JP2004168985A - Omega-3 polyunsaturated fatty acid-containing partial glyceride composition and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for efficiently producing an ω-3 type highly unsaturated fatty acid-containing partial glycerides, especially, their monoglycerides. <P>SOLUTION: An ω-3 type highly unsaturated fatty acid-containing partial glyceride composition is obtained by reacting an ω-3 type highly unsaturated fatty acid-containing fatty acid and/or its ester with glycerol under a reduced-pressure atmosphere in the presence of a lipase which does not substantially recognize a triglyceride as a substrate but recognizes a monoglyceride and/or a diglyceride as the substrate. <P>COPYRIGHT: (C)2004,JPO

Description

[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an omega-3 polyunsaturated fatty acid-containing partial glyceride composition and a method for producing the same.
[0002]
[Prior art]
In recent years, ω-3 polyunsaturated fatty acids such as eicosapentaenoic acid (hereinafter referred to as “EPA”) and docosahexaenoic acid (hereinafter referred to as “DHA”) have preventive effects on adult diseases such as arteriosclerosis and thrombosis. It has been reported that it has many physiological actions such as anticancer action, learning ability enhancement action, etc., and is attracting attention as a material for pharmaceuticals, health supplements, foods for specified health use and the like. Recently, in addition to products in which gelatin capsules are filled with EPA and DHA, many EPA and DHA-enriched foods added to foods such as sausages, miso, canned foods, and bread have been developed.
[0003]
EPA and DHA are naturally present in triglycerides and therefore have low affinity for water, and cannot be added to aqueous foods such as soft drinks unless a large amount of emulsifier is used. Further, even if EPA or DHA is added to an aqueous food by such a method, the amount is at most about 10 mg / 100 ml, which cannot be added to the extent that physiological activity is exhibited.
[0004]
It is conventionally known that monoglyceride has an emulsifying action. In the case of EPA or DHA-containing monoglyceride, EPA or DHA in an amount sufficient to exhibit physiological activity is added to an aqueous food such as soft drink. Very advantageous.
[0005]
Methods for producing monoglycerides have been studied for a long time and have already been industrialized. For example, a glycerolysis method of synthesizing monoglyceride by adding about 0.1% of a metal catalyst to a mixture of fat and oil and glycerin and reacting the mixture at 200 to 240 ° C. with stirring is known. In this synthesis method, palmitic acid or Monoglycerides of saturated fatty acids such as stearic acid and monoglycerides of monounsaturated fatty acids such as oleic acid and erucic acid can be produced with high quality. However, since this synthesis method is carried out at a high temperature, polyunsaturated fatty acids having many double bonds are susceptible to polymerization by heat, and monoglycerides of high quality polyunsaturated fatty acids cannot be produced.
[0006]
Therefore, a method for producing monoglycerides by hydrolyzing natural fats and oils using enzymes having mild reaction conditions has been attracting attention. In this method, it is possible to accumulate a certain amount of monoglyceride in the course of hydrolysis of fats and oils. However, monoglyceride is also hydrolyzed with the progress of hydrolysis, so that it is difficult to produce a sufficient amount of monoglyceride to meet the industrial cost.
[0007]
On the other hand, Yamane et al. Have proposed a method for producing a highly unsaturated fatty acid-containing partial glyceride by lipase using a fatty acid containing a highly unsaturated fatty acid or an ester thereof and glycerin as raw materials (Japanese Patent Laid-Open No. 10-265795). According to this method, the polyunsaturated fatty acid can be concentrated and used in the fatty acid, and a glyceride composition having a composition in which the total of partial glycerides is larger than that of triglycerides can be produced. However, the method of Yamane et al. Also makes up about 40% of the total glycerides produced, and only about 20% of monoglycerides. In this case, sufficient emulsifying power cannot be exerted, so that the application is limited. Furthermore, according to the method of Yamane et al., The amount of glycerin to be added must be at least 30 times the molar amount of the polyunsaturated fatty acid and is not a practical method.
[0008]
Yamaguchi et al. Have proposed a method for producing partial glycerides using lipase with fatty acids and glycerin as raw materials (Japanese Patent No. 1724053). According to this method, it is possible to produce a partial glyceride in which 95% or more is a monoglyceride by using a lipase belonging to the genus Penicillium. However, most of the fatty acids used in the method of Yamaguchi et al. Are saturated fatty acids and monounsaturated fatty acids, and examples of polyunsaturated fatty acids are only linoleic acid and linolenic acid. There is no example in which a fatty acid containing DHA or DHA is used as a raw material.
[0009]
[Patent Document 1]
Japanese Patent Application Laid-Open No. 10-265795 [Patent Document 2]
Japanese Patent No. 1724053
[Problems to be solved by the invention]
An object of the present invention is to provide a method capable of efficiently producing an ω-3 polyunsaturated fatty acid-containing partial glyceride, particularly a monoglyceride.
[0011]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to solve the above problems, and as a result, in the presence of a lipase that does not substantially recognize triglyceride as a substrate and recognizes monoglyceride and / or diglyceride as a substrate, By reacting a fatty acid containing an unsaturated fatty acid and / or an ester thereof with glycerin in a reduced-pressure atmosphere, the triglyceride is hardly contained, and the monoglyceride has a mass ratio of at least twice that of diglyceride, and the mass ratio of the ω-3 series is higher. Saturated fatty acid-containing partial glyceride products were successfully obtained.
[0012]
That is, the present invention includes the following inventions.
(1) In the presence of a lipase that does not substantially recognize triglyceride as a substrate and recognizes monoglyceride and / or diglyceride as a substrate, a fatty acid containing an ω-3 highly unsaturated fatty acid and / or an ester thereof and glycerin are used. An omega-3 polyunsaturated fatty acid-containing partial glyceride composition obtained by reacting under reduced pressure atmosphere.
(2) In the presence of a lipase that does not substantially recognize triglyceride as a substrate and recognizes monoglyceride and / or diglyceride as a substrate, a fatty acid containing an ω-3 polyunsaturated fatty acid and / or an ester thereof and glycerin are used. A method for producing a partially glyceride composition containing an ω-3 polyunsaturated fatty acid, wherein the reaction is carried out under a reduced pressure atmosphere.
[0013]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in detail.
[0014]
The partial glyceride as used herein refers to monoglyceride or diglyceride or a mixture of both. The ω-3 polyunsaturated fatty acid has two or more double bonds, and the first double bond from the terminal side of the methyl group is a fatty acid in which the first double bond exists between the third and fourth carbons. This includes, for example, DHA and EPA. The fatty acid containing ω-3 polyunsaturated fatty acid refers to a mixture of fatty acids containing ω-3 polyunsaturated fatty acid such as DHA and EPA as one of the constituent fatty acids. Further, the ω-3 series polyunsaturated fatty acid-containing partial glyceride is a partial glyceride containing an ω-3 series polyunsaturated fatty acid as a fatty acid component of the partial glyceride, that is, a composition analysis of fatty acids constituting the partial glyceride was carried out. It means a partial glyceride containing an ω-3 polyunsaturated fatty acid as one of its constituent fatty acids.
[0015]
In the method of the present invention, not only pure ω-3 polyunsaturated fatty acids or esters thereof but also those prepared from fats and oils containing ω-3 polyunsaturated fatty acids or esters thereof can be used. Such fats and oils are not particularly limited as long as they contain ω-3 polyunsaturated fatty acids, but are, for example, fish oils such as sardine oil, tuna oil, bonito oil, and marine-derived fats and microorganisms such as krill oil. And the like.
[0016]
The fatty acid containing an ω-3 polyunsaturated fatty acid and / or an ester thereof used as a raw material in the present invention can be obtained, for example, as follows.
[0017]
When preparing from the above-mentioned marine-derived fats and oils derived from microorganisms, etc., these fats and oils are hydrolyzed or esterified to obtain fatty acids containing ω-3 highly unsaturated fatty acids and / or esters thereof. Can be. This hydrolysis reaction or esterification reaction can be carried out by a known method, but is preferably carried out using an enzyme capable of causing the reaction to proceed at room temperature, for example, a lipase. In addition, as an alcohol component for esterification, a monohydric alcohol such as methanol and ethanol can be used.
[0018]
After completion of the hydrolysis reaction or esterification reaction, the produced fatty acid containing the ω-3 polyunsaturated fatty acid and / or its ester can be used as it is in the next reaction as a raw material of the method of the present invention, or The ω-3 polyunsaturated fatty acid or ester thereof may be concentrated or purified by a known method to increase the concentration of ω-3 polyunsaturated fatty acid or ester thereof, and used as a raw material. Examples of the concentration method or the purification method include methods such as a distillation method, a wintering method, a supercritical extraction method, and a chromatographic method.
[0019]
Next, the fatty acid containing the ω-3 type highly unsaturated fatty acid and / or its ester is reacted with glycerin in the presence of lipase. As the lipase used in the present invention, a lipase that recognizes monoglyceride and / or diglyceride as a substrate but does not substantially recognize triglyceride as a substrate, that is, a lipase having specificity for monoglyceride and / or diglyceride is preferable. Such lipases include, for example, lipases derived from the genus Penicillium, such as Penicillium cyclopium and Penicillium camembertii, and lipases derived from the genus Bacillus, such as Bacillus stearothermophilus. The lipase may be used as it is, but it is more economical if it is used by immobilizing it on a carrier such as celite, calcium carbonate, ion exchange resin or the like, since it can be used repeatedly.
[0020]
The amount of the lipase to be added may be appropriately determined depending on the reaction conditions, and is not particularly limited, but is preferably 100 U or more, more preferably 200 to 1000 U, per 1 g of the mixture of the fatty acid and / or its ester and glycerin. Here, 1 U of enzyme is the amount of enzyme that releases 1 μmol of oleic acid per minute in hydrolysis using monoolein as a substrate. Glycerin used in the present invention is not particularly limited, and commercially available glycerin can be used. The amount of glycerin to be used is at least an equivalent, more preferably 3 to 10 times the molar amount of the fatty acid. Although larger amounts can be used without particularly affecting the reaction, they are not economical.
[0021]
The reaction temperature is not particularly limited as long as the reaction proceeds, but if the temperature is higher than 50 ° C, the reactivity is reduced. Therefore, it is usually 5 to 40 ° C, preferably 10 to 35 ° C. The reaction time can be appropriately determined in consideration of other reaction conditions, but is usually 10 hours or more, preferably 24 hours or more.
[0022]
The reaction between the ω-3 type highly unsaturated fatty acid and / or its ester and glycerin is performed under reduced pressure. Although the pressure reduction condition is not particularly limited as long as it is lower than normal pressure, the reaction is usually performed under a reduced pressure atmosphere of 30 mmHg or less, preferably 15 mmHg or less. By performing the treatment under reduced pressure, the amount of monoglyceride produced can be increased.
[0023]
After completion of the reaction, unreacted fatty acids and their esters are removed by a conventional method, for example, extraction with an organic solvent such as hexane, vacuum distillation, alkali treatment, etc., to obtain a partially glyceride-containing ω-3 type highly unsaturated fatty acid composition. be able to. The omega-3 polyunsaturated fatty acid-containing partial glyceride composition of the present invention thus obtained is a monoglyceride component of DHA, a monoglyceride of EPA, and a monoglyceride of another fatty acid as a monoglyceride component, and DHA and / or a diglyceride component as a diglyceride component. Contains diglycerides containing EPA, diglycerides containing DHA or EPA and other fatty acids, diglycerides containing other fatty acids, and substantially no triglycerides.
[0024]
Although the composition containing the ω-3 polyunsaturated fatty acid-containing partial glyceride obtained as described above may be further separated and purified into its monoglyceride and diglyceride by a known method such as distillation, it may be used. Even when the mixture or composition containing the monoglyceride and the diglyceride is used as it is, a sufficient emulsifying action can be exhibited. Further, if necessary, purification operations such as decolorization and deodorization may be performed by a conventional method.
[0025]
According to the method of the present invention, a partial glyceride containing an ω-3 polyunsaturated fatty acid, particularly a monoglyceride containing an ω-3 polyunsaturated fatty acid can be selectively obtained. It is also possible to obtain at least 80% of the saturated fatty acid-containing partial glycerides as monoglycerides. More specifically, substantially no triglyceride is produced, and the ω-3 polyunsaturated fatty acid-containing monoglyceride is at least twice, preferably at least three times, more preferably at least five times the amount of the diglyceride. It is possible to obtain at a mass ratio greater than the amount.
[0026]
【Example】
Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to the following examples.
In the following examples, TG means triglyceride, DG means diglyceride, and MG means monoglyceride.
[0027]
(Example 1)
Sardine oil was hydrolyzed with lipase, and a fatty acid mixture having an increased EPA concentration was obtained by molecular distillation (EPA 33.2% by mass, average molecular weight 295). Then, the fatty acid mixture and glycerin at a molar ratio of 5 times were mixed, and 400 g of a lipase derived from the genus Penicillium (Lipase G Amano Enzyme) was added to 1 g of the mixture. Under a reduced pressure atmosphere for 24 hours.
[0028]
After completion of the reaction, the lipid composition (% by mass) of the obtained glyceride fraction was examined, and it was TG: DG: MG = 0: 14.6: 85.4. The EPA composition ratio (the ratio of EPA to fatty acids constituting glyceride) in the glyceride fraction was 35.6% by mass.
[0029]
(Comparative Example 1)
The reaction was carried out in the same manner as in Example 1 except that the reaction was not performed under reduced pressure atmosphere but under normal pressure.
[0030]
After completion of the reaction, the lipid composition (% by mass) of the obtained glyceride fraction was examined. As a result, TG: DG: MG = 0: 40.3: 59.7. The EPA composition ratio in the glyceride fraction was 36.5% by mass.
[0031]
Comparing the results of Example 1 and Comparative Example 1, there was no significant difference in the EPA composition ratio in the glyceride fraction, but the lipid composition in the obtained glyceride fraction was significantly different. In Example 1, where the reaction was carried out, it was confirmed that the production ratio of MG was significantly increased as compared with Comparative Example 1 in which the reaction was carried out under normal pressure.
[0032]
(Comparative Example 2)
The reaction was carried out in the same manner as in Example 1 except that a lipase derived from the genus Rhizomucor (Novozyme 388 Novozymes Japan) was used instead of the lipase derived from the genus Penicillium.
[0033]
That is, a fatty acid (33.2% by mass of EPA, average molecular weight of 295) and glycerin in a molar ratio of 5 times were mixed, and 400 g of a lipase derived from the genus Rhizomucol (Novozyme 388 Novozymes Japan) was added to 1 g of this mixture. The reaction was performed for 24 hours under a reduced pressure atmosphere of a reaction temperature of 30 ° C. and a stirring speed of 500 rpm and 5 mmHg.
[0034]
After completion of the reaction, the lipid composition (% by mass) of the obtained glyceride fraction was examined, and it was TG: DG: MG = 0: 45.9: 54.1.
[0035]
(Comparative Example 3)
The reaction was carried out in the same manner as in Comparative Example 2 except that the reaction was not carried out under reduced pressure atmosphere but under normal pressure.
[0036]
That is, a fatty acid (33.2% of EPA, average molecular weight of 295) and glycerin in a molar ratio of 5 times were mixed, and 400 g of a lipase derived from Rhizomucor sp. The reaction was carried out at a temperature of 30 ° C., a stirring speed of 500 rpm and an atmospheric pressure atmosphere for 24 hours.
[0037]
After completion of the reaction, the lipid composition (% by mass) of the obtained glyceride fraction was examined, and it was TG: DG: MG = 9: 45.5: 45.5.
[0038]
From the experimental results of Comparative Example 2 and Comparative Example 3, when the lipase derived from Rhizomucor was used, the ratio of MG in the glyceride fraction of the product did not change so much even when the reaction was performed under reduced pressure atmosphere. The ratio between DG and MG was about 1: 1.
[0039]
(Example 2)
Tuna oil was subjected to ethyl ester by a conventional method, and an ester mixture having an increased concentration of ethyl ester of DHA (DHA-EE) was obtained by molecular distillation (DHA-EE: 68.2% by mass). Then, this DHA-EE and glycerin at a molar ratio of 5 times were mixed, and 400 g of a lipase derived from the genus Penicillium (Lipase G Amano enzyme) was added to 1 g of the mixture, the reaction temperature was 30 ° C., and the stirring speed was 500 rpm. The reaction was performed for 24 hours under a reduced pressure atmosphere of 5 mmHg.
[0040]
After completion of the reaction, the lipid composition (% by mass) of the obtained glyceride fraction was examined, and it was TG: DG: MG = 0: 17.6: 82.4. The DHA composition ratio in the glyceride fraction was 64.1% by mass.
[0041]
【The invention's effect】
According to the method of the present invention, an ω-3 polyunsaturated fatty acid-containing partial glyceride can be efficiently produced. Specifically, in the method of the present invention, triglycerides are hardly produced, and it is possible to produce a monoglyceride containing an ω-3 polyunsaturated fatty acid at a mass ratio more than twice that of the diglyceride. Monoglycerides of -3 type highly unsaturated fatty acids can be efficiently produced.
[0042]
Further, the omega-3 polyunsaturated fatty acid-containing partial glyceride composition of the present invention contains an omega-3 polyunsaturated fatty acid such as DHA or EPA having excellent physiological activity as a fatty acid component of glyceride, and is further emulsified. Since it contains a large amount of monoglycerides having an effect, it is possible to provide an aqueous food containing a high concentration of ω-3 highly unsaturated fatty acids.

Claims (2)

In the presence of a lipase which does not substantially recognize triglyceride as a substrate and recognizes monoglyceride and / or diglyceride as a substrate, a fatty acid containing an ω-3 highly unsaturated fatty acid and / or an ester thereof and glycerin are reduced under reduced pressure atmosphere. Ω-based highly unsaturated fatty acid-containing partial glyceride composition obtained by the reaction of In the presence of a lipase which does not substantially recognize triglyceride as a substrate and recognizes monoglyceride and / or diglyceride as a substrate, a fatty acid containing an ω-3 highly unsaturated fatty acid and / or an ester thereof and glycerin are reduced under reduced pressure atmosphere. A process for producing a partial glyceride composition containing an ω-3 polyunsaturated fatty acid, the method comprising reacting the composition.