JP2017060439A - Method for improving or maintaining stable state in oxidation reaction of edible oil - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for improving a stable state of an oxidation reaction in an edible oil by using a trace quantity of a hydrophilic natural antioxidant.SOLUTION: A method for improving a stable state of an oxidation reaction in an edible oil comprises: a process (a) of mixing at least one kind of a hydrophilic natural antioxidant in an oil having high polarity at a temperature state of 5 to 200°C to provide a mixture of an antioxidant containing 0.04 to 50 wt.% of the hydrophilic natural antioxidant and the oil; and a process (b) of mixing the mixture of the antioxidant and the oil in the edible oil so that the hydrophilic natural antioxidant has concentration of 10 to 1000 ppm based on weight.SELECTED DRAWING: None

Description

  The technical field of the present invention is to stabilize the edible oil in the oxidation reaction.

  Edible oils, especially edible oils that contribute to health, such as fish oil and soybean oil, contain large amounts of monounsaturated fatty acids and / or polyunsaturated fatty acids.

  According to past research results, polyunsaturated fatty acids have the effect of lowering blood cholesterol levels and reducing the frequency of diseases in blood vessels, as in the case of ω-3 unsaturated fatty acids. doing.

  However, due to the presence of double bonds in these unsaturated fatty acids, the lipids of the unsaturated fatty acids are prone to oxidation, and as a result, the properties of the unsaturated fatty acids are altered and the unsaturated fatty acids have a predetermined density. The period that can remain in the state of having a must also be limited.

  Various antioxidants are used to prevent oxidation of edible oils.

  However, it has been pointed out that two components, butylhydroxyl salt (BHT) and butylhydroxynol (BHA), which are usually used as antioxidants for lipids, cause tumors in the body.

  Vitamin E, well known as another antioxidant, has been found to be ineffective at least reducing the peroxide value in fish oil.

  In contrast, natural antioxidants such as epigallocatechin gallate (EGCG) collected from tea and carnosic acid collected from rosemary are extremely safe for the body and have a healthy anti-cancer effect. The above preferable aspect can be exhibited.

  However, these antioxidants have been regarded as unsuitable for use in oils and fats because of their high hydrophilicity.

  Thus, realization of edible oils that can have health-friendly properties over a long period of time has been demanded.

  There is a need to develop an effective and economical method that can detect suitable antioxidants and improve the stability of edible oils during oxidation.

  In response to such a request, for example, in Patent Document 1, a predetermined amount of soybean lecithin (phosphatidylcholine) 0.1% to 1%, polyphenol extracted from green tea 0.01% to 1%, propyl gallate 0% The composition which mix | blends 0.1%-1% of 2 types or 3 types of -0.1% to edible oil as antioxidant is proposed.

  According to Patent Document 1, the value of the peroxide value is less when the antioxidant is blended than when not blended, at a stage after 20 or 40 days at 60 ° C. On the other hand (Tables 2 and 3), it was clearly shown that delicious edible oils were obtained by uniformly mixing the antioxidant and the edible oil with a mixer (Example 1 and Example 2). Has been.

  However, in the case of Patent Document 1, while at least two kinds of antioxidants are required, a ratio of 0.1% to 1% with respect to edible oil is required, but these antioxidants are expensive. The above mixing ratio is never reasonable.

Japanese Examined Patent Publication No. 7-83777

  The basic object of the present invention is to provide a method for improving the stable state of an oxidation reaction in edible oil by using a trace amount of a hydrophilic natural antioxidant.

In order to solve the above problems, the basic configuration of the present invention is as follows.
a. Hydrophilicity by mixing at least one hydrophilic natural antioxidant in an oil with high polarity at a temperature of 5 to 200 ° C., preferably 10 to 100 ° C., more preferably 25 to 40 ° C. A step of obtaining a mixture of an antioxidant and an oil containing 0.04 to 50% by weight, preferably 0.04 to 40% by weight, more preferably 0.04 to 20% by weight of a natural antioxidant of
b. The mixture of the antioxidant and the oil so that the hydrophilic natural antioxidant in the edible oil has a concentration of 10 to 1000 ppm, preferably 50 to 500 ppm, more preferably 100 to 200 ppm, based on weight. A method of improving the stable state in the oxidation reaction of edible oil by the step of mixing,
Consists of.

  In the case of the present invention based on the above basic structure, the hydrophilic natural antioxidant is dispersed in the edible oil in a trace amount of 1000 ppm at most through the oil having high polarity, and both are sufficiently mixed. As a result, it is possible to improve or maintain a stable state in the oxidation reaction of the edible oil and to obtain an effect of improving health such as an anticancer effect.

In order to explain that the mixed state can be maintained, the polar group (for example, HO-, O ₂ N-, H ₂ N-, HOOC-) possessed by the oil in the step a is hydrophilic and natural oxidation. While having an affinity with an inhibitor, it is possible to achieve the mixing of b and to maintain the mixed state by a surface-active action by the hydrophobic group due to its own oiliness having an affinity with edible oil. it can.

  When used in food products, natural antioxidants are safer and more favorable than artificially synthesized antioxidants.

  In the method of the present invention, when a hydrophilic natural antioxidant is dispersed in a hydrophobic edible oil such as fish oil and soybean oil, an oil having a high polarity is associated with the above-mentioned surface active action. Adopted as an intermediate solvent.

  In such a method, dispersion of the natural antioxidant at the interface between oil and air is promoted, and the antioxidant function by the natural antioxidant is further improved.

  Hydrophilic natural antioxidants include polyphenol-containing compositions, antioxidant components extracted from plants, epigallocatechin gallate (EGCG), catechin, epicatechin, epiga

Examples include, but are not limited to, locatechin, epicatechin gallate, quercetin, esperidin, pterostilbene, proanthocyanidins, and carnosic acid.

  The composition containing polyphenol includes at least one of green tea, black tea, white tea and oolong tea, and plant-extracted antioxidant ingredients include apple, orange or citrus, blueberry, rosemary, and sesame At least one of the extracted antioxidant components is included.

  One representative example of a hydrophilic natural antioxidant is EGCG, and another representative example is carnosic acid.

  On the other hand, propylene glycol caprylate, a monoglyceride that is a medium chain, or a triglyceride that is a medium chain corresponds to an oil having high polarity.

  An example of the triglyceride that is an intermediate chain is capryl triglyceride.

  The state of the mixture of the hydrophilic natural antioxidant and the highly polar oil is either a solution or an emulsion.

  In the case of the embodiment of the present invention in which propylene glycol caprylate is employed as the oil having high polarity, the state of the mixture of the antioxidant and the oil is a solution.

  A typical processing method of mixing at least one hydrophilic natural antioxidant into a highly polar oil is realized by ultrasonic vibration.

  Edible oils applicable to the present invention include fish oil and other vegetable oils.

  In the method of the present invention, the edible oil can be carried out by particularly selecting a pretreatment step of removing the oxidative component having polarity before mixing with the mixture of the antioxidant and the oil.

  In such a pretreatment step, the edible oil is first filtered through silica gel chromatography and then extracted from the silica gel by adding a non-polar volatile solvent, and finally the edible oil is extracted. Nonpolar volatile solvents are excluded by evaporating from edible oil.

  In the above pretreatment, hexane and other non-polar volatile solvents can be employed, but the volume ratio of silica gel to edible oil is 1: 1 to 1:20.

  Details concerning the implementation of the present invention are further described in the following examples.

  And the characteristic, subject, and effect of this invention can be grasped | ascertained clearly from the following description and a claim.

  The embodiments described below are described as individual specific examples, but are not intended to limit the disclosure of the configuration contents by other examples.

Improved stability to oxidation reaction in fish oil based on EGCG 1.2 g EGCG was dissolved in 8 g propylene glycol caprylate and a clear clear solution was produced by ultrasonic vibration.

  The dissolution was performed in a temperature range of 25 ° C. to 40 ° C., but the temperature was influenced by the degree of ultrasonic vibration.

  The antioxidant oil solution thus obtained contained EGCG at a concentration of 13% by weight.

  Next, in order to remove polar oxidizing components from fish oil, hexane was packed into a separation column using silicon gel by wet containment method.

  90 g of fish oil (large herring oil) was sequentially added to the separation column using silicon gel.

  In this case, the volume ratio of silicon gel to fish oil is 1: 1.

  The filtration method using a vacuum pump was performed as follows.

  After the silicon gel separation column was washed with 180 ml of hexane, the hexane was evaporated in vacuum.

  After evaporation of hexane in vacuum, 70 ml of purified fish oil could be obtained.

  An anti-oxidant oil solution containing EGCG is blended in a ratio of 1: 749 to refined fish oil and then mixed vigorously under swirling motion to The mixture became clear and transparent.

  From the transparent state, it can be confirmed that EGCG and fish oil are mixed with each other by the surface-active action of the antioxidant oil solution.

  The fish oil mixture thus obtained contained EGCG at a concentration of 173 ppm.

  The peroxide value of the fish oil mixture was measured after 3 days storage in a dark room at 60 ° C.

  For detection of peroxide values, a mixture of 2.00 ± 0.02 g of fish oil is in an Erlenmeyer flask (conical flask) with a volume of 100 ml as a test sample and sealed by glass. Was housed.

  Next, 12 ml of a mixed solution of acetic acid and chloroform (volume ratio is 3: 2) is added to the flask, and the swirling motion with respect to the flask is continued until the sample by the mixing is completely dissolved. did.

  After 0.2 ml of saturated potassium iodide solution is added to the flask and swirled for 1 minute, 30 ml of distilled water is added to the flask, and iodide is extracted from the chloroform layer in the flask. Vibrated vigorously until the end.

  Finally, 0.1N (0.1N) sodium thiosulfate, ie 7.9 g / L thiosulfate

Sodium acid was used with the starch solution as an indicator for titrating oxidized iodide, and the titration was continued until the blue-gray color disappeared in the upper aqueous layer.

  As a result, the peroxide value in the mixture of fish oil containing EGCG at a concentration of 173 ppm was in the case of control, i.e., the same process as described above without adding EGCG (hereinafter referred to as this). Thus, the case where the same process is performed without adding a natural antioxidant is abbreviated as “control case”, and the sample obtained by the control is abbreviated as “control sample”). It shows that it is decreasing.

  Usually, the highest content of BHA in fish oil is 0.2 g / kg, ie 200 ppm.

  However, according to previous counts, a sample of fish oil containing 200 ppm of BHA under comparable conditions only reduces the peroxide value by only 7.8% compared to the control sample.

  The mixture of EGCG and fish oil thus obtained is not only excellent in flavor at the initial stage, but also excellent in flavor at the stage after 3 days, compared to the control sample. confirmed.

  Thus, the method of Example 1 presents the unexpected effect of improving the stability of fish oil against oxidation while having a trace content of EGCG 173 ppm.

Improved stability to oxidation reaction in fish oil based on carnosic acid 1.2 g carnosic acid was dissolved in 8 g propylene glycol caprylate and a clear transparent solution was produced by ultrasonic vibration.

  The dissolution was performed in a temperature range of 25 ° C. to 40 ° C., but the temperature was influenced by the degree of ultrasonic vibration.

  The antioxidant oil solution thus obtained contained carnosic acid at a concentration of 13%.

  The fish oil was purified via silicon gel chromatography according to the procedure of Example 1.

  By blending a solution of antioxidant oil containing carnosic acid in a ratio of 1: 749 to refined fish oil, the fish oil is mixed vigorously under swirling motion. And the mixture became clear and transparent, and mixing of carnosic acid and fish oil could be confirmed.

  The fish oil mixture thus obtained contained carnosic acid at a concentration of 173 ppm.

  The fish oil mixture was stored at 60 ° C. in a dark room for 3 days, and then the peroxide value was measured according to the procedure of Example 1.

  As a result, the peroxide value of the mixture of fish oil containing carnosic acid at a concentration of 173 ppm was reduced by 41.9% compared to the control.

  The mixture of carnosic acid and fish oil obtained in this way is not only superior in flavor at the initial stage, but also significantly superior in flavor after three days compared to the control sample. Was confirmed.

  Thus, the method of Example 2 has an unexpected effect of improving the oxidation state of fish oil while having a trace content of 173 ppm carnosic acid.

  The results of Examples 1 and 2 show that even in the case of fish oil, which is an easily oxidizable edible oil, peroxidation as shown in Tables 2 and 3 of Patent Document 1 by a very small amount of natural antioxidant. If it is considered that the number of days that have passed is comparable to the degree of the decrease in the physical value or that the number of days that have elapsed is an order of magnitude smaller, it is possible to infer a state of decrease in the peroxide value that exceeds the above degree.

  Therefore, also in the case of edible oils other than fish oil, the stable state in the oxidation reaction can be sufficiently improved by the method of the present invention.

  The reason that such an effect can be exerted is that a hydrophilic natural antioxidant and an edible oil such as fish oil and soybean oil are intimately mixed due to the surface-active action of the oil having a high polarity that is the object of blending in a Is derived from the fact that

  The present invention improves the stability of the oxidation reaction in fish oil and other edible oils, while ensuring the health promoting effect of natural antioxidants, and thus can be used in the field of all foods containing edible oils. .

Claims (15)

a. At least one hydrophilic natural antioxidant is mixed in a highly polar oil at a temperature of 5 to 200 ° C. to contain 0.04 to 50% by weight of the hydrophilic natural antioxidant. Obtaining a mixture of an antioxidant and an oil,
b. The stable state in the oxidation reaction of the edible oil is obtained by mixing the mixture of the antioxidant and the oil in the edible oil so that the hydrophilic natural antioxidant has a concentration of 10 to 1000 ppm based on the weight. How to improve.   Compositions in which natural antioxidants having hydrophilicity include polyphenols, antioxidants extracted from plants, epigallocatechin gallate (EGCG), catechin, epicatechin, epigallocatechin, epicatechin gallate, quercetin , Esperidin, pterostilbene, proanthocyanidin, carnosic acid, and the composition containing polyphenol is at least one of green tea, black tea, white tea, and oolong tea, and it is extracted from plants. The method for improving the stable state in the oxidation reaction of edible oil according to claim 1, wherein the oxide is an antioxidant extracted from any of apple, orange or citrus, blueberry, rosemary, and sesame. .   2. The oxidation of edible oil according to claim 1, wherein the antioxidant oil having high polarity is any one of propylene glycol caprelite, medium chain monoglyceride, or medium chain triglyceride. A method to improve the stable state in the reaction.   The method for improving a stable state in an oxidation reaction of an edible oil according to claim 3, wherein the medium chain triglyceride is capryl triglyceride.   The method for improving the stable state in the oxidation reaction of edible oil according to claim 1, wherein at least one natural antioxidant having hydrophilicity is mixed with oil having high polarity by ultrasonic vibration.   The oxidative reaction of edible oil according to claim 1, characterized in that at least one natural antioxidant having hydrophilicity is mixed with oil having high polarity at a temperature of 25 to 40 ° C. How to make a stable state.   Prior to mixing the edible oil with the mixture of antioxidant and oil, the edible oil is filtered through silica gel chromatography to remove non-polar volatile solvents to remove polar oxidizing components from the edible oil. In the oxidation reaction of the edible oil according to claim 1, wherein the edible oil is extracted from the silica gel by the action, and the non-polar volatile solvent is removed from the edible oil by evaporation. A way to improve the steady state.   8. The method for stabilizing the edible oil oxidation reaction according to claim 7, wherein the edible oil is fish oil.   The method for improving the stable state in the oxidation reaction of edible oil according to claim 7, wherein the nonpolar and volatile solvent is hexane.   The method for improving the stable state in the oxidation reaction of edible oil according to claim 7, wherein the volume ratio of the silica gel to the edible oil is from 1: 1 to 1:20.   The method for improving the stable state in the oxidation reaction of edible oil according to claim 1, wherein the mixture of the antioxidant and the oil is a solution.   The method for improving a stable state in an oxidation reaction of an edible oil according to claim 11, wherein the antioxidant oil having high polarity is propylene glycol caprylate.   The method for improving a stable state in an oxidation reaction of an edible oil according to claim 1, wherein the mixture of antioxidant oils and fats is an emulsion.   The method for improving the stable state in the oxidation reaction of edible oil according to claim 1, wherein the mixture of the antioxidant and the oil has 0.04 to 20% by weight of a natural antioxidant.   In the oxidation reaction of edible oil according to claim 1, wherein the natural antioxidant having hydrophilicity is in a concentration of 100 to 200 ppm based on weight after mixing the antioxidant fat mixture into edible oil. A method to improve or improve the steady state.