CN113272355A - 树脂组合物和金属基覆铜层叠板 - Google Patents
树脂组合物和金属基覆铜层叠板 Download PDFInfo
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- CN113272355A CN113272355A CN201980085971.1A CN201980085971A CN113272355A CN 113272355 A CN113272355 A CN 113272355A CN 201980085971 A CN201980085971 A CN 201980085971A CN 113272355 A CN113272355 A CN 113272355A
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Images
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
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
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- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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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
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- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
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Abstract
本发明的树脂组合物用于形成由金属板(101)、应力缓和层(102)和铜箔(103)依次层叠而构成的金属基覆铜层叠板(100)的应力缓和层(102),所述树脂组合物含有:具有聚醚结构的环氧树脂、苯氧基树脂和散热性填料,且满足25℃时的储能模量为0.01GPa以上1.6GPa以下的特性。
Description
技术领域
本发明涉及树脂组合物和金属基覆铜层叠板。
背景技术
迄今为止,对金属基覆铜层叠板进行了各种开发。作为这种技术,例如已知专利文献1中记载的技术。专利文献1中记载了一种高散热用引线框基板,其由金属板(铜)、绝缘材料(含有热固性树脂和高散热性填料)、引线框材料(铜)依次层叠而成(专利文献1的权利要求书、图1)。
现有技术文献
专利文献
专利文献1:日本特开2014-99574号公报
发明内容
发明要解决的技术问题
然而,本发明人进行研究的结果,发现:在上述专利文献1中记载的金属基覆铜层叠板中,在耐焊料龟裂性和剥离强度方面尚有改善的余地。
用于解决技术问题的手段
本发明人进一步进行研究的结果,发现:通过与苯氧基树脂一并同时使用具有聚醚结构的环氧树脂,含有它们的树脂组合物的固化物具有能够适合用于配置在金属板与铜箔之间的应力缓和层的特性。本发明人根据这样的见解进一步深入研究的结果,发现:通过适当地控制该树脂组合物的固化物的弹性模量,在由金属板、应力缓和层和铜箔依次层叠而构成的金属基覆铜层叠板中,能够提高耐焊料龟裂性和剥离强度,从而完成了本发明。
根据本发明,提供一种树脂组合物,其用于形成由金属板、应力缓和层和铜箔依次层叠而构成的金属基覆铜层叠板的所述应力缓和层,所述树脂组合物的特征在于,含有:具有聚醚结构的环氧树脂;苯氧基树脂;和散热性填料,使用动态粘弹性测定机,在测定温度:-50℃~200℃、升温速度:5℃/分钟、频率:1Hz、拉伸模式的条件下,对将该树脂组合物在80℃加热处理30分钟、在180℃加热处理60分钟而得到的样品进行测定,测得的25℃时的储能模量为0.01GPa以上1.6GPa以下。
并且,根据本发明,提供一种金属基覆铜层叠板,其特征在于,包括:作为散热部件发挥功能的金属板;设置在所述金属板上的应力缓和层;和设置在所述应力缓和层上的电路形成用的厚膜铜箔,所述应力缓和层由树脂层构成,所述树脂层由上述的树脂组合物构成。
发明效果
根据本发明,能够提供耐焊料龟裂性和剥离强度优异的树脂组合物和使用该树脂组合物的金属基覆铜层叠板。
附图说明
上述的目的和其他的目的、特征和优点,通过下面说明的优选实施方式及其附带的下述附图将会变得更明确。
图1是示意性地表示本实施方式的金属基覆铜层叠板的一个例子的截面图。
图2是示意性地表示本实施方式的电子装置的一个例子的截面图。
具体实施方式
以下,使用附图对本发明的实施方式进行说明。另外,在所有附图中,对相同的构成要件标注相同的附图标记,并适当省略说明。并且,图为概略图,与实际的尺寸比率并不一致。
下面对本实施方式的树脂组合物的概要进行说明。
本实施方式的树脂组合物包含具有聚醚结构的环氧树脂、苯氧基树脂和散热性填料,用于形成由金属板、应力缓和层和铜箔依次层叠而构成的金属基覆铜层叠板的应力缓和层。
并且,该树脂组合物具有如下特性:使用动态粘弹性测定机,在测定温度:-50℃~200℃、升温速度:5℃/分钟、频率:1Hz、拉伸模式的条件下,对将该树脂组合物在80℃加热处理30分钟、在180℃加热处理60分钟而得到的样品进行测定,测得的25℃时的储能模量为0.01GPa以上1.6GPa以下。
根据本发明人的见解,发现:通过与苯氧基树脂一并同时使用具有聚醚结构的环氧树脂,含有它们的树脂组合物的固化物具有能够适合用于配置在金属板与铜箔之间的应力缓和层的特性。
并且,通过适当地控制该树脂组合物的固化物的弹性模量以使其成为上述上限值以下,能够提高由金属板、应力缓和层和铜箔依次层叠而构成的金属基覆铜层叠板的耐焊料龟裂性。
在本实施方式中,上述25℃时的储能模量的上限值例如为1.6GPa以下,优选为1.5GPa以下,更优选为1.0GPa以下。由此,能够提高耐焊料龟裂性和剥离强度。另一方面,上述25℃时的储能模量的下限值并无特别限定,例如可以为0.01GPa以上,优选为0.05GPa以上,更优选为0.10GPa以上。也可以是根据金属基覆铜层叠板中的金属板的线膨胀系数来选择适当的储能模量。
在本实施方式中,例如能够通过适当地选择树脂组合物中包含的各成分的种类和配方量、树脂组合物的制备方法等,来控制上述储能模量。其中,作为用于使上述储能模量成为所期望的数值范围的要素,例如可举出具有聚醚结构的环氧树脂、苯氧基树脂的使用、固化剂和散热性填料的种类的适当选择、这些成分的含量的调整等。
根据本实施方式,能够在包括搭载在金属基覆铜层叠板上的电子部件的电子装置中提供连接可靠性优异的结构。
以下,对本实施方式的树脂组合物进行详细说明。
上述树脂组合物中,作为环氧树脂,包含具有聚醚结构的环氧树脂。由此,能够降低树脂组合物的固化物的弹性模量,并且能够提高剥离强度。
上述具有聚醚结构的环氧树脂可以包含由下述通式(I)表示的化合物。由下述通式(I)表示的化合物具有适当长度的聚醚结构,因此,能够使固化物低弹性化,而且在两个末端具有反应性官能团(例如,环氧基),因此,能够提高反应性从而提高剥离强度。
上述通式(I)中,R1和R2分别独立地表示氢原子或甲基,G表示缩水甘油基。m和n分别独立地为1以上的整数,且满足由3≤(m+n)≤20表示的关系。
并且,通过包含具有聚醚结构的环氧树脂,能够提高金属基覆铜层叠板的应力缓和力。例如,在制造电子装置的情况下,即使在急剧的加热/冷却的环境下,也能够抑制在将电子部件和金属基覆铜层叠板接合的焊接部或其附近发生龟裂等不良情况。这样能够提高金属基覆铜层叠板的热循环特性。
上述树脂组合物中,作为环氧树脂,除了包含具有聚醚结构的环氧树脂以外,还可以包含其他的环氧树脂(A)。
上述环氧树脂(A)可以包含具有芳香环结构和脂环结构(脂环式碳环结构)中的至少任一者的环氧树脂(A1)。通过使用这样的环氧树脂(A1),能够提高玻璃化转变温度,并且提高树脂层102的导热性。
作为具有芳香环或脂肪环结构的环氧树脂(A1),例如可举出双酚A型环氧树脂、双酚F型环氧树脂、双酚S型环氧树脂、双酚E型环氧树脂、双酚M型环氧树脂、双酚P型环氧树脂、双酚Z型环氧树脂等双酚型环氧树脂、苯酚酚醛清漆型环氧树脂、甲酚酚醛清漆型环氧树脂、四酚基乙烷型酚醛清漆型环氧树脂等酚醛清漆型环氧树脂、联苯型环氧树脂、具有亚联苯基骨架的酚芳烷基型环氧树脂等芳基亚烷基型环氧树脂、萘型环氧树脂等环氧树脂等。可以单独使用其中的1种,也可以同时使用2种以上。
并且,上述树脂组合物中,作为环氧树脂,可以含有液态环氧树脂。
上述液态环氧树脂能够表现出将树脂组合物B阶段化时的片材的可挠性。
作为上述液态环氧树脂,可以使用具有2个以上的环氧基且在室温25℃时为液态的环氧化合物。
作为上述液态环氧树脂,例如可以包含选自双酚A二缩水甘油醚、双酚F二缩水甘油醚、烷基二缩水甘油醚和脂环式环氧树脂中的一种以上。并且,作为上述液态环氧树脂,也可以使用上述具有聚醚结构的环氧树脂。它们可以单独使用,也可以将2种以上组合使用。
上述液态环氧树脂的环氧当量的下限值例如为200g以上,优选为300g/eq以上,进一步优选为350g/eq以上。上述液态环氧树脂的环氧当量的上限值并无特别限定,例如可以为700g/eq以下。
相对于除散热性填料以外的树脂组合物的总固体成分100质量%,上述具有聚醚结构的环氧树脂的含量例如为5质量%~50质量%,优选为10质量%~45质量%,更优选为15质量%~40质量%。通过使上述具有聚醚结构的环氧树脂的含量成为上述下限值以上,能够降低固化物的弹性模量,并且提高剥离强度。并且,通过使上述具有聚醚结构的环氧树脂的含量成为上述上限值以下,能够实现与其他特性的平衡。
相对于除散热性填料以外的树脂组合物的总固体成分100质量%,上述环氧树脂的含量例如为20质量%~65质量%,优选为25质量%~60质量%,更优选为30质量%~60质量%。
树脂组合物中,作为环氧树脂,也可以包含具有聚醚结构的环氧树脂和液态环氧树脂。此时,树脂组合物中,具有聚醚结构的环氧树脂的含量/液态环氧树脂的含量为0.8~4.0,优选为0.9~3.5,更优选为1.0~3.0。通过使它们的含量之比在这样的范围内,能够实现树脂组合物的涂敷性与作为膜的低弹性的平衡。
在本实施方式中,树脂组合物的固体成分是指树脂组合物中的不挥发成分,是指除水和溶剂等挥发成分以外的剩余部分。在含有溶剂的情况下,相对于树脂组合物的总固体成分的含量是指相对于树脂组合物中除溶剂以外的总固体成分(100质量%)的含量。
上述树脂组合物包含散热性填料。由此,能够提高固化物的导热性。
作为上述散热性填料,可以使用导热性优异的公知的填料,例如可举出氧化铝。它们可以单独使用,也可以将2种以上组合使用。
氧化铝可以具有平均粒径不同的2种以上的成分。例如,可以是,氧化铝为平均粒径不同的3种成分(大粒径、中粒径、小粒径)的混合体系,大粒径成分为球状,中粒径成分和小粒径成分为多面体状。
氧化铝可以包含平均粒径属于5.0μm以上50μm以下、优选5.0μm以上25μm以下的第1粒径范围,并且圆度为0.80以上1.0以下、优选0.85以上0.95以下的大粒径氧化铝。
并且,氧化铝也可以包含平均粒径属于1.0μm以上且小于5.0μm的第2粒径范围,并且圆度为0.50以上0.90以下、优选0.70以上0.80以下的中粒径氧化铝。
并且,氧化铝也可以包含平均粒径属于0.1μm以上且小于1.0μm的第3粒径范围,并且圆度为0.50以上0.90以下、优选0.70以上0.80以下的小粒径氧化铝。
在此,粒径可以使用激光衍射式粒度分布测定装置SALD-7000,通过对氧化铝进行1分钟超声波处理使其分散在水中来进行测定。
通过使用具有适当粒径的氧化铝,能够提高氧化铝的填充性,使氧化铝颗粒彼此的接触面积更大。其结果,能够进一步提高固化物的导热性。而且,能够进一步提高固化物的焊料耐热性、抗弯性、绝缘性。并且,通过使用这样的氧化铝,能够进一步提高应力树脂层与金属板之间的密合性。通过这些的协同效应,能够进一步提高金属基覆铜层叠板的绝缘可靠性。
相对于该树脂组合物100体积%,上述散热性填料(或氧化铝)的含量例如为40体积%以上85体积%以下,优选为45体积%以上80体积%以下,更优选为55体积%以上75体积%以下。通过使上述散热性填料的含量成为上述下限值以上,能够提高固化物的导热性,从而实现散热性优异的电子装置。另一方面,通过使上述散热性填料的含量成为上述上限值以下,能够实现与其他特性的平衡。并且,能够提高制造稳定性。
上述树脂组合物含有苯氧基树脂。通过含有苯氧基树脂,能够提高固化物的抗弯性,因此,能够抑制由氧化铝的高填充引起的操作性的降低。
作为上述苯氧基树脂,例如可举出具有双酚骨架的苯氧基树脂、具有萘骨架的苯氧基树脂、具有蒽骨架的苯氧基树脂、具有联苯骨架的苯氧基树脂等。并且,还可以使用具有多种这些骨架的结构的苯氧基树脂。
其中,优选使用双酚A型或双酚F型苯氧基树脂。也可以使用具有双酚A骨架和双酚F骨架两者的苯氧基树脂。
上述苯氧基树脂的重均分子量并无特别限定,但优选为4.0×104以上8.0×104以下。
另外,苯氧基树脂的重均分子量为通过凝胶渗透色谱法(GPC)测定的聚苯乙烯换算值。
例如,相对于除散热性填料以外的树脂组合物的总固体成分100质量%,上述苯氧基树脂的含量例如为15质量%~60质量%,优选为18质量%~55质量%,更优选为20质量%~50质量%。
树脂组合物中,具有聚醚结构的环氧树脂的含量/苯氧基树脂的含量为0.7~4.0,优选为0.8~3.0,更优选为0.9~2.5。通过使它们的含量之比在这样的范围内,能够使由树脂组合物构成的膜的应力缓和力适当,能够提高耐焊料龟裂性、剥离强度和绝缘可靠性。
上述树脂组合物可以含有固化剂。
作为上述固化剂(固化催化剂),例如可举出:环烷酸锌、环烷酸钴、辛酸锡、辛酸钴、双乙酰丙酮钴(II)、三乙酰丙酮钴(III)等有机金属盐;双氰胺、二亚乙基三胺、三亚乙基四胺、间苯二甲胺、二氨基二苯基甲烷、二氨基二乙基二苯基甲烷、间苯二胺、二氨基二苯砜、异佛尔酮二胺、降冰片烯二胺、三乙胺、三丁胺、二氮杂双环[2,2,2]辛烷等胺类固化剂;2-苯基-咪唑、2-苯基-4-甲基咪唑、2-乙基-4-甲基咪唑、2-乙基-4-乙基咪唑、2-苯基-4-甲基-5-羟基咪唑、2-苯基-4,5-二羟基咪唑等咪唑类固化剂;三苯基膦、三对甲苯基膦、四苯基硼四苯基磷、三苯基膦-三苯基硼烷、1,2-双-(二苯基膦)乙烷等有机磷化合物;苯酚、双酚A、壬基酚等酚化合物;乙酸、苯甲酸、水杨酸、对甲苯磺酸等有机酸等或它们的混合物。作为固化剂,可以是包括这些物质的衍生物在内单独使用1种,也可以是包括这些物质的衍生物在内同时使用2种以上。
其中,从获得接合性优异、在较低温度下反应且耐热性优异的固化物的观点出发,优选胺类固化剂、咪唑类固化剂,从低弹性化的观点出发,更优选咪唑类固化剂。
固化催化剂的含量并无特别限定,相对于树脂组合物的总固体成分100质量%,固化催化剂的含量例如为0.05质量%以上3.0质量%以下。
上述树脂组合物可以含有偶联剂。偶联剂能够提高环氧树脂与氧化铝的界面的湿润性。
作为上述偶联剂,只要是通常使用的偶联剂,则可以使用任何偶联剂,具体而言,优选使用选自环氧基硅烷偶联剂、阳离子硅烷偶联剂、氨基硅烷偶联剂、钛酸酯类偶联剂和硅油型偶联剂中的1种以上的偶联剂。
上述偶联剂的添加量取决于氧化铝的比表面积,因此并无特别限定,但是相对于氧化铝100质量份优选为0.05质量份以上3质量份以下,尤其优选为0.1质量份以上2质量份以下。
上述树脂组合物可以在不损害本发明的效果的范围内含有其他成分。作为其他成分,可举出抗氧化剂、均化剂等。
接着,对金属基覆铜层叠板100进行说明。
图1是示意性地表示金属基覆铜层叠板100的一个例子的截面图。
图1的金属基覆铜层叠板100具有金属板101、树脂层102和金属层103。金属板101、树脂层102和金属层103构成依次层叠的层叠结构。金属板101作为散热部件发挥功能。树脂层102为应力缓和层。金属层103用于形成电路形成。
金属板101为含有Ag或Cu作为主要成分的金属材料的板状部件。主要成分是指金属材料中的含有比率例如为80质量%以上,更优选为85质量%以上。金属板101可以为由金属构成的板状基板,也可以为由含有其他半导体元素或金属元素的合金构成的板状基板。作为其他半导体元素或金属元素,例如可以含有Si、Fe、Cu、Mn、Mg、Cr、Zn、Ti等。它们可以单独使用,也可以将2种以上组合使用。
其中,从比铜基板轻且低成本的观点出发,金属板101可以使用铝板或合金铝板。
金属板101的厚度可以为能够发挥作为基板的支撑部件的功能的程度的厚度,例如为0.5mm~3.0mm,更优选为1.0mm~2.0mm。金属板101可以由单层或多层的层叠体构成。
树脂层102由树脂层构成,该树脂层由上述树脂组合物构成。具体而言,树脂层102由上述树脂组合物的固化物构成。
树脂层102的厚度可以适当选择,例如为30μm~300μm,优选为30μm~200μm,更优选为50μm~120μm。
金属层103由铜箔构成,更优选由厚膜铜箔构成。金属层103只要由以Cu为主要成分的金属材料构成即可,可以具有Al、Ni、Fe、Sn等其他金属元素。它们可以单独使用,也可以将2种以上组合使用。
金属层103的厚度例如为10μm~80μm,优选为15μm~70μm。通过使金属层103厚膜化,能够减小电阻,因此,能够实现可适用于大电流的金属基覆铜层叠板100。
接着,对金属基覆铜层叠板100的制造方法进行说明。
在准备的金属板101上形成由树脂组合物构成的B阶段状态的树脂层。
形成树脂层的方法可以使用将上述树脂组合物涂敷在金属层103上并进行干燥的方法或将层叠膜状树脂层的方法。
接着,在树脂层的表面上形成金属板101。形成金属板101的方法可以使用利用压制等对树脂层和金属板101进行加压、加热处理的方法。在进行该加压、加热处理时,在树脂层为B阶段状态的情况下,可以使该树脂层固化。
由此,获得金属基覆铜层叠板100。
然后,根据需要,可以通过将金属层103蚀刻成规定的图案等来形成金属电路层105。由此,获得具有金属板101、树脂层102和金属电路层105的金属基覆铜层叠板100。
另外,金属基覆铜层叠板100可以具有将金属板101、树脂层102和金属电路层105的单位结构层叠多个而得到的多层结构。
并且,金属基覆铜层叠板100可以在最外层具有阻焊层。阻焊层可以具有用于使能够与后述的电子部件连接的电极部露出的开口。
接着,对本实施方式的电子装置1进行说明。
图2是示意性地表示电子装置1的一个例子的截面图。
图2的电子装置1包括:金属基覆铜层叠板100;设置在金属基覆铜层叠板100上的电子部件11;和将它们连接的连接部(焊料15)。该电子装置1可以包括图2中未图示的公知的其他部件。例如,电子装置1可以包括用于将电子部件11密封的密封部件。
电子部件11为晶体管、发光二极管(LED)等半导体元件、电阻、电容器等各种发热元件。它们可以单独使用,也可以将2种以上组合使用。
电子装置1为用于搭载在混合动力汽车、燃料电池车和电动汽车等汽车或飞机、火箭等交通工具中的用途、搭载在便携式设备的内部那样的狭窄的空间中的用途等的电子设备。电子装置1例如为功率半导体装置、LED照明装置、逆变器装置等半导体装置。
根据本实施方式,即使电子装置1长时间或反复放置在温度剧烈变化的环境下,作为应力缓和层的树脂层102也能够稳定地降低因金属基覆铜层叠板100与电子部件11之间产生的热膨胀系数差而产生的应力。
在金属基覆铜层叠板100的金属板101由铝板或合金铝板构成的情况下,铝虽然轻,但是具有根据环境温度而大幅伸缩的特性,因此,铝基覆铜层叠板中的金属板101与电子部件11之间的热膨胀系数的背离变大。
根据本发明人的研究,发现:与使用铜板的情况相比,对树脂层102要求更高的应力缓和特性。
对此,树脂层102被低弹性模量化,因此,通过使用应力缓和特性优异的树脂组合物的固化物,能够抑制因它们之间的热膨胀系数的背离(失配)而导致焊料15产生龟裂。
并且,由上述树脂组合物的固化物构成的树脂层102能够具有剥离强度、热导率、绝缘性等也优异的特性。
因此,金属基覆铜层叠板100能够适合用作用于搭载LED等电子部件11的散热电路基板。
并且,电子装置1具有在金属基覆铜层叠板100上搭载有电子部件11的结构,因此,耐焊料龟裂性优异,即使在从低温环境至高温环境、或在它们之间变动那样的严酷的环境下,连接可靠性也优异。
以上,对本发明的实施方式进行了说明,但是这些仅为本发明的例示,也可以采用上述以外的各种构成。并且,本发明并不限定于上述实施方式,能够实现本发明的目的的范围内的变形、改进等也包括在本发明中。
[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。
表1所示的原料成分的信息如下。
(苯氧基树脂)
·苯氧基树脂1:具有双酚F骨架和双酚A骨架的苯氧基树脂(三菱化学株式会社(Mitsubishi Chemical Corporation)制造、4275、重均分子量6.0×104、双酚F骨架与双酚A骨架的比率=75:25)
(环氧树脂)
·环氧树脂1:双酚F型环氧树脂(DIC株式会社(DIC Corporation)制造、830S、液态环氧树脂、环氧当量:170g/eq)
·环氧树脂2:聚醚型环氧树脂(EP-4005、株式会社艾迪科(ADEKA Corporation)制造、在25℃为液体、粘度0.8Pa·s、环氧当量510g/eq)
·环氧树脂3:全丙烯酸结构的丙烯酸树脂(东亚合成株式会社(TOAGOSEI CO.,LTD.)制造、ARUFON UG-4010、重均分子量:2,900)
·环氧树脂4:含有聚丁二烯骨架的环氧化聚丁二烯(株式会社大赛璐(DaicelCorporation)制造、PB3600、重均分子量:5,900)
(固化剂)
·固化剂1:咪唑(四国化成株式会社(SHIKOKU CHEMICALS CORPORATION)制造、商品名:2P4MZ)
·固化剂2:双氰胺(德固赛公司(Degussa AG)制造)
·固化剂3:酚醛清漆型酚醛树脂(住友电木株式会社(Sumitomo Bakelite Co.,Ltd.)制造、商品名:PR-51470)
(偶联剂)
·硅烷偶联剂1:γ-环氧丙氧基丙基三甲氧基硅烷(信越有机硅株式会社(Shin-Etsu Silicone Co.,Ltd.)制造、KBM-403)
(散热性填料)
·散热性填料1:球状氧化铝(平均粒径:22μm、圆度:0.91、新日铁住金材料株式会社(NIPPON STEEL&SUMIKIN MATERIALS CO.,LTD.)制造、AX-25)
·散热性填料2:多面体状氧化铝(平均粒径:4μm、圆度:0.75、日本轻金属株式会社(Nippon Light Metal Company,Ltd.)制造、LS-210)
·散热性填料3:多面体状氧化铝(平均粒径:0.7μm、圆度:0.71、Nippon LightMetal Co.,Ltd.制造、LS-250)
[表1]
<树脂组合物的制备>
根据表1所示的配合比率,将各成分在环己酮中溶解、混合,使用高速搅拌装置进行搅拌,得到以固体成分基准计为80质量%的清漆状的树脂组合物。
<金属基覆铜层叠板的制作>
作为金属箔,使用厚度18μm的铜箔(古河电路铜箔株式会社(Furukawa CircuitFoil Co.,Ltd.)制造、GTSMP)。利用缺角轮涂敷机(comma coater)在铜箔的粗化面上涂敷清漆状的树脂组合物,在100℃加热干燥3分钟,在150℃加热干燥3分钟,得到带树脂厚度80μm的树脂的铜箔。
将所得到的带树脂铜箔和1.5mm厚的铝板(#4045)贴合,利用真空压制,在压制压力100kg/cm2、80℃、30分钟、180℃、60分钟的条件下进行压制,得到金属基覆铜层叠板(绝缘树脂层的厚度:80μm)。
(热导率)
从金属基覆铜层叠板剥离铜箔和铝板,得到绝缘树脂层。然后,测量绝缘树脂层的厚度方向上的热导率。具体而言,由利用激光闪光法(半衰期法(half-time method))测定的热扩散系数(α)、利用DSC法测定的比热(Cp)、按照JIS-K-6911测定的密度(ρ),使用下式计算出热导率。热导率的单位为W/m·K。热导率[W/m·K]=α[m2/s]×Cp[J/kg·K]×ρ[g/cm3]
(储能模量(E’))
从金属基覆铜层叠板剥离铜箔和铝板,得到绝缘树脂层。然后,对绝缘树脂层进行切削,得到8×20mm的试验片。利用动态粘弹性测定装置,在拉伸模式、频率1Hz、升温速度5℃/分钟的条件下,在-50℃~200℃的温度范围内进行测定。然后,得到25℃时的储能模量(GPa)。
(绝缘击穿电压)
利用研磨锯(grinder saw)将金属基覆铜层叠板切割成100mm×100mm之后,通过蚀刻将铜箔除去,制作出试样。使用耐电压试验器(MODEL7473、华仪电子(EXTECHElectronics)公司制造),使电极与绝缘树脂层和铝板接触,对两个电极施加交流电压,使电压以0.5kV/秒的速度上升。将金属基覆铜层叠板的绝缘树脂层击穿的电压作为绝缘击穿电压(kV)。
(剥离强度)
利用研磨锯将金属基覆铜层叠板切割成100mm×25mm之后,通过蚀刻制作出中央留有100mm×10mm的铜箔的试样,测定23℃时的铜箔与绝缘树脂层之间的剥离强度(kN/m)。剥离强度测定是按照JIS C 6481进行的。
(焊料耐热性)
利用研磨锯将金属基覆铜层叠板切割成50mm×50mm之后,通过蚀刻制作出留有1/2的铜箔的试样,按照JIS C 6481进行评价。评价是在260℃的焊料槽中浸渍30秒钟之后检查外观有无异常。
评价基准○:无异常
×:有异常(整体上存在膨胀的部位)
发现实施例1~3的树脂组合物热导率高,能够实现与比较例1~3相比能够低弹性化,与比较例1~3相比剥离强度高,与比较例2、3相比耐焊料龟裂性、绝缘可靠性优异的金属基覆铜层叠板。这样的金属基覆铜层叠板能够适合用作用于搭载LED等电子部件的散热电路基板。
本申请以2018年12月26日申请的日本申请特愿2018-243315号为基础要求优先权,并将其公开的全部内容援用于此。
Claims (10)
1.一种树脂组合物,其用于形成由金属板、应力缓和层和铜箔依次层叠而构成的金属基覆铜层叠板的所述应力缓和层,
所述树脂组合物的特征在于,含有:
具有聚醚结构的环氧树脂;
苯氧基树脂;和
散热性填料,
使用动态粘弹性测定机,在测定温度:-50℃~200℃、升温速度:5℃/分钟、频率:1Hz、拉伸模式的条件下,对将该树脂组合物在80℃加热处理30分钟、在180℃加热处理60分钟而得到的样品进行测定,测得的25℃时的储能模量为0.01GPa以上1.6GPa以下。
3.根据权利要求1或2所述的树脂组合物,其特征在于:
含有固化剂。
4.根据权利要求3所述的树脂组合物,其特征在于:
所述固化剂包含咪唑类固化剂。
5.根据权利要求1至4中任一项所述的树脂组合物,其特征在于:
所述散热性填料包含氧化铝。
6.根据权利要求5所述的树脂组合物,其特征在于:
所述氧化铝包含平均粒径不同的2种以上的氧化铝。
7.根据权利要求1至6中任一项所述的树脂组合物,其特征在于:
相对于该树脂组合物100体积%,所述散热性填料的含量为40体积%以上85体积%以下。
8.根据权利要求1至7中任一项所述的树脂组合物,其特征在于:
含有液态环氧树脂。
9.根据权利要求1至8中任一项所述的树脂组合物,其特征在于:
所述金属板为铝基板。
10.一种金属基覆铜层叠板,其特征在于,包括:
作为散热部件发挥功能的金属板;
设置在所述金属板上的应力缓和层;和
设置在所述应力缓和层上的电路形成用的厚膜铜箔,
所述应力缓和层由树脂层构成,所述树脂层由权利要求1至9中任一项所述的树脂组合物构成。
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US20110159296A1 (en) * | 2008-08-18 | 2011-06-30 | Sekisui Chemical Co., Ltd. | Insulating sheet and laminated structure |
CN107708999A (zh) * | 2015-08-25 | 2018-02-16 | 三井金属矿业株式会社 | 带树脂层的金属箔、覆金属层叠板和印刷电路板的制造方法 |
JP2018184525A (ja) * | 2017-04-26 | 2018-11-22 | 信越化学工業株式会社 | 低温硬化型液状エポキシ樹脂組成物 |
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JP2015010098A (ja) * | 2013-06-26 | 2015-01-19 | Dic株式会社 | 熱接着シート及び物品 |
US20160362582A1 (en) * | 2015-06-13 | 2016-12-15 | Mitsubishi Plastics, Inc. | Adhesive film |
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US20110159296A1 (en) * | 2008-08-18 | 2011-06-30 | Sekisui Chemical Co., Ltd. | Insulating sheet and laminated structure |
CN107708999A (zh) * | 2015-08-25 | 2018-02-16 | 三井金属矿业株式会社 | 带树脂层的金属箔、覆金属层叠板和印刷电路板的制造方法 |
JP2018184525A (ja) * | 2017-04-26 | 2018-11-22 | 信越化学工業株式会社 | 低温硬化型液状エポキシ樹脂組成物 |
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