CN111763930B - 一种非钯活化镀铜工艺及其敏化剂、活化剂 - Google Patents

一种非钯活化镀铜工艺及其敏化剂、活化剂 Download PDF

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CN111763930B
CN111763930B CN202010673449.XA CN202010673449A CN111763930B CN 111763930 B CN111763930 B CN 111763930B CN 202010673449 A CN202010673449 A CN 202010673449A CN 111763930 B CN111763930 B CN 111763930B
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朱祖光
王世雄
熊汉峰
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Chibi Jumao New Material Technology Co ltd
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Abstract

本发明提供一种非钯活化镀铜工艺,包括以下步骤:步骤S1:除油;步骤S2:粗化:采用粗化液对工件进行粗化,然后进行超声水洗;步骤S3:敏化:将水洗后的工件放入敏化剂中敏化,敏化剂包括以下组分和浓度配比:甲基磺酸锡5‑100g/L、酒石酸1‑50g/L、抗坏血酸1‑10g/L、柠檬酸5‑50g/L、2,4‑氨基吡啶1‑20g/L、氨基硅烷偶联剂1‑10ml/L、表面活性剂1‑10ml/L;步骤S4:活化:将敏化后的工件放入活化剂中活化,活化剂包括以下组分和浓度配比:硝酸银1‑20g/L、氨水1‑50ml/L、EDTA1‑50g/L、三乙醇胺1‑20ml/L、2,4‑氨基吡啶0.5‑5g/L、磷酸酯表面活性剂0.1‑10ml/L;步骤S5:预铜;步骤S6:厚铜。本发明提供一种生产成本低、镀层结合结合力好、绿色环保的非钯活化镀铜工艺及其敏化剂、活化剂。

Description

一种非钯活化镀铜工艺及其敏化剂、活化剂
技术领域
本发明属于化学镀铜技术领域,特别涉及非钯活化镀铜工艺及其敏化剂、活化剂。
背景技术
随着5G技术的兴起与高速发展,5G手机天线工艺是在PC料手机壳上镭雕线路后,再进行活化镀铜镀镍金属化工艺来完成制备。通常的活化镀铜镀镍金属化的工艺步骤为:PC料、PPS料或者陶瓷料进过除油→粗化→超声波→敏化→活化→触发铜/镍→厚铜/镍工艺完成镀铜或者镀镍。这种活化镀铜镀镍金属化工艺可以应用在PPS料的5G基站振子、陶瓷介质滤波器的生产中。
目前,现有技术的活化镀铜镀镍金属化的工艺中是需要通过钯离子或者胶体钯作为氧化活化剂将钯离子还原成钯金属,最后再以钯金属为晶核沉积铜单质或者镍单质完成镀铜/镀镍工艺。但是,钯离子作为原料的成本高居不下,并且采用钯作为活化剂的操作工序操作难以控制,特别是PC料5G手机天线,活化与水洗的时间掌握不当,容易漏镀、溢镀。
因此,需要研究革新一种生产成本低、镀层结合结合力好、绿色环保的非钯活化镀铜工艺及其敏化剂、活化剂。
发明内容
本发明的目的是提供一种生产成本低、镀层结合结合力好、绿色环保的非钯活化镀铜工艺及其敏化剂、活化剂。
本发明的上述技术目的是通过以下技术方案得以实现的:一种非钯活化镀铜工艺,包括以下步骤:
步骤S1:除油:将工件置于清洗液中超声清洗除去表面油污;
步骤S2:粗化:采用粗化液对工件进行粗化,然后进行超声水洗;
步骤S3:敏化:将水洗后的工件放入敏化剂中敏化,所述敏化剂包括以下组分和浓度配比:甲基磺酸锡5-100g/L、酒石酸1-50g/L、抗坏血酸1-10g/L、柠檬酸5-50g/L、2,4-氨基吡啶1-20g/L、氨基硅烷偶联剂1-10ml/L、表面活性剂1-10ml/L;
步骤S4:活化:将敏化后的工件放入活化剂中活化,所述活化剂包括以下组分和浓度配比:硝酸银1-20g/L、氨水1-50ml/L、EDTA1-50g/L、三乙醇胺1-20ml/L、2,4-氨基吡啶0.5-5g/L、磷酸酯表面活性剂0.1-10ml/L;
步骤S5:预铜:将工件浸入预铜液中快速镀上一层薄铜层;
步骤S6:厚铜:将工件置于厚铜液中,缓慢均匀镀成厚铜层。
通过采用上述技术方案,PC/PPS/ABS/PE等碳链形成的塑料或者陶瓷工件经过粗化后会在工件表面形成无数均匀密布的微小孔,并且粗化液与塑料官能团进行反应,将其中的官能团键断裂,使小孔内带有负电荷,便于后序敏化、活化过程中带正电的金属离子和胶体粒子吸附沉积,再进入敏化过程,敏化剂中的具有还原性的Sn2+被微小孔表面的负电荷相吸引,均匀分布在小孔内表面,而后在活化过程中,Ag+具有氧化性,Ag+被Sn2+还原成单质Ag吸附在小孔中形成锚着效应,再进入预铜工序中,Ag形成活性晶核不断使Cu单质沉积在Ag晶核表面,形成Cu沉积金属层,再以Cu沉积金属层形成晶核不断沉积Cu单质,最后形成镀铜层。
作为本发明的进一步设置,在步骤S3和步骤S4之间还包括步骤S3’:水洗:将敏化后的工件置于装有去离子水的水洗槽中浸泡1-5min。
通过采用上述技术方案,Sn2+在敏化剂中为pH<2的酸性环境,然后再经过水洗工序中在去离子水浸液中Sn2+进行水解反应生成Sn(OH)2,再进入活化工序中与Ag+络合反应生成Sn(OH)2-Ag胶体,以Sn(OH)2-Ag胶体为活化中心,Cu2+反应活性更强,能有效提高镀铜反应的反应效率。
作为本发明的进一步设置,步骤S2中粗化液包括以下组分和重量配比:氢氧化钠50-200g、过硫酸铵20-50g和氟氢化铵1-10g。
通过采用上述技术方案,粗化液中为氢氧化钠、过硫酸铵和氟氢化铵,氟氢化铵能提高微小孔形成外小内大的收口型凹坑的比例,提高后序金属离子、胶体粒子乃至铜单质吸附沉积的吸附结合力,最终铜层在这种收口型的凹坑形成像铆钉一样的结构,提高铜层的结合力。
作为本发明的进一步设置,步骤S3中氨基硅烷偶联剂为hk-550。
作为本发明的进一步设置,步骤S3中表面活性剂为氟碳表面活性剂FC。
作为本发明的进一步设置,步骤S4中磷酸酯表面活性剂为异构十三醇醚磷酸酯。
作为本发明的进一步设置,工艺应用的工件为PC、PPS、ABS、PE塑料或陶瓷的一种或多种。
本发明还提供一种非钯活化镀铜工艺的敏化剂,包括以下组分和浓度配比:甲基磺酸锡5-100g/L、酒石酸1-50g/L、抗坏血酸1-10g/L、柠檬酸5-50g/L、2,4-氨基吡啶1-20g/L、氨基硅烷偶联剂1-10ml/L、表面活性剂1-10ml/L。
本发明还提供一种非钯活化镀铜工艺的活化剂,包括以下组分和浓度配比:硝酸银1-20g/L、氨水1-50ml/L、EDTA1-50g/L、三乙醇胺1-20ml/L、2,4-氨基吡啶0.5-5g/L、磷酸酯表面活性剂0.1-10ml/L。
通过采用上述技术方案,敏化剂中锡离子与活化剂银离子共同作用,替代钯胶体形成Sn(OH)2-Ag胶体的铜离子活化中心,有效降低的生产成本,形成的镀铜层镀铜均匀,有效提高镀铜层的平整度和结合力,并且在敏化剂中添加了2,4-氨基吡啶,能有效促进Sn2+吸附在微小孔中,并且2,4-氨基吡啶能有效提高Sn2+的分散性,提高镀铜层的均匀性和镀铜结合力。
本发明的有益效果是:
1.本发明采用含锡离子的敏化剂与含银离子的活化剂配合使用,在制备工艺中不含贵金属钯,有效降低镀铜/镀镍的生产成本。
2.本发明最后采用预铜和厚铜两步操作,在预过程中,镀铜反应的速度快并且活性高,然后进入厚铜步骤,反应减缓,但是镀铜层不断加厚,镀铜的均匀性提高,有效提高镀铜层的平整性和与工件的结合力,操作过程中不会产生漏镀和溢镀现象,大大提高了产品的合格率。
3.本发明工艺步骤简单,操作方便,经济效益好。
具体实施方式
下面将对实施例中的技术方案进行清楚、完整地描述。显然,所描述的实施例仅仅是本发明的一部分实施例,而不是全部的实施例。基于本发明的实施例,本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施例1
本发明提供一种非钯活化镀铜工艺的敏化剂,包括以下组分和浓度配比:甲基磺酸锡5g/L、酒石酸1g/L、抗坏血酸1g/L、柠檬酸5g/L、2,4-氨基吡啶1g/L、氨基硅烷偶联剂1ml/L、表面活性剂1ml/L。
本发明还提供一种非钯活化镀铜工艺的活化剂,包括以下组分和浓度配比:硝酸银1g/L、氨水1ml/L、EDTA1g/L、三乙醇胺1ml/L、2,4-氨基吡啶0.5g/L、磷酸酯表面活性剂0.1ml/L。
实施例2
本发明提供一种非钯活化镀铜工艺的敏化剂,包括以下组分和浓度配比:甲基磺酸锡100g/L、酒石酸50g/L、抗坏血酸10g/L、柠檬酸50g/L、2,4-氨基吡啶20g/L、氨基硅烷偶联剂10ml/L、表面活性剂10ml/L。
本发明还提供一种非钯活化镀铜工艺的活化剂,包括以下组分和浓度配比:硝酸银20g/L、氨水50ml/L、EDTA50g/L、三乙醇胺20ml/L、2,4-氨基吡啶5g/L、磷酸酯表面活性剂10ml/L。
实施例3
本发明提供一种非钯活化镀铜工艺的敏化剂,包括以下组分和浓度配比:甲基磺酸锡50g/L、酒石酸25g/L、抗坏血酸5g/L、柠檬酸25g/L、2,4-氨基吡啶10g/L、氨基硅烷偶联剂5ml/L、表面活性剂5ml/L。
本发明还提供一种非钯活化镀铜工艺的活化剂,包括以下组分和浓度配比:硝酸银10g/L、氨水25ml/L、EDTA25g/L、三乙醇胺10ml/L、2,4-氨基吡啶2.5g/L、磷酸酯表面活性剂5ml/L。
实施例4
本实施例采用上述实施例1中的非钯活化镀铜工艺的活化剂和敏化剂进行非钯活化镀铜工艺,包括如下步骤:
步骤S1:除油:将工件置于清洗液中超声清洗除去表面油污;
步骤S2:粗化:采用粗化液对工件进行粗化,然后进行超声水洗;
步骤S3:敏化:将水洗后的工件放入敏化剂中敏化,所述敏化剂包括以下组分和浓度配比:甲基磺酸锡5g/L、酒石酸1g/L、抗坏血酸1g/L、柠檬酸5g/L、2,4-氨基吡啶1g/L、氨基硅烷偶联剂1ml/L、表面活性剂1ml/L;
步骤S4:活化:将敏化后的工件放入活化剂中活化,所述活化剂包括以下组分和浓度配比:硝酸银1g/L、氨水1ml/L、EDTA1g/L、三乙醇胺1ml/L、2,4-氨基吡啶0.5g/L、磷酸酯表面活性剂0.1ml/L;
步骤S5:预铜:将工件浸入预铜液中快速镀上一层薄铜层;
步骤S6:厚铜:将工件置于厚铜液中,缓慢均匀镀成厚铜层。
实施例5
本实施例采用上述实施例1中的非钯活化镀铜工艺的活化剂和敏化剂进行非钯活化镀铜工艺,包括如下步骤:
步骤S1:除油:将工件置于清洗液中超声清洗除去表面油污;
步骤S2:粗化:采用粗化液对工件进行粗化,然后进行超声水洗;
步骤S3:敏化:将水洗后的工件放入敏化剂中敏化,所述敏化剂包括以下组分和浓度配比:甲基磺酸锡100g/L、酒石酸50g/L、抗坏血酸10g/L、柠檬酸50g/L、2,4-氨基吡啶20g/L、氨基硅烷偶联剂10ml/L、表面活性剂10ml/L;
步骤S4:活化:将敏化后的工件放入活化剂中活化,所述活化剂包括以下组分和浓度配比:硝酸银20g/L、氨水50ml/L、EDTA50g/L、三乙醇胺20ml/L、2,4-氨基吡啶5g/L、磷酸酯表面活性剂10ml/L;
步骤S5:预铜:将工件浸入预铜液中快速镀上一层薄铜层;
步骤S6:厚铜:将工件置于厚铜液中,缓慢均匀镀成厚铜层。
实施例6
本实施例采用上述实施例3中的非钯活化镀铜工艺的活化剂和敏化剂进行非钯活化镀铜工艺,包括如下步骤:
步骤S1:除油:将工件置于清洗液中超声清洗除去表面油污;
步骤S2:粗化:采用粗化液对工件进行粗化,然后进行超声水洗;
步骤S3:敏化:将水洗后的工件放入敏化剂中敏化,所述敏化剂包括以下组分和浓度配比:甲基磺酸锡50g/L、酒石酸25g/L、抗坏血酸5g/L、柠檬酸25g/L、2,4-氨基吡啶10g/L、氨基硅烷偶联剂5ml/L、表面活性剂5ml/L;
步骤S4:活化:将敏化后的工件放入活化剂中活化,所述活化剂包括以下组分和浓度配比:硝酸银10g/L、氨水25ml/L、EDTA25g/L、三乙醇胺10ml/L、2,4-氨基吡啶2.5g/L、磷酸酯表面活性剂5ml/L;
步骤S5:预铜:将工件浸入预铜液中快速镀上一层薄铜层;
步骤S6:厚铜:将工件置于厚铜液中,缓慢均匀镀成厚铜层。
实施例4~6都达到较佳的镀镍效果,在显微镜下观察,可以看出,铜层上镀铜均匀、细腻、平整、颜色鲜亮,操作沉积速度可以达到18-20mu/h,镀层5um盐雾试验可达48h以上,百格测试等级可达到5B,进一步工序镀镍3-5μm钝化干燥烘烤后,盐雾试验可达72h以上,百格测试等级可达到5B。

Claims (8)

1.一种非钯活化镀铜工艺,其特征在于:包括以下步骤:
步骤S1:除油:将工件置于清洗液中超声清洗除去表面油污;
步骤S2:粗化:采用粗化液对工件进行粗化,然后进行超声水洗,所述粗化液包括以下组分和重量配比:氢氧化钠50-200g、过硫酸铵20-50g和氟氢化铵1-10g;
步骤S3:敏化:将水洗后的工件放入敏化剂中敏化,所述敏化剂包括以下组分和浓度配比:甲基磺酸锡5-100g/L、酒石酸1-50g/L、抗坏血酸1-10g/L、柠檬酸5-50g/L、2,4-氨基吡啶1-20g/L、氨基硅烷偶联剂1-10ml/L、表面活性剂1-10ml/L;
步骤S4:活化:将敏化后的工件放入活化剂中活化,所述活化剂包括以下组分和浓度配比:硝酸银1-20g/L、氨水1-50ml/L、EDTA 1-50g/L、三乙醇胺1-20ml/L、2,4-氨基吡啶0.5-5g/L、磷酸酯表面活性剂0.1-10ml/L;
步骤S5:预铜:将工件浸入预铜液中快速镀上一层薄铜层;
步骤S6:厚铜:将工件置于厚铜液中,缓慢均匀镀成厚铜层。
2.根据权利要求1所述的非钯活化镀铜工艺,其特征在于:在步骤S3和步骤S4之间还包括步骤S3’:水洗:将敏化后的工件置于装有去离子水的水洗槽中浸泡1-5min。
3.根据权利要求1所述的非钯活化镀铜工艺,其特征在于:所述步骤S3中氨基硅烷偶联剂为hk-550。
4.根据权利要求1所述的非钯活化镀铜工艺,其特征在于:所述步骤S3中表面活性剂为氟素表面活性剂FC。
5.根据权利要求1所述的非钯活化镀铜工艺,其特征在于:所述步骤S4中磷酸酯表面活性剂为异构十三醇醚磷酸酯。
6.根据权利要求1所述的非钯活化镀铜工艺,其特征在于,所述工艺应用的工件为PC、PPS、ABS、PE塑料或陶瓷的一种或多种。
7.一种根据权利要求1所述的非钯活化镀铜工艺的活化剂,其特征在于:包括以下组分和浓度配比:甲基磺酸锡5-100g/L、酒石酸1-50g/L、抗坏血酸1-10g/L、柠檬酸5-50g/L、2,4-氨基吡啶1-20g/L、氨基硅烷偶联剂1-10ml/L、表面活性剂1-10ml/L。
8.一种根据权利要求1所述的非钯活化镀铜工艺的敏化剂,其特征在于:包括以下组分和浓度配比:硝酸银1-20g/L、氨水1-50ml/L、EDTA 1-50g/L、三乙醇胺1-20ml/L、2,4-氨基吡啶0.5-5g/L、磷酸酯表面活性剂0.1-10ml/L。
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