JP3222314B2 - Method for producing fat powder containing polyunsaturated fatty acids - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polyunsaturated fatty acid
The present invention relates to a method for producing a fat and oil powder, which can be used in a wide range of fields, particularly as foods, pharmaceuticals and feeds, and contains a highly unsaturated fatty acid, or a lower alcohol ester or a glyceride thereof, and has good sensory evaluation and oxidation. The present invention relates to a method for producing a highly unsaturated fatty acid-containing fat and oil powder having excellent stability.

[0002]

2. Description of the Related Art α-linolenic acid, γ-linolenic acid, dihomo-γ-linolenic acid, arachidonic acid (hereinafter abbreviated as AA), eicosapentaenoic acid (hereinafter abbreviated as EPA), docosapentaenoic acid (hereinafter abbreviated as EPA) Polyunsaturated fatty acids (hereinafter abbreviated as PUFA) such as DPA (abbreviated as DPA) and docosahexaenoic acid (hereinafter abbreviated as DHA) are used in a wide range of fields such as foods, pharmaceuticals and feeds due to their broad functionality and physiological activity. It is conceived to be used, and in fact some are already manufactured and sold.

[0003] However, fats and oils containing PUFAs generally oxidize very quickly, and thus many of the PUFA-containing products currently on the market are enclosed in soft gelatin capsules or stored at low temperatures in containers filled with nitrogen gas. However, there are restrictions when used in the above applications.

[0004] In order to solve such problems, many methods are known for producing PUFA-containing fats and oils powders.

[0005] That is, soy protein and wheat protein (Ibuki and Iwami: Journal of the Society for Study of Soy Protein Nutrition, 11, 17-22 (1990)) and egg white (Taguchi et al .: Agric. Bi)
ol. Chem., 52, 539-545 (1988)), gelatin, casein, proteins such as skim milk powder and their partially decomposed products, starch, dextrin, cyclodextrin, lactose, sucrose, gum arabic, carrageenan, alginic acid ( Methods using saccharides such as sodium) and agar are known.

[0006] These PUFA-containing fats and oils powders are mixed with emulsifiers such as fatty acid monoglyceride, sucrose fatty acid ester and propylene glycol fatty acid ester together with excipients, and after mixing and emulsification, spray drying (SD) method or It is dried and powdered by freeze-drying (FD) method.

[0007]

However, the oxidative stability of the PUFA-containing fats and oils powders obtained by the above method is insufficient in any case, and it is difficult to prevent a decrease in sensory evaluation with the progress of oxidation. Therefore, there was a limit in expanding its use.

The present invention has been made in view of the conventional problems as described above, and has as its object the purpose of the present invention is to provide good sensory evaluation and excellent oxidative stability, and to be widely used as foods, pharmaceuticals, feeds and the like. Polyunsaturated fatty acids available in various fields
An object of the present invention is to provide a method for producing an oil-containing powder .

[0009]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have a physiological activity.
Fats and oils containing 10% by weight or more of PUFA or at least one selected from lower alcohol esters or glycerides thereof are uniformly dispersed in an aqueous solution obtained by mixing and dissolving defatted soybeans, and then mechanically emulsified. / W Emulsion was prepared and spray-dried (SD) or freeze-dried (FD), and it was found that a PUFA-containing fat and oil powder having excellent oxidation stability could be obtained, and the present invention was reached. The details are described below.

[0010] PUFAs having physiological activity include α-linolenic acid, γ-linolenic acid, dihomo-γ-linolenic acid, A
A, EPA, DPA, DHA, etc.

[0011] Natural products containing 10% by weight or more of the above PUFA can also be used as the PUFA of the present invention.

Examples of the natural products include linseed oil and perilla oil as raw materials for α-linolenic acid, evening primrose oil as raw material for γ-linolenic acid, γ-linolenic acid, dihomo-γ-linolenic acid, AA and EPA. Microbial fats and oils as raw materials, EPA,
Fish oil is a raw material for DHA.

As the lower alcohol ester of PUFA, its methyl ester, ethyl ester and the like are preferable.

As the glyceride, Mono, G,
In addition to triglycerides, phospholipids and saccharide lipids are included.

[0015] The PUFA-containing fat or oil is a PU having a physiological activity.
Only one of FA or its lower alcohol ester or its glyceride can be used, or a mixture of two or more thereof.

That is, only one of the fatty acids containing PUFA having the above physiological activity, the lower alcohol esters containing the lower alcohol esters thereof, and the glycerides containing the glycerides is selected and used as PUFA-containing fats and oils. In addition, in an appropriate combination, a fatty acid containing PUFA having the above physiological activity, or a lower alcohol ester containing the lower alcohol ester thereof, or a glyceride containing the glyceride, two or more selected from PUFA Oils and fats may be contained. In any case, PUFA having the above physiological activity is contained in its constituent fatty acids in 10%.
% Or more should be included.

In pulverizing the above PUFA-containing fats and oils,
It is important to select excipients that have excellent oxidative stability and can be used in foods, pharmaceuticals, feeds, and the like.

Therefore, proteins such as soy protein, defatted soybean, wheat protein, egg white, gelatin, casein, skim milk powder,
And powdered PUFA-containing fats and oils using carbohydrates such as starch, dextrin, cyclodextrin, lactose, sucrose, gum arabic, carrageenan, alginic acid (sodium) and agar as excipients. A comparison of oxidative stability revealed that defatted soybeans were specifically effective in oxidative stability of PUFA-containing fats and oils powder.

The defatted soybean is produced as a by-product during the usual soybean oil extraction and refining process.
It is used in the fields of food and feed. Therefore, so-called soybean protein such as extracted soybean protein, concentrated soybean protein, isolated soybean protein, etc. obtained by further purifying and processing the defatted soybean as a raw material, is defined, classified, and compositionally. They are completely different in physical properties and have different uses.

The defatted soybean used in the present invention refers to a soybean oil extracted from a raw soybean by solvent extraction or squeezing extraction.
It is obtained by removing the solvent and the like from the extraction residue, but naturally includes those obtained by further processing such as alcohol treatment, heat treatment, and pulverization treatment as needed.

The effectiveness of defatted soybeans depends on their emulsifying properties, higher-order structure of proteins, and changes in functions of other saccharides, fibers, trace components, etc., and the oxidative stability of the fats and oils powder after drying. Is presumed to have contributed to

The amount of defatted soybean used is 5 to 95% by weight in the fat and oil powder.
%, More preferably 20 to
It is in the range of 60% by weight.

In order to obtain a more stable PUFA-containing fat and oil powder, it is desirable to use an antioxidant.

The above antioxidants include tocopherol,
In addition to lecithin, known antioxidants such as organophosphate compounds, glutathione, eugenol, ascorbic acid, ascorbic acid ester, protein hydrolyzate, 2-bidroxy-benzophenone derivative, spice extract, tea extract, SOD, etc. It can be used as needed. In particular, the use of lecithin forms a lamellar complex with proteins in defatted soybeans, alters the higher order structure of the protein, reduces β-structure, increases random coils, and ultimately increases emulsifying activity. This may contribute to the oxidative stability of the PUFA-containing fats and oils powder, and has an effect more than a simple antioxidant. However, in the present invention, the use of these antioxidants is merely an auxiliary means and is not a necessary condition.

As described above, the fat and oil powder in the present invention is composed of fats and oils containing PUFA and defatted soybeans. May be used alone or in combination of two or more.

In order to improve the mechanical operability and productivity in the drying step described later, or to improve the processability (for example, coating, granulation, tableting, etc.) of the obtained product, various proteins and carbohydrates are used. , An emulsifier, etc. can be optionally added.

The above-mentioned proteins, carbohydrates, emulsifiers and the like include soybean protein such as extracted soybean protein, concentrated soybean protein, isolated soybean protein, proteins such as wheat protein, egg white, gelatin, casein, skim milk powder, and partially decomposed products thereof. Emulsifiers such as starch, dextrin, cyclodextrin, lactose, sucrose, gum arabic, carrageenan, alginic acid (sodium), sugars such as agar, fatty acid monoglyceride, sucrose fatty acid ester, propylene glycol fatty acid ester, etc.
Examples include nucleic acids, amino acids, organic acids, flavors, colorings, and other food additives.

However, in the present invention, the use of these components used for foods, medicines, feeds and the like is merely an auxiliary means and not a necessary condition.

In the method for producing a PUFA-containing fat or oil powder of the present invention, the fat or oil containing PUFA is obtained by mixing and dissolving defatted soybeans.
After homogeneously dispersed in the dispersed aqueous solution, it is mechanically emulsified to prepare an O / W emulsion.

For the emulsification, a mechanical emulsification method such as a high-speed stirring system, a high-pressure system or an ultrasonic system can be used.
5 to 80% by weight of PUFA-containing fats and oils in a solution obtained by dispersing and dissolving 5 to 95% by weight, preferably 20 to 60% by weight in an appropriate amount of water.
%, Preferably 20 to 60% by weight, is uniformly dispersed and emulsified.

Here, the appropriate amount of water to be used is appropriately about 50 to 500 parts by weight per 100 parts by weight of the excipient (coating agent), but the amount is adjusted depending on the physical properties of the contents. It is necessary.

The emulsifying conditions are about 10 to 30 minutes (5000 to 15000 rpm) in the case of a high-speed stirring type, and 100 to 200 kg /
A pressure of cm ² is appropriate, but in the present invention, the emulsification conditions themselves are not necessary, as long as conditions sufficient to prepare an O / W emulsion are satisfied.

Further, components other than fats and oils containing PUFAs and defatted soybeans are added to an aqueous phase or an oil phase in advance before emulsification.
Emulsification may be carried out together, or after addition of the emulsification, it may be newly added, mixed, dispersed, or dissolved.

The above liquid mixture is dried by spray drying (spray drying, SD) or freeze drying (freeze drying, FD) to form a powder.

In the case of the spray drying method, the inlet temperature, the outlet temperature,
Drying conditions such as the amount of liquid to be sent and the drying conditions such as product temperature, degree of vacuum and drying time in the case of freeze-drying method vary depending on the physical properties of the undiluted solution, the content of the mixture, restrictions on machine operation, etc. Can not be specified. However, in the present invention, the drying method and the drying conditions are not necessary conditions.

The PUFA-containing fat and oil powder prepared by the above method may be stored as it is because of its high oxidation stability, or may be stored in a packaging material having a high gas barrier property in the presence of an oxygen scavenger. You can leave it. Furthermore, it can be reprocessed into granules, tablets and the like and stored. Also other foods,
It can also be stored by mixing with raw materials used for pharmaceuticals, feeds, and the like.

Further, when PUFA-containing fats and oils powders are used in foods, pharmaceuticals, feeds, etc., the increase in POV and the appearance of oxidized odor can be suppressed, and a product of good quality can be obtained. It is possible to expand dramatically.

[0038]

[Function] After uniformly dispersing an oil or fat containing at least 10% by weight of at least one selected from physiologically active PUFA or its lower alcohol ester or its glyceride in an aqueous solution in which defatted soybeans are mixed and dissolved. , Mechanically emulsified to prepare an O / W emulsion, which is spray-dried (SD) or freeze-dried (FD) to give PU with excellent oxidation stability.
FA-containing fat and oil powder can be obtained.

The effectiveness of defatted soybeans is related to their emulsifying properties, higher-order structure of proteins, and changes in functions of other carbohydrates, fibers, trace components, etc., and the oxidative stability of the fat and oil powder after drying. Is presumed to have contributed to

[0040]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited by these examples.

<Example 1, Comparative Example 1, Comparative Example 2, Comparative Example 3> 60 parts by weight of defatted soybean (commercial product, manufactured by Company A) was suspended and dispersed in 300 parts by weight of water, and the suspension was dispersed. Is treated with a stirring homogenizer (manufactured by Tokushu Kika Kogyo Co., Ltd.), 40 parts by weight of linseed oil (commercial product, manufactured by Company B) is added little by little, and after all mixing is completed, the mixture is stirred at 12,000 rpm for 20 minutes. The mixture was homogenized (emulsified, dispersed) under ice cooling. Subsequently, this stock solution was spray-dried with a spray dryer (manufactured by Yamato Kagaku Co., Ltd.) to obtain 63 parts by weight of a highly unsaturated fatty acid-containing (linseed oil) fat or oil powder. The composition of linseed oil is as follows.

Linseed oil composition: α-linolenic acid purity in fatty acid composition 55.3% (GC analysis, Area%) Peroxide value (POV, meq / Kg) 0.5 Sensory evaluation: Colorless and transparent to pale yellow transparent, almost odorless

For comparison, instead of defatted soybean, instead of defatted soybean, isolated soybean protein (commercially available, manufactured by Company A; Comparative Example 1), sodium caseinate (commercially available, manufactured by Company C; Comparative Example 2), dextrin (DE10, commercially available product) , Manufactured by Company D; Comparative Example 3) to obtain linseed oil powder. Recovery rate in each case is 60
6868%. Table 1 shows the quality of the linseed oil powder immediately after pulverization together with Example 1.

[0044]

[Table 1]

After powdering, each of the prototypes was placed under the condition of 40 ° C. (open standing) for 30 days, quality was evaluated, and the oxidation stability was compared. The results are shown in Table 2.

[0046]

[Table 2]

That is, in Example 1 using defatted soybeans as an excipient, the physical properties immediately after powdering were almost the same as those in Comparative Example, but the POV after 30 days was low, and the sensory evaluation was Was also good, and the change over time tended to be extremely small. From this, the effectiveness of using defatted soybeans as an excipient for highly unsaturated fatty acid-containing fats and oils (linseed oil) is clear, and the effect of the present invention has been proven.

<Example 2> A defatted soybean pulverized product (commercial product,
A) (50 parts by weight) was suspended and dispersed in 180 parts by weight of water, and 50 parts by weight of purified skipjack oil (commercial product, manufactured by Company B) was added little by little to the suspension and mixed well. The mixture was homogenized (emulsified and dispersed) at 200 kg / cm ² with a high-pressure homogenizer (manufactured by Nippon Seiki Seisakusho). Subsequently, this undiluted solution was freeze-dried with a freeze dryer (manufactured by Tokyo Rika Kikai Co., Ltd.) to obtain a highly unsaturated fatty acid-containing (purified bonito oil) oil powder 84
A part by weight was obtained (defatted soybean section). The composition of the refined skipjack oil is as follows.

Composition of refined skipjack oil: EPA purity in fatty acid composition 6.5% (GC analysis, Area%) DPA purity in fatty acid composition 2.7% (GC analysis, Area%) DHA purity in fatty acid composition 27.3% (GC analysis , Area%) Peroxide value (POV, meq / Kg) 0.7 Sensory evaluation: Transparent, pale yellow, with very weak fishy odor

Further, the same treatment as in the above defatted soybean section is carried out.
Grinded defatted soy instead of 50 parts by weight defatted soy
When 50 parts by weight of 30 parts by weight and 20 parts by weight of gum arabic (commercially available, manufactured by E Company) are used (use of gum arabic), 2 parts by weight of soybean lecithin (commercially available, manufactured by Company B) as an antioxidant And 0.1 parts by weight of tocopherol (commercially available, manufactured by Company B) (addition of antioxidant); and 1 part by weight of glycerin fatty acid ester (commercially available, manufactured by Company F) as emulsifier (addition of emulsifier) Were examined in the same manner to obtain a purified skipjack oil powder. Recovery was in each case in the range of 80-90%. Table 3 shows the quality of the refined skipjack oil powder immediately after powdering.

[0051]

[Table 3]

After powderization, each prototype was placed under the condition of 40 ° C. (open standing) for 30 days, quality was evaluated, and the oxidation stability was compared. Table 4 shows the results.

[0053]

[Table 4]

That is, the POV was low in all the test plots,
In addition, since the sensory evaluation is also good, the effectiveness of using a defatted soybean pulverized product as an excipient for highly unsaturated fatty acid-containing fats and oils (refined skipjack oil), and using some excipients other than defatted soybeans The effectiveness of using an antioxidant, the effectiveness of using an emulsifier is clear,
The effect of the present invention has been proven. This means that when defatted soybeans that have been subjected to processing such as alcohol treatment, heat treatment, and crushing treatment are used, various proteins other than defatted soybeans, and when some excipients such as saccharides are used in combination, tocopherol, lecithin, etc. This demonstrates that the addition of an antioxidant and the addition of a food additive such as an emulsifier are not factors that hinder the effects of the present invention.

Example 3 40 parts by weight of a defatted soybean alcohol-treated product (commercially available, manufactured by Company A) was suspended in 160 parts by weight of water.
20 parts by weight of free γ-linolenic acid (commercially available, manufactured by Company B), 20 parts by weight of dihomo-γ-linolenic acid (commercially available, manufactured by Company B), and arachidonic acid (commercially available) 20 parts by weight of a mixture, a total of 60 parts by weight, was added little by little, and after all the mixing was completed, an ultrasonic emulsifier (Tokusai Kika Kogyo Co., Ltd.)
), And homogenized (emulsification, dispersion). continue,
This stock solution was spray-dried in the same manner as in Example 1 to obtain 67 parts by weight of a highly unsaturated fatty acid-containing oil or fat powder. The compositions of γ-linolenic acid, dihomo-γ-linolenic acid, and AA are as follows.

Composition of γ-linolenic acid: purity of γ-linolenic acid in fatty acid composition 98.8% (GC analysis, Area%) Peroxide value (POV, meq / Kg) 0.4 Composition of dihomo-γ-linolenic acid: fatty acid composition Dihomo-γ-linolenic acid purity 97.5% in GC (GC analysis, Area%) Peroxide value (POV, meq / Kg) 0.5 AA composition: DHA purity in fatty acid composition 98.2% (GC analysis, Area%) Peroxidation Prices (POV, meq / Kg) 0.7

The quality of the highly unsaturated fatty acid-containing fat and oil powder immediately after powdering was evaluated by placing the powder under conditions of 40 ° C. (open standing) for 30 days, and comparing the oxidation stability with the results. It is shown in FIG.

[0058]

[Table 5]

That is, in Example 3, since the POV was low and the sensory evaluation was good, γ-linolenic acid,
The effectiveness of using alcohol-treated defatted soybeans on the oxidation stability of dihomo-γ-linolenic acid and AA-containing fats and oils powder is evident, and the effects of the present invention have been proven. This demonstrates that the use of defatted soybeans that have been subjected to processing such as alcohol treatment, heat treatment, and pulverization is not a factor that hinders the effects of the present invention.

<Example 4> A defatted soybean pulverized product (commercial product,
A) (40 parts by weight) was suspended and dispersed in 200 parts by weight of water, and the suspension was treated with a stirring homogenizer.
Ethyl ester (commercial product, manufactured by Company B) (60 parts by weight) was added little by little, and after all the mixing was completed, homogenization treatment (emulsification, dispersion) was performed at 10,000 rpm for 30 minutes under ice cooling. Subsequently, this stock solution was spray-dried in the same manner as in Example 1 to obtain 61 parts by weight of an EPA ethyl ester-containing oil and fat powder. The composition of EPA ethyl ester is as follows.

Composition of EPA ethyl ester: EPA purity in fatty acid composition 93.8% (GC analysis, Area%) DHA purity in fatty acid composition Not detected (GC analysis, Area%) Peroxide value (POV, meq / Kg) 0.5 Sensory evaluation: Transparent, pale yellow, with very weak fishy odor

The quality of the EPA ethyl ester-containing fat and oil powder immediately after powdering was evaluated by sensory evaluation after placing the powder under the condition of 40 ° C. (open standing) for 30 days, and the results of comparison of oxidation stability are shown in Table 6. Shown in

[0063]

[Table 6]

That is, in Example 4, since the POV was low and the sensory evaluation was good, the effectiveness of using defatted soybean on the oxidative stability of EPA ethyl ester-containing fat and oil powder was apparent. The effect of the invention has been proven.

Example 5 The EPA ethyl ester-containing fat and oil powder obtained in Example 4 was treated with a 1% starch solution in a fluidized bed granulator (manufactured by Okawara Seisakusho Co., Ltd.), and the recovery was
95% yielded oil-fat powder granules containing EPA ethyl ester. Immediately after granulation and after placing the granules under the condition of 40 ° C. (open standing) for 30 days, the quality was evaluated, and the results of comparing the oxidation stability are shown in Table 7.

[0066]

[Table 7]

That is, almost no deterioration of the product was observed during the granulation step, and the value of POV after 30 days was low.
In addition, the sensory evaluation was good, and the state of dispersion in the aqueous solution was also good. This is a necessary finding when the product obtained by the present invention is further processed to expand the application, and also demonstrates the effect of the present invention.

Example 6 In order to tablet 200 mg of the EPA ethyl ester-containing fat and oil powder granules obtained in Example 5,
The mixture was subjected to tableting to obtain EPA ethyl ester-containing oil and fat powder tablets. For tableting, upper sucrose 122.8 mg, lactose 61.9 mg, gum arabic 6.1 mg, gelatin 2.5 mg, crystalline cellulose 1.
0mg, calcium carbonate 3.9mg, talc 0.8mg, shellac
Use 200 mg of 1.0 mg as sugar coating, 400 mg per tablet
Sugar-coated tablets. Table 8 shows the results of quality evaluation of this tablet immediately after compression and after the tablet was placed under the condition of 40 ° C. (open standing) for 30 days, and the oxidation stability was compared.

[0069]

[Table 8]

That is, almost no deterioration of the product was observed during the tableting process, and the value of POV after 30 days was low.
Moreover, it was also good in sensory test, and it was clarified that the oxidation stability was improved by tableting. This is a necessary finding when the product obtained by the present invention is further processed to expand the application, and also demonstrates the effect of the present invention.

[0071]

As described above, in the present invention, a defatted soybean is used as an excipient to obtain a highly unsaturated fatty acid-containing fat and oil powder, so that it has good organoleptic evaluation and excellent oxidative stability. This has the effect of obtaining a highly unsaturated fatty acid-containing oil and fat powder that can be used in a wide range of fields such as foods, medicines and feeds.

Claims (4)

(57) [Claims] 1. A method for producing a highly unsaturated fatty acid-containing fat or oil powder comprising powdering a fat or oil containing at least one polyunsaturated fatty acid or a lower alcohol ester or a glyceride thereof, wherein said fat or oil is solvent-extracted from raw soybean. Or for squeeze extraction
After extracting more soybean oil, it is obtained by removing the solvent from the extraction residue.
After uniformly dispersing in an aqueous solution obtained by mixing and dissolving defatted soybeans and an antioxidant , emulsification is performed to prepare an O / W emulsion, which is then powdered by a spray drying method or a freeze drying method. A method for producing a highly unsaturated fatty acid-containing fat or oil powder. 2. The polyunsaturated fatty acid containing polyunsaturated fatty acid according to claim 1, wherein the polyunsaturated fatty acid or the lower alcohol ester or the glyceride thereof contained in the one or more is contained by 10% by weight or more in the material fat. A method for producing fat and oil powder. 3. The polyunsaturated fatty acid is one or two selected from α-linolenic acid, γ-linolenic acid, dihomo-γ-linolenic acid, arachidonic acid, eicosapentaenoic acid, docosapentaenoic acid, and docosahexaenoic acid. The method for producing a highly unsaturated fatty acid-containing fat or oil powder according to claim 1, wherein the powder is at least one kind of polyunsaturated fatty acid. 4. The method according to claim 1, wherein the defatted soybean is contained in the fat and oil powder in an amount of 5 to 95% by weight.