JPH10140152A - Antioxidant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an antioxidant which inhibits the phenomenon that an aliphatic unsaturated compound, especially fat and oil forms a peroxide because its double bond or bonds are spontaneously oxidized upon standing. SOLUTION: This antioxidant is the one used for an aliphatic unsaturated compound, especially an unsaturated fatty acid or an unsaturated fatty acid glyceride and comprising a mixture of potassium carbonate, potassium hydrogencarbonate or a mixture thereof with potassium carbonate with potassium hydrogencarbonate. The antioxidant used is such an amount that 10-800mg of potassium carbonate, potassium hydrogencarbonate or a mixture of potassium carbonate with potassium hydrogen carbonate is used per gram equivalent of the atomic groups >C=C<. In actual use, it is suspended with a surfactant.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aliphatic compound having an unsaturated bond, in particular, fats and oils. Oxidation inhibitor.

[0002]

2. Description of the Related Art Conventionally, α-tocopherol (hereinafter referred to as “vitamin E”) has been used in fats and oils, butter, margarine, and foods, medicines, cosmetics, and the like containing them in order to prevent deterioration in quality due to oxidation of fat. Oxidation inhibitors such as dibutylhydroxytoluene, erythorbic acid, sodium erythorbate, isopropyl citrate, and ascorbic acids have been used.

[0003]

However, oxidation inhibitors are generally expensive and have not had a satisfactory effect on highly unsaturated fats and oils. In addition, since the compound is a relatively complicated compound, the oxidation inhibitor itself decomposes during storage for a long period of time, and the effect may not be sufficiently exhibited. The present invention provides an antioxidant which is an inexpensive and stable substance and has an effect comparable to that of a conventionally used antioxidant.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide an aliphatic compound having an unsaturated bond containing potassium carbonate, potassium bicarbonate or a mixture of potassium carbonate and potassium bicarbonate, particularly an unsaturated fatty acid or unsaturated fatty acid. The amount of the antioxidant used in the present invention is as follows: potassium carbonate, potassium hydrogencarbonate, or a mixture of potassium carbonate and potassium hydrogencarbonate per atomic group,> C = C <1 gram equivalent. Is characterized by being blended in an amount of 10 to 800 mg or suspended in a surfactant for practical use.

That is, the present invention has been completed by finding that a salt comprising a potassium group and a carbonate group has a remarkable oxidation inhibitory effect on unsaturated fatty acids. A satisfactory effect was not obtained when the anion corresponding to potassium was other than a carbonate ion, and no satisfactory effect was obtained when a salt composed of a carbonate ion and another cation was used. Potassium bicarbonate was also effective, but the effective usage under the same conditions increased 2-5 times. In the present invention K ⁺ and CO ₃ ^- ratio of is presumed to be important.
The reason why such a readily available stable salt has an oxidation inhibitory effect cannot be elucidated yet, but a remarkable effect has been confirmed with respect to linoleic acid, docosahexaenoic acid (hereinafter referred to as DHA), sardine oil and the like.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The aliphatic compound having an unsaturated bond in the present invention is an aliphatic compound having an atomic group,> C = C <, and does not include an aromatic compound. In particular, unsaturated fatty acids having a carboxyl group at the terminal, and mono-, di-, and tri-glycerides of unsaturated fatty acids can be exemplified. An effective antioxidant is essential for highly unsaturated oils containing many unsaturated fatty acids such as DHA.

[0007] Linoleic acid having two atomic groups,> C = C <in one minute, is added with various inorganic salts in the amounts shown in Table 1 and stored under a high load of 70 ° C., and is obtained in an amount of 2.25. The amount of lipid peroxide after one day was measured by the thiocyanic acid method (iron iron method), and the results are shown in Table 1. In other words, this is an evaluation method for measuring lipid peroxide (hydroperoxide) generated by lipid peroxidation. In this method, iron (II) is oxidized to iron (III) by the lipid peroxide, and the iron (III) is converted to ammonium thiocyanate. Redan iron, Fe (SC)
This is a method for colorimetric determination of N).

[0008] The measuring method is as follows. Preparation of induction reaction solution (1) Dissolve 14.02 mg of linoleic acid in 1.0 ml of ethanol. (2) 1.0 ml of 0.1 M phosphate buffer (pH = 7)
Add. (3) Dissolve the antioxidant sample in water to make 0.5 ml. The above (1), (2) and (3) are mixed and sealed in a 5 ml test tube with a lid, and this is used as an induction reaction solution. This induction reaction solution was stored under a high load of 70 ° C. for 2.25 days, and 0.1 ml was collected in a 10 ml test tube with time.
4.7 ml of 5% ethanol and 0.1 ml of a 30% ammonium thiocyanate aqueous solution were added, and 0.1 ml of a 0.02 M aqueous solution of FeCl ₂ in 0.1% hydrochloric acid was added, followed by thorough stirring. Measure the absorbance at 500 nm. In the following experiments, the measurement was performed by a method according to this.

[0009]

[Table 1]

As is evident from Table 1, potassium carbonate exhibited remarkable antioxidant activity, followed by potassium bicarbonate which exhibited excellent antioxidant activity. Since the combination of 2 gram equivalent of potassium and 1 gram equivalent of carbonic acid group shows high antioxidant activity, in the case of potassium bicarbonate, the carbonic acid group for potassium group is insufficient, and it is assumed that the antioxidant activity is somewhat inferior. did. Therefore, the antioxidant active substance in the present invention is potassium carbonate or potassium hydrogen carbonate, and both may be used as a mixture.

When only potassium carbonate is used, the amount of the antioxidant active substance used in the present invention is as follows: atomic group,> C = C
<As K ₂ CO ₃ per 1 gram equivalent 10 to 400
mg, preferably 20-150 mg. K ₂ CO ₃
If the amount of addition is less than 10 mg, no significant effect is exhibited,
If it exceeds 400 mg, the effect reaches the upper limit, and further antioxidant activity cannot be expected. When potassium bicarbonate alone is used, the atomic group,> C = C <20 to 800 mg, preferably 40 to 800 mg as KHCO ₃ per gram equivalent.
３００300 mg. If the amount of KHCO ₃ added is less than 20 mg, no significant effect is exhibited, and if it exceeds 800 mg, further antioxidant activity cannot be expected.

Further, in the present invention, it can be used in combination with other conventionally used antioxidants such as vitamin E, ascorbic acids, dibutylhydroxytoluene and erythorbic acid. Not only can a synergistic effect be obtained by using in combination with other antioxidants, but also in a small amount such that little effect is recognized alone, without reducing the effects of other antioxidants, in the long term Can increase the long-term effect when used together.

The oxidation inhibitor of the present invention is a water-soluble substance. Therefore, when the antioxidant of the present invention is mixed with a substance which is difficult to dissolve, it is mixed with a surfactant in a suspended state, preferably as a water-in-oil emulsion. Examples of the surfactant include glycerin fatty acid ester, sucrose fatty acid ester, sorbitan fatty acid ester, lecithin and the like. The antioxidant of the present invention can be widely used in medicines, foods, cosmetic bases, feeds for aquatic products (culture, etc.), feeds for animals (including livestock animals such as cattle and pigs and pets), and the like.

[0014]

EXAMPLE 1 The amount of potassium in potassium carbonate and potassium hydrogen carbonate was 200 ppm based on linoleic acid (atomic group,> C = C <1,
47.2 ppm as K ₂ CO _{3 with} respect to gram equivalent, K
FIG. 1 shows the relationship between the number of days elapsed and the absorbance when an induction reaction solution was prepared by the above-described method so as to obtain HCO _{3 (} 68.4 ppm) and kept at 70 ° C. As is clear from FIG. 1, potassium bicarbonate also has an antioxidant activity comparable to potassium carbonate.

EXAMPLE 2 The amount of potassium carbonate was determined based on the pp of potassium relative to linoleic acid.
m. Sample without potassium carbonate, 50 ppm to 400 ppm as potassium (atomic group,> C =
C <1 gram equivalent, K ₂ CO ₃ 11.8 to 94.4
ppm) was kept at 70 ° C. for 10 days, and the amount of lipid peroxide generated every day was measured. The results are shown in FIG. Judging from FIG. 2, it is remarkably effective to add linoleic acid at 100 ppm or more as K.

Example 3 A test was conducted for the synergistic effect when vitamin E and the oxidation inhibitor of the present invention were used in combination. A sample with 40 ppm of potassium added to linoleic acid, a sample with 40 ppm of vitamin E added, 40 ppm of potassium and vitamin E4
The sample to which 0 ppm was added and the sample to which no antioxidant was added were each kept at 70 ° C. for 10 days, and lipid peroxide generated every day from the third day was measured.
It was shown to. Judging from FIG. 3, when used in combination with vitamin E, the antioxidant of the present invention does not adversely affect the effect of vitamin E, and has an effect of suppressing the generation of lipid peroxide in the long term. That is, when used in combination with vitamin E, the effect of sustaining the action of the vitamin E oxidation inhibitor was maintained even when used in combination with vitamin E, even if it was used in a very small amount that exhibited little effect by itself.

Example 4 The effect of the antioxidant of the present invention on fish oil (sardines) was
It was measured by V (peroxide value) measurement method (iodometry titration method). The principle of this method is based on a reaction in which lipid hydroperoxide is reduced by potassium iodide under acidic conditions, and the liberated iodine is titrated with sodium thiosulfate. The results obtained are shown in FIG. In addition, a similar experiment was performed for a control to which no oxidation inhibitor was added, and the results are also shown in FIG. The measuring method is as follows.

In a 20 ml glass bottle with a lid, 0.025 g of fat and oil is mixed, and a mixed solution of chloroform and glacial acetic acid (chloroform:
Glacial acetic acid = 2: 3) Add 3 ml, shake gently to dissolve, and add 0.055 ml of a saturated potassium iodide solution under a nitrogen atmosphere.
After stirring for 1 minute, the mixture is left in a dark place at room temperature for 5 minutes. Then, add 3 ml of water, shake well, add 1 to 2 drops of starch indicator, and titrate with 0.01N sodium thiosulfate standard solution.The end point is when the blue color of the starch disappears. PV was determined by the equation. Peroxide value = (A × F) × 10 / B where A = 0.01N sodium thiosulfate standard solution usage (ml) F = 0.01N sodium thiosulfate standard solution titer B = sample collection amount ( g) PV (peroxide value) means iodine released when potassium iodide is added to a sample based on the above measurement method.
It is expressed in milliequivalents to g.

[0019]

According to the present invention, potassium carbonate and potassium hydrogen carbonate are
According to the present invention, which has been found out to have an antioxidant effect on aliphatic unsaturated compounds, it is incorporated into unsaturated fats and oils, and pharmaceuticals, foods, cosmetics, marine feeds, livestock feeds and the like containing the same. Oxidation of an aliphatic compound having an unsaturated bond is suppressed by an inexpensive compound, and its efficacy is maintained.

[Brief description of the drawings]

FIG. 1 shows K ₂ CO ₃ and KHCO ₃ (K-200).
4 is a graph showing the antioxidant effect of the present invention (ppm).

FIG. 2 is a graph showing the antioxidant effect of different concentrations of K ₂ CO ₃ .

FIG. 3 is a graph showing the antioxidant effect when used in combination with vitamin E.

FIG. 4 is a graph showing the antioxidant effect of K ₂ CO ₃ on fish oil.

Claims (4)

[Claims] 1. An oxidation inhibitor for an aliphatic compound having an unsaturated bond, comprising potassium carbonate, potassium hydrogen carbonate or a mixture of potassium carbonate and potassium hydrogen carbonate. 2. The antioxidant according to claim 1, wherein the aliphatic compound having an unsaturated bond is an unsaturated fatty acid or a glyceride of an unsaturated fatty acid. 3. An aliphatic unsaturated compound comprising 10 to 800 mg of potassium carbonate, potassium bicarbonate or a mixture of potassium carbonate and potassium bicarbonate per 1 gram equivalent of an atomic group,> C = C <1 gram equivalent. An oxidation inhibitor for a compound having a saturated bond. 4. An oxidation inhibitor characterized by suspending potassium carbonate, potassium bicarbonate or a mixture of potassium carbonate and potassium bicarbonate using a surfactant.