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CN1876891B - 使不导电基底直接金属化的方法 - Google Patents

使不导电基底直接金属化的方法 Download PDF

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CN1876891B
CN1876891B CN200610094568XA CN200610094568A CN1876891B CN 1876891 B CN1876891 B CN 1876891B CN 200610094568X A CN200610094568X A CN 200610094568XA CN 200610094568 A CN200610094568 A CN 200610094568A CN 1876891 B CN1876891 B CN 1876891B
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安德烈亚斯·柯尼希斯霍芬
安德烈亚斯·默比乌斯
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Abstract

本发明提供了一种使不导电基底金属化的方法，包括至少下列步骤：使基底与含金属的活化剂溶液接触；使基底与金属盐溶液接触，所述的基底已经与活化剂溶液接触，所述金属盐溶液包括：至少一种可被活化剂溶液中的金属还原的金属，络合剂，以及至少一种选自锂、钠、钙、铷和铯组成的组的金属；然后用金属对已处理的基底进行无电流涂覆或电镀涂覆；其特征在于金属盐溶液包括盐的形式的选自锂、钠、钙、铷和铯组成的组的金属，所述的盐的形式选自氟化物、氯化物、碘化物、溴化物、硝酸盐、硫酸盐或它们的混合物组成的组。

Description

使不导电基底直接金属化的方法
本发明涉及使不导电基底直接金属化的方法。
由现有技术可知使不导电基底例如印刷电路板的板或塑料造型直接金属化的不同方法。
因此，欧洲专利申请EP 0 538 006公开了一种直接金属化的方法，其中用含钯锡胶体的活化剂溶液来活化基底，并且在活化后使其与含足量离子的后活化剂溶液接触，在给定反应条件下进行歧化反应。然后用酸溶液处理该经处理的基底。
欧洲专利EP 0 616 053公开了同样的方法，但是其中金属组合物含有最高氧化态形式的待沉积金属。
现有技术的方法的共同点在于，大技术规模地使用所述方法导致一些问题，例如由于盐沉积在装置部件上造成积垢。这导致不充分涂覆，因此根据现有技术运行的装置必须定时净化并除去积垢。
在现有技术的方法中，因为空气中的二氧化碳(black damp)进入碱性溶液并随后溶解形成碳酸盐，所以经过几小时后，低溶解度的碳酸锂沉淀在加热元件与槽壁上。碳酸锂对过程的流动性有不利影响，因为脱落的小颗粒导致粗糙性并因此造成较高程度的浪费，并且由于加热元件的积垢而大大降低了加热功率，因而一方面电流能量的消耗增加，另一方面只可能借助额外的加热元件来保持运行温度。
本发明的目的是提供直接金属化的改进方法，其能够克服现有技术的问题尤其是积垢引起的问题。
该目的通过使不导电基底金属化的方法而实现，该方法包括下列步骤：
使基底与含金属的活化剂溶液接触；
使基底与金属盐溶液接触，所述的基底已经与活化剂溶液接触，所述金属盐溶液包括：至少一种可被活化剂溶液中的金属还原的金属，络合剂，以及至少一种选自锂、钠、钙(calium)、铷和铯(cesium)组成的组的金属；
然后用金属对已处理的基底进行无电流涂覆或电镀涂覆；
其特征在于金属盐溶液包括盐的形式的选自锂、钠、钙、铷和铯组成的组的金属，所述的盐的形式选自氟化物、氯化物、碘化物、溴化物、硝酸盐、硫酸盐或它们的混合物组成的组。
有利地，在用含金属的活化剂溶液处理前对不导电的基底进行预处理。这种预处理可以包括例如酸浸步骤。
含金属的活化剂溶液由金属-金属胶体的溶液组成，其具有第一芯金属以及胶态包裹芯的第二胶体金属。芯金属优选为至少一种选自银、金、铂或钯组成的组的金属。胶体金属优选为至少一种选自铁、锡、铅、钴或锗组成的组的金属。
其它本领域已知的活化剂溶液也可用于本发明的方法。
用活化剂溶液处理后，使经处理的基底与金属盐溶液接触，所述金属盐溶液包括：至少一种可被活化剂溶液中的金属还原的金属，络合剂，以及至少一种选自锂、钠、钙、铷和铯(cesion)组成的组的金属。
有利地，金属-金属胶体中的胶体金属起到含金属的活化剂溶液中还原金属的作用。作为可被胶体金属还原的金属，具有相应较高的标准电极电势并因此可被胶体金属还原的每种金属均可使用。特别适合的是铜、银、金、镍、钯、铂、铋或它们的混合物。
作为络合剂，有利地，络合剂的用量足以防止可被胶体金属还原的金属的微溶盐的沉淀。
适合的络合剂为例如单乙醇胺、EDTA、酒石酸、乳酸、柠檬酸、草酸、水杨酸、其盐或混合物以及它们的混合物。
有利地，金属盐溶液具有碱性pH值，其在约pH 10与pH 14之间，优选在约pH 11.5与约pH 13.5之间，最优选在约pH 12.5与约pH 13.5之间。为设定pH值，可向金属盐溶液中加入相应的氢氧化物、其它碱化剂和/或缓冲物质。
有利地，已用活化剂溶液处理的基底的接触在约20℃与约90℃之间，优选在约30℃与约80℃之间，最优选在约40℃与75℃之间进行。
用本发明的金属盐溶液处理基底导致导电结构无电流沉积在基底表面上。因此，然后用金属对经处理的基底进行无电流涂覆或电镀涂覆，例如镀铜或镀镍，是可能的。
除了本发明的方法之外，本发明还涉及金属盐溶液，其可根据本方法以上述方式用于金属的无电流沉积。
通过本发明的方法以及本发明的金属盐溶液至少部分地防止了工艺中存在的金属离子的微溶盐的形成。因此，完全可能得到较长的运行时间以及较短的停机时间，停机是出于维护的目的，尤其是去除装置中的积垢。
下列实施例说明了本发明方法的实施方案，但是本发明并不局限于此。
实施例1
在硫铬浴(sulphochromic bath)中使ABS工件接触并变粗糙。然后在含200mg/l钯、30g/l氯化锡(II)及300ml/l浓盐酸的胶体活化剂(activar)溶液中将工件洗涤并调理。之后，将工件第二次洗涤并随后浸没在下述金属盐溶液中，从而在不导电的塑料表面上形成导电薄膜：
1.0mol/l氢氧化钾
0.5mol/l氯化锂
0.4mol/l酒石酸钙钠
0.015mol/l硫酸铜
再次洗涤工件并随后通过施加电压在酸处理的(acid polished)铜电解液中金属化。通过该过程，ABS工件顺利取得了可用的及装饰性的金属化涂层。
实施例2
在硫铬浴中使ABS工件接触并变粗糙。然后在含200mg/l钯、30g/l氯化锡(II)及300ml/l浓盐酸的胶体活化剂溶液中将工件洗涤并调理。之后，将工件第二次洗涤并随后浸没在下述金属盐溶液中，从而在不导电的塑料表面上形成导电薄膜：
0.5mol/l氯化钠
0.5mol/l氢氧化锂
0.5mol/l溴化钙
0.4mol/l酒石酸钙钠
0.015mol/l硫酸铜
再次洗涤工件并随后通过施加电压在酸处理的铜电解液中金属化。通过该过程，ABS工件顺利取得了可用的及装饰性的金属化涂层。
通过本发明的方法避免或明显减少了现有技术中已知的沉淀问题。通过使用本发明的方法，装置的部件例如加热元件上的轻微积垢仅在数月后才发生。但是停工时间(dead time)已最小化，因为定时除去积垢已不再必要。

Claims (9)

1.一种使不导电基底金属化的方法，包括至少下列步骤：
使基底与含金属的活化剂溶液接触；
使基底与金属盐溶液接触，所述的基底已经与活化剂溶液接触，所述金属盐溶液包括：至少一种可被活化剂溶液中的金属还原的金属，络合剂，以及至少一种选自锂、钠、钙、铷和铯组成的组的金属；
然后用金属对已处理的基底进行无电流涂覆或电镀涂覆；
其特征在于金属盐溶液包括盐的形式的选自锂、钠、钙、铷和铯组成的组的金属，所述的盐的形式选自氟化物、氯化物、碘化物、溴化物、硝酸盐、硫酸盐或它们的混合物组成的组。
2.根据权利要求1所述的方法，其特征在于含金属的活化剂溶液包括金属-金属胶体，其具有作为芯的第一芯金属以及包裹芯金属的第二胶体金属，其中芯金属是选自银、金、铂和钯的至少一种，并且胶体金属是选自铁、锡、铅、钴和锗的至少一种。
3.根据前面任一权利要求所述的方法，其特征在于金属盐溶液包括络合剂，所述络合剂选自单乙醇胺、EDTA、酒石酸、乳酸、柠檬酸、草酸、水杨酸、其盐以及它们的混合物组成的组。
4.根据权利要求1或2所述的方法，其特征在于，金属盐溶液具有碱性pH值，其在pH 10与pH 14之间。
5.根据权利要求4所述的方法，其特征在于，金属盐溶液的pH值在pH 11.5与pH 13.5之间。
6.根据权利要求5所述的方法，其特征在于，金属盐溶液的pH值在pH 12.5与pH 13.5之间。
7.根据权利要求1或2所述的方法，其特征在于，金属盐溶液具有用于接触的温度，其在20℃与90℃之间。
8.根据权利要求7的方法，其特征在于，金属盐溶液具有用于接触的温度在30℃与80℃之间。
9.根据权利要求8的方法，其特征在于，金属盐溶液具有用于接触的温度在40℃与75℃之间。
CN200610094568XA 2005-06-10 2006-06-09 使不导电基底直接金属化的方法 Expired - Fee Related CN1876891B (zh)

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EP2305856A1 (en) * 2009-09-28 2011-04-06 ATOTECH Deutschland GmbH Process for applying a metal coating to a non-conductive substrate
DE102010012204B4 (de) 2010-03-19 2019-01-24 MacDermid Enthone Inc. (n.d.Ges.d. Staates Delaware) Verbessertes Verfahren zur Direktmetallisierung von nicht leitenden Substraten
CN107132216A (zh) * 2016-02-29 2017-09-05 福建大北农水产科技有限公司 一种养殖水体氨氮快速检测试剂盒
CN105839159B (zh) * 2016-05-23 2018-08-03 中山恒亿电镀有限公司 一种聚乙烯塑料电镀工艺
KR102783057B1 (ko) * 2019-04-04 2025-03-17 아토테크 도이칠란트 게엠베하 운트 콤파니 카게 금속화를 위해 비전도성 또는 탄소-섬유 함유 기판의 표면을 활성화하기 위한 방법
GB2587662A (en) * 2019-10-04 2021-04-07 Macdermid Inc Prevention of unwanted plating on rack coatings for electrodeposition
CN119302041A (zh) * 2022-06-02 2025-01-10 朗姆研究公司 电镀工具中的金属盐沉淀物的移除

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US20060280872A1 (en) 2006-12-14
JP2006342428A (ja) 2006-12-21
EP1734156A1 (de) 2006-12-20
CN1876891A (zh) 2006-12-13
KR20060128739A (ko) 2006-12-14

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