印制线路板酸性镀铜整平剂的合成与应用
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摘要
对市售印制线路板酸铜添加剂(YL-603)进行了剖析。通过常压蒸馏、萃取和化学沉淀法对YL-603进行了分离,利用红外光谱、核磁共振氢谱和X-射线衍射等方法对分离产物进行了表征。结果表明:YL-603以水作溶剂,剩余组分的质量百分含量约为18.8%;YL-603含有聚乙二醇(PEG),其质量百分含量约为9.8%;YL-603含有H_2SO_4,溶液的pH=0.98。
以N-乙烯基咪唑、卤代化合物、丙烯酸乙酯为原料,在偶氮双异丁腈(AIBN)引发聚合下,合成了系列N-乙烯基咪唑聚合物:聚溴化N-乙烯基-N'-丁基咪唑鎓盐(QPVIBr)、聚氯化N-乙烯基-N'-丁基咪唑鎓盐(QPVICI)、聚碘化N-乙烯基-N'-乙基咪唑鎓盐(QPVII)、聚氯化N-乙烯基-N'-苄基咪唑鎓盐(QPVIBCI)、聚氯化N-乙烯基-N'-环氧丙基咪唑鎓盐(QPVIECI)、聚N-乙烯基咪唑-丙烯酸乙酯(VI-EA)以及聚溴化N-乙烯基-N'-丁基咪唑-丙烯酸乙酯(QVI-EA)。利用红外光谱、核磁氢谱、元素分析、紫外光谱等方法对合成产物的结构进行了表征与分析。
通过对合成的N-乙烯基咪唑聚合物的阴极极化曲线测试,结果表明:QPVIBr和QVI-EA对酸性镀铜有显著的阴极极化作用;通过交流阻抗测试,结果表明:QPVIBr和QVI-EA对酸性镀铜有显著的化学反应阻抗。最后选择QPVIBr和QVI-EA作为酸性镀铜整平剂。
通过电镀实验,结果表明:含有QPVIBr或QVI-EA的酸性镀铜液均可获得表面光亮平整、结晶颗粒细致的铜镀层,且镀液的覆盖能力强;含QPVIBr整平剂的酸性镀铜比YL-603获得的镀层更具有平整性;自配的酸铜添加剂在镀液中的组成为PEG(6000)2.24 g/L、聚二硫二丙烷磺酸钠(SPS)26 mg/L、脂肪胺乙氧基磺化物(AESS)0.02 g/L、QPVIBr1.0-1.8 mL/L或QVI-EA 1.2-2.2 mL/L。
This paper was conducted on the acidic copper brightener (YL-603) which was applied for the processing of printed circuit board. The YL-603 was separated via atmospheric distillation, extract separation and chemical precipitation. The components of YL-603 were characterized and identified by IR, ~1H-NMR, and X-ray diffraction. The results are shown as follows: the sample of YL-603 contained water used as solvent, and 18.8 % for percentage mass content of the other contents; The percentage mass content of Polyethylene glycol(PEG) is 9.8 %; Sulfuric acid is also in existence and the pH of YL-603 is 0.98.
Under the free radical initiator of a,a'-azobisisobutyroniytile, poly(N-vinyl-N'-butylimidazoliniumbromize)(QPVIBr), poly(N-vinyl-N'-butylimidazoliniumchloride)(QPVICI), poly(N-vinyl-N'-vinylimidazoliniumiodide)(QPVII), poly(N-vinyl-N'-benzylimidazoliniumchloride)(QPVIBCI), poly(N-vinyl-N'-epoxypropylimidazoliniumchloride)(QPVIECI), poly(N-vinylimidazole-co-ethylacrylate)(VI-EA) andpoly(N-vinyl-N'-butylimidazoliniumbromize-co-ethylacrylate)(QVI-EA) were synthesized from N-vinylimidazole, halogenide and ethylacrylate(EA). The structures of products were characterized by IR, ~1H-NMR, UV, EA, etc.
The synthesized compounds were filtrated as acidic copper leveler according to the cathodic polarization curves. The results indicated that both QPVIBr and QVI-EA can promote the copper ion into polarization in PCB acidic copper plating bath greatly. Moreover, it was found that both of them have obvious chemical reaction impedance on copper eletrodeposition by the detection of impedance spectroscopy. Finally, the QPVIBr and QVI-EA were chosen as acidic copper leveler.
The merits of QPVIBr and QVI-EA were discovered and presented in the electroplating experiments. When these two reagents were added in acidic copper plating bath, the brightening, leveling and fine coatings can be obtained. Moreover, better coverage ability of the plating bath than before was also found. The acidic copper plating bath added with QPVIBr can obtain more uniform coatings than YL-603. In the end, the optimal contents of additives in acidic copper bath constitutes were optimized as follows: PEG(6000)2.24 g/L, SPS 26 mg/L, AESS 0.02 g/L, QPVIBr 1.0-1.8 mL/L or QVI-EA 1.2-2.2 mL/L。
以N-乙烯基咪唑、卤代化合物、丙烯酸乙酯为原料,在偶氮双异丁腈(AIBN)引发聚合下,合成了系列N-乙烯基咪唑聚合物:聚溴化N-乙烯基-N'-丁基咪唑鎓盐(QPVIBr)、聚氯化N-乙烯基-N'-丁基咪唑鎓盐(QPVICI)、聚碘化N-乙烯基-N'-乙基咪唑鎓盐(QPVII)、聚氯化N-乙烯基-N'-苄基咪唑鎓盐(QPVIBCI)、聚氯化N-乙烯基-N'-环氧丙基咪唑鎓盐(QPVIECI)、聚N-乙烯基咪唑-丙烯酸乙酯(VI-EA)以及聚溴化N-乙烯基-N'-丁基咪唑-丙烯酸乙酯(QVI-EA)。利用红外光谱、核磁氢谱、元素分析、紫外光谱等方法对合成产物的结构进行了表征与分析。
通过对合成的N-乙烯基咪唑聚合物的阴极极化曲线测试,结果表明:QPVIBr和QVI-EA对酸性镀铜有显著的阴极极化作用;通过交流阻抗测试,结果表明:QPVIBr和QVI-EA对酸性镀铜有显著的化学反应阻抗。最后选择QPVIBr和QVI-EA作为酸性镀铜整平剂。
通过电镀实验,结果表明:含有QPVIBr或QVI-EA的酸性镀铜液均可获得表面光亮平整、结晶颗粒细致的铜镀层,且镀液的覆盖能力强;含QPVIBr整平剂的酸性镀铜比YL-603获得的镀层更具有平整性;自配的酸铜添加剂在镀液中的组成为PEG(6000)2.24 g/L、聚二硫二丙烷磺酸钠(SPS)26 mg/L、脂肪胺乙氧基磺化物(AESS)0.02 g/L、QPVIBr1.0-1.8 mL/L或QVI-EA 1.2-2.2 mL/L。
This paper was conducted on the acidic copper brightener (YL-603) which was applied for the processing of printed circuit board. The YL-603 was separated via atmospheric distillation, extract separation and chemical precipitation. The components of YL-603 were characterized and identified by IR, ~1H-NMR, and X-ray diffraction. The results are shown as follows: the sample of YL-603 contained water used as solvent, and 18.8 % for percentage mass content of the other contents; The percentage mass content of Polyethylene glycol(PEG) is 9.8 %; Sulfuric acid is also in existence and the pH of YL-603 is 0.98.
Under the free radical initiator of a,a'-azobisisobutyroniytile, poly(N-vinyl-N'-butylimidazoliniumbromize)(QPVIBr), poly(N-vinyl-N'-butylimidazoliniumchloride)(QPVICI), poly(N-vinyl-N'-vinylimidazoliniumiodide)(QPVII), poly(N-vinyl-N'-benzylimidazoliniumchloride)(QPVIBCI), poly(N-vinyl-N'-epoxypropylimidazoliniumchloride)(QPVIECI), poly(N-vinylimidazole-co-ethylacrylate)(VI-EA) andpoly(N-vinyl-N'-butylimidazoliniumbromize-co-ethylacrylate)(QVI-EA) were synthesized from N-vinylimidazole, halogenide and ethylacrylate(EA). The structures of products were characterized by IR, ~1H-NMR, UV, EA, etc.
The synthesized compounds were filtrated as acidic copper leveler according to the cathodic polarization curves. The results indicated that both QPVIBr and QVI-EA can promote the copper ion into polarization in PCB acidic copper plating bath greatly. Moreover, it was found that both of them have obvious chemical reaction impedance on copper eletrodeposition by the detection of impedance spectroscopy. Finally, the QPVIBr and QVI-EA were chosen as acidic copper leveler.
The merits of QPVIBr and QVI-EA were discovered and presented in the electroplating experiments. When these two reagents were added in acidic copper plating bath, the brightening, leveling and fine coatings can be obtained. Moreover, better coverage ability of the plating bath than before was also found. The acidic copper plating bath added with QPVIBr can obtain more uniform coatings than YL-603. In the end, the optimal contents of additives in acidic copper bath constitutes were optimized as follows: PEG(6000)2.24 g/L, SPS 26 mg/L, AESS 0.02 g/L, QPVIBr 1.0-1.8 mL/L or QVI-EA 1.2-2.2 mL/L。
引文
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[6]余德超,谈定生.电镀铜技术在电子材料中的应用[J].电镀与涂饰,2006,2(26):43-47
[7]烈炜,郭田炜,赵志祥.酸性镀铜添加剂及其工艺的发展回顾[J].材料保护,2001,34(11):19-21
[8]杨秀芳.酸性光亮镀铜的研究[J].陕西科技大学学报,2004,1(22):29-31
[9]周绍民,张瀛洲,姚土冰,等.某些光亮酸性镀铜添加剂的作用机理[J].厦门大学学报,1980,(1):54-70
[10]陈德宝.酸性光亮镀铜光亮剂添加方法的改进[J].电镀与精饰,1 982,4(4):39-42
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[13]叶云川.镀铜添加剂SH110微观整平研究[J].电镀与精饰,1990,12(4):27-33
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