Highly unsaturated fatty acids-containing emulsified formulation

Abstract

To provide a highly unsaturated fatty acids-containing emulsified formulation that is highly water-soluble and can be distributed and stored at room temperature and a method for manufacturing the same.SOLUTION: There is provided an emulsified formulation that contains (A) highly unsaturated fatty acid-containing fats and oils; (B) (b1) oil-soluble radical-scavenging antioxidants having a phenolic hydrogen and / or (b2) oil-soluble antioxidants of oxidation-reduction type; and (C) (c1) water-soluble radical-scavenging antioxidants with phenolic hydrogen and / or (c2) water-soluble antioxidants of oxidation-reduction type, wherein the content of (A) is 5 mass% to 60 mass%, the total content of (B) and (C) is 0.01 mass% to 10 mass%, the ratio of (B) / (C) is 0.2 to 5, and the emulsified particle diameter is 150 nm or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention provides a method for making oils and fats containing highly unsaturated fatty acids water-soluble and stable against oxidation, and The present invention relates to an emulsion preparation containing highly unsaturated fatty acids that can be added or blended into processed foods and the like. [Background technology]

[0002] Eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA), arachidonic acid (A Polyunsaturated fatty acids such as α-linolenic acid, γ-linolenic acid, and α-linolenic acid are effective in preventing arteriosclerosis and improving brain function. There have been many reports on the biological regulation functions of the enzymes, such as activation, and their physiological functions have been attracting attention. These polyunsaturated fatty acids are not only in the form of free fatty acids but also in the form of alkyl esters, triacylglycerols, and It exists in the body in various forms of fats and oils, such as glycerol, phospholipids, and glycolipids, but is generally found in fish oil. It is supplied as fats and oils in the form of triacylglycerols, such as vegetable oils like perilla oil and linseed oil. On the other hand, processed foods such as beverages contain a large amount of water, so oils and fats It is difficult to mix it as it is, and preparation processing such as emulsification and dispersion is required. The formulations are available in various forms such as emulsions and powders.

[0003] On the other hand, polyunsaturated fatty acids have many unsaturated bonds, making them unstable to oxidation and difficult to process. However, there is a problem in that the product is oxidized and degraded during storage, resulting in deterioration in quality such as odor and discoloration. Generally, tocopherol, ascorbic acid, butylhydroxyanisole, etc. are used to prevent the oxidation of fats and oils. The use of antioxidants such as butylated hydroxytoluene (BHA) and butylhydroxytoluene (BHT) is common. Although it is effective, it is not effective enough when simply added to oils containing highly unsaturated fatty acids with many unsaturated bonds. Furthermore, in systems containing compounds with different polarities, such as emulsions, the results are not comparable to those of homogeneous systems. It has also been reported that different antioxidant activities are exhibited (Non-Patent Document 1).

[0004] Various methods have been reported to stabilize emulsion preparations containing highly unsaturated fatty acids. For example, tocopherol, phospholipids, ascorbic acid, etc. are added to oils and seafood extracts to form polysaccharides. A method of emulsifying with an emulsifier such as glycerin fatty acid ester (Patent Document 1), a method of adding ascorbic acid to the aqueous phase, Water-soluble antioxidants such as acetic acid and erythorbic acid are added, and sesame oil and ascorbic acid are added to the oil phase. A method of emulsifying by adding an oil-soluble antioxidant-containing component such as ester or tocopherol (Patent Document 2) Antioxidants such as ascorbic acid and catechin and polyhydric alcohol are added, and HLB10 The above polyglycerin fatty acid ester, sucrose fatty acid ester, and lecithin are used to make emulsions. However, in all of these cases, the type and amount of antioxidant components are unclear. In terms of balance, the oxidation stability is not sufficient. [Prior art documents] [Non-patent literature]

[0005] [Non-Patent Document 1] W. Porte et al, J. Agric. Food Chem., 37, 615 (1989) [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 5-86395 [Patent Document 2] Japanese Patent Application Publication No. 6-298642 [Patent Document 3] Japanese Patent Application Publication No. 7-227227 Summary of the Invention [Problem to be solved by the invention]

[0007] Polyunsaturated fatty acids or fats containing polyunsaturated fatty acids and two types of phenolic hydrogen An oil-soluble radical scavenging antioxidant having two kinds of oxidation-reduction types and / or an oil-soluble By combining it with a water-soluble antioxidant and adjusting the blending ratio appropriately, it can be used in processed foods containing water. A technique for obtaining a water-soluble preparation containing highly unsaturated fatty acids that can be stably formulated into (Patent Publication No. 2022-29516). As a result, the highly unsaturated fatty acid-containing water-soluble preparations described in Patent Documents 1 to 3 The above-mentioned problem has been significantly improved. Water-soluble preparations containing highly unsaturated fatty acids must be distributed and stored in a refrigerated environment and must have sufficient oxidation stability. Therefore, highly unsaturated fatty acids that can be distributed and stored at room temperature There was a demand for an emulsion formulation containing this ingredient. From the above, an object of the present invention is to provide a highly unsaturated fat that is insoluble in water and has low oxidation stability. It can stably dissolve oils and fats containing acids in water and can be stably blended into processed foods containing water. and to provide an emulsion preparation containing highly unsaturated fatty acids that can be distributed and stored at room temperature. do. [Means for solving the problem]

[0008] The present invention relates to the following. [1] (A) Oils and fats containing highly unsaturated fatty acids and (B) (b1) oils having phenolic hydrogen (b2) an oil-soluble radical scavenging antioxidant and / or (b3) an oil-soluble antioxidant exhibiting oxidation-reduction properties (C) (c1) a water-soluble radical-scavenging antioxidant having a phenolic hydrogen atom and and / or (c2) a water-soluble antioxidant exhibiting oxidation-reduction properties, and an emulsion preparation exhibiting sufficient solubility, the content of (A) being 5% by mass to 60% by mass, (B) and The total content of (C) is 0.01% by mass to 10% by mass, and the ratio of (B) / (C) is 0.2 to 5 and an emulsion preparation containing highly unsaturated fatty acids, wherein the emulsion particle size is 150 nm or less. [2] (b1) is one of tocopherol, gallic acid fatty acid ester, BHA, and BHT (b2) is selected from the group consisting of ascorbic acid fatty acid esters and ubiquinone. and (c1) is one or more of tea catechins, anthocyanins, and chlorogenic acid. One or more of the above, and (c2) is ascorbic acid and its metal salts, erythorsol [1] The highly unsaturated fatty acid-containing product is one or more of acetic acid and its metal salts. Emulsifying preparation. [3] (A) Polyunsaturated fatty acids are eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA), [1] or [2], which contains either DHA or α-linolenic acid. Contains emulsified formulation. [4] Oil was extracted from the highly unsaturated fatty acid-containing emulsion preparation stored at 40°C, and the standard oil content was measured. When measuring the peroxide value (POV) by potentiometric titration, the number of times that POV30 is reached is The highly unsaturated fatty acid-containing emulsion preparation according to [1] or [2], wherein the time required for the emulsion preparation to reach the intended state is 90 days or more. [5] The following ingredients (A), (B), and (C): (A) oils and fats containing highly unsaturated fatty acids, (B) (b 1) an oil-soluble radical-scavenging antioxidant having a phenolic hydrogen atom and / or (b2) an acid (C) (c1) Water-soluble antioxidants having phenolic hydrogen atoms (c2) a radical scavenging antioxidant and / or (c3) a water-soluble antioxidant exhibiting an oxidation-reduction type A method for producing oils and fats containing highly unsaturated fatty acids, comprising a step of mixing (A) and (B). The content of (B) and (C) is 5% by mass to 60% by mass, and the total content of (B) and (C) is 0.01% by mass to 10% by mass. The ratio of (B) / (C) is 0.2 to 5, and the emulsion particle size is adjusted to 150 nm or less. The method for producing an emulsion preparation containing highly unsaturated fatty acids further comprises the step of: [6] (b1) is one of tocopherol, gallic acid fatty acid ester, BHA, and BHT or two or more of the above, and (b2) is one of ascorbic acid fatty acid esters and ubiquinone. one or more kinds, and (c1) is selected from the group consisting of tea catechins, anthocyanins, and chlorogenic acid. (c2) is one or more of ascorbic acid and its metal salts, erythorbic acid and The highly unsaturated fatty acid-containing emulsion according to [5], which is one or more of the following: Manufacturing method of the agent. [7] The polyunsaturated fatty acid (A) contains any one of DHA, EPA, and α-linolenic acid. A method for producing an emulsion preparation containing highly unsaturated fatty acids according to [5] or [6]. [Effects of the Invention]

[0009] The present invention provides improved oxidation stability and water resistance compared to conventional water-soluble formulation techniques containing highly unsaturated fatty acids. It has excellent compounding stability in processed foods containing water, and is highly unsaturated fatty acids in processed foods containing water. Fat and oil containing fatty acids can be effectively added and blended. In addition, conventionally, it was necessary to distribute and store the product in a refrigerated state at about 5°C. The emulsion formulation containing highly unsaturated fatty acids has improved oxidation stability compared to conventional formulations, resulting in a reduction of approximately 2%. It is expected that it will be possible to distribute and store it at room temperature, between 0℃ and 25℃. DETAILED DESCRIPTION OF THE INVENTION

[0010] The present invention will be described below with reference to the following embodiments, but the present invention is not limited to the following embodiments. It is not something that can be done.

[0011] [Highly unsaturated fatty acid-containing emulsion preparation] The present invention provides (A) an oil or fat containing highly unsaturated fatty acids; (B) (b1) an oil-soluble radical scavenging antioxidant having a phenolic hydrogen atom and / or (b2) an oil-soluble antioxidant exhibiting oxidation-reduction properties; (C) (c1) A water-soluble radical-scavenging antioxidant having a phenolic hydrogen atom and / or (c2) a water-soluble antioxidant exhibiting an oxidation-reduction type; An emulsified preparation that exhibits good solubility in water, The content of (A) is 5% by mass to 60% by mass, The total content of (B) and (C) is 0.01% by mass to 10% by mass, The ratio of (B) / (C) is 0.2 to 5; The present invention relates to an emulsion preparation containing highly unsaturated fatty acids, the emulsion particle size of which is 150 nm or less.

[0012] This highly unsaturated fatty acid-containing emulsion formulation has higher oxidation stability and is more effective in processed foods containing water than conventional products. It has excellent compounding stability in products. It is also used in processed foods containing water as a highly unsaturated fatty acid. Furthermore, conventionally, refrigerated distribution is carried out at around 5°C. However, emulsion formulations containing highly unsaturated fatty acids have better oxidation stability than conventional formulations. It is expected that this improvement will enable distribution and storage at room temperature, approximately 20℃ to 25℃. Each requirement will be explained below.

[0013] (A) Oils and fats containing highly unsaturated fatty acids are used as foods or food additives. There is no particular limitation on the type of polyunsaturated fatty acid. For example, eicosapentaenoic acid is EPA, docosahexaenoic acid (DHA), arachidonic acid (ARA), alpha-linolenic acid Acid, gamma-linolenic acid, eicosatetraenoic acid (ETA), eicosatrienoic acid (ETE) , linoleic acid, stearidonic acid (SDA), etc., and as for fats and oils, triacylglycerol These include glycerol, phospholipids, glycolipids, etc., and one or more of these may be used. Polyunsaturated fatty acids are fatty acids that have two or more unsaturated bonds.

[0014] (A) The content of oils and fats containing highly unsaturated fatty acids is the total amount of highly unsaturated fatty acid-containing emulsion preparations. Relative to the total mass of the cellulose, the content is 5% by mass to 60% by mass, preferably 7% by mass to 50% by mass, and more preferably 1% by mass. The blending amount is 0% by mass to 40% by mass. If the blending amount is less than 5% by mass, a large blending amount is required. Economical problems may arise, and if the content exceeds 60% by mass, problems may arise in the stability of the formulation, such as separation and oil floating. This causes problems and is undesirable.

[0015] (b1) The oil-soluble radical-scavenging antioxidant having phenolic hydrogen is used in food or There is no particular limitation on the type of additive as long as it can be used as a food additive. For example, tocopherol esters of gallic acid, BHA (butyl hydroxyanisole), BHT (dibutyl Hydroxytoluene), oil-soluble catechin, etc., and one or more of these may be used. It is possible.

[0016] (b2) Oil-soluble antioxidants that exhibit oxidation-reduction are not used as foods or food additives. There are no particular limitations on the type of substance, as long as it can be used. Examples include ubiquinones, ascorbic acid esters, etc. These may be used alone or in combination of two or more.

[0017] (c1) The water-soluble radical-scavenging antioxidant having phenolic hydrogen is used in food or There are no particular limitations on the type of additives that can be used as food additives, including anthocyanins, Water-soluble polyphenols such as tea extracts and coffee extracts, especially anthocyanins and tea catechins Examples of such compounds include chlorogenic acid and chlorogenic acid, and these compounds can be used alone or in combination.

[0018] (c2) Water-soluble antioxidants that exhibit oxidation-reduction are not used as foods or food additives. There are no particular limitations on the type of substance, as long as it can be used in a suitable manner. Examples include ascorbic acid and its salts, erythorbic acid, and the like. bic acids and their salts, especially ascorbic acid and its metal salts, erythorbic acid and its salts Metal salts are exemplified, and one or more of these can be used. However, ascorbic acid Acid and erythorbic acid are excluded from the above antioxidants because they increase the peroxide value. It is preferable to

[0019] Let the sum of (b1) and (b2) be (B), and the sum of (c1) and (c2) be (C). When the total amount of the antioxidants (B) and (C) used in the present invention is Preferably, the content is 0.01% by mass to 10% by mass relative to the entire unsaturated fatty acid-containing emulsion preparation. , more preferably 0.03% by mass to 8% by mass, and even more preferably 0.05% by mass to 6% by mass. If the blending amount is less than 0.01 mass %, the antioxidant effect is insufficient, and If the content exceeds 100% by mass, the balance of the entire formulation is lost, causing problems such as separation and coloration. Not likely.

[0020] The ratio of (B) to (C), (B) / (C), is preferably 0.2 to 5, more preferably The ratio is preferably 0.3 to 4, and more preferably 0.4 to 3. When the ratio is less than 0.2 On the other hand, if it exceeds 5, a sufficient antioxidant effect cannot be obtained, which is not preferable.

[0021] The emulsion particle size of the highly unsaturated fatty acid-containing emulsion preparation is preferably 150 nm or less. The emulsion particle size of 150 or more provides sufficient oxidation stability. The method for adjusting the emulsion particle size is based on the type and amount of fat and oil and the emulsifier. The conditions vary depending on the type of combination, but generally the emulsion particle size is determined by the amount of shearing during the emulsification process. In the case of a homomixer, the shear energy is inversely proportional to the amount of shear energy, which is indicated by the number of rotations. It is expressed by multiplying the shear strength by the shear time. For specific examples of emulsion preparation, see the Examples section. It was written.

[0022] Incidentally, various studies have been conducted on the emulsification stability, oxidation stability, etc. of edible oils. (For example, Goro Kajimoto, Stability of Edible Oils, Cooking Science, 1981, Vol. 14, No. 4) (See, for example, No. 147-202.) The term "emulsion stability" used here refers to the stability of the emulsion against phase inversion and the oil-water transition. "Oxidative stability" refers to the degree to which a substance can exist stably without separating into two substances. This refers to the degree to which it is difficult to accept.

[0023] For example, it has been reported that there is a correlation between emulsion stability and emulsion particle size. (Toshiyuki Suzuki, Fundamentals of Emulsification Technology (Phase Diagrams and Emulsions), Journal of the Japanese Society of Cosmetic Chemists, 2010, (See Vol. 44, No. 2, pp. 103-117.) However, there is a correlation between oxidative stability and emulsion particle size. was not revealed. Another study found that fish oil and soybean oil emulsions exhibited a particle size range of 6.5 to 39.0 μm. The effect of emulsion particle size on the oxidative stability of emulsions has been investigated (e.g., For example, Kazuo Miyashita, Study on the oxidation stability of unsaturated lipids in aqueous systems, Oleoscience, 2006 (See Vol. 6, No. 12, pp. 585-591.) Here, the soybean oil emulsion is The smaller the particle size, the lower the oxidation stability, while the larger the particle size of fish oil, the lower the oxidation stability. The opposite results have been reported. Further studies have shown that glycerol docosahexaenoate, glyceryl trilinoleate, and The results of a survey on the oxidation stability and emulsion particle size of triacylglycerols were reported. (Naohiro Gotoh et al, J. Oleo Sci., 59, (12), 631-639 (2010)). However, There was no mention of the relationship between oxidative stability and emulsion particle size.

[0024] Thus, the relationship between oxidative stability and emulsion particle size in emulsion preparations containing highly unsaturated fatty acids has been previously Therefore, in the present invention, highly unsaturated fats When the emulsion particle size of the acid-containing emulsion preparation is 150 nm or less, sufficient oxidation stability is obtained. It is truly surprising to find that.

[0025] In addition to the above-mentioned documents, Japanese Patent Application Laid-Open No. 08-154576 (particularly, Example 3), 272892 (particularly Example 1), WO 2004 / 048496 (particularly In Example 3), an emulsion composition containing highly unsaturated fatty acids is disclosed. However, there is no description suggesting a correlation between oxidation stability and emulsion particle size. In this case, Example 3 of JP-A-08-154576 was prepared as a reference example, and the results are compared with those of the present invention. The comparison revealed a clear difference between the present invention and the reference example.

[0026] (others) The highly unsaturated fatty acid-containing emulsion preparation may contain any of the ingredients used in publicly known foods, as long as it does not impair the effects of the present invention. Emulsifiers that can be used include polyglycerol esters, monoglycerides, etc. esters, sugar esters, sorbitan esters, lecithins, thickening polysaccharides, etc. These may be added alone or in combination of two or more.

[0027] The highly unsaturated fatty acid-containing emulsion preparation may be any of known foods or food additives as long as it does not impair the effects of the present invention. For example, the base ingredients may contain oil, water, alcohol, etc. As an excipient, sugars, polysaccharides, starches, and as an added ingredient, organic acids It may contain additives such as inorganic salts, preservatives, fragrances, chelating agents, specific gravity adjusters, and viscosity adjusters. can.

[0028] There is no particular limitation on the machinery used to manufacture highly unsaturated fatty acid-containing emulsion preparations. Not only mixers, agitators, dispersers, homomixers, homogenizers, high pressure Homogenizer, ultra-high pressure homogenizer, ball mill, colloid mill, planetary mill, wet type OB mill, rotary grinder, kneader, kneader, spray dryer, vacuum dryer, free Machines such as a screen dryer and a vibrating screen can be used alone or in combination.

[0029] The form of the highly unsaturated fatty acid-containing emulsion preparation is not particularly limited as long as it does not impair the effects of the invention. In the usual preparation method, it is often in the form of a liquid formulation, but it is mixed with excipients and spray-dried. It can also be used by powdering it through processes such as drying, vacuum drying, freeze drying, etc. [Example]

[0030] The present invention will now be described in detail with reference to examples, but the present invention is not limited to these examples. It's not something like that.

[0031] In the present examples and comparative examples, DHA algal oil (manufactured by BASF) was used as the DHA-containing fat. EPA (Maruha Nichiro) is an oil containing EPA, and flaxseed oil is an oil containing α-linolenic acid. Ni-oil (manufactured by Nisshin Oil Mills), Emix 70 (manufactured by Mitsubishi Chemical Foods) as tocopherol (manufactured by Fuji Chemical Industry Co., Ltd.), BHA, BHT (manufactured by JGC Universal Co., Ltd.) Ascorbic acid palmitate, sodium ascorbate, ascorbic acid, Sodium erythorbate, coenzyme Q10 (both manufactured by Watanabe Chemical Co., Ltd.), tea catechin Tocopherol, blueberry extract, and coffee extract (all manufactured by Tokiwa Plant Chemical Co., Ltd.) were used. For rolls, the tocopherol concentration of the raw material is calculated based on the concentration in the raw oil and fat, and then added. The amounts added in the table are expressed as converted total amounts added.

[0032] Preparation Example 1: Preparation of highly unsaturated fatty acid-containing emulsion preparations (Examples 1 to 5, Comparative Examples 1 to 5) Comparative example 3)] 40% by mass of glycerin (manufactured by Sakamoto Pharmaceutical Co., Ltd.), 5% by mass of Sunsoft Q-17S (manufactured by Taiyo Kabushiki Kaisha) After heating the mixture to 80°C, it was homogenized using a homomixer at 6000 rpm for 5 minutes. After cooling to 40°C, 5% by mass of Coconard MT (Kao Corporation) and the highly unsaturated fatty acid (A) listed in Table 1 were added. Fatty acid-containing oil and (B) antioxidant were added. The antioxidant for fatty acid esters was The rest was dissolved in Coconard MT and added. The mixture was homogenized using a mixer at 40°C and 6000 rpm for 10 minutes, and then the antioxidant (C) was added. The inhibitor and the remaining amount of water were added, and the mixture was treated at 40°C in a homomixer at 6000 rpm for various times. If necessary, the mixture is further emulsified with a high-pressure homogenizer at 450 kg / cm 2 Article The homogenization treatment was carried out under the conditions of Examples 1 to 5 and Comparative Examples 1 to 5, which have different emulsion particle sizes. An emulsion was obtained.

[0033] [Water solubility evaluation] The solubility of 1% aqueous solutions of the examples and comparative examples was confirmed and judged according to the following criteria. ◎: Dissolves quickly and uniformly after dilution ○: Stirring is required after dilution, but dissolves uniformly △: Some of the material dissolves with stirring, but some remains undissolved and some precipitate remains. ×: Not soluble

[0034] [POV Rating] After extracting oil from the preparation stored at 40°C, the oil was measured by potentiometric titration according to the standard method for analyzing fats and oils. The peroxide value (POV) was measured using a Titrando (Metrohm). We checked the number of days. Generally, in oxidation stability tests, a 10°C increase in temperature will reach the specified POV. The number of days to reach the specified POV at 40°C is 90 days. If this is the case, it can be assumed that the material has oxidation stability for one year or more at room temperature (20°C).

[0035] [Table 1]

[0036] As shown in Table 1, in Example 1, the content of (A) oils and fats containing highly unsaturated fatty acids was 15% by mass, The total content of (B) and (C) was 0.30% by mass, and the ratio of (B) / (C) was 0.67. As a result, an emulsion preparation containing highly unsaturated fatty acids with an emulsion particle size of 95 nm was obtained. The efficacy was good, and the time to reach POV30 was 105 days.

[0037] In Example 2, (A) the content of oils and fats containing highly unsaturated fatty acids was 35% by mass, (B) and The total content of (C) is 0.42% by mass, the ratio of (B) / (C) is 1.10, and the emulsion particles The emulsion preparation containing highly unsaturated fatty acids with a particle diameter of 132 nm was obtained. The number of days to reach POV30 was 102 days.

[0038] In Example 3, (A) the content of oils and fats containing highly unsaturated fatty acids was 20% by mass, (B) and The total content of (C) is 0.35% by mass, the ratio of (B) / (C) is 2.18, and the emulsion particles The emulsion preparation containing highly unsaturated fatty acids with a particle diameter of 135 nm was obtained. The time it took to reach POV30 was 98 days.

[0039] In Example 4, (A) the content of oils and fats containing highly unsaturated fatty acids was 15% by mass, (B) and The total content of (C) is 5.00 mass%, the ratio of (B) / (C) is 3.17, and the emulsion particles The emulsion preparation containing highly unsaturated fatty acids with a particle diameter of 145 nm was obtained. The time it took to reach POV30 was 90 days.

[0040] In Example 5, (A) the content of oils and fats containing highly unsaturated fatty acids was 20% by mass, (B) and The total content of (C) is 0.49% by mass, the ratio of (B) / (C) is 0.96, and the emulsion particles The emulsion preparation containing highly unsaturated fatty acids with a particle diameter of 88 nm was obtained. The time to reach POV30 was 125 days.

[0041] In Comparative Example 1, the content of (A) oils and fats containing highly unsaturated fatty acids was 15% by mass, and (B) and The total content of (C) is 0.92% by mass, the ratio of (B) / (C) is 45, and the emulsion particle size is The emulsion preparation containing highly unsaturated fatty acids with a particle size of 145 nm was obtained. The time to reach POV30 was 55 days.

[0042] In Comparative Example 2, the content of (A) oils and fats containing highly unsaturated fatty acids was 35% by mass, and (B) and The total content of (C) is 0.26% by mass, the ratio of (B) / (C) is 0.86, and the emulsion particles The emulsion preparation containing highly unsaturated fatty acids with a particle diameter of 1051 nm was obtained. The results were favorable, with POV30 being reached in 21 days.

[0043] In Comparative Example 3, the content of (A) oils and fats containing highly unsaturated fatty acids was 35% by mass, and (B) and The total content of (C) is 0.42% by mass, the ratio of (B) / (C) is 1.10, and the emulsion particles The emulsion preparation containing highly unsaturated fatty acids with a particle diameter of 200 nm was obtained. The time it took to reach POV30 was 49 days.

[0044] In Comparative Example 4, the content of (A) oils and fats containing highly unsaturated fatty acids was 15% by mass, and (B) and The total content of (C) is 0.42% by mass, the ratio of (B) / (C) is 0.40, and the emulsion particles The emulsion preparation containing highly unsaturated fatty acids with a particle diameter of 172 nm was obtained. The time it took to reach POV30 was 67 days.

[0045] In Comparative Example 5, the content of (A) oils and fats containing highly unsaturated fatty acids was 20% by mass, (B) and The total content of (C) is 0.52% by mass, the ratio of (B) / (C) is 0.04, and the emulsion particles The emulsion preparation containing highly unsaturated fatty acids with a particle diameter of 135 nm was obtained. The time it took to reach POV30 was 58 days.

[0046] From the above results, it can be seen that in Examples 1 to 5, the content of (A) is 5% by mass to 60% by mass, The total content of (B) and (C) is 0.01% by mass to 10% by mass, and the ratio of (B) / (C) The emulsion contains highly unsaturated fatty acids with an emulsion ratio of 0.2 to 5 and an emulsion particle size of 150 nm or less. Moreover, Examples 1 to 5 exhibited extremely good water solubility, and The number of days to reach POV is 90 days or more, and the number of days to reach POV is 30 compared to Comparative Examples 1 to 5. In Examples 1 to 5, the number of days to reach POV30 at 40°C was clearly extended. Since the shelf life was more than 90 days, it is believed that the product can be stored at room temperature for more than one year. In Examples 1 to 5, the emulsion particle size was determined based on the PO This was proportional to the number of days to reach V30. From these results, it can be seen that the smaller the emulsion particle size, the better the oxidation stability. Similarly, in Comparative Examples 2 to 4, the emulsion particle size and oxidation stability were A proportional relationship was suggested. The polyunsaturated fatty acids contained in Examples 1 to 5 are DHA, E, and the like, which are abundant in fish oil. PA and α-linolenic acid, which is found in large amounts in vegetable oils such as flaxseed oil. Regarding the emulsification particle size and the soluble fatty acid content, regardless of the type of polyunsaturated fatty acid, such as fish oil or vegetable oil, The correlation of oxidation stability was demonstrated.

[0047] Comparing Example 4 and Comparative Example 1, (A) the content of oils and fats containing highly unsaturated fatty acids is the same. The total content of (B) and (C) is within the range of 0.01% by mass to 10% by mass, and the emulsification The particle size was 145 nm when it was less than 150 nm. However, the ratio of (B) / (C) The values ​​were 3.17 for Example 4 and 45 for Comparative Example 1, which were significantly different. The number of days to reach the target was 90 days for Example 4 and 55 days for Comparative Example 1. It took a long time to reach POV30. From these results, when the ratio of (B) / (C) is 5 or less, the water solubility is good and the POV30 It is possible to obtain an emulsion formulation containing highly unsaturated fatty acids with excellent oxidation stability, with a time to reach 90 days or more. It was shown that...

[0048] Comparing Example 3 and Comparative Example 5, (A) the content of oils and fats containing highly unsaturated fatty acids is the same. The total content of (B) and (C) is within the range of 0.01% by mass to 10% by mass, and the emulsification The particle size was 135 nm when it was less than 150 nm. However, the ratio of (B) / (C) The POV30 was 2.18 in Example 3 and 0.04 in Comparative Example 5, which were significantly different. The number of days to reach the target was 98 days for Example 3 and 58 days for Comparative Example 5. It took a long time to reach POV30. On the other hand, highly unsaturated fatty acid-containing emulsion preparations Example 1 to Example 2, which have good water solubility and excellent oxidation stability, Of the 5, the lower limit of the ratio (B) / (C) is 0.67. From these results, when the ratio of (B) / (C) is 0.2 or more, the water solubility is good and the POV The emulsion formulation containing highly unsaturated fatty acids has excellent oxidation stability and reaches 30 days or more for 90 days. It was shown that this can be done.

[0049] Comparing Example 4 and Comparative Example 4, (A) the content of oils and fats containing highly unsaturated fatty acids is the same. The total content of (B) and (C) is within the range of 0.01% by mass to 10% by mass, and (B The ratio of (C) / (D) is in the range of 0.2 to 5. However, the emulsion particle size is 14 in Example 4. 5 nm, and Comparative Example 4 had a particle size of 172 nm, and the particle size of the emulsion in Comparative Example 4 exceeded 150 nm. The number of days to reach POV30 was 90 days for Example 4 and 67 days for Comparative Example 4. The number of days to reach POV30 was longer than in Comparative Example 4. From these results, when the emulsion particle size is 150 nm or less, water solubility is good and POV30 It is possible to obtain an emulsion formulation containing highly unsaturated fatty acids with excellent oxidation stability for 90 days or more. It was shown that:

[0050] [Reference Preparation Example: Preparation of an emulsion formulation containing highly unsaturated fatty acids] According to Example 3 of JP-A-08-154576, specifically, the following procedure was performed: As a reference example, an oil emulsion preparation containing highly unsaturated fatty acids was obtained. Put decaglycerin monooleate [product name: Sanso] into a 1 liter stainless steel beaker. Futo Q-17S (manufactured by Taiyo Kagaku Co., Ltd.) 15g, sodium ascorbate 10g, catechin [Product name: Sancatechin E, manufactured by Mitsui Norin Co., Ltd.] 0.25g, Sorbitol [Product name: Sol 75 g of Vitol C (manufactured by Nikken Chemical Co., Ltd.) and 129.75 g of water were added and completely dissolved. To the solution, add 10g of monoglycerin fatty acid ester and lecithin [Sun Lecithin W-1 5g of extract tocopherol, 5% by weight of EPA, 27% by weight of DHA Refined tuna oil containing 250% of DHA [product name: Sun Omega DHA27, manufactured by Nippon Oil & Fats Co., Ltd.] The oil phase containing the 1000g of sucrose was gradually mixed and stirred. The mixture was homogenized at 1000 rpm for 10 minutes to obtain a homogenous highly unsaturated fatty acid-containing oil emulsion formulation (Reference Example ) was obtained. In this reference preparation example, the homogenization treatment step is carried out using the compound used in JP-A-08-154576. The microfluidizer used in the experiment was replaced with a homomixer, but the homomixer treatment However, the particle size obtained is similar to that obtained with the Microfluidizer treatment.

[0051] [Water solubility evaluation] The solubility of the 1% aqueous solution of the Reference Example was confirmed and judged according to the following criteria.

[0052] [POV Rating] After extracting oil from the preparation stored at 40°C, the oil was measured by potentiometric titration according to the standard method for analyzing fats and oils. The peroxide value (POV) was measured using a Titrando (Metrohm). We checked the number of days.

[0053] In the reference example, (A) the content of oils and fats containing highly unsaturated fatty acids is 50% by mass, (B) and ( The total content of (B) and (C) is 3.05% by mass, the ratio of (B) / (C) is 0.49, and the emulsion particles The emulsion preparation containing highly unsaturated fatty acids with a particle diameter of 232 nm was obtained. It quickly dissolved uniformly after dilution. The time required to reach POV30 was 41 days.

[0054] The emulsified particle size of the reference example is larger than 150 nm, and the time required to reach POV30 is less than 90 days. Comparison of Examples 1 to 5 with Reference Example shows that when the emulsion particle size is 150 nm or less, Highly unsaturated fat with good solubility and excellent oxidation stability, achieving POV30 for over 90 days It was shown that an acid-containing emulsion preparation could be obtained. [Industrial Applicability]

[0055] The highly unsaturated fatty acid-containing emulsion preparation according to the present invention is stably water-soluble, and therefore, it can be used in a variety of applications including those containing water. The polyunsaturated fatty acid-containing food of the present invention can be added or blended into processed foods containing polyunsaturated fatty acids. Emulsified formulations have high oxidation stability, so they are expected to be distributed and stored at room temperature.

Claims

1. (A) an oil or fat containing a highly unsaturated fatty acid; (B) (b1) an oil-soluble radical scavenging antioxidant having a phenolic hydrogen atom and / or (b2) an oil-soluble antioxidant exhibiting an oxidation-reduction type; (C) (c1) A water-soluble radical scavenging antioxidant having a phenolic hydrogen atom and / or (c2) a water-soluble antioxidant exhibiting an oxidation-reduction type; An emulsion preparation that exhibits good solubility in water, The content of the (A) is 5% by mass to 60% by mass, The total content of (B) and (C) is 0.01% by mass to 10% by mass, The ratio of (B) / (C) is 0.2 to 5; A highly unsaturated fatty acid-containing emulsion preparation, having an emulsion particle size of 150 nm or less.

2. The (b1) is one of tocopherol, gallic acid fatty acid ester, BHA, and BHT. one or more species, The (b2) is one or more of ascorbic acid fatty acid esters and ubiquinone. and The (c1) is one or more of tea catechins, anthocyanins, and chlorogenic acids. and The (c2) is ascorbic acid and its metal salts, or erythorbic acid and its metal salts.

2. The highly unsaturated fatty acid-containing emulsion preparation according to claim 1, wherein the highly unsaturated fatty acid-containing emulsion preparation comprises one or more of the following:

3. The polyunsaturated fatty acid (A) contains any one of DHA, EPA, and α-linolenic acid.

3. The highly unsaturated fatty acid-containing emulsion preparation according to claim 1 or 2.

4. Oil was extracted from the highly unsaturated fatty acid-containing emulsion preparation stored at 40°C, and a standard oil and fat analysis was performed. When the peroxide value (POV) is measured by potentiometric titration, the POV reaches 30.

3. The highly unsaturated fatty acid-containing emulsion preparation according to claim 1, wherein the time until the formation of the polyunsaturated fatty acid-containing emulsion preparation is 90 days or more.

5. The following components (A), (B), and (C): (A) an oil or fat containing highly unsaturated fatty acids; (B) (b1) an oil-soluble radical scavenging antioxidant having a phenolic hydrogen atom and / or (b2) an oil-soluble antioxidant exhibiting an oxidation-reduction type; (C) (c1) A water-soluble radical scavenging antioxidant having a phenolic hydrogen atom and / or (c2) a water-soluble antioxidant exhibiting an oxidation-reduction type; A method for producing an oil or fat containing highly unsaturated fatty acid, comprising a step of mixing The content of the (A) is 5% by mass to 60% by mass, The total content of (B) and (C) is 0.01% by mass to 10% by mass, The ratio of (B) / (C) is 0.2 to 5; The highly unsaturated fatty acid-containing emulsion further includes a step of adjusting the emulsion particle size to 150 nm or less. Method of manufacturing the formulation.

6. The (b1) is one of tocopherol, gallic acid fatty acid ester, BHA, and BHT. one or more species, The (b2) is one or more of ascorbic acid fatty acid esters and ubiquinone. and The (c1) is one or more of tea catechins, anthocyanins, and chlorogenic acids. and The (c2) is ascorbic acid and its metal salts, or erythorbic acid and its metal salts. The method for producing an emulsion preparation containing highly unsaturated fatty acids according to claim 5, wherein the highly unsaturated fatty acid is one or more of the following:

7. The polyunsaturated fatty acid (A) contains any one of DHA, EPA, and α-linolenic acid. A method for producing the highly unsaturated fatty acid-containing emulsion preparation according to claim 5 or 6.

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