CN101001980B - 锡表面的耐腐蚀性改进 - Google Patents

锡表面的耐腐蚀性改进 Download PDF

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CN101001980B
CN101001980B CN2005800259655A CN200580025965A CN101001980B CN 101001980 B CN101001980 B CN 101001980B CN 2005800259655 A CN2005800259655 A CN 2005800259655A CN 200580025965 A CN200580025965 A CN 200580025965A CN 101001980 B CN101001980 B CN 101001980B
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tin
based surface
acid compounds
phosphinic acid
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范崇伦
约瑟夫·A·艾比斯
徐晨
爱德华·J·Jr·库德瑞克
文森特·Jr·派纳卡西奥
伊格尔·扎瓦瑞尼
克里斯蒂安·里埃特曼
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MacDermid Enthone Inc
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Abstract

一种提高工件上的锡基表面的耐腐蚀性的方法，该方法涉及使锡基表面与包括膦酸化合物和水的组合物接触，以便在锡基涂层上形成磷基膜，从而抑制锡基表面的腐蚀。包含膦酸的组合物具有浓度高达约30％体积的有机溶剂和水。

Description

锡表面的耐腐蚀性改进
发明领域：
本发明涉及抑制锡基表面腐蚀的方法和组合物，并且涉及抑制这种表面腐蚀和提高可焊性。
背景技术：
锡基涂层经常应用于铜和镍基工件的表面，如电接插件、工程、功能的和装饰装置的表面，以免铜或镍基表面被氧化或失去光泽，和/或提高可焊性。在空气或在其它氧化性环境中温度上升的条件下，电子仪器组件导线和电接插件的涂锡表面在制造和装配成电子器件之间的运输和存储过程中容易形成氧化膜。厚度一般仅仅约50-200埃(
Figure G05825965520070202D000011
)的氧化物涂层，使涂锡表面褪色，并且赋予被许多消费者认为不可接受的淡黄色。而且，该氧化物可以降低涂覆电线端的接触电阻。无褪色的表面比氧化物涂覆的表面具有更低的接触电阻和更好的可焊性。
S.Chen等人在美国专利No.6,136,460中公开减少锡的氧化的方法，该方法涉及在锡基质中具有比锡更消极的氧化物形成自由能的元素的内含物。其中，这种元素包括钾、钠、钙、铬、锰、镁、铝、钒、锌、铟和磷。这种内含物可以通过该元素电解沉积到锡表面上，使表面浸入该元素的溶体中，或浸入该元素的盐溶液中，接着通过高温重熔技术实现。高温暴露使该方法对于一些温度敏感的应用不受欢迎，并且增加处理时间、成本和设备要求。
H.E.Fuchs等人在美国专利No.5,853,797公开一种用于提供涂覆电接触表面的腐蚀保护的方法和溶液，包括将这种表面暴露到包含膦酸酯、润滑剂和各种挥发性的有机溶剂的溶液中。这种用于处理的溶剂的蒸发充满对环境忧虑，如处理、危害工人、和垃圾处理物流。
上述方法具有固有的缺点如高的处理温度、费用、和困难的溶剂。因此，需要低温的、对环境友好、和廉价的方法，对锡基表面提供防褪色、抗氧化的试剂，以便防止电学接头和电接插件在存储和运输期间常遇的黄化和氧化。本发明提供满足这种需要的溶液。
发明内容：
因此，本发明的目的之一是提供一种赋予锡基表面耐腐蚀性并且提高其可焊性的方法和组合物。
简要地说，因此，本发明涉及一种提高工件的锡基表面的耐腐蚀性的方法，该方法包括使锡基表面与包括膦酸化合物和水的组合物接触，以便在锡基涂层上形成磷基膜，从而抑制锡基表面的腐蚀。
本发明还涉及多种用于提高工件锡基表面的耐腐蚀性的组合物，该组合物包括约0.01和约10w/v％的膦酸化合物和水，并且这种组合物或者也可以包含浓度高达约30％体积的有机溶剂。
还公开了本发明的其它目的和特征。
附图简述：
图1是根据本发明形成的用于封装的电子元件的导线的横截面。
图2是电子组件。
图3是导线结构。
图4是电接插件。
图5和6是在实施例中讨论的试验件的照片。
图7是实施例的试验数据的图示。
图1-4是图示的，而不是按比例绘制的。
对应的附图标记在所有附图中表示对应的部件。
具体实施方式：
在一个方面，本发明涉及一种提高工件锡基表面的耐腐蚀性的方法。为了说明，一个这样的工件是电子元件如封装电子组件的电子导线，或是电接插件；但是本发明适合用于任何锡基表面，不管其是否是电子器件、工程、功能、装饰、或其它的部件。关于电子器件的锡基表面，该方法提高耐腐蚀性并且在包括一部分锡基表面重熔的焊锡操作之前的存储期间保护锡基表面的可焊性。
根据本发明，将锡基表面浸入组合物，或者与组合物接触，以便在锡基表面上形成磷基膜，该组合物包括膦酸化合物和水。这个膜抑制锡基表面的腐蚀。水优选去离子水。膦酸化合物具有化学式：
Figure G05825965520070202D000031
其中R是烃基或取代烃基，并且H离子可以被钠或钾替代形成膦酸盐。在一个实施方式中，其中R是长链线性或支链取代基，并且H离子可以被钠或钾替代形成膦酸盐。在优选的实施方式中，该膦酸化合物是通式为CH3(CH2)nP(O)(OH)2的膦酸，其中n是5到17。在一个目前优选的实施方式中，组合物包含辛基膦酸作为膦酸化合物。人们相信：PO3 -2部分促进该化合物连接到基质表面。
除非另有指示，在本文中所述的“取代烃基”部分是用至少一个非碳原子取代的烃基部分，包括碳链原子被杂原子如氮、氧、硅、磷、硼、硫、或卤素原子取代的部分。烃基部分可以被一个或多个下列取代基取代：卤素、杂环、烷氧基、链烯氧基、链炔氧基、芳氧基、羟基、保护的羟基、羟基碳酰基、酮类的、酰基、酰氧基、硝基、氨基、胺基、硝基、膦酰基、氰基、硫醇、酮缩醇乙缩醛、酯和醚。其中，合适的化合物是例如癸基磷酸、辛基磷酸、乙烯基亚磷酸、来自于Zip-ChemProducts(Morgan Hill，California)的石脑油(ZC-026)、和双官能分子如包括羧酸部分的膦酸化合物。
通常，膦酸化合物的浓度范围在约0.01到10重量/体积％(wt/vol％)(1重量/体积％＝在1升中为10克)。小于0.01％的浓度在腐蚀保护中无效果，而大于10％重量的浓度容易导致材料粘度太高，对大部分应用无用。
本发明的多种实施方式之一是使用包括膦酸化合物、水和在某些环境下可能需要的其它任选组分的组合物。存在其它的实施方式，其中该组合物包含膦酸化合物、有机溶剂、水、和在某些环境可能需要的其它任选组分。并且有其它的实施方式，该实施方式基本上由这些组分组成，即不包含那些实质影响本发明的基本性能的额外组分。在明确排除组分的实施方式中，这种排除对获得那些组合物的一些附加性能如简单、低成本、可预测性、降低相互作用的风险、和稳定性是关键的。
在本发明的一个实施方式中，使用有机溶剂，有助于膦酸化合物的溶解，但是仅仅在一个有限的程度。尤其是，这个实施方式的组合物包含不超过约30％体积(vol.％)的有机溶剂，并且在一些实施方式中，小于约5％体积的有机溶剂。有机溶剂可以是醇，并且在一个优选实施方式中，该有机溶剂是乙醇。在这个实施方式中，上面提到的忧虑基本上降低。有利地，通过将这种有机溶剂的浓度保持在低的水平，诸如处理、危害工人、垃圾处理成物流、闪点和费用的忧虑基本上降低。
在另一个实施方式中，组合物基本上无有机溶剂。这个实施方式包含膦酸化合物和水。有利地，通过除去有机溶剂，诸如处理、危害工人、和垃圾处理变成物流、和费用的忧虑被清除。
本发明还涉及包含更少水的浓缩物，它在使用之前被稀释。
在执行本发明的方法中，通过浸入、喷流、喷洒、或刷洗，使要处理的锡基表面暴露在本发明的组合物中。在一个实施方式中的曝露时间为约1秒和约60秒之间。组合物的温度在约20℃和约45℃之间。通常不漂洗所处理的表面。有时候，漂洗该表面以便增加表面的亮度。然而，这种漂洗能降低膜的有效性，因为它部分除去膜。允许组合物在表面上风干，以便留下薄的磷基膜，估计厚度在约5
Figure G05825965520070202D000051
和约10000
Figure G05825965520070202D000052
之间。
在干燥之后，将部件存储和/或运输到后续的制造操作中，在此这些部件通过金属连接技术即焊接与电子器件结合。在膜沉淀和真实的制造操作时刻之间，明确避免所处理的表面暴露到大于约230℃的温度。在制造操作中，当涉及将表面连接到装置基质的装配操作的部分时，锡表面在大于约230℃的温度下重熔。因此，担负磷膜的锡基表面首次暴露到大于约230℃的温度是一种连接操作。
在一个方面，本发明的方法涉及导线13(图1)，它是任何使用导线的标准电子组件例如图2所述的组件中的一部分。
图1显示具有导电基底金属10和锡或锡合金涂层11的导线13的电子组件14的一部分横截面。基底金属可以是铜、铜合金、铁、铁合金、或任何适合用于电子元件的其它金属。应用锡或锡合金涂层，对金属特征提供耐腐蚀性和可焊性。所使用的锡合金的实例包括Sn-Bi、Sn-Cu、和Sn-Ag。通常在应用封装14之后，对暴露的导线10应用Sn涂层11。然而，任选地，在该方法早期，对图3所示的导线结构30应用Sn涂层。
根据本发明的一个实施方式所处理类型的电子组件是用图3所示的导线结构30制造的。在得到图1中的组件14的封装步骤之前，将电子器件33定位在衬垫31上，并且通过电线联结32连接到导线13。
在另一个方面，本发明包括如图4所示的电接插件。一般对暴露部分11应用Sn涂层，并且根据本发明，该Sn涂层与本发明的含磷组合物接触。
这些图是图示的，并且各种相应的层不是按比例绘制的。
在以下实施例中对本发明进一步详细说明。
实施例1：
将具有锡基表面的铜片浸入本发明三种不同的组合物的平衡离子水中约10秒：
A-1.2重量/体积％的辛基磷酸；22％体积的乙醇
AA-1.6重量/体积％的辛基磷酸；0.2％体积的乙醇
AAA-1.6重量/体积％的辛基磷酸；0％的乙醇
在85℃和85％的相对湿度(RH)条件下，这些片材，和根据本发明具有锡基表面而无磷基组合物处理的铜片，被暴露在蒸汽中老化。此后，观察样品的褪色(淡黄色)如下：其中X是直至第一观测到褪色的天数：
表1锡涂层上的褪色测验结果
  后处理   天
  未处理   0＜X≤2
  A   88＜X≤106
  AA   73＜X≤91
  AAA   73＜X≤91
这些结果说明：用本发明的方法和组合物A、AA、和AAA，甚至在两个月之后也没有显著的褪色。
                        实施例2
对没有进行本发明处理的镀态的铜片和对通过用本发明组合物A浸泡约10秒处理的铜片进行照像。85℃/85％RH蒸汽老化23天之后的照像如图5所示。这些说明：在镀态的样品中褪色，而在根据本发明处理的样品中没有褪色。
                        实施例3
对没有进行本发明处理的镀态的铜片和对通过用本发明组合物A浸泡约10秒处理的铜片进行照像。85℃/85％RH蒸汽老化106天之后的照像如图6所示。这些说明：在镀态的样品中严重腐蚀，而在根据本发明处理的样品中的边缘处仅仅较小的褪色。
                        实施例4
在85℃和85％的相对湿度的条件下进行蒸汽老化18小时镀锡的样品进行可焊性润湿平衡试验(Joint Industry Standard J-STD-002)。润湿平衡试验条件是：Sn63Pb37焊接剂、235℃、R-型未活化的焊剂。在没有接受本发明处理的镀态的样品上进行五次试验的结果如图7A所示。这些结果显示：宽的读数偏差，和长的润湿时间(平均零点交叉定时，ZCT＞3.40秒)。
在接受本发明处理(在水中1.6重量/体积％的辛基磷酸和0.2％的乙醇)的样品上进行五次试验的结果如图7B所示。这些结果显示：锡基表面的氧化减轻。样品在蒸汽老化之后提供相当低的润湿时间读数(平均ZCT＝1.36+0.12秒)和窄的读数偏差。因此，用耐腐蚀材料处理显著提高了锡基表面的湿润性和可焊性。
本发明不局限于上述实施方式，并且可以进行各种改进。上述优选实施方式的说明只是旨在告知本领域普通技术人员本发明的原则和实际应用，使本领域普通技术人员可以以许多形式采用并应用本发明，并且可以最适合特定用途的要求。
参考整个说明书(包括下列权利要求书)中术语“包含”的使用，应该注意：除非上下文有其它含义，否则根据基本含义使用这些术语，并且清楚理解为解释包含而不是排除，并且在分析整个说明书中这些术语中每一个均如此解释。

Claims (25)

1.一种用于提高工件的锡基表面的耐腐蚀性的方法，所述方法包括：
使锡基表面与包括膦酸化合物、水和浓度小于5％体积的醇的组合物接触，以便在锡基涂层上形成磷基膜，从而抑制锡基表面的腐蚀，其中所述的膦酸化合物的浓度范围为0.01到10％w/v并且具有以下化学式的结构：
Figure FSB00000307086400011
其中R为烃基或取代烃基，并且H离子可以被钠或钾替代以便形成膦酸盐。
2.根据权利要求1所述的方法，其中R是取代烃基并且被至少一个非碳原子取代，所述非碳原子选自包括氮、氧、硅、磷、硼、硫和卤素原子的群组。
3.根据权利要求1所述的方法，其中R是取代烃基并且被选自包括卤素、杂环、烷氧基、链烯氧基、链炔氧基、芳氧基、羟基、保护的羟基、羟基碳酰基、酮类、酰基、酰氧基、硝基、氨基、胺基、硝基、膦酰基、氰基、硫醇、酮缩醇、乙缩醛、酯和醚的群组的取代物取代。
4.根据权利要求1所述的方法，其中所述磷酸化合物为浓度在0.01到10％w/v之间的膦酸，所述膦酸化合物具有通式：CH3(CH2)nP(O)(OH)2，其中n是5到17。
5.根据权利要求1所述的方法，其中所述工件是其上具有锡基表面的电子元件，所述电子元件上的锡基表面与包括膦酸化合物和水的组合物接触，以便在锡基表面上形成磷基膜，从而抑制锡基表面的腐蚀。
6.根据权利要求1所述的方法，其中所述工件是其上具有锡基表面用于在焊接操作中提供可焊表面的电子元件，所述电子元件的锡基表面与包括膦酸化合物和水的组合物接触，以便在锡基表面上形成磷基膜，从而抑制锡基表面的腐蚀并且在包括一部分锡基表面重熔的焊接操作之前的存储过程中保持电子元件的锡基涂层的可焊性。
7.根据权利要求6所述的方法，其中所述组合物包括：
膦酸化合物；
浓度小于5％体积的乙醇；和
水。
8.根据权利要求1-3或5-7中任何一项所述的方法，其中所述膦酸化合物具有通式：CH3(CH2)nP(O)(OH)2，其中n是5到17。
9.根据权利要求1-7中任何一项所述的方法，其中所述膦酸化合物是辛基磷酸。
10.一种用于提高工件的锡基表面耐腐蚀性的方法，所述方法包括：使锡基表面与包括膦酸化合物、水和浓度小于30％体积的乙醇的组合物接触，以便在锡基涂层上形成磷基膜，从而抑制锡基表面的腐蚀，其中所述的膦酸化合物的浓度范围为0.01到10％w/v，并且具有以下化学式的结构：
其中R为烃基或取代烃基，并且H离子可以被钠或钾替代形成膦酸盐。
11.根据权利要求10所述的方法，其中R是取代烃基并且被至少一个非碳原子取代，所述非碳原子选自包括氮、氧、硅、磷、硼、硫和卤素原子的群组。
12.根据权利要求10所述的方法，其中R是取代烃基并且被选自包括卤素、杂环、烷氧基、链烯氧基、链炔氧基、芳氧基、羟基、保护的羟基、羟基碳酰基、酮类、酰基、酰氧基、硝基、氨基、胺基、膦酰基、氰基、硫醇、酮缩醇、乙缩醛、酯和醚的群组的取代物取代。
13.根据权利要求10所述的方法，其中所述组合物包括：
膦酸化合物；
浓度小于5％体积的乙醇；和
水。
14.根据权利要求10所述的方法，其中所述磷酸化合物为浓度在0.01到10％w/v之间的膦酸，所述膦酸化合物具有通式：CH3(CH2)nP(O)(OH)2，其中n是5到17。
15.根据权利要求10所述的方法，其中所述工件是其上具有锡基表面的电子元件，所述电子元件上的锡基表面与包括膦酸化合物和水的组合物接触，以便在锡基表面上形成磷基膜，从而抑制锡基表面的腐蚀。
16.根据权利要求10所述的方法，其中所述工件是其上具有锡基表面以便在焊接操作中提供可焊表面的电子元件，所述电子元件的锡基表面与包括膦酸化合物和水的组合物接触，以便在锡基表面上形成磷基膜，从而抑制锡基表面的腐蚀并且在包括一部分锡基表面重熔的焊接操作之前的存储过程中保护电子元件的锡基涂层的可焊性。
17.根据权利要求16所述的方法，其中所述组合物包括：
膦酸化合物；
浓度小于5％体积的乙醇；和
水。
18.根据权利要求10到13或15到17中任何一项所述的方法，其中所述膦酸化合物具有通式：CH3(CH2)nP(O)(OH)2，其中n是5到17。
19.根据权利要求10到17中任何一项所述的方法，其中所述膦酸化合物是辛基磷酸。
20.一种用于提高工件锡基表面的耐腐蚀性的组合物，所述组合物包括：
浓度为0.01到10％w/v的膦酸化合物，其化学式为：
Figure FSB00000307086400041
其中R是烃基或取代烃基，并且H离子可被钠或钾替代，以便形成膦酸酯盐；
浓度达到5％体积的乙醇；和
水。
21.根据权利要求20所述组合物，其中所述膦酸化合物具有通式为：CH3(CH2)nP(O)(OH)2，其中n是5到17。
22.根据权利要求20所述的组合物，其中所述膦酸化合物是辛基磷酸。
23.一种用于提高工件锡基表面的耐腐蚀性的组合物，所述组合物包括：
浓度在0.01到10％w/v之间的膦酸化合物，其化学式为：
Figure FSB00000307086400042
其中R是烃基或取代烃基，并且H离子可被钠或钾替代，以便形成膦酸酯盐；
浓度达到30％体积的乙醇；和
水。
24.根据权利要求23所述组合物，其中所述膦酸化合物具有通式：CH3(CH2)nP(O)(OH)2，其中n是5到17。
25.根据权利要求23所述的组合物，其中所述膦酸化合物是辛基磷酸。
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JP5306646B2 (ja) 2013-10-02
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