CN102264491A - 可热分解聚合物涂布的金属粉末 - Google Patents

可热分解聚合物涂布的金属粉末 Download PDF

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CN102264491A
CN102264491A CN2009801517953A CN200980151795A CN102264491A CN 102264491 A CN102264491 A CN 102264491A CN 2009801517953 A CN2009801517953 A CN 2009801517953A CN 200980151795 A CN200980151795 A CN 200980151795A CN 102264491 A CN102264491 A CN 102264491A
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metallic particles
polymer
cyanoacrylate
coating
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CN102264491B (zh
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P·刘
B·奥尔森
M·J·霍洛韦
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Halima Chemicals Group Co ltd
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Abstract

本发明涉及聚合物涂布的金属粉末，如用于形成焊接合金和焊接膏的金属粉末。所述金属粉末用氰基丙烯酸酯的可固化组合物涂布。本发明涉及聚合物涂布的金属粉末，如用于形成焊接合金和焊接膏的金属粉末。金属粉末用氰基丙烯酸酯的可固化组合物涂布，并且一旦固化，金属粉末上的涂层为氰基丙烯酸酯聚合物。

Description

可热分解聚合物涂布的金属粉末
技术领域
本发明涉及聚合物涂布的金属粉末，如用于形成焊接合金、锡球和焊接膏的金属粉末。金属粉末用可热分解聚合物如氰基丙烯酸酯聚合物或二环戊二烯(“DCPD”)低聚物涂布。
背景技术
焊料广泛用于半导体封装和半导体器件的组装中。
例如，锡球用于半导体封装的组装中，如在倒装晶片的应用中。
焊接膏通常用于在电路板上对电子元件进行表面组装的焊接。焊接膏是有用的，因为其可以用在电路板的选定区域上，当电路板穿过焊料回流过程时，在形成永久粘合之前，其粘着特征能够将电子元件固定住而不需额外的粘合剂。
焊接膏通常包含焊接粉末、树脂组分如松香、活化剂如有机酸或胺、流变控制剂、增稠剂和溶剂。通常通过诸如丝网印刷、分配、和转移印刷的技术将焊接膏涂布在电路板上。然后，将电子元件放置在电路板上，将焊接膏回流，借此将焊料充分加热以使其熔融，而后再充分冷却使其固化。
在工业上使用焊接膏的一个问题是其通常具有短的不可预料的保存期，例如，典型地从约一个月到六个月。保存期的不稳定至少部分是由于从制备焊接粉末到将其与助焊剂混合形成焊接膏的时间之间的间隔的变化，从而导致焊接粉末的氧化程度的变化。所述氧化的粉末不能与未氧化粉末一样回流。另外，当焊接粉末与本身具有腐蚀性的助焊剂混合时，焊接粉末通常与焊剂反应，从而氧化该粉末并降低助焊剂的酸性，从而降低助焊剂的有效性。因此，焊接膏的性能通常随时间而恶化。而且，焊接粉末与助焊剂之间的反应通常导致焊接膏的粘度显著上升，这可能使印制焊接膏变得困难，如果可能取决于印刷密度。
已经有尝试通过在冷冻条件下储存焊接膏来降低焊接粉末和助焊剂之间的反应速率，从而增加焊接膏的保存期。然而，冷冻对于补偿焊接粉末在与焊接膏掺混之前的氧化程度的变化上是无效的。
还有报道称已经用不与焊接膏反应的材料涂布焊接粉末。例如，美国专利4,994,326公开了将不溶于或几乎不溶于焊接膏载体的涂层剂用作涂料，其包括基于有机硅和氟的那些，例如硅油、有机硅基高分子化合物、氟化硅油、氟硅树脂和氟代烃基高分子化合物。
′326专利还公开了相当大量的用于焊接粉末的涂料。尽管这相当大量的涂料对抑制焊接粉末的氧化可能是有效的，但是通常，大量涂料是不期望的，因为它们可产生屏障，抑制焊料的回流。而且，这样的大量的涂料可能导致物理障碍和/或杂质，这导致差的回流性质，如助焊剂对基底的不充分润湿，这可导致焊料差的分布和不连续的焊料连接。
另外，′326专利公开了氟代烃的应用，其在涂布焊接粉末中用作溶剂。目前，氟代烃被认为是环境污染物，其使用通常是不期望的。
美国专利6,416,863涉及一种封装焊接金属粉末的方法，其中通过在焊接粉末的表面上进行聚合反应而为粉末提供聚合物保护薄层，步骤如下：
a)生产粉末和疏水液体的悬浮液，
b)在连续搅拌下添加链长为C1-C20的阳离子表面活性剂而在步骤(a)的疏水层上形成帚状结构，从而在每个金属颗粒上产生疏水表面层，
c)搅拌步骤a)和b)的混合物，直到形成粘稠均质体，
d)向步骤c)的均质体中添加可自由基聚合的单体，形成热塑性聚合物，其玻璃温度Tg比焊接粉末的固相线温度低至少60℃，
e)添加有机引发剂，以引发界面聚合反应，从而掺入步骤b)的疏水层，并形成具有助焊剂性质的热塑性聚合物保护层，
f)连续搅拌下将步骤e)的均质体加入到水性制剂中使得所述制剂含有乳化剂用于悬浮液稳定，并且控制聚合反应温度为50℃-90℃，并保持该温度至少120分钟，和
g)冷却，洗涤和回收步骤e)和f)的封装的焊接粉末。适用于形成封装壁的单体为可自由基聚合单体，优选甲基丙烯酸2-羟乙酯或甲基丙烯酸甲酯。
美国专利5,328,522涉及一种焊接膏，其包含：
(i)助焊剂，和
(ii)涂布的焊接粉末，所述粉末包含用聚对二甲苯(熔点低于焊料颗粒)涂布的焊接颗粒，基于涂布的焊接粉末的总重量，所述聚对二甲苯的量为约0.001-约0.5wt％，并有效抑制焊接膏中焊接颗粒的氧化，而基本上不抑制涂布的焊接粉末的回流性质。
美国专利4,452,861(Okamoto)描述了用氰基丙烯酸酯聚合物封装的焊接颗粒。封装颗粒以防止由于反应性或腐蚀性环境造成的降解。所述氰基丙烯酸酯聚合物被用于涂布磷颗粒等，所述磷颗粒等被用作阴极射线管等的涂料。铈活化的硫化钙磷粉末是被涂布的示例性材料。
美国专利申请公开2005/0171273描述了用于形成各向异性导电接合的可固化组合物，其包含：
(i)一定量的第一基本未固化的可固化组分；和
(ii)用第二可固化组分的固化产物涂布的导电颗粒，其中所述涂布的导电颗粒分散在所述第一可固化组分中。
虽然有目前的技术，还是期望提供可固化组合物作为金属颗粒的涂料，特别是适用于焊接膏的那些。
发明内容
因此，本发明提供一种在其至少一部分表面上涂布了由至少一种反应性单体形成的可热降解聚合物的金属粉末。
所述反应性单体的固化产物的主要功能是物理上隔离金属颗粒防止其受到环境降解如氧化或与助焊剂介质的化学反应。通常，聚合物涂层用作对氧化的物理屏障，而涂布的金属颗粒储存在金属粉末和/或焊接膏中备用。
用于涂布的反应性单体期望是氰基丙烯酸酯。氰基丙烯酸酯在与金属颗粒接触时固化，因此从易于固化的有利点来看，是期望的保护剂的选择。当氰基丙烯酸酯聚合物分解时，如在处于加工温度期间，如在焊料回流期间达到的温度，其残余物仅仅是氰基丙烯酸酯单体。氰基丙烯酸酯聚合物具有上限温度，高于所述温度，聚合物恢复成制造其的单体。然而，大多数聚合物的上限温度都高于其降解温度。因此实际上，那些聚合物实际上观察不到其上限。其它聚合物，如氰基丙烯酸酯聚合物，具有非常低的上限温度(通常为约120-约150℃)。
氰基丙烯酸酯单体通常可以由下式表示：
Figure BPA00001390361000041
其中R1是C1-C40烷基、C3-C40环烷基、或C2-C40烯基，其任选具有羟基或烷氧基官能性和/或醚键。
适合的氰基丙烯酸酯单体为烷基、烯基和烷氧基氰基丙烯酸酯，更特别的是其中所述酯的烷基或烯基具有最多10个碳原子。氰基丙烯酸酯单体可以选自氰基丙烯酸的甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、正己基、异己基、正庚基、异庚基、正辛基、正壬基、烯丙基、甲氧基乙基、乙氧基乙基、3-甲氧基丁基和甲氧基异丙基酯。
氰基丙烯酸酯还可以含有(与氰基丙烯酸酯相容的)染料和颜料，以可以检查涂料在金属颗粒上覆盖程度，或者涂料在颗粒上的覆盖程度。
适合的着色剂的实例包括1-羟基-4-[4-甲基苯氨基]-9，10蒽醌(D+CViolet No.2)；6-羟基-5-[(4-磺苯基)偶氮]-2-萘磺酸的二钠盐(FD+C YellowNo.6)；9-(邻羧基苯基)-6-羟基-2，4，5，7-四碘-3H-呫吨-3-酮的二钠盐的一水合物(FD+C Red No.3)；2-(13二氢-3-氧-5-硫-2H-2-亚吲哚基)-2，3-二氢-3-氧-1H-吲哚-5-磺酸二钠盐(FD+C Blue No.2)；和酞菁(2-)铜。
如果待涂布的金属颗粒与氰基丙烯酸酯的反应有些慢，那么可以在氰基丙烯酸酯中使用固化加速剂。其包括在国际专利申请公开WO 01/85861中公开的加速剂，在此将其全部并入作为参考。其它适用的固化加速剂的实例包括美国专利6,475,331(Grismala)和6,294,629(O′Dwyer)，在此将这两个专利的全部内容并入作为参考。
其它聚合物也可用作金属粉末的保护剂，条件是其上限温度在聚合物的降解温度之下，并在金属颗粒的熔点之下。因此，具有可用的上限温度的聚合物的上限温度为25-250℃。在金属颗粒是焊接粉末的情况下，可以使用上限温度为25-250℃的聚合物。特别可以使用上限温度为80-200℃。例如，可以使用DCPD聚合物。
在特定应用中，将金属颗粒置于两个基底之间，例如在两个导电基底之间，如在半导体封装应用中，因而颗粒必须是充分未涂布的，以在其桥连的基底之间形成导电通路。在这种环境下，基底可以充分地桥连在一起，以使金属颗粒“变平”(通过挤压而变形)并充分破坏涂层。
金属颗粒可以是单一粒径的，即，基本上相同的规格尺寸。这可能是重要的，如果形成的接合间隙是半导体封装或组装，例如期望是颗粒尺寸。然而，可以使用不同规格尺寸的颗粒，以具有较宽的直径分布，如在至少一个规格尺寸中平均为约0.5-约100μm，期望是约3-约50μm。特别是，期望涂布的颗粒是球形的。
期望地，颗粒上的涂层小于约3μm，更特别是约0.001-约0.2μm，如0.004-约0.4μm，例如约0.01-约0.1μm。颗粒上的涂层也可以作为涂布加工后颗粒上的增重的函数来确定。
金属颗粒上的聚合物涂层赋予金属颗粒稳定性，以及赋予使用涂布的金属颗粒的配方稳定性，这是通过降低颗粒对于环境污染物的反应性，或者在配方例如焊接膏的情况下，对于其它用于形成配方的组分的反应性。
在焊料回流加工的情况下，施加焊接膏之后，至少一些金属颗粒的聚合物涂层通过暴露于回流期间达到的高温而被至少部分去除，从而暴露出金属颗粒的表面，即焊接粉末。所述聚合物涂层也可以通过物理破坏而至少部分去除(例如通过对颗粒施加足够的压力以使其变形，导致涂层破坏)。
聚合物涂布的金属颗粒可以用于许多应用中。一个主要的终端应用通常是在电子工业中，特别在焊接膏中，如在倒装晶片应用中，以及锡球应用中。
聚合物涂布的金属颗粒和由其制备的配方如焊接膏，以及锡球可以特别用于在半导体晶片和基底之间建立电连接。
可以使用任何类型/形状的金属颗粒。特别地，颗粒可以是球形或趋于球形。金属颗粒的适合金属包括元素金属，如锡、银、铜、铅、锌、铟、铋、和稀土金属或合金，如锡/银/铜、锡/铋、锡/铅和锡/铟/铋合金。
本发明还涉及一种在金属颗粒上形成聚合物涂层的方法，其包括如下步骤：
a)提供若干金属颗粒；
b)在适合的条件下施加氰基丙烯酸酯或其它可热分解聚合物如DCPD聚合物，以基本上涂布大多数金属颗粒的至少一部分表面；和
c)在氰基丙烯酸酯的情况下，使氰基丙烯酸酯固化成为金属颗粒的聚合物涂层。
本发明还涉及一种形成焊接膏的方法，其包括如下步骤：
a)提供氰基丙烯酸酯或其它可热分解聚合物如DCPD聚合物涂布的焊接粉末；
b)提供两种或多种选自以下的焊接膏组分：松香、活化剂、流变控制剂、增稠剂、或溶剂；和
c)将所述氰基丙烯酸酯或其它可热分解聚合物如DCPD聚合物涂布的焊接粉末与所述焊接膏组分混合，形成焊接膏。
通过将金属颗粒暴露于丙烯酸酯组分的蒸气中，可以在颗粒表面上形成聚合的氰基丙烯酸酯的均匀涂层。气相沉积可以使均匀的涂层施加在颗粒上。例如，可以将颗粒暴露于在常温下产生的任何适合的蒸气中，或可以升高温度以产生蒸气。在氰基丙烯酸酯的情况下，蒸气与颗粒表面的接触可足以使反应性单体聚合。可以使用流动床反应器来制备涂布的金属颗粒。可以将反应性单体的蒸气注入到反应器的流动床中。典型的涂层的厚度是小于1μm。本领域技术人员将认识到，其它施加反应性单体以形成聚合物涂层的方法是明显的，例如将颗粒置于基本上未固化的反应性单体中。
本发明将参考以下非限制性实施例进行描述。
实施例
实施例1
氰基丙烯酸酯涂布方法
设计氰基丙烯酸酯涂布方法以不包括任何外部催化剂，使得聚合通过金属表面本身引发，从而使要形成的氰基丙烯酸酯聚合物在金属表面上生长。
将500g类型4的焊接粉末(锡、铜和银合金)(平均粒径为30μm)和1L无水甲苯置于2L圆底烧瓶中。而后加入0.2g氰基丙烯酸丁酯，将烧瓶置于旋转蒸发器上，以100rpm旋转烧瓶使混合均匀。1小时后，将反应混合物过滤以去除溶剂，用新鲜甲苯冲洗焊接粉末两次以去除任何残余的未直接形成在焊料粉末上的氰基丙烯酸酯聚合物。在室温下将涂布的焊接粉末干燥。
实施例2
焊接膏的配制
将涂布的焊接粉末(类型4；锡、铜和银合金)与助焊剂和其它焊接膏组分混合，形成焊接膏，所述涂布的焊接粉末中的一些氰基丙烯酸酯涂布的焊料颗粒类似于实施例1中描述的那些。一些焊接膏用聚合物涂布的焊接粉末制备，其中聚合物涂层在一种情况下由甲基丙烯酸甲酯制成，而在另一种情况下由马来酰亚胺制成。
通过两种方法测试焊接膏的性能，储存期，每种方法的描述如下：
1.锡球测试
2.粘度测试
锡球测试
通过不锈钢印刷模板将焊接膏印刷在玻璃载片上，而后回流并检测锡球的迹象。
1.用刮刀刀片作为橡皮辊，使用印刷模板将焊接膏印刷在载玻片上。印刷模板厚度为0.1mm，具有3个间隔均匀地分布在印刷模板上的直径约5mm的孔。
2.在焊浴中，在250℃下加热玻璃载片5秒钟或直到其回流。
3.从焊浴中取出载片，在冷却之前将主要的锡球从载片上滚落。
4.在10倍双目显微镜上评价载片，计算每个印板上锡球的数目。
5.取较低的两个印板的平均数，并与下表比较。
  观察   评价
  0-10个小球   通过
  ＞10个小球   不合格
粘度测试
布氏粘度计使用旋转粘度计的原理：通过感应在恒定速度下旋转浸没在样品中的T型条状转子所需要的扭矩测定粘度。扭矩与浸没的转子上的粘滞阻力成比例，因此与焊接膏的粘度成比例。在特定温度下，对用前述方式制备的焊接膏进行测试。
1.将样品置于25℃下6小时。
2.在6小时后，将样品从25℃下取出，开启并去除内塞。刮去任何粘附在塞上的焊接膏并加入到样品中。
3.用抹刀轻轻搅拌焊接膏30秒，小心避免引入空气。
4.用升降支架上的带有TF转子的布氏粘度计RVDV-II+。设定转速为5rpm。
5.设定升降支架的底部移动至焊接膏表面下40mm。设定转子在焊接膏表面下3mm。
6.开启转子旋转并使升降支架下降。
7.记录下降的最低点的粘度。
用甲基丙烯酸甲酯和马来酰亚胺聚合物以类似于上述用于氰基丙烯酸酯即氰基丙烯酸丁酯的方法涂布焊接粉末。在如此涂布的焊接粉末上进行锡球测试，表明这种焊接粉末不适用于焊接膏配方，因为该聚合物是不可热分解的，并且在达到其上限温度之前开始降解。未涂布的焊接粉末作为对照。
锡球测试
Figure BPA00001390361000091
结果显示，依据锡球测试，当与对照样品相比时，用甲基丙烯酸甲酯涂布的焊接粉末不合格，而由氰基丙烯酸酯形成的聚合物涂层作为焊接粉末的保护剂表现良好，因为氰基丙烯酸酯聚合物在焊料回流温度下是可热分解的。
粘度测试
参考下表，与对照样品相比，用甲基丙烯酸甲酯聚合物涂布的焊接粉末没有改善粘度测试的性能。
Figure BPA00001390361000101
参考下表，与对照样品相比，用氰基丙烯酸辛酯聚合物涂布的焊接粉末随着时间显示出有利的粘度增大，并且能够经受5周的粘度测试而没有不合格，而对照样品却不是这样。
Figure BPA00001390361000102

Claims (16)

1.一种在其至少部分表面上涂布可热分解聚合物的金属颗粒，其中所述可热分解聚合物的上限温度在该可热分解聚合物的降解温度之下，并在所述金属颗粒的熔点之下。
2.依据权利要求1的金属颗粒，其中所述可热分解聚合物是氰基丙烯酸酯聚合物或二环戊二烯聚合物。
3.依据权利要求2的金属颗粒，其中所述氰基丙烯酸酯聚合物由氰基丙烯酸酯单体制成，所述单体具有以下结构：
Figure FPA00001390360900011
其中R1是C1-C40烷基、C3-C40环烷基、或C2-C40烯基，并任选具有羟基或烷氧基官能团和/或醚键。
4.依据权利要求3的金属颗粒，其中所述氰基丙烯酸酯选自氰基丙烯酸的甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、正己基、异己基、正庚基、异庚基、正辛基、正壬基、烯丙基、甲氧基乙基、乙氧基乙基、3-甲氧基丁基和甲氧基异丙基酯。
5.依据权利要求1的金属颗粒，其中所述金属颗粒是焊料。
6.依据权利要求1的金属颗粒，其中所述金属颗粒由元素金属制成。
7.依据权利要求1的金属颗粒，其中所述金属颗粒由合金制成。
8.依据权利要求1的金属颗粒，其中所述金属颗粒由选自锡、银、铜、铅、锌、铟、铋、和稀土金属的元素金属制成。
9.依据权利要求1的金属颗粒，其中所述金属颗粒由选自锡/银/铜、锡/铋、锡/铅和锡/铟/铋合金的合金制成。
10.一种焊接膏组合物，其包含依据权利要求1的涂布金属颗粒。
11.权利要求10的焊料膏组合物，其中相对于总组分，所述涂布金属颗粒的量为约10-约98重量％。
12.依据权利要求1的金属颗粒，其中在所述金属颗粒上的聚合物涂层的厚度小于约5μm。
13.依据权利要求1的金属颗粒，其中在所述金属颗粒上的聚合物涂层的厚度为约0.0001-约3.0μm。
14.依据权利要求1的金属颗粒，其中在所述金属颗粒上的聚合物涂层的厚度为约0.001-约1μm。
15.一种形成聚合物涂布的金属颗粒的方法，其包括以下步骤：
a)提供若干金属颗粒；
b)在适合的条件下施加单体或可热分解聚合物，以基本上涂布大多数所述金属颗粒的至少一部分表面；和
c)在单体的情况下，使所述单体固化成为金属颗粒上的聚合物涂层。
16.一种形成焊接膏的方法，其包括以下步骤：
a)提供用氰基丙烯酸酯聚合物涂布的焊接粉末；
b)提供焊接膏组分；和
c)将所述用聚合物涂布的焊接粉末与所述焊接膏组分混合，以形成焊接膏。
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KR20110089352A (ko) 2011-08-05
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