[0016] 以下，詳細說明關於本發明之聚醯亞胺前驅物組成物、聚醯亞胺樹脂之製造方法及聚醯亞胺樹脂。 尚且，本說明書中使用「~」所表示之範圍係意指包括該範圍之「~」前後記載之兩端範圍。 [0017] [聚醯亞胺前驅物組成物] 本發明之聚醯亞胺前驅物組成物含有下述式(1)所示之半縮醛酯化合物、1分子中具有至少2個第一級胺基之聚胺基化合物，及水性媒體，且上述聚胺基化合物包含醯肼化合物。 [0018][0019] 上述式中，n、R1
、R2
、R3
、R4
、R5
及X係各自與式(1)中之n、R1
、R2
、R3
、R4
、R5
及X相同意義。 [0020] 上述式(1)所示之半縮醛酯化合物係對下述式(A)所示之環狀不飽和醚化合物之碳間不飽和鍵加成下述式(B)所示之四羧酸之羧基而成之化合物。 [0021][0022] 式(1)中，n為0或1，R1
、R2
、R3
、R4
及R5
係各自獨立為氫原子、鹵素原子或1價之有機基，亦可互相結合而形成環狀構造，X為4價之有機基。 [0023] 尚且，本發明之聚醯亞胺前驅物組成物中，式(1)中之與X鍵結之羧基亦可電離而成為羧酸根陰離子。 於此情況，本發明之聚醯亞胺前驅物組成物中之上述式(1)所示之半縮醛酯化合物之羧酸根陰離子部分 (-COO-
)，與1分子中具有至少2個第1級胺基之聚胺基化合物之銨陽離子部分(-NH3 +
)亦可成對而成為如下述式所示之鹽構造。 [0024][0025] 式(A)中之n、R1
、R2
、R3
、R4
及R5
，以及式(B)中之X係各自與上述式(1)中之n、R1
、R2
、R3
、R4
、R5
及X相同意義。 [0026] 藉由上述式(A)所示之環狀不飽和醚化合物之碳間不飽和鍵加成上述式(B)所示之四羧酸之羧基，而形成下述式所示之半縮醛酯鍵。 [0027][0028] 上述式中之R1
係與上述式(1)中之R1
相同意義。 [0029] 藉此而形成之半縮醛酯鍵具有對水解之耐性，且不易引起因羧基之保護基脫離所造成之羧基之脫保護。因此，上述式(1)所示之半縮醛酯化合物在水性媒體中之穩定性高，其結果係本發明之聚醯亞胺前驅物組成物之保存穩定性優異。 [0030] 又，藉此形成之半縮醛酯鍵藉由加熱至170℃以上而快速被分解，且由於上述式(A)所示之環狀不飽和醚化合物脫離，故在以200℃以上加熱之醯亞胺化處理之前為止可保護羧基。並且，已脫離之上述式(A)所示之環狀不飽和醚化合物由於在加熱中氣化，硬化物中之上述式(A)所示之環狀不飽和醚化合物之殘存量極少，且不損及取得之聚醯亞胺樹脂之耐溶劑性及耐水性。又，在構成聚醯亞胺樹脂之聚胺部位使用醯肼化合物時，分子內之醯亞胺基之間隔接近，而可取得提升素材硬度之效果。 [0031] 藉此，本發明之聚醯亞胺前驅物組成物在保存時羧基受到保護而在穩定之狀態，並且硬化後幾乎成為純粹之聚醯亞胺樹脂。又，由於硬化後之硬化膜之強度提升，故可取得富有剝離性之素材。 [0032] 〈式(1)所示之半縮醛酯化合物〉 可使本發明之聚醯亞胺前驅物組成物含有單獨1種類之式(1)所示之半縮醛化合物，或亦可含有2種類以上之組合。 [0033] 《各記號之意義》 (n) n為0或1。 [0034] (R1
、R2
、R3
、R4
及R5
) R1
、R2
、R3
、R4
及R5
係各自獨立為氫原子、鹵素原子或1價之有機基，亦可互相結合而形成環狀構造。 [0035] ((鹵素原子)) 鹵素原子並無特別限定，可舉出例如，氟原子、氯原子、溴原子及碘原子，較佳為氟原子。 [0036] ((1價之有機基)) 1價之有機基並無特別限定，較佳為1價之烴基。 作為1價之烴基，可舉出例如，烷基、烯基、炔基、環烷基、環烯基及芳基等，以烷基為佳，較佳為碳數1~3之烷基(C1-3
烷基)，更佳為甲基。在此，作為C1-3
烷基，可舉出如甲基、乙基、丙基及異丙基(丙烷-2-基)。 [0037] 又，上述1價之烴基之氫原子亦可經鹵素原子或羥基所取代。在此，鹵素原子並無特別限定，較佳為氟原子。 [0038] 並且，上述1價之有機基係以不包含與胺基或羧基具有反應性之官能基為佳。在此，作為與胺基具有反應性之基，可舉出例如，羧基、羧酸酐基、羰基、醛基及鹵化羰基，但並非受限於此等。又，作為與羧基具有反應性之官能基，可舉出例如，胺基、羥基、羧基及乙烯氧基，但並非受限於此等。 [0039] ((環狀構造)) 環狀構造並無特別限定，可舉出例如，可具有取代基之芳香族烴環或可具有取代基之脂環式烴環。 例如，n=0時，R2
與R4
或R4
與R5
亦可互相結合而形成可具有取代基之芳香族碳六員環。 [0040] (X) X為4價之有機基。 [0041] ((4價之有機基)) 作為4價之有機基，可舉出例如，從乙烯、丙烷等之在基本骨架具有鏈式烴之化合物，環己烷等之在基本骨架具有環式烴之化合物，苯、萘等之在基本骨架具有芳香族烴之化合物，二苯甲酮等之具有二苯甲酮骨架之化合物，二苯基醚等之具有二苯基醚骨架之化合物、二苯基碸等之具有二苯基碸骨架之化合物，或聯苯等之具有聯苯骨架之化合物等去除任意4個氫原子而成之基。但，並非係受到該等所限定者。 [0042] 又，上述4價之有機基係以不包含與胺基具有反應性之官能基為佳。在此，作為與胺基具有反應性之基，可舉出例如，羧基、羧酸酐基、羰基、醛基及鹵化羰基(halogenocarbonyl)，但並非受該等所限定。 [0043] 《式(1)所示之半縮醛酯化合物之具體例》 以下說明式(1)所示之半縮醛酯化合物之具體例。但，式(1)所示之半縮醛酯化合物並非係受限於以下所說明之具體例者。 [0044] (2,3-二氫呋喃衍生物) 式(1)所示之半縮醛酯化合物之一種具體例為下述式(1-1)所示之2,3-二氫呋喃衍生物。 該當於式(1)中，n=0之情況。 [0045][0046] 式(1-1)中，R1
、R2
、R4
、R5
及X係各自與式(1)中之R1
、R2
、R4
、R5
及X相同意義。 較佳為式(1-1)中，R1
、R2
、R4
及R5
皆為氫原子。 [0047] (3,4-二氫-2H-吡喃衍生物) 式(1)所示之半縮醛酯化合物之另一種具體例為下述式(1-2)所示之3,4-二氫-2H-吡喃衍生物。 該當於式(1)中，n=1之情況。 [0048][0049] 式(1-2)中，R1
、R2
、R4
、R5
及X係各自與式(1)中之R1
、R2
、R4
、R5
及X相同意義。 較佳為式(1-2)中，R1
、R2
、R4
及R5
皆為氫原子。 [0050] (1-苯並呋喃衍生物) 式(1)所示之半縮醛酯化合物之再另一種具體例為下述式(1-3)所示之1-苯並呋喃衍生物。 該當於式(1)中，n=0，且，R4
與R5
互相結合而形成可具有取代基之芳香族碳六員環之情況。 [0051][0052] 式(1-3)中，R1
、R2
、R4
、R5
及X係各自與式(1)中之R1
、R2
、R4
、R5
及X相同意義。 又，R6
、R7
、R8
及R9
係各自獨立為氫原子、鹵素原子或1價之有機基，亦可互相結合而形成環狀構造。 在此，鹵素原子、1價之有機基及環狀構造係如關於R1
、R2
、R4
及R5
之說明中所述。 較佳為式(1-3)中，R1
、R2
、R4
、R5
、R6
、R7
、R8
及R9
皆為氫原子。 [0053] 〈1分子中具有至少2個第一級胺基之聚胺基化合物〉 1分子中具有至少2個第一級胺基之聚胺基化合物(以下，亦有單稱為「聚胺基化合物」之情況)包含醯肼化合物，與醯肼化合物以外之聚胺基化合物。 聚胺基化合物係可組合選自由醯肼化合物以外之聚胺基化合物所成群之1種類以上之聚胺基化合物，與選自由醯肼化合物所構成群之1種類以上之醯肼化合物而使用。 [0054] 聚胺基化合物中之醯肼化合物之比例並無特別限定，以3~50質量%為佳，較佳為3~40質量%，更佳為4~30質量%，較更佳為4~10質量%。本發明之聚醯亞胺前驅物組成物所含有之聚胺基化合物中之醯肼化合物之比例在此範圍內時，會不損及水分散性而使使本發明之聚醯亞胺前驅物組成物硬化而成之聚醯亞胺樹脂之硬度更加提升。 [0055] 《醯肼化合物以外之聚胺基化合物》 作為醯肼化合物以外之聚胺基化合物，可舉出如下述式(2)所示者。 [0056][0057] 式(2)中，m為2以上之整數，Y為m價之有機基或包含矽氧烷鍵之m價之有機矽基。 又，式(2)中，第一級胺基係直接鍵結於碳原子。 又，水性媒體中，式(2)所示之聚胺基化合物之胺基 (-NH2
)亦可成為銨陽離子(-NH3 +
)。 m之上限値並無特別限定，以2000為佳，較佳為600。 [0058] 醯肼化合物以外之聚胺基化合物係可單獨使用1種類，或可組合使用2種類以上。 [0059] (有機聚胺) 本說明書中，醯肼化合物以外之聚胺基化合物當中，將Y為m價之有機基之聚胺基化合物稱為有機聚胺。 [0060] 作為m價之有機基，可舉出例如，從乙烯、丙烷等之在基本骨架具有鏈式烴之化合物，環己烷等之在基本骨架具有環式烴之化合物，苯、萘等之在基本骨架具有芳香族烴之化合物，二苯甲酮等之具有二苯甲酮骨架之化合物，二苯基醚等之具有二苯基醚骨架之化合物、二苯基碸等之具有二苯基碸骨架之化合物，或聯苯等之具有聯苯骨架之化合物等去除任意m個氫原子而成之基等。但，並非係受限於該等者。 [0061] 又，上述m價之有機基係以不包含與羧基具有反應性之基為佳。在此，作為與羧基具有反應性之基，可舉出例如，胺基、羥基、羧基及乙烯氧基等，但不受限於此等。 [0062] 作為有機聚胺，具體地可舉出例如，p-伸苯基二胺、m-伸苯基二胺、o-伸苯基二胺、3,3’-二胺基二苯基醚、3,4’-二胺基二苯基醚、4,4’-二胺基二苯基醚、3,3’-二胺基二苯基硫醚、3,4’-二胺基二苯基硫醚、4,4’-二胺基二苯基硫醚、3,3’-二胺基二苯基碸、3,4’-二胺基二苯基碸、4,4’-二胺基二苯基碸、3,3’-二胺基二苯甲酮、4,4’-二胺基二苯甲酮、3,4’-二胺基二苯甲酮、3,3’-二胺基二苯基甲烷、4,4’-二胺基二苯基甲烷、3,4’-二胺基二苯基甲烷、2,2-二(3-胺基苯基)丙烷、2,2-二(4-胺基苯基)丙烷、2-(3-胺基苯基)-2-(4-胺基苯基)丙烷、2,2-二(3-胺基苯基)-1,1,1,3,3,3-六氟丙烷、2,2-二(4-胺基苯基)-1,1,1,3,3,3-六氟丙烷、2-(3-胺基苯基)-2-(4-胺基苯基)-1,1,1,3,3,3-六氟丙烷、1,1-二(3-胺基苯基)-1-苯基乙烷、1,1-二(4-胺基苯基)-1-苯基乙烷、1-(3-胺基苯基)-1-(4-胺基苯基)-1-苯基乙烷、1,3-雙(3-胺基苯氧基)苯、1,3-雙(4-胺基苯氧基)苯、1,4-雙(3-胺基苯氧基)苯、1,4-雙(4-胺基苯氧基)苯、1,3-雙(3-胺基苄醯基)苯、1,3-雙(4-胺基苄醯基)苯、1,4-雙(3-胺基苄醯基)苯、1,4-雙(4-胺基苄醯基)苯、1,3-雙(3-胺基-α,α-二甲基苄基)苯、1,3-雙(4-胺基-α,α-二甲基苄基)苯、1,4-雙(3-胺基-α,α-二甲基苄基)苯、1,4-雙(4-胺基-α,α-二甲基苄基)苯、1,3-雙(3-胺基-α,α-貳三氟甲基苄基)苯、1,3-雙(4-胺基-α,α-貳三氟甲基苄基)苯、1,4-雙(3-胺基-α,α-貳三氟甲基苄基)苯、1,4-雙(4-胺基-α,α-貳三氟甲基苄基)苯、2,6-雙(3-胺基苯氧基)苄腈、2,6-雙(3-胺基苯氧基)吡啶、4,4’-雙(3-胺基苯氧基)聯苯、4,4’-雙(4-胺基苯氧基)聯苯、雙[4-(3-胺基苯氧基)苯基]酮、雙[4-(4-胺基苯氧基)苯基]酮、雙[4-(3-胺基苯氧基)苯基]硫醚、雙[4-(4-胺基苯氧基)苯基]硫醚、雙[4-(3-胺基苯氧基)苯基]碸、雙[4-(4-胺基苯氧基)苯基]碸、雙[4-(3-胺基苯氧基)苯基]醚、雙[4-(4-胺基苯氧基)苯基]醚、2,2-雙[4-(3-胺基苯氧基)苯基]丙烷、2,2-雙[4-(4-胺基苯氧基)苯基]丙烷、2,2-雙[3-(3-胺基苯氧基)苯基]-1,1,1,3,3,3-六氟丙烷、2,2-雙[4-(4-胺基苯氧基)苯基]-1,1,1,3,3,3-六氟丙烷、1,3-雙[4-(3-胺基苯氧基)苄醯基]苯、1,3-雙[4-(4-胺基苯氧基)苄醯基]苯、1,4-雙[4-(3-胺基苯氧基)苄醯基]苯、1,4-雙[4-(4-胺基苯氧基)苄醯基]苯、1,3-雙[4-(3-胺基苯氧基)-α,α-二甲基苄基]苯、1,3-雙[4-(4-胺基苯氧基)-α,α-二甲基苄基]苯、1,4-雙[4-(3-胺基苯氧基)-α,α-二甲基苄基]苯、1,4-雙[4-(4-胺基苯氧基)-α,α-二甲基苄基]苯、4,4’-雙[4-(4-胺基苯氧基)苄醯基]二苯基醚、4,4’-雙[4-(4-胺基-α,α-二甲基苄基)苯氧基]二苯甲酮、4,4’-雙[4-(4-胺基-α,α-二甲基苄基)苯氧基]二苯基碸、4,4’-雙[4-(4-胺基苯氧基)苯氧基]二苯基碸、3,3’-二胺基-4,4’-二苯氧基二苯甲酮、3,3’-二胺基-4,4’-二聯苯氧基二苯甲酮、3,3’-二胺基-4-苯氧基二苯甲酮、3,3’-二胺基-4-聯苯氧基二苯甲酮、6,6’-雙(3-胺基苯氧基)-3,3,3’,3’-四甲基-1,1’-螺二氫茚、6,6’-雙(4-胺基苯氧基)-3,3,3’,3’-四甲基-1,1’-螺二氫茚、1,3-雙(3-胺基丙基)四甲基二矽氧烷、1,3-雙(4-胺基丁基)四甲基二矽氧烷、α,ω-雙(3-胺基丙基)聚二甲基矽氧烷、α,ω-雙(3-胺基丁基)聚二甲基矽氧烷、雙(胺基甲基)醚、雙(2-胺基乙基)醚、雙(3-胺基丙基)醚、雙[2-(胺基甲氧基)乙基]醚、雙[2-(2-胺基乙氧基)乙基]醚、雙[2-(3-胺基丙氧基)乙基]醚、1,2-雙(胺基甲氧基)乙烷、1,2-雙(2-胺基乙氧基)乙烷、1,2-雙[2-(胺基甲氧基)乙氧基]乙烷、1,2-雙[2-(2-胺基乙氧基)乙氧基]乙烷、乙二醇雙(3-胺基丙基)醚、二乙二醇雙(3-胺基丙基)醚、三乙二醇雙(3-胺基丙基)醚、乙二胺、1,3-二胺基丙烷、1,4-二胺基丁烷、1,5-二胺基戊烷、1,6-二胺基己烷、1,7-二胺基庚烷、1,8-二胺基辛烷、1,9-二胺基壬烷、1,10-二胺基癸烷、1,11-二胺基十一烷、1,12-二胺基十二烷、1,2-二胺基環己烷、1,3-二胺基環己烷、1,4-二胺基環己烷、1,2-二(2-胺基乙基)環己烷、1,3-二(2-胺基乙基)環己烷、1,4-二(2-胺基乙基)環己烷、雙(4-胺基環己基)甲烷、2,6-雙(胺基甲基)雙環[2.2.1]庚烷、及2,5-雙(胺基甲基)雙環[2.2.1]庚烷等。 [0063] 又，作為有機聚胺，也可使用上述有機聚胺之芳香環上之氫原子之一部分或全部被選自由氟原子、甲基、甲氧基、三氟甲基及三氟甲氧基所成群之取代基所取代之有機聚胺。 [0064] 並且，作為有機聚胺，除了上述有機聚胺之外，也可使用1分子中具有2個以上第一級胺基(-NH2
)之聚合物(包含第一級胺基且與羧基具有反應性之基者除外)。作為此種有機聚胺，可舉出例如，聚苯乙烯、聚丙烯酸、聚胺基甲酸酯、聚醯胺或聚醯亞胺等之主鏈或側鏈經由2個以上第一級胺基所修飾者。更具體而言，利用聚合物側鏈之羧基與乙烯亞胺之反應性，而在丙烯酸系共聚物之側鏈接枝聚乙烯亞胺而成之含第一級胺基之丙烯酸系聚合物、以過剩量之二胺或三胺使四羧酸二酐伸長而成之聚醯胺酸樹脂、以過剩量之二胺或三胺使胺基甲酸酯預聚物伸長而成之聚胺基甲酸酯脲樹脂，或以過剩量之二胺或三胺使環氧樹脂伸長而成之變性環氧樹脂等。 [0065] 又，上述1分子中具有2個以上第一級胺基之聚合物係以不包含第一級胺基以外之與羧基具有反應性之基。在此，作為與羧基具有反應性之基，可舉出例如，羥基、羧基或乙烯氧基等，但並不受限於該等。 [0066] 有機聚胺在更因應目的，亦可使用在上述有機聚胺之芳香環上氫原子之一部或全部導入作為取代機基之在聚醯亞胺生成後進行交聯反應之際成為交聯點之乙炔基、苯並環丁烯-1-基、乙烯基、烯丙基、氰基、及異丙烯基之任意1種或2種以上。 [0067] 有機聚胺係可根據目的之物性而適宜選擇。 作為有機聚胺，在使用p-伸苯基二胺等之剛硬二胺時，可使最終取得之聚醯亞胺變成低膨脹率。 作為剛硬之有機二胺，可舉出例如，在同一芳香環上鍵結2個胺基之二胺(芳香族二胺)。作為此種芳香族二胺之具體例，可舉出如p-伸苯基二胺、m-伸苯基二胺、1,4-二胺基萘、1,5-二胺基萘、2、6-二胺基萘、2,7-二胺基萘，及1,4-二胺基蒽。又，亦可使用聚胺之樹枝狀分子(dendrimer)。 [0068] 並且，作為有機聚胺，可舉出如2個以上之芳香環藉由單鍵而鍵結，且2個以上之胺基分別在各個別之芳香族環上直接鍵結或作為取代基之一部分而鍵結之有機聚胺。 作為此種有機聚胺之具體例，可舉出如聯苯胺及甲苯胺。 [0069] 並且，作為有機聚胺，也可使用在苯環具有取代基之有機聚胺。此等取代基為1價之有機基，但該等亦可互相結合。 作為此種有機聚胺之具體例，可舉出如2,2’-二甲基-4,4’-二胺基聯苯、2,2’-貳三氟甲基-4,4’-二胺基聯苯、3,3’-二氯-4,4’-二胺基聯苯、3,3’-二甲氧基-4,4’-二胺基聯苯、及3,3’-二甲基-4,4’-二胺基聯苯。 [0070] 作為上述以外之有機聚胺，可使用例如，胺基乙基化丙烯酸聚合物等。胺基乙基化丙烯酸聚合物，其之一種較佳態樣係可舉出如於側鏈接枝聚乙烯亞胺而成之含有第1級胺基之丙烯酸系聚合物。胺基乙基化丙烯酸聚合物之主鏈為由包含(甲基)丙烯酸酯及(甲基)丙烯酸之單體所形成之(甲基)丙烯酸聚合物。胺基乙基化丙烯酸聚合物係可舉出如具有複數第1級胺基者作為較佳之態樣之一。胺基乙基化丙烯酸聚合物之重量平均分子量係以5,000~100,000為佳。 [0071] 上述胺基乙基化丙烯酸聚合物亦可形成氫鹵酸鹽，例如，鹽酸鹽、氫溴酸鹽等之鹽。 又，胺基乙基化丙烯酸聚合物係可舉出如水溶性者作為較佳態樣之一。 作為展現水溶性之胺基乙基化丙烯酸聚合物之市售品，可舉出例如，Polyment(商標)NK-100PM、Polyment (商標)NK-200PM(皆為日本觸媒公司製)。 [0072] (矽氧烷系聚胺) 本說明書中，在醯肼化合物以外之聚胺基化合物當中，將Y為包含矽氧烷鍵之m價之有機矽基即聚胺基化合物稱為矽氧烷系聚胺。 [0073] 作為包含矽氧烷鍵之m價之有機矽基，可舉出例如，將下述式所示之有機矽化合物之1價之烴基之氫原子當中m個取代成單鍵者。 [0074][0075] 上述式中，k為1以上之整數，R11
、R12
、R13
、R14
、R21
及R22
係各自獨立表示1價之烴基，k≧2時，複數之R21
可互為相同亦可互為相異，複數之R22
可互為相同亦可互為相異。 [0076] 作為矽氧烷系聚胺，具體地可舉出例如，1,3-雙(3-胺基丙基)四甲基二矽氧烷。但，並非係僅受限於此者。 [0077] 在使用矽氧烷系聚胺時，可降低使本發明之聚醯亞胺前驅物組成物硬化而成之聚醯亞胺樹脂之彈性率，且降低玻璃轉移溫度。 [0078] (能與矽氧烷系聚胺併用之有機聚胺) 作為能與上述矽氧烷系聚胺併用之有機聚胺，從耐熱性之觀點，以芳香族聚胺為佳，以芳香族二胺為較佳。芳香族聚胺也可使用1種類以上。 並且，因應目的之物性，可併用芳香族二胺以外之有機聚胺。作為此種有機聚胺，以脂肪族聚胺為佳，以脂肪族二胺為較佳。脂肪族二胺也可使用1種類以上。 在併用芳香族聚胺與其以外之有機聚胺時，芳香族聚胺以外之有機聚胺之使用量係以不超過有機聚胺之總量(不包含矽氧烷系聚胺，僅為有機聚胺之量)之60莫耳%之範圍為佳，以不超過40莫耳%之範圍為較佳。 [0079] 《醯肼化合物》 作為醯肼化合物，可從1分子中具有1個醯肼基與1個以上第一級胺基之單醯肼化合物、1分子中具有2個醯肼基之二醯肼化合物、及1分子中具有3個以上醯肼基之聚醯肼化合物當中適宜選擇使用。 尚且，醯肼基為下述式所示之基。又，水性媒體中，醯肼基之亞胺基部分(＞NH)可成為亞胺陽離子(＞NH2 +
)，胺基部分(-NH2
)可成為銨陽離子(-NH3 +
)。 [0080][0081] 醯肼化合物係可單獨使用1種類，或可將2種類以上組合使用。 作為醯肼化合物，以使用選自由二醯肼化合物及聚醯肼化合物所成群之1種類以上為佳，以使用選自由二醯肼化合物所成群之1種類以上為較佳。 [0082] (二醯肼化合物) 作為二醯肼化合物，可舉出例如，下述式(3)所示之醯肼化合物。 [0083][0084] 式(3)中，Z表示單鍵、2價之脂肪族基或2價之芳香族基。 [0085] 例如，作為Z為單鍵之二醯肼化合物，可舉出如草酸二醯肼。 又，例如，作為Z為2價之脂肪族基之二醯肼化合物，可舉出如丙二酸二醯肼、琥珀酸二醯肼、戊二酸二醯肼、己二酸二醯肼、庚二酸二醯肼、辛二酸二醯肼、壬二酸二醯肼、癸二酸二醯肼、十二烷二酸二醯肼、馬來酸二醯肼、富馬酸二醯肼、二甘醇酸二醯肼、酒石酸二醯肼、蘋果酸二醯肼、及伊康酸二醯肼。 並且，例如，作為Z為2價之芳香族基之二醯肼化合物，可舉出如酞酸二醯肼、異酞酸二醯肼、對酞酸二醯肼、2,6-萘甲二酸二醯肼、4,4-雙苯二醯肼、1,4-萘甲酸二醯肼、及2,6-吡啶二酸二醯肼。 [0086] 作為二醯肼化合物，以使用選自由己二酸二醯肼、癸二酸二醯肼、酞酸二醯肼及異酞酸二醯肼所成群之1種類以上為佳，以使用選自由酞酸二醯肼及異酞酸二醯肼所成群之1種類以上為較佳，以使用異酞酸二醯肼為更佳。 [0087] (聚醯肼化合物) 作為聚醯肼化合物，可舉出例如，將聚丙烯酸等已樹脂化之素材以胼修飾，且經多官能化而得者。 [0088] 〈水性媒體〉 本發明之聚醯亞胺前驅物組成物含有水性媒體。 水性媒體係將水作為主成分之媒體。水係可使用離子交換水、蒸餾水、去離子蒸餾水、RO(Reverse Osmosis；逆浸透)水等。在此，將水作為主成分係指包含水60質量%以上，較佳包含75質量%以上，更佳包含90質量%以上。 藉由使用水性媒體，可減低環境負荷。 [0089] 水性媒體在對基材賦予濕潤性、防腐效果為目的，亦可包含環境負荷為小且不對水之揮發性、乾燥性產生不良影響之公知之醇或醚。例如，可舉出如甲醇、乙醇、n-丙醇、2-丙醇(異丙基醇)、n-丁醇、異丁醇、t-丁醇、丁基溶纖劑、丙二醇單甲基醚、及1-(2-羥基乙基)-2-吡咯啶酮等。 此等醇或醚係可單獨使用1種類，或可將2種類以上組合使用。 [0090] 對水性媒體添加醇時之水性媒體中之醇之比率係以作成1質量%以上40質量%以下為佳，以作成5質量%以上25質量%以下為較佳。醇之比率為1質量%以上時，發揮塗佈組成物對基材之濕潤性改善效果，且抑制基材上塗佈組成物之排斥。又，醇之比率為40質量%以下時，聚醯亞胺前驅物組成物不會析出結晶，也變得容易在基材上將塗佈組成物配置成膜狀。醇之比率在未滿1質量%時，添加醇所成之改善效果會有變得不充分之情況。又，醇之比率在超過40質量%時，聚醯亞胺前驅物組成物會有析出結晶之情況，會有變得難以在基材上將聚醯亞胺前驅物組成物配置成膜狀的憂慮。 [0091] 〈任意成分〉 本發明之聚醯亞胺前驅物組成物亦可更加含有以下記載之任意成分。 [0092] 《揮發性胺》 在以使本發明之聚醯亞胺前驅物組成物之穩定性提升為目的，亦可添加揮發性胺。 本發明之聚醯亞胺前驅物組成物所能含有之揮發性胺之種類並無特別限定，可舉出例如，氨、三甲基胺、三乙基胺、三丁基胺及N-甲基嗎啉。此等揮發性胺係可單獨使用1種類，或可將2種類以上組合使用。 本發明之聚醯亞胺前驅物組成物所能含有之揮發性胺之含量並無特別限定，以不超過在環狀不飽和醚化合物與四羧酸之加成反應所不使用之羧基之莫耳數為佳。 [0093] 《聚合物成分》 本發明之聚醯亞胺前驅物組成物只要不損及其之特性，亦可更含有聚醯亞胺以外之聚合物成分。 將聚合物成分添加至本發明之聚醯亞胺前驅物組成物之情況，例如，可將各成分藉由輥混合、班伯里混合、螺桿混合、攪拌混合等之適宜之混合方法進行配合來調製。 [0094] 《其他添加劑》 本發明之聚醯亞胺前驅物組成物在因應必要，可更加含有選自由補強材、填充劑、防老化劑、防氧化劑、光安定劑、防焦劑、其他交聯遲延劑、塑化劑、加工助劑、滑劑、黏著劑、潤滑劑、難燃劑、防黴劑、防帶電劑、著色劑及界面活性劑所成群之1種類以上之添加劑。 [0095] 《有機溶劑》 本發明之聚醯亞胺前驅物組成物中，除了水性媒體所包含之醇、醚等之有機溶劑、揮發性胺所包含之有機溶劑、及不可避免所混入之微量有機溶劑，以實質上不含有有機溶劑為佳。在此，「實質上不含有有機溶劑」係指本發明之聚醯亞胺前驅物組成物中之有機溶劑之含量係相對於聚醯亞胺前驅物組成物全體為0.1質量%以下。 作為較佳實質上不含有之有機溶劑，可舉出例如，N-甲基-2-吡咯啶酮、1-(2-羥基乙基)-2-吡咯啶酮、二甲亞碸、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基己內醯胺、丙酮、γ-丁內酯、甲基乙基酮及甲基異丁基酮等之高環境負荷之有機溶劑。 [0096] 〈聚醯亞胺前驅物組成物之黏度〉 本發明之聚醯亞胺前驅物組成物之黏度並無特別限定，以0.1~300Pa･s為佳，較佳為0.2~50Pa・s，更佳為0.3 ~10Pa・s，最佳為0.1~10Pa・s。本發明之聚醯亞胺前驅物組成物之黏度在此範圍內時，本發明之聚醯亞胺前驅物組成物之塗佈性會成為更加良好者。 尚且，本發明之聚醯亞胺前驅物組成物之黏度係使用E型黏度計(TV-22，東機產業公司製)測量而得之22℃中之黏度。 [0097] [聚醯亞胺前驅物組成物之調製方法] 本發明之聚醯亞胺前驅物組成物之調製方法並非係受到特別限定者，例如，可藉由實施如後述本發明之聚醯亞胺樹脂之製造方法之第一步驟及第二步驟進行調製。 [0098] [聚醯亞胺樹脂之製造方法] 本發明之聚醯亞胺樹脂之製造方法包括以下之第一步驟、第二步驟，及第三步驟。 [0099] 又，取代使用藉由實施第一步驟及第二步驟調製而成之聚醯亞胺前驅物組成物，而改用本發明之聚醯亞胺前驅物組成物之聚醯亞胺樹脂之製造方法也係包括在本發明之聚醯亞胺樹脂之製造方法。 [0100] 〈第一步驟〉 第一步驟係混合下述式(A)所示之環狀不飽和醚化合物(以下亦有單稱為「環狀不飽和醚化合物」之情況)、下述式(B)所示之四羧酸(以下亦有單稱為「四羧酸」之情況)，及水性媒體，進行攪拌，而合成下述式(A)所示之環狀不飽和醚化合物與下述式(B)所示之四羧酸之加成物的步驟。 [0101][0102] 式(A)中之n、R1
、R2
、R3
、R4
及R5
，以及式(B)中之X係分別與上述式(1)中之n、R1
、R2
、R3
、R4
、R5
及X相同意義。 [0103] 第一步驟中，環狀不飽和醚化合物與四羧酸之加成物[式(1)所示之半縮醛酯化合物]係在水性媒體中受到合成。因此，第一步驟中，取得上述式(1)所示之半縮醛酯化合物分散於水性媒體之水性組成物。此水性組成物除了含有上述式(1)所示之半縮醛酯化合物及水性媒體之外，也可含有未反應之環狀不飽和醚化合物及四羧酸，又，亦可含有相對於四羧酸1分子加成2~4分子之環狀不飽和醚化合物而成之半縮醛酯化合物，並且，在使用後述觸媒時，亦可含有該觸媒。 [0104] 《式(A)所示之環狀不飽和醚化合物》 第一步驟中，式(A)所示之環狀不飽和醚化合物係可單獨使用1種類，或可將2種類以上組合使用。 [0105] 以下，例舉式(A)所示之環狀不飽和醚化合物之具體例進行說明。尚且，式(A)所示之環狀不飽和醚化合物並非係受於以下說明之具體例者。 [0106] (2,3-二氫呋喃或其衍生物) 式(A)所示之環狀不飽和醚化合物之較佳一態樣為下述式(A-1)所示之2,3-二氫呋喃或其衍生物。 [0107][0108] 上述式(A-1)係該當於上述式(A)中n=0之情況。 上述式(A-1)中之R1
、R2
、R4
及R5
係各自與式(A)中之R1
、R2
、R4
及R5
相同意義。 作為上述式(A-1)所示之化合物，以2,3-二氫呋喃為佳。 [0109] (3,4-二氫-2H-吡喃) 式(A)所示之環狀不飽和醚化合物之其他較佳之一態樣為下述式(A-2)所示之3,4-二氫-2H-吡喃或其衍生物。 [0110][0111] 上述式(A-2)係該當於上述式(A)中n=1之情況。 上述式(A-2)中之R1
、R2
、R3
、R4
及R5
係各自與式(A)中之R1
、R2
、R3
、R4
及R5
相同意義。 作為上述式(A-2)所示之化合物，以3,4-二氫-2H-吡喃為佳。 [0112] (1-苯並呋喃或其衍生物) 式(A)所示之環狀不飽和醚化合物之另一較佳一態樣為下述式(A-3)所示之1-苯並呋喃或其衍生物。 [0113][0114] 上述式(A-3)係該當於上述式(A)中n=0且R4
與R5
形成可具有取代基(R6
~R9
)之芳香族碳六員環之情況。 上述式(A-3)中之R1
、R2
、R4
及R5
係各自與式(A)中之R1
、R2
、R4
及R5
相同意義。 上述式(A-3)中之R6
、R7
、R8
及R9
係各自與上述式(1-3)中之R6
、R7
、R8
及R9
相同意義。 作為上述式(A-3)所示之化合物，以1-苯並呋喃為佳。 [0115] 《式(B)所示之四羧酸》 第一步驟中，式(B)所示之四羧酸係可單獨使用1種類，或可將2種類以上組合使用。 [0116] 以下例舉式(B)所示之四羧酸之具體例。尚且，式(B)所示之四羧酸並非係受限於以下例舉之具體例者。 [0117] 作為式(B)所示之四羧酸，具體地可舉出例如，1,2,4,5-苯四羧酸(苯均四酸)、1,2,3,4-苯四羧酸(苯四甲酸，mellophanic acid)、2,3,6,7-萘四羧酸、1,4,5,8-萘四羧酸、1,2,5,6-萘四羧酸、3,4,9,10-苝四羧酸、2,3,6,7-蒽四羧酸、1,2,7,8-菲四羧酸、3,3’,4,4’-二苯甲酮四羧酸、2,2’,3,3’-二苯甲酮四羧酸、雙｛4-[4-(1,2-二羧基)苯氧基]苯基｝酮、雙｛4-[3-(1,2-二羧基)苯氧基]苯基｝酮、雙｛4-[4-(1,2-二羧基)苯氧基]苯基｝酮、雙｛4-[3-(1,2-二羧基)苯氧基]苯基｝酮、3,3’,4,4’-聯苯四羧酸、2,2’,3,3’-聯苯四羧酸、2,2’,6,6’-聯苯四羧酸、雙(3,4-二羧基苯基)醚、4,4’-雙[4-(1,2-二羧基)苯氧基]聯苯、4,4’-雙[3-(1,2-二羧基)苯氧基]聯苯、雙(2,3-二羧基苯基)甲烷、雙(3,4-二羧基苯基)甲烷、1,1-雙(2,3-二羧基苯基)乙烷、2,2-雙(3,4-二羧基苯基)丙烷、2,2-雙(2,3-二羧基苯基)丙烷、2,2-雙｛4-[4-(1,2-二羧基)苯氧基]苯基｝丙烷、2,2-雙｛4-[3-(1,2-二羧基)苯氧基]苯基｝丙烷、2,2-雙(3,4-二羧基苯基)-1,1,1,3,3,3-六氟丙烷、2,2-雙(2,3-二羧基苯基)-1,1,1,3,3,3-六氟丙烷、2,2-雙｛4-[4-(1,2-二羧基)苯氧基]苯基｝-1,1,1,3,3,3-六氟丙烷、2,2-雙｛4-[3-(1,2-二羧基)苯氧基]苯基｝-1,1,1,3,3,3-六氟丙烷、1,3-雙[(3,4-二羧基)苄醯基]苯、1,4-雙[(3,4-二羧基)苄醯基]苯、雙(3,4-二羧基苯基)碸、雙｛4-[4-(1,2-二羧基)苯氧基]苯基｝碸、雙｛4-[3-(1,2-二羧基)苯氧基]苯基｝碸、雙｛4-[4-(1,2-二羧基)苯氧基]苯基｝硫醚、及雙｛4-[3-(1,2-二羧基)苯氧基]苯基｝硫醚等。 [0118] 又，作為式(B)所示之四羧酸，從使本發明之聚醯亞胺前驅物組成物乾燥、硬化而得之聚醯亞胺樹脂之耐熱性、線熱膨脹係數等之觀點，以芳香族四羧酸為佳，以1,2,4,5-苯四羧酸(苯均四酸)、1,2,3,4-苯四羧酸(苯四甲酸)、2,3,6,7-萘四羧酸、3,3’,4,4’-二苯甲酮四羧酸、3,3’,4,4’-聯苯四羧酸、2,3,3’,4’-聯苯四羧酸、2,3,2’,3’-聯苯四羧酸、2,2’,6,6’-聯苯四羧酸、雙(3,4-二羧基苯基)醚、2,2-雙(3,4-二羧基苯基)-1,1,1,3,3,3-六氟丙烷、或雙(3,4-二羧基苯基)醚為佳。 [0119] 並且，作為式(B)所示之四羧酸，從半縮醛酯鍵之穩定性之觀點，以3,3’,4,4’-聯苯四羧酸、2,3,3’,4’-聯苯四羧酸、2,3,2’,3’-聯苯四羧酸、或雙(3,4-二羧基苯基)醚為佳。 [0120] 《水性媒體》 與在關於本發明之聚醯亞胺前驅物組成物所說明之水性媒體相同。 [0121] 《第一步驟之詳細說明》 第一步驟中，藉由混合上述式(A)所示之環狀不飽和醚化合物、上述式(B)所示之四羧酸，及水性媒體並進行攪拌，而可調製出上述式(A)所示之環狀不飽和醚化合物與上述式(B)所示之四羧酸之加成物[式(1)所示之半縮醛酯化合物]之水性組成物。 根據此方法，由於不需使用高環境負荷之有機溶劑，並且在水性媒體中環狀不飽和醚化合物與四羧酸進行反應而可取得半縮醛酯化合物之水性組成物，故並無回收反應生成物之半縮醛酯化合物再混合至水性媒體中之必要，而可刪減步驟數。 環狀不飽和醚化合物之莫耳數通常係相對於四羧酸之莫耳數，以作成0.5~4倍之莫耳數為佳，以作成1~2倍之莫耳數為較佳。 混合環狀不飽和醚化合物、四羧酸，及水性媒體之方法並無特別限定。 例如，可藉由混合含有環狀不飽和醚化合物及水性媒體之水性組成物，與含有四羧酸及水性媒體之水性組成物並進行攪拌，而混合環狀不飽和醚化合物、四羧酸，及水性媒體。 又，例如，可藉由對含有四羧酸及水性媒體之水性組成物添加環狀不飽和醚化合物並進行攪拌，而混合環狀不飽和醚化合物、四羧酸，及水性媒體。 又，可舉出例如，可對含有環狀不飽和醚化合物及水性媒體之水性組成物添加四羧酸並進行攪拌之方法等。 [0122] 進行混合及攪拌時之溫度(反應溫度)只要係能進行加成反應之溫度，即無特別限定，以5~60℃為佳，以20~50℃為較佳，以約25℃為更佳。 攪拌時間只要能充分進行加成反應之時間，即無特別限定，以30分鐘~6小時為佳，以30分鐘~3小時為較佳，以約1小時為更佳。 在調製上述包含加成物之水性組成物時之環境並無特別限定，可使用如大氣環境、氮環境、惰性氣體環境等之環境。 又，上述用以調製包含加成物之水性組成物之形式可為連續式，亦可為批次式。 [0123] 《觸媒》 在含有環狀不飽和醚化合物、四羧酸，及水性媒體之混合液中，可更加含有促進環狀不飽和醚化合物與四羧酸之反應用之觸媒。 作為此種觸媒，可舉出例如，促進環狀不飽和醚化合物之不飽和鍵與四羧酸之羧基之加成反應用之觸媒。 此種觸媒並無特別限定，作為具體例，可舉出如藉由羧酸而促使高酸性度之四氯化鈦、四氯化錫等之烯醇形成者。 觸媒係可單獨使用1種類，或可將2種類以上組合使用。 [0124] 〈第二步驟〉 第二步驟為混合上述第一步驟合成之加成物、1分子中具有至少2個第一級胺基之聚胺基化合物，及水性媒體並進行而調製出聚醯亞胺前驅物組成物的步驟。 [0125] 《加成物》 第一步驟所合成之加成物。 上述加成物為分散於水性媒體之水性組成物之形態。 [0126] 《1分子中具有至少2個第一級胺基之聚胺基化合物》 與關於本發明之聚醯亞胺前驅物組成物中所說明之1分子中具有至少2個第一級胺基之聚胺基化合物相同。 [0127] 《水性媒體》 與關於本發明之聚醯亞胺前驅物組成物中所說明之水性媒相同。 尚且，第一步驟使用之水性媒體，與第二步驟使用之水性媒體可為相同種類，亦可為相異種類，但以同種類為佳。 [0128] 《第二步驟之詳細說明》 第二步驟中，藉由混合第一步驟所合成之加成物[式(1)所示之半縮醛酯化合物]、1分子中具有至少2個第一級胺基之聚胺基化合物(以下單稱為「聚胺基化合物」)，及水性媒體並進行攪拌，而可調製聚醯亞胺前驅物組成物。 根據此方法，與上述第一步驟相同，不需使用高環境負荷之有機溶劑，進而可刪減步驟數。 混合第一步驟所合成之加成物、聚胺基化合物，及水性媒體之方法並無特別限定。 例如，可藉由混合含有加成物及水性媒體之水性組成物、含有聚胺基化合物及水性媒體之水性組成物並進行攪拌，而混合加成物、聚胺基化合物，及水性媒體。 又，例如，可藉由對含有加成物及水性媒體之水性組成物添加聚胺基化合物並進行攪拌，而混合加成物、聚胺基化合物，及水性媒體。 [0129] 又，可更加混合上述本發明之聚醯亞胺前驅物組成物可含有之任意成分。 [0130] 進行混合及攪拌時之溫度並無特別限定，以5~45℃為佳，以20~30℃為較佳，以約25℃為更佳。 攪拌時間並無特別限定，以30分鐘~6小時為佳，以1小時~3小時為較佳，以約2小時為更佳。 調製聚醯亞胺前驅物組成物時之環境並無特別限定，可使用如大氣環境、氮環境、惰性氣體環境等之環境。 又，調製聚醯亞胺前驅物組成物製用之形式可為連續式，亦可為批次式。 [0131] 〈第三步驟〉 第三步驟為加熱處理第二步驟所調製之聚醯亞胺前驅物組成物，使其硬化，而製造出聚醯亞胺樹脂的步驟。 [0132] 《聚醯亞胺前驅物組成物》 第二步驟所調製之聚醯亞胺前驅物組成物。 本發明之聚醯亞胺前驅物組成物，且為含有上述式(1)所示之半縮醛酯化合物、1分子中具有至少2個第一級胺基之聚胺基化合物，及水性媒體之水性組成物。 [0133] 《加熱處理》 加熱處理係以作成由乾燥聚醯亞胺前驅物組成物之乾燥階段、進行羧基之脫保護之脫保護階段，及，進行由四羧酸與聚胺化合物之醯亞胺化所成之硬化的硬化階段所構成3階段，或以作成由乾燥聚醯亞胺前驅物組成物之乾燥階段，與進行羧基之脫保護及進行由四羧酸與聚胺化合物之醯亞胺化所成之硬化之脫保護・硬化階段所構成之2階段為佳。 [0134] (乾燥階段) 藉由加熱聚醯亞胺前驅物組成物使其乾燥，而可提高聚醯亞胺前驅物組成物之成形性。 加熱溫度並無特別限定，以80℃以上為佳，較佳為80℃~100℃。 又，加熱時間並無特別限定，以3分鐘~1小時為佳，較佳為15分鐘~45分鐘。 [0135] (脫保護階段) 藉由加熱經乾燥之聚醯亞胺前驅物組成物，引起脫離反應，式(1)所示之半縮醛酯化合物解離成式(A)所示之環狀不飽和醚化合物，與式(B)所示之四羧酸。藉此，四羧酸之羧基受到脫保護，而變得能藉由與聚胺基化合物之醯亞胺化來硬化。在此，式中之n、R1
、R2
、R3
、R4
及R5
及X係如同先前所說明。尚且，四羧酸也可脫水而成為無水物。 [0136][0137] 加熱溫度並無特別限定，以170℃以上未滿200℃為佳。 又，加熱時間並無特別限定，以3分鐘~1小時為佳，較佳為15分鐘~45分鐘。 [0138] (硬化階段) 藉由加熱羧基已脫保護之聚醯亞胺前驅物組成物，引起四羧酸與聚胺基酸之醯亞胺化(脫水閉環)，促使聚醯亞胺前驅物組成物硬化。 尚且，下述式為說明四羧酸與二胺之醯亞胺化之反應式。 [0139][0140] 加熱溫度並無特別限定，以200℃~400℃為佳。 又，加熱時間並無特別限定，以5分鐘~2小時為佳，較佳為10分鐘~50分鐘。 [0141] (脫保護・硬化階段) 藉由加熱上述乾燥階段中經乾燥之聚醯亞胺前驅物組成物，將羧基予以脫保護，進行四羧酸與聚胺化合物之醯亞胺化，而使聚醯亞胺前驅物組成物硬化，取得硬化物之聚醯亞胺樹脂。 加熱溫度並無特別限定，以200℃~400℃為佳。 又，加熱時間並無特別限定，以5分鐘~2小時為佳，較佳為10分鐘~50分鐘。 [0142] 上述各階段中之加熱方法，並無特別限定，可使用加熱板、加壓加熱、蒸氣加熱、烤箱加熱及熱風加熱等之過往公知之方法。 本發明之聚醯亞胺樹脂之製造方法係以規定形狀進行加壓加熱後，藉由蒸氣加熱、烤箱加熱或熱風加熱等更進行加熱為佳。 [0143] 〈本發明之聚醯亞胺樹脂之製造方法之特徵點〉 本發明之聚醯亞胺樹脂之製造方法之特徵點之一在於使用含有上述式(1)所示之半縮醛酯化合物(加成物)、聚胺基化合物，及水性媒體之聚醯亞胺前驅物組成物。由於半縮醛鍵具有對水解之耐性，故上述式(1)所示之半縮醛酯化合物不易引起在源自上述式(A)所示之環狀不飽和醚化合物之部分之從上述式(B)所示之四羧酸部分之脫離反應，且四羧酸之羧基不易脫保護。藉此，上述聚醯亞胺前驅物組成物展現優異儲藏穩定性。 本發明之聚醯亞胺樹脂之製造方法之另一特徵點在於上述式(1)所示之半縮醛酯化合物(加成物)藉由加熱引起脫離反應，而分解成源自上述式(A)所示之環狀不飽和醚化合物之部分，與上述式(B)所示之四羧酸部分，故可容易進行四羧酸之羧基之脫保護。 本發明之聚醯亞胺樹脂之製造方法之更加另一之特徵點在於、聚胺基化合物藉由包含醯肼化合物，可提升使上述聚醯亞胺前驅物硬化而成之聚醯亞胺樹脂之硬度。而係由於藉由四羧酸與醯肼化合物之醯亞胺化所形成之醯亞胺基間之距離接近所造成者。 [0144] [聚醯亞胺樹脂] 本發明之聚醯亞胺樹脂係本發明之聚醯亞胺前驅物組成物硬化而成之聚醯亞胺樹脂。 使本發明之聚醯亞胺前驅物組成物硬化之方法並無特別限定，例如，可藉由實施上述本發明之聚醯亞胺樹脂之製造方法之第三步驟使其硬化，而可取得聚醯亞胺樹脂。 [0145] 本發明之聚醯亞胺樹脂在例如汽車等之輸送機械、一般機器・裝置、電子・電器、建築等之廣泛領域中，有用作為密封・遮蔽材、緩衝・保護材、電線被覆材、工業用帶類、軟管・硬管類、膜・片類等，又，亦係有用作為電極材料、熱傳導劑、導電劑等經粒子化之素材之黏合劑材料。 [0146] 以下例舉實施例及比較例，更加具體說明本發明，但本發明並非係受限於該等實施例者。 [實施例] [0147] [實施例1] 〈聚醯亞胺前驅物組成物之調製〉 對具備攪拌機之可拆式燒瓶(100mL；筒型)添加2,3,3,4-聯苯四羧酸(2.9g)及水(35.0g)，在25℃中攪拌混合10分鐘後，添加2,3-苯並呋喃(1.0g)，更在25℃中攪拌混合45分鐘，而取得四羧酸衍生物之水分散液。 對取得之水分散液，添加苯乙烯丙烯醯基型聚胺(日本觸媒公司製，Polyment(商標)NK-200PM；不揮發殘分56質量%，胺價2.55mmol/g-solid；m=60)(10.0g)、異酞酸二醯肼(0.5g)，在25℃中攪拌混合2小時，而取得聚醯亞胺前驅物之乳白色分散液(聚醯亞胺前驅物組成物)。 [0148] [實施例2] 〈聚醯亞胺前驅物組成物之調製〉 除了取代水(35.0g)而改用水(35.3g)，及取代2,3-苯並呋喃(1.0g)而改用2,3-二氫呋喃(0.7g)以外，其他係與實施例1同樣地操作而取得聚醯亞胺前驅物之乳白色分散液(聚醯亞胺前驅物組成物)。 [0149] [實施例3] 〈聚醯亞胺前驅物組成物之調製〉 除了取代水(35.0g)而改用水(35.2g)，及取代2,3-苯並呋喃(1.0g)而改用3,4-二氫-2H-吡喃(0.8g)以外，其他係與實施例1同樣地操作而取得聚醯亞胺前驅物之乳白色分散液(聚醯亞胺前驅物組成物)。 [0150] [實施例4] 〈聚醯亞胺前驅物組成物之調製〉 除了取代2,3,3,4-聯苯四羧酸(2.9g)而改用3,3’,4,4’-二苯甲酮四羧酸(2.9g)以外，其他係與實施例1同樣地操作而取得聚醯亞胺前驅物之乳白色分散液(聚醯亞胺前驅物組成物)。 [0151] [實施例5] 〈聚醯亞胺前驅物組成物之調製〉 除了取代2,3,3,4-聯苯四羧酸(2.9g)而改用4,4’-氧二酞酸(2.9g)以外，其他係與實施例1同樣地操作而取得聚醯亞胺前驅物之乳白色分散液(聚醯亞胺前驅物組成物)。 [0152] [實施例6] 〈聚醯亞胺前驅物組成物之調製〉 除了取代異酞酸二醯肼(0.5g)而改用己二酸二醯肼(0.25g)以外，其他係與實施例1同樣地操作而取得聚醯亞胺前驅物之乳白色分散液(聚醯亞胺前驅物組成物)。 [0153] [比較例1] 〈聚醯亞胺前驅物組成物之調製〉 對具備攪拌機之可拆式燒瓶(100mL；筒型)添加2,3,3,4-聯苯四羧酸(2.9g)及水(40.7g)，在25℃中攪拌混合10分鐘後，添加2,3-苯並呋喃(1.0g)，並且在25℃中攪拌混合45分鐘，而取得四羧酸衍生物之水分散液。 對取得之水分散液添加苯乙烯丙烯醯基型聚胺(日本觸媒公司製，Polyment(商標)NK-200PM；不揮發殘分56質量%、胺價2.55mmol/g-solid；m=60)(13.5g)，在25℃中攪拌混合2小時，而取得聚醯亞胺前驅物之淡黃色透明溶液(聚醯亞胺前驅物組成物)。 [0154] [比較例2] 〈聚醯亞胺前驅物組成物之調製〉 除了取代水(40.7g)而改用水(41.0g)，及取代2,3-苯並呋喃(1.0g)而改用2,3-二氫呋喃(0.7g)以外，其他係與比較例1同樣地操作，而取得聚醯亞胺前驅物之乳白色分散液(聚醯亞胺前驅物組成物)。 [0155] [比較例3] 〈聚醯亞胺前驅物組成物之調製〉 除了取代水(40.7g)而改用水(40.9g)，取代2,3-苯並呋喃(1.0g)而改用3,4-二氫-2H-吡喃(0.8g)以外，其他係與比較例1同樣地操作而取得聚醯亞胺前驅物之乳白色分散液(聚醯亞胺前驅物組成物)。 [0156] [比較例4] 〈聚醯亞胺前驅物組成物之調製〉 對具備攪拌機之可拆式燒瓶(100mL；筒型)添加2,3,3,4-聯苯四羧酸(2.9g)及水(40.7g)，在25℃中攪拌混合10分鐘而取得混合液。 其次，對可拆式燒瓶內之混合液添加苯乙烯丙烯醯基型聚胺(日本觸媒公司製，Polyment(商標)NK-200PM；不揮發殘分56質量%、胺價2.55mmol/g-solid；m=60) (13.5g)，在25℃中攪拌混合2小時。 但，無法取得均勻之樹脂溶液或分散液，而變成樹脂成分沉澱之結果。 [0157] [塗佈性・儲藏穩定性] 〈試驗方法〉 使用E型黏度計(東機產業股份有限公司製，型號TV-22)測量聚醯亞胺前驅物組成物之剛調製後在22℃中之黏度。 其次，將聚醯亞胺前驅物組成物(30.0g)採取至玻璃瓶，隨及靜置在25℃之恆溫室內。測量剛調製後，以及從靜置日起算1日後、3日後及7日後，在22℃中之黏度。 塗佈性及儲藏穩定性之評價係根據以下之評價基準實施。 [0158] (塗佈性之評價基準) 22℃中之黏度： 0.1~1.5Pa・s・・・・・・容易流動，塗佈性良好 無法測量黏度・・・・・・難以流動，且塗佈性不良 [0159] (儲藏穩定性之評價基準) 從剛調製後之黏度所增加之黏度： 10%以內・・・・・・・・・儲藏穩定性為良好 超過10%・・・・・・・・・儲藏穩定性為不良 [0160] 〈測量結果〉 將剛調製後、1日後、3日後及7日後在22℃中之黏度展示於表1。尚且，表1中，「N.A.」表示無法測量黏度。 [0161][0162] 〈評價結果〉 實施例1~6之聚醯亞胺前驅物組成物及比較例1~3之聚醯亞胺前驅物組成物皆為低黏度且塗佈性，並且無時間經過所造成之黏度增加，且儲藏穩定性優異。 [0163] [耐溶劑性] 〈試驗方法〉 將剛調製後之聚醯亞胺前驅物組成物採取至玻璃瓶，隨及靜置於25℃之恆溫室內。使用剛調製後，以及從靜置日起算1日後、3日後及7日後之聚醯亞胺前驅物組成物，根據以下之操作順序製作附硬化膜之玻璃基材，並進行耐溶劑性試驗。 在玻璃基材之一側之表面上，將聚醯亞胺前驅物組成物以乾燥塗膜之厚度成為40μm之方式進行塗佈。塗佈後，使用加熱板以90℃進行30分鐘加熱處理後，使用恆溫乾燥爐，以250℃進行30分鐘加熱處理，而在玻璃基材之一側之表面上形成由聚醯亞胺樹脂所構成之硬化膜。 以包含NMP(N-甲基-2-吡咯啶酮)之布摩擦硬化膜之表面，基於以下之評價基準評價硬化膜之耐溶劑性。 [0164] (耐溶劑性之評價基準) 無變化・・・・・・・・・・・・・耐溶劑性為良好 硬化膜之表面產生膨潤或浸蝕・・・耐溶劑性為不良 [0165] 〈評價結果〉 在表2之「耐溶劑性」之欄展示耐溶劑性之評價結果。 「A」表示耐溶劑性為良好，「X」表示耐溶劑性不良。 使實施例1~6之聚醯亞胺前驅物組成物硬化而成之聚醯亞胺樹脂及使比較例1~3之聚醯亞胺前驅物組成物硬化而成之聚醯亞胺樹脂皆展現良好之耐溶劑性。 [0166] [耐水性] 〈試驗方法〉 將剛調製後之聚醯亞胺前驅物組成物採取至玻璃瓶，隨及靜置於25℃之恆溫室內。使用剛調製後，以及從靜置日起算1日後、3日後及7日後之聚醯亞胺前驅物組成物，根據以下之操作順序製作附硬化膜之玻璃基材，並進行耐水性試驗(熱水含浸試驗)。 在玻璃基材之一側之表面上，將聚醯亞胺前驅物組成物以乾燥塗膜之厚度成為40μm之方式進行塗佈。塗佈後，使用加熱板，以90℃進行30分鐘加熱處理後，使用恆溫乾燥爐，以250℃進行30分鐘加熱處理，在玻璃基材之一側之表面上形成由聚醯亞胺樹脂所構成之硬化膜。 將已形成硬化膜之玻璃基材浸漬於90℃之熱水並放置10分鐘後，以目視觀察硬化膜，基於以下之評價基準評價硬化膜之耐水性。 [0167] (耐水性之評價基準) 無變化・・・・・・・・・・・・・・耐水性為良好 硬化膜之表面產生白化或膨潤・・・・耐水性不良 [0168] 〈評價結果〉 在表2之「耐水性」之欄展示耐水性之評價結果。 「A」表示耐水性良好，「X」表示耐水性不良。 使實施例1~6之聚醯亞胺前驅物組成物硬化而成之聚醯亞胺樹脂及使比較例1~3之聚醯亞胺前驅物組成物硬化而成之聚醯亞胺樹脂皆展現良好之耐水性。 [0169] [剝離性] 〈試驗方法〉 將剛調製後之聚醯亞胺前驅物組成物採取至玻璃瓶，隨及靜置於25℃之恆溫室內。使用剛調製後，以及從静置日起算1日後、3日後及7日後之聚醯亞胺前驅物組成物，將厚度3mm之PTFE(聚四氟乙烯)板作為進行塗佈之基材，以乾燥塗膜之厚度成為40μm之方式進行塗佈。塗佈後，使用加熱板，以90℃進行30分鐘加熱處理後，根據以下之評價基準來評價使用恆溫乾燥爐在250℃下經過30分鐘加熱處理之聚醯亞胺硬化膜之從基材之剝離性。 [0170] (剝離性之評價基準) 能從基材地簡單剝離・・・剝離性良好 無法從基材剝離・・・・・剝離性不良 [0171] 〈評價結果〉 在表2之「剝離性」之欄展示耐水性之評價結果。 「A」表示剝離性良好，「X」表示剝離性不良。 使實施例1之聚醯亞胺前驅物組成物硬化而成之聚醯亞胺樹脂係能從基材簡單地剝離，而展現良好之剝離性。 但，使比較例1之聚醯亞胺前驅物組成物硬化而成之聚醯亞胺樹脂並無法從基材剝離，而剝離性不良。 [0172] 〈耐溶劑性、耐水性及剝離性之評價結果〉 在表2展示耐溶劑性、耐水性及剝離性之評價結果(A、X)。尚且，表2中，「N.A.」表示無法評價耐溶劑性、耐水性或剝離性。 [0173][0174][0175] [耐熱性] 〈試驗方法〉 熱重量測量裝置(DTG-60，島津製作所製)測量從玻璃基材剝離使實施例1~6之聚醯亞胺前驅物組成物硬化而成之聚醯亞胺樹脂而得取之硬化膜的5%重量減少溫度。 尚且，使比較例1~3之聚醯亞胺前驅物組成物硬化而成聚醯亞胺樹脂由於無法從玻璃基材剝離，故並未實施耐熱性之試驗。 [0176] 〈試驗結果〉 實施例1~6之硬化膜之5%重量減少溫度皆為300℃以上。 此即係教示已進行醯亞胺縮合反應，且可謂係具備聚醯亞胺樹脂相應之耐熱性之素材。 [0177] [總結] 如以上所示，實施例1~6之聚醯亞胺前驅物組成物之塗佈性及儲藏穩定性優異，且使該聚醯亞胺前驅物組成物硬化而成之聚醯亞胺樹脂(硬化物)之耐溶劑性及耐水性優異。 並且，使實施例1~6之聚醯亞胺前驅物組成物硬化而成之聚醯亞胺樹脂(硬化物)之剝離性亦優。 相對於此，比較例1~3與實施例1~6相同，聚醯亞胺前驅物組成物之塗佈性及儲藏穩定性優異，且使該聚醯亞胺前驅物組成物硬化而成之聚醯亞胺樹脂(硬化物)之耐溶劑性及耐水性亦優。 但，在與實施例1~6相比，比較例1~3中使聚醯亞胺前驅物組成物硬化而成之聚醯亞胺樹脂(硬化物)之剝離性較差。[0016] Hereinafter, the polyimide precursor composition of the present invention, a method for producing a polyimide resin, and a polyimide resin will be described in detail. Also, the range indicated by "~" in this specification means the two ends of the range described before and after "~" in this range. [Polyimide precursor composition] 醯 The polyimide precursor composition of the present invention contains a hemiacetal ester compound represented by the following formula (1), and has at least two first stages in one molecule. An amino-based polyamine compound, and an aqueous medium, and the polyamine compound includes a hydrazine compound. [0018][0019] In the above formula, n, R1
, R2
, R3
, R4
, R5
And X are each n and R in formula (1)1
, R2
, R3
, R4
, R5
And X have the same meaning. [0020] The hemiacetal ester compound represented by the above formula (1) is added to the intercarbon unsaturated bond of the cyclic unsaturated ether compound represented by the following formula (A) by the following formula (B) A compound formed by the carboxyl group of a tetracarboxylic acid. [0021][0022] In formula (1), n is 0 or 1, R1
, R2
, R3
, R4
And R5
Each is independently a hydrogen atom, a halogen atom, or a monovalent organic group, and may be combined with each other to form a cyclic structure, and X is a tetravalent organic group. [0023] Furthermore, in the polyfluorene imide precursor composition of the present invention, the carboxyl group bonded to X in formula (1) can also be ionized to become a carboxylate anion. In this case, in the polyimide precursor composition of the present invention, the carboxylate anion portion (-COO) of the hemiacetal ester compound represented by the above formula (1)-
), With the ammonium cation portion (-NH) of a polyamine compound having at least 2 primary amine groups in 1 molecule3 +
) May form a salt structure as shown in the following formula in pairs. [0024]N, R in formula (A)1
, R2
, R3
, R4
And R5
, And X in formula (B) is respectively the same as n and R in formula (1).1
, R2
, R3
, R4
, R5
And X have the same meaning. [0026] A carboxyl group of a tetracarboxylic acid represented by the above formula (B) is added by an inter-carbon unsaturated bond of the cyclic unsaturated ether compound represented by the above formula (A) to form a half represented by the following formula Acetal ester bond. [0027]R in the above formula1
Is the same as R in the above formula (1)1
The same meaning. [0029] The hemiacetal ester bond formed by this has resistance to hydrolysis, and does not easily cause deprotection of the carboxyl group caused by detachment of the protective group of the carboxyl group. Therefore, the hemiacetal ester compound represented by the formula (1) has high stability in an aqueous medium. As a result, the polyimide precursor composition of the present invention has excellent storage stability. [0030] In addition, the hemiacetal ester bond thus formed is rapidly decomposed by heating to 170 ° C or higher, and the cyclic unsaturated ether compound represented by the above formula (A) is released, so the temperature is higher than 200 ° C. The carboxyl group is protected until the imidization treatment by heating. In addition, since the cyclic unsaturated ether compound represented by the above formula (A) is gasified during heating, the residual amount of the cyclic unsaturated ether compound represented by the above formula (A) in the hardened material is extremely small, and Does not impair the solvent resistance and water resistance of the obtained polyimide resin. In addition, when a hydrazine compound is used in the polyamine portion constituting the polyfluorene imide resin, the interval between the fluorene imino groups in the molecule is close, and the effect of improving the hardness of the material can be obtained. [0031] Thus, the polyimide precursor composition of the present invention is protected in a stable state during storage, and hardened into a pure polyimide resin after hardening. In addition, since the strength of the cured film after hardening is improved, a material with rich peelability can be obtained. [0031] <Semiacetal compound represented by formula (1)>〉 The polyfluorene imide precursor composition of the present invention may contain a single type of hemiacetal compound represented by formula (1), or it may be Contains 2 or more types of combinations. 003 [0033] "Meaning of each sign" (n) n is 0 or 1. [0034] (R1
, R2
, R3
, R4
And R5
) R1
, R2
, R3
, R4
And R5
Each is independently a hydrogen atom, a halogen atom, or a monovalent organic group, and may be bonded to each other to form a cyclic structure. [0035] ((Halogen atom)) The halogen atom is not particularly limited, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferred. [0036] ((monovalent organic group)) The monovalent organic group is not particularly limited, but is preferably a monovalent hydrocarbon group. Examples of the monovalent hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, and an aryl group. An alkyl group is preferred, and an alkyl group having 1 to 3 carbon atoms ( C1-3
Alkyl), more preferably methyl. Here, as C1-3
Examples of the alkyl group include methyl, ethyl, propyl, and isopropyl (propane-2-yl). [0037] The hydrogen atom of the monovalent hydrocarbon group may be substituted with a halogen atom or a hydroxyl group. Here, the halogen atom is not particularly limited, but a fluorine atom is preferred. [0038] The monovalent organic group preferably does not include a functional group having reactivity with an amine group or a carboxyl group. Here, examples of the group having reactivity with an amine group include, but are not limited to, a carboxyl group, a carboxylic acid anhydride group, a carbonyl group, an aldehyde group, and a halogenated carbonyl group. Examples of the functional group having reactivity with a carboxyl group include, but are not limited to, an amine group, a hydroxyl group, a carboxyl group, and a vinyloxy group. [0039] ((cyclic structure)) The cyclic structure is not particularly limited, and examples thereof include an aromatic hydrocarbon ring which may have a substituent or an alicyclic hydrocarbon ring which may have a substituent. For example, when n = 0, R2
With R4
Or R4
With R5
They may also be combined with each other to form an aromatic carbon six-membered ring which may have a substituent. [0040] (X) X is a tetravalent organic group. ((Tetravalent organic group)) As the tetravalent organic group, for example, compounds having a chain hydrocarbon in a basic skeleton such as ethylene and propane, and cyclohexane having a ring in a basic skeleton Compounds of formula hydrocarbons, compounds having aromatic hydrocarbons in the basic skeleton such as benzene and naphthalene, compounds having benzophenone skeleton such as benzophenone, compounds having diphenyl ether skeleton such as diphenyl ether, A compound obtained by removing any four hydrogen atoms from a compound having a diphenylfluorene skeleton such as diphenylfluorene, or a compound having a biphenyl skeleton such as biphenyl. However, it is not limited by these. [0042] It is preferable that the above-mentioned tetravalent organic group does not include a functional group having reactivity with an amine group. Here, examples of the group having reactivity with an amine group include a carboxyl group, a carboxylic acid anhydride group, a carbonyl group, an aldehyde group, and a halogenocarbonyl group, but are not limited thereto. [0043] "Specific Examples of Hemiacetal Ester Compounds Represented by Formula (1)" Specific examples of hemiacetal ester compounds represented by the formula (1) will be described below. However, the hemiacetal ester compound represented by formula (1) is not limited to the specific examples described below. (2,3-dihydrofuran derivative) A specific example of the hemiacetal ester compound represented by the formula (1) is a 2,3-dihydrofuran derivative represented by the following formula (1-1) Thing. Should be in the case of n = 0 in equation (1). [0045]In formula (1-1), R1
, R2
, R4
, R5
And X are each corresponding to R in formula (1)1
, R2
, R4
, R5
And X have the same meaning. Is preferably R in the formula (1-1)1
, R2
, R4
And R5
They are all hydrogen atoms. (3,4-dihydro-2H-pyran derivative) Another specific example of the hemiacetal ester compound represented by the formula (1) is 3,4 represented by the following formula (1-2) -A dihydro-2H-pyran derivative. Should be in the case of n = 1 in equation (1). [0048][0049] In the formula (1-2), R1
, R2
, R4
, R5
And X are each corresponding to R in formula (1)1
, R2
, R4
, R5
And X have the same meaning. Is preferably R in the formula (1-2)1
, R2
, R4
And R5
They are all hydrogen atoms. (1-Benzofuran derivative) Still another specific example of the hemiacetal ester compound represented by formula (1) is a 1-benzofuran derivative represented by the following formula (1-3). Should be in Equation (1), n = 0, and R4
With R5
In the case of combining with each other to form an aromatic carbon six-membered ring which may have a substituent. [0051]In formula (1-3), R1
, R2
, R4
, R5
And X are each corresponding to R in formula (1)1
, R2
, R4
, R5
And X have the same meaning. Again, R6
, R7
, R8
And R9
Each is independently a hydrogen atom, a halogen atom, or a monovalent organic group, and may be bonded to each other to form a cyclic structure. Here, the halogen atom, monovalent organic group, and cyclic structure are as described for R1
, R2
, R4
And R5
As described in the description. Is preferably R in the formula (1-3)1
, R2
, R4
, R5
, R6
, R7
, R8
And R9
They are all hydrogen atoms. [0053] <Polyamine compound having at least two primary amine groups in one molecule> (1) Polyamine compound having at least two primary amine groups in one molecule (hereinafter, also referred to simply as "polyamine In the case of the "base compound", the hydrazine compound and polyamine compounds other than the hydrazine compound are included. The polyamine compound can be used in combination of one or more polyamine compounds selected from the group consisting of polyamine compounds other than the hydrazine compound and one or more types of hydrazine compounds selected from the group consisting of the hydrazine compound. . [0054] The proportion of the hydrazine compound in the polyamine compound is not particularly limited, and is preferably 3 to 50% by mass, more preferably 3 to 40% by mass, more preferably 4 to 30% by mass, and more preferably 4 to 10% by mass. When the ratio of the hydrazine compound in the polyamine-based compound contained in the polyimide precursor composition of the present invention is within this range, the water-dispersible property is not impaired and the polyimide precursor of the present invention is made. The hardness of the polyimide resin hardened by the composition is further improved. [0055] "Polyamine compound other than hydrazine compound" As a polyamine compound other than the hydrazine compound, there can be mentioned the following formula (2). [0056][0057] In the formula (2), m is an integer of 2 or more, and Y is an m-valent organic group or an m-valent organic silicon group including a siloxane bond. In addition, in the formula (2), the first amine group is directly bonded to a carbon atom. In addition, in an aqueous medium, the amine group (-NH of the polyamine compound represented by formula (2)2
) Can also become ammonium cation (-NH3 +
). The upper limit m is not particularly limited, but is preferably 2000, more preferably 600. [0058] Polyamine compounds other than hydrazine compounds can be used alone or in combination of two or more. [0059] (Organic Polyamine) In the present specification, among polyamine compounds other than hydrazine compounds, polyamine compounds in which Y is an m-valent organic group are referred to as organic polyamines. [0060] Examples of the m-valent organic group include compounds having a chain hydrocarbon in a basic skeleton such as ethylene and propane, compounds having a cyclic hydrocarbon in a basic skeleton such as cyclohexane, benzene, naphthalene, and the like. Compounds having aromatic hydrocarbons in the basic skeleton, compounds having a benzophenone skeleton such as benzophenone, compounds having a diphenyl ether skeleton such as diphenyl ether, and compounds having diphenyl ether such as diphenylphosphonium A compound having a basic fluorene skeleton, or a compound having a biphenyl skeleton such as biphenyl, and the like obtained by removing arbitrary m hydrogen atoms. However, it is not limited to them. [0061] The m-valent organic group preferably does not include a group having reactivity with a carboxyl group. Examples of the group having reactivity with a carboxyl group include, but are not limited to, an amine group, a hydroxyl group, a carboxyl group, and a vinyloxy group. [0062] Specific examples of the organic polyamine include p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, and 3,3'-diaminodiphenyl. Ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenylsulfide, 3,4'-diamine Diphenyl sulfide, 4,4'-diaminodiphenylsulfide, 3,3'-diaminodiphenylphosphonium, 3,4'-diaminodiphenylphosphonium, 4,4 ' -Diaminodiphenylhydrazone, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3, 3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2-bis (3-aminophenyl) Propane, 2,2-bis (4-aminophenyl) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 2,2-bis (3-amino Phenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2- (3-aminophenyl) -2- (4-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 1,1-bis (3-aminophenyl) ) -1-phenylethane, 1,1-bis (4-aminophenyl) -1-phenylethane, 1- (3-aminophenyl) -1- (4-aminophenyl) ) -1-phenylethane, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3-amino Phenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminobenzylfluorenyl) benzene, 1,3-bis (4-aminobenzylhydrazone) Phenyl) benzene, 1,4-bis (3-aminobenzylfluorenyl) benzene, 1,4-bis (4-aminobenzylfluorenyl) benzene, 1,3-bis (3-amino-α, α -Dimethylbenzyl) benzene, 1,3-bis (4-amino-α, α-dimethylbenzyl) benzene, 1,4-bis (3-amino-α, α-dimethyl Benzyl) benzene, 1,4-bis (4-amino-α, α-dimethylbenzyl) benzene, 1,3-bis (3-amino-α, α-fluorenetrifluoromethylbenzyl ) Benzene, 1,3-bis (4-amino-α, α-fluorenetrifluoromethylbenzyl) benzene, 1,4-bis (3-amino-α, α-fluorenetrifluoromethylbenzyl) ) Benzene, 1,4-bis (4-amino-α, α-fluorenetrifluoromethylbenzyl) benzene, 2,6-bis (3-aminophenoxy) benzonitrile, 2,6-bis (3-aminophenoxy) pyridine, 4,4'-bis (3-aminophenoxy) biphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, bis [4 -(3-aminophenoxy) phenyl] one, bis [4- (4-aminophenoxy) phenyl] one, bis [4- (3-aminophenoxy) phenyl] sulfur Ether, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] fluorene, Bis [4- (4-aminophenoxy) phenyl] fluorene, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) benzene Group] ether, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2, 2-bis [3- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) (Phenyl) phenyl] -1,1,1,3,3,3-hexafluoropropane, 1,3-bis [4- (3-aminophenoxy) benzylfluorenyl] benzene, 1,3-bis [4- (4-aminophenoxy) benzylfluorenyl] benzene, 1,4-bis [4- (3-aminophenoxy) benzylfluorenyl] benzene, 1,4-bis [4- ( 4-aminophenoxy) benzylfluorenyl] benzene, 1,3-bis [4- (3-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [ 4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (3-aminophenoxy) -α, α-dimethylbenzyl Phenyl] benzene, 1,4-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, 4,4'-bis [4- (4-aminophenoxy) (Benzyl) benzyl] diphenyl ether, 4,4'-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] benzophenone, 4,4'- Bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] diphenylphosphonium, 4,4'-bis [4- (4-aminophenoxy) phenoxy ] Diphenylphosphonium, 3, 3'-diamino-4,4'-diphenoxybenzophenone, 3,3'-diamino-4,4'-diphenoxybenzophenone, 3,3'- Diamino-4-phenoxybenzophenone, 3,3'-diamino-4-biphenoxybenzophenone, 6,6'-bis (3-aminophenoxy)- 3,3,3 ', 3'-tetramethyl-1,1'-spirodihydroindane, 6,6'-bis (4-aminophenoxy) -3,3,3', 3'- Tetramethyl-1,1'-spirodihydroindane, 1,3-bis (3-aminopropyl) tetramethyldisilazane, 1,3-bis (4-aminobutyl) tetramethyl Didimethylsiloxane, α, ω-bis (3-aminopropyl) polydimethylsiloxane, α, ω-bis (3-aminobutyl) polydimethylsiloxane, bis ( Aminomethyl) ether, bis (2-aminoethyl) ether, bis (3-aminopropyl) ether, bis [2- (aminomethoxy) ethyl] ether, bis [2- ( 2-aminoethoxy) ethyl] ether, bis [2- (3-aminopropyloxy) ethyl] ether, 1,2-bis (aminomethoxy) ethane, 1,2- Bis (2-aminoethoxy) ethane, 1,2-bis [2- (aminomethoxy) ethoxy] ethane, 1,2-bis [2- (2-aminoethoxy) ) Ethoxy] ethane, ethylene glycol bis (3-aminopropyl) ether, diethylene glycol bis (3-aminopropyl) ether, triethylene glycol bis (3-aminopropyl) Ether, ethylenediamine , 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane Alkane, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,2-bis (2-aminoethyl) cyclohexane Alkanes, 1,3-bis (2-aminoethyl) cyclohexane, 1,4-bis (2-aminoethyl) cyclohexane, bis (4-aminocyclohexyl) methane, 2,6 -Bis (aminomethyl) bicyclo [2.2.1] heptane, and 2,5-bis (aminomethyl) bicyclo [2.2.1] heptane, etc. [0063] As the organic polyamine, a part or all of the hydrogen atoms on the aromatic ring of the organic polyamine may be selected from the group consisting of a fluorine atom, a methyl group, a methoxy group, a trifluoromethyl group, and a trifluoromethoxy group. Organic polyamines substituted by groups of substituents. [0064] In addition, as the organic polyamine, in addition to the organic polyamine described above, one or more molecules having two or more primary amine groups (-NH2
) Polymers (except those that contain a primary amine group and are reactive with a carboxyl group). Examples of such an organic polyamine include, for example, polystyrene, polyacrylic acid, polyurethane, polyamidine, or polyimide in the main chain or side chain via two or more primary amine groups. Modified by. More specifically, by using the reactivity of the carboxyl group of the polymer side chain and ethyleneimine, and grafting polyethyleneimine to the side of the acrylic copolymer, an acrylic polymer containing a primary amine group is used. Excessive amount of diamine or triamine is a polyamine resin obtained by elongating tetracarboxylic dianhydride, and excessive amount of diamine or triamine is used to extend a urethane prepolymer. Ester urea resin, or denatured epoxy resin made by stretching epoxy resin with excess amount of diamine or triamine. [0065] Further, the polymer having two or more primary amine groups in the above molecule does not include a group reactive with a carboxyl group other than the primary amine group. Here, examples of the group having reactivity with a carboxyl group include a hydroxy group, a carboxyl group, and a vinyloxy group, but are not limited thereto. [0066] The organic polyamine may be used in accordance with the purpose, and a part or all of the hydrogen atoms introduced into the aromatic ring of the organic polyamine as a substituent may be used when the crosslinking reaction is performed after the polyfluorene is formed. Any one or more of ethynyl, benzocyclobuten-1-yl, vinyl, allyl, cyano, and isopropenyl at the crosslinking point. [0067] The organic polyamine system can be appropriately selected according to the physical properties of the object. As an organic polyamine, when a rigid diamine such as p-phenylene diamine is used, the finally obtained polyimide can have a low expansion ratio. As the rigid organic diamine, for example, a diamine (aromatic diamine) in which two amine groups are bonded to the same aromatic ring is mentioned. Specific examples of such an aromatic diamine include p-phenylene diamine, m-phenylene diamine, 1,4-diaminonaphthalene, 1,5-diaminonaphthalene, 2 , 6-diaminonaphthalene, 2,7-diaminonaphthalene, and 1,4-diaminoanthracene. A dendrimer of polyamine may also be used. [0068] Further, as the organic polyamine, for example, two or more aromatic rings are bonded by a single bond, and two or more amine groups are directly bonded or substituted as respective aromatic rings. An organic polyamine bonded to a part of a group. Specific examples of such an organic polyamine include benzidine and toluidine. [0069] Further, as the organic polyamine, an organic polyamine having a substituent on a benzene ring can also be used. These substituents are monovalent organic groups, but these may be combined with each other. Specific examples of such an organic polyamine include 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-fluorenetrifluoromethyl-4,4'- Diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, and 3,3 '-Dimethyl-4,4'-diaminobiphenyl. [0070] As the organic polyamine other than the above, for example, an aminoethylated acrylic polymer or the like can be used. A preferred aspect of the aminoethylated acrylic polymer is, for example, an acrylic polymer containing a first-order amino group formed by branching polyethyleneimine into a side chain. The main chain of the amino ethylated acrylic polymer is a (meth) acrylic polymer formed from a monomer including (meth) acrylate and (meth) acrylic acid. As one of the preferable aspects, an aminoethylated acrylic polymer system is exemplified by those having a plurality of primary amine groups. The weight average molecular weight of the aminoethylated acrylic polymer is preferably from 5,000 to 100,000. [0071] The above aminoethylated acrylic polymer may also form a hydrohalide, such as a salt of a hydrochloride, a hydrobromide, or the like. In addition, as the amino ethylated acrylic polymer, water-soluble ones can be mentioned as one of the preferable aspects. As commercially available products of the amino ethylated acrylic polymer exhibiting water solubility, for example, Polymer (trademark) NK-100PM, Polymer (trademark) NK-200PM (both manufactured by Nippon Catalytic Corporation) are mentioned. (Siloxanes-based polyamine) In the present specification, among polyamine compounds other than hydrazine compounds, polyamine compounds in which Y is an m-valent organic silicon group containing a siloxane bond are referred to as silicon. Oxane-based polyamines. [0073] Examples of the m-valent organosilicon group containing a siloxane bond include those in which m of a monovalent hydrocarbon group of the organosilicon compound represented by the following formula is substituted with a single bond. [0074][0075] In the above formula, k is an integer of 1 or more, and R11
, R12
, R13
, R14
, Rtwenty one
And Rtwenty two
They are each independently a monovalent hydrocarbon group. When k ≧ 2, plural Rtwenty one
Can be the same or different from each other, plural Rtwenty two
They can be the same or different from each other. [0076] Specific examples of the siloxane-based polyamine include 1,3-bis (3-aminopropyl) tetramethyldisilazane. However, it is not limited to this. [0077] When a siloxane-based polyamine is used, the elasticity of the polyimide resin obtained by curing the polyimide precursor composition of the present invention can be reduced, and the glass transition temperature can be reduced. [0078] (Organic polyamine that can be used in combination with a silicone polyamine) As an organic polyamine that can be used in combination with the above-mentioned silicone polyamine, an aromatic polyamine is preferred from the viewpoint of heat resistance, and aromatic Group diamines are preferred. An aromatic polyamine can also be used 1 type or more. In addition, depending on the physical properties of the purpose, organic polyamines other than aromatic diamines may be used in combination. As such an organic polyamine, an aliphatic polyamine is preferable, and an aliphatic diamine is preferable. One or more types of aliphatic diamines may be used. When using aromatic polyamines and other organic polyamines in combination, the amount of organic polyamines other than aromatic polyamines should not exceed the total amount of organic polyamines (does not include siloxane-based polyamines, only organic polyamines) A range of 60 mol% is preferred, and a range of no more than 40 mol% is more preferred. [0079] "Hydrazine compound" As a hydrazine compound, two hydrazine groups having one hydrazine group and one or more primary amine groups in one molecule, and two hydrazine groups in one molecule A hydrazine compound and a polyhydrazine compound having three or more hydrazine groups in one molecule are suitably selected and used. However, the hydrazino group is a group represented by the following formula. Also, in an aqueous medium, the imino group (> NH) of the hydrazino group can become an imine cation (> NH).2 +
), Amine moiety (-NH2
) Can become ammonium cation (-NH3 +
). [0080]The hydrazine compound may be used alone or in combination of two or more. As the hydrazine compound, it is preferable to use one or more kinds selected from the group consisting of a dihydrazide compound and a polyhydrazine compound, and it is more preferable to use one or more kinds selected from the group consisting of a dihydrazide compound. [0082] (Dihydrazine compound) As the dihydrazine compound, for example, a hydrazine compound represented by the following formula (3) is mentioned. [0083][0084] In the formula (3), Z represents a single bond, a divalent aliphatic group, or a divalent aromatic group. [0085] Examples of the dihydrazine compound in which Z is a single bond include dihydrazine oxalate. Examples of the dihydrazide compound in which Z is a divalent aliphatic group include dihydrazine malonate, dihydrazine succinate, dihydrazine glutarate, dihydrazine adipic acid, Dihydrazine pimelate, dihydrazine suberate, dihydrazide azelarate, dihydrazine sebacate, dihydrazine dodecanedioate, dihydrazide maleate, dihydrazide fumarate Dihydrazide diglycolate, dihydrazide tartrate, dihydrazide malate, and dihydrazide iconate. In addition, for example, as the dihydrazine compound in which Z is a divalent aromatic group, dihydrazide phthalate, dihydrazide isophthalate, dihydrazide terephthalate, and 2,6-naphthyldimethylene Acid dihydrazine, 4,4-bisphenyldihydrazine, 1,4-naphthoic acid dihydrazine, and 2,6-pyridinediacid dihydrazide. [0086] As the dihydrazine compound, one or more types selected from the group consisting of dihydrazine adipate, dihydrazine sebacate, dihydrazine phthalate, and dihydrazide isophthalate are preferably used. It is preferable to use one or more types selected from the group consisting of dihydrazine phthalate and dihydrazide isophthalate, and it is more preferable to use dihydrazide isophthalate. [0087] (Polyhydrazine compound) As the polyhydrazine compound, for example, a material obtained by modifying a resinized material such as polyacrylic acid with fluorene and polyfunctionalizing it can be mentioned. [0088] <Aqueous Media> The polyimide precursor composition of the present invention contains an aqueous medium. Water-based media is media with water as the main component. As the water system, ion-exchanged water, distilled water, deionized distilled water, RO (Reverse Osmosis) water, and the like can be used. Here, using water as a main component means that it contains 60% by mass or more of water, preferably 75% by mass or more, and more preferably 90% by mass or more. The environmental impact can be reduced by using water-based media. [0089] The aqueous medium may contain a known alcohol or ether for the purpose of imparting wettability and anticorrosive effect to a substrate, and having a small environmental load and not adversely affecting water volatility and drying properties. Examples include methanol, ethanol, n-propanol, 2-propanol (isopropyl alcohol), n-butanol, isobutanol, t-butanol, butyl cellosolve, propylene glycol monomethyl ether, And 1- (2-hydroxyethyl) -2-pyrrolidone.醇 These alcohols or ethers can be used singly or in combination of two or more kinds. [0090] When the alcohol is added to the aqueous medium, the ratio of the alcohol in the aqueous medium is preferably 1 mass% or more and 40 mass% or less, and more preferably 5 mass% or more and 25 mass% or less. When the ratio of the alcohol is 1% by mass or more, the effect of improving the wettability of the coating composition on the substrate is exhibited, and the repellency of the coating composition on the substrate is suppressed. In addition, when the ratio of the alcohol is 40% by mass or less, the polyimide precursor composition does not precipitate crystals, and it becomes easy to arrange the coating composition in a film form on the substrate. When the ratio of the alcohol is less than 1% by mass, the improvement effect obtained by adding the alcohol may be insufficient. When the ratio of the alcohol exceeds 40% by mass, the polyimide precursor composition may precipitate and crystallize, and it may become difficult to arrange the polyimide precursor composition on the substrate into a film form. concern. [0091] <Optional Component> The polyimide precursor composition of the present invention may further contain any of the components described below. [0092] "Volatile Amine" In order to improve the stability of the polyfluorene imide precursor composition of the present invention, a volatile amine may be added. The kind of volatile amines that can be contained in the polyimide precursor composition of the present invention is not particularly limited, and examples thereof include ammonia, trimethylamine, triethylamine, tributylamine, and N-methyl Morpholine. These volatile amines may be used singly or in combination of two or more kinds. The content of the volatile amine that can be contained in the polyfluorene imide precursor composition of the present invention is not particularly limited, so as not to exceed the carboxyl group not used in the addition reaction of the cyclic unsaturated ether compound and the tetracarboxylic acid. Ear count is preferred. [0093] "Polymer Component" 醯 The polyimide precursor composition of the present invention may further contain a polymer component other than polyimide, as long as it does not impair its characteristics. When a polymer component is added to the polyimide precursor composition of the present invention, for example, the components can be compounded by a suitable mixing method such as roll mixing, Banbury mixing, screw mixing, and mixing. modulation. [0094] "Other Additives" The polyimide precursor composition of the present invention may further contain a material selected from the group consisting of reinforcing materials, fillers, anti-aging agents, antioxidants, light stabilizers, anti-scorching agents, and other additives. One or more types of additives in a group consisting of delayed retarders, plasticizers, processing aids, slip agents, adhesives, lubricants, flame retardants, antifungal agents, antistatic agents, colorants and surfactants. [0095] "Organic Solvent" In the polyimide precursor composition of the present invention, in addition to organic solvents such as alcohols and ethers included in aqueous media, organic solvents included in volatile amines, and traces of unavoidable mixing The organic solvent is preferably not substantially containing an organic solvent. Here, "substantially free of an organic solvent" means that the content of the organic solvent in the polyimide precursor composition of the present invention is 0.1% by mass or less based on the entire polyimide precursor composition. Examples of the organic solvent which is preferably substantially not contained include, for example, N-methyl-2-pyrrolidone, 1- (2-hydroxyethyl) -2-pyrrolidone, dimethylarsin, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylcaprolactam, acetone, γ-butyrolactone, methyl ethyl ketone and methyl isobutyl ketone, etc. High environmental load organic solvents. [0096] <Viscosity of Polyfluorene Imide Precursor Composition> The viscosity of the polyfluorene imide precursor composition of the present invention is not particularly limited, and is preferably 0.1 to 300 Pa · s, more preferably 0.2 to 50 Pa · s. , More preferably 0.3 to 10 Pa · s, and most preferably 0.1 to 10 Pa · s. When the viscosity of the polyimide precursor composition of the present invention is within this range, the coating property of the polyimide precursor composition of the present invention will be more favorable. Moreover, the viscosity of the polyimide precursor composition of the present invention is a viscosity at 22 ° C. measured using an E-type viscometer (TV-22, manufactured by Toki Sangyo Co., Ltd.). [Method for preparing polyimide precursor composition] 方法 The method for preparing polyimide precursor composition of the present invention is not particularly limited, and for example, the polymer of the present invention can be implemented as described later. The first step and the second step of the method for producing an imine resin are prepared. [0098] [Manufacturing method of polyimide resin] 方法 The manufacturing method of polyimide resin of the present invention includes the following first step, second step, and third step. In addition, instead of using the polyimide precursor composition prepared by performing the first step and the second step, the polyimide resin of the polyimide precursor composition of the present invention is used instead. The manufacturing method is also a manufacturing method of the polyfluorene imide resin included in the present invention. [First Step] (1) The first step is a step of mixing a cyclic unsaturated ether compound represented by the following formula (A) (hereinafter sometimes referred to as a "cyclic unsaturated ether compound") and The tetracarboxylic acid shown in (B) (hereinafter also referred to as "tetracarboxylic acid") and the aqueous medium are stirred to synthesize a cyclic unsaturated ether compound represented by the following formula (A) A step of an adduct of a tetracarboxylic acid represented by the following formula (B). [0101]N, R in formula (A)1
, R2
, R3
, R4
And R5
, And X in formula (B) is respectively different from n and R in formula (1)1
, R2
, R3
, R4
, R5
And X have the same meaning. [0103] In the first step, an adduct of a cyclic unsaturated ether compound and a tetracarboxylic acid [semiacetal compound represented by formula (1)] was synthesized in an aqueous medium. Therefore, in the first step, an aqueous composition in which the hemiacetal compound represented by the formula (1) is dispersed in an aqueous medium is obtained. This aqueous composition may contain an unreacted cyclic unsaturated ether compound and a tetracarboxylic acid in addition to the hemiacetal ester compound and the aqueous medium represented by the formula (1), and may also contain A hemiacetal ester compound obtained by adding 2 to 4 molecules of a cyclic unsaturated ether compound to one molecule of a carboxylic acid may also contain the catalyst when a catalyst described later is used. [0104] "Cyclic unsaturated ether compound represented by formula (A)" (1) In the first step, the cyclic unsaturated ether compound represented by formula (A) may be used alone or in combination of two or more kinds. use. [0105] Hereinafter, specific examples of the cyclic unsaturated ether compound represented by the formula (A) will be described. It should be noted that the cyclic unsaturated ether compound represented by the formula (A) is not limited to the specific examples described below. (2,3-Dihydrofuran or a derivative thereof) A preferable aspect of the cyclic unsaturated ether compound represented by the formula (A) is 2,3 represented by the following formula (A-1) -Dihydrofuran or a derivative thereof. [0107][0108] The above formula (A-1) is a case where n = 0 in the above formula (A). RR in the above formula (A-1)1
, R2
, R4
And R5
R and R in formula (A)1
, R2
, R4
And R5
The same meaning. As the compound represented by the above formula (A-1), 2,3-dihydrofuran is preferred. (3,4-dihydro-2H-pyran) Another preferable aspect of the cyclic unsaturated ether compound represented by the formula (A) is 3, which is represented by the following formula (A-2), 4-Dihydro-2H-pyran or a derivative thereof. [0110][0111] The above formula (A-2) is a case where n = 1 in the above formula (A). RR in the above formula (A-2)1
, R2
, R3
, R4
And R5
R and R in formula (A)1
, R2
, R3
, R4
And R5
The same meaning. As the compound represented by the above formula (A-2), 3,4-dihydro-2H-pyran is preferred. (1-benzofuran or a derivative thereof) Another preferable aspect of the cyclic unsaturated ether compound represented by the formula (A) is 1-benzene represented by the following formula (A-3) Benzofuran or a derivative thereof. [0113][0114] The above formula (A-3) should be equivalent to n = 0 and R in the above formula (A).4
With R5
May form a substituent (R6
~ R9
) Of the aromatic carbon six-membered ring. RR in the above formula (A-3)1
, R2
, R4
And R5
R and R in formula (A)1
, R2
, R4
And R5
The same meaning. RR in the above formula (A-3)6
, R7
, R8
And R9
Is the same as R in the above formula (1-3)6
, R7
, R8
And R9
The same meaning. As the compound represented by the above formula (A-3), fluorene is preferably 1-benzofuran. [0115] "Tetracarboxylic acid represented by formula (B)" (1) In the first step, the tetracarboxylic acid represented by formula (B) may be used singly or in combination of two or more kinds. [0116] Specific examples of the tetracarboxylic acid represented by the formula (B) are given below. The tetracarboxylic acid represented by the formula (B) is not limited to the specific examples exemplified below. Specific examples of the tetracarboxylic acid represented by the formula (B) include 1,2,4,5-benzenetetracarboxylic acid (mellitic acid), 1,2,3,4-benzene Tetracarboxylic acid (mellophanic acid), 2,3,6,7-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid , 3,4,9,10-fluorenetetracarboxylic acid, 2,3,6,7-anthracene tetracarboxylic acid, 1,2,7,8-phenanthrenetetracarboxylic acid, 3,3 ', 4,4'- Benzophenone tetracarboxylic acid, 2,2 ', 3,3'-benzophenone tetracarboxylic acid, bisfluorene 4- [4- (1,2-dicarboxy) phenoxy] phenylfluorenone, Bisfluorene 4- [3- (1,2-dicarboxy) phenoxy] phenylfluorenone, bisfluorene 4- [4- (1,2-dicarboxy) phenoxy] phenylfluorenone, bisfluorene 4- [3- (1,2-dicarboxy) phenoxy] phenylfluorenone, 3,3 ', 4,4'-biphenyltetracarboxylic acid, 2,2', 3,3'-biphenyl Tetracarboxylic acid, 2,2 ', 6,6'-biphenyltetracarboxylic acid, bis (3,4-dicarboxyphenyl) ether, 4,4'-bis [4- (1,2-dicarboxy) Phenoxy] biphenyl, 4,4'-bis [3- (1,2-dicarboxy) phenoxy] biphenyl, bis (2,3-dicarboxyphenyl) methane, bis (3,4- Dicarboxyphenyl) methane, 1,1-bis (2,3-dicarboxyphenyl) ethane, 2,2-bis (3,4-dicarboxyphenyl) propane, 2,2-bis (2, 3-dicarboxyphenyl) propane, 2,2-bisfluorene 4- [4- (1, 2-dicarboxy) phenoxy] phenylphosphonium propane, 2,2-bisfluorene 4- [3- (1,2-dicarboxy) phenoxy] phenylphosphonium propane, 2,2-bis (3, 4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (2,3-dicarboxyphenyl) -1,1,1,3,3, 3-hexafluoropropane, 2,2-bisfluorene 4- [4- (1,2-dicarboxy) phenoxy] phenylfluorene-1,1,1,3,3,3-hexafluoropropane, 2 , 2-bisfluorene 4- [3- (1,2-dicarboxy) phenoxy] phenylfluorene-1,1,1,3,3,3-hexafluoropropane, 1,3-bis [(3 , 4-dicarboxy) benzylfluorenyl] benzene, 1,4-bis [(3,4-dicarboxy) benzylfluorenyl] benzene, bis (3,4-dicarboxyphenyl) fluorene, bisfluorene 4- [ 4- (1,2-dicarboxy) phenoxy] phenylfluorene, bisfluorene 4- [3- (1,2-dicarboxy) phenoxy] phenylfluorene, bisfluorene 4- [4- (1,2-dicarboxy) phenoxy] phenylphosphonium sulfide, and bisfluorene 4- [3- (1,2-dicarboxy) phenoxy] phenylphosphonium sulfide and the like. [0118] In addition, as the tetracarboxylic acid represented by the formula (B), the heat resistance and linear thermal expansion coefficient of the polyimide resin obtained by drying and curing the polyimide precursor composition of the present invention are obtained. From the viewpoint, aromatic tetracarboxylic acid is preferred, and 1,2,4,5-benzenetetracarboxylic acid (mellitic acid), 1,2,3,4-benzenetetracarboxylic acid (mellitic acid), 2 , 3,6,7-naphthalenetetracarboxylic acid, 3,3 ', 4,4'-benzophenonetetracarboxylic acid, 3,3', 4,4'-biphenyltetracarboxylic acid, 2,3, 3 ', 4'-biphenyltetracarboxylic acid, 2,3,2', 3'-biphenyltetracarboxylic acid, 2,2 ', 6,6'-biphenyltetracarboxylic acid, bis (3,4- Dicarboxyphenyl) ether, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane, or bis (3,4-dicarboxyphenyl) ) Ether is preferred. In addition, as the tetracarboxylic acid represented by the formula (B), from the viewpoint of the stability of the hemiacetal ester bond, 3,3 ', 4,4'-biphenyltetracarboxylic acid, 2,3, 3 ', 4'-biphenyltetracarboxylic acid, 2,3,2', 3'-biphenyltetracarboxylic acid, or bis (3,4-dicarboxyphenyl) ether is preferred. [0120] "Aqueous Media" is the same as the aqueous media described in relation to the polyimide precursor composition of the present invention. [Detailed description of the first step] (1) In the first step, a cyclic unsaturated ether compound represented by the above formula (A), a tetracarboxylic acid represented by the above formula (B), and an aqueous medium are mixed. With stirring, an adduct of a cyclic unsaturated ether compound represented by the above formula (A) and a tetracarboxylic acid represented by the above formula (B) [semiacetal ester compound represented by the formula (1) can be prepared ] Water-based composition. According to this method, since an organic solvent with a high environmental load is not required, and an cyclic unsaturated ether compound and a tetracarboxylic acid are reacted in an aqueous medium to obtain an aqueous composition of a hemiacetal ester compound, there is no recovery reaction. It is necessary to mix the hemiacetal compound of the product into the aqueous medium, and the number of steps can be reduced. The molar number of the cyclic unsaturated ether compound is usually relative to the molar number of the tetracarboxylic acid, preferably 0.5 to 4 times the molar number, and more preferably 1 to 2 times the molar number. The method of mixing the cyclic unsaturated ether compound, the tetracarboxylic acid, and the aqueous medium is not particularly limited. For example, the cyclic unsaturated ether compound and the tetracarboxylic acid may be mixed by mixing the aqueous composition containing the cyclic unsaturated ether compound and the aqueous medium and the aqueous composition containing the tetracarboxylic acid and the aqueous medium, And water-based media. In addition, for example, a cyclic unsaturated ether compound, a tetracarboxylic acid, and an aqueous medium can be mixed by adding a cyclic unsaturated ether compound to an aqueous composition containing a tetracarboxylic acid and an aqueous medium and stirring them. Further, for example, a method in which a tetracarboxylic acid is added to an aqueous composition containing a cyclic unsaturated ether compound and an aqueous medium and the mixture is stirred may be mentioned. [0122] The temperature (reaction temperature) during mixing and stirring is not particularly limited as long as it is a temperature at which an addition reaction can be performed, preferably 5 to 60 ° C, more preferably 20 to 50 ° C, and approximately 25 ° C. For the better. The stirring time is not particularly limited as long as it is sufficient for the addition reaction to occur, and is preferably 30 minutes to 6 hours, more preferably 30 minutes to 3 hours, and more preferably about 1 hour.环境 The environment when preparing the above-mentioned aqueous composition containing an adduct is not particularly limited, and an environment such as an atmospheric environment, a nitrogen environment, an inert gas environment, etc. can be used. In addition, the above-mentioned form for preparing an aqueous composition containing an adduct may be a continuous type or a batch type.触 [Catalyst] In a mixed solution containing a cyclic unsaturated ether compound, a tetracarboxylic acid, and an aqueous medium, a catalyst for promoting a reaction between the cyclic unsaturated ether compound and the tetracarboxylic acid may be further contained. As such a catalyst, for example, a catalyst for promoting an addition reaction between an unsaturated bond of a cyclic unsaturated ether compound and a carboxyl group of a tetracarboxylic acid can be mentioned. The catalyst is not particularly limited, and specific examples include enol-forming agents such as titanium tetrachloride and tin tetrachloride which promote high acidity with carboxylic acids. The catalyst system can be used alone or in combination of two or more. [0124] <Second Step> (2) The second step is to mix the adducts synthesized in the first step, a polyamine compound having at least two primary amine groups in one molecule, and an aqueous medium to prepare a polymer. Step of hydrazone imine precursor composition. [0125] "Additions" Additions synthesized in the first step. The adduct is in the form of an aqueous composition dispersed in an aqueous medium. "Polyamine compound having at least two primary amine groups in one molecule" (1) and at least two primary amines in one molecule described in the polyimide precursor composition of the present invention The polyamine compounds are the same. [0127] "Aqueous Media" is the same as the aqueous medium described in the polyimide precursor composition of the present invention. Also, the aqueous medium used in the first step and the aqueous medium used in the second step may be the same type or different types, but the same type is preferred. [0128] "Detailed description of the second step" (1) In the second step, the adduct [semiacetal compound represented by formula (1)] synthesized by mixing the first step has at least two in one molecule. The polyamine compound of the first amine group (hereinafter simply referred to as "polyamine compound") and the aqueous medium are stirred to prepare a polyfluorene imide precursor composition. According to this method, it is the same as the first step described above, and it is not necessary to use organic solvents with high environmental load, and the number of steps can be reduced. The method of mixing the adduct, the polyamine compound, and the aqueous medium synthesized in the first step is not particularly limited. For example, the adduct, the polyamine compound, and the aqueous medium can be mixed by mixing and stirring the aqueous composition containing the adduct and the aqueous medium, and the aqueous composition containing the polyamine compound and the aqueous medium. In addition, for example, by adding a polyamine compound to an aqueous composition containing an adduct and an aqueous medium and stirring them, the adduct, the polyamine compound, and the aqueous medium can be mixed. [0129] Furthermore, any of the components that can be contained in the polyimide precursor composition of the present invention described above can be further mixed. [0130] The temperature during mixing and stirring is not particularly limited, but is preferably 5 to 45 ° C, more preferably 20 to 30 ° C, and more preferably about 25 ° C. The stirring time is not particularly limited, but it is preferably 30 minutes to 6 hours, more preferably 1 hour to 3 hours, and even more preferably about 2 hours. The environment when the polyfluorene imide precursor composition is prepared is not particularly limited, and an environment such as an atmospheric environment, a nitrogen environment, an inert gas environment, and the like can be used. In addition, the preparation method for preparing the polyfluorene imide precursor composition may be a continuous type or a batch type. [0131] <Third Step> (3) The third step is a step of heat-treating the polyimide precursor composition prepared in the second step and curing it to produce a polyimide resin. [0132] "Polyimide precursor composition" (2) The polyimide precursor composition prepared in the second step. The polyimide precursor composition of the present invention comprises a hemiacetal compound represented by the above formula (1), a polyamine compound having at least two primary amine groups in one molecule, and an aqueous medium. Water-based composition. [0133] "Heat treatment" (1) Heat treatment is performed to prepare a drying stage from a dried polyimide precursor composition, a deprotection stage to perform deprotection of a carboxyl group, and a sublimation process from a tetracarboxylic acid and a polyamine compound. Three stages of the hardening stage of the hardening formed by amination, or the drying stage of drying the polyimide precursor composition, and the deprotection of carboxyl groups and the sublimation of tetracarboxylic acids and polyamine compounds The two stages of the hardening deprotection and hardening stages formed by the amination are preferred. [0134] (Drying Stage) 加热 The polyimide precursor composition can be dried by heating and drying the polyimide precursor composition. The heating temperature is not particularly limited, but is preferably 80 ° C or higher, and more preferably 80 ° C to 100 ° C. The heating time is not particularly limited, but it is preferably 3 minutes to 1 hour, and more preferably 15 minutes to 45 minutes. (Deprotection stage) (1) By heating the dried polyimide precursor composition to cause a dissociation reaction, the hemiacetal compound represented by the formula (1) is dissociated into a cyclic ring represented by the formula (A) An unsaturated ether compound and a tetracarboxylic acid represented by formula (B). As a result, the carboxyl group of the tetracarboxylic acid is deprotected, and it becomes hardenable by hydrazone imidization with a polyamine compound. Here, n and R in the formula1
, R2
, R3
, R4
And R5
And X are as previously explained. In addition, tetracarboxylic acid can also be dehydrated to become anhydrous. [0136][0137] The heating temperature is not particularly limited, but it is preferably from 170 ° C to 200 ° C. The heating time is not particularly limited, but it is preferably 3 minutes to 1 hour, and more preferably 15 minutes to 45 minutes. (Hardening stage) (1) The polyimide precursor composition which has been deprotected by heating the carboxyl group is caused to cause imidization (dehydration ring-closing) of the tetracarboxylic acid and the polyamino acid, and the polyimide precursor is promoted. The composition is hardened. Furthermore, the following formula is a reaction formula illustrating the hydrazone imidization of a tetracarboxylic acid and a diamine. [0139][0140] The heating temperature is not particularly limited, but is preferably 200 ° C to 400 ° C. The heating time is not particularly limited, but it is preferably 5 minutes to 2 hours, and more preferably 10 minutes to 50 minutes. [0141] (Deprotection and hardening stage) (1) The carboxyl group is deprotected by heating the polyimide precursor composition that has been dried in the above-mentioned drying stage to perform the imidization of the tetracarboxylic acid and the polyamine compound, and The polyimide precursor composition is cured to obtain a cured polyimide resin. The heating temperature is not particularly limited, and preferably 200 ° C to 400 ° C. The heating time is not particularly limited, but it is preferably 5 minutes to 2 hours, and more preferably 10 minutes to 50 minutes. [0142] The heating method in each of the above stages is not particularly limited, and conventionally known methods such as a hot plate, pressure heating, steam heating, oven heating, and hot air heating can be used.方法 The method for producing a polyimide resin according to the present invention is preferably heat-pressed by steam heating, oven heating, or hot air heating after a predetermined shape is heated under pressure. [Characteristics of the method for producing a polyimide resin according to the present invention] 发明 One of the characteristic points of the method for producing a polyimide resin according to the present invention is to use a hemiacetal ester containing the formula (1) Compounds (adducts), polyamine compounds, and polyimide precursor compositions of aqueous media. Since the hemiacetal bond has resistance to hydrolysis, the hemiacetal ester compound represented by the above-mentioned formula (1) is unlikely to cause the part derived from the cyclic unsaturated ether compound represented by the above-mentioned formula (A) from the above-mentioned formula. The detachment reaction of the tetracarboxylic acid moiety shown in (B), and the carboxyl group of the tetracarboxylic acid is not easily deprotected. Thereby, the aforementioned polyimide precursor composition exhibits excellent storage stability. Another feature of the method for producing a polyimide resin according to the present invention is that the hemiacetal ester compound (addition product) represented by the above formula (1) is decomposed into ions derived from the above formula ( The part of the cyclic unsaturated ether compound represented by A) and the tetracarboxylic acid moiety represented by the above formula (B) can easily deprotect the carboxyl group of the tetracarboxylic acid. A further feature of the method for producing a polyimide resin according to the present invention is that the polyimide resin can improve the polyimide resin formed by curing the polyimide precursor by including a hydrazine compound. Of hardness. It is caused by the close distance between the sulfonium imino groups formed by the sulfonium imidization of a tetracarboxylic acid and a hydrazine compound. [0144] [Polyimide resin] The polyimide resin of the present invention is a polyimide resin obtained by curing the polyimide precursor composition of the present invention. The method for hardening the polyimide precursor composition of the present invention is not particularly limited. For example, the polyimide resin of the present invention can be hardened by performing the third step of the method for producing a polyimide resin of the present invention, thereby obtaining a polymer.醯 imine resin. [0145] The polyimide resin of the present invention is useful as a sealing / shielding material, a buffering / protecting material, and a wire covering material in a wide range of fields, such as transportation machinery for automobiles, general machinery and equipment, electronics, electrical appliances, and construction. , Industrial tapes, hoses, rigid tubes, membranes, sheets, etc., and also used as adhesive materials such as electrode materials, heat conductive agents, conductive agents and other particulate materials. [0146] The following examples and comparative examples are given to explain the present invention more specifically, but the present invention is not limited to these examples. [Example] [0147] [Example 1] "Preparation of Polyimide Precursor Composition" To a separable flask (100 mL; barrel type) equipped with a stirrer was added 2,3,3,4-biphenyl tetra Carboxylic acid (2.9g) and water (35.0g) were stirred and mixed at 25 ° C for 10 minutes, then 2,3-benzofuran (1.0g) was added, and the mixture was stirred and mixed at 25 ° C for 45 minutes to obtain tetracarboxylic acid. Aqueous dispersion of acid derivatives. To the obtained aqueous dispersion, a styrene-acryl fluorene-based polyamine (manufactured by Japan Catalyst Corporation, Polymer (trademark) NK-200PM; non-volatile residue 56% by mass, amine value 2.55 mmol / g-solid; m = 60) (10.0 g), dihydrazine isophthalate (0.5 g), and stirred and mixed at 25 ° C for 2 hours to obtain a milky white dispersion (polyimide precursor composition) of the polyimide precursor. [Example 2] <Preparation of Polyfluorene Imide Precursor Composition> Instead of water (35.0 g), use water (35.3 g) instead of 2,3-benzofuran (1.0 g). A milky white dispersion (polyimide precursor composition) of a polyimide precursor was obtained in the same manner as in Example 1 except that 2,3-dihydrofuran (0.7 g) was used instead. [Example 3] "Preparation of Polyfluorene Imide Precursor Composition" (i) Instead of replacing water (35.0 g) with water (35.2 g), and replacing 2,3-benzofuran (1.0 g) with Instead of using 3,4-dihydro-2H-pyran (0.8 g), a milky-white dispersion (polyimide precursor composition) was obtained in the same manner as in Example 1 to obtain a polyimide precursor. . [Example 4] <Preparation of Polyfluorene Imide Precursor Composition> Instead of replacing 2,3,3,4-biphenyltetracarboxylic acid (2.9 g), use 3,3 ', 4,4 Except for '-benzophenone tetracarboxylic acid (2.9 g), it carried out similarly to Example 1, and obtained the milky white dispersion liquid (polyimide precursor composition) of the polyfluorene imide precursor. [Example 5] <Preparation of Polyfluorene Imide Precursor Composition> Instead of replacing 2,3,3,4-biphenyltetracarboxylic acid (2.9 g), use 4,4'-oxodiphthalic acid Except for the acid (2.9 g), a milky-white dispersion (polyimide precursor composition) of a polyimide precursor was obtained in the same manner as in Example 1. [Example 6] <Preparation of Polyfluorene Imide Precursor Composition> In addition to replacing dihydrazide isophthalate (0.5 g) with dihydrazide adipate (0.25 g), other Example 1 was carried out in the same manner to obtain a milky white dispersion of the polyamidine precursor (polyamidine precursor composition). [Comparative Example 1] <Preparation of Polyfluorene Imide Precursor Composition> To a separable flask (100 mL; cylindrical type) equipped with a stirrer, 2,3,3,4-biphenyltetracarboxylic acid (2.9 g) and water (40.7 g), stirred at 25 ° C for 10 minutes, then added 2,3-benzofuran (1.0g), and stirred at 25 ° C for 45 minutes to obtain a tetracarboxylic acid derivative. Water dispersion. To the obtained aqueous dispersion was added styrene-acrylic acid-based polyamine (manufactured by Japan Catalyst Corporation, Polymer (trademark) NK-200PM; 56% by mass of nonvolatile residue, amine value of 2.55mmol / g-solid; m = 60 ) (13.5 g), and stirred and mixed at 25 ° C. for 2 hours to obtain a pale yellow transparent solution of the polyfluorene imide precursor (polyimide precursor composition). [Comparative Example 2] <Preparation of Polyfluorene Imide Precursor Composition> Instead of water (40.7 g), use water (41.0 g) instead of 2,3-benzofuran (1.0 g). Other than 2,3-dihydrofuran (0.7 g), a milky white dispersion (polyimide precursor composition) of the polyimide precursor was obtained in the same manner as in Comparative Example 1. [Comparative Example 3] <Preparation of Polyfluorene Imide Precursor Composition> Instead of water (40.7 g), use water (40.9 g) instead of 2,3-benzofuran (1.0 g). Except for 3,4-dihydro-2H-pyran (0.8 g), a milky-white dispersion (polyimide precursor composition) of a polyimide precursor was obtained in the same manner as in Comparative Example 1. [Comparative Example 4] <Preparation of Polyfluorene Imide Precursor Composition> To a separable flask (100 mL; barrel type) equipped with a stirrer, 2,3,3,4-biphenyltetracarboxylic acid (2.9 g) and water (40.7 g), and stirred and mixed at 25 ° C for 10 minutes to obtain a mixed solution. Next, a styrene-acryl fluorene-based polyamine (manufactured by Japan Catalyst Corporation, Polymer (trademark) NK-200PM) was added to the mixed liquid in the separable flask; the nonvolatile residue was 56% by mass, and the amine value was 2.55mmol / g- solid; m = 60) (13.5 g), and stirred at 25 ° C for 2 hours. However, it is not possible to obtain a uniform resin solution or dispersion, which results in the precipitation of resin components. [Coatability and Storage Stability] <Test Method> 测量 The E-type viscometer (manufactured by Toki Sangyo Co., Ltd., model TV-22) was used to measure the polyimide precursor composition at 22 immediately after preparation. Viscosity in ℃. Secondly, the polyimide precursor composition (30.0 g) was taken into a glass bottle, and then left to stand in a constant temperature room at 25 ° C. The viscosity at 22 ° C was measured immediately after preparation, and after 1 day, 3 days, and 7 days from the day of standing. The evaluation of coating properties and storage stability was performed based on the following evaluation criteria. [0158] (Evaluation Criteria for Coating Properties) 黏 Viscosity at 22 ° C: 0.1 ~ 1.5Pa · s ······ Easy to flow, good coating properties, viscosity cannot be measured ..., difficult to flow, and coating Poor cloth properties [0159] (Evaluation criteria for storage stability) Viscosity increased from the viscosity immediately after preparation: Within 10% ............ Good storage stability is over 10% ......・ ・ ・ · Poor storage stability [0160] <Measurement results> 表 Table 1 shows the viscosity at 22 ° C immediately after preparation, after 1 day, after 3 days, and after 7 days. In addition, in Table 1, "N.A." indicates that the viscosity cannot be measured. [0161][0162] <Evaluation Results> The polyimide precursor composition of Examples 1 to 6 and the polyimide precursor composition of Comparative Examples 1 to 3 all had low viscosity and coating properties, and no time passed. Increased viscosity and excellent storage stability. [0163] [Solvent resistance] <Test method> Take the prepared polyimide precursor composition into a glass bottle, and then place it in a constant temperature room at 25 ° C. Using the polyimide precursor composition immediately after preparation, and after 1 day, 3 days, and 7 days from the stand-by date, a glass substrate with a cured film was prepared according to the following procedure, and a solvent resistance test was performed. On a surface on one side of the glass substrate, a polyimide precursor composition was applied so that the thickness of the dry coating film became 40 μm. After coating, heat treatment was performed at 90 ° C for 30 minutes using a hot plate, and then heat treatment was performed at 250 ° C for 30 minutes using a constant temperature drying oven, and a polyimide resin was formed on the surface of one side of the glass substrate Composition of hardened film.摩擦 The surface of the cured film was rubbed with a cloth containing NMP (N-methyl-2-pyrrolidone), and the solvent resistance of the cured film was evaluated based on the following evaluation criteria. [0164] (Evaluation Criteria for Solvent Resistance) No change ............... Solvent resistance is good for swelling or erosion of the surface of a cured film .... Solvent resistance is poor. [0165] <Evaluation Results> (1) The results of the evaluation of the solvent resistance are shown in the "Solvent resistance" column in Table 2. "A" indicates good solvent resistance, and "X" indicates poor solvent resistance. The polyimide resin obtained by curing the polyimide precursor composition of Examples 1 to 6 and the polyimide resin obtained by curing the polyimide precursor composition of Comparative Examples 1 to 3 are both Exhibits good solvent resistance. [0166] [Water resistance] <Test method> 采取 Take the polyimide precursor composition immediately after preparation into a glass bottle, and then place it in a constant temperature room at 25 ° C. Using the polyimide precursor composition immediately after preparation and after 1 day, 3 days, and 7 days from the stand-by date, a glass substrate with a cured film was prepared according to the following operation sequence, and a water resistance test (heat Water impregnation test). On a surface on one side of the glass substrate, a polyimide precursor composition was applied so that the thickness of the dry coating film became 40 μm. After coating, heat treatment was performed at 90 ° C for 30 minutes using a hot plate, and then heat treatment was performed at 250 ° C for 30 minutes using a constant temperature drying furnace to form a polyimide resin on the surface of one side of the glass substrate. Composition of hardened film.浸渍 After the glass substrate on which the cured film has been formed is immersed in hot water at 90 ° C. and left for 10 minutes, the cured film is visually observed, and the water resistance of the cured film is evaluated based on the following evaluation criteria. [0167] (Evaluation Criteria for Water Resistance) No change ............... Water resistance means whitening or swelling of the surface of a good hardened film .... Poor water resistance. [0168] <Evaluation Results> 展示 The results of the evaluation of water resistance are shown in the "Water resistance" column of Table 2. "A" indicates good water resistance, and "X" indicates poor water resistance. The polyimide resin obtained by curing the polyimide precursor composition of Examples 1 to 6 and the polyimide resin obtained by curing the polyimide precursor composition of Comparative Examples 1 to 3 are both Exhibits good water resistance. [0169] [Peelability] <Test method> 刚 Take the polyimide precursor composition immediately after preparation into a glass bottle and leave it in a constant temperature room at 25 ° C. Using the polyimide precursor composition immediately after preparation, and one day, three days, and seven days after standing, a PTFE (polytetrafluoroethylene) plate with a thickness of 3 mm was used as the substrate for coating. Coating was performed so that the thickness of the dry coating film became 40 μm. After coating, the substrate was heat-treated at 90 ° C for 30 minutes using a hot plate, and then evaluated based on the following evaluation criteria from the substrate of the polyimide hardened film that was heat-treated at 250 ° C for 30 minutes using a constant temperature drying furnace. Peelability. [0170] (Evaluation Criteria for Peelability) Can be easily peeled from the substrate ... Good peelability cannot be peeled from the substrate ... Poor peelability [0171] <Evaluation Results> 「" Peelability "in Table 2 The column "" shows the results of the evaluation of water resistance. "A" indicates good peelability, and "X" indicates poor peelability. The polyimide resin obtained by curing the polyimide precursor composition of Example 1 can be easily peeled from the substrate, and exhibits good peelability. However, the polyimide resin obtained by curing the polyimide precursor composition of Comparative Example 1 cannot be peeled from the substrate, and the peelability is poor. [0172] <Evaluation Results of Solvent Resistance, Water Resistance, and Peeling Properties> Table 2 shows the evaluation results of solvent resistance, water resistance, and peeling properties (A, X). In addition, in Table 2, "N.A." shows that solvent resistance, water resistance, or peelability cannot be evaluated. [0173][0174][Heat resistance] <Test method> A thermogravimetric measuring device (DTG-60, manufactured by Shimadzu Corporation) measures a polymer obtained by peeling from a glass substrate and hardening the polyimide precursor composition of Examples 1 to 6. 5% imide resin to obtain a cured film of 5% weight reduction temperature. However, since the polyimide resin obtained by curing the polyimide precursor composition of Comparative Examples 1 to 3 cannot be peeled from the glass substrate, no heat resistance test was performed. [0176] <Test Results> The 5% weight reduction temperatures of the cured films of Examples 1 to 6 were all 300 ° C or higher. This is the teaching that the fluorene imine condensation reaction has been carried out, and it can be said that it has the corresponding heat resistance of polyfluorene resin. [Summary] (1) As shown above, the polyimide precursor composition of Examples 1 to 6 was excellent in coating properties and storage stability, and was obtained by curing the polyimide precursor composition. Polyimide resin (hardened material) is excellent in solvent resistance and water resistance. In addition, the polyimide resin (hardened product) obtained by curing the polyimide precursor composition of Examples 1 to 6 is also excellent in peelability. On the other hand, Comparative Examples 1 to 3 are the same as Examples 1 to 6. The polyimide precursor composition is excellent in coating properties and storage stability, and is obtained by curing the polyimide precursor composition. Polyimide resin (hardened material) is also excellent in solvent resistance and water resistance. However, in comparison with Examples 1 to 6, Comparative Examples 1 to 3 had poorer release properties of the polyimide resin (cured material) obtained by curing the polyimide precursor composition.