CN117229769A - 半导体纳米粒子复合体、及其分散液、组合物和固化膜 - Google Patents

半导体纳米粒子复合体、及其分散液、组合物和固化膜 Download PDF

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Publication number
CN117229769A
CN117229769A CN202311018670.1A CN202311018670A CN117229769A CN 117229769 A CN117229769 A CN 117229769A CN 202311018670 A CN202311018670 A CN 202311018670A CN 117229769 A CN117229769 A CN 117229769A
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semiconductor nanoparticle
nanoparticle composite
ligand
semiconductor
fatty acid
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Chinese (zh)
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城户信人
森山乔史
佐佐木洋和
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Shoei Chemical Inc
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Shoei Chemical Inc
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    • C08G65/00Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
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    • C09K11/88Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
    • C09K11/881Chalcogenides
    • C09K11/883Chalcogenides with zinc or cadmium
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    • H01B1/00Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
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    • C08G65/00Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32Polymers modified by chemical after-treatment
    • C08G65/329Polymers modified by chemical after-treatment with organic compounds
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  • Luminescent Compositions (AREA)
  • Polyethers (AREA)
  • Optical Filters (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
CN202311018670.1A 2019-06-13 2020-05-26 半导体纳米粒子复合体、及其分散液、组合物和固化膜 Pending CN117229769A (zh)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP2019110307 2019-06-13
JP2019-110307 2019-06-13
JP2019142425A JP7354659B2 (ja) 2019-06-13 2019-08-01 半導体ナノ粒子複合体、半導体ナノ粒子複合体分散液、半導体ナノ粒子複合体組成物および半導体ナノ粒子複合体硬化膜
JP2019-142425 2019-08-01
PCT/JP2020/020686 WO2020250663A1 (ja) 2019-06-13 2020-05-26 半導体ナノ粒子複合体、半導体ナノ粒子複合体分散液、半導体ナノ粒子複合体組成物および半導体ナノ粒子複合体硬化膜
CN202080043418.4A CN114127225A (zh) 2019-06-13 2020-05-26 半导体纳米粒子复合体、半导体纳米粒子复合体分散液、半导体纳米粒子复合体组合物和半导体纳米粒子复合体固化膜

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CN202080043418.4A Division CN114127225A (zh) 2019-06-13 2020-05-26 半导体纳米粒子复合体、半导体纳米粒子复合体分散液、半导体纳米粒子复合体组合物和半导体纳米粒子复合体固化膜

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CN117229769A true CN117229769A (zh) 2023-12-15

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CN202311018670.1A Pending CN117229769A (zh) 2019-06-13 2020-05-26 半导体纳米粒子复合体、及其分散液、组合物和固化膜
CN202080043418.4A Pending CN114127225A (zh) 2019-06-13 2020-05-26 半导体纳米粒子复合体、半导体纳米粒子复合体分散液、半导体纳米粒子复合体组合物和半导体纳米粒子复合体固化膜

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US (2) US12054657B2 (https=)
JP (3) JP7354659B2 (https=)
KR (2) KR20240152968A (https=)
CN (2) CN117229769A (https=)
TW (3) TWI857867B (https=)
WO (1) WO2020250663A1 (https=)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116390997A (zh) * 2020-10-15 2023-07-04 Dic株式会社 含纳米结晶的组合物、油墨组合物、光转换层及发光元件
CN116420439A (zh) * 2021-08-30 2023-07-11 京东方科技集团股份有限公司 量子点材料、量子点发光器件及其制备方法
JP2023036307A (ja) * 2021-09-02 2023-03-14 Dic株式会社 発光性ナノ粒子複合体、インク組成物、光変換層およびカラーフィルタ
WO2023032208A1 (ja) * 2021-09-06 2023-03-09 シャープ株式会社 ナノ粒子組成物、ナノ粒子含有膜、発光素子、波長変換部材、表示装置、およびナノ粒子含有膜の製造方法
CN119310124B (zh) * 2024-11-06 2025-12-05 武汉纺织大学 一种基于核磁共振波谱半高宽的磁纳米粒子质量浓度计算方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000351959A (ja) * 1999-06-10 2000-12-19 Tokyo Magnetic Printing Co Ltd 遊離砥粒スラリー組成物
JP2002121549A (ja) * 2000-06-26 2002-04-26 Mitsubishi Chemicals Corp 半導体超微粒子
US20040007169A1 (en) * 2002-01-28 2004-01-15 Mitsubishi Chemical Corporation Semiconductor nanoparticles and thin film containing the same
CN101570647A (zh) * 2008-04-28 2009-11-04 富士胶片株式会社 有机颜料组合物及其制法、着色感光性树脂组合物、滤色器
US20140340438A1 (en) * 2013-05-14 2014-11-20 Seiko Epson Corporation Ink jet recording apparatus and ink jet recording method
CN106905497A (zh) * 2017-03-22 2017-06-30 京东方科技集团股份有限公司 量子点复合物、中间体及其制备方法和应用
CN109075222A (zh) * 2016-04-26 2018-12-21 昭荣化学工业株式会社 量子点材料及量子点材料的制造方法

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002162501A (ja) 2000-11-28 2002-06-07 Mitsubishi Chemicals Corp 半導体結晶粒子を含有する薄膜状成形体、及びその用途
JP5881045B2 (ja) 2011-10-11 2016-03-09 国立研究開発法人産業技術総合研究所 量子ドット含有チタン化合物及びその製造方法、並びに該量子ドット含有チタン化合物を用いた光電変換素子
KR20180067628A (ko) * 2015-11-12 2018-06-20 후지필름 가부시키가이샤 코어 셸 입자, 코어 셸 입자의 제조 방법 및 필름
EP3425021B1 (en) * 2016-02-29 2020-07-08 FUJIFILM Corporation Semiconductor nanoparticles, dispersion liquid, and film
WO2018016589A1 (ja) 2016-07-20 2018-01-25 富士フイルム株式会社 量子ドット含有組成物、波長変換部材、バックライトユニット、および液晶表示装置
CN106479503A (zh) 2016-09-29 2017-03-08 Tcl集团股份有限公司 一种量子点固态膜及其制备方法
EP3327813B1 (en) 2016-11-25 2021-06-30 Samsung Electronics Co., Ltd. Light emitting device and display device including quantum dot
EP3635069B1 (en) 2017-06-08 2023-06-07 Merck Patent GmbH A composition comprising semiconducting light-emitting nanoparticles having thiol functional surface ligands
CN118421317A (zh) * 2019-06-13 2024-08-02 昭荣化学工业株式会社 半导体纳米粒子复合体及其分散液、组合物和固化膜
WO2020250833A1 (ja) * 2019-06-13 2020-12-17 昭栄化学工業株式会社 半導体ナノ粒子複合体、半導体ナノ粒子複合体分散液、半導体ナノ粒子複合体組成物、半導体ナノ粒子複合体硬化膜および半導体ナノ粒子複合体の精製方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000351959A (ja) * 1999-06-10 2000-12-19 Tokyo Magnetic Printing Co Ltd 遊離砥粒スラリー組成物
JP2002121549A (ja) * 2000-06-26 2002-04-26 Mitsubishi Chemicals Corp 半導体超微粒子
US20040007169A1 (en) * 2002-01-28 2004-01-15 Mitsubishi Chemical Corporation Semiconductor nanoparticles and thin film containing the same
CN101570647A (zh) * 2008-04-28 2009-11-04 富士胶片株式会社 有机颜料组合物及其制法、着色感光性树脂组合物、滤色器
US20140340438A1 (en) * 2013-05-14 2014-11-20 Seiko Epson Corporation Ink jet recording apparatus and ink jet recording method
CN109075222A (zh) * 2016-04-26 2018-12-21 昭荣化学工业株式会社 量子点材料及量子点材料的制造方法
CN106905497A (zh) * 2017-03-22 2017-06-30 京东方科技集团股份有限公司 量子点复合物、中间体及其制备方法和应用

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TW202411401A (zh) 2024-03-16
TW202108736A (zh) 2021-03-01
TWI833967B (zh) 2024-03-01
KR20220024185A (ko) 2022-03-03
KR102809556B1 (ko) 2025-05-19
JP7804892B2 (ja) 2026-01-23
JP7574889B2 (ja) 2024-10-29
JP2024180509A (ja) 2024-12-26
WO2020250663A1 (ja) 2020-12-17
JP7354659B2 (ja) 2023-10-03
US20240352311A1 (en) 2024-10-24
JP2023155249A (ja) 2023-10-20
US20220259492A1 (en) 2022-08-18
JP2020204756A (ja) 2020-12-24
TWI909650B (zh) 2025-12-21
TW202500716A (zh) 2025-01-01
CN114127225A (zh) 2022-03-01
TWI857867B (zh) 2024-10-01
US12054657B2 (en) 2024-08-06
KR20240152968A (ko) 2024-10-22
US12365836B2 (en) 2025-07-22

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