TW201741132A - 附有樹脂之金屬箔、撓性印刷電路板 - Google Patents
附有樹脂之金屬箔、撓性印刷電路板 Download PDFInfo
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Abstract
本發明之課題在於提供一種可良好維持密著性、撓性、耐熱性、電路充填性而同時不失樹脂成形時的流動性低、可抑制溢出的附有樹脂之金屬箔。於金屬箔依序形成有第1絕緣層及第2絕緣層。第1絕緣層係以聚醯亞胺樹脂層、聚醯胺醯亞胺樹脂層、液晶聚合物樹脂層、氟樹脂層或聚伸苯基醚樹脂層形成。第2絕緣層係以半硬化狀態之聚烯烴樹脂層形成。聚烯烴樹脂層含有成分(A)聚烯烴系彈性體及成分(B)熱硬化性樹脂。前述成分(A)聚烯烴系彈性體在聚烯烴樹脂層整體所佔比率為50~95質量%。
Description
發明領域 本發明涉及一種附有樹脂之金屬箔及撓性印刷電路板,尤其與用於製造撓性印刷電路板等印刷電路板之附有樹脂之金屬箔及用於各種電子機器之撓性印刷電路板有關。
發明背景 小型・薄型的電子機器多使用撓性印刷電路板,最近因進一步高密度化・薄型化之需求,也提高了撓性印刷電路板多層化的需要,同時其所需品質相當嚴格。以往就撓性印刷電路板之多層化材料係使用接合片或覆蓋膜作為絕緣層,並使用銅箔等金屬箔作為導體層。近年為了達成薄型化之要求而提出了一種附有樹脂之金屬箔(譬如參考專利文獻1)。
另外,就多層印刷基板之製法周知有一使多孔基板與形成有銅圖案之印刷基板之間夾持具有與多孔基板之孔相對應之孔的薄膜狀接著劑,進行加熱加壓而積層成形之製法(譬如參考專利文獻2)。在該製法,為了不讓接著劑溢出孔,會於多孔基板上載置熱可塑性樹脂片來進行加熱加壓而積層成形。
為了將上述多層印刷基板薄型化,有考慮使用附有樹脂之多孔金屬箔來替代多孔基板及薄膜狀接著劑。具體上係將附有樹脂之多孔金屬箔的樹脂重疊於印刷基板上,並於附有樹脂之多孔金屬箔的金屬箔上載置熱可塑性樹脂片,進行加熱加壓而積層成形。在該成形時,熱可塑性樹脂片會熱變形而充填孔,藉此可抑制附有樹脂之多孔金屬箔的樹脂溢出孔。
但,由於印刷基板表面形成有銅圖案而呈現凹凸,所以使用熱可塑性樹脂片進行加熱加壓時,印刷基板表面的凹凸可能會於附有樹脂之多孔金屬箔的金屬箔表面上以凹凸呈現。如此一來,金屬箔表面就變凹凸而損害其平滑性,於是該處就很難高密度地安裝上零件。
爰此,有研究研討不使用熱可塑性樹脂片而採用流動性高之物來作為附有樹脂之多孔金屬箔的樹脂。此時,樹脂於成形時容易流動而讓印刷基板表面的凹凸變平整,進而確保其上之金屬箔表面的平滑性。此外,密著性、撓性、耐熱性、電路充填性也良好。但因為附有樹脂之多孔金屬箔的樹脂流動性高,所以有該樹脂溢出孔的問題。 先前技術文獻
專利文獻 專利文獻1:國際公開第2009/145224號 專利文獻2:日本特開平5-191046號公報
發明概要 本發明目的在於提供一種可良好維持密著性、撓性、耐熱性、電路充填性又同時不失樹脂於成形時的流動性低、可抑制溢出的附有樹脂之金屬箔及撓性印刷電路板。
本發明之一態樣的附有樹脂之金屬箔係於金屬箔依序形成有第1絕緣層及第2絕緣層者,前述第1絕緣層係以聚醯亞胺樹脂層、聚醯胺醯亞胺樹脂層、液晶聚合物樹脂層、氟樹脂層或聚伸苯基醚樹脂層形成,前述第2絕緣層係以半硬化狀態之聚烯烴樹脂層形成,同時前述聚烯烴樹脂層含有成分(A)聚烯烴系彈性體及成分(B)熱硬化性樹脂,前述成分(A)聚烯烴系彈性體在前述聚烯烴樹脂層整體所佔比率為50~95質量%。
用以實施發明之形態 以下說明本發明之實施形態。 <附有樹脂之金屬箔>
針對本實施形態之附有樹脂之金屬箔30加以說明。附有樹脂之金屬箔30可作為後述撓性印刷電路板40之材料使用。圖1A~圖1F顯示附有樹脂之金屬箔30的具體例。附有樹脂之金屬箔30於金屬箔50依序形成有第1絕緣層21及第2絕緣層22。
第1絕緣層21係以聚醯亞胺樹脂層9、聚醯胺醯亞胺樹脂層8、液晶聚合物樹脂層4、氟樹脂層5或聚伸苯基醚樹脂層6形成。第1絕緣層21可含有熱硬化性樹脂及熱可塑性樹脂中之至少一者。
在圖1A所示附有樹脂之金屬箔30中,第1絕緣層21係以聚醯亞胺樹脂層9形成。聚醯亞胺樹脂層9係以含有聚醯亞胺樹脂作為主成分之聚醯亞胺樹脂組成物形成。該聚醯亞胺樹脂組成物中譬如亦可含有聚醚醯亞胺樹脂、聚醚碸樹脂。
在圖1B所示附有樹脂之金屬箔30中,第1絕緣層21係以聚醯胺醯亞胺樹脂層8形成。聚醯胺醯亞胺樹脂層8係以含有聚醯胺醯亞胺樹脂作為主成分之聚醯胺醯亞胺樹脂組成物形成。該聚醯胺醯亞胺樹脂組成物中譬如亦可含有聚醚醯亞胺樹脂、聚醚碸樹脂。
在圖1C所示附有樹脂之金屬箔30中,第1絕緣層21係以液晶聚合物樹脂層4形成。液晶聚合物樹脂層4係以含有液晶聚合物樹脂作為主成分之液晶聚合物樹脂組成物形成。液晶聚合物樹脂具有對羥苯甲酸與各種成分(譬如6-羥基-2-萘甲酸)行直鏈狀酯鍵結而成的結構。
在圖1D所示附有樹脂之金屬箔30中,第1絕緣層21係以氟樹脂層5形成。氟樹脂層5係以含有氟樹脂作為主成分之氟樹脂組成物形成。氟樹脂係將含氟之烯烴聚合而得之合成樹脂。氟樹脂之具體例可舉如聚四氟乙烯。
在圖1E所示附有樹脂之金屬箔30中,第1絕緣層21係以聚伸苯基醚樹脂層6形成。聚伸苯基醚樹脂層6係以含有聚伸苯基醚樹脂作為主成分之聚伸苯基醚樹脂組成物形成。聚伸苯基醚樹脂為2,6-二甲基苯醚的聚合物。聚伸苯基醚樹脂包含改質聚伸苯基醚樹脂。改質聚伸苯基醚樹脂係聚伸苯基醚樹脂與聚苯乙烯樹脂等其他樹脂的聚合物摻合體。改質聚伸苯基醚樹脂的成形流動性佳。
在圖1F所示附有樹脂之金屬箔30中,第1絕緣層21係以塗敷層211及薄膜層212構成。塗敷層211及薄膜層212分別係以聚醯亞胺樹脂層9、聚醯胺醯亞胺樹脂層8、液晶聚合物樹脂層4、氟樹脂層5或聚伸苯基醚樹脂層6形成。亦即,圖1F所示附有樹脂之金屬箔30的第1絕緣層21係以選自於由聚醯亞胺樹脂層9、聚醯胺醯亞胺樹脂層8、液晶聚合物樹脂層4、氟樹脂層5及聚伸苯基醚樹脂層6所構成群組中之2層所形成。構成第1絕緣層21之塗敷層211及薄膜層212的2層可為相同的樹脂層亦可為不同的樹脂層。
如此一來,圖1A~圖1F之所有情況,特別是藉由第1絕緣層21以聚醯亞胺樹脂層9、聚醯胺醯亞胺樹脂層8、液晶聚合物樹脂層4、氟樹脂層5或聚伸苯基醚樹脂層6形成,都能提高附有樹脂之金屬箔30之耐熱性及尺寸穩定性,也能提高以該附有樹脂之金屬箔30作為材料而製造之撓性印刷電路板40的耐熱性及尺寸穩定性。另,第1絕緣層21可含有熱硬化性樹脂及熱可塑性樹脂中之至少其一,所以可為硬化狀態,可為半硬化狀態,也可為固化狀態。
第2絕緣層22係以半硬化狀態之聚烯烴樹脂層3形成。半硬化狀態係指硬化反應之中間階段狀態,中間階段則為清漆狀態之A階段與已呈硬化狀態之C階段之間的階段。半硬化狀態之聚烯烴樹脂層3係在室溫下硬化到不沾黏的程度,且於進一步加熱暫且熔融後完全硬化而成為C階段之聚烯烴樹脂層3。聚烯烴樹脂層3係以含有聚烯烴樹脂作為主成分之聚烯烴樹脂組成物形成。
聚烯烴樹脂層3含有成分(A)聚烯烴系彈性體及成分(B)熱硬化性樹脂,且成分(A)聚烯烴系彈性體在聚烯烴樹脂層3整體中所佔比率為50~95質量%。如此一來,聚烯烴樹脂層3含有許多成分(A)聚烯烴系彈性體時,可減低樹脂(尤其是聚烯烴樹脂組成物)於成形時的流動性,抑制溢出。再者,可增加附有樹脂之金屬箔30及以其作為材料所製造之撓性印刷電路板40的柔軟性,令撓性更為提高。成分(A)聚烯烴系彈性體在聚烯烴樹脂層3整體中所佔比率若低於50質量%,就無法充分提高撓性。又,成分(A)聚烯烴系彈性體的熱膨脹係數大,所以成分(A)聚烯烴系彈性體在聚烯烴樹脂層3整體中所佔比率一旦超過95質量%,成形時之尺寸變化就會變大而增加成形後撓性印刷電路板40的翹曲。
成分(A)聚烯烴系彈性體宜為選自於由聚苯乙烯-聚(乙烯/丙烯)嵌段-聚苯乙烯共聚物、聚苯乙烯-聚(乙烯-乙烯/丙烯)嵌段-聚苯乙烯共聚物、聚苯乙烯-聚(乙烯/丁烯)嵌段-聚苯乙烯共聚物、聚苯乙烯-聚異戊二烯嵌段共聚物、加氫聚苯乙烯-聚異戊二烯-聚丁二烯嵌段共聚物、聚苯乙烯-聚(丁二烯/丁烯)嵌段-聚苯乙烯共聚物、乙烯-甲基丙烯酸環氧丙酯共聚物、乙烯-甲基丙烯酸環氧丙酯-丙烯酸甲酯共聚物及乙烯-甲基丙烯酸環氧丙酯-乙酸乙烯酯共聚物所構成群組中之1種或2種以上。
成分(B)熱硬化性樹脂宜為選自於由環氧樹脂、酚樹脂、雙馬來亞醯胺樹脂及兩末端乙烯基之聚伸苯基醚寡聚物所構成群組中之1種或2種以上。環氧樹脂可舉如二環戊二烯型環氧樹脂。
聚烯烴樹脂層3可進一步含有成分(C)硬化促進劑。硬化促進劑可舉如2-乙基-4-甲咪唑。
聚烯烴樹脂層3可進一步含有成分(D)充填材。充填材可舉如二氧化矽。
聚烯烴樹脂層3在180℃下處理60分鐘後的儲存彈性模數於25℃~150℃下為105
~108
Pa為宜。藉此可提高撓性印刷電路板40之耐熱衝擊性,可進一步提高回焊時的焊接耐熱性。
接下來說明附有樹脂之金屬箔30的製造方法。
圖1A~圖1E所示附有樹脂之金屬箔30譬如可以下列方式製造。
首先於銅箔等金屬箔50之表面塗敷液態的聚醯亞胺樹脂組成物、液態的聚醯胺醯亞胺樹脂組成物、液態的液晶聚合物樹脂組成物、液態的氟樹脂組成物或液態的聚伸苯基醚樹脂組成物後,進行加熱乾燥而形成以聚醯亞胺樹脂層9、聚醯胺醯亞胺樹脂層8、液晶聚合物樹脂層4、氟樹脂層5或聚伸苯基醚樹脂層6構成之第1絕緣層21。
接下來,於該第1絕緣層21之表面塗敷液態的聚烯烴樹脂組成物後,進行加熱乾燥而形成以聚烯烴樹脂層3構成之第2絕緣層22。以此方式可製造圖1A~圖1E所示附有樹脂之金屬箔30。在該附有樹脂之金屬箔30中,第1絕緣層21為硬化狀態、半硬化狀態或固化狀態,第2絕緣層22則為半硬化狀態。
圖1A~圖1E所示附有樹脂之金屬箔30亦可以下列方式製造。
首先於銅箔等金屬箔50之表面壓接聚醯亞胺薄膜、聚醯胺醯亞胺薄膜、液晶聚合物薄膜、氟樹脂薄膜或聚伸苯基醚薄膜作為薄膜狀物,而形成以聚醯亞胺樹脂層9、聚醯胺醯亞胺樹脂層8、液晶聚合物樹脂層4、氟樹脂層5或聚伸苯基醚樹脂層6構成之第1絕緣層21。
接下來,於該第1絕緣層21之表面塗敷液態的聚烯烴樹脂組成物後,進行加熱乾燥而形成以聚烯烴樹脂層3構成之第2絕緣層22。以此方式亦可製造圖1A~圖1E所示附有樹脂之金屬箔30。在此附有樹脂之金屬箔30中,第1絕緣層21為硬化狀態、半硬化狀態或固化狀態,第2絕緣層22則為半硬化狀態。
圖1F所示附有樹脂之金屬箔30譬如可以下列方式製造。
於銅箔等金屬箔50之表面塗敷液態的聚醯亞胺樹脂組成物、液態的聚醯胺醯亞胺樹脂組成物、液態的液晶聚合物樹脂組成物、液態的氟樹脂組成物或液態的聚伸苯基醚樹脂組成物而形成塗敷層211。
接下來於該塗敷層211之表面重疊聚醯亞胺薄膜、聚醯胺醯亞胺薄膜、液晶聚合物薄膜、氟樹脂薄膜或聚伸苯基醚薄膜而形成薄膜層212。
接著於該薄膜層212之表面塗敷液態的聚烯烴樹脂組成物後進行加熱乾燥。以此方式可製造圖1C所示附有樹脂之金屬箔30。在此附有樹脂之金屬箔30中,以塗敷層211及薄膜層212構成之第1絕緣層21為聚醯亞胺樹脂層9、聚醯胺醯亞胺樹脂層8、液晶聚合物樹脂層4、氟樹脂層5或聚伸苯基醚樹脂層6,第2絕緣層22則為半硬化狀態之聚烯烴樹脂層3。第1絕緣層21可為硬化狀態,可為半硬化狀態,亦可為固化狀態。 <撓性印刷電路板>
針對本實施形態之撓性印刷電路板40加以說明。撓性印刷電路板40具有上述附有樹脂之金屬箔30之第1絕緣層21的硬化物或固化物及第2絕緣層22之硬化物作為絕緣層2。圖2顯示撓性印刷電路板40之具體例。圖2所示撓性印刷電路板40具備絕緣薄膜7、導體層1、絕緣層2、金屬箔50及非貫通孔13。另,撓性印刷電路板40亦包含軟硬複合印刷電路板(flex-rigid printed wiring board)。
絕緣薄膜7可舉如聚醯亞胺薄膜、聚醯胺醯亞胺薄膜、液晶聚合物薄膜、氟樹脂薄膜、聚伸苯基醚薄膜。
導體層1係於絕緣薄膜7之表面上形成為預定的圖案形狀。導體層1係以存在於絕緣層2內之內部電路11及存在於絕緣層2外之外部電路12所構成。
絕緣層2形成於絕緣薄膜7之表面。該絕緣層2係以上述附有樹脂之金屬箔30之第1絕緣層21的硬化物或固化物及第2絕緣層22之硬化物形成。
金屬箔50形成於絕緣層2之表面。該金屬箔50係以上述附有樹脂之金屬箔30的金屬箔50形成。亦可利用蝕刻等除去該金屬箔50不要的部分而於絕緣層2表面形成電路。
非貫通孔13係貫通絕緣層2及金屬箔50且未貫通絕緣薄膜7之孔。在非貫通孔13之底面露出絕緣薄膜7的表面並於該表面形成有外部電路12。
圖2所示撓性印刷電路板40譬如可以下列方式製造。
首先如圖3所示,準備表面形成有導體層1之絕緣薄膜7及形成有貫通孔14之附有樹脂之金屬箔30。
接著將附有樹脂之金屬箔30的第2絕緣層22重疊至絕緣薄膜7之表面,進行加熱加壓而積層成形。以此方式可製造圖2所示撓性印刷電路板40。
在此,第2絕緣層22係以上述聚烯烴樹脂層3形成,所以成形時聚烯烴樹脂組成物不易從第2絕緣層22流動,可抑制其溢出至非貫通孔13內而被覆外部電路12等情況。而且,上述聚烯烴樹脂組成物在成形時並非完全不流動,而是具有不溢出非貫通孔13內之程度的流動性,所以電路充填性良好。亦即,成形時聚烯烴樹脂組成物可充填內部電路11、11間之間隙,讓絕緣薄膜7表面的凹凸變平整。此外,成形時不是以像專利文獻2所記載之熱可塑性樹脂片的緩衝材來擠壓附有樹脂之金屬箔30之金屬箔50表面,而是以鏡板擠壓。所以,成形後可確保金屬箔50表面的平滑性。而且,在以上述方式製得的撓性印刷電路板40,金屬箔50係以絕緣層2牢固地接著於絕緣薄膜7,所以金屬箔50對於絕緣薄膜7的密著性良好。如此一來,在製造撓性印刷電路板40時若能使用本實施形態之附有樹脂之金屬箔30作為材料,可良好地維持密著性、撓性、耐熱性、電路充填性的同時,成形時之樹脂(尤其是聚烯烴樹脂組成物)的流動性低,還能抑制溢出。
從以上所述實施形態可知,本發明之第1態樣的附有樹脂之金屬箔(30)係於金屬箔(50)依序形成有第1絕緣層(21)及第2絕緣層(22)的附有樹脂之金屬箔(30)。
前述第1絕緣層(21)係以聚醯亞胺樹脂層(9)、聚醯胺醯亞胺樹脂層(8)、液晶聚合物樹脂層(4)、氟樹脂層(5)或聚伸苯基醚樹脂層(6)形成。
前述第2絕緣層(22)係以半硬化狀態之聚烯烴樹脂層(3)形成。
前述聚烯烴樹脂層(3)含有成分(A)聚烯烴系彈性體及成分(B)熱硬化性樹脂。
前述成分(A)聚烯烴系彈性體在前述聚烯烴樹脂層(3)整體所佔比率為50~95質量%。
根據第1態樣,可良好維持密著性、撓性、耐熱性、電路充填性的同時,成形時之樹脂流動性低,還能抑制溢出。
本發明之第2態樣之附有樹脂之金屬箔(30)中,前述成分(A)聚烯烴系彈性體係選自於由聚苯乙烯-聚(乙烯/丙烯)嵌段-聚苯乙烯共聚物、聚苯乙烯-聚(乙烯-乙烯/丙烯)嵌段-聚苯乙烯共聚物、聚苯乙烯-聚(乙烯/丁烯)嵌段-聚苯乙烯共聚物、聚苯乙烯-聚異戊二烯嵌段共聚物、加氫聚苯乙烯-聚異戊二烯-聚丁二烯嵌段共聚物、聚苯乙烯-聚(丁二烯/丁烯)嵌段-聚苯乙烯共聚物、乙烯-甲基丙烯酸環氧丙酯共聚物、乙烯-甲基丙烯酸環氧丙酯-丙烯酸甲酯共聚物及乙烯-甲基丙烯酸環氧丙酯-乙酸乙烯酯共聚物所構成群組中之1種或2種以上。
本發明之第3態樣之附有樹脂之金屬箔(30)中,前述成分(B)熱硬化性樹脂為選自於由環氧樹脂、酚樹脂、雙馬來亞醯胺樹脂及兩末端乙烯基之聚伸苯基醚寡聚物所構成群組中之1種或2種以上。
本發明之第4態樣之附有樹脂之金屬箔(30)中,前述聚烯烴樹脂層(3)更含有成分(C)硬化促進劑。
本發明之第5態樣之附有樹脂之金屬箔(30)中,前述聚烯烴樹脂層(3)更含有成分(D)充填材。
本發明之第6態樣之附有樹脂之金屬箔(30)中,前述聚烯烴樹脂層(3)在180℃下處理60分鐘後之儲存彈性模數於25℃~150℃下為105
~108
Pa。
根據第6態樣可提高撓性印刷電路板(40)之耐熱衝擊性,可進一步提高回焊時的焊接耐熱性。
本發明之一態樣的撓性印刷電路板(40)具有前述附有樹脂之金屬箔(30)的前述第1絕緣層(21)及前述第2絕緣層(22)之硬化物作為絕緣層(2)。
根據一態樣之撓性印刷電路板(40),可良好維持密著性、撓性、耐熱性、電路充填性的同時,成形時之樹脂流動性低還能抑制溢出。 實施例
以下,以實施例來具體說明本發明,惟本發明不受以下實施例限定。 (實施例1)
實施例1係由實施例1-(1)~實施例1-(11)之11種實施例構成。該等實施例除了第2絕緣層不同以外,其餘皆同。
準備Panasonic Corporation製「R-F552」(於銅箔表面塗敷液態的聚醯亞胺樹脂組成物並將其加熱乾燥而製成之2層澆鑄撓性覆銅積層板,銅箔厚度為12μm、硬化狀態之聚醯亞胺樹脂層厚度為12.5μm者)。
於聚醯亞胺樹脂層表面塗敷表3所示(1)~(11)之樹脂組成的聚烯烴樹脂組成物,並將之加熱乾燥而形成厚50μm之半硬化狀態的聚烯烴樹脂層。如此一來,即可獲得於金屬箔(銅箔)依序形成有第1絕緣層(硬化狀態之聚醯亞胺樹脂層)及第2絕緣層(半硬化狀態之聚烯烴樹脂層)的附有樹脂之金屬箔。構成表3所示(1)~(11)之聚烯烴樹脂組成物的成分(A)~(D)之具體製造商名稱及商品名等列於表4。 (實施例2)
實施例2係由實施例2-(1)~實施例2-(11)之11種實施例構成。該等實施例除了第2絕緣層不同以外,其餘皆同。
於厚12μm之銅箔表面塗敷液態的聚醯胺醯亞胺樹脂組成物,並將之加熱乾燥而形成厚12.5μm之硬化狀態的聚醯胺醯亞胺樹脂層。
液態的聚醯胺醯亞胺樹脂組成物係以下述方式調製。藉由將苯偏三酸酐(Nacalai股份有限公司製)192g、4,4’-二異氰酸基-3,3’-二甲基聯苯211g、2,4-二異氰酸甲苯35g、二氮雜二環十一烯(San-Apro Ltd.製)1g及N,N-二甲基乙醯胺(DMAC、Nacalai股份有限公司製)2482g摻合將聚合物濃度調整成15質量%,再將所得混合物加熱並以1小時使其昇溫至100℃,接著將混合物維持在100℃6小時,使反應進行。接著,進一步於混合物添加DMAC 1460g藉此將聚合物濃度調整成10質量%,接著將混合物冷卻至室溫。藉此獲得一液態的聚醯胺醯亞胺樹脂組成物作為溶解有聚醯胺醯亞胺之樹脂溶液。
接著於聚醯胺醯亞胺樹脂層表面塗敷表3所示(1)~(11)之樹脂組成的聚烯烴樹脂組成物,並將之加熱乾燥而形成厚50μm之半硬化狀態的聚烯烴樹脂層。如此一來,即可獲得於金屬箔(銅箔)依序形成有第1絕緣層(硬化狀態之聚醯胺醯亞胺樹脂層)及第2絕緣層(半硬化狀態之聚烯烴樹脂層)的附有樹脂之金屬箔。構成表3所示(1)~(11)之聚烯烴樹脂組成物的成分(A)~(D)之具體製造商名稱及商品名等列於表4。 (比較例1)
形成環氧樹脂層來替代實施例1中之聚烯烴樹脂層。除此以外之內容皆與實施例1相同。
用以形成環氧樹脂層之環氧樹脂組成物之樹脂組成列於表3之(12)。構成該環氧樹脂組成物之成分(E)~(I)的具體製造商名稱、商品名則列於表4。上述樹脂組成中之碳二亞胺改質聚醯胺係如下述首先合成出碳二亞胺化合物後,使用該碳二亞胺化合物來進行合成。 (合成碳二亞胺化合物)
使4,4’-二環己基甲烷二異氰酸酯590g、異氰酸環己酯62.6g及碳二亞胺化觸媒(3-甲基-1-苯基-2-環磷烯1-氧化物)6.12g在180℃下反應48小時而獲得4,4’-二環己基甲烷碳二亞胺樹脂(聚合度=10)作為碳二亞胺化合物。 (合成碳二亞胺改質聚醯胺)
於1公升分離式燒瓶內添加酯共聚醯胺樹脂(商品名:「CM8000」、東麗股份有限公司製)50.0g及異丙醇與甲苯之混合溶劑(質量混合比4:6)450.0g並加以攪拌使其溶解。於所得溶液中添加上述碳二亞胺化合物(4,4’-二環己基甲烷碳二亞胺樹脂)5.0g後,將燒瓶浸漬於120℃之油浴中在迴流下加熱攪拌3小時,然後進行減壓乾燥除去溶媒而獲得碳二亞胺改質聚醯胺。
對以上述方式製得之碳二亞胺改質聚醯胺進行紅外線分光光度測定,結果得在2120cm-1
下確認有顯示碳二亞胺基存在之吸收峰值。此外對上述碳二亞胺改質聚醯胺進行示差掃描熱量測定,結果觀測到一吸熱峰值。又,上述碳二亞胺改質聚醯胺之玻璃轉移溫度(Tg)為120℃,減5%重量之溫度為320℃,溶液黏度為860mPa・s。 (比較例2)
形成環氧樹脂層來替代實施例1中之聚烯烴樹脂層。除此以外之內容皆與實施例1相同。
用以形成環氧樹脂層之環氧樹脂組成物之樹脂組成列於表3之(13)。構成該環氧樹脂組成物之成分(E)~(I)的具體製造商名稱、商品名則列於表4。上述樹脂組成中之碳二亞胺改質聚醯胺係以與比較例1相同的方法合成。 (銅箔剝離強度)
於厚25μm之聚醯亞胺薄膜兩面重疊貼合附有樹脂之金屬箔之第2絕緣層,並在180℃下加熱加壓成形1小時而製作出試樣。測定將該試樣之金屬箔(銅箔)朝與試樣表面呈90°方向剝離時的銅箔剝離強度。測定結果列於表1及表2。 (撓性)
準備一於厚25μm之聚醯亞胺薄膜單面上以厚18μm之電解銅箔形成有MIT圖案之電路的撓性印刷電路板。於該撓性印刷電路板兩面重疊貼合附有樹脂之金屬箔之第2絕緣層,在180℃下加熱加壓成形1小時後以整面蝕刻除去兩面之附有樹脂之金屬箔的金屬箔而製作出試樣。使用該試樣進行MIT試驗。測定條件係設定為在彎折鉗之R=0.38mm、荷重500gf且每分鐘175次之頻率下進行彎折,並以無法取得電路導通之彎折次數來評估撓性。具體上係以100次以上視為「合格」,低於100次視為「不合格」。評估結果列於表1及表2。 (焊接耐熱性)
於厚25μm之聚醯亞胺薄膜兩面重疊貼合附有樹脂之金屬箔之第2絕緣層,並在180℃下加熱加壓成形1小時而製作出試樣。將該試樣分別浸漬於加熱至260℃及288℃之焊錫槽中60秒後,觀察外觀藉以評估焊接耐熱性。無膨脹或剝離等外觀異常發生者視為「合格」,其餘皆視為「不合格」。評估結果列於表1及表2。 (電路充填性)
準備一以厚35μm之軋延銅箔形成有櫛形圖案之電路的撓性印刷電路板,並於該撓性印刷電路板之電路形成面上重疊貼合附有樹脂之金屬箔的第2絕緣層,在180℃下加熱加壓成形1小時而製作出試樣。以肉眼觀察該試樣之截面來評估電路充填性。電路間全被樹脂充填者視為「合格」,其餘皆視為「不合格」。評估結果列於表1及表2。 (樹脂流動性)
於附有樹脂之金屬箔開一直徑10mm之孔後,將該附有樹脂之金屬箔的第2絕緣層重疊貼合至電解銅箔之亮面,在170℃下加熱加壓成形30分鐘而製作出試樣。此時,藉由測定樹脂流至孔之內側的長度來評估樹脂流動性。流出量為1.0mm以下者視為「合格」,其餘皆視為「不合格」。評估結果列於表1及表2。
在實施例1、2的各實施例中,第2絕緣層不論是以11種中之哪一種聚烯烴樹脂組成物形成,各評估項目之結果都不變。
如從表1及表2可確認,各實施例之密著性(銅箔剝離強度)、撓性、耐熱性(焊接耐熱性)良好,而且即使樹脂不易流動,電路充填性依舊優異。
相對於此,各比較例之密著性、撓性、耐熱性、電路充填性雖佳,樹脂卻容易流動。
1‧‧‧導體層 2‧‧‧絕緣層 3‧‧‧聚烯烴樹脂層 4‧‧‧液晶聚合物樹脂層 5‧‧‧氟樹脂層 6‧‧‧聚伸苯基醚樹脂層 7‧‧‧絕緣薄膜 8‧‧‧聚醯胺醯亞胺樹脂層 9‧‧‧聚醯亞胺樹脂層 11‧‧‧內部電路 12‧‧‧外部電路 13‧‧‧非貫通孔 14‧‧‧貫通孔 21‧‧‧第1絕緣層 22‧‧‧第2絕緣層 30‧‧‧附有樹脂之金屬箔 40‧‧‧撓性印刷電路板 50‧‧‧金屬箔 211‧‧‧塗敷層 212‧‧‧薄膜層
圖1A~圖1F係顯示本發明實施形態之附有樹脂之金屬箔多項範例的概略截面圖。
圖2係顯示本發明實施形態之撓性印刷電路板的概略截面圖。
圖3係顯示本發明實施形態之撓性印刷電路板之製造步驟的概略截面圖。
3‧‧‧聚烯烴樹脂層
4‧‧‧液晶聚合物樹脂層
5‧‧‧氟樹脂層
6‧‧‧聚伸苯基醚樹脂層
8‧‧‧聚醯胺醯亞胺樹脂層
9‧‧‧聚醯亞胺樹脂層
21‧‧‧第1絕緣層
22‧‧‧第2絕緣層
30‧‧‧附有樹脂之金屬箔
50‧‧‧金屬箔
211‧‧‧塗敷層
212‧‧‧薄膜層
Claims (8)
- 一種附有樹脂之金屬箔,係於金屬箔依序形成有第1絕緣層及第2絕緣層者, 前述第1絕緣層係以聚醯亞胺樹脂層、聚醯胺醯亞胺樹脂層、液晶聚合物樹脂層、氟樹脂層或聚伸苯基醚樹脂層形成, 前述第2絕緣層係以半硬化狀態之聚烯烴樹脂層形成,同時前述聚烯烴樹脂層含有成分(A)聚烯烴系彈性體及成分(B)熱硬化性樹脂, 前述成分(A)聚烯烴系彈性體在前述聚烯烴樹脂層整體所佔比率為50~95質量%。
- 如請求項1之附有樹脂之金屬箔,其中前述成分(A)聚烯烴系彈性體為選自於由聚苯乙烯-聚(乙烯/丙烯)嵌段-聚苯乙烯共聚物、聚苯乙烯-聚(乙烯-乙烯/丙烯)嵌段-聚苯乙烯共聚物、聚苯乙烯-聚(乙烯/丁烯)嵌段-聚苯乙烯共聚物、聚苯乙烯-聚異戊二烯嵌段共聚物、加氫聚苯乙烯-聚異戊二烯-聚丁二烯嵌段共聚物、聚苯乙烯-聚(丁二烯/丁烯)嵌段-聚苯乙烯共聚物、乙烯-甲基丙烯酸環氧丙酯共聚物、乙烯-甲基丙烯酸環氧丙酯-丙烯酸甲酯共聚物及乙烯-甲基丙烯酸環氧丙酯-乙酸乙烯酯共聚物所構成群組中之1種或2種以上。
- 如請求項1之附有樹脂之金屬箔,其中前述成分(B)熱硬化性樹脂為選自於由環氧樹脂、酚樹脂、雙馬來亞醯胺樹脂及兩末端乙烯基之聚伸苯基醚寡聚物所構成群組中之1種或2種以上。
- 如請求項2之附有樹脂之金屬箔,其中前述成分(B)熱硬化性樹脂為選自於由環氧樹脂、酚樹脂、雙馬來亞醯胺樹脂及兩末端乙烯基之聚伸苯基醚寡聚物所構成群組中之1種或2種以上。
- 如請求項1之附有樹脂之金屬箔,其中前述聚烯烴樹脂層更含有成分(C)硬化促進劑。
- 如請求項1之附有樹脂之金屬箔,其中前述聚烯烴樹脂層更含有成分(D)充填材。
- 如請求項1至6中任一項之附有樹脂之金屬箔,其中前述聚烯烴樹脂層在180℃下處理60分鐘後之儲存彈性模數於25℃~150℃下為105 ~108 Pa。
- 一種撓性印刷電路板,具有如請求項1至7中任一項之附有樹脂之金屬箔的前述第1絕緣層及前述第2絕緣層之硬化物作為絕緣層。
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JP (2) | JP7320768B2 (zh) |
KR (1) | KR20180111809A (zh) |
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JPH0719972B2 (ja) * | 1986-08-29 | 1995-03-06 | 富士通株式会社 | 多層プリント板用樹脂付き銅箔 |
JPH0521911A (ja) * | 1991-07-11 | 1993-01-29 | Sumitomo Electric Ind Ltd | 配線板 |
JP2944308B2 (ja) | 1991-11-08 | 1999-09-06 | 三菱電機株式会社 | 多層プリント基板の製法 |
JP2003342441A (ja) * | 1998-05-13 | 2003-12-03 | Nippon Zeon Co Ltd | ブロック共重合体組成物、その製造方法及び粘着剤組成物 |
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JP4461698B2 (ja) | 2003-04-14 | 2010-05-12 | Dic株式会社 | 接着剤組成物、フレキシブル配線基板、及びカバーレイフィルム |
JP5094323B2 (ja) * | 2007-10-15 | 2012-12-12 | 新光電気工業株式会社 | 配線基板の製造方法 |
WO2009145224A1 (ja) | 2008-05-27 | 2009-12-03 | パナソニック電工株式会社 | プリント配線板用エポキシ樹脂組成物、ソルダーレジスト組成物、樹脂フィルム、樹脂シート、プリプレグ、樹脂付き金属箔、カバーレイ、フレキシブルプリント配線板 |
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TWI544843B (zh) * | 2011-11-22 | 2016-08-01 | 松下知識產權經營股份有限公司 | 可撓性貼金屬基材、可撓性貼金屬基材之製造方法、印刷配線板、多層可撓印刷配線板、及軟硬複合印刷配線板 |
CN104663007B (zh) * | 2012-09-20 | 2017-10-24 | 株式会社可乐丽 | 电路基板及其制造方法 |
KR102166235B1 (ko) | 2012-11-28 | 2020-10-15 | 히타치가세이가부시끼가이샤 | 실록산 화합물, 변성 이미드 수지, 열경화성 수지 조성물, 프리프레그, 수지 부착 필름, 적층판, 다층 프린트 배선판 및 반도체 패키지 |
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JPWO2017130947A1 (ja) | 2018-11-15 |
JP7320768B2 (ja) | 2023-08-04 |
KR20180111809A (ko) | 2018-10-11 |
WO2017130947A1 (ja) | 2017-08-03 |
JP2022133347A (ja) | 2022-09-13 |
CN108702840A (zh) | 2018-10-23 |
US10751976B2 (en) | 2020-08-25 |
US20190061320A1 (en) | 2019-02-28 |
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