CN1953868B - 无铬的防晦暗粘合促进处理组合物 - Google Patents
无铬的防晦暗粘合促进处理组合物 Download PDFInfo
- Publication number
- CN1953868B CN1953868B CN200480028993.8A CN200480028993A CN1953868B CN 1953868 B CN1953868 B CN 1953868B CN 200480028993 A CN200480028993 A CN 200480028993A CN 1953868 B CN1953868 B CN 1953868B
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- China
- Prior art keywords
- coating
- ions
- ion
- zinc
- antitarnish
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- Expired - Lifetime
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 15
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
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Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
-
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Abstract
本发明涉及含水的防晦暗且促进粘合的处理组合物,其包括锌离子;选自钨离子、钼离子、钴离子、镍离子、锆离子、钛离子、锰离子、钒离子、铁离子、锡离子、铟离子、银离子、及其结合中的金属离子;和任选地,不含钾或钠离子的电解质;其中该处理组合物基本上不含铬,和其中该处理组合物能够在材料上形成涂层,其中该涂层增强聚合物对该材料的粘合。本发明还涉及用上述处理组合物涂布的材料,和使用上述组合物涂布材料的方法。
Description
发明背景
1.发明领域
本发明涉及抗晦暗且促进粘合的处理组合物,和更特别地,涉及基本上不含铬的抗晦暗且促进粘合的处理组合物。
2.现有技术的简要说明
对于各种应用,例如印刷电路、电子封装、机动车车身装饰(例如,铝对PVC或ABS塑料)、钢丝带束层轮胎和油漆或其它聚合物涂层来说,长期寻求金属的抗晦暗和在金属与聚合物之间的强力粘合。例如,对于印刷电路应用来说,因寿命要求Cu箔抗晦暗,且耐受在印刷电路的加工中在层压和焊接过程中的热暴露。防晦暗涂层还防止一旦在部件的使用寿命期间因湿度和温度暴露导致的Cu氧化并与聚合物基底的反应。这一功能对于维持Cu和聚合物之间良好的粘结是关键的。对于电子封装应用来说,要求在金属插孔和围绕金属插孔的模塑塑料绝缘鞘之间的电子连接器内良好的粘合。作为第二个实例,在电子封装件的组装中,金属引线框(leadframe)内的内部引线可封装在聚合物模塑树脂内,以容纳集成电路。
通过用对聚合物树脂形成更强力粘结的第二金属涂布金属基底,来改进在聚合物树脂与金属基底之间的粘合。合适的涂层包括耐火氧化物形成金属,例如镍和镍合金,或金属间化合物形成涂层,例如在铜基底上的锡。在Crane等人的美国专利No.4888449中公开了这些涂层,以及其它,在此通过参考将其全文引入。
目前,在电子应用中,含锌/铬(ZnCr)的涂层广泛用于铜箔和引线框上,以改进抗晦暗和金属对聚合物基底的粘结强度。典型地在含NaOH、Zn和Cr(VI)离子的碱性溶液内,电沉积这些涂层,形成提供抗晦暗的Zn/Cr氧化物的混合物。
美国专利No.4387006公开了处理在印刷线路板中使用的铜箔表面的方法。在含有锌离子和铬(VI)离子的铬酸锌水溶液内电解处理铜箔,并将铜箔浸渍在含有氨基硅烷、硅酸钠和/或硅酸钾的水溶液内。
美国专利No.5230932、No.5098796和No.5022968公开了改进铜和铜基合金材料的抗晦暗和抗氧化的技术与组合物。通过在含有NaOH、锌离子和Cr(VI)离子的含水电解质内浸渍,电解涂布该材料。该涂层在超过190℃的温度下提供抗晦暗性。
Chen的美国专利No.5250363公开了改进金属基底的抗晦暗和抗氧化的技术。将该基底浸渍在含有NaOH、锌离子和Cr(VI)离子的水溶液内,并将铬-锌涂层电解施涂到基底上。该涂层在超过230℃的温度下提供抗晦暗性,且通过在硫酸内浸渍容易除去。
同样要求保护的是,在一定条件下,这些涂层中的数种涂层可降低引线框与模塑料之间的透湿性。这一效果可大大地降低“爆裂玉米(pop corn)效应”,认为所述爆裂玉米效应因当器件处于焊接温度(例如约230℃的温度)时,由在小片连接桨状物(paddle)下方捕获的累积湿气形成水蒸气而引起。认为因裂纹和脱层导致水蒸气的这种生成是器件故障的原因。此外,随着工业淘汰含铅和其它元素的焊料(这主要由于环境担心和严格的法规导致),可供替代的焊料可具有甚至更高的焊接温度,和金属/聚合物的粘合特征可能变得更加重要。
已知许多组合物提供金属与聚合物之间的粘合。Parthasarathi等人的美国专利No.5573845公开了一种复合材料,其具有所需表面保护层(finish)的金属核心。表观厚度小于275埃的针状(结节状)表面涂层与至少一部分金属核心相邻。在没有显著改变金属核心的表面保护层的情况下,表面涂层可从金属核心上除去。
Parthasarathi等人的美国专利No.5449951公开了一种对聚合物树脂具有增强的粘合性的引线框。用含铬、锌或铬与锌的混合物的薄层涂布该引线框。涂布的引线框对聚合物树脂显示出改进的粘合性。
在Lee等人的国际公开号WO 00/74131A1中,公开了一种组装半导体器件封装件的方法,其中形成器件/引线框组件,并在器件/引线框组件的暴露表面上沉积粘合增强涂层,接着封装。该涂层是金属涂层,所述金属涂层可以是无机Zn-Cr涂层。这一公开出版物特意在此通过参考全文引入。
Ogawa等人的美国专利No.5252855公开了通过阳极氧化基底,形成针状晶体的聚集体,从而改进铜基础金属基底与聚合物树脂之间的粘合。铝合金基底的阳极化增强聚合物粘结的强度,正如在Mahulikar等人的美国专利No.4939316中所公开的。其它满意的涂层包括厚度为300-5000埃的抗氧化材料,正如Yamazaki等人的美国专利No.5192995中所公开的。
根据上述现有技术的公开内容,经常在浸渍浴中使用钠(Na)和/或钾(K)。然而,钠和钾离子的缺点是这些离子潜在地可扩散到硅片内并引起所生产的器件故障。在文献中充分地记载了这种故障(参见,例如“Metallization Contamination”,Microelectronic DefectsDatabase,CALCE Electronic Products and Systems Center,University of Maryland,2000年4月12日,证明了来自模塑料、小片涂层和小片连接涂层内的氯化物和钠污染;和Barnes与Robinson,“The Impact of Ionic Impurities in Die AttachAdhesives on Device Performance”,Proceedings of 34thElectronics Components Conf.,1984年5月,第68页,证明了小片连接粘合剂为离子污染的特定源)。
另外,在电镀溶液中存在Cr(VI)离子引起处理和处置方面的环境担心。尽管数十年来,全世界一直在使用含Cr(VI)的电镀浴,但由于对健康和环境影响的增长担心导致使用Cr(VI)正接受愈加细致的检查。因此,希望或者用毒性较小的Cr(III)浴替代Cr(VI)电镀浴或者完全省去Cr。
因此,本领域需要提供一种含水的促进粘合且抗晦暗的处理组合物,它基本上不含铬(VI)且利用不含钾或钠离子的任选电解质。认为本发明满足了这一需求。
发明概述
一方面,本发明涉及含水的防晦暗且促进粘合的处理组合物,其包括锌离子;选自钨离子、钼离子、钴离子、镍离子、锆离子、钛离子、锰离子、钒离子、铁离子、锡离子、铟离子、银离子、及其结合中的金属离子;和任选地,不含钾或钠离子的电解质;其中该处理组合物基本上不含铬,和其中该处理组合物能够在材料上形成涂层,其中该涂层增强聚合物对该材料的粘合。
另一方面,本发明涉及用防晦暗和粘合处理涂层涂布的材料,所述处理涂层包括:锌或氧化锌原子;和选自钨、钼、钴、镍、锆、钛、锰、钒、铁、锡、铟、银、及其结合中的金属或金属氧化物原子;其中该涂层基本上不含铬,和其中该涂层在250℃下提供至少30分钟的抗晦暗性,和其中该涂层含有增强聚合物对该材料粘合性的结节结构。
再一方面,本发明涉及用防晦暗且促进粘合的涂层涂布的材料的形成方法,该方法包括下述步骤:使该材料与含水的防晦暗且促进粘合的处理组合物接触,所述处理组合物包括锌离子;选自钨离子、钼离子、钴离子、镍离子、锆离子、钛离子、锰离子、钒离子、铁离子、锡离子、铟离子、银离子、及其结合中的金属离子;和任选地,不含钾或钠离子的电解质;其中该处理组合物基本上不含铬,和在该材料上沉积防晦暗且促进粘合的涂层的条件下,使电流流经该处理组合物,形成用防晦暗且促进粘合的涂层涂布的材料,其中该涂层增强聚合物对该材料的粘合。
在本发明的下述详细说明中,将更详细地描述本发明的这些和其它方面。
附图简述
根据下述详细说明结合附图,将更充分地理解本发明,其中:
图1(a)、1(b)和1(c)示出了根据本发明的组合物和方法处理的表面分别在2、5和10秒的电镀时间之后的扫描电子显微照片(SEM);和
图2示出了柱状图,该柱状图描述了各种表面处理和它们对模塑料与处理表面之间粘结强度的影响。
发明详述
发明人令人惊讶地发现,能够生产含水的防晦暗且促进粘合的处理组合物,其使得可在金属与聚合物之间形成强力粘结,并解决在处理和处置这种组合物时的环境和健康影响。根据本发明,发明人现已发现一种含水的防晦暗且促进粘合的处理组合物,其在聚合物材料与金属之间具有改进的粘结性,使用不含Na/K的电镀溶液防止用这种元素污染硅片,且基本上不含铬(VI),结果在处理这种溶液时消除了涉及环境和健康的问题。
如上所述,本发明涉及一种含水的防晦暗且促进粘合的处理组合物,其包括:(1)锌离子;(2)选自钨离子、钼离子、钴离子、镍离子、锆离子、钛离子、锰离子、钒离子、铁离子、锡离子、铟离子、银离子、及其结合中的金属离子;和(3)任选地,不含钾或钠离子的电解质;其中该处理组合物基本上不含铬,和其中所述处理组合物在材料或基底上形成涂层,该涂层增强聚合物对该材料或基底的粘合。以下将更加详细地讨论这些组分中的每一种。
本发明处理组合物中的锌离子组分可衍生于使得能在水溶液中形成显著大量锌离子的任何锌盐。有用的锌盐的实例包括,但不限于,硫酸锌、氧化锌、氯化锌、氟硼酸锌、乙酸锌、及其结合。还要理解,也可在本发明的组合物中或者单独或者结合使用上述锌盐的水合物。在一个优选的实施方案中,例如,锌盐是七水合硫酸锌(ZnSO4·7H2O)。
优选地,基于组合物的总体积,锌离子以约0.1-约100g/L,和更优选约0.5-约50g/L,和最优选约0.5-约20g/L的用量存在于本发明的组合物内。在一个优选的实施方案中,锌盐是七水合硫酸锌(ZnSO4·7H2O),和在本发明的组合物内的用量范围为约2-约80g/L。
本发明的含水的防晦暗且促进粘合的处理组合物进一步包括可与锌形成共沉积物且导致在材料或基底表面上沉积总体为结节结构的金属离子。有用的金属离子包括钨离子、钼离子、钴离子、镍离子、锆离子、钛离子、锰离子、钒离子、铁离子、锡离子、铟离子和银离子。在本发明的处理组合物中,可单独或结合使用金属离子。
金属离子可衍生于相应的金属盐,或其水合物,或金属酸。可用于本发明组合物的金属盐或金属盐的水合物的实例包括硫酸镍或硫酸镍水合物、钼酸铵、氧化钼、高锰酸钾、硫酸锰、及其结合。金属酸的实例包括钼酸、钨酸、钨硅酸、及其结合。在一个优选的例举实施方案中,金属离子是钼离子、钨离子、或其结合。本发明不限于这些实例,并且可使用其它金属盐、或其水合物、或金属酸。
优选地,基于组合物的总份数,金属离子以约5-约20000ppm,和更优选约15-约2000ppm,和最优选约25-约300ppm的用量存在于组合物内。
在许多情况下,锌盐提供本发明的组合物足够的电导率,使得锌和金属离子可沉积在材料或基底上。然而,若锌盐的浓度低,则可能不存在充足的电导率以供组合物的合适电解沉积。在这种情况下,优选添加额外的电解质到处理组合物中,以便可发生合适的沉积。可使用任何水溶性盐作为电解质,然而,希望这种电解质不含钠或钾。正如在WO00/74131中所述,在含水电镀组合物内存在钠或钾离子导致这些离子扩散到根据WO00/74131的教导处理的硅片内,和随后电子器件出现故障。因此,优选不含钠或钾的电解质。
可用的电解质的非限制性实例包括硫酸铵、硼酸、柠檬酸、葡糖酸、氢氧化铷、氯化铵、及其结合。一般来说,电解质组分的用量为约1g/L-约500g/L,和更优选约5g/L-约200g/L,和最优选约10g/L-约50g/L。
如上所述,本发明的含水、防晦暗且促进粘合的处理组合物基本上不含铬。铬的存在仅仅来自于原料化学品或环境中的不可避免的污染。正如此处所定义的,“基本上不含铬”通常是指基于组合物的总重量,铬的含量低于约0.001wt%。已表明铬(VI)有毒且具有环境、健康和安全缺陷。因此,认为基本上不含铬的本发明的组合物不具有这些缺陷。
可通过在水中混合适量锌与金属化合物,和任选的电解质,确立每一组分所需的浓度,从而制造本发明的处理组合物。通过添加酸(例如,硼酸、硫酸、盐酸、柠檬酸、葡糖酸等等)或不含钠或钾的碱(例如,氢氧化钙、氢氧化镁、氢氧化铷、氢氧化铵等等),确立溶液的pH。对于本发明的处理组合物来说,优选的pH范围为约0.5-约14.0;更优选的pH范围为约1.5-约13.5;最优选的pH范围为约2.5-约13.0。另外,若本发明的组合物具有在中性范围内的pH(例如,pH5-9),则可需要络合剂,例如柠檬酸或葡糖酸的盐,以维持在电镀溶液内处于可溶状态的金属离子。
一般来说,可通过施加涂层的已知方法施涂本发明的不含铬的防晦暗且促进粘合的处理组合物。例如,在涂布材料或基底之前,可在商业碱性清洁剂或NaOH中电清洁该材料或基底,以除去任何残留的润滑剂、油、灰尘或表面氧化物。清洁剂的例举浓度典型地为30g/L和浴温为130且电流密度为30asf(安培/平方英尺)经20秒。然而,可使用本领域已知的任何所需的清洁参数。在清洁之后,将样品浸渍在5%硫酸溶液内以活化表面。
在沉积过程中,下述条件是所需的。在沉积过程中电镀浴的温度范围优选为约100-约150,更优选约110-约140,和最优选约120-约140。沉积过程中所使用的电流密度范围可优选是约2-约200asf,更优选约5-约100asf,和最优选约5-约30asf。沉积时间范围可优选是约1-约200秒,更优选约2-约50秒,和最优选约2-约20秒。
当在材料或基底上沉积时,本发明的组合物形成含有结节结构的涂层,正如图1(a)、1(b)和1(c)所示。涂层厚度范围优选是约15-约500埃,这取决于沉积条件(正如以下将更加详细地讨论的)。每16平方微米上平均具有优选约25-约1000个结节结构,和最优选平均密度为约50-约500个结节结构/平方微米。每一结节结构的平均长度优选为约0.01微米-约1微米,和更优选平均长度为约0.05-约0.5微米。优选的长径比(长度比直径)优选为约1∶1-约8∶1,和更优选约2∶1-约6∶1。
认为大多数结节结构没有从表面上垂直地延伸,而是从表面上以各种角度延伸,从而形成交叉网。在单个结节结构之间的空隙上流动的聚合物沿着在间隙之间的曲折路径行进,和一旦固化,聚合物看起来机械地原地锁定。涂层还增强材料或基底对聚合物的粘合。相对于不具有结节结构的表面,在基底表面上存在结节结构增强聚合物粘合剂的机械锁定。例如,可在使样品暴露于85%RH/80-85℃下168小时,紧跟着在约260℃的焊料内热振动120秒之后,获得范围优选大于1000psi,和更优选1100-2400psi的粘结强度,这取决于聚合物粘合剂的类型。涂层坚固地粘结到金属基底上且在金属基底和涂层之间的界面处或者在涂层本身内部不易于分离,因为这是采用氧化物涂层情况下典型的。在没有本发明所述的结节状防晦暗涂层的情况下,金属与聚合物之间的粘结强度典型地不到以上所述的的一半。
在储存、加工或使用过程中复合材料可暴露的温度下,涂层赋予抗氧化性。这些温度典型地为最多约250℃。尽管涂层具有不连续的空隙和间隙,但没有空隙和间隙完全延伸穿过涂层或导致氧化位点。除了抗氧化性以外,涂层还提供抗腐蚀性,结果稀释在工业环境或者在操作者的手指上发现的氯化物、硫化物和其它污染物浓度。
本发明所述的防晦暗促进粘合的涂层和施涂方法可应用到任何导体上以及在基于电化学原理的任何工艺步骤内。可电镀例如,铜和铜合金以及镍、铁、铝、钢、不锈钢、锌、锡、银、钯、金、钛、碳和足够导电使电流流过的任何其它材料或基底。另外,也可使得甚至已金属化的非导体本身被电镀。在另一实例中,方便的是在引线框制造工艺中,在镀银之后施涂这种防晦暗涂层。视需要,可在随后的银汽提工艺中,在其中要求布线粘结的位置处,使用掩模除去这一涂层,典型地采用所述银汽提工艺除去背镀层或银的溢出电镀层。或者,可在IC芯片连接和布线粘结之后,施涂这一防晦暗涂层。不需要这种方式,除去在布线粘结区域内的这一涂层。
通过下述实施例进一步详细地描述本发明。所有份数和百分数以重量计,和所有温度为摄氏度,除非另有说明。
实施例
实施例1
在商业碱性清洁剂中电清洁C110铜箔(>99.9%Cu和<0.05%0),从表面上除去残留的润滑剂、污染物和氧化物。然后在含有10g/LZnSO4·7H2O、10g/L(NH4)2SO4和25ppm W(钨,钨硅酸形式)的溶液内浸渍清洁过的铜箔。经2、5和10秒的时间间隔,施加10安培/平方英尺(ASF)的电镀电流到0.035ft2的区域上。然后漂洗并干燥样品。图1(a)、1(b)和1(c)表明在三个时间间隔处处理过的表明的扫描电子显微照片(SEM)。在每一情况下,可看到结节形态。
使用Scotch 600胶带对铜箔样品进行胶粘试验。首先将胶带压制到电镀表面上,然后从该表面上撕开。在电镀样品上留下可见的胶粘物,这表明结节结构沉积在铜箔上。
进一步对该样品进行250℃烘烤30分钟。样品在烘烤之后没有显示出氧化,同时未处理的部分严重氧化。这一结果表明,沉积的涂层提供良好的抗晦暗性。使用如上所述的Scotch 600胶带对烘烤的样品进一步进行胶粘试验。在电镀样品上留下可见的胶粘物,从而再次表明在铜箔表面上存在结节结构。
实施例2
将在一侧上具有纯铜树枝状晶体和在另一侧上裸露的C110铜箔样品浸渍在5wt%H2SO4中30秒,除去任何已有的表面氧化物。将该样品放置在夹具内,所述夹具暴露仅仅一个表面于含有10g/LZnSO4·7H2O、20g/L(NH4)2SO4和25ppm W的含水电镀组合物下,并经5秒施加10ASF的电镀电流到0.104ft2的区域上。然后漂洗并干燥样品。在第二样品上反复这一工序,暴露相反表面于相同溶液和电镀电流下。进一步对样品进行95℃/55%RH试验60分钟,以模拟在炎热和潮湿条件下的长期储存性。随后在190℃下烘烤样品30分钟,且表明没有氧化。未处理的部分严重氧化。这表明涂层提供良好的抗晦暗性。
实施例3
在商业碱性清洁剂中电清洁C110铜箔,从表面上除去残留的润滑剂、污染物和氧化物。在含有5g/L ZnSO4·7H2O、3g/L NiSO4·6H2O、50ml KMnO4N/10和2.5ml/L MITIQUE(无机酸组合物,其含有1-3%的钼酸铵;Hubbard Hall,Waterbury,CT)的溶液内,经5秒施加5ASF的电镀电流到0.035ft2的区域上。然后漂洗并干燥样品,和使用Scotch 600胶带对其进行胶粘试验。首先将胶带压制到电镀表面上,然后从该表面上撕开。在电镀样品上留下可见的胶粘物。这一结果表明沉积了结节结构。
进一步对该样品进行250℃×10分钟的烘烤试验,和该样品在烘烤之后没有显示出氧化。未处理的部分严重氧化。这一结果表明,该涂层提供良好的抗晦暗性。
实施例4
在商业碱性清洁剂中电清洁厚度为0.03英寸的C7025铜箔(96.2%Cu,3.0%Ni,0.65%Si和0.15%Mg),从表面上除去残留的润滑剂、污染物和氧化物。在含有10g/L ZnSO4·7H2O和1.5ml/L MITIQUE的溶液内,经10秒施加10ASF的电镀电流到0.035ft2的区域上。然后漂洗并干燥样品。使用Scotch 600的胶粘试验导致胶粘物转移到处理表面上,和表明获得结节或糙化表面。电镀额外的样品,使用Sumicon6300模塑料封装,并进行168小时的85%RH/85℃的湿度测试,正如在测试标准IPC/JEDEC J-STD-020A中所述。在暴露之后,样品在约260℃下在焊料中飘浮120秒,并在撕开试验中测量粘合强度,在所述撕开试验中,使用Instron拉伸测试机,封装的金属样品从模塑料上撕开并记录分离力。当与没有暴露于该温度/湿度下的样品相比较时,发现粘结强度很少损失。相比之下,不具有结节处理的样品典型地损失其起始粘结强度的50%以上。
实施例5
在商业碱性清洁剂中电清洁C110铜箔,从表面上除去残留的润滑剂、污染物和氧化物。在含有10g/L ZnSO4·7H2O和45ppm MoO3的溶液内,经10秒施加10ASF的电镀电流到0.035ft2的区域上。然后漂洗并干燥样品,和使用Scotch 600胶带对其进行胶粘试验。首先将胶带压制到电镀表面上,然后从该表面上撕开。在电镀样品上留下可见的胶粘物。这一结果表明沉积了结节结构。
进一步对该样品进行250℃×10分钟的烘烤试验,和该样品在烘烤之后没有显示出氧化。未处理的部分严重氧化。这一结果表明,该涂层提供良好的抗晦暗性。
实施例6
在商业碱性清洁剂中电清洁厚度为0.03英寸的C7025铜箔,从表面上除去残留的润滑剂、污染物和氧化物。在含有10g/L ZnSO4·7H2O和30ppm Mo(钼酸形式)的溶液内,经10秒施加10ASF的电镀电流到0.035ft2的区域上。然后漂洗并干燥样品,和使用Scotch 600胶带对其进行胶粘试验。胶粘试验导致胶粘物转移到处理表面上,和表明获得结节或糙化表面。电镀额外的样品,使用Sumicon 6300和ShinetsuKMC-289-3ECS模塑料封装,进行168小时的85%RH/85℃的湿度测试,正如在IPC/JEDEC J-STD-020A中所述。在暴露之后,样品在约260℃下在焊料中飘浮120秒,并测量粘合强度。正如图2所示,当与未暴露的样品相比时,发现粘结强度很少损失。
实施例7
在商业碱性清洁剂中电清洁厚度为0.03英寸的C7025铜箔,从表面上除去残留的润滑剂、污染物和氧化物。在含有15g/L ZnSO4·7H2O、15g/L(NH4)2SO4和25ppm W(钨硅酸形式)的溶液内,经5秒施加10ASF的电镀电流到0.035ft2的区域上。然后漂洗并干燥样品,和使用Scotch 600胶带对其进行胶粘试验。首先将胶带压制到电镀表面上,然后从该表面上撕开。在电镀样品上留下可见的胶粘物。这一结果表明沉积了结节结构。
进一步对该样品进行250℃×10分钟的烘烤试验,和该样品在烘烤之后没有显示出氧化。未处理的部分严重氧化。这一结果表明,该涂层提供良好的抗晦暗性。
电镀额外的样品,使用Sumicon 6300和Shineto KMC-289-3ECS模塑料封装,进行168小时的85%RH/85℃的湿度测试,正如在IPC/JBDEC J-STD-020A中所述。在暴露之后,样品在约260℃下在焊料中飘浮120秒,并测量粘合强度。正如图2所示,当与未暴露的样品相比时,发现粘结强度没有损失。
实施例8
在商业碱性清洁剂中电清洁厚度为0.03英寸的C7025铜箔,从表面上除去残留的润滑剂、污染物和氧化物。在含有12.5g/L NaOH、2.25g/L锌和0.65g/L W的溶液内,经4秒施加5ASF的电镀电流到0.035ft2的区域上。然后漂洗并干燥样品。使用Scotch600胶带对样品进行胶粘试验。首先将胶带压制到电镀表面上,然后从该表面上撕开。在电镀样品上留下可见的胶粘物。这一结果表明沉积了结节结构。
进一步对该样品进行250℃×30分钟的烘烤试验,和该样品在烘烤之后没有显示出氧化。未处理的部分严重氧化。这一结果表明,该涂层提供良好的抗晦暗性。
Claims (9)
1.一种用防晦暗和粘合处理涂层涂布的材料,所述防晦暗和粘合处理涂层包括:
锌或氧化锌;和
至少一种选自钨、钼、钴、镍、锆、钛、锰、钒、铁、锡、铟、银、及其结合中的金属或金属氧化物;
其中所述涂层基本上不含铬,和其中所述涂层在250℃下提供至少30分钟的抗晦暗性,和其中所述涂层含有增强聚合物对所述材料粘合性的结节结构。
2.权利要求1的涂布的材料,其中所述材料包括选自铜、铜合金、镍、铁、铝、钢、不锈钢、锌、锡、银、钯、金、钛、碳、金属化非导体、及其结合中的材料。
3.权利要求1的涂布的材料,其中在所述材料上的所述涂层的厚度为15-500埃。
4.权利要求1的涂布的材料,其中所述涂层含有25-1000个所述结节结构/16平方微米。
5.权利要求1的涂布的材料,其中所述结节结构各自具有0.01微米-1微米的平均长度,和1∶1-8∶1的长径比(长度比直径)。
6.权利要求1的涂布的材料,其包括涂布的基底。
7.权利要求6的涂布的材料,其包括电子器件。
8.权利要求6的涂布的材料,其包括器件/引线框组件。
9.权利要求6的涂布的材料,其中在使所述涂布的基底暴露于85%RH/80-85℃下168小时,紧跟着在约260℃的焊料内热振动120秒之后,增强的粘合强度大于1000psi。
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CN200480028993.8A Expired - Lifetime CN1953868B (zh) | 2003-09-02 | 2004-08-31 | 无铬的防晦暗粘合促进处理组合物 |
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US (2) | US6852427B1 (zh) |
EP (1) | EP1709215A4 (zh) |
JP (2) | JP2007508448A (zh) |
KR (1) | KR101368879B1 (zh) |
CN (1) | CN1953868B (zh) |
MY (1) | MY149149A (zh) |
TW (1) | TWI369296B (zh) |
WO (1) | WO2005021836A2 (zh) |
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JP4644718B2 (ja) | 2008-01-31 | 2011-03-02 | 株式会社日立製作所 | 金属/樹脂接着構造体及び樹脂封止型半導体装置とその製造方法 |
US20120168075A1 (en) * | 2008-03-21 | 2012-07-05 | Enthone Inc. | Adhesion promotion of metal to laminate with multi-functional molecular system |
US8076003B2 (en) * | 2008-09-26 | 2011-12-13 | Infineon Technologies Ag | Coating composition and a method of coating |
ATE513066T1 (de) | 2008-10-13 | 2011-07-15 | Atotech Deutschland Gmbh | Verfahren zur verbesserung der haftung zwischen silberoberflächen und harzmaterialien |
JP2010171271A (ja) | 2009-01-23 | 2010-08-05 | Renesas Technology Corp | 半導体装置およびその製造方法 |
TWI468550B (zh) * | 2009-04-14 | 2015-01-11 | Enthone | 以多官能分子系統促進金屬黏著成層合體 |
US20110220511A1 (en) * | 2010-03-12 | 2011-09-15 | Xtalic Corporation | Electrodeposition baths and systems |
US9694562B2 (en) * | 2010-03-12 | 2017-07-04 | Xtalic Corporation | Coated articles and methods |
US9338896B2 (en) | 2012-07-25 | 2016-05-10 | Enthone, Inc. | Adhesion promotion in printed circuit boards |
KR20150077943A (ko) * | 2013-12-30 | 2015-07-08 | 일진머티리얼즈 주식회사 | 동박, 이를 포함하는 전기부품 및 전지 |
CN109075150B (zh) | 2016-03-11 | 2022-03-01 | 德国艾托特克公司 | 引线框结构,引线框式表面粘着型电子装置及其制造方法 |
US10246593B2 (en) | 2016-07-20 | 2019-04-02 | The Boeing Company | Sol-gel coating compositions including corrosion inhibitor-encapsulated layered double hydroxide and related processes |
US10246594B2 (en) | 2016-07-20 | 2019-04-02 | The Boeing Company | Corrosion inhibitor-incorporated layered double hydroxide and sol-gel coating compositions and related processes |
US10428226B2 (en) | 2016-07-20 | 2019-10-01 | The Boeing Company | Sol-gel coating compositions and related processes |
US10421869B2 (en) | 2017-01-09 | 2019-09-24 | The Boeing Company | Sol-gel coating compositions including corrosion inhibitor-encapsulated layered metal phosphates and related processes |
CN109056004A (zh) * | 2018-08-23 | 2018-12-21 | 安徽江杰实业有限公司 | 一种不锈钢管用电镀液 |
EP3705607A1 (en) | 2019-03-08 | 2020-09-09 | COVENTYA S.p.A. | Composition and process for the protection of precious metal substrates by an organic nanolayer |
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- 2004-08-31 JP JP2006525381A patent/JP2007508448A/ja active Pending
- 2004-08-31 EP EP04782625A patent/EP1709215A4/en not_active Ceased
- 2004-08-31 CN CN200480028993.8A patent/CN1953868B/zh not_active Expired - Lifetime
- 2004-08-31 KR KR1020127031563A patent/KR101368879B1/ko active IP Right Grant
- 2004-09-01 MY MYPI20043563A patent/MY149149A/en unknown
- 2004-09-02 TW TW093126569A patent/TWI369296B/zh active
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2005
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Also Published As
Publication number | Publication date |
---|---|
TW200523108A (en) | 2005-07-16 |
US20050048298A1 (en) | 2005-03-03 |
MY149149A (en) | 2013-07-15 |
US6852427B1 (en) | 2005-02-08 |
EP1709215A2 (en) | 2006-10-11 |
KR20130018912A (ko) | 2013-02-25 |
EP1709215A4 (en) | 2008-08-27 |
WO2005021836A2 (en) | 2005-03-10 |
CN1953868A (zh) | 2007-04-25 |
WO2005021836A3 (en) | 2006-12-28 |
JP2007508448A (ja) | 2007-04-05 |
KR101368879B1 (ko) | 2014-03-03 |
JP2010111951A (ja) | 2010-05-20 |
TWI369296B (en) | 2012-08-01 |
US20050121330A1 (en) | 2005-06-09 |
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