羊羹、カ
ステラ、パン、パイ、シュークリーム、ドーナツ等の菓
子、アイスクリーム、シャーベット、アイスキャンデー
等の冷菓、ゼリー、ヨーグルト、プリン等の各種デザー
ト類、ハム、ソーセージ、カマボコ、ハンペン、チクワ
等の畜肉製品や水産練り製品やその原材料のすり身、ジ
ャム、マーマレード等の各種ジャム類、千枚漬、べった
ら漬等の各種漬物等の食品、ペットや家畜の各種飼料、
アイライン、マスカラ、マニキュア等の各種化粧品、マ
ウスウオッシュ、練り歯磨き、舌下錠、粉末胃薬等の各
種医薬品等がある。As examples of uses, seasonings and sweeteners such as kelp extract, dashi stock, noodle soup, dressing, mayonnaise, tabletop sweetener, mirin, gum, chocolate, biscuits, cookies, caramel, candy,
Rice crackers, hail, sugar, mochi, manju, fertilizer, yokan, castella, bread, pies, cream puffs, confections such as donuts, ice cream, sorbet, frozen desserts such as popsicles, jelly, yogurt, pudding and other desserts, Meat products such as ham, sausages, fish paste, hampen, chikuwa, and fish paste products and their raw materials such as surimi, jams, various jams such as marmalade, foods such as thousand pickles, and pickles, and various feeds for pets and livestock.
There are various cosmetics such as eyeliner, mascara and nail polish, mouthwash, toothpaste, sublingual tablets, various medicines such as powdered stomach medicine and the like.
【００３２】[0032]
【００３３】以下に、実施例を挙げて本発明の内容を更
に具体的に説明するが、本発明の範囲はこれらに限定さ
れるものではない。尚、例中の％は、特に断らない限り
重量％を表すものとする。Hereinafter, the contents of the present invention will be described more specifically with reference to examples, but the scope of the present invention is not limited to these. In the examples,% means% by weight unless otherwise specified.
【００３４】[0034]
【実施例−１】[Example-1]
【００３５】生コンブ（Laminaria japonica）（宮城県
唐桑産、平成４年５月採取）４００ｇに１４０ｇの粉砕
塩を満遍無く加えて、６日間１５℃の暗所に塩蔵した。
塩蔵後、３００ｇのコンブを取り出し、６００ｍｌのエ
タノールを加えて１分間洗浄した。次に、洗浄液を捨
て、再度６００ｍｌのクロロフィル類抽出のためのエタ
ノールを加えてコンブを浸漬し、２４時間室温で暗所に
置いて抽出し、コンブを取り出し、抽出した液を０．４
５μｍのメンブランフィルターで濾過し、クロロフィル
類組成物を含有したエタノール溶液を得た。更に、ろ液
を軽い減圧下で濃縮してエタノールを除去し、０．８１
ｇのクロロフィル類組成物−１を得た。To 400 g of raw kelp (Laminaria japonica) (produced in Karakuwa, Miyagi Prefecture, collected in May 1992), 140 g of crushed salt was uniformly added, and the mixture was salted in a dark place at 15 ° C. for 6 days.
After salting, 300 g of kelp was taken out, 600 ml of ethanol was added, and the mixture was washed for 1 minute. Next, the washing solution was discarded, 600 ml of ethanol for extracting chlorophylls was added again to immerse the kelp, and the kelp was extracted in a dark place at room temperature for 24 hours.
The mixture was filtered through a 5 μm membrane filter to obtain an ethanol solution containing the chlorophyll composition. Further, the filtrate was concentrated under a light reduced pressure to remove ethanol, and
g of chlorophyll composition-1 was obtained.
【００３６】[0036]
【実施例−２】[Example-2]
【００３７】実施例−１で抽出操作をした後取り出した
コンブに３００ｍｌのエタノールを加え、実施例−１と
同様に抽出、濾過、濃縮して０．２２ｇのクロロフィル
類組成物−２を得た。300 ml of ethanol was added to the kelp extracted after the extraction operation in Example-1, and extraction, filtration and concentration were carried out in the same manner as in Example-1 to obtain 0.22 g of chlorophyll composition-2. .
【００３８】[0038]
【実施例−３】[Example-3]
【００３９】実施例−１で用いたコンブに代えて、生ワ
カメ［Undaria pinnatifida (Harvey) Suringar］（韓
国産、平成４年５月採取）を用いた他は、実施例−１と
同一の操作を行い、２．０７１７ｇのクロロフィル類組
成物−３を得た。The same procedure as in Example-1 except that raw seaweed [Undaria pinnatifida (Harvey) Suringar] (produced in Korea, collected in May 1992) was used in place of the kelp used in Example-1. Then, 2.0717 g of a chlorophyll composition-3 was obtained.
【００４０】[0040]
【実施例−４】[Example-4]
【００４１】実施例−３で抽出操作をした後取り出した
ワカメに３００ｍｌのエタノールを加え、実施例−３と
同様に抽出、濾過、濃縮して０．２４１８ｇのクロロフ
ィル類組成物−４を得た。クロロフィル類組成物−３及
び４を合わせ、組成比をＨＰＬＣで確認したところ、化
合物（１）：化合物（２）＝４２．９：１０．１であっ
た。300 ml of ethanol was added to the wakame seaweed that had been extracted in Example 3 and extracted, filtered and concentrated in the same manner as in Example 3 to obtain 0.2418 g of a chlorophyll composition-4. . When the composition ratios of the chlorophyll compositions 3 and 4 were combined and confirmed by HPLC, the result was that compound (1): compound (2) = 42.9: 10.1.
【００４２】[0042]
【実施例−５】[Example-5]
【００４３】実施例−１及び実施例−２でそれぞれ得た
ものを合わせ、１．０３ｇのクロロフィル類組成物と
し、その組成比をＨＰＬＣで確認したところ、化合物
（１）：化合物（２）＝４８．５：２６．９であった。
この組成物を、ヘキサン：アセトン＝３：１の混合溶媒
を用いて１６０ｇのシリカゲルカラムに通して精製し、
７３．２ｍｇのクロロフィル類組成物−５を得た。The compositions obtained in Example-1 and Example-2 were combined to obtain 1.03 g of a chlorophyll composition, and the composition ratio was confirmed by HPLC. As a result, compound (1): compound (2) = It was 48.5: 26.9.
The composition was purified by passing through a 160 g silica gel column using a mixed solvent of hexane: acetone = 3: 1,
73.2 mg of chlorophyll composition-5 was obtained.
【００４４】[0044]
【実施例−６】[Example-6]
【００４５】実施例−５で得られたクロロフィル類組成
物−５の一部を用いて、ＨＰＬＣの分取カラム（Senshu
pak Silica-5301-N、０℃、ヘキサン：イソプロパノー
ル：メタノール＝１００：０．８：０．４、５ｍｌ／ｍ
ｉｎ．、４２５ｎｍ）により分離精製し、クロロフィル
類組成物、即ち、化合物（１）と化合物（２）とをそれ
ぞれ得た。A part of the chlorophyll composition-5 obtained in Example-5 was used to prepare an HPLC preparative column (Senshu).
pak Silica-5301-N, 0 ° C., hexane: isopropanol: methanol = 100: 0.8: 0.4, 5 ml / m
in. 425 nm) to separate and purify the chlorophyll composition, that is, the compound (1) and the compound (2), respectively.
【００４６】[0046]
【比較例−１】[Comparative Example-1]
【００４７】化学合成法［Ｐ．Ｍ．Ｓｃｈａｂｅｒら、
ジャーナル・オブ・クロマトグラフィー（Ｊｏｕｒｎａ
ｌ ｏｆ Ｃｈｒｏｍａｔｏｇｒａｐｈｙ），３１６
（１９８４）ｐ２５］により１０位をＯＨ化したクロロ
フィルａ’及び１０位をＯＨ化したクロロフィルａを調
製し、この物を対照品とした。Chemical synthesis method [P. M. Schaber et al.
Journal of Chromatography (Journa
l of Chromatography), 316
(1984) p25], chlorophyll a ′ having the 10-position OH and chlorophyll a having the 10-position OH were prepared and used as control products.
【００４８】[0048]
【確認試験−１】[Confirmation test-1]
【００４９】比較例−１で得た対照品と実施例−６で得
た本発明に係るクロロフィル類組成物とのＨＰＬＣ（Ne
opak 120-5SI、０℃、ヘキサン：イソプロパノール：メ
タノール＝１００：０．８：０．４、１．２ｍｌ／ｍｉ
ｎ．、 ４２５ｎｍ）の溶出スペクトルを比較した結果、
両者の溶出スペクトルは一致した。HPLC (Ne of the control product obtained in Comparative Example-1 and the chlorophyll composition according to the present invention obtained in Example-6)
opak 120-5SI, 0 ° C., hexane: isopropanol: methanol = 100: 0.8: 0.4, 1.2 ml / mi
n. , 425 nm) as a result of comparison of elution spectra,
Both elution spectra were in agreement.
【００５０】[0050]
【確認試験−２】[Confirmation test-2]
【００５１】比較例−１で得た対照品（１０位がＯＨ化
されたクロロフィルａ′，１０位がＯＨ化されたクロロ
フィルａ）と、実施例−６で得た本発明に係るクロロフ
ィル類組成物［化合物（１），化合物（２）］との可視
光線の吸収スペクトルを、それぞれ常法で測定した。得
られた結果について、図１に、本発明に係る化合物
（１）及び対照品であるクロロフィルａ’の可視光線の
吸収スペクトルを示す。また、図２に、本発明に係る化
合物（２）及び対照品であるクロロフィルａの可視光線
の吸収スペクトルを示す。得られた結果から、対照品の
構造と実施例−６で得られた本発明に係るクロロフィル
類組成物の構造とに相違が無いことが支持される。な
お、図１，図２中、本発明に係る化合物（１）及び化合
物（２）は実線で示し、対照品であるクロロフィルａ及
びクロロフィルａ′は点線で示したが、ほぼ同一の線と
なっている。The control product obtained in Comparative Example-1 (chlorophyll a'in which 10-position is OH, chlorophyll a in which 10-position is OH) and the composition of chlorophyll according to the present invention obtained in Example-6 The visible light absorption spectra of the compound [compound (1), compound (2)] were measured by a conventional method. Regarding the obtained results, FIG. 1 shows visible light absorption spectra of the compound (1) according to the present invention and chlorophyll a ′ as a control product. Further, FIG. 2 shows absorption spectra of visible light of the compound (2) of the present invention and chlorophyll a which is a control product. The obtained results support that there is no difference between the structure of the control product and the structure of the chlorophyll composition according to the present invention obtained in Example-6. 1 and 2, the compound (1) and the compound (2) according to the present invention are shown by solid lines, and the chlorophyll a and chlorophyll a'which are the control products are shown by dotted lines, but they are almost the same line. ing.
【００５２】[0052]
【確認試験−３】[Confirmation test-3]
【００５３】比較例−１で得た対照品（１０位がＯＨ化
されたクロロフィルａ′，１０位がＯＨ化されたクロロ
フィルａ）と、実施例−６で得た本発明に係るクロロフ
ィル類組成物［化合物（１），化合物（２）］との常法
によるＣＤ（円偏光２色性）スペクトルを、それぞれ測
定した。得られた結果について、図３に、本発明に係る
化合物（１）及び化合物（２）のＣＤスペクトルを示
す。また、図４に、対照品であるクロロフィルａ′及び
クロロフィルａのＣＤスペクトルを示す。得られた結果
から、対照品の構造と実施例−６で得られた本発明に係
るクロロフィル類組成物の構造とに相違が無いことが支
持される。The control product obtained in Comparative Example-1 (chlorophyll a'where the 10th position was OH, chlorophyll a where the 10th position was OH) and the chlorophyll composition according to the present invention obtained in Example-6 The CD (circular dichroism) spectra of the product [compound (1), compound (2)] were measured by a conventional method. Regarding the obtained results, FIG. 3 shows the CD spectra of the compound (1) and the compound (2) according to the present invention. Further, FIG. 4 shows the CD spectra of chlorophyll a ′ and chlorophyll a which are the control products. The obtained results support that there is no difference between the structure of the control product and the structure of the chlorophyll composition according to the present invention obtained in Example-6.
【００５４】[0054]
【確認試験−４】[Confirmation test-4]
【００５５】比較例−１で得た対照品中の１０位をＯＨ
化したクロロフィルａと、実施例−６で得た本発明に係
るクロロフィル類組成物の中の化合物（２）との13Ｃ−
ＮＭＲ（核磁気共鳴）スペクトルを、それぞれ測定し
た。得られた結果について、図５に、本発明に係る化合
物（２）の13Ｃ−ＮＭＲスペクトルを示す。また、図６
に、対照品であるクロロフィルａの13Ｃ−ＮＭＲスペク
トルを示す。得られた結果から、対照品の構造と実施例
−６で得られた本発明に係るクロロフィル類の構造とに
相違が無いことが支持される。The 10th position in the control product obtained in Comparative Example-1 was OH.
13 C-of the converted chlorophyll a and the compound (2) in the chlorophyll composition according to the present invention obtained in Example-6
The NMR (nuclear magnetic resonance) spectra were measured respectively. Regarding the obtained results, FIG. 5 shows the 13 C-NMR spectrum of the compound (2) according to the present invention. In addition, FIG.
The 13 C-NMR spectrum of chlorophyll a which is a control product is shown in FIG. The obtained results support that there is no difference between the structure of the control product and the structure of the chlorophylls according to the present invention obtained in Example-6.
【００５６】[0056]
【００５７】濃度が４．７×１０-5モル／ｌになるよう
に、実施例−６で得た本発明に係る化合物（１）及び比
較例−１で得た対照品中の１０位をＯＨ化したクロロフ
ィルａを、それぞれエタノールに溶解した。各溶液１０
ｍｌをそれぞれ５０ｍｌの三角フラスコに入れ、パラフ
ィルムで密閉し、２５℃で暗所に置いた。また、各溶液
１０ｍｌを同様に用意して２５℃で２０００ルックスの
明所に置いた。各試料について、エタノール中に於ける
光安定性の経時変化を、可視光線の吸収スペクトルの赤
色帯（Ｒｅｄ ｂａｎｄ）での減少率で測定した。得ら
れた結果について、図７に、本発明に係る化合物（１）
及び対照品であるクロロフィルａの赤色帯での光吸収率
と保存時間との関係を示す。図７に示された結果から、
暗所の場合、２０００ルックスの明所の場合共に、化合
物（１）のほうが、クロロフィルａよりも顕著に安定で
あることが判る。特に、化合物（１）は、暗所で保管し
た場合には、クロロフィルａよりも遥かに安定であるこ
とが判る。The 10th position in the compound (1) according to the present invention obtained in Example 6 and the 10th position in the control product obtained in Comparative Example-1 was adjusted so that the concentration became 4.7 × 10 -5 mol / l. The OH-modified chlorophyll a was dissolved in ethanol. Each solution 10
Each ml was placed in a 50 ml Erlenmeyer flask, sealed with parafilm, and placed in the dark at 25 ° C. In addition, 10 ml of each solution was prepared in the same manner and placed at a light of 2000 lux at 25 ° C. For each sample, the change with time in photostability in ethanol was measured by the rate of decrease in the absorption band of visible light in the red band. Regarding the obtained results, FIG. 7 shows the compound (1) according to the present invention.
3 shows the relationship between the light absorption rate of chlorophyll a, which is a control product, and the storage time in the red band. From the results shown in FIG.
It can be seen that the compound (1) is significantly more stable than chlorophyll a both in the dark and in the light of 2000 lux. In particular, it can be seen that the compound (1) is much more stable than chlorophyll a when stored in the dark.
【００５８】[0058]
【００５９】以上に説明したように、本発明を実施する
ことにより、天然の藻類中の不安定なChl a を安定な化
合物（１）及び化合物（２）に変化させることが可能に
なり、且つ、それから該物質を抽出することによって、
比較的安定なクロロフィル類組成物が、従来の化学的合
成法による場合よりも遥かに経済的に提供される。つま
り、本発明により、天然系色素であるクロロフィル類組
成物の食品等各種用途向け緑色色素としての使用が可能
になる。As described above, by carrying out the present invention, it becomes possible to change unstable Chla in natural algae into stable compounds (1) and (2), and , And then by extracting the substance,
Relatively stable chlorophyll compositions are provided much more economically than by conventional chemical synthetic methods. That is, according to the present invention, it becomes possible to use the chlorophyll composition which is a natural pigment as a green pigment for various applications such as foods.
【図１】本発明に係る化合物（１）及び対照品であるク
ロロフィルａ’の可視光線の吸収スペクトルを示す図FIG. 1 is a diagram showing visible light absorption spectra of compound (1) according to the present invention and chlorophyll a ′ as a control product.
【図２】本発明に係る化合物（２）及び対照品であるク
ロロフィルａの可視光線の吸収スペクトルを示す図FIG. 2 is a diagram showing visible light absorption spectra of compound (2) according to the present invention and chlorophyll a as a control product.
【図３】本発明に係る化合物（１）及び化合物（２）の
ＣＤスペクトルを示す図FIG. 3 is a diagram showing CD spectra of compound (1) and compound (2) according to the present invention.
【図４】対照品であるクロロフィルａ′及びクロロフィ
ルａのＣＤスペクトルを示す図FIG. 4 is a diagram showing CD spectra of chlorophyll a ′ and chlorophyll a which are control products.
【図５】本発明に係る化合物（２）の13Ｃ−ＮＭＲスペ
クトルを示す図FIG. 5 is a diagram showing a 13 C-NMR spectrum of a compound (2) according to the present invention.
【図６】対照品であるクロロフィルａの13Ｃ−ＮＭＲス
ペクトルを示す図FIG. 6 is a diagram showing a 13 C-NMR spectrum of chlorophyll a which is a control product.
【図７】本発明に係る化合物（１）及び対照品であるク
ロロフィルａの赤色帯での光吸収率と保存時間との関係
を示す図FIG. 7 is a graph showing the relationship between the light absorption rate of the compound (1) according to the present invention and the control product, chlorophyll a, in the red band and the storage time.
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成４年１１月１８日[Submission date] November 18, 1992
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】全文[Correction target item name] Full text
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【書類名】 明細書[Document name] Statement
【発明の名称】 クロロフィル類組成物の新規製造法Title: New method for producing chlorophyll composition
【特許請求の範囲】[Claims]
【化１】 [Chemical 1]
【発明の詳細な説明】Detailed Description of the Invention
【０００１】[0001]
【産業上の利用分野】[Industrial applications]
【０００２】本発明は、天然系緑色色素として有用なク
ロロフィル類組成物の新規製造法に関する。The present invention relates to a novel method for producing a chlorophyll composition which is useful as a natural green pigment.
【０００３】[0003]
【従来の技術】[Prior art]
【０００４】クロロフィル類はマグネシウムを含む緑色
色素として知られており、広く植物に含有されていて含
有量が最も多いのがクロロフィルａ（Chl a ということ
がある）であるが、この物質やその類縁体は光や温度、
化学物質等に対して極めて不安定なものが多く、更に、
水に対する溶解性も低いこと等から製造及びその利用に
困難を伴うとされてきた。Chlorophyll is known as a green pigment containing magnesium, and it is widely contained in plants, and the highest content is chlorophyll a (sometimes called Chla). Body is light and temperature,
Many are extremely unstable to chemical substances, etc.
It has been considered to be difficult to manufacture and use because of low solubility in water.
【０００５】実際に、マグネシウムに代えて銅を用いた
類縁体が一部のガム等の食品に使用されている他は、食
品向け色素としては殆ど実用化されていない。Actually, except that an analog using copper instead of magnesium is used in some foods such as gums, it has hardly been put into practical use as a dye for foods.
【０００６】一方、クロロフィル類の中の化合物（１）
［下記一般式（Ａ）でＲ1 がＯＨ基、Ｒ2 がＣＯＯＣＨ
3 基の場合］及び化合物（２）［下記一般式（Ａ）でＲ
1 がＣＯＯＣＨ3 、Ｒ2 がＯＨ基の場合］は比較的安定
であり、その化学合成法［Ｐ．Ｍ．Ｓｃｈａｂｅｒら、
ジャーナル・オブ・クロマトグラフィー（Ｊｏｕｒｎａ
ｌ ｏｆ Ｃｈｒｏｍａｔｏｇｒａｐｈｙ），３１６
（１９８４）ｐ２５］は知られているが、藻類からの発
見例や製造例は未だ報告されていない。On the other hand, the compound (1) among chlorophylls
[In the general formula (A) below, R 1 is an OH group and R 2 is COOCH.
In the case of 3 groups] and compound (2) [R in the following general formula (A)]
1 is COOCH 3 and R 2 is an OH group] is relatively stable, and its chemical synthesis method [P. M. Schaber et al.
Journal of Chromatography (Journa
l of Chromatography), 316
(1984) p25] is known, but no discovery example or production example from algae has been reported yet.
【０００７】[0007]
【化２】 [Chemical 2]
【０００８】つまり、天然系色素であるクロロフィル類
を食品向け緑色色素として実用化することが望まれてお
り、数多く知られているクロロフィル類の中でも、光や
化学物質に対する安定性及び水に対する溶解性の優れた
クロロフィル類が要望されていた。That is, it is desired to put chlorophylls, which are natural pigments, into practical use as green pigments for foods, and among many known chlorophylls, stability to light and chemical substances, and solubility to water. The excellent chlorophylls have been demanded.
【０００９】[0009]
【発明が解決しようとする課題】[Problems to be Solved by the Invention]
【００１０】しかしながら、比較的安定な化合物（１）
や化合物（２）は天然物中に見い出されておらず、従来
の化学的合成法では、あまりにも高価になってしまい実
用性に難点が残るので、クロロフィル類を食品等の用途
の緑色色素として実用化するには、経済的な天然物原料
から優れた性質のクロロフィル類を製造する方法の開発
が課題とされていたのである。However, the relatively stable compound (1)
Neither compound nor compound (2) has been found in natural products, and conventional chemical synthesis methods are too expensive and have problems in practicality. Therefore, chlorophylls are used as green pigments for applications such as foods. In order to put it into practical use, the development of a method for producing chlorophylls having excellent properties from economical natural raw materials had been a challenge.
【００１１】[0011]
【課題を解決するための手段】[Means for Solving the Problems]
【００１２】本発明者等は、上記課題を解決するため
に、鋭意研究を重ねた結果、塩蔵したコンブ及びワカメ
中にChl a よりも安定性及び水に対する溶解性が優れた
クロロフィル類組成物、即ち化合物（１）及び化合物
（２）が多く生成することを発見し、その抽出、精製に
成功し、更に、各種藻類の処理条件及び抽出条件を検討
した結果、本発明を完成するに至った。The inventors of the present invention have conducted extensive studies in order to solve the above-mentioned problems, and as a result, a chlorophyll composition which is more stable and more soluble in water than Chla in salted kelp and seaweed, That is, it was discovered that a large amount of compound (1) and compound (2) were produced, the extraction and purification thereof were successful, and the treatment conditions and extraction conditions of various algae were examined. As a result, the present invention was completed. .
【００１３】以下に本発明の内容を詳細に説明する。The contents of the present invention will be described in detail below.
【００１４】即ち、第一の本発明は、褐藻類、緑藻類、
紅藻類の中から選ばれる藻類を塩蔵した後、クロロフィ
ル類を抽出することを特徴とするクロロフィル類組成物
の新規製造法である。That is, the first aspect of the present invention is to provide brown algae, green algae,
It is a novel method for producing a chlorophyll composition, which comprises extracting an chlorophyll after salting an alga selected from red algae.
【００１５】第二の本発明は、抽出されるクロロフィル
類が一般式（Ａ）で表される化合物（１）［一般式
（Ａ）でＲ1 がＯＨ基、Ｒ2 がＣＯＯＣＨ3 基の場合］
及び化合物（２）［一般式（Ａ）でＲ1 がＣＯＯＣＨ
3 、Ｒ2 がＯＨ基の場合］を主成分として含有する前記
第一記載のクロロフィル類組成物の新規製造法である。In the second aspect of the present invention, the chlorophylls to be extracted are compounds (1) represented by the general formula (A) [in the general formula (A), R 1 is an OH group and R 2 is a COOCH 3 group. ]
And compound (2) [in the general formula (A), R 1 is COOCH
3 , when R 2 is an OH group] as a main component.
【００１６】[0016]
【化３】 [Chemical 3]
【００１７】本発明の原料である藻類は、褐藻類、緑藻
類、紅藻類の中から選ばれるが、具体的に好ましい藻類
は、コンブ目（Laminariales）に属するマコンブ（Lami
naria japonica Areschoug）、ミツイシコンブ（Lamina
ria angustata Kjellman）、ナガコンブ（Laminaria an
gustata var. longissima Miyabe）、オニコンブ（Lami
naria diabolica Miyabe）等、アナメ属（Agarum）、ス
ジメ属（Costaria）、アラメ属（Eisenia ）、ワカメ属
（Undaria ）、ホンダワラ属（Sargassum ）、ヒジキ属
（Hijikia ）等に属する各種褐藻類、アオサ目（Ulvale
s ）に属するアナアオサ（Ulva pertusa）、ヒトエグサ
（Monostroma nitidum Wittrock ）、ヒロハノヒトエグ
サ（Monostroma Latissimum ）、エゾヒトエグサ（Mono
stroma angicava ）等の各種緑藻類、アサクサノリ（Po
rphyra tenera ）等のチノリモ属（Porphyridium）に属
する各種紅藻類が挙げられる。The algae used as the raw material of the present invention is selected from brown algae, green algae and red algae, and specifically preferred algae are mackerels (Lamiriales) belonging to the order Laminariales.
naria japonica Areschoug), Mitsuishikonbu (Lamina)
ria angustata Kjellman), Nagakonbu (Laminaria an)
gustata var. longissima Miyabe), onikonbu (Lami
naria diabolica Miyabe, etc., various brown algae belonging to the genus Agarum, the genus Costaria, the genus Eisenia, the genus Wakame, the genus Undaria, the genus Sargassum, the genus Hijikia, etc. (Ulvale
s), Ulva pertusa, Monostroma nitidum Wittrock, Monostroma Latissimum, and Ezohito
Stroma angicava) and other green algae, Asakusanori (Po
Rphyra tenera) and various red algae belonging to the genus Porphyridium.
【００１８】一方、ホウレンソウ等の野菜や各種牧草、
木の葉等の陸上植物を本発明に記載された方法で処理す
ることもできるが、それらは一般に、セルロースやヘミ
セルロース、リグニンを成分とする強固な膜の中にクロ
ロフィル類が存在するので、本発明に必須の操作の他に
充分な抽出率を得るための操作を追加することが必要な
場合が多い。On the other hand, vegetables such as spinach and various grasses,
Although land plants such as leaves can be treated by the method described in the present invention, they are generally present in the present invention because chlorophylls are present in a strong membrane composed of cellulose, hemicellulose, and lignin. It is often necessary to add an operation for obtaining a sufficient extraction rate in addition to the essential operation.
【００１９】前記各種藻類に含有されている天然色素
は、殆どがChl a を主成分とするものであり、仮にこの
ものを抽出したとしても極めて不安定であり、到底各種
用途の緑色色素として用いることができない。Most of the natural pigments contained in the various algae have Chla as a main component, and even if they are extracted, they are extremely unstable and are used as green pigments for various purposes. I can't.
【００２０】本発明を実施することにより得られる化合
物（１）及び化合物（２）は、それに較べて安定であ
り、本発明の工程の一部である塩蔵操作により初めて生
成する。The compounds (1) and (2) obtained by carrying out the present invention are comparatively stable, and are first produced by the salting operation which is a part of the process of the present invention.
【００２１】その塩蔵操作は、藻類の種類等によって条
件を加減する必要があるが、例えば、コンブを例に取る
と、陸揚げした藻類を５０〜１００℃程度の湯を用いて
短時間湯通しし、水洗した後、生の藻体１ｋｇに対して
１００〜５００ｇ程度の塩を加えて暗所、例えばタンク
等の中に好ましくは８時間〜３０日程度、更に好ましく
は２４時間〜７日程度貯蔵することによって実施され
る。For the salting operation, it is necessary to adjust the conditions depending on the type of algae. For example, taking kelp as an example, landed algae are boiled for a short time using hot water at about 50 to 100 ° C., After washing with water, 100 to 500 g of salt is added to 1 kg of raw algal cells and stored in a dark place, for example, a tank or the like, preferably for 8 hours to 30 days, more preferably for 24 hours to 7 days. It is carried out by
【００２２】本発明において、クロロフィル類組成物の
抽出に有利に用いられる有機溶剤としては、エタノー
ル、メタノール、アセトン、ヘキサン、ジエチルエーテ
ル、酢酸エチルエステル等が挙げられるが、抽出の効率
やクロロフィル類の収率、更には、精製する際に除去し
やすいことや人体に対する安全性が比較的高いこと等か
ら、中でも好ましい溶剤は、エタノール及びアセトンで
ある。In the present invention, examples of the organic solvent advantageously used for extracting the chlorophyll composition include ethanol, methanol, acetone, hexane, diethyl ether, acetic acid ethyl ester, and the like. Among them, ethanol and acetone are preferable solvents because of their yield, ease of removal during purification, and relatively high safety to the human body.
【００２３】本発明を実施する際の好ましい抽出温度
は、５〜６０℃、更に好ましくは１５〜３０℃であり、
好ましい抽出時間は１〜７２時間、更に好ましくは８〜
２４時間である。The preferred extraction temperature for carrying out the present invention is 5 to 60 ° C, more preferably 15 to 30 ° C.
The preferable extraction time is 1 to 72 hours, more preferably 8 to
24 hours.
【００２４】抽出温度が５℃未満の場合には抽出に時間
がかかったり抽出されるクロロフィル類の量が少なかっ
たりすることがあるので好ましくなく、６０℃を超える
場合には目的物であるクロロフィル類の構造が変化した
り分解することがあるので好ましくない。When the extraction temperature is lower than 5 ° C., it may take a long time to extract or the amount of chlorophylls extracted may be small, which is not preferable, and when it exceeds 60 ° C., the target chlorophylls may be obtained. It is not preferable because the structure of the may change or decompose.
【００２５】また、抽出時間が１時間未満の場合にはク
ロロフィル類が充分に抽出されないことが多いので好ま
しくなく、７２時間を超える場合には抽出時間を長くし
ても抽出されるクロロフィル類の量が殆ど増加しないの
で経済的に意味が無い。When the extraction time is less than 1 hour, chlorophylls are often not sufficiently extracted, which is not preferable. When the extraction time exceeds 72 hours, the amount of chlorophylls extracted even if the extraction time is lengthened. Is almost meaningless because it hardly increases.
【００２６】以上の操作の後、溶媒に溶けた状態でのク
ロロフィル類組成物を得ることができ、この物をそのま
ま各種用途に使用することも可能であるが、更に、公知
の方法、例えば、濃縮、乾燥等の操作で溶媒を除去した
後粉末状のクロロフィル類組成物とすることもできる。After the above operation, a chlorophyll composition in a state of being dissolved in a solvent can be obtained, and this composition can be used as it is for various purposes. Further, known methods such as, for example, The solvent may be removed by operations such as concentration and drying to obtain a powdery chlorophyll composition.
【００２７】また、必要に応じて、抽出により得られた
クロロフィル類組成物を、それ自体は公知の方法、例え
ばゼオライトやアルミナやシリカゲルを用いたクロマト
分離操作等によって更に精製することも可能である。If necessary, the chlorophyll composition obtained by extraction can be further purified by a method known per se, for example, a chromatographic separation operation using zeolite, alumina or silica gel. .
【００２８】その精製操作の際には、目的物の分解を避
ける意味から、できる限り加熱しないか又は加熱条件を
温和にすることが好ましく、使用する溶媒も、目的物の
溶解性が良好で、目的物の構造や性質に悪影響を与えな
い等の意味から、ヘキサン、アセトン、ジエチルエーテ
ル、酢酸エチルエステル、エタノール、メタノールから
選ばれる１種又は２種以上のものが好ましく、中でも最
も好ましいのはヘキサンとアセトンとの混合溶媒であ
る。During the purification operation, it is preferable not to heat or to moderate the heating condition as much as possible in order to avoid decomposition of the target substance. The solvent used also has good solubility of the target substance, One or two or more selected from hexane, acetone, diethyl ether, acetic acid ethyl ester, ethanol, and methanol are preferable because they do not adversely affect the structure and properties of the target substance, and most preferable are hexane. And a mixed solvent of acetone.
【００２９】以上に説明したように、本発明を実施する
ことにより、天然の藻類中の不安定なChl a を安定な化
合物（１）及び化合物（２）に変化させることが可能に
なり、且つ、それから該物質を抽出することによって、
比較的安定なクロロフィル類組成物が、従来の化学的合
成法による場合よりも遥かに経済的に提供される。As explained above, by carrying out the present invention, it becomes possible to change unstable Chla in natural algae into stable compounds (1) and (2), and , And then by extracting the substance,
Relatively stable chlorophyll compositions are provided much more economically than by conventional chemical synthetic methods.
【００３０】本発明により得られた緑色色素化合物
（１）及び化合物（２）並びにそれらの含有物であるク
ロロフィル類組成物は、液状、粉末、顆粒、成形物等の
何れの形態での製品化も自由であり、その用途にも格別
の制約は無い。The green pigment compound (1) and the compound (2) obtained by the present invention, and the chlorophyll composition containing them are commercialized in any form such as liquid, powder, granules and molded products. Is also free, and there are no particular restrictions on its use.
【００３１】用途の一例を挙げれば、コンブエキス、ダ
シの素、麺つゆ、ドレッシング、マヨネーズ、卓上甘味
料、みりん、等の調味料や甘味料、ガム、チョコレー
ト、ビスケット、クッキー、キャラメル、キャンデー、
煎餅、あられ、かりん糖、餅類、饅頭、求肥、羊羹、カ
ステラ、パン、パイ、シュークリーム、ドーナツ等の菓
子、アイスクリーム、シャーベット、アイスキャンデー
等の冷菓、ゼリー、ヨーグルト、プリン等の各種デザー
ト類、ハム、ソーセージ、カマボコ、ハンペン、チクワ
等の畜肉製品や水産練り製品やその原材料のすり身、ジ
ャム、マーマレード等の各種ジャム類、千枚漬、べった
ら漬等の各種漬物等の食品、ペットや家畜の各種飼料、
アイライン、マスカラ、マニキュア等の各種化粧品、マ
ウスウオッシュ、練り歯磨き、舌下錠、粉末胃薬等の各
種医薬品等がある。As examples of uses, seasonings and sweeteners such as kelp extract, dashi stock, noodle soup, dressing, mayonnaise, tabletop sweetener, mirin, gum, chocolate, biscuits, cookies, caramel, candy,
Rice crackers, hail, sugar, mochi, manju, fertilizer, yokan, castella, bread, pies, cream puffs, confections such as donuts, ice cream, sorbet, frozen desserts such as popsicles, jelly, yogurt, pudding and other desserts, Meat products such as ham, sausage, fish paste, hampen, chikuwa, and fish paste products and their raw materials such as surimi, jams, various jams such as marmalade, foods such as thousand pickles, and pickles, and various feeds for pets and livestock,
There are various cosmetics such as eyeliner, mascara and nail polish, mouthwash, toothpaste, sublingual tablets, various medicines such as powdered stomach medicine and the like.
【００３２】[0032]
【実施例】【Example】
【００３３】以下に、実施例を挙げて本発明の内容を更
に具体的に説明するが、本発明の範囲はこれらに限定さ
れるものではない。尚、例中の％は、特に断らない限り
重量％を表すものとする。Hereinafter, the contents of the present invention will be described more specifically with reference to examples, but the scope of the present invention is not limited to these. In the examples,% means% by weight unless otherwise specified.
【００３４】[0034]
【実施例−１】[Example-1]
【００３５】生コンブ（Laminaria japonica）（宮城県
唐桑産、平成４年５月採取）４００ｇに１４０ｇの粉砕
塩を満遍無く加えて、６日間１５℃の暗所に塩蔵した。
塩蔵後、３００ｇのコンブを取り出し、６００ｍｌのエ
タノールを加えて１分間洗浄した。次に、洗浄液を捨
て、再度６００ｍｌのクロロフィル類抽出のためのエタ
ノールを加えてコンブを浸漬し、２４時間室温で暗所に
置いて抽出し、コンブを取り出し、抽出した液を０．４
５μｍのメンブランフィルターで濾過し、クロロフィル
類組成物を含有したエタノール溶液を得た。更に、ろ液
を軽い減圧下で濃縮してエタノールを除去し、０．８１
ｇのクロロフィル類組成物−１を得た。To 400 g of raw kelp (Laminaria japonica) (produced in Karakuwa, Miyagi Prefecture, collected in May 1992), 140 g of crushed salt was uniformly added, and the mixture was salted in a dark place at 15 ° C. for 6 days.
After salting, 300 g of kelp was taken out, 600 ml of ethanol was added, and the mixture was washed for 1 minute. Next, the washing solution was discarded, 600 ml of ethanol for extracting chlorophylls was added again to immerse the kelp, and the kelp was extracted in a dark place at room temperature for 24 hours.
The mixture was filtered through a 5 μm membrane filter to obtain an ethanol solution containing the chlorophyll composition. Further, the filtrate was concentrated under a light reduced pressure to remove ethanol, and
g of chlorophyll composition-1 was obtained.
【００３６】[0036]
【実施例−２】[Example-2]
【００３７】実施例−１で抽出操作をした後取り出した
コンブに３００ｍｌのエタノールを加え、実施例−１と
同様に抽出、濾過、濃縮して０．２２ｇのクロロフィル
類組成物−２を得た。300 ml of ethanol was added to the kelp extracted after the extraction operation in Example-1, and extraction, filtration and concentration were carried out in the same manner as in Example-1 to obtain 0.22 g of chlorophyll composition-2. .
【００３８】[0038]
【実施例−３】[Example-3]
【００３９】実施例−１で用いたコンブに代えて、生ワ
カメ［Undaria pinnatifida (Harvey) Suringar］（韓
国産、平成４年５月採取）を用いた他は、実施例−１と
同一の操作を行い、２．０７１７ｇのクロロフィル類組
成物−３を得た。The same procedure as in Example-1 except that raw seaweed [Undaria pinnatifida (Harvey) Suringar] (produced in Korea, collected in May 1992) was used in place of the kelp used in Example-1. Then, 2.0717 g of a chlorophyll composition-3 was obtained.
【００４０】[0040]
【実施例−４】[Example-4]
【００４１】実施例−３で抽出操作をした後取り出した
ワカメに３００ｍｌのエタノールを加え、実施例−３と
同様に抽出、濾過、濃縮して０．２４１８ｇのクロロフ
ィル類組成物−４を得た。クロロフィル類組成物−３及
び４を合わせ、組成比をＨＰＬＣで確認したところ、化
合物（１）：化合物（２）＝４２．９：１０．１であっ
た。300 ml of ethanol was added to the wakame seaweed that had been extracted in Example 3 and extracted, filtered and concentrated in the same manner as in Example 3 to obtain 0.2418 g of a chlorophyll composition-4. . When the composition ratios of the chlorophyll compositions 3 and 4 were combined and confirmed by HPLC, the result was that compound (1): compound (2) = 42.9: 10.1.
【００４２】[0042]
【実施例−５】[Example-5]
【００４３】実施例−１及び実施例−２でそれぞれ得た
ものを合わせ、１．０３ｇのクロロフィル類組成物と
し、その組成比をＨＰＬＣで確認したところ、化合物
（１）：化合物（２）＝４８．５：２６．９であった。
この組成物を、ヘキサン：アセトン＝３：１の混合溶媒
を用いて１６０ｇのシリカゲルカラムに通して精製し、
７３．２ｍｇのクロロフィル類組成物−５を得た。The compositions obtained in Example-1 and Example-2 were combined to obtain 1.03 g of a chlorophyll composition, and the composition ratio was confirmed by HPLC. As a result, compound (1): compound (2) = It was 48.5: 26.9.
The composition was purified by passing through a 160 g silica gel column using a mixed solvent of hexane: acetone = 3: 1,
73.2 mg of chlorophyll composition-5 was obtained.
【００４４】[0044]
【実施例−６】[Example-6]
【００４５】実施例−５で得られたクロロフィル類組成
物−５の一部を用いて、ＨＰＬＣの分取カラム（Senshu
pak Silica-5301-N、０℃、ヘキサン：イソプロパノー
ル：メタノール＝１００：０．８：０．４、５ｍｌ／ｍ
ｉｎ．、４２５ｎｍ）により分離精製し、クロロフィル
類組成物、即ち、化合物（１）と化合物（２）とをそれ
ぞれ得た。A part of the chlorophyll composition-5 obtained in Example-5 was used to prepare an HPLC preparative column (Senshu).
pak Silica-5301-N, 0 ° C., hexane: isopropanol: methanol = 100: 0.8: 0.4, 5 ml / m
in. 425 nm) to separate and purify the chlorophyll composition, that is, the compound (1) and the compound (2), respectively.
【００４６】[0046]
【比較例−１】[Comparative Example-1]
【００４７】化学合成法［Ｐ．Ｍ．Ｓｃｈａｂｅｒら、
ジャーナル・オブ・クロマトグラフィー（Ｊｏｕｒｎａ
ｌ ｏｆ Ｃｈｒｏｍａｔｏｇｒａｐｈｙ），３１６
（１９８４）ｐ２５］により１０位をＯＨ化したクロロ
フィルａ′及び１０位をＯＨ化したクロロフィルａを調
製し、この物を対照品とした。Chemical synthesis method [P. M. Schaber et al.
Journal of Chromatography (Journa
l of Chromatography), 316
(1984) p25], chlorophyll a ′ having OH at the 10-position and chlorophyll a having OH at the 10-position were prepared and used as control products.
【００４８】[0048]
【確認試験−１】[Confirmation test-1]
【００４９】比較例−１で得た対照品と実施例−６で得
た本発明に係るクロロフィル類組成物とのＨＰＬＣ（Ne
opak 120-5SI、０℃、ヘキサン：イソプロパノール：メ
タノール＝１００：０．８：０．４、１．２ｍｌ／ｍｉ
ｎ．、 ４２５ｎｍ）の溶出スペクトルを比較した結果、
両者の溶出スペクトルは一致した。HPLC (Ne of the control product obtained in Comparative Example-1 and the chlorophyll composition according to the present invention obtained in Example-6)
opak 120-5SI, 0 ° C., hexane: isopropanol: methanol = 100: 0.8: 0.4, 1.2 ml / mi
n. , 425 nm) as a result of comparison of elution spectra,
Both elution spectra were in agreement.
【００５０】[0050]
【確認試験−２】[Confirmation test-2]
【００５１】比較例−１で得た対照品（１０位がＯＨ化
されたクロロフィルａ′，１０位がＯＨ化されたクロロ
フィルａ）と、実施例−６で得た本発明に係るクロロフ
ィル類組成物［化合物（１），化合物（２）］との可視
光線の吸収スペクトルを、それぞれ常法で測定した。得
られた結果について、図１に、本発明に係る化合物
（１）及び対照品である１０位をＯＨ化したクロロフィ
ルａ′の可視光線の吸収スペクトルを示す。また、図２
に、本発明に係る化合物（２）及び対照品である１０位
をＯＨ化したクロロフィルａの可視光線の吸収スペクト
ルを示す。得られた結果から、対照品の構造と実施例−
６で得られた本発明に係るクロロフィル類組成物の構造
とに相違が無いことが支持される。なお、図１，図２
中、本発明に係る化合物（１）及び化合物（２）は実線
で示し、対照品である１０位をＯＨ化したクロロフィル
ａ及び１０位をＯＨ化したクロロフィルａ′は点線で示
したが、ほぼ同一の線となっている。The control product obtained in Comparative Example-1 (chlorophyll a'in which 10-position is OH, chlorophyll a in which 10-position is OH) and the composition of chlorophyll according to the present invention obtained in Example-6 The visible light absorption spectra of the compound [compound (1), compound (2)] were measured by a conventional method. With respect to the obtained results, FIG. 1 shows visible light absorption spectra of the compound (1) according to the present invention and chlorophyll a ′, which is a control product and has 10-position OH. Also, FIG.
FIG. 3 shows visible light absorption spectra of compound (2) according to the present invention and chlorophyll a, which is a control product and has 10-position OH. From the results obtained, the structure of the control product and the Example-
It is supported that there is no difference in the structure of the chlorophyll composition according to the present invention obtained in 6. 1 and 2
Among them, the compound (1) and the compound (2) according to the present invention are shown by a solid line, and the chlorophyll a having 10-position OH and the chlorophyll a ′ having 10-position OH are shown by dotted lines. The lines are the same.
【００５２】[0052]
【確認試験−３】[Confirmation test-3]
【００５３】比較例−１で得た対照品（１０位がＯＨ化
されたクロロフィルａ′，１０位がＯＨ化されたクロロ
フィルａ）と、実施例−６で得た本発明に係るクロロフ
ィル類組成物［化合物（１），化合物（２）］との常法
によるＣＤ（円偏光２色性）スペクトルを、それぞれ測
定した。得られた結果について、図３に、本発明に係る
化合物（１）及び化合物（２）のＣＤスペクトルを示
す。また、図４に、対照品である１０位をＯＨ化したク
ロロフィルａ′及び１０位をＯＨ化したクロロフィルａ
のＣＤスペクトルを示す。得られた結果から、対照品の
構造と実施例−６で得られた本発明に係るクロロフィル
類組成物の構造とに相違が無いことが支持される。The control product obtained in Comparative Example-1 (chlorophyll a'where the 10th position was OH, chlorophyll a where the 10th position was OH) and the chlorophyll composition according to the present invention obtained in Example-6 The CD (circular dichroism) spectra of the product [compound (1), compound (2)] were measured by a conventional method. Regarding the obtained results, FIG. 3 shows the CD spectra of the compound (1) and the compound (2) according to the present invention. In addition, in FIG. 4, the chlorophyll a ′ in which the 10-position is OH and the chlorophyll a in which the 10-position is OH are the control products.
2 shows the CD spectrum of The obtained results support that there is no difference between the structure of the control product and the structure of the chlorophyll composition according to the present invention obtained in Example-6.
【００５４】[0054]
【確認試験−４】[Confirmation test-4]
【００５５】比較例−１で得た対照品中の１０位をＯＨ
化したクロロフィルａと、実施例−６で得た本発明に係
るクロロフィル類組成物の中の化合物（２）との13Ｃ−
ＮＭＲ（核磁気共鳴）スペクトルを、それぞれ測定し
た。得られた結果について、図５に、本発明に係る化合
物（２）の13Ｃ−ＮＭＲスペクトルを示す。また、図６
に、対照品である１０位をＯＨ化したクロロフィルａの
13Ｃ−ＮＭＲスペクトルを示す。得られた結果から、対
照品の構造と実施例−６で得られた本発明に係るクロロ
フィル類の構造とに相違が無いことが支持される。The 10th position in the control product obtained in Comparative Example-1 was OH.
13 C-of the converted chlorophyll a and the compound (2) in the chlorophyll composition according to the present invention obtained in Example-6
The NMR (nuclear magnetic resonance) spectra were measured respectively. Regarding the obtained results, FIG. 5 shows the 13 C-NMR spectrum of the compound (2) according to the present invention. In addition, FIG.
In addition, the chlorophyll a of which the 10-position is OH
13 C-NMR spectrum is shown. The obtained results support that there is no difference between the structure of the control product and the structure of the chlorophylls according to the present invention obtained in Example-6.
【００５６】[0056]
【比較試験】[Comparison test]
【００５７】濃度が４．７×１０-5モル／ｌになるよう
に、実施例−６で得た本発明に係る化合物（１）及びク
ロロフィルａを、それぞれエタノールに溶解した。各溶
液１０ｍｌをそれぞれ５０ｍｌの三角フラスコに入れ、
パラフィルムで密閉し、２５℃で暗所に置いた。また、
各溶液１０ｍｌを同様に用意して２５℃で２０００ルッ
クスの明所に置いた。各試料について、エタノール中に
於ける光安定性の経時変化を、可視光線の吸収スペクト
ルの赤色帯（Ｒｅｄ ｂａｎｄ）での減少率で測定し
た。得られた結果について、図７に、本発明に係る化合
物（１）及びクロロフィルａの赤色帯での光吸収率と保
存時間との関係を示す。図７に示された結果から、暗所
の場合、２０００ルックスの明所の場合共に、化合物
（１）のほうが、クロロフィルａよりも顕著に安定であ
ることが判る。特に、化合物（１）は、暗所で保管した
場合には、クロロフィルａよりも遥かに安定であること
が判る。The compound (1) of the present invention obtained in Example 6 and chlorophyll a were dissolved in ethanol so that the concentration was 4.7 × 10 -5 mol / l. Add 10 ml of each solution to a 50 ml Erlenmeyer flask,
It was sealed with parafilm and placed in the dark at 25 ° C. Also,
10 ml of each solution was similarly prepared and placed in the light of 2000 lux at 25 ° C. For each sample, the change with time in photostability in ethanol was measured by the rate of decrease in the absorption band of visible light in the red band. Regarding the obtained results, FIG. 7 shows the relationship between the light absorption rate of the compound (1) according to the present invention and chlorophyll a in the red band and the storage time. From the results shown in FIG. 7, it can be seen that the compound (1) is significantly more stable than chlorophyll a in both the dark place and the bright place of 2000 lux. In particular, it can be seen that the compound (1) is much more stable than chlorophyll a when stored in the dark.
【００５８】[0058]
【発明の効果】【The invention's effect】
【００５９】以上に説明したように、本発明を実施する
ことにより、天然の藻類中の不安定なChl a を安定な化
合物（１）及び化合物（２）に変化させることが可能に
なり、且つ、それから該物質を抽出することによって、
比較的安定なクロロフィル類組成物が、従来の化学的合
成法による場合よりも遥かに経済的に提供される。つま
り、本発明により、天然系色素であるクロロフィル類組
成物の食品等各種用途向け緑色色素としての使用が可能
になる。As described above, by carrying out the present invention, it becomes possible to change unstable Chla in natural algae into stable compounds (1) and (2), and , And then by extracting the substance,
Relatively stable chlorophyll compositions are provided much more economically than by conventional chemical synthetic methods. That is, according to the present invention, it becomes possible to use the chlorophyll composition which is a natural pigment as a green pigment for various applications such as foods.
【図面の簡単な説明】[Brief description of drawings]
【図１】本発明に係る化合物（１）及び対照品である１
０位をＯＨ化したクロロフィルａ′の可視光線の吸収ス
ペクトルを示す図FIG. 1 is a compound (1) according to the present invention and a control product 1
The figure which shows the absorption spectrum of visible light of chlorophyll a'which made 0-position OH.
【図２】本発明に係る化合物（２）及び対照品である１
０位をＯＨ化したクロロフィルａの可視光線の吸収スペ
クトルを示す図FIG. 2 is a compound (2) according to the present invention and a control product 1
The figure which shows the absorption spectrum of the visible light of the chlorophyll a which made 0-position OH.
【図３】本発明に係る化合物（１）及び化合物（２）の
ＣＤスペクトルを示す図FIG. 3 is a diagram showing CD spectra of compound (1) and compound (2) according to the present invention.
【図４】対照品である１０位をＯＨ化したクロロフィル
ａ′及び１０位をＯＨ化したクロロフィルａのＣＤスペ
クトルを示す図FIG. 4 is a diagram showing CD spectra of chlorophyll a ′ in which 10-position is OH and chlorophyll a in which 10-position is OH, which are control products.
【図５】本発明に係る化合物（２）の13Ｃ−ＮＭＲスペ
クトルを示す図FIG. 5 is a diagram showing a 13 C-NMR spectrum of a compound (2) according to the present invention.
【図６】対照品である１０位をＯＨ化したクロロフィル
ａの13Ｃ−ＮＭＲスペクトルを示す図FIG. 6 is a diagram showing a 13 C-NMR spectrum of chlorophyll a in which the 10-position is OH-ized as a control product.
【図７】本発明に係る化合物（１）及びクロロフィルａ
の赤色帯での光吸収率と保存時間との関係を示す図FIG. 7: Compound (1) according to the present invention and chlorophyll a
Graph showing the relationship between light absorption rate in the red band and storage time
【手続補正２】[Procedure Amendment 2]
【補正対象書類名】図面[Document name to be corrected] Drawing
【補正対象項目名】全図[Correction target item name] All drawings
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【図３】 [Figure 3]
【図１】 [Figure 1]
【図５】 [Figure 5]
【図２】 [Fig. 2]
【図４】 [Figure 4]
【図６】 [Figure 6]
【図７】 [Figure 7]
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ａ２３Ｌ 1/337 Ｚ (Ｃ１２Ｐ 17/18 Ｃ１２Ｒ 1:89） ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Internal reference number FI technical display location A23L 1/337 Z (C12P 17/18 C12R 1:89)
Claims (2)
る藻類を塩蔵した後、クロロフィル類を抽出することを
特徴とするクロロフィル類組成物の新規製造法。1. A novel method for producing a chlorophyll composition, which comprises extracting an chlorophyll after salting an alga selected from brown algae, green algae and red algae.
（Ａ）で表される化合物（１）［一般式（Ａ）でＲ1 が
ＯＨ基、Ｒ2 がＣＯＯＣＨ3 基の場合］及び化合物
（２）［一般式（Ａ）でＲ1 がＣＯＯＣＨ3 、Ｒ2 がＯ
Ｈ基の場合］を主成分として含有する請求項１記載のク
ロロフィル類組成物の新規製造法。 【化１】 2. A compound (1) wherein the extracted chlorophyll is represented by the general formula (A) [when R 1 is an OH group and R 2 is a COOCH 3 group in the general formula (A)] and a compound (2) ) [In the general formula (A), R 1 is COOCH 3 and R 2 is O.
In the case of H group] as a main component, the novel method for producing a chlorophyll composition according to claim 1. [Chemical 1]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04287096A JP3128712B2 (en) | 1992-10-02 | 1992-10-02 | New production method of chlorophyll composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04287096A JP3128712B2 (en) | 1992-10-02 | 1992-10-02 | New production method of chlorophyll composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06113872A true JPH06113872A (en) | 1994-04-26 |
| JP3128712B2 JP3128712B2 (en) | 2001-01-29 |
Family
ID=17713009
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP04287096A Expired - Lifetime JP3128712B2 (en) | 1992-10-02 | 1992-10-02 | New production method of chlorophyll composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3128712B2 (en) |
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