JP3884242B2 - Method for producing emulsified composition - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は、互いに殆ど溶解しない二種の液体のエマルション即ち乳化組成物の製造方法に関し、特に、水中油型乳化組成物又は油中水型乳化組成物の製造方法に関する。また本発明は、乳化油脂組成物に関し、特に、水中油型乳化油脂組成物又は油中水型乳化油脂組成物の製造方法に関する。さらに、本発明は、化学薬品の乳化組成物の製造方法に関し、特に化学薬品の水中油型乳化組成物又は油中水型乳化油脂組成物の製造方法に関する。さらにまた、本発明は、医薬品の乳化組成物の製造方法に関し、特に医薬品の水中油型乳化組成物又は油中水型乳化組成物の製造方法に関する。さらに本発明は、化粧品の乳化油脂組成物の製造方法に関し、特に化粧品の水中油型乳化油脂組成物又は油中水型乳化油脂組成物の製造方法に関する。さらにまた、本発明は、飲料及び食品用の乳化油脂組成物の製造方法に関し、特に飲料及び食品用の水中油型乳化油脂組成物又は油中水型乳化油脂組成物の製造方法に関する。さらに加えて、本発明は、農薬の水中油型乳化組成物又は油中水型乳化組成物の製造方法に関する。本発明は、粒子径分布が狭く非常に均一な粒子径を有する乳化油脂組成物等の乳化組成物の製造方法に関する。
【０００２】
【従来の技術】
乳化油脂組成物は、化粧品においては、例えば、皮脂成分を、乳化させた乳剤性ローション、乳液、バニシングクリーム、コールドクリームなどの水中油型乳化物乳剤や、例えば、油中水型のコールドクリーム、栄養クリームなどの油中水型乳剤がある。また、医薬においても、主剤を乳化させた水中油型及び油中水型の乳剤や乳剤性軟膏などがある。食品では、食用油脂を、乳化させた、例えばマヨネーズ、マーガリン、クリーム、アイスクリームといった乳化物製品が多い。そしてまた、農薬の分野においても、農薬を、水中油型及び油中水型の乳化物乳剤が使用されている。このような乳化物を製造するには、分散相の微細化及び微細分散相の安定化を図る必要がある。
【０００３】
最近では、多孔質ガラス膜を使用することにより、簡単にしかも内相粒子が非常に均一な乳化物を作製することができるので、粒径の小さい内相粒子の乳化物製品は、多孔質ガラス膜等の多孔質膜により製造されている。
このような均一な孔径を有する多孔質膜を使用して、１０μｍ以下の平均粒子径を有する乳化油脂組成物を製造する乳化油脂組成物の製造方法としては、再乳化させる多孔質膜の孔径に対して１〜２０倍の平均粒子径を有する予備乳化油脂組成物を、油相部と水相部とから乳化剤を用いて予め製造し、該予備乳化油脂組成物を均一な孔径を有する多孔質膜を通過させることにより、再乳化させて、前記多孔質膜の孔径に対して１〜３倍の平均粒子径を有する乳化油脂組成物を製造する方法が提案されている。
【０００４】
【発明が解決しようとする課題】
しかし、以上のような乳化油脂組成物の製造方法においては、通過させる多孔質膜の孔径、即ち、乳化膜の孔径に対して1乃至３倍の粒子径を有する乳化油脂組成物を製造する場合に、乳化膜の孔径に対して２０倍以上の平均粒子径を有する乳化油脂組成物は，せん断応力に対する流動特性の変化率が大きいので、せん断応力の微妙な変化に対して定常的に乳化膜を通過させることができない。そして、乳化させた場合には、乳化された粒子に変形を生じ、均一な乳化油脂組成物が得られないばかりか、油相と水相が分離した状態の乳化油脂組成物が得られることとなるために、乳化膜の孔径に対して１〜２０倍の平均粒子径を有する予備乳化油脂組成物を予め調製することが必要とされており、そのため多くの手間を要して問題とされている。
また、乳化膜の孔径に対して１〜２０倍の平均粒子径を有する予備乳化油脂組成物を乳化膜により再乳化して得られる乳化油脂組成物の平均粒子径は、再乳化したときに通過した多孔質膜、即ち乳化膜の孔径の１〜３倍が限度であり、これより微細な、つまり、再乳化したときに通過した多孔質膜の孔径より小さい平均粒子径を有する乳化油脂組成物を製造することは難しいために、得られる乳化油脂組成物の分散相粒子の平均粒子径は、再乳化の過程で通過する多孔質膜の孔径により制限されることとなって、問題とされている。
しかも、乳化油脂組成物において、界面活性剤の使用量が多いと、例えば、化学薬品、医薬、化粧品、食品及び農薬などへの使用に制限が課せられることとなり、問題とされている。
本発明は、従来の多孔質膜を使用する乳化油脂組成物の製造方法における分散相(内相)粒子の微細化に係る問題点を解決することを目的としている。
【０００５】
【課題を解決するための手段】
本発明者らは、乳化剤の使用量が少ない予備乳化油脂組成物等の乳化組成物を均一な孔径を有する多孔質膜を通過させて、該多孔質膜の孔径より小さい平均粒径を有する乳化組成物を製造できることを発見して、本発明に至った。
本発明は、前記再乳化させるときに通過させる多孔質膜の孔径に対して１倍未満の平均粒子径を有する乳化油脂組成物等の乳化組成物を、製造することが可能な乳化組成物の製造方法を提供することを目的としている。
また、本発明は、前記再乳化させるときに通過させる多孔質膜の孔径に対して１倍未満の平均粒子径を有する乳化組成物を、使用する乳化剤の量を１重量％以下の量で、製造することが可能な乳化組成物の製造方法を提供することを目的としている。
【０００６】
即ち、本発明は、互いに溶解しない二種の液体の予備乳化組成物を乳化剤を用いて予め製造し、この製造された予備乳化組成物を均一な孔径を有する多孔質乳化膜を通過させて、再乳化させることにより１０μｍ以下の平均粒子径を有する乳化組成物を製造する乳化組成物の製造方法において、再乳化の際に通過させる５μｍ以下の均一な孔径を有する多孔質乳化膜の孔径に対して２０倍を超える平均粒子径を有し、分散相濃度が１０乃至５０重量％の予備乳化組成物を製造し、この得られた予備乳化組成物を、１ＭＰａ以上の圧力をかけながら、５μｍ以下の均一な孔径を有する多孔質乳化膜を、通過面積２５ｃｍ２あたり、１．５乃至３５ｍｌ／秒の通過速度で通過させて、前記乳化膜の孔径に対して１倍未満の平均粒子径を有し、単分散係数が０．６以下の乳化組成物を製造することを特徴とする乳化組成物の製造方法にあり、また、本発明においては、互いに溶解しない二種の液体の予備乳化組成物を、乳化剤を用いて予め製造し、この製造された予備乳化組成物を均一な孔径を有する多孔質乳化膜を通過させて、再乳化させることにより１０μｍ以下の平均粒子径を有する乳化組成物を製造する乳化組成物の製造方法において、再乳化の際に通過させる５μｍ以下の均一な孔径を有する多孔質乳化膜の孔径に対して２０倍を超える平均粒子径を有し、分散相濃度が１０乃至５０重量％の予備乳化組成物を、１％以下の濃度で乳化剤を含む外相部と内相部から予め製造し、この得られた予備乳化組成物を、１ＭＰａ以上の圧力をかけながら、前記５μｍ以下の均一な孔径を有する多孔質乳化膜を、通過面積２５ｃｍ２あたり、１．５乃至３５ｍｌ／秒の通過速度で通過させて、前記乳化膜の孔径に対して１倍未満の平均粒子径を有し、単分散係数が０．６以下の乳化組成物を製造することを特徴とする乳化組成物の製造方法にある。
【０００７】
【発明の実施の形態】
本発明において、互いに溶解しない二種の液体の乳化組成物は、例えば、水と油のように、互いに殆ど溶解しない二種の液体の乳化物（即ちエマルション）又は互いに混ざり合わない二種の液体の乳化物（即ちエマルション）を意味する。このような乳化組成物としては、化学薬品、医薬品、化粧品、食品，化成品若しくは農薬の乳化物（即ちエマルション）があり、さらに詳しくは、化学薬品、医薬品、化粧品、食品，化成品若しくは農薬における水中油型乳化物（エマルション）又は油中水型乳化物（エマルション）がある。
乳化組成物が、乳化油脂組成物である場合には、化学薬品、医薬品、化粧品、食品，化成品若しくは農薬における水中油型油脂乳化組成物又は油中水型乳化油脂組成物がある。
本発明は、予備乳化油脂組成物を、油相部と水相部から乳化剤を用いて予め製造し、この製造された予備乳化油脂組成物を均一な孔径を有する多孔質乳化膜を通過させて、再乳化させることにより乳化油脂組成物を製造する。
【０００８】
本発明においては、乳化油脂組成物を製造する場合に、再乳化の際に通過させる均一な孔径を有する多孔質乳化膜の孔径に対して２０倍を超える平均粒子径の粒子を有する予備乳化油脂組成物を、０．１ＭＰａ以上の圧力をかけながら、前記均一な孔径を有する多孔質乳化膜を通過させて、前記乳化膜の孔径に対して１倍未満の平均粒子径を有する乳化油脂組成物を製造し、また、この場合に、本発明においては、再乳化の際に通過させる均一な孔径を有する多孔質乳化膜の孔径に対して２０倍を超える平均粒子径を有する予備乳化油脂組成物を、１％以下の濃度で乳化剤を含む外相部と内相部から予め製造し、この製造された予備乳化油脂組成物を、０．１ＭＰａ以上の圧力をかけながら、前記均一な孔径を有する多孔質乳化膜を通過させて、前記乳化膜の孔径に対して１倍未満の平均粒子径を有する乳化油脂組成物を製造する。
【０００９】
本発明においては、予備乳化油脂組成物を含めて予備乳化組成物は、第一の液相部と第一の液相部に溶け合わない第二の液相部の予備乳化組成物を乳化剤の存在下に、例えば、攪拌器、コロイドミル、ホモジナイザーその他の液々混合機により攪拌混合又は高速攪拌混合することにより製造することができる。予備乳化組成物が予備乳化油脂組成物である場合は、油相及び水相の混合液を、乳化剤を使用して慣用の乳化方法、例えば、攪拌器、コロイドミル、ホモジナイザーその他の液々混合機により攪拌混合又は高速攪拌混合することにより製造することができる。この予備乳化組成物を製造する場合にも、膜処理により製造することができる。
【００１０】
乳化組成物にあっては、第一の液相部及び第二の液相部の何れか一方若しくは双方に乳化剤である界面活性剤を添加混合することにより、第一の液相部を第二の液相部内に、若しくは、第二の液相部を第一の液相部内に分散させて、予備乳化組成物を製造することができる。また乳化油脂組成物にあっては、水相又は油相の何れか一方又は双方に、乳化剤である界面活性剤を添加混合することにより、油相を水相内に、又は、水相を油相内に分散させて、予備乳化油脂組成物を製造することができる。
【００１１】
このような乳化剤である界面活性剤としては、陰イオン界面活性剤又は非イオン界面活性剤を使用することが出来る。例えば、ドデシル硫酸ナトリウム（ＳＤＳ）、ポリオキシエチレン硬化ひまし油（ＨＣＯ６０）、ポリグリセリン脂肪酸エステル（Ｑ１８Ｓ）、縮合リシノレイン酸エステル（ＰＧＣＲ）などを使用することができる。例えば、医薬、食品及び化粧品等において、乳化油脂組成物中に使用される乳化剤の量は少ないのが好ましい。
【００１２】
そこで、本発明においては、使用する乳化剤は、外相若しくは内相(分散相)又は外相及び内相に添加することができる。例えば、乳化油脂組成物において、乳化剤を、外相(連続相)に添加する場合には、１重量％以下の量で添加するのが好ましく、更に好ましくは、外相に、０．５重量％以下の量で添加されるのが好ましい。例えば、水中油型乳化油脂組成物の場合は、添加される乳化剤は水相に添加されるのが好ましく、水相にその量は、１重量％以下、好ましくは、０．７重量％以下、さらに好ましくは０．５重量％以下である。そのように、乳化油脂組成物中に使用される乳化剤の量を少なくするためにも、そのＨＬＢは、１０．０以上のものであるのが好ましい。本発明において、予備乳化組成物は、複数回に亘って予備乳化されてもよく、この場合は、予備乳化組成物の分散粒子の粒径を、予備乳化の回数毎に段階的に小さくすることができる。
【００１３】
本発明において、乳化膜として使用される多孔質膜としては、シラス多孔質ガラス製の乳化膜(以下、ＳＰＧ乳化膜という)を使用することができるが、その他に，限外濾過膜等の膜処理に一般に使用される膜を使用することができる。再乳化に使用される多孔質膜である乳化膜は、予備乳化組成物の通過の態様に応じて、管状，平板状等の種々の形状に形成することができる。本発明において、予備乳化組成物の再乳化は、乳化膜により区分された室の一方に予備乳化組成物を入れて、予備乳化組成物に、例えば、該室内に窒素ガス等の不活性ガス圧力により又はポンプ若しくはプランジャー等の機械的圧力により圧力をかけて、予備乳化組成物を、多孔質膜を通して、他方の室に押し出すことにより、再乳化することができる。
【００１４】
再乳化の際に、予備乳化成物に加えられる圧力は、例えば、予備乳化油脂組成物の場合で、０．１ＭＰａ（１ｋｇｆ／ｃｍ２）以上であるのが好ましい。しかし、予備乳化組成物の平均粒子径が多孔質膜の孔径に対して２０倍を超えて再乳化するときは、予備乳化組成物に加えられる圧力は、１ＭＰａ以上とするのが好ましい。しかし、多孔質膜の孔径が大きいほど、膜を通過する予備乳化組成物に加えられる圧力は、小さくすることができる。予備乳化組成物を再乳化する場合に、再乳化処理を複数回例えば二段階に分けて行うことができる。この場合は、最初の再乳化処理圧力に比して、後続の再乳化処理圧力を低くすることができるので好ましい。
【００１５】
本発明において、攪拌混合等により、再乳化に先立って予備乳化された乳化組成物の分散粒子径を、再乳化の際に通される多孔質膜の孔径に対して20倍を超える大きさに形成すると、再乳化の乳化操作が容易となって、好ましい。
【００１６】
【実施例】
以下に、本発明の実施例を説明するが、本発明は以下の例示及び説明により、何ら限定されるものではない。
例1．
本例は、食品用の水中油型の乳化油脂組成物の例である。本例において、予備乳化機として、ホモジナイザー（ウルトラタラックスＴ２５：商品名、株式会社井内盛栄堂製）を使用した。このホモジナイザーの混合槽内に、水相部のポリグリセリン脂肪酸エステルの２％水溶液７５重量部を入れ、この水相部に、油相部の縮合リシノレイン酸エステル１％を含有する大豆油２５重量部を加えて、回転子を回転数９５００ｒｐｍで１分間回転させて予備乳化した。この予備乳化により得られた予備乳化油脂組成物は、大豆油を内相とし、水を外相とする水中油型の乳化油脂組成物であり、内相は２５％であり、その内相粒子の平均粒子径は４８．７４μｍであった。本例における予備乳化油脂組成物の平均粒子径は、予備乳化油脂組成物の再乳化処理の際に通過するＳＰＧ乳化膜の孔径２．４μｍに対して２０．３倍であり，予備乳化粒子の単分散係数(σ)は、０．９０であった。
この予備乳化油脂組成物を、直径１０ｍｍ，長さ１００ｍｍ及び厚さが1ｍｍで、平均孔径が２．４μｍの円筒状ＳＰＧ乳化膜を備える清本鐵工株式会社製の乳化装置を使用して再乳化した。この予備乳化油脂組成物を、前記ＳＰＧ乳化膜を通過させる押し出しは窒素ガスの圧力によった。本例において、このＳＰＧ乳化膜を通過させるための窒素ガスの押出し圧力は、１．５ＭＰａであり、ＳＰＧ乳化膜を通る予備乳化油脂組成物の流速は、通過面積２５ｃｍ２あたり、３５ｍｌ／秒であった。再乳化された乳化油脂組成物においては、その平均粒子径は２．３７μｍであって、前記ＳＰＧ乳化膜の孔径２．４μｍに対して０．９９倍であり，その再乳化粒子の単分散係数（σ）は、０．５４であった。ここで、単分散係数(σ)は、
式：
単分散係数(σ)＝（粒径の小さい方からの粒子分布量の積算値が９０重量％
の粒径と、粒径の小さい方からの粒子分布量の積算値が
１０重量％の粒径との差）÷（粒径の小さい方からの粒
子分布量の積算値が５０重量％の粒径）
により与えられる。
【００１７】
例２．
本例は、医薬品用の水中油型の乳化油脂組成物の例である。本例において、予備乳化機として、ホモジナイザー（ウルトラタラックスＴ２５：商品名、株式会社井内盛栄堂製）を使用した。このホモジナイザーの混合槽内に、水相部の、ＮａＣｌの０．３％水溶液及びポリオキシエチレン硬化ひまし油の１％水溶液の混合溶液８７．５重量部を入れた。この水相部に、油相部の大豆油１２．５重量部を加えて、回転子を回転数９５００ｒｐｍで１分間回転させて予備乳化した。この予備乳化により得られた予備乳化油脂組成物は、大豆油を内相とし、水を外相とする水中油型の乳化油脂組成物であり、内相は１２．５重量％であり、その内相粒子の平均粒子径は５９．４４μｍであった。この予備乳化油脂組成物の平均粒子径は、予備乳化油脂組成物の再乳化処理の際に通過するＳＰＧ乳化膜の孔径０．９４μｍに対して６３．２倍であり，その予備乳化粒子の単分散係数（σ）は、１．００であった。
この予備乳化油脂組成物を、直径１０ｍｍ，長さ１００ｍｍ及び厚さ1ｍｍで、平均孔径が０．９４μｍの円筒状ＳＰＧ乳化膜を備える清本鐵工株式会社製の乳化装置を使用して再乳化した。この予備乳化油脂組成物が、前記ＳＰＧ乳化膜を通過する押し出しは窒素ガスの圧力によった。本例において、このＳＰＧ乳化膜を通過させるための窒素ガスの押出し圧力は、３．００ＭＰａであり、ＳＰＧ乳化膜を通る予備乳化油脂組成物の流速は、通過面積２５ｃｍ２あたり、２．７ｍｌ／秒であった。再乳化された乳化油脂組成物においては、その平均粒子径は０．９２μｍであって、前記ＳＰＧ乳化膜の孔径０．９４μｍに対して０．９８倍であり、その再乳化粒子の単分散係数（σ）は、０．５５であった。
【００１８】
例３．
本例は、化成品用の水中油型の乳化油脂組成物の例である。本例において、予備乳化機として、ハイパワースターラＨＰＳ−１００ (商品名：株式会社井内盛栄堂製)を使用した。このスターラの混合槽内に、水相部のドデシル硫酸ナトリウム０．２％水溶液の５０重量部を入れ、この水相部に、油相部の菜種油５０重量部を加えて、回転子を回転数８００ｒｐｍで５分間回転させて予備乳化した。この予備乳化により得られた予備乳化油脂組成物は、菜種油を内相とし、水を外相とする水中油型の乳化油脂組成物であり、内相は５０％であり、その内相粒子の平均粒子径は８６．３６μｍであった。この予備乳化油脂組成物の平均粒子径は、予備油脂乳化組成物の再乳化処理の際に通過するＳＰＧ乳化膜の孔径３．２μｍに対して２７．０倍であり、その予備乳化粒子の単分散係数(σ)は、１．４０であった。
この予備乳化油脂組成物を、直径１０ｍｍ，長さ１００ｍｍ及び厚さ1ｍｍで、平均孔径が３．２μｍの円筒状ＳＰＧ乳化膜を備える清本鐵工株式会社製の乳化装置を使用して再乳化した。予備乳化油脂組成物を、前記ＳＰＧ乳化膜を通過させる押し出しは窒素ガスの圧力によった。本例において、このＳＰＧ乳化膜を通過させるための窒素ガスの押出し圧力は、１．０ＭＰａであり、前記ＳＰＧ乳化膜を通過する流速は、通過面積２５ｃｍ２あたり、毎秒５．０ｍｌであった。再乳化された乳化油脂組成物においては、その平均粒子径は２．９３μｍであって、前記ＳＰＧ乳化膜の孔径に対して０．９２倍であり、その再乳化粒子の単分散係数（σ）は、０．６０であった。
【００１９】
例４．
本例は、化成品用の水中油型の乳化油脂組成物の例である。本例において、予備乳化機として、ハイパワースターラＨＰＳ−１００(商品名：株式会社井内盛栄堂製)を使用した。このスターラの混合槽内に、水相部のドデシル硫酸ナトリウム０．２％水溶液の５０重量部を入れ、この水相部に、油相部の菜種油５０重量部を加えて、回転子を回転数８００ｒｐｍで５分間回転させて予備乳化した。この予備乳化により得られた予備乳化油脂組成物は、菜種油を内相とし、水を外相とする水中油型の乳化油脂組成物であり、内相は５０％であり、外相は５０％であり、その内相粒子の平均粒子径は７７．８３μｍであった。予備油脂乳化組成物の再乳化処理の際に通過するこの予備乳化油脂組成物の平均粒子径は、予備油脂乳化組成物の再乳化処理の際に通過するＳＰＧ乳化膜の孔径３．２μｍに対して２４．３倍であり，その予備乳化粒子の単分散係数(σ)は、１．６０であった。
この予備乳化油脂組成物を、直径１０ｍｍ，長さ１００ｍｍ及び厚さ1ｍｍで、平均孔径が３．２μｍの円筒状ＳＰＧ乳化膜を備える清本鐵工株式会社製の乳化装置を使用して再乳化した。予備乳化油脂組成物を前記ＳＰＧ乳化膜を通過させる押し出しは窒素ガスの圧力によった。本例において、このＳＰＧ乳化膜を通過させるための窒素ガスの押出し圧力は、１．５ＭＰａで、予備油脂乳化組成物が前記ＳＰＧ乳化膜を通過する流速は、通過面積２５ｃｍ２あたり、毎秒１５．０ｍｌであった。再乳化された乳化油脂組成物においては、その平均粒子径は２．４９μｍであって、前記ＳＰＧ乳化膜の孔径の３．２μｍに対して０．７８倍であり、その再乳化粒子の単分散係数(σ)は、０．６０である。
【００２０】
例５．
本例は、化成品用の水中油型の乳化油脂組成物の例である。本例において、予備乳化機として、ハイパワースターラＨＰＳ−１００ (商品名：株式会社井内盛栄堂製)を使用した。このスターラの混合槽内に、水相部のドデシル硫酸ナトリウム０．２％水溶液の５０重量部を入れ、この水相部に、油相部の、縮合リシノレイン酸エステル５％を含む菜種油５０重量部を加えて、回転子を回転数１０００ｒｐｍで１０分間回転させて予備乳化した。この予備乳化により得られた予備乳化油脂組成物は、菜種油を内相とし、水を外相とする水中油型の乳化油脂組成物であり、内相は５０％であり、外相は５０％であり、その内相粒子の平均粒子径は６９．３８μｍであった。この予備乳化油脂組成物の平均粒子径は、予備油脂乳化組成物の再乳化処理の際に通過するＳＰＧ乳化膜の孔径０．９４μｍに対して７３．８倍であり，予備乳化粒子の単分散係数（σ）は、１．４４であった。
この予備乳化油脂組成物を、直径１０ｍｍ，長さ１００ｍｍ及び厚さ1ｍｍで、平均孔径が０．９４μｍの円筒状ＳＰＧ乳化膜を備える清本鐵工株式会社製の乳化装置を使用して再乳化した。この予備乳化油脂組成物の再乳化について、前記ＳＰＧ乳化膜を通過させる押し出しは窒素ガスの圧力によった。本例において、このＳＰＧ乳化膜を通過させるための窒素ガスの押出し圧力は、３．０ＭＰａであり、前記ＳＰＧ乳化膜を通過する流速は、通過面積２５ｃｍ２あたり、毎秒１．５ｍｌであった。再乳化された乳化油脂組成物においては、その平均粒子径は０．９３μｍであって、前記ＳＰＧ乳化膜の孔径０．９４μｍに対して０．９９倍であり、その再乳化粒子の単分散係数(σ)は、０．５４である。
【００２１】
例６．
本例は、化成品用の水中油型の乳化油脂組成物の例である。本例において、予備乳化機として、ハイパワースターラＨＰＳ−１００ (商品名：株式会社井内盛栄堂製)を使用した。このスターラの混合槽内に、水相部のドデシル硫酸ナトリウム０．２％水溶液の９０重量部を入れ、この水相部に、油相部の菜種油１０重量部を加えて、回転子を回転数１６００ｒｐｍで１０分間回転させて予備乳化した。この予備乳化により得られた予備乳化油脂組成物は、菜種油を内相とし、水を外相とする水中油型の乳化油脂組成物であり、内相は１０％であり、外相は９０％であり、その内相粒子の平均粒子径は９６．８４μｍであった。この予備乳化油脂組成物の平均粒子径は、予備油脂乳化組成物の再乳化処理の際に通過するＳＰＧ乳化膜の孔径０．９４μｍに対して１０３．０倍であり，予備乳化粒子の単分散係数(σ)は、０．９６であった。
この予備乳化油脂組成物を、直径１０ｍｍ，長さ１００ｍｍ及び厚さ1ｍｍで、平均孔径が０．９４μｍの円筒状ＳＰＧ乳化膜を備える清本鐵工株式会社製の乳化装置を使用して再乳化した。この予備乳化油脂組成物について前記ＳＰＧ乳化膜を通過させる押し出しは窒素ガスの圧力によった。本例において、このＳＰＧ乳化膜を通過させるための窒素ガスの押出し圧力は、３．５０ＭＰａであり、前記ＳＰＧ乳化膜を通過する流速は、通過面積２５ｃｍ２あたり、毎秒８．６ｍｌであった。再乳化された乳化油脂組成物においては、その平均粒子径は０．９２μｍであって、前記ＳＰＧ乳化膜の孔径０．９４μｍに対して０．９８倍であり、その再乳化粒子の単分散係数（σ）は、０．５４である。
【００２２】
例７．
本例は、水中油型の乳化油脂組成物の例である。本例において、予備乳化機として、ホモジナイザー（ウルトラタラックスＴ２５：商品名、株式会社井内盛栄堂製）を使用した。このホモジナイザーの混合槽内に、水相部の、ＮａＣｌの０．３％水溶液及びポリオキシエチレン硬化ひまし油の１％水溶液の混合溶液８７．５重量部を入れた。この水相部に、油相部の大豆油１２．５重量部を加えて、回転子を回転数８０００ｒｐｍで２分間回転させて予備乳化した。この予備乳化により得られた予備乳化油脂組成物は、大豆油を内相とし、水を外相とする水中油型の乳化油脂組成物であり、内相は１２．５％であり、その内相粒子の平均粒子径は９７．４２μｍであった。この予備乳化油脂組成物の平均粒子径は、予備乳化油脂組成物の再乳化処理の際に通過するＳＰＧ乳化膜の孔径３．２μｍに対して３０．４倍であり，その予備乳化粒子の単分散係数(σ)は、０．７８であった。
この予備乳化油脂組成物を、直径１０ｍｍ，長さ１００ｍｍ及び厚さ1ｍｍで、平均孔径が３．２μｍの円筒状ＳＰＧ乳化膜を備える清本鐵工株式会社製の乳化装置を使用して再乳化した。この予備乳化油脂組成物が、前記ＳＰＧ乳化膜を通過する押し出しは窒素ガスの圧力によった。本例において、このＳＰＧ乳化膜を通過させるための窒素ガスの押出し圧力は、１．２０ＭＰａであった。再乳化された乳化油脂組成物の平均粒子径は２．８９μｍであって、前記ＳＰＧ乳化膜の孔径３．２μｍに対して０．９０倍であり、その再乳化粒子の単分散係数(σ)は、０．５５であった。
【００２３】
以上の実施例において、ドデシル硫酸ナトリウムは、親水性の界面活性剤であり、和光純薬工業株式会社製のものを使用した。ポリオキシエチレン硬化ひまし油は、親水性の界面活性剤であり、日光ケミカルス株式会社製のものを使用した。ポリグリセリン脂肪酸エステルは、親水性の界面活性剤であり、太陽化学株式会社製のものを使用した。縮合リシノレイン酸エステルは、疎水性の界面活性剤であり、阪本薬品工業株式会社製のものを使用した。大豆油及び菜種油は、夫々、市販の精製品を使用した。水は蒸留水製造装置により製造された市販の蒸留水、例えばヤマト科学株式会社製のものを使用した。ＮａＣｌは、市販の試薬特級の塩化ナトリウム、例えば、和光
純薬工業株式会社製のものを使用した。また、ＳＰＧ乳化膜は、ＳＰＧテクノ株式会社製のものを使用した。また、以上の実施例において、乳化油脂組成物中の分散粒子の粒度分布測定は、島津製作所製のレーザー
回折式粒度分布測定装置ＳＡＬＤ−２０００Ｊを使用して測定した。
【００２４】
【発明の効果】
本発明は、再乳化の際に通過させる均一な孔径を有する多孔質乳化膜の孔径に対して２０倍を超える平均粒子径を有する予備乳化組成物を、乳化剤を含む外相部と内相部とから予め製造し、この製造された予備乳化組成物を、０．１ＭＰａ以上の圧力をかけながら、前記均一な孔径を有する多孔質乳化膜を通過させて、前記乳化膜の孔径に対して１倍未満の平均粒子径を有する乳化組成物、例えば乳化油脂組成物を製造するので、従来の乳化膜を使用して困難とされていた、例えば１μｍより小さい平均粒径の分散粒子を有する乳化組成物を製造することを可能にすると共に、乳化剤の使用量を少なくして、粒子径分布が狭い範囲内にある均一な分散粒子を有する乳化組成物を製造することを可能とするものである。また本発明は、従来法に比して、微細で均一な分散粒子を有する乳化組成物例えば乳化油脂組成物を、乳化剤の含有量を少なくして製造できるものであり、化学薬品、医薬、食品、化粧品及び農薬の分野において、その果たす影響は大きく、産業上有用である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing two liquid emulsions or emulsion compositions that are hardly soluble in each other, and more particularly, to a method for producing an oil-in-water emulsion composition or a water-in-oil emulsion composition. The present invention also relates to an emulsified oil / fat composition, and more particularly to a method for producing an oil-in-water emulsified oil / fat composition or a water-in-oil emulsified oil / fat composition. Furthermore, the present invention relates to a method for producing an emulsified composition of a chemical, and particularly relates to a method of producing an oil-in-water emulsion composition or a water-in-oil emulsified fat composition of a chemical. Furthermore, the present invention relates to a method for producing an emulsified composition of a pharmaceutical product, and particularly relates to a method for producing an oil-in-water emulsion composition or a water-in-oil emulsion composition of a pharmaceutical product. Furthermore, the present invention relates to a method for producing a cosmetic emulsified oil / fat composition, and more particularly to a method for producing a cosmetic oil-in-water emulsified oil / fat composition or a water-in-oil emulsified oil / fat composition. Furthermore, the present invention relates to a method for producing an emulsified oil / fat composition for beverages and foods, and particularly relates to a method for producing an oil-in-water emulsified oil / fat composition or water-in-oil emulsified oil / fat composition for beverages and foods. In addition, the present invention relates to a method for producing an agrochemical oil-in-water emulsion composition or a water-in-oil emulsion composition. The present invention relates to a method for producing an emulsified composition such as an emulsified oil composition having a narrow particle size distribution and a very uniform particle size.
[0002]
[Prior art]
The emulsified oil / fat composition is, for example, in cosmetics, an oil-in-water emulsion emulsion such as an emulsion lotion in which a sebum component is emulsified, an emulsion, a vanishing cream, a cold cream, or a water-in-oil cold cream, There are water-in-oil emulsions such as nutritional creams. Also in medicine, there are oil-in-water and water-in-oil emulsions and emulsion ointments in which the main agent is emulsified. In food, there are many emulsion products such as mayonnaise, margarine, cream and ice cream, in which edible fats and oils are emulsified. Also in the field of agrochemicals, oil-in-water and water-in-oil emulsion emulsions are used as agrochemicals. In order to produce such an emulsion, it is necessary to make the dispersed phase fine and stabilize the fine dispersed phase.
[0003]
Recently, by using a porous glass membrane, it is possible to easily prepare an emulsion in which inner phase particles are very uniform. Manufactured by a porous membrane such as a membrane.
As a method for producing an emulsified oil / fat composition having an average particle diameter of 10 μm or less using a porous film having such a uniform pore diameter, the pore diameter of the porous film to be re-emulsified is used. On the other hand, a pre-emulsified oil / fat composition having an average particle size of 1 to 20 times is prepared in advance using an emulsifier from an oil phase part and an aqueous phase part, and the pre-emulsified oil / fat composition has a uniform pore size. There has been proposed a method for producing an emulsified oil / fat composition having an average particle size of 1 to 3 times the pore size of the porous membrane by re-emulsifying by passing through the membrane.
[0004]
[Problems to be solved by the invention]
However, in the above method for producing an emulsified oil / fat composition, an emulsified oil / fat composition having a particle diameter of 1 to 3 times the pore diameter of the porous film to be passed, that is, the pore diameter of the emulsified film is produced. In addition, the emulsified oil composition having an average particle size of 20 times or more the pore size of the emulsified membrane has a large rate of change in the flow characteristics with respect to the shear stress. Can not pass. When emulsified, the emulsified particles are deformed, and a uniform emulsified oil / fat composition cannot be obtained, and an emulsified oil / fat composition in a state where the oil phase and the aqueous phase are separated is obtained. Therefore, it is necessary to prepare in advance a pre-emulsified oil / fat composition having an average particle size of 1 to 20 times the pore size of the emulsified membrane. Yes.
Moreover, the average particle diameter of the emulsified oil / fat composition obtained by re-emulsifying the pre-emulsified oil / fat composition having an average particle diameter of 1 to 20 times the pore diameter of the emulsified film with the emulsified film passes when re-emulsified. The emulsified fat composition has an average particle size smaller than the pore size of the porous membrane that is finer, that is, passed through when re-emulsified. Since the average particle size of the dispersed phase particles of the resulting emulsified oil / fat composition is limited by the pore size of the porous membrane that passes in the process of re-emulsification, it is considered a problem. Yes.
Moreover, in the emulsified oil / fat composition, if the amount of the surfactant used is large, for example, use in chemicals, pharmaceuticals, cosmetics, foods, agricultural chemicals and the like is restricted, which is a problem.
An object of the present invention is to solve the problems associated with the refinement of dispersed phase (inner phase) particles in a conventional method for producing an emulsified oil composition using a porous membrane.
[0005]
[Means for Solving the Problems]
The inventors of the present invention pass an emulsified composition such as a pre-emulsified oil composition with a small amount of emulsifier through a porous membrane having a uniform pore size, and emulsify having an average particle size smaller than the pore size of the porous membrane. It was discovered that a composition can be produced, leading to the present invention.
The present invention relates to an emulsion composition capable of producing an emulsion composition such as an emulsion composition having an average particle size of less than 1 times the pore size of the porous membrane that is passed when re-emulsifying. The object is to provide a manufacturing method.
Further, the present invention provides an emulsified composition having an average particle size of less than 1 time with respect to the pore size of the porous membrane that is passed when re-emulsifying, and the amount of emulsifier used is an amount of 1% by weight or less, It aims at providing the manufacturing method of the emulsion composition which can be manufactured.
[0006]
That is, in the present invention, two types of preliminarily emulsified compositions that do not dissolve each other are produced in advance using an emulsifier, and the produced preliminarily emulsified composition is passed through a porous emulsion membrane having a uniform pore size, In the method for producing an emulsion composition for producing an emulsion composition having an average particle diameter of 10 μm or less by re-emulsification, the pore diameter of the porous emulsion film having a uniform pore diameter of 5 μm or less that is passed during re-emulsification A pre-emulsified composition having an average particle diameter of more than 20 times and a dispersed phase concentration of 10 to 50% by weight.1A porous emulsified membrane having a uniform pore size of 5 μm or less is applied with a passage area of 25 cm while applying a pressure of MPa or more.21.5 to35The emulsion composition having an average particle diameter of less than 1 time with respect to the pore diameter of the emulsion film and having a monodispersion coefficient of 0.6 or less is passed through at a passage speed of ml / second. In the method for producing an emulsified composition, and in the present invention, two kinds of liquid pre-emulsified compositions that are not soluble in each other are produced in advance using an emulsifier, and the produced pre-emulsified composition is obtained with a uniform pore size. In a method for producing an emulsified composition having an average particle size of 10 μm or less by passing through a porous emulsified membrane and re-emulsified, a uniform of 5 μm or less that is allowed to pass during re-emulsification An outer phase part containing a pre-emulsified composition having an average particle size exceeding 20 times the pore size of a porous emulsion membrane having a pore size and a dispersed phase concentration of 10 to 50% by weight and containing an emulsifier at a concentration of 1% or less And pre-manufactured from the internal phase, this The pre-emulsified composition obtained was1While applying a pressure of MPa or more, the porous emulsified membrane having a uniform pore size of 5 μm or less was passed through a passage area of 25 cm.21.5 to35The emulsion composition having an average particle diameter of less than 1 time with respect to the pore diameter of the emulsion film and having a monodispersion coefficient of 0.6 or less is passed through at a passage speed of ml / second. It exists in the manufacturing method of an emulsion composition.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, the two liquid emulsion compositions that do not dissolve each other are, for example, two liquid emulsions (that is, emulsions) that hardly dissolve each other, such as water and oil, or two liquids that do not mix with each other. An emulsion (i.e., an emulsion). Such emulsified compositions include emulsions (ie, emulsions) of chemicals, pharmaceuticals, cosmetics, foods, chemicals or agricultural chemicals (ie, emulsions), and more particularly in chemicals, pharmaceuticals, cosmetics, foods, chemicals or agricultural chemicals. There are oil-in-water emulsions (emulsions) or water-in-oil emulsions (emulsions).
When the emulsified composition is an emulsified oil / fat composition, there is an oil-in-water oil / fat emulsified composition or a water-in-oil emulsified oil / fat composition in chemicals, pharmaceuticals, cosmetics, foods, chemicals or agricultural chemicals.
In the present invention, a pre-emulsified oil / fat composition is produced in advance using an emulsifier from an oil phase part and an aqueous phase part, and the produced pre-emulsified oil / fat composition is passed through a porous emulsion film having a uniform pore size. An emulsified oil / fat composition is produced by re-emulsification.
[0008]
In the present invention, when an emulsified oil / fat composition is produced, a pre-emulsified oil / fat having particles having an average particle diameter exceeding 20 times the pore diameter of a porous emulsion film having a uniform pore diameter to be passed during re-emulsification An emulsified oil / fat composition having an average particle diameter of less than 1 times the pore diameter of the emulsified film by passing the composition through the porous emulsified film having the uniform pore diameter while applying a pressure of 0.1 MPa or more. In this case, in the present invention, the pre-emulsified oil / fat composition having an average particle size exceeding 20 times the pore size of the porous emulsion membrane having a uniform pore size to be passed during re-emulsification Is prepared in advance from an outer phase part and an inner phase part containing an emulsifier at a concentration of 1% or less, and the prepared pre-emulsified fat composition is applied with a pore having the uniform pore diameter while applying a pressure of 0.1 MPa or more. Pass through the emulsified membrane , To produce the emulsified oil composition having an average particle size of less than 1 times the pore size of the emulsion layer.
[0009]
In the present invention, the pre-emulsified composition, including the pre-emulsified oil / fat composition, is prepared by using the pre-emulsified composition of the second liquid phase part that does not dissolve in the first liquid phase part and the first liquid phase part. In the presence, it can be produced, for example, by stirring and mixing or high-speed stirring and mixing with a stirrer, colloid mill, homogenizer or other liquid-liquid mixer. When the pre-emulsified composition is a pre-emulsified oil / fat composition, the mixture of the oil phase and the aqueous phase is mixed with a conventional emulsification method using an emulsifier, for example, a stirrer, a colloid mill, a homogenizer or other liquid mixer. Can be produced by stirring and mixing at a high speed. Even when this pre-emulsified composition is produced, it can be produced by membrane treatment.
[0010]
In the emulsified composition, a surfactant as an emulsifier is added to and mixed with one or both of the first liquid phase part and the second liquid phase part, whereby the first liquid phase part is changed to the second liquid phase part. In this liquid phase part or the second liquid phase part can be dispersed in the first liquid phase part to prepare a pre-emulsified composition. In addition, in the emulsified oil / fat composition, a surfactant as an emulsifier is added to and mixed with either or both of the aqueous phase and the oil phase, so that the oil phase is contained in the aqueous phase or the aqueous phase is oil. It can be dispersed in the phase to produce a pre-emulsified oil / fat composition.
[0011]
As the surfactant which is such an emulsifier, an anionic surfactant or a nonionic surfactant can be used. For example, sodium dodecyl sulfate (SDS), polyoxyethylene hydrogenated castor oil (HCO 60), polyglycerin fatty acid ester (Q18S), condensed ricinoleic acid ester (PGCR) and the like can be used. For example, in medicine, food, cosmetics, etc., it is preferable that the amount of emulsifier used in the emulsified oil / fat composition is small.
[0012]
Therefore, in the present invention, the emulsifier to be used can be added to the external phase or the internal phase (dispersed phase) or the external phase and the internal phase. For example, in an emulsified oil and fat composition, when an emulsifier is added to the outer phase (continuous phase), it is preferably added in an amount of 1% by weight or less, more preferably 0.5% by weight or less in the outer phase. Preferably it is added in an amount. For example, in the case of an oil-in-water emulsified oil and fat composition, the added emulsifier is preferably added to the aqueous phase, and the amount in the aqueous phase is 1% by weight or less, preferably 0.7% by weight or less, More preferably, it is 0.5 wt% or less. As such, the amount of emulsifier used in the emulsified oil compositionTheIn order to reduce the HLB, the HLB is preferably 10.0 or more. In the present invention, the pre-emulsified composition may be pre-emulsified a plurality of times. In this case, the particle size of the dispersed particles of the pre-emulsified composition is reduced stepwise for each number of pre-emulsifications. Can do.
[0013]
In the present invention, as a porous membrane used as an emulsifying membrane, an emulsified membrane made of shirasu porous glass (hereinafter referred to as SPG emulsified membrane) can be used, but in addition, a membrane such as an ultrafiltration membrane. Membranes commonly used for processing can be used. The emulsified membrane, which is a porous membrane used for re-emulsification, can be formed into various shapes such as a tubular shape and a flat plate shape according to the mode of passage of the pre-emulsified composition. In the present invention, the re-emulsification of the pre-emulsified composition is carried out by putting the pre-emulsified composition in one of the chambers separated by the emulsified membrane, and then in the pre-emulsified composition, for example, an inert gas pressure such as nitrogen gas in the chamber. Or by a mechanical pressure such as a pump or a plunger to re-emulsify the pre-emulsified composition through the porous membrane and into the other chamber.
[0014]
The pressure applied to the pre-emulsified composition at the time of re-emulsification is, for example, 0.1 MPa (1 kgf / cm in the case of the pre-emulsified oil / fat composition).2) Or more. However, when the average particle size of the pre-emulsified composition exceeds 20 times the pore size of the porous membrane and is re-emulsified, the pressure applied to the pre-emulsified composition is preferably 1 MPa or more. However, the larger the pore size of the porous membrane, the smaller the pressure applied to the pre-emulsified composition that passes through the membrane. When the pre-emulsified composition is re-emulsified, the re-emulsification treatment can be performed a plurality of times, for example, in two stages. In this case, it is preferable because the subsequent re-emulsification processing pressure can be made lower than the initial re-emulsification processing pressure.
[0015]
In the present invention, the dispersed particle size of the emulsified composition pre-emulsified prior to re-emulsification by stirring and mixing, etc., is larger than 20 times the pore size of the porous membrane passed during re-emulsification. When formed, the emulsification operation of re-emulsification becomes easy, which is preferable.
[0016]
【Example】
Examples of the present invention will be described below, but the present invention is not limited to the following examples and explanations.
Example 1.
This example is an example of an oil-in-water emulsified fat composition for food. In this example, a homogenizer (Ultra Turrax T25: trade name, manufactured by Inoue Seieido Co., Ltd.) was used as a preliminary emulsifier. In this homogenizer mixing tank, 75 parts by weight of a 2% aqueous solution of polyglycerin fatty acid ester in the aqueous phase is placed, and 25 parts by weight of soybean oil containing 1% of condensed ricinoleate in the oil phase is added to the aqueous phase. Was added, and the rotor was rotated at 9500 rpm for 1 minute for preliminary emulsification. The pre-emulsified oil / fat composition obtained by this pre-emulsification is an oil-in-water emulsified oil / fat composition having soybean oil as the internal phase and water as the external phase, the internal phase being 25%, The average particle size was 48.74 μm. The average particle size of the pre-emulsified oil / fat composition in this example is 20.3 times the pore size of 2.4 μm of the SPG emulsified membrane that passes during the re-emulsification treatment of the pre-emulsified oil / fat composition. The monodispersion coefficient (σ) was 0.90.
This pre-emulsified oil / fat composition was re-used using an emulsifier manufactured by Kiyomoto Seiko Co., Ltd. equipped with a cylindrical SPG emulsion membrane having a diameter of 10 mm, a length of 100 mm, a thickness of 1 mm, and an average pore diameter of 2.4 μm. Emulsified. The extrusion of the pre-emulsified oil / fat composition through the SPG emulsion film was performed by the pressure of nitrogen gas. In this example, the extrusion pressure of the nitrogen gas for passing through the SPG emulsion film is 1.5 MPa, and the flow rate of the pre-emulsified oil and fat composition passing through the SPG emulsion film has a passage area of 25 cm.2It was 35 ml / sec. In the re-emulsified emulsified oil / fat composition, the average particle size is 2.37 μm, which is 0.99 times the pore size of 2.4 μm of the SPG emulsified membrane, and the monodispersion coefficient of the re-emulsified particles (Σ) was 0.54. Where the monodispersion coefficient (σ) is
formula:
Monodispersion coefficient (σ) = (The integrated value of the particle distribution from the smaller particle size is 90% by weight.
And the integrated value of the particle distribution from the smaller particle size is
Difference from the particle size of 10% by weight) / (grains from smaller particle size)
Particle size with integrated value of 50% by weight
Given by.
[0017]
Example 2.
This example is an example of an oil-in-water emulsified oil and fat composition for pharmaceuticals. In this example, a homogenizer (Ultra Turrax T25: trade name, manufactured by Inoue Seieido Co., Ltd.) was used as a preliminary emulsifier. In this homogenizer mixing tank, 87.5 parts by weight of a mixed solution of a 0.3% aqueous solution of NaCl and a 1% aqueous solution of polyoxyethylene hydrogenated castor oil in the aqueous phase was placed. To this aqueous phase portion, 12.5 parts by weight of soybean oil in the oil phase portion was added, and the rotor was pre-emulsified by rotating at a rotational speed of 9500 rpm for 1 minute. The pre-emulsified oil / fat composition obtained by this pre-emulsification is an oil-in-water emulsified oil / fat composition having soybean oil as the internal phase and water as the external phase, and the internal phase is 12.5% by weight. The average particle size of the phase particles was 59.44 μm. The average particle size of this pre-emulsified oil / fat composition is 63.2 times the pore size of 0.94 μm of the SPG emulsified membrane that passes during the re-emulsification treatment of the pre-emulsified oil / fat composition. The dispersion coefficient (σ) was 1.00.
This pre-emulsified oil / fat composition was re-emulsified using an emulsifier manufactured by Kiyomoto Seiko Co., Ltd. equipped with a cylindrical SPG emulsified membrane having a diameter of 10 mm, a length of 100 mm and a thickness of 1 mm and an average pore diameter of 0.94 μm. did. The extrusion of the pre-emulsified oil / fat composition through the SPG emulsion film was based on the pressure of nitrogen gas. In this example, the extrusion pressure of nitrogen gas for passing through this SPG emulsion membrane is 3.00 MPa, and the flow rate of the pre-emulsified oil and fat composition passing through the SPG emulsion membrane is a passage area of 25 cm.2It was 2.7 ml / sec. In the re-emulsified emulsified oil / fat composition, the average particle size is 0.92 μm, which is 0.98 times the pore size of 0.94 μm of the SPG emulsion membrane, and the monodispersion coefficient of the re-emulsified particles (Σ) was 0.55.
[0018]
Example 3
This example is an example of an oil-in-water emulsified oil / fat composition for a chemical product. In this example, a high power stirrer HPS-100 (trade name: manufactured by Seiei Inoue Co., Ltd.) was used as a preliminary emulsifier. In this stirrer mixing tank, 50 parts by weight of 0.2% aqueous sodium dodecyl sulfate solution in the aqueous phase part is added, and 50 parts by weight of rapeseed oil in the oil phase part is added to the aqueous phase part, and the rotor is rotated. The mixture was pre-emulsified by rotating at 800 rpm for 5 minutes. The pre-emulsified oil / fat composition obtained by this pre-emulsification is an oil-in-water emulsified oil / fat composition having rapeseed oil as the internal phase and water as the external phase, the internal phase being 50%, and the average of the internal phase particles. The particle size was 86.36 μm. The average particle size of this pre-emulsified oil / fat composition is 27.0 times the pore size of 3.2 μm of the SPG emulsion membrane that passes during the re-emulsification treatment of the pre-emulsified oil / fat composition. The dispersion coefficient (σ) was 1.40.
This pre-emulsified oil / fat composition was re-emulsified using an emulsifier manufactured by Kiyomoto Seiko Co., Ltd. equipped with a cylindrical SPG emulsion membrane having a diameter of 10 mm, a length of 100 mm and a thickness of 1 mm and an average pore diameter of 3.2 μm. did. The extrusion of the pre-emulsified oil / fat composition through the SPG emulsion film was based on the pressure of nitrogen gas. In this example, the extrusion pressure of the nitrogen gas for passing through the SPG emulsion film is 1.0 MPa, and the flow rate through the SPG emulsion film has a passage area of 25 cm.2It was 5.0 ml per second. In the re-emulsified emulsified oil / fat composition, the average particle diameter is 2.93 μm, which is 0.92 times the pore diameter of the SPG emulsion film, and the monodispersion coefficient (σ) of the re-emulsified particles Was 0.60.
[0019]
Example 4
This example is an example of an oil-in-water emulsified oil / fat composition for a chemical product. In this example, a high power stirrer HPS-100 (trade name: manufactured by Inoue Seieido Co., Ltd.) was used as a preliminary emulsifier. In this stirrer mixing tank, 50 parts by weight of 0.2% aqueous sodium dodecyl sulfate solution in the aqueous phase part is added, and 50 parts by weight of rapeseed oil in the oil phase part is added to the aqueous phase part, and the rotor is rotated. The mixture was pre-emulsified by rotating at 800 rpm for 5 minutes. The pre-emulsified oil / fat composition obtained by this pre-emulsification is an oil-in-water emulsified oil / fat composition having rapeseed oil as the internal phase and water as the external phase, the internal phase being 50% and the external phase being 50%. The average particle size of the internal phase particles was 77.83 μm. The average particle size of the pre-emulsified oil / fat composition that passes during the re-emulsification treatment of the pre-oil / fat emulsion composition is 3.2 μm with respect to the pore size of 3.2 μm of the SPG emulsion membrane that passes during the re-emulsification treatment of the pre-oil / fat emulsion composition The monodispersion coefficient (σ) of the pre-emulsified particles was 1.60.
This pre-emulsified oil / fat composition was re-emulsified using an emulsifier manufactured by Kiyomoto Seiko Co., Ltd. equipped with a cylindrical SPG emulsion membrane having a diameter of 10 mm, a length of 100 mm and a thickness of 1 mm and an average pore diameter of 3.2 μm. did. The extrusion of the pre-emulsified oil / fat composition through the SPG emulsion film was based on the pressure of nitrogen gas. In this example, the extrusion pressure of nitrogen gas for passing through the SPG emulsion membrane is 1.5 MPa, and the flow rate of the preliminary oil and fat emulsion composition passing through the SPG emulsion membrane is 25 cm.2It was 15.0 ml per second. In the re-emulsified emulsified oil / fat composition, the average particle diameter is 2.49 μm, which is 0.78 times the pore diameter of 3.2 μm of the SPG emulsion film, and the monodisperse of the re-emulsified particles The coefficient (σ) is 0.60.
[0020]
Example 5.
This example is an example of an oil-in-water emulsified oil / fat composition for a chemical product. In this example, a high power stirrer HPS-100 (trade name: manufactured by Seiei Inoue Co., Ltd.) was used as a preliminary emulsifier. 50 parts by weight of a 0.2% aqueous solution of sodium dodecyl sulfate in the aqueous phase is placed in the mixing tank of the stirrer, and 50 parts by weight of rapeseed oil containing 5% of condensed ricinoleate in the oil phase is added to the aqueous phase. Was added, and the rotor was rotated at 1000 rpm for 10 minutes for preliminary emulsification. The pre-emulsified oil / fat composition obtained by this pre-emulsification is an oil-in-water emulsified oil / fat composition having rapeseed oil as the internal phase and water as the external phase, the internal phase being 50% and the external phase being 50%. The average particle size of the internal phase particles was 69.38 μm. The average particle size of the pre-emulsified oil / fat composition is 73.8 times the pore size of 0.94 μm of the SPG emulsified membrane that passes during the re-emulsification treatment of the pre-emulsified oil / fat composition. The coefficient (σ) was 1.44.
This pre-emulsified oil / fat composition was re-emulsified using an emulsifier manufactured by Kiyomoto Seiko Co., Ltd. equipped with a cylindrical SPG emulsified membrane having a diameter of 10 mm, a length of 100 mm and a thickness of 1 mm and an average pore diameter of 0.94 μm. did. Regarding the re-emulsification of the pre-emulsified oil / fat composition, the extrusion through the SPG emulsified membrane was performed by the pressure of nitrogen gas. In this example, the extrusion pressure of nitrogen gas for passing through the SPG emulsion film is 3.0 MPa, and the flow rate through the SPG emulsion film has a passage area of 25 cm.2It was 1.5 ml per second. In the re-emulsified emulsified oil / fat composition, the average particle size is 0.93 μm, which is 0.99 times the pore size of 0.94 μm of the SPG emulsion membrane, and the monodispersion coefficient of the re-emulsified particles (σ) is 0.54.
[0021]
Example 6
This example is an example of an oil-in-water emulsified oil / fat composition for a chemical product. In this example, a high power stirrer HPS-100 (trade name: manufactured by Seiei Inoue Co., Ltd.) was used as a preliminary emulsifier. In the mixing tank of this stirrer, 90 parts by weight of 0.2% aqueous solution of sodium dodecyl sulfate in the aqueous phase part is added, and 10 parts by weight of rapeseed oil in the oil phase part is added to this aqueous phase part, and the rotor is rotated at a rotational speed. The mixture was pre-emulsified by rotating at 1600 rpm for 10 minutes. The pre-emulsified oil / fat composition obtained by this pre-emulsification is an oil-in-water emulsified oil / fat composition in which rapeseed oil is the inner phase and water is the outer phase, the inner phase is 10%, and the outer phase is 90%. The average particle size of the internal phase particles was 96.84 μm. The average particle size of the pre-emulsified oil / fat composition is 103.0 times the pore size of 0.94 μm of the SPG emulsified membrane that passes during the re-emulsification treatment of the pre-emulsified oil / fat composition. The coefficient (σ) was 0.96.
This pre-emulsified oil / fat composition was re-emulsified using an emulsifier manufactured by Kiyomoto Seiko Co., Ltd. equipped with a cylindrical SPG emulsified membrane having a diameter of 10 mm, a length of 100 mm and a thickness of 1 mm and an average pore diameter of 0.94 μm. did. The extrusion of the pre-emulsified oil / fat composition through the SPG emulsion film was based on the pressure of nitrogen gas. In this example, the extrusion pressure of the nitrogen gas for passing through the SPG emulsion film is 3.50 MPa, and the flow rate through the SPG emulsion film has a passage area of 25 cm.2It was 8.6 ml per second. In the re-emulsified emulsified oil / fat composition, the average particle size is 0.92 μm, which is 0.98 times the pore size of 0.94 μm of the SPG emulsion membrane, and the monodispersion coefficient of the re-emulsified particles (Σ) is 0.54.
[0022]
Example 7.
This example is an example of an oil-in-water emulsified oil and fat composition. In this example, a homogenizer (Ultra Turrax T25: trade name, manufactured by Inoue Seieido Co., Ltd.) was used as a preliminary emulsifier. In this homogenizer mixing tank, 87.5 parts by weight of a mixed solution of a 0.3% aqueous solution of NaCl and a 1% aqueous solution of polyoxyethylene hydrogenated castor oil in the aqueous phase was placed. To this aqueous phase portion, 12.5 parts by weight of soybean oil in the oil phase portion was added, and the rotor was pre-emulsified by rotating at 8000 rpm for 2 minutes. The pre-emulsified oil / fat composition obtained by this pre-emulsification is an oil-in-water emulsified oil / fat composition having soybean oil as the internal phase and water as the external phase, and the internal phase is 12.5%. The average particle size of the particles was 97.42 μm. The average particle size of the pre-emulsified oil / fat composition is 30.4 times the pore size of 3.2 μm of the SPG emulsion membrane that passes during the re-emulsification treatment of the pre-emulsified oil / fat composition. The dispersion coefficient (σ) was 0.78.
This pre-emulsified oil / fat composition was re-emulsified using an emulsifier manufactured by Kiyomoto Seiko Co., Ltd. equipped with a cylindrical SPG emulsion membrane having a diameter of 10 mm, a length of 100 mm and a thickness of 1 mm and an average pore diameter of 3.2 μm. did. The extrusion of the pre-emulsified oil / fat composition through the SPG emulsion film was based on the pressure of nitrogen gas. In this example, the extrusion pressure of nitrogen gas for passing through this SPG emulsion film was 1.20 MPa. The average particle size of the re-emulsified emulsified oil / fat composition is 2.89 μm, which is 0.90 times the pore size of 3.2 μm of the SPG emulsion membrane, and the monodispersion coefficient (σ) of the re-emulsified particles Is 0.55It was.
0023]
In the above Examples, sodium dodecyl sulfate is a hydrophilic surfactant, and one manufactured by Wako Pure Chemical Industries, Ltd. was used. Polyoxyethylene hydrogenated castor oil is a hydrophilic surfactant, and a product manufactured by Nikko Chemicals Co., Ltd. was used. Polyglycerin fatty acid ester is a hydrophilic surfactant, and one manufactured by Taiyo Kagaku Co., Ltd. was used. Condensed ricinoleic acid ester is a hydrophobic surfactant, and one made by Sakamoto Yakuhin Kogyo Co., Ltd. was used. For soybean oil and rapeseed oil, commercially available refined products were used, respectively. As the water, commercially available distilled water produced by a distilled water production apparatus, for example, manufactured by Yamato Scientific Co., Ltd. was used. NaCl is a commercially available reagent-grade sodium chloride such as Wako.
A product made by Junyaku Kogyo Co., Ltd. was used. Moreover, the SPG emulsification film made by SPG Techno Co., Ltd. was used. In the above examples, the particle size distribution measurement of the dispersed particles in the emulsified oil / fat composition was performed by a laser manufactured by Shimadzu Corporation.
It measured using the diffraction type particle size distribution analyzer SALD-2000J.
0024]
【The invention's effect】
The present invention relates to a pre-emulsified composition having an average particle size exceeding 20 times the pore size of a porous emulsion membrane having a uniform pore size to be passed during re-emulsification, an outer phase portion and an inner phase portion containing an emulsifier, The pre-emulsified composition produced in advance is passed through the porous emulsified membrane having the uniform pore size while applying a pressure of 0.1 MPa or more, and is 1 time the pore size of the emulsified membrane. An emulsified composition having an average particle size of less than 1 μm, for example, an emulsified composition having an average particle size of less than 1 μm, which has been considered difficult to produce using an emulsified oil composition, for example, an emulsified oil and fat composition It is possible to produce an emulsified composition having uniformly dispersed particles in which the particle size distribution is within a narrow range by reducing the amount of emulsifier used. Further, the present invention can produce an emulsified composition having fine and uniform dispersed particles, for example, an emulsified oil and fat composition, with a reduced content of the emulsifier as compared with the conventional method, In the field of cosmetics and agrochemicals, it has a great influence and is industrially useful.
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| JP4639929B2 (en) * | 2005-04-26 | 2011-02-23 | 株式会社エクォス・リサーチ | Carbon airgel and method for producing the same |
| JP5168529B2 (en) * | 2005-06-15 | 2013-03-21 | エス・ピー・ジーテクノ株式会社 | Method and apparatus for producing emulsion using porous material |
| US8153180B2 (en) * | 2005-09-06 | 2012-04-10 | Pepsico, Inc. | Method and apparatus for making beverages |
| JP4981312B2 (en) * | 2005-11-01 | 2012-07-18 | 清本鐵工株式会社 | Emulsification method and emulsifier |
| ES2524120T3 (en) | 2010-12-28 | 2014-12-04 | Unilever N.V. | Method for the production of an emulsion |
| JP6191999B2 (en) | 2013-01-10 | 2017-09-06 | 国立大学法人九州大学 | Method and apparatus for producing a composition in which a dispersed phase is dispersed in a continuous phase |
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