JP2006050946A - Microcapsule using pectin as wall material - Google Patents
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- 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
- A61K9/48—Preparations in capsules, e.g. of gelatin, of chocolate
- A61K9/50—Microcapsules having a gas, liquid or semi-solid filling; Solid microparticles or pellets surrounded by a distinct coating layer, e.g. coated microspheres, coated drug crystals
- A61K9/5005—Wall or coating material
- A61K9/5021—Organic macromolecular compounds
- A61K9/5036—Polysaccharides, e.g. gums, alginate; Cyclodextrin
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- 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
- A23L29/00—Foods or foodstuffs containing additives; Preparation or treatment thereof
- A23L29/20—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents
- A23L29/206—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents of vegetable origin
- A23L29/231—Pectin; Derivatives thereof
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23P—SHAPING OR WORKING OF FOODSTUFFS, NOT FULLY COVERED BY A SINGLE OTHER SUBCLASS
- A23P10/00—Shaping or working of foodstuffs characterised by the products
- A23P10/30—Encapsulation of particles, e.g. foodstuff additives
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Abstract
Description
本発明は、ペクチンを壁材とするマイクロカプセルに関する The present invention relates to a microcapsule using pectin as a wall material.
近年、健康志向の高まりから栄養補助食品、機能性食品などの健康食品が注目されている。これらの食品に含まれる内容成分の保護、安定化、味・臭いのマスキングのためにカプセルが用いられている。カプセルにも様々な種類があるが、錠剤などのハードカプセル、ソフトカプセル、シームレスカプセル、従来のマイクロカプセルは粒径が０．３ｍｍ〜２ｃｍであり、喫食時に舌で知覚できる大きさである。その為、食品にこれらのカプセルを配合すると食感が変化してしまう。マヨネーズなどの乳化物タイプの食品は粒径が５μｍ以下であり、喫食時に舌で知覚できない大きさである。しかし、乳化物タイプの食品は加熱安定性・保存安定性、マスキングの困難性、コスト、などの点で課題がある。 In recent years, health foods such as nutritional supplements and functional foods have attracted attention due to the growing health-consciousness. Capsules are used to protect and stabilize the contents contained in these foods and mask taste and odor. There are various types of capsules, but hard capsules such as tablets, soft capsules, seamless capsules, and conventional microcapsules have a particle size of 0.3 mm to 2 cm, and can be perceived by the tongue when eating. Therefore, when these capsules are mixed with food, the texture changes. Emulsion-type foods such as mayonnaise have a particle size of 5 μm or less, and cannot be perceived by the tongue when eating. However, emulsion-type foods have problems in terms of heat stability / storage stability, difficulty in masking, and cost.
また、従来のマイクロカプセルにおいてはその壁材として牛、豚、鳥、魚などの動物由来のタンパクが用いられてきたが、非動物性の素材に対する市場の要求も高まっている。 Moreover, in the conventional microcapsules, protein derived from animals such as cows, pigs, birds, and fish has been used as the wall material, but the market demand for non-animal materials is also increasing.
非動物性の素材を壁材としたマイクロカプセルの製造法として、多糖類と油状物質のエマルションを多価陽イオン塩水溶液に滴下し、多糖類と多価イオンとの間に架橋結合を形成せしめて固形化させるマイクロカプセルが知られている（特許文献１参照）。 As a method for producing microcapsules using non-animal materials as a wall material, an emulsion of polysaccharides and oily substances is dropped into an aqueous solution of polyvalent cation salt to form a crosslink between the polysaccharide and polyvalent ions. There are known microcapsules that are solidified (see Patent Document 1).
しかしながら、エマルションを多価陽イオン塩水溶液に滴下する該滴下法では、粒径がノズル径やぬれ性に依存するためミリオーダーの比較的大きなカプセルしかできない。また、ひとつのカプセル中に複数の油滴が存在する多芯カプセルであるため、１カプセル当りの内包量が少ないという課題がある。 However, in the dropping method in which the emulsion is dropped into the aqueous polyvalent cation salt solution, since the particle diameter depends on the nozzle diameter and wettability, only a comparatively large capsule on the order of millimeters can be produced. Moreover, since it is a multi-core capsule in which a plurality of oil droplets exist in one capsule, there is a problem that the amount of encapsulation per capsule is small.
乳化剤を使用せずメジアン径が３μｍ以下のマイクロカプセルも知られている（特許文献２参照）。 A microcapsule having a median diameter of 3 μm or less without using an emulsifier is also known (see Patent Document 2).
しかしながら該発明は、壁材としてタンパク質を用いることが必須である。また予備乳化や圧力処理等などの操作が必要であるなど製造方法が複雑である。 However, in the invention, it is essential to use protein as a wall material. In addition, the manufacturing method is complicated such as operations such as preliminary emulsification and pressure treatment.
天然由来多糖類を含有した平均粒径が０．１〜５０μｍの微粒子が知られている（特許文献３参照）。 Fine particles having an average particle diameter of 0.1 to 50 μm containing natural polysaccharides are known (see Patent Document 3).
しかしながら該発明は多芯カプセルの製造法であるため、多孔質ガラス膜による膜乳化や、濃度調整工程、不溶化工程など複雑な工程が多段階必要である。また多芯カプセルであるため１カプセル当りの内包量も少なくなる。 However, since the invention is a method for producing a multi-core capsule, complicated steps such as membrane emulsification with a porous glass membrane, concentration adjustment step, and insolubilization step are required. Moreover, since it is a multi-core capsule, the amount of encapsulation per capsule is reduced.
水溶性多糖類などの水溶性高分子を外水相に配合したＷ／Ｏ／Ｗ複合エマルションが知られている（特許文献４参照）。 A W / O / W composite emulsion in which a water-soluble polymer such as a water-soluble polysaccharide is blended in an outer aqueous phase is known (see Patent Document 4).
しかしながら該発明のエマルションにはメジアン径が２０〜２０００ｎｍと小さいものも含まれるが、該発明は水、油性成分、親油性乳化剤の組成比に特徴がある。その為、乳化剤が必須の構成要件であるだけでなく、使用できる油性成分も限定されてしまう。 However, the emulsions of the invention include those having a median diameter as small as 20 to 2000 nm, but the invention is characterized by the composition ratio of water, an oily component, and a lipophilic emulsifier. Therefore, an emulsifier is not only an essential component, but also the oily components that can be used are limited.
香料等を食用ガム質の膜により内包するマイクロカプセルが知られている（特許文献５参照）。 There is known a microcapsule in which a fragrance is encapsulated by an edible gum-like film (see Patent Document 5).
該発明のカプセル製法としてコアセルベート法とシームレス法が挙げられているが、コアセルベート法の場合、高分子の小滴（コアセルベート）を芯物質（油）の表面に集めて形成させるためカプセル膜厚はコアセルベート滴より必ず大きくなる（参照：Multi-layered gelatin/acacia microcapsules by complex coaservation method, Journal of chemical engineering of japan, 793-798 vol.30 No.5 1997）。また、シームレス法の場合はカプセル粒径がノズル径やぬれ性に依存するため、該発明のマイクロカプセルは粒径が数百μｍ以下にすることは困難である。なお、本発明においてコアセルベート法（コアセルべーション法）とは、高分子溶液中にあらかじめ不溶性の芯物質粒子（油など）を分散しておき、次いで高分子濃度、温度、ｐHなどの変数をコアセルベーションが起こる領域の値に調整しコアセルベート滴を生成させ、芯物質粒子の表面に集めマイクロカプセルを製造することをいう。 Although the coacervate method and the seamless method are mentioned as the capsule manufacturing method of the present invention, in the case of the coacervate method, since the polymer droplets (coacervate) are collected and formed on the surface of the core material (oil), the capsule film thickness is coacervate It is always larger than the droplet (see: Multi-layered gelatin / acacia microcapsules by complex coaservation method, Journal of chemical engineering of japan, 793-798 vol.30 No.5 1997). In the case of the seamless method, since the capsule particle diameter depends on the nozzle diameter and wettability, it is difficult for the microcapsules of the present invention to have a particle diameter of several hundred μm or less. In the present invention, the coacervate method (coacervation method) means that insoluble core material particles (oil, etc.) are dispersed in advance in a polymer solution, and then variables such as polymer concentration, temperature, pH, etc. This refers to the production of microcapsules by adjusting the value of the region where the cervation occurs to produce coacervate droplets and collecting them on the surface of the core material particles.
天然高分子を用いたカプセルも知られている（特許文献６参照） Capsules using natural polymers are also known (see Patent Document 6).
しかし該発明は、シームレスカプセルであるため粒径が大きい。 However, since the invention is a seamless capsule, the particle size is large.
本発明は前記のような課題を解決するためになされたものである。本発明の目的はマイクロカプセルを提供することである。 The present invention has been made to solve the above-described problems. An object of the present invention is to provide a microcapsule.
上記課題を解決すべく検討した結果、ペクチンを含む水相と油相でＯ／Ｗエマルションを作製した後、多価陽イオンを混合することにより、油溶性物質を内包し、メジアン径が０．０１〜１００μｍであるマイクロカプセルが製造できることを見出し、本発明を完成させるに至った。更に具体的には内包物が油溶性であり、カプセルの壁材が非動物性であるペクチンであり、カプセルの材料として界面活性剤・乳化剤が必須でなく、調製が簡易であり、安定性が良く、かつ１カプセル当りの油内包量の多いマイクロカプセルが好ましいことを見出した。本発明は特に、医薬品、食品、健康食品等の分野、動物用飼料分野、化粧品、バス・トイレタリーなどの分野において有用である。 As a result of studying to solve the above problems, an O / W emulsion was prepared with an aqueous phase containing pectin and an oil phase, and then mixed with a polyvalent cation to encapsulate an oil-soluble substance and have a median diameter of 0. The inventors have found that microcapsules having a size of 01 to 100 μm can be produced, and have completed the present invention. More specifically, the inclusion is oil-soluble, and the capsule wall material is non-animal pectin. No surfactant or emulsifier is essential as the capsule material, and the preparation is simple and stable. It has been found that microcapsules which are good and have a large amount of oil inclusion per capsule are preferable. The present invention is particularly useful in the fields of pharmaceuticals, foods, health foods, animal feeds, cosmetics, baths and toiletries.
即ち本発明は、１）０．０１〜１０重量％のペクチンを含む水相と油相でＯ／Ｗエマルションを作製した後、多価陽イオンを混合することで得られる、壁材にペクチン多価陽イオンゲルを含み、油溶性物質を内包し、メジアン径が０．０１〜１００μｍであるマイクロカプセルを含み、また、２）０．０１〜１０重量％のペクチンを含む水相と油相でＯ／Ｗエマルションを作製した後、カルシウムイオンを混合することで得られる、壁材にペクチンカルシウムゲルを含み、油溶性物質を内包し、メジアン径が０．０１〜１００μｍであるマイクロカプセルを含み、また、３）Ｏ／Ｗエマルションを作成するときに乳化剤を用いないことを特徴とする１）又は２）のマイクロカプセルを含み、また、４）ペクチンがアミド基を持つことを特徴とする１）ないし３）のマイクロカプセルを含み、また、５）内包する油溶性物質がＷ／Ｏエマルションであることを特徴とする１）ないし４）のマイクロカプセルを含み、また、６）Ｏ／Ｗエマルションを作製し、多価陽イオンを混合した後に、ペクチンメチルエステラーゼを添加することを特徴とする１）ないし５）のマイクロカプセルを含み、また、７）ペクチンメチルエステラーゼを添加した後に、多価陽イオンを添加することを特徴とする６）のマイクロカプセルを含む。 That is, the present invention is as follows. 1) After producing an O / W emulsion with an aqueous phase and an oil phase containing 0.01 to 10% by weight of pectin, the wall material obtained by mixing multivalent cations It contains a cation gel, contains an oil-soluble substance, contains a microcapsule having a median diameter of 0.01 to 100 μm, and 2) O in an aqueous phase and an oil phase containing 0.01 to 10% by weight of pectin. / W emulsion obtained by mixing calcium ions, including pectin calcium gel in the wall material, encapsulating oil-soluble substances, including microcapsules having a median diameter of 0.01 to 100 μm, and 3) including the microcapsules of 1) or 2), characterized in that no emulsifier is used when preparing an O / W emulsion, and 4) characterized in that the pectin has an amide group 1) to 3) microcapsules, 5) the encapsulated oil-soluble substance is a W / O emulsion, and 1) to 4) microcapsules, and 6) O / 1) to 5) microcapsules characterized by adding a pectin methylesterase after preparing a W emulsion and mixing a polyvalent cation, and 7) adding a pectin methylesterase, 6) microcapsules characterized by adding a valent cation.
本発明によれば、喫食時に知覚しない大きさ、具体的にはメジアン径が１００μｍ以下のマイクロカプセルを製造することができる。また、内包物が油溶性であり、カプセルの壁材が非動物性であるペクチンであり、カプセルの材料として界面活性剤・乳化剤が必須でなく、調製が簡易であり、安定性が良く、かつ１カプセル当りの油内包量の多いマイクロカプセルを提供することができる。 According to the present invention, it is possible to manufacture a microcapsule having a size that is not perceived during eating, specifically, a median diameter of 100 μm or less. Further, the inclusion is oil-soluble, the capsule wall material is non-animal pectin, a surfactant / emulsifier is not essential as the capsule material, the preparation is simple, the stability is good, and A microcapsule having a large amount of oil inclusion per capsule can be provided.
本発明においてマイクロカプセルとはメジアン径が０．０１〜１００μｍのカプセルを意味する。カプセルの安定性の点や人が感知せず摂取できるという点からはメジアン径が小さいことが好ましい。人が感知せず摂取するにはメジアン径が１００μｍ以下、より好ましくは１０μｍ以下であることがより好ましい。本発明においてはマイクロカプセルの中に有効成分を導入することもできるが、内包効率の点からはメジアン径は０．１μｍ以上であることが好ましい。また本発明におけるカプセルの製造方法は、メジアン径が０．０１〜１００μｍのカプセルを製造できるものであれば良く、超音波を用いる方法、撹拌法、高圧押し出し法などがあげられる。複数管のノズルを用いてシームレスカプセルを製造する方法やコアセルベート法による製造方法、打錠によるカプセルの製造方法ではメジアン径が０．０１〜１００μｍのカプセルを製造することが出来ないため本発明には用いることができない。 In the present invention, the microcapsule means a capsule having a median diameter of 0.01 to 100 μm. The median diameter is preferably small from the viewpoint of the stability of the capsule and the fact that it can be ingested by humans. For ingestion by humans, the median diameter is 100 μm or less, more preferably 10 μm or less. In the present invention, an active ingredient can be introduced into the microcapsule, but the median diameter is preferably 0.1 μm or more from the viewpoint of the encapsulation efficiency. Moreover, the capsule manufacturing method in this invention should just be what can manufacture a capsule with a median diameter of 0.01-100 micrometers, and the method of using an ultrasonic wave, the stirring method, a high pressure extrusion method, etc. are mention | raise | lifted. In the present invention, a capsule having a median diameter of 0.01 to 100 μm cannot be produced by a method of producing a seamless capsule using a nozzle of a plurality of tubes, a production method by a coacervate method, or a production method of a capsule by tableting. Cannot be used.
本発明においてカプセルの壁材となる材料は、ペクチンであることが重要である。ペクチン濃度は、水溶液中に０．０１〜１０％、より好ましくは０．１〜３％、更に好ましくは１〜３％である。ペクチン濃度が高すぎるとカプセルが凝集する点で好ましくなく、ペクチン濃度が低すぎるとカプセルの安定性が低く内包油が分離する点で好ましくない。 In the present invention, it is important that the material used as the wall of the capsule is pectin. The pectin concentration is 0.01 to 10% in the aqueous solution, more preferably 0.1 to 3%, and still more preferably 1 to 3%. If the pectin concentration is too high, it is not preferable in that the capsules aggregate, and if the pectin concentration is too low, the stability of the capsule is low and it is not preferable in that the encapsulated oil is separated.
カプセルの壁材となるペクチンはアミド化されていると疎水結合によりゲル強度が増す点で好ましい。 It is preferable that the pectin as the wall material of the capsule is amidated in that the gel strength is increased by the hydrophobic bond.
水相と混合される溶液は、油溶性物質であれば特に限定はないが、取り扱いやコスト、安全性の点から食用油であるとより好ましい。油溶性物質中に薬剤や食用の栄養成分などの目的物質をあらかじめ混合させておくことで、マイクロカプセルとその内包物を別々に製造することなく一度に目的物質を含有したマイクロカプセルを製造することができ好ましい。また油溶性物質がＷ／Ｏエマルションであっても良く、その場合、水溶性の薬剤や食用の栄養成分などを内包できる点で好ましい。本文中では、特に断りのない限りはマイクロカプセルの内容物が疎水性の例で説明する。 The solution mixed with the aqueous phase is not particularly limited as long as it is an oil-soluble substance, but is more preferably an edible oil from the viewpoint of handling, cost, and safety. Producing microcapsules containing the target substance at once without separately manufacturing the microcapsules and their inclusions by mixing the target substances such as drugs and edible nutritional components in advance with oil-soluble substances This is preferable. The oil-soluble substance may be a W / O emulsion, which is preferable in that it can contain a water-soluble drug, an edible nutritional component, and the like. In the text, unless otherwise specified, the contents of the microcapsules will be described with an example of being hydrophobic.
本発明においては、ペクチンを含む水相と油相でＯ／Ｗエマルションを作製した後に多価陽イオンと混合することが重要である。更に安定性の点から、多価陽イオンはカルシウムイオンであることが好ましい。
またカルシウムイオン濃度は、０．０１〜１０００ｍＭ、より好ましくは０．０１〜１００ｍＭ、更に好ましくは１〜１０ｍＭである。多価陽イオン濃度が高すぎると、カプセルが凝集する点で好ましくなく、多価陽イオン濃度が低すぎるとカプセルの安定性が低く内包油が分離する点で好ましくない。
In the present invention, it is important that an O / W emulsion is prepared with an aqueous phase containing pectin and an oil phase and then mixed with a polyvalent cation. Furthermore, from the viewpoint of stability, the polyvalent cation is preferably a calcium ion.
The calcium ion concentration is 0.01 to 1000 mM, more preferably 0.01 to 100 mM, and still more preferably 1 to 10 mM. If the polyvalent cation concentration is too high, it is not preferable in terms of aggregation of the capsules, and if the polyvalent cation concentration is too low, it is not preferable in terms of low stability of the capsules and separation of the encapsulated oil.
一般的にエマルション、サスペンションを作製する際に乳化剤を加えることが知られている。本発明においても、例えばシュガーエステル、モノグリセライド、ソルビタンエステル等の乳化剤を加えてマイクロカプセルを形成できるが、本発明では食品、医薬品として摂取する場合の安全性、臭い、コスト等の理由のためカプセル被膜の材料に乳化剤を含まなくてもマイクロカプセルを安定的に形成することが出来ることも特徴である。 In general, it is known to add an emulsifier when preparing an emulsion or suspension. Also in the present invention, microcapsules can be formed by adding an emulsifier such as sugar ester, monoglyceride, sorbitan ester, etc., but in the present invention, the capsule coating film is used for reasons such as safety, odor, and cost when ingested as a food or medicine. It is also a feature that microcapsules can be stably formed even if the material does not contain an emulsifier.
本発明において、カプセル調製後にペクチンメチルエステラーゼ（以下、ＰＭＥという場合有り）と反応させることでカプセルの加熱負荷に対する構造安定性、内包物安定性が向上する。ＰＭＥに多価陽イオン、好ましくはカルシウムイオン添加を行うことによりカプセルの加熱負荷に対する構造安定性、内包物安定性が更に向上する。ＰＭＥ濃度は２〜３００ｍＰＥＵ／ｍｌ、好ましくは２０〜３００ｍＰＥＵ／ｍｌである。ＰＭＥ濃度が高すぎるとカプセルが凝集する点で好ましくなく、ＰＭＥ濃度が低すぎると安定性向上効果が少ない点で好ましくない。ここでＰＥＵとは、Pectin Esterase Unitの略であり、ＰＭＥ１ｍｌが１分間にペクチンのメチルエステルを分解して１ｍ ｍｏｌの酸を生産する能力を示す単位である。 In the present invention, the structure stability and inclusion stability against the heating load of the capsule are improved by reacting with pectin methylesterase (hereinafter sometimes referred to as PME) after preparation of the capsule. By adding a polyvalent cation, preferably calcium ion, to the PME, the structural stability and inclusion stability of the capsule against heating load are further improved. The PME concentration is 2 to 300 mPEU / ml, preferably 20 to 300 mPEU / ml. If the PME concentration is too high, it is not preferable in that the capsules aggregate, and if the PME concentration is too low, it is not preferable in that the effect of improving the stability is small. Here, PEU is an abbreviation for Pectin Esterase Unit, which is a unit that indicates the ability of 1 ml of PME to produce 1 mmol of acid by decomposing methyl ester of pectin in 1 minute.
またＰＭＥに対して多価陽イオン、具体的にはカルシウムイオン等を添加することは必須ではないが、加熱負荷に対する安定性を高めるためにカルシウムイオンを添加する場合は、０．０１〜２０ｍＭの濃度、より好ましくは１〜１０ｍＭの濃度である。カルシウムイオン濃度が高すぎるとカプセルが凝集する点で好ましくなく、カルシウムイオン濃度が低すぎると安定性向上効果が少ない点で好ましくない。またカルシウムイオンを加えないとカルシウムイオンにキレートされないフリーのカルボキシル基が過剰となりカプセルが凝集したりカプセル壁構造が弱くなったりする。 In addition, it is not essential to add polyvalent cations, specifically calcium ions, etc. to PME, but when adding calcium ions to increase the stability against heating load, 0.01-20 mM The concentration is more preferably 1 to 10 mM. If the calcium ion concentration is too high, it is not preferable in that the capsules aggregate, and if the calcium ion concentration is too low, it is not preferable in that the effect of improving the stability is small. If calcium ions are not added, free carboxyl groups that are not chelated by calcium ions become excessive, and the capsules aggregate or the capsule wall structure becomes weak.
また、カプセル調製前にＰＭＥ処理を行うとカプセル調製時に全体がゲル化しカプセルが形成されない。よってカプセル調製後にＰＭＥ処理や塩化カルシウム添加を行うことにより、カプセル壁がさらに強化される。 In addition, if PME treatment is performed before capsule preparation, the whole gels during capsule preparation and no capsule is formed. Therefore, the capsule wall is further strengthened by performing PME treatment or calcium chloride addition after capsule preparation.
超音波装置を用いたペクチンカプセルの製造 Production of pectin capsules using an ultrasonic device
ペクチン（商品名「ＬＭ−１０４ＡＳ」、ＣＰＫｅｌｃｏ ＪＡＰＡＮ製）と脱イオン水を混合し、２％ペクチン水溶液を調製した。次に５０ｍｌステンレスチューブに２％ペクチン水溶液２７ｍｌと大豆油（味の素製油株式会社製）３ｍｌを加え、ステンレスチューブの周囲を氷冷した状態で超音波処理機Ｓｏｎｉｆｉｅｒ２５０（Ｂｒａｎｓｏｎ社製）により、出力１４５Ｗで２分間処理を行った。超音波処理開始後３０秒経過したところでマイクロシリンジポンプＩＣ３１００（ＫＤ Ｓｃｉｅｎｔｉｆｉｃ社製）を用いて７．３ｍＭ塩化カルシウム２ｍｌを１２７ｍｌ／ｈ の速度で添加したところ、乳白色の分散液を得た。 Pectin (trade name “LM-104AS”, manufactured by CPKelco JAPAN) and deionized water were mixed to prepare a 2% aqueous pectin solution. Next, 27 ml of 2% pectin aqueous solution and 3 ml of soybean oil (Ajinomoto Oil Co., Ltd.) are added to a 50 ml stainless tube, and the stainless steel tube is cooled with ice with an ultrasonic processor Sonifier 250 (Branson) at an output of 145 W. Treated for 2 minutes. After 30 seconds from the start of the ultrasonic treatment, 2 ml of 7.3 mM calcium chloride was added at a rate of 127 ml / h using a micro syringe pump IC3100 (manufactured by KD Scientific) to obtain a milky white dispersion.
大豆油をＮｉｌｅ Ｒｅｄ、ペクチンをＲｈｏｄａｍｉｎｅで蛍光染色した前記分散液を、共焦点レーザースキャン顕微鏡 ＬＳＭ５１０（Ｃａｒｌ Ｚｅｉｓｓ社製）にて観察したところ、大豆油を内包したマイクロカプセルの形成が確認された。またマイクロカプセル分散液の粒度分布をレーザー回折式粒度分布計ＬＡ９２０（堀場製作所社製）にて測定したところシングルピークであり、マイクロカプセルの外径のメジアン径は１．３μｍであった。 When the dispersion liquid obtained by fluorescently staining soybean oil with Nile Red and pectin with Rhodamine was observed with a confocal laser scanning microscope LSM510 (manufactured by Carl Zeiss), formation of microcapsules containing soybean oil was confirmed. Further, when the particle size distribution of the microcapsule dispersion was measured with a laser diffraction particle size distribution analyzer LA920 (manufactured by Horiba, Ltd.), it was a single peak, and the median diameter of the outer diameter of the microcapsule was 1.3 μm.
マイクロカプセルの壁材の検討 Examination of wall material of microcapsule
マイクロカプセルの壁材と陽イオンとして以下の組み合わせを用いた。
１）ペクチン０．０２〜５％、塩化カルシウム０〜７００ｍＭ、
２）アルギン酸０．２５〜１％、塩化カルシウム０〜０．１Ｍ、
３）ＰＧＡ１〜４０％、みょうばん２〜２００ｍＭ、
４）κ-カラギーナン０．１〜１％、塩化カリウム０〜０．２Ｍ、
５）ι-カラギーナン０．１〜１％、塩化カルシウム０〜０．２Ｍ、
６）ゼラチン−アラビアガム（１対１混合物）０．０１〜０．１％
これらの組み合わせでそれぞれの最適条件を検討し、
１）ペクチン２％、塩化カルシウム７ｍＭ、
２）アルギン酸０．２５％、塩化カルシウム０．０５Ｍ、
３）ＰＧＡ１％、みょうばん５ｍＭ、
４）κ-カラギーナン０．５％、塩化カリウム０．０２Ｍ、
５）ι-カラギーナン０．５％、塩化カルシウム０．２Ｍ、
６）ゼラチン−アラビアガム０．０１％
を選定した。そして各壁材と各陽イオンを用い実施例１と同様の方法により製造したマイクロカプセル分散液を調製した。
The following combinations were used as wall materials and cations for microcapsules.
1) Pectin 0.02-5%, calcium chloride 0-700 mM,
2) Alginic acid 0.25 to 1%, calcium chloride 0 to 0.1M,
3) PGA 1-40%, Alum 2-200mM,
4) κ-carrageenan 0.1-1%, potassium chloride 0-0.2M,
5) ι-carrageenan 0.1-1%, calcium chloride 0-0.2M,
6) Gelatin-Gum arabic (1: 1 mixture) 0.01-0.1%
We examine each optimum condition with these combinations,
1) Pectin 2%, calcium chloride 7 mM,
2) Alginic acid 0.25%, calcium chloride 0.05M,
3) PGA 1%, alum 5 mM,
4) κ-carrageenan 0.5%, potassium chloride 0.02M,
5) ι-carrageenan 0.5%, calcium chloride 0.2M,
6) Gelatin-gum arabic 0.01%
Was selected. And the microcapsule dispersion liquid manufactured by the method similar to Example 1 using each wall material and each cation was prepared.
各マイクロカプセルの油内包率（％）（各サンプルを遠心しカプセルに内包されていない油を分離することで内包油量を測定し、全油量に対する内包油量の割合をだしたもの。油含有量はソックスレー法によった）、メジアン径（μｍ）、カプセル数（×１０１２個／Ｌ）を測定した。結果を表１示す。 Oil inclusion rate (%) of each microcapsule (The amount of oil included was measured by centrifuging each sample and separating the oil not included in the capsule, and the ratio of the amount of oil included relative to the total oil amount was obtained. The content was determined by the Soxhlet method), the median diameter (μm), and the number of capsules (× 10 12 / L). The results are shown in Table 1.
表１から、ＰＧＡ、κ-カラギーナン、ι-カラギーナン、ゼラチン−アラビアゴムは油内包率が３０％以下と小さいが、ペクチンは油内包率９７％、アルギン酸は油内包率９４％と内包率が大きく好ましいことが判明した。特にペクチンはメジアン径も１μｍと小さいため好ましく、カプセル数も１５０×１０１２個／Ｌと多く好ましいことが判明し、マイクロカプセル素材として有望であることが判明した。 From Table 1, PGA, κ-carrageenan, ι-carrageenan, and gelatin-gum arabic have small inclusion ratios of 30% or less, but pectin has a high inclusion ratio of 97% and alginic acid has a high inclusion ratio of 94%. It turned out to be preferable. In particular, pectin is preferable because it has a median diameter as small as 1 μm, and the number of capsules is found to be as large as 150 × 10 12 / L, which proves promising as a microcapsule material.
超高剪断処理機を用いたペクチンカプセルの製造 Production of pectin capsules using an ultra-high shearing machine
ペクチン（商品名「ＬＭ−１０４ＡＳ」、ＣＰＫｅｌｃｏ ＪＡＰＡＮ製）と脱イオン水を混合し、２％ペクチン水溶液を調製した。次に超高剪断処理機（日本精機製作所（株）特注機）の攪拌容器に２％ペクチン水溶液８１ｍｌと大豆油（味の素製油株式会社製）９ｍｌを加え、容器の周囲を冷却した状態で超高剪断処理機により、９５００ｒｐｍで３分間処理を行った。攪拌開始後１分経過したところで７．３ｍＭ塩化カルシウム６ｍｌを１分間添加したところ、乳白色の分散液を得た。 Pectin (trade name “LM-104AS”, manufactured by CPKelco JAPAN) and deionized water were mixed to prepare a 2% aqueous pectin solution. Next, add 81 ml of 2% aqueous pectin solution and 9 ml of soybean oil (Ajinomoto Oil Co., Ltd.) to the stirring vessel of the ultra high shearing machine (Nippon Seiki Seisakusho Co., Ltd.) The treatment was performed at 9500 rpm for 3 minutes using a shearing machine. When 1 minute passed after the start of stirring, 6 ml of 7.3 mM calcium chloride was added for 1 minute to obtain a milky white dispersion.
マイクロカプセル分散液の粒度分布をレーザー回折式粒度分布計ＬＡ９２０（堀場製作所社製）にて測定したところシングルピークであり、マイクロカプセルの外径のメジアン径は４．１μｍであった。 When the particle size distribution of the microcapsule dispersion was measured with a laser diffraction particle size distribution analyzer LA920 (manufactured by Horiba, Ltd.), it was a single peak, and the median diameter of the outer diameter of the microcapsule was 4.1 μm.
ペクチン濃度、カルシウム濃度がマイクロカプセルの粒径に与える影響 Effects of pectin concentration and calcium concentration on the particle size of microcapsules
ペクチン（ＬＭ−１０４ＡＳ ＣＰＫｅｌｃｏ ＪＡＰＡＮ）の濃度を０．０２％、０．２％、２％、５％と変化させ、実施例１と同様の方法によりマイクロカプセルを調製した。
また、各濃度のペクチンについて、塩化カルシウムを３０秒後に２ｍｌ添加したが、その塩化カルシウム濃度を０ｍＭ、７ｍＭ、７０ｍＭ、７００ｍＭ、と変化させた。
Microcapsules were prepared in the same manner as in Example 1, except that the concentration of pectin (LM-104AS CPKelco JAPAN) was changed to 0.02%, 0.2%, 2%, and 5%.
Further, 2 ml of calcium chloride was added after 30 seconds for each concentration of pectin, but the calcium chloride concentration was changed to 0 mM, 7 mM, 70 mM, and 700 mM.
各マイクロカプセルの粒径を表２に示す。なお表に示している数字は特に断りがない限りメジアン径（μｍ）を示す。なお、ゲル化が激しくサンプルが一つの塊となり、粒度分布測定不可能なものを「凝集」と示した。 The particle size of each microcapsule is shown in Table 2. The numbers shown in the table indicate the median diameter (μm) unless otherwise specified. In addition, the gelation was severe and the sample became one lump, and the particle size distribution measurement impossible was indicated as “aggregation”.
表２に示すように、ペクチン濃度、塩化カルシウム濃度が高くなるにつれて粒子同士が凝集する傾向が得られた。なお、２％ペクチン、７ｍＭ塩化カルシウムの条件において最も凝集が少なく、メジアン径が小さいカプセルが得られた。 As shown in Table 2, there was a tendency for the particles to aggregate as the pectin concentration and calcium chloride concentration increased. In addition, a capsule having the smallest aggregation and a small median diameter was obtained under the conditions of 2% pectin and 7 mM calcium chloride.
ペクチンのエステル化度、アミド基の有無によるマイクロカプセルの安定性評価 Evaluation of microcapsule stability by the degree of esterification of pectin and the presence or absence of amide groups
以下の表３の様に、エステル化度（ＤＥ値）を３１、３４、３６と変化させたペクチンと、種類をＬＭＡ、ＬＭＣと変化させたペクチンを用いて実施例１と同様の方法によりマイクロカプセルを調製した。調製したマイクロカプセルを１２０℃で３０分加熱処理し、加熱前後の安定性を評価した。 As shown in Table 3 below, the pectin in which the degree of esterification (DE value) was changed to 31, 34, and 36 and the pectin in which the type was changed to LMA and LMC were used in the same manner as in Example 1 to make micro Capsules were prepared. The prepared microcapsules were heat-treated at 120 ° C. for 30 minutes, and the stability before and after heating was evaluated.
加熱前後のメジアン径、カプセル数を表４に示す。調製後のマイクロカプセル分散液は全て分離のない白濁液となっていた。加熱後ＬＭＡ（アミド化タイプ）では安定分散していたが、ＬＭＣである１２ＣＧ、１３ＣＧは共に分離した。 Table 4 shows the median diameter before and after heating and the number of capsules. All of the microcapsule dispersions after preparation were white turbid liquids without separation. After heating, LMA (amidation type) was stably dispersed, but LCG 12CG and 13CG were both separated.
表４に示すように、すべてのマイクロカプセルが加熱後、凝集もしくは合一してメジアン径が大きくなった。しかし、ＬＭＡペクチンは、エステル化度が高いほどメジアン径変化は少なくＤＥ値が３６の１０１ＡＳはメジアン径変化が約１．５倍と少なく粒度分布もシングルピークのままであり、カプセルの構造安定性が最も高かった。ＬＭＣペクチンは加熱することにより凝集もしくは合一が格段に進み、メジアン径が大きくなるためマイクロカプセルの調製に適していないことが分かった。 As shown in Table 4, all the microcapsules were aggregated or united after heating to increase the median diameter. However, LMA pectin has less change in median diameter as the degree of esterification is higher, and 101AS with DE value of 36 has about 1.5 times change in median diameter and the particle size distribution remains a single peak, and the structural stability of the capsule Was the highest. It was found that LMC pectin is not suitable for the preparation of microcapsules because aggregation or coalescence proceeds markedly by heating and the median diameter increases.
ペクチンメチルエステラーゼ、カルシウム濃度がマイクロカプセルの安定性に与える影響 Effects of pectin methylesterase and calcium concentration on microcapsule stability
実施例１と同様の方法により製造したマイクロカプセル分散液５ｍＬと濃度を変化させたＰＭＥ溶液５ｍＬを混合し、ｐＨ４、反応温度４０℃、反応時間４時間の条件で振とう機で反応させ、その後濃度を変化させた塩化カルシウム溶液を１ｍｌ添加した。混合したＰＭＥ（製品名：ＮＯＶＯ ＳＨＡＰＥ、ノボザイム社製）濃度は、０、２．５、２５、２５０、５００ｍＰＥＵ／ｍｌであり、添加した塩化カルシウム濃度は７、１０、１５、２５、４５０ｍＭである。その結果を表５に示す。 5 mL of the microcapsule dispersion produced by the same method as in Example 1 and 5 mL of the PME solution having a changed concentration were mixed, and reacted with a shaker under the conditions of pH 4, reaction temperature 40 ° C., and reaction time 4 hours. 1 ml of calcium chloride solution with varying concentration was added. The mixed PME (product name: NOVO SHAPE, manufactured by Novozyme) concentration is 0, 2.5, 25, 250, 500 mPEU / ml, and the added calcium chloride concentration is 7, 10, 15, 25, 450 mM. . The results are shown in Table 5.
表５から、ＰＭＥ濃度５００ｍＰＥＵ／ｍｌでは全ての塩化カルシウム濃度において、ＰＭＥ濃度２５０ｍＰＥＵ／ｍｌでは１５ｍＭ以上の塩化カルシウムで、それ以外のＰＭＥ濃度では２５ｍＭ以上の塩化カルシウムで全体がゲル化することが判明した。 From Table 5, it is found that the whole gelation occurs at all calcium chloride concentrations at a PME concentration of 500 mPEU / ml, at 15 mM or more of calcium chloride at a PME concentration of 250 mPEU / ml, and at 25 mM or more of calcium chloride at other PME concentrations. did.
ＰＭＥ処理後の塩化カルシウム添加の有無が加熱耐性に与える影響 Effect of the presence or absence of calcium chloride after PME treatment on heat resistance
実施例１と同様の方法により製造したマイクロカプセル分散液に濃度を変化させたＰＭＥ溶液を混合し、その後７ｍＭ塩化カルシウム１ｍｌを添加したサンプル、無添加のサンプルを作製した（すべてｐＨ４）。これに対し１２０℃、３０分加熱を行い、加熱前後のメジアン径を測定した。混合したＰＭＥ（製品名：ＮＯＶＯ ＳＨＡＰＥ、ノボザイム社製）濃度は、０、２．５、２５、２５０ｍＰＥＵ／ｍｌであった。その結果を表６に示す。
なお、コントロール（Ｃｏｎｔ．）は実施例１の製法により作製したマイクロカプセルを用いた。
A microcapsule dispersion prepared by the same method as in Example 1 was mixed with a PME solution having a changed concentration, and then a sample to which 1 ml of 7 mM calcium chloride was added and an additive-free sample were prepared (all pH 4). On the other hand, it heated at 120 degreeC for 30 minutes, and measured the median diameter before and behind a heating. The concentration of the mixed PME (product name: NOVO SHAPE, manufactured by Novozyme) was 0, 2.5, 25, 250 mPEU / ml. The results are shown in Table 6.
In addition, the control (Cont.) Used the microcapsule produced by the manufacturing method of Example 1.
表６から、ＰＭＥ処理を行った後に塩化カルシウムを添加しないものについてはＰＭＥ濃度が高いほど加熱後合一もしくは凝集してメジアン径が大きくなるが、ＰＭＥ処理を行った後に塩化カルシウムを添加したものは、加熱後であってもメジアン径が維持されることが判明した。上記結果より、ＰＭＥ処理を行う場合にはＰＭＥ処理の後に、塩化カルシウムを添加することによりカプセルの構造が加熱負荷に対して耐性をもつことが判明した。またＰＭＥ濃度が０〜２５０ｍＰＥＵ／ｍｌの間では、２５０ｍＰＥＵ／ｍｌのＰＭＥに塩化カルシウムを添加したカプセルが最も安定性が高く好ましいことが判明した。 From Table 6, for those in which calcium chloride is not added after PME treatment, the median diameter increases as the PME concentration increases after heating or coalescing or aggregation, but calcium chloride is added after PME treatment Was found to maintain the median diameter even after heating. From the above results, it was found that when PME treatment is performed, the capsule structure is resistant to heating load by adding calcium chloride after the PME treatment. Further, it was found that capsules obtained by adding calcium chloride to 250 mPEU / ml PME had the highest stability when the PME concentration was between 0 and 250 mPEU / ml.
本発明によれば、喫食時に知覚しない大きさのマイクロカプセルを製造することができる。 According to the present invention, a microcapsule having a size that is not perceived during eating can be produced.
Claims (7)
The microcapsule according to claim 6, wherein a polyvalent cation is added after adding pectin methylesterase.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004234470A JP2006050946A (en) | 2004-08-11 | 2004-08-11 | Microcapsule using pectin as wall material |
| PCT/JP2005/014975 WO2006016713A1 (en) | 2004-08-11 | 2005-08-10 | Microcapsule using pectin as wall material |
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| Application Number | Priority Date | Filing Date | Title |
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| JP2004234470A JP2006050946A (en) | 2004-08-11 | 2004-08-11 | Microcapsule using pectin as wall material |
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| JP2006050946A true JP2006050946A (en) | 2006-02-23 |
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| JP2004234470A Pending JP2006050946A (en) | 2004-08-11 | 2004-08-11 | Microcapsule using pectin as wall material |
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| Country | Link |
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| JP (1) | JP2006050946A (en) |
| WO (1) | WO2006016713A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112314948A (en) * | 2020-10-26 | 2021-02-05 | 北京壹诺药业有限公司 | Microcapsule for embedding functional grease and preparation method thereof |
| WO2022114234A1 (en) * | 2020-11-30 | 2022-06-02 | 富士フイルム株式会社 | Edible oil-containing microcapsule, microcapsule dispersion, production method for edible oil-containing microcapsule, and meat alternative |
| WO2023008581A1 (en) * | 2021-07-30 | 2023-02-02 | 富士フイルム株式会社 | Fatty mass composition and meat alternative |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102188037B (en) * | 2010-03-08 | 2013-12-04 | 宏芳香料（昆山）有限公司 | Microcapsule granule and preparation process thereof |
| CN103271424B (en) * | 2013-05-28 | 2015-08-12 | 上海交通大学 | A kind of preparation method of essence microcapsule |
| CN114869857B (en) * | 2022-05-12 | 2023-04-04 | 郑州大学第一附属医院 | Argatroban particles, preparation and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP4900984B2 (en) * | 1997-07-15 | 2012-03-21 | 武田薬品工業株式会社 | Manufacturing method of sustained-release preparation |
| DE19962427A1 (en) * | 1999-12-22 | 2001-07-12 | Nutrinova Gmbh | Encapsulated multifunctional, biologically active food component, process for their production and their application |
| WO2002082924A1 (en) * | 2001-04-10 | 2002-10-24 | Basf Health & Nutrition A/S | Microcapsules |
| JP2003055219A (en) * | 2001-08-06 | 2003-02-26 | Lion Corp | Microcapsule, tablet and compounding agent for food and medicine |
| JP3818384B2 (en) * | 2004-03-30 | 2006-09-06 | 独立行政法人食品総合研究所 | Emulsion production apparatus, reaction apparatus, microcapsule production method using the reaction apparatus, microtube production method, and microtube |
-
2004
- 2004-08-11 JP JP2004234470A patent/JP2006050946A/en active Pending
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2005
- 2005-08-10 WO PCT/JP2005/014975 patent/WO2006016713A1/en active Application Filing
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112314948A (en) * | 2020-10-26 | 2021-02-05 | 北京壹诺药业有限公司 | Microcapsule for embedding functional grease and preparation method thereof |
| WO2022114234A1 (en) * | 2020-11-30 | 2022-06-02 | 富士フイルム株式会社 | Edible oil-containing microcapsule, microcapsule dispersion, production method for edible oil-containing microcapsule, and meat alternative |
| WO2023008581A1 (en) * | 2021-07-30 | 2023-02-02 | 富士フイルム株式会社 | Fatty mass composition and meat alternative |
| JP7446529B2 (en) | 2021-07-30 | 2024-03-08 | 富士フイルム株式会社 | Fat mass composition and meat substitute |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2006016713A1 (en) | 2006-02-16 |
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