JP3666526B2 - Production method of endoplasmic reticulum dispersion - Google Patents

Description

（但し、式中Ｒ¹は炭素数１０〜２４のアルキル基又はアルケニル基、Ｒ²は炭素数１〜３のアルキル基、炭素数１０〜２４のアルキル基又はアルケニル基であり、Ｒ¹及びＲ²はそれぞれ無置換であってもよく、−Ｏ−，−ＣＯＮＨ−，−ＣＯＯ−等の官能基で分断もしくは−ＯＨ等の官能基で置換されていてもよい。Ｒ³は炭素数１〜３のアルキル基、Ｒ⁴は炭素数１〜３のアルキル基又はベンジル基であり、Ｘはハロゲン原子又はモノアルキル硫酸基である。）
Ｒ⁵−ＯＨ …（２）
（但し、式中Ｒ⁵は炭素数１２〜２２のアルキル基である。）
【００１０】
上記膜形成成分としては、具体的に式（１）の第４級アンモニウム塩としてステアリルトリメチルアンモニウムクロライド、ジステアリルジメチルアンモニウムクロライド、ドデシルトリメチルアンモニウムクロライド、ジ牛脂アルキルジメチルアンモニウムブロマイド、ジオレイルジメチルアンモニウムクロライド、オレイルトリメチルアンモニウムクロライド等、アミノ酸系カチオン界面活性剤としてヤシ油脂肪酸Ｌ−アルギニンエチル−ＤＬ−ピロリドンカルボン酸、４−グアニジノブチルラウリルアミド酢酸等が例示され、第３級アミン塩としてジステアリルメチルアミン塩酸塩、ジオレイルメチルアミン塩酸塩、ジステアリルメチルアミン硫酸塩等が例示され、これらの第３級アミン塩の場合、アルキル鎖は、−ＣＯＯ−，−ＣＯＮＨ−等の官能基で分断されていてもよい。また、イミダゾリン塩として１−オクタデカノイルアミノエチル−２−ヘプタデシルイミダゾリン塩酸塩、１−オクタデセノイルアミノエチル−２−ヘプタデセニルイミダゾリン塩酸塩等、イミダゾリニウム塩としてメチル−１−牛脂アミドエチル−２−牛脂アルキルイミダゾリニウムメチルサルフェート、メチル−１−ヘキサデカノイルアミドエチル−２−ペンタデシルイミダゾリニウムクロライド、エチル−１−オクタデセノイルアミドエチル−２−ヘプタデセニルイミダゾリニウムエチルサルフェート等、式（２）の高級アルコールとしてセトステアリルアルコール，ドデシルアルコール，セチルアルコール，ステアリルアルコール，ベヘニルアルコール等が例示される。これらの膜形成成分は、製造される小胞体分散液の用途、目的により適宜選定することができ、例えば上記分散液が衣料用仕上げ剤又は化粧料である場合、衣料用仕上げ剤基剤として使用されるカチオン界面活性剤又は化粧料の基剤として使用されるカチオン界面活性剤と高級アルコール等が好適に使用される。
【００１１】
上記膜形成成分の使用量は分散液全体に対して１〜４０重量％程度、好ましくは３〜３０重量％程度である。配合量が少なすぎると油分の内包が困難となる場合があり、一方、過剰量配合すると、小胞体形成が困難となる場合がある。
【００１２】
本発明では、上記膜形成成分による膜形成を容易にするために、上記膜形成成分と共にエチレングリコール，プロピレングリコール，グリセリン等の多価アルコールやエタノール，イソプロピルアルコール等の低級アルコールなどの有機溶剤、ステアリン酸，オレイン酸等の脂肪酸及びポリオキシエチレンアルキルエーテル，ソルビタン脂肪酸エステル，ポリオキシエチレンソルビタン脂肪酸エステル等の各種乳化剤などの添加剤を通常の使用量で配合することもできる。
【００１３】
次に、油分としては、衣料用仕上げ剤、化粧料、医薬品、洗浄剤などの各種分野の製品に使用されている疎水性の油分を使用することができるが、通常、衣類の風合いを変える、皮膚に保湿効果を与える、髪に栄養を与える、抗菌・殺菌効果を与えるなどの機能を持つものが好適に使用される。具体的には、例えばシリコーンオイル，環状シリコーン，変性シリコーンなどの合成油、流動パラフィン，流動イソパラフィン，パラフィンワックスなどの鉱油、ホホバ油，オリーブ油，オリーブスクワラン，ヒマシ油，カルナウバワックスなどの植物油、ラノリン，スクワラン，ミンク油などの動物油、ラウリン酸ヘキシル，パルミチン酸イソプロピル，オレイン酸，ステアリン酸などを挙げることができ、さらに具体的機能として、トリクロサン，ヒノキチオール，トリクロカルバン，イソプロピルメチルフェノールなどの油溶性の抗菌・殺菌剤、ブチルパラベン，プロピルパラベン，安息香酸，サリチル酸，ソルビン酸などの油溶性の防腐剤、ジブチルヒドロキシトルエン，ブチルヒドロキシアニソール，トコフェロールなどの油溶性の酸化防止剤、リナロール，シトロネロール，ゲラニオール，ゲラニルアセテートなどの油溶性の香料、その他油溶性のＵＶ吸収剤，防虫剤，保湿剤等を挙げることができ、これらは１種単独で又は２種以上を適宜組み合わせて使用することができる。
【００１４】
上記油分の使用量は、分散液全体に対して０．１〜２０重量％程度とすると好適であり、上記膜形成成分に対する比率は、膜形成成分に対して油分を１：１以下とすることが望ましく、膜形成成分より油分が多くなると二分子膜多層構造での包含が不十分となる場合がある。なお、使用する油分の融点が高い場合は、上記のような低級アルコールなどの有機溶媒や他の液体油分に溶かして用いてもよい。
【００１５】
また、水相成分としては、水の他に乳化剤，分散安定剤，低温安定化剤，無機塩類，色素及びその他の各種水溶性有効成分等が例示される。具体的には、乳化剤としてポリオキシエチレンノニルフェニルエーテル，ポリオキシエチレンオクチルフェニルエーテル，グリセリン脂肪酸エステル，ポリオキシエチレンソルビタン脂肪酸エステル，ポリオキシエチレンアルキルエーテル，脂肪酸ポリエチレングリコール等の非イオン界面活性剤など、分散安定剤としてポリアクリル酸，カルボキシメチルセルロース、カルボキシビニルポリマーなど、低温安定化剤としてエチレングリコール，プロピレングリコール，グリセリンなど、無機塩類として塩化ナトリウム，塩化カルシウム等の塩酸塩，硫酸ナトリウム塩等の硫酸塩など、色素としてアシッドレッド１３８，アシッドブルー９，アシッドイエロー１４１，リアクティブブルー、その他の各種水溶性有効成分としてイソチアゾロンなどの抗菌剤、ヒドロキシエタンジホスホン酸などの酸化防止剤などが挙げられる。なお、上記水相成分の使用量は通常量とすることができる。
【００１６】
本発明の製造方法では、上述した膜形成成分と油分と水相の一部とを混合しながら高剪断を付加して混練することによって液晶組成物を形成させた後、該液晶組成物に水相の残量を添加・混合することによって、上記膜形成成分からなる二分子膜多層構造に上記油分が包含された小胞体分散液を製造する。この場合、連続相は水相となる。
【００１７】
ここで、液晶組成物の形成温度は、膜形成成分の相転移温度（Ｔｃ）以上であることを必要とする。液晶組成物形成温度がＴｃに満たないと、液晶が形成されない。液晶組成物の形成温度とＴｃとの温度差は、特に制限されるものではなく、液晶形成が可能な温度範囲内で適宜選定することができるが、通常、液晶組成物の形成温度がＴｃよりも５〜２０℃、特に１０〜１５℃程度高いことが望ましい。
【００１８】
また、液晶組成物を形成するために上記膜形成成分及び油分と共に混合される水相量は、使用する膜形成成分と油分の種類によって適宜選定されるが、通常、使用される水相の全量の１０〜５０％であって、液晶組成物中における油相（膜形成成分及び油分）：水相＝１：０．５〜１：２となる量である。そして、上記膜形成成分と油分と水相の一部とを混合する場合、容器内にこれらを添加する順序は特に制限されず、全部を同時に添加してもよい。
【００１９】
上記各成分を混合しながら、高剪断を付加して混練する装置は、その機種は特に制限されないが、系の粘度が液晶組成物が形成されるに従って高くなることを考慮すれば、高粘度物を全体混合でき、且つ剪断力の高い羽根を有するものが望ましい。ここで、撹拌装置のタイプとしては、１組の羽根によって上記撹拌特性を確保できる装置と複数組の羽根によって上記撹拌特性を確保できる装置との２種類に大別できるので、以下、それぞれの装置に分けて本発明の製造方法において付加される剪断について説明する。
【００２０】
まず、１組の羽根で全体混合と高剪断力を確保できる装置について図面を用いて説明する。このタイプの装置の場合、図１に示すように、通常、攪拌特性を考えると、剪断力は撹拌槽１内での羽根２先端の周速が支配的であり、全体混合については、撹拌槽１全体における単位液体積当たりの羽根２の回転による動力や撹拌槽１全体における単位液体積当たりの羽根２の吐出流量が支配的である。従って、本発明において高剪断を付加するには、羽根２先端の周速に着目する必要があり、本発明の場合、羽根２先端の周速Ｕｔ［ｍ／ｓ］のレベルが、装置の大きさにはかかわらず、５ｍ／ｓ以上２５ｍ／ｓ以下、好ましくは７ｍ／ｓ以上２５ｍ／ｓ以下、より好ましくは１０ｍ／ｓ以上２５ｍ／ｓ以下とすることによって、高剪断を付加することができる。なお、羽根２先端の周速Ｕｔは、下記式により算出することができる。
【００２１】
Ｕｔ＝π×ｎ×ｄ
ｎ：羽根回転数［ｒｐｓ］，ｄ：羽根径［ｍ］
【００２２】
この場合、上記周速Ｕｔによって剪断の程度は規定できるが、全体混合力を確保するには、装置の大きさに関するファクターを考慮する必要があり、そのためには下記式で定義される見掛けの剪断速度によって規定することが望ましい。
【００２３】
見掛けの剪断速度＝Ｕｔ／（Ｄ−ｄ）
Ｕｔ：剪断速度［ｍ／ｓ］，ｄ：羽根径［ｍ］，Ｄ：撹拌槽径［ｍ］
【００２４】
通常の混練装置の場合、羽根２先端の周速Ｕｔを一定にすると、装置が大きくなるにつれて羽根２と撹拌槽１との間の距離が大きくなり、見掛けの剪断速度の値は小さくなるものである。このような見掛けの剪断速度を用いて本発明の高剪断を規定する場合、見掛けの剪断速度が１００〜１０００［ｓ^-1］程度であることが好ましい。
【００２５】
また、剪断力と全体混合の同時確保をするには、羽根径ｄと撹拌槽径Ｄとの比ｄ／Ｄを０．７以上にすることが好ましい。なお、その上限は０．９以下であることが好ましい。このような撹拌特性を有する具体的な装置としては、例えばラインミキサー、パワーミキサー、スパイラルミキサーなどを使用すると好適である。
【００２６】
次に、複数組の羽根を備えた装置としては、図２に示すように、高剪断を与えることができる羽根２とその周囲を囲う内径Ｄ´のステーター３、全体混合を行なうことができる掻き取り型の羽根４とを備えた装置が使用される。このような装置の場合、本発明の高剪断を付加するには、羽根２先端の周速Ｕｔ［ｍ／ｓ］のレベルを５ｍ／ｓ以上、好ましくは７ｍ／ｓ以上２５ｍ／ｓ以下、より好ましくは１０ｍ／ｓ以上２５ｍ／ｓ以下とすると共に、上記Ｄに代えてステーター３の内径Ｄ´を用いて算出された見掛けの剪断速度を１，０００〜１０，０００［ｓ^-1］程度とすることが好ましい。また、複数組の羽根を備えた装置の場合、上記装置とは別に図３に示すように、通常高剪断を与えることができる羽根２と全体混合を行なうことができる掻き取り型の羽根４とを備えた装置も使用される。このような装置の場合、本発明の高剪断を付加するには、上記と同様に羽根２先端の周速に着目する必要があり、その程度は、５ｍ／ｓ以上、好ましくは７ｍ／ｓ以上２５ｍ／ｓ以下、より好ましくは１０ｍ／ｓ以上２５ｍ／ｓ以下とすることによって、高剪断を付加することができる。
【００２７】
上記のような複数組の羽根を備えた装置において、上記撹拌特性を付与できる羽根２としては、ホモミキサー、ディスパーミキサーなどが例示されるが、通常これらの羽根径と撹拌槽径との比ｄ／Ｄは、０．２〜０．４程度であり、系の粘度が液晶組成物が形成されるに従って高くなることを考慮すれば、このような羽根２のみでは撹拌槽の全体を混合するには力不足である。そこで、高粘度物の混合に適した掻き取り型の羽根４が好適に併用されるが、この場合、高剪断を付加する羽根２に効率的に液を供給するためには、掻き取り型の羽根４の先端の周速として１ｍ／ｓ以上の流動を付加することが好ましい。
【００２８】
これらの撹拌特性を有する具体的な装置としては、例えばアジホモミキサー、逆流ミキサー、ハイブリッドミキサーなどを使用すると好適である。
【００２９】
本発明は、このような混練工程によって、膜形成成分と油分と水相の一部とからなる混合液から液晶組成物を形成するものであるが、かかる工程において液晶組成物が形成されたか否かは、液晶組成物が形成された場合、系の粘度が数１００〜数万Ｐ（ポイズ）と高くなるので、この粘度変化を利用して確認することができる。
【００３０】
ここで、このような液晶組成物が形成された系を凍結した後に裁断し、その裁断表面の型を取って、透過型電子顕微鏡で観察したところ、多層構造の存在が認められた。この多層構造は、膜形成成分による二分子膜と水層とにより形成されたものであり、この場合、膜形成成分の分子は、互いにその疎水基を膜の内側に向けて配列するので、油分はこのような二分子の疎水基間に微小単位で分散されていると考えられる。
【００３１】
本発明の製造方法は、上記液晶組成物と水相の残部とを混合して、目的とする小胞体分散液を得るものであるが、この場合、混合温度は、上記膜形成成分の相転移温度以下でも製造可能であるが、膜形成成分が固まってくることを考慮すれば、上記相転移温度以上で行なうことが好ましい。また、液晶組成物と残りの水相の添加順序は、特に問わず、例えば同時に添加してもよい。そして、この混合・分散工程における剪断力は、特に制限されず、通常の乳化分散工程における程度の剪断力、即ち、通常の乳化分散に使用される機械の通常使用範囲であればよいが、本発明の場合、液晶組成物の粘度が高いという点を考慮すれば、滞留時間を長くして、剪断のかかる時間を増やすことが望ましい。
【００３２】
従って、本発明の上記混合・分散工程においては、通常の乳化分散用の装置が使用されるが、このような装置としては、通常、高剪断型分散装置が使用され、具体的には、ホモミキサー、マイルダー、クレアミックス、ラインミキサー、アジホモミキサー、ホモミックラインフロー、ディスパーミキサー、逆流ミキサーなどを挙げることができ、これらは１種単独で又は２種以上を適宜組み合わせて使用してもよい。また、この場合、系の粘度は、数１０〜数１００ｃＰ（センチポイズ）程度であるので、掻き取り羽根はあっても無くてもよい。
【００３３】
なお、本発明の製造方法は、上記工程によって得られた小胞体分散液に、さらに色素などを添加してもよく、また、分散工程後に冷却を行ってもよい。さらに、仕上げ段階（小胞体分散液が形成された段階）における温度は、膜形成成分の転移点以上であってもよく、相転移点以下となって二分子膜多層構造の二分子膜が固まっている状態となっていてもよい。
【００３４】
本発明の製造方法によって得られた小胞体分散液は、この小胞体分散液のみで製品化することも可能であり、さらに他の製品にこの小胞体分散液を原料として配合することもできる。従って、これらの小胞体分散液は、衣料用仕上げ剤や化粧料，洗浄剤などとしてそのまま使用することもでき、またこれらの原料として他の原料を混ぜて使用することもできる。
【００３５】
【発明の効果】
本発明の小胞体分散液の製造方法によれば、油分が二分子膜多層構造にしっかり包まれた小胞体を水中に安定的に分散させることができるので、Ｏ／Ｗ型エマルジョンに比べて油分包含の安定性が向上すると共に、他の成分の存在によって小胞体が容易に破壊されることがない小胞体分散液を得ることができる。また、本発明の小胞体分散液の製造方法によれば、保存中に分散液中に油分が分離することがなく保存安定性に優れる小胞体分散液が得られ、特に小胞体の平均粒径を０．１〜０．５μｍ程度に微細化できるのみならず、様々な油分を包含することができる。
【００３６】
本発明の製造方法により製造された小胞体分散液は、油分が界面活性剤などからなる二分子膜多層構造に取り込まれているため、繊維や毛髪への吸着性能が高く、油分を無駄なく吸着させることができるので、例えば油分としてシリコーンや抗菌剤を使用して柔軟剤を調製すると、衣服にシリコーンによるすべり作用や抗菌剤による抗菌機能を付与することができる。また、例えば油分としてシリコーンや有効成分としてオリーブ油、スクワラン等を使用してヘアーリンスを調製すると、毛髪にシリコーンによるすべり作用や上記有効成分によるしっとり感を付与することができる。さらに、流動パラフィンを包んだ小胞体分散液を台所用洗剤などの洗浄剤に添加すると、皮膚を保護することができる。このように、本発明の製造方法により製造された小胞体分散液は、種々の用途に有効に利用することができる。
【００３７】
【実施例】
以下、実施例及び比較例を示して本発明を具体的に説明するが、本発明は下記の実施例に制限されるものではない。
【００３８】
［実施例１〜４、比較例１，２］
表１に示す膜形成成分と油分と水相成分の一部とを、あらかじめ５０℃に加温しておき、これらを表１に示す液晶形成装置内に仕込み、表１に示す撹拌特性値下で表１に示す時間混練して、液晶組成物を得た。次いで、この液晶組成物と予め５０℃に加熱した残りの水相とを表１に記載した分散装置の容器内に仕込み、高剪断下でこれらを分散させて、所定の小胞体分散液を得た。
【００３９】
得られた小胞体分散液につき、以下の評価を行った。結果を表１に併記する。小胞体の確認
分散液を偏光顕微鏡を用いて直交偏光条件下で６００倍で観察し、二分子膜多層構造を持つ小胞体の存在を示す十字ニコル像が現れたか否かを調べ、以下の判定基準によって判定した。
＜判定基準＞
〇：十字ニコルが広い範囲にわたって見える
△：十字ニコルが一部見える
×：十字ニコルが見えない
安定性の評価
分散液を室温に冷却し、１日間放置した後、分散液の１０ヶ所以上をサンプリングして位相差顕微鏡で観察を行った。位相差顕微鏡の倍率は６００倍で、１サンプルにつき１０ヶ所以上の場所を観察し、二分子膜多層構造で包まれていない油分が存在するか否かを調べ、下記基準により判定した。また、同じ分散液を５０℃の恒温槽に１ヶ月間及び３ヶ月間放置した後、液面に油分の浮きがあるか否かを目視観察し、下記基準により判定した。なお、実施例２の分散液及び比較例１の分散液を５０℃３カ月保存した後の光学顕微鏡（倍率６００倍）写真をそれぞれ図４（実施例２）及び図５（比較例１）に示す。なお、図５において、大きな粒子が油滴であり、図４及び図５によれば、本発明の小胞体分散液には比較例１の小胞体分散液（従来の小胞体分散液）に比べて、粒径の小さい小胞体が分散していることが認められる。
＜位相差顕微鏡の判定基準＞
〇：二分子膜多層構造で包まれていない油分が認められない
×：二分子膜多層構造で包まれていない油分が存在する
＜保存安定性の判定基準＞
〇：液面に油滴が存在しない
×：液面に油滴が存在する
【００４０】
【表１】

【００４１】
表１の結果によれば、液晶組成物形成時の周速（Ｕｔ）を５ｍ／ｓ以上とすると共に、見掛けの剪断速度を１００〜１，０００（ｓ^-1）として高剪断を付加した本発明の製造方法の場合（実施例１〜３）及びアジホモミキサーを使用して高剪断を付加した場合（実施例４）は、過酷保存条件下でも安定な小胞体分散液が得られるのに対して、液晶組成物を周速（Ｕｔ）５ｍ／ｓ未満の低剪断下で形成した場合（比較例１）は、得られた小胞体分散液が過酷保存条件下では耐えられないことが認められる。一方、各成分を手撹拌し、液晶組成物を形成せずに膜形成成分と油分とを水相中に分散した場合（比較例２）は、小胞体がある程度は形成されたようではあるが、油分は封入されなかった。
【００４２】
［実施例５〜１３］
表２に示す膜形成成分と油分と水相の一部とを、あらかじめ５０℃に加温しておき、これらをラインミキサー（実施例１と同じ装置・撹拌特性値）に供給し、高剪断下で３０秒間混練して、液晶組成物を得た。次いで、この液晶組成物と予め５０℃に加熱した残りの水相とを表１に記載した分散装置の容器内に仕込み、高剪断下でこれらを分散させて、所定の小胞体分散液を得た。
【００４３】
得られた小胞体分散液につき、小胞体の存在の確認及び小胞体の安定性を実施例１〜４と同様の方法で評価した。結果を表２に併記する。
【００４４】
【表２】

【００４５】
表２の結果によれば、本発明の製造方法によって、種々の油分を取り込んだ小胞体の分散液が得られ、これらの小胞体分散液は過酷保存条件下でも安定であることが認められる。
【００４６】
［実施例１４〜２０］
上記実施例５〜１３において、各組成に代えて表３に示す組成を用いる以外は、実施例５〜１３と同様の方法によって分散液を調製し、得られた分散液の小胞体の存在の確認及び小胞体の安定性を実施例５〜１３と同様の方法で評価した。結果を表３に併記する。
【００４７】
【表３】

【００４８】
表３の結果によれば、本発明の製造方法は、種々の膜形成成分によって油分を安定的に取り込んだ小胞体分散液が得られることが認められる。
【００４９】
次に、上記実施例１で得られた小胞体分散液を衣料用柔軟剤として女性用ストッキングの処理を行い、対照として従来の柔軟剤処理によるストッキングとの使用感を１０名のパネラーによって比較評価したところ、８名のパネラーが、実施例１による処理を行ったストッキングの方が、従来の柔軟剤処理によるストッキングよりも引っかからず、はきやすいという評価をした。
【００５０】
また、上記実施例９で製造した小胞体分散液を衣料用柔軟剤として、靴下の処理を行い、対照として市販の柔軟剤（ライオン（株）製ソフランＣ）で処理を行ったものを左右別々に１０名のパネラーが１日履いて、靴下を脱いだときのにおいを評価したところ、７名のパネラーが実施例９で処理したものが市販品よりもいやなにおいがしないという評価をした。
【図面の簡単な説明】
【図１】本発明において液晶組成物を形成する装置の一例の概略断面図である。
【図２】本発明において液晶組成物を形成する装置の他の例の概略断面図である。
【図３】本発明において液晶組成物を形成する装置のさらに他の例の概略断面図である。
【図４】実施例２の小胞体分散液の５０℃３カ月保存後の光学顕微鏡写真である。
【図５】比較例１の小胞体分散液の５０℃３カ月保存後の光学顕微鏡写真である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing an endoplasmic reticulum dispersion capable of stably encapsulating oils such as hydrocarbons, ester oils, silicone oils, and oil-soluble antibacterial agents in a bilayer multilayer structure composed of film-forming components.
[0002]
[Prior art and problems to be solved by the invention]
Conventionally, there are liposomes as particles having a bilayer multi-layer structure, and this is particularly for the purpose of retaining a water-soluble substance in the membrane, and an oil component cannot be wrapped by a general method for producing liposomes.
[0003]
On the other hand, JP-A-6-269656 describes that an oil component is retained in a vesicle structure as a method for producing an oil-in-water emulsion. An oil-in-water emulsion obtained by this production method, It was difficult to keep the oil completely under storage conditions. Japanese Patent Publication No. 63-33414 proposes a method for producing a dispersion of particles having a bilayer multilayer structure. In this method, the resulting dispersion is incorporated into the bilayer multilayer structure. It is the aqueous phase that does not disclose anything in which oil has been incorporated. Furthermore, Japanese Patent Application Laid-Open No. 5-19489 discloses that a fragrance is emulsified with a nonionic active agent to form a structured emulsion including a liquid crystal structure surrounding the fragrance, and this structured emulsion is dispersed in a detergent composition. In this method, the non-aqueous phase is dispersed directly in the total amount of the aqueous phase and mixed under low shear conditions to form a structured emulsion. Not only can it be produced, but there is also a problem that the stability of the particles in the dispersion at high temperatures is poor.
[0004]
The present invention has been made in order to solve the above-mentioned circumstances, and has good storage stability of vesicles in which oil is contained in a bilayer multilayer structure, and is capable of obtaining vesicles having a fine particle size. It aims at providing the manufacturing method of a vesicle dispersion.
[0005]
Means for Solving the Problem and Embodiment of the Invention
  As a result of intensive studies to solve the above-mentioned problems, the present inventor kneaded a specific ratio of the film-forming component, the oil component, and a part of the aqueous phase while adding the specific high shear while mixing the whole. As a result, the oil component was dispersed in a minute unit in the bilayer multilayer structure by the film forming component.Of specific viscosityA liquid crystal composition is formed, and this liquid crystal composition and the remaining aqueous phase are mixed to produce an endoplasmic reticulum dispersion, which stabilizes the endoplasmic reticulum that contains oil in the bilayer multilayer structure. In particular, the present inventors have found that fine and uniform vesicles having an average particle size of about 0.1 to 0.5 μm are formed, and have made the present invention.
[0006]
Therefore, the present invention forms a liquid crystal composition by kneading a system comprising a film-forming component, an oil component, and a part of an aqueous phase with high shear applied at a temperature equal to or higher than the phase transition of the film-forming component. After that, the remaining amount of the aqueous phase is added to and mixed with the liquid crystal composition to form an endoplasmic reticulum dispersion liquid in which the oil is incorporated into a bilayer multilayer structure composed of a film-forming component. A method for producing a vesicle dispersion is provided.
[0007]
Hereinafter, the present invention will be described in more detail. The method for producing an endoplasmic reticulum dispersion of the present invention uses a film-forming component, an oil component, and an aqueous phase component.
[0008]
Here, as the film forming component, the kind is not particularly limited as long as it forms a bilayer multilayer, but a quaternary ammonium salt, a tertiary amine salt represented by the following general formula (1), One or more selected from cationic surfactants such as imidazoline salts, imidazolinium salts, amino acid-based cationic surfactants, or the above-mentioned cationic surfactant and a higher alcohol represented by the following general formula (2) A quaternary ammonium salt is particularly preferred among these.
[0009]
[Chemical 1]

(However, R in the formula¹Is an alkyl or alkenyl group having 10 to 24 carbon atoms, R²Is an alkyl group having 1 to 3 carbon atoms, an alkyl group having 10 to 24 carbon atoms or an alkenyl group, and R¹And R²May be unsubstituted, may be separated by a functional group such as —O—, —CONH—, —COO—, or may be substituted with a functional group such as —OH. R^ThreeIs an alkyl group having 1 to 3 carbon atoms, R^FourIs an alkyl group having 1 to 3 carbon atoms or a benzyl group, and X is a halogen atom or a monoalkyl sulfate group. )
R^Five-OH (2)
(However, R in the formula^FiveIs an alkyl group having 12 to 22 carbon atoms. )
[0010]
Specific examples of the film-forming component include stearyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, dodecyl trimethyl ammonium chloride, di-tallow alkyl dimethyl ammonium bromide, dioleyl dimethyl ammonium chloride as quaternary ammonium salts of formula (1), Examples of oleyltrimethylammonium chloride include coconut oil fatty acid L-arginine ethyl-DL-pyrrolidone carboxylic acid, 4-guanidinobutyl lauryl acetic acid, etc. Salt, dioleylmethylamine hydrochloride, distearylmethylamine sulfate, and the like. In these tertiary amine salts, the alkyl chain is -COO-, -CO. A functional group may be split such H-. In addition, 1-octadecanoylaminoethyl-2-heptadecylimidazoline hydrochloride, 1-octadecenoylaminoethyl-2-heptadecenylimidazoline hydrochloride, etc. as imidazoline salt, methyl-1- as imidazolinium salt, etc. Tallow amidoethyl-2-tallow alkylimidazolinium methyl sulfate, methyl-1-hexadecanoylamidoethyl-2-pentadecylimidazolinium chloride, ethyl-1-octadecenoylamidoethyl-2-heptadecenylimidazo Examples of higher alcohols of formula (2) such as linium ethyl sulfate include cetostearyl alcohol, dodecyl alcohol, cetyl alcohol, stearyl alcohol, and behenyl alcohol. These film-forming components can be appropriately selected depending on the use and purpose of the produced endoplasmic reticulum dispersion. For example, when the dispersion is a garment finish or a cosmetic, it is used as a garment finish base. A cationic surfactant used as a base for cosmetics or cosmetics and a higher alcohol are preferably used.
[0011]
The amount of the film-forming component used is about 1 to 40% by weight, preferably about 3 to 30% by weight, based on the entire dispersion. If the blending amount is too small, it may be difficult to encapsulate the oil. On the other hand, if an excessive amount is blended, formation of the endoplasmic reticulum may be difficult.
[0012]
In the present invention, in order to facilitate film formation with the film-forming component, an organic solvent such as polyhydric alcohols such as ethylene glycol, propylene glycol, and glycerin and lower alcohols such as ethanol and isopropyl alcohol, stearin, and the film-forming component. Fatty acids such as acid and oleic acid and additives such as various emulsifiers such as polyoxyethylene alkyl ether, sorbitan fatty acid ester, and polyoxyethylene sorbitan fatty acid ester can be blended in a usual amount.
[0013]
Next, as the oil, it is possible to use a hydrophobic oil used in products in various fields such as clothing finishes, cosmetics, pharmaceuticals, detergents, etc., but usually change the texture of clothing, Those having functions such as moisturizing skin, nourishing hair, antibacterial and bactericidal effects are preferably used. Specifically, synthetic oils such as silicone oil, cyclic silicone and modified silicone, mineral oil such as liquid paraffin, liquid isoparaffin, paraffin wax, vegetable oil such as jojoba oil, olive oil, olive squalane, castor oil, carnauba wax, lanolin , Squalane, mink oil and other animal oils, hexyl laurate, isopropyl palmitate, oleic acid, stearic acid, etc., and more specific functions are oil-soluble such as triclosan, hinokitiol, triclocarban, isopropylmethylphenol Antibacterial and bactericidal agents, oil-soluble preservatives such as butylparaben, propylparaben, benzoic acid, salicylic acid and sorbic acid, and oil-soluble properties such as dibutylhydroxytoluene, butylhydroxyanisole and tocopherol Antioxidants, oil-soluble fragrances such as linalool, citronellol, geraniol, and geranyl acetate, and other oil-soluble UV absorbers, insect repellents, moisturizers, and the like can be mentioned. They can be used in appropriate combinations.
[0014]
The amount of the oil used is preferably about 0.1 to 20% by weight with respect to the entire dispersion, and the ratio of the oil to the film forming component is 1: 1 or less with respect to the film forming component. When the oil content is larger than the film-forming component, inclusion in the bilayer multilayer structure may be insufficient. In addition, when the melting | fusing point of the oil component to be used is high, you may melt | dissolve and use in organic solvents, such as the above lower alcohols, and other liquid oil components.
[0015]
Examples of the aqueous phase component include emulsifiers, dispersion stabilizers, low-temperature stabilizers, inorganic salts, dyes and other various water-soluble active ingredients in addition to water. Specifically, nonionic surfactants such as polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkyl ether, and fatty acid polyethylene glycol as an emulsifier, Polyacrylic acid, carboxymethylcellulose, carboxyvinyl polymer, etc. as dispersion stabilizers, ethylene glycol, propylene glycol, glycerin, etc. as low temperature stabilizers, hydrochlorides such as sodium chloride and calcium chloride, sulfates such as sodium sulfate, etc. as inorganic salts Acid Red 138, Acid Blue 9, Acid Yellow 141, Reactive Blue as pigments, and isothiazolone as various other water-soluble active ingredients Which antimicrobial agents, such as anti-oxidants, such as hydroxyethane diphosphonic acid. In addition, the usage-amount of the said water phase component can be made into a normal amount.
[0016]
In the production method of the present invention, a liquid crystal composition is formed by adding high shear while kneading the above-described film-forming component, oil, and a part of the aqueous phase, and then kneading the liquid crystal composition with water. By adding and mixing the remaining amount of the phase, an endoplasmic reticulum dispersion in which the oil is contained in the bilayer multilayer structure composed of the film-forming component is produced. In this case, the continuous phase is an aqueous phase.
[0017]
Here, the formation temperature of the liquid crystal composition needs to be equal to or higher than the phase transition temperature (Tc) of the film forming component. If the liquid crystal composition formation temperature is less than Tc, no liquid crystal is formed. The temperature difference between the formation temperature of the liquid crystal composition and Tc is not particularly limited and can be appropriately selected within a temperature range in which liquid crystal can be formed. Usually, the formation temperature of the liquid crystal composition is higher than Tc. Is preferably 5 to 20 ° C, particularly about 10 to 15 ° C.
[0018]
  The amount of the aqueous phase mixed with the film-forming component and the oil component to form the liquid crystal composition is appropriately selected depending on the type of the film-forming component and the oil component to be used. 10 to 50%, and the oil phase (film-forming component and oil content) in the liquid crystal composition: water phase = 1: 0.5 to 1: 2In quantityis there. And when mixing the said film formation component, oil component, and a part of water phase, the order which adds these in a container in particular is not restrict | limited, You may add all simultaneously.
[0019]
An apparatus for kneading by adding high shear while mixing each of the above components is not particularly limited, but considering that the viscosity of the system increases as the liquid crystal composition is formed, It is desirable to have a blade having high shearing force and capable of mixing the whole. Here, the type of the stirring device can be roughly divided into two types, that is, a device that can secure the stirring characteristics with one set of blades and a device that can secure the stirring characteristics with a plurality of sets of blades. The shear applied in the production method of the present invention will be described separately.
[0020]
  First, an apparatus that can ensure overall mixing and high shear force with one set of blades will be described with reference to the drawings. In the case of this type of apparatus, as shown in FIG. 1, in general, considering the stirring characteristics, the shearing force is dominated by the peripheral speed at the tip of the blade 2 in the stirring tank 1. The power by the rotation of the blade 2 per unit liquid volume in the whole 1 and the discharge flow rate of the blade 2 per unit liquid volume in the entire stirring tank 1 are dominant. Therefore, in order to apply high shear in the present invention, it is necessary to pay attention to the peripheral speed at the tip of the blade 2. In the present invention, the level of the peripheral speed Ut [m / s] at the tip of the blade 2 is large. Regardless of the size, 5m / s or more25 m / s or lessPreferably, high shear can be added by setting it to 7 m / s or more and 25 m / s or less, more preferably 10 m / s or more and 25 m / s or less. The peripheral speed Ut at the tip of the blade 2 can be calculated by the following equation.
[0021]
Ut = π × n × d
n: blade rotation speed [rps], d: blade diameter [m]
[0022]
In this case, although the degree of shearing can be defined by the peripheral speed Ut, in order to secure the overall mixing force, it is necessary to consider factors related to the size of the device. For that purpose, the apparent shearing defined by the following equation is required. It is desirable to define by speed.
[0023]
Apparent shear rate = Ut / (D−d)
Ut: Shear rate [m / s], d: Blade diameter [m], D: Agitation tank diameter [m]
[0024]
In the case of a normal kneading device, if the peripheral speed Ut at the tip of the blade 2 is kept constant, the distance between the blade 2 and the stirring tank 1 increases as the device increases, and the apparent shear rate value decreases. is there. When the high shear of the present invention is specified using such an apparent shear rate, the apparent shear rate is 100 to 1000 [s.^-1] Is preferable.
[0025]
Further, in order to ensure the shearing force and the entire mixing at the same time, the ratio d / D between the blade diameter d and the stirring tank diameter D is preferably 0.7 or more. The upper limit is preferably 0.9 or less. As a specific apparatus having such a stirring characteristic, for example, a line mixer, a power mixer, a spiral mixer or the like is preferably used.
[0026]
Next, as shown in FIG. 2, as an apparatus having a plurality of sets of blades, a blade 2 capable of giving high shear and a stator 3 having an inner diameter D ′ surrounding the blade 2 and a scraper capable of performing overall mixing. A device with a take-off blade 4 is used. In the case of such an apparatus, in order to add the high shear according to the present invention, the level of the peripheral speed Ut [m / s] at the tip of the blade 2 is 5 m / s or more, preferably 7 m / s or more and 25 m / s or less. Preferably, the apparent shear rate calculated using the inner diameter D ′ of the stator 3 in place of the D is 1,000 to 10,000 [s.^-1It is preferable to set it to a degree. Further, in the case of a device provided with a plurality of sets of blades, as shown in FIG. 3 separately from the above device, a blade 2 that can normally give high shear, and a scraped blade 4 that can perform overall mixing, A device equipped with is also used. In the case of such an apparatus, in order to add the high shear of the present invention, it is necessary to pay attention to the peripheral speed at the tip of the blade 2 as described above, and the degree is 5 m / s or more, preferably 7 m / s or more. High shear can be added by setting it to 25 m / s or less, more preferably 10 m / s or more and 25 m / s or less.
[0027]
In the apparatus provided with a plurality of blades as described above, examples of the blade 2 that can impart the stirring characteristics include a homomixer and a disper mixer, but the ratio d between the blade diameter and the stirring tank diameter is usually d. / D is about 0.2 to 0.4, and considering that the viscosity of the system becomes higher as the liquid crystal composition is formed, only the blade 2 like this mixes the entire stirring tank. Is underpowered. Therefore, a scraping blade 4 suitable for mixing a high-viscosity material is preferably used together. In this case, in order to efficiently supply the liquid to the blade 2 to which high shear is applied, a scraping blade 4 is used. It is preferable to add a flow of 1 m / s or more as the peripheral speed at the tip of the blade 4.
[0028]
As specific apparatuses having these stirring characteristics, it is preferable to use, for example, an azimuth homomixer, a reverse flow mixer, a hybrid mixer, or the like.
[0029]
The present invention forms a liquid crystal composition from a liquid mixture comprising a film-forming component, an oil component, and a part of an aqueous phase by such a kneading process. Whether or not the liquid crystal composition is formed in this process. When the liquid crystal composition is formed, the viscosity of the system becomes as high as several hundred to several tens of thousands P (poise), and can be confirmed using this change in viscosity.
[0030]
Here, the system in which such a liquid crystal composition was formed was frozen and then cut, and the cut surface mold was taken and observed with a transmission electron microscope. The presence of a multilayer structure was observed. This multilayer structure is formed by a bilayer film and an aqueous layer formed of a film-forming component. In this case, since the molecules of the film-forming component are arranged with their hydrophobic groups facing the inside of the film, the oil content Are considered to be dispersed in minute units between the hydrophobic groups of these two molecules.
[0031]
In the production method of the present invention, the liquid crystal composition and the remainder of the aqueous phase are mixed to obtain a target vesicle dispersion. In this case, the mixing temperature is the phase transition of the film-forming component. Although it can be produced at a temperature below the temperature, it is preferable to carry out at a temperature above the phase transition temperature in view of the fact that the film-forming component is solidified. The order of addition of the liquid crystal composition and the remaining aqueous phase is not particularly limited, and for example, they may be added simultaneously. The shearing force in the mixing / dispersing step is not particularly limited, and may be within the normal use range of a machine used for ordinary emulsification dispersion, that is, a shearing force of a degree in a usual emulsification dispersion step. In the case of the invention, considering the fact that the viscosity of the liquid crystal composition is high, it is desirable to increase the residence time and increase the shearing time.
[0032]
Therefore, in the above mixing / dispersing step of the present invention, an ordinary emulsifying and dispersing apparatus is used, and as such an apparatus, a high shear type dispersing apparatus is usually used. A mixer, a milder, a Clare mix, a line mixer, an azimuth homomixer, a homomic line flow, a disper mixer, a backflow mixer etc. can be mentioned, These may be used individually by 1 type or in combination of 2 or more types. . In this case, since the viscosity of the system is about several tens to several hundreds cP (centipoise), the scraping blade may or may not be provided.
[0033]
In the production method of the present invention, a dye or the like may be further added to the endoplasmic reticulum dispersion obtained in the above step, and cooling may be performed after the dispersing step. Furthermore, the temperature in the finishing stage (the stage where the endoplasmic reticulum dispersion is formed) may be above the transition point of the film-forming component, and below the phase transition point, the bilayer film of the bilayer multilayer structure is solidified. It may be in the state.
[0034]
The endoplasmic reticulum dispersion obtained by the production method of the present invention can be made into a product using only this endoplasmic reticulum dispersion, and further, the endoplasmic reticulum dispersion can be blended as a raw material with other products. Therefore, these endoplasmic reticulum dispersion liquids can be used as they are as finishing agents for clothing, cosmetics, cleaning agents, and the like, and other raw materials can be mixed and used as these raw materials.
[0035]
【The invention's effect】
According to the method for producing an endoplasmic reticulum dispersion of the present invention, the endoplasmic reticulum in which the oil is firmly enclosed in the bilayer multilayer structure can be stably dispersed in water. It is possible to obtain an endoplasmic reticulum dispersion in which inclusion stability is improved and the endoplasmic reticulum is not easily destroyed by the presence of other components. In addition, according to the method for producing an endoplasmic reticulum dispersion of the present invention, an endoplasmic reticulum dispersion having excellent storage stability without oil separation in the dispersion during storage can be obtained, and in particular, the average particle size of the endoplasmic reticulum can be obtained. Can be refined to about 0.1 to 0.5 μm, and various oils can be included.
[0036]
Since the endoplasmic reticulum dispersion produced by the production method of the present invention is incorporated in a bilayer multilayer structure composed of a surfactant or the like, the adsorption performance to fibers and hair is high, and the oil is adsorbed without waste. Therefore, for example, when a softening agent is prepared using silicone or an antibacterial agent as an oil component, it is possible to impart a sliding action by the silicone or an antibacterial function by the antibacterial agent to the clothes. For example, when a hair rinse is prepared using silicone as an oil component and olive oil, squalane or the like as an active ingredient, it is possible to impart a sliding action by silicone or a moist feeling due to the active ingredient to hair. Furthermore, when the endoplasmic reticulum dispersion liquid wrapped with liquid paraffin is added to a cleaning agent such as a kitchen detergent, the skin can be protected. Thus, the endoplasmic reticulum dispersion liquid manufactured by the manufacturing method of this invention can be utilized effectively for various uses.
[0037]
【Example】
EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.
[0038]
[Examples 1 to 4, Comparative Examples 1 and 2]
The film-forming component shown in Table 1, the oil component, and a part of the aqueous phase component are preheated to 50 ° C., and these are charged into the liquid crystal forming apparatus shown in Table 1, and the stirring characteristic values shown in Table 1 are satisfied. And kneading for the time shown in Table 1 to obtain a liquid crystal composition. Next, the liquid crystal composition and the remaining aqueous phase heated to 50 ° C. in advance are charged into the container of the dispersion apparatus described in Table 1, and dispersed under high shear to obtain a predetermined vesicle dispersion. It was.
[0039]
The following evaluation was performed about the obtained endoplasmic reticulum dispersion liquid. The results are also shown in Table 1.Check the endoplasmic reticulum
The dispersion was observed with a polarizing microscope at a magnification of 600 under orthogonal polarization conditions to examine whether or not a crossed Nicol image indicating the presence of a vesicle having a bilayer multilayer structure appeared, and was determined according to the following criteria. .
<Criteria>
○: Crossed Nicols can be seen over a wide range
Δ: Some crossed Nicols are visible
×: Cross Nicole is not visible
Evaluation of stability
The dispersion was cooled to room temperature and allowed to stand for 1 day, then 10 or more locations of the dispersion were sampled and observed with a phase contrast microscope. The magnification of the phase contrast microscope was 600 times, and 10 or more places were observed per sample, and it was examined whether or not there was an oil component not encapsulated in the bilayer multilayer structure, and the following criteria were used. The same dispersion was allowed to stand in a thermostatic bath at 50 ° C. for 1 month and 3 months, and then whether the oil surface floated was visually observed and judged according to the following criteria. 4 (Example 2) and FIG. 5 (Comparative Example 1) are photographs of an optical microscope (600 times magnification) after the dispersion of Example 2 and the dispersion of Comparative Example 1 were stored at 50 ° C. for 3 months, respectively. Show. In FIG. 5, the large particles are oil droplets. According to FIGS. 4 and 5, the vesicle dispersion of the present invention is compared with the vesicle dispersion of Comparative Example 1 (conventional vesicle dispersion). Thus, it can be seen that vesicles having a small particle size are dispersed.
<Criteria for phase contrast microscope>
◯: Oil not wrapped in bilayer multilayer structure is not recognized
×: There is an oil component that is not wrapped in a bilayer multilayer structure.
<Criteria for storage stability>
○: No oil droplets on the liquid surface
×: Oil droplets exist on the liquid surface
[0040]
[Table 1]

[0041]
According to the results in Table 1, the peripheral speed (Ut) at the time of forming the liquid crystal composition is 5 m / s or more, and the apparent shear rate is 100 to 1,000 (s^-1In the case of the production method of the present invention to which high shear is added (Examples 1 to 3) and the case where high shear is applied using an Ajihomo mixer (Example 4), the small size is stable even under severe storage conditions. Whereas a vesicle dispersion is obtained, when the liquid crystal composition is formed under low shear at a peripheral speed (Ut) of less than 5 m / s (Comparative Example 1), the obtained vesicle dispersion is subjected to severe storage conditions. It is recognized that it cannot be tolerated under. On the other hand, when each component is hand-stirred and the film-forming component and the oil component are dispersed in the aqueous phase without forming a liquid crystal composition (Comparative Example 2), it seems that vesicles are formed to some extent. The oil was not encapsulated.
[0042]
[Examples 5 to 13]
The film-forming components, oil, and part of the aqueous phase shown in Table 2 are preheated to 50 ° C., and these are supplied to a line mixer (the same apparatus and stirring characteristic values as in Example 1), and high shear The mixture was kneaded for 30 seconds to obtain a liquid crystal composition. Next, the liquid crystal composition and the remaining aqueous phase heated to 50 ° C. in advance are charged into the container of the dispersion apparatus described in Table 1, and dispersed under high shear to obtain a predetermined vesicle dispersion. It was.
[0043]
About the obtained endoplasmic reticulum dispersion liquid, confirmation of existence of an endoplasmic reticulum and stability of an endoplasmic reticulum were evaluated by the method similar to Examples 1-4. The results are also shown in Table 2.
[0044]
[Table 2]

[0045]
According to the results in Table 2, it is recognized that dispersions of vesicles incorporating various oils are obtained by the production method of the present invention, and these vesicle dispersions are stable even under severe storage conditions.
[0046]
[Examples 14 to 20]
In the above Examples 5 to 13, a dispersion was prepared by the same method as in Examples 5 to 13 except that the compositions shown in Table 3 were used instead of the respective compositions, and the presence of vesicles in the obtained dispersions. Confirmation and stability of the endoplasmic reticulum were evaluated in the same manner as in Examples 5-13. The results are also shown in Table 3.
[0047]
[Table 3]

[0048]
According to the results in Table 3, it can be seen that the production method of the present invention can obtain an endoplasmic reticulum dispersion in which oil is stably taken in by various film-forming components.
[0049]
Next, the stockings for women were treated with the ER dispersion obtained in Example 1 as a softener for clothing, and the feeling of use with stockings by conventional softener treatment was compared and evaluated by 10 panelists as a control. As a result, eight panelists evaluated that the stockings subjected to the treatment according to Example 1 did not catch more than the stockings obtained by the conventional softener treatment and were easy to wear.
[0050]
In addition, the vesicle dispersion liquid produced in Example 9 was treated as a softener for clothing, socks were treated, and as a control, a commercial softener (Sophane C manufactured by Lion Co., Ltd.) was used as a control. When 10 panelists wore one day and evaluated the smell when they took off the socks, 7 panelists evaluated that those treated in Example 9 did not smell more savory than the commercial product.
[Brief description of the drawings]
FIG. 1 is a schematic cross-sectional view of an example of an apparatus for forming a liquid crystal composition in the present invention.
FIG. 2 is a schematic cross-sectional view of another example of an apparatus for forming a liquid crystal composition in the present invention.
FIG. 3 is a schematic cross-sectional view of still another example of an apparatus for forming a liquid crystal composition in the present invention.
4 is an optical micrograph of the endoplasmic reticulum dispersion liquid of Example 2 after storage at 50 ° C. for 3 months. FIG.
FIG. 5 is an optical micrograph of the endoplasmic reticulum dispersion liquid of Comparative Example 1 after storage at 50 ° C. for 3 months.

Claims (2)

One or more cationic surfactants selected from quaternary ammonium salts, tertiary amine salts, imidazoline salts, imidazolinium salts and amino acid cationic surfactants represented by the following general formula (1) A system comprising a film-forming component, an oil component, and a part of an aqueous phase, the mass ratio of which is an oil phase (film-forming component and oil component): water phase = 1: 0.5-1: 2. at a temperature of phase transition more film-forming components, in a stirred tank having a blade, and kneaded in a state where the peripheral speed of the blade tip (Ut) was added following high shear 5 m / s or more 25 m / s, viscosity After forming a liquid crystal composition of several hundred to several tens of thousands P (poise), the remaining amount of the aqueous phase is added to and mixed with the liquid crystal composition, and the oil component is added to the bilayer multilayer structure composed of film forming components. Formed vesicle dispersion with an average particle size of 0.1 to 0.5 μm Method for producing a vesicle dispersion, characterized in that.

Wherein R ¹ is an alkyl group or alkenyl group having 10 to 24 carbon atoms, R ² is an alkyl group having 1 to 3 carbon atoms, an alkyl group or alkenyl group having 10 to 24 carbon atoms, and R ¹ and R ² may be unsubstituted, may be divided by a functional group of —O—, —CONH—, —COO— or substituted with a functional group of —OH, and R ³ has 1 to ³ carbon atoms. (The alkyl group, R ⁴ is an alkyl group having 1 to 3 carbon atoms or a benzyl group, and X is a halogen atom or a monoalkyl sulfate group.) The method for producing an endoplasmic reticulum dispersion according to claim 1, wherein the film-forming component is a quaternary ammonium salt represented by the following general formula (3).

(However, wherein R ^6, R ⁷ are each an alkyl group or alkenyl group having 10 to 24 carbon atoms, -O -, - CONH- or -COO - of .R ⁸ which are separated by a functional group of the carbon A C 1-3 alkyl group, R ⁹ is a C 1-3 alkyl group or a benzyl group, and X is a halogen atom or a monoalkyl sulfate group.

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