200835720 九、發明說明： 【發明所屬之技術領域】 本發明關於聚醯亞胺薄膜及其製法。更詳而言，關於所 添加無機粒子不露出，在薄膜中均勻分散的狀態下發生表 面突起，可良好地控制表面狀態，薄膜的行進性、黏著性 及尺寸安定性優異，而且可適應於撓性配線基板（FPC)或薄 膜上晶片（C OF)的自動光學檢査系統（AOI)之聚醯亞胺薄膜 及其製法。 【先前技術】 已知聚醯亞胺薄膜於耐熱性、耐寒性、耐藥品性、電絶 緣性及機械強度等方面具有優異的特性，廣泛利用於電線 的電絶緣材料、絕熱材、撓性配線基板（F PC)的基礎薄膜、 1C的捲帶自動接合（TAB)用的載帶薄膜、及ic的引線框固 定用膠帶等。於此等之中，特別是在FPC、TAB用載帶及 引線固定用膠帶等的用途中，通常經由各種黏著劑來黏合 聚醯亞胺薄膜與銅箔而使用。 聚醯亞胺在使用於此等用途時，重要的實用特性係薄膜 的滑性（易滑性）。於各式各樣的薄膜加工步驟中，藉由確保 薄膜支撐體（例如輥）與薄膜的易滑性、及薄膜彼此的易滑性 ，可提高各步驟的操作性、處理性，而且可回避薄膜上皺 紋等不良處的發生。 另一方面，於聚醯亞胺的主要用途之撓性配線板用途中 ，通常經由各種黏著劑來與銅箔黏合，但是聚醯亞胺由於 其化學構造及耐藥品（溶劑）安定性而使得與銅箔的黏合性 200835720 不足的情況係多的’現狀爲對聚醯亞胺施予鹼處理、電暈 處理、電漿處理、噴砂處理等的表面處理後，使與銅箔黏 著。 又，於最近電子零件的細間距化方面，尤其在FPC的檢 査中，往常以目視來檢查線寬、異物等係爲主流，但由於 導入自動光學檢査系統（AOI)，於以混有無機粉體的習知處 方所製造的耐熱性薄膜中，關於行進性雖然可得到充分滿 足者，但於AOI中，由於無機粉體過大，隨著最近的FPC ^ 等之窄間距化，該粒子係被判斷爲異物，其成爲自動檢査 系統之大障礙。 於以往的聚醯亞胺薄膜之易滑化技術中，已知有將惰性 無機化合物（例如鹼土類金屬的正磷酸鹽.、無水磷酸氫鈣、 焦磷酸鈣、矽石、滑石）加到聚醯胺酸中的方法（參照專利文 獻1 )，以及藉由微細粒子在薄膜表面上形成微細突起後， 施予電漿處理的方法（參照專利文獻2)。然而，由於此等所 示的無機粒子之粒徑大，有不適應於自動光學檢査系統的 ®問題。 又，已知有於聚醯亞胺表層中，使平均粒徑爲0.0 1〜 1 ΟΟμπι之無機質粒子之各粒子的一部分分別被埋設而保持 著，使一部分露出的前述無機質粒子所成的多數突起在該 薄膜的表面層中以1x10〜5χ108個/mm2存在的方法（參照專 利文獻3)。該方法之特徵爲藉由積極地使無機粒子露出表 面，減低薄膜表面的摩擦係數，而有效地得到易滑性效果 ，但由於無機質粒子以一部分露出，而在接面的其它薄膜 200835720 表面上發生擦傷，有招致外觀不良的問題。 專利文獻1 :特開昭62-6 8 8 5 2號公報 專利文獻2 :特開2000- 1 9 1 8 1 0號公報 專利文獻3 :特開平5 -25 29 5號公報 【發明內容】 發明所欲解決的問顯 本發明係以解決上述先前技術的問題點當作課題，進行 檢討而達成結果。 因此，本發明之目的爲提供薄膜的行進性、黏著性及尺 寸安定性優異，且可適應於撓性配線基板（FPC)或薄膜上晶 片（COF)的自動光學檢査系統（AOI)之聚醯亞胺薄膜及其製 法。 解決問題的手段 爲了達成上述目標，依照本發明，提供一種聚醯亞胺薄 膜，其特徵爲以當作二胺成分的對伸苯二胺及4,4’-二胺基 二苯基醚、當作酸二酐成分的均苯四甲酸二酐二酐作爲主 要構成成分，經由醯亞胺化而製造的聚醯亞胺薄膜，粒徑 在0.01〜1 ·5μπι的範圍內，且平均粒徑爲0.05〜0·7μιη，以 及具有粒徑0.1 5〜0.60 μπι的粒子佔全部粒子中80體積％以 上的比例之粒度分佈的無機粒子，係以每薄膜樹脂重量而 言0·1〜0.9重量％的比例分散在薄膜中。 再者，於本發明的聚醯亞胺薄膜中，可舉出以下皆爲較 佳的條件： 上述聚醯亞胺薄膜的各構成成分之比例係：1 〇〜5 0莫耳 200835720 %之對伸苯二胺及50〜90莫耳％之4,4’ -二胺基二苯基醚當作 二胺成分，100莫耳％之均苯四甲酸二酐當作酸二酐成分， 上述無機粒子係以每薄膜樹脂重量而言〇·3〜〇·8重量％ 的比例被含有， 上述無機粒子的平均粒徑爲〇· 1〜， 上述無機粒子的平均粒徑爲〇 . 3〜〇 . 5 μ m， 起因於上述無機粒子的突起係存在於薄膜表面，該突起 的高度爲2μηι以上者之數目係5個/40 cm見方以下，及 薄膜厚度爲5〜75 μιη。 又，上述本發明的聚醯亞胺薄膜之製法的特徵爲使由對 伸苯二胺及4,4’-二胺基二苯基醚所構成的二胺成分、與由 均笨四甲酸二酐所構成的四羧酸二酐成分，在極性有機溶 劑中反應而製造聚醯胺酸，將其醯亞胺化後，成形爲薄膜 時，粒徑在0.01〜1.5μπι的範圍內，而且平均粒徑爲0.05 〜0.7μιη，以及具有粒徑0.15〜0·60μπι的粒子佔全部粒子中 8 〇體積％以上的比例之粒度分佈的無機粒子，係被分散於與 上述極性有機溶劑相同之極性有機溶劑而成爲漿體，將此 漿體加到聚醯亞胺製程中的聚醯胺酸溶液內，上述無機粒 子係每樹脂重量有0.1〜0.9重量％的比例。 發明的效果 依照本發明，如以下之說明，可得到所添加無機粒子不 露出，在薄膜中均勻分散的狀態下發生表面突起，可良好 地控制表面狀態，薄膜的行進性、黏著性及尺寸安定性優 異，而且可適應於撓性配線基板（FPC)或薄膜上晶片（C0F) 200835720 的自動光學檢査系統（AOI)之聚醯亞胺薄膜。 【實施方式】 實施發明的最佳形態 以下詳細說明本發明。 首先，說明於得到本發明的聚醯亞胺薄膜時，前驅物的 聚醯胺酸。 於本發明中，例如使以芳香族四羧酸二酐成分及芳香族 二胺成分或此兩者當作主成分的化學物質，在有機溶劑中 ^ 進行加成聚合，以得到清漆狀聚醯胺酸。於主要構成成分 各自使用當作芳香族二胺成分的對伸苯二胺及4,4’-二胺基 二苯基醚，當作芳香族四羧酸二酐成分的均苯四甲酸二酐 。即，以對伸苯二胺、4,4’-二胺基二苯基醚、及均苯四甲 酸二酐等3種類當作必要構成成分，僅藉由此等3種類， 或除了此等3種類亦添加少量的其它成分來獲得。較佳使 用當作二胺成分的1 〇〜5 0莫耳％之對伸苯二胺及5 0〜9 0莫 耳％之4，4’-二胺基二苯基醚，當作酸二酐成分的1〇〇莫耳％ 之均苯四甲酸二酐來獲得。對伸苯二胺若過多則變硬，而 若過少則太柔軟，故較佳爲1〜70莫耳％，更佳爲5〜60莫 耳％，特佳爲10〜50莫耳％。4,4、二胺基二苯基醚若過多 則變柔軟，而若過少則變硬’故較佳爲2 0〜9 9莫耳。/。，更 佳爲40〜95莫耳％’特佳爲50〜90莫耳％。 於本發明中，如上述地，亦可添加對伸苯二胺或4,4^ 二胺基二苯基醚以外的少量其它二胺。又，也可添加均苯 四甲酸二酐以外的少量其它酸二酐。具體地，作爲其它二 -9- 200835720 胺及酸二酐，可舉出以下者，惟不受此等所限定。 (1) 酸二酐 3,3’，4,4’-聯苯基四羧酸二酐、2,3’，3,4’-聯苯基四羧酸二 酐、3,3’，4,4’-二苯甲酮四羧酸二酐、2,3,6,7-萘二羧酸二酐 、2,2-雙（3,4-二羧基苯基）醚、吡啶-2,3,5,6-四羧酸二酐、 1，2,4,5-萘四羧酸二酐、1，4,5,8-萘四羧酸二酐、1，4,5,8-十 氫萘四羧酸二酐、4,8_二甲基-1，2,5,6-六氫萘四羧酸二酐、 2,6-二氯-1，4,5,8-萘四羧酸二酐、2,7-二氯-1，4,5,8-萘四羧酸 ® 二酐、2,3,6,7-四氯-1，4,5,8-萘四羧酸二酐、1，8,9，10·菲四 竣酸二酐、2,2-雙（2,3-二狻基苯基）丙烷二酐、1，1-雙（3,4-二羧基苯基）乙烷二酐、1，1-雙（2，3_二羧基苯基）乙烷二酐、 雙（2,3-二羧基苯基）甲烷二酐、雙（3,4-二羧基苯基）甲烷二 酐、雙（3,4-二羧基苯基）楓二酐、苯-1，2,3,4-四羧酸二酐、 3,4,3’，4’-二苯甲酮四羧酸二酐等。 (2) 二胺 3，4’-二胺基二苯基醚、3,3’-二胺基二苯基醚、間伸苯二 β 胺、4,4’-二胺基二苯基丙烷、3,4’-二胺基二苯基丙烷、3,3’-二胺基二苯基丙烷、4,4’-二胺基二苯基甲烷、3,4’-二胺基 二苯基甲烷、3,3’-二胺基二苯基甲烷、聯苯胺、4,4’-二胺 基二苯基硫化物、3,4’ -二胺基二苯基硫化物、3，3’-二胺基 二苯基硫化物、4,4’-二胺基二苯基颯、3,4 5-二胺基二苯基 颯、3,3’-二胺基二苯基颯、2,6-二胺基吡啶、雙-(4-胺基苯 基）二乙基矽烷、3,3’-二氯聯苯胺、雙- (4-胺基苯基）乙基氧 化膦、雙-(4-胺基苯基）苯基氧化膦、雙-(4-胺基苯基）-Ν-苯 -10- 200835720 基胺、雙-(4-胺基苯基）-N-甲基胺、1，5-二胺基萘、3，3，-二 甲基-4,4’-二胺基聯苯基、3,4，-二甲基-3’，4-二胺基聯苯基 3，3’-二甲氧基聯苯胺、2,4-雙（ρ-β-胺基-第三丁基苯基）醚、 雙（ρ-β-胺基·第三丁基苯基）醚、ρ-雙（2-甲基-4_胺基戊基） 苯、Ρ-雙-(1，1-二甲基-5-胺基戊基）苯、m-苯二甲基二胺、 p-苯二甲基二胺、1，3-二胺基金剛烷、3,3’-二胺基-1，1，-二 胺基金剛烷、3，3 ’ -二胺基甲基1，1，-二金剛烷、雙（p -胺基環 己基）甲烷、六亞甲二胺、七亞甲二胺、八亞甲二胺、九亞 ^ 甲二胺、十亞甲二胺、3 -甲基七亞甲二胺、4,4，-二甲基七 亞甲二胺、2,11-二胺基十二烷、i，2-雙（3-胺基丙氧基）乙烷 、2,2-二甲基伸丙二胺、3-甲氧基六伸乙二胺、2,5-二甲基 六亞甲二胺、2,5 -二甲基七亞甲二胺、5 -甲基九亞甲二胺、 1，4-二胺基環己烷、1，12-二胺基十八烷、2,5-二胺基-1，3,4-曙二唑、2,2-雙（4-胺基苯基）六氟丙烷、N-(3-胺基苯基）-4-胺基苯甲醯胺、4 -胺基苯基-3 -胺基苯甲酸酯等。 ^ 又’於本發明中，作爲聚醯胺酸溶液之形成時所使用的 有機溶劑之具體例子，例如可舉出二甲亞颯、二乙亞颯等 的亞颯系溶劑、Ν，Ν·二甲基甲醯胺、N，N-二乙基甲醯胺等 的甲醯胺系溶劑、N，N-二甲基乙醯胺、N，N_二乙基乙醯胺 等的乙醯胺系溶劑、N -甲基-2 -吡咯啶酮、N _乙烯基-2 -吡咯 啶酮等的吡咯啶酮系溶劑、苯酚、〇-、心或p-甲酚、二甲 苯酚、鹵化苯酚、兒茶酚等的酚系溶劑、或六甲基磷醯胺 、γ - 丁內酯等的非質子性極性溶劑，此等可被單獨使用或當 作混合物使用，再者如二甲苯、甲苯的芳香族烴之使用係 -11- 200835720 亦可能。 聚合方法係可藉由眾所周知的任一種方法來進行，例如 有如下的方法。 (1) 首先將芳香族二胺成分的全量置入溶劑中，然後以與 芳香族二胺成分的全量成爲等量的方式，添加芳香族四羧 酸類成分及使聚合的方法。 (2) 首先將芳香族四羧酸類成分的全量置入溶劑中，然後 以與芳香族四羧酸類成分成爲等量的方式，添加芳香族二 _ 胺成分。 (3) 將一方的芳香族二胺化合物置入溶劑中後，對於反應 成分而言，在芳香族四羧酸類化合物成爲9 5〜1 0 5莫耳％的 比率下，以反應所必要的時間混合後，添加另一方的芳香 族二胺化合物，接著以全部芳香族二胺成分與全部芳香族 四竣酸類成分成爲大致等量的方式，添加芳香族四殘酸類 化合物，使聚合的方法。 (4) 將芳香族四羧酸類化合物置入溶劑中後，對於反應成 ^ 分而言，在一方的芳香族二胺化合物成爲‘ 95〜1 05莫耳％的 比率下’以反應所必要的時間混合後，添加芳香族四羧酸 類化合物，接著以全部芳香族二胺成分與全部芳香族四羧 酸類成分成爲大致等量的方式，添加另一方的芳香族二胺 化合物，使聚合的方法。 (5) 於溶劑中使一方的芳香族二胺成分與芳香族四羧酸 類以任一者成爲過剩的方式進行反應，以調製聚醯胺酸溶 液（A)，在另一溶劑中使另一方的芳香族二胺成分與芳香族 -12- 200835720 四羧酸類以任一者成爲過剩的方式進行反應’以調製聚醯 胺酸溶液（B)。混合如此所得的各聚_胺酸溶液（A)與（B)， 完成聚合的方法。此時，在調製聚醯胺酸溶液（A)時，當芳 香族二胺成分爲過剩的情況，於聚醯胺酸溶液（B)中使芳香 族四羧酸成分過剩，而且於聚醯胺酸溶液（A)中芳香族四羧 酸成分爲過剩的情況，於聚醯胺酸溶液（B)中使芳香族二胺 成分過剩，混合聚醯胺酸溶液（A)與（B)，以此等反應中所使 用的全部芳香族二胺成分與全部芳香族四羧酸類成分成爲 # 大致等量的方式來調整。 再者，聚合方法係不受此等所限定，亦可以使用其它眾 所周知的方法。 . 如此所得到的聚醯胺酸溶液，係含有5〜40重量％的固 體成分，較佳含有1 〇〜3 0重量％的固體成分，而且其黏度 之布魯克菲爾德黏度計的測定値爲1〇〜2000Pa· s，較佳爲 100〜1000Pa，s，由於安定地送液，故較宜使用。又，有機 溶劑溶液中的聚醯胺酸亦可被部分地醯亞胺化。 ^ 爲了於本發明的薄膜表面上形成突起，添加於樹脂中的 無機粒子必須對於前述聚醯亞胺薄.膜製程中所接觸的全部 化學物質而言爲不溶。 作爲本發明中所可使用的無機粒子，可合適地舉出 Si02(矽石）、Ti02、CaHPCU、Ca2P207 等。其中，以溶膠· 凝膠法之濕式粉碎法所製造的矽石，由於在清漆狀聚醯胺 酸溶液中安定，而且物理安定，不會影響聚醯亞胺的諸物 性，故係較宜。 -13- 200835720 再者，微細矽石粉使用均勻分散在N，N-二甲基甲醯胺、 N，N-二甲基乙醯胺、二甲亞颯、正甲基吡咯啶酮等的極性 溶劑中而成爲分散在極性溶劑的矽石漿體，由於防止凝聚 ，故係較宜。該漿體由於粒徑非常小，故沈降速度慢且安 定。又，即使沈降也能藉由再攪拌而容易再分散。 於本發明中，爲了在聚醯亞胺薄膜的表面上形成突起， 所添加的無機粒子之粒徑在〇 . 0 1〜1 . 5 μπι的範圍內，且平均 粒徑在〇·〇5μηι〜0.7μηι的範圍，更佳在0.1〜0·6μιη的範圍 Φ ，特隹在〇·3〜0.5 μπι的範圍時，不僅該聚醯亞胺薄膜在自 動光學檢査系統的檢査係沒有問題而可適應，而且不會發 生薄膜的機械物性等之降低而可使用。相反地，平均粒徑 若低於此等範圍，則得不到對薄膜的充分易滑性，而若超 過則在自動檢査系統中該粒子係被判斷爲異物而造成障礙 ，故係不宜。又，由於一般薄膜的厚度爲5 μ m〜7 5 μ m，故 該粒徑範圍內的粒子係不會露出聚醯胺薄膜的表面。 無機粒子的添加量較佳係每薄膜樹脂重量含有0.1〜0.9 • 重量％的比例，更佳爲含有〇 . 3〜0 · 8重量％的比例。若爲0.1 重量％以下，則由於薄膜表面的突起數亦不足，得不到對薄 膜的充分易滑性，輸送性變差，捲繞於輥時薄膜的捲繞形 態亦惡化，故係不宜。相反地，若爲〇 · 9重量％以上，雖然 薄膜的易滑性良好，但由於粒子的異常凝聚導致粗大突起 的增加，結果在自動檢査系統中被判斷異物而造成障礙， 故係不宜。 藉由形成無機粒子的表面突起，薄膜表面積亦擴大，見 -14- 200835720 到充分粗面化的錨固效果，亦不會損害黏著性。 無機粒子的粒度分佈爲窄的分佈，即類似大小的粒子佔 全部粒子的比例高者爲良好，具體地較佳爲粒徑0.1 5〜 0·60μιη的粒子佔全部粒子中80體積％以上的比例。低於該 範圍的0 · 1 5 μιη以下的粒子之佔有比例若變高，則由於薄膜 的易滑性降低，故係不宜。又，在無機粒子漿體的送液時 ，可藉由5μιη的截濾器或ΙΟμιη截濾器來去除粗粒子，但若 0.6 0 μιη以上的粒子之佔有比例變高，則不僅由於過濾器的 ^ 堵塞會頻繁發生而損害製程安定性，而且由於容易發生粒 子的粗大凝聚，故係不宜。 於起因於無機粒子的薄膜表面突起中，高度2μιη以上的 突起數目較佳爲5個/40cm見方以下，更佳爲3個/40cm見 方以下，特佳爲1個/40cm見方以下。若比其多，則在自動 檢査系統中該粒子會被判斷爲異物而造成障礙，故係不宜 〇 於本發明中，使如此的無機粒子分散於與聚醯亞胺的製 ^ 造時所使用的有機溶劑相同的極性溶劑中而成爲漿體，將 該漿體加到聚醯亞胺製程中的聚醯胺酸溶液後，使脫環化 脫溶劑，而得到聚醯亞胺薄膜係較宜.，但於聚醯胺酸聚合 前的有機溶劑中添加無機粒子漿體後，經由聚醯胺酸聚合 、脫環化脫溶劑以得聚醯亞胺薄膜等，可在脫環化脫溶劑 前的步驟之任何步驟中添加無機粒子漿體。 其次，說明本發明的聚醯亞胺薄膜之製法。 作爲將聚醯亞胺薄膜製膜的方法，可舉出將聚醯胺酸溶 -15- 200835720 液以薄膜狀流延，加熱地脫環化脫溶劑而得到聚醯亞胺薄 膜之方法，及於聚醯胺酸溶液中混合環化觸媒及脫水劑， 使化學地脫環化而作成凝膠薄膜，將其加熱脫溶劑以得到 聚醯亞胺薄膜的方法，後者由於可壓低所得到的聚醯亞胺 薄膜之熱膨脹係數，故係較宜。 於使化學地脫環化之方法中，首先調製上述聚醯胺酸溶 液。 上述聚醯胺酸溶液係可含有環化觸媒（醯亞胺化觸媒）、 ® 脫水劑及膠化延遲劑等。 作爲本發明所使用的環化觸媒之具體例子，可舉出三甲 胺、三伸乙二胺等的脂肪族三級胺、二甲基苯胺等的芳香 族三級胺、及異喹啉、吡啶、β-甲基吡啶等的雜環三級胺等 ，較佳爲使用選自於雜環式三級胺的至少一種類之胺。 作爲本發明所使用的脫水劑之具體例子，可舉出醋酸酐 、丙酸酐、丁酸酐等的脂肪族羧酸酐、及苯甲酸酐等的芳 香族羧酸酐等，較佳爲醋酸酐及/或苯甲酸酐。 ® 作爲從聚醯胺酸溶液來製造聚醯亞胺薄膜的方法，可以 將含有環化觸媒及脫水劑的聚醯胺酸溶液從附縫口的噴嘴 流延到支撐體上以成形爲薄膜狀，在支撐體上進行一部分 的醯亞胺化以成爲具有自支撐性的的凝膠薄膜後，從支撐 體剝離，作加熱乾燥/醯亞胺化，進行熱處理。 上述聚醯胺酸溶液係通過附縫口的噴嘴而成形爲薄膜 狀，流延到經加熱的支撐體上，在支撐體上作熱閉環反應 ，成爲具有自支撐性的凝膠薄膜，從支撐體剝離。 -16- 200835720 上述支撐體係金屬製的回轉圓筒或循環帶，其溫度係藉 由液體或氣體的熱媒、及/或電熱器等的輻射熱來控制。 上述凝膠薄膜係藉由來自支撐體的受熱及/或熱風或電 熱器等的熱源之受熱，而被加熱到3 0〜2 0 0 °C，較佳加熱到 40〜150°C，作閉環反應，使游離的有機溶劑等之揮發成分 被乾燥，而具有自支撐性，從支撐體剝離。 從上述支撐體所剝離的凝膠薄膜，藉由通常的回轉輥來 邊控制行進速度，邊在行進方向作拉伸。拉伸係在14(TC以 φ 下的溫度以1 . 〇 5〜1.9倍、較佳1 .1〜1 . 6倍、更佳1 . 1〜1 . 5 倍的倍率來實施。在行進方向所拉伸的凝膠薄膜係被導入 拉幅裝置，以拉幅機夾具抓住寬度方向兩端部，邊隨著拉 幅機夾具前進，邊對寬度方向作拉伸。 上述乾燥區所乾燥的薄膜係被熱風、紅外線加熱器等加 熱15秒至10分鐘。接著，藉由熱風及/或電熱器等，在250 〜5 00的溫度進行15秒至20分鐘的熱處理。較佳爲邊調整 對行進方向的拉伸倍率及對寬度方向的拉伸倍率，邊將所 φ 得到的聚醯亞胺薄膜之薄膜厚度調整到5〜7 5 μιη。比該範 圔更厚或更薄係不宜的，因爲製膜性會顯著降低。 實施例 以下使用實施例來說明本發明。 以下說明本發明中的各種物性之測定方法。 [摩擦係數（靜摩擦係數）]200835720 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to a polyimide film and a process for the preparation thereof. More specifically, when the inorganic particles to be added are not exposed, surface protrusions are generated in a state where the film is uniformly dispersed, and the surface state can be favorably controlled, and the film has excellent ductility, adhesion, and dimensional stability, and can be adapted to scratching. A polyimine film of an automatic optical inspection system (AOI) of a wiring board (FPC) or a film on film (COF) and a method of manufacturing the same. [Prior Art] Polyimine films are known to have excellent properties in terms of heat resistance, cold resistance, chemical resistance, electrical insulation, and mechanical strength, and are widely used for electric insulating materials, heat insulating materials, and flexible wiring of electric wires. A base film of a substrate (F PC), a carrier tape for automatic tape bonding (TAB) of 1C, and a tape for fixing a lead frame of ic. Among these, in particular, in the use of tapes for FPC, TAB tapes, and lead fixing tapes, a polyimide film and a copper foil are usually bonded via various adhesives. When the polyimine is used for such applications, an important practical property is the slipperiness (slipiness) of the film. In various film processing steps, by ensuring the smoothness of the film support (for example, a roll) and the film, and the slipperiness of the films, the operability and handleability of each step can be improved, and the avoidance can be avoided. The occurrence of defects such as wrinkles on the film. On the other hand, in the use of flexible wiring boards for the main use of polyimine, it is usually bonded to copper foil via various adhesives, but polyimine is made due to its chemical structure and chemical resistance (solvent) stability. Adhesion to copper foil 200835720 Insufficient condition is the case where the surface of the polyimine is subjected to alkali treatment, corona treatment, plasma treatment, sand blasting, etc., and then adhered to the copper foil. In addition, in the recent fine pitching of electronic parts, especially in the inspection of FPC, it is common to visually check the line width and foreign matter, etc., but the introduction of an automatic optical inspection system (AOI) is to mix inorganic powder. In the heat-resistant film produced by the conventional prescription, although the ductility is sufficiently satisfied, in the AOI, since the inorganic powder is too large, the particle system is narrowed by the recent narrow pitch of FPC^ or the like. Judging as a foreign object, it becomes a major obstacle to the automatic inspection system. In the conventional slippage technique of polyimide film, it is known to add an inert inorganic compound (for example, an orthophosphate of an alkaline earth metal, anhydrous calcium hydrogen phosphate, calcium pyrophosphate, vermiculite, talc) to the polymerization. A method of lysine (refer to Patent Document 1), and a method in which fine particles are formed on the surface of the film by fine particles, and then subjected to plasma treatment (see Patent Document 2). However, due to the large particle size of the inorganic particles, there is a problem of ® that is not suitable for an automatic optical inspection system. Further, it is known that a part of each of the inorganic particles having an average particle diameter of 0.01 to 1 ΟΟμπι is embedded in the surface layer of the polyimide, and a plurality of protrusions of the exposed inorganic particles are partially formed. In the surface layer of the film, it is present in a manner of 1 x 10 to 5 χ 108 / mm 2 (see Patent Document 3). The method is characterized in that the inorganic particles are actively exposed to the surface to reduce the friction coefficient of the surface of the film, thereby effectively obtaining the slippery effect, but since the inorganic particles are partially exposed, they occur on the surface of the other film 200835720. Scuffing, there are problems that cause poor appearance. [Patent Document 1] JP-A-62-6 8 8 5 2 Patent Document 2: JP-A-2000-119 The present invention has been made in order to solve the problems of the prior art described above and to conduct a review to achieve a result. Accordingly, an object of the present invention is to provide a film which is excellent in ductility, adhesion, and dimensional stability, and which can be adapted to an automatic optical inspection system (AOI) of a flexible wiring substrate (FPC) or a wafer-on-film (COF). Imine film and its preparation method. Means for Solving the Problems In order to achieve the above object, according to the present invention, there is provided a polyimine film characterized by p-phenylenediamine and 4,4'-diaminodiphenyl ether as a diamine component. As a main constituent component of pyromellitic dianhydride dianhydride as an acid dianhydride component, a polyimide film produced by ruthenium imidization has a particle diameter of 0.01 to 1 · 5 μm and an average particle diameter. The inorganic particles having a particle size distribution of 0.05 to 0.07 μm and having a particle diameter of 0.15 to 0.60 μm in a ratio of 80% by volume or more of all particles are from 0.1 to 0.9% by weight per film resin. The proportion is dispersed in the film. Further, in the polyimine film of the present invention, the following conditions are preferred: The ratio of each constituent component of the polyimide film is: 1 〇 〜 50 摩尔 200835720 % Phenylenediamine and 50~90 mol% of 4,4'-diaminodiphenyl ether as diamine component, 100 mol% of pyromellitic dianhydride as acid dianhydride component, the above inorganic The particle size is contained in a ratio of 〇3 to 88 wt% per weight of the film resin, and the average particle diameter of the inorganic particles is 〇·1~, and the average particle diameter of the inorganic particles is 〇. 3~〇. 5 μ m, the protrusions due to the above inorganic particles are present on the surface of the film, and the number of the protrusions is 2 μm or more, the number is 5 or less, and the film thickness is 5 to 75 μm. Further, the method for producing a polyimine film of the present invention is characterized in that a diamine component composed of p-phenylenediamine and 4,4'-diaminodiphenyl ether is used, and The tetracarboxylic dianhydride component composed of an anhydride is reacted in a polar organic solvent to produce a poly-proline acid, and when it is imidized, it is formed into a film, and the particle diameter is in the range of 0.01 to 1.5 μm, and the average The inorganic particles having a particle size distribution of 0.05 to 0.7 μm and having a particle diameter of 0.15 to 0·60 μm in a ratio of 8% by volume or more of all particles are dispersed in the same polarity as the above polar organic solvent. The slurry is slurried, and the slurry is added to a polyaminic acid solution in a polyimine process, and the inorganic particles are present in a ratio of 0.1 to 0.9% by weight per resin. Advantageous Effects of Invention According to the present invention, as described below, it is possible to obtain a surface protrusion without being exposed to the inorganic particles, and to uniformly control the surface state, and to control the surface state, the film progressability, adhesion, and dimensional stability. It is excellent in properties and can be applied to a polyimine film of an automatic optical inspection system (AOI) of a flexible wiring substrate (FPC) or a wafer on film (C0F) 200835720. [Embodiment] BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. First, a poly-proline which is a precursor of the polyimide film of the present invention will be described. In the present invention, for example, a chemical substance containing an aromatic tetracarboxylic dianhydride component and an aromatic diamine component or both as a main component is subjected to addition polymerization in an organic solvent to obtain a varnish-like polyfluorene. Amino acid. For the main constituents, p-phenylenediamine and 4,4'-diaminodiphenyl ether, which are aromatic diamine components, are used as the pyromellitic dianhydride of the aromatic tetracarboxylic dianhydride component. . In other words, three types, such as p-phenylenediamine, 4,4'-diaminodiphenyl ether, and pyromellitic dianhydride, are used as essential constituents, and only three types, or other than these, are used. Three types are also added with a small amount of other ingredients. It is preferred to use 1 〇 to 50 mol% of p-phenylenediamine as a diamine component and 4,4'-diaminodiphenyl ether of 50 to 90 mol% as acid 2 The anhydride component is obtained by using 1% by mole of pyromellitic dianhydride. If the amount of the phenylenediamine is too large, it becomes hard, and if it is too small, it is too soft, so it is preferably from 1 to 70 mol%, more preferably from 5 to 60 mol%, particularly preferably from 10 to 50 mol%. If the 4,4 or diaminodiphenyl ether is too soft, it becomes soft, and if it is too small, it becomes hard, so it is preferably 2 0 to 9 9 mol. /. More preferably, the temperature is 40 to 95%, and the optimum is 50 to 90% by mole. In the present invention, as described above, a small amount of other diamine other than phenylenediamine or 4,4-diaminodiphenyl ether may be added. Further, a small amount of other acid dianhydride other than pyromellitic dianhydride may be added. Specifically, the other two -9-200835720 amines and acid dianhydrides are exemplified, but are not limited thereto. (1) Acid dianhydride 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3',3,4'-biphenyltetracarboxylic dianhydride, 3,3',4 , 4'-benzophenonetetracarboxylic dianhydride, 2,3,6,7-naphthalenedicarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)ether, pyridine-2, 3,5,6-tetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,4,5,8- Decalin tetracarboxylic dianhydride, 4,8-dimethyl-1,2,5,6-hexahydronaphthalene tetracarboxylic dianhydride, 2,6-dichloro-1,4,5,8-naphthalene Tetracarboxylic dianhydride, 2,7-dichloro-1,4,5,8-naphthalenetetracarboxylic acid® dianhydride, 2,3,6,7-tetrachloro-1,4,5,8-naphthalene Carboxylic dianhydride, 1,8,9,10·phenanthrene phthalic anhydride, 2,2-bis(2,3-dimercaptophenyl)propane dianhydride, 1,1-bis (3,4- Dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, double (3,4 -dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl) maple dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 3,4,3',4' - benzophenone tetracarboxylic dianhydride or the like. (2) Diamine 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, meta-phenylene diamine, 4,4'-diaminodiphenylpropane , 3,4'-diaminodiphenylpropane, 3,3'-diaminodiphenylpropane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenyl Methane, 3,3'-diaminodiphenylmethane, benzidine, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3 '-Diaminodiphenyl sulfide, 4,4'-diaminodiphenylanthracene, 3,4 5-diaminodiphenylanthracene, 3,3'-diaminodiphenylanthracene, 2,6-diaminopyridine, bis-(4-aminophenyl)diethyldecane, 3,3'-dichlorobenzidine, bis-(4-aminophenyl)ethylphosphine oxide, double -(4-Aminophenyl)phenylphosphine oxide, bis-(4-aminophenyl)-indole-benzene-10- 200835720 amine, bis-(4-aminophenyl)-N-methyl Amine, 1,5-diaminonaphthalene, 3,3,-dimethyl-4,4'-diaminobiphenyl, 3,4,-dimethyl-3',4-diamine linkage Phenyl 3,3'-dimethoxybenzidine, 2,4-bis(ρ-β-amino-t-butylphenyl) ether, bis(ρ-β-amino group · T-butylphenyl)ether, ρ-bis(2-methyl-4-aminopentyl)benzene, fluorene-bis-(1,1-dimethyl-5-aminopentyl)benzene, M-phthaldimethyldiamine, p-phthaldimethyldiamine, 1,3-diamine adamantane, 3,3'-diamino-1,1,-diamine fundane, 3, 3 '-Diaminomethyl 1,1,-diadamantane, bis(p-aminocyclohexyl)methane, hexamethylenediamine, heptamethylenediamine, octamethyldiamine, 九亚^甲Diamine, decethylenediamine, 3-methylheptamethyldiamine, 4,4,-dimethylheptamethyldiamine, 2,11-diaminododecane, i,2-dual ( 3-aminopropoxy)ethane, 2,2-dimethylpropanediamine, 3-methoxyhexamethylenediamine, 2,5-dimethylhexamethylenediamine, 2,5 - dimethyl heptamethylenediamine, 5-methyl ninethylenediamine, 1,4-diaminocyclohexane, 1,12-diaminooctadecane, 2,5-diamino- 1,3,4-oxadiazole, 2,2-bis(4-aminophenyl)hexafluoropropane, N-(3-aminophenyl)-4-aminobenzamide, 4-amine Phenyl-3-amino benzoate and the like. Further, in the present invention, specific examples of the organic solvent used in the formation of the polyaminic acid solution include an anthraquinone solvent such as dimethyl hydrazine or diethyl hydrazine, and hydrazine. A methacrylate solvent such as dimethylformamide or N,N-diethylformamide, or N,N-dimethylacetamide or N,N-diethylacetamide. A pyrrolidinone solvent such as an amine solvent, N-methyl-2-pyrrolidone or N-vinyl-2-pyrrolidone, phenol, hydrazine, heart or p-cresol, xylenol, halogenated a phenolic solvent such as phenol or catechol, or an aprotic polar solvent such as hexamethylphosphonium or γ-butyrolactone, which may be used alone or as a mixture, and further such as xylene. The use of aromatic hydrocarbons of toluene is also possible from -11 to 200835720. The polymerization method can be carried out by any of the well-known methods, for example, the following method. (1) First, an aromatic tetracarboxylic acid component is added to the solvent in the same amount as the total amount of the aromatic diamine component, and a method of polymerization is carried out. (2) First, the entire amount of the aromatic tetracarboxylic acid component is placed in a solvent, and then the aromatic diamine component is added in an equal amount to the aromatic tetracarboxylic acid component. (3) After the aromatic diamine compound is placed in a solvent, the reaction time is required for the reaction of the aromatic tetracarboxylic acid compound at a ratio of 95 to 105 mol%. After the mixing, the other aromatic diamine compound is added, and then the aromatic tetrabasic acid compound is added in such a manner that the entire aromatic diamine component and the entire aromatic tetradecanoic acid component are substantially equalized, and the polymerization is carried out. (4) After the aromatic tetracarboxylic acid compound is placed in a solvent, it is necessary for the reaction to be carried out at a ratio of '95 to 105 mol% of one aromatic diamine compound. After the time is mixed, an aromatic tetracarboxylic acid compound is added, and then the other aromatic diamine component and the entire aromatic tetracarboxylic acid component are added in substantially equal amounts, and the other aromatic diamine compound is added to polymerize. (5) The one of the aromatic diamine component and the aromatic tetracarboxylic acid are allowed to react in excess in the solvent to prepare the polyaminic acid solution (A), and the other solvent is used in the other solvent. The aromatic diamine component and the aromatic -12-200835720 tetracarboxylic acid are reacted in such a manner that either of them is excessively prepared to prepare a polyaminic acid solution (B). The poly-amino acid solutions (A) and (B) thus obtained are mixed to complete the polymerization. In this case, when the polyamine acid solution (A) is prepared, when the aromatic diamine component is excessive, the aromatic tetracarboxylic acid component is excessive in the polyaminic acid solution (B), and the polyamine is used. When the aromatic tetracarboxylic acid component is excessive in the acid solution (A), the aromatic diamine component is excessive in the polyaminic acid solution (B), and the polyaminic acid solutions (A) and (B) are mixed to The total amount of the aromatic diamine component used in these reactions is adjusted to be approximately equal to the total aromatic tetracarboxylic acid component. Further, the polymerization method is not limited to these, and other well-known methods can also be used. The polyamic acid solution thus obtained contains 5 to 40% by weight of a solid component, preferably 1 to 30% by weight of a solid component, and the Brookfield viscometer of the viscosity is determined to be 1〇. ~2000Pa·s, preferably 100~1000Pa, s, because it is safe to supply liquid, it is better to use. Further, the poly-proline in the organic solvent solution may also be partially imidized. In order to form protrusions on the surface of the film of the present invention, the inorganic particles added to the resin must be insoluble to all of the chemicals exposed in the above-mentioned polyimide film process. As the inorganic particles usable in the present invention, SiO 2 ( vermiculite), TiO 2 , CaHPCU, Ca 2 P 207 or the like can be suitably used. Among them, the vermiculite produced by the wet pulverization method of the sol-gel method is stable in the varnish-like polyaminic acid solution, and is physically stable, and does not affect the physical properties of the polyimine, so it is more suitable. . -13- 200835720 Furthermore, the fine vermiculite powder is uniformly dispersed in the polarities of N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl hydrazine, n-methylpyrrolidone and the like. In the solvent, the vermiculite slurry dispersed in the polar solvent is preferably prevented from agglomerating. Since the slurry has a very small particle size, the sedimentation speed is slow and stable. Further, even if it settles, it can be easily redispersed by stirring. In the present invention, in order to form protrusions on the surface of the polyimide film, the particle diameter of the inorganic particles to be added is in the range of 1. 0 1 to 1. 5 μπι, and the average particle diameter is 〇·〇5μηι~ The range of 0.7 μηι, more preferably in the range of 0.1 to 0.6 μm, Φ, especially in the range of 〇·3 to 0.5 μπι, not only the polyimide film can be adapted to the inspection system of the automatic optical inspection system. Moreover, it can be used without causing a decrease in the mechanical properties of the film or the like. On the other hand, if the average particle diameter is less than these ranges, sufficient slipperiness to the film is not obtained, and if it exceeds, the particle system is judged to be a foreign matter in the automatic inspection system, which is an obstacle, and thus it is not preferable. Further, since the thickness of the general film is from 5 μm to 7 5 μm, the particles in the particle size range do not expose the surface of the polyimide film. The amount of the inorganic particles added is preferably from 0.1 to 0.9% by weight per part of the weight of the film resin, more preferably from 3% to 8% by weight. When the amount is 0.1% by weight or less, the number of projections on the surface of the film is insufficient, and sufficient smoothness to the film is not obtained, and the conveyability is deteriorated. When the film is wound around the roll, the winding state of the film is also deteriorated, which is not preferable. On the other hand, when it is 9% by weight or more, the film is excellent in slipperiness, but the coarse protrusions are increased due to abnormal aggregation of particles, and as a result, foreign matter is judged in the automatic inspection system to cause an obstacle, which is not preferable. By forming the surface protrusions of the inorganic particles, the surface area of the film is also enlarged, see -14-200835720 to fully roughen the anchoring effect, and the adhesion is not impaired. The particle size distribution of the inorganic particles is a narrow distribution, that is, a particle having a similar size accounts for a high proportion of all particles, and specifically, a particle having a particle diameter of 0.1 5 to 0·60 μm is preferably a ratio of 80% by volume or more of all particles. . When the proportion of particles below 0 · 15 μmη below this range is increased, the slipperiness of the film is lowered, which is not preferable. Further, when the inorganic particle slurry is supplied, the coarse particles can be removed by a 5 μm filter or a ΙΟμιη filter, but if the proportion of particles of 0.60 μm or more becomes high, not only the filter is blocked. It will occur frequently and impair the stability of the process, and it is not suitable because of the coarse aggregation of particles. In the film surface protrusion caused by the inorganic particles, the number of protrusions having a height of 2 μm or more is preferably 5 pieces/40 cm square or less, more preferably 3 pieces/40 cm square or less, and particularly preferably 1 piece/40 cm square or less. If it is more than this, the particles are judged to be foreign matter in the automatic inspection system and cause an obstacle, so it is not suitable for the present invention to disperse such inorganic particles in the production of polyimine. The organic solvent is used as a slurry in the same polar solvent, and the slurry is added to the polyaminic acid solution in the polyimine process, and the decyclization is desolvated to obtain a polyimine film. However, after adding an inorganic particle slurry to an organic solvent before polymerization of polyglycolic acid, it can be obtained by polypyridic acid polymerization or decarboxylation to obtain a polyimide film, etc., before decarboxylation and solvent removal. The inorganic particle slurry is added in any step of the step. Next, a process for producing a polyimide film of the present invention will be described. As a method of forming a film of a polyimide film, a method of obtaining a polyimine film by casting a polylysine solution -15-200835720 in a film form, and deactivating the solvent by heating, and Mixing a cyclized catalyst and a dehydrating agent in a polyamic acid solution to chemically de-cyclize to form a gel film, and heating and desolvating the solvent to obtain a polyimide film, which is obtained by being capable of being depressed The thermal expansion coefficient of the polyimide film is preferred. In the method of chemically decyclizing, the above polylysine solution is first prepared. The polyamic acid solution may contain a cyclization catalyst (an imidization catalyst), a dehydrating agent, a gelation retarder, and the like. Specific examples of the cyclized catalyst used in the present invention include aliphatic tertiary amines such as trimethylamine and triethylenediamine, aromatic tertiary amines such as dimethylaniline, and isoquinoline. As the heterocyclic tertiary amine such as pyridine or β-methylpyridine, it is preferred to use an amine selected from at least one of the heterocyclic tertiary amines. Specific examples of the dehydrating agent to be used in the present invention include aliphatic carboxylic anhydrides such as acetic anhydride, propionic anhydride, and butyric anhydride, and aromatic carboxylic anhydrides such as benzoic anhydride, and preferably acetic anhydride and/or Benzoic anhydride. ® As a method for producing a polyimide film from a polyaminic acid solution, a polyamic acid solution containing a cyclized catalyst and a dehydrating agent can be cast from a nozzle of a slit to a support to form a film. In the form of a quinone imidization on the support to form a self-supporting gel film, it is peeled off from the support, heated and dried, and imidized, and heat-treated. The polyamic acid solution is formed into a film shape by a nozzle attached to the slit, cast onto the heated support, and is subjected to a thermal closed-loop reaction on the support to form a self-supporting gel film. Body peeling. -16- 200835720 The above-mentioned support system is made of a metal rotary cylinder or an endless belt whose temperature is controlled by the radiant heat of a liquid or gas heat medium and/or an electric heater. The gel film is heated to 30 to 200 ° C by heating from a heat source of a support and/or a hot air or an electric heater, and is preferably heated to 40 to 150 ° C for a closed loop. The reaction causes the volatile component such as a free organic solvent to be dried, and has self-supporting property and is peeled off from the support. The gel film peeled off from the support is stretched in the traveling direction while controlling the traveling speed by a usual turning roll. The stretching is carried out at a magnification of 14 (TC) at a temperature of φ of 1.5 to 1.9 times, preferably 1.1 to 1.6 times, more preferably 1. 1 to 1. 5 times. The stretched gel film is introduced into a tenter device, and the tenter jig is grasped at both ends in the width direction, and stretched in the width direction as the tenter jig advances. The drying zone is dried. The film is heated by hot air, an infrared heater, etc. for 15 seconds to 10 minutes, and then heat-treated at a temperature of 250 to 500 at 15 to 20 minutes by hot air and/or electric heater, etc. The film stretching thickness of the polyimide film obtained by φ is adjusted to 5 to 7 5 μηη in the stretching ratio in the traveling direction and the stretching ratio in the width direction, which is thicker or thinner than the fan. The film forming property is remarkably lowered. EXAMPLES Hereinafter, the present invention will be described using examples. Hereinafter, the measurement methods of various physical properties in the present invention will be described. [Coefficient of Friction (Static Friction Coefficient)]
重疊薄膜的處理面彼此，根據JIS Κ-7 1 25 ( 1 999)來測定 。即，使用滑動係數測定裝置Slip TesteMTECHNO NEEDS -17- 200835720 股份有限公司製），重疊薄膜處理面彼此，於其上放置200 克的秤錘，將薄膜的一方固定，將另一方以100mm/分鐘作 拉伸，測定摩擦係數。 [黏著力] 就黏著性評價方法而言，具體地係以IP C - F C - 2 4 1的方 法爲基礎，以市售的熱塑性聚醯亞胺黏著劑來黏合聚醯亞 胺薄膜與銅箔，在硬板上固定薄膜，進行測定而求得。 [自動光學檢査（AOI)] ® 使用ORBOTECH公司製的SK-75來檢查基底薄膜。將 可區別異物與微粒子的情況評價爲「A」，另一方面將異物 與微粒子的大小類似而無法區別兩者的情況評價爲「C」， 將其中間評價爲[B]。 [無機粒子的評價] 使用堀場製作所的雷射繞射/散射式粒度分佈測定裝置 LA-9 1 0，對已分散在極性溶劑中試料進行測定、解析，由 結果讀取粒徑範圍、平均粒徑、粒徑0.15〜0.60 μηι者在全 β 部粒子中的佔有率。 [異常突起數] 於薄膜的每40cm見方面積中，計算高度2μπι以上的突 起數。高度測定係以LAZERTECH(股）製掃描型雷射顯微鏡 「1LM15W」，使用 NIKON 製 100 倍透鏡（CF Plan 100χ/0·95〇>/0 EPI) ’在「SURFACE1」模式對薄膜表面進行 拍攝·解析而確認。 -18- 200835720 [薄膜厚度] 使用 Mitutoyo 製 Lightmatic(Series318)來測定。 [線膨脹係數] 使用島津製作所製TMA-50，在測定溫度範圍：50〜200 °C、升溫速度：1 0 °C /分鐘的條件下進行測定。 其次，說明聚醯胺酸溶液的合成例。 [合成例1] 以莫耳比爲1 00/75/25的比例來準備均苯四甲酸二酐（ 分子量218.12)/4，4’-二胺基二苯基醚（分子量200.24)/對伸 苯二胺（分子量108.14)，使成爲在D MAc (N，N-二甲基乙醯 胺）中的18·5重量％溶液而聚合，得到3 000p〇ise的聚醯胺 酸溶液。 [合成例2 ] 以莫耳比爲1 00/70/3 0的比例來準備均苯四甲酸二酐（ 分子量218.12)/4,4，-二胺基二苯基醚（分子量200.24)/對伸 苯二胺（分子量108.14)，使成爲在DMAc(N，N-二甲基乙醯 胺）中的18.5重量％溶液而聚合，得到3 000p〇iSe的聚醯胺 酸溶液。 [合成例3 ] 以莫耳比爲 1 00/80/20的比例來準備均苯四甲酸二酐（ 分子量218_12)/4,4，-二胺基二苯基醚（分子量200.24)/對伸 苯二胺（分子量108.14)，使成爲在DMAc(N，N-二甲基乙醯 胺）中的18.5重量％溶液而聚合，得到3 000poiSe的聚醯胺 酸溶液。 -19- 200835720 [合成例4] 以莫耳比爲100/50/50的比例來準備均苯四甲酸二酐（ 分子量218·12)/4,4，-二胺基二苯基醚（分子量2〇〇 24)/對伸 苯二胺（分子量1〇8」4)，使成爲在〇“八(^(11二甲基乙醯 月女）中的18.5重重％丨谷液而聚合’得到3000p〇ise的聚酸胺 酸溶液。 [合成例5] 以旲耳比爲 100/60/40的比例來準備均苯四甲酸二酌1( ® 分子量21 8,1 2)/4,4，-二胺基二苯基醚（分子量200.24)/對伸 苯二胺（分子量108.14)，使成爲在DM Ac(N，N-二甲基乙醯 胺）中的18.5重量。/〇溶液而聚合，得到3 000p〇ise的聚醯胺 酸溶液。 [合成例6 ] 以莫耳比爲 5 0/5 0的比例來混合均苯四甲酸二酐（分子 量218.12)/4,4，_二胺基二苯基醚（分子量200.24)，使成爲在 I DMAc(N，N-二甲基乙醯胺）中的18.5重量％溶液而聚合，得 到3 000p oise的聚醯胺.酸溶液。 [實施例1] 全部粒子的粒徑係滿足在Ο.ΟΙμιη以上且1·5μιη以下， 將平均粒徑0·32μιη、粒徑0. 1 5〜0·60μιη的粒子在全部粒子 中爲87.5體積％之矽石的Ν，Ν-二甲基乙醯胺漿體，加到合 成例1所得到的聚醯胺酸溶液中，該粒子係每樹脂重量有 〇 · 3重量％，進行充分攪拌 '分散。於該聚醯胺酸溶液中， 以相對於聚醯胺酸溶液言5 0重量％的比例來混合及攪拌由 -20- 200835720 醋酸酐（分子量102· 09)與異喹啉所成的轉化劑。此時，對於 聚醯胺酸的醯胺酸基而言，以醋酸酐及異喹啉各自成爲2.0 及0.4莫耳當量的方式來調製。將所得到的混合物從τ型縫 型模頭流延到回轉的90 °C之不銹鋼製圓筒上，得到殘餘揮 .發成分爲5 5重量％、厚度約〇 . 〇 5 mm的具有自支撐性之凝膠 薄膜。從圓筒剝離該凝膠薄膜，抓住其兩端，在加熱爐中 進行2 0 0 °C X 3 0秒、3 5 0 °C X 3 0砂、5 5 0 °C X 3 0秒的處理，得 到厚度3 8 μπι的聚醯亞胺薄膜。表1中顯示所得到的聚醯亞 ®胺薄膜之特性。 [實施例2〜7] 除了所使用的聚醯胺酸溶液、矽石的平均粒徑、粒徑 0.15〜0·60μπι的粒子佔全部粒子中的比例分別如表1地設 定以外，與實施例1同樣地得到3 8 μπι厚度聚醯亞胺薄膜， 對各特性作評價，顯示於表1中。 [實施例8] 0 全部粒子的粒徑係收納在0.0 1 μ m以上且1 . 5 μ m以下， 將平均粒徑〇·37μπι、粒徑0.15〜0.60μιη的粒子在全部粒子 中爲86.5體積％之矽石的Ν，Ν-二甲基乙醯胺漿體，加到合 成例1所得到的聚醯胺酸溶液中，該粒子係每樹脂重量有 〇 · 3 5重量％，進行充分攪拌、分散。於該聚醯胺酸溶液中， 以相對於聚醯胺酸溶液而言50重量％的比例來混合及攪拌 由醋酸酐（分子量1 02.09)與異喹啉所成的轉化劑。此時，對 於聚醯胺酸的醯胺酸基而言，以醋酸酐及異喹啉各自成爲 2.0及〇·4莫耳當量的方式來調製。將所得到的混合物從Τ -21- 200835720 型縫型模頭流延到回轉的90 °C之不銹鋼製圓筒上，得到殘 餘揮發成分爲55重量％、厚度約〇 .05mm的具有自支撐性之 凝膠薄膜。從圓筒剝離該凝膠薄膜，抓住其兩端，在加熱 爐中進行2 0 0 °C X 3 〇秒、3 5 0 °C X 3 0砂、5 5 〇。(： X 3 0秒的處理 ，得到厚度25 μιη的聚醯亞胺薄膜。 表2中顯示所得到的聚醯亞胺薄膜之特性。 [實施例9] 除了圓筒的回^速度與實施例8相同，從圓筒剝離後的 ^ 凝膠薄膜輸送速度（製膜速度）加快爲實施例8的2倍，得到 1 2 · 5 μηι厚度的薄膜以外，與實施例8同樣地作，對所得到 的聚醯亞胺薄膜作各特性的評價，顯示於表2中。 [實施例1〇] 除了圓筒的回轉速度與實施例8相同，從圓筒剝離後的 凝膠薄膜輸送速度（製膜速度）加快爲實施例8的4倍，得到 7.5 μ m厚度的薄膜以外，與實施例8同樣地作，對所得到的 聚醯亞胺薄膜作各特性的評價，顯示於表2中。 [實施例11] 除了圓fe的回轉速度與實施例8相同，從圓筒剝離後的 凝膠薄膜輸送速度（製膜速度）爲實施例8的二分之_速度 ，得到50μιη厚度的薄膜以外，與實施例8同樣地作，對所 得到的聚醯亞胺薄膜作各特性的評價，顯示於表2中。 [實施例12] 除了圓筒的回轉速度與實施例8相同，從_筒剝離後的 凝膠薄膜輸送速度（製膜速度）爲實施例8的三分^ +速胃 -22- 200835720 ，得到7 5 μπι厚度的薄膜以外，與實施例8同樣地作，對所 得到的聚醯亞胺薄膜作各特性的評價，顯示於表2中。 [比較例1] 除了不添加矽石以外，與實施例1同樣地作，得到3 8 μιη 厚度的聚醯亞胺薄膜。對所得到的聚醯亞胺薄膜進行特性 的評價，顯示於表3中。得到靜摩擦係數高且滑性差的薄 膜。而且黏著力亦低。 [比較例2] w 全部粒子的粒徑係滿足在0 · 1 μπι以上且4.5 μηι以下，將 平均粒徑Ι.ίμιη、粒徑0.15〜0·60μιη的粒子在全部粒子中 爲27.3體積％的磷酸氫鈣之Ν，Ν·二甲基乙醯胺漿體，加到 合成例6所得到的聚醯胺酸溶液中，該粒子係每樹脂重量 有0.2重量％，進行充分攬拌、分散。於該聚醯胺酸溶液中 ，以相對於聚醯胺酸溶液而言50重量％的比例來混合及攪 拌由醋酸酐（分子量1 02.09)與異喹啉所成的轉化劑。此時， 對於聚醯胺酸的醯胺酸基而言，以醋酸酐及異喹啉各自成The treated surfaces of the superposed films were measured according to JIS Κ-7 1 25 (1 999). In other words, using a sliding coefficient measuring device Slip Teste MTECHNO NEEDS -17-200835720 Co., Ltd., the film processing surfaces were placed on each other, and a 200 gram weight was placed thereon to fix one of the films, and the other was made at 100 mm/min. Stretching and measuring the coefficient of friction. [Adhesive strength] In terms of the adhesion evaluation method, specifically based on the method of IP C - FC - 2 4 1 , a commercially available thermoplastic polyimide adhesive is used to bond the polyimide film and the copper foil. The film was fixed on a hard plate and measured. [Automatic Optical Inspection (AOI)] ® The base film was inspected using SK-75 manufactured by ORBOTECH. The case where the foreign matter and the fine particles were distinguishable was evaluated as "A". On the other hand, the case where the size of the foreign matter and the fine particles were similar and the difference between the two was evaluated as "C", and the middle was evaluated as [B]. [Evaluation of Inorganic Particles] Using a laser diffraction/scattering particle size distribution measuring apparatus LA-9 1 0 in a Horiba, the sample was measured and analyzed in a sample dispersed in a polar solvent, and the particle size range and average particle were read from the results. The occupancy rate of the diameter and particle diameter of 0.15 to 0.60 μηι in the total β-particles. [Number of Abnormal Protrusions] The number of protrusions having a height of 2 μm or more was calculated for every 40 cm of the film. The height measurement system is a laser scanning microscope "1LM15W" manufactured by LAZERTECH Co., Ltd., using a NIKON 100x lens (CF Plan 100χ/0·95〇>/0 EPI) to shoot the film surface in the "SURFACE1" mode. · Confirmation and confirmation. -18- 200835720 [Film thickness] Measured using Mitutoyo Lightmatic (Series 318). [Linear expansion coefficient] The measurement was carried out under the conditions of a measurement temperature range of 50 to 200 ° C and a temperature increase rate of 10 ° C / min using TMA-50 manufactured by Shimadzu Corporation. Next, a synthesis example of a polyaminic acid solution will be described. [Synthesis Example 1] Pyromellitic dianhydride (molecular weight: 218.12) / 4,4'-diaminodiphenyl ether (molecular weight: 200.24) / pair extension was prepared at a molar ratio of 100/75/25. Phenylenediamine (molecular weight: 108.14) was polymerized as a 18.5% by weight solution in D MAc (N,N-dimethylacetamide) to obtain a 3 000 p〇ise polylysine solution. [Synthesis Example 2] Pyromellitic dianhydride (molecular weight: 218.12) / 4,4,-diaminodiphenyl ether (molecular weight: 200.24) / pair was prepared at a molar ratio of 100/70/30. The phenylenediamine (molecular weight: 108.14) was polymerized to obtain a 18.5% by weight solution in DMAc (N,N-dimethylacetamide) to obtain a polyglycine solution of 3 000 p〇iSe. [Synthesis Example 3] Pyromellitic dianhydride (molecular weight 218_12) / 4,4,-diaminodiphenyl ether (molecular weight: 200.24) / pair extension was prepared at a molar ratio of 100/80/20. Phenylenediamine (molecular weight: 108.14) was polymerized as a 18.5% by weight solution in DMAc (N,N-dimethylacetamide) to obtain a polyamic acid solution of 3 000 poiSe. -19- 200835720 [Synthesis Example 4] Preparation of pyromellitic dianhydride (molecular weight 218·12)/4,4,-diaminodiphenyl ether at a molar ratio of 100/50/50 (molecular weight 2〇〇24)/p-phenylenediamine (molecular weight 1〇8”4), which was polymerized as a 18.5 wt% glutamic acid solution in 〇(8 (^ dimethyl hydrazine) 3000p〇ise of a polyamic acid solution. [Synthesis Example 5] Prepare pyromellitic acid in a ratio of 100/60/40 to prepare 1 (TM molecular weight 21 8,1 2)/4,4, -Diaminodiphenyl ether (molecular weight: 200.24) / p-phenylenediamine (molecular weight: 108.14), polymerized to obtain 18.5 wt. / hydrazine solution in DM Ac (N,N-dimethylacetamide) , a solution of 3 000 p〇ise of polyaminic acid was obtained. [Synthesis Example 6] Pyromellitic dianhydride (molecular weight 218.12) / 4,4,-diamine was mixed at a molar ratio of 5 0/5 0 Diphenyl ether (having a molecular weight of 200.24) was polymerized as a 18.5% by weight solution in I DMAc (N,N-dimethylacetamide) to obtain a 3,000 Å polyisamide acid solution. Example 1] The particle size of all particles is above Ο.ΟΙμιη 1, Ν-dimethylacetamide slurry having an average particle diameter of 0·32 μm and a particle diameter of 0.15 to 0·60 μm, which is 87.5 vol% of all particles in all particles, It is added to the polyaminic acid solution obtained in Synthesis Example 1, and the particles are 〇·3 wt% per weight of the resin, and are sufficiently stirred and dispersed. In the polyamic acid solution, relative to poly-proline A ratio of 50% by weight of the solution is used to mix and stir the conversion agent formed by -20-200835720 acetic anhydride (molecular weight 102·09) and isoquinoline. At this time, for the proline group of polyglycine The acetic anhydride and the isoquinoline were each adjusted to have a molar ratio of 2.0 and 0.4. The obtained mixture was cast from a τ-type slit die to a 90 °C stainless steel cylinder to obtain a residue. A self-supporting gel film having a thickness of about 55% by weight and a thickness of about 〇5 mm. The gel film is peeled off from the cylinder, and both ends are grasped, and the mixture is heated in a heating furnace. °CX 3 0 seconds, 3 5 0 °CX 3 0 sand, 5 5 0 °CX 3 0 seconds treatment, get a thickness of 3 8 μπι Amine film. The properties of the obtained polyfluorene® amine film are shown in Table 1. [Examples 2 to 7] In addition to the polyamine solvent solution used, the average particle size of the vermiculite, and the particle diameter of 0.15 to 0·60 μm A polyimide film having a thickness of 38 μm was obtained in the same manner as in Example 1 except that the ratio of the particles to the total particles was set as shown in Table 1, and each characteristic was evaluated and shown in Table 1. [Example 8] 0 The particle diameter of all the particles was contained in 0.01 μm or more and 1.5 μm or less, and the particles having an average particle diameter of 37·37 μm and a particle diameter of 0.15 to 0.60 μm were 86.5 by volume in all the particles. The ruthenium of %, Ν-dimethylacetamide slurry was added to the polyamic acid solution obtained in Synthesis Example 1, and the particles were 〇·35 wt% per weight of the resin, and thoroughly stirred. ,dispersion. In the polyamic acid solution, a conversion agent composed of acetic anhydride (molecular weight 1 02.09) and isoquinoline was mixed and stirred at a ratio of 50% by weight based on the polyaminic acid solution. In this case, the proline group of polylysine is prepared such that each of acetic anhydride and isoquinoline is 2.0 and 莫·4 molar equivalent. The obtained mixture was cast from a Τ -21-200835720 type slit die to a rotating 90 °C stainless steel cylinder to obtain a self-supporting property of a residual volatile component of 55 wt% and a thickness of about 〇.05 mm. Gel film. The gel film was peeled off from the cylinder, and both ends were grasped, and 200 ° C X 3 〇 seconds, 350 ° C X 3 0 sand, and 5 5 Torr were carried out in a heating furnace. (: X 3 0 second treatment, a polyimide film having a thickness of 25 μm was obtained. The properties of the obtained polyimide film were shown in Table 2. [Example 9] In addition to the speed of the cylinder and the examples In the same manner as in Example 8, the gel film transport speed (film forming speed) after peeling from the cylinder was increased to twice that of Example 8, and a film having a thickness of 12.5 μm was obtained, and the same procedure as in Example 8 was carried out. The obtained polyimine film was evaluated for each characteristic and shown in Table 2. [Example 1] The gel film transport speed after peeling from the cylinder was the same as in Example 8 except that the rotation speed of the cylinder was the same. The film speed was increased to four times that of Example 8, and a film having a thickness of 7.5 μm was obtained. The same properties as in Example 8 were carried out, and the properties of the obtained polyimide film were evaluated and shown in Table 2. [Example 11] The speed of rotation of the gel film (film formation speed) after peeling from the cylinder was the same as that of Example 8, except that the film having a thickness of 50 μm was obtained. The obtained polyimine film was obtained in the same manner as in Example 8. The evaluation of each characteristic is shown in Table 2. [Example 12] The gel film transport speed (film formation speed) after peeling from the cylinder was the same as that of Example 8 except that the rotation speed of the cylinder was the same as in Example 8. In the same manner as in Example 8, except that a film having a thickness of 75 μm was obtained, the evaluation of each characteristic of the obtained polyimine film was shown in Table 2. Comparative Example 1 A polyimide film having a thickness of 38 μm was obtained in the same manner as in Example 1 except that vermiculite was not added. The properties of the obtained polyimide film were evaluated in Table 3. A film having a high coefficient of static friction and poor slipperiness was obtained, and the adhesion was also low. [Comparative Example 2] w The particle size of all particles satisfies 0. 1 μπι or more and 4.5 μηι or less, and the average particle diameter is Ι.ίμιη, granules. The particles having a diameter of 0.15 to 0·60 μm are 27.3 vol% of calcium hydrogen phosphate in all the particles, and a ruthenium dimethyl acetamide slurry is added to the polyamic acid solution obtained in Synthesis Example 6, The particle system has a weight of 0.2% by weight per resin, and is fully mixed and divided. In the polyamic acid solution, a conversion agent composed of acetic anhydride (molecular weight 1 02.09) and isoquinoline is mixed and stirred at a ratio of 50% by weight relative to the polyaminic acid solution. For the proline group of polyproline, the acetic anhydride and the isoquinoline are each formed.
W 爲2.0及0.4莫耳當量的方式來調製。將所得到的混合物從 Τ型縫型模頭流延到回轉的9 0 °C之不銹鋼製圓筒上，得到 殘餘揮發成分爲5 5重量％、厚度約〇 . 〇 5 mm的具有自支撐性 之凝膠薄膜。從圓筒剝離該凝膠薄膜，抓住其兩端，在加 熱爐中進行2 0 0 °C X 3 0秒、3 5 0 °C X 3 0砂、5 5 0 °C X 3 0秒的處 理，得到厚度3 8 μπι的聚醯亞胺薄膜。 表3中顯示所得到的聚醯亞胺薄膜之特性。Α0Ι檢査係 無法區別異物與微粒子，而且異常突起亦發生許多。又， -23- 200835720 由於線膨脹係數高，尺寸變化大。 [比較例3 ] 除了使用粒徑範圍在〇.〇1〜〇·3 μπι、平均粒徑0·08 μιη、 添加量0.35重量％、粒徑0.15〜0.60 μιη的粒子佔全部粒子 中的比例爲3 1.4體積％的矽石以外，與比較例2同樣地得 到3 8 μπι厚度的聚醯亞胺薄膜，對特性作評價，顯示於表3 中。得到靜摩擦係數高、滑性亦稍差的薄膜。又，由於線 膨脹係數高，尺寸變化大。 A [比較例4] 除了使用粒徑範圍在〇·〇1〜1·5μπι、平均粒徑〇·4μπι、 添加量〇 . 3 5重量％、粒徑〇 · 1 5〜0 · 6 0 μιη的粒子佔全部粒子 中的比例爲7 2.6體積％的矽石以外，與比較例2同樣地得 到3 8 μιη厚度的聚醯亞胺薄膜，對特性作評價，·顯示於表3 中。於此例中，由於〇 . 9〜1 . 3 μπι的粒徑之佔有率係佔全體 的22.3體積％，此爲原因的異常突起數變多。而且’ ΑΟΙ ^ 檢査結果係難以區別異物與微粒子。再者，由於線膨脹係 數高，尺寸變化大。 [比較例5] 除了使用合成例1所得到的聚醯胺酸溶液以外’與比較 例2同樣地得到3 8 μιη厚度的聚醯亞胺薄膜。對所得到的聚 醯亞胺薄膜進行特性的評價，顯示於表3中。ΑΟΙ檢査係無 法區別異物與微粒子，異常突起亦多發生。 -24- 200835720W is modulated in a manner of 2.0 and 0.4 molar equivalents. The obtained mixture was cast from a 缝-type slit die to a rotating stainless steel cylinder of 90 ° C to obtain a self-supporting property of a residual volatile component of 55 wt% and a thickness of about 〇5 mm. Gel film. The gel film was peeled off from the cylinder, and both ends were grasped, and subjected to treatment in a heating furnace at 200 ° C for 30 seconds, 350 ° C X 3 sand, and 550 ° C for 30 seconds. A polyimide film having a thickness of 3 8 μm. The properties of the obtained polyimide film are shown in Table 3. The Α0Ι inspection system is incapable of distinguishing between foreign matter and microparticles, and there are many abnormal protrusions. Also, -23- 200835720 due to the high coefficient of linear expansion, the dimensional change is large. [Comparative Example 3] The ratio of particles having a particle diameter ranging from 〇.〇1 to 〇3 μπι, an average particle diameter of 0·08 μηη, an addition amount of 0.35% by weight, and a particle diameter of 0.15 to 0.60 μm was used. A polyimine film having a thickness of 38 μm was obtained in the same manner as in Comparative Example 2 except for 1.4% by volume of vermiculite, and the characteristics were evaluated and shown in Table 3. A film having a high static friction coefficient and a slightly slippery property is obtained. Further, since the coefficient of linear expansion is high, the dimensional change is large. A [Comparative Example 4] The particle size range is in the range of 〇·〇1 to 1·5 μπι, the average particle diameter 〇·4 μπι, the amount of addition 〇3.5 5% by weight, and the particle size 〇·1 5~0 · 6 0 μηη A polyimine film having a thickness of 3 8 μm was obtained in the same manner as in Comparative Example 2 except that the ratio of the particles to the total particles was 72.6 % by volume. The characteristics were evaluated and shown in Table 3. In this example, the occupation ratio of the particle diameter of 〇 9 to 1.3 μm is 22.3 vol% of the total, and the number of abnormal protrusions due to this is increased. Moreover, the results of the 'ΑΟΙ ^ inspection are difficult to distinguish between foreign matter and microparticles. Furthermore, since the coefficient of linear expansion is high, the dimensional change is large. [Comparative Example 5] A polyimine film having a thickness of 38 μm was obtained in the same manner as in Comparative Example 2 except that the polyamic acid solution obtained in Synthesis Example 1 was used. The characteristics of the obtained polyimide film were evaluated in Table 3. The ΑΟΙ inspection system cannot distinguish between foreign matter and microparticles, and abnormal protrusions occur frequently. -24- 200835720
實施例7 合成例5 0.01 〜1.5 0.45 0.40 87.5 00 to 1 0.55 < ο <Ν (Ν 12.2 實施例6 合成例4 0.01 〜1.5 0.55 0.30 86.5 00 cn 0.51 < ο CN <Ν α\ 實施例5 合成例1 0.01 〜1.5 0.37 0.80 87.2 00 cn 1 I 0.45 ι 1 i (Ν (Ν 16.9 實施例4 合成例3 0.01 〜1·5 0.37 0.55 87.4 00 cn 0.46 1 < τ-Η (Ν (Ν 18.8 實施例3 合成例2 0·01 〜1·5 0.45 . 0.30 86.9 00 m 0.47 < ο 15.4 實施例2 合成例1 0.01 〜1.5 0.37 _1 0.35 86.5 00 cn 0.51 < ο <Ν <Ν 1-4 實施例1 1 合成例1 0·01 〜1.5 0.32 0.30 87.5 00 m 0.53 < ο (Ν (Ν 17.2 聚醯胺酸溶液 粒徑範圍(μπι) 平均粒徑(μπι) 添加量(重量％) ? IS 二 Ϊ C；擗 薄膜厚度(μπι) 靜摩擦係數 ΑΟΙ 異常突起數(個） 黏著力(N/cm) 線膨脹係數(ppm/°C ) — ς(Ν_ 200835720Example 7 Synthesis Example 5 0.01 to 1.5 0.45 0.40 87.5 00 to 1 0.55 < ο < Ν (Ν 12.2 Example 6 Synthesis Example 4 0.01 to 1.5 0.55 0.30 86.5 00 cn 0.51 < ο CN <Ν α\ Implementation Example 5 Synthesis Example 1 0.01 to 1.5 0.37 0.80 87.2 00 cn 1 I 0.45 ι 1 i (Ν (Ν 16.9 Example 4 Synthesis Example 3 0.01 to 1.5 0.37 0.55 87.4 00 cn 0.46 1 < τ-Η (Ν ( Ν 18.8 Example 3 Synthesis Example 2 0·01 ～1·5 0.45 . 0.30 86.9 00 m 0.47 < ο 15.4 Example 2 Synthesis Example 1 0.01 to 1.5 0.37 _1 0.35 86.5 00 cn 0.51 < ο < Ν < Ν 1-4 Example 1 1 Synthesis Example 1 0·01 ～1.5 0.32 0.30 87.5 00 m 0.53 < ο (Ν (2 17.2 Polyamide solution particle size range (μπι) Average particle size (μπι) Addition amount ( %%Ϊ C; 擗 film thickness (μπι) static friction coefficient 异常 number of abnormal protrusions (number) adhesion (N/cm) coefficient of linear expansion (ppm/°C) — ς(Ν_ 200835720
csl撇 實施例12 合成例1 0_01〜1.5 0.37 0.35 86.5 0.46 < 〇 CM CM 17.6 實施例11 合成例1 0.01〜1.5 0.37 0.35 86.5 S 0.47 < 〇 CM CM 17.2 實施例10 合成例1 0.01〜1.5 I 0.37 0.35 86.5 1〇 0.50 < Τ— 16.5 實施例9 合成例1 0.01〜1.5 0.37 0.35 86.5 12.5 0.47 < 〇 16.5 實施例8 合成例1 0.01〜1.5 0.37 0.35 86,5 LO CNJ 0.52 < CM CM 17.4 聚醯胺酸溶液 i 粒徑範圍(μΠΊ) 平均粒徑(μηι) 添加量(重量％) 粒徑 0.15〜0_60μηι 的佔有率(體積％)) 薄膜厚度(μρη) 靜摩擦係數 ΑΟΙ 異常突起數(個） 黏著力（N/cm) 線膨脹係數(ppm/°c) 9(N丨 200835720Csl撇 Example 12 Synthesis Example 1 0_01 to 1.5 0.37 0.35 86.5 0.46 < 〇CM CM 17.6 Example 11 Synthesis Example 1 0.01 to 1.5 0.37 0.35 86.5 S 0.47 < 〇CM CM 17.2 Example 10 Synthesis Example 1 0.01 to 1.5 I 0.37 0.35 86.5 1〇0.50 < Τ - 16.5 Example 9 Synthesis Example 1 0.01 to 1.5 0.37 0.35 86.5 12.5 0.47 < 〇 16.5 Example 8 Synthesis Example 1 0.01 to 1.5 0.37 0.35 86, 5 LO CNJ 0.52 < CM CM 17.4 Polyamide solution i Particle size range (μΠΊ) Average particle size (μηι) Addition amount (% by weight) Particle size 0.15~0_60μηι occupancy (% by volume) Film thickness (μρη) Static friction coefficient 异常 Abnormal number of protrusions (a) Adhesion (N/cm) Linear expansion coefficient (ppm/°c) 9(N丨200835720
Co撇 比較例5 合成例1 0·1〜4.5 τ— 0.2 27.3 00 C0 0.46 〇 Ο) C0 CN 17.2 比較例4 合成例6 0.01〜1·5 寸 〇· 0.35 72.6 00 C0 I 0.48 ω 寸 CM CM 26.2 比較例3 合成例6 0.01 〜0.3 0.08 0.35 31.4 00 00 0.82 < 〇 卜 T— 25.8 比較例2 合成例6 0·1 〜4.5 T— CM Ο 27.3 00 00 0.45 〇 00 CO CM 26.1 比較例1 合成例1 I I 1 I 〇〇 C0 2.32 < 〇 τ— 17.6 聚醯胺酸溶液 j 粒徑範圍hm) 平均粒徑(μηΐ) 添加量(重量％) 粒徑 0.15〜0·60μΓη 的佔有率(體積％) 薄膜厚度(μηη) 靜摩擦係數 Α0Ι 異常突起數(個） 黏著力（N/cm) 線膨脹係數(ppm/°c) •广τ· 200835720 由表1〜3的結果可明知，主要以當作二胺成分的對伸 苯二胺及4,4’-二胺基二苯基醚、當作酸二酐成分的均苯四 甲酸二酐，經由醯亞胺化而製造的聚醯亞胺薄膜，以粒徑 在0·01〜1.5μιη的範圍內，且平均粒徑爲〇.〇5〜〇.7μπι無機 粒子當作主體的粉體，以每薄膜樹脂重量而言0.1〜0.9重 量％的比例均勻分散在薄膜中的本發明之聚醯亞胺薄膜，由 於保持優異的易滑性、尺寸安定性、黏著性，且粗大粒子 所致的突起數亦少，故ΑΟΙ檢査時將該粒子判斷爲異物的 ® 障礙亦少，因此適合於用於形成微細配線的撓性配線基板 (FPC)或薄膜上晶片（COF)等之用途。 產業上的利用可能性 本發明的聚醯亞胺薄膜由於薄膜的行進性、黏著性及尺寸 安定性優異，而且可適應於撓性配線基板（FPC)或薄膜上晶 片（COF)的自動光學檢査系統（ΑΟΙ)，故ΑΟΙ檢査判斷無機 粒子爲異物的障礙亦少，適合於用於形成微細配線的撓性 配線基板（FPC)或薄膜上晶片（COF)等之用途。 •【圖式簡單說明】 姐〇 /\\\ 【元件符號說明】 無0 -28-Co撇Comparative Example 5 Synthesis Example 1 0·1 to 4.5 τ—0.2 27.3 00 C0 0.46 〇Ο) C0 CN 17.2 Comparative Example 4 Synthesis Example 6 0.01 to 1·5 inch 〇·0.35 72.6 00 C0 I 0.48 ω inch CM CM 26.2 Comparative Example 3 Synthesis Example 6 0.01 to 0.3 0.08 0.35 31.4 00 00 0.82 < 〇 T T - 25.8 Comparative Example 2 Synthesis Example 6 0·1 ～4.5 T—CM Ο 27.3 00 00 0.45 〇00 CO CM 26.1 Comparative Example 1 Synthesis Example 1 II 1 I 〇〇C0 2.32 < 〇τ - 17.6 Polyamide solution j particle size range hm) average particle diameter (μηΐ) addition amount (% by weight) particle size 0.15~0·60μΓη occupancy rate ( Volume %) Film thickness (μηη) Static friction coefficient Α0Ι Number of abnormal protrusions (number) Adhesion (N/cm) Linear expansion coefficient (ppm/°c) • Wide τ· 200835720 The results from Tables 1 to 3 are known, mainly Polyphenylene diamine and 4,4'-diaminodiphenyl ether, which are diamine components, and pyromellitic dianhydride, which is an acid dianhydride component, are produced by ruthenium imidization. The amine film is a powder having a particle diameter in the range of 0·01 to 1.5 μm and an average particle diameter of 〇.〇5~〇.7μπι as the main body. The polyimine film of the present invention uniformly dispersed in a film in a ratio of 0.1 to 0.9% by weight per film resin, which is excellent in slipperiness, dimensional stability, adhesion, and protrusion due to coarse particles Since the number of particles to be judged as foreign matter is small at the time of inspection, it is suitable for use in a flexible wiring board (FPC) or a wafer on film (COF) for forming fine wiring. INDUSTRIAL APPLICABILITY The polyimide film of the present invention is excellent in film travelability, adhesiveness, and dimensional stability, and can be adapted to automatic optical inspection of a flexible wiring substrate (FPC) or a wafer-on-film (COF). Since the system has a small number of obstacles for detecting the inorganic particles as foreign matters, it is suitable for use in a flexible wiring board (FPC) or a wafer on film (COF) for forming fine wiring. • [Simple diagram description] Sister /\\\ [Component Symbol Description] No 0 -28-