JP2020150822A - Oils and fats, method for producing oils and fats, and oxidation inhibitor for oils and fats - Google Patents

Abstract

To provide oils and fats with its oxidation degradation being suppressed.SOLUTION: Oils and fats contain at least one chalcogen-containing compound selected from the following formulae (1) (2) (3).SELECTED DRAWING: None

Description

The present invention relates to fats and oils containing a specific chalcogen-containing compound, a method for producing the same, and an oxidation inhibitor for fats and oils.

The main constituents of fats and oils are fatty acids, but among them, fatty acids with double bonds such as linoleic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid (EPA), and docosahexaenoic acid (DHA), which are called essential fatty acids, are It is essential for human physiological and metabolic processes and must be ingested as food.

In recent years, it has been reported that ingestion of fats and oils containing polyunsaturated fatty acids such as EPA and DHA contained in fish oil reduces triglyceride in blood and improves cognitive function, and consumer needs are increasing. ing. These fats and oils are used in foods and cosmetics in the form of fatty acids or fats and oils.

On the other hand, fats and oils such as fish oil are known to oxidize very quickly because they contain many double bonds.

In order to solve these problems, addition of antioxidants such as tocopherol and rosemary extract (Patent Document 1) is generally performed.
However, the effect of these antioxidants on suppressing the oxidative deterioration of fats and oils was insufficient.
In addition, tocopherol has an optimum amount of addition that has the strongest antioxidant power, and there is a limit to the expected antioxidant power.

In recent years, selenium-containing compounds (Patent Document 2) and sulfur-containing compounds (Patent Document 3) having a biological antioxidant effect have been proposed, but there are no examples of applying these to fats and oils.

Japanese Unexamined Patent Publication No. 2008-303396 Japanese Unexamined Patent Publication No. 2011-121914 Japanese Unexamined Patent Publication No. 2013-116876

The present invention has been made in view of the above problems, and an object of the present invention is to provide an oil or fat in which oxidative deterioration is suppressed.
Another object of the present invention is to provide an oxidation inhibitor for fats and oils that suppresses oxidative deterioration of fats and oils.
Another object of the present invention is to provide foods, pharmaceuticals, and cosmetics containing fats and oils whose oxidative deterioration is suppressed.

As a result of repeated studies to solve the above problems, the present inventor contains a selenium-containing compound (Patent Document 2) and a sulfur-containing compound (Patent Document 3) having a biological antioxidant effect, which have been discovered in recent years, in fats and oils. It has been found that the problem of oxidative deterioration of fats and oils can be solved by making the mixture, and the present invention has been reached.

That is, the gist of the present invention is as follows.

[1] Contains at least one chalcogen-containing compound selected from the group consisting of a compound represented by the following formula (1), a compound represented by the following formula (2), and a compound represented by the following formula (3). , Oils and fats.

(In the formula, M ¹ and M ² are S, Se or Te, M ¹ and M ² may be the same or different, and R is a hydrogen atom, glutathiol group, or cystenyl group. )

[2] The fat or oil according to [1], which further contains tocopherol.

[3] The fat or oil according to [1] or [2], further containing a polar solvent having an octanol partition coefficient of 0.05 or more.

[4] The fat or oil according to any one of [1] to [3], wherein the content of the chalcogen-containing compound is 10 ppb or more.

[5] Any of [1] to [4], which comprises at least one selected from the group consisting of ginkgo biloba extract, γ-aminobutyric acid, curcumin, sesamin, indigestible dextrin, hesperidin, and phosphatidylserine. The fats and oils described in.

[6] The fat or oil according to any one of [1] to [5], wherein the fat and oil is derived from fish oil.

[7] The fat or oil according to any one of [1] to [6], which comprises at least one fat or oil selected from the group consisting of docosahexaenoic acid, eicosapentaenoic acid, and arachidonic acid.

[8] A food containing the fat or oil according to any one of [1] to [7].

[9] A pharmaceutical product containing the fat or oil according to any one of [1] to [7].

[10] A cosmetic product containing the oil or fat according to any one of [1] to [7].

[11] Contains at least one chalcogen-containing compound selected from the group consisting of a compound represented by the following formula (1), a compound represented by the following formula (2), and a compound represented by the following formula (3). , Oxidation inhibitor for fats and oils.

(In the formula, M ¹ and M ² are S, Se or Te, M ¹ and M ² may be the same or different, and R is a hydrogen atom, glutathiol group, or cystenyl group. )

[12] The oxidation inhibitor for fats and oils according to [11], which further contains tocopherol.

[13] The oxidation inhibitor for fats and oils according to [11] or [12], which further contains a polar solvent having an octanol partition coefficient of 0.05 or more.

[14] The oxidation inhibitor for fats and oils according to any one of [11] to [13], which further contains an emulsifier.

[15] The oxidation inhibitor for fats and oils according to any one of [11] to [14], wherein the content of the chalcogen-containing compound is 10 ppm or more.

[16] The oxidation inhibitor for fats and oils according to any one of [11] to [15], which is an oxidation inhibitor for fats and oils derived from fish oil.

[17] At least one chalcogen-containing compound selected from the group consisting of a compound represented by the following formula (1), a compound represented by the following formula (2), and a compound represented by the following formula (3), and octanol. A method for producing a fat or oil, which comprises a step of mixing with a polar solvent having a partition coefficient of 0.05 or more and then mixing with the fat or oil.

(In the formula, M ¹ and M ² are S, Se or Te, M ¹ and M ² may be the same or different, and R is a hydrogen atom, glutathiol group, or cystenyl group. )

According to the present invention, there are provided foods, pharmaceuticals, and cosmetics containing fats and oils with suppressed oxidative deterioration and fats and oils with suppressed oxidative deterioration.
Further, according to the present invention, an oxidation inhibitor for fats and oils having an excellent effect of suppressing oxidation deterioration of fats and oils is provided.

Embodiments of the present invention will be described in detail below.
The description of the constituent elements described below is an example (representative example) of the embodiment of the present invention, and the present invention is not specified in these contents unless the gist thereof is exceeded.

The fat and oil of the present invention is at least one chalcogen-containing compound selected from the group consisting of a compound represented by the following formula (1), a compound represented by the following formula (2) and a compound represented by the following formula (3). (Hereinafter, it may be referred to as "the chalcogen-containing compound of the present invention"). The fat and oil of the present invention is preferably produced by mixing the calcogen-containing compound of the present invention with a polar solvent having an octanol partition coefficient of 0.05 or more according to the method for producing the fat and oil of the present invention, and then mixing the fat and oil with the fat and oil. be able to.
The oxidation inhibitor for fats and oils of the present invention contains the chalcogen-containing compound of the present invention.

(In the formula, M ¹ and M ² are S, Se or Te, M ¹ and M ² may be the same or different, and R is a hydrogen atom, glutathiol group, or cystenyl group. )

[mechanism]
Although the details of the mechanism of suppressing the oxidation of fats and oils produced by the present invention are not clear, the antioxidative property of the chalcogen-containing compound of the present invention due to the ethenthio (ethencalcogen) urea group donating protons and the chalcogen causes it. It is presumed to be due to the reduction of peroxide.

[Chalcogen-containing compounds]
M ¹ and M ² in the formulas (1) to (3) representing the chalcogen-containing compound of the present invention are chalcogen elements S, Se or Te, but S and Se are preferable, and the strength of antioxidant power is high. From the point of view, Se is particularly preferable.

For example, the chalcogen-containing compound in which M ¹ is Se and R is a hydrogen atom in the formula (1) is 3- (2-hydroseleno-1H-imidazol-5-yl) -2- (trimethylaminoio) probe, and is of the formula (2) The compound in which M ^{1 of} 2) is Se is 3- (2-selenoxo-2,3-dihydro-1H-imidazol-4-yl) -2- (trimethylamino) probe. All of these chalcogen-containing compounds are monomeric. The compound in the formula (1) in which M ¹ is Se and R is a hydrogen atom has a molecular structure in which a selenol group is bonded to a carbon atom at the 2-position of the pyrimidine ring, and the selenol group is in an equilibrium state with a selenol ketone group. Since it forms a tautomer in, it has two chemical forms, a selenol type (formula (1)) and a selenoketone type (formula (2)), depending on the conditions of the solvent in the solution state. .. In the presence of a non-polar solvent whose equilibrium is inclined to the selenol-type isomer, an oxidized dimer is easily formed, while in a polar solvent, the chemical equilibrium is biased to the selenoket-type isomer and it mainly exists as a monomer. Has the property of

Further, the chalcogen-containing compound in which M ¹ and M ² of the formula (3) are Se is a dimer of the chalcogen-containing compound in which M ¹ of the formula (1) is represented by Se and forms diselenide via a selenol group. The body.
Similarly, when M ¹ is S or Te, the formulas (1) and (2) are tautomers. Formula (3) is an oxidized dimer of formula (1), but M ¹ and M ² may be different. Further, for example, a chalcogen-containing compound in which M ¹ is S and a chalcogen-containing compound in which Se may be used in combination.

In formula (1), R is a hydrogen atom, a glutathiol group, or a cystenyl group.
That is, the chalcogen-containing compound in which R is a hydrogen atom in the formula (1) can be bonded to a thiol compound such as glutathione, cysteine, acetylcysteine, or homocysteine.

The chalcogen-containing compound of the present invention may be a natural product or a synthetic product.
Examples of natural products containing chalcogen-containing compounds include fish, especially tuna, marlin, mackerel and the like.

The form of the chalcogen-containing compound of the present invention in the fat and oil of the present invention and the oxidation inhibitor for fats and oils may be a purified one or one added as a composition containing the chalcogen-containing compound.
Further, the fat and oil and the oxidation inhibitor for fat and oil of the present invention may contain only one kind of the chalcogen-containing compound of the present invention, or may contain two or more kinds.

[Fat and oil]
The fat and oil of the present invention may be any one containing at least one of the above-mentioned chalcogen-containing compounds of the present invention, and is not particularly limited.
When the chalcogen-containing compound of the present invention in the fat and oil contains Se, the total amount of selenium derived from the chalcogen-containing compound is not particularly limited, but is usually 10 ppb or more, preferably 20 ppb or more, more preferably 30 ppb or more, still more preferably 40 ppb. As mentioned above, it is particularly preferably 60 ppb or more, and usually 500 ppm or less. When the content of the chalcogen-containing compound of the present invention in the fat and oil is within the above-mentioned preferable range, the effect of suppressing the oxidation of the fat and oil can be sufficiently obtained.
The amount of selenium can be measured by an atomic absorption spectrophotometer, an inductively coupled plasma emission spectrometry method, or an inductively coupled plasma mass spectrometer.

The fat and oil of the present invention is not particularly limited as long as it contains the chalcogen-containing compound of the present invention, but it is preferable to further contain tocopherol because a synergistic effect of antioxidant power is exhibited. The tocopherol contained in the fat and oil may be a preparation containing the tocopherol described below.

The preparation containing tocopherol in the present invention contains tocopherol (vitamin E), and preferably the amount of γ-tocopherol in the total tocopherol exceeds 40% by mass.
The total content of tocopherol in the preparation containing tocopherol is preferably 5 to 99% by mass, particularly preferably 8 to 90% by mass. When the content of tocopherol is not less than the above lower limit, it is not necessary to excessively increase the amount of the preparation to be added in order to suppress the oxidation of fats and oils, while when it is not more than the above upper limit, a stable preparation can be obtained.

Further, the content of γ-tocopherol in the preparation containing tocopherol is preferably 20 to 90% by mass, particularly 40 to 80% by mass in the total tocopherol, and the content of γ-tocopherol is within the above range. , Oxidation of fats and oils can be stably suppressed.

The preparation containing tocopherol may contain other components in addition to tocopherol and emulsifier, and examples of other components include antioxidants such as vitamin C, rosmarinic acid, and chlorogenic acid. These other components are preferably contained in a preparation containing tocopherol in a content of about 0.1 to 90% by mass.

The content of tocopherol in the fat and oil of the present invention is usually 0.01% by mass or more, preferably 0.02% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.2% by mass or more, particularly. It is preferably 0.3% by mass or more, usually 40% by mass or less, preferably 5% by mass or less, more preferably 2% by mass or less, still more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less. is there. When the content of tocopherol in the fat and oil of the present invention is within the above-mentioned preferable range, the effect of suppressing the oxidation of the fat and oil can be sufficiently obtained by the synergistic effect with the chalcogen-containing compound of the present invention.

The fat and oil of the present invention is not particularly limited as long as it contains the calcogen-containing compound of the present invention, but the octanol partition coefficient of 0.05 or more is further increased because the calcogen-containing compound of the present invention does not dissolve in the fat and oil. It preferably contains a polar solvent.
The octanol partition coefficient of the polar solvent is preferably 0.05 or more, more preferably 0.2 or more, still more preferably 0.3 or more, and usually 1.0 or less, preferably 0.6 or less. When the octanol partition coefficient of the polar solvent is in the above-mentioned preferable range, the chalcogen-containing compound of the present invention can be easily dispersed, and the effect of suppressing oxidative deterioration of fats and oils can be sufficiently obtained.

Specific examples of the polar solvent having an octanol distribution coefficient of 0.05 or more include one or more of isopropyl alcohol, acetic acid, acetone, ethanol, and methanol, and acetic acid and acetone are among them for economic reasons. Ethanol is preferred and is preferred for safety and sensory reasons.

The content of the polar solvent having an octanol partition coefficient of 0.05 or more in the fat or oil is not particularly limited, but is usually 10% by mass or more, preferably 20% by mass or more, based on the calcogen-containing compound of the present invention in the fat or oil. It is more preferably 50% by mass or more, usually 200% by mass or less, preferably 100% by mass or less, and more preferably 80% by mass or less. When the content of the polar solvent having an octanol partition coefficient of 0.05 or more in the fat or oil is within the above-mentioned preferable range, the chalcogen-containing compound of the present invention can be effectively dispersed and the effect of suppressing the oxidation of the fat or oil can be sufficiently obtained. ..

The fat and oil of the present invention is not particularly limited as long as it contains a chalcogen-containing compound, but for example, it is preferable to further contain an emulsifier in order to stably disperse it in foods, cosmetics, and pharmaceuticals containing water. ..

The emulsifier is preferably a food emulsifier, and may be a synthetic emulsifier or a natural emulsifier. Specifically, examples of the synthetic emulsifier include sucrose fatty acid ester, glycerin fatty acid ester, polyglycerin fatty acid ester, organic acid glycerin fatty acid ester, lactic acid fatty acid ester, and sorbitan fatty acid ester. Natural emulsifiers include polysaccharides such as processed starch and dextrin, plant lecithin, egg yolk lecithin, fractionated lecithin, enzyme-treated lecithin, enzymatically decomposed lecithin and other lecithin, saponin, kiraya saponin, soybean saponin and other saponins, and spingo. Examples thereof include lipids, phospholipids such as vegetable lecithin and animal lecithin, and glycolipids such as bile powder and tomato glycolipid. Of these, glycerin fatty acid ester, sucrose fatty acid ester, and polysaccharide are preferably used, and among the polysaccharides, sodium octenyl succinate starch and dextrin are particularly preferable.
One of these may be used alone, or two or more thereof may be mixed and used.

The content of the emulsifier in the fat is usually 0.01 to 20% by mass, particularly preferably 0.1 to 5% by mass. When the content of the emulsifier is within the above range, it can be stably dispersed in foods, cosmetics and pharmaceuticals containing water.
The emulsifier may be contained in fats and oils as an emulsifier contained in the above-mentioned preparation containing tocopherol, for example.

The fat and oil of the present invention is not particularly limited as long as it contains the chalcogen-containing compound of the present invention, but other components include ginkgo biloba extract, γ-aminobutyric acid, curcumin, sesamin, indigestible dextrin, and hesperidin. , Phosphatidylserine may be contained.

The fat or oil of the present invention is not particularly limited as long as it contains the chalcogen-containing compound of the present invention, but a fat or oil containing one or more unsaturated fatty acids having an unsaturated bond is preferable. As the unsaturated fatty acid contained in the fat and oil of the present invention, unsaturated fatty acids such as oleic acid, linoleic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid (EPA), and docosahexaenoic acid (DHA) are preferable, and among them, unsaturated bonds are formed. An unsaturated fatty acid having two or more is preferable, an unsaturated fatty acid having three or more unsaturated bonds, and more preferably an arachidonic acid, an eicosapentaenoic acid (EPA), and a docosahexaenoic acid having four or more unsaturated bonds. (DHA) is preferable, and DHA, EPA, and arachidonic acid are most preferable.

The fats and oils of the present invention are particularly preferably fats and oils containing 5% by mass or more of DHA and EPA, and are preferably derived from fish oil because they contain a large amount of the above unsaturated fatty acids and can be stably supplied.

The fats and oils of the present invention can be used as foods, cosmetics, pharmaceutical additives and the like.

As food applications, for example, it is used for supplements and processed foods containing fish oil, supplements containing perilla oil and perilla oil, and processed foods.
In addition, as cosmetic applications, it is used in beauty essences, facial masks, protective emulsions, protective creams, and the like.
Further, as a pharmaceutical application, it is used for stabilizing unstable compounds and the like.

[Manufacturing method of fats and oils]
The fat and oil of the present invention can be produced, for example, by mixing the fat and oil with the chalcogen-containing compound of the present invention, but in order to further enhance the effect of suppressing the oxidative deterioration of the fat and oil, the chalcogen-containing compound of the present invention and the octanol partition coefficient After mixing a polar solvent having a value of 0.05 or more, it is preferable to mix the obtained mixture with fats and oils. As described above, by mixing the chalcogen-containing compound of the present invention with a polar solvent having an octanol partition coefficient of 0.05 or more in advance and then mixing with the fat and oil, the chalcogen-containing compound of the present invention is dissolved in the fat and oil, and thus oil oxidation It is presumed that the deterioration suppression effect can be further enhanced.

The mixing ratio when mixing the chalcogen-containing compound of the present invention and the polar solvent having an octanol partition coefficient of 0.05 or more is such that the amount of the polar solvent having an octanol partition coefficient of 0.05 or more is the above-mentioned fat or oil of the present invention. It is preferable to mix them so that the octanol partition coefficient with respect to the content of the chalcogen-containing compound of the present invention is 0.05 or more.

Further, in the case of producing the fat and oil of the present invention containing tocopherol and the like, the above-mentioned preparation containing tocopherol and other additives may be added and mixed with the fat and oil, but the preparation containing tocopherol and other additives may be mixed. The mixture of the chalcogen-containing compound of the present invention and a polar solvent having an octanol partition coefficient of 0.05 or more may be mixed before, after, or at the same time. When the chalcogen-containing compound of the present invention and a polar solvent having an octanol partition coefficient of 0.05 or more are mixed, a preparation containing tocopherol or other additives may be mixed together.

[Oxidation inhibitor for fats and oils]
The oxidation inhibitor for fats and oils of the present invention contains the chalcogen-containing compound of the present invention.
The oxidation inhibitor for fats and oils of the present invention may contain tocopherol, a polar solvent having an octanol distribution coefficient of 0.05 or more, an emulsifier, etc. in addition to the chalcogen-containing compound of the present invention, and the content thereof is particularly limited. However, the amount may be such that it satisfies these contents in the above-mentioned fats and oils. For example, when the chalcogen-containing compound of the present invention in the oxidation inhibitor for fats and oils of the present invention contains Se, it contains chalcogen. The total selenium content derived from the compound is usually 10 ppm or more, preferably 100 ppm or more, more preferably 0.1% by mass or more, still more preferably 0.2% by mass or more, and particularly preferably 0.4% by mass or more. When the content of the chalcogen-containing compound of the present invention in the oxidation inhibitor for fats and oils is within the above-mentioned preferable range, the oxidation inhibitory effect of the fats and oils can be sufficiently suppressed without excessively increasing the amount of the oxidation inhibitor for fats and oils added to the fats and oils. Obtainable.

The oxidation inhibitor for fats and oils of the present invention may contain tocopherol or a preparation containing the above-mentioned tocopherol, in which case the content of tocopherol in the oxidation inhibitor for fats and oils of the present invention is usually 10% by mass or more. The content of tocopherol in the oxidation inhibitor for fats and oils of the present invention is preferably 20% by mass or more, more preferably 40% by mass or more, further preferably 60% by mass or more, and particularly preferably 90% by mass or more. When it is in a suitable range, the effect of suppressing the oxidation of fats and oils can be sufficiently obtained with a good synergistic effect.

The oxidation inhibitor for fats and oils of the present invention preferably further contains the polar solvent having the above-mentioned octanol partition coefficient of 0.05 or more for the same reason as in the above-mentioned fats and oils.
The content of the polar solvent having an octanol partition coefficient of 0.05 or more in the oxidation inhibitor for fats and oils of the present invention is not particularly limited, but is usually 0 with respect to the chalcogen-containing compound of the present invention in the oxidation inhibitor for fats and oils. It is 001% by mass or more, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and usually 20% by mass or less, preferably 10% by mass or less, more preferably 1% by mass or less. When the content of the polar solvent having an octanol partition coefficient of 0.05 or more in the oxidation inhibitor for fats and oils is within the above preferable range, the chalcogen-containing compound of the present invention is effectively dispersed to sufficiently suppress the oxidation of fats and oils. Obtainable.

The oxidation inhibitor for fats and oils of the present invention may further contain an emulsifier in order to stably disperse the fats and oils in foods, cosmetics and pharmaceuticals containing water.
Examples of the emulsifier include those exemplified as the emulsifier contained in the above-mentioned fats and oils, and one type may be used alone or two or more types may be used in combination.

The content of the emulsifier in the oxidation inhibitor for fats and oils of the present invention is usually 10% by mass or less, particularly preferably 5% by mass or less. When the content of the emulsifier is within the above range, the fat and oil to which the emulsifier is added can be stably dispersed in foods, cosmetics and pharmaceuticals containing water.

The antioxidant for fats and oils of the present invention may also contain ginkgo biloba extract, γ-aminobutyric acid, curcumin, sesamin, indigestible dextrin, hesperidin, and phosphatidylserine as other components.

The oxidation inhibitor for fats and oils of the present invention is particularly suitable as an oxidation inhibitor for fats and oils derived from fish oil for the same reason as in the above description of the fats and oils of the present invention.
Further, the oxidation inhibitor for fats and oils of the present invention is added to the fats and oils so that the content of the chalcogen-containing compound and other components of the present invention in the fats and oils is within the above-mentioned preferable range.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the description of the following Examples as long as the gist of the present invention is not exceeded.

In the following, Emix 70L (manufactured by Mitsubishi Chemical Foods Co., Ltd.) was used as the mixed tocopherol.
As the preparation containing the chalcogen-containing compound, the preparation containing 20 ppm of the compounds ¹ to 3 in which M ¹ is Se in the formulas (1) to (3) as the total amount of selenium (hereinafter referred to as “chalcogen-containing preparation”) was used. ..

(Comparative Example 1)
By removing tocopherol by distilling corn oil, fat and oil A containing no tocopherol was obtained.

(Comparative Example 2)
Mixed tocopherol was added to the fat and oil A in an amount of 0.1% by mass as the content in the fat and oil to obtain the fat and oil B.

(Example 1)
A chalcogen-containing preparation / ethanol mixed solution was obtained by dissolving in ethanol (octanol partition coefficient: 0.3) so that the concentration of the chalcogen-containing preparation was 40% by mass. Next, a chalcogen-containing preparation / ethanol mixed solution was added to the fat and oil A so that the chalcogen-containing preparation content in the fat and oil was 0.2% by mass to obtain the fat and oil C (the total selenium content in the fat and oil C was 40 ppb). ).

(Example 2)
Oil D was obtained in the same manner as in Example 1 except that the chalcogen-containing preparation / ethanol mixed solution was added to the oil A so that the content of the chalcogen-containing preparation in the oil was 0.4% by mass (in the oil D). Total selenium content 80 ppb).

(Example 3)
Further, fat E was obtained in the same manner as in Example 1 except that mixed tocopherol was added so as to have a content of 0.1% by mass in the fat (total selenium content 40 ppb in the fat E).

(Example 4)
Further, the fat and oil F was obtained in the same manner as in Example 2 except that mixed tocopherol was added so as to have a content of 0.1% by mass in the fat and oil (total selenium content in the fat and oil F was 80 ppb).

(Example 5)
A fat and oil G was obtained in the same manner as in Example 4 except that the chalcogen-containing preparation was added as it was so that the chalcogen-containing preparation content of the fat and oil was 0.4% by mass without being dissolved in ethanol (in the fat and oil G). Total selenium content 80 ppb).

(Measurement of oxidation inhibitory effect)
The oxidation inhibitory effect of fats A to G was measured as follows.
About 10 g of each of the fats and oils A to G was placed in a test tube and stored in a constant temperature bath at 40 ° C. The fats and oils after 14 days of storage were analyzed according to the peroxide value test method (potentiometric titration standard fats and oils analysis method 2.5.2.2) and evaluated according to the following criteria. The peroxide value is a numerical value expressed in (meq / kg) as the amount of lipid peroxide produced by oxidizing the lipid, and the smaller this value is, the more excellent the oxidation suppressing effect is. The results are shown in Table 1.

(Evaluation criteria)
1: Peroxide value 13.9 or less 2: Peroxide value 14.0 or more, 15.9 or less 3: Peroxide value 16.0 or more, 17.9 or less 4: Peroxide value 18.0 or more, 19.9 Below 5: Peroxide value 20.0 or more

(Discussion)
Since corn oil contains a large amount of linoleic acid, linolenic acid, oleic acid, etc., it is easily oxidized, and the peroxide value significantly increased when the mixed tocopherol or selenonein-containing preparation was not added (fat A).
Further, even if mixed tocopherol, which is a conventionally known antioxidant, was added, a sufficient antioxidant effect was not exhibited (fat B).
On the other hand, the chalcogen-containing preparation suppressed the increase in peroxide value by adding it after dissolving it in ethanol (fat C). Further, the effect was more remarkable by increasing the addition amount of the chalcogen-containing preparation (fat and oil D).
Furthermore, the effect of the chalcogen-containing preparation was higher when it was added together with mixed tocopherol than when it was added alone (fat E, fat F).
Further, it was clarified that the effect is more exerted when the chalcogen-containing preparation is dissolved in ethanol and added to the fat (fat F) than when it is directly added to the fat (fat G).

(Comparative Example 3)
Fish oil (containing 390 mg / g of DHA and 45 mg / g of EPA) having a tocopherol content of 3000 ppm was designated as fat and oil H.

(Comparative Example 4)
A tea extract (manufactured by Mitsubishi Chemical Foods Co., Ltd., Sunfood oily) was added to the fat and oil H so that the content in the fat and oil was 3% by mass to obtain the fat and oil I.

(Comparative Example 5)
Rosemary extract (RM Keeper OS, manufactured by Mitsubishi Chemical Foods Co., Ltd.) was added to the fat and oil H so that the content in the fat and oil was 3% by mass to obtain the fat and oil J.

(Comparative Example 6)
An astaxanthin-containing preparation (astaxanthin content of 5% by mass) was added to the fat and oil H so that the content in the fat and oil was 3% by mass to obtain the fat and oil K.

(Example 6)
A chalcogen-containing preparation / ethanol mixed solution was obtained by dissolving in ethanol (octanol partition coefficient: 0.3) so that the concentration of the chalcogen-containing preparation was 40% by mass. Next, a chalcogen-containing preparation / ethanol mixed solution was added to the fat and oil H so that the content of the chalcogen-containing preparation in the fat and oil was 0.4% by mass to obtain the fat and oil L (total selenium content in the fat and oil L 80 ppb). ..

(Measurement of oxidation inhibitory effect)
The oxidation inhibitory effect of fats and oils H to L was measured as follows.
About 3 g of each of the fats and oils H to L was placed in a test tube and stored in a constant temperature bath at 40 ° C. The fats and oils 21 days after storage were analyzed according to the peroxide value test method (potentiometric titration standard fats and oils analysis method 2.5.2.2), and evaluated according to the following criteria. The results are shown in Table 2.
(Evaluation criteria)
1: Peroxide value less than 40 2: Peroxide value 40 or more and less than 60 3: Peroxide value 60 or more and less than 80 4: Peroxide value 80 or more and less than 100 5: Peroxide value 100 or more

(Discussion)
Since fish oil contains a large amount of polyunsaturated fatty acids such as DHA and EPA, it is easily oxidized, and even if it contains tocopherol, which is a conventionally known antioxidant, it shows a sufficient antioxidant effect. There was no (oil H). Furthermore, by adding tea extract, rosemary extract, and astaxanthin known as antioxidants to fats and oils H, an oxidation inhibitory effect is exhibited (fat and oils I to K), but chalcogen-containing preparations are contained. It was clarified that a more remarkable antioxidant effect was exhibited when the mixture was allowed to be used (oil L).

From the results of the above Examples and Comparative Examples, the following can be understood.
-The fats and oils containing the chalcogen-containing compound of the present invention suppress oxidative deterioration.
-By mixing the chalcogen-containing compound of the present invention with a polar solvent having an octanol partition coefficient of 0.05 or more and then mixing the mixture with fats and oils, the effect of suppressing oxidation is improved.
-Tocopherol alone has the same antioxidant effect as that without any addition, but by combining the chalcogen-containing compound of the present invention with tocopherol, a synergistic effect is exhibited, and the oxidation-suppressing effect is higher than that of the chalcogen-containing compound of the present invention alone. The effect is further improved.

Claims (17)

An oil or fat containing at least one chalcogen-containing compound selected from the group consisting of a compound represented by the following formula (1), a compound represented by the following formula (2), and a compound represented by the following formula (3).

(In the formula, M ¹ and M ² are S, Se or Te, M ¹ and M ² may be the same or different, and R is a hydrogen atom, glutathiol group, or cystenyl group. ) The fat or oil according to claim 1, further containing tocopherol. The fat or oil according to claim 1 or 2, further comprising a polar solvent having an octanol partition coefficient of 0.05 or more. The fat or oil according to any one of claims 1 to 3, wherein the total selenium content derived from the chalcogen-containing compound is 10 ppb or more. The invention according to any one of claims 1 to 4, which comprises at least one selected from the group consisting of ginkgo biloba extract, γ-aminobutyric acid, curcumin, sesamin, indigestible dextrin, hesperidin, and phosphatidylserine. Oils and fats. The fat or oil according to any one of claims 1 to 5, wherein the fat or oil is derived from fish oil. The fat or oil according to any one of claims 1 to 6, which comprises at least one fat or oil selected from the group consisting of docosahexaenoic acid, eicosapentaenoic acid, and arachidonic acid. A food containing the fat or oil according to any one of claims 1 to 7. A pharmaceutical product containing the fat or oil according to any one of claims 1 to 7. A cosmetic product containing the fat or oil according to any one of claims 1 to 7. For fats and oils, which contains at least one chalcogen-containing compound selected from the group consisting of a compound represented by the following formula (1), a compound represented by the following formula (2), and a compound represented by the following formula (3). Oxidation inhibitor.

(In the formula, M ¹ and M ² are S, Se or Te, M ¹ and M ² may be the same or different, and R is a hydrogen atom, glutathiol group, or cystenyl group. ) The oxidation inhibitor for fats and oils according to claim 11, further containing tocopherol. The oxidation inhibitor for fats and oils according to claim 11 or 12, further comprising a polar solvent having an octanol partition coefficient of 0.05 or more. The oxidation inhibitor for fats and oils according to any one of claims 11 to 13, further comprising an emulsifier. The oxidation inhibitor for fats and oils according to any one of claims 11 to 14, wherein the total selenium content derived from the chalcogen-containing compound is 10 ppm or more. The oxidation inhibitor for fats and oils according to any one of claims 11 to 15, which is an oxidation inhibitor for fats and oils derived from fish oil. At least one chalcogen-containing compound selected from the group consisting of the compound represented by the following formula (1), the compound represented by the following formula (2), and the compound represented by the following formula (3), and the octanol partition coefficient A method for producing a fat or oil, which comprises a step of mixing with a polar solvent of 0.05 or more and then mixing with the fat or oil.

(In the formula, M ¹ and M ² are S, Se or Te, M ¹ and M ² may be the same or different, and R is a hydrogen atom, glutathiol group, or cystenyl group. )