JP3527520B2 - Method for solidifying polyunsaturated fatty acids - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for solidifying polyunsaturated fatty acids, and more particularly to a method for solidifying fats and oils containing highly unsaturated fatty acids which are highly oxidatively deteriorated and hydrolyzates thereof. Is.

[0002]

2. Description of the Related Art Oils containing a large amount of fatty acids having a particularly high degree of unsaturation, such as fish oil, and free fatty acids thereof, and further those obtained by concentrating the desired fatty acid into an ethyl ester, have various physiological effects, for example, It is reported to have the effects of eliminating fatigue from the skin, improving blood lipids, improving memory / reflex response, etc., and is expected to find increased use as health foods and pharmaceuticals.

However, these oils, free fatty acids and their esters have a serious problem in storage due to deterioration due to oxidation and generation of bad odor associated therewith. As a method for preventing oxidation, besides nitrogen encapsulation, natural products such as tocopherol, catechin and lecithin as antioxidants and synthetic products such as DHT are used depending on the application. According to these methods, the effect of improving the antioxidant can be seen, but at present it is not as stable as general vegetable oils and fats. On the other hand, pulverization of fats and oils is a necessary process for expanding the application as food.

[0004]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention As a conventional technique for solidifying unsaturated fatty acids, (1) the one disclosed in JP-A-3-50293 discloses a hydrolyzate of zein which is an antioxidant tocopherol. However, the effect of tocopherol, which prevents the oxidation of oil, is only slightly improved. And, as those using zein as an antioxidant component, (2) JP-A-3-50292, (3) J. Agri
c. Food Chem., VOL. 39, 351-355 (1919) and (4) Agri
c. Biol Chem., Vol.51 3301-3307 (1987) and the like are disclosed.

The above publication (2) discloses a test example in which 9 parts by weight of zein is used and mixed by stirring with 1 part by weight of fish oil containing 25% of eicosapentaenoic acid (hereinafter referred to as EPA). This mixture was in the form of powder, and oxygen was gradually consumed every day, and progress of oxidation was observed. And above
According to the technique disclosed in the document (3), 9 parts by weight of zein is added to an organic solvent solution (9 parts by weight of ethyl ether) of 1 part by weight of methyl linoleate, and the mixture is stirred and mixed. By heating in a highly active environment, zein melts to some extent and becomes a resinous block. Since this is a resinous block, the surface area is small and the contact between the zein and the oil and fat is increased, so that the stability is improved. However, it takes several days or more to set into blocks, and in order to make fatty acid-containing zein with high oxidation stability in a stationary state, it is necessary to distribute fatty acids evenly in advance. Yes, it is necessary to increase the ratio of zein to fats and oils and fatty acids.

Next, in the above-mentioned document (4), linoleic acid is mixed with an ethanol solution of zein in a ratio of 1/4 of zein, and spray-dried to pulverize linoleic acid. In this method, since the ethanol solution of zein tends to have a high viscosity, a solution having a solid content of 7% is spray-dried. Further, since the powder of zein tends to adhere during spray drying, the workability deteriorates by adhering to the inside of the drying tower, or a large amount of ethanol is spray-dried, so the cost becomes high when trapping, and when it is dissipated. Safety etc. becomes a problem.
On the other hand, with regard to pulverization, various methods of impregnating starch or the like or encapsulating with cyclodextrin have been investigated. Although it can be pulverized by these methods, its oxidative stability is insufficient. Furthermore, Japanese Patent Application No. 4-3460
In the technology disclosed in Japanese Patent Publication No. 90, it is necessary to hydrolyze oils and fats in advance to prepare fatty acids, monoglycerides and diglycerides, it is necessary to use flammable substances such as ethanol, and there are facility restrictions regarding safety. Receiving, ethanol recovery equipment, cost, etc. are required.

The present invention has been made in view of the above-mentioned problems of the prior art, and an object thereof is to solidify and stabilize fats and oils containing highly unsaturated fatty acids that are highly oxidized and deteriorated and their hydrolyzates. A method for solidifying polyunsaturated fatty acids, which can be processed safely and at low cost, and can impart a shape and properties that are easy to use in applications such as foods, feeds and pharmaceuticals.

[0008]

Means and Actions for Solving the Problems
As a result of diligent study on the solution of the above problems, lipids and zein composed of fats and oils containing highly unsaturated fatty acids and their hydrolysates were mixed and kneaded while heating to solidify, resulting in poor oxidation after drying and solidification. I found that it rarely happens.

The present invention is based on the above findings,
The gist thereof is a lipid and zein composed of any one kind or a combination of two or more kinds selected from highly unsaturated fatty acid-containing fats and oils, highly unsaturated fatty acid-containing diglyceride, highly unsaturated fatty acid monoglyceride or highly unsaturated free fatty acid. While heating and in the temperature range of 60-180 ℃
In addition, it is a method for solidifying highly unsaturated fatty acids, which is characterized by carrying out a mixing / kneading treatment without adding an alcohol solvent .

The lipids to be treated in the present invention are oils containing a large amount of fatty acids with a particularly high degree of unsaturation, such as fish oil, and the products obtained by hydrolysis thereof. The hydrolyzate is a lipid containing a polyunsaturated fatty acid-containing diglyceride, a polyunsaturated fatty acid monoglyceride, a polyunsaturated free fatty acid and a mixture thereof, and also vitamin A and the like. Further, examples of the polyunsaturated free fatty acid include docosahexaenoic acid (hereinafter referred to as DHA) and EPA.

The above-mentioned lipid and zein are preferably mixed in a proportion of 0.5-10 parts of zein to 1 part of lipid. Further, it is desirable to prevent the deterioration of oxidation by injecting an inert gas such as nitrogen into the kneading device as much as possible to perform substitution. And the processing temperature is 6
It is preferably in the range of 0 to 180 ° C. 180 ° C
This is because the zein is altered in the above, and the dissolution of zein
60 ℃ for easy melting and efficient processing
The above is preferable. Furthermore, when the lipid and zein are mixed and kneaded while being heated in the temperature range of 60 to 180 ° C., it is desirable to add water as necessary. And, as the water content, 3 to 150 parts by weight is suitable for 100 parts by weight of zein. This is because the melting temperature of zein becomes lower as the amount of water increases to a certain extent, deterioration of fatty acids can be avoided, the torque at the time of kneading becomes small, and a large amount of lipids can be uniformly mixed.

By mixing and kneading the above lipids and zein while heating, a solid in which the unsaturated fatty acid as the component thereof is extremely difficult to oxidize can be produced. In the present invention, the lipid is not significantly separated unless the kneading operation is performed, and even if it is not separated, it is difficult to uniformly disperse the lipid, so that the antioxidant effect is not sufficiently exhibited. Here, the antioxidant effect of zein is not simply due to the coating of the lipid, but it is important that the zein and the lipid are uniformly mixed and are close to each other at the molecular level. In the present invention, in order to sufficiently knead the zein and the lipid with high torque by industrial means while heating, batch operation such as a twin-screw kneader or continuous operation with a single-screw or multi-screw extruder is preferable. . When a kneading device having high mixing efficiency is used, the amount of zein required for oxidation stability can be relatively reduced. However, the devices that can be used in the present invention are not limited to those described above.

Further, in the present invention, the kneaded product obtained by mixing and kneading the zein and the lipid while heating,
Depending on the temperature, water content or kneading conditions, one or more forms selected from block form, stick form, flake form, chip form and powder form can be prepared using known means. The present invention will be described below based on examples.

[0014]

【Example】

Example 1 Using a raw material having the following blending ratio and using a closed batch-type kneading mixer, a mixing and kneading process was performed under nitrogen filling according to the following conditions to obtain a light yellowish brown powder and granular form. A mixture was obtained. Then, this mixture was crushed with a cutter mixer, and 63 g of powder containing granules having a particle size of 20 mesh or less
Got Raw material: Zein 40g Fish oil fatty acid 20g (DHA5g) Water 12g Processing temperature: 80 ° C Processing time: 20 minutes Stirring blade: Non-meshing type

Example 2 Using the materials in the following mixing ratios, using a Labo Plastomill (manufactured by Toyo Seiki Seisakusho Co., Ltd.), mixing and kneading treatment was carried out under the following conditions to obtain a light yellowish brown powder. Mixed small pieces were obtained, which were crushed with a pin mill to obtain 96 g of powder. Materials used: Zein 60g Fish oil 40g (DHA10g) Water 20g Treatment temperature: 90 ° C Treatment time: 15 minutes Stirring blade: Non-meshing type

Example 3 Using a raw material mixture having the following blending ratio, a small twin-screw extruder was used, and a mixing / kneading treatment was carried out under the following conditions. The extrudate is milky white and has a length of 5 to 100.
Obtained as mm, coarse, wet pellets. The pellets were ground immediately after drying. Raw materials used: zein / fish oil (EPA 30%) / water = 60
/ 60/15 mixture barrel: L = 600 mm, inner diameter = 30φ Barrel temperature: 90 ° C. Die: 2φ × 10 hole screw: Same direction meshing type, same rotation speed: 80 rpm Processing amount: 150 g / hr

Comparative Example 1 Raw materials having the following blending ratios were placed in a pressure-resistant glass bottle, covered with a lid, heated in a microwave oven to the boiling point of water, and heated for 40 seconds to completely melt the zein. After cooling, the whole became a lump, but the oil that had exuded separated and stayed at the top. Ingredients used: Zein 60g Fish oil 40g (DHA 10g) Water 20g

Comparative Example 2 Raw materials having the following mixing ratios were put in a beaker and heated at 120 ° C. for 1 hour.
It was autoclaved for 5 minutes, cooled, vacuum dried, and crushed with a cutter mixer to obtain a powder containing granules of 20 mesh or less. Ingredients used: Zein 180g Fish oil fatty acid 20g (DHA5g) Water 54g

The change in peroxide value after storing the samples obtained in Example 1, Example 2, Example 3 and Comparative Example 2 at 35 ° C. for 1 month in the dark is shown below (detection limit). 2meq / k
g). Peroxide value (meq / kg) Initially after storage at 35 ° C. in the dark for 1 month Example 1 2 3 Example 2 0 0 Example 3 2 0 Comparative Example 2 0 540

[0020]

The present invention provides a highly unsaturated fatty acid-containing fat or oil,
Heating lipid and zein composed of any one kind or a combination of two or more kinds selected from highly unsaturated fatty acid-containing diglyceride, highly unsaturated fatty acid monoglyceride or highly unsaturated free fatty acid in a temperature range of 60 to 180 ° C. While mixing and without adding alcohol solvent
A method for solidifying highly unsaturated fatty acids, which is characterized by kneading treatment. According to the present invention, a fat or oil containing a highly unsaturated fatty acid that is highly oxidatively deteriorated or a hydrolyzate thereof is solidified and stabilized. In addition to the above, it is possible to impart a shape and properties that are easy to use in the food, feed and pharmaceutical industries. Further, since it can be continuously industrially produced in large quantities and an organic solvent such as ethanol is not used, it is possible to provide a solidification method which can be processed safely and at low cost.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI C09K 15/34 C11B 5/00 C11B 5/00 A23D 9/00 516 (72) Inventor Tokunasa Yanai 2-20 Hinode, Funabashi, Chiba Prefecture -2 Showa Sangyo Kaisha, Ltd. Research Institute (72) Inventor Hisato Kato 2-20-2 Hinode Funabashi, Chiba Prefecture Showa Sangyo Co., Ltd. Research Institute (56) Reference JP-A-3-121198 (JP, A) ) JP-A-3-50292 (JP, A) JP-A-6-192681 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C11B 15/00 A23D 9/00 A23L 1 / 03 A61K 47/42 C09K 15/34 C11B 5/00 C07C 69/587

Claims (5)

(57) [Claims] 1. A lipid composed of any one kind or a combination of two or more kinds selected from highly unsaturated fatty acid-containing oils and fats, highly unsaturated fatty acid-containing diglycerides, highly unsaturated fatty acid monoglycerides and highly unsaturated free fatty acids. A method of solidifying highly unsaturated fatty acids, which comprises mixing and kneading zein in a temperature range of 60 to 180 ° C. and adding no alcohol solvent . 2. A polyunsaturated fatty acid-containing oil or fat, a polyunsaturated fatty acid-containing diglyceride, a polyunsaturated fatty acid monoglyceride or a polyunsaturated free fatty acid, or a combination of two or more thereof. A step of mixing and kneading the lipid and zein in a temperature range of 60 to 180 ° C. without adding an alcohol solvent, and the kneaded product obtained in the previous step in a block shape, a stick shape, a flake shape, A method for solidifying highly unsaturated fatty acids, comprising the step of preparing into one or more forms selected from chips or powders. 3. The method for solidifying polyunsaturated fatty acids according to claim 1, wherein the polyunsaturated fatty acid-containing fat is fish oil. 4. The polyunsaturated fatty acid is docosahexaenoic acid or eicosapentaenoic acid.
The method for solidifying polyunsaturated fatty acids according to 1. 5. The polyunsaturated fatty acids according to claim 1, wherein water is added during the mixing / kneading treatment while heating in the temperature range of 60 to 180 ° C. Solidification method.