The present invention relates to an antioxidant oil and fat composition with high antioxidative activity comprising food or food additives, and to the production method thereof.
The addition of a water-soluble antioxidant to oil and fat has been known to achieve an oxidation-preventing effect (Patent Literature (PTL) 1).
PTL 2 discloses oil and fat comprising water-soluble tea polyphenol and an emulsifier, and having oxidative stability.
PTL 3 discloses that the antioxidative activity of chlorogenic acids with a specific composition is improved with a further addition of a sugar.
PTL 4 discloses a tea extract-containing oily composition for deodorization and anti-oxidization comprising a solid phase containing a tea extract and an oil phase containing an oil component and an emulsifier with an HLB of 10 or less, the solid phase being dispersed in the oil phase, wherein the tea extract-containing solid phase comprises fine particles having an average particle size of 5 μm or less, and wherein the content of water or alcoholic aqueous solution in the solid phase is 30 wt % or less.
PTL 5 discloses an oil-soluble antioxidant comprising a water-soluble antioxidant component derived from a natural product and having an average particle size of 40 to 120 nm, the oil-soluble antioxidant being transparently dispersible in oil and fat.
PTL 6 discloses a lipophilic antioxidant obtained by emulsifying gallic acid, a water-soluble antioxidant, and an oil-soluble antioxidant into a water-in-oil type emulsion with a lipophilic emulsifying agent.
PTL 7 discloses an oil and fat composition comprising (A) 0.0001 to 1 part by weight of ascorbic acid and/or a salt thereof and (B) 0.0001 to 1 part by weight of at least one member selected from citric acid, citric acid salts, malic acid, and malic acid salts, per 100 parts by weight of oil and fat.
TBHQ (tertiary butylhydroquinone) has been reported to serve as a strong synthetic antioxidant (Non-patent Literature (NPL) 1), and can be used as an index in screening for a novel antioxidant (NPL 2).
An object of the present invention is to provide, using a simple method, an antioxidant oil and fat composition with unprecedentedly strong oxidative stability. This antioxidant oil and fat composition desirably maintains its effect for a long period of time.
The use of the technique disclosed in PTL 1 or PTL 2 makes it possible to obtain oil and fat with oxidative stability that has been improved to some extent.
However, PTL 1 basically discloses oil and fat for frying, and a certain amount or more of water is not assumed to be contained in the oil and fat. In fact, PTL 1 nowhere suggests an effect on polyunsaturated fatty acid-containing oil and fat, which are far more susceptible to oxidative deterioration than oil and fat for frying.
Similar to PTL 1, PTL 2 also discloses oil and fat that are preferably used for cooking with heat, e.g., for frying, and a certain amount or more of water is not assumed to be contained in the oil and fat. Further, PTL 2 nowhere suggests an effect on polyunsaturated fatty acid-containing oil and fat.
In terms of PTL 3, since chlorogenic acids with a specific composition must be used, the versatility was low. Further, the antioxidant of PTL 3 is basically water-soluble; therefore, the use thereof as an agent for preventing oxidation of oil and fat is difficult. PTL 3 nowhere suggests achieving extremely strong antioxidative activity in oils and fats, which is an object of the present invention.
In PTL 4, dehydration is substantially performed to obtain a tea extract as a solid, which is dispersed in oil. PTL 4 nowhere suggests an oxidation-preventing effect that is strong enough to prevent oxidation of PUFA oils.
Examples in PTL 5 show many restrictions such that the antioxidant is substantially limited to catechins, and that it is necessary to use a water-soluble emulsifier. Moreover, the antioxidative activity achieved is less than 1.5 times that of the control oil (corn oil); thus, it could hardly be believed possible to impart oxidative stability to polyunsaturated fatty acid-containing oil and fat, which have much lower oxidative stability than that of corn oil.
In PTL 6, the use of gallic acid and an oil-soluble antioxidant is essential, which makes the preparation complicated. Further, the evaluation performed in PTL 6 is only with respect to lard. Thus, the effect on polyunsaturated fatty acid-containing oil and fat, which have much lower oxidative stability than that of lard, cannot be expected.
Some of the Examples in PTL 6 use glucose. According to PTL 6, however, the use of glucose is only for expectation of obtaining the effect of a sugar-amino reaction product; PTL 6 nowhere suggests that the presence of a sugar itself improves the effect of water-soluble antioxidant.
In PTL 7, it is essential to use at least one of citric acid, citrates, malic acid, or malates; and this may adversely affect the flavor, depending on the amount used. Although the specification discloses using a sugar alcohol or liquid sugar as a solvent for emulsification to obtain a water-in-oil product, the sugar alcohol or liquid sugar is nowhere used in the Examples, and the effects thereof are nowhere disclosed.
Although TBHQ is known to serve as a strong antioxidant, the use thereof for food is not currently approved in Japan. It is presumed that a substance having antioxidative activity greater than that of TBHQ is actually required to further improve the oxidative stability of oil and fat that contain a large amount of polyunsaturated fatty acids. As a matter of course, such a substance must be able to be used as food.
In view of the related art, although some antioxidative activity was declared, only limited antioxidative activity was actually demonstrated, and no substance existed that showed antioxidative activity high enough to impart oxidative stability to oils with low stability, such as polyunsaturated fatty acid-containing oils and fats. Thus, it appeared impossible to further improve the antioxidative activity in this field.
Nevertheless, the present inventors further conducted extensive research to consequently find that an antioxidant oil and fat composition shows an extremely strong oxidation stabilizing effect, the antioxidant oil and fat composition comprising an aqueous phase containing a water-soluble antioxidant and a carbohydrate, and having a certain degree or more of water-soluble solids content, the aqueous phase being dispersed in an oil phase, wherein the antioxidant oil and fat composition contains a certain amount of water. The present invention has thus been accomplished.
More specifically, the present invention relates to the following:
(1) An antioxidant oil and fat composition with a water content of 0.5 to 18 wt % comprising
an aqueous phase containing a water-soluble antioxidant in an amount of 2.5 to 65 wt %, and further containing a carbohydrate in an amount such that the aqueous phase has a total water-soluble solids content of 18 to 79 wt %,
wherein 1 to 38 wt % of the aqueous phase is dispersed in an oil phase.
(2) The antioxidant oil and fat composition according to Item (1), wherein the oil phase contains at least one oil-soluble emulsifier selected from polyglycerol condensed ricinoleates, sugar esters, glycerol fatty acid esters, or lecithins, in an amount that is 0.7 to 9 times the weight amount of the water.
(3) The antioxidant oil and fat composition according to Item (1), wherein the water-soluble antioxidant is at least one member selected from vitamin C, an amino acid, or catechin.
(4) The antioxidant oil and fat composition according to Item (2), wherein the water-soluble antioxidant is at least one member selected from vitamin C, an amino acid, or catechin.
(5) The antioxidant oil and fat composition according to Item (3), wherein the amino acid is at least one member selected from glycine, glutamic acid, alanine, proline, lysine, tryptophan, methionine, valine, serine, histidine, isoleucine, leucine, phenylalanine, arginine, threonine, cysteine, aspartic acid, glutamine, or asparagine.
(6) The antioxidant oil and fat composition according to Item (4), wherein the amino acid is at least one member selected from glycine, glutamic acid, alanine, proline, lysine, tryptophan, methionine, valine, serine, histidine, isoleucine, leucine, phenylalanine, arginine, threonine, cysteine, aspartic acid, glutamine, or asparagine.
(7) The antioxidant oil and fat composition according to Item (6), wherein the carbohydrate is at least one member selected from sugar alcohols, glucose, sucrose, dextrins, maltose, or oligosaccharides.
(8) The antioxidant oil and fat composition according to any one of Items (1) to (5), wherein the carbohydrate is at least one member selected from sugar alcohols, glucose, sucrose, dextrins, maltose, or oligosaccharides.
(9) A method for producing an antioxidant oil and fat composition, the method comprising the following steps of:
1: preparing an aqueous phase containing a water-soluble antioxidant in an amount of 2.5 to 65 wt %, and further containing a carbohydrate in an amount such that the aqueous phase has a total water-soluble solids content of 18 to 79 wt %; and
2: dispersing the aqueous phase in an oil phase such that the percentage of the aqueous phase becomes 1 to 38 wt % to obtain an antioxidant oil and fat composition with a water content of 0.5 to 18 wt %.
(10) The production method according to Item (9), the method comprising the step of adding, to the oil phase, at least one oil-soluble emulsifier selected from polyglycerol condensed ricinoleates, sugar esters, glycerol fatty acid esters, or lecithins, in an amount that is 0.7 to 9 times the weight amount of the water contained in the antioxidant oil and fat composition.
(11) The production method according to Item (9),
wherein the water-soluble antioxidant is at least one member selected from vitamin C, an amino acid, or catechin.
(12) The production method according to Item (10), wherein the water-soluble antioxidant is at least one member selected from vitamin C, an amino acid, or catechin.
(13) The production method according to Item (11), wherein the amino acid is at least one member selected from glycine, glutamic acid, alanine, proline, lysine, tryptophan, methionine, valine, serine, histidine, isoleucine, leucine, phenylalanine, arginine, threonine, cysteine, aspartic acid, glutamine, or asparagine.
(14) The production method according to Item (12), wherein the amino acid is at least one member selected from glycine, glutamic acid, alanine, proline, lysine, tryptophan, methionine, valine, serine, histidine, isoleucine, leucine, phenylalanine, arginine, threonine, cysteine, aspartic acid, glutamine, or asparagine.
(15) The production method according to Item (9), wherein the carbohydrate is at least one member selected from sugar alcohols, glucose, sucrose, dextrins, maltose, or oligosaccharides.
(16) The production method according to Item (10), wherein the carbohydrate is at least one member selected from sugar alcohols, glucose, sucrose, dextrins, maltose, or oligosaccharides.
(17) The production method according to Item (11), wherein the carbohydrate is at least one member selected from sugar alcohols, glucose, sucrose, dextrins, maltose, or oligosaccharides.
(18) The production method according to Item (12), wherein the carbohydrate is at least one member selected from sugar alcohols, glucose, sucrose, dextrins, maltose, or oligosaccharides.
(19) The production method according to Item (13), wherein the carbohydrate is at least one member selected from sugar alcohols, glucose, sucrose, dextrins, maltose, or oligosaccharides.
(20) The production method according to Item (14), wherein the carbohydrate is at least one member selected from sugar alcohols, glucose, sucrose, dextrins, maltose, or oligosaccharides.
(21) A method for producing an antioxidant oil and fat composition, the method comprising the step of dehydrating 12 to 76 wt % of water from the antioxidant oil and fat composition obtained by the production method of any one of Items (9) to (20) to obtain an antioxidant oil and fat composition with a water content of 0.5 to 18 wt %.
(22) An unsaturated fatty acid-containing oil and fat composition comprising 0.1 to 100 wt % of the antioxidant oil and fat composition according to any one of Items (1) to (7).
(23) An unsaturated fatty acid-containing oil and fat composition comprising 0.1 to 100 wt % of the antioxidant oil and fat composition according to Item (8).
(24) The unsaturated fatty acid-containing oil and fat composition according to Item (22), comprising DHA and EPA in a total amount of 0.1 to 60 wt %.
(25) The unsaturated fatty acid-containing oil and fat composition according to Item (23), comprising DHA and EPA in a total amount of 0.1 to 60 wt %.
In other words, the invention includes the following.
(31) An antioxidant oil and fat composition with a water content of 0.5 to 18 wt % comprising
an aqueous phase containing a water-soluble antioxidant in an amount of 2.5 to 65 wt %, and further containing a carbohydrate in an amount such that the aqueous phase has a total water-soluble solids content of 18 to 79 wt %,
wherein 1 to 38 wt % of the aqueous phase is dispersed in an oil phase.
(32) The antioxidant oil and fat composition according to Item (31), wherein the oil phase contains at least one oil-soluble emulsifier selected from polyglycerol condensed ricinoleates, sugar esters, glycerol fatty acid esters, or lecithins, in an amount that is 0.7 to 6.8 times the weight amount of the water.
(33) The antioxidant oil and fat composition according to Item (31) or (32), wherein the water-soluble antioxidant is at least one member selected from vitamin C, an amino acid, or catechin.
(34) The antioxidant oil and fat composition according to Item (33), wherein the amino acid is at least one member selected from glycine, alanine, valine, threonine, serine, proline, or phenylalanine.
(35) The antioxidant oil and fat composition according to any one of Items (31) to (34), wherein the carbohydrate is at least one member selected from sugar alcohols, glucose, sucrose, dextrins, maltose, or oligosaccharides.
(36) A method for producing an antioxidant oil and fat composition, the method comprising the following steps of:
1: preparing an aqueous phase containing a water-soluble antioxidant in an amount of 2.5 to 65 wt %, and further containing a carbohydrate in an amount such that the aqueous phase has a total water-soluble solids content of 18 to 79 wt %; and
2: dispersing the aqueous phase in an oil phase such that the percentage of the aqueous phase becomes 1 to 38 wt % to obtain an antioxidant oil and fat composition with a water content of 0.5 to 18 wt %.
(37) The production method according to Item (36), the method comprising the step of adding, to the oil phase, at least one oil-soluble emulsifier selected from polyglycerol condensed ricinoleates, sugar esters, glycerol fatty acid esters, or lecithins, in an amount that is 0.7 to 6.8 times the weight amount of the water contained in the antioxidant oil and fat composition.
(38) The production method according to Item (36) or (37), wherein the water-soluble antioxidant is at least one member selected from vitamin C, an amino acid, or catechin.
(39) The production method according to Item (38), wherein the amino acid is at least one member selected from glycine, alanine, valine, threonine, serine, proline, or phenylalanine.
(40) The production method according to any one of Items (36) to (39), wherein the carbohydrate is at least one member selected from sugar alcohols, glucose, sucrose, dextrins, maltose, or oligosaccharides.
(41) An unsaturated fatty acid-containing oil and fat composition comprising 0.1 to 100 wt % of the antioxidant oil and fat composition according to any one of Items (31) to (35).
(42) The unsaturated fatty acid-containing oil and fat composition according to Item (41), comprising DHA and EPA in a total amount of 0.1 to 40 wt %.
(43) A method for producing an unsaturated fatty acid-containing oil and fat composition, the method comprising adding the oil and fat composition according to any one of Items (31) to (35) to unsaturated fatty acid-containing oil and fat to obtain an unsaturated fatty acid-containing oil and fat composition comprising the oil and fat composition in an amount of 0.1 to 99 wt %.
(44) A method for preventing oxidation of unsaturated fatty acid-containing oil and fat, the method comprising adding the oil and fat composition according to any one of Items (31) to (35) to unsaturated fatty acid-containing oil and fat to obtain an unsaturated fatty acid-containing oil and fat composition comprising the oil and fat composition in an amount of 0.1 to 99 wt %.
The invention also includes the following.
(51) An oil and fat composition with a water content of 1.9 to 18 wt % satisfying the following requirements:
1. 3 to 65 wt % of a water-soluble antioxidant is contained in an aqueous phase;
2. the aqueous phase optionally contains a carbohydrate and has a total water-soluble solids content of 18 to 75 wt %; and
3. the aqueous phase in an amount of 4.3 to 38 wt % with a particle size of 300 nm or less is dispersed in an oil phase.
(52) The oil and fat composition according to Item (51), wherein the aqueous phase contains at least one carbohydrate selected from sugar alcohols, glucose, sucrose, or dextrins.
(53) The oil and fat composition according to Item (51), wherein the oil phase contains at least one oil-soluble emulsifier selected from polyglycerol condensed ricinoleates, sugar esters, or glycerol fatty acid esters, in an amount that is 0.7 to 6.8 times the weight amount of the water.
(54) The oil and fat composition according to Item (52), wherein the oil phase contains at least one oil-soluble emulsifier selected from polyglycerol condensed ricinoleates, sugar esters, or glycerol fatty acid esters, in an amount that is 0.7 to 6.8 times the weight amount of the water.
(55) The oil and fat composition according to Item (52), wherein the water-soluble antioxidant is at least one member selected from vitamin C, an amino acid, or catechin.
(56) The oil and fat composition according to Item (53), wherein the water-soluble antioxidant is at least one member selected from vitamin C, an amino acid, or catechin.
(57) The oil and fat composition according to Item (54), wherein the water-soluble antioxidant is at least one member selected from vitamin C, an amino acid, or catechin.
(58) The oil and fat composition according to Item (56), wherein the amino acid is at least one member selected from glycine, proline, or serine.
(59) The oil and fat composition according to Item (57), wherein the amino acid is at least one member selected from glycine, proline, or serine.
(60) A method for producing an oil and fat composition, comprising the following steps:
1. preparing an aqueous phase containing a water-soluble antioxidant in an amount of 3 to 65 wt %, optionally containing a carbohydrate, and having a total water-soluble solids content of 18 to 75 wt %; and
2. adding the aqueous phase to an oil phase to obtain a water-in-oil oil and fat composition comprising the aqueous phase in an amount of 4.3 to 38 wt % with a particle size of 300 nm or less, and having a water content of 1.9 to 18 wt %.
(61) The production method according to Item (60), wherein the carbohydrate is at least one member selected from sugar alcohols, glucose, sucrose, or dextrins.
(62) The production method according to Item (61), wherein the oil phase contains at least one oil-soluble emulsifier selected from polyglycerol condensed ricinoleates, sugar esters, or glycerol fatty acid esters, in an amount that is 0.7 to 6.8 times the weight amount of the water in the oil and fat composition.
(63) The production method according to Item (62), wherein the water-soluble antioxidant is at least one member selected from vitamin C, an amino acid, or catechin.
(64) The production method according to Item (63), wherein the amino acid is at least one member selected from glycine, proline, or serine.
(65) The production method according to Item (63), wherein the oil and fat composition is subjected to partial dehydration to dehydrate 12 to 76% of water contained in the oil and fat composition so that the oil and fat composition has a water content of 1.9 to 18 wt %.
(66) The production method according to Item (61), wherein the water-soluble antioxidant is at least one member selected from vitamin C, glycine, proline, serine, or catechin, and wherein the oil and fat composition is subjected to partial dehydration to dehydrate 12 to 76% of water contained in the oil and fat composition so that the oil and fat composition has a water content of 1.9 to 18 wt %.
(67) The production method according to Item (64), wherein the oil and fat composition is subjected to partial dehydration to dehydrate 12 to 76% of water contained in the oil and fat composition so that the oil and fat composition has a water content of 1.9 to 18 wt %.
(68) The production method according to Item (60), wherein the oil phase contains at least one oil-soluble emulsifier selected from polyglycerol condensed ricinoleates, sugar esters, or glycerol fatty acid esters, in an amount that is 0.7 to 6.8 times the weight amount of the water in the oil and fat composition, wherein the water-soluble antioxidant is at least one member selected from vitamin C, glycine, proline, serine, or catechin, and wherein the oil and fat composition is subjected to partial dehydration to dehydrate 12 to 76% of water contained in the oil and fat composition so that the oil and fat composition has a water content of 1.9 to 18 wt %.
(69) A method for producing unsaturated fatty acid-containing oil and fat, the method comprising adding the oil and fat composition according to Item (57) to unsaturated fatty acid-containing oil and fat to obtain unsaturated fatty acid-containing oil and fat comprising the oil and fat composition in an amount of 0.1 to 40 wt %.
(70) A method for preventing oxidation of unsaturated fatty acid-containing oil and fat, the method comprising adding the oil and fat composition according to Item (57) to unsaturated fatty acid-containing oil and fat to obtain unsaturated fatty acid-containing oil and fat comprising the oil and fat composition in an amount of 0.1 to 40 wt %.
The present invention provides an antioxidant oil and fat composition with extremely high antioxidative activity using general-purpose edible starting materials. The invention also provides a polyunsaturated fatty acid-containing oil and fat etc. with high oxidative stability using the antioxidant oil and fat composition.
The antioxidant oil and fat composition according to the present invention has high antioxidative activity. The antioxidant oil and fat composition according to the present invention can be used by only mixing with a target to which antioxidative activity is intended to be imparted. The antioxidant oil and fat composition according to the present invention is an oil and fat composition in the form of water-in-oil emulsion. Thus, for use with oils and fats, the antioxidant oil and fat composition according to the present invention can be easily dispersed in the oils and fats.
The target oils and fats to be used may be any oils and fats, as long as they contain unsaturated fatty acids. The antioxidant oil and fat composition according to the present invention can thus also be used to improve the stability of commonly used oils and fats, such as soybean oil and rapeseed oil. Additionally, when the antioxidant oil and fat composition according to the present invention is used with oil and fat containing fatty acids with multiple unsaturated bonds, i.e., PUFA, the antioxidant oil and fat composition according to the present invention demonstrates remarkable performance, leading to preferable results. In the present invention, docosahexaenoic acid may be sometimes abbreviated as “DHA,” and eicosapentaenoic acid may be sometimes abbreviated as “EPA.” Further, in the present invention, oil and fat containing large amounts of DHA and EPA may be sometimes simply referred to as “PUFA oils.”
The effect in terms of the oxidative stability of the antioxidant oil and fat composition according to the present invention is evaluated by adding a predetermined amount of the antioxidant oil and fat composition to predetermined oil and fat, storing the resulting mixture at a constant temperature, and measuring its peroxide value (POV). Suppression of the increase in the POV for a longer period of time represents higher oxidative stability. A specific measurement method is described in the Examples; the test is an accelerated test, which is performed at a temperature higher than the temperature in expected use, and so stirring is required.
The POV is denoted in “meq/kg.” In the present invention, when the term “POV” is simply stated, the unit thereof is meq/kg.
A CDM test, which involves a simple measurement method, can also provide a certain evaluation index. The term “CDM” (a Conductometric Determination Method) as used herein refers to a value (time) that represents the oxidative stability of oil and fat, and the value can serve as an index for evaluation of oxidative stability. When a higher CDM value (time) is measured, the oxidative stability is more excellent.
The CDM test can be performed using a dedicated test device “Rancimat.” In terms of this method as well, a specific measurement method is described in the Examples. This test is an accelerated test, which is performed at a temperature higher than the temperature in expected use, and involves a measurement method comprising bubbling air; thus, the results are presented under stirring conditions. The antioxidant oil and fat composition according to the present invention, which contains a certain degree of water, is measured at 96° C., rather than 120° C., which is a commonly applied measurement temperature.
The numerical values obtained as a result of the CDM test are denoted as time (hr). In the present invention, the unit of a simple expression such as “a CDM value” is also time (hr).
The water-soluble antioxidant as used herein is an antioxidant that is soluble in water. Specific examples include vitamin C (in this specification, sometimes abbreviated as “VC”), catechin, tea extracts, amino acids, and Myrica rubra extracts; with vitamin C, tea extracts, and amino acids being preferable; and vitamin C and amino acids being more preferable.
Of amino acids, it is preferable to use at least one amino acid selected from glycine, glutamic acid, alanine, proline, lysine, tryptophan, methionine, valine, serine, histidine, isoleucine, leucine, phenylalanine, arginine, threonine, cysteine, aspartic acid, glutamine, or asparagine. It is more preferable to use at least one amino acid selected from glycine, glutamic acid, alanine, proline, lysine, tryptophan, methionine, valine, serine, histidine, isoleucine, leucine, or phenylalanine; and it is even more preferable to use at least one amino acid selected from glycine, glutamic acid, alanine, proline, lysine, tryptophan, or methionine.
It is also possible to add the water-soluble antioxidant as a salt. For example, sodium glutamate may be added instead of glutamic acid, and sodium aspartate may be added instead of aspartic acid. In a similar manner, sodium ascorbate may be used instead of vitamin C.
In the present invention, even when the term “water-soluble antioxidant” or “amino acid” is simply used, the scope of these terms also encompass salts thereof.
In the present invention, these water-soluble antioxidants may be used alone or in combination by suitably selecting from the above. With the use of an appropriate water-soluble antioxidant, an antioxidant oil and fat composition that has strong antioxidative activity can be obtained.
In tea extracts, catechin is said to be the main cause of this activity. Thus, even when a tea extract is used, the tea extract may be referred to as “catechin.” Catechin and tea extracts may also be collectively referred to as “polyphenols.”
Needless to say, the term “water-soluble antioxidant” as used herein is not limited to encompass those that have been known as water-soluble antioxidants, but also encompasses water-soluble components that were newly found to have antioxidative activity. For amino acids, in particular, those that were newly found to have antioxidative activity by this study are also encompassed.
The present invention is characterized by achieving antioxidative activity with the use of vitamin C, which is approved for use in many countries and whose safety have been confirmed through long eating experience, the antioxidative activity being greater than that achieved with the use of synthetic antioxidants.
In the present invention, the amount of the water-soluble antioxidant contained in the aqueous phase is 2.5 to 65 wt %, preferably 10 to 63 wt %, and more preferably 13 to 60 wt %. The use of an appropriate water-soluble antioxidant in an appropriate amount makes it possible to obtain an antioxidant oil and fat composition having strong antioxidative activity.
The aqueous phase in the present invention is a mixture of water and starting materials that are water-soluble from among the starting materials of the antioxidant oil and fat composition.
The amount of the aqueous phase in the antioxidant oil and fat composition according to the present invention must be within a range of 1 to 38 wt %, preferably 3 to 34 wt %, and more preferably 5 to 30 wt %. With an appropriate amount of the aqueous phase, the antioxidant oil and fat composition according to the present invention exerts strong antioxidative activity.
In the present invention, the aqueous phase with a higher water-soluble solids content achieves more preferred antioxidative activity. In the present invention, the water-soluble solids content in the aqueous phase is 18 to 79 wt %, preferably 30 to 79 wt %, and more preferably 35 to 79 wt %. The water-soluble solids content here includes the amount of the water-soluble antioxidant.
Various materials that can be used as food or food additives may be used as water-soluble solids, in addition to the water-soluble antioxidants. In particular, carbohydrates, which are inexpensive and have an effect of further increasing antioxidative activity, are preferable. The carbohydrate is preferably at least one member selected from sugar alcohols, oligosaccharides, various monosaccharides, such as glucose, various disaccharides, such as sucrose and maltose, or dextrins; more preferably a sugar alcohol, glucose, sucrose, dextrins, or maltose; and even more preferably sucrose or a sugar alcohol.
Of sugar alcohols, preferred are glycerol, maltitol, sorbitol, erythritol, reduced palatinose, lactitol, xylitol, and mannitol, more preferred are glycerol, maltitol, sorbitol, and erythritol, and even more preferred are sorbitol and erythritol.
Adjusting the water-soluble solids content in the aqueous phase to an appropriate value by using an appropriate carbohydrate or, as necessary, two or more appropriate carbohydrates makes it possible to prevent the occurrence of precipitation, and obtain an antioxidant oil and fat composition having strong antioxidative activity.
The oil phase as used in the present invention is obtained by dissolving in oil one or more oil-soluble components from among the starting materials of the antioxidant oil and fat composition according to the present invention. Here, examples of usable oils include soybean oil, rapeseed oil, fractionated palm oil, polyunsaturated fatty acid-containing oils and fats, and other various edible oils and fats. From the viewpoint of the production process, however, it is more advantageous to use soybean oil or the like as the oil and fat used at this stage, and use the prepared antioxidant oil and fat composition by mixing with polyunsaturated fatty acid-containing oil and fat. If the starting materials include no oil-soluble components other than oil, then the oil itself is referred to as an oil phase.
An oil-soluble emulsifier is optionally used as an oil-soluble component as a starting material in the present invention. In the present invention, emulsifiers having an HLB of 7 or less and lecithins are defined as oil-soluble emulsifiers. The oil-soluble emulsifier is preferably at least one member selected from polyglycerol esters, sugar esters, sorbitan esters, monoglycerol fatty acid esters, or lecithins. The oil-soluble emulsifier is more preferably a polyglycerol ester, a sugar ester, a distilled monoglyceride, or a lecithin, particularly preferably a polyglycerol ester, and most preferably a polyglycerol condensed ricinoleic acid ester (polyglycerol ester of polyricinoleic acid). The term “polyglycerol condensed ricinoleate (polyglycerol polyricinoleate)” may be abbreviated as “PGPR.”
The amount of the oil-soluble emulsifier contained in the antioxidant oil and fat composition is preferably 0.7 to 9 times, more preferably 0.7 to 6.8 times, and even more preferably 0.7 to 5 times the weight amount of the water. The use of an appropriate oil-soluble emulsifier in an appropriate amount as required can provide an antioxidant oil and fat composition having strong antioxidative activity.
In the antioxidant oil and fat composition according to the present invention, the aqueous phase with a particle size of 300 nm or less is dispersed in the oil phase. The particle size is more preferably 160 nm or less, and even more preferably 130 nm or less.
Adjusting the particle size to an appropriate value makes it possible to stably achieve strong antioxidative activity. The occurrence of precipitation indicates that the particle size is greater than 300 nm. This means that precipitation should not be visually observed. When no precipitation occurs, it is confirmed that the particle size is 300 nm or less. Therefore, in the Examples in which precipitation does not occur, the particle size is shown as 300 nm or less.
In the present invention, the particle size is measured using the following device under the following conditions.
Device name: Zetasizer Nano S; Manufacturer: Malvern
The measurement is performed by diluting 10 μl of an oil and fat composition to be measured in 2 ml of hexane.
(The measurement results of the sample on the first day after preparation are used for evaluation.)
Temperature: 20.0° C.
Equilibrium time: 240 seconds
Cell: Glass cell
Measurement angle: 173°
Positioning method: Optimum position selected
Selection of automatic attenuation: Yes
The antioxidant oil and fat composition according to the present invention has a water content of 0.5 to 18 wt %. The water content is more preferably 1 to 15 wt %, and even more preferably 1.5 to 13 wt %.
An appropriate amount of water prevents precipitation from occurring in the antioxidant oil and fat composition, and enables an achievement of high antioxidative activity. Needless to say, the water refers to water that is incorporated from the aqueous phase.
In the present invention, the antioxidant oil and fat composition described above is mixed with unsaturated fatty acid-containing oil and fat to give an unsaturated fatty acid-containing oil and fat composition having antioxidative activity.
The amount of antioxidant oil and fat composition contained in the unsaturated fatty acid-containing oil and fat composition is preferably 0.1 to 100 wt %, more preferably 3 to 95 wt %, and even more preferably 5 to 91 wt %. Incorporation of an appropriate amount of the antioxidant oil and fat composition can achieve preferable antioxidative activity.
The oil and fat used in the preparation of the antioxidant oil and fat composition may be unsaturated fatty acid-containing oil and fat, and in this case, the antioxidant oil and fat composition is equal to the unsaturated fatty acid-containing oil and fat composition. That is, the amount of the antioxidant oil and fat composition contained in the unsaturated fatty acid-containing oil and fat composition is 100 wt %.
In the present invention, the antioxidant oil and fat composition according to the present invention containing the water-soluble antioxidant at a higher concentration tends to achieve greater antioxidative activity. Specifically, in systems in which the same amount of water-soluble antioxidant is used in PUFA oil, the antioxidative activity tends to become higher with a small amount of the antioxidant oil and fat composition that contains a large amount of water-soluble antioxidant, rather than with a large amount of the antioxidant oil and fat composition that contains a small amount of water-soluble antioxidant.
The antioxidant oil and fat composition according to the present invention contains the water-soluble antioxidant at a concentration of preferably 1 to 25 wt %, more preferably 2 to 15 wt %, and most preferably 3.5 to 7 wt %. When the concentration is adjusted to be within the preferred range, preferable antioxidative activity can be obtained.
In the present invention, the amount of DHA and EPA in the unsaturated fatty acid-containing oil and fat composition is preferably 0.1 to 60 wt %, more preferably 1 to 50 wt %, and even more preferably 5 to 40 wt %.
Incorporation of appropriate amounts of DHA and EPA makes it possible to obtain an unsaturated fatty acid-containing oil and fat composition with promising physiological effects etc.
Hereafter, examples of the method for preparing an antioxidant oil and fat composition according to the present invention are described.
In the present invention, a water-soluble antioxidant and a carbohydrate are dissolved in water to prepare an aqueous phase. Here, these components must be contained in the aqueous phase in a substantially dissolved state. The determination of whether these components are substantially dissolved is made by introducing 5 ml of the aqueous phase into a 20-ml centrifugal tube, followed by centrifugal separation (3000×g, 1 minute) at 20° C. If no precipitate is visually observed even after this process, the components are determined as being substantially dissolved. In the present invention, the expression such as “contained in the aqueous phase” means “being present in the aqueous phase in the dissolved state.”
If precipitate is observed in the aqueous phase, it is possible that the antioxidant oil and fat composition does not have high antioxidative activity.
The oil phase is prepared by dissolving one or more oil-soluble components in oil and fat. In the present invention, an oil-soluble emulsifier is optionally used as an oil-soluble component.
Subsequently, the oil phase and the aqueous phase are mixed and emulsified to give an oil and fat composition in the form of water-in-oil emulsion. To perform emulsification here, a commonly used emulsifying device is used to thus easily obtain a preferable antioxidant oil and fat composition. Specific examples of usable emulsifying device include a high-pressure homogenizer, an ultrasonic emulsifying device, and a two-component impingement-type emulsifying device, which is also called a wet-jet mill. The use of an appropriate emulsifying device makes it possible to obtain a predetermined antioxidant oil and fat composition. Emulsification with the use of a high-pressure homogenizer is commonly performed at 30 to 40 MPa and 10 to 30 passes.
The use of a commonly used emulsifying device can easily reduce the particle size; this possibly relates to the fact that the aqueous phase contains a high degree of water-soluble solids in the dissolved state.
In the present invention, emulsification is preferably performed using an appropriate emulsifying device so that the particle size becomes 300 nm or less. The particle size is more preferably 160 nm or less, and even more preferably 130 nm or less. Adjusting the particle size to below a certain degree makes it possible to obtain a preferable antioxidant oil and fat composition, in terms of the antioxidative activity and its stability.
In the present invention, it is preferable to dehydrate a portion of water after emulsification. The method for dehydration is not limited, and dehydration may be performed by bubbling gas or under reduced pressure. For dehydration, partial dehydration of 12 to 76 wt %, and more preferably 20 to 67 wt %, of water contained in the prepared emulsified product is preferred. By performing appropriate partial dehydration, an antioxidant oil and fat composition having strong antioxidative activity is obtained. Further, by performing appropriate partial dehydration, the occurrence of precipitation can be delayed, whereby the commodity value is improved.
The precipitation is believed to be caused by the primary action of the antioxidant oil and fat composition; thus, when precipitation occurs, it is believed to be impossible to achieve antioxidative activity without stirring. If continuous stirring is required to achieve high antioxidative activity, the use thereof is very difficult. Thus, no precipitation preferably occurs in the antioxidant oil and fat composition according to the present invention.
Even after partial dehydration is performed, the antioxidant oil and fat composition according to the present invention contains a certain amount of water. Therefore, it could be difficult to use oil and fat containing the antioxidant oil and fat composition as oil and fat for cooking with heat, such as for frying.
More specifically, the antioxidant oil and fat composition according to the present invention is particularly suitably used for, for example, stabilizing polyunsaturated fatty acid-containing oil and fat, such as PUFA oils.
The Examples are described below.
For the “sugar powder” in the formulations, pulverized sugar was used.
Samples of formulations shown in Table 1-1 were prepared in accordance with the “Method for preparing an antioxidant oil and fat composition (study 1).”
The obtained samples were evaluated by the “Method of evaluation of oxidative stability based on CDM (study 1).” Table 1-2 shows the results.
In this study, although an actual measurement of the particle size with the use of a device was not performed after the emulsifying operation, because it was visually confirmed that precipitation etc. did not occur, the particle sizes were all considered to be 300 nm or less.
The results revealed that the addition of the prepared antioxidant oil and fat compositions of predetermined formulations greatly improved the oxidative stability of fish oil. The improving effect was greater than that of TBHQ.
Samples of formulations shown in Table 2-1 were prepared in accordance with the “Method for preparing an oil and fat composition (study 2).”
The obtained samples were evaluated by the “Method of evaluation of oxidative stability based on POV (study 2).” Table 2-2 shows the results.
In this study as well, an actual measurement of the particle size with the use of a device was not performed after the emulsifying operation; however, because it was visually confirmed that precipitation etc. did not occur in the samples of the Examples, the particle sizes in the Examples were all considered to be 300 nm or less.
Samples of formulations shown in Table 2-3 were prepared in accordance with the “Method for preparing an oil and fat composition (study 2).”
The obtained samples were evaluated by the “Method of evaluation of oxidative stability based on CDM (study 2-2).” Table 2-4 shows the results.
In this study as well, an actual measurement of the particle size with the use of a device was not performed after the emulsifying operation; however, because it was visually confirmed that precipitation etc. did not occur in the samples of the Examples, the particle sizes in the Examples were all considered to be 300 nm or less.
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Samples of formulations shown in Table 3-1 were prepared in accordance with the “Method for preparing an oil and fat composition (study 3).” The obtained samples were evaluated by the “Method of evaluation of oxidative stability based on CDM (study 3).” Table 3-2 shows the results.
In Example 3-15 and Comparative Example 3-9, evaluation was performed in accordance with the “Method of evaluation of oxidative stability based on POV (study 3).” Table 3-3 shows the results.
For the samples in which precipitation was observed at the time of the measurement, basically, the CDM value was not measured.
(The DCM value of 3.0 g of soybean oil measured under the conditions of 2 above was 20 hrs.)
As a control, a product obtained by mixing 4 parts by weight of the same tuna oil per 1 part by weight of soybean oil was used.
Samples of formulations shown in Table 3-4 were prepared in accordance with the “Method for preparing an oil and fat composition (study 3-2).” The obtained samples were evaluated by the “Method of evaluation of oxidative stability based on CDM (study 3-2).” Table 3-5 shows the results.
Samples of formulations shown in Table 4-1 were prepared in accordance with the “Method for preparing an antioxidant oil and fat composition (study 4).” The obtained samples were evaluated in accordance with the “Method of evaluation of oxidative stability based on CDM (study 4).” Table 4-2 shows the results.
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Amino acids have different solubility according to their type; amino acids of low solubility dissolved less in an aqueous phase, and accordingly, tended to achieve less antioxidative activity. Nevertheless, it was confirmed that the use of all of the amino acids had a tendency of achieving increased antioxidative activity.
To compare the antioxidative activity of each amino acid, comparative analysis was performed by adjusting the concentration of each amino acid in the aqueous phase to 144 mM or 25 mM.
Samples of formulations shown in Table 4-3 were prepared in accordance with the “Method for preparing an oil and fat composition (study 4).” The obtained samples were evaluated in accordance with the “Method of evaluation of oxidative stability based on CDM (study 4-2).” Table 4-4 shows the results.
Samples of formulations shown in Table 5-1 were prepared in accordance with the “Method for preparing an oil and fat composition (study 5).” The obtained samples were evaluated in accordance with the “Method of evaluation of oxidative stability based on CDM (study 5).” Table 5-2 shows the results.
Samples of formulations shown in Table 6-1 were prepared in accordance with the “Method for preparing an oil and fat composition (study 6).” The obtained samples were evaluated by the “Method of evaluation of oxidative stability based on CDM (study 6).” Table 6-2 shows the results.
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The difference in the antioxidative activity as a result of the difference in the production method was analyzed.
Samples of formulations shown in Table 7-1 were prepared in accordance with the “Method for preparing an oil and fat composition (study 7).” As shown in Table 7-2, samples for measurement of antioxidative activity were prepared using the obtained samples, and were subjected to Rancimat to measure the CDM value. The measurement was performed at 96° C., at an air-blowing rate of 20.0 L/h with a sample-introducing amount of 3.0 g (amount of water: 70 ml). The “Samples for measurement of antioxidative activity” were prepared by mixing the components in accordance with the formulations, and lightly stirring the mixture for homogenization.
Table 7-3 shows the CDM values. The samples with a CDM value 1.5 times or more greater than that of Comparative Example 7-1 were evaluated as pass.
The antioxidant oil and fat compositions were prepared by varying the concentration of the antioxidant such that the amounts of the antioxidant in the compositions were consequently equal to each other, and the CDM value was measured.
Table 7-3 indicates that the antioxidant oil and fat composition containing the antioxidant at a predetermined concentration had high antioxidative activity.
It was also confirmed that the antioxidant oil and fat composition of Example 7-4, which contained the antioxidant at a higher concentration, achieved higher antioxidative activity.
Oil and fat compositions of formulations “before” the dehydration step of tests A to X shown in Table 8-1 were prepared in accordance with the “Method for preparing an oil and fat composition (study 8).” Subsequently, partial dehydration was performed with nitrogen aeration. The formulations “after” the dehydration step shown in Table 8-1 refer to the compositions after dehydration according to calculations, considering the mass reduced as a result of the dehydration operation as dehydrated water.
Table 8-1 shows the particle size of each sample as required.
The obtained samples were evaluated in accordance with the “Method of evaluation of oxidative stability based on CDM (study 3).”
Table 8-2 shows the results.
The oil and fat compositions obtained in the present invention were compared in terms of antioxidative activity.
Table 9-1 shows the samples. The effect was confirmed based on the measurement of POV (peroxide value). The details of the evaluation were described below in the “Method of evaluation of oxidative stability based on POV (study 9).”
As shown in
Due to its low oxidative stability, the use of PUFA oil was limited in many cases. However, it is presumed that the use of the oil and fat composition according to the present invention has made it possible to use PUFA oil in a manner similar to that of general-purpose oils and fats, such as soybean oil.
In this study, a sensory evaluation was also performed by a method in which an unpleasant odor was confirmed. Here as well, the occurrence of an unpleasant odor such as a fishy odor was greatly prevented in PUFA oil with which the oil and fat composition according to the present invention was used, indicating that general-purpose use was possible. Heretofore, fish oil etc. could have an unpleasant odor before the peroxide value actually increases, and for this reason, it was presumed that the occurrence of an unpleasant odor could be caused by a factor other than oxidation. However, the use of the oil and fat composition according to the present invention having overwhelmingly strong antioxidative activity prevented the occurrence of an unpleasant odor, which suggested that oxidation was the main cause of the occurrence of an unpleasant odor such as a fishy odor.
Number | Date | Country | Kind |
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PCT/JP2016/056457 | Mar 2016 | JP | national |
2016-115392 | Jun 2016 | JP | national |
Filing Document | Filing Date | Country | Kind |
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PCT/JP2017/007906 | 2/28/2017 | WO | 00 |