Lipid composition

Abstract

To provide a means effective in suppressing oxidative deterioration of fats and oils containing polyunsaturated fatty acid containing DHA and to provide a method capable of determining near olfactory sense of human being by specifying a component that becomes an index of oxidative deterioration of fat and acid containing DHA.SOLUTION: A lipid composition containing lipids composed of polyunsaturated fatty acids as constituent fatty acids, wherein a composition ratio of polyunsaturated fatty acids among all constituent fatty acids of the lipids is 15% or more, the moisture content is 600 ppm or less, perfluorooctanesulfonic acid is 0.1 ppb or less, and perfluorooctanoic acid is 0.1 ppb or less. It is preferable that the composition contains 2-(2-pentenyl)furan at less than 0.0095 ppm, and 2,4-heptadienal at less than 2.600 ppm.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a lipid composition containing polyunsaturated fatty acids.

Background Art

[0002] In recent years, the health benefits of polyunsaturated fatty acids have been reported in large numbers, and the demand has been increasing accordingly. In particular, it can be said that the fact that canned seafood products have attracted the spotlight among consumers is an indication of this. Also, among the approved foods utilizing the functional food labeling system, there are many products that tout the health effects of these polyunsaturated fatty acids. The polyunsaturated fatty acids referred to here include, for example, docosahexaenoic acid (DHA), eicosapentaenoic acid (EPA), α-linolenic acid, and the like. Fish oil extracted and purified from seafood has attracted attention as a material rich in these polyunsaturated fatty acids, particularly DHA and EPA.

[0003] Oils and fats compositions containing polyunsaturated fatty acids may contain moisture. For example, Patent Document 1 describes a method for producing oils and fats containing long-chain polyunsaturated fatty acids, which includes a contact treatment step with rosemary and an adsorption treatment step with chemically activated activated carbon, and has a moisture content of 3% by weight or less. In this document, as an effect of this production method, it is stated that oils and fats containing long-chain polyunsaturated fatty acids with improved oxidative stability and good flavor can be obtained by an easy method. Also, in Example 1, 100 parts of deacidified tuna oil (acid value = 0.10, peroxide value = 5.5, iodine value = 184, EPA + DHA content = 28.0%) was subjected to a rosemary treatment and decolorization step and a deodorization step, and it is described that the moisture content in the oils and fats was 0.01 - 0.10% through these steps. Further, Patent Document 2 describes an oil comprising (i) at least about 30% by weight of one or more polyunsaturated fatty acids having at least 4 carbon-carbon double bonds; (ii) at least one first antioxidant; and (iii) means for improving oxidative stability, and having a fishy odor of less than 1.5. In this document, as an example, an oil having a content of a predetermined polyunsaturated fatty acid of at least about 400 mg / g of oil, and having a moisture and volatile matter% with a standard value of at most 0.02 and a result of <0.01 is described.

[0004] Perfluoroalkyl compounds and polyfluoroalkyl compounds (PFAS) have been used in industry and household products since the 1940s, but are known to be difficult to decompose in the environment and have environmental persistence and bioaccumulation, and in recent years, the health effects and environmental risks have been discussed in various countries.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0006] Polyunsaturated fatty acids contain many double bonds in their chemical structures, generally have poor oxidation stability, and rapid flavor deterioration. This is because the double bonds of fatty acids easily react with active oxygen in the air through free radical generation to form hydroperoxide forms. These hydroperoxide forms further continuously react and decompose with new free radicals such as active oxygen to generate compounds exhibiting unique odors such as unsaturated aldehydes and ketones. Through the studies of the present inventors, it has been found that the decomposition of polyunsaturated fatty acids during storage may be promoted by the moisture in the oil and fat composition. Therefore, it is desirable that the moisture content in the oil and fat composition be low. Conventional evaluations of lipids based on measurement values by acid value, peroxide value, and the rancimat method measure compounds generated during decomposition (peroxidized compounds, unsaturated aldehydes, ketones, etc.), but do not necessarily reflect the unpleasant odor felt by humans from deteriorated lipids. There are few reports using odor components showing a high contribution to deteriorated lipids as an index.

[0007] Also, in the lipid composition, it is desirable that PFAS be reduced.

Means for Solving the Problems

[0008] The present inventors have found that by controlling the moisture contained in the lipid composition, the generation of odor components can be reduced. Also, when the amount of a specific component (PFOS) is within a specific range, it has been found that the unique odor during the deterioration of the oil and fat composition is also small, and the present invention has been completed.

[0009] In addition, the present inventors have searched for components involved in the odor of lipids and have found about 100 components out of several hundred aroma components contained in lipids having polyunsaturated fatty acids as constituent fatty acids that can be sensed by the human nose. Furthermore, from among them, important components that can be sensed as an odor even in small amounts (relatively low thresholds) have been identified. Also, by individually measuring the concentrations of such components in the lipid, it has been found how important it is to suppress the odor components, and it has also been found that a composition with the suppressed odor can be provided as follows.

[0010] This application provides the following. [1] A lipid composition containing a lipid having polyunsaturated fatty acids as constituent fatty acids, wherein the composition ratio of polyunsaturated fatty acids in all constituent fatty acids of the lipid is 15% or more, the water content is 600 ppm or less, the perfluorooctanesulfonic acid is 0.1 ppb or less, and the perfluorooctanoic acid is 0.1 ppb or less, the composition. [2] The composition according to [1], wherein the water content is 300 ppm or less. [3] The composition according to any one of [1] or [2], containing an antioxidant. [4] The composition according to any one of [1] to [3], wherein 2,4-heptadienal is less than 2.600 ppm. [5] The composition according to any one of [1] to [4], wherein 2-(2-pentenyl)furan is less than 0.0095 ppm. A method for inspecting the degree of deterioration of a lipid composition, which uses as an index any one selected from the group consisting of 1-penten-3-one, 2,6-nonadienal, 2-methyl-2-cyclopentene-1-one, 2-(2-pentenyl)furan, 2,4-decadienal, 4-heptenal, and 2,4-heptadienal, and contains a lipid having a polyunsaturated fatty acid as a constituent fatty acid.

[0011] [7] A method for producing a lipid composition containing a lipid having a polyunsaturated fatty acid as a constituent fatty acid, with a reduced unpleasant odor, and having a composition ratio of the polyunsaturated fatty acid in all constituent fatty acids of the lipid of 15% or more, comprising the following steps: A step of obtaining a fraction from the raw material, wherein the water content is 600 ppm or less, 2-(2-pentenyl)furan is less than 0.0095 ppm, and 2,4-heptadienal is less than 2.600 ppm. [8] A method for reducing the unpleasant odor of a lipid composition containing a lipid having a polyunsaturated fatty acid as a constituent fatty acid, and having a composition ratio of the polyunsaturated fatty acid in all constituent fatty acids of the lipid of 15% or more, characterized by obtaining a fraction from the raw material that satisfies the following: The water content is 600 ppm or less, 2-(2-pentenyl)furan is less than 0.0095 ppm, and 2,4-heptadienal is less than 2.600 ppm. [9] A lipid composition containing a lipid having a polyunsaturated fatty acid as a constituent fatty acid, wherein the composition ratio of the polyunsaturated fatty acid in all the constituent fatty acids of the lipid is 15% or more, the water content is 600 ppm or less, 2-(2-pentenyl)furan is less than 0.0095 ppm, and 2,4-heptadienal is less than 2.600 ppm.

[10] A lipid composition containing a lipid having a polyunsaturated fatty acid as a constituent fatty acid, wherein the composition ratio of the polyunsaturated fatty acid in all the constituent fatty acids of the lipid is 15% or more, the acid value is 0.5 or less and the peroxide value is 2.0 meq / kg or less, the water content is 600 ppm or less, 2-(2-pentenyl)furan is less than 0.0095 ppm, and 2,4-heptadienal is less than 2.600 ppm. [Effect of the Invention]

[0012] According to the present invention, a lipid composition with less unpleasant odor can be provided. According to the present invention, a lipid composition can be provided in which perfluoroalkyl compounds and perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA), which are a kind of polyfluoroalkyl compounds (PFAS), are below the detection limit. [Brief Description of the Drawings]

[0013]

Figure 1

[0014] Regarding the present invention, when indicating ratios, composition ratios, concentrations (ppm, %, etc.), they are based on mass unless otherwise specified.

[0015] <Lipid Composition> The present invention relates to a lipid composition containing a lipid having a polyunsaturated fatty acid as a constituent fatty acid, and having a relatively high composition ratio of the polyunsaturated fatty acid in all the constituent fatty acids of the lipid.

[0016] (Lipid) Lipids include fats and oils, phospholipids, and glycolipids. Fats and oils include substances having a triacylglycerol (triglyceride), diacylglycerol, or monoacylglycerol structure, fatty acids, and fatty acid esters. Phospholipids refer to lipids having phosphorus in the form of phosphoric acid, and include glycerophospholipids and sphingomyelin phospholipids. Glycolipids include glyceroglycolipids and sphingosine glycolipids.

[0017] (Polyunsaturated Fatty Acid, Fatty Acid Composition) In the composition of the present invention, the composition ratio of the polyunsaturated fatty acid in all the constituent fatty acids of the lipid is relatively high.

[0018] Polyunsaturated fatty acids (polyenoic acids, Poly Unsaturated Fatty Acids, PUFAs) refer to unsaturated fatty acids having two or more unsaturated bonds, particularly double bonds. Examples of polyunsaturated fatty acids include linoleic acid (C18:2), γ-linolenic acid (C18:3), and arachidonic acid (C20:4) which are n-6 fatty acids, and α-linolenic acid (C18:3), eicosapentaenoic acid (EPA) (C20:5), and docosahexaenoic acid (DHA) (C22:6) which are n-3 fatty acids. Among polyunsaturated fatty acids, preferred examples are n-3 polyunsaturated fatty acids, or polyunsaturated fatty acids having four or more, more preferably five or more unsaturated bonds. Even more preferred examples are EPA and / or DHA, and a more preferred example is DHA. Hereinafter, among lipids having a polyunsaturated fatty acid as a constituent fatty acid, the lipid having DHA as a constituent fatty acid may be described as an example, but the description also applies to the case where other polyunsaturated fatty acids are constituent fatty acids.

[0019] The lipids contained in the composition of the present invention may contain, as constituent fatty acids, fatty acids other than polyunsaturated fatty acids, that is, saturated fatty acids (SFA) and monoene fatty acids (monounsaturated fatty acids, MUFA). Examples of such constituent fatty acids include myristic acid (C14:0), palmitic acid (C16:0), stearic acid (C18:0), oleic acid (C18:1, n9c), and eicosenoic acid (C20:1).

[0020] In a preferred embodiment, the composition ratio of polyunsaturated fatty acids in all constituent fatty acids of the lipid is 15% or more, preferably 18% or more, more preferably 20% or more, still more preferably 22% or more, and even more preferably 50% or more, regardless of the polyunsaturated fatty acid. The upper limit of the composition ratio of polyunsaturated fatty acids in all constituent fatty acids is not particularly limited regardless of the polyunsaturated fatty acid, but is, for example, 82% or less, may be 80% or less, preferably 75% or less, more preferably 70% or less, and still more preferably 60% or less. In some cases, it may be 46% or less, preferably 40% or less, more preferably 35% or less, and still more preferably 30% or less. Such a composition ratio is particularly preferably applicable when the polyunsaturated fatty acid is DHA. In the present invention, when expressing the composition ratio of a specific fatty acid in all constituent fatty acids of the lipid in %, it is based on the area of the chart when the fatty acid composition is analyzed by gas chromatography, unless otherwise specified.

[0021] The content of components other than lipids in the composition of the present invention is, for example, 10.0% or less, preferably 8.0% or less, more preferably 7.5% or less, and still more preferably 7.0% or less.

[0022] The iodine value of the lipid composition of the present invention is, for example, 155 g / 100 g or more, preferably 160 g / 100 g or more, and is, for example, 250 g / 100 g or less, preferably 220 g / 100 g or less, more preferably 210 g / 100 g or less. The iodine value can be measured by the Wijs method.

[0023] The acid value (the number of mg of potassium hydroxide required to neutralize the free fatty acids contained in 1 g of oil and fat) of the lipid composition of the present invention is, for example, 0.5 or less, preferably 0.4 or less, more preferably 0.3 or less, and even more preferably 0.2 or less. The peroxide value (sometimes referred to as "POV") of the lipid composition of the present invention is preferably 2.0 meq / kg or less, more preferably 0.5 meq / kg or less. The peroxide value represents the amount of peroxide, which is a primary product generated at the initial stage of the auto-oxidation of oil and fat. The values of the acid value and the peroxide value can be measured by the method described in the Standard Oil and Fat Analysis Test Method, 2003 Edition (compiled by the Japan Oil Chemists' Society).

[0024] The saponification value (the number of mg of potassium hydroxide required to saponify 1 g of oil and fat) of the lipid composition of the present invention is, for example, 220 or less, preferably 210 or less, more preferably 200 or less, and even more preferably 190 or less. The lower limit value may be, for example, 150 or more, 160 or more, or 170 or more regardless of the upper limit value.

[0025] (Raw material) The composition of the present invention can be prepared using various natural products containing lipids having polyunsaturated fatty acids as constituent fatty acids as raw materials. Examples of raw materials include fish oil and microorganisms. Fish oil includes those obtained from fish meat and those obtained from fish eggs. Examples of microorganisms include Labyrinthulales. Labyrinthulales are eukaryotic microorganisms that are closely related to algae such as brown algae and diatoms but are heterotrophic and do not perform photosynthesis, and are known for accumulating lipids having polyunsaturated fatty acids such as DHA and EPA as constituent fatty acids in cells.

[0026] The type of fish from which the fish oil is derived is not particularly limited as long as it contains a large amount of lipids having polyunsaturated fatty acids as constituent fatty acids, but it is preferably a fish of the mackerel subfamily, the swordfish family, the marlin family, the salmon family, the herring family, the cod family, or the jack family. The mackerel subfamily includes the mackerel tribe (Scomberomorus, Scomber), the Spanish mackerel tribe (Acanthocybium, Scomberomorus, Niphon), the frigate mackerel tribe (Auxis, Thunnus, Cybiosarda, Orcynopsis), and the tuna tribe (Euthynnus, Sarda, Soudan, Narrow-barred mackerel, Thunnus), but it is more preferably tuna (Bluefin tuna, Skipjack tuna, Yellowfin tuna, Bigeye tuna), swordfish, skipjack tuna, soudan (Maru soudan, Hira soudan), sarda, chub mackerel (True mackerel), mackerel, Spanish mackerel, mackerel, skipjack tuna. The salmon family includes the genus Oncorhynchus, the genus Salmo, the genus Brachymystax, and the genus Itu, but it is more preferably a fish of the genus Oncorhynchus or the genus Salmo. Examples of fish of the genus Oncorhynchus include whitefish, silver salmon (Coho salmon, Silver salmon), pink salmon (Pink salmon), cherry salmon, yamame, Taiwanese salmon, early summer salmon, amago, Biwa salmon (Ameno fish), nijimasu (Steelhead), masunosuke (King salmon), red salmon, hime salmon, kuni salmon. Examples of fish of the genus Salmo include Atlantic salmon (Atlantic salmon), brown trout. The herring family includes the herring subfamily, the sprat subfamily, the konoshiro subfamily, and the Ehiravinae subfamily, but it is preferably a fish of the herring subfamily and the genus Clupea. Examples of fish of the genus Clupea include herring, Atlantic herring, sardine (Sardine, Japanese pilchard, Japanese halfbeak). The cod family includes the genus Gadus (Cod), the genus Micromesistius (Blue whiting), the genus Gadiculus, the genus Trisopterus, the genus Microgadus, the genus Eleginus, the genus Merlangius, the genus Melanogrammus, the genus Pollachius, the genus Boreogadus, and the genus Arctogadus, but it is preferably a fish of the genus Gadus. Examples of fish of the genus Gadus include Alaska pollock, cod, Atlantic cod, Greenland cod.The Carangidae family includes the Eucinostominae subfamily, the Scomberoidinae subfamily, the Pseudocaranxinae subfamily, and the Caranginae subfamily, and fish of the Pseudocaranxinae subfamily are preferred. The Pseudocaranxinae subfamily includes the Trachurus genus, the Decapterus genus, the Caranx genus, and the Pseudocaranx genus, and fish of the Caranx genus are preferred. Examples of fish of the Caranx genus include the Japanese amberjack, the greater amberjack, and the yellowtail kingfish.

[0027] When referring to fish eggs in the present invention, unless otherwise specified, the degree of processing is not limited. Therefore, regarding the present invention, when referring to a fish egg lipid composition, it also includes a lipid composition using as a raw material a fish egg extract, fish egg oil, a refined fish egg oil, a dried product of any of them, etc. In a particularly preferred embodiment, the composition of the present invention is prepared from muscle eggs, ikura (salmon roe), kazunoko (herring roe), nasunoko (mullet roe), or processed products thereof.

[0028] Even when the raw material is a microorganism, the type of microorganism is not particularly limited as long as it contains a large amount of lipids having polyunsaturated fatty acids as constituent fatty acids. Microorganisms of the Labyrinthulomycetes are roughly classified into Labyrinthulids belonging to the Labyrinthulaceae family and Thraustochytriids belonging to the Schizochytriaceae family, and the former is more suitable in terms of growth and lipid accumulation. Examples of more specific microorganisms of the Labyrinthulomycetes include microorganisms belonging to the genus Aurantiochytrium, the genus Thraustochytrium, the genus Ulkenia, the genus Parietichytrium, the genus Labyrinthula, the genus Aplanochytrium, the genus Oblongichytrium, or the genus Schizochytrium.

[0029] (Moisture) The water content in the composition of the present invention is preferably low. According to the studies of the present inventors, when the water content in the lipid composition exceeds a certain concentration, deterioration is accelerated, the amount of aroma components increases, and an oxidized odor is strongly felt. The water content in the composition is 600 ppm or less, preferably 500 ppm or less, more preferably 400 ppm or less, still more preferably 350 ppm or less, still more preferably 300 ppm or less, and still more preferably 250 ppm or less, regardless of the concentrations of other components. The lower limit of the water content in the composition is 10 ppm or more, preferably 20 ppm or more, more preferably 30 ppm or more, still more preferably 40 ppm or more, still more preferably 50 ppm or more, still more preferably 80 ppm or more, still more preferably 100 ppm or more, still more preferably 120 ppm or more, and still more preferably 150 ppm or more, regardless of the upper limit value.

[0030] In addition, when referring to the amount or concentration of water in the present invention, unless otherwise specified, it is the value measured by a method for measuring water in food. A person skilled in the art can select an appropriate measurement method according to the form of the oil and fat composition and the level of water contained therein. Examples of the measurement method include the Karl Fischer method, the method using a water activity measuring device (water activity measurement method), and the method using a moisture meter (drying loss method). The Karl Fischer method has two methods: volumetric titration method and coulometric titration method. Generally, when the water content is 1% or more, the volumetric titration method is selected, and when it is 1% or less, the coulometric titration method is selected.

[0031] (Oxidized odor index component) The present invention relates to an index component of the oxidized odor (sometimes referred to as an unpleasant odor) of a lipid composition containing a lipid having a polyunsaturated fatty acid as a constituent fatty acid. The following seven components are components identified by the present inventors as indicators of the oxidized odor of polyunsaturated fatty acids that can be sensed even in small amounts (relatively low threshold values). This application is the first to clarify the relationship between these components and the oxidized odor of polyunsaturated fatty acids. Also, in a lipid composition having an oxidized odor, it is also the first in this application to show the amount of 2-(2-pentenyl)furan and / or 2,4-heptadienal contained, not as a relative value but as an absolute amount (see the Examples section).

[0032] 1-penten-3-one, 2,6-nonadienal, 2-methyl-2-cyclopentene-1-one, 2-(2-pentenyl)furan, 2,4-decadienal, 4-heptenal, and 2,4-heptadienal

[0033] In the case of a component having an optical isomer based on an asymmetric carbon or a geometric isomer based on a double bond, unless otherwise specified, any one of them may be used as an indicator of the oxidized odor, or a mixture thereof may be used as an indicator of the oxidized odor. Hereinafter, the concentration of each of the seven components in the composition will be described, but the concentration is the total concentration of those isomers unless otherwise specified in the case of a component having an optical isomer or a geometric isomer.

[0034] From the perspective that acid odor is acceptable as a food, the concentration of 2-(2-pentenyl)furan in the composition is less than 0.0095 ppm, preferably 0.0088 ppm or less, more preferably 0.0086 ppm or less, still more preferably 0.0083 ppm or less, and even more preferably 0.0080 ppm or less, regardless of the concentrations of other components.

[0035] Also, the concentration of 2,4-heptadienal in the composition is less than 2.600 ppm, preferably 2.400 ppm or less, more preferably 2.350 ppm or less, still more preferably 2.300 ppm or less, and even more preferably 2.200 ppm or less, and even more preferably 2.100 ppm or less, regardless of the concentrations of other components. More specifically, the concentration of (E,Z)2,4-heptadienal in the composition is less than 2.590 ppm, preferably 2.350 ppm or less, more preferably 2.280 ppm or less, still more preferably 2.240 ppm or less, and even more preferably 2.200 ppm or less, and even more preferably 2.100 ppm or less. The concentration of (E,E)2,4-heptadienal in the composition is less than 0.028 ppm, preferably 0.026 ppm or less, more preferably 0.025 ppm or less, still more preferably 0.024 ppm or less, and even more preferably 0.023 ppm or less.

[0036] It is preferable that either 2-(2-pentenyl)furan or 2,4-heptadienal satisfies such requirements, and it is more preferable that both satisfy such requirements.

[0037] The concentration of 1-penten-3-one in the composition is less than 0.139 ppm, preferably 0.138 ppm or less, more preferably 0.130 ppm or less, still more preferably 0.1 ppm or less, and even more preferably 0.07 ppm or less, regardless of the concentrations of other components.

[0038] The concentration of 2,6-nonadienal in the composition is less than 0.005 ppm, preferably 0.0045 ppm or less, more preferably 0.004 ppm or less, still more preferably 0.0035 ppm or less, and even more preferably 0.003 ppm or less, regardless of the concentrations of other components.

[0039] The concentration of 2,4-decadienal in the composition is less than 0.11 ppm, preferably 0.1 ppm or less, more preferably 0.075 ppm or less, still more preferably 0.05 ppm or less, and even more preferably 0.025 ppm or less, regardless of the concentrations of other components.

[0040] The amount or concentration of the oxidized odor component can be measured by a technique well-known to those skilled in the art, such as analyzing the components collected by the dynamic headspace method using a gas chromatograph-mass spectrometer (GC-MS).

[0041] The above seven components can be used as indicators when inspecting the degree of deterioration of a lipid composition containing a lipid having polyunsaturated fatty acids as constituent fatty acids. The determination values for each component can appropriately utilize the above values shown as the concentrations in the composition. For example, when determining a lipid composition using 1-penten-3-one as an indicator, the concentration of this component in the target lipid composition is measured. When it is less than 0.139 ppm, preferably 0.138 ppm or less, more preferably 0.130 ppm or less, still more preferably 0.100 ppm or less, and even more preferably 0.070 ppm or less, it can be determined that there is no oxidative deterioration.

[0042] Conventional evaluation of lipids based on the acid value, peroxide value, and measurement values by the rancimat method measures the total amount of products formed by oxidation. In contrast, the evaluation of lipid compositions using the indicator components of the oxidized odor disclosed in the present application directly measures the components with high contribution in the oxidized odor, enabling an evaluation closer to the sensory characteristics.

[0043] (Perfluoroalkyl compounds and polyfluoroalkyl compounds (PFAS)) In the composition of the present invention, perfluoroalkyl compounds and polyfluoroalkyl compounds (perfluoroalkyl substances and polyfluoroalkyl substances, abbreviated as PFAS) are reduced. PFAS is a general term for more than 4,730 organic fluorine compounds. Representative examples of PFAS include perfluorooctanesulfonic acid (PFOS) (the prefix "per" may also be referred to as "penta", the same applies hereinafter), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), perfluorohexanesulfonic acid (PFHxS), perfluorobutanesulfonic acid (PFBS), perfluorobutanoic acid (PFBA), perfluoropentanesulfonic acid (PFPeS), perfluoropentanoic acid (PFPeA), perfluorohexanoic acid (PFHxA), perfluoroheptanesulfonic acid (PFHpS), perfluoroheptanoic acid (PFHpA), perfluorooctanesulfonamide (PFOSA), perfluoro-3,7-dimethyloctanoic acid (PF-3,7-DMOA), perfluorodecanesulfonate (PFDS), perfluorodecanoic acid (PFDA), perfluoroundecanoic acid (PFUnA), perfluorododecanoic acid (PFDoA), perfluorotridecanoic acid (PFTrA), perfluorotetradecanoic acid (PFTA), 7H-dodecafluorooctanoic acid (HPFHpA), 2H,2H-perfluorodecanoic acid (H2PFDA), 2H,2H,3H,3H-perfluoroundecanoic acid (H4PFUnA), 1H,1H,2H,2H-perfluorohexanesulfonic acid (4:2FTS), 6:2 fluorotelomer sulfonate (6:2FTS).

[0044] In one aspect, in the composition of the present invention, at least one of PFOS and PFOA among PFASs is, for example, 1 ppb or less, preferably 0.1 ppb or less, more preferably 0.05 ppb or less, and even more preferably 0.01 ppb or less. In a preferred aspect, PFOS and PFOA among PFASs are, for example, 1 ppb or less, preferably 0.1 ppb or less, more preferably 0.05 ppb or less, and even more preferably 0.01 ppb or less.

[0045] The concentration of PFASs in the composition can be measured by a method for measuring PFASs in food. As an example of the measurement method, a liquid chromatography-mass spectrometry (LC-MS / MS) method can be mentioned.

[0046] The reduction of PFASs in the composition can be carried out by treatment using an adsorbent such as activated carbon. Representative PFOS and PFOA among PFASs are water-soluble and have an affinity for proteins, so they can be reduced by washing with water, oil-water separation, and activated carbon treatment.

[0047] (Adjustment of water content, method for producing lipid composition) The adjustment of the water content in the composition can be carried out by treatment using an adsorbent such as activated carbon or by a distillation process. One of the preferred treatments is a combination of treatment with an adsorbent such as activated carbon and distillation, and a treatment that repeats them. The composition of the present invention can be prepared, for example, by subjecting an oil or fat containing a highly unsaturated fatty acid obtained from fish or shellfish or microalgae to deacidification and degumming as necessary, and then treating it by combining vacuum distillation, adsorption, and steam distillation. There is no limitation on the oil or fat treatment conditions, and general conditions applicable to oils or fats containing highly unsaturated fatty acids can be used. For example, vacuum distillation can be carried out at 1 to 100 mTorr, preferably 5 to 50 mTorr, with a short residence time. For example, the adsorption can be carried out by treating the oil with 0.05 to 10% by weight, preferably 0.1 to 5% by weight of activated carbon and / or activated clay at a temperature of 50 to 120°C, preferably 50 to 100°C for 5 to 120 minutes, preferably 10 to 80 minutes. For example, steam distillation can be carried out with a steam amount of 0.5% by weight or more, preferably 1 to 10% by weight, based on the oil, at a temperature of 120 to 220°C, preferably 130 to 200°C, at 10 Torr or less, preferably 8 Torr or less, for 30 to 180 minutes, preferably 60 to 180 minutes. Also, each step can be repeated as necessary. In a preferred embodiment, steam distillation is carried out, and vacuum distillation and treatment with an adsorbent are carried out. It is more preferable to carry out vacuum distillation and treatment with an adsorbent before steam distillation.

[0048] (Antioxidant) The composition of the present invention may contain an antioxidant (sometimes also referred to as an antioxidant). The antioxidant is not particularly limited as long as it is an acceptable substance for addition to food, and various substances can be used. Examples of antioxidants include butylhydroxytoluene (BHT), butylhydroxyanisole (BHA), vitamins (e.g., tocopherol, retinol, β-carotene, ascorbic acid), vitamin derivatives (e.g., retinyl acetate, retinyl palmitate, ascorbyl palmitate, magnesium ascorbyl phosphate, tocopheryl acetate), flavonoids, polyphenol compounds, citric acid, nordihydroguaiaretic acid, thioctic acid (lipoic acid), dihydrolipoic acid, glycolic acid, and esters thereof. Preferably, it is highly effective against polyunsaturated fatty acids, and examples of such substances include BHT, tocopherol (vitamin E, V.E), BHA, rosemary extract (referring to a substance mainly composed of carnosic acid, carnosol, and rosmarol obtained from the leaves or flowers of rosemary), catechin, gallic acid, and propyl gallate.

[0049] The amount of the antioxidant in the composition can be adjusted as appropriate. Specifically, it can be 50 ppm or more, preferably 100 ppm or more, more preferably 200 ppm or more, and even more preferably 300 ppm or more. The upper limit is not particularly limited, and for example, it can be 30,000 ppm, can be 20,000 ppm or less, preferably 15,000 ppm or less, more preferably 10,000 ppm or less, and even more preferably 9,000 ppm or less. When multiple types of antioxidants are used, they may be used in such a way that the total amount is the above-mentioned amount.

[0050] <Others> (Route of administration, etc.) The composition of the present invention is suitable for oral ingestion or administration.

[0051] (Use) The composition of the present invention can be used to allow the ingestion of polyunsaturated fatty acids. In addition, the composition can be used for various applications based on the functions of polyunsaturated fatty acids. As the functions of DHA, which is a type of polyunsaturated fatty acid, inhibition of platelet aggregation, reduction of blood triglyceride levels, reduction of blood cholesterol levels, improvement of brain function, maintenance of memory, improvement of sleep quality, etc. are known. As the functions of DHA-bound phospholipids, allergy suppression, improvement of liver function, improvement of erythrocyte deformability, stroke suppression, whitening, improvement of cognitive function, etc. are known. There is also a report that DHA-bound phospholipids typified by PDPC affect the differentiation and proliferation of HL-60 human promyelocytic leukemia cells (J. Jpn. Oil Chem. Soc. 46(4), 1997).

[0052] In a preferred embodiment, the composition can be used to improve metabolic syndrome, lipid metabolism, glucose metabolism, and cognitive function. Metabolic syndrome refers to a condition in which visceral obesity is combined with high blood pressure, high blood sugar, or lipid metabolism abnormality, making the patient susceptible to heart disease, stroke, etc., and is diagnosed when the waist circumference is 85 cm or more for men and 90 cm or more for women, and two or more of the three parameters of blood pressure, blood sugar, and lipid are outside the standard values. The deviation from the standard values ​​refers to blood pressure: systolic (maximum) blood pressure ≧130 mmHg and / or diastolic (minimum) blood pressure ≧85 mmHg, blood sugar: fasting blood sugar ≧110 mg / dL, and lipid: hypertriglyceridemia, i.e., blood triglyceride ≧150 mg / dL, and / or hypo-HDL cholesterolemia, i.e., blood HDL <40 mg / dL. Targets for improving cognitive function include patients with Alzheimer's disease.

[0053] (subject) The compositions of the present invention are suitable for ingesting or administering polyunsaturated fatty acids to subjects, including infants, children, adults (15 years of age or older), middle-aged and elderly people (65 years of age or older), those in the midst of illness or recovery, pregnant women, women who have just given birth, men, and women.

[0054] (dose) The intake amount / dosage of the composition of the present invention may be 100mg to 10000mg per day, preferably 300mg to 5000mg, and more preferably 500mg to 2500mg. According to the "Dietary Reference Intakes for Japanese (2015 Edition)" by the Ministry of Health, Labor and Welfare, the dietary intake standard for n-3 fatty acids is 2.1 to 2.4g / day for men aged 15 years or older, 1.6 to 2.0g / day for women aged 15 years or older, and 1.8g / day for pregnant and lactating women. The composition of the present invention can also be used within these ranges.

[0055] The composition of the present invention may be administered / ingested once a day or multiple times a day, for example, three times per meal. Since the composition uses an active ingredient derived from fish eggs with rich eating experience, it is suitable for long-term ingestion. Therefore, it may be ingested repeatedly or over a long period, for example, for 3 days or more, preferably 1 week or more, more preferably 4 weeks or more, and particularly preferably 1 month or more, and can be continuously administered / ingested.

[0056] (Form) The composition of the present invention can be used as a raw material in the manufacture of general foods, health functional foods, pharmaceuticals, and quasi-drugs. General foods, etc., unless otherwise specified, include not only those for humans but also those for animals other than humans. Health functional foods include foods for specified health uses, foods with nutritional functions, and foods with functional claims. Foods, unless otherwise specified, include not only solids but also liquids such as beverages, drink agents, liquid foods, and soups. Foods include all general health foods such as special-purpose foods, dietary supplements, health supplements, supplements (for example, those in various dosage forms such as capsules and tablets), and beauty foods (for example, diet foods).

[0057] As one of the preferred embodiments, there is provided a food composition or a pharmaceutical composition in the form of a supplement or a beverage containing the composition of the present invention.

[0058] (Other components, additives) The composition of the present invention, and the food composition or pharmaceutical composition containing the composition of the present invention may contain other active ingredients and nutritional components that are acceptable as foods or pharmaceuticals. Examples of such components include vitamins (e.g., vitamin A, vitamin B1, vitamin B2, vitamin B6, vitamin B12, vitamin C, vitamin D, vitamin E, vitamin K, biotin, folic acid, pantothenic acid, and nicotinic acids), minerals (e.g., copper, zinc, iron, cobalt, manganese), amino acids (e.g., lysine, arginine, glycine, alanine, glutamic acid, leucine, isoleucine, valine), carbohydrates (glucose, sucrose, fructose, maltose, trehalose, erythritol, maltitol, palatinose, xylitol, dextrin), dietary fiber, proteins, other lipids, and the like.

[0059] The composition of the present invention, and the food composition or pharmaceutical composition containing the composition of the present invention may further contain additives that are acceptable as foods or pharmaceuticals. Examples of such additives include antioxidants, stabilizers, stabilizing agents, colorants, preservatives, inert carriers (solid or liquid carriers), excipients, surfactants, binders, disintegrants, lubricants, solubilizing aids, suspending agents, coating agents, buffers, pH adjusters, emulsifiers, sweeteners, flavors, acidulants, and natural substances.

[0060] (Others) The present invention can be applied to foods that contain a large amount of lipids containing polyunsaturated fatty acids as constituent fatty acids. The amount of DHA contained per 100 g of edible portion can be 500 mg or more, preferably 1000 mg or more, more preferably 1250 mg or more, even more preferably 1500 mg or more, even more preferably 2000 mg or more, and even more preferably 2500 mg or more.

[0061] The composition of the present invention or a food composition containing the same, etc. may contain polyunsaturated fatty acids, and it is possible to indicate that they contain such components, their functions, and that they can be used for ingestion, and it is also possible to indicate specific targets for which ingestion is recommended (for example, those who are concerned about neutral fat, those who want to ingest DHA, etc.). The indication can be made directly or indirectly. Examples of direct indication are descriptions on tangible objects such as the product itself, package, container, label, tag, etc., and examples of indirect indication are advertising and promotional activities by means of places or means such as flyers, pamphlets, exhibitions, storefronts, websites, books, newspapers, magazines, television, radio, mailed items, e-mails, voices, etc.

[0062] Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples.

Examples

[0063] [Search and determination of important aroma components of the oxidized odor of lipids containing polyunsaturated fatty acids] 1. Estimation of important aroma components of oxidized odor <Accelerated deterioration> A fish oil product (DHA content in the oil and fat is 19% by mass or more, and γ-tocopherol is blended as an antioxidant) that meets the following specifications sold by Maruha Nichiro Co., Ltd. was divided into small portions to fill a 110 mL glass vial (product number; 9-852-10) manufactured by AS ONE Corporation, and stored in a thermostat set at 40 °C for 2 weeks. After storage, oxygen was sealed and further stored at 40 °C for 1 week.

[0064] The product used meets the following specifications. · Acid value: 0.5 mg / g or less · Iodine value: 160 - 200 g / 100 g · Saponification value: 170 - 200 mg / g · Peroxide value: 2.0 meq / kg or less · Color tone: 4 or less (Gardner)

[0065] The obtained deteriorated oil exhibited a sharp and metallic smell, and it was confirmed that it had an oxidized odor. The DHA content mentioned here was measured by the following method.

[0066] <DHA Content Measurement> Into a stoppered test tube, 6 mg of methyl tricosanoate was precisely weighed as an internal standard substance, and then 30 mg of lipid was precisely weighed. Next, 1.5 mL of 0.5 mol / L NaOH methanol solution was added, and after nitrogen substitution, it was heated at 100 °C for 9 minutes (the process of forming free substances from glyceride forms). After cooling, 2 mL of boron trifluoride methanol complex - methanol solution was added, and after nitrogen substitution, it was heated at 100 °C for 7 minutes (the process of methyl esterification of free substances). After cooling, 3 mL of trimethylpentane (containing 0.1% dibutylhydroxytoluene) was added and stirred for 3 minutes. Then 7 mL of distilled water was added and stirred for 30 seconds. The upper - layer trimethylpentane layer was separated and diluted 50 - fold with trimethylpentane (containing 0.1% dibutylhydroxytoluene) (purification process). This was dehydrated with anhydrous sodium sulfate and analyzed by gas chromatography. The DHA content was determined (g / 100 g) from the area value and weighing value of methyl tricosanoate, and the area ratio of DHA. Also, the composition ratio of DHA in all constituent fatty acids is the ratio of the area value corresponding to DHA to the area value obtained by excluding the peaks derived from the dilution solvent, methyl tricosanoate, and dibutylhydroxytoluene from the total peak area of the chromatogram.

[0067] Gas Chromatograph Operating Conditions Model: GC - 17A (Shimadzu) Detector: FID Column: J&W DB - 23 0.25 mm×30 m Temperature: Injection port 250 °C Column 50 °C (1 min) → 170 °C (10 °C / min) → 210 °C (1.2 °C / min) Detector 250 °C Gas flow rate: He (carrier gas) 113 kPa (1 min) → 164 kPa (4.2 kPa / min) → 181 kPa (0.5 kPa / min) Nitrogen (make-up gas) 90 kPa Hydrogen 60 kPa Air 50 kPa

[0068] <Aroma extraction> The above deteriorated oil (40 g) was collected in an Erlenmeyer flask, dichloromethane (Kanto Chemical, pesticide analysis grade) (120 mL) was added, and the aroma of the deteriorated oil was extracted by the Solvent Assisted Flavor Extraction (hereinafter referred to as SAFE) method. The obtained extract was concentrated to 10 mL and made up to volume.

[0069] <Aroma analysis method 1> GC-MS (7890-5977 MSD) manufactured by Agilent Technologies and MPS, DHS, and TDU manufactured by Gerstel were used. The GC-MS is equipped with ODP3 and single PFC manufactured by Gerstel, which will be described later. 300 μL of the aroma extract placed in a 10 mL glass vial was heated to 80 °C under a nitrogen stream and circulated for 30 minutes to adsorb the aroma components onto the TDU tube (Carbopack B manufactured by Gerstel). Then, the aroma components were desorbed at 280 °C with the TDU, recollected by CIS, and desorbed at 250 °C. After further collecting it with a cold trap (CTS2 manufactured by Gerstel, trapping temperature -100 °C), the aroma components were desorbed by heating CTS2 to 280 °C and introduced into the analytical column (InertCap Pure Wax, length 60 m, inner diameter 0.25 mm, film thickness 0.25 μm). The temperature rising conditions were maintained at 40 °C for 10 minutes, then the temperature was raised to 230 °C at a gradient of 5 °C / min and held for 20 minutes. The average linear velocity was 20.6 cm / sec. The components were estimated using the NIST library, and the compounds were identified by measuring commercially available standards. Only for 2-(2-pentenyl)furan, the synthesized compound according to the method of Smagla et al. as described below was used as a standard (M. S. Smagla, et al. J. Am. Oil Chem. Soc. 1979, 56, 516.).

[0070] <Synthesis of 2-(2-Pentenyl)furan> Under a nitrogen atmosphere, furan (2.5 mL) and tetrahydrofuran (30 mL) were added to a 100 mL two-necked round-bottom flask, and the mixture was cooled to -25 °C using a dry ice-ethanol refrigerant. Subsequently, 25 mL of n-butyllithium (1.6 M in hexane) was added dropwise, and the mixture was stirred at -15 °C for 4 hours. After stirring, (E)-1-bromo-2-pentene (5 g) was added dropwise, and the mixture was stirred at -15 °C for 1 hour and then reacted overnight at room temperature. The next morning, ice was added little by little to the reaction solution to stop the reaction. The mixture was extracted twice with diethyl ether (30 mL), and the organic layer was dehydrated with anhydrous sodium sulfate. After natural filtration, the filtrate was purified by atmospheric distillation and vacuum distillation to obtain 2.21 g (yield 48%) of 2-(2-pentenyl)furan, a colorless transparent solution with a boiling point of 65 - 67 °C (3.0 kPa). This 2-(2-pentenyl)furan was used as a trans-rich standard in the following analysis.

[0071] <Aroma Analysis Method 2> An Agilent Technologies GC-MS (7890-5977 MSD) and Gerstel's MPS and TDU were used. After moving the TDU tube (2,6-diphenylene oxide polymer) to the TDU, the aroma components were desorbed at 300 °C, re-collected in the CIS, and the aroma components were desorbed at 250 °C. After further collecting it with a cold trap (Gerstel's CTS2, collection temperature -100 °C), the aroma components were desorbed by heating the CTS2 to 280 °C and introduced into the analytical column (InertCap Pure Wax, length 60 m, inner diameter 0.25 mm, film thickness 0.25 μm). The temperature rising conditions were maintained at 40 °C for 10 minutes, then the temperature was raised to 230 °C at a gradient of 5 °C / min and held for 20 minutes. Also, the average linear velocity was 20.6 cm / sec.

[0072] <GC-Olfactometry Analysis> Analysis was performed by 7 evaluators involved in the development of lipids containing polyunsaturated fatty acids. The analysis used the above GC-MS equipped with Gerstel's odor sniffing device ODP3. The evaluators had received regular basic taste and olfactory training and were regularly involved in handling products related to fish oil and had sufficient recognition of its aroma. The evaluators had previously carried out a word extraction and aggregation operation on the oxidized odor of fish oil (Chemistry and Biology. 50(11):818-824, 2012), shared the recognition of each evaluation term, and then conducted the evaluation.

[0073] <Aroma Extract Dilution Analysis (hereinafter AEDA)> Regarding AEDA, it is described in, for example, Chemistry and Biology Vol. 55, No. 11, 2017, P743-749. Following this, it was carried out according to the following procedure. The dilution ratio of the extract in this method was set as the lowest concentration at which the odor characteristics felt from the stock solution do not change. Specifically, the stock extract was successively diluted with dichloromethane (4, 8, 16, 32, 64-fold dilutions), and the odor characteristics were compared by evaluators using odor paper (Daiichi Yakuhin Kogyo Co., Ltd.). As a result, it was confirmed that the 8-fold dilution solution retained the odor characteristics of the stock solution, while the characteristics were lost in the 16-fold dilution solution. From the above, the concentration used for AEDA was determined to be the 8-fold dilution solution.

[0074] <Results> 155 aroma characteristics were detected from the stock solution, and 56 components were detected from the 8-fold dilution solution. Among these, there were 10 aromas that 43% or more (3 people) of the evaluators could detect in the dilution solution. These 10 components were considered as candidates for important aroma components of the oxidation odor of lipids containing polyunsaturated fatty acids. As the breakdown of the aroma characteristics, there were many components characteristic of oxidation odor such as "sour, grass, plastic, metal, stinkbug", and components related to the odor of chemicals such as "disinfectant solution".

[0075]

Table 1

[0076] 2. Repeated concentration and omission tests using a fractionation device The 10 components found by AEDA are candidates for important aroma components of the oxidation odor of lipids containing polyunsaturated fatty acids. However, since there are unidentified compounds, and generally aroma components are detected by humans as a so-called composite odor in which a plurality of compounds are mixed, and may be detected as aroma characteristics different from the odor detected from a single compound, analysis of the odor of these 10 components mixed is necessary especially for determining compounds with high contribution. Therefore, aroma collection using GC-MS equipped with a fractionation mechanism (singlePFC manufactured by Gerstel) and an aroma burnout device (Thermal Extractor manufactured by Gerstel) was considered.

[0077] <Fraction collection of aroma components> The basic analysis method is as described in the above-mentioned <Aroma Analysis Method 1>, but the sample used was deteriorated oil (500 - 1000 μL). This time, in order to fractionate the compounds shown in the above table, a single PFC manufactured by Gerstel was used to collect the said compounds in a TDU tube. That is, a flow path switching mechanism (valve switching) was installed in the flow path after the column outlet, and the flow path was switched according to the elution time of the target compound. The target compound was collected by installing a TDU tube (2,6-diphenylene oxide polymer) for aroma collection at the outlet (ODP3) of the switched flow path.

[0078] <Thermal Extractor conditions> ·Total Flow 163 mL / min, Vent: 11.3 mL / min ·Flow meter scale: 200 mL, Pressure: 0.4 MPa ·Initial temperature: 100 °C, held for 0 min, heated at 20 °C / min → 160 °C, held for 3 min ·Collection bag: Azwan-made odor bag (250 mm × 250 mm, capacity 3 L) As described above, the heating and nitrogen gas flow conditions were set. The TDU tube that had collected the aroma was set in the main body, and an odor collection bag was installed on the opposite side of the main body, and the fractionated aroma was collected in the bag.

[0079] <Results> (Omission test of deteriorated aroma using PFC (Preparative Fraction Collector)) Using deteriorated oil (500 μL) as a sample, the target 10 components were fractionally collected 10 times. As a result of re-analyzing the collected TDU tubes by GC-MS (the analytical method is the aforementioned <Aroma Analysis Method 2>), it was confirmed that all the target peaks had been collected. Fractional collection was performed again, and the obtained TDU tubes were baked out using a Thermal Extractor, and the collected aroma was confirmed by the above 7 evaluators. As a result, it had aroma characteristics characteristic of oxidized odor and also had the characteristics of lipids containing deteriorated polyunsaturated fatty acids. That is, it was confirmed that the composite odor composed of the target 10 components already exhibited the same odor characteristics as deteriorated fish oil.

[0080] Next, in order to confirm which of the obtained important aroma components had a high contribution to the composite odor, an omission test by fractional collection was carried out in the test plots shown in the following table ("+" in the table is the compound fractionally collected, and "-" is the compound not targeted for collection). As a result, the composite aroma obtained when the unknown compounds (test plots 2 and 3) were excluded did not change from the control (test plot 1; hereinafter referred to as the control). This means that the contribution of the unknown compounds to the oxidized odor composite aroma is low. On the other hand, when 2-(2-pentenyl)furan was excluded (test plot 4), the aroma characteristics were significantly different from those of the control. This means that 2-(2-pentenyl)furan has a high contribution as an aroma component constituting the oxidized odor found in this AEDA test and is an especially important component as an index. There are no reported examples of this compound as an important aroma component of oxidized odor in the analysis of the composite odor of lipids containing deteriorated polyunsaturated fatty acids. Also, considering that a trans-rich standard product obtained by organic synthesis was used and its retention time (RT) was consistent with that of the standard product, it was strongly presumed to contain the trans form.

[0081] From the above results, (1), (3), (4), (5), (6), (7), and (10) shown in the above table were determined as important aroma components of the oxidized odor of lipids containing polyunsaturated fatty acids.

[0082] [Table 2]

[0083] (Public Literature on 2-(2-Pentenyl)furan (supplement)) Elmore et al. analyzed the aroma components of roasted muscle from cattle fed diets containing different types of oils. As a result, 2-(2-pentenyl)furan (analyzed as E / Z mixture) was significantly higher in roasted meat from cattle fed diets containing fish oil (highest C22:6 content) than in control diets (no ω-3). However, the authors speculated that this compound may have a high threshold and therefore may not contribute much to the important aroma components of roasted meat (JS Elmore, et al. J. Agric. Food. Chem. 1999, 47, 1619.).

[0084] [Preparation of lipid composition with adjusted water content] In order to obtain a deacidified and degummed fish oil with a peroxide value of 0.5 meq / kg or less and an acid value of 0.5 or less (both peroxide value and acid value were determined using the analytical method described in the 2003 edition of the Standard Methods for the Analysis of Fats, Oils and Oils (compiled by the Japan Oil Chemists' Society)), a refined fish oil was obtained by combining reduced pressure distillation, adsorption and steam distillation according to the method described in the above section (Adjustment of water content, production method of lipid composition). Analysis of the refined fish oil found that the composition ratio of DHA to the total fatty acids was 22.6% and EPA was 5.9%, respectively, with a peroxide value of 0.1 and an acid value of 0.1.

[0085] The obtained fish oil (20 mL) was placed in a 50 mL glass vial, and 10 μL or 40 μL of ultrapure water was added thereto and stirred well to prepare fish oil with 500 ppm or 2000 ppm of water added, respectively.

[0086] A sample with sufficient water removed from the obtained fish oil was also prepared. That is, the fish oil (30 mL) was collected in a 50 mL round-bottom glass container, anhydrous sodium sulfate (odorless) (6 g) was added thereto, and after thorough stirring, centrifugation was performed (3000 rpm, 5 minutes), and the supernatant was collected.

[0087] For these, a moisture content analysis and an accelerated degradation test were conducted.

[0088] <Analysis of Moisture Content> It was measured by the Karl Fischer method (volumetric titration) by entrusting (a certain foundation) Japan Food Analysis Center or JFE Techno Research.

[0089] The results are shown in the table below. The moisture in the fish oil without added water was 200 ppm. The moisture in the fish oil with 500 ppm or 2000 ppm of added water was 700 ppm and 2200 ppm, respectively. This means that the added water was directly reflected as the content, suggesting that fish oil with adjusted moisture content could be prepared.

[0090]

Table 3

[0091] <Analysis of PFAS> (Method) It was entrusted to Eurofins Food Testing Co., Ltd., and the PFAS in the above-mentioned fish oil without added water was analyzed by an analytical method using LC-MSMS.

[0092] (Analysis Results) Perfluorooctanesulfonic acid (PFOS) was less than 0.10 ng / g, and perfluorooctanoic acid (PFOA) was less than 0.10 ng / g.

[0093]

Table 4

[0094] <Accelerated Degradation Test> The above four types of fish oil (fish oil without water added, fish oil with water added equivalent to 500 ppm, fish oil with water added equivalent to 2000 ppm, and dehydrated fish oil by adding anhydrous sodium sulfate) were left standing in a constant temperature machine at 50 °C for 3 days. At this time, the lid of the vial (screw tube bottle 9-852-09 manufactured by AS ONE) was tightened, and the headspace was stored without any special replacement by nitrogen gas flow or the like.

[0095] Anhydrous sodium sulfate (6 g) was added to each fish oil after standing for 3 days, and it was left standing for a while (excluding the fish oil that had already been dehydrated). Then, the supernatant (10 mL) was collected in a 50 mL glass vial and used for the sensory evaluation and aroma component analysis shown below. Here, the dehydration by adding anhydrous sodium sulfate is for the following reasons: (1) to prevent the evaluation sensitivity from decreasing due to feeling moisture from the fish oil during the sensory evaluation, (2) because storing the fish oil sample with moisture would be a factor in degradation during storage, and (3) because the presence of moisture in the fish oil would interfere with the measurement during analysis. However, removing the moisture after degradation does not affect the evaluation results. The fish oil without water added had a barely detectable oxidized odor even after the degradation test and was evaluated as acceptable for food use.

[0096] ·Regarding the Discrimination Evaluation Method The aluminum foil was wrapped around the glass vial so that the evaluator could not confirm the properties of the oil and fat. Also, the fish oil was provided after heating it in a water bath heated to 50 °C. Two types of fish oil were presented to the evaluator to smell and compare the aromas, and the sample that was felt to have a stronger oxidized odor was presented. That is, the "fish oil without water added" product was used as the comparison standard, and the intensity of the oxidized odor of each fish oil shown in the above table was evaluated.

[0097] The results are shown in the following table. Compared with the fish oil without water added, both the fish oil with water added and the dehydrated fish oil had a stronger oxidized odor.

[0098]

Table 5

[0099] <Aroma Component Analysis> The amount of oxidized odor components in the four types of fish oil shown in the above table was determined by calculating it as a relative quantification value with respect to a standard deteriorated fish oil with a known concentration. That is, first, commercially available fish oil was deteriorated under certain conditions, and the quantification value of the aroma components was obtained as the component analysis result of the standard deteriorated fish oil through SAFE extraction and GC-MS analysis.

[0100] (Preparation of standard deteriorated fish oil) The fish oil product sold by Maruha Nichiro Co., Ltd. (the same one used in the section of "1. Estimation of important aroma components of oxidized odor") (100 mL) was collected into a screw-cap bottle (1 L; product number 2-077-05) manufactured by Iwaki Co., Ltd. After enclosing oxygen in the headspace, aluminum foil was wrapped around the outer periphery and stored at 50 °C for 2 days.

[0101] (Aroma extraction (SAFE extraction)) The deteriorated fish oil (40 g) was collected into an Erlenmeyer flask, 3 times the amount (120 mL) of dichloromethane 5000 (pure chemical, pesticide analysis grade) was added, and the aroma components were extracted using a SAFE extraction device manufactured by Kiriyama Seisakusho. The obtained extract was made up to 100 mL to obtain an aroma extract. Further, the extract was concentrated 10-fold by a nitrogen stream to obtain a measurement sample.

[0102] (Aroma analysis method 1) GC-MS (7890-5977) manufactured by Agilent Technologies and MPS, DHS, and TDU manufactured by Gerstel were used. 300 μL of the standard solution and the measurement sample placed in a 10 mL glass vial were heated to 80 °C under a nitrogen stream and circulated for 30 minutes to adsorb the aroma components onto a TDU tube (Carbopack B). Then, the aroma components were desorbed at 300 °C, re-collected by CIS, and desorbed at 250 °C. After further collecting it with a cold trap (CTS2 manufactured by Gerstel, collection temperature -100 °C), the aroma components were desorbed by heating to 280 °C and introduced into an analysis column (InertCap Pure Wax manufactured by GL Sciences, length 60 m, inner diameter 0.25 mm, film thickness 0.25 μm).

[0103] The temperature increase conditions were to maintain at 40 °C for 10 minutes, then increase the temperature to 230 °C at a gradient of 5 °C / min and hold for 20 minutes. Also, the average linear velocity was 20.6 cm / sec.

[0104] (Analysis results of standard deteriorated fish oil) The results are shown in the following table.

[0105]

Table 6

[0106] Next, the four types of fish oil shown in Table 6 were each analyzed by GC-MS, and from the ratio of the area value and content of each component peak obtained with respect to the standard deteriorated fish oil, the aroma component values in the water-added fish oil, water-unadded fish oil, and dehydrated fish oil were obtained. The analysis results of the oxidation odor components in each deteriorated fish oil are shown below (in the following table). (1) In the water-added fish oil, compared with the water-unadded fish oil, the amounts of both 2-(2-pentenyl)furan and 2,4-heptadienal, which are aroma components after accelerated deterioration, increased. This supports the results of the sensory evaluation. That is, when the moisture in the fish oil exists above a certain concentration, the deterioration is accelerated, the amount of aroma components increases, and a strong oxidation odor is felt. (2) On the other hand, in the dehydrated fish oil added with sodium sulfate anhydrous, compared with the water-unadded fish oil, the amount of 2,4-heptadienal after accelerated deterioration also increased. This supports the results of the sensory evaluation. That is, even when the moisture in the fish oil is below a certain concentration, the deterioration is accelerated, the amount of aroma components increases, and a strong oxidation odor is felt.

[0107] From the above, it was found that adjusting the moisture content in the fish oil to a certain specific concentration range is important from the perspective of suppressing the generation of oxidation odor.

[0108]

Table 7

[0109] <Time-course changes of 2-(2-pentenyl)furan and 2,4-heptadienal over 4 days in the accelerated degradation test> Oxygen was filled into the headspace of a glass vial containing fish oil (a fish oil product sold by Maruha Nichiro Co., Ltd. (the same as that used in the section of "1. Estimation of important aroma components of oxidation odor", except that it does not contain an antioxidant)), and aluminum foil was wound around the outer periphery of the container and stored in a thermostat at 40 °C. At 3 h, 1 d, 2 d, 3 d, and 4 d after the start of storage, sampling (500 μL) was taken into a glass vial (10 mL) as an analytical sample. After opening, oxygen was filled again and the sample was deteriorated again under light shielding with aluminum foil. The collected fish oil was sealed with nitrogen in the headspace and stored at -80 °C until the start of analysis. The generation amounts of 2-(2-pentenyl)furan and 2,4-heptadienal at each time point are shown in Figure 1.

[0110] [Analysis of highly purified fish oil with high DHA] According to the above-mentioned [Preparation of lipid composition with adjusted water content], a purified fish oil (high DHA purified fish oil) with a DHA composition ratio of 55.5% and an EPA composition ratio of 7.5% in all constituent fatty acids, a peroxide value of 0.2, and an acid value of 0.1 was obtained. The evaluator did not feel an oxidation odor when smelling the highly purified fish oil with high DHA.

[0111] Also, the water content was analyzed in the same manner as the above-mentioned <Analysis of water content>. The water content was 200 ppm, which was 600 ppm or less. Furthermore, according to the sections of (Aroma extraction (SAFE extraction)) and (Aroma analysis method 1) of <Analysis of aroma components>, the aroma components of the highly purified fish oil with high DHA were analyzed instead of the deteriorated fish oil, and the following results were obtained.

Table 8

[0112] From the above results, even in a lipid composition with a high composition ratio of polyunsaturated fatty acids, a tendency similar to that confirmed in the present application was observed.

[0113] [Food production examples] <Capsule (food composition in the form of a supplement)> Fish oil (derived from tuna, DHA content 20%, moisture content 200 ppm or less) and an antioxidant are uniformly mixed to prepare a mixture with a final concentration of the antioxidant of 4060 ppm. The obtained mixture is filled into the prepared soft capsule shell by a conventional method to obtain soft capsules. It is possible to ingest 503 mg or more of DHA and EPA combined based on a daily dose of 4 capsules.

Claims

1. A lipid composition containing a lipid having polyunsaturated fatty acids as constituent fatty acids, wherein the composition ratio of the polyunsaturated fatty acids in all the constituent fatty acids of the lipid is 15% or more, the water content is 600 ppm or less, the perfluorooctanesulfonic acid is 0.1 ppb or less and the perfluorooctanoic acid is 0.1 ppb or less.

2. The composition according to claim 1, wherein the water content is 300 ppm or less.

3. The composition according to claim 1, containing an antioxidant.

4. The composition according to any one of claims 1 to 3, wherein 2-(2-pentenyl)furan is less than 0.0095 ppm.

5. The composition according to claim 4, wherein 2,4-heptadienal is less than 2.600 ppm.

6. A method for inspecting the degree of deterioration of a lipid composition containing a lipid having polyunsaturated fatty acids as constituent fatty acids, using any one selected from the group consisting of 1-penten-3-one, 2,6-nonadienal, 2-methyl-2-cyclopentene-1-one, 2-(2-pentenyl)furan, 2,4-decadienal, 4-heptenal, and 2,4-heptadienal as an index.

7. A method for producing a lipid composition with reduced unpleasant odor, containing a lipid having polyunsaturated fatty acids as constituent fatty acids and having a composition ratio of polyunsaturated fatty acids in all the constituent fatty acids of the lipid of 15% or more, comprising the following steps: A step of obtaining a fraction from the raw material, wherein the water content is 600 ppm or less, 2-(2-pentenyl)furan is less than 0.0095 ppm, and 2,4-heptadienal is less than 2.600 ppm.

8. A method for reducing the unpleasant odor of a lipid composition containing a lipid having polyunsaturated fatty acids as constituent fatty acids and having a composition ratio of polyunsaturated fatty acids in all the constituent fatty acids of the lipid of 15% or more, characterized by obtaining a fraction from the raw material that satisfies the following: The water content is 600 ppm or less, 2-(2-pentenyl)furan is less than 0.0095 ppm, and 2,4-heptadienal is less than 2.600 ppm.

9. A lipid composition containing a lipid having a polyunsaturated fatty acid as a constituent fatty acid, wherein the composition ratio of the polyunsaturated fatty acid in all the constituent fatty acids of the lipid is 15% or more, the water content is 600 ppm or less, 2-(2-pentenyl)furan is less than 0.0095 ppm, and 2,4-heptadienal is less than 2.600 ppm.

10. A lipid composition containing a lipid having a polyunsaturated fatty acid as a constituent fatty acid, wherein the composition ratio of the polyunsaturated fatty acid in all the constituent fatty acids of the lipid is 15% or more, the acid value is 0.5 or less and the peroxide value is 2.0 meq / kg or less, the water content is 600 ppm or less, 2-(2-pentenyl)furan is less than 0.0095 ppm, and 2,4-heptadienal is less than 2.600 ppm.

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