JP2012130856A - Method for producing emulsifier production material, emulsifier production material, and method for producing emulsifier - Google Patents
Method for producing emulsifier production material, emulsifier production material, and method for producing emulsifier Download PDFInfo
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- BIABMEZBCHDPBV-UHFFFAOYSA-N dipalmitoyl phosphatidylglycerol Chemical compound CCCCCCCCCCCCCCCC(=O)OCC(COP(O)(=O)OCC(O)CO)OC(=O)CCCCCCCCCCCCCCC BIABMEZBCHDPBV-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
Description
本発明は、乳化剤製造用材料の製造方法、乳化剤製造用材料、及び乳化剤の製造方法に関する。 The present invention relates to a method for producing an emulsifier-producing material, an emulsifier-producing material, and a method for producing an emulsifier.
従来、機能性油性基剤又は機能性顆粒を水に乳化分散させる場合には、機能性油性基剤の所要ＨＬＢや顆粒表面の性質に応じて界面活性剤を選択し、乳化分散を行っていた。また、乳化剤として用いられる界面活性剤の所要ＨＬＢ値は、Ｏ／Ｗ型エマルションを作る場合とＷ／Ｏ型エマルションを作る場合とのそれぞれに応じて使い分ける必要があり、しかも、熱安定性や経時安定性が十分でないため、多種多様な界面活性剤を混合して用いていた（非特許文献１〜４等参照）。 Conventionally, when emulsifying and dispersing a functional oil base or functional granule in water, a surfactant was selected according to the required HLB of the functional oil base and the properties of the granule surface, and emulsified and dispersed. . In addition, the required HLB value of the surfactant used as an emulsifier needs to be properly used depending on whether an O / W type emulsion is made or a W / O type emulsion, and further, thermal stability and aging Since the stability is not sufficient, a wide variety of surfactants are mixed and used (see Non-Patent Documents 1 to 4).
しかしながら、界面活性剤は、生分解性が低く、泡立ちの原因となるので、環境汚染等の深刻な問題となっている。また、機能性油性基剤の乳化製剤の調製法として、ＨＬＢ法、転相乳化法、転相温度乳化法、ゲル乳化法等の物理化学的な乳化方法が一般に行われているが、いずれも油／水界面の界面エネルギーを低下させ、熱力学的に系を安定化させる作用をエマルション調製の基本としているので、最適な乳化剤を選択するために非常に煩雑かつ多大な労力を有しており、まして、多種類の油が混在していると、安定に乳化させることは殆ど不可能であった。 However, since the surfactant has low biodegradability and causes foaming, it is a serious problem such as environmental pollution. In addition, as a method for preparing an emulsified preparation of a functional oil base, physicochemical emulsification methods such as an HLB method, a phase inversion emulsification method, a phase inversion temperature emulsification method, and a gel emulsification method are generally performed. Since the basis of emulsion preparation is to reduce the interfacial energy at the oil / water interface and to stabilize the system thermodynamically, it is very cumbersome and labor intensive to select the most suitable emulsifier In addition, when many kinds of oils are mixed, stable emulsification is almost impossible.
そこで、特許文献１には、自発的に閉鎖小胞を形成する両親媒性物質により形成され、２００ｎｍ〜８００ｎｍの粒度分布を有する親水性ナノ粒子を含有する乳化剤が開示されている。特許文献１において乳化剤は、両親媒性物質を水に添加して数分間撹拌することで分散させた後、分散液を冷水に滴下することで製造している。 Therefore, Patent Document 1 discloses an emulsifier containing hydrophilic nanoparticles formed of an amphiphilic substance that spontaneously forms closed vesicles and having a particle size distribution of 200 nm to 800 nm. In Patent Document 1, an emulsifier is produced by adding an amphiphile to water and dispersing it by stirring for several minutes, and then dropping the dispersion into cold water.
しかし、特許文献１に示される製造方法では、得られる親水性ナノ粒子の径にばらつきが大きく、とりわけ粒径が小さい親水性ナノ粒子の収率が低いため、乳化剤の乳化機能が充分に発揮されていない、もしくは乳化剤の均質性が不充分である。 However, in the production method shown in Patent Document 1, the resulting hydrophilic nanoparticles have a large variation in diameter, and the emulsifying function of the emulsifier is sufficiently exhibited because the yield of hydrophilic nanoparticles having a small particle size is particularly low. Or the homogeneity of the emulsifier is insufficient.
本発明は、以上の実情に鑑みてなされたものであり、親水性ナノ粒子の粒子径のばらつきを抑制できる、もしくは小粒径の親水性ナノ粒子の収率を向上できる乳化剤製造用材料の製造方法、乳化剤製造用材料、及び乳化剤の製造方法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 can produce an emulsifier-producing material that can suppress variation in the particle size of hydrophilic nanoparticles or can improve the yield of small-sized hydrophilic nanoparticles. It is an object to provide a method, a material for producing an emulsifier, and a method for producing an emulsifier.
本発明者らは、両親媒性物質の二分子膜の層状体を含む材料を撹拌し、層状体から二分子膜の親水性ナノ粒子を形成することで、粒子径のばらつきの少ない、特に小径の割合が大きい親水性ナノ粒子が得られることを見出し、本発明を完成するに至った。具体的に、本発明は以下のようなものを提供する。 The present inventors stir a material containing a bilayer film of an amphiphile, and form hydrophilic nanoparticles of the bilayer film from the layer, thereby reducing variation in particle diameter, particularly small diameter. The present inventors have found that hydrophilic nanoparticles having a large ratio can be obtained, and have completed the present invention. Specifically, the present invention provides the following.
（１） 両親媒性分子からなる両親媒性物質の二分子膜の層状体を水に分散させる工程を有する乳化剤製造用材料の製造方法。 (1) A method for producing an emulsifier-producing material, comprising a step of dispersing a bilayer film of an amphiphilic substance composed of amphiphilic molecules in water.
（２） 前記分散の間及び／又は前に水を加熱し、前記層状体の形成を促進する工程をさらに有する（１）記載の製造方法。 (2) The production method according to (1), further comprising a step of heating water during and / or before the dispersion to promote the formation of the layered body.
（３） 前記両親媒性物質を、乳化剤製造用材料に対して０．１〜２０質量％の濃度で水中に分散させる（１）又は（２）記載の製造方法。 (3) The production method according to (1) or (2), wherein the amphiphilic substance is dispersed in water at a concentration of 0.1 to 20% by mass with respect to the material for producing an emulsifier.
（４） 前記両親媒性分子は、脂肪酸エステル、リン脂質、ポリオキシエチレンヒマシ油、及びこれらの誘導体からなる群より選ばれる１種以上である（１）から（３）いずれか記載の製造方法。 (4) The production method according to any one of (1) to (3), wherein the amphiphilic molecule is at least one selected from the group consisting of fatty acid esters, phospholipids, polyoxyethylene castor oil, and derivatives thereof. .
（５） 両親媒性分子の二分子膜の層状体が水に分散した分散液を含む乳化剤製造用材料。 (5) An emulsifier-producing material comprising a dispersion in which a bilayer film of amphiphilic molecules is dispersed in water.
（６） 前記両親媒性分子の含有量は、乳化剤製造用材料に対して０．１〜２０質量％である（５）記載の乳化剤製造用材料。 (6) The emulsifier-producing material according to (5), wherein the content of the amphiphilic molecule is 0.1 to 20% by mass with respect to the emulsifier-producing material.
（７） 前記両親媒性分子は、脂肪酸エステル、リン脂質、ポリオキシエチレンヒマシ油、及びこれらの誘導体からなる群より選ばれる１種以上である（５）又は（６）記載の乳化剤製造用材料。 (7) The material for producing an emulsifier according to (5) or (6), wherein the amphiphilic molecule is at least one selected from the group consisting of fatty acid esters, phospholipids, polyoxyethylene castor oil, and derivatives thereof. .
（８） （１）から（４）いずれか記載の製造方法で製造される乳化剤製造用材料、又は（５）から（７）いずれか記載の乳化剤製造用材料を撹拌することで、前記層状体から前記二分子膜の親水性ナノ粒子を形成する工程を有する乳化剤の製造方法。 (8) By stirring the emulsifier-producing material produced by any one of the production methods according to (1) to (4) or the emulsifier-producing material according to any one of (5) to (7), the layered body The manufacturing method of the emulsifier which has the process of forming the hydrophilic nanoparticle of the said bimolecular film from.
（９） 前記撹拌を、液中に存在する粒子の平均粒子径が２０ｎｍ〜８００ｎｍになるまで行う（８）記載の製造方法。 (9) The production method according to (8), wherein the stirring is performed until an average particle size of particles present in the liquid becomes 20 nm to 800 nm.
本発明によれば、両親媒性物質の二分子膜の層状体を含む材料を撹拌し、層状体から二分子膜の親水性ナノ粒子を形成することで、粒子径のばらつきの少ない、特に小径の割合が大きい親水性ナノ粒子が得られる。これにより、親水性ナノ粒子の粒子径のばらつきを抑制できる、もしくは小粒径の親水性ナノ粒子の収率を向上できる。 According to the present invention, a material containing a bilayer membrane of an amphiphilic substance is stirred, and hydrophilic nanoparticles of the bilayer membrane are formed from the lamellar body. A hydrophilic nanoparticle with a large ratio is obtained. Thereby, the dispersion | variation in the particle diameter of a hydrophilic nanoparticle can be suppressed, or the yield of the hydrophilic nanoparticle of a small particle diameter can be improved.
以下、本発明の実施形態を説明するが、これが本発明を限定するものではない。 Hereinafter, although embodiment of this invention is described, this does not limit this invention.
＜乳化剤製造用材料及びその製造方法＞
本発明に係る乳化剤製造用材料の製造方法は、両親媒性分子からなる両親媒性物質の二分子膜の層状体を水に分散させる工程を有する。かかる方法は従来乳化剤の製造方法として使用されてきており、得られる組成物は、二分子膜のラメラ液晶である層状体のみならず、層状体から形成された二分子膜の親水性ナノ粒子（閉鎖小胞体）も少量含み得るが、親水性ナノ粒子の存在量が充分でないため、乳化機能が充分に発揮されていない。
<Emulsifier production material and production method thereof>
The method for producing an emulsifier producing material according to the present invention includes a step of dispersing a layered body of a bilayer film of an amphiphilic substance composed of amphiphilic molecules in water. Such a method has been conventionally used as a method for producing an emulsifier, and the composition obtained is not only a layered body that is a bilayer lamellar liquid crystal, but also a bilayer hydrophilic nanoparticle formed from a layered body ( (Closed endoplasmic reticulum) may also be included in a small amount, but since the abundance of hydrophilic nanoparticles is not sufficient, the emulsifying function is not sufficiently exhibited.
しかし、本発明におけるこの方法は、乳化剤製造用材料の製造方法であり、得られる乳化剤製造用材料は後述の通り、撹拌される。これにより、得られる乳化剤は、小径である二分子膜の親水性ナノ粒子を多量に含み、より優れた乳化機能を呈する。 However, this method in the present invention is a method for producing an emulsifier-producing material, and the resulting emulsifier-producing material is stirred as described later. Thereby, the obtained emulsifier contains a large amount of bimolecular hydrophilic nanoparticles having a small diameter and exhibits a more excellent emulsifying function.
本発明で用いる両親媒性物質としては、特に限定されないが、脂肪酸エステル、リン脂質、ポリオキシエチレンヒマシ油、及びこれらの誘導体からなる群より選ばれる１種以上であることが好ましい。 Although it does not specifically limit as an amphipathic substance used by this invention, It is preferable that it is 1 or more types chosen from the group which consists of fatty acid ester, phospholipid, polyoxyethylene castor oil, and these derivatives.
脂肪酸エステルとしては、グリセリン脂肪酸エステル，ショ糖脂肪酸エステル，ソルビタン脂肪酸エステル，プロピレングリコール脂肪酸エステル等が挙げられる。中でも、グリセリン脂肪酸エステル及びソルビタン脂肪酸エステルは、従来の方法では親水性ナノ粒子の製造が困難であった点で、本発明において有用である。 Examples of the fatty acid ester include glycerin fatty acid ester, sucrose fatty acid ester, sorbitan fatty acid ester, and propylene glycol fatty acid ester. Among these, glycerin fatty acid esters and sorbitan fatty acid esters are useful in the present invention in that it is difficult to produce hydrophilic nanoparticles by conventional methods.
リン脂質としては、卵黄レシチン又は大豆レシチン等、もしくは下記の一般式３で示される構成のうち、炭素鎖長１２のＤＬＰＣ（１，２−Ｄｉｌａｕｒｏｙｌ−ｓｎ−ｇｌｙｃｅｒｏ−３−ｐｈｏｓｐｈｏ−ｒａｃ−１−ｃｈｏｌｉｎｅ）、炭素鎖長１４のＤＭＰＣ（１，２−Ｄｉｍｙｒｉｓｔｏｙｌ−ｓｎ−ｇｌｙｃｅｒｏ−３−ｐｈｏｓｐｈｏ−ｒａｃ−１−ｃｈｏｌｉｎｅ）、炭素鎖長１６のＤＰＰＣ（１，２−Ｄｉｐａｌｍｉｔｏｙｌ−ｓｎ−ｇｌｙｃｅｒｏ−３−ｐｈｏｓｐｈｏ−ｒａｃ−１−ｃｈｏｌｉｎｅ）が採用可能である。 Examples of phospholipids include egg yolk lecithin and soybean lecithin, or DLPC (1,2-Dilauroyl-sn-glycero-3-phospho-rac-1-) having a carbon chain length of 12 in the structure represented by the following general formula 3. choline), DMPC (1,2-Dimyristol-sn-glycero-3-phospho-rac-1-choline) having a carbon chain length of 14, DPPC (1,2-Dipalmitoyyl-sn-glycero-3-choline) having a carbon chain length of 16 phospho-rac-1-choline) can be employed.
一般式３
また、下記の一般式４で示される構成のうち、炭素鎖長１２のＤＬＰＧ（１，２−Ｄｉｌａｕｒｏｙｌ−ｓｎ−ｇｌｙｃｅｒｏ−３−ｐｈｏｓｐｈｏ−ｒａｃ−１−ｇｌｙｃｅｒｏｌ）のＮａ塩又はＮＨ４塩、炭素鎖長１４のＤＭＰＧ（１，２−Ｄｉｍｙｒｉｓｔｏｙｌ−ｓｎ−ｇｌｙｃｅｒｏ−３−ｐｈｏｓｐｈｏ−ｒａｃ−１−ｇｌｙｃｅｒｏｌ）のＮａ塩又はＮＨ４塩、炭素鎖長１６のＤＰＰＧ（１，２−Ｄｉｐａｌｍｉｔｏｙｌ−ｓｎ−ｇｌｙｃｅｒｏ−３−ｐｈｏｓｐｈｏ−ｒａｃ−１−ｇｌｙｃｅｒｏｌ）のＮａ塩又はＮＨ４塩を採用してもよい。 In addition, among the structures represented by the following general formula 4, DLPG (1,2-Diilauroyl-sn-glycero-3-phospho-rac-1-glycerol) Na salt or NH4 salt, carbon chain of carbon chain length 12 Na or NH4 salt of DMPG having a length of 14 (1,2-Dimyristol-sn-glycero-3-phospho-rac-1-glycerol), DPPG having a carbon chain length of 16 (1,2-Dipalmitoyyl-sn-glycero-3) -Phospho-rac-1-glycerol) Na salt or NH4 salt may be employed.
一般式４
また、下記の一般式１で表されるポリオキシエチレンヒマシ油の誘導体、もしくは一般式２で表されるジアルキルアンモニウム誘導体、トリアルキルアンモニウム誘導体、テトラアルキルアンモニウム誘導体、ジアルケニルアンモニウム誘導体、トリアルケニルアンモニウム誘導体、又はテトラアルケニルアンモニウム誘導体のハロゲン塩の誘導体も挙げられる。 In addition, a polyoxyethylene castor oil derivative represented by the following general formula 1, or a dialkylammonium derivative, a trialkylammonium derivative, a tetraalkylammonium derivative, a dialkenylammonium derivative, a trialkenylammonium derivative represented by the general formula 2 Or a derivative of a halogen salt of a tetraalkenyl ammonium derivative.
一般式１
式中、エチレンオキシドの平均付加モル数であるＥは、３〜１００である。Ｅが過大になると、両親媒性物質を溶解する良溶媒の種類が制限されるため、親水性ナノ粒子の製造の自由度が狭まる。Ｅの上限は好ましくは５０であり、より好ましくは４０であり、Ｅの下限は好ましくは５である。 In the formula, E, which is the average added mole number of ethylene oxide, is 3 to 100. If E is excessive, the type of good solvent that dissolves the amphiphilic substance is limited, and thus the degree of freedom in producing hydrophilic nanoparticles is narrowed. The upper limit of E is preferably 50, more preferably 40, and the lower limit of E is preferably 5.
一般式２
式中、Ｒ１及びＲ２は、各々独立して炭素数８〜２２のアルキル基又はアルケニル基であり、Ｒ３及びＲ４は、各々独立して水素又は炭素数１〜４のアルキル基であり、ＸはＦ、Ｃｌ、Ｂｒ又はＩである。 In the formula, R 1 and R 2 are each independently an alkyl group or alkenyl group having 8 to 22 carbon atoms, R 3 and R 4 are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms, and X is F, Cl, Br or I.
二分子膜の層状体の水への分散は、両親媒性物質及び水を混合し、必要に応じて僅かな時間（例えば５〜１５分間）撹拌することで行うことができる。ただし、分散媒である水の温度が低いと、層状体が充分に形成されず、結果的に、得られる親水性ナノ粒子の収率の悪化、親水性ナノ粒子の製造効率の低下（つまり製造時間の延長）が懸念される。そこで、本発明の方法は、水への分散の間及び／又は前に、水を加熱し、層状体の形成を促進する工程をさらに有することが好ましい。これにより、層状体の形成が熱エネルギーによって促進されるため、親水性ナノ粒子の収率の向上、製造効率の向上が期待できる。なお、層状体の形成の促進は、加熱の前後において粒度分布を測定し、平均粒子径が変化していることにより確認することができる。 The dispersion of the bilayer membrane into water can be performed by mixing the amphiphile and water and stirring for a short time (for example, 5 to 15 minutes) as necessary. However, when the temperature of the water as the dispersion medium is low, the layered body is not sufficiently formed, resulting in a deterioration in the yield of the obtained hydrophilic nanoparticles and a decrease in the production efficiency of the hydrophilic nanoparticles (that is, production). (Extended time) is a concern. Therefore, it is preferable that the method of the present invention further includes a step of heating water to promote formation of a layered body during and / or before dispersion in water. Thereby, since formation of a layered body is promoted by thermal energy, improvement in the yield of hydrophilic nanoparticles and improvement in production efficiency can be expected. The promotion of the formation of the layered body can be confirmed by measuring the particle size distribution before and after heating and changing the average particle size.
水の加熱は、不充分であると、層状体の形成が充分に促進されない一方、過剰であると、両親媒性物質の変性、エネルギー効率の低下等が懸念される。そこで、加熱時の水温は、特に限定されないが、下限が４０℃、好ましくは５０℃であり、上限が８０℃、好ましくは７０℃の範囲であってよい。 If the heating of water is insufficient, the formation of the layered body is not sufficiently promoted. On the other hand, if it is excessive, there is a concern that the amphiphile may be denatured and the energy efficiency is lowered. Thus, the water temperature at the time of heating is not particularly limited, but the lower limit may be 40 ° C, preferably 50 ° C, and the upper limit may be 80 ° C, preferably 70 ° C.
また、加熱後に液体を冷却（例えば５〜１０℃）し、さらに加熱するという工程を１回〜複数回に亘り行ってもよい。これにより、両親媒性物質が有する親水基への水の浸入が促されるため、より優れた親水性ナノ粒子を得ることができる。 Moreover, you may perform the process of cooling a liquid after heating (for example, 5-10 degreeC), and heating further once to several times. Thereby, since the penetration | invasion of the water to the hydrophilic group which an amphiphilic substance has is promoted, the more excellent hydrophilic nanoparticle can be obtained.
両親媒性物質の量は、過小であると製造効率が悪化する一方、過大であると、層状体からの二分子膜の親水性ナノ粒子の形成に多大な時間を要する。そこで、乳化剤製造用材料に対する両親媒性物質の濃度は、下限が好ましくは０．１質量％であり、上限が好ましくは２０質量％である。なお、両親媒性物質の濃度の許容上限は、用いる両親媒性物質によって異なり、例えばポリオキシエチレンヒマシ油の誘導体は高濃度では針状結晶を形成しやすいため、制限される一方、脂肪酸エステル、リン脂質はこのような問題がなく、ほぼ制限されない。 If the amount of the amphiphilic substance is too small, the production efficiency is deteriorated. On the other hand, if the amount is too large, it takes a long time to form the bilayer hydrophilic nanoparticles from the layered body. Therefore, the lower limit of the concentration of the amphiphilic substance relative to the emulsifier-producing material is preferably 0.1% by mass, and the upper limit is preferably 20% by mass. The allowable upper limit of the concentration of the amphiphile varies depending on the amphiphile used. For example, a derivative of polyoxyethylene castor oil is likely to form needle crystals at a high concentration, and is thus limited. Phospholipids do not have these problems and are almost unrestricted.
＜乳化剤の製造方法＞
本発明の乳化剤の製造方法は、前述の乳化剤製造用材料を撹拌することで、層状体から二分子膜の親水性ナノ粒子を形成する工程を有する。これにより、得られる乳化剤は、小径である二分子膜の親水性ナノ粒子を多量に含み、より優れた乳化機能を呈する。
<Method for producing emulsifier>
The manufacturing method of the emulsifier of this invention has the process of forming the hydrophilic nanoparticle of a bilayer from a layered body by stirring the above-mentioned material for emulsifier manufacture. Thereby, the obtained emulsifier contains a large amount of bimolecular hydrophilic nanoparticles having a small diameter and exhibits a more excellent emulsifying function.
この工程における撹拌は、前述の乳化剤製造用材料の製造過程における分散のための撹拌とは異なり、用いる両親媒性物質の種類や量に応じて、必要充分に激しく行う必要がある。例示的な撹拌条件において、水温の下限は４０℃であることが好ましく、より好ましくは５０℃であり、上限は８０℃であることが好ましく、より好ましくは７０℃である。また、撹拌速度は、下限が１２００ｒｐｍであることが好ましく、より好ましくは２０００ｒｐｍであり、上限が１６０００ｒｐｍであることが好ましく、より好ましくは１００００ｒｐｍである。時間は、下限が３０分間であることが好ましく、より好ましくは５０分間、さらに好ましくは５５分間であり、上限は９０分間であることが好ましく、より好ましくは７０分間、さらに好ましくは７５分である。 Agitation in this step needs to be performed vigorously and sufficiently depending on the type and amount of the amphiphile used, unlike the agitation for dispersion in the production process of the above-mentioned emulsifier production material. In the exemplary stirring conditions, the lower limit of the water temperature is preferably 40 ° C, more preferably 50 ° C, and the upper limit is preferably 80 ° C, more preferably 70 ° C. The lower limit of the stirring speed is preferably 1200 rpm, more preferably 2000 rpm, and the upper limit is preferably 16000 rpm, more preferably 10,000 rpm. The lower limit of the time is preferably 30 minutes, more preferably 50 minutes, even more preferably 55 minutes, and the upper limit is preferably 90 minutes, more preferably 70 minutes, still more preferably 75 minutes. .
別の側面において、撹拌は、液中に存在する粒子の平均粒子径が、レーザー回折光散乱装置を用いた測定値において２０ｎｍ〜８００ｎｍになるまで行うことが好ましい。これにより、乳化剤は、乳化に関わる親水性ナノ粒子を多量に含むため、優れた乳化機能を有することができる。撹拌は、平均粒子径が２０ｎｍ〜６００ｎｍになるまで行うことがより好ましい。 In another aspect, the stirring is preferably performed until the average particle diameter of the particles present in the liquid is 20 nm to 800 nm as measured using a laser diffracted light scattering apparatus. Thereby, since the emulsifier contains a large amount of hydrophilic nanoparticles involved in emulsification, it can have an excellent emulsifying function. The stirring is more preferably performed until the average particle size becomes 20 nm to 600 nm.
乳化剤において、親水性ナノ粒子の乳化対象への付着力を高めるために、親水性ナノ粒子をイオン化してもよい。カチオン化のためには、イオン性界面活性剤として、アルキル又はアルケニルトリメチルアンモニウム塩（炭素鎖長１２〜２２）、好ましくは、炭素鎖長１６のヘキサデシルトリメチルアンモニウムブロミド（Ｈｅｘａｄｅｃｙｌｔｒｉｍｅｔｈｙｌａｍｍｏｎｉｕｍ Ｂｒｏｍｉｄｅ：以下、ＣＴＡＢという）、アニオン化のためには、アルキル硫酸エステル塩（ＣｎＳＯ４ −Ｍ＋炭素鎖長８〜２２、Ｍ：アルカリ金属、アルカリ土類金属、アンモニウム塩等）、アルキルスルホン酸塩（ＣｎＳＯ３ − Ｍ＋ 炭素鎖長８〜２２、Ｍ：アルカリ金属、アルカリ土類金属、アンモニウム塩等）等を用いることができる。 In the emulsifier, the hydrophilic nanoparticles may be ionized in order to increase the adhesion force of the hydrophilic nanoparticles to the emulsification target. For cationization, alkyl or alkenyl trimethylammonium salt (carbon chain length 12 to 22), preferably hexadecyltrimethylammonium bromide (Hexadecyltrimethylammonium Bromide: hereinafter referred to as CTAB) is used as an ionic surfactant. ), for the anion of the alkyl sulfates (CnSO 4 - M + carbon chain length 8 to 22, M: alkali metals, alkaline earth metals, ammonium salts, etc.), alkyl sulfonates (CnSO 3 - M + Carbon chain length of 8 to 22, M: alkali metal, alkaline earth metal, ammonium salt, etc.) can be used.
かかる本発明の乳化剤は、水酸基を有する重縮合ポリマー粒子の結合体を含む顆粒（例えばデンプン顆粒；特開２００６−２３９６６６号公報参照）から製造される乳化剤と異なり、水素結合を回復させるための熟成工程が不要である点で有利である。また、本発明の乳化剤は、水酸基を有する重縮合ポリマー粒子の結合体を含む顆粒から製造される乳化剤よりも変性されにくいので、さらに多様な対象を乳化することができる点でも有利である。 Such an emulsifier of the present invention is different from an emulsifier produced from a granule containing a conjugate of polycondensation polymer particles having a hydroxyl group (for example, starch granule; see JP-A-2006-239666), and is aged for recovering hydrogen bonds. This is advantageous in that a process is unnecessary. The emulsifier of the present invention is also advantageous in that it can be emulsified more variously because it is less denatured than an emulsifier produced from granules containing a conjugate of polycondensation polymer particles having a hydroxyl group.
具体的には、乳化剤に、水相に分配される物質を適宜添加し又は添加せずに、油性物質と混合することで、油性物質を含む油相と、水相とが分散したエマルションを製造できる。なお、油性物質とは、油のみ又は油を主成分として含む物質をいう。詳細な使用手順は、特許第３８５５２０３号公報に記載されている。 Specifically, an emulsion in which an oil phase containing an oily substance and an aqueous phase are dispersed is produced by mixing the oily substance with or without adding a substance that is distributed to the aqueous phase as appropriate to the emulsifier. it can. In addition, an oily substance means the substance which contains only oil or oil as a main component. A detailed use procedure is described in Japanese Patent No. 3855203.
また、本発明の乳化剤は、機能性油性基剤と水、又は機能性顆粒と水等の界面に対して、熱安定性や経時安定性に優れた乳化分散系を形成できる。このため、本発明の乳化分散剤は、長期間に亘る幅広い温度領域での安定な乳化に使用できる。また、一種類の乳化分散剤を用いて、被乳化油剤の所要ＨＬＢ値又は機能性顆粒の表面状態に関係なく、油性物質を乳化分散できるので、炭化水素系油剤やシリコン系油剤の乳化にも使用できる。このため、多種類の混在している油を併せて乳化するためにも使用できる。従って、本発明の親水性ナノ粒子及び乳化剤は、軽油、Ａ重油、Ｃ重油、タール、バイオディーゼル燃料、再生重油、廃食油、化粧油、シリコーン油、フッ素系油剤、植物系油剤、動物性油剤（牛脂、魚油等）、潤滑油等の種々の油への水の乳化に使用し得る。 Further, the emulsifier of the present invention can form an emulsified dispersion system having excellent thermal stability and stability over time with respect to the interface between the functional oil base and water or the functional granules and water. For this reason, the emulsifying dispersant of the present invention can be used for stable emulsification in a wide temperature range over a long period of time. In addition, it is possible to emulsify and disperse oily substances using one type of emulsifying dispersant regardless of the required HLB value of the oil to be emulsified or the surface state of the functional granules. Can be used. For this reason, it can also be used to emulsify a mixture of various types of oil. Therefore, the hydrophilic nanoparticles and the emulsifier of the present invention include light oil, heavy oil A, heavy oil C, tar, biodiesel fuel, recycled heavy oil, waste cooking oil, cosmetic oil, silicone oil, fluorine oil, vegetable oil, animal oil. It can be used for emulsification of water in various oils such as beef tallow and fish oil and lubricating oils.
＜実施例＞
グリセリンステアリン酸エステルを水に１．０質量％の量となるように添加して分散液を８０℃に加熱し、１時間に亘って５００ｒｐｍの速度で撹拌した。撹拌後の液について動的光散乱光度計「ＦＰＡＲ−１０００」（大塚電子社製）で粒度分布を測定したところ、親水性ナノ粒子の存在を示すピークが１８０ｎｍ付近に確認された。
<Example>
Glycerine stearate was added to water in an amount of 1.0% by mass, and the dispersion was heated to 80 ° C. and stirred at a speed of 500 rpm for 1 hour. When the particle size distribution of the liquid after stirring was measured with a dynamic light scattering photometer “FPAR-1000” (manufactured by Otsuka Electronics Co., Ltd.), a peak indicating the presence of hydrophilic nanoparticles was confirmed around 180 nm.
（評価）
実施例の分散液を、種々の質量比でＡ−重油と、室温でホモミキサーを用いて、８０００ｒｐｍで約５分間撹拌して乳化した。乳化状態を観察し、相分離が見られなかった条件の範囲を表１に示す。
(Evaluation)
The dispersions of the examples were emulsified with A-heavy oil at various mass ratios by stirring at 8000 rpm for about 5 minutes using a homomixer at room temperature. Table 1 shows the range of conditions under which the emulsified state was observed and phase separation was not observed.
表１に示されるように、実施例の乳化剤は、種々の油を幅広い範囲の混合量比に亘って安定に乳化し、乳化機能に優れることが分かった。 As shown in Table 1, it was found that the emulsifiers of Examples emulsify various oils stably over a wide range of mixing ratios and have an excellent emulsifying function.
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| JP3855203B2 (en) * | 2004-04-05 | 2006-12-06 | 学校法人神奈川大学 | Emulsifying dispersant, emulsifying dispersion method using the same, and emulsion |
| JP2007009087A (en) * | 2005-06-30 | 2007-01-18 | Lion Corp | Powdery detergent composition improved in solubility at low temperature |
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