CN107848261A - 带树脂的铜箔、及印刷电路板 - Google Patents
带树脂的铜箔、及印刷电路板 Download PDFInfo
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- CN107848261A CN107848261A CN201680043391.2A CN201680043391A CN107848261A CN 107848261 A CN107848261 A CN 107848261A CN 201680043391 A CN201680043391 A CN 201680043391A CN 107848261 A CN107848261 A CN 107848261A
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- Prior art keywords
- resin
- copper foil
- curing agent
- mass parts
- filler
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000011347 resin Substances 0.000 title claims abstract description 102
- 229920005989 resin Polymers 0.000 title claims abstract description 102
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000011889 copper foil Substances 0.000 title claims abstract description 45
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 24
- 239000000945 filler Substances 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 12
- 238000013329 compounding Methods 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 9
- -1 siloxane backbone Chemical group 0.000 claims description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- 150000002148 esters Chemical group 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 125000005842 heteroatom Chemical group 0.000 claims description 6
- 150000002460 imidazoles Chemical class 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 6
- 150000001768 cations Chemical class 0.000 claims description 5
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- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical group C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
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- 239000003999 initiator Substances 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 claims 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims 1
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- 239000011737 fluorine Substances 0.000 claims 1
- 230000005540 biological transmission Effects 0.000 abstract description 8
- 125000004185 ester group Chemical group 0.000 abstract 2
- 238000001723 curing Methods 0.000 description 18
- 239000002585 base Substances 0.000 description 17
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
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- 238000000034 method Methods 0.000 description 6
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- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 4
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- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
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- 235000011194 food seasoning agent Nutrition 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
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- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
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- DPZSNGJNFHWQDC-ARJAWSKDSA-N (z)-2,3-diaminobut-2-enedinitrile Chemical compound N#CC(/N)=C(/N)C#N DPZSNGJNFHWQDC-ARJAWSKDSA-N 0.000 description 1
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 1
- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 description 1
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- HWRRQRKPNKYPBW-UHFFFAOYSA-N 2,4-dimethylcyclohexan-1-amine Chemical compound CC1CCC(N)C(C)C1 HWRRQRKPNKYPBW-UHFFFAOYSA-N 0.000 description 1
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- RAZLJUXJEOEYAM-UHFFFAOYSA-N 2-[bis[2-(2,6-dioxomorpholin-4-yl)ethyl]azaniumyl]acetate Chemical compound C1C(=O)OC(=O)CN1CCN(CC(=O)O)CCN1CC(=O)OC(=O)C1 RAZLJUXJEOEYAM-UHFFFAOYSA-N 0.000 description 1
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- YTWBFUCJVWKCCK-UHFFFAOYSA-N 2-heptadecyl-1h-imidazole Chemical class CCCCCCCCCCCCCCCCCC1=NC=CN1 YTWBFUCJVWKCCK-UHFFFAOYSA-N 0.000 description 1
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Abstract
提供:通过使用介电常数及介电损耗角正切低的双马来酰亚胺树脂能够提高传输特性、能够在不进行紫外线照射下制造的带树脂的铜箔、及使用其的印刷电路板。带树脂的铜箔、及使用其的印刷电路板,所述带树脂的铜箔是将树脂组合物层叠于铜箔而成的,所述树脂组合物含有下述通式(I)所示的双马来酰亚胺树脂、固化剂、及填料,填料的配混量相对于树脂成分100质量份为10~200质量份,所述树脂组合物在80℃下的复数粘度为1×103Pa·s~5×105Pa·s。其中,下述通式(I)中,X表示脂肪族、脂环式或芳香族的烃基、且主链的碳数为10~30的烃基,Y表示脂肪族、脂环式或芳香族的烃基,n表示1~20的范围的数。
Description
技术领域
本发明涉及主要在印刷电路板的制造中使用的带树脂的铜箔、及使用其的印刷电路板。
背景技术
随着智能电话等信息终端的普及,能高速处理的处理器、通信模块登场,在安装它们的电路基板中流动的电信号的传输速度正在高速化,因此提高传输特性的多层基板等基板材料的要求增高。
多层基板可以如下制造:在芯基板的表面重叠对铜箔涂布B阶的热固化性树脂而得到的带树脂的铜箔,边加热边进行压制,由此固化而形成多层化层,接着通过激光加工形成导通孔,进行镀覆将层间连接后,对铜箔进行蚀刻,从而形成电路,由此来制造。
为了提高基板的传输特性,要求基板中所用的带树脂的铜箔中使用介电常数及介电损耗角正切低的树脂,作为其例子,氟树脂、液晶聚合物等正在实用化。但是,氟树脂的密合性、柔性、及加工性差,液晶聚合物的密合性及加工性差。因此,作为可解决这些问题的方案,提出了使用双马来酰亚胺树脂,但使用其的情况下,存在熔融粘度低、在压制成型时发生树脂的流动的问题。因此,如专利文献1,公开了通过在压制前进行紫外线照射来进行临时固化、成为B阶状的技术。但是,根据树脂层的厚度,产生了紫外线照射发生偏差、无法使双马来酰亚胺树脂均匀地固化的问题;添加至双马来酰亚胺树脂中的阻燃剂、固化剂、耐磨耗剂等填料阻断紫外线,妨碍双马来酰亚胺树脂的固化的问题。
因此,使用双马来酰亚胺树脂的情况下,要求能够在不进行紫外线照射下制造的带树脂的铜箔。
现有技术文献
专利文献
专利文献1:日本特开2003-243836号公报
发明内容
发明要解决的问题
本发明是鉴于上述而做出的,其目的在于,提供:通过使用介电常数及介电损耗角正切低的双马来酰亚胺树脂能够提高传输特性、能够在不进行紫外线照射下制造的带树脂的铜箔;及,使用其的印刷电路板。
用于解决问题的方案
本发明的带树脂的铜箔为了解决上述问题,使层叠于铜箔上的树脂组合物含有下述通式(I)所示的双马来酰亚胺树脂、固化剂、及填料,使填料的配混量相对于树脂成分100质量份为10~200质量份,使在80℃下的复数粘度为1×103Pa·s~5×105Pa·s。
其中,式(I)中,X表示脂肪族、脂环式或芳香族的烃基、且主链的碳数为10~30的烃基,这些基团任选具有杂原子、取代基或硅氧烷骨架,Y表示脂肪族、脂环式或芳香族的烃基,这些基团任选具有杂原子、取代基、苯基醚骨架、磺酰骨架或硅氧烷骨架,n表示1~20的范围的数。
上述通式(I)所示的双马来酰亚胺化合物可以为如下化合物:通式(I)中的X以碳数10~30的烷基为主链、该烷基中的彼此邻接的碳所键合的2个侧链部分地形成环状结构。
上述填料可以为二氧化硅和/或氟树脂粉,上述固化剂可以为选自自由基引发剂、咪唑系固化剂、及阳离子系固化剂中的1种或2种以上。
可以使用这些带树脂的铜箔来制作印刷电路板。
发明的效果
根据本发明的带树脂的铜箔,可以提供:通过使用介电常数及介电损耗角正切低的双马来酰亚胺树脂,能够提高传输特性、能够减少压制成型时的树脂组合物的流动、能够在不进行紫外线照射下制造的带树脂的铜箔。
具体实施方式
以下,更具体地对本发明的实施方式进行说明。
本实施方式的带树脂的铜箔是将树脂组合物层叠于铜箔的表面的一部分或全部而成的,所述树脂组合物含有双马来酰亚胺树脂、固化剂、及填料,填料的配混量相对于树脂成分100质量份为10~200质量份,所述树脂组合物在80℃下的复数粘度为1×103Pa·s~5×105Pa·s。
作为双马来酰亚胺树脂,使用下述通式(I)所示的物质。
其中,式(I)中,X表示脂肪族、脂环式、或芳香族的烃基、且主链的碳数为10~30的烃基,这些基团任选具有杂原子、取代基、或硅氧烷骨架。X优选为脂肪族或脂环式烃、或者经脂环式烃基修饰的脂肪族烃基,也包括侧链在内的碳数更优选为10~55、进一步优选为10~40。特别优选的是X以碳数10~30的烷基为主链、该烷基中的彼此邻接的碳所键合的2个侧链部分地形成环状结构的化合物。
Y表示脂肪族、脂环式、或芳香族的烃基,这些基团任选具有杂原子、取代基、苯基醚骨架、磺酰骨架、或硅氧烷骨架。Y优选为芳香族烃基。
n为重复单元数,表示1~20的范围的数,从可获得柔软的树脂的方面出发,优选1~15的范围、更优选1~10的范围。n为20以下时,可获得强度优异的带树脂的铜箔。双马来酰亚胺化合物可以单独使用1种n为1~20的化合物,也可以组合使用2种以上,更优选为n为1~10的化合物的混合物。
上述双马来酰亚胺化合物的制造方法没有特别限定,例如可以通过使酸酐与二胺进行缩合反应后、脱水进行环化(酰亚胺化)的公知的方法来制造。
作为其制造中能使用的酸酐的例子,可列举出聚丁二烯-接枝-马来酸酐;聚乙烯-接枝-马来酸酐;聚乙烯-马来酸酐交替共聚物;聚马来酸酐-1-十八碳烯交替共聚物;聚丙烯-接枝-马来酸酐;聚(苯乙烯-马来酸酐)共聚物;苯均四酸酐;马来酸酐、琥珀酸酐;1,2,3,4-环丁烷四羧酸二酐;1,4,5,8-萘四羧酸二酐;3,4,9,10-苝四羧酸二酐;双环(2.2.2)辛-7-烯-2,3,5,6-四羧酸二酐;二亚乙基三胺五乙酸二酐;乙二胺四乙酸二酐;3,3’,4,4’-二苯甲酮四羧酸二酐;3,3’,4,4’-联苯四羧酸二酐;4,4’-氧双邻苯二甲酸酐;3,3’,4,4’-二苯基砜四羧酸二酐;2,2’-双(3,4-二羧基苯基)六氟丙烷二酐;4,4’-双酚A二邻苯二甲酸酐;5-(2,5-二氧代四氢)-3-甲基-3-环己烯-1,2-二甲酸酐;乙二醇双(偏苯三酸酐);氢醌二邻苯二甲酸酐;烯丙基纳迪克酸酐(allyl nadic anhydride);2-辛烯-1-基琥珀酸酐;邻苯二甲酸酐;1,2,3,6-四氢邻苯二甲酸酐;3,4,5,6-四氢邻苯二甲酸酐;1,8-萘二甲酸酐;戊二酸酐;十二烯基琥珀酸酐;十六烯基琥珀酸酐;六氢邻苯二甲酸酐;甲基六氢邻苯二甲酸酐;十四烯基琥珀酸酐等。
另外,作为二胺的例子,可列举出1,10-二氨基癸烷;1,12-二氨基十二烷;二聚体二胺;1,2-二氨基-2-甲基丙烷;1,2-二氨基环己烷;1,2-二氨基丙烷;1,3-二氨基丙烷;1,4-二氨基丁烷;1,5-二氨基戊烷;1,7-二氨基庚烷;1,8-二氨基薄荷烷;1,8-二氨基辛烷;1,9-二氨基壬烷;3,3’-二氨基-N-甲基二丙基胺;二氨基马来腈;1,3-二氨基戊烷;9,10-二氨基菲;4,4’-二氨基八氟联苯;3,5-二氨基苯甲酸;3,7-二氨基-2-甲氧基芴;4,4’-二氨基二苯甲酮;3,4-二氨基二苯甲酮;3,4-二氨基甲苯;2,6-二氨基蒽醌;2,6-二氨基甲苯;2,3-二氨基甲苯;1,8-二氨基萘;2,4-二氨基甲苯;2,5-二氨基甲苯;1,4-二氨基蒽醌;1,5-二氨基蒽醌;1,5-二氨基萘;1,2-二氨基蒽醌;2,4-异丙苯二胺;1,3-二(氨甲基)苯;1,3-二(氨甲基)环己烷;2-氯-1,4-二氨基苯;1,4-二氨基-2,5-二氯苯;1,4-二氨基-2,5-二甲基苯;4,4’-二氨基-2,2’-双(三氟甲基)联苯;双(氨基-3-氯苯基)乙烷;双(4-氨基-3,5-二甲基苯基)甲烷;双(4-氨基-3,5-二乙基苯基)甲烷;双(4-氨基-3-乙基二氨基芴;二氨基苯甲酸;2,3-二氨基萘;2,3-二氨基苯酚;-5-甲基苯基)甲烷;双(4-氨基-3-甲基苯基)甲烷;双(4-氨基-3-乙基苯基)甲烷;4,4’-二氨基苯基砜;3,3’-二氨基苯基砜;2,2-双(4-(4-氨基苯氧基)苯基)砜;2,2-双(4-(3-氨基苯氧基)苯基)砜;4,4’-氧代二苯胺;4,4’-二氨基二苯硫醚;3,4’-氧代二苯胺;2,2-双(4-(4-氨基苯氧基)苯基)丙烷;1,3-双(4-氨基苯氧基)苯;4,4’-双(4-氨基苯氧基)联苯;4,4’-二氨基-3,3’-二羟基联苯;4,4’-二氨基-3,3’-二甲基联苯;4,4’-二氨基-3,3’-二甲氧基联苯;Bisaniline M;Bisaniline P;9,9-双(4-氨基苯基)芴;邻联甲苯胺砜;亚甲基双(邻氨基苯甲酸);1,3-双(4-氨基苯氧基)-2,2-二甲基丙烷;1,3-双(4-氨基苯氧基)丙烷;1,4-双(4-氨基苯氧基)丁烷;1,5-双(4-氨基苯氧基)丁烷;2,3,5,6-四甲基-1,4-苯二胺;3,3’,5,5’-四甲基联苯胺;4,4’-二氨基苯甲酰替苯胺;2,2-双(4-氨基苯基)六氟丙烷;聚氧亚烷基二胺类(例如,Huntsman的Jeffamine D-230、D400、D-2000及D-4000);1,3-环己烷双(甲基胺);间苯二甲基二胺;对苯二甲基二胺;双(4-氨基-3-甲基环己基)甲烷;1,2-双(2-氨基乙氧基)乙烷;3(4),8(9)-双(氨基甲基)三环(5.2.1.02,6)癸烷、1,2-双(氨基辛基)-3-辛基-4-己基-环己烷等。这些当中,从获得表现出优异的介电特性、强度的带树脂的铜箔的观点出发,优选为烷基链的主链的碳数为10~30的二胺。
上述双马来酰亚胺化合物也可以使用市售的化合物,作为优选的例子,可以适当地使用DESIGNER MOLECURES Inc.制的BMI-3000(利用二聚体二胺、均苯四酸二酐及马来酸酐合成)、BMI-1500、BMI-2550、BMI-1400、BMI-2310、BMI-3005等。
上述中,作为本发明中特别适合使用的双马来酰亚胺化合物的DESIGNERMOLECURES Inc.制的BMI-3000由下述的结构式表示。式中,n为1~20的范围的数。
作为固化剂,没有特别限定,可以单独使用选自自由基引发剂、咪唑系固化剂、及阳离子系固化剂中的1种,也可以混合2种以上来使用。
作为自由基系固化剂(聚合引发剂)的例子,可列举出过氧化二异丙苯、叔丁基过氧化异丙苯、叔丁基过氧化氢、过氧化氢异丙苯、偶氮系化合物等。
作为咪唑系固化剂的例子,可列举出咪唑、2-十一烷基咪唑、2-十七烷基咪唑、2-乙基咪唑、2-苯基咪唑、2-乙基-4-甲基咪唑、1-氰基乙基-2-十一烷基咪唑、2,4-二氨基-6-〔2’-甲基咪唑基-(1’)〕-乙基均三嗪等。
作为阳离子系固化剂的例子,可列举出三氟化硼的胺盐、对甲氧基苯重氮六氟磷酸盐、二苯基碘鎓六氟磷酸盐、三苯基锍、四正丁基鏻四苯基硼酸盐、四正丁基鏻-o,o-二乙基二硫代磷酸盐等所代表的鎓盐系化合物。
固化剂的配混量没有特别限定,相对于树脂成分100质量份优选为0.5~30质量份、更优选为1~20质量份、进一步优选为1~15质量份。为0.5质量份以上时,由于获得密合性,因此可实现充分的固化,为30质量份以下时,能够在不损害操作性的范围内确保适用期。
作为填料,没有特别限定,适合使用二氧化硅、氟树脂粉,也可以组合使用两者。
作为二氧化硅的例子,可列举出合成二氧化硅、非晶质二氧化硅(湿式或干式)、胶态二氧化硅、中空二氧化硅、多孔二氧化硅等。从能够进一步降低介电常数的方面出发,优选中空二氧化硅。
作为氟树脂粉的例子,可列举出全氟烷氧基氟树脂、四氟化乙烯·六氟化丙烯共聚物、乙烯·四氟化乙烯共聚物、乙烯·氯三氟乙烯共聚物。
氟树脂粉的粒径没有特别限定,平均粒径优选为0.2μm~30μm。
填料的配混量相对于树脂成分100质量份优选为10~200质量份、更优选为20~200质量份。
填料为氟树脂粉时的配混量相对于树脂成分100质量份优选为40~200质量份、更优选为60~180质量份。
本发明的层叠于带树脂的铜箔上的树脂组合物可以通过以规定量配混上述各成分并与根据需要使用的溶剂一起充分混合来获得。
作为溶剂,没有特别限定,适合使用有机溶剂,作为其具体例,可列举出甲乙酮、甲苯、甲醇、四氢化萘等。这些溶剂可以单独使用1种,也可以混合2种以上来使用。
溶剂的配混量没有特别限定,相对于树脂成分100质量份优选为20~200质量份、更优选为30~150质量份、进一步优选为30~100质量份。
需要说明的是,上述树脂组合物中也可以在不脱离本发明目的的范围内添加以往以来有时在同种树脂组合物中所添加的添加剂。
上述树脂组合物在不包含溶剂的状态下的、在80℃下的复数粘度优选为1×103Pa·s~5×105Pa·s、更优选为1×104Pa·s~5×105Pa·s、进一步优选为5×104Pa·s~5×105Pa·s。
在80℃下的复数粘度为1×103Pa·s以上时,即使不利用紫外线进行临时固化,在压制成型时也不易发生树脂组合物的流动,容易成型。另外,在80℃下的复数粘度为5×105Pa·s以下时,树脂组合物的流动性为适度的,在多层基板成型时能够填埋图案铜箔等的高度差。
需要说明的是,为了提高密合性,上述树脂组合物中可以在不给介电常数或介电损耗角正切带来不良影响的范围内混合环氧树脂。
作为环氧树脂,只要分子内含有环氧基即可,作为具体例,可列举出双酚A型环氧树脂、双酚F型环氧树脂、缩水甘油胺系环氧树脂、缩水甘油醚系环氧树脂、缩水甘油酯系环氧树脂等。
使用环氧树脂时,环氧树脂的配混量没有特别限定,在树脂成分100质量份中优选为1~25质量份、更优选为2~20质量份、进一步优选为2~15质量份。
上述树脂组合物可以用于带树脂的铜箔。此处,带树脂的铜箔是指在铜箔上涂布作为基材的半固化状的树脂而得到的复合材料。
本发明的带树脂的铜箔的制造方法没有特别限定,例如可以如下来获得带树脂的铜箔:将上述树脂组合物以厚度均匀的方式涂布于经脱模处理的聚对苯二甲酸乙二醇酯(PET)薄膜上,使溶剂干燥,从而制作薄膜,将该薄膜贴附于铜板,边加热边进行压制使其固化,由此获得带树脂的铜箔。此时,压制的条件没有特别限定,优选在加热温度为80~130℃、面压力为5~20kg/cm2的条件下边加热5~10分钟边进行压制。
该带树脂的铜箔可以用于覆铜层叠板、柔性印刷电路板等印刷电路板。
覆铜层叠板为印刷电路板用的材料中的一种,是指将上述组合物或使上述组合物浸渗于玻璃布等纤维基材而成者与铜箔贴合而得到的物体。
覆铜层叠板的制造方法没有特别限定,例如可以按照以往的方法、通过以本发明的带树脂的铜箔的树脂面接触纤维基材的方式进行贴附、边加热边压制而成型来制作覆铜层叠板。对于此时的压制条件,优选在加热温度为160~200℃、面压力为15~40kg/cm2的条件下压制30~120分钟,更优选在加热温度为160~180℃、面压力为20~30kg/cm2的条件下压制30~90分钟。需要说明的是,可以在纤维基材的两面设置带树脂的铜箔。
柔性印刷电路板是指在贴合有由具有柔软性的绝缘体形成的薄膜(聚酰亚胺等)和铜箔等导电性金属的基材上形成有电气电路的基板。
柔性印刷电路板的制造方法没有特别限定,例如可以按照以往的方法、通过对覆铜层叠板进行图案蚀刻而形成电路并对覆盖层进行热压接来获得柔性印刷电路板。优选在此时的加热温度为160~200℃、面压力为15~40kg/cm2的条件下压制30~120分钟,更优选在加热温度为160~180℃、面压力为20~30kg/cm2的条件下压制30~90分钟。
[实施例]
以下示出本发明的实施例,但本发明不受以下实施例的限定。需要说明的是,在以下,配混比例等在没有特别说明下采用质量基准。
按照下述表1所示的配方,将双马来酰亚胺树脂、环氧树脂、固化剂、及填料混合,得到用于在铜箔上层叠的树脂组合物。
表1中的各成分的详细情况如下。
·双马来酰亚胺树脂:DESIGNER MOLECULES INC.制“BMI-3000CG”、50质量%甲苯溶液
·环氧树脂:Printec Corporation制“VG3101L”、50质量%甲乙酮溶液
·自由基系固化剂:过氧化氢异丙苯
·咪唑系固化剂:四国化成工业株式会社制“2E4MZ(2-乙基-4-甲基咪唑)”
·阳离子系固化剂:四正丁基鏻四苯基硼酸盐
·二氧化硅:东洋化成株式会社制“WG1000”
·氟树脂粉:株式会社喜多村制“KTL-500F”
将得到的上述树脂组合物以厚度为约100μm的方式涂布于经脱模处理的PET薄膜,在50℃下使溶剂干燥30分钟,制作薄膜。
关于得到的上述树脂组合物及薄膜,对复数粘度、介电常数·介电损耗角正切、剪切强度、树脂组合物的流动、及高度差填埋性进行测定并评价。
·复数粘度:将6张得到的薄膜重叠,制成测定试样。在下述装置及测定条件下测定复数粘度。
装置名:Anton Paar公司制MCR302(Modular Compact Rheometer)
摆动角:0.1%
频率:1Hz
测定范围:25~200℃
升温速度:5℃/分钟
·介电常数·介电损耗角正切:将得到的上述树脂组合物流入至深度0.7mm、长度120mm、宽度70mm的模中,用金属刮刀使表面平坦后,在常温下放置24小时,使溶剂干燥。其后,放入至厚度0.5mm、长度110mm、宽度70mm的氟树脂制模中,用氟树脂片夹住模的上下,以180℃、1MPa进行压制60分钟,得到成型品。压制机使用高温真空压制机(KVHC-II型)北川精机株式会社制。
将得到的成形品沿纵向以约2mm宽度切割,制作样品。利用空腔谐振器摄动法,对3个样品测定介电常数、介电损耗角正切并求出平均值。网络分析仪使用AgilentTechnologies公司制E8361A、空腔谐振器使用株式会社关东电子应用开发制CP531(10GHz)。
介电常数的值为2.5以下时,能够适合用于传输特性优异的印刷电路板。介电损耗角正切的值为0.005以下时,能够适合用于传输特性优异的印刷电路板。
·剪切强度:将得到的上述树脂组合物涂布于铜板并干燥,根据JIS K 6850,测定焊料浸渍试验前后的剪切强度。需要说明的是,焊料浸渍试验为使试验片在260℃的焊料槽中漂浮30秒钟。
剪切强度的值为3MPa以上时,能够适合用于印刷电路板,更优选为4MPa以上。
·树脂组合物的流动:将得到的上述薄膜切割成长方形(20cm×15cm),与相同尺寸的铜箔(厚度18μm)的光泽面重叠,用高温真空压制机(KVHC-II型北川精机株式会社制)在130℃、1MPa的条件压制5分钟,从而得到带树脂的铜箔。接着,用光学显微镜(80倍)观察带树脂的铜箔,评价树脂组合物的流动的程度。树脂组合物的流动如果为0.3mm以下则记为“○”、树脂组合物的流动如果大于0.3mm则记为“×”。
·高度差填埋性:,在铜箔厚度35μm、制作有线和间隔(line and space)(线/间隔)100μm/100μm的图案的柔性印刷基板上,在170℃、面压力为2.5MPa下将得到的带树脂的铜箔压制60分钟。用光学显微镜(80倍)观察该样品的截面,评价高度差是否被组合物填充。如果高度差被组合物填充则记为“○”、如果在高度差中确认到空隙则记为“×”。
[表1]
结果如表1所示,对于使用了含有双马来酰亚胺树脂、固化剂、填料、且填料的配混量相对于树脂成分100质量份为10~200质量份、在80℃下的复数粘度为1×103Pa·s~5×105Pa·s的树脂组合物的实施例,由于具有适度的流动性,因此在压制时未发生树脂组合物的流动、能够使树脂组合物固化,另外,树脂组合物能够填埋高度差。
另一方面,对于使用了填料的含量少、在80℃下的复数粘度低于1×103Pa·s的树脂组合物的比较例1,由于树脂组合物的复数粘度过低,因此在压制成型时发生树脂组合物的流动。对于比较例2,由于树脂组合物的复数粘度过高,因此不能填埋高度差。另外,剪切强度不足3、未能得到足够的强度。
Claims (5)
1.一种带树脂的铜箔,其是将树脂组合物层叠于铜箔的表面的一部分或全部而成的,
所述树脂组合物含有下述通式(I)所示的双马来酰亚胺树脂、固化剂、及填料,
所述填料的配混量相对于树脂成分100质量份为10~200质量份,
所述树脂组合物在80℃下的复数粘度为1×103Pa·s~5×105Pa·s,
其中,式(I)中,X表示脂肪族、脂环式、或芳香族的烃基、且主链的碳数为10~30的烃基,这些基团任选具有杂原子、取代基、或硅氧烷骨架,Y表示脂肪族、脂环式、或芳香族的烃基,这些基团任选具有杂原子、取代基、苯基醚骨架、磺酰骨架、或硅氧烷骨架,n表示1~20的范围的数。
2.根据权利要求1所述的带树脂的铜箔,其特征在于,所述通式(I)所示的双马来酰亚胺化合物是如下化合物:通式(I)中的X以碳数10~30的烷基为主链、该烷基中的彼此邻接的碳所键合的2个侧链部分地形成环状结构。
3.根据权利要求1或2所述的带树脂的铜箔,其特征在于,所述填料为二氧化硅和/或氟树脂粉。
4.根据权利要求1~3中任一项所述的带树脂的铜箔,其特征在于,所述固化剂为选自自由基引发剂、咪唑系固化剂、及阳离子系固化剂中的1种或2种以上。
5.一种印刷电路板,其是使用权利要求1~4中任一项所述的带树脂的铜箔而成的。
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