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

• Project/Area Number: 18681015
• Research Category: Grant-in-Aid for Young Scientists (A)
• Allocation Type: Single-year Grants
• Research Field: Nanostructural science
• Research Institution: Kanagawa University
• Principal Investigator: KUDO Hiroto Kanagawa University, 工学部, 助教 (30343635)
• Co-Investigator(Renkei-kenkyūsha): 西久保 忠臣
• Project Period (FY): 2006 – 2008
• Project Status: Completed (Fiscal Year 2008)
• Budget Amount: ¥30,290,000 (Direct Cost: ¥23,300,000、Indirect Cost: ¥6,990,000); Fiscal Year 2008: ¥2,210,000 (Direct Cost: ¥1,700,000、Indirect Cost: ¥510,000); Fiscal Year 2007: ¥2,210,000 (Direct Cost: ¥1,700,000、Indirect Cost: ¥510,000); Fiscal Year 2006: ¥25,870,000 (Direct Cost: ¥19,900,000、Indirect Cost: ¥5,970,000)
• Keywords: 動的共有結合化学 / 縮合反応 / X線構造解析 / レゾルシノール / ジアルデヒド / ラダー型環状オリゴマー / ラダーポリマー / 包接能 / ビスアルデヒド / 分子レジスト

Research Abstract

レゾルシノールと1,5-ペンンタンジアールの縮合反応により、ラダー型環状オリゴマーが選択的に合成されることを見出し、動的共有結合化学反応システムに基づくことを明らかにした。その構造をnoria(ノーリア=水車:ラテン語)と命名した。ノーリアは、ルビジウムを選択的に包接することが判明した。さらに、この反応システムを他のアルカンジアールに適応したところ、遇奇効果が存在することが判明し、選択的ラダーポリマーの新しい合成法をも見出した。合成したnoriaの水酸基に光脱保護反応性基を導入し、電子線(EB)レジストおよび、極端紫外線(EUV)レジスト特性について検討した結果、26〜70nmまでの高解像度が得られることが判明した。これらのことは、次世代レジスト材料として有用であることを示した。

Research Products

• [Journal Article] アセタール残基を有するnoria (ラダー型環状オリゴマー) 誘導体の合成とその光脱保護反応 (2009)
  • Author(s): 工藤宏人・渡辺大輔・西久保忠臣
  • Journal Title: 高分子論文集 66(1) Pages: 10-16
  • NAID: 10024759783
  • Peer Reviewed
• [Journal Article] A novel noria (water-wheel-like cyclic oligomer) derivatives as a chemically amplified electron-beam resist material (2008)
  • Author(s): Hiroto Kudo, Daisuke Watanabe. Tadatomi Nishikubo, Ken Maruyama, Daisuke Shimizu, Toshiyuki Kai, Tsutomu Shimokawa, Christopher K. Ober
  • Journal Title: Journal of Materials Chemistry 18 Pages: 3588-3592
• [Journal Article] One-Pot Synthesis of a Novel Ladder Polymer of Calixarene via Condensation Reaction of Resorcinol and Alkanedial Based on Dynamic Covalent Chemistry (2008)
  • Author(s): Hiroto Kudo, Kyosuke Shigematsu, Kouji Mitani, Tadatomi Nishikubo, Noriko C. Kasuga, Hideyuki. Uekusa, and Yuji Ohashi
  • Journal Title: Macromolecules 41,(6) Pages: 2030-2036
• [Journal Article] A novel noria (water-wheel-like cyclic oligomer) derivatives as a chemically amplified electron-beam resist material (2008)
  • Author(s): Hiroto Kudo, Daisuke Watanabe, Tadatomi Nishikubo, Ken Maruyama, Daisuke Shimizu, Toshiyuki Kai, Tsutomu Shimokawa, Christopher K. Ober
  • Journal Title: Journal of Materials Chemistry 18 Pages: 3588-3592
  • Peer Reviewed
• [Journal Article] A Novel Approach to Cyclic Polysulfides via the Controlled Ring-ex pansion Polymerization of Cyclic Thiourethane with Thiiranes (2008)
  • Author(s): Hiroto Kudo, Masaaki Sato, Ry osuke Wakai, Tadashi Iwamoto, and Tadatomi Nishikubo
  • Journal Title: Macromolecules 41(3) Pages: 521-523
  • Peer Reviewed
• [Journal Article] One-Pot Synthesis of a Novel Ladder Polymer of Calixarene via Condensation Reaction of Resorcinol and Aikanedial Based on Dynamic Covalent Chemistry (2008)
  • Author(s): H. Kudo, K. Shigematsu, K. Mitani, T. Nishikubo, N. C. Kasuga, H. Uekusa, and Y. Ohashi,
  • Journal Title: Macromolecules 41, (6) Pages: 230-2036
  • Peer Reviewed
• [Journal Article] Synthesis and Properties of Photo-cross-linkable Hyperbranched Poly (urethane)s Both Containing Termianl Methacryloyl Groups and Carboxyl Groups (2007)
  • Author(s): K. Maruyama, H. Kudo, T. Ikehara, T. Nishikubo, I. Nishimura、 A. Sshishido, and T. Ikeda
  • Journal Title: Macromolecules, 40, (14) Pages: 4895-4900
  • Peer Reviewed
• [Journal Article] Synthesis of Self-Photosensitizing Polyesters Containing Donor-Acceptor Norbomadiene Moieties and Benzophenone Groups and The (2007)
  • Author(s): Y. Ono, N. Kawashima, H. Kudo, T. Nishikubo, and T. Nagai
  • Journal Title: J. Polym. Sci. Part A. Polym. Chem. 45, (14) Pages: 2978-2988
  • Peer Reviewed
• [Journal Article] Phenolic Molecular Glasses as Resists for Next Generation Lithography (2007)
  • Author(s): Xavier Andre, Jin Kyun Lee, Anuja DeSilva, Christopher K.Ober, Heidi B.Cao, Hai Deng, Hiroto Kudo, Daisuke WVatanabe, Tadatomi Nishikubo
  • Journal Title: SPIE Vol. 6519
• [Journal Article] Large Refractive Index Change during Photo Crosslinking Reaction of Poly(silsesquioxane) Derivatives Containing Cinnamoyl Moieties in the Side Chains (2007)
  • Author(s): Hiroto Kudo, Masaru, Yamamoto, Tadatomi Nishikubo
  • Journal Title: Journal of Network Polymer, Japan Vol. 28 Pages: 11-18
• [Journal Article] 光重合性基と熱硬化反応性基を有するハイブリッド型ポリマーの合成とその性質 (2007)
  • Author(s): 能坂 麻美, 工藤 宏人, 西久保 忠臣
  • Journal Title: ネットワークポリマー Vol. 28 Pages: 19-31
• [Journal Article] Synthesis of Macrocycles by the Ring-crossover Reaction of Cyclic Dithioester (2007)
  • Author(s): Hiroto Kudo, Shinya Makino, Tadatomi Nishikubo
  • Journal Title: J. Polym. Sci. Part A. Polym. Chem. 45 Pages: 680-687
• [Journal Article] Molecular Water-Wheel (Noria) from Simple Condensation of Resorcinol and Alkanedial (2006)
  • Author(s): Hiroto Kudo, Rieko Hayashi, Kouji Mitani, Tsutomu Yokozawa, Noriko C. Kasuga,and Tadatomi Nishikubo
  • Journal Title: Angewandte Chemie Int. Ed 45 Pages: 7948-7952
• [Journal Article] Molecular Water-Wheel (Noria) from Simple Condensation of Resorcinol and Alkanedial (2006)
  • Author(s): Hiroto Kudo, Rieko Hayashi, Kouji Mitani, Tsutomu Yokozawa, Noriko C, Kasuga, Tadatomi Nishikubo
  • Journal Title: Angewandte Chemie Int. Ed. 45 Pages: 7948-7952
• [Journal Article] Novel Materials for Large Change in Refractive Index : Synthesis and Photochemical Reaction of the Ladder-like Poly(silsesquioxane) Containing Norbornadiene, Azobenzene, and Anthracene Groups in the Side Chains (2006)
  • Author(s): Hiroto Kudo, Masaru Yamamoto, Tadatomi Nishikubo
  • Journal Title: Macromolecules 39 Pages: 1759-1765
• [Presentation] ラダー型環状オリゴマーの合成と性質およびその機能化 (2008)
  • Author(s): 工藤宏人
  • Organizer: 第57回高分子討論会2G17
  • Place of Presentation: 大阪市立大学
  • Year and Date: 2008-09-24
• [Presentation] Synthesis and Application of Ladder Cyclic Oligomer (noria) and Ladder Polymer obtained by New Dynamic Covalent Chemistry System (2008)
  • Author(s): Hiroto KUDO
  • Organizer: International Symposium on Polymer Chemistry
  • Place of Presentation: Hefei in Chaina
• [Presentation] Synthesis and Application of Ladder Cyclic Oligomer (noria) and Ladder Polymer Obtained by New Dynamic Covalent, Chemistry System (2008)
  • Author(s): Hiroto KUDO
  • Organizer: International Symposium on Polymer Che mistry
  • Place of Presentation: Hefei, China
• [Presentation] 環状オリゴマーを基盤とした光機能性材料の開発 (2007)
  • Author(s): 工藤宏人
  • Organizer: 平成19年度神奈川県ものづくり技術交流会
  • Place of Presentation: 神奈川県産業技術センター
  • Year and Date: 2007-10-26
• [Presentation] 環状オリゴマーを基盤とした光機能性材料の開発 (2007)
  • Author(s): 工藤 宏人
  • Organizer: 平成19年度神奈川県ものづくり技術交流会
  • Place of Presentation: 神奈川産業技術センター
  • Year and Date: 2007-10-26
• [Presentation] 環状オリゴマーを基盤とした光機能性材料(レジスト、屈折率変換材料)の開発 (2007)
  • Author(s): 工藤宏人
  • Organizer: 高分子討論会
  • Place of Presentation: 名古屋工業大学
  • Year and Date: 2007-09-20
• [Presentation] 環状オリゴマリを基盤とした光壌能牲材料(レジスト、屈折率変換材料)の開発 (2007)
  • Author(s): 工藤 宏人
  • Organizer: 高分子討論会
  • Place of Presentation: 名古屋工業大学
  • Year and Date: 2007-09-20