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CN104005008A - 镀覆催化剂和方法 - Google Patents

镀覆催化剂和方法 Download PDF

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Publication number
CN104005008A
CN104005008A CN201410062057.4A CN201410062057A CN104005008A CN 104005008 A CN104005008 A CN 104005008A CN 201410062057 A CN201410062057 A CN 201410062057A CN 104005008 A CN104005008 A CN 104005008A
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solution
monomer
polymkeric substance
electron
catalyst
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CN104005008B (zh
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邝淑筠
周卫娟
周文佳
D·C·Y·陈
D·K·W·余
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DuPont Electronic Materials International LLC
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Rohm and Haas Electronic Materials LLC
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Abstract

本发明涉及一种镀覆催化剂和方法。一种溶液，所述溶液包含贵金属纳米颗粒和由至少两种下列单体聚合而成的聚合物：(1)包含两个或更多个羧基或羧酸盐基团的单体，以及(2)具有可供应π电子特征体的单体。所述溶液可以用作在非导电性表面上无电镀覆金属的工艺的催化剂。

Description

镀覆催化剂和方法
技术领域
本发明涉及包含贵金属纳米颗粒的催化剂溶液，更具体来说，涉及包含用特定化合物稳定化的贵金属纳米颗粒的催化剂溶液，该催化剂溶液可以用来对非导电性基材进行无电金属镀覆，以及用于制造电子器件和装饰涂层。
背景技术
无电金属沉积或镀覆可以用来在无电源的条件下，在非导电性表面或介电表面上沉积金属或金属的混合物。在非导电性基材或介电基材上的镀覆被用于各种工业领域，包括装饰性镀覆以及电子器件的制造。这些主要应用中的一种是制造印刷电路板。为了在基材上无电沉积金属，经常需要对基材的表面进行预处理或者敏化，使得表面对沉积过程具有催化性。人们开发了各种方法来对表面进行催化。
US3,011,920公开了一种用来对基材进行催化的方法，该方法是将所述基材浸泡在胶体催化剂溶液中，该胶体催化剂溶液是用钯离子和二价锡离子制备的，形成钯-锡胶体。该方法需要在对基材表面进行催化之后进行加速步骤，从而使得催化剂芯暴露出来。US3,904,792公开了对胶体钯-锡催化剂的改良，从而能够在酸性较低的环境下提供催化剂。用酸的另一种可溶性盐部分地代替盐酸。此种钯-锡催化剂体系仍然存在大量的局限性。催化剂胶体SnCl4 2-的外壳很容易被氧化，因此催化剂颗粒的尺寸会变大，会造成其催化性表面积的显著损失。另外，由于环保方面的要求，人们开发了用于无电镀覆的不含锡的催化剂。
含氮的聚合物与钯具有良好的结合能力，因此文献中广泛描述了用含氮聚合物合成钯纳米颗粒作为催化剂。US4,725,314描述了使用有机悬浮剂（例如聚乙烯基吡咯烷酮）保护胶体，从而在水溶液中制备催化性被吸附物的方法。US20120097548A公开了使用谷胱甘肽和钯形成纳米颗粒的稳定水溶液，该水溶液可以用来催化无电金属沉积。US20120145555A公开了使用含氮的杂环化合物（例如组氨酸或尿刊酸）来催化无电金属沉积。但是，含氮的聚合物不仅与钯具有良好的相互作用，而且与铜也具有良好的相互作用。此种连接很难去除，互连缺陷问题会导致电子器件可靠性出现问题。另外，此种催化剂经常在碱性介质中发挥作用。在此碱性介质中，内层的铜表面或者基底铜会很容易被氧化。这会导致互连缺陷的问题。
US4,652,311A公开了使用聚丙烯酸和聚丙烯酰胺作为悬浮剂。在存在悬浮剂的条件下，用温和的还原剂还原钯离子。为了发挥稳定作用，避免颗粒进一步生长，需要加入可溶性醇溶液。醇更容易推动还原反应完全进行，并且对颗粒产生稳定化效果，防止其发生聚集。其在碱性范围下起作用并且钯浓度为10-2,000ppm。WO2011/030638A公开了使用聚丙烯酸作为分散剂，由此可以避免钯胶体的聚集和沉降。使用邻苯二酚来抑制钯的氧化，同时使用铜-酸抑制剂来限制铜胶体或氢氧化铜的形成。
但是，人们仍然需要开发同时在镀浴稳定性、吸附能力和催化活性方面实现平衡的胶体催化剂体系。
发明内容
本发明的发明人发现了一种贵金属胶体催化剂体系，其包含用特定种类的聚合物稳定化的贵金属纳米颗粒，所述聚合物是由至少两种下列单体聚合形成的：(1)包含两个或更多个羧基或羧酸盐基团的单体，以及(2)具有可供应π电子特征体的单体。
这种不含锡的催化剂体系对无电镀覆具有良好的稳定性和有前景的催化活性。另外，所述新开发的胶体催化剂体系能够减小钯浓度，具有很宽的操作范围，能够在很宽的pH范围内有效地工作，能够用于工业用途。
附图说明
本发明的申请文件包括至少一幅彩色的附图。本专利包括彩色附图的副本将根据要求，在支付所需的费用之后由专利局提供。
图1显示了在测试样品上进行无电镀铜的镀覆覆盖测试的结果;
图2显示了用于无电镀铜的钯胶体催化剂的催化活性曲线图。
具体实施方式
在本说明书中，除非上下文明确有不同的说明，以下缩写具有下述含义：g=克;mg=毫克;ml=毫升;L=升;m=米;min.=分钟;s=秒;h.=小时;ppm=百万分之份数;M=摩尔;mM=毫摩尔;g/L=克/升。
本文所用术语“沉积”和“镀覆”可以互换使用。在说明书中，术语“催化”和“活化”可互换使用。在说明书中，术语“包含贵金属纳米颗粒的溶液”和“催化剂溶液”可互换使用。前缀“一个”和“一种”表示单数和复数形式。
本发明提供了用于无电镀覆的溶液，所述溶液包含贵金属纳米颗粒和由至少两种下列单体聚合而成的聚合物：(1)包含两个或更多个羧基或羧酸盐基团的单体，以及(2)具有可供应π电子特征体的单体。
关于以上单体(1)的要求，本发明的发明人发现，由至少一种包含两个或更多个羧基或羧酸盐基团的单体聚合而成的聚合物能够用作贵金属（例如银）的稳定剂。本发明人发现，具有可供应π电子特征体的单体(2)能够与单体(1)协作起来提高纳米颗粒的稳定性，甚至当纳米颗粒的贵金属为二价金属（例如钯）的情况下也是如此。
单体(1)在该单体内包含两个或更多个羧基或羧酸盐基团。换而言之，所述单体是不饱和的多羧酸或其盐。因此，用于本发明的聚合物在其重复单元中包含至少两个羧基或羧酸盐基团。单体(1)的例子包括马来酸、富马酸、衣康酸、以及它们的盐。优选使用马来酸。
单体(2)在其单体结构中包括可供应π电子特征体。所谓“可供应π电子的能力”表示π键中的电子可供利用，能够在本发明中为金属纳米颗粒/离子之间的相互作用作出贡献。人们已知，π电子位于由原子轨道重叠形成的π键之内。可供应π电子的特征体是包含π电子的官能团,在本发明中，该特征体可供与金属纳米颗粒/离子相互作用。可供应π电子的特征体的例子包括C=C结构,苯环，以及这些特征体上的供电子取代基。这些可供应π电子的特征体能够通过与金属原子的空轨道发生相互作用，从而提供额外的稳定性。
较佳的是，所述单体(2)选自：芳族乙烯基单体、芳族烯丙基单体和链二烯。这些单体具有供应π电子的能力。芳族乙烯基单体的例子包括苯乙烯；取代的苯乙烯，例如甲基苯乙烯、乙基苯乙烯、叔丁基苯乙烯、4-苯乙烯磺酸或乙烯基苯甲醚、α-甲基苯乙烯、β-甲基苯乙烯和反式茴香醚（trans-anithole）。芳族烯丙基单体的例子包括烯丙基苯、取代的烯丙基苯，例如烯丙基苯甲醚、烯丙基甲苯和4-烯丙基邻苯二酚。链二烯的例子包括1,3-丁二烯,异戊二烯,2,3-二甲基-1,3-丁二烯,1,3-戊二烯,2-甲基-1,3-戊二烯,3-甲基-1,3-戊二烯,1-甲氧基-1,3-丁二烯,2,3-二甲氧基-1,3-丁二烯和反式-1-苯基-1,3-丁二烯。
较佳的是，所述单体(2)之内不含电负性原子或者吸电子基团。因为π键是由形成散布的电子云的松散保持的电子组成的，因此π键很容易发生扭曲。对于包含π键的简单体系（例如双键）,当存在氧之类的电负性原子的时候,电子云容易朝向氧发生扭曲，使得供应π键电子用于所述相互作用的能力变得很低。另一方面，如果双键中不含电负性原子,例如为C=C,则π电子会在该键中均匀地共用，因此供应π电子用于所述用途的能力会很高。再例如，苯乙烯是一种具有可供应的π电子的单体。但是，如果苯乙烯被卤化物或NO2之类的吸电子基团取代的话，苯环上的π电子密度会降低，因此特征体供应π电子的能力会降低。
用于本发明的聚合物是由以上所述的至少两种单体，即单体(1)和单体(2)聚合而成的聚合物。所述聚合物可以通过任意已知的方法制备。用于该已知方法的例子是链增长聚合以及自由基聚合。
由于在重复单元中包含两个源自单体(1)的羧基,与包含由含有一个羧基的单体聚合制得的聚合物（例如聚丙烯酸）的溶液相比，本发明的聚合物在用于本发明的时候，在很宽的pH值范围内获得良好的结果，得到稳定的催化剂溶液。本发明使用的聚合物与由含有一个羧基的单体聚合得到的聚合物之间的区别在于包含这些聚合物的溶液的pKa的差异。用于本发明的包含所述聚合物的溶液具有至少两个pKa值，与之形成对比的是，包含聚丙烯酸的溶液具有一个pKa，约为4.58。
虽然不希望被理论所限制，但是认为本发明的聚合物同时作为缓冲剂以及贵金属纳米颗粒的稳定剂，因此包含用于本发明所用的聚合物的溶液在很宽的pH范围内，在胶体催化剂的反应活性和稳定性方面实现更佳的平衡。因为单体(2)可供应π电子,用于本发明的聚合物在单体(1)的协作下获得了更稳定的催化剂溶液,甚至当纳米颗粒的贵金属是二价金属（例如钯）的时候也是如此。源自单体(1)和单体(2)的单元的摩尔比为0.1至10,优选为0.5至2。
用于所述溶液的聚合物的分子量(Mw)为400至700,000,更优选为800-10,000。Mw越高则胶体稳定性越好，但是对催化活性有直接的牺牲，也即是说，可能导致差的催化活性。
本发明的催化剂溶液包含由至少一种单体(1)和单体(2)聚合而成的聚合物，以及贵金属纳米颗粒。本发明的贵金属纳米颗粒由任意贵金属提供，只要该金属可以作为催化剂即可。贵金属的例子是银、金、铂、钯、铑、钌、铱和锇。较佳的是，所述贵金属是二价金属。更佳的是，所述贵金属是钯。可以使用贵金属的混合物，例如银和钯的混合物。以催化剂溶液的总量为基准计，贵金属纳米颗粒的量为0.01-100克/升,优选为0.1-10克/升,最优选为0.2-1.0克/升。
以催化剂溶液的总量为基准计，所述催化剂溶液中聚合物优选的量为0.05-20克/升,更优选为0.5-2.0克/升。
任选的，本发明可以包含一种或多种通常用于无电镀覆催化剂组合物的各种添加剂，例如表面活性剂、缓冲剂、络合剂和pH调节剂。pH调节剂可以包括碱，例如氢氧化钠和氢氧化钾；以及简单的酸，例如硫酸、草酸、乙酸、柠檬酸和其他简单的羧酸。pH调节剂的用量及其选择是基于目标pH值进行的。
本发明使用的溶剂优选是水，例如自来水或去离子水。任何其他的溶剂，例如醇或溶剂的混合物可以用于本发明，只要该溶剂能够与水相溶即可。
通常，本发明的溶液的pH值为2-10。本发明的溶液的优选pH值取决于纳米颗粒制备过程中的聚合物以及还原剂的种类和用量。较佳的是，本发明的典型溶液的pH值通常大于3,更优选pH值为5-9,更优选pH为碱性，也即是说，pH值为大于7至小于或等于9。
本发明的溶液是纳米颗粒的稳定溶液，可以作为催化剂，用来对待镀敷材料的非导电性表面进行无电镀覆。较佳的是，本发明的溶液不会形成可观察到的沉淀。更优选地，本发明的溶液在加速老化测试和加速储存期测试之后不会形成目测可观察到的沉淀。加速老化测试是通过以下方式进行的：将溶液置于40℃的浴中，在空气鼓泡条件下保持2周；加速储存期测试是通过以下方式进行的：将所述溶液置于-20℃和60℃的条件下48小时。
可以通过在溶液中将贵金属离子、聚合物和还原剂混合起来，来制备本发明的溶液。较佳的是，用来制备本发明的溶液的方法为：(a)制备一种溶液，该溶液包含贵金属离子以及至少由单体(1)和单体(2)聚合而成的聚合物,以及(b)在对所述溶液进行搅拌的同时，将还原剂加入所述溶液中。
用于本发明的贵金属离子可以用任意贵金属源提供，只要所述贵金属能够溶于溶剂即可。可以将有机酸或无机酸与贵金属源一起使用，以助于将贵金属溶解于溶液中。贵金属元素选自以上所述的那些元素，例如银、铂、钯、铑、钌、铱和锇,如上文所述，优选的贵金属元素是钯。
优选的贵金属离子源是贵金属的有机盐或无机盐。优选的贵金属离子源的例子包括：金属硝酸盐、金属亚硝酸盐、金属卤化物、金属氧化物、金属乙酸盐、金属硫酸盐、金属亚硫酸盐、金属氰化物、金属葡糖酸盐、金属氟代硼酸盐、金属烷基磺酸盐、金属硫代硫酸盐、以及金属硫氰酸盐。金属盐的例子包括但不限于，二氯化钯，硫酸钯,四氯代钯(II)酸钠,二氯二胺合钯(II),硝酸钯,乙酸钯,四氯代钯(II)酸铵,四氯代钯(II)酸钾,硝酸银,乙酸银,硫酸银,甲磺酸银,对甲苯磺酸银,苯甲酸银,磷酸银和三氟代乙酸银。
贵金属离子的量取决于金属盐的溶解度以及本发明溶液中所需的贵金属纳米颗粒的浓度。例如，以催化剂溶液的总量为基准计，钯盐的用量（以金属计）可以为0.01-100克/升,优选0.1-10克/升,更优选0.2-1.0克/升。
用来对贵金属离子进行还原的还原剂可以是任何能够将溶解的贵金属离子还原成还原的贵金属形式、而且不会形成影响该催化剂溶液的催化的副产物的还原剂。优选的还原剂是二甲基氨基硼烷,硼氢化钠,肼,次磷酸钠,水合肼,抗坏血酸,异抗坏血酸,硫酸羟胺,甲酸和甲醛。
还原剂的量是足以对所需的贵金属离子进行还原的任意的量。还原剂优选的量可以用与贵金属的摩尔比来确定，还原剂摩尔量是贵金属离子摩尔量的0.5倍至2倍。通常，基于催化剂溶液中金属浓度的总量以及反应中采用的还原剂的选择，还原剂的量为0.2-200mM,更优选为2-20mM。
用来制备本发明的溶液的方法为：(a)制备一种溶液，该溶液包含贵金属离子以及至少由单体(1)和单体(2)聚合而成的聚合物,以及(b)在对所述溶液进行搅拌的同时，将还原剂加入所述溶液中。
该方法的第一步是制备溶液的步骤，该溶液包含贵金属离子和至少由单体(1)和(2)聚合而成的聚合物。所述包含贵金属离子和聚合物的溶液可以通过任意方法制备。例如，将聚合物溶解在例如水之类的溶剂中，然后向该溶液中加入贵金属盐或者贵金属盐的水溶液;或者将贵金属离子溶解在溶剂中，然后将聚合物或聚合物的溶液加入该溶液中。
该方法的第二步是在对所述溶液进行搅拌的同时，向该溶液中加入还原剂。该步骤中还原剂的量是足以形成所需的贵金属纳米颗粒的任意的量。
在对上述溶液进行搅拌的同时，将还原剂加入该溶液中。在剧烈搅拌的条件下,所述金属离子会被还原成金属，快速形成大量纳米晶体，这些纳米晶体作为进一步颗粒生长的晶种。如果搅拌的程度不足,会造成粒度不均一，一部分颗粒生长得较大，可能容易沉淀。换而言之，通过剧烈的搅拌，可以形成具有较窄的粒度分布的较小的纳米颗粒。混合速率通常可以为200-1000rpm。
在第二步骤过程中，溶液的温度为10-40℃,通常近似处于室温(20℃)。
虽然不希望被理论所限制，但是发明人认为在存在本发明的聚合物的情况下形成稳定的贵金属纳米颗粒的机理如下:在催化剂合成过程中，包含羧基的聚合物在不同pH值情况下可能会具有不同的质子化程度。如果质子化程度增大,则贵金属纳米颗粒/离子暴露的更多（稳定性较低），可能很容易聚集。当贵金属是诸如钯的二价金属的时候，这种趋势会显著增大。但是，如果在暴露的Pd附近存在可供应π电子的特征体的话，π电子会与Pd的空d轨道发生相互作用，一定程度上对其发挥稳定化效果。
本发明人将两种聚合物与二价贵金属（钯）一起测试。第一种聚合物在重复单元内包含两个羧基，但是在羧基附近（形成纳米颗粒的位置）没有可供应π电子的特征体。第二种聚合物在羧基附近具有可供应π电子的特征体(双键)。因为通过第二聚合物中可供应π电子的特征体使得贵金属（钯）稳定化,包含所述第二聚合物和钯的溶液为均一的溶液，而不是像使用第一聚合物形成的溶液那样形成凝胶状悬浮液。
预测的可供应π电子的特征体的效果:
优选的用来制备胶体催化剂溶液的方法为：制备包含0.2-1.0克/升钯离子和0.5-2.0克/升聚(丁二烯-马来酸(1:1))的溶液,然后在20-40℃的温度下，在剧烈搅拌（200-1000rpm）的条件下加入2-20mM二甲基氨基硼烷。
本发明的溶液包含贵金属纳米颗粒以及至少由单体(1)和单体(2)聚合而成的聚合物,其为本发明的胶体催化剂，可以用于制造印刷电路板的无电镀覆工艺。通过钻孔、冲压或本领域已知的任意其它方法，在所述印刷电路板中形成通孔。在形成所述通孔之后，用水和常规的有机溶液冲洗所述印刷电路板，从而对印刷电路板进行清洁和脱脂，然后对通孔壁进行去污。通常通孔的去污首先是进行溶剂溶胀。
可以通过任意常规的溶剂溶胀来对通孔进行去污。溶剂溶胀使用的材料包括但不限于二醇醚以及其相关的醚乙酸酯。可以使用常规用量的二醇醚及其相关的醚乙酸酯。这些溶剂溶胀材料是本领域众所周知的。可以在商业上购得的溶剂溶胀材料包括但不限于CIRCUPOSIT CONDITIONERTM3302,CIRCUPOSIT HOLE PREPTM3303和CIRCUPOSIT HOLE PREPTM4120，这些产品均可购自陶氏电子材料公司（Dow Electronic Materials）。
任选地，用水对通孔进行冲洗。然后对通孔施加促进剂。可以使用常规的促进剂。这些促进剂包括硫酸、铬酸、碱金属高锰酸盐或等离子蚀刻。通常使用碱金属高锰酸盐作为促进剂。可以在市场上购得的促进剂的例子是可以购自陶氏电子材料公司的产品CIRCUPOSIT PROMOTERTM4130。
任选地，用水再次对通孔进行冲洗。然后对通孔施加中和剂，以中和掉促进剂留下的任何残余物。可以使用常规的中和剂。通常，所述中和剂是包含一种或多种胺的碱性水溶液，或者3重量％的过氧化物和3重量％的硫酸的溶液。任选地，用水对通孔进行冲洗，然后对印刷电路板进行干燥。
在去污操作之后，可以对通孔施加酸性或碱性调节剂。可以使用常规的调节剂。这些调节剂可以包括一种或多种阳离子型表面活性剂、非离子型表面活性剂、络合剂和pH调节剂或缓冲剂。可以在市场上购得的酸性调节剂包括但不限于可以购自陶氏电子材料公司的产品CIRCUPOSITCONDITIONERTM3320和CIRCUPOSIT CONDITIONERTM3327。合适的碱性调节剂包括但不限于包含一种或多种季胺和多胺的碱性表面活性剂水溶液。可以在市场上购得的碱性表面活性剂包括但不限于可以购自陶氏电子材料公司的产品CIRCUPOSIT CONDITIONERTM231,3325和860。任选地，在所述调节步骤之后，用水对通孔进行冲洗。
在调节步骤之后，对通孔进行微蚀刻。可以使用常规的微蚀刻组合物。微蚀刻是设计用来在暴露的铜（例如内层和表面蚀刻）上提供微观粗糙化的铜表面，以提高随后沉积的无电镀覆物质和电镀物质的附着性。微蚀刻材料包括但不限于60-120克/升的过硫酸钠或氧代单过硫酸钠或氧代单过硫酸钾以及硫酸(2%)混合物，或者一般的硫酸/过氧化氢。可以在市场上购得的微蚀刻组合物的例子包括可以购自陶氏电子材料公司的产品CIRCUPOSIT PROMOTERTM3330。任选地，用水对通孔进行冲洗。
然后对微蚀刻之后的通孔进行预浸渍。可以使用任何能够除去铜表面上氧化铜、并且不会影响催化剂溶液的酸性溶液。预浸渍材料的例子包括草酸、乙酸、抗坏血酸、酚酸、磷酸、硼酸、以及它们的盐。任选地，用冷水对通孔进行冲洗。
然后将上文所述包含贵金属纳米颗粒的催化剂溶液施加于所述通孔。然后在不采用加速步骤的情况下，用碱性无电镀覆组合物对通孔壁镀铜。可以采用任意常规的无电镀浴。可以在市场上购得的无电铜镀浴包括但不限于可以购自陶氏电子材料公司的CIRCUPOSITTM880无电铜镀浴。
在将铜沉积在通孔的壁上之后，任选地用水对通孔进行冲洗。任选地，可以对沉积在通孔壁上的金属施加抗失光泽组合物。可以使用常规的抗失光泽组合物。抗失光泽组合物的例子包括可购自陶氏电子材料公司的产品ANTI TARNISHTM7130和CUPRATECTM3。所述通孔可以任选地在高于30℃的温度下用热水冲洗，然后可以对印刷电路板进行干燥。
实施例
试验方法
通过对用以下所述的工艺进行无电镀铜的测试样品进行观察，从而评价催化剂的性质。使用购自圣仪公司（Shengyi）的常规的FR-4层压板和SY-1141作为测试样品。使用裸露的层压板用于表面覆盖测试。使用具有内层铜的Cu覆盖层压板进行背光测试。
（1）将测试样品切割成1×6厘米2的尺寸，用SiC#240对其边缘进行喷砂处理，然后在RO(反渗透)水中清洗数次，吹气干燥。
（2）按照表1所示，通过溶胀、氧化、中和、调节和微蚀刻步骤进行加工。
（3）然后如各个实施例所示，在pH值为2.9至10.9的各种pH值之下，将测试样品在40℃的催化剂溶液中浸泡10分钟。测试样品用去离子水洗涤。
（4）在35℃或40℃的温度下进行15分钟的无电镀铜。
表1.用于无电铜沉积测试的工艺流程
1.镀覆覆盖测试
测试样品的镀覆覆盖测试是使用以下所述的镀覆覆盖分级表进行的。
完全覆盖–测试样品超过95%的表面区域被镀覆。
高–测试样品超过75%至小于95％的表面区域被镀覆。
中–测试样品超过50%至小于75％的表面区域被镀覆。
见图1：低–测试样品超过5%至小于50％的表面区域被镀覆。
无覆盖–测试样品小于5%的表面区域被镀覆。
2.背光测试
根据以下所述的过程进行背光测试。
将从每块板上取下的1毫米厚的横截片材放置在常规的光学显微镜下，所述显微镜为50倍放大，透射模式。将显微镜下观察到的光的量与欧洲背光登记标准0-5相比较，从而确定沉积铜的质量。如果未观察到光，则横截片材是全黑的，其背光等级为5.0。这表示完全铜覆盖。如果光通过整个横截片材，没有深色区域，则表明壁上铜金属沉积极少，或者没有铜金属沉积，该横截片材的评级为0。如果横截片材有一部分深色区域和浅色区域，则与标准相比较，在0-5之间评级。
3.加速老化测试(AAT)
通过如下方式进行加速老化测试;
制备具有50毫升固定体积的催化剂加工浴或者浓缩物，然后在浴温40℃、以10毫升/分钟的速率空气鼓泡的条件下保持7天或者数周，从而对所述溶液进行加速老化测试。然后使用这些加速老化催化剂工作浴再次进行覆盖测试和背光测试，以鉴别是否丧失催化活性。与此同时，还可以进行其他的对应的测试，例如紫外可见吸收光谱测试。
实施例1-4：使用不同钯盐的Pd-PBDMA催化剂体系
实施例1：
步骤1-称取2.38克聚(丁二烯-马来酸)1:1摩尔(Mw=10,000-15,000)溶液(42%),将其溶解在25毫升去离子(DI)水中;在搅拌条件下，在3升的烧杯中，将其与780毫升去离子水混合;然后在搅拌的同时，将1.0克二氯二胺合钯(II)加入该溶液中。用NaOH将pH值调节到3.0至4.0。
步骤2-在使用磁力搅拌器以500rpm的转速进行剧烈搅拌的同时，向上述溶液快速注入7毫升新鲜制备的1.0摩尔/升的二甲基氨基硼烷(DMAB)，并继续搅拌超过1小时，制得Pd纳米颗粒(Pd催化剂浓缩物)。
步骤3-为了储存制备的纳米颗粒，在注入还原剂开始3-4之后，将pH值调节到9.0-9.5。总体积最高达最终体积1升。
Pd浓缩物的组分如下。
Pd催化剂浓缩物:
Pd离子:0.5克/升
作为稳定剂的PBDMA:1.0克/升
DMAB:7.0mM
使用去离子水将所述制得的Pd催化剂浓缩物稀释至[Pd2+]浓度为15ppm,然后进行表1所示的无电镀铜过程。各种工作浴在1天的加速老化测试（AAT）之前和之后，pH值为2、3、5和7的条件下树脂覆盖和背光等级结果见表2。
实施例2-4
按照实施例1所述的方式制备Pd催化剂浓缩物，区别在于，将钯盐(二氯二胺合钯(II))分别换成二氯化钯(实施例2),四氯合钯(II)酸钠(实施例3)以及硫酸钯(实施例4)，储存pH值换成如表2所示的值。按照与实施例1相同的过程进行无电镀铜,结果见表2。
表2
Y:被铜镀覆的树脂
WB1-天AAT:1天AAT的工作浴
“---“:催化剂显示无树脂覆盖
NA：不适用
测试结果表明包含用马来酸（包含两个羧基的单体）和丁二烯（具有可供应π电子的特征体）合成的稳定剂的催化剂能够在可调节的pH值条件下工作。由于包含稳定剂的溶液具有两个pKa值,因此在不同pH值范围内的催化活性是不同的。
实施例5：钯浓度的影响
按照与实施例1相同的方式制备Pd催化剂浓缩物，区别在于，使用以下的钯源和条件。将制得的Pd催化剂浓缩物稀释至[Pd2+]浓度为5,10,15,25,50和100ppm,然后采用与实施例1相同的过程进行无电镀铜。
（Pd催化剂浓缩物）
Pd离子:0.5克/升(Pd源:Na2PdCl4)
作为稳定剂的PBDMA:1.0克/升
DMAB:7.0mM
(其他条件)
合成温度:20-25℃
合成之后的储存pH值:8.9
催化剂工作浴pH:4.0
结果列于图2，图2显示了实施例5中的Pd胶体催化剂体系的催化曲线。
从测试结果可以看到,包含用马来酸（包含两个羧基的单体）以及丁二烯（可供应π电子的特征体）合成的稳定剂的催化剂至少能够在10ppm的浓度下工作。这是很低的浓度和温和的条件。各样品的背光值同样列于图2。所提供的值是10-15个孔的平均背光读数，其中每种样品最低的背光等级列于括号中。
实施例6-9：催化剂浓缩物耐受AAT的稳定性
按照与实施例1相同的方式制备了Pd催化剂浓缩物，区别在于，将稳定剂换成聚(4-苯乙烯磺酸-共-马来酸)钠盐(PSSA-co-MA,实施例7),聚(苯乙烯-交替-马来酸)钠盐(PSMA,实施例8),聚(丙烯酸)(PAA,实施例9)。各种稳定剂的化学结构和Mw列于表5。在制备催化剂浓缩物之后,进行如上文所述的加速老化测试(AAT)。
Pd催化剂浓缩物:
Pd离子:0.5克/升(Pd源:Na2PdCl4或(NH3)2PdCl2)
稳定剂：1.0克/升
DMAB:7.0mM
结果见表3。
表3：稳定剂的pKa与表现出催化活性的pH范围之间的关系。
*在AAT过程中产生过多的泡沫。这会显著影响测试体积。实施例9是比较例。
从测试结果可以看到,包含可供应π电子的特征体的稳定剂在很宽的pH范围内，能够耐受加速老化条件而保持催化剂的稳定性，不会失去催化活性。
实施例10-20：稳定剂的影响
按照与实施例1相同的方式制备Pd催化剂浓缩物，区别在于，稳定剂和钯源按照表4和表5所示改变。按照与实施例1相同的方式进行无电镀铜。结果列于表4和5。
表4：聚合物官能团或特征体对稳定性的影响与Pd胶体催化剂性能之间的关系。
表5：Pd催化剂的合成详细信息，以及相应的催化剂工作浴中的Pd浓度/pH范围。
*可工作pH范围表示在该pH范围内，催化剂工作浴能够在裸露的层压板上实现高树脂覆盖(76%–94%)。
参见表4,实施例6、7和8的稳定剂都同时包括以下特征：(1)在重复单元内含有两个羧基，(2)强供应π电子性特征体。实施例6、7和8的Pd胶体催化剂是稳定的，具有很高的背光性能。
实施例13的稳定剂具有可供应π电子的特征体(聚(4-苯乙烯磺酸钠))，但是不含羧基。实施例13的催化剂虽然稳定性很高，但是背光性能不佳。因为缺少羧基,该催化剂无法在不同的pH值条件下实现不同的质子化程度，因此无法具有不同的稳定化程度。催化剂的高稳定性取决于稳定剂的强酸性，这是因为磺酸基是强酸基。
实施例14,15和16的稳定剂在重复单元中包含两个羧基，但是没有可供应π电子的特征体。实施例14未形成稳定的催化剂,实施例15和16形成了稳定的催化剂，但是背光测试效果不佳。这些结果表明需要同时包含(1)位于重复单元中的至少两个羧基以及(2)可供应π电子的特征体，才能制得在很宽pH值范围内具有高稳定性和良好背光性能的Pd催化剂,特别是对于弱酸条件。
实施例21-24：用PBDMA稳定化的银胶体催化剂
实施例21：
按照与实施例1相同的方式制备了Ag催化剂浓缩物，区别在于，将Pd源和用量改变为1.7克硝酸银(AgNO3)，还原剂(DMAB)的用量改变为20mM。所得Ag催化剂浓缩物如下所示。
Ag催化剂浓缩物:
Ag离子:1.08克/升
还原剂(DMAB):20mM
将Ag催化剂浓缩物稀释至270ppm，采用实施例1所述的过程进行无电镀铜。
实施例22-24：
按照与实施例21相同的方式制备Ag催化剂浓缩物，区别在于，Ag离子以及PBDMA的用量按照表6所示的方式变化。将Ag催化剂浓缩物稀释至270ppm，采用实施例1所述的过程进行无电镀铜。
表6：在不同工作浴pH值范围内的Ag催化活性
参见表6,PBDMA也使得银纳米颗粒稳定化,所述包含用PBDMA稳定化的银纳米颗粒的溶液表现出催化活性。

Claims (8)

1.一种溶液，所述溶液包含贵金属纳米颗粒和由至少两种下列单体聚合而成的聚合物：(1)包含两个或更多个羧基或羧酸盐基团的单体，以及(2)具有可供应π电子特征体的单体。
2.如权利要求1所述的溶液，其特征在于，所述单体(2)选自芳族乙烯基单体和链二烯。
3.如权利要求1所述的溶液，其特征在于，所述单体(2)选自苯乙烯、取代的苯乙烯和丁二烯。
4.如权利要求1所述的溶液，其特征在于，所述单体(1)是马来酸或其盐。
5.如权利要求1所述的溶液，其特征在于，所述贵金属纳米颗粒是二价金属。
6.如权利要求5所述的溶液，其特征在于，所述贵金属纳米颗粒是钯。
7.一种制备溶液的方法，所述溶液包含贵金属纳米颗粒和由至少两种下列单体聚合而成的聚合物：(1)包含两个或更多个羧基或羧酸盐基团的单体，以及(2)具有可供应π电子特征体的单体，所述方法包括：
a)制备一种溶液，所述溶液包含贵金属离子和由至少两种下列单体聚合而成的聚合物：(1)包含两个或更多个羧基或羧酸盐基团的单体，以及(2)具有可供应π电子特征体的单体；以及
b)在对所述溶液进行搅拌的同时，将还原剂加入所述溶液中。
8.一种在非导电性表面上无电镀覆金属的方法，所述方法包括以下步骤:
a)将待镀覆的基材浸没在权利要求1所述的溶液中;以及
b)对所述基材进行无电镀覆。
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