JP2014114398A - Ionic liquid polymer-containing composite particulates and method for manufacturing the same - Google Patents
Ionic liquid polymer-containing composite particulates and method for manufacturing the same Download PDFInfo
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- 229920000642 polymer Polymers 0.000 title claims abstract description 106
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 94
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 238000000034 method Methods 0.000 title description 5
- 239000002245 particle Substances 0.000 claims abstract description 66
- 239000000178 monomer Substances 0.000 claims description 49
- 239000010419 fine particle Substances 0.000 claims description 33
- 239000007788 liquid Substances 0.000 claims description 29
- 238000012674 dispersion polymerization Methods 0.000 claims description 28
- 239000011258 core-shell material Substances 0.000 claims description 9
- 238000010526 radical polymerization reaction Methods 0.000 claims description 2
- 239000011859 microparticle Substances 0.000 claims 2
- 230000008878 coupling Effects 0.000 abstract 1
- 238000010168 coupling process Methods 0.000 abstract 1
- 238000005859 coupling reaction Methods 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
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- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 12
- 239000004926 polymethyl methacrylate Substances 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 10
- -1 2- Imidazolinium cations Chemical class 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
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- 229910052757 nitrogen Inorganic materials 0.000 description 5
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
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- RPQWYTBSMHZFTN-UHFFFAOYSA-N 2-(4,5-dihydroimidazol-1-yl)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCN1CCN=C1 RPQWYTBSMHZFTN-UHFFFAOYSA-N 0.000 description 2
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- 230000000052 comparative effect Effects 0.000 description 2
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
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- 238000005406 washing Methods 0.000 description 2
- QLLUAUADIMPKIH-UHFFFAOYSA-N 1,2-bis(ethenyl)naphthalene Chemical compound C1=CC=CC2=C(C=C)C(C=C)=CC=C21 QLLUAUADIMPKIH-UHFFFAOYSA-N 0.000 description 1
- OKGNMRKOGWTADH-UHFFFAOYSA-N 1,4-dihydropyrimidine Chemical compound C1C=CNC=N1 OKGNMRKOGWTADH-UHFFFAOYSA-N 0.000 description 1
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 1
- CLNJSRYUVYWNQM-UHFFFAOYSA-N 1-ethenyl-2,3-dimethylimidazolidine Chemical compound CC1N(C)CCN1C=C CLNJSRYUVYWNQM-UHFFFAOYSA-N 0.000 description 1
- VPNMTSAIINVZTK-UHFFFAOYSA-N 1-ethenyl-3-methylimidazol-3-ium Chemical compound C[N+]=1C=CN(C=C)C=1 VPNMTSAIINVZTK-UHFFFAOYSA-N 0.000 description 1
- XSIFEEYVDZKEPV-UHFFFAOYSA-N 1-ethenyl-3-methylimidazolidine Chemical compound CN1CCN(C=C)C1 XSIFEEYVDZKEPV-UHFFFAOYSA-N 0.000 description 1
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- YPPBVNCVKSCXRB-UHFFFAOYSA-N 2-[(3-cyano-2-methylpentan-3-yl)diazenyl]-2-ethyl-3-methylbutanenitrile Chemical compound CCC(C(C)C)(C#N)N=NC(CC)(C#N)C(C)C YPPBVNCVKSCXRB-UHFFFAOYSA-N 0.000 description 1
- OWTQQPNDSWCHOV-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical compound OCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO OWTQQPNDSWCHOV-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- PCCMCVOWICDLKV-UHFFFAOYSA-N 3-(4,5-dihydroimidazol-1-yl)propyl prop-2-enoate Chemical compound C=CC(=O)OCCCN1CCN=C1 PCCMCVOWICDLKV-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229910017008 AsF 6 Inorganic materials 0.000 description 1
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- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- REHCISZUJVXFRA-UHFFFAOYSA-N C(C)N(C1=[N+](C=C(N1C=C)C)C)CC Chemical compound C(C)N(C1=[N+](C=C(N1C=C)C)C)CC REHCISZUJVXFRA-UHFFFAOYSA-N 0.000 description 1
- FGZSONSGYIPQIH-UHFFFAOYSA-N C1CCN(CN1C=C)C Chemical compound C1CCN(CN1C=C)C FGZSONSGYIPQIH-UHFFFAOYSA-N 0.000 description 1
- DYOCYWFSFWSVPD-UHFFFAOYSA-N C=CC(=O)OCCN1CCCN=C1 Chemical compound C=CC(=O)OCCN1CCCN=C1 DYOCYWFSFWSVPD-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- DLQYTGXECTXDHD-UHFFFAOYSA-N [Li].C(C=C)(=O)OCCC=1NC=CN1 Chemical compound [Li].C(C=C)(=O)OCCC=1NC=CN1 DLQYTGXECTXDHD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
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- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 description 1
- DTPCFIHYWYONMD-UHFFFAOYSA-N decaethylene glycol Chemical compound OCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO DTPCFIHYWYONMD-UHFFFAOYSA-N 0.000 description 1
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 description 1
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- 239000001257 hydrogen Substances 0.000 description 1
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- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- ZARXZEARBRXKMO-UHFFFAOYSA-N n,n-bis(ethenyl)aniline Chemical compound C=CN(C=C)C1=CC=CC=C1 ZARXZEARBRXKMO-UHFFFAOYSA-N 0.000 description 1
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- 229960000834 vinyl ether Drugs 0.000 description 1
Abstract
Description
本発明は、イオン液体ポリマー含有複合微粒子およびその製造方法に関する。 The present invention relates to ionic liquid polymer-containing composite fine particles and a method for producing the same.
常温においても溶融した塩であるイオン液体は、環境適応型媒体としての利用に加え、イオン伝導性や二酸化炭素吸収能等、様々な機能を有しており、アニオン種・カチオン種を設計することによって、磁性や液晶性、蛍光特性等を発現することから、機能性材料としての応用が期待され、各種検討が行われている。近年では、力学特性や加工性等の観点から、イオン液体の特性を保持したまま「固体化」するためのイオン液体ポリマーについても検討されるようになってきた（例えば、特許文献１）。しかし、特許文献１では、その用途はポリマー電解質にとどまり、イオン液体の多種の機能を応用展開できるものではなかった。 The ionic liquid, which is a salt melted even at room temperature, has various functions such as ion conductivity and carbon dioxide absorption capacity in addition to its use as an environmentally adaptable medium. Design anion and cation species. Therefore, it is expected to be applied as a functional material, and various studies have been conducted. In recent years, from the viewpoints of mechanical properties and workability, ionic liquid polymers for “solidifying” while maintaining the properties of ionic liquids have been studied (for example, Patent Document 1). However, in Patent Document 1, the use is limited to the polymer electrolyte, and the various functions of the ionic liquid cannot be applied and developed.
一方、イオン性液体の有する帯電防止能に着目し、基材にイオン性液体のポリマー層を結合させた技術が開発されている（特許文献２、３等）。しかし、いずれの技術においても基材が必要であり、用途が限定されるという問題点があった。 On the other hand, paying attention to the antistatic ability of an ionic liquid, a technique in which a polymer layer of the ionic liquid is bonded to a base material has been developed (Patent Documents 2, 3, etc.). However, any technique requires a base material, and there is a problem in that its use is limited.
本発明は、イオン液体の有する各種機能を有効に発揮させるため、基材にイオン液体ポリマーを結合させるのではなく、幅広い用途への展開が期待できるイオン液体ポリマーの複合微粒子を提供することを課題として掲げた。 An object of the present invention is to provide composite particles of an ionic liquid polymer that can be expected to be used in a wide range of applications, instead of binding an ionic liquid polymer to a base material in order to effectively exhibit various functions of the ionic liquid. As listed.
上記課題を解決した本発明は、１個の粒子中に、非イオン液体ポリマーとイオン液体ポリマーとが、少なくとも一部において相分離した状態で存在していることを特徴とするイオン液体ポリマー含有複合微粒子である。この場合において、非イオン液体ポリマーの表面張力の極性成分γt pが、イオン液体ポリマーの表面張力の極性成分γi pとの差Δγが１４ｍＮ／ｍ以下であることが好ましい。 The present invention that has solved the above problems is characterized in that a nonionic liquid polymer and an ionic liquid polymer are present in one particle in a state of being phase-separated at least partially. Fine particles. In this case, the difference Δγ between the polar component γ t p of the surface tension of the nonionic liquid polymer and the polar component γ i p of the surface tension of the ionic liquid polymer is preferably 14 mN / m or less.
また、上記イオン液体ポリマー含有複合微粒子が、非イオン液体ポリマーが海、イオン液体ポリマーが島である海島構造を有しているか、あるいは、海島構造に代えてまたは加えて、非イオン液体ポリマーがコア、イオン液体ポリマーがシェルであるコアシェル構造を有していることが好ましい。 The composite particles containing the ionic liquid polymer may have a sea-island structure in which the non-ionic liquid polymer is the sea and the ionic liquid polymer is the island, or the non-ionic liquid polymer is the core instead of or in addition to the sea-island structure. The ionic liquid polymer preferably has a core-shell structure that is a shell.
イオン液体ポリマーが、ラジカル重合性不飽和基を有するイオン液体モノマーを必須的に含むモノマー成分のラジカル重合により得られたものであることは、本発明の好適な実施態様である。 It is a preferred embodiment of the present invention that the ionic liquid polymer is obtained by radical polymerization of a monomer component that essentially contains an ionic liquid monomer having a radical polymerizable unsaturated group.
本発明には、非イオン液体ポリマーのシード粒子の存在下、イオン液体モノマーが溶解し、イオン液体ポリマーは溶解しない溶媒中で、シード分散重合することを特徴とするイオン液体ポリマー含有複合微粒子の製造方法も含まれ、この場合において、イオン液体モノマーを含むモノマー成分を、分割添加することが好ましい。 In the present invention, production of composite particles containing ionic liquid polymer, characterized in that seed dispersion polymerization is performed in a solvent in which ionic liquid monomer is dissolved and ionic liquid polymer is not dissolved in the presence of seed particles of nonionic liquid polymer. A method is also included. In this case, it is preferable to add a monomer component containing an ionic liquid monomer in a divided manner.
本発明のイオン液体ポリマー含有複合微粒子は、イオン液体ポリマーが熱可塑性ポリマー等の非イオン液体ポリマーと複合されているため、フィルム化や他の形状の成形体への成形等が容易であり、イオン液体ポリマーが有する種々の機能を発揮させるのに極めて有用である。また、本発明のイオン液体ポリマー含有複合微粒子を別のポリマーに添加して帯電防止性等の機能を付与する目的にも使用することができる。 The ionic liquid polymer-containing composite fine particles of the present invention are easily formed into a film or molded into another shape because the ionic liquid polymer is combined with a nonionic liquid polymer such as a thermoplastic polymer. It is extremely useful for exhibiting various functions of the liquid polymer. Moreover, the ionic liquid polymer-containing composite fine particles of the present invention can be used for the purpose of adding functions such as antistatic properties by adding to another polymer.
本発明のイオン液体ポリマー含有複合微粒子は、１個の粒子中に、非イオン液体ポリマーとイオン液体ポリマーとが少なくとも一部において相分離した状態で存在しているものである。すなわち、非イオン液体ポリマーと、イオン液体ポリマーとは共重合体を形成しているのではなく、粒子内の少なくとも一部において、それぞれ独立のポリマーとして存在している。 The ionic liquid polymer-containing composite fine particles of the present invention are those in which a nonionic liquid polymer and an ionic liquid polymer are present in a phase separated state at least partially in one particle. That is, the nonionic liquid polymer and the ionic liquid polymer do not form a copolymer, but exist as independent polymers in at least a part of the particles.
存在形態としては、非イオン液体ポリマーが海、イオン液体ポリマーが島である海島構造、非イオン液体ポリマーがコア、イオン液体ポリマーがシェルであるコアシェル構造、両者が共存したコアシェル海島構造が挙げられ、このような相分離状態が１個の粒子の中に一部でもあれば、本願発明の複合粒子となる。上記の構造の中でも、イオン液体ポリマーが少量でもその諸機能を充分に発揮することのできるコアシェル構造の粒子が最も好ましい。コアシェル構造は、本発明の複合微粒子をフィルム化したとき等に、シェルが連続相を形成しやすく、帯電防止能や導電性を発揮しやすいためである。 Existence forms include the sea-island structure in which the nonionic liquid polymer is the sea, the ionic liquid polymer is the island, the core-shell structure in which the non-ionic liquid polymer is the core, and the core-shell sea-island structure in which both coexist, If such a phase-separated state is a part of one particle, the composite particle of the present invention is obtained. Among the above structures, particles of a core-shell structure that can sufficiently exhibit their functions even with a small amount of ionic liquid polymer are most preferable. The core-shell structure is because, when the composite fine particles of the present invention are formed into a film, the shell easily forms a continuous phase and easily exhibits antistatic ability and conductivity.
イオン液体ポリマーを得るためのイオン液体モノマーとは、下記式（１）で表され、常温で溶融塩であり、イオン伝導性を有する化合物である。
Ｐ+Ｑ- …（１）
［式中、Ｐ+はカチオンを、Ｑ-はアニオンを表し、Ｐ+および／またはＱ-はラジカル重合性不飽和基を含む。］
The ionic liquid monomer for obtaining the ionic liquid polymer is a compound represented by the following formula (1), which is a molten salt at room temperature and has ionic conductivity.
P + Q - ... (1)
[Wherein P + represents a cation, Q − represents an anion, and P + and / or Q − includes a radically polymerizable unsaturated group. ]
Ｐ+がラジカル重合性不飽和基を含む場合のカチオンの具体例としては、１−メチル−３−ビニルイミダゾリニウム、１，２−ジメチル−３−ビニルイミダゾリニウム、１−メチル−３−（メタ）アクリロイルオキシエチルイミダゾリニウム、１，３−ジメチル−２−（メタ）アクリロイルオキシプロピルイミダゾリニウム、２−メチル−３−ビニルアミノ−１，３，４−トリメチルイミダゾリニウム、２−ジメチルアミノ−１，４−ジメチル−３−（メタ）アクリロイルオキシエチルイミダゾリニウム等のイミダゾリニウムカチオン；１−メチル−３−ビニルイミダゾリウム、１−メチル−３−（メタ）アクリロイルオキシエチルイミダゾリウム、２−メチル−２−（メタ）アクリロイルオキシエチルアミノ−１，３，４−トリメチルイミダゾリウム、２−ジエチルアミノ−１，４−ジメチル−３−ビニルイミダゾリウム等のイミダゾリウムカチオン；１−メチル−３−ビニル−１，４，５，６−テトラヒドロピリミジニウム、１，３−ジメチル−２−（メタ）アクリロイルオキシエチル−１，４，５，６−テトラヒドロピリミジニウム、２−メチル−２−（メタ）アクリロイルオキシエチルアミノ−１，３，４−トリメチル−１，４，５，６−テトラヒドロピリミジニウム等のテトラヒドロピリミジニウムカチオン；１−メチル−３−（メタ）アクリロイルオキシエチル−１，４−または１，６−ジヒドロピリミジニウム等のジヒドロピリミジニウムカチオン；１−メチル−３−ビニルフォスフォニウムカチオン等のフォスフォニウムカチオン；２−（メタ）アクリロイルオキシエチルトリメチルアンモニウム等の（メタ）アクリロイルオキシアルキルトリアルキルアンモニウムカチオン等が挙げられる。また、ビニル基や（メタ）アクリロイル基を有するアリサイクリックカチオンも使用可能である。 Specific examples of the cation when P + contains a radically polymerizable unsaturated group include 1-methyl-3-vinylimidazolinium, 1,2-dimethyl-3-vinylimidazolinium, 1-methyl-3- (Meth) acryloyloxyethylimidazolinium, 1,3-dimethyl-2- (meth) acryloyloxypropylimidazolinium, 2-methyl-3-vinylamino-1,3,4-trimethylimidazolinium, 2- Imidazolinium cations such as dimethylamino-1,4-dimethyl-3- (meth) acryloyloxyethylimidazolinium; 1-methyl-3-vinylimidazolium, 1-methyl-3- (meth) acryloyloxyethylimidazole Lithium, 2-methyl-2- (meth) acryloyloxyethylamino-1,3,4-trimethylimi Imidazolium cations such as zolium and 2-diethylamino-1,4-dimethyl-3-vinylimidazolium; 1-methyl-3-vinyl-1,4,5,6-tetrahydropyrimidinium, 1,3-dimethyl- 2- (meth) acryloyloxyethyl-1,4,5,6-tetrahydropyrimidinium, 2-methyl-2- (meth) acryloyloxyethylamino-1,3,4-trimethyl-1,4,5 Tetrahydropyrimidinium cations such as 6-tetrahydropyrimidinium; dihydropyrimidinium cations such as 1-methyl-3- (meth) acryloyloxyethyl-1,4- or 1,6-dihydropyrimidinium; Phosphonium cations such as methyl-3-vinylphosphonium cation; 2- (meth) acryloyloxy And (meth) acryloyloxyalkyltrialkylammonium cations such as ethyltrimethylammonium. An alicyclic cation having a vinyl group or a (meth) acryloyl group can also be used.
Ｑ-がラジカル重合性不飽和基を含む場合のアニオンの具体例としては、ビニル基や（メタ）アクリロイル基を有するカルボン酸、スルホン酸、リン酸およびこれらのエステルが挙げられる。 Q - Specific examples of the anion in the case of including a radically polymerizable unsaturated group is a carboxylic acid having a vinyl group or a (meth) acryloyl group, a sulfonic acid, phosphoric acid and their esters.
Ｐ+がラジカル重合性不飽和基を含む場合、Ｑ-はラジカル重合性不飽和基を持っていなくてもよく、そのようなアニオンの具体例としては、ＢＦ4、ＰＦ6、ＡｓＦ6、ＣＦ3ＳＯ3、Ｃ（ＣＦ3ＳＯ2）3、Ｎ（ＣＦ3ＣＦ2ＳＯ2）2、Ｎ（ＣＦ3ＳＯ2）2、Ｎ（ＦＳＯ2）2等が挙げられる。 When P + contains a radically polymerizable unsaturated group, Q − may not have a radically polymerizable unsaturated group, and specific examples of such anions include BF 4 , PF 6 , AsF 6 , CF 3 SO 3 , C (CF 3 SO 2 ) 3 , N (CF 3 CF 2 SO 2 ) 2 , N (CF 3 SO 2 ) 2 , N (FSO 2 ) 2 and the like.
Ｑ-がラジカル重合性不飽和基を含む場合、Ｐ+はラジカル重合性不飽和基を持っていなくてもよく、そのようなカチオンの具体例としては、ラジカル重合性不飽和基を含有するＰ+として例示したカチオンの中で、ビニル基や（メタ）アクリロイル基を水素やアルキル基に置き換えたカチオンが挙げられる。 When Q − contains a radically polymerizable unsaturated group, P + may not have a radically polymerizable unsaturated group. Specific examples of such cations include P containing a radically polymerizable unsaturated group. Among the cations exemplified as + , cations in which a vinyl group or a (meth) acryloyl group is replaced with hydrogen or an alkyl group can be mentioned.
非イオン液体ポリマーのシード粒子中で、イオン液体ポリマーを重合する際には、イオン液体ポリマーの特性を損なわない範囲（例えば、イオン液体モノマーと他のモノマーからなるモノマー成分（以下、イオン液体ポリマー用モノマー成分ということがある）１００質量％中、５０質量％以下）で、イオン液体モノマーではない他のモノマーを一部用いてもよく、このような併用可能な他のモノマーとしては、カルボキシル基、スルホン酸基、リン酸基、およびこれらの塩基等を有するモノマー；２−ヒドロキシエチル（メタ）アクリレートのような水酸基含有モノマー；（メタ）アクリルアミド、Ｎ−ビニルピロリドン等の含窒素モノマー；メチル（メタ）アクリレート等のアルキル（メタ）アクリレート；エチレンおよびブタジエン等の脂肪族不飽和炭化水素類ならびに塩化ビニル等の脂肪族不飽和炭化水素類のハロゲン置換体；スチレンおよびα−メチルスチレン等の芳香族不飽和炭化水素類；ビニルエーテル類等が挙げられる。 When polymerizing the ionic liquid polymer in the seed particles of the non-ionic liquid polymer, a range that does not impair the characteristics of the ionic liquid polymer (for example, a monomer component composed of an ionic liquid monomer and another monomer (hereinafter, for ionic liquid polymer) (It may be called a monomer component) 50% by mass or less in 100% by mass), and a part of the other monomer that is not an ionic liquid monomer may be used. Monomers having sulfonic acid groups, phosphoric acid groups, and bases thereof; hydroxyl group-containing monomers such as 2-hydroxyethyl (meth) acrylate; nitrogen-containing monomers such as (meth) acrylamide and N-vinylpyrrolidone; methyl (meta ) Alkyl (meth) acrylates such as acrylate; ethylene and butadiene, etc. Halogen-substituted derivatives of aliphatic unsaturated hydrocarbons and aliphatic and vinyl chloride unsaturated hydrocarbons, aromatic unsaturated hydrocarbons such as styrene and α- methylstyrene; vinyl ethers.
本発明のイオン液体ポリマー含有複合微粒子のもう一つの必須成分は、非イオン液体ポリマーである。非イオン液体ポリマーとしては、熱可塑性ポリマーあるいは熱可塑性ポリマーを架橋した架橋熱可塑性ポリマーが好ましい。熱可塑性ポリマーや架橋熱可塑性ポリマーは、複合微粒子をフィルム化や他の形状に成形する際に、ハンドリング性が良好で、本発明の複合微粒子の用途展開を大幅に広げることができる。 Another essential component of the ionic liquid polymer-containing composite fine particles of the present invention is a nonionic liquid polymer. The nonionic liquid polymer is preferably a thermoplastic polymer or a crosslinked thermoplastic polymer obtained by crosslinking a thermoplastic polymer. The thermoplastic polymer and the crosslinked thermoplastic polymer have good handling properties when the composite fine particles are formed into a film or formed into another shape, and can greatly expand the application development of the composite fine particles of the present invention.
本発明では、後述するシード分散重合によって複合微粒子を製造するが、シード分散重合のシード粒子として機能するためには、非イオン液体ポリマーの表面張力の極性成分γt pと、イオン液体ポリマーの表面張力の極性成分γi pとの差γt p−γi p＝Δγが１４ｍＮ／ｍ（室温）以下であることが好ましい。 In the present invention, composite fine particles are produced by seed dispersion polymerization described later. In order to function as seed particles for seed dispersion polymerization, the polar component γ t p of the surface tension of the nonionic liquid polymer and the surface of the ionic liquid polymer are used. It is preferable that the difference γ t p −γ i p = Δγ of the tension with respect to the polar component γ i p is 14 mN / m or less (room temperature).
表面張力γLは、接触角θを用いたＹｏｕｎｇ−Ｏｗｅｎｓの式によれば、下記で表される。 The surface tension γ L is expressed as follows according to the Young-Owens equation using the contact angle θ.
ここで、γs dは液体を載せて接触角を測定するときの固体（ポリマー）の表面張力の分散成分、γL dは接触角の測定に用いた液体の表面張力の分散成分、γs pは固体（ポリマー）の表面張力の極性成分、γL pは接触角の測定に用いた液体の表面張力の極性成分である。表面張力が既知の２種の液体で接触角を測定し、連立方程式を解けば各成分の値が求まる。本発明では、水（γL＝７２．８、γL p＝５１、γL d＝２１．８）とヨウ化メチレン（γL＝５０．８、γL p＝１．３、γL d＝４９．５）とを用いて求めた。このようにして求めた非イオン液体ポリマーの表面張力の極性成分γt pと、イオン液体ポリマーの表面張力の極性成分γi pとの差γt p−γi p＝Δγが１４ｍＮ／ｍ以下であれば、後述するシード分散重合の際に、非イオン液体ポリマーのシード粒子の中にイオン液体ポリマー用モノマー成分が入り込みやすく、本発明の複合微粒子が得られやすいことが本発明者等に見出されている。Δγが１４ｍＮ／ｍ（室温）を超えるような非イオン液体ポリマーとイオン液体ポリマーの組み合わせは、シード分散重合の際に、シード粒子の中にイオン液体ポリマー用モノマー成分が入り込みにくくなって、イオン液体ポリマー用モノマー成分のみからなるポリマー粒子が多く生成するため好ましくない。 Here, γ s d is a dispersion component of the surface tension of the solid (polymer) when the contact angle is measured by placing a liquid, γ L d is a dispersion component of the surface tension of the liquid used for measuring the contact angle, and γ s p is a polar component of the surface tension of the solid (polymer), and γ L p is a polar component of the surface tension of the liquid used for measuring the contact angle. By measuring the contact angle with two types of liquids with known surface tensions and solving the simultaneous equations, the values of each component can be obtained. In the present invention, water (γ L = 72.8, γ L p = 51, γ L d = 21.8) and methylene iodide (γ L = 50.8, γ L p = 1.3, γ L d = 49.5). The difference γ t p −γ i p = Δγ between the polar component γ t p of the surface tension of the nonionic liquid polymer thus obtained and the polar component γ i p of the surface tension of the ionic liquid polymer is 14 mN / m or less. Therefore, the present inventors have found that the monomer component for the ionic liquid polymer can easily enter the seed particles of the nonionic liquid polymer during the seed dispersion polymerization described later, and the composite fine particles of the present invention can be easily obtained. Has been issued. The combination of the nonionic liquid polymer and the ionic liquid polymer in which Δγ exceeds 14 mN / m (room temperature) makes it difficult for the monomer component for the ionic liquid polymer to enter the seed particles during the seed dispersion polymerization. Since many polymer particles consisting only of the monomer component for the polymer are generated, it is not preferable.
非イオン液体ポリマーとしては、イオン液体ポリマーのγi pが比較的大きいことから、γt pの大きい比較的親水性のポリマーが好ましい。よって、非イオン液体ポリマーの合成の際には親水性が比較的高いモノマーを用いることが好ましく、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート等が好適である。これらは１種または２種以上を混合して、重合に供することができる。 As the nonionic liquid polymer, a relatively hydrophilic polymer having a large γ t p is preferable because the ionic liquid polymer has a relatively large γ i p . Therefore, in the synthesis of the nonionic liquid polymer, it is preferable to use a monomer having a relatively high hydrophilicity. For example, methyl (meth) acrylate, ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and the like are suitable. is there. These may be used alone or in combination of two or more.
また、ポリマーのγt pが小さく、上記Δγが１４ｍＮ／ｍ以下にならない場合でも、コアをそのような疎水性ポリマーとして、シェルをΔγが１４ｍＮ／ｍ以下になるようなポリマーでシード粒子を構成することで、本発明の複合微粒子を得ることが可能である。 Even if the polymer γ t p is small and the Δγ is not less than 14 mN / m, the core is made of such a hydrophobic polymer, and the shell is made of a polymer that makes the Δγ less than 14 mN / m. By doing so, it is possible to obtain the composite fine particles of the present invention.
非イオン液体ポリマーは、架橋熱可塑性ポリマーであってもよい。架橋熱可塑性ポリマーを合成するには、一分子中にラジカル重合性不飽和基を２個以上有する架橋性モノマーを、上記メチル（メタ）アクリレートやエチル（メタ）アクリレートモノマーと共重合させればよい。 The nonionic liquid polymer may be a cross-linked thermoplastic polymer. In order to synthesize a crosslinked thermoplastic polymer, a crosslinkable monomer having two or more radically polymerizable unsaturated groups in one molecule may be copolymerized with the above methyl (meth) acrylate or ethyl (meth) acrylate monomer. .
架橋性モノマーとしては、ジビニルベンゼン、ジビニルナフタレン、およびこれらの誘導体等の芳香族ジビニル化合物；トリメチロールプロパンジ（またはトリ）（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、デカエチレングリコールジ（メタ）アクリレート、ペンタデカエチレングリコールジ（メタ）アクリレート、等の（メタ）アクリル系モノマー；Ｎ，Ｎ−ジビニルアニリン、ジビニルエーテル、ジビニルサルファイド、ジビニルスルホン酸等が挙げられ、これらの１種または２種以上を用いることができる。これらの架橋性モノマーは、架橋熱可塑性ポリマーの原料モノマー１００質量％中、１０質量％以下の使用が好ましく、５質量％以下の使用がより好ましい。この程度の使用量であれば、Δγに影響を及ぼすことはない。 Examples of crosslinkable monomers include aromatic divinyl compounds such as divinylbenzene, divinylnaphthalene, and derivatives thereof; trimethylolpropane di (or tri) (meth) acrylate, ethylene glycol di (meth) acrylate, and diethylene glycol di (meth) acrylate. , (Meth) acrylic monomers such as triethylene glycol di (meth) acrylate, decaethylene glycol di (meth) acrylate, pentadecaethylene glycol di (meth) acrylate; N, N-divinylaniline, divinyl ether, divinyl sulfide , Divinyl sulfonic acid and the like, and one or more of these can be used. These crosslinkable monomers are preferably used in an amount of 10% by mass or less, more preferably 5% by mass or less, in 100% by mass of the raw material monomer of the crosslinked thermoplastic polymer. With this amount of use, Δγ is not affected.
次に、本発明の複合微粒子の製造方法について説明する。本発明では、複合微粒子をシード分散重合によって合成する。本発明で用いるシード分散重合とは、非イオン液体ポリマー粒子をシード粒子として溶媒中に分散させた状態で、溶媒にイオン液体ポリマー用モノマー成分を溶解させ、重合開始剤を添加して重合させる方法である。シード粒子中にイオン液体ポリマー用モノマー成分が吸収されてシード粒子の粒径が大きくなり、溶媒中に他の粒子（イオン液体ポリマー用モノマー成分のみのポリマー粒子）が分散していなければ、シード分散重合が起こったことを確認できる。 Next, the method for producing composite fine particles of the present invention will be described. In the present invention, composite fine particles are synthesized by seed dispersion polymerization. The seed dispersion polymerization used in the present invention is a method in which nonionic liquid polymer particles are dispersed in a solvent as seed particles, the monomer component for the ionic liquid polymer is dissolved in the solvent, and a polymerization initiator is added to perform polymerization. It is. If the monomer component for the ionic liquid polymer is absorbed in the seed particle and the particle size of the seed particle becomes large, and other particles (polymer particles of only the monomer component for the ionic liquid polymer) are not dispersed in the solvent, the seed dispersion It can be confirmed that polymerization has occurred.
シード粒子とイオン液体ポリマー用モノマー成分の使用量の比率は特に限定されないが、シード粒子とイオン液体ポリマー用モノマー成分の合計を１００質量％としたときに、イオン液体ポリマー用モノマー成分を１〜７５質量％とすることが好ましい。 The ratio of the use amount of the seed particle and the monomer component for the ionic liquid polymer is not particularly limited, but when the total of the seed particle and the monomer component for the ionic liquid polymer is 100% by mass, the monomer component for the ionic liquid polymer is 1 to 75%. It is preferable to set it as the mass%.
溶媒は、非イオン液体ポリマーやイオン液体ポリマーを溶解せず、イオン液体ポリマー用モノマー成分は溶解できるものを用いる必要があり、例えば、水；メタノール、エタノール等の低級アルコール；酢酸メチル、酢酸エチル等のエステル類等を、単独でまたは混合して使用することができる。溶媒は、シード粒子とイオン液体ポリマー用モノマー成分の合計使用量１質量部に対し、１〜１００質量部程度が好ましい。 It is necessary to use a solvent that does not dissolve the nonionic liquid polymer or the ionic liquid polymer and that can dissolve the monomer component for the ionic liquid polymer, such as water; lower alcohols such as methanol and ethanol; methyl acetate, ethyl acetate, and the like. These esters and the like can be used alone or in combination. As for a solvent, about 1-100 mass parts is preferable with respect to 1 mass part of total usage-amount of a seed particle and the monomer component for ionic liquid polymers.
重合開始剤としては、従来公知のアゾ系化合物や過酸化物が使用可能である。例えば、アゾ系化合物としては、２，２’−アゾビスイソブチロニトリル、２，２’−アゾビス（２，４−ジメチルバレロニトリル）、２，２’−アゾビス（２，３−ジメチルブチロニトリル）、２，２’−アゾビス−（２−メチルブチロニトリル）、２，２’−アゾビス（４−メトキシ−２，４−ジメチルバレロニトリル）、２，２’−アゾビス（２，３，３−トリメチルブチロニトリル）、２，２’−アゾビス（２−イソプロピルブチロニトリル）等が、過酸化物としては、ベンゾイルパーオキサイド、クメンハイドロパーオキサイド、シクロヘキサノンパーオキサイド、ｔ−ブチルハイドロパーオキサイド、ジイソプロピルベンゼンハイドロパーオキサイド等が挙げられ、これらのうちの１種または２種以上を用いることができる。重合開始剤は、イオン液体ポリマー用モノマー成分１００質量部に対し、０．１〜５質量部程度、用いることが好ましい。 As the polymerization initiator, conventionally known azo compounds and peroxides can be used. For example, azo compounds include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,3-dimethylbutyro). Nitrile), 2,2′-azobis- (2-methylbutyronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2,3,3) 3-trimethylbutyronitrile), 2,2'-azobis (2-isopropylbutyronitrile) and the like are peroxides such as benzoyl peroxide, cumene hydroperoxide, cyclohexanone peroxide, t-butyl hydroperoxide And diisopropylbenzene hydroperoxide, and one or more of these can be used. The polymerization initiator is preferably used in an amount of about 0.1 to 5 parts by mass with respect to 100 parts by mass of the monomer component for ionic liquid polymer.
具体的なシード分散重合としては、溶媒中に非イオン液体ポリマー粒子を分散させ、イオン液体ポリマー用モノマー成分と重合開始剤を添加して重合を行う。機械的撹拌を行うことが望ましい。分散安定剤として、部分鹸化ポリビニルアルコール、カルボキシメチルセルロース、ポリビニルピロリドン等を用いて、分散安定性を高めてもよい。これらの分散安定剤は、溶媒１００質量部に対し、０．１〜１０質量部程度、使用することが好ましい。 As specific seed dispersion polymerization, nonionic liquid polymer particles are dispersed in a solvent, and a monomer component for ionic liquid polymer and a polymerization initiator are added to perform polymerization. It is desirable to perform mechanical stirring. Dispersion stability may be enhanced by using partially saponified polyvinyl alcohol, carboxymethyl cellulose, polyvinyl pyrrolidone, or the like as the dispersion stabilizer. These dispersion stabilizers are preferably used in an amount of about 0.1 to 10 parts by mass with respect to 100 parts by mass of the solvent.
イオン液体ポリマー用モノマー成分は、最初に一括添加してもよく、何回かに分けて分割添加してもよく、滴下してもよい。コアシェル構造を作りやすいという点からは、分割添加か滴下が好ましく、この場合は重合開始剤と共に分割添加や滴下を行うことが好ましい。分割添加の場合は、イオン液体ポリマー用モノマー成分全量を５分割以上に分割して行うことが好ましい。 The monomer component for the ionic liquid polymer may be added all at once, or may be added in several divided portions, or may be dropped. From the viewpoint that a core-shell structure can be easily formed, divided addition or dropping is preferable. In this case, it is preferable to perform divided addition or dropping together with the polymerization initiator. In the case of divided addition, it is preferable to divide the total amount of monomer components for the ionic liquid polymer into 5 or more.
重合は窒素等の不活性ガス雰囲気で行い、重合温度は１０〜１００℃程度、重合時間は、１〜１００時間程度が好ましい。 Polymerization is performed in an inert gas atmosphere such as nitrogen, the polymerization temperature is preferably about 10 to 100 ° C., and the polymerization time is preferably about 1 to 100 hours.
なお、シード粒子は、乳化重合で合成してもよいし、上記シード分散重合にならって分散重合（シード粒子の不存在下での分散重合）で合成してもよい。シード粒子の分子量は、Ｍｗで１００００〜３００００程度が好ましい。なお、イオン液体ポリマーの分子量は、Ｍｗで１００００〜１００００００程度が好ましい。 The seed particles may be synthesized by emulsion polymerization, or may be synthesized by dispersion polymerization (dispersion polymerization in the absence of seed particles) following the seed dispersion polymerization. The molecular weight of the seed particles is preferably about 10,000 to 30,000 in terms of Mw. The molecular weight of the ionic liquid polymer is preferably about 10,000 to 1,000,000 in terms of Mw.
シード粒子の粒径と、イオン液体ポリマー用モノマー成分の量を制御することで、本発明の複合微粒子の粒径を制御することができる。用途にもよるが、複合微粒子の平均粒径は０．１μｍ〜数十μｍ程度が好ましい。なお、本発明の平均粒径は、１００個以上の複合微粒子のＳＥＭ写真を画像処理ソフト（「ＷｉｎＲＯＯＦ」；三谷商事社製）で解析して、平均粒径ｄｎと変動係数（ＣＶ）を算出したものである。 By controlling the particle size of the seed particles and the amount of the monomer component for the ionic liquid polymer, the particle size of the composite fine particles of the present invention can be controlled. Although depending on the application, the average particle size of the composite fine particles is preferably about 0.1 μm to several tens of μm. The average particle size of the present invention is calculated by analyzing an SEM photograph of 100 or more composite fine particles with image processing software (“WinROOF”; manufactured by Mitani Corporation) and calculating the average particle size dn and coefficient of variation (CV). It is a thing.
次に、実施例および比較例を用いて本発明を具体的に説明するが、本発明は、これらの実施例の態様に何ら限定されるものではなく、本発明の趣旨を逸脱しない範囲で適宜変更することが可能である。 Next, the present invention will be specifically described using examples and comparative examples. However, the present invention is not limited to the modes of these examples, and may be appropriately selected without departing from the spirit of the present invention. It is possible to change.
＜ポリスチレンシード粒子の合成＞
ガラス管に、スチレン１ｇ、アゾイソブチロニトリル０．０１ｇ、ポリビニルピロリドン（「ポリビニルピロリドンＫ−３０」；ナカライテスク社から入手；Ｍｗ４０，０００）０．２ｇ、エタノール６ｇを仕込み、窒素置換してから、ガラス管を密封し、６０℃の水浴を備えた振盪器で、８０サイクル／分で振盪させながら、２４時間重合を行い、ポリスチレンのシード粒子を合成した。このシード粒子は、平均粒径ｄｎが１．７μｍであった。
<Synthesis of polystyrene seed particles>
A glass tube was charged with 1 g of styrene, 0.01 g of azoisobutyronitrile, 0.2 g of polyvinylpyrrolidone (“polyvinylpyrrolidone K-30”; obtained from Nacalai Tesque; Mw 40,000), and 6 g of ethanol, and the atmosphere was replaced with nitrogen. Then, the glass tube was sealed, and polymerization was performed for 24 hours with a shaker equipped with a 60 ° C. water bath at 80 cycles / minute to synthesize polystyrene seed particles. The seed particles had an average particle diameter dn of 1.7 μm.
＜［２−（メタクリロイルオキシ）エチル］トリメチルアンモニウム・ビス（トリフルオロメタンスルホン）アミドの合成＞
［２−（メタクリロイルオキシ）エチル］トリメチルアンモニウム・クロライドの均一な水溶液中に、リチウムビス（トリフルオロメタンスルホン）アミド塩水溶液を等モルになるように添加し、イオン液体のアニオン交換を利用することで、疎水性イオン液体モノマーの［２−（メタクリロイルオキシ）エチル］トリメチルアンモニウム・ビス（トリフルオロメタンスルホン）（下式［ＭＴＭＡ］［ＴＦＳＡ］）を合成した。生成物は、蒸留水にて充分に洗浄し、不純物を取り除いた。
<Synthesis of [2- (methacryloyloxy) ethyl] trimethylammonium bis (trifluoromethanesulfone) amide>
By adding an equimolar amount of an aqueous lithium bis (trifluoromethanesulfone) amide salt solution to a uniform aqueous solution of [2- (methacryloyloxy) ethyl] trimethylammonium chloride and utilizing anion exchange of the ionic liquid Then, [2- (methacryloyloxy) ethyl] trimethylammonium bis (trifluoromethanesulfone) (the following formula [MTMA] [TFSA]) as a hydrophobic ionic liquid monomer was synthesized. The product was thoroughly washed with distilled water to remove impurities.
＜ポリメチルメタクリレートシード粒子の合成＞
ガラス管に、メチルメタクリレート０．６ｇ、アゾイソブチロニトリル０．００６ｇ、前記ポリビニルピロリドン「Ｋ−３０」０．０６ｇ、メタノール３．８ｇ、水１．６ｇを仕込み、窒素置換してから、ガラス管を密封し、６０℃の水浴を備えた振盪器で、８０サイクル／分で振盪させながら、５時間重合を行い、ポリメチルメタクリレートのシード粒子を合成した。このシード粒子は、平均粒径ｄｎが２．８μｍ、変動係数（ＣＶ）は３．４％であった。
<Synthesis of polymethylmethacrylate seed particles>
A glass tube was charged with 0.6 g of methyl methacrylate, 0.006 g of azoisobutyronitrile, 0.06 g of the polyvinyl pyrrolidone “K-30”, 3.8 g of methanol, and 1.6 g of water. The tube was sealed, and polymerization was carried out for 5 hours in a shaker equipped with a 60 ° C. water bath at 80 cycles / minute to synthesize polymethylmethacrylate seed particles. The seed particles had an average particle diameter dn of 2.8 μm and a coefficient of variation (CV) of 3.4%.
比較例１
ガラス管に、ポリスチレンシード粒子０．２５ｇ、［ＭＴＭＡ］［ＴＦＳＡ］０．２５ｇ、アゾイソブチロニトリル０．００２５ｇ、エタノール２．５ｇを仕込み、窒素置換してから、ガラス管を密封し、６０℃の水浴を備えた振盪器で、８０サイクル／分で振盪させながら、１０時間、シード分散重合を行った。その結果を図１に示す。図１（ａ）は、ポリスチレンのシード粒子のＳＥＭ写真であり、図１（ｂ）はシード分散重合後の粒子のＳＥＭ写真である。シード分散重合後の粒子の平均粒径は１．７μｍであり、シード分散重合前後で変化がなく、また、図１（ｂ）から明らかなように、ポリスチレンのシード粒子よりも大きい粒子が認められることから、イオン液体モノマーである［ＭＴＭＡ］［ＴＦＳＡ］単独のホモポリマーが生成していることがわかる。ポリスチレンのγt pは２．５ｍＮ／ｍであり、ポリ［ＭＴＭＡ］［ＴＦＳＡ］のγi pは１７．０ｍＮ／ｍであって、Δγが１４．５ｍＮ／ｍであるため、シード分散重合の際に、ポリスチレンのシード粒子の中に、イオン液体モノマーである［ＭＴＭＡ］［ＴＦＳＡ］が入り込めず、溶媒中で単独重合してしまったことが確認できた。
Comparative Example 1
A glass tube was charged with 0.25 g of polystyrene seed particles, 0.25 g of [MTMA] [TFSA], 0.0025 g of azoisobutyronitrile, and 2.5 g of ethanol, and the atmosphere was purged with nitrogen. The seed dispersion polymerization was carried out for 10 hours while shaking at 80 cycles / min in a shaker equipped with a water bath at 0 ° C. The result is shown in FIG. FIG. 1 (a) is an SEM photograph of polystyrene seed particles, and FIG. 1 (b) is an SEM photograph of particles after seed dispersion polymerization. The average particle diameter of the particles after seed dispersion polymerization is 1.7 μm, and there is no change before and after seed dispersion polymerization. As is clear from FIG. 1B, particles larger than polystyrene seed particles are observed. This indicates that a homopolymer of [MTMA] [TFSA] alone, which is an ionic liquid monomer, is produced. Since γ t p of polystyrene is 2.5 mN / m, γ i p of poly [MTMA] [TFSA] is 17.0 mN / m and Δγ is 14.5 mN / m, In this case, it was confirmed that the ionic liquid monomer [MTMA] [TFSA] could not enter the polystyrene seed particles and was homopolymerized in the solvent.
実施例１
ガラス管に、ポリメチルメタクリレートシード粒子０．２５ｇ、［ＭＴＭＡ］［ＴＦＳＡ］０．２５ｇ、「Ｖ−７０」（和光純薬工業社製；２，２’−アゾビス（４−メトキシ−２，４−ジメチルバレロニトリル））０．００２５ｇ、エタノール２．５ｇを仕込み、窒素置換してから、ガラス管を密封し、３０℃の水浴を備えた振盪器で、８０サイクル／分で振盪させながら、１０時間、シード分散重合を行った。重合後、エタノールで遠心洗浄し、本発明の複合微粒子を得た。その結果を図２に示す。図２（ａ）は、ポリメチルメタクリレートのシード粒子のＳＥＭ写真であり、図２（ｂ）はシード分散重合後の複合微粒子のＳＥＭ写真である。シード分散重合後の粒子の平均粒径は３．４μｍ（変動係数４．３％）であって、シード分散重合前の２．８μｍ（変動係数３．４％）に比べて明らかに大きくなっており、ポリメチルメタクリレートのシード粒子の中にイオン液体モノマーである［ＭＴＭＡ］［ＴＦＳＡ］が入り込んで重合したことが確認できた。ポリメチルメタクリレートのγt pは８．５ｍＮ／ｍであり、ポリ［ＭＴＭＡ］［ＴＦＳＡ］のγi pは前記したとおり１７．０ｍＮ／ｍであるので、Δγは８．５ｍＮ／ｍとなり、本発明の好適範囲である１４ｍＮ／ｍ以下だったことから、シード分散重合の際に、ポリメチルメタクリレートのシード粒子の中にイオン液体モノマーである［ＭＴＭＡ］［ＴＦＳＡ］がうまく入り込んで重合したものと考えられる。図３には、得られた複合微粒子の拡大ＳＥＭ写真を示した。１個の粒子の中に点々と散らばる小さな黒い点と、粒子の周囲を縁取る黒い部分がポリ［ＭＴＭＡ］［ＴＦＳＡ］であることから、ポリメチルメタクリレートが海、ポリ［ＭＴＭＡ］［ＴＦＳＡ］が島である海島構造と、コアシェル構造の両方の構造を採っていることがわかる。
Example 1
In a glass tube, 0.25 g of polymethylmethacrylate seed particles, [MTMA] [TFSA] 0.25 g, “V-70” (manufactured by Wako Pure Chemical Industries, Ltd .; 2,2′-azobis (4-methoxy-2,4 -Dimethylvaleronitrile)) 0.0025 g and ethanol 2.5 g were charged, and the atmosphere was purged with nitrogen. Then, the glass tube was sealed, and shaken at 80 cycles / minute with a shaker equipped with a 30 ° C. water bath. The seed dispersion polymerization was performed for a time. After the polymerization, centrifugal washing with ethanol was performed to obtain composite fine particles of the present invention. The result is shown in FIG. FIG. 2A is an SEM photograph of polymethyl methacrylate seed particles, and FIG. 2B is an SEM photograph of composite fine particles after seed dispersion polymerization. The average particle diameter of the particles after seed dispersion polymerization is 3.4 μm (variation coefficient 4.3%), which is clearly larger than 2.8 μm before seed dispersion polymerization (variation coefficient 3.4%). It was confirmed that [MTMA] [TFSA], which is an ionic liquid monomer, entered the polymethylmethacrylate seed particles and polymerized. Since γ t p of polymethyl methacrylate is 8.5 mN / m and γ i p of poly [MTMA] [TFSA] is 17.0 mN / m as described above, Δγ is 8.5 mN / m. Since the preferred range of the invention was 14 mN / m or less, during seed dispersion polymerization, [MTMA] [TFSA], which is an ionic liquid monomer, was successfully polymerized into the seed particles of polymethyl methacrylate. Conceivable. FIG. 3 shows an enlarged SEM photograph of the obtained composite fine particles. Since the small black dots scattered in one particle and the black part bordering the periphery of the particle are poly [MTMA] [TFSA], polymethylmethacrylate is the sea, and poly [MTMA] [TFSA] is It can be seen that the island has both a sea-island structure, which is an island, and a core-shell structure.
実施例２
ガラス管に、ポリメチルメタクリレートシード粒子１．０ｇ、［ＭＴＭＡ］［ＴＦＳＡ］０．２ｇ、前記「Ｖ−７０」０．０１ｇ、エタノール１０ｇを仕込み、窒素置換してから、ガラス管を密封し、３０℃の水浴を備えた振盪器で、８０サイクル／分で振盪させた。振盪開始から２時間後に、０．２ｇの［ＭＴＭＡ］［ＴＦＳＡ］と前記「Ｖ−７０」０．００２ｇを加え、４時間後、６時間後および８時間後も同様に０．２ｇの［ＭＴＭＡ］［ＴＦＳＡ］と前記「Ｖ−７０」０．００２ｇを加え、合計１０時間、シード分散重合を行った。重合後、エタノールで遠心洗浄し、本発明の複合微粒子を得た。その結果を図４、図５に示す。図４（ａ）は、ポリメチルメタクリレートのシード粒子のＳＥＭ写真であり、図４（ｂ）および図５はシード分散重合後の複合微粒子のＳＥＭ写真である。シード分散重合後の粒子の平均粒径は３．３μｍ（変動係数７．５％）であって、シード分散重合前の２．８μｍに比べて明らかに大きくなっており、ポリメチルメタクリレートのシード粒子の中にイオン液体モノマーである［ＭＴＭＡ］［ＴＦＳＡ］が入り込んで重合したことが確認できた。また、図５からわかるように、［ＭＴＭＡ］［ＴＦＳＡ］を分割添加した場合、きれいなコアシェル構造の複合微粒子が得られた。
Example 2
A glass tube was charged with 1.0 g of polymethyl methacrylate seed particles, 0.2 g of [MTMA] [TFSA], 0.01 g of the above-mentioned “V-70”, and 10 g of ethanol. After replacing with nitrogen, the glass tube was sealed, Shake at 80 cycles / min on a shaker with 30 ° C. water bath. Two hours after the start of shaking, 0.2 g of [MTMA] [TFSA] and 0.002 g of the above-mentioned “V-70” were added, and 0.2 g of [MTMA] was similarly applied after 4, 6 and 8 hours. ] [TFSA] and 0.002 g of the above "V-70" were added, and seed dispersion polymerization was performed for a total of 10 hours. After the polymerization, centrifugal washing with ethanol was performed to obtain composite fine particles of the present invention. The results are shown in FIGS. 4A is an SEM photograph of polymethylmethacrylate seed particles, and FIG. 4B and FIG. 5 are SEM photographs of composite fine particles after seed dispersion polymerization. The average particle size of the particles after seed dispersion polymerization is 3.3 μm (variation coefficient 7.5%), which is clearly larger than 2.8 μm before seed dispersion polymerization. It was confirmed that [MTMA] [TFSA], which is an ionic liquid monomer, entered and polymerized. As can be seen from FIG. 5, when [MTMA] [TFSA] was added in a divided manner, fine composite particles having a core-shell structure were obtained.
本発明の複合微粒子は、帯電防止材料、固体電解質、電池用角膜、二酸化炭素吸着カラム等、様々な分野に適用可能である。 The composite fine particles of the present invention can be applied to various fields such as antistatic materials, solid electrolytes, battery corneas, carbon dioxide adsorption columns and the like.
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| JP2003286324A (en) * | 2002-01-25 | 2003-10-10 | Daicel Chem Ind Ltd | Aqueous resin dispersion and its production method |
| JP2011213862A (en) * | 2010-03-31 | 2011-10-27 | Kuraray Co Ltd | Ion-conductive curable composition |
| JP2012074351A (en) * | 2010-08-31 | 2012-04-12 | Japan Advanced Institute Of Science & Technology Hokuriku | Ion conductive material and use thereof |
| JP2013533329A (en) * | 2010-05-18 | 2013-08-22 | スリーエム イノベイティブ プロパティズ カンパニー | Polymerizable ionic liquid composition |
| JP2014500905A (en) * | 2010-11-30 | 2014-01-16 | メルク パテント ゲーエムベーハー | Particles for electrophoretic display |
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|---|---|---|---|---|
| JP2003286324A (en) * | 2002-01-25 | 2003-10-10 | Daicel Chem Ind Ltd | Aqueous resin dispersion and its production method |
| JP2011213862A (en) * | 2010-03-31 | 2011-10-27 | Kuraray Co Ltd | Ion-conductive curable composition |
| JP2013533329A (en) * | 2010-05-18 | 2013-08-22 | スリーエム イノベイティブ プロパティズ カンパニー | Polymerizable ionic liquid composition |
| JP2012074351A (en) * | 2010-08-31 | 2012-04-12 | Japan Advanced Institute Of Science & Technology Hokuriku | Ion conductive material and use thereof |
| JP2014500905A (en) * | 2010-11-30 | 2014-01-16 | メルク パテント ゲーエムベーハー | Particles for electrophoretic display |
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| JP2018203966A (en) * | 2017-06-09 | 2018-12-27 | シャープ株式会社 | Fluorescent body-containing particle, light-emitting device using the same, and florescent body-containing sheet |
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