KR19980024248A - Manufacturing method of stabilized fats and oils, obtained fats and oils containing the fats and oils - Google Patents

Abstract

The present invention relates to a method for producing stabilizing fats and oils, and the stabilizing fats and oils containing stabilizing fats and oils. The present invention relates to a fat or oil containing a large amount of unstable polyunsaturated fatty acid, such as a stabilized method of monoglycerides of refined fish oil, a stabilized oil obtained and a food containing the stabilized oil.

Description

Manufacturing method of stabilized fats and oils, obtained fats and oils containing the fats and oils

The present invention relates to a method for producing stabilizing fats and oils, and the stabilizing fats and oils containing stabilizing fats and oils. The present invention relates to a fat or oil containing a large amount of unstable polyunsaturated fatty acid, such as a stabilized method of monoglycerides of refined fish oil, a stabilized oil obtained and a food containing the stabilized oil.

In the present invention, stabilization is used in the sense of oxidative stabilization.

In recent years, especially when fats and oils containing unsaturated fatty acids are known to have a physiological effect, especially from the health-oriented side, these fats and oils are widely used for addition to food and feed. However, when added to foods, feeds, etc., even if the stability of fats and oils is secured in foods, feeds, and the like, the odor is generated even by slight oxidation in the manufacturing process. Various considerations were needed for the handling of fats and oils, such as the need to close the container which contained gas, and the use was limited.

As the demand for fats and oils containing unsaturated fatty acids is increasing, there is a strong demand for solving the problem of stability in handling.

One aspect of stabilization of fats and oils is powdering. In order to obtain a stable fat powder, a method of encapsulating the fat or oil in a microcapsule or powdering the fat or oil by cyclodextrin is employed. However, there are problems such as complicated manufacturing operation, poor productivity, breakdown of capsules during storage, and limited types of capsules that can be used as food, feed, and the like. Moreover, in order to stabilize fats and oils conventionally, adding antioxidant is performed. In this case, it is also known to improve antioxidant properties by combining a plurality of antioxidants or adding synergists such as phosphoric acid and citric acid ascorbic acid. By the way, in the case of fats and oils which are very poor in stability, such as fish oil, only the combination of the antioxidant and synergistic agent generally considered has a limit to the improvement of stability.

Emulsifiers are used in a wide range of foods because they have various effects in addition to their main emulsification function. Among these emulsifiers, fatty acid esters of polyalcohols (monoglycerides, sucrose esters, propylene glycol series, sorbitan emulsifiers) have been reported to be effective in preventing oxidation of swine oil (Clear et al., Oil Science, 34,470 (1985)). However, the effect is not large, and synergistic effect with tocopherol, which is a representative antioxidant, is also confirmed, but it is not large, and there is little used for the purpose of stabilizing fats and oils because palm oil has no effect and there is not enough antioxidant effect or the target oil is limited. .

An object of the present invention is to provide a method for producing stabilized fats and oils with improved storage stability, obtained oils and fats and foods containing the stabilized fats and oils.

1 is an explanatory diagram showing a change in the POV of various holdings.

2 is an explanatory diagram showing the amount of oxygen in the head spaces of various holdings.

3 is an explanatory diagram showing a change in the POV of the holding of the second embodiment.

4 is an explanatory diagram showing the amount of oxygen in the head space of the fat and oil of the second embodiment.

5 is an explanatory diagram showing a change in the POV of the holding of Comparative Example 1. FIG.

6 is an explanatory diagram showing the amount of oxygen in the head space of the fats and oils of the comparative example 1;

7 is an explanatory diagram showing the effect of monoglycerides on the refined fish oil of Example 5.

The present inventors have made various studies to stabilize fats and oils (fats and oils containing a lot of highly unsaturated acids), and as a result, the oxidation stability of fats and oils can be significantly improved by adding monoglycerides, especially among polyalcohol emulsifiers. We found that there was number. In addition, it has been found that the effect of the addition of monoglycerides thereof is large in fats and oils which serve as an addition control, especially in fats and oils containing polyphenols as antioxidants. In addition, it has been found that foods containing stabilizing fats and oils have not had various problems such as generation of odors caused by oxidation of fats and oils.

The fats and oils which are object of this invention are the fats and oils or aquatic animal oil which contain a lot of polyunsaturated fatty acid. Polyunsaturated fatty acid means a fatty acid having an unsaturated degree of 3 or more. Examples of the polyunsaturated fatty acid having an unsaturated degree of 3 or more include α-linolenic acid, arachidonic acid, eicosapentaenoic acid, and docosahexaenoic acid. In addition, polyunsaturated fatty acids include ester derivatives such as methyl esters, ethyl esters, triglycerides, diglycerides and monoglycerides of fatty acids thereof, carboxylic acid derivatives such as amides and methylamides, and aliphatic alcohols.

Eicosapentaenoic acid is a general term for unsaturated fatty acids having 5 double bonds with 20 carbon atoms, but as a natural product, the positions of the double bonds are 5, 8, 11, 14, 17, and all cis-type linear unsaturated ω3-based Point to fatty acids. Docosahexaenoic acid is a straight-chain hexaenoic acid having 22 carbon atoms having a cis double bond at 4, 7, 10, 13, 16, and 19 positions. Its naturally occurring EPA and DHA are included in natural oils and fats, especially in marine oils, such as mackerel, sardines, and cod, or as derivatives such as glycerides.

The present invention can be used as long as it is a raw material containing a polyunsaturated fatty acid having the above unsaturated degree of 3 or more. Raw materials containing polyunsaturated fatty acids are raw materials of all stages of purification, such as sardines, mackerel, saury, tuna, crustaceans such as sea shrimp, crude fish oil, animal and vegetable oils, and lipids derived from microorganisms. Although it is possible to do this, Preferably it is the raw material which carried out the deoxidation process from the remainder of the added monoglyceride. The fish oil used in the present invention includes tuna crystalline oil that occurs when the tuna fish oil is frozen and is centrifuged or filtered.

The oil milked from the fish raw material can be deoxidized and decolorized according to a conventional method (after), and then the fat or oil component containing the polyunsaturated fatty acid can be concentrated by a freezing process. The deoxidation and decolorizing oil are produced, for example, as follows.

The fish raw material is homogenized in heat water to extract fat-soluble components, and centrifuged to separate the solids, water and oil into three phases to obtain fish oil. Use this oil as crude oil. The main stream is heated to 7 占 폚, and phosphoric acid and caustic soda are added to remove foreign substances such as oxides, rubbers, and water in the crude oil. Centrifugation is used to separate the water layer. The crude oil is washed with hot water at 80 ° C, dried to remove moisture, and then the color components in the crude oil are removed to obtain the above deoxidized and decolorized oil.

The freezing step is a step of crystallizing and separating the oil having low unsaturation by cooling the oil. This crystal can be easily fractionated by separation methods such as filtration and centrifugation. However, since the mother liquor remains in the fractionated crystalline oil, the crystalline oil contains 50 to 80% by weight of the polyunsaturated fatty acid of the fish oil before freezing treatment. When fish oil containing a large amount of polyunsaturated fatty acids is used as a raw material, many unsaturated fatty acids are also included in the crystalline oil generated during freezing. For example, 5 volumes of organic solvents are mixed with 1 volume of deoxidized oil and rapidly cooled to -40 to 50 ° C. As a result, high solidification point maintenance such as saturated fatty acid contained in the deoxidized decolorized oil solidifies. This can be separated by centrifugation or filtration to increase the concentration of polyunsaturated fatty acids. Unsaturated fatty acids and saturated fatty acids coexist in tuna oil, and unsaturated fatty acids remain in tuna crystal oil. In one example of freezing, 8% by weight EPA and 28% by weight DHA are included in frozen oil, while 15% by weight EPA and 7% by weight DHA are included in crystalline oil. Tuna crystalline oil is purified and used after removing different flavors and odors. This crystalline oil has a high melting point, and when added to aquatic products such as Nectar, it gives a feeling of melting in the mouth and has a good effect on the taste.

Since the oxidation of fats and oils changes its flavor and color and lowers the nutritional value, it is important for edible fats and oils to prevent the oxidation. The rancidity of edible oils and fats is due to hydrolysis and automatic oxidation. The change in flavor due to automatic oxidation is due to decomposition products of hydrogen peroxide produced by oxidation, and for example, propionaldehyde, 2-pentenal, caproaldehyde, acetaldehyde, crotonaldehyde and the like can be obtained from the automatic oxidation of soybean oil.

The unpleasant smell of fish oil is due to the oxidation of polyunsaturated fatty acids, which give off a characteristic fishy smell. Changes by automatic oxidation are remarkable in foods containing fats and oils containing polyunsaturated fatty acids, such as fish oil, but even in saturated glycerides, fatty acids are produced by hydrolysis and the taste is impaired.

In refined oils such as fish oil, soybean oil, flax oil, and rapeseed oil containing linolenic acid, tetraenoic acid and the like, unpleasant odor may occur or color deterioration even at an extremely early stage of oxidation. This phenomenon is called Modori. This color of bleached crude oil is due to the oxidation of vitamin E, Chromann-5,6-ginone. Factors influencing the oxidation of fats and oils include fatty acid composition, temperature, irradiation of light, oxidation promoters such as metal or metal soap. In general, vegetable oils contain natural antioxidants such as vitamin E and Gosipol.

Among the antioxidants, which are chemicals that prevent oxidation of oils and fats, food supplements are approved for BHT (2,6-di-tert-butyl-p-cresol) and 2 (3) -tert-butyl-4-hydroxy. Anisol (BHA), ethyl protocatechuate, glutaric acid isoamyl, boric acid propyl, nordihydroguaiarechinic acid, guayac.

Antioxidants are effective in extending the induction period of the automatic oxidation of fats and oils, to suppress the rise of the peroxide value of fats and oils, and to improve the stability of AOM (active oxygen method). The use of synergists such as phosphoric acid, vitamin C and citric acid is effective.

It is not effective because there is no stabilizing power by the monoglyceride formulation. This may be the effect of residual fatty acid salts. Monoglycerides to be used as stabilizers of the present invention as long as it has a stabilizing ability, any preparation method (transesterification reaction of glycerin and fatty acids, transesterification reaction of glycerin and fats and oils), purification step (self-emulsifying, undistilled monoglycerides, distillation) Monoglycerides) may be used.

Most preferred monoglycerides having high stabilizing ability to be used as stabilizers of the present invention are non-fat-free, non-distilled monoglycerides with low fatty acid salts. The reason for this is that self-emulsifying monoglycerides rich in fatty acid salts are colored and oxidized by their salts. In the stabilizing ability, undistilled monoglycerides are higher than distilled monoglycerides. It is not clear why undistilled monoglycerides with low monoglyceride content have higher stabilizing ability than distilled monoglycerides, but it is presumed to be due to the synergistic effect (change in maintenance interface) of glycerin and diglycerides.

Although the kind of fatty acid which comprises a monoglyceride is not limited, the stabilizing ability is so stable that the fatty acid chain length is short, and the side which is low in unsaturation is stable. However, since monoglycerides containing fatty acids of less than 12 carbon atoms are poor in flavor and added to saturated fatty acids having high carbon number, the viscosity of the fats and oils increases and is dissolved in oils and fats, so it is preferably 12 or more carbon atoms, most preferably 14 to 18 carbon atoms. Fatty acids having one saturated or double bond are preferred.

Although the fats and oils stabilized by adding this monoglyceride can be used independently, you may mix with other fats and oils excellent in stability (plant holding etc.).

When the fats and oils stabilized by adding this monoglyceride are used for foods, quality deterioration, such as generation | occurrence | production of the oily odor from the oils and fats, flavor deterioration, and fading, can be suppressed. For example, foods in which fresh fish meat has been added to a mince fat oil (particularly fish oil) will lose their flesh color after a storage time. In particular, nectar, which is made from tuna meat, is a big problem because the vivid red color of tuna disappears due to synergistic progress of oxidation of fats and fats of myoglobin. In order to solve this problem, a method of adding a water-soluble antioxidant or a more stable vegetable oil is known. However, either of them has a taste problem or a low ω-3 type highly unsaturated fatty acid is not solved. However, when the fats and oils stabilized by adding this monoglyceride are used as nectar fats, the discoloration of tuna meat is suppressed considerably by suppressing oxidation of the polyunsaturated fatty acid by preservation. Since it was confirmed by the present inventor for the first time that addition to a nectar has not only a stabilizing effect but also a physical property improving effect, it filed a separate application.

Moreover, in recent years, the food which became easy to ingest by adding (omega) -3 highly unsaturated fatty acid to O / W emulsion type drink is proposed. However, even in this case, the amount of addition is limited because of problems such as a change in beauty due to oxidation of polyunsaturated fatty acids, deterioration of smell, etc. during the storage period. However, when the fats and oils stabilized by adding this monoglyceride are added to a beverage as O / W emulsion, deterioration of the flavor of a beverage can be suppressed by suppressing the oxidation of the polyunsaturated fatty acid only after storage.

The present invention will be described in detail with reference to the following examples. The present invention is not limited to these examples.

Example 1

The following monoglyceride formulations were added to refined fish oil (5% by weight of EPA, 20% by weight of DHA, 0.5% by weight of tocopherol, and 0.005% by weight of tea extract) to adjust the stabilization and maintenance. Used monoglyceride formulations

1. Distilled Monoglycerides

Sun soft NO.8070 [manufactured by Daiyo Chemical Co., Ltd.]

2. Undistilled Monoglycerides

NO.O-30 [manufactured by Daiyo Chemical Co., Ltd.] (Main body of oleic acid)

Sun soft NO.2500 [manufactured by Daiyo Chemical Co., Ltd.]

The stabilization fat and oil were put into a brown bottle, stored at 60 ° C, and stored to quantify peroxide (POV).

In addition, 10 g of the prepared stabilized oil and fat was placed in a glass tube (300 mm) having a volume of 125 ml, closed with a diaphragm, stored at 60 ° C., and the oxygen concentration in the head space was measured by gas chromatography.

The change in POV is shown in FIG. 1, and the amount of oxygen in the head space is shown in FIG.

These data show that the addition of monoglycerides to fish oil suppresses the formation of peroxides, the oxygen content in the head space is high, the oxygen uptake rate is also suppressed, and stabilized. In addition, it can be seen from the result of the distilled monoglyceride (primary oleate) of FIG. 2 that the stabilizing ability is improved as the amount of monoglyceride added increases.

Example 2

The following monoglyceride formulations were added to refined fish oil (7% by weight of EPA, 24% by weight of DHA, 0.5% by weight of tocopherol and 0.005% by weight of tea extract) to adjust the stabilization and maintenance.

Used monoglycerides

Undistilled Monoglycerides Sun soft No. 0-30

Sun soft NO. 1330 Daiyo Chemical Co., Ltd. (Main Stearic Acid)

This stabilization oil and fat was used for the preservation test as in Example 1.

The change in POV is shown in FIG. 3, and the headspace oxygen amount is shown in FIG.

From these results, it turns out that fats and oils stabilize by adding monoglycerides.

Comparative Example 1

Except having added 2 weight% of emulsifiers less than monoglyceride below, all were processed like Example 1, and the storage test was done.

The change in POV is shown in FIG. 5, and the amount of oxygen in the head space is shown in FIG.

Emulsifier

Sugar ester urethral sugar ester O-170, S-170 [Mitsubishi Chemical Foods Co., Ltd. product]

Polyglycerine Sun soft Q-1710 S, Sun soft Q-1810 S [manufactured by Daiyo Chemical Co., Ltd.]

Organic Monoglycerides Sun soft NO.623 M [manufactured by Daiyo Chemical Co., Ltd.]

From these results, it is the oleic acid sugar ester which shows the holding | maintenance stabilization effect in POV and oxygen absorption amount. Moreover, the effect was not high compared with monoglyceride if the addition amount was the same.

Example 3

90% by weight of tuna fish meat was cut into 3-5 mm squares with a knife and 2% by weight of undistilled monoglyceride (Sun soft NO.O-30) obtained in Example 1 was added, and 10% by weight of tuna crystal oil was added thereto. Stir-mix for 1 minute with a Kenwood mixer. The meat was stored at 5 ° C. for 1 day, and the color tone was shown in Table 1 as a value and b value using a Minolta color difference meter CR-200.

a value b value Maintenance free 5.6 13.5 Keep monoglycerides added 6.9 12.5

The monoglyceride addition oil and fat remain much red from the one with a high value, and the yellow color does not come from the one with a low b value. This result indicates that the maintenance of monoglyceride addition prevents the discoloration of tuna meat as compared to the maintenance of no addition.

Example 4

The emulsion was prepared under the following composition and conditions, heat treatment was performed at 85 ° C. for 15 minutes, and stored at room temperature. As the oil and fat of monoglyceride, oil and fat containing 2% by weight of undistilled monoglyceride (Sun soft NO.O-30) was added to refined fish oil. As a comparison, purified fish oil without monoglycerides was used.

Emulsion composition

3g refined fish oil (5% by weight of EPA, 35% by weight of DHA, 0.5% by weight of tocopherol)

Polyglycerine (Sun soft Q 18 S) 6g

30g per fructose glucose

Tea Extract [(San Ullon, Suntory Co., Ltd.] 2mg

200 g of water

Emulsification Condition

TK Homo Mixer 6000 rpm 5 minutes

→ High pressure homogenizer (made by APV-GAULIN) 300kgf / ㎠

The sensory evaluation of the emulsion after storage at room temperature is shown in Table 2. As can be seen from Table 2, it can be seen that the maintenance of monoglyceride addition is stable even in the state of the emulsion.

Day 2 Day 4 Maintenance free I can smell fish Fish smell strong Keep monoglycerides added No fish smell Barely smell of fish

Example 5

Formulated monoglycerides in refined fish oil ① (7% by weight EPA, 24% by weight DHA, 0.5% by weight tocopherol, 0.005% by weight tea extract) and refined fish oil ② (7% by weight EPA, 24% by weight DHA, 0.5% by weight tocopherol) [Sun soft NO.O-30, manufactured by Daiyo Chemical Co., Ltd.] was added to adjust the maintenance of monoglyceride addition. The monoglyceride addition oil and fat was put in a brown bottle, stored at 37 ° C and opened to quantify peroxide (POV). The change in POV is described in FIG.

In Figure 7, the antioxidant effect of the monoglycerides can be seen that the smell of fats and oils added to the tea extract formulation of polyphenols in refined fish oil.

The oxidation stability of the fats and oils which consist of unsaturated fatty acids can be improved significantly. It can also provide such stabilization. For example, when the refined fish oil is added to food, feed, etc., it can be obtained in a stable form that can usually handle the refined fish oil. It is also possible to provide such a stabilized control oil. Stabilization can be provided without the need to add synthetic antioxidants.

Claims (9)

A method for producing stabilized fats and oils, comprising adding monoglycerides as stabilizers to fats and oils containing highly unsaturated fatty acids. The method for producing stabilizing fats and oils according to claim 1, further comprising adding glycerin. The method for producing stabilizing fats and oils according to claim 1 or 2, wherein undistilled monoglycerides are used as monoglycerides. The method for producing a stabilizing fat or oil according to claim 1, 2 or 3, wherein 90% by weight or more of the fatty acids constituting the monoglyceride is 12 or more and 18 or less. The method for producing stabilizing fats and oils according to claim 1, 2, 3 or 4, wherein the fatty acid constituting the monoglyceride is saturated fatty acid. The method according to any one of claims 1 to 5, wherein the fat or oil containing polyunsaturated fatty acid is purified fish oil. The method for producing stabilized fats and oils according to claim 6, wherein the refined fish oil contains tocopherol and / or polyphenols as antioxidants. 8. The method for producing stabilized fats and oils according to claim 7, wherein the refined fish oil contains tocopherol and polyphenols as antioxidants. Food containing the stabilization fat of Claim 8.