JPH09111237A - Antioxidant for docosahexaenoic acids - Google Patents

Abstract

(57) [Summary] (Correction) [PROBLEMS] To provide an excellent antioxidant that prevents docosahexaenoic acids from changing over time. An antioxidant for docosahexaenoic acids containing tocopherol, L-ascorbic acid fatty acid ester and tea extract as active ingredients.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an antioxidant for docosahexaenoic acids (hereinafter referred to as DHAs). More specifically, it relates to an antioxidant of docosahexaenoic acids containing tocopherol, L-ascorbic acid fatty acid ester and tea extract as active ingredients.

[0002]

Ω-3 polyunsaturated fatty acids such as docosahexaenoic acid and eicosapentaenoic acid (hereinafter abbreviated as EPA) have physiological actions such as cholesterol lowering, thrombosis prevention and carcinogenic action. In addition, recent studies have pointed out that DHA has physiological effects not found in other ω-3 fatty acids, such as improvement in memory and learning ability, and brain development in infants. Application development as a raw material for functional foods and health foods and as a raw material for pharmaceuticals has become popular. These highly unsaturated fatty acids are contained in fish oils such as sardines, mackerel, bonito, and tuna in a large amount as free fatty acids or fatty acids constituting fats, and in particular bonito,
30-40% DHA for orbital fat on the head of tuna
It is included.

However, although these highly unsaturated fatty acids and fish oil do not have an unpleasant off-taste which is peculiar to fish odor at the beginning of purification, they are unstable because they have many unsaturated bonds.
With the passage of time, it is oxidized by the action of oxygen, light, heat, microorganisms, etc., and an offensive odor is generated. This off-flavor is called the so-called return odor (off-flavor),
The occurrence of this returning odor causes troubles in use such as significantly reducing the value of a product containing DHAs, and thus DHAs-containing products have various functionalities. Makes it difficult to develop
Preventing deterioration of type A or generation of returning odor has become an urgent issue to be solved.

Several proposals have already been made to solve the above problems. For example, a lipophilic antioxidant obtained by emulsifying an aqueous solution containing a tea extract with a synergist of a hydroxycarboxylic acid and an oil-soluble antioxidant active substance with one or more specific amounts of a lipophilic emulsifier is proposed, According to this invention, it is described that it is effective in preventing the oxidation of animal and vegetable oils and fats such as butter and fish oil (see Japanese Patent Publication No. 3-49315). In addition, a tea product extract component, one or more polyhydroxy compounds, one or more organic acids, and a marine product quality-preserving agent (see Japanese Patent Publication No. 5-66084), which is highly unsaturated as a constituent fatty acid. Fatty acid (DH
A, EPA), a method for masking fishy odor in which a fat-soluble ginger flavor is present in a food containing lipid (see JP-A-6-189717), and an emulsion composition further containing docosahexaenoic acid oil and vitamin C (See JP-A-7-107938).

On the other hand, the inventors of the present invention have continued their research for some time in order to solve the above problems. As a result,
We have proposed a docosahexaenoic acid and / or a stabilizer for fish oil (Japanese Patent Application No. 7-47188) containing an extract of leaf of Nanten and vitamin C as active ingredients.

[0006]

However, in order to prevent troubles such as deterioration odors or returning odors due to the change with time of DHAs which develop with the passage of time, the techniques proposed hitherto have some results. However, it is not always satisfactory, and there is a strong demand for development of a stabilizer and an antioxidant capable of preventing the generation of a deterioration odor or a returning odor due to the change over time of DHAs.

[0007]

The present inventors have conventionally proposed D
We have conducted intensive studies on antioxidants that contribute to the stabilization of HAs, and have achieved some results. As a result of further research, by combining three components, tocopherol, L-ascorbic acid fatty acid ester, and tea extract, which are conventionally known to have an antioxidant function as a single component, each component was isolated. The present invention has been completed by discovering that, compared with the case where it is used, a remarkable effect is exerted in preventing the generation of a deterioration odor or a returning odor due to the aging of DHAs, and the conventional problems can be solved at once.

That is, the present invention is an antioxidant for docosahexaenoic acids, which comprises tocopherol, L-ascorbic acid fatty acid ester and tea extract as active ingredients.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described more specifically below. The tocopherol, L-ascorbic acid fatty acid ester and tea extract used in the present invention are all easily available on the market. The tocopherol of the present invention is an oil-soluble compound called vitamin E. Tocopherol is α-
There are known compounds having various chemical structures such as γ-type, β-type, γ-type and δ-type, and any of them can be used in the present invention. Further, it can be used without distinction between a natural product collected from a natural product or a synthetic product synthesized by a chemical method.

The L-ascorbic acid fatty acid ester used in the present invention is an oil-soluble compound that is easily available on the market. As the kind of the ester, for example, L-ascorbic acid palmitic acid ester, L-ascorbic acid stearic acid ester and the like can be mentioned. The amount used is not particularly limited, but to 1 part by weight of tocopherol, About 0.1 to about 20 parts by weight, more preferably about 0.2 to
It can be about 10 parts by weight. If it is less than 0.1 part by weight, the effect is insufficient, and if it exceeds 20 parts by weight, the effect is not changed and it is uneconomical.

The tea extract used in the present invention may be either a water-soluble or an oil-soluble tea extract, but since it acts more directly on DHAs, It is more preferable that the oil and fat containing the above is dissolved together with tocopherol and L-ascorbic acid fatty acid ester. For this reason, it is preferable to use the oil-soluble tea extract. As the oil-soluble tea extract, commercially available products such as Sankatol No. 1 (manufactured by Taiyo Kagaku Co., Ltd.), sun hood oiliness (manufactured by Sankyo Co., Ltd.), and sun catechin oiliness (manufactured by Mitsui Norin Co., Ltd.) can be used.

The blending ratio of the tea extract and tocopherol in the present invention is not particularly limited, but for example, 0.5 parts of the tea extract is added to 1 part by weight of tocopherol.
A range of ˜50 parts by weight, more preferably 5 to 20 parts by weight is suitable. If you mix a large amount of tea extract outside this range,
There is a problem that the tea odor derived from the tea extract becomes strong, and when it is too small, the synergistic effect due to the combined use is not recognized, and the effect as an antioxidant of DHAs cannot be expected so much.

DH to which the antioxidant of the present invention is used
Examples of the type A include DHA, fish oil, a mixture of DHA obtained by mixing fish oil with DHA, and fish oil. DH
A is present as a free fatty acid or its triglyceride in fish oils such as sardines, mackerel, bonito and tuna.

Preferred DHAs to be used in the present invention are, for example, sardines, mackerel, bonito,
Examples thereof include fish oils obtained from fish such as tuna, and fish oils containing a large amount of DHA collected from bonito and tuna heads are particularly preferable. Further, a fish oil containing a high amount of DHA by further refining it can be mentioned. As the purification method, for example, skipjack, orbital fat present in the head of tuna is heated, and the oil is separated to decolorize and deodorize it by activated carbon treatment, and the crystalline substance is removed at -20 to -40 ° C (winter). Ring) and the like, and the DHA content of the orbital fat is about 20 to 30% by weight for tuna and about 30 to 45% by weight for skipjack. ~ 40 wt%, DHA up to about 35-50 wt%
The content of is increased.

Furthermore, D other than orbital fat of skipjack and tuna
As a method for purifying HA raw materials, for example, fish oils such as skipjack, tuna, sardines and mackerel, for example, purification methods by physical separation means such as distillation, fractional crystallization and chromatography;
There is a purification method by a chemical means such as mixing the fish oil with a silver nitrate solution having a concentration of 60% or more and separating it from other fatty acids by utilizing the binding property of DHA with silver, and a transesterification reaction using lipase. The fish oil having a DHA content of 20% or more and any mixture thereof by the method of increasing the DHA content of triglyceride by
It can be exemplified as the A-rich fish oil.

In using the antioxidant of the present invention, the tocopherol and L-obtained as described above are used.
Only a mixture of ascorbic acid fatty acid ester and tea extract may be used, or a mixture of these mixtures with a suitable diluent,
It may be used in the form of a composition with a filler or carrier. As such a diluent, bulking agent or carrier,
For example, gum arabic, dextrin, glucose, solid diluents such as sucrose, extenders or carriers, water or ethanol, propylene glycol, alcohols such as glycerin or fatty acid ester of polyglycerin, sucrose fatty acid ester, sorbitan fatty acid ester, Examples include liquid diluents such as glycerin fatty acid ester, extenders, or carriers.

The antioxidant of the present invention can be used in any dosage form, for example, powder, granule, liquid, emulsion, paste or any other suitable dosage form. For example, gum arabic, dextrin, etc. may be added, and spray-drying method, powdery form using a drying means such as freeze-drying method, may be used in the form of granules, for example, ethanol, propylene glycol, It can also be used as a liquid dosage form obtained by dissolving it in glycerin, an emulsifier or a mixture thereof, and emulsifying and dispersing. Further, in using the antioxidant of the present invention, the antioxidant of the present invention and other known antioxidants such as vitamin C, rosemary extract, enzyme-treated rutin, licorice extract, lecithin, gallic acid ester, etc. It may be used in the form of a blended mixture.

The antioxidant of the present invention comprising a mixture of tocopherol, L-ascorbic acid fatty acid ester and tea extract can be added directly to DHAs and mixed to obtain light, oxygen, heat, microorganisms, etc. of the DHAs. It is possible to prevent the generation of a deterioration odor or a returning odor with the passage of time, or by adding the DHA to a product mixed with the product, the DHA in the product and the light, oxygen, or oxygen of the product,
It is also possible to effectively prevent the generation of a deterioration odor or a returning odor due to a change with time due to heat, microorganisms and the like. Examples of such products include food / drinks / favorites, feed / feeds, health / medicines, and cosmetics. For example,
Individual products include beverages such as fruit juice-free beverages, beverages containing fruit juice, lactic acid bacteria beverages and powdered beverages; frozen desserts such as ice cream, sherbet and frozen desserts; desserts such as pudding, jellies, bavarois and yogurt; other drops and candies. Foods and beverages such as chocolate, bean paste, processed meat products, grilled meat sauce, pickles, etc .; Health and pharmaceutical products such as tablets, liquid oral medicines, powdered oral medicines, poultices, etc .; soaps, detergents, Mention may be made of cosmetics such as shampoo.

The antioxidant of the present invention comprising tocopherol, L-ascorbic acid fatty acid ester and tea extract is added to DHs or products containing the same in an amount of DH.
It can be appropriately selected depending on the DHA content or concentration in the DHAs contained in A or the product, but it is generally about 2 to 70% by weight, preferably 5 to 50% by weight based on the DHAs contained. % Ranges can often be employed. If the addition amount is less than 2% by weight, the effect is insufficient, and if the addition amount exceeds 70% by weight, the effect does not change, which is uneconomical and has a bad influence on DHA-containing products.

[0020]

EXAMPLES Hereinafter, the antioxidant of the present invention will be described in more detail with reference to examples. Example 1 100 g of purified fish oil containing 20% by weight DHA, 4 g of tocopherol, 1 g of L-ascorbic acid palmitate, 20 g of tea extract and 4 g of rosemary extract were added to a mixture of 711 g of glycerin, 40 g of decaglycerin monooleate and 40 g of decaglycerin monooleate. Mix 120 g of soft water. This mixed solution is pre-stirred and dispersed, and then emulsified at 8,000 rpm for 10 minutes using a TK homomixer (made by Tokushu Kika Kogyo Co., Ltd.) to obtain a particle size of about 0.3-
980 g of a uniform emulsion composition of 0.5 μm was obtained.

Comparative Example 1 Purified fish oil containing 20% by weight DHA
Glycerin 735 was added to a mixture consisting of 100 g, tocopherol 4 g and L-ascorbic acid palmitate 1 g.
g, decaglycerin monooleate 40 g and soft water 120 g. This mixed liquid was treated in the same manner as in the emulsification treatment method of Example 1 to obtain 980 g of a uniform emulsified composition.

Comparative Example 2 Purified fish oil containing 20% by weight DHA
100 g, glycerin 740 g, decaglycerin monooleate
Mix 40g and 120g soft water. This mixed solution was emulsified in the same manner as in Example 1 to obtain 980 g of a uniform emulsified composition.

(Storage stability test of emulsified compositions of Example 1 and Comparative Examples 1 and 2) 20 g of each emulsified composition prepared in Example 1, Comparative Example 1 and Comparative Example 2 was put in a 100 cc transparent glass bottle. The samples were stored at 50 ° C for 30 days in the dark, and the changes in flavor with time were compared. Table 1 shows the results. However, each symbol in the table indicates the following evaluation criteria. (The same applies to Tables 2 to 3 below)-: No off-taste or off-flavor is observed. ±: A slight off-taste and off-odor was slightly observed. +: Generation of a slightly unpleasant off-taste and off-odor is observed. ++: Generation of a considerably unpleasant off-flavor and off-flavor was observed. ++: Remarkably unpleasant off-taste and off-flavor was observed.

[0024]

[Table 1]

As is clear from the results in Table 1, Example 1
The emulsified composition of No. 3 had a stable flavor without change even after 30 days, whereas the comparative example had a bad taste and an offensive odor, and the sample of Comparative Example 2 had a considerably unpleasant offensive taste even after 10 days. However, an offensive odor was observed, and the storage stability of flavor was poor.

(Example 2, Comparative Examples 3 to 4) (Preparation of purified fish oil drink containing DHA) 240 g of granulated sugar,
8 g of citric acid was dissolved in water to prepare 2,000 g of beverage syrup. To three containers each containing 200 g of this syrup, 0.4 g of each emulsified composition of Example 1, Comparative Example 1 and Comparative Example 2 was individually added, and hot pack filling was performed at 90 ° C., followed by cooling. I got a drink. (Hereinafter, they are referred to as DHA-containing purified fish oil beverages of Example 2 and Comparative Examples 3 to 4, respectively.)

(DH prepared in Example 2 and Comparative Examples 3 to 4)
Heat Resistance Test of A-Containing Purified Fish Oil Beverage) Each beverage obtained as described above was stored at 40 ° C. for 14 days, and the time-dependent change in flavor was sensory observed and tested. Table 2 shows the results.

[0028]

[Table 2]

As is clear from the results of Table 2, Example 2
The DHA-containing purified fish oil beverage of No. 2 showed a slight deterioration in the flavor after 14 days, but did not deteriorate the flavor at all until 7 days, showing an excellent heat resistance effect. On the other hand, the DHA-containing purified fish oil beverage of Comparative Example was observed to have off-taste and off-flavor, and particularly the DHA-containing purified fish oil beverage of Comparative Example 4 was observed to have a considerably unpleasant off-taste and off-odor even after 7 days, and the flavor storage stability was It was bad.

(DH prepared in Example 2 and Comparative Examples 3 to 4)
Light resistance test of A-containing purified fish oil beverages) The DHA-containing purified fish oil beverages prepared in Example 2 and Comparative Examples 3 to 4 were irradiated with sunlight (1,200 Langley), and the time-dependent change in flavor was sensory evaluated. Moreover, the TBA value was measured in order to evaluate the oxidation state of DHA in the beverage after sunlight irradiation. Table 3 shows the results. The TBA value is measured by "Oil Chemistry 18,699 ~ 7
18 (1969) ”.

[0031]

[Table 3]

As is clear from the results of Table 3, Example 2
The DHA-containing purified fish oil beverage of No. 2 was found to have an excellent effect on light resistance as compared with that of Comparative Examples 3 to 4.

[0033]

By using the antioxidant of the present invention, it is possible to sufficiently prevent the deterioration of docosahexaenoic acids due to oxygen, light, heat, microorganisms and the like.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location // A23L 3/3472 A23L 3/3472 3/3544 3/3544 501 501 501

Claims (1)

[Claims] 1. An antioxidant for docosahexaenoic acids, which comprises tocopherol, L-ascorbic acid fatty acid ester and tea extract as active ingredients.