CN103041858B - 用于化学镀的稳定的不含锡催化剂 - Google Patents
用于化学镀的稳定的不含锡催化剂 Download PDFInfo
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- CN103041858B CN103041858B CN201210395248.3A CN201210395248A CN103041858B CN 103041858 B CN103041858 B CN 103041858B CN 201210395248 A CN201210395248 A CN 201210395248A CN 103041858 B CN103041858 B CN 103041858B
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- Prior art keywords
- catalyst
- palladium
- substrate
- copper
- metal
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- 238000000034 method Methods 0.000 claims description 33
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- 239000010949 copper Substances 0.000 claims description 28
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Abstract
将包含钯金属的纳米微粒和纤维素衍生物的催化剂用于化学镀。钯催化剂不含锡。
Description
技术领域
本发明涉及用于化学镀的不含锡的钯催化剂的稳定水溶液。进一步地，本发明涉及用于化学镀的不含锡的钯催化剂的稳定水溶液、其中催化剂包括钯金属的纳米微粒和纤维素或纤维素衍生物。
背景技术
化学镀金属沉积法是用于基底表面沉积金属层的众所周知的方法。绝缘体表面的化学镀需要预先使用催化剂。最常用的催化或激活绝缘体的方法，如用于生产印刷电路板的薄板基底的非导电部分，是用酸性氯化物介质中的锡/钯胶体水溶液来处理基底。胶体的结构已被广泛研究过。通常来说，胶体包括被锡离子(II)的稳定层包围的钯金属核，所述锡离子实质上是作为避免悬浮液中胶体聚结的表面稳定基团的SnCl3 -配合物壳层。
在活化方法中，锡/钯胶体催化剂吸附到绝缘体基底上，如含有环氧或聚胺的基底，以活化化学金属沉积。理论上，催化剂用作电子转移路径载体，将电子在化学镀槽中从还原剂转移到金属离子上。尽管化学镀的性能受诸多因素影响，如镀层溶液的添加组分，但活化步骤是控制化学镀的速率和机理的关键。
近年来，随着电子装置尺寸的减小以及对其性能需求的增加，在电子电路组装行业中对无缺陷电子线路的需求在逐渐增加。尽管几十年来在商业上已将锡/钯胶体用作化学镀的催化剂，并提供了可接受的服务，但随着对电子设备质量要求的进一步提高，该类催化剂的诸多弊端也逐渐凸显出来。锡/钯胶体的稳定性是主要的考虑因素。如上所述的锡/钯胶体用一层锡离子(II)进行稳定，其反阴离子能够阻止钯的聚结。催化剂对空气敏感、容易氧化成锡(IV)，这样胶体不能保持其胶体结构。化学镀过程中温度的升高和搅拌会进一步促进这种氧化。如果锡(II)的浓度降至危险水平，如接近于零，钯金属微粒会尺寸变大、产生聚结和沉积，从而失去催化活性。由此便增加了对更稳定的催化剂的需求。另外，钯的高成本和价格波动也促使行业上寻求更廉价的金属。
已付出相当多的努力寻找新型的改进催化剂。因为钯的成本高，很多努力致力于发展不含钯的催化剂，比如胶体银催化剂。另外一个研究方向则是开发不含锡的钯催化剂，这是因为氯化锡成本高以及氧化的锡需要单独的加速步骤。在金属喷镀过程中加速步骤是额外的步骤，该步骤经常会剥落基底尤其是玻璃纤维基底上的催化剂，从而在镀层基底表面中留下不希望的空区。然而，这种不含锡的催化剂用于印刷电路板生产中的通孔的镀时则表现为活性和可靠性不足。并且，这种催化剂通常在储存中活性会逐渐降低，从而导致该催化剂不稳定、不适于商业应用。
已研究用于锡复合物的另一稳定部分，如聚乙烯基吡咯烷酮(PVP)和树状聚合物。多个研究团体在文献中已公开了由稳定且均一的PVP保护的纳米微粒。文献中已报道了其它的金属胶体，如部分钯被非贵金属取代的银/钯和铜/钯；然而，至今为止还没有商业上可接受的替代催化剂。商业上已开始使用离子钯催化剂变体，但其需要额外的还原步骤。因此对稳定、可靠的化学镀催化剂仍有需求。
发明内容
催化剂水溶液包括一种或多种抗氧化剂，钯金属的纳米微粒，以及一种或多种选自具有如下通式的聚合物和以下反应产物的化合物：
其中R1，R2，R3，R4，R5，R6和R7相同或不同，其选自-H，CH2COOX，-C(O)-CH3，-C(O)-(CH2)z-CH3以及
其中n表示至少为2的整数，z表示至少为1的整数以及X表示-H或是反阳离子，所述反应产物是以下物质的的反应产物：具有如下通式的聚合物
其中R9，R10，R11，R12，R13，R14和R15相同或不同，其选自-H，-CH3，-CH2CH3，-CH2OH，-[CH2CHR8]x-OH，-CH2CH(OH)CH3和-(CH2CHR8O)y-H，前提是R9，R10，R11，R12，R13，R14和R15中至少一个为-CH2OH，-[CH2CHR8]x-OH，-CH2CH(OH)CH3或-(CH2CHR8O)y-H，其中R8表示-H或-CH3，x和y是至少为1的整数，n和z如上所述；季化合物，具有如下通式：
其中m为1至16的整数，Y表示卤素，Z-表示反阴离子，R16，R17和R18相同或不同，其为-H，-CH3或-(CH2)p-CH3，R19为-H或-CH3，p为1至9的整数，以及一种或多种交联剂；和催化剂不含锡。
方法包括：
a)提供基底；
b)将催化剂水溶液施加到基底上，催化剂水溶液包括一种或多种抗氧化剂，钯金属的纳米微粒，以及一种或多种选自具有如下通式聚合物和以下所述反应产物的化合物；
其中R1，R2，R3，R4，R5，R6和R7相同或不同，其选自-H，-CH2COOX，-C(O)-CH3，-C(O)-(CH2)z-CH3以及
其中n表示至少为2的整数，z是至少为1的整数以及X为-H或是反阳离子，所述反应产物是以下物质的反应产物：具有如下通式的聚合物
其中R9，R10，R11，R12，R13，R14和R15相同或不同，其选自-H，-CH3，-CH2CH3，-CH2OH，-[CH2CHR8]x-OH，-CH2CH(OH)CH3以及-(CH2CHR8O)y-H，前提是R9，R10，R11，R12，R13，R14和R15中至少一个为-CH2OH，-[CH2CHR8]x-OH，-CH2CH(OH)CH3或-(CH2CHR8O)y-H，其中R8为-H或-CH3。，x和y是至少为1的整数，n和z如上所述；和季化合物，具有如下通式：
其中m为1至16的整数，Y表示卤素，Z-表示反阴离子，R16，R17和R18相同或不同，其为-H，-CH3或-(CH2)p-CH3，以及R19为-H或-CH3，以及p为1至9的整数，以及一种或多种交联剂；其中，催化剂不含锡；以及
c)使用化学镀槽将金属化学沉积到基底上。
该催化剂可用于将金属化学镀到包括绝缘材料在内的基底上，并且，其在储存和化学镀过程中均能保持稳定；原因在于，与常规的锡/钯催化剂相比，该催化剂不易氧化。纤维素稳定剂的作用同氯化锡在常规锡/钯催化剂中的稳定作用，但纤维素稳定剂可生物降解，这样它们不会产生像处理氯化锡时的环境危害。纤维素稳定剂可大量使用，其成本仅为氯化锡的一小部分。制备稳定剂的原材料可由实际上无处不在的植物轻易获得。纤维素稳定的钯催化剂无需加速步骤即可进行化学镀和获得基底、甚至是印刷电路板的通孔壁的良好的金属覆盖率。
除了文中明确表明，下述在说明书全文所用的简称具有如下含义：g＝克；mg＝毫克；ml＝毫升；L＝升；cm＝厘米；m＝米；mm＝毫米；μm＝微米；nm＝纳米；ppm＝百万分含量；℃＝摄氏度；g/L＝克每升；DI＝去离子化；wt％＝重量百分含量；以及Tg＝玻璃化转变温度。
本发明全文所用的术语“印刷电路板”和“印刷线路板”可互换使用。本说明书全文的术语“镀”和“沉积”可互换使用。除非特别指明，所有的用量是重量百分含量。所有的数值范围均包含在内并可以任何方式结合，只要逻辑上这些数值范围总量为100％。
催化剂水溶液包括钯金属的纳米微粒，以及一种或多种具有如下通式的稳定聚合物：
其中，其中R1，R2，R3，R4，R5，R6和R7相同或不同，其选自-H，-CH2COOX，-C(O)-CH3，-C(O)-(CH2)z-CH3以及
其中n表示至少为2的整数，通常为2至20的整数，优选为2至15，更优选5至10，z是至少为1的整数，通常为1至10，优选2至5，以及X是-H或是反阳离子，如钠，钾，氨离子或碱土金属离子，通常为钠或钾。优选地，R1，R2，R3，R4，R5，R6和R7中至少一个是-C(O)-CH3或-CH2COOX，更优选地，R2，R3，R5，R6和R7中至少一个是-CH2COOX，优选当R1，R2，R3，R4，R5，R6或R7不是C(O)-CH3或-CH2COOX时，是-H。具体的聚合物是羧甲基纤维素，醋酸纤维素。催化剂不含锡。
稳定聚合物也可是以下物质的反应产物：具有下述通式的聚合物：
其中R9，R10，R11，R12，R13，R14和R15相同或不同，其选自-H，-CH3，-CH2CH3，-CH2OH，-[CH2CHR8]x-OH，-CH2CH(OH)CH3以及-(CH2CHR8O)y-H，前提是R9，R10，R11，R12，R13，R14和R15中至少一个为-CH2OH，-[CH2CHR8]x-OH，-CH2CH(OH)CH3或-(CH2CHR8O)y-H，优选地，R10，R11，R13，R14和R15中至少一个为-[CH2CHR8]x-OH或-(CH2CHR8O)y-H，其中R8是-H或-CH3，x和y是至少为1的整数，通常为1至10，优选2-5，n和z如上所述；季化合物，具有如下通式：
其中m为1至16的整数，Y表示卤素，如氟，氯，溴或碘，优选卤素是氯，Z-表示反阴离子，如卤化物(如氟化物，氯化物，溴化物或碘化物，优选氯化物)，硝酸盐，亚硝酸盐，磷酸盐，氢氧化物或羧酸盐，比如醋酸盐或丙酸盐，R16，R17和R18相同或不同，其为-H，-CH3或-(CH2)p-CH3，以及R19是-H或-CH3，以及p为1至9的整数，以及一种或多种交联剂。所述催化剂不含锡。具体的季化合物是缩水甘油基三甲基氯化铵，2，3-环氧丙基-N，N，N-三甲基氯化铵，3-氯-2-羟丙基-N，N，N-三甲基氯化铵，3-氯-2-羟丙基-N，N，N-二甲基乙醇基氯化铵和1，3-双-(3-氯-2-羟丙基-N，N-二甲基氨)-N-二氯丙烷。优选的纤维素衍生物和季氨盐化合物的反应产物是羟乙基纤维素和脱水甘油三甲基氯化铵的反应产物。
交联剂的实施例包括但不限于甲醛，羟甲基化氮化合物，如二羟甲基脲和二羟甲基亚乙基脲和二羟甲基咪唑啉酮；二羧酸，如马来酸；二醛，如乙二醛；双环氧化合物，如1，2，3，4-双环氧丁烷和1，2，5，6-双环氧己烷；二异氰酸酯；二乙烯基化合物，如二乙烯基硫砜；二卤化合物，如二氯乙酮，二氯乙酸，1，3-二氯丙-2-醇，二氯乙烷，2，3-二溴-1-丙醇，2，3-二氯-1-丙醇和2，2-二氯乙醚；卤代醇，如表氯醇；双(环氧丙基)醚；乙烯基环己烯二氧化物；乙二醇-双(环氧丙基)醚；乙烯基环己烯二氧化物；乙二醇-双(环氧丙基)醚；1，3-双(β-羟基-Γ-氯丙氧基)醚；1，3-双(β-羟基-Γ-氯丙氧基)乙烷；亚甲基双(丙烯酰胺)；N，N’-二羟甲基(亚甲基双(丙烯酰胺))；三丙烯酰六氢三嗪；丙烯酰氨基亚甲基氯乙酰胺；2，4，6-三氯嘧啶；2，4，5，6-四氯嘧啶；三聚氯化氰；三烯丙基氰脲酸酯氯氧化磷；双(丙烯酰氨基)乙酸；双-环氧化合物和卤代环氧化物，如1，3-双(缩水甘油二甲基铵)二氯丙烷和表氯醇。优选的交联剂是双环氧和卤代环氧化物。
可使用本领域和文献中已知的方法制备聚合物，许多是可市场上可获得的。商业可获得的羧甲基纤维素钠的实施例是购自阿斯兰(Ashland)的AQUALON、以及商业上可获得的羟甲基纤维素和缩水甘油三甲基氯化铵的聚合物是购自爱美科公司(AmercholCorporation)的UCAREJR-125。制备纤维素和纤维素衍生物和季铵盐化合物聚合物的方法参见US5,780,616公开的内容。
聚合物的重均分子量可变。典型地，其范围起自10,000或更大，更为典型的是从10,000至300,000。
催化剂水溶液中含有足够量的稳定聚合物以提供纳米微粒的稳定。催化剂水溶液中可含有上述的各种稳定聚合物的混合物。进行小型的试验来确定具体的稳定剂或结合使用稳定剂的用量以稳定催化剂。通常来讲，催化剂水溶液中包含的一种或多种稳定聚合物的用量是10mg/L至10g/L，优选20mg/L至1g/L。
催化剂水溶液中包含一种或多种抗氧化剂。可使用常规的抗氧化剂及其常规的用量。通常地，所含抗氧化剂的量为0.1g/L至10g/L，优选0.2g/L至5g/L。所述抗氧化剂包括但不限于抗坏血酸，酚酸，多酚化合物，例如但不限于羟基苯甲酸及其衍生物，镓酸，羟基苯甲醛，邻苯二酚，对苯二酚，儿茶酸和类黄酮。
含有一种或多种还原剂以将钯离子还原成钯金属。可使用已知的将钯离子还原成钯的常规还原剂。所述还原剂包括但不限于二甲基铵硼烷，氢硼化钠，抗坏血酸，异抗坏血酸，次磷酸钠，水合肼，甲酸和甲醛。所含还原剂的量基本上可将全部钯离子还原成钯金属。所述量是常规用量、是所属领域技术人员熟知的。
钯金属源包括任何可溶于水的钯盐。所述盐可提供10ppm至5000ppm，优选300ppm至1500ppm量的钯金属。水溶性钯盐包括但不限于氯化钠钯，氯化钯，醋酸钯，氯化钾钯和硝酸钯。
组成催化剂水溶液的各组分可以任何顺序组合。可使用本领域和文献中已知的任何合适的方法制备催化剂水溶液。组分的具体参数和用量可在不同的方法中作出改变，一般来说，首先将一种或多种稳定聚合物溶解在足量水中。将一种或多种钯金属源的水溶液通过剧烈搅拌与稳定剂溶液混合得到均匀混合物。然后将含一种或多种还原剂的水溶液在剧烈搅拌下与稳定剂和钯盐的混合物相混合从而将钯离子还原成钯金属。通常方法步骤和溶液在室温下进行；然而，可调整温度以助于溶解反应组分和促进金属离子的还原。不局限于理论，稳定剂可涂覆或包围钯微粒的部分或大部分以稳定催化剂溶液。钯金属微粒和稳定剂的粒径尺寸范围为1nm至1000nm，或者2nm至500nm。优选粒径尺寸范围为2nm至300nm，更优选2nm至100nm，最优选2nm至10nm。
可将一种或多种酸加入催化剂中以得到小于7的pH，优选1-6.5，更优选2-6。可使用足够量的无机酸或有机酸以得到所需范围的pH。也可使用无机和有机酸的混合物。无机酸的实施例包括盐酸，硫酸和硝酸。有机酸包括单或多羧酸，如二羧酸。有机酸的实施例是苯甲酸及其衍生物，如羟基苯甲酸，抗坏血酸，异-抗坏血酸，苹果酸，马来酸，镓酸，醋酸，柠檬酸和酒石酸。
催化剂可用于化学镀多种已知的能用于进行化学镀的各种基底。基底包括但不限于，包括如玻璃、陶瓷、瓷、树脂、纸、布及其混合物的无机和有机基底材料。金属包层和无金属包层材料可是使用催化剂镀金属的基底。
基底也包括印刷电路板。所述印刷电路板包括金属包层和无金属包层，其使用了热固性树脂，热塑性树脂及其混合物，包括纤维，如玻璃纤维和前述的浸渍的具体实施方式。
热塑性树脂包括但不限于缩醛树脂，丙烯酸酯，如丙烯酸甲酯，纤维素树脂，如乙酸乙酯，丙酸纤维素，纤维素醋酸丁酸盐(celluloseacetatebutyreate)和硝酸纤维素，聚醚，尼龙，聚乙烯，聚苯乙烯，苯乙烯混合物，例如丙烯腈苯乙烯和共聚物和丙烯腈-丁二烯苯乙烯共聚物，聚碳酸酯，聚氯三氟乙烯，和乙烯基聚合物和共聚物，例如醋酸乙烯酯，乙烯醇，乙烯基丁缩醛，氯乙烯，氯乙烯-醋酸酯共聚物，偏二氯乙烯和乙烯基甲醛(formal)。
热固性树脂包括但不限于邻苯二甲酸丙烯基酯，呋喃，三聚氰胺-甲醛，苯酚-甲醛和苯酚-糠醛共聚物，其单独使用或与下述树脂混合：丁二烯丙烯腈共聚物或丙烯腈-丁二烯-苯乙烯共聚物，聚丙烯酸酯，有机硅氧聚合物，尿素甲醛，环氧树脂，烯丙基树脂，邻苯二甲酸甘油酯以及聚酯。
多孔材料包括但不限于纸，木材，玻璃纤维，布和纤维，例如天然和合成纤维，如棉纤维和聚酯纤维。
催化剂可用于镀低和高Tg的树脂。低Tg树脂具有低于160℃的Tg，高Tg树脂具有160℃及以上的Tg的树脂。通常高Tg树脂具有160℃至280℃的Tg，或者为170℃至240℃。高Tg聚合物树脂包括但不限于聚四氟乙烯(PTFE)和聚四氟乙烯混合物。所述混合物包括，例如含聚苯醚的PTFE和氰酸酯。其他类包含具有高Tg树脂的聚合物树脂，包括但不限于环氧树脂，如双功能或多功能环氧树脂，双马来酰亚胺/三嗪和环氧树脂(BT环氧)，环氧/聚苯醚树脂，丙烯腈丁二烯苯乙烯，聚碳酸酯(PC)，聚苯醚(PPO)，聚苯醚(PPE)，聚苯硫醚(PPS)，聚硫砜(PS)，聚酰胺，聚酯如聚对苯二酸乙二酯(PET)和聚对苯二酸丁二酯(PBT)，聚醚酮(PEEK)，液晶聚合物，聚氨酯，聚醚酰亚胺，环氧化物以及它们的复合物。
催化剂可用于在通孔壁或印刷电路板的通孔上沉积金属。催化剂可用于生产印刷电路板的水平或垂直加工。
催化剂水溶液可用于常规化学镀槽。可以预期，该催化剂可用于化学沉积任何可化学镀的金属，通常，所述金属选自铜，铜合金，镍或镍合金。更通常地，金属选自铜和铜合金，最通常地使用铜。
可使用常规的化学镀铜或铜合金槽。通常铜离子源包括但不限于铜的可溶性卤化物，硝酸盐，醋酸盐，硫酸盐和铜的其它有机或无机酸盐。可使用一种或多种所述铜盐的混合物以得到铜离子。实施例包括硫酸铜，如五水硫酸铜，氯化铜，硝酸铜，氢氧化铜和氨基磺酸铜。可在组合物中使用常规量的铜盐。通常组合物中的铜离子浓度范围是0.5g/L至30g/L，或者是1g/L至20g/L，再或者是5g/L至10g/L。
在化学镀组合物中也可以包括一种或多种合金金属。所述合金金属包括但不限于镍和锡。铜合金的例子包括铜/镍和铜/锡。通常地，铜合金是铜/镍。
镍和镍合金化学镀槽的镍离子源可包括一种或多种常规镍的水溶液盐。镍离子源包括但不限于硫酸镍和卤化镍。化学镀合金组合物中也可包括常规量的镍离子源。通常所含镍离子的量为0.5g/L至10g/L，或是1g/L至5g/L。
用于基底金属化的方法步骤可依赖于被沉积表面是金属或是绝缘体而改变。利用了催化剂的方法中采用化学镀基底的常规步骤；但是，聚合物水溶液稳定的钯催化剂则不同于在许多传统化学镀方法，其不需要加速步骤。相应地，优选在使用催化剂时不用加速步骤。通常地，将催化剂施加到化学镀金属的基底表面后使用金属镀槽。化学镀参数如温度和时间是常规的。可使用常规的基底制备方法，如基底表面的清洁或去油污，表面的粗糙化或微-粗糙化，表面的蚀刻或微-蚀刻，溶胀应用，通孔去污和多种漂洗和防锈处理。所述方法和配制都是本领域已知和文献中公开的。
通常地，当金属镀的基底是绝缘材料如印刷电路板的表面或者通孔的壁，所述板用水清洗、以及漂洗和防锈后，对通孔壁进行去污处理。通常地，最初用溶胀来预处理或软化绝缘表面或通孔去污。
可使用任何常规的溶胀。具体的类型可根据绝缘材料的类型而改变。绝缘体的例子如上所述。可进行小型实验以确定溶胀适用于特殊的绝缘材料。绝缘材料的Tg经常决定了所用溶胀的类型。溶胀包括但不限于乙二醇醚和与其结合的醋酸醚。可使用常规量的乙二醇醚和与其结合的醋酸醚。常规可用的溶胀例子是CIRCUPOSITCONDITIONERTM3302，CIRCUPOSITHOLEPREPTM3303和CIRCUPOSITHOLEPREPTM4120(可由美国马萨诸塞州莫尔伯勒市的罗门哈斯电子材料有限公司(RohmandHaasElectronicMaterial)获得)。
可选择地，基底和通孔用水进行清洗。然后使用助剂。可使用常规的助剂。所述助剂包括硫酸，铬酸，碱性高锰酸盐或等离子蚀刻。通常地使用碱性高锰酸钾作为助剂。商业可用的助剂的例子是CIRCUPOSITPROMOTERTM4130，可由美国马萨诸塞州莫尔伯勒市的罗门哈斯电子材料有限公司(RohmandHaasElectronicMaterial)获得。
可选择地，再用水清洗基底和通孔。然后使用中和剂中和助剂的残渣。可使用常规的中和剂。通常地，中和剂是含有一种或多种胺或3wt％过氧化物和3wt％硫酸溶液的碱性水溶液。可选择地，基底和通孔用水清洗后干燥。
溶胀和去污后，使用酸性或碱性调节剂。可用常规调节剂。所述调节剂包括一种或多种阳离子表面活性剂，非离子表面活性剂，络合剂和pH调节剂或缓冲剂。商业可用的酸调节剂的例子是CIRCUPOSITCONDITIONERTM3320和CIRCUPOSITCONDITIONERTM3327，其可由美国马萨诸塞州莫尔伯勒市的罗门哈斯电子材料有限公司(RohmandHaasElectronicMaterial)获得。合适的碱调节剂包括但不限于含有一个或多个季胺和聚胺的碱性表面活性剂水溶液。商业可用的碱性表面活性剂的例子是可由罗门哈斯电子材料有限公司获得的CIRCUPOSITCONDITIONERTM231，3325，813和860。可选择地，基底和通孔用水进行清洗。
调节之后进行微-蚀刻。可使用常规的微-蚀刻组分。设计微-蚀刻以在暴露金属(例如，内层和表面蚀刻)的金属表面提供微-粗糙化以促进随后化学沉积的吸附和之后的化学镀。微-蚀刻包括但不限于60g/L至120g/L的过硫酸钠或氧化单过硫酸钠或钾和硫酸(2％)的混合物，或者是一般的硫酸/过氧化氢。商业可用的微-蚀刻组分的例子是可由罗门哈斯电子材料有限公司获得的CIRCUPOSITMICROETCHTM3330。可选择地，用水清洗基底。
任选地，然后对微-蚀刻基底和通孔进行预浸。可使用常规的通常pH为3-5的无机酸或有机酸的预浸水溶液。无机酸溶液的例子是2％至5％的盐酸。可选择地，基底用冷水清洗。
然后将稳定的纳米微粒催化剂用于基底和通孔。可选择地，在催化剂处理后用水清洗基底和通孔。
然后用化学镀槽将金属如铜，铜合金，镍或镍合金镀基底和通孔壁。通常地，铜镀在通孔壁上。镀的时间和温度是常规的。通常地，金属沉积在20℃-80℃，更通常地在30℃-60℃下进行。可将基底浸渍在化学镀槽中或将镀液喷射到基底上。通常地，沉积可进行5秒至30分钟；然而，可根据基底上金属的厚度调整镀的时间。
可选择地，对金属进行防变色处理。可使用常规的防变色组分。商业可获得的防变色的例子是ANTITARNISHTM7130(可由罗门哈斯电子材料有限公司获得)。可选择地，清洗基底然后干燥电路板。
进一步的加工可包括常规的感光成像处理以及进一步地将金属沉积在基底上如铜，铜合金，锡和锡合金的化学金属沉积。
可使用催化剂在基底上进行化学镀金属，该基底包括绝缘体材料的基底、并且该催化剂在储存和化学镀过程中均能保持稳定，原因在于，相比于常规的锡/钯催化剂，上述催化剂不易氧化。纤维素稳定剂与氯化锡在常规锡/钯催化剂中所起功能一样，但纤维素稳定剂可生物降解、不会产生处理氯化锡时的环境危害。纤维素稳定剂可大量使用，其费用是氯化锡的一部分。用于制备稳定剂的原材料容易由所处可见的植物获得。用纤维素稳定的钯催化剂无需加速步骤即可进行化学镀、以及获得基底、甚至是印刷电路板的通孔壁的良好的金属覆盖率。
具体实施方式
下述实施例仅意在解释本发明、不对本发明的范围构成限制。
实施例1
羧甲基纤维素/钯催化剂的制备：室温下，将40mg羧甲基纤维素的钠盐溶解在烧杯里的250ml去离子水中。边搅拌，边加入含172mgNa2PdCl2的10ml去离子水，然后剧烈搅拌混合物。剧烈搅拌下，将含250mgNaBH4的10ml去离子水加入混合溶液中。溶液快速地从黄色变为黑色，其意味着钯离子还原为钯金属。钯金属的平均微粒尺寸是5nm。微粒用transmission电子显微镜测量。该合成的催化剂的溶液用ACCUMETAB15pH表测量的pH在8至9之间。将含有催化剂水溶液的烧杯放置在50℃的水浴中保持至少12小时以检测其稳定性。12小时后观察溶液，没有可见的沉淀即表明催化剂仍然保持稳定。
催化剂溶液用作原液，以及将8等份稀释到纳米颗粒浓度为25ppm。用抗坏血酸将各等分的pH调至3.5。
测试六个不同的薄板：NP-175，370HR，TUC-752，SY-1141，SY-1000-2，以及FR-408。NP-175得自南亚公司(Nanya)，370HR和FR-408得自Isola，TUC-752得自台湾联合技术公司(TaiwanUnionTechnologyCorporation)，以及SY-1141，SY-1000得自盛意(Shengyi)。Tg值的范围为140℃至180℃。每个薄板为5cm×12cm。每个薄板的表面用下述方法进行处理：
1.每个薄板浸入包括体积为1：2的乙二醇二甲醚和水的溶胀中，80℃下处理7分钟；
2.然后从溶胀中取出每个薄板，用流动冷水清洗4分钟；
3.然后在pH超过10、80℃温度下，用含1％高锰酸钾的高锰酸钾水溶液处理每个薄板10分钟；
4.然后用流动冷水清洗每个薄板4分钟；
5.然后在室温下用含3wt％过氧化物和3wt％硫酸的中和剂溶液处理每个薄板2分钟；
6.然后用流动冷水清洗每个薄板4分钟；
7.然后将每个薄板浸入含有3％CIRCUPOSITCONDITIONERTM231的酸性调节剂水溶液的水槽中，在40℃处理5分钟；
8.然后用流动冷水清洗每个薄板4分钟；
9.然后用MICROETCHTM748在室温下处理每个薄板2分钟以微-蚀刻薄板；
10.然后用流动冷水清洗每个薄板4分钟；
11然后在40℃下用前述制备的羧甲基纤维素/钯催化剂各等分的其中之一灌注薄板6分钟；
12.然后用流动冷水清洗通孔5分钟；
13.然后将薄板浸入40℃、pH为13的CIRCUPOSITTM880化学铜镀槽中，铜在薄板上沉积18分钟；
14.然后用冷水清洗镀铜薄板2分钟；
15.然后将每个镀铜薄板放入常规的对流炉中，105℃下干燥20分钟；
16.干燥每个镀铜薄板后，将其放入常规的实验干燥器中20分钟，直至其冷却至室温，以及；
17.用常规透明胶带实验法检测每个铜薄板的吸附情况。
所有的镀铜薄板都经过刻痕胶带测试。在从铜薄板上移除胶带时，没有观察到铜金属粘附在刻痕胶带上。
实施例2
如实施例1所述，制备25ppm的羧甲基纤维素/钯催化剂的水溶液。用抗坏血酸将催化剂水溶液的pH值调至3.5。测量钯催化剂的平均微粒尺寸为5nm。提供如上所述的含有多个通孔的六种类型的薄板。采用相同的方法步骤制得可传导的通孔并且其薄板的表面处理的参数如实施例1中所述。使用催化剂后，用如实施例1所述的相同的化学镀铜槽来化学镀所述的通孔。
镀后将每块板被切成片以暴露出通孔的铜镀壁。从每个板的切片通孔壁取出多个1mm厚的切片以确定板的通孔壁的覆盖率。使用欧洲背光分级量表。取自每块板的1mm切片放在常规可选的50X倍放大率的显微镜下。铜沉积量是由显微镜下观测到的光的量来确定。如果观测不到光，切片完全是黑的，背光分级是5级，其表示通孔的完全的铜覆盖率。如光通过全部切片不存在黑暗区，则表示很少甚至于没有铜沉积在壁上，切片是0级。如果切片有一些黑暗区，还有光区，其级别在0和5之间。6个薄板的25ppm的羧甲基纤维素/钯催化剂的背光分级都在5级范围内，从4.5变化至更高，其显示从行业标准来看，所述的催化剂通常是商业上可接受的。
Claims (4)
1.一种化学沉积金属的方法，包括：
a)提供基底；
b)把催化剂水溶液涂覆到基底上，催化剂水溶液包括一种或多种抗氧化剂，钯金属的纳米微粒，以及一种或多种选自具有如下通式的聚合物的化合物：
其中R1，R2，R3，R4，R5，R6和R7相同或不同，其选自-H，-CH2COOX，C(O)-CH3，-C(O)-(CH2)z-CH3以及
其中n表示至少为2的整数，z是至少为1的整数以及X表示-H或反阳离子；其中R2，R3，R5，R6和R7中的至少一个是-CH2COOH；其中，所述催化剂水溶液不含锡；以及
c)用化学镀槽将金属化学沉积到基底上。
2.根据权利要求1的方法，其中基底包含多个通孔。
3.根据权利要求1的方法，其中化学镀槽选自铜，铜合金，镍和镍合金槽。
4.根据权利要求1的方法，其中纳米微粒是1nm至1000nm。
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| US20150024123A1 (en) * | 2013-07-16 | 2015-01-22 | Rohm And Haas Electronic Materials Llc | Catalysts for electroless metallization containing iminodiacetic acid and derivatives |
| CN103556134B (zh) * | 2013-11-13 | 2015-11-25 | 湖南省化讯应用材料有限公司 | 非电解镀镍的预处理方法 |
| US20170171987A1 (en) * | 2015-12-14 | 2017-06-15 | Rohm And Haas Electronic Materials Llc | Environmentally friendly stable catalysts for electroless metallization of printed circuit boards and through-holes |
| US20170171988A1 (en) * | 2015-12-14 | 2017-06-15 | Rohm And Haas Electronic Materials Llc | Environmentally friendly stable catalysts for electroless metallization of printed circuit boards and through-holes |
| EP3181724A3 (en) * | 2015-12-14 | 2017-08-16 | Rohm and Haas Electronic Materials LLC | Environmentally friendly stable catalysts for electroless metallization of printed circuit boards and through-holes |
| US20170251557A1 (en) * | 2016-02-29 | 2017-08-31 | Rohm And Haas Electronic Materials Llc | Horizontal method of electroless metal plating of substrates with ionic catalysts |
| US10619059B1 (en) | 2019-06-20 | 2020-04-14 | Science Applications International Corporation | Catalyst ink for three-dimensional conductive constructs |
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