TW202239889A - Polyimide precursor varnish and method for producing same, polyimide and method for producing same, flexible device, and laminate for wiring board - Google Patents

Abstract

Provided are a polyimide film and a precursor thereof with which it is possible to obtain a transparent polyimide that is most suitable for a transparent base material for a laminate for a flexible device and a wiring board and has low coloration and high transmittance. A polyimide precursor varnish and a method for producing the same, a polyimide and a method for producing the same, a flexible device, and a laminate for a wiring board, the polyimide precursor varnish comprising a polyimide precursor and an organic solvent, the organic solvent of the polyimide precursor varnish having a yellowness YI of 2.0 or less, b * of 1.0 or less, and c * of 1.0 or less. The polyimide precursor varnish has a yellowness (YI) of less than 5.0 and a b * of less than 2.0.

Description

Translated fromChinese

聚醯亞胺前體清漆及其製造方法、聚醯亞胺及其製造方法、可撓性器件及配線基板用層疊體Polyimide precursor varnish and method for producing same, polyimide and method for producing same, flexible device and laminate for wiring board

本發明是有關於一種透明的聚醯亞胺前體、及聚醯亞胺。The invention relates to a transparent polyimide precursor and polyimide.

液晶顯示裝置、有機電致發光（electroluminescence，EL）裝置等顯示裝置或觸控式螢幕被用作以電視之類的大型顯示器或行動電話、個人電腦、智慧手機等小型顯示器為代表的各種顯示器的構成構件。 例如，有機EL裝置一般是在作為支撐基材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這些氣密密封而製成。另外，觸控式螢幕成為將形成有第一電極的第一玻璃基板與形成有第二電極的第二玻璃基板經由絕緣層（介電層）接合而成的構成。Display devices such as liquid crystal display devices and organic electroluminescence (EL) devices, or touch screens are used for various displays including large displays such as televisions and small displays such as mobile phones, personal computers, and smartphones. constitute components. For example, in an organic EL device, a thin film transistor (thin film transistor, TFT) is generally formed on a glass substrate as a supporting substrate, and then an electrode, a light-emitting layer, and an electrode are sequentially formed on it. These are made hermetically sealed. In addition, the touch screen has a structure 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 bonded via an insulating layer (dielectric layer).

即，這些構成構件為在玻璃基板上形成有TFT、電極、發光層等各種功能層的層疊體。藉由將所述玻璃基板替換成樹脂基板，可對使用現有的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器件。另一方面，與玻璃相比，樹脂的尺寸穩定性、透明性、耐熱性、耐濕性、膜的強度等較差，因此正進行各種研究。That is, these constituent members are laminates in which various functional layers such as TFTs, electrodes, and light-emitting layers are formed on a glass substrate. By replacing the above-mentioned glass substrate with a resin substrate, it is possible to reduce the thickness, weight and flexibility of the constituent members using the existing glass substrate. It is expected to use it to obtain flexible devices such as flexible displays. On the other hand, resins are inferior to glass in terms of dimensional stability, transparency, heat resistance, moisture resistance, film strength, etc., and therefore various studies are being conducted.

作為此種樹脂基板材料，聚醯亞胺因耐熱性或尺寸穩定性優異而為有希望的材料之一，期待應用於有機EL裝置用基板、觸控式螢幕基板、彩色濾光片基板等需要透明性的可撓性器件。As such a resin substrate material, polyimide is one of the promising materials because of its excellent heat resistance and dimensional stability, and it is expected to be used in substrates for organic EL devices, touch screen substrates, color filter substrates, etc. Transparent flexible devices.

面向可撓性器件的透明聚醯亞胺基板是藉由以下方式來獲得：以玻璃基板為支撐基材，在所述支撐基材上形成透明聚醯亞胺膜，繼而在透明聚醯亞胺膜上安裝電子零件後剝離支撐基材。The transparent polyimide substrate facing the flexible device is obtained by the following method: a glass substrate is used as a supporting substrate, a transparent polyimide film is formed on the supporting substrate, and then a transparent polyimide film is formed on the transparent polyimide After mounting electronic parts on the film, the support substrate is peeled off.

例如，專利文獻1公開一種自載體基板剝離而製造的可撓性器件用的含氟聚醯亞胺膜，玻璃化轉變溫度為300℃以上，熱分解溫度為500℃以上，熱膨脹係數為20 ppm/K以下。但是，未對透明性進行研究。 專利文獻2報告一種藉由使用400 nm下的透光率為89%以上的有機溶劑而透明性高的聚醯亞胺膜。但是，為了對溶劑進行精製，不僅需要繁雜的工序，而且即便溶劑的透光率高，所獲得的聚醯亞胺有時也會著色，因此僅藉由提高溶劑的透光率並不足以獲得高透明的聚醯亞胺。 [現有技術文獻] [專利文獻]For example, Patent Document 1 discloses a fluorine-containing polyimide film for flexible devices manufactured by peeling off from a carrier substrate, with a glass transition temperature of 300°C or higher, a thermal decomposition temperature of 500°C or higher, and a thermal expansion coefficient of 20 ppm /K below. However, transparency was not studied. Patent Document 2 reports a polyimide film having high transparency by using an organic solvent having a light transmittance of 89% or more at 400 nm. However, in order to purify the solvent, not only complicated steps are required, but also the obtained polyimide may be colored even if the light transmittance of the solvent is high, so it is not enough to obtain Highly transparent polyimide. [Prior art literature] [Patent Document]

[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2013-23597號公報[Patent Document 1] Japanese Patent Laid-Open No. 2012-040836 [Patent Document 2] Japanese Patent Laid-Open No. 2013-23597

本發明的目的在於提供一種可獲得對於可撓性器件及配線基板用層疊體用的透明基材而言最合適的具有低著色、高透過率的透明聚醯亞胺的聚醯亞胺膜及其前體。The object of the present invention is to provide a polyimide film which can obtain a transparent polyimide having low coloring and high transmittance which is most suitable for a transparent base material for a laminate for a flexible device and a wiring board, and its precursor.

本發明者等人進行了努力研究，結果發現，著眼於聚醯亞胺前體清漆或聚醯亞胺的調整、製造時使用的有機溶劑，對於低著色度（黃色指數（yellowness index，YI））、色彩值L*、a*、b*，藉由使用特定的溶劑，可獲得低著色且高透過率的聚醯亞胺前體清漆或聚醯亞胺，從而完成了本發明。The inventors of the present invention conducted diligent research, and as a result, it was found that the adjustment of the polyimide precursor varnish or the polyimide, and the organic solvent used in the production, are effective for low coloration (yellowness index (YI) ), color values L*, a*, b*, by using a specific solvent, a polyimide precursor varnish or polyimide with low coloration and high transmittance can be obtained, thus completing the present invention.

即，本發明是一種聚醯亞胺前體清漆，包含聚醯亞胺前體及有機溶劑，所述聚醯亞胺前體清漆的特徵在於，所述有機溶劑的黃色度YI為2.0以下，b*為1.0以下，所述聚醯亞胺前體清漆的黃色度（YI）未滿5.0，b*未滿2.0。That is, the present invention is a polyimide precursor varnish comprising a polyimide precursor and an organic solvent, wherein the polyimide precursor varnish is characterized in that the yellowness YI of the organic solvent is 2.0 or less, b* is 1.0 or less, the yellowness (YI) of the polyimide precursor varnish is less than 5.0, and b* is less than 2.0.

本發明的聚醯亞胺前體清漆優選為有機溶劑在光路長1 cm、400 nm波長下的透光率為85%以上且未滿89%。 本發明的聚醯亞胺前體清漆優選為有機溶劑為選自由N,N-二甲基乙醯胺、N,N-二甲基甲醯胺、N-甲基-2-吡咯烷酮、N-乙基-2-吡咯烷酮、二甲基咪唑烷酮、及γ-丁內酯所組成的群組中的一種以上。The polyimide precursor varnish of the present invention preferably has an organic solvent light transmittance of 85% or more and less than 89% at an optical path length of 1 cm and a wavelength of 400 nm. The polyimide precursor varnish of the present invention is preferably an organic solvent selected from N,N-dimethylacetamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, N- One or more species selected from the group consisting of ethyl-2-pyrrolidone, dimethylimidazolidinone, and γ-butyrolactone.

本發明是一種聚醯亞胺前體清漆的製造方法，是製造包含聚醯亞胺前體及有機溶劑的聚醯亞胺前體清漆的方法，所述聚醯亞胺前體清漆的製造方法的特徵在於，使用黃色度YI為2.0以下、b*為1.0以下的有機溶劑作為所述有機溶劑，獲得黃色度YI未滿5.0、b*未滿2.0的聚醯亞胺前體清漆。The present invention is a method for producing a polyimide precursor varnish, a method for producing a polyimide precursor varnish comprising a polyimide precursor and an organic solvent, and the method for producing the polyimide precursor varnish A polyimide precursor varnish having a yellowness YI of less than 5.0 and a b* of less than 2.0 is obtained using an organic solvent having a yellowness YI of 2.0 or less and b* of 1.0 or less as the organic solvent.

本發明是一種聚醯亞胺，是對包含聚醯亞胺前體及有機溶劑的聚醯亞胺前體清漆進行醯亞胺化而成，所述聚醯亞胺的特徵在於，所述有機溶劑的黃色度YI為2.0以下，b*為1.0以下，聚醯亞胺的黃色度YI（厚度10 μm換算值）為30以下，總透光率為80%以上。The present invention is a polyimide, which is obtained by imidizing a polyimide precursor varnish containing a polyimide precursor and an organic solvent. The polyimide is characterized in that the organic The yellowness YI of the solvent is 2.0 or less, b* is 1.0 or less, the yellowness YI of the polyimide (thickness 10 μm conversion value) is 30 or less, and the total light transmittance is 80% or more.

本發明是一種聚醯亞胺的製造方法，是製造對包含聚醯亞胺前體及有機溶劑的聚醯亞胺前體清漆進行醯亞胺化而成的聚醯亞胺的方法，所述聚醯亞胺的製造方法的特徵在於，使用黃色度YI為2.0以下、b*為1.0以下的有機溶劑作為所述有機溶劑，獲得黃色度YI（厚度10 μm換算值）為30以下、總透光率為80%以上的聚醯亞胺。The present invention is a method for producing polyimide, which is a method for producing polyimide obtained by imidizing a polyimide precursor varnish containing a polyimide precursor and an organic solvent. The method for producing polyimide is characterized in that an organic solvent having a yellowness YI of 2.0 or less and b* of 1.0 or less is used as the organic solvent to obtain a yellowness YI (thickness 10 μm conversion value) of 30 or less and a total transparency. Polyimide with a light rate of more than 80%.

本發明是一種可撓性器件，其特徵在於，包括包含所述聚醯亞胺的聚醯亞胺層、以及形成於所述聚醯亞胺層上的功能層。 本發明是一種配線基板用層疊體，其特徵在於，具有包含所述聚醯亞胺的聚醯亞胺層、以及在所述聚醯亞胺層的單面或兩面上的金屬層。The present invention is a flexible device characterized by comprising a polyimide layer comprising the polyimide, and a functional layer formed on the polyimide layer. The present invention is a laminate for a wiring board, characterized by comprising a polyimide layer containing the polyimide described above, and metal layers on one or both surfaces of the polyimide layer.

根據本發明，著眼於聚醯亞胺前體清漆或聚醯亞胺的調整、製造時使用的有機溶劑，對於黃色度（YI）、色彩值L*、a*、b*，使用特定的溶劑，由此可達成提供低的著色且高的透光率的聚醯亞胺前體清漆或聚醯亞胺。According to the present invention, focusing on the adjustment and production of polyimide precursor varnishes and organic solvents used in the production of polyimide, specific solvents are used for yellowness (YI) and color values L*, a*, and b* , thereby achieving a polyimide precursor varnish or polyimide that provides low coloring and high light transmittance.

本發明的聚醯亞胺前體清漆包含聚醯亞胺前體及有機溶劑，有機溶劑的黃色度YI為2.0以下，b*為1.0以下，光路長1 cm、400 nm波長下的透光率為85%以上。 本發明者等人觀察到，即便在使用透光率為89%以上的溶劑作為有機溶劑的情況下，所獲得的聚醯亞胺前體或聚醯亞胺也有著色，透光率低，僅透光率高時，對於獲得高透明的聚醯亞胺前體或聚醯亞胺是不充分的，研究存在更有效的參數，從而完成了本發明。發現其有效的參數為黃色度（YI）、色彩值L*、a*、b*，特別是黃色度YI、及色彩值b*會顯著影響聚醯亞胺前體清漆或聚醯亞胺的透明性。The polyimide precursor varnish of the present invention comprises a polyimide precursor and an organic solvent, the yellowness YI of the organic solvent is less than 2.0, b* is less than 1.0, the optical path length is 1 cm, and the light transmittance at a wavelength of 400 nm more than 85%. The inventors of the present invention have observed that even when a solvent having a light transmittance of 89% or more is used as an organic solvent, the obtained polyimide precursor or polyimide is colored, the light transmittance is low, and only When the light transmittance is high, it is not sufficient to obtain a highly transparent polyimide precursor or polyimide, and the existence of more effective parameters has been investigated, thereby completing the present invention. The parameters found to be effective are the yellowness (YI), the color values L*, a*, b*, especially the yellowness YI, and the color value b* can significantly affect the performance of polyimide precursor varnishes or polyimides. transparency.

在本發明的聚醯亞胺前體清漆中，作為有機溶劑，黃色度YI必須為2.0以下，b*必須為1.0以下。黃色度YI值、b*值中的任一者不滿足所述條件的有機溶劑中無法表現出本發明的效果。 有機溶劑的黃色度YI優選為1.90以下，更優選為1.50以下。b*值優選為0.90以下，更優選為0.85以下。In the polyimide precursor varnish of the present invention, as an organic solvent, the yellowness YI must be 2.0 or less, and b* must be 1.0 or less. The effect of the present invention cannot be exhibited in an organic solvent that does not satisfy the above-mentioned conditions in either the yellowness YI value or the b* value. The yellowness YI of the organic solvent is preferably 1.90 or less, more preferably 1.50 or less. The b* value is preferably 0.90 or less, more preferably 0.85 or less.

雖然關於其他色彩值L*、a*並非必需，但作為有機溶劑，可自色彩值L*優選為90.0以上、更優選為93.0以上的有機溶劑中選擇。在本發明中，即便是L*值為97.0以下或96.0以下的有機溶劑也可優選地使用。作為有機溶劑，可自色彩值a*優選為-0.10～-0.80、更優選為-0.20～-0.70的有機溶劑中選擇。The other color values L* and a* are not essential, but the organic solvent can be selected from organic solvents whose color value L* is preferably 90.0 or more, more preferably 93.0 or more. In the present invention, even an organic solvent having an L* value of 97.0 or less or 96.0 or less can be preferably used. The organic solvent can be selected from those whose color value a* is preferably -0.10 to -0.80, more preferably -0.20 to -0.70.

本發明的聚醯亞胺前體清漆優選為作為有機溶劑，光路長1 cm、400 nm波長下的透光率為85%以上即可，透光率無須為89%以上。即便是透光率未滿89%、未滿88%或未滿87%的有機溶劑也可優選地使用。若為透光率未滿89%的有機溶劑，則即便並非為繁雜的精製也可容易地製造，就所述方面而言優選。The polyimide precursor varnish of the present invention is preferably used as an organic solvent, with an optical path length of 1 cm and a light transmittance of 85% or more at a wavelength of 400 nm. The light transmittance does not need to be 89% or more. Even an organic solvent having a light transmittance of less than 89%, less than 88%, or less than 87% can be preferably used. If it is an organic solvent with a light transmittance of less than 89%, it can be easily produced without complicated purification, which is preferable in this point.

本發明的聚醯亞胺前體清漆優選為作為有機溶劑，純度為99.8%以上即可，純度無須為99.9%以上。即便是純度未滿99.9%的有機溶劑也可優選地使用。若為純度未滿99.9%的有機溶劑，則即便並非為繁雜的精製也可製造，就所述方面而言優選。The polyimide precursor varnish of the present invention is preferably used as an organic solvent with a purity of 99.8% or higher, but does not need to be 99.9% or higher. Even an organic solvent with a purity of less than 99.9% can be preferably used. If it is an organic solvent with a purity of less than 99.9%, it can be produced without complicated purification, which is preferable in this point.

作為有機溶劑，只要滿足所述黃色度YI、色彩值，則可使用聚醯亞胺前體或聚醯亞胺的調整、製造時使用的各種有機溶劑。例如可列舉：N,N-二甲基乙醯胺（N,N-dimethyl acetamide，DMAC）、N,N-二甲基甲醯胺（N,N-dimethyl formamide，DMF）、N-甲基-2-吡咯烷酮（N-methyl-2-pyrrolidone，NMP）、N-乙基-2-吡咯烷酮（N-ethyl-2-pyrrolidone，NEP）、二甲基咪唑烷酮（dimethyl imidazolidinone，DMI）、或γ-丁內酯（γ-butyrolactone，GBL）等。也可將這些混合而使用。As the organic solvent, as long as the above-mentioned yellowness YI and color value are satisfied, various organic solvents used for the adjustment and production of the polyimide precursor or polyimide can be used. For example, N,N-dimethylacetamide (N,N-dimethyl acetamide, DMAC), N,N-dimethylformamide (N,N-dimethyl formamide, DMF), N-methyl -2-pyrrolidone (N-methyl-2-pyrrolidone, NMP), N-ethyl-2-pyrrolidone (NEP), dimethyl imidazolidinone (dimethyl imidazolidinone, DMI), or γ-butyrolactone (γ-butyrolactone, GBL), etc. These can also be used in mixture.

本發明的聚醯亞胺前體清漆的黃色度（YI）必須未滿5.0，b*必須未滿2.0。黃色度YI值、b*值中的任一者不滿足所述條件的聚醯亞胺前體清漆中無法獲得所期望的聚醯亞胺。 聚醯亞胺前體清漆的黃色度YI優選為4.00以下，更優選為3.00以下。b*值優選為1.50以下，更優選為1.00以下。The yellowness (YI) of the polyimide precursor varnish of this invention must be less than 5.0, and b* must be less than 2.0. A desired polyimide cannot be obtained from the polyimide precursor varnish whose yellowness YI value and b* value do not satisfy the above conditions. The yellowness YI of the polyimide precursor varnish is preferably 4.00 or less, more preferably 3.00 or less. The b* value is preferably 1.50 or less, more preferably 1.00 or less.

雖然關於其他色彩值L*、a*並非必需，但作為聚醯亞胺前體清漆，可自色彩值L*優選為90.0以上、更優選為93.0以上的聚醯亞胺前體清漆中選擇。在本發明中，即便是L*值為97.0以下的聚醯亞胺前體清漆也可優選地使用。作為聚醯亞胺前體清漆，可自色彩值a*優選為-2.0～2.0、更優選為-1.0～1.0的聚醯亞胺前體清漆中選擇。Although other color values L* and a* are not essential, the polyimide precursor varnish can be selected from polyimide precursor varnishes whose color value L* is preferably 90.0 or more, more preferably 93.0 or more. In the present invention, even a polyimide precursor varnish having an L* value of 97.0 or less can be preferably used. The polyimide precursor varnish can be selected from polyimide precursor varnishes whose color value a* is preferably -2.0 to 2.0, more preferably -1.0 to 1.0.

本發明的聚醯亞胺前體只要具有下述通式（1）所表示的結構單元，且具有源自酸二酐（A）的結構單元與源自二胺（B）的結構單元，則可廣範圍地應用。 [化1]

此處，A表示酸二酐殘基，B表示二胺殘基。As long as the polyimide precursor of the present invention has a structural unit represented by the following general formula (1), and has a structural unit derived from an acid dianhydride (A) and a structural unit derived from a diamine (B), then Can be widely used. [chemical 1]

Here, A represents an acid dianhydride residue, and B represents a diamine residue.

作為原料的酸二酐及二胺的組合可列舉：芳香族酸二酐/芳香族二胺、芳香族酸二酐/脂肪族二胺、脂肪族酸二酐/芳香族二胺、脂肪族酸二酐/脂肪族二胺，但優選為包含芳香族成分。在包含脂肪族成分的情況下，優選為具有脂環結構。在要求耐熱性的用途中，優選為芳香族酸二酐與芳香族二胺的組合。Combinations of acid dianhydride and diamine as raw materials include aromatic acid dianhydride/aromatic diamine, aromatic acid dianhydride/aliphatic diamine, aliphatic acid dianhydride/aromatic diamine, aliphatic acid Dianhydride/aliphatic diamine, but preferably contains aromatic components. When containing an aliphatic component, it is preferable to have an alicyclic structure. For applications requiring heat resistance, a combination of an aromatic acid dianhydride and an aromatic diamine is preferable.

作為酸二酐，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、均苯四甲酸二酐、3,3',4,4'-聯苯四羧酸二酐、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'-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、萘-1,2,6,7-四羧酸二酐、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、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、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。也可為這些的混合物。Examples of the acid dianhydride include: 4,4'-(2,2'-hexafluoroisopropylidene)diphthalic dianhydride, naphthalene-2,3,6,7-tetracarboxylic dianhydride , Naphthalene-1,2,5,6-tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3 '-Biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2, 2',3,3'-Benzophenone tetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, naphthalene-1,2,4,5-tetracarboxylic Acid dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, naphthalene-1,2,6,7-tetracarboxylic 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 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, 3,3',4,4'-p-terphenyltetracarboxylic dianhydride, 2,2',3,3'-p-terphenyltetracarboxylic dianhydride, 2,3, 3',4'-terphenyltetracarboxylic 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, 1,1-bis(2,3-dicarboxyphenyl)ethanedianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethanedianhydride, perylene-2,3,8,9- Tetracarboxylic dianhydride, perylene-3,4,9,10-tetracarboxylic dianhydride, perylene-4,5,10,11-tetracarboxylic dianhydride, perylene-5,6,11,12-tetracarboxylic Acid dianhydride, phenanthrene-1,2,7,8-tetracarboxylic dianhydride, phenanthrene-1,2,6,7-tetracarboxylic dianhydride, phenanthrene-1,2,9,10-tetracarboxylic di anhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic acid 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, bis{3,5-bis(trifluoromethane base)phenoxy}pyromellitic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 5,5'-bis(trifluoromethyl)-3,3 ',4,4'-tetracarboxybiphenyldianhydride, 2,2',5,5'-tetrakis(trifluoromethyl)-3,3',4,4'-tetracarboxybiphenyldianhydride, 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)trifluoro Methylphthalic 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)bis Carboxyphenoxy}bis(trifluoromethyl)biphenyl dianhydride, bis{(trifluoromethyl)dicarboxyphenoxy}diphenylether dianhydride, bis(dicarboxyphenoxy)bis(trifluoro Methyl) biphenyl dianhydride, etc. Mixtures of these are also possible.

優選為4,4'-(2,2'-六氟亞異丙基)二鄰苯二甲酸二酐（4,4'-(2,2'-hexafluoroisopropylidene)diphthalic dianhydride，6FDA）、4,4'-氧基二鄰苯二甲酸二酐（4,4'-oxydiphthalic dianhydride，ODPA）、均苯四甲酸二酐（pyromellitic dianhydride，PMDA）、3,3',4,4'-聯苯四羧酸二酐（3,3',4,4'-biphenyl tetracarboxylic dianhydride，BPDA）、或1,2,3,4-環丁烷四羧酸二酐。 其中，只要聚醯亞胺前體清漆的黃色度（YI）未滿5.0、b*未滿2.0，則並不限定於這些。Preferably 4,4'-(2,2'-hexafluoroisopropylidene)diphthalic dianhydride (4,4'-(2,2'-hexafluoroisopropylidene)diphthalic dianhydride, 6FDA), 4,4 '-Oxydiphthalic dianhydride (4,4'-oxydiphthalic dianhydride, ODPA), pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic Acid dianhydride (3,3',4,4'-biphenyl tetracarboxylic dianhydride, BPDA), or 1,2,3,4-cyclobutane tetracarboxylic dianhydride. However, as long as the yellowness (YI) of the polyimide precursor varnish is less than 5.0 and b* is less than 2.0, it is not limited to these.

作為二胺，例如可列舉：2,2-雙(三氟甲基)聯苯胺、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、2,2'-二甲基-4,4'-二氨基聯苯、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、對苯二胺、間苯二胺、4,6-二甲基-間苯二胺、2,5-二甲基-對苯二胺、2,4-二氨基均三甲苯、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、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、3,3'-二氨基二苯基醚、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-叔丁基苯基)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(1,3-二甲基-5-氨基戊基)苯、1,5-二氨基萘、2,6-二氨基萘、2,4-雙(β-氨基-叔丁基)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、5-氨基-2-(4-氨基苯基)苯並咪唑、或二氨基丙基四甲基二矽氧烷等。也可為這些的混合物。Examples of diamines include: 2,2-bis(trifluoromethyl)benzidine, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy) Benzene, 1,4-bis(4-aminophenoxy)benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'- Diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, p-phenylenediamine, m-phenylenediamine, 4,6-dimethyl-m-phenylenediamine Amine, 2,5-dimethyl-p-phenylenediamine, 2,4-diamino-mesitylene, 4,4'-methylenebis-o-toluidine, 4,4'-methylenebis-2 ,6-xylidine, 4,4'-methylene-2,6-diethylaniline, 2,4-toluenediamine, 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'-diaminodiphenylsulfide, 3,3'-diaminodiphenyl Base sulfide, 3,3'-diaminodiphenyl ether, benzidine, 3,3'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3, 3'-dimethoxybenzidine, 4,4'-diamino-p-terphenyl, 3,3'-diamino-p-terphenyl, bis(p-β-amino-tert-butylphenyl)ether, Bis(p-β-methyl-δ-aminopentyl)benzene, p-bis(2-methyl-4-aminopentyl)benzene, p-bis(1,3-dimethyl-5-aminopentyl) Base) benzene, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,4-bis(β-amino-tert-butyl)toluene, 2,4-diaminotoluene, m-xylene-2, 5-diamine, p-xylene-2,5-diamine, m-xylylenediamine, p-xylylenediamine, 5-amino-2-(4-aminophenyl)benzimidazole, or diaminopropyl Tetramethyldisiloxane, etc. Mixtures of these are also possible.

優選為2,2-雙(三氟甲基)聯苯胺（2,2-bis(trifluoromethyl)benzidine，TFMB）、1,3-雙(3-氨基苯氧基)苯（1,3-bis(3-aminophenoxyl)benzene，APB）、1,3-雙(4-氨基苯氧基)苯（1,3-bis(4-aminophenoxyl)benzene，TPE-R）、1,4-雙(4-氨基苯氧基)苯、4,4'-二氨基二苯基醚、對苯二胺（p-phenylenediamine，p-PDA）、4,6-二甲基-間苯二胺、2,5-二甲基-對苯二胺、2,4-二氨基均三甲苯、2,4-甲苯二胺、間苯二胺、2,2'-二甲基-4,4'-二氨基聯苯、或5-氨基-2-(4-氨基苯基)苯並咪唑。 其中，只要聚醯亞胺前體清漆的黃色度（YI）未滿5.0、b*未滿2.0，則並不限定於這些。Preferably 2,2-bis(trifluoromethyl)benzidine (2,2-bis(trifluoromethyl)benzidine, TFMB), 1,3-bis(3-aminophenoxy)benzene (1,3-bis( 3-aminophenoxyl)benzene, APB), 1,3-bis(4-aminophenoxy)benzene (1,3-bis(4-aminophenoxyl)benzene, TPE-R), 1,4-bis(4-amino Phenoxy)benzene, 4,4'-diaminodiphenyl ether, p-phenylenediamine (p-PDA), 4,6-dimethyl-m-phenylenediamine, 2,5-di Methyl-p-phenylenediamine, 2,4-diamino mesitylene, 2,4-toluenediamine, m-phenylenediamine, 2,2'-dimethyl-4,4'-diaminobiphenyl, or 5-amino-2-(4-aminophenyl)benzimidazole. However, as long as the yellowness (YI) of the polyimide precursor varnish is less than 5.0 and b* is less than 2.0, it is not limited to these.

本發明的聚醯亞胺前體清漆例如對於源自在聚醯亞胺前體的結構中具有醚基的單體的結構單元為源自全部單體的結構單元的10%以上、更優選為50%以上的聚醯亞胺前體而言有用。另外，對於源自具有氟原子的單體的結構單元為源自全部單體的結構單元的10%以上、更優選為50%以上的聚醯亞胺前體而言也有用。具有如這些那樣的結構單元的聚醯亞胺前體及聚醯亞胺膜的透明性優異，因此在使用構成本發明的有機溶劑的情況下（即，在聚醯亞胺前體的情況下設為聚醯亞胺前體清漆的情況下，在聚醯亞胺膜的情況下將所述聚醯亞胺前體清漆醯亞胺化而獲得的情況下），可獲得具有更優異的透明性的聚醯亞胺前體清漆及聚醯亞胺膜。 其中，只要聚醯亞胺前體清漆的黃色度（YI）未滿5.0、b*未滿2.0，則並不限定於這些。In the polyimide precursor varnish of the present invention, for example, the structural unit derived from a monomer having an ether group in the structure of the polyimide precursor is 10% or more of the structural units derived from all monomers, more preferably Useful for more than 50% polyimide precursors. In addition, it is also useful for polyimide precursors in which the structural units derived from monomers having fluorine atoms account for 10% or more, more preferably 50% or more, of the structural units derived from all monomers. The polyimide precursor and the polyimide film having such structural units are excellent in transparency, so when using the organic solvent that constitutes the present invention (that is, in the case of the polyimide precursor In the case of a polyimide precursor varnish, in the case of a polyimide film obtained by imidizing the polyimide precursor varnish), more excellent transparency can be obtained. Permanent polyimide precursor varnish and polyimide film. However, as long as the yellowness (YI) of the polyimide precursor varnish is less than 5.0 and b* is less than 2.0, it is not limited to these.

本發明的聚醯亞胺前體可藉由以0.9～1.1的摩爾比使用酸二酐與二胺，並在有機溶劑中進行聚合的公知的方法來製造。例如，藉由在氮氣流下，向有機溶劑中加入作為原料單體的酸二酐、二胺，在室溫～80℃下反應數小時～數天來獲得。 相對於單體合計量100重量份，有機溶劑例如可在200重量份～1500重量份、優選為300重量份～900重量份的範圍內使用。The polyimide precursor of this invention can be manufactured by the well-known method which uses an acid dianhydride and a diamine by the molar ratio of 0.9-1.1, and polymerizes in an organic solvent. For example, it can be obtained by adding acid dianhydride and diamine as raw material monomers to an organic solvent under a nitrogen stream, and reacting at room temperature to 80° C. for several hours to several days. The organic solvent can be used in the range of, for example, 200 to 1500 parts by weight, preferably 300 to 900 parts by weight with respect to 100 parts by weight of the total amount of monomers.

本發明的聚醯亞胺是將本發明的聚醯亞胺前體清漆醯亞胺化而獲得。醯亞胺化可藉由熱醯亞胺化法或化學醯亞胺化法進行。熱醯亞胺化例如藉由在支撐基材上將聚醯亞胺前體清漆進行製膜，並預乾燥後，在室溫～450℃左右的溫度下進行熱處理來進行。化學醯亞胺化例如在聚醯亞胺前體清漆中加入公知的脫水劑以及/或催化劑（例如醋酸酐作為脫水劑，吡啶、異喹啉、N-甲基咪唑作為催化劑），例如在30℃～60℃下進行化學脫水。 舉例說明瞭熱醯亞胺化的優選條件。使用塗敷器在玻璃、金屬、樹脂等任意的支撐基材上將聚醯亞胺前體組合物進行製膜，在150°C以下的溫度下預乾燥2～60分鐘後，為了去除溶劑進而醯亞胺化，通常在室溫至470°C左右的溫度下進行10分鐘至20小時左右的熱處理，更優選10分鐘至4小時左右。得到所需的聚醯亞胺薄膜時的熱處理溫度可達280°C。根據所需的機械性能，也可以在 280°C 和 470°C 之間改變熱處理溫度。更優選地，當最高成膜溫度為340至460°C時，構成本發明的有機溶劑不易對本發明的聚醯亞胺前體清漆和聚醯亞胺的透明性產生不利影響，其結果是，本發明優選聚醯亞胺，因為它在膜的透過率和機械性能(CTE、拉伸強度、拉伸伸長率、彈性係數)之間具有極好的平衡。對於化學醯亞胺化，在聚醯亞胺前體組合物（也稱為聚醯胺酸）的溶液中加入脫水劑和催化劑，在30～60℃進行化學脫水。乙酸酐是典型的脫水劑，吡啶是催化劑。對於熱醯亞胺化，如果選擇酸二酐、二胺類和溶劑類的組合，可以在比較短的時間內完成醯亞胺化，包括預熱在內的熱處理可以在60分鐘內完成。也可以作為溶解在溶劑中的聚醯亞胺前體組合物的溶液來進行製膜。The polyimide of the present invention is obtained by imidizing the polyimide precursor varnish of the present invention. The imidization can be performed by thermal imidization or chemical imidization. The thermal imidization is performed, for example, by forming a film of a polyimide precursor varnish on a support substrate, predrying it, and then performing heat treatment at a temperature of about room temperature to 450°C. Chemical imidization, for example, adding known dehydrating agent and/or catalyst (such as acetic anhydride as dehydrating agent, pyridine, isoquinoline, N-methylimidazole as catalyst) in polyimide precursor varnish, for example at 30 Chemical dehydration is carried out at ℃～60℃. Preferred conditions for thermal imidization are illustrated. The polyimide precursor composition is formed into a film on any supporting substrate such as glass, metal, resin, etc. using an applicator, and after pre-drying at a temperature of 150°C or less for 2 to 60 minutes, the solvent is removed. For imidization, heat treatment is usually performed at a temperature from room temperature to about 470° C. for about 10 minutes to 20 hours, more preferably about 10 minutes to 4 hours. The heat treatment temperature when obtaining required polyimide film can reach 280 ℃. Depending on the required mechanical properties, it is also possible to vary the heat treatment temperature between 280°C and 470°C. More preferably, when the maximum film-forming temperature is 340 to 460°C, the organic solvent constituting the present invention is less likely to adversely affect the transparency of the polyimide precursor varnish and polyimide of the present invention, as a result, Polyimide is preferred for the present invention because it has an excellent balance between membrane permeability and mechanical properties (CTE, tensile strength, tensile elongation, modulus of elasticity). For chemical imidization, a dehydrating agent and a catalyst are added to the solution of the polyimide precursor composition (also known as polyamic acid), and chemical dehydration is carried out at 30-60°C. Acetic anhydride is a typical dehydrating agent, and pyridine is a catalyst. For thermal imidization, if a combination of acid dianhydride, diamines and solvents is selected, imidization can be completed in a relatively short time, and heat treatment including preheating can be completed within 60 minutes. Film formation can also be performed as a solution of a polyimide precursor composition dissolved in a solvent.

本發明的聚醯亞胺前體及聚醯亞胺的聚合度並無特別限定，例如作為聚醯亞胺前體溶液的利用E型粘度計測定的粘度，優選為500 cP～100,000 cP、更優選為1,000 cP～15,000 cP的範圍。聚醯亞胺前體的分子量可利用凝膠滲透色譜（gel permeation chromatography，GPC）法來求出。作為聚醯亞胺前體，例如，以數量平均分子量（Mn）計為15,000～250,000，以重量平均分子量（Mw）計為30,000～800,000的範圍。聚醯亞胺的分子量也位於與其聚醯亞胺前體的分子量相同的範圍內。The polyimide precursor of the present invention and the degree of polymerization of the polyimide are not particularly limited. For example, the viscosity of the polyimide precursor solution measured by an E-type viscometer is preferably 500 cP to 100,000 cP or more. It is preferably in the range of 1,000 cP to 15,000 cP. The molecular weight of the polyimide precursor can be determined by a gel permeation chromatography (GPC) method. As a polyimide precursor, it is the range of 15,000-250,000 in number average molecular weight (Mn), and 30,000-800,000 in weight average molecular weight (Mw), for example. The molecular weight of the polyimide is also in the same range as that of its polyimide precursor.

將本發明的聚醯亞胺前體醯亞胺化而獲得的聚醯亞胺作為基準厚度，在厚度10 μm的聚醯亞胺膜的狀態下（厚度10 μm換算值），聚醯亞胺的黃色度為30以下，也可為20以下。總透光率在80%以上，也可為85%以上。The polyimide obtained by imidizing the polyimide precursor of the present invention is used as a reference thickness. In the state of a polyimide film with a thickness of 10 μm (thickness 10 μm conversion value), the polyimide The yellowness is 30 or less, and may be 20 or less. The total light transmittance is above 80%, and can also be above 85%.

本發明的聚醯亞胺可提供500 nm下的透光率為70%以上、也可為83%以上，另一方面308 nm下的透光率為1%以下的聚醯亞胺。在可撓性器件的製造中，藉由對可撓性基板進行鐳射照射，可在不損傷形成在聚醯亞胺膜上的元件等的情況下剝離支撐基材，可優選地應用鐳射剝離工藝。 作為支撐基材，可使用公知的基材，例如可列舉：玻璃、金屬箔等無機基材、以及聚醯亞胺等耐熱性樹脂膜。The polyimide of the present invention can provide a polyimide having a light transmittance of 70% or more at 500 nm, or 83% or more, and a light transmittance of 1% or less at 308 nm. In the manufacture of flexible devices, by irradiating the flexible substrate with laser light, the supporting base material can be peeled off without damaging the elements formed on the polyimide film, etc., and the laser lift-off process can be preferably applied . As a support base material, a well-known base material can be used, For example, inorganic base materials, such as glass and metal foil, and heat-resistant resin films, such as polyimide, are mentioned.

本發明的聚醯亞胺的熱膨脹係數（coefficient of thermal expansion，CTE）也低，例如為20 ppm/K以下。關於拉伸物性，也可表現出拉伸強度為100 Mpa以上、拉伸伸長率為5%以上、彈性係數為10 GPa以下。The coefficient of thermal expansion (coefficient of thermal expansion, CTE) of the polyimide of this invention is also low, for example, it is 20 ppm/K or less. With regard to tensile properties, the tensile strength may be 100 MPa or more, the tensile elongation may be 5% or more, and the modulus of elasticity may be 10 GPa or less.

本發明的聚醯亞胺作為透明聚醯亞胺，可用於各種可撓性器件。本發明的聚醯亞胺適合作為帶功能層的聚醯亞胺膜。聚醯亞胺膜也可包含多層聚醯亞胺。 本發明的聚醯亞胺可在其聚醯亞胺層上形成各種功能層而製成層疊體。若列舉功能層的例子，則可列舉：液晶顯示裝置、有機EL顯示裝置、觸控式螢幕、液晶顯示器、有機EL顯示器、彩色濾光片、電子紙為首的顯示裝置、以及這些的構成零件。作為在聚醯亞胺層的單面或兩面具有金屬層的配線基板用層疊體（覆銅層疊體（copper clad laminate，CCL））也是有用的。 [實施例]As a transparent polyimide, the polyimide of the present invention can be used in various flexible devices. The polyimide of the present invention is suitable as a polyimide film with a functional layer. The polyimide film may also comprise multiple layers of polyimide. The polyimide of the present invention can be formed into a laminate by forming various functional layers on the polyimide layer. Examples of functional layers include liquid crystal display devices, organic EL display devices, touch screens, liquid crystal displays, organic EL displays, color filters, display devices including electronic paper, and components thereof. It is also useful as a laminate for a wiring board (copper clad laminate (CCL)) having a metal layer on one or both surfaces of the polyimide layer. [Example]

以下，藉由實施例更具體地說明本發明。示出實施例及比較例中使用的材料的縮寫及評價方法。Hereinafter, the present invention will be described more specifically by way of examples. Abbreviations and evaluation methods of materials used in Examples and Comparative Examples are shown.

（酸二酐） ·6FDA：4,4'-(2,2'-六氟亞異丙基)二鄰苯二甲酸二酐 ·ODPA：4,4'-氧基二鄰苯二甲酸二酐 ·PMDA：均苯四甲酸二酐 ·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 ·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） ·BAPS：雙[4-(氨基苯氧基)苯基]碸 ·AAPBI：5-氨基-2-(4-氨基苯基)苯並咪唑 （溶劑） ·如表1所示，使用YI、L*、a*、b*、純度、透光率（T）各自不同的溶劑（S1～S10）。NMP是N-甲基-2-吡咯烷酮。DMAC是N,N-二甲基乙醯胺。(acid dianhydride) 6FDA: 4,4'-(2,2'-hexafluoroisopropylidene)diphthalic dianhydride ODPA: 4,4'-oxydiphthalic dianhydride PMDA: pyromellitic dianhydride CBDA: 1,2,3,4-cyclobutane tetracarboxylic dianhydride (diamine) TFMB: 2,2-bis(trifluoromethyl)benzidine ・BY16-871: Diaminopropyltetramethyldisiloxane (manufactured by Toray Dow Corning, amine equivalent 125 g/mol) BAPS: bis[4-(aminophenoxy)phenyl]pyridine AAPBI: 5-amino-2-(4-aminophenyl)benzimidazole (solvent) · As shown in Table 1, solvents (S1 to S10) different in YI, L*, a*, b*, purity, and light transmittance (T) were used. NMP is N-methyl-2-pyrrolidone. DMAC is N,N-dimethylacetamide.

[溶劑與清漆的透光率、黃色度YI、L*、a*、b*] 使用島津（SHIMADZU）UV-3600分光光度計、光路長1 cm的石英標準單元進行測定。以超純水為空白，測定了溶劑在400 nm下的透光率。另外，基於下述數學式（1）所表示的計算式來算出YI（黃色度）。 [數式1] YI=100×（1.2879X-1.0592Z）/Y···（1） 在式（1）中，X、Y、Z是由日本工業標準（Japanese Industrial Standards，JIS）Z 8722規定的試驗片的三刺激值。 根據三刺激值X、Y、Z求出色彩值的L*、a*、b*。 此處，L*表示亮度，若接近0則表示黑色，若接近100則表示白色。a*表示綠色～紅色，負表示綠色，正表示紅色。b*表示藍色～黃色，負表示藍色，正表示黃色。a*、b*的數值均越大表示顏色越強烈。將清漆稀釋至固體成分為10 wt%至11 wt%後測量清漆。[Light transmittance, yellowness YI, L*, a*, b* of solvent and varnish] Measurements were performed using a Shimadzu (SHIMADZU) UV-3600 spectrophotometer with a quartz standard unit with an optical path length of 1 cm. Using ultrapure water as a blank, the light transmittance of the solvent at 400 nm was measured. In addition, YI (yellowness) was calculated based on a calculation formula represented by the following formula (1). [Formula 1] YI=100×(1.2879X-1.0592Z)/Y···(1) In the formula (1), X, Y, and Z are the tristimulus values of the test piece specified in Japanese Industrial Standards (JIS) Z 8722. Calculate the L*, a*, b* of the color value according to the tristimulus value X, Y, Z. Here, L* represents brightness, and when it is close to 0, it represents black, and when it is close to 100, it represents white. a* represents green to red, negative represents green, and positive represents red. b* represents blue to yellow, negative represents blue, and positive represents yellow. The larger the values of a* and b*, the stronger the color. The varnish was measured after it was diluted to a solids content of 10 to 11 wt%.

[膜的透光率、黃色度YI、L*、a*、b*] 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及500 nm下的透光率（T@308、T@500）。 基於所述數學式（1）所表示的計算式來算出YI（黃色度）。 利用下述數學式（2），算出換算為厚度10 μm後的值YI（10）。 [數式2] YI（10）=YI/厚度×10···（2） 在數學式（2）中，“厚度”是各評價膜的實際的厚度。 根據三刺激值X、Y、Z求出色彩值的L*、a*、b*。[Light transmittance of the film, yellowness YI, L*, a*, b*] The light transmittance (T@308, T@500) at 308 nm and 500 nm was obtained for the polyimide film (50 mm × 50 mm) using a Shimadzu (SHIMADZU) UV-3600 spectrophotometer. YI (yellowness) is calculated based on the calculation formula represented by the above formula (1). The value YI(10) converted to a thickness of 10 μm was calculated using the following mathematical formula (2). [Formula 2] YI(10)=YI/thickness×10···(2) In the mathematical formula (2), "thickness" is the actual thickness of each evaluation film. Calculate the L*, a*, b* of the color value according to the tristimulus value X, Y, Z.

[總光線透過率（T.T.）] 利用日本電色工業公司製造的霧度計（HAZE METER）NDH500，依據JIS K7136對聚醯亞胺膜（50 mm×50 mm）測定總光線透過率（T.T.）。[Total light transmittance (T.T.)] The total light transmittance (T.T.) of the polyimide film (50 mm×50 mm) was measured in accordance with JIS K7136 using a haze meter (HAZE METER) NDH500 manufactured by Nippon Denshoku Kogyo Co., Ltd.

[粘度] 利用帶恒溫水槽的錐板式粘度計（東機美（Tokimec）公司製造），對合成例中獲得的聚醯胺酸溶液在25℃下測定粘度。[viscosity] The viscosity of the polyamic acid solution obtained in the synthesis example was measured at 25° C. using a cone-plate viscometer (manufactured by Tokimec) with a constant temperature water tank.

[分子量Mw] 分子量是利用凝膠滲透色譜儀（東曹股份有限公司製造，商品名：HLC-8220GPC）進行測定。使用聚苯乙烯作為標準物質，展開溶媒是使用N,N-二甲基乙醯胺。[Molecular weight Mw] The molecular weight was measured with a gel permeation chromatography (manufactured by Tosoh Corporation, trade name: HLC-8220GPC). Polystyrene was used as a standard substance, and N,N-dimethylacetamide was used as a developing solvent.

[熱膨脹係數（CTE）] 利用熱機械分析（TMA/SS6100）裝置，一面對聚醯亞胺膜（3 mm×15 mm）施加30 mN的負荷，一面以一定的升溫速度（10℃/min）自30℃升溫至450℃，自此起，自450℃降溫，並根據降溫時的350℃至100℃的聚醯亞胺膜的伸長量（線膨脹）測定熱膨脹係數。[Coefficient of Thermal Expansion (CTE)] Using a thermomechanical analysis (TMA/SS6100) device, a load of 30 mN was applied to the polyimide film (3 mm × 15 mm), and the temperature was raised from 30 °C to 450 °C at a certain heating rate (10 °C/min). °C, from then on, the temperature is lowered from 450 °C, and the thermal expansion coefficient is measured according to the elongation (linear expansion) of the polyimide film from 350 °C to 100 °C when the temperature is lowered.

[拉伸試驗] 準備聚醯亞胺膜（10 mm×15 mm）的試驗片，使用騰喜龍（Tensilon）萬能試驗機（奧立特（Orientec）股份有限公司製造，RTA-250），以拉伸速度10 mm/min依照IPC-TM-650, 2.4.19進行拉伸試驗，算出拉伸伸長率、拉伸強度、彈性係數。[Stretching test] Prepare a test piece of polyimide film (10 mm × 15 mm), using a Tensilon universal testing machine (manufactured by Orientec Co., Ltd., RTA-250) at a tensile speed of 10 mm/ min Carry out a tensile test according to IPC-TM-650, 2.4.19, and calculate the tensile elongation, tensile strength, and modulus of elasticity.

[純度] 純度是利用氣相色譜儀法進行測定。[purity] Purity was determined by gas chromatography.

使用的溶劑如下述表1所示那樣（S1～S10）。The solvents used were as shown in Table 1 below (S1 to S10).

[表1]溶劑S1S2S3S4S5S6S7S8S9S10種類NMPNMPNMPNMPNMPDMACDMACDMACDMACDMACYI1.331.860.651.552.110.7318.089.4611.966.39L*94.8398.7295.1096.5697.3599.797.4299.1798.8699.43a*-0.58-0.24-0.35-0.48-0.300.011.40.81-1.07-0.54b*0.800.970.360.891.110.2710.45.356.853.55純度（%）99.899.899.999.999.9610099.899.999.899.9T（%）@400 nm85.9095.6086.1390.0690.9198.4561.5979.2573.8985.97[Table 1] solvent S1 S2 S3 S4 S5 S6 S7 S8 S9 S10 type NMP NMP NMP NMP NMP DMAC DMAC DMAC DMAC DMAC YI 1.33 1.86 0.65 1.55 2.11 0.73 18.08 9.46 11.96 6.39 L* 94.83 98.72 95.10 96.56 97.35 99.7 97.42 99.17 98.86 99.43 a* -0.58 -0.24 -0.35 -0.48 -0.30 0.01 1.4 0.81 -1.07 -0.54 b* 0.80 0.97 0.36 0.89 1.11 0.27 10.4 5.35 6.85 3.55 purity(%) 99.8 99.8 99.9 99.9 99.96 100 99.8 99.9 99.8 99.9 T(%)@400nm 85.90 95.60 86.13 90.06 90.91 98.45 61.59 79.25 73.89 85.97

實施例1 在氮氣流下，在1000 ml的可分離式燒瓶中使78.84 g的TFMB溶解在765 g的溶劑S1中。繼而，加入9.50 g的ODPA與46.66 g的PMDA。將所述溶液在40℃下加熱30分鐘，使內容物溶解，之後在室溫下將溶液持續攪拌30小時進行聚合反應，從而獲得分子量（Mw）10萬以上的聚醯亞胺（polyimide，PI）前體清漆（粘稠的溶液）V1。Example 1 Under nitrogen flow, 78.84 g of TFMB were dissolved in 765 g of solvent S1 in a 1000 ml separable flask. Then, 9.50 g of ODPA and 46.66 g of PMDA were added. The solution was heated at 40°C for 30 minutes to dissolve the contents, and then the solution was continuously stirred at room temperature for 30 hours to carry out polymerization reaction, so as to obtain polyimide (polyimide, PI) with a molecular weight (Mw) of 100,000 or more ) Precursor Varnish (viscous solution) V1.

實施例2 在氮氣流下，在2000 ml的可分離式燒瓶中使169.88 g的TFMB溶解在1700 g的溶劑S1中。繼而，加入49.29 g的ODPA與80.84 g的PMDA。將所述溶液在40℃下加熱30分鐘，使內容物溶解，之後在室溫下將溶液持續攪拌30小時進行聚合反應，從而獲得分子量（Mw）10萬以上的聚醯亞胺（PI）前體清漆（粘稠的溶液）V2。Example 2 Under nitrogen flow, 169.88 g of TFMB were dissolved in 1700 g of solvent S1 in a 2000 ml separable flask. Then, 49.29 g of ODPA and 80.84 g of PMDA were added. The solution was heated at 40°C for 30 minutes to dissolve the contents, and then the solution was continuously stirred at room temperature for 30 hours to carry out a polymerization reaction, thereby obtaining a polyimide (PI) precursor with a molecular weight (Mw) of 100,000 or more. Body Varnish (Viscous Solution) V2.

實施例3 在氮氣流下，在100 ml的可分離式燒瓶中使8.56 g的TFMB溶解在85 g的溶劑S2中。繼而，加入2.07 g的ODPA與4.37 g的PMDA。將所述溶液在40℃下加熱30分鐘，使內容物溶解，之後在室溫下將溶液持續攪拌30小時進行聚合反應，從而獲得分子量（Mw）10萬以上的聚醯亞胺（PI）前體清漆（粘稠的溶液）V3。Example 3 Under nitrogen flow, 8.56 g of TFMB were dissolved in 85 g of solvent S2 in a 100 ml separable flask. Then, 2.07 g of ODPA and 4.37 g of PMDA were added. The solution was heated at 40°C for 30 minutes to dissolve the contents, and then the solution was continuously stirred at room temperature for 30 hours to carry out a polymerization reaction, thereby obtaining a polyimide (PI) precursor with a molecular weight (Mw) of 100,000 or more. Body Varnish (viscous solution) V3.

實施例4 在氮氣流下，在300 ml的可分離式燒瓶中使25.48 g的TFMB溶解在255 g的溶劑S4中。繼而，加入7.39 g的ODPA與12.13 g的PMDA。將所述溶液在40℃下加熱30分鐘，使內容物溶解，之後在室溫下將溶液持續攪拌30小時進行聚合反應，從而獲得分子量（Mw）10萬以上的聚醯亞胺（PI）前體清漆（粘稠的溶液）V4。Example 4 Under nitrogen flow, 25.48 g of TFMB were dissolved in 255 g of solvent S4 in a 300 ml separable flask. Then, 7.39 g of ODPA and 12.13 g of PMDA were added. The solution was heated at 40°C for 30 minutes to dissolve the contents, and then the solution was continuously stirred at room temperature for 30 hours to carry out a polymerization reaction, thereby obtaining a polyimide (PI) precursor with a molecular weight (Mw) of 100,000 or more. Body Varnish (viscous solution) V4.

實施例5 在氮氣流下，在100 ml的可分離式燒瓶中使3.02 g的BY16-871溶解在70 g的溶劑S3中。繼而，向所述溶液中加入9.04 g的TFMB。攪拌10分鐘後，加入17.93 g的6FDA。將所述溶液在40℃下加熱30分鐘，使內容物溶解，之後在室溫下將溶液持續攪拌30小時進行聚合反應，從而獲得分子量（Mw）10萬以上的聚醯亞胺前體清漆（粘稠的溶液）V5。Example 5 Under nitrogen flow, 3.02 g of BY16-871 were dissolved in 70 g of solvent S3 in a 100 ml separable flask. Next, 9.04 g of TFMB was added to the solution. After stirring for 10 minutes, 17.93 g of 6FDA were added. The solution was heated at 40°C for 30 minutes to dissolve the contents, and then the solution was continuously stirred at room temperature for 30 hours to carry out a polymerization reaction, thereby obtaining a polyimide precursor varnish with a molecular weight (Mw) of 100,000 or more ( viscous solution) V5.

實施例6 在氮氣流下，在5000 ml的可分離式燒瓶中使424.57 g的TFMB溶解在4250 g的溶劑S3中。攪拌10分鐘後，加入73.40 g的6FDA與252.03 g的PMDA。將所述溶液在40℃下加熱30分鐘，使內容物溶解，之後在室溫下將溶液持續攪拌30小時進行聚合反應，從而獲得分子量（Mw）10萬以上的聚醯亞胺前體清漆（粘稠的溶液）V6。Example 6 Under nitrogen flow, 424.57 g of TFMB were dissolved in 4250 g of solvent S3 in a 5000 ml separable flask. After stirring for 10 minutes, 73.40 g of 6FDA and 252.03 g of PMDA were added. The solution was heated at 40°C for 30 minutes to dissolve the contents, and then the solution was continuously stirred at room temperature for 30 hours to carry out a polymerization reaction, thereby obtaining a polyimide precursor varnish with a molecular weight (Mw) of 100,000 or more ( viscous solution) V6.

比較例1 在氮氣流下，在300 ml的可分離式燒瓶中使25.69 g的TFMB溶解在4250 g的溶劑S5中。攪拌10分鐘後，加入6.21 g的ODPA與13.10 g的PMDA。將所述溶液在40℃下加熱30分鐘，使內容物溶解，之後在室溫下將溶液持續攪拌30小時進行聚合反應，從而獲得分子量（Mw）未滿10萬的聚醯亞胺前體清漆（粘稠的溶液）V7。Comparative example 1 Under nitrogen flow, 25.69 g of TFMB were dissolved in 4250 g of solvent S5 in a 300 ml separable flask. After stirring for 10 minutes, 6.21 g of ODPA and 13.10 g of PMDA were added. The solution was heated at 40°C for 30 minutes to dissolve the contents, and then the solution was continuously stirred at room temperature for 30 hours to carry out a polymerization reaction to obtain a polyimide precursor varnish with a molecular weight (Mw) of less than 100,000 (viscous solution) V7.

實施例7、實施例8、比較例2～比較例5 將二胺、酸二酐、溶劑替換成表2所示的調配組成，使用100 ml單獨的燒瓶和68 g溶劑，與實施例1同樣地進行聚合反應，實施例7、實施例8獲得分子量（Mw）10萬以上的聚醯亞胺前體清漆，比較例2～比較例5獲得分子量（Mw）未滿10萬的聚醯亞胺前體清漆。Embodiment 7, embodiment 8, comparative example 2～comparative example 5 Diamine, acid dianhydride, solvent are replaced with the deployment composition shown in table 2, use 100 ml separate flask and 68 g solvent, carry out polymerization reaction in the same way as Example 1, embodiment 7, embodiment 8 obtain molecular weight ( Mw) is a polyimide precursor varnish of 100,000 or more, and Comparative Examples 2 to 5 obtained a polyimide precursor varnish with a molecular weight (Mw) of less than 100,000.

將所述實施例1～實施例8、比較例1～比較例5的調配匯總示於表2中。 [表2]  實施例 1實施例 2實施例 3實施例 4實施例 5實施例 6比較例 1比較例 2實施例 7比較例 3比較例 4比較例 5實施例 8二胺TFMB78.84169.888.5625.489.04424.5725.696.796.799.856.866.79 BY16-871    3.02        AAPBI           0.53   BAPS              7.01酸二酐  ODPA9.5049.292.077.39  6.21   1.65 4.99PMDA46.6680.844.3712.13 252.0313.104.034.03 3.494.04 CBDA           4.62   6FDA    17.9373.40 1.171.17  1.18 溶劑 S1S1S2S4S3S3S5S7S6S8S9S10S1 765170085255704250255      清漆 V1V2V3V4V5V6V7V8V9V10V11V12V13Table 2 summarizes the formulations of Examples 1 to 8 and Comparative Examples 1 to 5. [Table 2] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative example 1 Comparative example 2 Example 7 Comparative example 3 Comparative example 4 Comparative Example 5 Example 8 diamine TFMB 78.84 169.88 8.56 25.48 9.04 424.57 25.69 6.79 6.79 9.85 6.86 6.79 BY16-871 3.02 AAPBI 0.53 BAPS 7.01 Acid dianhydride ODPA 9.50 49.29 2.07 7.39 6.21 1.65 4.99 PMDA 46.66 80.84 4.37 12.13 252.03 13.10 4.03 4.03 3.49 4.04 CBDA 4.62 6FDA 17.93 73.40 1.17 1.17 1.18 solvent S1 S1 S2 S4 S3 S3 S5 S7 S6 S8 S9 S10 S1 765 1700 85 255 70 4250 255 varnish V1 V2 V3 V4 V5 V6 V7 V8 V9 V10 V11 V12 V13

對所述實施例1～實施例8、比較例1～比較例5中獲得的聚醯亞胺（PI）前體清漆評價光學物性。利用與分別合成各PI前體清漆時使用的溶劑同種的溶劑進行稀釋。然後利用分光光度計測定PI前體清漆的YI、a*、b*、在400 nm下的透光率。將其結果示於表3中。The optical properties of the polyimide (PI) precursor varnishes obtained in Examples 1 to 8 and Comparative Examples 1 to 5 were evaluated. Dilution was performed with the same solvent as that used when synthesizing each PI precursor varnish. Then, the YI, a*, b*, and light transmittance at 400 nm of the PI precursor varnish were measured by a spectrophotometer. The results are shown in Table 3.

進而，使用所述實施例1～實施例8、比較例1～比較例5中獲得的聚醯亞胺（PI）前體清漆，將其聚醯亞胺化，並評價光學物性。即，向各PI前體清漆中加入與分別合成時使用的溶劑同種的溶劑，將固體成分稀釋至11 wt%±1 wt%左右以便於粘度容易進行塗敷，然後在作為支撐基材的100 μm的玻璃基板上，使用旋塗機，以醯亞胺化後的聚醯亞胺層的厚度成為約10 μm的方式進行塗敷。繼而，在120℃下加熱10分鐘並加以乾燥而進行溶劑去除。接下來，在氮環境中，以一定的升溫速度（3℃/min～10℃/min）自室溫升溫至350℃～450℃的範圍，進而保持1~30分鐘。之後，在氮環境中恢復至室溫，自烘箱中取出，從而在支撐基材上形成聚醯亞胺層。之後，剝離支撐基材，獲得各聚醯亞胺（PI）膜。所述剝離是藉由以下方式來進行：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，利用鑷子自支撐基材進行剝離。 對以所述方式獲得的各聚醯亞胺（PI）膜評價厚度、308 nm與500 nm波長下的透光率、總光線透過率、以及CTE、拉伸強度、拉伸伸長率、彈性係數。將其結果示於表3中。Furthermore, using the polyimide (PI) precursor varnish obtained in said Example 1 - Example 8, and Comparative Example 1 - Comparative Example 5, it was polyimidized, and the optical physical property was evaluated. That is, add the same solvent as the solvent used in the respective synthesis to each PI precursor varnish, dilute the solid content to about 11 wt% ± 1 wt% so that the viscosity can be easily applied, and then the 100 µm glass substrates were coated using a spin coater so that the imidized polyimide layer had a thickness of about 10 µm. Then, it heated at 120 degreeC for 10 minutes, dried, and solvent removal was performed. Next, in a nitrogen atmosphere, the temperature is raised from room temperature to a range of 350° C. to 450° C. at a constant temperature increase rate (3° C./min to 10° C./min), and then kept for 1 to 30 minutes. Thereafter, it was returned to room temperature in a nitrogen environment, and taken out from the oven to form a polyimide layer on the supporting substrate. After that, the supporting substrate was peeled off to obtain each polyimide (PI) film. The peeling is carried out by using a dicing knife to cut only one round of incisions on the formed polyimide layer to determine the peeling range, and then peeling off from the supporting substrate with tweezers. The thickness, light transmittance at wavelengths of 308 nm and 500 nm, total light transmittance, and CTE, tensile strength, tensile elongation, modulus of elasticity were evaluated for each polyimide (PI) film obtained in the above manner . The results are shown in Table 3.

[表3]  實施例1實施例2實施例3實施例4實施例5實施例6比較例1比較例2實施例7比較例3比較例4比較例 5實施例8溶劑 S1S1S2S4S3S3S5S7S6S8S9S10S1清漆 V1V2V3V4V5V6V7V8V9V10V11V12V13粘度（cP）12272624438585609300035004818160035001100100015003400固體成分（wt%）11.0012.0011.0010.5011.0011.009.7011.0011.0011.0011.0011.0011.00YI1.571.851.303.291.201.405.8120.71  1.8  13.74  13.43  9.441.3L*100.33101.75101.1398.80100.10100.0097.7595.8  100.1397.54  98.47  98.23102.19a*-0.37-0.54-0.37-0.29-0.35-0.28-0.30-1.57  -0.21  -0.7  -1.31  -0.87-0.55b*0.871.110.731.750.680.904.3411.85  0.93  7.62  7.76  5.320.82T（%）@400 nm86.9189.3590.2281.9591.0090.0073.7850.4  84.9  61.92  63.90  66.892.38製 膜 條 件製膜最高溫度 （℃）420385450450370370450400400400400350350製膜最高溫度的保持時間(分)30303030303030222222製膜昇溫速度 (℃/min)444433466661010膜厚度（μm）10.58.69.28.39.3610.1911.78.79.810.214.5YI（10）12.410.3722.228.31.7810.436.48.37.420.186.85.06YI13.09.020.423.51.77.936.97.58.717.57.96.977.35T（%）@308 nm0.000.000.000.000.010.000.000.000.000.000.000.000.00T（%）@500 nm84.584.480.178.486.386.568.887.485.981.685.585.8396.15總光線透過率（%）85.186.782.681.091.08874.988.187.883.48788.4289.46CTE（ppm/K）1.111.29.810.9694.99.85.14.9229.84.963拉伸強度（MPa）292257250250113239184189224150210165183拉伸伸長率（%）172632256.9197.64.114.83.53.83.215彈性係數（GPa）8.75.96.95.93.25.96.17.37.46.36.96.75.2[產業上的可利用性][table 3] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative example 1 Comparative example 2 Example 7 Comparative example 3 Comparative example 4 Comparative Example 5 Example 8 solvent S1 S1 S2 S4 S3 S3 S5 S7 S6 S8 S9 S10 S1 varnish V1 V2 V3 V4 V5 V6 V7 V8 V9 V10 V11 V12 V13 Viscosity (cP) 12272 6244 3858 5609 3000 3500 4818 1600 3500 1100 1000 1500 3400 Solid content (wt%) 11.00 12.00 11.00 10.50 11.00 11.00 9.70 11.00 11.00 11.00 11.00 11.00 11.00 YI 1.57 1.85 1.30 3.29 1.20 1.40 5.81 20.71 1.8 13.74 13.43 9.44 1.3 L* 100.33 101.75 101.13 98.80 100.10 100.00 97.75 95.8 100.13 97.54 98.47 98.23 102.19 a* -0.37 -0.54 -0.37 -0.29 -0.35 -0.28 -0.30 -1.57 -0.21 -0.7 -1.31 -0.87 -0.55 b* 0.87 1.11 0.73 1.75 0.68 0.90 4.34 11.85 0.93 7.62 7.76 5.32 0.82 T(%)@400nm 86.91 89.35 90.22 81.95 91.00 90.00 73.78 50.4 84.9 61.92 63.90 66.8 92.38 Membrane conditions Maximum film forming temperature (°C) 420 385 450 450 370 370 450 400 400 400 400 350 350 The holding time of the highest temperature for film formation (minutes) 30 30 30 30 30 30 30 2 2 2 2 2 2 Film heating rate (℃/min) 4 4 4 4 3 3 4 6 6 6 6 10 10 membrane Thickness (μm) 10.5 8.6 9.2 8.3 9.3 6 10.1 9 11.7 8.7 9.8 10.2 14.5 YI (10) 12.4 10.37 22.2 28.3 1.78 10.4 36.4 8.3 7.4 20.1 8 6.8 5.06 YI 13.0 9.0 20.4 23.5 1.7 7.9 36.9 7.5 8.7 17.5 7.9 6.97 7.35 T(%)@308nm 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 T(%)@500nm 84.5 84.4 80.1 78.4 86.3 86.5 68.8 87.4 85.9 81.6 85.5 85.83 96.15 Total light transmittance (%) 85.1 86.7 82.6 81.0 91.0 88 74.9 88.1 87.8 83.4 87 88.42 89.46 CTE (ppm/K) 1.1 11.2 9.8 10.9 69 4.9 9.8 5.1 4.9 twenty two 9.8 4.9 63 Tensile strength (MPa) 292 257 250 250 113 239 184 189 224 150 210 165 183 Tensile elongation (%) 17 26 32 25 6.9 19 7.6 4.1 14.8 3.5 3.8 3.2 15 Elastic coefficient (GPa) 8.7 5.9 6.9 5.9 3.2 5.9 6.1 7.3 7.4 6.3 6.9 6.7 5.2 [industrial availability]

本發明的聚醯亞胺前體清漆及聚醯亞胺可優選地用作可撓性器件或配線基板用層疊體用的透明材料。The polyimide precursor varnish and polyimide of the present invention can be preferably used as a transparent material for a flexible device or a laminate for a wiring board.

Claims (8)

Translated fromChinese

一種聚醯亞胺前體清漆，包含聚醯亞胺前體及有機溶劑，所述聚醯亞胺前體清漆的特徵在於，所述有機溶劑的黃色度黃色指數為2.0以下，b*為1.0以下，所述聚醯亞胺前體清漆的黃色度黃色指數未滿5.0，b*未滿2.0。A polyimide precursor varnish, comprising a polyimide precursor and an organic solvent, the polyimide precursor varnish is characterized in that the yellowness index of the organic solvent is below 2.0, and b* is 1.0 Hereinafter, the yellowness index of the polyimide precursor varnish is less than 5.0, and b* is less than 2.0.如請求項1所述的聚醯亞胺前體清漆，其中有機溶劑在光路長1 cm、400 nm波長下的透光率為85%以上且未滿89%。The polyimide precursor varnish as described in Claim 1, wherein the light transmittance of the organic solvent at an optical path length of 1 cm and a wavelength of 400 nm is more than 85% and less than 89%.如請求項1或請求項2所述的聚醯亞胺前體清漆，其中有機溶劑為選自由N,N-二甲基乙醯胺、N,N-二甲基甲醯胺、N-甲基-2-吡咯烷酮、N-乙基-2-吡咯烷酮、二甲基咪唑烷酮、及γ-丁內酯所組成的群組中的一種以上。The polyimide precursor varnish as described in claim 1 or claim 2, wherein the organic solvent is selected from N,N-dimethylacetamide, N,N-dimethylformamide, N-formaldehyde One or more of the group consisting of yl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethylimidazolidinone, and γ-butyrolactone.一種聚醯亞胺前體清漆的製造方法，是製造包含聚醯亞胺前體及有機溶劑的聚醯亞胺前體清漆的方法，所述聚醯亞胺前體清漆的製造方法的特徵在於，使用黃色度黃色指數為2.0以下、b*為1.0以下的有機溶劑作為所述有機溶劑，獲得黃色度黃色指數未滿5.0、b*未滿2.0的聚醯亞胺前體清漆。A kind of manufacture method of polyimide precursor varnish, is to manufacture the method for the polyimide precursor varnish comprising polyimide precursor and organic solvent, the manufacture method of described polyimide precursor varnish is characterized in that , using an organic solvent having a yellowness index of 2.0 or less and b* of 1.0 or less as the organic solvent, to obtain a polyimide precursor varnish whose yellowness index is less than 5.0 and b* is less than 2.0.一種聚醯亞胺，是對包含聚醯亞胺前體及有機溶劑的聚醯亞胺前體清漆進行醯亞胺化而成，所述聚醯亞胺的特徵在於，所述有機溶劑的黃色度黃色指數為2.0以下，b*為1.0以下，聚醯亞胺的黃色度黃色指數厚度10 μm換算值為30以下，總透光率為80%以上。A polyimide is formed by imidizing a polyimide precursor varnish comprising a polyimide precursor and an organic solvent. The polyimide is characterized in that the yellow color of the organic solvent is The yellowness index is less than 2.0, b* is less than 1.0, the yellowness index of polyimide is less than 30 when the thickness is 10 μm, and the total light transmittance is more than 80%.一種聚醯亞胺的製造方法，是製造對包含聚醯亞胺前體及有機溶劑的聚醯亞胺前體清漆進行醯亞胺化而成的聚醯亞胺的方法，所述聚醯亞胺的製造方法的特徵在於，使用黃色度黃色指數為2.0以下、b*為1.0以下的有機溶劑作為所述有機溶劑，獲得黃色度黃色指數厚度10 μm換算值為30以下、總透光率為80%以上的聚醯亞胺。A method for producing a polyimide, which is a method of producing a polyimide formed by imidizing a polyimide precursor varnish comprising a polyimide precursor and an organic solvent, the polyimide The method for producing an amine is characterized in that an organic solvent having a yellowness index of 2.0 or less and a b* of 1.0 or less is used as the organic solvent to obtain a yellowness index of 30 or less in terms of a thickness of 10 μm and a total light transmittance of 30 or less. More than 80% polyimide.一種可撓性器件，其特徵在於，包括包含如請求項5所述的聚醯亞胺的聚醯亞胺層、以及形成於所述聚醯亞胺層上的功能層。A flexible device, characterized in that it comprises a polyimide layer comprising polyimide as described in claim 5, and a functional layer formed on the polyimide layer.一種配線基板用層疊體，其特徵在於，具有包含如請求項5所述的聚醯亞胺的聚醯亞胺層、以及在所述聚醯亞胺層的單面或兩面上的金屬層。A laminate for a wiring board, comprising a polyimide layer containing the polyimide according to claim 5, and metal layers on one or both surfaces of the polyimide layer.