JP3861941B2 - Oil composition containing highly unsaturated fatty acid with improved hydration - Google Patents
Oil composition containing highly unsaturated fatty acid with improved hydration Download PDFInfo
- Publication number
- JP3861941B2 JP3861941B2 JP08990997A JP8990997A JP3861941B2 JP 3861941 B2 JP3861941 B2 JP 3861941B2 JP 08990997 A JP08990997 A JP 08990997A JP 8990997 A JP8990997 A JP 8990997A JP 3861941 B2 JP3861941 B2 JP 3861941B2
- Authority
- JP
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- Prior art keywords
- fatty acid
- unsaturated fatty
- highly unsaturated
- reaction
- lipase
- 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.)
- Expired - Lifetime
Links
- 235000021122 unsaturated fatty acids Nutrition 0.000 title claims description 20
- 150000004670 unsaturated fatty acids Chemical class 0.000 title claims description 20
- 239000000203 mixture Substances 0.000 title claims description 18
- 230000036571 hydration Effects 0.000 title claims description 8
- 238000006703 hydration reaction Methods 0.000 title claims description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 40
- 239000004367 Lipase Substances 0.000 claims description 25
- 102000004882 Lipase Human genes 0.000 claims description 25
- 108090001060 Lipase Proteins 0.000 claims description 25
- 235000019421 lipase Nutrition 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 235000019197 fats Nutrition 0.000 claims description 23
- 235000020777 polyunsaturated fatty acids Nutrition 0.000 claims description 23
- 125000005456 glyceride group Chemical group 0.000 claims description 21
- 235000011187 glycerol Nutrition 0.000 claims description 19
- -1 alcohol ester Chemical class 0.000 claims description 12
- MBMBGCFOFBJSGT-KUBAVDMBSA-N all-cis-docosa-4,7,10,13,16,19-hexaenoic acid Chemical class CC\C=C/C\C=C/C\C=C/C\C=C/C\C=C/C\C=C/CCC(O)=O MBMBGCFOFBJSGT-KUBAVDMBSA-N 0.000 claims description 11
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 9
- 229930195729 fatty acid Natural products 0.000 claims description 9
- 239000000194 fatty acid Substances 0.000 claims description 9
- 150000004665 fatty acids Chemical class 0.000 claims description 9
- 235000020673 eicosapentaenoic acid Nutrition 0.000 claims description 5
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 claims description 4
- YZXBAPSDXZZRGB-DOFZRALJSA-N arachidonic acid Chemical compound CCCCC\C=C/C\C=C/C\C=C/C\C=C/CCCC(O)=O YZXBAPSDXZZRGB-DOFZRALJSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 claims description 3
- JAZBEHYOTPTENJ-JLNKQSITSA-N all-cis-5,8,11,14,17-icosapentaenoic acid Chemical compound CC\C=C/C\C=C/C\C=C/C\C=C/C\C=C/CCCC(O)=O JAZBEHYOTPTENJ-JLNKQSITSA-N 0.000 claims description 2
- 235000021342 arachidonic acid Nutrition 0.000 claims description 2
- 229940114079 arachidonic acid Drugs 0.000 claims description 2
- 229960005135 eicosapentaenoic acid Drugs 0.000 claims description 2
- JAZBEHYOTPTENJ-UHFFFAOYSA-N eicosapentaenoic acid Natural products CCC=CCC=CCC=CCC=CCC=CCCCC(O)=O JAZBEHYOTPTENJ-UHFFFAOYSA-N 0.000 claims description 2
- 229940040461 lipase Drugs 0.000 claims 1
- 239000003921 oil Substances 0.000 description 24
- 239000003925 fat Substances 0.000 description 22
- 238000000034 method Methods 0.000 description 19
- 235000020669 docosahexaenoic acid Nutrition 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 7
- 150000003626 triacylglycerols Chemical class 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 235000013305 food Nutrition 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 235000021588 free fatty acids Nutrition 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 241000589774 Pseudomonas sp. Species 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- OGBUMNBNEWYMNJ-UHFFFAOYSA-N batilol Chemical class CCCCCCCCCCCCCCCCCCOCC(O)CO OGBUMNBNEWYMNJ-UHFFFAOYSA-N 0.000 description 3
- 235000013361 beverage Nutrition 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000000199 molecular distillation Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000000194 supercritical-fluid extraction Methods 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 150000002632 lipids Chemical class 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 241000146387 Chromobacterium viscosum Species 0.000 description 1
- 241000555825 Clupeidae Species 0.000 description 1
- 241000238424 Crustacea Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 241000235527 Rhizopus Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229940090949 docosahexaenoic acid Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- ITNKVODZACVXDS-YNUSHXQLSA-N ethyl (4Z,7Z,10Z,13Z,16Z,19Z)-docosahexaenoate Chemical compound CCOC(=O)CC\C=C/C\C=C/C\C=C/C\C=C/C\C=C/C\C=C/CC ITNKVODZACVXDS-YNUSHXQLSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000019688 fish Nutrition 0.000 description 1
- 230000000887 hydrating effect Effects 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 229940127554 medical product Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 235000019512 sardine Nutrition 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Fats And Perfumes (AREA)
Description
【０００１】
【産業の属する技術分野】
本発明は、水和性を高めた部分グリセリドを主体とした高度不飽和脂肪酸含有油脂組成物に関する。
本発明において、高度不飽和脂肪酸（以下「ＰＵＦＡ」と略称することもある。）は、エイコサペンタエン酸（以下「ＥＰＡ」と略称することもある。）やドコサヘキサエン酸（以下「ＤＨＡ」と略称することもある。）などの１分子あたり１８個以上の炭素原子と３個以上の二重結合を有する脂肪酸を意味する。
また、本発明において、部分グリセリドはモノグリセリドやジグリセリドのように、グリセリン１分子に１または２分子の脂肪酸がエステル結合したものを意味する。
【０００２】
【従来の技術】
近年ＥＰＡやＤＨＡに代表されるＰＵＦＡの生理作用が明らかにされるのに伴い、食品や医療品などにもこれらＰＵＦＡが広く利用されるようになった。しかし、一般にＰＵＦＡは天然ではトリグリセリド中に存在しているため水に対する親和性が低く、そのままでは食品に幅広く応用することができないという問題があった。
【０００３】
この問題は乳化剤を併用することによってある程度解決することができるが、ＰＵＦＡ自体に乳化性を付与することができれば、十分な効果を発揮するだけの量のＰＵＦＡを食品などに添加する上で極めて有利である。
【０００４】
このような考えに基づいた油脂として「部分グリセリド含有油脂」という考え方がある。これは部分グリセリド、特にモノグリセリドが乳化剤としての性質を有することから、ＰＵＦＡ含有油脂に対してリパーゼなどで加水分解反応あるいはグリセロリシス反応を行い、部分グリセリドを生成することによって油脂自体に乳化性を付与するものである。このような報告例として特開平８−６０１８１（加水分解反応）や特開平８−２１４８９２（グリセロリシス反応）がある。しかしこれらの方法では原料油を構成脂肪酸まで分解しないため、例えば前者ではＤＨＡ濃度６０％強までしか濃縮されなかった。また後者の方法では原料と比較して基本的にＰＵＦＡの濃縮が無いなど、ＰＵＦＡの含有量の点で問題があった。
【０００５】
ＰＵＦＡの濃縮については、ウィンタリングやリパーゼによる加水分解法など種々の方法が盛んに研究されてきた。しかし、例えばウィンタリングではＤＨＡ濃度３５％程度が限界とされているなど、特定のＰＵＦＡを非常に高い濃度で含有する油脂を得るには問題があった。
【０００６】
一方、ＰＵＦＡ含有油脂を構成脂肪酸にまで分解した場合には、超臨界流体抽出法、尿素付加法、分子蒸留法、クロマトグラフ法などにより比較的容易に高度な濃縮が可能であることが知られている。このようにして濃縮されたＰＵＦＡとグリセリンからリパーゼの存在下、油脂を調製した例として長田ら〔日本水産学会誌，５７，１１９−１２５（１９９１）〕の報告や、特開平５−９５７９２などがある。これらの方法によれば非常に高濃度にＰＵＦＡを含有した油脂を得ることが可能であり、しかもリパーゼを用いると常温常圧で反応が進行するため、熱などによって酸化しやすいＰＵＦＡに適用しても品質の高い油脂を得ることが期待できる。しかし、前者の方法は合成効率が低く、未反応の脂肪酸が２０〜３０％存在した。また後者の方法で得られる油脂は高純度のトリグリセリドなので、その構造上水に対する親和性は期待できなかった。
【０００７】
【発明が解決しようとする課題】
本発明は高度不飽和脂肪酸を高濃度に含有し、なおかつ水に対する親和性を有する油脂を提供することを目的とする。本発明は、例えば透明性の高い飲料の用途に供するのに適した、水和性を高め非常に高濃度にＰＵＦＡを含有した油脂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、高純度原料由来の、部分グリセリド（モノグリセリドおよびジグリセリド）の合計がトリグリセリドより多いグリセリド組成をもつことを特徴とする水和性を高めた高度不飽和脂肪酸含有油脂組成物を要旨としている。
本発明の水和性を高めた高度不飽和脂肪酸含有油脂組成物は、リパーゼの存在下、高度不飽和脂肪酸あるいはそのアルコールエステルに対して過剰量のグリセリンを添加して反応を行うことによって製造することができる。
【０００９】
また、本反応における高度不飽和脂肪酸あるいはそのアルコールエステルは、公知の濃縮方法、例えば超臨界流体抽出法、尿素付加法、分子蒸留法、クロマトグラフ法などにより高度に濃縮されたものでも反応を進行させることができる。さらにまた、本反応では高度不飽和脂肪酸あるいはそのアルコールエステルとグリセリンの反応によって、部分グリセリドを主体とした油脂が生成する。その際、水あるいはアルコールが副産物として生じるが、これら副産物は逆反応の基質となり、反応の進行を妨げることがある。このとき、反応系を減圧条件下に置くことによって反応がより進行し、目的とする油脂を効率的に得ることができる。
【００１０】
すなわち本発明は、リパーゼの存在下、必要により減圧条件下で、高純度の高度不飽和脂肪酸あるいはそのアルコールエステルと過剰量のグリセリンとを反応させることによって生成した、部分グリセリド（モノグリセリドおよびジグリセリド）の合計がトリグリセリドより多いグリセリド組成をもつことを特徴とする水和性を高めた高度不飽和脂肪酸含有油脂組成物を要旨としている。
【００１１】
すなわち本発明の水和性を高めた高度不飽和脂肪酸含有油脂組成物は、リパーゼの存在下、高度に濃縮された高度不飽和脂肪酸あるいはそのアルコールエステルと過剰量のグリセリンとの反応によって生成することを特徴とする、グリセリドのうち部分グリセリドの合計がトリグリセリドより多いことを特徴とする高度不飽和脂肪酸含有油脂組成物の製造方法である。
以下、本発明を詳細に説明する。
【００１２】
【発明の実施の形態】
本発明に用いる高度不飽和脂肪酸あるいはそのアルコールエステルは、アラキドン酸（Ｃ２０：４ω６）、ＥＰＡ（Ｃ２０：５ω３）、ＤＨＡ（Ｃ２２：６ω３）などのＰＵＦＡを含有するものであればどのようなものでも良い。このようなＰＵＦＡはイワシ、マグロなどの魚類や、甲殻類などの海産動物、ある種の微生物が生産することが知られている。例えばマグロ油ではパルミチン酸１４．６％、オレイン酸１７．２％に対して、ＤＨＡ２２．０％と大量に含まれていることが知られている。
【００１３】
ＰＵＦＡは天然ではトリグリセリドとして存在するため、本発明に使用するには構成脂肪酸まで分解し、遊離脂肪酸あるいはそのアルコールエステルに変換する必要がある。遊離脂肪酸は公知の方法、すなわちケン化やリパーゼによる加水分解などによって容易に得ることができる。また、脂肪酸のアルコールエステルも公知の方法、すなわちアルコーリシス反応によって容易に得ることができる。このとき用いるアルコールは一価のアルコールならどのようなものでも良いが、用途に応じて選択することもできる。例えば食品として利用する場合にはエタノールを選択することが望ましい。
【００１４】
本発明においては、出発原料が高度不飽和脂肪酸あるいはそのアルコールエステルの形であるため、４０％以上の任意の濃度に、好ましくは６０％以上の任意の濃度に公知の濃縮法で精製することができる。すなわち、上記のようにして得た遊離脂肪酸あるいはそのアルコールエステルは、超臨界流体抽出法、尿素付加法、分子蒸留法、クロマトグラフ法などの公知の濃縮法によって、任意の濃度に精製して本発明に使用することができる。例えばＤＨＡであれば、加水分解法によるＤＨＡ濃縮の限界である約６０％を超えた高濃度に濃縮することも可能であるし、必要に応じて９０％以上の高純度まで精製してもよい。例えば、透明飲料などのように多量の油脂を添加できない食品に利用する場合は、高純度に精製した原料の利用が望ましい。
【００１５】
本発明に用いるグリセリンは市販されていて容易に入手できるものを利用することができる。
【００１６】
本発明に用いるリパーゼは、高度不飽和脂肪酸あるいはそのアルコールエステルとグリセリンの反応を触媒してグリセリドを生成するものであればどのようなものでもよいが、Ｐｓｅｕｄｏｍｏｎａｓ ｓｐ．やＣｈｒｏｍｏｂａｃｔｅｒｉｕｍ ｖｉｓｃｏｓｕｍ、Ｒｈｉｚｏｐｕｓ ｄｅｌｅｍａｒなどの微生物に由来するリパーゼが好ましい例として例示される。これらはいずれも市販されていて容易に入手可能である。これらのリパーゼは必要に応じてセライトや炭酸カルシウム、イオン交換樹脂などの坦体に固定化して利用することができる。
【００１７】
リパーゼの添加量は、高度不飽和脂肪酸あるいはそのアルコールエステル１モルに対して１万ユニット以上、望ましくは５０万ユニット以上添加する。リパーゼ反応はリパーゼが失活しない温度において進行する。この温度はリパーゼの種類や固定化の有無によって変化するので一概には言えないが、利用するリパーゼに応じて適宜選択すればよい。例えば、Ｐｓｅｕｄｏｍｏｎａｓ ｓｐ．リパーゼを炭酸カルシウムに固定化したリパーゼを用いた場合には２５℃前後が適している。
【００１８】
本発明における高度不飽和脂肪酸あるいはそのアルコールエステルに対するグリセリンの量比は、グリセリンが過剰になるように加えなければならず、モル比で３０倍以上添加することが望ましい。
【００１９】
上記の方法によって得られた油脂中に存在する未反応のグリセリンや脂肪酸は公知の方法、例えばアルカリ脱酸、水蒸気蒸留、溶剤抽出、イオン交換樹脂などの方法で除去することができる。このようにしてグリセリド部を分取することによって、上記の目的を達成した油脂を得ることができる。
【００２０】
なお、脂質組成の分析は次のようにして行うことができる。すなわち、反応物からグリセリンや遊離脂肪酸を除去した後にクロマロッド−ＳIII（ヤトロン製）にスポットし、ヘキサン／ジエチルエーテル／酢酸（８７：１３：０．２）で１回目の展開を行う。この条件では部分グリセリドは原点からあまり動かないが、アルコールエステルとトリグリセリドは分離する。イアトロスキャン（ヤトロン製）によってアルコールエステルとトリグリセリドのピークのみ分析したのち、クロロホルム／アセトン（９８：２）で２回目の展開を行うと、部分グリセリドは１，３−ジグリセリド、１，２−ジグリセリド、２−モノグリセリド、１−モノグリセリドの順で分離するので、これを分析する。
【００２１】
【実施例】
以下、本発明を実施例によりさらに詳細に説明するが、これらの実施例によって本発明はなんら限定されるものではない。
【００２２】
実施例１
純度９０％以上のＤＨＡエチルエステル（以下、「ＤＨＡ−ＥＥ」と略称する。）とグリセリンをモル比１：５０で混合し、ここに炭酸カルシウムに固定化したＰｓｅｕｄｏｍｏｎａｓ ｓｐ．由来リパーゼを加えた。固定化リパーゼはＤＨＡ−ＥＥ ０．００１モルに対して４０００ユニットを添加した。固定化リパーゼはリパーゼの水溶液を炭酸カルシウムの微粉末と室温で約１時間混合、ろ過後、残渣を冷アセトンで洗浄し、減圧乾燥して調製した。
【００２３】
真空ポンプで反応系を吸引することによって真空度を５ｍｍＨｇ以下に保ちながら、２５℃において３００ｒｐｍで攪拌を行った。１０時間後に得られた反応物から固定化リパーゼを除去して、反応産物を得た。反応産物の組成の分析結果を表１に示した。
【００２４】
【表１】
このように、真空度５ｍｍＨｇ以下の減圧条件を保ち、生成するエタノールを除去することによって、原料のＤＨＡ−ＥＥのほとんどがグリセリンと反応してグリセリドを生成した。また、部分グリセリドの合計（５０．４５％）はトリグリセリド（４４．９３％）よりも多かった。
【００２６】
比較例１
減圧しない（真空度７６０ｍｍＨｇ）こと以外は実施例１と同じ条件で反応を行った。この反応によって得られた反応産物の組成の分析結果を表１に示した。このように、減圧しない場合には反応性が著しく低下し、原料ＤＨＡ−ＥＥが約６割も未反応だった。
【００２７】
比較例２
真空度７ｍｍＨｇであること以外は実施例１と同じ条件で反応を行った。この反応によって得られた反応産物の組成の分析結果を表１に示した。
このように、減圧を行うことによって比較例１よりも反応性は向上したものの、実施例１と比較して真空度が低いため、原料ＤＨＡ−ＥＥが約４割も未反応だった。
【００２８】
実施例２
ＤＨＡ−ＥＥとグリセリンのモル比を１：３０から１：７５に変化させた以外は実施例１と同様の条件で２４時間反応を行った。得られた反応産物の脂質組成を表２に示した。
【００２９】
【表２】
このように、グリセリンをＤＨＡ−ＥＥに対してモル比で３０倍を超えて添加すると反応が効率的に進行し、ほとんどすべてのＤＨＡ−ＥＥがグリセリンと反応してグリセリドを生成した。
【００３１】
【発明の効果】
高度不飽和脂肪酸を高濃度に含有し、なおかつ水に対する親和性を有する油脂を提供することができる。透明性の高い飲料などの用途に供することができる、水和性を高め非常に高濃度にＰＵＦＡを含有した油脂を提供することができる。[0001]
[Technical field to which industry belongs]
The present invention relates to a highly unsaturated fatty acid-containing oil or fat composition mainly composed of partially glycerides having improved hydration properties.
In the present invention, a highly unsaturated fatty acid (hereinafter sometimes abbreviated as “PUFA”) is eicosapentaenoic acid (hereinafter sometimes abbreviated as “EPA”) or docosahexaenoic acid (hereinafter abbreviated as “DHA”). Meaning fatty acids having 18 or more carbon atoms and 3 or more double bonds per molecule.
Further, in the present invention, partial glyceride means a glycerin molecule in which 1 or 2 fatty acids are ester-bonded like monoglyceride or diglyceride.
[0002]
[Prior art]
In recent years, as the physiological effects of PUFAs typified by EPA and DHA have been clarified, these PUFAs have been widely used in foods and medical products. However, in general, PUFA is naturally present in triglycerides and thus has a low affinity for water, and cannot be widely applied to food as it is.
[0003]
This problem can be solved to some extent by using an emulsifier in combination, but if emulsification can be imparted to the PUFA itself, it is extremely advantageous in adding an amount of PUFA sufficient to exert a sufficient effect to foods and the like. It is.
[0004]
There is a concept of “partially glyceride-containing oil” as an oil based on such an idea. This is because partial glycerides, especially monoglycerides, have properties as emulsifiers, so that the fats and oils themselves are emulsified by producing a partial glyceride by subjecting PUFA-containing fats and oils to a hydrolysis reaction or glycerolysis reaction with lipase or the like. Is. Examples of such reports include JP-A-8-60181 (hydrolysis reaction) and JP-A-8-214892 (glycerolysis reaction). However, in these methods, since the raw material oil is not decomposed to the constituent fatty acids, for example, the former was concentrated only to a DHA concentration of 60% or more. Further, the latter method has a problem in terms of PUFA content, such as basically no PUFA concentration compared to the raw material.
[0005]
Regarding the concentration of PUFA, various methods such as wintering and lipase hydrolysis have been actively studied. However, there is a problem in obtaining fats and oils containing a specific PUFA at a very high concentration, for example, in wintering, the DHA concentration is limited to about 35%.
[0006]
On the other hand, when PUFA-containing fats and oils are decomposed into constituent fatty acids, it is known that high concentration can be relatively easily performed by supercritical fluid extraction, urea addition, molecular distillation, chromatography, etc. ing. As an example of preparing fats and oils in the presence of lipase from PUFA and glycerin thus concentrated, a report by Nagata et al. [Journal of Japanese Society of Fisheries Science, 57, 119-125 (1991)], JP-A-5-95792, etc. is there. According to these methods, it is possible to obtain fats and oils containing PUFA at a very high concentration, and when lipase is used, the reaction proceeds at room temperature and normal pressure. Can be expected to obtain high quality oils and fats. However, the former method has low synthesis efficiency, and 20 to 30% of unreacted fatty acids were present. Moreover, since the fats and oils obtained by the latter method are high-purity triglycerides, the affinity for water could not be expected due to their structure.
[0007]
[Problems to be solved by the invention]
An object of this invention is to provide the fats and oils which contain highly unsaturated fatty acid in high concentration, and have affinity with water. An object of the present invention is to provide an oil and fat containing PUFA at a very high concentration and having high hydration property, which is suitable for use in, for example, a highly transparent beverage.
[0008]
[Means for Solving the Problems]
The gist of the present invention is a highly unsaturated fatty acid-containing oil and fat composition having improved hydration characteristics, characterized by having a glyceride composition in which the sum of partial glycerides (monoglycerides and diglycerides) is higher than that of triglycerides. .
The highly unsaturated fatty acid-containing oil and fat composition having improved hydration properties according to the present invention is produced by adding an excess amount of glycerin to the highly unsaturated fatty acid or an alcohol ester thereof in the presence of lipase and performing the reaction. be able to.
[0009]
The highly unsaturated fatty acid or alcohol ester thereof in this reaction can be reacted even if it is highly concentrated by a known concentration method such as supercritical fluid extraction method, urea addition method, molecular distillation method, or chromatographic method. Can be made. Furthermore, in this reaction, fats and oils mainly composed of partial glycerides are produced by the reaction of highly unsaturated fatty acids or alcohol esters thereof with glycerin. At this time, water or alcohol is produced as a by-product, but these by-products serve as a substrate for the reverse reaction and may hinder the progress of the reaction. At this time, the reaction proceeds more by placing the reaction system under a reduced pressure condition, and the desired oil and fat can be obtained efficiently.
[0010]
That is, the present invention relates to partial glycerides (monoglycerides and diglycerides) produced by reacting high-purity polyunsaturated fatty acids or alcohol esters thereof with an excess amount of glycerin in the presence of lipase under reduced pressure as necessary. The gist of the present invention is a highly unsaturated fatty acid-containing oil and fat composition with improved hydration, characterized by having a glyceride composition that is greater than triglycerides.
[0011]
That is, the highly unsaturated fatty acid-containing fat and oil composition having enhanced hydrating properties of the present invention is produced by the reaction of a highly concentrated highly unsaturated fatty acid or its alcohol ester with an excess amount of glycerin in the presence of lipase. Is a method for producing a highly unsaturated fatty acid-containing fat composition characterized in that the total of partial glycerides in the glyceride is greater than that of triglycerides.
Hereinafter, the present invention will be described in detail.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
The polyunsaturated fatty acid or alcohol ester thereof used in the present invention may be any as long as it contains a PUFA such as arachidonic acid (C20: 4ω6), EPA (C20: 5ω3), DHA (C22: 6ω3). good. Such PUFAs are known to be produced by fish such as sardines and tuna, marine animals such as crustaceans, and certain microorganisms. For example, tuna oil is known to contain a large amount of DHA 22.0% against palmitic acid 14.6% and oleic acid 17.2%.
[0013]
Since PUFA exists in nature as a triglyceride, it must be decomposed into constituent fatty acids and converted to free fatty acids or alcohol esters thereof for use in the present invention. The free fatty acid can be easily obtained by a known method, that is, saponification or hydrolysis with lipase. Further, alcohol esters of fatty acids can be easily obtained by a known method, that is, an alcoholysis reaction. Any alcohol can be used as long as it is a monohydric alcohol, but it can be selected according to the intended use. For example, when used as food, it is desirable to select ethanol.
[0014]
In the present invention, since the starting material is in the form of a highly unsaturated fatty acid or an alcohol ester thereof, it can be purified by a known concentration method to an arbitrary concentration of 40% or more, preferably 60% or more. it can. That is, the free fatty acid or its alcohol ester obtained as described above is purified to an arbitrary concentration by a known concentration method such as a supercritical fluid extraction method, urea addition method, molecular distillation method, or chromatographic method. Can be used for invention. For example, in the case of DHA, it can be concentrated to a high concentration exceeding about 60%, which is the limit of DHA concentration by hydrolysis, and may be purified to a high purity of 90% or more as necessary. . For example, when used for foods such as transparent beverages to which a large amount of fats and oils cannot be added, it is desirable to use raw materials that have been purified to a high purity.
[0015]
The glycerin used in the present invention is commercially available and can be easily obtained.
[0016]
The lipase used in the present invention may be any lipase that generates a glyceride by catalyzing the reaction of a highly unsaturated fatty acid or an alcohol ester thereof and glycerin, but Pseudomonas sp. Lipases derived from microorganisms such as Chromobacterium viscosum and Rhizopus delmar are exemplified as preferred examples. These are all commercially available and easily available. These lipases can be used by immobilizing them on a carrier such as celite, calcium carbonate, or ion exchange resin, if necessary.
[0017]
The amount of lipase added is 10,000 units or more, preferably 500,000 units or more per 1 mol of highly unsaturated fatty acid or alcohol ester thereof. The lipase reaction proceeds at a temperature at which the lipase is not inactivated. Since this temperature varies depending on the type of lipase and the presence or absence of immobilization, it cannot be generally stated, but it may be appropriately selected according to the lipase used. For example, Pseudomonas sp. When lipase in which lipase is immobilized on calcium carbonate is used, around 25 ° C. is suitable.
[0018]
In the present invention, the amount ratio of glycerin to the highly unsaturated fatty acid or alcohol ester thereof should be added so that glycerin becomes excessive, and it is desirable to add 30 times or more in molar ratio.
[0019]
Unreacted glycerin and fatty acids present in the fats and oils obtained by the above method can be removed by known methods such as alkali deoxidation, steam distillation, solvent extraction, ion exchange resin and the like. Thus, by separating the glyceride part, an oil and fat that achieves the above-mentioned purpose can be obtained.
[0020]
The analysis of the lipid composition can be performed as follows. That is, after removing glycerin and free fatty acid from the reaction product, it is spotted on Chromarod-SIII (manufactured by Yatron) and developed for the first time with hexane / diethyl ether / acetic acid (87: 13: 0.2). Under this condition, partial glycerides do not move much from the origin, but alcohol esters and triglycerides are separated. After analyzing only the peak of alcohol ester and triglyceride by Iatroscan (manufactured by Yatron) and then developing for the second time with chloroform / acetone (98: 2), partial glycerides are 1,3-diglyceride and 1,2-diglyceride , 2-monoglyceride and 1-monoglyceride are separated in this order and analyzed.
[0021]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited at all by these Examples.
[0022]
Example 1
A DHA ethyl ester having a purity of 90% or more (hereinafter abbreviated as “DHA-EE”) and glycerin were mixed at a molar ratio of 1:50, and Pseudomonas sp. Origin lipase was added. The immobilized lipase was added at 4000 units per 0.001 mol of DHA-EE. The immobilized lipase was prepared by mixing an aqueous solution of lipase with a fine powder of calcium carbonate at room temperature for about 1 hour, filtering, washing the residue with cold acetone, and drying under reduced pressure.
[0023]
The reaction system was aspirated with a vacuum pump and stirred at 300 rpm at 25 ° C. while keeping the degree of vacuum at 5 mmHg or less. Immobilized lipase was removed from the reaction product obtained after 10 hours to obtain a reaction product. The analysis results of the reaction product composition are shown in Table 1.
[0024]
[Table 1]
As described above, by maintaining the reduced pressure condition with a vacuum degree of 5 mmHg or less and removing the generated ethanol, most of the raw material DHA-EE reacted with glycerin to produce glyceride. Further, the total of partial glycerides (50.45%) was larger than that of triglycerides (44.93%).
[0026]
Comparative Example 1
The reaction was performed under the same conditions as in Example 1 except that the pressure was not reduced (vacuum degree: 760 mmHg). The analysis results of the composition of the reaction product obtained by this reaction are shown in Table 1. Thus, when the pressure was not reduced, the reactivity was remarkably lowered, and the raw material DHA-EE was about 60% unreacted.
[0027]
Comparative Example 2
The reaction was performed under the same conditions as in Example 1 except that the degree of vacuum was 7 mmHg. The analysis results of the composition of the reaction product obtained by this reaction are shown in Table 1.
Thus, although the reactivity improved compared with the comparative example 1 by performing pressure reduction, since the degree of vacuum was low compared with the example 1, about 40% of raw material DHA-EE was unreacted.
[0028]
Example 2
The reaction was carried out for 24 hours under the same conditions as in Example 1 except that the molar ratio of DHA-EE to glycerin was changed from 1:30 to 1:75. Table 2 shows the lipid composition of the obtained reaction product.
[0029]
[Table 2]
Thus, when glycerol was added more than 30 times by molar ratio with respect to DHA-EE, reaction advanced efficiently, and almost all DHA-EE reacted with glycerol and produced | generated the glyceride.
[0031]
【The invention's effect】
It is possible to provide a fat containing highly unsaturated fatty acid at a high concentration and having affinity for water. It is possible to provide fats and oils that have high hydration properties and contain PUFA in a very high concentration, which can be used for applications such as highly transparent beverages.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP08990997A JP3861941B2 (en) | 1997-03-26 | 1997-03-26 | Oil composition containing highly unsaturated fatty acid with improved hydration |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP08990997A JP3861941B2 (en) | 1997-03-26 | 1997-03-26 | Oil composition containing highly unsaturated fatty acid with improved hydration |
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| Publication Number | Publication Date |
|---|---|
| JPH10265795A JPH10265795A (en) | 1998-10-06 |
| JP3861941B2 true JP3861941B2 (en) | 2006-12-27 |
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| US6762203B2 (en) | 1999-08-03 | 2004-07-13 | Kao Corporation | Oil composition |
| JP3752127B2 (en) | 2000-03-21 | 2006-03-08 | 花王株式会社 | Oil composition |
| JP4995377B2 (en) * | 2001-04-26 | 2012-08-08 | 花王株式会社 | Oil composition |
| US6956058B2 (en) | 2001-04-26 | 2005-10-18 | Kao Corporation | Method for improving insulin resistance |
| JP2008220236A (en) * | 2007-03-12 | 2008-09-25 | Taiyo Corp | Method for producing middle-chain and long-chain fatty acid monoglyceride |
| JP6390255B2 (en) * | 2014-08-07 | 2018-09-19 | 横浜ゴム株式会社 | Rubber composition and pneumatic tire |
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