JP2014128763A - Method for forming w/o type emulsion, method for manufacturing spherical particle, and spherical particle - Google Patents
Method for forming w/o type emulsion, method for manufacturing spherical particle, and spherical particle Download PDFInfo
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- JP2014128763A JP2014128763A JP2012287922A JP2012287922A JP2014128763A JP 2014128763 A JP2014128763 A JP 2014128763A JP 2012287922 A JP2012287922 A JP 2012287922A JP 2012287922 A JP2012287922 A JP 2012287922A JP 2014128763 A JP2014128763 A JP 2014128763A
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- emulsion
- oil phase
- aqueous
- forming
- liquid
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- 239000000839 emulsion Substances 0.000 title claims abstract description 137
- 239000012798 spherical particle Substances 0.000 title claims abstract description 94
- 238000000034 method Methods 0.000 title claims abstract description 67
- 238000004519 manufacturing process Methods 0.000 title claims description 32
- 239000012071 phase Substances 0.000 claims abstract description 191
- 239000007788 liquid Substances 0.000 claims abstract description 73
- 239000012528 membrane Substances 0.000 claims abstract description 57
- 239000008346 aqueous phase Substances 0.000 claims abstract description 54
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- 229910052751 metal Inorganic materials 0.000 claims description 37
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- 230000015572 biosynthetic process Effects 0.000 claims description 6
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- 238000000790 scattering method Methods 0.000 description 2
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- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
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- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
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- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
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- 239000004166 Lanolin Substances 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
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- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical class C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
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- 235000019774 Rice Bran oil Nutrition 0.000 description 1
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- YMCOHQVWOBMDCZ-UHFFFAOYSA-L Zinc undecylenate Chemical compound [Zn+2].[O-]C(=O)CCCCCCCCC=C.[O-]C(=O)CCCCCCCCC=C YMCOHQVWOBMDCZ-UHFFFAOYSA-L 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
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- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 description 1
- 229940063655 aluminum stearate Drugs 0.000 description 1
- BBMXVTPBLPQMAE-UHFFFAOYSA-K aluminum;docosanoate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCCCCCC([O-])=O BBMXVTPBLPQMAE-UHFFFAOYSA-K 0.000 description 1
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- HIAAVKYLDRCDFQ-UHFFFAOYSA-L calcium;dodecanoate Chemical compound [Ca+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O HIAAVKYLDRCDFQ-UHFFFAOYSA-L 0.000 description 1
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- MFGZXPGKKJMZIY-UHFFFAOYSA-N ethyl 5-amino-1-(4-sulfamoylphenyl)pyrazole-4-carboxylate Chemical compound NC1=C(C(=O)OCC)C=NN1C1=CC=C(S(N)(=O)=O)C=C1 MFGZXPGKKJMZIY-UHFFFAOYSA-N 0.000 description 1
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- 125000002524 organometallic group Chemical group 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
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- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
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- 230000004044 response Effects 0.000 description 1
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- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
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- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000010907 stover Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 125000005590 trimellitic acid group Chemical class 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 229940098697 zinc laurate Drugs 0.000 description 1
- 229940105125 zinc myristate Drugs 0.000 description 1
- 229940012185 zinc palmitate Drugs 0.000 description 1
- GAWWVVGZMLGEIW-GNNYBVKZSA-L zinc ricinoleate Chemical compound [Zn+2].CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O.CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O GAWWVVGZMLGEIW-GNNYBVKZSA-L 0.000 description 1
- 229940100530 zinc ricinoleate Drugs 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- LPEBYPDZMWMCLZ-CVBJKYQLSA-L zinc;(z)-octadec-9-enoate Chemical compound [Zn+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O LPEBYPDZMWMCLZ-CVBJKYQLSA-L 0.000 description 1
- IJQXGKBNDNQWAT-UHFFFAOYSA-L zinc;docosanoate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCCCCCC([O-])=O IJQXGKBNDNQWAT-UHFFFAOYSA-L 0.000 description 1
- GPYYEEJOMCKTPR-UHFFFAOYSA-L zinc;dodecanoate Chemical compound [Zn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O GPYYEEJOMCKTPR-UHFFFAOYSA-L 0.000 description 1
- GJAPSKMAVXDBIU-UHFFFAOYSA-L zinc;hexadecanoate Chemical compound [Zn+2].CCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCC([O-])=O GJAPSKMAVXDBIU-UHFFFAOYSA-L 0.000 description 1
- GBFLQPIIIRJQLU-UHFFFAOYSA-L zinc;tetradecanoate Chemical compound [Zn+2].CCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCC([O-])=O GBFLQPIIIRJQLU-UHFFFAOYSA-L 0.000 description 1
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Abstract
Description
本発明は、Ｗ／Ｏ型エマルションの形成方法、当該Ｗ／Ｏ型エマルションの形成方法を用いた球状粒子の製造方法、当該球状粒子の製造方法により製造される球状粒子に関する。 The present invention relates to a method for forming a W / O emulsion, a method for producing spherical particles using the method for forming a W / O emulsion, and spherical particles produced by the method for producing the spherical particles.
従来、粒子径の均一な球状粒子を製造する方法としては種々の方法が知られている。例えば、ゾルゲル法の１種であるＳｔｏｂｅｒ法（ストーバー法）ではシリコンの金属アルコキシドをアルカリ触媒で加水分解させて粒子径の均一な球状シリカを製造する方法がある。しかし、この方法においては、シリコンアルコキシド以外の金属アルコキシドは加水分解反応速度が極めて速いため、球状シリカ以外の球状金属酸化物粒子を得ることは困難であった。 Conventionally, various methods are known as methods for producing spherical particles having a uniform particle diameter. For example, the Stober method (Stover method), which is a kind of sol-gel method, includes a method of producing spherical silica having a uniform particle size by hydrolyzing silicon metal alkoxide with an alkali catalyst. However, in this method, since metal alkoxides other than silicon alkoxide have a very high hydrolysis reaction rate, it has been difficult to obtain spherical metal oxide particles other than spherical silica.
一方、有機材料の球状粒子を製造する方法としては、Ｗ／Ｏ型、Ｏ／Ｗ型、あるいはＷ／Ｏ／Ｗ型等のエマルションを用いた乳化重合法や膜乳化法が良く知られており（例えば特許文献１参照）、一般に普及している。そこで、金属や無機質の粒子径の均一な球状粒子を製造する方法としてこの膜乳化法を応用し、マイクロ流路である微小孔を有する隔壁や多孔質の隔壁を介して金属や水性液体を油相中に流入（注入）させてエマルションを形成させ、得られるエマルションから均一な粒子径の金属や金属酸化物粒子を製造する方法も提案されている（例えば特許文献２〜５参照）。 On the other hand, as a method for producing spherical particles of an organic material, an emulsion polymerization method using a W / O type, O / W type, or W / O / W type emulsion or a membrane emulsification method is well known. (See, for example, Patent Document 1), which is widely used. Therefore, this membrane emulsification method is applied as a method for producing spherical particles having a uniform particle size of metal or inorganic material, and the metal or aqueous liquid is oiled through the partition walls having micropores that are microchannels or the porous partition walls. There has also been proposed a method for producing metal or metal oxide particles having a uniform particle diameter from an emulsion obtained by inflow (injection) into a phase to form an emulsion (see, for example, Patent Documents 2 to 5).
しかしながら、従来のエマルションを形成する方法では、エマルションを安定に存在させるために界面活性剤又は分散剤を併用し、これらを水相や油相中に添加しておく必要がある。ここでエマルション形成時に界面活性剤や分散剤（以下、「界面活性剤等」と表記する場合がある）を用いた場合、界面活性剤等と油相の液体成分との分離精製が困難であるため、エマルションの形成方法やこのエマルションを用いた均一な球状粒子の製造方法では、用いた油相の液体は使用後の再使用が難しく廃棄処分せざるを得ないという問題点があった。
一方、近年、地球温暖化や環境汚染等への問題から環境に優しい材料やプロセスヘの要求が強くなってきており、このようなエマルションの形成方法や均一な球状粒子の製造方法においても、油相を再使用することにより廃棄処分を行う必要のないプロセス、すなわち界面活性剤等を用いない環境対応型プロセスヘのニーズが高まってきている。
However, in the conventional method of forming an emulsion, it is necessary to use a surfactant or a dispersant together in order to make the emulsion exist stably, and to add these to the water phase or the oil phase. Here, when a surfactant or a dispersant (hereinafter sometimes referred to as “surfactant etc.”) is used at the time of forming the emulsion, it is difficult to separate and purify the surfactant etc. and the liquid component of the oil phase. Therefore, in the method of forming an emulsion and the method of producing uniform spherical particles using this emulsion, there has been a problem that the oil phase liquid used is difficult to reuse after use and must be disposed of.
On the other hand, in recent years, the demand for environmentally friendly materials and processes has become stronger due to problems with global warming and environmental pollution, and the oil phase is also used in such emulsion formation methods and uniform spherical particle production methods. There is an increasing need for a process that does not require disposal by reusing, that is, an environmentally friendly process that does not use a surfactant or the like.
本発明は、上記事情に鑑みてなされたものであって、界面活性剤等を使用しないで安定なエマルションを形成させることが可能なＷ／Ｏ型エマルションの形成方法、当該Ｗ／Ｏ型エマルションの形成方法を用いた球状粒子の製造方法、当該球状粒子の製造方法により製造される球状粒子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 a method for forming a W / O emulsion capable of forming a stable emulsion without using a surfactant or the like, It aims at providing the spherical particle manufactured by the manufacturing method of the spherical particle using the formation method, and the manufacturing method of the said spherical particle.
本発明者等は、界面活性等を使用しないで安定なエマルションを形成させる方法について鋭意検討し、油相中で水相の液滴（水相液滴）が生成する過程及び油相中での水相液滴の合一化過程について詳細な検討を行った。その結果、水相の液体を管状の多孔質膜体の内部へ透過（通過）させて内部の油相の液体中へ注入することにより油相中に球状のＷ／Ｏ型エマルションを形成させる方法において、特定の条件を制御することにより、界面活性剤等を使用しないで安定なＷ／Ｏ型エマルションが形成されることを見出した。さらに、該Ｗ／Ｏ型エマルションから水相液滴中の溶媒成分を除去して、固形分を油相中で固化させることにより、形状や粒度均一性に優れた球状粒子を形成させることを見出し、本発明を完成するに至った。本発明は下記のとおりである。 The present inventors diligently studied a method for forming a stable emulsion without using surface activity, etc., and the process of forming water phase droplets (water phase droplets) in the oil phase and in the oil phase. A detailed study on the coalescence process of water phase droplets was conducted. As a result, a method for forming a spherical W / O emulsion in the oil phase by allowing the liquid in the aqueous phase to permeate (pass) into the tubular porous membrane and inject it into the liquid in the oil phase inside. In the above, it was found that by controlling specific conditions, a stable W / O emulsion can be formed without using a surfactant or the like. Furthermore, the solvent component in the water phase droplet is removed from the W / O type emulsion, and the solid content is solidified in the oil phase, thereby forming a spherical particle having excellent shape and particle size uniformity. The present invention has been completed. The present invention is as follows.
［１］ 管状の多孔質膜体の管内部に油相の液体を流し管外部に水相の液体を流し、該水相の液体を、前記多孔質膜体を透過させ、管内部を流れる前記油相の液体中へ注入することにより、前記油相の液体中に球状の水相液滴を形成するＷ／Ｏ型エマルションを形成する方法であって、
次の（１）〜（３）の各式を満たすように前記Ｗ／Ｏ型エマルションを形成する、Ｗ／Ｏ型エマルションの形成方法。
[1] An oil phase liquid is allowed to flow inside a tube of a tubular porous membrane body, an aqueous phase liquid is allowed to flow outside the tube, and the aqueous phase liquid is allowed to permeate the porous membrane body and flow inside the tube. A method of forming a W / O type emulsion that forms spherical aqueous phase droplets in the oil phase liquid by injecting into the oil phase liquid,
A method for forming a W / O emulsion, wherein the W / O emulsion is formed so as to satisfy the following formulas (1) to (3).
φ＜（１／３００）・〔（３λ）／（Ｃｐ・Ｒｅ・ρ・ｕ2）〕0.5・・・（１）
Ｃｐ＝１８・（Ｒｅ）-0.6 ・・・・・・（２）
Ｒｅ＝（ｕ・Ｌ）／μ ・・・・・・（３）
φ <(1/300) · [(3λ) / (Cp · Re · ρ · u 2 )] 0.5 (1)
Cp = 18 ・ (Re) -0.6・ ・ ・ ・ ・ ・ (2)
Re = (u · L) / μ (3)
（ただし、
φ：油相中に形成させる水相の液滴径
ρ：油相液体の比重
μ：油相液体の動粘度
ｕ：多孔質膜体の管状内部を流れる油相（あるいはエマルション）の流速
λ：水相液体の表面張力
ｌ：多孔質膜の孔径
Ｌ：多孔質膜体の管の内径、である。）
(However,
φ: droplet diameter of the water phase formed in the oil phase ρ: specific gravity of the oil phase liquid μ: kinematic viscosity of the oil phase liquid u: flow velocity of the oil phase (or emulsion) flowing inside the tubular membrane body λ: Surface tension 1 of aqueous phase liquid: pore diameter L of porous membrane L: inner diameter of tube of porous membrane body. )
［２］ 前記油相の液体中の前記水相液滴を１体積％以上かつ１５体積％以下とする［１］に記載のＷ／Ｏ型エマルションの形成方法。
［３］ 前記Ｗ／Ｏ型エマルションが、界面活性剤及び分散剤を含まない［１］又は［２］に記載のＷ／Ｏ型エマルションの形成方法。
［４］ 前記水相の液体が、金属塩水溶液、金属微粒子の水系分散液、金属酸化物微粒子の水系分散液、金属微粒子及び金属酸化物微粒子の水系分散液、金属酸化物前駆体の水系分散液、及び金属アルコキシドの加水分解液のいずれかである［１］〜［３］のいずれかに記載のＷ／Ｏ型エマルションの形成方法。
[2] The method for forming a W / O emulsion according to [1], wherein the aqueous phase droplets in the oil phase liquid are 1% by volume or more and 15% by volume or less.
[3] The method for forming a W / O emulsion according to [1] or [2], wherein the W / O emulsion does not contain a surfactant and a dispersant.
[4] The aqueous phase liquid is an aqueous metal salt solution, an aqueous dispersion of metal fine particles, an aqueous dispersion of metal oxide fine particles, an aqueous dispersion of metal fine particles and metal oxide fine particles, or an aqueous dispersion of a metal oxide precursor. The method for forming a W / O emulsion according to any one of [1] to [3], which is either a liquid or a hydrolyzed liquid of a metal alkoxide.
［５］ 上記［１］〜［４］のいずれかに記載のＷ／Ｏ型エマルションの形成方法により形成されたエマルションを油相中で固化させることによって球状粒子を製造する球状粒子の製造方法。
［６］ 前記エマルションが固形物形成性成分を含有し、前記エマルションを油相中で固化させる方法が、当該エマルションを加熱することにより水相液滴中の溶媒成分を蒸発除去させる方法である［５］に記載の球状粒子の製造方法。
[5] A method for producing spherical particles, wherein spherical particles are produced by solidifying an emulsion formed by the method for forming a W / O emulsion according to any one of [1] to [4] in an oil phase.
[6] The emulsion contains a solid-forming component, and the method of solidifying the emulsion in the oil phase is a method of evaporating and removing the solvent component in the aqueous phase droplets by heating the emulsion. [5] The method for producing spherical particles according to [5].
［７］ 上記［５］又は［６］に記載の球状粒子の製造方法により製造されてなる球状粒子。 [7] Spherical particles produced by the method for producing spherical particles according to [5] or [6] above.
本発明によれば、界面活性剤や分散剤を使用しないで安定なエマルションを形成させることが可能なＷ／Ｏ型エマルションの形成方法、当該Ｗ／Ｏ型エマルションの形成方法を用いた球状粒子の製造方法、当該球状粒子の製造方法により製造される球状粒子を提供することができる。
本発明のＷ／Ｏ型エマルションの形成方法によれば、界面活性剤や分散剤を用いないで安定なエマルションを形成可能となるので、油相の液体成分の再使用が可能となり、低コストで地球環境対応に優れたＷ／Ｏ型エマルションの形成方法を提供することができる。
さらに、このようなエマルションを使用して金属や無機質の均一な球状粒子を製造することにより、産業的に有用な均一な球状粒子を低コストで地球環境対応に優れた方法で製造することが可能となる。
According to the present invention, a method for forming a W / O emulsion capable of forming a stable emulsion without using a surfactant or a dispersant, and a method for forming spherical particles using the method for forming a W / O emulsion. The spherical particle manufactured by the manufacturing method and the manufacturing method of the said spherical particle can be provided.
According to the method for forming a W / O type emulsion of the present invention, a stable emulsion can be formed without using a surfactant or a dispersant, so that the liquid component of the oil phase can be reused at low cost. It is possible to provide a method for forming a W / O emulsion excellent in response to the global environment.
Furthermore, by using such emulsions to produce uniform spherical particles of metals and inorganic materials, it is possible to produce industrially useful uniform spherical particles at a low cost and in an excellent manner for the global environment. It becomes.
本発明のＷ／Ｏ型エマルションの形成方法及び球状粒子の製造方法、並びに当該球状粒子の製造方法により製造される球状粒子を実施するための形態について説明する。
なお、この形態は、発明の趣旨をより良く理解させるために具体的に説明するものであり、特に指定のない限り、本発明を限定するものではない。
The form for implementing the spherical particle manufactured by the formation method of the W / O type emulsion of this invention, the manufacturing method of spherical particle, and the manufacturing method of the said spherical particle is demonstrated.
This embodiment is specifically described for better understanding of the gist of the invention, and does not limit the present invention unless otherwise specified.
（Ｗ／Ｏ型エマルションの形成方法）
本実施形態では、多孔質膜を介して油相中に水相の微小液滴を生成させ、いわゆるＷ／Ｏ型エマルションを形成させる。
より具体的には、管状の多孔質膜体の管内部に油相成分を一定速度で流し、多孔質膜体の管外部から水相成分を圧入させて、一定速度で流れている油相中に多孔質膜体を通過した水相の微小液滴を生成させる方法である。
(Method for forming W / O type emulsion)
In this embodiment, fine droplets of an aqueous phase are generated in an oil phase through a porous membrane, and a so-called W / O emulsion is formed.
More specifically, the oil phase component is allowed to flow at a constant speed inside the tube of the tubular porous membrane body, and the water phase component is pressed from outside the tube of the porous membrane body so that the oil phase component is flowing at a constant speed. In this method, fine droplets in the aqueous phase that have passed through the porous film body are generated.
本実施形態における油相中での水相液滴の生成メカニズムでは、水相液体が多孔質膜を介して流動中の油相液体に接触し、該水相液体が膜開口部から流出して流動油相液体中である大きさになると、油相液体からの流れの抵抗力により水相液体が膜開口部から引きちぎられることによつて油相液体中に水相の液滴が生成される。本発明に係る水相液滴の大きさ（φ）は、水相液体の表面張力（λ）及び多孔質膜孔径（ｌ）が水相液体が引きちぎられるときの力に対応する要因として、油相液体の流速（ｕ）、油相液体の比重（ρ）、油相液体の動粘度（μ）、及び管状多孔質膜体の管の内径（Ｌ）が流動している油相液体から水相液体にかかる力に対応する要因として作用することから、これらの値を調整することによって制御することが可能である。 In the generation mechanism of aqueous phase droplets in the oil phase in the present embodiment, the aqueous phase liquid contacts the flowing oil phase liquid through the porous membrane, and the aqueous phase liquid flows out from the opening of the membrane. When it reaches a certain size in the fluid oil phase liquid, water phase droplets are generated in the oil phase liquid by the water phase liquid being torn from the membrane opening due to the flow resistance force from the oil phase liquid. . The size (φ) of the aqueous phase droplet according to the present invention is a factor corresponding to the force when the aqueous phase liquid is torn off due to the surface tension (λ) and the porous membrane pore diameter (l) of the aqueous phase liquid. The flow rate of the phase liquid (u), the specific gravity (ρ) of the oil phase liquid, the kinematic viscosity (μ) of the oil phase liquid, and the inner diameter (L) of the tube of the tubular porous membrane body to water Since it acts as a factor corresponding to the force applied to the phase liquid, it is possible to control by adjusting these values.
一方、油相中における水相液滴の安定性（エマルション安定性）は、主として油相中の水相液滴の合一化の有無によって決まる。すなわち、界面活性剤等を用いないで流動している油相中の水相液滴を安定化させる（液滴を合一化させない）ためには、やはり水相液滴の大きさ（φ）と、水相液体の表面張力（λ）、多孔質膜孔径（ｌ）、油相液体の流速（ｕ）、油相液体の比重（ρ）、油相液体の動粘度（μ）、及び管状多孔質膜体の管の内径（Ｌ）との間に一定の条件が必要となる。そこで、これら各値の関係を検討した結果、次の（１）から（３）式を満足させることにより、安定なＷ／Ｏ型エマルションが形成されることが見出された。
なお、本発明において、水相液滴の大きさ（φ）はメディアン径（Ｄ50）をさす。
On the other hand, the stability of the aqueous phase droplets in the oil phase (emulsion stability) is mainly determined by the presence or absence of coalescence of the aqueous phase droplets in the oil phase. That is, in order to stabilize the water phase droplets in the flowing oil phase without using a surfactant or the like (do not unite the droplets), the size of the water phase droplets (φ) And surface tension (λ) of the water phase liquid, porous membrane pore diameter (l), flow velocity of the oil phase liquid (u), specific gravity of the oil phase liquid (ρ), kinematic viscosity (μ) of the oil phase liquid, and tubular A certain condition is required between the inner diameter (L) of the tube of the porous membrane body. As a result of examining the relationship between these values, it was found that a stable W / O emulsion can be formed by satisfying the following equations (1) to (3).
In the present invention, the size (φ) of the water phase droplet refers to the median diameter (D 50 ).
φ＜（１／３００）・〔（３λ）／（Ｃｐ・Ｒｅ・ρ・ｕ2）〕0.5・・・（１）
Ｃｐ＝１８・（Ｒｅ）-0.6 ・・・（２）
Ｒｅ＝（ｕ・Ｌ）／μ ・・・（３）
すなわち、これら（１）から（３）式の条件を満足させることが本発明の必須条件である。
φ <(1/300) · [(3λ) / (Cp · Re · ρ · u 2 )] 0.5 (1)
Cp = 18 · (Re) −0.6 (2)
Re = (u · L) / μ (3)
That is, it is an indispensable condition of the present invention to satisfy these conditions (1) to (3).
これら制御要因の設定範囲については、上記（１）から（３）式を満たす限り特に制限を設けるものではないが、管状の多孔質膜体の内部を流動させることの可能な油相成分の現実的な粘度はせいぜい３０００ｃｓ（センチストークス）が上限であり、これより高い粘度では流動性が不足する。また、１０ｃｓ未満ではエマルションの安定性が悪く、水相液滴のサイズ分布が大きくなるので好ましくない。 The setting range of these control factors is not particularly limited as long as the above formulas (1) to (3) are satisfied, but the reality of the oil phase component that can flow inside the tubular porous membrane body The maximum viscosity is at most 3000 cs (centistokes), and if the viscosity is higher than this, the fluidity is insufficient. On the other hand, if it is less than 10 cs, the stability of the emulsion is poor, and the size distribution of the water phase droplets becomes large, which is not preferable.
より安定的なエマルションを形成する観点から、（１）式の右辺の値をＸとした場合に、下記式を満たすことが好ましい。
０．０５Ｘ≦φ≦０．９Ｘ（より好ましくは、０．１Ｘ≦φ≦０．７Ｘ）
From the viewpoint of forming a more stable emulsion, when the value of the right side of the formula (1) is X, it is preferable to satisfy the following formula.
0.05X ≦ φ ≦ 0.9X (more preferably, 0.1X ≦ φ ≦ 0.7X)
油相の成分については、液状の有機媒体であって水相の液体との相溶性がないことが必要である。液体の相溶性については溶解性パラメータ、水素結合力、誘電率等様々な指標があるが、例えば溶解性パラーメータであれば、水相の液体（溶解性パラーメータ大）と有機媒体（溶解性パラメータ小）との差が２以上となるような組み合わせが好ましい。
また後述のように、本実施形態の球状粒子の製造方法は、本実施形態のエマルションを加熱して、水相液滴中の溶媒成分を蒸発除去することによって固形分を固化させて製造する方法が好ましい。このことから、油相を形成する液状の有機媒体は、その沸点が水相の溶媒（分散媒）よりも高く、かつ共沸しないものであることが好ましい。
このような有機媒体としては、有機溶剤、鉱物油、植物油、シリコーンオイル、イオン性液体等を用いることができる。
The oil phase component needs to be a liquid organic medium and not compatible with the water phase liquid. There are various indicators such as solubility parameters, hydrogen bonding strength, dielectric constant, etc. for the compatibility of liquids. For example, in the case of solubility parameters, aqueous phase liquid (large solubility parameter) and organic medium (small solubility parameter) A combination that makes the difference from 2) 2 or more is preferable.
As will be described later, the method for producing the spherical particles of the present embodiment is a method of heating the emulsion of the present embodiment and solidifying the solid content by evaporating and removing the solvent component in the aqueous phase droplets. Is preferred. For this reason, the liquid organic medium forming the oil phase preferably has a boiling point higher than that of the aqueous phase solvent (dispersion medium) and does not azeotrope.
As such an organic medium, an organic solvent, mineral oil, vegetable oil, silicone oil, ionic liquid, or the like can be used.
有機溶剤または合成油としては、フタル酸エステル、アジピン酸エステル、トリメリット酸エステル、リン酸エステル、フェニルエーテル、オレフィンオリゴマー、ポリブデン、アルキルベンゼン、シクロアルカン類等が挙げられる。
鉱物油としては、ニュートラル油、ブライトストック等のパラフィン油やナフテン油等が挙げられる。
植物油や動物油としては、大豆油、菜種油、米ぬか油、ラノリン油、鮫油等が挙げられる。
シリコーンオイルとしては、ジメチルポリシロキサン、メチルフェニルポリシロキサン、アルキル変性ポリシロキサン、脂肪酸エステル変性ポリシロキサン等が挙げられる。
イオン性液体としては、イミダゾリウム塩、ピリジニウム塩、アンモニウム塩、ピロリジニウム塩、ホスホニウム塩、スルホニウム塩等が挙げられる。
Examples of the organic solvent or synthetic oil include phthalic acid esters, adipic acid esters, trimellitic acid esters, phosphoric acid esters, phenyl ethers, olefin oligomers, polybutenes, alkylbenzenes, and cycloalkanes.
Examples of the mineral oil include paraffin oil such as neutral oil and bright stock, naphthenic oil, and the like.
Examples of vegetable oils and animal oils include soybean oil, rapeseed oil, rice bran oil, lanolin oil, and coconut oil.
Examples of the silicone oil include dimethylpolysiloxane, methylphenylpolysiloxane, alkyl-modified polysiloxane, and fatty acid ester-modified polysiloxane.
Examples of the ionic liquid include imidazolium salts, pyridinium salts, ammonium salts, pyrrolidinium salts, phosphonium salts, sulfonium salts and the like.
また、管状の多孔質膜体の管内部を流れる油相液体（又はエマルション）の流速は、乱流による異常な液滴の成長や分裂による不均一化を防止させるため、その流速は層流の範囲であることが好ましい。流速の上限値としては、式（３）で示されるＲｅ値が４００以下であることが好ましく、１００以下であればより好ましい。Ｒｅ値が４００を超える場合では、流速が速すぎるために流動している油相中の水相液滴同士の衝突合一化による液滴成長が生じやすくなる結果液滴のサイズ分布が大きくなりやすく、さらに乱流が発生した場合には異常な液滴の成長や分裂による不均一化により、液滴のサイズ分布がより大きくなるため好ましくない。
なお、流速が低い場合には基本的に層流となるために、Ｒｅ値の下限に限定はないが、エマルション形成時の要因を考慮すると、実質的に２以上であることが好ましく、５以上であればより好ましい。
Also, the flow velocity of the oil phase liquid (or emulsion) flowing inside the tubular porous membrane body prevents abnormal droplet growth due to turbulent flow and non-uniformity due to breakup. A range is preferable. As the upper limit value of the flow rate, the Re value represented by the formula (3) is preferably 400 or less, and more preferably 100 or less. When the Re value exceeds 400, since the flow velocity is too high, droplet growth is likely to occur due to collision coalescence of water phase droplets in the flowing oil phase, resulting in a large droplet size distribution. In addition, if a turbulent flow is further generated, it is not preferable because the size distribution of the droplets becomes larger due to abnormal droplet growth and non-uniformity due to fragmentation.
In addition, since it becomes a laminar flow basically when the flow rate is low, there is no limitation on the lower limit of the Re value, but it is preferably substantially 2 or more in consideration of the factor at the time of emulsion formation. Is more preferable.
管状の多孔質膜体については、特に制限するものではないが、多孔質膜の開口率や孔径均一性は得られるＷ／Ｏエマルションにおける水相液滴の量や液滴径の分布に影響し、ひいては該Ｗ／Ｏエマルションより得られる球状粒子の生産性や粒度分布に影響を与えるので、開孔率が高く、孔径の精度や均一性の高い多孔質膜体であることが好ましい。このような多孔質体としては、中空糸型の限外濾過膜やマイクロフィルター膜を挙げることができる。多孔質膜体の材質については本発明の本質的な効果に何ら影響を与えないので特に制限されない。また、多孔質膜体の管の内径と多孔質膜の孔径は、前記（１）から（３）式を満たす条件であれば特に限定されない。ただし、実用的な観点から、多孔質膜の孔径は０．００１μｍ以上かつ０．５μｍ以下が好ましく、０．００５μｍ以上かつ０．３μｍ以下がより好ましくい。 The tubular porous membrane is not particularly limited, but the aperture ratio and pore size uniformity of the porous membrane affect the amount of water phase droplets and the distribution of droplet sizes in the resulting W / O emulsion. In addition, since it affects the productivity and particle size distribution of the spherical particles obtained from the W / O emulsion, it is preferable that the porous film body has a high porosity and high pore diameter accuracy and uniformity. Examples of such a porous body include hollow fiber type ultrafiltration membranes and microfilter membranes. The material of the porous membrane is not particularly limited because it does not affect the essential effects of the present invention. Further, the inner diameter of the tube of the porous membrane body and the pore diameter of the porous membrane are not particularly limited as long as the conditions satisfy the expressions (1) to (3). However, from a practical viewpoint, the pore diameter of the porous membrane is preferably 0.001 μm or more and 0.5 μm or less, and more preferably 0.005 μm or more and 0.3 μm or less.
本実施形態のＷ／Ｏエマルションにおける水相の液体は、金属塩水溶液、金属微粒子の水系分散液、金属酸化物微粒子の水系分散液、金属微粒子及び金属酸化物微粒子の水系分散液、金属酸化物前駆体の水系分散液、金属アルコキシドの加水分解液、のいずれかであることが好ましい。金属塩水溶液としては金属の塩化物、硝酸塩、硫酸塩、炭酸塩、有機酸塩等の水溶液のほか、水ガラス、錫酸ナトリウム、アルミン酸ナトリウム等の金属のアルカリ塩等の水溶液があり、それぞれの溶解度の範囲内での金属塩溶液を用いることができる。 The aqueous phase liquid in the W / O emulsion of the present embodiment includes an aqueous metal salt solution, an aqueous dispersion of metal fine particles, an aqueous dispersion of metal oxide fine particles, an aqueous dispersion of metal fine particles and metal oxide fine particles, and a metal oxide. It is preferably either an aqueous dispersion of a precursor or a hydrolyzate of a metal alkoxide. In addition to aqueous solutions of metal chlorides, nitrates, sulfates, carbonates, organic acid salts, etc., metal salt aqueous solutions include aqueous solutions of metal alkali salts such as water glass, sodium stannate, sodium aluminate, etc. It is possible to use a metal salt solution within the solubility range of.
また、金属微粒子、金属酸化物微粒子、金属微粒子及び金属酸化物微粒子、金属酸化物前駆体の水系分散液としては、公知の液相還元法によつて得られる貴金属や卑金属の各種金属コロイド液、公知の技術によつて製造されたシリカ、アルミナ、セリア、ジルコニア、チタニア等の金属酸化物ゾルや水酸化物等の金属酸化物前駆体ゾル等を用いることができる。これら分散液における微粒子の平均分散粒子径（メジアン径 ｄ５０）については、多孔質膜の孔径の１／３以下とすることが好ましい。これを超える場合には、多孔質膜が閉塞し易くなるので連続的安定なエマルションの製造が難しくなるおそれがある。 In addition, as an aqueous dispersion of metal fine particles, metal oxide fine particles, metal fine particles and metal oxide fine particles, metal oxide precursor, various metal colloid liquids of noble metals and base metals obtained by a known liquid phase reduction method, Metal oxide sols such as silica, alumina, ceria, zirconia, and titania produced by a known technique, metal oxide precursor sols such as hydroxides, and the like can be used. The average dispersed particle diameter (median diameter d50) of the fine particles in these dispersions is preferably 1/3 or less of the pore diameter of the porous membrane. When exceeding this, since it becomes easy to block | close a porous membrane, there exists a possibility that manufacture of a continuous stable emulsion may become difficult.
金属アルコキシドの加水分解液としては、金属アルコキシドのメタノールやエタノールのアルコール溶液に水あるいは酸の触媒を添加して加水分解させた、金属アルコキシド加水分解物溶液等を用いることができる。 As the metal alkoxide hydrolyzate, a metal alkoxide hydrolyzate solution obtained by adding water or an acid catalyst to an alcohol solution of metal alkoxide in methanol or ethanol can be used.
本実施形態のエマルションの形成方法としては、管状の多孔質膜体の管内部に油相成分を一定速度で流し、多孔質膜体の管外部から水相成分を圧入させて一定速度で流れている油相中に水相液滴を生成させる方法が採られる。このとき、圧入させる水相成分の量は、油相中に対する水相液滴の体積割合が１％以上かつ１５％以下であることが好ましく、２％以上かつ１０％以下であればより好ましい。
水相の体積割合が１５％以下であることで、管の断面積に対する液滴の断面積が概ね１／３より小さくなるので、水相液滴同士の衝突合一化による液滴成長が抑えられ、液滴のサイズ分布も狭くすることができるほか、得られる粒子における球状の形状も良好なものとすることができる。また、水相の体積割合が１％以上であることで、特にこのエマルションを用いて球状粒子を製造する際の生産性及び経済性を良好なものとすることができる。
As a method for forming an emulsion of the present embodiment, an oil phase component is allowed to flow at a constant speed inside a tube of a tubular porous membrane body, and a water phase component is injected from the outside of the porous membrane body to flow at a constant speed. A method of generating water phase droplets in the oil phase is taken. At this time, the amount of the water phase component to be injected is such that the volume ratio of the water phase droplets to the oil phase is preferably 1% or more and 15% or less, and more preferably 2% or more and 10% or less.
Since the volume ratio of the aqueous phase is 15% or less, the cross-sectional area of the liquid droplet with respect to the cross-sectional area of the tube is substantially smaller than 1/3. In addition, the size distribution of the droplets can be narrowed, and the spherical shape of the obtained particles can be improved. In addition, when the volume ratio of the aqueous phase is 1% or more, productivity and economic efficiency can be improved particularly when spherical particles are produced using this emulsion.
本実施形態のエマルション形成方法によれば、界面活性剤及び分散剤を用いることなくＷ／Ｏ型のエマルションを安定して生成させることができる。また、生成させる水相液滴としては、概ね１００μｍより小さいサイズの液滴を得ることができる。 According to the emulsion forming method of the present embodiment, a W / O type emulsion can be stably generated without using a surfactant and a dispersant. Moreover, as a water phase droplet to produce | generate, the droplet of the size smaller than about 100 micrometers can be obtained.
なお、界面活性剤及び分散剤としては、例えば、陰イオン界面活性剤、陽イオン界面活性剤、非イオン界面活性剤、高分子界面活性剤、フッ素系界面活性剤、有機金属界面活性剤等が挙げられる。また、例えばフラックス、油性界面活性剤（油溶性界面活性剤）、金属石鹸、飽和脂肪酸、不飽和脂肪酸等も挙げられる。
油性界面活性剤としては、例えばソルビタン系、ポリオキシエチレン・ソルビタン系、ポリオキシエチレン・フェニルエーテル系、ショ糖脂肪酸エステル系、ポリグリセリン系等の油性界面活性剤が挙げられる。金属石鹸としては、例えばステアリン酸鉛、ステアリン酸亜鉛、ステアリン酸カルシウム、オレイン酸カルシウム、リシノール酸カルシウム、ラウリン酸カルシウム、ベヘン酸カルシウム、オクタン酸カルシウム、ラウリン酸亜鉛、パルミチン酸亜鉛、ミリスチン酸亜鉛、ウンデシレン酸亜鉛、オレイン酸亜鉛、リシノール酸亜鉛、ベヘン酸亜鉛、サリチル酸亜鉛、ナフテン酸亜鉛、ステアリン酸マグネシウム、ミリスチン酸マグネシウム、オレイン酸マグネシウム、ステアリン酸アルミニウム、ベヘン酸アルミニウム、オクタン酸アルミニウム、オレイン酸鉛、オクタン酸鉛、ナフテン酸鉛のほか、コバルト石鹸、ニッケル石鹸、鉄石鹸、銅石鹸、マンガン石鹸、スズ石鹸、リチウム石鹸等が挙げられる。飽和脂肪酸としては、例えば酪酸、カプロン酸、カプリル酸、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、アラキジン酸、ベヘニン酸等が挙げられる。不飽和脂肪酸としては、例えばオレイン酸、リノール酸、リノレン酸、エルカ酸等が挙げられる。そして、本発明ではこれらを含有させないことが好ましい。
Examples of surfactants and dispersants include anionic surfactants, cationic surfactants, nonionic surfactants, polymer surfactants, fluorosurfactants, and organometallic surfactants. Can be mentioned. Moreover, for example, flux, oil-based surfactant (oil-soluble surfactant), metal soap, saturated fatty acid, unsaturated fatty acid and the like can be mentioned.
Examples of the oily surfactant include oily surfactants such as sorbitan, polyoxyethylene / sorbitan, polyoxyethylene / phenyl ether, sucrose fatty acid ester, and polyglycerol. Examples of metal soaps include lead stearate, zinc stearate, calcium stearate, calcium oleate, calcium ricinoleate, calcium laurate, calcium behenate, calcium octoate, zinc laurate, zinc palmitate, zinc myristate, undecylenate Zinc, zinc oleate, zinc ricinoleate, zinc behenate, zinc salicylate, zinc naphthenate, magnesium stearate, magnesium myristate, magnesium oleate, aluminum stearate, aluminum behenate, aluminum octoate, lead oleate, octane In addition to lead oxide and lead naphthenate, cobalt soap, nickel soap, iron soap, copper soap, manganese soap, tin soap, lithium soap and the like can be mentioned. Examples of the saturated fatty acid include butyric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, and behenic acid. Examples of the unsaturated fatty acid include oleic acid, linoleic acid, linolenic acid, erucic acid and the like. And in this invention, it is preferable not to contain these.
（球状粒子の製造方法）
本実施形態の球状粒子は、上記に述べた方法で生成したＷ／Ｏ型エマルションにおける水相液滴中の固形物形成性成分を油相中で固化させて球状の固化物とすることで得ることができる。
なおここで、「固形物形成性成分」とは、水相の液体中で水系溶媒中に溶解している成分、ないしは水系分散媒中に分散している成分をいい、水相の液体が金属塩水溶液であれば金属塩が、金属微粒子や金属酸化物微粒子の水系分散液であれば各分散微粒子が、金属酸化物前駆体の水系分散液であれば金属酸化物前駆体が、金属アルコキシドの加水分解液であれば金属アルコキシドの加水分解物が、それぞれ該当する。
(Method for producing spherical particles)
The spherical particles of the present embodiment are obtained by solidifying solid-form forming components in water phase droplets in the W / O type emulsion produced by the above-described method in an oil phase to obtain spherical solidified products. be able to.
Here, the “solid-form forming component” means a component dissolved in an aqueous solvent in an aqueous phase liquid or a component dispersed in an aqueous dispersion medium, and the aqueous phase liquid is a metal. In the case of an aqueous salt solution, the metal salt is formed. In the case of an aqueous dispersion of metal fine particles or metal oxide fine particles, each dispersed fine particle is formed. In the case of an aqueous dispersion of a metal oxide precursor, the metal oxide precursor is formed of a metal alkoxide. If it is a hydrolysis liquid, the hydrolyzate of metal alkoxide corresponds, respectively.
水相液滴中の固形物形成性成分を固化させる方法としては、水相液滴や水相液滴から形成される固化物の形状が変形したり、水相液滴の合一化や分裂が実質的に起こったりしない方法であれば特に限定されない。
その方法としては、固形物形成性成分と反応して固形物形成性成分を固形分に変化させる物質をＷ／Ｏ型エマルション中に添加する方法でもよく、例えば水相液滴中に溶解している金属塩と反応して沈殿物を形成する成分の添加、水相液滴中に分散している微粒子を凝集・沈降させる凝集剤の添加、金属アルコキシドの加水分解物をゲル化させるゲル化剤の添加等を挙げることができる。
As a method of solidifying the solid-forming component in the aqueous phase droplet, the shape of the solid phase formed from the aqueous phase droplet or the aqueous phase droplet is deformed, or the aqueous phase droplet is coalesced or broken up. There is no particular limitation as long as the method does not substantially occur.
The method may be a method in which a substance that reacts with the solid-formable component to change the solid-formable component into a solid content is added to the W / O emulsion, for example, dissolved in an aqueous phase droplet. Addition of components that react with metal salts to form precipitates, addition of flocculants that aggregate and settle fine particles dispersed in water phase droplets, and gelling agents that gel metal alkoxide hydrolysates And the like.
また、水相液滴中の固形物形成性成分を固化させる方法としては、Ｗ／Ｏ型エマルションを加熱することにより水相液滴中の溶媒成分を蒸発除去させる方法でもよい。この方法であれば、新たな物質を添加することなく固形物形成性成分を固化して球状の固形物を形成でき、従って油相中に新たな成分が添加されることがないから、油相の液体成分の再使用が可能となり、よって低コストで地球環境対応に優れたＷ／Ｏ型エマルションの形成と球状粒子の形成が可能となることから好ましい。 Further, as a method for solidifying the solid-form forming component in the aqueous phase droplet, a method of evaporating and removing the solvent component in the aqueous phase droplet by heating the W / O type emulsion may be used. With this method, the solid-formable component can be solidified to form a spherical solid without adding a new substance, and therefore no new component is added to the oil phase. This is preferable because the liquid component can be reused, and thus it is possible to form a W / O emulsion and spherical particles that are low in cost and excellent in adapting to the global environment.
Ｗ／Ｏ型エマルションを加熱することにより水相液滴中の溶媒成分を蒸発除去することで固形物形成性分を固化させて球状の固化物とし、球状粒子を形成する方法としては、上記に述べた方法で作成したＷ／Ｏ型エマルションを加熱容器に回収し、加熱して、水相液滴中の溶媒成分を蒸発除去すればよい。
加熱温度は、常圧下又は減圧下において水相液滴中の溶媒成分の沸点以上とする。沸点よりも１０℃以上高い温度とすればより好ましい。その理由として、加熱温度が水相液滴中の溶媒成分の沸点高いほど、エマルション中から水相溶媒成分の除去が容易となるためである。なお、油相成分も同時に蒸発してしまってはＷ／Ｏ型エマルション自体が形成されなくなるから、加熱温度は油相成分の沸点未満である必要があり、また油相成分と水相の溶媒（分散媒）とは共沸しないものであることが好ましい。
なおここで、本工程以後のハンドリング時において、球状の固化物の形状を保持させるために、球状固化物中の残留溶媒量は１５％程度以下とすることが好ましい。
As a method for forming spherical particles by solidifying the solid-formable component by evaporating and removing the solvent component in the water phase droplets by heating the W / O type emulsion, The W / O emulsion prepared by the method described above may be recovered in a heating container and heated to evaporate and remove the solvent component in the aqueous phase droplet.
The heating temperature is set to be equal to or higher than the boiling point of the solvent component in the aqueous phase droplet under normal pressure or reduced pressure. More preferably, the temperature is higher by 10 ° C. than the boiling point. This is because the higher the boiling point of the solvent component in the aqueous phase droplet, the easier the removal of the aqueous phase solvent component from the emulsion. If the oil phase component also evaporates at the same time, the W / O emulsion itself is not formed. Therefore, the heating temperature must be lower than the boiling point of the oil phase component, and the oil phase component and the aqueous phase solvent ( The dispersion medium is preferably non-azeotropic.
Here, in the handling after the present step, in order to maintain the shape of the spherical solidified product, the amount of residual solvent in the spherical solidified product is preferably about 15% or less.
以上のようにして水相液滴中の溶媒を除去させることにより、油相成分中に球状の固形物からなる球状粒子を含む生成物が得られる。この生成物から、通常の濾過装置や遠心分離装置等の固液分離装置を用いて球状粒子と油相成分とを分離して、球状粒子を得ることができる。このとき、必要に応じて、油相成分と相溶性のある有機溶剤で球状粒子に付着している油相成分を溶解除去しても良い。
このようにして得られた球状粒子は、粒子の機械的強度が小さいので、必要に応じて乾燥や焼結処理を行い、粒子の機械的強度を向上させることができる。また熱分解処理あるいは熱還元処理等の処理を行い、エマルションから直接形成された粒子の特性を変化させることで、要求される特性を有する球状粒子を得ることもできる。
By removing the solvent from the aqueous phase droplets as described above, a product containing spherical particles composed of spherical solids in the oil phase component is obtained. From this product, the spherical particles can be obtained by separating the spherical particles and the oil phase component using a solid-liquid separation device such as a normal filtration device or a centrifugal separation device. At this time, if necessary, the oil phase component adhering to the spherical particles may be dissolved and removed with an organic solvent compatible with the oil phase component.
Since the spherical particles obtained in this way have a low mechanical strength, the particles can be dried and sintered as necessary to improve the mechanical strength of the particles. Further, by performing a treatment such as a thermal decomposition treatment or a thermal reduction treatment to change the properties of the particles directly formed from the emulsion, spherical particles having the required properties can be obtained.
本実施形態によれば、粒度分布が狭く、かつ平均粒子径Ｄ50が概ね０．１μｍから１０μｍの範囲を有する金属や無機質の球状粒子を製造することが可能となる。 According to the present embodiment, it is possible to produce metal or inorganic spherical particles having a narrow particle size distribution and an average particle diameter D 50 in the range of about 0.1 μm to 10 μm.
図１に、本実施形態のＷ／Ｏ型エマルション及び球状粒子の形成に用いられる装置の一形態を示す模式図である。
本形態では、管状の多孔質膜体１の管内部に、油相成分２を一定速度で流し、多孔質膜体１の管外部から水相成分３を圧入させて、一定速度で流れている油相４中に多孔質膜体を通過した水相の微小液滴５を生成させ、Ｗ／Ｏ型エマルション６を形成する。油相成分の流量（流速）は油相用ポンプ７と流量調整バルブ（１）９で、水相成分の流量（流速ないしは加圧力）は水相用ポンプ８と流量調整バルブ（２）１０でそれぞれ調整する。
形成されたＷ／Ｏ型エマルション６’は、エマルション回収タンク１１に集められ、加熱装置１２で加熱されることで水相成分の溶媒が除去され、油相成分２’中に球状粒子１３を含む生成物１４が得られる。この生成物１４から図示しない固液分離等を行い、必要に応じて熱処理等を行うことにより、本実施形態の球状粒子を得ることができる。
FIG. 1 is a schematic view showing an embodiment of an apparatus used for forming a W / O emulsion and spherical particles of this embodiment.
In this embodiment, the oil phase component 2 is flowed into the tube of the tubular porous membrane 1 at a constant speed, and the water phase component 3 is press-fitted from the outside of the tube of the porous membrane 1 to flow at a constant speed. Water phase micro droplets 5 that have passed through the porous film body are generated in the oil phase 4 to form a W / O type emulsion 6. The flow rate (flow velocity) of the oil phase component is between the oil phase pump 7 and the flow rate adjusting valve (1) 9, and the flow rate (flow rate or pressure) of the water phase component is at the water phase pump 8 and the flow rate adjusting valve (2) 10. Adjust each one.
The formed W / O emulsion 6 ′ is collected in the emulsion recovery tank 11, heated by the heating device 12, the solvent of the water phase component is removed, and the oil phase component 2 ′ contains spherical particles 13. Product 14 is obtained. By performing solid-liquid separation (not shown) or the like from the product 14 and performing heat treatment or the like as necessary, the spherical particles of the present embodiment can be obtained.
本発明の球状粒子の製造方法により得られる球状粒子は、種々の用途に適用することができる。例えば、蛍光体材料、誘電体材料及び金属顔料等の各種機能性粒子に適用することができる。これらについては、その製造時に界面活性剤等を用いないことから、球状粒子内部や表面に混入した界面活性剤等に基づく不純物（イオン性不純物や有機物）を含有することがないので、本発明により得られる各種機能性球状粒子の特性を低下又は劣化させることがない。
また、本発明の球状粒子の製造方法により得られる球状粒子は、油相中で固化形成するため、固化時において周囲の油相から均一な圧力を受けることで良好な球状性が維持される。従って、流動性や混合性に優れた粒子を得ることができる。
The spherical particles obtained by the method for producing spherical particles of the present invention can be applied to various uses. For example, the present invention can be applied to various functional particles such as a phosphor material, a dielectric material, and a metal pigment. About these, since a surfactant or the like is not used at the time of production, impurities (ionic impurities or organic substances) based on a surfactant or the like mixed in or inside the spherical particles are not contained. The characteristics of the various functional spherical particles obtained are not reduced or deteriorated.
Further, since the spherical particles obtained by the method for producing spherical particles of the present invention are solidified in the oil phase, good spherical properties are maintained by receiving uniform pressure from the surrounding oil phase during solidification. Accordingly, particles having excellent fluidity and mixing properties can be obtained.
以下、実施例及び比較例により本発明を具体的に説明するが、本発明はこれらの実施例によって限定されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited by these Examples.
「実施例１」
図１に示す球状粒子製造装置を組立てて球状粒子の作製を行った。
管状多孔質膜体には、（株）キッツマイクロフイルター社製の中空糸モジュール、ポリフィックスＦＴ１１（孔径０．１μｍ、内径３．１７５ｍｍ、材質ポリオレフィン）を用いた。
油相成分（油相の液体）として、信越化学（株）社製のシリコーンオイル、ＫＦ９６−１０ｃｓ（粘度１０ｃｓ、比重０．９３５ｇ／ｍｌ）を用いた。水相成分として、住友大阪セメント（株）社製のナノジルコニア５重量％分散液（表面張力７２ｍＮ／ｍ、比重１．０５ｇ／ｍｌ、平均分散粒子径９ｎｍ）を用いた。
油相成分及び水相成分（水相の液体）の流量（流速）の調整は、それぞれ流量調整バルブ（１）及びバルブ（２）のバルブ開度により行った。油相成分の流量は５０ｍｌ／分（このとき多孔質膜管内の油相成分の流速は０．１０５ｍ／ｓ）、水相成分の流量（供給速度）は５ｍｌ／分、油相成分に対する水相成分の割合は１０体積％として、実施例１のＷ／Ｏ型エマルションを生成させた。
"Example 1"
The spherical particle production apparatus shown in FIG. 1 was assembled to produce spherical particles.
As the tubular porous membrane, a hollow fiber module manufactured by KITZ Microfilter Co., Ltd., Polyfix FT11 (pore diameter 0.1 μm, inner diameter 3.175 mm, material polyolefin) was used.
As an oil phase component (oil phase liquid), silicone oil KF96-10cs (viscosity 10 cs, specific gravity 0.935 g / ml) manufactured by Shin-Etsu Chemical Co., Ltd. was used. As a water phase component, a 5% by weight nano-zirconia dispersion (surface tension 72 mN / m, specific gravity 1.05 g / ml, average dispersed particle size 9 nm) manufactured by Sumitomo Osaka Cement Co., Ltd. was used.
The flow rate (flow velocity) of the oil phase component and the water phase component (aqueous phase liquid) was adjusted by the valve opening degrees of the flow rate adjustment valve (1) and the valve (2), respectively. The flow rate of the oil phase component is 50 ml / min (at this time, the flow rate of the oil phase component in the porous membrane tube is 0.105 m / s), the flow rate of the water phase component (supply rate) is 5 ml / min, and the water phase relative to the oil phase component The W / O emulsion of Example 1 was generated with the proportion of the component being 10% by volume.
生成させたＷ／Ｏ型エマルションについて、その安定性を見るために生成直後のエマルション粒径と２４時間２５℃静置後のエマルション粒径を測定した。測定は、大塚電子（株）社製のレーザ回折散乱法、粒度分布測定装置ＤＬＳ８０００によリメディアン径（Ｄ50）を測定した。
これらエマルションの生成条件、及び得られたエマルションの測定結果について表１に示す。なお、表中の「ＮＺ分散液」とは、「ナノジルコニア分散液」をさす。
In order to check the stability of the produced W / O emulsion, the emulsion particle size immediately after production and the emulsion particle size after standing at 25 ° C. for 24 hours were measured. The measurement was performed by measuring the remedian diameter (D 50 ) using a laser diffraction scattering method and a particle size distribution measuring apparatus DLS8000 manufactured by Otsuka Electronics Co., Ltd.
Table 1 shows the conditions for producing these emulsions and the measurement results of the obtained emulsions. In the table, “NZ dispersion” refers to “nanozirconia dispersion”.
次いで、このエマルションを１３０℃で６時間加熱し、水相成分の溶媒である水を蒸発除去させて球状粒子を形成した。次いで、室温まで冷却した後、濾過装置にて油相成分と球状粒子の分離を行い、アセトンにて球状粒子の洗浄後、乾燥機にて１２０℃−２４時間乾燥させ、ジルコニアナノ粒子からなる、実施例１の多孔質球状粒子を作製した。さらに、得られたジルコニアナノ粒子からなる多孔質球状粒子を５００℃−２時間焼成して焼結させ、ジルコニアナノ粒子からなる、実施例１の緻密な球状ジルコニア粒子を作製した。
乾燥した多孔質球状粒子及び焼成した緻密な球状粒子について、レーザ回折散乱法によりメディアン径（Ｄ50）を測定した。また、走査型電子顕微鏡（ＳＥＭ）に撮影した代表粒子５個について画像処理（ＪＴrim）を行い次式により円形度を求めた（より１に近い値が円形（球状））。
円形度＝４πＳ／Ｌ2 Ｓ：面積、 Ｌ：周囲長
なお、画像処理は他のソフト（方法）を用いてもよい。
これらの測定結果を表１に示す。
Next, this emulsion was heated at 130 ° C. for 6 hours to evaporate and remove the water phase solvent, thereby forming spherical particles. Subsequently, after cooling to room temperature, the oil phase component and spherical particles are separated by a filtration device, washed with spherical particles with acetone, dried in a dryer at 120 ° C. for 24 hours, and composed of zirconia nanoparticles. The porous spherical particles of Example 1 were produced. Furthermore, the obtained porous spherical particles composed of zirconia nanoparticles were fired and sintered at 500 ° C. for 2 hours to produce dense spherical zirconia particles of Example 1 composed of zirconia nanoparticles.
The median diameter (D 50 ) of the dried porous spherical particles and the fired dense spherical particles was measured by a laser diffraction scattering method. Further, image processing (JTrim) was performed on five representative particles photographed with a scanning electron microscope (SEM), and the degree of circularity was obtained by the following equation (a value closer to 1 is circular (spherical)).
Circularity = 4πS / L 2 S: Area, L: Perimeter Length Note that other software (method) may be used for image processing.
These measurement results are shown in Table 1.
「実施例２」
油相成分（油相の液体）として、信越化学（株）社製のシリコーンオイル、ＫＦ９６−１００ｃｓ（粘度１００ｃｓ、比重０．９６５ｇ／ｍｌ）を用い、油相成分の流量を１００ｍｌ／分（このとき多孔質膜管内の油相成分の流速は０．２１１ｍ／s）、水相成分の流量（供給速度）を１０ｍｌ／分、油相成分に対する水相成分の割合を１０体積％とした以外は実施例１と同様にして、実施例２のＷ／Ｏ型エマルション及び球状ジルコニア粒子を作製し、評価した。
これらエマルションの生成条件、得られたエマルションの測定結果、及び球状粒子の測定結果について表１に示す。
"Example 2"
Silicon oil, KF96-100cs (viscosity 100 cs, specific gravity 0.965 g / ml) manufactured by Shin-Etsu Chemical Co., Ltd. is used as the oil phase component (oil phase liquid), and the flow rate of the oil phase component is 100 ml / min (this Sometimes the flow rate of the oil phase component in the porous membrane tube is 0.211 m / s), the flow rate (supply rate) of the water phase component is 10 ml / min, and the ratio of the water phase component to the oil phase component is 10% by volume. In the same manner as in Example 1, the W / O emulsion and spherical zirconia particles of Example 2 were prepared and evaluated.
Table 1 shows the conditions for producing these emulsions, the measurement results of the obtained emulsion, and the measurement results of the spherical particles.
「実施例３」
油相成分の流量を５００ｍｌ／分（このとき多孔質膜管内の油相成分の流速１．０５ｍ／s）、水相成分の流量（供給速度）を５０ｍｌ／分、油相成分に対する水相成分の割合を１０体積％とした以外は実施例２と同様にして、実施例３のＷ／Ｏ型エマルション及び球状ジルコニア粒子を作製し、評価した。
これらエマルションの生成条件、得られたエマルションの測定結果、及び球状粒子の測定結果について表１に示す。
"Example 3"
The flow rate of the oil phase component is 500 ml / min (at this time, the flow rate of the oil phase component in the porous membrane tube is 1.05 m / s), the flow rate of the water phase component (supply speed) is 50 ml / min, and the water phase component relative to the oil phase component The W / O emulsion and spherical zirconia particles of Example 3 were prepared and evaluated in the same manner as in Example 2 except that the ratio was 10% by volume.
Table 1 shows the conditions for producing these emulsions, the measurement results of the obtained emulsion, and the measurement results of the spherical particles.
「実施例４」
油相成分の流量を１０００ｍｌ／分（このとき多孔質膜管内の油相成分の流速２．１１ｍ／s）、水相成分の流量（供給速度）を５０ｍｌ／分、油相成分に対する水相成分の割合を５体積％とした以外は実施例２と同様にして、実施例４のＷ／Ｏ型エマルション及び球状ジルコニア粒子を作製し、評価した。
これらエマルションの生成条件、得られたエマルションの測定結果、及び球状粒子の測定結果について表１に示す。
Example 4
The flow rate of the oil phase component is 1000 ml / min (at this time the flow rate of the oil phase component in the porous membrane tube is 2.11 m / s), the flow rate of the water phase component (supply speed) is 50 ml / min, and the water phase component relative to the oil phase component The W / O emulsion and spherical zirconia particles of Example 4 were prepared and evaluated in the same manner as in Example 2 except that the ratio was 5 vol%.
Table 1 shows the conditions for producing these emulsions, the measurement results of the obtained emulsion, and the measurement results of the spherical particles.
「実施例５」
油相成分として、信越化学（株）社製のシリコーンオイル、ＫＦ９６−１０００ｃｓ（粘度１０００ｃｓ、比重０．９７ｇ／ｍｌ）を用い、油相成分の流量を２０００ｍｌ／分（このとき多孔質膜管内の油相成分の流速４．２１ｍ／s）、水相成分の流量（供給速度）を５０ｍｌ／分、油相成分に対する水相成分の割合を２．５体積％とした以外は実施例２と同様にして、実施例５のＷ／Ｏ型エマルション及び球状ジルコニア粒子を作製し、評価した。
これらエマルションの生成条件、得られたエマルションの測定結果、及び球状粒子の測定結果について表１に示す。
"Example 5"
As the oil phase component, silicone oil KF96-1000cs (viscosity 1000 cs, specific gravity 0.97 g / ml) manufactured by Shin-Etsu Chemical Co., Ltd. was used, and the flow rate of the oil phase component was 2000 ml / min (in this case, the porous membrane Example 2 except that the oil phase component flow rate was 4.21 m / s), the water phase component flow rate (supply rate) was 50 ml / min, and the ratio of the water phase component to the oil phase component was 2.5% by volume. Thus, the W / O emulsion and spherical zirconia particles of Example 5 were prepared and evaluated.
Table 1 shows the conditions for producing these emulsions, the measurement results of the obtained emulsion, and the measurement results of the spherical particles.
「実施例６」
球状粒子製造装置及び管状多孔質膜体は、実施例１と同様の構成とした。
油相成分として、信越化学（株）社製のシリコーンオイル、ＫＦ９６−１００ｃｓ（粘度１００ｃｓ、比重０．９６５ｇ／ｍｌ）を用いた。水相成分として、銀水性コロイド３重量％分散液（表面張力７２ｍＮ／ｍ、比重１．０６ｇ／ｍｌ、分散粒子径２０ｎｍ）を用いた。
油相成分の流量を５００ｍｌ／分（このとき多孔質膜管内の油相成分の流速は１．０５ｍ／ｓ）、水相成分の流量（供給速度）を５０ｍｌ／分、油相成分に対する水相成分の割合を１０体積％とし、実施例１と同様にして、実施例６のＷ／Ｏ型エマルションを生成させた。生成させたＷ／Ｏ型エマルションの安定性は、実施例１と同様に評価した。
"Example 6"
The spherical particle manufacturing apparatus and the tubular porous membrane were configured in the same manner as in Example 1.
As an oil phase component, silicone oil manufactured by Shin-Etsu Chemical Co., Ltd., KF96-100cs (viscosity 100cs, specific gravity 0.965 g / ml) was used. As an aqueous phase component, a silver aqueous colloid 3% by weight dispersion (surface tension 72 mN / m, specific gravity 1.06 g / ml, dispersed particle diameter 20 nm) was used.
The flow rate of the oil phase component is 500 ml / min (at this time, the flow rate of the oil phase component in the porous membrane tube is 1.05 m / s), the flow rate of the water phase component (supply rate) is 50 ml / min, and the water phase relative to the oil phase component The W / O emulsion of Example 6 was produced in the same manner as in Example 1 except that the component ratio was 10% by volume. The stability of the produced W / O emulsion was evaluated in the same manner as in Example 1.
次いで、このエマルションを１３０℃で６時間加熱し、水相成分の溶媒である水を蒸発除去させて球状粒子を形成した。次いで、室温まで冷却した後、濾過装置にて油相成分と球状粒子の分離を行い、アセトンにて球状粒子の洗浄後、乾燥機にて１２０℃−２４時間乾燥させ、銀ナノ粒子からなる、実施例６の多孔質球状粒子を作製した。さらに、得られた銀ナノ粒子からなる多孔質球状粒子を３００℃−２時間焼成して銀粒子を融着させ、銀ナノ粒子からなる、実施例６の緻密な球状銀粒子を作製した。
乾燥した多孔質球状粒子及び焼成した緻密な球状粒子は、実施例１と同様に評価した。測定結果を表１に示す。
Next, this emulsion was heated at 130 ° C. for 6 hours to evaporate and remove the water phase solvent, thereby forming spherical particles. Next, after cooling to room temperature, the oil phase component and spherical particles are separated with a filtration device, washed with spherical particles with acetone, dried in a dryer at 120 ° C. for 24 hours, and composed of silver nanoparticles. The porous spherical particles of Example 6 were produced. Furthermore, the porous spherical particles made of the obtained silver nanoparticles were fired at 300 ° C. for 2 hours to fuse the silver particles, and the fine spherical silver particles of Example 6 made of silver nanoparticles were produced.
The dried porous spherical particles and the fired dense spherical particles were evaluated in the same manner as in Example 1. The measurement results are shown in Table 1.
「実施例７」
水相成分として、多木化学（株）社製のチタニアゾル、Ｍ−６の５重量％分散液（表面張力７２ｍＮ／ｍ、比重１．０３ｇ／ｍｌ、平均分散粒子径３０ｎｍ）を用いたこと以外は実施例６と同様にして、実施例７のＷ／Ｏ型エマルションを生成させた。生成させたＷ／Ｏ型エマルションの安定性は、実施例１と同様に評価した。
"Example 7"
Other than using titania sol manufactured by Taki Chemical Co., Ltd. as a water phase component, 5 wt% dispersion of M-6 (surface tension 72 mN / m, specific gravity 1.03 g / ml, average dispersed particle size 30 nm) Produced a W / O emulsion of Example 7 in the same manner as in Example 6. The stability of the produced W / O emulsion was evaluated in the same manner as in Example 1.
次いで、このエマルションから、実施例１と同様にして、チタニアナノ粒子からなる、実施例７の多孔質球状粒子を作製した。さらに、得られたチタニアナノ粒子からなる多孔質球状粒子を実施例１と同様に焼成して焼結させ、チタニアナノ粒子からなる、実施例７の緻密な球状ジルコニア粒子を作製した。
乾燥した多孔質球状粒子及び焼成した緻密な球状粒子は、実施例１と同様に評価した。測定結果を表１に示す。
Next, porous spherical particles of Example 7 made of titania nanoparticles were produced from this emulsion in the same manner as in Example 1. Furthermore, the obtained porous spherical particles made of titania nanoparticles were fired and sintered in the same manner as in Example 1 to produce dense spherical zirconia particles of Example 7 made of titania nanoparticles.
The dried porous spherical particles and the fired dense spherical particles were evaluated in the same manner as in Example 1. The measurement results are shown in Table 1.
「実施例８」
水相成分として、日本化学工業（株）社製のコロイダルシリカ、シリカドール４０Ｌの５重量％分散液（表面張力７２ｍＮ／ｍ、比重１．０２ｇ／ｍｌ、分散粒子径３０ｎｍ）を用いたこと以外は実施例６と同様にして、実施例８のＷ／Ｏ型エマルションを生成させた。生成させたＷ／Ｏ型エマルションの安定性は、実施例１と同様に評価した。
"Example 8"
Other than using 5% by weight dispersion of colloidal silica and silica dol 40L (surface tension 72 mN / m, specific gravity 1.02 g / ml, dispersed particle diameter 30 nm) manufactured by Nippon Chemical Industry Co., Ltd. as an aqueous phase component Produced a W / O emulsion of Example 8 in the same manner as in Example 6. The stability of the produced W / O emulsion was evaluated in the same manner as in Example 1.
次いで、このエマルションから、実施例１と同様にして、シリカナノ粒子からなる、実施例８の多孔質球状粒子を作製した。さらに、得られたシリカナノ粒子からなる多孔質球状粒子を７００℃−２時間焼成して焼成して焼結させ、シリカ粒子からなる、実施例８の緻密な球状シリカ粒子を作製した。
乾燥した多孔質球状粒子及び焼成した緻密な球状粒子は、実施例１と同様に評価した。測定結果を表１に示す。
Next, in the same manner as in Example 1, porous spherical particles of Example 8 made of silica nanoparticles were produced from this emulsion. Furthermore, the obtained porous spherical particles made of silica nanoparticles were fired at 700 ° C. for 2 hours, fired and sintered, thereby producing dense spherical silica particles of Example 8 made of silica particles.
The dried porous spherical particles and the fired dense spherical particles were evaluated in the same manner as in Example 1. The measurement results are shown in Table 1.
「比較例１」
球状粒子製造装置及び管状多孔質膜体は、実施例１と同様の構成とした。
油相成分として、信越化学（株）社製のシリコーンオイル、ＫＦ９６−１ｃｓ（粘度１ｃｓ、比重０．８１８ｇ／ｍｌ）を用いた。水相成分として、住友大阪セメント（株）社製のナノジルコニア５重量％分散液（表面張力７２ｍＮ／ｍ、比重１．０５ｇ／ｍｌ、分散粒子径９ｎｍ）を用いた。
油相成分の流量を５０ｍｌ／分（このとき多孔質膜管内の油相成分の流速は０．１０５ｍ／ｓ）、水相成分の流量（供給速度）を５ｍｌ／分、油相成分に対する水相成分の割合を１０体積％とし、実施例１と同様にして、比較例１のＷ／Ｏ型エマルションを生成させた。
"Comparative Example 1"
The spherical particle manufacturing apparatus and the tubular porous membrane were configured in the same manner as in Example 1.
As an oil phase component, silicone oil manufactured by Shin-Etsu Chemical Co., Ltd., KF96-1cs (viscosity 1 cs, specific gravity 0.818 g / ml) was used. As a water phase component, a 5% by weight nano zirconia dispersion (surface tension 72 mN / m, specific gravity 1.05 g / ml, dispersed particle diameter 9 nm) manufactured by Sumitomo Osaka Cement Co., Ltd. was used.
The flow rate of the oil phase component is 50 ml / min (at this time, the flow rate of the oil phase component in the porous membrane tube is 0.105 m / s), the flow rate of the water phase component (supply rate) is 5 ml / min, and the water phase relative to the oil phase component The W / O emulsion of Comparative Example 1 was produced in the same manner as in Example 1 except that the component ratio was 10% by volume.
生成させたＷ／Ｏ型エマルションの安定性を、実施例１と同様に評価した。その結果、生成した直後はエマルション状態が確認され、エマルション粒径の測定も可能であつたが、２４時間２５℃静置後には、エマルション状態は消失して油相と水相の２相分離状態となった。このため、比較例１では球状粒子を得ることができなかった。 The stability of the produced W / O emulsion was evaluated in the same manner as in Example 1. As a result, the emulsion state was confirmed immediately after generation, and the emulsion particle size could be measured, but after standing at 25 ° C. for 24 hours, the emulsion state disappeared and the oil phase and the aqueous phase were separated into two phases. It became. For this reason, in Comparative Example 1, spherical particles could not be obtained.
「比較例２」
油相成分の流量を１００ｍｌ／分（このとき多孔質膜管内の油相成分の流速０．２１１ｍ／s）、水相成分の流量（供給速度）を５ｍｌ／分、油相成分に対する水相成分の割合を５体積％とした以外は比較例１と同様にして、比較例２のＷ／Ｏ型エマルションを生成させた。
"Comparative Example 2"
The flow rate of the oil phase component is 100 ml / min (at this time the flow rate of the oil phase component in the porous membrane tube is 0.211 m / s), the flow rate of the water phase component (supply rate) is 5 ml / min, and the water phase component relative to the oil phase component The W / O emulsion of Comparative Example 2 was produced in the same manner as in Comparative Example 1 except that the ratio was 5 vol%.
生成させたＷ／Ｏ型エマルションの安定性を、実施例１と同様に評価した。その結果、生成した直後はエマルション状態が確認され、エマルション粒径の測定も可能であったが、２４時間２５℃静置後には、エマルション状態は消失して油相と水相の２相分離状態となった。このため、比較例２では球状粒子を得ることができなかった。 The stability of the produced W / O emulsion was evaluated in the same manner as in Example 1. As a result, the emulsion state was confirmed immediately after generation, and the emulsion particle size could be measured, but after standing for 24 hours at 25 ° C., the emulsion state disappeared and the oil phase and the aqueous phase were separated into two phases. It became. For this reason, spherical particles could not be obtained in Comparative Example 2.
「比較例３」
球状粒子製造装置及び管状多孔質膜体は、実施例１と同様の構成とした。
油相成分として、信越化学（株）社製のシリコーンオイル、ＫＦ９６−１００ｃｓ（粘度１００ｃｓ、比重０．９６５ｇ／ｍｌ）を用いた。水相成分として、住友大阪セメント（株）社製のナノジルコニア水−メタノール分散液の５重量％液（表面張力３２ｍＮ／ｍ、比重１．０４ｇ／ｍｌ、分散粒子径９ｎｍ）を用いた。
油相成分の流量を１０００ｍｌ／分（このとき多孔質膜管内の油相成分の流速は２．１１ｍ／ｓ）、水相成分の流量（供給速度）を５０ｍｌ／分、油相成分に対する水相成分の割合を５体積％とし、実施例１と同様にして、比較例３のＷ／Ｏ型エマルションを生成させた。
“Comparative Example 3”
The spherical particle manufacturing apparatus and the tubular porous membrane were configured in the same manner as in Example 1.
As an oil phase component, silicone oil manufactured by Shin-Etsu Chemical Co., Ltd., KF96-100cs (viscosity 100cs, specific gravity 0.965 g / ml) was used. As a water phase component, a 5 wt% liquid (surface tension 32 mN / m, specific gravity 1.04 g / ml, dispersed particle diameter 9 nm) of nano zirconia water-methanol dispersion manufactured by Sumitomo Osaka Cement Co., Ltd. was used.
The flow rate of the oil phase component is 1000 ml / min (at this time, the flow rate of the oil phase component in the porous membrane tube is 2.11 m / s), the flow rate of the water phase component (supply speed) is 50 ml / min, and the water phase relative to the oil phase component The W / O emulsion of Comparative Example 3 was produced in the same manner as in Example 1 except that the component ratio was 5% by volume.
生成させたＷ／Ｏ型エマルションの安定性を、実施例１と同様に評価した。その結果、２４時間経過後のメディアン径（Ｄ50）は生成直後に比較して３倍程度大きくなっており、本例のエマルションの安定性が悪いことが示された。このため、比較例３では球状粒子を安定して得ることができなかった。 The stability of the produced W / O emulsion was evaluated in the same manner as in Example 1. As a result, the median diameter (D 50 ) after 24 hours was about 3 times as large as that immediately after production, indicating that the stability of the emulsion of this example was poor. For this reason, in Comparative Example 3, spherical particles could not be obtained stably.
「比較例４」
球状粒子製造装置及び管状多孔質膜体は、実施例１と同様の構成とした。
油相成分として、信越化学（株）社製のシリコーンオイル、ＫＦ９６−１ｃｓ（粘度１ｃｓ、比重０．８１８ｇ／ｍｌ）を用いた。水相成分として、住友大阪セメント（株）社製のナノジルコニア水−メタノール分散液の５重量％液（表面張力３２ｍＮ／ｍ、比重１．０４ｇ／ｍｌ、分散粒子径９ｎｍ）を用いた。
油相成分の流量を２５ｍｌ／分（このとき多孔質膜管内の油相成分の流速は０．０５３ｍ／ｓ）、水相成分の流量（供給速度）を５ｍｌ／分、油相成分に対する水相成分の割合を５体積％とし、実施例１と同様にして、比較例４のＷ／Ｏ型エマルションを生成させた。
“Comparative Example 4”
The spherical particle manufacturing apparatus and the tubular porous membrane were configured in the same manner as in Example 1.
As an oil phase component, silicone oil manufactured by Shin-Etsu Chemical Co., Ltd., KF96-1cs (viscosity 1 cs, specific gravity 0.818 g / ml) was used. As a water phase component, a 5 wt% liquid (surface tension 32 mN / m, specific gravity 1.04 g / ml, dispersed particle diameter 9 nm) of nano zirconia water-methanol dispersion manufactured by Sumitomo Osaka Cement Co., Ltd. was used.
The flow rate of the oil phase component is 25 ml / min (at this time, the flow rate of the oil phase component in the porous membrane tube is 0.053 m / s), the flow rate of the water phase component (supply rate) is 5 ml / min, and the water phase relative to the oil phase component The W / O emulsion of Comparative Example 4 was produced in the same manner as in Example 1 except that the component ratio was 5% by volume.
生成させたＷ／Ｏ型エマルションの安定性を、実施例１と同様に評価した。その結果、生成した直後はエマルション状態が確認され、エマルション粒径の測定も可能であったが、２４時間２５℃静置後には、エマルション状態は消失して油相と水相の２相分離状態となった。このため、比較例４では球状粒子を得ることができなかった。 The stability of the produced W / O emulsion was evaluated in the same manner as in Example 1. As a result, the emulsion state was confirmed immediately after generation, and the emulsion particle size could be measured, but after standing for 24 hours at 25 ° C., the emulsion state disappeared and the oil phase and the aqueous phase were separated into two phases. It became. For this reason, spherical particles could not be obtained in Comparative Example 4.
実施例１〜８の各実施例においては、式（１）の右辺の値（計算値）が、左辺の値である「油相中に形成された水相の液滴径」に比べて大であることから、界面活性剤や分散剤が存在しない状態でも安定したＷ／Ｏ型エマルションが形成されており、これにより形状や粒度均一性に優れた球状粒子を形成させることができた。一方、比較例１〜４においては、式（１）の右辺の値が左辺の値に比べて小であったため、界面活性剤や分散剤が存在しない状態では安定したＷ／Ｏ型エマルションが形成できず、このため形状や粒度均一性に優れた球状粒子も得ることができなかった。 In each of Examples 1 to 8, the value (calculated value) on the right side of Equation (1) is larger than the value on the left side, which is the “droplet diameter of the aqueous phase formed in the oil phase”. Therefore, a stable W / O emulsion was formed even in the absence of a surfactant or a dispersant, whereby spherical particles having excellent shape and particle size uniformity could be formed. On the other hand, in Comparative Examples 1 to 4, since the value on the right side of Formula (1) was smaller than the value on the left side, a stable W / O emulsion was formed in the absence of a surfactant or dispersant. For this reason, spherical particles excellent in shape and particle size uniformity could not be obtained.
１ 管状の多孔質膜体
２、２’ 油相成分
３ 水相成分
４ 一定速度で流れている油相
５ 水相の微小液滴
６、６’ Ｗ／Ｏ型エマルション
７ 油相用ポンプ
８ 水相用ポンプ
９ 流量調整バルブ（１）
１０ 流量調整バルブ（２）
１１ エマルション回収タンク
１２ 加熱装置
１３ 球状粒子
１４ 生成物
DESCRIPTION OF SYMBOLS 1 Tubular porous membrane 2, 2 'Oil phase component 3 Water phase component 4 Oil phase 5 flowing at constant speed Water phase micro droplet 6, 6' W / O type emulsion 7 Oil phase pump 8 Water Phase pump 9 Flow control valve (1)
10 Flow control valve (2)
11 Emulsion recovery tank 12 Heating device 13 Spherical particles 14 Product
Claims (7)
次の（１）〜（３）の各式を満たすように前記Ｗ／Ｏ型エマルションを形成する、Ｗ／Ｏ型エマルションの形成方法。
φ＜（１／３００）・〔（３λ）／（Ｃｐ・Ｒｅ・ρ・ｕ2）〕0.5・・・（１）
Ｃｐ＝１８・（Ｒｅ）-0.6 ・・・・・・（２）
Ｒｅ＝（ｕ・Ｌ）／μ ・・・・・・（３）
（ただし、
φ：油相中に形成させる水相の液滴径
ρ：油相液体の比重
μ：油相液体の動粘度
ｕ：多孔質膜体の管状内部を流れる油相（あるいはエマルション）の流速
λ：水相液体の表面張力
ｌ：多孔質膜の孔径
Ｌ：多孔質膜体の管の内径、である。） An oil phase liquid is allowed to flow inside the tubular porous membrane body, an aqueous phase liquid is allowed to flow outside the tube, the aqueous phase liquid is allowed to permeate the porous membrane body, and the oil phase liquid flowing inside the tube A method of forming a W / O type emulsion that forms spherical aqueous phase droplets in the oil phase liquid by injecting into the liquid,
A method for forming a W / O emulsion, wherein the W / O emulsion is formed so as to satisfy the following formulas (1) to (3).
φ <(1/300) · [(3λ) / (Cp · Re · ρ · u 2 )] 0.5 (1)
Cp = 18 ・ (Re) -0.6・ ・ ・ ・ ・ ・ (2)
Re = (u · L) / μ (3)
(However,
φ: droplet diameter of the water phase formed in the oil phase ρ: specific gravity of the oil phase liquid μ: kinematic viscosity of the oil phase liquid u: flow velocity of the oil phase (or emulsion) flowing inside the tubular membrane body λ: Surface tension 1 of aqueous phase liquid: pore diameter L of porous membrane L: inner diameter of tube of porous membrane body. )
前記エマルションを油相中で固化させる方法が、当該エマルションを加熱することにより水相液滴中の溶媒成分を蒸発除去させる方法である請求項５に記載の球状粒子の製造方法。 The emulsion contains a solid-forming component,
The method for producing spherical particles according to claim 5, wherein the method of solidifying the emulsion in the oil phase is a method of evaporating and removing the solvent component in the aqueous phase droplets by heating the emulsion.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04154605A (en) * | 1990-10-16 | 1992-05-27 | Agency Of Ind Science & Technol | Inorganic uniform fine sphere and preparation thereof |
| JPH09191824A (en) * | 1996-01-23 | 1997-07-29 | Kanegafuchi Chem Ind Co Ltd | Method for producing liquid water-in-oil emulsion |
| JP2005040710A (en) * | 2003-07-22 | 2005-02-17 | Asahi Glass Co Ltd | Method for producing inorganic spherical body |
| WO2009034769A1 (en) * | 2007-09-11 | 2009-03-19 | Agc Si-Tech Co., Ltd. | Porous membrane, process for production of the same, and process for production of inorganic spheres |
| JP2011115730A (en) * | 2009-12-04 | 2011-06-16 | Kyushu Univ | Method for producing composition in which dispersed phase is finely dispersed into continuous phase, and device for producing the composition |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04154605A (en) * | 1990-10-16 | 1992-05-27 | Agency Of Ind Science & Technol | Inorganic uniform fine sphere and preparation thereof |
| JPH09191824A (en) * | 1996-01-23 | 1997-07-29 | Kanegafuchi Chem Ind Co Ltd | Method for producing liquid water-in-oil emulsion |
| JP2005040710A (en) * | 2003-07-22 | 2005-02-17 | Asahi Glass Co Ltd | Method for producing inorganic spherical body |
| WO2009034769A1 (en) * | 2007-09-11 | 2009-03-19 | Agc Si-Tech Co., Ltd. | Porous membrane, process for production of the same, and process for production of inorganic spheres |
| JP2011115730A (en) * | 2009-12-04 | 2011-06-16 | Kyushu Univ | Method for producing composition in which dispersed phase is finely dispersed into continuous phase, and device for producing the composition |
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