JP2549399B2 - Method for purifying highly unsaturated fatty acid triglyceride and ester - Google Patents
Method for purifying highly unsaturated fatty acid triglyceride and esterInfo
- Publication number
- JP2549399B2 JP2549399B2 JP62296849A JP29684987A JP2549399B2 JP 2549399 B2 JP2549399 B2 JP 2549399B2 JP 62296849 A JP62296849 A JP 62296849A JP 29684987 A JP29684987 A JP 29684987A JP 2549399 B2 JP2549399 B2 JP 2549399B2
- Authority
- JP
- Japan
- Prior art keywords
- ester
- fatty acid
- acid
- unsaturated fatty
- highly unsaturated
- 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
- 150000002148 esters Chemical class 0.000 title claims description 38
- 238000000034 method Methods 0.000 title claims description 34
- 235000021122 unsaturated fatty acids Nutrition 0.000 title claims description 33
- 150000004670 unsaturated fatty acids Chemical class 0.000 title claims description 24
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 title claims description 23
- MBMBGCFOFBJSGT-KUBAVDMBSA-N all-cis-docosa-4,7,10,13,16,19-hexaenoic acid Chemical compound 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 68
- 235000019198 oils Nutrition 0.000 claims description 38
- 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 35
- 235000020673 eicosapentaenoic acid Nutrition 0.000 claims description 35
- 229960005135 eicosapentaenoic acid Drugs 0.000 claims description 35
- JAZBEHYOTPTENJ-UHFFFAOYSA-N eicosapentaenoic acid Natural products CCC=CCC=CCC=CCC=CCC=CCCCC(O)=O JAZBEHYOTPTENJ-UHFFFAOYSA-N 0.000 claims description 35
- 235000020669 docosahexaenoic acid Nutrition 0.000 claims description 34
- 229940090949 docosahexaenoic acid Drugs 0.000 claims description 34
- 235000019197 fats Nutrition 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 241001125048 Sardina Species 0.000 claims description 17
- 235000019512 sardine Nutrition 0.000 claims description 17
- 125000004494 ethyl ester group Chemical group 0.000 claims description 16
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 12
- 229930195729 fatty acid Natural products 0.000 claims description 12
- 239000000194 fatty acid Substances 0.000 claims description 12
- -1 unsaturated fatty acid ester Chemical class 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 8
- 150000004665 fatty acids Chemical class 0.000 claims description 7
- 235000021323 fish oil Nutrition 0.000 claims description 6
- 235000011187 glycerol Nutrition 0.000 claims description 4
- 235000020777 polyunsaturated fatty acids Nutrition 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims 1
- 239000003921 oil Substances 0.000 description 32
- 239000003925 fat Substances 0.000 description 17
- 235000019441 ethanol Nutrition 0.000 description 12
- 238000000746 purification Methods 0.000 description 9
- 239000002904 solvent Substances 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 6
- 239000004202 carbamide Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000004587 chromatography analysis Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 235000013402 health food Nutrition 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 2
- 241000269821 Scombridae Species 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 235000019688 fish Nutrition 0.000 description 2
- 235000020640 mackerel Nutrition 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000001766 physiological effect Effects 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 2
- 239000013076 target substance Substances 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 150000003626 triacylglycerols Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 208000007536 Thrombosis Diseases 0.000 description 1
- 238000011276 addition treatment Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 230000036772 blood pressure Effects 0.000 description 1
- MAMJNXVNGGBHFN-UHFFFAOYSA-N docosa-1,3,5,7,9,11-hexaene Chemical compound CCCCCCCCCCC=CC=CC=CC=CC=CC=C MAMJNXVNGGBHFN-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007721 medicinal effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002537 thrombolytic effect Effects 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Fats And Perfumes (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、高度不飽和脂肪酸トリグリセリド及びエス
テルの精製方法、特にエイコサペンタエン酸及び／又は
ドコサヘキサエン酸の高度不飽和脂肪酸を含有する高度
不飽和脂肪酸トリグリセリド及びエステルの精製方法に
関する。The present invention relates to a method for purifying highly unsaturated fatty acid triglycerides and esters, and more particularly to highly unsaturated fatty acids containing highly unsaturated fatty acids such as eicosapentaenoic acid and / or docosahexaenoic acid. The present invention relates to a method for purifying triglycerides and esters.
高度不飽和脂肪酸のエイコサペンタエン酸及び／又は
ドコサヘキサエン酸は、その生理活性のため、医薬品や
健康食品へ利用されつつある。例えば、血栓形成防止、
血栓溶解、血圧低下、血中コレステロール値の低下等の
生理活性、薬効がある。上記エイコサペンタエン酸とド
コサヘキサエン酸は、トリグリセリド、エステルの２つ
のタイプで現在、医薬品、健康食品に利用されている。The highly unsaturated fatty acids eicosapentaenoic acid and / or docosahexaenoic acid are being used in medicines and health foods because of their physiological activity. For example, prevention of thrombus formation,
It has physiological activity and medicinal effects such as thrombolysis, lowering blood pressure, and lowering blood cholesterol level. The above-mentioned eicosapentaenoic acid and docosahexaenoic acid are currently used in pharmaceuticals and health foods in two types, triglyceride and ester.
従来、エイコサペンタエン酸及び／又はドコサヘキサ
エン酸のトリグリセライドの精製方法としては、例え
ば、イワシ油等の油脂を原料とし、該油脂を溶媒に溶解
し、その溶液を冷却して低温下に静置することにより目
的物質を析出させ、然る後その析出成分を分離する、所
謂ウインタリング法が利用されている。また、エイコサ
ペンタエン酸及び／又はドコサヘキサエン酸のエステル
の精製方法としては、例えば、イワシ油等の油脂から調
製したエステルを原料とし、尿素を含有した溶媒に溶解
し、その溶液を40〜60℃に放置することにより目的物質
以外のものを析出させ、然る後その析出成分を分離、除
去する、所謂尿素付加法が利用されている。Conventionally, as a method for purifying triglyceride of eicosapentaenoic acid and / or docosahexaenoic acid, for example, an oil or fat such as sardine oil is used as a raw material, the oil or fat is dissolved in a solvent, and the solution is cooled and allowed to stand at a low temperature. A so-called wintering method is used in which the target substance is precipitated by the method described above, and then the precipitated component is separated. Further, as a method for purifying the ester of eicosapentaenoic acid and / or docosahexaenoic acid, for example, starting from an ester prepared from fats and oils such as sardine oil, dissolved in a solvent containing urea, and the solution is heated to 40 to 60 ° C. A so-called urea addition method is used in which a substance other than the target substance is deposited by allowing it to stand, and then the deposited component is separated and removed.
しかしながら、上記のエイコサペンタエン酸やドコサ
ヘキサエン酸のトリグリセライドをウインタリング法に
よりイワシ油から精製する場合には、原料のイワシ油
を、例えば、その６倍もの大量のアセトン（溶媒）に溶
解し、その溶液を−35℃という低温に長時間（例えば、
24時間）静置しなければならない。そのため材料コス
ト、設備コスト及びエネルギーコストが嵩む等の問題が
あった。However, when purifying the above triglycerides of eicosapentaenoic acid and docosahexaenoic acid from sardine oil by the wintering method, the raw material sardine oil is dissolved in, for example, 6 times as much acetone (solvent) as that solution. To -35 ° C for a long time (for example,
You have to leave it for 24 hours. Therefore, there is a problem that material cost, equipment cost and energy cost increase.
また、上記二つの酸と一価アルコール（例えば、エチ
ルアルコール）とのエステルの精製に上記尿素付加法を
適用する場合は、原料のエステルを、やはり大量のメタ
ノール（溶媒）に溶解しなければならず、また、添加し
た尿素を回収する設備も必要となりやはり、コストが嵩
む問題があり、また、上記尿素添加法では精々70％程度
迄しか精製できないため、医薬として要求される高純度
に精製することができないという問題もあった。When the above urea addition method is applied to the purification of an ester of the above two acids and a monohydric alcohol (for example, ethyl alcohol), the starting ester must be dissolved in a large amount of methanol (solvent). In addition, there is a problem that the cost is increased because a facility for recovering the added urea is also required, and since the above urea addition method can purify only up to about 70%, it is purified to a high purity required as a medicine. There was also the problem of not being able to do it.
そこで、一般に、上記二つの酸と一価アルコールとの
エステルの高純度の精製にはクロマトグラフ法が採用さ
れているが、この場合も、材料コストや設備コストが嵩
む等の問題がある。Therefore, in general, a chromatographic method is used for high-purity purification of the ester of the above two acids and a monohydric alcohol, but in this case as well, there are problems such as increased material costs and equipment costs.
従って、本発明の目的は、エイコサペンタエン酸及び
／又はドコサヘキサエン酸のトリグリセライド及び／又
はエステルを、溶媒を使用せず、しかも低温処理、尿素
付加処理を行うことなく精製できる精製方法を提供する
ことにある。Therefore, an object of the present invention is to provide a purification method capable of purifying the triglyceride and / or ester of eicosapentaenoic acid and / or docosahexaenoic acid, without using a solvent, and without performing low temperature treatment and urea addition treatment. is there.
本発明の他の目的は、エイコサペンタエン酸及び／又
はドコサヘキサエン酸又はその他の脂肪酸と一価アルコ
ールとのエステルを、クロマトグラフ法によらずに高純
度に精製できる精製方法を提供することにある。Another object of the present invention is to provide a purification method capable of purifying an ester of eicosapentaenoic acid and / or docosahexaenoic acid or other fatty acid and a monohydric alcohol to high purity without using a chromatographic method.
本発明者等は、鋭意研究した結果、高度不飽和脂肪酸
成分として少なくともエイコサペンタエン酸及び／又は
ドコサヘキサエン酸を含む、高度不飽和脂肪酸のトリグ
リセライドを含有する液体の油脂やその油脂から調製し
た混合エステルに高圧を作用させると、該エイコサペン
タエン酸及び／又はドコサヘキサエン酸に富んだ成分を
析出させることができることを知見した。The present inventors, as a result of diligent research, include at least eicosapentaenoic acid and / or docosahexaenoic acid as a highly unsaturated fatty acid component, and a liquid oil or fat containing triglyceride of a highly unsaturated fatty acid or a mixed ester prepared from the oil or fat. It has been found that a component rich in eicosapentaenoic acid and / or docosahexaenoic acid can be precipitated by applying a high pressure.
本発明は、上記知見によりなされたもので、高度不飽
和脂肪酸成分として少なくともエイコサペンタエン酸及
び／又はドコサヘキサエン酸を含む、高度不飽和脂肪酸
又はその他の脂肪酸とグリセリンとのエステルであるト
リグリセライドを含有する油脂に常温で高圧を作用さ
せ、少なくとも上記エイコサペンタエン酸及び／又はド
コサヘキサエン酸を含むトリグリセライドを析出させ、
その析出成分を分離することを特徴とする高度不飽和脂
肪酸トリグリセライドの精製方法（第１の発明）を提供
することによって上記の目的を達成したものである。The present invention has been made based on the above findings, and contains at least eicosapentaenoic acid and / or docosahexaenoic acid as a highly unsaturated fatty acid component, a fat or oil containing triglyceride which is an ester of highly unsaturated fatty acid or other fatty acid and glycerin. A high pressure at room temperature to precipitate triglyceride containing at least the above-mentioned eicosapentaenoic acid and / or docosahexaenoic acid,
The above object is achieved by providing a method for purifying highly unsaturated fatty acid triglycerides (first invention), which is characterized in that the precipitated components are separated.
また、本発明は、高度不飽和脂肪酸成分として少なく
ともエイコサペンタエン酸及び／又はドコサヘキサエン
酸を含む、高度不飽和脂肪酸、あるいはその他の脂肪酸
又は他の脂肪酸と一価アルコールとのエステルを含有す
る混合エステルに、常温で高圧を作用させ、少なくとも
上記エイコサペンタエン酸及び／又はドコサヘキサエン
酸のエステルを析出させ、その析出成分を分離すること
を特徴とする高度不飽和脂肪酸エステルの精製方法（第
２の発明）を提供することによって上記目的を達成した
ものである。Further, the present invention provides a highly unsaturated fatty acid containing at least eicosapentaenoic acid and / or docosahexaenoic acid as a highly unsaturated fatty acid component, or a mixed ester containing an ester of another fatty acid or another fatty acid and a monohydric alcohol. A high-unsaturated fatty acid ester purification method (second invention) is characterized in that high pressure is applied at room temperature to precipitate at least the ester of eicosapentaenoic acid and / or docosahexaenoic acid, and the precipitated components are separated. The above object is achieved by the provision.
以下、本発明の高度不飽和脂肪酸トリグリセライド及
び／又はエステルの精製方法をその実施態様に基づいて
詳述する。Hereinafter, the method for purifying the highly unsaturated fatty acid triglyceride and / or ester of the present invention will be described in detail based on its embodiment.
先ず、第１の発明について説明する。 First, the first invention will be described.
第１の発明の高度不飽和脂肪酸トリグリセライドの精
製方法は、先ず、高度不飽和脂肪酸成分として少なくと
もエイコサペンタエン酸及び／又はドコサヘキサエン酸
を含む、高度不飽和脂肪酸のトリグリセライドを含有す
る油脂に、常温で高圧を作用させる。そして、その高圧
を作用させた状態を維持しながら所定時間静置し、少な
くとも上記エイコサペンタエン酸及び／又はドコサヘキ
サエン酸のトリグリセライドを析出させる。その後、析
出成分を適切な手段で分離し、目的とするエイコサペン
タエン酸及び／又はドコサヘキサエン酸のトリグリセラ
イドの精製を達成する。The method for purifying highly unsaturated fatty acid triglyceride of the first invention is as follows. First, an oil or fat containing a highly unsaturated fatty acid triglyceride containing at least eicosapentaenoic acid and / or docosahexaenoic acid as a highly unsaturated fatty acid component is subjected to high pressure at room temperature. To act. Then, while maintaining the state in which the high pressure is applied, the mixture is allowed to stand for a predetermined time to precipitate at least the triglyceride of eicosapentaenoic acid and / or docosahexaenoic acid. Then, the precipitated components are separated by an appropriate means to achieve the desired purification of eicosapentaenoic acid and / or docosahexaenoic acid triglyceride.
上記油脂は、少なくともエイコサペンタエン酸及び／
又はドコサヘキサエン酸をトリグリセライドの脂肪酸成
分として含んでいるものであれば特に制限されるもので
なく、例えば、イワシ油、サバ油等の海産魚の魚油等を
好ましい例として挙げることができる。The above-mentioned fat and oil is at least eicosapentaenoic acid and / or
Alternatively, it is not particularly limited as long as it contains docosahexaenoic acid as a fatty acid component of triglyceride, and preferred examples thereof include marine fish fish oil such as sardine oil and mackerel oil.
上記油脂に作用させる高圧は、特に制限されるもので
なく、原料の油脂の種類及び精製する高度不飽和脂肪酸
の種類に応じて適切な圧力が選択されるものであるが、
好ましい範囲として1,000〜5,000kg/cm2を、更に好まし
い範囲として2,500〜4,500kg/cm2を挙げることができ
る。The high pressure applied to the fat or oil is not particularly limited, and an appropriate pressure is selected according to the type of raw material fat and oil and the type of highly unsaturated fatty acid to be purified,
A preferable range is 1,000 to 5,000 kg / cm 2, and a further preferable range is 2,500 to 4,500 kg / cm 2 .
また、上記油脂への加圧方法は、加圧容器内に収容さ
れている油脂に所望の高圧を作用させることができるも
のであれば特に制限されるものでない。上記油脂に作用
させる圧力は、一度所望の強さで加圧した後は、単に圧
力弁を閉じておくだけでその加圧状態を維持できるた
め、極めて経済的である。The method for pressurizing the oil or fat is not particularly limited as long as it can apply a desired high pressure to the oil or fat contained in the pressure vessel. The pressure applied to the oil or fat is extremely economical since it can be maintained in a pressurized state by simply closing the pressure valve after the pressure is once increased to a desired level.
第２の発明は、上述の第１の発明における油脂の代わ
りに、原料として、その油脂から調製した高度不飽和脂
肪酸成分として少なくともエイコサペンタエン酸及び／
又はドコサヘキサエン酸を含む、高度不飽和脂肪酸と一
価アルコールとのエステルを含有する混合エステルを使
用する以外は、略上記第１の発明と同様である。The second invention is, in place of the oil and fat in the above-mentioned first invention, at least eicosapentaenoic acid and / or as a raw material, a highly unsaturated fatty acid component prepared from the oil and fat.
Alternatively, it is substantially the same as the first invention except that a mixed ester containing an ester of a polyunsaturated fatty acid and a monohydric alcohol containing docosahexaenoic acid is used.
上記混合エステルとしては、上記高度不飽和脂肪酸成
分が含まれていれば特に制限されるものでなく、例え
ば、イワシ油、サバ油等の海産魚の魚油等の油脂から調
製されるエステルを挙げることができる。The mixed ester is not particularly limited as long as it contains the highly unsaturated fatty acid component, and examples thereof include esters prepared from fats and oils such as fish oil of marine fish such as sardine oil and mackerel oil. it can.
また、一価アルコールも、メチルアルコール、エチル
アルコール又はプロピルアルコール等、特に制限なく使
用できる。In addition, monohydric alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol and the like can be used without particular limitation.
上記混合エステルの調製は、イワシ油のエチルエステ
ルの場合を例にして説明すれば、おおよそ次のようにし
て行うことができる。The above-mentioned mixed ester can be prepared in the following manner, taking the case of ethyl ester of sardine oil as an example.
即ち、先ず、イワシ油をナトリウムエチラート含有エ
タノールに溶解し、60〜70℃、１時間放置し、エステル
化反応を起こさせる。エステル化反応終了後、水でゆす
ぎ、遊離してきたグリセリンを除去し、調製する。That is, first, sardine oil is dissolved in ethanol containing sodium ethylate and left at 60 to 70 ° C. for 1 hour to cause an esterification reaction. After completion of the esterification reaction, it is rinsed with water to remove glycerin that has been liberated, and then prepared.
また、第２の発明では、原料の混合エステルに加える
圧力を特定の値に制御することにより、特定の高度不飽
和脂肪酸を酸成分とするエステルを選択的に高濃度で精
製することも可能である。これは、本発明者等の鋭意研
究の結果初めて知見されたものである。Further, in the second invention, by controlling the pressure applied to the mixed ester as a raw material to a specific value, it is possible to selectively purify an ester containing a specific highly unsaturated fatty acid as an acid component at a high concentration. is there. This was discovered for the first time as a result of intensive studies by the present inventors.
即ち、具体的には後に実施例で詳述するが、例えば、
イワシ油から調製されたエチルエステルに4,000kg/cm2
の所定の圧力を作用させると、エイコサペンタエン酸の
エチルエステルを高濃度に精製することができ、また、
同様に上記エチルエステルに、4,200kg/cm2の所定の圧
力を作用させると、ドコサヘキサエン酸のエチルエステ
ルを高濃度に精製することができる。この場合、上記両
エチルエステルを、何れも90％以上の高濃度に精製する
ことができるので、本発明による第２の発明はクロマト
グラフ法に代わる簡便な精製方法として提供できる。
尚、上記の所定の圧力は限定されたものでなく、混合エ
ステルを調製する原料の種類、該混合エステルを形成す
る一価アルコールの種類、その他の条件によって適宜適
切な強さの圧力が選択されるものである。That is, as will be specifically described later in Examples, for example,
4,000 kg / cm 2 for ethyl ester prepared from sardine oil
By applying a predetermined pressure of, the ethyl ester of eicosapentaenoic acid can be purified to a high concentration, and
Similarly, when a predetermined pressure of 4,200 kg / cm 2 is applied to the ethyl ester, the ethyl ester of docosahexaenoic acid can be purified to a high concentration. In this case, since both of the above ethyl esters can be purified to a high concentration of 90% or more, the second invention of the present invention can be provided as a simple purification method replacing the chromatographic method.
The above-mentioned predetermined pressure is not limited, and a pressure having an appropriate strength is appropriately selected depending on the types of raw materials for preparing the mixed ester, the type of monohydric alcohol forming the mixed ester, and other conditions. It is something.
次に、実施例を挙げ、本発明の高度不飽和脂肪酸トリ
グリセライド又はエステルの精製方法を更に具体的に説
明する。Next, the method for purifying the highly unsaturated fatty acid triglyceride or ester of the present invention will be described more specifically with reference to Examples.
実施例１ 圧力容器内に所定量のイワシ油（油脂）を入れ、該イ
ワシ油に室温（約20℃）で3,500kg/cm2の高圧を作用さ
せ、圧力弁を閉じて該高圧状態を１時間維持した。その
後、圧力容器内を２分間かけて徐々に常圧に戻した。Example 1 A predetermined amount of sardine oil (oil and fat) was placed in a pressure vessel, a high pressure of 3,500 kg / cm 2 was applied to the sardine oil at room temperature (about 20 ° C.), and the pressure valve was closed to bring the high pressure state to 1 Maintained for hours. After that, the pressure inside the pressure vessel was gradually returned to normal pressure over 2 minutes.
次いで、上記圧力容器の内容物を濾過し、析出成分を
分離した。尚、上記析出成分は、室温で放置したら約10
分で融解した。Then, the content of the pressure vessel was filtered to separate the precipitated component. It should be noted that the above-mentioned precipitated component is about 10 when left at room temperature.
It melted in minutes.
本実施例では、当初イワシ油に含まれていたエイコサ
ペンタエン酸の含有率を、約16％から約35％に、また、
ドコサヘキサエン酸の含有率を、約10％から約20％に、
それぞれ向上させることができた。In this example, the content of eicosapentaenoic acid originally contained in sardine oil was changed from about 16% to about 35%,
Increase the content of docosahexaenoic acid from about 10% to about 20%,
I was able to improve each.
このように、本発明によれば、溶媒を使用せず、しか
も冷却することもなく、単に高圧を作用させるだけで短
時間（ウインタリング法の1/24）でもエイコサペンタエ
ン酸を含むトリグリセライド及びドコサヘキサエン酸を
含むトリグリセライドの精製が達成された。As described above, according to the present invention, triglyceride and docosahexaene containing eicosapentaenoic acid can be used for a short time (1/24 of the wintering method) by simply applying high pressure without using a solvent and without cooling. Purification of triglyceride containing acid was achieved.
実施例２ 先ず、イワシ油100gを、ナトリウムエチラート1gを含
有するエタノール500mlに溶解し、60〜70℃下で１時間
放置し、エステル化反応を行わせた。エステル化反応終
了後、水でゆすいで遊離してきたグリセリンを除去し、
エイコサペンタエン酸の含有率が約16％、ドコサヘキサ
エン酸の含有率が約10％である脂肪酸エチルエステル
（混合エステル）を調製した。Example 2 First, 100 g of sardine oil was dissolved in 500 ml of ethanol containing 1 g of sodium ethylate and allowed to stand at 60 to 70 ° C. for 1 hour to carry out an esterification reaction. After completion of the esterification reaction, rinsed with water to remove the released glycerin,
A fatty acid ethyl ester (mixed ester) having an eicosapentaenoic acid content of about 16% and a docosahexaenoic acid content of about 10% was prepared.
次いで、圧力容器内に、上記脂肪酸エチルエステルを
入れ、該脂肪酸エチルエステルに室温（約20℃）で4,00
0kg/cm2の高圧を作用させ、圧力弁を閉じて該高圧状態
を３時間維持した。その後、圧力容器内を２分間かけて
徐々に常圧に戻した。Then, the above fatty acid ethyl ester was placed in a pressure vessel, and the fatty acid ethyl ester was stirred at room temperature (about 20 ° C) for 4,000
A high pressure of 0 kg / cm 2 was applied, the pressure valve was closed, and the high pressure state was maintained for 3 hours. After that, the pressure inside the pressure vessel was gradually returned to normal pressure over 2 minutes.
次いで、上記圧力容器の内容物（結晶状の析出物が浮
遊していた）を濾過し、析出成分を分離した。尚、上記
析出成分は、室温で１時間放置しても完全に融解しなか
った。Then, the content of the pressure vessel (the crystalline precipitate was suspended) was filtered to separate the precipitated components. The deposited components did not completely melt even when left at room temperature for 1 hour.
上記析出成分は、エイコサペンタエン酸のエチルエス
テルの純度が90％であった。The precipitated component had a purity of ethyl ester of eicosapentaenoic acid of 90%.
このように、本発明によれば、溶媒を使用せず、しか
も冷却することもなく、単に所定の高圧を作用させるだ
けで短時間でエイコサペンタエン酸のエチルエステルを
高純度に精製することができた。従って、この方法は、
クロマトグラフ法に代わる高純度精製方法として提供で
きる。As described above, according to the present invention, the ethyl ester of eicosapentaenoic acid can be purified to a high purity in a short time by simply applying a predetermined high pressure without using a solvent and without cooling. It was Therefore, this method
It can be provided as a high-purity purification method that replaces the chromatographic method.
実施例３ 上記実施例２と同様にして脂肪酸エチルエステルを調
製し、該脂肪酸エチルエステルに作用させる圧力を4,50
0kg/cm2とし、他は上記実施例２と同様に実施した。常
圧に戻した後の圧力容器内には、半結晶状の個体が析出
していた。この析出成分は、ドコサヘキサエン酸のエチ
ルエステルの純度が95％であった。Example 3 A fatty acid ethyl ester was prepared in the same manner as in Example 2 above, and the pressure applied to the fatty acid ethyl ester was adjusted to 4,50.
It was 0 kg / cm 2, and the same procedure as in Example 2 was carried out. A semi-crystalline solid was deposited in the pressure vessel after returning to normal pressure. This precipitated component had a purity of ethyl ester of docosahexaenoic acid of 95%.
このように、本発明によれば、ドコサヘキサエン酸の
エチルエステルについても極めて高純度に精製すること
ができた。Thus, according to the present invention, the ethyl ester of docosahexaenoic acid could be purified to an extremely high purity.
本発明の高度不飽和脂肪酸トリグリセライド及びエス
テルの精製方法によれば、エイコサペンタエン酸及び／
又はドコサヘキサエン酸のトリグリセライドを、溶媒を
使用せず、しかも低温処理を行うことなく容易に精製す
ることができる。また、エイコサペンタエン酸及び／又
はドコサヘキサエン酸と一価アルコールとのエステル
を、クロマトグラフ法によらなくとも容易に、しかも高
純度に精製することができる。従って、エイコサペンタ
エン酸及び／又はドコサヘキサエン酸のトリグリセライ
ド及び／又はエステルを、医薬として、又は健康食品と
して、安価で提供することが可能となる。According to the method for purifying highly unsaturated fatty acid triglycerides and esters of the present invention, eicosapentaenoic acid and / or
Alternatively, triglyceride of docosahexaenoic acid can be easily purified without using a solvent and without performing low temperature treatment. Further, an ester of eicosapentaenoic acid and / or docosahexaenoic acid and a monohydric alcohol can be easily and highly purified without using a chromatographic method. Therefore, it becomes possible to provide the triglyceride and / or ester of eicosapentaenoic acid and / or docosahexaenoic acid as a medicine or a health food at a low cost.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 若目田 篤 東京都中央区月島３丁目２番９号 大洋 漁業株式会社大洋研究所内 (72)発明者 八塚 信明 東京都中央区月島３丁目２番９号 大洋 漁業株式会社大洋研究所内 (72)発明者 西川 正純 東京都中央区月島３丁目２番９号 大洋 漁業株式会社大洋研究所内 (56)参考文献 特表 平３−500054（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Atsushi Wakameda 3-2-9 Tsukishima, Chuo-ku, Tokyo Taiyo Fisheries Co., Ltd. Ocean Research Laboratory (72) Inventor Nobuaki Yatsuka 3-2-9 Tsukishima, Chuo-ku, Tokyo Ocean Fisheries Co., Ltd. Ocean Research Laboratory (72) Inventor Masazumi Nishikawa 3-2-9 Tsukishima, Chuo-ku, Tokyo Ocean Fisheries Co., Ltd. Ocean Research Laboratory (56) References Tokukaihei 3-500054 (JP, A)
Claims (9)
イコサペンタエン酸及び／又はドコサヘキサエン酸を含
む、高度不飽和脂肪酸又はその他の脂肪酸とグリセリン
とのエステルであるトリグリセライドを含有する油脂に
常温で高圧を作用させ、少なくとも上記エイコサペンタ
エン酸及び／又はドコサヘキサエン酸を含むトリグリセ
ライドを析出させ、その析出成分を分離することを特徴
とする高度不飽和脂肪酸トリグリセライドの精製方法。1. A high pressure is applied to a fat or oil containing triglyceride which is an ester of glycerin with a highly unsaturated fatty acid or other fatty acid containing at least eicosapentaenoic acid and / or docosahexaenoic acid as a highly unsaturated fatty acid component. A method for purifying highly unsaturated fatty acid triglyceride, which comprises depositing triglyceride containing at least the above-mentioned eicosapentaenoic acid and / or docosahexaenoic acid, and separating the deposited components.
である、特許請求の範囲第（１）項記載の高度不飽和脂
肪酸トリグリセライドの精製方法。 2. The method for purifying a highly unsaturated fatty acid triglyceride according to claim 1, wherein the high pressure is within a range of 1,000 to 5,000 kg / cm 2 .
魚油である、特許請求の範囲第（１）項記載の高度不飽
和脂肪酸トリグリセライドの精製方法。3. The method for purifying highly unsaturated fatty acid triglyceride according to claim 1, wherein the oil or fat is sardine oil and / or other fish oil.
イコサペンタエン酸及び／又はドコサヘキサエン酸を含
む、高度不飽和脂肪酸、又はその他の脂肪酸と一価アル
コールとのエステルを含有する混合エステルに、常温で
高圧を作用させ、少なくとも上記エイコサペンタエン酸
及び／又はドコサヘキサエン酸のエステルを析出させ、
その析出成分を分離することを特徴とする高度不飽和脂
肪酸エステルの精製方法。4. A mixed ester containing a polyunsaturated fatty acid or an ester of another fatty acid and a monohydric alcohol containing at least eicosapentaenoic acid and / or docosahexaenoic acid as a polyunsaturated fatty acid component is subjected to high pressure at room temperature. To act to precipitate at least the ester of eicosapentaenoic acid and / or docosahexaenoic acid,
A method for purifying a highly unsaturated fatty acid ester, which comprises separating the precipitated component.
である、特許請求の範囲第（４）項記載の高度不飽和脂
肪酸エステルの精製方法。5. The method for purifying a highly unsaturated fatty acid ester according to claim 4, wherein the high pressure is within a range of 1,000 to 5,000 kg / cm 2 .
せ、エイコサペンタエン酸又はドコサヘキサエン酸の何
れか一方のエステルを選択的に析出させ、該エイコサペ
ンタエン酸又はドコサヘキサエン酸のエステルを高純度
で分離する、特許請求の範囲第（４）項記載の高度不飽
和脂肪酸エステルの精製方法。6. A specific high pressure is applied to the mixed ester to selectively precipitate either one of eicosapentaenoic acid and docosahexaenoic acid, and the ester of eicosapentaenoic acid or docosahexaenoic acid is separated with high purity. A method for purifying a highly unsaturated fatty acid ester according to claim (4).
その他の魚油から調製されたエチルエステルである、第
（４）項記載の高度不飽和脂肪酸エステルの精製方法。7. The method for purifying a highly unsaturated fatty acid ester according to claim 4, wherein the mixed ester is an ethyl ester prepared from sardine oil and / or other fish oil.
されたエチルエステルに、4,000kg/cm2の圧力を作用さ
せ、エイコサペンタエン酸のエチルエステルを析出させ
る、特許請求の範囲第（７）項記載の高度不飽和脂肪酸
エステルの精製方法。8. An ethyl ester prepared from sardine oil and / or other fish oil is subjected to a pressure of 4,000 kg / cm 2 to precipitate an ethyl ester of eicosapentaenoic acid. A method for purifying a highly unsaturated fatty acid ester according to the item.
されたエチルエステルに、4,500kg/cm2の圧力を作用さ
せ、ドコサヘキサエン酸のエチルエステルを析出させ
る、特許請求の範囲第（７）項記載の高度不飽和脂肪酸
エステルの精製方法。9. The ethyl ester prepared from sardine oil and / or other fish oil is subjected to a pressure of 4,500 kg / cm 2 to precipitate the ethyl ester of docosahexaenoic acid, wherein the ethyl ester is precipitated. A method for purifying a highly unsaturated fatty acid ester as described.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62296849A JP2549399B2 (en) | 1987-11-25 | 1987-11-25 | Method for purifying highly unsaturated fatty acid triglyceride and ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62296849A JP2549399B2 (en) | 1987-11-25 | 1987-11-25 | Method for purifying highly unsaturated fatty acid triglyceride and ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01139548A JPH01139548A (en) | 1989-06-01 |
| JP2549399B2 true JP2549399B2 (en) | 1996-10-30 |
Family
ID=17838956
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62296849A Expired - Lifetime JP2549399B2 (en) | 1987-11-25 | 1987-11-25 | Method for purifying highly unsaturated fatty acid triglyceride and ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2549399B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2267137T5 (en) * | 1996-03-28 | 2014-03-14 | Dsm Ip Assets B.V. | Microbial oil containing polyunsaturated fatty acid and method of producing oil from pasteurized and granulated biomass |
| JP4887553B2 (en) * | 2000-07-18 | 2012-02-29 | 株式会社カネカ | Separation of edible oils and fats |
-
1987
- 1987-11-25 JP JP62296849A patent/JP2549399B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01139548A (en) | 1989-06-01 |
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