JP7473960B2 - Water-soluble preparations containing highly unsaturated fatty acids - Google Patents

Description

The present invention relates to a water-soluble preparation containing highly unsaturated fatty acids that can be added or blended into processed foods containing water by solubility in water of highly unsaturated fatty acids or oils and fats containing highly unsaturated fatty acids in a stable manner against oxidation.

There have been many reports on the biological regulation functions of polyunsaturated fatty acids such as eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA), arachidonic acid (ARA), α-linolenic acid, and γ-linolenic acid, including the prevention of arteriosclerosis and activation of brain function, and their physiological functions have been attracting attention. These polyunsaturated fatty acids exist in the body not only in the form of free fatty acids but also in various oil and fat forms such as alkyl esters, triacylglycerols, phospholipids, and glycolipids, but are generally supplied as oil and fat in the form of triacylglycerols such as fish oil, perilla oil, and vegetable oils such as linseed oil. On the other hand, processed foods such as beverages contain a large amount of water, making it difficult to mix oils and fats in their original state, and preparation processing such as emulsification and dispersion is required, and processed oil-containing preparations are available in the form of emulsions, powders, and other formulations.

On the other hand, highly unsaturated fatty acids are unstable to oxidation due to the large number of unsaturated bonds, and are subject to oxidative modification during formulation processing and storage, resulting in quality degradation such as odor deterioration and discoloration. Generally, antioxidants such as tocopherol, ascorbic acid, butyl hydroxyanisole (BHA), and butyl hydroxytoluene (BHT) are used to prevent the oxidation of oils and fats, but simply adding them to oils and fats containing highly unsaturated fatty acids, which have many unsaturated bonds, is not effective enough, and it has also been reported that formulations of compounds with different polarities, such as emulsions, show antioxidant effects different from those in homogeneous systems (Non-Patent Document 1).

Various methods have been reported for stabilizing water-soluble preparations containing highly unsaturated fatty acids. For example, there is a method in which tocopherol, phospholipids, ascorbic acid, etc. are added to oils and seafood extracts and emulsified with an emulsifier such as polyglycerol fatty acid ester (Patent Document 1), a method in which a water-soluble antioxidant such as ascorbic acid or erythorbic acid is added to the aqueous phase, and an oil-soluble antioxidant-containing component such as sesame oil, ascorbic acid ester, tocopherol, etc. is added to the oil phase and emulsified (Patent Document 2), and a method in which an antioxidant such as ascorbic acid or catechin and a polyhydric alcohol are added, and a milk-soluble preparation containing a polyglycerol fatty acid ester with an HLB of 10 or more, a sucrose fatty acid ester, and lecithin is used to emulsify the oil phase. Disclosed are a method for obtaining an emulsion (Patent Document 3), a powder obtained by adding tocopherol or phospholipids to highly unsaturated fatty acids including monoglycerides, and then drying the emulsion to which casein or soy protein or the like is added (Patent Document 4), a method for emulsifying oils and fats containing highly unsaturated fatty acids with micellar casein, a water-soluble antioxidant, an oil-soluble antioxidant, sugars such as trehalose, and an emulsifier, and then drying the resulting powder (Patent Document 5), and a method for blending antioxidant components of sesame with ascorbic acid or an ascorbic acid ester (Patent Document 6). However, none of these methods can be said to have sufficient oxidation stability in terms of the balance of the types and amounts of antioxidant components blended.

On the other hand, a technology has been disclosed in which highly unsaturated fatty acids are microencapsulated using a gelatin cross-linking enzyme to obtain a stable powder (Patent Document 7), but the cross-linked microcapsules are insoluble in water, making it difficult to apply this to foods that contain a lot of moisture.

W. Porte et al., J. Agric. Food Chem., 37, 615 (1989)

Japanese Patent Application Laid-Open No. 5-86395 Japanese Patent Application Laid-Open No. 6-298642 Japanese Patent Application Laid-Open No. 7-227227 Japanese Patent Application Laid-Open No. 6-172782 JP 2019-41721 A International Publication No. 2004/048496 JP 2019-68744 A

The object of the present invention is to provide a water-soluble preparation containing highly unsaturated fatty acids that is not water-soluble and has low oxidation stability, and that can stably solubilize highly unsaturated fatty acids or oils and fats containing highly unsaturated fatty acids, and can be stably blended with processed foods and the like that contain water.

The present inventors have discovered that an emulsion or powder preparation containing (A) highly unsaturated fatty acids or oils and fats containing highly unsaturated fatty acids, (B) (b1) an oil-soluble radical scavenging antioxidant having phenolic hydrogen and/or (b2) an oil-soluble antioxidant exhibiting oxidation-reduction type, (C) (c1) a water-soluble radical scavenging antioxidant having phenolic hydrogen and/or (c2) a water-soluble antioxidant exhibiting oxidation-reduction type, and exhibiting good solubility in water, in which the content of (A) is 5% to 60% by mass, the total content of (B) and (C) is 0.01% to 10% by mass, the ratio of (B)/(C) is 0.2 to 5, and the ratio of ((b1)+(c1))/((b2)+(c2)) is 0.2 to 5, allows highly unsaturated fatty acids or oils and fats containing highly unsaturated fatty acids to be stably blended with processed foods and the like containing water, thereby completing the present invention.

That is, the present invention is as follows.
[1] (A) a highly unsaturated fatty acid or an oil or fat containing a highly unsaturated fatty acid;
(B) (b1) an oil-soluble radical scavenging antioxidant having a phenolic hydrogen and/or (b2) an oil-soluble antioxidant exhibiting an oxidation-reduction type,
(C) A highly unsaturated fatty acid-containing water-soluble preparation containing (c1) a water-soluble radical-scavenging antioxidant having a phenolic hydrogen atom and/or (c2) a water-soluble antioxidant exhibiting an oxidation-reduction type (excluding ascorbic acid and erythorbic acid),
A water-soluble preparation containing highly unsaturated fatty acids, characterized in that the content of (A) is 5% by mass to 60% by mass, the total content of (B) and (C) is 0.01% by mass to 10% by mass, the ratio of (B)/(C) is 0.2 to 5, and the ratio of ((b1)+(c1))/((b2)+(c2)) is 0.2 to 5.
[2] The highly unsaturated fatty acid-containing water-soluble preparation according to the above [1], wherein (b1) is one or more of tocopherol, gallic acid fatty acid ester, BHA, and BHT.
[3] The highly unsaturated fatty acid-containing water-soluble preparation according to the above [1] or [2], wherein (b2) is one or more of an ascorbic acid fatty acid ester and ubiquinone.
[4] The water-soluble preparation containing highly unsaturated fatty acids according to any one of [1] to [3] above, wherein (c1) is one or more of tea catechins, anthocyanins, and chlorogenic acid.
[5] The water-soluble preparation containing highly unsaturated fatty acids according to any one of [1] to [4], wherein (c2) is one or more of metal salts of ascorbic acid and metal salts of erythorbic acid.
[6] The highly unsaturated fatty acid-containing water-soluble preparation according to any one of [1] to [5] above, wherein the highly unsaturated fatty acid (A) includes any one of eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA), and α-linolenic acid.
[7] The highly unsaturated fatty acid-containing water-soluble preparation according to any one of [1] to [6], wherein the preparation is in the form of an emulsion.
[8] The highly unsaturated fatty acid-containing water-soluble preparation according to any one of [1] to [6], wherein the preparation is in the form of a powder.

The present invention is a novel technology that has superior oxidation stability and blending stability in processed foods containing water compared to conventional water-soluble formulation technologies containing highly unsaturated fatty acids, and is characterized by the ability to effectively add and blend highly unsaturated fatty acids or oils and fats containing highly unsaturated fatty acids in the field of processed foods containing water.

The (A) highly unsaturated fatty acid or fats and oils containing highly unsaturated fatty acids used in the present invention are not particularly limited in type as long as they are used as foods or food additives. For example, highly unsaturated fatty acids include eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA), arachidonic acid (ARA), α-linolenic acid, γ-linolenic acid, eicosatetraenoic acid (ETA), eicosatrienoic acid (ETE), linoleic acid, and stearidonic acid (SDA). Fat and oil include triacylglycerol, phospholipid, and glycolipid, and one or more of these can be used. Note that highly unsaturated fatty acids refer to fatty acids having two or more unsaturated bonds.

The content of the (A) highly unsaturated fatty acid or oils and fats containing highly unsaturated fatty acids in the highly unsaturated fatty acid-containing water-soluble preparation of the present invention is 5% by mass to 60% by mass, preferably 7% by mass to 50% by mass, and more preferably 10% by mass to 40% by mass, based on the entire highly unsaturated fatty acid-containing water-soluble preparation of the present invention. If the blending amount is less than 5% by mass, a large blending amount is required, which causes problems in terms of economy, and if it exceeds 60% by mass, problems with the stability of the preparation, such as separation and oil floating, are undesirable.

The oil-soluble radical scavenging antioxidant having a phenolic hydrogen (b1) used in the present invention is not particularly limited in type as long as it is used as a food or food additive, and examples thereof include tocopherols, gallic acid esters, BHA (butyl hydroxyanisole), BHT (dibutyl hydroxytoluene), oil-soluble catechin, etc., and one or more of these can be used.

The type of the oil-soluble antioxidant (b2) showing an oxidation-reduction type used in the present invention is not particularly limited as long as it is used as a food or food additive, and examples of such antioxidants include ubiquinones and ascorbic acid esters, and one or more of these can be used.

The water-soluble radical scavenging antioxidant having a phenolic hydrogen (c1) used in the present invention is not particularly limited in type as long as it is used as a food or food additive, and examples of the antioxidant include water-soluble polyphenols such as anthocyanins, tea extracts, and coffee extracts, and one or more of these can be used.

The water-soluble oxidation-reduction type antioxidant (c2) used in the present invention is not particularly limited in type as long as it is used as a food or food additive, and examples thereof include ascorbic acids and their salts, erythorbic acids and their salts, and in particular metal salts of ascorbic acid and metal salts of erythorbic acid, and one or more of these can be used. However, ascorbic acid and erythorbic acid increase the peroxide value, it is preferable to exclude them from the above antioxidants.

When the sum of (b1) and (b2) above is (B), and the sum of (c1) and (c2) is (C), the total amount of (B) and (C) used in the present invention is preferably 0.01% to 10% by mass, more preferably 0.03% to 8% by mass, and even more preferably 0.05% to 6% by mass, based on the entire highly unsaturated fatty acid-containing water-soluble preparation of the present invention. If the amount is less than 0.01% by mass, the antioxidant effect is insufficient, and if it exceeds 10% by mass, the balance of the entire preparation is lost, causing problems such as separation and coloring, which is undesirable.

The ratio of (B) to (C) used in the present invention, (B)/(C), is preferably 0.2 to 5, more preferably 0.3 to 4, and even more preferably 0.4 to 3. If the ratio is less than 0.2 or more than 5, a sufficient antioxidant effect cannot be obtained, which is not preferable.

The ratio ((b1)+(c1))/((b2)+(c2)) used in the present invention is preferably 0.2 to 5, more preferably 0.3 to 4, and even more preferably 0.4 to 3. If the ratio is less than 0.2 or exceeds 5, a sufficient antioxidant effect cannot be obtained, which is not preferred.

In the highly unsaturated fatty acid-containing water-soluble preparation of the present invention, emulsifiers used in known foods can be used as long as they do not impair the effects of the present invention. Examples include polyglycerol esters, monoglycerol esters, sugar esters, sorbitan esters, lecithins, thickening polysaccharides, etc., which can be added alone or in combination of two or more kinds.

The highly unsaturated fatty acid-containing water-soluble preparation of the present invention can be blended with known food or food additive raw materials as long as the effects of the present invention are not impaired. For example, base components such as oils, water, alcohols, and waxes can be blended, excipients such as sugars, polysaccharides, and starches can be blended, and additive components such as organic acids, inorganic salts, preservatives, flavorings, chelating agents, specific gravity adjusters, and viscosity adjusters can be blended.

The machines used for producing the highly unsaturated fatty acid-containing water-soluble preparation of the present invention are not particularly limited, and machines such as mixers, agitators, dispersers, homomixers, homogenizers, high-pressure homogenizers, ultra-high-pressure homogenizers, ball mills, colloid mills, planetary mills, wet OB mills, rotary grinders, kneaders, kneaders, spray dryers, vacuum dryers, freeze dryers, and vibrating sieves can be used alone or in combination.

The form of the highly unsaturated fatty acid-containing water-soluble preparation of the present invention is not particularly limited as long as it does not impair the effects of the present invention. In typical preparation methods, the preparation is often in the form of a liquid preparation, but it can also be used after mixing with an excipient and powdering it by spray drying, vacuum drying, freeze drying, or other processing.

The present invention will now be described in detail with reference to examples, but the present invention is not limited to these examples.

In this embodiment and comparative example, DHA algal oil (manufactured by BASF) was used as the DHA-containing oil, EPA (manufactured by Maruha Nichiro) was used as the EPA-containing oil, linseed oil (manufactured by Nisshin Oil Mills) was used as the α-linolenic acid-containing oil, and Emix 70 (manufactured by Mitsubishi Chemical Foods), propyl gallate (manufactured by Fuji Chemical Industry Co., Ltd.), BHA, BHT (all manufactured by Nikki Universal Co., Ltd.), ascorbyl palmitate, sodium ascorbate, ascorbic acid, sodium erythorbate, coenzyme Q10 (all manufactured by Watanabe Chemical Co., Ltd.), tea catechin, blueberry extract, coffee extract (all manufactured by Tokiwa Phytochemical Co., Ltd.) were used as the tocopherol. The tocopherol was added by converting the tocopherol concentration of the raw material and the concentration contained in the raw material oil, and the amount added in the table is shown as the converted total amount added.

[Preparation Example 1: Preparation of highly unsaturated fatty acid-containing emulsion (Examples 1 to 5, Comparative Examples 1 to 3)]
40% by mass of glycerin (manufactured by Sakamoto Yakuhin Co., Ltd.) and 5% by mass of Sunsoft Q-17S (manufactured by Taiyo Kagaku Co., Ltd.) were heated to 80°C, and homogenized for 5 minutes at 6000 rpm using a homomixer. After cooling to 40°C, 5% by mass of Coconard MT (manufactured by Kao Corporation) and the highly unsaturated fatty acid-containing oils and fats (A) and antioxidants (B) shown in Table 1 were added. The antioxidants of fatty acid esters were dissolved in a small amount of ethanol, and the other antioxidants were dissolved in Coconard MT and added. Then, the mixture was homogenized for 10 minutes at 6000 rpm using a homomixer at 40°C, and the antioxidant (C) and the remaining water were added, and the mixture was homogenized for 10 minutes at 6000 rpm using a homomixer at 40°C to obtain emulsions of Examples 1 to 5 and Comparative Examples 1 to 3.

[Preparation Example 2: Preparation of highly unsaturated fatty acid-containing powder (Examples 6 to 8, Comparative Examples 4 and 5)]
The oil or fat containing highly unsaturated fatty acids (A) shown in Table 2, the antioxidant (B) dissolved in a small amount of ethanol, 10% by mass of trehalose and the antioxidant (C), and the remainder of reduced maltose syrup (manufactured by Watanabe Chemical Co., Ltd.) were added and kneaded using a kneader for 4 hours or more, and then dried under reduced pressure at 60°C for 3 days. The mixture was then pulverized using a rotary pulverizer and separated using a 30 mesh sieve to obtain powders of Examples 6 to 8 and Comparative Examples 4 and 5.

[Preparation Example 3: Preparation of highly unsaturated fatty acid-containing powder (Examples 9 to 10, Reference Example 1 , Comparative Example 6)]
12% by mass of Arabic Coal SS (manufactured by SANEI PHARMACEUTICAL CO., LTD.), 9% by mass of Pine Index #2 (manufactured by Matsutani Chemical Co., Ltd.), and the remaining water excluding the highly unsaturated fatty acid-containing fats and oils (A) and antioxidants shown in Table 2 were heated to 80°C, homogenized for 5 minutes at 6000 rpm using a homomixer, cooled to 40°C, and then a mixture of the antioxidants (C) and the highly unsaturated fatty acid-containing fats and oils (A) and the antioxidants (B) shown in Table 2 was added, and homogenized for 30 minutes at 7000 rpm using a homomixer. The resulting emulsion was fed to a spray dryer with an inlet temperature of 145°C and an atomizer rotation speed of 30,000 rpm at a liquid feed rate of 30 mL/min while being heated to 55°C, and further separated using a 30 mesh sieve to obtain powders of Examples 9 to 10, Reference Example 1 , and Comparative Example 6.

[Water solubility evaluation]
The solubility of 1% aqueous solutions of the Examples and Comparative Examples was confirmed and judged according to the following criteria.
◎: Dissolves quickly and uniformly after dilution. ○: Requires stirring after dilution, but dissolves uniformly. △: Partially dissolves with stirring, but remains undissolved or precipitate remains. ×: Does not dissolve.

[Peroxide value evaluation]
After extracting the oil from the preparation, the peroxide value (POV) was measured using 888 Titrando (Metrôm) in accordance with the potentiometric titration method of the standard method for the analysis of fats and oils, and the number of days required to reach the specified POV was confirmed.

As is clear from Table 1, Examples 1 to 5 exhibited extremely good water solubility, and the number of days required for the POV to reach 10 was significantly extended compared to Comparative Examples 1 to 3.

As is clear from Table 2, the powders of Examples 6 to 8 obtained in Preparation Example 2 exhibited extremely good water solubility, and the number of days until the POV reached 30 was clearly extended compared to Comparative Examples 4 and 5. In addition, the powders of Examples 9 to 10 and Reference Example 1 obtained in Preparation Example 3 exhibited good water solubility, and the number of days until the POV reached 30 was clearly extended compared to Comparative Example 6.

Claims (8)

(A) a highly unsaturated fatty acid or an oil or fat containing a highly unsaturated fatty acid;
(B) (b1) an oil-soluble radical scavenging antioxidant having a phenolic hydrogen atom and (b2) an oil-soluble antioxidant exhibiting an oxidation-reduction type,
(C) A highly unsaturated fatty acid-containing water-soluble preparation containing (c1) a water-soluble radical-scavenging antioxidant having a phenolic hydrogen atom and/or (c2) a water-soluble antioxidant exhibiting an oxidation-reduction type (excluding ascorbic acid and erythorbic acid),
the content of (A) is 10 % by mass to 40 % by mass, the total content of (B) and (C) is 0.01% by mass to 10% by mass, the ratio of (B)/(C) is 0.67 to 5, and the ratio of ((b1)+(c1))/((b2)+(c2)) is 0.2 to 5;
A highly unsaturated fatty acid-containing water-soluble preparation, wherein (c2) is one or more of a metal salt of ascorbic acid and a metal salt of erythorbic acid . The highly unsaturated fatty acid-containing water-soluble preparation according to claim 1, wherein (b1) is one or more of tocopherol, gallic acid fatty acid ester, BHA, and BHT. The highly unsaturated fatty acid-containing water-soluble preparation according to claim 1 or 2, wherein (b2) is one or more of an ascorbic acid fatty acid ester and ubiquinone. The highly unsaturated fatty acid-containing water-soluble preparation according to any one of claims 1 to 3, wherein (c1) is one or more of tea catechins, anthocyanins, and chlorogenic acid. 5. The highly unsaturated fatty acid-containing water-soluble preparation according to claim 1, wherein the highly unsaturated fatty acid (A) comprises any one of eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA), and α-linolenic acid. 6. The highly unsaturated fatty acid-containing water-soluble preparation according to claim 1, wherein the preparation is in the form of an emulsion. 6. The highly unsaturated fatty acid-containing water-soluble preparation according to claim 1, wherein the preparation is in the form of a powder. The highly unsaturated fatty acid-containing water-soluble preparation according to any one of claims 1 to 5, wherein (C) comprises (c1) a water-soluble radical-scavenging antioxidant having a phenolic hydrogen and (c2) a water-soluble antioxidant exhibiting an oxidation-reduction type (excluding ascorbic acid and erythorbic acid).