CN103071950A - 可固化胺、羧酸助焊剂组合物和焊接方法 - Google Patents

可固化胺、羧酸助焊剂组合物和焊接方法 Download PDF

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Publication number
CN103071950A
CN103071950A CN2012105663134A CN201210566313A CN103071950A CN 103071950 A CN103071950 A CN 103071950A CN 2012105663134 A CN2012105663134 A CN 2012105663134A CN 201210566313 A CN201210566313 A CN 201210566313A CN 103071950 A CN103071950 A CN 103071950A
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Prior art keywords
acid
alkyl
flux composition
solder flux
aryl
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CN103071950B (zh
Inventor
A·V·多博
M·R·温克尔
M·K·贾伦杰
K·S·侯
刘向前
A·A·皮尔拉
G·N·鲁滨逊
I·汤姆林森
D·D·弗莱明
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Angus Chemical Co
Dow Global Technologies LLC
Rohm and Haas Electronic Materials LLC
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
    • B23K35/3612—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest with organic compounds as principal constituents
    • B23K35/3618—Carboxylic acids or salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K1/00—Soldering, e.g. brazing, or unsoldering
    • B23K1/0008—Soldering, e.g. brazing, or unsoldering specially adapted for particular articles or work
    • B23K1/0016—Brazing of electronic components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K1/00—Soldering, e.g. brazing, or unsoldering
    • B23K1/20—Preliminary treatment of work or areas to be soldered, e.g. in respect of a galvanic coating
    • B23K1/203—Fluxing, i.e. applying flux onto surfaces
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
    • B23K35/362—Selection of compositions of fluxes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
    • C07C211/02—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C211/09—Diamines
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C07C215/02—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
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    • H05K3/3489—Composition of fluxes; Methods of application thereof; Other methods of activating the contact surfaces
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K2101/00—Articles made by soldering, welding or cutting
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Abstract

可固化胺、羧酸助焊剂组合物和焊接方法。提供了一种可固化助焊剂组合物，其包括，作为起始组分的：一种每分子具有至少两个环氧乙烷基团的树脂组分；羧酸；和式I所示的胺类助焊剂：以及，任选地，固化剂。还提供了一种利用可固化助焊剂组合物焊接电接触点的方法。

Description

可固化胺、羧酸助焊剂组合物和焊接方法
技术领域
本发明涉及一种可固化助焊剂组合物，包括，作为起始成分的：一种每分子具有至少两个环氧乙烷基团的树脂组分；羧酸；和式I所示的胺类助焊剂，其中R1，R2，R3和R4独立地选自氢、取代的C1-80烷基、未取代的C1-80烷基、取代的C7-80芳烷基和未取代的C7-80芳烷基；其中R7和R8是独立地选自C1-20烷基、取代的C1-20烷基、C6-20芳基和取代的C6-20芳基，或者其中R7和R8与它们连接的碳原子一起形成任选被C1-6烷基取代的C3-20环烷基环；其中R10和R11独立地选自C1-20烷基、取代的C1-20烷基、C6-20芳基和取代的C6-20芳基，或者其中R10和R11与它们连接的碳原子一起形成任选被C1-6烷基取代的C3-20环烷基环；并且，其中R9选自氢、C1-30烷基、取代的C1-30烷基、C6-30芳基和取代的C6-30芳基；以及，任选地，固化剂。本发明还涉及一种使用可固化的助焊剂组合物焊接电接触点的方法。
背景技术
助焊剂是用于制造电气装置的重要工具，包括装配电子元件(例如半导体芯片)到基材上(例如印制电路板、印刷电路卡、有机基材、硅转接板、其它半导体芯片)。
倒装芯片法是一种用于装配电子元件到基材上的日益重要的方法。在用于将半导体芯片装配到基材上的倒装芯片法的一个实例中，在位于该半导体芯片上的接触点(例如触板、触针)上提供焊料(例如作为焊球)。换言之，在位于基材上相应的接触点(例如触板、镀铜通孔)上提供焊料。将助焊剂用于焊料，以清除可能存在于焊料表面上、或者存在于半导体芯片或基材的触点表面上的氧化物层。在回流期间，助焊剂也起到通过焊料提供增加的触点润湿性(wetting)的作用。随后，使半导体芯片上的焊料或触点与基材上相应的触点或焊料物理接触。随后将半导体芯片和/或基材上的焊料加热至回流。冷却时，在半导体芯片与基材之间形成互连。典型地，随后将这些互连包封(例如用环氧树脂)以提高半导体芯片/基材组件的可靠性。即，封装树脂有助于减小可能由半导体芯片和基材的热膨胀系数不同而产生的应变(strain)。
对用于上述工艺的助焊剂的实际选择非常重要。很多常规的助焊剂的使用，导致形成了不希望的离子残渣，其可能降低设备产品的可靠性。因此，该不希望的离子残渣必须从设备清除。然而，在形成焊接互连后半导体芯片和基材(例如印制电路板)之间的距离非常小的事实妨碍了对该设备的清洁。这使得清除在焊接过程中形成的任何不希望的离子残渣的工艺相当复杂。
通常，采用可固化有机材料(典型地含有有机或者无机填料)来填充半导体芯片与基材之间的缝隙，并用来加强半导体芯片和基材之间电互连的焊接接头。这些底部填充(underfill)材料依赖于毛细作用填充该缝隙。
半导体芯片和基材之间的缝隙必须完全填充，以给电器元件产品提供最大的可靠性。然而，当将可固化的有机材料应用于半导体芯片与基材间的缝隙周围时，可能会在缝隙中心区留下空隙。随着电器元件的尺寸缩小(即，缝隙的高度变小)，毛细管作用的限制作用导致非填充中心区扩大。
为处理这个问题，一些人在基材中对应于接近缝隙区域中心的位置设置孔。随后通过该孔将底部填充材料供应到缝隙及周围。然而，这种方法要求设计设备来提供一个无电路区域，以便于定位中心孔。
关于底部填充问题的另一方法已经开始被称为“无流动(no flow)”工艺，其中在焊接之前，将底部填充材料预先施加到半导体芯片和/或基材上。随后，这种材料在焊接时占据半导体芯片和基材之间的缝隙，以形成互连的组件并固化(典型地通过加热)。
在该无流动工艺中，已知使用一种能提供助焊和包封功能的底部填充材料。该材料减少将半导体芯片封装到基材上所需要步骤的数量。即，这些材料将助焊和底部填充步骤合二为一，并且不需要清洁步骤。
Pennlsl等在美国专利No.5,128,746中公开了一种该无流动底部填充材料。Pennlsl等公开了一种含有用于回流焊接电器元件和基材的助焊剂的热可固化粘合剂，包括当加热到焊接温度时从电器元件或者基材清除氧化物层并且至少部分固化的粘合剂，所述粘合剂基本上由热固性树脂，含量足以从所述元件或所述基材上清除所述氧化物层的助焊剂，以及当热可固化粘合剂受热时与热固性树脂反应并使之固化的固化剂组成。
Chen等在美国专利No.7,303,944中公开了另一种无流动底部填充方法。Chen等公开的方法包括：在基材表面上的触板上施加含有松香化合物的酸酐加成物作为助焊剂的底部填充材料；放置具有活性表面的微电子器件，并在活性表面的多个触板上设置有多个焊料块(solder bump)，相对与基材；该多个焊料块设置在无流动底部填充材料中；用助焊剂从焊料块除去金属氧化物；通过加热到高于焊料熔点的温度来回流焊料；并固化底部填充材料。
很多常规的无流动底部填充材料(像那些著名的)都建立在环氧化学上，并依赖于羧酸或者酸酐提供助焊作用。同时，周期性地采用有机醇类作为加速剂，只要它们与酸酐起反应形成羧酸助焊试剂。然而，在焊接和封装过程中羧酸有挥发倾向。这是不希望的，因为它能在半导体芯片和基材之间的缝隙中产生孔隙，降低产品设备的可靠性。因此，仍然需要有利于在电器元件内制造可靠焊接和包封互连(即，半导体芯片和印制电路板之间的互连)的可固化助焊剂。
发明内容
本发明提供一种可固化助焊剂组合物，包括，作为起始成分的：一种每分子具有至少两个环氧乙烷基团的树脂组分；羧酸；和式I所示的胺类助焊剂：
Figure BSA00000828942100031
其中R1，R2，R3和R4独立地选自氢、取代的C1-80烷基、未取代的C1-80烷基、取代的C7-80芳烷基和未取代的C7-80芳烷基；其中R7和R8是独立地选自C1-20烷基、取代的C1-20烷基、C6-20芳基和取代的C6-20芳基，或者其中R7和R8与它们连接的碳原子一起形成任选被C1-6烷基取代的C3-20环烷基环；其中R10和R11独立地选自C1-20烷基、取代的C1-20烷基、C6-20芳基和取代的C6-20芳基，或者其中R10和R11与它们连接的碳原子一起形成任选被C1-6烷基取代的C3-20环烷基环；并且，其中R9选自氢、C1-30烷基、取代的C1-30烷基、C6-30芳基和取代的C6-30芳基；以及，任选地，一种固化剂。
本发明提供一种形成封闭的(encapsulated)冶金(metallurgical)接头的方法，包括：提供一种本发明的可固化助焊剂组合物；提供多个第一电接触点；提供多个相应的第二电接触点；提供一种焊料；将可固化的助焊剂组合物施加于多个第一电接触点和多个相应的第二电接触点中的至少一个；将多个第一电接触点置于靠近多个相应的第二电接触点处；将焊料加热至高于其回流温度形成熔融焊料，并将熔融焊料暴露于多个第一电接触点和多个相应的第二电接触点；将多个第一电接触点和多个相应的第二电接触点的可固化的助焊剂组合物置于与熔融焊料接触，并在多个第一电接触点和多个相应的第二电接触点之间形成多个电连接；以及，固化树脂组分，封闭多个电连接。
具体实施方式
设计本发明的可固化助焊剂组合物以促进具有焊接的和包封的电互连的电器元件的制造。例如，优选地设计本发明的可固化助焊剂组合物，以在半导体设备的制造中起到无流动底部填充制剂的作用。
在这里及从属权利要求中使用的术语“无流动底部填充组合物”表示一种可固化助焊剂组合物，其表现出焊接助焊活性和潜在的固化作用，以促进焊接互连的包封。
在这里及从属权利要求中使用的、与本发明的可固化助焊剂组合物有关的术语“储存稳定性”(在单包装系统(one pack system)中)表示在55℃存储一周后，可固化助焊剂组合物粘度的增加少于5％，其中粘度采用布鲁克菲尔德DV-1+粘度计、在20℃使用设定在100rpm的布鲁克菲尔德#S00轴进行测量。
在这里及从属权利要求中使用的、与本发明的可固化助焊剂组合物有关的术语“储存稳定”表示可固化助焊剂组合物表现出储存稳定性。
本发明的可固化助焊剂组合物包括(基本上由以下组分组成)，作为起始成分的：一种每分子具有至少两个环氧乙烷基团的树脂组分；羧酸；式I所示的胺类助焊剂；以及，任选地，一种固化剂。优选地，该可固化的助焊剂组合物包括少于10wt％的材料，该材料通过热重分析(TGA)测定，从25℃开始以10℃/分钟的温度梯度加热到250℃时挥发。从底部填充组合物释放气体倾向于在半导体芯片和基材之间的缝隙中引起空隙，导致关系到这种产品成套的设备的潜在可靠性。
用于本发明的可固化助焊剂组合物的树脂组分包括每分子具有至少两个环氧乙烷基团的材料。优选地，所用的树脂组分是每分子具有至少两个环氧化物基团的环氧树脂，例如，取代或者未取代的脂族、脂环族、芳香族和杂环环氧聚合物(polyepoxide)。更优选地，该树脂组分为环氧树脂，其选自双酚型环氧树脂(例如双酚A型环氧树脂、双酚F型环氧树脂、双酚S型环氧树脂)；芳香族二缩水甘油醚；芳香族多官能缩水甘油醚；脂族二缩水甘油醚和脂族多官能缩水甘油醚。更优选地，该树脂组分为双酚型环氧树脂。最优选地，该树脂组分为双酚A型环氧树脂。可固化助焊剂组合物优选包括10到99wt％(更优选20到90wt％；再更优选30到75wt％，最优选30到50wt％)的树脂组分。
用于本发明的可固化助焊剂组合物的树脂组分任选地进一步包括每分子具有至少3个环氧乙烷基团的材料。每分子具有至少3个环氧乙烷基团的材料任选地包括在树脂组分中，以提高固化的树脂产品的玻璃化转变温度，并降低制剂的胶凝时间。
优选地，用于本发明助焊剂组合物中的羧酸选自C8-20的脂族单羧酸、C2-20的脂族二羧酸、C6-20的芳香羧酸及其混合物。更优选地，用于本发明助焊剂组合物中的羧酸选自辛酸、壬酸、十一烷酸、十二烷酸、十三酸、十四酸、十五酸、十六酸、十七酸、硬脂酸、羟基硬脂酸、油酸、亚油酸、α-亚麻酸、二十酸(icosanoic acid)、草酸、丙二酸、丁二酸、苹果酸、戊二酸、己二酸、庚二酸、辛二酸、安息香酸、邻苯二甲酸、间苯二甲酸、对苯二甲酸、苯连三酸、苯偏三酸、苯均三酸、苯偏四甲酸、苯连四甲酸、苯均四酸、苯六甲酸、甲苯甲酸、二甲苯甲酸、二甲基苯甲酸、均三甲苯酸、苯连四甲酸、肉桂酸、水杨酸、安息香酸(例如安息香酸、2，3-二羟基安息香酸、2，4-二羟基安息香酸、2，5-二羟基安息香酸(龙胆酸)、2，6-二羟基安息香酸、3，5-二羟基安息香酸、3，4，5-三羟基安息香酸(没食子酸))、萘甲酸(例如萘甲酸、1，4-二羟-2-萘甲酸；3，5-二羟-2-萘甲酸；3，7-二羟-2-萘甲酸)、酚酞啉、双酚酸及其混合物。更优选地，用于本发明助焊剂组合物中的羧酸选自萘甲酸(例如萘甲酸、1，4-二羟-2-萘甲酸；3，5-二羟-2-萘甲酸；3，7-二羟-2-萘甲酸)、硬脂酸、羟基硬脂酸、油酸、亚油酸、α-亚麻酸、二十酸及其混合物。且更优选地，用于本发明助焊剂组合物中的羧酸选自萘甲酸(例如萘甲酸、1，4-二羟-2-萘甲酸；3，5-二羟-2-萘甲酸；3，7-二羟-2-萘甲酸)、硬脂酸、羟基硬脂酸、油酸及其混合物。最优选地，用于本发明助焊剂组合物中的羧酸选自萘甲酸、C18羧酸及其混合物，其中萘甲酸选自1，4-二羟-2-萘甲酸；3，5-二羟-2-萘甲酸；且C18羧酸选自硬脂酸、羟基硬脂酸和油酸。
本发明的可固化助焊剂组合物中使用的胺类助焊剂符合式I，其中R1，R2，R3和R4独立选自氢，取代的C1-80烷基，未取代的C1-80烷基，取代的C7-80芳烷基和未取代的C7-80芳烷基(优选其中R1，R2，R3和R4独立选自氢，取代的C1-20烷基，未取代的C1-20烷基，取代的C7-30芳烷基和未取代的C7-30芳烷基)；其中R7和R8独立地选自C1-20烷基、取代的C1-20烷基、C6-20芳基和取代的C6-20芳基(或者，其中R7和R8与它们连接的碳原子一起形成任选地被C1-6烷基取代的C3-20环烷基环)；其中R10和R11独立地选自C1-20烷基、取代的C1-20烷基、C6-20芳基和取代的C6-20芳基(或者，其中R10和R11与它们连接的碳原子一起形成任选地被C1-6烷基取代的C3-20环烷基环)；并且，其中R9选自氢、C1-30烷基、取代的C1-30烷基、C6-30芳基和取代的C6-30芳基。优选地，R1，R2，R3和R4中的0到3个是氢。根据式I的胺类助焊剂的R1，R2，R3，R4，R7，R8，R9，R10和R11基团可任选地进行选择，以提供具有给定用途所需要流变性质的胺类助焊剂；以促进与羧酸的助焊配合物的形成；任选地，使胺类助焊剂与给定的溶剂包装相容，该溶剂包装用于将胺类助焊剂输送到待焊接表面；并且，任选地，使该胺类助焊剂与给定的用于焊接后形成封装的钎焊接头(例如，用于常规的倒装芯片法底部填充涂层)的封装组合物(例如，环氧树脂)相容。根据式I的胺类助焊剂的R1，R2，R3，R4，R7，R8，R9，R10和R11基团还优选选择以提供具有≥125℃的沸点温度(更优选≥250℃)的胺类助焊剂，其通过示差扫描量热法以10℃/分钟的温度梯度从25℃开始测定。
优选地，用于本发明的可固化助焊剂组合物的胺类助焊剂符合式I；其中R1，R2，R3和R4独立地选自氢、取代的C1-80烷基、未取代的C1-80烷基、取代的C7-80芳烷基和未取代的C7-80芳烷基；其中取代的C1-80烷基和取代的C7-80芳烷基中的取代基选自-OH、-OR5、-COR5、-COR5、-C(O)R5、-CHO、-COOR5、-OC(O)OR5、-S(O)(O)R5、-S(O)R5、-S(O)(O)NR5 2、-OC(O)NR6 2、-C(O)NR6 2、-CN、-N(R6)-、以及-NO2中的至少一个(优选-OH，-OR5，-COR5-，-COR5，-C(O)R5，-CHO，-COOR5，-OC(O)OR5，-S(O)(O)R5，-S(O)R5，-S(O)(O)NR5 2，-OC(O)NR6 2，-C(O)NR6 2，-CN和-NO2中的至少一个)；其中R5选自C1-28烷基、C3-28环烷基、C6-15芳基、C7-28芳基烷基和C7-28烷基芳基；其中R6选自氢、C1-28烷基、C3-28环烷基、C6-15芳基、C7-28芳烷基和C7-28烷基芳基。取代的C1-80烷基和取代的C7-80芳基烷基可包含取代基的组合。例如，取代的C1-80烷基和取代的C7-80芳基烷基可：包括超过一个的同一类型取代基(例如，两个-OH)；包括超过一种类型的取代基(例如，-OH和-COR5-)；含有超过一种类型的取代基，相同类型的取代基超过一个(例如，两个-OH和一个-OR5)。
优选地，用于本发明的可固化助焊剂组合物的胺类助焊剂符合结构式I；其中R7和R8独立地选自C1-20烷基、取代的C1-20烷基、C6-20芳基和取代的C6-20芳基(或者，其中R7和R8与它们连接的碳原子一起形成任选地被C1-6烷基取代的C3-20环烷基环)；其中取代的C1-20烷基和取代的C6-20芳基中的取代基选自-OH、苯基、C1-14烷基、-OR12、-COR12-、-COR12、-C(O)R12、-CHO、-COOR12、-OC(O)OR12、-S(O)(O)R12、-S(O)R12、-S(O)(O)NR12 2、-OC(O)NR13 2、-C(O)NR13 2、-CN、-N(R13)-和-NO2中的至少一种(优选-OH、-OR12，-COR12-，-COR12、-C(O)R12、-CHO、-COOR12、-OC(O)OR12、-S(O)(O)R12、-S(O)R12、-S(O)(O)NR12 2、-OC(O)NR13 2、-C(O)NR13 2、-CN和-NO2中的至少一种)；其中R12选自C1-19烷基、C3-19环烷基、C6-19芳基、C7-19芳烷基和C7-19烷基芳基；以及其中R13选自氢、C1-19烷基、C3-19环烷基、C6-19芳基、C7-19芳烷基和C7-19烷基芳基。取代的C1-20烷基和取代的C6-20芳基可包括取代基的组合。例如，取代的C1-20烷基和取代的C6-20芳基包括超过一个的同一类型取代基(例如，两个-OH)；包括超过一种类型的取代基(例如，-OH和-COR12-)；含有超过一种类型的取代基，相同类型的取代基超过一个(例如，两个-OH和一个-OR12)。
优选地，用于本发明的可固化助焊剂组合物的胺类助焊剂符合结构式I：其中R10和R11独立地选自C1-20烷基、取代的C1-20烷基、C6-20芳基和取代的C6-20芳基(或者，其中R10和R11与它们连接的碳原子一起形成任选地被C1-6烷基取代的C3-20环烷基环)；并且，其中取代的C1-20烷基和取代的C6-20芳基中的取代基选自-OH、-OR12、-COR12-、-COR12、-C(O)R12、-CHO、-COOR12、-OC(O)OR12、-S(O)(O)R12、-S(O)R12、-S(O)(O)NR12 2、-OC(O)NR13 2、C(O)NR13 2、-CN、-N(R13)-和-NO2中的至少一种(优选-OH、-OR12、-COR12-、-COR12、-C(O)R12、-CHO、-COOR12、-OC(O)OR12、-S(O)(O)R12、-S(O)R12、-S(O)(O)NR12 2、-OC(O)NR13 2、-C(O)NR13 2、-CN和-NO2中的至少一种)；其中R12选自C1-19烷基、C3-19环烷基、C6-19芳基、C7-19芳烷基和C7-19烷基芳基；并且其中R13选自氢、C1-19烷基、C3-19环烷基、C6-19芳基、C7-19芳烷基和C7-19烷基芳基。取代的C1-20烷基和取代的C6-20芳基可包括取代基的组合。例如，取代的C1-20烷基和取代的C6-20芳基可：包括超过一个的同一类型取代基(例如，两个-OH)；包括超过一种类型的取代基(例如，-OH和-COR12-)；含有超过一种类型的取代基，相同类型的取代基超过一个(例如，两个-OH和一个-OR12)。
优选地，用于本发明的可固化助焊剂组合物的胺类助焊剂符合结构式I；其中R9选自氢、C1-30烷基、取代的C1-30烷基、C6-30芳基和取代的C6-30芳基；并且，其中取代的C1-30烷基和取代的C6-30芳基中的取代基选自-OH、-OR14、-COR14-、-COR14、-C(O)R14、-CHO、-COOR14、-OC(O)OR14、-S(O)(O)R14、-S(O)R14、-S(O)(O)NR14 2、-OC(O)NR15 2、-C(O)NR15 2、-CN、-N(R15)-和-NO2中的至少一种(优选-OH、-OR14、-COR14-、-COR14、-C(O)R14、-CHO、-COOR14、-OC(O)OR14、-S(O)(O)R14、-S(O)R14、-S(O)(O)NR14 2、-OC(O)NR15 2、-C(O)NR15 2、-CN以及-NO2中的至少一种)；其中R14选自C1-29烷基、C3-29环烷基、C6-29芳基、C7-29芳烷基和C7-29烷基芳基；并且其中R15选自氢、C1-29烷基、C3-29环烷基、C6-29芳基、C7-29芳烷基和C7-29烷基芳基。取代的C1-30烷基和取代的C6-30芳基可包括取代基的组合，例如，取代的C1-30烷基和取代的C6-30芳基可：包括超过一个的同一类型取代基(例如，两个-OH)；包括超过一种类型的取代基(例如，-OH和-COR14-)；含有超过一种类型的取代基，相同类型的取代基超过一个(例如，两个-OH和一个-OR14)。
更优选地，用于本发明的可固化助焊剂组合物的胺类助焊剂符合结构式I；其中R1，R2，R3和R4独立地选自氢、取代的C1-20烷基、未取代的C1-20烷基、取代的C7-30芳烷基和未取代的C7-30芳烷基；并且，其中在取代的C1-20烷基和取代的C7-30芳烷基中的取代基选自-OH、-OR16、-COR16-、-COR16、-C(O)R16、-CHO、-COOR16、-OC(O)OR16、-S(O)(O)R16、-S(O)R16、-S(O)(O)NR16 2、-OC(O)NR17 2、-C(O)NR17 2、-CN、-N(R17)-和-NO2中的至少一种(优选-OH、-OR16、-COR16-、-COR16、-C(O)R16、-CHO、-COOR16、-OC(O)OR16、-S(O)(O)R16、-S(O)R16、-S(O)(O)NR16 2、-OC(O)NR17 2、-C(O)NR17 2、-CN以及-NO2中的至少一种)；其中R16选自C1-19烷基、C3-19环烷基、C6-15芳基、C7-19芳烷基和C7-19烷基芳基；其中R17选自氢、C1-19烷基、C3-19环烷基、C6-15芳基、C7-19芳烷基和C7-19烷基芳基；其中R7和R8独立地选自C1-4烷基和C1-4羟基烷基(更优选地，其中R7和R8独立地选自甲基和羟甲基；最优选地其中R7和R8都是甲基)；其中R10和R11独立地选自C1-4烷基和C1-4羟基烷基(更优选地，其中R10和R11独立地选自甲基和羟甲基；最优选地其中R10和R11都是甲基)；以及，其中R9选自氢、C1-10烷基、C1-10羟基烷基、苯基、羟基苯基、C7-10烷基芳基、C7-10芳基烷基和萘基(更优选地，其中R9选自氢、C1-4烷基、C1-4羟基烷基、苯基、羟基苯基、C7烷基芳基和C7芳基烷基；最优选地其中R9选自甲基和苯基)。R1，R2，R3和R4选自其中的取代的C1-20烷基和取代的C7-30芳基烷基可包括取代基的组合。例如，取代的C1-20烷基和取代的C7-30芳基烷基可：包括超过一个的同一类型取代基(例如，两个-OH)；包括超过一种类型的取代基(例如，-OH和-COR16-)；含有超过一种类型的取代基，相同类型的取代基超过一个(例如，两个-OH和一个-OR16)。优选地，R1，R2，R3和R4中的0到3个是氢。更优选地，R1，R2，R3和R4中的1到3个是氢。更优选地，R1，R2，R3和R4中的2到3个是氢。更优选地，R1，R2，R3和R4中的两个是氢。最优选地，R1和R2之一是氢并且R3和R4之一是氢。
更优选地，用于本发明的助焊剂组合物的胺类助焊剂符合结构式I；其中R1，R2，R3和R4独立地选自氢、-CH2CH(OH)R18和-CH2CH(OH)CH2-O-R18；其中R18选自氢、C1-28烷基、C6-15芳基、C7-28芳基烷基和C7-28烷基芳基(优选地，其中R18选自C5-10烷基、C3-10环烷基、C6-15芳基和C7-15烷基芳基；最优选地，其中R18选自C8烷基、C7烷基芳基和C10萘基)；其中R7和R8独立地选自C1-4烷基和C1-4羟基烷基(更优选地，其中R7和R8独立地选自甲基和羟甲基；最优选地其中R7和R8都是甲基)；其中R10和R11独立地选自C1-4烷基和C1-4羟基烷基(更优选地，其中R10和R11独立地选自甲基和羟甲基；最优选地，其中R10和R11都是甲基)；以及，其中R9选自氢、C1-10烷基、C1-10羟基烷基、苯基、羟基苯基、C7-10烷基芳基、C7-10芳基烷基和萘基(更优选地，其中R9选自氢、C1-4烷基、C1-4羟基烷基、苯基、羟基苯基、C7烷基芳基和C7芳基烷基；最优选地，其中R9选自甲基和苯基)。优选地，R1，R2，R3和R4中的0到3个是氢。更优选地，R1，R2，R3和R4中的1到3个是氢。更优选地，R1，R2，R3和R4中的2到3个是氢。再优选地，R1，R2，R3和R4中的两个是氢。最优选地，R1和R2之一是氢并且R3和R4之一是氢。
更优选地，用于本发明的可固化助焊剂组合物的胺类助焊剂符合结构式I；其中R1，R2，R3和R4独立地选自氢、-CH2CH(OH)R18和CH2CH(OH)CH2-O-R18基团；其中R18选自氢、C1-28烷基、C3-28环烷基、C6-16芳基、C7-28芳基烷基和C7-28烷基芳基(优选地，其中R18选自C5-10烷基、C6-16芳基和C7-15烷基芳基；更优选地，其中R18选自C8烷基、C7烷基芳基、萘基、联苯基和取代的C12-16联苯基；最优选地，其中R18选自C8烷基、C7烷基芳基和萘基)；其中R7和R8都是甲基；其中R10和R11都是甲基；并且，其中R9选自甲基和苯基。优选地，R1，R2，R3和R4中的0到3个是氢。更优选地，R1，R2，R3和R4中的1到3个是氢。更优选地，R1，R2，R3和R4中的2到3个是氢。再优选地，R1，R2，R3和R4中的两个是氢。最优选地，R1和R3是氢；并且R2和R4选自-CH2CH(OH)R18和-CH2CH(OH)CH2-O-R18。
优选地，本发明的可固化助焊剂组合物包括，作为起始成分的：羧酸和如式I所示的胺类助焊剂，胺类助焊剂胺氮相对于羧酸酸含量(-COOH)的当量比为1∶1到20∶1(更优选1∶1到10∶1，最优选1∶1到4∶1)。优选地，当结合时，羧酸和式I所示胺类助焊剂形成助焊配合物。优选地，形成的助焊配合物为酸基复合物。优选地，温度加热到230℃时助焊复合物表现出通过热重分析(TGA)以10℃/分钟的温度梯度从25℃开始测定的≤25wt％的失重率(更优选≤20wt％；最优选≤15wt％)。
本发明的可固化助焊剂组合物任选地进一步包括固化剂。常规的固化剂可以与树脂组分和胺类助焊剂一起使用，只要固化剂能固化树脂组分。常规的固化剂包括例如多官能酚、多官能醇、胺、咪唑化合物、酸酐、有机磷化合物及其卤化物。优选地，所用的任何固化剂应该是潜在的固化剂(即，在≤225℃的温度下不会引发树脂组分胶凝的固化剂)，允许焊料没有干扰地回流，并促进在单包装系统(one pack systems)中可固化助焊剂组合物的储存稳定。
本发明的可固化助焊剂组合物任选地进一步包括溶剂。溶剂任选地包括在本发明的助焊剂组合物中，以促进树脂组分和胺类助焊试剂到待焊接表面的传递。优选地，可固化助焊剂组合物包括1到70wt％的溶剂(更优选1到35wt％的溶剂；最优选1到20wt％的溶剂)。用于本发明可固化助焊剂组合物的溶剂优选为下述有机溶剂，该有机溶剂选自烃(例如十二烷、十四烷)；芳香烃(例如苯、甲苯、二甲苯、三甲苯、苯甲酸丁酯、十二烷基苯)；酮类(例如甲基乙基酮、甲基异丁基酮、环己酮)；醚类(例如四氢呋喃、1，4-二
Figure BSA00000828942100111
烷和四氢呋喃(1，4-dioxaneandtetrahydrofuran)、1，3-二烷(dioxalane)、二丙二醇二甲醚)；醇类(例如2-甲氧基乙醇、2-丁氧基乙醇、甲醇、乙醇、异丙醇、α萜品醇、苄醇、2-己基癸醇)；酯类(例如乙酸乙酯、乳酸乙酯、乙酸丁酯、己二酸二乙酯、邻苯二甲酸二乙酯、二甘醇单丁基乙酸酯、丙二醇单甲醚乙酸酯、乳酸乙酯、2-羟基异丁酸甲酯、丙二醇单甲醚乙酸酯)；以及酰胺(例如N-甲基吡咯烷酮、N，N-二甲基甲酰胺和N，N-二甲基乙酰胺)；二元醇衍生物(例如溶纤剂(cellosolve)、丁基溶纤剂)；二元醇(例如乙二醇、二甘醇、双丙甘醇、三甘醇、已二醇、1，5-戊二醇)；二元醇醚(例如丙二醇单甲醚、甲基卡必醇、丁基卡必醇)；以及石油溶剂(例如石油醚、石脑油)。更优选地，用于本发明助焊剂组合物的溶剂为选自甲基乙基酮；2-丙醇；丙二醇单甲醚；丙二醇单甲醚乙酸酯；乳酸乙酯和2-羟基异丁酸甲酯的有机溶剂。最优选地，用于本发明助焊剂组合物的溶剂是丙二醇单甲醚。
本发明的可固化助焊剂组合物任选地进一步包括增稠剂。优选地，可固化助焊剂组合物包括0到30wt％的增稠剂。用于本发明可固化助焊剂组合物的增稠剂可以选自非固化树脂材料(即，每分子＜2个反应官能团)，例如，非固化的酚醛清漆树脂(novolac resin)。用于可固化助焊剂组合物的增稠剂，优选表现出比树脂成分(以其未固化形式)表现的高的粘度。当存在时，该增稠剂可以基于可固化助焊剂组合物的总重以0.1到35wt％的量使用。
本发明的可固化助焊剂组合物任选地进一步包括触变剂。优选地，可固化助焊剂组合物含有1到30wt％的触变剂。用于本发明可固化助焊剂组合物的触变剂可以选自脂肪酸酰胺(例如硬脂酰胺、羟基硬脂酸双酰胺)；脂肪酸酯(例如蓖麻蜡、蜂蜡、巴西棕榈蜡)；有机触变剂(例如聚乙二醇、聚环氧乙烷、甲基纤维素、乙基纤维素、羟乙基纤维素、羟丙基纤维素、一缩二甘油(diglycerine)单油酸酯、一缩二甘油月桂酸酯(deglycerine laurate)、十甘油油酸酯(decaglycerine oleate)、一缩二甘油单月桂酸酯、山梨醇月桂酸酯)；无机触变剂(例如硅粉、高岭土粉)。优选地，使用的触变剂选自聚乙二醇和脂肪酸酰胺。
本发明的可固化助焊剂组合物任选地进一步包括无机填料。无机填料可以选自氧化铝、氢氧化铝、硅铝酸盐、堇青石、锂铝硅酸盐、铝酸镁、氢氧化镁、粘土、滑石、三氧化锑、五氧化二锑、氧化锌、胶体二氧化硅、热解法二氧化硅、玻璃粉、石英粉和玻璃微球粒。当存在时，本发明的可固化助焊剂组合物优选含有0到70wt％(更优选0到35wt％，再优选0到20wt％；最优选0.1到20wt％)的无机填料。
本发明的可固化助焊剂组合物，任选地，进一步包括抗氧化剂。当存在时，本发明的可固化助焊剂组合物优选含有0.01到30wt％(更优选0.01到20wt％)的抗氧化剂。
本发明的可固化助焊剂组合物任选地进一步包括反应稀释剂。优选地，该任选的反应稀释剂应该表现出比树脂成分(以其未固化形式)表现的低的粘度。反应稀释剂可优选地选自单官能团环氧化物(例如C6-28烷基缩水甘油醚；C6-28脂肪酸缩水甘油酯；C6-28烷基苯酚缩水甘油醚)和某些多官能团环氧化物(例如三羟甲基丙烷三缩水甘油醚、二缩水甘油基苯胺)。当存在时，反应稀释剂可以按＜50wt％(根据树脂组分的重量)的量使用。
本发明的可固化助焊剂组合物任选地进一步包括常规的脱气剂。据认为脱气剂在焊料回流期间提高待焊接表面的润湿度。当存在时，脱气剂可以按基于可固化助焊剂组合物的总重、以＜1wt％的量使用。
本发明的可固化助焊剂组合物任选地进一步包括常规的消泡剂。据信，消泡剂在焊料回流期间可提高待焊接表面的润湿度，并且在可固化助焊剂组合物固化时降低气体夹杂缺陷。当存在时，该消泡剂可按＜1wt％可固化助焊剂组合物的量使用。
本发明的可固化助焊剂组合物任选地进一步包括常规的粘合促进剂。常规的粘合促进剂包括硅烷，例如，缩水甘油氧基丙基三甲氧基硅烷(glycidoxypropyl trimethoxysilane)；γ-氨基丙基三甲氧基硅烷(γ-amino propyltrithosysilane)；三甲氧基甲硅烷基丙酸酯化异氰酸酯；β-(3，4-环氧环己基)乙基三乙氧基硅烷；缩水甘油氧基丙基二乙氧基甲基硅烷(glycidoxypropyldiethoxymethylsilane)；β-(3，4-环氧环己基)乙基三甲氧基硅烷；γ-缩水甘油氧基丙基(glycidoxypropyl)三乙氧基硅烷；γ-巯基丙基三甲氧基硅烷；N-β-(氨基乙基)-γ-氨基丙基三甲氧基硅烷；双(三甲氧基甲硅烷基丙基)胺；以及γ-脲丙基三乙氧基硅烷(γ-ureidopropyltriethoxysilane)。当存在时，粘合促进剂可按＜2wt％可固化助焊剂组合物的量使用。
本发明的可固化助焊剂组合物任选地进一步包括常规的阻燃剂。常规的阻燃剂包括溴化合物(例如十溴二苯醚、四溴双酚A、四溴邻苯二甲酸酐、三溴苯酚)；磷化合物(例如磷酸三苯酯、磷酸三(甲苯)酯、磷酸三(二甲苯基)酯、磷酸甲酚二苯酯)；金属氢氧化物(例如氢氧化镁、氢氧化铝)；红磷及其改性产物；锑化合物(例如三氧化锑、五氧化二锑)；以及三嗪化合物(例如三聚氰胺、氰尿酸、三聚氰胺氰尿酸酯)。当存在时，阻燃剂可以按0.01到35wt％(优选地0.01到10wt％)可固化助焊剂组合物的量使用。
本发明的可固化助焊剂组合物任选地进一步包括选自消光剂、着色剂、分散稳定剂、螯合剂、热塑性颗粒、UV防渗剂、流平剂和还原剂的附加添加剂。
本发明的可固化助焊剂组合物可以作为包括所有组分的单包装体系提供。或者，可固化助焊剂组合物可以以双包装体系提供；其中在第一部分中提供树脂成分，且胺类助焊剂和任选的固化剂包含在在第二部分内；并且，其中第一部分和第二部分在使用前复合。
本发明的可固化助焊剂组合物可用于例如电子元件、电子模块和印制电路板的生产。可固化助焊剂组合物可以施加到表面上，该表面要通过任何常规技术焊接，包括液体喷雾技术、液体发泡技术、取浸技术、波技术(wavetechnique)、或者任何其它能将液体或者半固体分配到硅片或基材上的常规技术。
本发明的可固化助焊剂组合物任选地进一步包括焊粉；其中可固化助焊剂组合物为焊锡膏。优选地，焊粉为选自下面的合金：Sn/Pb、Sn/Ag、Sn/Ag/Cu、Sn/Cu、Sn/Zn、Sn/Zn/Bi、Sn/Zn/Bi/In、Sn/Bi和Sn/In(优选地，其中焊粉是选自下面的合金：63wt％Sn/37wt％Pb、96.5wt％Sn/3.5wt％Ag、96wt％Sn/3.5wt％Ag/0.5wt％Cu、96.4wt％Sn/2.9wt％Ag/0.5wt％C、96.5wt％Sn/3wt％Ag/0.5wt％Cu、42wt％Sn/58wt％Bi、99.3wt％Sn/0.7wt％Cu、91wt％Sn/9wt％Zn和89wt％Sn/8wt％Zn/3wt％Bi)。
本发明的焊锡膏优选包括：1到50wt％(更优选5到30wt％，最优选5到15wt％)的树脂组分和助焊配合物(由羧酸和式I所示胺类助焊剂结合形成的)的结合和50到99wt％的焊料粉。焊锡膏可以通过常规技术混合，例如，通过使用用于这种操作的常规设备将焊料粉与胺类助焊剂以及树脂组分捏合和混合。
焊锡膏可以用于例如电子元件、电子模块和印制电路板的生产中。焊锡膏可以通过任何常规技术(包括使用焊料印刷机或者丝网印刷机通过常规的焊料罩来印刷焊锡膏)施加到待焊接的表面。
本发明的可固化助焊剂组合物中使用的式I所示胺类助焊剂可以使用本领域技术人员已知的常规合成技术制备得到。
本发明的可固化助焊剂组合物中所用的助焊配合物可以通过以下方法制得，例如：(a)将式I所示的胺类助焊剂与羧酸相结合(参见，例如实施例5)；或(b)在制备根据式I的胺类助焊剂过程中的某个时间加入羧酸。优选地，本发明的可固化助焊剂组合物中所用的助焊配合物通过将根据式I的胺类助焊剂与羧酸结合来制备。任选地，根据式I的助焊剂和羧酸可以在溶剂中结合(例如，1，3-二
Figure BSA00000828942100141
烷)，以促进助焊配合物的形成。然后可以将溶剂蒸发留下助焊配合物。
本发明的多个包封的电互连的形成方法可任选地为倒装芯片焊接法的一部分，其中将半导体芯片装配到印制电路板上，其中该半导体芯片包括多个第一电接触点，且其中印制电路板包括多个相应的第二电接触点。在该倒装芯片方法中，本发明的可固化助焊剂组合物适用于多个第一电接触点和多个相应的第二电接触点中的任何一个或者两个，以促进多个第一电接触点与多个第二电接触点焊剂连接以形成电互连。优选地，该倒装芯片焊接法进一步包括固化步骤，其中树脂成分被固化，包封多个第一电接触点与多个第二电接触点之间的电互连。
在形成本发明的多个包封电互连的方法期间，本发明的可固化助焊剂组合物优选地施加到印制电路板上，用或不用平滑涂抹，位于多个第一电接触点上。焊料优选以焊球形式施加到半导体芯片上相应的多个第二电接触点。然后将附有焊料的半导体芯片置于经可固化助焊剂组合物处理的印制电路板上。然后将半导体芯片与印制电路板对准，并将焊料加热至高于其回流温度。在回流期间，可固化助焊剂组合物作为助焊剂并促进焊料粘着于印制电路板上的多个第一电接触点上，在多个第一电接触点和多个相应的第二电接触点之间形成电互连。然后将树脂组分固化以包封多个电互连。
在回流期间，焊料融化并流动以形成多个电互连。可固化助焊剂组合物优选地不应该胶凝，直至焊料已经流动并形成多个电互连后；否则，印制电路板和半导体芯片可能不能正确对准。优选地，可固化助焊剂组合物中的树脂成分在焊料回流形成包封电互连之后完全固化。
现在将本发明的一些实施方式详细描述在下列实施例中。
实施例1：胺类助焊剂的合成
采用以下方法制备2，6-二氨基-2，5，6-三甲基庚-3-醇胺类助焊剂。首先，采用以下合成方法制备2，5，6-三甲基-2，6-二硝基庚-3-醇中间体
Figure BSA00000828942100151
具体地，在三口圆底烧瓶中安装搅拌棒、热电偶、盖上带有氮气入口的滴液漏斗和冷凝器。然后向该烧瓶充入2-硝基丙烷(50g，0.56mol，5.0当量)和催化量的1，8-二氮杂双环[5.4.0]十一-7-烯。然后将烧瓶的内容物在氮气下搅拌30分钟。然后将巴豆醛(crotonaldehyde)(7.9g，9.2mL，0.112摩尔，1.0当量)在二十分钟内滴加到烧瓶中。然后将烧瓶的内容物在氮气下搅拌5-6小时，在此期间可观察到白色固体从溶液中沉淀出来。此时，GC分析显示在反应混合物中不存在任何巴豆醛。使烧瓶的内容物在氮气下搅拌过夜。然后将沉淀物从溶液中真空滤出，并用水完全洗涤得白色固体。空气干燥该中间体固体，随后在45℃真空干燥。所需要的中间体二硝基醇的总收率是72％(27.8g)。核磁共振试验(“NMR”)和液相色谱法(“LC”)显示该中间体＞99％的纯度。
其次，产物2，6-二氨基-2，5，6-三甲基庚-3-醇胺类助焊剂然后由中间体二硝基醇采用以下合成方法制备
Figure BSA00000828942100152
具体地，25g中间体二硝基醇与14.2g作为催化剂的RaNi 3111溶于200mL甲醇中。该混合物然后在高压釜中于60℃在4，137kPa(600psi)氢气压力下进行氢化。在包括过滤催化剂和除去甲醇的步骤之后，获得低粘度液体产物11g(59％收率)。NMR和气相色谱-质谱(“GC-MS”)分析确认存在所需要的产物2，6-二氨基-2，5，6-三甲基庚-3-醇胺类助焊剂。化学电离质谱(CI-MS)显示[M+H]＝189，并且GC分析显示产物的纯度为94％。该物质的沸点在0.68kPa(5.1托)下是125℃到135℃。13C NMR(CDCl3)：δ16.8，25.2，27.9，30.8，34.7，42.2，51.8，52.8和77.3ppm。
实施例2：胺类助焊剂的合成
2，6-二氨基-2，6-二甲基-5-苯基庚-3-醇胺类助焊剂采用以下方法制备。首先，2，6-二甲基-2，6-二硝基-5-苯基庚-3-醇中间体采用以下合成方法制备
Figure BSA00000828942100161
具体地，在三口圆底烧瓶中安装搅拌棒、热电偶、盖上带有氮气入口的滴液漏斗和冷凝器。然后向该烧瓶充入2-硝基丙烷(101.1g，1.14mol，6.0当量)和催化量的1，8-二氮杂双环[5.4.0]十一-7-烯(“DBU”)。然后将烧瓶的内容物在氮气下搅拌20分钟。然后将反式肉桂醛(25.0g，0.19摩尔，1.0当量)在二十分钟内滴加到烧瓶中。在滴加反式肉桂醛期间，可观察到大约22℃的放热曲线。反式肉桂醛完全加入后，烧瓶内容物加热到50℃并在此温度保持4小时。然后使该混合物冷却到室温。当烧瓶内容物达到36.8℃时，从溶液中形成淡黄色固体。然后通过布氏漏斗过滤烧瓶内容物，并且用戊烷和醚完全洗涤回收的中间体二氨基醇粉末。然后将中间体二氨基醇粉末真空干燥1小时。所需要的二氨基醇中间体的总收率是62％(36g)。NMR分析显示二氨基醇中间体＞99％的纯度。1HNMR(CDCl3)：δ1.45-2.27(m，15H)，3.52-3.54(m，1H)，3.67-3.74(m，1H)，7.17-7.34(m，5H)。13C NMR(CDCl3)：δ20.8，22.4，23.2，25.8，31.3，50.3，72.9，91.5，91.6，128.1，128.7，129.4，136.6ppm。
其次，然后产物2，6-二氨基-2，6-二甲基5-苯基庚-3-醇胺类助焊剂采用如下的合成方法由该二硝基醇中间体制备
Figure BSA00000828942100162
具体地，50g二硝基醇中间体与24.3g作为催化剂的RaNi 3111溶于300mL甲醇。然后该混合物在高压釜内于60℃在4137kPa(600psi)的氢气压力下进行氢化。在包括过滤催化剂和除去甲醇的步骤之后，获得40g(68％收率)高粘度液体产物。NMR和气相色谱-质谱(“GC-MS”)分析确认存在所需要的产物2，6-二氨基-2，6-二甲基-5-苯基庚-3-醇多胺类助焊剂。化学电离质谱(CI-MS)显示[M+H]＝251，并且GC分析显示高压釜直接得到的产物的纯度为78％。存在的其余物质似乎是从逆向亨利反应获得的单加成物。这种产物然后通过真空蒸馏纯化到96.2％的纯度。纯化产物的沸点在0.67kPa(5.0托)下测定为150℃到160℃。1HNMR(CDCl3)：δ0.91-0.99(m，12H)，1.67-1.81(m，3H)，2.71-2.76(m，2H)，7.08-7.23(m，5H)。13CNMR(CDCl3)：δ24.6，27.9，28.3，29.8，31.6，51.8，52.6，54.2，75.9，126.3，127.8，129.4，142.0ppm。
实施例3：胺类助焊剂的合成
具有下式结构的胺类助焊剂
Figure BSA00000828942100171
采用以下方法制备。具体地，向带有搅拌棒的反应容器中加入实施例1的产物(0.05mol)。然后将该反应器置于具有磁力搅拌功能的电热套上。然后将该反应容器用氮气惰性化，并且然后在环境温度下在搅拌下将(0.1mol)2-乙基己基缩水甘油醚(由蒙特功能材料公司(Momentive Performance Materials)供应)加入到该反应容器中。然后将电热套的设定温度升高到75℃，使反应容器的内容物继续搅拌两(2)小时。然后将电热套的设定温度提高到140℃，并使反应容器的内容物再继续搅拌两(2)小时。电热套的设定温度然后降低到80℃并将该反应容器抽真空，将容器压力降低到30mm Hg。使该反应容器的内容物在此条件下额外继续搅拌两(2)小时，以提供助焊剂产物。通过热重分析法(TGA)在25℃开始采用10℃/分钟的温度梯度测量该助焊剂产物加热到250℃时的失重百分比。测得该助焊剂产物的失重(WL)是9wt％。
实施例4：胺类助焊剂的合成
具有下式的胺类助焊剂
Figure BSA00000828942100181
采用以下方法制备。具体地，向带有搅拌棒的反应容器中加入实施例2的产物(0.05mol)。然后将该反应器置于具有磁力搅拌功能的电热套上。然后将该反应容器用氮气惰性化，然后在室温下在搅拌下将(0.1mol)2-乙基己基缩水甘油醚(由蒙特功能材料公司供应)加入到该反应容器中。然后将电热套的设定温度升高到75℃，使反应容器的内容物继续搅拌两(2)小时。然后将电热套的设定温度提高到140℃，并使反应容器的内容物再继续搅拌两(2)小时。电热套的设定温度然后降低到80℃并将该反应容器抽真空，将容器压力降低到30mmHg。使该反应容器的内容物在此条件下额外继续搅拌两(2)小时，以提供助焊剂产物。通过热重分析法(TGA)在25℃开始采用10℃/分钟的温度梯度测量该助焊剂产物加热到250℃时的失重百分比。测得该助焊剂产物的失重(WL)是5wt％。
实施例5：助焊配合物的制备
将根据实施例3所述步骤制备的胺类助焊剂(4g)与1，4-二羟基-2-萘甲酸(0.37g)在1，3-二氧戊环(1.5g)中在环境条件下手工混合，以形成具有胺类助焊剂胺氮相对于羧酸酸含量(-COOH)的当量比为约2∶1的助焊配合物。然后通过加热至80℃30分钟将1，3-二氧戊环从助焊复合物中除去。
然后通过热重分析法(TGA)在25℃开始采用10℃/分钟的温度梯度测量该助焊复合物加热到230℃时的失重百分比。测得该助焊复合物的失重(WL)是20.2wt％。
实施例6：助焊配合物的制备
将根据实施例4所述步骤制备的胺类助焊剂(4g)与1，4-二羟基-2-萘甲酸(0.37g)在环境条件下用铲子手工混合，以形成具有胺类助焊剂胺氮相对于羧酸酸含量(-COOH)的当量比为1.8∶1的助焊配合物。
通过热重分析法(TGA)在25℃开始采用10℃/分钟的温度梯度测量该助焊复合物加热到250℃时的失重百分比。测得该助焊复合物的失重(WL)是13.6wt％。
实施例7：可固化助焊剂组合物的制备
根据实施例6制得的助焊配合物与液态环氧树脂以1∶1的重量比结合以形成可固化助焊剂组合物，该液态环氧树脂为表氯醇与双酚A的反应产物(由陶氏化学公司(The Dow Chemical Company)以D.E.R.TM331TM供应)。
实施例8：助焊能力的评估
根据实施例7制备的可固化助焊剂组合物的助焊能力采用以下步骤来评估的。铜片用作待焊接的电接触点。将一小滴根据实施例7制得的可固化助焊剂组合物分配到铜片的待焊接表面上。将四个0.381mm直径的无铅焊球(95.5wt％Sn/4.0wt％Ag/0.5wt％Cu)投入到铜片上的可固化助焊剂组合物液滴中。所用的无铅焊料的熔化范围是217到221℃。然后将铜片放在预热到145℃的电炉上并保持两(2)分钟。然后将铜片放在预热到260℃的另一电炉上并且在此保持直到焊料达到回流条件。然后将铜片从热源移开，并且通过(a)原始放置的4个焊球的熔化和聚结程度，(b)评估流动性和延展性的最终聚结焊料的尺寸以及(c)焊料与铜片表面的焊接强度进行评价。采用0到4共4个等级来描述助焊复合物的助焊能力，其中：
0＝在焊滴之间没有熔合和没有焊料结合于铜片；
1，2＝焊滴之间部分至完全熔合，但没有焊料结合于铜片；
3＝焊滴之间完全熔合，但极少的焊料延展和流动；
4＝焊滴之间完全熔合，在铜片表面有良好的焊料延展和流动，并且焊料连接于铜片。

Claims (10)

1.一种可固化助焊剂组合物，所述组合物包括作为起始成分的：
每分子具有至少两个环氧乙烷基团的树脂组分；
羧酸；和，
式I所示的胺类助焊剂：
Figure FSA00000828942000011
其中R1，R2，R3和R4独立地选自氢、取代的C1-80烷基、未取代的C1-80烷基、取代的C7-80芳烷基和未取代的C7-80芳烷基；其中R7和R8是独立地选自C1-20烷基、取代的C1-20烷基、C6-20芳基和取代的C6-20芳基，或者其中R7和R8与它们连接的碳原子一起形成任选被C1-6烷基取代的C3-20环烷基环；其中R10和R11独立地选自C1-20烷基、取代的C1-20烷基、C6-20芳基和取代的C6-20芳基，或者其中R10和R11与连接它们的碳原子一起形成任选被C1-6烷基取代的C3-20环烷基环；并且，其中R9选自氢、C1-30烷基、取代的C1-30烷基、C6-30芳基和取代的C6-30芳基；以及
任选地，固化剂。
2.权利要求1的可固化助焊剂组合物，其中羧酸选自C8-20脂肪族单羧酸；C2-20脂肪族二羧酸；C6-20芳族羧酸；和它们的混合物。
3.权利要求2的可固化助焊剂组合物，其中羧酸选自辛酸；壬(nonanioc)酸；十一烷酸；十二烷酸；十三烷酸；肉豆蔻酸；十五烷酸；十六烷酸；十七烷酸；硬脂酸；羟基硬脂酸；油酸；亚油酸；α-亚麻酸；二十烷酸；草酸；丙二酸；琥珀酸；苹果酸；戊二酸；己二酸；庚二酸；辛二酸；苯甲酸；邻苯二甲酸；间苯二甲酸；对苯二甲酸；连苯三酸；偏苯三酸；均苯三酸；苯偏四甲酸；连苯四酸；均苯四酸；苯六甲酸；甲基苯甲酸；二甲苯甲酸(xylic acid)；二甲基苯甲酸；均三甲苯酸；连苯四酸；肉桂酸；水杨酸；苯甲酸；萘酸；酚酞啉；双酚酸和它们的混合物。
4.权利要求1的可固化助焊剂组合物，其中可固化助焊剂组合物显示出助焊剂胺氮相对于羧酸酸含量(-COOH)的当量比为1∶1到20∶1。
5.权利要求1的可固化助焊剂组合物，其中R1，R2，R3和R4所选自的取代的C1-80烷基和取代的C7-80芳烷基中的取代基选自-OH、-OR5、-COR5-、-COR5、-C(O)R5、-CHO、-COOR5、-OC(O)OR5、-S(O)(O)R5、-S(O)R5、-S(O)(O)NR5 2、-OC(O)NR6 2、-C(O)NR6 2、-CN、-N(R6)-、以及-NO2中的至少一种；其中R5选自C1-28烷基、C3-28环烷基、C6-15芳基、C7-28芳基烷基和C7-28烷基芳基；其中R6选自氢、C1-28烷基、C3-28环烷基、C6-15芳基、C7-28芳烷基和C7-28烷基芳基。
6.权利要求1的可固化助焊剂组合物，其中其中R1，R2，R3和R4中的1到3个是氢。
7.权利要求1的可固化助焊剂组合物，其中R1，R2，R3和R4独立地选自氢、-CH2CH(OH)R18和-CH2CH(OH)CH2-O-R18；其中R18选自氢、C1-28烷基、C3-28环烷基、C6-28芳基、C7-28芳基烷基和C7-28烷基芳基；其中R7和R8均为甲基；其中R10和R11均为甲基；以及，其中R9选自甲基和苯基；以及，其中R1，R2，R3和R4中的0到3个是氢。
8.权利要求4的可固化助焊剂组合物，其中，R1和R2之一是氢；并且R3和R4之一是氢。
9.权利要求1的可固化助焊剂组合物，，进一步包含焊粉。
10.一种形成封闭的冶金接头的方法，所述方法包括：
提供根据权利要求1的可固化助焊剂组合物；
提供多个第一电接触点；
提供多个相应的第二电接触点；
提供焊料；
将可固化助焊剂组合物施加于所述多个第一电接触点和所述多个相应的第二电接触点中的至少一个；
将所述多个第一电接触点置于靠近所述多个相应的第二电接触点处；
将所述焊料加热至高于其回流温度的温度以形成熔融焊料，并将熔融焊料暴露于所述多个第一电接触点和多个相应的第二电接触点；
将得自所述多个第一电接触点和多个相应的第二电接触点的可固化助焊剂组合物置于与熔融焊料接触，并在所述多个第一电接触点和多个相应的第二电接触点之间形成多个电连接；以及，
固化树脂组分，封闭所述多个电连接。
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