WO2016009964A1 - Process for producing fatty-acid-containing emulsion using ultrasonic wave - Google Patents

Process for producing fatty-acid-containing emulsion using ultrasonic wave Download PDF

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WO2016009964A1
WO2016009964A1 PCT/JP2015/069923 JP2015069923W WO2016009964A1 WO 2016009964 A1 WO2016009964 A1 WO 2016009964A1 JP 2015069923 W JP2015069923 W JP 2015069923W WO 2016009964 A1 WO2016009964 A1 WO 2016009964A1
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unsaturated fatty
emulsion
fatty acid
emulsification
acid
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PCT/JP2015/069923
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French (fr)
Japanese (ja)
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祥史 山谷
一輝 丸山
亜紗美 後迫
裕介 柿▲崎▼
創作 市川
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マルハニチロ株式会社
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    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23D—EDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS, COOKING OILS
    • A23D7/00—Edible oil or fat compositions containing an aqueous phase, e.g. margarines
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23G—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
    • A23G9/00—Frozen sweets, e.g. ice confectionery, ice-cream; Mixtures therefor
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L2/00—Non-alcoholic beverages; Dry compositions or concentrates therefor; Their preparation
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K39/00—Medicinal preparations containing antigens or antibodies
    • A61K39/39—Medicinal preparations containing antigens or antibodies characterised by the immunostimulating additives, e.g. chemical adjuvants
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/10—Dispersions; Emulsions
    • A61K9/107—Emulsions ; Emulsion preconcentrates; Micelles

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  • the present invention relates to a method for producing an ⁇ -3 unsaturated fatty acid-containing oil-in-water (O / W type) emulsion using ultrasound and its use.
  • ⁇ -3 unsaturated fatty acids such as docosahexaenoic acid and eicosapentaenoic acid have various actions such as platelet aggregation inhibitory action, blood cholesterol lowering action, brain function improving action (Patent Documents 1 and 2), and antiallergic action. It has been known.
  • omega-3 unsaturated fatty acids such as docosahexaenoic acid and eicosapentaenoic acid are oil-soluble components. As it is, it cannot be added to water-soluble components, and the range of application has been limited in addition to foods.
  • omega-3 unsaturated fatty acids such as docosahexaenoic acid and eicosapentaenoic acid are much less oxidatively stable than linoleic acid, which is an ⁇ -6 unsaturated fatty acid.
  • various antioxidant means have been taken in utilizing ⁇ -3 unsaturated fatty acids such as docosahexaenoic acid and eicosapentaenoic acid and oils and fats containing them.
  • Examples of the method for preventing the oxidation of ⁇ -3 unsaturated fatty acid include, for example, a method of mixing ⁇ -3 unsaturated fatty acid with an antioxidant such as tocopherol and catechin, a method of encapsulating ⁇ -3 unsaturated fatty acid with gelatin and the like, Examples thereof include a method of enclosing ⁇ -3 unsaturated fatty acid in an inert gas atmosphere.
  • an easily oxidizable fat-soluble component is blended as an O / W / O-type dispersed composite emulsion that contains an easily oxidizable fat-soluble component in the inner phase oil and an organically modified clay mineral in the outer phase oil.
  • Patent Document 3 Method of preventing oxidation
  • Patent Document 4 Method of making pH in emulsion containing protein component acidic from isoelectric point of protein component
  • Patent Document 5 Low DE maltodextrin, melting point from about 25 ° C
  • Patent Document 5 a method for preparing a composition containing oil encapsulated with a higher emulsifier
  • the object of the present invention is to provide a production method that maintains the oxidation stability of an O / W emulsion containing ⁇ -3 unsaturated fatty acids such as docosahexaenoic acid and eicosapentaenoic acid in response to the above-mentioned demands.
  • the method for producing an O / W emulsion according to the present invention comprises an ⁇ -3 unsaturated oil having an oxidation stability by emulsifying an oil phase and an aqueous phase containing an ⁇ -3 unsaturated fatty acid with ultrasonic waves having a frequency of 20 kHz or more and an output of 200 W or more. It is characterized by obtaining an O / W type emulsion containing 3 unsaturated fatty acids.
  • the O / W type emulsion containing an omega-3 unsaturated fatty acid having oxidation stability according to the present invention is produced by the above production method.
  • the O / W type emulsion containing an omega-3 unsaturated fatty acid having oxidative stability is any one of foods, supplements, pharmaceuticals, animal drugs, feeds and supplementary feeds containing ⁇ -3 unsaturated fatty acid components.
  • it can be applied to foods such as dressings, supplements such as drinks, pharmaceuticals such as vaccines, enteral nutrients and veterinary drugs, feeds such as alternative milk for livestock, and supplementary feeds.
  • an ultrasonic wave is used to produce an O / W type emulsion by emulsification of an aqueous phase and an oil phase containing an ⁇ -3 unsaturated fatty acid, so that ⁇ - such as docosahexaenoic acid and eicosapentaenoic acid is used.
  • the O / W emulsion containing O 3 unsaturated fatty acid can be maintained in oxidation stability, and an O / W emulsion containing ⁇ -3 unsaturated fatty acid having long-term storage stability can be provided.
  • the black triangle indicates the hydroperoxide amount in high-pressure emulsification
  • the black square indicates the hydroperoxide amount in ultrasonic emulsification. It is a figure which shows the relationship between the wrinkle average droplet diameter of the emulsion prepared by the ultrasonic emulsification method, and a polydispersity index.
  • the black rhombus indicates the droplet diameter
  • the black square indicates the polydispersity index (PdI).
  • PdI polydispersity index
  • the black rhombus indicates the droplet diameter
  • the black square indicates the polydispersity index (PdI).
  • the first of the present invention is an O / W containing an oxidatively stable ⁇ -3 unsaturated fatty acid characterized by emulsification using an ultrasonic generator having a frequency of 20 kHz or more and an output of 200 W or more.
  • a second aspect of the present invention is to produce an O / W emulsion containing an ⁇ -3 unsaturated fatty acid, characterized in that the average droplet diameter is 250 nm or less and the polydispersity index is less than 0.3, using the above method. It is a method to do.
  • Examples of the ⁇ -3 unsaturated fatty acid that is the subject of the present invention include docosahexaenoic acid and eicosapentaenoic acid.
  • a surfactant or an emulsifier can be used to disperse oil droplets containing an ⁇ -3 unsaturated fatty acid in the aqueous phase.
  • the surfactant or emulsifier can be selected according to the intended use of the O / W emulsion containing the ⁇ -3 unsaturated fatty acid.
  • sucrose fatty acid ester, ascorbic acid fatty acid ester, sorbitan fatty acid ester, lecithin, and monoglyceride are particularly preferable. If necessary, at least one of a surfactant and an emulsifier can be used.
  • the addition amount of at least one of the surfactant and the emulsifier is sufficient to be 0.01 to 2 (w / v)% based on the whole emulsion (oil phase + liquid phase).
  • a water-soluble or fat-soluble antioxidant, an inclusion compound such as cyclodextrin, a chelating agent, a pH adjuster, or the like can be used in combination.
  • any oil and fat can be used without particular limitation.
  • fish oil containing ⁇ -3 unsaturated fatty acid microalgal extract oil, sesame oil containing ⁇ -6 unsaturated fatty acid
  • Ordinary animal and vegetable oils and fats such as soybean oil can also be used.
  • the fish oil is preferably a fish oil containing an omega-3 unsaturated fatty acid in a proportion of 0 to 99.9% by weight, particularly preferably a fish oil containing an omega-3 unsaturated fatty acid in a proportion of 10 to 70% by weight, most preferably 20 to Fish oil containing ⁇ -3 unsaturated fatty acid in a proportion of 40% by weight can be used.
  • oil and fat for the oil phase does not contain ⁇ -3 unsaturated fatty acid or the content of ⁇ -3 unsaturated fatty acid does not reach the target amount, Or you may adjust the content of omega-3 unsaturated fatty acid by adding the fats and oils containing omega-3 unsaturated fatty acid.
  • the oil phase can contain various fat-soluble additives depending on the intended use of the O / W type emulsion containing ⁇ -3 unsaturated fatty acid.
  • Water can be used as a material constituting the aqueous phase for emulsion production.
  • Various types of water-soluble additives can also be contained in the aqueous phase depending on the intended use of the O / W emulsion containing an ⁇ -3 unsaturated fatty acid.
  • examples of such additives include proteins such as casein, whey protein, gelatin, and degradation products thereof, and at least one of them can be used.
  • the ratio of the water phase to the oil phase can be selected from the range of 99.9: 0.1 to 50:50 (weight basis).
  • An oil phase and an aqueous phase are prepared, and preliminarily emulsified as necessary, followed by ultrasonic emulsification.
  • ultrasonic waves used for emulsification ultrasonic waves having a frequency of 20 kHz or more and an output of 200 W or more are used.
  • the upper limit of the frequency and output is not particularly limited, but the frequency can be 1 MHz or less and the output can be 16 kW or less.
  • a method of irradiation capable of the desired ultrasonic emulsification such as a method of continuous irradiation for a predetermined time, a method of intermittent irradiation for a predetermined time, or the like can be selected.
  • the energy input per unit area of the emulsion by ultrasonic waves in the emulsification process can be calculated by the following equation.
  • -Energy per unit area (kJ / m 3 ) Current (A) x Voltage (V) x Time (sec) / Emulsion surface area (m 3 )
  • the energy applied per unit area is preferably in the range of 0.01 to 1.0 kJ / m 3 .
  • the ultrasonic emulsification is preferably performed until the average droplet diameter in the O / W emulsion is 250 nm or less and the polydispersity index is less than 0.3.
  • the lower limits of the average droplet diameter and the polydispersity index are not particularly limited, but ultrasonic emulsification may be performed so that the average droplet diameter is 50 nm or more and the polydispersity index is 0.01 or more.
  • the liquid temperature during ultrasonic emulsification is preferably 4 to 50 ° C., particularly preferably 4 to 40 ° C., and most preferably 4 to 10 ° C.
  • the O / W type emulsion containing an ⁇ -3 unsaturated fatty acid obtained by the production method of the present invention is an ultrasonic wave with low administration energy when oil droplets containing an ⁇ -3 unsaturated fatty acid are dispersed in an aqueous phase.
  • ⁇ -3 unsaturated fatty acid is contained in the oil droplets so that it has high oxidative stability and has long-term storage stability.
  • a / W type emulsion can be obtained.
  • the ⁇ -3 unsaturated fatty acid-containing O / W emulsion according to the present invention can be suitably used as a raw material for producing various products containing ⁇ -3 unsaturated fatty acids. Examples of such products include foods, supplements, pharmaceuticals and animal drugs, feeds and supplementary feeds.
  • the ⁇ -3 unsaturated fatty acid-containing O / W emulsion according to the present invention can be added to various products as described above while maintaining the form of the emulsion, and can be particularly suitably used as a material for the product in the form of an emulsion. .
  • Examples of the product in the form of an emulsion include mayonnaise, dressing, ice cream, drink, enteral nutrition, vaccine adjuvant, adjuvant vaccine, livestock substitute milk, and the like.
  • the ⁇ -3 unsaturated fatty acid-containing O / W emulsion according to the present invention can be used for blending ⁇ -3 unsaturated fatty acids.
  • Example 1 (Method) Preparation of emulsion components, aqueous phase and oil phase Table 1 shows the emulsion components.
  • DHA-containing refined fish oil was DHA-containing refined fish oil from Maruha Nichiro Co., Ltd.
  • the starch degradation product, casein hydrolyzate, and water were mixed and dissolved in a 60 ° C. hot water bath to obtain an aqueous phase.
  • DHA-containing purified fish oil, glycerin fatty acid ester, and lecithin were mixed and dissolved in a water bath at 80 ° C. to obtain an oil phase.
  • Preparation of emulsion by each emulsification method and ultrasonic emulsification method is performed after pre-emulsification treatment with a stirrer (three-one motor 1200G, Heidon) at a stirring rotation speed of 9,600 rpm for 5 minutes. This was carried out using an electrostrictive vibrator type ultrasonic emulsifier (UD-201, Tommy Seiko, ultrasonic wave number 20 KHz). Emulsification was performed for 10 minutes at an oscillation output of 200 W. The ultrasonic wave was intermittently irradiated for 0.5 second in 1 second.
  • Emulsion preparation by high-pressure emulsification method was performed by pre-emulsification treatment at 9,600 rpm for 5 minutes using a stirring emulsifier (Polytron PT3100, Kinematica), then Nanomizer NM2-L100 (Yoshida Kikai Kogyo Co., Ltd.) ).
  • the operation pressure during the emulsification treatment was fixed at 175 Mpa, and the emulsification treatment was carried out with one treatment.
  • the preliminary emulsification treatment it can be visually confirmed that the water phase and the oil phase are homogenized, and an average droplet diameter of about 500 nm to 1 mm is used as a guideline for completion.
  • the emulsion temperature during all emulsification operations was controlled below 40 ° C to prevent the oxidation of the oil contained in the emulsion.
  • Emulsion was stored at 50 ° C in the dark for 30 days, diluted to 1/2000 with 50 mM NaCl aqueous solution, ⁇ average droplet size (hydrodynamic diameter) and polydispersity
  • the index (PdI) was measured by dynamic light scattering method. Determination of hydroperoxide contained in the emulsion The emulsion prepared by each emulsification method was stored at 50 ° C. in the dark for 10 days, and the concentration of hydroperoxide contained in the sample was determined using the iron thiocyanate method.
  • the amount of cumene hydroperoxide which is a standard substance of lipid peroxide, was plotted with the horizontal axis and the absorbance as the vertical axis, and a regression line was obtained by the least square method to prepare a calibration curve. Using this calibration curve, the peroxide value of the emulsion was expressed in terms of hydroperoxide equivalent (POV value (nmol / l)). Energy per unit area The energy input per unit area of the emulsion was calculated according to the following formula.
  • FIG. 1 shows the wrinkle average droplet diameter and polydispersity index of the emulsion prepared by the ultrasonic emulsification method.
  • the initial droplet size was about 150 nm, and there was almost no change even after 30 days of storage. Similarly, PdI did not change from about 0.1 and maintained high monodispersity.
  • FIG. 2 shows the average droplet diameter and polydispersity index of the emulsion prepared by the high pressure emulsification method. The initial droplet size was about 100 nm, and there was almost no change even after 30 days of storage, but PdI was about 0.16 from about 0.1 to 30 days after the initial release, indicating that the monodispersity decreased It was.
  • FIG. 1 shows the wrinkle average droplet diameter and polydispersity index of the emulsion prepared by the ultrasonic emulsification method.
  • the initial droplet size was about 150 nm, and there was almost no change even after 30 days of storage. Similarly, PdI did not change from about 0.1 and maintained
  • Example 2 (Method) Preparation of emulsion components, aqueous phase and oil phase
  • the aqueous phase and oil phase were prepared in the same manner as in Example 1.
  • Preparation of emulsion by each emulsification method / Ultrasonic emulsification method The emulsion was prepared in the same manner as in Example 1.
  • -Stir emulsification method Emulsion preparation by the stir emulsification method was performed using a stir emulsifier (Polytron PT3100, Kinematica).
  • the oil phase and the aqueous phase were mixed and emulsified for 5 minutes at a stirring speed of 24,000 rpm.
  • the emulsion temperature during all emulsification operations was controlled below 40 ° C to prevent the oxidation of the oil contained in the emulsion.
  • Measurement of droplet size distribution and dispersion stability The emulsion immediately after the emulsification treatment was stored at 50 ° C. in the dark for 16 days, diluted to a concentration of 1/2000 with 50 mM NaCl aqueous solution, and the average droplet size (hydrodynamics) Diameter) and polydispersity index (PdI) were measured by dynamic light scattering method. Determination of hydroperoxide contained in the emulsion The emulsion prepared by each emulsification method was stored at 50 ° C.
  • FIG. 4 shows the mean droplet diameter and polydispersity index of the emulsion prepared by the ultrasonic emulsification method.
  • the initial droplet size was about 200 nm, and there was almost no change even after 16 days of storage. Similarly, PdI also increased slightly from about 0.15 and reached about 0.2 on the 16th day.
  • FIG. 5 shows the average droplet diameter and polydispersity index of the emulsion prepared by the stirring emulsification method.
  • the initial droplet size was about 260 nm, which increased with time, and was about 350 nm on the 16th day of storage.
  • PdI also increased to about 0.4 after about 0.25 to 16 days, and thus monodispersity was considered to be low.
  • FIG. 4 shows the mean droplet diameter and polydispersity index of the emulsion prepared by the ultrasonic emulsification method.
  • the initial droplet size was about 200 nm, and there was almost no change even after 16 days of storage. Similarly, PdI

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Abstract

A process for producing an O/W type emulsion by emulsifying an aqueous phase and an oily phase comprising an ω-3 unsaturated fatty acid, said process comprising utilizing a method of emulsification with an ultrasonic wave having a frequency of 20 kHz or higher and an output of 200 W or higher, thereby maintaining the oxidative stability of the ω-3 unsaturated fatty acid contained in the oil droplets of the O/W type emulsion. This ultrasonic emulsification method can solve the problem wherein the long-term stability of ω-3 unsaturated fatty acids remains unsolved even when any of various oxidation prevention methods is used and wherein when ingesting the ω-3 unsaturated fatty acids, there are cases where the emulsions feel unpleasant because of an oxidized flavor and a fully satisfactory oxidation prevention effect cannot be obtained. The ultrasonic emulsification method makes it possible to provide the production process for maintaining the oxidative stability of an O/W type emulsion containing an ω-3 unsaturated fatty acid such as docosahexaenoic acid or eicosapentaenoic acid.

Description

超音波を用いた脂肪酸含有エマルジョンの製造方法Method for producing fatty acid-containing emulsion using ultrasonic wave
　本発明は、超音波を用いたω-3不飽和脂肪酸含有水中油滴（O/W型）エマルジョンの製造方法及びその用途に関する。 The present invention relates to a method for producing an ω-3 unsaturated fatty acid-containing oil-in-water (O / W type) emulsion using ultrasound and its use.
　ドコサヘキサエン酸、エイコサペンタエン酸等のω-3不飽和脂肪酸は、血小板凝集抑制作用、血中コレステロール低下作用、脳機能改善作用（特許文献１、２）、抗アレルギー作用等の種々の作用を有することが知られている。また、ドコサヘキサエン酸、エイコサペンタエン酸等のω-3不飽和脂肪酸は油溶性成分である。そのままでは、水溶性成分への添加はできず、食品への添加などでは応用範囲が限定されていた。したがって、様々な食品にω-3不飽和脂肪酸を添加するには、O/W型エマルジョンや粉末油脂への調製が求められてきた。
　しかしながら、ドコサヘキサエン酸、エイコサペンタエン酸等のω-3不飽和脂肪酸はω-6不飽和脂肪酸であるリノール酸等に比べて、酸化安定性が非常に悪く、酸化されると不快な臭いや味を呈する。そのため、ドコサヘキサエン酸、エイコサペンタエン酸等のω-3不飽和脂肪酸及びそれを含有する油脂の利用にあたっては、種々の酸化防止手段が講じられている。
　ω-3不飽和脂肪酸の酸化防止方法としては、例えば、ω-3不飽和脂肪酸をトコフェロール、カテキン等の抗酸化剤と混合する方法、ゼラチン等でω-3不飽和脂肪酸をカプセル化する方法、不活性ガス雰囲気中にω-3不飽和脂肪酸を封入する方法等を挙げることができる。また、内相油中に易酸化性の脂溶性成分を配合し、外相油中に有機変性粘土鉱物を含む、O/W/O型の分散された複合エマルジョンとして易酸化性の脂溶性成分の酸化を防止する方法（特許文献３）、蛋白成分を含むエマルジョン中のpHを蛋白成分の等電点より酸性にする方法（特許文献４）、低ＤＥマルトデキストリンを含み、融点が約25℃よりも高い乳化剤により封入された油を含む組成物を調製する方法（特許文献５）等の工夫がなされている。 Ω-3 unsaturated fatty acids such as docosahexaenoic acid and eicosapentaenoic acid have various actions such as platelet aggregation inhibitory action, blood cholesterol lowering action, brain function improving action (Patent Documents 1 and 2), and antiallergic action. It has been known. Moreover, omega-3 unsaturated fatty acids such as docosahexaenoic acid and eicosapentaenoic acid are oil-soluble components. As it is, it cannot be added to water-soluble components, and the range of application has been limited in addition to foods. Therefore, in order to add ω-3 unsaturated fatty acids to various foods, preparation to O / W type emulsions and powdered oils and fats has been required.
However, omega-3 unsaturated fatty acids such as docosahexaenoic acid and eicosapentaenoic acid are much less oxidatively stable than linoleic acid, which is an ω-6 unsaturated fatty acid. Present. Therefore, various antioxidant means have been taken in utilizing ω-3 unsaturated fatty acids such as docosahexaenoic acid and eicosapentaenoic acid and oils and fats containing them.
Examples of the method for preventing the oxidation of ω-3 unsaturated fatty acid include, for example, a method of mixing ω-3 unsaturated fatty acid with an antioxidant such as tocopherol and catechin, a method of encapsulating ω-3 unsaturated fatty acid with gelatin and the like, Examples thereof include a method of enclosing ω-3 unsaturated fatty acid in an inert gas atmosphere. In addition, an easily oxidizable fat-soluble component is blended as an O / W / O-type dispersed composite emulsion that contains an easily oxidizable fat-soluble component in the inner phase oil and an organically modified clay mineral in the outer phase oil. Method of preventing oxidation (Patent Document 3), Method of making pH in emulsion containing protein component acidic from isoelectric point of protein component (Patent Document 4), Low DE maltodextrin, melting point from about 25 ° C In addition, there have been devised methods such as a method for preparing a composition containing oil encapsulated with a higher emulsifier (Patent Document 5).
特開平１－２７９８２７号公報Japanese Patent Laid-Open No. 1-279827 特開平２－４９７２３号公報JP-A-2-49723 特表２００６－５１４５４１号公報Special table 2006-514541 gazette 特開平０９－２７６６７６号公報JP 09-276676 A 特表平２０１３－５３０６８４号公報JP-T-2013-530684 Publication
　しかし、上記の各種酸化防止方法を用いても、ω-3不飽和脂肪酸の長期の安定性には問題が残り、ω-3不飽和脂肪酸の摂取にあたっては酸化臭による不快感があり、十分に満足できる酸化防止効果が得られない場合がある。
　本発明の目的は、上記のような要望に応え、ドコサヘキサエン酸、エイコサペンタエン酸等のω-3不飽和脂肪酸を含むO/W型エマルジョンの酸化安定性を保つ製造方法を提供することである。 However, even with the above-mentioned various antioxidant methods, there remains a problem with the long-term stability of ω-3 unsaturated fatty acids. A satisfactory antioxidant effect may not be obtained.
The object of the present invention is to provide a production method that maintains the oxidation stability of an O / W emulsion containing ω-3 unsaturated fatty acids such as docosahexaenoic acid and eicosapentaenoic acid in response to the above-mentioned demands.
　本発明にかかるO/W型エマルジョンの製造方法は、ω-3不飽和脂肪酸を含む油相と水相を周波数20kHz以上、出力200Ｗ以上の超音波により乳化して、酸化安定性を有するω-3不飽和脂肪酸を含むO/W型エマルジョンを得ることを特徴とする。
　本発明にかかる酸化安定性を有するω-3不飽和脂肪酸を含むO/W型エマルジョンは、上記の製造方法により製造されたものであることを特徴とする。 The method for producing an O / W emulsion according to the present invention comprises an ω-3 unsaturated oil having an oxidation stability by emulsifying an oil phase and an aqueous phase containing an ω-3 unsaturated fatty acid with ultrasonic waves having a frequency of 20 kHz or more and an output of 200 W or more. It is characterized by obtaining an O / W type emulsion containing 3 unsaturated fatty acids.
The O / W type emulsion containing an omega-3 unsaturated fatty acid having oxidation stability according to the present invention is produced by the above production method.
　本発明にかかる酸化安定性を有するω-3不飽和脂肪酸を含むO/W型エマルジョンは、ω-3不飽和脂肪酸成分を含む食品、補助食品、医薬品、動物薬、飼料及び補助飼料のいずれかの製品の製造において、ω-3不飽和脂肪酸成分配合用として使用することができる。例えば、ドレッシング等の食品、ドリンク等の補助食品、ワクチン、経腸栄養剤等の医薬品及び動物薬、家畜用代替乳等の飼料及び補助飼料に応用することができる。 The O / W type emulsion containing an omega-3 unsaturated fatty acid having oxidative stability according to the present invention is any one of foods, supplements, pharmaceuticals, animal drugs, feeds and supplementary feeds containing ω-3 unsaturated fatty acid components. Can be used for blending ω-3 unsaturated fatty acid component. For example, it can be applied to foods such as dressings, supplements such as drinks, pharmaceuticals such as vaccines, enteral nutrients and veterinary drugs, feeds such as alternative milk for livestock, and supplementary feeds.
　本発明によれば、水相と、ω-3不飽和脂肪酸を含む油相との乳化によるO/W型エマルジョンの製造に超音波を利用することより、ドコサヘキサエン酸、エイコサペンタエン酸等のω-3不飽和脂肪酸を含むO/W型エマルジョンの酸化安定性を保つことができ、長期保存性を有するω-3不飽和脂肪酸含有O/W型エマルジョンを提供することができる。 According to the present invention, an ultrasonic wave is used to produce an O / W type emulsion by emulsification of an aqueous phase and an oil phase containing an ω-3 unsaturated fatty acid, so that ω- such as docosahexaenoic acid and eicosapentaenoic acid is used. The O / W emulsion containing O 3 unsaturated fatty acid can be maintained in oxidation stability, and an O / W emulsion containing ω-3 unsaturated fatty acid having long-term storage stability can be provided.
超音波乳化法で調製したエマルジョンのΖ平均液滴径と多分散指数の関係を示す図である。黒菱形は液滴径を、黒四角は多分散指数(PdI)を示す。It is a figure which shows the relationship between the wrinkle average droplet diameter of the emulsion prepared by the ultrasonic emulsification method, and a polydispersity index. The black rhombus indicates the droplet diameter, and the black square indicates the polydispersity index (PdI). 高圧乳化法で調製したエマルジョンのΖ平均液滴径と多分散指数の関係を示す図である。黒菱形は液滴径を、黒四角は多分散指数(PdI)を示す。It is a figure which shows the relationship between the wrinkle average droplet diameter of the emulsion prepared by the high pressure emulsification method, and a polydispersity index. The black rhombus indicates the droplet diameter, and the black square indicates the polydispersity index (PdI). 各乳化法で作製したエマルジョンのヒドロペルオキシド量の経時変化を示す図である。黒三角は高圧乳化におけるヒドロペルオキシド量を、黒四角は超音波乳化におけるヒドロペルオキシド量を示す。It is a figure which shows the time-dependent change of the hydroperoxide amount of the emulsion produced by each emulsification method. The black triangle indicates the hydroperoxide amount in high-pressure emulsification, and the black square indicates the hydroperoxide amount in ultrasonic emulsification. 超音波乳化法で調製したエマルジョンのΖ平均液滴径と多分散指数の関係を示す図である。黒菱形は液滴径を、黒四角は多分散指数(PdI)を示す。It is a figure which shows the relationship between the wrinkle average droplet diameter of the emulsion prepared by the ultrasonic emulsification method, and a polydispersity index. The black rhombus indicates the droplet diameter, and the black square indicates the polydispersity index (PdI). 撹拌乳化法で調製したエマルジョンのΖ平均液滴径と多分散指数の関係を示す図である。黒菱形は液滴径を、黒四角は多分散指数(PdI)を示す。It is a figure which shows the relationship between the wrinkle average droplet diameter of the emulsion prepared by the stirring emulsification method, and a polydispersity index. The black rhombus indicates the droplet diameter, and the black square indicates the polydispersity index (PdI). 各乳化法で作製したエマルジョンのヒドロペルオキシド量の経時変化を示す図である。黒菱形は攪拌乳化におけるヒドロペルオキシド量を、黒四角は超音波乳化におけるヒドロペルオキシド量を示す。It is a figure which shows the time-dependent change of the hydroperoxide amount of the emulsion produced by each emulsification method. The black rhombus indicates the hydroperoxide amount in the stirring emulsification, and the black square indicates the hydroperoxide amount in the ultrasonic emulsification.
　本発明者等は、ドコサヘキサエン酸、エイコサペンタエン酸等のω-3不飽和脂肪酸を含むO/W型エマルジョンの酸化安定性を保つ方法の研究を進めていくうちに、撹拌乳化法、高圧乳化法、超音波乳化法のうち、超音波乳化法にて製造したエマルジョンが酸化安定性に優れていることを見出し、本発明を完成させるに至った。
　即ち、本発明の第一は、周波数20kHz以上、出力200Ｗ以上の超音波発生装置を用いて、乳化することを特徴とする、酸化安定性の高い、ω-3不飽和脂肪酸を含むO/W型エマルジョンを製造する方法である。本発明の第二は、前記方法を用いて、平均液滴径が250nm以下、多分散指数が0.3未満であることを特徴とする、ω-3不飽和脂肪酸を含むO/W型エマルジョンを製造する方法である。本発明の対象となるω-3不飽和脂肪酸としては、例えばドコサヘキサエン酸、エイコサペンタエン酸が挙げられる。 While the inventors proceeded with research on a method for maintaining the oxidative stability of O / W type emulsions containing omega-3 unsaturated fatty acids such as docosahexaenoic acid and eicosapentaenoic acid, the stirring emulsification method and the high pressure emulsification method Of the ultrasonic emulsification methods, the emulsion produced by the ultrasonic emulsification method was found to have excellent oxidation stability, and the present invention was completed.
That is, the first of the present invention is an O / W containing an oxidatively stable ω-3 unsaturated fatty acid characterized by emulsification using an ultrasonic generator having a frequency of 20 kHz or more and an output of 200 W or more. A method for producing a mold emulsion. A second aspect of the present invention is to produce an O / W emulsion containing an ω-3 unsaturated fatty acid, characterized in that the average droplet diameter is 250 nm or less and the polydispersity index is less than 0.3, using the above method. It is a method to do. Examples of the ω-3 unsaturated fatty acid that is the subject of the present invention include docosahexaenoic acid and eicosapentaenoic acid.
　本発明において、ω-3不飽和脂肪酸を含む油滴を水相中に分散させるために、界面活性剤又は乳化剤を用いることができる。界面活性剤又は乳化剤は、ω-3不飽和脂肪酸を含むO/W型エマルジョンの目的とする用途に応じて選択することができる。界面活性剤又は乳化剤としては、ショ糖脂肪酸エステル、アスコルビン酸脂肪酸エステル、ソルビンタン脂肪酸エステル、レシチン、モノグリセリドが特に好ましい。必要に応じて、界面活性剤及び乳化剤の少なくとも１種を用いることができる。
　なお、界面活性剤及び乳化剤の少なくとも１種の添加量は、エマルジョン全体（油相＋液相）を基準として、0.01～2(w/v)%で充分である。また、乳化処理において、水溶性もしくは脂溶性の抗酸化剤、又はサイクロデキストリン等の包接用化合物、キレート剤、pH調整剤等を併用することも可能である。 In the present invention, a surfactant or an emulsifier can be used to disperse oil droplets containing an ω-3 unsaturated fatty acid in the aqueous phase. The surfactant or emulsifier can be selected according to the intended use of the O / W emulsion containing the ω-3 unsaturated fatty acid. As the surfactant or emulsifier, sucrose fatty acid ester, ascorbic acid fatty acid ester, sorbitan fatty acid ester, lecithin, and monoglyceride are particularly preferable. If necessary, at least one of a surfactant and an emulsifier can be used.
The addition amount of at least one of the surfactant and the emulsifier is sufficient to be 0.01 to 2 (w / v)% based on the whole emulsion (oil phase + liquid phase). In the emulsification treatment, a water-soluble or fat-soluble antioxidant, an inclusion compound such as cyclodextrin, a chelating agent, a pH adjuster, or the like can be used in combination.
　エマルジョン製造用の油相を構成する材料としては、油脂であれば特に制限なく使用できるが、例えば、ω-3不飽和脂肪酸を含む魚油、微細藻類抽出油、ω-6不飽和脂肪酸を含むゴマ油、大豆油などの一般の動植物油脂等も用いることができる。
　魚油としては、好ましくは0～99.9重量％の割合でω-3不飽和脂肪酸を含む魚油、特に好ましくは10～70重量％の割合でω-3不飽和脂肪酸を含む魚油、最も好ましくは20～40重量%の割合でω-3不飽和脂肪酸を含む魚油を用いることができる。
　なお、油相用の油脂がω-3不飽和脂肪酸を含まない場合やω-3不飽和脂肪酸の含有量が目的とする量に達していない場合は、油脂に、ω-3不飽和脂肪酸自体あるいはω-3不飽和脂肪酸を含む油脂を添加してω-3不飽和脂肪酸の含有量を調整してもよい。
　油相には、ω-3不飽和脂肪酸を含むO/W型エマルジョンの目的とする用途に応じて各種脂溶性の添加剤を含有させることができる。 As a material constituting the oil phase for producing an emulsion, any oil and fat can be used without particular limitation. For example, fish oil containing ω-3 unsaturated fatty acid, microalgal extract oil, sesame oil containing ω-6 unsaturated fatty acid Ordinary animal and vegetable oils and fats such as soybean oil can also be used.
The fish oil is preferably a fish oil containing an omega-3 unsaturated fatty acid in a proportion of 0 to 99.9% by weight, particularly preferably a fish oil containing an omega-3 unsaturated fatty acid in a proportion of 10 to 70% by weight, most preferably 20 to Fish oil containing ω-3 unsaturated fatty acid in a proportion of 40% by weight can be used.
If the oil and fat for the oil phase does not contain ω-3 unsaturated fatty acid or the content of ω-3 unsaturated fatty acid does not reach the target amount, Or you may adjust the content of omega-3 unsaturated fatty acid by adding the fats and oils containing omega-3 unsaturated fatty acid.
The oil phase can contain various fat-soluble additives depending on the intended use of the O / W type emulsion containing ω-3 unsaturated fatty acid.
　エマルジョン製造用の水相を構成する材料としては、水を用いることができる。水相にも、ω-3不飽和脂肪酸を含むO/W型エマルジョンの目的とする用途に応じて各種水溶性の添加剤を含有させることができる。このような添加剤としては、カゼイン、乳清タンパク質、ゼラチン等のタンパク質、及びそれらの分解物等を挙げることができ、これらの少なくとも１種を用いることができる。 Water can be used as a material constituting the aqueous phase for emulsion production. Various types of water-soluble additives can also be contained in the aqueous phase depending on the intended use of the O / W emulsion containing an ω-3 unsaturated fatty acid. Examples of such additives include proteins such as casein, whey protein, gelatin, and degradation products thereof, and at least one of them can be used.
　水相と油相の割合は、99.9：0.1～50：50（重量基準）の範囲から選択することができる。
　油相と水相を調製し、必要に応じて予備乳化処理を行ってから超音波による乳化を行う。乳化に用いる超音波としては、周波数20kHz以上、出力200Ｗ以上の超音波が用いられる。周波数及び出力の上限は特に限定されないが、周波数は1MHz以下、出力は16kW以下とすることができる。
　油相と水相の混合物への超音波の照射方法としては、所定時間連続照射する方法、所定時間間欠照射する方法等、目的とする超音波乳化が可能となる照射方法を選択することができる。 The ratio of the water phase to the oil phase can be selected from the range of 99.9: 0.1 to 50:50 (weight basis).
An oil phase and an aqueous phase are prepared, and preliminarily emulsified as necessary, followed by ultrasonic emulsification. As ultrasonic waves used for emulsification, ultrasonic waves having a frequency of 20 kHz or more and an output of 200 W or more are used. The upper limit of the frequency and output is not particularly limited, but the frequency can be 1 MHz or less and the output can be 16 kW or less.
As a method of irradiating the mixture of the oil phase and the aqueous phase with ultrasonic waves, a method of irradiation capable of the desired ultrasonic emulsification, such as a method of continuous irradiation for a predetermined time, a method of intermittent irradiation for a predetermined time, or the like can be selected. .
　乳化処理における超音波によりエマルジョンの単位面積あたりに投入されるエネルギーは、以下の式により算出することができる。
・単位面積あたりにかかるエネルギー(kJ/m3)＝電流(A)×電圧(V)×時間(sec)/エマルジョン全体の表面積(m3)
　この単位面積あたりにかかるエネルギーは、0.01～1.0 kJ/m3の範囲にあることが好ましい。 The energy input per unit area of the emulsion by ultrasonic waves in the emulsification process can be calculated by the following equation.
-Energy per unit area (kJ / m 3 ) = Current (A) x Voltage (V) x Time (sec) / Emulsion surface area (m 3 )
The energy applied per unit area is preferably in the range of 0.01 to 1.0 kJ / m 3 .
　超音波乳化はO/W型エマルジョンにおける平均液滴径が250nm以下、多分散指数が0.3未満となるまで行うことが好ましい。また、平均液滴径及び多分散指数の下限は特に限定されないが、平均液滴径が50nm以上、多分散指数が0.01以上となるように超音波乳化を行えばよい。
　超音波乳化を行う際の液温は、好ましくは4～50℃、特に好ましくは4～40℃、最も好ましくは、4～10℃である。
　本発明の製造方法により得られるω-3不飽和脂肪酸を含むO/W型エマルジョンは、水相中へのω-3不飽和脂肪酸を含む油滴の分散の際に、投与エネルギーの少ない超音波を用いることによって、O/W型エマルジョンの安定した形成をω-3不飽和脂肪酸の酸化安定性を保った状態で行うことができる。更に、こうして得られたO/W型エマルジョンではω-3不飽和脂肪酸が油滴中に含まれることで高い酸化安定性を有し、長期保存安定性に優れたω-3不飽和脂肪酸含有O/W型エマルジョンを得ることができる。 The ultrasonic emulsification is preferably performed until the average droplet diameter in the O / W emulsion is 250 nm or less and the polydispersity index is less than 0.3. The lower limits of the average droplet diameter and the polydispersity index are not particularly limited, but ultrasonic emulsification may be performed so that the average droplet diameter is 50 nm or more and the polydispersity index is 0.01 or more.
The liquid temperature during ultrasonic emulsification is preferably 4 to 50 ° C., particularly preferably 4 to 40 ° C., and most preferably 4 to 10 ° C.
The O / W type emulsion containing an ω-3 unsaturated fatty acid obtained by the production method of the present invention is an ultrasonic wave with low administration energy when oil droplets containing an ω-3 unsaturated fatty acid are dispersed in an aqueous phase. By using this, it is possible to stably form an O / W emulsion while maintaining the oxidation stability of the ω-3 unsaturated fatty acid. Furthermore, in the O / W type emulsion thus obtained, ω-3 unsaturated fatty acid is contained in the oil droplets so that it has high oxidative stability and has long-term storage stability. A / W type emulsion can be obtained.
　本発明にかかるω-3不飽和脂肪酸含有O/W型エマルジョンは、ω-3不飽和脂肪酸を含む各種製品の製造用素材として好適に利用することができる。このような製品としては、食品、補助食品、医薬品及び動物薬、飼料及び補助飼料等を挙げることがでる。本発明にかかるω-3不飽和脂肪酸含有O/W型エマルジョンはエマルジョンの形態を保持した状態で上記のような各種製品に添加することができ、エマルジョン形態の製品の素材として特に好適に利用できる。このようなエマルジョンの形態の製品としては、マヨネーズ、ドレッシング、アイスクリーム、ドリンク、経腸栄養剤、ワクチン用アジュバント、アジュバントワクチン、家畜用代替乳等を挙げることができる。これらの製品の製造において、ω-3不飽和脂肪酸配合用として本発明にかかるω-3不飽和脂肪酸含有O/W型エマルジョンを利用することができる。 The ω-3 unsaturated fatty acid-containing O / W emulsion according to the present invention can be suitably used as a raw material for producing various products containing ω-3 unsaturated fatty acids. Examples of such products include foods, supplements, pharmaceuticals and animal drugs, feeds and supplementary feeds. The ω-3 unsaturated fatty acid-containing O / W emulsion according to the present invention can be added to various products as described above while maintaining the form of the emulsion, and can be particularly suitably used as a material for the product in the form of an emulsion. . Examples of the product in the form of an emulsion include mayonnaise, dressing, ice cream, drink, enteral nutrition, vaccine adjuvant, adjuvant vaccine, livestock substitute milk, and the like. In the production of these products, the ω-3 unsaturated fatty acid-containing O / W emulsion according to the present invention can be used for blending ω-3 unsaturated fatty acids.
　以下、実施例により本発明を更に具体的に説明するが、本発明の範囲は、以下の実施例に限定されるものではない。 Hereinafter, the present invention will be described more specifically by way of examples. However, the scope of the present invention is not limited to the following examples.
　（実施例１）
　（方法）
　エマルジョンの構成成分、水相及び油相の調製方法
　エマルジョンの構成成分を表１に示した。DHA含有精製魚油はマルハニチロ(株)のDHA含有精製魚油を使用した。澱粉分解物、カゼイン加水分解物、および水を混合し、60℃の湯浴で溶解し、これを水相とした。DHA含有精製魚油、グリセリン脂肪酸エステル、およびレシチンを混合し、80℃の湯浴で溶解し、これを油相とした。 (Example 1)
(Method)
Preparation of emulsion components, aqueous phase and oil phase Table 1 shows the emulsion components. DHA-containing refined fish oil was DHA-containing refined fish oil from Maruha Nichiro Co., Ltd. The starch degradation product, casein hydrolyzate, and water were mixed and dissolved in a 60 ° C. hot water bath to obtain an aqueous phase. DHA-containing purified fish oil, glycerin fatty acid ester, and lecithin were mixed and dissolved in a water bath at 80 ° C. to obtain an oil phase.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　各乳化方法によるエマルジョンの調製
・超音波乳化法
　超音波乳化法によるエマルジョンの調製は、撹拌機(スリーワン　モータ1200G,Heidon)を用いて撹拌回転数9,600rpmで5分間、予備乳化処理を行った後、電気歪振動子型超音波乳化機(UD-201,トミー精工,超音波波数20KHz)を用いて行った。発振出力200Wで10分間乳化処理を行った。超音波は、1秒間のうち0.5秒間照射する間欠照射を行った。
・高圧乳化法
　高圧乳化法によるエマルジョンの調製は、撹拌乳化機(Polytron PT3100,Kinematica)を用いて9,600rpmで5分間、予備乳化処理を行った後、ナノマイザーNM2-L100(吉田機械興業(株))を用いて行った。乳化処理時の操作圧力を175Mpaに固定し、処理回数を1回として乳化処理を行った。
　予備乳化処理は、目視で水相と油相が均質化されたことが確認でき、平均液滴径500nm～1mm程度を終了の目安とする。
　すべての乳化操作時のエマルジョンの温度は40℃以下に制御し、エマルジョンに含まれる油の酸化促進を防いだ。 Preparation of emulsion by each emulsification method and ultrasonic emulsification method Preparation of emulsion by ultrasonic emulsification method is performed after pre-emulsification treatment with a stirrer (three-one motor 1200G, Heidon) at a stirring rotation speed of 9,600 rpm for 5 minutes. This was carried out using an electrostrictive vibrator type ultrasonic emulsifier (UD-201, Tommy Seiko, ultrasonic wave number 20 KHz). Emulsification was performed for 10 minutes at an oscillation output of 200 W. The ultrasonic wave was intermittently irradiated for 0.5 second in 1 second.
・ High-pressure emulsification method Emulsion preparation by high-pressure emulsification method was performed by pre-emulsification treatment at 9,600 rpm for 5 minutes using a stirring emulsifier (Polytron PT3100, Kinematica), then Nanomizer NM2-L100 (Yoshida Kikai Kogyo Co., Ltd.) ). The operation pressure during the emulsification treatment was fixed at 175 Mpa, and the emulsification treatment was carried out with one treatment.
In the preliminary emulsification treatment, it can be visually confirmed that the water phase and the oil phase are homogenized, and an average droplet diameter of about 500 nm to 1 mm is used as a guideline for completion.
The emulsion temperature during all emulsification operations was controlled below 40 ° C to prevent the oxidation of the oil contained in the emulsion.
　液滴径分布および分散安定性の測定
　エマルジョンを50℃、暗所で30日間静置保存し、50mM NaCl水溶液で1/2000に希釈し、Ζ平均液滴径(流体力学的直径)および多分散指数(PdI)を動的光散乱法により測定した。
　エマルジョンに含まれるヒドロペルオキシドの定量
　各乳化法で作製したエマルジョンは、50℃、暗所で10日間静置保存し、鉄チオシアネート法を用いて試料に含まれるヒドロペルオキシド濃度を求めた。
　過酸化脂質の標準物質であるクメンヒドロペルオキシド量を横軸、吸光度を縦軸としてプロットし、最少二乗法により回帰直線を求め、検量線を作成した。この検量線を用いてエマルジョンの過酸化物価をヒドロペルオキシド当量(POV値(nmol/l))で示した。
　単位面積あたりにかかるエネルギー
　下記の式に従い、エマルジョンの単位面積あたりに投入されたエネルギーを計算した。
・単位面積あたりにかかるエネルギー(kJ/m3)=電流(A)×電圧(V)×時間(sec)/エマルジョン全体の表面積(m3)/1000
・エマルジョン全体の表面積(m3)= 4π×(Ζ平均液滴径(nm)/109/2)2×エマルジョンの総数
・エマルジョンの総数=油相体積/エマルジョン1個当たりの体積
・エマルジョン1個当たりの体積= 4/3×π×（Ζ平均液滴径(nm)/109/2）3 Measurement of droplet size distribution and dispersion stability Emulsion was stored at 50 ° C in the dark for 30 days, diluted to 1/2000 with 50 mM NaCl aqueous solution, Ζaverage droplet size (hydrodynamic diameter) and polydispersity The index (PdI) was measured by dynamic light scattering method.
Determination of hydroperoxide contained in the emulsion The emulsion prepared by each emulsification method was stored at 50 ° C. in the dark for 10 days, and the concentration of hydroperoxide contained in the sample was determined using the iron thiocyanate method.
The amount of cumene hydroperoxide, which is a standard substance of lipid peroxide, was plotted with the horizontal axis and the absorbance as the vertical axis, and a regression line was obtained by the least square method to prepare a calibration curve. Using this calibration curve, the peroxide value of the emulsion was expressed in terms of hydroperoxide equivalent (POV value (nmol / l)).
Energy per unit area The energy input per unit area of the emulsion was calculated according to the following formula.
・ Energy per unit area (kJ / m 3 ) = Current (A) x Voltage (V) x Time (sec) / Emulsion surface area (m 3 ) / 1000
Emulsion total surface area (m 3) = 4π × ( Ζ mean droplet diameter (nm) / 10 9/2 ) 2 × volume emulsion 1 per Total = oil phase volume / emulsion of the total number emulsion of the emulsion volume per individual = 4/3 × π × ( Ζ mean droplet diameter (nm) / 10 9/2 ) 3
　（結果）
　図１に超音波乳化法で調製したエマルジョンのΖ平均液滴径と多分散指数を示した。初発の液滴径は約150nmであり、保存30日目でもほとんど変化は見られなかった。同様にPdIも約0.1から変化せず、高い単分散性を保っていた。
　図２に高圧乳化法で調製したエマルジョンのΖ平均液滴径と多分散指数を示した。初発の液滴径は約100nmであり、保存30日目でもほとんど変化は見られなかったが、PdIは初発約0.1から30日後では約0.16となっており、単分散性が低下したことが分かった。
　図３に各乳化法で作製したエマルジョンのヒドロペルオキシド量の経時変化を示した。超音波乳化法で作製したエマルジョンのヒドロペルオキシド量は保存10日目においても初発からほとんど変化しなかったことから、酸化安定性は高いことが示された。一方、高圧乳化で作製したエマルジョンでは、経時的に上昇し、初発0から、10日目では450nmol-CuOOH/L-Oilに上昇したことから、酸化安定性は低いと考えられた。 
　表２に各乳化法で調製した時のエマルジョン単位面積あたりにかかるエネルギーを示した。超音波乳化法は、エネルギー量が小さく、平均液滴径200nm以下で、単分散であるエマルジョンを調製でき、高圧乳化法より効率的な方法である。 (result)
FIG. 1 shows the wrinkle average droplet diameter and polydispersity index of the emulsion prepared by the ultrasonic emulsification method. The initial droplet size was about 150 nm, and there was almost no change even after 30 days of storage. Similarly, PdI did not change from about 0.1 and maintained high monodispersity.
FIG. 2 shows the average droplet diameter and polydispersity index of the emulsion prepared by the high pressure emulsification method. The initial droplet size was about 100 nm, and there was almost no change even after 30 days of storage, but PdI was about 0.16 from about 0.1 to 30 days after the initial release, indicating that the monodispersity decreased It was.
FIG. 3 shows the change with time of the hydroperoxide amount of the emulsion prepared by each emulsification method. The amount of hydroperoxide in the emulsion prepared by the ultrasonic emulsification method did not change from the first on the 10th day of storage, indicating that the oxidation stability was high. On the other hand, the emulsion produced by high-pressure emulsification increased with time and increased to 450 nmol-CuOOH / L-Oil from the first day to 450 nmol, indicating that the oxidation stability was low.
Table 2 shows the energy per unit area of emulsion when prepared by each emulsification method. The ultrasonic emulsification method is a more efficient method than the high pressure emulsification method because it can prepare a monodisperse emulsion with a small energy amount and an average droplet diameter of 200 nm or less.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　（実施例２）
　（方法）
　エマルジョンの構成成分、水相及び油相の調製方法
　水相及び油相は、実施例１と同様の方法で調製した。
　各乳化方法によるエマルジョンの調製
・超音波乳化法
　エマルジョンは、実施例１と同様の方法で調製した。
・撹拌乳化法
　撹拌乳化法によるエマルジョンの調製は撹拌乳化機(Polytron PT3100,Kinematica)を用いて行った。油相と水相を混合し、撹拌回転数を24,000rpmで5分間乳化処理を行った。
　すべての乳化操作時のエマルジョンの温度は40℃以下に制御し、エマルジョンに含まれる油の酸化促進を防いだ。
　液滴径分布および分散安定性の測定
　乳化処理直後のエマルジョンを50℃、暗所で16日間静置保存し、50mM NaCl水溶液で1/2000の濃度に希釈し、Ζ平均液滴径(流体力学的直径)および多分散指数(PdI)を動的光散乱法により測定した。
　エマルジョンに含まれるヒドロペルオキシドの定量
　各乳化法で作製したエマルジョンは、50℃、暗所で10日間静置保存し、鉄チオシアネート法を用いて試料に含まれるヒドロペルオキシド濃度を求めた。
　過酸化脂質の標準物質であるクメンヒドロペルオキシド量を横軸、吸光度を縦軸としてプロットし、最少二乗法により回帰直線を求め、検量線を作成した。この検量線を用いてエマルジョンの過酸化物価をヒドロペルオキシド当量(POV値(mmol/l))で示した。
　単位面積あたりにかかるエネルギー
　単位面積あたりにかかるエネルギーは、実施例１と同様の方法で計算した。 (Example 2)
(Method)
Preparation of emulsion components, aqueous phase and oil phase The aqueous phase and oil phase were prepared in the same manner as in Example 1.
Preparation of emulsion by each emulsification method / Ultrasonic emulsification method The emulsion was prepared in the same manner as in Example 1.
-Stir emulsification method Emulsion preparation by the stir emulsification method was performed using a stir emulsifier (Polytron PT3100, Kinematica). The oil phase and the aqueous phase were mixed and emulsified for 5 minutes at a stirring speed of 24,000 rpm.
The emulsion temperature during all emulsification operations was controlled below 40 ° C to prevent the oxidation of the oil contained in the emulsion.
Measurement of droplet size distribution and dispersion stability The emulsion immediately after the emulsification treatment was stored at 50 ° C. in the dark for 16 days, diluted to a concentration of 1/2000 with 50 mM NaCl aqueous solution, and the average droplet size (hydrodynamics) Diameter) and polydispersity index (PdI) were measured by dynamic light scattering method.
Determination of hydroperoxide contained in the emulsion The emulsion prepared by each emulsification method was stored at 50 ° C. in the dark for 10 days, and the concentration of hydroperoxide contained in the sample was determined using the iron thiocyanate method.
The amount of cumene hydroperoxide, which is a standard substance of lipid peroxide, was plotted with the horizontal axis and the absorbance as the vertical axis, and a regression line was obtained by the least square method to prepare a calibration curve. Using this calibration curve, the peroxide value of the emulsion was expressed in terms of hydroperoxide equivalent (POV value (mmol / l)).
Energy applied per unit area The energy applied per unit area was calculated in the same manner as in Example 1.
　（結果）
　図４に超音波乳化法で調製したエマルジョンのΖ平均液滴径と多分散指数を示した。初発の液滴径は約200nmであり、保存16日目でもほとんど変化は見られなかった。同様にPdIも約0.15から若干上昇し、16日目では約0.2となった。
　図５に撹拌乳化法で調製したエマルジョンのΖ平均液滴径と多分散指数を示した。初発の液滴径は約260nmであり、継時的に上昇し、保存16日目では約350nmであった。また、PdIも約0.25から16日後では約0.4に上昇したことから、単分散性は低いと考えられた。
　図６に各乳化法で作製したエマルジョンのヒドロペルオキシド量の経時変化を示した。超音波乳化法で作製したエマルジョンのヒドロペルオキシド量は保存10日目においても初発からほとんど変化しなかったことから、酸化安定性は高いと考えられた。一方、撹拌乳化で作製したエマルジョンでは、経時的に上昇し、初発0に対して、10日目では4.5mmol-CuOOH/L-Oilに上昇したことから、酸化安定性は低いと考えられた。
　表３に各乳化法で調製した時のエマルジョン単位面積あたりに投入されたエネルギーを示した。超音波乳化法は、エネルギー量が小さく、平均液滴径200nm以下で、単分散であるエマルジョンを調製でき、撹拌乳化法より効率的な方法である。 (result)
FIG. 4 shows the mean droplet diameter and polydispersity index of the emulsion prepared by the ultrasonic emulsification method. The initial droplet size was about 200 nm, and there was almost no change even after 16 days of storage. Similarly, PdI also increased slightly from about 0.15 and reached about 0.2 on the 16th day.
FIG. 5 shows the average droplet diameter and polydispersity index of the emulsion prepared by the stirring emulsification method. The initial droplet size was about 260 nm, which increased with time, and was about 350 nm on the 16th day of storage. In addition, PdI also increased to about 0.4 after about 0.25 to 16 days, and thus monodispersity was considered to be low.
FIG. 6 shows the change with time of the hydroperoxide amount of the emulsion prepared by each emulsification method. The hydroperoxide content of the emulsion prepared by the ultrasonic emulsification method hardly changed from the first on the 10th day of storage, so it was considered that the oxidation stability was high. On the other hand, the emulsion produced by stirring emulsification increased with time and increased to 4.5 mmol-CuOOH / L-Oil on the 10th day compared with the initial 0, so the oxidation stability was considered to be low.
Table 3 shows energy input per unit area of emulsion when prepared by each emulsification method. The ultrasonic emulsification method is a more efficient method than the stirring emulsification method because it can prepare a monodisperse emulsion having a small energy amount and an average droplet diameter of 200 nm or less.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003

Claims (6)

  1. 　ω-3不飽和脂肪酸を含む油相と水相を周波数20kHz以上、出力200Ｗ以上の超音波により乳化して、酸化安定性を有するω-3不飽和脂肪酸を含むO/W型エマルジョンを得ることを特徴とするO/W型エマルジョンの製造方法。 An oil phase and an aqueous phase containing ω-3 unsaturated fatty acids are emulsified with ultrasonic waves having a frequency of 20 kHz or more and an output of 200 W or more to obtain an O / W type emulsion containing ω-3 unsaturated fatty acids having oxidation stability. A method for producing an O / W emulsion characterized by the following.
  2. 　前記O/W型エマルジョンの平均液滴径が250nm以下、多分散指数が0.3未満であることを特徴とする請求項１に記載の製造方法。 The method according to claim 1, wherein the O / W emulsion has an average droplet diameter of 250 nm or less and a polydispersity index of less than 0.3.
  3. 　請求項１に記載の製造方法により製造されたことを特徴とするω-3不飽和脂肪酸を含むO/W型エマルジョン。 An O / W emulsion containing an ω-3 unsaturated fatty acid produced by the production method according to claim 1.
  4. 　平均液滴径が250nm以下、多分散指数が0.3未満であることを特徴とする請求項３に記載のω-3不飽和脂肪酸を含むO/W型エマルジョン。 The O / W emulsion containing an ω-3 unsaturated fatty acid according to claim 3, wherein the average droplet diameter is 250 nm or less and the polydispersity index is less than 0.3.
  5. 　ω-3不飽和脂肪酸成分を含む食品、補助食品、医薬品、動物薬、飼料及び補助飼料のいずれかの製品の製造において、請求項３または４に記載のω-3不飽和脂肪酸を含むO/W型エマルジョンの前記ω-3不飽和脂肪酸成分配合用としての使用方法。 In the production of any of foods, supplements, pharmaceuticals, animal drugs, feeds and supplementary feeds containing ω-3 unsaturated fatty acid components, O / containing ω-3 unsaturated fatty acids according to claim 3 or 4 A method of using the W-type emulsion for blending the ω-3 unsaturated fatty acid component.
  6. 　前記製品がマヨネーズ、ドレッシング、アイスクリーム、ドリンク、経腸栄養剤、ワクチン用アジュバント、アジュバントワクチン、家畜用代替乳等のエマルジョン形態の製品である請求項５に記載の使用方法。 The method according to claim 5, wherein the product is a product in the form of an emulsion such as mayonnaise, dressing, ice cream, drink, enteral nutrient, vaccine adjuvant, adjuvant vaccine, livestock substitute milk or the like.
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