JPWO2014141742A1 - コア−シェル型ナノ粒子及びその製造方法 - Google Patents
コア−シェル型ナノ粒子及びその製造方法 Download PDFInfo
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- JPWO2014141742A1 JPWO2014141742A1 JP2014527995A JP2014527995A JPWO2014141742A1 JP WO2014141742 A1 JPWO2014141742 A1 JP WO2014141742A1 JP 2014527995 A JP2014527995 A JP 2014527995A JP 2014527995 A JP2014527995 A JP 2014527995A JP WO2014141742 A1 JPWO2014141742 A1 JP WO2014141742A1
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- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 description 1
- ZGSOBQAJAUGRBK-UHFFFAOYSA-N propan-2-olate;zirconium(4+) Chemical compound [Zr+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] ZGSOBQAJAUGRBK-UHFFFAOYSA-N 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000010069 protein adhesion Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910001112 rose gold Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- YOUIDGQAIILFBW-UHFFFAOYSA-J tetrachlorotungsten Chemical compound Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical class [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- WOZZOSDBXABUFO-UHFFFAOYSA-N tri(butan-2-yloxy)alumane Chemical compound [Al+3].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-] WOZZOSDBXABUFO-UHFFFAOYSA-N 0.000 description 1
- MYWQGROTKMBNKN-UHFFFAOYSA-N tributoxyalumane Chemical compound [Al+3].CCCC[O-].CCCC[O-].CCCC[O-] MYWQGROTKMBNKN-UHFFFAOYSA-N 0.000 description 1
- ZLGWXNBXAXOQBG-UHFFFAOYSA-N triethoxy(3,3,3-trifluoropropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC(F)(F)F ZLGWXNBXAXOQBG-UHFFFAOYSA-N 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- BJDLPDPRMYAOCM-UHFFFAOYSA-N triethoxy(propan-2-yl)silane Chemical compound CCO[Si](OCC)(OCC)C(C)C BJDLPDPRMYAOCM-UHFFFAOYSA-N 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- LGROXJWYRXANBB-UHFFFAOYSA-N trimethoxy(propan-2-yl)silane Chemical compound CO[Si](OC)(OC)C(C)C LGROXJWYRXANBB-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- OBROYCQXICMORW-UHFFFAOYSA-N tripropoxyalumane Chemical compound [Al+3].CCC[O-].CCC[O-].CCC[O-] OBROYCQXICMORW-UHFFFAOYSA-N 0.000 description 1
- MDDPTCUZZASZIQ-UHFFFAOYSA-N tris[(2-methylpropan-2-yl)oxy]alumane Chemical compound [Al+3].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-] MDDPTCUZZASZIQ-UHFFFAOYSA-N 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical class [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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Abstract
Description
本発明のコア−シェル型ナノ粒子におけるコア部は、金属のナノ粒子である。金属種としては、一級アミノ基および/または二級アミノ基を有するポリアミンセグメント(b1)を有する化合物(B)がその表面にポリマー層として固定化できれば、特に限定されず、たとえば、貴金属、遷移金属、希土類金属、およびこれらの合金や混合物などが使用できる。好ましくは、Au、Ag、Pt、Pd、Cu、Al、Ni、Co、Si、Snおよびこれらの合金や混合物からなるナノ粒子であり、さらに好ましくは、Au、Ag、Pt、Pd、Cu、Siおよびこれらの合金や混合物からなるナノ粒子である。最も好ましいのは、金又は銀のナノ粒子である。
本発明において、化合物(B)中のポリアミンセグメント(b1)としては、一級アミノ基及び/又は二級アミノ基を有し、前記金属ナノ粒子(A)の表面に安定なポリマー層を形成できれば特に限定されず、例えば、分岐状ポリエチレンイミン、直鎖状ポリエチレンイミン、ポリアリルアミン、ポリビニルピリジンなどからなるセグメントが挙げられる。目的とする酸化物(C)をマトリックスとするシェル層を効率的に製造できる観点により、分岐状ポリエチレンイミンセグメントであることが望ましい。また、ポリアミンセグメント(b1)の分子量としては、酸化物ソース(C’)のゾルゲル反応を行う際の溶液における溶解度と、金属ナノ粒子(A)表面への固定化とのバランスを取って、安定なポリマー層を形成できる範囲であれば特に制限されないが、好適に安定な層を形成できる観点から、ポリアミンセグメントの重合単位の繰り返し単位数が5−10,000の範囲であることが好ましく、特に10−8,000の範囲であることが好ましい。
シェル層にある酸化物(C)は、金属ナノ粒子(A)表面に存在しているポリアミンセグメント(b1)層を反応場かつ触媒として、酸化物ソース(C’)のゾルゲル反応により析出し、安定な酸化物シェル層を形成できれば、特に限定されず、たとえば、シリコン、チタン、ジルコニウム、アルミニウム、イットリウム、亜鉛、錫の酸化物、およびこれらの複合/混合酸化物であってもよい。金属ナノ粒子(A)表面に容易かつ選択的なゾルゲル反応によって、制御された酸化物(C)を効率的に形成できる観点から、シリカ、酸化チタン、酸化ジルコニウムが好ましく、シリカと酸化チタンが最も好ましい。
本発明のコア−シェル型ナノ粒子は、金属ナノ粒子からなるコア層(A)と、ポリアミンセグメント(b1)を有する化合物(B)と酸化物(C)とを主成分とする複合体からなるシェル層とを有するコア−シェル型ナノ粒子である。ここで、主成分とするとは、意図的に第三成分を導入しない限りにおいて、化合物(B)と酸化物(C)以外の成分が入らないことをいうものである。このシェル層は、酸化物(C)が形成するマトリックスに化合物(B)が複合化されてなる有機無機複合体である。
本発明のコア−シェル型ナノ粒子の製造方法は、表面に一級アミノ基および/または二級アミノ基を有するポリアミンセグメント(b1)を有する化合物(B)層を有する金属ナノ粒子(A)の存在下で、酸化物ソース(C’)のゾルゲル反応により酸化物(C)を析出させる工程を有することを特徴とする。さらに、前記工程で酸化物(C)を形成させた後、有機シランのゾルゲル反応を行う工程を有すると、ポリシルセスキオキサン(D)を導入することもできる。
前記で得られたコア−シェル型ナノ粒子のシェル層に存在する化合物(B)、すなわち有機成分を除去することで、金属コア―酸化物シェルの構成を有するコア−シェル型ナノ粒子を形成することができる。化合物(B)の除去方法としては、焼成処理や溶剤洗浄の方法が挙げられるが、有機成分である化合物(B)を完全に除去できる点から、焼成炉中での焼成処理法が好ましい。
合成したコア−シェル型ナノ粒子の分散溶液をエタノールで希釈し、それを炭素蒸着された銅グリッドに乗せ、サンプルを日本電子株式会社製、JEM−2200FSにて観察を行った。
試料の約100mgをろ紙にとり、PPフィルムをかぶせて蛍光X線測定(ZSX1002P/理学電機工業株式会社)を行った。
合成したコア−シェル型ナノ粒子粉体を白金パンにてTGA(SIIナノテクノロジー株式会社製、TG/DTA6300)測定を行った
焼成は、株式会社アサヒ理化製作所製セラミック電気管状炉ARF−100K型にAMF−2P型温度コントローラ付きの焼成炉装置にて行った。
分岐状ポリエチレンイミン(SP003、株式会社日本触媒製、平均分子量300)の0.2gとテトラクロロ金(III)酸(和光製薬)の0.2gとを4mL水に溶解させた。反応を室温にて24時間行った。混合直後は薄い黄色であったが、反応と共に変化し、24時間後には綺麗なワインレッドの金ナノ粒子の分散液を得た。TEM観察により、得られた金ナノ粒子の直径が5nm−30nmであることを確認した。
共重合体は分岐状ポリエチレンイミン中のアミノ基にポリエチレングリコール鎖を結合させることで合成できる。特開2010−118168号公報の合成例1に示された方法に従って、平均分子量が10,000の分岐状ポリエチレンイミンと数平均分子量が5,000のポリエチレングリコールとの共重合体を合成した。該共重合体の中にエチレンイミン単位対エチレングリコール単位のモル比は1:3である。
合成例1で得られた金ナノ粒子の水分散液用いて、金の含有量の0.25%の水分散液を10mL作成した。この分散液にMS51(メトキシシランの4量体)の0.25mLをシリカソースとして加えた。得られた分散溶液を室温にて4時間攪拌した後、エタノールでの洗浄、再分散を経て、コア−シェル型金ナノ粒子の分散液を得た。TEM観察により、得られた粒子が金ナノ粒子の表面に4nmのシェル層を有することが確認出来た(図1)。また、TEM評価により、溶液中での金ナノ粒子表面以外のnon−templatedシリカ形成は観察されなかった。これは金ナノ粒子表面に存在するポリエチレンイミンがシリカ析出の際の足場と触媒として機能し、シリカ形成は選択的に金ナノ粒子の表面で行うことを強く示唆する。
Langmuir,2006,22(6),11022−11027に示された方法に従って、ポリジメチルアミノエチルメタクリレート(PDMA)を用いて、金ナノ粒子を合成した。実施例1に参考して、シリカ析出を行ったところ、金ナノ粒子の表面だけでの選択的なシリカシェル形成はできなかった。これは、分岐状ポリエチレンイミンと比べて、三級アミンだけを持つPDMAは金ナノ粒子の表面に安定な親水性の高いポリアミン層の形成が困難であるためと考えられる。
合成例2で得られた銀ナノ粒子の水分散液(濃度0.75%)の25mLにMS51の0.25mLをシリカソースとして加えた。得られた分散溶液を室温にて4時間攪拌した後、エタノールでの洗浄、再分散を経て、コア−シェル型銀ナノ粒子の分散液を得た。TEM観察により、得られた粒子が銀ナノ粒子の表面に9nmのシェル層を有することが確認出来た(図2)。乾燥したコア−シェル型銀ナノ粒子粉体を蛍光X線測定により評価したところ、粒子中シリカの含有量は11%であった。
合成例2で得られた銀ナノ粒子の水分散液(濃度0.75%)の25mLにMS51の0.05mLをシリカソースとして加えた。得られた分散溶液を室温にて4時間攪拌した後、エタノールでの洗浄、再分散を経て、コア−シェル型銀ナノ粒子の分散液を得た。TEM観察により、得られた粒子が銀ナノ粒子の表面に3nmのシェル層を有することが確認出来た(図3)。
合成例2で得られた銀ナノ粒子の水分散液(濃度0.75%)の25mLにMS51の0.25mLをシリカソースとして加えた。得られた分散溶液を室温にて40min攪拌した後、エタノールでの洗浄、再分散を経て、コア−シェル型銀ナノ粒子の分散液を得た。TEM観察により、得られた粒子が銀ナノ粒子の表面に5nmのシェル層を有することが確認出来た(図4)。
実施例4で合成されたコア−シェル銀ナノ粒子粉体を空気中500℃で焼成した。焼成したサンプルの分散性を評価したところ、媒体中での優れた再分散性を確認した。TEM観察により、銀ナノ粒子の表面にシリカシェル層構造が維持できていることを確認した(図5)。
合成例2で得られた銀ナノ粒子の水分散液(濃度0.75%)の25mLにMS51の0.25mLをシリカソースとして加えた。得られた分散溶液を室温にて40min攪拌した後に、トリメチルメトキシシランの0.1mLを加えた。得られた溶液を室温にて24時間攪拌して、エタノールでの洗浄、乾燥を経て、ポリシルセスキオキサンを有するコア−シェル型ナノ粒子を得た。この粒子は、水やエタノールへの優れた再分散性を有する。更に、液状エポキシ樹脂(DIC株式会社製EPICLON 850S)や、ウレタン樹脂水分散体等、他の化合物への分散性も良好であることを確認した。
Claims (13)
- 金属ナノ粒子(A)からなるコア層と、
一級アミノ基および/または二級アミノ基を有するポリアミンセグメント(b1)を有する化合物(B)と酸化物(C)とを主成分とする複合体からなるシェル層と、
を有することを特徴とするコア−シェル型ナノ粒子。 - 前記ポリアミンセグメントを有する化合物(b1)中に、更にノ二オン性有機セグメント(b2)を含有する請求項1記載のコア−シェル型ナノ粒子。
- 前記ノ二オン性有機セグメント(b2)がポリエチレングリコールからなるセグメントである請求項2記載のコア−シェル型ナノ粒子。
- 更にシェル層にポリシルセスキオキサン(D)を含有する請求項1〜3の何れか1項記載のコア−シェル型ナノ粒子。
- 前記金属ナノ粒子(A)が金又は銀のナノ粒子である請求項1〜4の何れか1項記載のコア−シェル型ナノ粒子。
- 前記ポリアミンセグメント(b1)がポリエチレンイミンからなるセグメントである請求項1〜5の何れか1項記載のコア−シェル型ナノ粒子。
- 前記酸化物(C)がシリカ又は酸化チタンである請求項1〜6の何れか1項記載のコア−シェル型ナノ粒子。
- 金属ナノ粒子(A)からなるコア層と、酸化物(C)とを主成分とするシェル層と、を有することを特徴とするコア−シェル型ナノ粒子。
- 請求項1〜7の何れか1項記載のコア−シェル型ナノ粒子から有機成分を除去したものである請求項8記載のコア−シェル型ナノ粒子。
- 表面に一級アミノ基および/または二級アミノ基を有するポリアミンセグメント(b1)を有する化合物(B)層を有する金属ナノ粒子(A)の存在下で酸化物ソース(C’)のゾルゲル反応を行うことを特徴とするコア−シェル型ナノ粒子の製造方法。
- 請求項1〜7の何れか1項記載のコア−シェル型ナノ粒子を得るものである請求項10記載の製造方法。
- 更に有機シランのゾルゲル反応を行う、請求項10記載のコア−シェル型粒子の製造方法。
- 表面に一級アミノ基および/または二級アミノ基を有するポリアミンセグメント(b1)を有する化合物(B)層を有する金属ナノ粒子(A)の存在下で酸化物ソース(C’)のゾルゲル反応を行ってから有機成分を除去することを特徴とするコア−シェル型ナノ粒子の製造方法。
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