CN102812099A - 电子部件用液状粘接剂以及胶带 - Google Patents
电子部件用液状粘接剂以及胶带 Download PDFInfo
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- CN102812099A CN102812099A CN201180015590XA CN201180015590A CN102812099A CN 102812099 A CN102812099 A CN 102812099A CN 201180015590X A CN201180015590X A CN 201180015590XA CN 201180015590 A CN201180015590 A CN 201180015590A CN 102812099 A CN102812099 A CN 102812099A
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Abstract
Description
技术领域
本发明涉及用于粘接构成半导体装置的引线架(lead frame)周边部件之间例如引脚、半导体芯片装载用板、散热板、半导体芯片本身等的电子部件用液状粘接剂以及胶带。
本申请基于并要求于2010年3月25日提交的日本专利申请第2010-069063号的优先权权益,并其全部内容结合于此作为参考。
背景技术
现有技术中,树脂密封型半导体装置内所使用的胶带包括引线架固定用带、TAB带等。
例如,通过固定引线架的引脚(lead pin),引线架固定用胶带被用于帮助提高引线架自身及半导体组装(assembling)工序整体的生产成品率以及生产率。
通常在引线架制造商将这种固定用胶带轻敲在引线架上之后发货给半导体制造商,在半导体制造商装载IC之后用树脂密封。
为此,理所当然要求引线架固定用胶带具有半导体水平的一般可靠性以及轻敲(tapping)时的操作性,还要求在刚刚轻敲后具有充分的室温粘接力以及能够耐受半导体装置组装工序中的加热的充分耐热性等。
现有技术中,作为用于这种用途的胶带,例如,使用有在聚酰亚胺膜等支撑体膜上单独涂布聚丙烯腈、聚丙烯酸酯或丙烯腈-丁二烯共聚物等合成橡胶类树脂等、或者涂布由其他树脂改性后的产物或与其他树脂混合而成的粘接剂,并作为B阶段状态的胶带。
近年正在开发或制造如图1至图3所示结构的树脂密封型半导体装置(半导体封装件(package))。
图1的树脂密封型半导体装置具有如下结构:引脚线3和板(plane)2通过粘接层6连接,半导体芯片1装载在板2上,并与半导体芯片1和引脚线3之间的接合引线(bonding wire)4一起被树脂5密封。
此外,图2的装置具有以下结构:引脚线3和半导体芯片1通过粘接层6被固定,并与接合引线4一起被树脂5密封。
图3的装置具有以下结构:半导体芯片1被装载在压料垫(die pad)7之上,电极8通过粘接层6被固定,且半导体芯片1和电极8之间以及电极8和引脚线3之间分别通过接合引线4连接并被树脂5密封。
作为图1至图3所示的结构的树脂密封型半导体装置中的粘接层,已知有能够在较低温下粘接、固化并具有充分的耐热性及可靠性等的粘接剂(例如参照专利文献1)。
另外,可靠性是指,即使在后述的试验(PCBT:Pressure Cooker BiasedTest:压力锅偏压试验)条件下也不会发生漏电、短路。
但是,对于这种粘接剂而言,要求进一步提高其耐迁移性。
所谓耐迁移性是指,在迁移试验中不发生短路,不生成枝状晶体。
现有技术文献
专利文献
专利文献1:特开平09-176593号公报
发明内容
发明要解决的技术问题
鉴于以上问题,本发明的目的是提供一种能够在低温下粘接、固化,并具有充分的耐热性及可靠性、且耐迁移性优异的电子部件用液状粘接剂以及胶带。
解决技术问题的技术方案
本发明通过以下技术方案,可以解决上述技术问题。
(1)一种电子部件用液状粘接剂,其特征在于,是将作为组分(a)的丙烯腈-丁二烯共聚物、作为组分(b)的酚醛树脂、作为组分(c)的含有两个以上马来酰亚胺基的化合物溶解到有机溶剂中而得的液状粘接剂,所述组分(c)包含由下式(1)表示的化合物以及由下式(2)表示的化合物。
(2)根据(1)所述的电子部件用液状粘接剂,其特征在于,所述组分(a)的门尼粘度为50M1+4100℃~90M1+4100℃,丙烯腈含量为5质量%~50质量%。
(3)根据(1)所述的电子部件用液状粘接剂,其特征在于,所述组分(a)是具有羧基的丙烯腈-丁二烯共聚物。
(4)根据(1)所述的电子部件用液状粘接剂,其特征在于,所述组分(b)是包含可熔型烷基酚的酚醛树脂。
(5)根据(1)所述的电子部件用液状粘接剂,其特征在于,所述组分(b)并用可熔型酚和酚醛清漆型酚。
(6)根据(1)所述的电子部件用液状粘接剂,其特征在于,所述组分(c)中,由上式(1)以及上式(2)表示的化合物的质量比为3∶3至3∶45。
(7)根据(1)所述的电子部件用液状粘接剂,其特征在于,相对于组分(a)100质量份,组分(b)和组分(c)的总和为10质量份~900质量份,且组分(b)在组分(b)和组分(c)的总和中所占的质量比为10质量%~90质量%。
(8)根据(1)所述的电子部件用液状粘接剂,其特征在于,所述电子部件用液状粘接剂还包括作为组分(d)的二胺化合物。
(9)根据(8)所述的电子部件用液状粘接剂,其特征在于,所述组分(d)是由下式(3)表示的化合物。
(10)根据(8)所述的电子部件用液状粘接剂,其特征在于,所述组分(d)是由下式(4)表示的化合物,其重均分子量为200~7000。
(11)根据(1)所述的电子部件用液状粘接剂,其特征在于,所述电子部件用液状粘接剂的粒径为1μm以下的填充剂占固体成分总量的4质量%~40质量%。
(12)一种胶带,其特征在于,在耐热性膜的至少一面形成有通过涂布(1)所述的电子部件用液状粘接剂并干燥而得的粘接层。
(13)根据(12)所述的胶带,其特征在于,耐热性膜是聚酰亚胺膜。
(14)一种胶带,其特征在于,在剥离性膜的至少一面形成有通过涂布权利要求1所述的电子部件用液状粘接剂并干燥而得的粘接层。
发明的技术效果
根据本发明,可以提供一种能够在低温下粘接、固化并具有充分的耐热性及可靠性、且耐迁移性优异的电子部件用液状粘接剂以及胶带。
即,本发明的电子部件用液状粘接剂,由于能够在低温下粘接或固化并具有充分的耐热性及可靠性且耐迁移性优异,因此使用了其的本发明的胶带例如作为引线架固定用胶带、TAB胶带等,能够适用于粘接构成半导体装置的引线架周边部件之间,例如引脚、半导体芯片装载用板、散热板、半导体芯片本身等。
附图说明
图1表示使用了本发明或现有胶带的树脂密封型半导体装置(半导体封装件)的一例的剖面图;
图2表示使用了本发明或现有胶带的树脂密封型半导体装置的其他例子的剖面图;以及
图3表示使用了本发明或现有胶带的树脂密封型半导体装置的另一其他例的剖面图。
具体实施方式
以下对本发明进行详细说明。
首先,对电子部件用液状粘接剂的优选实施例进行说明。但本发明并不限于这些实施例。
本发明的电子部件用液状粘接剂的特征在于,是将作为组分(a)的丙烯腈-丁二烯共聚物、作为组分(b)的酚醛树脂、作为组分(c)的含有两个以上马来酰亚胺基的化合物溶解到有机溶剂中而得的液状粘接剂,所述组分(c)并用由下式(1)及下式(2)表示的化合物。
【化学式1】
【化学式2】
以下对各组分进行说明。
组分(a):
作为组分(a)的丙烯腈-丁二烯共聚物,可以全部使用公知的物质,但优选具有羧基的丙烯腈-丁二烯共聚物。
其理由是,加热时的熔融粘度变高,热稳定性提高,且与其他树脂的相溶性提高、绝缘性稳定,树脂的拉伸强度提高。
具有羧基的丙烯腈-丁二烯共聚物中羧基当量优选为1000~20000。
此外,羧基当量是根据数均分子量计算得到的值。
此外,优选门尼粘度为50M1+4(100℃)~90M1+4(100℃)的物质。
其理由是,门尼粘度处于上述范围内,则热稳定性良好、耐热性提高。
此外,由于溶剂溶解性提高、熔融粘度降低,在作为粘接剂使用时操作性、粘接性良好,因此优选。
如果门尼粘度低于上述范围的下限,则树脂耐热性降低而无法获得半导体组装工序所必需的耐热性。而且,粘接剂的B阶段的熔融粘度下降、加工时流向引线架的粘接剂增多,使加工性降低,因此不优选。另一方面,如果门尼粘度超过上述范围的上限,则粘接剂难以熔融、流动性下降,与引线架的轻敲性降低。而且对溶剂的溶解性下降,制备粘接剂的操作性降低,因此不优选。
接着,上述共聚物的丙烯腈含量优选为5质量%~50质量%,更加优选为10质量%~40质量%。
当丙烯腈含量位于上述范围内时,由于耐热性、溶剂溶解性处于合适的范围,绝缘性稳定且可靠性提高,因此优选。
如果低于上述范围的下限,则树脂耐热性降低而无法获得半导体组装工序所必需的耐热性,因此并不优选。另一方面,如果超过上述范围的上限,则溶剂溶解性下降(制成粘接剂的操作性降低),因此不优选。而且,耐迁移性也降低。
组分(b):
作为组分(b)的酚醛树脂可以使用公知的物质,但从能够使粘接温度、粘接剂的固化温度低温化并获得充分的粘接力的角度考虑,优选是包含可熔型烷基酚的酚醛树脂。
并且,进一步优选并用可熔型酚和酚醛清漆型酚。
另外,优选可熔型酚醛树脂和酚醛清漆型酚醛树脂的质量比为100∶5~100∶100,进一步优选为100∶10~100∶50。
其理由是,通过并用可熔型酚和酚醛清漆型酚,能够抑制表面缝褶(tuck)、并抑制引线架加工时的输送不良。
而且,由于酚醛清漆型酚醛树脂单独使用时固化性差,因此如果酚醛清漆型酚醛树脂相对于可熔型酚醛树脂的质量比过剩,则粘接剂的固化性下降、耐迁移性降低,因而不优选。
具体而言可以例举出可熔型的对叔丁基苯酚和酚醛清漆型的对叔丁基苯酚等。
组分(c):
作为组分(c)即含有两个以上马来酰亚胺基的化合物,需要并用由上式(1)以及(2)所示的化合物。
其理由是,能够使粘接温度、粘接剂的固化温度低温化并获得高粘接力。并且,通过并用,热稳定性提高,热时粘接性提高。进而,与其他树脂的相溶性增大、耐迁移性优异。
此外,由上式(1)以及(2)所示的化合物的质量比优选为3∶3~3∶45,更加优选为3∶3.9~3∶19.5,进一步优选为1∶3~1∶7。
本发明的电子部件用液状粘接剂优选还含有作为组分(d)的二胺化合物,更优选含有组分(d)为由下式(3)或(4)所示的化合物。
化学式3
H2N-R1-NH2 (3)
(式中,R1表示二价芳香基)
化学式4
(式中,R2表示丙烯基或苯氧基亚甲基,n表示0至7的整数)
其理由是,通过作为马来酰亚胺的固化剂而使用,能够调整固化温度。
作为上式(3)所示化合物,例如,可以列举出如下物质。本发明中上述二价芳香基没有特别限定。二价芳香基是指含有芳香基的二价基团,根据需要可以选择任何基团。例如,苯基数量不限,而且根据需要也可以具有取代基。3,3’-二氨基联苯、3,4’-二氨基联苯、4,4’-二氨基联苯、3,3’-二氨基二苯基甲烷、3,4’-二氨基二苯基甲烷、4,4’-二氨基二苯基甲烷、2,2-(3,3’-二氨基二苯基)丙烷、2,2-(3,4’-二氨基二苯基)丙烷、2,2-(4,4’-二氨基二苯基)丙烷、2,2-(3,3’-二氨基二苯基)六氟丙烷、2,2-(3,4’-二氨基二苯基)六氟丙烷、2,2-(4,4’-二氨基二苯基)六氟丙烷、3,3’-二氨基二苯醚、3,4’-二氨基二苯醚、4,4’-二氨基二苯醚、3,3’-二氨基二苯硫醚、3,4’-二氨基二苯硫醚、4,4’-二氨基二苯硫醚、3,3’-二氨基二苯砜、3,4’-二氨基二苯砜、4,4’-二氨基二苯砜、1,3-双[1-(3-氨基苯)-1-甲基乙基]苯、1,3-双[1-(4-氨基苯)-1-甲基乙基]苯、1,4-双[1-(3-氨基苯)]苯、1,3-双(3-氨基苯氧基)苯、1,3-双(4-氨基苯氧基)苯、1,4-双(3-氨基苯氧基)苯、1,4-双(4-氨基苯氧基)苯、3,3’-双(3-氨基苯氧基)二苯醚、3,3’-双(4-氨基苯氧基)二苯醚、3,4’-双(3-氨基苯氧基)二苯醚、3,4’-双(4-氨基苯氧基)二苯醚、4,4’-双(3-氨基苯氧基)二苯醚、4,4’-双(4-氨基苯氧基)二苯醚、1,4-双[1-(4-氨基苯基)-1-甲基乙基-双(3-氨基苯氧基)]联苯、3,3’-双(4-氨基苯氧基)联苯、3,4’-双(3-氨基苯氧基)联苯、3,4’-双(4-氨基苯氧基)联苯、4,4’-双(3-氨基苯氧基)联苯、4,4’-双(4-氨基苯氧基)联苯、双[4-(3-氨基苯氧基)苯基]砜、双[4-(4-氨基苯氧基)苯基]砜、2,2-双[3-(3-氨基苯氧基)苯基]丙烷、2,2-双[3-(4-氨基苯氧基)苯基]丙烷、2,2-双[4-(3-氨基苯氧基)苯基]丙烷、2,2-双[4-(4-氨基苯氧基)苯基]丙烷、2,2-双[3-(3-氨基苯氧基)苯基]六氟丙烷、2,2-双[3-(4-氨基苯氧基)苯基]六氟丙烷、2,2-双[4-(3-氨基苯氧基)苯基]六氟丙烷、2,2-双[4-(4-氨基苯氧基)苯基]六氟丙烷、9,9-双(3-氨基苯基)芴、9,9-双(4-氨基苯基)芴等。
优选由上式(4)所示的化合物的重均分子量为200~7000。
其理由是,由于易于溶解于溶剂,因而容易操作。
作为由上式(4)所示的化合物,例如可以列举出双(3-氨基丙基)四甲基二硅氧烷、氨基丙基末端的二甲基硅氧烷四倍体或八倍体、双(3-氨基苯氧甲基)四甲基二硅氧烷等,也可以混合使用上述化合物。
优选液状粘接剂的配合比例是,相对于组分(a)100质量份,组分(b)和组分(c)总和为10质量份~900质量份。更优选组分(b)和组分(c)总和为20质量份~800质量份的范围,进一步优选为50质量份~400质量份,特别优选为100质量份~400质量份的范围。
如果组分(b)和组分(c)总和在上述范围内,则涂布并固化后粘接层的耐热性特别是玻璃化转移温度(Tg)、纵弹性率(Young rate)提高,适于发明目的的用途。
此外,将粘接层固化至B阶段时,粘接层本身不变脆而操作性变好,存在与作为支撑体的耐热性膜的密合性也好的趋势。
此时,从操作性、固化树脂特性考虑,优选组分(b)在组分(b)和组分(c)总和中所占的质量比例为10质量%~90质量%,更优选为20质量%~53质量%。
另外,组分(c)和组分(d)的配合比例是,相对于组分(c)的马来酰亚胺基1摩尔当量,组分(d)的氨基优选为0.01摩尔当量~2.0摩尔当量,更优选设定为0.1摩尔当量~1.0摩尔当量的范围。
如果组分(d)的氨基当量在上述范围内,则将粘接层固化至B阶段时,粘接层自身不变脆而操作性良好,并且与作为支撑体的耐热性膜的密合性变好。
另外,混合时不发生凝胶化,因此能够对粘接剂进行调整。
组分(a)、组分(b)、组分(c)以及组分(d)的混合在溶解上述组分的溶剂中进行。
可以根据需要选择溶剂,例如可以列举出,N-甲基-2-吡咯烷酮、N,N-二甲基乙酰胺、N,N-二甲基甲酰胺、二甲亚砜、环丁砜、六甲基磷酸三酰胺、1,3-二甲基-2-咪唑烷酮、己烷、苯、甲苯、二甲苯、甲基乙基甲酮、丙酮、***、四氢呋喃、二噁烷、1,2-二甲氧基乙烷、二甘醇二甲醚、甲基溶纤剂、乙酸溶纤剂、甲醇、乙醇、丙醇、异丙醇、醋酸甲酯、醋酸乙酯、乙腈、二氯甲烷、氯仿、四氯化碳、氯苯、二氯苯、二氯乙烷、三氯乙烷等。为了溶解各组分,可以从上述溶剂中选择适当的种类和加以量使用。
为了促进上述组分(a)之间以及组分(b)之间的加成反应,根据需要也可以向液状粘接剂中添加反应促进剂。
作为反应促进剂的示例可以列举出,二氮杂二环辛烷、或过氧化甲乙酮、过氧化环己烷(cyclohexane peroxide)、过氧化-3,3,5-三甲基环己酮、过氧化甲基环己酮、过氧化乙酰乙酸甲酯、过氧化乙酰丙酮、1,1-二(叔丁基过氧化)-3,3,5-三甲基环己烷、1,1-二(叔丁基过氧化)环己烷、2,2-二(叔丁基过氧化)辛烷、正丁基-4,4-二(叔丁基过氧化)戊酸酯、2,2-二(叔丁基过氧化)丁烷、叔丁基过氧化氢、异丙苯过氧化氢、二异丙苯过氧化氢、对甲烷过氧化氢、2,5-二甲基己烷-2,5-二过氧化氢、1,1,3,3-四甲基丁基过氧化氢、二叔丁基过氧化物、过氧化叔丁基异丙苯、二异丙苯基过氧化物、α,α-二(叔丁基过氧化-间异丙基)苯、2,5-二甲基-2,5-双(叔丁基过氧化)己烷、2,5-二甲基-2,5-双(叔丁基过氧化)己炔、乙酰过氧化物、异丁基过氧化物、辛酰基过氧化物、癸酰基过氧化物、苯甲酰基过氧化物、月桂酰基过氧化物、3,5,5-三甲基己酰基过氧化物、过氧化丁二酸(スクシニックァシッドパ一ォキサイド)、2,4-二氯苯甲酰基过氧化物、间甲苯酰基过氧化物、过氧化二碳酸二异丙酯、过氧化二碳酸二(2-乙基己基)酯、过氧化二碳酸二正丙酯、二(4-叔丁基环己基)过氧化二碳酸酯、二-肉豆蔻酰过氧化二碳酸酯、二(2-乙氧基乙基)过氧化二碳酸酯、二甲氧基异丙基过氧化二碳酸酯、二(3-甲基-3-甲氧基丁基)过氧化二碳酸酯、二烯丙基过氧化二碳酸酯、过氧化乙酸叔丁酯、过氧化异丁酸叔丁酯、过氧化新戊酸叔丁酯、过氧化新癸酸叔丁酯、过氧化新癸酸枯基酯、过氧化(2-乙基己酸)叔丁酯、过氧化-3,5,5-三甲基己酸叔丁酯、过氧化月桂酸叔丁酯、过氧化苯甲酸叔丁酯、过氧化间苯二甲酸二叔丁酯、2,5-二甲基-2,5-二(苯甲酰过氧化)己烷、叔丁基过氧化马来酸、叔丁基过氧化异丙基碳酸酯、过氧化辛酸枯基酯、过氧化新癸酸叔己酯、过氧化新戊酸叔己酯、过氧化新己酸叔丁酯、乙酰基环己基硫酰过氧化物、过氧化烯丙基碳酸叔丁酯等有机过氧化物、1,2-二甲基咪唑、1-甲基-2-乙基咪唑、2-甲基咪唑、2-乙基-4-甲基咪唑、2-十一烷基咪唑、2-十七烷基咪唑、2-苯基咪唑、1-苄基-2-甲基咪唑、1-苄基-2-苯基咪唑、1-苄基-2-苯基咪唑偏苯三酸盐、1-苄基-2-乙基咪唑、1-苄基-2-乙基-5-甲基咪唑、2-乙基咪唑、2-异丙基咪唑、2-苯基-4-苄基咪唑、1-氰乙基-2-甲基咪唑、1-氰乙基-2-乙基-4-甲基咪唑、1-氰乙基-2-十一烷基咪唑、1-氰乙基-2-异丙基咪唑、1-氰乙基-2-苯基咪唑、1-氰乙基-2-甲基咪唑鎓偏苯三甲酸酯(1-シァノェチル-2-メチルイミダゾリゥムトリメリテ一ト)、1-氰乙基-2-苯基咪唑鎓偏苯三甲酸酯、2,4-二氨基-6-[2’-甲基咪唑基-(1’)]-乙基-s-三嗪、2,4-二氨基-6-[2’-乙基-4-甲基咪唑基-(1’)]-乙基-s-三嗪、2,4-二氨基-6-[2’-十一烷基咪唑基-(1’)]-乙基-s-三嗪、2-甲基咪唑鎓异氰酸加成物、2-苯基咪唑鎓异氰酸加成物、2,4-二氨基-6-[2’-甲基咪唑基-(1’)]-乙基-s-三嗪-三嗪-异氰酸加成物、2-苯基-4,5-二羟甲基咪唑、2-苯基-4-苄基-5-羟甲基咪唑、4,4’-亚甲基-二(2-乙基-5-甲基咪唑)、1-氨乙基-2-甲基咪唑、1-氰乙基-2-苯基-4,5-二(氰基乙氧基甲基)咪唑、1-十二烷基-2-甲基-3-苄基咪唑鎓氯化物、2-甲基咪唑苯并***加成物、1-氨乙基-2-乙基咪唑、1-(氰基乙基氨基乙基)-2-甲基咪唑、N,N’-[2-甲基咪唑基-(1)-乙基]-己二酰二酰胺(N,N’-[2-メチルイミダゾリル-(1)-ェチル]-ァジポイルジァミド)、N,N’-二(2-甲基咪唑基-1-乙基)脲、N-(2-甲基咪唑基-1-乙基)脲、N,N’-[2-甲基咪唑基-(1)-乙基]十二烷二醇二酰胺、N,N’-[2-甲基咪唑基-(1)-乙基]二十烷二醇二酰胺、1-苄基-2-苯基咪唑盐酸盐等咪唑类、三苯基膦等反应促进剂。这些可以单独使用,也可以两种以上混合使用。
另外,为了稳定用作胶带时的轻敲(テ一ピング)特性,可以使液状粘接剂中含有粒径1μm以下的填充剂。
轻敲特性的稳定是指,在将胶带热压接在引线上时,防止因粘接剂熔融而引起从胶带端面发生溢出,且保持粘接层具有适当的厚度、维持粘接性。
填充剂含量优选设定为总固体量的4质量%~40质量%,优选为9质量%~24质量%的范围。
如果含量在上述范围内,则轻敲特性的稳定化效果增大,而且胶带的粘接强度提高、层叠等加工性变好。
作为填充剂例如可以使用二氧化硅、石英粉、氧化铝、碳酸钙、氧化镁、金刚石粉、云母、氟树脂、锆石粉等。
另外,对于液状粘接剂,根据需要,也可以在反应结束后即干燥后取出,用有机溶剂、水、或有机溶剂和水的混合物清洁之后,再次溶解于根据需要而选择的有机溶剂并作为粘接剂使用。
作为能够用于清洁的有机溶剂,可以列举出丙酮、甲基乙基甲酮、己烷、苯、甲苯、二甲苯、甲醇、乙醇、丙醇、***、四氢呋喃、醋酸甲酯、醋酸乙酯、乙腈、二氯甲烷、氯仿、四氯化碳、氯苯、二氯苯、二氯乙烷、三氯乙烷等。
接着,对本发明的胶带进行说明。
本发明的胶带的特征在于,在耐热性膜或剥离性膜的至少一面上形成有涂布了上述电子部件用液状粘接剂并干燥而得的粘接层。
此时,优选涂布厚度在5μm~100μm、特别是10μm~50μm的范围。
作为耐热性膜,例如可以列举出聚酰亚胺、聚苯硫醚、聚醚、聚乙二酰脲(polyparabanic acid)以及聚对苯二甲酸乙二酯等耐热性树脂的膜、环氧树脂-玻璃纤维布、环氧树脂-聚酰亚胺-玻璃纤维布等复合耐热膜等,特别优选聚酰亚胺膜。
优选耐热性膜的厚度设定为7.5μm~130μm、优选为12.5μm~75μm的范围。可以根据需要选择耐热性膜的形状和尺寸。
如果在上述范围内,则胶带具有足够的硬度,容易冲裁操作。
作为剥离性膜优选厚度为1μm~200μm、优选为10μm~100μm范围的剥离性膜,作为临时支撑体发挥作用。可以根据需要选择剥离性膜的形状和尺寸。作为可使用的剥离性膜,可以列举出聚丙烯膜、氟树脂类膜、聚乙烯膜、聚对苯二甲酸乙二酯膜、纸以及根据情况通过硅树脂来赋予其剥离性而得到的剥离性膜等。
上述剥离性膜的90°剥离强度优选为0.01g/cm~7.0g/cm的范围。
如果剥离强度在上述范围内,则输送胶带时剥离性膜不会轻易地从粘接层剥离,而且使用时剥离性膜可以干净地从粘接层剥离,操作性变好。
此外,对于耐热性膜上形成了粘接层的情况,也可以在粘接层上进一步设置保护膜。
作为保护膜,可以使用与上述剥离性膜相同的物质。
实施例
以下基于实施例对本发明进行更详细地说明。
实施例1
组分(a):
丙烯腈-丁二烯共聚物(不含羧基、门尼粘度70M1+4100℃、丙烯腈含量27%) 100质量份
组分(b):
对叔丁基苯酚型可溶酚醛树脂(商品名:“CKM-1282”、昭和高分子公司制) 50质量份
对叔丁基苯酚和Bis-A的共聚型酚醛清漆型酚醛树脂(CKM-2400、昭和高分子公司制) 20质量份
组分(c):
市售的由上述式(1)所示的化合物 30质量份
市售的由上述式(2)所示的化合物 50质量份
组分(d):
1,3-双(3-氨基丙基)-1,1,3,3-四甲基二硅氧烷 0.25质量份
上述组分添加至四氢呋喃中,充分混合、溶解,并调整为占固体的比率为30质量%,得到了实施例1的电子部件用液状粘接剂。
此外,相对于马来酰亚胺基1摩尔当量,氨基的摩尔当量为0.51。
实施例2
组分(a)变更如下。
组分(a):
羧基改性丁二烯-丙烯腈共聚物(羧基当量100,门尼粘度60M1+4100℃,丙烯腈含量27%) 100质量份
除此之外与实施例1相同,得到了实施例2的电子部件用液状粘接剂。
实施例3
组分(b)变更如下。
组分(b):
对叔丁基苯酚型可溶酚醛树脂(CKM-1282、昭和高分子公司制)
70质量份
除此之外与实施例1相同,得到了实施例3的电子部件用液状粘接剂。
实施例4
组分(b)变更如下。
组分(b):
对叔丁基苯酚型可溶型酚醛树脂(商品名:“CKM-1282”、昭和高分子公司制) 50质量份
对叔丁基苯酚和Bis-A的共聚型酚醛清漆型酚醛树脂(CKM-2400、昭和高分子公司制) 40质量份
除此之外与实施例1相同,得到了实施例4的电子部件用液状粘接剂。
实施例5
组分(c)变更如下。
组分(c):
市售的由上述式(1)所示的化合物 15质量份
市售的由上述式(2)所示的化合物 65质量份
除此之外与实施例1相同,得到了实施例5的电子部件用液状粘接剂。
实施例6
组分(d)变更如下。
组分(d):
化学式5
除此之外与实施例1相同,得到了实施例6的电子部件用液状粘接剂。
实施例7
组分(b)以及组分(c)变更如下。
组分(b):
对叔丁基苯酚型可溶酚醛树脂(商品名:“CKM-1282”、昭和高分子公司制) 16.6质量份
对叔丁基苯酚和Bis-A的共聚型酚醛清漆型酚醛树脂(CKM-2400、昭和高分子公司制) 6.7质量份
组分(c):
市售的由上述式(1)所示的化合物 10质量份
市售的由上述式(2)所示的化合物 16.7质量份
除此之外与实施例1相同,得到了实施例7的电子部件用液状粘接剂。
实施例8
组分(b)以及组分(c)变更如下。
组分(b):
对叔丁基苯酚型可溶酚醛树脂(商品名:“CKM-1282”、昭和高分子公司制) 33.3质量份
对叔丁基苯酚和Bis-A的共聚型酚醛清漆型酚醛树脂(CKM-2400、昭和高分子公司制) 13.4质量份
组分(c):
市售的由上述式(1)所示的化合物 20质量份
市售的由上述式(2)所示的化合物 33.3质量份
除此之外与实施例1相同,得到了实施例8的电子部件用液状粘接剂。
实施例9
组分(b)以及组分(c)变更如下。
组分(b):
对叔丁基苯酚型可溶酚醛树脂(商品名:“CKM-1282”、昭和高分子公司制) 133.3质量份
对叔丁基苯酚和Bis-A的共聚型酚醛清漆型酚醛树脂(CKM-2400、昭和高分子公司制) 53.4质量份
组分(c):
市售的由上述式(1)所示的化合物 80质量份
市售的由上述式(2)所示的化合物 133.3质量份
除此之外与实施例1相同,得到了实施例9的电子部件用液状粘接剂。
实施例10
组分(b)以及组分(c)变更如下。
组分(b):
对叔丁基苯酚型可溶酚醛树脂(商品名:“CKM-1282”、昭和高分子公司制) 266.6质量份
对叔丁基苯酚和Bis-A的共聚型酚醛清漆型酚醛树脂(CKM-2400、昭和高分子公司制) 106.7质量份
组分(c):
市售的由上述式(1)所示的化合物 160质量份
市售的由上述式(2)所示的化合物 266.7质量份
除此之外与实施例1相同,得到了实施例10的电子部件用液状粘接剂。
实施例11
组分(b)以及组分(c)变更如下。
组分(b):
对叔丁基苯酚型可溶酚醛树脂(商品名:“CKM-1282”、昭和高分子公司制) 85.7质量份
对叔丁基苯酚和Bis-A的共聚型酚醛清漆型酚醛树脂(CKM-2400、昭和高分子公司制) 34.3质量份
组分(c):
市售的由上述式(1)所示的化合物 11.2质量份
市售的由上述式(2)所示的化合物 18.8质量份
除此之外与实施例1相同,得到了实施例11的电子部件用液状粘接剂。
实施例12
组分(b)以及组分(c)变更如下。
组分(b):
对叔丁基苯酚型可溶酚醛树脂(商品名:“CKM-1282”、昭和高分子公司制) 32.1质量份
对叔丁基苯酚和Bis-A的共聚型酚醛清漆型酚醛树脂(CKM-2400、昭和高分子公司制) 12.9质量份
组分(c):
市售的由上述式(1)所示的化合物 39.4质量份
市售的由上述式(2)所示的化合物 65.6质量份
除此之外与实施例1相同,得到实施例12的电子部件用液状粘接剂。
实施例13
组分(b)以及组分(c)变更如下。
组分(b):
对叔丁基苯酚型可溶酚醛树脂(商品名:“CKM-1282”、昭和高分子公司制) 21.4质量份
对叔丁基苯酚和Bis-A的共聚型酚醛清漆型酚醛树脂(CKM-2400、昭和高分子公司制) 8.6质量份
组分(c):
市售的由上述式(1)所示的化合物 45质量份
市售的由上述式(2)所示的化合物 75质量份
除此之外与实施例1相同,得到了实施例13的电子部件用液状粘接剂。
实施例14
组分(b)以及组分(c)变更如下。
组分(b):
对叔丁基苯酚型可溶酚醛树脂(商品名:“CKM-1282”、昭和高分子公司制) 10.7质量份
对叔丁基苯酚和Bis-A的共聚型酚醛清漆型酚醛树脂(CKM-2400、昭和高分子公司制) 4.3质量份
组分(c):
市售的由上述式(1)所示的化合物 50.6质量份
市售的由上述式(2)所示的化合物 84.4质量份
除此之外与实施例1相同,得到了实施例14的电子部件用液状粘接剂。
实施例15
组分(c)变更如下。
组分(c):
市售的由上述式(1)所示的化合物 5质量份
市售的由上述式(2)所示的化合物 75质量份
除此之外与实施例1相同,得到了实施例15的电子部件用液状粘接剂。
实施例16
组分(c)变更如下。
组分(c):
市售的由上述式(1)所示的化合物 10质量份
市售的由上述式(2)所示的化合物 70质量份
除此之外与实施例1相同,得到了实施例16的电子部件用液状粘接剂。
实施例17
组分(c)变更如下。
组分(c):
市售的由上述式(1)所示的化合物 20质量份
市售的由上述式(2)所示的化合物 60质量份
除此之外与实施例1相同,得到了实施例17的电子部件用液状粘接剂。
实施例18
组分(c)变更如下。
组分(c):
市售的由上述式(1)所示的化合物 40质量份
市售的由上述式(2)所示的化合物 40质量份
除此之外与实施例1相同,得到了实施例18的电子部件用液状粘接剂。
比较例1
组分(c)变更如下。
组分(c):
市售的由上述式(1)所示的化合物 80质量份
除此之外与实施例1相同,得到不含式(2)所示化合物的比较例1的电子部件用液状粘接剂。
比较例2
组分(c)变更如下。
组分(c):
市售的由上述式(2)所示的化合物 80质量份
除此之外与实施例1相同,得到不含式(1)所示化合物的比较例2的电子部件用液状粘接剂。
实施例以及比较例的主要条件示于表1。
表1
将上述实施例1至实施例18以及比较例1、2的电子部件用液状粘接剂涂布在聚酰亚胺膜的两面,使干燥后粘接层的厚度为20μm,在热风循环型干燥机中、160℃下干燥5分钟,制作成使用了实施例1至实施例18以及比较例1、2的粘接剂的胶带。
接着,用使用了实施例1至实施例18以及比较例1、2的粘接剂的胶带,按照下述步骤组装用于图1所示的半导体封装件的与板贴合的引线架。
胶带的冲裁:利用金属模将胶带冲裁成环状。
胶带的临时粘接(仮接着):将板放置在加热板(hot plate)上,用金属棒(rod)将冲裁成环状的胶带挤压在板上以临时粘接。
临时粘接条件为140℃/2秒/4Kgf/cm2。
引线架的组装:对在上述工序中临时粘接了胶带的板与引线架(Cu材质)本体进行校准,在加热后的加热板上进行加热加压,通过胶带来贴合引线架(Cu材质)和板。
另外,贴合条件为140℃/2秒/4Kgf/cm2。
胶带凝固(cure):放入氮气取代后的热风循环型烘箱内使其热固化。
另外,热固化条件为200℃/1小时。
接着,使用制成的与板贴合的引线架(Cu材质),按照以下步骤组装半导体封装件。
芯片接合(die bonding):用芯片接合用银糊料将半导体芯片粘接在与板贴合后的引线架的板部分,在150℃下固化2小时。
引线接合(wire bonding):利用引线接合器(wire bonder),用金属线将半导体芯片上的引线焊垫(wire pad)和引脚的内部引线端部的镀银部分相连接。
模塑(moulding):用环氧类成型剂进行了传递模。
后处理工序:实施复位(homing)、冲切(die cut)、外引线部的电镀等工序,后处理成封装件。
评价
低温粘接、固化
对实施例1至实施例18以及比较例1、2的胶带进行是否能够容易且迅速地与被粘接体即板或引脚线粘接的评价。
具体而言,在铜板上在100℃、140℃或180℃下贴附(轻敲)胶带之后,测量10mm宽的带在室温下的90°剥离强度(粘接力)。
结果示于表2。
表2
然后,以粘接力在4.2N/cm以上作为可粘接,按以下标准对“低温粘接、固化”进行评价。
◎:在100℃可以粘接。实用性优异。
○:在140℃可以粘接。实用上没有问题。
△:在180℃可以粘接。可以实用。
×:在180℃不能粘接。实用上存在问题。
低温粘接、固化的评价结果示于表5。
耐热性
如下所述,基于空隙、剪切粘接力进行评价。
空隙
在使粘接剂固化时,通过显微镜视觉判断粘接剂内产生的空隙是否达到实用上存在问题的程度。
具体而言,在140℃下在铜板上贴附(轻敲)胶带之后,在30℃/70%RH下进行72小时湿度控制保管,制作成试验用样品。
接着,将试验用样品在160℃的加热部件上放置1分钟,通过显微镜视觉判断带和铜板之间的空隙状态。
剪切粘接力
制作样品
在140℃下将裁剪成宽5mm×长75mm的胶带贴附(轻敲)在20mm×20mm的铜板的端部(一片的中央部)。
贴附面积为25mm2(尺寸为5mm×5mm),未粘贴到铜材料的胶带长为70mm。
测量剪切粘接强度
将上述样品固定在160℃的加热部件上之后,将带的未粘贴到铜板的部分连接至万能拉伸试验机,测量了剪切粘接强度。
测量时铜板-拉伸试验机的卡盘(chuck)间距为50mm,拉伸速度为50mm/分钟。
此外,为了使测量温度稳定,将样品固定于加热部件,过5秒钟后开始测量。
结果示于表3。
表3
然后,按以下标准对“耐热性”进行评价。
◎:没有空隙且剪切粘接强度为40N/cm2以上(实用上完全没有问题)
○:没有空隙且剪切粘接强度为20N/cm2以上不足40N/cm2(实用上没有问题)
△:没有空隙但剪切粘接强度不足20N/cm2(实用上没有问题)
×:有空隙且剪切粘接强度不足20N/cm2(实用上存在问题)
耐热性评价结果示于表5。
引脚的尺寸稳定性
使粘接剂固化时,基于引脚的位置偏移是否达到实用上存在问题的程度而进行评价。
具体而言,使用金属模将胶带冲裁成外尺寸为22mm×内尺寸为20mm的正方形(环)之后,用热压贴附在评价用引线架(QFP208脚)的规定位置。
热压条件为压力5kgf/cm2、压接时间为0.3秒。压接温度为120℃~140℃(将引脚线上的粘接剂厚度为15μm~18μm的温度作为可贴附温度)。
此外,所使用的引线架的管脚间距(pin pitch)为168μm。
引脚位置偏移的测量
在带刚贴附后以及在热风循环型烘箱中以200℃/1小时处理后,用显微镜测量引线架的管脚间距。
压接温度以及测量结果示于表4。
表4
然后,按以下标准对“引脚的尺寸稳定性”进行评价。
○:带刚贴附后的管脚间距以及在热风循环型烘箱中以200℃/1小时处理后的管脚间距,两者都在168μm±10%以内。
△:带刚贴附后的管脚间距以及在热风循环型烘箱中以200℃/1小时处理后的管脚间距,两者都超过168μm±10%、在168μm±15%以内。
×:带刚贴附后的管脚间距以及在热风循环型烘箱中以200℃/1小时处理后的管脚间距,两者都超过168μm±15%。
引脚的尺寸稳定性评价结果示于表5。
可靠性
对如上所述得到的封装件进行PCBT试验(Pressure Cooker BiasedTest)。
在施加100V电压、130℃、2atm、85%RH条件下进行电气可靠性试验。
然后,按以下标准对“可靠性”进行评价。
○:240小时没有发生短路
×:240小时内发生短路
可靠性评价结果示于表5。
耐迁移性
上述可靠性试验之后,研磨封装件使粘接剂面露出,用显微镜进行观察。
然后,按以下标准对“耐迁移性”进行评价。
◎:没有确认产生枝状晶体,引脚也没有发生变色。
○:没有确认产生枝状晶体,但引脚发生变色。
×:产生枝状晶体
耐迁移性评价结果示于表5。
操作性
对引线架组装时胶带的轻敲等使用时的操作性(卷曲、移动性)以及胶带粘接剂表面的缝褶,按以下标准进行“操作性”评价。
○:没有缝褶非常容易操作
△:缝褶少容易操作
×:有缝褶不易操作
评价结果示于表5。
表5
评价结果
从表5可知,实施例1至实施例18的胶带全部为△以上,实用上不存在问题。
特别是,实施例5、实施例9、实施例16以及实施例17,低温粘接、固化、耐热性、耐迁移性优异。实施例2低温粘接、固化、耐热性、耐迁移性更加优异。
与此相对,比较例1的胶带在可靠性试验中发生短路、耐迁移性中产生枝状晶体,因此实用上存在问题。
而且,比较例2的胶带在耐热性以及引脚线的尺寸稳定性上实用上存在问题。
工业实用性
能够提供一种能够在低温下粘接、固化,具有充分的耐热性以及可靠性,且耐迁移性优异的电子部件用液状粘接剂以及胶带。
符号说明
1 半导体芯片 2 板
3 引脚线 4 接合引线
5 树脂 6 粘接层
7 压料垫 8 电极
Claims (14)
2.根据权利要求1所述的电子部件用液状粘接剂,其特征在于,
所述组分(a)的门尼粘度为50M1+4100℃~90M1+4100℃,丙烯腈含量为5质量%~50质量%。
3.根据权利要求1所述的电子部件用液状粘接剂,其特征在于,
所述组分(a)是具有羧基的丙烯腈-丁二烯共聚物。
4.根据权利要求1所述的电子部件用液状粘接剂,其特征在于,
所述组分(b)是包含可熔型烷基酚的酚醛树脂。
5.根据权利要求1所述的电子部件用液状粘接剂,其特征在于,
所述组分(b)并用可熔型酚和酚醛清漆型酚。
6.根据权利要求1所述的电子部件用液状粘接剂,其特征在于,
所述组分(c)中,由上式(1)以及上式(2)表示的化合物的质量比为3∶3至3∶45。
7.根据权利要求1所述的电子部件用液状粘接剂,其特征在于,
相对于组分(a)100质量份,组分(b)和组分(c)的总和为10质量份~900质量份,且组分(b)在组分(b)和组分(c)的总和中所占的质量比为10质量%~90质量%。
8.根据权利要求1所述的电子部件用液状粘接剂,其特征在于,
所述电子部件用液状粘接剂还包括作为组分(d)的二胺化合物。
9.根据权利要求8所述的电子部件用液状粘接剂,其特征在于,
所述组分(d)是由下式(3)表示的化合物,
化学式3
H2N-R1-NH2 (3),
式中,R1表示二价芳香基。
11.根据权利要求1所述的电子部件用液状粘接剂,其特征在于,
所述电子部件用液状粘接剂的粒径为1μm以下的填充剂占固体成分总量的4质量%~40质量%。
12.一种胶带,其特征在于,
在耐热性膜的至少一面形成有通过涂布权利要求1所述的电子部件用液状粘接剂并干燥而得的粘接层。
13.根据权利要求12所述的胶带,其特征在于,
耐热性膜是聚酰亚胺膜。
14.一种胶带,其特征在于,
在剥离性膜的至少一面形成有通过涂布权利要求1所述的电子部件用液状粘接剂并干燥而得的粘接层。
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JP2001019920A (ja) * | 1999-07-08 | 2001-01-23 | Tomoegawa Paper Co Ltd | 電子部品用接着剤及び接着テープ |
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JP2002129116A (ja) * | 2000-10-26 | 2002-05-09 | Tomoegawa Paper Co Ltd | 半導体装置用接着テープ |
JP2004352963A (ja) * | 2003-05-30 | 2004-12-16 | Tomoegawa Paper Co Ltd | 電子部品用接着テープ |
CN101012369A (zh) * | 2006-01-30 | 2007-08-08 | 国家淀粉及化学投资控股公司 | 热界面材料 |
JP2009158817A (ja) * | 2007-12-27 | 2009-07-16 | Tomoegawa Paper Co Ltd | Qfn用熱硬化型樹脂組成物及びそれを用いたqfn用接着シート |
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CN112626569A (zh) * | 2020-12-01 | 2021-04-09 | 云南漫风鸟科技有限公司 | 一种锌冶炼电解锌阴极铝板的防腐工艺 |
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JP5486081B2 (ja) | 2014-05-07 |
CN102812099B (zh) | 2014-12-03 |
KR20120124479A (ko) | 2012-11-13 |
JPWO2011118664A1 (ja) | 2013-07-04 |
TWI429723B (zh) | 2014-03-11 |
WO2011118664A1 (ja) | 2011-09-29 |
TW201202370A (en) | 2012-01-16 |
KR101401162B1 (ko) | 2014-05-29 |
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