Updated on 2026/06/03

写真a

 
KUDO Hiroto
 
Organization
Faculty of Chemistry, Materials and Bioengineering Professor
Title
Professor
Contact information
メールアドレス
External link

Degree

  • Doctor of Engineering ( 2000.3 )

Research Interests

  • 光機能性材料

  • 有機化学

  • 高分子化学

Research Areas

  • Nanotechnology/Materials / Structural materials and functional materials

  • Nanotechnology/Materials / Polymer chemistry

  • Life Science / Bioorganic chemistry

Education

  • Tokyo Institute of Technology   Graduate School, Division of Integrated Science and Engineering

    2000

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  • Tokyo Metropolitan University   Graduate School, Division of Engineering

    1997

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  • Tokyo University of Agriculture and Technology   Faculty of Engineering

    - 1995

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  • Tokyo Metropolitan University   Graduate School, Division of Engineering

    1997

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Research History

  • 東京工業大学 非常勤講師 有機・高分子物質特別講義第三(大学院)担当

    2012.10

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  • Kansai University   Faculty of Chemistry , Materials and Bioengineering, Department of Chemistry and Materials Engineering

    2012.4

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  • University of Hyogo

    2011.9

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  • 神奈川大学 准教授(工学部 物質生命化学科)

    2009.4 - 2012.3

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  • 横浜国立大学 工学府 非常勤講師 高分子化学 担当

    2009.4 - 2010.9

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  • 神奈川大学 助教 (工学部 物質生命化学科)

    2007.4 - 2009.3

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  • 神奈川大学 助手(工学部 応用化学科)

    2001.4 - 2007.3

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  • 山形大学大学院 ベンチャービジネスラボラトリー 講師(中核的研究機関研究員)

    2000.4 - 2001.3

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Professional Memberships

Committee Memberships

  • JST物質・デバイス領域共同研究拠点   共同研究推進委員会委員  

    2018.4 - Present   

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    Committee type:Government

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  • 有機合成化学協会   代議員  

    2016.4 - Present   

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    Committee type:Academic society

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  • ラドテック研究会   理事  

    2012.4 - Present   

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    Committee type:Academic society

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  • 大阪ニュークリアサイエンス   参事  

    2012.4 - Present   

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    Committee type:Academic society

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  • 日本化学会   代議員  

    2010.4 - 2012.3   

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    Committee type:Academic society

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  • 高分子学会   評議委員  

    2010.4 - 2012.3   

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    Committee type:Academic society

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Papers

  • <scp>UV</scp>‐Curable High‐Refractive‐Index Resin Based on Polysulfide With Pendant Methacrylate Formed by Selective Cationic Ring‐Opening Polymerization of Thiirane

    Hiroto Kudo, Koichi Hirose, Ryota Tsutsui, Hiroyuki Maekawa, Hiroaki Uchiyama

    Journal of Polymer Science   2025.3

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    Publishing type:Research paper (scientific journal)   Publisher:Wiley  

    ABSTRACT

    In this paper, we aimed to synthesize polysulfide with pendant methacryloyl groups in the side chain. They are expected to have great potential for various applications as UV‐curable higher‐refractive‐index resins. Thiiran‐2‐ylmethyl methacrylate (TMA) could be synthesized by the reaction of glycidyl methacrylate with thiourea using conc. H<sub>2</sub>SO<sub>4</sub> as a catalyst. Selective ring‐opening polymerization of TMA could be achieved using CuCl<sub>2</sub> as an initiator in CHCl<sub>3</sub> at 25°C, yielding the corresponding polysulfide polyTMA<sub>(MA)</sub> with pendant methacryloyl groups in the side chain in high yield. The copolymerization of TMA and phenoxypropylene sulfide (PPS) was also performed to give poly(TMA<sub>(MA)m</sub>‐co‐PPS<sub>n</sub>) with M<sub>n</sub> = 1330–1940 (M<sub>w</sub>/M<sub>n</sub> = 1.03–2.02) in high yields. The UV‐curing reaction of thin films of polyTMA<sub>(MA)</sub> and poly(TMA<sub>(MA)m</sub>‐co‐PPS<sub>n</sub>) containing a photo‐radical initiator proceeded smoothly under UV light, quantitatively affording the corresponding cured thin films. The refractive indices of the thin films before and after UV irradiation were determined by ellipsometry. Among them, poly(TMA<sub>(MA)22</sub>‐co‐PPS<sub>78</sub>) showed the highest refractive index value (n = 1.763) after the UV‐curing reaction.

    DOI: 10.1002/pol.20250018

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  • Star-Shaped Polymers with Helical Polyacetylene Arms. Comparison of Solution- and Solid-State Properties with Linear Helical Polyacetylenes

    Shota Mino, Kosuke Matsui, Masahide Goto, Akiyuki Ryoki, Takeyuki Suzuki, Kazushi Fujimoto, Hiromitsu Sogawa, Hiroto Kudo, Fumio Sanda

    Macromolecules   57 ( 22 )   10824 - 10834   2024.11

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    Publishing type:Research paper (scientific journal)   Publisher:American Chemical Society (ACS)  

    DOI: 10.1021/acs.macromol.4c01509

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  • Synthesis of Resist Materials Containing Hemiacetal Groups and Their Resist Sensitivity

    Kouta Iwane, Hiroto Kudo, Kazumasa Okamoto, Takahiro Kozawa

    Journal of Photopolymer Science and Technology   37 ( 3 )   287 - 292   2024.6

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    Publishing type:Research paper (scientific journal)   Publisher:Technical Association of Photopolymers, Japan  

    DOI: 10.2494/photopolymer.37.287

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  • Synthesis of Botryosin-type Resist Material Containing Acetal Groups in the Main Chain and Its Sensitivity

    Riku Akabane, Kazumasa Okamoto, Takahiro Kozawa, Hiroto Kudo

    Journal of Photopolymer Science and Technology   37 ( 3 )   293 - 298   2024.6

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    Publishing type:Research paper (scientific journal)   Publisher:Technical Association of Photopolymers, Japan  

    DOI: 10.2494/photopolymer.37.293

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  • Synthesis and properties of highly thermally stable ultrathin films of fluorine‐containing hyperbranched polybenzoxazoles

    Hiroyuki Maekawa, Kosyu Nakamura, Hiroto Kudo

    Journal of Polymer Science   2023.11

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    Publishing type:Research paper (scientific journal)   Publisher:Wiley  

    Abstract

    In this paper, we aimed to develop ultrathin films of hyperbranched polybenzoxazole with a thickness in the range between 1 and 100 nm. They are expected to have great potential for various applications as functional materials due to their high thermal stability, good chemical resistance and mechanical strength. The synthesis of various hyperbranched poly(o‐hydroxyamide)s as precursors of polybenzoxazole was examined by the polycondensation of 2,2‐bis(3‐amino‐4‐hydroxyphenyl)propane (AHP) and 2,2‐bis(3‐amino‐4‐hydroxyphenyl)hexafluoropropane (AHFP) with 1,3,5‐benzenetricarbonyl trichloride (BCC), yielding the corresponding hyperbranched poly(o‐hydroxyamide), poly(AHFP<sub>m</sub>‐co‐AHP<sub>n</sub>‐co‐BCC<sub>2.0</sub>), with M<sub>n</sub> in the range between 12,870 and 22,210 in satisfactory yields. Poly(AHFP<sub>3.0</sub>‐co‐BCC<sub>2.0</sub>), poly(AHFP<sub>2.25</sub>‐co‐AHP<sub>0.75</sub>‐co‐BCC<sub>2.0</sub>), and poly(AHFP<sub>1.50</sub>‐co‐AHP<sub>1.50</sub>‐co‐BCC<sub>2.0</sub>) showed good solubility and film‐forming ability, and ultrathin films 8.9–88.6 nm thick were prepared on silicon wafers. Heating of the ultrathin films of poly(AHFP<sub>m</sub>‐co‐AHP<sub>n</sub>‐co‐BCC<sub>2.0</sub>) on a hot plate at 350 °C for 1 h afforded the corresponding ultrathin films of hyperbranched polybenzoxazole, poly(AHFP<sub>m</sub>‐cyclo‐AHP<sub>n</sub>‐cyclo‐BCC<sub>2.0</sub>), with a thickness of 5.3–82.4 nm. Double‐layer thin films consisting of resist materials on top of hyperbranched polybenzoxazole were also prepared.

    DOI: 10.1002/pol.20230659

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  • Design of High-sensitive Resist Materials Based on Polyacetals

    Hiroyuki Maekawa, Yutaro Iwashige, Hiroki Yamamoto, Kazumasa Okamoto, Takahiro Kozawa, Hiroto Kudo

    Journal of Photopolymer Science and Technology   36 ( 1 )   31 - 39   2023.6

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    Publishing type:Research paper (scientific journal)   Publisher:Technical Association of Photopolymers, Japan  

    DOI: 10.2494/photopolymer.36.31

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  • Synthesis and Resist Sensitive Property of Iodine-Containing Materials using Extreme Ultraviolet (EUV) Exposure Tool

    Yutaro Iwashige, Hiroto Kudo, Kazumasa Okamoto, Takahiro Kozawa

    Journal of Photopolymer Science and Technology   35 ( 1 )   41 - 47   2022

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    Publishing type:Research paper (scientific journal)  

    DOI: 10.2494/photopolymer.35.41

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  • Programmed Dynamic Covalent Chemistry System of Addition-condensation Reaction of Phenols and Aldehydes

    Hiroto Kudo, Daisuke Shimoyama, Ryo Sekiya, Takeharu Haino

    Chemistry Letters   50 ( 4 )   825 - 831   2021.4

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    Publishing type:Research paper (scientific journal)   Publisher:The Chemical Society of Japan  

    DOI: 10.1246/cl.200773

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  • Higher Sensitive Extreme Ultraviolet (EUV) Resist Materials Derived From <i>p-t</i>-Butylcalix[n]arenes (n = 4 and 8) Invited Reviewed

    Hiroyuki Maekawa, Hiroto Kudo, Takeo Watanabe, Hiroki Yamamoto, Kazumasa Okamoto, Takahiro Kozawa

    Journal of Photopolymer Science and Technology   33 ( 1 )   45 - 51   2020.7

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    Authorship:Corresponding author   Language:English   Publishing type:Research paper (scientific journal)   Publisher:Technical Association of Photopolymers, Japan  

    DOI: 10.2494/photopolymer.33.45

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  • Living Ring-Expansion Polymerization of Thiirane with Cyclic Monocarbamothioates Reviewed

    Hiroto Kudo, Kazunori Naritomi, Shuto Onishi, Hiroyuki Maekawa, Evan A. Q. Mondarte, Kasinan Suthiwanich, Tomohiro Hayashi

    Macromolecules   53 ( 12 )   4733 - 4740   2020.6

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    Authorship:Lead author, Corresponding author   Language:English   Publishing type:Research paper (scientific journal)   Publisher:American Chemical Society (ACS)  

    DOI: 10.1021/acs.macromol.0c00687

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  • ノーリア骨格をテンプレートとした空孔内に水酸基を有する架橋化合物の合成とそれらの金属イオン包接性能 Invited Reviewed

    工藤 宏人, 宮前 翼, 上田 正人, 村山 憲弘, 林 順一

    65 - 71   2020.4

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    Authorship:Lead author, Corresponding author   Language:Japanese   Publishing type:Research paper (scientific journal)  

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  • Synthesis and Property of Tellurium-Containing Molecular Resist Materials for Extreme Ultraviolet Lithography System Invited Reviewed

    Hiroto Kudo, Mari Fukunaga, Teppei Yamada, Shinji Yamakawa, Takeo Watanabe, Hiroki Yamamoto, Kazumasa Okamoto, Takahiro Kozawa

    Journal of Photopolymer Science and Technology   32 ( 6 )   805 - 810   2020.1

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    Authorship:Lead author, Corresponding author   Language:English   Publishing type:Research paper (scientific journal)   Publisher:Technical Association of Photopolymers, Japan  

    DOI: 10.2494/photopolymer.32.805

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  • Feet-to-Feet Connected Trisresorcinarenes Reviewed

    Daisuke Shimoyama, Ryo Sekiya, Hiroto Kudo, Takeharu Haino

    Organic Letters   22 ( 2 )   352 - 356   2020.1

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    Publishing type:Research paper (scientific journal)   Publisher:American Chemical Society (ACS)  

    DOI: 10.1021/acs.orglett.9b03693

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  • One-dimensional arrangement of NORIA in the solid-state

    Daisuke Shimoyama, Ryo Sekiya, Hiroyuki Maekawa, Hiroto Kudo, Takeharu Haino

    CrystEngComm   22 ( 28 )   4740 - 4747   2020

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    Publishing type:Research paper (scientific journal)   Publisher:Royal Society of Chemistry (RSC)  

    <p>NORIA is a synthetic macrocycle consisting of twelve resorcinol rings. By cocrystallization of NORIA with benzene, NORIA organized one-dimensional array.</p>

    DOI: 10.1039/d0ce00650e

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  • Synthesis of hyperbranched polyacetals containing C-(4-t-butylbenz)calix[4]resorcinarene: Resist properties for extreme ultraviolet (EUV) lithography Reviewed

    Kudo Hiroto

    Reactive & Functional Polymers   131, 361 - 367   2018.8

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  • Synthesis and Metal-Complexation Ability of Cross-Linking Materials Containing Noria-Templated Cavities with Pendant Carboxylic Acid Groups

    Hiroto Kudo, Tsubasa Miyamae, Kouta Kitagawa, Kohei Isoi, Norihiro Murayama, Jun'ichi Hayashi

    ChemistrySelect   3 ( 8 )   2223 - 2228   2018.2

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:Wiley-Blackwell  

    DOI: 10.1002/slct.201703099

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  • Synthesis and Metal-Complexation Ability of Cross-Linking Materials Containing Noria-Templated Cavities with Pendant Carboxylic Acid Groups Reviewed

    Hiroto Kudo, Tsubasa Miyamae, Kouta Kitagawa, Kohei Isoi, Norihiro Murayama, Jun'ichi Hayashi

    ChemistrySelect   3 ( 8 )   2223 - 2228   2018.2

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    DOI: 10.1002/slct.201703099

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  • Synthesis and Property of Tannic Acid Derivatives and Their Application for Extreme Ultraviolet Laser Lithography System (vol 31, pg 221, 2018)

    Hiroto Kudo, Shizuya Ohori, Hiroya Takeda, Hiroki Ogawa, Takeo Watanabe, Hiroki Yamamoto, Takahiro Kozawa

    JOURNAL OF PHOTOPOLYMER SCIENCE AND TECHNOLOGY   31 ( 6 )   759 - 759   2018

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  • Study on resist performance of noria derivatives modified with various protection ratios of acetal moieties by means of extreme ultraviolet irradiation Reviewed

    Hiroki Yamamoto, Hiroto Kudo, Takahiro Kozawa

    J. Photopolym. Sci. Technol   30, 627 - 631   2017.6

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  • ε-カプロラクタムとエポキシ樹脂類の熱硬化反応と得られた架橋硬化物の性質 Reviewed

    工藤宏人, 歩谷健太郎

    ネットワークポリマー   32, 81 -85   2017.4

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  • Synthesis and Property of Tellurium-Containing Polymer for Extreme Ultraviolet Resist Material

    Mari Fukunaga, Hiroki Yamamoto, Takahiro Kozawa, Takeo Watanabe, Hiroto Kudo

    JOURNAL OF PHOTOPOLYMER SCIENCE AND TECHNOLOGY   30 ( 1 )   103 - 107   2017

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  • Chemically amplified molecular resists based on noria derivatives containing adamantyl ester groups for electron beam lithography Reviewed

    Hiroki Yamamoto, Seiichi Tagawa, Takahiro Kozawa, Hiroto Kudo, Kazumasa Okamoto

    JOURNAL OF VACUUM SCIENCE & TECHNOLOGY B   34 ( 4 )   041606   2016.7

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    DOI: 10.1116/1.4953068

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  • Mechanistic Study of Ring-Opening Copolymerization of epsilon-Caprolactam with Epoxide: Development of Novel Thermosetting Epoxy Resin System

    Hiroto Kudo, Kentaro Buya

    JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY   54 ( 14 )   2220 - 2228   2016.7

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    DOI: 10.1002/pola.28095

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  • Synthesis and Resist Properties of Hyperbranched Polyacetals

    Hiroto Kudo, Shuhei Matsubara, Hiroki Yamamoto, Takahiro Kozawa

    JOURNAL OF PHOTOPOLYMER SCIENCE AND TECHNOLOGY   28 ( 1 )   125 - 129   2015

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  • Calixarene-polymers via simple polymerization of t-butylcalix[8]arenes (A8-type monomer) with hexamethylene diisocyanate (B2-type monomer); molecular bunch of grapes (botryosin)

    Hiroto Kudo, Motohiro Shizuma, Kosuke Kubo, Tomohiro Hayashi

    Chemistry Letters   44 ( 12 )   1765 - 1767   2015

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:Chemical Society of Japan  

    DOI: 10.1246/cl.150840

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  • Study on Resist Performance of Chemically Amplified Molecular Resists based on Cyclic Oligomer

    Yamamoto Hiroki, Kudo Hiroto, Kozawa Takahiro

    JSAP Annual Meetings Extended Abstracts   2014.2   1440 - 1440   2014.9

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    Language:Japanese   Publisher:The Japan Society of Applied Physics  

    DOI: 10.11470/jsapmeeting.2014.2.0_1440

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  • Study on resist performance of chemically amplified molecular resists based on cyclic oligomers

    Hiroki Yamamoto, Hiroto Kudo, Takahiro Kozawa

    Microelectronic Engineering   133, 16 - 22   2014.2

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  • Novel epoxy thermosetting resin system using ε-caprolactam

    Hiroto Kudo, Hiroki Ogawa, Kazunori Naritomi, Yuka Murata, Hiroki Kano, Mitsukazu Ochi

    Chemistry Letters   43 ( 9 )   1450 - 1452   2014

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    DOI: 10.1246/cl.140497

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  • Synthesis of Cyclic polysulfides: Controlled Ring-Expansion Polymerization of Cyclic tetrathioester with Thiirane

    KUDO,Hiroto

    52, 857 - 866   2013.12

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  • 末端にメタクリロイル残基を有するハイパーブランチポリエーテルの合成とそれらのUV硬化性樹脂への応用 Reviewed

    工藤 宏人

    ネットワークポリマー   35, No1, 2 - 9 (2014)   2013.12

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  • UV硬化性ハイパーブランチポリマーおよび環状オリゴマーの合成と性質 Reviewed

    工藤 宏人

    ネットワークポリマー   34(5) 233 -244 (2013)   2013.8

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  • Synthesis and property of noria (water-wheel like macrocycle) derivatives with pendant alkoxyl and adamantyl ester groups, and their application for extreme ultraviolet resist

    Nobumitsu Niina, Hiroto Kudo, Hiroaki Oizumi, Toshiro Itani, Tadatomi Nishikubo

    THIN SOLID FILMS   534   459 - 464   2013.5

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    Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.1016/j.tsf.2013.02.016

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  • 極端紫外線用分子レジスト材料の開発 Reviewed

    工藤 宏人

    日本接着学会誌   49(6) 211 - 223 (2013)   2013.3

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  • Extreme Ultraviolet Resist Fabricated Using Water Wheel-Like Cyclic Oligomer with Pendant Adamantyl Ester Groups

    工藤宏人, 関浩之, 老泉博昭, 井谷 俊郎, 西久保 忠臣

    Jpn. J. Appl. Phys.   50, 121602-1-6   2012.12

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  • Impregnation of waterwheel supramolecules as proton carriers in Nafion-perfluorinated ionomer membranes

    Nadzrinahamin A. Nazir, Hiruto Kudo, Tadatomi Nishikubo, Thein Kyu

    JOURNAL OF MATERIALS SCIENCE   47 ( 20 )   7269 - 7279   2012.10

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    DOI: 10.1007/s10853-012-6681-y

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  • 動的共有結合化学システムによるラダー型環状オリゴマーの合成と、それらを基盤とした光機能性材料(UV硬化樹脂・分子レジスト)への応用 Reviewed

    工藤宏人, 西久保 忠臣

    有機合成化学協会誌5月号(総合論文)   vol. 70, 492-507   2012.6

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  • Extreme Ultraviolet (EUV)-Resist Material Based on Noria (Water Wheel-like Macrocycle) Derivatives with Pendant Alkoxyl and Adamantyl Ester Groups

    Hiroto Kudo, Nobumitsu Niina, Tomoharu Sato, Hiroaki Oizumi, Toshiro Itani, Takuro Miura, Takeo Watanabe, Hiroo Kinoshita

    JOURNAL OF PHOTOPOLYMER SCIENCE AND TECHNOLOGY   25 ( 5 )   587 - 592   2012

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  • Synthesis of hyperbranched fluorinated polymers with controllable refractive indices

    宮坂 誠, 小池 直之, 藤原 祐介, 工藤宏人, 西久保 忠臣

    Polymer Journal   43, 325-329   2011.12

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  • Synthesis and Property of Tellurium-containing Polymers Obtained by Simple Condensation Reaction of Tetrachlorotellurium and 1,3-Dimethoxybenzene

    Hiroto Kudo, Hideatsu Ishihara, Masashi Tomita

    CHEMISTRY LETTERS   40 ( 7 )   762 - 764   2011.7

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    DOI: 10.1246/cl.2011.762

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  • Multicomponent negative-type photoresist based on Noria analog with 12 ethoxy groups

    新名伸光, 工藤宏人, 丸山 研, 甲斐 俊之, 下川 努, 老泉博昭, 井谷 俊郎, 西久保 忠臣

    Polymer Journal   43, 407-413   2011.1

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  • Condensation reaction of phenols with 1,5-pentanedial for synthesis of noria-like ladder-cyclic oligomer by dynamic covalent chemistry mechanism

    Hiroyuki Seki, Shingo Kuwabara, Hiroto Kudo, Tadatomi Nishikubo

    Chemistry Letters   40 ( 5 )   464 - 466   2011

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    DOI: 10.1246/cl.2011.464

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  • Synthesis of Polycarbosilanes by A(2)+B-n (n=2, 3, and 4) Type Hydrosilylation Reaction and Evaluation of Their Refractive Index Properties

    Hiroto Kudo, Yusuke Fujiwara, Makoto Miyasaka, Tadatomi Nishikubo

    JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY   48 ( 24 )   5746 - 5751   2010.12

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    DOI: 10.1002/pola.24379

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  • Controlled Insertion Reaction of Thiirane into Carbamothioate: Novel Synthesis of Well-Defined Polysulfide

    工藤宏人, 佐藤 憲一郎, 西久保 忠臣

    Macromolecules   43(23), 9655-9659   2010.11

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  • Synthesis of hyperbranched polycarbonate by novel polymerization of di-tert-butyl tricarbonate with 1,1,1-tris(4-hydroxyphenyl)ethane

    Makoto Miyasaka, Taichi Takazoe, Hiroto Kudo, Tadatomi Nishikubo

    POLYMER JOURNAL   42 ( 11 )   852 - 859   2010.11

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    DOI: 10.1038/pj.2010.82

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  • Model reactions of calixarenes and their esterified derivatives with glycidyl phenyl ether for thermal curing reactions of epoxy resins

    Shengang Xu, 工藤宏人, 西久保 忠臣, 中村 真也, 沼田 秀一

    Polymer Journal   42 (6) 456 - 463   2010.10

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  • Synthesis and Photo-Cross-Linking Reaction of Noria Derivatives Containing Photoreactive Groups

    工藤宏人, 新名伸光, 林 理英子, 小島 健, 西久保 忠臣

    Macromolecules   43(10), 4822-4826   2010.10

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  • Synthesis of a photocrosslinkable hyperbranched polyester containing methacryloyl groups by the reaction of 1,4-bis(chloromethyl)benzene with 1,3,5-benzenetricarboxylic acid followed by reaction with methacrylic acid

    Ken Maruyama, Toshiaki Hirabayashi, Hiroto Kudo, Tadatomi Nishikubo

    POLYMER JOURNAL   42 ( 10 )   790 - 794   2010.10

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    DOI: 10.1038/pj.2010.74

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  • Synthesis and characterization of hyperbranched polymer consisting of silsesquioxane derivatives

    Makoto Miyasaka, Yusuke Fujiwara, Hiroto Kudo, Tadatomi Nishikubo

    POLYMER JOURNAL   42 ( 10 )   799 - 803   2010.10

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    DOI: 10.1038/pj.2010.79

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  • Thermal cured epoxy resins using certain calixarenes and their esterified derivatives as curing agents

    Shengang Xu, 工藤宏人, 工藤宏人, 中村 真也, 沼田 秀一

    Journal of Polymer Science, Part A: Polymer Chemistry   48(9), 1931-1942   2010.9

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  • Refractive index changes of thin films of photoreactive α-, β-, and γ-cyclodextrin derivatives upon photoirradiation

    工藤宏人, 井上 直美, 西久保 忠臣

    Thin Solid Films   518(12), 3204-3211   2010.8

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  • Synthesis and Photo-Cross-Linking Reaction of Noria Derivatives Containing Photoreactive Groups Reviewed

    工藤宏人, 新名伸光, 林 理英子, 小島 健, 西久保 忠臣

    Macromolecules   43(10), 4822-4826   2010.4

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  • Extreme Ultraviolet (EUV)-Resist Materials of Noria (Water Wheel-Like Cyclic Oligomer) Derivatives containing Acetal Moieties

    Hiroto Kudo, Mayumi Jinguji, Tadatomi Nishikubo, Hiroaki Oizumi, Toshiro Itani

    JOURNAL OF PHOTOPOLYMER SCIENCE AND TECHNOLOGY   23 ( 5 )   657 - 664   2010

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  • Negative-type extreme ultraviolet Resist Materials based on Water-Wheel-like Cyclic Oligomer (Noria)

    Hiroyuki Seki, Yuki Kato, Hiroto Kudo, Hiroaki Oizumi, Toshiro Itani, Tadatomi Nishikubo

    JAPANESE JOURNAL OF APPLIED PHYSICS   49 ( 6 )   2010

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    DOI: 10.1143/JJAP.49.06GF06

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  • Novel extreme ultraviolet (EUV)-resist material based on noria (water wheel-like cyclic oligomer)

    Hiroto Kudo, Yuji Suyama, Hiroaki Oizumi, Toshiro Itani, Tadatomi Nishikubo

    JOURNAL OF MATERIALS CHEMISTRY   20 ( 21 )   4445 - 4450   2010

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    DOI: 10.1039/b925403j

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  • Synthesis of Noria-like Macrocycles Containing Alkoxy Groups based on a Dynamic Covalent Chemistry (DCC) System by the A2 + B4 Condensation

    新名伸光, 工藤宏人, 西久保 忠臣

    Chemistry Letters   38(12), 1198 - 1199   2009.2

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  • Induced Smectic Phase in Mixtures of Hyperbranched Polyester and Liquid Crystal Mesogens Reviewed

    Namil Kim, Tsang-Min Huang, Thein Kyu, Mami Nosaka, Hiroto Kudo, Tadatomi Nishikubo

    JOURNAL OF PHYSICAL CHEMISTRY B   112 ( 42 )   13225 - 13230   2008.10

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    DOI: 10.1021/jp803893k

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  • Synthesis of star polymer by atom transfer radical polmerization with resorcinol-core multifunctional initiator: The construction of nanocapsule via hydrolysis and olefin metathesis reaction of the obtained star polymer Reviewed

    Atsushi Nagai, Toshiaki Hirabayashi, Hiroto Kudo, Tadatomi Nishikubo

    JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY   46 ( 14 )   4879 - 4888   2008.7

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    DOI: 10.1002/pola.22824

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  • One-pot synthesis of a novel ladder polymer of calixarene via condensation reaction of resofcinol and alkanedial based on dynarruic covalent chemistry Reviewed

    Hiroto Kudo, Kyosuke Shigematsu, Kouji Milani, Tadatomi Nishikubo, Noriko C. Kasuga, Hidehiro Uekusa, Yuji Ohashi

    MACROMOLECULES   41 ( 6 )   2030 - 2036   2008.3

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    DOI: 10.1021/ma7019573

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  • Temperature dependence of refractive index of films of well-defined linear and star-shaped polystyrenes Reviewed

    Hiroto Kudo, Hideyuki Aoki, Tadatomi Nishikubo

    CHEMISTRY LETTERS   37 ( 3 )   282 - 283   2008.3

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  • A novel approach to cyclic polysulfides via the controlled ring-expansion polymerization of cyclic thiourethane with thirianes Reviewed

    Hiroto Kudo, Masaaki Sato, Ryosuke Wakai, Tadashi Iwamoto, Tadatomi Nishikubo

    MACROMOLECULES   41 ( 3 )   521 - 523   2008.2

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    DOI: 10.1021/ma7026287

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  • Polymerization and Isomerization of Oxetanes using Heteropolyacid as a Catalyst Reviewed

    Tetsunori Soga, Hiroto Kudo, Tadatomi Nishikubo, Satoshi Sato

    POLYMER JOURNAL   40 ( 9 )   832 - 836   2008

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    DOI: 10.1295/polymj.PJ2008080

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  • Synthesis and Properties of Hybrid Hyperbranched Polymers Containing Oxetane Moiety in the Main Chain and Terminal Oxetanyl, Methacryloyl and Carboxyl Groups

    NOSAKA Mami, KUDO Hiroto, NISHIKUBO Tadatomi

    Journal of Network Polymer,Japan   29 ( 2 )   73 - 85   2008

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    The polyaddition reaction of 1, 3, 5-trisglycidyloxybenzene (TGOB) with 3, 3-bis (4-carboxylphenyloxymethyl) oxetane (CPOMO), methacrylic acid (MAA), and 3-carboxyl-3-ethyloxetane (CEO) was carried out in the presence of tetrabutylammonium bromide (TBAB) as a catalyst at 90°C for 18 h to give the hybrid hyperbranched polymer (HBP-OX-MA-CA) (<I>M</I><SUB>n</SUB>'s = 5200, <I>M</I><SUB>w</SUB><I>/M</I><SUB>n</SUB>=2.21) with terminal oxetanyl, methacryloyl, and carboxyl groups in 80 % yield. Certain curing reactions of HBP-OX-MA-CA were performed in the film state using appropriate photo-acid generator, photo-radical initiator, or tetraphenylphosphonium iodide (TPPI) as a catalyst to give the corresponding cured films. The thermal properties of resulting cured films were examined, and it was found that hybrid cured film by photo-initiated radical polymerization + photo-initiated cationic polymerization + thermal reaction of oxetane groups with carboxyl groups showed higher <I>T</I><SUB>g</SUB> than the other cured films by each reaction such as photo-initiated radical polymerization, photo-initiated cationic polymerization, and thermal reaction of oxetane groups with carboxyl groups.

    DOI: 10.11364/networkpolymer1996.29.73

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  • A novel thermal curing reaction of oxetane resin with active diester Reviewed

    Tadatomi Nishikubo, Hiroto Kudo, Hiroshi Nomura

    POLYMER JOURNAL   40 ( 4 )   310 - 316   2008

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    DOI: 10.1295/polymj.PJ2007171

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  • A novel noria (water-wheel-like cyclic oligomer) derivative as a chemically amplified electron-beam resist material Reviewed

    Hiroto Kudo, Daisuke Watanabe, Tadatomi Nishikubo, Ken Maruyama, Daisuke Shimizu, Toshiyuki Kai, Tsutomu Shimokawa, Christopher K. Ober

    JOURNAL OF MATERIALS CHEMISTRY   18 ( 30 )   3588 - 3592   2008

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    DOI: 10.1039/b805394d

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  • Phenolic molecular glasses as resists for next generation lithography Reviewed

    Xavier Andre, Jin Kyun Lee, Anuja De Silva, Nelson Felix, Christopher K. Ober, Heidi B. Cao, Hai Deng, Hiroto Kudo, Daisuke Watanabe, Tadatomi Nishikubo

    ADVANCES IN RESIST MATERIALS AND PROCESSING TECHNOLOGY XXIV   6519   2007

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    DOI: 10.1117/12.722919

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  • 側鎖にビシクロオルトエステル類を有するポリマーの合成とその光架橋反応および光架橋前後の屈折率特性

    曽我 哲徳, 工藤 宏人, 西久保 忠臣

    ネットワークポリマー   28   65 - 68   2007

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    DOI: 10.11364/networkpolymer1996.28.Supplement_65

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  • 低屈折率材料の開発を目的とした新しい含フッ素ポリマーの合成とその機能化

    小池 直之, 工藤 宏人, 西久保 忠臣

    ネットワークポリマー   28   77 - 80   2007

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    DOI: 10.11364/networkpolymer1996.28.Supplement_77

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  • ビスアルキルハライド類とトリメシン酸との反応による光架橋性ハイパーブランチポリエステルの合成と特性

    平林 聡明, 工藤 宏人, 西久保 忠臣

    ネットワークポリマー   28   85 - 88   2007

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    DOI: 10.11364/networkpolymer1996.28.Supplement_85

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  • ハイパーブランチポリカーボネートの合成とその光機能化

    高添 泰地, 工藤 宏人, 西久保 忠臣

    ネットワークポリマー   28   81 - 84   2007

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    DOI: 10.11364/networkpolymer1996.28.Supplement_81

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  • 動的共有結合化学を基盤としたラダー型環状オリゴマーおよびラダーポリマーの合成

    工藤 宏人, 林理 英子, 重松 享輔, 西久保 忠臣

    ネットワークポリマー   28   89 - 92   2007

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    DOI: 10.11364/networkpolymer1996.28.Supplement_89

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  • Synthesis and Properties of Dual-curable Polymers Containing Oxetanyl, Methacryloyl and Carboxyl Grous

    NOSAKA Mami, KUDO Hiroto, NISHIKUBO Tadatomi

    Journal of Network Polymer,Japan   28 ( 1 )   19 - 31   2007

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    The polyaddition reactions of 3, 3-bis (4-carboxylphenyloxymethyl) oxetane (OX) to bisepoxides [bisphenol A diglycidylether (BPGE), 4, 4′-bisglycidyloxybiphenyl (GBiPhe), and 1, 4-bisglycidyloxybenzene (GPhe)] were carried out in the presence of tetrabutylammonium bromide (TBAB) at 90°C for 24 h to give the polymers (P<SUB>1</SUB>-OX, P<SUB>2</SUB>-OX, and P<SUB>3</SUB>-OX) with <I>M</I><SUB>n</SUB>′s = 14000, 13800 and 13300 in 91, 89, and 88% yields, respectively. The reactions of P<SUB>1</SUB>-OX, P<SUB>2</SUB>, -OX, and P<SUB>3</SUB>-OX with methacrylic anhydride were performed to give the corresponding dual-curable polymers (P<SUB>1</SUB>-OX-MA, P<SUB>2</SUB>-OX-MA, and P<SUB>3</SUB>-OX-MA) with both methacryloyl and oxetanyl groups in the side chains. Furthermore, the reactions of P<SUB>1</SUB>-OX, P<SUB>2</SUB>-OX, and P<SUB>3</SUB>-OX with tetrahydrophthalic anhydride were performed to give the corresponding dualcurable polymers (P<SUB>1</SUB>-OX-CA, P<SUB>2</SUB>-OX-CA and P<SUB>3</SUB>-OX-CA) with both carboxyl and oxetanyl groups in the side chains. The photo-polymerization reactions of P<SUB>1</SUB>-OX-MA, P<SUB>2</SUB>-OX-MA, and P<SUB>3</SUB>-OX-MA were performed in a film state using a photo-radical initiator or a photo-acid generator. The thermally curing reactions of P<SUB>1</SUB>-OX-CA, P<SUB>2</SUB>-OX-CA and P<SUB>3</SUB>-OX-CA were performed in a film state using TPPI. Thus combining both the photo and thermal reactions, dually-curing reactions were successfully performed in a film state using the photo-radical initiator and the photo-acid generator to give the corresponding cured films. The thermal properties of resulting cured films were examined.

    DOI: 10.11364/networkpolymer1996.28.19

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  • 光重合性基と熱硬化反応性基を有するハイブリッド型ハイパーブランチポリマーの合成とその光および熱硬化反応

    能坂 麻美, 工藤 宏人, 西久保 忠臣

    ネットワークポリマー   27   13 - 16   2006

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    DOI: 10.11364/networkpolymer1996.27.Supplement_13

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  • Molecular waterwheel (Noria) from a simple condensation of resorcinol and an alkanedial Reviewed

    Hiroto Kudo, Rieko Hayashi, Kouji Mitani, Tsutomit Yokozawa, Noriko C. Kasuga, Tadatond Nishikubo

    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION   45 ( 47 )   7948 - 7952   2006

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    DOI: 10.1002/anie.200603013

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  • 側鎖に光異性化反応基を有するポリマー類の合成とその光反応特性および屈折率変化

    工藤 宏人, 西久保 忠臣

    ネットワークポリマー   27   17 - 20   2006

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    DOI: 10.11364/networkpolymer1996.27.Supplement_17

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  • Development of Novel UV-and Thermal Curing Materials Based on Oxetane Resins

    NISHIKUBO Tadatomi, KUDO Hiroto

    Journal of Network Polymer,Japan   27 ( 1 )   38 - 45   2006

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    This paper reviews our recent studies concerning the new addition reactions of oxetanes with certain materials and the synthesis of new functional polymers by the new reactions of oxetanes. The reactions of oxetanes with certain materials proceeded smoothly under appropriate reaction conditions using quaternary onium salts as catalysts to afford the corresponding 1 : 1 adducts selectively in satisfactory yields. From applying these reactions of bis (oxetane) s, certain new functional polymers with pendant chloromethyl groups or hydroxyl groups were obtained. Also, it was found that polyfunctional oxetanes (oxetane resins) had high photochemical reactivity and good thermal stability. These results showed the oxetane resins to be useful for UV-and thermal-curing technologies.

    DOI: 10.11364/networkpolymer1996.27.38

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  • Syntheses and Photochemical Properties of the Polymers with Pendant Azobenzene and Anthracene Moieties

    YAMAMOTO Masaru, KUDO Hiroto, ONO Yoshitomo, NISHIKUBO Tadatomi

    Journal of Network Polymer,Japan   27 ( 1 )   10 - 19   2006

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    We examined the syntheses and photochemical properties of the polymers with pendant azobenzene (AZ) and anthracene (AT) moieties. The photochemical reactions of the obtained polymers were performed in the film state with 250-W high-pressure mercury lamp. The photochemical valence isomerization of trans-AZ and photochemical dimerization of AT were observed to proceed smoothly, resulting in giving the cis-AZ and AT-dimer, respectively. The stored thermal energy of the irradiated polymers was evaluated by differential scanning calorimetry to be 1.01-27.70 kJ/mol. Furthermore, the change in the refractive-indices (Δn's = 0.010-0.075) was observed to occur before and after the photochemical reactions.

    DOI: 10.11364/networkpolymer1996.27.10

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  • 側鎖にメタクリロイル基を有する環状ポリスルフィドの合成とその光硬化反応および硬化物の特性

    牧野 真也, 工藤 宏人, 西久保 忠臣

    ネットワークポリマー   26   9 - 12   2005

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    DOI: 10.11364/networkpolymer1996.26.Supplement_9

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  • メタクリロイル基を有するハイパーブランチポリマーの合成とその光硬化反応および得られた硬化物の特性

    丸山 研, 工藤 宏人, 池原 飛之, 西久保 忠臣

    ネットワークポリマー   26   1 - 4   2005

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    DOI: 10.11364/networkpolymer1996.26.Supplement_1

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  • 光カチオン重合性基と光ラジカル重合性基を有するハイブリット型高分子の合成とその光反応および熱硬化反応

    能坂 麻美, 工藤 宏人, 西久保 忠臣

    ネットワークポリマー   26   17 - 20   2005

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    DOI: 10.11364/networkpolymer1996.26.Supplement_17

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  • オキセタン類のカチオン開環共重合による新規デンドリティック高分子の合成と機能化

    青木 英行, 工藤 宏人, 西久保 忠臣

    ネットワークポリマー   26   13 - 16   2005

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    DOI: 10.11364/networkpolymer1996.26.Supplement_13

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  • Novel Photofunctional Materials Based on Cyclic Oligomers : Synthesis and Photochemical Reactions of Calixarene-and Cyclodextrin-Derivatives Containing Polymerizable Groups, Protective Groups, and Photo-Isomerizable Groups

    KUDO Hiroto, KAMEYAMA Atsushi, NISHIKUBO Tadatomi

    Journal of Network Polymer,Japan   26 ( 2 )   98 - 110   2005

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    This paper reviews our recent studies concerning the synthesis and photochemical reactions of the calixarene-derivatives and cyclodextrin-derivatives containing polymerizable groups, protective groups, and photo-isomerizable groups. It was found that the synthesized materials had high thermal stability, good film-forming property, and high photochemical reactivity. It is expected that the obtained materials are useful for EB-and UV-curing technologies and photo-resist systems. Furthermore, the large refractive-indices changes were observed before and after photo-isomerization of calixarene-derivatives. It is also expected that the obtained calixarene derivatives are widely used for novel optoelectronics materials.

    DOI: 10.11364/networkpolymer1996.26.98

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  • シクロデキストリンを基盤とした光硬化材料の合成と性質

    井上 奈緒美, 工藤 宏人, 西久保 忠臣

    ネットワークポリマー   26   5 - 8   2005

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    DOI: 10.11364/networkpolymer1996.26.Supplement_5

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  • 3,3-ビス (ヒドロキシメチル) オキセタンのアニオン開環重合と得られたポリマーの機能性化

    工藤 宏人, 森田 亜也子, 西久保 忠臣

    ネットワークポリマー   25   115 - 118   2004

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    DOI: 10.11364/networkpolymer1996.25.Supplement_115

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  • Synthesis and photochemical reaction of high-performance UV-curing oligomers Reviewed

    T Nishikubo, A Kameyama, H Kudo

    PHOTOINITIATED POLYMERIZATION   847   363 - 377   2003

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  • 新しい多分岐ポリマーの合成と機能化

    森田 亜也子, 工藤 宏人, 西久保 忠臣

    ネットワークポリマー   24   153 - 156   2003

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    DOI: 10.11364/networkpolymer1996.24.Supplement_153

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  • 同一分子内にオキセタニル基とカルボキシル基を有するモノマーの合成と重付加反応および得られた多分岐ポリマーの光機能性化

    工藤 宏人, 仲神 岳彦, 西久保 忠臣

    ネットワークポリマー   24   149 - 152   2003

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    DOI: 10.11364/networkpolymer1996.24.Supplement_149

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  • 側鎖にオキセタニル基を有するポリエステルの合成とその光架橋反応

    工藤 宏人, 植田 健介, 佐野 直考, 西久保 忠臣

    ネットワークポリマー   23   191 - 194   2002

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    DOI: 10.11364/networkpolymer1996.23.Supplement_191

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Books

  • Control and Improvement of High-Refractive-Index Property of Transparent Polymers

    KUDO,Hiroto( Role: Edit)

    2019.12 

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  • 透明ポリマーの材料開発と高性能化 Reviewed

    工藤 宏人( Role: Sole author)

    シーエムシー出版  2015.1 

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  • 「光」の制御技術とその応用 事例集

    工藤 宏人( Role: Sole author)

    (株)技術情報協会  2014.3 

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    第5節 化学反応による屈折率変換技術

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  • 第5節 化学反応による屈折率変換技術

    工藤 宏人( Role: Sole author)

    光」の制御技術とその応用 事例集、(株)技術情報協会  2014.3 

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  • 電子部品用 機能性粘着・接着剤

    工藤 宏人

    シーエムシー出版  2013.8 

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    第八章「光学特性」

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  • 屈折率変化材料の開発

    工藤 宏人( Role: Contributor)

    シーエムシー ・ 透明高分子材料の高屈折率化と屈折率制御 

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Presentations

  • 極端紫外線リソグラフィー用レジスト材料の分子設計 Invited

    工藤 宏人

    フォトポリマー懇話会 第228回講演会  2018.10 

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  • Synthesis and Property of Tannic Acid Derivatives and Their Application for Extreme Ultraviolet Laser Lithography System Invited International conference

    KUDO,Hiroto

    The35th International Conference of Photopolymer Science and Technology  2018.6 

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    Language:English   Presentation type:Oral presentation (keynote)  

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  • 極端紫外線レジスト材料の開発 Invited

    工藤 宏人

    第11回リソグラフィ将来技術調査専門委員会(電気学会)  2017.5 

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  • Synthesis and Resist Properties of Calixarene Polymers with Pendant Haloalkyl Groups Invited International conference

    KUDO,Hiroto

    2016.6 

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  • 新規エポキシ樹脂硬化システムの開発とブドウの房状ポリマー(Botryosin)の合成と特性に関する研究

    工藤 宏人

    エポキシ樹脂技術協会 特別講演会  2016.2 

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  • ε-カプロラクタムとエポキシドによる開環共重合 Invited

    工藤 宏人

    2016.2 

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    Language:Japanese   Presentation type:Public lecture, seminar, tutorial, course, or other speech  

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Industrial property rights

  • 高分子および当該高分子の製造方法

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    Application no:2013-096035  Date applied:2013.4

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Awards

  • 高性能なネットワーク構造の創製を目的とした新規硬化反応の開発・学術賞

    2019.10   合成樹脂工業協会  

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    Country:Japan

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  • 合成樹脂工業協会・学術奨励賞

    2012.10   合成樹脂工業協会  

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    Country:Japan

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  • 高分子学会「日立化成賞」

    2007.9   高分子学会  

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    Country:Japan

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Research Projects

  • ハイパーブランチポリアセタールを基盤とした高解像性レジスト材料の開発

    Grant number:16808244  2016

    科学技術振興機構  産学が連携した研究開発成果の展開/研究成果展開事業/マッチングプランナープログラム

    工藤 宏人

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  • Synthesis and property of novel tellurium containing polymers

    Grant number:24655106  2012.4 - 2014.3

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research  Grant-in-Aid for Challenging Exploratory Research

    KUDO Hiroto

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    Grant amount:\3900000 ( Direct Cost: \3000000 、 Indirect Cost:\900000 )

    We examined the condensation reaction of TeCl4 with certain aromatic compounds biphenyl, diphenyl ether, and diphenyl sulfide in CHCl3 using AlCl3 at 60 oC fro 48 h. As the result, no polymer obtained. Furthermore, condensation reaction of TeCl4 and triphenyl methane (TPM) was examined in the same way, to give corresponding polymers poly(Te-TPM)with Mn's = 2070 ~ 6860 in 52 ~ >99% yields. This polymer had good solubility, good film-forming property, high thermal stability, and high refractive index property. Furthermore, we examined the reaction of bis(4-hydroxy phenyl)tellurium dichloride (HPT) and phthaloyl dichloride using pyridine in dimethylacetamide at room temperature for 48 h, to afford corresponding polyesters with Mn's = 6020 ~ 9200 in 76 ~ 83% yields. The synthesized polyesters had good solubility, good film-forming property, high thermal stability, and high refractive index property.

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  • Synthesis of Cyclic Oligomers by the Dynamic Covalent Chemistry Mechanism and their Application for Resist Materials

    Grant number:22350088  2010 - 2012

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research  Grant-in-Aid for Scientific Research (B)

    KUDO Hiroto

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    Grant amount:\19760000 ( Direct Cost: \15200000 、 Indirect Cost:\4560000 )

    A new dynamic covalent chemistry (DCC) system in the reaction of resorcinol and 1,5-pentanedial could be achieved, yielding a only soluble oligomer noria (noria means water wheel in Latin) in high yield, resembling a water-wheel in appearance. Application of the noria derivatives with pendant photo-reactive groups were examined for UV-curing materials and photo-resist materials. The obtained noria derivatives had good solubility, good film-forming ability, high thermal stability, and high photo-chemical reactivity. Furthermore, certain new ladder cyclic oligomers could be synthesized using a similar approach to that employed for the synthesis of noria and their application as next generation resist materials was also investigated

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  • 超分子化学を利用した高屈折率材料の開発

    Grant number:19655084  2007 - 2008

    日本学術振興会  科学研究費助成事業  萌芽研究

    工藤 宏人, 西久保 忠臣

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    Grant amount:\3400000 ( Direct Cost: \3400000 )

    1-アザ-18-クラウン-6-エーテル(1-Aza-18-C-6)骨格を有するスチレンタイプのモノマー(VBA18-C-6)を合成し、そのラジカル重合により対応するポリマー(M_n=1-2万程度)を合成した。合成したポリマーをシリコンウエハー上へのスピンコートにより薄膜を形成させた。形成したポリマーの薄膜をKI水溶液中に24時問浸漬した。その結果、フィルムが水に溶解して、膜圧の減少が起こり、正確な屈折率の評価は困難であった。そこで、架橋膜の作成を試みた。架橋部位としてオキセタニル基を有するスチレン誘導体を合成し、このモノマーとVBA18-C-6との共重合(仕込み比;10:1)を行い、合成したポリマーのフィルムを作成し、光架橋させ、水に不溶な架橋膜を作成した。次に、このポリマーフィルムをKI又はLiI水溶液に浸漬し、屈折率を測定した。しかし、ポリマーフィルムの屈折率の上昇は観測されなかった。このことからポリマーフィルムが光架橋したことにより、ポリマーの膨潤性が低下したために、包接化が起こらなかったと思われる。そこで、次に架橋部位の割合を減らした共重合(仕込み比;10:0.5)を行い、同様の検討を行った結果、薄膜の位置によっては屈折率が大幅に上昇し、屈折率は2.39まで上昇することが判明した。しかしながら、薄膜の表面は均一ではなく、位置によっては屈折率が全く上昇せずに、むしろ低下する部位も存在した。このことは、カリウム塩が包接することによって、そのカウンターイオンのヨウ素により屈折率は大きく上昇しているが、その包接挙動が均一的に進行していないことを示した。均一に包接を進行させ、かつ包接後のポリマー薄膜が良好な均一膜を保てるポリマーを分子設計することが出来れば、2.0以上の高屈折率を有する薄膜が開発できる可能性を示した。

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  • Synthesis and Particular Property of Ladder-Type Cyclic Compounds Based on the Dynamic Covalent Chemistry

    Grant number:18681015  2006 - 2008

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research  Grant-in-Aid for Young Scientists (A)

    KUDO Hiroto

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    Grant amount:\30290000 ( Direct Cost: \23300000 、 Indirect Cost:\6990000 )

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  • 環拡大反応による大環状ポリマーの合成

    Grant number:15750107  2003 - 2005

    日本学術振興会  科学研究費助成事業  若手研究(B)

    工藤 宏人

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    Grant amount:\2700000 ( Direct Cost: \2700000 )

    前年度までは、環状高分子の合成法として、環状チオエステル化合物とチイラン類との挿入反応による重合挙動を明らかとした。この反応は、チオエステル部位へのチイラン類の挿入反応と、環の組み換え反応が同時に進行することを見出している。本年度では、チオエステル結合部分を動的共有結合であることに着目し、環状チオエステル化合物の環拡大反応挙動について検討を行った。
    環状ジチオエステル(CDE)の環拡大反応を、触媒としてテトラブチルアンモニウムクロリド(TBAC)を用い、NMP(0.5mol/L)中、70℃、種々の反応時間で行った結果、数平均分子量M_n=2100-4500のポリマーが収率91-95%で得られた。得られたポリマーの構造確認は、IR、^1H NMRおよび、MALDI-TOF massスペクトルにより行い、得られたポリマーは、CDEを繰り返し単位とする環状構造を有することが判明した。さらに、反応時間が24-96時間の場合、反応時間の経過に伴い、分子量は増加する傾向を示したが、さらに反応時間が長くなると、分子量は減少し、分子量分布は狭くなる傾向を示した。このことは、環の組み換え反応は、環の拡大-縮小の可逆反応であり、熱力学的に最も安定な構造体(M_n=2.1×10^3(m≒4),M_w/M_n=1.4)へと収束したことを示唆している。同様に環状テトラチオエステル(CTE)の環拡大重合を検討した結果、数平均分子量M_n=2800のオリゴマーが収率96%で得られた。得られたオリゴマーの構造確認を、IR、^1H NMRおよび質量分析により行った結果、フタリド骨格の形成が確認された。このことは、CTEのo-ジチオエステル骨格に起因した、フタリド骨格の形成により分子構造は乱れるが定量的に環状オリゴマーが得られることが明らかとなった。さらに、環状ヘキサチオエステル(CHE)の環拡大重合についても同様に検討を行った結果、分子量の増加はほとんど確認されなかった。このことは、CHEの安定な構造に起因して、見かけ上反応はほとんど進行せず、高分子量のポリマーが得られないことを示唆している。

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  • オキセタン誘導体のアニオン重合による新規ハイパーブランチポリマーの合成と機能評価

    Grant number:14655351  2002 - 2004

    日本学術振興会  科学研究費助成事業  萌芽研究

    西久保 忠臣, 工藤 宏人

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    Grant amount:\3000000 ( Direct Cost: \3000000 )

    我々は、これまで3-ヒドロキシメチルオキセタン類のアニオン開環重合を、塩基としてtert-ブトキシカリウム(t-BuOK)を用い、18-クラウン-6-エーテル(18-C-6)存在下、NMP中、種々の反応温度と反応時間で検討した。その結果、末端に1個のオキセタニル基と多数のヒドロキシル基を有するハイパーブランチポリエーテル(HBP-OH)が得られることを見出し、この化合物が新しい機能性ポリマーとしての展開が期待されることを報告している。
    本年度では、合成されたHBP-OHを用いて、新しい多分岐ポリマーの合成と機能化について検討した。HBP-OHの水酸基を保護し、カチオン共重合により、新規デンドリテイック高分子へと誘導した。得られたデンドリテイック高分子の水酸基の脱保護とメタクリロイル基の導入を行うことで機能化を遂行し、側鎖に多数のメタクリロイル基を有する機能性デンドリテイック高分子へ誘導した。得られた機能性高分子の光架橋反応を製膜中で検討したところ、光反応性は非常に優れていることが判明した。さらに、得られた架橋物は耐熱性に優れていることも分かった。また、HBP-OHと多官能性カルボン酸類との付加反応による新規多分岐ポリマーの合成とその光機能化について同様に検討を行った。比較検討のために、多官能性カルボン酸類として、ビスカルボン酸、トリカルボン酸、オクタカルボン酸化合物を用いて行った。その結果、得られた機能性化合物の光反応性および硬化物の物性は、より多分岐構造を有するほうが優れていることが判明した。さらに、合成した機能性多分岐ポリマーは新しいUV硬化樹脂として非常に有用であることを示した。

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  • 新規ハイパーブランチポリマーの合成に関する研究

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    Grant type:Competitive

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