JPH10330781A - Composition containing highly unsaturated fatty acid and/or ester thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an improved fish oil comps. which is odorless without emitting an unpleasant odor inherent in a fish oil even after a long storage or even when heated, and is excellent in storage stability and heat stability, an emulsion prepared therefrom, and foods and cosmetics contg. the compsn. or emulsion, and to provide a method for preparing the same. SOLUTION: An improved fish oil material is prepd. by mixing at least one fish oil material selected from among fish oils, highly unsatd. fatty acids derived from fish oils, and esters thereof with vinegar and/or a citrus fruit juice under stirring, leaving the resultant mixture standing, and separating and removing the water phase formed. The objective compsn. is prepd. by adding 10-120 pts.wt. vegetable oil alone or together with 0.05-1 pt.wt. at least one additive selected from among collagen, starch, and agar to 100 pts.wt. above-prepd. improved fish oil material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a method for producing a fish oil which has no odor even after storage for a long period of time without odor and has no odor when heated, and has excellent storage stability and heat stability. The present invention relates to an improved fish oil-based composition, a method for preparing the same, an emulsion prepared using the composition, and foods and cosmetics containing the composition or the emulsion, and a modified fish oil-based composition of the present invention. Contains a large amount of polyunsaturated fatty acids such as DHA and EPA useful for living organisms and esters thereof, and makes use of the above-mentioned properties such as long-term odorlessness, storage stability, and heat stability, and is used for foods, cosmetics,
It can be used effectively for other uses.

[0002]

BACKGROUND OF THE INVENTION Certain of the polyunsaturated fatty acids and their esters contained in fish oil are known to be extremely medically and nutritionally effective. For example, eicosapentaenoic acid (hereinafter referred to as “EPA”), which is one of the polyunsaturated fatty acids contained in fish oil, and its ester are capable of lowering cholesterol in blood,
Since it has thrombus suppression, it is effective for prevention and treatment of myocardial infarction, cerebral infarction, arteriosclerosis and the like. In addition, it is known that docosahexaenoic acid (hereinafter referred to as “DHA”), which is one of the polyunsaturated fatty acids contained in fish oil, and esters thereof have excellent effects such as improvement of learning function, antitumor, and antiallergy. Have been. In addition, EPA and D
HA is known to be effective also for atopic dermatitis and the like. Therefore, EPA contained in fish oil
Polyunsaturated fatty acids and their esters, such as and DHA, are being developed as foods, health foods, cosmetics, pharmaceuticals, etc. from the above-mentioned excellent properties,
Some are already marketed as health foods and pharmaceuticals.

[0003] However, polyunsaturated fatty acids and their esters have the disadvantage that the unsaturated bond portion is easily oxidized, causing rancidity and generating a characteristic unpleasant odor. To prevent this oxidation, natural tocopherols,
It has been attempted to add antioxidants and deodorants such as tea extract and ascorbic acid, but they have not been sufficiently effective. Attempts have also been made to mix DHA with a large amount of starch and wrap the DHA with starch powder to deodorize it. However, when the food obtained by this method is added to food, there is a disadvantage that a large amount of starch used to wrap the DHA affects the taste of the food, and the unpleasant odor caused by DHA is sufficiently prevented. However, there is a drawback that the amount of use is limited.

[0004]

Under the circumstances described above, the present inventor has proposed D
When breads are manufactured by adding a suspension composed of fish oil containing HA as a main component and vinegar or citrus juice to raw materials for bread making, DHA-containing breads having no unpleasant odor caused by fish oil can be obtained. And filed earlier (Japanese Unexamined Patent Publication No.
274806 and JP-A-7-270807). However, the DHA used in these methods
Suspension consisting of fish oil and vinegar or citrus juice whose main components are odorless at the time of preparation of the suspension and can be used effectively for the production of bread, but leaving the suspension unattended It has been found that odor tends to be generated with the passage of time, and there is room for improvement in the storage stability.

[0005] The inventors of the present invention have sought to obtain fish oil, or highly unsaturated fatty acids and esters thereof derived from fish oil, which have excellent storage stability and can maintain an odorless state even when stored for a long period of time. The research has been repeated for the purpose.
As a result, fish oil or a polyunsaturated fatty acid derived from fish oil and / or an ester thereof is added to at least one selected from vinegar and citrus juice, and mixed and stirred.
When the mixture (suspension) is allowed to stand and separated into an oil phase and an aqueous phase, and the aqueous phase is removed and the oil phase is recovered as a modified fish oil, highly unsaturated fatty acids such as DHA and EPA and / or The above-mentioned modified fish oil containing the ester was found to have no odor and no odor, did not generate an unpleasant odor even after long-term storage, and was excellent in storage stability. -8145).

The inventors of the present invention have disclosed the above-mentioned Japanese Patent Application No. Hei.
Although further studies have been made based on the invention of No. 8145,
As a result, when vegetable oil is added to the modified fish oil containing the polyunsaturated fatty acid and / or its ester obtained in the invention of Japanese Patent Application No. 9-8145, the odorless state is maintained even after long-term storage. It has been found that the composition has storage stability and does not generate an unpleasant odor when heated. In addition, the present inventors have found that, at that time, when at least one selected from collagen, starch and agar is further added, the clarity of the modified fish oil is further improved. In the production of foods and cosmetics containing fish oil and highly unsaturated fatty acids such as DHA and EPA derived therefrom and / or esters thereof, heat treatment is often performed in the production process of foods and cosmetics. Therefore, when the vegetable oil is added to the above-mentioned modified fish oil, the above-mentioned characteristics found by the present inventors that they can maintain an odorless state without generating an unpleasant odor even when heated, the fish oil and the advanced properties derived therefrom It can be said that it is extremely effective in terms of utilization of unsaturated fatty acids and / or esters thereof.

Therefore, at least one selected from vinegar and citrus juice is mixed and stirred with a fish oil-based material comprising at least one of fish oil, a highly unsaturated fatty acid derived from fish oil and an ester thereof, and the mixture is allowed to stand. For the modified fish oil-based material obtained by separating and removing the aqueous phase,
A composition containing a polyunsaturated fatty acid and / or an ester thereof (hereinafter, sometimes referred to as a "modified fish oil-based material composition" or "modified fish oil composition"), which is obtained by adding a vegetable oil or fat. ).

[0008] The present invention relates to a fish oil-based material comprising at least one of fish oil, a highly unsaturated fatty acid derived from fish oil and an ester thereof, and mixing and stirring at least one selected from vinegar and citrus juice. Characterized in that at least one selected from collagen, starch and agar, and vegetable oils and fats are added to a modified fish oil-based material obtained by separating and removing an aqueous phase after standing. A composition containing an unsaturated fatty acid and / or an ester thereof (hereinafter sometimes referred to as a “modified fish oil-based material composition” or a “modified fish oil composition”).

Further, according to the present invention, at least one selected from vinegar and citrus juice is added to a fish oil-based material comprising at least one of fish oil, highly unsaturated fatty acids derived from fish oil and esters thereof, and the mixture is stirred. Thereafter, the mixture is allowed to stand and separated into an aqueous phase and an oil phase, the aqueous phase is separated and removed, and the oil phase is recovered as a modified fish oil-based material. Then, a vegetable oil is added to the modified fish oil-based material. A method for preparing a composition (a modified fish oil-based material composition or a modified fish oil composition) containing a polyunsaturated fatty acid and / or an ester thereof, characterized in that:

According to the present invention, at least one selected from vinegar and citrus juice is added to a fish oil-based material comprising at least one of fish oil, highly unsaturated fatty acids derived from fish oil and esters thereof, and the mixture is stirred. Thereafter, the mixture is allowed to stand and separated into an aqueous phase and an oil phase, the aqueous phase is separated and removed, and the oil phase is recovered as a modified fish oil-based material. A composition containing a highly unsaturated fatty acid and / or an ester thereof (modified fish oil-based material composition or modified fish oil composition), characterized by adding at least one selected from agar and vegetable oils and fats. It is a preparation method.

Further, the present invention provides an emulsion obtained by emulsifying the above-mentioned composition (modified fish oil-based material composition or modified fish oil composition) containing a polyunsaturated fatty acid and / or an ester thereof; Foods and cosmetics to which the composition or the emulsion is added are included.

In the above-mentioned modified fish oil-based material composition (modified fish oil composition) and preparation method of the present invention,
Vegetable oils and fats are preferably added in a ratio of 10 to 120 parts by weight with respect to 100 parts by weight of the modified fish oil-based material, and at least one selected from collagen, starch and agar is added with respect to 100 parts by weight of the modified fish oil-based material. Is preferably 0.05 to
1 part by weight is added.

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. In the present invention, as a raw material for obtaining the modified fish oil-based material used for the modified fish oil-based material of the present invention, a fish oil-based material comprising at least one of fish oil, a highly unsaturated fatty acid derived from fish oil and an ester thereof is used. . Here, the term "fish oil" as used in the present invention means oils and fats collected from animals living in water (that is, fish oil in a broad sense), and includes fish oil (fish oil in a narrow sense) collected from fish, sea animal oil, liver oil and the like. I do. The above-mentioned fish oils (broadly defined fish oils) are all EPA, DH
A, contains other highly unsaturated fatty acids and / or esters thereof. The term "highly unsaturated fatty acid derived from fish oil" as used in the present invention refers to a fatty acid having two or more unsaturated bonds obtained by performing purification, separation, etc. from the above-mentioned fish oil in a broad sense. However, typical examples thereof include EPA and DHA. The term "esters of highly unsaturated fatty acids" used in the present invention refers to esters of the above-mentioned highly unsaturated fatty acids and glycerin (mono, di and / or triglycerides), and the above-mentioned highly unsaturated fatty acids and lower alcohols (Eg, methyl ester, ethyl ester, etc.).

In the present invention, as a fish oil-based material, unrefined fish oil, fish oil highly purified from lowly refined fish oil, and highly unsaturated fatty acids and / or esters thereof contained therein from fish oil may be used in combination with a plurality of types of highly refined fatty acids. Either a mixture of polyunsaturated fatty acids and / or esters obtained in the form of a mixture of unsaturated fatty acids and / or esters thereof, or a specific polyunsaturated fatty acid and / or esters thereof obtained from fish oil Can also be used. Generally, as fish oil-based materials, fish oil (fish oil in a narrow sense) collected from fish such as sardines, mackerel, cod, tuna, etc., low-refined oil or highly refined oil thereof, highly unsaturated fatty acids obtained from the fish oil, and / or Alternatively, an ester thereof is preferably used in terms of availability, cost, and the like. In the present invention, a fish oil-based material containing one or both of DHA and EPA at a ratio of 10% by weight or more is preferably used because it is effective in promoting health and preventing and treating diseases. Can be In the present invention, a commercially available fish oil-based material may be used, or a fish oil-based material may be collected or prepared and used for the present invention.

In the present invention, a modified fish oil-based material is prepared by adding at least one selected from vinegar and citrus juice to the above-mentioned fish oil-based material and performing a treatment. That is, to a fish oil-based material, at least one selected from vinegar and citrus juice is added, mixed and stirred,
When the resulting mixture (suspension) is allowed to stand, the upper layer becomes an oil phase and the lower layer becomes an aqueous phase, and separates into two layers. Thus, the lower aqueous phase is separated and removed, and the upper oil phase is reformed. Collect as high quality fish oil-based material.

As the vinegar used at that time, either brewed vinegar and / or synthetic vinegar can be used. Examples of brewed vinegar include rice vinegar, brown rice vinegar, grain vinegar such as malt vinegar, apple vinegar, and fruit vinegar such as grape vinegar.Examples of synthetic vinegar include acetic acid that is chemically synthesized. Examples thereof include those prepared by diluting with water and adding amino acids and sugars, and those obtained by adding acetic acid chemically synthesized to brewed vinegar. Examples of the citrus juice include fruit juices such as lime, lemon, pomelo, kabosu, grapefruit, summer tangerine, yuzu and sudachi, and concentrates thereof.

In the present invention, only one of the above-mentioned brewed vinegar, synthetic vinegar and citrus juice may be used, or two or more thereof may be used. When two or more types are used, a combination of two or more types of brewed vinegar, a combination of two or more types of synthetic vinegar, a combination of one or more types of brewed vinegar and one or more types of synthetic vinegar, a brewed vinegar And synthetic vinegar 1
Any one or a combination of two or more kinds of citrus juices or one or more kinds of citrus juices may be used. Among them, fruit vinegar such as apple vinegar is preferably used. Although the reason is not clear, apple cider vinegar contains a large number of organic acids such as malic acid, citric acid, oxalic acid, tartaric acid, etc. together with acetic acid, and they act synergistically. Guessed.

The addition ratio of vinegar and / or citrus juice to the fish oil-based material is 2 to 70 parts by weight with respect to 100 parts by weight of the fish oil-based material (when two or more vinegar and / or citrus juice are used, the total Amount), more preferably 4 to 40 parts by weight, even more preferably 5 to 20 parts by weight. If the added amount of vinegar and / or citrus juice is less than 5 parts by weight based on 100 parts by weight of the fish oil-based material, it becomes difficult to remove the unpleasant odor due to the fish oil-based material, while 70
If the amount is more than 10 parts by weight, the acid odor and sourness become strong, and the taste and flavor of the modified fish oil-based material tend to decrease.

Mixing and stirring after adding vinegar and / or citrus juice to the fish oil-based material may be performed using any of conventional mixing and stirring devices, for example, using a propeller mixer, a turbine mixer, a homomixer, or the like. Can be used. The temperature during mixing and stirring is generally about 10 to prevent deterioration of the fish oil-based material and solidification.
A temperature of 25 ° C. is preferably employed. The mixing and stirring time is not particularly limited, and may be performed until a uniform suspension is formed. In the case of using a general-purpose mixing and stirring device as described above, the stirring time is generally about 1 to 30 minutes. Is done. In addition, when mixing and stirring after adding vinegar and / or citrus juice to the fish oil-based material under an inert gas atmosphere such as nitrogen gas, the highly unsaturated fatty acids and / or It is preferable because the oxidation of the ester can be more effectively suppressed and a modified fish oil-based material having more excellent odorlessness can be obtained.

After a suspension is formed by the above-mentioned mixing and stirring treatment, the suspension is allowed to stand, and the oil phase (upper layer) and the aqueous phase (lower layer) are separated into layers. And the modified fish oil-based material is recovered. The resulting modified fish oil-based material is odorless, has no unpleasant odor peculiar to fish oil, can maintain an odorless state even when stored at room temperature for a long time, and is excellent in storage stability.

In the present invention, the modified fish oil-based material obtained above is added with vegetable oils and fats to maintain an odorless state even after long-term storage, and has excellent storage stability, and even when heated. A composition (a modified fish oil-based material composition or a modified fish oil composition) of the present invention, which does not generate an unpleasant odor and has excellent heat stability, is prepared. Any vegetable oils and fats that are safe for the human body can be used as the vegetable oils and fats to be added to the modified fish oil-based material, for example, grape oil, rice oil, wheat germ oil, olive oil, perilla oil, safflower oil, Examples include soybean oil, sesame oil, corn oil, cottonseed oil, safflower oil, salad oil, hydrogenated oil thereof, and the like, and one or more of the above-described vegetable oils and fats can be used. Among them, grape oil, rice oil, wheat germ oil, olive oil and / or perilla oil are preferably used in terms of storage stability and flavor.

The amount of the vegetable oil or fat to be added depends on the amount of the modified fish oil-based material 10
The amount is preferably from 10 to 120 parts by weight, more preferably from 30 to 100 parts by weight, based on 0 parts by weight. With respect to 100 parts by weight of the modified fish oil-based material, if the addition amount of the vegetable oil is less than 10 parts by weight, the thermal stability of the modified fish oil-based material is not sufficiently improved, while if it exceeds 120 parts by weight, The content of the modified fish oil-based material in the composition is reduced,
As a result, useful highly unsaturated fatty acids such as DHA and EPA in the modified fish oil-based material composition (modified fish oil composition) and / or
Or, the content ratio of the ester is relatively reduced, and even when used in foods, cosmetics, and other products, DHA
Or EPA or the like is not sufficiently exerted.

The method of adding the vegetable oil to the modified fish oil material is not particularly limited, and any method capable of uniformly mixing the vegetable oil in the modified fish oil material can be employed. Generally, 3
The mixing may be performed at a temperature of 0 ° C. or lower and higher than the solidification temperature of the modified fish oil-based material using the above-described general-purpose mixing and stirring device.

In the present invention, at least one selected from collagen, starch, and agar may be added to the modified fish oil-based material, if necessary, together with vegetable oils and fats. When at least one selected from collagen, starch and agar is added to the modified fish oil-based material, a modified fish oil-based material composition (modified fish oil composition) having extremely excellent clarity can be obtained. When at least one selected from collagen, starch, and agar is added, the amount of addition (when two or more types are used, the total amount) is modified fish oil-based material 1
It is preferably from 0.05 to 1 part by weight, particularly preferably from 0.05 to 0.2 part by weight, based on 00 parts by weight. If the amount of at least one selected from collagen, starch and agar exceeds 0.05 parts by weight, precipitation tends to occur.

As the collagen, any of collagen obtained from animal connective tissue, cartilage and tendon, and soluble gelatin obtained by heating them in water can be used. Among them, water-soluble gelatin is preferably used from the viewpoints of uniform mixing in the modified fish oil-based material, handleability, cost and the like. As the starch, potato starch, wheat starch, corn starch and the like can be used.
Among them, powdery starch is preferably used from the viewpoint of good handleability and good clarification action. In addition, as the agar, a red algae cell wall component is extracted, dehydrated and dried, and solid agar, square agar,
Any of thread agar, granule agar, and powder agar can be used. Among them, powdered agar is particularly preferably used from the viewpoint of good handleability and clarifying action.

The timing of addition of at least one selected from collagen, starch and agar to the modified fish oil-based material is not particularly limited, even before the addition of vegetable oils and fats and at the same time as the addition of vegetable oils and fats. Or after the addition of vegetable fats and oils. Among them, it is preferable to add at least one selected from collagen, starch and agar before adding the vegetable oil or fat from the viewpoint of obtaining a modified fish oil-based material composition having more excellent clarity.

The modified fish oil-based material composition (modified fish oil composition) of the present invention obtained as described above can be used by adding it to various foods, cosmetics, etc., or mixed directly with other components or with other components. It can be used as a medicine. And the above-mentioned product obtained by adding or using the modified fish oil-based material composition (modified fish oil composition) of the present invention,
Depending on the type of the polyunsaturated fatty acid and / or its ester contained in the modified fish oil-based material composition, the effect of lowering cholesterol in blood, myocardial infarction, cerebral infarction, prevention and treatment of arteriosclerosis, It has the effect of improving learning function, anti-tumor, anti-allergy and so on.

When the modified fish oil-based material composition of the present invention is used by adding it to food, the type of food is not particularly limited, and for example, bakery products such as breads, soybean products such as cooked rice, noodles, and tofu. Food, processed meat products such as sausage and ham, cakes, cookies, buns, rice crackers, ice cream, pudding, yokan, sweets such as candy, dairy products such as butter, yogurt, mayonnaise, dressing, soy sauce, miso, sauces, etc. And seasonings, sugars such as glucose and liquid oligosaccharides, fruit drinks, drinks such as soy milk and vegetable juice, konjac and the like.

Conventionally, fish oil and polyunsaturated fatty acids and / or ester products derived therefrom have, for example, about 10 to 30 mg of DHA, EPA and / or per loaf of bread due to unpleasant odor derived from fish oil. Or only its ester could be blended, but in the case of the modified fish oil-based material composition of the present invention, a high ratio of 100-300 mg per loaf of bread without impairing the flavor and taste of bread.
HA, EPA and / or an ester thereof can be blended, and a food which can sufficiently exhibit the above-mentioned excellent effects based on a highly unsaturated fatty acid such as DHA or EPA or an ester thereof can be obtained.

The modified fish oil-based material composition (modified fish oil composition) of the present invention obtained above can be prepared by using a method similar to a conventionally known method to obtain a suitable surfactant or the like. Can be emulsified in water to obtain an emulsion, and the resulting emulsion can be used for the production of foods as described above, or for example, an emulsion, hand cream, skin cream, massage cream, cosmetic It may be used for the manufacture of cosmetics such as water and packs, or for other uses.

[0031]

EXAMPLES The present invention will be specifically described below with reference to examples and the like, but the present invention is not limited thereto.

Example 1 [Preparation of Modified Fish Oil Composition] (1) Fish oil 10 containing DHA at a ratio of 27% by weight
0 parts by weight, 10 parts by weight of rice vinegar are added, and the mixture is kept at 10 ° C. under a nitrogen gas atmosphere, and a stirring speed of 500 revolutions / minute using a mixer equipped with two Fowler-type blades. For 5 minutes to form a suspension. (2) The suspension obtained in the above (1) is allowed to stand at room temperature for 24 hours to separate into an oil phase and an aqueous phase. Then, the lower aqueous phase is separated and removed, and the upper oil phase is removed. Was recovered to obtain an odorless modified fish oil. (3) To 100 parts by weight of the modified fish oil obtained in (2) above, 100 parts by weight of edible wheat germ oil were added, and the mixture was mixed and stirred well under a nitrogen gas atmosphere to obtain a modified fish oil composition containing DHA. Was prepared. (4) A part of the modified fish oil composition obtained in the above (3) is sampled, and in air, at 60 ° C, 70 ° C and 8 ° C, respectively.
After heating to a temperature of 0 ° C. for 10 minutes, the presence or absence of unpleasant odor was scored by five panelists according to the evaluation criteria shown in Table 1 below, and the average value was taken. As shown in FIG.

Example 2 [Preparation of Modified Fish Oil Composition] (1) Fish oil 10 containing 45% by weight of DHA
After adding 5 parts by weight of apple cider vinegar to 0 parts by weight and mixing and stirring as in (1) of Example 1 to form a suspension, the suspension is allowed to stand at room temperature for 24 hours. Then, after separating into an oil phase and an aqueous phase, the lower aqueous phase was separated and removed, and the upper oil phase was recovered to obtain an odorless modified fish oil. (2) 30 parts by weight of edible olive oil is added to 100 parts by weight of the modified fish oil obtained in the above (1), and the mixture is mixed and stirred well under a nitrogen gas atmosphere to obtain a modified fish oil composition containing DHA. Prepared. (3) A part of the modified fish oil composition obtained in the above (2) is sampled and subjected to a heat treatment in the same manner as in the case of (3) of Example 1 to obtain an unpleasant odor after heating. The presence or absence was scored by five panelists according to the evaluation criteria shown in Table 1 below, and the average was taken.
The results are shown in Table 2 below.

Example 3 [Preparation of Modified Fish Oil Composition] (1) Fish oil 10 containing 45% by weight of DHA
Example 1 by adding 10 parts by weight of apple cider vinegar to 0 parts by weight
After mixing and stirring to form a suspension in the same manner as in (1) above, the suspension is allowed to stand at room temperature for 24 hours to separate into an oil phase and an aqueous phase. The aqueous phase was separated and removed, and the upper oil phase was recovered to obtain an odorless modified fish oil. (2) To 100 parts by weight of the modified fish oil obtained in the above (1), 0.05 parts by weight of water-soluble gelatin was added and allowed to stand for 24 hours to obtain a fish oil excellent in transparency. (3) 100 parts by weight of edible grape oil is added to 100 parts by weight of the fish oil obtained in (2), and the mixture is mixed and stirred well under a nitrogen gas atmosphere to prepare a modified fish oil composition containing DHA. did. (4) A part of the modified fish oil composition obtained in the above (3) is collected as a sample, subjected to a heating treatment in the same manner as in the case of (3) of Example 1, and subjected to a heat treatment for unpleasant odor. The presence or absence was scored by five panelists according to the evaluation criteria shown in Table 1 below, and the average was taken.
The results are shown in Table 2 below.

Example 4 [Preparation of Modified Fish Oil Composition] (1) DHA obtained by transesterifying fish oil
Fish oil 10 containing 70% by weight of ethyl ester
Example 1 by adding 20 parts by weight of apple cider vinegar to 0 parts by weight
After mixing and stirring to form a suspension in the same manner as in (1) above, the suspension is allowed to stand at room temperature for 24 hours to separate into an oil phase and an aqueous phase. The aqueous phase was separated and removed, and the upper oil phase was recovered to obtain an odorless modified fish oil. (2) 100 parts by weight of edible rice oil is added to 100 parts by weight of the modified fish oil obtained in the above (1), and the mixture is mixed and stirred well under a nitrogen gas atmosphere to obtain a modified fish oil composition containing DHA. Was prepared. (3) A part of the modified fish oil composition obtained in the above (2) is sampled and subjected to a heat treatment in the same manner as in the case of (3) of Example 1 to obtain an unpleasant odor after heating. The presence or absence was scored by five panelists according to the evaluation criteria shown in Table 1 below, and the average was taken. The results were as shown in Table 2 below.

Example 5 [Preparation of Modified Fish Oil Composition] (1) A fish oil containing 25% by weight of EPA was used instead of a fish oil containing 27% by weight of DHA. A odorless modified fish oil was prepared in exactly the same manner as in Example 1, and a modified fish oil composition containing edible flour germ oil was prepared using the same in the same manner as in Example 1. (2) A part of the modified fish oil composition obtained in the above (1) was sampled and subjected to a heat treatment in the same manner as in the case of (3) of Example 1 to remove the unpleasant odor after heating. The presence or absence was scored by five panelists according to the evaluation criteria shown in Table 1 below, and the average was taken. The results were as shown in Table 2 below.

Example 6 [Preparation of Modified Fish Oil Composition] (1) Except that fish oil containing 55% by weight of EPA was used instead of fish oil containing 45% by weight of DHA A odorless modified fish oil was prepared in exactly the same manner as in Example 2, and a modified fish oil composition containing edible olive oil was prepared using the same in the same manner as in Example 2. (2) A part of the modified fish oil composition obtained in the above (1) was sampled and subjected to a heat treatment in the same manner as in the case of (3) of Example 1 to remove the unpleasant odor after heating. The presence or absence was scored by five panelists according to the evaluation criteria shown in Table 1 below, and the average was taken. The results were as shown in Table 2 below.

Example 7 [Preparation of Modified Fish Oil Composition] (1) Except that fish oil containing EPA at 45% by weight was used instead of fish oil containing DHA at 45% by weight. A odorless modified fish oil was prepared in exactly the same manner as in Example 3, and a modified fish oil composition containing edible grape oil was prepared using the same in the same manner as in Example 3. (2) A part of the modified fish oil composition obtained in the above (1) was sampled and subjected to a heat treatment in the same manner as in the case of (3) of Example 1 to remove the unpleasant odor after heating. The presence or absence was scored by five panelists according to the evaluation criteria shown in Table 1 below, and the average was taken. The results were as shown in Table 2 below.

Example 8 [Preparation of Modified Fish Oil Composition] (1) Fish oil containing 90% by weight of EPA ethyl ester instead of fish oil containing 70% by weight of DHA ethyl ester A modified fish oil composition containing edible rice oil was prepared in the same manner as in Example 4, except that odorless modified fish oil was prepared in the same manner as in Example 4. (2) A part of the modified fish oil composition obtained in the above (1) was sampled and subjected to a heat treatment in the same manner as in the case of (3) of Example 1 to remove the unpleasant odor after heating. The presence or absence was scored by five panelists according to the evaluation criteria shown in Table 1 below, and the average was taken. The results were as shown in Table 2 below.

Example 9 [Preparation of modified fish oil composition] (1) Fish oil 10 containing DHA at a ratio of 27% by weight
After adding 10 parts by weight of lemon juice to 0 parts by weight and mixing and stirring as in (1) of Example 1 to form a suspension, the suspension is allowed to stand at room temperature for 24 hours. Then, after separating into an oil phase and an aqueous phase, the lower aqueous phase was separated and removed, and the upper oil phase was recovered to obtain an odorless modified fish oil. (2) 30 parts by weight of edible olive oil is added to 100 parts by weight of the modified fish oil obtained in the above (1), and the mixture is mixed and stirred well under a nitrogen gas atmosphere to obtain a modified fish oil composition containing DHA. Prepared. (3) A part of the modified fish oil composition obtained in the above (2) is sampled and subjected to a heat treatment in the same manner as in the case of (3) of Example 1 to obtain an unpleasant odor after heating. The presence or absence was scored by five panelists according to the evaluation criteria shown in Table 1 below, and the average was taken. The results were as shown in Table 2 below.

<< Comparative Examples 1 to 3 >> [Preparation of Fish Oil Composition] (1) Fish oil 10 containing DHA at a ratio of 27% by weight
To 0 parts by weight, apple vinegar was added at a ratio of 5 parts by weight (Comparative Example 1), 10 parts by weight (Comparative Example 2) and 20 parts by weight (Comparative Example 3). A suspension was obtained by mixing and stirring in the same manner as described above.
The weight parts were added and mixed well at 25 ° C. in a nitrogen atmosphere to prepare three types of suspensions. (2) Each suspension obtained in the above (1) was heated in the air at 60 ° C., 70 ° C. and 80 ° C. for 10 minutes, respectively, and the presence or absence of unpleasant odor was evaluated in the following evaluation criteria shown in Table 1. According to the above, five panelists evaluated the scores, and the average value was obtained. The result was as shown in Table 2 below.

[0042]

[Table 1] Judgment criteria for odor of modified fish oil composition Rating: Content 4 points: Extremely good without any unpleasant odor peculiar to fish oil. 3 points: The odor derived from fish oil is faint, but almost unnoticeable and good. 2 points: The unpleasant odor peculiar to fish oil is considerable and poor. 1 point: Unpleasant odor peculiar to fish oil is strong and extremely poor.

[0043]

[Table 2]

From the results in Table 2 above, vinegar and / or citrus juice were added to fish oil containing polyunsaturated fatty acids such as DHA and EPA and / or esters thereof, mixed, stirred, and allowed to stand. In the modified fish oil composition of the present invention of Examples 1 to 9 obtained by adding a vegetable oil to the oil phase in which the upper oil phase was recovered as a modified fish oil, the unpleasant odor peculiar to the fish oil even when heated. No heat generation was observed, indicating that the composition was excellent in thermal stability. Furthermore, from the results of Example 2 and Example 6, it can be seen that when collagen is added together with vegetable oils and fats, the clarity of the modified fish oil composition is increased, and the quality is further improved. On the other hand, from the results of Comparative Examples 1 to 3 in Table 2 above, even when vinegar and vegetable oil are added to fish oil containing highly unsaturated fatty acids such as DHA and EPA and / or esters thereof. In the case of Comparative Examples 1 to 3, where vegetable oils and fats are directly added to a suspension obtained by adding vinegar to fish oil,
It can be seen that a fish oil composition having good heat stability was not obtained, and when heated, an unpleasant odor peculiar to fish oil was generated.

Example 10 [Addition of Modified Fish Oil Composition to Sweetener] (1) Modification before heat treatment obtained in Example 1 above to 78 parts by weight of a commercially available liquid sweetener 20 parts by weight of the fish oil composition was added, 2 parts by weight of an emulsifier (“Sugar Ester S1170” manufactured by Mitsubishi Chemical Corporation) was added, and the mixture was stirred at a rotation speed of 10,000 rpm for 3 minutes with a homomixer. An artificial sweetener containing a high quality fish oil composition was prepared. (2) 5 parts by weight of the artificial sweetener obtained in the above (1),
The mixture was stirred in 100 parts by weight of hot water at a temperature of 80 ° C. and the presence or absence of odor at that time was evaluated by five panelists according to the evaluation criteria shown in Table 1 above. The score was 18 and no unpleasant odor peculiar to fish oil was generated.

<< Examples 11 to 18 >> [Addition of modified fish oil composition to sweetener] (1) As modified fish oil composition, modified fish oil before heat treatment obtained in above Examples 2 to 9 An artificial sweetener containing a modified fish oil composition was prepared in exactly the same manner as in Example 10 except that the composition was used. (2) 5 parts by weight of the artificial sweetener obtained in the above (1),
The mixture was stirred in 100 parts by weight of hot water at a temperature of 80 ° C. and the presence or absence of odor at that time was evaluated by five panelists according to the evaluation criteria shown in Table 1 above. The score was 19 points, and no unpleasant odor peculiar to fish oil was generated.

Example 19 [Addition of modified fish oil composition to milk] 1 part by weight of the modified fish oil composition before heat treatment obtained in Example 1 above was added to 100 parts by weight of milk. After mixing well, the mixture was heated at 63 ° C. for 30 minutes. It was stored in a closed container at room temperature for 7 days, and then opened. Five panelists evaluated the presence or absence of odor at that time according to the evaluation criteria shown in Table 1 above. The total name was 20 points, no unpleasant odor peculiar to fish oil was generated, and the taste of milk did not change.

<< Examples 20 to 24 >> [Addition of modified fish oil composition to milk] As the modified fish oil composition, the modified fish oil composition before heat treatment obtained in Examples 2 to 6 above was used. A milk containing the modified fish oil composition was prepared in the same manner as in Example 19, except that the milk was heated at 63 ° C. for 30 minutes. It was stored in a sealed container at room temperature for 7 days, and then opened. Five panelists evaluated the presence or absence of odor at that time according to the evaluation criteria shown in Table 1 above. The total score of the five subjects was 18 or more, there was no unpleasant odor peculiar to fish oil, and the taste of milk did not change.

<< Example 25 >> [Production of bread containing modified fish oil composition] (1) Raw material for baking (100 parts by weight of strong flour, 3 parts by weight of yeast, 3 parts by weight of powdered milk, 5 parts by weight of sugar, water) (70 parts by weight, 2 parts by weight of salt, 7 parts by weight of margarine), kneaded with 100 parts by weight of flour, 100 parts by weight of flour and the modified fish oil composition obtained in Example 1 above, kneaded and fermented. We made bread dough. Take this bread dough at 25 ° C. for a floor time of 60 minutes, divide it, and bench
I took 0 minutes. Then, put in a bread mold, temperature 38 ℃,
After being kept under the condition of 90% humidity for 60 minutes, it was baked in an oven (baked at 190 ° C. for 45 minutes) to produce bread. (2) Five panelists evaluated the presence or absence of odor in the bread obtained in the above (1) according to the evaluation criteria shown in Table 1 above, and the score was 19 points in total of the five panelists. And had no unpleasant odor peculiar to fish oil, and was excellent in flavor. In addition, the outer phase of the bread obtained in this example,
The inner phase, sashimi, and texture were all as good as the bread produced in the same manner without adding the modified fish oil composition.

<< Examples 26 to 33 >> [Preparation of Bread Containing Modified Fish Oil Composition] The procedure of Example 26 was repeated except that the modified fish oil compositions obtained in Examples 2 to 9 were used. Bread was produced in exactly the same manner as in Example 25, and the presence or absence of odor in the obtained bread was evaluated by five panelists according to the evaluation criteria shown in Table 1 above. The total was 18 points or more, and there was no unpleasant odor peculiar to fish oil, and the flavor was excellent. Further, the bread, obtained in Examples 26 to 33, had good external phase, internal phase, citrus, and texture.

<< Example 34 >> [Production of tofu containing modified fish oil composition] (1) After boiling soybean, it is divided into soymilk and okara, and the resulting soymilk (10 to 12%) is mixed with 70 to 75%. Soy milk 1 at a temperature of ℃
About 0.003 parts by weight of bittern per part by weight and 0.3 parts by weight of the modified fish oil composition obtained in Example 2 were added, and the mixture was stirred in a stainless steel vault using a drawer. After leaving it for 20 minutes, it was put into a tofu mold box, and pressure was applied from above the lid with a hydraulic jack to produce cotton tofu. (2) Five panelists evaluated the presence or absence of odor in the tofu obtained in the above (1) in accordance with the evaluation criteria shown in Table 1 above.
The score was 0, there was no unpleasant odor peculiar to fish oil, and the flavor was excellent. Further, the texture of the tofu obtained in this example was as good as that of the ordinary tofu produced in the same manner without adding the modified fish oil composition.

<< Examples 35 to 42 >> [Production of tofu containing modified fish oil composition] The same procedure was carried out except that the modified fish oil compositions obtained in Examples 2 to 9 were used. Cotton tofu was produced in exactly the same manner as in Example 34, and the presence or absence of the odor was evaluated by five panelists based on the evaluation criteria shown in Table 1 above. Of 19 points or more, and there was no unpleasant odor peculiar to fish oil, and tofu excellent in flavor was obtained. Further, the texture of the tofu of the tofu obtained in Examples 35 to 42 was as good as the normal tofu produced in the same manner without adding the modified fish oil composition.

Example 43 Production of Emulsion Containing Modified Fish Oil Composition Raw materials for emulsion (15 parts by weight of ethyl alcohol, 12 parts by weight of propylene glycol, 3 parts by weight of glycerin, 2 parts by weight of stearic acid, 5 parts by weight of the modified fish oil composition obtained in Example 3 is added to 100 parts by weight of 1 part by weight of cetyl alcohol and 59 parts by weight of water), and mixed and stirred well at room temperature to produce an emulsion. did. The resulting emulsion is
It was odorless, did not have any unpleasant odor peculiar to fish oil, and did not generate any unpleasant odor even when left at room temperature for one month after production.

[0054]

According to the present invention, at least one selected from vinegar and citrus juice is mixed and stirred with a fish oil-based material comprising at least one of fish oil, highly unsaturated fatty acids derived from fish oil and esters thereof, and the mixture is allowed to stand. A modified fish oil-based material composition (modified fish oil composition) of the present invention obtained by adding a vegetable oil to a modified fish oil-based material (modified fish oil) obtained by separating and removing an aqueous phase, Foods, cosmetics, pharmaceuticals, as well as immediately after production, as well as being odorless even after long-term storage, with good storage stability, and no heat and no unpleasant odor when heated. And so on can be used very effectively in various fields. And the modified fish oil-based material composition of the present invention (modified fish oil composition)
Contains a large amount of polyunsaturated fatty acids such as DHA and EPA useful for the human body and / or esters thereof, so that the action of lowering cholesterol in blood, myocardial infarction, cerebral infarction, prevention and treatment of arteriosclerosis, It has excellent effects such as improvement of learning function, antitumor and antiallergy.
Further, in the present invention, when at least one selected from collagen, starch and agar is added together with the vegetable oil and fat, the above-mentioned modified fish oil-based material composition (modified fish oil composition) which is more excellent in clarity can be obtained. Obtainable.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI A23L 1/20 104 A23L 1/30 A 1/30 B A61K 7/00 K A61K 7/00 7/48 7/48 C09K 15 / 34 C09K 15/34 C11C 3/00 C11C 3/00 A23D 9/00 518

Claims (11)

[Claims] 1. A fish oil-based material comprising at least one of fish oil, a highly unsaturated fatty acid derived from fish oil and an ester thereof, is mixed with at least one selected from vinegar and citrus juice, and the mixture is allowed to stand. A composition containing a highly unsaturated fatty acid and / or an ester thereof, wherein a vegetable oil is added to a modified fish oil-based material obtained by separating and removing an aqueous phase. 2. A fish oil-based material comprising at least one of fish oil, a polyunsaturated fatty acid derived from fish oil and an ester thereof, and at least one kind selected from vinegar and citrus juice, and the mixture is stirred. A modified fish oil-based material obtained by separating and removing an aqueous phase, characterized in that at least one selected from collagen, starch and agar, and vegetable oils and fats are added, and a highly unsaturated fatty acid and And / or a composition containing the ester thereof. 3. 100 parts by weight of the modified fish oil-based material,
3. The composition according to claim 1, wherein vegetable oil is added in a ratio of 10 to 120 parts by weight. 4. With respect to 100 parts by weight of the modified fish oil-based material,
At least one selected from collagen, starch and agar
3. The method according to claim 2, wherein the seed is added in a proportion of 0.05 to 1 part by weight.
Or the composition of 3. 5. A fish oil-based material comprising at least one of fish oil, a highly unsaturated fatty acid derived from fish oil and an ester thereof, at least one selected from vinegar and citrus juice, and the mixture is stirred. Is allowed to stand to separate into an aqueous phase and an oil phase, the aqueous phase is separated and removed, the oil phase is recovered as a modified fish oil-based material, and then vegetable oil is added to the modified fish oil-based material. For preparing a composition containing a highly unsaturated fatty acid and / or an ester thereof. 6. A fish oil-based material comprising at least one of fish oil, a highly unsaturated fatty acid derived from fish oil and an ester thereof, at least one selected from vinegar and citrus juice, and the mixture is stirred. Is allowed to stand to separate into an aqueous phase and an oil phase, the aqueous phase is separated and removed, and the oil phase is recovered as a modified fish oil-based material. Then, the modified fish oil-based material is selected from collagen, starch and agar. Characterized by adding at least one, and vegetable oils,
A method for preparing a composition containing a polyunsaturated fatty acid and / or an ester thereof. 7. The modified fish oil-based material based on 100 parts by weight,
7. The method according to claim 5, wherein the vegetable oil is added in a ratio of 10 to 120 parts by weight. 8. With respect to 100 parts by weight of the modified fish oil-based material,
At least one selected from collagen, starch and agar
8. The method according to claim 6, wherein the seed is added in a ratio of 0.05 to 1 part by weight. 9. An emulsion prepared by using the composition according to any one of claims 1 to 4. 10. A food to which the composition according to any one of claims 1 to 4 or the emulsion according to claim 9 is added. 11. A cosmetic to which the composition according to claim 1 or the emulsion according to claim 9 is added.