JPH02295490A - Modification of hydrolyzed product of fat or oil - Google Patents
Modification of hydrolyzed product of fat or oilInfo
- Publication number
- JPH02295490A JPH02295490A JP1115000A JP11500089A JPH02295490A JP H02295490 A JPH02295490 A JP H02295490A JP 1115000 A JP1115000 A JP 1115000A JP 11500089 A JP11500089 A JP 11500089A JP H02295490 A JPH02295490 A JP H02295490A
- Authority
- JP
- Japan
- Prior art keywords
- fatty acids
- oil
- unsaturated fatty
- highly unsaturated
- fat
- 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.)
- Pending
Links
- 230000004048 modification Effects 0.000 title 1
- 238000012986 modification Methods 0.000 title 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims abstract description 25
- 150000004670 unsaturated fatty acids Chemical class 0.000 claims abstract description 25
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 102000004882 Lipase Human genes 0.000 claims abstract description 13
- 108090001060 Lipase Proteins 0.000 claims abstract description 13
- 239000004367 Lipase Substances 0.000 claims abstract description 13
- 235000019421 lipase Nutrition 0.000 claims abstract description 13
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 4
- 239000003921 oil Substances 0.000 claims description 31
- 239000003925 fat Substances 0.000 claims description 24
- 235000020978 long-chain polyunsaturated fatty acids Nutrition 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 235000019198 oils Nutrition 0.000 abstract description 32
- 150000004665 fatty acids Chemical class 0.000 abstract description 29
- 235000014113 dietary fatty acids Nutrition 0.000 abstract description 24
- 229930195729 fatty acid Natural products 0.000 abstract description 24
- 239000000194 fatty acid Substances 0.000 abstract description 24
- 125000005456 glyceride group Chemical group 0.000 abstract description 13
- 235000021323 fish oil Nutrition 0.000 abstract description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 abstract description 5
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 5
- 230000007062 hydrolysis Effects 0.000 abstract description 4
- 241000555825 Clupeidae Species 0.000 abstract description 2
- 235000019512 sardine Nutrition 0.000 abstract description 2
- 150000004671 saturated fatty acids Chemical class 0.000 abstract description 2
- 235000003441 saturated fatty acids Nutrition 0.000 abstract 1
- 235000019197 fats Nutrition 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000000470 constituent Substances 0.000 description 11
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 9
- 238000004587 chromatography analysis Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 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 description 7
- 238000007664 blowing Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 235000020669 docosahexaenoic acid Nutrition 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 150000003626 triacylglycerols Chemical class 0.000 description 5
- OGBUMNBNEWYMNJ-UHFFFAOYSA-N batilol Chemical class CCCCCCCCCCCCCCCCCCOCC(O)CO OGBUMNBNEWYMNJ-UHFFFAOYSA-N 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 241000222120 Candida <Saccharomycetales> Species 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 239000012024 dehydrating agents Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 241000588881 Chromobacterium Species 0.000 description 2
- 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 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 229940090949 docosahexaenoic acid Drugs 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 2
- 235000020660 omega-3 fatty acid Nutrition 0.000 description 2
- 229940012843 omega-3 fatty acid Drugs 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000004255 Butylated hydroxyanisole Substances 0.000 description 1
- 239000004322 Butylated hydroxytoluene Substances 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- 241001149724 Cololabis adocetus Species 0.000 description 1
- 206010020772 Hypertension Diseases 0.000 description 1
- 108010093096 Immobilized Enzymes Proteins 0.000 description 1
- 241000235395 Mucor Species 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 241000589516 Pseudomonas Species 0.000 description 1
- 241000269851 Sarda sarda Species 0.000 description 1
- 241000269821 Scombridae Species 0.000 description 1
- 241001504592 Trachurus trachurus Species 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 235000021342 arachidonic acid Nutrition 0.000 description 1
- 229940114079 arachidonic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 235000019282 butylated hydroxyanisole Nutrition 0.000 description 1
- CZBZUDVBLSSABA-UHFFFAOYSA-N butylated hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1.COC1=CC=C(O)C=C1C(C)(C)C CZBZUDVBLSSABA-UHFFFAOYSA-N 0.000 description 1
- 229940043253 butylated hydroxyanisole Drugs 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 229940095259 butylated hydroxytoluene Drugs 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- GVJHHUAWPYXKBD-UHFFFAOYSA-N d-alpha-tocopherol Natural products OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 1
- CYQFCXCEBYINGO-IAGOWNOFSA-N delta1-THC Chemical compound C1=C(C)CC[C@H]2C(C)(C)OC3=CC(CCCCC)=CC(O)=C3[C@@H]21 CYQFCXCEBYINGO-IAGOWNOFSA-N 0.000 description 1
- -1 di- Chemical compound 0.000 description 1
- 235000005911 diet Nutrition 0.000 description 1
- 230000037213 diet Effects 0.000 description 1
- 235000015872 dietary supplement Nutrition 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229940013317 fish oils Drugs 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 208000019622 heart disease Diseases 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 235000020640 mackerel Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000006014 omega-3 oil Substances 0.000 description 1
- 235000020665 omega-6 fatty acid Nutrition 0.000 description 1
- 229940033080 omega-6 fatty acid Drugs 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 229920006350 polyacrylonitrile resin Polymers 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 235000010384 tocopherol Nutrition 0.000 description 1
- 229960001295 tocopherol Drugs 0.000 description 1
- 229930003799 tocopherol Natural products 0.000 description 1
- 239000011732 tocopherol Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- GVJHHUAWPYXKBD-IEOSBIPESA-N α-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 0.000 description 1
Landscapes
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は油脂の改質方法に関し、詳しくは長鎖高度不胞
和脂肪酸を多量に含存する油脂加水分解物の改質方法に
関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for modifying fats and oils, and more particularly to a method for modifying hydrolyzed fats and oils containing a large amount of long-chain highly unfouled fatty acids.
なお本発明において長鎖高度不飽和脂肪酸とは、１分子
あたり２０個以上の炭素原子を有し、３個以上の二重結
合を有する脂肪酸を意味する。In the present invention, the long-chain highly unsaturated fatty acid means a fatty acid having 20 or more carbon atoms per molecule and having 3 or more double bonds.
？従来の技術）
近年、長鎖高度不飽和脂肪酸のもつ生理活性が注目され
、その利用について活発な検討がなされるようになった
。つまり、現代の日本人を含め欧米型の肉を中心とする
食生活ではω−６長鎖高度不飽和脂肪酸（メチル末端よ
り数えて６番目のＣ−Ｃ結合に二重結合を有する脂肪酸
、例えばアラキドン酸（ＡＡ，Ｃｚ。．４）、Ｔ−リノ
レン酸（ＧＬＡ，Ｃ＋ｓ＋ｉ）など）が完全に摂取過多
の状態にあり、ω−６脂肪酸とω−３脂肪酸（メチル末
端より数えて３番目のＣ−Ｃ結合に二重結合を有する脂
肪酸、例えばエイコサペンクエン酸（Ｅ Ｐ Ａ，Ｃ２
。，，）やドコサヘキサエン酸（ＤＨＡ，Ｃ２■ｌ６）
など）との間で摂取バランスのくずれが生じて、様々な
成人病（ガン、高血圧、心臓病など）の原因になってい
ると報告されている。そこでω−３脂肪酸摂取の補助食
品として魚油を原料としだ長鎖高度不飽和脂肪酸を含有
する油脂の製造は、その有用度が注目されてきた。? Prior Art) In recent years, the physiological activity of long-chain highly unsaturated fatty acids has attracted attention, and active studies have been conducted on their use. In other words, Western-style meat-based diets, including those of modern Japanese people, are associated with omega-6 long-chain highly unsaturated fatty acids (fatty acids with a double bond at the 6th C-C bond counting from the methyl end, e.g. Arachidonic acid (AA, Cz..4), T-linolenic acid (GLA, C+s+i), etc.) are in a completely excessive intake state, and ω-6 fatty acids and ω-3 fatty acids (3rd fatty acids counting from the methyl end) Fatty acids with a double bond in the C-C bond, such as eicosapencitric acid (E P A, C2
. ) and docosahexaenoic acid (DHA, C2■l6)
It has been reported that an imbalance in intake occurs between the two (e.g.) and causes various adult diseases (cancer, high blood pressure, heart disease, etc.). Therefore, the production of fats and oils containing long-chain polyunsaturated fatty acids using fish oil as a raw material has attracted attention for its usefulness as a supplement for omega-3 fatty acid intake.
（発明が解決しようとする課題）
天然に存在する長鎖高度不飽和脂肪酸はその存在形態は
トリグリセリドである。しかしながら、魚油をリパーゼ
による加水分解反応で処理すると、長鎖高度不飽和脂肪
酸は完全にトリグリセリド中に濃縮されるわけではなく
、その一部はジグリセリドまたはモノグリセリド中に濃
縮されるため、トリー、ジー、モノグリセリドの混合物
として製品が得られる。この混合物よりグリセリドのみ
を分取してトリー、ジー、モノグリセリドの組成比を調
べるとトリグリセリドの含有率は通常８０％以下である
。栄養補助製品の見地からすれば、トリグリセリドの含
有率がなるべく高い油脂ほど、吸収面、代謝面において
生体にとってより自然な油脂として受け入れられる。(Problems to be Solved by the Invention) Naturally existing long-chain highly unsaturated fatty acids exist in the form of triglycerides. However, when fish oil is treated with a hydrolysis reaction using lipase, the long-chain polyunsaturated fatty acids are not completely concentrated into triglycerides, but some of them are concentrated into diglycerides or monoglycerides. The product is obtained as a mixture of monoglycerides. When only glycerides are separated from this mixture and the composition ratio of tri-, di-, and monoglycerides is examined, the content of triglycerides is usually 80% or less. From the standpoint of nutritional supplement products, the higher the triglyceride content, the more natural the fat will be accepted by the living body in terms of absorption and metabolism.
長鎖高度不飽和脂肪酸を高濃度に含有する油脂の製造法
として、魚油を原料に、キャンディダ（Ｃａｎｄｉｄａ
）属リパーゼの選択的加水分解を利用した長鎖高度不飽
和脂肪酸高濃度含有油脂の製造法（特開昭５８−１６５
７９６）が知られている。ところが、この製造法により
得られる油脂は、トリグリセリドの含有率が７５％程．
度で、ジー、モノグリセリドが混合しており、食品素材
としての品質面においての問題が残されていた。As a method for producing fats and oils containing high concentrations of long-chain polyunsaturated fatty acids, Candida
Method for producing fats and oils containing high concentrations of long-chain highly unsaturated fatty acids using selective hydrolysis of lipases of the genus ) (JP-A-58-165
796) is known. However, the fats and oils obtained by this production method have a triglyceride content of about 75%.
The product contained a mixture of polyglyceride, monoglyceride, and monoglyceride, and there remained a problem with its quality as a food material.
本発明は、長鎖高度不飽和脂肪酸を高濃度に含有する高
純度のトリグリセリドが効率的に得られる改質方法を提
供することを目的とする。An object of the present invention is to provide a modification method capable of efficiently obtaining a highly purified triglyceride containing a high concentration of long-chain highly unsaturated fatty acids.
（課題を解決するための手段）
本発明は、長鎖高度不飽和脂肪酸を含存する油脂をリパ
ーゼを用いて加水分解した後、脱グリセリンして得られ
た部分加水分解物であって、長鎖高度不飽和脂肪酸を多
量に含むグリセリドと脂肪酸との混合物を、無触媒状態
下、連続的に脱水しながら１００℃〜１８０℃で加熱す
ることを特徴とする、トリグリセリド濃度を高めた長鎖
高度不飽和脂肪酸含有油脂加水分解物の改質方法である
。(Means for Solving the Problems) The present invention provides a partial hydrolyzate obtained by hydrolyzing fats and oils containing long-chain polyunsaturated fatty acids using lipase and then deglycerolizing them. Long-chain highly unsaturated fatty acids with increased triglyceride concentration are produced by heating a mixture of glycerides and fatty acids containing a large amount of highly unsaturated fatty acids at 100°C to 180°C while continuously dehydrating them under non-catalytic conditions. This is a method for modifying a saturated fatty acid-containing oil/fat hydrolyzate.
本発明に用いる長鎖高度不飽和脂肪酸含有油脂原料とし
ては海産動物油、特にイワシ、サバ、サンマ、アジ、マ
グロ、カツオ等から得られる魚油がエイコサペンクエン
酸やドコサヘキサエン酸を多く含むので好ましい。As the long-chain highly unsaturated fatty acid-containing fat and oil raw material used in the present invention, marine animal oils, particularly fish oils obtained from sardines, mackerel, saury, horse mackerel, tuna, bonito, etc., are preferred because they contain large amounts of eicosapencitric acid and docosahexaenoic acid.
本発明において加水分解に用いるリパーゼは特に制限は
なく、例えばキャンディダ属、シュードモナス属、クロ
モバクテリウム属、ムコール属等の微生物由来のリパー
ゼが使用できる。The lipase used for hydrolysis in the present invention is not particularly limited, and for example, lipases derived from microorganisms such as Candida, Pseudomonas, Chromobacterium, and Mucor can be used.
本発明の油脂加水分解物の改質方法は、長鎖高度不飽和
脂肪酸を構成脂肪酸として含有する油脂をリパーゼを用
いて酸価５０〜１５０まで加水分解し、加水分解物から
グリセリンを除き、長鎖高度不飽和脂肪酸を構成脂肪酸
として含有するグリセリドと脂肪酸の混合物を得る。こ
の混合物中の水分含有層を１ ， ＯＯＯｐｐｍ以下（
望ましくは５〜１００ｐｐｍ）に下げるため、真空加熱
法、ＮａｚＳＯいモレキュラーシーブ、高分子吸水剤な
どの脱水剤もしくは乾燥窒素・二酸化炭素の吹き込み、
またはそれらの組み合わせなどにより予備脱水する。モ
ノー、ジグリセリドからトリグリセリドの生成反応は脱
水反応であるため、トリグリセリド含有率の高い油脂を
得るためには反応系中の水分含量を常にこの範囲内に止
めておく必要がある。トリグリセリド生成反応は、脱水
剤を使用し大気下で行って良いが、魚油など長鎖高度不
飽和脂肪酸を多く含存する場合は、乾燥窒素・二酸化炭
素の吹き込みによる脱水法が、脂肪酸の劣化を防ぐ面に
おいて好ましい。The method for modifying a hydrolyzate of fats and oils of the present invention involves hydrolyzing fats and oils containing long-chain highly unsaturated fatty acids as constituent fatty acids to an acid value of 50 to 150 using lipase, removing glycerin from the hydrolyzate, and A mixture of glyceride and fatty acid containing a chain highly unsaturated fatty acid as a constituent fatty acid is obtained. The water-containing layer in this mixture is reduced to less than 1,000 ppm (
In order to reduce the concentration to 5 to 100 ppm (preferably 5 to 100 ppm), a vacuum heating method, a dehydrating agent such as a NazSO molecular sieve, a polymeric water absorbing agent, or blowing of dry nitrogen or carbon dioxide,
Or pre-dehydrate using a combination of these methods. Since the reaction for producing triglycerides from mono- and diglycerides is a dehydration reaction, the water content in the reaction system must always be kept within this range in order to obtain fats and oils with a high triglyceride content. The triglyceride production reaction can be carried out in the atmosphere using a dehydrating agent, but if the oil contains a large amount of long-chain polyunsaturated fatty acids, such as fish oil, dehydration by blowing dry nitrogen or carbon dioxide will prevent deterioration of the fatty acids. preferred in terms of
また、トコフエロール、アスコルビン酸、ＴＢＨＱ１ブ
チル化ヒドロキシアニソール、ブチル化ヒドロキシトル
エンを併用しても良い。Further, tocopherol, ascorbic acid, TBHQ1 butylated hydroxyanisole, and butylated hydroxytoluene may be used in combination.
反応は無触媒の状態で行うことができ、反応温度１００
〜１８０℃の範囲で行うのが好ましい。１００℃未満で
は反応油脂の固化及び反応速度が遅く、１８０℃を超え
ると長鎖高度不飽和脂肪酸の劣化が著しくなる。更に好
ましくは１５０−１８０’Ｃで行う。The reaction can be carried out in the absence of a catalyst, and the reaction temperature is 100°C.
It is preferable to carry out in the range of -180 degreeC. If it is less than 100°C, the solidification and reaction rate of the reacted fats and oils will be slow, and if it exceeds 180°C, the deterioration of the long-chain highly unsaturated fatty acids will become significant. More preferably, it is carried out at 150-180'C.
また、反応は撹拌したほうが望ましいが、静置でも反応
は進む。Further, although it is preferable to stir the reaction, the reaction proceeds even if the mixture is left standing.
このようにして１〜４８時間（好ましくは５〜１２時間
）反応後、クロマトグラフィー、結晶分別、分別蒸留、
液々分配、脱酸法などの公知の技術を用いてグリセリド
を分取し、トリグリセリド含有率９０〜１００％の油脂
を得る。After reacting in this way for 1 to 48 hours (preferably 5 to 12 hours), chromatography, crystal fractionation, fractional distillation,
Glycerides are fractionated using known techniques such as liquid-liquid distribution and deacidification methods to obtain fats and oils having a triglyceride content of 90 to 100%.
（発明の効果）
本発明の方法によれば、無触媒状態下、連続的に脱水反
応を進めながら加熱するので、長鎖高度不飽和脂肪酸を
高濃度に含有する高純度のトリグリセリドを容易に得る
ことができる。この方法は、触媒を必要としないので、
製造コストが低く、しかも非常に簡単な工程で実施でき
る。(Effects of the Invention) According to the method of the present invention, since heating is carried out while continuously proceeding with the dehydration reaction under non-catalytic conditions, it is easy to obtain highly purified triglycerides containing a high concentration of long-chain polyunsaturated fatty acids. be able to. This method does not require a catalyst, so
The manufacturing cost is low and it can be implemented in a very simple process.
（実施例） 以下、実施例を以て更に本発明を具体的に説明する。(Example) Hereinafter, the present invention will be explained in more detail with reference to Examples.
実施例１
魚油（ Ｉ Ｖ ＝ １７１．０，構成脂肪酸中の長鎖
高度不胞和脂肪酸２３．５％（ＥＰＡ１３％、Ｄ Ｍ
Ａ ８％））５０ｇにキャンディダシリンドラシエより
得られたリパーゼを油脂１ｇにつき１００ユニソトにな
るように■り取り、蒸留水５０ｇを加えて、撹拌しなが
ら室温で８時間反応させた。反応終了後、リパーゼを含
む水層を除去して、分解油を得た。この分解油の酸価は
１２８であった。この分解油の一部をとり脂肪酸部分を
アルカリ脱酸法により除いてグリセリドを分取し、トリ
ー、ジー、モノグリセリド比をＴＬＣ−クロマトスキャ
ナー法で分析した結果、トリグリセリド７５％、ジグリ
セリド２３％、モノグリセリド２％であった。また、そ
の構成脂肪酸中の長鎖高度不飽和脂肪酸含量は４７．３
％であった。Example 1 Fish oil (IV = 171.0, long chain highly unfouled fatty acids in the constituent fatty acids 23.5% (EPA 13%, DM
A: 8%)) Lipase obtained from Candida cylindrical lacquer was taken out in an amount of 100 units per gram of oil and fat, 50g of distilled water was added, and the mixture was allowed to react at room temperature for 8 hours with stirring. After the reaction was completed, the aqueous layer containing lipase was removed to obtain a cracked oil. The acid value of this cracked oil was 128. A portion of this decomposed oil was taken, the fatty acid portion was removed by alkaline deoxidation, and the glycerides were separated.The triglyceride, di-, and monoglyceride ratios were analyzed by TLC-chromatography. It was 2%. In addition, the content of long chain highly unsaturated fatty acids in its constituent fatty acids is 47.3
%Met.
この分解混合物を４０℃の温湯で３回水洗して脱グリセ
リンし、５０℃に昇温して乾燥窒素を吹き込みながら水
分含ｉｔｌ００ｐｐｍ以下に調整した。次に連続脱水用
の乾燥窒素を吹き込みながら１５０℃で１０時間反応さ
せた。This decomposition mixture was deglycerinated by washing with hot water at 40°C three times, and then heated to 50°C and adjusted to a moisture content of 100 ppm or less while blowing dry nitrogen. Next, the mixture was reacted at 150° C. for 10 hours while blowing dry nitrogen for continuous dehydration.
反応後の油脂の脂肪酸部分をアルカリ脱酸法により除い
てグリセリドを分取し、トリー、ジモノグリセリド比を
ＴＬＣ−クロマトスキャナー法で分析した結果、トリグ
リセリド９８％、ジグリセリド２％、モノグリセリドＯ
％であった。また、その構成脂肪酸中の長鎖高度不飽和
脂肪酸含量は４１．３％（ＥＰＡＩＩ％、ＤＨＡ２６％
）であった。After the reaction, the fatty acid part of the oil and fat was removed by alkaline deoxidation method to separate the glyceride, and the triglyceride and dimonoglyceride ratio was analyzed by TLC-chromatography scanner method. As a result, triglyceride 98%, diglyceride 2%, monoglyceride O
%Met. In addition, the content of long chain highly unsaturated fatty acids in its constituent fatty acids is 41.3% (EPA II%, DHA 26%
)Met.
実施例２
実施例１と同様に分解、脱グリセリンした魚油分解物を
、乾燥二酸化炭素を吹き込みながら１００℃で２４時間
反応させた。Example 2 A fish oil decomposition product that had been decomposed and deglycerinated in the same manner as in Example 1 was reacted at 100° C. for 24 hours while blowing dry carbon dioxide.
反応後の油脂の脂肪酸部分をアルカリ脱酸法により除い
てグリセリドを分取し、トリー、ジモノグリセリド比を
ＴＬＣ−クロマトスキャナー法で分析した結果、トリグ
リセリド９０％、ジグリセリド９％、モノグリセリド１
％であった。また、その構成脂肪酸中の長鎖高度不飽和
脂肪酸含量は４４．３％（Ｅ Ｐ Ａｌｌ％、ＤＨＡ２
９％）であった。After the reaction, the fatty acid part of the oil and fat was removed by alkaline deoxidation method to separate the glycerides, and the triglyceride and dimonoglyceride ratios were analyzed by TLC-chromatography.
%Met. In addition, the content of long chain highly unsaturated fatty acids in its constituent fatty acids is 44.3% (EP All%, DHA2
9%).
実施例３
魚油１００ｇにクロモバクテリウムリパーゼをアミノ化
ポリアクリロニトリル樹脂に固定化した固定化酵素を油
脂１ｇにつき５０ユニットになるように遣り取り、蒸留
水３０ｇを加えて、撹拌しなから３７゜Ｃで１２時間反
応させた。反応終了後、リパーゼを含む水層を除去して
、分解油を得た。この分解油の酸価は１２５であった。Example 3 An immobilized enzyme obtained by immobilizing Chromobacterium lipase on aminated polyacrylonitrile resin was added to 100 g of fish oil at a concentration of 50 units per 1 g of oil and fat, 30 g of distilled water was added, and the mixture was heated at 37°C without stirring. The reaction was allowed to proceed for 12 hours. After the reaction was completed, the aqueous layer containing lipase was removed to obtain a cracked oil. The acid value of this cracked oil was 125.
この分解油の一部をとり、脂肪酸部分をアルカリ脱酸法
により除いてグリセリドを分取し、トリ、ジー、モノグ
リセリド比をＴＬＣ−クロマトスキャナー法で分析した
結果、トリグリセリド７０％、ジグリセリド２５％、モ
ノグリセリド５％であった。また、その構成脂肪酸中の
長鎖高度不飽和脂肪酸含量は４６．２％であった。A portion of this decomposed oil was taken, and the fatty acid portion was removed by alkaline deoxidation to separate the glycerides.The ratio of tri-, di-, and monoglycerides was analyzed by TLC-chromatography, and the results showed that triglyceride was 70%, diglyceride was 25%, The monoglyceride content was 5%. Moreover, the content of long chain highly unsaturated fatty acids in its constituent fatty acids was 46.2%.
この分解混合物を４０℃の温湯で３回水洗して脱グリセ
リンし、５０℃に昇温しで乾燥窒素を吹き込みながら水
分含量１００ｐｐｍ以下に調整した。次に連続脱水のた
めのモレキュラーシーブ３Ａを１０重量％加え、振盪撹
拌し、１８０゜Ｃで１５時間反応させた。This decomposed mixture was washed three times with hot water at 40°C to deglycerinate it, heated to 50°C, and adjusted to a water content of 100 ppm or less while blowing dry nitrogen. Next, 10% by weight of Molecular Sieve 3A for continuous dehydration was added, shaken and stirred, and reacted at 180°C for 15 hours.
反応後の油脂の脂肪酸部分をアルカリ脱酸法により除い
て、グリセリドを分取し、トリー、ジーモノグリセリド
比をＴＬＣ−クロマトスキャナー法で分析した結果、ト
リグリセリド９７％、ジグリセリド３％、モノグリセリ
ド０％であった。また、その構成脂肪酸中の長鎖高度不
飽和脂肪酸含量は４０．４％（Ｅ Ｐ Ａ ９％、ＤＭ
Ａ２８％）であった。After the reaction, the fatty acid part of the oil and fat was removed by alkaline deoxidation method, the glyceride was separated, and the triglyceride and di-monoglyceride ratio was analyzed by TLC-chromatography. there were. In addition, the content of long-chain highly unsaturated fatty acids in its constituent fatty acids is 40.4% (EPA 9%, DM
A28%).
実施例４
実施例３と同様に固定化リパーゼで分解・脱グリセリン
した魚油分解物を６０℃まで昇温し、吸引脱水して水分
含ｉ ６０ｐｐｍまで脱水した。次に１６０゜Ｃに昇温
し、反応容器を真空度３ｍｍｌｌｇで吸引して脱水し、
１０時間反応させた。Example 4 A fish oil decomposition product that had been decomposed and deglycerinated with immobilized lipase in the same manner as in Example 3 was heated to 60° C. and dehydrated by suction to a water content of 60 ppm. Next, the temperature was raised to 160°C, and the reaction container was dehydrated by suction at a vacuum level of 3 mmllg.
The reaction was allowed to proceed for 10 hours.
反応後の油脂の脂肪酸部分をアルカリ脱酸法により除い
てグリセリドを分取し、トリー、ジーモノグリセリド比
をＴＬＣ−クロマトスキャナー法で分析した結果、トリ
グリセリド９８％、ジグリセリド２％、モノグリセリド
Ｏ％であった。また、その構成脂肪酸中の長鎖高度不飽
和脂肪酸含量は４２．７％（ＥＰＡＩＯ％、ＤＨＡ２７
％）であった。After the reaction, the fatty acid part of the oil and fat was removed by alkaline deoxidation method, the glyceride was separated, and the triglyceride and di-monoglyceride ratio was analyzed by TLC-chromatography scanner method. As a result, triglyceride was 98%, diglyceride was 2%, and monoglyceride was 0%. Ta. In addition, the content of long chain highly unsaturated fatty acids in its constituent fatty acids is 42.7% (EPAIO%, DHA27
%)Met.
比較例１
実施例１と同様に分解、脱グリセリン、脱水した魚油分
解物を反応温度７０゜Ｃで乾燥窒素供給方式により脱水
しながら２４時間反応を行った。Comparative Example 1 A fish oil decomposition product that had been decomposed, deglycerinated, and dehydrated in the same manner as in Example 1 was reacted for 24 hours at a reaction temperature of 70° C. while being dehydrated by dry nitrogen supply.
反応後の油脂の脂肪酸部分をアルカリ脱酸法により除い
てグリセリドを分取し、トリー、ジーモノグリセリド比
をＴＬＣ−クロマトスキャナー法で分析した結果、トリ
グリセリド８２％、ジグリセリド１６％、モノグリセリ
ド２％であった。また、その構成脂肪酸中の長鎖高度不
飽和脂肪酸含量は４５．６％（ＥＰＡ１２％、ＤＨＡ２
８％）であり、トリグリセリド比の大きな上昇は望めな
かった。After the reaction, the fatty acid part of the oil and fat was removed by alkaline deoxidation method, the glyceride was separated, and the triglyceride and di-monoglyceride ratio was analyzed by TLC-chromatography scanner method. As a result, the result was 82% triglyceride, 16% diglyceride, and 2% monoglyceride. Ta. In addition, the content of long chain highly unsaturated fatty acids in its constituent fatty acids is 45.6% (EPA 12%, DHA2
8%), and no significant increase in the triglyceride ratio could be expected.
比較例２
実施例１と同様に分解、脱グリセリン、脱水した魚油分
解物を１８０゜Ｃで振盪撹拌を行ったが、連続脱水のた
めの乾燥窒素の吹き込み及び脱水剤の添加は行わなかっ
た。Comparative Example 2 A fish oil decomposition product that had been decomposed, deglycerinated, and dehydrated in the same manner as in Example 1 was shaken and stirred at 180°C, but without blowing dry nitrogen or adding a dehydrating agent for continuous dehydration.
２４時間反応後の油脂の脂肪酸部分をアルカリ脱酸法に
より除いて、グリセリドを分取し、トリジー、モノグリ
セリド比をＴＬＣ−クロマトスキャナー法で分析した結
果、トリグリセリド７４％、ジグリセリド２３％、モノ
グリセリド３％であった。After 24 hours of reaction, the fatty acid portion of the oil was removed by alkaline deoxidation, the glycerides were separated, and the triglyceride and monoglyceride ratios were analyzed by TLC-chromatography. As a result, triglyceride was 74%, diglyceride was 23%, and monoglyceride was 3%. Met.
また、その構成脂肪酸中の長鎖高度不飽和脂肪酸含量は
４５．３％（ＥＰＡ１２％、ＤＨＡ２７％）であり、ト
リグリセリド比の上昇は望めなかった。Furthermore, the content of long-chain highly unsaturated fatty acids in its constituent fatty acids was 45.3% (EPA 12%, DHA 27%), and no increase in the triglyceride ratio could be expected.
Claims (1)
て加水分解した後、脱グリセリンして得られた部分加水
分解物であって、長鎖高度不飽和脂肪酸を多量に含むグ
リセリドと脂肪酸との混合物を、無触媒状態下、連続的
に脱水しながら１００℃〜１８０℃で加熱することを特
徴とする、トリグリセリド濃度を高めた長鎖高度不飽和
脂肪酸含有油脂加水分解物の改質方法。It is a partial hydrolyzate obtained by hydrolyzing fats and oils containing long-chain polyunsaturated fatty acids using lipase and then deglycerinizing them. A method for modifying a long-chain highly unsaturated fatty acid-containing hydrolyzate of fats and oils with increased triglyceride concentration, the method comprising heating the mixture at 100°C to 180°C while continuously dehydrating the mixture under non-catalytic conditions.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1115000A JPH02295490A (en) | 1989-05-10 | 1989-05-10 | Modification of hydrolyzed product of fat or oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1115000A JPH02295490A (en) | 1989-05-10 | 1989-05-10 | Modification of hydrolyzed product of fat or oil |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02295490A true JPH02295490A (en) | 1990-12-06 |
Family
ID=14651818
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1115000A Pending JPH02295490A (en) | 1989-05-10 | 1989-05-10 | Modification of hydrolyzed product of fat or oil |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02295490A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998018952A1 (en) * | 1996-10-30 | 1998-05-07 | Nippon Suisan Kaisha, Ltd. | Process for producing fats containing highly unsaturated fatty acids containing selectively concentrated docosahexaenoic acid |
| WO1999009119A1 (en) * | 1997-08-18 | 1999-02-25 | Kao Corporation | Process for producing diglycerides |
-
1989
- 1989-05-10 JP JP1115000A patent/JPH02295490A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998018952A1 (en) * | 1996-10-30 | 1998-05-07 | Nippon Suisan Kaisha, Ltd. | Process for producing fats containing highly unsaturated fatty acids containing selectively concentrated docosahexaenoic acid |
| WO1999009119A1 (en) * | 1997-08-18 | 1999-02-25 | Kao Corporation | Process for producing diglycerides |
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