KR20090114020A - Transesterified oils with improved oxidation stability - Google Patents

Abstract

PURPOSE: Transesterified oils are provided to ensure excellent oxidation stability compared with conventional mixed oils and to be used in the field including food and fodder. CONSTITUTION: Transesterified oils are prepared by mixing (a) oil containing 15-80 weight% of highly unsaturated C20-24 fatty acid having 4-6 double bonds and (b) at least one vegetable oil or animal fat with 3 or less of a double bond; and performing transesterification using lipase. The highly unsaturated fatty acid is selected from the group consisting of arachidonic acid, docosahexaenoic acid, and eicosapentaenoic acid.

Description

Transesterification maintenance with increased oxidation stability {TRANSESTERIFIED OILS WITH IMPROVED OXIDATION STABILITY}

 (1) a fat or oil containing 15 to 80% by weight of a polyunsaturated fatty acid containing 20 to 24 carbon atoms and 4 to 6 double bonds based on the total weight of the fat or oil; And (2) vegetable or animal fats and fats having three or more double bonds of three or less; and a method of preparing a transesterified fat or oil characterized in that the mixture is prepared by transesterification using a lipase.

The present invention also relates to food and animal feed containing the transesterified fats and fats produced by the above production method.

Arachidonic acid, docosahexaenophosphate (DHA), and eicosapentaenoic acid (EPA) are not only effective in preventing adult diseases such as atherosclerosis and thrombosis, but also have various physiological functions such as anti-cancer effects and strengthening learning effects. As polyunsaturated fatty acids known to have, they are often used in medicine and certain health foods and / or supplements. However, fats and oils containing arachidonic acid have a low oxidative stability and are easily oxidized to cause unpleasant odor (such as fishy smell) and deterioration. Therefore, there is a difficulty in applying the fat or oil in the food field.

Generally, antioxidants are used to enhance the oxidative stability of fats and oils. For example, tocopherol, rosemary extract as a natural antioxidant, ascorbyl palmitic acid, BHT, propyl gallate, etc. are used in the form of a single or complex composition as a synthetic antioxidant. However, it is difficult to achieve sufficient oxidative stability only by adding an antioxidant to fats and oils as mentioned above.

It is an object of the present invention to provide a transesterified fat or oil having increased oxidation stability compared to conventional polyunsaturated fatty acid-containing fats and oils.

(1) a fat or oil containing 15 to 80% by weight of a polyunsaturated fatty acid containing 20 to 24 carbon atoms and 4 to 6 double bonds based on the total weight of the fat or oil; And (2) vegetable or animal fats and fats having three or more double bonds of three or less; but providing a method for producing a transesterified fat or oil, characterized in that the mixture is prepared by transesterification using a lipase.

In addition, there is provided a food and animal feed containing the transesterified fats and fats produced by the above production method.

Hereinafter, the present invention will be described in detail.

The transesterified fats and oils of this invention are characterized by the dispersion of the polyunsaturated fatty acids in the fats and oils and the increased oxidation stability.

When a fat containing polyunsaturated fatty acid is exposed to air, the polyunsaturated fatty acid starts to oxidize, and the oxidation reaction has a problem of easily transitioning to another polyunsaturated fatty acid adjacent to one molecule.

In the present invention, a transesterification reaction using a lipase disperses the concentration of polyunsaturated fatty acids in one molecule by transferring the polyunsaturated fatty acids concentrated in one molecule to another, thereby preventing a series of oxidation reactions from occurring. By manufacturing the fat or oil, the above problem can be solved.

Accordingly, the present invention provides a method for improving the fats and oils containing polyunsaturated fatty acids such as arachidonic acid by lipase transesterification to produce a transesterified fats and oils in which polyunsaturated fatty acids are dispersed.

The transesterified fats and fats produced by the manufacturing method of this invention have the advantage that oxidative stability increases compared with the fats and oils which are not transesterified, and is easy to use for food, a supplement, etc.

The transesterification fats and oils excellent in the oxidation stability by this invention are 1) fats and oils containing 15-80 weight% of polyunsaturated fatty acids which contain 4-6 carbon atoms with 20-24 carbon atoms, and 4-6 double bonds; And (2) vegetable or animal fats and oils having at least three double bonds can be obtained by carrying out transesterification with lipases.

The "highly unsaturated fatty acid" of the present invention is not particularly limited as long as it has 20 to 24 carbon atoms and 4 to 6 or less double bonds, and non-limiting examples thereof include arachidonic acid and docosahexaenoic acid (DHA). ) And eicosapentaenoic acid (EPA). The polyunsaturated fatty acid may be produced by microorganisms, or may be used by purchasing a commercially available one.

The arachidonic acid is one of polyunsaturated fatty acids, about 10% of fatty acids constituting important organs such as blood and liver (e.g., the fatty acid composition ratio of phospholipids in human blood is 11% for arachidonic acid and 1% for eicosapentaenoic acid. Docosahexaenoic acid accounts for 3%). It is involved in the regulation of fluidity of the membrane as a major component of the cell membrane and has various functions in relation to metabolism, and also plays an important role as a direct precursor of prostaglandins. In particular, attention has recently been focused on constituent fatty acids of endogenous cannabinoids (2-arachidonoyl monoglycerol and anandamide), which exhibit the role of arachidonic acid as an infant nutrient and its neurostimulating action. Eating foods rich in linoleic acid generally converts it to arachidonic acid, but adult patients, people susceptible to adult diseases, infants, and the elderly are less likely to have enzymes involved in biosynthesis, which eventually leads to arachidonic acid deficiency. It is a good idea to consume arachidonic acid directly in the form of triglycerides.

The docosahexaenoic acid (DHA) or eicosapentaenoic acid (EPA) is a polyunsaturated fatty acid known to have a variety of physiological functions, including preventive effects, anticancer action and learning enhancement effects on adult diseases such as atherosclerosis and thrombosis As such, they are often used as medicines and certain health foods and / or supplements.

In the present invention, 'fat containing highly unsaturated fatty acid' means a fat or oil containing 15 to 80% by weight based on the total weight of the fat and unsaturated fatty acids.

In the present invention, 'vegetable fats' may be used as food, or may be converted fats and oils. The vegetable oil may be used as a source of saturated fatty acids for transesterification, and non-limiting examples thereof include olive oil, rapeseed oil, soybean oil, corn oil, medium chain fat, palm oil, palm kernel oil, cacao oil, coconut oil, soybean oil, safflower oil. , Olive oil, rice bran oil, sesame oil and the like, but is not limited thereto.

In the present invention, 'animal fats and oils' may be used for food, or may be converted fats and oils. The animal fats and oils include egg yolk, lard, and the like.

In the present invention, the 'lipase' may be an immobilized enzyme, or may be a powdered enzyme. The lipase may be produced by microorganisms belonging to the genus Rhizopus, Rhizomucor, Aspergillus, etc., and may be purchased. In order to enhance the reaction efficiency against polyunsaturated fatty acids and to impart stability for repeated use, lipases immobilized on the immobilized carrier can be preferably used. As the immobilization carrier, a celite, an ion exchange carrier, a ceramic, an adsorption carrier for adsorbing a protein, etc. may be used. For example, as celite, powdery diatomaceous earth and granular diatomaceous earth, as ion exchange resin, Dowex MARATHON WBA (Dow Chemical) and DIAION WA30 (Mitsubishi Kagaku), ceramics SM-10 (Nihon Kaishi), and as adsorption resin DIAION HP 20 (Mitsubishi Kagaku) can be used.

In the present invention, the transesterification reaction can be carried out in the range of 20 ~ 70 ℃, preferably can be carried out at 30 ~ 50 ℃.

The transesterified fats and fats prepared by the production method of the present invention may be prepared by mixing a polyunsaturated fatty acid-containing fat or oil and one or more vegetable or animal fats or oils having three or less double bonds, and may be prepared by adding a lipase. One example may be expressed as in the following schematic diagram 1.

[Schematic 1]

The schematic diagram simplifies the reaction of mixing a fat or oil containing two arachidonic acids (ARA) with a fat or oil containing a fatty acid (R2) having a high degree of unsaturation, but adding a lipase to transesterify it. As can be seen from the above diagram, it can be seen that the polyunsaturated fatty acid concentrated in one molecule can be dispersed by the addition of lipase. As described above, it is possible to obtain a transesterification oil having excellent oxidation stability according to the present invention by adding lipase (see Experimental Example 1).

In the present invention, the lipase may be added in a range of 0.1 to 2% based on the total weight of the mixed fat and oil, but is not limited thereto. The reaction time may be adjusted according to the amount of lipase added. As the enzyme reactor, a columnar reaction or a batch reactor can be used. After the reaction is completed, the reaction solution is filtered to remove the enzyme, and then purified by the usual method used for purification of fats and oils, such as deoxidation, deodorization, steam distillation, etc. to obtain a transesterified fat or oil.

The transesterified oils and fats produced by the present invention have superior oxidation stability as compared to conventional polyunsaturated fatty acid-containing fats and oils, and thus can be usefully used in food compositions and the like (see FIG. 1). As the food composition, not only general foods, but also functional foods, nutritional supplements, premature infant formulas, infant formulas, infant formulas, foods for pregnant women and foods for the elderly may be mentioned. Examples of foods containing fats and oils include natural foods containing original fats and oils such as meat, fish, and nuts, foods to which fats and oils are added during cooking such as soups, foods using fats and oils such as donuts, and fats and oils such as butter. Processed foods to which fats and oils are added at the time of processing foods, cookies, etc., and foods which spray or apply fats and oils at the time of final finishing processes, such as hard biscuits, are mentioned. It may also be added to agricultural products, fermented foods, livestock foods, fish foods or beverages that do not contain fats and oils. They may also be in the form of functional foods or pharmaceuticals, such as enteral nutrients, powders, granules, lozenges, peritoneal membranes, suspensions, emulsions, syrups and the like.

The transesterified fats and fats produced by the present invention can also be used in animal feeds and the like.

In the present invention, a transesterification reaction using lipase can be used to transfer a polyunsaturated fatty acid concentrated in one molecule to another molecule to obtain a transesterification fat in a form in which the polyunsaturated fatty acid is dispersed. That is, a transesterification fat with enhanced oxidation stability can be obtained. Therefore, the applicability of the polyunsaturated fatty acid in the food field can be enhanced.

Hereinafter, the present invention will be described in more detail with reference to Examples and Experimental Examples. However, the following examples are illustrative of the present invention, and the contents of the present invention are not limited by the examples.

[ Example  One]

Mix 100 g of olive oil derived from Algae and 100 g of olive oil containing 40% by weight of the arachidonic acid with respect to the total weight of fats and oils, and immobilized lipase was added to the mixture. Under stirring at a rate of 50 RPM and reacted for 24 hours. The reaction solution obtained by the above reaction was filtered through a filter paper, and then deoxidized and deodorized to obtain fats and oils.

[ Comparative example  One]

A fat or oil (BO) was obtained by deoxidizing and deodorizing a fat or oil obtained by mixing 100 g of oil derived from Algae and 100 g of olive oil containing 40% by weight of arachidonic acid based on the total weight of the fat or oil.

< Experimental Example  1>

1000 ppm of tocopherol, an antioxidant, was added to each of the fats and oils (SL) obtained in Example 1 and the fats and oils (BO) obtained in Comparative Example 1.

The sample weight was measured to be 3 g, air flow was 20 L / h, and the absorption solution was 60 ml distilled water. As a result of the measurement, a curve as shown in FIG. 1 was formed. In addition, the induction period at 10 ° C was determined by the correlation between the induction period and temperature. Induction period values obtained are shown in Table 1 below.

　 Induction period (hours) Induction period (10 degrees) 100 110 120 130 time Work month Comparative Example 1 (BO) 10 5 2.4 1.1 6209 258.70 8.62 Example 1 (SL) 14.5 7 3.2 1.4 16684.6 695.19 23.17

BO: Arachidonic acid oil and olive oil

SL: Fats and oils which transesterified oil and arachidonic acid oil with lipase

As can be seen in Table 1, fats containing arachidonic acid-containing fats and olive oil (BO) is a fat or oil obtained by transesterification reaction of arachidonic acid fats and olive oil with lipase in 8.62 months, 6209 hours induction period (SL The induction period at 10 degrees was 16684 hours and 23.17 months. That is, it can be seen that the fats and oils obtained by transesterification by lipase have higher oxidation stability.

[ Example  2]

150 g of olive oil derived from Algae containing 50% by weight of the total arachidonic acid and 50 g of olive oil are mixed, and an immobilized lipase is added to the mixture in an amount of 1% by weight based on the total weight of the mixed fat and oil. The reaction was stirred at a rate of 50 RPM for 24 hours. The reaction solution obtained by the reaction was filtered through a filter paper, and deoxidized and deodorized to prepare a fat or oil.

[ Comparative example  2]

A fat or oil (BO) was obtained by deoxidizing and deodorizing a fat or oil obtained by mixing 150 g of oil derived from Algae and 50 g of olive oil containing 40% by weight of arachidonic acid based on the total weight of the fat or oil.

[ Example  3]

A fat or oil was prepared in the same manner as in Example 1, except that 100 g of heavy chain fat (Sefol, Co., Ltd.) consisting of 8 to 10 fatty acid chains was used instead of olive oil.

[ Comparative example  3]

A fat or oil (BO) was obtained by deoxidizing and deodorizing a fat or oil obtained by mixing 100 g of an oil derived from Algae and 100 g of a heavy chain fat containing 40% by weight of arachidonic acid based on the total weight of the fat or oil.

[ Example  4]

A fat or oil was prepared in the same manner as in Example 1, except that a fat or oil derived from Algae containing 40% by weight of docosahexaenophosphoric acid (DHA) was used instead of arachidonic acid.

[ Comparative example  4]

The fats and oils (BO) were obtained by deoxidizing and deodorizing the fats and oils which mixed 100 g of the oils derived from Algae containing 40 weight% of docosahexaenoic acid (DHA), and 100 g of olive oil.

[ Example  5]

The fats and oils were prepared in the same manner as in Example 1, except that 50 g of oil derived from Algae containing 40% by weight of docosahexaenophosphate (DHA) instead of arachidonic acid was used and 150 g of heavy chain fat was used instead of olive oil. Prepared.

[ Comparative example  5]

A fat or oil (BO) was obtained by deoxidizing and deodorizing a fat and oil obtained by mixing 50 g of an oil derived from Algae containing 40% by weight of docosahexaenophosphate (DHA) and 150 g of a medium chain fat (Sefol, Inc.).

< Experimental Example  2>

Into each fat or oil (SL) obtained in Examples 2 to 5, and 1000 ppm of tocopherol, an antioxidant, was added to each of the fats and oils (BO) obtained in Comparative Examples 2 to 5, and a fat and oil rancidity induction period was obtained using a fat and oil oxidation measuring machine called Rancimat. Was measured and compared.

The sample weight was 3 g, air flow was 20 L / h, and the absorption solution was 60 ml distilled water, and the induction period at 10 degrees was calculated. The resulting value is shown in Table 2 below.

Induction period (months) Example 2 23.17 Comparative Example 2 8.62 Example 3 26.12 Comparative Example 3 10.12 Example 4 4.12 Comparative Example 4 12.12 Example 5 20.23 Comparative Example 5 7.12

Through Experimental Example 1 and Experimental Example 2, it can be seen that the transesterification fat prepared by transesterification using lipase has much better oxidation stability than a simple mixed fat without lipase addition.

Figure 1 shows a graph measuring the maintenance rancidity induction period of the fat (SL) prepared in Example 1 and the fat (BO) prepared in Comparative Example 1 (dotted line: fat (BO) prepared in Comparative Example 1, solid line) : Fats (SL) prepared in Example 1).

Claims (9)

(1) a fat or oil containing 15 to 80% by weight of a polyunsaturated fatty acid containing 20 to 24 carbon atoms and 4 to 6 double bonds based on the total weight of the fat or oil; And (2) at least one vegetable or animal fat or oil consisting of three or less double bonds; a method of producing a transesterified fat or oil, characterized in that the mixture is prepared by transesterification using a lipase. The method of claim 1, wherein the polyunsaturated fatty acid is selected from the group consisting of arachidonic acid, docosahexaenoic acid and eicosapentaenoic acid. According to claim 1, wherein the vegetable oil is in the group consisting of medium chain fat, olive oil, rapeseed oil, soybean oil, corn oil, medium chain fat, palm oil, palm kernel oil, cacao oil, coconut oil, soybean oil, safflower oil, olive oil, rice bran oil and sesame oil oil A process for the preparation of transesterified fats and oils characterized by being selected. The method of claim 1, wherein said animal fat or oil is egg yolk oil or lard. The method of claim 1, wherein the lipase is an immobilized enzyme or a powdered enzyme. The transesterified fats and fats produced by the manufacturing method of any one of Claims 1-5. 7. The transesterification fat and oil according to claim 6, wherein the transesterification fat and oil is superior in oxidative stability as compared to the non-esterified mixed fat and fat. Food containing the transesterified fats and oils of Claim 6. Animal feed containing the transesterified fats and oils of claim 6

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