JP3377560B2 - 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. And, as a conventional technique of a method for solidifying unsaturated fatty acids, as one using zein as an antioxidant component, (1) JP-A-3-502
No. 92, (2) J. Agric. Food Chem., VOL. 39, 351-35.
5 (1919), (3) Agric. Biol Chem., Vol. 51 3301-3.
307 (1987).

[0004]

As the prior art of the method for solidifying unsaturated fatty acids, the method disclosed in the above (1) publication uses 25% eicosapentaenoic acid (hereinafter referred to as EPA).
%, 1 part by weight of fish oil is used, and 9 parts by weight of zein is used and mixed by stirring. This mixture was in the form of powder, and oxygen was gradually consumed every day, and progress of oxidation was observed.

Then, according to the technique disclosed in the above (2), a solution of 1 part by weight of methyl linoleate in an organic solvent is used.
9 parts by weight of zein is added to 9 parts by weight of ethyl ether, and the mixture is stirred and mixed. After removing the solvent, the zein is melted to some extent to form a resinous block by heating in an environment with high water activity. 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.

Further, in the above-mentioned document (3), linoleic acid is mixed with an ethanol solution of zein at 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 recovered, and when it is released. Safety etc. becomes a problem.

Further, in the conventional technique disclosed in Japanese Patent Application No. 4-346090, it is necessary to hydrolyze oils and fats in advance to prepare fatty acids, monoglycerides and diglycerides, and it is necessary to use flammable substances such as ethanol. Yes, there will be facility restrictions, ethanol recovery equipment, and costs will be required.

On the other hand, pulverization of fats and oils is a necessary process for expanding the application as food, and this method is as follows.
Various methods of impregnating with starch or the like and including with cyclodextrin have been studied. Although it can be pulverized by these methods, its oxidative stability is insufficient. Then, the present applicant previously proposed Japanese Patent Application No. 5-61752, and although this method provides an excellent stability in oxidation, sufficient oxidation cannot be achieved unless the solidification conditions are well controlled. Stability cannot be obtained, and the solidified product becomes hard and the pulverizability is not sufficient. Furthermore, the above various methods have not been able to solve the problem that the untreated fish odor derived from fish oil or the like is retained.

The present invention has been made in view of the above-mentioned problems of the prior art, and an object thereof is a method for solidifying and stabilizing oils and fats containing highly unsaturated fatty acids which are highly oxidized and deteriorated and hydrolyzates thereof. Moreover, it is a method for solidifying highly unsaturated fatty acids, which can improve the grindability of the solidified product, is excellent in sensory evaluation of the product, and can be processed safely and at low cost.

[0010]

Means and Actions for Solving the Problems As a concrete means for solving the above problems, the present invention provides a highly unsaturated fatty acid-containing oil and fat, a highly unsaturated fatty acid-containing diglyceride, a highly unsaturated fatty acid monoglyceride, and a highly unsaturated fatty acid. This is a method for solidifying highly unsaturated fatty acids, in which a zein is mixed with a lipid composed of one or more selected from free fatty acids, and the mixture is subjected to moist heat treatment without kneading .

The lipids to be treated in the present invention are oils containing a large amount of fatty acids having a particularly high degree of unsaturation, such as fish oil, and 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 acids include docosahexaenoic acid (hereinafter referred to as DHA) and EPA.

As the zein used in the present invention by mixing it with the above-mentioned lipids, any commercially available zein can be used. The lipid and zein content is preferably 1.0 to 10 parts zein to 1 part lipid. Further, it is sufficient to mix the lipid and zein with a mixer such as a mixer, and it is not necessary to knead the mixture.

Next, the method of heat-treating the mixture of lipid and zein by wet heat treatment is to contact this with high temperature steam at 100 to 180 ° C. or add water to the mixture of lipid and zein. It is one of the methods of heat treatment. Then, the method of heat treatment by adding this water is a method of adding water to a mixture of lipid and zein to obtain a slurry-like or paste-like dispersion, and bringing it into contact with high-temperature steam, or added moisture. It is preferable to use a method of heating in a state in which the water does not evaporate and escape to the outside of the system.

Further, in the present invention, the temperature for the heat and humidity treatment is preferably a method in which high temperature steam of 100 to 180 ° C. is brought into contact with the steam treatment. This is because zein is altered at 180 ° C or higher. By this high temperature moist heat treatment, a uniform solid product in which the unsaturated fatty acid as the component is extremely hard to be oxidized and the lipid is not separated can be obtained. The solid product can be dried and ground if desired.

1 is a mixture of the above lipid and zein.
As a method of bringing into contact with high temperature steam of 00 to 180 ° C. to perform heat treatment with moist heat, a general apparatus used in the food industry can be used, and treatment can be performed in a relatively short time. The obtained product has a slightly hard plate-like or block-like shape and can be easily pulverized into granules if necessary. Further, although a product having excellent oxidative stability is obtained, some odor derived from fish oil or the like remains.

Further, a method of adding water to a mixture of lipid and zein and performing heat treatment can also be performed in a relatively short time using a general apparatus used in the food industry. The oxidation stability of can be improved. Then, if water is added to some extent and heat-treated as a slurry or paste, the product obtained after drying becomes a slightly porous and brittle mass, which has a property of being easily crushed, and can be pulverized. It's easy. Further, according to this method, the odor derived from fish oil or the like is eliminated, and a product having a good sensory evaluation can be obtained.

[0017]

【Example】

Example 1 No water, open on tray, autoclave for sterilization, vacuum drying. Zein ("Showa Zein DP" manufactured by Showa Sangyo Co., Ltd.) 70
Part, 30 parts of fish oil containing 27% of DHA are mixed, spread on a stainless steel tray to a thickness of about 2 cm, and placed in a moist heat sterilizer (autoclave device) at 121 ° C.
Heat treatment was performed for 60 minutes. After taking out the processed product, it was vacuum dried at 65 ° C. using a rotary vacuum pump. The dried product was crushed to an appropriate size with a hammer and then crushed with a coffee mill.

Example 2 No addition of water, open on tray,
Retort sterilizer, vacuum drying. Zein ("Showa Zein DP" manufactured by Showa Sangyo Co., Ltd.) 80
Part, 20 parts of fish oil containing 27% of DHA are mixed, spread on a stainless steel tray to a thickness of about 2 cm, and further, using a retort sterilizer (manufactured by Hisaka Seisakusho), 1
After steam heating at 40 ° C. for 30 minutes, it was dried and crushed in the same manner as in Example 1.

Example 3 With water, open on tray,
Retort sterilizer, vacuum drying. Zein (“Showa Zein DP” manufactured by Showa Sangyo Co., Ltd.) 20
Part, 5 parts of fish oil containing 27% of DHA and 50 parts of water are mixed to form a slurry, which is spread on a stainless steel tray to a thickness of about 2 cm, and a retort sterilizer is used to
After heat treatment with steam at 40 ° C. for 60 minutes, it was dried and pulverized in the same manner as in Example 1. After drying in the same manner as in Example 1, it was lightly crushed by hand and then crushed with a hammer mill (manufactured by Hosokawa Micron, trade name Pulverizer).

Example 4 No addition of water, open on tray,
Autoclave for sterilization, blast drying. Zein (Showa Zein DP manufactured by Showa Sangyo Co., Ltd.) 80
And 20 parts of fish oil containing 27% of DHA were mixed, spread on a stainless steel tray to a thickness of about 2 cm, placed in a wet heat sterilizer and heat-treated at 121 ° C. for 60 minutes. After taking out the processed material, after tearing it to an appropriate size by hand,
The dried product was blow-dried at 80 ° C., and the dried product was crushed with a coffee mill.

Example 5 Water-containing, sealed, retort sterilizer, vacuum dried. Zein (“Showa Zein DP” manufactured by Showa Sangyo Co., Ltd.) 20
Part, 5 parts of fish oil containing 27% of DHA and 75 parts of water are mixed to form a slurry, which is put in a packaging material for a retort and using a retort sterilizer (manufactured by Hisaka Seisakusho), 1
Heat treatment was performed at 40 ° C. for 30 minutes. After taking out the processed product, it was vacuum dried at 65 ° C. using a rotary vacuum pump. The dried product was crushed to an appropriate size with a hammer and then crushed with a coffee mill.

Comparative Example 1 No addition of water, open on tray,
Dry heat heating. Zein (Showa Zein DP manufactured by Showa Sangyo Co., Ltd.) 70
And 30 parts of fish oil containing 27% of DHA were mixed, spread on a stainless steel tray to a thickness of about 2 cm, and heat-treated at 130 ° C. for 30 minutes using a blow dryer. As a result, no change in appearance was observed as compared with that before the treatment.

Comparative Example 2 No addition of water, open on tray,
Dry-heat heating Temperature is out of range. Zein ("Showa Zein DP" manufactured by Showa Sangyo Co., Ltd.) 70
And 30 parts of fish oil containing 27% of DHA were mixed, spread on a stainless tray to a thickness of about 2 cm, and heat-treated at 200 ° C. for 30 minutes using a blow dryer. As a result, a brown mass was obtained. Then, this was crushed in the same manner as in Example 1.

The peroxide values (meq / meq / s) obtained by the above-mentioned Examples and Comparative Examples were stored in the dark at 55 ° C.
Table 1 shows the change with time in kg), Table 2 shows the result of color difference measurement, and Table 3 shows the result of sensory test.

[0025]

[Table 1] Peroxide value (me when stored in the dark at 55 ° C)
q / kg) change over time

[0026]

[Table 2] Results of color difference measurement

[0027]

[Table 3] Results of sensory test (Note) The sensory test, for those obtained in Examples 1 to 5,
As a result of attaching ranks 1 to 5 with less smell

As is clear from Table 1, the products obtained according to the present invention show little change in peroxide value over time and are excellent in oxidative stability. Further, as is clear from Table 3, it can be seen that when a mixture of lipid and zein is added with water to form a slurry and the mixture is directly heated by steam with wet heat as in Example 3, a substance with a small odor can be obtained. . Then, as in Example 5, even if it was made into a slurry, the one which was put into the packaging material and subjected to the heat treatment was equally excellent in the oxidation stability as compared with the one which was heat-heated without being put into the packaging material. However, it can be seen from the sensory evaluation side that the improvement effect is not sufficiently exhibited.

[0029]

INDUSTRIAL APPLICABILITY According to the present invention, lipids consisting of highly unsaturated fatty acid-containing fats and oils and zein are mixed, and the mixture is kneaded.
A method for solidifying highly unsaturated fatty acids, which comprises heat-moisture treatment in the absence of heat, but according to the present invention, an oil or fat containing a highly unsaturated fatty acid that is highly deteriorated in oxidation and its hydrolyzate are solidified and oxidized. It has excellent stability, can be easily pulverized, and has good sensory evaluation.
It can be used for applications such as feed and pharmaceutical industry.

In the processing, a general apparatus used in the food industry, for example, a retort sterilizer or an autoclave apparatus can be used, and since it can be processed in a relatively short time, it can be continuously processed in a large amount. Can be industrially produced and does not use an organic solvent such as ethanol, so that it can be processed safely and at low cost.

In the method of contacting a mixture of lipid and zein with high temperature steam, the obtained product has a slightly hard plate-like or block-like shape, and can be pulverized into granules if necessary. Further, when water is added to a mixture of lipid and zein and the mixture is heat-treated as a slurry or paste, the resulting product becomes a slightly porous and brittle mass, which is easily crushed and easily powdered. is there. Since this product has a reduced odor derived from fish oil and is obtained as a product with a good sensory evaluation, it can be widely used as a food product or a pharmaceutical product.

Front Page Continuation (72) Inventor Hisashi Kato 2-20-2 Hinode, Funabashi, Chiba Prefecture Showa Industrial Co., Ltd. (72) Inventor Tetsuya Wasa 2-20-2 Hinode, Funabashi, Chiba Showa Industrial Stock (56) Reference JP-A-6-271892 (JP, A) JP-A-3-50292 (JP, A) JP-A-3-121198 (JP, A) JP-A-6-192681 (JP , A) Jin Ye Wang, et al, Antioxidative Mechanism of Maize Z ein in Powder Model Systems Systems again Linoleate, J. Am. Agric. Food Chem m. , 1991, Vol. 39, No. 2, p. 351-355 Kimikazu Iwami, et al, Spray-Dried Gliadin Powders Incl usable of Linoleic Acid (Microcapsules), Agric. Biol. Chem. , 1987, Vol. 51, No. 12, p. 3301-3307 (58) Fields investigated (Int.Cl. ⁷ , DB name) C11B 15/00 A23D 9/007 A23L 3/00 C09K 15/34 C11B 5/00

Claims (6)

(57) [Claims] 1. A lipid and zein composed of one or more selected from highly unsaturated fatty acid-containing fats and oils, highly unsaturated fatty acid-containing diglyceride, highly unsaturated fatty acid monoglyceride, and highly unsaturated free fatty acid are mixed. , That
A method for solidifying highly unsaturated fatty acids, which comprises heat-moisture treatment in a state where the mixture is not kneaded . 2. The method of heat treatment by moist heat is a method in which a mixture of lipid and zein is brought into contact with high temperature steam, or a mixture of lipid and zein is added with water to form a slurry or paste, and The method for solidifying polyunsaturated fatty acids according to claim 1, which is one of the methods of heat-treating. 3. The method for solidifying polyunsaturated fatty acids according to claim 1, wherein the method of heat treatment with moist heat is a method of bringing a mixture of lipid and zein into contact with high temperature steam at 100 to 180 ° C. 4. The method of solidifying highly unsaturated fatty acids according to claim 1, 2 or 3, wherein the highly unsaturated fatty acid-containing oil or fat is fish oil. 5. The polyunsaturated fatty acid is docosahexaenoic acid or eicosapentaenoic acid.
Alternatively, the method for solidifying a polyunsaturated fatty acid according to item 4. 6. The method for solidifying polyunsaturated fatty acids according to claim 1, 2 or 3, wherein the mixing ratio of lipid and zein is 1.0 to 10 parts zein to 1 part lipid.