JP4001275B2 - Astaxanthin-containing pigment oil - Google Patents
Astaxanthin-containing pigment oil Download PDFInfo
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- JP4001275B2 JP4001275B2 JP2002182414A JP2002182414A JP4001275B2 JP 4001275 B2 JP4001275 B2 JP 4001275B2 JP 2002182414 A JP2002182414 A JP 2002182414A JP 2002182414 A JP2002182414 A JP 2002182414A JP 4001275 B2 JP4001275 B2 JP 4001275B2
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Description
【０００１】
【産業上の利用分野】
本発明は、甲殻類、特にオキアミに含有されるアスタキサンチン色素を主要色素成分とする色素油と、その製造方法に関する。より詳細には、本発明は、アスタキサンチンを主成分とするカロテノイド色素を含むオキアミ等魚介類を、乳酸菌、麹菌、酵母のいずれか１種、または２種以上を組み合わせて用いて発酵し、その後、圧搾、分別浮上させることにより、効率良く得られるアスタキサンチン含有色素油、必要に応じ濃縮したもの、ならびにそれらの製造法に関するものである。
【０００２】
【従来の技術】
食用色素には従来から使用されている合成着色料としては赤色、黄色、緑色、青色タール色素とそのアルミニウムキレートおよび酸化鉄や二酸化チタン、銅クロロフィリンナトリウム、鉄クロロフィリンナトリウム、水溶性アナトー、β−カロテンがその使用目的に応じ認可されている。これらは広く利用されているが、健康や安全性への関心の高まりとともに天然色素へ代わりつつある。
この様な天然色素としてはこれまでにβ−カロチン、パプリカ色素、アナトー色素、紅麹色素、コチニール、紅花色素等が市場にあり、よく利用されているが、原料のほとんどは輸入されており、供給、価格等に不安定なものが多く、また、耐光性、耐熱性、色素濃度、臭い等で満足の行くものがなく、新たな食用色素の開発が望まれている。
【０００３】
アスタキサンチンはβ−カロテン等のカロテノイド系色素の中でも最も赤色色調が高く、熱、光、ｐＨ等にたいする安定性も比較的良好である上、カニ、エビ、サケ等の生産食品から日常的に摂取していることから安全性の点から問題ない。さらに、アスタキサンチンは抗酸化性、免疫賦活等の有用機能を有していることも知られ、天然色素としてもこれまでにない新しい機能性色素として注目されている。
【０００４】
オキアミ、イサザアミ、クルマエビ、ブラックタイガー、ズワイガニ、タラバガニなどを始め、広く海産の甲殻類に含まれるアスタキサンチンは赤橙色であるために、天然物由来の色素として食用色素、化粧品色素あるいは養殖魚の体色改善剤などへの利用が期待され、これまで多くの研究開発がなされてきた。特に、オキアミは生物資源量が膨大であり、比較的酸化安定性が高いエステル型のアスタキサンチンを主成分とするため、抽出されたカロテノイド色素も酸化安定性があることから食品への利用が望まれていた。
【０００５】
しかしながら、アスタキサンチンを始めカロテノイド色素は脂溶性であるために、その抽出方法は、特公平３−４８８８４号公報に示されるようにヘキサン、エタノールなどによる有機溶剤抽出を行うものであったり、特開平６−２００１７９号公報に示されるように二酸化炭素を用いた超臨界ガスによる抽出を行う必要があるものであった。これらの方法は、有機溶剤回収にかかるランニングコスト、超臨界抽出装置導入に関わるイニシャルコストが大きく、製法としては完成しても実用化には課題が多く、実際の食用色素の生産には至っていないのが現状である。
【０００６】
【発明が解決しようとする課題】
オキアミを原料に用いて有機溶剤抽出した色素油は、トリグリセリドとリン脂質がほぼ同等含まれており、その主要な脂肪酸種は高度不飽和脂肪酸であるエイコサペンタエン酸、ドコサヘキサエン酸であるため酸化安定性が低いことが知られている。しかし、食品添加物であるトコフェロール存在下ではエチルエステル体が、トリグリセリド体や遊離体よりも酸化安定性が高いことが報告されている（遠藤泰志他、平成６年度日本水産学会春季大会講演要旨集、ｐ２４８）。
【０００７】
本発明は、安定性の高い良質なアスタキサン含有色素油を提供することを目的とする。より詳細には、本発明は、アスタキサンチンを含むカロテノイド色素を有機溶剤抽出、超臨界抽出などをせずに、安価に効率良く抽出し、安定性の高い良質なアスタキサン含有色素油を提供することを目的とする。
また、本発明は、脂肪酸エステル体や遊離脂肪酸などを主要脂質成分とする色素濃縮が行いやすい性状を有するアスタキサン含有色素油を提供することを目的とする。
さらに、本発明は、脂肪酸エステル主体のアスタキサン含有色素油を提供することを目的とする。
【０００８】
【課題を解決するための手段】
本発明は、乳酸菌発酵、麹菌発酵、酵母発酵のいずれか１つまたは２つ以上を組み合わせた発酵処理を行った水産物、好ましくは甲殻類、より好ましくはオキアミから抽出したアスタキサンチン含有色素油、好ましくはアスタキサンチン濃度が４００ｐｐｍ以上であるアスタキサンチン含有色素油を要旨としている。
【０００９】
また本発明は、主要色素成分がアスタキサンチンであり、脂質成分の主成分が脂肪酸エステルである水産物、好ましくは甲殻類、より好ましくはオキアミ由来のアスタキサンチン含有色素油、好ましくはアスタキサンチン濃度が４００ｐｐｍ以上であるアスタキサンチン含有色素油を要旨としている。
【００１０】
脂肪酸エステルの含有量が４０％以上である脂質成分を含有しており、その場合、本発明は、乳酸菌発酵、麹菌発酵、酵母発酵のいずれか１つまたは２つ以上を組み合わせた発酵処理を行った水産物、好ましくは甲殻類、より好ましくはオキアミから抽出した、脂肪酸エステルの含有量が４０％以上である脂質成分を含有するアスタキサンチン含有色素油、好ましくはアスタキサンチン濃度が４００ｐｐｍ以上であるアスタキサンチン含有色素油である。または主要色素成分がアスタキサンチンであり、脂質成分の主成分が含有量４０％以上の脂肪酸エステルである水産物、好ましくは甲殻類、より好ましくはオキアミ由来のアスタキサンチン含有色素油、好ましくはアスタキサンチン濃度が４００ｐｐｍ以上であるアスタキサンチン含有色素油である。
【００１１】
また、本発明は、カロテノイド色素を含む水産物、好ましくは甲殻類、より好ましくはオキアミを発酵処理した後、圧搾、分別浮上させるアスタキサンチン含有色素油の製造方法を要旨としている。
【００１２】
発酵処理が、乳酸菌発酵、麹菌発酵、酵母発酵のいずれか１つまたは２つ以上を組み合わせたものであり、その場合、本発明は、カロテノイド色素を含む水産物、好ましくは甲殻類、より好ましくはオキアミを乳酸菌発酵、麹菌発酵、酵母発酵のいずれか１つまたは２つ以上を組み合わせた発酵処理をした後、圧搾、分別浮上させるアスタキサンチン含有色素油の製造方法である。
【００１３】
【発明の実施の形態】
本発明の色素油の製造方法の概略は、以下の通りである。
アスタキサンチンを主成分とするカロテノイド色素を含むオキアミ等魚介類を、乳酸菌、麹菌、酵母のいずれか１種、または２種以上を組み合わせて用いて発酵し、その後、圧搾、分別浮上させることにより、効率良く色素油を製造するものである。さらに、得られた色素油をアルカリ脱酸などによる遊離脂肪酸除去、分子蒸留などによる脂肪酸エステルの除去により、色素含量を高めた色素油を製造することができる。
【００１４】
本発明の原料としては、アスタキサンチンを主成分とするカロテノイド色素を含有する水産物であれば用いることができるが、原料が容易に入手でき、また価格が安価で色素濃度の高いものが好ましい。例えば、南極オキアミ（Euphausia antarctica）、太平洋オキアミ（Euphausia pacifica）、イサザアミ（Neomysis intermedia）などが例示できるが、これら甲殻類のみに限定されるものではなく、魚介類の体内にアスタキサンチンを主成分とするカロテノイド色素を含有するものであれば原料とすることが可能である。
【００１５】
これらの原料をそのまま、あるいは加熱後に清水を加え、添加する微生物に適した塩濃度になるように加塩して発酵処理を行う。すなわち、オキアミ等魚介類に麹および／あるいは食塩水を混合して、さらに乳酸菌および酵母を添加し、発酵、熟成させ製造する。その時の食塩濃度は約１０〜２５％（W／W）になるように調整することが望ましい。この混合物を２０℃で５ヵ月間維持し発酵処理を行う。
【００１６】
本発明において、酵素、熟成のために使用する耐塩性微生物は、特に限定されない。例えば、耐塩性乳酸菌（Tetragenococcus halophilus, Tetragenococcus muriaticus）耐塩性酵母（Zygosaccharomyces rouxii, Torulopsis magnoliae, Torulopsis nodaensis）などが使用される。
【００１７】
発酵処理後、発酵混合物（以下、諸味という）を圧搾袋に充填して圧搾することによって固液分離を行い固形物を除去し、液状部分を採取する。この際、圧搾は通常の穀醤製造と同様に、徐々に加圧して、アスタキサンチン含量の低い液状部は除去し、押切りといわれる最大加圧時に採取される液状物を、さらに低温下、静置しておくことで分離してくるアスタキサンチンを主成分とするカロチノイド色素を分離取得することができる。
【００１８】
得られた色素油のアルカリ脱酸などによる遊離脂肪酸除去は、水酸化ナトリウム、水酸化カリウム、水酸化カルシウム等のアルカリを添加することにより生成する脂肪酸のアルカリ石鹸を除き、アスタキサンチン類を濃縮精製する。分子蒸留などによる脂肪酸エステルの除去は、分子蒸留装置を用いて減圧蒸留を行うことにより色素含量を高めた色素油を製造する。
【００１９】
【実施例】
本願発明の詳細を実施例で説明する。本願発明はこれら実施例によって何ら限定されるものではない。
【００２０】
実施例１
冷凍された未加熱オキアミ１００に対して、清水２０、塩２０を加えて３０分間ボイル冷却後、麹６０を添加し３日間空気撹拌した。次いで、この混合物（以下諸味）に乳酸菌Tetragenococcus halophilusを１×１０6/ml添加し諸味を２０℃に保った。その後、１ヵ月目に酵母Zygosaccharomyces rouxiiを１×１０/ml添加して４ヶ月間発酵させた。
この発酵工程を経て得られた諸味を圧搾袋に充填し、まず自然垂れ（自重、７時間）により流動性の高い液状部を除去し、更に予圧処理（５MPa、１２時間）して液状部分を除去した。
次いで、押切り処理（１５MPa、２４時間）して浸潤した含油液体を静置タンクに充填して、３日間静置分別した。その後、上層部分をデカンターにより分取してアスタキサンチン含有色素油を得た。得られた色素油の組成を表１に示した。
【００２１】
【表１】
実施例２
本発明の色素油を濃縮する方法を詳述する。実施例１により得られた色素油１００量部に、水酸化ナトリウム２０量部をパール状のまま添加して高速ミキサーにて３,０００〜４,０００rpm、３０分撹拌処理を行う。これにヘキサン２００量部を加えて更に撹拌し、濾過助剤（ハイフロスーパーセル）５量部を加えた後濾過処理を行った。得られた濾液を減圧濃縮して濃縮色素油Ａとした。組成を表２に示した。
【００２３】
【表２】
実施例３
本発明の色素油を濃縮する方法を更に詳述する。実施例１より得られた色素油を分子蒸留装置（日本車輌製）にて、０．１〜１．０Ｐａの減圧下、１２０〜１４０℃の加熱プレートにて薄膜化して減圧蒸留行った。得られた濃縮色素油（Ｂ）の組成を表３に示した。
【００２５】
【表３】
【発明の効果】
安定なエステル型のアスタキサンチンを高濃度に含有し、脂質成分としてはトリグリセライドではなく、脂肪酸エステルと遊離脂肪酸を主成分とする、従来にない脂質組成の色素油が提供できる。
また、発酵処理を施すことにより甲殻類由来の食用色素を、有機溶剤、超臨界ガスなどの装置を用いずに安価に製造できる。
色調、耐光性、着色性に優れるだけでなく、抗酸化活性、抗炎症作用、免疫賦活作用等の生理活性を有するアスタキサンチンを主要成分とする色素油を提供することができる。[0001]
[Industrial application fields]
The present invention relates to a pigment oil containing astaxanthin pigment contained in crustaceans, particularly krill, as a main pigment component, and a method for producing the pigment oil. More specifically, the present invention ferments using krill and other seafood containing a carotenoid pigment containing astaxanthin as a main component, using any one of lactic acid bacteria, koji molds, yeast, or a combination of two or more thereof, The present invention relates to an astaxanthin-containing pigment oil that is efficiently obtained by pressing and separating and floating, a concentrate concentrated as necessary, and a method for producing them.
[0002]
[Prior art]
Conventionally used synthetic colorants for food dyes include red, yellow, green, and blue tar dyes and their aluminum chelates, and iron oxide, titanium dioxide, copper chlorophyllin sodium, iron chlorophyllin sodium, water-soluble anato, β-carotene Are approved for their intended use. Although these are widely used, natural pigments are being replaced with increasing interest in health and safety.
As such natural pigments, β-carotene, paprika pigment, annatto pigment, sockeye pigment, cochineal, safflower pigment, etc. have been used in the market so far, but most of the raw materials are imported, There are many things that are unstable in supply, price, etc., and there is nothing satisfactory with respect to light resistance, heat resistance, dye concentration, odor, etc., and development of new food dyes is desired.
[0003]
Astaxanthin has the highest red color tone among carotenoid pigments such as β-carotene, has relatively good stability to heat, light, pH, etc., and is taken daily from production foods such as crab, shrimp and salmon. Therefore, there is no problem in terms of safety. Furthermore, astaxanthin is known to have useful functions such as antioxidant properties and immunostimulation, and has attracted attention as a new functional pigment that has never existed as a natural pigment.
[0004]
Astaxanthin, which is widely contained in marine crustaceans, including krill, isazaami, tiger prawn, black tiger, snow crab, and king crab, is red-orange, so it improves food color, cosmetic pigment, or cultured fish color as a natural pigment. Many researches and developments have been made so far. In particular, krill has an enormous amount of biological resources and is mainly composed of ester-type astaxanthin, which has relatively high oxidative stability. Therefore, the extracted carotenoid pigments are also oxidatively stable, so that they are expected to be used in foods. It was.
[0005]
However, since carotenoid pigments such as astaxanthin are fat-soluble, the extraction method is to perform organic solvent extraction with hexane, ethanol, etc. as disclosed in Japanese Patent Publication No. 3-48884. As described in Japanese Patent Publication No. 20001919, it was necessary to perform extraction with a supercritical gas using carbon dioxide. These methods have a large running cost for organic solvent recovery and initial cost for introducing a supercritical extraction device, and even if completed as a production method, there are many problems in practical use, and no actual food coloring has been produced. is the current situation.
[0006]
[Problems to be solved by the invention]
Pigment oil extracted from organic solvents using krill as a raw material contains almost equal amounts of triglycerides and phospholipids, and the main fatty acid species are highly unsaturated fatty acids, eicosapentaenoic acid and docosahexaenoic acid, which are oxidatively stable. Is known to be low. However, it has been reported that in the presence of tocopherol, which is a food additive, the ethyl ester form has higher oxidative stability than the triglyceride form and free form (Yoshishi Endo et al. P248).
[0007]
An object of the present invention is to provide a high-quality astaxane-containing pigment oil having high stability. More specifically, the present invention provides a high-quality, high-stability astaxane-containing pigment oil that efficiently and inexpensively extracts carotenoid pigments containing astaxanthin without organic solvent extraction or supercritical extraction. Objective.
Another object of the present invention is to provide an astaxane-containing pigment oil having a property that facilitates pigment concentration using fatty acid ester or free fatty acid as a main lipid component.
Furthermore, an object of the present invention is to provide an astaxane-containing pigment oil mainly composed of fatty acid esters.
[0008]
[Means for Solving the Problems]
The present invention is an astaxanthin-containing pigment oil extracted from a marine product, preferably a crustacean, more preferably krill, which has been subjected to a fermentation treatment combining any one or more of lactic acid bacteria fermentation, koji mold fermentation, yeast fermentation, The gist is an astaxanthin-containing pigment oil having an astaxanthin concentration of 400 ppm or more.
[0009]
In the present invention, the main pigment component is astaxanthin, and the main component of the lipid component is a marine product, preferably a crustacean, more preferably an astaxanthin-containing pigment oil derived from krill, preferably an astaxanthin concentration of 400 ppm or more. The gist of astaxanthin-containing pigment oil is used.
[0010]
It contains a lipid component having a fatty acid ester content of 40% or more. In this case, the present invention performs a fermentation treatment combining any one or two or more of lactic acid bacteria fermentation, koji mold fermentation, and yeast fermentation. Astaxanthin-containing pigment oil containing a lipid component having a fatty acid ester content of 40% or more, preferably astaxanthin-contained pigment oil having an astaxanthin concentration of 400 ppm or more, extracted from marine products, preferably crustaceans, more preferably krill It is. Alternatively, a marine product in which the main pigment component is astaxanthin and the lipid component is a fatty acid ester having a content of 40% or more, preferably a crustacean, more preferably an astaxanthin-containing pigment oil derived from krill, preferably an astaxanthin concentration of 400 ppm or more This is an astaxanthin-containing pigment oil.
[0011]
Further, the gist of the present invention is a method for producing an astaxanthin-containing pigment oil that is subjected to a fermentation treatment of a marine product containing a carotenoid pigment, preferably a crustacean, more preferably krill, and then pressed and fractionated.
[0012]
The fermentation treatment is a combination of any one or more of lactic acid bacteria fermentation, koji mold fermentation and yeast fermentation. In this case, the present invention is a marine product containing carotenoid pigments, preferably crustaceans, more preferably krill. Is a method for producing an astaxanthin-containing pigment oil that is subjected to a fermentation treatment in which any one or two or more of lactic acid bacteria fermentation, koji mold fermentation, and yeast fermentation are combined, and then pressed and fractionated.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
The outline of the method for producing the pigment oil of the present invention is as follows.
Efficiency can be obtained by fermenting krill and other seafood containing carotenoid pigments mainly composed of astaxanthin using any one or more of lactic acid bacteria, koji molds, and yeasts, and then pressing and separating and floating It often produces pigment oil. Furthermore, the obtained pigment oil can be produced by removing free fatty acids by alkali deoxidation or the like, or by removing fatty acid esters by molecular distillation or the like to increase the pigment content.
[0014]
As a raw material of the present invention, any marine product containing a carotenoid pigment mainly composed of astaxanthin can be used, but a raw material is easily available, is inexpensive and has a high pigment concentration. Examples include Antarctic krill ( Euphausia antarctica ), Pacific krill ( Euphausia pacifica ), Isaami ( Neomysis intermedia ), etc., but are not limited to these crustaceans. Any material that contains a carotenoid pigment can be used as a raw material.
[0015]
These raw materials are subjected to a fermentation treatment by adding fresh water as it is or after heating, and salting to a salt concentration suitable for the microorganism to be added. That is, it is produced by mixing salmon and / or saline with seafood such as krill, adding lactic acid bacteria and yeast, fermenting and aging. It is desirable to adjust the salt concentration at that time to be about 10 to 25% (W / W). This mixture is maintained at 20 ° C. for 5 months and subjected to fermentation treatment.
[0016]
In the present invention, enzymes and salt-resistant microorganisms used for aging are not particularly limited. For example, salt-tolerant lactic acid bacteria ( Tetragenococcus halophilus , Tetragenococcus muriaticus ), salt-tolerant yeast ( Zygosaccharomyces rouxii , Torulopsis magnoliae , Torulopsis nodaensis ) and the like are used.
[0017]
After the fermentation treatment, the fermentation mixture (hereinafter referred to as moromi) is filled into a compression bag and pressed to perform solid-liquid separation to remove the solid matter and collect a liquid portion. At this time, in the same manner as in the production of normal grain soy, the pressing is gradually performed to remove the liquid part having a low astaxanthin content, and the liquid material collected at the time of the maximum pressing, which is called press-cutting, is further cooled at a low temperature. A carotenoid pigment containing astaxanthin as a main component can be separated and obtained.
[0018]
Free fatty acid removal of the resulting pigment oil by alkaline deoxidation and the like is carried out by excluding alkaline soaps of fatty acids produced by adding alkali such as sodium hydroxide, potassium hydroxide, calcium hydroxide, etc., and astaxanthins are concentrated and purified. . The removal of the fatty acid ester by molecular distillation or the like produces a pigment oil having an increased pigment content by performing vacuum distillation using a molecular distillation apparatus.
[0019]
【Example】
The details of the present invention will be described in Examples. The present invention is not limited to these examples.
[0020]
Example 1
Fresh water 20 and salt 20 were added to the frozen unheated krill 100, and after boiling for 30 minutes, the straw 60 was added and air-stirred for 3 days. Next, 1 × 10 6 / ml of lactic acid bacteria Tetragenococcus halophilus was added to this mixture (hereinafter, moromi) to keep the moromi at 20 ° C. Thereafter, 1 × 10 / ml of yeast Zygosaccharomyces rouxii was added in the first month and fermented for 4 months.
The moromi obtained through this fermentation process is filled into a compression bag, first the liquid part with high fluidity is removed by natural dripping (self-weight, 7 hours), and further the pre-pressure treatment (5 MPa, 12 hours) is applied to the liquid part. Removed.
Next, the oil-impregnated liquid that had infiltrated after the press-off treatment (15 MPa, 24 hours) was filled in a stationary tank, and was left to stand for 3 days. Then, the upper layer part was fractionated with a decanter to obtain an astaxanthin-containing pigment oil. The composition of the obtained pigment oil is shown in Table 1.
[0021]
[Table 1]
Example 2
The method for concentrating the pigment oil of the present invention will be described in detail. To 100 parts by weight of the pigment oil obtained in Example 1, 20 parts by weight of sodium hydroxide is added in the form of a pearl and stirred at 3,000 to 4,000 rpm for 30 minutes with a high speed mixer. 200 parts by weight of hexane was added thereto, and the mixture was further stirred, and after 5 parts by weight of a filter aid (Hyflo Supercell) was added, filtration treatment was performed. The obtained filtrate was concentrated under reduced pressure to obtain concentrated pigment oil A. The composition is shown in Table 2.
[0023]
[Table 2]
Example 3
The method for concentrating the pigment oil of the present invention will be described in further detail. The pigment oil obtained from Example 1 was subjected to vacuum distillation using a molecular distillation apparatus (manufactured by Nippon Vehicle Co., Ltd.) with a thin film formed on a heating plate at 120 to 140 ° C. under a reduced pressure of 0.1 to 1.0 Pa. The composition of the concentrated pigment oil (B) obtained is shown in Table 3.
[0025]
[Table 3]
【The invention's effect】
It is possible to provide a pigment oil having an unprecedented lipid composition, which contains a stable ester-type astaxanthin at a high concentration and is mainly composed of a fatty acid ester and a free fatty acid instead of triglyceride as a lipid component.
Further, by applying a fermentation treatment, food colors derived from crustaceans can be produced at low cost without using an apparatus such as an organic solvent or a supercritical gas.
It is possible to provide a pigment oil mainly composed of astaxanthin having not only excellent color tone, light resistance and colorability but also physiological activities such as antioxidant activity, anti-inflammatory activity, and immunostimulatory activity.
Claims (7)
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