TWI719229B - 預浸體、覆金屬積層板及印刷配線板 - Google Patents
預浸體、覆金屬積層板及印刷配線板 Download PDFInfo
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Abstract
本發明涉及一種具有織布基材及樹脂組成物之半硬化物的預浸體。樹脂組成物含有(A1)及(A2)中之至少任一者、(B)、(C1)及(C2)。(A1)環氧樹脂,具有萘骨架及聯苯骨架中之至少任一骨架。(A2)酚樹脂,具有萘骨架及聯苯骨架中之至少任一骨架。(B)高分子聚物,具有式(b1)、式(b2)及式(b3)中之至少式(b2)及式(b3)所示結構,且重量平均分子量為20萬~85萬。(C1)第1充填材,以式(c1)所示第1矽烷耦合劑對第1無機充填材進行表面處理所得。(C2)第2充填材,以式(c2)所示第2矽烷耦合劑對第2無機充填材進行表面處理所得。 [化學式2] (R6)Si(R5)3
…(c1) [化學式3] (R8)Si(R7)3
…(c2)
Description
本揭示一般係涉及預浸體、覆金屬積層板及印刷配線板,較詳細來說係涉及具備織布基材及樹脂組成物之半硬化物的預浸體、使用前述預浸體形成的覆金屬積層板及使用前述覆金屬積層板形成的印刷配線板。
發明背景 以往,預浸體係使含熱硬化性樹脂之樹脂組成物浸潤織布基材並予以加熱乾燥直至成為半硬化狀態而形成(譬如參考專利文獻1-3)。然後於以此方式形成的預浸體積層金屬箔並予以加熱加壓成形,即可製造覆金屬積層板。再將該覆金屬積層板之金屬箔不要的部分除去並設置導體圖案,則可製造印刷配線板。之後將半導體元件安裝於該印刷配線板上予以密封,可製造出封裝件。
近年,於智慧型手機或輸入板PC多數採用的封裝件可舉如PoP(封裝層疊,Package on Package)。該PoP係多個一次封裝件(sub package)積層而成之形態,所以一次封裝件的安裝性及每個一次封裝件的電傳導可靠性便很重要。而且,當封裝件(亦含一次封裝件)在室溫下之翹曲絕對值愈小、或是使氣體環境溫度從室溫變化至260℃時的翹曲變化量愈少,愈能提升其安裝性及傳導可靠性。因此,現下盛行開發封裝件翹曲較小的基板材料。
現在,已提出能作為縮小封裝件翹曲之基板材料為以高剛性、低熱膨脹係數之方向性開發出來的材料。該提議也就是,剛性愈高、熱膨脹係數(CTE:coefficient of thermal expansion)愈低,愈能縮小封裝件之翹曲。
用於製造封裝件的印刷配線板在絕緣層厚度小於0.2mm時,這種薄型物件之絕緣層吸濕量很少,所以即使在焊接等時受到加熱,也能藉由構成絕緣層之樹脂的強度抑制絕緣層膨脹。
但,絕緣層厚度為0.2mm以上時,這種厚型物件之絕緣層吸濕量變多,這些所吸濕之水分若因焊接等而受到加熱而蒸發,構成絕緣層之樹脂便會斷裂,而於絕緣層發生膨脹。如此一來,尤其是以往偏厚的印刷配線板即存有吸濕耐熱性低的問題。 先前技術文獻 專利文獻
專利文獻1:日本專利特開第2006-137942號公報 專利文獻2:日本專利特開第2007-138152號公報 專利文獻3:日本專利特開第2008-007756號公報
本揭示目的在於提供一種可提升吸濕耐熱性的預浸體、覆金屬積層板及印刷配線板。 本揭示一態樣之預浸體具備:織布基材及浸潤至前述織布基材中之樹脂組成物的半硬化物。
前述樹脂組成物含有下述(A1)成分及下述(A2)成分中之至少任一成分、下述(B)成分、下述(C1)成分及下述(C2)成分。
(A1)環氧樹脂,具有萘骨架及聯苯骨架中之至少任一骨架。
(A2)酚樹脂,具有萘骨架及聯苯骨架中之至少任一骨架。
(B)高分子聚物,具有下述式(b1)、下述式(b2)及下述式(b3)中之至少下述式(b2)及下述式(b3)所示結構且重量平均分子量為20萬~85萬。 [化學式1]式(b1)中之x、式(b2)中之y及式(b3)中之z滿足下列關係式。x:y:z(莫耳分率)=0:0.95:0.05~0.2:0.6:0.2(惟,x+y+z≦1、0≦x≦0.2、0.6≦y≦0.95、0.05≦z≦0.2)。式(b2)中,R1為氫原子或甲基,R2則含有氫原子、烷基、環氧丙基及經環氧化烷基中之至少環氧丙基及經環氧化烷基之其一。式(b3)中,R3為氫原子或甲基,R4為Ph(苯基)、-COOCH2
Ph或-COO(CH2
)2
Ph。
(C1)第1充填材,以下述式(c1)所示第1矽烷耦合劑對第1無機充填材進行表面處理所得。 [化學式2] (R6)Si(R5)3
…(c1) 式(c1)中,R5為甲氧基或乙氧基,R6則於碳數3以上且18以下之脂肪族烷基末端具有異氰酸酯基、環氧丙基或胺基。
(C2)第2充填材,以下述式(c2)所示第2矽烷耦合劑對第2無機充填材進行表面處理所得。 [化學式3] (R8)Si(R7)3
…(c2) 式(c2)中,R7為甲氧基或乙氧基,R8則於碳數3以上且18以下之脂肪族烷基末端具有甲基丙烯醯基或乙烯基。 本揭示一態樣之覆金屬積層板具備前述預浸體的硬化物及接著於前述硬化物上的金屬箔。 本揭示一態樣之印刷配線板具備前述預浸體的硬化物及設於前述硬化物上的導體圖案。
用以實施發明之形態 [預浸體] 圖1顯示本實施形態之預浸體1。預浸體1具備織布基材5及浸潤於織布基材5中之樹脂組成物的半硬化物4。
在此,樹脂組成物的半硬化物4意指處於硬化反應中間階段之狀態的樹脂組成物。中間階段又稱B階段,為清漆狀態之A階段及呈完全硬化狀態之C階段之間的階段。在此階段進一步加熱且一經熔融後,便會完全硬化成樹脂組成物之硬化物。另,預浸體1為半硬化狀態,此表示構成預浸體1之樹脂組成物呈半硬化狀態。又,預浸體1之硬化物意指構成預浸體1之樹脂組成物呈完全硬化狀態。
接著說明樹脂組成物。樹脂組成物含有下述(A1)成分及下述(A2)成分中之至少任一成分。亦即,樹脂組成物可含有(A1)成分及(A2)成分兩者,亦可含有(A1)成分且不含(A2)成分,或可不含(A1)成分且含有(A2)成分。此外,樹脂組成物含有下述(B)成分、下述(C1)成分及下述(C2)成分。以下針對構成樹脂組成物之各成分依序說明。
說明(A1)成分。(A1)成分為高剛性成分之基質樹脂。具體上,(A1)成分為具有萘骨架及聯苯骨架中之至少任一骨架的環氧樹脂。如此一來,(A1)成分之環氧樹脂可具有萘骨架及聯苯骨架兩者、可具有萘骨架且不具聯苯骨架、或可不具萘骨架且具有聯苯骨架。以下,具有萘骨架且不具聯苯骨架之環氧樹脂有時會稱作含萘骨架之環氧樹脂。又,不具萘骨架且具有聯苯骨架之環氧樹脂有時會稱作含聯苯骨架之環氧樹脂。
說明(A2)成分。(A2)成分亦為高剛性成分之基質樹脂。具體上,(A2)成分為具有萘骨架及聯苯骨架中之至少任一骨架的酚樹脂。如此一來,(A2)成分之酚樹脂也同樣可具有萘骨架及聯苯骨架兩者、可具有萘骨架且不具聯苯骨架、或可不具萘骨架且具有聯苯骨架。以下,具有萘骨架且不具聯苯骨架之酚樹脂有時會稱作含萘骨架之酚樹脂。又,不具萘骨架且具有聯苯骨架之酚樹脂有時會稱作含聯苯骨架之酚樹脂。
如上述,(A1)成分及(A2)成分兩者具有萘骨架及聯苯骨架中之至少任一骨架,因此可提高預浸體1之硬化物的耐熱性(譬如焊接耐熱性)。尤其,因為萘骨架為剛直的骨架,所以只要(A1)成分及(A2)成分中之至少任一者具有萘骨架,即可進一步提高預浸體1之硬化物的耐熱性。預浸體1為覆金屬積層板2、印刷配線板3及封裝件的材料,所以也會提高該等之耐熱性。另,覆金屬積層板2及印刷配線板3有時會整合稱作基板。
說明(B)成分。(B)成分為低彈性成分,譬如環氧改質丙烯酸樹脂。具體上,(B)成分具有下述式(b1)、下述式(b2)及下述式(b3)中之至少下述式(b2)及下述式(b3)所示結構。 [化學式4]式(b1)中之x、式(b2)中之y及式(b3)中之z滿足下列關係式。x:y:z(莫耳分率)=0:0.95:0.05~0.2:0.6:0.2(惟,x+y+z≦1、0≦x≦0.2、0.6≦y≦0.95、0.05≦z≦0.2)。式(b2)中,R1為氫原子或甲基,R2則含有氫原子、烷基、環氧丙基及經環氧化烷基中之至少環氧丙基及經環氧化烷基之其一。式(b3)中,R3為氫原子或甲基,R4為Ph(苯基)、-COOCH2
Ph或-COO(CH2
)2
Ph。
亦即,(B)成分之主鏈具有式(b1)、式(b2)及式(b3)中之至少式(b2)及式(b3)所示結構。
(B)成分之主鏈具有式(b1)、式(b2)及式(b3)所示結構時,式(b1)、式(b2)及式(b3)所示結構之配列順序無特別限定。此時,(B)成分之主鏈上,式(b1)所示結構彼此可連續亦可不連續,式(b2)所示結構彼此可連續亦可不連續,並且,式(b3)所示結構彼此可連續亦可不連續。
(B)成分之主鏈具有式(b2)及式(b3)所示結構時也同樣地,式(b2)及式(b3)所示結構之配列順序無特別限定。此時,(B)成分之主鏈上,式(b2)所示結構彼此可連續亦可不連續,並且,式(b3)所示結構彼此可連續亦可不連續。
在此,補充說明式(b2)中之R2含有氫原子、烷基、環氧丙基及經環氧化烷基中之至少環氧丙基及經環氧化烷基之其一的意涵。前提上,1個式(b2)所示結構中之R2為1個。以下分就(B)成分僅具有一個式(b2)所示結構之情況及具有2個以上式(b2)所示結構之情況加以說明。
在前者亦即(B)成分具有1個式(b2)所示結構時,R2為環氧丙基或經環氧化烷基。
在後者亦即(B)成分具有2個以上式(b2)所示結構時,至少1個式(b2)所示結構中之R2為環氧丙基或經環氧化烷基,其餘的式(b2)所示結構中之R2則為氫原子或烷基。既然至少1個式(b2)所示結構中之R2為環氧丙基或經環氧化烷基,所以式(b2)所示結構中之R2亦可全部為環氧丙基或經環氧化烷基。
式(b3)所示結構具有Ph(苯基)、-COOCH2
Ph、-COO(CH2
)2
Ph。Ph、-COOCH2
Ph、-COO(CH2
)2
Ph為熱穩定,所以可提高預浸體1之硬化物的強度。因此,可提升以預浸體1作為材料製造而成之基板的吸濕耐熱性。
(B)成分在鄰接之碳原子間宜不具如雙鍵或三鍵等之不飽和鍵。亦即,(B)成分之鄰接的碳原子彼此宜由飽和鍵(單鍵)鍵結。藉此可減低歷時性的氧化,故可抑制失去彈性而變脆的情況。
(B)成分係重量平均分子量(Mw)在20萬~85萬之範圍內的高分子聚物。重量平均分子量的有效數字為2位數。將第3位數(千位數)四捨五入可得20萬或85萬的數值亦含在上述20萬~85萬之範圍內。(B)成分的重量平均分子量若小於20萬,有耐藥性變差之疑慮。相反地,(B)成分的重量平均分子量若大於85萬,有成形性變差之疑慮。(B)成分的重量平均分子量(Mw)宜在30萬~50萬之範圍內。
樹脂組成物中若含有(B)成分,便可藉由預浸體1之硬化物不易吸濕的特性,提高基板之耐濕性,從而可提升絕緣可靠性。又,即使預浸體1之硬化物吸濕了,因為構成該硬化物之樹脂的斷裂強度業已提升,所以還是可提升基板的吸濕耐熱性。尤其即使是絕緣層厚度為0.2mm以上之厚型的印刷配線板,也因為吸濕耐熱性業已提高,所以可抑制在焊接等之加熱時絕緣層膨脹的情況。當然,在絕緣層厚度小於0.2mm之薄型的印刷配線板也能提高吸濕耐熱性。
在此,(A1)成分及(A2)成分與(B)成分在樹脂組成物之半硬化狀態及硬化狀態下宜不相溶呈相分離狀態。藉此,可抑制預浸體1之硬化物的玻璃轉移溫度(Tg)降低,進而可提高基板及封裝件的耐熱性(譬如焊接耐熱性)。
(B)成分之環氧值宜在0.01~0.80eq/kg之範圍內。環氧值係(B)成分1kg中存有的環氧基當量數。(B)成分之環氧值若在上述範圍內,(A1)成分及(A2)成分與(B)成分便不易相溶,藉此可抑制預浸體1之硬化物的玻璃轉移溫度(Tg)降低,進而可提高基板及封裝件的耐熱性。(B)成分之環氧值較宜在0.06~0.40eq/kg之範圍內,更宜在0.14~0.28eq/kg之範圍內。
說明(C1)成分。(C1)成分係以下述式(c1)所示第1矽烷耦合劑對第1無機充填材進行表面處理所得的第1充填材。亦即,第1無機充填材為微粒子的集合體,係透過式(c1)所示第1矽烷耦合劑利用其反應基(藉由甲氧基或乙氧基水解而生成的矽烷醇)而化學鍵結於各微粒子表面上。如此一來,便能形成(C1)成分之第1充填材。 [化學式5] (R6)Si(R5)3
…(c1) 式(c1)中,R5為甲氧基或乙氧基,R6則於碳數3以上且18以下之脂肪族烷基末端具有異氰酸酯基、環氧丙基或胺基。
第1無機充填材之具體例可舉如球狀二氧化矽、硫酸鋇、氧化矽粉、碎二氧化矽、鍛燒滑石、鈦酸鋇、氧化鈦、黏土、氧化鋁、雲母、軟水鋁石、硼酸鋅、錫酸鋅、其他金屬氧化物及金屬水合物。
理想係樹脂組成物中不含平均粒徑在45μm以上之無機充填材。若含有這類粗粒子,尤其是薄型材料(預浸體1、覆金屬積層板2及印刷配線板3)便有絕緣可靠性降低之疑慮。另,平均粒徑意指利用雷射繞射散射法求得之粒度分布中累積值50%的粒徑。
式(c1)所示第1矽烷耦合劑係矽原子上鍵結有於末端具有特定官能基(異氰酸酯基、環氧丙基或胺基)之特定碳數之脂肪族烷基的三官能烷氧矽烷。
於脂肪族烷基之末端具有異氰酸酯基的矽烷耦合劑具體例可舉如3-異氰酸酯丙基三乙氧矽烷。
於脂肪族烷基之末端具有環氧丙基的矽烷耦合劑具體例可舉如3-環氧丙氧基丙基三甲氧矽烷、3-環氧丙氧基丙基三乙氧矽烷及3-環氧丙氧基辛基三甲氧矽烷。
於脂肪族烷基之末端具有胺基的矽烷耦合劑具體例可舉如N-2-(胺乙基)-3-胺丙基三甲氧矽烷、3-胺丙基三甲氧矽烷、3-胺丙基三乙氧矽烷及N-苯基-3-胺丙基三甲氧矽烷。
若以(c1)所示第1矽烷耦合劑對第1無機充填材進行表面處理,於第1充填材表面就會存在特定碳數的脂肪族烷基。該脂肪族烷基之末端鍵結有異氰酸酯基、環氧丙基或胺基,而該等反應基與(A1)成分之環氧樹脂及(A2)成分之酚樹脂的親和性高。因此,藉由該等反應基,(C1)成分之第1充填材可與(A1)成分之環氧樹脂及(A2)成分之酚樹脂行化學鍵結。另,(B)成分雖業經環氧改質(參照式(b2)),但因量少,故與(C1)成分之親和性低。因此,(A1)成分及(A2)成分與(B)成分在樹脂組成物之半硬化狀態及硬化狀態下容易構成不相溶而相分離的結構。
式(c1)所示第1矽烷耦合劑之反應基R6的脂肪族烷基碳數為3以上且18以下。脂肪族烷基之碳數若低於3,預浸體1之硬化物的彈性就會變得過大。
說明(C2)成分。(C2)成分係以下述式(c2)所示第2矽烷耦合劑對第2無機充填材進行表面處理所得的第2充填材。亦即,第2無機充填材為微粒子的集合體,係透過式(c2)所示第2矽烷耦合劑利用其反應基(甲氧基或乙氧基)而化學鍵結於各微粒子表面上。如此一來,便能形成(C2)成分之第2充填材。 [化學式6] (R8)Si(R7)3
…(c2) 式(c2)中,R7為甲氧基或乙氧基,R8則於碳數3以上且18以下之脂肪族烷基末端具有甲基丙烯醯基或乙烯基。
第2無機充填材之具體例可列舉與(C1)成分相同之物,亦即第1無機充填材之具體例。(C1)成分之第1無機充填材及(C2)成分之第2無機充填材於材質、平均粒徑等可相同亦可互異。
式(c2)所示第2矽烷耦合劑係矽原子上鍵結有於末端具有特定官能基(甲基丙烯醯基或乙烯基)之特定碳數之脂肪族烷基的三官能烷氧矽烷。另,甲基丙烯醯基(methacryloyl)的常用名為甲基丙烯醯基(methacryl)。
於脂肪族烷基之末端具有甲基丙烯醯基的矽烷耦合劑具體例可舉如3-甲基丙烯醯氧基丙基三甲氧矽烷、3-甲基丙烯醯氧基丙基三乙氧矽烷及3-甲基丙烯醯氧基辛基三甲氧矽烷。
於脂肪族烷基之末端具有乙烯基的矽烷耦合劑具體例可舉如乙烯基三甲氧矽烷及乙烯基三乙氧矽烷。
若以(c2)所示第2矽烷耦合劑對第2無機充填材進行表面處理,於第2充填材表面就會存在特定碳數的脂肪族烷基。該脂肪族烷基之末端鍵結有甲基丙烯醯基或乙烯基,而該等反應基與(B)成分之親和性高。因此,藉由該等反應基,(C2)成分之第2充填材可與(B)成分行化學鍵結。
式(c2)所示第2矽烷耦合劑之反應基R8的脂肪族烷基碳數為3以上且18以下。脂肪族烷基之碳數若低於3,預浸體1之硬化物的彈性就會變得過大。
一般就含有樹脂及無機充填材之樹脂組成物的硬化物來說,樹脂比無機充填材更容易吸濕。所以,在樹脂組成物之硬化物中,無機充填材若分散不均,無機充填材較稀疏的部分便存有多量的樹脂,故被吸取之水分也會變多;相反地,無機充填材較密集的部分不太存有樹脂,故被吸取之水分也會變少。亦即,無機充填材若分散不均,被吸取之水分也會分散不均。若針對這種樹脂組成物之硬化物進行吸濕耐熱性試驗,水分會偏局部分布,而該部分水分一旦蒸發便會產生膨脹。
針對此,在本實施形態係使用2種充填材(第1充填材及第2充填材)來提升吸濕耐熱性,該2種充填材係以2種矽烷耦合劑(第1矽烷耦合劑及第2矽烷耦合劑)對2種無機充填材(第1無機充填材及第2無機充填材)進行表面處理所得。亦即,(C1)成分之第1充填材與(A1)成分之環氧樹脂及(A2)成分之酚樹脂親和性高,(C2)成分之第2充填材則與(B)成分親和性高。因此,(C1)成分之第1充填材及(C2)成分之第2充填材整體會變得偏靠(A1)成分及(A2)成分附近,或是變得不易偏靠(B)成分附近。換言之,第1充填材及第2充填材整體在樹脂組成物之硬化物中能均勻分散。藉此,也能使水分均勻分散吸取。其結果可減低水分局部分布,抑制膨脹產生,從而可提升吸濕耐熱性。
又,樹脂組成物中若含有(C1)成分之第1充填材及(C2)成分之第2充填材,便可提升基板之尺寸穩定性。
以下說明(C1)成分之第1充填材及(C2)成分之第2充填材的共通事項。另,僅指稱充填材時,意指第1充填材及第2充填材兩者。又,僅指稱無機充填材時,意指第1無機充填材及第2無機充填材兩者。僅指稱矽烷耦合劑時,則意指式(c1)所示第1矽烷耦合劑及式(c2)所示第2矽烷耦合劑兩者。
脂肪族烷基具有緩和預浸體1在硬化後於熱膨脹或熱收縮時產生之應力的功能。若以矽烷耦合劑對無機充填材進行表面處理,無機充填材表面會形成源自脂肪族烷基的應力緩和層。藉由使(A1)成分、(A2)成分及(B)成分中存有具有應力緩和層之充填材,可對(A1)成分、(A2)成分及(B)成分發揮針對熱膨脹或熱收縮的應力緩和作用。其結果,含有充填材之預浸體1硬化後便不易引發熱變形。由此可進一步提升基板之吸濕耐熱性。使充填材表面存有脂肪族烷基而能產生應力緩和作用的理由,可列舉下述諸項。其理由之一,係藉由烷基之單鍵可自由轉動的特性,當(A1)成分、(A2)成分及(B)成分在熱膨脹或熱收縮的同時,充填材之烷基也跟著進行熱膨脹或熱收縮所致。
此外,以預浸體1作為材料所形成之覆金屬積層板2於開孔後進行去膠渣處理(去膠渣蝕刻)時,脂肪族烷基具有減少蝕刻量的功能。
在此,去膠渣處理意指以化學清孔(chemical hole cleaning)等除去利用雷射加工或鑽鑿加工進行開孔時所產生的樹脂膠渣。具體的去膠渣處理可舉如過錳酸處理。在過錳酸處理中係使用以鹼性過錳酸鉀為主成分之去膠渣液。
上述蝕刻量指被去膠渣處理削去的樹脂量。蝕刻量多時,進行開孔所形成的孔內徑有擴大之虞。所以,蝕刻量宜盡可能地少。
若如上述充填材表面存有脂肪族烷基,即可抑制去膠渣液浸透樹脂組成物之硬化物的內部,所以可減少蝕刻量。如此一來,即使進行去膠渣處理,也能抑制孔內徑擴大。
脂肪族烷基於末端具有異氰酸酯基、環氧丙基、胺基、甲基丙烯醯基或乙烯基,該等官能基會與(A1)成分、(A2)成分或(B)成分牢固地鍵結,所以可減少去膠渣處理時之蝕刻量。比起脂肪族烷基末端不具異氰酸酯基、環氧丙基、胺基、甲基丙烯醯基及乙烯基中之任一官能基的情況,更能減少去膠渣處理時的蝕刻量。
以矽烷耦合劑對無機充填材進行表面處理之方法可舉如直接處理法、整體摻混法(integral blending)及乾濃縮法(dry concentrate)。以矽烷耦合劑對無機充填材進行表面處理時,相對於無機充填材的矽烷耦合劑添加量無特別限定。可以下述式(1)來計算,於無機充填材表層整體形成矽烷耦合劑之單分子層所需的矽烷耦合劑量。該計算值之0.1~15倍量即為適宜的矽烷耦合劑添加量。此時,可更有效率發揮無機充填材的應力緩和作用。 WC
=WF
×SF
/SC
…(1) WC
:形成單分子層所需的矽烷耦合劑量(g) WF
:無機充填材之添加量(g) SF
:無機充填材之比表面積(m2
/g) SC
:矽烷耦合劑之最小被覆面積(m2
/g) (C1)成分或(C2)成分宜為平均粒徑100nm以下的奈米填料。(C1)成分或(C2)成分較宜為平均粒徑10~100nm的奈米填料。(C1)成分或(C2)成分中之任一平均粒徑為100nm以下時,可提升去膠渣處理之樹脂膠渣的除去效果。對此進一步詳細說明。吾人認為樹脂膠渣之主成分是高分子聚物的(B)成分。所以,第一種情況,當(C1)成分或(C2)成分中之任一者為上述奈米填料時,該奈米填料會均勻分散在樹脂膠渣中。而這種樹脂膠渣可輕易地透過去膠渣處理除去。第二種情況則是,(C1)成分及(C2)成分皆非上述奈米填料時,樹脂膠渣將幾乎僅由樹脂成分構成。這種樹脂膠渣得以比第一種情況更激進的去膠渣處理條件才能除去,而很難以與第一種情況相同條件之去膠渣處理除去。亦即,去膠渣處理條件相同時,比起(C1)成分及(C2)成分兩者的平均粒徑超過100nm之情況,(C1)成分或(C2)成分中之任一平均粒徑為100nm以下時較可輕易除去樹脂膠渣。如上述,吾人認為該理由是因為平均粒徑100nm以下之奈米填料可均勻分散在樹脂膠渣內所致。(C1)成分或(C2)成分中之任一平均粒徑為10nm以上時,可抑制清漆狀態的樹脂組成物增稠。另,以下僅指稱奈米填料時,意指平均粒徑100nm以下的第1充填材或第2充填材。
樹脂組成物中,(A1)成分及(A2)成分之合計與(B)成分的質量比宜為90:10~50:50,80:20~60:40較佳。換言之,相對於(A1)成分、(A2)成分及(B)成分合計100質量份,(B)成分含量宜為10~50質量份,較宜為20~40質量份。相對於(A1)成分之環氧樹脂的環氧當量1,(A2)成分之酚樹脂的羥基當量宜在0.2~1.1之範圍內。相對於樹脂組成物總量,(C1)成分及(C2)成分的合計含量宜為80質量%以下,50質量%以下較佳。(C1)成分及(C2)成分分別業經預定矽烷耦合劑進行表面處理時,此時的(C1)成分及(C2)成分含量係亦包含矽烷耦合劑之表面處理後的(C1)成分及(C2)成分之含量。(C1)成分與(C2)成分之比率(質量比)宜為98:2~60:40,較宜為95:5~80:20。換言之,相對於(C1)成分及(C2)成分合計100質量份,(C2)成分含量宜為2~40質量份,較宜為5~20質量份。
(C1)成分或(C2)成分為奈米填料時,相對於(A1)成分、(A2)成分及(B)成分合計100質量份,奈米填料宜在1~30質量份之範圍內,較宜在3~10質量份之範圍內。奈米填料若為1質量份以上,即可提升去膠渣處理之樹脂膠渣的除去效果。較詳細而言,去膠渣處理條件若相同,則比起奈米填料低於1質量份之情況,奈米填料為1質量份以上時較可輕易地除去樹脂膠渣。奈米填料若為30質量份以下,即可抑制清漆狀態的樹脂組成物增稠。
樹脂組成物亦可進一步含有添加劑。添加劑之具體例可舉如磷系阻燃劑。樹脂組成物若含有磷系阻燃劑,可提升預浸體1的硬化物、基板、封裝件之阻燃性。另,磷系阻燃劑雖容易吸濕,但在本實施形態係使用了以2種矽烷耦合劑對2種無機充填材進行表面處理所得的2種充填材,所以可提升吸濕耐熱性。磷系阻燃劑幾乎不會影響無機充填材之分散性。以樹脂組成物製造小型零件(譬如封裝件等)時,賦予阻燃性之必要性雖低,但以樹脂組成物製造大型零件(譬如母板等)時,賦予阻燃性之必要性便提高。因此,後者宜預先於樹脂組成物添加磷系阻燃劑。
樹脂組成物亦可進一步含有硬化促進劑。硬化促進劑可舉如咪唑類及其衍生物、有機磷系化合物、辛酸鋅等金屬皂類、二級胺類、三級胺類及四級銨鹽。
說明織布基材5。織布基材5只要是如圖2所示平織,即縱線51及橫線52幾乎呈正交交織者即無特別限定。織布基材5之具體例可舉如玻璃布等由無機纖維構成者,及如芳醯胺布等由有機纖維構成者。織布基材5之厚度宜在10~200μm之範圍內。
接下來說明本實施形態之預浸體1的物性。
以預浸體1之硬化物作為試料來進行動態黏彈性測定(DMA:dynamic mechanical analysis),可得損失正接(tanδ)圖表。該圖表(tanδ曲線)中,理想係100℃以下溫度區及200℃以上溫度區中各存在1個尖峰,較理想係60℃以下溫度區及200℃以上溫度區中各存在1個尖峰。200℃以上溫度區之尖峰為主分散尖峰。主分散尖峰與硬化物分子結構之主鏈運動有關,乃源自玻璃轉移溫度(Tg)。另一方面,100℃以下或60℃以下溫度區之尖峰為副分散尖峰。副分散尖峰與硬化物分子結構之側鏈運動有關,尤其源自(B)成分之高分子聚物。藉由使副分散尖峰從100℃以下往較低溫側位移至60℃以下,可賦予硬化物較高的伸長特性及更低的低彈性。
上述動態黏彈性測定係將頻率維持固定值(譬如10Hz)來進行。損失正接(tanδ)為損失彈性模數(E”)與儲存彈性模數(E’)之比。亦即損失正接(tanδ)=損失彈性模數(E”)/儲存彈性模數(E’)。損失正接(tanδ)之圖表係縱軸取損失正接(tanδ)、橫軸取溫度之圖表,顯示損失正接(tanδ)的溫度相依性。
預浸體1在硬化狀態下,損失彈性模數(E”)與儲存彈性模數(E’)之比在100℃以下溫度區及200℃以上溫度區中為0.05以上為宜,在60℃以下溫度區及200℃以上溫度區中為0.05以上較佳。尤宜在100℃以下溫度區及200℃以上溫度區中,損失正接(tanδ)之尖峰值皆為0.05以上,又更宜在60℃以下溫度區及200℃以上溫度區中,損失正接(tanδ)之尖峰值皆為0.05以上。
損失正接(tanδ)圖表中,100℃以下溫度區及200℃以上溫度區若各存在1個0.05以上之尖峰值,便有可能兼具(A1)成分及(A2)成分之高剛性成分及(B)成分之低彈性成分兩者的特徵。如上述,藉由使副分散尖峰從100℃以下往較低溫側位移至60℃以下,可賦予硬化物較高的伸長特性及更低的低彈性。
又,預浸體1在硬化狀態下於對織布基材5之縱線51或橫線52斜45°角方向(譬如圖2之兩箭頭方向)的拉伸伸長率宜為5%以上。拉伸伸長率之測定通常係以1片做成硬化狀態(C階段狀態)的預浸體1作為試料,亦可使用將多片以縱線51及橫線52之方向分別一致之方式積層並做成硬化狀態的預浸體1作為試料。拉伸伸長率之測定可藉由如下之拉伸試驗進行。首先,於拉伸試驗前測出於對縱線51或橫線52斜45°角方向之試料的長度(L0
)。此時,先將試料寬度調整成5mm。接著使用拉伸試驗機,在速度5mm/分鐘下將試料往對縱線51或橫線52斜45°角方向拉伸,並測定該試料在即將斷裂前的長度(L)。然後,利用下式(2)即可算出拉伸伸長率。 拉伸伸長率(%)={(L-L0
)/L0
}×100…(2) 以上述方法所得的拉伸伸長率若在5%以上,便能達成進一步減低封裝件翹曲。 [預浸體之製造方法]
首先調製樹脂組成物之清漆。於溶劑加入(A1)成分、(A2)成分、(B)成分並使該等溶解後,視需求添加摻合添加劑、硬化促進劑來調製基底清漆。在此,溶劑可舉如丙酮、甲基乙基酮、環己酮等酮系溶劑、甲苯、二甲苯等芳香族系溶劑及二甲基甲醯胺等含氮溶劑。接著於基底清漆加入(C1)成分、(C2)成分並使該等分散,即可調製樹脂組成物之清漆。使(C1)成分及(C2)成分分散時,亦可使用均質機、分散器、珠磨機等分散機。
接下來使清漆狀態(A階段狀態)之樹脂組成物浸潤織布基材5並將之加熱乾燥直到成為半硬化狀態(B階段狀態),即可製造預浸體1。 [覆金屬積層板]
本實施形態之覆金屬積層板2具備預浸體1之硬化物及接著於該硬化物上的金屬箔6。具體上如圖3所示,於預浸體1(較具體為樹脂組成物的半硬化物4)硬化形成之絕緣層41表面上接著有金屬箔6而形成覆金屬積層板2。此時,可於1片預浸體1之單面或雙面積層金屬箔6並予以加熱加壓成形,亦可將多片預浸體1疊合並於該單面或雙面積層金屬箔6後予以加熱加壓成形。半硬化狀態之預浸體1經由加熱,會如上述成為硬化狀態的絕緣層41。絕緣層41之厚度T1低於0.2mm時,可提升覆金屬積層板2之吸濕耐熱性,當然即使為0.2mm以上亦可提升覆金屬積層板2之吸濕耐熱性。覆金屬積層板2之絕緣層41的厚度T1上限為0.4mm左右。金屬箔6可舉如銅箔。積層成形譬如可使用多段式真空壓機及雙帶式壓機進行加熱加壓來施行。 [印刷配線板]
本實施形態之印刷配線板3具備預浸體1之硬化物及設於該硬化物上的導體圖案7。導體圖案7可除去部分覆金屬積層板2之金屬箔6來設置。導體圖案7之形成可藉由譬如減成法(subtractive process)來進行。圖4顯示印刷配線板3之一例。該印刷配線板3係利用減成法形成導體圖案7並利用增層法予以多層化的多層印刷配線板。絕緣層41內部的導體圖案7為內層圖案71,絕緣層41外部表面的導體圖案7為外層圖案72。此時,絕緣層41之厚度T2低於0.2mm時,可提升印刷配線板3之吸濕耐熱性,當然即使為0.2mm以上亦可提升印刷配線板3之吸濕耐熱性。印刷配線板3之絕緣層41的厚度T2上限為0.4mm左右。另,圖4中省略圖示織布基材5。
形成導體圖案7時,為了層連接,會對絕緣層41進行開孔。層連接意指不同層之導體圖案7彼此進行電傳導。孔可為貫通印刷配線板3之貫通孔(通孔,through hole)亦可為未貫通之非貫通孔(盲孔,blind hole)。如圖4所示,於貫通孔內面施行鍍敷等可形成通孔8,於非貫通孔內面施行鍍敷等可形成盲導通孔(blind via hole)9。雖省略圖示,不過亦可形成埋孔。孔內徑譬如在0.01~0.20mm之範圍內。孔深度譬如在0.02~0.80mm之範圍內。開孔可利用雷射加工或鑽鑿加工進行。
絕緣層41若含有(C1)成分及(C2)成分之充填材,由於矽烷耦合劑之脂肪族烷基的末端官能基為異氰酸酯基、環氧丙基、胺基、甲基丙烯醯基或乙烯基,因此可減少去膠渣處理時的蝕刻量。即使產生樹脂膠渣,只要以化學清孔等去膠渣處理洗淨孔內,便可進一步除去孔內之樹脂膠渣。藉此,可解決樹脂膠渣所造成的傳導不良,提升傳導可靠性。
絕緣層41若含有(C1)成分及(C2)成分之充填材,矽烷耦合劑之脂肪族烷基便會成為應力緩和層發揮作用,所以可縮小印刷配線板3之熱膨脹係數更能使其成為低彈性,也可賦予高度的伸長特性。因此可進一步提升印刷配線板3之吸濕耐熱性。
在此說明形成盲導通孔9時可利用的2種方法。2種方法為半加成法(SAP:Semi Additive Process)及改良半加成法(MSAP:Modified Semi Additive Process)。
首先,出示圖5A~圖5G說明SAP。
圖5A顯示內部具有內層圖案711且外部具有主面420的絕緣層42。
首先,如圖5B所示,對絕緣層42進行開孔而形成非貫通孔90。開孔可利用雷射加工進行。雷射L之具體例可舉如CO2
雷射及UV-YAG雷射。非貫通孔90係開口在絕緣層42之主面420之側。非貫通孔90之底面91為內層圖案711之表面。開孔時會產生樹脂膠渣49,該樹脂膠渣49會附著於非貫通孔90之底面91的內層圖案711表面。
接著,為了除去上述樹脂膠渣49,如圖5C所示進行去膠渣處理。此時,能將絕緣層42之主面420、非貫通孔90之內側面92及底面91予以粗化處理,並可同時從非貫通孔90之底面91及內側面92除去樹脂膠渣49。
接下來如圖5D所示,對絕緣層42之主面420、非貫通孔90之底面91及內側面92進行無電電鍍處理,而形成將為晶種層60的無電鍍層61。
接著如圖5E所示,於絕緣層42之主面420形成電鍍保護膜(plating resist)43。電鍍保護膜43係形成在絕緣層42之主面420上未形成外層圖案721的部分。
接下來如圖5F所示,進行電鍍處理,將鍍料62充填至未受電鍍保護膜43遮蓋的部分。
然後如圖5G所示,除去電鍍保護膜43,並同時以蝕刻除去夾在電鍍保護膜43與絕緣層42之主面420之間的晶種層60。如此一來便可形成將內層圖案711與外層圖案721電連接的盲導通孔9。尤其,盲導通孔9已充填有鍍料62,所以亦稱填充通路(filled via)。
在此,絕緣層42若不含(C1)成分及(C2)成分之充填材兩者,便如圖6B所示,於實施SAP後恐在內層圖案711與無電鍍層61之間形成殘留有樹脂膠渣49的填充通路。該樹脂膠渣49係連去膠渣處理也無法完整除去而殘留者。而且,如果像這樣殘留有樹脂膠渣49,便會產生樹脂膠渣49所造成的傳導不良,恐損及傳導可靠性。
相對地,若如本實施形態於絕緣層42含有(C1)成分及(C2)成分之充填材兩者,則如圖6A所示,實施SAP後可在內層圖案711與無電鍍層61之間形成無樹脂膠渣49殘留的填充通路。亦即,可輕易地藉由去膠渣處理除去樹脂膠渣49。藉此,可解決樹脂膠渣49所造成的傳導不良,提升傳導可靠性。另,無樹脂膠渣49殘留不僅指完全無殘留,還包含幾乎不會影響傳導可靠性之程度的微量殘留情況。
接下來出示圖7A~圖7G說明MSAP。
圖7A顯示內部具有內層圖案711且外部具有主面420的絕緣層42。於主面420設有非常薄的將為第1晶種層601的金屬箔63。
首先,如圖7B所示,對絕緣層42連同第1晶種層601一起進行開孔而形成非貫通孔90。開孔可利用雷射加工進行。雷射L之具體例可舉如CO2
雷射及UV-YAG雷射。非貫通孔90係開口在絕緣層42之主面420之側。非貫通孔90之底面91為內層圖案711之表面。開孔時會產生樹脂膠渣49,該樹脂膠渣49會附著於非貫通孔90之底面91的內層圖案711表面。
接著,為了除去上述樹脂膠渣49,如圖7C所示進行去膠渣處理。此時,能將設於絕緣層42之主面420的第1晶種層601、非貫通孔90之內側面92及底面91予以粗化處理,並可同時從非貫通孔90之底面91及內側面92除去樹脂膠渣49。
接下來如圖7D所示,對設於絕緣層42之主面420的第1晶種層601、非貫通孔90之底面91及內側面92進行無電電鍍處理,而形成將為第2晶種層602的無電鍍層61。
接著如圖7E所示,於絕緣層42之主面420形成電鍍保護膜43。電鍍保護膜43係形成在絕緣層42之主面420上未形成外層圖案721的部分。
接下來如圖7F所示,進行電鍍處理,將鍍料62充填至未受電鍍保護膜43遮蓋的部分。
然後如圖7G所示,除去電鍍保護膜43,並同時以蝕刻除去夾在電鍍保護膜43與絕緣層42之主面420之間的第1晶種層601及第2晶種層602。如此一來便可形成將內層圖案711與外層圖案721電連接的盲導通孔9。尤其,盲導通孔9已充填有鍍料62,所以亦稱填充通路。
在此,絕緣層42若不含(C1)成分及(C2)成分之充填材兩者,便如圖8B所示,於實施MSAP後恐在內層圖案711與無電鍍層61之間形成殘留有樹脂膠渣49的填充通路。該樹脂膠渣49係連去膠渣處理也無法完整除去而殘留者。而且,如果像這樣殘留有樹脂膠渣49,便會產生樹脂膠渣49所造成的傳導不良,恐損及傳導可靠性。
相對地,若如本實施形態於絕緣層42含有(C1)成分及(C2)成分之充填材兩者,則如圖8A所示,實施MSAP後可在內層圖案711與無電鍍層61之間形成無樹脂膠渣49殘留的填充通路。亦即,可輕易地藉由去膠渣處理除去樹脂膠渣49。藉此,可解決樹脂膠渣49所造成的傳導不良,提升傳導可靠性。另,無樹脂膠渣49殘留不僅指完全無殘留,還包含幾乎不會影響傳導可靠性之程度的微量殘留情況。 [封裝件]
於印刷配線板3上安裝半導體元件並加以密封,可製造FBGA(Fine pitch Ball Grid Array:細間距球柵陣列)等封裝件。將封裝件當作一次封裝件使用而將多個一次封裝件予以積層時,還可製造PoP(Package on Package:層疊封裝)等封裝件。如此一來便可製造各種形態的封裝件,但不論何種封裝件,皆透過(A1)成分、(A2)成分及(B)成分減低了翹曲並提高了吸濕耐熱性。亦即,藉由(A1)成分及(A2)成分可提高剛性,藉由(B)成分可降低彈性、緩和應力,因此無關封裝件之形態,皆通用地能減低封裝件翹曲。此外,藉由(A1)成分、(A2)成分及(B)成分亦可提高封裝件之吸濕耐熱性。
實施例 以下藉由實施例來具體說明本發明。 <清漆配方>
(A1)成分 ・含萘骨架之環氧樹脂(DIC股份有限公司製「HP-9500」) ・含聯苯骨架之環氧樹脂(日本化藥股份有限公司製「NC-3000-H」) (A2)成分 ・含萘骨架之酚樹脂(DIC股份有限公司製「HPC-9500P」) ・含聯苯骨架之酚樹脂(日本化藥股份有限公司製「GPH-103」) (B)成分 ・環氧改質丙烯酸樹脂(Nagase ChemteX Corporation製「PMS-12-82」) 其具有式(b1)、式(b2)及式(b3)所示結構,鄰接之碳原子間不具不飽和鍵,且重量平均分子量為50萬、環氧值為0.21eq/kg。 (C1)成分 ・異氰酸酯矽烷處理二氧化矽 其係業經3-異氰酸酯丙基三乙氧矽烷進行表面處理的球狀二氧化矽((股)Admatechs製「SC2500GNO」),平均粒徑為0.5μm(500nm)。 ・環氧矽烷處理二氧化矽 其係業經3-環氧丙氧基丙基三甲氧矽烷進行表面處理的球狀二氧化矽((股)Admatechs製「SC2500SEJ」),平均粒徑為0.5μm(500nm)。 (C2)成分 ・乙烯基矽烷處理二氧化矽 其係業經乙烯基三甲氧矽烷進行表面處理的球狀二氧化矽((股)Admatechs製「SC2500SVJ」),平均粒徑為0.5μm(500nm)。 ・甲基丙烯醯矽烷處理二氧化矽 其係業經3-甲基丙烯醯氧基丙基三甲氧矽烷進行表面處理的球狀二氧化矽((股)Admatechs製「YA050C-MJE」),平均粒徑為50nm。 (溶劑) ・甲基乙基酮 (添加劑) ・磷系阻燃劑(大塚化學股份有限公司製「SPB-100」) <預浸體>
以表1所示摻合量(質量份)於溶劑添加(A1)成分、(A2)成分、(B)成分並使該等溶解後,進一步加入摻合添加劑,接著加入(C1)成分、(C2)成分並使該等分散來調製出樹脂組成物之清漆。實施例1~5中,(A1)成分及(A2)成分與(B)成分不相溶呈相分離。另,使用(股)島津製作所製雷射繞射式粒度分布測定裝置「SALD-2100」確認(C1)及(C2)成分在清漆中之分散性。
接下來,使上述樹脂組成物之清漆浸潤織布基材(日東紡績股份有限公司製玻璃布「WEA116E」、厚88μm)使其硬化後厚度為100μm後,使其在130℃下加熱乾燥5分鐘直到成為半硬化狀態而製造出預浸體。 [覆金屬積層板]
將上述預浸體2片疊合並於該兩面積層作為金屬箔的銅箔(厚12μm)後,於真空條件下在2.94MPa(30kgf/cm2
)下加壓並在220℃下加熱60分鐘予以成形,而製造出作為覆金屬積層板之覆銅積層板(CCL)。覆金屬積層板之絕緣層厚度為200μm。再來以蝕刻除去覆金屬積層板兩面的金屬箔,而製造出厚0.2mm的未包覆板(unclad board)。 <基板特性>
進行下列物性評估。其結果列於表1。 [吸濕耐熱性]
將上述未包覆板裁切成正方形而獲得試驗片(大小5cm×5cm)。將該試驗片之端面研磨成平滑。再來,作為前處理將該試驗片放於100℃烘箱內1小時使其乾燥。然後使其在60℃、濕度60%、1大氣壓力(101.3kPa)之條件下分別吸濕0小時、12小時、24小時。接著將這些吸濕時間互異的3種試驗片浸漬於288℃之焊槽中120秒。然後,以目測確認從焊槽取出之試驗片上是否有產生膨脹。表1中,試驗片上未產生膨脹者標示為「S」,試驗片上產生1mm以下之膨脹者標示為「A」,試驗片上產生5mm以下之膨脹者標示為「B」,試驗片上產生超過5mm之膨脹者標示為「C」。 (分散性)
裁切上述未包覆板並研磨其截面後,以電子顯微鏡(SEM)在3000倍下觀察不存在織布基材的部位,評估無機充填材分散性的良否。圖9A為實施例1之電子顯微鏡照片,圖9B為比較例1之電子顯微鏡照片。白色部分為無機充填材,可知,圖9A中分散性良好,圖9B中分散性不良。實施例2~5結果與實施例1結果相同,比較例2結果則與比較例1結果相同。 (損失正接(tanδ)≧0.05的峰頂溫度)
將上述未包覆板於對織布基材之縱線方向斜45°角方向(斜向),以5mm寬裁切成短籤狀,做出長25mm之試料。針對該試料使用動態黏彈性測定裝置(SII Technology(股)製「DMS6100」),在夾具間距離10mm、升溫速度5℃/分鐘、拉伸模式之條件下進行動態黏彈性測定(DMA:dynamic mechanical analysis)。透過讀取該測定所得損失正接(tanδ)之圖表,求出tanδ≧0.05之峰頂溫度。 (彈性模數)
從上述測定所得損失正接(tanδ)之圖表讀取25℃下之儲存彈性模數(E’)並以此作為彈性模數。 (熱膨脹係數(CTE))
將上述未包覆板於平行於織布基材縱線的方向,以5mm寬裁切成短籤狀,做出長25mm之試料。針對該試料使用熱機械分析裝置(SII Technology(股)製「TMA6100」),在探針間距離15mm、拉伸荷重5mN之條件下進行測定。以該測定所得膨脹曲線之50~100℃的平均熱膨脹係數作為熱膨脹係數(CTE)。 (拉伸伸長率)
將上述未包覆板於對織布基材之縱線方向斜45°角方向(斜向),以5mm寬裁切成短籤狀,做出長80mm之試料。針對該試料,使用拉伸試驗機((股)島津製作所製「Autograph AGS-X」),在標線間距離60mm、5mm/分鐘之條件下進行拉伸試驗。然後,從進行拉伸試驗前的初始試料長度(L0
)與拉伸試驗期間試料將要斷裂前之長度(L),藉由下式算出拉伸伸長率。 拉伸伸長率(%)={(L-L0
)/L0
}×100 (拉伸斷裂強度)
從上述拉伸試驗中試料斷裂時的荷重F(N)與試料截面積S(mm2
),藉由下式算出拉伸斷裂強度。 拉伸斷裂強度(MPa)=F(N)/S(mm2
) (阻燃性) 按UL94規格進行垂直燃燒試驗。
如表1明示可確認,相較於比較例1、2,實施例1~5的無機充填材分散性較佳,吸濕耐熱性及拉伸斷裂強度較為優異。
從實施例1、2之對比可確認,即使(C1)成分之矽烷耦合劑具有異氰酸酯基或具有環氧丙基,皆可提升吸濕耐熱性。
從實施例1、3之對比可確認,即使(C2)成分之矽烷耦合劑具有乙烯基或具有甲基丙烯醯基,皆可提升吸濕耐熱性。
從實施例1、4之對比可確認,即使(A1)成分及(A2)成分具有萘骨架或具有聯苯骨架,皆可提升吸濕耐熱性。
從實施例1、5之對比可確認,不論有無磷系阻燃劑,皆可提升吸濕耐熱性。
1‧‧‧預浸體2‧‧‧覆金屬積層板3‧‧‧印刷配線板4‧‧‧樹脂組成物的半硬化物5‧‧‧織布基材6、63‧‧‧金屬箔7‧‧‧導體圖案8‧‧‧通孔9‧‧‧盲導通孔41、42‧‧‧絕緣層43‧‧‧電鍍保護膜49‧‧‧樹脂膠渣51‧‧‧縱線52‧‧‧橫線60‧‧‧晶種層61‧‧‧無電鍍層62‧‧‧鍍料71、711‧‧‧內層圖案72、721‧‧‧外層圖案90‧‧‧非貫通孔91‧‧‧底面92‧‧‧內側面420‧‧‧主面601‧‧‧第1晶種層602‧‧‧第2晶種層L‧‧‧雷射T1‧‧‧絕緣層41之厚度T2‧‧‧絕緣層41之厚度
圖1係顯示本揭示一實施形態之預浸體的概略截面圖。 圖2係顯示構成同上之預浸體之織布基材的概略俯視圖。 圖3係顯示本揭示一實施形態之覆金屬積層板的概略截面圖。 圖4係顯示本揭示一實施形態之印刷配線板的概略截面圖。 圖5中,圖5A~圖5G係顯示半加成法之一連串步驟的概略截面圖。 圖6中,圖6A係顯示於實施半加成法後,內層圖案與鍍料間未殘留樹脂膠渣之狀態的概略截面圖。圖6B係顯示於實施半加成法後,內層圖案與鍍料間殘留有樹脂膠渣之狀態的概略截面圖。 圖7中,圖7A~圖7G係顯示改良半加成(modified semi-additive)法之一連串步驟的概略截面圖。 圖8中,圖8A係顯示於實施改良半加成法後,內層圖案與鍍料間未殘留樹脂膠渣之狀態的概略截面圖。圖8B係顯示於實施改良半加成法後,內層圖案與鍍料間殘留有樹脂膠渣之狀態的概略截面圖。 圖9中,圖9A係顯示實施例1之無機充填材之分散狀態的電子顯微鏡照片。圖9B係顯示比較例1之無機充填材之分散狀態的電子顯微鏡照片。
1‧‧‧預浸體
4‧‧‧樹脂組成物的半硬化物
5‧‧‧織布基材
51‧‧‧縱線
52‧‧‧橫線
Claims (16)
- 一種預浸體,具備:織布基材及浸潤於前述織布基材中之樹脂組成物的半硬化物, 前述樹脂組成物含有下述(A1)成分及下述(A2)成分中之至少任一成分、下述(B)成分、下述(C1)成分及下述(C2)成分; (A1)環氧樹脂,具有萘骨架及聯苯骨架中之至少任一骨架; (A2)酚樹脂,具有萘骨架及聯苯骨架中之至少任一骨架; (B)高分子聚物,具有下述式(b1)、下述式(b2)及下述式(b3)中之至少下述式(b2)及下述式(b3)所示結構且重量平均分子量為20萬~85萬; [化學式1]式(b1)中之x、式(b2)中之y及式(b3)中之z滿足下列關係式;x:y:z(莫耳分率)=0:0.95:0.05~0.2:0.6:0.2(惟,x+y+z≦1、0≦x≦0.2、0.6≦y≦0.95、0.05≦z≦0.2);式(b2)中,R1為氫原子或甲基,R2則含有氫原子、烷基、環氧丙基及經環氧化烷基中之至少環氧丙基及經環氧化烷基之其一;式(b3)中,R3為氫原子或甲基,R4為Ph(苯基)、-COOCH2 Ph或-COO(CH2 )2 Ph; (C1)第1充填材,以下述式(c1)所示第1矽烷耦合劑對第1無機充填材進行表面處理所得; [化學式2] (R6)Si(R5)3 …(c1) 式(c1)中,R5為甲氧基或乙氧基,R6則於碳數3以上且18以下之脂肪族烷基末端具有異氰酸酯基、環氧丙基或胺基; (C2)第2充填材,以下述式(c2)所示第2矽烷耦合劑對第2無機充填材進行表面處理所得; [化學式3] (R8)Si(R7)3 …(c2) 式(c2)中,R7為甲氧基或乙氧基,R8則於碳數3以上且18以下之脂肪族烷基末端具有甲基丙烯醯基或乙烯基。
- 如請求項1之預浸體,其中前述(C1)成分或前述(C2)成分係平均粒徑為100nm以下的奈米填料。
- 如請求項2之預浸體,其中相對於前述(A1)成分、前述(A2)成分及前述(B)成分合計100質量份,前述奈米填料在1~30質量份之範圍內。
- 如請求項1之預浸體,其中前述樹脂組成物不含平均粒徑在45μm以上的無機充填材。
- 如請求項1之預浸體,其中前述(A1)成分和前述(A2)成分之合計與前述(B)成分的質量比為90:10~50:50。
- 如請求項1之預浸體,其中相對於前述樹脂組成物之總量,前述(C1)成分及前述(C2)成分的合計含量為80質量%以下。
- 如請求項1之預浸體,其中前述(C1)成分與前述(C2)成分的質量比為98:2~60:40。
- 如請求項1之預浸體,其中前述(A1)成分及前述(A2)成分與前述(B)成分不相溶呈相分離。
- 如請求項1之預浸體,其中前述(B)成分之環氧值在0.01~0.80eq/kg之範圍內。
- 如請求項1之預浸體,其中前述(B)成分在鄰接之碳原子間不具不飽和鍵。
- 如請求項1之預浸體,其中前述樹脂組成物更含有磷系阻燃劑。
- 如請求項1之預浸體,其中前述織布基材之厚度在10~200μm之範圍內。
- 如請求項1之預浸體,其在硬化狀態下於100℃以下溫度區及200℃以上溫度區內,損失彈性模數及儲存彈性模數之比為0.05以上。
- 如請求項1至13中任一項之預浸體,其在硬化狀態下於對前述織布基材之縱線或橫線斜45°角方向的拉伸伸長率為5%以上。
- 一種覆金屬積層板,具備如請求項1至14中任一項之預浸體的硬化物及接著於前述硬化物上的金屬箔。
- 一種印刷配線板,具備如請求項1至14中任一項之預浸體的硬化物及設於前述硬化物上的導體圖案。
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JP6861377B2 (ja) | 2021-04-21 |
CN109476862B (zh) | 2021-07-16 |
US11059260B2 (en) | 2021-07-13 |
TW201823323A (zh) | 2018-07-01 |
KR20190038538A (ko) | 2019-04-08 |
JPWO2018021113A1 (ja) | 2019-05-16 |
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