TW201922852A - Polyimide precursor and polyimide, laminate, flexible device having a low modulus of elasticity, low retardation, and high transparency - Google Patents

Polyimide precursor and polyimide, laminate, flexible device having a low modulus of elasticity, low retardation, and high transparency Download PDF

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TW201922852A
TW201922852A TW107136983A TW107136983A TW201922852A TW 201922852 A TW201922852 A TW 201922852A TW 107136983 A TW107136983 A TW 107136983A TW 107136983 A TW107136983 A TW 107136983A TW 201922852 A TW201922852 A TW 201922852A
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polyimide
diamine
carbon atoms
structural unit
dianhydride
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TWI791056B (en
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王宏遠
岡村勇哉
森亮
安藤敏男
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日商日鐵化學材料股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
    • C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075—Partially aromatic polyimides
    • C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Laminated Bodies (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)

Abstract

The present invention provides a polyimide having a low modulus of elasticity, low retardation, and high transparency, a precursor thereof, a laminate, and a flexible device. The polyimide precursor has a structural unit derived from a diamine and a structural unit derived from an acid dianhydride, and the polyimide precursor is characterized in comprising: i) the structural unit derived from aromatic diamine represented by the formula (1), and ii) the structural unit derived from the silicon-containing diamine represented by the formula (2) as a structural unit derived from a diamine. In the formula (1), Z1 and Z2 are each independently an alkyl group having 1 to 3 carbon atoms or a fluorine-substituted alkyl group having 1 to 3 carbon atoms. In the formula (2), m is an integer of 1 to 2.

Description

聚醯亞胺前體及聚醯亞胺、積層體、可撓性裝置Polyimide precursor and polyimide, laminated body, flexible device

本發明是有關於一種可用作形成顯示裝置的樹脂基板等的聚醯亞胺及其前體。The present invention relates to a polyimide and a precursor thereof that can be used as a resin substrate or the like for forming a display device.

有機電致發光（electroluminescence，EL）裝置等顯示裝置或觸控螢幕（touch panel）被用作以電視之類的大型顯示器、或行動電話、個人電腦、智能手機等小型顯示器為首的各種顯示器的構成構件。例如，有機EL裝置通常是在作為支撐基板的玻璃基板上形成薄膜電晶體（thin film transistor，TFT），進而在其上方依次形成電極、發光層及電極，並利用玻璃基板或多層薄膜等將它們氣密密封而製成。另外，觸控螢幕為形成有第1電極的第1玻璃基板與形成有第2電極的第2玻璃基板經由絕緣層（介電層）接合而成的構成。A display device such as an organic electroluminescence (EL) device or a touch panel is used for various displays including a large display such as a television, and a small display such as a mobile phone, a personal computer, and a smart phone. member. For example, an organic EL device usually forms a thin film transistor (TFT) on a glass substrate as a support substrate, and then sequentially forms an electrode, a light-emitting layer, and an electrode thereon, and uses a glass substrate or a multilayer film to form them. Made of hermetically sealed. The touch screen has a configuration in which a first glass substrate on which a first electrode is formed and a second glass substrate on which a second electrode is formed are connected via an insulating layer (dielectric layer).

這些構成構件是在玻璃基板上形成有各種功能層的積層體。通過將所述玻璃基板替換成樹脂基板，可對使用現有玻璃基板的構成構件進行薄型化、輕量化、可撓化。期待利用其來獲得可撓性顯示器等可撓性裝置。另一方面，樹脂的尺寸穩定性、透明性、耐熱性、耐濕性、膜的強度等比玻璃差，因此正進行各種研究。These constituent members are laminated bodies in which various functional layers are formed on a glass substrate. By replacing the glass substrate with a resin substrate, it is possible to reduce the thickness, weight, and flexibility of constituent members using a conventional glass substrate. It is expected to use this to obtain a flexible device such as a flexible display. On the other hand, dimensional stability, transparency, heat resistance, moisture resistance, and film strength of resins are inferior to those of glass, and various studies are being conducted.

例如，專利文獻1公開了一種使特定結構的聚醯亞胺前體溶液在無機基板上流延並進行乾燥及醯亞胺化而獲得的聚醯亞胺膜。所述聚醯亞胺膜的優點是透光率高且逸氣（out gas）少。 但熱膨脹係數（coefficient of thermal expansion，CTE）超過40 ppm/K，因此與玻璃基板等無機基板之間的CTE的差大。因此，容易發生翹曲，從而在形成裝置後會產生剝離或裂紋等，難以獲得形狀穩定性優異的可撓性裝置。For example, Patent Document 1 discloses a polyimide film obtained by casting a polyimide precursor solution having a specific structure on an inorganic substrate, drying and then imidizing the polyimide. The polyfluorene imide film has the advantages of high light transmittance and low out gas. However, the coefficient of thermal expansion (CTE) exceeds 40 ppm / K, so the difference between the CTE and inorganic substrates such as glass substrates is large. Therefore, warpage easily occurs, and peeling or cracking may occur after the device is formed, and it is difficult to obtain a flexible device having excellent shape stability.

另外，專利文獻2公開了一種使用具有酚性羥基的二胺與具有矽氧烷骨架的二胺而製造的聚醯亞胺樹脂。通過具有矽氧烷骨架而彈性係數降低。結果，殘餘應力降低，因此，可抑制所述積層體中翹曲的產生。 但所獲得的聚醯亞胺膜存在透明性（透光率）低、並且耐熱性低的問題。In addition, Patent Document 2 discloses a polyimide resin produced using a diamine having a phenolic hydroxyl group and a diamine having a siloxane skeleton. The elastic modulus is reduced by having a siloxane skeleton. As a result, the residual stress is reduced, and therefore, the occurrence of warpage in the laminated body can be suppressed. However, the obtained polyimide film has problems of low transparency (light transmittance) and low heat resistance.

另外，專利文獻3公開了一種使用2,2-雙(三氟甲基)聯苯胺（2,2-bis(trifluoromethyl)benzidine，TFMB）與具有長鏈的矽氧烷骨架的二胺而製造的聚醯亞胺。使用所述聚醯亞胺而製成的膜的透明性高，為低彈性係數且殘餘應力低，機械物性及耐熱性優異。 但所述聚醯亞胺相對於溶劑的溶解性低，且膜的透光率低。 進而，具有長鏈的矽氧烷骨架的二胺存在如下重大問題：其雖含有環狀矽氧烷化合物作為雜質，但所述環狀矽氧烷化合物的揮發性高，因此逸氣多。在逸氣多的情況下，例如在有機EL裝置的製造步驟中，在聚醯亞胺基板上形成各種功能層時，因逸氣成分而無法充分減壓，從而擔心引起所述功能層的形成不良。In addition, Patent Document 3 discloses a product produced by using 2,2-bis (trifluoromethyl) benzidine (TFMB) and a diamine having a long-chain siloxane skeleton. Polyimide. A film made using the polyimide has high transparency, a low coefficient of elasticity, low residual stress, and excellent mechanical properties and heat resistance. However, the polyimide has a low solubility in a solvent and a low light transmittance of the film. Furthermore, a diamine having a long-chain siloxane skeleton has a significant problem in that, although it contains a cyclic siloxane compound as an impurity, the cyclic siloxane compound is highly volatile and therefore has a lot of outgassing. In the case where there are many outgassing, for example, when forming various functional layers on a polyimide substrate in a manufacturing step of an organic EL device, the degassing component cannot sufficiently reduce the pressure, which may cause the formation of the functional layer. bad.

另外，專利文獻4公開了一種使用具有鏈長短的矽氧烷骨架的二胺、具有脂環結構的二胺及特定的芳香族四羧酸二酐而製造的聚醯亞胺。並公開了使用所述聚醯亞胺而製成的膜可應用為代替玻璃的透明基板材料。 但所述聚醯亞胺的透明性並不充分。In addition, Patent Document 4 discloses a polyfluorene imine produced by using a diamine having a siloxane skeleton having a short chain length, a diamine having an alicyclic structure, and a specific aromatic tetracarboxylic dianhydride. It is also disclosed that a film made using the polyimide can be used as a transparent substrate material instead of glass. However, the polyimide has insufficient transparency.

另外，為了在可撓性顯示器用途中應用樹脂基板，除所述物性以外，重要的是樹脂的雙折射（延遲）低。其是為了獲得鮮明的圖像而需要的物性，但在專利文獻1～專利文獻4中均未公開關於低雙折射的內容。In addition, in order to apply a resin substrate to a flexible display application, in addition to the physical properties described above, it is important that the resin has low birefringence (retardation). This is a physical property required for obtaining a sharp image, but none of Patent Documents 1 to 4 discloses low birefringence.

根據以上，為了將樹脂基板應用為可撓性裝置用的基板，需要兼具低彈性係數、低殘餘應力、低延遲、高透明性、低逸氣，但在現有技術中難以實現。 [現有技術文獻]Based on the above, in order to apply a resin substrate as a substrate for a flexible device, it is necessary to have both a low coefficient of elasticity, a low residual stress, a low delay, a high transparency, and a low outgas, but it is difficult to achieve it in the prior art. [Prior Art Literature]

[專利文獻] [專利文獻1] 日本專利特開2012-040836號公報 [專利文獻2] 日本專利特開2007-246920公報 [專利文獻3] 日本專利5948545號公報 [專利文獻4] 國際公開2017/159538號[Patent Literature] [Patent Literature 1] Japanese Patent Laid-Open Publication No. 2012-040836 [Patent Literature 2] Japanese Patent Laid-Open Publication No. 2007-246920 [Patent Literature 3] Japanese Patent Publication No. 5948545 [Patent Literature 4] International Publication 2017 / 159538

[發明所要解決的問題] 本發明的目的在於提供一種低彈性係數、低殘餘應力、低延遲、高透明性優異的聚醯亞胺及其前體。 [解決問題的技術手段][Problems to be Solved by the Invention] An object of the present invention is to provide a polyimide and a precursor thereof having a low coefficient of elasticity, low residual stress, low retardation, and high transparency. [Technical means to solve the problem]

本發明人等人進行了努力研究，結果發現特定結構的聚醯亞胺或其前體能夠滿足所述特性，從而完成了本發明。The present inventors conducted diligent research, and as a result, found that polyfluorene imine having a specific structure or a precursor thereof can satisfy the characteristics, and thus completed the present invention.

即，本發明是一種聚醯亞胺前體，其具有源自二胺的結構單元與源自酸二酐的結構單元，且所述聚醯亞胺前體的特徵在於，具有i）源自下述式（1）所表示的芳香族二胺的結構單元、以及ii）源自下述式（2）所表示的含矽二胺的結構單元作為源自二胺的結構單元。 [化1]（1） （式中，Z1 及Z2 分別獨立地為碳數1～3的烷基或碳數1～3的氟取代烷基） [化2]（2） （式中，R1 及R2 分別獨立地為碳數3～20的二價的脂肪族烴基、或碳數6～20的二價的芳香族烴基，R3 、R4 、R5 及R6 分別獨立地為碳數1～3的一價的脂肪族烴基、或碳數6～10的芳香族烴基，m為1～2的整數）That is, the present invention is a polyfluorene imide precursor having a structural unit derived from a diamine and a structural unit derived from an acid dianhydride, and the polyfluorene imide precursor is characterized by having i) The structural unit of the aromatic diamine represented by the following formula (1), and ii) the structural unit derived from the silyl diamine represented by the following formula (2) are structural units derived from the diamine. [Chemical 1] (1) (wherein Z 1 and Z 2 are each independently an alkyl group having 1 to 3 carbon atoms or a fluorine-substituted alkyl group having 1 to 3 carbon atoms) [Chem. 2] (2) (wherein R 1 and R 2 are each independently a divalent aliphatic hydrocarbon group having 3 to 20 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms; R 3 , R 4 , R 5 and R 6 are each independently a monovalent aliphatic hydrocarbon group having 1 to 3 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and m is an integer of 1 to 2)

本發明的聚醯亞胺前體理想的是包含源自二胺的全部結構單元的5莫耳%～80莫耳%的源自式（2）所表示的含矽二胺的結構單元。The polyfluorene imide precursor of the present invention desirably contains 5 mol% to 80 mol% of all structural units derived from diamine and is derived from a silicon diamine-containing structural unit represented by formula (2).

另外，本發明是一種聚醯亞胺，其具有源自二胺的結構單元與源自酸二酐的結構單元，且所述聚醯亞胺的特徵在於，具有i）源自所述式（1）所表示的芳香族二胺的結構單元、以及ii）源自所述式（2）所表示的含矽二胺的結構單元。In addition, the present invention is a polyfluorene imine having a structural unit derived from a diamine and a structural unit derived from an acid dianhydride, and the polyfluorene imine is characterized by having i) derived from the formula ( The structural unit of the aromatic diamine represented by 1), and ii) the structural unit derived from the silicon diamine represented by the said formula (2).

本發明的聚醯亞胺優選的是黃色度（yellow index，YI）為10以下，且可優選地用於透明樹脂基板用途。The polyfluorene imide of the present invention preferably has a yellow index (YI) of 10 or less, and can be preferably used for transparent resin substrate applications.

本發明的另一實施方式是一種在支撐體的表面上形成所述聚醯亞胺而成的積層體，且是一種在所述聚醯亞胺的表面上形成功能層而成的可撓性裝置。 [發明的效果]Another embodiment of the present invention is a laminated body formed by forming the polyfluorene imide on a surface of a support, and is a flexibility formed by forming a functional layer on the surface of the polyfluorene. Device. [Effect of the invention]

本發明的聚醯亞胺前體或由其獲得的聚醯亞胺兼具低彈性係數、低殘餘應力、低延遲、高透明性、低逸氣。生產性也良好。因此，適於用作顯示裝置、觸控螢幕等的樹脂基板用聚醯亞胺膜，且可優選地應用為在聚醯亞胺膜的表面上形成有顯示元件、發光元件、電路、銦錫氧化物（Indium Tin Oxide，ITO）等的導電膜、金屬網（metal mesh）、硬塗膜或者防止水分或氧等的滲透的阻氣（gas barrier）膜等功能層的可撓性裝置。The polyimide precursor of the present invention or the polyimide obtained from the polyimide precursor has low elastic coefficient, low residual stress, low delay, high transparency, and low outgassing. Productivity is also good. Therefore, it is suitable for use as a polyimide film for a resin substrate for a display device, a touch screen, and the like, and can be preferably applied as a display element, a light-emitting element, a circuit, indium tin formed on the surface of the polyimide film. Flexible devices for functional layers such as conductive films such as oxides (Indium Tin Oxide, ITO), metal meshes, hard coating films, or gas barrier films that prevent the penetration of moisture or oxygen.

本發明的聚醯亞胺前體具有源自二胺的結構單元與源自酸二酐的結構單元，且所述聚醯亞胺前體具有i）源自下述式（1）所表示的芳香族二胺的結構單元、以及ii）源自下述式（2）所表示的含矽二胺的結構單元。在對本發明的聚醯亞胺前體進行醯亞胺化而成的聚醯亞胺中，也原樣地擁有這些結構單元。 再者，聚醯亞胺前體及聚醯亞胺的結構單元及其比例取決於二胺與酸二酐的種類和使用比例，因此，結構單元的說明是通過二胺與酸二酐來進行說明。將二胺與酸二酐的使用比例設為分別源自所述二胺與所述酸二酐的結構單元的存在比例。The polyfluorene imide precursor of the present invention has a structural unit derived from a diamine and a structural unit derived from an acid dianhydride, and the polyfluorene imide precursor has i) derived from the following formula (1) The structural unit of the aromatic diamine and ii) are derived from the structural unit containing a silicon diamine represented by the following formula (2). The polyfluorene imide obtained by hydrazone-imidizing the polyfluorene imide precursor of the present invention also has these structural units as it is. Moreover, the structural units of polyimide precursors and polyimide and their proportions depend on the type and use ratio of diamine and acid dianhydride. Therefore, the description of the structural units is made by using diamine and acid dianhydride. Instructions. The use ratio of a diamine and an acid dianhydride is set as the existence ratio of the structural unit derived from the said diamine and the said acid dianhydride, respectively.

在下述式（1）所表示的芳香族二胺中， [化1]（1） Z1 及Z2 分別獨立地為碳數1～3的烷基或碳數1～3的氟取代烷基。優選為源自2,2'-雙(三氟甲基)聯苯胺、或2,2'-雙(三甲基)聯苯胺的結構單元。In the aromatic diamine represented by the following formula (1), [Chem. 1] (1) Z 1 and Z 2 are each independently an alkyl group having 1 to 3 carbon atoms or a fluorine-substituted alkyl group having 1 to 3 carbon atoms. It is preferably a structural unit derived from 2,2'-bis (trifluoromethyl) benzidine, or 2,2'-bis (trimethyl) benzidine.

在下述式（2）所表示的含矽二胺中， [化2]（2） R1 及R2 分別獨立地為碳數3～20的二價的脂肪族烴基、或碳數6～20的二價的芳香族烴基。優選為碳數1～6的伸烷基，尤其是亞甲基、伸乙基或伸丙基。R3 、R4 、R5 及R6 分別獨立地為碳數1～3的一價的脂肪族烴基、或碳數6～10的芳香族烴基。優選為甲基或苯基。m為1～2的整數。若m超過3，則延遲及彈性係數變高，黃色度（YI）惡化，透明度下降，且逸氣的產生變多，因此不優選。優選為m=1。In the silicon-containing diamine represented by the following formula (2), [Chem 2] (2) R 1 and R 2 are each independently a divalent aliphatic hydrocarbon group having 3 to 20 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms. Preferred is an alkylene group having 1 to 6 carbon atoms, especially methylene, ethylidene or propylidene. R 3 , R 4 , R 5 and R 6 are each independently a monovalent aliphatic hydrocarbon group having 1 to 3 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms. Preferred is methyl or phenyl. m is an integer of 1 to 2. If m exceeds 3, the retardation and the elastic coefficient are increased, the yellowness (YI) is deteriorated, the transparency is decreased, and the generation of outgass is increased, which is not preferable. Preferably, m = 1.

關於所述式（2）所表示的含矽二胺，就耐熱性、低延遲的觀點而言，優選的是包含全部二胺的5莫耳%～80莫耳%。優選為10莫耳%以上，更優選為15莫耳%以上。進而優選為20莫耳%以上。更進而優選為超過20莫耳%的範圍。From the viewpoint of heat resistance and low retardation, the silicon-containing diamine represented by the formula (2) is preferably 5 mol% to 80 mol% including all diamines. It is preferably 10 mol% or more, and more preferably 15 mol% or more. It is more preferably 20 mol% or more. More preferably, it is a range exceeding 20 mol%.

關於所述式（1）所表示的芳香族二胺，就耐熱性、低熱膨脹係數、透明性的觀點而言，優選的是包含全部二胺的30莫耳%以上，更優選為40莫耳%以上，進而優選為50莫耳%以上。The aromatic diamine represented by the formula (1) is preferably 30 mol% or more, and more preferably 40 mol, from the viewpoints of heat resistance, low thermal expansion coefficient, and transparency. % Or more, and more preferably 50 mol% or more.

除所述式（1）及所述式（2）所表示的二胺以外，還可使用其他二胺。在使用其他二胺的情況下，可在全部二胺的10莫耳%～70莫耳%的範圍內使用，優選為低於50莫耳%。In addition to the diamines represented by the formula (1) and the formula (2), other diamines may be used. When other diamines are used, they can be used in the range of 10 mol% to 70 mol% of all diamines, and preferably less than 50 mol%.

作為所述其他二胺，適宜為具有一個以上的芳香族環的二胺。若對所述二胺進行舉例，則可列舉：2,2'-二甲基-4,4'-二氨基聯苯（別名：2,2'-二甲基-聯苯胺）、3,3'-二甲基-4,4'-二氨基聯苯、4,4'-二氨基二苯基醚、3,4'-二氨基二苯基醚、4,6-二甲基間苯二胺、2,5-二甲基對苯二胺、2,4-二氨基-1,3,5-三甲苯、4,4'-亞甲基二鄰甲苯胺、4,4'-亞甲基二-2,6-二甲苯胺、4,4'-亞甲基-2,6-二乙基苯胺、2,4-甲苯二胺、間苯二胺、對苯二胺、4,4'-二氨基二苯基丙烷、3,3'-二氨基二苯基丙烷、4,4'-二氨基二苯基乙烷、3,3'-二氨基二苯基乙烷、4,4'-二氨基二苯基甲烷、3,3'-二氨基二苯基甲烷、2,2-雙[4-(4-氨基苯氧基)苯基]丙烷、4,4'-二氨基二苯基硫醚、3,3'-二氨基二苯基硫醚、4,4'-二氨基二苯基碸、3,3'-二氨基二苯基碸、4,4'-二氨基二苯基醚、3,3'-二氨基二苯基醚、1,3-雙(3-氨基苯氧基)苯、1,3-雙(4-氨基苯氧基)苯、1,4-雙(4-氨基苯氧基)苯、聯苯胺、3,3'-二氨基聯苯、3,3'-二甲基-4,4'-二氨基聯苯、3,3'-二甲氧基聯苯胺、4,4'-二氨基對三聯苯、3,3'-二氨基對三聯苯、雙(對β-氨基-第三丁基苯基)醚、雙(對β-甲基-δ-氨基戊基)苯、對雙(2-甲基-4-氨基戊基)苯、對雙(1,1-二甲基-5-氨基戊基)苯、1,5-二氨基萘、2,6-二氨基萘、2,4-雙(β-氨基-第三丁基)甲苯、2,4-二氨基甲苯、間二甲苯-2,5-二胺、對二甲苯-2,5-二胺、間二甲苯二胺、對二甲苯二胺、2,6-二氨基吡啶、2,5-二氨基吡啶、2,5-二氨基-1,3,4-噁二唑、呱嗪、5-氨基-2-(4-氨基苯基)苯並咪唑等。The other diamine is preferably a diamine having one or more aromatic rings. If the diamine is exemplified, 2,2'-dimethyl-4,4'-diaminobiphenyl (alias: 2,2'-dimethyl-benzidine), 3,3 '-Dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,6-dimethylisophenylene Amine, 2,5-dimethyl-p-phenylenediamine, 2,4-diamino-1,3,5-trimethylbenzene, 4,4'-methylenedi-o-toluidine, 4,4'-methylene Di-2,6-xylyleneamine, 4,4'-methylene-2,6-diethylaniline, 2,4-toluenediamine, m-phenylenediamine, p-phenylenediamine, 4,4 '-Diaminodiphenylpropane, 3,3'-diaminodiphenylpropane, 4,4'-diaminodiphenylethane, 3,3'-diaminodiphenylethane, 4,4 '-Diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 4,4'-diaminodi Phenylsulfide, 3,3'-diaminodiphenylsulfide, 4,4'-diaminodiphenylphosphonium, 3,3'-diaminodiphenylphosphonium, 4,4'-diaminodi Phenyl ether, 3,3'-diaminodiphenyl ether, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4- Bis (4-aminophenoxy) benzene, benzidine, 3,3'-diamine Biphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxybenzidine, 4,4'-diamino-p-terphenyl, 3,3 ' -Diamino-p-terphenyl, bis (p-β-amino-third-butylphenyl) ether, bis (p-β-methyl-δ-aminopentyl) benzene, p-bis (2-methyl-4-amino) Amyl) benzene, p-bis (1,1-dimethyl-5-aminopentyl) benzene, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,4-bis (β-amino- Tertiary butyl) toluene, 2,4-diaminotoluene, m-xylene-2,5-diamine, p-xylene-2,5-diamine, m-xylenediamine, p-xylenediamine, 2 1,6-diaminopyridine, 2,5-diaminopyridine, 2,5-diamino-1,3,4-oxadiazole, verazine, 5-amino-2- (4-aminophenyl) benzo Imidazole and so on.

所述其他二胺中，就反應快、且為高透明性的觀點而言，更優選為4,4'-二氨基二苯基醚、4,6-二甲基間苯二胺、2,5-二甲基對苯二胺、2,4-二氨基-1,3,5-三甲苯、2,4-甲苯二胺、間苯二胺、2,2'-二甲基-4,4'-二氨基聯苯、5-氨基-2-(4-氨基苯基)苯並咪唑或對苯二胺。進而優選的是適宜為2,2'-二甲基-4,4'-二氨基聯苯、5-氨基-2-(4-氨基苯基)苯並咪唑或4,4'-二氨基二苯基醚。Among the other diamines, from the viewpoint of fast reaction and high transparency, 4,4'-diaminodiphenyl ether, 4,6-dimethylm-phenylenediamine, 2, 5-dimethyl-p-phenylenediamine, 2,4-diamino-1,3,5-trimethylbenzene, 2,4-toluenediamine, m-phenylenediamine, 2,2'-dimethyl-4, 4'-diaminobiphenyl, 5-amino-2- (4-aminophenyl) benzimidazole or p-phenylenediamine. Further preferred are 2,2'-dimethyl-4,4'-diaminobiphenyl, 5-amino-2- (4-aminophenyl) benzimidazole or 4,4'-diaminodi. Phenyl ether.

作為酸二酐，可使用公知的酸二酐。例如可列舉：4,4'-(2,2'-六氟亞異丙基)二鄰苯二甲酸二酐、萘-2,3,6,7-四羧酸二酐、萘-1,2,5,6-四羧酸二酐、萘-1,2,6,7-四羧酸二酐、均苯四甲酸二酐、3,3',4,4'-聯苯四羧酸二酐、3,3',4,4'-二苯甲酮四羧酸二酐、2,2',3,3'-二苯甲酮四羧酸二酐、2,3,3',4'-二苯甲酮四羧酸二酐、萘-1,2,4,5-四羧酸二酐、萘-1,4,5,8-四羧酸二酐、4,8-二甲基-1,2,3,5,6,7-六氫萘-1,2,5,6-四羧酸二酐、4,8-二甲基-1,2,3,5,6,7-六氫萘-2,3,6,7-四羧酸二酐、2,6-二氯萘-1,4,5,8-四羧酸二酐、2,7-二氯萘-1,4,5,8-四羧酸二酐、2,3,6,7-四氯萘-1,4,5,8-四羧酸二酐、1,4,5,8-四氯萘-2,3,6,7-四羧酸二酐、2,2',3,3'-聯苯四羧酸二酐、2,3,3',4'-聯苯四羧酸二酐、3,3'',4,4''-對三聯苯四羧酸二酐、2,2'',3,3''-對三聯苯四羧酸二酐、2,3,3'',4''-對三聯苯四羧酸二酐、2,2-雙(2,3-二羧基苯基)-丙烷二酐、2,2-雙(3,4-二羧基苯基)-丙烷二酐、雙(2,3-二羧基苯基)醚二酐、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(2,3-二羧基苯基)碸二酐、雙(3,4-二羧基苯基)碸二酐、1,1-雙(2,3-二羧基苯基)乙烷二酐、1,1-雙(3,4-二羧基苯基)乙烷二酐、苝-2,3,8,9-四羧酸二酐、苝-3,4,9,10-四羧酸二酐、苝-4,5,10,11-四羧酸二酐、苝-5,6,11,12-四羧酸二酐、菲-1,2,7,8-四羧酸二酐、菲-1,2,6,7-四羧酸二酐、菲-1,2,9,10-四羧酸二酐、環戊烷-1,2,3,4-四羧酸二酐、吡嗪-2,3,5,6-四羧酸二酐、吡咯烷-2,3,4,5-四羧酸二酐、噻吩-2,3,4,5-四羧酸二酐、4,4'-氧基二鄰苯二甲酸二酐、(三氟甲基)均苯四甲酸二酐、二(三氟甲基)均苯四甲酸二酐、二(七氟丙基)均苯四甲酸二酐、五氟乙基均苯四甲酸二酐、雙{3,5-二(三氟甲基)苯氧基}均苯四甲酸二酐、2,2-雙(3,4-二羧基苯基)六氟丙烷二酐、5,5'-雙(三氟甲基)-3,3',4,4'-四羧基聯苯二酐、2,2',5,5'-四(三氟甲基)-3,3',4,4'-四羧基聯苯二酐、5,5'-雙(三氟甲基)-3,3',4,4'-四羧基二苯基醚二酐、5,5'-雙(三氟甲基)-3,3',4,4'-四羧基二苯甲酮二酐、雙{(三氟甲基)二羧基苯氧基}苯二酐、雙{(三氟甲基)二羧基苯氧基}苯二酐、三氟甲基苯二酐、雙(二羧基苯氧基)三氟甲基苯二酐、雙(二羧基苯氧基)雙(三氟甲基)苯二酐、雙(二羧基苯氧基)四(三氟甲基)苯二酐、2,2-雙{(4-(3,4-二羧基苯氧基)苯基}六氟丙烷二酐、雙{(三氟甲基)二羧基苯氧基}聯苯二酐、雙{(三氟甲基)二羧基苯氧基}雙(三氟甲基)聯苯二酐、雙{(三氟甲基)二羧基苯氧基}二苯基醚二酐、雙(二羧基苯氧基)雙(三氟甲基)聯苯二酐等。另外，這些酸二酐可單獨使用，或者也可併用兩種以上。As the acid dianhydride, a known acid dianhydride can be used. Examples include: 4,4 '-(2,2'-hexafluoroisopropylidene) diphthalic dianhydride, naphthalene-2,3,6,7-tetracarboxylic dianhydride, naphthalene-1, 2,5,6-tetracarboxylic dianhydride, naphthalene-1,2,6,7-tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic acid Dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 2,2', 3,3'-benzophenonetetracarboxylic dianhydride, 2,3,3 ', 4'-benzophenone tetracarboxylic dianhydride, naphthalene-1,2,4,5-tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, 4,8-di Methyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6 , 7-hexahydronaphthalene-2,3,6,7-tetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene -1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 1,4,5,8-tetracarboxylic Chloronaphthalene-2,3,6,7-tetracarboxylic dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic acid Dianhydride, 3,3 '', 4,4 ''-p-terephthalate dianhydride, 2,2 '', 3,3 ''-p-terephthalate dianhydride, 2,3,3 ``, 4 ''-terephthalic dianhydride, 2,2-bis (2,3-dicarboxyphenyl) -propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) ) -Propane dianhydride, bis (2,3-dicarboxyphenyl) ) Ether dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) fluorene dianhydride, Bis (3,4-dicarboxyphenyl) fluorene dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) Ethane dianhydride, fluorene-2,3,8,9-tetracarboxylic dianhydride, fluorene-3,4,9,10-tetracarboxylic dianhydride, fluorene-4,5,10,11-tetracarboxylic acid Dianhydride, pyrene-5,6,11,12-tetracarboxylic dianhydride, phenanthrene-1,2,7,8-tetracarboxylic dianhydride, phenanthrene-1,2,6,7-tetracarboxylic dianhydride Phenanthrene-1,2,9,10-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride Anhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, (Trifluoromethyl) pyromellitic dianhydride, bis (trifluoromethyl) pyromellitic dianhydride, bis (heptafluoropropyl) pyromellitic dianhydride, pentafluoroethyl pyromellitic dianhydride Anhydride, bis {3,5-bis (trifluoromethyl) phenoxy} pyromellitic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 5,5 '-Bis (trifluoromethyl) -3,3', 4,4'-tetracarboxybiphenyl dianhydride, 2,2 ', 5,5'-tetrakis (trifluoromethyl) -3,3', 4,4'- Tetracarboxybiphenyl dianhydride, 5,5'-bis (trifluoromethyl) -3,3 ', 4,4'-tetracarboxydiphenyl ether dianhydride, 5,5'-bis (trifluoromethyl) ) -3,3 ', 4,4'-tetracarboxybenzophenone dianhydride, bis {(trifluoromethyl) dicarboxyphenoxy} benzene dianhydride, bis {(trifluoromethyl) dicarboxybenzene Oxy} phthalic anhydride, trifluoromethylphthalic anhydride, bis (dicarboxyphenoxy) trifluoromethylphthalic anhydride, bis (dicarboxyphenoxy) bis (trifluoromethyl) phthalic anhydride, Bis (dicarboxyphenoxy) tetrakis (trifluoromethyl) phthalic anhydride, 2,2-bis {(4- (3,4-dicarboxyphenoxy) phenyl} hexafluoropropane dianhydride, bis { (Trifluoromethyl) dicarboxyphenoxy} biphenyl dianhydride, bis {(trifluoromethyl) dicarboxyphenoxy} bis (trifluoromethyl) biphenyl dianhydride, bis {(trifluoromethyl ) Dicarboxyphenoxy} diphenyl ether dianhydride, bis (dicarboxyphenoxy) bis (trifluoromethyl) biphenyl dianhydride, and the like. These acid dianhydrides may be used alone or in combination of two or more.

作為其他優選的四羧酸二酐，優選的是能夠對聚醯亞胺膜賦予強度與柔軟性的均苯四甲酸二酐、3,3',4,4'-聯苯四羧酸二酐、4,4'-氧基二鄰苯二甲酸二酐。就聚醯亞胺膜的熱膨脹係數（CTE）不過度上升且可控制在適當範圍內而言，更優選為均苯四甲酸二酐或3,3',4,4'-聯苯四羧酸二酐。 另外，就耐熱性、透明性優異且可將CTE控制在適當範圍內而言，優選為4,4'-(2,2'-六氟亞異丙基)二鄰苯二甲酸二酐、1,2,3,4-環丁烷四羧酸二酐、或4,4'-氧基二鄰苯二甲酸二酐。更優選為1,2,3,4-環丁烷四羧酸二酐。As other preferable tetracarboxylic dianhydrides, pyromellitic dianhydride and 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride which can impart strength and flexibility to a polyimide film are preferred. , 4,4'-oxydiphthalic dianhydride. To the extent that the coefficient of thermal expansion (CTE) of the polyimide film does not increase excessively and can be controlled within an appropriate range, pyromellitic dianhydride or 3,3 ', 4,4'-biphenyltetracarboxylic acid is more preferred. Dianhydride. In addition, in terms of excellent heat resistance and transparency, and CTE can be controlled within an appropriate range, 4,4 '-(2,2'-hexafluoroisopropylidene) diphthalic dianhydride, 1 , 2,3,4-cyclobutane tetracarboxylic dianhydride, or 4,4'-oxydiphthalic dianhydride. More preferred is 1,2,3,4-cyclobutane tetracarboxylic dianhydride.

本發明的聚醯亞胺前體可利用以0.9～1.1的莫耳比使用所述二胺與酸二酐並在有機極性溶媒中進行聚合的公知方法來製造。例如，可通過以下方式獲得：在氮氣氣流下使二胺溶解於N,N-二甲基乙醯胺、N-甲基-2-吡咯啶酮等非質子性醯胺系溶媒中後添加酸二酐，使它們在室溫下反應3小時～20小時左右。為了使反應快速進行，也可在40℃～80℃的溫度下加熱15分鐘（min）～5小時。此時，分子末端可由芳香族單胺或芳香族單羧酸二酐密封。作為溶媒，除所述以外還可列舉二甲基甲醯胺、2-丁酮、二乙二醇二甲醚、二甲苯、γ-丁內酯等，可使用一種，或者也可併用兩種以上。另外，為了提高溶解性，可追加二甲苯、己烷等。The polyfluorene imide precursor of the present invention can be produced by a known method in which the diamine and the acid dianhydride are used in a molar ratio of 0.9 to 1.1 and polymerized in an organic polar solvent. For example, it can be obtained by dissolving a diamine in an aprotic fluorene-based solvent such as N, N-dimethylacetamidine and N-methyl-2-pyrrolidone under a nitrogen gas stream, and then adding an acid. The dianhydride is allowed to react at room temperature for about 3 to 20 hours. In order to make the reaction proceed quickly, it may be heated at a temperature of 40 ° C to 80 ° C for 15 minutes (min) to 5 hours. At this time, the molecular terminal may be sealed with an aromatic monoamine or an aromatic monocarboxylic dianhydride. As the solvent, dimethylformamide, 2-butanone, diethylene glycol dimethyl ether, xylene, γ-butyrolactone, etc. can be mentioned in addition to the above. One kind may be used, or two kinds may be used in combination. the above. In order to improve the solubility, xylene, hexane, and the like may be added.

本發明的聚醯亞胺是對本發明的聚醯亞胺前體進行醯亞胺化而得。醯亞胺化可利用熱醯亞胺化法或化學醯亞胺化法等來進行。熱醯亞胺化是通過以下方式來進行：在玻璃、金屬、樹脂等任意的支撐基材上，使用塗敷器塗布聚醯亞胺前體，並在150℃以下的溫度下進行2分鐘～60分鐘預乾燥，然後，通常在室溫～360℃左右的溫度下進行10分鐘～20小時左右的熱處理以進行溶劑去除、醯亞胺化。在可獲得牢固的膜的情況下，熱處理溫度也可達到280℃。在280℃～360℃之間，能夠根據必要的機械特性來變更熱處理溫度。化學醯亞胺化是在聚醯亞胺前體（也稱為「聚醯胺酸（polyamic acid）」）溶液中添加脫水劑與催化劑，在30℃～60℃下進行化學性脫水。作為代表性的脫水劑，可例示乙酸酐，作為催化劑，可例示吡啶。熱醯亞胺化中，若對酸二酐或二胺的種類、溶劑的種類的組合進行選擇，則醯亞胺化會在比較短的時間內完成，從而包括預加熱在內也能夠進行60分鐘以內的熱處理。再者，在塗布聚醯亞胺前體時，可製成使聚醯亞胺前體溶解於公知的溶媒中而成的聚醯亞胺前體溶液來進行塗布。The polyfluorene imide of the present invention is obtained by fluorimiding the polyfluorene imine precursor of the present invention. The fluorene imidization can be performed by a thermal fluoridation method or a chemical fluoridation method. The thermal ammonium imidization is performed by coating a polyimide precursor on an arbitrary supporting substrate such as glass, metal, resin, etc. using an applicator, and performing the process at a temperature of 150 ° C. or less for 2 minutes to After pre-drying for 60 minutes, heat treatment is usually performed at a temperature of about room temperature to about 360 ° C. for about 10 minutes to about 20 hours to perform solvent removal and sulfonation. In the case where a strong film can be obtained, the heat treatment temperature can also reach 280 ° C. Between 280 ° C and 360 ° C, the heat treatment temperature can be changed according to necessary mechanical characteristics. Chemical ammonium imidization involves adding a dehydrating agent and a catalyst to a solution of a polyimide precursor (also referred to as "polyamic acid"), and performing chemical dehydration at 30 ° C to 60 ° C. A typical dehydrating agent is acetic anhydride, and a catalyst is pyridine. In thermal ammonium imidization, if the combination of the type of acid dianhydride or diamine and the type of solvent is selected, the ammonium imidization can be completed in a relatively short period of time, so that it can be performed including pre-heating. Heat treatment within minutes. When the polyimide precursor is applied, a polyimide precursor solution prepared by dissolving the polyimide precursor in a known solvent may be applied.

關於本發明的聚醯亞胺前體及聚醯亞胺的優選的聚合度，以聚醯亞胺前體溶液的利用E型黏度計測定的黏度換算，可為1,000 cP～100,000 cP，優選為處於3,000 cP～10,000 cP的範圍。另外，聚醯亞胺前體的分子量可利用膠體滲透層析（gel permeation chromatography，GPC）法來求出。聚醯亞胺前體的優選的分子量範圍（聚苯乙烯換算）理想的是數量平均分子量為15,000～250,000、重量平均分子量為30,000～800,000的範圍，但這些是標準，並非不可使用所述範圍外的所有聚醯亞胺前體。再者，聚醯亞胺的分子量也處於與其前體的分子量相同的範圍內。The preferred polymerization degree of the polyfluorene imide precursor and the polyfluorene imide of the present invention can be 1,000 cP to 100,000 cP in terms of the viscosity conversion of the polyimide precursor solution measured with an E-type viscometer, and is preferably It is in the range of 3,000 cP to 10,000 cP. The molecular weight of the polyfluorene imine precursor can be determined by a gel permeation chromatography (GPC) method. The preferred molecular weight range (in terms of polystyrene) of the polyimide precursor is preferably a range of a number average molecular weight of 15,000 to 250,000 and a weight average molecular weight of 30,000 to 800,000. Of all polyimide precursors. The molecular weight of polyimide is also in the same range as the molecular weight of its precursor.

對本發明的聚醯亞胺前體進行醯亞胺化而得的聚醯亞胺可為：在厚度10 μm～20 μm的聚醯亞胺膜的狀態下，黃色度（YI）為10以下、優選為6以下。更優選為4以下。若為所述範圍，則可適宜地用於有機EL裝置用TFT基板、觸控螢幕基板、彩色濾光片基板等要求透明性或著色少的基板。 就可撓性裝置用基板的耐熱性的觀點而言，玻璃轉移溫度（Tg）可為200℃以上、優選為250℃以上。另外，熱分解溫度（1%重量減少溫度，Td1）可為350℃以上。 彈性係數（E'）可為4 GPa以下。優選為3.5 GPa以下。此處，只要無特別的說明，則彈性係數為室溫下的拉伸彈性係數。若為所述範圍，則當製造有機EL裝置用TFT基板、觸控螢幕基板、彩色濾光片等中的功能層積層等可撓性裝置時，基板的殘餘應力少，且可撓性裝置的製造良率優異。 關於厚度方向的延遲Rth，以膜厚度10 μm換算而成的值（Rth10）優選為800 nm以下，更優選為500 nm以下，進而優選為200 nm以下。若為所述範圍，則例如在用作觸控螢幕基板的情況下，視認性等光學特性優異。 就可撓性裝置用基板的透明性的觀點而言，可為：在厚度10 μm～15 μm的膜的狀態下，可見光區域的全光線透過率為70%以上、優選為80%以上。在厚度10 μm～15 μm的聚醯亞胺膜的狀態下，450 nm的透光率優選為70%以上，更優選為80%以上。進而優選的是，除此以外，308 nm的透光率為3%以下，進而優選為低於1%，進而優選為低於0.1%。若為所述範圍，則吸收近紫外區域的光線，且紫外區域光線的透過率高。可一面保持可見光區域的透明性，一面吸收由準分子雷射器等發射的308 nm雷射光。結果，在有機EL裝置用基板、觸控螢幕基板、具有頂部發光（top emission）結構的彩色濾光片基板等可撓性裝置的製造步驟中，通過對可撓性基板進行雷射照射，可不對聚醯亞胺膜層上的顯示裝置造成損害地將支撐基材的玻璃剝離。即，可優選地應用雷射剝離（laser lift-off）法。 再者，所謂雷射剝離法，例如為如下技術：通過在支撐基材的玻璃上形成聚醯亞胺膜層，繼而在所述聚醯亞胺膜層上形成後述功能層而製成積層體。透過所述積層體的玻璃對聚醯亞胺膜的底面照射雷射，由此將玻璃與聚醯亞胺膜層剝離。The polyimide obtained by subjecting the polyimide precursor of the present invention to imidization may be as follows: in a state of a polyimide film having a thickness of 10 μm to 20 μm, the yellowness (YI) is 10 or less, It is preferably 6 or less. It is more preferably 4 or less. If it is the said range, it can use suitably for the board | substrate which requires transparency or little coloration, such as a TFT substrate for organic EL devices, a touchscreen substrate, and a color filter substrate. From the viewpoint of the heat resistance of the substrate for a flexible device, the glass transition temperature (Tg) may be 200 ° C or higher, and preferably 250 ° C or higher. In addition, the thermal decomposition temperature (1% weight reduction temperature, Td1) may be 350 ° C or higher. The coefficient of elasticity (E ') may be 4 GPa or less. It is preferably 3.5 GPa or less. Here, unless otherwise specified, the coefficient of elasticity is the coefficient of tensile elasticity at room temperature. If it is within the above range, when a flexible device such as a functional lamination layer in a TFT substrate for an organic EL device, a touch screen substrate, a color filter, or the like is manufactured, the residual stress of the substrate is small, and Excellent manufacturing yield. The retardation Rth in the thickness direction is preferably 800 nm or less, more preferably 500 nm or less, and still more preferably 200 nm or less in terms of a film thickness conversion value of 10 μm (Rth10). If it is the said range, when it is used as a touchscreen substrate, it will be excellent in optical characteristics, such as visibility. From the viewpoint of transparency of the substrate for a flexible device, in a state of a film having a thickness of 10 μm to 15 μm, the total light transmittance in the visible light region may be 70% or more, and preferably 80% or more. In the state of a polyimide film having a thickness of 10 μm to 15 μm, the light transmittance at 450 nm is preferably 70% or more, and more preferably 80% or more. Furthermore, it is more preferable that the light transmittance at 308 nm is 3% or less, more preferably less than 1%, and still more preferably less than 0.1%. If it is in the range, the light in the near ultraviolet region is absorbed, and the light transmittance in the ultraviolet region is high. While maintaining transparency in the visible light region, it absorbs 308 nm laser light emitted by excimer lasers and the like. As a result, in the manufacturing steps of a flexible device such as a substrate for an organic EL device, a touch screen substrate, and a color filter substrate having a top emission structure, the flexible substrate can be eliminated by laser irradiation. The display device on the polyimide film layer damages the glass supporting the substrate and peels off. That is, a laser lift-off method can be preferably applied. In addition, the so-called laser peeling method is, for example, a technique of forming a laminated body by forming a polyimide film layer on a glass supporting a substrate, and then forming a functional layer described later on the polyimide film layer . The bottom of the polyimide film is irradiated with laser light through the glass of the laminate, and the glass and the polyimide film layer are peeled off.

滿足所述特性的聚醯亞胺前體及聚醯亞胺是通過將本發明的聚醯亞胺前體及聚醯亞胺中作為必需或優選的結構單元而包含的所述式（1）所表示的芳香族二胺及所述式（2）所表示的含矽二胺的含量設為一定以上等來獲得。The polyfluorene imide precursor and the polyfluorene imide satisfying the characteristics are the formula (1) included by using the polyfluorene imide precursor and the polyfluorene imide of the present invention as necessary or preferred structural units. The obtained aromatic diamine and the content of the silicon-containing diamine represented by the formula (2) are set to a certain value or more.

將聚醯亞胺前體形成為聚醯亞胺的方法並無限制，在將聚醯亞胺用作樹脂基板的情況下，有利的是以膜狀或包含聚醯亞胺層的積層體的形式獲得。 優選的是可通過以下方式獲得聚醯亞胺積層體：將包含聚醯亞胺前體的樹脂溶液（樹脂組成物）塗布於基板上後進行乾燥、熱處理；或者將在液相中完成了醯亞胺化的樹脂溶液塗布於基材上並進行乾燥；或者將另行製作的聚醯亞胺膜貼附至另一基材上。就生產效率的觀點而言，理想的是如所述那樣在基材上進行醯亞胺化而直接形成積層體，並視需要將其剝離而形成膜。The method for forming the polyfluorene imide precursor into a polyfluorene is not limited. In the case where the polyfluorine is used as the resin substrate, it is advantageous in the form of a film or a laminate including a polyfluorine layer. obtain. Preferably, the polyfluorene imide laminate can be obtained by applying a resin solution (resin composition) containing a polyfluorene imide precursor on a substrate and then drying and heat-treating it; The imidized resin solution is coated on a substrate and dried; or a separately prepared polyimide film is attached to another substrate. From the viewpoint of production efficiency, it is desirable to directly form a laminated body by performing sulfonimidization on a substrate as described above, and peeling it as necessary to form a film.

本發明的聚醯亞胺適宜作為帶功能層的聚醯亞胺膜。所述情況下的聚醯亞胺膜可設為包含多層聚醯亞胺。在單層的情況下，可設為具有3 μm～50 μm的厚度。另一方面，在多層的情況下，只要為主要的聚醯亞胺層具有所述厚度的聚醯亞胺膜即可。此處所謂主要的聚醯亞胺層，是指在多層聚醯亞胺中厚度占最大比率的聚醯亞胺層，且為包含本發明的聚醯亞胺的層，優選的是可將其厚度設為3 μm～50 μm，進而優選為4 μm～30 μm。The polyfluorene imide of the present invention is suitable as a polyfluorene imine film with a functional layer. The polyimide film in this case can be set to include a multilayer polyimide. In the case of a single layer, the thickness may be 3 μm to 50 μm. On the other hand, in the case of multiple layers, it is sufficient if the main polyimide layer has a polyimide film having the thickness described above. The main polyfluorene imide layer herein refers to a polyfluorene imide layer having the largest thickness in the multilayer polyfluorene imide, and is a layer containing the polyfluorene imide of the present invention. The thickness is set to 3 μm to 50 μm, and more preferably 4 μm to 30 μm.

本發明的聚醯亞胺可形成具有所述聚醯亞胺層的積層體，並在所述聚醯亞胺層表面上形成具有各種功能的元件層等（功能層）。若對功能層進行舉例，則為以液晶顯示裝置、有機EL顯示裝置、觸控螢幕、電子紙為首的顯示裝置，可列舉：彩色濾光片等的顯示裝置或它們的構成零件。另外，還包括：包含有機EL照明裝置、觸控螢幕裝置、層疊有ITO等的導電性膜、觸控螢幕用膜、防止水分或氧等的滲透的阻氣膜、可撓性電路基板的構成零件等在內的隨附於所述顯示裝置而使用的各種功能裝置。即，此處所述的功能層不僅包括液晶顯示裝置、有機EL顯示裝置、及彩色濾光片等的構成零件，還包括將有機EL照明裝置、觸控螢幕裝置、有機EL顯示裝置的電極層或發光層、阻氣膜、黏接膜、薄膜電晶體（TFT）、液晶顯示裝置的配線層或透明導電層等的一種或兩種以上組合而成者。The polyfluorene imide of the present invention can form a laminate having the polyfluorene imine layer, and form an element layer or the like (functional layer) having various functions on the surface of the polyfluorene imine layer. If the functional layer is exemplified, it is a display device including a liquid crystal display device, an organic EL display device, a touch screen, and electronic paper, and examples thereof include display devices such as color filters or their constituent parts. In addition, it also includes a structure including an organic EL lighting device, a touch screen device, a conductive film laminated with ITO and the like, a film for a touch screen, a gas barrier film that prevents permeation of moisture and oxygen, and a flexible circuit board. Various functional devices including parts and the like that are used in conjunction with the display device. That is, the functional layer described here includes not only constituent components such as a liquid crystal display device, an organic EL display device, and a color filter, but also an electrode layer for organic EL lighting devices, touch screen devices, and organic EL display devices. Or a combination of one or more of a light-emitting layer, a gas barrier film, an adhesive film, a thin film transistor (TFT), a wiring layer of a liquid crystal display device, or a transparent conductive layer.

功能層的形成方法可根據目標裝置來適當地設定形成條件，通常可使用在聚醯亞胺膜上形成金屬膜、無機膜、有機膜等後視需要圖案化為規定的形狀、或進行熱處理等公知的方法來獲得。即，關於用以形成所述顯示元件的手段並無特別限制，例如可適當地選擇濺鍍、蒸鍍、化學氣相沉積（chemical vapor deposition，CVD）、印刷、曝光、浸漬等，在必要情況下也可在真空腔室內等進行所述製程處理。而且，對基板與聚醯亞胺膜進行的分離可在經由各種製程處理而形成功能層之後立即進行，也可在一定期間內與基材保持為一體而在即將以例如顯示裝置的形式利用之前進行分離去除。The formation method of the functional layer can be appropriately set according to the target device. Usually, a metal film, an inorganic film, an organic film, or the like can be formed on the polyimide film to be patterned into a predetermined shape as required, or heat-treated. Well-known methods to obtain. That is, the means for forming the display element is not particularly limited. For example, sputtering, vapor deposition, chemical vapor deposition (CVD), printing, exposure, dipping, and the like may be appropriately selected. If necessary, The process may be performed in a vacuum chamber or the like. Moreover, the separation between the substrate and the polyimide film can be performed immediately after forming a functional layer through various processing processes, or it can be kept integrated with the base material for a certain period of time, just before being used in the form of a display device, for example. Separation and removal.

以下，作為本發明的可撓性裝置的一例，對作為功能層的底部發光結構的有機EL顯示裝置的製造方法的概略進行說明。Hereinafter, as an example of the flexible device of the present invention, the outline of a method for manufacturing an organic EL display device as a bottom-emission structure of a functional layer will be described.

在本發明的聚醯亞胺膜上設置阻氣層而成為可阻止水分或氧的透濕的結構。接下來，在阻氣層的上表面形成包含薄膜電晶體（TFT）的電路構成層。所述情況下，在有機EL顯示裝置中主要選擇動作速度快的低溫多晶矽（low temperature poly-silicon，LTPS）-TFT作為薄膜電晶體。所述電路構成層是對在其上表面以矩陣狀配置有多個的像素區域中的各個形成例如包含ITO（Indium Tin Oxide）的透明導電膜的陽極電極而構成。進而，在陽極電極的上表面形成有機EL發光層，並在所述發光層的上表面形成陰極電極。所述陰極電極共通地形成於各像素區域。而且，以被覆所述陰極電極表面的方式再次形成阻氣層，進而在最表面，為了保護表面而設置密封基板。就可靠性的觀點而言，理想的是也在所述密封基板的陰極電極側的表面層疊阻止水分或氧的透濕的阻氣層。再者，有機EL發光層是由電洞注入層-電洞傳輸層-發光層-電子傳輸層等多層膜（陽極電極-發光層-陰極電極）形成，尤其有機EL發光層會因水分或氧而劣化，因此是利用真空蒸鍍來形成，從而也包括電極形成在內通常是在真空中連續地形成。A gas barrier layer is provided on the polyfluorene imide film of the present invention to have a structure that can prevent moisture or oxygen from passing through. Next, a circuit configuration layer including a thin film transistor (TFT) is formed on the upper surface of the gas barrier layer. In the above case, in the organic EL display device, a low temperature poly-silicon (LTPS) -TFT with a fast operating speed is mainly selected as the thin film transistor. The circuit configuration layer is constituted of an anode electrode in which a transparent conductive film including ITO (Indium Tin Oxide) is formed on each of a plurality of pixel regions arranged in a matrix on the upper surface thereof. Further, an organic EL light-emitting layer is formed on the upper surface of the anode electrode, and a cathode electrode is formed on the upper surface of the light-emitting layer. The cathode electrode is commonly formed in each pixel region. A gas barrier layer is formed again so as to cover the surface of the cathode electrode, and a sealing substrate is further provided on the outermost surface to protect the surface. From the viewpoint of reliability, it is desirable that a gas barrier layer that blocks moisture or oxygen is also laminated on the surface of the cathode electrode side of the sealing substrate. In addition, the organic EL light-emitting layer is formed of a multilayer film (anode electrode-light-emitting layer-cathode electrode) such as a hole injection layer, a hole transport layer, a light-emitting layer, and an electron transport layer. In particular, the organic EL light-emitting layer may be affected by moisture or oxygen. Deterioration is formed by vacuum evaporation, and thus it is usually formed continuously in a vacuum, including electrode formation.

自所述有機EL顯示裝置的發光層發出的光的波長主要為440 nm至780 nm，因此，作為有機EL顯示裝置中使用的透明樹脂基板，要求在所述波長區域中的平均透過率至少為80%以上。另一方面，在上文所述的利用紫外（ultraviolet，UV）雷射光的照射進行玻璃與聚醯亞胺層的剝離的情況下，若UV雷射光的波長下的透過率高，則需要另外設置吸收/剝離層，因此生產性降低。所述剝離中目前通常使用308 nm雷射裝置。為了在不設置所述吸收/剝離層的條件下進行剝離，聚醯亞胺本身需要充分吸收308 nm雷射光，理想的是儘量不使光透過。The wavelength of light emitted from the light-emitting layer of the organic EL display device is mainly 440 nm to 780 nm. Therefore, as a transparent resin substrate used in the organic EL display device, an average transmittance in the wavelength region is required to be at least More than 80%. On the other hand, in the case where the glass and the polyimide layer are peeled off by irradiation with ultraviolet (UV) laser light as described above, if the transmittance at the wavelength of the UV laser light is high, it is necessary to separately Since an absorption / release layer is provided, productivity is lowered. A 308 nm laser device is currently commonly used in the stripping. In order to perform the peeling without providing the absorption / release layer, the polyimide itself needs to sufficiently absorb 308 nm laser light, and it is desirable to prevent light from being transmitted as much as possible.

[實施例] 以下，基於實施例及比較例來對本發明進行具體說明。再者，本發明並不受這些內容限制。[Examples] Hereinafter, the present invention will be specifically described based on examples and comparative examples. The invention is not limited by these contents.

示出實施例及比較例中使用的材料的代號及評價方法。 （酸二酐） ·PMDA：均苯四甲酸二酐 ·6FDA：4,4'-(2,2'-六氟亞異丙基)二鄰苯二甲酸二酐 ·CBDA：1,2,3,4-環丁烷四羧酸二酐 （二胺） ·TFMB：2,2'-雙(三氟甲基)聯苯胺 ·AAPBZI：5-氨基-2-(4-氨基苯基)苯並咪唑 ·BY16-871：二氨基丙基四甲基二矽氧烷（東麗道康寧（Toray Dow Corning）製造，胺當量125 g/mol，式2的m=1） ·X-22-1660B-3：兩末端氨基改質甲基苯基矽酮（信越化學股份有限公司製造，胺當量2160 g/mol） （溶劑） ·NMP：N-甲基-2-吡咯啶酮The codes and evaluation methods of the materials used in the examples and comparative examples are shown. (Acid dianhydride) · PMDA: pyromellitic dianhydride · 6FDA: 4,4 '-(2,2'-hexafluoroisopropylidene) diphthalic dianhydride · CBDA: 1,2,3 , 4-cyclobutanetetracarboxylic dianhydride (diamine) · TFMB: 2,2'-bis (trifluoromethyl) benzidine · AAPBZI: 5-amino-2- (4-aminophenyl) benzo Imidazole · BY16-871: Diaminopropyltetramethyldisilazane (manufactured by Toray Dow Corning, amine equivalent 125 g / mol, m = 1 of formula 2) · X-22-1660B-3 ： Methylphenyl silicone modified by amino at both ends (manufactured by Shin-Etsu Chemical Co., Ltd., amine equivalent 2160 g / mol) (solvent) · NMP: N-methyl-2-pyrrolidone

（透光率T450及黃色度YI） 利用島津（SHIMADZU）UV-3600分光光度計對聚醯亞胺膜（50 mm×50 mm）求出450 nm下的透光率（T450）。 另外，基於下式（5）所表示的計算式來算出YI（黃色度）。 YI=100×(1.2879X-1.0592Z)/Y （5） X、Y、Z為試驗片的三刺激值，在日本工業標準（Japanese Industrial Standards，JIS）Z 8722中進行了規定。 算出下式（6）所表示的以厚度10 μm換算而成的值YI10。 YI10=YI/厚度*10 （6）(Light transmittance T450 and yellowness YI) The Shimadzu UV-3600 spectrophotometer was used to determine the light transmittance (T450) at 450 nm for the polyimide film (50 mm × 50 mm). In addition, YI (yellowness) is calculated based on a calculation formula represented by the following formula (5). YI = 100 × (1.2879X-1.0592Z) / Y (5) X, Y, and Z are the tristimulus values of the test piece, which are specified in Japanese Industrial Standards (JIS) Z 8722. A value YI10 converted to a thickness of 10 μm represented by the following formula (6) was calculated. YI10 = YI / thickness * 10 (6)

（熱膨脹係數：CTE） 利用熱機械分析（thermomechanical analysis，TMA）裝置，一面對聚醯亞胺膜（3 mm×15 mm）施加5.0 g的荷重，一面以一定的升溫速度（10℃/min）自30℃升溫至220℃，繼而，自200℃降溫至100℃，並根據降溫時的聚醯亞胺膜的伸長量測定熱膨脹係數。(Coefficient of Thermal Expansion: CTE) Using a thermomechanical analysis (TMA) device, a 5.0 g load is applied to the polyimide film (3 mm x 15 mm), and the temperature is increased at a certain rate (10 ° C / min) ) The temperature was increased from 30 ° C to 220 ° C, and then was lowered from 200 ° C to 100 ° C, and the thermal expansion coefficient was measured based on the elongation of the polyimide film at the time of temperature decrease.

（熱分解溫度：Td1） 利用精工（SEIKO）製造的熱重量分析（thermogravimetric，TG）裝置TG/DTA6200來測定使聚醯亞胺膜（10 mg～20 mg）在氮氣環境下以10℃/min的升溫速度自30℃升溫至550℃時的重量變化，將200℃下的重量設為零，將重量減少率為1%時的溫度設為熱分解溫度（Td1）。(Thermal decomposition temperature: Td1) The thermogravimetric (TG) device TG / DTA6200 manufactured by SEIKO was used to measure the polyimide film (10 mg-20 mg) in a nitrogen environment at 10 ° C / min. The change in weight when the temperature rise rate from 30 ° C to 550 ° C is set, the weight at 200 ° C is set to zero, and the temperature at which the weight reduction rate is 1% is set to the thermal decomposition temperature (Td1).

（玻璃轉移溫度；Tg） 利用動態熱機械分析裝置對聚醯亞胺膜（5 mm×70 mm）測定以5℃/min自23℃升溫至400℃時的動態黏彈性，並將顯示出tanδ極大值的溫度設為玻璃轉移溫度（Tg）。(Glass transition temperature; Tg) The dynamic viscoelasticity of a polyimide film (5 mm × 70 mm) was measured at a temperature of 5 ° C / min from 23 ° C to 400 ° C using a dynamic thermomechanical analysis device, and tanδ was displayed. The temperature at the maximum value was set as the glass transition temperature (Tg).

（拉伸彈性係數：E'） 使用張力測試儀（tension tester）對聚醯亞胺膜（12.4 mm×160 mm）一面施加10 kg的荷重，一面以50 mm/min進行拉伸試驗。(Tensile Elastic Coefficient: E ') A tensile tester was used to apply a 10 kg load to the polyimide film (12.4 mm × 160 mm), and the tensile test was performed at 50 mm / min.

（全光線透過率：TT） 利用霧度計對聚醯亞胺膜（50 mm×50 mm）測定全光線透過率。(Total light transmittance: TT) The haze meter was used to measure the total light transmittance of the polyimide film (50 mm × 50 mm).

（延遲：Rth10） 針對聚醯亞胺膜（50 mm×50 mm），使用雙折射、相位差評價裝置（光子晶格（Photonic-Lattice）股份有限公司製造的WPA-100），且為了變更入射至試樣的光的入射角而安裝使試樣旋轉的旋轉裝置，在波長543 nm下測定聚醯亞胺膜的延遲的入射角依賴性。對所述延遲的入射角依賴性的測定數據進行數值分析，求出厚度方向的延遲Rth。將以膜厚度10 μm換算後的值設為Rth10。 （殘餘應力） 使用東朋技術公司（Toho Technology）製造的薄膜應力測量裝置FLX-2320進行測量。在6吋矽晶片上形成10μm的聚醯亞胺膜，測量在成膜前後矽晶片的翹曲，並計算聚醯亞胺膜的殘餘應力。(Delay: Rth10) For polyimide film (50 mm × 50 mm), a birefringence and retardation evaluation device (WPA-100 manufactured by Photonic-Lattice Co., Ltd.) was used to change the incidence A rotating device that rotates the sample is attached to the incident angle of light to the sample, and the retardation incident angle dependence of the polyfluoreneimide film is measured at a wavelength of 543 nm. The retardation incident angle dependence measurement data was numerically analyzed to determine the retardation Rth in the thickness direction. The value converted into a film thickness of 10 μm was set to Rth10. (Residual stress) Measurement was performed using a thin film stress measuring device FLX-2320 manufactured by Toho Technology. A 10 μm polyimide film was formed on a 6-inch silicon wafer, the warpage of the silicon wafer before and after film formation was measured, and the residual stress of the polyimide film was calculated.

依照下述合成例1～合成例11，製備用以形成實施例及比較例的聚醯亞胺積層體中的聚醯亞胺層的樹脂溶液（聚醯亞胺前體溶液）。再者，將各聚醯亞胺前體溶液中的單體的重量（g）組成匯總示於表1中。A resin solution (polyimide precursor solution) for forming a polyimide layer in the polyimide laminate of the examples and comparative examples was prepared according to the following Synthesis Examples 1 to 11. In addition, the weight (g) composition of the monomer in each polyfluorene imide precursor solution is shown in Table 1.

合成例1 在氮氣氣流下，在100 ml的可分離式燒瓶中使3.02 g的BY16-871溶解於70 g的NMP中。繼而，在所述溶液中添加9.04 g的TFMB。攪拌10分鐘後添加17.93 g的6FDA。再者，將酸二酐（a）與二胺（b）的莫耳比（a/b）設為1.0。對所述溶液以40℃加熱10分鐘而使內容物溶解，其後，在室溫下對溶液持續攪拌10小時以進行聚合反應，獲得高聚合度的聚醯亞胺（polyimide，PI）前體A（黏稠的溶液）。Synthesis Example 1 Under nitrogen gas flow, 3.02 g of BY16-871 was dissolved in 70 g of NMP in a 100 ml separable flask. Then, 9.04 g of TFMB was added to the solution. After stirring for 10 minutes, 17.93 g of 6FDA was added. The molar ratio (a / b) of the acid dianhydride (a) and the diamine (b) was 1.0. The solution was heated at 40 ° C for 10 minutes to dissolve the contents, and then the solution was continuously stirred at room temperature for 10 hours to perform a polymerization reaction to obtain a polyimide (PI) precursor having a high degree of polymerization. A (viscous solution).

合成例2 在氮氣氣流下，在100 ml的可分離式燒瓶中使2.44 g的BY16-871溶解於70 g的NMP中。繼而，在所述溶液中添加11.44 g的TFMB。攪拌10分鐘後添加12.14 g的6FDA，接著添加3.98 g的PMDA。再者，將酸二酐（a）與二胺（b）的莫耳比（a/b）設為1.0。對所述溶液以40℃加熱10分鐘而使內容物溶解，其後，在室溫下對溶液持續攪拌10小時以進行聚合反應，獲得高聚合度的聚醯亞胺（PI）前體B（黏稠的溶液）。Synthesis Example 2 Under a stream of nitrogen, 2.44 g of BY16-871 was dissolved in 70 g of NMP in a 100 ml separable flask. Then, 11.44 g of TFMB was added to the solution. After stirring for 10 minutes, 12.14 g of 6FDA was added, followed by 3.98 g of PMDA. The molar ratio (a / b) of the acid dianhydride (a) and the diamine (b) was 1.0. The solution was heated at 40 ° C. for 10 minutes to dissolve the contents, and then the solution was continuously stirred at room temperature for 10 hours to perform a polymerization reaction to obtain a highly polymerized polyimide (PI) precursor B ( Viscous solution).

合成例3～合成例9 除將酸二酐（a）及二胺（b）變更為表1所示的質量（g）組成以外，與合成例1同樣地製備聚醯亞胺前體溶液，獲得聚醯亞胺（PI）前體C～聚醯亞胺（PI）前體I。Synthesis Example 3 to Synthesis Example 9 A polyimide precursor solution was prepared in the same manner as in Synthesis Example 1 except that the acid dianhydride (a) and diamine (b) were changed to the mass (g) composition shown in Table 1. Polyimide (PI) precursor C to polyimide (PI) precursor I were obtained.

合成例10～合成例11 除將酸二酐（a）及二胺（b）變更為表1所示的質量（g）組成以外，與合成例1同樣地製備聚醯亞胺前體溶液，獲得聚醯亞胺（PI）前體J～聚醯亞胺（PI）前體K。Synthesis Example 10 to Synthesis Example 11 A polyimide precursor solution was prepared in the same manner as in Synthesis Example 1 except that the acid dianhydride (a) and diamine (b) were changed to the mass (g) composition shown in Table 1. Polyimide (PI) precursor J to polyimide (PI) precursor K were obtained.

[表1] [Table 1]

實施例1 在合成例1中所獲得的聚醯亞胺前體溶液A中添加溶劑NMP而以黏度成為4000 cP的方式進行稀釋，然後使用棒塗機，以硬化後的聚醯亞胺厚度成為約10 μm的方式塗敷於75 μm的優匹萊克斯（UPILEX）-S膜的支撐基材上。接著，以100℃進行15分鐘加熱。然後，在氮氣環境中，以一定的升溫速度（3℃/min）自室溫升溫至340℃，中途在130℃下保持10 min，從而在支撐基材上形成聚醯亞胺層（聚醯亞胺A），獲得聚醯亞胺積層體A。然後，剝離聚醯亞胺基材而獲得聚醯亞胺（PI）膜A。所述剝離是通過以下方式來進行：利用切割刀僅對所形成的聚醯亞胺層切出一周切口以決定進行剝離的範圍後，利用鑷子自基板進行剝離。再者，這些膜的厚度示出於厚度一項中。Example 1 A solvent NMP was added to the polyfluorene imine precursor solution A obtained in Synthesis Example 1 to dilute the solution to a viscosity of 4000 cP, and then the thickness of the cured polyfluorene imine was changed with a bar coater to Approx. 10 μm is coated on a 75 μm UPILEX-S film support substrate. Then, it heated at 100 degreeC for 15 minutes. Then, in a nitrogen environment, the temperature was raised from room temperature to 340 ° C at a certain temperature increase rate (3 ° C / min), and maintained at 130 ° C for 10 minutes, thereby forming a polyimide layer (Polyimide) Amine A) to obtain a polyfluorene imide laminate A. Then, the polyimide substrate was peeled to obtain a polyimide (PI) film A. The peeling is performed by cutting a formed polyimide layer with a dicing knife only for one week to determine the range of peeling, and then peeling from the substrate with tweezers. In addition, the thickness of these films is shown in the thickness item.

實施例2～實施例5、比較例1～比較例2 除將合成例2～合成例5、合成例7、合成例8中所獲得的聚醯亞胺前體改為聚醯亞胺（PI）前體B～聚醯亞胺（PI）前體E、聚醯亞胺（PI）前體G、聚醯亞胺（PI）前體H中的任一者以外，與實施例1同樣地進行操作而獲得聚醯亞胺膜B～聚醯亞胺膜E、聚醯亞胺膜G、聚醯亞胺膜H。Example 2 to Example 5, Comparative Example 1 to Comparative Example 2 Except that the polyimide precursor obtained in Synthesis Example 2 to Synthesis Example 5, Synthesis Example 7, Synthesis Example 8 was changed to polyimide (PI ) Precursor B to polyimide (PI) precursor E, polyimide (PI) precursor G, or polyimide (PI) precursor H, the same as Example 1 The polyimide film B to the polyimide film E, the polyimide film G, and the polyimide film H were obtained by performing operations.

實施例6 在合成例6中所獲得的聚醯亞胺前體溶液F中添加溶劑NMP而以黏度成為4000 cP的方式進行稀釋，然後使用旋塗機，以硬化後的聚醯亞胺厚度成為約10 μm的方式塗敷於玻璃基板（旭硝子製造的AN100，尺寸=150 mm×150 mm，厚度=0.7 mm）上。接著，以100℃進行15分鐘加熱。然後，在氮氣環境中，以一定的升溫速度（3℃/min）自室溫升溫至340℃，中途在130℃下保持10 min，從而在玻璃基板上形成150 mm×150 mm的聚醯亞胺層（聚醯亞胺F），獲得聚醯亞胺積層體F。 對於所獲得的聚醯亞胺積層體F，使用準分子雷射加工機（波長308 nm）以300 mJ/cm2 的能量密度自支撐基材的玻璃基板側照射束尺寸為14 mm×1.2 mm、移動速度為6 mm/s的雷射，使支撐基材與聚醯亞胺層成為完全分離的狀態，利用切割刀決定剝離範圍，在切入一周切口後聚醯亞胺膜自玻璃自然剝離，獲得聚醯亞胺膜F。Example 6 A solvent NMP was added to the polyfluorene imine precursor solution F obtained in Synthesis Example 6 to dilute it so that the viscosity became 4000 cP, and then the thickness of the cured polyfluorene imide was changed by using a spin coater. Approx. 10 μm was applied on a glass substrate (AN100 manufactured by Asahi Glass, size = 150 mm × 150 mm, thickness = 0.7 mm). Then, it heated at 100 degreeC for 15 minutes. Then, in a nitrogen environment, the temperature was raised from room temperature to 340 ° C at a certain temperature increase rate (3 ° C / min), and maintained at 130 ° C for 10 minutes in the middle, so that a 150 mm x 150 mm polyimide was formed on the glass substrate. Layer (polyimide F) to obtain polyimide laminate F. With respect to the obtained polyfluorene imine laminate F, an excimer laser processor (wavelength 308 nm) was used to irradiate the glass substrate side of the support substrate at an energy density of 300 mJ / cm 2 with a beam size of 14 mm × 1.2 mm. The laser with a moving speed of 6 mm / s makes the supporting substrate and the polyimide layer completely separated, and uses a cutter to determine the peeling range. After cutting into a week, the polyimide film is naturally peeled from the glass. A polyimide film F was obtained.

實施例7 在合成例9中所獲得的聚醯亞胺前體溶液I中添加溶劑NMP而以黏度成為4000 cP的方式進行稀釋，然後使用棒塗機，以硬化後的聚醯亞胺厚度成為約10 μm的方式塗敷於75 μm的優匹萊克斯（UPILEX）-S膜的支撐基材上。接著，以100℃進行15分鐘加熱。然後，在氮氣環境中，以一定的升溫速度（3℃/min）自室溫升溫至300℃，中途在130℃下保持10 min，從而在支撐基材上形成聚醯亞胺層（聚醯亞胺I），獲得聚醯亞胺積層體I。然後，利用與實施例1相同的方法剝離聚醯亞胺基材而獲得聚醯亞胺膜I。Example 7 The solvent NMP was added to the polyimide precursor solution I obtained in Synthesis Example 9 to dilute it to a viscosity of 4000 cP. Then, the thickness of the cured polyimide was changed to a thickness using a bar coater. Approx. 10 μm is coated on a 75 μm UPILEX-S film support substrate. Then, it heated at 100 degreeC for 15 minutes. Then, in a nitrogen environment, the temperature was raised from room temperature to 300 ° C at a certain temperature increase rate (3 ° C / min), and maintained at 130 ° C for 10 minutes, so that a polyimide layer (Polyimide) was formed on the supporting substrate. Amine I) to obtain a polyfluorene imide laminate I. Then, the polyimide substrate was peeled off by the same method as in Example 1 to obtain a polyimide film I.

實施例8～實施例9 除將合成例10～合成例11中所獲得的聚醯亞胺前體改為聚醯亞胺（PI）前體J～聚醯亞胺（PI）前體K中的任一者以外，與實施例1同樣地進行操作而獲得聚醯亞胺膜J～聚聚醯亞胺膜K。Examples 8 to 9 Except that the polyimide precursor obtained in Synthesis Example 10 to Synthesis Example 11 was changed to polyimide (PI) precursor J to polyimide (PI) precursor K A polyimide film J to a polyimide film K were obtained in the same manner as in Example 1 except for any of them.

對所獲得的聚醯亞胺（PI）膜A～聚醯亞胺（PI）膜K進行各種評價。將結果示於表2與表3中。The obtained polyimide (PI) film A to polyimide (PI) film K were subjected to various evaluations. The results are shown in Tables 2 and 3.

[表2] [Table 2]

[表3] [table 3]

無no

無no

Claims (7)

一種聚醯亞胺前體，其特徵在於，具有源自二胺的結構單元與源自酸二酐的結構單元，其中，具有源自下述式（1）所表示的芳香族二胺的結構單元、以及源自下述式（2）所表示的含矽二胺的結構單元作為源自二胺的結構單元；（1） 式（1）中，Z1 及Z2 分別獨立地為碳數1～3的烷基或碳數1～3的氟取代烷基，（2） 式（2）中，R1 及R2 分別獨立地為碳數3～20的二價的脂肪族烴基、或碳數6～20的二價的芳香族烴基，R3 、R4 、R5 及R6 分別獨立地為碳數1～3的一價的脂肪族烴基、或碳數6～10的芳香族烴基，m為1～2的整數。A polyfluorene imine precursor comprising a structural unit derived from a diamine and a structural unit derived from an acid dianhydride, and having a structure derived from an aromatic diamine represented by the following formula (1) A unit derived from a diamine-containing structural unit represented by the following formula (2) as a structural unit derived from a diamine; (1) In the formula (1), Z 1 and Z 2 are each independently an alkyl group having 1 to 3 carbon atoms or a fluorine-substituted alkyl group having 1 to 3 carbon atoms, (2) In formula (2), R 1 and R 2 are each independently a divalent aliphatic hydrocarbon group having 3 to 20 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and R 3 and R 4 , R 5 and R 6 are each independently a monovalent aliphatic hydrocarbon group having 1 to 3 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and m is an integer of 1 to 2; 如申請專利範圍第1項所述的聚醯亞胺前體，其中，包含源自二胺的全部結構單元的5莫耳%～80莫耳%的源自所述式（2）所表示的含矽二胺的結構單元。The polyfluorene imide precursor according to item 1 of the scope of patent application, wherein 5 mole% to 80 mole% of all structural units derived from diamine are derived from the formula (2) Structural unit containing silamine. 一種聚醯亞胺，其特徵在於，具有源自二胺的結構單元與源自酸二酐的結構單元，其中，具有源自下述式（1）所表示的芳香族二胺的結構單元、以及源自下述式（2）所表示的含矽二胺的結構單元；（1） 式（1）中，Z1 及Z2 分別獨立地為碳數1～3的烷基或氟取代烷基，（2） 式（2）中，R1 及R2 分別獨立地為碳數3～20的二價的脂肪族烴基、或碳數6～20的二價的芳香族烴基，R3 、R4 、R5 及R6 分別獨立地為碳數1～3的一價的脂肪族烴基、或碳數6～10的芳香族烴基，m為1～2的整數。A polyimide having a structural unit derived from a diamine and a structural unit derived from an acid dianhydride, wherein the structural unit is derived from an aromatic diamine represented by the following formula (1), And derived from a silicon diamine-containing structural unit represented by the following formula (2); (1) In the formula (1), Z 1 and Z 2 are each independently an alkyl group having 1 to 3 carbon atoms or a fluorine-substituted alkyl group, (2) In formula (2), R 1 and R 2 are each independently a divalent aliphatic hydrocarbon group having 3 to 20 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and R 3 and R 4 , R 5 and R 6 are each independently a monovalent aliphatic hydrocarbon group having 1 to 3 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and m is an integer of 1 to 2; 如申請專利範圍第3項所述的聚醯亞胺，其中，黃色度為10以下。The polyimide according to item 3 of the scope of patent application, wherein the yellowness is 10 or less. 如申請專利範圍第3項所述的聚醯亞胺，其中，用於可撓性裝置用基板的用途。The polyfluorene imide according to item 3 of the scope of patent application, wherein the polyimide is used for a substrate for a flexible device. 一種積層體，其中，是在支撐體的表面上形成如申請專利範圍第5項所述的聚醯亞胺的層而成。A laminated body in which a polyimide layer as described in item 5 of the scope of patent application is formed on the surface of a support. 一種可撓性裝置，其中，是在如申請專利範圍第5項所述的聚醯亞胺的層的表面上形成功能層而成。A flexible device comprising a functional layer formed on a surface of a polyimide layer according to item 5 of the patent application scope.
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