WO2017149701A1

WO2017149701A1 - Fat or oil composition

Info

Publication number: WO2017149701A1
Application number: PCT/JP2016/056457
Authority: WO
Inventors: 真晴加藤; 美和子盛川; 将宏杉山
Original assignee: 不二製油グループ本社株式会社; 不二製油株式会社
Priority date: 2016-03-02
Filing date: 2016-03-02
Publication date: 2017-09-08

Abstract

The present invention addresses the problem of providing a fat or oil composition that exhibits unprecedentedly high oxidation stability by using a simple method. The present invention was accomplished by discovering that the effect of extremely high oxidation stability is achieved by a fat or oil composition which contains a water-soluble antioxidant, uses sugar as necessary, involves dispersion of a water phase containing at least a given amount of a water-soluble solid into an oil phase in a given particle diameter range, and also contains a prescribed amount of water.

Description

Oil composition

The present invention relates to an oil and fat composition comprising a food or food additive and having a strong antioxidant power, and a method for producing the same.

It is known that an antioxidant effect can be obtained by adding a water-soluble antioxidant to fats and oils (Patent Document 1).
Patent Document 2 describes an oil and fat imparted with oxidation stability using a water-soluble tea polyphenol and an emulsifier.
Patent Document 3 describes that, in the chlorogenic acids having a specific composition, the antioxidant activity is improved by further adding a saccharide.
Patent Document 4 discloses that “a solid phase containing a tea extract is an oily composition dispersed in an oil phase containing an oily component and an emulsifier having an HLB of 10 or less, and containing the tea extract. Deodorant / antioxidant tea extract-containing oily composition, wherein the solid phase is fine particles having an average particle size of 5 μm or less, and the water content or alcohol aqueous solution content in the solid phase is 30% by weight or less Is described.
Patent Document 5 describes “an oil-soluble antioxidant having a water-soluble antioxidant property derived from a natural product and having an average particle size of 40 to 120 nm that can be transparently dispersed in fats and oils”.

There is a report that TBHQ (tertiary butylhydroquinone) is a powerful synthetic antioxidant (Non-patent Document 1), and it may be used as an index when screening for a new antioxidant (Non-patent Document 1). Reference 2).

International Publication WO2O01 / 096506 Pamphlet International publication WO2013 / 172348 pamphlet JP-A-9-143465 JP 2000-229118 A JP 2013-159730 A

An object of the present invention is to provide an oil and fat composition having unprecedented strong oxidation stability by a simple method.

By using the techniques disclosed in Patent Documents 1 and 2, fats and oils having improved oxidation stability to a certain extent can be obtained.
However, patent document 1 is the fats and oils used for frying in principle, and the state containing a fixed amount or more of water is not assumed. In the first place, there is no suggestion of an effect on polyunsaturated fatty acid-containing fats and oils that are extremely susceptible to oxidative degradation than frying fats and oils.
Also in Patent Document 2, as in Patent Document 1, application to heating and cooking oils and fats such as frying is a preferred use, and a state of containing a certain amount or more of water is not assumed. And it is not suggested about the effect on polyunsaturated fatty acid-containing fats and oils.

In Patent Document 3, the composition of chlorogenic acids must be specified, and the versatility is low. In addition, it does not suggest that the present invention exhibits extremely strong antioxidant power, which is a problem.
In Patent Document 4, a tea extract that is substantially dehydrated and solid is dispersed in oil, and suggests a strong antioxidant effect that prevents oxidation of PUFA oil. Not what you want.
In Patent Document 5, the description of the examples shows that what can be used as an antioxidant is substantially limited to catechins, and it is necessary to use a water-soluble emulsifier. there were. In addition, its antioxidant power is less than 1.5 times that of control oil (corn oil), and PUFA oil, which has extremely low oxidative stability compared to corn oil, can impart oxidative stability. Was unthinkable.

TBHQ is known to be a powerful antioxidant, but it has not been approved for food use in Japan. Actually, in order to further improve the oxidative stability of fats and oils containing a large amount of polyunsaturated fatty acids, it has been estimated that an antioxidant power exceeding TBHQ is required. Of course it needs to be usable as food.

Even if you look at the prior art, there are some that have an anti-oxidant power, but the anti-oxidant power that is actually shown is limited, and oxidative stability is reduced to less stable oils such as PUFA oil. There is no anti-oxidant power that can be imparted, and it seemed difficult to further improve the antioxidant power in this field.
However, the present inventor has further studied earnestly. As a result, an oil composition containing a water-soluble antioxidant and, if necessary, water-soluble solids such as carbohydrates, and an aqueous phase containing a certain amount or more of water-soluble solids dispersed in the oil phase with a predetermined particle size or less The present invention was completed by finding that a material containing a predetermined amount of water exhibits a very strong oxidation stabilizing effect.

That is, the present invention
(1) An oil and fat composition containing 1.9 to 18% by weight of water that satisfies the following requirements:
1. Containing 3 to 65% by weight of a water-soluble antioxidant in the aqueous phase,
2. The aqueous phase contains saccharides as necessary, and contains a total of 18 to 75% by weight of water-soluble solids.
3. 4.3 to 38% by weight of the aqueous phase is dispersed in the oil phase with a particle size of 300 nm or less.
(2) The oil and fat composition according to (1), wherein the aqueous phase contains one or more saccharides selected from sugar alcohol, glucose, sucrose, and dextrin,
(3) The oil phase contains at least one oil-soluble emulsifier selected from polyglycerin condensed ricinolate, sugar ester, and glycerin fatty acid ester in an amount of 0.7 to 6.8 times the weight of water. The fat and oil composition according to the description,
(4) The oil phase contains one or more oil-soluble emulsifiers selected from polyglycerin condensed ricinolate, sugar ester, glycerin fatty acid ester, 0.7 to 6.8 times the weight of water, (2) The fat and oil composition according to the description,
(5) The oil and fat composition according to (2), wherein the water-soluble antioxidant is one or more selected from vitamin C, amino acids and catechins,
(6) The oil and fat composition according to (3), wherein the water-soluble antioxidant is one or more selected from vitamin C, amino acids, and catechins,
(7) The oil and fat composition according to (4), wherein the water-soluble antioxidant is one or more selected from vitamin C, amino acids and catechins,
(8) The oil and fat composition according to (6), wherein the amino acid is one or more selected from glycine, proline, and serine,
(9) The oil and fat composition according to (7), wherein the amino acid is one or more selected from glycine, proline, and serine,
(10) A method for producing an oil and fat composition by the following steps,
1. A step of preparing a water phase containing 3 to 65% by weight of a water-soluble antioxidant in the water phase, containing a saccharide if necessary, and a total of 18 to 75% by weight as a water-soluble solid content;
2. The water phase is added to the oil phase so that the water phase is 4.3 to 38% by weight, and the water content in the oil and fat composition is 1.9 to 18% by weight, so that the particle diameter is 300 nm or less. A process for making a water-in-oil type oil and fat composition,
(11) The production method according to (10), wherein the saccharide is one or more selected from sugar alcohol, glucose, sucrose, and dextrin,
(12) The oil phase contains at least one oil-soluble emulsifier selected from polyglycerin condensed ricinolate, sugar ester, and glycerin fatty acid ester in an amount of 0.7 to 6.8 times the weight of water in the oil and fat composition. (11) The production method according to
(13) The production method according to (12), wherein the water-soluble antioxidant is one or more selected from vitamin C, amino acids, and catechins,
(14) The production method according to (13), wherein the amino acid is one or more selected from glycine, proline, and serine,
(15) The production method according to (13), wherein 12 to 76% of the moisture contained in the oil and fat composition is partially dehydrated to make the moisture in the oil and fat composition 1.9 to 18% by weight,
(16) The water-soluble antioxidant is one or more selected from vitamin C, glycine, proline, serine and catechin, and 12 to 76% of the water contained in the oil and fat composition is partially dehydrated to obtain an oil and fat composition. The production method according to (11), wherein water in the product is 1.9 to 18% by weight,
(17) The production method according to (14), wherein 12 to 76% of the moisture contained in the oil and fat composition is partially dehydrated to make the moisture in the oil and fat composition 1.9 to 18% by weight,
(18) The oily phase contains at least one oil-soluble emulsifier selected from polyglycerin condensed ricinolate, sugar ester, and glycerin fatty acid ester in an amount of 0.7 to 6.8 times the weight of water in the oil and fat composition. The water-soluble antioxidant is at least one selected from vitamin C, glycine, proline, serine and catechin, and 12 to 76% of the water contained in the oil and fat composition is partially dehydrated, The production method according to (10), wherein the water content is 1.9 to 18% by weight,
(19) A method for producing an unsaturated fatty acid-containing oil or fat, wherein the oil or fat composition according to (7) is added to an unsaturated fatty acid-containing oil or fat so as to be 0.1 to 40% by weight,
(20) A method for preventing oxidation of unsaturated fatty acid-containing fats and oils, comprising adding the fat composition according to (7) to unsaturated fatty acid-containing fats so as to be 0.1 to 40% by weight,
It is about.
In other words,
(21) A water phase of 4.3 to 38% by weight containing a water-soluble antioxidant in an amount of 18 to 65% by weight in the aqueous phase is dispersed in the oil phase with a particle size of 300 nm or less, and a water content of 1.9 to 18 An oil and fat composition containing% by weight,
(22) Aqueous phase 4 containing 3 to 65% by weight of a water-soluble antioxidant in the aqueous phase, and further adding a saccharide such that the total amount of water-soluble solids in the aqueous phase is 18 to 75% by weight. An oil or fat composition containing 1.9 to 18% by weight of water, wherein 3 to 38% by weight is dispersed in the oil phase with a particle size of 300 nm or less,
(23) The oil phase contains at least one oil-soluble emulsifier selected from polyglycerin condensed ricinolate, sugar ester, and glycerin fatty acid ester in an amount of 0.7 to 6.8 times the weight of water. (21) Or the oil and fat composition according to (22),
(24) The oil and fat composition according to any one of (21) to (23), wherein the water-soluble antioxidant is one or more selected from vitamin C, amino acids, and catechins,
(25) The oil and fat composition according to (24), wherein the amino acid is one or more selected from glycine, proline, and serine,
(26) The oil / fat composition according to any one of (22) to (25), wherein the saccharide is one or more selected from sugar alcohol, glucose, sucrose, and dextrin,
(27) A method for producing an oil and fat composition by the following steps,
1. Preparing an aqueous phase containing 18-65% by weight of a water-soluble antioxidant in the aqueous phase;
2. Adding the aqueous phase to the oil phase such that the proportion of the aqueous phase is 4.3 to 38% by weight and the water content in the oil and fat composition is 1.9 to 18% by weight;
3. A step of making a water-in-oil emulsion so that the particle size of the aqueous phase is 300 nm or less,
(28) A method for producing an oil and fat composition by the following steps,
1. A step of preparing an aqueous phase containing 3 to 65% by weight of a water-soluble antioxidant in the aqueous phase and further containing a saccharide so that the total amount of water-soluble solids in the aqueous phase is 18 to 75% by weight;
2. Adding the aqueous phase to the oil phase such that the proportion of the aqueous phase is 4.3 to 38% by weight and the water content in the oil and fat composition is 1.9 to 18% by weight;
3. A step of making a water-in-oil emulsion so that the particle size of the aqueous phase is 300 nm or less,
(29) The oily phase contains at least one oil-soluble emulsifier selected from polyglycerin condensed ricinolate, sugar ester, and glycerin fatty acid ester in an amount of 0.7 to 6.8 times the weight of water in the oil and fat composition. , (27) or the production method according to (28),
(30) The production method according to any one of (27) to (29), wherein the water-soluble antioxidant is one or more selected from vitamin C, amino acids, and catechins,
(31) The production method according to (30), wherein the amino acid is one or more selected from glycine, proline, and serine,
(32) The production method according to any one of (27) to (31), wherein 12 to 76% of the moisture contained in the oil and fat composition is partially dehydrated.
(33) A method for producing an unsaturated fatty acid-containing fat or oil, wherein the fat or oil composition according to any one of (21) to (26) is added to an unsaturated fatty acid-containing fat or oil so as to be 0.1 to 40% by weight,
(34) A method for preventing oxidation of an unsaturated fatty acid-containing oil or fat, comprising adding the oil or fat composition according to any one of (21) to (26) to an unsaturated fatty acid-containing oil or fat so as to be 0.1 to 40% by weight. ,
(35) Soybean oil, wherein the oil or fat composition according to any one of (21) to (26) is contained in an oil or fat containing 10 to 70% by weight of a highly unsaturated fatty acid in an amount of 0.1 to 40% by weight. Highly unsaturated fatty acid-containing fats and oils having the above oxidation stability,
(36) The oil or fat composition according to any one of (21) to (26) is added to an oil or fat containing 10 to 70% by weight of a highly unsaturated fatty acid so as to be 0.1 to 40% by weight. A process for producing highly unsaturated fatty acid-containing fats and oils having oxidation stability higher than that of soybean oil,
(37) The oil or fat composition according to any one of (21) to (26) is added to an oil or fat containing 10 to 70% by weight of a highly unsaturated fatty acid so as to be 0.1 to 40% by weight. A method for imparting oxidation stability higher than that of soybean oil to highly unsaturated fatty acid-containing fats and oils,
It is about.

According to the present invention, it is possible to provide an oil and fat composition with extremely high antioxidant ability using edible raw materials that are widely used, and to provide highly unsaturated fatty acid-containing fats and oils having high oxidation stability using the composition. I can do it.

The oil and fat composition according to the present invention has a high antioxidant power.
As a mode of use, this is simply mixed with a subject to be given antioxidant power. Since the oil / fat composition according to the present invention is a water-in-oil emulsified oil / fat composition, when used for oil / fat, it can be easily dispersed in the oil / fat.
As fats and oils to be used, oils and fats containing unsaturated fatty acids can be widely used. Therefore, it can also be used to improve the stabilization of commonly used oils such as soybean oil and rapeseed oil. Moreover, when it uses for the fats and oils containing the fatty acid which has a some unsaturated bond called PUFA, the performance of the fats and oils composition which concerns on this invention is exhibited notably, and a preferable result can be obtained. In the present invention, docosahexaenoic acid may be abbreviated as DHA, and eicosapentaenoic acid may be abbreviated as EPA. In the present invention, fats and oils containing a large amount of these are sometimes simply referred to as “PUFA oil”.
The amount of the oil / fat composition according to the present invention depends on the amount of unsaturated fatty acid in the target oil / fat, etc., but is preferably added so that the oil / fat composition is 0.1 to 40% by weight. This amount is more desirably 3 to 30% by weight, and further desirably 7 to 20% by weight. Antioxidant power can be preferably imparted by adding an appropriate amount.

The effect relating to the oxidation stability of the oil and fat composition according to the present invention is achieved by measuring a peroxide value (POV) when a predetermined amount of the oil and fat composition is added to a predetermined oil and fat and stored at a constant temperature. It can be said that the longer the time during which the increase in the POV value is suppressed, the stronger the oxidation stability. Specific measurement methods are described in the examples.
As a simple evaluation method, a certain judgment index can be obtained by a CDM test. Here, CDM (Conductmetric Determination Method) is a value indicating the oxidation stability of fats and oils and can be used as an index for evaluating the oxidation stability. The longer the stability time by CDM, the better the oxidation stability.
The CDM test can be performed using dedicated test equipment (Rancimat). The specific measurement method of this method is also described in the examples. Both are accelerated tests that test at a higher temperature than the intended mode of use.
“Oxidative stability higher than soybean oil” refers to a case where the above-described measurement method exhibits oxidative stability exceeding that of soybean oil.

The water-soluble antioxidant referred to in the present invention is an antioxidant that is soluble in water. Specifically, vitamin C (sometimes abbreviated as VC in the present specification), catechin, tea extract, amino acid, bayberry extract can be given, more preferably vitamin C, amino acid, Vitamin C, glycine, proline and serine are desirable. In this invention, these can be selected suitably and 1 or more can be used. By using a suitable water-soluble antioxidant, it is possible to obtain an oil and fat composition exhibiting strong antioxidant power.
In addition, it goes without saying that the water-soluble antioxidants mentioned here are not limited to those conventionally known as water-soluble antioxidants, but also include water-soluble components that have been newly found to have antioxidant power. In particular, amino acids include those that have been newly found to have antioxidant power by this study. Among amino acids, proline, glycine, and serine are particularly desirable because of their strong antioxidant power.

In addition, when catechin is used alone as an antioxidant, the oil composition according to the present invention exhibits a certain antioxidant power, but when other water-soluble antioxidants such as vitamin C and proline are used. In comparison, its antioxidant power tends to be low. Therefore, in the present invention, it is desirable to mainly use other water-soluble antioxidants such as vitamin C, and catechins are desirably used only incidentally, not as antioxidants.
In particular, the present invention can develop an antioxidant power far exceeding that of a synthetic antioxidant in vitamin C, which can be said to be approved in many countries and has been confirmed to be safe from long dietary experiences. It has the feature in the point that can be done.

The amount of the water-soluble antioxidant in the present invention is required to be 3 to 65% by weight in the aqueous phase, more preferably 10 to 63% by weight, and still more preferably 16 to 60% by weight. is there. By using an appropriate amount of an appropriate water-soluble antioxidant, it is possible to obtain an oil and fat composition exhibiting a strong antioxidant power.

The aqueous phase in the present invention is a mixture of water and raw materials that are soluble in water.
In the oil and fat composition according to the present invention, the aqueous phase must be contained in an amount of 4.3 to 38% by weight, and this amount is more desirably 9 to 34% by weight, and further desirably 18 to 30% by weight. It is. By including an appropriate amount of the aqueous phase, the oil and fat composition according to the present invention exhibits a strong antioxidant power.

In the present invention, a more preferable antioxidant power is exhibited by containing a large amount of water-soluble solids in the aqueous phase. In addition, since the oil-fat composition which concerns on this invention is mainly used for a foodstuff, the water-soluble solid content used is a foodstuff or a food additive.
In the present invention, the amount of water-soluble solid in the aqueous phase is 18 to 75% by weight, and this amount is preferably 30 to 75% by weight, and more preferably 50 to 75% by weight. In addition, the quantity of water-soluble solid content said here contains the quantity of a water-soluble antioxidant.

As the water-soluble solid content other than the water-soluble antioxidant, various materials that can be used as foods or food additives can be used. In particular, carbohydrates are desirable because they are inexpensive and have the effect of further increasing antioxidant power. Among carbohydrates, it is desirable to use sugar alcohols, oligosaccharides, various monosaccharides including glucose, various disaccharides including sucrose, and dextrins, more preferably sugar alcohols, sucrose, and dextrins. Most preferably, it is sucrose, ie sugar.
If necessary, an appropriate saccharide is used, and the amount of water-soluble solid content in the aqueous phase is adjusted to an appropriate amount, whereby an oil and fat composition exhibiting a strong antioxidant power can be obtained.

The oil phase as used in the field of this invention means what dissolved the oil-soluble component in a raw material in oil. Here, various edible oils and fats such as soybean oil, rapeseed oil, and fractionated palm oil can be used as the oil. In addition, when there are no oil-soluble components other than oil in the raw material, the oil itself is referred to as an oil phase.
As the oil-soluble component in the raw material in the present invention, an oil-soluble emulsifier is used as necessary. In the present invention, an emulsifier having an HLB of 7 or less is defined as an oil-soluble emulsifier. As the oil-soluble emulsifier, one or more selected from polyglycerin esters, sugar esters, sorbitan esters, and monoglycerin fatty acid esters are desirable, more desirably polyglycerin esters, sugar esters, and distilled monoglycerides, and polyglycerin esters are particularly desirable. Of these, polyglycerin condensed ricinoleate is most preferred. Polyglycerin condensed ricinolate may be abbreviated as PGPR.
The amount of the oil-soluble emulsifier is preferably 0.7 to 6.8 times, more preferably 0.7 to 5 times, and still more preferably 0.7 to 6.8 times the weight of water in the state of the oil or fat composition. 7 to 2 times. If necessary, by using an appropriate amount of an appropriate oil-soluble emulsifier, an oil and fat composition exhibiting a strong antioxidant power can be obtained.

The oil and fat composition according to the present invention is characterized in that the aqueous phase is dispersed in the oil phase with a particle size of 300 nm or less. The particle size is more desirably 160 nm or less, and further desirably 130 nm or less.
By setting the particle size to an appropriate value, a strong antioxidant power can be stably expressed. When precipitation occurs, the particle size is larger than 300 nm. That is, it is necessary that no precipitation occurs visually, and it can be confirmed that the particle diameter is 300 nm or less because precipitation does not occur.

In the present invention, the particle size was measured with the apparatus and conditions described below.
Device name: Zetasizer Nano S, manufacturer: Malvern 10 μl of oil composition to be measured was diluted in 2 ml of hexane and measured.
(Measurement at the stage of the first day after sample preparation was rejected when it was 300 nm or more (that is, when precipitation occurred))
Temperature: 20.0 ℃
Equilibrium time: 240 seconds Cell: Glass cell Measurement angle: 173 °
Positioning method: Optimal position selection Automatic damping selection: Existence

The oil and fat composition according to the present invention contains 1.9 to 18% by weight of water. The water content is more desirably 3 to 15% by weight, and further desirably 5 to 13% by weight.
By containing appropriate moisture, precipitation does not occur in the oil and fat composition, and a strong antioxidant power can be exhibited. Needless to say, this moisture is brought into the water phase.

Hereafter, the preparation method of the oil-fat composition which concerns on this invention is demonstrated.
In the present invention, a water phase is prepared by dissolving a water-soluble antioxidant and, if necessary, other water-soluble solids such as carbohydrates in water. Here, these components need to be substantially dissolved in the aqueous phase. Whether or not it is substantially dissolved is determined by placing 5 ml of the aqueous phase into a 20 ml centrifuge tube at 20 ° C. and centrifuging at 3000 G for 1 minute. Also by the said process, it judges that it has melt | dissolved substantially referring to the state which cannot confirm a deposit visually.
In addition, when precipitation has arisen in the water phase, even if it mixes with an oil phase after that and emulsifies, a particle diameter may not become a predetermined value. In this case, an oil or fat composition having a high antioxidant power cannot be obtained.

The oil phase is prepared by dissolving oil-soluble components in fats and oils. In the present invention, an oil-soluble emulsifier is used as necessary as the oil-soluble component.
Next, the oil phase and the aqueous phase are mixed and emulsified to obtain a water-in-oil type emulsified fat composition. In this case, a preferred oil and fat composition can be easily obtained by using a commonly used emulsifier for emulsification. Specifically, a high-pressure homogenizer, an ultrasonic emulsifier, or a two-liquid collision type emulsifying device called a wet jet mill can be used. By using a suitable emulsifying device, a predetermined oil and fat composition can be obtained. The general emulsification conditions when using a high-pressure homogenizer are 30 to 40 MPa and 10 to 30 passes.
The use of a general emulsifier can easily make the particle size finer because the water phase contains a large amount of water-soluble solids in a dissolved state.

In the present invention, it is preferable to emulsify so that the particle diameter is 300 nm or less at the stage of the emulsification operation. Even when the particle diameter is not within the predetermined range at the emulsification stage, the particle diameter can be further reduced by appropriate partial dehydration thereafter. The oil and fat composition finally obtained needs to have a water phase of 300 nm or less and be dispersed in the oil phase.

Next, it is preferable to adjust the water content of the obtained emulsion by partial dehydration. This is because by adjusting the water content by partial dehydration, a water-soluble solid having a low solubility can be used, and the particle size can be made finer, thereby suppressing the occurrence of precipitation.
The conditions for partial dehydration can be set as appropriate. If a small amount of sample is prepared, partial dehydration can be achieved by heating to about 60 ° C. and stirring. It is also possible to perform partial dehydration under reduced pressure. In this case, a simple device such as an aspirator can be used. Generation of precipitation can be suppressed by partial dehydration.

As for the amount of water after partial dehydration, it is desirable to dehydrate 12 to 76% of the water contained in the original fat composition, and this value is more preferably 33 to 50%. This value is sometimes simply called dehydration rate.
Generation | occurrence | production of the precipitation in an oil-fat composition can be suppressed by carrying out partial dehydration of the water | moisture content of a suitable ratio. When dehydration is performed excessively, the oil and fat composition according to the present invention may become cloudy, and its antioxidant power may also decrease.
In addition, a dehydration rate can be calculated | required with the following formula | equation.
Dehydration rate = 1-(water content of sample after dehydration) / (water content of sample before dehydration)

When precipitation occurs in the oil and fat composition according to the present invention, the antioxidant effect seems to be limited to the periphery of the precipitation. Therefore, when using the oil-and-fat composition once precipitated, unevenness may appear in the antioxidant effect. Therefore, in order to exhibit the antioxidant effect even in a stationary state, it is necessary that the oil and fat composition according to the present invention does not cause precipitation at the time of use. That is, due to partial dehydration, the expiration date of the oil and fat composition according to the present invention in a stationary state can be extended.
In addition, after adding the oil-fat composition which concerns on this invention to the target oil-fat, generation | occurrence | production of precipitation seems to be suppressed. This is considered to be caused by the aggregation of the dispersed aqueous phase particles, and the effect of extending the physical distance between the aqueous phase particles.

In addition, due to moderate partial dehydration, a water-soluble antioxidant or the like having a solubility or higher may exist in the aqueous phase in calculation. However, visually, no turbidity is observed, and it seems that water-soluble solid content higher than solubility is dissolved in the aqueous phase.
This situation was confirmed at the large synchrotron radiation facility “SPring-8” with the cooperation of Professor Satoshi Ueno, Faculty of Bioproduction, Hiroshima University. As a result, data indicating that a solid content exceeding the solubility was present without precipitation was obtained.

In the present invention, it is necessary to leave a certain amount of water in the oil / fat composition even in the case of partial dehydration. Therefore, it may be difficult to use this oil-and-fat composition as it is as oil for cooking such as frying oil.
That is, the oil and fat composition according to the present invention is particularly suitable for uses such as stabilization of fats and oils containing highly unsaturated fatty acids, such as PUFA oil.
Examples will be described below.

Study 1 Regarding the necessity of oil-soluble emulsifiers, samples were prepared according to “○ Preparation method 1 of oil and fat composition” with the formulation shown in Table 1-1.
The obtained sample was diluted as shown in Table 1-2, and then evaluated according to “◯ CDM oxidation stability evaluation method 1”. The results are shown in Table 1-3.
In this study, the particle size after the emulsification operation was not actually measured with an apparatus, but it was confirmed that there was no precipitation or the like by visual observation, and all the particle sizes were estimated to be 300 nm or less.

Table 1-1

-“Sanphenon 90S” manufactured by Taiyo Kagaku Co., Ltd. was used as the catechin.
-As the palm fractionation oil 1, "Palm Ace 10" manufactured by Fuji Oil Co., Ltd. was used. IV was 67.
As the emulsifier, “CRS-75” (polyglycerin condensed ricinoleic acid ester: PGPR) manufactured by Sakamoto Pharmaceutical Co., Ltd. was used.
-In all the formulations, no precipitation was confirmed in the aqueous phase at the time of preparation.

○ Preparation method 1 of oil and fat composition
1. According to the formulation, catechin was dissolved in water to obtain an aqueous phase.
2. An emulsifier was dissolved in the oil according to the formulation to obtain an oil phase.
3. The aqueous phase was added to the oil phase and mixed with a homomixer.
4). Further, the sample was emulsified with a high-pressure homogenizer (37 MPa, 20 passes) to obtain a sample.

Table 1-2 Formulation 2

-As the palm fractionation oil 2, "Univers 100" manufactured by Fuji Oil Co., Ltd. was used. IV was 57.
-As the palm oil, “refined palm oil” manufactured by Fuji Oil Co., Ltd. was used.

○ CDM oxidation stability evaluation method 1
1. Each sample was evaluated for oxidation stability with a CDM measuring device (Metrome CDM tester “Rancimat”) under the conditions of 120 ° C., air blowing rate 20.0 L / h, sample loading amount 3.0 g. It was.
2. The CDM value of each sample was divided by the CDM value of the oil used for each dilution, and a value of 2.7 or higher was regarded as acceptable.

Table 1-3 Results

Discussion By using an appropriate amount of an aqueous phase containing a predetermined amount of water-soluble solids, an emulsion without precipitation was obtained. When each emulsion was present in a predetermined amount of oil and fat, strong antioxidant power was exhibited.
In this study, there was no significant difference depending on the presence or absence of the emulsifier.

Study 2 Regarding types of oil-soluble emulsifiers, samples were prepared according to “○ Preparation method 2 of oil and fat composition” with the formulation shown in Table 2-1.
The obtained samples were evaluated according to “Oxidation stability evaluation method 1 using POV”. The results are shown in Table 2-2.
In this study, the particle size after the emulsification operation was not actually measured by the apparatus. However, it was confirmed that there was no precipitation or the like for the sample corresponding to the example. The particle diameter was estimated to be 300 nm or less.

Table 2-1 Composition

○ POV oxidation stability evaluation method 1
1. 3 g of each sample was diluted 10 times with oil containing 19.8% EPA and 45.4% DHA.
The diluted fat of 2.1 was put into a 50 ml glass bottle, covered, put into a 60 ° C. incubator, and stirred at 80 rpm.
Sampling was performed on the 3.5th day, and POV (peroxide value) was measured. The POV was measured according to the standard oil analysis test method.
Samples with a POV of 14 or less on the 4.5th day were considered acceptable.

Table 2-2 Results

In all the test sections, no precipitation occurred after the emulsification operation.

In the discussion and the present study, it was confirmed that the oil and fat composition according to the present invention has a function of suppressing an increase in POV to half or less even when compared with TBHQ. Further, when an oil-soluble emulsifier was used in combination, the effect was further improved.
In the present invention, as the oil-soluble emulsifier to be used, polyglycerin ester, sugar ester, and distilled monoglyceride are preferable, and polyglycerin ester is particularly preferable, and polyglycerin condensed ricinoleic acid ester is most preferable.
・ Use of emulsifier with high HLB had a weak POV rise inhibitory effect.

Examination 3 Examination of various water-soluble solids Samples were prepared according to “○ Preparation method 2 of oil and fat composition” with the composition shown in Table 3-1. The obtained samples were evaluated according to “◯ CDM oxidation stability evaluation method 2”. The results are shown in Table 3-2.

Table 3-1 formulation

For dextrin 1, “Sandeck 150” manufactured by Sanwa Starch Co., Ltd. was used.
-"Fructooligosaccharide" manufactured by Wako Pure Chemicals was used as the fructooligosaccharide.
-As the maltodextrin, "Paindex # 4" manufactured by Matsutani Chemical Co., Ltd. was used.
-"Lightes Ultra" manufactured by Danisco Co. was used as the polydextrin.
-Polyglycerin condensed ricinoleic acid ester “CRS-75” manufactured by Sakamoto Pharmaceutical Co., Ltd. was used as the emulsifier.
・ For Whey Protein, “WPI895” manufactured by Fontera Japan Co., Ltd. was used.
-“Particle size (nm) 1st day” is a value obtained by measuring the particle size on the 1st day after the emulsification step. Here, no precipitation was generated, but a measurement result having a double peak was described as W. Moreover, it was set as "no precipitation" about the sample which confirmed that there was no precipitation visually.
-In all the formulations, no precipitation was confirmed in the aqueous phase at the time of preparation.

○ CDM oxidation stability evaluation method 2
1． Each sample was diluted 4-fold with PUFA oil (containing 19.8% EPA and 45.4% DHA).
2. Using a CDM measuring device (Metrohm CDM tester “Rancimat”), 3.0 g of the diluted sample of 2.1 was added at 96 ° C., an air blowing amount of 20.0 L / h, a specimen charging amount of 3.0 g, (water The oxidation stability was evaluated under the condition of 70 ml). Also, the PUFA oil alone used for dilution was measured in the same manner as the “CDM value of control oil”.
The CDM value of each diluted sample obtained in 3.2 was divided by the CDM value of the PUFA oil used for dilution (CDM value of the control fat / oil), and 2.3 or more was regarded as acceptable.
Note that the sample in which precipitation occurred during the measurement was rejected at that time (the particle diameter is larger than 300 nm), and thus CDM measurement was not performed.
(When measuring the CDM value of 3.0 g of soybean oil under the above conditions 2, it was 20 hr).

Table 3-2 Results

Discussion When vitamin C was used as an antioxidant and the type of carbohydrate to be coexisted was changed, the antioxidant power was improved as compared with those not using water-soluble solids, although there were differences.
Among sugars, sugar alcohols including sorbitol and erythritol were particularly excellent. As food materials, sugar, dextrin, fructooligosaccharide and maltodextrin were excellent.
From the viewpoint of cost and versatility, it was judged that the use of sugar was preferable.
In addition, since it turned out that an amino acid itself has antioxidant power, it excluded from consideration as water-soluble solid content other than a water-soluble antioxidant.
As for amino acids as antioxidants, proline and glycine were particularly excellent.
For proteins, the effect of improving antioxidant power was small, but the effect of reducing the particle size was recognized. It was thought to contribute to the extension of the storage period.
From the above, it has been clarified that various components can be used for water-soluble solids that may be used as food.

As a comparison, when the synthetic antioxidant "TBHQ" that is not approved in Japan was added to the PUFA oil used in "○ CDM oxidation stability evaluation method 2", 200 ppm which is the upper limit of addition amount in other countries was evaluated, The CDM value was 11.6 hr. That is, the oil and fat composition according to the present invention exhibited an antioxidant power equivalent to or higher than that of a synthetic antioxidant while using conventionally known food materials and food additives.

Study 4 Effects of partial dehydration 1
Samples were prepared in accordance with “Oil composition preparation method 3” with the formulation shown in Table 4-1. The obtained samples were evaluated according to “◯ CDM oxidation stability evaluation method 2”. The results are shown in Table 4-2.
In the “dehydration step” in the recipe, the state before dehydration is indicated as “front”, and the state after dehydration is indicated as “after”. Here, what was prepared with the composition described in the formulation was “before” the dehydration process, and the composition after the dehydration process “after” was dehydrated from the sample immediately before the dehydration process “before” in the table, and the amount of water decreased The composition calculated backward from is described.
Samples with a dehydration process of “-” were not dehydrated.

Table 4-1 Composition

-In all of the examples, no precipitation was confirmed in the aqueous phase at the time of preparation.
・ “Dehydration rate” describes what percentage of water contained in the sample before dehydration was dehydrated.

○ Preparation method 3 of oil and fat composition
1. The raw materials classified into the aqueous phase by mixing were mixed and dissolved to obtain an aqueous phase.
2. An emulsifier was dissolved in the oil according to the formulation to obtain an oil phase.
3. The aqueous phase was added to the oil phase and mixed with a homomixer to obtain an emulsion.
4). Further, the mixture was emulsified with a high-pressure homogenizer (37 MPa, 20 passes).
5. The temperature was raised to 60 ° C. while stirring with a stirrer.
6). When 12 to 76% of the water in the oil and fat composition was partially dehydrated, stirring was stopped as appropriate and the temperature was returned to room temperature.
Note: Samples with a dehydration step of “-” in the recipe table were not subjected to steps 5 and 6.

Table 4-2 Results

Note: Some of the samples before dehydration omitted measurement of CDM.

Discussion In Example 4-9, precipitation occurred on the 9th day of preparation. On the other hand, in Example 4-10 in which it was partially dehydrated, no precipitation was observed even on the 9th day.
On the other hand, in Example 4-20 in which Example 4-19 was partially dehydrated, precipitation occurred at the stage of the ninth day, but in Comparative Example 4-1, which was further dehydrated, precipitation occurred at the stage of the first day. occured.
As described above, it was shown that the occurrence of precipitation over time can be suppressed by appropriate partial dehydration.
In Comparative Examples 4-2 to 4 and Examples 4-25 to 27, it was confirmed that precipitation occurred after the emulsification operation when the water-soluble solid content in the aqueous phase was too small.

Study 5 Effects of partial dehydration, etc.2
Samples were prepared in accordance with “Oil composition preparation method 3” with the formulation shown in Table 5-1. The obtained samples were evaluated according to “◯ CDM oxidation stability evaluation method 2”. The results are shown in Table 5-2.
The relationship between the dehydration process “before” and “after” was the same as in Study 4.

Table 5-1

Note: The particle size “-” was not measured by an apparatus, but it was confirmed that no precipitation occurred visually.
-In all the formulations, no precipitation was confirmed in the aqueous phase at the time of preparation.

Table 5-2

Oil and fat composition having an antioxidant effect even if the kind and amount of the antioxidant used and the amount of sugar which is a water-soluble solid content are changed, provided that the amount of the antioxidant and the water-soluble solid content is the predetermined amount. It became clear that
・ It was suggested that by carrying out appropriate partial dehydration, the particle size becomes smaller and the storage period can be extended.

Examination 6 Confirmation of effect Comparison of the antioxidant power of the oil and fat composition obtained in the present invention was confirmed.
Samples are shown in Table 6-1. The effect was measured by measuring POV. The details of the evaluation method were the same as those described in “Oxidation stability evaluation method 2 using POV”.
The results are shown in FIG.

Table 6-1 Sample details

-PUFA oil used fats and oils containing EPA 19.8% and DHA 45.4%.

○ POV oxidation stability evaluation method 2
1. The fats and oils prepared according to the formulation shown in Table 6-1 were placed in a 50 ml glass bottle, capped, placed in a 60 ° C. incubator and stirred at 80 rpm.
2. Sampling was carried out in a timely manner, and POV (peroxide value) was measured. The POV was measured according to the standard oil analysis test method.

Discussion As shown in FIG. 1, when the oil and fat composition according to the present invention was used, the oxidation stability of PUFA oil was higher than that of soybean oil. Its antioxidant power exceeded that of the synthetic antioxidant TBHQ.
PUFA oils have been used in many cases due to their low oxidative stability, but by using the oil and fat composition according to the present invention, PUFA oil is similar to common oils and fats such as soybean oil. It was inferred that it could be used.

In addition, in this examination, sensory evaluation by the method of confirming odor was also performed. Here again, the PUFA oil using the oil / fat composition according to the present invention was able to be used for general purposes because generation of off-flavors such as fishy odor was strongly suppressed. Conventionally, in fish oil and the like, an off-flavor may be generated before the increase in the value of the peroxide value becomes apparent, and the occurrence of off-flavor has been assumed to have an element other than oxidation. However, in the present invention, by using an oil and fat composition having an overwhelmingly strong anti-oxidant power, it was possible to suppress the generation of off-flavors, so the occurrence of off-flavors such as fish oil is mainly due to oxidation. It has been suggested.

It is a figure which shows the antioxidant effect of the oil-fat composition which concerns on this invention.

Claims

An oil and fat composition containing 1.9 to 18% by weight of water that satisfies the following requirements.
1. 3 to 65% by weight of a water-soluble antioxidant is contained in the aqueous phase.
2. If necessary, the aqueous phase contains saccharides and contains a total of 18 to 75% by weight of water-soluble solids.
3. 4.3 to 38% by weight of the aqueous phase is dispersed in the oil phase with a particle size of 300 nm or less.
The fat and oil composition according to claim 1, wherein the aqueous phase contains one or more saccharides selected from sugar alcohol, glucose, sucrose, and dextrin.
The fat or oil according to claim 1, wherein the oil phase contains 0.7 to 6.8 times the weight of water of one or more oil-soluble emulsifiers selected from polyglycerin condensed ricinolate, sugar ester, and glycerin fatty acid ester. Composition.
The fat or oil according to claim 2, wherein the oil phase contains 0.7 to 6.8 times the weight of water of one or more oil-soluble emulsifiers selected from polyglycerin condensed ricinolate, sugar ester, and glycerin fatty acid ester. Composition.
The oil and fat composition according to claim 2, wherein the water-soluble antioxidant is one or more selected from vitamin C, amino acids, and catechins.
The fat and oil composition according to claim 3, wherein the water-soluble antioxidant is one or more selected from vitamin C, amino acid, and catechin.
The oil and fat composition according to claim 4, wherein the water-soluble antioxidant is one or more selected from vitamin C, amino acids, and catechins.
The fat composition according to claim 6, wherein the amino acid is one or more selected from glycine, proline, and serine.
The fat composition according to claim 7, wherein the amino acid is one or more selected from glycine, proline, and serine.
The manufacturing method of the oil-fat composition by the following processes.
1. A step of preparing an aqueous phase containing 3 to 65% by weight of a water-soluble antioxidant in the aqueous phase and containing a saccharide if necessary, so that the total amount of water-soluble solids is 18 to 75% by weight.
2. The water phase is added to the oil phase so that the water phase is 4.3 to 38% by weight, and the water content in the oil and fat composition is 1.9 to 18% by weight, so that the particle diameter is 300 nm or less. And a step of preparing a water-in-oil type oil and fat composition.
The manufacturing method of Claim 10 whose saccharide | sugar is 1 or more chosen from sugar alcohol, glucose, sucrose, and dextrin.
The oil phase contains at least one oil-soluble emulsifier selected from polyglycerin condensed ricinolate, sugar ester, and glycerin fatty acid ester in an amount of 0.7 to 6.8 times the weight of water in the oil or fat composition. 11. The production method according to 11.
The production method according to claim 12, wherein the water-soluble antioxidant is one or more selected from vitamin C, amino acid, and catechin.
The production method according to claim 13, wherein the amino acid is one or more selected from glycine, proline, and serine.
14. The production method according to claim 13, wherein 12 to 76% of the moisture contained in the oil and fat composition is partially dehydrated so that the moisture in the oil and fat composition is 1.9 to 18% by weight.
The water-soluble antioxidant is one or more selected from vitamin C, glycine, proline, serine, and catechin, and 12 to 76% of the water contained in the oil / fat composition is partially dehydrated. The production method according to claim 11, wherein the water content is 1.9 to 18% by weight.
15. The production method according to claim 14, wherein 12 to 76% of the moisture contained in the oil and fat composition is partially dehydrated to make the moisture in the oil and fat composition 1.9 to 18% by weight.
The oil phase contains at least one oil-soluble emulsifier selected from polyglycerin condensed ricinolate, sugar ester, and glycerin fatty acid ester in an amount of 0.7 to 6.8 times the weight of water in the oil and fat composition. The antioxidant is one or more selected from vitamin C, glycine, proline, serine, and catechin, and 12 to 76% of the moisture contained in the oil and fat composition is partially dehydrated, and the moisture in the oil and fat composition is reduced. The production method according to claim 10, wherein the content is 1.9 to 18% by weight.
A method for producing an unsaturated fatty acid-containing fat or oil, comprising adding the fat or oil composition according to claim 7 to an unsaturated fatty acid-containing fat or oil so as to be 0.1 to 40% by weight.
A method for preventing oxidation of an unsaturated fatty acid-containing oil or fat, comprising adding the oil or fat composition according to claim 7 to an unsaturated fatty acid-containing oil or fat so as to be 0.1 to 40 wt%.