TW202016174A - 透明聚醯亞胺膜 - Google Patents
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Abstract
本發明為一種透明聚醯亞胺膜,其係由共聚聚醯胺酸經由化學環化法製成,其中共該聚聚醯胺酸至少需具有半芳香族聚醯胺酸,該半芳香族聚醯胺酸是由1,2,3,4-環丁四羧二酐(CBDA)與2,2'-二(三氟甲基)二氨基聯苯(TFMB)反應組成,其中,該半芳香族聚醯胺酸之二酐莫爾數佔該共聚聚醯胺酸之酸酐總莫爾數之百分比20以上,使該透明聚醯亞胺膜具有光穿透度大於80%,色度b*小於5,CTE小於35ppm/℃。
Description
本發明係關於一種透明聚醯亞胺膜,特別係指以一種具有較低之熱膨脹係數,使其熱穩定性較佳。
聚醯亞胺薄膜具有優秀的耐熱性與機械性特性,因此常使用在具有高溫製程的軟性電路板應用領域。此外又因透明聚醯亞胺薄膜具有良好的耐彎折性與光學特性,因此近年來在電子顯示用顯示器領域中,對於光學特性、耐熱性的需求,聚醯亞胺薄膜是少數能符合上述要求的材料。
雖然透明聚醯亞胺薄膜具有良好的光學性,耐溫性,但在熱穩定性上仍然不足。在軟性電子材料的領域中,金屬線路需附著於聚醯亞胺膜上,因此線路的尺寸安定性會仰賴著聚醯亞胺膜的熱膨脹係數。一般透明聚醯亞胺膜的熱膨脹係數偏高,因此會造成附著於聚醯亞胺膜上的金屬線路在受熱的情況下尺寸安定性不佳。而為了降低透明聚醯亞胺膜的熱膨脹係數常使用剛性較高之芳香環二酸酐單體,其所形成的共聚聚醯亞胺薄膜可製作出具有較低熱膨脹係數之透明聚醯亞胺膜,但,如此會造成透光度較低(小於80%)與色度b*較黃等不良的影響。
本發明透明聚醯亞胺膜,其係由共聚聚醯胺酸經由化學環化法製成,其中共該聚聚醯胺酸至少需具有半芳香族聚醯胺酸,該半芳香族聚醯胺酸是由1,2,3,4-環丁四羧二酐(CBDA)與2,2'-二(三氟甲基)二氨基聯苯
(TFMB)反應組成,其中,該半芳香族聚醯胺酸之二酐莫爾數佔該共聚聚醯胺酸之酸酐總莫爾數之百分比20以上,使該透明聚醯亞胺膜具有光穿透度大於80%,色度b*小於5,CTE小於35ppm/℃。
S1‧‧‧TFMB加入DMAc
S2‧‧‧加入CBDA
S3‧‧‧形成半芳香族聚醯胺酸溶液
S4‧‧‧加入芳香族二胺
S5‧‧‧加入芳香族二酐
S6‧‧‧形成共聚聚醯胺酸溶液
S7‧‧‧共聚聚醯胺酸溶液加入DMAc
S8‧‧‧加入醋酸酐與3-甲基吡啶
S9‧‧‧刮刀進行塗佈
S10‧‧‧烘箱烘烤
S11‧‧‧形成透明聚醯胺膜
第1 圖為本發明共聚聚醯胺酸之製作流程圖。
第2 圖為本發明透明聚醯亞胺膜之製作流程圖。
一種透明聚醯亞胺膜,其係由共聚聚醯胺酸經由化學環化法製得而成,其中共聚聚醯胺酸至少需具有半芳香族聚醯胺酸,該半芳香族聚醯胺酸是由1,2,3,4-環丁四羧二酐(CBDA)與2,2'-二(三氟甲基)二氨基聯苯(TFMB)反應組成。其中,該半芳香族聚醯胺酸之二酐莫爾數佔該共聚聚醯胺酸之酸酐總莫爾數之百分比20以上,使該透明聚醯亞胺膜具有光穿透度大於80%,色度b*小於5,CTE小於35ppm/℃。
其中,該共聚聚醯胺酸亦可含有芳香族聚醯胺酸,該芳香族聚醯胺酸係由芳香族二胺與芳香族酸酐反應而得。其中芳香族二胺包含了2,2'-二(三氟甲基)二氨基聯苯(TFMB)、2,2'-雙[4-(4-氨基苯氧基苯基)]丙烷(BAPP)、2,2-雙[4-(4-氨基苯氧基)苯基]-1,1,1,3,3,3-六氟丙烷(HFBAPP)、5(6)-氨基-1-(4-氨基苯基)-1,3,3-三甲基茚滿(TMDA)、對苯二胺(PDA)、4,4'-二(4-氨基苯氧基)聯苯(BAPB)、2,2'-雙(三氟甲基)-4,4'-二氨基苯基醚(6FODA)、4,4'-雙(4-氨基苯氧基)二苯碸(BAPS)、9,9-雙(4-氨基苯基)芴(BAFL)、4,4'-二氨基二苯碸(44DDS)、4,4'-二氨基二苯醚(ODA)、4,4'-二氨基苯醯替苯胺(44DABA)、2,2-双(4-氨基苯基)六氟丙烷(Bis-A-AF)、間苯二胺(mPDA)、2,2-雙(3-氨基-4-羥基苯基)六氟丙烷(6FAP)、3,5-二氨基苯甲酸(35DABA)、2-(4-氨基苯基)-5-氨基苯並惡唑(5BPOA)、1,4-雙(4-氨基苯氧基)苯(TPEQ)、4,4'-[1,4-苯基雙(氧)]雙[3-(三氟甲基)苯胺](FAPB)。其中芳香族二酐包含了1,2,4,5-苯
四甲酸酐(PMDA)、3,3',4,4'-聯苯四羧酸二酐(BPDA)、4,4'-氧雙鄰苯二甲酸酐(ODPA)、3,3',4,4'-二苯甲酮四甲酸二酐(BTDA)、3,3,4,4-二苯基碸四羧酸二酸酐(DSDA)、2,3,3',4'-聯苯四甲酸二酐(α-BPDA)、4,4-六氟異丙基鄰苯二甲酸酐(6FDA)、4,4'-(4,4'-異丙基二苯氧基)二酞酸酐(BPADA)。
共聚聚醯胺酸之製作
請參閱第1圖,首先,將2,2'-二(三氟甲基)二氨基聯苯(TFMB),加入N,N-二甲基乙醯胺(DMAc)中(S1),待全部溶解後加入1,2,3,4-環丁四羧二酐(CBDA)(S2),攪拌反應六小時且溫度持續維持在25℃形成半芳香族聚醯胺酸溶液(S3)。將上述半芳香族聚醯胺酸溶液再添加另一芳香族二胺(S4),攪拌至完全溶解後再添加另一芳香族二酐(S5),攪拌一定時間而進行溶解及反應,並且溶液的溫度維持為25℃,最終得到固體含量為25%的共聚聚醯胺酸溶液(S6)。
透明聚醯亞胺膜之製作
請參閱第2圖,將共聚聚醯胺酸溶液中使用N,N-二甲基乙醯胺(DMAc)將其稀釋(S7),之後分別添加醋酸酐與3-甲基吡啶(S8),此時須注意具有1,2,3,4-環丁四羧二酐(CBDA)成分的配方在加入醋酸酐與3-甲基吡啶後會因溶解度下降造成稀出,在靜置約三到五分鐘後該析出物可逐漸回復流動性,待流動性回覆後將溶液塗佈到玻璃板後使用刮刀進行塗佈(S9)。將塗佈完成之樣品置放於50℃烘箱烘烤20分鐘,再緩慢升溫至170℃烘烤20分鐘後,再將烘箱升溫至260℃烘烤20分鐘為最終處理,而可得到10~80um厚度之透明聚醯亞胺膜。
<檢測方法>
下列實施例中所得到的透明聚醯亞胺膜的熱性質與光學性質使用以下方法量測。
(1)色度b*:依照ASTM E313規範使用Nippon Denshoku公司出品型號為NE-4000儀器量測。
(2)光穿透度:依照ISO 14782規範使用Nippon Denshoku公司出
品型號為NDH-2000N儀器量測。
(3)CTE:依照ASTM D696規範,使用TA Instruments公司出的型號Q400 TMA儀器量測。量測透明聚醯亞胺膜在100~200℃時的熱膨脹係數,升溫速率設定為10℃/min。為了除去因熱處理所造成的應力,藉由第一次量測除去殘餘應力後,以第二次量測結果做為實際值。
<實施例1>
共聚聚醯胺酸溶液之製造
將20.1克的2,2'-二(三氟甲基)二氨基聯苯(TFMB,0.0627mole,佔總二胺莫爾數比率0.315),加入412.5克的N,N-二甲基乙醯胺(DMAc),待全部溶解後加入11.723克的1,2,3,4-環丁四羧二酐(CBDA,0.0598mole,佔總酸酐莫爾百分比30%),攪拌反應六小時且溫度持續維持在25℃得到半芳香族聚醯胺酸溶液。將上述半芳香族聚醯胺酸溶液添加43.711克的2,2'-二(三氟甲基)二氨基聯苯(TFMB,0.1365mole),攪拌至完全溶解,再添加61.965克的4,4-六氟異丙基鄰苯二甲酸酐(6FDA,0.1395mole),攪拌一定時間而進行溶解及反應,並且溶液的溫度維持為25℃,最終得到固體含量為25%的共聚聚醯胺酸溶液。
透明聚醯亞胺膜的製作
在上述共聚聚醯胺酸溶液中取出54.4克,並使用N,N-二甲基乙醯胺(DMAc)將固體含量稀釋至17%,之後分別添加11.2毫升的醋酸酐與3.8毫升的3-甲基吡啶,在均勻攪拌後因溶解度下降導致凝膠化,待靜置五分鐘後回復流動性,將溶液塗佈到玻璃板後使用900μm間隙之刮刀進行塗佈。將塗佈完成之樣品置放於50℃烘箱烘烤20分鐘,再緩慢升溫至170℃烘烤20分鐘後,再將烘箱升溫至260℃烘烤20分鐘為最終處理。
上述所製成之透明聚醯亞胺膜其100~200℃間的熱膨脹係數為22ppm/℃,色度b*為1.1,光穿透度為89%。
<實施例2>
共聚聚醯胺酸溶液的製作
將27.800克的2,2'-二(三氟甲基)二氨基聯苯(TFMB,0.0868mole,佔總二胺莫爾數比率0.42),加入412.5克的N,N-二甲基乙醯胺(DMAc),待全部溶解後再加入16.214克的1,2,3,4-環丁四羧二酐(CBDA,0.0827mole,佔總酸酐莫爾百分比40%),攪拌反應六小時且溫度持續維持在25℃,得到半芳香族聚醯胺酸溶液。將上述半芳香族聚醯胺酸溶液添加38.391克的2,2'-二(三氟甲基)二氨基聯苯(TFMB,0.120mole),攪拌至完全溶解後再加入55.094克的4,4-六氟異丙基鄰苯二甲酸酐(6FDA,0.124mole),攪拌一定時間而進行溶解及反應,並且溶液的溫度維持為25℃,最終得到固體含量為25%的共聚聚醯胺酸溶液。
透明聚醯亞胺膜的製作
在上述共聚聚醯胺酸溶液中取出54.4克,並使用N,N-二甲基乙醯胺(DMAc)將固體含量稀釋至為17%,之後分別添加10.9毫升的醋酸酐與3.7毫升的3-甲基吡啶,在均勻攪拌後因溶解度下降導致凝膠化,待靜置五分鐘後回復流動性,將溶液塗佈到玻璃板後使用900μm間隙之刮刀進行塗佈。將塗佈完成之樣品置放於50℃烘箱烘烤20分鐘,再緩慢升溫至170℃烘烤20分鐘後,再將烘箱升溫至260℃烘烤20分鐘做為最終處理。
上述所製成之透明聚醯亞胺膜其100~200℃間的熱膨脹係數為23ppm/℃,色度b*為2.6,光穿透度為89%。
<實施例3>
共聚聚醯胺酸溶液的製作
將42.972克的2,2'-二(三氟甲基)二氨基聯苯(TFMB,0.1342mole,佔總二胺莫爾數比率0.625),加入412.5克的N,N-二甲基乙醯胺(DMAc),待全部溶解後加入21.053克的1,2,3,4-環丁四羧二酐(CBDA,0.1074mole,總酸酐莫爾百分比50%),,攪拌反應六小時且溫度持續維持在25℃,得到半芳香族聚醯胺酸溶液。再將上述半芳香族聚醯胺酸溶液添加25.783克的2,2'-二(三氟甲基)二氨基聯苯(TFMB,0.0805mole)攪拌至完全溶解後再加入47.691克的4,4-六氟異丙基鄰苯二甲酸酐(6FDA,0.1074mole),攪拌一
定時間而進行溶解及反應,並且溶液的溫度維持為25℃,最終得到固體含量為25%的共聚聚醯胺酸溶液。
透明聚醯亞胺膜的製作
在上述共聚聚醯胺酸溶液中取出54.4克,並使用N,N-二甲基乙醯胺(DMAc)將固體含量稀釋至為17%,之後分別添加12.0毫升的醋酸酐與4.1毫升的3-甲基吡啶,在均勻攪拌後因溶解度下降導致凝膠化,待靜置五分鐘回復流動性後,將溶液塗佈到玻璃板後使用900μm間隙之刮刀進行塗佈。將塗佈完成之樣品置放於50℃烘箱烘烤20分鐘,再緩慢升溫至170℃烘烤20分鐘後,再將烘箱升溫至260℃烘烤20分鐘做為最終處理。
上述所製成之透明聚醯亞胺膜其100~200℃間的熱膨脹係數為19ppm/℃,色度b*為2.7,光穿透度為89%。
<比較例1>
聚醯胺酸溶液的製作
將57.598克的2,2'-二(三氟甲基)二氨基聯苯(TFMB,0.1799mole),加入412.5克的N,N-二甲基乙醯胺(DMAc),待全部溶解後加入79.902克的4,4-六氟異丙基鄰苯二甲酸酐(6FDA,0.1799mole),添加時溫度控制為25℃,攪拌反應二十四小時且溫度持續維持在25℃,最終得到固體含量為25%的聚醯胺酸溶液。
透明聚醯亞胺膜的製作
在上述聚醯胺酸溶液中取出54.4克,並使用N,N-二甲基乙醯胺(DMAc)將固體含量稀釋至為17%,之後分別添加10.1毫升的醋酸酐與3.5毫升的3-甲基吡啶,在均勻攪拌後將溶液塗佈到玻璃板後使用900μm間隙之刮刀進行塗佈。將塗佈完成之樣品置放於50℃烘箱烘烤20分鐘,再緩慢升溫至170℃烘烤20分鐘後,再將烘箱升溫至260℃烘烤20分鐘做為最終處理。
上述所製成之透明聚醯亞胺膜其100~200℃間的熱膨脹係數為
51ppm/℃,色度b*為0.5,光穿透度為89%。
<比較例2>
共聚聚醯胺酸溶液的製作
將9.56克的2,2'-二(三氟甲基)二氨基聯苯(TFMB,0.0299mole,佔總二胺莫爾數比率0.158),加入412.5克的N,N-二甲基乙醯胺(DMAc),待全部溶解後加入5.562克的1,2,3,4-環丁四羧二酐(CBDA,0.0284mole,總酸酐莫爾百分比15%),攪拌反應六小時且溫度持續維持在25℃得到半芳香族聚醯胺酸溶液。將上述半芳香族聚醯胺酸溶液添加50.979克的2,2'-二(三氟甲基)二氨基聯苯(TFMB,0.1592mole),攪拌至完全溶解,再添加71.393克的4,4-六氟異丙基鄰苯二甲酸酐(6FDA,0.1607mole),攪拌一定時間而進行溶解及反應,並且溶液的溫度維持為25℃,最終得到固體含量為25%的共聚聚醯胺酸溶液。
透明聚醯亞胺膜的製作
在上述共聚聚醯胺酸溶液中取出40.40克,並使用N,N-二甲基乙醯胺(DMAc)將固體含量稀釋至20.2%,之後分別添加7.9毫升的醋酸酐與4.1毫升的3-甲基吡啶,在均勻攪拌後因溶解度下降導致凝膠化,待靜置五分鐘回復流動性後,將溶液塗佈到玻璃板後使用900μm間隙之刮刀進行塗佈。將塗佈完成之樣品置放於50℃烘箱烘烤20分鐘,再緩慢升溫至170℃烘烤20分鐘後,再將烘箱升溫至260℃烘烤20分鐘為最終處理。
上述所製成之透明聚醯亞胺膜其100~200℃間的熱膨脹係數40ppm/℃,色度b*為1.0,光穿透度為89%。
<比較例3>
聚醯胺酸溶液的製作
將59.236克的2,2'-雙(三氟甲基)-4,4'-二氨基苯基醚(6FODA,0.1799mole),加入412.5克的N,N-二甲基乙醯胺(DMAc),待全部溶解後加入78.264克的4,4-六氟異丙基鄰苯二甲酸酐(6FDA,0.1799mole),添加時溫度控制為25℃,攪拌反應二十四小時且溫度持續維持在25℃,最終得到固
體含量為25%的聚醯胺酸溶液。
透明聚醯亞胺膜的製作
在上述聚醯胺酸溶液中取出54.4克,並使用N,N-二甲基乙醯胺(DMAc)將固體含量稀釋至為17%,之後分別添加9.9毫升的醋酸酐與3.4毫升的3-甲基吡啶,在均勻攪拌後將溶液塗佈到玻璃板後使用900μm間隙之刮刀進行塗佈。將塗佈完成之樣品置放於50℃烘箱烘烤20分鐘,再緩慢升溫至170℃烘烤20分鐘後,再將烘箱升溫至260℃烘烤20分鐘做為最終處理。
上述所製成之透明聚醯亞胺膜其100~200℃間的熱膨脹係數52ppm/℃,色度b*為1.7,光穿透度為89%。
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。
S7‧‧‧共聚聚醯胺酸溶液加入DMAc
S8‧‧‧加入醋酸酐與3-甲基吡啶
S9‧‧‧刮刀進行塗佈
S10‧‧‧烘箱烘烤
S11‧‧‧形成透明聚醯胺膜
Claims (5)
- 一種透明聚醯亞胺膜,其係由共聚聚醯胺酸經由化學環化法製得而成,其中,該共聚聚醯胺酸至少需具有半芳香族聚醯胺酸,該半芳香族聚醯胺酸是由1,2,3,4-環丁四羧二酐(CBDA)與2,2'-二(三氟甲基)二氨基聯苯(TFMB)反應組成,其中,該半芳香族聚醯胺酸之二酐莫爾數佔該共聚聚醯胺酸之酸酐總莫爾數之百分比20以上,使該透明聚醯亞胺膜具有光穿透度大於80%,色度b*小於5,CTE小於35ppm/℃。
- 如申請專利範圍第1項所述之透明聚醯亞胺膜,其中,該共聚聚醯胺酸更含有芳香族聚醯胺酸,芳香族聚醯胺酸係由芳香族二胺與芳香族酸酐反應而得。
- 如申請專利範圍第2項所述之透明聚醯亞胺膜,其中,該芳香族二胺可為2,2'-二(三氟甲基)二氨基聯苯(TFMB)、2,2'-雙[4-(4-氨基苯氧基苯基)]丙烷(BAPP)、2,2-雙[4-(4-氨基苯氧基)苯基]-1,1,1,3,3,3-六氟丙烷(HFBAPP)、5(6)-氨基-1-(4-氨基苯基)-1,3,3-三甲基茚滿(TMDA)、對苯二胺(PDA)、4,4'-二(4-氨基苯氧基)聯苯(BAPB)、2,2'-雙(三氟甲基)-4,4'-二氨基苯基醚(6FODA)、4,4'-雙(4-氨基苯氧基)二苯碸(BAPS)、9,9-雙(4-氨基苯基)芴(BAFL)、4,4'-二氨基二苯碸(44DDS)、4,4'-二氨基二苯醚(ODA)、4,4'-二氨基苯醯替苯胺(44DABA)、2,2-双(4-氨基苯基)六氟丙烷(Bis-A-AF)、間苯二胺(mPDA)、2,2-雙(3-氨基-4-羥基苯基)六氟丙烷(6FAP)、3,5-二氨基苯甲酸(35DABA)、2-(4-氨基苯基)-5-氨基苯並惡唑(5BPOA)、1,4-雙(4-氨基苯氧基)苯(TPEQ)、4,4'-[1,4-苯基雙(氧)]雙[3-(三氟甲基)苯胺](FAPB)。
- 如申請專利範圍第2項所述之透明聚醯亞胺膜,其中,該芳香族二酐可為1,2,4,5-苯四甲酸酐(PMDA)、3,3',4,4'-聯苯四羧酸二酐(BPDA)、4,4'-氧雙鄰苯二甲酸酐(ODPA)、3,3',4,4'-二苯甲酮四甲酸二酐(BTDA)、3,3,4,4-二苯基碸四羧酸二酸酐(DSDA)、2,3,3',4'-聯苯四甲酸二酐(α-BPDA)、4,4-六氟異丙基鄰苯二甲酸酐(6FDA)、4,4'-(4,4'-異丙基二苯氧基)二酞酸酐 (BPADA)
- 如申請專利範圍第1項所述之透明聚醯亞胺膜,其中,該透明聚醯亞胺膜厚度為10~80um。
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