CN1406288A - 镀覆用预处理剂和使用它的金属镀覆方法 - Google Patents

镀覆用预处理剂和使用它的金属镀覆方法 Download PDF

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CN1406288A
CN1406288A CN01805746A CN01805746A CN1406288A CN 1406288 A CN1406288 A CN 1406288A CN 01805746 A CN01805746 A CN 01805746A CN 01805746 A CN01805746 A CN 01805746A CN 1406288 A CN1406288 A CN 1406288A
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伊森徹
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JX Nippon Mining and Metals Corp
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Abstract

本发明提供了一种金属镀覆的方法，所述的方法使得甚至在难以进行化学镀覆的材料上以一种有利的方式进行化学镀覆成为可能，以及提供了一种用于这一方法的预处理剂。要镀覆的制品用一种预处理剂处理，所述的预处理剂通过以下步骤来制备：分子中含有金属捕获官能基团的硅烷偶联剂溶液与含有在镀覆金属例如铜、镍等从化学镀覆溶液中沉积到要镀覆的制品表面上时有催化活性的金属的溶液混合，以致上述金属被上述硅烷偶联剂捕获；然后加入还原剂。此后，进行化学镀覆，以致在经上述预处理的制品表面上形成金属薄膜。然后，可进行所希望的金属镀覆。

Description

镀覆用预处理剂和使用它的金属镀覆方法
技术范围
本发明涉及一种用于低导电性材料、镜面制品、粉末等的表面用化学镀覆法金属镀覆的镀覆用预处理剂，以及使用这种预处理剂的金属镀覆方法。
背景技术
金属化学镀覆方法是一种在没有导电性的基材上形成金属涂膜的方法。在实施化学镀覆中，一种称为活化的方法通常用作化学镀覆预处理，在这一方法中贵金属例如钯等作为催化剂事先粘附到基材上。过去，一些方法已用作这样的活化方法，在这些方法中通过在PdCl2水溶液中浸泡然后用SnCl2的盐酸水溶液处理使Pd被吸附，或者用Sn和Pd的胶体溶液使Pd负载在表面上。这样的方法存在许多问题，例如高毒性Sn的使用，需要复杂的处理过程等。所以，最近提出了各种使用硅烷偶联剂的方法作为使这样的贵金属负载在经处理的表面上的方法，所述的硅烷偶联剂含有能与构成化学镀覆用催化剂的贵金属例如Pd等形成配合物的官能基团。(日本专利公报No.S59-52701、日本专利申请书公开No.S60-181294、日本专利申请书公开No.S61-194183、日本专利公报No.H3-44149)。在这些方法中，有这样一些方法，其中用镀覆催化剂固定剂和镀覆催化剂进行单独的处理，也就是这样一些方法，其中在偶联剂吸附在要镀覆的制品上以后，再负载构成催化剂的贵金属离子。但是，在这些情况下，视要镀覆制品的材料而定，可能是由于偶联剂处理使要镀覆制品的表面改变或者由于贵金属离子不能有效地负载，这些材料有时难以形成具有良好粘附性的均匀镀覆膜。此外，视要镀覆制品的材料和镀覆条件而定，或者是由于上述原因或者是由于钯没有足够的催化活性，在有些情况下，在使用氨基硅烷偶联剂和氯化钯的混合溶液时，也不可能得到均匀的镀覆膜。
发明公开内容
鉴于上述，本发明的一个目的是提供一种使用新型化学镀覆方法的金属镀覆方法，它甚至能在难以用于传统的化学镀覆方法的材料上进行理想的化学镀覆。本发明的另一目的是提供一种用于上述化学镀覆的金属镀覆用预处理剂。具体地说，本发明使得甚至使用具有弱还原能力的镀覆溶液例如铜镀覆溶液等实现有良好粘附性的均匀镀覆成为可能。
为了解决上述技术问题所进行的辛勤研究的结果，本发明人发现，通过以下步骤，甚至在难以使用传统的化学镀覆的镀覆材料上，可以理想的方式和简单的方法进行化学镀覆：通过用分子中含有金属捕获官能基团的硅烷偶联剂捕获金属然后加入还原剂制备的预处理剂进行镀覆制品的表面处理。这一发现使本发明完成。
具体地说，本发明提供：(1)一种金属镀覆方法，其特征在于，所述的方法包括用预处理剂处理要镀覆的制品，所述的预处理剂通过用分子中含有金属捕获官能基团的硅烷偶联剂捕获金属然后加入还原剂来制备；然后进行化学镀覆。(2)根据上述(1)的金属镀覆方法，其特征在于，金属捕获官能基团为胺。(3)根据上述(1)的金属镀覆方法，其特征在于，金属捕获官能基团为咪唑。(4)根据上述(1)的金属镀覆方法，其特征在于，金属为钯化合物。(5)一种金属镀覆方法，其特征在于，在分子中含有金属捕获官能基团的硅烷偶联剂为一种通过唑类化合物和环氧硅烷型化合物反应得到的硅烷偶联剂。(6)根据上述(1)的金属镀覆方法，其特征在于，还原剂为二甲基胺硼烷。(7)根据上述(1)的金属镀覆方法，其特征在于，金属镀覆层为铜或镍。(8)一种金属镀覆用预处理剂，其特征在于，预处理剂通过分子中含有金属捕获官能基团的硅烷偶联剂捕获金属然后加入还原剂来制备。
本发明的特征在于，使用规定的硅烷偶联剂，也就是这样一种硅烷偶联剂，其中构成高活性催化剂的金属被金属捕获官能基团捕获，以及将还原剂加到这一偶联剂中。
实施本发明的最好方式
在本发明的金属镀覆用预处理剂中，可通过加入还原剂使催化剂的活性提高，以致甚至可用具有弱还原能力的镀覆溶液进行还原。
含氮杂环化合物例如咪唑类等，包括伯胺、仲胺和叔胺都可用作金属捕获官能基团。
在本发明中，贵金属希望作为构成高活性催化剂的金属，可使用的贵金属化合物的例子包括钯、银、铂、金等的氯化物、氢氧化物、氧化物、硫酸盐和胺配合物(氨盐等)，当铜、镍等从化学镀覆溶液中沉积在要镀覆的制品表面时，它们具有催化活性。这些化合物中，氯化钯是特别优选的。通过将各自化合物的溶液混合来实现上述硅烷偶联剂对贵金属的捕获。与用于预处理剂的相同溶剂(后面描述的)可用作上述溶液的溶剂。
在本发明中使用的含有金属捕获官能基团的硅烷偶联剂可为任何一种有上述金属捕获官能基团的硅烷偶联剂；对这种偶联剂没有特别的限制。含有含氮杂环唑类化合物例如咪唑等的硅烷偶联剂是特别优选的。
由于分子中含氮杂环的存在，可通过含氮杂环的共轭和芳香性得到可有效显示镀覆催化剂活性的电子状态和取向，此外，因为该试剂为硅烷偶联剂，可实现试剂对要镀覆的制品的牢固粘附。
这样的含氮杂环唑类化合物的例子包括咪唑、噁唑、噻唑、硒唑、吡唑、异噁唑、异噻唑、三唑、噁二唑、噻二唑、四唑、噁三唑、噻三唑、五唑、吲唑、苯并咪唑、苯并三唑、吲唑等。本发明不限于这些化合物；但是，有咪唑环的化合物是特别优选的。
此外，将金属捕获官能基团引入其上的硅烷偶联剂为这样一种化合物，它有-SiX1X2X3基团，其中X1、X2和X3表示烷基、卤素原子、烷氧基等，以及可为任何一种可固定到要镀覆制品上的任何官能基团。X1、X2和X3可为相同的或不同的。在本发明中使用的含有金属捕获官能基团的硅烷偶联剂例如可通过上述含氮的杂环化合物与环氧硅烷型化合物反应来制得。这样的硅烷偶联剂例如在日本专利申请书公开No.H6-256358中公开并为已知的。
本发明的金属镀覆方法中，对要镀覆的材料性质没有限制。例如，本发明的镀覆方法可用于无机材料，例如玻璃、陶瓷等；塑料，例如聚酯、聚酰胺、聚酰亚胺、含氟树脂等或含有这些材料的薄膜、片材或纤维；绝缘材料，例如环氧树脂等制造的绝缘板，如果需要，它们可用玻璃布基材来增强；或半导体，例如Si晶片；或其他有低导电性的制品。即使要镀覆的制品为有镜面表面的制品例如玻璃板、Si晶片或其他半导体基材或粉末材料，本发明也可以有利的方式应用。这些粉末材料的例子包括玻璃小球、粉末状二硫化钼、粉末状氧化镁、粉末状石墨、粉末状SiC、粉末状氧化锆、粉末状氧化铝、粉末状氧化硅、云母片、玻璃纤维、氨化硅、粉末状聚四氟乙烯等。
在要化学镀覆的材料用通过分子中有至少一个金属捕获官能基团的硅烷偶联剂捕获金属然后加入还原剂制备的上述预处理剂处理的情况下，可使用通过将预处理剂溶于适合的溶剂中制得的溶液形式，所述的溶剂例如为水、甲醇、乙醇、2-丙醇、乙二醇、聚乙二醇等或这些溶剂混合制得的溶剂。特别是在使用水溶液的情况下，pH值对镀覆的特性有重大的影响。从固定镀覆催化剂的氮配合物形成的能力的观点出发，高pH值是优选的；但是，因为在高pH值的情况下溶液的稳定性下降，所以1.5-7的pH值是优选的。
关于用预处理剂处理镀覆制品的方法，通常使用这些方法，例如浸泡、刷涂、旋涂等。但是，本发明不限于这些方法；任何一种使带有贵金属离子和烷氧甲硅烷基的胺化合物粘附到要镀覆的制品表面的方法都可使用。在这种情况下，在30-80℃下的处理对于提高试剂的粘附性是有效的。
对硅烷偶联剂在处理溶液中的浓度没有限制；但是，0.001-10％(重量)的浓度易于使用。在浓度小于0.001％(重量)的情况下，粘附到基材表面的化合物数量减少，以致不能均匀地进行镀覆。另一方面，如果浓度大于10％(重量)，粘附的化合物数量过量，以致难以干燥，而在镀着的制品为粉末的情况下，常出现团聚。
次磷酸钠、硼氢化钠、二甲基胺硼烷等可作为上述还原剂的例子。
如果加入的还原剂数量太少，那么催化剂的活化不充分；另一方面，如果加入的数量太大，催化剂转变成金属并生成沉淀。还原剂按0.01-1000毫克/升、优选0.1-500毫克/升的比率加到溶液中是优选的，在此溶液中含有分子中含有金属捕获官能基团的硅烷偶联剂和作为镀覆催化剂的金属盐。很显然，加入的还原剂数量取决于还原剂的类型和金属盐的数量。
还原剂在室温下和搅拌下加入。还原剂也可在加热下加入。
为了在表面处理以后让所用的溶剂蒸发，通过将溶剂加热到溶剂的汽化温度以上足以使表面干燥。但是，在60-120℃进一步加热3-60分钟是希望的。
在水用作溶剂的情况下，干燥过程可省去，仅通过表面处理以后用水清洗就可镀覆。但是，在这种情况下，必需用水进行充分地清洗，以致不让催化剂带到镀覆溶液中。
关于进行预处理的温度，室温是足够的；但是，视要镀覆的制品而定，也有一些情况，加热是有效的。
当然，也可在镀覆预处理以前清洁要镀覆的制品。特别是在需要良好粘附性的情况下，也可使用利用铬酸等的传统蚀刻处理。
此外，也可能先进行化学镀覆，以致形成金属薄膜，从而使不导电的基材有某种程度的导电性，然后用贱金属进行化学镀覆或置换镀覆。
用本发明的化学镀覆法形成金属薄膜以后，可镀覆铜、镍、钴、锡、金等的金属镀覆层。通过以下实施例来具体描述本发明。
实施例
通过加入氯化钯和还原剂并将混合物在室温下放置1天以后，用肉眼观察沉淀物或产物来评价预处理溶液的稳定性。根据预处理以后对基材的覆盖率和粘附性来评价镀覆膜的粘附性。用镀覆用预处理剂的所有处理都在60℃加热下进行。此外，用盐酸水溶液来调节pH值。而且，上述粘附性用胶带剥离试验来评价。
实施例1
在室温和搅拌下，将氯化钯水溶液加到咪唑和γ-缩水甘油氧基丙基三甲氧基硅烷的等摩尔反应产物的0.05％(重量)水溶液中，如此制得氯化钯浓度为100毫克/升的溶液。用盐酸水溶液将这一溶液的pH值调节到2.4。按1毫克/升的比率将二甲基胺硼烷的水溶液加到这一溶液中。关于稳定性，将溶液放置1天，确定溶液是稳定的。将这一溶液加热到60℃，将聚酯布在溶液中浸泡5分钟。然后，用水充分清洗以后，在60℃下用铜镀覆溶液NKM-554(Nikko Metal Plating Co.，Ltd.制造)形成铜化学镀覆层。聚酯布全部被有良好粘附性的铜镀覆。
实施例2
在室温下，将聚酯纤维在实施例1中制备的镀覆用预处理剂中浸泡5分钟，然后用水充分清洗。随后，在75℃下，用加热到70℃的镍镀覆溶液Nikom 7N(Nikko Metal Plating Co.，Ltd.制造)进行镍化学镀覆。聚酯纤维全部被有良好粘附性的镍镀覆。
实施例3
将尼龙纱在实施例1中制备的镀覆用预处理剂中浸泡5分钟，然后用水充分清洗。随后，在75℃下，用加热到70℃的镍镀覆溶液Nikom 7N(Nikko Metal Plating Co.，Ltd制造)进行镍化学镀覆。尼龙纱全部被有良好粘附性的镍镀覆。
实施例4
在搅拌和室温下，将氯化钯水溶液加到咪唑和γ-缩水甘油氧基丙基三甲氧基硅烷的等摩尔反应产物的0.02％(重量)水溶液中，如此制得氯化钯浓度为40毫克/升的溶液。以45毫克/升的数量将二甲基胺硼烷水溶液加到这一溶液中。将这一溶液加热到60℃，然后将表面用氢氧化钠处理的氧化铝在这一溶液中浸泡10分钟，然后用水清洗。此后，用铜镀覆溶液KC-500(Nikko Metal Plating Co.，Ltd制造)在72℃下进行铜化学镀覆。氧化铝全部被有良好粘附性的铜镀覆。
对比例1
在搅拌和室温下，将氯化钯水溶液加到咪唑和γ-缩水甘油氧基丙基三甲氧基硅烷的等摩尔反应产物的0.05％(重量)水溶液中，如此制得氯化钯浓度为100毫克/升的溶液。用盐酸水溶液将这一溶液的pH值调节到2.4。将这一溶液加热到60℃，然后将聚酯布在溶液中浸泡5分钟，再用水充分清洗。此后，在60℃下用铜镀覆溶液NKM-554(NikkoMetal Plating Co.，Ltd制造)进行化学镀覆。聚酯布未被镀覆。
工业应用
如上所述，本发明的镀覆方法使得借助一简易的过程甚至在传统方法难以镀覆的基材例如不导电的塑料或这些基材的薄膜和纤维、低导电性的半导体例如Si晶片等、镜面制品以及粉末等上进行镀覆成为可能。具体地说，本发明使得甚至在使用弱还原能力的镀覆溶液例如铜镀覆溶液等的情况下进行具有良好粘附性的均匀镀覆成为可能。

Claims (8)

1.一种金属镀覆方法，其特征在于，所述的方法包括用一种预处理剂处理要镀覆的制品，所述的预处理剂通过用在分子中含有金属捕获官能基团的硅烷偶联剂捕获金属然后加入还原剂来制备；然后进行化学镀覆。
2.根据利要求1的金属镀覆方法，其特征在于，金属捕获官能基团为胺。
3.根据权利要求1的金属镀覆方法，其特征在于，金属捕获官能基团为咪唑。
4.根据权利要求1的金属镀覆方法，其特征在于，金属为钯化合物。
5.一种金属镀覆方法，其特征在于，分子中含有至少一个金属捕获官能基团的硅烷偶联剂为唑类化合物和环氧硅烷型化合物反应制得的硅烷偶联剂。
6.根据权利要求1的金属镀覆方法，其特征在于，还原剂为二甲基胺硼烷。
7.根据权利要求1的金属镀覆方法，其中金属镀覆层为铜或镍。
8.一种金属镀覆用预处理剂，其特征在于，所述的预处理剂通过用分子中含有金属捕获官能基团的硅烷偶联剂捕获金属，然后加入还原剂来制备。
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CN108250950A (zh) * 2018-01-17 2018-07-06 安徽工业大学 一种亲水高耐蚀型钢铁表面硅烷化处理剂及其合成方法
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TWI241357B (en) 2005-10-11
CN1261618C (zh) 2006-06-28
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EP1279750B1 (en) 2016-05-04
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