JP7270160B2 - emulsified isada oil - Google Patents

Description

The present invention relates to the emulsification of Isada oil.

Isada is the name in the Sanriku region, and the Japanese name is Euphausia pacifica (scientific name: Euphausia pacifica, also known as Pacific krill), and the oil extracted from the horned krill is called Isada oil. Isada oil is produced by known production methods including the method described in Patent Document 1.

Isada oil is a marine resource that naturally contains omega-3 fatty acids such as docosahexaenoic acid (DHA) and eicosapentaenoic acid (EPA), phospholipids, and astaxanthin. While fish oil contains polyunsaturated fatty acids (TG-HUFA) bound to triglycerides, approximately 30-65% of fatty acids in Isada oil exist in the form bound to phospholipids. There are many polyunsaturated fatty acids (PC-HUFA) bound to PC), and it has the characteristics of n-3 polyunsaturated fatty acids (PUFA) that are easy to mix with water. This is because the phosphoric acid bound to the phospholipid is hydrophilic, and the fatty acid moiety is hydrophobic, thus exhibiting amphiphilicity.

JP 2017-122067

Polyunsaturated fatty acids such as EPA and DHA that bind to phospholipids contain many double bonds, so they are easily oxidized, and when oxidized, they produce an unpleasant odor and taste, making it extremely difficult to maintain their quality. is a hindrance to However, the current situation is that there is absolutely no knowledge for stable emulsification of Isada oil.

The problem to be solved by the present invention is to provide a stable Isada oil emulsified composition, a powder, and a method for producing the powder.

The present invention encompasses the subject matter described in the following sections.

Section 1. This emulsified composition is obtained by emulsifying Isada oil with saponin.

Section 2. Item 1. The emulsified composition according to Item 1, further comprising an antioxidant.

Item 3. Item 3. The emulsified composition according to Item 1 or 2, wherein the saponin is Quillaja saponin.

Section 4. A powder obtained by adding an excipient to the emulsified composition according to any one of Items 1 to 3 and drying.

Item 5. A method for producing Isada oil-containing powder, comprising the steps of emulsifying Isada oil with saponin to produce an emulsified composition, and drying and pulverizing the emulsified composition.

Item 6. Item 6. A method according to Item 5, wherein the emulsification comprises mechanical emulsification with a homogenizer.

Item 7. 7. A method according to paragraph 5 or 6, wherein said drying comprises spray drying.

Since the emulsified composition and powder of the present invention are excellent in stability, particularly in emulsion stability and oxidation stability, they can be It can be widely used in over-the-counter drugs, OTC), quasi-drugs, cosmetics, etc.

In addition, according to the method for producing Isada oil-containing powder of the present invention, Isada oil can be effectively emulsified, so Isada oil-containing powder with excellent stability can be produced.

A photograph showing the temporal state of an oil-in-water emulsion containing Isada oil prepared using various emulsifiers. (a) quilayanin, (b) sodium caseinate, (c) emalup, (d) gum arabic, (e) modified starch. Graph of oil droplet size distribution in emulsion solutions prepared with various emulsifiers. Graph showing the oxidation stability over time of Isada oil and antioxidant-added oil at 25°C. (a) EPA residual rate. (b) DHA residual rate. A graph showing the oxidation stability over time of Isada oil and antioxidant-added oil at 90°C. (a) EPA residual rate. (b) DHA residual rate. The graph which shows the oil droplet size distribution of the solution after emulsification. Graph showing the reconstituted oil droplet size distribution of the produced powder. Graph showing the powder size distribution of the produced powder. Surface structure of various powders. Left: Mechanical emulsification 7500rpm Right: Antioxidant addition 7500rpm Fracture surface structure of various powders. Left: Mechanical emulsification 7500rpm Right: Antioxidant addition 7500rpm Graph showing the absorbance of antioxidant-free and additive powders. Oxidative stability of oils and prepared powders at 50°C. (a) EPA residual rate. (b) DHA residual rate. Fading change of astaxanthin in oils and powders made.

The present invention includes emulsified compositions obtained by emulsifying Isada oil with saponin.

The Isada oil is not particularly limited as long as it is an oil extracted from horned krill. For example, Isada oil can be produced using a known method for extracting krill oil, such as Japanese Patent Publication No. 2004-534800 and Table No. 2010/035749. An example of a preferred method for producing Isada oil is described in Patent Document 1.

The amount of Isada oil in the emulsified composition is preferably 5-80% by weight, preferably 10-70% by weight, relative to the total weight of the emulsified composition. The amount of Isada oil is preferably 10% by mass or more and less than 90% by mass, and preferably more than 50% by mass and less than 80% by mass, based on 100% by mass of the solid content of the emulsified composition.

Saponins are glycosides that are widely distributed in plants and consist of steroids and triterpenes bound to sugars, and are a general term for compounds that form a foamy colloidal aqueous solution. Saponins are known as emulsifiers and the inventors have found that saponins are particularly good emulsifiers for emulsifying Isada oil. The saponin includes, for example, quillaja saponin, yucca saponin, soybean saponin, carrot saponin, kikiyo saponin, senega saponin, etc. Quillaja saponin is preferred in terms of emulsifying and stabilizing Isada oil for a long period of time. Quillaja saponin is a saponin contained in the bark of the rose family plant Soap (scientific name: Quillaja saponaria Mol.), trade name "Quillayanin C-100" (Maruzen Pharmaceutical Co., Ltd.), trade name "Quillayanin" (Juzen Co., Ltd.). etc. are commercially available. Usually, the content of saponins in commercially available quillaya extracts and yucca extracts is 1-10% by mass. The saponins used in the present invention also include partially hydrolyzed saponins obtained by partially hydrolyzing saponins.

Since the emulsified composition of the present invention uses saponin as an emulsifier, the emulsified composition can be stably maintained for a long period of time with the oil droplets dispersed in the aqueous phase. In one embodiment, in the emulsified composition of the present invention, oil droplets were dispersed in the aqueous phase even after 1 hour after stirring for 3 minutes at 8000 rpm with a homogenizer at 25°C and atmospheric pressure (almost one atmosphere). It is in a stable state, preferably stable after 2 hours, more preferably stable after 3 hours.

The amount of saponin to be blended is not particularly limited, but is preferably 1 to 5% by mass, more preferably 3% by mass or less, relative to the total mass of the emulsified composition. Moreover, the amount of saponin is preferably 0.05% by mass or more and less than 5% by mass, more preferably 0.05 to 3% by mass, based on 100% by mass of the solid content of the emulsified composition.

The emulsion composition of the present invention may further contain an antioxidant. As the antioxidant, any known antioxidant such as rosemary extract and sodium ascorbate may be used. Extracts are preferred.

Although the amount of the antioxidant to be blended is not particularly limited, it is preferably 1 to 6% by mass, more preferably 3% by mass, based on the total mass of the emulsified composition. Also, the amount of the antioxidant is preferably 0.05% by mass or more and less than 6% by mass, more preferably 0.05 to 3% by mass, based on 100% by mass of the solid content of the emulsified composition.

When the emulsified composition is an oil-in-water emulsion, the average oil droplet diameter in the emulsion is preferably 3 μm or less, more preferably 2 μm or less.

The emulsified composition may contain additives other than saponin, such as emulsifiers, colorants, and flavors.

The present invention also includes a powder obtained by adding an excipient to the emulsified composition and drying. Adding excipients to Isada oil and pulverizing it is preferable from the viewpoint of improving oxidation stability, handleability, and moldability of Isada oil.

Excipients are additives added to improve moldability, and any known excipients may be used, but sugars are preferred, and polysaccharides are more preferred. Examples of polysaccharides include at least one selected from the group consisting of thickening polysaccharides, starch, maltodextrin (DE is about 10 to 20, DE is dextrose equivalent), and dextrin (DE 10 or less), and maltodextrin is preferable. Although the amount of the excipient to be blended is not particularly limited, it is preferably 40 to 80% by mass, more preferably 50 to 60% by mass, based on the solid content mass of the emulsified composition from the viewpoint of improving moldability.

The amount of Isada oil is preferably 10 to 50% by mass, more preferably 30 to 40% by mass, based on the mass of the powder.

The powder diameter of the powder is preferably 1-1000 μm, more preferably 10-200 μm.

The reconstituted oil droplet diameter, which is the average oil droplet diameter measured after the powder is placed in distilled water to disperse the oil droplets, is preferably 3 μm or less, more preferably 2 μm or less.

The present invention includes a method for producing a powder containing Isada oil, comprising the steps of emulsifying Isada oil with saponin to form an emulsified composition, and drying and pulverizing the emulsified composition.

The emulsification conditions for Isada oil are not particularly limited, but high-pressure emulsification is preferred for reducing the oil droplet size of the emulsion after emulsification and the oil droplet size reconstituted from the powder, and mechanical emulsification is preferred for oxidation stability. High-pressure emulsification is emulsification under pressure higher than atmospheric pressure, and the pressure applied to the sample containing Isada oil and saponin is preferably 10 MPa or more and 1000 MPa or less. Mechanical emulsification is emulsification by a stirring device such as a homogenizer or vortex. The rotation speed of the stirrer is preferably 5000-10000 rpm, and the stirring time is preferably 30 seconds-3 minutes.

The method for drying the emulsified composition is not particularly limited, and examples thereof include spray drying, drying using a solvent, and freeze drying. Spray drying is preferred from the viewpoint of the oxidation stability of Isada oil and Isada oil-containing powder. Spray drying involves spraying the emulsified composition into a gas and drying the sprayed emulsified composition.

Since the emulsified composition containing Isada oil and the powder obtained by drying the emulsified composition of the present invention are excellent in stability, they can be It can be widely used in pharmaceuticals (over-the-counter drugs, OTC), quasi-drugs, cosmetics, etc. The emulsified composition containing Isada oil of the present invention and the powder obtained by drying the emulsified composition are excellent in emulsion stability and can be excellent in oxidation stability.

EXAMPLES The present invention will be described in more detail with reference to Examples below, but the present invention is not limited to these.

Example 1 Selection of emulsifiers suitable for emulsifying Isada oil 1 . Observation of Isada oil emulsification with various emulsifiers
experimental method
A weighed amount of distilled water was poured into a stainless steel beaker, a weighed excipient and a weighed emulsifier were dissolved in order to form a water-soluble fraction, and a weighed amount of Isada oil was added thereto as an oil-soluble fraction. Isada oil, excipients, emulsifiers, and distilled water were mixed according to the compositions shown in Tables 2 and 3, and emulsified with a Polytron homogenizer (PT10-35, Kinematica GA, Littau, Switzerland) for 3 minutes at 8000 rpm. Immediately after, after 1 hour, after 2 hours, and after 3 hours, the state of the emulsion solution was observed with the naked eye. The source of each reagent is as follows.

Isada Oil Trade name “Koyo Crill GT”, Koyo Chemical Co., Ltd. The composition of Isada Oil was as shown in Table 1.

Excipient Maltodextrin (DE19), trade name "Paindex #4" (DE19), Matsutani Chemical Industry Co., Ltd.)
Emulsifier Quillayanin (Contains Quillajasaponin)
Sodium caseinate (product name: B-100D), Mitsubishi-Kagaku Foods Co., Ltd.
Enzymatic degradation product of milk casein Product name: Emaruup Morinaga Milk Industry Co., Ltd.
Gum Arabic Product name: Gum Arabic Ogawa Koryo Co., Ltd.
Modified starch Product name “PURITY GUM BE” Ingredion Japan K.K.

The stability of the resulting emulsions is shown in Figure 1. Unexpectedly, the emulsion prepared using Quilayanin Figure 1(a) did not show sedimentary solids and was stable without phase separation even after 3 hours. On the other hand, when sodium caseinate (Fig. 1(b)), Emulup (Fig. 1(c)), and gum arabic (Fig. 1(d)) were used as emulsifiers, the emulsion was not uniform, and a sediment-like substance formed at the top of the solution. It can be seen that the solid matter of When emulsified with a protein-based emulsifier such as sodium caseinate, emulup, or gum arabic, a sediment-like solid matter was generated. It is speculated that If a powder containing Isada oil is produced with sediment formed, it is conceivable that part of the sediment will be mixed on the surface and inside of the powder, and that part will become a passage for oxygen, resulting in a powder with low oxidation stability. Sodium caseinate, emalup and gum arabic are therefore not suitable as emulsifiers for the preparation of emulsified Isada oil. In addition, when an emulsion was prepared with modified starch (Fig. 1(e)), no sediment-like solids were formed (Fig. 1(e), left), but red suspended solids were present at the top of the emulsion. 1(e) center), here, when the emulsion was fractionated and dissolved in distilled water, a red suspended substance emerged (Fig. 1(e) right). From this result, it was found that modified starch can be emulsified without forming sediment, but its emulsifying ability is not sufficient in this experiment.

2. Oil droplet size distribution of emulsion containing Isada oil
experimental method
Example 1, 1. The diameter of oil droplets in emulsions containing Isada oil prepared using various emulsifiers was measured by a laser diffraction particle size distribution analyzer (SALD-7100, Shimadzu Corporation, Japan). Distilled water was used to disperse the oil droplets. Absorbance was measured at 1.70-0.20i. In this experiment, the average particle size was taken as the size of the oil droplets, and the average was obtained by measuring three times for each sample. When measuring the oil droplet diameter, the sediment was avoided in the emulsion with sediment, and the lower uniform part was sampled and measured. In the emulsion solution prepared using the modified starch, fractional measurement was performed while avoiding red suspended solids.

Results The average diameter of oil droplets in the emulsion solution is shown in Table 4 below, and the oil droplet size distribution is shown in FIG. According to Fig. 2, some oil droplets in the Isada oil-containing emulsion using sodium caseinate and gum arabic had very large diameters, indicating that sodium caseinate and gum arabic did not have sufficient emulsifying ability in this experiment. rice field. Moreover, it can be seen that the oil droplet size distribution of the modified starch in FIG. 2 is not a wide and uniform oil droplet size distribution. Therefore, modified starch was also shown to have insufficient emulsifying ability in this experiment. Regarding Kilayanin and Emulup, the oil droplet size distribution is also sharp, and it can be said that they are uniform emulsions. As mentioned above, it forms a sediment, so it is not suitable as an emulsifier used for emulsifying Isada oil, and it was shown that Quillayanin is suitable.

Example 2. Investigation of oxidation stability of Isada oil and prepared powder 1 . Effects of antioxidants on the stability of Isada oil
experimental method
In order to investigate the effect of antioxidants on the stability of Isada oil, storage experiments were carried out on Isada oil at 25°C. As an antioxidant, 5% by weight of rosemary extract (trade name "RM Keeper OSE", Mitsubishi Chemical Foods Co., Ltd.) was added to Isada oil (trade name "Koyokrill GT", Koyo Chemical Co., Ltd.). About 0.2 g of Isada oil was weighed, and 2 ml of DMF (N,N-dimethylformamide) was added to dissolve the oil. 2 ml of hexane was added and stirred with a vortex mixer (G-560 type, MS equipment) to extract oil. Thereafter, the hexane layer was collected, 0.5 ml was fractionated, methyl-esterified using a fatty acid methylation kit (Nacalai Tesque Co., Ltd.), and spectrally analyzed using a gas chromatograph mass spectrometer (GC-MSQP5050A, Shimadzu Corporation, Japan). The peak areas of eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA) were recorded. The value obtained by dividing the peak area of EPA and DHA after storage by the peak area of EPA and DHA before storage is defined as the residual ratio of EPA and DHA. evaluated.
In addition, the retention of EPA and DHA when Isada oil was kept at 90°C for 1-2 hours was also investigated.

Results The results of the experiment are shown in FIG. In Fig. 3(a), the retention rate of EPA after 7 days was about 79% for the oil without antioxidants and about 89% for the oil with antioxidants added. In other words, regarding EPA, the antioxidant-added oil retained nearly 90% even after being left at room temperature for a week, and the retention rate was about 10% higher than the antioxidant-free oil. In FIG. 3(b), the retention rate of DHA after 7 days was about 75% in the antioxidant-free oil and about 87% in the antioxidant-added oil.

Furthermore, FIG. 4 shows the residual ratio of EPA and DHA when Isada oil was kept at 90° C. for 1 to 2 hours. The addition of antioxidants improved the retention rate of EPA and DHA, indicating that the addition of antioxidants is useful for short-term high-temperature maintenance.

2. Preparation of powder by emulsification of emulsion solution with antioxidant and spray drying
experimental method
An antioxidant was added to the emulsion solution based on the composition table shown in Table 5, and a spray-dried powder was produced under the emulsification conditions of mechanical emulsification at 7500 rpm for 3 minutes using a Polytron homogenizer. The atomization conditions were an inlet temperature of 140 oC, a flow rate of 25 mL/min, an air volume of 110 kg/h, and an atomizer rotation speed of 10,000 rpm.

The average oil droplet size of the solution after emulsification, the viscosity of the solution after emulsification, the water content of the prepared powder, the reconstituted oil droplet size of the prepared powder, and the powder size of the prepared powder were measured.

Results Table 6 shows the average oil droplet diameter of the solution after emulsification, the viscosity of the solution after emulsification, the water content of the prepared powder, the reconstituted oil droplet diameter of the prepared powder, and the powder diameter of the prepared powder. FIG. 5 shows the oil droplet size distribution of the solution after emulsification, FIG. 6 shows the reconstituted oil droplet size distribution of the produced powder, and FIG. 7 shows the produced powder size distribution. 8 and 9 show the observation results of the surface structure and fracture surface structure of the produced powder by SEM (JSM-6060, JEOL, Japan). From Table 6, the oil droplet diameter after emulsification and the reconstituted oil droplet diameter were almost the same. As for the powder size, both powders were produced with a size of about 58 μm. Further, as shown in FIG. 8, many irregularities and wrinkles were observed in the surface structure of all powders. From FIG. 9, Isada oil entrapped in the powder was observed, and a plurality of solid ones were observed.

3. Effects of antioxidants on the aging stability of prepared powders
experimental method
2 above. We investigated the effect of adding antioxidants on the oxidation stability of the powders. FIG. 10 shows the absorbance measurement results of the antioxidant-free and antioxidant-added powders, FIG. 11 shows the retention rate of the EPA and DHA contents over time, and FIG. 12 shows the fading change of astaxanthin.

About 0.2 g of Isada oil or about 0.5 g of powder was weighed, and 2 ml of DMF (N,N-dimethylformamide) was added to dissolve the oil and powder. Then, 20 μl of the lysate was taken and diluted 100-fold with 2 ml of ethanol. Then, the mixture was centrifuged at 4000 rpm for 5 minutes using a centrifuge (KUBOTA2010, Kubota Seisakusho) to remove sugar. And the absorbance at 478 nm was recorded by a UV-visible spectrophotometer.

Results From FIG. 10, there was almost no difference in the absorbance spectrum between the powders before storage, regardless of the presence or absence of antioxidant addition. However, when comparing the spectrum after 2 weeks with and without antioxidants, the peak at around 478 nm for the powder without antioxidants disappeared, but the peak for the powder with antioxidants was observed even after 2 weeks. was confirmed to still exist. In addition, as shown in FIGS. 11(a) and (b), the residual rates of EPA and DHA after 2 weeks were improved. In particular, it appeared more remarkably in the examination result of DHA. Furthermore, from FIG. 12, it was found that the discoloration of astaxanthin was greatly suppressed in the prepared powder to which the antioxidant was added. Therefore, it was suggested that the addition of an antioxidant contributes to the oxidation stability of the produced powder.

Claims (11)

An emulsified composition containing an excipient in which isada oil is emulsified with saponin ,
For the solid content of the emulsified composition,
Isada oil is 10% by mass or more and less than 90% by mass,
An emulsified composition containing 0.05% by mass or more and less than 5% by mass of saponin. For the solid content of the emulsified composition,
Isada oil is 10% by mass or more and less than 90% by mass,
An emulsified composition comprising 0.05% by mass or more and less than 5% by mass of saponin and 40 to 80% by mass of an excipient. 3. The emulsified composition of claim 1 or 2, further comprising an antioxidant. 4. The emulsion composition of claim 3 , wherein the antioxidant comprises rosemary extract. The emulsified composition according to any one of claims 1 to 4 , wherein said saponin is Quillaja saponin. A powder obtained by drying the emulsified composition according to claim 1 . A step of emulsifying Isada oil with saponin to produce an emulsified composition containing an excipient, wherein 10% by mass or more and less than 90% by mass of Isada oil and 0.05% by mass of saponin relative to the solid content of the emulsified composition % or more and less than 5% by mass, a step of producing an emulsion composition ,
and a method for producing Isada oil-containing powder, comprising the steps of drying and pulverizing the emulsified composition. The method according to claim 7, wherein the excipient is 40 to 80% by weight based on the solid content of the emulsified composition. 8. The method of claim 7 , wherein emulsifying comprises mechanical emulsification with a homogenizer. A method according to any of claims 7-9, wherein said drying comprises spray drying. 8. The method of claim 7 , wherein the emulsified composition further comprises rosemary extract.

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