CN109890903A - 导热性膏和电子装置 - Google Patents
导热性膏和电子装置 Download PDFInfo
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- CN109890903A CN109890903A CN201780067775.2A CN201780067775A CN109890903A CN 109890903 A CN109890903 A CN 109890903A CN 201780067775 A CN201780067775 A CN 201780067775A CN 109890903 A CN109890903 A CN 109890903A
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- thermal conductivity
- conductivity cream
- methyl
- mass
- cream
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- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 description 1
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- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
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- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
- C09J163/04—Epoxynovolacs
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
- C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
- C08G59/4028—Isocyanates; Thioisocyanates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
- C08G59/621—Phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
- C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- 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
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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Abstract
本发明的导热性膏包含热固性树脂、固化剂、丙烯酸化合物和导热性填料,热固性树脂和固化剂中的至少一者包含具有联苯骨架的树脂,丙烯酸化合物包含(甲基)丙烯酸单体。
Description
技术领域
本发明涉及导热性膏和电子装置。
背景技术
在至今为止的导热性树脂组合物中,以提高导热性为目的进行了各种开发。作为这种技术,有专利文献1中记载的技术。根据该文献的记载,通过使用具有联苯骨架的环氧树脂,能够提高导热性(专利文献1的0031段)。
现有技术文献
专利文献
专利文献1:日本特开2013-151655号公报
发明内容
发明要解决的技术问题
然而,已弄清楚了上述文献中记载的导热性膏在导热性和金属密合性方面有改善的余地。
用于解决技术问题的手段
根据发明人的见解,弄清楚了通过使用具有联苯骨架的树脂和(甲基)丙烯酸单体(丙烯酸化合物),能够实现导热性和金属密合性优异的导热性膏。
根据本发明,提供一种导热性膏,其包含热固性树脂、固化剂、丙烯酸化合物和导热性填料,所述导热性膏的特征在于:
所述热固性树脂和所述固化剂中的至少一者包含具有联苯骨架的树脂,
所述丙烯酸化合物包含(甲基)丙烯酸单体。
另外,根据本发明,提供一种电子装置,其包括上述导热性膏的固化物。
发明效果
采用本发明,能够提供能够提高导热性和金属密合性的导热性膏和使用该导热性膏的电子装置。
附图说明
上述的目的和其他目的、特征和优点通过下面说明的优选实施方式和附随于其的下面的附图将变得进一步明确。
图1是表示本实施方式的半导体装置的一个例子的截面图。
具体实施方式
下面,利用附图对实施方式进行说明。在所有的附图中,对相同的构成要素赋予相同的符号,适当省略说明。
本实施方式的导热性膏可以包含热固性树脂、固化剂、丙烯酸化合物和导热性填料。在本实施方式的导热性膏中,热固性树脂和固化剂中的至少一者可以包含具有联苯骨架的树脂,丙烯酸化合物可以包含(甲基)丙烯酸单体。
本实施方式的导热性膏能够用于将印刷电路基板等基材和半导体元件等电子部件接合的粘接层。即,由本实施方式的导热性膏的固化物构成的树脂粘接层能够用作芯片粘结材料(die attach material)。通过使用本实施方式的导热性膏的固化物,能够实现电子部件的散热性优异、且电子部件与基材的金属密合性(吸湿后的金属密合性)优异的芯片粘结材料。
根据本实施方式,导热性膏通过包含具有联苯骨架的树脂和(甲基)丙烯酸单体,能够提高导热性和金属密合性。详细的机理虽然并不确定,但是可认为通过由源自联苯骨架的刚直结构带来的刚性的提高和(甲基)丙烯酸单体的密合力的增加,能够在导热性膏固化后充分抑制成为导热性下降的原因之一的分子运动,能够使导热性良好。即,本实施方式的导热性膏通过在维持导热性填料的含量的同时适当选择树脂的特性,能够高效率地提高导热性。另外,可认为通过由(甲基)丙烯酸单体产生的密合力的增加,当将导热性膏用作电子部件与基材的粘接层时,能够提高这些的芯片抗切强度(die shear strength)。
另外,即使在本实施方式的导热性膏中的导热性填料的含量低时,也能够维持高导热系数。即,即使在导热性填料含量低的导热性膏中也能够实现高导热系数。作为一个例子,即使在该导热性填料的含量为80质量%以下时,也能够实现导热系数为5W/mK以上,更优选为10W/mK以上。
下面,对本实施方式的导热性膏的成分进行说明。
(热固性树脂)
作为导热性膏中包含的热固性树脂,可以使用通过加热形成3维网眼结构的一般的热固性树脂。在本实施方式中,热固性树脂并无特别限定,例如可以包含选自氰酸酯树脂、环氧树脂、在1个分子内具有2个以上的自由基聚合性的碳-碳双键的树脂和马来酰亚胺树脂中的一种或两种以上。在这些之中,从提高导热性膏的粘接性的观点出发,尤其优选包含环氧树脂。
作为用作热固性树脂的环氧树脂,可以使用在1个分子内具有2个以上的缩水甘油基的所有单体、低聚物、聚合物,对其分子量和分子结构没有特别限定。作为本实施方式中的环氧树脂,例如可以举出联苯型环氧树脂;双酚A型环氧树脂、双酚F型环氧树脂、四甲基双酚F型环氧树脂等双酚型环氧树脂;茋型环氧树脂;苯酚酚醛清漆型环氧树脂、甲酚酚醛清漆型环氧树脂等酚醛清漆型环氧树脂;三酚基甲烷型环氧树脂、烷基改性三酚基甲烷型环氧树脂等多官能环氧树脂;具有亚苯基骨架的苯酚芳烷基型环氧树脂、具有亚联苯基骨架的苯酚芳烷基型环氧树脂等芳烷基型环氧树脂;二羟基萘型环氧树脂、对二羟基萘的二聚物进行缩水甘油醚化而获得的环氧树脂等萘酚型环氧树脂;异氰尿酸三缩水甘油酯、单烯丙基二缩水甘油基异氰尿酸酯等含有三嗪核的环氧树脂;双环戊二烯改性苯酚型环氧树脂等桥环烃化合物改性苯酚型环氧树脂。另外,作为环氧树脂,例如还可以使用对在1个分子内包含2个以上的缩水甘油基的化合物中的双酚A、双酚F、联苯酚(biphenol)等双酚化合物或者它们的衍生物、氢化双酚A、氢化双酚F、氢化联苯酚、环己二醇、环己烷二甲醇、环己烷二乙醇等具有脂环结构的二醇或它们的衍生物、丁二醇、己二醇、辛二醇、壬二醇、癸二醇等脂肪族二醇或它们的衍生物等进行环氧化而得到的2官能化合物、具有三羟基苯基甲烷骨架、氨基苯酚骨架的3官能化合物。作为热固性树脂的环氧树脂,可以包含选自上述例示的物质中的一种或两种以上。
在这些之中,从提高涂敷操作性和粘接性的观点出发,更优选包含双酚型环氧树脂,尤其优选包含双酚F型环氧树脂。另外,在本实施方式中,从更有效地提高涂敷操作性的观点出发,更优选包含在室温(25℃)为液态的液态环氧树脂。
用作热固性树脂的氰酸酯树脂没有特别限定,例如可以包含选自1,3-二氰氧基苯、1,4-二氰氧基苯、1,3,5-三氰氧基苯、1,3-二氰氧基萘、1,4-二氰氧基萘、1,6-二氰氧基萘、1,8-二氰氧基萘、2,6-二氰氧基萘、2,7-二氰氧基萘、1,3,6-三氰氧基萘、4,4’-二氰氧基联苯、双(4-氰氧基苯基)甲烷、双(3,5-二甲基-4-氰氧基苯基)甲烷、2,2-双(4-氰氧基苯基)丙烷、2,2-双(3,5-二溴-4-氰氧基苯基)丙烷、双(4-氰氧基苯基)醚、双(4-氰氧基苯基)硫醚、双(4-氰氧基苯基)砜、三(4-氰氧基苯基)亚磷酸酯、三(4-氰氧基苯基)磷酸酯、通过酚醛清漆树脂和卤化氰的反应而获得的氰酸酯类、以及通过将这些多官能氰酸酯树脂的氰酸酯基进行三聚化而形成的具有三嗪环的预聚物中的一种或两种以上。上述预聚物可以通过例如将无机酸、路易斯酸等酸、醇钠、叔胺类等碱、或碳酸钠等盐类作为催化剂使上述多官能氰酸酯树脂单体聚合而获得。
作为用作热固性树脂的在1个分子内具有2个以上的自由基聚合性的碳一碳双键的树脂,例如可以使用在分子内具有2个以上的(甲基)丙烯酰基的自由基聚合性丙烯酸树脂。在本实施方式中,作为上述丙烯酸树脂,可以包含作为分子量为500~10000的聚醚、聚酯、聚碳酸酯或聚(甲基)丙烯酸酯、且具有(甲基)丙烯酰基的化合物。当作为热固性树脂使用在1个分子内具有2个以上的自由基聚合性的碳-碳双键的树脂时,导热性膏例如可以包含热自由基聚合引发剂等聚合引发剂。
用作热固性树脂的马来酰亚胺树脂没有特别限定,例如可以包含选自N,N,-(4,4’-二苯甲烷)双马来酰亚胺、双(3-乙基-5-甲基-4-马来酰亚胺苯基)甲烷、2,2-双[4-(4-马来酰亚胺苯氧基)苯基]丙烷等双马来酰亚胺树脂中的一种或两种以上。
另外,本实施方式的热固性树脂可以包含具有联苯骨架的环氧树脂(联苯型环氧树脂)作为具有联苯骨架的树脂。由此,能够提高导热性膏的导热性和金属密合性。
具有联苯骨架的环氧树脂只要在其分子结构内具有联苯骨架并且具有2个以上的环氧基,对其结构就没有特别限定,例如可以举出利用环氧氯丙烷对联苯酚或其衍生物进行处理而得到的2官能环氧树脂、具有亚联苯基骨架的苯酚芳烷基型环氧树脂、具有亚联苯基骨架的萘酚芳烷基型环氧树脂等,这些可以单独使用,也可以混合使用。在这些之中,尤其是在分子内具有2个环氧基的环氧树脂成为耐热性的提高优异的环氧树脂,因此优选。作为这样的环氧树脂,可以举出联苯型环氧树脂、四甲基联苯型环氧树脂等利用环氧氯丙烷对联苯酚衍生物进行处理而得到的2官能环氧树脂;具有亚联苯基骨架的苯酚芳烷基型环氧树脂中环氧基为2个的苯酚芳烷基型环氧树脂(有时也表达为苯酚核体数为2);具有亚联苯基骨架的萘酚芳烷基型树脂中环氧基为2个的萘酚芳烷基型树脂等。
在本实施方式中,相对于导热性膏整体,导热性膏中的热固性树脂的含量例如优选为5质量%以上,更优选为6质量%以上,进一步优选为7质量%以上。由此,能够提高导热性膏的流动性,实现涂敷操作性的进一步提高。另一方面,相对于导热性膏整体,导热性膏中的热固性树脂的含量例如优选为30质量%以下,更优选为25质量%以下,进一步优选为15质量%以下。由此,能够提高使用导热性膏形成的粘接层的耐回流性(reflowresistance)和耐湿性。
(丙烯酸化合物)
本实施方式的导热性膏可以包含丙烯酸化合物。
作为本实施方式的丙烯酸化合物,优选包含(甲基)丙烯酸单体。在本实施方式中,(甲基)丙烯酸单体表示丙烯酸酯单体、甲基丙烯酸酯单体或它们的混合物,表示具有至少1个以上的官能团(丙烯酰基或甲基丙烯酰基)的单体。
在本实施方式中,(甲基)丙烯酸单体可以为具有2个以上的官能团的单体。由此,能够提高金属密合性。
本实施方式的(甲基)丙烯酸单体,与单体聚合而得到的丙烯酸聚合物不同,是具有至少1个以上的乙烯性不饱和双键的单体。作为该(甲基)丙烯酸单体的分子量没有特别限定,例如下限值可以为150以上,优选为160以上,更优选为180以上,另一方面,上限值可以为2000以下,优选为1000以下,更优选为600以下。
作为2官能(甲基)丙烯酸单体,例如可以举出丙三醇二(甲基)丙烯酸酯、三羟甲基丙烷二(甲基)丙烯酸酯、季戊四醇二(甲基)丙烯酸酯、二(甲基)丙烯酸锌、乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、1,3-丁二醇二(甲基)丙烯酸酯、1,10-癸二醇二(甲基)丙烯酸酯、四亚甲基二醇二(甲基)丙烯酸酯等。这些可以单独使用,也可以将2种以上组合使用。
本实施方式的(甲基)丙烯酸单体,除了(甲基)丙烯酸单体以外,还可以包含其他丙烯酸化合物。作为其他丙烯酸化合物,例如可以使用单官能丙烯酸酯、多官能丙烯酸酯、单官能甲基丙烯酸酯、多官能甲基丙烯酸酯、聚氨酯丙烯酸酯、聚氨酯甲基丙烯酸酯、环氧丙烯酸酯、环氧甲基丙烯酸酯、聚酯丙烯酸酯或尿素丙烯酸酯等的单体、低聚物、它们的混合物。这些可以使用1种或2种以上。
作为其他丙烯酸化合物,例如可以举出(甲基)丙烯酸2-羟乙酯、(甲基)丙烯酸2-羟丙酯、(甲基)丙烯酸3-羟丙酯、(甲基)丙烯酸2-羟丁酯、(甲基)丙烯酸3-羟丁酯、(甲基)丙烯酸4-羟丁酯、1,2-环己二醇单(甲基)丙烯酸酯、1,3-环己二醇单(甲基)丙烯酸酯、1,4-环己二醇单(甲基)丙烯酸酯、1,2-环己烷二甲醇单(甲基)丙烯酸酯、1,3-环己烷二甲醇单(甲基)丙烯酸酯、1,4-环己烷二甲醇单(甲基)丙烯酸酯、1,2-环己烷二乙醇单(甲基)丙烯酸酯、1,3-环己烷二乙醇单(甲基)丙烯酸酯、1,4-环己烷二乙醇单(甲基)丙烯酸酯、丙三醇单(甲基)丙烯酸酯、三羟甲基丙烷单(甲基)丙烯酸酯、季戊四醇单(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、新戊二醇单(甲基)丙烯酸酯等具有羟基的(甲基)丙烯酸酯或使这些具有羟基的(甲基)丙烯酸酯与二羧酸或其衍生物进行反应而获得的具有羧基的(甲基)丙烯酸酯等。作为在此可以使用的二羧酸,例如可以举出草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、马来酸、富马酸、邻苯二甲酸、四氢邻苯二甲酸、六氢邻苯二甲酸和它们的衍生物。
另外,作为其他丙烯酸化合物,例如还可以使用(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸异丁酯、(甲基)丙烯酸叔丁酯、(甲基)丙烯酸异癸酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸十三烷酯、(甲基)丙烯酸十六酯、(甲基)丙烯酸十八酯、(甲基)丙烯酸异戊酯、(甲基)丙烯酸异十八酯、(甲基)丙烯酸二十二酯、(甲基)丙烯酸2-乙基己酯、其他的(甲基)丙烯酸烷基酯、(甲基)丙烯酸环己酯、(甲基)丙烯酸叔丁基环己酯、(甲基)丙烯酸四氢糠酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸苯氧基乙酯、(甲基)丙烯酸异冰片酯、(甲基)丙烯酸缩水甘油酯、三羟甲基丙烷三(甲基)丙烯酸酯、单(甲基)丙烯酸锌、(甲基)丙烯酸二甲氨乙酯、(甲基)丙烯酸二乙氨乙酯、新戊二醇(甲基)丙烯酸酯、(甲基)丙烯酸三氟乙酯、(甲基)丙烯酸2,2,3,3-四氟丙酯、(甲基)丙烯酸2,2,3,3,4,4-六氟丁酯、(甲基)丙烯酸全氟辛酯、(甲基)丙烯酸全氟辛乙酯、(甲基)丙烯酸甲氧基乙酯、(甲基)丙烯酸丁氧基乙酯、(甲基)丙烯酸乙氧基二乙二醇酯、甲氧基聚亚烷基二醇单(甲基)丙烯酸酯、辛氧基聚亚烷基二醇单(甲基)丙烯酸酯、月桂氧基聚亚烷基二醇单(甲基)丙烯酸酯、硬脂氧基聚亚烷基二醇单(甲基)丙烯酸酯、烯丙氧基聚亚烷基二醇单(甲基)丙烯酸酯、壬基苯氧基聚亚烷基二醇单(甲基)丙烯酸酯、N,N’-亚甲基双(甲基)丙烯酰胺、N,N’-亚乙基双(甲基)丙烯酰胺、1,2-二(甲基)丙烯酰胺乙二醇、二(甲基)丙烯酰氧基甲基三环癸烷、N-(甲基)丙烯酰氧基乙基马来酰亚胺、N-(甲基)丙烯酰氧基乙基六氢邻苯二甲酰亚胺、N-(甲基)丙烯酰氧基乙基邻苯二甲酰亚胺、n-乙烯基-2-吡咯烷酮、苯乙烯衍生物、α-甲基苯乙烯衍生物等。
在本实施方式中,相对于导热性膏整体,(甲基)丙烯酸单体的含量的下限值例如为1质量%以上,优选为3质量%以上,更优选为5质量%以上。由此,能够提高喷出稳定性和金属密合性。另外,还能够降低粘度。相对于导热性膏整体,(甲基)丙烯酸单体的含量的上限值例如为15质量%以下,优选为12质量%以下,更优选为10质量%以下。由此,能够实现导热性膏的各种特性的平衡。
(导热性填料)
本实施方式的导热性膏可以包含导热性填料。
作为导热性填料,只要是导热性优异的填料就没有特别限定,例如可以包含金属、氧化物或氮化物。
作为上述金属填料,例如可以举出银粉、金粉、铜粉等金属粉。作为上述氧化物填料,例如可以举出滑石、烧制粘土、未烧制粘土、云母、玻璃等硅酸盐;氧化钛、氧化铝、氧化镁、勃姆石、二氧化硅、熔融二氧化硅等氧化物颗粒、或氢氧化铝、氢氧化镁、氢氧化钙等氢氧化物颗粒。作为上述氮化物填料,例如可以举出氮化铝、氮化硼、氮化硅、氮化碳等氮化物颗粒。
另外,作为本实施方式的导热性填料,可以包含硫酸钡、硫酸钙、亚硫酸钙等硫酸盐或亚硫酸盐;硼酸锌、偏硼酸钡、硼酸铝、硼酸钙、硼酸钠等硼酸盐、;钛酸锶、钛酸钡等钛酸盐等其他无机填充材料。
可以将这些单独使用也可以将2种以上组合使用。
作为本实施方式的导热性填料,从导电性的观点出发,优选含有选自银、铜、氧化铝中的一种以上。由此,能够提高长期操作性。
作为本实施方式的导热性填料的形状,可以举出片状、球状等。其中,从导热性膏的流动性的观点出发,优选为球状。
导热性填料的平均粒径D50的下限值例如可以为0.1μm以上,优选为0.3μm以上,更优选为0.5μm以上。由此,能够提高导热性膏的导热系数。另一方面,导热性填料的平均粒径D50的上限值例如可以为10μm以下,优选为8μm以下,更优选为5μm以下。由此,能够提高导热性膏的保存稳定性。
导热性填料的平均粒径D95的下限值例如可以为1μm以上,优选为2μm以上,更优选为3μm以上。由此,能够提高导热性膏的导热系数。另一方面,导热性填料的平均粒径D95的上限值例如可以为15μm以下,优选为13μm以下,更优选为10μm以下。由此,能够提高导热性膏的保存稳定性。
导热性填料的平均粒径例如可以利用激光衍射散射法或动态光散射法等进行测量。
在本实施方式中,相对于导热性膏整体,导热性膏中的导热性填料的含量例如优选为50质量%以上,更优选为60质量%以上。由此,能够更有效地提高使用导热性膏形成的粘接层的低热膨胀性、耐湿可靠性和耐回流性。另一方面,相对于导热性膏整体,导热性膏中的导热性填料的含量例如为88质量%以下,优选为83质量%以下,更优选为80质量%以下。由此,能够提高导热性膏的流动性,提高涂敷操作性和粘接层的均匀性。
(固化剂)
导热性膏例如可以包含固化剂。由此,能够提高导热性膏的固化性。固化剂例如可以包含选自脂肪族胺、芳香族胺、双氰胺、二酰肼化合物、酸酐和酚化合物中的一种或两种以上。在这些之中,从提高制造稳定性的观点出发,尤其优选包含双氰胺和酚化合物中的至少一者。
作为用作固化剂的二酰肼化合物,可以举出己二酸二酰肼、十二烷酸二酰肼、间苯二甲酸二酰肼、对羟苯甲酸二酰肼等羧酸二酰肼等。另外,作为用作固化剂的酸酐,可以举出邻苯二甲酸酐、四氢邻苯二甲酸酐、六氢邻苯二甲酸酐、内亚甲基四氢邻苯二甲酸酐、十二烯基琥珀酸酐、马来酸酐与聚丁二烯的反应物、马来酸酐与苯乙烯的共聚物等。
用作固化剂的酚化合物是在1个分子内具有2个以上的酚性羟基的化合物。更优选的1个分子内的酚性羟基的数量为2~5,尤其优选的1个分子内的酚性羟基数为2个或3个。由此,能够更有效地提高导热性膏的涂敷操作性,并且能够在固化时形成交联结构从而使导热性膏的固化物特性优异。上述酚化合物例如可以包含选自双酚F、双酚A、双酚S、四甲基双酚A、四甲基双酚F、四甲基双酚S、二羟基二苯醚、二羟基二苯甲酮、四甲基联苯酚、亚乙基双酚、甲基亚乙基双(甲基苯酚)、亚环己基双酚、联苯酚等双酚类及其衍生物、三(羟基苯基)甲烷、三(羟基苯基)乙烷等3官能酚类及其衍生物、苯酚酚醛清漆、甲酚酚醛清漆等通过使酚类和甲醛进行反应而获得的化合物中以2核体或3核体为主的化合物及其衍生物中的一种或两种以上。在这些之中,更优选包含双酚类,尤其优选包含双酚F。
另外,本实施方式的固化剂可以包含具有联苯骨架的酚醛树脂(酚化合物)作为具有联苯骨架的树脂。由此,能够提高导热性膏的导热性和金属密合性。
作为具有联苯骨架的酚醛树脂,只要在其分子结构内具有联苯骨架并且具有2个以上的酚基,对其结构就没有特别限定。
在本实施方式中,相对于导热性膏整体,导热性膏中的固化剂的含量优选为0.5质量%以上,更优选为1.0质量%以上。由此,能够更有效地提高导热性膏的固化性。另一方面,相对于导热性膏整体,导热性膏中的固化剂的含量优选为10质量%以下,更优选为7质量%以下。由此,能够提高使用导热性膏形成的粘接层的低热膨胀性、耐回流性和耐湿性。
在本实施方式中,相对于导热性膏整体,具有联苯骨架的树脂的含量的下限值例如为1质量%以上,优选为1.5质量%以上,更优选为2质量%以上。由此,能够提高导热性。相对于导热性膏整体,具有联苯骨架的树脂的含量的上限值例如为15质量%以下,优选为10质量%以下,更优选为7质量%以下。由此,能够实现导热系数与粘度等导热性膏的各种特性的平衡。
在本实施方式中,相对于导热性膏整体,具有联苯骨架的树脂和(甲基)丙烯酸单体的含量的下限值例如为3质量%以上,优选为5质量%以上,更优选为6质量%以上。由此,能够提高导热性和金属密合性。相对于导热性膏整体,具有联苯骨架的树脂和(甲基)丙烯酸单体的含量的上限值例如为20质量%以下,优选为18质量%以下,更优选为15质量%以下。由此,能够实现导热系数与固化特性等导热性膏的各种特性的平衡。
在本实施方式中,相对于具有联苯骨架的树脂和(甲基)丙烯酸单体的总量100质量%,(甲基)丙烯酸单体的含量的下限值例如为30质量%以上,优选为50质量%以上,更优选为60质量%以上。由此,能够提高导热性和金属密合性。相对于具有联苯骨架的树脂和(甲基)丙烯酸单体的总量100质量%,(甲基)丙烯酸单体的含量的上限值例如为95质量%以下,优选为90质量%以下,更优选为88质量%以下。由此,能够实现导热系数与固化特性等导热性膏的各种特性的平衡。
在本实施方式中,相对于导热性膏整体,具有联苯骨架的酚醛树脂和(甲基)丙烯酸单体的含量的下限值例如为3质量%以上,优选为5质量%以上,更优选为6质量%以上。由此,能够提高导热性和金属密合性。相对于导热性膏整体,具有联苯骨架的酚醛树脂和(甲基)丙烯酸单体的含量的上限值例如为20质量%以下,优选为18质量%以下,更优选为15质量%以下。由此,能够实现导热系数与固化特性等导热性膏的各种特性的平衡。
(固化促进剂)
导热性膏例如可以包含固化促进剂。
当使用环氧树脂作为热固性树脂时,作为固化促进剂,例如可以使用促进环氧树脂与固化剂的交联反应的固化促进剂。这样的固化促进剂例如可以包含选自咪唑类、三苯基膦或四苯基膦的盐类、二氮杂二环十一烯等胺系化合物及其盐类、过氧化叔丁基异丙苯、过氧化二异丙苯、α,α’-双(叔丁基过氧基间异丙基)苯、2,5-二甲基-2,5-二(叔丁基过氧基)己烷、2,5-二甲基-2,5-二(叔丁基过氧基)已炔-3等有机过氧化物中的一种或两种以上。在这些之中,优选使用2-甲基咪唑、2-乙基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑、2-苯基-4-甲基-5-羟甲基咪唑、2-苯基-4,5-二羟甲基咪唑、2-C11H23-咪唑、2-甲基咪唑与2,4-二氨基-6-乙烯基三嗪的加成物等咪唑化合物。其中,尤其优选的是融点为180℃以上的咪唑化合物。
当使用氰酸酯树脂作为热固性树脂时,作为固化促进剂,例如可以使用包含选自辛酸锌、辛酸锡、环烷酸钴、环烷酸锌、乙酰丙酮铁等有机金属配位化合物、氯化铝、氯化锡、氯化锌等金属盐、三乙胺、二甲基苄胺等胺类中的一种或两种以上的固化促进剂。
在本实施方式中,相对于导热性膏整体,导热性膏中的固化促进剂的含量优选为0.05质量%以上,更优选为0.1质量%以上。由此,能够提高导热性膏的固化性。另一方面,相对于导热性膏整体,导热性膏中的固化促进剂的含量优选为1质量%以下,更优选为0.8质量%以下。由此,能够更有效地提高导热性膏的流动性。
(反应性稀释剂)
导热性膏例如可以包含反应性稀释剂。
反应性稀释剂例如可以包含选自苯基缩水甘油醚、甲苯缩水甘油醚、叔丁基苯基缩水甘油醚等单官能的芳香族缩水甘油醚类、脂肪族缩水甘油醚类中的一种或两种以上。由此,能够更有效地提高涂敷操作性,并且实现粘接层的平坦化。
在本实施方式中,相对于导热性膏整体,导热性膏中的反应性稀释剂的含量优选为3质量%以上,更优选为4质量%以上。由此,能够更有效地提高导热性膏的涂敷操作性和粘接层的平坦性。另一方面,相对于导热性膏整体,导热性膏中的反应性稀释剂的含量优选为20质量%以下,更优选为15质量%以下。由此,能够抑制涂敷作业中的液体滴落的发生等,实现涂敷操作性的提高。而且,还能够提高导热性膏的固化性。
本实施方式的导热性膏可以不包含溶剂。这里所说的溶剂是指不具有参与导热性膏中包含的热固性树脂的交联反应的反应性基团的非反应性溶剂。不包含是指实质上不包含,是指非反应性溶剂相对于导热性膏整体的含量为0.1质量%以下的情况。
另一方面,本实施方式的导热性膏也可以包含非反应性溶剂。
作为上述非反应性溶剂,例如可以举出:包括由三丙二醇丁醚、戊烷、己烷、庚烷、环己烷和十氢化萘等例示的烷烃和环烷烃的烃溶剂、甲苯、二甲苯、苯、均三甲苯等芳香族溶剂、乙醇、丙醇、丁醇、戊醇、己醇、庚醇、辛醇、壬醇、癸醇、乙二醇单甲醚、乙二醇单乙醚、乙二醇单丙醚、乙二醇单丁醚、丙二醇单甲醚、丙二醇单乙醚、丙二醇单丙醚、丙二醇单丁醚、甲基甲氧基丁醇、α-松油醇、β-松油醇、己二醇、苄醇、2-苯乙醇、异十六醇、异十八醇、月桂醇、乙二醇、丙二醇或丙三醇等醇类;丙酮、甲基乙基酮、甲基异丁酮、环己酮、二丙酮醇(4-羟基-4-甲基-2-戊酮)、2-辛酮、异佛尔酮(3,5,5-三甲基-2-环己烯-1-酮)或二异丁基酮(2,6-二甲基-4-庚酮)等酮类;乙酸乙酯、乙酸丁酯、邻苯二甲酸二乙酯、邻苯二甲酸二丁酯、乙酰氧基乙烷、丁酸甲酯、己酸甲酯、辛酸甲酯、癸酸甲酯、甲基溶纤剂乙酸酯、乙二醇单丁醚乙酸酯、丙二醇单甲醚乙酸酯、1,2-二乙酰氧基乙烷、磷酸三丁酯、磷酸三甲苯酯或磷酸三戊酯等酯类;四氢呋喃、二丙醚、乙二醇二甲醚、乙二醇二乙醚、乙二醇二丁醚、丙二醇二甲醚、乙氧基乙醚、1,2-双(2-二乙氧基)乙烷或1,2-双(2-甲氧基乙氧基)乙烷等醚类;乙酸2-(2-丁氧基乙氧基)乙烷等酯醚类;2-(2-甲氧基乙氧基)乙醇等醚醇类;正链烷烃、异链烷烃、十二烷基苯、松节油、煤油或轻油等烃类;乙腈或丙腈等腈类;乙酰胺或N,N-二甲基甲酰胺等酰胺类;低分子量的挥发性硅油或挥发性有机改性硅油。可以将这些单独使用,也可以将2种以上组合使用。
导热性膏可以根据需要包含其他添加剂。作为其他添加剂,可以举出由环氧硅烷、巯基硅烷、氨基硅烷、烷基硅烷、尿基硅烷、乙烯基硅烷、硫化物硅烷等硅烷偶联剂、钛酸酯偶联剂、铝偶联剂、铝/锆偶联剂等例示的偶联剂、炭黑等着色剂、硅油、硅橡胶等固形低应力化成分、水滑石等无机离子交换体、消泡剂、表面活性剂、各种阻聚剂和抗氧化剂等。导热性膏可以包含这些添加剂中的一种或两种以上。
本实施方式的导热性膏例如可以为膏状。
在本实施方式中,导热性膏的制备方法没有特别限定,例如可以将上述的各成分进行预混合后,利用3个辊进行混炼,进而进行真空脱泡,从而获得膏状的树脂组合物。此时,例如通过在减压下进行预混合等适当地调整制备条件,能够有助于提高导热性膏的长期操作性。
对本实施方式的导热性膏的特性进行说明。
本实施方式的导热性膏的粘度的下限值例如可以为10Pa·s以上,优选为20Pa·s以上,更优选为30Pa·s以上。由此,能够提高导热性膏的操作性。另一方面,上述导热性膏的粘度的上限值例如可以为103Pa·s以下,优选为5×102Pa·s以下,更优选为2×102Pa·s以下。由此,能够提高涂敷性。
在本实施方式中,粘度可以在室温25℃利用布氏粘度计(Brookfieldviscometer)进行测量。
本实施方式的导热性膏,由下述的测量方法计算出的润湿扩展面积的比例能够为90%以上。
(润湿扩展面积的测量方法)
将该导热性膏以呈对角线状交叉的方式涂敷在引线框的表面。接着,在室温25℃静置8小时。接着,将2mm×2mm的硅裸片(silicon bare chip)经由该导热性膏安装在上述引线框上后,用X射线装置进行观察,计算该导热性膏的上述润湿扩展面积相对于上述硅裸片的表面的比例。
对本实施方式的电子装置(半导体装置100)进行说明。
图1是表示本实施方式的电子装置(半导体装置100)的一个例子的截面图。
本实施方式的电子装置(半导体装置100)包括本实施方式的导热性膏的固化物。该固化物例如如图1所示,能够用作将基材(基板30)和电子部件(半导体元件20)粘接的粘接层10。
本实施方式的半导体装置100例如可以包括基板30和经由粘接层10搭载在基板30上的半导体元件20。半导体元件20和基板30例如通过接合线40电连接。半导体元件20和接合线40例如由使环氧树脂组合物等固化而形成的模制树脂50密封。
基板30例如为引线框或有机基板。在图1中例示了基板30为有机基板的情况。在该情况下,在基板30中的与搭载半导体元件20的正面相反的一侧的背面形成例如多个焊球60。
在本实施方式的半导体装置100中,粘接层10通过使上述中例示的导热性膏固化而形成。因此,能够稳定地制造半导体装置100。
在本实施方式中,也能够将导热性膏应用于例如MAP(Mold Array Package:模具阵列封装)成形品的制造。在该情况下,利用喷射分配器法(jet dispenser method)将导热性膏涂敷在基板上的多个区域,由此在基板上形成多个粘接层后,在各粘接层上搭载半导体元件。由此,能够进一步提高生产效率。作为MAP成形品,例如可以举出MAP-BGA(BallGrid Array:球栅阵列)、MAP-QFN(Quad Flat Non-Leaded Package:四方扁平无引脚封装)。
实施例
下面,参照实施例对本发明进行详细说明,但是本发明并不受这些实施例的记载的任何限定。
(导热性膏的制备)
对各实施例和各比较例,分别按照表1所示的配比来配合各成分,在常压下进行5分钟的预混合,在70cmHg的减压下进行15分钟的预混合。接着,利用3个辊进行混炼,并进行脱泡,从而获得了导热性膏。表1中的各成分的详细内容如下述。表1中的单位是质量%。
(热固性树脂)
热固性树脂1:双酚F型环氧树脂(日本化药株式会社(Nippon Kayaku Co.,Ltd.)制造,SB-403S)
热固性树脂2:具有联苯骨架的环氧树脂(在室温25℃为固体,三菱化学株式会社(Mitsubishi Chemical Corporation)制造,YX-4000K,重均分子量Mw:354)
(固化剂)
固化剂1:具有联苯骨架的酚醛树脂(在室温25℃为固体,本州化学工业株式会社(Honshu Chemical Industry Co.,Ltd.)制造,联苯酚)
固化剂2:具有双酚F骨架的酚醛树脂(在室温25℃为固体,DIC株式会社(DICCorporation)制造,DIC-BPF)
(导热性填料)
导热性填料1:银粉(福田金属箔粉工业株式会社(Fukuda Metal Foil&PowderCo.,Ltd.)制造,AgC-2611,片状)
导热性填料2:银粉(同和电子材料株式会社(DOWA Electronics Materials Co.,Ltd.)制造,AG2-1C,球状)
导热性填料的D50、D95利用激光衍射散射法测量。将结果示于表1。
(丙烯酸化合物)
丙烯酸化合物1:(甲基)丙烯酸单体(二甲基丙烯酸1,6-己二醇酯,共荣社化学株式会社(Kyoeisha Chemical Co.,Ltd.)制造,LIGHT ESTER 1.6HX)
丙烯酸化合物2:(甲基)丙烯酸单体(二甲基丙烯酸乙二醇酯,共荣社化学株式会社制造,LIGHT ESTER EG)
(固化促进剂)
固化促进剂1:有机过氧化物(化药Akzo株式会社(Kayaku Akzo Corporation)制造,Perkadox BC)
固化促进剂2:咪唑系(2-苯基-4,5-二羟甲基咪唑,四国化成工业株式会社(SHIKOKU CHEMICALS CORPORATION)制造,2PHZ)
(溶剂)
溶剂1:三丙二醇丁醚(日本乳化剂株式会社(Nippon Nyukazai Co.,Ltd.)制造,BFTG)
(反应性稀释剂)
反应性稀释剂1:单环氧单体(叔丁基苯基缩水甘油醚,日本化药株式会社制造,SBT-H)
对所获得的导热性膏进行了如下评价。将评价结果示于表1、表2。
(粘度)
利用布氏粘度计(HADV-3Ultra,Spindle CP-51(角度1.565°,半径1.2cm)),在25℃、0.5rpm的条件下测量刚制作后的上述导热性膏的粘度。粘度的单位是Pa·S。将评价结果示于表1。
(导热系数)
使用所获得的导热性膏制作1cm见方、厚度1mm的盘状的试验片(固化条件是175℃、4小时。其中,从室温经过60分钟升温至175℃)。根据通过激光闪光法(t1/2法)测量的热扩散系数(α)、通过DSC法测量的比热(Cp)、依照JIS-K-6911测量的密度(ρ)来计算导热系数(=α×Cp×ρ),将导热系数为5W/m·K以上的情况评价为合格。导热系数的单位是W/m·K。将评价结果示于表1。
(室温保存性)
在5cc的注射器(武藏株式会社(Musashi Co.,Ltd.)制造)中装满所获得的导热性膏,盖上中塞、外塞后,放置在注射器架上并在25℃的恒温槽中进行48h的处理。之后,通过目视确认外观,确认导热性膏有无分离。在表2中,将没有分离的情况表示为○,将有分离的情况表示为×。将评价结果示于表2。
(润湿扩展性)
将所获得的导热性膏以呈对角线状交叉的方式涂敷在铜制的引线框的表面。接着,在室温25℃静置8小时。接着,以50g、50ms的负荷将具有2mm×2mm的表面的硅裸片(厚度0.525mm)经由该导热性膏安装在引线框上后,用X射线装置进行观察。通过对由X射线观察获得的图像进行二值化,计算出该导热性膏的润湿扩展面积相对于硅裸片的表面积100%的比例(%)。将评价结果示于表2。
(喷出稳定性(拉丝发生率))
将在5cc的注射器(武藏株式会社制造)中装满的所获得的导热性膏设置在Shotmaster 300(武藏株式会社制造)中,以喷出压力100kPa、喷出时间100ms实施打点涂敷(280个点)。之后,通过目视确认涂敷形状不是圆形的点的数量(拉丝数),计算出相对于280个点的比例,将其作为拉丝发生率(%)。将评价结果示于表1。
(吸湿后芯片抗切强度)
使用所获得的导热性膏,将镀银(Ag)片(长×宽×厚度:2mm×2mm×0.35mm)安装在支撑体镀银(Ag)框(新光电气工业株式会社(SHINKO ELECTRIC INDUSTRIES CO.,LTD.)制造,在铜的引线框上镀银(Ag)而得到)上,利用烘箱以175℃、60分钟(以升温速度5℃/分钟从25℃升温至175℃)的固化温度曲线进行固化从而制成样品1。
另外,使用所获得的导热性膏,将镀金(Au)片(长×宽×厚度:2mm×2mm×0.35mm)安装在镀金(Au)片(长×宽×厚度:5mm×5mm×0.35mm)上,利用烘箱以175℃、60分钟(以升温速度5℃/分钟从25℃升温至175℃)的固化温度曲线进行固化从而制成样品2。
对所获得的样品1、2,在85℃、湿度85%的条件下进行72小时吸湿处理后,测量260℃的热时芯片抗切强度(单位:N/1mm2)。将评价结果示于表1。
得知实施例1~4的导热性膏与比较例1、2相比,导热性(导热系数)和金属密合性(芯片抗切强度)优异。并且,得知实施例1~4的导热性膏的喷出稳定性、室温保存性和润湿扩展性也优异。
本申请以2016年10月31日申请的日本申请特愿2016-213663号为基础主张优先权,将其揭示的全部内容编入于此。
Claims (15)
1.一种导热性膏,其包含热固性树脂、固化剂、丙烯酸化合物和导热性填料,所述导热性膏的特征在于:
所述热固性树脂和所述固化剂中的至少一者包含具有联苯骨架的树脂,
所述丙烯酸化合物包含(甲基)丙烯酸单体。
2.根据权利要求1所述的导热性膏,其特征在于:
所述具有联苯骨架的树脂包含具有联苯骨架的酚醛树脂。
3.根据权利要求1或2所述的导热性膏,其特征在于:
该导热性膏的粘度为10Pa·s以上103Pa·s以下。
4.根据权利要求1至3中任一项所述的导热性膏,其特征在于:
所述导热性填料包含金属、氧化物或氮化物。
5.根据权利要求1至4中任一项所述的导热性膏,其特征在于:
所述导热性填料含有选自银、铜、氧化铝中的一种以上。
6.根据权利要求1至5中任一项所述的导热性膏,其特征在于:
所述导热性填料的平均粒径D50为0.1μm以上10μm以下。
7.根据权利要求1至6中任一项所述的导热性膏,其特征在于:
所述导热性填料的平均粒径D95为1μm以上15μm以下。
8.根据权利要求1至7中任一项所述的导热性膏,其特征在于:
相对于该导热性膏整体,所述导热性填料的含量为50质量%以上88质量%以下。
9.根据权利要求1至8中任一项所述的导热性膏,其特征在于:
由下述的测量方法计算出的润湿扩展面积的比例为90%以上,
润湿扩展面积的测量方法:
将该导热性膏以呈对角线状交叉的方式涂敷在引线框的表面,接着,在室温25℃静置8小时,接着,将2mm×2mm的硅裸片经由该导热性膏安装在所述引线框上后,计算该导热性膏的所述润湿扩展面积相对于所述硅裸片的表面的比例。
10.根据权利要求1至9中任一项所述的导热性膏,其特征在于:
不包含溶剂。
11.根据权利要求1至10中任一项所述的导热性膏,其特征在于:
相对于该导热性膏整体,所述具有联苯骨架的树脂和所述(甲基)丙烯酸单体的含量为3质量%以上20质量%以下。
12.根据权利要求1至11中任一项所述的导热性膏,其特征在于:
相对于所述具有联苯骨架的树脂和所述(甲基)丙烯酸单体的总量100质量%,所述(甲基)丙烯酸单体的含量为30质量%以上95质量%以下。
13.根据权利要求1至12中任一项所述的导热性膏,其特征在于:
包含反应性稀释剂。
14.根据权利要求1至13中任一项所述的导热性膏,其特征在于:
包含固化促进剂。
15.一种电子装置,其特征在于:
包括权利要求1至14中任一项所述的导热性膏的固化物。
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PCT/JP2017/038314 WO2018079533A1 (ja) | 2016-10-31 | 2017-10-24 | 熱伝導性ペーストおよび電子装置 |
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CN111276645A (zh) * | 2020-03-23 | 2020-06-12 | 成都科成精化科技有限公司 | 一种锂电池铝塑膜胶粘剂的填料增强体系设计方法 |
CN115023453A (zh) * | 2020-01-29 | 2022-09-06 | 住友电木株式会社 | 膏状树脂组合物、高导热性材料和半导体装置 |
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TWI700330B (zh) * | 2018-11-09 | 2020-08-01 | 台光電子材料股份有限公司 | 樹脂組合物及由其製成之物品 |
EP4053213B1 (en) * | 2019-10-30 | 2024-04-10 | Mitsubishi Chemical Corporation | Resin composition, cured product, composite molded body and semiconductor device |
JPWO2022097443A1 (zh) * | 2020-11-04 | 2022-05-12 |
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