JPH0715108B2 - Edible oil and fat products containing glycerides of eicosapentaenoic acid - Google Patents

Description

TECHNICAL FIELD The present invention relates to an edible oil / fat product containing a glyceride of eicosapentaenoic acid (hereinafter abbreviated as EPA).

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 it was reported that J. Dyerberg is particularly effective in preventing adult diseases [The Lancat. July 15, 117 (1978)].
Since then, research on it has become active, 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 has expanded. .

Therefore, an object of the present invention is to provide an edible oil / fat product containing EPA glyceride, which can be effectively used as a medicine or a dietary supplement.

[Prior art]

As mentioned above, EPA exists in nature as a fatty acid component of fish oil, but the EPA content in various fish oils is almost the same as that of oirami oil1.
6.5%, sardine oil 15.8%, pollock liver oil 12.6%, squid oil 10.2%, mackerel oil 8.1%, saury oil 4.9%, shark liver oil 3.
It is about 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 and JP-A-5-59644).
9-67241). 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, but only about 30% EPA content 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 EPA content of 30% or more, especially only EPA is bound. The glycerides it contains are not yet known.

[Problems to be Solved by the Invention]

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

For this reason, 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.

[Means for solving problems]

Therefore, by using a glyceride having a high content of EPA in which impurities other than fats and oils are reduced as much as possible, it is possible to prevent the above-mentioned deterioration phenomenon and consequently reduce the amount of EPA glyceride used, and as described above. The present invention has been completed based on the idea that the nutritional deterioration, flavor and deterioration of fish oil or fish oil concentrate can be reduced.

That is, the present invention is a transesterification reaction product with eicosapentaenoic acid lower alkyl ester, wherein the content of the acyl group of the higher fatty acid is 90% by weight or less of the total acyl groups, and the content of the eicosapentaenoyl group is The amount relates to an edible oil / fat product containing eicosapentaenoic acid glyceride whose amount is 30% by weight or more of all acyl groups and 40% by weight or more of acyl groups of higher fatty acids.

The glycerides of EPA used in the present invention are triacetin and EPA.
It can be produced by subjecting a lower alkyl ester of 1 to a transesterification reaction. The EPA lower alkyl ester used here is preferably a high purity one, but the EPA lower alkyl ester is also unstable and easily deteriorates, so that a high purity one is difficult to obtain commercially. Therefore, in the present invention, a product having a relatively low content of EPA lower alkyl ester can be used depending on the use of the product EPA glyceride. In the present invention, for example, a crude lower alkyl ester containing 30% by weight or more of EPA lower alkyl ester can be used.

In addition, one of the raw materials, triacetylene, is inexpensive and
Since by-product methyl acetate and the like have a low boiling point, they can be easily separated from glycerides. Furthermore, even if unreacted lower alkyl ester of EPA remains in the product of the present invention, it is not necessary to completely remove it because it is not a harmful substance itself. However, it is necessary for the purpose of the present invention that the crude organism contains 40% by weight or more of EPA as a higher fatty acid component.

An example of the method for producing the EPA glyceride used in the present invention and the method for producing the starting material EPA lower alkyl ester will be described in detail below.

To prepare lower alkyl ester of EPA, refined sardine oil is subjected to transesterification reaction with lower alcohol to obtain a fatty acid ester mixture (including higher fatty acid ester other than EPA). The fatty acid ester mixture was prepared by removing the saturated fatty acid ester by inclusion of urea, and the EPA content was 35-40%.
%, And then distilled repeatedly to obtain high-purity lower alkyl ester of EPA.

Next, the EPA glyceride used in the present invention is strongly nitrogen-containing.
Organic bases (diazabicycloundecene, etc.), strongly basic trees
Fat (Amberlyst A-26 Organo), alkali gold
Presence of genus alcoholates such as sodium methylate
Below, glycerides of lower fatty acids such as triacetin and high
Transesterification reaction with pure EPA lower alkyl ester
It is adjusted accordingly. Low in triacetin and high-purity EPA
Primary alkyl ester in the reactor at a ratio of 1: 1 to 5 mol
In addition, 1-5% by weight of the amount of these starting materials
Ummethylate was added, and the reaction was performed under heating, stirring, and reduced pressure.
Make progress. Lower fatty acid ester
Since tellur is generated, the reaction system can be removed by evaporating it under reduced pressure.
It is preferable to remove it to the outside. The reaction temperature is 60-200 ℃,
Preferably 80-100 ℃, reaction time 0.5-10 hours, preferably
For example, 1 to 3 hours is sufficient. Raw of lower fatty acid ester
When no further growth is observed, add water to the reaction mixture and
Stop responding. To prevent oxidation of EPA, reaction and
It is preferable to operate in an atmosphere of an inert gas such as nitrogen.
Yes.

Then, if necessary, the reaction solution is neutralized with an acid, water and an organic solvent such as ethyl acetate are added thereto and shaken if necessary, and after separating into two layers, the aqueous layer is removed and the organic layer is further washed with water. 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, the oily matter is fractionated by the difference in the number of fatty acid groups substituted by thin layer chromatography, silica gel column chromatography, etc. In addition, it is possible to separate by the boiling point difference by the molecular distillation method. For example, silica gel column chromatography is performed using ethyl acetate, acetone or the like. Collect each fraction while confirming the eluate by thin layer chromatography.

The present invention relates to an edible oil / fat product containing the EPA glyceride. The edible oil and fat product targeted by the present invention,
For example, there are margarine, chyo toning, edible oil, mayonnaise, dressing, butter, etc., and especially dressing, margarine and edible oil are preferable, and they can be produced by a usual method and formulation.

Next, the present invention will be described in more detail with reference to Reference Examples and Examples.

Reference Example 1 According to a conventional method, a purified sardine oil and ethyl alcohol were subjected to a transesterification reaction with a concentrated sulfuric acid catalyst, followed by purification. Was added to a 1000 ml four-necked flask, and the container was replaced with nitrogen. Stirring and heating were started, 120 g of triacetin was injected from the dropping funnel, and the pressure was reduced by an aspirator. Since the produced ethyl acetate was distilled off as the temperature of the reaction liquid increased, it was condensed and removed in a cooler. Oil bath temperature 80-100 ℃, reaction start 1
After a while, remove the oil bath from the reactor, cool the internal temperature to around room temperature, add 13 ml of acetic acid, then add ethyl acetate and water, shake, and let stand to separate the upper ethyl acetate layer. After separating and washing 3 times with 300 ml of water, the solvent was distilled off under reduced pressure to give 522 g of a light brown, transparent oil (i).
Got

Next, 190 g of the above oil (i) was subjected to thin-film centrifugal molecular distillation, and the unreacted ethyl ester 45.6 was distilled first.
After removing g, 142.5 g of an oily product (ii) was obtained. This oil (i
A part of i) was transesterified with methanol to prepare a fatty acid methyl ester. Gas chromatographic analysis was performed to investigate the fatty acid composition. About fatty acids
90% by weight was higher fatty acids, of which eicosapentaenoic acid was 40% by weight.

Conditions for gas chromatography (FID) Column: 10% DEGS Chromosorb WAW DMCS 60/80 (manufactured by Gaskuro Industrial Co., Ltd.) φ3 mm x 2 m glass Temperature: inlet 240 ° C oven 195 ° C carrier gas: nitrogen 50 ml / min Retention time: approx. 20 minutes Reference example 2 Triacetin 2.2 g, 90% eicosapentaenoic acid ethyl ester 10.0 g and sodium methylate 0.2 g were used for transesterification in the same manner as in Reference example 1 and post-treatment was carried out to give a pale brown, transparent oily substance. (I) Obtained 8.6 g.

Next, 1 g of the above oily substance was suspended in 50 g of silica gel (70-230 mesh, manufactured by Merck Ltd.) in hexane to form a glass tube φ3.
It was attached to a column packed cm × 30 cm. 200 ml of hexane,
The fractions eluted with 1000 ml of hexane-ether (95: 5, v / v) were collected and the solvent was distilled off under reduced pressure to obtain 0.24 g of a pale yellow transparent oily substance. When this material was separated by thin layer chromatography, it was unreacted eicosapentaenoic acid ethyl ester. Furthermore, 1000 ml of hexane-ether (85:15), 600 m of hexane-ether (70:30)
The fractions eluted with 200 ml of acetone were collected and the solvent was distilled off under reduced pressure to obtain 0.75 g of a pale brown and transparent oily substance (ii). Part of this oil was transesterified with methanol,
A fatty acid methyl ester was prepared. Gas chromatographic analysis was performed to investigate the fatty acid composition. About 90% by weight of fatty acids are higher fatty acids.
90% by weight was eicosapentaenoic acid.

Example 1 30% by weight of the oily substance (ii) obtained in Reference Example 1, 7% by weight of vinegar,
Sorbet solution 10% by weight, seasoning (salt 1.5% by weight, sugar
0.7% by weight, Western pepper 0.2% by weight, sodium glutamate 0.
1% by weight) 2.5% by weight, natural gum (xanthan gum) 0.
An emulsified dressing was produced as follows using 3% by weight, a stabilizer (RC-N81 Avicel) 3.7% by weight, corn starch 2.5% by weight, and water 44% by weight.

A mixture of natural gum, stabilizer, corn starch and water was stirred and mixed with heating until a paste was formed, and then, a sorbit solution and a seasoning were sequentially added. Then, the oily substance (ii) was added dropwise to emulsify, vinegar was added, and the mixture was homogenized with a colloid mill to produce dressing.

For comparison, a salad oil (manufactured by Nisshin Oil Co., Ltd.) was used in place of the oily substance (ii) to repeat the above operation to fabricate dressing.

When the physical properties and flavors of the two obtained dressings were compared, the dressing of the present invention was comparable to the comparative example and was satisfactory.

Example 2 40.35% by weight of the oil (ii) obtained in Reference Example 2, 16.1% by weight of safflower oil, 24.2% by weight of hydrogenated soybean oil (melting point 39 ° C.), water
16.05% by weight, 1.0% by weight of sodium chloride and 2.3% by weight of emulsifier and fragrance were blended to produce spreaded margarine on a small experimental margarine maker. The content of eicosapentaenoic acid contained in the obtained margarine is 36.3% by weight.
It was.

For comparison, 40.35% by weight refined fish oil, 16.
1% by weight, soybean hydrogenated oil (melting point 39 ° C) 24.2% by weight, water 16.05
Margarine was prepared in the same manner by blending wt%, salt 1.0 wt% and 2.3 wt% emulsifier and fragrance.

The time-dependent flavor of the margarine obtained in the above Example 2 was satisfactory, and the returning smell of fish oil odor was one month later (5 ° C).
It was not observed even when stored in).

The time-dependent changes in flavor and peroxide value (POV) are shown below.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-59-190948 (JP, A) JP-A-59-172596 (JP, A) JP-A-59-113099 (JP, A)

Claims (1)

[Claims] 1. A transesterification product of a lower alkyl ester of eicosapentaenoic acid and triacetin, wherein the content of the acyl groups of the higher fatty acid is 90% by weight or less of the total acyl groups, and the eicosapentaenoyl group is contained. Is an edible fat product containing eicosapentaenoic acid glyceride having a content of 30% by weight or more of all acyl groups and 40% by weight or more of acyl groups of higher fatty acids.