TWI520990B - Metal nano particle composite and its manufacturing method - Google Patents
Metal nano particle composite and its manufacturing method Download PDFInfo
- Publication number
- TWI520990B TWI520990B TW101102738A TW101102738A TWI520990B TW I520990 B TWI520990 B TW I520990B TW 101102738 A TW101102738 A TW 101102738A TW 101102738 A TW101102738 A TW 101102738A TW I520990 B TWI520990 B TW I520990B
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- Prior art keywords
- group
- metal
- film
- repeating unit
- aqueous medium
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- 239000002082 metal nanoparticle Substances 0.000 title claims description 94
- 239000002131 composite material Substances 0.000 title claims description 58
- 238000004519 manufacturing process Methods 0.000 title claims description 31
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- 239000006185 dispersion Substances 0.000 claims description 102
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 93
- 229910052737 gold Inorganic materials 0.000 claims description 93
- 239000010931 gold Substances 0.000 claims description 93
- 229910052751 metal Inorganic materials 0.000 claims description 51
- -1 aliphatic ketones Chemical class 0.000 claims description 50
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- 238000000034 method Methods 0.000 claims description 28
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- 125000006253 t-butylcarbonyl group Chemical group [H]C([H])([H])C(C(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- GJWMYLFHBXEWNZ-UHFFFAOYSA-N tert-butyl (4-ethenylphenyl) carbonate Chemical compound CC(C)(C)OC(=O)OC1=CC=C(C=C)C=C1 GJWMYLFHBXEWNZ-UHFFFAOYSA-N 0.000 description 1
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010887 waste solvent Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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Description
本發明係關於一種金屬奈米粒子複合體、其製造方法、金屬奈米粒子分散液、金屬奈米粒子分散膜形成用組合物及金屬奈米粒子分散膜。
金奈米粒子等金屬奈米粒子由於具有塊狀材料不具備之固有之性質,故於著色材料、螢光材料、偏光材料、奈米結晶材料、導電性材料等多方面之領域中利用。
上述金屬奈米粒子之製造方法可大致分為乾式法與濕式法,作為乾式法可列舉蒸鍍法,但必需特殊裝置。
與此相對,藉由濕式法可以簡便之操作而獲得金屬奈米粒子,作為其代表者已知有使保護劑與金屬離子共存於液相中,並於其中添加還原劑,藉此獲得金屬奈米粒子之方法。根據該方法,金屬奈米粒子擔載於保護劑上而形成金屬奈米粒子複合體,故可防止液體中之金屬奈米粒子之凝聚。
而且近年來,就提高於上述著色材料等中利用之情形時之有用性之觀點而言,要求提高液體中之複合體之穩定性、及包含該複合體之金屬奈米粒子分散液中之金屬奈米粒子之高濃度化。又,於該分散液中調配樹脂或交聯性化合物等之情形時、或使用該分散液製成分散膜之情形時期望分散性之改善。
而且,為有助於該等要求,已知降低分散液中剩餘之保護劑或還原劑、或者離子性雜質等之技術,作為此等技術揭示有電透析(專利文獻1);使用水藉由超過濾而置換溶劑之方法(專利文獻2);向水溶性之分散液中添加分散性矮化劑後,藉由離心分離而使金屬奈米粒子沈澱,從而除去分散媒之方法(專利文獻3);將非水溶性之分散液用大量脫離子水清洗之方法(專利文獻4);向非水溶性之分散液中添加大量不良溶劑而使凝聚物沈澱後,進行傾析或離心分離之方法(專利文獻5及6)等各種分散液之純化方法。
[專利文獻1]日本專利特開平11-80647號公報
[專利文獻2]日本專利特開2007-146279號公報
[專利文獻3]日本專利特開2009-62570號公報
[專利文獻4]日本專利特開2005-81501號公報
[專利文獻5]日本專利特開2006-37145號公報
[專利文獻6]日本專利特開2009-30170號公報
[專利文獻7]國際公開第08/056431號手冊
然而,於專利文獻1及2中所記載之電透析或超過濾中,由於易產生膜之堵塞而需要頻繁更換膜,故有成本提高之問題。又,於專利文獻3所記載之離心分離方法中,於使用粒徑較小之粒子之情形時,有不易進行離心分離而必需高速離心操作,且易產生奈米粒子彼此之凝聚,又,裝置之大型化亦較為困難之問題。又,於專利文獻4~6中所記載之使用水或不良溶劑之方法中,由於排出大量廢水或廢溶劑且必需裝置之大型化,故有可能提高成本之問題。
又,於專利文獻7中記載有使金擔載於臂部含有氧化乙烯重複單元之星型聚合物而成之具有氧化觸媒功能之金奈米粒子複合體。
然而,上述金奈米粒子複合體即便長期放置於液體中亦不會產生金奈米粒子之聚集等,經時保持穩定,但上述星型聚合物之保持金奈米粒子之作用尚不充分,若使液體中之金奈米粒子高濃度化,則有金凝聚而產生沈澱之問題。又,若於分散液中調配樹脂或交聯性化合物,則金容易析出而沈澱,故難以用作膜材之原料。
因此,本發明之課題在於提供一種經時穩定性及保持穩定性優異,且用作金屬奈米粒子分散膜之原料之金屬奈米粒子複合體、其製造方法、金屬奈米粒子分散液、金屬奈米粒子分散膜形成用組合物及金屬奈米粒子分散膜。
因此,本發明者等人為解決上述課題而進行努力研究,結果發現,於臂部除含有乙烯醚系重複單元以外亦含有特定之羥基苯乙烯系重複單元之星型聚合物上擔載金屬奈米粒子而成之金屬奈米粒子複合體,不僅經時穩定性優異,保持穩定性亦優異,用作金屬奈米粒子分散膜之原料。
即,(i)本發明提供一種金屬奈米粒子複合體,其係將(B)金屬奈米粒子擔載於星型聚合物上而成,該星型聚合物具有(A)中心核及鍵結於中心核之臂部,且臂部含有下述通式(1)所表示之重複單元及下述通式(2)所表示之重複單元。
[化1]
(式中,R1表示氫原子或碳數1~4之烷基)。
[化2]
(式中,R2表示甲基或乙基,k為1~10之整數)。
又,(ii)本發明提供一種金屬奈米粒子分散液,其含有上述(i)之複合體與水性介質。
進而,(iii)本發明提供一種金屬奈米粒子複合體之製造方法,其包括下述步驟(a)及(b)。
(a)使具有中心核及鍵結於中心核之臂部,且臂部含有下述通式(1)所表示之重複單元及下述通式(2)所表示之重複單元的星型聚合物與選自金屬鹽及金屬錯鹽中之至少1種以上於水性介質中接觸,而使選自金屬鹽及金屬錯鹽中之至少1種以上吸附於星型聚合物上之步驟。
[化3]
(式中,R1與上述意思相同)。
[化4]
(式中,R2及k與上述意思相同)。
(b)使步驟(a)中吸附之選自金屬鹽及金屬錯鹽中之至少1種以上與還原劑接觸之步驟。
進而,(iv)本發明提供一種金屬奈米粒子分散膜形成用組合物,其含有上述(i)之複合體,與選自交聯性化合物及膜形成用樹脂中之至少1種。
進而,(v)本發明提供一種金屬奈米粒子分散膜,其係使用上述(iv)之膜形成用組合物而獲得。
本發明之金屬奈米粒子複合體不僅經時穩定性優異,保持穩定性亦優異,且用作金屬奈米粒子分散膜之原料。因此,根據本發明可提供一種金屬奈米粒子之分散性優異、且用作金屬奈米粒子分散膜之原料之金屬奈米粒子分散液,又,可提供一種金屬奈米粒子之分散性優異之金屬奈米粒子分散膜形成用組合物及金屬奈米粒子分散膜。
又,根據本發明之製造方法,可簡便且容易地製造上述金屬奈米粒子複合體。
本發明之金屬奈米粒子複合體之特徵在於:金屬奈米粒子擔載於上述之星型聚合物上。
首先,對本發明之金屬奈米粒子複合體之各構成成分進行詳細說明。
<星型聚合物>
上述星型聚合物具有中心核及鍵結於該中心核之臂部。又,臂部含有上述重複單元(1)及上述重複單元(2)。
上述臂部較佳為含有鍵結於中心核之至少2個以上之聚合物鏈。作為該聚合物鏈,可列舉:含有重複單元(1)之聚合物鏈、含有重複單元(2)之聚合物鏈、含有重複單元(1)與重複單元(2)之嵌段體之聚合物鏈。
又,作為臂部,較佳為包含含有重複單元(1)之聚合物鏈與含有重複單元(2)之聚合物鏈之臂部、包含含有重複單元(1)與重複單元(2)之嵌段體之聚合物鏈之臂部。
又,式(1)中,R1為氫原子或碳數1~4之烷基,較佳為碳數1~4之烷基。作為該烷基,可列舉:甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基、異丁基。再者,式(1)中之羥基之位置為任意。
又,式(2)中,R2為甲基或乙基。又,k為1~10之整數,但較佳為1~6。
又,作為上述中心核,較佳為由二乙烯化合物衍生者,更佳為由芳香族二乙烯化合物或二乙烯醚化合物衍生者。
該等之中,特佳為由含有雙(乙烯氧基甲基)、雙(乙烯氧基乙基)、或雙(乙烯基苯氧基)之化合物衍生者。
又,就複合體之分離、回收之效率之方面而言,作為上述星型聚合物,較佳為於水性介質中具有下限臨界溶液溫度者。此處,所謂下限臨界溶液溫度,意指處於溶液狀態中以特定之溫度以下均勻溶解之狀態,但於特定之溫度以上會產生相分離之溫度。作為下限臨界溫度,較佳為10℃~80℃,更佳為15℃~60℃。
水性介質中具有下限臨界溶液溫度之聚合物具有如下特徵:於低於下限臨界溶液溫度之溫度時,會溶解於水性介質中,但於高於下限臨界溶液溫度之溫度時,會產生水性介質中聚合物之急劇脫水及伴隨其之疏水性相互作用所引起之相分離,對於水性介質之溶解性顯著降低。因此,如下所述,利用該性質使水性介質中之金屬奈米粒子複合體凝聚,可提高該複合體之分離、回收之效率。
上述下限臨界溶液溫度可藉由改變構成重複單元(2)之氧化乙烯之單元數或重複單元(2)中R2之種類而進行適當調整。即,下限臨界溶液溫度通常根據重複單元(2)所含之氧化乙烯鏈而表現,故藉由調整重複單元(2)之比例或聚合度之差異可獲得溫度應答性。
又,由於重複單元(2)所含之氧化乙烯鏈具有吸附成為金屬奈米粒子及其前驅物之金屬鹽或金屬錯鹽並穩定化之作用,故藉由提高星型聚合物中重複單元(2)之含量,可提高金屬奈米粒子複合體之經時穩定性。
另一方面,藉由使星型聚合物含有重複單元(1),可使金屬奈米粒子之擔載量增加。又,藉由提高重複單元(1)之含量,則與交聯性化合物之反應點增多,從而可提高作為下述分散膜之原料之有用性。
就兼具此種重複單元(1)與重複單元(2)之作用之觀點而言,重複單元(2)之含量較佳為相對於臂部之總重複單元為15~95莫耳%。另一方面,重複單元(1)之含量較佳為5~85莫耳%。星型聚合物之各重複單元之組成比可根據於活性陽離子聚合中使用之單體之比率而任意選擇。
又,上述星型聚合物之重量平均分子量(Mw)通常為1000~1,000,000,較佳為5000~500,000。又,分子量分佈(Mw/Mn)通常為1.0~3.0,較佳為1.0~2.0。
再者,上述重量平均分子量與相對平均分子量意思相同,且可藉由凝膠滲透層析(GPC)法根據標準聚苯乙烯校準曲線而求出。
又,上述星型聚合物之分支數通常為10~80支,較佳為10~70支,更佳為10~60支。該分支數只要基於下述實施例中記載之方法進行測定即可。
繼而,對於上述星型聚合物之製造方法進行說明。
上述星型聚合物可藉由如下方式而製造:例如使下述通式(3)所表示之化合物、
[化5]
(式中,R3表示氫或可藉由酸或鹼脫離之保護基,R1與上述意思相同)
下述通式(4)所表示之化合物、
[化6]
(式中,R2及k與上述意思相同)
及可能形成中心核之二乙烯化合物於存在起始原料及路易斯酸之情形時進行活性陽離子聚合,聚合反應結束後,根據需要使保護基脫保護。再者,化合物(3)、化合物(4)及二乙烯化合物之活性陽離子聚合之順序為任意,該等化合物可分別使用1種或2種以上。
又,R3之作為可藉由酸或鹼容易地脫離之保護基,可列舉:第三丁基等3級烷基;1-甲氧基乙基、1-乙氧基乙基、1-甲氧基丙基、2-四氫吡喃基、2-四氫呋喃基等烷氧基烷基;乙醯基、丙醯基、第三丁基羰基等醯基;甲氧基羰基、乙氧基羰基、丙氧基羰基、第三丁氧基羰基等烷氧基羰基;第三丁氧基羰基甲基等烷氧基羰基烷基;三甲基矽烷基、第三丁基二甲基矽基等烷基矽烷基等。
又,作為上述化合物(3),例如可列舉:對羥基苯乙烯、間羥基苯乙烯、鄰羥基苯乙烯、對異丙烯基酚、間異丙烯基酚、鄰異丙烯基酚等羥基苯乙烯類;對第三丁氧基苯乙烯、間第三丁氧基苯乙烯等第三丁氧基苯乙烯類;對(1-乙氧基乙氧基)苯乙烯、間(1-乙氧基乙氧基)苯乙烯、對(2-四氫吡喃)羥基苯乙烯、間(2-四氫吡喃)羥基苯乙烯等烷氧基烷氧基苯乙烯類;對乙醯氧基苯乙烯、間乙醯氧基苯乙烯、對第三丁基羰氧基苯乙烯、間第三丁基羰氧基苯乙烯等烷醯氧基苯乙烯類;對甲氧基羰氧基苯乙烯、間甲氧基羰氧基苯乙烯、對第三丁氧基羰氧基苯乙烯、間第三丁氧基羰氧基苯乙烯等烷氧基羰氧基苯乙烯類;對第三丁氧基羰基甲氧基苯乙烯、間第三丁氧基羰氧基甲基苯乙烯等烷氧基羰基烷氧基苯乙烯類;對三甲基矽烷氧基苯乙烯、間三甲基矽烷氧基苯乙烯、對第三丁基二甲基矽烷氧基苯乙烯、間第三丁基二甲基矽烷氧基苯乙烯等烷基矽烷氧基苯乙烯類等。該等之中,特佳為對羥基苯乙烯、對異丙烯基酚、對第三丁氧基苯乙烯、對乙醯氧基苯乙烯。
又,作為上述化合物(4),例如可列舉:2-甲氧基乙基乙烯醚、2-乙氧基乙基乙烯醚、2-(2-甲氧基乙氧基)乙基乙烯醚、2-(2-乙氧基乙氧基)乙基乙烯醚、2-(2-(2-甲氧基乙氧基)乙氧基)乙基乙烯醚、2-(2-(2-(2-甲氧基乙氧基)乙氧基)乙氧基)乙基乙烯醚、2-(2-(2-(2-乙氧基乙氧基)乙氧基)乙氧基)乙基乙烯醚等。
作為上述二乙烯化合物,只要能形成中心核即可,可列舉:雙(4-乙烯基苯氧基)甲烷、1,2-雙(4-乙烯基苯氧基)乙烷、1,3-雙(4-乙烯基苯氧基)丙烷、4,4'-[2,2'-氧雙(乙烷-2,1-二基)雙(氧基)]雙(乙烯苯)、雙[[4-[(4-乙烯基苯氧基)甲基]環己基]甲基]對苯二甲酸酯等芳香族二乙烯化合物;乙二醇二乙烯醚、雙酚A雙(乙烯氧基乙烯)醚、雙(乙烯氧基乙烯)醚、對苯二酚雙(乙烯氧基乙烯)醚、1,4-雙(乙烯氧基甲基)環己烷等二乙烯醚化合物。
又,上述起始原料中含有:水、乙醇、質子酸等生成質子之化合物、鹵代烷等生成碳陽離子之化合物。
作為起始原料,較佳為上述乙烯醚與生成質子之化合物的加成物等供陽離子化合物。具體而言,可列舉1-異丁氧基乙基乙酸酯等1-烷氧基乙基乙酸酯等。
路易斯酸只要使用於乙烯醚系單體或羥基苯乙烯系單體之陽離子聚合時通常使用之路易斯酸即可。具體而言,可較佳使用Et1.5AlCl1.5、TiCl4、TiBr4、BCl3、BF3、BF3‧OEt2、SnCl2、SnCl4、SbCl5、SbF5、WCl6、TaCl5、VCl5、FeCl3、ZnBr2、ZnCl4、AlCl3、AlBr3等有機金屬鹵化物或金屬鹵化物。該等路易斯酸亦可單獨使用,亦可併用複數個。
又,由於化合物(3)與化合物(4)中之陽離子聚合性不同,故使化合物(4)聚合時,較佳為將Et1.5AlCl1.5等有機鹵化鋁化合物用作路易斯酸,使化合物(3)聚合時,追加使用SnCl4或FeCl3等含有Al以外原子之金屬鹵化合物,可使化合物(3)之聚合速度加快。
又,臂部中之各聚合物鏈之結構可藉由適當選擇使形成臂部之各單體及形成中心核之二乙烯化合物進行活性聚合之順序而控制。
例如,使化合物(4)進行活性陽離子聚合後,添加二乙烯化合物而形成中心核,繼續使化合物(3)進行活性陽離子聚合,藉此可獲得星型聚合物,其具有含有重複單元(1)之聚合物鏈與含有重複單元(2)之聚合物鏈自中心核分別獨立伸長之結構。
又,使化合物(4)、化合物(3)依次進行活性陽離子聚合,最後添加二乙烯化合物而形成中心核,藉此可獲得星型聚合物,其具有含有重複單元(1)與重複單元(2)之嵌段體之聚合物鏈自中心核伸長之結構,且於外殼部具有重複單元(2)。
又,使用二乙烯化合物形成中心核之後,若使化合物(4)、化合物(3)依次進行活性陽離子聚合,則可獲得星型聚合物,其具有含有重複單元(1)與重複單元(2)之嵌段體之聚合物鏈自中心核伸長之結構,且於外殼部具有重複單元(1)。
又,聚合反應中亦可使用溶劑。溶劑並無特別限定,可列舉:苯、甲苯、二甲苯等芳香族烴溶劑;丙烷、正丁烷、異丁烷、正戊烷、正己烷、正庚烷、正辛烷、異辛烷、癸烷、十六烷、異戊烷等脂肪族烴系溶劑;二氯甲烷、氯乙烯、四氯化碳等鹵化烴系溶劑;四氫呋喃(THF)、二烷、二乙醚、二丁醚、乙二醇二乙醚等醚系溶劑等。該等之中,可較佳使用甲苯、二氯甲烷、己烷。該等溶劑可單獨使用或組合2種以上使用。
作為聚合溫度通常為-80~150℃,較佳為-78~80℃。又,聚合時間通常為10~250小時左右。
目標之星型聚合物藉由以期望之聚合度添加反應終止劑而停止聚合反應而獲得。作為反應終止劑只要為起到作為末端終止劑之作用之化合物及/具有使路易斯酸失去活性之作用之化合物即可。例如可列舉:甲醇、乙醇、丙醇等醇;二甲基胺、二乙基胺等胺;水、氨水、氫氧化鈉水溶液等。
再者,使用羥基由保護基所保護之羥基苯乙烯系單體之情形時,例如於作為上述聚合溶劑而例示之溶劑中,於鹽酸、硫酸等酸觸媒下,以反應溫度50~150℃,反應時間1~30小時進行反應,可使保護基脫離而形成羥基苯乙烯系重複單元。
<金屬奈米粒子>
構成金屬奈米粒子之金屬元素並未特別限定,但較佳為貴金屬。例如可列舉:金、銀、鉑、銅、釕、銠、鈀、鋨、銥等。其中,就與重複單元(2)中之氧化乙烯部位之配位性能、及兼具複合體之經時穩定性與保持穩定性之方面而言,較佳為金、銀、銅。
金屬奈米粒子之粒徑通常為1~30 nm,較佳為3~20 nm,特佳為5~10 nm。如下述實施例所記載,粒徑可藉由利用TEM(Transmission Electron Microscopy,穿透式電子顯微鏡)之觀察等而測定。
只要金屬奈米粒子之擔載量根據金屬之種類及電漿子之共振強度而進行適當調整即可,相對於1質量份星型聚合物通常為0.001~50質量份,較佳為0.005~30質量份,更佳為0.01~20質量份。將擔載量設為50質量份以下,藉此可提高抑制金屬奈米粒子凝聚之作用。另一方面,將擔載量設為0.001質量份以上,藉此可提高生產性且提高分散液或分散膜中之金屬奈米粒子之含量。
繼而,對於本發明之金屬奈米粒子複合體之製造方法進行說明。
本發明之金屬奈米粒子之製造方法包括上述步驟(a)及(b)。
<步驟(a)>
作為步驟(a),較佳為吸附步驟:使上述星型聚合物與選自金屬鹽及金屬錯鹽中之至少1種以上於上述水性介質中加以混合,而使選自金屬離子及金屬錯離子中之至少1種以上吸附於星型聚合物上。
上述金屬鹽及/或金屬錯鹽中較佳之金屬元素與上述之金屬奈米粒子相同。作為金屬鹽及/或金屬錯鹽,例如可列舉:氯金酸、硝酸銀、氯化鉑、硝酸銅、硫酸銅、氯化亞鉑、氯化鈀、乙酸鈀、硝酸鈀、氯化銠、乙酸銠、氯化釕、乙酸釕、氯化銥、乙酸銥等。
作為水性介質,例如可列舉:水、醇類、脂肪族酮類、脂肪族多元醇類、乙二醇衍生物、吡咯烷酮類等。再者,水性介質可單獨使用或使用2種以上。
作為上述醇類,可列舉:甲醇、乙醇、正丙醇、異丙醇、丁醇、異丁醇、第二丁醇、第三丁醇等碳數1~6左右之低級醇;作為上述脂肪族酮類,可列舉:丙酮、丁酮等。
作為上述脂肪族多元醇類,可列舉:乙二醇、二乙二醇、三乙二醇、聚乙二醇、丙二醇、二丙二醇、聚丙二醇、丙三醇等。
作為上述乙二醇衍生物,可列舉:乙二醇單甲醚、乙二醇單乙醚、乙二醇單丁醚、丙二醇單甲醚、丙二醇單乙醚、丙二醇單丁醚、二乙二醇單甲醚、二乙二醇單乙醚、二乙二醇單丁醚、三乙二醇單甲醚、三乙二醇單乙醚、二丙二醇單甲醚等單醚衍生物;乙二醇二甲醚、二乙二醇二甲醚、三乙二醇二甲醚、丙二醇二甲醚、二丙二醇二甲醚、三丙二醇二甲醚等二醚衍生物;乙二醇二乙酸酯、乙二醇單甲醚乙酸酯等酯衍生物等。
作為上述吡咯烷酮類,可列舉:2-吡咯烷酮、N-甲基-2-吡咯烷酮、2-唑啶酮、1,3-二甲基-2-咪唑啶酮等。
該等之中,較佳為水、醇類、脂肪族酮類、脂肪族多元醇類、吡咯烷酮類、該等之混合物,就金屬奈米粒子複合體之穩定性方面而言,較佳為水、醇類、脂肪族酮類、水與醇類之混合物。
又,作為水性介質之使用量,相對於1 mg星型聚合物較佳為0.3~10 mL,更佳為0.4~10 mL,特佳為0.5~10 mL。
<步驟(b)>
作為步驟(b),較佳為還原步驟:將還原劑添加至上述吸附步驟中獲得之溶液中,使吸附之選自金屬離子及金屬錯離子中之至少1種以上進行奈米粒子化。
作為上述還原劑並未特別限定,例如可列舉:氫硼化鈉等鹼金屬氫硼化鹽、膦酸鹽、次氯酸鹽、硫代硫酸鹽、亞硫酸鹽、二亞硫酸鹽等無機化合物;肼化合物、乙二胺、尿素、硫脲、二甲基胺硼烷等各種胺、二胺類及亞胺類;甲醛、乙醛、丙醛等各種醛類;甲硫醇、乙硫醇、丙硫醇等各種硫醇類;對苯二酚、鞣酸、檸檬酸或其鹽、琥珀酸或其鹽、抗壞血酸或其鹽等。
該等之中,較佳為氫硼化鈉等鹼金屬氫硼化鹽、肼化合物、檸檬酸或其鹽、琥珀酸或其鹽、抗壞血酸或其鹽,就還原能力或可加工性方面而言,特佳為氫硼化鈉。
還原劑之使用量相對於金屬鹽或金屬錯鹽通常為1~100莫耳當量,較佳為1~50莫耳當量。
本發明之製造方法亦可進而包括下述步驟(c)及(d)。該情形時星型聚合物為於水性介質中具有下限臨界溶液溫度者。
(c)將步驟(b)中獲得之含有金屬奈米粒子複合體之水性介質加熱至高於星型聚合物之下限臨界溶液溫度之溫度,而將其分離成包含金屬奈米粒子複合體之凝聚相與包含水性介質之液相,從而回收凝聚相之步驟
(d)以低於星型聚合物之下限臨界溶液溫度之溫度,將步驟(c)中回收之凝聚相分散於與步驟(a)中所使用之水性介質相同或不同之水性介質中之步驟
再者,所謂上述之高於下限臨界溶液溫度之溫度,為相對於下限臨界溶液溫度+10~50℃左右,所謂上述之低於下限臨界溶液溫度之溫度,為相對於下限臨界溶液溫度-10~30℃左右。
於步驟(c)中,將其分離成凝聚相與液相而回收凝聚相之方法並未特別限制,可利用過濾、傾析法、離心分離等於該領域中已知之分離方法。又,該分離方法之條件亦未特別限制,只要根據所生成之沈澱適當設定即可。於本發明中,較佳為分離方法之中通常之使用濾紙、親水性PTFE(Poly Tetra Fluoro Ethylene,聚四氟乙烯)過濾器、玻璃纖維過濾器、玻璃預濾器等濾材之過濾。
再者,步驟(d)中所使用之水性介質可使用步驟(a)中所列舉者。
如此,藉由包括上述步驟(a)及(b),視需要之步驟(c)及(d)之製造方法,可簡便且容易地獲得本發明之金屬奈米粒子複合體。
而且,如下述實驗例所記載,由於金屬奈米粒子擔載於上述之星型聚合物上,故上述金屬奈米粒子複合體於水性介質中具有優異之經時穩定性。
又,本發明之金屬奈米粒子複合體即便於水性介質中使金屬奈米粒子高濃度化(例如於水性介質中,金屬奈米粒子之含量較佳為1~5 g/L左右,更佳為2~5 g/L左右)、或含有交聯性化合物等,金屬奈米粒子亦不會引起聚集等而保持穩定,於水性介質中具有優異之保持穩定性。又,即便使分散液中含有交聯性化合物,上述複合體亦能保持穩定,故作為金屬奈米粒子分散膜之原料而極其有用。
繼而,對於本發明之金屬奈米粒子分散液進行說明。
本發明之金屬奈米粒子分散液之特徵在於:其含有上述之金屬奈米粒子複合體與上述之水性介質。
於本發明之金屬奈米粒子分散液中,除上述之金屬奈米粒子複合體、水性介質以外,亦可含有分散劑。
作為上述分散劑,可列舉:水溶性樹脂、包含寡糖類之水溶性糖組合物、界面活性劑等。
作為上述水溶性樹脂,例如可列舉:聚乙烯醇(PVA(聚合度100~5000左右))、改性聚乙烯醇系樹脂(陽離子改性聚乙烯醇、陰離子改性聚乙烯醇、矽烷醇改性聚乙烯醇)、聚乙烯縮醛、纖維素醚系樹脂[甲基纖維素(MC)、乙基纖維素(EC)、羥乙基纖維素(HEC)、羧甲基纖維素(CMC)、羥丙基纖維素(HPC)等]、甲殼素類、殼聚糖類、澱粉等含有羥基作為親水性結構單元之樹脂;聚乙二醇(PEG)、聚環氧乙烷(PEO)、聚環氧丙烷(PPO)、聚乙烯醚(PVE)等含有親水性醚鍵之樹脂;聚丙烯醯胺(PAAM)、聚乙烯吡咯烷酮(PVP)等含有親水性胺基或胺鍵之樹脂等。又,亦可列舉含有羧基作為解離性基之聚丙烯酸鹽、順丁烯二酸樹脂、海藻酸鹽、明膠類等。
該等之中,較佳為聚乙烯醇(PVA)、改性聚乙烯醇系樹脂、聚乙二醇(PEG)、聚環氧乙烷(PEO)、聚乙烯吡咯烷酮(PVP)、纖維素醚系樹脂。該等之中,較佳為聚乙烯醇(PVA)、改性聚乙烯醇系樹脂、聚乙二醇(PEG)、聚環氧乙烷(PEO)、聚乙烯吡咯烷酮(PVP)、纖維素醚系樹脂,特佳為聚乙烯醇(PVA)、改性聚乙烯醇系樹脂。
再者,分散劑可單獨使用或併用2種以上。
於金屬奈米粒子分散液總量中分散劑之含量例如為0.1~30質量%左右,較佳為0.5%~20質量%。
以與包括上述步驟(a)及(b)、視需要之步驟(c)及(d)之製造方法相同之方式,可簡便且容易地獲得本發明之金屬奈米粒子分散液。尤其是藉由經由步驟(c)及(d),以溫度控制之簡便操作,即可將其分離成包含金屬奈米粒子複合體之凝聚相與包含離子性雜質等之液相,故可經濟且簡便地獲得雜質較少之金屬奈米粒子分散液。
再者,使用上述分散劑之情形時,可添加至藉由上述步驟(a)~(b)或上述步驟(a)~(d)獲得之混合溶液中而使用,亦可於步驟(a)中,與星型聚合物一併添加。
而且,如下述實施例所記載,本發明之金屬奈米粒子分散液之分散性優異。又,即便使金屬奈米粒子高濃度化,或使金屬奈米粒子分散液中含有下述之交聯性化合物或膜形成用樹脂,亦能維持金屬奈米粒子之高度分散,故本發明之金屬奈米粒子分散液作為金屬奈米粒子分散膜之原料而極其有用。
繼而,對於本發明之金屬奈米粒子分散膜形成用組合物進行說明。
本發明之金屬奈米粒子分散膜形成用組合物之特徵在於:其含有上述金屬奈米粒子複合體、及選自交聯性化合物及膜形成用樹脂中之至少1種。
此種膜形成用組合物可大致分為2種:
(1)樹脂組合物:含有金屬奈米粒子複合體及膜形成用樹脂之組合物(不含交聯性化合物);及
(2)硬化性組合物:含有金屬奈米粒子複合體及交聯性化合物之組合物(亦可含有膜形成用樹脂)。
又,作為上述膜形成用組合物,較佳為含有上述之水性介質者。
<膜形成用樹脂>
作為膜形成用樹脂,可列舉上述之水溶性樹脂。又,當上述水性介質為水以外者之情形時,亦可使用非水溶性樹脂。
上述水溶性樹脂之中,藉由使用PVA、改性聚乙烯醇系樹脂、PEG、PEO、PVP、纖維素醚系樹脂,可提高成膜性。尤其藉由使用PVA、改性聚乙烯醇系樹脂,並與上述交聯性化合物共同使用,藉此,藉由羥基之作用從而形成三維交聯結構,可提高膜之強度或耐溶劑性等。
作為上述非水溶性之樹脂,較佳為丙烯酸樹脂。作為該丙烯酸樹脂,可列舉:甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丙酯、甲基丙烯酸丁酯等甲基丙烯酸低級烷基酯之聚合物或以該等為主成分之共聚物;丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸丁酯等丙烯酸低級烷基酯之聚合物或以該等為主成分之共聚物。該等之中,較佳為以聚甲基丙烯酸甲酯(PMMA)、甲基丙烯酸甲酯為主成分之共聚物(兩者均為Mw=104~106左右)。
再者,膜形成用樹脂可單獨使用或併用2種以上。
上述膜形成用樹脂之含量只要根據金屬含量適當選擇即可,於膜形成用組合物中通常為0.1~30質量%,較佳為0.5%~20質量%。使該含量為0.1質量%以上,藉此可簡便地獲得下述之金屬奈米粒子分散膜,而使其為30質量%以下,藉此可提高分散性。
<交聯性化合物>
作為交聯性化合物,較佳為藉由熱或酸與星型聚合物之酚性羥基產生脫水縮合反應、加成反應、陽離子聚合反應等而帶來交聯或高分子化等,從而可形成交聯膜者。作為此種交聯性化合物,例如可列舉:異氰酸酯類、胺基樹脂、酚醛樹脂、胺類、環氧化合物、氧雜環丁烷化合物、三聚氰胺衍生物、尿素衍生物等。又,亦可獲得矽烷之利用水解縮合反應之交聯體。
又,作為交聯性化合物,亦可併用具有至少一個自由基聚合性不飽和鍵之乙烯基化合物。該情形時,較佳為使用公知之光自由基聚合起始劑。作為具有自由基聚合性不飽和鍵之乙烯基化合物,例如可列舉含有丙烯醯基、甲基丙烯醯基、烯丙基等中之至少1個之乙烯基化合物。
於膜形成用組合物中,交聯性化合物之含量例如為0.1~40質量%,較佳為1~20質量%。
再者,上述膜形成用組合物可依據上述之金屬奈米粒子分散液之製造方法而製造。
而且,如下述實施例所記載,本發明之金屬奈米粒子分散膜形成用組合物即便使金屬奈米粒子高濃度化、或含有交聯性化合物或膜形成用樹脂,亦能維持金屬奈米粒子之高度分散,故作為金屬奈米粒子分散膜之原料極其有用。
繼而,對於本發明之金屬奈米粒子分散膜進行說明。
本發明之金屬奈米粒子分散膜係使用上述膜形成用組合物而獲得者,具體而言,使上述膜形成用組合物塗佈於基材上或成形為膜狀並進行固化,藉此而獲得者。
只要膜形成用組合物之塗佈依據常用方法進行即可,例如可藉由溶液鑄膜法、棒塗法、旋塗法、刮塗法、輥塗法、刮刀塗佈法、模塗法、凹版印刷塗佈法、浸塗法、噴墨塗佈法、分配塗佈法、噴塗法等而進行。
塗膜之固化主要可藉由加熱而進行。例如使用硬化性組合物之情形時,於硬化性組合物中所含交聯性化合物之交聯條件下加熱並使其硬化,藉此可獲得金屬奈米粒子分散膜。於該情形時,亦可對塗膜進行預乾燥除去水性介質後再進行熱硬化。
另一方面,使用不含交聯性化合物之上述樹脂組合物之情形時,藉由加熱、乾燥而除去水性介質,藉此可獲得金屬奈米粒子分散膜。
如下述實施例所記載,本發明之金屬奈米粒子分散膜即便使金屬奈米粒子高濃度化、或含有交聯性化合物或膜形成用樹脂,亦能維持金屬奈米粒子之高度分散。因此,本發明之金屬奈米粒子分散膜能應用於有機色素型太陽電池或感測器之電子設備或光學器件。
以下列舉實施例對本發明進行詳細說明,但本發明並不限定於下述實施例。
實施例中各特性之分析條件如下所述。
<聚合物之重量平均分子量(包括下述之相對分子量)及分子量分佈之測定>
上述之重量平均分子量(Mw)及分子量分佈(Mw/Mn)係使用搭載於GPC裝置[HLC-8320GPC(東梭製造)]上之RI檢測器,藉由凝膠滲透層析法(以下,亦稱為GPC)法,根據與標準聚苯乙烯校準曲線之比較而測定[管柱:LF804(Shodex公司製造)×3根,溶離液:四氫呋喃]。
<星型聚合物之絕對分子量之測定>
絕對分子量(Mw)係藉由GPC-黏度法測定[光散射測定裝置:DLS-6000AL(大塚電子製造),管柱:Shodex公司製造之KF-800D+KF-805L×2根,溶離液:四氫呋喃]。
<星型聚合物之分支數之算出>
分支數(f)係依據下式算出。
f=(形成臂部之單體之重量組分)×(絕對分子量)/(相對分子量)
<吸收光譜之測定>
吸收光譜係使用紫外可見分光光度計(V-570分光光譜儀:日本分光公司製造)測定。
<藉由穿透式電子顯微鏡(TEM)觀察>
金屬奈米粒子之TEM像係使用TEM(JEM-2010F型:日本電子製造),以加速電壓200 kV,將金屬奈米粒子分散液載於附有碳支持膜之Cu網上而觀察。
合成例1 星型聚合物A[TEGVE-核(CHDVE)-PIPP系星型聚合物]之合成
準備安裝有三通活栓之玻璃容器,將容器內氣體置換成氬氣,藉由加熱除去容器內之吸附水。繼而,向容器內添加0.18 M(15.2 g)2-(2-(2-(2-甲氧基乙氧基)乙氧基)乙氧基)乙基乙烯醚(以下亦稱為「TEGVE」)、4.3 M乙酸乙酯、17 mM之1-異丁氧基乙基乙酸酯(以下亦稱為「IBEA」)、及222 mL甲苯,使反應系統內部冷卻,當溫度達到-10℃時添加Et1.5AlCl1.5之甲苯溶液(使Et1.5AlCl1.5為13 mM)並開始聚合。
於TEGVE之轉化結束之時間點採取少量反應溶液,於其中添加含甲醇鈉之甲醇而停止反應。測定所獲得之TEGVE聚合物之重量平均分子量及分子量分佈,結果該聚合物為Mw=3000、Mw/Mn=1.12之單分散聚合物。
繼而,向上述之反應系統內添加33 mM(2.9 g)環己烷二甲醇二乙烯醚(以下亦稱為「CHDVE」),將反應系統內之溫度維持在-10℃而持續進行反應。
分時使用GPC監控CHDVE之乙烯基之轉化,於GPC之波形成為固定之時間點採取少量反應溶液,於其中添加含甲醇鈉之甲醇而停止反應。測定所獲得之TEGVE-核(CHDVE)系星型聚合物之重量平均分子量及分子量分佈,結果該聚合物為Mw=15000、Mw/Mn=1.25之單分散聚合物。又,根據該聚合物之圖表確認源自TEGVE之峰值已完全消失。
繼而,向上述之反應系統中添加對異丙烯基酚(以下亦稱為「PIPP」)之乙酸乙酯溶液(使PIPP為33 mM(2.0 g)),進而添加SnCl4之甲苯溶液(使SnCl4為53.5 mM)並持續反應5小時。其後,向反應系統中添加含甲醇鈉之甲醇(使甲醇鈉為5 M)而停止反應,從而獲得目標之星型聚合物A。
測定所獲得之星型聚合物A之重量平均分子量及分子量分佈,結果星型聚合物A係Mw=15400、Mw/Mn=1.36之單分散聚合物。
繼而,向上述之已停止反應之溶液中,添加5質量%離子交換樹脂[商品名:Amberlyst MSPS2-1‧DRY,Organo(股)製造],並於室溫下攪拌1小時。繼而,使該溶液通過矽藻土及孔徑1 μm之過濾器,以蒸發器進行減壓濃縮,從而純化星型聚合物A。
測定純化後之星型聚合物A之相對分子量、分子量分佈及絕對分子量,結果相對分子量(Mw)為14000、Mw/Mn為1.43、絕對分子量(Mw)為26700。又,根據相對分子量及絕對分子量算出之分支數(f)為12支。
合成例2 星型聚合物B[PIPP-TEGVE-核(CHDVE)系星
型聚合物]之合成
準備安裝有三通活栓之玻璃容器,將容器內氣體置換為氬氣,藉由加熱除去容器內之吸附水。繼而,向容器內添加26.9 mM(2.5 g)CHDVE、4.3 M乙酸乙酯、13.5 mM之IBEA、及185 mL甲苯,使反應系統內部冷卻,當溫度達到-10℃時添加Et1.5AlCl1.5之甲苯溶液(使Et1.5AlCl1.5為10.8 mM)並開始聚合。
分時使用GPC監控CHDVE之乙烯基之轉化,於GPC之波形成為固定之時間點採取少量反應溶液,於其中添加含甲醇鈉之甲醇而停止反應。測定所獲得之核(CHDVE)聚合物之重量平均分子量及分子量分佈,結果該聚合物為Mw=16900、Mw/Mn=1.77之單分散聚合物。
繼而,向上述之反應系統內添加0.17 M(15.2 g)TEGVE,將反應系統內之溫度維持在-10℃而持續進行反應。
於TEGVE之轉化結束之時間點採取少量反應溶液,於其中添加含甲醇鈉之甲醇而停止反應。測定所獲得之TEGVE-核(CHDVE)系星型聚合物之重量平均分子量及分子量分佈,結果該聚合物為Mw=45500、Mw/Mn=1.70之單分散聚合物。又,根據該聚合物之圖表確認源自CHDVE之峰值已完全消失。
繼而,向上述之反應系統內添加PIPP之乙酸乙酯溶液(使PIPP為27 mM(1.7 g)),進而添加150 mL之THF及FeCl3之乙酸乙酯溶液(使FeCl3為15.5 mM)並持續反應5小時。其後,向反應系統中添加含甲醇鈉之甲醇(使甲醇鈉為5 M)而停止反應,從而獲得目標之星型聚合物B。
測定所獲得之星型聚合物B之重量平均分子量及分子量分佈,結果星型聚合物B為Mw=49700、Mw/Mn=1.79之單分散聚合物。
繼而,向上述之已停止反應之溶液中,添加10質量%離子交換樹脂[商品名:Amberlyst MSPS2-1‧DRY,Organo(股)製造],並於室溫下攪拌1小時。繼而,使該溶液通過矽藻土及孔徑1 μm之過濾器,以蒸發器進行減壓濃縮,從而純化星型聚合物B。
測定純化後之星型聚合物B之相對分子量及分子量分佈,結果相對分子量(Mw)為45100、Mw/Mn為1.78。
合成例3 星型聚合物C[TEGVE-核(CHDVE)系星型聚合物]之合成
準備安裝有三通活栓之玻璃容器,將容器內氣體置換為氬氣,藉由加熱除去容器內之吸附水。繼而,向容器內添加0.18 M(15.2 g)TEGVE、4.3 M乙酸乙酯、17 mM之IBEA、222 mL甲苯,使反應系統內部冷卻,當溫度達到-10℃時添加Et1.5AlCl1.5之甲苯溶液(使Et1.5AlCl1.5為13 mM)並開始聚合。
於TEGVE之轉化結束之時間點採取少量反應溶液,於其中添加含甲醇鈉之甲醇而停止反應。測定所獲得之TEGVE聚合物之重量平均分子量及分子量分佈,結果該聚合物為Mw=3500、Mw/Mn=1.26之單分散聚合物。
繼而,向上述之反應系統內添加33 mM(2.9 g)CHDVE,將反應系統內之溫度維持在-10℃而持續進行反應。
分時使用GPC監控CHDVE之乙烯基之轉化,於GPC之波形成為固定之時間點,向反應系統內添加含甲醇鈉之甲醇(使甲醇鈉為5 M)而停止反應,獲得目標之星型聚合物C。
測定所獲得之星型聚合物C之重量平均分子量及分子量分佈,結果星型聚合物C為Mw=14400、Mw/Mn=1.27之單分散聚合物。
繼而,向上述之已停止反應之溶液中,添加5質量%離子交換樹脂[商品名:Amberlyst MSPS2-1‧DRY,Organo(股)製造],並於室溫下攪拌1小時。繼而,使該溶液通過矽藻土及孔徑1 μm之過濾器,以蒸發器進行減壓濃縮,從而純化星型聚合物C。
測定純化後之星型聚合物C之相對分子量及分子量分佈,結果相對分子量(Mw)為14400、Mw/Mn為1.29。
實施例1 金奈米粒子分散液之製造(1)
向100 mL玻璃製造之圓底燒瓶中添加27 mg合成例1中獲得之星型聚合物A、1.8 mL金屬含量1 mol/L之氯金酸水溶液(使金為354 mg)、及90 mL離子交換水,並攪拌。繼而,以維持攪拌之狀態添加相對於氯金酸為10莫耳當量之NaBH4,於室溫下進行1小時還原反應,獲得含有金奈米粒子複合體之金奈米粒子分散液。
上述分散液呈現紅色,且測定該分散液之吸收光譜時於540 nm附近觀察到源自金奈米粒子之電漿子之吸收,斷定生成金奈米粒子。
又,使用TEM觀察上述分散液時可確認所生成之金奈米粒子之粒徑約為8 nm,及粒子間之粒徑之不均勻非常少。結果示於圖1。
由該結果可知,即便使水性介質中之金奈米粒子高濃度化,使用星型聚合物A之金奈米粒子複合體亦保持金奈米粒子,保持穩定性優異。又,可知包含該複合體之分散液之分散性優異。
又,即便將上述分散液放置6個月以上後測定吸收光譜,吸收光譜上亦未觀察到變化。
由該結果可明確,金奈米粒子即便長時間放置後亦以高度分散之狀態擔載於星型聚合物A上,不引起凝聚或大小、形狀、形態之變化,以非常穩定之狀態而存在。
實施例2 銀奈米粒子分散液之製造(1)
向100 mL玻璃製造之圓底燒瓶中添加23 mg合成例1中獲得之星型聚合物A、7.85 μL金屬含量1 mol/L之硝酸銀水溶液(使銀為0.85 mg)、及74 mL離子交換水,並攪拌。繼而,以維持攪拌之狀態添加相對於硝酸銀為10莫耳當量之NaBH4,於室溫下進行1小時還原反應,獲得含有銀奈米粒子複合體之銀奈米粒子分散液。
上述分散液呈現黃色,且測定該分散液之吸收光譜時於395 nm附近觀察到源自銀奈米粒子之電漿子之吸收。
實施例3 金奈米粒子分散液之製造(2)
向100 mL玻璃製造之圓底燒瓶中添加27 mg合成例2中獲得之星型聚合物B、1.8 mL金屬含量1 mol/L之氯金酸水溶液(使金為354 mg)、及90 mL離子交換水,並攪拌。繼而,以維持攪拌之狀態添加相對於氯金酸為10莫耳當量之NaBH4,於室溫下進行1小時還原反應,獲得含有金奈米粒子複合體之金奈米粒子分散液。
上述分散液呈現紅色,且測定該分散液之吸收光譜時於535 nm附近觀察到源自金奈米粒子之電漿子之吸收,斷定生成金奈米粒子。
比較例1 金奈米粒子分散液之製造(3)
除使用合成例3中獲得之星型聚合物C代替星型聚合物A以外,藉由與實施例1相同之操作,製造金奈米粒子分散液。
所獲得之溶液為無色且觀察到沈澱物。又,測定該溶液之吸收光譜時於530 nm附近未觀察到電漿子之吸收,未獲得金奈米粒子分散液。
比較例2 金奈米粒子分散液之製造(4)
向100 mL玻璃製造之圓底燒瓶中添加2.7 mg合成例3中獲得之星型聚合物C、0.18 mL金屬含量1 mol/L之氯金酸水溶液(使金為35.4 mg)、及90 mL離子交換水,並攪拌。繼而,以維持攪拌之狀態添加相對於氯金酸為10莫耳當量之NaBH4,於室溫下進行1小時還原反應,獲得金奈米粒子水溶液。
所獲得之水溶液呈現紅色,且測定該水溶液之吸收光譜時於540 nm附近觀察到源自金奈米粒子之電漿子之吸收,斷定生成金奈米粒子。
實施例4 金奈米粒子分散液之製造(5)(乙醇溶液)
將50 mL實施例1中獲得之金奈米粒子分散液以較星型聚合物之下限臨界溶液溫度高10℃之溫度(60℃)加熱3小時,將其分離成凝聚相與水相之2相之溶液。此時,金奈米粒子以擔載於星型聚合物之狀態下析出至凝聚相。
繼而,將凝聚相以濾紙(0.1 μm)進行過濾而回收金奈米粒子複合體。將所回收之金奈米粒子複合體於40℃下溶解於50 mL乙醇中,獲得含有金奈米粒子複合體之金奈米粒子分散液。
所獲得之分散液溶解於乙醇中且呈現紅色。又,測定該分散液之吸收光譜時於540 nm附近觀察到源自金奈米粒子之電漿子之吸收,斷定生成金奈米粒子。
又,使用TEM觀察上述分散液,所生成之金奈米粒子具有與實施例1之金奈米粒子大致相同之粒徑(大約8 nm)及形狀。結果示於圖2。
根據該結果可確認,於金奈米粒子複合體之凝聚及再溶解操作時,不會引起金奈米粒子之凝聚或大小、形狀、形態之變化等。
實施例5 金奈米粒子分散液之製造(6)(丙酮溶液)
將50 mL實施例1中獲得之金奈米粒子分散液以較星型聚合物之下限臨界溶液溫度高20℃之溫度(70℃)加熱1小時,將其分離成凝聚相與水相之2相之溶液。此時,金奈米粒子以擔載於星型聚合物之狀態下析出至凝聚相。
繼而,將凝聚相以濾紙(0.1 μm)進行過濾而回收金奈米粒子複合體。將所回收之金奈米粒子複合體於40℃下溶解於7.9 mL丙酮中,獲得含有金奈米粒子複合體之金奈米粒子分散液。
所獲得之分散液溶解於丙酮中,且呈現紅色。又,測定該分散液之吸收光譜時於540 nm附近觀察到源自金奈米粒子之電漿子之吸收,斷定生成金奈米粒子。
實施例6 金奈米粒子分散液之製造(7)(添加PVA)
向實施例1中獲得之9 g金奈米粒子分散液中添加聚乙烯醇(WAKO製造,聚合度500,皂化度98)(以下亦稱為「PVA」)1 g,自室溫升溫直至95℃後,於95℃下放置2小時而使PVA完全溶解,獲得添加有PVA之金奈米粒子分散液。
所獲得之分散液呈現紅色,且金奈米粒子保持穩定而未引起聚集。
實施例7 金奈米粒子分散膜形成用組合物之製造(1)
<親水性溶膠凝膠液之調製>
將10 g四甲基矽烷(信越化學工業公司製造之LS 470)、15.04 g甲醇、9.4 g離子交換水及1.5 g之0.2 mol/L之鹽酸進行混合,於室溫下攪拌30分鐘,獲得親水性溶膠凝膠液。
<金奈米粒子分散膜形成用組合物之製造>
將1 g上述親水性溶膠凝膠液及5 g實施例6中獲得之金奈米粒子分散液加以混合,於室溫下攪拌24小時,藉此獲得金奈米粒子分散膜形成用組合物。
所獲得之膜形成用組合物呈現紅色,雖然其含有作為交聯性化合物之四甲基矽烷與高濃度之金奈米粒子,但金奈米粒子保持穩定而不引起聚集等。
實施例8 金奈米粒子分散膜形成用組合物之製造(2)
將5 g實施例5中獲得之金奈米粒子分散液與5 g之10質量%聚甲基丙烯酸甲酯(Aldrich製造,Mw=120000)丙酮溶液加以混合,獲得金奈米粒子分散膜形成用組合物。
所獲得之膜形成用組合物呈現紅色,雖然其含有聚甲基丙烯酸甲酯,但金奈米粒子保持穩定而不引起聚集等。
比較例3 金奈米粒子分散膜形成用組合物之製造(3)
除使用比較例2中獲得之金奈米粒子水溶液代替實施例1中獲得之金奈米粒子分散液以外,進行與實施例6及7相同之操作而製備金奈米粒子分散膜形成用組合物。
所獲得之膜形成用組合物為無色,可確認於反應容器之壁面有金奈米粒子之凝聚物,且金奈米粒子並未充分分散。
實施例9 金奈米粒子分散膜之製造(1)
將實施例7中獲得之膜形成用組合物注入至鋁製造之容器中,於95℃下加熱處理1小時,藉此製作硬化膜。
所獲得之硬化膜呈現紅色。又,上述硬化膜中之金奈米粒子保持高度分散且非常穩定之狀態。由該結果可知硬化時並未引起凝聚等。
比較例4 金奈米粒子分散膜之製造(2)
除使用比較例3中獲得之膜形成用組合物代替實施例7中獲得之膜形成用組合物以外,進行與實施例9相同之操作而製作硬化膜。所獲得之硬化膜為無色透明,未獲得金奈米粒子分散膜。
實施例10 金奈米粒子分散膜之製造(3)
將實施例6中獲得之分散液注入至鋁製造之容器中,於100℃下加熱處理1小時,製作金奈米粒子分散膜。
所獲得之分散膜呈現紅色。又,該分散膜儘管含有高濃度之金奈米粒子,但金奈米粒子保持高分散且非常穩定之狀態。
實施例11 金奈米粒子分散膜之製造(4)
將實施例8中獲得之膜形成用組合物注入至玻璃製造之培養皿中,於90℃下加熱處理1小時,製作金奈米粒子分散膜。
所獲得之分散膜呈現紅色。又,該分散膜儘管含有高濃度之金奈米粒子,但金奈米粒子保持高分散且非常穩定之狀態。
圖1係表示實施例1之金奈米粒子之TEM像之顯微鏡照片。
圖2係表示實施例4之金奈米粒子之TEM像之顯微鏡照片。
Claims (16)
- 一種金屬奈米粒子複合體,其係將(B)金屬奈米粒子擔載於(A)星型聚合物上而成,該星型聚合物具有中心核及鍵結於中心核之臂部,且臂部含有下述通式(1)所表示之重複單元及下述通式(2)所表示之重複單元,[化1]
- 如請求項1之複合體,其中金屬奈米粒子含有選自金、銀及銅中之1種以上之金屬元素。
- 如請求項1之複合體,其中臂部包含含有通式(1)所表示之重複單元之聚合物鏈、及含有通式(2)所表示之重複單元之聚合物鏈。
- 如請求項1之複合體,其中臂部包含聚合物鏈,該聚合物鏈含有通式(1)所表示之重複單元與通式(2)所表示之重複單元之嵌段體。
- 如請求項1之複合體,其中星型聚合物為於水性介質中具有下限臨界溶液溫度者。
- 一種金屬奈米粒子分散液,其含有如請求項1至5中任一項之複合體與水性介質。
- 如請求項6之分散液,其中水性介質為選自水、醇類、脂肪族酮類、脂肪族多元醇類、乙二醇衍生物及吡咯烷酮類中之1種以上。
- 如請求項6之分散液,其進而含有選自聚乙烯醇、改性聚乙烯醇系樹脂、聚乙二醇、聚環氧乙烷、聚乙烯吡咯烷酮及纖維素醚系樹脂中之1種以上之水溶性樹脂。
- 一種金屬奈米粒子複合體之製造方法,其包括下述步驟(a)及(b):(a)使具有中心核及鍵結於中心核之臂部,且臂部含有下述通式(1)所表示之重複單元及下述通式(2)所表示之重複單元的星型聚合物與選自金屬鹽及金屬錯鹽中之至少1種以上於水性介質中接觸,而使選自金屬鹽及金屬錯鹽中之至少1種以上吸附於星型聚合物上之步驟:[化3]
- 如請求項9之製造方法,其中選自金屬鹽及金屬錯鹽中之至少1種以上含有選自金、銀及銅中之1種以上之金屬元素。
- 如請求項9或10之製造方法,其中還原劑係選自鹼金屬氫硼化鹽、肼化合物、檸檬酸或其鹽、琥珀酸或其鹽、及抗壞血酸或其鹽中之1種以上。
- 如請求項9或10之製造方法,其進而包括下述步驟(c)~(d),且星型聚合物為於水性介質中具有下限臨界溶液溫度者:(c)將步驟(b)中獲得之含有金屬奈米粒子複合體之水性介質加熱至高於星型聚合物之下限臨界溶液溫度之溫度,而將其分離成包含金屬奈米粒子複合體之凝聚相與包含水性介質之液相,從而回收凝聚相之步驟;(d)以低於星型聚合物之下限臨界溶液溫度之溫度,將步驟(c)中回收之凝聚相分散於與步驟(a)中所使用之水性介質相同或不同之水性介質中。
- 如請求項9或10之製造方法,其中水性介質係選自水、醇類、脂肪族酮類、脂肪族多元醇類、乙二醇衍生物及吡咯烷酮類中之1種以上。
- 一種金屬奈米粒子分散膜形成用組合物,其含有如請求項1至5中任一項之複合體、與選自交聯性化合物及膜形成用樹脂中之至少1種。
- 如請求項14之膜形成用組合物,其中膜形成用樹脂係選自水溶性樹脂及丙烯酸樹脂中之至少1種。
- 一種金屬奈米粒子分散膜,其係使用如請求項14之膜形成用組合物而獲得。
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JP6484556B2 (ja) * | 2013-09-03 | 2019-03-13 | 丸善石油化学株式会社 | ビニルエーテル系星型ポリマー |
WO2016013426A1 (ja) * | 2014-07-22 | 2016-01-28 | 住友電気工業株式会社 | 金属微粒子分散液及び金属被膜 |
WO2016125581A1 (ja) * | 2015-02-06 | 2016-08-11 | 国立大学法人北海道大学 | 複合微粒子及び分散液並びにそれらの製造方法及び用途 |
CN104858416B (zh) * | 2015-05-04 | 2017-04-19 | 济南大学 | 立体五角星金纳米粒子及其制备方法 |
CN108883395B (zh) * | 2016-01-11 | 2021-07-09 | 北京光合新能科技有限公司 | 用于产生长链烃分子的等离激元纳米颗粒催化剂和方法 |
WO2017210060A2 (en) * | 2016-05-25 | 2017-12-07 | University Of Florida Research Foundation, Inc. | Light-driven synthesis of plasmonic nanoparticles and nanomaterials |
US20210002468A1 (en) * | 2018-03-07 | 2021-01-07 | Maruzen Petrochemical Co., Ltd. | Core/shell type polymer microparticles, dispersion of particles, and method for producing said microparticles |
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