TWI498453B - 鍍覆觸媒及方法 - Google Patents

鍍覆觸媒及方法 Download PDF

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TWI498453B
TWI498453B TW102100010A TW102100010A TWI498453B TW I498453 B TWI498453 B TW I498453B TW 102100010 A TW102100010 A TW 102100010A TW 102100010 A TW102100010 A TW 102100010A TW I498453 B TWI498453 B TW I498453B
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solution
polymer
noble metal
acid
metal
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TW201335423A (zh
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周溫家
鄺蘇寬
丹尼斯 杰耀 陳
丹尼斯 國偉 葉
周慧娟
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羅門哈斯電子材料有限公司
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Description

鍍覆觸媒及方法
本發明係關於一種包括貴金屬奈米粒子之觸媒溶液。更詳而言之，本發明係關於一種包括藉由特定化合物安定化之貴金屬奈米粒子的觸媒溶液，其係有用於對在電子裝置之製造中使用的非導電基板進行無電金屬鍍覆以及裝飾性塗覆。
無電金屬沉積或鍍覆係有用於在無電源之存在下，將金屬或金屬混合物沉積於非導電表面或介電表面上。於非導電基板或介電基板上鍍覆係涉及寬範圍之應用，包括裝飾性鍍覆及電子裝置製造。一種主要應用係印刷電路板之製造。將金屬無電沉積於基板上往往需要對該基板表面預處理或敏化，以使該表面對該沉積製程具有催化性。業經發展多種方法以催化該基板。
US 3,011,920揭露用以藉由將基板浸潤於膠體觸媒溶液中而催化該基板的方法，該觸媒溶液係藉由鈀離子與亞錫離子形成鈀-錫膠體而製備。該方法需要在催化該基板表面之後進行一加速步驟，從而曝露該觸媒核心。US 3,904,792揭露了改良膠體鈀-錫觸媒以提供較不酸性之 環境中的觸媒。部份鹽酸以該酸之可溶性鹽替換。此等鈀-錫觸媒系統係存在大量局限性。該觸媒膠體之外殼(SnCl4 )2- 很容易被氧化，因此，該等觸媒粒子成長為大尺寸並急劇地失去其催化性表面積。
US 4,725,314揭露於水溶液中製備催化性吸附質的製程，其係使用有機懸浮劑以保護該膠體具有最大維度不超過500埃。聚乙烯基吡咯烷酮可用作有機懸浮劑。
因為鈀之高成本，頗為可觀之嘗試業經聚焦於發展非貴重金屬觸媒系統之上。US 3,993,799揭露了使用非貴重金屬水合氧化物膠體來處理非導電基板，之後還原該基板上之該水合氧化物塗層，以達成對於後續之無電鍍覆的至少某種程度的活化。US 6,645,557揭露了一種形成導電金屬層的方法，其係藉由將非導電表面與含有亞錫鹽之水溶液接觸以形成敏化表面，之後將該敏化表面與含有銀鹽且具有自約5至約10之範圍內之pH的水溶液接觸以形成經催化之表面。
JP 10229280A揭露了一種觸媒溶液，其係由硝酸銀或硫酸銅，以及陰離子界面活性劑如聚氧乙烯十二烷基醚硫酸鈉及還原劑如硼氫化鈉所構成。JP 11241170A揭露了一種非鈀觸媒，其係包括鐵鹽、鎳鹽、鈷鹽及銀鹽之至少一者，與陰離子界面活性劑與還原劑協同使用。
JP 200144242A揭露了一種用於製備具有高導電性之高分散膠體金屬溶液的製造方法，該膠體金屬係含有至少一個胺基及一個羧基。US 7,166,152揭露了一種 銀膠體系預處理溶液，其係包含三種成份：(i)銀膠體粒子；(ii)選自具有可於該溶液中將銀離子還原為銀金屬之電勢之金屬離子的一種或多種離子；以及，(iii)選自羥基羧酸根離子、縮合磷酸根離子及胺羧酸根離子之一種或多種離子。通常，不含錫之膠體銀的水溶液比彼等包括亞錫離子之系統安定得多，亞錫離子於空氣攪動下容易氧化為錫(IV)。與鈀系統相比，膠體銀觸媒系統將降低成本且不安定性較低。此等膠體銀觸媒系統亦於無電鍍覆製程中顯示有發展前途之催化特性而不必犧牲互連可靠性。因此，所欲者係同時保持浴安定性、吸附能力及催化活性之平衡的膠體觸媒系統。
一種溶液，係包括貴金屬奈米粒子及聚合物，該聚合物係於該聚合物之重複單元中具有羧基及氮原子。
一種用於將金屬無電鍍覆於非導電表面之製程，係包括將待鍍覆之基板浸漬於包括貴金屬奈米粒子及聚合物的溶液中，該聚合物係於該聚合物之重複單元內具有羧基及氮原子；以及在不使用加速步驟下，施行該基板之無電鍍覆。
本發明之發明人現在業經發現，包括藉由具有羧基及氮原子之特定類型之聚合物安定化之貴金屬奈米粒子且不含錫的貴金屬膠體觸媒系統，於無電鍍覆中，係顯示良好之安定性及有發展前途之催化活性。
如本說明書通篇所使用者，除非其內容係明確另行指出者，下列縮寫係具有下述意義：g=公克；mg=毫克；ml=毫升；L=公升；m=公尺；cm=公分；min.=分鐘；s=秒；h=小時；ppm=每百萬份之份數；M=莫耳濃度；g/L=公克/公升；mmol=毫莫耳；Mw=分子量；rpm=每分鐘轉數；以及，DI=去離子。
如本說明書通篇所使用者，詞語「沉積」與「鍍覆」可互換地使用。本說明書通篇中，詞語「催化」與「活化」可互換地使用。本說明書通篇中，詞語「包含貴金屬奈米粒子之溶液」與「觸媒溶液」可互換地使用。
本發明係提供用於無電鍍覆之溶液，其係包含貴金屬奈米粒子以及具有羧基及氮原子之聚合物。
於本發明中使用之聚合物係需要羧基與氮原子兩者。較佳地，該聚合物係於其重複單元內具有羧基與氮原子兩者。如後文所示，與具有具氮原子但無羧基之聚合物如聚丙烯醯胺及聚乙烯基吡咯烷酮的溶液相比，包括具有羧基與氮原子兩者之聚合物的溶液係獲得使用安定之觸媒溶液的更佳結果。儘管不欲受縛於理論，咸信，羧基對於奈米粒子之靜電性安定化更為重要，而氮原子係有用於奈米粒子吸附。
於本發明中使用之聚合物係需要聚合物。 如後文所示，本發明之發明人施行了比較例，係使用含有L-天冬胺酸鹽替代該聚合物之溶液。L-天冬胺酸鹽係具有羧基與氮原子之低分子量的化合物。使用L-天冬胺酸鹽製備之奈米粒子並不像使用該聚合物製備者一樣安定，且前者將僅於鹼性pH介質中得以安定化。此外，與含有具有羧基及氮原子之聚合物的溶液的背光測試結果相比，對於含有L-天冬胺酸鹽製備之溶液的背光測試結果差。
用於該組成物之聚合物的分子量(Mw)係400至1,000,000，更佳係1000至10,000。
可用於本發明之聚合物較佳係聚胺基酸及其共聚物。聚胺基酸及其共聚物之實例係包括聚天冬胺酸、聚麩胺酸、聚藍藻素(polycyanophycin)、L-天冬胺酸與L-丙胺酸之共聚物、L-天冬胺酸與甘胺酸之共聚物、L-麩胺酸與甘胺酸之共聚物、苯丙胺酸與甘胺酸之共聚物。
其他較佳之聚合物係包括具有醯胺結構之單體與具有羧基之單體的共聚物。具有醯胺結構之單體的實例係丙烯醯胺、甲基丙烯醯胺、乙烯基吡咯烷酮、N-(羥甲基)甲基丙烯醯胺)以及2-丙烯醯胺基-2-甲基丙磺酸。具有羧基之單體的實例係丙烯酸、甲基丙烯酸、馬來酸及檸康酸(citracomic acid)。
該聚合物之量，以觸媒溶液之總量為基準計，較佳係0.05至20 g/L，更佳係0.5至5.0 g/L。
本發明之溶液的貴金屬奈米粒子係藉由具 有觸媒活性之任何貴金屬提供。貴金屬之實例係銀、金、鉑、鈀、銠、釕、銥及鋨。較佳係該貴金屬為銀。
可使用貴金屬之混合物，如銀與鈀之混合物。貴金屬奈米粒子之量係，以該溶液之重量為基準計，10至20000 ppm，較佳100至10000 ppm，最佳200至5000 ppm。
於本發明之溶液中，金屬與具有羧基及氮原子之聚合物的比係藉由金屬之莫耳數與該聚合物中羧基之莫耳數定之，如自1：0.1至1：10，較佳係自1：0.5至1：5。
視需要，本發明可包括常規用於無電鍍覆觸媒組成物中之多種佐劑的一者或多者，如界面活性劑、緩衝劑、錯合劑及pH調節劑。pH調節劑可包括鹼如，但不限於，氫氧化鈉及氫氧化鉀，以及酸如，但不限於，硫酸、草酸、醋酸、檸檬酸及其他簡單羧酸。pH調節劑之量係以目標pH值為基準。
於本發明中使用之溶劑較佳係水，如自來水或DI水。任何其他溶劑如醇或溶劑之混合物可用於本發明中，只要該溶劑可與水混合即可。
典型地，本發明之溶液係具有3至10之pH。本發明之溶液的較佳pH係取決於奈米粒子製備過程中聚合物及還原劑的類型及量。較佳地，典型之本發明之溶液係具有大於4之pH，更佳地，該pH係6至9，再更佳地，該pH係鹼性，亦即，其係具有大於7至9之pH。
本發明之溶液係有用於作為將待鍍覆材質之非導電表面予以無電鍍覆之觸媒的奈米粒子的安定溶液。較佳地，本發明之溶液不形成肉眼可見之沉澱物。更佳地，本發明之溶液不在加速老化測試以及加速存儲壽命測試之後形成肉眼可見之沉澱物。業經測試極限老化條件，如於40℃於鼓氣下存儲、高溫及低溫存儲。
本發明之溶液可藉由將貴金屬離子、聚合物及還原劑於溶液中組合而製備。較佳地，製備本發明之溶液的方法為：(a)製備包括貴金屬離子及具有羧基與氮原子之聚合物的溶液，以及，(b)於攪拌下將還原劑加入該溶液中。
於本發明中使用之貴金屬離子係藉由任何貴金屬源提供，只要該貴金屬可溶於溶劑即可。可將有機酸或無機酸與貴金屬源併用，以幫助該貴金屬溶解於溶液中。貴金屬元素係選自上揭之彼等，如銀、金、鈀、銠、釕、銥及鋨，且如上揭者，較佳之貴金屬元素係銀。
較佳之貴金屬離子源係貴金屬之有機鹽或無機鹽。較佳之貴金屬離子源的實例係包括，金屬硝酸鹽、金屬亞硝酸鹽、金屬鹵化物、金屬氧化物、金屬醋酸鹽、金屬硫酸鹽、金屬亞硫酸鹽、金屬氰化物、金屬葡萄糖酸鹽、金屬氟硼酸鹽、金屬烷基磺酸鹽、金屬硫代硫酸鹽及金屬硫氰酸鹽。金屬鹽之實例係包括，而不限於，硝酸銀、醋酸銀、硫酸銀、甲磺酸銀、對甲苯磺酸銀、苯甲酸銀、磷酸銀、三氟醋酸銀、硝酸鈀、氯化鈀、硫酸鈀、醋酸鈀、 四氯鈀酸鈉(sodium tetrachloropalladate)、四氯鈀酸銨、二氯二胺合鈀(palladium dichlorodiammine)及二氯四胺合鈀。
該等貴金屬離子之量係取決於該金屬鹽之溶解度以及貴金屬奈米粒子於本發明之溶液中的所欲濃度。舉例而言，銀鹽可以，以觸媒溶液之總量為基準計，0.01至100 g/L，較佳0.1至10 g/L，更佳0.1至5.0 g/L的量使用。
用於還原該等貴金屬離子之還原劑係任何能將所溶解之貴金屬離子還原為貴金屬形式而不形成會干擾該觸媒溶液催化性能之副產物的彼等還原劑。較佳之還原劑係二甲基胺基硼烷、硼氫化鈉、肼、次磷酸鈉、水合肼、抗壞血酸、異抗壞血酸、羥胺硫酸鹽、甲酸及甲醛。
還原劑之量可係足以還原所欲之貴金屬離子的任何之量。還原劑之較佳量係藉由貴金屬之倍數定之，例如為貴金屬離子之莫耳數的0.5至2倍。典型地，以該觸媒溶液中金屬濃度之總量以及對該反應中所使用之還原劑的選擇為基準，該量係0.01至10 g/L，更佳係0.01至2 g/L。
製備本發明之溶液的方法為，(a)製備包含貴金屬離子及具有羧基與氮原子之聚合物的溶液，以及，(b)於攪拌該溶液下將還原劑加入該溶液中。
該方法之第一步係製備包括貴金屬離子及具有羧基與氮原子之聚合物的溶液。包括該等貴金屬離子及聚合物之溶液可藉由任何方法製備。舉例而言，將該聚 合物溶解於溶劑如水中，隨後將貴金屬之鹽或貴金屬鹽之水溶液加入該溶液中；或將貴金屬離子溶解於溶劑中，隨後將該聚合物或該聚合物之溶液加入該溶液中。
該方法之第二步係於攪拌下將還原劑加入該溶液中。於此步驟中使用之還原劑的量係足以形成所欲之貴金屬奈米粒子的任何量。
還原劑係於攪拌下加入上述溶液中。於強烈攪拌條件下，該等金屬離子可被還原為金屬並快速形成作為奈米粒子進一步生長之種子的奈米晶體。若攪拌不充分，則粒子尺寸可能不均勻，且某些粒子可能生長得較大且可能容易沉澱。換言之，強烈攪拌允許於較窄粒子尺寸分佈內形成較小之奈米粒子。典型之混合速率可係自200至1000 rpm。
於第二步中，該溶液之溫度係10至40℃，典型係室溫左右或20℃。
儘管不欲受縛於理論，本發明之發明人相信，於本發明之聚合物之存在下形成安定之貴金屬奈米粒子的機制係如下述者：通常，該等奈米粒子係具有由於布朗運動、對流、重力及其他力而彼此聚集為膠體之趨勢，其可導致該膠體之凝集以及去安定化。膠體之靜電安定化及立體安定化係膠體安定化之兩種常見機制。於聚合物之存在下，如是製備之奈米粒子可藉由該等聚合性分子所環繞，且該等聚合性分子產生能對抗平衡粒子間之凡得瓦力的斥力。
用於製備膠體性觸媒溶液之較佳方法為製備包括1至5 g/L之銀離子及1至5 g/L之聚天冬胺酸鈉的溶液，隨後於20至40℃之強烈攪拌或200至800 rpm加入10至80 mmol/L之二甲基胺基硼烷。
含有貴金屬奈米粒子及具有羧基與氮原子之聚合物的溶液可用於印刷電路板的無電鍍覆製程中。通孔係藉由鑽孔或衝孔或該技藝中已知之任何其他方法形成於印刷電路板中。於形成該等通孔之後，以水及傳統之有機溶液沖洗該板以進行清潔及去油脂，將該等通孔壁進行表面去汙之後使用該板。典型地，該等通孔壁之表面去汙係以溶劑溶脹劑之施用為始。任何之傳統溶劑溶脹劑可用以將該等通孔進行表面去汙。溶劑溶脹劑係包括，但不限於，二醇醚類及其相應之醚醋酸酯類。可使用傳統之量的二醇醚類及其相應之醚醋酸酯類。此等溶劑溶脹劑係該技藝中習知者。可商購之溶劑溶脹劑係包括，但不限於，CIRCUPOSIT CONDITIONERTM 3302溶液、CIRCUPOSIT HOLE PREPTM 3303及CIRCUPOSIT HOLE PREPTM 4120溶液，其全部可自羅門哈斯電子材料公司(Rohm and Haas Electronic Materials,Marlborough,MA)獲得。
視需要，以水沖洗該等通孔。隨後將促進劑施用至該等通孔。可使用傳統之促進劑。此等促進劑係包括硫酸、鉻酸、鹼性高錳酸鹽或電漿蝕刻劑。典型係使用鹼性高錳酸鹽作為該促進劑。可商購之促進劑之實例為可自羅門哈斯電子材料公司購得之CIRCUPOSIT PROMOTERTM 4130溶液。
視需要，以水再次沖洗此等通孔。隨後將中和劑施用至該等通孔以中和該促進劑留下之任何殘質。可使用傳統之中和劑。典型地，該中和劑係含有一種或多種胺類之鹼性水溶液，或3 wt%過氧化物及3 wt%硫酸的溶液。視需要，以水沖洗該等通孔，並乾燥該印刷電路板。
於表面去汙之後，可將酸性或鹼性調節劑(conditioner)施用至該等通孔。可使用傳統之調節劑。此等調節劑可包括一種或多種陽離子性界面活性劑、非離子性界面活性劑、錯合劑及pH調整劑或緩衝劑。可商購之酸性調節劑係包括，但不限於，可自羅門哈斯電子材料公司購得之CIRCUPOSIT CONDITIONERTM 3320及CIRCUPOSIT CONDITIONERTM 3327溶液。適宜之鹼性調節劑係包括，但不限於，含有一種或多種四級胺類或多胺類之鹼性界面活性劑水溶液。可商購之鹼性界面活性劑係包括，但不限於，可自羅門哈斯電子材料公司購得之CIRCUPOSIT CONDITIONERTM 231、3325、813及860溶液。視需要，該等通孔係於調節之後以水沖洗。
於調節之後進行該等通孔之微蝕刻。可使用傳統之微蝕刻組成物。微蝕刻係設計為在經曝光之銅上提供微粗糙化之銅表面，如內層及表面蝕刻，以提升後續之所沉積之無電鍍覆及電鍍的黏著。微蝕刻劑係包括，但不限於，60 g/L至120 g/L過硫酸鈉或氧單過硫酸鈉或氧單過硫酸鉀及2%硫酸混合物，或通用硫酸/過氧化氫。可商 購之微蝕刻組成物的實例係包括可自羅門哈斯電子材料公司購得之CIRCUPOSIT MICROETCHTM 3330溶液。視需要，以水沖洗該等通孔。
隨後將預浸塗液施用至經微蝕刻之通孔。可使用任何之能移除銅表面上之銅氧化物而不干擾該觸媒溶液的酸性溶液。預浸塗液之實例係包括草酸、醋酸、抗壞血酸、酚酸、磷酸、硼酸、及其鹽。視需要，以冷水沖洗該等通孔。
隨後，將上揭之觸媒，亦即，包括貴金屬奈米粒子之溶液，施用至該等通孔。隨後，使用鹼性無電鍍覆組成物以銅鍍覆該等通孔之壁。可使用任何之傳統無電鍍覆浴。可商購之無電銅鍍覆浴係包括，但不限於，可自羅門哈斯電子材料公司購得之CIRCUPOSITTM 880無電銅鍍覆溶液。
將銅沉積於該等通孔之壁上之後，視需要以水沖洗該等通孔。視需要，可將抗鏽(anti-tarnish)組成物施用至沉積於該等通孔壁上之金屬上。可施用傳統之抗鏽組成物，抗鏽組成物之實例係包括可自羅門哈斯電子材料公司之ANTI TARNISHTM 7130及CUPRATECTM 3組成物。該等通孔可視需要以溫度超過30℃之熱水沖洗，隨後，可乾燥該等板。
下述實施例係欲以進一步詳細揭示本發明但並非欲以限制其範疇。
[實施例] 測試方法
藉由觀察根據下述之製程進行之測試片的無電銅鍍覆來評估觸媒之特性。使用來自盛益公司(Shengyi)之傳統FR-4層壓體、SY-1141(正常Tg)測試片。對於表面覆蓋率測試，係使用裸層壓體。對於背光測試，係使用具有銅內層之Cu包覆層壓體。
(1)將該測試片切割為1×6 cm2 小片，藉由SiC#240粒子砂磨其邊緣，隨後於RO(反透(Reverse Osmosis))水中清潔若干次並吹乾。
(2)透過表1中顯示之溶脹、氧化、中和、調節及微蝕刻步驟進行處理。
(3)將該測試片於40℃於每一實施例中揭示之具體pH的觸媒溶液中浸漬3至10分鐘。以去離子水洗滌該測試片。
(4)於40℃進行無電銅鍍覆15分鐘。
鍍覆覆蓋率測試
使用下述定義之鍍覆覆蓋率分級評分進行該測試片之鍍覆覆蓋率測試。
全覆蓋：測試片之表面上超過95%之面積被鍍覆。
高：測試片之表面上超過75%但低於95%之面積被鍍覆。
中：測試片之表面上超過50%但低於75%之面積被鍍覆。
低：測試片之表面上超過5%但低於50%之面積被鍍覆。
無覆蓋：測試片之表面上低於5%之面積被鍍覆。
背光測試
根據下述製程施行背光測試。
將來自每一板之1 mm厚的橫截面置於傳統光學顯微鏡下，設定為透射模式之50x放大。藉由將在該顯微鏡下觀察到之光的量與歐洲背光分級標準(European backlight Grading Scale,0至5)比較而確定銅沉積之數量。若未觀察到光，該切面完全黑暗，其係歸為背光等級之5.0級。這表明完全之銅覆蓋。若光穿透整個截面而無任何暗域，這表明非常少或無銅金屬沉積於該壁上，該截面係歸為0級。若截面具有某些暗域以及光域，他們與標準相比歸為0與5之間。
ICD測試
藉由下述ICD測試(互連缺陷測試)量測鍍覆之可靠性。
將含有至少30個孔徑為1 mm的孔之經鑽孔之MLB(多層板)測試片切割。藉由SiC紙以Grit#240打磨該測試片邊緣。於RO水中進行若干次超音波清潔。該製程係自表面去汙運行至PTH(經鍍覆之通孔)，並最終至銅電鍍。將該測試片每一邊緣之任何Cu打磨除去。將該測試片於125℃烘烤6 h。該測試片於乾燥室中冷卻。或者，於288℃進行焊劑浸塗10秒，於室溫冷卻110秒。重複該 循環6次。
於該測試片上預形成微截面，且該截面係於蝕刻之前進行ICD研究。計數互連區域內之缺陷的數目並依據標準計算之。
以20 ml銨溶液、20 ml水及10滴過氧化氫的氨溶液蝕刻該測試片。證實該ICD上缺陷的數目。
實施例1：Ag-PASP觸媒系統
步驟1：於攪拌下將1.0 g之聚琥珀醯亞胺與200 ml之去離子水混合，隨後，於攪拌下及於30至90℃加熱下將10 ml/L之1.0 mol/L氫氧化鈉溶液加入該混合溶液中。所獲得之化合物的Mw藉由GPC方法量測為約1100。
步驟2：將200 ml之上述溶液混合入800 ml之去離子水中，並於攪拌下將1.7 g之硝酸銀加入該溶液中。
步驟3：於使用磁力攪拌器以500 rpm強烈攪拌下，將10 ml之新鮮製備之2.0 mol/L二甲基胺基硼烷(DMAB)快速加入上述溶液中。再攪拌超過2 h。
於保持在40℃之溫度浴下，基於以10 mL/min之速率將測試溶液空氣鼓泡來施行加速老化測試。一個月後，該觸媒溶液仍處於良好狀態。
亦於-20℃及60℃施行48小時之加速有效期測試，未見肉眼可見之沉澱物且無催化活性損失。
實施例2：Ag-PASP觸媒系統
步驟1：於攪拌下將3.2 g之40%聚天冬胺酸鈉(PASP)溶液(Mw=3,000-5,000)與990 ml之去離子水混合。於攪拌下將1.7 g之硝酸銀加入該溶液中。
步驟2：於使用磁力攪拌器以500 rpm強烈攪拌下，將10ml之新鮮製備之2.0 mol/L二甲基胺基硼烷(DMAB)快速注射入上述溶液中。再攪拌2 h。所得溶液具有9.0之pH。
施行實施例1之加速老化測試劑加速有效期測試，並未觀察到沉澱物或混濁。
實施例3至13：Ag-PASP觸媒系統
如實施例2中所述者製備Ag-PASP觸媒溶液，但每一組分之濃度及溫度係依表2中所顯示者改變。
施行實施例2中之效能測試。覆蓋率測試、背光測試及ICD測試之結果係顯示於表3中。使用硫酸或氫氧化鈉調節pH。
實施例14至21：Ag-PGA觸媒系統
如實施例2中所述者製備Ag-聚麩胺酸溶液，但PASP係改變為聚麩胺酸(PGA)(Mw>500,000)，且每一組分之濃度係依表4中顯示者改變。
對實施例19施行效能測試。覆蓋率測試劑背光測試之結果係顯示於表5中。
實施例22至25：Ag-AA與AMPS共聚物的觸媒系統
如實施例2中所述者製備Ag-丙烯酸(AA)與2-丙烯醯胺基-2-甲基丙磺酸(AMPS)之共聚物的溶液，但將PASP改變為丙烯酸與2-丙烯醯胺基-2-甲基丙磺酸的共聚物(Mw=10,000)，且每一組分之濃度係依表6中顯示者改變。
對實施例24施行效能測試。覆蓋率測試劑背光測試之結果係顯示於表7中。
比較例1：Ag-ASP觸媒系統
如實施例2中所述者製備Ag-L-天冬胺酸鹽的溶液，但將PASP改變為L-天冬胺酸鹽(ASP)，將DMAB改變為NaBH4 ，且每一組分之濃度係依表8中顯示者改變。
對比較例1施行效能測試。覆蓋率測試劑背光測試之結果係顯示於表9中。
使用L-天冬胺酸鹽製備之奈米粒子並不如使用聚天冬胺酸鹽製備者安定，且其僅可於鹼性pH介質 中予以安定化，而使用聚天冬胺酸鹽製備之奈米粒子能於更寬之4至10之pH範圍內予以安定化。
比較例2至5：Ag-PAM觸媒系統
如實施例2者進行嘗試以獲得Ag-聚丙烯醯胺(PAM)溶液，但將PASP改變為0.2至2.0 g/L之PAM，且每一組分之濃度係依表10中顯示者改變。
惟，加入0.2或0.4 g/L之PAM作為安定劑及於注射還原劑之後10至20分鐘之後，出現褐色沉澱物。使用1.0 g/L之PAM，於老化1天之後，亦有沉澱物沉降於該容器底部。使用2.0g/L之PAM，反應發生得非常慢且立即造成膠體之形成。無法使用PAM作為安定劑來獲得安定之膠體觸媒。
比較例6至11：Ag-PVP觸媒系統
如實施例2者製備Ag-聚乙烯基吡咯烷酮(PVP)觸媒系統，但將PASP改變為0.2至9.0 g/L之PVP(Fluka K25,Mw=24,000)，且每一組分之濃度係依表11中 顯示者改變。
全部溶液皆顯示混濁外觀。
對比較例10施行效能測試。覆蓋率測試之結果係顯示於表12中。
如實施例及比較例中所揭示者，與含有其他成份之溶液相比，本發明之溶液(包含貴金屬奈米粒子及具有羧基與氮原子之聚合物的溶液)係具有高吸附能力及催化活性，以及良好之浴安定性。

Claims (6)

  1. 一種包含貴金屬奈米粒子及聚合物之溶液，該聚合物係於該聚合物之重複單元內包含羧基與氮原子。
  2. 如申請專利範圍第1項所述之溶液，其中，該聚合物係聚胺基酸。
  3. 如申請專利範圍第1項所述之溶液，其中，該聚合物係聚天冬胺酸鹽。
  4. 如申請專利範圍第1項所述之溶液，其中，該貴金屬係銀、金、鉑、鈀、銠、釕、銥或鋨。
  5. 一種製備包含貴金屬奈米粒子及具有羧基與氮原子之聚合物的方法，該方法係包含：製備包含貴金屬離子及具有羧基與氮原子之聚合物的溶液，於攪拌下，將還原劑加入該溶液中。
  6. 一種將金屬無電鍍覆於非導電表面上之製程，該製程係包含下列步驟：將待鍍覆之基板浸漬於如申請專利範圍第1項所述之溶液中，在不使用加速步驟下，施行該基板之無電鍍覆。
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