CN102803573A - 金属在塑料基板上的选择性沉积 - Google Patents

金属在塑料基板上的选择性沉积 Download PDF

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CN102803573A
CN102803573A CN2010800272044A CN201080027204A CN102803573A CN 102803573 A CN102803573 A CN 102803573A CN 2010800272044 A CN2010800272044 A CN 2010800272044A CN 201080027204 A CN201080027204 A CN 201080027204A CN 102803573 A CN102803573 A CN 102803573A
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CN102803573B (zh
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R·汉密尔顿
M·沃伊塔谢克
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MacDermid Acumen Inc
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Abstract

本发明涉及一种选择性地镀覆塑料制品的方法，该塑料制品包含第一聚合物树脂部分和第二聚合物树脂部分，其中该第一聚合物树脂部分不因磺化而可镀覆而该第二聚合物树脂部分因磺化而可镀覆。此方法包含将塑料制品磺化、活化该磺化的塑料制品以使其上接受镀覆和将经磺化且经活化的制品在化学镀浴中镀覆的步骤。该塑料制品被选择性地镀覆，使得第一聚合物树脂部分上无镀覆而第二聚合物树脂部分被化学镀覆。

Description

金属在塑料基板上的选择性沉积
技术领域
一般来说，本发明涉及金属在塑料基板的选择性沉积。
背景技术
例如，在形成印刷电路板中使用模塑的单片制品。在许多情形下，使用两个独立的模塑步骤来形成制品的两部分。例如双射成型为一种制造具有两个部分的装置的方法，各部分由不同的注塑聚合物制得。此方法也用于制造双色模塑塑料制品及将软塑料与硬塑料组合于单个模塑部件中。
典型的双射成型方法包括以下步骤：
1.模塑出第一射出物；
2.用第二聚合物包塑第一射出物；
3.蚀刻并活化暴露区域；及
4.以化学镀镍和/或化学镀铜镀覆以沉积镀覆材料。
除了使产品拥有所需的最终使用性能，所选用的两种聚合物必须在双射成型过程中兼容且必须提供合适的镀覆用表面。为了镀覆一种聚合物而不镀覆另一种聚合物，已经普遍地发现，必须在模塑处理后选择性地活化预镀覆的聚合物，或者使用其中沉积有催化剂的聚合物(即含特定百分比的钯的聚合物，例如Zaderej的第7,189,120号美国专利所述，其主题以引用方式全部并入此处)。双射(或多射)注塑方法的其它实例在Cleveland等人的第5,407,622号美国专利和Dailey等人的第6,601,296号美国专利中有描述，其主题以引用方式全部并入此处。已建议的其它方法还包括(i)将催化剂嵌入到所有塑料中然后通过选择性激光烧蚀将其选择性地曝光并活化，(ii)使用双射成型，其中第一射出物含催化毒物以防止在此区域镀覆，及(iii)双射(或多射)注塑，其中可镀覆射出物中塑料易于蚀刻以形成有助于催化与镀覆的表面而不可镀覆射出物不易被蚀刻。
可有助于催化与镀覆的典型塑料材料包括丙烯腈-丁二烯-苯乙烯(ABS)树脂、聚烯烃、聚氯乙烯、聚碳酸酯-丙烯腈-丁二烯-苯乙烯(PC/ABS)树脂和酚甲醛树脂等。
形成化学涂层(镀覆于塑料周围)的过程一般包括步骤(1)蚀刻基板；(2)中和该蚀刻的表面；(3)在含有氯化钯、氯化亚锡与氢氯酸的溶液或钯离子的酸性溶液中催化该中和的表面，继而(4)在促进剂溶液(其为酸或碱)中浸泡；及(4)在该活化的基板上形成金属涂层。通常将基板浸于蚀刻剂(一般为铬酸与硫酸的混合溶液)中对基板表面进行蚀刻。可通过将基板浸泡于含有镍或铜离子的化学镀浴中并通过化学还原浴中的金属离子将金属沉积在基板上(即化学镀覆)，从而在活化的基板上沉积金属涂层。所得金属涂层因其导电性而可用于后续电镀。一般在以上各步骤后用水清洗基板也是可取的。
此方法具有两大缺点：
(1)用于此方法的常规且成本最低的材料为丙烯腈-丁二烯-苯乙烯(ABS)、聚碳酸酯-丙烯腈-丁二烯-苯乙烯(PC/ABS)和聚碳酸酯(PC)。在使用铬酸与硫酸的混合物对这些材料中的每一种进行蚀刻时，在一定程度上，其对于同时在需要镀覆区上获得完全镀覆并在不需镀覆区上不镀覆留下了窄的操作窗；及
(2)由于包含铬酸，该蚀刻溶液从环境、健康与安全角度考虑不宜采用。
因此，需要提供一种不需要使用铬酸蚀刻剂对塑料进行选择性镀覆的方法，该塑料包括丙烯腈-丁二烯-苯乙烯和丙烯腈-丁二烯-苯乙烯/聚碳酸酯树脂。
早已运用聚合物的表面改性(如磺化)通过将疏水性表面改变成亲水性表面来改良聚合物特性。可使用数种方法实现磺化，包括使用气相三氧化硫、热浓硫酸和发烟硫酸等进行处理。磺化通过将磺基引入聚合物基板的表面区域而改变其化学结构。用三氧化硫气体及各种中和剂处理表面区域以改变塑料表面区域的分子结构的方法可对许多种聚合物有效。例如Neumann等人的第5,958,509号美国专利讨论建议将磺化用于活化模塑塑料制品的表面以使其上能够镀覆硅烷涂覆材料，其主题以引用方式全部并入此处。
在磺化过程中，SO3与存在于聚合物中的碳原子键合并形成C-SO3H。通常将该过程叙述为将硫原子(S)与聚合物的碳骨架中的碳原子(C)进行键合。基本上所有市售塑料和膜均含CH或NH键且可通过磺化处理，尽管本发明的发明人已发现基于被磺化的特定聚合物树脂，磺化会以不同速率进行。对含NH的材料，以C-SO3H为对照，其形成NSO3H。
一般来说，本发明涉及对模塑制品的磺化，所述模塑制品具有其上可进行化学镀覆的第一部分和其上基本抑制化学镀覆的第二部分。更具体地，本发明涉及形成印刷电路板用模塑坯件、模塑制品与制品的镀覆部分的方法，其由用来形成制品可镀覆部分与不可镀覆部分的两个独立的模塑步骤组成。
发明内容
本发明的一个目的为提供一种选择性金属化模塑制品的方法，该方法能够最小化或排除金属对模塑制品不可镀覆部分的黏附。
本发明的另一个目的为提供一种未使用铬酸/硫酸蚀刻步骤的可镀覆塑料品。
本发明的另一个目的为提供一种化学镀覆方法，其包括磺化步骤以选择性地镀覆模塑塑料制品。
为此，一般来说，本发明涉及一种选择性地镀覆塑料制品的方法，所述塑料制品包含第一聚合物树脂部分和第二聚合物树脂部分，其中该第一聚合物树脂部分不因磺化而可镀覆，而该第二聚合物树脂部分因磺化而可镀覆，此方法包含以下步骤：
a)将塑料制品磺化，其中第二聚合物树脂部分经磺化而可镀覆；
b)活化该磺化的塑料制品以使其上能够化学镀覆；
c)将经磺化并活化的制品在化学镀浴中进行镀覆；
由此，选择性地镀覆了塑料制品，使得第一聚合物树脂部分上无镀覆，而第二聚合物树脂部分上被化学镀覆。
具体实施方式
一般来说，本发明涉及在塑料制品上使用磺化步骤以使部分的塑料制品可镀覆。磺化使特定聚合物极性化，使得在催化步骤中使用的贵金属催化剂能够黏附于聚合物表面。
本发明的发明人已发现，因为不同聚合物树脂的磺化在相同条件下以不同的速率发生，所以对由多种聚合物树脂制成的制品进行的磺化有一定程度的选择性。具体地，本发明的发明人已发现，ABS与PC/ABS可极容易且充分地为了镀覆目的而磺化，而聚碳酸酯的磺化则相对地较困难且较缓慢。因此本发明涉及使用磺化使部分的双射成型或多次注塑塑料制品可镀覆而其余部分不可镀覆，从而使得制品可按所需图案进行选择性地镀覆。
由双射注塑成型(其中一种射出物为PC/ABS而另一射出物为PC)形成的制品经磺化可足以使PC/ABS部分可镀覆而PC射出物部分不可镀覆。然后将这些部件通过各种化学镀覆处理步骤处理，包括例如贵金属催化剂溶液，随之为催化剂还原溶液，继而化学镀铜或化学镀镍。化学镀金属可容易地且可靠地沉积于PC/ABS或ABS聚合物树脂表面，但是在聚碳酸酯区域不发生沉积。
为了防止任何化学镀金属镀覆在不可镀覆的部分上，可以在不可镀覆树脂中加入催化毒物化合物以阻碍后续应用的化学镀覆的化学作用在含催化毒物化合物的部分产生镀覆沉积的倾向。然后可将双射成型塑料部件通过利用胶体活化、促进的标准镀覆塑料工艺线进行处理，然后进行化学镀铜或化学镀镍的化学作用。如上所述，使用本发明的磺化步骤可省去铬酸/硫酸蚀刻步骤及其后续的中和步骤。本领域公知的其它镀覆塑料工艺也可用于本发明的实践中。
在一个具体实施方式中，本发明的方法涉及一种选择性地镀覆塑料制品的方法，所述塑料制品包含第一聚合物树脂部分和第二聚合物树脂部分，其中该第一聚合物树脂部分不因磺化而可镀覆，而该第二聚合物树脂部分因磺化而可镀覆，此方法包含以下步骤：
a)将塑料制品磺化，其中第二聚合物树脂部分因磺化而可镀覆；
b)活化该经磺化的塑料制品以使其上能够化学镀覆；
c)在化学镀浴中镀覆该经磺化并活化的制品；
由此，选择性地镀覆了塑料制品，使得第一聚合物树脂部分上无镀覆，而第二聚合物树脂部分上被化学镀覆。
在不使用铬酸的条件下，使用此处所述的磺化可以在较宽的工艺窗口内选择性地镀覆混合树脂制品、双射或多射成型的树脂制品。磺化可通过例如但非限于将制品暴露于发烟硫酸或气相三氧化硫中来完成。在本发明的一个具体实施方式中，优选气相三氧化硫。磺化步骤一般通过将制品置于能够充分磺化该制品的第二聚合物树脂部分的浓度的硫气氛中一段充足的时间来完成的。基于使用的特定硫试剂，磺化剂在硫气氛中的浓度一般在约1％～约25％重量的范围内。此外磺化时间一般在约1～约90的范围内。
双射注塑成型方法分别由不可镀覆聚合物与可镀覆聚合物之一形成第一“射出物”，然后由其中另一聚合物形成第二“射出物”，该第一“射出物”与第二“射出物”共同组成塑料部件。将两部分在压力下压入一个或多个封闭模具中，材料在模具孔穴内固化。经模塑材料保留模具的形状，然后将完成的模塑部件从模具孔穴排出。例如，在形成黏附金属用模塑制品(如具有电路图案的印刷电路板)时，双射成型成型方法以第一次注塑形成电路图案并以第双射成型在电路图案周围形成支撑体结构。其它双射成型和多射成型注塑方法也可用于本发明的实践中。
在经过磺化及塑料镀覆线(活化与化学镀覆)步骤处理后，仅一部分模塑部件可接纳化学镀覆而其它部分则不接纳。此处所述的创新工艺还排除了对不宜采用的铬酸/硫酸蚀刻步骤的需求。
产物为一种呈现改良了镀覆质量并减少了镀覆碎屑的模塑塑料部件，其也解决了关于对双射成型片多余镀覆的工业问题。
如上所述，双射成型片包含镀覆部分和非镀覆部分。镀覆部分与非镀覆部分的其它合适树脂的组合也为本领域技术人员所公知。
为了制备可镀覆塑料部分以在其上进行化学镀覆，将塑料部件通过几种典型化学镀覆循环(塑料镀覆循环)之一进行处理。各种公知的化学镀覆(塑料镀覆)循环皆可用于本发明。作为非限制性的实例，以下描述了若干个这些循环。
在一个具体实施方式中，在树脂磺化后，化学镀覆循环包括以下步骤：
1)胶体活化；
2)促进；及
3)化学镀镍或化学镀铜。
在该方法的各步骤之间一般插入有冷水洗涤的步骤。
在另一个具体实施方式中，在磺化后，化学镀覆循环包括以下步骤：
1)钯离子活化(酸或碱)；
2)离子性还原剂、次磷酸盐、二甲氨基硼烷(DMAB)、或在水中的氢化硼混合物；及
3)化学镀镍或化学镀铜。
在又一个具体实施方式中，在磺化后，化学镀覆循环包括以下步骤：
1)钯离子活化；
2)钯离子还原剂；及
3)化学镀镍或化学镀铜。
本领域公知的其它化学镀覆方法也适用于本发明。
虽然以上参照其具体实施方式对本发明进行了描述，显然在不背离此处公开的发明构思的情形下，其可进行许多变化、修改和变动。因而，本发明包含落入所附权利要求的宗旨和范围内的所有此类变化、修改及变动。此处列举的所有专利申请、专利、及其它公开出版物以引用方式整体地全部并入此处。

Claims (10)

1.一种选择性地镀覆塑料制品的方法，所述塑料制品包含第一聚合物树脂部分和第二聚合物树脂部分，其中所述第一聚合物树脂部分不因磺化而可镀覆，而所述第二聚合物树脂部分因磺化而可镀覆，所述方法包含以下步骤：
a)将所述塑料制品与磺化剂接触，使得所述第二聚合物树脂部分因磺化而可镀覆；
b)将所述经磺化的塑料制品与活化剂接触，以使其上接受化学镀覆；
c)将该经磺化且经活化的塑料制品在化学镀浴中进行镀覆；
由此，选择性地镀覆了所述塑料制品，使得所述第一聚合物树脂部分上无镀覆而所述第二聚合物树脂部分上被化学镀覆。
2.如权利要求1所述的方法，其中所述第一聚合物树脂部分包含聚碳酸酯树脂。
3.如权利要求2所述的方法，其中所述第二聚合物树脂部分包含丙烯腈-丁二烯-苯乙烯(ABS)树脂或ABS/聚碳酸酯树脂。
4.如权利要求1所述的方法，其中化学镀浴包含化学镀铜或化学镀镍。
5.如权利要求1所述的方法，其中所述活化剂包含金属胶体催化剂，并且其中所述金属胶体催化剂包含选自钯、铂、金和银的金属。
6.如权利要求1所述的方法，其中所述塑料制品是通过双射成型形成的，其中将所述第一聚合物树脂部分与所述第二聚合物树脂部分在压力下压入一个或多个封闭模具中并且所述材料在模具孔穴内固化。
7.如权利要求1所述的方法，其中在不使用铬酸/硫酸蚀刻步骤下选择性地镀覆所述塑料制品。
8.如权利要求1所述的方法，其中磺化剂包含发烟硫酸或气相三氧化硫。
9.如权利要求8所述的方法，其中磺化剂包含气相三氧化硫。
10.如权利要求8所述的方法，其中将所述塑料制品与所述磺化剂接触的时间为约1至约90秒/分钟。
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