CN1906179A - 带氰尿酸酯核的顺丁烯二酰亚胺树脂 - Google Patents
带氰尿酸酯核的顺丁烯二酰亚胺树脂 Download PDFInfo
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Classifications
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- C—CHEMISTRY; METALLURGY
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- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/30—Only oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Plural Heterocyclic Compounds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
具有结构(I)的异氰尿酸酯化合物或树脂，其中Y是一个羟基基团－OH或一个式(II)所示的顺丁烯二酰亚胺基团，且至少有一个Y是顺丁烯二酰亚胺基团，同时Q为任何二价的有机部分，脂肪族或芳族。
Description
技术领域
[0001]本发明涉及含有一个氰尿酸酯核的顺丁烯二酰亚胺化合物或树脂，它们适合作为半导体组件粘合剂或封装剂使用。
背景技术
[0002]具有顺丁烯二酰亚胺端基和一个芳核或一个亚烷基主链的树脂在本领域是已知的。具有丙烯酸酯端基和一个异氰尿酸酯核的树脂在本领域也是已知的。这些树脂可用作粘合剂、封装剂，和密封剂。然而，半导体工业对半导体组件制作过程中所用的这类材料有着苛刻的要求，并不断需求性能更佳的新树脂。本发明树脂由于改进了粘性和高温模量而具有应用前景。
发明内容
[0003]本发明是一种具有一个异氰尿酸酯核和自核辐射出的烃臂的末端接有一个或多个顺丁烯二酰亚胺基团的化合物。化合物结构如下：
其中Y是一个羟基-OH或一个顺丁烯二酰亚胺基团
且至少有一个Y是顺丁烯二酰亚胺基团，同时Q为任何二价的有机部分，脂肪族或芳族。该有机部分可以呈线型或环形，包含碳碳不饱和键或杂原子，如氧，氮和硫。有机部分也可以包含官能团，如酰胺，氨基甲酸酯，羧基，酯，硫代基和脲基团。典型的Q基团有聚酯，聚氨酯，聚硅氧烷，或简单的亚烷基或亚烯基部分。可以改变从核辐射出的臂结构来满足专业人员的需要。有关臂结构的实例及合成方法将在本说明书的后续部分公开。
附图的简要说明
[0004]图1为实例1的核磁共振(NMR)谱图。
本发明的详细说明
[0005]本发明粘合剂组合物中所用的异氰尿酸酯化合物是可固化的化合物，即它们能够发生聚合反应，聚合可产生交联也可不产生交联。在本说明书中，固化就表示聚合，交联或不交联。按本领域的理解，交联就是两个聚合物链通过一个化学元素，分子基团，或一个化合物构成的桥结合在一起，一般经由加热或辐照而发生。随交联密度增加，材料的性质也会从热塑性转变成热固性。
[0006]粘合剂组合物还要包括至少一种自由基引发剂，这是一种能分解成含一个或多个未配对电子的高活性和寿命通常较短的分子碎片的化学物质，它能够通过链反应机理引发化学反应。自由基引发剂的量占有机化合物(不包括任何填料)重量的0.1-10％，优选为0.1-3.0％。自由基固化机理决定了固化反应快速进行，同时组合物在固化前又可以储存很长时间。优选的自由基引发剂包括过氧化物，如过辛酸丁酯和二枯基过氧化物，以及偶氮化合物，如2，2’-偶氮二(2-甲基-丙腈)和2，2’-偶氮二(2-甲基-丁腈)。
[0007]做为选择，粘合剂组合物也可以含有光敏引发剂来代替自由基引发剂，于是固化过程可以由紫外辐照来引发。光敏引发剂的用量占有机化合物(不包括任何填料)重量的0.1-10％，优选为1-5.0％。在一些情况下，可能同时需要光引发和热引发。例如，先由紫外辐照引发固化反应，而在随后的工艺过程中通过加热实现自由基固化来完成整个固化过程。
[0008]通常，这些组合物在80-200℃的温度范围内发生固化，同时在不到1分钟至60分钟的时间内完成固化。不言而喻，每个粘合剂组合物的时间-温度固化曲线是不同的，因此可以设计不同的组合物以提供适合具体的工业制造工艺的固化性能。
[0009]适合添加到粘合剂中的导体填料有银，铜，金，钯，铂。在一些情况下可能需要加入非导体填料，例如若要调节粘合剂的流变性就可以加入氧化铝，二氧化硅，和聚四氟乙烯。
[0010]也可以加入其它添加剂，如粘性促进剂。添加剂的加入类型和用量是本领域已知的。
[0011]这些组合物在商业接受的范围内可用作模具连接的粘合剂。对于80×80mil2硅模上粘合剂的压模剪切力，商业接受值为室温下大于或等于1kg，240℃下大于或等于0.5kg，同时对于用于500×500mil2模具的粘合剂的扭曲变形，商业接受值为室温下小于或等于70μm。
[0012]制造这些材料的典型合成方法包括马来酸酐与一种氨基酸反应生成酰胺酸加合物。加合物脱水关环形成带羧基官能团的顺丁烯二酰亚胺环。顺丁烯二酰亚胺上的羧基官能团进一步与1，3，5-三(2-羟乙基)氰尿酸上的羟基官能团反应形成带氰尿酸酯核的顺丁烯二酰亚胺树脂。
[0013]酰胺酸加合物是通过将溶于适当溶剂如乙腈中的马来酸酐与1摩尔当量的溶于乙酸的氨基酸，如6-氨基己酸或β-丙氨酸反应形成的。反应在室温下进行，一般要经过3-4小时。用过滤法收集产物，再用冷乙腈洗涤并干燥，从而得到酰胺酸加合物。酰胺酸加合物与三乙胺在甲苯中混合并加热(110-150℃范围内)数小时使其脱水并闭环。收集并除去反应过程中产生的水，蒸发掉有机溶剂，用2M的HCl调节pH到2以中和产品的碱性。用乙酸乙酯萃取所合成的带羧基官能团的顺丁烯二酰亚胺、并用MgSO4干燥，然后蒸发掉溶剂。典型的顺丁烯二酰亚胺包括6-顺丁烯二酰亚胺基己酸和3-顺丁烯二酰亚胺基丙酸。
[0014]将顺丁烯二酰亚胺在硫酸与适当的溶剂，如甲苯中与1，3，5-三(2-羟乙基)氰尿酸反应，形成带异氰尿酸酯核的顺丁烯二酰亚胺。调节反应物的摩尔当量数以获得对氰尿酸酯的预期取代程度。反应在加热回流的条件下进行，直到由反应产生的理论量的水被除去。过滤混合物，滤液在三乙胺中清洗1小时，随后再用20％的NaCl溶液清洗3次。收集有机相，用二氧化硅干燥，再蒸发掉溶剂，便得到带氰尿酸酯核的顺丁烯二酰亚胺。在这些产物中，臂链通过一个酯官能团与氰尿酸酯核连接。
[0015]除了实例1公开的化合物，上述方法也可以用来制备多种具有不同取代程度和由顺丁烯二酰亚胺封端的不同臂长的化合物。以下是另外一些典型化合物。
[0019]在另一实施方案中，带氰尿酸酯核的顺丁烯二酰亚胺含有氨基甲酸酯官能团。制备这类化合物的合成方法包括制备带羧基官能团的顺丁烯二酰亚胺的酰基氯类似物，再将酰基氯与叠氮钠反应形成带异氰酸酯官能团的顺丁烯二酰亚胺，最后再将异氰酸酯与1，3，5-三(2-羟乙基)氰尿酸反应。
[0020]带羧基官能团的顺丁烯二酰亚胺在典型的条件下(如，50℃反应3小时)与过量的亚硫酰氯反应形成酰基氯。蒸馏脱除所有残存的亚硫酰氯，剩下带酰基氯官能团的顺丁烯二酰亚胺。在剧烈搅拌下慢慢将带酰基氯官能团的顺丁烯二酰亚胺逐滴加入冷的(10℃)预先制备好的含水，甲苯，和催化量苄基三乙基氯化铵的叠氮钠溶液中。持续搅拌溶液数小时，起初约15℃，随后在20℃左右。分离出有机相，用浓度为2N的碳酸氢钠水溶液和水依次清洗，用MgSO4干燥并过滤。将滤液缓慢加热到回流温度，并保持回流直到不再产生氮气。溶液再加热回流30分钟，冷却后用旋转蒸发器浓缩。浓缩物在高真空下蒸馏以制得带异氰酸酯官能团的顺丁烯二酰亚胺。
[0021]根据对氰尿酸酯核预期的取代程度，将1-3摩尔当量的带异氰酸酯官能团的顺丁烯二酰亚胺(相对于每摩尔当量的1，3，5-三(2-羟乙基)氰尿酸)溶解在甲苯中，该溶液在氮气保护下加热到70℃。将溶解于甲苯中的1摩尔当量的1，3，5-三(2-羟乙基)氰尿酸于数分钟内加入到异氰酸酯溶液中，所得混合物在70℃下再加热3-4小时。反应结束后将混合物冷却到室温，用蒸馏水洗涤3次，分离有机层，用MgSO4干燥，过滤，在真空下脱除溶剂得到产品。
[0022]用上述方法制得的典型化合物包括
[0025]在另一实施方案中，可以用带异氰酸酯官能团的氰尿酸酯为起始物来制备含有氨基甲酸酯功能团的带氰尿酸酯核的顺丁烯二酰亚胺。例如，可用购自Bayer公司的Desmodur N3300化合物为起始物，其结构式如下所示：
[0026]将1摩尔当量的起始化合物溶解在甲苯中，置于氮气下，溶液加热到70℃。根据预期的取代程度，将1-3摩尔当量的N-羟烷基-顺丁烯二酰亚胺(按照J.M.S.Pure Appl.Chem.，A36(3)，355，1999J.Bartus，W.L.Simonsick，和O.Vogl，制备)溶于甲苯，然后于数分钟内加入到异氰酸酯溶液中，所得混合物在70℃下再加热3-4小时。反应结束后冷却到室温，用蒸馏水洗涤混合物3次，分离有机层，用MgSO4干燥，过滤，在真空下脱除溶剂得到产品。用这种方法制得的典型化合物的结构如下：
实施例
[0028]实施例1
[0029]酰胺酸加合物，6-顺丁烯二酰亚胺基己酸的合成。将1摩尔当量的顺丁烯二酸酐乙腈溶液加入到1摩尔当量的6-氨基己酸乙酸溶液中。混合物在室温下反应3小时。过滤掉所形成的白色晶体，用冷乙腈洗涤并干燥滤液，制得酰胺酸加合物。将酰胺酸与三乙胺在甲苯中混合。将混合物在130℃加热2小时并用Dean-Stark分水器收集水。蒸发有机溶剂，同时用2M的HCl调节至pH为2。用乙酸乙酯萃取并用MgSO4干燥，蒸发掉有机溶剂后得到6-顺丁烯二酰亚胺基己酸(MCA)。
[0030]氰尿酸酯的合成：在1立升的烧瓶中加入1，3，5-三(2-羟乙基)氰尿酸(25.00g，96mmol)，6-顺丁烯二酰亚胺基己酸(60.65g，287mmol)，硫酸(1.00g，10mmol)，和甲苯(400mL)。反应容器带有一个顶部搅拌器，Dean-Stark分水器，和冷凝器。将瓶内混合物加热到115℃并使其回流。当收集的水量达到计算值时停止反应。反应后将烧瓶冷却到室温，过滤混合物。将三乙胺(12.4g，123mmol)加入烧瓶并搅拌1小时。随后用20％的NaCl溶液(3×400mL)洗涤混合物。收集有机相并加入硅胶(50g)，搅拌1小时，过滤，在真空下脱除有机溶剂从而得到透明但呈浅黄色的液体。收率约50％。这种三官能团顺丁烯二酰亚胺树脂在50℃时的粘度为26,000cPs，同时根据TGA分析，在200℃时的挥发度为0.12％。NMR谱图见附图1。
[0031]实施例2。将一种包含10份重量双顺丁烯二酰亚胺树脂，10份重量环氧树脂，10份重量丙烯酸树脂和15份重量二乙基甲基丙烯酸乙二醇酯，有效量固化剂和粘合促进剂的树脂制剂，与45％重量的银片掺混在一起。向该组合物中加入2.5份重量的实施例1化合物，同时对比例中加入2.5份重量具有如下结构的带氰尿酸酯核的丙烯酸酯化合物。
[0032]
[0033]测定对比制剂和包含带氰尿酸酯核的顺丁烯二酰亚胺制剂的体积电阻率和压模剪切力。每种制剂的体积电阻率均约为0.00002ohm-cm。每种制剂的粘结强度用200℃下固化2分钟后涂银铅架上的500×500mil硅模在260℃的压模剪切力来表示。与对比制剂相比，本发明的顺丁烯二酰亚胺制剂具有0.36Kg的优良的压模剪切力，而对比配方的压模剪切力为0.25Kg。
Claims (9)
1.具有以下结构的一种化合物
其中Y是一个羟基基团-OH或一个顺丁烯二酰亚胺基团
至少有一个Y是顺丁烯二酰亚胺基团，同时Q为二价有机部分。
2.根据权利要求1所述的化合物，其结构为
3.根据权利要求1所述的化合物，其结构为
4.根据权利要求1所述的化合物，其结构为
5.根据权利要求1所述的化合物，其结构为
6.根据权利要求1所述的化合物，其结构为
7.根据权利要求1所述的化合物，其结构为
8.根据权利要求1所述的化合物，其结构为
9.根据权利要求1所述的化合物，其结构为
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| JP5543155B2 (ja) * | 2009-08-20 | 2014-07-09 | 康男 三枝 | 重合性化合物、硬化物及び重合性化合物の製造方法 |
| JP2018528282A (ja) | 2015-07-14 | 2018-09-27 | ヘンケル アイピー アンド ホールディング ゲゼルシャフト ミット ベシュレンクテル ハフツング | ワンドロップフィルシーラント用途のためのビスマレイミド樹脂 |
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| WO1998007759A1 (en) * | 1996-08-23 | 1998-02-26 | First Chemical Corporation | Polymerization processes using aliphatic maleimides |
| JP3599160B2 (ja) * | 1997-05-16 | 2004-12-08 | 大日本インキ化学工業株式会社 | マレイミド誘導体を含有する活性エネルギー線硬化性組成物及び該活性エネルギー線硬化性組成物の硬化方法 |
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| SG85658A1 (en) * | 1998-07-02 | 2002-01-15 | Nat Starch Chem Invest | Package encapsulants prepared from allylated amide compounds |
| US6265530B1 (en) * | 1998-07-02 | 2001-07-24 | National Starch And Chemical Investment Holding Corporation | Die attach adhesives for use in microelectronic devices |
| US6350840B1 (en) * | 1998-07-02 | 2002-02-26 | National Starch And Chemical Investment Holding Corporation | Underfill encapsulants prepared from allylated amide compounds |
| EP1016659B1 (en) | 1998-12-29 | 2003-09-24 | Dainippon Ink And Chemicals, Inc. | Bismaleimides comprising mesogenic groups and oligomeric liquid crystalline bismaleimides |
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| EP1716124A1 (en) | 2006-11-02 |
| EP1716124B1 (en) | 2011-12-14 |
| ATE537156T1 (de) | 2011-12-15 |
| TW200628454A (en) | 2006-08-16 |
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