JP2019170218A - Long-chain polyunsaturated fatty acid-containing oil and fat composition - Google Patents

Abstract

To prevent the occurrence of a fishy odor of a long-chain polyunsaturated fatty acid-containing food.SOLUTION: The present invention provides a long-chain polyunsaturated fatty acid-containing oil and fat containing a specific amount of a malonylisoflavone glycoside poorly soluble in oil and fat.SELECTED DRAWING: None

Description

  The present invention relates to a long-chain polyunsaturated fatty acid-containing oil and fat composition. More specifically, the present invention relates to a long-chain polyunsaturated fatty acid-containing oil and fat composition that suppresses the generation of fishy odor, which is required for foods containing long-chain polyunsaturated fatty acid-containing oils and fats.

  In recent years, it has been known that fats and oils containing long-chain polyunsaturated fatty acids have physiological effects, and these fats and oils are widely used as additions to health foods and feeds for health reasons. Yes. In particular, n-3 long-chain polyunsaturated fatty acids containing 5 or 6 double bonds such as eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA) reduce blood neutral fat and cholesterol, rheumatoid arthritis Many actions such as alleviation of symptoms, prevention of thrombus formation, antiallergic action, etc. have been reported, and many consumers have become recognized as functional foods. In the present specification, fats and oils containing long-chain polyunsaturated fatty acids as constituent fatty acids are referred to as long-chain polyunsaturated fatty acid-containing fats and oils. In 2005, the Ministry of Health, Labor and Welfare established a target intake (adult) of 1 g / day for EPA and DHA in total, and the use of fats and oils containing EPA and DHA at high concentrations is desired. Such long-chain polyunsaturated fatty acid-containing fats and oils are very poor in oxidative stability compared to edible oils such as soybean oil and rapeseed oil, are easily oxidized by oxygen, heat, light, etc., and have adverse health effects. May produce peroxides of concern. (Delete)

  For this reason, techniques for improving oxidation stability are being studied. By adding vitamin C and vitamin E, which are antioxidants commonly used in known fats and oils, roasted sesame oil, ascorbic acid ester, and herbal extracts are added to fats and oils containing polyunsaturated fatty acids. A method of stabilizing the water (Patent Document 1), a method of adding a lipophilic antioxidant (Patent Document 2) containing a bayberry extract, a rosemary extract, etc., a tocopherol / ascorbic acid and a tea extract (Patent Document) 3) A method of adding ascorbic acid or a derivative thereof and another organic acid or a derivative thereof (Patent Document 4), A method of treating edible marine animal and vegetable oil with silica gel using a rosemary extract (Patent Document 5) Although the method of performing a deodorizing treatment in which water vapor is contacted at less than 140 ° C. (Patent Document 6) is known, oxidation of fats and oils containing long-chain polyunsaturated fatty acids is known. Not satisfactory as a method of improving the qualitative, it is desired more excellent oxidation Act.

JP-A-2-189394 JP 2007-185138 A JP-A-9-111237 Japanese Patent Laid-Open No. 9-235584 JP 2000-144168 JP2015-40297

  As described above, Patent Documents 1 to 6 seemed to be a versatile technique for improving the oxidative stability of long-chain polyunsaturated fatty acid-containing fats and oils, but they generated significant fish odor when used for food. It turned out that it was not able to suppress enough.

  Recognizing such prior art, an object of the present invention is to suppress the generation of fishy odor caused by oils containing long-chain polyunsaturated fatty acids.

  As a result of intensive studies in order to solve the above problems, the present inventors have added a specific amount of malonyl isoflavone glycoside, which is hardly soluble in fats and oils, to a long-chain polyunsaturated fatty acid-containing fat. As a result, the inventors have found that the occurrence of water vapor can be remarkably suppressed, thereby completing the present invention.

That is, the present invention is (1) a long-chain polyunsaturated fatty acid-containing oil or fat composition containing 5-1000 ppm of malonyl isoflavone glycoside,
(2) The long-chain polyunsaturated fatty acid-containing oil or fat composition according to (1), wherein the content of the long-chain polyunsaturated fatty acid having 5 or more double bonds in the constituent fatty acid composition is 20% by mass or more,
(3) The oil composition containing a long-chain polyunsaturated fatty acid according to (1) or (2), wherein water phase particles containing malonyl isoflavone glycoside are dispersed in the oil phase,
(4) The long-chain polyunsaturated fatty acid-containing oil or fat composition according to (3), wherein the malonyl isoflavone glycoside is present in a dissolved state in the aqueous phase particles,
(5) The long-chain polyunsaturated fatty acid-containing oil and fat composition according to (4), comprising 0.001 to 1 part by weight of an aqueous phase with respect to 100 parts by weight of the long-chain polyunsaturated fatty acid-containing oil and fat composition,
(6) The oil composition containing a long-chain polyunsaturated fatty acid according to any one of (1) to (5), wherein an oil-soluble emulsifier is dissolved in the oil phase,
(7) A food using the long-chain polyunsaturated fatty acid-containing oil or fat composition according to any one of (1) to (6),
(8) A method for suppressing fish odor generation of a long-chain polyunsaturated fatty acid-containing oil or fat composition, comprising 5 to 1000 ppm of malonyl isoflavone glycoside,
(9) A long-chain polyunsaturated fatty acid-containing oil or fat composition containing 5-1000 ppm of malonyl isoflavone glycoside is used. A method for suppressing the generation of fish odor,
(10) Long chain polyunsaturated fatty acid containing 5-1000 ppm of malonyl isoflavone glycoside, in which water phase particles in which malonyl isoflavone glycoside is dissolved are dispersed in an oil phase in which an oil-soluble emulsifier is dissolved Production method of oil and fat composition,
(11) The long-chain polyunsaturated fatty acid-containing oil / fat composition according to (10), wherein 0.001 to 1 part by weight of the aqueous phase is dispersed with respect to 100 parts by weight of the long-chain polyunsaturated fatty acid-containing oil / fat composition. Is a manufacturing method.

According to the present invention, it is possible to suppress the generation of fishy odor, and it is possible to use long-chain polyunsaturated fatty acid-containing fats and oils that are highly adaptable to foods at a lower cost than before.
As a preferred embodiment, the generation of fishy odor of long-chain polyunsaturated fatty acid-containing fats and oils can be suppressed over a long period. Moreover, also in foods using the long-chain polyunsaturated fatty acid-containing fats and oils of the present invention, the generation of fishy odor caused by the long-chain polyunsaturated fatty acid-containing fats and oils can be suppressed.
As a more preferred embodiment, by adding a relatively small amount of an antioxidant substance, oxidation stability can be improved in addition to suppression of fish odor generation.
Moreover, the long-chain polyunsaturated fatty acid-containing fats and oils of the present invention do not need to be encapsulated, emulsified or powdered for the purpose of avoiding contact with air, unlike conventional long-chain polyunsaturated fatty acid-containing fats and oils. Therefore, although it can be distributed in liquid form, it can be used without being limited to the use range in liquid form. Specifically, the long-chain polyunsaturated fatty acid-containing fats and oils obtained by the production method of the present invention can be used to obtain emulsions, process into powders and capsules, etc. It can be used for a wider range of applications, including the range of use of polyunsaturated fatty acid-containing fats and oils.

  The long-chain polyunsaturated fatty acid-containing fat of the present invention contains a long-chain polyunsaturated fatty acid having 5 or more double bonds and 20 or more carbon atoms. The type of fatty acid having 5 or more double bonds is not particularly limited, but docosahexaenoic acid (DHA; C22: 6), eicosapentaenoic acid (EPA; C20: 5), docosapentaenoic acid (DPA; C22: 5) Can be illustrated. The content of the long-chain polyunsaturated fatty acid in the constituent fatty acid composition is preferably 20% by mass or more, and examples include oils and fats obtained from various animal and vegetable oils such as fish oil and vegetable oils, microorganisms, and algae. When the content of the long-chain polyunsaturated fatty acid is less than 20% by mass, it is not preferable in terms of cost and production efficiency. The effect of the present invention is also effective in a long-chain polyunsaturated fatty acid-containing blended fat and oil obtained by mixing two or more of the long-chain polyunsaturated fatty acid-containing fat and oil of the present invention and other fats and oils.

In the present invention, it is desirable that an oil-soluble emulsifier is dissolved in the oil phase. In addition, an oil-soluble emulsifier is an emulsifier which melt | dissolves in fats and oils, and refers to the emulsifier whose HLB is 7 or less in this invention. As the oil-soluble emulsifier, one or more selected from polyglycerin ester, sugar ester, sorbitan ester, and monoglycerin fatty acid ester is desirable, more desirably polyglycerin ester, sugar ester, and distilled monoglyceride are preferable, and polyglycerin ester is particularly preferable. Of these, polyglycerin condensed ricinoleate is most preferred. The polyglycerol condensed ricinoleic acid ester may be abbreviated as PGPR. The amount of the oil-soluble emulsifier in the oil phase is preferably 0.004 to 1% by mass, more preferably 0.01 to 0.3% by mass. By using an appropriate amount of an appropriate emulsifier, a long-chain polyunsaturated fatty acid-containing oil and fat that can efficiently suppress the generation of fishy odor can be obtained.

In the present invention, the source of the effect of suppressing the generation of fishy odor is presumed to be malonyl isoflavone glycoside.
The content of malonyl isoflavone glycoside is 5-1000 ppm, preferably 5-800 ppm, more preferably 5-500 ppm. If the content of malonyl isoflavone glycoside is less than the lower limit, the ability to suppress the generation of fishy odor will be insufficient, such being undesirable. Moreover, since it will become bitter and unpleasant if it exceeds an upper limit, there is no necessity of making it contain exceeding an upper limit. The malonyl isoflavone glycoside used in the present invention includes malonyl daidzin, malonyl genistin and the like that have been confirmed to exist as the main component of the isoflavone compound in soybean. In the present invention, malonyl isoflavone glycoside that is soluble in water and hardly soluble in fats and oils is contained in the fats and oils. As a preferred embodiment, the long-chain polyunsaturated fatty acid-containing oil and fat composition of the present invention can suppress the generation of fishy odor not only immediately after production but also after storage.

  Furthermore, content of the preferable malonyl isoflavone glycoside for suppressing generation | occurrence | production of the fishy odor after a preservation | save and improving a flavor is 10-500 ppm, More preferably, it is 30-500 ppm, More preferably, it is 60-500 ppm.

  As the malonyl isoflavone glycoside used in the present invention, for example, an isoflavone compound powder produced from okara or defatted soybean or a composition contained in an isoflavone-containing composition extracted and concentrated from a soybean goblet can be used. . The content of malonyl isoflavone glycoside in the isoflavone-containing composition as described above is preferably 10% by weight or more, more preferably 20% by weight or more, and most preferably 30% by weight or more. In order to increase the content of malonyl isoflavone glycoside when the content of malonyl isoflavone glycoside in the isoflavone containing composition is 10% by weight or less, a relatively large amount of isoflavone containing composition that is hardly soluble in fats and oils is blended When it does, since it becomes easy to produce turbidity in oil and fat, it is not preferable.

  In addition, the isoflavone-containing composition containing malonyl isoflavone glycoside includes isoflavone glycoside and aglycone, and the present invention has no problem as long as it contains malonyl isoflavone glycoside in the above content. Can be used for As a preferred embodiment of the present invention, it is preferable to contain a malonyl isoflavone glycoside dissolved in water phase particles. Such an embodiment is preferable because fish odor can be suppressed to the maximum.

  The long-chain polyunsaturated fatty acid-containing fat containing the malonyl isoflavone glycoside of the present invention is prepared by dissolving a material containing malonyl isoflavone glycoside in water to prepare an aqueous phase. Further, if necessary, an oil-soluble emulsifier is dissolved in fats and oils to prepare an oil phase. Next, the long-chain polyunsaturated fatty acid-containing oil and fat can be obtained by mixing the water phase into the oil phase and emulsifying it into a water-in-oil type.

  The preferable aspect of the long-chain polyunsaturated fatty acid-containing fat / oil of the present invention is more preferably 0.001 to 1 part by weight of an aqueous phase with respect to 100 parts by weight of the long-chain polyunsaturated fatty acid-containing fat / fat composition. Is 0.003 to 0.8 part by weight, more preferably 0.005 to 0.5 part by weight.

(Quantitative method for isoflavones)
A sample corresponding to 1 to 10 mg as an isoflavone was accurately weighed, and 25 mL of 70% (v / v) ethanol was added thereto. After stirring and extracting at room temperature for 30 minutes, the mixture was centrifuged to obtain an extract. The residue was subjected to the same extraction operation twice more. A total of 3 times of the extract was made up to a volume of 100 mL with 70% (v / v) ethanol, and filtered through a 0.45 μm PVDF filter as a test solution.
There are 12 types of standard tests for isoflavones, namely daidzin, genistin, glycitin, daidzein, genistein, glycitein, malonyldaidine, malonylgenistin, malonylglycitin, acetyldidine, acetylgenistin, acetylglycitin (Wako Pure Chemical Industries, Ltd.) Was used to confirm approximately the same retention time peak. In the quantitative test, 12 kinds of isoflavone concentrations (Daidin equivalent values) were quantified using a Daidine standard product, and the true isoflavone concentration was calculated by multiplying by the following quantitative coefficient.
Quantitative coefficient of isoflavone: daidzin (1.000), genistin (0.814), glycitin (1.090), malonyl daidzin (1.444), malonylgenistin (1.095), malonylglycitin (1.351) , Acetyldidine (1.094), acetylgenistin (1.064), acetylglycitin (1.197), daidzein (0.583), genistein (0.528), glycitein (0.740) and various isoflavone concentrations The amount of isoflavones was determined from the sum of The HPLC conditions of the test solution and standard solution were as follows. The malonyl isoflavone glycoside content was calculated by the total amount of malonyl daidzin, malonylgenistin, and malonyl glycitin.

(HPLC conditions)
Column: YMC-Pack ODS-AM-303 (4.6 × 250 mm)
Mobile phase: Liquid A acetonitrile: water: acetic acid = 15: 85: 0.1 (v / v / v)
Liquid B acetonitrile: water: acetic acid = 35: 65: 0.1 (v / v / v)
Liquid A → Liquid B Linear concentration gradient (50 minutes)
Flow rate: 1.0 ml / min Temperature: 25 ° C
Detection: UV254nm
Injection volume: 10 μl

  EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated in detail, the spirit of this invention is not limited to a following example. In the examples, “%” and “parts” mean weight basis.

Study 1
Preparation of long chain polyunsaturated fatty acid containing fat

  In accordance with the formulation shown in Table 1, a long-chain polyunsaturated fatty acid-containing oil and fat was prepared in accordance with the fish odor control. The preparation method was in accordance with “○ Method for preparing fish odor generation-suppressed long-chain polyunsaturated fatty acid-containing fat”.

(About the additive used)
-Polyglycerin condensed ricinoleic acid ester “CRS-75” manufactured by Sakamoto Pharmaceutical Co., Ltd. was used as the oil-soluble emulsifier.
-“Soyaflavone HG” manufactured by Fuji Oil Co., Ltd. was used as an isoflavone material containing malonyl isoflavone glycoside.
-Among oil-soluble antioxidants, "RIKEN E Oil 705" manufactured by Riken Vitamin was used as vitamin E, and "Vitamin C Palmitate" manufactured by Mitsubishi Chemical Foods was used as vitamin C palmitate.
Of the water-soluble antioxidants, “L-ascorbic acid” manufactured by Pure Chemical Co., Ltd. was used as vitamin C, and “Sunphenon 90S” manufactured by Taiyo Chemical Co., Ltd. was used as the tea extract.
-"Soy white squeezed oil" manufactured by Fuji Oil Co., Ltd. was used as a fat for preparing DHA / EPA.

○ Prevention of fish odor generation Method for preparing long-chain polyunsaturated fatty acid containing fat To 100 parts of deacidified bran oil (acid value = 0.10, peroxide value = 5.5, iodine value = 184, EPA + DHA content = 28.0%), 3.0 parts of activated clay was added, and the degree of vacuum was 1 After decolorization treatment at 6 kPa (12 torr) and 120 ° C. for 15 minutes, the solution was separated by filter paper. Next, steam deodorization treatment was performed on 100 parts of decolorized oil at a vacuum degree of 0.4 kPa (3 torr) or less, 180 ° C., 180 minutes, and 3 parts of steam added to obtain purified fish oil. The POV immediately after production was 0 meq / kg, and the EPA + DHA content was 27.5%.
2. In blending, raw materials classified into the oil phase were melted and mixed to prepare an oil phase with an EPA + DHA content of 26.1%.
3. In blending, raw materials classified as aqueous phase were dissolved in water to prepare an aqueous phase. In Comparative Example 2, a powdery isoflavone material was mixed with an oil phase to prepare.
4). The water phase was mixed with the oil phase and emulsified to obtain a water-in-oil emulsion.

○ Sensory Evaluation Method for Long-Chain Polyunsaturated Fatty Acid-Containing Fats and Oils The long-chain polyunsaturated fatty acid-containing fats and oils immediately after production have a taste of fish as a fish odor, and ten-level sensory evaluation by 10 panelists. went. The evaluation results are shown in Table 2.
Oils and fats with an evaluation of 4 or more were judged good.
Fish odor: The larger the number, the weaker the fish odor, and the smaller the number, the stronger the fish odor.

○ Preservation test method for long-chain polyunsaturated fatty acid-containing fats and oils · Put 50 g of uniformly mixed fats and oils in a 100 ml glass bottle and seal.
Store the glass bottle at 40 ° C. for 14 days.
・ Peroxide value (POV) and flavor evaluation are performed after storage.

○ Sensory evaluation method of stored long-chain polyunsaturated fatty acid-containing fats and oils The long-chain polyunsaturated fatty acid-containing fats and oils deteriorated by the storage test are 10 steps by 10 panelists, with the taste evaluation item being fish odor. It was performed by sensory evaluation. The evaluation results are shown in Table 2.
Oils and fats with an evaluation of 4 or more were judged good.
Fish odor: The larger the number, the weaker the fish odor, and the smaller the number, the stronger the fish odor.

(Discussion)
-From Examples 1-6 and Comparative Examples 1-8, if it was normal, it confirmed that generation | occurrence | production of the fish odor concerning an invention was suppressed notably on the conditions which fish odor generate | occur | produces and are not suitable for food. Moreover, since POV increased similarly to the comparative example 1, it confirmed that this effect was not acquired with the conventional antioxidant.
-From Examples 7-8, it confirmed that the increase in POV was suppressed and fish odor was further suppressed by using together with a known antioxidant.
-From the comparison of Example 4 and Comparative Example 2, in the comparative example 2, the oil and fat composition in which the isoflavone material was not dissolved in water and was dispersed in the fat and oil in a solid state, the fish odor could not be suppressed. . From Example 4, it is clear that the effect of suppressing fishy odor is enhanced by dispersing the isoflavone material in an oil and fat state in the form of an aqueous solution.

Study 2
Using the long-chain polyunsaturated fatty acid-containing oil and fat prepared in Study 1, the effect was verified by preparing a sand filling.

  The composition of the sand filling is shown in Table 3. The sand filling was prepared in accordance with “○ Preparation method of sand filling containing long-chain polyunsaturated fatty acid”.

○ Preparation method of long-chain polyunsaturated fatty acid-containing sand filling Parky Y (melting point 33 ° C, Fuji Oil Co., Ltd.) consisting of fat and oil transesterified oil mainly containing palm oil and fat containing 12 or less carbon atoms 37.5 parts dissolved at 60 ° C., and then cooled to 23 ° C. while stirring with a whipper to make a paste, 2.5 parts long-chain polyunsaturated fatty acid-containing oil and fat, 40 parts sugar, Sand filling was prepared by adding 20 parts of whole milk powder and whipping. The specific gravity of the sand filling was 0.85.

○ Sensory evaluation method of sand filling Sand filling immediately after trial production was performed by sensory evaluation in 10 stages by 10 panelists, with the flavor evaluation item being fish odor. The evaluation results are shown in Table 4.
Oils and fats with an evaluation of 5 or more were judged good.
Fish odor: The larger the number, the weaker the fish odor, and the smaller the number, the stronger the fish odor.

○ Preservation test method for fats and oils containing long-chain polyunsaturated fatty acids ・ Fill 80g in a 100ml plastic container and seal.
Store the container at 25 ° C. for 180 days.
・ After storage, evaluate the flavor.

○ Sensory evaluation method of preserved sand filling Sand filling deteriorated by a preservation test was performed by sensory evaluation in 10 stages by 10 panelists, with the taste evaluation item being fish odor. The evaluation results are shown in Table 4.
Oils and fats with an evaluation of 5 or more were judged good.
Fish odor: The larger the number, the weaker the fish odor, and the smaller the number, the stronger the fish odor.

(Discussion)
-From Examples 1-8 and Comparative Examples 1-8, even in foods, the occurrence of fishy odor according to the present invention is significantly suppressed under conditions where fishy odor is generated and is not suitable for food use. It was confirmed.
-From the comparison of Example 4 and Comparative Example 2, in the comparative example 2, the oil and fat composition in which the isoflavone material was not dissolved in water and was dispersed in the fat and oil in a solid state, the fish odor could not be suppressed. . From Example 4, it is clear that the effect of suppressing fishy odor is enhanced by dispersing the isoflavone material in an oil and fat state in the form of an aqueous solution.

  According to the present invention, it is possible to use long-chain polyunsaturated fatty acid-containing fats and oils that suppress the generation of fishy odor and are highly adaptable to foods at a lower cost than before.

Claims (11)

  A long-chain polyunsaturated fatty acid-containing oil or fat composition containing 5-1000 ppm of malonyl isoflavone glycoside.   The long-chain polyunsaturated fatty acid-containing oil or fat composition according to claim 1, wherein the content of the long-chain polyunsaturated fatty acid having 5 or more double bonds in the constituent fatty acid composition is 20% by mass or more.   The oil composition containing a long-chain polyunsaturated fatty acid according to claim 1 or 2, wherein water phase particles containing malonyl isoflavone glycoside are dispersed in the oil phase.   The long-chain polyunsaturated fatty acid-containing oil or fat composition according to claim 3, wherein the malonyl isoflavone glycoside is present in a state dissolved in the aqueous phase particles.   The long-chain polyunsaturated fatty acid-containing oil or fat composition according to claim 4, comprising 0.001 to 1 part by weight of an aqueous phase with respect to 100 parts by weight of the long-chain polyunsaturated fatty acid-containing oil and fat composition.   The oil-and-fat composition containing a long-chain polyunsaturated fatty acid according to any one of claims 1 to 5, wherein an oil-soluble emulsifier is dissolved in the oil phase.   The foodstuff using the long-chain polyunsaturated fatty acid containing oil-fat composition of any one of Claims 1-6.   A method for suppressing the generation of fishy odor in a long-chain polyunsaturated fatty acid-containing oil composition comprising 5 to 1000 ppm of malonyl isoflavone glycoside.   Fish odor generation of food containing a long-chain polyunsaturated fatty acid-containing oil or fat composition, characterized by using a long-chain polyunsaturated fatty acid-containing oil or fat composition containing 5-1000 ppm of malonyl isoflavone glycoside How to suppress.   A long-chain polyunsaturated fatty acid-containing oil and fat composition containing 5-1000 ppm of malonyl isoflavone glycoside, in which water phase particles in which malonyl isoflavone glycoside is dissolved are dispersed in an oil phase in which an oil-soluble emulsifier is dissolved Manufacturing method.   The long-chain polyunsaturated fatty acid-containing oil / fat composition according to claim 10, wherein the aqueous phase is dispersed in an amount of 0.001 to 1 part by weight per 100 parts by weight of the long-chain polyunsaturated fatty acid-containing oil / fat composition. Manufacturing method.