JPH0819044B2 - Eicosapentaenoic acid glyceride - Google Patents

Description

TECHNICAL FIELD The present invention relates to a glycerin ester (glyceride) of eicosapentaenoic acid (hereinafter abbreviated as EPA) for edible oil and fat products.

[Conventional technology]

EPA is abundant in nature as one of the fatty acids of fish oil. Polyunsaturated fatty acids such as EPA have been attracting attention in nutrition for a long time, but especially J. Dyerberg
Is effective in the prevention of adult diseases [[The Lance
t. ”Luly 15, 117 (1978)], research on it has been actively conducted, and it is known that it plays an important role in life support as a prostaglandin starting material, and its application to pharmaceuticals and dietary supplements is expanding. It has started to be done.

As mentioned above, EPA exists in nature as a fatty acid component of fish oil, etc., but the EPA content in various fish oils is almost 16.5% oirami oil, 15.8% sardine oil, 12.6% pollack liver oil.
%, Squid oil 10.2%, mackerel oil 8.1%, saury oil 4.9%, shark liver oil about 3.6% (Oil chemical gas chromatography data 1978-198).
0). As a method for separating and purifying glycerides bound with EPA from these oils, a low temperature crystallization method (JP-A-59-59644,
59-67241). With this method, it is possible to separate up to about 25% EPA. Also known are separation and purification methods such as chromatography, solvent extraction and molecular distillation. However, only EPA content of about 30% is obtained by the concentration method.

On the other hand, the glyceride form of EPA is said to be advantageous for digestion and absorption, so EPA glycerides with a high EPA content are required, but glycerides containing 30 to 70 mol% of EPA are bound. Is not yet known.

The present applicant has already filed an earlier patent application (JP-A-61-43143).
Although the specification discloses a glyceride having an EPA content of 30% or more and a method for producing the glyceride, there is room for research and development for further facilitating solidification of margarine when the glyceride is used as an oil and fat component of margarine. Has been done.

[Problems to be solved by the invention]

As it is already known, fish oil causes autoxidation when it is left in the air, resulting in reduced nutritional value and poor flavor. This is also the case with EPA-containing fats and oils components obtained by concentrating from fish oil, etc., and this deterioration phenomenon proceeds by a free radical chain reaction, and hydroperoxides accumulate in the fats and oils, and their decomposition products cause toxic and spoilage odors. Its use is limited because of its cause.

Therefore, EPA glycerides obtained by concentrating from fish oil and the like have attracted attention as dietary supplements and have been considered as food additives, but foods using them have not been put into practical use.

Further, as described above, the present applicant has already developed a glyceride having a high EPA binding ratio and a method for producing the same. However, the EPA glyceride obtained by this already-developed method inevitably contains a low-grade substance The fatty acid triglyceride-derived lower fatty acid acyl group is left behind, and the EPA glyceride produced by the presence of this lower fatty acid acyl group has a low melting point, which is used as a raw material for solid fat and oil products margarine and shortening. There was a problem in using it as an ingredient. Therefore, EPA glycerides having a higher melting point, that is, easily solidified, were required.

[Means for solving problems]

Therefore, if impurities other than oils and fats are reduced as much as possible and a glyceride having a high EPA content, preferably only EPA is obtained, the amount of EPA glyceride used can be reduced, resulting in the aforementioned fish oil or fish oil. The idea that nutritional deterioration and flavor deterioration seen in the concentrate can be reduced, and if a higher fatty acid glyceride is used instead of the lower fatty acid glyceride to be transesterified with the lower alkyl ester of EPA in the method developed by the present applicant, Therefore, based on the idea that it may be possible to obtain a glyceride containing EPA as a product in a high concentration and having a high melting point, EP
When the lower alkyl ester of A was transesterified with hydrogenated hydrogenated oil (higher fatty acid glyceride), it was possible to obtain a product with a high concentration of EPA, a high melting point and an excellent flavor as an edible oil and fat product. Thus, the present invention has been completed.

That is, the present invention is a EPA glyceride for edible oil and fat products, wherein the EPA acyl group obtained by subjecting a lower fatty acid ester of EPA and a hydrogenated hydrogenated oil to a transesterification reaction contains 30 to 70 mol% or more of all acyl groups. Regarding

The raw material EPA lower alkyl ester is preferably a high purity one, but as described above, the EPA lower alkyl ester is also unstable and easily deteriorates, so that a high purity one is difficult to obtain commercially. Thus, in some cases, the product EPA glyceride may have a relatively low EPA lower alkyl ester content, such as 30% or more.
Crude lower alkyl esters containing lower alkyl esters of EPA can also be used.

To prepare the lower alkyl ester of EPA, the refined sardine oil is subjected to a transesterification reaction with a lower alcohol to obtain a fatty acid ester mixture. The fatty acid ester mixture was mixed with urea to remove the saturated fatty acid ester and the EPA content of 35.
After adjusting to -40%, distillation is repeated to obtain high-purity EPA ester.

The glyceride which is one of the raw materials needs to contain an acyl group of a higher fatty acid, and hydrogenated hydrogenated oil is used in the present invention. As the hydrogenated hydrogenated oil, a commercially available hydrogenated oil such as hydrogenated hydrogenated palm oil is preferable.

 Then, a strong nitrogen-containing organic base (diazabicycloundece
Etc.), strong basic resin (Amberlyst A-26 Organo
Company), alkali metal alcoholates such as sodium methyl
Examples of higher fatty acid triglycerides in the presence of laths
For example, hydrogenated palm oil and high-purity EPA lower alkyl ester
It is prepared by a transesterification reaction with. As above
Triglycerides of higher fatty acids and lower alcohols of high-purity EPA
Killester was added to the reactor at a ratio of 1: 1 to 5 mol, and
1 to 5% by weight of sodium methyl ester based on the amount of these starting materials
Add a plate, heat and stir to allow the reaction to proceed. reaction
The temperature is 60 to 200 ° C, preferably 80 to 100 ° C, and the reaction time is 0.
5-10 hours, preferably 1-3 hours are sufficient. reaction
With longer times, EPA highly substituted grease
Ceride is obtained, but oxidation or polymerization reaction occurs
Then, the reaction is stopped when EPA is replaced by about 70 mol%.
It Water can be added to the reaction mixture to stop the reaction.
The reaction and operation should be nitrogen-free to prevent oxidation of EPA.
It is preferable to carry out in any inert gas atmosphere.

If necessary, the reaction solution is neutralized with an acid, water and, if necessary, an organic solvent such as ethyl acetate are added and shaken to separate the two layers. Next, the organic layer is separated, and when a solvent is used, the solvent is distilled off under reduced pressure to obtain a light brown, transparent oily substance containing EPA.

Further, it is preferable to decolorize the oily substance using 1 to 2% by weight of activated clay. Since the decolorized oil contains unreacted and formed lower alkyl ester, the temperature is 190 to 220 ° C.,
Distill for 60 minutes at a vacuum of 3-5 Torr. 3-5 after distillation
% Steam at a temperature of 190-220 ℃, vacuum degree of 3-5 Tor
Repeat steam distillation at r for 60 minutes. Oils obtained by distillation are triglycerides of higher fatty acids containing EPA and diglycerides of higher fatty acids containing some EPA.

The glyceride of the present invention has an eicosapentaenoyl group of 30
Since it is a glyceride of 70 to 70 mol% and 70 to 30 mol% of the acyl group of the higher fatty acid derived from hydrogenated hydrogenated oil, its melting point is lower than that of hydrogenated hydrogenated oil. Therefore, the melting point of the oil / fat component is not increased even when it is mixed with edible oil / fat products such as dressing and edible oil, which is preferable. The fats and oils products to be used in the present invention include margarine, shortening, mayonnaise, butter and the like, but margarine and shortening are particularly preferable. The blending amount of the triglyceride of the present invention into an oil or fat product is not particularly limited, but care should be taken so as not to impair the taste and flavor of the oil and fat product itself, and it should be half or less, preferably about 10%.

Next, the present invention will be described in more detail by way of examples.

Example A purified sardine oil and ethyl alcohol were subjected to a transesterification reaction with a concentrated sulfuric acid catalyst according to a conventional method, and then purified. The obtained 90% pure EPA ethyl ester (500 g) and hardened palm oil (mp52 ° C) (500 g) were mixed, and the mixture and sodium methylate (10 g) were added to a 1000 ml four-necked flask, and the container was placed. It was replaced with nitrogen gas. After replacement,
Heating was started, and the reaction was carried out at 90 ° C. for 30 minutes while stirring.

After the reaction was completed, water was added to deactivate the catalyst, and the mixture was washed 3 times with twice the amount of warm water to obtain 957 g of a light brown transparent oily substance.

Next, add 2% by weight of activated clay to the oily substance and the temperature is 100 ° C.
Decolorization was performed for 30 minutes under reduced pressure to obtain 912 g of a filtered oily substance.

The filtered oily substance was distilled at a temperature of 200 ° C. and a vacuum degree of 5 Torr for 60 minutes. Further, steam deodorization was carried out for 60 minutes by blowing in 3% steam to obtain 430 g of a distillate and 450 g of a pale yellow oil. The obtained pale yellow oily substance had no fishy odor immediately after deodorization and was tasteless and odorless. 1 g of this oil is hexane
It was dissolved in 5 ml and the glyceride composition was examined by gas chromatography (FID) under the following conditions. 94.5 for triglycerides
% By weight. At the same time, the oily substance was transesterified with methanol to prepare a fatty acid methyl ester. Then, in order to investigate the fatty acid composition, gas chromatography (FID) analysis was performed under the following conditions. Eicosapentaenoic acid was 45.5% by weight.

Conditions for gas chromatography (FID) (1) Triglyceride composition analysis Column: Diasolid ZT (manufactured by Nippon Chromato Kogyo Co., Ltd.) φ3 mm × 0.5 m Made of stainless steel Temperature: Inlet 300 ° C Oven 150 ° C → 340 ° C (temperature rise 10 ° C / min) ) Carrier gas: Nitrogen 80ml / min (2) Fatty acid composition analysis Column: 15% DEGS Chromosorb WAW DMCS mesh60 / 80 (manufactured by Gaskuro Industrial Co., Ltd.) Temperature: Inlet 235 ℃, oven 195 ℃ Carrier gas: Nitrogen 40ml / min This Was used to produce spread margarine in the following blending ratio. The compounding ratio is 80.7% by weight of a pale yellow oily substance, water.
16.0% by weight, 1.0% by weight of sodium chloride and 2.3% by weight of an emulsifier and a fragrance were mixed, and spread margarine was produced by a small experimental margarine maker.

Comparative Example For comparison, 70% by weight of refined fish oil containing 25% EPA and 30% by weight of soybean hydrogenated oil (mp39 ° C) were mixed to obtain a mixture.
A spread margarine was produced in the same manner as described in Examples, with 80.7% by weight as the blended fat and oil. The EPA content of this margarine was 17.3% by weight.

The spread margarines produced in Examples and Comparative Examples were stored at 5 ° C. and −25 ° C., respectively, and the changes in flavor and peroxide value (POV) were examined over time.

The results are shown in Table 1. In the spread margarine according to the example, the peroxide value (POV) and the returning smell of fish oil odor were both satisfactory.

Continuation of the front page (56) References JP-A-60-204739 (JP, A) JP-A-60-234588 (JP, A) BIORHEOLOGY. 22 [3] (1985), 221-226

Claims (1)

[Claims] 1. An edible oil and fat product, wherein the eicosapentanoyl group obtained by the transesterification reaction of hydrogenated hydrogenated oil and a lower alkyl ester of eicosapentaenoic acid is 30 to 70 mol% of all acyl groups in a glyceride. Eicosapentaenoic acid glyceride.