CN104136658B - 无电镀镍浴 - Google Patents

无电镀镍浴 Download PDF

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CN104136658B
CN104136658B CN201380007827.9A CN201380007827A CN104136658B CN 104136658 B CN104136658 B CN 104136658B CN 201380007827 A CN201380007827 A CN 201380007827A CN 104136658 B CN104136658 B CN 104136658B
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electroless nickel
plating baths
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C.C.费尔斯
B.迪尔布施
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Atotech Deutschland GmbH and Co KG
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Abstract

本发明涉及适合在塑性工艺上镀覆应用的无电镀镍浴。所述镀浴不含诸如铅离子和氨的危险物质，且允许镍磷合金在不高于55℃的镀覆温度下沉积在塑料底材上。此外，从浸渍型镀铜浴沉积铜到镍磷涂层上不需要活化步骤，这使得加工步骤减少且减少废水产生。

Description

无电镀镍浴
发明领域
本发明涉及用于低温沉积具有4-11重量%的磷含量的镍磷合金的无电镀镍浴。得到的镍磷沉积物可在塑性工艺上的镀覆期间用来自浸镀铜浴的铜直接涂布。
发明背景
在工业上广泛使用出于装饰和电磁阻抗屏蔽目的的在塑性工艺上的电镀。所述工艺施用到诸如淋浴喷头、移动电话盖和散热器护栅的各种塑料部件。一种主要的工艺路径包括在预处理并活化欲涂布的塑料底材之后的无电镀步骤。所应用的无电镀方法通常是无电沉积铜或镍。沉积到活化的塑料底材上的金属或金属合金层充当随后通过电镀法沉积的其他金属层的全区域导电表面。用于所述目的的主要塑料材料为ABS (丙烯腈-丁二烯-苯乙烯共聚物)、ABS/PC共混物和PA。在无电沉积铜或镍之后施用的主要电镀方法为电镀铜、镍和最后电镀铬。所述方法在本领域中公知且例如描述在EP 0 616 053 B1中。
如果镍合金通过无电镀法沉积，则对于无电镀镍法和所使用的镀镍浴的需求是多样的。
在本领域中已知能够沉积具有在4-11重量%范围内的磷含量的镍磷合金的无电镀镍浴。
可用于将镍磷合金沉积到导电的SnO2表面上的无电镀镍浴公开在US 2002/0187266 A1中。所述无电镀镍浴可含有硫代水杨酸作为稳定剂。然而，公开的镀覆温度高达70℃且镀浴需要诸如铅离子的危险物质。
包含硫化物离子以及硫化物离子控制剂的无电镀镍浴公开在US 2,762,723中。适合作为硫离子控制剂的化合物选自无机硫化物、其他硫代化合物、铋和铅离子。
发明概述
因此，本发明的一个目的在于提供用于在塑性工艺上镀覆的无电镀镍浴，其能够沉积具有在4-11重量%范围内、优选在6-9重量%范围内的磷含量的镍磷合金以在不高于55℃、优选低于40℃的镀浴温度下沉积所述合金，其节约能源且其不含诸如铅和氨的危险组分。此外，本发明的一个目的在于提供无电镀镍浴，其允许沉积镍磷涂层，所述镍磷涂层可在连续工艺步骤中在铜沉积之前通过将底材浸渍在例如硫酸中而在不活化所述镍磷涂层的情况下用来自浸镀铜浴的铜涂布。这使得工艺步骤的数目减少且减少废水产生。
该目的用权利要求1的无铅且无铵的(ammonium-free)无电镀镍浴实现，所述无电镀镍浴包含镍盐、作为还原剂的次磷酸盐化合物、络合剂混合物和稳定剂组分混合物。
通过使用下文更详细描述的镀浴施用根据本发明的镀覆机制，可获得镍磷沉积物，其含磷量低且适合通过浸渍铜直接镀覆。
在不加以束缚的情况下，认为在通过本发明的方法获得的镍磷沉积物上直接浸镀是可能的，因为该镍沉积物具有较低的磷以及铋含量，这两者都不利地影响铜沉积。
发明详述
本发明人已经意外地发现，在活化的塑料底材上的镍磷涂层可从无氨且无铅的无电镀镍浴中沉积以便在低温下沉积具有4-11重量%的磷含量的镍磷合金，它们适合直接沉积浸渍铜，所述镀浴包含：
1.
i. 镍离子源；
ii. 次磷酸根离子源；
iii. 络合剂混合物，其包含：
a) 选自羟基羧酸、二羟基羧酸及其盐的至少一种第一络合剂和
b) 选自亚氨基琥珀酸、亚氨基二琥珀酸、其盐和衍生物的至少一种第二络合剂；
iv. 稳定剂混合物，其包含：
a) 铋离子，和
b) 选自巯基苯甲酸、巯基羧酸和巯基磺酸及其盐的至少一种化合物。
本发明的无电镀镍浴的优势在于a) 在所述镀浴中不需要氨和铅和b) 在从浸镀铜浴中沉积铜之前不需要活化镍磷层。
本发明的无电镀镍浴含有以0.5g/l-5g/l、更优选2.5g/l-4g/l的浓度的镍离子。所述镍离子源选自水溶性镍盐。优选的镍盐源选自氯化镍、硫酸镍、甲烷磺酸镍及碳酸镍。
本发明的无电镀镍浴还含有还原剂，所述还原剂选自次磷酸盐化合物，诸如次磷酸钠和次磷酸钾。在所述镀浴中次磷酸根离子的浓度优选为10g/l-35g/l、更优选为20g/l-27g/l。
本发明的无电镀镍浴还含有络合剂的混合物，所述络合剂的混合物由选自羟基羧酸、二羟基羧酸及其盐的至少一种第一络合剂构成。
所述至少一种第二络合剂选自亚氨基琥珀酸、亚氨基二琥珀酸、其衍生物及其盐。
所述至少一种第一络合剂优选选自羟基丙二酸、乙醇酸、乳酸、柠檬酸、扁桃酸、酒石酸、苹果酸、对酒石酸、琥珀酸、天门冬氨酸及其盐。在所述至少一种第一络合剂的盐中的阳离子选自锂、钠和钾。最优选的第一络合剂选自琥珀酸、glycinic酸和乙醇酸。
所述至少一种第一络合剂的浓度为1g/l-50g/l，更优选为10g/l-20g/l。
选自亚氨基琥珀酸、二亚氨基琥珀酸(diiminosuccinic acid)、其衍生物或其盐的所述至少一种第二络合剂选自亚氨基琥珀酸、亚氨基二琥珀酸、其衍生物及其盐。在亚氨基琥珀酸衍生物的盐中的阳离子选自锂、钠和钾。
所述至少一种第二络合剂的浓度为0.2g/l-10g/l，更优选为0.8g/l-5g/l。
本发明的无电镀镍浴组合物还含有由两种组分组成的稳定剂混合物：
铋盐，
巯基苯甲酸、巯基羧酸和巯基磺酸及其盐。
加到所述无电镀镍浴中的铋盐为选自硝酸铋、酒石酸铋、硫酸铋、氧化铋和碳酸铋的水溶性铋盐。在所述无电镀镍浴中铋离子的浓度为0.5mg/l-100mg/l，优选为0.5mg/l-30mg/l，更优选为1mg/l-30mg/l。
所述巯基苯甲酸、其衍生物或盐选自2-巯基苯甲酸、3-巯基苯甲酸、4-巯基苯甲酸、其盐及其混合物。优选所述巯基苯甲酸或其衍生物的盐选自锂、钠和钾盐及上述盐的混合物。所述至少一种巯基苯甲酸或其盐的浓度为0.1mg/l-100mg/l，更优选为0.5mg/l-30mg/l。
所述巯基羧酸选自3-巯基丙酸、3-巯基-2-甲基丙酸、2-巯基丙酸、巯基乙酸、4-巯基丁酸、3-巯基异丁酸。优选所述巯基羧酸不是巯基乙酸。更优选所述巯基羧酸选自3-巯基丙酸、3-巯基-2-甲基丙酸、2-巯基丙酸、4-巯基丁酸、3-巯基异丁酸。
所述巯基磺酸选自2-巯基-1-乙烷磺酸、3-巯基-1-丙烷磺酸、4-巯基-1-丁烷磺酸。
所述至少一种巯基羧酸或巯基磺酸或其盐的浓度为0.1mg/l-100mg/l，更优选为0.5mg/l-30mg/l。
本发明的镍磷镀浴的pH值为6.5-11.5，优选为6.5-9.0。
所述镍磷镀浴在镀覆期间保持在20-55℃、优选25-35℃、更优选27-32℃的温度下。
镀覆时间为4-120分钟。
在镍合金的沉积期间，通常采用轻微搅拌镀浴；其搅拌可为轻微的空气搅拌、机械搅拌、通过泵送使浴循环、转动滚镀等。也可对镀覆溶液进行定期或连续的过滤处理以降低其中污染物的水平。在一些实施方案中，也可在定期或连续基础上进行浴成分的补充以维持成分的浓度且特别是镍离子和次磷酸根离子的浓度以及维持pH水平在所要极限内。
所述镍磷镀浴可优选用于镀覆非导电性塑料底材，其通常包括以下步骤：
a) 提供导电种子层(seed layer)到所述塑料底材上，
b) 通过使所述塑料底材与上述镀浴组合物接触而施用镍磷涂层到所述塑料底材上，
c) 任选用水冲洗所述镀覆的塑料底材和
d) 通过使所述塑料底材与包含铜离子的浸镀铜浴接触将铜涂层施用到所述镍磷涂层上。
在步骤d)中的铜浸镀之前不需要对所述镍磷涂层进行另外的活化步骤。
根据步骤a)非导电底材可通过各种方法活化，所述方法例如描述在Handbuch derLeiterplattentechnik，第4卷，2003，第292-300页中。这些方法包括形成包含碳粒子、Pd胶体或导电聚合物的导电层。这些方法中的一些描述在专利文献中且实例如下：
欧洲专利EP 0 616 053描述施用金属涂层到非导电底材(没有无电镀涂层)的方法包括：
a. 使所述底材与包含贵金属/IVA族金属溶胶的活化剂接触以获得处理过的底材；
b. 使所述处理过的底材与具有高于11-pH 13的pH的自加速且补充浸渍金属组合物接触，所述自加速且补充浸渍金属组合物包含以下各物的溶液：
(i)Cu(II)、Ag、Au或Ni可溶性金属盐或其混合物，
(ii)IA族金属氢氧化物，
(iii)包括对于所述金属盐的金属离子具有0.73-21.95的累计形成常数(cumulative formation constant)log K的有机材料的络合剂。
美国专利5,503,877描述非导电底材的金属化，其包括使用络合物以在非金属底材上产生金属种子。这些金属种子提供随后电镀的足够电导率。该方法在本领域中已知为所谓的“Neoganth”法。
优选施用以下工艺顺序：
a) 通过在含有100-400g/l CrO3和100-500g/l硫酸的水溶液中在50-80℃的高温下首先蚀刻例如ABS塑料底材的底材而将导电种子层提供到所述塑料底材上，
b) 通过使所述塑料底材与上述镀浴组合物接触而将镍磷涂层施用到所述塑料底材上，
c) 任选用水冲洗所述镀覆的塑料底材和
d) 通过使所述塑料底材与包含铜离子和硫酸的浸镀铜浴接触将铜涂层施用到所述镍磷涂层上。
通常，浸镀铜浴含有铜离子源，例如硫酸铜。铜离子浓度可根据镀覆方法而改变。其例如可在0.5-1.0g/l范围内。通常，其为弱酸性的且含有诸如硫酸的无机酸。如果需要，则可加入另外的添加剂，如表面活性剂。所述添加剂在本领域中已知。
此后，所述涂布的底材可用铜、铬、镍等通过本领域已知的电化学方法来进一步金属化。
实施例
现在将参考以下非限制性实施例说明本发明。
在沉积镍磷材料之前对用于所有实施例的ABS底材材料进行预处理：
首先将ABS底材在加热到65℃的含有360g/l CrO3和360g/l浓硫酸的水溶液中蚀刻6分钟。接着，将底材用水冲洗，浸泡到亚硫酸氢钠(sodium hydrogene sulfite)的水溶液中且再次用水冲洗。接着，将ABS底材浸泡到300ml/l浓盐酸的水溶液中，在由300ml/l浓盐酸、250mg/l氯化钯和17g/l氯化锡(II)组成的水溶液中活化1分钟且再次用水冲洗。
在由无电镀镍浴沉积镍磷合金涂层之后，将实施例1-4的ABS底材用水冲洗且随后在没有任何进一步的活化的情况下使其经受保持在35℃下的包含0.7g/l铜离子和1.7g/l浓硫酸的浸镀铜浴2分钟。
在溶解沉积物之后，镍磷合金沉积物的磷含量用AAS (原子吸收光谱法)测量。
得到的铜涂层的接触电阻率用标准万用表且在触尖之间的距离为1cm下测量。样品的接触电阻率越低，用铜涂布的镍磷层的覆盖度越好。
实施例1-根据本发明
镍磷合金从含有3.5g/l镍离子、25g/l次磷酸根离子(相当于11.9g/l磷)、5g/l柠檬酸和2.5g/l亚氨基二琥珀酸作为络合剂混合物及2.7mg/l铋离子和12.8mg/l 2-巯基苯甲酸作为稳定剂混合物的水性无电镀镍浴中沉积。
该无电镀镍浴的操作温度保持在35℃下且将ABS试片浸泡到镀浴中10分钟。
获得具有7.9重量%的磷含量的镍磷合金沉积物。
接着，将如此涂布的底材用水冲洗且随后在没有任何活化的情况下直接浸泡在保持在35℃下的包含0.7g/l铜离子和1.7g/l浓硫酸的浸镀铜浴中历时2分钟。将整个镍磷合金层用铜层涂布。
该镍磷合金且因此镀铜ABS试片的接触电阻在0.1Ω-1.6Ω/cm范围内，其对应于适合随后电镀的高电导率。
实施例2-根据本发明
使用含有相同化合物的无电镀镍浴重复实施例1，不同之处在于作为稳定剂的2-巯基苯甲酸由15mg/l 3-巯基丙酸代替。
获得具有7.6重量%的磷含量的镍磷合金沉积物。
接着，将如此涂布的底材用水冲洗且随后在没有任何活化的情况下直接浸泡在保持在35℃下的包含0.7g/l铜离子和1.7g/l浓硫酸的浸镀铜浴中历时2分钟。将整个镍磷合金层用铜层涂布。
该镍磷合金且因此镀铜ABS试片的接触电阻在0.2Ω-1.4Ω/cm范围内，其对应于适合随后电镀的高电导率。
实施例3-对比实施例
使用含相同化合物的无电镀镍浴重复实施例1，不同之处在于省略2-巯基苯甲酸。
获得具有11.2重量%的磷含量的镍磷合金沉积物。
当用上述铜浸镀溶液处理沉积的镍磷合金时，无法浸镀铜。
该镍磷合金的接触电阻在40Ω-60Ω/cm范围内。
实施例4-对比实施例
使用含相同化合物的无电镀镍浴重复实施例1，不同之处在于省略亚氨基二琥珀酸。
获得具有11.2重量%的磷含量的镍磷合金沉积物。
当用上述铜浸镀溶液处理沉积的镍磷合金时，无法浸镀铜。
该镍磷合金的接触电阻在50Ω-70Ω/cm范围内。
实施例5-根据本发明
镍磷合金从含有3.5g/l镍离子、25g/l次磷酸根离子(相当于11.9g/l磷)、5g/l柠檬酸和2.5g/l亚氨基二琥珀酸作为络合剂混合物及1mg/l铋离子和2mg/l 2-巯基苯甲酸作为稳定剂混合物的水性无电镀镍浴中沉积。该无电镀镍浴的pH值为8.0。
该无电镀镍浴的操作温度保持在35℃下且将ABS试片浸泡到镀浴中10分钟。
获得具有7.23重量%的磷含量和0.19重量%的铋含量的镍磷合金沉积物。沉积速率为1.53µm/h。
实施例6-根据本发明
使用含有相同化合物的无电镀镍浴重复实施例5，不同之处在于作为稳定剂的2-巯基苯甲酸由5mg/l巯基乙酸代替。
获得具有8.5重量%的磷含量和0.13重量%的铋含量的镍磷合金沉积物。沉积速率为1.40µm/h。
实施例7-对比实施例
使用含有相同化合物的无电镀镍浴重复实施例5，不同之处在于在络合剂混合物中的亚氨基二琥珀酸被2.5g/l琥珀酸代替。
获得具有11.4重量%的磷含量和0.22重量%的铋含量的镍磷合金沉积物。沉积速率为1.43µm/h。
实施例8-对比实施例
使用含有相同化合物的无电镀镍浴重复实施例5，不同之处在于作为稳定剂的2-巯基苯甲酸由2mg/l硫代二甘醇酸代替。
获得具有12.4重量%的磷含量和0.22重量%的铋含量的镍磷合金沉积物。沉积速率为1.28µm/h。
实施例9-根据本发明
镍磷合金从含有3.5g/l镍离子、25g/l次磷酸根离子(相当于11.9g/l磷)、5g/l柠檬酸和2.5g/l亚氨基二琥珀酸作为络合剂混合物及4mg/l铋离子和5mg/l 2-巯基苯甲酸作为稳定剂混合物的水性无电镀镍浴中沉积。该无电镀镍浴的pH值为8.6。
该无电镀镍浴的操作温度保持在35℃下且将ABS试片浸泡到镀浴中10分钟。
获得具有8.9重量%的磷含量的镍磷合金沉积物。
实施例10-根据本发明
使用含有相同化合物的无电镀镍浴重复实施例9，不同之处在于作为稳定剂的2-巯基苯甲酸由5mg/l的3-巯基-1-丙烷磺酸代替。
获得具有8.6重量%的磷含量的镍磷合金沉积物。

Claims (18)

1.用于沉积具有4-11重量%的磷含量的镍磷合金的无氨且无铅的无电镀镍浴，其包含：
i. 镍离子源；
ii. 次磷酸根离子源；
iii. 络合剂混合物，其包含：
a) 选自羟基羧酸、二羟基羧酸及其盐的至少一种第一络合剂和
b) 选自亚氨基琥珀酸、亚氨基二琥珀酸、其盐和衍生物的至少一种第二络合剂；
iv. 稳定剂混合物，其包含：
a) 铋离子，和
b) 选自巯基苯甲酸、巯基羧酸和巯基磺酸及其盐的至少一种化合物；
其中，所述至少一种第一络合剂的浓度为1g/l-50g/l，
所述至少一种第二络合剂的浓度为0.2g/l-10g/l，
铋离子的浓度为0.5mg/l-100mg/l，
所述巯基苯甲酸、巯基羧酸和巯基磺酸或其盐的浓度为0.1mg/l-100mg/l。
2.权利要求1的无电镀镍浴，其中所述至少一种第一络合剂选自羟基丙二酸、乙醇酸、乳酸、柠檬酸、扁桃酸、酒石酸、苹果酸、对酒石酸、琥珀酸、天门冬氨酸及其盐。
3.上述权利要求中任一项的无电镀镍浴，其中所述次磷酸根离子的浓度为10g/l-35g/l。
4.权利要求1或2的无电镀镍浴，其中所述至少一种第一络合剂的浓度为10g/l-20g/l。
5.权利要求1或2的无电镀镍浴，其中所述至少一种第二络合剂的浓度为0.8g/l-5g/l。
6.权利要求1或2的无电镀镍浴，其中铋离子的浓度为0.5mg/l-30mg/l。
7.权利要求1或2的无电镀镍浴，其中铋离子的浓度为1mg/l-30mg/l。
8.权利要求1或2的无电镀镍浴，其中所述巯基苯甲酸衍生物选自2-巯基苯甲酸、3-巯基苯甲酸、4-巯基苯甲酸、其盐及其混合物。
9.权利要求1或2的无电镀镍浴，其中所述巯基羧酸选自3-巯基丙酸、3-巯基-2-甲基丙酸、2-巯基丙酸、巯基乙酸、4-巯基丁酸和3-巯基异丁酸。
10.权利要求1或2的无电镀镍浴，其中所述巯基磺酸选自2-巯基-1-乙烷磺酸、3-巯基-1-丙烷磺酸、4-巯基-1-丁烷磺酸。
11.权利要求1或2的无电镀镍浴，其中所述巯基苯甲酸、巯基羧酸和巯基磺酸或其盐的浓度为0.5mg/l-30mg/l。
12.权利要求1或2的无电镀镍浴，其中所述磷含量为6-9重量%。
13.权利要求1或2的无电镀镍浴，其中所述镀浴的pH值为6.5-11.5。
14.金属镀覆非导电底材的方法，其包括以下步骤：
i. 提供导电种子层到所述非导电底材上；
ii. 通过使所述非导电底材与权利要求1-12中任一项的镀浴组合物接触而将镍磷涂层施用到所述非导电底材上；
iii. 任选用水冲洗所述镀覆的底材；和
iv. 通过使所述底材与包含铜离子的浸镀铜浴接触将铜涂层施用到所述镍磷涂层上。
15.权利要求14的方法，其中用于将镍磷涂层施用到所述非导电底材上的镀浴保持在20-55℃的温度下。
16.权利要求14的方法，其中用于将镍磷涂层施用到所述非导电底材上的镀浴保持在25-35℃的温度下。
17.权利要求14或16的方法，其中所述非导电底材为由ABS或ABS/PC共混物制成的塑料底材。
18.权利要求14或16的方法，其还包括：
v. 将至少一个电解沉积金属层施用到在步骤iv中沉积的浸渍铜层上，其中所述至少一个电解沉积层选自铜、镍、铬或其合金。
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