TW201811871A - Polyimide precursor and polyimines formed from the polyimine precursor excellent in low thermal expansivity and film forming property, can be easily peeled from a supporting substrate, and has excellent heat resistance or high transparency - Google Patents

Polyimide precursor and polyimines formed from the polyimine precursor excellent in low thermal expansivity and film forming property, can be easily peeled from a supporting substrate, and has excellent heat resistance or high transparency Download PDF

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TW201811871A
TW201811871A TW106126674A TW106126674A TW201811871A TW 201811871 A TW201811871 A TW 201811871A TW 106126674 A TW106126674 A TW 106126674A TW 106126674 A TW106126674 A TW 106126674A TW 201811871 A TW201811871 A TW 201811871A
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polyimide
dianhydride
structural unit
precursor
diamine
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TWI786055B (en
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王宏遠
石山貴也
森本敏弘
平石克文
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新日鐵住金化學股份有限公司
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Abstract

To provide a polyimide and a precursor thereof, the polyimide is excellent in low thermal expansivity and film forming property, can be easily peeled from a supporting substrate, and has excellent heat resistance or high transparency. A polyimide precursor, and a polyimide obtained by subjecting the polyimide precursor to imidation, the polyimide precursor having a structural unit derived from a diamine and a structural unit derived from an acid dianhydride, and having (i) a structural unit derived from an aromatic diamine represented by the following formula (1), and (ii) a structural unit derived from 2,2'-bis(trifluoromethyl)benzidine or 1,2,3,4-cyclobutanetetracarboxylic dianhydride, in formula (1), Z is NH or O.

Description

聚醯亞胺前體及由所述聚醯亞胺前體生成的聚醯亞胺Polyfluorene imine precursor and polyfluorene imine formed from the polyfluorene imine precursor

本發明是有關於一種可用作形成兼具高透明性、低熱膨脹係數、高耐熱性、雷射剝離（laser lift-off）特性的顯示裝置的支持基材等的聚醯亞胺及其前體。The present invention relates to a polyimide which can be used as a support substrate for forming a display device having high transparency, low thermal expansion coefficient, high heat resistance, and laser lift-off characteristics, and the like. body.

關於以電視般的大型顯示器、或行動電話、個人電腦、智慧型手機等小型顯示器為首的各種顯示器用途中所使用的有機電致發光（electroluminescence，EL）裝置，通常是在作為支持基板的玻璃基板上形成薄膜電晶體（thin film transistor，TFT），進而在其上依次形成電極、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。有機EL裝置的結構中，有自支持基板側輸出光的底部發光（bottom emission）結構與自支持基板的相反側輸出光的頂部發光（top emission）結構，可根據用途靈活使用。對於底部發光結構的支持基材而言需要透明材料，但對頂部發光結構的支持基材而言也可為非透明材料。Organic electroluminescence (EL) devices used in various display applications, including large TV-like displays, or small displays such as mobile phones, personal computers, and smartphones, are usually glass substrates used as support substrates. A thin film transistor (TFT) is formed thereon, and then an electrode, a light emitting layer, and an electrode are sequentially formed thereon, and a glass substrate or a multilayer film is used to hermetically seal them. The organic EL device has a bottom emission structure that outputs light from the supporting substrate side and a top emission structure that outputs light from the opposite side of the supporting substrate, and can be used flexibly depending on the application. A transparent material is required for the supporting substrate of the bottom emitting structure, but a non-transparent material may also be used for the supporting substrate of the top emitting structure.

通過將這種有機EL裝置的支持基材從以前的玻璃基板替換為樹脂，可實現薄型･輕量･可撓化，從而可進一步拓寬有機EL裝置的用途。然而，樹脂的尺寸穩定性、透明性、耐熱性、耐濕性、膜的強度等通常比玻璃差，因此正進行各種研究。By replacing the supporting substrate of such an organic EL device from a conventional glass substrate with a resin, it is possible to realize a thin, lightweight, flexible, and further widen the use of the organic EL device. However, dimensional stability, transparency, heat resistance, moisture resistance, film strength, and the like of resins are generally inferior to those of glass, and various studies are being performed.

作為可用作可撓性顯示器用塑膠基材等的材料，已知有聚醯亞胺膜。例如，專利文獻1公開了一種包括聚醯亞胺膜與無機基板的層疊體、及自所述層疊體剝離而得的聚醯亞胺膜，所述聚醯亞胺膜是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得。所述聚醯亞胺膜形成為透光率高且逸氣（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差大，容易發生翹曲，從而在形成器件後會產生剝離或裂紋等，難以獲得形狀穩定性優異的有機EL裝置等的器件。As a material that can be used as a plastic substrate for a flexible display and the like, a polyimide film is known. For example, Patent Document 1 discloses a polyimide film including a laminate of a polyimide film and an inorganic substrate, and a polyimide film obtained by peeling from the laminate, the polyimide film being a polymer having a specific structure. The fluorene imine precursor solution is cast on an inorganic substrate, dried, and fluorinated. The polyfluorene film is formed with high light transmittance and low out gas, but the coefficient of thermal expansion (CTE) exceeds 40 ppm / K, so the CTE between the polyimide film and an inorganic substrate such as a glass substrate The difference is large, and warpage easily occurs, so that peeling or cracking may occur after the device is formed, and it is difficult to obtain a device such as an organic EL device having excellent shape stability.

另外，專利文獻2、專利文獻5公開了一種將聚醯亞胺膜自載體基板剝離而製造的顯示器件、光接收器件等可撓性器件基板形成用的聚醯亞胺前體樹脂組合物，並記載了所述聚醯亞胺膜示出300℃以上的玻璃轉移溫度與20 ppm/K以下的熱膨脹係數。In addition, Patent Documents 2 and 5 disclose a polyimide precursor resin composition for forming a flexible device substrate such as a display device and a light-receiving device produced by peeling a polyimide film from a carrier substrate. It is also described that the polyimide film shows a glass transition temperature of 300 ° C. or higher and a thermal expansion coefficient of 20 ppm / K or lower.

有機EL裝置對水分的耐受力弱，作為發光層的EL元件的特性會因水分而降低。因此，在使用樹脂作為支持基材的情況下，為了防止水分或氧侵入有機EL裝置內，優選的是吸濕率低的樹脂。另外，作為有機EL基板，通常使用以氧化矽或氮化矽為代表的無機系材料，這些無機系材料的CTE通常為0 ppm/K～10 ppm/K。相對於此，通常的聚醯亞胺的CTE大於10 ppm/K，因此，若僅將聚醯亞胺應用於有機EL裝置的支持基材，則有時會發生因熱應力而產生翹曲或裂紋，或者產生剝離等問題。專利文獻6將2,3,6,7-萘四羧酸二酐用作聚醯亞胺材料，但熱膨脹係數大於20 ppm/K而有可能發生翹曲。Organic EL devices have a low resistance to moisture, and the characteristics of an EL element as a light-emitting layer are reduced due to moisture. Therefore, in the case where a resin is used as a supporting substrate, in order to prevent moisture or oxygen from entering the organic EL device, a resin having a low moisture absorption rate is preferred. In addition, as the organic EL substrate, inorganic materials such as silicon oxide or silicon nitride are generally used, and the CTE of these inorganic materials is usually 0 ppm / K to 10 ppm / K. In contrast, the CTE of ordinary polyimide is greater than 10 ppm / K. Therefore, if polyimide is used only as a supporting substrate for an organic EL device, warpage or thermal stress may occur. Cracks, or problems such as peeling. Patent Document 6 uses 2,3,6,7-naphthalenetetracarboxylic dianhydride as a polyimide material, but the thermal expansion coefficient is greater than 20 ppm / K, and warpage may occur.

與此呼應地，也對設置於顯示裝置上的觸控面板的薄型化、輕量化、可撓化進行積極研究。In response to this, active research is also being conducted on the reduction in thickness, weight, and flexibility of the touch panel provided on the display device.

作為觸控面板的主要方式，大致分為檢測光的變化的方式與檢測電特性的變化的方式。作為檢測電特性的變化的方式，已知有電阻膜方式與靜電電容耦合方式。進而，靜電電容耦合方式中有表面型與投影型兩種方式，但就適於應對作為智慧手機等中不可欠缺的功能的多點觸控（multi touch）辨識（多點辨識）的觀點而言，投影型備受矚目。As a main method of the touch panel, it is roughly divided into a method of detecting a change in light and a method of detecting a change in electrical characteristics. As a method for detecting a change in electrical characteristics, a resistive film method and a capacitive coupling method are known. Furthermore, there are two types of electrostatic coupling methods: surface type and projection type, but from the viewpoint of multi-touch recognition (multi-point recognition) suitable for coping with indispensable functions in smartphones and the like. The projection type has attracted much attention.

投影型電容耦合方式的觸控面板沿縱橫方向設有兩列電極列（第1電極與第2電極），並可通過對手指觸碰畫面時電極的靜電電容變化進行測定來精密地檢測接觸位置。具體的結構為形成有第1電極的第1基板與形成有第2電極的第2基板經由絕緣層（介電層）接合而成的構成。為了薄型化、輕量化、可撓化，可通過將形成電極的基板從以前的玻璃基板替換為具有彎曲性的樹脂基材來實現。另外，將第1電極與第2電極形成於一個基板上也可推進進一步的薄型化、輕量化。The projection type capacitive coupling touch panel is provided with two rows of electrodes (the first electrode and the second electrode) in the vertical and horizontal directions, and can accurately detect the contact position by measuring the change in the electrostatic capacitance of the electrode when the finger touches the screen. . A specific structure is a structure in which a first substrate on which a first electrode is formed and a second substrate on which a second electrode is formed are bonded via an insulating layer (dielectric layer). In order to reduce the thickness, weight, and flexibility, this can be achieved by replacing the substrate on which the electrode is formed from a conventional glass substrate with a flexible resin substrate. In addition, by forming the first electrode and the second electrode on one substrate, further reduction in thickness and weight can be promoted.

在將觸控面板基板的一部分或全部替換為樹脂基材的情況下，聚醯亞胺受到關注。關於所述情況下的聚醯亞胺，就防止發生翹曲等的觀點而言，理想的也是CTE為35 ppm/K以下。When a part or all of the touch panel substrate is replaced with a resin substrate, polyimide has attracted attention. Regarding the polyimide in this case, it is also desirable that the CTE is 35 ppm / K or less from the viewpoint of preventing warpage and the like.

專利文獻6中公開了一種由包含3,3',4,4'-聯苯四羧酸二酐的芳香族四羧酸二酐與2-(4'-胺基苯基)-5-胺基苯并咪唑而得的聚醯亞胺膜，但僅限於電路基板用途。另外，專利文獻7公開了一種由亞異丙基雙(4-伸苯基氧基-4-鄰苯二甲酸)二酐與6-胺基-2-(對胺基苯基)苯并咪唑而得的聚醯亞胺，但其也僅限於金屬層疊基板用途。Patent Document 6 discloses an aromatic tetracarboxylic dianhydride containing 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and 2- (4'-aminophenyl) -5-amine. Polyimide film derived from benzimidazole, but only for circuit board applications. In addition, Patent Document 7 discloses an isopropylidene bis (4-phenyleneoxy-4-phthalic acid) dianhydride and 6-amino-2- (p-aminophenyl) benzimidazole The obtained polyfluorene imine is also limited to metal laminated substrate applications.

專利文獻8、專利文獻9中公開了一種通過具有苯並噁唑結構的芳香族二胺與酸二酐的反應而獲得的聚醯亞胺前體及由其生成的聚醯亞胺，但未教示與特定的酸二酐或二胺的組合。Patent Documents 8 and 9 disclose a polyfluorene imide precursor obtained by the reaction of an aromatic diamine having a benzoxazole structure and an acid dianhydride, and a polyfluorene imine formed therefrom. Teach in combination with a specific acid dianhydride or diamine.

已知一種在支持基板上流延聚醯亞胺前體的溶液並進行熱醯亞胺化而獲得層疊體的方法（專利文獻3）。另外，也報告了將低線膨脹係數的聚醯亞胺膜直接層疊於支持基板上的情況（專利文獻4），但因支持基板與聚醯亞胺前體的組合，剝離變得困難。A method is known in which a solution of a polyfluorene imide precursor is cast on a support substrate and subjected to thermal fluoridation to obtain a laminate (Patent Document 3). In addition, a case where a polyimide film having a low linear expansion coefficient is directly laminated on a support substrate has been reported (Patent Document 4), but the combination of the support substrate and the polyimide precursor makes peeling difficult.

若考慮以上方面，則當將顯示裝置用的支持基材從玻璃基板替換為樹脂基材時，需要能夠至少同時滿足低CTE、高耐熱性、高透明性、與支持基材的易剝離特性，但難以生產出全部滿足所述特性的材料。 [現有技術文獻] [專利文獻]Taking the above into consideration, when replacing a support substrate for a display device from a glass substrate with a resin substrate, it is necessary to be able to satisfy at least low CTE, high heat resistance, high transparency, and easy peeling characteristics from the support substrate. However, it is difficult to produce a material that satisfies all of these characteristics. [Prior Art Literature] [Patent Literature]

[專利文獻1]日本專利特開2012-40836號公報 [專利文獻2]日本專利特開2010-202729號公報 [專利文獻3]日本專利特開昭64-774號公報 [專利文獻4]日本專利特開2012-35583號公報 [專利文獻5]日本專利特開2015-93915號公報 [專利文獻6]日本專利第5716493號公報 [專利文獻7]日本專利第4433655號公報 [專利文獻8]日本專利第5699607號公報 [專利文獻9]日本專利特開2015-214122號公報[Patent Literature 1] Japanese Patent Laid-Open Publication No. 2012-40836 [Patent Literature 2] Japanese Patent Laid-Open Publication No. 2010-202729 [Patent Literature 3] Japanese Patent Laid-Open Publication No. 64-774 [Patent Literature 4] Japanese Patent Japanese Patent Application Publication No. 2012-35583 [Patent Document 5] Japanese Patent Application Publication No. 2015-93915 [Patent Document 6] Japanese Patent Publication No. 5716493 [Patent Document 7] Japanese Patent Publication No. 4433655 [Patent Document 8] Japanese Patent Japanese Patent No. 5699607 [Patent Document 9] Japanese Patent Laid-Open No. 2015-214122

[發明所要解決的問題] 本發明的目的在於提供一種熱膨脹低且製膜性優異，可容易地自支持基材剝離，耐熱性或高透明性優異的聚醯亞胺及其前體。另外，目的在於提供一種為了易於進行與支持基材的剝離而具有良好的雷射剝離特性的聚醯亞胺及其前體。[Problems to be Solved by the Invention] An object of the present invention is to provide a polyimide and a precursor thereof that have low thermal expansion and excellent film-forming properties, can be easily peeled from a supporting substrate, and have excellent heat resistance or high transparency. Another object is to provide a polyimide and a precursor thereof that have good laser peeling characteristics in order to facilitate peeling from a supporting substrate.

[解決問題的技術手段] 本發明者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可滿足所述特性，從而完成了本發明。 即，本發明為一種具有源自二胺的結構單元與源自酸二酐的結構單元的聚醯亞胺前體，其特徵在於：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2,2'-雙(三氟甲基)聯苯胺的結構單元或源自1,2,3,4-環丁烷四羧酸二酐的結構單元。 [化1]式（1） （式（1）中，Z為NH或O） 所述聚醯亞胺前體理想的是滿足以下中的任一項以上。[Technical Means for Solving the Problem] The inventors of the present invention conducted diligent research, and as a result, found that polyfluorene imine having a specific structure or a precursor thereof satisfies the above characteristics, and completed the present invention. That is, the present invention is a polyfluorene imine precursor having a structural unit derived from a diamine and a structural unit derived from an acid dianhydride, and is characterized in that it has i) an aromatic group derived from the following formula (1) Structural unit of the group diamine, and ii) a structural unit derived from 2,2'-bis (trifluoromethyl) benzidine or a structure derived from 1,2,3,4-cyclobutanetetracarboxylic dianhydride unit. [Chemical 1] In the formula (1) (in the formula (1), Z is NH or O) The polyfluorene imide precursor preferably satisfies any one or more of the following.

1）包含源自所有酸二酐的結構單元的50莫耳%以上的源自1,2,3,4-環丁烷四羧酸二酐的結構單元。 2）包含源自所有二胺的結構單元的50莫耳%以上的源自2,2'-雙(三氟甲基)聯苯胺的結構單元。 3）包含源自二胺的所有結構單元的5莫耳%以上的源自所述式（1）所表示的芳香族二胺的結構單元。 4）在氮氣環境下對所述聚醯亞胺前體進行醯亞胺化而得的聚醯亞胺的黃色度為6以下，且自250℃變化為100℃時的線膨脹係數為35 ppm/K以下。 5）對所述聚醯亞胺前體進行醯亞胺化而得的聚醯亞胺的308 nm的透光率為5%以下，430 nm的透光率為70%以上。1) 50 mol% or more of structural units derived from all acid dianhydrides are structural units derived from 1,2,3,4-cyclobutanetetracarboxylic dianhydride. 2) A structural unit derived from 2,2'-bis (trifluoromethyl) benzidine containing 50 mol% or more of structural units derived from all diamines. 3) 5 mol% or more of all the structural units derived from the diamine are structural units derived from the aromatic diamine represented by the formula (1). 4) The yellowness of the polyfluorene imine obtained by fluorimidinating the polyfluorene imide precursor under a nitrogen environment is 6 or less, and the linear expansion coefficient when the temperature changes from 250 ° C to 100 ° C is 35 ppm / K or less. 5) The polyfluorene imine obtained by fluorimidinating the polyfluorene imine precursor has a light transmittance of 308 nm or less and a light transmittance of 430 nm or more of 70%.

另外，本發明為一種具有源自二胺的結構單元與源自酸二酐的結構單元的聚醯亞胺，其特徵在於：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2,2'-雙(三氟甲基)聯苯胺的結構單元或源自1,2,3,4-環丁烷四羧酸二酐的結構單元。In addition, the present invention is a polyfluorene imide having a structural unit derived from a diamine and a structural unit derived from an acid dianhydride, and characterized in that it has i) an aromatic diamine derived from the formula (1) Structural units of amines, and ii) structural units derived from 2,2'-bis (trifluoromethyl) benzidine or structural units derived from 1,2,3,4-cyclobutanetetracarboxylic dianhydride.

所述聚醯亞胺理想的是滿足以下中的任一項以上。 1）黃色度為6以下，自250℃變化為100℃時的熱膨脹係數為35 ppm/K以下。 2）308 nm的透光率為5%以下，430 nm的透光率為70%以上。The polyimide preferably satisfies any one or more of the following. 1) The yellowness is 6 or less, and the thermal expansion coefficient when changing from 250 ° C to 100 ° C is 35 ppm / K or less. 2) The transmittance of 308 nm is less than 5%, and the transmittance of 430 nm is more than 70%.

將本發明的其他實施方式或與本發明相關的發明示於以下。 1）一種由所述聚醯亞胺形成的聚醯亞胺膜。 所述聚醯亞胺膜優異地用於可撓性器件用途。 2）一種在所述聚醯亞胺膜上設置功能層而成的帶功能層的聚醯亞胺膜。 3）所述聚醯亞胺膜的作為可撓性顯示器用可撓性基材的用途、觸控面板用途、彩色濾光片用途，或者所述聚醯亞胺膜的作為用以形成顯示元件、發光元件、電路、導電膜、金屬網（metal mesh）、硬塗膜或阻氣（gas barrier）膜等功能層的可撓性基材的用途。The other embodiment of this invention or the invention related to this invention is shown below. 1) A polyimide film formed from the polyimide. The polyfluoreneimide film is excellent for use in flexible devices. 2) A polyimide film with a functional layer, in which a functional layer is provided on the polyimide film. 3) The use of the polyimide film as a flexible substrate for a flexible display, the use of a touch panel, the use of a color filter, or the use of the polyimide film as a display element , Flexible substrates for functional layers such as light emitting elements, circuits, conductive films, metal meshes, hard coating films, or gas barrier films.

進而，另一實施方式為一種樹脂組合物，其特徵在於：含有所述聚醯亞胺前體與溶媒。 進而，另一實施方式為一種聚醯亞胺膜，其特徵在於：其是將所述樹脂組合物塗布於支持基板的表面上，繼而對其進行加熱而對聚醯亞胺前體進行醯亞胺化而形成。Furthermore, another embodiment is a resin composition containing the said polyfluorene imide precursor and a solvent. Furthermore, another embodiment is a polyimide film, characterized in that the resin composition is coated on the surface of a support substrate, and then the polyimide precursor is subjected to heating. Formed by amination.

進而，另一實施方式為一種聚醯亞胺膜的製造方法，其特徵在於具備：將所述樹脂組合物塗布於支持基板的表面上的步驟；對其進行加熱而對聚醯亞胺前體進行醯亞胺化以形成聚醯亞胺膜的步驟；以及將所述聚醯亞胺膜自支持基板剝離而獲得聚醯亞胺膜的步驟。 進而，另一實施方式為一種層疊體，其特徵在於：具備支持基板及聚醯亞胺膜，所述層疊體是在支持基板的表面上將所述樹脂組合物延展開，並對其進行加熱而對聚醯亞胺前體進行醯亞胺化以形成聚醯亞胺膜而得。另外，一種層疊體的製造方法，其特徵在於具備：在支持基板的表面上將所述樹脂組合物延展開的步驟；以及對其進行加熱而對聚醯亞胺前體進行醯亞胺化以形成聚醯亞胺膜，從而獲得包括支持基板及聚醯亞胺膜的層疊體的步驟。Furthermore, another embodiment is a method for producing a polyimide film, comprising: a step of applying the resin composition to a surface of a support substrate; and heating the polyimide precursor to the polyimide precursor. Performing a step of ammonium imidization to form a polyimide film; and a step of peeling the polyimide film from a support substrate to obtain a polyimide film. Furthermore, another embodiment is a laminate including a support substrate and a polyimide film, and the laminate is configured to expand the resin composition on the surface of the support substrate and heat the resin composition. The polyimide precursor is obtained by performing imidization to form a polyimide film. In addition, a method for producing a laminated body, comprising: a step of expanding the resin composition on a surface of a support substrate; and heating the polyimide precursor to perform imidization of the polyimide precursor to A step of forming a polyimide film to obtain a laminate including a support substrate and a polyimide film.

進而，另一實施方式為一種基板、圖像顯示裝置、光學材料或電子器件，其特徵在於：含有或具有所述聚醯亞胺或聚醯亞胺膜。 進而，另一實施方式為一種帶功能層的聚醯亞胺膜的製造方法，其通過在支持基板上對所述樹脂組合物進行塗布･乾燥･熱處理而獲得聚醯亞胺膜，然後在聚醯亞胺膜上形成功能層後，自支持基板將所述聚醯亞胺膜連同功能層一起剝離而獲得帶功能層的聚醯亞胺膜。 所述帶功能層的聚醯亞胺膜的製造方法中，支持基板優選包括無機基板，功能層優選為顯示元件、發光元件、電路、氧化銦錫（indium tin oxid，ITO）等的導電膜、金屬網、硬塗膜或者防止水分或氧等的滲透的阻氣膜。 [發明的效果]Furthermore, another embodiment is a substrate, an image display device, an optical material, or an electronic device, characterized in that it contains or has the polyimide or polyimide film. Furthermore, another embodiment is a method for producing a polyimide film with a functional layer, which is obtained by applying, drying, and heat-treating the resin composition on a support substrate, and then After the functional layer is formed on the fluorene imine film, the polyfluorene imine film is peeled together with the functional layer from the supporting substrate to obtain a polyfluorene film with a functional layer. In the method for manufacturing a polyimide film with a functional layer, the supporting substrate preferably includes an inorganic substrate, and the functional layer is preferably a conductive film such as a display element, a light-emitting element, a circuit, indium tin oxide (ITO), or the like. Metal mesh, hard coating film, or gas barrier film to prevent penetration of moisture, oxygen, etc. [Effect of the invention]

本發明的聚醯亞胺前體或由其而得的聚醯亞胺因耐熱性、透明性高，為低熱膨脹性，且易於進行與支持基板的剝離，故適於用作顯示裝置等的支持基材用聚醯亞胺膜，可提供生產性優異的聚醯亞胺膜，因此可優選地用作形成顯示元件、發光元件、電路、ITO等的導電膜、金屬網、硬塗膜或者防止水分或氧等的滲透的阻氣膜等功能層的可撓性基材。The polyimide precursor of the present invention or a polyimide obtained from the polyimide precursor is suitable for display devices and the like because of its high heat resistance and transparency, low thermal expansion, and easy peeling from a support substrate. A polyimide film for a supporting substrate can provide a polyimide film having excellent productivity, and is therefore preferably used as a conductive film, metal mesh, hard coating film, or the like for forming a display element, a light-emitting element, a circuit, ITO, or the like. A flexible base material for a functional layer such as a gas barrier film that prevents penetration of moisture and oxygen.

本發明的聚醯亞胺前體具有源自所述式（1）所表示的芳香族二胺的結構單元（U1）、以及源自2,2'-雙(三氟甲基)聯苯胺（別名：2,2'-雙(三氟甲基)-4,4'-二胺基聯苯）的結構單元（U2）或源自1,2,3,4-環丁烷四羧酸二酐的結構單元（U3）。本發明的聚醯亞胺前體有具有結構單元（U1）與結構單元（U2）的情況、具有結構單元（U1）與結構單元（U3）的情況、以及具有結構單元（U1）與結構單元（U2）及結構單元（U3）的情況。 式（1）中，Z為NH或O。The polyfluorene imide precursor of the present invention has a structural unit (U1) derived from the aromatic diamine represented by the formula (1), and a 2,2′-bis (trifluoromethyl) benzidine ( Alias: Structural unit (U2) of 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl) or derived from 1,2,3,4-cyclobutane tetracarboxylic acid di Structural unit (U3) of anhydride. The polyfluorene imide precursor of the present invention may include a structural unit (U1) and a structural unit (U2), a structural unit (U1) and a structural unit (U3), and a structural unit (U1) and a structural unit. (U2) and structural unit (U3). In formula (1), Z is NH or O.

將本發明的聚醯亞胺前體中所含的結構單元的一例示於式（2）及式（3）。 [化2] （2） （3） 如根據所述式（2）及式（3）可知，聚醯亞胺前體可由下述式（4）表示。 [-OCX(COOH)2 CO-HN-Y-NH-] （4） 另一方面，聚醯亞胺可由下述式（5）表示。 [-N(OC)2 X(CO)2 N-Y-] （5）An example of the structural unit contained in the polyfluorene imide precursor of this invention is shown in Formula (2) and Formula (3). As can be seen from the formulas (2) and (3), the polyimide precursor can be represented by the following formula (4). [-OCX (COOH) 2 CO-HN-Y-NH-] (4) On the other hand, polyfluorene imine can be represented by the following formula (5). [-N (OC) 2 X (CO) 2 NY-] (5)

式（2）～式（5）中，X是自酸二酐去除兩個酸二酐基而生成的四價殘基。式（4）～式（5）中，Y是自二胺去除兩個胺基而生成的二價殘基。In the formulae (2) to (5), X is a tetravalent residue formed by removing two acid dianhydride groups from the acid dianhydride. In the formulae (4) to (5), Y is a divalent residue formed by removing two amine groups from a diamine.

在酸二酐為1,2,3,4-環丁烷四羧酸二酐的情況下，為下述式（6）所示的1,2,3,4-環丁烷-四基。 [化3]（6）When the acid dianhydride is 1,2,3,4-cyclobutanetetracarboxylic dianhydride, it is 1,2,3,4-cyclobutane-tetrayl represented by the following formula (6). [Chemical 3] (6)

再者，在結構單元的說明中，使用源自二胺的結構單元或源自酸二酐的結構單元等用語，但這是為了方便起見，只要是可提供如式（2）～式（6）所示的結構單元者即可，並不限定於源自它們的結構單元。具體而言，所述式（4）～式（5）中，將源自酸二酐的結構單元解釋為X，將源自二胺的結構單元解釋為Y，而不應解釋為意指原料或製造法。而且，聚醯亞胺前體的結構單元及其比例取決於二胺與酸二酐的種類及使用比例，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。In the description of the structural unit, terms such as a structural unit derived from a diamine or a structural unit derived from an acid dianhydride are used. However, this is for convenience, as long as the formulas (2) to ( 6) The structural units shown may be used, and are not limited to the structural units derived from them. Specifically, in the formulae (4) to (5), the structural unit derived from an acid dianhydride is interpreted as X, and the structural unit derived from a diamine is interpreted as Y, and should not be interpreted as meaning a raw material. Or manufacturing method. In addition, the structural units of polyimide precursors and their ratios depend on the type and use ratio of diamine and acid dianhydride. Therefore, the description of the structural units is explained by using diamine and acid dianhydride. 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.

所述式（2）及式（3）所表示的聚醯亞胺前體是使用式（1）所表示的芳香族二胺作為二胺的例子，但作為二胺，除此以外也可為2,2'-雙(三氟甲基)聯苯胺。另外，式（2）及式（3）中，右端的苯環中的結合鍵的位置不受限定，優選為4-位。The polyfluorene imine precursors represented by the formulas (2) and (3) are examples using the aromatic diamine represented by the formula (1) as the diamine, but as the diamine, other than 2,2'-bis (trifluoromethyl) benzidine. In addition, in formulas (2) and (3), the position of the bonding bond in the benzene ring at the right end is not limited, and it is preferably the 4-position.

本發明的聚醯亞胺前體及聚醯亞胺可通過使用作為二胺的式（1）所表示的芳香族二胺或包含所述芳香族二胺與2,2'-雙(三氟甲基)聯苯胺的二胺、與包含或不包含1,2,3,4-環丁烷四羧酸二酐的酸二酐來進行反應而獲得。在使用包含2,2'-雙(三氟甲基)聯苯胺的二胺混合物作為二胺的情況下，酸二酐可不包含1,2,3,4-環丁烷四羧酸二酐，在使用包含式（1）所表示的芳香族二胺但不包含2,2'-雙(三氟甲基)聯苯胺的二胺的情況下，酸二酐包含1,2,3,4-環丁烷四羧酸二酐。The polyfluorene imide precursor and the polyfluorene imide of the present invention can be obtained by using an aromatic diamine represented by formula (1) as a diamine or containing the aromatic diamine and 2,2'-bis (trifluoro It is obtained by reacting a diamine of methyl) benzidine with an acid dianhydride with or without 1,2,3,4-cyclobutanetetracarboxylic dianhydride. In the case where a diamine mixture containing 2,2'-bis (trifluoromethyl) benzidine is used as the diamine, the acid dianhydride may not include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, When a diamine containing an aromatic diamine represented by the formula (1) but not including 2,2'-bis (trifluoromethyl) benzidine is used, the acid dianhydride contains 1,2,3,4- Cyclobutane tetracarboxylic dianhydride.

即，可使用作為通常的製法而已知的以下方法：利用四羧酸二酐與二胺的反應而獲得聚醯亞胺前體（也稱為聚醯胺酸（polyamic acid或polyamide acid）），通過對所述聚醯亞胺前體進行熱處理而引起的閉環反應來形成聚醯亞胺。That is, the following method known as a general production method can be used: a polyimide precursor (also referred to as a polyamic acid or a polyamide acid) obtained by a reaction of a tetracarboxylic dianhydride and a diamine, The polyfluorene imine is formed by a ring-closing reaction caused by heat treatment of the polyfluorene imine precursor.

作為二胺，使用式（1）所表示的芳香族二胺、或包含所述芳香族二胺與2,2'-雙(三氟甲基)聯苯胺的混合物。式（1）所表示的芳香族二胺中有Z為NH的苯并咪唑系的二胺、以及Z為O的苯并噁唑系的二胺，可為任一者，也可併用兩者。As the diamine, an aromatic diamine represented by the formula (1) or a mixture containing the aromatic diamine and 2,2′-bis (trifluoromethyl) benzidine is used. The aromatic diamine represented by the formula (1) includes a benzimidazole-based diamine in which Z is NH and a benzoxazole-based diamine in which Z is O. Either one may be used, or both may be used in combination. .

就耐熱性、低熱膨脹的觀點而言，式（1）所表示的芳香族二胺使用量可為所有二胺的5莫耳%以上、優選為20莫耳%以上、更優選為50莫耳%以上。From the viewpoint of heat resistance and low thermal expansion, the amount of the aromatic diamine used in the formula (1) may be 5 mol% or more, preferably 20 mol% or more, and more preferably 50 mol of all the diamines. %the above.

作為另一優選的實施方式，就耐熱性、低熱膨脹及透明性的平衡性的觀點而言，式（1）所表示的芳香族二胺與2,2'-雙(三氟甲基)聯苯胺的合計使用量可為所有二胺的50莫耳%以上，更優選為80莫耳%以上。As another preferred embodiment, the aromatic diamine represented by formula (1) is linked to 2,2'-bis (trifluoromethyl) in terms of the balance between heat resistance, low thermal expansion, and transparency. The total amount of aniline used may be 50 mol% or more, and more preferably 80 mol% or more, of all diamines.

作為另一優選的實施方式，就430 nm中的透明性及低黃色度的觀點而言，2,2'-雙(三氟甲基)聯苯胺的使用量可為所有二胺的5莫耳%以上、優選為20莫耳%以上、更優選為50莫耳%以上、進而優選為80莫耳%以上。As another preferred embodiment, the amount of 2,2′-bis (trifluoromethyl) benzidine may be 5 moles of all diamines from the viewpoint of transparency and low yellowness at 430 nm. % Or more, preferably 20 mol% or more, more preferably 50 mol% or more, and still more preferably 80 mol% or more.

作為四羧酸二酐，就低熱膨脹或透明性的觀點而言，可優選地使用1,2,3,4-環丁烷四羧酸二酐。As the tetracarboxylic dianhydride, 1,2,3,4-cyclobutane tetracarboxylic dianhydride can be preferably used from the viewpoint of low thermal expansion or transparency.

1,2,3,4-環丁烷四羧酸二酐的使用量優選為所有酸二酐的50莫耳%以上，更優選為80莫耳%以上。The used amount of 1,2,3,4-cyclobutanetetracarboxylic dianhydride is preferably 50 mol% or more, and more preferably 80 mol% or more of all acid dianhydrides.

在使用2,2'-雙(三氟甲基)聯苯胺作為二胺的情況下，因2,2'-雙(三氟甲基)聯苯胺可賦予耐熱性、低熱膨脹或透明性，故可不使用1,2,3,4-環丁烷四羧酸二酐，但宜使用所有酸二酐的10莫耳%以上、優選為50莫耳%以上的1,2,3,4-環丁烷四羧酸二酐。When 2,2'-bis (trifluoromethyl) benzidine is used as the diamine, since 2,2'-bis (trifluoromethyl) benzidine can impart heat resistance, low thermal expansion, or transparency, 1,2,3,4-cyclobutane tetracarboxylic dianhydride may not be used, but it is preferable to use more than 10 mol%, preferably 50 mol% or more of 1,2,3,4-cyclo Butane tetracarboxylic dianhydride.

而且，可為：1,2,3,4-環丁烷四羧酸二酐的使用量為所有酸二酐的50莫耳%以上、優選為80莫耳%以上，且式（1）所表示的芳香族二胺的使用量為所有二胺的5莫耳%以上、優選為50莫耳%以上、更優選為80莫耳%以上，或者式（1）所表示的芳香族二胺與2,2'-雙(三氟甲基)聯苯胺的使用量的合計為所有二胺的50莫耳%以上、優選為80莫耳%以上。關於併用式（1）所表示的芳香族二胺與2,2'-雙(三氟甲基)聯苯胺的情況下的兩者的使用量的比例，可為相對於前者1莫耳，後者為0.1莫耳～20莫耳的範圍。In addition, the use amount of 1,2,3,4-cyclobutanetetracarboxylic dianhydride may be 50 mol% or more, preferably 80 mol% or more of all acid dianhydrides, and the formula (1) The amount of the aromatic diamine used is 5 mol% or more, preferably 50 mol% or more, and more preferably 80 mol% or more of all the diamines, or the aromatic diamine represented by formula (1) and The total amount of 2,2'-bis (trifluoromethyl) benzidine used is 50 mol% or more, preferably 80 mol% or more, of all diamines. The ratio of the amounts of the aromatic diamine and 2,2'-bis (trifluoromethyl) benzidine used in the case where the formula (1) is used in combination may be 1 mole relative to the former and the latter It is in the range of 0.1 mol to 20 mol.

所有酸二酐中的1,2,3,4-環丁烷四羧酸二酐的使用比例（莫耳%）成為源自酸二酐的所有結構單元中的源自1,2,3,4-環丁烷四羧酸二酐的結構單元的含量（莫耳%）。關於源自二胺的所有結構單元中的源自所述式（1）所表示的芳香族二胺的結構單元的含量（莫耳%）等也同樣如此。The proportion of 1,2,3,4-cyclobutanetetracarboxylic dianhydride (mole%) in all acid dianhydrides becomes 1,2,3, Content of the structural unit of 4-cyclobutanetetracarboxylic dianhydride (mole%). The same applies to the content (mole%) of the structural unit derived from the aromatic diamine represented by the formula (1) among all the structural units derived from the diamine.

而且，可使用所有二胺的5莫耳%以上、優選為50莫耳%以上的所述式（1）所表示的芳香族二胺，以將所述結構單元（U1）設為源自二胺的所有結構單元的5莫耳%以上。另外，可包含源自2,2'-雙(三氟甲基)聯苯胺的結構單元（U2），更優選的是包含源自二胺的所有結構單元的50莫耳%以上的結構單元（U2）、及源自酸二酐的所有結構單元的50莫耳%以上的源自1,2,3,4-環丁烷四羧酸二酐的結構單元（U3）。Further, the aromatic diamine represented by the formula (1) may be used in an amount of 5 mol% or more, preferably 50 mol% or more of all diamines, so that the structural unit (U1) is derived from diamine. More than 5 mole% of all structural units of the amine. In addition, it may contain a structural unit (U2) derived from 2,2′-bis (trifluoromethyl) benzidine, and more preferably a structural unit containing 50 mol% or more of all structural units derived from diamine ( U2) and structural units (U3) derived from 1,2,3,4-cyclobutanetetracarboxylic dianhydride of 50 mol% or more of all structural units derived from acid dianhydride.

作為四羧酸二酐，在使用2,2'-雙(三氟甲基)聯苯胺的情況下並無特別的限制，優選的是使用1,2,3,4-環丁烷四羧酸二酐。The tetracarboxylic dianhydride is not particularly limited when 2,2'-bis (trifluoromethyl) benzidine is used. It is preferable to use 1,2,3,4-cyclobutanetetracarboxylic acid. Dianhydride.

無論是否使用1,2,3,4-環丁烷四羧酸二酐，均可使用其他四羧酸二酐。在使用其他四羧酸二酐的情況下，可在所有酸二酐的10莫耳%～70莫耳%的範圍內使用。優選為50莫耳%以下，更優選為20莫耳%以下。再者，在使用2,2'-雙(三氟甲基)聯苯胺的情況下，當使用其他四羧酸二酐時，可在所有酸二酐的10莫耳%～100莫耳%的範圍內使用，但優選為50莫耳%以下，更優選為20莫耳%以下。Regardless of whether 1,2,3,4-cyclobutane tetracarboxylic dianhydride is used, other tetracarboxylic dianhydrides can be used. In the case of using other tetracarboxylic dianhydride, it can be used in the range of 10 mol% to 70 mol% of all acid dianhydrides. It is preferably 50 mol% or less, and more preferably 20 mol% or less. Furthermore, in the case of using 2,2'-bis (trifluoromethyl) benzidine, when other tetracarboxylic dianhydrides are used, the amount of It is used within the range, but is preferably 50 mol% or less, and more preferably 20 mol% or less.

作為所述其他四羧酸二酐，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}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，所述其他四羧酸二酐可單獨使用，或者也可併用兩種以上。Examples of the other tetracarboxylic dianhydride 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 dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 2,2', 3,3'-benzophenonetetracarboxylic acid Dianhydride, 2,3,3 ', 4'-benzophenonetetracarboxylic dianhydride, naphthalene-1,2,4,5-tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetra Carboxylic dianhydride, 4,8-dimethyl-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 acid 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-tetrachloronaphthalene-2,3,6,7-tetracarboxylic dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 2,3,3 ', 4'-Biphenyltetracarboxylic dianhydride, 3,3' ', 4,4' '-p-terphenyltetracarboxylic dianhydride, 2,2' ', 3,3' '-p-terphenyltetracarboxylic dianhydride Carboxylic dianhydride, 2,3,3 '', 4 ''-p-terphenylene tetracarboxylic dianhydride, 2,2-bis (2,3-dicarboxyphenyl) -propane dianhydride, 2,2- Bis (3,4-dicarboxyphenyl)- Alkane 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 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, fluorene-2,3,8,9-tetracarboxylic dianhydride, fluorene-3,4,9,10-tetracarboxylic dianhydride苝, 4, -5,10,11-tetracarboxylic dianhydride, 苝 -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, pyridine Tetrazine-2,3,5,6-tetracarboxylic dianhydride, 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) benzene Tetracarboxylic dianhydride, pentafluoroethyl pyromellitic dianhydride, 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} phthalic anhydride, bis {(trifluoromethyl) dicarboxyphenoxy} trifluoromethylphthalic anhydride, bis (dicarboxyphenoxy) trifluoromethylbenzene Dianhydride, 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) dicarboxybenzene Oxy} bis (trifluoromethyl) biphenyl dianhydride, bis {(trifluoromethyl) dicarboxyphenoxy} diphenyl ether dianhydride, bis (dicarboxyphenoxy) bis (trifluoromethyl) ) Biphenyl dianhydride and so on. The other tetracarboxylic dianhydrides may be used alone, or two or more of them may be used in combination.

就高耐熱性與低熱膨脹性的觀點而言，優選為萘-2,3,6,7-四羧酸二酐、均苯四甲酸二酐、或3,3',4,4'-聯苯四羧酸二酐。另外，就透明性的觀點而言，優選為4,4'-(2,2'-六氟亞異丙基)二鄰苯二甲酸二酐、或4,4'-氧基二鄰苯二甲酸二酐。From the viewpoints of high heat resistance and low thermal expansion, naphthalene-2,3,6,7-tetracarboxylic dianhydride, pyromellitic dianhydride, or 3,3 ', 4,4'-covalent Pyromellitic dianhydride. From the viewpoint of transparency, 4,4 '-(2,2'-hexafluoroisopropylidene) diphthalic dianhydride or 4,4'-oxydiphthalic acid is preferred. Formic acid dianhydride.

作為其他優選的四羧酸二酐，以對聚醯亞胺膜賦予強度與柔軟性為目的，可列舉：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等。就可獲得低熱膨脹性的聚醯亞胺膜而言，優選的是均苯四甲酸二酐或3,3',4,4'-聯苯四羧酸二酐。As another preferred tetracarboxylic dianhydride, for the purpose of imparting strength and flexibility to a polyimide film, examples include pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic acid. Dianhydride, 4,4'-oxydiphthalic dianhydride, etc. In order to obtain a polyfluorene imide film having low thermal expansion, pyromellitic dianhydride or 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride is preferred.

再者，1,2,3,4-環丁烷四羧酸二酐就賦予高耐熱性與低熱膨脹性及透明性的方面而言優異。Furthermore, 1,2,3,4-cyclobutane tetracarboxylic dianhydride is excellent in terms of imparting high heat resistance, low thermal expansion, and transparency.

作為二胺，除式（1）所表示的芳香族二胺、或所述芳香族二胺與2,2'-雙(三氟甲基)聯苯胺以外，也可使用其他二胺。在使用其他二胺的情況下，可在所有二胺的10莫耳%～70莫耳%的範圍內使用，優選為小於50莫耳%。As the diamine, in addition to the aromatic diamine represented by the formula (1), or the aromatic diamine and 2,2′-bis (trifluoromethyl) benzidine, 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'-二胺基聯苯（別名：2,2'-二甲基-聯苯胺）、3,3'-二甲基-4,4'-二胺基聯苯、4,4'-二胺基二苯基醚、3,4'-二胺基二苯基醚、4,6-二甲基間苯二胺、2,5-二甲基對苯二胺、2,4-二胺基-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'-二胺基二苯基丙烷、3,3'-二胺基二苯基丙烷、4,4'-二胺基二苯基乙烷、3,3'-二胺基二苯基乙烷、4,4'-二胺基二苯基甲烷、3,3'-二胺基二苯基甲烷、2,2-雙[4-(4-胺基苯氧基)苯基]丙烷、4,4'-二胺基二苯基硫醚、3,3'-二胺基二苯基硫醚、4,4'-二胺基二苯基碸、3,3'-二胺基二苯基碸、4,4'-二胺基二苯基醚、3,3'-二胺基二苯基醚、1,3-雙(3-胺基苯氧基)苯、1,3-雙(4-胺基苯氧基)苯、1,4-雙(4-胺基苯氧基)苯、聯苯胺、3,3'-二胺基聯苯、3,3'-二甲基-4,4'-二胺基聯苯、3,3'-二甲氧基聯苯胺、4,4'-二胺基對三聯苯、3,3'-二胺基對三聯苯、雙(p-β-胺基-第三丁基苯基)醚、雙(p-β-甲基-δ-胺基戊基)苯、p-雙(2-甲基-4-胺基戊基)苯、p-雙(1,1-二甲基-5-胺基戊基)苯、1,5-二胺基萘、2,6-二胺基萘、2,4-雙(β-胺基-第三丁基)甲苯、2,4-二胺基甲苯、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、2,6-二胺基吡啶、2,5-二胺基吡啶、2,5-二胺基-1,3,4-噁二唑、哌嗪等。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-dimethyl M-phenylene diamine, 2,5-dimethyl p-phenylenediamine, 2,4-diamino-1,3,5-trimethylbenzene, 4,4'-methylene di-o-tolylamine, 4, 4'-methylenebis-2,6-dimethyltoluidine, 4,4'-methylene-2,6-diethylaniline, 2,4-toluenediamine, m-phenylenediamine, p-xylene Amine, 4,4'-diaminodiphenylpropane, 3,3'-diaminodiphenylpropane, 4,4'-diaminodiphenylethane, 3,3'-diamine Diphenylethane, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 2,2-bis [4- (4-aminophenoxy) benzene Group] propane, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenylsulfonium, 3,3'- Diaminodiphenylphosphonium, 4,4'-diaminodiphenyl 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 Dibenzyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxybenzidine, 4,4'-diamine para-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-aminopentyl) benzene, p-bis (1,1-dimethyl-5-aminopentyl) benzene, 1,5-diaminonaphthalene, 2,6-diamine Naphthalene, 2,4-bis (β-amino-third butyl) toluene, 2,4-diaminotoluene, m-xylene-2,5-diamine, p-xylene-2,5-di Amine, m-xylylenediamine, p-xylylenediamine, 2,6-diaminopyridine, 2,5-diaminopyridine, 2,5-diamino-1,3,4-oxadiazole, Piperazine and others.

所述二胺中，優選為2,2'-二甲基-4,4'-二胺基聯苯、4,4'-二胺基二苯基醚、4,6-二甲基間苯二胺、2,5-二甲基對苯二胺、2,4-二胺基-1,3,5-三甲苯、2,4-甲苯二胺、間苯二胺、或對苯二胺，就反應迅速、高透明性的觀點而言，適宜為2,2'-二甲基-4,4'-二胺基聯苯、或4,4'-二胺基二苯基醚。Among the diamines, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, and 4,6-dimethylm-phenylene are preferred. Diamine, 2,5-dimethyl-p-phenylenediamine, 2,4-diamino-1,3,5-trimethylbenzene, 2,4-toluenediamine, m-phenylenediamine, or p-phenylenediamine From the viewpoints of rapid reaction and high transparency, 2,2'-dimethyl-4,4'-diaminobiphenyl or 4,4'-diaminodiphenyl ether is suitable.

本發明的聚醯亞胺的前體可利用以0.9～1.1的莫耳比使用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。具體而言，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-吡咯烷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。此時，分子末端可由芳香族單胺或芳香族單羧酸二酐封閉。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，也可使用一種或併用兩種以上。The polyfluorene imide precursor of the present invention can be produced by a known method using a diamine and an acid dianhydride in a molar ratio of 0.9 to 1.1 and polymerizing in an organic polar solvent. Specifically, it can be obtained by dissolving a diamine in an aprotic fluorene-based solvent such as N, N-dimethylacetamide 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 this case, the molecular terminal may be blocked by an aromatic monoamine or an aromatic monocarboxylic dianhydride. Examples of the solvent include dimethylformamide, 2-butanone, diethylene glycol dimethyl ether, xylene, and γ-butyrolactone, and one or two or more of them may be used in combination.

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、樹脂等任意的支持基材上，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。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可進行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 support substrate such as glass, metal, resin, etc. using an applicator, and performing the temperature at 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. 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 the thermal ammonium imidization, if the combination of the type of acid dianhydride or diamine and the type of solvent is selected, the ammonium imidization is 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或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～40,000 cP，優選處於3,000 cP～5,000 cP的範圍。另外，聚醯亞胺前體的分子量可利用凝膠滲透層析（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，但此僅為標準，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。Regarding the preferred degree of polymerization of the polyimide precursor or polyimide of the present invention, it may be 1,000 cP to 40,000 cP in terms of the viscosity conversion of the polyimide precursor solution measured with an E-type viscometer, preferably at The range is from 3,000 cP to 5,000 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 polyfluorene imide 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. However, this is only a standard, and the range cannot be used. Out of all polyimide precursors. The molecular weight of polyimide is also in the same range as the molecular weight of its precursor.

本發明的聚醯亞胺前體可為：在氮氣環境下對其進行醯亞胺化而得的聚醯亞胺的黃色度為6以下，優選為4以下。若為所述範圍，則可優選地用於有機EL裝置用TFT基板、觸控面板基板、彩色濾光片基板等要求透明性或為無色的基板。The polyfluorene imide precursor of the present invention may have a yellowness of 6 or less, preferably 4 or less. Within this range, it can be preferably used for a substrate that requires transparency or is colorless, such as a TFT substrate for an organic EL device, a touch panel substrate, and a color filter substrate.

而且，熱膨脹係數（CTE）可為35 ppm/K以下。優選為30 ppm/K以下。此處，只要無特別的說明，則CTE為自250℃變化為100℃時的線膨脹係數（亦稱「熱膨脹係數」）。若為所述範圍，則當製造有機EL裝置用TFT基板、觸控面板基板、彩色濾光片等中的功能層層疊體等可撓性器件時，可抑制基板的翹曲，可撓性器件的製造良率優異。In addition, the coefficient of thermal expansion (CTE) can be 35 ppm / K or less. It is preferably 30 ppm / K or less. Here, unless otherwise specified, the CTE is a coefficient of linear expansion (also referred to as a "thermal expansion coefficient") when it changes from 250 ° C to 100 ° C. Within this range, when flexible devices such as functional layer laminates in TFT substrates for organic EL devices, touch panel substrates, color filters, and the like are manufactured, warping of the substrate can be suppressed, and flexible devices The manufacturing yield is excellent.

進而，對所述聚醯亞胺前體進行醯亞胺化而得的聚醯亞胺可為：308 nm的透光率為5%以下，430 nm的透光率為70%以上、優選為80%以上。308 nm的透光率更優選為3%以下，進而優選為小於1%，進而優選為小於0.1%。此處，本發明的聚醯亞胺在用作聚醯亞胺膜的情況下、優選的是用於可撓性器件用途的情況下、更優選的是用作在聚醯亞胺膜上設置功能層而成的帶功能層的聚醯亞胺膜的情況下，只要無特別的說明，則所述透光率為對所述膜進行測定而得的值。在其他優選的實施方式中，所述透光率為在厚度10 μm～15 μm的膜狀態下測定而得的值，在所述範圍的任一者中，只要可提供所述透射率即可。在更優選的實施方式中，所述透光率為在厚度13 μm的膜狀態下測定而得的值。所述情況下，可為將在厚度13 μm左右的膜狀態下測定而得的值換算為13 μm的膜而得的值。Furthermore, the polyfluorene imide obtained by fluorimidinating the polyfluorene imine precursor may have a light transmittance of 308 nm or less, and a light transmittance of 430 nm or more, preferably 70% or more. More than 80%. The light transmittance at 308 nm is more preferably 3% or less, still more preferably less than 1%, and still more preferably less than 0.1%. Here, when the polyfluorene imide of the present invention is used as a polyfluorene imide film, preferably when it is used for a flexible device, it is more preferably used as a polyimide film. In the case of a polyfluorene imide film with a functional layer made of a functional layer, the light transmittance is a value obtained by measuring the film unless otherwise specified. In another preferred embodiment, the light transmittance is a value measured in a film state with a thickness of 10 μm to 15 μm, and in any of the ranges, the transmittance may be provided. . In a more preferred embodiment, the light transmittance is a value measured in a film state with a thickness of 13 μm. In this case, a value obtained by converting a value measured in a film state with a thickness of about 13 μm into a 13 μm film can be obtained.

以所述方式吸收近紫外區域的光線並提高紫外區域光線的透射率。若為所述範圍，則可在保持可見光區域的透明性的同時吸收308 nm的雷射光。其結果，可通過對有機EL裝置用基板、觸控面板基板、具有頂部發光結構的彩色濾光片基板等可撓性基板進行雷射照射而不對透明聚醯亞胺（polyimide，PI）層上的顯示裝置造成損傷地將PI自玻璃剝離，從而可利用雷射剝離法優選地進行製造。In this way, light in the near-ultraviolet region is absorbed and transmittance of the light in the ultraviolet region is increased. Within this range, laser light at 308 nm can be absorbed while maintaining transparency in the visible light region. As a result, a flexible substrate such as a substrate for an organic EL device, a touch panel substrate, and a color filter substrate having a top-emission structure can be irradiated with laser light without applying a transparent polyimide (PI) layer. The display device is peeled from the glass by causing damage to the display device, and thus can be preferably manufactured by a laser peeling method.

本發明的聚醯亞胺具有源自二胺的結構單元與源自酸二酐的結構單元，且具有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2,2'-雙(三氟甲基)聯苯胺的結構單元或源自1,2,3,4-環丁烷四羧酸二酐的結構單元。此處，關於源自二胺的結構單元與源自酸二酐的結構單元的說明與所述聚醯亞胺前體的說明相同。而且，本發明的聚醯亞胺也為本發明的聚醯亞胺前體的醯亞胺化物。醯亞胺化是通過對聚醯亞胺前體進行脫水、閉環來進行，但結構單元的排列被維持為相同。The polyfluorene imide of the present invention has a structural unit derived from a diamine and a structural unit derived from an acid dianhydride, and has i) a structural unit derived from an aromatic diamine represented by the formula (1), and ii ) A structural unit derived from 2,2'-bis (trifluoromethyl) benzidine or a structural unit derived from 1,2,3,4-cyclobutanetetracarboxylic dianhydride. Here, the description of the structural unit derived from a diamine and the structural unit derived from an acid dianhydride is the same as that of the polyfluorene imine precursor. Moreover, the polyfluorene imide of the present invention is also a phosphonium imide of a polyfluorene imine precursor of the present invention. The fluorene imidization is performed by dehydrating and ring-closing the polyfluorene imide precursor, but the arrangement of the structural units is maintained the same.

本發明的聚醯亞胺的黃色度可為6以下、優選為4以下。另外，CTE可為35 ppm/K以下、優選為30 ppm/K以下、更優選為20 ppm/K以下。The polyimide of the present invention may have a yellowness of 6 or less, and preferably 4 or less. The CTE may be 35 ppm / K or less, preferably 30 ppm / K or less, and more preferably 20 ppm / K or less.

本發明的聚醯亞胺的308 nm的透光率可為5%以下，430 nm的透光率可為70%以上。另外，就透明性的觀點而言，可見區域的所有光線的透光率可為70%以上、優選為80%以上。而且，就耐熱性的觀點而言，玻璃轉移溫度可為360℃以上、優選為400℃以上。另外，Td1熱分解溫度（1%重量減少溫度）可為300℃以上。308 nm的透光率更優選為3%以下，進而優選為小於1%，進而優選為小於0.1%。The polyfluorene imide of the present invention may have a light transmittance of 308 nm or less, and a light transmittance of 430 nm may be more than 70%. In addition, from the viewpoint of transparency, the light transmittance of all light rays in the visible region may be 70% or more, and preferably 80% or more. From the viewpoint of heat resistance, the glass transition temperature may be 360 ° C or higher, and preferably 400 ° C or higher. In addition, the thermal decomposition temperature (1% weight reduction temperature) of Td1 may be 300 ° C or higher. The light transmittance at 308 nm is more preferably 3% or less, still more preferably less than 1%, and still more preferably less than 0.1%.

滿足所述特性的聚醯亞胺前體及聚醯亞胺可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結構單元（U1）～結構單元（U3）的含量設為一定以上等來獲得。The polyfluorene imide precursor and the polyfluorene imide satisfying the above-mentioned characteristics can include the structural unit (U1) of the polyfluorene imine precursor and the polyfluorene imide of the present invention as necessary or preferred structural units. The content of the structural unit (U3) is obtained by setting it to a certain level or more.

將聚醯亞胺前體形成為聚醯亞胺的方法並無限制，在將聚醯亞胺用作支持基材的情況下，有利的是以膜狀或包含聚醯亞胺層的層疊體的形式獲得。The method for forming a polyfluorene imide precursor into a polyfluorene imine is not limited. In the case where a polyfluorene imine is used as a supporting substrate, it is advantageous to use a polyimide layer or a polyimide layer. Form of acquisition.

優選的是可通過以下方式獲得聚醯亞胺層疊體：將包含聚醯亞胺前體的樹脂溶液（樹脂組合物）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，理想的是如上所述般在基材上進行醯亞胺化而直接形成層疊體，並視需要對其進行剝離而形成膜。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 laminate by performing fluorimidation on a substrate as described above, and peeling it to form a film as necessary.

另外，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。In addition, 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層疊體，並可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、觸控面板、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、觸控面板裝置、層疊有ITO等的導電性膜、觸控面板用膜、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、觸控面板裝置、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 polyimide of the present invention can form a laminate having the polyimide layer, and an element layer or the like (functional layer) having various functions can be formed on the surface of the polyimide 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 panel, 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 panel device, a conductive film laminated with ITO and the like, a film for a touch panel, 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 that combines an organic EL lighting device, a touch panel device, and an organic EL display device. 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.

另外，功能層的形成方法可根據目標器件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、或進行熱處理等的公知的方法來獲得。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。In addition, 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 a polyimide film and patterned into a predetermined shape as required, or It can be obtained by a known method such as heat treatment. 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.

作為使聚醯亞胺膜容易自基板剝離並防止延伸的方法，有雷射剝離法。例如日本專利特表2007-512568公報中公開了：在玻璃板上形成聚醯亞胺的黃色膜，繼而在所述黃色膜上形成薄膜電子元件，然後透過玻璃對黃色膜的底面照射紫外（UV）雷射光，由此可將玻璃與黃色膜剝離。根據所述方法，聚醯亞胺膜是利用UV雷射光而自玻璃分離，因此在剝離時完全不會產生應力，從而為優選的方法。然而，也公開了：不同於黃色膜，透明塑膠不吸收UV雷射光，因此需要預先在膜下設置非晶矽之類的吸收/剝離層。As a method for easily peeling the polyfluoreneimide film from the substrate and preventing stretching, there is a laser peeling method. For example, Japanese Patent Publication No. 2007-512568 discloses that a yellow film of polyimide is formed on a glass plate, and then a thin-film electronic component is formed on the yellow film, and then the bottom surface of the yellow film is irradiated with ultraviolet (UV) through the glass. ) Laser light, which can peel the glass from the yellow film. According to the method, since the polyimide film is separated from the glass by UV laser light, no stress is generated at the time of peeling, which is a preferred method. However, it is also disclosed that, unlike a yellow film, transparent plastic does not absorb UV laser light, so it is necessary to provide an absorption / stripping layer such as amorphous silicon under the film in advance.

另外，日本專利特表2012-511173公報中公開了：為了利用UV雷射光的照射進行玻璃板與聚醯亞胺層的剝離而使用300 nm～410 nm的範圍的雷射。此外，作為剝離方法，可列舉：自玻璃側照射雷射，將具備顯示部的樹脂基材自玻璃分離的方法；在玻璃基板上塗布形成剝離層後，在剝離層上塗布聚醯亞胺樹脂，並在有機EL顯示裝置的製造步驟完成後自剝離層剝離聚醯亞胺層的方法；對無機層的表面進行偶合劑處理後，利用UV照射等進行所述偶合劑的圖案化處理，從而形成具有剝離強度不同的良好黏接部分與易剝離部分的層疊體，並自其進行剝離的方法等。In addition, Japanese Patent Publication No. 2012-511173 discloses that a laser in a range of 300 to 410 nm is used for peeling a glass plate from a polyimide layer by irradiation with UV laser light. In addition, examples of the peeling method include a method of irradiating a laser from a glass side and separating a resin substrate including a display portion from the glass; and applying a polyimide resin to the peeling layer after forming a peeling layer on a glass substrate. And a method of peeling the polyfluoreneimide layer from the release layer after the manufacturing step of the organic EL display device is completed; after the surface of the inorganic layer is subjected to a coupling agent treatment, the coupling agent is patterned by UV irradiation or the like, thereby A method of forming a laminated body having a good adhesive portion and an easily peelable portion having different peel strengths, and peeling it therefrom.

自有機EL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裝置中使用的支持基材，要求在所述波長區域中的平均透射率至少為80%以上。另一方面，在上文所述的利用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射率高，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，理想的是盡力不使光透過。The wavelength of light emitted from the light-emitting layer of the organic EL device is mainly 440 nm to 780 nm. Therefore, as a supporting substrate used in the organic EL device, the average transmittance in the wavelength region is required to be at least 80% or more. On the other hand, in the case where the glass and the polyimide layer are peeled by the irradiation of the UV laser light as described above, if the transmittance at the wavelength of the UV laser light is high, it is necessary to separately provide an absorption / release layer. Therefore, productivity is reduced. A 308 nm laser device is currently commonly used in the stripping. In order to perform the peeling without providing the absorbing / stripping layer, the polyimide itself needs to sufficiently absorb 308 nm laser light, and it is desirable to try to prevent light from being transmitted.

以下，作為功能層而以底部發光結構的有機EL顯示裝置為代表例，對其製造方法的概略進行說明。Hereinafter, an organic EL display device having a bottom emission structure as a functional layer will be described as a representative example, and an outline of a manufacturing method thereof will be described.

對用以形成功能層的樹脂基材設置阻氣層而成為可阻止水分或氧的透濕的結構。接著，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畫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畫素區域。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發光層是由空穴注入層-空穴輸送層-發光層-電子輸送層等多層膜（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 resin base material for forming the functional layer to have a moisture-permeable structure capable of preventing moisture or oxygen. 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 formed of an anode electrode in which a plurality of pixel regions where a plurality of pixel regions are arranged in a matrix form, for example, a transparent conductive film including ITO (Indium Tin Oxide). 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. Furthermore, 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.

接著，對用作液晶顯示裝置或有機EL顯示裝置等顯示裝置的輸入單元的觸控面板的概略進行說明。如上所述，顯示裝置的薄型･輕量化以及可撓化的進展顯著，與此呼應地，也對設置於顯示裝置上的觸控面板的薄型化、輕量化、可撓化進行積極研究。Next, an outline of a touch panel used as an input unit of a display device such as a liquid crystal display device or an organic EL display device will be described. As described above, the progress in reducing the thickness, weight, and flexibility of display devices has been remarkable. In response to this, the thickness, weight, and flexibility of touch panels provided on display devices have also been actively studied.

對觸控面板也具有同樣的要求，從而進行了如上所述的研究。 [實施例]The touch panel also has the same requirements, so the research described above was performed. [Example]

以下，基於實施例及比較例對本發明進行具體說明。再者，本發明並不受這些內容限制。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） ･BPDA：3,3',4,4'-聯苯四羧酸二酐 ･CBDA：1,2,3,4-環丁烷四羧酸二酐 ･6FDA：4,4'-(2,2'-六氟亞異丙基)二鄰苯二甲酸二酐 （二胺） ･AAPBZI：5-胺基-2-(4-胺基苯基)苯并咪唑 ･TFMB：2,2'-雙(三氟甲基)聯苯胺 ･m-TB：2,2'-二甲基-4,4'-二胺基聯苯 ･AAPBZO：5-胺基-2-(4-胺基苯基)苯并噁唑 （溶劑） ･NMP：N-甲基-2-吡咯烷酮 （透光率及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308 nm、355 nm、400 nm及430 nm下的透光率（T308、T355、T400、T430）。 另外，基於下述計算式來算出YI（黃色度）。 YI=100×(1.2879X-1.0592Z)/Y X、Y、Z為試驗片的三刺激值，在日本工業標準（JIS）Z 8722中進行了規定。The codes and evaluation methods of the materials used in the examples and comparative examples are shown. (Acid dianhydride) ･ BPDA: 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride ･ CBDA: 1,2,3,4-cyclobutanetetracarboxylic dianhydride FDA6FDA: 4,4 '-(2,2'-hexafluoroisopropylidene) diphthalic dianhydride (diamine) ･ AAPBZI: 5-amino-2- (4-aminophenyl) benzimidazole 咪 TFMB: 2,2'-bis (trifluoromethyl) benzidine ･ m-TB: 2,2'-dimethyl-4,4'-diaminobenzidine ･ AAPBZO: 5-amino-2- (4 -Aminophenyl) benzoxazole (solvent) ･ NMP: N-methyl-2-pyrrolidone (light transmittance and YI) Using a Shimadzu UV-3600 spectrophotometer on a polyfluoreneimide film (50 mm × 50 mm) to determine the transmittance (T308, T355, T400, T430) at 308 nm, 355 nm, 400 nm, and 430 nm. In addition, YI (yellowness) was calculated based on the following calculation formula. YI = 100 × (1.2879X-1.0592Z) / Y X, Y, and Z are tristimulus values of the test piece, and are specified in Japanese Industrial Standard (JIS) Z 8722.

進而，在N2 環境下，使所述膜以一定的速度（3℃/min）自室溫升溫至300℃，保持30 min，其後恢復為室溫，將膜取出並測定加熱處理後的YI（YI300℃）。Furthermore, the film was heated from room temperature to 300 ° C at a certain rate (3 ° C / min) under a N 2 environment for 30 minutes, and then returned to room temperature. The film was taken out and the heat-treated YI was measured. (YI300 ° C).

（CTE） 利用熱機械分析（thermomechanical analysis，TMA）裝置，一邊對3 mm×15 mm尺寸的聚醯亞胺膜施加5.0 g的荷重，一邊以一定的升溫速度（10℃/min）自30℃升溫至280℃，繼而，自250℃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。(CTE) Using a thermomechanical analysis (TMA) device, while applying a 5.0 g load to a polyimide film having a size of 3 mm × 15 mm, the temperature was increased from 30 ° C at a constant temperature increase rate (10 ° C / min). The temperature was raised to 280 ° C, and then the temperature was lowered from 250 ° C to 100 ° C. 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） 在氮氣環境下，利用精工（SEIKO）製造的熱重量分析（thermogravimetric，TG）裝置TG/DTA6200來測定使10 mg～20 mg的聚醯亞胺膜以一定的速度自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) Under a nitrogen environment, a thermogravimetric (TG) device TG / DTA6200 manufactured by SEIKO was used to measure a 10 to 20 mg polyimide film at a constant speed from 30 ° C. The change in weight when the temperature was raised to 550 ° C. The weight at 200 ° C. was set to zero, and the temperature at which the weight reduction rate was 1% was set to the thermal decomposition temperature (Td1%).

（雷射剝離；LLO（laser lift-off）） 對於聚醯亞胺層與玻璃基板的層疊體，使用準分子雷射加工機（波長308 nm）自支持基材（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，並將支持基材與聚醯亞胺層完全分離的狀態（由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）設為○，將塗敷基材與聚醯亞胺層的整個面或一部分無法分離、或者聚醯亞胺層發生了變色的狀態設為×。(Laser lift-off): For a laminate of a polyimide layer and a glass substrate, an excimer laser processing machine (wavelength 308 nm) is used to irradiate the beam size from the supporting substrate (glass substrate) side. It is a laser with a movement speed of 14 mm × 1.2 mm and a movement speed of 6 mm / s, and the support substrate and the polyimide layer are completely separated (the peeling range is determined by the cutting knife, and the polyimide is cut after cutting into a week. The film was naturally peeled from the glass) was set to ○, and the state in which the coating substrate and the entire surface or a part of the polyimide layer could not be separated or the polyimide layer was discolored was set to ×.

（LED）：將直至可將聚醯亞胺層與玻璃基板剝離的雷射照射能量密度（mJ/cm2 ）簡稱為LED（laser energy density）。能量密度越高越難以剝離。也考慮到雷射照射裝置的壽命，優選的是照射能量密度小。(LED): Laser irradiation energy density (mJ / cm 2 ) until the polyimide layer can be peeled from the glass substrate is simply referred to as LED (laser energy density). The higher the energy density, the more difficult it is to peel. In consideration of the life of the laser irradiation device, it is preferable that the irradiation energy density is small.

（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500℃時的動態黏彈性，並求出玻璃轉移溫度（tanδ極大值：℃）。(Glass transition temperature; Tg) A dynamic thermomechanical analysis device was used to measure the dynamic viscoelasticity of the polyimide film (5 mm × 70 mm) when the temperature was raised from 23 ° C to 500 ° C at 5 ° C / min, and the glass transition was determined. Temperature (tanδ maximum: ° C).

依照下述合成例1～合成例8，製備用以形成實施例及比較例的聚醯亞胺層疊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組成匯總示於表1與表2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 8. Table 1 and Table 2 summarize the weight composition of the monomers in each polyfluorene imide precursor solution.

合成例1 在氮氣氣流下，在100 ml的可分離式燒瓶中使8.5575 g的TFMB溶解於85 g的NMP中。繼而，在所述溶液中添加0.6678 g的AAPBZI。攪拌10分鐘後添加5.7757 g的CBDA。再者，將酸二酐（a）與二胺（b）的莫耳比（a/b）設為0.990。對所述溶液以40℃加熱10分鐘而使內容物溶解，其後，在室溫下將溶液持續攪拌24小時以進行聚合反應，獲得高聚合度的聚醯亞胺前體A（黏稠的無色溶液）。Synthesis Example 1 Under nitrogen gas flow, 8.5575 g of TFMB was dissolved in 85 g of NMP in a 100 ml separable flask. Then, 0.6678 g of AAPBZI was added to the solution. After stirring for 10 minutes, 5.7757 g of CBDA was added. The molar ratio (a / b) of the acid dianhydride (a) to the diamine (b) was set to 0.990. 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 24 hours to perform a polymerization reaction to obtain a highly polymerized polyimide precursor A (thick colorless Solution).

合成例2～合成例9 除將酸二酐及二胺變更為表1與表2所示的質量組成以外，與合成例1同樣地製備聚醯亞胺前體溶液，獲得聚醯亞胺前體B～聚醯亞胺前體I。Synthesis Example 2 to Synthesis Example 9 A polyimide precursor solution was prepared in the same manner as in Synthesis Example 1 except that the acid dianhydride and diamine were changed to the mass compositions shown in Tables 1 and 2. Before obtaining polyimide Body B to polyimide precursor I.

[表1] [Table 1]

[表2] [Table 2]

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，然後使用旋塗機，以硬化後的聚醯亞胺厚度成為約13 μm的方式塗敷於玻璃基板（康寧（Corning）製造的E-XG，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300℃，中途在130℃下保持10 min，從而在玻璃基板上形成150 mm×150 mm的第1聚醯亞胺層（聚醯亞胺A），獲得聚醯亞胺層疊體A。Example 1 A solvent NMP was added to the polyimide 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 polyimide was changed to a thickness using a spin coater. Approx. 13 μm was applied on a glass substrate (E-XG manufactured by Corning, 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 300 ° C. at a constant temperature increase rate (3 ° C./min), and maintained at 130 ° C. for 10 minutes, so that a first polymer of 150 mm × 150 mm was formed on the glass substrate. An imine layer (polyimide A) to obtain a polyimide laminate A.

實施例2～實施例6、比較例1～比較例3 除將聚醯亞胺前體改為聚醯亞胺前體B～聚醯亞胺前體I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層疊體B～聚醯亞胺層疊體I。聚醯亞胺前體與聚醯亞胺層疊體的符號相對應，意指由聚醯亞胺前體B獲得聚醯亞胺層疊體B，關於符號C及以後的符號也同樣如此。Examples 2 to 6 and Comparative Examples 1 to 3 were the same as in Example 1 except that the polyfluorene imine precursor was changed to any one of the polyfluorene imine precursor B to the polyfluorene imine precursor I. The same procedure was performed to obtain polyfluoreneimide laminate B to polyfluoreneimide laminate I. The polyimide precursor corresponds to the symbol of the polyimide laminate, which means that the polyimide laminate B is obtained from the polyimide precursor B, and the same applies to the symbol C and subsequent symbols.

關於所獲得的聚醯亞胺層疊體A～聚醯亞胺層疊體I，測定雷射剝離（LLO）及LED。將結果示於表3及表4中。With respect to the obtained polyimide laminate A to polyimide laminate I, laser peeling (LLO) and LED were measured. The results are shown in Tables 3 and 4.

關於上述以外的測定，是自層疊體剝離聚醯亞胺膜後進行，所述情況下的層疊體是使用75 μm的聚醯亞胺膜來作為基板，以代替玻璃基板，除此以外依照上文所述製作而成。將詳細的製作條件示於以下。Measurements other than the above are performed after the polyimide film is peeled from the laminate. In this case, the polyimide film with a thickness of 75 μm is used as a substrate instead of a glass substrate. Made as described here. The detailed production conditions are shown below.

在合成例1～合成例9中所獲得的聚醯胺酸（polyamide acid）溶液A～聚醯胺酸溶液I中添加溶劑NMP而以黏度成為3000 cP的方式進行稀釋，然後塗敷於75 μm的聚醯亞胺膜（尤皮賴克斯（Upilex）-S）基板上。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℃（比較例2、比較例3為360℃），中途在130℃下保持10 min，從而獲得聚醯亞胺層疊膜。然後，剝離聚醯亞胺基材而形成聚醯亞胺膜A～聚醯亞胺膜I。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。A solvent NMP was added to the polyamic acid solution A to the polyamic acid solution I obtained in Synthesis Example 1 to Synthesis Example 9 to dilute it so that the viscosity became 3000 cP, and then applied to 75 μm. Polyimide film (Upilex-S) 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 constant temperature increase rate (3 ° C / min) (Comparative Example 2, Comparative Example 3 was 360 ° C), and maintained at 130 ° C for 10 minutes, thereby obtaining polyfluorene. Imine laminated film. Then, the polyfluorene imide substrate is peeled off to form a polyfluorene film A to a polyfluorene film I. 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.

關於所獲得的聚醯亞胺膜A～聚醯亞胺膜I，分別進行CTE、透光率、YI、Td1及Tg等各種評價。將結果示於表3與表4中。Various evaluations, such as CTE, light transmittance, YI, Td1, and Tg, were performed on the obtained polyfluorene imine film A to polyfluorene imine film I. The results are shown in Tables 3 and 4.

[表3] [table 3]

[表4] [Table 4]

無no

無no

Claims (9)

一種聚醯亞胺前體，具有源自二胺的結構單元與源自酸二酐的結構單元，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2,2'-雙(三氟甲基)聯苯胺的結構單元或源自1,2,3,4-環丁烷四羧酸二酐的結構單元；式（1） （式（1）中，Z為NH或O）。A polyfluorene imide precursor having a structural unit derived from a diamine and a structural unit derived from an acid dianhydride. The polyfluorene imide precursor is characterized by having i) derived from the following formula (1): Represented by the structural unit of an aromatic diamine, and ii) a structural unit derived from 2,2'-bis (trifluoromethyl) benzidine or derived from 1,2,3,4-cyclobutanetetracarboxylic acid di Structural unit of anhydride Formula (1) (In Formula (1), Z is NH or O). 如申請專利範圍第1項所述的聚醯亞胺前體，其包含源自二胺的所有結構單元的5莫耳%以上的源自芳香族二胺的結構單元。The polyfluorene imide precursor according to item 1 of the scope of patent application, which contains 5 mol% or more of the structural unit derived from the aromatic diamine of all the structural units derived from the diamine. 如申請專利範圍第1項或第2項所述的聚醯亞胺前體，其包含源自酸二酐的所有結構單元的50莫耳%以上的源自1,2,3,4-環丁烷四羧酸二酐的結構單元。The polyimide precursor according to item 1 or item 2 of the patent application scope, which contains more than 50 mol% of all structural units derived from acid dianhydride derived from 1,2,3,4-ring The structural unit of butanetetracarboxylic dianhydride. 如申請專利範圍第1項或第2項所述的聚醯亞胺前體，其包含源自二胺的所有結構單元的50莫耳%以上的源自2,2'-雙(三氟甲基)聯苯胺的結構單元。The polyfluorene imide precursor according to item 1 or item 2 of the patent application scope, which contains more than 50 mole% of all structural units derived from diamine and is derived from 2,2′-bis (trifluoromethyl) A structural unit of benzidine. 如申請專利範圍第1項或第2項所述的聚醯亞胺前體，其中在氮氣環境下對所述聚醯亞胺前體進行醯亞胺化而得的聚醯亞胺的黃色度為6以下，且自250℃變化為100℃時的熱膨脹係數為35 ppm/K以下。The polyimide precursor according to item 1 or item 2 of the scope of application for a patent, wherein the polyimide obtained by performing amidine imidization on the polyimide precursor under a nitrogen atmosphere has a yellowness of the polyimide The coefficient of thermal expansion when it is 6 or less and changes from 250 ° C to 100 ° C is 35 ppm / K or less. 如申請專利範圍第1項或第2項所述的聚醯亞胺前體，其中對所述聚醯亞胺前體進行醯亞胺化而得的聚醯亞胺的308 nm的透光率為5%以下，430 nm的透光率為70%以上。The polyfluorene imide precursor according to item 1 or 2 of the scope of application for a patent, wherein the polyfluorene imide obtained by fluorimiding the polyfluorene imine precursor has a light transmittance of 308 nm. It is 5% or less, and the light transmittance at 430 nm is 70% or more. 一種聚醯亞胺，具有源自二胺的結構單元與源自酸二酐的結構單元，所述聚醯亞胺的特徵在於：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2,2'-雙(三氟甲基)聯苯胺的結構單元或源自1,2,3,4-環丁烷四羧酸二酐的結構單元；式（1） （式（1）中，Z為NH或O）。A polyfluorene imine having a structural unit derived from a diamine and a structural unit derived from an acid dianhydride, the polyfluorene imide is characterized by having i) an aromatic group derived from the following formula (1) Structural units of diamine, and ii) structural units derived from 2,2'-bis (trifluoromethyl) benzidine or structural units derived from 1,2,3,4-cyclobutanetetracarboxylic dianhydride ; Formula (1) (In Formula (1), Z is NH or O). 如申請專利範圍第7項所述的聚醯亞胺，其黃色度為6以下，自250℃變化為100℃時的熱膨脹係數為35 ppm/K以下。According to the polyimide described in item 7 of the scope of patent application, the yellowness is 6 or less, and the thermal expansion coefficient when the temperature changes from 250 ° C to 100 ° C is 35 ppm / K or less. 如申請專利範圍第7項或第8項所述的聚醯亞胺，其308 nm的透光率為5%以下，430 nm的透光率為70%以上。According to the polyimide described in item 7 or item 8 of the scope of patent application, the light transmittance of 308 nm is less than 5%, and the light transmittance of 430 nm is more than 70%.
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