CN100467666C - 催化剂组合物和沉积方法 - Google Patents
催化剂组合物和沉积方法 Download PDFInfo
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- CN100467666C CN100467666C CNB200410061665XA CN200410061665A CN100467666C CN 100467666 C CN100467666 C CN 100467666C CN B200410061665X A CNB200410061665X A CN B200410061665XA CN 200410061665 A CN200410061665 A CN 200410061665A CN 100467666 C CN100467666 C CN 100467666C
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Abstract
用于在基底上沉积一种或多种金属或金属合金薄膜的组合物和方法。该组合物包含催化剂，一种或多种载体颗粒和一种或多种水溶性或水分散性有机化合物。可以通过化学镀或电解沉积在该基底上沉积金属或金属合金。
Description
技术领域
本发明针对一种含水催化剂组合物和在基底上沉积超薄金属或金属合金层的方法。更具体地，本发明针对一种含水催化剂组合物和在基底上沉积超薄金属或金属合金层的方法，其中，该含水催化剂具有高表面积的颗粒。
背景技术
许多行业中技术人员希望在基底上覆盖或形成一个或多个金属或金属合金层，这些行业中使用了催化剂。这种催化剂用于金属或金属合金的化学沉积。化学沉积或化学镀是基于添加到沉积镀液中的化学还原剂的存在。这种化学制剂可向基底金属提供电子，基底金属将电子传递给镀液中带正电的金属离子从而将这些离子还原成金属，这与在电解或电镀液中电流将金属离子还原成金属的方式相同。
化学镀可产生若干理想的结果。使用电解电镀方法的技术人员通常难以在具有裂缝或孔洞的基底上沉积均匀厚度的金属层。这种属性在许多行业例如电子行业中是重要的，电子行业中印制电路或印制线路板要求在高纵横比的通孔中电镀均匀的金属沉积物。化学镀的其它性质和应用是可以在非导体上直接产生的沉积物，具有比电解电镀孔隙更少的沉积物，以及通常具有非常规的化学，力学或磁学性质(例如更高的硬度和抗磨损性)的沉积物。
化学镀的另一个属性是该过程是自动催化的而且沉积发生在催化表面。因此，需要一种催化剂。用于金属化学沉积中的催化剂根据待沉积的金属或金属合金和制品的用途在组成上变化很大。除印制线路板的制造以外，使用催化剂的化学镀也可用于多种装饰性制品的制造，和许多其它电子用途例如用于形成电磁干扰(EMI)和射频干扰(RFI)的屏蔽。
EMI辐射是由于从微波设备到家用计算机的多种形式的电子设备的运行而引起的。该辐射的发生是由于电子设备在60Hz至1000MHz以上的频率范围内发出“噪声”，并被其它设备或被作为天线的输电线的传导所吸收。EMI辐射可以干扰其它设备而且已知可以引起多种问题例如干扰警用移动无线电，通讯系统，科学测试设备和心脏起搏器。
限制电磁辐射的抑制(containment)的一种方法是使用EMI屏蔽罩来抑制该辐射。抑制需要特殊的屏蔽材料，元件，和结构，这些材料，元件和结构能阻止所产生的能量的泄漏并阻止其起到干扰源的作用。
作为被该屏蔽材料反射或吸收的结果，电场强度减弱的程度决定了电磁抑制的效果。屏蔽效率是由作为未屏蔽EMI发射与屏蔽EMI发射的比值的对数函数来计算，并以分贝(db)表示。由于其对数特性，对于给定波长或频率的电磁辐射，屏蔽效率提高30db代表涂层的屏蔽效率提高了1000％。例如，具有30db屏蔽效率的涂层可除去全部EMI辐射的99.9％。60db的涂层可除去全部EMI辐射的99.9999％。
商业上已使用了许多不同的屏蔽方法。一种方法涉及在电子设备的塑料外壳上涂覆金属涂层。这样的方法包括电镀沉积，喷涂例如通过电弧喷涂或喷涂涂料形式的金属，阴极溅射，化学金属喷镀和真空金属喷镀。金属涂层已包括铜，银，铬，镍，金和锌。这样的方法受到许多缺点的影响，例如宏观或微观裂缝，涂层剥落，有限的屏蔽效果，涂层中金属的氧化，热塑性基底的畸变，和昂贵的涂覆设备。
形成EMI屏蔽的更适合的方法是通过化学沉积在不导电的外壳材料上沉积金属。非导体如塑料的化学沉积涉及将部件浸入一系列的水性镀液中，这些镀液既对该部件的表面进行沉积调制又提供金属镀覆。常规的预处理步骤之后，将该部件浸入含贵金属例如胶体锡/钯的催化剂中，使非导电的表面催化以便沉积所需的镀覆金属。催化之后，将该部件浸入包含溶解金属的化学镀镀液中，该镀液与镀覆催化剂接触从而可引起该金属的镀层沉积在催化表面上。
虽然前述化学镀的催化剂和方法优于许多较早的用于处理EMI屏蔽问题的方法，但该化学镀方法不是有选择性的。将整个部件浸入该胶体催化剂溶液中，随后将该部件浸入金属电镀液中。结果是该金属既沉积在该非导体部件的外表面又沉积在部件的内表面。如果美观对于电子部件的市场重要的话，电子部件的外部金属涂覆外壳是不需要的。典型地，该行业对其外壳进行涂覆。这是耗时且浪费的步骤，特别是在经常使外壳形成所需颜色的情形中。因此，该行业开发了在非导电基底上选择性沉积金属的改良方法。
美国专利5,076,841公开了通过化学镀的方法在非导体上选择性沉积金属的方法。在该非导体上需要镀金属的部分喷涂或涂覆催化剂。在涂覆催化剂之前对该非导体不需要镀金属的部分进行掩盖。然后将该已催化或已上底涂层(primed)的非导体浸入适合的化学镀金属镀液。金属或金属合金便可沉积在该非导体上涂覆催化剂的选择性的部位上。
该’841专利的催化剂是贵金属的水合氧化物例如氧化银，氧化钯，和氧化铂。也可以使用铜的水合氧化物。该金属水合氧化物是以胶体形式沉积在惰性，不规则形状，胶状载体颗粒上，例如碳，各种类型的硅石包括合成煅烧硅石，合成沉淀硅石，化石源硅石(硅藻土)，碎屑状天然硅石(粉状或微粉化砂)；矾土；和颜料如二氧化钛。该胶体颗粒是不规则形状的而且具有锯齿边缘从而能穿透基底表面。载体颗粒的范围是约0.1至500微米且具有100至900m2/gm范围的表面积。该催化剂可以是水基或有机溶剂基的。该催化剂组合物中包含多种成膜树脂。
另外该催化组合物包含一种有机溶剂以便溶剂化或调整其上涂覆该催化剂的基底，从而促进催化剂与基底的结合或附着。基底的溶剂化允许催化剂对基底的渗透，然而，这种溶剂化作用可以在基底上引起表面缺陷。溶剂化可产生粗糙的表面因此沉积在基底上的金属层可形成锁钥结合(lock and key)。不规则的表面可以产生不均匀的金属层，这可产生不均匀的屏蔽。另外，使用溶剂溶胀会危害技术人员和环境，因为许多溶剂是有毒，致癌的且需要特殊且昂贵的处理程序。这种溶剂的实例包括丙酮，甲基乙基酮，甲苯，异丙醇，醚和醚乙酸酯和丙二醇烷基醚乙酸酯。因此，存在对能在非导电基底上形成金属层的改良组合物和方法的需求。
发明内容
本发明的组合物包含催化剂，一种或多种具有5至900nm的平均颗粒尺寸的载体，和一种或多种水溶性或水分散性有机化合物。本发明的组合物不使用有机溶剂，因为该水溶性或水分散性的有机化合物提供了充分的粘附方式使该组合物粘附至非导电基底。因此，当使用本组合物时可避免使用溶剂溶胀对非导电表面的粗化，因此从该组合物除去了许多潜在有害化合物。涂覆该催化剂的纳米尺寸的载体颗粒增加了催化剂的有效面积，因此允许在基底上设置连续的催化层。该催化层允许化学镀金属成核并穿过该催化层生长至基底，从而允许该基底与沉积金属产生电接触。
在另一个实施方案中本发明针对一种在基底上沉积金属或金属合金的方法，该方法包括将催化组合物涂覆至该基底，该催化组合物包含催化剂，一种或多种具有5至900nm的平均颗粒尺寸的载体，和一种或多种水溶性或水分散性有机化合物；和在带有该催化组合物的基底上沉积金属或金属合金。
在另一个实施方案中本发明针对一种包含具有金属或金属合金层基底的制品，该金属或金属合金层具有10微米或更小的厚度和50mΩ/cm2或更小的电阻。利用本发明的组合物和方法制造的制品可用于许多电子器件，例如用于包含嵌入无源元件(passive)如电阻和电容的印制电路或线路板，EMI屏蔽，RFI屏蔽，光电器件，用于ESD外罩的聚合物或陶瓷纤维，和许多制品上的装饰性部件。本发明的组合物和方法可以用于许多使用金属沉积的行业。
附图说明
图1是本发明的催化剂组合物上的铜沉积的2000倍SEM。
图2是显示ABS基底上铜成核的2000倍SEM。
图3是作为底涂层干膜重量的函数的铜厚度和表面电阻的曲线图。
图4是作为时间的函数的铜厚度和表面电阻的曲线图。
具体实施方式
正如在本说明书全文中所使用的下列缩写词具有如下含义，除非上下文另外明确指出：℃＝摄氏度；gm＝克；mg＝毫克；L＝升；mL＝毫升；A＝安培；m＝米；dm＝分米；mm＝毫米；μm＝微米；cm＝厘米；nm＝纳米；mΩ＝毫欧姆；cps＝厘泊；kV＝千伏特；SEM＝扫描电子显微照片；本说明书全文中可互换地使用术语“镀”和“沉积”；本说明书全文中可互换地使用术语“印制线路板”和“印制电路板”；本说明书全文中可互换地使用术语“薄膜”和“层”；在本发明的范围之内“水溶性”意思是化合物或聚合物在常态温度(1大气压下0℃以上至100℃)下在水中膨胀或溶解；在本发明的范围之内“水分散性”意思是在常温下化合物或聚合物在水中形成乳液，微乳液或悬浮液。所有的数值范围均包含端值且可以任何顺序结合，除非在逻辑上限制该数值范围至100％。
本发明的组合物包含催化金属的水合氧化物或氢氧化物形式的催化剂，并具有一种或多种惰性载体或填充物颗粒和一种或多种水溶性或水分散性的有机化合物，该催化剂分散于水性稀释剂中。认为惰性载体或填充物颗粒在金属或金属合金沉积过程中不参与该催化反应。本发明的组合物可形成水性浆料。
可以通过本领域中已知的任何适合的方法形成催化金属的水合氧化物或氢氧化物。例如，可以使用搅拌，pH调整和必要的加热获得金属盐的溶解，从而通过制备所需金属的盐的水溶液来形成金属水合氧化物。此后，允许或促使水解和成核反应以控制的速率在溶液中进行。该反应进行直到原位形成水合氧化物。允许该水解反应继续进行直到超过该溶液的溶解度极限从而形成分离的分散相。这种方法对于本领域的技术人员是熟知的。
可以使用可形成水合氧化物或氢氧化物且具有催化性质的任何适合的金属来实施本发明。适合金属的实例包括银，金，铂，钯，铟，铷，钌，铑，锇，和铱。其它催化金属的实例包括铜，钴，镍和铁(以三价铁的氧化态)。典型的催化金属包括银，金，钯，和铂。更典型地，银，金和钯是贵金属的选择，且最典型地，银是催化金属的选择。前面的金属列表并不是穷尽的，可以使用能形成水合氧化物或氢氧化物且对于待沉积的金属或金属合金具有催化性质的任何金属来实施本发明。
金属催化剂的选择取决于有待于在基底上沉积的金属或金属合金。在金属或金属合金的化学镀中，该催化金属的氧化/还原电位比待沉积的金属或金属合金具有更大的电正性(“贵”)。例如，据报道下列金属对铜，铜合金，铅，铅合金，镍，镍合金，和钴的沉积具有催化作用：银，碲，铂，铊，钒，金，锗，硒，铁，锡和钯，且典型使用金，钯，铂和银。更典型地使用银或金来沉积铜或铜合金。最典型地使用银来沉积铜或铜合金。
将以金属的水合氧化物或金属氢氧化物形式的催化剂与一种或多种惰性载体混合形成水性浆料。所使用的惰性载体可以是具有一定平均颗粒直径的任何适合的水不溶性化合物，该平均颗粒直径例如5nm至900nm，或例如20nm至600nm，或50nm至500nm。虽然不受理论限制，作为其水合氧化物或氢氧化物的催化金属吸附在该惰性载体颗粒上，因此增加了该催化剂的有效催化面积，相比具有更大平均尺寸的载体颗粒，这允许该金属催化剂与镀液产生更紧密的接触。认为这种紧密的接触能形成超薄的催化薄膜。这种催化薄膜当为干态时其厚度范围可以是10nm至10微米或者例如50nm至10微米。认为金属离子以金属方式沉积是穿过该催化组合物成核并与基底形成电接触，从而在基底上形成连续的金属或金属合金薄膜。这种成核作用在许多应用中是非常有用的，例如当构造印制线路板上的迹线时，对于片式电容器，电容器或电子元件的焊料盘，通常其中需要电接触。
适合的载体包括但不限于，各种水不溶性盐和无机物或它们的混合物。这种适合的惰性载体的实例包括但不限于，多价阳离子和阴离子对的化合物，金属氧化物，硅酸盐，氧化硅或它们的混合物。该惰性载体在本发明的浆料中的含量是该水合氧化物或氢氧化物化合物中的催化金属重量的例如30倍至更多，或例如是该水合氧化物或氢氧化物化合物中的催化金属重量的55倍至330倍，或例如是该催化金属重量的60至300倍。超细惰性载体颗粒的表面积的范围可以是1000m2/gm至8000m2/gm或例如1100m2/gm至6000m2/gm或例如15m2/gm至3000m2/gm。
适合的多价阳离子和阴离子对的化合物的实例包括但不限于，钡，钙，镁，和锰不溶于水的盐，例如硫酸钡，氢氧化钙，氢氧化镁，氢氧化锰，或它们的混合物。更典型地使用钡盐和钙盐例如硫酸钡或氢氧化钙或它们的化合物。最典型使用例如硫酸钡的钡盐。
适合的金属氧化物的实例包括但不限于，氧化铁，氧化铝，二氧化钛，碳酸钙，氧化锌，氧化镁，氧化铯，氧化铬，氧化铪，氧化锆，或它们的混合物。更典型地使用氧化铝，碳酸钙，氧化锌，或它们的混合物。氧化铝和碳酸钙或它们的混合物是最典型使用的氧化物。
适合的硅酸盐的实例包括但不限于，宝石(除金刚石以外)，绿宝石，石棉，粘土，长石，云母，滑石，沸石(天然和合成沸石)或它们的混合物。天然沸石的实例包括方沸石，菱沸石，片沸石，钠沸石，辉沸石和杆沸石(thomosonite)。沸石，粘土，云母或它们的混合物石更典型使用的硅酸盐。
可以在本发明的浆料中使用任何适合的水溶性或水分散性有机化合物。认为该有机化合物是作为该催化剂和载体颗粒的粘结剂。认为该有机化合物会与基底形成结合。虽然不受理论限制，认为该有机化合物是通过氢键，离子键，共价键，范德华力或它们的组合与基底结合的。也可能包括其它类型的化学结合和静电力。该有机化合物与基底的结合能力省去了对用来膨胀或粗糙化基底表面的溶剂的需要。因此，许多不合要求的对技术人员有毒性和对环境有危害的溶剂被排除在本发明的组合物之外。
适合的水溶性或水分散性有机化合物的实例包括但不限于，聚氨酯和环氧化物或它们的混合物。其它适合的水溶性或水分散性有机化合物包括但不限于，聚合物例如丙烯酸的均聚物或共聚物，乳酸的均聚物或共聚物，聚酰胺，聚酯，醇酸树脂，乙烯与丙烯酸酯或乙酸乙烯酯的共聚物，氯化或未氯化的氯乙烯均聚物或共聚物，乙酸乙烯酯或丙酸乙烯酯，环化或氯化橡胶，硝酸纤维素，乙基或羟乙基纤维，香豆素-茚树脂，萜树脂，聚乙烯醇缩醛树脂，纤维素酯例如乙酰丁酸纤维素和乙酰丙酸纤维素，虫胶，聚烷基二醇，淀粉，碳水化合物和其它天然树脂中的一种或其组合。另外，也可以使用微细尺寸的离子交换材料作为分散剂。例如适合的离子交换树脂包括那些具有烯，苯乙烯，丙烯酸和乙烯基主链的材料，其中包含季胺基，氨基乙酸，羧基和磺酸基官能团。这样的有机化合物构成该催化组合物的5％重量比至60％重量比或例如10％重量比至45％重量比或例如20％重量比至35％重量比的。
适合的聚氨酯的实例包括但不限于，水基聚氨酯组合物，这种组合物可以是聚氨酯的离子性水分散体，该分散体包含离子或亲水官能团以及主链中疏水的聚烯烃链节。该分散体可以是阳离子或阴离子的。这样的水性分散体在本领域内是众所周知的且可以从市场上买到而且可以通过文献中公开的多种方法制得。
一个制备水基聚氨酯-聚烯烃分散体的方法的实施例包括，通过在预聚物链中包含有效数量的水分散侧羧基，或阳离子盐基团或它们的组合使异氰酸酯封端(terminated)的聚氨酯预聚物变得可水分散。典型地，侧羧基或阳离子基团构成预聚物的0.5％重量比至10％重量比。形成这种预聚物的方法对于本领域的技术人员是熟知的。美国专利4,644,030中公开了制备这种预聚物和水基聚氨酯-聚烯烃分散体的方法。可选地，该预聚物可以没有羧基或阳离子盐基团，在这种情形中，该预聚物通过分散剂如一种或多种非离子表面活性剂的帮助在水中分散。
可以通过本领域中已知的任何适合方法来制备异氰酸酯封端的聚氨酯预聚物。文献中公开了多种方法。一个制备异氰酸酯封端的聚氨酯预聚物的方法的实施例包括使每一分子包含平均至少2个活性氢原子的有机材料如二醇或聚酯型多元醇与化学计量过剩的有机二异氰酸酯反应。本领域中适合于制备异氰酸酯封端聚氨酯预聚物的许多有机二异氰酸酯是众所周知的而且许多可以从市场上买到。该有机材料可以包含至少一个非反应性的侧羧基，该侧羧基可以是盐的形式或在预聚物形成期间或之后与适当的碱性材料中和成盐的形式。这种含羧基的反应物的实例是α，α-二羟甲基(C2至C10)链烷酸，例如2，2-二羟甲基丙酸。
除聚酯型多元醇以外，也可以使用其它多元醇或它们的混合物，其中包括但不限于聚已内酯，聚碳酸酯，聚丁二烯树脂(羟基封端的丁二烯均聚物)，基于环氧乙烷、环氧丙烷和四氢呋喃的聚醚，或它们的混合物。
适合的聚异氰酸酯的实例包括但不限于，亚甲基二异氰酸环己烷，亚乙基二异氰酸酯，亚丙基二异氰酸酯，亚丁基-1，3-二异氰酸酯，1，6-六亚甲基二异氰酸酯，2，2，4-三甲基-六亚甲基二异氰酸酯，2，4-二甲基-6-乙基亚辛基二异氰酸酯，亚环己基二异氰酸酯，亚环戊基二异氰酸酯，1，4-二异氰酸甲基-环己烷，1，3-二异氰酸乙基-环已烷，甲代亚苯基二异氰酸酯，3，3，5-三甲基-1-异氰酸-5-异氰酸甲基-环己烷，2-亚丁基-1，4-二异氰酸酯，异佛尔酮二异氰酸酯，1，6-六亚甲基二异氰酸酯缩二脲，1，6-六亚甲基二异氰酸酯三聚体，异佛尔酮二异氰酸酯三聚体，被以1，6-六亚甲基二异氰酸酯三聚体封端的2-羟乙基甲基丙烯酸酯封端的双酚A二甲基丙烯酸酯，或它们的混合物。
许多前述的二异氰酸酯可以由Lyondell(位于Houston，TX)或Bayer(位于Pittsburgh，PA)购得。可从市场上购得的聚异氰酸酯另外的实例包括MONDUR CB(3摩尔甲苯二异氰酸酯与1摩尔三羟甲基丙烷的加合物，Mobay Chem.)，DESMODUR-N(1，6-己烷二异氰酸酯的三官能缩二脲，Mobay Chem.)，ISONATE143L(聚二异氰酸酯二苯基异氰酸酯，Upjohn)。
可选地，适当比例的该有机活性含氢反应物材料或该有机异氰酸酯反应物材料可包含至少一个烯键式不饱和基，这个比例足以在该聚氨酯聚合物中包含0.5％重量比至60％重量比或更多源自于这种包含不饱和基的反应物的单元。对于聚合聚氨酯分散体中液态惰性单体材料，当经历随后的原位烯基加成聚合条件时这种基团可提供交联的能力。可以对用于这个目的的有机反应物材料以任何适合的形式或连接具有这些不饱和基，例如醚，酯，或碳-碳连接。这种含活性氢材料的实例包括但不限于，甘油单烯丙基醚，甘油甲基丙烯酸酯，N，N-二羟甲基-1丁烯，羟基封端聚(丁二烯)，丙烯酸羟乙酯，丙烯酸羟丙酯，或它们的混合物。这种含异氰酸酯的反应物的实例包括单不限于，2-甲基-5-乙烯基苯-1，4-二异氰酸酯和1-(α-异氰酸-α-甲基)乙基-3(α-甲基)乙烯基苯(m-TMI，Amer.Cyanamid)。烯不饱和可以出现在沿该聚氨酯链的侧基中，端基中，或作为链内部的链节或它们的任何组合。
可以在惰性液态可聚合烯键式不饱和单体材料的存在下进行异氰酸酯封端的聚氨酯预聚物的合成。这种单体材料在本领域中是众所周知的，可产生聚烯烃(包括取代聚烯烃)或“乙烯基加成聚合物”，即通过一种单体或多种单体的混合物的加成聚合，该单体包含一种或多种内部终端可聚合烯键式不饱和基团。这种类型的聚合被称作悬浮聚合而且可以在自由基乙烯基聚合催化剂或氧化还原体系的存在下进行，其中该单体在烯键式双键处互相加合从而产生主要由碳原子组成的聚合物链。
单体材料在形成预聚物的反应条件下典型为液态。该单体材料起溶剂，稀释剂或载体介质的作用。可选地，可以向该反应介质中添加有机溶剂。适合的单体的实例包括但不限于，可聚合烯键式不饱和烃，羧酸，酯和醚，例如丙烯酸和甲基丙烯酸的游离酸和酯，乙烯醇的酯和醚，和苯乙烯。示例性实例包括丁二烯，异戊二烯，苯乙烯和取代苯乙烯，丙烯酸、甲基丙烯酸和顺丁烯二酸的游离的酸和较低烷基(C1至C6)酯，乙酸乙烯酯，丁酸酯，丙烯酸酯和甲基丙稀酸酯，己二醇，二丙烯酸酯，乙烯基甲基、丙基和丁基醚，二乙烯醚，乙烯硫醚，三羟甲基丙烷三丙烯酸酯，2-丁烷-1，4-二醇二丙烯酸酯，或它们的混合物。
前述的适合单体材料的示例性实例既包含单烯键式又包含多烯键式的不饱和材料，后者可在乙烯基加成聚合条件下提供交联的能力。多不饱和材料包括但不限于，双烯键式不饱和材料，且使用时可以以较少数量与单烯键式不饱和材料混合，即以该可聚合烯键式不饱和单体的1至小于50％重量比范围的数量。该单体材料可以由一种这样的单烯键式不饱和材料或它们的混合物组成。
在该预聚物链中除包含侧阴离子羧酸盐基团以外，另外可以通过在链中包含相当比例(即有效数量)的侧水分散阳离子盐基来提供所需的水分散性。这样的阳离子盐基团包括单不限于，季铵基，可加入的(insertable)，例如通过使用适当比例的包含叔胺或烷基卤化物的含活性氢有机反应物并随后通过分别与烷基卤化物或叔胺反应使这些基团季铵化。预聚物中叔胺基的有机或无机酸盐也是有效的水分散阳离子盐基。
可以对该预聚物进行常规的链延长，随后与可聚合烯键式不饱和单体材料进行乙烯基加成聚合从而使该单体材料原位聚合。这种方法在本领域中是众所周知的。适合的增链剂的实例是可与异氰酸酯基反应的多胺例如脂肪族多胺。20％重量比至60％重量比范围的不变固体含量代表聚合的完成。当为阴离子型时该水性分散体具有7至9.5的pH，而当为阳离子型时具有2至10的pH。在18℃至25℃下粘度的范围是25至200cps。
适合的水分散或水溶性环氧树脂的实例包括但不限于，由多种酚制成的环氧树脂，酚例如双酚A，双酚F，双酚S，双酚AD，对苯二酚，间苯二酚，甲基间苯二酚，双酚，四甲基双酚，二羟基萘，四溴双酚A，二羟基二苯醚，二羟基二苯甲酮，二羟基二苯基砜酚酚醛清漆树脂，甲酚酚醛清漆树脂，双酚A酚醛清漆树脂，双环戊二烯苯酚树脂，萜烯酚树脂，苯酚芳烷基树脂，萘酚酚醛清漆树脂或溴化苯酚酚醛清漆树脂，或多种酚类化合物例如通过多种酚和多种醛缩聚反应得到的多元酚树脂，例如羟基苯甲醛，巴豆醛或乙二醛，和表卤代醇。此外，例如由各种胺化合物如二氨基二苯甲烷，氨基苯酚或二甲苯二胺，和表卤代醇制成的环氧树脂。也可以使用由各种羧酸制成的环氧树脂，羧酸例如甲基六羟基邻苯二甲酸或二聚体酸(dimmer acid)，和表卤代醇。可以使用不同环氧树脂的混合物。许多前述的环氧树脂可以从市场上购得或可以通过文献中公开的方法进行制备。
典型地，使用源自于双酚A，双酚S，双酚F的环氧树脂或酚醛清漆树脂，或通过双酚A和表卤代醇反应得到的环氧树脂，或它们的混合物。更典型地，使用源自双酚A的环氧树脂，酚醛清漆树脂或通过双酚A和表卤代醇反应得到的环氧树脂，或它们的混合物。最典型地，使用源自双酚A的环氧树脂。
可选地，只要不干扰金属沉积的催化作用，可以向本发明的催化组合物中加入表面活性剂。适合的表面活性剂包括阴离子型，阳离子型，两性型，非离子型或它们的混合物。以常规数量包含表面活性剂。适合的非离子表面活性剂的实例是BASF以商标
和出售的环氧乙烷/环氧丙烷共聚物。
可选地，可以向该催化组合物中加入聚结剂。可以向该催化组合物中加入任何适合的聚结剂。适合的聚结剂的实例包括但不限于，乙二醇和乙二醇醚或它们的混合物。以常规数量使用聚结剂。
可选地，本发明的催化剂组合物中可以包含附加的附着力促进有机化合物。这种附着力促进组分包括但不限于，三嗪，酚，醛，丙烯酸酯，咪唑，丙烯酰胺，苯并三唑，丙二酸盐(或酯)，乙酰乙酸(或酯)，氯化聚烯烃，氨基甲酸乙酯如Eastman Chemical AP 440-1，环氧丁烯，丙烯酸缩水甘油酯，烷氧基硅烷化合物如β-(3，4-环氧环己基)乙基三乙氧基硅烷，二(三甲氧基甲硅烷基丙基)胺，γ-氨丙基三甲氧基硅烷和氨烷基硅氧烷。
可以通过本领域中已知的任何适合的方法将本发明的催化组合物的成分相互混合。一种方法是利用高剪切分散使催化剂覆盖该超细惰性填充物，然后在低剪切搅拌下向该填充物中加入树脂。适合的剪切速率完全在本领域的技术人员的能力范围之内而且可以进行少量试验以确定对于给定组成的最优剪切速率。可以在如15℃至35℃的温度下进行混合，更典型为18℃至25℃。组分的混合可得到一种水性浆料，可以通过本领域中已知的任何适合的方法将该浆料涂覆至基底。例如，可以通过将基底浸入该浆料或用适合的喷涂设备如喷漆枪(air gun)将浆料喷涂在基底上从而涂覆该浆料。刷涂是涂覆该催化组合物的方法的另一个实例。可选地，可以在涂覆催化组合物之前在基底上施用一个具有所需图案的掩模或工具，以便可以将催化组合物选择性的沉积在该基底上，从而可以在镀覆过程中将金属或金属合金薄膜沉积选择性地沉积在基底上。
在基底表面上形成了0.5至30微米的湿膜，或例如1至20微米或例如5至15微米的湿膜。然后使该湿膜干燥。可以通过任何适合的方法进行干燥。一个实例是将该薄膜在空气中干燥。在空气中干燥可持续20分钟至2小时，更典型为60分钟至90分钟。然而，根据干燥室的环境条件干燥时间可以更短或更长。干膜重量的范围可以是0.5gm/m2至10gm/m2，或例如1gm/m2至5gm/m2。
可以将本发明的催化剂组合物涂覆到任何适合的基底上。这种基底的实例包括但不限于，非导体例如塑料，该塑料可以是热塑性或者热固性的树脂。热塑性树脂的实例包括但不限于，通用塑料如PE(聚乙烯)，PVC(聚氯乙烯)，PS(聚苯乙烯)，PP(聚丙稀)，ABS(丙烯腈-丁二烯-苯乙烯)，AS(丙烯腈-苯乙烯)，PMMA(聚甲基丙烯酸甲酯)，PVA(聚乙酸乙烯酯)，PVDC(聚偏氯乙烯)，PPO(聚苯醚)，和PET(聚对苯二甲酸乙二醇酯)；通用工程塑料例如PA(聚酰胺)，POM(聚缩醛)，PC(聚碳酸酯)；PPE(改性聚苯醚)，PBT(聚对苯二酸丁二醇酯)，GE-PET(玻璃纤维增强聚对苯二甲酸乙二醇酯)和UHPE(超高分子量聚乙烯)；和超级工程塑料例如PSF(聚砜)，PES(聚醚砜)，PPS(聚苯硫醚)，PAR(多芳基化合物)，PAI(聚酰胺酰亚胺)，PEEK(聚醚醚酮)，PI(聚酰亚胺)和氟碳树脂。示例性的热固性树脂包括但不限于，酚醛树脂，脲醛树脂，三聚氰胺树脂，醇酸树脂，不饱和聚酯，环氧树脂，邻苯二甲酸二烯丙酯聚合物，聚氨酯和有机硅树脂。
可以在本发明的实施中用作基底的其它材料包括但不限于，橡胶，陶瓷通常包括陶瓷纤维，硅酸盐，玻璃包括非硅酸盐玻璃和玻璃纤维，木材，纤维增强塑料，织物，和纸。
该催化组合物或底涂层在基底上干燥以后，使用任何适合的固化程序对该干燥底涂层进行固化。许多这样的程序在本领域中是众所周知的。一种方法是将具有干燥底涂层的基底放置于普通烘箱中然后加热至所需的固化温度并持续适当时间。例如，可以在50℃至120℃的温度下进行固化，或者在例如70℃至100℃下进行固化。用于固化的时间段的范围可以是5分钟至90分钟。可以向该组合物中加入固化剂。可以使用任何适合的固化剂。适合的固化剂的实例是胺类固化剂例如可从市场上购得的
AR419，咪唑类固化剂例如1-乙基-4甲基-1H-咪唑，锡基固化剂例如二月桂酸二丁基锡，硫醇化二丁锡，二丁基二(十二烷基硫)锡烷等，这些固化剂在本领域中是众所周知的。
固化以后，可以通过本领域中已知的任何适合方法在该催化组合物上沉积金属或金属合金。如果使用图样工具或掩模涂覆该催化剂组合物，可以选择性的沉积该金属或金属合金。典型地，通过化学金属沉积使金属沉积在具有底涂层的基底上。使用化学镀液对具有已固化催化剂底涂层的基底进行喷涂或者将该基底浸入该镀液并保持足够的时间以便在基底上沉积连续的金属或金属合金薄膜。这种程序在金属电镀工业中是众所周知的。
任何可以通过化学沉积来沉积的金属都可以用来实施本发明。可以使用该催化剂组合物进行化学沉积的适合金属的实例包括但不限于，铜，镍，钴，铬，铁，锡，铅，铝，镁，铬，铍，钨，碲，钨，钼，硼，铊，钒，钛，锗，硒，锌，和它们的合金。可以用来实施本发明的合金的实例包括但不限于，铜/镍，铜/银，铜/锡，铜/铋，锡/银，锡/铅，镍/钒，镍/硼，镍/磷，钴/磷，和镍/钴/磷。可以使用该催化剂组合物进行沉积的其它金属包括但不限于，金，银，铂，钯，铟，铑，钌，铱，锇，和它们的合金。典型地，使用该催化剂组合物来沉积铜，镍，钴，铅，金，银，铂，钯和它们的合金，更典型用来沉积铜，镍，金，铂，钯和它们的合金。最典型地使用该催化剂组合物来沉积铜和铜合金。
用于在基底上沉积金属或金属合金的化学镀镀液在本领域中是众所周知的且在组成上可以变化。例如化学金属镀液可以包含一种或多种稀释剂可溶金属盐作为待沉积的金属或金属合金源，配位剂，螯合剂，还原剂，稳定剂，和光亮剂。正如本领域的技术人员所熟知的，这种化学镀液中还可以包含其它成分。
使用该催化组合物沉积的连续金属或金属合金薄膜可以在厚度上有所变化，例如10nm至10微米或例如0.1微米至5微米，或例如0.5微米至2微米。
该金属或金属合金薄膜的表面电阻可以有所变化。这样的表面电阻可以是50mΩ/cm2或更少，或例如0.05mΩ/cm2至30mΩ/cm2，或例如1mΩ/cm2至15mΩ/cm2。
图1是ABS基底的横截面的2000倍SEM，该ABS基底上涂覆有本发明的催化剂组合物(沿SEM长度方向不规则地隆起和延伸)和包覆在该催化组合物上的铜金属的薄层(和底涂层的暗色相和粗糙的表面外观形成对比的亮色薄膜)。所使用的催化剂是水合氧化银。没有发现可见的穿透该底涂层的孔或缺陷。通过化学沉积的该铜镀层在催化剂底涂层上形成了连续的镀层。
图2是ABS基底的横截面的2000倍SEM，该ABS基底(亮色区域下方的黑色区域)上具有本发明的水合氧化银催化剂组合物和该催化剂组合物上的连续铜金属层(靠近SEM中央的最明显隆起物但在铜镀层下沿该SEM的长度方向延伸)。该连续的铜金属层是通过化学镀沉积在该催化剂组合物上。该隆起另一侧的连续铜镀层已经通过该催化剂组合物在该ABS基底上成核并与该基底形成电接触。
该金属或金属合金薄膜的表面硬度可能会变化。如通过ASTM D3363所测得的典型的表面硬度的范围是6B至6H，且更典型地具有更高的硬度(3H或更高)以便在电镀之后的组装过程中保护金属或金属合金镀层的完整，该组装过程中可能发生对该镀层连续性的破坏。这种硬度对于EMT屏蔽需要的，因为对于EMI屏蔽该情形中金属中的孔或裂缝可以危害该金属层的屏蔽性能。ASTM D3363程序在本领域中是众所周知的并且硬度是使用具有不同石墨硬度的铅笔来测试的。
使用该催化剂组合物和方法制造的物品可以用于许多电子设备中，例如包含嵌入无源元件如电阻和电容的印制电路或线路板，EMI屏蔽，RFI屏蔽，光电器件，用于ESD外罩的聚合物或陶瓷纤维，和许多物品上的装饰部件。
可选地，通过这里公开的催化剂和方法沉积的金属和金属合金薄膜可以进一步与一种或多种另外的金属或金属合金金属化。这种另外的金属层或金属合金层的厚度范围可以是0.5微米至更高，或例如10微米至20微米。可以通过化学金属沉积或通过电解沉积这种另外的金属或金属合金层。化学金属沉积也包括浸入金属化法。这种另外的金属化方法在本领域中是众所周知的。
电解沉积包括DC(直流)电镀和脉冲(正向和反向)电镀，以及使用它们的组合的电镀方法。电流密度可以根据沉积的金属或金属合金而变化，这对本领域的技术人员是熟知的。例如可以用来电解沉积许多金属的适当的电流密度范围是0.5A/dm2至100A/dm2，或例如5A/dm2至30A/dm2。可以电解沉积的金属的实例包括但不限于，铜，镍，钴，锡，铋，贵金属和它们的合金。
可以沉积的化学镀金属包括但不限于，铜，镍，钴，铬，镁，铝，钨，碲，铍，铋，铅，硼，铊，钒，钛，锗，硒，铁，锡和它们的合金。其它金属包括但不限于，金，银，钯，铂，铑，钌，锇，铱，和它们的合金。可以通过浸入工艺沉积的适当金属的实例包括但不限于，金和银。
引入下列实施例以便对本发明的一些实施方案进行举例说明。
实施例1
本发明的催化底涂层
通过在室温下(18℃至20℃)混合50gm硝酸银(AgNO3)与10gm氢氧化钠(NaOH)制备水合氢氧化银的母液，这形成了褐色的水合氧化银沉淀物。使该沉淀物沉淀下来然后用足量去离子水使pH达到9。
然后将0.1gm该水合氧化银加入到一含水组合物中，该组合物包含2.5gm平均颗粒尺寸为300nm的硫酸钡(BaSO4)，0.25gm平均颗粒尺寸为550nm的氧化铁(Fe2O3)和8.75gm水。在使用搅拌装置产生的高剪切搅拌下将该固体在水中分散。然后加入1.2gm平均分子量为1300当量的双酚A环氧树脂，并在使用搅拌装置产生的低剪切搅拌下混合直到形成均匀的浆料。
将包含0.33gm分子量为284当量的胺类固化剂，0.1gm丙二醇甲基醚和1gm水的溶液与包含水合氧化银的该浆料混合直到所有的成分形成均匀浆料。惰性填充物与金属催化剂的比值为30比1。
实施例2
本发明的催化底涂层
将0.045gm来自实施例1的原料水合氧化银加入一含水组合物中，该组合物包含2.5gm平均颗粒尺寸为300nm的硫酸钡(BaSO4)，0.15gm平均颗粒尺寸为550nm的氧化铁(Fe2O3)，0.5gm二(乙二醇)丁基醚，和9gm水。使用高剪切搅动使固体在水中分散。使用低剪切搅动向该浆料中加入0.8gm主链中包含疏水链节的水分散聚氨酯树脂和0.01gm烷氧基硅烷交联剂。惰性填充物与金属催化剂的比值为65比1。
实施例3
本发明的催化底涂层
将0.045gm来自实施例1的原料水合氧化银加入一含水组合物中，该组合物包含3.6gm平均颗粒尺寸为300nm的硫酸钡(BaSO4)，0.25gm平均颗粒尺寸为550nm的氧化铁(Fe2O3)，0.5gm二(乙二醇)丁基醚，和6gm水。使用高剪切搅动使固体在水中分散。然后使用低剪切搅动向该浆料中加入0.8gm主链中包含疏水链节的水分散聚氨酯树脂。惰性填充物与金属催化剂的比值为94比1。
实施例4
本发明的催化底涂层
将0.043gm来自实施例1的原料水合氧化银加入一含水组合物中，该组合物包含4.5gm平均颗粒尺寸为550nm的氧化铁(Fe2O3)，0.5gm二(乙二醇)丁基醚，和6gm水。使用高剪切搅动使固体在水中分散。使用低剪切搅动向该浆料中加入0.8gm主链中包含疏水链节的水分散聚氨酯树脂和0.01gm烷氧基硅烷交联剂。惰性填充物与金属催化剂的比值为114比1。
实施例5
对比催化剂底涂层
通过在100mL水中溶解硝酸银制备重量百分比浓度为0.25的硝酸银(AgNO3)溶液，并用氢氧化钠(NaOH)将pH提高至7。然后将其pH提高到8至9的范围以形成银的水合氧化物沉淀。然后对该沉淀物进行过滤并用去离子水冲洗。
将4gm该水合氧化银与19gm氧化硅(Type OK 412)和溶剂搅拌混合。所用的溶剂为35gm异丙醇，40gm乙酸乙酯和23克丙酮。然后在搅拌和超声波搅拌下加入346mL清漆(购自Bee chemicals的L123聚碳酸酯清漆)以分散所有的团块。惰性填充物与金属催化剂的比值为5.2比1。
实施例6
对比测试
将本发明范围内的四个催化剂组成(实施例1至4)与本发明范围之外的对照催化剂组成(实施例5)进行对比。对五种不同聚合物基底的6个试样进行了测试。下表中公开了所用聚合物的类型和催化剂的平均性能如沉积在各个基底上的铜的粘附力(Adh.)和硬度(Hard.)。
通过喷漆枪将这些组成涂覆至该试样从而形成14微米厚度的湿膜(实施例1至4)并涂覆对照样形成厚度为90微米的湿膜。将这些试样在20℃下空气干燥90分钟然后在普通对流烘箱中在65℃下固化30分钟。
然后使用市售的化学镀铜电镀系统(来自Shipley Company，L.L.C.的
80)对每个试样沉积铜。该化学铜沉积在43℃下持续45分钟后完成从而沉积1.5微米厚的铜层。对于所有的试样，表面电阻率小于10mΩ/cm2。
根据ASTM3359对粘附力进行测试，其中在该试样上划出间距2mm的交叉图案并将
胶带粘在所划标记上然后撕开并查看是否有任何所划的涂层脱落。根据被胶带除去的材料的数量，给出5B至1B的等级，其中5B表示无脱落而1B具有35至65％的脱落。从上表中可以看出在ABS，ABS/PC和PC上组成1至4与对照样相当，组成1和2表明可粘附至Nylon和而对照样(实施例5)根本不粘附。
根据ASTM3363对各个基底上铜薄膜的硬度进行测试，其中使用6B(最软)至6H(最硬)不同硬度的铅笔以固定角度在固定的载荷下划过电镀的表面。所用不引起薄膜破裂的最硬铅笔便是该涂层的“硬度”。该测试是粘附/磨损测试从而不但测试薄膜的硬度而且测试薄膜的粘附性和抗损伤性。如表中所示，所有通过本发明的催化剂组合物形成的电镀薄膜均表现出比对照样(实施例5)显著更高的硬度(9铅笔硬度)。
实施例7
铜薄膜表面电阻率
通过在一升水中混入50gm硝酸银来制备水合氧化银然后混入足够数量的氢氧化钠使该混合物的pH达到9以形成褐色的水合氧化银沉淀。
将该水合氧化银过滤并用去离子水冲洗。然后将0.045gm这种水合氧化银加入到一含水组合物中，该组合物包含2.5gm平均颗粒尺寸为300nm的硫酸钡(BaSO4)，0.15gm平均颗粒尺寸为550nm的氧化铁(Fe2O3)，0.5gm二(乙二醇)丁基醚，和9gm水。使用高剪切搅拌将该固体在水中分散。然后使用低剪切搅动加入0.8gm主链中包含疏水链节的水分散聚氨酯树脂。
使用喷漆枪用该水合氧化银催化剂涂覆六个ABS试样以形成1gm/m2，2.5gm/m2，3.5gm/m2，5.5gm/m2，6.5gm/m2和8gm/m2的干催化剂涂层。在普通对流烘箱中在65℃下固化30分钟。然后使用Coppermerse
80铜化学镀镀液在每个试样上电镀1.5微米厚的铜薄膜。电镀在40℃下进行并持续40分钟从而在每个试样上形成1.5微米厚的薄膜。
使用喷漆枪用该水合氧化银催化剂涂覆第二批六个ABS试样以形成1gm/m2，2gm/m2，3gm/m2，4gm/m2，6.5gm/m2和8.5gm/m2的干催化剂涂层。在普通对流烘箱中在65℃下固化30分钟。然后使用
80铜化学镀镀液在每个试样上电镀1.5微米厚的铜薄膜。电镀在38℃下进行并持续40分钟。
利用Versatronic R-100电阻计用4电极探针系统来测量这十二个试样中每个试样的表面电阻率。图3显示了铜厚度和表面电阻率相对于试样上催化剂干重量的曲线图。得到了4mΩ/cm2的平均表面电阻率。图3中所示的数据显示3.5gm/m2以上的涂层重量没有显著提高表面电阻率，这表明在3.5gm/m2的涂层重量下已存在足够的催化剂覆盖该基底表面。
图4显示了铜厚度和表面电阻率相对于时间的曲线图。使用上述的催化剂和
80化学镀镀液在一个ABS基底上电镀铜。电镀在43℃下进行。该干燥催化剂层为4gm/m2。在0，9，19，25，32，40，50，55和65分钟的时间间隔处测量铜的厚度和表面电阻率。如图4所示使用本发明的催化剂对于1微米的铜厚度得到了5mΩ/cm2的表面电阻率。对于大于1微米至2.5微米的铜薄膜厚度得到了小于5mΩ/cm2的表面电阻率。
实施例8
钯的水合氧化物催化剂
在100mL水中溶解1％重量比的氯化钯溶液。搅拌该溶液直到氯化钯溶解。向该溶液中加入足量氢氧化钠来提供3的pH以便形成褐色的水合物氧化物的分散体。然后过滤该分散体并用去离子水冲洗。
然后使用声波混合器将0.1gm钯的水合氧化物与8gm平均颗粒直径为500nm的硫酸钡，和2gm主链中包含疏水链节的聚氨酯的阳离子分散体混合。向该分散体中加入足量水使体积达到500mL。搅拌该分散体从以形成浆料。可以将该催化剂的底涂层涂敷到有待于从化学镀金属镀液中沉积金属的聚合物或陶瓷基底上。该成品上的金属镀层可以起到EMI或RFI屏蔽的作用。
实施例9
铂的水合氧化物催化剂
80℃下在100mL稀盐酸中溶解相应的盐从而形成1％重量比的二氯化亚铂溶液。在室温下冷却之后，用氢氧化钠将该溶液的pH提高至3从而形成铂的水合氧化物的沉淀物。对该沉淀物进行过滤并用去离子水冲洗。
然后将0.1gm该沉淀物与5gm平均颗粒尺寸为50nm的氧化铁，5gm平均颗粒尺寸为120nm的硫酸钡和3gm主链中含疏水聚烯烃链节的聚氨酯混合。使用高剪切混合设备搅拌该组合物以形成浆料。
可以将该催化剂的底涂层涂敷到有待于从化学镀金属镀液中沉积金属的聚合物或陶瓷基底上。基底上形成的该金属薄膜可以起到EMI屏蔽的作用。
实施例10
铜的水合氧化物催化剂
通过在100mL水中溶解氯化铜从而形成1％重量比的氯化铜溶液。然后将该溶液加热到70℃并用氢氧化钠将pH调节至6。形成了铜的水合氧化物的分散体。
将0.2gm铜的水合氧化物与15gm平均尺寸为400nm的方沸石颗粒连同2gm双酚S型环氧树脂混合，并加入足量的水使体积达1升。使用高剪切搅拌设备进行混合。
可以使用该浆料作为催化剂底涂层，可利用该催化剂底涂层在聚合物或陶瓷基底上使用化学金属电镀液沉积金属薄膜。对于各种电子制品，该金属薄膜可以起到RFI屏蔽的作用。
实施例11
金的水合氧化物催化剂
在100mL水中溶解氯化金从而形成1％重量比的氯化金溶液。用足量的氢氧化钠在2天时间内将该溶液的pH提高到5。在提高pH期间，对该溶液进行连续不断的搅拌并加热至40℃以形成褐色的金的水合氧化物沉淀。将该沉淀物过滤并冲洗。
将0.3gm该沉淀物与15gm平均直径为100nm的硅酸盐颗粒，5gm平均尺寸为10nm的硫酸钡颗粒，和3gm双酚F型环氧树脂混合，并加入足量水使体积达到1升。使用高剪切搅拌设备进行混合。
可以将该催化剂底涂层实施到聚合物或陶瓷基底上，然后可以利用化学金属电镀液在该基底上电镀金属薄膜。在电子制品中该金属薄膜可以起到EMI屏蔽的作用。
Claims (14)
1.一种组合物，该组合物用于沉积在基底上，形成催化层，该催化层允许化学镀金属成核并穿过该催化层生长至基底，其中该组合物包含催化剂，一种或多种具有5nm至900nm的平均颗粒尺寸的载体，和构成该组合物的5-60wt％的一种或多种水溶性或水分散性水基聚氨酯、一种或多种水溶性或水分散性环氧化物或它们的混合物，所述水基聚氨酯含有离子或亲水官能团以及主链中疏水的聚烯烃链节，其中该组合物不使用有机溶剂。
2.权利要求1的组合物，其中该催化剂包括催化金属的水合金属氧化物。
3.权利要求2的组合物，其中该催化金属包括银，金，铂，钯，铟，铷，钌，铑，锇，铱，铜，钴，镍，或铁。
4.权利要求1的组合物，其中该载体颗粒包括多价阳离子和阴离子对，金属氧化物，氧化硅，或它们的混合物。
5.权利要求4的组合物，其中该多价阳离子和阴离子对包括钡，钙，镁，锰的不溶于水的盐，或它们的混合物。
6.如权利要求1所述的组合物，其中该催化剂包括催化金属的氢氧化物。
7.如权利要求4所述的组合物，其中所述金属氧化物选自氧化铁、氧化铝、二氧化钛、氧化锌、氧化镁、氧化铯、氧化铬、氧化铪、氧化锆或者它们的混合物。
8.权利要求1所述的组合物，其中该载体颗粒包括硅酸盐。
9.如权利要求4所述的组合物，其中该载体颗粒包括碳酸钙。
10.一种方法，包括下列步骤:
a)将催化组合物涂覆到基底上，形成催化层，该催化层允许化学镀金属成核并穿过该催化层生长至基底，其中该催化组合物包含催化剂，一种或多种具有5nm至900nm的平均颗粒尺寸的载体，和构成该组合物的5-60wt％的一种或多种水溶性或水分散性水基聚氨酯、一种或多种水溶性或水分散性环氧化物或它们的混合物，所述水基聚氨酯包含离子或亲水官能团以及主链中疏水的聚烯烃链节，其中该组合物不使用有机溶剂；和
b)在带有该催化组合物的基底上沉积金属或金属合金。
11.权利要求10的方法，该方法还包括在基底上沉积金属或金属合金之前对该催化组合物进行固化的步骤。
12.权利要求10的方法，其中该金属或金属合金沉积物具有50mΩ/cm2或更小的表面电阻。
13.一种采用权利要求10所述的方法制得的制品，其包含基底和在该基底上成核的金属或金属合金。
14.权利要求13的制品，其中该金属或金属合金薄膜具有10nm至10微米的厚度。
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| US48086403P | 2003-06-24 | 2003-06-24 | |
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Also Published As
| Publication number | Publication date |
|---|---|
| US7842636B2 (en) | 2010-11-30 |
| US20090253573A1 (en) | 2009-10-08 |
| EP1491656A1 (en) | 2004-12-29 |
| KR20050001338A (ko) | 2005-01-06 |
| US7510993B2 (en) | 2009-03-31 |
| US7825058B2 (en) | 2010-11-02 |
| US20050025960A1 (en) | 2005-02-03 |
| US20090192029A1 (en) | 2009-07-30 |
| TW200513546A (en) | 2005-04-16 |
| KR101109006B1 (ko) | 2012-01-31 |
| JP5095909B2 (ja) | 2012-12-12 |
| CN1572903A (zh) | 2005-02-02 |
| TWI311162B (en) | 2009-06-21 |
| JP2005013983A (ja) | 2005-01-20 |
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