TW202017978A - Polyimide film, flexible device using same and preparation process thereof - Google Patents

Abstract

According to the present invention, a polyimide film is obtained from a polyamic acid prepared by using diamines a diaminodiphenyl sulfone (DDS) and an amine-terminal methylphenylsiloxane oligomer and two or more tetracarboxylic dianhydrides as polymerization components. The pore distribution in the polyimide film is controlled 1% or less and/or the average size of phase separation domains is controlled to 10 nm or less, thereby providing a flexible device that are free from mechanical defects such as LTPS (low temperature polysilicon) thin film even in a high temperature processes such as low temperature polysilicon processes.

Description

聚醯亞胺膜以及使用其的可撓性裝置Polyimide film and flexible device using the same

本申請主張基於2018年8月20日申請的韓國專利申請10-2018-0096802號與10-2018-0096803號、以及2019年8月16日申請的韓國專利申請10-2019-0100199號的優先權的利益，且相應韓國專利申請的文獻所揭示的所有內容均作為本說明書的一部分而包含在內。This application claims priority based on Korean Patent Applications 10-2018-0096802 and 10-2018-0096803 filed on August 20, 2018, and Korean Patent Application 10-2019-0100199 filed on August 16, 2019 Benefits, and all the contents disclosed in the corresponding Korean patent application documents are included as part of this specification.

本發明是有關於一種於高溫製程下耐熱性優異的聚醯亞胺膜以及使用其的可撓性裝置。The present invention relates to a polyimide film excellent in heat resistance under a high-temperature process and a flexible device using the same.

最近，於顯示器領域中，重視製品的輕量化及小型化。由於玻璃基板的情況存在重、易破裂且難以進行連續製程的限制，因此代替玻璃基板以將具有輕、柔軟且可進行連續製程的優點的塑膠基板應用於手機、筆記型電腦、個人數位助理（personal digital assistant，PDA）等的研究正在活躍地進行。Recently, in the field of displays, emphasis has been placed on reducing the weight and size of products. Due to the limitations of glass substrates that are heavy, easily broken, and difficult to perform continuous processes, instead of glass substrates, plastic substrates with the advantages of light, soft, and continuous processes can be applied to mobile phones, notebook computers, and personal digital assistants ( Personal digital assistant (PDA) and other research are being actively carried out.

特別是，聚醯亞胺（polyimide，PI）樹脂具有合成容易且可製成薄膜型膜、並且無需用於硬化的交聯劑的優點，因此最近因電子製品的輕量化及精密化現象而作為積體化原材料大量用於液晶顯示器（liquid crystal display，LCD）、電漿顯示器（plasma display panel，PDP）等半導體材料。另外，欲將PI樹脂用於具有輕且柔軟的性質的可撓性顯示器基板（可撓性塑膠顯示器基板（flexible plastic display board））的研究正在活躍地進行。In particular, polyimide (PI) resin has the advantages of being easy to synthesize, can be made into a thin film, and does not require a cross-linking agent for curing. Therefore, it has recently been used as a lightweight and precision phenomenon for electronic products. The integrated raw materials are widely used in semiconductor materials such as liquid crystal displays (LCD) and plasma display panels (PDP). In addition, research on the use of PI resins for flexible display substrates (flexible plastic display boards) with light and soft properties is being actively conducted.

將聚醯亞胺樹脂膜化而製備的是聚醯亞胺（PI）膜，通常，聚醯亞胺膜是以如下方法製備：使芳香族二酐（dianhydride）與芳香族二胺或芳香族二異氰酸酯進行溶液聚合，製備聚醯胺酸衍生物溶液後，將其塗佈於矽晶圓或玻璃等，並藉由熱處理使其硬化（醯亞胺化）。A polyimide (PI) film is prepared by filming the polyimide resin. Generally, the polyimide film is prepared by the following method: an aromatic dianhydride (dianhydride) and an aromatic diamine or aromatic After diisocyanate is solution polymerized to prepare a solution of a polyamic acid derivative, it is coated on a silicon wafer or glass, etc., and hardened by heat treatment (imidization).

伴隨有高溫製程的可撓性裝置要求於高溫下的耐熱性，特別是使用低溫多晶矽（low temperature polysilicon，LTPS）製程的有機發光二極體（organic light emitting diode，OLED）裝置的情況，製程溫度有時接近500℃。但是於此種溫度下，即使耐熱性優異的聚醯亞胺亦容易發生由加水分解引起的熱分解。因此，為了製備可撓性裝置，需要開發一種可表現出優異的耐熱性的聚醯亞胺膜。Flexible devices with high-temperature processes require heat resistance at high temperatures, especially in the case of organic light emitting diode (OLED) devices using low-temperature polysilicon (LTPS) processes, process temperatures Sometimes close to 500℃. However, at such a temperature, even polyimide excellent in heat resistance is susceptible to thermal decomposition caused by hydrolysis. Therefore, in order to prepare a flexible device, it is necessary to develop a polyimide film that can exhibit excellent heat resistance.

[發明所欲解決之課題][Problems to be solved by the invention]

本發明欲解決的課題是提供一種高溫下的耐熱性得到提高的聚醯亞胺膜。The problem to be solved by the present invention is to provide a polyimide film with improved heat resistance at high temperatures.

本發明欲解決的另一課題是提供使用所述聚醯亞胺膜的可撓性裝置及其製備製程。 [解決課題之手段]Another subject to be solved by the present invention is to provide a flexible device using the polyimide film and its preparation process. [Means to solve the problem]

為了解決本發明的課題， 提供一種聚醯亞胺膜，是包含聚合成分的聚合及醯亞胺化產物的聚醯亞胺膜，所述聚合成分包含：二胺成分，包含具有下述化學式1的結構的二胺與胺封端的甲基苯基矽氧烷低聚物；以及 二酐成分，包含兩種以上的四羧酸二酐；且膜內氣孔（pore）的分佈率為1%以下： [化學式1]

。In order to solve the problems of the present invention, there is provided a polyimide film, which is a polyimide film containing a polymerized and imidized product of a polymerized component, the polymerized component including: a diamine component, including the following chemical formula 1 The structure of diamine and amine-terminated methylphenylsiloxane oligomer; and dianhydride components, including more than two kinds of tetracarboxylic dianhydride; and the distribution rate of pores in the membrane (pore) is less than 1% : [Chemical Formula 1]

.

另外，本發明提供一種聚醯亞胺膜，是包含聚合成分的聚合及醯亞胺化產物的聚醯亞胺膜，所述聚合成分包含：二胺成分，包含具有下述化學式1的結構的二胺與胺封端的甲基苯基矽氧烷低聚物；以及 二酐成分，包含兩種以上的四羧酸二酐； 於源自所述化學式1的二胺的聚醯亞胺基質分散有源自所述胺封端的甲基苯基矽氧烷低聚物的多個域，所述多個域的平均大小為10 nm以下。In addition, the present invention provides a polyimide film, which is a polyimide film containing a polymerized and imidized product of a polymerized component, the polymerized component including: a diamine component, including a structure having the following chemical formula 1 Diamine and amine-terminated methylphenylsiloxane oligomers; and The dianhydride component contains two or more tetracarboxylic dianhydrides; The polyimide matrix derived from the diamine of the chemical formula 1 is dispersed with multiple domains derived from the amine-terminated methylphenylsiloxane oligomer, and the average size of the multiple domains is 10 Below nm.

根據一實施例，所述胺封端的甲基苯基矽氧烷低聚物可具有下述化學式2的結構。 [化學式2]

於所述式中，p及q為莫耳分率且為p+q=100時，p為70～90，q為10～30。According to an embodiment, the amine-terminated methylphenylsiloxane oligomer may have the structure of Chemical Formula 2 below. [Chemical Formula 2]

In the above formula, p and q are mole fractions and p+q=100, p is 70 to 90, and q is 10 to 30.

根據一實施例，所述二酐成分可包含聯苯四羧酸二酐（biphenyltetracarboxylic dianhydride，BPDA）及均苯四甲酸二酐（pyromellitic dianhydride，PMDA）。According to an embodiment, the dianhydride component may include biphenyltetracarboxylic dianhydride (BPDA) and pyromellitic dianhydride (PMDA).

根據一實施例，所述二酐成分可以6：4至8：2的莫耳比包含BPDA與PMDA。According to an embodiment, the dianhydride component may include BPDA and PMDA in a molar ratio of 6:4 to 8:2.

根據一實施例，所述聚合成分以整體聚合成分的總重量為基準而可包含5重量%至30重量%的所述胺封端的甲基苯基矽氧烷低聚物。According to an embodiment, the polymerized component may include 5 to 30% by weight of the amine-terminated methylphenylsiloxane oligomer based on the total weight of the entire polymerized component.

根據一實施例，所述聚合成分以整體二胺成分為基準而可包含1莫耳%～10莫耳%的所述胺封端的甲基苯基矽氧烷低聚物。According to an embodiment, the polymerization component may include 1 mol% to 10 mol% of the amine-terminated methylphenylsiloxane oligomer based on the overall diamine component.

根據一實施例，所述聚醯亞胺膜的模數可為2.2 GPa以下，且伸長率為20%以上。According to an embodiment, the modulus of the polyimide film may be 2.2 GPa or less, and the elongation is 20% or more.

根據一實施例，所述聚醯亞胺膜的玻璃轉移溫度（Tg）可為230℃以上。According to an embodiment, the glass transition temperature (Tg) of the polyimide film may be above 230°C.

本發明亦提供一種包含所述聚醯亞胺膜的可撓性裝置。The invention also provides a flexible device including the polyimide film.

本發明亦提供一種可撓性裝置的製備製程，包含如下步驟： 使二胺成分與二酐成分反應來製備聚醯亞胺前驅物組成物，所述二胺成分包含所述化學式1的二胺及胺封端的甲基苯基矽氧烷低聚物，所述二酐成分包含兩種以上的四羧酸二酐； 將所製備的聚醯亞胺前驅物組成物塗佈於載體基板上； 藉由對所述聚醯亞胺前驅物組成物進行加熱而醯亞胺化，從而形成聚醯亞胺膜； 於所述聚醯亞胺膜上形成元件；以及 將形成有元件的所述聚醯亞胺膜自所述載體基板剝離。The invention also provides a preparation process of a flexible device, which includes the following steps: A polyimide precursor composition is prepared by reacting a diamine component and a dianhydride component, the diamine component comprising the diamine of the Chemical Formula 1 and an amine-terminated methylphenylsiloxane oligomer, the The dianhydride component contains two or more tetracarboxylic dianhydrides; Coating the prepared polyimide precursor composition on the carrier substrate; Heating the polyimide precursor composition to imide it to form a polyimide film; Forming an element on the polyimide film; and The polyimide film formed with the element is peeled from the carrier substrate.

根據一實施例，所述製備製程可包含選自由LTPS（低溫多晶矽）薄膜製備製程、氧化銦錫（indium tin oxide，ITO）薄膜製備製程或氧化物（Oxide）薄膜製備製程所組成的群組中的一種以上的製程。 [發明的效果]According to an embodiment, the manufacturing process may include a group selected from the group consisting of an LTPS (low temperature polysilicon) thin film manufacturing process, an indium tin oxide (ITO) thin film manufacturing process or an oxide (Oxide) thin film manufacturing process More than one process. [Effect of invention]

本發明藉由將包含二胺基二苯基碸（diaminodiphenyl sulfone，DDS）與胺封端的甲基苯基矽氧烷低聚物的二胺、以及兩種以上的四羧酸二酐作為聚合成分，並將聚醯亞胺膜內氣孔（pore）的分佈率調節至1%以下，或者/並且將相分離域的大小調節至10 nm以下，從而可提供一種可撓性裝置，於如LTPS（Low Temperature Polysilicon）製程、ITO製程或氧化物製程的高溫製程下在形成的無機膜亦不產生如龜裂般的機械性缺陷。In the present invention, a diamine containing diaminodiphenyl sulfone (DDS) and an amine-terminated methylphenylsiloxane oligomer, and two or more tetracarboxylic dianhydrides are used as polymerization components , And adjust the distribution rate of pores in the polyimide membrane to less than 1%, or/and adjust the size of the phase separation domain to less than 10 nm, so as to provide a flexible device, such as LTPS ( Low Temperature Polysilicon) process, ITO process or oxide process under high temperature process does not produce mechanical defects like cracks in the formed inorganic film.

本發明可施加各種變化且可具有多種實施例，欲根據例示於附圖及詳細說明而詳細地對特定實施例進行說明。但是，應理解的是並非欲將本發明限定於特定的實施形態，本發明包括包含於本發明的思想及技術範圍的所有變換、均等物及代替物。於本發明的說明書中，於判斷出對相關習知技術的具體說明會使本發明的要旨變得含糊不清的情況時，省略對所述相關習知技術的詳細的說明。The present invention can apply various changes and can have various embodiments, and it is intended to explain specific embodiments in detail based on the illustrations and the detailed description. However, it should be understood that the present invention is not intended to be limited to a specific embodiment, and the present invention includes all modifications, equivalents, and substitutes included in the idea and technical scope of the present invention. In the description of the present invention, when it is judged that the detailed description of the related art will make the gist of the invention ambiguous, the detailed description of the related art will be omitted.

於本說明書中，所有的化合物或官能基若未特別提及，則可為取代的或未經取代的化合物或官能基。此處，「取代的」意指包含於化合物或官能基的至少一個氫被選自由如下組成的群組中的取代基代替：鹵素原子、碳個數為1至10的烷基、鹵化烷基、碳個數為3至30的環烷基、碳個數為6至30的芳基、羥基、碳個數為1至10的烷氧基、羧基、醛基、環氧基、氰基、硝基、胺基、磺酸基及其等的衍生物。In this specification, all compounds or functional groups may be substituted or unsubstituted compounds or functional groups unless otherwise mentioned. Here, "substituted" means that at least one hydrogen contained in the compound or functional group is replaced by a substituent selected from the group consisting of: a halogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group , Cycloalkyl having 3 to 30 carbons, aryl having 6 to 30 carbons, hydroxyl, alkoxy having 1 to 10 carbons, carboxyl, aldehyde, epoxy, cyano, Nitro, amine, sulfonic acid and their derivatives.

根據本發明的一方面，提供一種聚醯亞胺膜，是包含聚合成分的聚合及醯亞胺化產物的聚醯亞胺膜，所述聚合成分包含：二胺成分，包含下述化學式1的化合物及兩末端胺改質的二甲基矽氧烷（dimethylsiloxane，DMS）-二苯基矽氧烷（diphenylsiloxane，DPS）低聚物；以及 二酐成分，包含兩種以上的四羧酸二酐；且膜內氣孔（pore）分佈率為1%以下： [化學式1]

。According to an aspect of the present invention, there is provided a polyimide film, which is a polyimide film containing a polymerized and imidized product of a polymerized component, the polymerized component including: a diamine component, including the following chemical formula 1 Compound and amine modified dimethylsiloxane (DMS)-diphenylsiloxane (DPS) oligomer at both ends; and dianhydride component, including two or more tetracarboxylic dianhydrides ; And the distribution rate of pores in the membrane is below 1%: [Chemical Formula 1]

.

根據本發明的另一方面，提供一種聚醯亞胺膜，是包含聚合成分的聚合及醯亞胺化產物的聚醯亞胺膜，所述聚合成分包含：二胺成分，包含所述化學式1的化合物及兩末端胺改質的二甲基矽氧烷（DMS）-二苯基矽氧烷（DPS）低聚物；以及 二酐成分，包含兩種以上的四羧酸二酐；於源自所述化學式1的二胺的聚醯亞胺基質分散有源自所述胺封端的甲基苯基矽氧烷低聚物的多個域，所述多個域的平均大小為10 nm以下。According to another aspect of the present invention, there is provided a polyimide film, which is a polyimide film containing a polymerized and imidized product of a polymerized component, the polymerized component including: a diamine component, including the chemical formula 1 Compounds and amine-modified dimethylsiloxane (DMS)-diphenylsiloxane (DPS) oligomers at both ends; and The dianhydride component contains two or more kinds of tetracarboxylic dianhydride; the polyimide matrix derived from the diamine of the chemical formula 1 is dispersed with a methylphenylsiloxane oligomer derived from the amine end. Multiple domains, the average size of the multiple domains is below 10 nm.

由所述化學式1表示的化合物可為選自由例如4,4-(二胺基二苯基)碸（以下，4,4-DDS）、3,4-(二胺基二苯基)碸（3,4-DDS）及3,3-(二胺基二苯基)碸（3,3-DDS）所組成的群組中的一種以上。The compound represented by the chemical formula 1 may be selected from, for example, 4,4-(diaminodiphenyl) lanthanum (hereinafter, 4,4-DDS), 3,4-(diaminodiphenyl) lanolin ( More than one of the group consisting of 3,4-DDS) and 3,3-(diaminodiphenyl) ash (3,3-DDS).

本發明藉由於聚醯胺酸的製備過程中，使用胺封端的甲基苯基矽氧烷低聚物與化學式1的DDS（diaminodiphenyl sulfone）作為聚合成分，從而可於進行包含矽氧烷低聚物結構的聚醯亞胺膜的製備製程時明顯減少可能產生的氣孔（pore）的比率。形成於聚醯亞胺膜的氣孔因可使之後形成於聚醯亞胺膜上的無機膜產生龜裂（crack），因此欠佳。In the present invention, the amine-terminated methylphenylsiloxane oligomer and the chemical formula 1 DDS (diaminodiphenyl sulfone) are used as the polymerization component in the preparation process of polyamic acid, so that the oligomerization containing silicone can be carried out The preparation process of the polyimide film with the structure of the object obviously reduces the ratio of possible pores during the manufacturing process. The pores formed on the polyimide film can cause cracks in the inorganic film formed on the polyimide film, which is not preferable.

於包含胺封端的甲基苯基矽氧烷低聚物結構的聚醯亞胺膜的製備製程中，於高溫硬化製程時會發生矽氧烷低聚物結構的鏈的斷裂與重新排列，且藉由此種過程會於聚醯亞胺膜內部產生氣孔。此時，於具有模數高的結構的聚醯亞胺、即具有剛性（rigid）結構的聚醯亞胺中，於高溫下的流動性（mobility）不高，而於所述的過程中產生的氣孔殘留於膜內部，從而使膜內氣孔的比率變高。反之，本發明的聚醯亞胺膜藉由使用如DDS（diaminodiphenyl sulfone）般具有柔軟的結構的二胺，而於高溫下的流動性（mobility）高，氣孔可於膜形成過程中排出至外部，因此最終可使存在於膜內部的氣孔的比率明顯減少。In the preparation process of the polyimide film containing the amine-terminated methylphenylsiloxane oligomer structure, the chain breakage and rearrangement of the silicone oligomer structure will occur during the high temperature curing process, and Through this process, pores are generated inside the polyimide film. At this time, in the polyimide having a structure with a high modulus, that is, the polyimide having a rigid structure, the mobility at high temperature is not high, but is generated in the process Of pores remain inside the membrane, thereby increasing the ratio of pores in the membrane. On the contrary, the polyimide membrane of the present invention uses a diamine with a soft structure like DDS (diaminodiphenyl sulfone), which has high mobility at high temperature, and the pores can be discharged to the outside during the formation of the membrane Therefore, the ratio of pores existing inside the membrane can be significantly reduced.

此時，氣孔分佈率可如下般進行測定。At this time, the porosity distribution rate can be measured as follows.

將藉由FIB-SEM（Focused Ion Beam Scanning Electron Microscopes）以100,000倍率對聚醯亞胺膜測定的影像（image）固定為100 mm×80 mm，之後以2 mm×2 mm對區域進行細分，並以整體區域（總計2000個區域）為基準，測定氣孔（pore）存在的區域的比率。於圖1示出利用FIB-SEM影像的氣孔分佈率的測定方法。The image measured by FIB-SEM (Focused Ion Beam Scanning Electron Microscopes) at a magnification of 100,000 was fixed to 100 mm×80 mm, and then the area was subdivided by 2 mm×2 mm, and Based on the overall area (a total of 2000 areas) as a reference, the ratio of areas where pores exist is measured. FIG. 1 shows a method of measuring the porosity distribution ratio using FIB-SEM images.

例如，氣孔存在的區域存在兩個（2ea）的情況，氣孔分佈率如下。For example, if there are two (2ea) in the area where stomata exist, the stomata distribution rate is as follows.

氣孔分佈率（%）=2/2000 × 100=0.1%Stomatal distribution rate (%)=2/2000 × 100=0.1%

由於包含如胺封端的甲基苯基矽氧烷低聚物的矽氧烷結構的聚醯亞胺鏈可表現出極性，因此與不包含矽氧烷結構的聚醯亞胺鏈會產生因極性差異引起的相分離，因此矽氧烷結構會不均勻地分佈於聚醯亞胺基質中。於此情況下，不僅難以表現出如由矽氧烷結構引起的聚醯亞胺的強度提高及應力緩和效果的物性提高效果，而且可因相分離導致霧度（haze）增加而使膜的透明性下降。特別是，於包含矽氧烷低聚物結構的二胺具有高分子量的情況，由其製備的聚醯亞胺鏈更明顯地表現出極性，且聚醯亞胺鏈間的相分離現象可更為明顯地表現出來。為了避免此種問題，於使用低分子量的矽氧烷低聚物的情況下，為了獲得應力緩和等效果，應添加大量的矽氧烷低聚物，而於此情況下，產生於低的溫度下產生Tg等問題，從而可使聚醯亞胺膜的物理特性下降。Since the polyimide chain containing a siloxane structure such as an amine-terminated methylphenylsiloxane oligomer can show polarity, the polyimide chain containing no siloxane structure will have a polarity. Due to the phase separation caused by the difference, the silicone structure will be unevenly distributed in the polyimide matrix. In this case, it is not only difficult to show the physical properties of polyimide due to the siloxane structure, such as the strength improvement and stress relaxation effect, but also the transparency of the film due to the increase in haze due to phase separation. Sexual decline. In particular, in the case where the diamine containing a siloxane oligomer structure has a high molecular weight, the polyimide chain prepared from it exhibits more obvious polarity, and the phase separation phenomenon between the polyimide chains can be more For obvious performance. In order to avoid such problems, when using low molecular weight siloxane oligomers, in order to obtain effects such as stress relaxation, a large amount of siloxane oligomers should be added, and in this case, it is generated at a low temperature Problems such as Tg may occur, which may degrade the physical properties of the polyimide film.

藉此，本發明藉由使用胺封端的甲基苯基矽氧烷低聚物與化學式1的二胺，從而可使矽氧烷低聚物結構更均勻地分佈於聚醯亞胺基質中而無相分離。In this way, by using an amine-terminated methylphenylsiloxane oligomer and the diamine of Chemical Formula 1, the structure of the silicone oligomer can be more evenly distributed in the polyimide matrix. No phase separation.

根據本發明的一方面，提供一種聚醯亞胺膜，所述聚醯亞胺膜將因包含源自此種胺封端的甲基苯基矽氧烷的結構的聚醯亞胺產生的相分離域的平均大小調節為10 nm以下。此時，相分離域意指分佈於聚醯亞胺基質內的胺封端的甲基苯基矽氧烷域。此種相分離域的大小意指於聚醯亞胺的FIB-SEM（Focused Ion Beam Scanning Electron Microscopes）影像中包圍相應區域的白色圓的最大直徑。According to an aspect of the present invention, there is provided a polyimide film that separates phases generated by polyimide containing a structure derived from such an amine-terminated methylphenylsiloxane The average size of the domain is adjusted below 10 nm. At this time, the phase separation domain means an amine-terminated methylphenylsiloxane domain distributed in the polyimide matrix. The size of this phase-separated domain means the maximum diameter of the white circle surrounding the corresponding region in the FIB-SEM (Focused Ion Beam Scanning Electron Microscopes) image of the polyimide.

於本發明的聚醯亞胺膜中，所述相分離域的平均大小為10 nm以下，例如，1 nm至10 nm的非常小的大小的相分離域、即表示源自胺封端的甲基苯基矽氧烷的域。由於在聚醯亞胺膜中，此種相分離的大小為10 nm以下，因而可具有連續相，且因此可保持耐熱性與機械物性，並將殘留應力最小化。於不具有如上所述般的連續相的情況下，雖存在減小殘留應力的效果，但耐熱性與機械物性明顯減小，從而難以用於製程。In the polyimide membrane of the present invention, the average size of the phase separation domain is 10 nm or less, for example, a very small phase separation domain of 1 nm to 10 nm, that is, a methyl group derived from an amine end Phenylsiloxane domain. In the polyimide membrane, the size of this phase separation is 10 nm or less, so it can have a continuous phase, and thus can maintain heat resistance and mechanical properties, and minimize residual stress. Without the continuous phase as described above, although there is an effect of reducing residual stress, heat resistance and mechanical properties are significantly reduced, making it difficult to use in the process.

較佳為包含胺封端的甲基苯基矽氧烷結構的部分（域）於聚醯亞胺基質內以連續相連接，此處，連續相意指奈米尺寸的域均勻地分佈於聚醯亞胺基質內的形狀。It is preferable that the part (domain) containing the amine-terminated methylphenylsiloxane structure is connected in a continuous phase in the polyimide matrix, where the continuous phase means that the nano-sized domain is uniformly distributed in the polyimide The shape within the imine matrix.

因此，本發明藉由於聚醯胺酸的製備過程中，使用胺封端的甲基苯基矽氧烷低聚物與化學式1的DDS（diaminodiphenyl sulfone）作為聚合成分，雖然出現由胺封端的甲基苯基矽氧烷引起的相分離，但其平均大小可為10 nm以下而變得非常小，且相分離域均勻地分佈於聚醯亞胺基質內，從而可減少因相分離而會出現的問題點。例如，可減少因相分離而會出現的霧度的產生，藉此可獲得具有更透明的特性的聚醯亞胺。另外，胺封端的甲基苯基矽氧烷結構以連續相存在，因此可提高聚醯亞胺的機械強度及應力緩和效果。因此種特性，本發明的聚醯亞胺膜不僅具有光學特性，而且減少於塗佈-硬化後基板彎曲的程度，從而可提供平的聚醯亞胺膜。Therefore, in the present invention, due to the preparation process of the polyamic acid, the amine-terminated methylphenylsiloxane oligomer and the DDS (diaminodiphenyl sulfone) of Chemical Formula 1 are used as the polymerization components, although the amine-terminated methyl group appears Phase separation caused by phenylsiloxane, but the average size can be very small below 10 nm, and the phase separation domain is evenly distributed in the polyimide matrix, which can reduce the occurrence of phase separation question. For example, it is possible to reduce the occurrence of haze that may occur due to phase separation, thereby obtaining a polyimide with more transparent characteristics. In addition, the amine-terminated methylphenylsiloxane structure exists as a continuous phase, so it can improve the mechanical strength and stress relaxation effect of polyimide. Because of this characteristic, the polyimide film of the present invention not only has optical characteristics, but also is reduced to the extent that the substrate bends after coating-hardening, thereby providing a flat polyimide film.

所述聚醯亞胺膜所包含的相分離域的分佈率於聚醯亞胺膜內可為約25%至60%，較佳可為50%以下或40%以下。The distribution ratio of the phase separation domains contained in the polyimide membrane in the polyimide membrane may be about 25% to 60%, preferably 50% or less or 40% or less.

此時，如圖2所示，所述相分離域的分佈率可以如下方式計算：將由FIB-SEM分析的100,000倍率的影像固定為100 mm×70 mm，之後以2 mm×2 mm對區域進行細分，將各個區域區分為白色（white）或黑色（black）區域後，計算出於整體區域中白色區域的比率。At this time, as shown in FIG. 2, the distribution ratio of the phase separation domain can be calculated as follows: fix the 100,000 magnification image analyzed by FIB-SEM to 100 mm×70 mm, and then perform the area measurement by 2 mm×2 mm After subdividing and dividing each area into white or black areas, the ratio of white areas in the overall area is calculated.

例如，於整體區域為1750個，白色區域為650個的情況， 可藉由相分離域分佈率%=（650/1750）×100=32%來計算。For example, when the total area is 1750 and the white area is 650, It can be calculated by the distribution ratio of phase separation domain %=(650/1750)×100=32%.

於在聚醯亞胺膜中如上所述般測定的相分離分佈率為25%以下的情況下，殘留應力高，於進行薄膜電晶體（thin film transistor，TFT）製程時，會發生基板的彎曲，而於分佈率為60%以上的情況，會出現由過度的相分離引起的Tg下降及渾濁（霧度）現象。In the case where the phase separation distribution rate measured in the polyimide film as described above is 25% or less, the residual stress is high, and the thin film transistor (TFT) manufacturing process may cause the substrate to warp However, in the case where the distribution rate is more than 60%, there will be a decrease in Tg and turbidity (haze) caused by excessive phase separation.

根據一實施例，所述胺封端的甲基苯基矽氧烷低聚物可具有下述化學式2的結構。According to an embodiment, the amine-terminated methylphenylsiloxane oligomer may have the structure of Chemical Formula 2 below.

[化學式2]

於所述式中，p及q為莫耳分率且為p+q=100時，p為70～90，q為10～30。[Chemical Formula 2]

In the above formula, p and q are mole fractions and p+q=100, p is 70 to 90, and q is 10 to 30.

根據一實施例，所述化學式2的二胺相對於聚醯亞胺共聚物的整體固體成分、即聚醯亞胺樹脂前驅物的重量或所述聚合成分（二胺成分及酸二酐成分）的總重量而可為5重量%至30重量%，較佳為10重量%至25重量%，進而較佳為可添加10重量%至20重量%。According to an embodiment, the weight of the diamine of the chemical formula 2 relative to the entire solid component of the polyimide copolymer, that is, the precursor of the polyimide resin, or the polymerization component (diamine component and acid dianhydride component) The total weight may be 5% to 30% by weight, preferably 10% to 25% by weight, and more preferably 10% to 20% by weight.

若過多地添加包含所述化學式2的結構的二胺，可使聚醯亞胺膜的如模數（modulus）等機械特性下降，膜強度減小，而於製程過程中會產生膜被撕裂等物理損傷。另外，於過多地添加具有化學式2的結構的二胺的情況，會出現源自具有所述矽氧烷結構的高分子的Tg，藉此，於350℃以下的低的製程溫度下出現Tg，於進行350℃以上的無機膜沈積製程時，因高分子的流動現象而於膜表面產生皺紋，從而會產生無機膜裂開的現象。If too much diamine containing the structure of the chemical formula 2 is added, the mechanical properties of the polyimide film, such as the modulus, may decrease, the strength of the film may decrease, and the film may be torn during the manufacturing process Etc. physical damage. In addition, when too much diamine having the structure of Chemical Formula 2 is added, Tg derived from the polymer having the above-mentioned siloxane structure will appear, whereby Tg will appear at a low process temperature of 350° C. or lower, When the inorganic film deposition process at 350°C or higher is performed, wrinkles are generated on the surface of the film due to the flow phenomenon of the polymer, which may cause the phenomenon of cracking of the inorganic film.

具有所述化學式2的結構的二胺化合物的分子量可為4000 g/mol以上。根據一實施例，所述分子量可為5000 g/mol以下，或4500 g/mol以下。此處分子量意指重量平均分子量，分子量計算可使用藉由使用核磁共振（nuclear magnetic resonance，NMR）分析或酸鹼滴定法來計算胺當量的方式。The molecular weight of the diamine compound having the structure of Chemical Formula 2 may be 4000 g/mol or more. According to an embodiment, the molecular weight may be 5000 g/mol or less, or 4500 g/mol or less. The molecular weight here means a weight average molecular weight, and the molecular weight calculation may use a method of calculating the amine equivalent weight by using nuclear magnetic resonance (NMR) analysis or acid-base titration.

於包含所述化學式2的結構的矽氧烷低聚物的分子量為小於4000 g/mol的情況下，可使耐熱性下降，例如可使所製備的聚醯亞胺的玻璃轉移溫度（Tg）下降，或使熱膨脹係數過度地增加。When the molecular weight of the siloxane oligomer containing the structure of Chemical Formula 2 is less than 4000 g/mol, the heat resistance can be reduced, for example, the glass transition temperature (Tg) of the prepared polyimide can be reduced Decrease, or excessively increase the coefficient of thermal expansion.

根據一實施例，包含所述化學式2的結構的兩末端二胺改質的矽氧烷低聚物於整體二胺中可包含1莫耳%至20莫耳%，且較佳可為1莫耳%以上、10莫耳%以下或5莫耳%以下。According to an embodiment, the modified siloxane oligomer at both ends of the diamine containing the structure of Chemical Formula 2 may contain 1 mol% to 20 mol% in the overall diamine, and preferably 1 mol% More than 10% of ears, less than 10 mol% or less than 5 mol%.

本發明的聚醯亞胺膜包含兩種以上的四羧酸二酐作為聚合成分，可較佳為同時包含BPDA（biphenyltetracarboxylic dianhydride）及PMDA（pyromellitic dianhydride）作為四羧酸二酐。另外，可較佳為以6：4至8：2或5：5至7：3的莫耳比包含BPDA與PMDA。The polyimide film of the present invention contains two or more kinds of tetracarboxylic dianhydride as a polymerization component, and may preferably contain both BPDA (biphenyltetracarboxylic dianhydride) and PMDA (pyromellitic dianhydride) as tetracarboxylic dianhydride. In addition, it may be preferable to include BPDA and PMDA in a molar ratio of 6:4 to 8:2 or 5:5 to 7:3.

於用以製備本發明的聚醯亞胺膜的所述聚醯胺酸聚合時，可更包含除BPDA及PMDA以外的四羧酸二酐，例如可更包含含有選自下述化學式3a至化學式3h結構的四價有機基團的四羧酸二酐。When the polyamic acid used to prepare the polyimide film of the present invention is polymerized, it may further contain tetracarboxylic dianhydride other than BPDA and PMDA, for example, it may further contain a compound selected from the following chemical formula 3a to the chemical formula Tetracarboxylic dianhydride with a tetravalent organic group of 3h structure.

[化學式3a]

[化學式3b]

[化學式3c]

[化學式3d]

[化學式3e]

[化學式3f]

[化學式3g]

[化學式3h]

於化學式3a至化學式3h中，R₁₁ 至R₂₄ 可分別獨立地為選自如下的取代基：選自由-F、-Cl、-Br及-I所組成的群組中的鹵素原子、羥基（-OH）、硫醇基（-SH）、硝基（-NO₂ ）、氰基、碳個數為1至10的烷基、碳個數為1至4的鹵代烷氧基、碳個數為1至10的鹵代烷基、碳個數為6至20的芳基， a1為0至2的整數，a2為0至4的整數，a3為0至8的整數，a4及a5分別獨立地為0至3的整數，並且a7及a8可分別獨立地為0至3的整數，a10及a12分別獨立地為0至3的整數，a11為0至4的整數，a15及a16分別獨立地為0至4的整數，a17及a18分別獨立地為0至4的整數，a6、a9、a13、a14、a19、a20分別獨立地為0至3的整數， n為1至3的整數， A11至A16可分別獨立地自由單鍵、-O-、-CR'R''-、-C(=O)-、-C(=O)O-、-C(=O)NH-、-S-、-SO₂ -、伸苯基及其組合所組成的群組中進行選擇，此時R'及R''分別獨立地自由氫原子、碳個數為1至10的烷基及碳個數為1至10的氟烷基所組成的群組進行選擇。[Chemical Formula 3a]

[Chemical Formula 3b]

[Chemical Formula 3c]

[Chemical formula 3d]

[Chemical Formula 3e]

[Chemical Formula 3f]

[Chemical formula 3g]

[Chemical formula 3h]

In Chemical Formula 3a to Chemical Formula 3h, R ₁₁ to R ₂₄ may each independently be a substituent selected from the group consisting of a halogen atom and a hydroxyl group selected from the group consisting of -F, -Cl, -Br, and -I ( -OH), thiol (-SH), nitro (-NO ₂ ), cyano, alkyl with 1 to 10 carbons, haloalkoxy with 1 to 4 carbons, and carbon 1 to 10 haloalkyl, aryl group having 6 to 20 carbons, a1 is an integer of 0 to 2, a2 is an integer of 0 to 4, a3 is an integer of 0 to 8, a4 and a5 are independently 0 Integers to 3, and a7 and a8 can be independently integers from 0 to 3, a10 and a12 are independently integers from 0 to 3, a11 is an integer from 0 to 4, a15 and a16 are independently 0 to 3 The integer of 4, a17 and a18 are independently integers of 0 to 4, a6, a9, a13, a14, a19, a20 are independently integers of 0 to 3, n is an integer of 1 to 3, A11 to A16 can be Independently free single bond, -O-, -CR'R''-, -C(=O)-, -C(=O)O-, -C(=O)NH-, -S-,- Select from the group consisting of SO ₂ -, phenylene, and combinations thereof, in which case R′ and R″ are independently free of hydrogen atoms, alkyl groups with 1 to 10 carbons, and carbon numbers of 1. The group consisting of fluoroalkyl groups up to 10 is selected.

此處，化學式中所表示的*表示結合部位。Here, * represented in the chemical formula represents a binding site.

於用以製備本發明的聚醯亞胺膜的聚醯胺酸聚合時，二胺成分可更包含除化學式1的DDS及化學式2的胺封端的甲基苯基矽氧烷以外的二胺，例如可更包含具有如下述化學式4般的結構的二胺。When the polyamic acid used to prepare the polyimide film of the present invention is polymerized, the diamine component may further include diamines other than the DDS of Chemical Formula 1 and the amine-terminated methylphenylsiloxane of Chemical Formula 2, For example, it may further contain a diamine having a structure like the following Chemical Formula 4.

[化學式4]

於化學式4中， R₃₁ 、R₃₂ 分別獨立地為選自如下的取代基：選自由-F、-Cl、-Br及-I所組成的群組中的鹵素原子、羥基（-OH）、硫醇基（-SH）、硝基（-NO₂ ）、氰基、碳個數為1至10的烷基、碳個數為1至4的鹵代烷氧基、碳個數為1至10的鹵代烷基、碳個數為6至20的芳基，較佳可為選自鹵素原子、鹵代烷基、烷基、芳基及氰基的取代基。例如，所述鹵素原子可為氟（-F），鹵代烷基為包含氟原子的碳個數為1至10的氟烷基，可自氟甲基、全氟乙基、三氟甲基等中進行選擇，所述烷基可自甲基、乙基、丙基、異丙基、第三丁基、戊基、己基中進行選擇，所述芳基可自苯基、萘基中進行選擇，更佳可為氟原子及氟烷基等包含氟原子的氟類取代基。[Chemical Formula 4]

In Chemical Formula 4, R ₃₁ and R ₃₂ are each independently a substituent selected from the group consisting of a halogen atom, a hydroxyl group (-OH) selected from the group consisting of -F, -Cl, -Br, and -I, Thiol group (-SH), nitro group (-NO ₂ ), cyano group, alkyl group with carbon number 1 to 10, halogenated alkoxy group with carbon number 1 to 4, carbon number with 1 to 10 The halogenated alkyl group and the aryl group having 6 to 20 carbon atoms are preferably a substituent selected from a halogen atom, a halogenated alkyl group, an alkyl group, an aryl group, and a cyano group. For example, the halogen atom may be fluorine (-F), and the halogenated alkyl group is a fluoroalkyl group having 1 to 10 carbon atoms containing fluorine atoms, which may be selected from fluoromethyl, perfluoroethyl, trifluoromethyl, etc. For selection, the alkyl group can be selected from methyl, ethyl, propyl, isopropyl, third butyl, pentyl, and hexyl groups, and the aryl group can be selected from phenyl and naphthyl groups, More preferably, it may be a fluorine-based substituent containing a fluorine atom such as a fluorine atom and a fluoroalkyl group.

此時，「氟類取代基」不僅意指「氟原子取代基」，而且指「含有氟原子的取代基」全部。At this time, "fluorine-based substituents" means not only "fluorine atom substituents" but also all "fluorine atom-containing substituents".

Q可自由單鍵、-O-、-CR'R''-、-C(=O)-、-C(=O)O-、-C(=O)NH-、-S-、-SO₂ -、伸苯基及其組合所組成的群組中進行選擇，此時所述R'及R''分別獨立地自由氫原子、碳個數為1至10的烷基及碳個數為1至10的氟烷基所組成的群組進行選擇。Q can be free single bond, -O-, -CR'R''-, -C(=O)-, -C(=O)O-, -C(=O)NH-, -S-, -SO ₂ -, select from the group consisting of phenylene and its combinations, in which case R'and R'' are independently free of hydrogen atoms, alkyl groups with carbon numbers 1 to 10 and carbon numbers are The group consisting of 1 to 10 fluoroalkyl groups is selected.

用以製備本發明的聚醯亞胺膜的前驅物組成物可更包含接著促進劑，相對於100重量份的整體固體成分，接著促進劑可包含0.05重量份至3重量份，較佳為0.05重量份至2重量份。The precursor composition used to prepare the polyimide film of the present invention may further include an adhesion promoter, and the accelerator may include 0.05 to 3 parts by weight relative to 100 parts by weight of the entire solid component, preferably 0.05 Parts by weight to 2 parts by weight.

根據一實施例，所述接著促進劑可包含下述化學式5或化學式6的結構。According to an embodiment, the adhesion promoter may include the structure of Chemical Formula 5 or Chemical Formula 6 below.

[化學式5]

[化學式6]

於化學式5及化學式6中， Q₁ 為碳個數為1至30的四價有機基團或由R_a -L-R_b 表示的四價有機基團，R_a 及R_b 分別獨立地為選自取代或未經取代的碳個數為4至10的脂肪族、碳個數為6至24的芳香族、碳個數為3至24的環狀脂肪族的一價有機基團，L自由單鍵、-O-、-CR'R''-、-C(=O)-、-C(=O)O-、-C(=O)NH-、-S-、-SO₂ -、伸苯基及其組合所組成的群組中進行選擇，此時R'及R''分別獨立地自由氫原子、碳個數為1至10的烷基及碳個數為1至10的氟烷基所組成的群組進行選擇，更佳為L可選自-SO₂ -、-CO-、-O-、C(CF₃ )₂ ， Q₂ 為碳個數為1至30的二價有機基團或由R_c -L-R_d 表示的二價有機基團，R_c 及R_d 分別獨立地為選自取代或未經取代的碳個數為4至10的脂肪族、碳個數為6至24的芳香族、碳個數為3至24的環狀脂肪族的一價有機基團，L自由單鍵、-O-、-CR'R''-、-C(=O)-、-C(=O)O-、-C(=O)NH-、-S-、-SO₂ -、伸苯基及其組合所組成的群組中進行選擇，此時R'及R''分別獨立地自由氫原子、碳個數為1至10的烷基及碳個數為1至10的氟烷基所組成的群組進行選擇， R₁ 及R₃ 分別獨立地為碳個數為1至5的烷基， R₂ 及R₄ 分別獨立地為氫原子或碳個數為1至5的烷基，更佳為乙基， a及b分別獨立地為1至3的整數。[Chemical Formula 5]

[Chemical Formula 6]

In Chemical Formula 5 and Chemical Formula 6, Q ₁ is a tetravalent organic group having 1 to 30 carbon atoms or _a tetravalent organic group represented by R _a -LR _b , and R _a and R _b are independently selected from Monovalent organic group of substituted or unsubstituted aliphatic with 4 to 10 carbons, aromatic with 6 to 24 carbons, cyclic aliphatic with 3 to 24 carbons, L free Bond, -O-, -CR'R''-, -C(=O)-, -C(=O)O-, -C(=O)NH-, -S-, -SO ₂ -, extension Choose from the group consisting of phenyl and its combination, in which case R'and R'' are independently free of hydrogen atoms, alkyl groups with 1 to 10 carbon atoms, and fluoroalkanes with 1 to 10 carbon atoms. Group selected from the group, preferably L can be selected from -SO ₂ -, -CO-, -O-, C(CF ₃ ) ₂ , Q ₂ is a divalent organic carbon number of 1 to 30 Group or a divalent organic group represented by R _c -LR _d , R _c and R _d are each independently selected from substituted or unsubstituted aliphatic having 4 to 10 carbons and having 6 carbons Aromatic to 24, cyclic aliphatic monovalent organic groups with 3 to 24 carbons, L free single bond, -O-, -CR'R''-, -C(=O)-, -C(=O)O-, -C(=O)NH-, -S-, -SO ₂ -, phenylene and their combinations to select, at this time R'and R'' Are independently selected from the group consisting of a hydrogen atom, an alkyl group with a carbon number of 1 to 10 and a fluoroalkyl group with a carbon number of 1 to 10, and R ₁ and R ₃ are independently a carbon number of The alkyl group of 1 to 5, R ₂ and R ₄ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, more preferably an ethyl group, and a and b are each independently an integer of 1 to 3.

例如，所述Q₁ 可為選自下述化學式5a至化學式5s的四價有機基團，但並不限定於此。

For example, the Q ₁ may be a tetravalent organic group selected from the following Chemical Formula 5a to Chemical Formula 5s, but is not limited thereto.

於所述化學式6中，Y可為選自下述化學式6a至化學式6t的二價有機基團，但並不限定於此。

In the above Chemical Formula 6, Y may be a divalent organic group selected from the following Chemical Formula 6a to Chemical Formula 6t, but is not limited thereto.

包含所述化學式5及化學式6的結構的接著促進劑不僅可提高與無機層的接著力，而且與聚醯胺酸的反應性低。於添加通常的提高接著力的添加劑、即如異氰酸基三乙氧基矽烷（isocyanato triethoxysilane，ICTEOS）、胺基丙基三乙氧基矽烷（aminopropyltriethoxysilane，APTEOS）的烷氧基矽烷類添加劑的情況，可減小因聚醯胺酸與所述添加劑的副反應出現的黏度的上升，因此可提高於常溫下的儲存穩定性。The adhesion promoter including the structures of Chemical Formula 5 and Chemical Formula 6 not only improves the adhesion with the inorganic layer, but also has low reactivity with polyamide. In order to add common additives to improve adhesion, such as isocyanato triethoxysilane (isocyanato triethoxysilane (ICTEOS), aminopropyltriethoxysilane (aminopropyltriethoxysilane, APTEOS) alkoxysilane additives In this case, the increase in viscosity due to the side reaction of polyamide and the additive can be reduced, and thus the storage stability at normal temperature can be improved.

先前用作可撓性顯示器基板的高耐熱聚醯亞胺為了提高與用作載體基板的玻璃或沈積有無機層的玻璃基板的接著性，使用於玻璃上塗佈接著促進劑來制模的方法，但此種現有的接著促進劑因塗佈接著促進劑而產生異物或要求附加的塗佈製程而於製程方面存在經濟性低的限制。另外，於向聚醯亞胺樹脂前驅物直接添加接著促進劑的情況下，胺基與聚醯胺酸的羧基構成鹽而析出從而使接著性下降的問題亦隨之而來。In order to improve the adhesion to glass used as a carrier substrate or a glass substrate deposited with an inorganic layer, a high-heat-resistant polyimide used as a flexible display substrate in the past, a method of applying an adhesion promoter to the glass for molding However, such an existing adhesion promoter has a limitation of low economical efficiency in the production process due to the generation of foreign matter by coating the adhesion promoter or requiring an additional coating process. In addition, in the case where the adhesion promoter is directly added to the polyimide resin precursor, the problem arises that the amine group and the carboxyl group of the polyamic acid form a salt and precipitate out, thereby deteriorating the adhesion.

另外，亦存在合成接著促進劑並直接添加至聚醯亞胺前驅物而可使接著性提高的先行技術，但由於使用具有比較剛性結構的酸酐，因此存在如下問題點：硬化後於接著促進劑部分出現相位差延遲現象，導致使最終所製備的聚醯亞胺膜的厚度方向的相位差值上升的結果。另外，於使用如4,4'-氧雙鄰苯二甲酸酐（4,4'-oxydiphthalic anhydride，ODPA）般的包含柔軟的結構的接著促進劑的情況下，藉由結構的柔軟性而相位差值不變高，但存在Tg變低的傾向。In addition, there are also advanced technologies for synthesizing an adhesion promoter and adding it directly to the polyimide precursor to improve the adhesion. However, since an acid anhydride having a relatively rigid structure is used, there is the following problem: after hardening, the adhesion promoter A phase retardation phenomenon occurs in part, which results in an increase in the phase difference value in the thickness direction of the polyimide film finally prepared. In addition, in the case of using an adhesion promoter containing a soft structure like 4,4'-oxydiphthalic anhydride (ODPA), the phase is determined by the softness of the structure The difference is not high, but there is a tendency for Tg to become low.

根據較佳的實施例，接著促進劑可具有芴（fluorene）骨架，該情況可最大的保持接著促進的效果，並因芴骨架而產生分子間的自由體積而不對填充密度（packing density）造成影響，並表現出等方性的特性。另外，因大量包含芳香族的結構特徵而耐熱性亦優異。即，即便於聚醯亞胺樹脂前驅物混合使用接著促進劑亦不析出，可將異物的產生最小化，與基板的接著力優異，且於塗佈硬化後不對所製成的聚醯亞胺膜的光學物性、即厚度方向的相位差造成影響，從而可提供一種等方性的聚醯亞胺膜。According to a preferred embodiment, the adhesion promoter may have a fluorene skeleton, which can maximize the effect of adhesion promotion, and the free volume between molecules is generated due to the fluorene skeleton without affecting the packing density. And show the characteristic of equivalence. In addition, it has excellent heat resistance due to a large amount of aromatic structural features. That is, even if the adhesion promoter is used in combination with the polyimide resin precursor, it does not precipitate, which minimizes the generation of foreign substances, has excellent adhesion to the substrate, and does not disperse the polyimide after coating hardening. The optical properties of the film, that is, the phase difference in the thickness direction are affected, thereby providing an isotropic polyimide film.

根據本發明的一實施例，二酐成分與二胺成分可以1：0.9～0.9：1、1：0.98～0.98：1或1：0.99～0.99：1的莫耳比進行反應，較佳為為了提高反應性及提高製程性，所述二酐成分可相對於二胺成分以過多的量進行反應，或二胺成分相對於二酐成分以過多的量進行反應。根據較佳的實施例，較佳為二酐成分相對於二胺以過多的量進行反應（例如，二酐：二胺=1：0.995～0.999）。According to an embodiment of the present invention, the dianhydride component and the diamine component can be reacted at a molar ratio of 1:0.9 to 0.9:1, 1:0.98 to 0.98:1, or 1:0.99 to 0.99:1, preferably for To improve reactivity and improve processability, the dianhydride component may react in an excessive amount relative to the diamine component, or the diamine component may react in an excessive amount relative to the dianhydride component. According to a preferred embodiment, it is preferable that the dianhydride component reacts in an excessive amount relative to the diamine (for example, dianhydride:diamine=1:0.995 to 0.999).

作為於所述聚醯胺酸聚合反應時可使用的有機溶劑，可為如下等：γ-丁內酯、1,3-二甲基-2-咪唑啶酮、甲基乙基酮、環己酮、環戊酮、4-羥基-4-甲基-2-戊酮等酮類；甲苯、二甲苯、四甲基苯等芳香族烴類；乙二醇單***、乙二醇單甲醚、乙二醇單丁醚、二乙二醇單***、二乙二醇單甲醚、二乙二醇單丁醚、丙二醇單甲醚、丙二醇單***、二丙二醇二***、三乙二醇單***等二醇醚類（溶纖劑）；乙酸乙酯、乙酸丁酯、乙二醇單***乙酸酯、乙二醇單丁醚乙酸酯、二乙二醇單***乙酸酯、二丙二醇單甲醚乙酸酯、乙醇、丙醇、乙二醇、丙二醇、卡必醇、二甲基丙醯胺（dimethylpropionamide，DMPA）、二乙基丙醯胺（diethylpropionamide，DEPA）、二甲基乙醯胺（dimethylacetamide，DMAc）、N,N-二乙基乙醯胺、二甲基甲醯胺（dimethylformamide，DMF）、二乙基甲醯胺（diethylformamide，DEF）、N-甲基吡咯啶酮（N-methyl pyrrolidone，NMP）、N-乙基吡咯啶酮（N-ethyl pyrrolidone，NEP）、N,N-二甲基甲氧基乙醯胺、二甲基亞碸、吡啶、二甲基碸、六甲基磷醯胺、四甲基脲、N-甲基己內醯胺、四氫呋喃、間二噁烷、對二噁烷、1,2-二甲氧基乙烷、雙(2-甲氧基乙基)醚、1,2-雙(2-甲氧基乙氧基)乙烷、雙[2-(2-甲氧基乙氧基)]醚、愛庫阿米德（Equamide）M100、愛庫阿米德（Equamide）B100，且可單獨使用其等中的一種或可使用兩種以上的混合物。As the organic solvent that can be used during the polymerization of the polyamide, the following may be mentioned: γ-butyrolactone, 1,3-dimethyl-2-imidazolidinone, methyl ethyl ketone, cyclohexane Ketones such as ketone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone; aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene; ethylene glycol monoethyl ether, ethylene glycol monomethyl ether , Ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol mono Glycol ethers (cellosolve) such as ether; ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethyl ether Propylene glycol monomethyl ether acetate, ethanol, propanol, ethylene glycol, propylene glycol, carbitol, dimethylpropionamide (DMPA), diethylpropionamide (DEPA), dimethyl Dimethylacetamide (DMAc), N,N-diethylacetamide, dimethylformamide (DMF), diethylformamide (DEF), N-methylpyrrolidine N-methyl pyrrolidone (NMP), N-ethyl pyrrolidone (NEP), N,N-dimethyl methoxyacetamide, dimethyl sulfoxide, pyridine, dimethyl Glyphosate, hexamethylphosphoramide, tetramethylurea, N-methylcaprolactam, tetrahydrofuran, m-dioxane, p-dioxane, 1,2-dimethoxyethane, bis(2 -Methoxyethyl)ether, 1,2-bis(2-methoxyethoxy)ethane, bis[2-(2-methoxyethoxy)]ether, acuamid ( Equamide) M100, Equamide B100, and one of them can be used alone or a mixture of two or more can be used.

例如，作為可用於所述二胺與酸二酐的聚合反應的有機溶劑，可包含於25℃下分配係數（LogP值）為正數的溶劑，所述有機溶劑的沸點可為300℃以下，更具體而言分配係數LogP值可為0.01至3、或0.01至2、或0.1至2。For example, as the organic solvent that can be used for the polymerization reaction of the diamine and the acid dianhydride, a solvent having a positive partition coefficient (LogP value) at 25°C may be included. The boiling point of the organic solvent may be 300°C or less. Specifically, the distribution coefficient LogP value may be 0.01 to 3, or 0.01 to 2, or 0.1 to 2.

所述分配係數可使用高級化學發展有限公司（ACD/Labs）的ACD/Percepta平台（platform）的ACD/LogP模組（module）來進行計算，ACD/LogP模組利用分子的二維（2 dimensional，2D）結構並利用基於定量結構性質關係（Quantitative Structure-Property Relationship，QSPR）方法論的演算法（algorithm）。代表性的溶劑於25℃下的分配係數（LogP值）如下。

The distribution coefficient can be calculated using the ACD/LogP module of the ACD/Percepta platform (ACD/Labs) of the Advanced Chemical Development Co., Ltd. (ACD/Labs). The ACD/LogP module uses the molecular two-dimensional (2 dimensional) , 2D) structure and use algorithm based on Quantitative Structure-Property Relationship (QSPR) methodology. The partition coefficient (LogP value) of representative solvents at 25°C is as follows.

所述分配係數（LogP）為正數的溶劑可為選自如下的一種以上：二甲基丙醯胺（dimethylpropionamide，DMPA）、二乙基丙醯胺（diethylpropionamide，DEPA）、N,N-二乙基乙醯胺（N,N-diethylacetamide，DEAc）、N,N-二乙基甲醯胺（N,N-diethylformamide，DEF）、N-乙基吡咯啶酮（N-ethylpyrrolidone，NEP），特別是可為其等中的醯胺類溶劑。The solvent with a positive distribution coefficient (LogP) may be one or more selected from the following: dimethylpropionamide (DMPA), diethylpropionamide (DEPA), N,N-diethyl N, N-diethylacetamide (DEAc), N, N-diethylformamide (DEF), N-ethylpyrrolidone (NEP), especially It can be used as an amide-based solvent.

使所述四羧酸二酐與二胺反應的方法可根據溶液聚合等通常的聚醯亞胺樹脂前驅物聚合製備方法實施，具體而言，可藉由於使二胺溶解於有機溶劑中後，向最終取得的混合溶液添加四羧酸二酐使其進行聚合反應來製備。The method for reacting the tetracarboxylic dianhydride with the diamine can be carried out according to a general method for preparing a polyimide resin precursor polymerization such as solution polymerization, specifically, after dissolving the diamine in an organic solvent, Tetracarboxylic dianhydride is added to the finally obtained mixed solution and subjected to polymerization reaction to prepare.

所述聚合反應可於非活性氣體或氮氣流下實施，且可於無水條件下實施。The polymerization reaction can be carried out under a flow of inert gas or nitrogen, and can be carried out under anhydrous conditions.

另外，所述聚合反應時可於反應溫度為-20℃至80℃、較佳為0至80℃下實施。反應溫度過高的情況，反應性高而分子量會變得過大，且前驅物組成物的黏度上升，從而會不利於製程方面。In addition, the polymerization reaction can be carried out at a reaction temperature of -20°C to 80°C, preferably 0 to 80°C. When the reaction temperature is too high, the reactivity is high and the molecular weight becomes too large, and the viscosity of the precursor composition increases, which is not conducive to the process.

包含所述聚醯胺酸的聚醯亞胺樹脂前驅物組成物可為溶解於有機溶劑中的溶液的形態，具有此種形態的情況，例如於有機溶劑中合成聚醯亞胺樹脂前驅物的情況下，溶液亦可為獲得的反應溶液本身，或亦可為用其他溶劑對該反應溶液進行稀釋而成。又，於以固體粉末獲得聚醯亞胺樹脂前驅物的情況下，亦可為使其溶解於有機溶劑來作為溶液而成。例如，於進行聚合反應時，使用LogP為正數的有機溶劑，作為之後混合的有機溶劑，可混合使用LogP為負數的有機溶劑。The polyimide resin precursor composition containing the polyamic acid may be in the form of a solution dissolved in an organic solvent. In this case, for example, the synthesis of the polyimide resin precursor in an organic solvent In this case, the solution may be the obtained reaction solution itself, or may be obtained by diluting the reaction solution with another solvent. In addition, when a polyimide resin precursor is obtained from a solid powder, it may be prepared as a solution by dissolving it in an organic solvent. For example, when performing a polymerization reaction, an organic solvent with a positive LogP is used, and as an organic solvent to be mixed later, an organic solvent with a negative LogP can be mixed and used.

根據一實施例，可添加有機溶劑對組成物的固體成分含量進行調節，以使整體聚醯亞胺樹脂前驅物的含量為8重量%至25重量%，較佳為可調節為10重量%至25重量%、更佳為10重量%至20重量%以下。According to an embodiment, an organic solvent may be added to adjust the solid content of the composition, so that the content of the overall polyimide resin precursor is 8% to 25% by weight, preferably 10% to 25% by weight, more preferably 10% by weight to 20% by weight or less.

又，可調節所述聚醯亞胺樹脂前驅物組成物以具有2,000 cP以上、或3,000 cP以上、或4,000 cP以上的黏度，且較佳為調節所述聚醯亞胺樹脂前驅物組成物的黏度以具有10,000 cP以下、較佳為9,000 cP以下、更佳為8,000 cP以下的黏度。聚醯亞胺樹脂前驅物組成物的黏度超過10,000 cP的情況，對聚醯亞胺膜進行加工時，脫泡的效率性下降，不僅製程方面的效率下降，而且所製備的膜因產生氣泡而表面照度不佳，從而可使電氣、光學、機械特性下降。Furthermore, the polyimide resin precursor composition can be adjusted to have a viscosity of 2,000 cP or more, or 3,000 cP or more, or 4,000 cP or more, and it is preferable to adjust the polyimide resin precursor composition The viscosity may have a viscosity of 10,000 cP or less, preferably 9,000 cP or less, and more preferably 8,000 cP or less. When the viscosity of the polyimide resin precursor composition exceeds 10,000 cP, when processing the polyimide film, the efficiency of degassing decreases, not only the efficiency of the manufacturing process decreases, but also the prepared film is caused by bubbles. Poor surface illumination, which can reduce electrical, optical, and mechanical properties.

又，本發明的聚醯亞胺的分子量可具有10,000 g/mol至200,000 g/mol、或20,000 g/mol至100,000 g/mol、或30,000 g/mol至100,000 g/mol的重量平均分子量。另外，本發明的聚醯亞胺的分子量分佈（Mw/Mn）為1.1至2.5較佳。重量平均分子量Mw及數平均分子量Mn使用凝膠滲透層析法並藉由標準聚苯乙烯換算求得。於聚醯亞胺的重量平均分子量或分子量分佈脫離所述範圍的情況，存在膜會難以形成、或者使透射度、耐熱性及機械特性等聚醯亞胺類膜的特性下降之虞。Also, the molecular weight of the polyimide of the present invention may have a weight average molecular weight of 10,000 g/mol to 200,000 g/mol, or 20,000 g/mol to 100,000 g/mol, or 30,000 g/mol to 100,000 g/mol. In addition, the molecular weight distribution (Mw/Mn) of the polyimide of the present invention is preferably 1.1 to 2.5. The weight average molecular weight Mw and the number average molecular weight Mn were determined by standard polystyrene conversion using gel permeation chromatography. When the weight average molecular weight or molecular weight distribution of the polyimide is out of the above range, the film may be difficult to form, or the characteristics of the polyimide-based film such as transmittance, heat resistance, and mechanical properties may decrease.

進而，藉由使所述聚合反應最終取得的聚醯亞胺樹脂前驅物醯亞胺化，從而可製備透明聚醯亞胺膜。Furthermore, a transparent polyimide film can be prepared by imidizing the polyimide resin precursor finally obtained in the polymerization reaction.

根據一實施例，如上所述般獲得的聚醯亞胺膜組成物可經過如下步驟來製備聚醯亞胺膜： 將所述聚醯亞胺樹脂前驅物組成物塗佈於基板上的步驟；以及 對塗佈的所述樹脂前驅物組成物進行熱處理的步驟。According to an embodiment, the polyimide film composition obtained as described above can be prepared through the following steps to prepare a polyimide film: The step of coating the polyimide resin precursor composition on the substrate; and A step of heat-treating the applied resin precursor composition.

此時，作為所述基板，可使用玻璃、金屬基板或塑膠基板等而無特別限制，其中，亦可較佳為使用玻璃基板：於針對聚醯亞胺樹脂前驅物的醯亞胺化及硬化製程中，熱穩定性及化學穩定性優異，亦無需單獨的脫模劑進行處理，且可對硬化後形成的聚醯亞胺類膜無損傷且容易地進行分離。At this time, as the substrate, a glass, metal substrate, plastic substrate, or the like can be used without particular limitation. Among them, a glass substrate can also be preferably used: for the imidization and curing of the polyimide resin precursor In the process, it has excellent thermal stability and chemical stability, and does not require a separate release agent for processing. It can also easily separate the polyimide film formed after curing without damage.

又，可根據通常的塗佈方法實施所述塗佈製程，具體而言可利用旋轉塗佈法、棒塗法、輥塗法、氣刀法、凹版法、反向輥法、吻輥法、刮刀法、噴塗法、浸漬法、或塗刷法等。其中，可更佳為藉由可進行連續製程，且可增加聚醯亞胺的醯亞胺化率的流延（casting）法實施。In addition, the coating process can be carried out according to a general coating method, specifically, a spin coating method, a bar coating method, a roll coating method, an air knife method, a gravure method, a reverse roll method, a kiss roll method, Scraper method, spraying method, dipping method, or brushing method, etc. Among them, it can be more preferably implemented by a casting method that can perform a continuous process and can increase the imidate ratio of polyimide.

又，可按照以最終製備的聚醯亞胺膜具有適合於顯示器基板用的厚度的厚度範圍，而將所述聚醯亞胺類溶液塗佈至基板上。In addition, the polyimide-based solution may be applied to the substrate so that the polyimide film finally prepared has a thickness range suitable for a display substrate.

具體而言，可按照10 μm至30 μm的厚度的量進行塗佈。於塗佈所述聚醯亞胺樹脂前驅物組成物後，於進行硬化製程之前，可更選擇性地實施用以去除存在於聚醯亞胺樹脂前驅物組成物內的溶劑的乾燥製程。Specifically, the coating can be performed in a thickness of 10 μm to 30 μm. After coating the polyimide resin precursor composition, and before performing the hardening process, a drying process for removing the solvent present in the polyimide resin precursor composition can be more selectively performed.

可根據通常的方法實施所述乾燥製程，具體而言可於140℃以下，或80℃至140℃的溫度下實施。若乾燥製程的實施溫度小於80℃，則乾燥製程變長，於超過140℃的情況，醯亞胺化局部進行，從而難以形成具有均勻的厚度的聚醯亞胺膜。The drying process can be carried out according to a general method, specifically, it can be carried out at a temperature of 140°C or lower, or 80°C to 140°C. If the implementation temperature of the drying process is less than 80°C, the drying process becomes longer, and if it exceeds 140°C, the imidization proceeds locally, making it difficult to form a polyimide film having a uniform thickness.

進而，將所述聚醯亞胺樹脂前驅物組成物塗佈於基板，於紅外線（infrared，IR）烘箱、熱風烘箱或熱板上進行熱處理，此時，所述熱處理溫度可為300℃至500℃，較佳為320℃至480℃的溫度範圍，亦可於所述溫度範圍下進行多步驟加熱處理。所述熱處理製程可於20分鐘至70分鐘的持續時間內進行，且較佳為可於20分鐘至60分鐘左右的時間期間進行。Furthermore, the polyimide resin precursor composition is coated on the substrate and heat-treated in an infrared (IR) oven, hot air oven or hot plate. In this case, the heat treatment temperature may be 300°C to 500°C ℃, preferably 320 ℃ to 480 ℃ temperature range, multi-step heat treatment can also be performed in the temperature range. The heat treatment process may be performed for a duration of 20 minutes to 70 minutes, and preferably may be performed for a time period of approximately 20 minutes to 60 minutes.

之後，可根據通常的方法將形成於基板上的聚醯亞胺膜自基板剝離，從而製備聚醯亞胺膜。After that, the polyimide film formed on the substrate can be peeled from the substrate according to a general method to prepare a polyimide film.

如上所述般製備的聚醯亞胺膜的模數為2.2 GPa以下，例如可為0.1 GPa至2.0 GPa，伸長率可為20%以上。若所述彈性率小於0.1 GPa，則膜的剛性低，面對外部衝擊容易破裂，若所述彈性率超過2.2 GPa，則膜的剛性雖然優異，但會產生不能確保充分的柔軟性的問題。The modulus of the polyimide film prepared as described above is 2.2 GPa or less, for example, it can be 0.1 GPa to 2.0 GPa, and the elongation can be 20% or more. If the modulus of elasticity is less than 0.1 GPa, the rigidity of the film is low, and it is easy to break in response to external impact. If the modulus of elasticity exceeds 2.2 GPa, the rigidity of the membrane is excellent, but there is a problem that sufficient flexibility cannot be ensured.

另外，本發明的聚醯亞胺膜的玻璃轉移溫度（Tg）可為230℃以上。In addition, the glass transition temperature (Tg) of the polyimide film of the present invention may be 230°C or higher.

另外，本發明的聚醯亞胺膜隨溫度變化的熱穩定性會優異，例如於100℃至400℃溫度範圍內，經過n+1次加熱及冷卻製程後的熱膨脹係數可具有-10 ppm/℃至100 ppm/℃的值，較佳為具有-7 ppm/℃至90 ppm/℃的值，更佳為可為80 ppm/℃以下。In addition, the thermal stability of the polyimide film of the present invention with temperature changes will be excellent. For example, in the temperature range of 100°C to 400°C, the thermal expansion coefficient after n+1 heating and cooling processes may have -10 ppm/ The value of °C to 100 ppm/°C preferably has a value of -7 ppm/°C to 90 ppm/°C, and more preferably 80 ppm/°C or less.

另外，本發明的聚醯亞胺膜厚度方向的相位差（R_th ）具有-100 nm至+100 nm的值，從而可表現出等方性，並使視覺感受性提高。In addition, the phase difference (R _th ) in the thickness direction of the polyimide film of the present invention has a value of -100 nm to +100 nm, so that it can exhibit isotropy and improve visual sensibility.

根據一實施例，所述聚醯亞胺膜與載體基板的接著力可為5 gf/in以上，且較佳可為10 gf/in以上。According to an embodiment, the adhesion force between the polyimide film and the carrier substrate may be 5 gf/in or more, and preferably 10 gf/in or more.

另外，本發明提供一種可撓性裝置的製備製程，包含如下步驟： 將包含聚醯胺酸的前驅物組成物塗佈於載體基板上，所述聚醯胺酸是將包含DDS（diaminodiphenyl sulfone）與胺封端的甲基苯基矽氧烷低聚物的二胺、與兩種以上的四羧酸二酐作為聚合成分製備而成； 藉由對所述前驅物組成物進行加熱而使聚醯胺酸醯亞胺化，從而形成聚醯亞胺膜； 於所述聚醯亞胺膜上形成元件；以及 將形成有元件的所述聚醯亞胺膜自所述載體基板剝離。In addition, the present invention provides a manufacturing process of a flexible device, which includes the following steps: The precursor composition containing polyamic acid is coated on the carrier substrate. The polyamic acid is a diamine containing a methylphenyl siloxane oligomer containing DDS (diaminodiphenyl sulfone) and an amine. It is prepared with two or more kinds of tetracarboxylic dianhydride as a polymerization component; Forming polyimide film by heating the precursor composition to imide polyimidamide; Forming an element on the polyimide film; and The polyimide film formed with the element is peeled from the carrier substrate.

特別是，所述可撓性裝置的製備製程可包含LTPS（low temperature polysilicon）薄膜製備製程、ITO薄膜製備製程或氧化物薄膜製備製程。In particular, the manufacturing process of the flexible device may include an LTPS (low temperature polysilicon) film manufacturing process, an ITO film manufacturing process or an oxide film manufacturing process.

例如，於包含如下步驟的LTPS薄膜製備製程以後，藉由雷射剝離等對載體基板與聚醯亞胺膜進行剝離，從而可得到包含LTPS層的可撓性裝置： 於聚醯亞胺膜上形成包含SiO₂ 的阻斷層的步驟； 於所述阻斷層上沈積非晶矽（Amorphous silicon，a-Si）薄膜的步驟； 於450℃±50℃的溫度下對沈積的所述a-Si薄膜進行熱處理的脫氫退火步驟；以及 利用準分子雷射等使所述a-Si薄膜結晶化的步驟。For example, after the LTPS film preparation process including the following steps, the carrier substrate and the polyimide film are stripped by laser peeling, etc., so that a flexible device including an LTPS layer can be obtained: on the polyimide film A step of forming a blocking layer containing SiO ₂ ; a step of depositing an amorphous silicon (a-Si) thin film on the blocking layer; the deposited a- at a temperature of 450°C±50°C The dehydrogenation annealing step of heat treatment of the Si thin film; and the step of crystallizing the a-Si thin film using excimer laser or the like.

聚醯亞胺膜內的氣孔（pore）於進行LTPS（low temperature polysilicon）TFT製程時，藉由高溫的熱處理製程而會於無機膜（聚矽薄膜）上誘發龜裂。因此，本發明藉由將此種聚醯亞胺膜內氣孔的比率調節為1%以下，或者/並且將相分離域的平均大小調節為10 nm以下，從而可抑制或明顯減少無機膜層龜裂的產生。The pores in the polyimide film during the LTPS (low temperature polysilicon) TFT process will induce cracks on the inorganic film (polysilicon film) through a high temperature heat treatment process. Therefore, in the present invention, by adjusting the ratio of pores in such a polyimide membrane to 1% or less, or/and adjusting the average size of the phase separation domain to 10 nm or less, the inorganic film layer turtle can be suppressed or significantly reduced The generation of cracks.

氧化物薄膜製程與利用矽的製程相比而可於低的溫度下進行熱處理，例如ITO TFT製程的熱處理溫度可為200℃±50℃，氧化物TFT製程的熱處理溫度可為320℃±50℃。The oxide thin film process can be heat-treated at a lower temperature than the process using silicon. For example, the heat treatment temperature of the ITO TFT process can be 200°C±50°C, and the heat treatment temperature of the oxide TFT process can be 320°C±50°C. .

以下，對本發明的實施例進行詳細說明，以使本發明所屬技術領域中具有通常知識者可容易地實施。但是，本發明可表現為各種不同的形態，且並不限定於此處所說明的實施例。Hereinafter, the embodiments of the present invention will be described in detail so that those with ordinary knowledge in the technical field to which the present invention pertains can easily implement them. However, the present invention can be expressed in various forms, and is not limited to the embodiments described here.

>實施例1>BPDA-PMDA（6:4）/DDS/DPS-DMS 10 wt% 於流通有氮氣流的反應器內填充DEAc（N,N-diethylacetamide）後，於將反應器的溫度保持為25℃的狀態下，於相同的溫度下添加0.15096 mol的4,4'-DDS（4,4'-diaminodiphenyl sulfone）並使其溶解。於相同的溫度下，向添加有所述DDS的溶液添加0.0611 mol的PMDA（pyromellitic dianhydride）以及0.0917 mol的BPDA（3,3',4,4'-biphenyltetracarboxylic dianhydride），於24小時的持續時間內進行攪拌後添加0.00199 mol的兩末端胺改質的DPS-DMS（diphenylsiloxane-dimethylsiloxane co-oligomer，分子量4360 g/mol），於80℃下4小時的持續時間內進行攪拌。之後，除去油浴（oil bath）恢復至室溫，獲得透明的聚醯胺酸的DEAc溶液。>Example 1>BPDA-PMDA (6:4)/DDS/DPS-DMS 10 wt% After filling DEAc (N, N-diethylacetamide) in the reactor with nitrogen flow, 0.15096 mol of 4,4'-DDS (0.15096 mol) was added at the same temperature while maintaining the reactor temperature at 25°C. 4,4'-diaminodiphenyl sulfone) and dissolve it. At the same temperature, add 0.0611 mol of PMDA (pyromellitic dianhydride) and 0.0917 mol of BPDA (3,3',4,4'-biphenyltetracarboxylic dianhydride) to the DDS-added solution for a duration of 24 hours After stirring, 0.0099 mol of both-terminal modified amine-modified DPS-DMS (diphenylsiloxane-dimethylsiloxane co-oligomer, molecular weight 4360 g/mol) was added, and the mixture was stirred at 80°C for 4 hours. After that, the oil bath was removed and the temperature was returned to room temperature to obtain a transparent DEAc solution of polyamide.

>實施例2至實施例12>BPDA-PMDA/DDS/DPS-DMS 除使BPDA及PMDA的莫耳比與DPS-DMS添加量如表1至表3記載所示般變化以外，以與實施例1相同的方法製備透明的聚醯胺酸的DEAc溶液。>Example 2 to Example 12>BPDA-PMDA/DDS/DPS-DMS A DEAc solution of transparent polyamide was prepared in the same manner as in Example 1, except that the molar ratio of BPDA and PMDA and the amount of DPS-DMS added were changed as shown in Tables 1 to 3.

>實施例13至實施例15> 除使DPS-DMS含量分別為25 wt%、20 wt%及5 wt%之外，以與實施例9相同的方法製備聚醯胺酸溶液。>Example 13 to Example 15> A polyamic acid solution was prepared in the same manner as in Example 9, except that the DPS-DMS content was 25 wt%, 20 wt%, and 5 wt%, respectively.

>比較例1>BPDA_PMDA（6：4）_DDS 於流通有氮氣流的反應器內填充DEAc後，於將反應器的溫度保持為25℃的狀態下，於相同的溫度下添加0.08497 mol的4,4'-DDS並使其溶解。於相同的溫度下向添加有所述DDS的溶液添加0.03399 mol的PMDA及0.005098 mol的BPDA，於24小時的持續時間內進行攪拌後，獲得透明的聚醯胺酸的DEAc溶液。>Comparative Example 1>BPDA_PMDA (6:4)_DDS After DEAc was filled in the reactor through which a nitrogen flow was flowing, 0.08497 mol of 4,4'-DDS was added and dissolved at the same temperature while maintaining the temperature of the reactor at 25°C. To the solution to which the DDS was added, 0.03399 mol of PMDA and 0.005098 mol of BPDA were added at the same temperature, and after stirring for a duration of 24 hours, a transparent polyacrylic acid DEAc solution was obtained.

>比較例2>BPDA_PMDA（6：4）/TFMB/DPS-DMS 10 wt% 於流通有氮氣流的反應器內填充DEAc後，於將反應器的溫度保持為25℃的狀態下，於相同的溫度下添加0.1121 mol的2,2'-雙(三氟甲基)聯苯胺（2,2'-Bis(trifluoromethyl)benzidine，TFMB）並使其溶解。於相同的溫度下向添加有所述TFMB的溶液添加0.0453 mol的PMDA及0.0679 mol的BPDA，於24小時的持續時間內進行攪拌後添加0.00168 mol的兩末端胺改質的DPS-DMS（分子量4360 g/mol），於80℃下4小時的持續時間內進行攪拌。之後除去油浴恢復至室溫，獲得透明的聚醯胺酸的DEAc溶液。>Comparative Example 2>BPDA_PMDA (6:4)/TFMB/DPS-DMS 10 wt% After filling the reactor with nitrogen flow through DEAc, while maintaining the reactor temperature at 25°C, add 0.1121 mol of 2,2'-bis(trifluoromethyl)benzidine at the same temperature (2,2'-Bis(trifluoromethyl)benzidine, TFMB) and dissolve it. At the same temperature, 0.0453 mol of PMDA and 0.0679 mol of BPDA were added to the solution to which the TFMB was added, and after stirring for 24 hours, 0.00168 mol of both-terminal amine-modified DPS-DMS (molecular weight 4360 g/mol), stirring at 80°C for a duration of 4 hours. After that, the oil bath was removed and returned to room temperature to obtain a transparent DEAc solution of polyamide.

>比較例3>BPDA_PMDA（6：4）/TFMB/DPS-DMS 15 wt% 除了使DPS-DMS添加量變為15 wt%之外，以與比較例2相同的方法製備透明的聚醯胺酸的DEAc溶液。>Comparative Example 3>BPDA_PMDA (6:4)/TFMB/DPS-DMS 15 wt% A transparent DEAc solution of polyamide was prepared in the same manner as Comparative Example 2 except that the amount of DPS-DMS added was changed to 15 wt%.

>比較例4>BPDA_PMDA（6：4）/TFMB/DPS-DMS 18 wt% 除了使DPS-DMS添加量變為18 wt%之外，以與比較例2相同的方法製備透明的聚醯胺酸的DEAc溶液。>Comparative Example 4>BPDA_PMDA (6:4)/TFMB/DPS-DMS 18 wt% A transparent DEAc solution of polyamide was prepared in the same manner as Comparative Example 2 except that the amount of DPS-DMS added was changed to 18 wt%.

>實驗例1> 將於實施例1至實施例12及比較例1至比較例4中製備的各個聚醯亞胺樹脂前驅物溶液旋轉塗佈於玻璃基板上。將塗佈有聚醯亞胺前驅物溶液的玻璃基板放置於烘箱並以5℃/min的速度進行加熱，於80℃下保持30分鐘、於400℃下保持30分鐘進行硬化製程來製備聚醯亞胺膜。對各個膜的物性進行測定並示於下述表1至表3。>Experiment example 1> Each polyimide resin precursor solution prepared in Examples 1 to 12 and Comparative Examples 1 to 4 was spin-coated on a glass substrate. The glass substrate coated with the polyimide precursor solution was placed in an oven and heated at a rate of 5°C/min, held at 80°C for 30 minutes, and held at 400°C for 30 minutes for a hardening process to prepare a polyimide Imine membrane. The physical properties of each film were measured and shown in Tables 1 to 3 below.

>黏度> 溶液的黏度利用晚期流變儀（late rheometer）（型號名LVDV-III Ultra，博勒飛（Brookfield）製造）將5 ml的聚丙烯酸（polyacrylic acid，PAA）溶液裝於容器，降低旋軸（Spindle）並調節每分鐘轉數（revolutions per minute，rpm），於攪拌力矩（torque）為80的時點等待1分鐘，之後測定攪拌力矩無變化時的黏度值。此時，使用的旋軸為52Z，溫度為25℃。>viscosity> For the viscosity of the solution, use a late rheometer (model name LVDV-III Ultra, manufactured by Brookfield) to put 5 ml of polyacrylic acid (PAA) solution in a container and lower the spindle ) And adjust revolutions per minute (rpm), wait for 1 minute at the moment when the torque is 80, and then measure the viscosity value when there is no change in the torque. At this time, the rotation axis used was 52Z, and the temperature was 25°C.

>氣孔的分佈率> 將由FIB-SEM（Focused Ion Beam Scanning Electron Microscopes）以100,000倍率測定聚醯亞胺膜的影像固定為100 mm×80 mm，之後以2 mm×2 mm對區域進行細分，並以總計2000個區域為基準，計算存在氣孔（pore）的區域的比率（參照圖1）。 圖1示出利用實施例4的膜的FIB-SEM影像的氣孔分佈率的測定方法。由於存在氣孔的區域存在2個，因此氣孔分佈率為0.1%。 氣孔分佈率（%）=[2/2000] × 100=0.1%>The distribution rate of pores> The image of the polyimide film measured by FIB-SEM (Focused Ion Beam Scanning Electron Microscopes) at a magnification of 100,000 is fixed to 100 mm × 80 mm, and then the area is subdivided by 2 mm × 2 mm, and the total area is 2000 As a reference, calculate the ratio of the area where pores exist (see Figure 1). FIG. 1 shows a method of measuring the porosity distribution ratio using the FIB-SEM image of the film of Example 4. FIG. Since there are two regions where pores exist, the pore distribution rate is 0.1%. Stomatal distribution rate (%)=[2/2000] × 100=0.1%

圖3表示不包含DPS-DMS的聚醯亞胺、即比較例1的聚醯亞胺膜的FIB-SEM。根據圖3可知，於不包含DPS-DMS的聚醯亞胺的情況下，可知於膜內不產生氣孔。FIG. 3 shows the FIB-SEM of the polyimide film that does not include DPS-DMS, that is, the polyimide film of Comparative Example 1. FIG. It can be seen from FIG. 3 that, in the case where the polyimide does not include DPS-DMS, it can be seen that no pores are generated in the film.

圖4a至圖4c是與DPS-DMS含量變化對應的實施例及比較例的聚醯亞胺膜的FIB-SEM影像。於包含DPS-DMS的情況，可知於比較例的聚醯亞胺膜中，隨著DPS-DMS的含量增加，氣孔的產生量以大幅增加，但於由二胺包含DDS的實施例的聚醯亞胺膜的情況下，可知即便DPS-DMS的含量增加，氣孔的產生亦幾乎不出現。具體而言，圖4a是對DPS-DMS的含量為18 wt%的實施例4及比較例4的膜進行比較表示。與實施例4的情況留有2個氣孔區域而具有0.1%的氣孔分佈率相反，於比較例4的情況下，表現出21%的非常高的氣孔分佈率，於比較例2的情況下，表現出4.6%的氣孔分佈率。4a to 4c are FIB-SEM images of polyimide films of Examples and Comparative Examples corresponding to changes in DPS-DMS content. In the case where DPS-DMS is included, it can be seen that in the polyimide film of the comparative example, as the content of DPS-DMS increases, the amount of generated pores increases significantly, but in the example of the polyamine containing DDS from the diamine In the case of the imine film, it can be seen that even if the content of DPS-DMS increases, the generation of pores hardly occurs. Specifically, FIG. 4a is a comparative representation of the films of Example 4 and Comparative Example 4 with a DPS-DMS content of 18 wt%. Contrary to the case of Example 4, leaving two pore areas and having a pore distribution rate of 0.1%, in the case of Comparative Example 4, it showed a very high pore distribution rate of 21%, in the case of Comparative Example 2, Shows a 4.6% stomatal distribution rate.

>黃色度（YI）> 黃色度藉由卡樂愛（Color Eye）7000A進行測定。>Yellowness (YI)> The yellowness was measured with Color Eye 7000A.

>霧度（Haze）> 使用霧度計（Haze Meter）HM-150並藉由美國材料試驗協會（American Society for Testing Materials，ASTM）D1003的方法測定霧度。>Haze> Haze meter (Haze Meter) HM-150 was used and the haze was measured by the method of American Society for Testing Materials (ASTM) D1003.

>透射度> 透射度根據日本工業規格（Japanese Industrial Standards，JIS）K 7105並藉由透射率計（型號名HR-100，村上色彩技術研究所（Murakami Color Research Laboratory）製造）對針對450 nm、550 nm、及633 nm波長的透射率進行測定。>Transmittance> The transmittance is based on Japanese Industrial Standards (JIS) K 7105 and is measured for 450 nm, 550 nm, and 450 nm by a transmissometer (model name HR-100, manufactured by Murakami Color Research Laboratory), and The transmittance at 633 nm was measured.

>厚度方向相位差（R_th ）> 厚度方向相位差（R_th ）利用埃克索斯坎（Axoscan）進行測定。將膜剪為固定的大小來測定厚度，之後利用埃克索斯坎（Axoscan）測定相位差，為了補償相位差值而修正為C-板（C-plate）方向，並輸入測定的厚度。將測定波長設為550 nm。>Thickness phase difference (R _th )> Thickness phase difference (R _th ) was measured using Axoscan. Cut the film to a fixed size to measure the thickness, then use Axoscan to measure the phase difference, correct the phase difference to correct the C-plate (C-plate) direction, and enter the measured thickness. Set the measurement wavelength to 550 nm.

>玻璃轉移溫度（Tg）及熱膨脹係數（Coefficient of Thermal Expansion，CTE）> 將膜準備成5 mm×20 mm大小後，利用附件裝載試樣。使實際測定的膜的長度統一為16 mm。將拉伸膜的力設定為0.02 N，並藉由熱機械分析儀（Thermomechanical analyzer，TMA）（TA公司的Q400）測定於100℃至400℃的溫度範圍內以5 ℃/min的升溫速度進行第一次升溫製程，之後於400℃至100℃的溫度範圍內以4 ℃/min的冷卻速度進行冷卻（cooling）後，再次於100℃至450℃的溫度範圍內以5 ℃/min的升溫速度進行第二次升溫製程時的熱膨脹變化情形。 此時，於第二次升溫製程中，將在升溫區間觀察到的反曲點設為Tg。>Glass transition temperature (Tg) and Coefficient of Thermal Expansion (CTE)> After preparing the membrane to a size of 5 mm × 20 mm, use the accessory to load the sample. The length of the film actually measured was unified to 16 mm. The force of the stretched film was set to 0.02 N, and it was measured by a thermomechanical analyzer (TMA) (Q400 of TA Corporation) at a temperature increase rate of 5°C/min within a temperature range of 100°C to 400°C The first heating process, after cooling at a cooling rate of 4 °C/min in the temperature range of 400 °C to 100 °C, and then at a temperature of 5 °C/min in the temperature range of 100 °C to 450 °C Changes in thermal expansion during the second heating process at speed. At this time, in the second temperature-raising process, the inflection point observed in the temperature-raising interval is defined as Tg.

>熱分解溫度（Td1%）及重量減少率（%）> 利用熱重分析儀（Thermal Gravimetric Analyzer，TGA）於氮環境下測定聚合物的重量減少率為1%時的溫度。 測定於350℃下保持60分鐘時的重量減少率。 測定於380℃下保持60分鐘時的重量減少率。>Thermal decomposition temperature (Td1%) and weight reduction rate (%)> A thermogravimetric analyzer (Thermal Gravimetric Analyzer, TGA) was used to determine the temperature at which the weight reduction rate of the polymer was 1% under a nitrogen environment. The weight reduction rate when kept at 350°C for 60 minutes was measured. The weight reduction rate when kept at 380°C for 60 minutes was measured.

>模數、拉伸強度及伸長率> 於拉伸試驗器（英斯特朗（Instron）有限公司製造：英斯特朗（Instron）3342）中以10 mm/min的速度對長度5 mm×50 mm、厚度10 μm的膜進行拉伸，測定模數（GPa）、拉伸強度（MPa）、伸長率（%）。>Modulus, tensile strength and elongation> In a tensile tester (manufactured by Instron Co., Ltd.: Instron 3342), a film with a length of 5 mm×50 mm and a thickness of 10 μm was stretched at a speed of 10 mm/min , Determination of modulus (GPa), tensile strength (MPa), elongation (%).

>殘留應力及彎曲度（Bow）值測定> 使用殘留應力測定裝置（天可（TENCOR）公司的FLX2320）預先測定晶圓（wafer）的[彎曲量]後，藉由旋轉塗層機（spin coater）將樹脂組成物塗佈於厚度為525 μm的6英吋（in）矽晶圓上，使用（光洋林德伯格（KOYO lindberg）公司製造）烘箱，並於氮環境下，實施250℃30分鐘及400℃60分鐘的加熱硬化處理，硬化後製備附著有厚度為10 μm的樹脂膜的矽晶圓。使用殘留應力測定裝置測定該晶圓的彎曲量，藉由真實彎曲度（Real Bow）值測定產生於矽晶圓與樹脂膜之間的殘留應力。>Determination of residual stress and bending value (Bow)> After measuring the [bending amount] of the wafer in advance using a residual stress measuring device (FLX2320 from TENCOR), the resin composition was applied to a thickness of 525 μm by a spin coater 6-inch (in) silicon wafer, using an oven (manufactured by KOYO lindberg), under a nitrogen atmosphere, heat hardening at 250 ℃ for 30 minutes and 400 ℃ for 60 minutes, after hardening preparation A silicon wafer with a resin film with a thickness of 10 μm attached. A residual stress measuring device was used to measure the amount of bending of the wafer, and the residual stress generated between the silicon wafer and the resin film was measured by the Real Bow value.

[表1]

[Table 1]

[表2]

[Table 2]

[表3]

[table 3]

[表4]

[Table 4]

根據表1至表4可知，實施例的聚醯亞胺膜藉由同時使用DPS-DMS與DDS作為二胺，將聚醯亞胺膜內的氣孔分佈率控制為1%以下，從而可提供一種使模數具有2.2 GPa以下的值，且伸長率為20%以上的具有適當的剛性與彈性的聚醯亞胺膜。It can be seen from Tables 1 to 4 that the polyimide membranes of the examples control the porosity distribution rate in the polyimide membrane to 1% or less by using DPS-DMS and DDS as diamines at the same time, thereby providing a A polyimide film having appropriate rigidity and elasticity with a modulus of 2.2 GPa or less and an elongation of 20% or more.

>實驗例2>>Experimental example 2>

將自實施例9及比較例1與比較例2中製備的各個聚醯亞胺膜組成物旋轉塗佈於玻璃基板上。將塗佈有聚醯亞胺前驅物溶液的玻璃基板置於烘箱並以5 ℃/min的速度進行加熱，於80℃下保持30分鐘、400℃下保持30分鐘進行硬化製程來製備聚醯亞胺膜。Each polyimide film composition prepared in Example 9 and Comparative Examples 1 and 2 was spin-coated on a glass substrate. The glass substrate coated with the polyimide precursor solution was placed in an oven and heated at a rate of 5 ℃/min, held at 80 ℃ for 30 minutes, and 400 ℃ for 30 minutes for a hardening process to prepare polyasia Amine membrane.

以如圖2所示般的方法測定所述聚醯亞胺膜的相分離域的分佈率。於100,000倍率下將FIB-SEM（Focused Ion Beam Scanning Electron Microscopes）影像固定為100 mm×70 mm，並以2 mm×2 mm對區域進行細分，以總計1750個區域為基準區分為白色與黑色區域。於整體區域中計算白色區域的比率。The distribution ratio of the phase separation domain of the polyimide membrane was measured by the method as shown in FIG. 2. The FIB-SEM (Focused Ion Beam Scanning Electron Microscopes) image is fixed to 100 mm × 70 mm at 100,000 magnification, and the area is subdivided by 2 mm × 2 mm, which is divided into white and black areas based on a total of 1750 areas. . Calculate the ratio of white areas in the overall area.

若以與所述相同的方法測定實施例9的相分離域分佈率，則總計1750個區域中存在650個白色區域，因此表現出約32%的相分離域分佈率。When the phase separation domain distribution rate of Example 9 was measured by the same method as described above, since there were 650 white areas among the total 1750 areas, the phase separation domain distribution rate was approximately 32%.

比較例1的膜不包含DPS-DMS結構，因而如圖3所示般未出現相分離。比較例2的膜藉由使用TFMB代替DDS作為二胺，從而於膜內大量產生奈米氣孔（nanopore）而無法確認相分離域的存在。The membrane of Comparative Example 1 does not include the DPS-DMS structure, and therefore, as shown in FIG. 3, phase separation does not occur. By using TFMB instead of DDS as the diamine in the membrane of Comparative Example 2, a large number of nanopores were generated in the membrane, and the existence of the phase separation domain could not be confirmed.

另一方面，圖5是實施例11（DPS-DMS 15 wt%）、及實施例13至實施例15（DPS-DMS分別為25 wt%、20 wt%、5 wt%）的聚醯亞胺膜的FIB-SEM影像（×100,000）。可確認膜內氣孔幾乎不存在且相分離域均勻地分佈。On the other hand, FIG. 5 is the polyimide of Example 11 (DPS-DMS 15 wt%), and Examples 13 to 15 (DPS-DMS are 25 wt%, 20 wt%, and 5 wt%, respectively) FIB-SEM image of the film (×100,000). It can be confirmed that there are almost no pores in the membrane and the phase separation domains are evenly distributed.

>實驗例3>>Experimental example 3>

於350℃下於自實施例4及比較例2與比較例4中製備的聚醯亞胺膜上沈積SiO₂ 。使所述SiO₂ 層的厚度為2000 Å。此後於380℃下兩小時的持續時間內對形成有SiO₂ 層的聚醯亞胺膜加熱進行熱處理。SiO _{2 was} deposited on the polyimide films prepared in Example 4 and Comparative Example 2 and Comparative Example 4 at 350°C. The thickness of the SiO ₂ layer is 2000 Å. Thereafter, the polyimide film on which the SiO ₂ layer was formed was heat-treated for a duration of two hours at 380°C.

圖6是對形成有SiO₂ 層的聚醯亞胺膜進行拍攝的照片。根據圖6可知，若於氣孔分佈率為1%以上的比較例2及比較例4的膜沈積SiO₂ 層之後進行熱處理，則於所述SiO₂ 層產生龜裂，但可知如實施例4般於沈積於氣孔存在為1%以下（0.1%）的膜上的SiO₂ 層完全不產生龜裂。6 is a photograph of a polyimide film formed with a SiO ₂ layer. As can be seen from FIG. 6, if the SiO ₂ layer is deposited on the films of Comparative Example 2 and Comparative Example 4 having a pore distribution rate of 1% or more, cracks are generated in the SiO ₂ layer, but it can be seen that it is as in Example 4. The SiO ₂ layer deposited on the film with pores of 1% or less (0.1%) does not generate cracks at all.

以上，詳細地對本發明內容的特定的部分進行了記述，對本發明所屬技術領域內具有通常知識者而言應明白的是，此種具體的記述僅為較佳的實施方式，並不藉此限制本發明的範圍。因此，本發明的實質的範圍藉由隨附的申請專利範圍與其等同物來定義。The specific parts of the content of the present invention have been described in detail above. It should be understood by those of ordinary knowledge in the technical field to which the present invention belongs that such specific description is only a preferred embodiment and is not intended to be limiting The scope of the invention. Therefore, the essential scope of the present invention is defined by the accompanying patent application scope and its equivalent.

無no

圖1是用以說明根據聚醯亞胺膜的聚焦離子束掃描電子顯微鏡（Focused Ion Beam Scanning Electron Microscopes，FIB-SEM）影像而對聚醯亞胺膜內氣孔（pore）的分佈率進行測定的方法。 圖2是用以說明根據聚醯亞胺膜的FIB-SEM（Focused Ion Beam Scanning Electron Microscopes）影像而對相分離域的分佈率進行測定的方法。 圖3是表示比較例1的聚醯亞胺膜的FIB-SEM影像。 圖4a至圖4c是針對比較例及實施例的聚醯亞胺膜而比較相同的二苯基矽氧烷-二甲基矽氧烷低聚物（diphenylsiloxane-dimethylsiloxane co-oligomer，DPS-DMS）含量下的FIB-SEM影像。 圖5是實施例11、實施例13、實施例14、及實施例15的聚醯亞胺膜的FIB-SEM影像。 圖6是表示於比較例3與比較例4及實施例1的聚醯亞胺膜沈積SiO₂ 及進行熱處理後的狀態的照片。FIG. 1 is used to explain the measurement of the distribution rate of pores in a polyimide film based on the image of a focused ion beam scanning electron microscope (FIB-SEM) of the polyimide film. method. FIG. 2 is a diagram illustrating a method of measuring the distribution ratio of a phase separation domain based on FIB-SEM (Focused Ion Beam Scanning Electron Microscopes) image of a polyimide film. 3 is a FIB-SEM image showing the polyimide film of Comparative Example 1. FIG. 4a to 4c are the same diphenylsiloxane-dimethylsiloxane co-oligomer (DPS-DMS) compared to the polyimide film of the comparative example and the example FIB-SEM image under the content. 5 is a FIB-SEM image of the polyimide film of Example 11, Example 13, Example 14, and Example 15. FIG. 6 is a photograph showing a state after SiO _{2 is} deposited and heat-treated on the polyimide film of Comparative Example 3, Comparative Example 4, and Example 1. FIG.

Claims (14)

一種聚醯亞胺膜，是包含聚合成分的聚合及醯亞胺化產物的膜，所述聚合成分包含：二胺成分，包含具有下述化學式1的結構的二胺與胺封端的甲基苯基矽氧烷低聚物；以及 二酐成分，包含兩種以上的四羧酸二酐；所述聚醯亞胺膜內氣孔分佈率為1%以下， [化學式1]

。A polyimide film is a film containing a polymerized and imidized product of a polymerized component, the polymerized component including: a diamine component, including a diamine having the structure of the following Chemical Formula 1 and an amine-terminated methylbenzene Siloxane oligomer; and dianhydride components, including two or more tetracarboxylic dianhydrides; the porosity distribution rate in the polyimide membrane is less than 1%, [Chemical Formula 1]

. 如申請專利範圍第1項所述的聚醯亞胺膜，其中所述氣孔分佈率是於將所述聚醯亞胺膜的100,000倍率的聚焦離子束掃描電子顯微鏡影像固定為100 mm×80 mm且細分為2 mm×2 mm時，計算的整體區域中氣孔存在的區域的比率。The polyimide film as described in item 1 of the patent application scope, wherein the porosity distribution rate is fixed at 100 mm × 80 mm by a focused ion beam scanning electron microscope image of the 100,000 magnification of the polyimide film And when it is subdivided into 2 mm×2 mm, the ratio of the area where the pore exists in the whole area is calculated. 一種聚醯亞胺膜，是包含聚合成分的聚合及醯亞胺化產物的聚醯亞胺膜，所述聚合成分包含：二胺成分，包含具有下述化學式1的結構的二胺與胺封端的甲基苯基矽氧烷低聚物；以及 二酐成分，包含兩種以上的四羧酸二酐；於源自下述化學式1的二胺的聚醯亞胺基質分散有源自所述胺封端的甲基苯基矽氧烷低聚物的多個域，所述多個域的平均大小為10 nm以下， [化學式1]

。A polyimide film is a polyimide film containing a polymerized and imidized product of a polymerized component, the polymerized component including: a diamine component, including a diamine having the structure of the following Chemical Formula 1 and an amine seal Terminal methylphenylsiloxane oligomer; and dianhydride component, including two or more tetracarboxylic dianhydrides; dispersed in the polyimide matrix derived from the diamine of the following chemical formula 1 is derived from the Multiple domains of amine-terminated methylphenylsiloxane oligomers, the average size of the multiple domains is below 10 nm, [Chemical Formula 1]

. 如申請專利範圍第3項所述的聚醯亞胺膜，其中所述域的分佈率為25%～60%，且 所述域的分佈率是於將所述聚醯亞胺膜的100,000倍率的聚焦離子束掃描電子顯微鏡影像固定為100 mm×70 mm且細分為2 mm×2 mm時，並在區分為白色區域與黑色區域後計算的整體區域中白色區域的比率。The polyimide membrane as described in item 3 of the patent application scope, wherein the distribution rate of the domain is 25% to 60%, and The distribution rate of the domain is when the 100,000 magnification focused ion beam scanning electron microscope image of the polyimide film is fixed to 100 mm×70 mm and subdivided into 2 mm×2 mm, and is divided into white areas The ratio of the white area in the overall area calculated after the black area. 如申請專利範圍第1項或第3項所述的聚醯亞胺膜，其中所述胺封端的甲基苯基矽氧烷低聚物具有下述化學式2的結構： [化學式2]

於化學式2中，p及q為莫耳分率且為p+q=100時，p為70～90，q為10～30。The polyimide film as described in Item 1 or Item 3 of the patent application scope, wherein the amine-terminated methylphenylsiloxane oligomer has the structure of the following Chemical Formula 2: [Chemical Formula 2]

In Chemical Formula 2, p and q are mole fractions and p+q=100, p is 70 to 90, and q is 10 to 30. 如申請專利範圍第1項或第3項所述的聚醯亞胺膜，其中所述二酐成分包含聯苯四羧酸二酐及均苯四甲酸二酐。The polyimide film according to item 1 or 3 of the patent application scope, wherein the dianhydride component includes biphenyltetracarboxylic dianhydride and pyromellitic dianhydride. 如申請專利範圍第1項或第3項所述的聚醯亞胺膜，其中所述聚合成分以所述聚合成分的總重量為基準而使所述胺封端的甲基苯基矽氧烷低聚物為5重量%至30重量%。The polyimide film according to item 1 or item 3 of the patent application range, wherein the polymerization component makes the amine-terminated methylphenylsiloxane low based on the total weight of the polymerization component The polymer is 5% to 30% by weight. 如申請專利範圍第1項或第3項所述的聚醯亞胺膜，其中所述聚合成分以整體所述二胺成分為基準而包含1莫耳%～10莫耳%的所述胺封端的甲基苯基矽氧烷低聚物。The polyimide film according to item 1 or item 3 of the patent application range, wherein the polymer component contains the amine sealer at 1 mol% to 10 mol% based on the entire diamine component The terminal methyl phenyl siloxane oligomer. 如申請專利範圍第6項所述的聚醯亞胺膜，其中所述二酐成分以6：4至8：2的莫耳比包含所述聯苯四羧酸二酐與所述均苯四甲酸二酐。The polyimide film as described in item 6 of the patent application range, wherein the dianhydride component contains the biphenyltetracarboxylic dianhydride and the homobenzene four in a molar ratio of 6:4 to 8:2 Formic dianhydride. 如申請專利範圍第1項或第3項所述的聚醯亞胺膜，其中所述聚醯亞胺膜的模數為2.2 GPa以下，伸長率為20%以上。The polyimide film as described in item 1 or 3 of the patent application range, wherein the modulus of the polyimide film is 2.2 GPa or less, and the elongation is 20% or more. 如申請專利範圍第1項或第3項所述的聚醯亞胺膜，其中所述聚醯亞胺膜的玻璃轉移溫度為230℃以上。The polyimide film according to item 1 or item 3 of the patent application scope, wherein the glass transition temperature of the polyimide film is 230° C. or higher. 一種可撓性裝置，其基板包含如申請專利範圍第1項或第3項所述的聚醯亞胺膜。A flexible device, the substrate of which includes the polyimide film as described in the first or third patent application. 一種可撓性裝置的製備製程，包含如下步驟： 使二胺成分與二酐成分反應來製備樹脂前驅物組成物，所述二胺成分包含具有下述化學式1的結構的二胺及胺封端的甲基苯基矽氧烷低聚物，所述二酐成分包含兩種以上的四羧酸二酐； 將所製備的所述樹脂前驅物組成物塗佈於載體基板上； 藉由對所述樹脂前驅物組成物進行加熱而醯亞胺化，從而形成如申請專利範圍第1項或第3項所述的聚醯亞胺膜； 於所述聚醯亞胺膜上形成元件；以及 將形成有所述元件的所述聚醯亞胺膜自所述載體基板剝離， [化學式1]

。A preparation process of a flexible device includes the following steps: reacting a diamine component with a dianhydride component to prepare a resin precursor composition, the diamine component including a diamine having the structure of the following Chemical Formula 1 and an amine-terminated Methylphenylsiloxane oligomer, the dianhydride component contains two or more tetracarboxylic dianhydrides; the prepared resin precursor composition is coated on a carrier substrate; The resin precursor composition is heated to be imidized to form a polyimide film as described in item 1 or 3 of the patent application scope; forming an element on the polyimide film; and to form The polyimide film with the element peeled from the carrier substrate, [Chemical Formula 1]

. 如申請專利範圍第13項所述的可撓性裝置的製備製程，其中所述製備製程包含選自由低溫多晶矽薄膜製備製程、氧化銦錫薄膜製備製程以及氧化物薄膜製備製程所組成的群組中的一種以上的製程。The manufacturing process of the flexible device as described in item 13 of the patent application scope, wherein the manufacturing process includes a group selected from the group consisting of a low-temperature polycrystalline silicon thin film manufacturing process, an indium tin oxide thin film manufacturing process and an oxide thin film manufacturing process More than one process.

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