CN1188589A - 铜表面保护用有机－金属复合涂料 - Google Patents

铜表面保护用有机－金属复合涂料 Download PDF

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CN1188589A
CN1188589A CN96194860A CN96194860A CN1188589A CN 1188589 A CN1188589 A CN 1188589A CN 96194860 A CN96194860 A CN 96194860A CN 96194860 A CN96194860 A CN 96194860A CN 1188589 A CN1188589 A CN 1188589A
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metal
coating
organic compound
copper
metal particle
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CN1095623C (zh
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V·达里卡
V·布鲁西克
R·萨拉夫
M·盖尼斯
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International Business Machines Corp
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    • B23K35/001—Interlayers, transition pieces for metallurgical bonding of workpieces
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Abstract

本发明公开了采用包含选自取代或未取代的苯并咪唑、烷基咪唑、苯并三唑及烷基三唑的有机化合物及可为焊料润湿的金属或金属焊料的金属微粒的有机金属涂层来保护如层压的电子线路板基体的含铜表面。该金属微粒能以加热金属化合物如贵金属的乙酸盐、乙酰丙酮酸盐及碳酸盐的方法在“现场”形成。

Description

铜表面保护用有机-金属复合涂料
本发明涉及保护含铜表面免遭腐蚀的方法，具体地说，本发明涉及抑制用来制作印制电路的铜基体腐蚀的方法，以使这种电路板在经钎焊安装其它元件前，能够贮存适当的时间。本发明也涉及由本发明方法制得的经保护的铜制品。
铜及其合金是电子领域中最常用的金属，尤其是用作印制电路板电和印制电路卡的印制导电电路。
印制电路板制成后，在将电子元件和器件插入和钎焊在印制电路板上之前，常常需贮存长达一年或一年以上。不幸的是，铜和铜合金往往会与存在于空气中的种种物质(如氧、水蒸汽、二氧化碳、氯及硫)发生反应。而这又会使得在经过一段时间后的含铜材料20的可焊性下降。为了防止这类含铜表面腐蚀并保持其可焊性，已经提出这种种方法。例如，已建议在裸印制电路板完成后的较短期间内，将焊料涂敷在含铜表面上。虽然已经发现，该方法在保持电路板、卡的可焊性方面是有效的，但这是一种既费时又费用高的方法，而且这种方法还会使高密度印制电路中的细导线发生短路而产生有害的后果。
保持可焊性的另一种常用方法是采用浸锡技术来保护铜。但是，该技术的费用是较高的，而且锡在相对湿度高的条件下易受水蒸汽腐蚀。
此外，已经提出了许多采用各种吡咯类化合物抑制铜腐蚀的建议。例如，美国专利3933531、4134959、4123562、4373656、4395294以及4402847提出了采用吡咯类化合物来处理铜的种种方法。然而，由于这些方法提供的对铜的保护程度不如费用高的技术(如浸锡技术)那样好，因此吡咯类化合物的处理效果还不能完全令人满意。
根据表面安装组件方法的最新趋势，已经产生了直到在装配线上进行钎焊操作前对铜焊点及电镀通孔使用与之相容的表面涂料加以保护以防止氧化和腐蚀的需要。这些趋势是1)采用混杂(杂化)工艺；2)组件需要进行多次加热循环；3)取消组装后清洗操作；4)采用不活泼的“不需清洗”的及没有挥发性有机化合物(VOC)的焊膏及助焊剂；5)高VO成分(细沥青)；以及6)采用2“不需清洗的”和没有VOC的焊膏及助焊剂；5)高VO成分(细沥青)以及6)采用导电粘合剂代替焊料。为了跟上这些变化，用于铜表面的保护涂料必须由那些能完全满足上述要求并且能节省成本的材料来取代。
苯并三唑和焊料涂覆热空气整平技术(Hot Air Solder Levelling(HASL))是在电子工业广泛应用的涂覆方式，用以保护铜表面及其可焊性。然而，苯并三唑经不起多次加热循环和HASL，除成本高之外，在印制电路卡中还会产生热应力，从而引起翘曲或IP分离问题。经HASL技术处理的印制电路板10，由于焊料的厚度不同和隆起也不能使表面保持同平面。涂料工业已通过开发经得起多次热循环、能保护铜表面免遭氧化的咪唑基涂料来解决这些问题。然而，这类涂料的涂层较厚(0.3-0.5微米)，当采用低腐蚀性的“不需清除的”助熔剂并进行波焊操作15时，在达到所需的可焊性或毛细作用程度方面会产生问题。咪唑涂层在进行所谓“钉床式接触”(“Bed of Nails”)试验时也会产生问题，这些问题是由于接触下层铜表面的探针上形成了阻隔层或由于重复试验后探针的尖顶被绝缘的残留的包覆而引起的。像在无电除镍的面上经浸金或浸钯形成的金属涂层虽能解决厚有机涂层的绝缘性问题，但由于贵金属20成本高、浸涂过程缓慢，因而这类涂层常常是价格很高的。松香或树脂基涂料(预涂助焊剂)能经得起多次加热循环，但需要能用溶剂清洗的焊膏及助焊剂，所以，不利于环境安全，因而越来越少用了。
为了满足先进技术的要求，显而易见需要既具有有机涂料优点又具有金属涂料优点的高性能的涂料和方法，从而优化电子元件组装期间涂层的性能。
本发明包括在铜及其合金上形成有机涂层的涂料组合物及方法，这种涂料的抑制腐蚀效果至少要与先有技术采用的吡咯涂料相同.本发明的复合涂料组合物包含至少一种抑制腐蚀的有机化合物，选自取代或未取代的苯并咪唑、烷基咪唑、苯并三唑及烷基三唑；以及由可为焊料润湿的金属或包括锡-铅焊料的金属焊料所组成的金属微粒。复合涂料组合物还可含一种有机溶剂或水性溶剂以及至少一种选自酸性的碱金属亚硫酸氢盐15、酸性芳胺以及乙二醇的除氧剂。金属微粒的平均粒径与涂层厚度差不多，平均粒径优选在约0.2-2微米之间，更优选0.5-2微米。可为焊料润温的金属选自Pd、Sn、Ag、Au、Cu、Ni、涂镍的铜及Ni-Pd合金。金属焊料通常可以是含约62％锡和38％铅20的低熔焊料混合物或与低熔焊料相近的含约60％锡和40％铅的焊料。Sn、Bi基焊料和Ag基焊料也可用作常规Sn-Pb焊料的替代品。该涂料组合物可含至少一种在加热时会产生可为焊料润湿的金属微粒的、选自乙酸金属盐、乙酰丙酮酸金属盐及碳酸金属盐的金属化合物来替代实际金属微粒。
本发明的供涂敷一种含铜或铜合金的金属基体的方法包括下列步骤：
a)将含选自取代的或未取代的苯并咪唑、烷基咪唑、苯并三唑及烷基三唑的抑制腐蚀的有机化合物以及选自可为焊料润湿的金属和焊料的金属微粒的一种涂料组合物涂敷在所述基体上；
b)用水漂洗涂敷的表面；及
c)干燥涂层组合物。
对于这种方法来说，该组合物可以金属微粒悬浮在有机化合物中的悬浮体的形态被涂敷，或者该组合物可包含在加热时能产生可为焊料润湿的金属微粒的金属化合物。对于后一种情况，可在贮存已涂敷的基体前加热涂层以产生金属微粒，或者可通过钎焊时的热量来形成金属微粒。另一方法，可通过分别涂敷金属微粒和有机化合物，可以先涂金属微粒或者先涂有机化合物，在“现场”形成组合物。金属表面可用金属卤化物(如Pd Cl或SnCl)进行“接种”，然后当金属表面浸入含悬浮的金属微粒的有机化合物中时会吸引金属微粒。
除了上述a)、b)及c)步骤外，该方法优选包括预先用合适的清洁剂清洁基体，接着用水漂洗，用一种氧化剂如过硫酸碱金属盐进行微蚀刻，用一种酸如硫酸去氧化，再用水漂洗后干燥的步骤.优选在最后漂洗前将基体浸入如苯并三唑溶液中。
本发明还提供含铜及表面保护涂层的金属基体，该表面涂层包括：
a)一种铜与一种选自取代或未取代的苯并咪唑、烷基咪唑、苯并三唑及烷基三唑的抑制腐蚀的有机化合物相配合的内层，及
b)一种包含有机化合物与选自可为焊料润湿的金属及焊料的金属微粒的外层。
表面保护涂层可按照常规方法借助加热、助焊剂与焊料，在涂层形成后的任何时候进行钎焊。涂层中存在的金属微粒会从焊料吸收热量并增强焊料的毛细流动。当有机涂层经加热被破坏时可形成金属微粒。
一般说来，本方法涉及涂敷一种含选自苯并咪唑、烷基咪唑、苯并三唑及烷基三唑的抑制腐蚀的有机化合物和选自可为焊料润湿的金属及焊料的金属微粒的涂料组合物，来实施保护印制电路板的含铜表面。
附图的简要说明
图1展示涂覆有常规有机涂料的导电铜焊点。
图2展示图1的涂有有机涂料的铜焊点的表面安装工艺(SMT)钎焊的焊料再流平机理。
图3展示涂敷有本发明有机金属涂层的图1铜焊点。
图4展示图3的涂有有机金属涂层的铜焊点的表面安装工艺(SMT)钎焊的焊料再流平机理。
图5展示孔的铜表面涂有常规有机涂层的常规电镀通孔(PTH)。
图6展示插入图5电镀通孔中的引线的波焊机理。
图7展示孔的铜表面涂敷本发明有机金属涂层的电镀通孔。
图8展示插入图7电镀通孔中引线的波焊机理，其中孔的铜表面涂敷本发明有机金属涂层。
本发明的详细说明
根据本发明的欲防止腐蚀的表面是如通常用于电子元件制作的铜及铜合金的表面。
抑制腐蚀的有机化合物可以是至少一种如下所述的苯并咪唑、烷基咪唑、苯并三唑或烷基三唑。这些化合物可以是未取代的形态或为常见的取代基如低级烷基、卤素或硝基所取代的形态。
苯并咪唑类是以通式(I)表示的化合物：式中R1表示烷基或氢，R2、R3、R4及R5每个分别表示低级烷基基团、卤素原子、硝基基团或氢原子。具体实例包括苯并咪唑、2-甲基苯并咪唑、5-甲苯并咪唑、5，6-二甲基苯并咪唑、2-丙基-4，5-二甲基苯并咪唑、2-丁基-5-硝基苯并咪唑、2-戊基-5，6-二氯苯并咪唑以及2-十七烷基-5-甲基苯并咪唑。
苯并三唑类是以通式(II)表示的化合物：式中R1、R2、R3和R4表示与式(I)中R2至R5相同的取代基，具体实例包括1-甲基苯并三唑和5-甲基苯并三唑。
烷基咪唑类是以通式(III)表示的化合物、
Figure A9619486000083
式中R1是含2至约5个碳原子的烷基基团，R2和R3可以是与式(I)中R2至R5相同的基团。具体的实例包括2-戊基咪唑、2-庚基咪唑、2-癸基咪唑、2-十一烷基咪唑、2-十二烷基咪唑、2-十三烷基咪唑、2-十四烷基咪唑、2-十七烷基咪唑、2-十一烷基-4-甲基咪唑及2-十七烷基-4-甲基咪唑。
烷基三唑类是以通式(IV)表示的化合物：式中R1是含1至约6个碳原子的烷基基团。具体实例包括R1是甲基或乙基的烷基三唑。
涂料组合物可含适用的有机溶剂或水性溶剂以溶解有机化合物并获得所要求的粘度，优选的粘度范围为约1-约100厘泊。任何能溶解有机化合物的适用溶剂都可以采用。然而，当有机化合物中含有长链烷基基团时，只用水是不能溶解该化合物的，应采用有机溶剂或含水有机溶剂。适用的有机溶剂包括低级醇、羟基酮类(glycolketones)、芳族和脂族烃以及卤化碳。可用于本发明中的优选有机溶剂包括(但不受此限制)：甲醇、乙醇、1-丙醇、2-丙醇、乙二醇、丙二醇、丙酮、乙腈、二恶烷、吡啶、二甲基吡啶、苯、甲苯、正己烷、三氯乙烯以及四氯化碳。
虽然涂层产生保护作用的原理还不是十分清楚，但保护作用可能是基于美国专利3933531(in colt 2)中提出的机理进行的。铜或铜合金的表面可能与咪唑(或三唑)环中的-NH-基团发生反应并在铜原了与咪唑分子间形成了某种类型的键。该-NH-基团会起一种锚接的作用。由反应产生的氢原子能以吸附氢的形态被吸附在铜金属上。然后，另一个咪唑分子的一个-NH-基团能与键合在铜表面上的咪唑叔氮原子相缔合，而这些叔氮原子与-NH-基团通过氢键连接在一起。烷基基团(如存在)胶团(micelles)的形成也有助于这种氢键的形成。因此，一旦咪唑已经沉积或粘附到铜表面上，其它咪唑分子通过氢键和有可能形成的胶团而一个接一个地逐渐被吸引到已粘附的咪唑分子上，于是铜表面上形成了薄的咪唑涂层。该机理也可解释为，在基体金属表面形成了Cu+离子，该Cu+离子在铜表面与吸附的苯并咪唑分子发生反应而形成了一种三维的但薄的Cu(I)-苯并咪唑配合物。总之，在基体上粘附了厚约1-5rim，在水或醇中不溶的薄膜。
可是，据认为，正如下面详述的，大部分含金属微粒的涂料并不粘附在铜上，只是在内层上面形成一保护涂层。保护层的厚度与悬浮的金属微粒的粒径成比例。
涂料组合物还可任选地含至少一种选自酸性的碱金属亚硫酸氢盐、酸性芳胺及乙二醇的除氧剂。
金属微粒选自可被焊料润湿的金属和金属焊料。所谓“焊料可润湿的”是指当金属微粒暴露在熔融的焊料中时，微粒表面能均匀程度或大或小地被焊料覆盖，而微粒本身不熔化。或者，焊料微粒往往会被熔融的焊料本身所吸收。这类可为焊料润湿的金属包括(但不受此限制)Pd、Sn、Ag、Au、Cu、Ni、涂镍的铜及Ni-Pd合金。锡-铅焊料可含约3-约90重量％锡和约10-约97％铅，但优选的是含约62％锡和38％铅的低熔混合物。也可采用Sn-Bi和Ag基焊料。微粒的平均粒径应与欲形成的外涂层厚度相适应，通常为约0.2-2微米，优选约0.5-1微米。
金属微粒也可由涂料组合物和/或涂层经加热在“现场”形成，甚至可使用加热时能形成可为焊料润湿的元素金属的金属的或有机金属化合物，通过将元件焊接到铜焊点进行加热时来形成金属微粒。这样形成的微粒形状是均匀一致的，平均粒径在范围10的约0.2-约2微米之间。这种化合物包括贵金属的乙酸盐、乙酰丙酮酸盐及碳酸盐。具体的化合物包括(但不受此限制)乙酸钯、乙酰丙酮酸银及碳酸银。
涂敷工艺的重要步骤是涂敷含有机化合物和金属微粒的涂料组合物，之后，用水清洗以除去过量的涂料并干燥之。然而，在涂敷前优选用至少一种适用的清洁剂清洁铜表面以除去有机污染物和少量的铜氧化物。适用的清洁剂包括过硫酸钠溶液、无机酸组合物如盐酸及碱性预处理剂如碳酸氢钠和碳酸钠。也可采用专用清洁剂如“Cutek HL41”和“Accuclean”(Enthone公司制造)。可采用Enthone OMI公司的工业化“Entek”方法。用专用清洁剂Entek Cleaner SC-IOIDE清洁后能使铜表面的润湿性更好，用水漂洗后，将基体浸入Entek MicroetchME-1020中以使铜表面变粗糙。再漂洗一次后，将基体浸入硫酸中除去氧化物，再漂洗，再浸入含苯并三唑的Entek Cu-56溶液中，再次漂洗并干燥之。经这样清洁处理后，该表面应在水中漂洗.然后用氧化剂(如过硫酸钠)通过微蚀刻使表面粗糙化。随后将该表面浸入无机酸(如硫酸)中脱氧化。然后优选将该基体浸入含一种如苯并三唑(ENTEKCu-56溶液，Enthone公司提供)化合物的溶液中。最后，用水漂洗表面并吹干以除去水分。
可借助任何适用的方法实施涂料组合物的涂敷，这些方法应能在铜表面上形成铜-有机配合物，并能在铜表面上形成含可为焊料润湿的金属微粒分散体的均匀有机物质涂层。可采用包括浸涂、刷涂以及喷涂的种种方法将金属微粒在有机化合物中的分散体涂覆在表面上。或者，如上所述，也可以同样方法将有机化合物和金属化合物或当加热时会形成金属微粒的金属有机化合物的溶液涂覆在表面上。在适当时候，可将已涂覆的基体加热以形成金属微粒，或者，在加热将元件钎焊到基体上时，“现场”局部地形成金属微粒。
金属微粒与有机化合物可以分别涂覆，可在有机化合物涂覆前或涂覆后将金属微粒接种在基体表面上。可用任何适用的方法如刷涂或喷涂涂覆金属微粒，但是优选采用静电喷涂以保证粘附性并使损耗降至最低。可藉适当的方法如超声搅抖使金属微粒稳定地分散在有机化合物溶液中。
下面以非限制性的假想实施例对本发明作进一步的说明。
假想的和对照实施例
实施例A：SMT钎焊
图1展示了包括铜焊点(12)的印制电路板层压板(10)(如FR4)，已涂覆有常规的苯并咪唑或诸如此类的有机涂料，形成了一层薄的铜-有机配合物表面涂层(14)和一层较厚的有机物质表面涂层(16)。如图2所示，当涂上焊膏(18)并经加热，焊料必须完全透过整个有机涂层厚度到达铜表面。图3展示了用本发明有机金属涂料涂覆的类似的印制电路板(10)和铜焊点(12)。在金属表面上形成相同的一层薄的铜-有机配合物层(14)，但较厚的外层(15)含分散的金属微粒(17)。因此，如图4所示，涂上焊膏(18)  并经加热时，因有机物质的分解，熔融的焊料容易润湿并流入分散的金属微粒之间，并使其与金属微粒粘合起来，通过毛细作用使焊料达到铜表面。
实施例B：电镀通孔的波焊
图5展示了印制电路板(10)中的电镀通孔(20)。铜箔层(22)覆盖孔内印制电路板的边角，孔内涂覆有能形成铜-有机配合物层(24)和较厚的有机物质(26)的常规有机物涂层。在图6中，当金属引线(28)插入图5的孔中和波形焊料(30)从下面导入孔中焊住引线时会遇到问题，这是由于焊料必须透过有机层才能到达铜表面，并且很明显，由于表面张力阻止波形焊料很深地渗入孔表面与引线间的空间中所致。图7展示了印制电路板(10)中涂覆有本发明含金属微粒(34)的有机金属涂料(32)的相同的电镀通孔(20)。在图8中，当波形焊料(30)从下接触有机金属涂层时，借助焊料与金属微粒的粘合，焊料容易渗入到铜表面，同时由于毛细作用焊料容易通过微粒与引线(28)间的空间。这一结果表明，这是一种快速焊接方法，这种方法提供了引线与印刷电路板中电镀通孔之间优良的焊接点。

Claims (19)

1.一种用于含铜金属的复合涂料组合物，包含至少一种选自苯并咪唑、烷基咪唑、苯并三唑、烷基三唑的抑制腐蚀的有机化合物以及可为焊料润湿的金属或金属焊料的金属微粒。
2.根据权利要求1的涂料组合物，其中还包含至少一种选自低级醇、二醇、酮、芳香烃及水的溶剂。
3.根据权利要求1的涂料组合物，其中还包含一种选自酸性碱金属的亚硫酸氢盐、酸性芳胺及乙二醇的除氧剂。
4.根据权利要求1的涂料组合物，其中所述有机化合物选自苯并咪唑。
5.根据权利要求1的涂料组合物，其中所述金属微粒的平均粒径为约0.2-约2微米之间。
6.根据权利要求5的涂料组合物，其中平均粒径为约0.5-约1微米之间。
7.根据权利要求1的涂料组合物，其中所述可为焊料润湿的金属选自Pd、Sn、Ag、Au、Cu、Ni、涂镍的铜以及Ni-Pd合金。
8.根据权利要求2的涂料组合物，其中所述涂料组合物的粘度范围为约1-约100厘泊之间。
9.根据权利要求1的组合物，其中包含至少一种在加热时会产生可为焊料润湿的金属微粒的有机金属化合物。
10.根据权利要求9的组合物，其中所述金属化合物选自贵金属乙酸盐、贵金属乙酰丙酮酸盐及贵金属碳酸盐。
11.一种涂覆含铜或含铜合金的金属基体的方法，包括下述步骤：
a)将包含选自苯并咪唑、烷基咪唑、苯并三唑、烷基咪唑的有机化合物及选自可为焊料润湿的金属和金属焊料的金属微粒的涂料组合物涂覆到所述基体上；
b)用水漂洗涂敷过的表面；以及
c)干燥。
12.根据权利要求11的方法，其中所述组合物是以所述金属微粒在有机化合物中的悬浮物形式被涂覆的。
13.根据权利要求11的方法，其中所述组合物的涂覆步骤是：先将金属微粒涂覆在所述基体上，然后再将所述有机化合物涂覆在金属微粒上。
14.根据权利要求11的方法，其中所述组合物的涂覆步骤是：先将有机化合物涂覆在所述基体上，然后再将所述金属微粒涂覆在有机化合物上。
15.根据权利要求11的方法，其中所述组合物的涂覆步骤是：先涂覆所述有机化合物与至少一种选自贵金属乙酸盐、贵金属乙酰丙酮盐及贵金属碳酸盐的金属化合物的溶液，然后加热所述溶液，“现场”形成金属微粒。
16.根据权利要求11的方法，其中还包括用适当清洁剂清洁所述基体、用水漂洗、用氧化剂微蚀刻、脱氧、用水漂洗以及干燥的预处理步骤。
17.一种含铜的金属基体，其特征在于，至少一个表面是被下述物质保护的：
a)一种铜与一种选自苯并咪唑、烷基咪唑、苯并三唑及烷基三唑的抑制腐蚀的有机化合物相配合的内层；及
b)一种包含所述有机化合物与选自可为焊料润湿的金属和金属焊料的金属微粒的外层。
18.一种采用加热、助焊剂和焊料将金属元件钎焊到经涂覆的权利要求17的金属基体上的方法。
19.一种保护印制电路板铜表面的方法，是通过涂覆包含选自苯并咪唑、烷基咪唑，苯并三唑及烷基三唑的有机化合物和选自可为焊料润湿的金属及锡-铅焊料的金属微粒的涂料组合物来实现的。
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JP3329572B2 (ja) * 1994-04-15 2002-09-30 福田金属箔粉工業株式会社 印刷回路用銅箔およびその表面処理方法

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CN1298491C (zh) * 2002-02-28 2007-02-07 播磨化成株式会社 析出型焊锡组合物及焊锡析出方法
CN102489894A (zh) * 2011-12-05 2012-06-13 贵研铂业股份有限公司 一种新型复合焊料
CN102489894B (zh) * 2011-12-05 2013-09-11 贵研铂业股份有限公司 一种复合焊料及其用途
CN107614497A (zh) * 2015-05-28 2018-01-19 艺康美国股份有限公司 新颖腐蚀抑制剂
CN107614497B (zh) * 2015-05-28 2021-08-03 艺康美国股份有限公司 腐蚀抑制剂
US11306400B2 (en) 2015-05-28 2022-04-19 Ecolab Usa Inc. 2-substituted imidazole and benzimidazole corrosion inhibitors
CN110463362A (zh) * 2017-02-08 2019-11-15 加拿大国家研究委员会 修饰金属导电层的方法
CN109337568A (zh) * 2018-08-29 2019-02-15 华月圆 一种金属基材长效防腐面漆及其制备方法

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HK1018999A1 (en) 2000-01-14
CN1095623C (zh) 2002-12-04
AU5561696A (en) 1997-11-07
KR100269830B1 (ko) 2000-10-16
WO1997039610A1 (en) 1997-10-23
US5960251A (en) 1999-09-28
KR19990022285A (ko) 1999-03-25

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