高分子 Vol.63 No.2
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特集 薄さを極めた高分子
展望 COVER STORY: Highlight Reviews
高分子薄膜のガラス転移
Glass Transition of Polymer Thin Filmes
金谷 利治・井上 倫太郎
Toshiji KANAYA, Rintaro INOUE
<要旨> 高分子を薄膜にするとバルクとは異なる興味深い物性が発現する。本稿では、高分子薄膜のガラス転移現象、特にガラス転移温度に着目して、最近の主だった進歩と今後の課題についてその展望を述べる。
Keywords: Polymer Thin Film / Glass Transition Temperature / Confinmemt / Surface Effect / Interfacial Effect / Distribution of Glass Transition Temperature
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高分子ナノ吸着層
Nano-Architectures and Dynamics of Polymer Chains Adsorbed on Planar Solid Surfaces
古賀 忠典
Tadanori KOGA
<要旨>高分子の表面・界面は、粘着、乾燥、摩擦、塗布などさまざまな工業上重要な多くの問題に関係しているのみならず、生体界面でも重要な役割を果たしている。本稿では、高分子・固体界面に着目し、量子ビームを用いた「その場」観察により明らかになった高分子ナノ吸着層の存在および高分子薄膜の内部構造・物性に及ぼすその効果について紹介する。
Keywords: Adsorbed Layer / Polymer Melt / Solid Interface / Flattened Conformation / Nanoconfinement Effects / Long-Range Perturbations
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自己組織化高分子薄膜を利用した電子デバイスの超微細加工
Ultrafine Fabrication Using Self-Assembled Polymer Thin Film
浅川 鋼児
Koji ASAKAWA
<要旨>電子デバイスは、加工寸法の微細化で高性能化と低価格化を同時に実現してきた。しかし、装置や材料コストの高騰で、いよいよ限界が見えている。これを打破するため、一昔前であれば夢物語でしかなかった自己組織化で得られる高分子の超微細構造の適用が真剣に研究開発されている。
Keywords: Block Copolymer Lithography / Directed Self-Assembly / Electronic Device Fabrication / Hard Disk Drive / Optical Device / Memory Device
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トピックス COVER STORY: Topics and Products
ハイブリッド高分子ナノ集積体
Hybrid Polymer Nanoassembly
三ツ石 方也・宮下 徳治
Masaya MITSUISHI, Tokuji MIYASHITA
<要旨> We demonstrate flexible design of hybrid polymer nanoassemblies based on nanoparticle arrays and polymer nanosheets. Using excellent film formation ability of acrylamide-based amphiphic polymers at the air-water interface, well defined hybrid polymer nanoassemblies were constructed at the monoparticle layer level. Hybrid polymer nanoassemblies enable to elucidate the structure-property relationship in terms of light-matter interaction at confined spaces as well as open up a new scientific field for nanophotonics and nanoelectronics applications. Several examples such as luminescence oxygen sensor application and emission control of hybrid polymer nanoassemblies assembled on a silver grating surface are described.
Keywords: Polymer Nanosheet / Hybrid Polymer Nanoassembly / Localized Surface Plasmon / Waveguide / Nanoparticle
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界面から誘起する薄膜中の半導体高分子鎖の垂直配向
End-On Orientation of Semiconducting Polymers in Thin Films Induced by Surface Segregation
但馬 敬介
Keisuke TAJIMA
<要旨> Controlling the orientation of highly anisotropic semiconducting polymers in thin films is important for the high performance of organic electronic devices. We have recently developed simple ways to achieve unique end-on (vertical) orientation by utilizing the surface segregation of the end-fluoroalkylated poly(3-butylthiophene) (P3BTF). In P3BTF/polystyrene (PS) blend films, a highly ordered end-on orientation of the conjugated backbone was observed in the surface-segregated layer of the crystalline P3BT-F. Furthermore, when the film was spin-coated from a mixture of P3BT-F and poly(3-butylthiophene) (P3BT), the chain orientation of P3BT-F at the surface forced the P3BT in the bulk of the film to adopt the end-on orientation because of the high crystallinity of P3BT. The electronic conductivity measured perpendicular to the film surface also reflected the end-on orientation in the bulk, resulting in a more than 30-fold enhancement of the hole mobility. This strategy could be applied to other crystalline semiconducting polymers and has great promise for controlling the optical and electronic properties of polymer films.
Keywords: Semiconducting Polymers / Chain Orientation /
Thin Films / Surface Segregation / Self-Assembly / Anisotropy / Charge Mobility / Crystalization
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中性子反射率法による高分子薄膜の構造解析
Structure Analysis of Polymer Thin Film Using Neutron Reflectometry
山田 悟史
Norifumi L. YAMADA
<要旨> Neutron reflectometry is one of the powerful tools to investigate surface and interfacial structures of materials in the spatial range from nm to sub-μm. Because hydrogen and deuterium atoms have different scattering length for neutrons, this method can distinguish deuterated materials from normal ones in the mixture of soft-condensed matters, such as polymer blends, bio-mimic membranes, and so on. Furthermore, high transmissivity of neutrons to materials enables us to probe deeply-buried interfaces such as solid/liquid interfaces in a non-destructive way. SOFIA is a horizontal type neutron reflectometer in Japan Proton Accelerator Research Complex (J-PARC). Thanks to a careful treatment for background, we can measure a reflectivity profile down to 10-7. Furthermore, the high-flux pulsed neutron beam at J-PARC enables us to perform a time-slicing measurement with a wide wavelength band and short time slices. In this paper, I introduce a specification of SOFIA and some usage examples of SOFIA for polymer samples.
Keywords: Surface and Interfacial Structures / Soft Matter / Neutron Reflectometry
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液晶に支配された液晶性ブロックコポリマー薄膜
Liquid Crystalline Block Copolymer Thin Film Dominated by Liquid Crystal
小村 元憲
Motonori KOMURA
<要旨>Liquid crystalline block copolymer, PEO-b-PMA(Az), forms a highly ordered microphase separated film with perpendicularly oriented cylinders on various substrates by thermal annealing, because homeotropic anchoring of the liquid crystalline mesogens to air-film interface induces nucleation of liquid crystallization and simultaneous order-order transition from sphere to cylinder microphase separations from the interface. In the case of a thick film, homogeneous anchoring of the mesogens to a Si substrate was also observed. Based on this phenomenon, we succeeded in direct observation of both, perpendicular and parallel cylinder formations by temperature-controlled atomic force microscopy with introduction of a temperature gradient between sample stage and cantilever tip. Furthermore, the liquid crystalline block copolymer shows the smallest microphase separated structures because of the exclusion effect of other materials by liquid crystallization that added to thermodynamic repulsive force between blocks represented by χ parameter. Hierarchical microphase separated structures of such a well-designed block copolymer will afford a further progress in block copolymer lithography and fabrication of functional nanomaterials.
Keywords: Microphase Separation / Liquid Crytal / Cylinder / Order-Order Transition / In-situ Observation
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SPring-8におけるGISAXSを用いた高分子薄膜構造研究
Studies on Polymer Thin Film Structure by Grazing Incidence Small Angle X-ray Scattering at SPring-8
小川 紘樹
Hiroki OGAWA
<要旨> To gain a better understanding of the function of polymer thin films, one should measure the multi-scale structures from the surface roughness down to the atomically truncated structures at micro area as well as the formation process inside the film. In this article, structural studies of polymer thin films using synchrotron radiation grazing incidence (GI) small-angle X-ray scattering (SAX) is reviewd, and recent development of GI ultra SAX and in-situ GISAX measurement during spin-coating process is also introduced.
Keywords: Polymer Thin Film / GISAXS / GIUSAXS / Dewetting / Spin-Coating
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グローイングポリマー Polymer Science and I: A Personal Account
生体組織へ積極的に働きかける機能材料創製を目指して
Towards Construction of Functional Materials for Effectively Promoting Living Tissues
多賀谷 基博
Motohiro TAGAYA
<要旨> This manuscript introduces interfacial biological phenomena, preparative nanobiomaterials, and the biomedical applications, leading to functional nanobiosystems as enhanced biocompatibility. In future, the author’s work will contribute to the biomedical fields such as biosensor, drug delivery system, bioimaging and tissue engineering materials.
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高分子科学最近の進歩 Front-Line Polymer Science
セルロースナノ結晶の新展開
Novel Development of Cellulose Nanocrystals
芹澤 武
Takeshi SERIZAWA

<要旨> Cellulose composed of β-1,4-linked anhydro-d-glucose repeating units is the most abundant organic polymer in the biosphere. In nature, crystalline elementary fibrils are formed during biosynthesis, and are hierarchically assembled into larger fibers with other biomolecules. Acid treatment of natural cellulose sources isolates cellulose nanocrystals (CNCs) with rod-like shapes. In this review, the preparation, physical/chemical properties, surface functionalization, and composite materials of CNCs are described. Then, the hydrolytic activities of CNCs, recently developed by our group as their novel functions, are introduced.
Keywords: Cellulose / Nanocrystal / Acid Treatment / Suspension / Surface Functionalization / Composite Material / Hydrolytic Activity

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