CN110168015A - 树脂组合物、带树脂铜箔、介电层、覆铜层压板、电容器元件以及内置电容器的印刷电路板 - Google Patents
树脂组合物、带树脂铜箔、介电层、覆铜层压板、电容器元件以及内置电容器的印刷电路板 Download PDFInfo
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- CN110168015A CN110168015A CN201880005716.7A CN201880005716A CN110168015A CN 110168015 A CN110168015 A CN 110168015A CN 201880005716 A CN201880005716 A CN 201880005716A CN 110168015 A CN110168015 A CN 110168015A
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- resin
- dielectric layer
- capacitor
- resin combination
- copper foil
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Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/33—Thin- or thick-film capacitors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/043—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
本发明提供一种树脂组合物,当用作电容器元件或内置电容器的印刷电路板的介电层时,该树脂组合物能够确保优异的电路密合性,并且改善高温高湿下的电容器元件的容量稳定性和绝缘性。该树脂组合物含有树脂成分和介电填料,树脂成分含有环氧树脂、活性酯树脂和芳香族聚酰胺树脂。
Description
技术领域
本发明涉及树脂组合物、带树脂铜箔、介电层、覆铜层压板、电容器元件以及内置电容器的印刷电路板。
背景技术
作为用于制造覆铜层压板、印刷电路板的树脂组合物,已知内置电容器的印刷电路板用树脂组合物。该树脂组合物通过固化而用作电容器中的介电层。例如,专利文献1(日本专利第4148501号公报)中记载了一种内置电容器的印刷电路板用树脂组合物,其(以100重量份的树脂成分计)含有20~80重量份的环氧树脂和20~80重量份的芳香族聚酰胺树脂,(以100wt%的树脂组合物计)含有75~85wt%的介电填料。另外,专利文献2(国际公开第2009/008471号)中记载了一种内置电容器的印刷电路板制造用树脂组合物,其(以100重量份的树脂成分计)含有25~60重量份的环氧树脂、28~60重量份的活性酯树脂、1~20重量份的聚乙烯醇缩醛树脂,(以100wt%的树脂组合物计)含有65~85wt%的介电填料。
另一方面,已知一种能够实现树脂组合物的固化物的低介电损耗角正切,并且能够抑制对固化物进行开孔加工和粗糙化处理后的导通孔内的残渣(smear)的树脂组合物。例如,专利文献3(日本特开2016-156019号公报)中记载了一种树脂组合物,其是含有(A)环氧树脂、(B)活性酯化合物、(C)残渣抑制成分和(D)无机填料的树脂组合物,其中,以该树脂组合物的非挥发性组分为100质量%时,(B)活性酯化合物的含量为5质量%以上,以该树脂组合物的非挥发性组分为100质量%时,(C)残渣抑制成分为0.001~10质量%,以该树脂组合物的非挥发性组分为100质量%时,(D)无机填料为70质量%以上,(C)残渣抑制成分为橡胶颗粒。
现有技术文献
专利文献
专利文献1:日本专利第4148501号公报
专利文献2:国际公开第2009/008471号
专利文献3:日本特开2016-156019号公报
专利文献4:日本特开2004-277460号公报
发明内容
但是,印刷电路板广泛用于便携式电子设备等电子通信设备中。尤其是随着近年来便携式电子通信设备等的轻薄短小化和高功能化的发展,降低印刷电路板中的干扰等成为技术问题。对于降低干扰来说,电容器很重要,但是为了实现高性能,期望这种电容器能够小型化和薄化至可以组装至印刷电路板的内层的程度。与此同时,期望其具有即使在更严苛的高温高湿的环境下也能够保持所需的电容的容量稳定性。
因此,为了实现便携式电子设备等电子通信设备的高性能,期望能够抑制印刷电路板内置电容器在高温高湿下的电容降低或介电常数降低。为此,希望对构成电容器的介电层的树脂层作进一步的改善。另一方面,也期望树脂层与电路之间具有高的密合性(即电路密合性)。
本发明人等此次发现,通过将含有介电填料的同时还含有环氧树脂、活性酯树脂和芳香族聚酰胺树脂的树脂组合物用作电容器的介电层,能够确保优异的电路密合性,并且抑制高温高湿下的电容降低或介电常数降低。
因此,本发明的目的在于提供一种当用作电容器的介电层时,能够确保优异的电路密合性,并且抑制高温高湿下的电容降低或介电常数降低的树脂组合物。
根据本发明的一个实施方式,提供一种含有树脂成分和介电填料的树脂组合物,其中,
所述树脂成分含有环氧树脂、活性酯树脂和芳香族聚酰胺树脂。
根据本发明的另一实施方式,提供一种带树脂铜箔,其含有铜箔和设置于所述铜箔的至少一面的权利要求1~5中任一项所述的树脂组合物。
根据本发明的另一实施方式,提供一种介电层,其是所述树脂组合物固化而得到的层。
根据本发明的另一实施方式,提供一种覆铜层压板,其依次具备第一铜箔、所述介电层和第二铜箔。
根据本发明的另一实施方式,提供一种电容器元件,其具有所述介电层。
根据本发明的另一实施方式,提供一种内置电容器的印刷电路板,其具有所述介电层。
附图说明
图1是示出例1~8中的带树脂铜箔、覆铜层压板以及评价用电路的制作工序的图。
具体实施方式
下文中,对本发明的实施方式进行说明。需要说明的是,本说明书中用“X~Y”的形式表示的数值范围的含义是“X以上且Y以下”。
树脂组合物
本发明的树脂组合物含有树脂成分和介电填料。并且,该树脂成分含有环氧树脂、活性酯树脂和芳香族聚酰胺树脂。这样,通过将含有介电填料的同时还含有环氧树脂、活性酯树脂和芳香族聚酰胺树脂的树脂组合物用作电容器的介电层,能够确保优异的电路密合性,并且抑制高温高湿下的电容降低或介电常数降低。即,含有本发明的树脂组合物的介电层原本的静电容量高,即使在高温高湿下其高的静电容量也不易降低。另外,含有本发明的树脂组合物的介电层,即使在高温高湿下也不易发生电路构成成分(通常为Cu等金属)的迁移,因而能够长期保持层间绝缘性。因此,介电层在高温高湿下介电常数不易降低,从而高温高湿下的电容也不易降低。因为如此,含有本发明的树脂组合物的介电层的电路密合性也优异,不易发生电容器中的电路剥离。
本发明的树脂组合物,相对于100重量份的树脂成分,优选含有9~85重量份的芳香族聚酰胺树脂和5~50重量份的活性酯树脂,优选含有10~80重量份的芳香族聚酰胺树脂和10~40重量份的活性酯树脂,更优选芳香族聚酰胺树脂为15~70重量份和活性酯树脂为12~38重量份,进一步优选芳香族聚酰胺树脂为25~60重量份和活性酯树脂为15~35重量份,特别优选芳香族聚酰胺树脂为30~50重量份和活性酯树脂为20~30重量份。以这种含量,能够更有效地发挥上述本发明的效果。
环氧树脂只要是分子内具有2个以上的环氧基,能够用于电气和电子材料用途即可,无特别限定。作为环氧树脂的例子,可列举出双酚A型环氧树脂、双酚F型环氧树脂、双酚S型环氧树脂、苯酚酚醛清漆型环氧树脂、联苯酚醛清漆型环氧树脂、甲酚酚醛清漆型环氧树脂、脂环式环氧树脂、缩水甘油胺型环氧树脂、萘型环氧树脂、蒽型环氧树脂、双环戊二烯型环氧树脂以及它们的任意组合。从保持固化物的耐热性的角度出发,优选芳香族环氧树脂或多官能环氧树脂,更优选苯酚酚醛清漆型环氧树脂、萘型环氧树脂、甲酚酚醛清漆型环氧树脂或联苯酚醛清漆型环氧树脂。这些环氧树脂对保持固化物的耐热性是有效的。
活性酯树脂作为与环氧树脂发生反应并固化的环氧树脂固化剂发挥作用。对于活性酯树脂并无特别限定,可以使用公知的活性酯树脂。例如,也可以使用专利文献4(日本特开2004-277460号公报)中公开的活性酯化合物。另外,也可以使用市售的活性酯化合物。作为市售的活性酯化合物的例子,可列举出含有双环戊二烯结构的活性酯系固化剂、含有萘结构的活性酯系固化剂、含有苯酚酚醛清漆的乙酰化物的活性酯系固化剂、以及含有苯酚酚醛清漆的苯甲酰化物的活性酯系固化剂,优选可列举出含有萘结构的活性酯系固化剂、以及含有双环戊二烯二酚结构的活性酯系固化剂。作为含有双环戊二烯二酚结构的活性酯系固化剂的例子,可列举出EXB9451、EXB9460、EXB9460S、HPC-8000-65T(DIC株式会社制造)。作为含有萘结构的活性酯系固化剂的例子,可列举出EXB9416-70BK(DIC株式会社制造)。作为含有苯酚酚醛清漆的乙酰化物的活性酯系固化剂的例子,可列举出DC808(三菱化学株式会社制造)。作为含有苯酚酚醛清漆的苯甲酰化物的活性酯系固化剂的例子,可列举出YLH1026(三菱化学株式会社制造)。使用上述的活性酯树脂时,能够确保环氧树脂固化物的耐热性,并且降低吸水率。
树脂组合物相对于100重量份的树脂成分含有25~60重量份的芳香族聚酰胺树脂和15~35重量份的活性酯树脂的情况下,活性酯树脂的含量优选相对于环氧树脂的1当量的环氧基,以羟基换算计为0.75~1.25当量的量。活性酯树脂的含量相对于环氧树脂为0.75当量以上时,环氧树脂不容易自聚,防止由于环氧树脂分子较少而使固化反应终止,因而能够得到介电损耗角正切大的介电层,而且没有活性酯树脂的羟基残留。另外,活性酯树脂的配混量相对于环氧树脂为1.25当量以下时,在固化后的介电层中活性酯树脂不容易因为未反应而残留,能够防止介电层的耐热特性劣化。
芳香族聚酰胺树脂有助于提高树脂层的耐热性。芳香族聚酰胺树脂是指通过芳香族二胺与二羧酸的缩聚而合成的树脂。作为用于上述缩聚中的芳香族二胺的例子,可列举出3,4’-二氨基二苯醚、4,4’-二氨基二苯醚、4,4’-二氨基二苯基甲烷、3,3’-二氨基二苯基砜、间苯二甲胺、3,3’-二氨基二苯醚等以及它们的任意组合。另外,作为用于上述缩聚中的二羧酸的例子,可列举出草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、邻苯二甲酸、间苯二甲酸、对苯二甲酸、富马酸以及它们的任意组合。为了赋予芳香族聚酰胺树脂耐热性,二羧酸优选为芳香族二羧酸,作为芳香族二羧酸的例子,可列举出邻苯二甲酸、间苯二甲酸、对苯二甲酸、富马酸以及它们的任意组合。尤其优选分子内含有酚羟基的芳香族聚酰胺树脂。另外,在不损害耐热性的范围内,该芳香族聚酰胺树脂也可以在分子内适当含有赋予芳香族聚酰胺树脂挠性的化学键作为柔性链,也可以是与聚酰胺树脂形成交联性聚合物合金而以局部聚集状态存在的物质。作为能够带来赋予芳香族聚酰胺树脂挠性的化学键作为柔性链的化合物的例子,可列举出例如丁二烯、乙烯-丙烯共聚物、苯乙烯-丁二烯共聚物、羧酸-丁二烯共聚物、丙烯腈-丁二烯共聚物、聚氨酯、聚氯丁二烯、硅氧烷等。通过使用上述的芳香族聚酰胺,能够确保环氧树脂固化物的柔软性而提高剥离强度可靠性,并且还能提高耐热性。
为了促进树脂的反应,优选向树脂成分中添加固化促进剂。作为固化促进剂的优选的例子,可列举出咪唑系和胺系固化促进剂。从树脂组合物的保存稳定性、固化的效率化的角度出发,相对于100质量%的树脂组合物中的非挥发性组分,固化促进剂的含量优选为0.01~3质量%,更优选为0.1~2质量%。
由于咪唑系固化促进剂与环氧树脂发生固化反应后,是作为环氧树脂的一部分结合到分子结构中,而不会作为离子发生游离,因此能够使树脂层的介电特性、绝缘可靠性优异。对于咪唑系固化促进剂的含量,考虑树脂层的组成等各种条件,适当确定能够实现所需的固化的量即可,无特别限定。作为咪唑固化促进剂的例子,可列举出2-十一烷基咪唑、2-十七烷基咪唑、2-乙基-4-甲基咪唑、2-苯基-4-甲基咪唑、1-氰乙基-2-十一烷基咪唑、1-氰乙基-2-乙基-4-甲基咪唑、2-乙基-4-甲基咪唑、1-氰乙基-2-苯基咪唑、2-苯基-4,5-二羟甲基咪唑、2-苯基-4-甲基-5-羟甲基咪唑、2-甲基咪唑、1,2-二甲基咪唑、2-苯基咪唑、1-苄基-2-甲基咪唑、1-苄基-2-甲基咪唑、1-苄基-2-苯基咪唑、1-氰乙基-2-甲基咪唑、1-氰乙基-2-十一烷基咪唑偏苯三酸盐、1-氰乙基-2-苯基咪唑偏苯三酸盐、2,4-二氨基-6-[2’-甲基咪唑基-(1’)]-乙基-均三嗪、2,4-二氨基-6-[2’-十一烷基咪唑基-(1’)]-乙基-均三嗪、2,4-二氨基-6-[2’-乙基-4’-甲基咪唑基-(1’)]-乙基-均三嗪、2,4-二氨基-6-[2’-甲基咪唑基-(1’)]-乙基-均三嗪异氰脲酸加成物、2-苯基咪唑异氰脲酸加成物、2,3-二氢-1H-吡咯并[1,2-a]苯并咪唑、1-十二烷基-2-甲基-3-苄基咪唑氯化物、2-甲基咪唑啉、2-苯基咪唑啉以及它们的任意组合。作为咪唑系固化促进剂的优选的例子,可列举出2-甲基咪唑、2-乙基-4-甲基咪唑、2-苯基-4-甲基咪唑、2-苯基-4-甲基-5-羟甲基咪唑,其中,从树脂层的半固化(B阶)状态下的化学稳定性的角度出发,可以列举出具有苯基的咪唑系固化促进剂2-苯基-4-甲基咪唑、2-苯基-4-甲基-5-羟甲基咪唑作为更优选的例子。其中,特别优选地可列举出2-苯基-4-甲基-5-羟甲基咪唑。
作为胺系固化促进剂的例子,可列举出三乙胺、三丁胺等三烷基胺、4-二甲氨基吡啶、苄基二甲胺、2,4,6,-三(二甲氨基甲基)苯酚、1,8-二氮杂双环(5,4,0)-十一烯以及它们的任意组合。
介电填料是给作为介电层的树脂组合物带来所需的高静电容量的成分,可以使用公知的物质。优选的介电填料含有选自由BaTiO3、SrTiO3、Pb(Zr,Ti)O3、PbLaTiO3、PbLaZrO和SrBi2Ta2O9组成的组中的至少1种。从提高介电层形成的电容器的静电容量的角度出发,特别优选介电填料为BaTiO3。相对于100重量份的树脂组合物的固体成分,树脂组合物中的介电填料的优选的含量为60~95重量份,更优选为70~90重量份,进一步优选为70~80重量份。
根据需要,树脂组合物也可以进一步含有填料分散剂。通过进一步含有填料分散剂,在混炼树脂清漆和介电填料时,能够提高介电填料的分散性。作为填料分散剂,可以适当使用能够使用的公知的物质,无特别限定。作为优选的填料分散剂的例子,可列举出作为离子系分散剂的膦酸型、阳离子型、羧酸型、阴离子型分散剂,以及作为阴离子系分散剂的醚型、酯型、脱水山梨糖醇酯型、二酯型、单甘油酯型、环氧乙烷加成型、乙二胺基型(ethylene diamine base type)、酚醛型(phenol type)分散剂等。此外,还可列举出硅烷偶联剂、钛酸酯偶联剂、铝酸酯偶联剂等偶联剂。
带树脂铜箔
本发明的树脂组合物优选作为带树脂铜箔的树脂使用。从以使树脂组合物彼此相对地层压2张带树脂铜箔形成介电层的角度出发,优选带树脂铜箔中的树脂组合物为半固化状态。通过预先形成为带树脂铜箔的形态,能够高效地进行电容器元件、内置电容器的印刷电路板的制造,而无需另外形成树脂层或介电层。即,根据本发明优选的方式,提供一种带树脂铜箔,其含有铜箔和设置于铜箔的至少一面的树脂组合物。通常,树脂组合物为树脂层的形态,通过凹版涂布方式将树脂组合物涂布在铜箔上并干燥,以使干燥后的树脂层的厚度达到规定的厚度,得到带树脂铜箔。该涂布的方式可以为任意的方式,除了凹版涂布方式外,也可以采用模涂方式、刮刀涂布方式等。此外,也可以使用刮刀、刮棒涂布机等进行涂布。
对树脂层的厚度无特别限定,只要作为介电层结合至电容器中时能够确保所需的静电容量即可,但优选为0.1~15μm,更优选为0.2~10μm,进一步优选为0.5~5.0μm。若为这些范围内的厚度,则具有容易实现高静电容量、通过树脂组合物的涂布容易形成树脂层、容易确保与铜箔间的充分的密合性等优点。
铜箔既可以为电解制箔或压延制箔后的金属箔(所谓的生箔),也可以为至少任一个表面上实施了表面处理的表面处理箔的形态。表面处理可以为用于提高或赋予金属箔表面以任何一种性质(例如防锈性、耐湿性、耐化学性、耐酸性、耐热性以及与基板的密合性)的各种表面处理。表面处理可以在金属箔的至少一面上进行,也可以在金属箔的两面上进行。作为对铜箔进行的表面处理的例子,可列举出防锈处理、硅烷处理、粗糙化处理、阻隔层形成处理等。
优选铜箔的树脂层侧的表面的根据JIS B0601-2001测定的十点平均粗糙度Rzjis为2.0μm以下,更优选为1.5μm以下,进一步优选为1.0μm以下,特别优选为0.5μm以下。在这样的范围内时,能够使树脂层的厚度更薄。对于铜箔的树脂层侧的表面的十点平均粗糙度Rzjis的下限值,无特别限定,从提高与树脂层的密合性的角度出发,Rzjis优选为0.005μm以上,更优选为0.01μm以上,进一步优选为0.05μm以上。
对铜箔的厚度无特别限定,优选为0.1~100μm,更优选为0.5~70μm以下,进一步优选为2~70μm以下,特别优选为10~70μm以下,最优选为10μm~35μm以下。若为这些范围内的厚度,则可以采用作为形成印刷电路板的布线的常规图案形成方法的MSAP(改良型半加成法)法、SAP(半加成法)法、减成法等工艺方法。不过,当铜箔的厚度为例如10μm以下等时,本发明的带树脂铜箔也可以是为了提高操作性而在具有剥离层和载体的带载体铜箔的铜箔表面上形成有树脂层的铜箔。
介电层
优选将本发明的树脂组合物固化形成介电层。即,根据本发明优选的方式,提供一种介电层,其是本发明的树脂组合物固化而得到的层。树脂组合物的固化可以基于公知的方法进行,但优选通过真空热压进行。介电层的厚度只要能够确保所需的静电容量即可,无特别限定,但优选为0.2~30μm,更优选为0.5~20μm,进一步优选为1~8μm,最优选为2~6μm。若为这些范围内的厚度,则具有容易实现高静电容量、通过树脂组合物的涂布容易形成树脂层、容易确保与铜箔间的充分的密合性等优点。
覆铜层压板
本发明的树脂组合物或包含其的介电层优选适用于覆铜层压板。即,根据本发明优选的方式,提供一种覆铜层压板,其依次具备第一铜箔、上述的介电层和第二铜箔。通过采用覆铜层压板的形态,可以优选地制造含有本发明的树脂组合物作为介电层的电容器元件、内置电容器的印刷电路板。对覆铜层压板的制作方法无特别限定,但例如可以通过以使树脂层彼此相对地层压2张上述的带树脂铜箔,并在高温下进行真空压制来制造覆铜层压板。
电容器元件以及内置电容器的印刷电路板
优选将本发明的树脂组合物或含有其的介电层结合至电容器元件中。即,根据本发明优选的方式,提供一种电容器元件,其具有上述的介电层。对电容器元件的构造无特别限定,可以采用公知的构造。特别优选的形态是结合有电容器或其介电层作为印刷电路板的内层部分的内置电容器的印刷电路板。即,根据本发明特别优选的方式,提供一种内置电容器的印刷电路板,其具有上述的介电层。特别地,通过使用本发明的带树脂铜箔,能够基于公知的方法高效地制造电容器元件、内置电容器的印刷电路板。
实施例
通过下述的例子对本发明进行更具体的说明。
例1~7
(1)树脂清漆的制备
首先,准备如下所示的树脂成分、咪唑系固化促进剂和介电填料作为树脂清漆用原料成分。
-环氧树脂:联苯酚醛清漆型环氧树脂,日本化药株式会社制造,NC-3000
-活性酯树脂:DIC株式会社制造,HPC-8000-65T
-芳香族聚酰胺树脂:日本化药株式会社制造,BPAM-155
-咪唑固化促进剂:四国化成工业株式会社制,2P4MHZ,添加量1.0wt%(相对于100wt%的树脂成分)
-介电填料:BaTiO3,日本化学工业株式会社制造,AKBT-M
-填料分散剂:钛酸酯系偶联剂,Ajinomoto Fine-Techno Co.,Inc.制造,KR-44
根据表1所示的配混比(重量比)称量上述树脂清漆用原料成分。进一步地,添加环戊酮作为溶剂,在60℃下搅拌。确认树脂清漆的透明性后,回收树脂清漆。
(2)与填料的混炼
分别称量环戊酮、介电填料和填料分散剂。通过分散机将称量的溶剂、介电填料和填料分散剂浆料化。确认浆料化后,称量树脂清漆,通过分散机将其与含有介电填料的浆料一起混炼,得到树脂组合物4。
(3)树脂涂布
如图1所示,使用刮棒涂布机将得到的树脂组合物4涂布在铜箔2(三井金属矿业株式会社制造,厚度35μm,表面粗糙度Rz=0.5μm)使其厚度达到1.5μm,然后,在加热至130℃的烘箱中干燥3分钟,使树脂为半固化状态。由此得到带树脂铜箔6。
(4)压制
如图1所示,以使树脂组合物4彼此相对地层压2张带树脂铜箔6,在压力40kgf/cm2、200℃下实施90分钟的真空压制,使树脂组合物4为固化状态。由此得到含有固化的树脂组合物4作为介电层的覆铜层压板8。
(5)电路形成和评价
在得到的覆铜层压板8的一面或两面上进行蚀刻形成用于各种评价的电路10,进行下述的各种评价。
<评价1:剥离强度>
在覆铜层压板的一面上进行蚀刻制作10mm宽的直线状电路后,通过自动绘图以50mm/分钟的剥离速度剥离电路,测定其剥离强度。根据IPC-TM-650 2.4.8进行该测定。按照下述的标准对测定的剥离强度进行评价。结果如表1所示。
-评价A:0.8kgf/cm以上(良)
-评价B:0.4kgf/cm以上且小于0.8kgf/cm(可)
-评价C:小于0.4kgf/cm(不可)
<评价2:热处理后的静电容量的降低率>
首先,在覆铜层压板的一面上进行蚀刻制作直径0.5英寸(12.6mm)的圆形电路后,通过LCR测试仪(日置电气株式会社制造,LCR HiTESTER 3532-50)测定频率1kHz下的静电容量。根据IPC-TM-650 2.5.2进行该测定。结果如表1所示。
然后,将完成了上述测定的样品放入230℃的烘箱中110分钟后,再次测定静电容量,计算热处理前后的静电容量的降低率。按照下述的标准对算出的静电容量的降低率进行评价。结果如表1所示。
-评价AA:小于2%(最佳)
-评价A:2%以上且小于3%(良)
-评价B:3%以上且小于6%(可)
-评价C:6%以上(不可)
<评价3:层间绝缘性保持时间>
在覆铜层压板的两面上进行蚀刻制作直径0.5英寸(12.6mm)的圆形电路后,将布线焊接至上部电极和下部电极,将布线连接至迁移测量用仪器。将评价电路放入85℃和85%RH的恒温恒湿槽中,施加电压3V的负荷,测量保持1×105Ω以上的绝缘电阻的时间。按照下述的标准对测量的层间绝缘性保持时间进行评价。结果如表1所示。
-评价AA:1000小时以上(最佳)
-评价A:500小时以上且小于1000小时(良)
-评价B:200小时以上且小于500小时(可)
-评价C:小于200小时(不可)
<综合评价>
将评价1~3的评价结果套用至下述的基准中,进行综合评价。结果如表1所示。
-评价AA:所有的评价都判定为A以上(最佳)
-评价A:没有判定为C的,且判定为B的有1个(良)
-评价B:没有判定为C的,且判定为B的有2个(可)
-评价C:至少有1个判定为C(不可)
例8(比较)
除了使用20.0重量份的酚醛树脂(明和化成株式会社制造,MEH-7500)代替活性酯树脂,将环氧树脂的配混比增加至40.0重量份以外,与例3同样地进行树脂清漆的制备和各种评价。结果如表1所示。
例9(比较)
除了使用聚乙烯醇缩丁醛树脂(积水化学工业制造,KS-5Z)代替芳香族聚酰胺树脂以外,与例2同样地进行树脂清漆的制备和各种评价。结果如表1所示。
例10(比较)
除了不使用芳香族聚酰胺树脂,将环氧树脂的配混比增加至56.0重量份,活性酯树脂的配混比增加至44.0重量份以外,与例1同样地进行树脂清漆的制备和各种评价。结果如表1所示。
[表1]
Claims (11)
1.一种树脂组合物,其是含有树脂成分和介电填料的树脂组合物,
所述树脂成分含有环氧树脂、活性酯树脂和芳香族聚酰胺树脂。
2.根据权利要求1所述的树脂组合物,其中,相对于100重量份的所述树脂成分,含有9~85重量份的所述芳香族聚酰胺树脂和15~35重量份的所述活性酯树脂。
3.根据权利要求1或2所述的树脂组合物,其中,所述介电填料含有选自由BaTiO3、SrTiO3、Pb(Zr,Ti)O3、PbLaTiO3、PbLaZrO和SrBi2Ta2O9组成的组中的至少1种。
4.根据权利要求1~3中任一项所述的树脂组合物,其中,所述介电填料为BaTiO3。
5.根据权利要求1~4中任一项所述的树脂组合物,其中,相对于100重量份的所述树脂组合物的固体成分,含有60~95重量份的所述介电填料。
6.一种带树脂铜箔,其含有铜箔和设置于所述铜箔的至少一面的权利要求1~5中任一项所述的树脂组合物。
7.一种介电层,其是权利要求1~5中任一项所述的树脂组合物固化而得到的层。
8.根据权利要求7所述的介电层,其中,所述介电层的厚度为0.2~30μm。
9.一种覆铜层压板,其依次具备第一铜箔、权利要求7或8所述的介电层和第二铜箔。
10.一种电容器元件,其具有权利要求7或8所述的介电层。
11.一种内置电容器的印刷电路板,其具有权利要求7或8所述的介电层。
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