JPH06172782A - Powder of fat and oil containing highly unsaturated fatty acid - Google Patents

Abstract

PURPOSE:To obtain fat and oil powder having high oxidation stability by using a fat and oil containing highly unsaturated fatty acids and monoglycerides. CONSTITUTION:A fat and oil containing (at least 0.1wt.%) monoglyceride containing highly unsaturated fatty acids such as alpha-linolenic acid, gamma-linolenic acid, dihomo-gamma-linolenic acid, arachidonic acid, eicosapentaenoic acid and docosahexanoic acid as the constituent fatty acids is mixed with a phospholipid and an antioxidant such as tocopherol. The obtained mixture is uniformly emulsified and dispersed in a solution of an excipient comprising a protein such as casein or soy been protein, its decomposition product and a sugar such as milk sugar or starch. The obtained dispersion is dried by freeze drying or air drying to obtain the fat and oil powder of high oxidation stability.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a highly unsaturated fatty acid-containing oil and fat powder, and more particularly to a highly unsaturated fatty acid-containing oil and fat powder having excellent oxidation stability.

[0002]

BACKGROUND OF THE INVENTION Polyunsaturated fatty acids (hereinafter abbreviated as PUFA)
Due to its wide range of physiological activities, it is considered to be used in foods, pharmaceuticals, feeds, etc., and in some fields it has already been implemented ("Development and application of functional lipids", supervised by Kiyotaka Sato et al.,
CMC, (1992)).

Here, PUFA means α-linolenic acid, γ-
Linolenic acid, dihomo-γ-linolenic acid, arachidonic acid,
It refers to a fatty acid group composed of one or more selected from eicosapentaenoic acid and docosahexaenoic acid.

[0004]

However, in general, PUFA
Because of its extremely fast oxidation, most of the products currently on the market are enclosed in gelatin soft capsules, etc., or stored at low temperature in a container filled with nitrogen gas,
There are restrictions when used for the above purposes. In order to solve such problems, a method for producing a PUFA-containing oil / fat powder having high oxidation stability is disclosed in JP-A-60-49097, JP-A-60-49097, and JP-A-62-49097.
-126933, JP 62-158213, JP 63-44844
No. 3, JP-A-3-297364 and other methods have been proposed,
These methods are insufficient to prevent the progress of oxidation.

On the other hand, monoglyceride (hereinafter abbreviated as MG) is used as an emulsifier in a wide range of industrial fields.
It is also used in large quantities as glycerin fatty acid ester for foods ("Food emulsifiers and emulsification technology", Hygiene Technical Association).
(1979)). Usually, PUFA is present in the form of glyceride (mainly triglyceride, hereinafter abbreviated as TG). However, PUFA containing MG (hereinafter referred to as “FAFA”) is hydrolyzed enzymatically or nonenzymatically. , PUFA-MG) can be adjusted. For enzymatically adjusting MG, for example, a lipase-catalyzed hydrolysis method of TG (JP-A-60-102192).
No. 6, JP-A-62-228289, JP-A-3-103499, JP-A-3-
108489, JP-A-3-187385, etc.), transesterification (synthesis) method (JP-A-59-118094, JP-A-59-118095, JP-A-61-257192, JP-A-62-201591) , JP-A-63-29
6698, JP-A-3-262492, etc.) and many other methods are known. Moreover, in order to non-enzymatically adjust MG, "Emulsifiers for Food and Emulsification Technology, Hygiene Technology Society (1979)",
Many methods are known, including the method described in Japanese Patent Laid-Open No. 1-268663.

However, nothing is known about the oxidative stability of fats and oils containing PUFA-MG.
Phospholipids typified by soybean lecithin and egg yolk lecithin are particularly effective in preventing the oxidation of ω-3 PUFA, as disclosed in JP-A-61-112020, JP-A-3-297364 and Hara Setsuko. Others: Known as shown in Oil Chemistry, 41, 130-135 (1992), etc. However, the antioxidant effect of the addition of phospholipids to the oil / fat powder containing PUFA-MG is not known.

As described above, it has been known individually about the powdering of PUFA, the method of adjusting MG, the antioxidant effect of adding phospholipids to PUFA, etc. It has not been known to obtain PUFA-containing powders, and thus there have been limits to the expansion of PUFA applications.

The present invention has been made in view of the conventional problems as described above, and an object thereof is to use PUFA as a functional oil component having physiological activity in foods, pharmaceuticals, feeds, etc. In expanding the above, it is an object to provide a highly unsaturated fatty acid-containing oil / fat powder having excellent oxidation stability.

[0009]

[Means for Solving the Problems] In order to achieve the above object, as a result of intensive studies to obtain PUFA powders having excellent oxidation stability, as a result, fats and oils containing PUFA-MG have been added as antioxidants such as phospholipids and tocopherols. After mixing with, protein such as casein, soybean protein, etc. and their degradation products or sugar, etc. are uniformly emulsified and dispersed, and this is spray dried (SD, spray dried), freeze dried (FD, freeze dried). ), It was found that a PUFA-containing oil / fat powder excellent in oxidation stability can be obtained by drying by means such as hot air drying (AD), and the present invention has been accomplished. Details will be described below.

As a PUFA raw material having physiological activity, α-
All glycerolipids having one or more PUFA molecules such as linolenic acid, γ-linolenic acid, dihomo-γ-linolenic acid, arachidonic acid, eicosapentaenoic acid and docosahexaenoic acid as its constituent fatty acids are included. For example, linseed oil, perilla oil (α-linolenic acid raw material), fungal lipids such as filamentous fungi (γ-linolenic acid, dihomo-γ-linolenic acid, arachidonic acid, eicosapentaenoic acid raw material), fish oil (eicosapentaenoic acid, Docosahexaenoic acid raw material) and the like, and any glycerolipid containing 5.0% (weight ratio) or more of these functional PUFAs in the constituent fatty acids is regarded as the PUFA raw material used in the present invention.

Fats and oils containing PUFA-MG are prepared enzymatically or non-enzymatically. As a method for enzymatically adjusting fats and oils containing PUFA-MG, for example, when TG is used as glycerolipid, it is general to use lipase as a catalyst,
It is known as described above. As a treatment method, various methods such as a batch method and a continuous method (bioreactor method) are known. In the present invention, fat or oil to be a product contains 0.1% or more of MG by any enzymatic means. If you do, you can reach your goal. As a non-enzymatic method for preparing fats and oils containing PUFA-MG, for example, when TG is used as a raw material,
There are numerous methods based on the (partial) hydrolysis method (“New Edition Fatty Acid Chemistry”, Keiichi Inaba et al., Koshobo, 1981). Further, when glycerin and PUFA (and its ester) are used as raw materials, as a method for synthesizing them, known means such as the above-mentioned (Japanese Patent Laid-Open No. 1-268663) are known. Even if it is an enzymatic means, if 0.1% or more of MG is contained in the fat or oil to be the product, the object of the present invention to “obtain a highly unsaturated fatty acid-containing fat or oil powder having high oxidation stability” can be achieved. I can.

0.1% or more of PUFA adjusted in this way
-The oils and fats containing MG are refined by various processes such as deoxidation, deodorization and decolorization, if necessary. Depending on the purpose, in order to satisfy the conditions of the present invention, a concentration step may be added so that the MG content in the product is 0.1% or more. These methods are described in the book ("Actual production of edible oils and fats", written by Takaaki Miyakawa, Kou Shobo, 198).
8; "Comprehensive Lipid Science", Hikaru Kayama, Koseisha Koseikaku, 198
As detailed in 9). In any case, using fats and oils containing 0.1% or more of PUFA-MG is one of the basic requirements of the present invention for “obtaining highly unsaturated fatty acid-containing fats and oil powders with high oxidation stability”, and The purification and concentration steps are not always necessary as long as the above condition is satisfied.

0.1% or more of PUFA adjusted in this way
-For oils and fats containing MG, phospholipids can be added in an amount of 1.0% or more and 30.0% or less (weight ratio) in order to enhance synergistically the oxidation stability. Here, the phospholipids refer to glycerophospholipids, sphingophospholipids, phosphonolipids, etc., but in reality, glycerophospholipids (mainly phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidylserine, etc.) are used from an industrial viewpoint such as price and quality. , Phosphatidylinositol, and mixtures of these lyso forms and the like) are preferably used. Glycerophospholipids are generally contained in a large amount in soybean lecithin, egg yolk lecithin and the like, and are used in the fields of foods, pharmaceuticals, feeds, etc. In the present invention, these lecithins can be used as phospholipids. Although commercially available lecithin is composed of various grades (having different phospholipid purities), the final phospholipid content itself is important in the present invention.

When the amount of phospholipid added to fats and oils containing 0.1% or more of PUFA-MG is 1.0% or less, there is little effect on oxidative stability, and when it is 30.0% or more, problems such as blocking due to physical properties after pulverization are caused. Therefore, it is desirable to add 1.0% or more and 30.0% or less (weight ratio) because it causes a problem that the lecithin odor becomes strong organoleptically.

As antioxidants to be used in combination, various kinds are known, such as vitamin E (tocopherol), ascorbic acid, ascorbyl palmitate, catechins, and spice extracts. Even if the kind of the agent and the amount used are arbitrarily selected, they do not contradict the basic requirements of the present invention.

On the other hand, many means are known for producing oil and fat powder. Particularly, regarding the pulverization of fats and oils containing PUFA, JP-A-60-49097, JP-A-62-126933, and JP-A-63
-44844, Japanese Patent Application Laid-Open No. 3-297364, and the like, proteins (casein, sodium caseinate, soybean protein, gelatin, milk, milk powder, whey, egg white, etc.), sugars (starch, dextrin) as excipients. , Cyclodextrin, lactose, sucrose, maltose, glucose, isomerized sugar, hydrogenated maltose, hydrogenated glucose, arabic gum, guar gum, xanthan gum, tragacanth gum, carrageenan, pectin, mannan, etc. are generally used. In the present invention, any kind of excipient and mixing ratio may be used. The content of fats and oils in the powder after pulverization must be 1.0% or more (weight ratio) as the minimum amount that the functional lipid can express its physiological activity due to the characteristics of the product as a powdered fat and oil. Is.

The above-mentioned raw materials are, for example, for PUFA-MG and PUFA-MG equivalent to 1.0% (weight ratio) or more based on the total solid content in a solution in which proteins, sugars and the like are previously dissolved.
1.0% or more and 30% or less (weight ratio) of phospholipids and PUFA-MG, an arbitrary amount of antioxidant is added, mixed fat-soluble components are added, dispersed with a homomixer (trade name), etc., and sample before drying Can be At this time, the total solid content in the solution is not limited, but it is naturally limited by mechanical operation conditions in the mixing step, operability of the dryer, drying efficiency, and the like. Further, depending on the intended use of the highly-unsaturated fatty acid-containing oil and fat powder used as a product (foods, pharmaceuticals, feeds, etc.), it is also included in the scope of the present invention when flavors, seasonings, medicinal ingredients, nutritional ingredients, etc. are added separately. It is natural that

The above mixed solution can be dried and powdered by a known means such as spray drying, freeze drying, hot air drying and the like. In the present invention, the drying method itself does not limit the idea of the present invention by any means.

By the above method, a highly unsaturated fatty acid-containing oil / fat powder having high oxidation stability can be prepared. When this product is used for foods, pharmaceuticals, feeds, etc., the occurrence of fishy odor, the increase of POV, etc. are suppressed, and a product of good quality with high oxidative stability can be obtained.

[0020]

In the present invention, since the content of monoglyceride present in the highly unsaturated fatty acid-containing fats and oils containing monoglycedide is 0.1% or more by weight, the highly unsaturated fatty acid-containing fat and oil powder having excellent oxidation stability can be obtained. You can

[0021]

EXAMPLES Next, the present invention will be described in more detail by way of examples, but these are examples and the present invention is not limited to these examples.

[Example 1] Method for preparing fats and oils containing 0.1% or more of PUFA-MG In this example, eicosapentaenoic acid (hereinafter abbreviated as EPA) was selected as the PUFA, and 0.1% from fish oil was selected.
The method for enzymatically adjusting fats and oils containing PUFA-MG described above will be described.

1. Raw material oils and fats to be used As raw material oils and fats for MG adjustment, EPA20 (TG) (trade name; manufactured by Ikeda Gokuka Kogyo Co., Ltd.) was used after all the compounding components such as soybean lecithin and natural vitamin E were removed. The raw material oil and fat was edible fish oil refined from sardine oil in steps such as deoxidation, decolorization, concentration and deodorization, and had the following properties. MG purity (in total lipid composition) Undetected (TLC / FID method) EPA purity (in total fatty acid composition) 21.3% (gas chromatography method) Acid value (AV) 0.1 (Japan Oil Chemistry Association method) Peroxide value (POV) ) 0.2 (Japan Oil Chemistry Association method) Color tone Light yellow transparent odor Slightly peculiar flavor (fish odor) Based on the above properties, it was presumed that most of the raw material fats and oils were composed of TG. This raw material fat will be referred to as "EPA20".
Called.

2. Enzymatic preparation method of MG The above-mentioned raw material fats and oils are partially hydrolyzed with an enzyme to give MG content.
The following method was used to adjust 0.1% or more of "fats and fats containing 5.0% or more of PUFA".

As the enzyme, lipase derived from Rhizops niveus was used. The composition of the reaction solution (pH around 7.0 before the start of the reaction) is as follows. Raw oil and fat (EPA20) 49.5 parts Lipase 0.5 part Water 50.0 parts Total 100.0 parts The reaction was carried out at 40 ° C for 3 hours, and the reaction was terminated by heating at 90 to 95 ° C for 10 minutes. During this time, pH
No adjustments were made. After removing water from the solution after the reaction by centrifugation (3000 rpm, 10 minutes), the oil and fat was further purified by steam distillation, molecular distillation, acid clay treatment, etc., and deodorized and decolorized purified oil of the following properties Got MG purity (in total lipid composition) 5.5% (TLC / FID method) EPA purity (in total fatty acid composition) 21.2% (gas chromatography method) Peroxide value (POV) 0.2 (Japan Oil Chemistry Association method) Acid value (AV 42.9 (Japan Oil Chemistry Association method) Color tone Light yellow transparent Smell This product has a slight peculiar flavor (fish odor) and is hereinafter referred to as "EPA20E (undeoxidized oil)". The MG content of this product satisfied both the MG content (0.1% or more) and the PUFA content (5.0% or more) specified in the present invention.

EPA20E (undeoxidized oil) has a high AV because free fatty acids generated by the hydrolysis of TG remain during the enzymatic reaction, and this has a high AV, which may limit the range of use in foods. Therefore, this was further repeatedly treated by an alkali deoxidizing method, a molecular distillation method, a vacuum distillation method or the like to obtain a refined oil having the following properties in which free fatty acids were removed and AV was reduced.

MG purity (in total lipid composition) 5.8% (TLC / FID method) EPA purity (in total fatty acid composition) 21.6% (gas chromatography method) Peroxide value (POV) 0.1 (Japan Oil Chemistry Association method) Acid Value (AV) 0.3 (Japan Oil Chemistry Association method) Color tone Light yellow transparent Odor A slight peculiar flavor (fish odor) is referred to as "EPA20E (deoxidized oil)" hereinafter. The MG content of this product satisfied both the MG content (0.1% or more) and the PUFA content (5.0% or more) specified in the present invention.

The EPA20E (undeoxidized oil) and EPA20E (deoxidized oil) thus obtained are used (purpose).
Prototypes shown in the following examples were carried out for the EPA 20 while properly using. In the case of the present embodiment, EPA is used as an example of PUFA-MG, but it goes without saying that each PUFA-MG can be adjusted by the same process in the case of other PUFAs (described in the text). .

Example 2 By spray drying method (SD)
Preparation of PUFA-containing oil / fat powder The EPA-containing oil / fat powder was adjusted according to the following formulation (Table 1), and the quality was compared.

[Table 1] That is, soybean protein, lactose, and starch are added to 300 parts of water, mixed and dissolved, and this solution is treated with TK Homomixer MARK (manufactured by Tokushu Kika Kogyo) while EPA20
, EPA20E (undeoxidized oil), soybean lecithin, etc. are added little by little, and after all mixing is completed, 10000 rpm
At 10 minutes, homogenization treatment (emulsification / dispersion) was performed under ice cooling. Subsequently, this solution was spray-dried under the following conditions with a spray dryer (Parbis mini spray (GA-21 type), manufactured by Yamato Scientific Co., Ltd.) to obtain a powder. Spray drying conditions: Inlet temperature 180 ° C Outlet temperature 100 ° C Liquid transfer rate 2.5 ml / min Spraying pressure 1.2 kg / cm ² The quality of the obtained powder is shown in Table 2. The solid content recovery rate is 65 to 70% in each section.

[0030]

[Table 2] When the qualities of the above powders were compared after 30 days at 40 ° C. (open standing), the results shown in Table 3 were obtained.

The sensory evaluation was shown by an average linguistic expression with a panel of 5 members of Ikeda Institute for Food Research.

That is, blank (EPA20 + phospholipid)
When comparing the EPA20E (undeoxidized oil) group (phospholipid-added group) and the powdered product and after 30 days, the latter containing MG has a low POV and good sensory evaluation results. The intent of the present invention on the oxidative stability of PUFA-containing fat powders containing MG has been demonstrated. Furthermore, when comparing the EPA20E (undeoxidized oil) group with the phospholipid-free group and the phospholipid-added group, the latter containing phospholipid had a low POV both immediately after pulverization and after 30 days, and The result of the sensory evaluation was also good, and the effect of the present invention on the oxidative stability of the PUFA-containing oil and fat powder containing phospholipids has been proved.

[0033]

[Table 3] [Example 3] Adjustment of PUFA-containing oil / fat powder by freeze-drying method (FD) The EPA-containing oil / fat powder was adjusted according to the following formulation (Table 4), and the quality was compared.

[0034]

[Table 4] That is, casein, gum arabic, and starch were added to 200 parts of water, mixed and dissolved, and this solution was treated with TK Homomixer MARK II (manufactured by Tokushu Kika Kogyo Co., Ltd.) while EPA20 (V2), A fat-soluble mixture such as EPA20E (deoxidized oil) and soybean lecithin was added little by little, and after all mixing was completed, homogenization treatment (emulsification / dispersion) was performed at 10,000 rpm for 10 minutes under ice cooling. . Then, put the sample in a plastic bag with a thickness of about 1
The sample was placed in a centimeter of 1 cm and pre-frozen at -25 ° C. This frozen sample was freeze-dried for 20 hours (0.2 Torr or less, final product temperature 4
(0 ° C.) treatment and pulverization to obtain a product (powder).

Table 5 shows the quality of the obtained (product) powder.

[0036]

[Table 5] When the qualities of the above powders were compared after 30 days under the condition of 40 ° C. (open standing), the results shown in Table 6 were obtained. The sensory evaluation was shown by an average linguistic expression using a panel of Ikeda Institute for Food Research (5 persons).

[0037]

[Table 6] In other words, comparing the blank (EPA20) and EPA20E (deoxidized oil) section (no phospholipid added),
After 30 days, in the latter containing MG, the POV was low and the results of sensory evaluation were also good.
The effect of the present invention on the oxidative stability of FA-containing oil and fat powder has been proved.

Further, when comparing the EPA20E (deoxidized oil) group with the phospholipid-free group and the phospholipid-added group, the latter containing phospholipid had a low POV both immediately after pulverization and after 30 days, Moreover, the result of the sensory evaluation was also good, and the effect of the present invention on the oxidation stability of the PUFA-containing oil and fat powder containing phospholipids has been proved.

Example 4 PUFA blended with other antioxidant
Comparison with oil and fat powder content Tocopherol and ascorbic acid are taken as antioxidants that are often used in the fields of foods, pharmaceuticals, and feeds.
An example of a comparative experiment with PUFA-MG and phospholipid used in the present invention is shown. The formulation is shown in Table 7.

[0040]

[Table 7] After mixing and emulsifying the above components in the same manner as in Example 1,
The product was obtained by spray drying with a spray dryer in the same manner.

Table 8 shows the quality of the obtained powder. The solid content recovery rate is 65 to 70% in each section. The sensory evaluation was shown by an average linguistic expression using a panel of Ikeda Institute for Food Research (5 persons).

[0042]

[Table 8] When the qualities of the above powders were compared after 30 days under the condition of 40 ° C. (open standing), the results shown in Table 9 were obtained.

The sensory evaluation is shown by an average linguistic expression with a panel of Ikeda Institute for Food Research (5 persons).

[0044]

[Table 9] The following is clear from the above results.

1. EPA20 usage zone (no antioxidant added) and EP
From the comparison of POV value and sensory evaluation (fish odor) of A20E (deoxidized oil) use group (no phospholipid added), PUFA-M containing MG
By using G, the stability of fats and oils after pulverization is significantly improved.

2. PUFA-MG containing MG is used based on the comparison of POV value and sensory evaluation (fish odor) of EPA20 use group (with ascorbic acid or tocopherol added) and EPA20E (deoxidized oil) use group (without phospholipid added). As a result, the stability of fats and oils after pulverization is better than when ascorbic acid or tocopherol is used.

3. The value of POV in the EPA20E (deoxidized oil) use group with and without phospholipid addition,
From the comparison of sensory evaluation (fish odor) and the like, the stability of the oil / fat after pulverization is significantly improved by adding phospholipid in the formulation.

From the above results, in obtaining a PUFA-containing oil / fat powder having high oxidation stability, the advantages of using PUFA-MG and the advantages of adding phospholipids to further improve the oxidation stability are found. It was proven.

[0049]

As described and demonstrated above, the present invention provides the PUFA-containing oil and fat powder with high oxidation stability,
It is possible to expand the range of use of PUFA in foods, pharmaceuticals, feeds, etc., and ultimately contribute to the maintenance and improvement of health.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI Technical indication location A61K 35/78 J 7167-4C Q 7167-4C C 7167-4C C11B 5/00 2115-4H

Claims (5)

[Claims] 1. The content of monoglyceride present in fats and oils containing polyunsaturated fatty acids containing monoglyceride is expressed by weight ratio.
A highly unsaturated fatty acid-containing oil / fat powder characterized by being 0.1% or more. 2. The highly unsaturated fatty acid-containing fat powder according to claim 1, wherein the amount of the highly unsaturated fatty acid-containing fat containing monoglyceride in the powder is 1.0% or more by weight. 3. The polyunsaturated fatty acid content present in the polyunsaturated fatty acid-containing oil containing monoglyceride is 5.0% or more by weight ratio.
The highly-unsaturated fatty acid-containing oil and fat powder described. 4. The polyunsaturated fatty acid is α-linolenic acid, γ
-Linolenic acid, dihomo-γ-linolenic acid, arachidonic acid, eicosapentaenoic acid, docosahexaenoic acid, one or more polyunsaturated fatty acids according to claim 1 to 3, characterized in that Oil and fat powder containing saturated fatty acids. 5. The phospholipid is contained in the highly unsaturated fatty acid-containing fat or oil containing the monoglyceride contained in the highly unsaturated fatty acid-containing fat or oil powder in a range of 1.0% to 30.0% by weight. The highly unsaturated fatty acid-containing oil and fat powder according to 1 to 4.