JP4084871B2

JP4084871B2 - A method for improving the quality of pigment concentrate concentrates of anthocyanin-containing plants.

Info

Publication number: JP4084871B2
Application number: JP33201897A
Authority: JP
Inventors: 和保三木; 祐二郎伊藤; 覚真野; 哲男上田; 隆次郎椎名; 久七宮沢
Original assignee: 日農化学工業株式会社; 株式会社鹿光生物科学研究所
Priority date: 1997-02-10
Filing date: 1997-12-02
Publication date: 2008-04-30
Anticipated expiration: 2017-12-02
Also published as: JPH10279825A

Description

【０００１】
【発明の属する技術分野】
本発明は、赤キャベツ等のアントシアニン含有植物を原料とし、無極性の多孔質重合樹脂で精製処理された食品用のアントシアニン含有植物の色素精製濃縮液の品質の改良方法に関するものである。
【０００２】
【従来の技術】
従来、赤キャベツ等のアントシアニン含有植物から抽出したアントシアニン色素を精製する方法として、無極性の多孔質重合樹脂を用いる方法が知られており、本発明者らも、無極性の多孔質重合樹脂を用いた「赤キャベツ色素の製造方法」を出願している（特願平８−７０３１２号）。
【０００３】
上記の「赤キャベツ色素の製造方法」（特願平８−７０３１２号）にも記載したように、赤キャベツ色素液の精製に無極性の多孔質重合樹脂を使用すると、赤キャベツ色素液中のキャベツ臭および不純物蛋白質の大部分を取り除くことができるという大きな利点がある。特に、キャベツ臭を除くことは、限外濾過法を含む各種の濾過法では困難である。
【０００４】
しかしながら、後述の実験例１に示したように、無極性の多孔質重合樹脂を使用して精製したアントシアニン含有植物の色素液は、保存中に温度が１５℃以下に低下すると、アントシアニン色素の結晶が生成し、沈殿しやすいことが判明した。
【０００５】
また、アントシアニン含有植物の色素精製濃縮液は、温度が高い程、色価の減少が大きく、低温保存が必要な製品である。
【０００６】
【発明が解決しようとする課題】
本発明が解決しようとする課題は、無極性の多孔質重合樹脂を用いて精製したアントシアニン含有植物の色素液に発生するアントシアニン色素結晶の沈殿生成を防止する手段、すなわちアントシアニン含有植物の色素精製濃縮液の低温安定性の改良方法を提供することである。
【０００７】
【課題を解決するための手段】
本発明者らは、上記課題を解決するために鋭意研究を重ねた結果、無極性の多孔質重合樹脂を用いて精製したアントシアニン含有植物の色素液に特定の糖類および糖アルコールを添加することにより上記課題が解決できることを見いだし本発明を完成するに至った。
【０００８】
すなわち、本発明は、
（１）アントシアニン含有植物の色素抽出液を無極性の多孔質重合樹脂で処理した後濃縮して得られるアントシアニン色素精製濃縮液に、ソルビトール、還元澱粉糖化物、デキストリンおよびトレハローズからなる群より選ばれる少なくとも１種の化合物を添加することによって、アントシアニン色素精製濃縮液の色素結晶の生成を防止することを特徴とするアントシアニン含有植物の色素精製濃縮液の品質の改良方法、
（２）アントシアニン含有植物が、赤キャベツ、ムラサキイモ、シソまたはアカダイコンである前記（１）項に記載のアントシアニン含有植物の色素精製濃縮液の品質の改良方法、
（３）無極性の多孔質重合樹脂が、スチレン系樹脂またはアクリル酸系樹脂であることを特徴とする前記（１）項に記載のアントシアニン含有植物の色素精製濃縮液の品質の改良方法、
（４）ソルビトール、還元澱粉糖化物、デキストリンおよびトレハローズからなる群より選ばれる少なくとも１種の化合物の添加量が、赤キャベツ色素精製濃縮液当たり４重量％以上であることを特徴とする前記（１）項に記載のアントシアニン含有植物の精製濃縮液の品質の改良方法、
に関するものである。
【０００９】
【発明の実施の形態】
本発明方法の品質の改良方法の対象となるアントシアニン含有植物の精製濃縮液は、アントシアニン含有植物の色素抽出液を無極性の多孔質重合樹脂で精製処理した後濃縮して得られるものである。
【００１０】
本発明におけるアントシアニン含有植物は、植物細胞中にアントシアニン色素を含む植物であれば特に限定されないが、例えば、赤キャベツ、ムラサキイモ、シソおよびアカダイコン等を挙げることができる。
【００１１】
アントシアニン含有植物の色素抽出液を無極性の多孔質重合樹脂で処理する方法は、特に限定されないが、例えば以下のような方法を挙げることができる。
【００１２】
まず原料となるアントシアニン含有植物の色素抽出液とは、原料のアントシアニン含有植物を色素抽出可能な程度に裁断し、適量の水を加え、硫酸、塩酸等の鉱酸またはクエン酸、リンゴ酸等の有機酸によりｐＨ１．５〜３．０程度の酸性側に保った後、濾過処理することにより得られる透明な抽出液である。
【００１３】
このアントシアニン含有植物の色素抽出液を無極性の多孔質重合樹脂で精製するには、無極性の多孔質重合樹脂を充填したカラムに色素抽出液を通液すればよい。無極性の多孔質重合樹脂とは、スチレン系樹脂、アクリル酸系樹脂等の合成樹脂であり、例えば、ＨＰ−２０、ＨＰ−５０、ＳＰ−２０６、ＳＰ−８２５（三菱化成工業（株）製）等や、アンバーライトＸＡＤ−２、ＸＡＤ−４（有機化学工業（株）製）等を挙げることができる。通液は、例えばＳＶ＝１〜１０の範囲で行えばよい。
【００１４】
無極性の多孔質重合樹脂への通液処理により、アントシアニン色素および植物臭と蛋白質の大部分は樹脂に吸着され、水溶性ミネラル（例えば、水溶性ナトリウム、カリウム、カルシウム等の塩類）や疎水構造を持たない親水性物質（例えば炭水化物）は樹脂に吸着されずに流失し、続く樹脂の水洗により、水溶性ミネラルや親水性物質の除去はさらに完全になる。
【００１５】
次いで吸着されたアントシアニン色素を親水性有機溶媒を用いて、無極性の多孔質重合樹脂から溶出させる。溶出に用いる親水性有機溶媒としては、例えば、エタノール、メタノール、アセトン等を挙げることができが、食用色素用としてエタノールが、さらに８０％エタノール水溶液が好ましい。
【００１６】
無極性の多孔質重合樹脂で精製したアントシアニン含有植物の色素抽出液は、このまま濃縮して色素精製濃縮液としてもよいが、さらに残存する少量の臭気や蛋白質等の不純物をゼオライト、パーライト、カオリン等の不溶性鉱物性物質を用いて除去したり、水蒸気蒸留により低分子の揮発性物質を除去してもよい。
【００１７】
アントシアニン含有植物の色素溶出液は、真空濃縮等の公知の手段によって濃縮することにより色素精製濃縮液が得られる。濃縮することには、以下のような効果がある。
【００１８】
（１）食品に対するアントシアニン色素液の添加量を減らすことができるので、食品の風味、組織性状に対する影響を防ぐことができる。
【００１９】
（２）濃縮により体積が減少しており、使用や保存に便利である。
【００２０】
（３）濃縮により体積が減少しており、包材費、輸送費を節約できる。
【００２１】
（４）濃縮により、色価の低下速度が抑制される。
【００２２】
濃縮は、濃縮液の色価が、４００〜１５００程度になるまで濃縮することが好ましい。
【００２３】
こうして調製したアントシアニン色素精製濃縮液に、ソルビトール、還元澱粉糖化物、デキストリンおよびトレハローズからなる群より選ばれる少なくとも１種を添加することにより、無極性の多孔質重合樹脂処理によりえた赤キャベツ色素精製濃縮液の低温保存時における色素結晶の析出を防止することができる。無極性の多孔質重合樹脂で精製処理したアントシアニン色素精製濃縮液の色素結晶の生成を防止する物質のうち、微生物により発酵されにくいソルビトールや還元澱粉糖化物が効果が高く好ましい。
【００２４】
色素結晶の析出を防止するこれらの化合物の添加量は、製品となるアントシアニン色素精製濃縮液当たり、４〜３０％の範囲で適宜選択すればよい。４％未満では、色素結晶の生成を防止する効果が少なく、また３０％を超えて添加しても効果は増加せずコスト増となるため好ましくない。
【００２５】
最終的にアントシアニン色素精製濃縮液とするには、水およびクエン酸、必要ならば苛性ソーダを加えて、ｐＨ１．５〜３．０、色価４００〜１０００程度に調整して、所望の色価を有する製品とすればよい。なお、必要ならば、微生物の増殖を抑制するためにエタノールを加えてもよい。
【００２６】
後述する実験例１から明らかなように、無極性の多孔質重合樹脂で処理した赤キャベツ色素精製濃縮液は、低温保存中に色素の結晶を生成するのに対し、樹脂処理をしない対照の色素濃縮液は色素の結晶を生成しない。また、両色素濃縮液中の色素に差が認められないことから、色素結晶の生成の有無は、両濃縮液中の色素以外の成分の差に起因することを示唆している。
【００２７】
成分の差について、対照の色素濃縮液中には、色素分子を保護する物質（保護物質）が存在し、これが色素分子の集合を防ぎ、その結果結晶の生成成長を抑制するものと推定される。
【００２８】
これに対し、無極性の多孔質重合樹脂で処理した赤キャベツ色素液では、上記保護物質がないため、色素分子が集合し、結晶に成長するものと思われる。
【００２９】
無極性の多孔質重合樹脂は、疎水性構造を有する物質（例えばアントシアニン、蛋白質等）を吸着するが、疎水性構造を有しない親水性物質（例えば炭水化物等）を吸着せず、これらは流失する。
【００３０】
色素結晶の生成成長を妨げる前記色素分子保護物質は、無極性の多孔質重合樹脂に吸着されずに流失する親水性の成分に含まれているものと思われる。なお、この流失区分中の保護物質の同定あるいは回収は極めて困難である。
【００３１】
【実施例】
以下に、本発明を実施例により詳細に説明するが、本発明はこれらの実施例に限定されることはない。
【００３２】
実験例１
（１）赤キャベツ色素の抽出液
赤キャベツを裁断し、ｐＨ２．５〜３．０のクエン酸溶液に浸漬し、１夜放置後濾過し、透明な色素抽出液（色価約８）を得た。
【００３３】
赤キャベツの色価は、赤キャベツ色素液をＭｕｃｌｌｖａｉｎｅ緩衝液ｐＨ３．０で適当に希釈し、波長５３２ｎｍ（赤キャベツ色素の最大吸収波長）の吸光度を測定し、吸光値を希釈前の濃度に換算して（Ｅ１００％、１ｃｍ５３２ｎｍ）で表示したものである。以後の色価は、この方法に準じて測定した。
【００３４】
（２）濃縮色素液の調製
上記の透明な赤キャベツ色素抽出液を真空濃縮して、色価約１２００の濃縮色素液を得た。この濃縮色素液にクエン酸、および水、必要ならば苛性ソーダを加えて、ｐＨ２．８の色価８５０および色価４００の赤キャベツ色素濃縮液を調製した。この色素濃縮液は、無極性の多孔性重合樹脂を使用していないから、以後それぞれ「対照色価８５０色素液」および「対照色価４００色素液」と略称する。
【００３５】
（３）無極性の多孔質重合樹脂処理をした濃縮色素液の調製
「赤キャベツ色素の製造方法」（特願平８−７０３１２号）の実施例１の記載に準じて、上記の透明な赤キャベツ色素抽出液を、無極性の多孔質重合樹脂（三菱化成（株）製、「ＨＰ−２０」）カラムで処理し、赤キャベツ色素を樹脂に吸着させ、次いで樹脂を水洗後、８０％エチルアルコール水溶液で赤キャベツ色素を溶出した。溶出した色素液を、真空濃縮して、色価約１２００の濃縮色素溶液を得た。
【００３６】
この濃縮色素液に、クエン酸および水、必要ならば、苛性ソーダを加えて（２）と同様に、ｐＨ２．８の色価８５０および色価４００の赤キャベツ色素濃縮液を調製した。以後、この色素濃縮液をそれぞれ、「樹脂処理色価８５０色素液」および「樹脂処理色価４００色素液」と略称する。
【００３７】
（４）濃縮色素液の冷蔵保存試験
上記の「対照色価８５０色素液」、「対照色価４００色素液」、「樹脂処理色価８５０色素液」、「樹脂処理色価４００色素液」を、それぞれ褐色瓶に入れて冷蔵庫（８℃以下）に３週間保存した後、遠心分離し分離液の色価を測定し、色価減少率を算出した。結果を表１に示す。なお色価減少率は、下記式により求めた。
【００３８】
【数１】

【００３９】
【表１】

【００４０】
表１の結果から明らかなように、「対照色価４００色素液」および「対照色価８５０色素液」は、３週間低温で保存しても色価の減少率は４％以下であるのに対し、無極性の多孔質重合樹脂で処理した色素液は、色価が大きく減少している。
【００４１】
すなわち、冷蔵３週間保存で色価は、「樹脂処理色価４００色素液」で１２％、「樹脂処理色価８５０色素液」で２２％減少している。
【００４２】
この「樹脂処理色価４００色素液」、「樹脂処理色価８５０色素液」を保存した褐色瓶の瓶底には多量の赤紫色結晶沈殿が見られた。この赤紫色結晶は、液中で加温すると溶解した。
【００４３】
上記の冷蔵保存により生成した多量の赤紫色結晶を含む「樹脂処理色価４００色素液」および「樹脂処理色価８５０色素液」を約５０℃に加温して結晶を溶解して、室温に冷却した後色価を測定すると、保存前の色素液とほとんど差のない色価に復元した。色価が復元した色素液の吸光度を測定した吸収曲線は、「対照色価４００色素液」、「対照色価８５０色素液」および保存前の「対照色価４００色素液」、「対照色価８５０色素液」の吸収曲線に一致した。測定結果を図１に示す。
【００４４】
また、対照色素液、保存前の色素液および復元した色素液の色調（Ｌ，ａ，ｂ値）を測定した。その結果を表２に示す。表２の結果から明らかなように、ΔＥはいずれも１以下で、肉眼的にも色調の変化は認められなかった。
【００４５】
【表２】

【００４６】
以上の実験結果から、冷蔵保存で生成する赤紫色結晶は、赤キャベツ色素そのものであること、および色素自体は、対照と樹脂処理色素で差がないことを示している。
【００４７】
なお、「対照色価４００色素液」および「対照色価８５０色素液」は、キャベツ臭が強く、食品用の色素としては不適当であった。
【００４８】
実施例１
実験例１に準じて、無極性の多孔質重合樹脂で処理した赤キャベツ色素精製濃縮液（色価約１２００）を調製した。得られた赤キャベツ色素精製濃縮液を約４０℃に加温し、食品工業に利用可能な親水性物質の中から、表３に示すような各種の糖類、糖アルコール、親水性乳化剤を加え直接溶解した。
【００４９】
表３に示す物質を溶解した赤キャベツ色素精製濃縮液に、クエン酸、水、必要ならば苛性ソーダを加えてｐＨ２．８、色価８５０の色素液を調製し、冷蔵庫（８℃以下）に３週間保存後、遠心分離して上層の色価を測定した。その結果を表３に示す。表中の色素減少率は色素結晶生成量に比例する。
【００５０】
【表３】

【００５１】
表３に示した結果から明らかなように、本発明のソルビトール、還元澱粉糖化物、デキストリン、トレハローズを添加した色素精製濃縮液は、低温で保存しても色価減少率が少なく、すなわち結晶の生成量が少ないことが分かる。一方、本発明以外のブドウ糖、果糖、乳糖および麦芽糖などの糖類や、ショ糖脂肪酸エステルやポリグリセリン脂肪酸エステルを添加したものは、低温保存すると色素結晶が生成し、低温安定性がよくなかった。
【００５２】
実施例２
赤キャベツ２０Ｋｇを適当に裁断し、水８０．０リットルを加え、硫酸を添加してｐＨ２．４に調整し、赤キャベツ色素抽出液７７リットルを得た。無極性の多孔質重合樹脂（「ＨＰ−２０」三菱化成工業（株）製）２．５リットルを充填したカラムに、得られた色素抽出液を、ＳＶ＝５で通液した。通液後、色素を吸着した無極性の多孔質重合樹脂を水洗し、親水性有機溶媒（８０％エタノール）５リットルをカラムに通液し、色素を溶出させた。
【００５３】
得られた溶出液を、４０℃で減圧濃縮して色価１２００の色素濃縮液を得た。この色素濃縮液を濾紙にて減圧濾過後、５本の１００ｍｌ褐色瓶（Ｎｏ．１〜Ｎｏ．５）に、７０．０ｇずつ秤取し、ｐＨを３．０以下にするために、クエン酸２．０ｇをＮｏ．１〜Ｎｏ．５の各褐色瓶に添加した。Ｎｏ．１を対照とし、Ｎｏ．２にソルビトール１５％、Ｎｏ．３に還元澱粉糖化物１５％、Ｎｏ．４にトレハローズ１５％、Ｎｏ．５にデキストリン１５％を加えて溶解後、それぞれの褐色瓶に水を加えて１００．０ｇ（色価８４０）に調整し、冷蔵庫（８℃以下）に３週間保存した。保存後、内容物をよく混合し１００ｍｌ遠心管に移し、３０００ｒｐｍで１０分間遠心分離し、上層液の色価を測定した。保存後の色価および色価減少率を表４に示す。
【００５４】
【表４】

【００５５】
表４に示した結果から明らかなように、本発明の化合物を加えない対照品（Ｎｏ．１）の色価は１９％減少し、また保存品には多量の赤紫色の結晶の沈殿が見られたのに対し、本発明の化合物を添加したＮｏ．２〜Ｎｏ．５では、結晶状の沈殿はほとんど見られず、色価の減少率も３％以下であった。
【００５６】
実施例３
赤キャベツの色素抽出液（ｐＨ２．６、色価９）７０リットルを、無極性の多孔質重合樹脂（「ＳＰ−２０６」、三菱化成工業（株）製）２リットルを充填したカラムにＳＶ＝４で通液し、ついで４リットルの水で水洗後、８０％エタノール４．５リットルで色素を溶出し、溶出液を減圧濃縮して色価１５００の溶出液３７０グラムを得た。この色素濃縮液を濾紙にて減圧濾過し、３本の１００ｍｌ褐色瓶（Ｎｏ．１〜Ｎｏ．３）に５５．０ｇずつ秤取し、ｐＨを３．０以下にするためにクエン酸２．０ｇを、また微生物の増殖を防止するためにエタノール２０ｇを加えた。
【００５７】
Ｎｏ．１には水２３ｇを加え総計１００ｇ（色価８２５）とした。Ｎｏ．２にはソルビトール液（ソルビトール７０％）２０ｇ、水３ｇを加えて計１００ｇとした。Ｎｏ．３には還元澱粉糖化物（商品名：「アマミール」、東和化成工業（株）製）２０ｇ、水３ｇを加え計１００ｇとした。Ｎｏ．１〜Ｎｏ．３を冷蔵庫（８℃以下）に３週間保存した。保存後、内容物をよく混合し１００ｍｌ遠心管に移し、３０００ｒｐｍで１０分間遠心分離し、上層液の色価を測定した。保存後の色価および色価減少率を表５に示す。
【００５８】
【表５】

【００５９】
表５に示した結果から明らかなように、ソルビトールや還元澱粉糖化物を加えない対照品（Ｎｏ．１）は色価が２３％減少し、また保存品には多量の赤紫色の結晶の沈殿が見られたのに対し、ソルビトール、還元澱粉糖化物を添加したＮｏ．２、Ｎｏ．３では、結晶状の沈殿はほとんど見られず、色価の減少率も３％以下であった。
【００６０】
実施例４
ムラサキイモ色素の抽出液、ｐＨ２．３、色価Ｅ^100%５３０ｎｍ＝１５．０（ｐＨ３．０、Ｍｃｌｌｖａｉｎｅｂｕｆｆｅｒ）５０Ｌを無極性の多孔質重合樹脂（商品名「ＨＰ−２０」、三菱化成工業（株）製）２Ｌを充填したカラムにＳＶ＝３にて通液し、水洗４Ｌ後，７０％（Ｖ／Ｖ）エタノール４Ｌを用いて色素を溶出し、溶出液を減圧濃縮してＥ^100%５３０ｎｍ＝１５００の色素液を４２０ｇ得た。この色素濃縮液を濾紙にて減圧濾過し、３本の１００ｍｌ褐色瓶（Ｎｏ．１〜Ｎｏ．３）に５５．０ｇずつ秤取し、ｐＨ３．０以下にするためにクエン酸（結晶）２．０ｇを、また微生物の増殖を防止するためにエタノール２０ｇを加えた。
【００６１】
Ｎｏ．１には、水２３ｇを加え総計１００ｇ（色価８２５）とした。Ｎｏ．２にはソルビトール液（ソルビトール７０％）２０ｇ、水３ｇを加えて計１００ｇとした。Ｎｏ．３には還元澱粉糖化物（商品名「アマミール」、東和化成工業（株）製）２０ｇ、水３ｇを加え計１００ｇとした。Ｎｏ．１〜Ｎｏ．３の褐色瓶を冷蔵庫（８℃以下）に３週間保存した。保存後、内容物をよく混合し、１００ｍｌ遠心管に移し、３０００ｒｐｍで１０分間遠心分離し、上層液の色価を測定した。保存後の色価および色価減少率を表６に示す。
【００６２】
【表６】

【００６３】
表６に示した結果から明らかなように、ムラサキイモを原料とするアンシアニン色素精製濃縮液において、ソルビトールや還元澱粉を加えない対照品（Ｎｏ．１）は色価が２１．２％減少し、また保存品には多量の赤紫色の結晶の沈澱が見られたのに対し、ソルビトール、還元澱粉糖化物を添加したＮｏ．２、Ｎｏ．３では、結晶状の沈澱はほとんど認められず、色価の減少率も３％以下であった。実施例５
シソ色素の抽出液、ｐＨ２．１、色価Ｅ^100%５２０ｎｍ＝７．０（ｐＨ３．０、Ｍｃｌｌｖａｉｎｅｂｕｆｆｅｒ）７０Ｌを無極性の多孔質重合樹脂（商品名「ＳＰ−２０７」、三菱化成工業（株）製）２Ｌを充填したカラムにＳＶ＝４にて通液し、水洗４Ｌ後、８０％（Ｖ／Ｖ）エタノール４Ｌ用いて色素を溶出し、溶出液を減圧濃縮してＥ^100%５２０ｎｍ＝１５００の色素液を２６０ｇ得た。この色素濃縮液を濾紙にて減圧濾過し、３本の１００ｍｌ褐色瓶（Ｎｏ．１〜Ｎｏ．３）に４２．０ｇずつ秤取し、ｐＨ３．０以下にするためにクエン酸（結晶）２．０ｇを、また微生物の増殖を防止するためにエタノール１５ｇを加えた。Ｎｏ．１には、水４１ｇを加え総計１００ｇ（色価６３０）とした。Ｎｏ．２にはソルビトール液（ソルビトール７０％）２０ｇ、水２１ｇを加えて計１００ｇとした。Ｎｏ．３には還元澱粉糖化物（商品名「アマミール」、東和化成工業（株）製）２０ｇ、水２１ｇを加え計１００ｇとした。Ｎｏ．１〜Ｎｏ．３の褐色瓶を冷蔵庫（８℃以下）に３週間保存した。保存後、内容物をよく混合し、１００ｍｌ遠心管に移し、３０００ｒｐｍで１０分間遠心分離し、上層液の色価を測定した。保存後の色価および色価減少率を表７に示す。
【００６４】
【表７】

【００６５】
表７に示した結果から明らかなように、シソを原料とするアントシアニン色素精製濃縮液において、ソルビトールや還元澱粉を加えない対照品（Ｎｏ．１）は色価が４１．４％減少し、また保存品には多量の赤色の結晶の沈澱が見られたのに対し、ソルビトール、還元澱粉糖化物を添加したＮｏ．２、Ｎｏ．３では、結晶状の沈澱は僅かで、色価の減少率も６．５％以下であった。
【００６６】
実施例６
アカダイコン色素の抽出液、ｐＨ２．３、色価Ｅ^100%５１０ｎｍ＝４．１（ｐＨ３．０、Ｍｃｌｌｖａｉｎｅｂｕｆｆｅｒ）９０Ｌを無極性の多孔質重合樹脂（商品名「ＳＰ−２０７」、三菱化成工業（株）製）２Ｌを充填したカラムにＳＶ＝４にて通液し、水洗４Ｌ後、８５％（Ｖ／Ｖ）エタノール４Ｌ用いて色素を溶出し、溶出液を減圧濃縮してＥ^100%５１０ｎｍ＝１５００の色素液を２１０ｇ得た。この色素濃縮液を濾紙にて減圧濾過し、３本の１００ｍｌ褐色瓶（Ｎｏ．１〜Ｎｏ．３）に４２．０ｇずつ秤取し、ｐＨ３．０以下にするためにクエン酸（結晶）２．０ｇを、また微生物の増殖を防止するためにエタノール１５ｇを加えた。
【００６７】
Ｎｏ．１には、水４１ｇを加え総計１００ｇ（色価６３０）とした。Ｎｏ．２にはソルビトール液（ソルビトール７０％）２０ｇ、水２１ｇを加えて計１００ｇとした。Ｎｏ．３には還元澱粉糖化物（商品名「アマミール」、東和化成工業（株）製）２０ｇ、水２１ｇを加え計１００ｇとした。Ｎｏ．１〜Ｎｏ．３の褐色瓶を冷蔵庫（８℃以下）に３週間保存した。保存後、内容物をよく混合し、１００ｍｌ遠心管に移し、３０００ｒｐｍで１０分間遠心分離し、上層液の色価を測定した。保存後の色価および色価減少率を表８に示す。
【００６８】
【表８】

【００６９】
表８に示した結果から明らかなように、アカダイコンを原料とするアントシアニン色素精製濃縮液において、ソルビトールや還元澱粉を加えない対照品（Ｎｏ．１）は色価が３０．２％減少し、また保存品には多量の赤橙色の結晶の沈澱が見られたのに対し、ソルビトール、還元澱粉糖化物を添加したＮｏ．２、Ｎｏ．３では、結晶状の沈澱は僅かで、色価の減少率も４％以下であった。
【００７０】
【発明の効果】
無極性の多孔質重合樹脂により処理されたアントシアニン色素精製濃縮液は、色素結晶が生成しやすく、商品として通用しがたくまた使用上不便である。本発明により色素結晶の生成は防止され、無極性多孔質重合樹脂処理により精製されたアントシアニン含有植物の色素精製濃縮液の品質が改良される。
【図面の簡単な説明】
【図１】実験例１における、赤キャベツ色素の吸光度の測定結果を示す図。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for improving the quality of a purified pigment concentrate of anthocyanin-containing plants for foods, which is made from an anthocyanin-containing plant such as red cabbage and purified with a nonpolar porous polymer resin.
[0002]
[Prior art]
Conventionally, as a method for purifying an anthocyanin pigment extracted from an anthocyanin-containing plant such as red cabbage, a method using a nonpolar porous polymer resin is known, and the present inventors have also proposed a nonpolar porous polymer resin. An application has been filed for the “method for producing a red cabbage pigment” (Japanese Patent Application No. 8-70312).
[0003]
As described in the above “Method for producing red cabbage dye” (Japanese Patent Application No. 8-70312), when a nonpolar porous polymer resin is used for purification of red cabbage dye liquid, There is a great advantage that most of the cabbage odor and impurity proteins can be removed. In particular, it is difficult to remove cabbage odor by various filtration methods including an ultrafiltration method.
[0004]
However, as shown in Experimental Example 1 described later, when the anthocyanin-containing plant pigment solution purified using a nonpolar porous polymer resin is reduced to a temperature of 15 ° C. or lower during storage, anthocyanin pigment crystals Was formed and was found to precipitate easily.
[0005]
Further, an anthocyanin-containing plant pigment refining concentrate is a product that needs to be stored at a low temperature because the color value decreases more greatly as the temperature increases.
[0006]
[Problems to be solved by the invention]
The problem to be solved by the present invention is a means for preventing precipitation of anthocyanin pigment crystals generated in a pigment solution of an anthocyanin-containing plant purified using a nonpolar porous polymer resin, that is, pigment purification and concentration of an anthocyanin-containing plant. It is to provide a method for improving the low temperature stability of a liquid.
[0007]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventors have added specific sugars and sugar alcohols to the pigment solution of an anthocyanin-containing plant purified using a nonpolar porous polymer resin. The inventors have found that the above problems can be solved and have completed the present invention.
[0008]
That is, the present invention
(1) An anthocyanin pigment refining concentrate obtained by treating an anthocyanin-containing plant pigment extract with a nonpolar porous polymer resin and concentrating it is selected from the group consisting of sorbitol, reduced starch saccharified product, dextrin and trehalose A method for improving the quality of a pigment purified concentrate of an anthocyanin-containing plant, characterized by preventing the formation of pigment crystals of the anthocyanin pigment purified concentrate by adding at least one compound;
(2) The method for improving the quality of the pigment purified concentrate of an anthocyanin-containing plant according to (1) above, wherein the anthocyanin-containing plant is red cabbage, purple potato, perilla or red radish,
(3) The method for improving the quality of a pigment purified concentrate of an anthocyanin-containing plant according to (1), wherein the nonpolar porous polymer resin is a styrene resin or an acrylic acid resin,
(4) The addition amount of at least one compound selected from the group consisting of sorbitol, reduced starch saccharified product, dextrin and trehalose is 4% by weight or more per red cabbage pigment purified concentrate (1) A method for improving the quality of the purified concentrated solution of the anthocyanin-containing plant according to item),
It is about.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
The purified concentrated solution of an anthocyanin-containing plant that is the object of the method for improving the quality of the method of the present invention is obtained by purifying a pigment extract of an anthocyanin-containing plant with a nonpolar porous polymerization resin and then concentrating it.
[0010]
The anthocyanin-containing plant in the present invention is not particularly limited as long as it contains an anthocyanin pigment in plant cells, and examples thereof include red cabbage, purple potato, perilla and red radish.
[0011]
The method of treating the anthocyanin-containing plant pigment extract with a nonpolar porous polymer resin is not particularly limited, and examples thereof include the following methods.
[0012]
First, the pigment extract of the anthocyanin-containing plant that is the raw material is cut to the extent that the raw anthocyanin-containing plant can be pigment-extracted, added with an appropriate amount of water, and mineral acids such as sulfuric acid and hydrochloric acid or citric acid, malic acid, etc. It is a transparent extract obtained by filtration after maintaining the acid side with an organic acid at a pH of about 1.5 to 3.0.
[0013]
In order to purify the pigment extract of this anthocyanin-containing plant with a nonpolar porous polymer resin, the pigment extract may be passed through a column filled with the nonpolar porous polymer resin. The nonpolar porous polymer resin is a synthetic resin such as a styrene resin or an acrylic acid resin. For example, HP-20, HP-50, SP-206, SP-825 (manufactured by Mitsubishi Chemical Industries, Ltd.) And Amberlite XAD-2, XAD-4 (manufactured by Organic Chemical Industry Co., Ltd.) and the like. The liquid flow may be performed in the range of SV = 1 to 10, for example.
[0014]
By passing the liquid through a non-polar porous polymer resin, most of the anthocyanin pigment and plant odor and protein are adsorbed to the resin, resulting in water-soluble minerals (for example, salts such as water-soluble sodium, potassium and calcium) and hydrophobic structures. Hydrophilic substances (for example, carbohydrates) that do not have water are washed away without being adsorbed on the resin, and subsequent water washing of the resin further completes the removal of water-soluble minerals and hydrophilic substances.
[0015]
Next, the adsorbed anthocyanin dye is eluted from the nonpolar porous polymer resin using a hydrophilic organic solvent. Examples of the hydrophilic organic solvent used for elution include ethanol, methanol, acetone, and the like. For food dyes, ethanol is preferable, and an 80% ethanol aqueous solution is more preferable.
[0016]
An anthocyanin-containing plant pigment extract purified with a nonpolar porous polymer resin may be concentrated as it is to obtain a pigment-purified concentrate. However, residual impurities such as odors and proteins may be added to zeolite, perlite, kaolin, etc. Insoluble mineral substances may be removed, or low molecular weight volatile substances may be removed by steam distillation.
[0017]
The pigment eluate of an anthocyanin-containing plant is concentrated by a known means such as vacuum concentration to obtain a pigment purified concentrate. Concentrating has the following effects.
[0018]
(1) Since the addition amount of the anthocyanin coloring liquid with respect to foodstuffs can be reduced, the influence with respect to the flavor and structure | tissue property of foodstuffs can be prevented.
[0019]
(2) The volume is reduced by concentration, which is convenient for use and storage.
[0020]
(3) The volume is reduced by concentration, and the packaging material cost and transportation cost can be saved.
[0021]
(4) The reduction rate of the color value is suppressed by the concentration.
[0022]
Concentration is preferably performed until the color value of the concentrated solution reaches about 400 to 1,500.
[0023]
By adding at least one selected from the group consisting of sorbitol, reduced starch saccharified product, dextrin and trehalose to the purified anthocyanin pigment purified concentrate thus prepared, the red cabbage pigment purified and concentrated obtained by treatment with a nonpolar porous polymer resin It is possible to prevent the precipitation of dye crystals when the liquid is stored at a low temperature. Of the substances that prevent the formation of dye crystals of the anthocyanin dye purified concentrate purified with a nonpolar porous polymer resin, sorbitol and reduced starch saccharified products that are difficult to be fermented by microorganisms are preferred because of their high effects.
[0024]
What is necessary is just to select suitably the addition amount of these compounds which prevent precipitation of a pigment crystal | crystallization in the range of 4-30% per the anthocyanin pigment refinement | concentration concentrate used as a product. If it is less than 4%, the effect of preventing the formation of dye crystals is small, and even if added over 30%, the effect is not increased and the cost is increased, which is not preferable.
[0025]
In order to finally obtain an anthocyanin pigment refining concentrate, water and citric acid, and if necessary, caustic soda are added to adjust the pH to 1.5 to 3.0 and a color value of about 400 to 1000 to obtain a desired color value. What is necessary is just to have it. If necessary, ethanol may be added to suppress the growth of microorganisms.
[0026]
As will be apparent from Experimental Example 1 described later, the red cabbage dye purified concentrate treated with a nonpolar porous polymer resin produces dye crystals during low-temperature storage, whereas the control dye without resin treatment is used. The concentrate does not produce pigment crystals. Moreover, since there is no difference between the dyes in the two concentrated liquids, it is suggested that the presence or absence of dye crystals is caused by a difference in components other than the dyes in the two concentrated liquids.
[0027]
Regarding the difference in ingredients, there is a substance (protective substance) that protects the dye molecules in the control dye concentrate, which is presumed to prevent aggregation of the dye molecules and consequently suppress the formation and growth of crystals. .
[0028]
On the other hand, in the red cabbage dye solution treated with the nonpolar porous polymer resin, since there is no protective substance, the dye molecules are gathered to grow into crystals.
[0029]
Nonpolar porous polymer resin adsorbs substances having a hydrophobic structure (eg, anthocyanins, proteins, etc.), but does not adsorb hydrophilic substances (eg, carbohydrates, etc.) not having a hydrophobic structure, and these are washed away. .
[0030]
The dye molecule protecting substance that prevents the formation and growth of dye crystals is considered to be contained in a hydrophilic component that is washed away without being adsorbed by the nonpolar porous polymer resin. In addition, it is extremely difficult to identify or recover the protective substance in this runoff section.
[0031]
【Example】
Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.
[0032]
Experimental example 1
(1) Red cabbage pigment extract The red cabbage is cut, immersed in a citric acid solution having a pH of 2.5 to 3.0, left to stand overnight, and filtered to obtain a transparent pigment extract (color value of about 8). It was.
[0033]
The color value of red cabbage was determined by appropriately diluting the red cabbage dye solution with Muclvaine buffer pH 3.0, measuring the absorbance at a wavelength of 532 nm (the maximum absorption wavelength of the red cabbage dye), and converting the absorbance value to the concentration before dilution. (E100%, 1 cm, 532 nm). The subsequent color values were measured according to this method.
[0034]
(2) Preparation of concentrated dye solution The transparent red cabbage dye extract described above was vacuum concentrated to obtain a concentrated dye solution having a color value of about 1200. Citric acid, water, and, if necessary, caustic soda were added to the concentrated dye solution to prepare a red cabbage dye concentrated solution having a color value of 850 and a color value of 400. Since this non-polar porous polymer resin is not used, this dye concentrate is hereinafter abbreviated as “control color value 850 dye solution” and “control color value 400 dye solution”, respectively.
[0035]
(3) Preparation of concentrated dye liquid treated with nonpolar porous polymer resin According to the description in Example 1 of “Method for producing red cabbage dye” (Japanese Patent Application No. 8-70312), the above transparent red The cabbage dye extract is treated with a non-polar porous polymer resin (manufactured by Mitsubishi Kasei Co., Ltd., “HP-20”) column to adsorb the red cabbage dye to the resin, and then the resin is washed with water and then 80% ethyl. The red cabbage pigment was eluted with an aqueous alcohol solution. The eluted dye solution was concentrated in vacuo to obtain a concentrated dye solution having a color value of about 1200.
[0036]
To this concentrated dye solution, citric acid and water, and if necessary, caustic soda were added to prepare a red cabbage dye concentrate solution having a color value of 850 and a color value of 400 as in (2). Hereinafter, the dye concentrates are abbreviated as “resin-treated color value 850 dye solution” and “resin-treated color value 400 dye solution”, respectively.
[0037]
(4) Refrigerated storage test of concentrated dye solution The above-mentioned “control color value 850 dye solution”, “control color value 400 dye solution”, “resin-processed color value 850 dye solution”, “resin-processed color value 400 dye solution” Each was placed in a brown bottle and stored in a refrigerator (8 ° C. or lower) for 3 weeks, and then centrifuged to measure the color value of the separated solution, and the color value reduction rate was calculated. The results are shown in Table 1. The color value reduction rate was determined by the following formula.
[0038]
[Expression 1]

[0039]
[Table 1]

[0040]
As is apparent from the results in Table 1, the “control color value 400 dye solution” and “control color value 850 dye solution” had a color value decrease rate of 4% or less even when stored at a low temperature for 3 weeks. On the other hand, the color value of the dye solution treated with the nonpolar porous polymer resin is greatly reduced.
[0041]
That is, the color value decreased by 12% for the “resin-treated color value 400 dye solution” and 22% for the “resin-treated color value 850 dye solution” after storage for 3 weeks in the refrigerator.
[0042]
A large amount of reddish purple crystal precipitates was observed at the bottom of the brown bottle storing the “resin-treated color value 400 dye solution” and “resin-treated color value 850 dye solution”. The reddish purple crystals dissolved when heated in the liquid.
[0043]
The “resin-treated color value 400 dye solution” and “resin-treated color value 850 dye solution” containing a large amount of reddish purple crystals produced by refrigerated storage are heated to about 50 ° C. to dissolve the crystals, When the color value was measured after cooling, the color value was almost the same as that of the dye solution before storage. The absorption curves obtained by measuring the absorbance of the dye solution having the restored color value are “control color value 400 dye solution”, “control color value 850 dye solution”, “control color value 400 dye solution”, and “control color value” before storage. This corresponds to the absorption curve of “850 dye solution”. The measurement results are shown in FIG.
[0044]
Further, the color tone (L, a, b value) of the control dye solution, the dye solution before storage and the restored dye solution was measured. The results are shown in Table 2. As is clear from the results in Table 2, ΔE was 1 or less, and no change in color tone was observed macroscopically.
[0045]
[Table 2]

[0046]
From the above experimental results, it is shown that the reddish purple crystal produced by refrigerated storage is a red cabbage dye itself, and that the dye itself is not different between the control and the resin-treated dye.
[0047]
The “control color value 400 dye solution” and the “control color value 850 dye solution” had a strong cabbage odor and were inappropriate as food colorants.
[0048]
Example 1
According to Experimental Example 1, a red cabbage pigment purified concentrated solution (color value: about 1200) treated with a nonpolar porous polymer resin was prepared. The obtained red cabbage pigment refining concentrate is heated to about 40 ° C., and various saccharides, sugar alcohols and hydrophilic emulsifiers as shown in Table 3 are directly added from the hydrophilic substances that can be used in the food industry. Dissolved.
[0049]
Add the cigarette, water, and if necessary, caustic soda to the red cabbage pigment refining concentrate in which the substances shown in Table 3 are dissolved to prepare a pigment solution having a pH of 2.8 and a color value of 850, and store it in the refrigerator (8 ° C or lower). After storage for a week, the color value of the upper layer was measured by centrifugation. The results are shown in Table 3. The dye reduction rate in the table is proportional to the dye crystal production.
[0050]
[Table 3]

[0051]
As is clear from the results shown in Table 3, the purified pigment concentrate containing the sorbitol, reduced starch saccharified product, dextrin, and trehalose of the present invention has a small color value reduction rate even when stored at a low temperature. It can be seen that the amount produced is small. On the other hand, saccharides such as glucose, fructose, lactose and maltose other than the present invention, and those added with sucrose fatty acid ester or polyglycerin fatty acid ester produced dye crystals when stored at low temperature, and the low-temperature stability was not good.
[0052]
Example 2
20 kg of red cabbage was appropriately cut, 80.0 liters of water was added, and sulfuric acid was added to adjust to pH 2.4 to obtain 77 liters of red cabbage pigment extract. The obtained pigment extract was passed through SV = 5 through a column packed with 2.5 liters of a nonpolar porous polymer resin (“HP-20” manufactured by Mitsubishi Kasei Kogyo Co., Ltd.). After passing through the solution, the nonpolar porous polymer resin adsorbing the dye was washed with water, and 5 liters of a hydrophilic organic solvent (80% ethanol) was passed through the column to elute the dye.
[0053]
The obtained eluate was concentrated under reduced pressure at 40 ° C. to obtain a dye concentrate having a color value of 1200. After filtering this dye concentrate under reduced pressure with a filter paper, 70.0 g each was weighed into five 100 ml brown bottles (No. 1 to No. 5) and the pH was adjusted to 3.0 or less. 2.0 g No. 1-No. 5 to each amber bottle. No. No. 1 as a control, No. 1 2, sorbitol 15%, No. 2 3 is 15% reduced starch saccharified, 4 is trehalose 15%, After 15% dextrin was added to 5 and dissolved, water was added to each brown bottle to adjust to 100.0 g (color value 840) and stored in a refrigerator (8 ° C. or lower) for 3 weeks. After storage, the contents were mixed well, transferred to a 100 ml centrifuge tube, centrifuged at 3000 rpm for 10 minutes, and the color value of the upper layer liquid was measured. Table 4 shows the color value and the color value decrease rate after storage.
[0054]
[Table 4]

[0055]
As is apparent from the results shown in Table 4, the color value of the control product (No. 1) to which the compound of the present invention was not added was reduced by 19%, and a large amount of reddish purple crystals were precipitated in the preserved product. In contrast, No. 1 to which the compound of the present invention was added was added. 2-No. No. 5 showed almost no crystalline precipitate, and the color value reduction rate was 3% or less.
[0056]
Example 3
A column packed with 70 liters of red cabbage pigment extract (pH 2.6, color value 9) and 2 liters of a nonpolar porous polymer resin ("SP-206", manufactured by Mitsubishi Kasei Kogyo Co., Ltd.) 4 and then washed with 4 liters of water, the pigment was eluted with 4.5 liters of 80% ethanol, and the eluate was concentrated under reduced pressure to obtain 370 grams of an eluate having a color value of 1500. The dye concentrate was filtered under reduced pressure with filter paper, weighed 55.0 g each in three 100 ml brown bottles (No. 1 to No. 3), and citric acid 2. 0 g and 20 g ethanol were added to prevent microbial growth.
[0057]
No. 1, 23 g of water was added to make a total of 100 g (color value 825). No. 2 was added 20 g of sorbitol solution (70% sorbitol) and 3 g of water to make a total of 100 g. No. 3 was added 20 g of reduced starch saccharified product (trade name: “AMAMIR” manufactured by Towa Kasei Kogyo Co., Ltd.) and 3 g of water to make a total of 100 g. No. 1-No. 3 was stored in a refrigerator (8 ° C. or lower) for 3 weeks. After storage, the contents were mixed well, transferred to a 100 ml centrifuge tube, centrifuged at 3000 rpm for 10 minutes, and the color value of the upper layer liquid was measured. Table 5 shows the color value and the color value reduction rate after storage.
[0058]
[Table 5]

[0059]
As is apparent from the results shown in Table 5, the control product (No. 1) to which no sorbitol or reduced starch saccharified product was added had a color value decreased by 23%, and a large amount of reddish purple crystals were precipitated in the stored product. Was observed, whereas sorbitol and reduced starch saccharified product were added. 2, no. No. 3 showed almost no crystalline precipitate, and the color value reduction rate was 3% or less.
[0060]
Example 4
Murasaki potato pigment extract, pH 2.3, color value E ^100%, 530 nm = 15.0 (pH 3.0, Mclvaine buffer) 50 L nonpolar porous polymer resin (trade name “HP-20”, Mitsubishi Chemical Industries) (Made by Co., Ltd.) A column filled with 2 L was passed at SV = 3, and after washing with water 4 L, the dye was eluted with 4 L of 70% (V / V) ethanol, and the eluate was concentrated under reduced pressure to obtain E ^100. 420 g of a dye solution of ^% 530 nm = 1500 was obtained. This dye concentrate was filtered under reduced pressure with a filter paper, weighed 55.0 g each in three 100 ml brown bottles (No. 1 to No. 3), and citric acid (crystal) 2 to adjust the pH to 3.0 or less. 0.0 g and 20 g ethanol were added to prevent microbial growth.
[0061]
No. In 1, 23 g of water was added to make a total of 100 g (color value 825). No. 2 was added 20 g of sorbitol solution (70% sorbitol) and 3 g of water to make a total of 100 g. No. 3 was added 20 g of reduced starch saccharified product (trade name “AMAMIR”, manufactured by Towa Kasei Kogyo Co., Ltd.) and 3 g of water to make a total of 100 g. No. 1-No. 3 brown bottles were stored in a refrigerator (8 ° C. or lower) for 3 weeks. After storage, the contents were mixed well, transferred to a 100 ml centrifuge tube, centrifuged at 3000 rpm for 10 minutes, and the color value of the upper layer liquid was measured. Table 6 shows the color value and the color value decrease rate after storage.
[0062]
[Table 6]

[0063]
As is clear from the results shown in Table 6, in the purified anthocyanin pigment concentrate using purple potato as a raw material, the control product (No. 1) to which sorbitol or reduced starch is not added has a color value reduced by 21.2%. In the preserved product, a large amount of reddish purple crystals were precipitated, whereas No. 1 containing sorbitol and reduced starch saccharified product was added. 2, no. In No. 3, almost no crystalline precipitate was observed, and the color value reduction rate was 3% or less. Example 5
Extract of perilla pigment, pH 2.1, color value E ^100% 520 nm = 7.0 (pH 3.0, Mclvaine buffer) 70 L was applied to nonpolar porous polymer resin (trade name “SP-207”, Mitsubishi Kasei Kogyo ( (Made by Co., Ltd.) A column packed with 2 L was passed through SV = 4, washed with water 4 L, then the pigment was eluted with 4 L of 80% (V / V) ethanol, and the eluate was concentrated under reduced pressure to obtain E ^100% 520 nm. = 260 g of a dye solution of 1500 was obtained. The dye concentrate was filtered under reduced pressure with filter paper, weighed 42.0 g each in three 100 ml brown bottles (No. 1 to No. 3), and citric acid (crystal) 2 to adjust the pH to 3.0 or less. 0.0 g and 15 g ethanol were added to prevent microbial growth. No. 1, 41 g of water was added to make a total of 100 g (color value 630). No. To 2 was added 20 g of sorbitol solution (70% sorbitol) and 21 g of water to make a total of 100 g. No. 3 was added 20 g of reduced starch saccharified product (trade name “AMAMIR” manufactured by Towa Kasei Kogyo Co., Ltd.) and 21 g of water to make a total of 100 g. No. 1-No. 3 brown bottles were stored in a refrigerator (8 ° C. or lower) for 3 weeks. After storage, the contents were mixed well, transferred to a 100 ml centrifuge tube, centrifuged at 3000 rpm for 10 minutes, and the color value of the upper layer liquid was measured. Table 7 shows the color value and the color value decrease rate after storage.
[0064]
[Table 7]

[0065]
As is apparent from the results shown in Table 7, in the purified anthocyanin pigment concentrate using perilla as a raw material, the control product (No. 1) to which sorbitol or reduced starch is not added has a color value reduced by 41.4%, In the preserved product, a large amount of red crystals were precipitated, whereas No. 1 containing sorbitol and reduced starch saccharified product was added. 2, no. In No. 3, the crystalline precipitate was slight and the color value reduction rate was 6.5% or less.
[0066]
Example 6
Red radish pigment extract, pH 2.3, color value E ^100% 510 nm = 4.1 (pH 3.0, Mclvaine buffer) 90 L nonpolar porous polymer resin (trade name “SP-207”, Mitsubishi Chemical Industries) (Made by Co., Ltd.) A column filled with 2 L was passed at SV = 4, washed with water 4 L, then the dye was eluted with 4 L of 85% (V / V) ethanol, the eluate was concentrated under reduced pressure, and E ^100% 210 g of a dye solution with 510 nm = 1500 was obtained. The dye concentrate was filtered under reduced pressure with filter paper, weighed 42.0 g each in three 100 ml brown bottles (No. 1 to No. 3), and citric acid (crystal) 2 to adjust the pH to 3.0 or less. 0.0 g and 15 g ethanol were added to prevent microbial growth.
[0067]
No. 1, 41 g of water was added to make a total of 100 g (color value 630). No. To 2 was added 20 g of sorbitol solution (70% sorbitol) and 21 g of water to make a total of 100 g. No. 3 was added 20 g of reduced starch saccharified product (trade name “AMAMIR” manufactured by Towa Kasei Kogyo Co., Ltd.) and 21 g of water to make a total of 100 g. No. 1-No. 3 brown bottles were stored in a refrigerator (8 ° C. or lower) for 3 weeks. After storage, the contents were mixed well, transferred to a 100 ml centrifuge tube, centrifuged at 3000 rpm for 10 minutes, and the color value of the upper layer liquid was measured. Table 8 shows the color value and the color value decrease rate after storage.
[0068]
[Table 8]

[0069]
As is clear from the results shown in Table 8, in the purified anthocyanin pigment concentrate using red radish as a raw material, the control product (No. 1) to which sorbitol or reduced starch is not added has a color value reduced by 30.2%. In the preserved product, a large amount of reddish orange crystals were precipitated, whereas No. sorbitol and reduced starch saccharified product were added. 2, no. In No. 3, the crystalline precipitate was slight, and the color value reduction rate was 4% or less.
[0070]
【The invention's effect】
An anthocyanin dye refining concentrate treated with a nonpolar porous polymer resin is easy to produce dye crystals, is not suitable for commercial use, and is inconvenient in use. According to the present invention, the production of pigment crystals is prevented, and the quality of the pigment purified concentrate of anthocyanin-containing plants purified by treatment with a nonpolar porous polymer resin is improved.
[Brief description of the drawings]
1 is a graph showing the results of measuring the absorbance of a red cabbage dye in Experimental Example 1. FIG.

Claims

At least one selected from the group consisting of sorbitol, reduced starch saccharified product, dextrin and trehalose is added to an anthocyanin pigment refined concentrate obtained by treating a pigment extract of an anthocyanin-containing plant with a nonpolar porous polymer resin and concentrating it. A method for improving the quality of a pigment purified concentrate of an anthocyanin-containing plant, characterized in that the formation of pigment crystals of the anthocyanin pigment purified concentrate is prevented by adding the above compound.

The method for improving the quality of an anthocyanin-containing plant pigment-purified concentrate according to claim 1, wherein the anthocyanin-containing plant is red cabbage, purple potato, perilla or red radish.

The method for improving the quality of an anthocyanin-containing plant pigment refining concentrate according to claim 1, wherein the nonpolar porous polymer resin is a styrene resin or an acrylic resin.

The addition amount of at least one compound selected from the group consisting of sorbitol, reduced starch saccharified product, dextrin and trehalose is 4% by weight or more per red cabbage pigment purified concentrate. A method for improving the quality of a purified concentrate of an anthocyanin-containing plant.