JP5415510B2 - Method for producing oil-in-water emulsion - Google Patents

Method for producing oil-in-water emulsion Download PDF

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JP5415510B2
JP5415510B2 JP2011240532A JP2011240532A JP5415510B2 JP 5415510 B2 JP5415510 B2 JP 5415510B2 JP 2011240532 A JP2011240532 A JP 2011240532A JP 2011240532 A JP2011240532 A JP 2011240532A JP 5415510 B2 JP5415510 B2 JP 5415510B2
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善也 伏見
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Japan Tobacco Inc
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本発明は、安価で安心、安全な食品用水中油型エマルジョン組成およびその製造方法であり、容易に実質的に透明な水中油型のマイクロエマルジョンとすることができ、フレーバー物質などの疎水性物質を可溶化し、食品に添加することができる食品用水中油型マイクロエマルジョンの製造方法に関する。   The present invention is an inexpensive, safe and safe oil-in-water emulsion composition for food and a method for producing the same, and can be easily made into a substantially transparent oil-in-water microemulsion, and a hydrophobic substance such as a flavor substance can be obtained. The present invention relates to a method for producing an oil-in-water microemulsion for food that can be solubilized and added to food.

マイクロエマルジョンに関する研究は、近年急速に発展してきており、食品にもこの技術を応用する試みが多数行われている。
例えば、特許文献1に開示されているように水相に水、補助界面活性剤およびポリオールが1:1〜4、油相に溶媒および補助溶媒が1〜2:1で、油相と界面活性剤が1:1〜2の自己集合構造をもつ液体濃厚物がある。
Research on microemulsions has developed rapidly in recent years, and many attempts have been made to apply this technology to foods.
For example, as disclosed in Patent Document 1, the water phase is water, the auxiliary surfactant and the polyol are 1: 1 to 4, the oil phase is the solvent and the auxiliary solvent is 1 to 2: 1, and the oil phase and the surface activity. There is a liquid concentrate in which the agent has a self-assembled structure of 1: 1 to 2.

あるいは、特許文献2に開示されているようにフレーバーにHLB16〜19の蔗糖脂肪酸エステルあるいはポリグリセリン脂肪酸エステルとリゾレシチンを含有させ、ホモミキサーにより3000〜10000rpmで撹拌することにより得られている。   Alternatively, as disclosed in Patent Document 2, the sucrose fatty acid ester of HLB 16-19 or polyglycerin fatty acid ester and lysolecithin are contained in the flavor and stirred at 3000-10000 rpm with a homomixer.

あるいは、特許文献3に開示されているように調味成分と、組成物全量に対して、0.1〜50質量%の、平均粒径1μm以下の油滴状態にある油脂とを含む液状もしくはペースト状調味料組成物がある。   Alternatively, as disclosed in Patent Document 3, a liquid or paste comprising a seasoning component and 0.1 to 50% by mass of oil and fat in an oil droplet state having an average particle size of 1 μm or less based on the total amount of the composition There is a seasoning composition.

一方、脂肪酸を用いたマイクロエマルジョンに関する相挙動の研究も近年盛んに行われている。例えば、非特許文献1のモノオレイン酸/エタノール/水混合物からの液状ミセル性不連続立方晶メソ相に関する研究;非特許文献2のモノオレインとオレイン酸ナトリウムの水性分散系でのベシクル生成と他の構造に関する研究;非特許文献3のオレイン酸ナトリウムとオレイン酸の混合物からなるモノオレイン水溶液系における相挙動に関する研究;非特許文献4の脂肪酸アルギニンのKCl水溶液中の構造形成に関する研究;などが開示されている。   On the other hand, research on the phase behavior of microemulsions using fatty acids has been actively conducted in recent years. For example, non-patent document 1 study on liquid micellar discontinuous cubic mesophase from monooleic acid / ethanol / water mixture; non-patent document 2 vesicle formation in aqueous dispersion of monoolein and sodium oleate and others Research on phase structure in monoolein aqueous solution system consisting of sodium oleate and oleic acid mixture of Non-Patent Document 3; Study on structure formation of fatty acid arginine in KCl aqueous solution of Non-Patent Document 4; Has been.

これら非特許文献1〜4は、単一脂肪酸を用いた単純な2相系、3相系の相挙動に関する基礎研究であり、食品に用いられる油脂の構成脂肪酸のような複雑な系や、食品成分中の強いpH緩衝能下での相挙動とは、全く異なるものである。   These Non-Patent Documents 1 to 4 are basic studies on simple two-phase and three-phase system behaviors using a single fatty acid, such as complex systems such as constituent fatty acids of fats and oils used in foods, foods The phase behavior under strong pH buffering ability in the components is quite different.

特表2005−532049号公報Special table 2005-532049 gazette 特許第3419351号公報Japanese Patent No. 3419351 特許第3162554号公報Japanese Patent No. 3162554

Colloids Surf., Vol. 299, No. 1-3, P133-145Colloids Surf., Vol. 299, No. 1-3, P133-145 J. Colloid Interface Sci., Vol. 257, No. 2, P310-320J. Colloid Interface Sci., Vol. 257, No. 2, P310-320 Langmuir, Vol. 17, No. 25, P7742-7751Langmuir, Vol. 17, No. 25, P7742-7751 コロイドおよび界面化学討論会講演要旨集 (2005) P99Proceedings of the Colloid and Interface Chemistry Conference (2005) P99

しかしながら、前述した従来技術のうち、特許文献1,2に開示された従来技術は、食品には使用できない強力な界面活性剤を用いたり、食品用に許可されている乳化剤を用いることが前提となっている。しかしながら、近年の消費者における安全・安心な食品への嗜好は、安全性評価を実施している食品添加物でさえ、忌避する傾向にあり、消費者ニーズを十分満たした方法とは言えない。   However, among the conventional techniques described above, the conventional techniques disclosed in Patent Documents 1 and 2 are based on the premise that a strong surfactant that cannot be used for foods or an emulsifier that is permitted for foods is used. It has become. However, recent consumer preferences for safe and secure foods tend to avoid even food additives that have been evaluated for safety, and cannot be said to be a method that sufficiently satisfies consumer needs.

さらに、特許文献3においては、食品に油脂由来のコク味を付与することを目的とした技術であり、マイクロエマルジョン化されていないため、液状食品などに添加した場合には、白濁し、食品の商品価値を大きく損ねてしまう。   Furthermore, in patent document 3, it is the technique aiming at providing the rich taste derived from fats and oils to food, and since it is not microemulsified, when added to liquid food etc., it becomes cloudy, The merchandise value is greatly impaired.

本発明は、前記事情に鑑みてなされ、界面活性剤や乳化剤を用いず、食品として許容される材料の組み合わせによって、透明な水中油型エマルジョンを提供することを目的とする。   The present invention has been made in view of the above circumstances, and an object thereof is to provide a transparent oil-in-water emulsion by using a combination of materials acceptable as food without using a surfactant or an emulsifier.

前記目的を達成するため、本発明は、トリグリセリン脂肪酸エステルに、その3つの脂肪酸残基の内の2つを加水分解するリパーゼを作用させて脂肪酸を得て、水と、前記脂肪酸と、アルコールと、塩基性アミノ酸とを、脂肪酸/水の質量組成比が1以下かつ脂肪酸/アルコールの質量組成比が1未満となるように混合し、キトサン又はキトサンの分解物又はグルコサミンを添加した後に系のpHを6〜8の範囲に調整して、界面活性剤及び乳化剤を含まない水中油型エマルジョンを得ることを特徴とする水中油型エマルジョンの製造方法を提供する。 In order to achieve the above object, the present invention provides triglycerin fatty acid ester with a lipase that hydrolyzes two of the three fatty acid residues to obtain a fatty acid, water, the fatty acid, alcohol And basic amino acid are mixed so that the mass composition ratio of fatty acid / water is 1 or less and the mass composition ratio of fatty acid / alcohol is less than 1, and chitosan or a degradation product of chitosan or glucosamine is added . Provided is a method for producing an oil-in-water emulsion, characterized in that the pH is adjusted to a range of 6 to 8 to obtain an oil-in-water emulsion that does not contain a surfactant and an emulsifier .

本発明の水中油型エマルジョンの製造方法において、各材料を混合し多孔質膜を透過させて水中油型エマルジョンを得ることが好ましい。   In the method for producing an oil-in-water emulsion of the present invention, it is preferable to obtain an oil-in-water emulsion by mixing each material and permeating the porous membrane.

本発明の水中油型エマルジョンの製造方法において、エマルジョンのpHを調整する前に、蛋白質又は蛋白質の分解物を添加することが好ましい。   In the method for producing an oil-in-water emulsion of the present invention, it is preferable to add a protein or a protein degradation product before adjusting the pH of the emulsion.

本発明の水中油型エマルジョンの製造方法は、アルコールと、塩基性アミノ酸とを、脂肪酸/水の質量組成比が1以下かつ脂肪酸/アルコールの質量組成比が1未満となるように混合し、系のpHを6〜8の範囲に調整することによって、実質的に透明な水中油型エマルジョンを製造することができる。
本発明の水中油型エマルジョンの製造方法において、必須成分の1つである脂肪酸を、トリグリセリン脂肪酸エステルをその3つの脂肪酸残基の内の2つを加水分解するリパーゼを作用させて得ることによって、植物油などの安価で安全な原料から脂肪酸を得ることができる。
本発明の水中油型エマルジョンの製造方法において、各材料を混合し多孔質膜を透過させて水中油型エマルジョンを得ることによって、pH6付近の弱酸性領域でのエマルジョンの透明化および安定化を図ることができる。
本発明の水中油型エマルジョンの製造方法において、エマルジョンのpH調整前に、該エマルジョンに蛋白質又は蛋白質の分解物、又はキトサン又はキトサンの分解物又はグルコサミンを添加することで、水で希釈しても白濁しないエマルジョンを製造することができる。
The method for producing an oil-in-water emulsion of the present invention comprises mixing an alcohol and a basic amino acid so that the mass composition ratio of fatty acid / water is 1 or less and the mass composition ratio of fatty acid / alcohol is less than 1. A substantially transparent oil-in-water emulsion can be produced by adjusting the pH of the emulsion to a range of 6-8.
In the method for producing an oil-in-water emulsion of the present invention, a fatty acid that is one of the essential components is obtained by allowing a triglycerin fatty acid ester to act on a lipase that hydrolyzes two of the three fatty acid residues. Fatty acids can be obtained from cheap and safe raw materials such as vegetable oils.
In the method for producing an oil-in-water emulsion of the present invention, each material is mixed and permeated through a porous membrane to obtain an oil-in-water emulsion, thereby making the emulsion transparent and stable in a weakly acidic region near pH 6. be able to.
In the method for producing an oil-in-water emulsion of the present invention, before the pH of the emulsion is adjusted, protein or protein degradation product, chitosan or chitosan degradation product or glucosamine may be added to the emulsion to dilute with water. An emulsion that does not become cloudy can be produced.

実施例5におけるリモネン残存率の比較結果を示すグラフである。It is a graph which shows the comparison result of the limonene residual rate in Example 5. 実施例6におけるエマルジョンへのTO溶解度の測定結果を示すグラフである。6 is a graph showing measurement results of TO solubility in an emulsion in Example 6.

本発明の水中油型エマルジョンは、水と、脂肪酸と、アルコールと、塩基性アミノ酸とを含み、脂肪酸/水の質量組成比が1以下かつ脂肪酸/アルコールの質量組成比が1未満であり、系のpHが6〜8の範囲であることを特徴とする。   The oil-in-water emulsion of the present invention comprises water, a fatty acid, an alcohol, and a basic amino acid, the mass composition ratio of fatty acid / water is 1 or less, and the mass composition ratio of fatty acid / alcohol is less than 1, The pH is in the range of 6-8.

本発明において、水は、食品製造用として許容される水、例えば、水道水、滅菌ろ過した地下水、鉱泉水、イオン交換水、蒸留水などを使用可能である。   In the present invention, water that can be used for food production, for example, tap water, sterilized groundwater, mineral water, ion exchange water, distilled water, and the like can be used.

本発明の水中油型エマルジョンにおいて、脂肪酸は、炭化水素のモノカルボン酸を示し、一般に食用に供される油脂の構成脂肪酸であれば、炭素数や2重結合の数など特に限定されない。ただし、脂肪酸が2種以上の脂肪酸混合物である場合、該脂肪酸混合物の脂肪酸組成は炭素数18以上の飽和脂肪酸(例えば、ステアリン酸など)の組成比が10質量%以下であることが好ましい。前記飽和脂肪酸の組成比が10質量%を超えると、製造したエマルジョンに白濁が生じる恐れがある。本発明の水中油型エマルジョンにおいて、脂肪酸の含量は、20質量%以上であることが好ましい。脂肪酸の含量が20質量%以上であると、その水中油型エマルジョンにトリグリセリンエステルなどの疎水性物質を加える場合、疎水性物質の溶解度が格段に高まる。   In the oil-in-water emulsion of the present invention, the fatty acid indicates a hydrocarbon monocarboxylic acid, and is not particularly limited as long as it is a constituent fatty acid of fats and oils generally used for food. However, when the fatty acid is a mixture of two or more fatty acids, the fatty acid composition of the fatty acid mixture preferably has a composition ratio of a saturated fatty acid having 18 or more carbon atoms (eg, stearic acid) of 10% by mass or less. If the composition ratio of the saturated fatty acid exceeds 10% by mass, the produced emulsion may be clouded. In the oil-in-water emulsion of the present invention, the fatty acid content is preferably 20% by mass or more. When the content of fatty acid is 20% by mass or more, when a hydrophobic substance such as triglycerin ester is added to the oil-in-water emulsion, the solubility of the hydrophobic substance is remarkably increased.

本発明の水中油型エマルジョンにおいて、アルコールは、食品製造用として許容されるアルコールを用いることができるが、エタノールが最も好ましい。本発明において、アルコール含量は、10質量%以上とすることが好ましい。   In the oil-in-water emulsion of the present invention, alcohol that can be used for food production can be used as alcohol, and ethanol is most preferable. In the present invention, the alcohol content is preferably 10% by mass or more.

本発明において、塩基性アミノ酸は、ヒスチジン、アルギニン、リジンなどであり、これらはそれぞれ単独で、又は複数種を混合した状態で用いることができる。この塩基性アミノ酸は、精製された塩基性アミノ酸を添加しても良いし、塩基性アミノ酸を含む抽出エキスや蛋白加水分解物などの利用も可能である。本発明の水中油型エマルジョンにおける塩基性アミノ酸の添加量は、実質的に溶解でき得る量であれば特に限定されないが、好ましくは、0.01〜1.00質量%の範囲がより好ましい。水中油型エマルジョンにおいて塩基性アミノ酸が含まれないと安定なエマルジョンを製造するために系のpHを8よりも高いpHにする必要があり、口腔内に入れた場合に刺激が強く、食品として好ましくなくなる。塩基性アミノ酸の溶解度を超えた量を添加した場合には、溶け残ったアミノ酸が沈降し、当然ながら沈降した塩基性アミノ酸には、エマルジョンの安定効果はなく、コストの上昇やアミノ酸による苦味やエグ味が見られるために好ましくない。   In the present invention, basic amino acids are histidine, arginine, lysine, and the like, and these can be used alone or in a mixed state. As this basic amino acid, a purified basic amino acid may be added, and an extract or protein hydrolyzate containing the basic amino acid may be used. The amount of basic amino acid added in the oil-in-water emulsion of the present invention is not particularly limited as long as it can be substantially dissolved, but is preferably in the range of 0.01 to 1.00% by mass. If basic amino acids are not contained in an oil-in-water emulsion, the pH of the system needs to be higher than 8 in order to produce a stable emulsion. Disappear. If an amount exceeding the solubility of the basic amino acid is added, the undissolved amino acid will settle, and naturally the precipitated basic amino acid will not have an emulsion stabilizing effect, resulting in increased costs, bitterness and Since taste is seen, it is not preferable.

本発明において、水、脂肪酸、およびアルコールの3成分の質量組成比は、脂肪酸/水の質量組成比が1以下かつ脂肪酸/アルコールの質量組成比が1未満とする。脂肪酸/水の質量組成比が1を超える場合には、油水が分離し易くなる。また、脂肪酸/アルコールの質量組成比が1を超える場合にも、油水が分離し易くなる。   In the present invention, the mass composition ratio of the three components of water, fatty acid, and alcohol is such that the mass composition ratio of fatty acid / water is 1 or less and the mass composition ratio of fatty acid / alcohol is less than 1. When the mass composition ratio of fatty acid / water exceeds 1, oily water is easily separated. Also, when the mass composition ratio of fatty acid / alcohol exceeds 1, oil and water are easily separated.

本発明の水中油型エマルジョンは、系のpHが6〜8の範囲である。pHが6未満であると、油滴の平均粒径が大きくなって白濁したり、又は油水が分離してエマルジョンが形成できなくなる。一方、pHが8を超えると、エマルジョンの安定性に大きな問題は無いが、口腔内に入れた場合に刺激が強く、食品として好ましくなくなる。   The oil-in-water emulsion of the present invention has a system pH in the range of 6-8. If the pH is less than 6, the average particle diameter of the oil droplets becomes large and becomes cloudy, or the oil and water are separated and an emulsion cannot be formed. On the other hand, when the pH exceeds 8, there is no big problem in the stability of the emulsion, but when put in the oral cavity, the irritation is strong and it is not preferable as a food.

本発明の水中油型エマルジョンには、モノグリセリン脂肪酸エステルを添加することができる。モノグリセリン脂肪酸エステルとしては、食品製造用として許容される各種モノグリセリン脂肪酸エステルを使用することが可能であるが、食品に用いられるトリグリセリン脂肪酸エステルをその3つの脂肪酸残基の内の2つを加水分解するリパーゼを作用させ、生成させることにより、食品添加物の添加を必要とせず特に好ましい。この場合のモノグリセリン脂肪酸エステルの組成比としては、添加した又はリパーゼにより生成した脂肪酸の50mol%以下であることが好ましい。   A monoglycerin fatty acid ester can be added to the oil-in-water emulsion of the present invention. As monoglycerin fatty acid esters, various monoglycerin fatty acid esters that are acceptable for food production can be used, but triglycerin fatty acid esters used in foods are divided into two of the three fatty acid residues. It is particularly preferable that a lipase that is hydrolyzed is allowed to act and is produced, so that no addition of food additives is required. In this case, the composition ratio of the monoglycerin fatty acid ester is preferably 50 mol% or less of the fatty acid added or produced by lipase.

本発明の水中油型エマルジョンには、疎水性物質を含有させることもできる。疎水性物質としては、リモネンなどの香気成分やオイルベースの合成フレーバー、天然物から超臨界二酸化炭素などを使用し抽出した天然フレーバー、ビタミンEやビタミンAなどの脂溶性ビタミン類、ドコサヘキサエン酸(DHA)、エイコサペンタエン酸(EPA)等の高度不飽和脂肪酸(PUFA)およびそのグリセリンエステル、トリグリセリン脂肪酸エステルなどが挙げられる。なお、好ましいトリグリセリン脂肪酸エステルとしては、サラダ油、大豆油、綿実油、オリーブ油、コーン油、ごま油などの食用油などが挙げられる。本発明の水中油型エマルジョンに疎水性物質を添加する場合、その添加量は、水中油型エマルジョンの脂肪酸量に対し10%以下であることが好ましく、5%以下がさらに好ましい。前記範囲で疎水性物質を添加すれば、油水分離せずに疎水性物質が水中油型エマルジョンに溶解し、透明な性状を維持することができる。   The oil-in-water emulsion of the present invention may contain a hydrophobic substance. Hydrophobic substances include fragrance ingredients such as limonene, oil-based synthetic flavors, natural flavors extracted from natural products using supercritical carbon dioxide, fat-soluble vitamins such as vitamin E and vitamin A, docosahexaenoic acid (DHA) ), Polyunsaturated fatty acids (PUFA) such as eicosapentaenoic acid (EPA), glycerin esters thereof, and triglycerin fatty acid esters. Preferred triglycerin fatty acid esters include edible oils such as salad oil, soybean oil, cottonseed oil, olive oil, corn oil, and sesame oil. When a hydrophobic substance is added to the oil-in-water emulsion of the present invention, the amount added is preferably 10% or less, more preferably 5% or less, based on the amount of fatty acid in the oil-in-water emulsion. If the hydrophobic substance is added within the above range, the hydrophobic substance dissolves in the oil-in-water emulsion without oil / water separation, and the transparent property can be maintained.

さらに本発明の水中油型エマルジョンには、蛋白質又は蛋白質の分解物、キトサン、キサンチン、グルコサミンからなる群から選択される1種又は2種以上を添加することができる。蛋白質又は蛋白質の分解物としては、食品製造用として許容される各種の蛋白質のうち、水溶性の蛋白質又はその分解物が挙げられ、例えば、ゼラチンが好ましい。またキトサン、キサンチン、グルコサミンは、各種の市販品の中から適宜選択して用いることができる。これらの蛋白質又は蛋白質の分解物、キトサン、キサンチン、グルコサミンを本発明の水中油型エマルジョンに添加することで、エマルジョンの安定性が高められ、水で希釈した場合にも白濁しないエマルジョンを得ることができる。   Furthermore, 1 type, or 2 or more types selected from the group which consists of protein or the degradation product of protein, chitosan, xanthine, and glucosamine can be added to the oil-in-water emulsion of this invention. Examples of the protein or protein degradation product include water-soluble proteins or degradation products among various proteins that are acceptable for food production. For example, gelatin is preferable. Chitosan, xanthine, and glucosamine can be appropriately selected from various commercially available products. By adding these proteins or protein degradation products, chitosan, xanthine, and glucosamine to the oil-in-water emulsion of the present invention, the stability of the emulsion is improved, and an emulsion that does not become cloudy even when diluted with water can be obtained. it can.

本発明の水中油型エマルジョンにおいて、エマルジョン中の油滴の平均粒径は、200nm以下であることが好ましい。油滴の平均粒径を200nm以下とすることにより、実質的に透明で長時間安定な水中油型エマルジョンを製造することができる。   In the oil-in-water emulsion of the present invention, the average particle diameter of oil droplets in the emulsion is preferably 200 nm or less. By setting the average particle size of the oil droplets to 200 nm or less, an oil-in-water emulsion that is substantially transparent and stable for a long time can be produced.

本発明の水中油型エマルジョンの製造方法は、水と、脂肪酸と、アルコールと、塩基性アミノ酸とを、脂肪酸/水の質量組成比が1以下かつ脂肪酸/アルコールの質量組成比が1未満となるように混合し、系のpHを6〜8の範囲に調整して、本発明に係る前記水中油型エマルジョンを得ることを特徴としている。   In the method for producing an oil-in-water emulsion of the present invention, water, fatty acid, alcohol, and basic amino acid have a fatty acid / water mass composition ratio of 1 or less and a fatty acid / alcohol mass composition ratio of less than 1. And the pH of the system is adjusted in the range of 6 to 8 to obtain the oil-in-water emulsion according to the present invention.

本発明の水中油型エマルジョンの製造方法において、前記各成分を混合して均一なエマルジョンを製造する手順、製造設備等は、特に限定されない。典型的な製造手順を例示すれば、次のようになる。
(a)まず、所定量の水に、所定量の塩基性アミノ酸を添加して溶解し、
(b)次いで、この水を撹拌しながら、所定量の脂肪酸を加え、
(c)次いで更に攪拌しながら所定量のアルコールを加え、
(d)次いで得られたエマルジョンのpHをモニターしながら、水酸化ナトリウムなどのpH調整剤を添加して、系のpHを6〜8の範囲の所望のpH値に調整して、本発明の実質的に透明な水中油型エマルジョンを得る。
なお、この製造手順は単なる例示であり、本発明の製造方法は本例示のみに限定されない。
In the method for producing an oil-in-water emulsion of the present invention, the procedure, production equipment and the like for producing a uniform emulsion by mixing the components are not particularly limited. A typical manufacturing procedure is illustrated as follows.
(A) First, a predetermined amount of basic amino acid is added and dissolved in a predetermined amount of water,
(B) Then, while stirring this water, a predetermined amount of fatty acid is added,
(C) Then, a predetermined amount of alcohol is added with further stirring,
(D) Then, while monitoring the pH of the obtained emulsion, a pH adjusting agent such as sodium hydroxide is added to adjust the pH of the system to a desired pH value in the range of 6-8, and A substantially clear oil-in-water emulsion is obtained.
This manufacturing procedure is merely an example, and the manufacturing method of the present invention is not limited to this example.

本発明の製造方法の好ましい実施形態として、各材料を混合し多孔質膜を透過させて水中油型エマルジョンを得ることが挙げられる。この多孔質膜としては、市販のアルミナフィルターなどを用いることができ、細孔径が徐々に小さくなる複数段のフィルターに混合液を順次通過させて膜乳化するプロセスを行うことが好ましい。   As a preferred embodiment of the production method of the present invention, it is possible to obtain an oil-in-water emulsion by mixing each material and permeating through a porous membrane. As this porous membrane, a commercially available alumina filter or the like can be used, and it is preferable to carry out a process of emulsifying the membrane by sequentially passing the mixed solution through a plurality of stages of filters in which the pore diameter gradually decreases.

本発明の水中油型エマルジョンの製造方法において、必須成分の1つである脂肪酸を得るために、トリグリセリン脂肪酸エステルにその3つの脂肪酸残基の内の2つを加水分解するリパーゼを作用させて分解させ、脂肪酸を生成させ、この脂肪酸を他の必須成分と混合して水中油型エマルジョンを製造することもできる。これによって、植物油などの安価で安全な原料から脂肪酸を得ることができる。   In the method for producing an oil-in-water emulsion of the present invention, a lipase that hydrolyzes two of the three fatty acid residues is allowed to act on a triglycerin fatty acid ester in order to obtain a fatty acid that is one of the essential components. It can also be decomposed to produce fatty acids, which can be mixed with other essential ingredients to produce an oil-in-water emulsion. Thereby, fatty acids can be obtained from inexpensive and safe raw materials such as vegetable oils.

トリグリセリン脂肪酸エステルとしては、サラダ油、大豆油、綿実油、オリーブ油、コーン油、ごま油などの食用油などが挙げられる。またリパーゼとしては、トリグリセリドの三つの脂肪酸残基のうち二つを加水分解するリパーゼを用いることが望ましい。このようなリパーゼとしては、例えば、カンディダ・ルゴサ(Candida rugosa)の産生するリパーゼが挙げられる。このリパーゼは、トリグリセリドの1位および2位のエステル結合を加水分解し、脂肪酸を遊離させる。リパーゼの反応条件としては、使用するリパーゼの至適条件で使用すればよく、特に限定するものではないが、一般的には、室温〜50℃、pHは5〜8付近で使用される。   Triglycerin fatty acid esters include edible oils such as salad oil, soybean oil, cottonseed oil, olive oil, corn oil, and sesame oil. As the lipase, it is desirable to use a lipase that hydrolyzes two of the three fatty acid residues of triglyceride. Examples of such lipases include lipases produced by Candida rugosa. This lipase hydrolyzes the ester bonds at the 1-position and 2-position of triglyceride to liberate fatty acids. The reaction conditions for the lipase may be the optimum conditions for the lipase to be used, and are not particularly limited. In general, the lipase is used at room temperature to 50 ° C., and the pH is around 5 to 8.

次に実施例により本発明を更に詳細に説明するが、実施例により本発明を限定するものではない。
実施例および比較例中の%表記は、特記しない限り質量%を示す。
実施例における各測定条件は、下記の通りである。
EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited by an Example.
Unless otherwise specified,% notation in Examples and Comparative Examples indicates mass%.
Each measurement condition in the examples is as follows.

<エマルジョン中の油滴の平均粒径の測定方法>
エマルジョン中の油滴の平均粒径は、ゼータサイザーナノZS(マルマーン社製)により測定した。
<Measurement method of average particle diameter of oil droplets in emulsion>
The average particle diameter of the oil droplets in the emulsion was measured by Zetasizer Nano ZS (manufactured by Marman).

<エマルジョンの性状>
試料のエマルジョンを24時間静置し、その透明性、油水分離の有無、白濁の有無について目視で調べた。また、室温静置48時間後又は1ヶ月後について調べた場合には、表中に「性状2」と記し、その室温静置時間を併記した。
<Emulsion properties>
The sample emulsion was allowed to stand for 24 hours, and the transparency, presence / absence of oil / water separation, and presence / absence of white turbidity were examined visually. Moreover, when it investigated about 48 hours after room temperature standing or one month later, it described as "property 2" in the table | surface, and indicated the room temperature standing time together.

[実施例1]
ヒスチジン(和光純薬工業社製、試薬特級)0.1質量部をイオン交換水に溶解し、オレイン酸(和光純薬工業社製、試薬特級)5,10,20,又は30質量部を添加後、スターラーで撹拌しながら、エタノール(和光純薬工業社製、試薬特級)40質量部を添加し、系のpHを水酸化ナトリウムを用いて調整し、表1に示すNo.1〜No.4のエマルジョンを作製した。また、比較例として、ヒスチジンを用いない場合(比較例1)、エタノールを用いない場合(比較例2)も同様に作製した。
[Example 1]
Dissolve 0.1 parts by mass of histidine (Wako Pure Chemical Industries, reagent special grade) in ion-exchanged water, and add 5, 10, 20, or 30 parts by mass of oleic acid (made by Wako Pure Chemical Industries, reagent special grade) Thereafter, while stirring with a stirrer, 40 parts by mass of ethanol (manufactured by Wako Pure Chemical Industries, Ltd., special grade reagent) was added, and the pH of the system was adjusted with sodium hydroxide. 1-No. 4 emulsions were made. In addition, as a comparative example, a case where histidine was not used (Comparative Example 1) and a case where ethanol was not used (Comparative Example 2) were similarly produced.

Figure 0005415510
Figure 0005415510

表1に示すNo.1〜No.4、および比較例1,2の各試料について、脂肪酸/水の質量組成比、脂肪酸/アルコールの質量組成比、平均粒径および性状を比較した。結果を表2に示す。各エマルジョンのpHは表2に示す通りとした。   No. shown in Table 1. 1-No. 4 and the samples of Comparative Examples 1 and 2, the fatty acid / water mass composition ratio, the fatty acid / alcohol mass composition ratio, the average particle diameter, and the properties were compared. The results are shown in Table 2. The pH of each emulsion was as shown in Table 2.

Figure 0005415510
Figure 0005415510

表2に示す通り、ヒスチジンを含まない比較例1では、pHを9に調整しても、静置24時間後、油水の分離が見られた。また、アルコールを含まない比較例2でも、油水の分離が見られた。
一方、本実施例のNo.1〜No.4では、透明な水中油型エマルジョンが生成し、室温静置状態で1ヶ月以上、状態の変化は観察されなかった。
As shown in Table 2, in Comparative Example 1 containing no histidine, even when the pH was adjusted to 9, separation of oil and water was observed after 24 hours of standing. Moreover, also in the comparative example 2 which does not contain alcohol, isolation | separation of oil-water was seen.
On the other hand, no. 1-No. In No. 4, a transparent oil-in-water emulsion was formed, and no change in state was observed for more than 1 month when allowed to stand at room temperature.

(pHの有効範囲)
実施例1で作製したNo.4と同一組成のエマルジョンについて、系のpHを表3に示す通りに変化させた場合の平均粒径とエマルジョンの性状(安定性)について調べた。その結果を表3に示す。
(Effective range of pH)
No. 1 prepared in Example 1. For the emulsion having the same composition as No. 4, the average particle size and the properties (stability) of the emulsion when the pH of the system was changed as shown in Table 3 were examined. The results are shown in Table 3.

Figure 0005415510
Figure 0005415510

表3に示す通り、pH6未満のエマルジョンは不安定であり、静置24時間以内に油水の分離が見られた。
pH6以上のエマルジョンは、安定で小粒径のエマルジョンが得られた。
pH9を超えたものは、エマルジョンの安定性に大きな問題はなく、むしろ平均粒径が小さくなり安定であるが、口腔内に入れた場合に刺激が強く、食品としての好ましさに欠けた。
As shown in Table 3, the emulsion having a pH of less than 6 was unstable, and oil-water separation was observed within 24 hours of standing.
Emulsions having a pH of 6 or more gave stable and small-sized emulsions.
When the pH was over 9, there was no major problem in the stability of the emulsion. Rather, the average particle size was small and stable, but when placed in the oral cavity, the irritation was strong and the food was not preferred.

(アルコールの有効範囲)
実施例1のNo.1のエマルジョンにおける水とエタノールの比率を、表4に示す通りに変更し、それ以外は実施例1と同様にしてNo.5〜No.8のエマルジョンを作製した。各エマルジョンのpHは表5に示す通りとした。
(Effective range of alcohol)
No. of Example 1 The ratio of water and ethanol in the emulsion of No. 1 was changed as shown in Table 4, and other than that, in the same manner as in Example 1, No. 1 was obtained. 5-No. 8 emulsions were made. The pH of each emulsion was as shown in Table 5.

Figure 0005415510
Figure 0005415510

表4に示すNo.5〜No.8の各試料について、脂肪酸/水の質量組成比、脂肪酸/アルコールの質量組成比、平均粒径および性状を、No.1のエマルジョンと比較した。その結果を表5に示す。   No. shown in Table 4 5-No. For each sample of No. 8, the mass composition ratio of fatty acid / water, the mass composition ratio of fatty acid / alcohol, the average particle diameter, and the properties are shown in Comparison with one emulsion. The results are shown in Table 5.

Figure 0005415510
Figure 0005415510

表5に示す通り、通常、解乳化剤として使用されるアルコールが、本発明では、脂肪酸/アルコールの質量組成比が1未満で安定したエマルジョンを作製するための材料となっている。また、アルコールが10質量%以上の組成比であった方が、エマルジョンがさらに安定化することが分かった。   As shown in Table 5, the alcohol usually used as a demulsifier is a material for producing a stable emulsion having a fatty acid / alcohol mass composition ratio of less than 1 in the present invention. It was also found that the emulsion was further stabilized when the composition ratio of alcohol was 10% by mass or more.

[実施例2]
表6に示す通り、実施例1で作製したNo.4のエマルジョンにおいて、ヒスチジンに代えてアルギニン(和光純薬工業社製、試薬特級)を添加したエマルジョン(No.9)、リジン(和光純薬工業社製、試薬特級)を添加したエマルジョン(No.10)をそれぞれ作製した。エマルジョンのpHは表7に示す通りとした。
[Example 2]
As shown in Table 6, No. 1 prepared in Example 1 was obtained. In the emulsion of No. 4, an emulsion (No. 9) in which arginine (made by Wako Pure Chemical Industries, special grade) is added instead of histidine, and an emulsion (No. 9) made by adding lysine (made by Wako Pure Chemical Industries, special grade). 10) were produced respectively. The pH of the emulsion was as shown in Table 7.

Figure 0005415510
Figure 0005415510

No.9〜10のそれぞれのエマルジョンについて、平均粒径および性状について調べた。その結果を、No.4のエマルジョンの結果と併せて表7に示す。   No. For each of 9-10 emulsions, the average particle size and properties were examined. The results are The results are shown in Table 7 together with the results of emulsion No. 4.

Figure 0005415510
Figure 0005415510

表7に示す通り、ヒスチジン以外の塩基性アミノ酸(アルギニンおよびリジン)を用いた場合においても、ヒスチジンの場合と同様に透明なエマルジョンを作製できた。   As shown in Table 7, even when basic amino acids other than histidine (arginine and lysine) were used, a transparent emulsion could be produced as in the case of histidine.

[実施例3]
実施例1のNo.4と同じ組成のエマルジョンにモノオレイン酸グリセロールを0.1質量部添加して、No.11のエマルジョンを作製した。
[Example 3]
No. of Example 1 To the emulsion having the same composition as in No. 4, 0.1 part by mass of glycerol monooleate was added. Eleven emulsions were made.

Figure 0005415510
Figure 0005415510

各エマルジョンのpHは表9に示す通りとした。No.4およびNo.11のエマルジョンについて、平均粒径、性状(室温静置24時間後)および性状2(室温静置1ヶ月後)を調べた。その結果を表9に示す。   The pH of each emulsion was as shown in Table 9. No. 4 and no. For the emulsion No. 11, the average particle size, properties (after 24 hours at room temperature) and properties 2 (after 1 month at room temperature) were examined. The results are shown in Table 9.

Figure 0005415510
Figure 0005415510

表9に示す通り、本発明のエマルジョンは、モノグリセリン脂肪酸エステルを含むことにより、さらに安定したエマルジョンを調製することが可能である。   As shown in Table 9, the emulsion of the present invention can prepare a more stable emulsion by containing a monoglycerin fatty acid ester.

[実施例4]
実施例1のNo.4の組成をベースとし、オレイン酸の一部を炭素数18の飽和脂肪酸であるステアリン酸に置換してエマルジョン(No.12〜No.14)を作製した。
ヒスチジン(和光純薬工業社製、試薬特級)0.1質量部をイオン交換水に溶解し、表10の組成比に従いオレイン酸(和光純薬工業社製、試薬特級)を添加後、スターラーで撹拌しながら、ステアリン酸(和光純薬工業社製、試薬特級)を組成比に従い添加した。系の温度を70℃とし、ステアリン酸を溶解させ、エタノール(和光純薬工業社製、試薬特級)40質量部を添加した後、エタノールが揮発しないよう密閉し、撹拌した。加熱を停止し、系の温度が40℃となった時点で、系のpHを水酸化ナトリウムを用いて6.3に調整し、表10に示すNo.12〜No.14のエマルジョンを作製した。
[Example 4]
No. of Example 1 Based on the composition of No. 4, emulsions (No. 12 to No. 14) were prepared by replacing part of oleic acid with stearic acid, which is a saturated fatty acid having 18 carbon atoms.
Dissolve 0.1 parts by mass of histidine (made by Wako Pure Chemical Industries, Ltd., reagent grade) in ion-exchanged water, add oleic acid (made by Wako Pure Chemical Industries, Ltd., reagent grade) according to the composition ratio in Table 10, and then use a stirrer. While stirring, stearic acid (manufactured by Wako Pure Chemical Industries, Ltd., reagent grade) was added according to the composition ratio. The temperature of the system was set to 70 ° C., stearic acid was dissolved, 40 parts by mass of ethanol (made by Wako Pure Chemical Industries, Ltd., reagent special grade) was added, and the mixture was sealed and stirred so that ethanol did not volatilize. When the heating was stopped and the temperature of the system reached 40 ° C., the pH of the system was adjusted to 6.3 using sodium hydroxide. 12-No. 14 emulsions were made.

Figure 0005415510
Figure 0005415510

得られたNo.12〜No.14のエマルジョンについて、平均粒径および性状を調べた。その結果を、No.4のエマルジョンの結果と併せて表11に記す。   No. obtained 12-No. The average particle size and properties of 14 emulsions were examined. The results are The results are shown in Table 11 together with the results of emulsion No. 4.

Figure 0005415510
Figure 0005415510

表11に示す通り、炭素数18以上の飽和脂肪酸が脂肪酸組成の10質量%以上含まれると、温度の低下と共に白色の沈殿が徐々に発生し、安定なエマルジョンとは言えなくなった。   As shown in Table 11, when a saturated fatty acid having 18 or more carbon atoms was contained in an amount of 10% by mass or more of the fatty acid composition, a white precipitate was gradually generated as the temperature decreased, and it could not be said to be a stable emulsion.

[実施例5]
実施例1で作製した比較例1とNo.1の各エマルジョンに、リモネン(和光純薬工業社製、試薬特級)0.1%を添加し、開放状態でスターラーで撹拌し、経時的にサンプリングしてリモネン残存率(%)を高速液体クロマトグラフィー(HPLC)で測定した。その結果を図1のグラフにまとめて記す。
[Example 5]
Comparative Example 1 prepared in Example 1 and No. Add 1% of limonene (special grade reagent, manufactured by Wako Pure Chemical Industries, Ltd.) to each emulsion of No. 1, stir with an open stirrer, and sample over time to determine the residual rate of limonene (%) by high performance liquid chromatography. Measured by chromatography (HPLC). The results are summarized in the graph of FIG.

図1の結果より、比較例1では、1週間後のリモネン残存率がほぼ0%になっているのに対し、実施例1のNo.1では、90%近くの残存率があり、本発明によるエマルジョンは、疎水性物質をエマルジョン内に取り込み、かつ高い徐放性を示すことが明らかである。   From the results shown in FIG. 1, in Comparative Example 1, the limonene remaining rate after one week was almost 0%, whereas the No. In 1, there is a residual rate close to 90%, and it is clear that the emulsion according to the present invention incorporates a hydrophobic substance into the emulsion and exhibits high sustained release.

[実施例6]
実施例1で作製したNo.1〜No.4の水中油型エマルジョンにトリオレイン酸グリセロール(和光純薬工業社製、試薬特級;以下、TOと略記する)を添加し、エマルジョンに取り込まれ、かつ透明を維持できる量を測定した。測定した結果をTO溶解度(μl/100ml)として図2に記す。
[Example 6]
No. 1 prepared in Example 1. 1-No. Glycerol trioleate (manufactured by Wako Pure Chemical Industries, Ltd., reagent grade; hereinafter abbreviated as TO) was added to the oil-in-water emulsion of No. 4, and the amount that could be incorporated into the emulsion and maintained transparent was measured. The measurement results are shown in FIG. 2 as TO solubility (μl / 100 ml).

図2の結果から、エマルジョンの構成脂肪酸含量が20%の時、TOに対する溶解度の変曲点を示しており、構成脂肪酸が20%以上で急速にTO溶解度の増加が見られた。   From the result of FIG. 2, when the constituent fatty acid content of the emulsion is 20%, the inflection point of the solubility with respect to TO is shown, and when the constituent fatty acid is 20% or more, the TO solubility is rapidly increased.

[実施例7]
ヒスチジン(和光純薬工業社製、試薬特級)0.1質量部およびリパーゼAY−30(天野エンザイム社製)0.1質量部をイオン交換水に溶解し、サラダ油(日清オイリオ社製)30質量部を添加し、スターラーで撹拌しながら、室温で15時間後、エタノール(和光純薬工業社製、試薬特級)40質量部を添加し、系のpHを水酸化ナトリウムを用いて、6.5に調整した。
[Example 7]
0.1 parts by mass of histidine (manufactured by Wako Pure Chemical Industries, Ltd., reagent grade) and 0.1 parts by mass of lipase AY-30 (manufactured by Amano Enzyme) are dissolved in ion-exchanged water, and salad oil (manufactured by Nisshin Eulio) 30 After adding 15 parts by mass and stirring with a stirrer, after 15 hours at room temperature, 40 parts by mass of ethanol (made by Wako Pure Chemical Industries, Ltd., reagent grade) is added, and the pH of the system is adjusted with sodium hydroxide. Adjusted to 5.

Figure 0005415510
Figure 0005415510

前記のように作製した実施例7のエマルジョンの組成および性状は、表13および表14に示す通りであった。   The composition and properties of the emulsion of Example 7 produced as described above were as shown in Table 13 and Table 14.

Figure 0005415510
Figure 0005415510

Figure 0005415510
Figure 0005415510

また、この実施例7のエマルジョンにおいて、炭素数18以上の飽和脂肪酸の合計量は、脂肪酸組成中3%であった。   In the emulsion of Example 7, the total amount of saturated fatty acids having 18 or more carbon atoms was 3% in the fatty acid composition.

[実施例8]
実施例7で作製した水中油型エマルジョンに、スターラーで撹拌しながら、表15に示す添加量でサラダ油を添加していき、その時のエマルジョンの平均粒径および性状を観察した。
[Example 8]
While stirring with a stirrer, salad oil was added to the oil-in-water emulsion prepared in Example 7 at the addition amount shown in Table 15, and the average particle size and properties of the emulsion at that time were observed.

Figure 0005415510
Figure 0005415510

通常、透明状態を維持するには、可視光波長以下である50nm以下のエマルジョン粒径とすることが望ましいが、本実施例のように、エマルジョンの構成脂肪酸組成と、添加した疎水性物質の脂肪酸組成が近い場合には、光に対する屈折率が近くなるため、平均粒径が200nm程度であっても透明に見え、かつ安全なエマルジョンが得られる。   Usually, in order to maintain a transparent state, it is desirable to set the emulsion particle size to 50 nm or less which is not more than the visible light wavelength. However, as in this example, the constituent fatty acid composition of the emulsion and the fatty acid of the added hydrophobic substance When the composition is close, the refractive index with respect to light is close, so that even if the average particle size is about 200 nm, a transparent and safe emulsion can be obtained.

[実施例9]
ヒスチジン含量が1.6%である、かつお煮汁エキスNP−40(日本水産社製)の10%水溶液に、リパーゼAY−30を0.1%溶解し、スターラーで撹拌しながら、サラダ油30%を添加した。室温で15時間後、エタノール40%を添加して、水酸化ナトリウムでpHを6.5に調整した。その結果、かつお煮汁エキス由来の茶褐色の液色であり、実施例7と同様の透明なエマルジョンが得られた。
[Example 9]
In a 10% aqueous solution of bonito soup extract NP-40 (manufactured by Nihon Suisan Co., Ltd.) having a histidine content of 1.6%, 0.1% of lipase AY-30 is dissolved, and stirred with a stirrer, 30% salad oil is added. Added. After 15 hours at room temperature, 40% ethanol was added and the pH was adjusted to 6.5 with sodium hydroxide. As a result, a brownish brown liquid color derived from bonito soup extract was obtained, and a transparent emulsion similar to Example 7 was obtained.

ヒスチジンは、中性付近の緩衝能が強いのに加え、食品中に多量に含まれるアミノ酸であり、特に回遊魚の魚肉に多量に含まれる。従って、ヒスチジンを改めて添加しなくとも、食品由来成分として、本発明に使用することができるため、塩基性アミノ酸の中でも、ヒスチジンは、本発明において特に好ましい。   Histidine is an amino acid contained in a large amount in foods, in addition to having a strong buffer capacity near neutrality, and is particularly contained in a large amount in migratory fish. Therefore, since histidine can be used in the present invention as a food-derived component without adding histidine again, histidine is particularly preferable in the present invention among basic amino acids.

[実施例10]
ヒスチジン(和光純薬工業社製、試薬特級)0.1質量部およびリパーゼAY−30(天野エンザイム社製)0.1質量部をイオン交換水に溶解し、サラダ油(日清オイリオ社製)30質量部を添加し、スターラーで撹拌しながら、室温で15時間撹拌後、エタノール(和光純薬工業社製、試薬特級)40質量部を添加し、魚ゼラチン(マルハ社製)の10%水溶液10質量部を添加した。系のpHを水酸化ナトリウムを用いて、6.5に調整し、実施例10のエマルジョンを作製した。
[Example 10]
0.1 parts by mass of histidine (manufactured by Wako Pure Chemical Industries, Ltd., reagent grade) and 0.1 parts by mass of lipase AY-30 (manufactured by Amano Enzyme) are dissolved in ion-exchanged water, and salad oil (manufactured by Nisshin Eulio) 30 After adding 15 parts by mass and stirring with a stirrer for 15 hours at room temperature, 40 parts by mass of ethanol (made by Wako Pure Chemical Industries, Ltd., reagent grade) is added, and 10% aqueous solution of fish gelatin (manufactured by Maruha) 10 Part by weight was added. The pH of the system was adjusted to 6.5 using sodium hydroxide to produce the emulsion of Example 10.

前記実施例7のエマルジョンは、エマルジョン自体は安定であるが、それを水で希釈すると、系の平衡が崩れ、白濁した後、油水分離が見られる。
これに対し、実施例10のエマルジョンは、系のpHを調整する前に、蛋白質などの保護コロイド成分を添加することにより、作製したエマルジョンを水で希釈しても、白濁しないエマルジョンが得られた。
In the emulsion of Example 7, the emulsion itself is stable. However, when the emulsion is diluted with water, the equilibrium of the system is lost and the mixture becomes white turbid, followed by oil-water separation.
In contrast, the emulsion of Example 10 was obtained by adding a protective colloid component such as a protein before adjusting the pH of the system, so that an emulsion that did not become cloudy was obtained even when the prepared emulsion was diluted with water. .

[実施例11]
ヒスチジン(和光純薬工業社製、試薬特級)0.1質量部およびリパーゼAY−30(天野エンザイム社製)0.1質量部をイオン交換水に溶解し、サラダ油(日清オイリオ社製)30質量部を添加し、スターラーで撹拌しながら、室温で15時間後、エタノール(和光純薬工業社製、試薬特級)40質量部を添加し、水溶性キトサン(和光純薬工業社製、試薬特級)あるいはグルコサミン(和光純薬工業社製、試薬特級)の10%水溶液10質量部を添加した。系のpHを水酸化ナトリウムを用いて、6.5に調整し、実施例11のエマルジョンを作製した。
[Example 11]
0.1 parts by mass of histidine (manufactured by Wako Pure Chemical Industries, Ltd., reagent grade) and 0.1 parts by mass of lipase AY-30 (manufactured by Amano Enzyme) are dissolved in ion-exchanged water, and salad oil (manufactured by Nisshin Eulio) 30 After adding 15 parts by mass and stirring with a stirrer, after 15 hours at room temperature, 40 parts by mass of ethanol (manufactured by Wako Pure Chemical Industries, Ltd., reagent grade) is added, and water-soluble chitosan (manufactured by Wako Pure Chemical Industries, Ltd., reagent grade) ) Or 10 parts by mass of a 10% aqueous solution of glucosamine (manufactured by Wako Pure Chemical Industries, Ltd., special grade reagent). The pH of the system was adjusted to 6.5 using sodium hydroxide to produce the emulsion of Example 11.

実施例10と同様、キトサンあるいはグルコサミンを添加した場合でも、希釈による白濁を防止することが可能であった。
これら蛋白質やキトサンは、NH-基を持つ高分子化合物で、本発明のエマルジョン中に含まれる脂肪酸のカルボキシル基と相互作用をし、エマルジョンの安定化に寄与するものと考えられ、これらの分解物もまた、同様の効果を示すものと考えられる。
Similar to Example 10, even when chitosan or glucosamine was added, it was possible to prevent white turbidity due to dilution.
These proteins and chitosan are high molecular compounds having NH 2 -groups, which interact with the carboxyl groups of fatty acids contained in the emulsion of the present invention, and are thought to contribute to the stabilization of the emulsion. Objects are also considered to show similar effects.

[実施例12]
実施例1のpH有効範囲の特定(表3参照)でpH6の青白い白濁エマルジョンをメンブランフィルター(MIPORE社製)細孔径0.45μmを通過させ、次にアルミナフィルター(WHATMAN社製)細孔径0.2μm,0.1μm,0.02μmの膜を順に通過させた。その結果、青白い白濁エマルジョンが透明なエマルジョンとなり、そのときの平均粒径は、38nmであった。
[Example 12]
In the specification of the effective pH range of Example 1 (see Table 3), a pale white cloudy emulsion having a pH of 6 was passed through a membrane filter (MIPORE) having a pore size of 0.45 μm, and then an alumina filter (WHATMAN) having a pore size of 0. 2 μm, 0.1 μm, and 0.02 μm membranes were sequentially passed. As a result, the pale white emulsion became a transparent emulsion, and the average particle size at that time was 38 nm.

通常の食品は、pHが6付近の弱酸性であることが多く、多孔質膜にエマルジョンを通過させることにより、弱酸性領域のpHでのエマルジョンの透明化および安定化を図ることができた。   Ordinary foods are often weakly acidic with a pH of around 6. By allowing the emulsion to pass through a porous membrane, it was possible to achieve transparency and stabilization of the emulsion at a pH in the weakly acidic region.

本発明は、安価で安心、安全な食品用水中油型エマルジョン組成およびその製造方法であり、容易に実質的に透明な水中油型のマイクロエマルジョンとすることができ、フレーバー物質などの疎水性物質を可溶化し、食品に添加することができる食品用水中油型マイクロエマルジョンの製造方法に関する。   The present invention is an inexpensive, safe and safe oil-in-water emulsion composition for food and a method for producing the same, and can be easily made into a substantially transparent oil-in-water microemulsion, and a hydrophobic substance such as a flavor substance can be obtained. The present invention relates to a method for producing an oil-in-water microemulsion for food that can be solubilized and added to food.

Claims (3)

トリグリセリン脂肪酸エステルに、その3つの脂肪酸残基の内の2つを加水分解するリパーゼを作用させて脂肪酸を得て、水と、前記脂肪酸と、アルコールと、塩基性アミノ酸とを、脂肪酸/水の質量組成比が1以下かつ脂肪酸/アルコールの質量組成比が1未満となるように混合し、キトサン又はキトサンの分解物又はグルコサミンを添加した後に系のpHを6〜8の範囲に調整して、界面活性剤及び乳化剤を含まない水中油型エマルジョンを得ることを特徴とする水中油型エマルジョンの製造方法。 A triglycerin fatty acid ester is allowed to act on a lipase that hydrolyzes two of the three fatty acid residues to obtain a fatty acid. Water, the fatty acid, alcohol, and a basic amino acid are mixed with fatty acid / water. The mass composition ratio is 1 or less and the mass composition ratio of the fatty acid / alcohol is less than 1, and after adding chitosan or a degradation product of chitosan or glucosamine, the pH of the system is adjusted to a range of 6-8. A method for producing an oil-in-water emulsion, characterized by obtaining an oil-in-water emulsion that does not contain a surfactant and an emulsifier . 各材料を混合し多孔質膜を透過させて水中油型エマルジョンを得ることを特徴とする請求項1に記載の水中油型エマルジョンの製造方法。   The method for producing an oil-in-water emulsion according to claim 1, wherein each material is mixed and permeated through a porous membrane to obtain an oil-in-water emulsion. エマルジョンのpHを調整する前に、蛋白質又は蛋白質の分解物を添加することを特徴とする請求項1又は2に記載の水中油型エマルジョンの製造方法。   The method for producing an oil-in-water emulsion according to claim 1 or 2, wherein a protein or a degradation product of the protein is added before adjusting the pH of the emulsion.
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