JPH07227227A - Stable emulsified composition and food containing the same - Google Patents

Abstract

(57) [Abstract] [Objective] DHA, EPA, and at least one derivative of these acids, or a natural oil containing them, which is stable to oxidation, does not generate odor, and can be stored for a long period of time. Provided are a stable emulsion composition containing an active ingredient and a stable food containing the emulsion composition. [Structure] At least one of DHA, EPA and derivatives of these acids as an active ingredient or a natural oil containing them, an emulsifier in an amount sufficient to emulsify at least the active ingredient, an antioxidant, and a hydrophilic property. The medium is a polyglycerin fatty acid ester having an HLB of 10 or more (fatty acid having 12 to 20 carbon atoms) or a sucrose fatty acid ester (fatty acid having 12 to 20 carbon atoms) and / or lecithin and is hydrophilic. A stable emulsion composition characterized in that the medium is a polyhydric alcohol or a water-containing polyhydric alcohol, and a food obtained by adding the same.

Description

Detailed Description of the Invention

[0001]

The present invention relates to docosahexaenoic acid,
The present invention relates to a stable emulsion composition of eicosapentaenoic acid and at least one derivative of these acids or a natural oil containing them. The emulsified composition of the present invention is preferably used for various foods such as beverages, frozen desserts, confectionery, dairy products, bakery products, and processed aquaculture products.

[0002]

BACKGROUND OF THE INVENTION Docosahexaenoic acid (hereinafter referred to as DHA) and eicosapentaenoic acid (hereinafter referred to as EPA) are straight chain highly unsaturated fatty acids mainly contained in fish oil. , It has been reported to have physiological activities such as a blood cholesterol lowering action, an anticancer action, an antithrombotic action, and a learning ability improving action, and it is one of the most noticeable food materials at present.

However, since EPA has 5 double bonds in one molecule and DHA has 6 double bonds in one molecule, it is extremely easy to use a slight amount of oxygen, heat, light or an oxidation catalyst. It is known that the fish will be oxidized and produce return fish (fish odor) peculiar to fish oil. Various techniques have been proposed in order to prevent oxidation or prevent fish odor from occurring when using fish oil containing such straight chain highly unsaturated fatty acids.

For example, fish oil-added milk powder mixed with vitamin C and / or its salt (JP-A-4-346749), capsules coated with an edible coating agent by adding tocopherol and / or lecithin to polyunsaturated fatty acids. Margarine dispersed (JP-A-2-203741), Tween 2
There is known a method of stabilizing ω-3 unsaturated fatty acid with an emulsifier such as 0, sucrose fatty acid ester, sorbitan fatty acid ester, lecithin (JP-A-6-49479).

However, no satisfactory effect has been obtained in any case, and it is desired to obtain a more stable emulsion composition. Therefore, the present inventors have found that DHA and E
As a result of extensive studies on a method of stably dispersing PA and the like in a hydrophilic medium, a stable emulsion composition is obtained by using a specific emulsifier and a polyhydric alcohol or a hydrous polyhydric alcohol as the hydrophilic medium. They have found that they can be achieved and have completed the present invention.

[0006]

The present invention provides at least one active ingredient such as docosahexaenoic acid, eicosapentaenoic acid and derivatives of these acids, or a natural oil containing them, which is sufficient to emulsify at least the active ingredient. Consisting of an appropriate amount of emulsifier, antioxidant, and hydrophilic medium,
The emulsifier is a polyglycerin fatty acid ester having an HLB of 10 or more (fatty acid having 12 to 20 carbon atoms) alone or sucrose fatty acid ester (fatty acid having 12 to 20 carbon atoms) and / or lecithin, and the hydrophilic medium is a polyhydric alcohol. Alternatively, the present invention provides a stable emulsion composition which is a water-containing polyhydric alcohol, and a food containing the same.

The emulsified composition of the present invention contains DHA, EPA, a derivative of these acids or a natural oil containing them as an active ingredient, and these active ingredients are uniformly and uniformly dispersed as an oil droplet in a hydrophilic medium. Is an emulsified composition.
In the emulsified composition of the present invention, HLB10 is used as an emulsifier.
Polyglycerin fatty acid ester above (carbon number of fatty acid
12-20) It is stable to use polyhydric alcohol or hydrous polyhydric alcohol as a hydrophilic medium, either alone or as a mixture with sucrose fatty acid ester (carbon number of fatty acid 12-20) and / or lecithin Is essential to hold.

Hereinafter, each component in the emulsion composition of the present invention will be described in detail. DHA, EPA and derivatives of these acids as active ingredients in the emulsion composition of the present invention (hereinafter collectively referred to as active ingredients of DHA, EPA and derivatives of these acids) are either synthetic or natural products. Or in the form of natural oil containing these acids. The synthetic products include not only chemically synthesized products but also products produced by microorganisms and the like. Natural products are DH
A, EPA or a natural oil containing a derivative of these acids, which has been extracted and purified by a known method such as squeezing, solvent extraction, steam distillation, molecular distillation, supercritical fluid extraction, or column chromatography. To do. The active ingredient in the present invention may be a pure product or a crude product.

The natural oil used in the present invention means DHA,
It means an oil derived from a natural product containing EPA or derivatives of these acids. The natural oil used in the present invention is not particularly limited, and those derived from all sources such as seaweed, microorganisms, animals and plants can be used. Preferred examples of natural oils include fish oils (for example, squid oil, sardine oil, krill oil, bonito oil, mackerel oil, salmon oil, saury oil, cod oil, tuna oil, etc.), egg yolk oil, oil derived from algae, and the like. However, fish oils and oils derived from algae are more preferred. Further, the natural oil in the present invention, the above-mentioned natural oil, various treatments (for example, degumming treatment such as phosphoric acid treatment, deoxidation treatment with alkali such as caustic soda, bleaching treatment with activated clay, steam, etc. Those which have been subjected to deodorizing treatment such as distillation) and those which have been concentrated by, for example, fractionation, fractionation, enzyme treatment and the like are also included.

DHA and EPA used in the present invention
It is preferable that the derivative of (1) exhibits at least the physiological activity possessed by DHA or EPA, and in the present invention, all the derivatives exhibiting such physiological activity are included. DHA
Examples of derivatives of EPA and EPA include salts, amides, phospholipids, monoglycerides, diglycerides, esters (eg, methyl ester, ethyl ester, propyl ester, sucrose ester, etc.), among which monoglyceride, diglyceride, ethyl Esters are preferred.

The content of the active ingredient in the emulsion composition of the present invention is generally 0.0001 to 50% by weight, preferably 0.1 to 25% by weight. The content of such an active ingredient is appropriately selected in consideration of the intended use of the emulsified composition, the purification purity of the active ingredient, the content of the active ingredient in the natural oil, the concentration of the natural oil containing the active ingredient, and the like. To be done. For example, when the active ingredient is a pure product, it is about 0 in consideration of the strength of its physiological activity.
The concentration can be as low as 0001 to 0.1% by weight, or when stronger activity is desired, a higher concentration such as about 0.1 to 50% by weight is taken into consideration in consideration of the absence of impure oil. You can also do it. Further, when the active ingredient is in the form of natural oil, if the natural oil is concentrated, its physiological activity becomes stronger, so that the concentration can be lowered, and on the other hand, since the impure oil content is decreased, the concentration is high. Can also be

In the present invention, HLB10 is used as an emulsifier.
At least polyglycerin fatty acid ester having 12 to 20 carbon atoms in the fatty acid is used. Such polyglycerin fatty acid ester has particularly high emulsion stability under acidic conditions as compared with other emulsifiers, and keeps DHA, EPA, derivatives of these acids and natural oils containing them stable for a long time under acidic conditions. be able to. The polyglycerin fatty acid ester can be used alone or, if desired, as a mixture thereof with a sucrose fatty acid ester, a mixture thereof with a lecithin, or a mixture thereof with a sucrose fatty acid ester and a lecithin. Sucrose fatty acid ester and lecithin act as an auxiliary to stabilize the emulsion.
For example, when the emulsion composition of the present invention is used in a beverage or the like, it is preferable to use a mixture of polyglycerin fatty acid ester and sucrose fatty acid ester and / or lecithin as an emulsifier.

When lecithin is used as an emulsifier, it is generally difficult to dissolve it in water, so it is desirable to dissolve it in edible oils and fats (eg, coconut oil, γ-linolenic acid oil, etc.) in advance. The amount of edible oil / fat used at that time is about 1: 1 to 1:20 (weight ratio) with respect to lecithin. The emulsifier in the present invention is used at least in an amount sufficient to emulsify the active ingredient in the emulsified composition. By an amount sufficient to emulsify the active ingredient is meant an amount sufficient to disperse the oil droplets, which are the disperse phase, uniformly and homogeneously in the hydrophilic medium. The content of the emulsifier in the emulsified composition is generally about 0.01 to 20% by weight, preferably about 0.5 to 10% by weight. The content of the emulsifier is appropriately selected within the above range in consideration of the content of the active ingredient and the like. Generally, the ratio of emulsifier to active ingredient is preferably 1: 0.1 to 1: 1 (weight ratio).

The emulsion composition of the present invention may contain various additives including the above-mentioned edible oil and fat (solvent of lecithin) and oil-soluble components as described below. The content of the emulsifier can be increased depending on the type and the amount used. However, in general, the emulsifier content is sufficient within the above range. When a mixture of polyglycerin fatty acid ester and sucrose fatty acid ester and / or lecithin is used as an emulsifier in the present invention, a mixture such that the proportion of polyglycerin fatty acid ester in the mixture is at least 50% by weight is used. It is preferably used. Specifically, the mixing ratio of polyglycerin fatty acid ester and sucrose fatty acid ester is preferably about 1: 0.05 to 1: 1 (weight ratio), and the mixing ratio of polyglycerin fatty acid ester and lecithin is about 1: 0.00
5 to 1: 0.5 (weight ratio) is preferable. The mixing ratio of polyglycerin fatty acid ester, sucrose fatty acid ester and lecithin is preferably about 1: 0.05: 0.005 to 1: 1: 0.5 (weight ratio).

Regarding the polyglycerin fatty acid ester used in the present invention, HLB is 10 or more, preferably 12
-20, more preferably 13-16, even more preferably 14
~ 16, the fatty acid has 12 or more carbon atoms, preferably 12 ~
It is 20, more preferably 14-18. The average degree of polymerization of glycerin is preferably 6 to 15, more preferably 8 to 10. Preferred examples of polyglycerin fatty acid ester include hexaglycerin monostearate, decaglycerin monostearate, decaglycerin monooleate, decaglycerin monomyristate, decaglycerin monopalmitate, and the like. Among them, decaglycerin monostearate, decaglycerin monooleate, and decaglycerin monopalmitate are particularly preferable. In the present invention, these polyglycerin fatty acid esters may be used alone or in combination.

The content of the polyglycerin fatty acid ester in the emulsion composition is preferably about 0.01 to 20% by weight,
About 0.2-10% by weight is especially preferred. The content of the polyglycerin fatty acid ester is appropriately selected within the above range in consideration of the content of the active ingredient, the usage amount of sucrose fatty acid ester and lecithin described below, and the like. The sucrose fatty acid ester used in the present invention preferably has an HLB of 10 or more and a fatty acid having 12 or more carbon atoms, more preferably 12 to 20. Preferred examples of the sucrose fatty acid ester include sucrose monostearate, sucrose monooleate, sucrose monopalmitate and the like. In the present invention, these sucrose fatty acid esters can be used alone or in combination.

The content of the sucrose fatty acid ester in the emulsion composition is preferably about 0.1 to 5% by weight. The content of the sucrose fatty acid ester is appropriately selected within the above range in consideration of the content of the active ingredient, the usage amount of the polyglycerin fatty acid ester, the usage amount of lecithin described below, and the like.
Lecithin used in the present invention means phospholipids such as phosphatidylcholine, phosphatidylethanolamine, phosphatidylinositol, phosphatidic acid, phosphatidylserine, and sphingomyelin.
In the present invention, these components are collectively referred to as lecithin.

As the lecithin used in the present invention, those derived from all sources such as animals, plants, yeasts and molds can be used. Preferable examples of lecithin used in the present invention include plant lecithin (for example, soybean lecithin, corn lecithin, rapeseed lecithin, etc.), egg yolk lecithin, fractionated lecithin, enzymatically decomposed lecithin, etc., among them, soybean lecithin, egg yolk Lecithin and enzymatically decomposed lecithin are more preferable. In the present invention, these lecithins can be used alone or in combination.

The fractionated lecithin means a substance obtained by fractionating a specific component from plant lecithin or egg yolk lecithin using an organic solvent such as ethanol and utilizing the difference in solubility. Enzymatic degradation lecithin is a plant lecithin, egg yolk lecithin, fractionated lecithin, etc. with phospholipase acting, hydrolysis,
It means a substance obtained by carrying out a transfer reaction or the like. Various types of enzyme-decomposed lecithin can be obtained depending on the type of lecithin and the type of phospholipase. In the present invention, these are collectively referred to as enzyme-decomposed lecithin. In the present invention, any type of enzymatically decomposed lecithin can be used.

The content of lecithin in the emulsion composition is preferably about 0.001 to 2% by weight. The content of lecithin is appropriately selected within the above range in consideration of the content of the active ingredient, the usage amounts of the polyglycerin fatty acid ester and the sucrose fatty acid ester, and the like. In the present invention, a polyhydric alcohol or a hydrous polyhydric alcohol is used as the hydrophilic medium. When these hydrophilic media are used, the generation of fishy odor can be prevented more than when water alone is used as a medium, and an emulsion composition having high storage stability can be obtained.
Further, by using these hydrophilic media, it is possible to obtain an emulsified composition having a smaller particle size of oil droplets with the same energy as compared with the case of using water alone as a medium, such as soft drinks. It is particularly advantageous when an emulsion composition having a small oil droplet particle size is desired.

The water content of the water-containing polyhydric alcohol used in the present invention is preferably about 50% by weight or less, more preferably about 30% by weight or less. Preferable examples of the polyhydric alcohol include glycerin, sorbitol, propylene glycol and the like, and of these, glycerin and sorbitol are more preferable. Preferred examples of the water-containing polyhydric alcohol include about 60 to 90% by weight of glycerin water, about 50 to
70 wt% sorbitol water and the like can be mentioned.

Preferred examples of the antioxidant used in the present invention include ascorbic acid, isoascorbic acid or salts thereof (eg, alkali metal salts, alkaline earth metal salts, etc.), catechins, catechins-containing natural extracts. And the like. Specifically, L-ascorbic acid, L-
Ascorbic acid such as sodium ascorbate, erythorbate, sodium erythorbate; catechins such as gallocatechin, epigallocatechin, epicatechin, epigallocatechin gallate, epicatechin gallate; tea extract, apple extract, grape seed extract, Examples include sunflower seed extract, natural extracts containing catechins such as rice bran extract, and among these, L-ascorbic acid,
L-sodium ascorbate and tea extract are preferred.
These antioxidants can be used alone or in a mixture of two or more.

The catechin-containing natural extract is, for example, tea (eg, green tea, oolong tea, black tea, roasted tea, etc.) leaves, apple pulp, grape seeds, sunflower seeds, etc., and water, organic solvents such as ethanol, chloroform, etc. And can be obtained by purification by a known method. The catechin-containing natural extract used in the present invention may be a pure product or a crude product.

In addition to the above antioxidants, for example, tocopherols (eg, extracted tocopherol, dl-α-
Tocopherol, etc.), polyphenols (eg rutin,
Myricetin, myricitrin, etc., spice extracts (eg, rosemary, sage, etc.), acids derived from natural products (eg, chlorogenic acid, caffeic acid, ferulic acid, gallic acid, etc.), dibutylhydroxytoluene (BHT), butyl A known antioxidant such as hydroxyanisole (BHA) can be used in combination. These antioxidants can also be used in one kind or in a mixture of two or more kinds, and when these antioxidants and the above-mentioned antioxidants are used in combination, it is more effective to prevent the return odor peculiar to fish odor.

The antioxidant of the present invention is preferably used in an amount not less than the amount necessary to consume dissolved oxygen in the emulsion composition, and generally 0.001 to 20% by weight, preferably 0.0
It is 1 to 20% by weight. The amount of the antioxidant used is within the above range depending on the type or content of unsaturated fatty acid in the active ingredient, the purity of the active ingredient, the type of antioxidant, the amount of dissolved oxygen in the emulsion composition, and the like. Fluctuates with. Further, when several types of antioxidants are used in the present invention, the amount of each antioxidant used is appropriately determined within the above range depending on the type of the antioxidant, the purpose of use of the emulsion composition, etc. To be done.

If desired, other additives may be added to the emulsified composition of the present invention for the purpose of improving the emulsifying property, heat resistance, acid resistance, storage stability, and emulsifying stability in foods of the emulsified composition. May be included. Such additives include DH
Any known food additive may be used as long as it is not a substance that promotes the oxidation of A, EPA or derivatives of these acids, and may be oil-soluble or water-soluble. Examples of such additives include high molecular polysaccharides (eg, soluble starch, dextrin, cyclodextrin, gum arabic, pectin, xanthan gum, etc.), preservatives (eg, paraoxybenzoic acid esters, benzoic acid, etc.), Specific gravity adjusting agent [SAIB (sucrose acetate isobutyrate)], protein degradation product (eg: casein, gelatin etc.), vitamin, pigment (eg α-carotene, β-carotene, lycopene etc.), fragrance, unsaturated fatty acid (Example: α-linolenic acid, γ-linolenic acid, linoleic acid, etc.) and the like. The amounts of these additives used are appropriately determined according to the purpose of use.

In the emulsified composition of the present invention, the particle size of oil droplets in the emulsified composition is preferably 0.25 μm or less, more preferably 0.2 μm or less, depending on the intended use. By doing so, for example, turbidity generated when used for water-based foods such as soft drinks, neck ring (particles of oil droplets in the emulsified composition floating and gathering on the beverage surface due to a difference in specific gravity) It is possible to prevent the precipitation and precipitation, and it is possible to obtain a stable food product without adjusting the specific gravity. Further, in that case, since the specific gravity adjusting agent (SAIB) is not used, the emulsified composition can be produced without any heating operation in the production process.

The emulsified composition of the present invention is produced by previously mixing and dissolving each of the water-soluble component and the oil-soluble component separately, and adding the oil-soluble component mixture to the water-soluble component mixture to uniformly and uniformly disperse the mixture. can do. When preparing the emulsified composition, it is preferable to use an emulsifying machine such as a colloid mill, a homomixer, or a high-pressure homogenizer, and it is desirable to suppress the heat generated during the emulsification by a cooling device or the like.

The emulsified composition thus obtained is stable against oxidation, does not generate odor, and can be stored for a long period of time, and is used for beverages, frozen desserts, confectionery, dairy products, bakery products, It is suitable for use in various food products such as processed livestock products. The food containing the emulsion composition of the present invention has characteristics of the food itself (for example, shape, smell, taste, texture, color tone, etc.).
It is a food containing DHA, EPA or a derivative of these acids without deteriorating the risk of necking or precipitation.

The emulsified composition of the present invention can be used as various food additives, for example, in various foods.
It may be semi-solid or solid. Specific examples thereof include the following. Beverages: carbonated drinks, fruit drinks, dairy drinks, vegetable drinks, soy milk, etc. Frozen desserts: ice cream, popsicles, sorbets, etc. Confectionery: jelly, candy, gum, cookies, cakes,
Chocolate, pies, biscuits, pudding, etc. Dairy products: milk, yogurt, cheese, butter, margarine, mayonnaise, salad dressing, etc. Bakery products: Bread, noodles, pasta, etc. Processed livestock products: ham, sausage, kamaboko, chikuwa, etc. Seasonings: miso, sauce, sauce, etc. Cooked products: omelet, omelet, curry, stew, hamburger, croquette, soup, Okonomiyaki, dumplings, etc .: Animal feed, pharmaceuticals, quasi-drugs, etc.

The amount of the emulsified composition of the present invention to be used for the above foods is generally DH which is the active ingredient.
A, EPA or derivatives of these acids or natural oils containing them are added to the food in an amount of about 0.0001 to 1% by weight, preferably about 0.001 to 0.1% by weight. It

The emulsion composition of the present invention can be used in various foods by utilizing known methods. Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. In the following examples,
Unless otherwise indicated,% represents% by weight.

[0033]

Examples Example 1: Polyglycerin fatty acid ester
Effect of type The polyglycerin fatty acid ester shown in Table 1 was used as an emulsifier, and the emulsified composition was prepared using the active ingredient, antioxidant and hydrophilic medium shown below, and its stability was tested.

Formulation of emulsified composition: content (%) [active ingredient] refined fish oil 20 (DHA content about 25%, EPA content about 10%) [emulsifier] polyglycerin fatty acid ester (see Table 1) 5 [ Antioxidant] L-Ascorbic acid 0.5 [Hydrophilic medium] Water 24.5 Glycerin 50 Total 100 (Emulsion composition production method and stability test method) Water, glycerin, polyglycerin fatty acid ester and L-ascorbin An acid was dissolved, and then purified fish oil was added thereto, and the mixture was stirred and dispersed, followed by emulsification using a homogenizer to prepare an emulsified composition. This emulsion composition was allowed to stand at room temperature or 60 ° C. for 1 week, and then its state was observed. The results are shown in Table 1. In Table 1, ◯ indicates that there is no abnormality, and x indicates that the emulsion composition is separated into two layers.

[0035]

[Table 1]

From Table 1, it is clear that polyglycerin fatty acid ester having HLB of 13 or more, glycerin average degree of polymerization of 8 or more, and fatty acid having 14 or more carbon atoms has excellent effects.

Example 2: Polyglycerin fatty acid ester
Effect of the added amount of the active ingredient, the emulsifier, the antioxidant, and the hydrophilic medium shown below are used to produce an emulsified composition by varying the contents of the active ingredient and the emulsifier as shown in Table 2, Its stability was tested.

Formulation of emulsified composition: Content (%) [Active ingredient] Purified fish oil See Table 2 (DHA content about 25%, EPA content about 10%) [Emulsifier] Decaglycerin monooleate See Table 2 [Antioxidant] L-Ascorbic acid 0.5 [Hydrophilic medium] Glycerin 40 Water Total residual amount 100

(Manufacturing Method of Emulsion Composition and Stability Testing Method) Glycerin, decaglycerin monooleate and L-ascorbic acid were dissolved in water, and then purified fish oil was added thereto and dispersed by stirring. An emulsified composition was produced by emulsifying using a homogenizer. After leaving this emulsion composition at room temperature for 1 week, the state was observed. The results are shown in Table 2. In Table 2, ◯ indicates that there is no abnormality, and x indicates that the emulsion composition is separated into two layers.

[0040]

[Table 2]

From Table 2, purified fish oil (DH
When A content of about 25%, EPA content of about 10%) is used,
It is clear that when the polyglycerin fatty acid ester is added so that the ratio of the polyglycerin fatty acid ester to the active ingredient is 1: 0.05 (40: 2) or more, it has an excellent effect.

Example 3 Effect of Water Content of Hydrophilic Medium Hydrophilic medium (glycerin water) or water shown below,
An emulsion composition was prepared using the active ingredient, the emulsifier and the antioxidant, and its stability was tested.

Formulation of emulsified composition: content (%) [active ingredient] refined fish oil 20 20 20 20 (DHA content about 25%, EPA content about 10%) [emulsifier] decaglycerin monooleate 5 5 5 5 [Antioxidant] Ascorbic acid 1 1 1 1 [Hydrophilic medium] Glycerin-30 52 74 Water 74 44 22- Total 100 100 100 100 Hydrophilic medium water content (%) 100 60 30 0

(Method for producing emulsified composition and method for testing stability) Decaglycerin monooleate and ascorbic acid were dissolved in the above-mentioned hydrophilic medium, and then purified fish oil was added thereto and dispersed by stirring, followed by homogenization. An emulsified composition was produced by emulsifying with.
This emulsified composition was diluted 1000 times with ion-exchanged water and its flavor was evaluated. In addition, the particle size of oil droplets in the emulsified composition was measured. The particle size of the oil droplets is measured by laser diffraction particle size distribution analyzer SA
It was measured using LD-110 (manufactured by Shimadzu Corporation). Furthermore, this emulsion composition was stored at 40 ° C. for 2 weeks, then similarly diluted 1000 times with ion-exchanged water, its flavor was evaluated, and the particle size of oil droplets in the emulsion composition was measured.

The results are shown in Table 3. The symbols in Table 3 indicate the evaluation according to the following flavor evaluation criteria. Flavor evaluation criteria:-; No fishy odor is felt. +: A slight fishy odor is felt. ++: I feel a fishy odor. ++++: A strong fishy odor is felt.

[0046]

[Table 3]

As is clear from Table 3, the emulsified composition produced using the hydrophilic medium having a water content of about 30% or less was produced using water alone or a hydrophilic medium having a high water content. Compared with the emulsified composition, generation of fishy odor was prevented and excellent storage stability was exhibited. In addition, the smaller the water content of the medium, the smaller the particle size of the oil droplets.

Example 4: Effect of the type of antioxidant An emulsion composition was prepared using the antioxidants shown in Table 4 and the following active ingredients, emulsifiers and hydrophilic media,
Its stability was tested.

Formulation of emulsified composition: content (%) [active ingredient] refined fish oil 20 (DHA content about 25%, EPA content about 10%) [emulsifier] decaglycerin monostearate 5 [antioxidant ] See Table 4 1 [Hydrophilic medium] Water 24 Glycerin 50 Total 100

(Manufacturing Method of Emulsion Composition and Stability Testing Method) Glycerin, decaglycerin monostearate and an antioxidant were dissolved in water, and then purified fish oil was added thereto and dispersed by stirring, followed by homogenization. An emulsified composition was produced by emulsifying with. However, among the antioxidants in Table 4, extracted tocopherol,
The L-ascorbic acid palmitate was dissolved in purified fish oil to prepare an emulsion composition. 40 this emulsified composition
After storing at 1 ° C for 1 week, it was diluted 1000 times with ion-exchanged water and its flavor was evaluated. The results are shown in Table 4. The symbols in Table 4 indicate the evaluation according to the above-mentioned flavor evaluation standard.

[0051]

[Table 4]

From Table 4, it is clear that L-ascorbic acid, sodium L-ascorbate, erythorbic acid, tea extract, apple extract, grape seed extract and sunflower seed extract have excellent antioxidant effects. Is.

Example 5: Effect of Antioxidant Addition Amount The content of the antioxidant was varied as shown in Table 5 by using the active ingredient, emulsifier, antioxidant and hydrophilic medium shown below. Then, an emulsion composition was prepared and its stability was tested.

Formulation of emulsified composition: Content (%) Purified fish oil 20 (DHA content about 25%, EPA content about 10%) [Emulsifier] Decaglycerin monostearate 5 [Antioxidant] L-Ascorbin Acid See Table 5 Tea Extract See Table 5 [Hydrophilic medium] Glycerin 50 Water Total residual amount 100

(Method for producing emulsified composition and method for stability test) Glycerin, decaglycerin monostearate and antioxidant (L-ascorbic acid or tea extract) were dissolved in water, and then purified fish oil was dissolved in the solution. Was added, and the mixture was stirred and dispersed, and then emulsified using a homogenizer to produce an emulsified composition. 40 this emulsified composition
After storing at 1 ° C for 1 week, it was diluted 1000 times with ion-exchanged water and its flavor was evaluated. The results are shown in Table 5. The symbol in Table 5 indicates the evaluation according to the flavor evaluation standard.

[0056]

[Table 5]

From Table 5, purified fish oil (DH
A content of about 25%, EPA content of about 10%)
It can be seen that L-ascorbic acid exhibits an antioxidant effect when added in an amount of 0.001% or more, and tea extract exhibits an antioxidant effect when added in an amount of 1% or more. It is considered that the antioxidant exhibits an antioxidant effect when added in an amount not less than the amount required to consume the dissolved oxygen in the emulsion composition.

Example 6: Influence of the type of emulsifier A mixture of decaglycerin monostearate and the emulsifier shown in Table 6 was used as an emulsifier, and the active ingredient, antioxidant and hydrophilic medium shown below were used. It was used to produce an emulsified composition and its stability in carbonated drinks was tested.

Formulation of emulsified composition: content (%) [active ingredient] purified fish oil 20 (DHA content about 25%, EPA content about 10%) [emulsifier] decaglycerin monostearate 5 other emulsifiers ( Table 6) 0.5 [antioxidant] L-ascorbic acid 0.5 [hydrophilic medium] water 24 glycerin 50 total 100

(Method for producing emulsified composition and carbonated beverage and method for stability test) Glycerin, polyglycerin fatty acid ester, emulsifier shown in Table 6 and L-ascorbic acid were dissolved in water, and then purified fish oil was dissolved therein. After additionally stirring and dispersing, an emulsified composition was produced by emulsifying with a homogenizer. Using this emulsified composition,
Make a carbonated drink syrup with the following prescription and use this syrup
By adding carbonated water to 50 g to make 200 ml,
A carbonated drink was prepared. After allowing the carbonated drink to stand at room temperature for one month, the state of the carbonated drink (whether neck ring was formed or not) was observed. The results are shown in Table 6. The symbol in Table 6 shows the evaluation according to the following evaluation criteria.

Evaluation Criteria: −; Neck ring is not generated. +: Neck ring is slightly generated. ++: Neck ring is generated. ++++: Neck rings are produced in large quantities. Formulation of syrup for carbonated drinks: Fructose-glucose liquid sugar (Brix 75 °) 26 g Citric acid 0.4 g L-ascorbic acid 0.1 g Emulsion composition 0.2 g Ion-exchanged water 23.3 g Total 50 g

[0062]

[Table 6]

From Table 6, when the emulsified composition was used in a carbonated beverage, a mixture of decaglycerin monostearate and sucrose monooleate as an emulsifier,
Alternatively, when a mixture of decaglycerin monostearate and lecithin is used, decaglycerin monostearate alone or a mixture of decaglycerin monostearate and glycerin monooleate and decaglycerin monostearate and sorbitan It can be seen that it has an excellent effect as compared with the case of using the mixture with the monooleic acid ester.

Example 7: Effect of Presence or Absence of Antioxidant An emulsion composition containing the antioxidant (emulsion composition A) was prepared by using the following active ingredients, emulsifiers, antioxidants, and hydrophilic media. , And an emulsion composition containing no antioxidant (emulsion composition B) was produced. Yogurts were prepared with these emulsified compositions A or B and their stability was tested.

Formulation of emulsified composition: Content (%) AB [Active ingredient] Purified fish oil 20 20 (DHA content about 25%, EPA content about 10%) [Emulsifier] Decaglycerin monooleate 2 2 Sucrose monostearate 1 1 [Antioxidant] Tea extract None 3 [Hydrophilic medium] Water 37 34 Glycerin 40 40 Total 100 100

(Method for producing emulsified composition and yogurt and method for stability test) Glycerin, an emulsifier and an antioxidant (an antioxidant is added only when producing the emulsified composition B) are dissolved in water, and then this is added. The purified fish oil was added to and stirred and dispersed, and then emulsified using a homogenizer to prepare an emulsified composition A or B. Using the emulsified composition A or B, a yogurt having the following formulation was prepared.
After sterilizing this yogurt and cooling, 1% of a lactic acid bacterium culture was added, and the mixture was filled in a polyethylene transparent cup and cultured at 28 ° C. for 20 hours. Next, fluorescent light irradiation (2000lux, 1 week)
After that, the flavor was evaluated. The results are shown in Table 7.
The average value in Table 7 is a value according to the following evaluation criteria.

Formulation of yogurt: Milk 50% Skim milk powder 5% Emulsion composition 1% Ion-exchanged water 44% Total 100%

Flavor evaluation criteria: 5 points: No fishy odor is felt. 4 points: A slight fishy odor is felt. 3 points: A smell of fish is felt. 2 points: A strong fishy odor is felt. 1 point: An extremely strong fish odor is felt.

[0069]

[Table 7]

It can be seen from Table 7 that the emulsified composition containing the emulsifier and the antioxidant exhibits a superior effect as compared with the emulsified composition containing only the emulsifier (without the antioxidant).

Example 8: Effect of particle size of oil droplets 4 g of polyglycerin aliphatic ester and 0.5 g of sodium L-ascorbate were added to a mixture of 45 g of glycerin and 20 g of water.
To the solution in which and were dissolved, 20 g of fish oil, 8 g of refined coconut oil and 0.5 g of soybean lecithin were dissolved, and the mixture was stirred and dispersed, and then emulsified with a high pressure homogenizer to obtain oil droplet particles. A uniform emulsion composition of 0.20 μm was produced (invention product 1). The particle size of the oil droplets was measured using a laser diffraction particle size distribution analyzer SALD-110 (manufactured by Shimadzu Corporation). Further, the same operation as in the production method of the product 1 of the present invention was performed except that the oil droplet particles of the emulsified composition were reduced to about 0.7 μm by lowering the pressure of the high-pressure homogenizer, and the oil droplet particles were emulsified to about 0.7 μm. A composition was obtained (Comparative product 1).

(1) The product 1 of the present invention was stored at 60 ° C. for one week and then diluted 1000 times with ion-exchanged water. Regarding the flavor of this diluted solution, a sensory test was conducted on 10 professional panelists. The results are shown in Table 8. The sensory evaluation average value in Table 8 is a value according to the following evaluation criteria.

Sensory evaluation criteria: 5 points: No offensive odor is felt. 4 points: Almost no offensive odor is felt. 3 points: A slight returning odor (fish odor) is felt. 2 points: A considerable returning odor (fish odor) is felt. 1 point: A strong returning odor (fish odor) is felt.

[0074]

[Table 8]

As is clear from the results shown in Table 8, the product 1 of the present invention barely feels the returning odor derived from DHA even after storage at 60 ° C. for 1 week.

(2) Fructose glucose liquid sugar 160 g, citric acid
0.5 g was dissolved in 90 g of water, and 1 g of the product 1 of the present invention or the comparative product 1 was added to this solution, and the total amount was adjusted to 1 liter with carbonated water. After filling the bottle, the bottle was stoppered and sterilized at 85 ° C. for 20 minutes to obtain a carbonated beverage. The carbonated beverage thus obtained was allowed to stand at 60 ° C. for 10 days, and the beverage after storage was observed. The results are shown in Table 9. Each symbol in the table has the following meaning. -R: No neck ring is observed. ± R: Neck ring is slightly recognized. + R: A clear neck ring is recognized. ++ R: Remarkable neck ring is recognized.

[0077]

[Table 9]

As is clear from the results of Table 9, Comparative product 1
Occurrence of neck ring was observed in the beverage using No. 1, but no neck ring was observed in the beverage using Inventive Product 1. Therefore, it is understood from Example 8 that when the emulsified composition is used in a carbonated beverage, the smaller the particle diameter of the oil droplet is, the more stable it is.

Example 9: Safety of Lactic Acid Bacteria Drink Containing Emulsion Composition
Qualitative An emulsified composition was produced using the active ingredient, emulsifier, antioxidant and hydrophilic medium shown below. A lactic acid bacterium beverage was prepared using this emulsified composition, and its stability was tested.

Formulation of emulsified composition: content (%) [active ingredient] purified fish oil 50 (DHA content about 50%, EPA content about 15%) [emulsifier] decaglycerin monooleate 7 sucrose monostearin Acid ester 3 Enzymolytic lecithin 0.5 [Antioxidant] Sodium L-ascorbate 1 [Hydrophilic medium] Glycerin 30 Water 8.5 Total 100

(Method for producing emulsified composition and lactic acid bacterium beverage and method for stability test) An antioxidant and an emulsifier were dissolved in a hydrophilic medium, and then the active ingredient was added thereto and dispersed by stirring, and then a homogenizer was used. By emulsifying
An emulsified composition was produced. Using this emulsified composition, lactic acid bacteria beverages A and B having the following formulations were prepared. Formulation of lactic acid bacterium beverage: Content (Kg) A B [component] skim milk powder 1 1 lactic acid bacterium culture 1 1 ion-exchanged water 20 20 [component] sugar 8 8 skim milk powder 2 2 pectin 0.4 0.4 citric acid 0. 1 0.1 Emulsified composition 1 None Purified fish oil None 0.5 (DHA content about 50%, EPA content about 15%) Fragrance (yogurt flavor) 0.1 0.1 Water 66.4 66.9 Total 100 100

Fermented milk was prepared using the components by a conventional method and sterilized and cooled in advance. A lactic acid bacterium beverage was prepared by adding this to the mixture of components and homogenizing with a homogenizer. The prepared lactic acid bacterium beverage was refrigerated and stored for 2 weeks, and its flavor was evaluated by 10 panelists. The results are shown in Table 10. The average value in Table 10 is an evaluation according to the flavor evaluation standard shown in Example 7.

[0083]

[Table 10]

From Table 10, it can be seen that the lactic acid bacteria beverage containing purified fish oil suppresses the generation of fish odor by containing the emulsion composition of the present invention.

Example 10: Stabilization of purines containing emulsified composition
Properties An emulsified composition was produced using the active ingredient, emulsifier, antioxidant and hydrophilic medium shown below. Purines were prepared using this emulsified composition and tested for stability.

Formulation of emulsified composition: Content (%) [Active ingredient] Purified fish oil 5 (DHA content about 5%, EPA content about 0.1%) [Emulsifier] Decaglycerin monostearate 3 Sucrose monoolein Acid ester 1 [Antioxidant] Sunflower seed extract 5 [Hydrophilic medium] Glycerin 50 Water 36 Total 100

(Method for producing emulsified composition and pudding and stability test method) An emulsified composition was produced in the same manner as in Example 9. A pudding having the following formulation was prepared using this emulsified composition. Purine formulation: Content (Kg) Full-fat sweetened condensed milk 6 Skim milk powder 5 Refined coconut oil 4 Sugar 9 Sweetened egg yolk 8 Gelling agent 0.5 Perfume 0.2 Emulsion composition 0.5 Water 66.8 Total 100

After dissolving the above raw materials, sterilization was performed at 85 ° C. for 10 minutes. Then, the mixture was homogenized with a homogenizer, then charged into a container and cooled to prepare a pudding.
The prepared pudding was stored at 7 ° C. for 2 weeks, and then its flavor was evaluated. As a result, the flavor was not deteriorated.

Example 11: Wiener grass containing emulsified composition
Stability of sage The emulsified composition was produced using the active ingredient, emulsifier, antioxidant and hydrophilic medium shown below. Wiener sausage was prepared using this emulsified composition and its stability was tested.

Formulation of emulsified composition: content (%) [active ingredient] purified fish oil 10 (DHA content about 35%, EPA content about 10%) [emulsifier] decaglycerin monostearate 2 decaglycerin monoolein Acid ester 3 [Antioxidant] Erythorbic acid 0.5 [Hydrophilic medium] D-sorbitol 60 Water 24.5 Total 100

(Method for Producing Emulsion Composition and Wiener Sausage and Stability Test Method) An emulsion composition was produced in the same manner as in Example 9. Using this emulsion composition, a Wiener sausage having the following formulation was prepared. Formula of Wiener Sausage: [Component A] Content (Kg) Pork Ude Meat 7 Pork Fat 1 Iced Water 2 10 [Component B] Salt 150 Sodium Nitrite 5 Polymerized Sodium Phosphate 50 Spice Mix 50 L-Glutamate 10 Sugar 20 Sorbin Potassium acid 20 Starch 300 Emulsion composition 200 Total 805 A dough is prepared according to a conventional method using the above components A and B,
It was filled in sheep intestine, dried, smoked, sterilized and cooled to prepare a wiener sausage.

The prepared wiener sausage was stored in the refrigerator for 2 weeks and then tasted. As a result, it had a good flavor and no fishy odor was felt.

Example 12: Soft drink water containing emulsified composition
Stability An emulsified composition was produced using the active ingredient, emulsifier, antioxidant, hydrophilic medium and other oil-soluble ingredients shown below. Soft drinks were prepared using this emulsified composition and their stability was tested.

Formulation of Emulsion Composition: Content (%) [Active ingredient] Purified fish oil 5 (DHA content about 35%, EPA content about 10%) [Other oil-soluble ingredients] β-carotene 0.5 in Chain triglyceride 5 orange oil 0.5 SAIB (sucrose acetate isobutyrate) 10 [emulsifier] decaglycerin monooleate 6 enzymatically decomposed lecithin 0.1 [antioxidant] L-ascorbic acid 0.5 [hydrophilic medium ] Glycerin 50 Water 22.4 Total 100

(Manufacturing method of emulsified composition and soft drink and stability test method) An antioxidant and an emulsifier are dissolved in a hydrophilic medium, and then the active ingredient and other oil-soluble ingredients are dissolved by heating. After adding the mixed solution and stirring and dispersing,
An emulsified composition was produced by emulsifying using a homogenizer.

Using this emulsified composition, a soft drink having the following formulation was prepared. Soft drink formulation: Content (Kg) Fructose dextrose liquid sugar 15 orange transparent juice (1/5 concentrated) 0.2 L-ascorbic acid 0.1 citric acid (crystal) 0.2 sodium citrate 0.05 orange Flavor 0.1 Emulsion composition 0.2 Water 84.15 Total 100 The above raw materials were mixed, dissolved, sterilized and cooled to prepare soft drink.

The prepared soft drink was stored at room temperature for 3 months, and then its flavor was evaluated. As a result, no fishy odor was felt. For the beverages before and after storage, the oil content was extracted with n-hexane, and the POV (Peroxide Valu
e) was measured. The results are shown in Table 11. PO in Table 11
The unit of V is meq / Kg.

[0098]

[Table 11]

As is clear from Table 11, even after storage at room temperature for 3 months, almost no increase in POV was observed.

Example 13: Hard Can Containing Emulsion Composition
Stability of Day An emulsified composition was produced using the active ingredient, emulsifier, antioxidant, hydrophilic medium, and other oil-soluble ingredients shown below. A hard candy was prepared using this emulsion composition, and its stability was tested.

Formulation of Emulsion Composition: Content (%) [Active ingredient] Refined fish oil 10 (DHA content about 25%, EPA content about 10%) [Other oil-soluble ingredients] γ-linolenic acid oil (γ -Linolenic acid content 25%) 10 [Emulsifier] Decaglycerin palmitate 6 Soybean lecithin 0.5 [Antioxidant] Apple extract 1 Extracted tocopherol 0.5 [Hydrophilic medium] Glycerin 72 Total 100

(Method for producing emulsified composition and hard candy and method for stability test) An antioxidant and an emulsifier were dissolved in a hydrophilic medium, and then the active ingredient and other oil-soluble ingredients were dissolved therein. The mixed solution was added, and the mixture was stirred and dispersed, and then emulsified using a homogenizer to produce an emulsified composition.

A hard candy having the following formulation was prepared using this emulsified composition. Hard candy formula: Content (Kg) Sugar 60 Starch syrup 40 Citric acid (crystal) 0.7 L-Ascorbic acid 0.05 Dye 0.05 Fragrance 0.3 Emulsion composition 0.4 Water 20 Total 100 A hard candy was prepared according to a conventional method.

The prepared hard candy was stored at room temperature for 3 months, and then the flavor was evaluated. As a result, no fishy odor was felt.

[0105]

The emulsion composition of the present invention is stable against oxidation, does not generate odor, and can be stored for a long period of time.
A stable emulsion composition containing, as an active ingredient, DHA, EPA, or at least one derivative of these acids or a natural oil containing these, and beverages, frozen desserts, confectionery, dairy products, bakery products, processed aquaculture products, etc. Can be suitably used for various foods.

When the emulsified composition of the present invention is used, a stable composition containing DHA, EPA or a derivative of these acids can be prepared without impairing the characteristics (eg, shape, odor, taste, texture, color tone) of the food itself. Various foods can be provided. Further, according to the emulsified composition of the present invention, neck ring and precipitation can be prevented from being generated when added to an aqueous food product having any specific gravity.

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Claims (22)

[Claims] 1. Docosahexaenoic acid as an active ingredient,
At least one of eicosapentaenoic acid and derivatives of these acids, or a natural oil containing them, an emulsifier in an amount sufficient to emulsify at least the active ingredient, an antioxidant, and a hydrophilic medium. Polyglycerin fatty acid ester with HLB of 10 or more (fatty acid has 12 to 20 carbon atoms)
A stable emulsified composition characterized by being a sucrose fatty acid ester (a fatty acid having 12 to 20 carbon atoms) and / or lecithin alone and a hydrophilic medium being a polyhydric alcohol or a hydrous polyhydric alcohol. 2. The emulsion composition according to claim 1, wherein the active ingredient is a natural oil containing docosahexaenoic acid, eicosapentaenoic acid or derivatives of these acids. 3. The emulsified composition according to claim 1, wherein the natural oil is fish oil, egg yolk oil or oil derived from algae. 4. The content of at least one of docosahexaenoic acid, eicosapentaenoic acid and derivatives of these acids or the natural oil containing them in the emulsion composition is about 0.0001.
The emulsified composition according to claim 1, which is about 50% by weight. 5. The polyglycerin fatty acid ester is 6-
The emulsion composition according to claim 1, having an average degree of polymerization of glycerin of 15. 6. The polyglycerin fatty acid ester is HL
The emulsified composition according to claim 1, wherein B 13 or more, the fatty acid has 14 to 20 carbon atoms, and the glycerin has an average polymerization degree of 8 to 15. 7. The emulsified composition according to claim 1, wherein the polyglycerin fatty acid ester is decaglycerin monostearate, decaglycerin monooleate or decaglycerin monopalmitate. 8. The mixing ratio (weight ratio) of the polyglycerin fatty acid ester and the sucrose fatty acid ester is about 1: 0.05-.
The emulsified composition according to claim 1, which is 1: 1. 9. The emulsion composition according to claim 1, wherein the mixing ratio (weight ratio) of the polyglycerin fatty acid ester and lecithin is about 1: 0.005 to 1: 0.5. 10. The emulsified composition according to claim 1, wherein the mixing ratio (weight ratio) of polyglycerin fatty acid ester, sucrose fatty acid ester, and lecithin is about 1: 0.05: 0.005 to 1: 1: 0.5. 11. The emulsifier content of the emulsion composition is about 0.
The emulsified composition according to claim 1, which is 01 to 20% by weight. 12. The emulsified composition according to claim 1, wherein the content of the polyglycerin fatty acid ester is about 0.01 to 20% by weight in the emulsified composition. 13. The emulsion composition according to claim 1, wherein the polyhydric alcohol as the hydrophilic medium is glycerin, sorbitol or propylene glycol. 14. The emulsion composition according to claim 1, wherein the water-containing polyhydric alcohol as the hydrophilic medium has a water content of about 50% by weight or less. 15. The antioxidant is one or a mixture of two or more selected from the group consisting of ascorbic acid, isoascorbic acid and salts thereof, catechins, natural extracts containing catechins, and tocopherols. Claim 1
The emulsified composition described. 16. The emulsion composition according to claim 15, wherein the antioxidant is a mixture of ascorbic acid, isoascorbic acid or a salt thereof, and catechins or a catechin-containing natural extract. 17. The emulsified composition according to claim 1, wherein the content of the antioxidant is about 0.001 to 20% by weight in the emulsified composition. 18. The emulsified composition according to claim 1, wherein the ratio (weight ratio) of the emulsifier to the active ingredient is about 1: 0.1 to 1: 1. 19. The emulsified composition according to claim 1, which further contains an edible oil and fat when lecithin is used as an emulsifier. 20. The content of docosahexaenoic acid and / or eicosapentaenoic acid in food is about 0.0001 to 1% by weight.
A liquid or semi-solid food product obtained by adding the emulsified composition according to claim 1 to 21. The liquid food is a carbonated drink, a lactic acid bacterium drink,
The food according to claim 20, which is a fruit drink or milk. 22. The food according to claim 20, wherein the semi-solid food is yogurt or pudding.