JP2006333792A - Composition for preventing oxidation of highly unsaturated fatty-acid food and method for preventing oxidation by using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition for preventing oxidation of a highly unsaturated fatty acid-containing food and the highly unsaturated fatty acid-containing food having high oxidation stability. <P>SOLUTION: The present invention provides a composition having antioxidant effect by adding it to oil and fat food , namely, an antioxidant composition for foods composed of a combination of α-lipoic acid and vitamin C, and also provides a highly unsaturated fatty acid-containing food containing the antioxidant composition for foods, being stable to oxidation and excellent in taste. The present invention further provides a composition for prevention of oxidation of the highly unsaturated fatty acid-containing food containing at least 0.0025-1.25 wt.% lipoic acid and 0.025-1.25 wt.% vitamin C based on highly unsaturated fatty acid content in the highly unsaturated fatty acid-containing food. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention relates to an antioxidant composition for highly unsaturated fatty acid-containing foods.
The present invention also relates to an antioxidant method for highly unsaturated fatty acid-containing foods using an antioxidant composition containing vitamin C and lipoic acid.
Furthermore, the present invention relates to a method for improving the quality of a highly unsaturated fatty acid-containing food using the antioxidant composition and a highly unsaturated fatty acid-containing food using the antioxidant composition.

  Polyunsaturated fatty acids have various physiological functions and are used in various foods and have recently attracted attention as food ingredients. Among highly unsaturated fatty acids, especially docosahexaenoic acid and α-linolenic acid are called ω-3 fatty acids, and their characteristic functions possessed by ω-3 fatty acids are expected to be applied to food applications. ing. In addition, ω-6 polyunsaturated fatty acids represented by arachidonic acid also have a specific physiological activity. In the field of food nutrition, polyunsaturated fatty acids are one of the nutrients attracting attention in recent years, such as the balance of ω-3 fatty acids and ω-6 fatty acids being actively discussed.

  However, it is known that polyunsaturated fatty acids have many active methylene groups in the molecule and have extremely low stability against oxidation. Oxidation of lipids containing polyunsaturated fatty acids is a concern for the reduction of preference quality and nutritional value due to the generation of odors. In addition, in terms of safety, the occurrence of toxicity due to the formation of peroxides This is a serious problem even for highly unsaturated fatty acids. A highly unsaturated fatty acid glycerin derivative is sold as a food material, but its application to food is not so advanced because its use is limited due to its low oxidative stability. Therefore, it is very important to prevent the oxidation of fat-containing foods, particularly highly unsaturated fatty acid-containing foods.

  In general, for the purpose of preventing food oxidation, butylhydroxyanisole (a mixture of BHA, 2-tert-butyl-4-hydroxyanisole and 3-tert-butyl-4-hydroxyanisole), dibutylhydroxytoluene (BHT, 2,6-di -tert-butyl-4-hydroxytoluene) and other phenolic synthetic antioxidants have been used, but problems have been pointed out in terms of safety, and the use of safer antioxidants for foods Is desired. In particular, it has been confirmed that BHA has the potential to cause pre-gastric cancer in rats and has been converted to an antioxidant containing natural materials such as tocopherol. However, at present, tocopherol is widely used as an antioxidant used in oil-containing foods, but it can be said that it has a sufficient effect in terms of antioxidant effects on highly unsaturated fatty acid-containing foods. Absent. Moreover, in order to assist this antioxidant effect, combined use with a rosemary or green tea extract or the like (see Patent Documents 1 and 2) has been attempted, but it is still difficult to say that it has a sufficient antioxidant effect.

On the other hand, α-lipoic acid discovered as a protozoan growth factor is abundant in the liver, kidney, heart and the like in vivo, and is known to act as a coenzyme in a state of being bound to protein. Furthermore, regarding foods, the effect on the oxidation of vegetable oil, pork fat and the like in a state where they are not bound to the protein of α-lipoic acid has already been investigated (see Non-Patent Document 1). However, the antioxidant effect of α-lipoic acid in such a state has only been confirmed for pork fat with a low iodine value, such as highly unsaturated fatty acids with a high iodine value, especially DHA and EPA. Its antioxidant effect has not been confirmed against fish oil containing.
Japanese Patent Laid-Open No. 9-272892 Japanese Patent Laid-Open No. 10-195434 Drinda et al. Z Lebensm Unters Forsch A (1999) 208: 270-276

  For the purpose of preventing the oxidation of highly unsaturated fatty acid-containing foods, development of a safer antioxidant for foods such as tocopherol that has a stable antioxidant effect such as BHA is desired. Yes.

As a result of intensive investigations to show the antioxidant effect even in fats and oils with a wide range of iodine values, the composition using vitamin C and α-lipoic acid contains highly unsaturated fatty acids such as fish oil It has been found that it has a significant antioxidant effect. The present invention is characterized by adding a crude composition containing vitamin C and α-lipoic acid to a highly unsaturated fatty acid-containing food.
As a result of intensive research to obtain an antioxidant composition for highly unsaturated fatty acid-containing foods that exhibited an antioxidant effect even in a wide range of iodine-valued oils and fats, the present inventors have found that raw materials for highly unsaturated fatty acid-containing foods In addition, by using at least vitamin C and α-lipoic acid as an antioxidant composition, it has a remarkable antioxidant effect on foods containing highly unsaturated fatty acids such as fish oil, and has high oxidation stability for a long period of time. The present inventors have found that a highly unsaturated fatty acid-containing food product that can be maintained and has no quality deterioration can be obtained. Furthermore, the present invention provides a combination of vitamin C and α-lipoic acid containing a vitamin C derivative selected from one or more ascorbic acid ester groups selected from stearic acid, palmitic acid, oleic acid and the like. The present invention was also completed by finding a method for producing a high antioxidant effect by adding it to a raw material for producing a lipid-containing food containing a highly unsaturated fatty acid. It came to do.
The present invention provides a highly unsaturated fatty acid-containing food, an antioxidant composition that prevents oxidation of a raw lipid and highly unsaturated fatty acid, at least by a combination of vitamin C and α-lipoic acid.

  The present invention provides a composition having an antioxidant effect when added to fat and oil foods, and an antioxidant composition for foods comprising a combination of α-lipoic acid and vitamin C. In addition, the present invention provides a highly unsaturated fatty acid-containing food that is more stable against oxidation and that has an excellent taste, and that contains the food antioxidant composition.

  Vitamin C of the present invention means ascorbic acid (CAS No50-81-7) or a derivative thereof or a salt thereof, and can be added to foods, and the antioxidant effect of the highly unsaturated fatty acid-containing foods of the present invention For example, ascorbic acid, sodium ascorbate, ascorbic acid derivatives such as ascorbic acid derivatives, etc., and ascorbic acid esters include ascorbic acid, stearic acid, palmitic acid, oleic acid, etc. Monoesters esterified with fatty acids such as ascorbic acid stearate, ascorbyl palmitate, etc. Ascorbic acid derivatives include phosphoric acid esters of ascorbic acid or glycosides of ascorbic acid. The vitamin C of the present invention can be one or two of the above. Ascorbic acid or a derivative thereof may be a salt, and can be used without particular limitation as long as it is acceptable for food, for example, Examples include alkali metal salts such as sodium salt and potassium salt, ammonium salts, organic amine salts such as triethanolamine salt and triethylamine salt, and basic amino acid salts such as lysine salt and arginine salt. Ascorbic acid or a derivative thereof or a salt thereof may be contained alone, or may be contained in combination of two or more, and may be appropriately selected and used.Vitamin C of the present invention is highly unsaturated. 0.025 to 1.25% by weight, preferably 0.05 to 1.125% by weight, more preferably 0.125% to 1.00% by weight based on the weight of the highly unsaturated fatty acid in the fatty acid-containing food Containing. Amount types, the dosage form will vary depending upon the application or the like, may be suitably selected and used.

  The α-lipoic acid of the present invention means α-lipoic acid or a derivative thereof or a salt thereof, and can be added to foods, particularly if it has an antioxidant effect on the highly unsaturated fatty acid-containing foods of the present invention. It is not limited. α-Lipoic acid is a so-called sulfur-containing vitamin-like active substance, also called thioctic acid, which is chemically converted to 1,2-dithiolane-3-pentanoic acid [CAS No.62- 46-4] is widely distributed in animals and plants, and examples of the derivatives of α-lipoic acid include α-lipoic acid, dihydrolipoic acid, alkyl or alkenyl esters and amides thereof, and the like. Examples of the salt of lipoic acid include alkali salts such as sodium salt and potassium salt, as well as amine salts, ammonium salts, etc. α-lipoic acid or a derivative thereof or a salt thereof can be contained alone. The α-lipoic acid of the present invention may be used in combination with two or more kinds, and the α-lipoic acid of the present invention is 0.0025 to 1.25 based on the weight of the highly unsaturated fatty acid in the highly unsaturated fatty acid-containing food. % By weight, preferably 0.01 to 0.5% Contains more preferably 0.0625% 0.125% by weight. The amount types, the dosage form will vary depending upon the application or the like, may be suitably selected and used.

The method for preventing oxidation of a highly unsaturated fatty acid-containing food of the present invention is not limited to a method of using vitamin C and lipoic acid in a highly unsaturated fatty acid-containing food, but for food when added to food. The antioxidant may be a solid such as a powder or a granule, or may be a liquid, and is in a state of being dissolved, dispersed, suspended, or emulsified in a liquid substrate such as water or oil. Also good.
In the present invention, when using the antioxidant composition of a highly unsaturated fatty acid-containing food containing vitamin C and α-lipoic acid in the highly unsaturated fatty acid-containing food, vitamin C and α-lipoic acid are in powder form or It may be a solid such as a granule, may be a liquid, and may be dissolved, dispersed, suspended, or emulsified in a liquid substrate such as water or oil. At the time of addition, after dissolving in a solvent that can be used in foods such as ethanol in advance, it is added directly to the oil or fat food, or a liquid dissolved, dispersed, or suspended in a liquid substrate such as water is added to the raw material to remove the solvent In addition, an emulsion obtained by adding an emulsifier may be added. Although it may be added directly to the raw material, it is preferred that it is once dissolved in a small amount of oil and fat and then added to the oil and fat food. When dissolved and added in fats and oils, the fats and oils to be dissolved may be any fats and oils that can be added to food, but the fats and oils in which the antioxidant composition is easy to dissolve, for example, short of 2 to 12 carbon atoms. What is necessary is just to melt | dissolve antioxidant composition in the triglyceride of a chain fatty acid, a medium chain fatty acid, etc., and to add to a raw material. Furthermore, the composition containing α-lipoic acid and vitamin C has a green tea extract, a rosemary extract, and citric acid, lecithin, etc. Since it may also contribute to further stabilization, it can be optionally added after confirming the effect.

  When α-lipoic acid which is an active ingredient of the antioxidant composition of the present invention is added, the treatment temperature is preferably 60 ° C. or lower. More preferably, it is 50 ° C. or lower. When the treatment temperature is 60 ° C. or higher, α-lipoic acid may be polymerized and decomposed, and thus the treatment temperature is preferably lower than that.

The antioxidant composition contained in the highly unsaturated fatty acid-containing food of the present invention can be obtained simply by mixing a combination containing at least vitamin C and α-lipoic acid. The additive concentration is appropriately changed depending on the method of use for the highly unsaturated fatty acid-containing food, but vitamin C is 0.025 to 1.25% by weight, preferably 0.05 to the weight of the highly unsaturated fatty acid of the highly unsaturated fatty acid-containing food. ˜1.125% by weight, more preferably 0.125% to 1.00% by weight, and α-lipoic acid may contain 0.0025 to 1.25% by weight, preferably 0.01 to 0.5% by weight, more preferably 0.0625% to 0.125% by weight. When a smaller amount is added, there is a possibility that a sufficient antioxidant effect of the highly unsaturated fatty acid of the highly unsaturated fatty acid-containing food cannot be expected. On the other hand, if a larger amount is added, it is not appropriate because it may bring about an oxidation promoting effect.
Further, the blending amount varies depending on the type, dosage form, application, etc., but may be appropriately selected and used.

  The highly unsaturated fatty acid-containing food of the present invention may be a food containing a highly unsaturated fatty acid, and may be a food containing fats and oils having a high iodine value. For example, the highly unsaturated fatty acid contained in the highly unsaturated fatty acid-containing food of the present invention includes rapeseed oil, mustard oil, cottonseed oil, palm oil, rice bran oil, almond oil, hazelnut oil, corn oil, sunflower oil, peanut oil, olive oil, Examples include grape seed oil, pine nut oil and egg yolk extract oil. The highly unsaturated fatty acid-containing food of the present invention may contain a highly unsaturated fatty acid that is a lipid, and is not limited to the iodine value of the highly unsaturated fatty acid, but is preferably 5% or more, more preferably 10% or more. It may be used for food from the aspect of nutrition and functionality. For example, as oils and fats having an iodine value of 130 or more and extremely unstable in oxidation stability, for example, soybean oil, safflower oil, evening primrose oil, borage oil, perilla oil, sesame oil, linseed oil, herring oil, sardine oil, Examples include bonito oil, tuna oil, saury oil, menhaden oil, scallop oil, squid oil, cod liver oil, shark liver oil, whale oil, and seal oil. The antioxidant of the highly unsaturated fatty acid-containing food of the present invention is suitable in that it effectively exhibits an antioxidant effect on the food containing the above highly unsaturated fatty acid. Examples of the highly unsaturated fatty acid-containing food of the present invention include edible oils, margarines, confectionery, seasonings, and dairy products. For example, edible oils such as salad oil and white squeezed oil, supplement foods filled in these edible oil soft capsules, shortening, fat spread, margarines such as margarine, biscuits, cookies, cakes, candy, jelly, chocolate, rice crackers , Confectionery such as candy, tablet confectionery, soy sauce, miso, sauce, sauce, mayonnaise, seasoning such as dressing, dairy products such as yogurt, cheese, butter, coffee whitener, whipped cream, milk and the like.

Examples of the present invention will be described below, but the present invention is not limited to these examples. In Examples, various properties were measured and evaluated by the following methods.
The method for measuring the peroxide value was performed according to AOCS (AOCSCd86-90). The acid value was measured according to the standard oil and fat analysis test method (2.3.2.1-1996). The sensory test was carried out by directly smelling the sample, and the evaluation was carried out by a panel of 5 people, and the scoring was carried out in 5 stages from 1 (bad) to 5 (good).

(Example 1)
An antioxidant composition prepared by dissolving α-lipoic acid (97%, manufactured by Degussa) and ascorbyl palmitate (95%, manufactured by DSM Nutrition Japan) in ethanol of 99.5% purity, has an iodine value of 185, an acid 0.1%, peroxide value 0.4, refined skipjack oil containing 40% polyunsaturated fatty acids (product name: DHA27C-RD), final concentration of α-lipoic acid 0.025% by weight, ascorbyl palmitate The oil / fat food added to 0.1 wt% was placed in a brown glass bottle, sealed, and stored at 40 ° C. for 1 week. The results are shown in Table 1.

  The fat and oil foods after 1 week of storage had almost no increase in acid value and peroxide value, and maintained a good flavor. From this result, it can be seen that the mixture of α-lipoic acid and vitamin C can be an effective antioxidant composition for foods containing highly unsaturated fatty acids, and in addition, by applying this antioxidant composition, highly unsaturated fatty acids It was shown that it is possible to provide fat and oil foods with high commercial value.

(Example 2)
Α-lipoic acid (97%, manufactured by Degussa) against refined skipjack oil (product name: DHA27C-RD) containing iodine value 185, acid value 0.1, peroxide value 0.4 and highly unsaturated fatty acid 40% ) 0.05% by weight, ascorbic acid palmitate ester (95%, manufactured by DSM Nutrition Japan) 0.1% by weight and α-tocopherol (96%, manufactured by DSM Nutrition Japan) 0.1% by weight in a brown glass bottle Placed, sealed and stored at 40 ° C for 1 week. The results are shown in Table 2.

  Oil and fat foods after 1 week of storage are highly unsaturated fatty acid-containing foods that have no increase in acid value and peroxide value, have good flavor, and have a quality suitable for consumption as food. It was shown that there is.

(Example 3)
Purified seal oil containing iodine value 195, acid value 0.3, peroxide value 0.1, and highly unsaturated fatty acid 42% (for Spirulina Laboratories product name: Harp Seal Oil), α-lipoic acid (96%, manufactured by Degussa) ) And 0.05% by weight of ascorbic acid palmitate ester (95%, manufactured by DSM Nutrition Japan) were added to a fat and oil food product in a brown glass bottle, sealed, and stored at 40 ° C. for 1 week. The acid value after storage was 0.3, the peroxide value was 1.2, and the sensory evaluation score was 4.6, maintaining a good state even after storage. From these results, it is possible to effectively suppress oxidation by using vitamin C and α-lipoic acid even in oily foods derived from marine animals that have a high content of highly unsaturated fatty acids and are susceptible to quality degradation due to oxidation. It has been shown.

(Example 4)
Purified sardine oil (produced by Nippon Chemical Feed) containing iodine value 170, acid value 0.1, peroxide value 0.05, highly unsaturated fatty acid 30%, α-lipoic acid (96%, manufactured by Degussa) 0.03% by weight, An oil / fat food supplemented with 0.1% by weight of ascorbyl palmitate (95%, manufactured by DSM Nutrition Japan) was placed in a brown glass bottle, sealed, and stored at 40 ° C. for 1 week. When the peroxide value was measured, there was almost no increase and the flavor remained in a good state.

(Comparative Example 1)
Purified skipjack oil with iodine value of 185, acid value of 0.1, peroxide value of 0.4 (product containing 40% highly unsaturated fatty acid, product name: DHA27C-RD), put in a brown glass bottle, sealed, and 40 ° C Stored for 1 week. The results are shown in Table 3.

  The fat and oil food one week after storage increased to a peroxide value of 30 or more, and it was shown that the quality changed to an undesirable quality when taken as a food. The flavor changed to a strong oxidation odor, and the evaluation score decreased from 5 to 1.1.

(Comparative Example 2)
Purified skipjack oil with iodine value of 185, acid value of 0.1 and peroxide value of 0.4% containing 40% highly unsaturated fatty acid (product name: DHA27C-RD), α-lipoic acid (96%, manufactured by Degussa) Was added to a brown glass bottle, sealed, and stored at 40 ° C. for 1 week. The fat-and-oil food was added with 0.025 wt% and α-tocopherol (96%, manufactured by DSM Nutrition Japan) 0.1 wt%.
The results are shown in Table 4.

The fat food after one week of storage had a peroxide value of 20 or higher, and the flavor had changed to an unpleasant odor as food. From this result, it was shown that even when α-lipoic acid and α-tocopherol were used in combination, the oxidation of fats and oils containing highly unsaturated fatty acids could not be completely suppressed.

Claims (7)

  A composition for antioxidants of highly unsaturated fatty acid-containing foods containing vitamin C and lipoic acid.   2. The antioxidant composition for a highly unsaturated fatty acid-containing food according to claim 1, comprising 0.0025 to 1.25% by weight of lipoic acid based on the content of the highly unsaturated fatty acid in the highly unsaturated fatty acid-containing food. The vitamin C contains at least one or more selected from ascorbic acid, sodium ascorbate, and ascorbic acid derivatives obtained by esterifying ascorbic acid with a fatty acid selected from the group consisting of stearic acid, palmitic acid and oleic acid. A composition for antioxidants of highly unsaturated fatty acid-containing foods.   2. The antioxidant composition for a highly unsaturated fatty acid-containing food according to claim 1, comprising 0.025 to 1.25% by weight of vitamin C based on the content of the highly unsaturated fatty acid in the highly unsaturated fatty acid-containing food.   A method for preventing oxidation of a highly unsaturated fatty acid-containing food, comprising using vitamin C and lipoic acid in a highly unsaturated fatty acid-containing food.   A method for preventing oxidation of a highly unsaturated fatty acid-containing food, comprising vitamin C and lipoic acid in a highly unsaturated fatty acid-containing food containing a glycerin ester derived from a marine animal as a highly unsaturated fatty acid.   A highly unsaturated fatty acid-containing food comprising an antioxidant composition for a highly unsaturated fatty acid-containing food containing vitamin C and lipoic acid.