JP2018016776A - Antioxidant, oil-and-fat composition containing antioxidant and oily food product containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a safe antioxidant which can improve the oxidative stability of an oil / fat composition and an oil-based food using the same as compared with the conventional one, and can suppress a change in flavor and appearance due to oxidation for a long period of time. provide. SOLUTION: A flavonoid compound (excluding a calcon compound) containing 1 to 5 hydroxyl groups and having no gallate structure in the B ring, 6 hydroxyl groups, having a carbonyl group in the C ring, and a C ring. A polyphenol compound (excluding dihydrokercetin) containing at least one of a group consisting of flavonoid compounds and carbonon compounds having no carbon-carbon double bond between the carbon at the 2-position and the carbon at the 3-position, and an alkali. A substance is included as an additive component to an object that suppresses oxidation. [Selection diagram] Fig. 1

Description

  The present invention relates to an antioxidant, an oil / fat composition containing an antioxidant, and an oily food containing the same.

  Fats and oils such as butter and margarine, cakes containing fats and oils, baked confectionery such as biscuits, cookies and crackers, and fried foods such as potato chips and fried noodles have a good taste due to containing fats and oils On the other hand, the deterioration of flavor over time is a big problem. As the oxidation of fats and oils progresses, the taste, smell, texture, etc. of these oily foods also decrease.

  From such a viewpoint, many antioxidant treatments have been applied to the oil and fat composition and the oil-based food containing the same. For example, a method of encapsulating an antioxidant in a container or packaging, a method of adding various antioxidants such as tocopherol, ascorbic acid, polyphenol and the like to oils and fats are widely adopted (Non-patent Document 1). Moreover, the method of adding alkaline substances, such as calcium carbonate and potassium carbonate, to fats and oils is also employ | adopted (patent documents 1, 2).

  However, the method described in Patent Document 1 is a method in which an alkaline earth metal carbonate such as calcium carbonate is added alone to fats and oils, and a satisfactory antioxidant ability cannot always be obtained. Similarly to Patent Document 1, the method described in Patent Document 2 is a method in which an alkali metal carbonate such as potassium carbonate is added alone to fats and oils, and a satisfactory antioxidant ability is not necessarily obtained. .

  Therefore, an antioxidant containing a polyphenol typified by catechin contained in a tea extract and an emulsifier, a two-component antioxidant comprising a mixture A containing a polyphenol and a mixture B containing an alkaline agent, etc. Has been proposed (Patent Documents 3 and 4). In the antioxidant described in Patent Document 3, it has been proposed to use specific polyphenols such as tea catechin and epigallocatechin gallate, which are tea extracts and components thereof, as polyphenols. In the antioxidant product described in Patent Document 4, it is proposed to use a coffee bean extract in addition to the tea extract as the mixture A containing polyphenols. Furthermore, an edible fat and oil containing an antioxidant substance using a tea extract and an emulsifier in combination and a food using the same have been proposed (Patent Document 5).

JP 59-152998 A JP-A-2015-57979 JP 2000-21880 A JP 2008-156278 A International publication WO2013 / 172348 pamphlet

Introduction to Edible Oils and Fats <Revised 2nd Edition>

  However, the antioxidants described in Patent Documents 3 and 4 simply examine the antioxidant ability of tea extract as a polyphenol and a specific polyphenol as a component thereof, or a mixture of a coffee bean extract and an alkaline substance. I was only doing. Moreover, in any of Patent Documents 3 and 4, no study has been made on the use of the obtained antioxidant for edible fats and oils and oil-based foods and oily foods using the same.

  In the edible oil and fat containing the antioxidant substance described in Patent Document 5, there is a problem that the effect of suppressing the deterioration of flavor and color due to the oxidation of the fat and oil is not necessarily sufficient, and the fat and the food using the same Improvement of oxidation stability has been desired.

  The present invention has been made in view of the circumstances as described above, and it is possible to improve the oxidative stability of an oil and fat composition and an oil-based food using the oil composition as compared with the prior art. It is an object to provide a safe antioxidant capable of suppressing changes in appearance.

  In order to solve the above problems, the antioxidant of the present invention is characterized by the following points.

  (1) A flavonoid compound containing 1 to 5 hydroxyl groups and having no gallate structure in the B ring (excluding the chalcone compound), containing 6 hydroxyl groups, having a carbonyl group in the C ring, A polyphenol compound (excluding dihydroquercetin) containing at least one member selected from the group consisting of a flavonoid compound and a chalcone compound having no carbon-carbon double bond between the carbon at the 2nd position and the carbon at the 3rd position; and an alkaline substance Is added as a component added to the object to suppress oxidation.

  (2) It is preferable that the alkaline substance is at least one selected from the group consisting of monovalent carboxylates and alkali metal salts.

The oil and fat composition of the present invention is characterized by the following points.
(3) It contains the antioxidant according to the invention (1) or (2) and an oil or fat.

  (4) The alkaline substance is preferably at least one of the group consisting of monovalent carboxylates and alkali metal salts.

  (5) In the said invention (3) or (4), it is preferable that the compounding quantity of a polyphenol compound is 20-5000 ppm with respect to oil.

  (6) In any one of the above inventions (3) to (5), the blending amount of the alkaline substance is preferably 30 to 10,000 ppm for oil as sodium oleate.

  The oil-based food of the present invention is characterized by the following points.

  (7) The oil composition according to any one of the inventions (3) to (6) is contained.

  ADVANTAGE OF THE INVENTION According to this invention, it is possible to improve the oxidation stability of an oil-fat composition and an oil-based foodstuff using the same compared with the past, and it is safe anti-oxidation which can suppress the change of the flavor and external appearance by oxidation over a long period of time. An oxidant is realized.

It is the graph which showed the relationship between the addition amount of an alkaline substance, and the synergistic effect of CDM extension. The addition amount of the alkaline substance shown on the horizontal axis indicates the sodium oleate equivalent amount (ppm).

  The present invention is described in detail below.

  The antioxidant of the present invention comprises (A) 1 to 5 hydroxyl groups, a flavonoid compound having no gallate structure in the B ring (however, excluding chalcone compounds), (B) 6 hydroxyl groups, A flavonoid compound having a carbonyl group in the ring and having no carbon-carbon double bond between the 2-position carbon and 3-position carbon of the C ring, and (C) including at least one selected from the group consisting of chalcone compounds It is characterized by containing a polyphenol compound (excluding dihydroquercetin) and an alkaline substance as an additive component to an object for suppressing oxidation.

  Here, the polyphenol compound is a general term for compounds having two or more phenolic hydroxyl groups (hydroxyl groups bonded to an aromatic ring such as a benzene ring or a naphthalene ring) in the same molecule. It is classified into compounds, lignan compounds, curcumin compounds, coumarin compounds, and flavonoid compounds. Among these, a flavonoid compound, which is a typical polyphenol compound, is a phenyl having a diphenylpropane structure in which two benzene rings of A ring and B ring are connected by three carbon atoms as shown in the following general formula. A general term for a group of compounds.

  Flavonoid compounds are further classified as follows according to the structure of the C ring consisting of 3 carbon atoms. (A) a flavone having one double bond in the C ring and having a carbonyl group at the 4-position of the C ring; (b) a flavonol having a hydroxyl group bonded to the 3-position of the C ring of the flavone; An isoflavone in which the ring bond position is replaced from the 2nd position to the 3rd position of the C ring; (d) a flavane in which the C ring contains neither a double bond nor a carbonyl group; (Catechin), (f) flavanone having a carbonyl group at the 4-position of the C ring, (g) flavanonol having a hydroxyl group bonded to the 3-position of the C-ring of flavanone, and (h) oxygen at the 1-position of the C-ring of flavone is reduced. Chalcones opened at the position, (i) Anthocyanidins having two double bonds in the C ring and oxygen at the 1 position on the C ring charged to +. As for chalcone, under acidic conditions, the ring closes and becomes flavanone.

  Examples of such a polyphenol compound (A) include kaempferol, quercetin, (+)-catechin, epicatechin, daidzein, 4′-hydroxyflavanone, 6-hydroxyflavanone, apigenin, baicalein, hesperetin, naringenin, erio Examples include dicthiol. Examples of the polyphenol compound (B) include dihydromyricetin. Examples of the polyphenol compound (C) include isoliquiritigenin, butein and the like.

  In the present invention, as the polyphenol compound, the above-mentioned various types of flavonoid compounds, chalcone compounds, and glycosides thereof are also included in the flavonoid compounds.

  These polyphenol compounds include, for example, a synthetic product having a purity of 95% or more obtained by chemical synthesis, a high-purity synthetic product having a purity of 98% or more, and a synthetic product of a plurality of polyphenol compounds. Mixture, extract obtained by extracting each part such as leaves, flowers, seeds, stems, roots, etc. of the plant containing the polyphenol compound with a solvent, high purity obtained by purifying the extract (95% The use of the above natural products and mixtures thereof is exemplified.

  Examples of a method for extracting a polyphenol compound from each part of a plant include an extraction method using an organic solvent, water or a mixed solvent thereof, a subcritical extraction method using carbon dioxide or water, and a critical extraction method. .

  Examples of the solvent used for the organic solvent extraction include water, ethanol, ethyl acetate, acetone, and a mixed solvent thereof from the viewpoint of safety and the like. It is preferable to consider that the obtained extract is further concentrated as necessary, and purified by a method such as distillation or recrystallization.

  When using a plant extract containing a polyphenol compound, the purity of the polyphenol compound in the extract is preferably 50% by mass or more, more preferably 60% by mass or more, and 80% by mass or more. Is more preferable. In addition, the upper limit of the purity of the polyphenol compound in the said extract is 100 mass%.

  In the oil-and-fat composition containing the antioxidant of the present invention and the oil-based food using the same, it is preferable to use a high-purity product as the polyphenol compound from the viewpoint of suppressing a decrease in flavor and texture, particularly natural. It is preferable to use a high-purity product. In addition, from the above viewpoint, the blending amount of the polyphenol compound is preferably in the range of 20 to 5000 ppm for the oil, more preferably 50 to 5000 ppm from the viewpoint of antioxidant ability, and an oily food is provided. It is more preferable that it is 50-1000 ppm from a viewpoint of time flavor, hue, and cost.

  The alkaline substance used in the present invention is allowed to be added to food and is not particularly limited as long as it shows alkalinity. For example, alkali metal or alkaline earth metal hydroxide, carbonate, organic Examples include acid salts, alkoxide compounds, fatty acid salts and the like. Specifically, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium methoxide, sodium ethoxide, calcium hydroxide, sodium hydroxide, potassium hydroxide, sodium citrate, potassium citrate, sodium phosphate And potassium phosphate, sodium lactate, potassium lactate, sodium oleate, sodium acetate and the like. These alkaline substances may be used alone or in combination of two or more. Considering the addition to oily foods, it is preferable to use weak alkalis because strong alkalis may cause hydrolysis of fats and oils.

  In consideration of adding to such fats and oils, such an alkaline substance is preferably considered to be at least one of the group consisting of monovalent carboxylates and alkali metal salts having good dispersibility in fats and oils. . Moreover, since it is preferable to disperse | distribute an alkaline substance uniformly in fats and oils, it melt | dissolves in a solvent and using as an alkaline solution is preferable.

  Among alkaline substances, citrates and phosphates have low dispersibility in fats and oils, and thus it is considered difficult to obtain an effect when added directly to fats and oils. When using such an alkaline substance with low dispersibility in fats and oils, 1) a method in which the alkaline substance is once dissolved in water and contacted with a polyphenol compound, and then dried, or 2) a raw material for oily food Among them, a method of adding an alkali substance to a raw material containing moisture, mixing with an oil and fat composition containing a polyphenol compound, and cooking by heating can be applied. By applying such a method, it is possible to uniformly disperse the alkaline substance in the oily food and to exhibit a predetermined antioxidant ability (oxidation stability).

  Examples of the solvent that can be used for dissolving the alkaline substance include water and alcohols such as methanol and ethanol. In particular, it is preferable to use water. These solvents may be used alone or in combination of two or more.

  As a preferable density | concentration of an alkaline solution, the range of 0.01-5 mol / L is illustrated, for example.

  In the present invention, an emulsifier exhibiting alkalinity can also be used as the alkaline substance. In consideration of use in foods, it is preferable to use an emulsifier that is allowed to be used as a food additive.

  By using an emulsifier as the alkaline substance, the dispersibility of the polyphenol compound can be improved, and the antioxidant ability (oxidation stability) can be improved.

  Examples of such an emulsifier include glycerin fatty acid ester, polyglycerin fatty acid ester, sucrose fatty acid ester, sorbitan fatty acid ester, propylene glycol fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and lecithin. These emulsifiers may be used alone or in combination of two or more. Furthermore, it is also possible to use together with alkaline substances other than said emulsifier.

  As the emulsifier, any emulsifier can be used as long as it contains an alkaline substance. Particularly, when the content of the alkaline substance is high, the amount added can be reduced, and the taste caused by the emulsifier is reduced. It is preferable because it is possible.

  Of the above-mentioned emulsifiers, it is preferable to use at least one selected from the group consisting of a glycerin fatty acid ester, a polyglycerin fatty acid ester, and a sucrose fatty acid ester, from the viewpoint of the effect of improving oxidation stability.

Examples of the glycerin fatty acid ester include monoglycerin fatty acid ester (monoglyceride) and organic acid monoglycerin fatty acid ester. More specifically, for example, monoglycerol C ₈ -C ₂₄ fatty acid ester, acetic acid monoglycerol C ₈ -C ₂₄ fatty acid ester, citric acid monoglycerol C ₈ -C ₂₄ fatty acid ester, succinic acid monoglycerol C ₈ -C ₂₄ fatty acid esters, diacetyl tartaric acid monoglyceride C ₈ -C ₂₄ fatty acid esters, lactic acid monoglycerol C ₈ -C ₂₄ fatty acid esters and the like.

Examples of the polyglycerin fatty acid ester include a compound in which a fatty acid is ester-bonded to polyglycerin in which 2 to 10 glycerins are condensed or a compound in which polyricinoleic acid in which 3 to 5 ricinoleic acids are condensed is bonded to polyglycerin. is as glycerin condensation ricinoleic acid ester exemplified, it is preferable considering the use of polyglycerol C ₈ -C ₂₄ fatty acid esters.

Sucrose fatty acid esters include sucrose C ₈ -C ₂₄ fatty acid esters. (C ₈ -C ₂₄ means the number of carbon atoms of the fatty acid bonded.)
The emulsifiers are polyglycerin fatty acid ester (polyglycerin fatty acid ester, polyglycerin condensed ricinoleic acid ester), glycerin fatty acid ester (organic acid monoglycerin fatty acid ester, monoglyceride), sucrose fatty acid, particularly from the viewpoint of good oxidation stability. Esters are preferably used, and commercially available products include CR-ED (polyglycerin condensed ricinoleic acid ester, Sakamoto Yakuhin Kogyo Co., Ltd.), Poem PR-100 (polyglycerin condensed ricinoleic acid ester, Sakamoto Yakuhin Kogyo Co., Ltd.). , Sunsoft 818H (polyglycerin condensed ricinoleic acid ester, Taiyo Kagaku Co., Ltd.), Poem V200 (reactive monoglyceride, manufactured by Riken Vitamin Co., Ltd.), Poem B-40 (succinic acid monoglycerin fatty acid ester, Riken vitamin strain) Company made), ER-290 (sucrose erucic acid fatty acid ester, manufactured by Mitsubishi Chemical Foods Co., Ltd.), and the like.

  Moreover, from the viewpoint of addition to fats and oils or oily foods, the emulsifier preferably has an HLB value of 7 or less. If the HLB value is 7 or less, the dispersion of the emulsifier in the oil-based food is good.

  Moreover, when adding the antioxidant of this invention to fats and oils and using it as frying oil, a glycerol fatty acid ester (an organic acid monoglycerol fatty acid ester, monoglyceride) is used suitably as an emulsifier from a viewpoint that it is hard to brown.

  Since an emulsifier such as glycerin fatty acid ester is obtained by adding an alkali catalyst to glycerin and a fatty acid and reacting them, it has been reported that a fatty acid salt remains in the emulsifier (for example, JP-A-2000-287631). No. publication etc.). Such a fatty acid salt is considered to function as an alkaline substance.

  About content of the alkaline substance in an emulsifier, it can be measured by the "soap test" (a reference | standard oil-and-fat analysis test method <Japan Oil Chemical Society> 2.6.2-1996 <soap>).

  In the “soap test”, the alkali content is titrated with hydrochloric acid, measured, and calculated as sodium oleate (soap) equivalent. The alkaline substance in the above emulsifier is considered to be mainly a fatty acid salt, but even when other alkali is contained, it is measured as a sodium oleate equivalent amount. For this reason, in this specification, the compounding quantity of the known alkaline substance is also described in terms of sodium oleate equivalent (ppm).

  The blending amount of such an alkaline substance in fats and oils is 30 to 10,000 ppm as oil oleate as sodium oleate from the point of obtaining a sufficient effect of improving oxidative stability and the flavor of oily foods containing an antioxidant. It is preferable that when it is used in oily foods, it is more preferably 500 to 10,000 ppm from the viewpoint that flavor deterioration due to free fatty acids does not occur.

  The blending ratio of the polyphenol compound and the alkali substance is, for example, the blending amount of the polyphenol compound (ppm) × the blending amount of the alkali substance (ppm) ≧ 7000 (however, the blending amount of the polyphenol compound is 10 ppm or more, the blending of the alkali substance) The amount is 37 ppm or more, and the blending amount of the alkaline substance is exemplified as sodium oleate equivalent amount).

  If the blending ratio of the polyphenol compound and the alkaline substance satisfies the above conditions, the antioxidant ability higher than the antioxidant ability when the polyphenol compound alone or the alkali substance alone is added is recognized. And synergistic effect of alkaline substances. Therefore, the antioxidant of the present invention can improve the oxidative stability of oil and fat compositions and oil-based foods using the same, and suppress changes in flavor and appearance due to oxidation over a long period of time. It is safe when taken as food.

  The antioxidant of the present invention is an antioxidant for foods, preferably an antioxidant for oil and fat compositions and an antioxidant for oily food oils. Although the antioxidant of this invention should just be mix | blended with the oil-and-fat composition or the oil-based food containing this oil-and-fat composition, it is preferable to make it contain in edible fats and oils. The oil / fat composition containing the antioxidant of the present invention is an oil / fat having improved oxidation stability. Moreover, the oil-based foodstuff containing the oil-fat composition containing the antioxidant of this invention turns into a foodstuff with improved oxidation stability.

  The fats and oils containing the antioxidant of the present invention may be edible fats and oils, whether animal fats or vegetable oils, such as soybean oil, rapeseed oil, cottonseed oil, safflower oil, corn oil, rice oil, olive oil, sesame oil. Plant oils such as palm oil, palm oil, palm kernel oil, perilla oil, fish oils such as tuna oil, sardine oil, animal oils such as lard, beef tallow, milk fat, etc., fractionated oils, transesterified oils, hardened oils, etc. .

  In addition, foods, especially oily foods containing fats and oils, include baked confectionery such as cookies and biscuits (including crackers) cakes, steamed confectionery such as bread, steamed bread, steamed cake, Chinese bun and steamed bun, rice confectionery, Fried confectionery such as donuts, churros, frozen confectionery such as ice cream, cooked foods (snaked confectionery such as potato chips, fried potatoes, croquettes, fried foods such as fried noodles such as fried noodles such as fried tempura and instant ramen, okonomiyaki, grilled meat, etc. Baked goods, fried vegetables, fried foods such as fried noodles, meats such as sausages and hamburgers, stews). Among these, it is preferable to use it for foods including the step of heating oils and fats, such as confectionery (cookies, biscuits, crackers, cakes, etc.), fried foods, fried foods, grilled foods, snacks for spraying oils and fats, rice confectionery, etc. More preferably, it is used for baked goods (cookies, biscuits, crackers, cakes, etc.) and fried foods (fried noodles, potato chips, etc.).

  In order to obtain the effect of improving oxidation stability in the present invention, a step of blending a polyphenol compound and an alkaline substance may be included in an arbitrary step of the production process of oily food.

  For example, blending oils and fats, polyphenol compounds and alkali substances individually, adding one of polyphenol compounds and alkali substances to fats and oils, blending either one individually, polyphenol compounds and alkali substances and fats and oils And the like. In addition, in the case of foods that include a heating process of fats and oils such as baked goods and fried foods, polyphenol compounds and alkaline substances are included in fats and oils for kneading baked goods and cooking oils such as fried oil of fried foods. Is preferably added in advance.

  By using an emulsifier as the alkaline substance, the antioxidant of the present invention can be uniformly dispersed in food. For this reason, in an oil-based foodstuff, an antioxidant ability can be exhibited without variation.

  Also in these oil-based foods, the blending amount and blending ratio of the polyphenol compound and the alkaline substance are the same as in the case of the antioxidant.

  As an oil-and-fat composition of the present invention, a polyphenol compound and an alkaline substance can be blended with the above-described oil and fat. Examples of the method for producing an oil and fat composition include a method in which an alkali substance is dispersed in an oil and fat in which a polyphenol compound is dispersed, a method in which a polyphenol compound is dispersed in an oil and fat in which an alkali substance is dispersed, and an oil and fat in which a polyphenol compound is dispersed. And a method of mixing a fat and oil in which an alkaline substance is dispersed, a method of dispersing a mixture of a polyphenol compound and an alkaline substance in the fat and oil, and the like.

  Moreover, in order to improve the dispersibility of polyphenol, it can also mix | blend with alcohol, such as ethanol and an alcohol formulation, and water. In the case of adding water, it is preferable to use after dehydration in consideration of long-term storage stability. Above all, from the viewpoint that the dispersibility of the polyphenol compound is improved, a uniform product can be obtained, and it can be used without dehydration, etc., the polyphenol compound dispersed in ethanol is blended with the fat and oil in which the alkaline substance is dispersed. The method is more preferably considered.

  In the present invention, the above fat composition can be rapidly cooled and used as a plastic fat.

  Moreover, the emulsion which added the water phase to the said oil-fat composition can be rapidly cooled and kneaded, and it can also be set as a plastic fat.

  The form of the emulsion containing an aqueous phase includes a water-in-oil type, an oil-in-water type, an oil-in-water type, and a water-in-oil-in-water type, and the content of the aqueous phase is preferably 0.6 to 40 mass. %, More preferably 2 to 35% by mass. As a form containing an aqueous phase, a water-in-oil type is preferable, and margarine is exemplified.

  Moreover, shortening is also illustrated as a form which used fats and oils as plastic fats and oils.

  The plastic fat can be produced by a known method. For example, the oil phase containing the oil and fat composition of the present invention can be heated and rapidly cooled and chilled by a cooling mixer such as a combinator, perfector, bottor, or nexus. In addition, in the form containing an aqueous phase, the oil phase containing the oil and fat composition of the present invention and the aqueous phase are appropriately heated, mixed and emulsified, and then cooled and mixed with a combinator, perfector, bottor, nexus, etc. The machine can be quickly cooled and kneaded. After quenching with a cooling mixer, aging (tempering) may be performed as necessary.

  When added to a confectionery, the oil and fat composition of the present invention is added as a plastic oil and fat from the viewpoint that the operability during production of the confectionery and the confectionery is not dispersed evenly and dispersed in the confectionery. More preferably.

  If the oil-fat composition of the present invention does not impair the effects of the present invention, a known antioxidant can be used in combination. As the antioxidant used in combination, natural and synthesized antioxidants can be used. For example, various tocopherols (α, β, γ, δ etc.), L-ascorbic acid stearate, L-ascorbic acid palmitate, erythorbine Examples include sodium acid and catechins.

  A fragrance | flavor, a pigment | dye, silicone, etc. can be added to the oil-fat composition of this invention as needed.

  EXAMPLES Hereinafter, although it demonstrates still in detail based on the Example of this invention, this invention is not limited to these Examples at all.

  In addition, the soap test was measured according to 2.6.2-1996 (soap) of the standard fats and oils analysis test method (Japan Oil Chemical Society).

<Experiment 1. Oxidation stability evaluation test of fats and oils with various polyphenol compounds>
(Reference example)
As an alkaline substance in palm oil, 0.05% (w / w) sodium acetate (AcONa, manufactured by Kokusan Chemical Co., Ltd., purity 98.5%), 0.05% (w / w) sodium oleate (OleNa, Wako Pure Chemical Industries, Ltd., purity 60.0% or higher), 1% (w / w) CR-ED (polyglycerin condensed ricinoleic acid ester, Sakamoto Pharmaceutical Co., Ltd.) which is a commercially available emulsifier exhibiting alkalinity Each was dissolved to obtain three types of samples. In addition, about the said alkaline substance and the emulsifier which shows alkalinity, the soap test was done and the sodium oleate conversion value was calculated | required. For example, 0.05% (w / w) sodium acetate has a sodium oleate equivalent value of 1828 ppm, and 1% CR-ED has a sodium oleate equivalent value of 122 ppm. As described above, sodium oleate has a purity of 60% or more and also contains stearic acid in addition to oleic acid. Therefore, even if the addition amount is 0.05% (w / w), olein The sodium acid equivalent value is 449 ppm.

  CDM (hr) of palm oil alone and CDM (hr) of the obtained sample were measured. The measurement of CDM is a method for evaluating the oxidation stability of fats and oils, which is listed as an official method in the Standard Oils and Fats Analysis Method and the American Petroleum Institute, and collects volatile decomposition products generated by fats and oils oxidation in pure water. Then, the conductivity is continuously measured, and the time to the bending point at which the rate of change rapidly increases is obtained. [CDM test (Conductometric Determination Method): standard oil analysis method 2.5.1.2-1996 (edited by the Japan Oil Chemists' Society) CDM value was determined, specifically, oil heated to 120 ° C. The volatile decomposition products generated by oxidation were collected in water, and the time (hr) until the inflection point at which the water conductivity changed rapidly was investigated. It shows that the nature is high.

Example 1
After dissolving 0.05% (w / w) sodium acetate as an alkaline substance in palm oil, 4′-hydroxyflavanone (manufactured by Tokyo Chemical Industry Co., Ltd., 4′-hydroxyflavanone content 99.9% as a polyphenol compound) 1% (w / v) ethanol solution was prepared, 2 mL was added to 100 g of palm oil and stirred to obtain a sample having a polyphenol content of 200 ppm of oil. The CDM (hr) of palm oil to which only 4′-hydroxyflavanone was added and the CDM (hr) of the obtained sample were measured. Moreover, it calculated about the synergistic effect of a polyphenol compound and an alkaline substance from the following formula.

  {(CDM when polyphenol compound and alkali substance are used together)-(CDM with palm oil alone)}-{(CDM when polyphenol compound is added)-(CDM alone with palm oil)}-{(CDM when alkali substance is added) -(CDM with palm oil alone)} (1)

(Example 2)
Palm to which only 6-hydroxyflavanone was added in the same manner as in Example 1 except that the polyphenol compound was changed to 6-hydroxyflavanone (Tokyo Chemical Industry Co., Ltd., 6-hydroxyflavanone content 99.3%). The CDM (hr) of the oil and the CDM (hr) of the obtained sample were measured. Moreover, it calculated about the synergistic effect of a polyphenol compound and an alkaline substance.

(Example 3)
Except that the polyphenol compound was changed to daidzein (manufactured by Tokyo Chemical Industry Co., Ltd., daidzein content 99.9%), the CDM (hr) of palm oil to which only daidzein was added was obtained in the same manner as in Example 1. The CDM (hr) of the obtained sample was measured. Moreover, it calculated about the synergistic effect of a polyphenol compound and an alkaline substance.

Example 4
As an alkaline substance in palm oil, 0.05% (w / w) sodium acetate, 0.05% (w / w) sodium oleate, 1% (w / w) CR-ED (Sakamoto Pharmaceutical Co., Ltd.) Except that the polyphenol compound was changed to apigenin (manufactured by Wako Pure Chemical Industries, Ltd., apigenin content 99.3%). In the same manner as in Example 1, the CDM (hr) of palm oil to which only apigenin was added and the CDM (hr) of the obtained sample were measured. Moreover, it calculated about the synergistic effect of a polyphenol compound and an alkaline substance.

(Example 5)
CDM (hr) of palm oil to which only baicalein was added was obtained in the same manner as in Example 4 except that the polyphenol compound was changed to baicalein (manufactured by Tokyo Chemical Industry Co., Ltd., baicalein content 98.8%). The CDM (hr) of the obtained sample was measured. Moreover, it calculated about the synergistic effect of a polyphenol compound and an alkaline substance.

(Example 6)
CDM (hr) of palm oil to which only hesperetin was added was obtained in the same manner as in Example 4 except that the polyphenol compound was changed to hesperetin (manufactured by Wako Pure Chemical Industries, Ltd., hesperetin content 99.6%). The CDM (hr) of the obtained sample was measured. Moreover, it calculated about the synergistic effect of a polyphenol compound and an alkaline substance.

(Example 7)
CDM (hr) of palm oil to which only naringenin was added was obtained in the same manner as in Example 4 except that the polyphenol compound was changed to naringenin (manufactured by Tokyo Chemical Industry Co., Ltd., naringenin content 95.8%). The CDM (hr) of each sample was measured. Moreover, it calculated about the synergistic effect of a polyphenol compound and an alkaline substance.

(Example 8)
CDM (hr) of palm oil to which only kaempferol was added in the same manner as in Example 4 except that the polyphenol compound was changed to kaempferol (manufactured by Tokyo Chemical Industry Co., Ltd., kaempferol content 99.8%). The CDM (hr) of the obtained sample was measured. Moreover, it calculated about the synergistic effect of a polyphenol compound and an alkaline substance.

Example 9
CDM of palm oil to which only eriodictythiol was added in the same manner as in Example 4 except that the polyphenol compound was changed to eriodictyol (manufactured by PhytoLab GmbH & Co. KG, eriodictyol content 100%). hr), and the CDM (hr) of the obtained sample was measured. Moreover, it calculated about the synergistic effect of a polyphenol compound and an alkaline substance.

(Example 10)
As an alkaline substance in palm oil, 0.05% (w / w) sodium oleate and 1% (w / w) CR-ED were dissolved, and the polyphenol compound was quercetin (manufactured by Tokyo Chemical Industry Co., Ltd., containing quercetin). Except that the amount was changed to 99.4%), the CDM (hr) of palm oil to which only quercetin was added and the CDM (hr) of the obtained sample were measured in the same manner as in Example 1. Moreover, it calculated about the synergistic effect of a polyphenol compound and an alkaline substance.

(Example 11)
Except that the polyphenol compound was changed to (+)-catechin (manufactured by Tokyo Chemical Industry Co., Ltd., (+)-catechin content 99.8%), only (+)-catechin was obtained in the same manner as in Example 4. The CDM (hr) of the added palm oil and the CDM (hr) of the obtained sample were measured. Moreover, it calculated about the synergistic effect of a polyphenol compound and an alkaline substance.

Example 12
CDM (hr) of palm oil to which only epicatechin was added in the same manner as in Example 4 except that the polyphenol compound was changed to epicatechin (Wako Pure Chemical Industries, Ltd., epicatechin content 100%). CDM (hr) of the obtained sample was measured. Moreover, it calculated about the synergistic effect of a polyphenol compound and an alkaline substance.

(Example 13)
1% (w / w) CR-ED was dissolved in palm oil as an alkaline substance, and the polyphenol compound was changed to dihydromyricetin (manufactured by PhytoLab GmbH & Co. KG, dihydromyricetin content 98.7%). Except that, CDM (hr) of palm oil to which only dihydromyricetin was added and CDM (hr) of the obtained sample were measured in the same manner as in Example 1. Moreover, it calculated about the synergistic effect of a polyphenol compound and an alkaline substance.

(Example 14)
Palm to which isoliquiritigenin alone was added in the same manner as in Example 1 except that the polyphenol compound was changed to isoliquiritigenin (manufactured by Tokyo Chemical Industry Co., Ltd., isoliquiritigenin content 97.1%). The CDM (hr) of the oil and the CDM (hr) of the obtained sample were measured. Moreover, it calculated about the synergistic effect of a polyphenol compound and an alkaline substance. Isochiritigenin is a chalcone compound.

(Example 15)
CDM (hr) of palm oil to which only butane was added was obtained in the same manner as in Example 1 except that the polyphenol compound was changed to butane (Tokyo Chemical Industry Co., Ltd., butane content 99.8%). The CDM (hr) of each sample was measured. Moreover, it calculated about the synergistic effect of a polyphenol compound and an alkaline substance. Butein is a chalcone compound.

(Comparative Example 1)
CDM of palm oil to which only dihydrorobinetin was added was obtained in the same manner as in Example 4 except that the polyphenol compound was changed to dihydrorobinetin (manufactured by EXTRASYNTHES, content of dihydrorobinetin 95%). ), And the CDM (hr) of the obtained sample was measured. Moreover, it calculated about the synergistic effect of a polyphenol compound and an alkaline substance.

(Comparative Example 2)
As alkaline substances in palm oil, 0.05% (w / w) sodium acetate and 0.05% (w / w) sodium oleate are dissolved, and the polyphenol compound is myricetin (manufactured by Tokyo Chemical Industry Co., Ltd., myricetin). Except that the content was changed to 97.8%), the CDM (hr) of palm oil to which only myricetin was added and the CDM (hr) of the obtained sample were measured in the same manner as in Example 1. Moreover, it calculated about the synergistic effect of a polyphenol compound and an alkaline substance.

(Comparative Example 3)
CDM of palm oil to which only epigallocatechin was added in the same manner as in Example 4 except that the polyphenol compound was changed to epigallocatechin (Wako Pure Chemical Industries, Ltd., epigallocatechin content 100%). hr), and the CDM (hr) of the obtained sample was measured. Moreover, it calculated about the synergistic effect of a polyphenol compound and an alkaline substance.

(Comparative Example 4)
Palm to which only epigallocatechin gallate was added in the same manner as in Example 4 except that the polyphenol compound was changed to epigallocatechin gallate (manufactured by Tokyo Chemical Industry Co., Ltd., epigallocatechin gallate content 98.8%). The CDM (hr) of the oil and the CDM (hr) of the obtained sample were measured. Moreover, it calculated about the synergistic effect of a polyphenol compound and an alkaline substance.

(Comparative Example 5)
CDM (hr) of palm oil to which only flavanone was added in the same manner as in Example 1 except that the polyphenol compound was changed to flavanone (manufactured by Tokyo Chemical Industry Co., Ltd., flavanone content 99.8%), and sample obtained CDM (hr) was measured. Moreover, it calculated about the synergistic effect of a polyphenol compound and an alkaline substance.

(Comparative Example 6)
As an alkaline substance in palm oil, 0.05% (w / w) sodium acetate and 1% (w / w) CR-ED were dissolved, and the polyphenol compound was chlorogenic acid (chlorogenic acid, manufactured by Wako Pure Chemical Industries, Ltd. Except that the acid content was changed to 99.8%), the CDM (hr) of palm oil to which only chlorogenic acid was added and the CDM (hr) of the obtained sample were measured in the same manner as in Example 1. Moreover, it calculated about the synergistic effect of a polyphenol compound and an alkaline substance.

  Table 1 shows the CDM measurement results of the above Reference Examples, Examples 1 to 15 and Comparative Examples 1 to 6, and the synergistic effect when the polyphenol compound and the alkaline substance are used in combination.

<Experiment 2. Evaluation of oxidation stability when the amount of alkali substance added is changed>
Experiments on changes in oxidation stability when the amount of alkaline substance added to palm oil is changed. And evaluated in the same manner. As alkaline substances, CR-ED, sodium acetate (AcONa), and sodium hydroxide (NaOH) were added in amounts of 30, 100, 500, 2000, 5000, 10,000, and 15000 ppm in terms of sodium oleate, respectively. As the polyphenol compound, 200 ppm naringenin was used in the same manner as in Example 7. The results are shown in Tables 2-4.

  As shown in Table 2, when CR-ED was used as the alkaline substance, it was confirmed that the apparent CDM value continued to increase in a concentration-dependent manner up to 10,000 ppm as the alkaline substance amount. However, regarding the synergistic effect of CR-ED and naringenin, the CDM value increased in a concentration-dependent manner up to 5000 ppm in terms of sodium oleate and the oxidation stability was improved, but high concentrations of 10000 ppm and 15000 ppm. When CR-ED was added, it was confirmed that the synergistic effect with naringenin tends to decrease.

  As shown in Table 3, it was confirmed that when sodium acetate was used as the alkaline substance, the apparent CDM value continued to increase in a concentration-dependent manner, and showed a higher value than when CR-ED was added. It was. Furthermore, regarding the synergistic effect of sodium acetate and naringenin, it was confirmed that the CDM value increased depending on the concentration of sodium acetate, and the oxidation stability was improved.

  As shown in Table 4, when sodium hydroxide is used as the alkaline substance, as in the case of using sodium acetate, the apparent CDM value and the synergistic effect when sodium hydroxide and naringenin are used in combination are shown. It was confirmed that all of the CDM values increased in a concentration-dependent manner and the oxidation stability was improved. On the other hand, it was confirmed that the value of the apparent CDM was at a lower level than when CR-ED and sodium acetate were used as alkaline substances.

  FIG. 1 shows a graph of CDM values showing a synergistic effect when the above three kinds of alkaline substances and naringenin are used in combination.

  As shown in FIG. 1, when sodium acetate or sodium hydroxide was added as an alkaline substance, it was confirmed that the synergistic effect of CDM extension increased according to the amount of addition. On the other hand, when CR-ED, which is an emulsifier containing an alkaline substance, is added, a synergistic effect of CDM extension is recognized depending on the addition amount up to 5000 ppm in terms of sodium oleate. It was confirmed that the synergistic effect of was reduced.

<Experiment 3. Evaluation of oxidation stability when the amount of polyphenol compound added is changed>
Experiments on changes in oxidation stability when the amount of polyphenol compound added to palm oil is changed. And evaluated in the same manner. As polyphenol, naringenin was added at 20, 50, 200, 500, 1000, 2000 ppm. For the adjustment of naringenin, a 1% (w / v) ethanol solution was used as in Example 7. As an alkaline substance, sodium acetate was added so that it might become 1828 ppm in conversion of sodium oleate. The results are shown in Table 5.

  As shown in Table 5, it was confirmed that the synergistic effect of CDM extension increases as the amount of naringenin increases.

<Experiment 4. Fly test using polyphenol compound and alkaline substance in combination>
Six types of frying oil shown in Table 6 were prepared and subjected to a frying test.
A frying oil was obtained by adding 200 ppm of naringenin or epigallocatechin gallate (EGCg) as a polyphenol compound and 500 ppm of sodium acetate as an alkaline substance to palm oil alone or palm oil. For the adjustment of naringenin and epigallocatechin gallate (EGCg), a 1% (w / v) ethanol solution was used as in Example 7 and Comparative Example 4.
Using the obtained frying oil, fried noodles were produced, and their CDM (hr) was measured.

<Manufacture of fried noodles>
A commercially available raw Chinese noodle (Hachiban noodle workshop) (about 130 g) was boiled with hot water for 1 minute and then fried with 140 ° C. frying oil for 3 minutes to obtain fried noodles.

<CDM measurement>
The fried noodles were finely crushed and 3 g was used to measure the CDM of the fried noodles. The results are shown in Table 6.

<Evaluation of color change>
In the frying test, the frying oil (fry oil heated at 140 ° C. for 5 minutes) before adding the fried noodles was analyzed with a Robibond colorimeter using a 5.25 inch cell (standard oil analysis test method) According to 2.2.11-1996 (Robibond method) of the Japan Oil Chemists' Society, the color tones of these sample fat compositions are shown in Table 7.

  As shown in Table 6, in the fried noodles manufactured using frying oil in which a polyphenol compound and an alkaline substance were blended in fats and oils, it was confirmed that CDM was extended as compared to fried noodles manufactured with fried oil containing only fats and oils.

  Moreover, as shown in Table 7, in the evaluation of the color tone change, epigallocatechin gallate was intensely colored and could not be measured.

  For this reason, it was confirmed that the present invention is effective not only in the oil / fat composition but also in oily foods such as fried foods using the oil / fat composition, with less antioxidant ability and less color change.

<Experiment 5. Evaluation of change in color tone of oil composition over time>
200 ppm naringenin as a polyphenol compound in palm oil (naringenin used a 1% (w / v) ethanol solution as in Example 7), sample A added with 1% CR-ED as an alkaline substance, and a polyphenol compound Sample B prepared in the same manner as Sample A except that it was changed to 200 ppm of epigallocatechin gallate (epigallocatechin gallate was 1% (w / v) ethanol solution as in Comparative Example 4). After standing in a thermostatic bath at 0 ° C. for 3 days, using a 5.25 inch cell with a Robibond colorimeter, 2.2.11-1996 of the standard fat analysis method (Japan Oil Chemistry Society) According to the Robibond method), the color tone of these sample fat compositions was evaluated. The results are shown in Table 8.

  As shown in Table 8, sample A containing naringenin had an R value of 1.9 and a Y value of 18 by a Robibond colorimeter, and even when exposed to high temperatures for a long time, the fat composition was almost colored. Not confirmed. On the other hand, in sample B containing epigallocatechin gallate, which is a tea extract, the R value by the Robibond colorimeter was 8.8, the Y value was 54, and it was confirmed that the fat composition changed to reddish brown. This is considered to show that among the polyphenol compounds, catechins containing epigallocatechin gallate have a low function of suppressing the browning of the oil and fat composition.

  Therefore, it is considered preferable to add a polyphenol compound other than catechins to the oil and fat composition used for cooking oily foods.

<Experiment 6. Evaluation of oxidation stability by various emulsifiers>
(Reference example)
As an alkali substance in palm oil, Poem V200 (reactive monoglyceride, manufactured by Riken Vitamin Co., Ltd.) of 6.67% (w / w) oil, which is a commercially available emulsifier exhibiting alkalinity, 2.32% (w / w) ER-290 (sucrose erucic acid fatty acid ester, manufactured by Mitsubishi Chemical Foods Co., Ltd.) was dissolved to obtain two types of samples. In addition, about the emulsifier which shows alkalinity which is said alkaline substance, the soap test was done and the sodium oleate conversion value was calculated | required. For example, Poem V200 has a sodium oleate equivalent value of 1826 ppm and ER-290 of 5252 ppm.

  In addition, the amount of each emulsifier added is as follows. In the same manner as CR-ED (polyglycerin condensed ricinoleic acid ester) which is an emulsifier, a sodium oleate equivalent value was adjusted to 122 ppm. The results are shown in Table 9.

  From Table 9, regardless of the type of emulsifier, any emulsifier exhibiting alkalinity could be confirmed to improve the antioxidant ability when used in combination with the polyphenol compound of the present invention.

Claims (7)

  A flavonoid compound containing 1 to 5 hydroxyl groups and having no gallate structure on the B ring (excluding the chalcone compound), containing 6 hydroxyl groups, having a carbonyl group on the C ring, A flavonoid compound having no carbon-carbon double bond between carbon and 3-position carbon, a polyphenol compound containing at least one member selected from the group consisting of chalcone compounds (excluding dihydroquercetin), and an alkaline substance, An antioxidant that is added as a component added to the target to suppress oxidation.   The antioxidant according to claim 1, wherein the alkaline substance is at least one member selected from the group consisting of monovalent carboxylates and alkali metal salts.   The oil-fat composition containing the antioxidant of Claim 1 or 2, and fats and oils.   The oil and fat composition according to claim 3, wherein the alkaline substance is at least one member selected from the group consisting of monovalent carboxylates and alkali metal salts.   The oil-and-fat composition according to claim 3 or 4, wherein a blending amount of the polyphenol compound is 20 to 5000 ppm with respect to the oil.   The fat and oil composition according to any one of claims 3 to 5, wherein a blending amount of the alkaline substance is 30 to 10,000 ppm with respect to oil as sodium oleate. The oil-based foodstuff containing the oil-fat composition as described in any one of Claims 3-6.

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