JP5039291B2 - Oil composition - Google Patents

Description

  The present invention relates to an oil / fat composition having a high glycerin difatty acid ester content mainly composed of an ω3 unsaturated fatty acid.

  Oils and fats containing ω3-unsaturated fatty acids as constituent fatty acids are known to have useful health functions (Non-Patent Document 1, etc.), since they have many unsaturated double bonds in one molecule, When this oil is applied to a product, a return odor is generated during storage, and the commercial value is significantly reduced. Therefore, in order to improve the return odor, a technique using a tea extract (Patent Document 1), a method using L-ascorbic acid ester (Patent Document 2), a method of adding an extract of rosemary and sage (Patent Document) Document 3), a technique of blending phosphatidylethanolamine or phosphatidylserine (Patent Document 4), etc. has been proposed, but the present situation is that a sufficient effect has not been obtained.

On the other hand, an oil and fat composition having a high content of glycerin difatty acid ester having an ω3-unsaturated fatty acid has been disclosed (Patent Documents 5, 6, etc.).
In addition, by combining glycerin difatty acid ester and phosphatidic acid, techniques for suppressing sputtering during fried cooking and techniques for stabilizing emulsification are known (Patent Documents 7, 8, etc.).
Furthermore, since glycerin difatty acid ester is likely to be crystallized by low-temperature storage such as a refrigerator, there is also a technique of containing a specific crystal inhibitor (Patent Document 9).
JP-A-2-55785 Japanese Patent Laid-Open No. 5-140584 JP 2000-144168 A JP-A-2-208390 JP 2001-40386 A JP 2001-262180 A JP-A-2-291228 JP-A-3-89936 JP 2002-176852 A Journal of Japan Oil Chemists' Society, Vol. 48, No. 10, pp. 1017-1024, 1999

As described above, although the ω3-unsaturated fatty acid-containing fats and oils have an excellent health function, it is known that the commercial value is remarkably lowered due to a return odor during storage. In addition, glycerin difatty acid ester is liable to produce fats and oils crystals at low temperatures, which may cause inconvenience in appearance and processing characteristics when blended with food.
Accordingly, an object of the present invention is to provide an oil / fat composition having a high glycerin difatty acid ester content, which has a remarkably improved return odor of ω3 unsaturated fatty acids, has a good flavor, and is excellent in product characteristics and processing characteristics. is there.

  The present inventor examined the above problems and found that the addition of phosphatidic acid improves the return odor of ω3-unsaturated fatty acids with glycerin difatty acid esters over conventional fats (glycerin trifatty acid esters). I found. Further, glycerin difatty acid ester-rich oils and fats are excellent in health functions such as an obesity preventing action and a body weight gain inhibiting action, and an improvement in health function effects is expected by using ω3 unsaturated fatty acid as a main component. However, there was a case where crystals were formed as described above. In this case, by combining with phosphatidic acid, it has been found that the return odor is remarkably improved and the flavor is improved and the low-temperature resistance is improved, so that both problems can be solved simultaneously. Further, by adding an organic carboxylic acid and / or salt thereof to the fat of component (A) and then performing a deodorization treatment, the return odor is remarkably improved, the flavor is improved, and the oxidation stability is also improved. I found out. When the oil and fat composition obtained in this way is applied to various products, it has been found that the fat and oil familiarity, texture, appearance, workability, emulsification and other processing characteristics, and oxidation stability are remarkably excellent. .

That is, the present invention includes the following components (A) and (B):
(A) Oil and fat containing glycerin monofatty acid ester 0.1 to 10% by mass, glycerin difatty acid ester 20 to 95% by mass, glycerin trifatty acid ester 4.9 to 79.9% by mass, and glycerin difatty acid Fat and oil composition containing 15 to 90% by mass of ω3-unsaturated fatty acid in the fatty acid constituting the ester: 100 parts by mass (B) phosphatidic acid and / or salt thereof: 0.003 to 10 parts by mass Is to provide.
Further, the present invention provides an oil or fat composition obtained by subjecting an oil or fat of component (A) to an oil or fat composition obtained by an esterification reaction of a fatty acid derived from fat or oil and glycerin or a transesterification reaction of fat or oil with glycerin. It provides the above-described oil / fat composition, which is produced by performing a deodorization treatment after adding a salt thereof.
Furthermore, the present invention adds an organic carboxylic acid, a derivative thereof and / or a salt thereof to an oil or fat composition obtained by an esterification reaction of a fatty acid derived from fat or oil or a transesterification reaction of fat or oil with glycerin, Provided is a method for producing the oil and fat composition as described above, wherein (B) phosphatidic acid and / or a salt thereof is added in an amount of 0.003 to 10 parts by mass with respect to 100 parts by mass of the component (A) obtained by performing the deodorization treatment. Is.

  According to the present invention, in the glycerin difatty acid ester-rich oil containing a specific amount of ω3-unsaturated fatty acids with excellent health functions, the return odor peculiar to ω3-unsaturated fatty acids is remarkably improved, the flavor is good, and the low temperature resistance Therefore, it is possible to obtain an oil / fat composition excellent in appearance, familiar to the material, excellent texture, workability, emulsification and the like. Moreover, the application to various foodstuffs is possible, and it can be set as the oil-fat composition excellent in processing characteristics.

  The fat of component (A) used in the fat and oil composition of the present invention contains 20 to 95% by mass of glycerin difatty acid ester (DG) (hereinafter “mass%” is simply described as “%”). Further, it is preferably contained in an amount of 22 to 80%, particularly 25 to 50%, and more preferably less than 30 to 40% from the viewpoints of improvement of return odor, physiological effect, industrial productivity, and processing characteristics.

  In the glycerin difatty acid ester in the present invention, 15 to 90% of the constituent fatty acid is an ω3-unsaturated fatty acid, but it is further 30 to 80%, particularly 40 to 70%, especially 50 to 60%. It is preferable in terms of odor improvement, physiological effects, industrial productivity, and processing characteristics. Examples of the ω3 unsaturated fatty acid include α-linolenic acid (ALA, C18: 3), eicosapentaenoic acid (EPA, C20: 5), and docosahexaenoic acid (DHA, C22: 6). The content of docosahexaenoic acid in the ω3-unsaturated fatty acid is preferably 50% by mass or more, more preferably 60 to 98%, and particularly preferably 70 to 95%, from the viewpoint of physiological effect and return odor improvement.

  Of the fatty acids constituting the glycerin difatty acid ester, the content of saturated fatty acids is preferably 30% or less, more preferably 0 to 20%, especially 1 to 15%, and particularly 2 to 12%. It is preferable in terms of improvement, physiological effects, processing characteristics, and industrial productivity. As the saturated fatty acid, those having 14 to 24 carbon atoms, particularly 16 to 22 carbon atoms are preferable, and palmitic acid and stearic acid are most preferable. The short / medium chain saturated fatty acid having 13 or less carbon atoms is preferably 2% or less, more preferably 0 to 1% and substantially 0% from the viewpoint of flavor.

  In particular, the content of oleic acid (C18: 1) among the fatty acids constituting the glycerin difatty acid ester is preferably 0.1 to 50%, more preferably 3 to 30%, especially 5 to 20%, especially 8 -15% is preferable from the viewpoints of improved return odor, physiological effects, and fatty acid intake balance.

  The content of linoleic acid (C18: 2) among the fatty acids constituting the glycerin difatty acid ester is preferably 0.01 to 20%, more preferably 0.1 to 10%, especially 0.3 to 5%, 0.5 to 2% is preferable in terms of appearance and fatty acid intake balance.

  Among the fatty acids constituting the glycerin difatty acid ester, the content of trans-type unsaturated fatty acid is preferably 0 to 10%, more preferably 0.1 to 5%, particularly 0.5 to 3.5%. Is preferable in terms of physiological effects, improvement of return odor, processing characteristics, and industrial productivity. The remaining constituent fatty acids preferably have 14 to 24 carbon atoms, particularly 16 to 22 carbon atoms.

The content of glycerin trifatty acid ester (TG) in the oil and fat of component (A) used in the present invention is 4.9 to 79.9% in terms of physiological effects, industrial productivity, and processing characteristics. Is preferably 30 to 75%, in particular 50 to 70%, more preferably 60 to 65%.
The constituent fatty acid of the glycerin trifatty acid ester is preferably 70 to 100%, more preferably 80 to 99%, particularly 85 to 98%, especially 90 to 97% of unsaturated fatty acids having 10 to 24 carbon atoms and more preferably 16 to 22 carbon atoms. Preferably there is.
Of the constituent fatty acids, the content of linoleic acid is preferably less than 5% by mass, more preferably less than 3% by mass, and particularly preferably less than 2% by mass, from the viewpoint of appearance and fatty acid intake balance.

  The content of the glycerin monofatty acid ester (MG) in the oil and fat of the component (A) used in the present invention is 0.1 to 10% in terms of improved return odor, processing characteristics, industrial productivity, and the like. Is preferably 0.5 to 8%, more preferably 1 to 7%, and particularly preferably 1.5 to 5%. The constituent fatty acid of the glycerin monofatty acid ester is preferably the same constituent fatty acid as that of the glycerin difatty acid ester from the viewpoint of industrial productivity.

  In addition, the free fatty acid (salt) (FFA) contained in the fat of component (A) used in the present invention should be reduced to 10% or less, preferably 0.01 to 5%, and more preferably 0. A content of 02 to 2%, particularly 0.05 to 1%, particularly 0.1 to 0.5% is preferable from the viewpoints of improvement of return odor, processing characteristics, and industrial productivity.

  The origin of the component (A) fat used in the present invention may be either vegetable or animal fat. Specific examples of the raw material include fish oil such as bonito oil, sardine oil, and tuna oil, and vegetable oil such as linseed oil, perilla oil, soybean oil, and rapeseed oil. In addition, those obtained by separating and mixing these oils and fats, and those obtained by adjusting the fatty acid composition by hydrogenation or transesterification can be used as raw materials.

  The fats and oils of the component (A) used for this invention can be obtained by the esterification reaction of the fatty-acid derived fatty acid and glycerol mentioned above, the transesterification reaction of fats and oils and glycerol, etc. Excess monoacylglycerol produced by the reaction can be removed by molecular distillation or chromatography. These reactions can be carried out by chemical reaction using an alkali catalyst or the like, but the reaction is carried out under mildly enzymatic conditions using lipase having no 1,3-position selectivity and / or no position selectivity. Is preferable in terms of flavor and the like.

  The fat of component (A) used in the present invention is obtained by adding an organic carboxylic acid, a derivative thereof and / or a salt thereof to the fat obtained by the esterification reaction or transesterification reaction (hereinafter referred to as fat (A1)). It is preferable from the viewpoint of improving the return odor, improving the flavor, and improving the oxidation stability, by adding, mixing, stirring, etc., performing the treatment and performing purification operations such as washing with water, decoloring, and deodorizing. . Specific examples of the organic carboxylic acid and / or salt thereof include citric acid, succinic acid, maleic acid, oxalic acid, aconitic acid, itaconic acid, citraconic acid, tartaric acid, fumaric acid, malic acid, and / or a salt thereof. Among them, citric acid, tartaric acid, malic acid and / or a salt thereof are preferable. Examples of these derivatives include citric acid mono-diglyceride, succinic acid mono-diglyceride, lactic acid mono-diglyceride, and / or a salt thereof.

  Content of organic carboxylic acid, its derivative (s), and / or their salts is 0.001-10 mass parts with respect to 100 mass parts of fats and oils (A1), Furthermore, 0.01-5 mass parts, Especially 0.1-1 is. It is preferable to set it as a mass part, especially 0.05-0.5 mass part from the point which improves a return odor, makes a flavor favorable, and improves oxidation stability. The contact time between the fat (A1) and the organic carboxylic acid, derivative thereof and / or salt thereof is preferably 10 to 120 minutes, more preferably 20 to 60 minutes. The contact temperature is preferably 50 to 80 ° C, more preferably 60 to 70 ° C.

  The contacting method of the fat (A1) with the organic carboxylic acid, its derivative and / or their salt may be simply adding the organic carboxylic acid and / or their salt to the fat (A1), mixing and stirring. It is preferable to add an aqueous solution of organic carboxylic acid, a derivative thereof and / or a salt thereof so as to be in the range of the addition amount from the viewpoints of stirring efficiency, workability and the like. In this case, the concentration of the organic carboxylic acid, derivative thereof and / or salt thereof in the aqueous solution is 0.1 to 40% by mass, more preferably 1 to 20% by mass, and particularly 5 to 12% by mass. It is preferable from the viewpoints of efficiency and ease of work.

  The fat mixed with the aqueous solution of the organic carboxylic acid, derivative thereof and / or salt thereof is preferably washed successively with water. In addition, it is not necessary to perform dehydration operation and adsorption operation. Washing with water is preferably carried out by mixing the fats and oils with water and then separating the water. In addition, the water used for this water washing may contain lower alcohols, such as about 0.01-10 mass% ethanol and isopropanol. Here, the amount of water used for one water washing is preferably 5 to 200% by mass, more preferably 10 to 50% by mass with respect to the fats and oils. The washing temperature is preferably 25 to 95 ° C. Washing with water is performed 1 to 5 times.

  When contacting organic carboxylic acid, its derivative (s), and / or their salts as an aqueous solution, it may be continuously mixed for 0.1 to 10 minutes, preferably 0.2 to 5 minutes, using a line mixer. Here, the line mixer refers to a device that mixes while flowing a fluid using a baffle plate or a mechanical stirrer provided in a pipe. Moreover, mixing time means the average residence time of the fats and oils in a line mixer. The use of the line mixer is industrially advantageous because it is continuously mixed by passing through the mixer and the oil and fat do not need to stay in the tank. The mixing is preferably performed by mechanical stirring and mixing. The tip peripheral speed of the mixing blade of the mixer is 1 to 20 m / s, particularly 2 to 10 m / s. It is preferable from the point.

  By the organic carboxylic acid treatment, the amount of transition metal in the fat (A1) before the deodorization treatment is 5 ppm or less, further 2 ppm or less, particularly 1 ppm or less to improve the return odor, improve the flavor and improve the oxidation. This is preferable from the viewpoint of improving stability.

  In addition, from the viewpoint of setting the amount of transition metal in the fat (A1) to 5 ppm or less, in addition to using organic carboxylic acid, derivatives thereof and / or salts thereof, for example, adsorption method, chromatography, chelating agent treatment, etc. It can also be adopted. Examples of the adsorption method include adsorption methods using activated clay, acidic clay, silica gel, zeolite, activated carbon, ion exchange resin and the like. Specifically, for example, after mixing the fats and oils with the adsorbent, the adsorbents and the fats and oils may be filtered, or the fats and oils may be circulated through the adsorption tower filled with the adsorbent. Chromatography includes a method using an organic solvent as an eluent and zeolite as a fixed layer. Specifically, for example, it is performed by performing a pseudo moving bed type operation.

  It is preferable to deodorize the fats and oils that have been brought into contact with the fats and oils (A1) and the organic carboxylic acid, derivatives thereof and / or salts thereof. As the deodorizing treatment, steam distillation is preferable. Steam distillation is preferably performed under conditions of 180 ° C. or less from the viewpoint of suppressing the decrease in the purity of diglyceride and improving the flavor. The amount of water vapor to be used is preferably 0.5 to 20% by mass, particularly 1 to 10% by mass with respect to the fat and oil.

  Examples of the deodorizing method include tray deodorization, thin film deodorization, etc., but the thin film is used to improve the return odor, improve the flavor, improve the oxidation stability, and reduce the trans unsaturated fatty acid. Deodorization is preferred. Thin film deodorization is a method in which the oil is brought into contact with water vapor in a thin film state. As the contact means, flowing down in the distillation column filled with the structure-packed material and circulating water vapor so as to counter-current contact with the oil improves the return odor and improves the flavor. In addition, it is preferable from the viewpoint of improving oxidation stability and reducing trans-type unsaturated fatty acids. The fats and oils form a thin film to flow down the surface of the packing when flowing down the distillation column filled with the structure packing.

The conditions for bringing the oil and fat into contact with water vapor are preferably the following conditions from the viewpoints of economy, deodorization efficiency, and quality. Oil temperature is preferably 140 to 250 ° C., more preferably 150 to 220 ° C., particularly preferably 160 to 190 ° C., contact time is preferably 1 to 15 minutes, more preferably 1 to 10 minutes, and particularly preferably 2 to 10 minutes. 2 kPa, more preferably 0.05 to 1 kPa, and particularly preferably 0.1 to 0.8 kPa, and the amount of water vapor is 0.1 to 10% by weight, more preferably 0.2 to 5% by weight, particularly 0.2 to It is preferable that it is 2 mass%.
The flow rate of the fats and oils is preferably 1 to 20 ton / h, more preferably ^{2 to} 10 ton / h per unit cross-sectional area (m ² ) of the filler from the viewpoint of stability of deodorizing operation, deodorizing efficiency, and productivity.
The structure filler is preferably a regular filler having a specific surface area of 200 to 700 m <2> / m <3>.

  In the oil and fat composition of the present invention, the phosphatidic acid of component (B) and / or its salt is added in an amount of 0.003 to 100 parts by mass of component (A) in terms of improved return odor, low temperature resistance, processing characteristics and flavor. 10 to 10 parts by mass, preferably 0.005 to 5 parts by mass, more preferably 0.01 to 3 parts by mass, further 0.015 to 1 part by mass, and particularly 0.018 to 0.1 parts by mass. Parts, particularly 0.02 to 0.05 parts by mass.

  The component (B) phosphatidic acid and / or salt thereof used in the present invention may be used in combination with other phospholipids. However, in terms of improved return odor, low temperature resistance, flavor, and processing characteristics, The phosphatidic acid and / or salt thereof is preferably contained in an amount of 30% or more, more preferably 60 or more, particularly preferably 80% or more. The upper limit is 100%, but from the viewpoint of industrial productivity, it is preferably 95% or less, more preferably 93% or less, and particularly preferably 90% or less. By setting the content of the phosphatidic acid and / or salt thereof of the component (B) in the phospholipid to 30% or more, not only the return odor is improved, but a good flavor with a refreshing feeling is imparted.

  In addition to the component (B) phosphatidic acid and / or salt thereof, examples of the phospholipid used in the present invention include phosphatidylcholine (PC), phosphatidylethanolamine (PE), phosphatidylinositol (PI), and the like. You may contain food materials, such as soybean oil, rapeseed oil, and corn oil. The content of lyso form and PI in the phospholipid is preferably 10% or less, respectively.

  Examples of the material containing phosphatidic acid and / or a salt thereof include Benecoat BMI-40L (Kao Corporation), Sun Lecithin W-1 (Taiyo Kagaku Corporation), and the like.

  The component (B) used in the present invention is obtained by subjecting natural soybean lecithin, egg yolk lecithin and the like to an enzyme treatment and a modification reaction. After the modification, it is produced by washing and extraction operations using a solvent such as ethanol and hexane, followed by purification.

  Moreover, it is preferable to contain the antioxidant of a component (C) in the oil-fat composition of this invention. The presence of the component (B) not only increases the oil solubility of the component (C), but also exhibits a synergistic effect with the component (B), and exhibits a remarkable return odor improving effect and low-temperature resistance.

The content of the antioxidant is preferably 0.01 to 2 parts by mass, more preferably 0.012 to 100 parts by mass with respect to 100 parts by mass of the component (A) from the viewpoints of return odor improvement, coloring prevention, low temperature resistance and the like. It is preferably 1 part by weight, especially 0.013 to 0.1 part by weight, more preferably 0.015 to 0.03 part by weight.
In the CDM test method (2.5.1.2-1996) described in Japan Oil Chemistry Association “Standard Oil Analysis Test Method”, it is preferable to add an antioxidant so that the induction time is 0.5 hours or more. Further, it is preferably 1 to 20 hours, particularly 2 to 10 hours, particularly 3 to 4 hours. The induction time referred to here is the apparatus of the test method, in which clean air is fed while heating the fat sample at 120 ° C., and volatile substances generated by oxidation are collected in water. This is the time (hr) until the bending point changes.

  Any antioxidant can be used as long as it is usually used in foods. For example, natural antioxidants such as catechin, tocopherol, butylhydroxytoluene (BHT), butylhydroxyanisole (BHA), tertiary butylhydroquinone (TBHQ), ascorbic acid or a derivative thereof, rosemary extract, and the like can be mentioned. , Tocopherol, ascorbic acid or a derivative thereof, and rosemary extract are preferable, and it is more preferable to use these in combination.

As tocopherol, α, β, γ, δ-tocopherol or a mixture thereof can be used. In particular, from the viewpoint of oxidation stability, δ-tocopherol is preferable. Tocopherol is preferably formulated as a commercial product of vitamin E. For example, Emix D, Emix 80 (Eisai Co., Ltd.), MDE-6000 (Yatsushiro Co., Ltd.), E Oil-400 (RIKEN Vitamin ( Co., Ltd.), ET-840R (Honen Corporation) and the like.
In the present invention, the content of vitamin E is preferably 0.0001 to 1 part by mass, more preferably 0.0005 to 0.01 part by mass, particularly preferably 0.0008 to 100 parts by mass of component (A) as tocopherol. 0.005 parts by mass, especially 0.001 to 0.002 parts by mass are preferred.

Ascorbic acid or a derivative thereof, higher fatty acid esters, for example, those having an acyl group having 12 to 22 carbon atoms are more preferable, L-ascorbic acid palmitic acid ester, L-ascorbic acid stearic acid ester are particularly preferable, and L-ascorbic acid. Acid palmitate is most preferred.
In the present invention, the content of ascorbic acid or a derivative thereof is preferably 0.0001 to 1 part by weight, more preferably 0.001 to 0.5 parts by weight, particularly 100 parts by weight as component (A). 0.003 to 0.1 parts by mass, particularly 0.005 to 0.01 parts by mass is preferred.

The catechin is preferably extracted from tea with a solvent such as water or ethanol, and more preferably purified from decaffeinated.
In the present invention, the content of catechin is preferably 0.0001 to 1 part by weight, more preferably 0.0005 to 0.1 part by weight, and particularly preferably 0.001 to 0 parts by weight as catechin with respect to 100 parts by weight of component (A). .05 parts by mass, especially 0.002 to 0.01 parts by mass is preferred.

  As the rosemary extract, a powder raw material is preferably a residue after oil extraction by steam distillation, or one extracted with acetone, ethanol, methanol, ethyl ether, hexane or the like. In the present invention, the content of the rosemary extract is preferably from 0.0001 to 5 parts by mass, more preferably from 0.001 to 1 part by mass, particularly from 0.01 to 0. 5 parts by mass, especially 0.02 to 0.1 parts by mass are preferred.

  In the oil and fat composition used in the present invention, it is preferable to further contain plant sterols as component (D). Plant sterols are components having a cholesterol lowering effect, and in the present invention, the component (D) is a mass of (D) :( A) = 0.0005: 1-5: 1 with respect to the component (A). The ratio is preferably 0.003: 1 to 1: 1, particularly 0.012: 1 to 0.2: 1, and more preferably 0.02: 1 to 0.047: 1. This is desirable in terms of physiological effects, appearance, processing characteristics, and the like. Here, as plant sterols, for example, α-sitosterol, β-sitosterol, stigmasterol, campesterol, α-sitostanol, β-sitostanol, stigmasteranol, campestanol, cycloartenol and the like, and These fatty acid esters, ferulic acid esters, cinnamic acid esters and the like are exemplified. In the present invention, it is preferable to use plant sterols and / or plant sterol fatty acid esters as plant sterols.

  The oil and fat composition of the present invention preferably further contains an organic acid and / or a salt thereof. Examples of the salt of the organic acid include alkali metal and alkaline earth metal salts, and sodium salt and calcium salt are preferable. The content of the organic acid and / or salt thereof is preferably 0.0001 to 1 part by mass, more preferably 0.0002 to 0.5 part by mass, and further 0.0003 to 0, relative to 100 parts by mass of the component (A). .1 part by mass, particularly 0.0004 to 0.01 part by mass is preferable in terms of improving the return odor and flavor. The organic acid and / or salt thereof needs to have 2 to 8 carbon atoms, preferably 2 to 6 and more preferably 4 to 6. Of these, hydroxycarboxylic acids having 2 to 8 carbon atoms, dicarboxylic acids, tricarboxylic acids, salts thereof, and derivatives thereof are preferable. Specific examples of these hydroxycarboxylic acids, dicarboxylic acids, and tricarboxylic acids are citric acid, succinic acid, maleic acid, oxalic acid, aconitic acid, itaconic acid, citraconic acid, tartaric acid, fumaric acid, and malic acid. Citric acid, tartaric acid, and malic acid are preferable. Examples of these derivatives include citric acid mono-diglyceride, succinic acid mono-diglyceride, and lactic acid mono-diglyceride.

  As the organic acid, an extract containing an organic acid or a herbal medicine can be used. As the extract and herbal medicine, products marketed in the form of powders, concentrates and the like produced by extracting from fruits such as lemon, yuzu and plum can be used. When using an extract or a crude drug, the organic acid contained in the extract or the crude drug may be added within the above range.

In the present invention, the content of the organic acid in the oil and fat composition can be measured by an HPLC method, a colorimetric method using orthonitrophenylhydrazine, or the like. For example, the colorimetric measurement of citric acid is performed according to the following method.
Add 20 g of oil heated to 60 ° C. into a 100 mL separatory funnel, add 5 mL of warm water at 60 ° C., and shake vigorously for 2 minutes. Next, the mixture is allowed to stand for separation, and the lower layer is used as a sample solution. Put 2 mL of this sample solution, 1 mL of ONPH solution (* 1) and 1 mL of ETC solution (* 2) into a 10 mL volumetric flask, seal tightly and heat at 40 ° C. for 30 minutes. Next, 1 mL of 1.5 mol / L sodium hydroxide solution is added and heated at 60 ° C. for 15 minutes. After cooling to room temperature, the absorbance at 540 nm is measured. The citric acid content is determined by the following formula from a calibration curve prepared using an aqueous citric acid solution with a known concentration.

  Citric acid content in fats and oils = citric acid amount determined from calibration curve ÷ 4

* 1 ONPH solution: A solution in which 53.6 mg of orthonitrophenylhydrazine hydrochloride (ONPH) is dissolved in 10 mL of 0.2 mol / L hydrochloric acid.
* 2 ETC solution: A solution in which 287.6 mg of 1-ethyl-3- (3-dimethylaminopropyl) -carbodiimide hydrochloride (ETC) was dissolved in 10 mL of a 6% aqueous pyridine solution.

  In the oil and fat composition of the present invention, phosphatidic acid and / or a salt thereof, further an antioxidant, if necessary, a plant sterol, silicone, an organic acid (salt), and the like are added to the oil and fat having the above composition, and the mixture is appropriately heated and stirred. Can be obtained. Antioxidants such as ascorbic acid derivatives and tocopherols may be added after dissolving in a solvent such as ethanol in advance.

The oil and fat composition thus obtained is good in terms of flavor, texture, appearance, workability, emulsification, familiarity with raw materials, etc., and can be applied to various foods.
As food, it can be used for processed oils and fats containing the oil and fat composition as part of the food. Examples of such processed oils and fats include health foods, functional foods, foods for specified health use, and the like that exhibit specific functions to promote health. Specific products include bakery foods such as bread, cakes, biscuits, pies, pizza crusts and bakery mixes, oil-in-water emulsions such as soups, sauces, dressings, mayonnaise, coffee whiteners, ice creams, whipped creams, Water-in-oil emulsion such as margarine, spread, butter cream, snack confectionery such as potato chips, confectionery such as chocolate, caramel, candy, dessert, meat processed food such as ham, sausage, hamburger, milk, cheese, yogurt, etc. Examples include dairy products, dough, enrober oils and fats, filling oils and fats, noodles, frozen foods, retort foods, beverages and roux. In addition to the oil and fat composition described above, food raw materials generally used can be added depending on the type of processed oil and fat food. The amount of the oil / fat composition of the present invention to be added to food varies depending on the type of food, but is generally 0.1 to 100%, particularly preferably 1 to 80%.

  In addition, from the relation of formulation preparation, when fats and oils derived from food raw materials are included, the mass ratio of the fats and oils derived from food raw materials and the oil and fat composition of the present invention is preferably 95: 5 to 1:99, 95 : 5 to 5:95 is more preferable, 85:15 to 5:95 is more preferable, and 40:60 to 5:95 is particularly preferable.

  The oil and fat composition of the present invention can be used for an oil-in-water emulsion. The mass ratio of the oil phase to the water phase is oil phase / water phase = 1/99 to 90/10, preferably 10/90 to 80/20, and particularly preferably 30/70 to 75/25. It is preferable to contain an emulsifier in an amount of 0.01 to 5%, particularly 0.05 to 3%. Examples of emulsifiers include egg protein, soybean protein, milk protein, proteins separated from these proteins, various proteins such as (partial) degradation products of these proteins, sucrose fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester Glycerin fatty acid monoester, polyglycerin fatty acid ester, polyglycerin condensed ricinoleic acid ester, glycerin organic acid fatty acid ester, propylene glycol fatty acid ester, lecithin or enzymatic degradation product thereof. The stabilizer is preferably contained in an amount of 0 to 5%, particularly 0.01 to 2%. Examples of the stabilizer include thickening polysaccharides such as xanthan gum, gellan gum, guar gum, carrageenan, pectin, tragacanth gum, and konjac mannan, starch, and the like. In addition, salt, sugar, vinegar, fruit juice, seasonings such as seasonings, flavors such as spices and flavors, colorants, preservatives, antioxidants, and the like can be used. Using these raw materials, oil-in-water type oil-and-fat-containing foods such as mayonnaise, dressing, coffee whitener, ice cream, whipped cream and beverages can be prepared by conventional methods.

  The oil and fat composition of the present invention can be used for a water-in-oil emulsion. The mass ratio of the water phase to the oil phase is water phase / oil phase = 85/15 to 1/99, preferably 80/20 to 10/90, and particularly preferably 70/30 to 35/65. It is preferable to contain an emulsifier in an amount of 0.01 to 5%, particularly 0.05 to 3%. Examples of emulsifiers include egg protein, soybean protein, milk protein, proteins separated from these proteins, various proteins such as (partial) degradation products of these proteins, sucrose fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester Glycerin fatty acid monoester, polyglycerin fatty acid ester, polyglycerin condensed ricinoleic acid ester, glycerin organic acid fatty acid ester, propylene glycol fatty acid ester, lecithin or enzymatic degradation product thereof. Also, salt, sugar, vinegar, fruit juice, seasonings such as seasonings, flavors such as spices and flavors, stabilizers such as thickening polysaccharides and starches, colorants, preservatives, antioxidants, etc. are used. be able to. Using these raw materials, a water-in-oil type oil-containing food such as margarine, spread, butter cream and the like can be prepared by a conventional method.

  The oil and fat composition of the present invention has an excellent physiological activity such as an anti-obesity action, an anti-platelet aggregation inhibitory action, and a brain function improvement by using a glycerin difatty acid ester containing an ω3-unsaturated fatty acid such as DHA as a main component. Have Because of having such excellent properties, the oil and fat composition of the present invention can be used for pharmaceuticals in the form of capsules, tablets, granules, powders, liquids, gels and the like. As pharmaceuticals, in addition to the oil and fat composition described above, excipients, disintegrants, binders, lubricants, surfactants, alcohols, water, water-soluble polymers, sweeteners, and flavoring agents that are generally used depending on the form. In addition, it can be produced by adding a sour agent or the like. The amount of the oil / fat composition of the present invention to be added to a pharmaceutical product varies depending on the use and form of the pharmaceutical product, but is generally 0.1 to 80%, more preferably 0.2 to 50%, and particularly 0.5 to 30%. Is preferred. Moreover, it is preferable to administer 0.2-50g per day as an oil-fat composition divided into 1 to several times. The administration period is preferably 1 month or more, 2 months or more, and 3 to 12 months.

  The oil and fat composition of the present invention can be used for feed. As feed, for example, feed for livestock used for cattle, pigs, chickens, sheep, horses, goats, etc., feed for small animals used for rabbits, rats, mice, etc., feed for seafood used for eel, Thailand, hamachi, shrimp, etc. Examples include pet food used for dogs, cats, small birds, squirrels, and the like. The blending amount of the oil and fat composition of the present invention in the feed varies depending on the use of the feed and the like, but is generally 1 to 30%, particularly preferably 1 to 20%. The oil and fat composition of the present invention can be used by replacing all or part of the oil and fat in the feed.

In addition to the oil and fat composition described above, the feed is produced by mixing with commonly used feed ingredients such as meat, protein, grains, bran, potatoes, sugars, vegetables, vitamins, minerals and the like.
Meats include cattle, pigs, sheep (mutton or lamb), rabbits, kangaroos and other livestock meat, beef and its by-products, processed products (rendered products of meatballs, meatbone meal, chicken meal, etc.), tuna And seafood such as bonito, horse mackerel, sardines, scallops, scallops, and fish meal (fish meal). Examples of the protein include milk proteins such as casein and whey, animal proteins such as egg protein, and plant proteins such as soybean protein. Examples of cereals include wheat, barley, rye, milo, and corn. Rice bran includes rice bran and bran. Examples of potatoes include soybean meal. The total amount of meat, protein, grains, bran and potatoes in the feed is preferably 5 to 93.9%.

  Examples of the saccharide include glucose, oligosaccharide, sugar, molasses, starch, liquid sugar and the like, and preferably 5 to 80% in the feed. As vegetables, vegetable extracts etc. are illustrated and it is preferable to contain 1-30% in feed. Examples of vitamins include A, B1, B2, D, E, niacin, pantothenic acid, carotene, and the like, and 0.05 to 10% in feed is preferable. Examples of minerals include calcium, phosphorus, sodium, potassium, iron, magnesium, zinc and the like, and it is preferable to contain 0.05 to 10% in the feed. In addition, a gelling agent, a shape-retaining agent, a pH adjuster, a seasoning, a preservative, a nutritional reinforcing agent and the like that are generally used in feed can be contained as necessary.

The following fats and oils were produced.
[Manufacture of fats and oils 1]
Tuna oil (Sanki Feed Industry Co., Ltd.) was hydrolyzed with lipase-AY (Amano Enzyme Co., Ltd.), and then centrifuged to separate the oil phase, and the raw oil / fat composition (AV value, 123.3). ). By subjecting this to distillation, free fatty acids were removed, and fats and oils A were prepared through decolorization and deodorization steps. The acid value of the fat A was 0.2. Table 1 shows the fatty acid composition and glyceride composition of fat A. The acid value was measured based on the standard fat analysis method (2.3.1-1996). The fatty acid composition was analyzed by gas chromatography, and the glyceride composition was analyzed by liquid chromatography. In the table, FA represents free fatty acid, MG represents glycerin monofatty acid ester, DG represents glycerin difatty acid ester, and TG represents glycerin trifatty acid ester.

(Preparation of phospholipid)
A modification reaction was performed by enzymatic treatment of soybean lecithin to prepare phospholipids X to Z containing phosphatidic acid (PA), phosphatidylcholine (PC), and phosphatidylethanolamine (PE). Phospholipid X contains 100 parts by mass of Benecoat BMI 40L (Kao Corporation) containing 40% PA and 60% corn oil, and L-α phosphatidylcholine as a PC, a soybean-derived reagent (Wako Pure Chemical Industries, Ltd.) 73 parts by mass, 60 parts by mass of L-α phosphatidylethanolamine distearoyl reagent (Wako Pure Chemical Industries, Ltd.) and 100 parts by mass of corn oil were used as PE. Phospholipid Y is 100 parts by mass of Benecoat BMI 40L (Kao Corporation), 5300 parts by mass of L-α phosphatidylcholine as a PC, a soybean-derived reagent (Wako Pure Chemical Industries, Ltd.), and L-α phosphatidylethanol as PE. A mixture of 1100 parts by mass of amine distearoyl reagent (Wako Pure Chemical Industries, Ltd.) and 3350 parts by mass of corn oil was used. Phospholipid Z used was Benecoat BMI 40L (Kao Corporation) containing 40% PA and 60% corn oil.

[Analysis method]
(1) Fatty acid glyceride composition 2 mL of tetrahydrofuran (THF) is dissolved in 0.1 g of sample oil. After dissolution, it was filtered through a tetrafluoroethylene resin membrane (PTFE membrane, Advantech Toyo Co., Ltd.) and subjected to liquid chromatography (HPLC) to measure the glyceride composition.
HPLC conditions Apparatus: Hitachi, Ltd. Column; G-2500, G-2000 (Tosoh Corporation)
Column temperature: 30 ° C
Detector: L-3350 RI Monitor (Hitachi, Ltd.)
Flow rate: THF, 0.4 mL / min (2) Fatty acid composition of glyceride The oil was analyzed according to the Japan Oil Chemistry Association "standard oil analysis test method" (2.4.2.2.-1996).
(3) Composition of phospholipid The contents of phosphatidic acid (PA), phosphatidylcholine (PC), and phosphatidylethanolamine (PE), which are typical phospholipids, are oil chemistry, 35 (12), P1018 to 1024, ( 1986). The molecular weights were determined as PA, PC, and PE 704, 790, and 748, respectively.

[Return odor test]
For fats and oils A, phospholipids X to Z, tea extract (catechin), rosemary extract (RM), vitamin C palmitate (VCP), tocopherol (VE) antioxidants were added or not added, Table 3 Inventive products 1 to 12 and comparative products 1 to 5 shown in FIG. Table 3 shows the results of sensory evaluation of these blending compositions and odors during heating. As a method for evaluating the return odor, 3 g of a sample was weighed and applied to a stainless steel petri dish, and then the petri dish was heated with a hot plate to evaluate the smell. The temperature was 100 ° C., and samples after 60 seconds and 240 seconds were evaluated.

[Evaluation criteria for return odor]
Return odor ○: No smell △: Slight fish odor ×: Fish odor

[Low temperature resistance test]
Invention products 1 to 12 and comparative products 1 to 5 shown in Table 3 were prepared, and low temperature resistance was evaluated by measuring the cloud point. The evaluation method uses FP90 / 81HT (Mettler Toledo Co., Ltd.) which is a cloud point measuring device, and after storing the products 1 to 12 of the present invention and the comparative products 1 to 5 in a thermostatic bath at 30 ° C. for 1 hour, The mixture was cooled from 30 ° C. to −13 ° C. at a rate of 0.5 ° C./min, the light transmittance was measured over time, and the inflection point was taken as the cloud point.

From Table 3, it was found that the return odor of fish odor at 100 ° C. can be reduced by increasing the amount of PA added to fat A. It was also found that the effect of reducing the return odor of fishy odor is enhanced by further adding and using tea extract typified by catechin, rosemary extract, vitamin C palmitate, and tocopherol.
It was also found that by increasing the amount of PA added to the fat A, the cloud point can be reduced and the low-temperature resistance is improved regardless of the phospholipid origin. Due to this characteristic, even when the food using the oil composition of the present invention is actually refrigerated and stored in a refrigerator or the like, crystals do not form, the appearance of the food is kept good, and in the case of an emulsified food, storage stability is maintained. Can be expected to be effective. It was also found that the low temperature tolerance improving effect was enhanced by further adding and using tea extract typified by catechin, rosemary extract, vitamin C palmitate and tocopherol.

[Manufacture of fats and oils 2]
Tuna oil (manufactured by Sanki Feed Industry Co., Ltd.) was hydrolyzed with lipase-AY (Amano Enzyme Co., Ltd.), and then centrifuged to separate the oil phase and to obtain a raw oil / fat composition (AV value, 123. 3). This was subjected to a distillation operation to remove free fatty acids and prepare a deoxidized oil. The acid value was 0.8. An aqueous solution containing 0.2 part by mass of citric acid with respect to 100 parts by mass of deacidified oil was prepared and added to the oil. After stirring at 70 ° C. for 30 minutes, washing with water, decolorization and deodorization were carried out to produce fat and oil A ′. Table 4 shows the fatty acid composition and glyceride composition of the fat A ′.

[Return odor and oxidation stability test]
For fats and oils A or A ′, phospholipid Z, tea extract (catechin), rosemary extract (RM), vitamin C palmitate (VCP), tocopherol (VE) antioxidant is added or not added, Invention products 13 and 14 shown in Table 5 and Comparative product 6 were prepared. Table 5 shows the composition of these compounds and the results of sensory evaluation of the odor during heating. As a method for evaluating the return odor, 15 g of a test product was weighed and added to a glass bottle (Nippon Rika Glass Co., Ltd.) having an inner diameter of 24 mm and a height of 55 mm with a cap. Four samples were prepared for each test product. The product was stored in a 60 ° C. thermostatic chamber protected from light while being exposed to the atmosphere. Before storage, after storage, 1, 3 and 5 hours, each sample bottle was taken out and cooled to 20-30 ° C. in a desiccator. After cooling, the peroxide value and the return odor were evaluated, and the average value of 4 samples of each test product was calculated.

[Peroxide value measurement method]
The analysis was carried out according to the Japan Oil Chemistry Association "standard oil and fat analysis test method" (2.4-1996). First, a mixed solution of chloroform and acetic acid in a ratio of 2: 3 was prepared as a solvent (solution A). Further, a saturated aqueous potassium iodide solution, a 0.01 mol / l sodium thiosulfate standard solution, and an aqueous starch solution were used as titrants. An oil and fat sample was correctly weighed in an Erlenmeyer flask, dissolved in solution A, a saturated potassium iodide aqueous solution was dropped, and the mixture was shaken and reacted. Further water was added and the mixture was shaken for 1 minute and then allowed to stand. Starch solution was added as an indicator and titrated with sodium thiosulfate standard solution.

  From Table 5, the comparative product without acid treatment and the product without PA (Comparative Product 6) tended to have a higher peroxide value due to storage and a stronger return odor. Moreover, what performed only PA mixing | blending (this invention product 13) did not raise a peroxide value easily, and the return odor reduced. Furthermore, in the oil-treated oil and fat that was also subjected to PA blending (Invention product 14), the increase in the peroxide value was further suppressed, and the return odor was further reduced.

Claims (6)

Next component (A) The fats and oils composition which contains 0.003-10 mass parts of components (B) with respect to 100 mass parts .
(A) Oil and fat containing glycerin monofatty acid ester 0.1 to 10% by mass, glycerin difatty acid ester 20 to 95% by mass, glycerin trifatty acid ester 4.9 to 79.9% by mass, and glycerin difatty acid ω3-unsaturated fatty acid content in the fatty acid constituting the ester is 30-90 wt% oil fat (B) phosphatidic acid and / or salts thereof   Furthermore, the fat and oil composition of Claim 1 which contains 0.01-2 mass parts of component (C) antioxidant with respect to 100 mass parts of component (A).   Furthermore, the fats and oils composition of Claim 1 or 2 which contains a component (D) plant sterol by the mass ratio of (D) :( A) = 0.0005: 1-5: 1 with respect to the component (A). object.   The fat and oil composition according to any one of claims 1 to 3, wherein the content of docosahexaenoic acid in the ω3 unsaturated fatty acid is 50% by mass or more.   The oil and fat of component (A) is obtained by adding an organic carboxylic acid, a derivative thereof and / or a salt thereof to an oil or fat composition obtained by esterification reaction of fatty acid derived from fat and oil or glycerin and transesterification reaction of fat and glycerin. The oil / fat composition according to any one of claims 1 to 4, which is produced by performing a deodorizing treatment after the addition.   Deodorizing treatment is performed after adding an organic carboxylic acid, a derivative thereof and / or a salt thereof to an oil or fat composition obtained by esterification reaction of fatty acid derived from fat or oil and glycerin or transesterification reaction between fat or glycerin. The manufacturing method of the oil-fat composition of Claim 1 which adds 0.003-10 mass parts of (B) phosphatidic acid and / or its salt with respect to 100 mass parts of components (A) obtained by this.