TW201700541A - 聚醯亞胺積層膜、聚醯亞胺積層膜之製造方法、熱塑性聚醯亞胺之製造方法、及撓性貼金屬箔積層體之製造方法 - Google Patents

聚醯亞胺積層膜、聚醯亞胺積層膜之製造方法、熱塑性聚醯亞胺之製造方法、及撓性貼金屬箔積層體之製造方法 Download PDF

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TW201700541A
TW201700541A TW105110184A TW105110184A TW201700541A TW 201700541 A TW201700541 A TW 201700541A TW 105110184 A TW105110184 A TW 105110184A TW 105110184 A TW105110184 A TW 105110184A TW 201700541 A TW201700541 A TW 201700541A
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block
thermoplastic
film
polyimide
elastic modulus
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TW105110184A
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TWI683836B (zh
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細貝誠二
後裕之
齋藤隼平
小野和宏
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鐘化股份有限公司
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Abstract

本發明使用包含熱塑性聚醯亞胺層之聚醯亞胺積層膜，作為剝離強度較高、且能夠抑制鹼性環境下產生之龜裂之聚醯亞胺積層膜，該熱塑性聚醯亞胺層包含380℃下之儲存彈性模數為0.15GPa以上之區塊A、及380℃下之儲存彈性模數為0.10GPa以下之區塊B。

Description

聚醯亞胺積層膜、聚醯亞胺積層膜之製造方法、熱塑性聚醯亞胺之製造方法、及撓性貼金屬箔積層體之製造方法
本發明係關於一種能夠較佳地用於撓性貼金屬箔積層板之聚醯亞胺積層膜、聚醯亞胺積層膜之製造方法、熱塑性聚醯亞胺之製造方法、及撓性貼金屬箔積層體之製造方法。
近年，隨著電子機器之高性能化、高功能化、及小型化迅速發展，對電子機器中所使用之電子零件之小型化、及輕量化要求亦越來越高。基於上述要求，對於半導體元件封裝方法、或安裝有半導體元件之配線板，亦要求更高密度、高功能、且高性能者。
重要電子零件之一中有軟性印刷配線板(以下，亦稱為FPC)。於製造FPC之情形時，通常將具有柔韌性之較薄之絕緣膜層作為核心膜(以下，亦有時稱為基礎膜、或基材)，於該核心膜之表面經由包含各種接著材料之接著層，藉由加熱及壓接而貼合金屬箔層，製成撓性貼金屬箔積層板。進而，藉由於撓性貼金屬箔積層板上形成電路圖案，於該電路圖案之表面形成覆蓋層(覆蓋層膜)，製成FPC。
包含上述絕緣膜層、接著層、及金屬箔層三層之軟性印刷配線 板(三層FPC)中，一直以來，聚醯亞胺膜等作為絕緣膜層而被廣泛使用。其原因在於聚醯亞胺膜具有優異之耐熱性、及電特性等。作為接著層，通常使用環氧樹脂系、或丙烯酸系樹脂系等熱固性接著劑。該等熱固性接著劑之優勢在於，能於較低溫度下進行接著。然而，隨著該等熱固性接著劑耐熱性欠佳，進而可撓性、或電可靠性等三層FPC所要求之特性變得嚴峻，而認為使用熱固性接著劑之三層FPC難以應對。相對於此，使用絕緣膜層中直接設有金屬箔層之FPC、或作為接著層而使用熱塑性聚醯亞胺膜之FPC(以下，亦稱為兩層FPC)。該兩層FPC具有較三層FPC優異之特性，今後可期望有更多之需求。FPC中，除上述使用特性，最近對降低成本之要求亦變得越來越高。因此，FPC製造步驟自先前之批次式(非連續步驟)正在向捲對捲式(以下，亦稱為連續步驟)之加工方法改變。
[先前技術文獻] [專利文獻]
[專利文獻1]日本公開專利公報「日本專利特開平06-120659號公報(1994年4月28日公開)」
[專利文獻2]日本公開專利公報「日本專利特開2012-186377號公報(2012年9月27日公開)」
[專利文獻3]國際公開WO2008/114642號(2008年9月25日公開)
雖兩層FPC具有如此優異特性，但新的問題正在變得顯著。較佳地用於兩層FPC之聚醯亞胺積層膜，於作為核心膜之非熱塑性聚醯亞胺膜之至少單面上具有包含熱塑性聚醯亞胺層之接著層。將該聚醯亞胺積層膜加工成FPC時，有使聚醯亞胺積層膜與鹼性水溶液接觸之步驟，要求聚醯亞胺積層膜之耐鹼性。捲對捲式中，聚醯亞胺積層膜需 要耗費較先前之批次式之情形更高之負荷，其結果為，如下問題變得顯著：先前之批次式中之鹼處理中並未承認之於聚醯亞胺積層膜內產生龜裂之問題。
先前，關於控制對顯影、蝕刻處理、抗蝕劑剝離之各步驟中所使用之鹼性溶液之耐性的聚醯亞胺(例如，專利文獻1、2)，有進行過報告。然而，該等材料，雖於先前之批次式之FPC製造步驟中並未出現問題，但於上述捲對捲式之連續FPC製造步驟中出現問題，至今仍未提供有即便經過如此步驟亦不會產生龜裂之聚醯亞胺材料。
又，揭示有具有如下特徵之技術(專利文獻3)：積層於耐熱性聚醯亞胺膜上之接著層含有熱塑性聚醯亞胺，該熱塑性聚醯亞胺具有結晶性。然而，上述技術係以吸濕焊料耐受性為對象之技術，專利文獻3中，關於上述此種膜之於鹼性條件下之龜裂，無揭示亦無暗示。
本發明之目的在於提供一種聚醯亞胺積層膜，該聚醯亞胺積層膜係於聚醯亞胺積層膜上設金屬箔作為撓性貼金屬箔積層板，進而以捲對捲式連續地製造軟性印刷配線板時，能夠抑制起因於鹼性環境下之龜裂發生且改良鹼性環境下之強韌性。又，本發明之另一目的在於提供一種剝離強度較高之聚醯亞胺積層膜。
鑒於上述狀況，本發明者等人為解決上述問題進行銳意研究，結果發現藉由以下新型聚醯亞胺積層膜能夠解決上述問題，從而完成本發明。
<1>本發明之聚醯亞胺積層膜，其特徵在於包含熱塑性聚醯亞胺層，該熱塑性聚醯亞胺層包含380℃下之儲存彈性模數為0.15GPa以上之區塊A、及380℃下之儲存彈性模數為0.10GPa以下之區塊B。
<2>本發明之聚醯亞胺積層膜，較佳為上述區塊A為至少包含4,4'-雙(4-胺基苯氧基)聯苯(BAPB)、及3,3',4,4'-聯苯四羧酸二酐 (BPDA)之區塊成分，上述區塊B為至少包含2,2'-雙[4-(4-胺基苯氧基)苯基]丙烷(BAPP)之二胺、及均苯四甲酸二酐(PMDA)之區塊成分。
<3>本發明之聚醯亞胺積層膜，較佳為以80℃浸漬於鹼性溶液中10分鐘時，重量減少率為未達2重量%者。
<4>本發明之聚醯亞胺積層膜，較佳為上述熱塑性聚醯亞胺層為380℃下之儲存彈性模數為0.05GPa以下者。
<5>本發明之熱塑性聚醯亞胺之製造方法，其特徵在於包含以下步驟：使380℃下之儲存彈性模數為0.15GPa以上之區塊A、與380℃下之儲存彈性模數為0.10GPa以下之區塊B共聚。
<6>本發明之聚醯亞胺積層膜之製造方法，其特徵在於具有以下步驟：對包含380℃下之儲存彈性模數為0.15GPa以上之區塊A、及380℃下之儲存彈性模數為0.10GPa以下之區塊B之熱塑性聚醯亞胺層、非熱塑性聚醯亞胺層進行積層。
<7>本發明之撓性貼金屬箔積層體之製造方法，其特徵在於具有以下步驟：對包含熱塑性聚醯亞胺層之聚醯亞胺積層膜、及金屬箔進行積層，該熱塑性聚醯亞胺層包含380℃下之儲存彈性模數為0.15GPa以上之區塊A、及380℃下之儲存彈性模數為0.10GPa以下之區塊B。
<8>本發明之撓性貼金屬箔積層體之製造方法，較佳為上述積層步驟係藉由熱層壓法、或流延法而進行。
本發明之聚醯亞胺積層膜，即便於由捲對捲式進行之連續之FPC製造步驟中，亦能夠抑制龜裂之發生。
本發明能夠實現剝離強度較高之聚醯亞胺積層膜。
1‧‧‧聚醯亞胺積層膜
2‧‧‧不織布
3‧‧‧金屬板
4‧‧‧牛皮紙
5‧‧‧氯乙烯樹脂膜
6‧‧‧脫模膜
7‧‧‧電解銅箔
10‧‧‧積層材料(2、3、4、5、6)
11‧‧‧撓性金屬箔積層體
圖1係對實施例中之撓性金屬箔積層體之浸漬除膠渣液時之耐龜 裂性之測定方法進行表示之圖式。
以下，對本發明之實施形態進行說明，但本發明並未限定於此。本發明並不限定於以下說明之各構成，可於申請專利範圍所示之範圍內進行各種變更，將不同實施形態或實施例中分別揭示之技術手段進行適當的組合而獲得之實施形態或實施例亦包含於本發明之技術範圍內。又，本說明書中所記載之學術文獻及專利文獻於本說明書中全部作為參考文獻而引用。再者，本說明書中若無特別記載，則表示數值範圍之「A~B」之含義分別為「A以上(包含A且較A大)B以下(包含B且較B小)」。
本發明者等人為了改良聚醯亞胺積層膜於鹼性環境下之強韌性，而對聚醯亞胺之分子設計進行銳意研究，結果發現：聚醯亞胺積層膜中所具備之構成熱塑性聚醯亞胺層之熱塑性聚醯亞胺之凝集結構對鹼性環境下之聚醯亞胺積層膜之強韌性影響極大，且可兼具該強韌性、及熱塑性聚醯亞胺所具有之接著性等加工特性。根據熱塑性聚醯亞胺之分子設計，本發明者等人最初發現之見解為鹼性環境下之聚醯亞胺積層膜之強韌性得到改良。
所謂本發明中之熱塑性聚醯亞胺，意指由藉由動態黏彈性測定裝置(DMA)而測定之損失彈性模數除以儲存彈性模數而獲得之損失係數(tanδ)之峰頂溫度求出之玻璃轉移溫度(Tg)為150℃~350℃之範圍者。
所謂本發明中之非熱塑性聚醯亞胺，意指通常即便加熱亦不顯示軟化、及接著性之聚醯亞胺。更具體而言，所謂本發明中之非熱塑性聚醯亞胺，係指以膜之狀態於380℃加熱2分鐘時，膜不會產生褶皺或褶皺延伸，且膜保持形狀之聚醯亞胺。
(聚醯亞胺積層膜)
本發明之聚醯亞胺積層膜，其特徵在於包含熱塑性聚醯亞胺層，該熱塑性聚醯亞胺層包含380℃下之儲存彈性模數為0.15GPa以上之區塊A、及380℃下之儲存彈性模數為0.10GPa以下之區塊B。
本發明中，「區塊A」、「區塊B」及「包含區塊A與區塊B之熱塑性聚醯亞胺」各自之儲存彈性模數可使用動態黏彈性測定裝置而測定。首先，分別製造單獨包含區塊A之聚醯亞胺、單獨包含區塊B之聚醯亞胺、及使區塊A與區塊B共聚而成之聚醯亞胺。將自該等聚醯亞胺而獲得之膜用作試片，測定各試片之動態黏彈性。相對於溫度之值製作繪製有動態黏彈性之值的圖表，自該圖表，讀取380℃下之動態黏彈性之值。380℃下之動態黏彈性之值成為「區塊A」、「區塊B」及「包含區塊A與區塊B之熱塑性聚醯亞胺」各自之380℃下之儲存彈性模數。
本發明中，較佳為區塊A之380℃下之儲存彈性模數為0.15GPa以上，更佳為區塊A之380℃下之儲存彈性模數為0.16GPa以上。若區塊A之380℃下之儲存彈性模數為0.15GPa以上，則能夠實現耐鹼性優異之聚醯亞胺積層膜。再者，本發明之聚醯亞胺積層膜，較佳為於以80℃浸漬於鹼性溶液(pH13，例如3%氫氧化鈉水溶液)中10分鐘時，重量減少率未達浸漬前之重量之2.0重量%，若為此種聚醯亞胺積層膜則耐鹼性優異。
又，本發明中，較佳為區塊B之380℃下之儲存彈性模數為0.10GPa以下，更佳為區塊B之380℃下之儲存彈性模數為0.8GPa以下。若區塊B之380℃下之儲存彈性模數為0.10GPa以下，則聚醯亞胺積層膜與金屬箔層之密接性優異。
本發明之熱塑性聚醯亞胺層之380℃下之儲存彈性模數，較佳為0.05GPa以下，更佳為0.04GPa以下。若熱塑性聚醯亞胺層之380℃下之儲存彈性模數為0.05GPa以下，則聚醯亞胺積層膜與金屬箔層之密 接性優異。
(熱塑性聚醯亞胺層)
構成熱塑性聚醯亞胺層之熱塑性聚醯亞胺，可藉由包含使380℃下之儲存彈性模數為0.15GPa以上之區塊A、與380℃下之儲存彈性模數為0.10GPa以下之區塊B共聚之步驟的方法製造。
關於獲得作為本發明中之熱塑性聚醯亞胺層之前驅物的熱塑性聚醯胺酸(以下，有時亦稱為聚醯胺酸)之方法進行說明。
(熱塑性聚醯胺酸之原料單體)
能夠對成為本發明中所使用之熱塑性聚醯亞胺層之前驅物的熱塑性聚醯胺酸進行合成之原料單體，只要為可形成380℃下之儲存彈性模數為0.15GPa以上之區塊A、及380℃下之儲存彈性模數為0.10GPa以下之區塊B者即可，可使用通常使用之芳香族二胺及芳香族酸二酐。
以下，對形成本發明之熱塑性聚醯亞胺之區塊成分之單體進行說明。
作為可較佳地用作芳香族二胺之例，可列舉2,2'-雙[4-(4-胺基苯氧基)苯基]丙烷、4,4'-二胺基二苯丙烷、4,4'-二胺基二苯甲烷、4,4'-二胺基二苯硫醚、3,3'-二胺基二苯基碸、4,4'-二胺基二苯基碸、4,4'-氧基二苯胺(4,4'-二胺基二苯醚)、3,3'-氧基二苯胺、3,4'-氧基二苯胺、4,4'-二胺基二苯二乙基矽烷、4,4'-二胺基二苯基矽烷、4,4'-二胺基二苯基乙基氧化膦、4,4'-二胺基二苯基N-甲基胺、4,4'-二胺基二苯基N-苯胺、1,4-二胺基苯(對苯二胺)、雙{4-(4-胺基苯氧基)苯基}碸、雙{4-(3-胺基苯氧基)苯基}碸、4,4'-雙(4-胺基苯氧基)聯苯、4,4'-雙(3-胺基苯氧基)聯苯、1,3-雙(3-胺基苯氧基)苯、1,3-雙(4-胺基苯氧基)苯、1,3-雙(3-胺基苯氧基)苯、3,3'-二胺基二苯甲酮、4,4'-二胺基二苯甲酮、2,2-雙(4-胺基苯氧基苯)丙烷等，可單獨使用該等或併用複數 個。
又，作為可較佳地用作芳香族酸二酐之例，可列舉均苯四甲酸二酐、2,3,6,7-萘四羧酸二酐、3,3',4,4'-聯苯四羧酸二酐、1,2,5,6-萘四羧酸二酐、2,2',3,3'-聯苯四羧酸二酐、3,3',4,4'-二苯甲酮四羧酸二酐、2,2',3,3'-二苯甲酮四羧酸二酐、4,4'-氧鄰苯二甲酸二酐、3,4'-氧鄰苯二甲酸二酐、2,2-雙(3,4-二羧基苯基)丙酸二酐、3,4,9,10-二萘嵌苯四羧酸二酐、雙(3,4-二羧基苯基)丙酸二酐、1,1-雙(2,3-二羧基苯基)乙烷二酐、1,1-雙(3,4-二羧基苯基)乙烷二酐、雙(2,3-二羧基苯基)甲酸二酐、雙(3,4-二羧基苯基)乙酸二酐、氧二鄰苯二甲酸二酐、雙(3,4-二羧基苯基)磺酸二酐、對伸苯基雙(偏苯三甲酸單酯酸酐)、伸乙基雙(偏苯三甲酸單酯酸酐)、雙酚A雙(偏苯三甲酸單酯酸酐)及該等之類似物等。
作為較佳地用於包含於本發明之熱塑性聚醯亞胺層中之區塊A之芳香族二胺，可例示4,4'-雙(4-胺基苯氧基)聯苯、4,4'-二胺基二苯醚、對苯二胺等。又，作為較佳地用於包含於本發明之熱塑性聚醯亞胺層中之區塊A之芳香族酸二酐，可例示3,3',4,4'-聯苯四羧酸二酐、3,3',4,4'-二苯甲酮四羧酸二酐、2,2',3,3'-二苯甲酮四羧酸二酐等。
作為較佳地用於包含於本發明之熱塑性聚醯亞胺層中之區塊B之芳香族二胺，可例示2,2'-雙[4-(4-胺基苯氧基)苯基]丙烷、4,4'-二胺基二苯醚、1,3-雙(4-胺基苯氧基)苯等。又，作為較佳地用於包含於本發明之熱塑性聚醯亞胺層中之區塊B之芳香族酸二酐，可例示均苯四甲酸二酐、氧二鄰苯二甲酸二酐等。
本發明中，該等芳香族二胺及芳香族酸二酐中，區塊A為至少包含4,4'-雙(4-胺基苯氧基)聯苯(BAPB)及3,3',4,4'-聯苯四羧酸二酐(BPDA)之區塊成分，區塊B為至少包含2,2'-雙[4-(4-胺基苯氧基)苯基]丙烷(BAPP)之二胺及均苯四甲酸二酐(PMDA)之區塊成分，且區塊A 及區塊B分別為使包含上述芳香族二胺及芳香族酸二酐之聚醯胺酸進行醯亞胺化而成者，就儲存彈性模數之表現而言，特佳。
(區塊A與區塊B之組成比)
關於本發明中之包含於熱塑性聚醯亞胺中之區塊A與區塊B之組成比，較佳為(區塊A之量：區塊B之量)為(30莫耳%：70莫耳%)~(70莫耳%：30莫耳%)之範圍。
(熱塑性聚醯胺酸之製造時所用之溶劑)
製造熱塑性聚醯胺酸時所用之溶劑，若為溶解熱塑性聚醯胺酸之溶劑則可使用任何物質，但可較佳地使用醯胺系溶劑即N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯烷酮等，尤其是可較佳地使用N,N-二甲基甲醯胺、N,N-二甲基乙醯胺。
(熱塑性聚醯胺酸之製造)
本發明中之熱塑性聚醯胺酸之製造方法，若為可形成包含區塊A及區塊B之熱塑性聚醯亞胺，即包含380℃下之儲存彈性模數為0.15GPa以上之區塊A、及380℃下之儲存彈性模數為0.10GPa以下之區塊B之熱塑性聚醯亞胺層的方法，則可使用公知之任何方法。例如，藉由下述步驟(a)~(c)，而能夠製造熱塑性聚醯胺酸：(a)使芳香族二胺、及芳香族酸二酐以芳香族二胺過量之狀態於有機極性溶劑中進行反應，獲得兩末端具有胺基之預聚物之步驟；(b)將與步驟(a)中所使用者之結構不同之芳香族二胺，追加添加至上述有機極性溶劑中之步驟；(c)進而，將與步驟(a)中所使用者之結構不同之芳香族酸二酐，以整個步驟中之芳香族二胺與芳香族酸二酐實質上成為相等莫耳之方式，添加至上述有機極性溶劑中而進行聚合之步驟。
或者，藉由下述步驟(a)~(c)，而能夠製造熱塑性聚醯胺酸：(a)使芳香族二胺、及芳香族酸二酐以芳香族酸二酐過量之狀態 於有機極性溶劑中進行反應，獲得兩末端具有酸酐基之預聚物之步驟；(b)將與步驟(a)中所使用者之結構不同之芳香族酸二酐，追加添加至上述有機極性溶劑中之步驟；(c)進而，將與步驟(a)中所使用者之結構不同之芳香族二胺，以整個步驟中之芳香族二胺與芳香族酸二酐實質上成為相等莫耳之方式，添加至上述有機極性溶劑中而進行聚合之步驟。
(熱塑性聚醯胺酸之固形物成分濃度)
熱塑性聚醯胺酸之固形物成分濃度並無特別限定，但若為5重量%~35重量%之範圍內，則可獲得具有充分機械強度之熱塑性聚醯亞胺。
(熱塑性聚醯胺酸之組成)
本發明之熱塑性聚醯胺酸中，可加入填料、熱穩定劑、抗氧化劑、紫外線吸收劑、抗靜電劑、阻燃劑、顏料、染料、脂肪酸酯、有機潤滑劑(例如蠟)等各種添加劑。
(非熱塑性聚醯亞胺)
本發明之聚醯亞胺積層膜可為於非熱塑性聚醯亞胺膜之至少單面具有本發明之熱塑性聚醯亞胺層者。以下，對本發明中所使用之非熱塑性聚醯亞胺膜之例進行說明。
可用於非熱塑性聚醯亞胺膜中之非熱塑性聚醯亞胺之製造中所使用之芳香族二胺，雖並無特別限定，但可列舉2,2'-雙[4-(4-胺基苯氧基)苯基]丙烷、4,4'-二胺基二苯丙烷、4,4'-二胺基二苯甲烷、4,4'-二胺基二苯硫醚、3,3'-二胺基二苯基碸、4,4'-二胺基二苯基碸、4,4'-氧基二苯胺(4,4'-二胺基二苯醚、)、3,3'-氧基二苯胺、3,4'-氧基二苯胺、4,4'-二胺基二苯二乙基矽烷、4,4'-二胺基二苯基矽烷、4,4'-二胺基二苯基乙基氧化膦、4,4'-二胺基二苯基N-甲基胺、4,4'-二胺基二苯 基N-苯胺、1,4-二胺基苯(對苯二胺)、雙{4-(4-胺基苯氧基)苯基}碸、雙{4-(3-胺基苯氧基)苯基}碸、4,4'-雙(4-胺基苯氧基)聯苯、4,4'-雙(3-胺基苯氧基)聯苯、1,3-雙(3-胺基苯氧基)苯、1,3-雙(4-胺基苯氧基)苯、1,3-雙(3-胺基苯氧基)苯、3,3'-二胺基二苯甲酮、4,4'-二胺基二苯甲酮、2,2-雙(4-胺基苯氧基苯)丙烷等，可單獨使用該等或併用複數個。
可用於非熱塑性聚醯亞胺膜中之非熱塑性聚醯亞胺之製造中所用之芳香族酸二酐，亦並無特別限定，但可列舉均苯四甲酸二酐、2,3,6,7-萘四羧酸二酐、3,3',4,4'-聯苯四羧酸二酐、1,2,5,6-萘四羧酸二酐、2,2',3,3'-聯苯四羧酸二酐、3,3',4,4'-二苯甲酮四羧酸二酐、2,2',3,3'-二苯甲酮四羧酸二酐、4,4'-氧鄰苯二甲酸二酐、3,4'-氧鄰苯二甲酸二酐、2,2-雙(3,4-二羧基苯基)丙酸二酐、3,4,9,10-二萘嵌苯四羧酸二酐、雙(3,4-二羧基苯基)丙酸二酐、1,1-雙(2,3-二羧基苯基)乙烷二酐、1,1-雙(3,4-二羧基苯基)乙烷二酐、雙(2,3-二羧基苯基)甲酸二酐、雙(3,4-二羧基苯基)乙酸二酐、氧二鄰苯二甲酸二酐、雙(3,4-二羧基苯基)磺酸二酐、對伸苯基雙(偏苯三甲酸單酯酸酐)、伸乙基雙(偏苯三甲酸單酯酸酐)、雙酚A雙(偏苯三甲酸單酯酸酐)及該等之類似物等。
作為非熱塑性聚醯亞胺之前驅物之聚醯胺酸(以下，有時亦稱為非熱塑性聚醯胺酸)係藉由使上述芳香族二胺與芳香族酸二酐於有機溶劑中以實質上成為大致相等莫耳之方式混合並反應而獲得。
製造非熱塑性聚醯胺酸時所使用之有機溶劑，若為溶解非熱塑性聚醯胺酸之溶劑則可使用任何物質。可較佳地使用例如醯胺系溶劑即N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯烷酮等，可更佳地使用N,N-二甲基甲醯胺、N,N-二甲基乙醯胺。非熱塑性聚醯胺酸之固形物成分濃度並無特別限定，若為5重量%~35重量%之範圍 內，則可獲得具有充分機械強度之非熱塑性聚醯亞胺膜。
關於作為原料之芳香族二胺與芳香族酸二酐之添加順序，亦無特別限定，但除原料之化學結構外，亦可藉由控制添加順序，而控制所獲得之非熱塑性聚醯亞胺之特性。
亦可以改善滑動性、導熱性、導電性、耐電暈性、環剛度等膜之各種特性為目的，向上述非熱塑性聚醯胺酸中添加填料。作為填料可使用任何物質，但作為較佳例，可列舉二氧化矽、氧化鈦、氧化鋁、氮化矽、氮化硼、磷酸氫鈣、磷酸鈣、雲母等。
又，於不損害作為所獲得之非熱塑性聚醯亞胺膜、或聚醯亞胺積層膜之特性之範圍內，亦可於上述非熱塑性聚醯胺酸中混合環氧樹脂、苯氧樹脂等熱固性樹脂，聚醚酮、聚醚醚酮等熱塑性樹脂。作為該等樹脂之添加方法，可列舉若該樹脂為可溶於溶劑者，則向作為非熱塑性聚醯亞胺之前驅物之聚醯胺酸中添加該樹脂之方法。若聚醯亞胺亦為可溶於溶劑者，則亦可將該樹脂添加至聚醯亞胺溶液中。若該樹脂為不溶於溶劑者，則可列舉將作為上述非熱塑性聚醯亞胺之前驅物之聚醯胺酸預先醯亞胺化後，將聚醯亞胺與該樹脂以熔融混練之方式複合化之方法。然而，所獲得之撓性貼金屬箔積層體之焊料耐熱性或加熱收縮率等有可能惡化，故本發明中較理想為不使用具有熔融性之聚醯亞胺。因此，與聚醯亞胺混合之樹脂之較理想為使用可溶性者。
(非熱塑性聚醯亞胺膜之製造)
上述非熱塑性聚醯亞胺膜之製造方法，較佳為包含以下步驟：i)於有機溶劑中使芳香族二胺與芳香族四羧酸二酐反應而獲得非熱塑性聚醯胺酸溶液之步驟；ii)將包含上述非熱塑性聚醯胺酸溶液之製膜摻雜劑自模嘴流延於支撐體上，而形成樹脂膜(有時亦稱為樹脂層或液膜)之步驟； iii)將樹脂膜於支撐體上加熱而製成具有自我支撐性之凝膠膜後，自支撐體剝離凝膠膜之步驟；及iv)進而加熱凝膠膜，使剩餘之醯胺酸進行醯亞胺化且使其乾燥而獲得非熱塑性聚醯亞胺膜之步驟。
ii)以後之步驟大致區分為熱醯亞胺化法與化學醯亞胺化法。熱醯亞胺化法為如下方法：不使用脫水閉環劑等，而將聚醯胺酸溶液作為製膜摻雜劑僅僅流延於支撐體上並加熱，藉此促進醯亞胺化。另一者之化學醯亞胺化法為如下方法：將向聚醯胺酸溶液中添加脫水閉環劑及觸媒中至少任一者作為醯亞胺化促進劑而成者，用作製膜摻雜劑，促進醯亞胺化。雖可使用任一方法，但化學醯亞胺化法於生產性方面優異。
作為脫水閉環劑，可較佳地使用以乙酸酐為代表之酸酐。作為觸媒，可較佳地使用脂肪族三級胺、芳香族三級胺、雜環式三級胺等三級胺。
作為流延製膜摻雜劑之支撐體，可較佳地使用玻璃板、鋁箔、環形不鏽鋼帶、不鏽鋼鼓等。根據最終獲得之膜之厚度、生產速度，設定製膜摻雜劑之加熱條件，相對於製膜摻雜劑進行部分醯亞胺化或乾燥中至少一者後，自支撐體剝離而獲得聚醯胺酸膜(以下，稱為凝膠膜)。
固定上述凝膠膜之端部，一面避免硬化時之收縮一面使其乾燥，自凝膠膜去除水、殘留溶劑、醯亞胺化促進劑，並且將剩餘之醯胺酸完全醯亞胺化，從而獲得含有聚醯亞胺之膜。關於加熱條件，只要根據最終獲得之膜之厚度、生產速度適當地設定即可。
(聚醯亞胺積層膜之製造)
作為製造本發明之聚醯亞胺積層膜之方法，可於上述ii)步驟中使用具有複數個流路之共擠壓模嘴，同時形成包含熱塑性聚醯胺酸及 非熱塑性聚醯胺酸之複數層樹脂膜，亦可於上述i)步驟中合成非熱塑性聚醯胺酸，繼而進行至上述ii)~iv)步驟並且暫時回收非熱塑性聚醯亞胺膜後，於其上以塗佈等方式形成新的包含熱塑性聚醯胺酸之樹脂膜。醯亞胺化需要非常高之溫度，故於設置聚醯亞胺以外之樹脂膜之情形時，為了抑制熱分解而較佳為採取後者方法。再者，於藉由塗佈而設置熱塑性聚醯亞胺層之情形時，可於非熱塑性聚醯亞胺膜上塗佈熱塑性聚醯胺酸，其後進行醯亞胺化，亦可將能夠形成熱塑性聚醯亞胺層之熱塑性聚醯亞胺溶液塗佈於非熱塑性聚醯亞胺膜上並使其乾燥。
藉由將本發明之聚醯亞胺積層膜與金屬箔進行積層，而能夠製造用於加工成FPC之撓性貼金屬箔積層體。作為於金屬箔上形成聚醯亞胺積層膜之方法，可列舉：a)以上述之方式獲得聚醯亞胺積層膜後，藉由加熱加壓於聚醯亞胺積層膜上貼合金屬箔而獲得撓性貼金屬箔積層體之方法(熱層壓法)；b)於金屬箔上流延含有熱塑性聚醯胺酸溶液或非熱塑性聚醯胺酸溶液中至少任一溶液之複數層有機溶劑溶液，藉由加熱，自有機溶劑溶液去除溶劑、進行醯亞胺化而獲得撓性貼金屬箔積層體之方法(流延法)；c)於金屬箔上流延含有熱塑性聚醯亞胺酸溶液或非熱塑性聚醯亞胺酸溶液中至少任一含有聚醯亞胺之熔融液，藉由冷卻該熔融液而獲得撓性貼金屬箔積層體之方法(流延法)。
其中，若使聚醯亞胺具有熔融性，則所獲得之撓性貼金屬箔積層體之焊料耐熱性或加熱收縮率等有可能會變差，故較佳為使用a)或b)之方法。若聚醯亞胺為溶劑可溶性者，則可使用含有聚醯亞胺之有機溶劑溶液代替含有聚醯胺酸之有機溶劑溶液。以下，對a)及b)之詳 細內容進行說明。
a)之方法中，藉由向所獲得之聚醯亞胺膜以加熱加壓之方式貼合金屬箔之熱層壓，而獲得本發明之撓性貼金屬箔積層體。關於貼合金屬箔之方法、條件，只要適當地選擇先前公知者即可。
b)之方法中，對於在金屬箔上流延含有聚醯胺酸之有機溶劑溶液之機器並無特別限定，可使用模嘴塗佈機或缺角輪塗佈機(註冊商標)、反向塗佈機、刮刀塗佈機等先前公知之機器。關於用於去除溶劑、進行醯亞胺化之加熱機器，亦可利用先前公知之機器，可列舉例如熱風爐、遠紅外線爐。與a)之方法相同地，能夠藉由化學醯亞胺化法而縮短加熱時間、提高生產性。然而，於醯亞胺化之過程中，作為脫水閉環劑之酸酐中會生成酸，故存在根據金屬箔之種類而發生氧化之情況。關於添加脫水閉環劑，較佳為根據金屬箔之種類或加熱條件適當地選擇。於設置本發明中之熱塑性聚醯亞胺層及非熱塑性聚醯亞胺膜之情形等設置複數層聚醯亞胺樹脂膜之情形時、或者亦設置聚醯亞胺以外之樹脂膜之情形時，可較佳地使用複數次重複上述流延、加熱步驟、或藉由共擠壓或連續流延而形成複數層流延層繼而一次性加熱之方法。b)之方法中，於醯亞胺化結束之同時，獲得撓性貼金屬箔積層體。於樹脂膜之兩面設置金屬箔時，只要藉由加熱加壓於相反側之樹脂膜面貼合金屬箔即可。
金屬箔並無特別限定，可使用任何金屬箔。可較佳地使用例如銅、不鏽鋼、鎳、鋁、及該等金屬之合金等。又，一般之貼金屬積層板，多用壓延銅、電解銅等銅，但於本發明中亦能夠較佳地使用。
又，作為上述金屬箔，可視目的而選擇已表面處理者、或具有表面粗糙度等各種特性者。進而，上述金屬箔之表面亦可塗佈防銹層或耐熱層或接著層。關於上述金屬箔之厚度並無特別限定，只要為根據其用途而能發揮充分功能之厚度即可。
本發明之聚醯亞胺積層膜整體之厚度較佳為7μm~60μm。於其範圍內，亦厚度較薄之膜製成FPC時之彎曲性提高，故較佳。但，若厚度低於7μm，則存在加工時之操作變得困難之情況。若厚度高於60μm，則存在製成FPC時之彎曲性降低或薄型化變難之情況。
[實施例]
以下，根據實施例對本發明進行具體說明，但本發明並不僅限於該等實施例。
又，於表1中表示合成例1~9之測定結果，於表2中表示實施例1~4及比較例1~5之測定結果。
(動態黏彈性測定(DMA))
關於儲存彈性模數，藉由SII奈米科技公司製造之DMS6100於空氣環境下測定動態黏彈性，相對於測定溫度製成繪製有tanδ之圖表，自該圖表讀取380℃下之儲存彈性模數。測定構成合成例1~9之熱塑性聚醯亞胺層、合成例1~4、8、9之熱塑性聚醯亞胺層之區塊A及區塊B各自之儲存彈性模數。玻璃轉移溫度(Tg(℃))設為損失彈性模數除以儲存彈性模數而獲得之損失係數(tanδ)之峰頂之溫度。
‧樣本測定範圍：寬度9mm、夾具間距20mm
‧測定溫度範圍：0℃~440℃
‧升溫速度：3℃/分鐘
‧應變振幅：10μm
‧測定頻率：5Hz
‧最小張力/壓縮力：100mN
‧張力/壓縮增益：1.5
‧力幅初始值：100mN
(重量減少率測定)
準備3張切成3cm×7cm之膜，以50℃加熱30分鐘後，測量初期 重量W0。於樣本加熱至80℃之3%氫氧化鈉水溶液中浸漬10分鐘。浸漬後，以純水進行洗淨，以50℃乾燥30分鐘後測量重量W1。使用下述式子求出重量減少率。
重量減少率(%)=(W0-W1)/W0×100
(有無龜裂)
以下述方法評價撓性金屬箔積層體之浸漬除膠渣液時之耐龜裂性(具體而言，為有無龜裂)。
自實施例及比較例中所獲得之撓性金屬箔積層體，切下長度方向20cm、寬度25cm大小之積層體。對所切下之積層體之一側之金屬箔層進行蝕刻處理，形成配線寬度250μm、配線間隔250μm之圖案。未形成圖案之一側之金屬箔則全部去除。將與配線伸長方向平行之方向設為長度方向，切下長度方向10cm、寬度1.5cm之試片。將該試片如圖1所示般夾於緩衝材料中，於180℃、3.8kgf/cm2之條件下進行60分鐘之熱壓(第一次熱壓)。
繼而，於10cm×12cm之FR4基板(環氧玻璃基板，厚度0.4mm)之中央部鑽孔1cm×10cm，於邊緣部分貼附雙面膠帶。以上述熱壓後之試片之端部與雙面膠帶重合之方式，將試片排列於FR4基板之開口部，於180℃、30kgf/cm2之條件下進行60分鐘之熱壓(第二次熱壓)。
於第二次熱壓後，將試片自FR4基板剝離，將該試片依序浸漬於保持50℃之膨潤液(Securigant P，Atotech公司製造)中90秒，保持65℃之除膠渣液(Securigant P500 P-Etch，Atotech公司製造)中300秒，保持40℃之中和液(Securigant P500，Atotech公司製造)中40秒。浸漬後，用水洗淨後以60℃乾燥10分鐘，獲得乾燥後之試片。
對於乾燥後之試片，對第二次熱壓時與FR4基板重合之部分以光學顯微鏡實施觀察，確認有無龜裂產生。關於耐龜裂性，將未確認有龜裂者評為「◎」，將確認有龜裂但龜裂之大小(長度方向)為未達1 μm者評為「○」，將確認有龜裂者評為「×」。再者，使用光學顯微鏡而確認之龜裂(破裂、分裂)不論其大小均設為龜裂。光學顯微鏡之倍率設為用於判斷被認為龜裂之部分之最佳倍率。
(剝離強度之測定方法)
於所製作之多層聚醯亞胺膜之兩面配置厚度12μm之電解銅箔(3EC-M3S-HTE(K)，三井金屬製造)，以層壓溫度360℃、壓力0.8t、線速1m/min之條件進行熱壓接。依據JIS C6471之「6.5抗剝強度」對包含銅箔及聚醯亞胺膜之樣本進行解析。具體而言，將1mm寬度之金屬箔部分於剝離角度90度、100mm/分鐘之條件下剝離，測定其負荷。剝離強度為12N/cm以上時評為「○」，剝離強度為未達12N/cm時評為「×」。
(熱塑性聚醯亞胺前驅物之合成)
(合成例1)
以反應系統內保持20℃之狀態，向N,N-二甲基乙醯胺(以下，亦稱為DMF)167.7kg中，添加4,4'-雙(4-胺基苯氧基)聯苯(以下，亦稱為BAPB)4.87kg，於氮氣環境下一面攪拌一面慢慢添加3,3',4,4'-聯苯四羧酸二酐(以下，亦稱為BPDA)3.24kg。目視確認BPDA溶解後，添加2,2'-雙[4-(4-胺基苯氧基)苯基]丙烷(以下，亦稱為BAPP)12.67kg。繼而，添加均苯四甲酸二酐(以下，亦稱為PMDA)6.88kg攪拌30分鐘。以固形物成分濃度達到7%之方式調製0.7kg之PMDA溶解於DMF中之溶液，一面留意黏度上升一面將該溶液慢慢添加至上述反應溶液中，於黏度達到300泊時結束聚合(區塊A：BAPB-BPDA，區塊B：BAPP-PMDA)。
(合成例2)
以反應系統內保持20℃之狀態，向DMF 172.0kg中加入4,4'-二胺基二苯醚(以下，亦稱為ODA)6.78kg，於氮氣環境下一面攪拌一面 慢慢添加BPDA 9.19kg。目視確認BPDA溶解後，添加BAPP 7.48kg。繼而，添加PMDA 4.15kg攪拌30分鐘。以固形物成分濃度達到7%之方式調製0.7kg之PMDA溶解於DMF中之溶液，一面留意黏度上升一面將該溶液慢慢添加至上述反應溶液中，於黏度達到300泊時結束聚合(區塊A：ODA-BPDA，區塊B：BAPP-PMDA)。
(合成例3)
以反應系統內保持20℃之狀態，向DMF 172.0kg中加入BAPB 5.04kg，於氮氣環境下一面攪拌一面慢慢添加BPDA 3.35kg。目視確認BPDA溶解後，添加BAPP 11.23kg、ODA 0.91kg。繼而，添加PMDA 7.11kg攪拌30分鐘。以固形物成分濃度達到7%之方式調製0.7kg之PMDA溶解於DMF中之溶液，一面留意黏度上升一面將該溶液慢慢添加至上述反應溶液中，於黏度達到300泊時結束聚合(區塊A：BAPB-BPDA，區塊B：BAPP-ODA-PMDA)。
(合成例4)
以反應系統內保持20℃之狀態，向DMF 172.0kg中加入BAPB 7.49kg、ODA 1.36kg，於氮氣環境下一面攪拌一面慢慢添加BPDA 7.31kg。目視確認BPDA溶解後，添加BAPP 7.42kg。繼而，添加PMDA 4.09kg攪拌30分鐘。以固形物成分濃度達到7%之方式調製0.7kg之PMDA溶解於DMF中之溶液，一面留意黏度上升一面將該溶液慢慢添加至上述反應溶液中，於黏度達到300泊時結束聚合(區塊A：BAPB-ODA-BPDA，區塊B：BAPP-PMDA)。
(合成例5)
以反應系統內保持20℃之狀態，向DMF 172.0kg中加入BPDA 12.43kg，於氮氣環境下一面攪拌一面慢慢添加BAPB 15.02kg攪拌30分鐘。以固形物成分濃度達到7%之方式調製0.7kg之BAPB溶解於DMF中之溶液，一面留意黏度上升一面將該溶液慢慢添加至上述反應 溶液中，於黏度達到300泊時結束聚合(區塊A、B：無)。
(合成例6)
以反應系統內保持20℃之狀態，向DMF 172.0kg中加入BAPP 18.28kg，於氮氣環境下一面攪拌一面慢慢添加PMDA 9.38kg攪拌30分鐘。以固形物成分濃度達到7%之方式調製0.7kg之PMDA溶解於DMF中之溶液，一面留意黏度上升一面將該溶液慢慢添加至上述反應溶液中，於黏度達到300泊時結束聚合(區塊A、B：無)。
(合成例7)
以反應系統內保持20℃之狀態，向DMF 172.0kg中加入BAPB 4.87kg、BAPP 12.67kg，於氮氣環境下攪拌，確認BAPB、BAPP溶解。添加BPDA 3.24kg、PMDA 6.88kg攪拌30分鐘。以固形物成分濃度達到7%之方式調製0.7kg之PMDA溶解於DMF中之溶液，一面留意黏度上升一面將該溶液慢慢添加至上述反應溶液中，於黏度達到300泊時結束聚合(區塊A、B：無)。
(合成例8)
以反應系統內保持20℃之狀態，向DMF 167.6kg中加入BAPB 8.85kg，於氮氣環境下一面攪拌一面慢慢添加BPDA 6.36kg。目視確認BPDA溶解後，添加1,3-雙(4-胺基苯氧基)苯(以下，亦稱為TPE-R)7.02kg。繼而，添加PMDA 5.45kg攪拌30分鐘。以固形物成分濃度達到7%之方式調製0.7kg之PMDA溶解於DMF中之溶液，一面留意黏度上升一面將該溶液慢慢添加至上述反應溶液中，於黏度達到300泊時結束聚合(區塊A：BAPB-BPDA，區塊B：TPE-R-PMDA)。
(合成例9)
以反應系統內保持20℃之狀態，向DMF 167.4kg中加入3,4'-二胺基二苯醚(以下，亦稱為3,4'-ODA)5.03kg，於氮氣環境下一面攪拌一面慢慢添加BPDA 6.65kg。目視確認BPDA溶解後，添加BAPP 10.30 kg。繼而，添加PMDA 5.69kg攪拌30分鐘。以固形物成分濃度達到7%之方式調製0.7kg之PMDA溶解於DMF中之溶液，一面留意黏度上升一面將該溶液慢慢添加至上述反應溶液中，於黏度達到300泊時結束聚合(區塊A：3,4'-ODA-BPDA，區塊B：BAPP-PMDA)。
(非熱塑性聚醯亞胺前驅物之合成及膜)
(合成例10)
以反應系統內保持20℃之狀態，向DMF 170.0kg中添加ODA 5.50kg、BAPP 2.82kg，於氮氣環境下攪拌。目視確認ODA、BAPP溶解後，添加BTDA 4.43kg。目視確認BTDA溶解後，添加PMDA 7.79kg，確認溶解後攪拌30分鐘。添加p-PDA 3.42kg、ODA 0.55kg，目視確認溶解後，慢慢添加PMDA 7.79kg攪拌30分鐘。
最後，以固形物成分濃度達到7%之方式調製0.8kg之BAPP溶解於DMF中之溶液，一面留意黏度上升一面將該溶液慢慢添加至上述反應溶液中，於黏度達到3000泊時結束聚合。
向該聚醯胺酸溶液中添加相對於聚醯胺酸溶液以重量比50%計之包含乙酸酐/異喹啉/DMF(重量比為2.0/0.6/2.8)之醯亞胺化促進劑，以攪拌器連續攪拌。將該混合物自T模嘴擠出，流延於不鏽鋼製之環帶上。將該樹脂膜以130℃×100秒加熱後，自環帶上剝離具有自我支撐性之Gel膜。將該Gel膜固定於拉幅夾，以250℃×15秒、350℃×87秒使其乾燥並醯亞胺化，獲得厚度12.5μm之聚醯亞胺膜。
(實施例1)
於合成例10中所獲得之聚醯亞胺膜之兩面上，以每一面之最終厚度達到3.0μm之方式塗佈合成例1中所獲得之聚醯胺酸溶液，以140℃乾燥2分鐘。繼而，以350℃加熱1分鐘進行醯亞胺化，獲得總厚度18.5μm之聚醯亞胺積層膜。
於所獲得之聚醯亞胺積層膜之兩面上，配置厚度12.5μm之電解 銅箔(3EC-M3S-THE，三井金屬製造)，進而於兩面電解銅箔之外側配置保護膜(Apical 125NPI：Kaneka製造，厚度125μm)，自該保護膜之外側，於層壓溫度360℃、層壓壓力265N/cm(27kgf/cm2)、層壓速度1.0m/分鐘之條件下進行熱層壓，製作撓性金屬箔積層體。
(實施例2)
除使用合成例2中所獲得之聚醯亞胺膜代替合成例1中所獲得之聚醯亞胺膜以外，進行與實施例1相同之操作，製作撓性金屬箔積層體。
(實施例3)
除使用合成例3中所獲得之聚醯亞胺膜代替合成例1中所獲得之聚醯亞胺膜以外，進行與實施例1相同之操作，製作撓性金屬箔積層體。
(實施例4)
除使用合成例4中所獲得之聚醯亞胺膜代替合成例1中所獲得之聚醯亞胺膜以外，進行與實施例1相同之操作，製作撓性金屬箔積層體。
(比較例1)
除使用合成例5中所獲得之聚醯亞胺膜代替合成例1中所獲得之聚醯亞胺膜以外，進行與實施例1相同之操作，製作撓性金屬箔積層體。
(比較例2)
除使用合成例6中所獲得之聚醯亞胺膜代替合成例1中所獲得之聚醯亞胺膜以外，進行與實施例1相同之操作，製作撓性金屬箔積層體。
(比較例3)
除使用合成例7中所獲得之聚醯亞胺膜代替合成例1中所獲得之 聚醯亞胺膜以外，進行與實施例1相同之操作，製作撓性金屬箔積層體。
(比較例4)
除使用合成例8中所獲得之聚醯亞胺膜代替合成例1中所獲得之聚醯亞胺膜以外，進行與實施例1相同之操作，製作撓性金屬箔積層體。
(比較例5)
除使用合成例9中所獲得之聚醯亞胺膜代替合成例1中所獲得之聚醯亞胺膜以外，進行與實施例1相同之操作，製作撓性金屬箔積層體。
(參考例)
以下表示用於測定合成例1~4、8、9之區塊A、區塊B各自之儲存彈性模數的聚醯胺酸之合成例、及膜之製造例。分別使用相等莫耳量之合成例1~4、8、9之單個區塊A、或單個區塊B，獲得聚醯胺酸溶液。向該聚醯胺酸溶液中添加相對於聚醯胺酸溶液以重量比50%計之包含乙酸酐/異喹啉/DMF(重量比為2.0/0.6/2.8)之醯亞胺化促進劑，以攪拌器連續攪拌。將該混合物自T模嘴擠出，流延於不鏽鋼製之環帶上。將該樹脂膜以130℃×100秒加熱後，自環帶上剝離具有自我支撐性之Gel膜。將該Gel膜固定於拉幅夾，以250℃×15秒、300℃×87秒使其乾燥並醯亞胺化，獲得厚度12.5μm之熱塑性聚醯亞胺膜。亦將該等熱塑性聚醯亞胺膜之黏彈性測定結果示於表1。
[產業上之可利用性]
本發明可用於製造軟性印刷配線板之領域中。

Claims (8)

  1. 一種聚醯亞胺積層膜，其特徵在於：其具備熱塑性聚醯亞胺層，該熱塑性聚醯亞胺層包含380℃下之儲存彈性模數為0.15GPa以上之區塊A、及380℃下之儲存彈性模數為0.10GPa以下之區塊B。
  2. 如請求項1之聚醯亞胺積層膜，其中上述區塊A為至少包含4,4'-雙(4-胺基苯氧基)聯苯(BAPB)、及3,3',4,4'-聯苯四羧酸二酐(BPDA)之區塊成分，上述區塊B為至少包含2,2'-雙[4-(4-胺基苯氧基)苯基]丙烷(BAPP)之二胺、及均苯四甲酸二酐(PMDA)之區塊成分。
  3. 如請求項1之聚醯亞胺積層膜，其中上述聚醯亞胺積層膜為以80℃浸漬於鹼性溶液中10分鐘時，重量減少率為未達2重量%者。
  4. 如請求項1至3中任一項之聚醯亞胺積層膜，其中上述熱塑性聚醯亞胺層為380℃下之儲存彈性模數為0.05GPa以下者。
  5. 一種熱塑性聚醯亞胺之製造方法，其特徵在於包含如下步驟：使380℃下之儲存彈性模數為0.15GPa以上之區塊A、與380℃下之儲存彈性模數為0.10GPa以下之區塊B共聚。
  6. 一種聚醯亞胺積層膜之製造方法，其特徵在於具有如下步驟：對包含380℃下之儲存彈性模數為0.15GPa以上之區塊A、及380℃下之儲存彈性模數為0.10GPa以下之區塊B的熱塑性聚醯亞胺層，與非熱塑性聚醯亞胺層進行積層。
  7. 一種撓性貼金屬箔積層體之製造方法，其特徵在於具有如下步驟：即對包含熱塑性聚醯亞胺層之聚醯亞胺積層膜、與金屬箔進行積層， 該熱塑性聚醯亞胺層包含380℃下之儲存彈性模數為0.15GPa以上之區塊A、及380℃下之儲存彈性模數為0.10GPa以下之區塊B。
  8. 如請求項7之撓性貼金屬箔積層體之製造方法，其中上述積層步驟藉由熱層壓法、或流延法而進行。
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