TW202014452A - 可剝離之聚醯亞胺複合膜 - Google Patents
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Abstract
本發明為一種可剝離之聚醯亞胺複合膜,其包括有一第一聚醯亞胺膜,其具有相對的第一、第二表面;及第二聚醯亞胺膜,其附著於該第一聚醯亞胺膜的第一表面,其中,該第一聚醯亞胺膜與該第二聚醯亞胺膜之熱膨脹係數差異大於或等於9um/m ℃,使其可以互相剝離者。
Description
本發明係關於一種可剝離之聚醯亞胺複合膜,特別係指一種可製成超薄聚醯亞胺膜者。
於印刷電路板中,為了保護金屬線路,通常會於其上設置聚醯亞胺保護層(coverlay)。隨著技術發展及產品需求,印刷電路板之尺寸趨向輕、薄、及多功能化,降低印刷電路板之整體厚度亦為業界重要發展目標,其中,聚醯亞胺保護層之薄化已成為印刷電路板整體設計之重要指標之一。
然而,受限於習知聚醯亞胺膜之製程能力,超薄聚醯亞胺膜確實有開發上的難度。已知目前市售最薄聚醯亞胺保護層之厚度可低於10微米;然而,欲以現有的雙軸延伸工藝製備低於5微米以下之聚醯亞胺膜,幾乎是不可能達到的目標。且,也必須考量下游應用時之佈膠操作性之問題。
據此,對於超薄聚醯亞胺膜之產品及其相關製程仍有其需求。
本發明係提供一種可剝離之聚醯亞胺複合膜,其包括有一第一聚醯亞胺膜,其具有相對的第一、第二表面;及一第二聚醯亞胺膜,其附著於該第一聚醯亞胺膜的第一表面,其中,該第一聚醯亞胺膜與該第二聚醯亞胺膜之熱膨脹係數差異大於9um/m ℃,使其可以互相剝離者。
10‧‧‧第一聚醯亞胺膜
12‧‧‧第二聚醯亞胺膜
第1圖係本發明可剝離之聚醯亞胺複合膜之剖視圖。
第2圖係本發明可剝離之聚醯亞胺複合膜之示意圖。
本實施例中,請參閱第1圖式,第一聚醯亞胺膜10具有6微米以下之厚度,較佳為5微米以下,例如:0.1至5微米。於實施例中,第一聚醯亞胺層10之厚度可為0.1、1、2、2.5、3、4、4.5微米、或前述任兩點間之數值。
第二聚醯亞胺膜12之厚度並未特別限制,可採用一般聚醯亞胺膜之厚度。於部分實施例中,第二聚醯亞胺膜12之厚度為5至50微米。於部分實施例中,第二層聚醯亞胺膜12之厚度可為20微米以上。
請配合參閱第2圖式,其中,該第一聚醯亞胺膜10與第二聚醯亞胺膜12之熱膨脹係數差異大於或等於9um/m ℃,使其可以互相剝離者。
視需要,可於形成該第一聚醯亞胺膜10與第二聚醯亞胺膜後,進一步進行雙軸延伸處理,據此可增進該聚醯亞胺膜之強度。由於聚醯亞胺膜厚度越薄則越難以進行雙軸延伸處理,因此,已知目前市售之超薄聚醯亞胺膜幾乎無法於製程中進行雙軸延伸處理,對於其薄膜強度會造
成不利的影響。惟,本發明之聚醯亞胺複合膜由於直接形成第一聚醯亞胺膜10於第二聚醯亞胺膜12上,因此可視需要進行雙軸延伸處理,而不會對薄膜造成不利的影響,例如破裂。
本發明之聚醯亞胺複合膜可利用熱轉化或化學轉化的方式形成。若採用化學轉化的方式,則於塗佈步驟前,可將脫水劑及催化劑添加至聚醯胺酸溶液中。前述所使用之溶劑、脫水劑及催化劑均可為本技術領域習知者。該溶劑可為非質子性極性溶劑,例如二甲基乙醯胺(DMAC)、N,N'-二甲基甲醯胺(DMF)、N-甲基吡咯啶酮(NMP)、二甲亞碸(DMSO)、四甲基碸、N,N'-二甲基-N,N'-丙烯基脲(DMPU)等。該脫水劑可為脂肪族酸酐(如醋酸酐及丙酸酐)、芳香族酸酐(如苯酸酐及鄰苯二甲酸酐)等。該催化劑可為雜環三級胺(例如甲吡啶(picoline)、吡啶等)、脂肪族三級胺(例如三乙基胺(TEA)等)、芳香族三級胺(例如二甲苯胺等)等。聚醯胺酸:脫水劑:催化劑之莫耳比為1:2:1,即對每莫耳之聚醯胺酸,使用約2莫耳之脫水劑及約1莫耳之催化劑。
於本發明中,由二胺單體及二酐單體經縮合反應而形成聚醯亞胺,且該二胺與該二酐以約為等莫耳之比例(1:1)進行反應,例如0.9:1.1、或0.98:1.02。
構成該可剝離基底層主結構之聚醯亞胺及聚醯亞胺層之聚醯亞胺並未特別限制。
於實施例中,該二胺單體可為4,4'-二胺基二苯醚(4,4'-oxydianiline(4,4'-ODA))、對苯二胺(phenylenediamine(p-PDA))、2,2’-雙(三氟甲基)聯苯胺(2,2'-Bis(trifluoromethyl)benzidine(TFMB))、1,3-雙(4'-
胺基苯氧基)苯(1,3-bis(4-aminophenoxy)benzene(TPER))、1,4-雙(4-胺基苯氧基)苯(1,4-bis(4-aminophenoxy)benzene(TPEQ))、4,4’-二胺基-2,2’-二甲基-1,1’-聯苯(2,2'-dimethyl[1,1'-biphenyl]-4,4'-diamine(m-TB-HG))、1,3-雙(3-胺基苯氧基)苯(1,3’-Bis(3-aminophenoxy)benzene(APBN))、3,5-二胺基三氟甲苯(3,5-Diaminobenzotrifluoride(DABTF))、2,2'-雙[4-(4-胺基苯氧基苯基)]丙烷(2,2'-bis[4-(4-aminophenoxy)phenyl]propane(BAPP))、6-胺基-2-(4-胺基苯基)-苯并噁唑(6-amino-2-(4-aminophenyl)benzoxazole(6PBOA))、5-胺基-2-(4-胺基苯基)-苯并噁唑(5-amino-2-(4-aminophenyl)benzoxazole(5PBOA))等,可單獨使用或組合使用。
於實施例中,該二酐單體可為3,3',4,4'-聯苯四羧酸二酸酐(3,3',4,4'-biphenyltetracarboxylic dianhydride(BPDA))、2,2-雙[4-(3,4-二羧基苯氧基)苯基]丙烷二酸酐(2,2-bis[4-(3,4dicarboxyphenoxy)phenyl]propane dianhydride(BPADA))、均苯四甲酸二酸酐(pyromellitic dianhydride(PMDA))、4,4'-(六氟異丙烯)二酞酸酐(2,2'-Bis-(3,4-Dicarboxyphenyl)hexafluoropropane dianhydride(6FDA))、二苯醚四甲酸二酸酐(4,4-Oxydiphthalic anhydride(ODPA))、苯酮四羧酸二酸酐(Benzophenonetetracarboxylic dianhydride(BTDA))、3,3',4,4'-二環己基四甲酸二酐(3,3',4,4'-dicyclohexyltetracarboxylic acid dianhydride(HBPDA)等,可單獨使用或組合使用。
於一些實施例中,第一聚醯亞胺膜10之單體包括下列成分:二胺可為4,4'-二胺基二苯醚(4,4'-ODA)、對苯二胺(p-PDA)、2,2’-雙(三氟甲基)聯苯胺(TFMB),可單獨或組合使用;該二酐可為均苯四甲酸二酐
(PMDA)、3,3',4,4'-聯苯四羧酸二酐(BPDA)、2,2-雙[4-(3,4-二羧基苯氧基)苯基]丙烷二酐(BPADA),可單獨或組合使用。
於實施例中,第一聚醯亞胺膜10可使用與第二聚醯亞胺膜完全相同、部分相同、或不同之單體。於一些實施例中,第二聚醯亞胺膜12所使用之二胺可為4,4'-二胺基二苯醚(4,4'-ODA)、對苯二胺(p-PDA)、2,2’-雙(三氟甲基)聯苯胺(TFMB),可單獨或組合使用;以及,二酐可為均苯四甲酸二酐(PMDA)、3,3',4,4'-聯苯四羧酸二酐(BPDA)、2,2-雙[4-(3,4-二羧基苯氧基)苯基]丙烷二酐(BPADA),可單獨或組合使用。
實施例1
先將所需要之二胺ODA單體加入DMAc溶劑中,攪拌並且等待其溶解,再將二酸酐PMDA單體緩慢加入上述溶液中,使黏度提升至160,000cps,最終控制其固含量約為18%,以上為第一聚醯亞胺膜之配方;而第二聚醯亞胺膜之配方之二胺單體分別為ODA和PDA,兩者比例是80:20,二酸酐單體則全部由PMDA所組成。
實施例2
本實施例先將所需要之二胺ODA單體加入DMAc溶劑中攪拌溶解,再將二酸酐PMDA單體緩慢加入,PMDA加入後此溶液黏度會持續上升,當黏度提升至160,000cps左右即可,最終控制其固含量約為18%,以上為第一聚醯亞胺膜之配方,而第二聚醯亞胺膜之配方之二胺單體分別為ODA和PDA,兩者比例是70:30,二酸酐單體則全部由PMDA所組成。
實施例3
本實施例第一聚醯亞胺膜10之配方為ODA和PMDA,其聚合程序如前實施例,而第二聚醯亞胺層之配方由二胺單體以及二酸酐單體所構成,分別為TFMB和6FDA。
比較例
比較例之第一聚醯亞胺膜10之配方如實施例由ODA和PMDA所構成,而第二聚醯亞胺層之配方之二胺單體分別為ODA和PDA,兩者比例是85:15,二酸酐單體則是由PMDA所組成。
由此實施例與比較例的測試結果顯示,兩層聚醯亞胺膜之熱膨脹係數差異大於9um/m ℃時,可以使兩層聚醯亞胺膜貼附性減低,並且使其可以相互剝離。因此,本發明在相同厚度之聚醯亞胺膜基準下,可藉由於兩層聚醯亞胺膜之熱膨脹係數差異,控制其產品可以剝離與否,可剝離者可以使聚醯亞胺膜上膠等後段製程中,使其製程較容易控制,以提升產品良率。
表一為一第一聚醯亞胺膜與第二聚醯亞胺膜之二胺單體比例之剝離性評估結果,由結果可以得知藉由變更二胺單體造成熱膨脹係數(CTE)之差異,兩層之熱膨脹係數差異控制於9um/m ℃以上,可以達到可剝離的效果。
上述特定實施例之內容係為了詳細說明本發明,然而,該等實施例係僅用於說明,並非意欲限制本發明。熟習本領域之技藝者可理解,在不悖離後附申請專利範圍所界定之範疇下針對本發明所進行之各種變化或修改係落入本發明之一部分。
10‧‧‧第一聚醯亞胺膜
12‧‧‧第二聚醯亞胺膜
Claims (3)
- 一種可剝離之薄聚醯亞胺複合膜,係包括有:一第一聚醯亞胺膜,其具有第一及第二表面;及一第二聚醯亞胺膜,其係附著於該第一聚醯亞胺層的第一表面,其中,該第一聚醯亞胺層與該第二聚醯亞胺層之熱膨脹係數差異大於9um/m ℃,使兩者可以相互剝離。
- 如申請專利範圍第1項所述之可剝離之薄聚醯亞胺複合膜,其中,該第一聚醯亞胺膜係由選自4,4'-二胺基二苯醚(ODA)、對苯二胺(PDA)、所成群組之二胺及選自由均苯四甲酸二酐(PMDA)、3,3',4,4'-聯苯四羧酸二酐(BPDA)所成群組之二酐反應而得。
- 如申請專利範圍第1項所述之可剝離之薄聚醯亞胺複合膜,其中,該第二聚醯亞胺膜係由選自4,4'-二胺基二苯醚(ODA)、對苯二胺(PDA)、所成群組之二胺及選自由均苯四甲酸二酐(PMDA)、3,3',4,4'-聯苯四羧酸二酐(BPDA)所成群組之二酐反應而得。
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Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
TW107135227A TW202014452A (zh) | 2018-10-05 | 2018-10-05 | 可剝離之聚醯亞胺複合膜 |
US16/592,845 US20200109244A1 (en) | 2018-10-05 | 2019-10-04 | Peelable polyimide composite film |
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TW107135227A TW202014452A (zh) | 2018-10-05 | 2018-10-05 | 可剝離之聚醯亞胺複合膜 |
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TW202014452A true TW202014452A (zh) | 2020-04-16 |
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TW107135227A TW202014452A (zh) | 2018-10-05 | 2018-10-05 | 可剝離之聚醯亞胺複合膜 |
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US (1) | US20200109244A1 (zh) |
TW (1) | TW202014452A (zh) |
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2018
- 2018-10-05 TW TW107135227A patent/TW202014452A/zh unknown
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2019
- 2019-10-04 US US16/592,845 patent/US20200109244A1/en not_active Abandoned
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US20200109244A1 (en) | 2020-04-09 |
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