TWI735640B - Polyimide precursor, resin composition, resin film and manufacturing method thereof - Google Patents

Polyimide precursor, resin composition, resin film and manufacturing method thereof Download PDF

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TWI735640B
TWI735640B TW106129267A TW106129267A TWI735640B TW I735640 B TWI735640 B TW I735640B TW 106129267 A TW106129267 A TW 106129267A TW 106129267 A TW106129267 A TW 106129267A TW I735640 B TWI735640 B TW I735640B
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polyimide
less
low
resin composition
temperature polysilicon
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TW106129267A
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TW201813993A (en
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栗下佑香
米谷昌樹
清水建樹
金田隆行
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日商旭化成股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
    • C08G73/1064—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C08G73/1025—Preparatory processes from tetracarboxylic acids or derivatives and diamines polymerised by radiations
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/16—Polyester-imides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/133305—Flexible substrates, e.g. plastics, organic film

Abstract

本發明提供一種殘留應力較低、翹曲較少、高溫區域中之黃度(YI值)較小、伸長率較高之聚醯亞胺前驅體、聚醯亞胺樹脂膜及其製造方法。 本發明係一種低溫多晶矽TFT元件之基板用之樹脂組合物，其包含使二胺成分與酸二酐成分聚合而獲得之聚醯亞胺前驅體、及溶劑，並且聚醯亞胺前驅體包含 (a)下述通式(1)：

Figure 106129267-A0101-11-0001-1
所表示之結構。The invention provides a polyimide precursor, a polyimide resin film and a manufacturing method thereof with lower residual stress, lower warpage, lower yellowness (YI value) in high-temperature regions, and higher elongation. The present invention is a resin composition for a substrate of a low-temperature polysilicon TFT element, which comprises a polyimide precursor obtained by polymerizing a diamine component and an acid dianhydride component, and a solvent, and the polyimide precursor includes ( a) The following general formula (1):
Figure 106129267-A0101-11-0001-1
The structure represented.

Description

聚醯亞胺前驅體、樹脂組合物、樹脂膜及其製造方法Polyimide precursor, resin composition, resin film and manufacturing method thereof

本發明例如係關於一種用於製造用於撓性器件之基板的聚醯亞胺前驅體、樹脂組合物、樹脂膜及其製造方法。The present invention, for example, relates to a polyimide precursor, resin composition, resin film and manufacturing method thereof used for manufacturing a substrate for flexible devices.

一般而言，於要求高耐熱性之用途中使用聚醯亞胺樹脂之膜作為樹脂膜。一般之聚醯亞胺樹脂係於藉由使芳香族羧酸二酐與芳香族二胺進行溶液聚合而製造聚醯亞胺前驅體後，於高溫下進行熱醯亞胺化，或使用觸媒進行化學醯亞胺化而製造之高耐熱樹脂。 聚醯亞胺樹脂係不溶、不融之超耐熱性樹脂，具有耐熱氧化性、耐熱特性、耐放射線性、耐低溫性、耐化學品性等優異之特性。因此，聚醯亞胺樹脂被用於包括電子材料之廣泛領域中。作為電子材料領域中之聚醯亞胺樹脂之應用例，例如可列舉絕緣塗佈劑、絕緣膜、半導體之保護膜、TFT-LCD(Thin Film Transistor-Liquid Crystal Display，薄膜電晶體-液晶顯示裝置)之電極保護膜等。最近，業界正研究代替先前於顯示器材料之領域中所使用之玻璃基板，而採用利用其輕量、柔軟性之無色透明撓性基板。 於製造作為撓性基板之聚醯亞胺樹脂膜之情形時，於適當之支持體上塗佈含有聚醯亞胺前驅體之組合物而形成塗膜後，進行熱處理使其醯亞胺化，藉此獲得聚醯亞胺樹脂膜。作為上述支持體，例如使用玻璃、矽、氮化矽、氧化矽、金屬等。於製造於此種支持體上具有聚醯亞胺膜之積層體時，為了進行聚醯亞胺前驅體之乾燥及醯亞胺化，需要250℃以上之高溫下之加熱處理。因該加熱處理而於上述積層體中產生殘留應力，從而產生翹曲、剝離等深刻之問題。其原因在於與構成上述支持體之材料相比，聚醯亞胺之線熱膨脹係數較大。 作為熱膨脹係數較小之聚醯亞胺材料，由3,3',4,4'-聯苯四羧酸二酐與對苯二胺所形成之聚醯亞胺最廣為人知。已報告雖依存於膜厚及製作條件，但該聚醯亞胺膜顯示出非常低之線熱膨脹係數(非專利文獻1)。 又，已報告分子鏈中具有酯結構之聚醯亞胺因具有適度之直線性及剛直性，故而顯示出較低之線熱膨脹係數(專利文獻1)。 然而，包含上述文獻中所記載之聚醯亞胺的一般之聚醯亞胺樹脂因較高之芳香環密度而著色為茶色或黃色，故而可見光線區域之透光率較低，因此難以用於要求無色透明性之領域。例如，由3,3',4,4'-聯苯四羧酸二酐與對苯二胺所獲得之上述非專利文獻1之聚醯亞胺係膜厚10 μm時之黃度(YI值)高達40以上，於無色透明性之方面而言不充分。 關於膜之黃度，例如已知使用具有氟原子之單體之聚醯亞胺顯示出極低之黃度(專利文獻2)。 又，揭示有兼具較低之黃度與較低之Rth的聚醯亞胺前驅體(專利文獻3)。 [先前技術文獻] [專利文獻] [專利文獻1]日本專利第4627297號說明書 [專利文獻2]日本專利特表2010-538103號公報 [專利文獻3]國際公開第2014/148441號 [非專利文獻] [非專利文獻1]最新聚醯亞胺 日本聚醯亞胺研究會編 NTSGenerally speaking, a polyimide resin film is used as a resin film for applications requiring high heat resistance. General polyimide resin is prepared by solution polymerization of aromatic carboxylic acid dianhydride and aromatic diamine to produce polyimide precursor, and then undergo thermal imidization at high temperature, or use a catalyst Highly heat-resistant resin produced by chemical imidization. Polyimide resin is an insoluble, non-meltable super heat-resistant resin with excellent properties such as thermal oxidation resistance, heat resistance, radiation resistance, low temperature resistance, and chemical resistance. Therefore, polyimide resins are used in a wide range of fields including electronic materials. As application examples of polyimide resins in the field of electronic materials, for example, insulating coating agents, insulating films, semiconductor protective films, TFT-LCD (Thin Film Transistor-Liquid Crystal Display, Thin Film Transistor-Liquid Crystal Display) ) The electrode protective film, etc. Recently, the industry is researching to replace the glass substrates previously used in the field of display materials, and use colorless transparent flexible substrates that take advantage of its light weight and flexibility. In the case of manufacturing a polyimide resin film as a flexible substrate, a composition containing a polyimide precursor is coated on an appropriate support to form a coating film, and then heat treatment is performed to make it imidize. In this way, a polyimide resin film is obtained. As the above-mentioned support, for example, glass, silicon, silicon nitride, silicon oxide, metal, etc. are used. When manufacturing a laminate with a polyimide film on such a support, in order to dry and imidize the polyimide precursor, a heat treatment at a high temperature of 250° C. or more is required. Due to this heat treatment, residual stress is generated in the above-mentioned laminate, and serious problems such as warpage and peeling occur. The reason is that the coefficient of linear thermal expansion of polyimide is larger than that of the material constituting the above-mentioned support. As a polyimide material with a small thermal expansion coefficient, the polyimide formed by 3,3',4,4'-biphenyltetracarboxylic dianhydride and p-phenylenediamine is the most widely known. It has been reported that although it depends on the film thickness and production conditions, the polyimide film shows a very low linear thermal expansion coefficient (Non-Patent Document 1). In addition, it has been reported that polyimide having an ester structure in the molecular chain exhibits a low linear thermal expansion coefficient because of its moderate linearity and rigidity (Patent Document 1). However, the general polyimide resin containing the polyimide described in the above literature is colored brown or yellow due to the higher aromatic ring density, so the light transmittance in the visible light region is low, so it is difficult to use Fields requiring colorless transparency. For example, the non-patent document 1 obtained from 3,3',4,4'-biphenyltetracarboxylic dianhydride and p-phenylenediamine has the yellowness (YI value) of the polyimide film at a thickness of 10 μm ) It is as high as 40 or more, which is insufficient in terms of colorlessness and transparency. Regarding the yellowness of the film, for example, it is known that polyimide using a monomer having a fluorine atom exhibits extremely low yellowness (Patent Document 2). In addition, a polyimide precursor having both a low yellowness and a low Rth is disclosed (Patent Document 3). [Prior Art Document] [Patent Document] [Patent Document 1] Japanese Patent No. 4627297 Specification [Patent Document 2] Japanese Patent Publication No. 2010-538103 [Patent Document 3] International Publication No. 2014/148441 [Non-Patent Document ] [Non-Patent Document 1] The latest polyimide, Japan Polyimide Research Association, NTS

[發明所欲解決之問題] 再者，為了將聚醯亞胺樹脂應用作無色透明撓性基板，除了透明性以外，亦要求與基板之殘留應力較小，玻璃轉移溫度較高，Rth(延遲)較低等。 先前，以顯示器之顯示驅動為目的而製作之TFT之器件類型為非晶矽或IGZO(Indium Gallium Zinc Oxide，銦鎵鋅氧化物)，故而製程溫度為350℃以下。 另一方面，最近伴隨著TFT之器件類型變為低溫多晶矽(以下記為LTPS)，製程溫度達到400℃以上，而期望即便於此種高溫熱歷程後亦發揮上述物性之膜。 然而，公知之透明聚醯亞胺之物性特性不足以用作顯示器用之耐熱性無色透明基板。 進而，本發明者進行確認，結果得知專利文獻1中所記載之聚醯亞胺樹脂雖然顯示出較低之線熱膨脹係數，但存在如下問題：剝離後之聚醯亞胺樹脂膜之黃度(YI值)較大，此外殘留應力較高。 關於黃度，得知專利文獻2、3中所記載之聚醯亞胺膜雖然於300℃左右之溫度區域中顯示出較低之黃度，但於400℃以上之高溫熱歷程後黃度(YI值)明顯劣化。 本發明係鑒於上述所說明之問題點而成者。因此，本發明之目的在於提供一種於TFT之器件類型為LTPS之情形時可合適地使用的高溫熱歷程後之黃度(YI值)較小、與玻璃基板之殘留應力較小、玻璃轉移溫度較高、Rth(延遲)較低之聚醯亞胺樹脂膜及其製造方法以及積層體。 [解決問題之技術手段] 本發明者等人為了解決上述問題而反覆進行努力研究。結果發現使包含特定結構之聚醯亞胺前驅體之樹脂組合物硬化而獲得之聚醯亞胺樹脂膜係高溫區域中之黃度(YI值)較小，與基板之殘留應力較小。又，亦發現包含特定結構之聚醯亞胺膜與LTPS層之積層體於製成有機EL(Electroluminescence，電致發光)器件時並無翹曲，點亮試驗亦良好，雷射剝離後之灰分較少，基於該等知識見解而完成了本發明。 即，本發明係如以下所述者。 [1] 一種低溫多晶矽TFT元件之基板用之樹脂組合物，其特徵在於：其包含使二胺成分與酸二酐成分聚合而獲得之聚醯亞胺前驅體、及溶劑，並且 上述聚醯亞胺前驅體包含 (a)下述通式(1)： [化1]

Figure 02_image005
所表示之結構。 [2] 如[1]所記載之低溫多晶矽TFT元件之基板用之樹脂組合物，其中上述聚醯亞胺前驅體包含下述通式(2)： [化2]
Figure 02_image007
所表示之結構。 [3] 如[1]或[2]所記載之低溫多晶矽TFT元件之基板用之樹脂組合物，其中上述聚醯亞胺前驅體之重量平均分子量為4萬以上且30萬以下。 [4] 如[1]至[3]中任一項所記載之低溫多晶矽TFT元件之基板用之樹脂組合物，其中於將上述樹脂組合物中所含之固形物成分之總重量設為100質量%時，該固形物成分中所含有之分子量未達1,000之分子之量未達5質量%。 [5] 如[4]所記載之低溫多晶矽TFT元件之基板用之樹脂組合物，其中上述固形物成分中所含有之上述分子量未達1,000之分子之量為1質量%以下。 [6] 如[1]至[5]中任一項所記載之低溫多晶矽TFT元件之基板用之樹脂組合物，其中上述聚醯亞胺前驅體於將上述二胺成分與上述酸二酐成分之總質量設為100質量%時，包含 下述式(3)： [化3]
Figure 02_image009
(式中，存在複數個之R3 及R4 分別獨立地為碳數1~20之一價之有機基，而且h為3~200之整數) 所表示之結構之矽酮二胺成分之含量未達6質量%。 [7] 如[6]所記載之低溫多晶矽TFT元件之基板用之樹脂組合物，其中上述矽酮二胺成分之含量為5.9質量%以下。 [8] 如[7]所記載之低溫多晶矽TFT元件之基板用之樹脂組合物，其中上述矽酮二胺成分之含量為3質量%以下。 [9] 如[1]至[8]中任一項所記載之低溫多晶矽TFT元件之基板用之樹脂組合物，其中上述聚醯亞胺前驅體於將上述二胺成分之總莫耳數設為100莫耳%時，上述聚醯亞胺前驅體所含之下述通式(4)： [化4]
Figure 02_image011
(式中，R1 、R2 、R3 分別獨立地表示碳數1~20之一價之有機基。n表示0或1。而且a、b及c為0~4之整數) 所表示之二胺之量為48莫耳%以下。 [10] 如[9]所記載之低溫多晶矽TFT元件之基板用之樹脂組合物，其中上述聚醯亞胺前驅體所含之上述通式(4)所表示之二胺之量未達1莫耳%。 [11] 如[10]之低溫多晶矽TFT元件之基板用之樹脂組合物，其中上述聚醯亞胺前驅體所含之上述通式(4)所表示之二胺之量為0.9莫耳%以下。 [12] 如[9]所記載之低溫多晶矽TFT元件之基板用之樹脂組合物，其中上述聚醯亞胺前驅體包含4-胺基苯基-4-胺基苯甲酸酯作為上述通式(4)所表示之二胺成分。 [13] 如[1]至[12]中任一項所記載之低溫多晶矽TFT元件之基板用之樹脂組合物，其中上述聚醯亞胺前驅體於將上述二胺成分之總莫耳數設為100莫耳%時，上述4-胺基苯基-4-胺基苯甲酸酯之含量為48莫耳%以下。 [14] 如[13]所記載之低溫多晶矽TFT元件之基板用之樹脂組合物，其中上述聚醯亞胺前驅體之上述4-胺基苯基-4-胺基苯甲酸酯之含量未達1莫耳%。 [15] 如[14]所記載之低溫多晶矽TFT元件之基板用之樹脂組合物，其中上述聚醯亞胺前驅體之上述4-胺基苯基-4-胺基苯甲酸酯之含量未達0.9莫耳%。 [16] 如[1]至[15]中任一項所記載之低溫多晶矽TFT元件之基板用之樹脂組合物，其中上述聚醯亞胺前驅體包含二胺基二苯基碸作為上述二胺成分。 [17] 如[16]所記載之低溫多晶矽TFT元件之基板用之樹脂組合物，其中上述聚醯亞胺前驅體於將上述二胺成分之總莫耳數設為100莫耳%時，上述二胺基二苯基碸之含量為90莫耳%以上。 [18] 如[1]至[17]中任一項所記載之低溫多晶矽TFT元件之基板用之樹脂組合物，其中上述聚醯亞胺前驅體包含均苯四甲酸二酐作為上述酸二酐成分。 [19] 如[18]所記載之低溫多晶矽TFT元件之基板用之樹脂組合物，其中上述聚醯亞胺前驅體於將上述酸二酐成分之總莫耳數設為100莫耳%時，上述均苯四甲酸二酐之含量為90莫耳%以上。 [20] 如[1]至[19]中任一項所記載之低溫多晶矽TFT元件之基板用之樹脂組合物，其中將上述樹脂組合物於430℃下加熱1小時而獲得之聚醯亞胺膜之黃度於膜厚10 μm時為20以下。 [21] 如[20]所記載之低溫多晶矽TFT元件之基板用之樹脂組合物，其中將上述樹脂組合物於430℃下加熱1小時而獲得之聚醯亞胺膜之黃度於膜厚10 μm時為13以下。 [22] 如[1]至[21]中任一項所記載之低溫多晶矽TFT元件之基板用之樹脂組合物，其中將上述樹脂組合物於430℃下加熱1小時而獲得之聚醯亞胺膜之玻璃轉移溫度為360℃以上。 [23] 如[22]所記載之低溫多晶矽TFT元件之基板用之樹脂組合物，其中將上述樹脂組合物於430℃下加熱1小時而獲得之聚醯亞胺膜之玻璃轉移溫度為470℃以上。 [24] 如[1]至[23]中任一項所記載之低溫多晶矽TFT元件之基板用之樹脂組合物，其中將上述樹脂組合物於430℃下加熱1小時而獲得之聚醯亞胺膜之延遲於膜厚10 μm時為1000 nm以下。 [25] 如[24]所記載之低溫多晶矽TFT元件之基板用之樹脂組合物，其中將上述樹脂組合物於430℃下加熱1小時而獲得之聚醯亞胺膜之延遲於膜厚10 μm時為140 nm以下。 [26] 一種樹脂膜之製造方法，其特徵在於包括如下步驟： 於支持體之表面上塗佈如[1]至[25]中任一項所記載之樹脂組合物之步驟； 由上述樹脂組合物形成聚醯亞胺樹脂膜之步驟；及 將上述聚醯亞胺樹脂膜自上述支持體剝離之步驟。 [27] 如技術方案26所記載之樹脂膜之製造方法，其中於將上述聚醯亞胺樹脂膜自上述支持體剝離之步驟之前，進行自上述支持體側照射雷射之步驟。 [28] 一種顯示器之製造方法，其包括藉由如技術方案[26]或[27]所記載之方法而製造樹脂膜之方法。 [29] 一種積層體之製造方法，其包括如下步驟： 於支持體之表面上塗佈如[1]至[25]中任一項所記載之樹脂組合物之步驟； 由上述樹脂組合物形成聚醯亞胺樹脂膜之步驟；及 於上述聚醯亞胺樹脂膜上形成低溫多晶矽TFT之步驟。 [30] 如[29]所記載之積層體之製造方法，其進而包括將上述聚醯亞胺樹脂膜自上述支持體剝離之步驟。 [31] 一種撓性器件之製造方法，其包括如[29]或[30]所記載之積層體之製造方法。 [32] 一種積層體，其特徵在於包括： 包含下述通式(5)： [化5]
Figure 02_image013
所表示之聚醯亞胺之聚醯亞胺層、與低溫多晶矽TFT層。 [33] 如[32]所記載之積層體，其中上述聚醯亞胺層中所含之分子量未達1,000之分子之量未達5質量%。 [34] 一種聚醯亞胺膜，其特徵在於：於430℃下經加熱時之膜厚10 μm時之黃度為20以下，殘留應力為25 MPa以下，伸長率為15%以上。 [發明之效果] 由本發明之樹脂組合物所獲得之聚醯亞胺膜係高溫區域中之黃度(YI值)較小，與基板之殘留應力較小，玻璃轉移溫度較高，Rth(延遲)較低。 又，包含由本發明之樹脂組合物所獲得之聚醯亞胺膜與低溫多晶矽TFT之積層體係翹曲較少，霧度較低，熱循環試驗之結果良好。[Problem to be solved by the invention] Furthermore, in order to apply polyimide resin as a colorless and transparent flexible substrate, in addition to transparency, the residual stress with the substrate is also required to be small, the glass transition temperature is high, and Rth (retardation) ) Inferior. Previously, the device type of TFT manufactured for the purpose of display driving of a display is amorphous silicon or IGZO (Indium Gallium Zinc Oxide), so the process temperature is below 350°C. On the other hand, as the device type of TFT has recently changed to low-temperature polysilicon (hereinafter referred to as LTPS), the process temperature has reached 400° C. or more, and it is desired that the film exhibits the above-mentioned physical properties even after such a high-temperature thermal history. However, the physical properties of the known transparent polyimide are not enough to be used as a heat-resistant colorless transparent substrate for displays. Furthermore, the inventors confirmed that the polyimide resin described in Patent Document 1 shows a low linear thermal expansion coefficient, but has the following problem: the yellowness of the polyimide resin film after peeling (YI value) is larger, and the residual stress is higher. Regarding the yellowness, it is known that the polyimide films described in Patent Documents 2 and 3 show low yellowness in a temperature range of about 300°C, but yellowness after a high temperature thermal history of 400°C or higher. (YI value) is significantly degraded. The present invention was made in view of the problems explained above. Therefore, the object of the present invention is to provide a device that can be suitably used when the device type of TFT is LTPS. The yellowness (YI value) after high temperature thermal history is small, the residual stress with the glass substrate is small, and the glass transfer Polyimide resin film with higher temperature and lower Rth (retardation), its manufacturing method and laminate. [Technical Means to Solve the Problem] The inventors of the present invention have repeatedly studied hard to solve the above-mentioned problems. As a result, it was found that the polyimide resin film obtained by curing the resin composition containing the polyimide precursor of the specific structure has a lower yellowness (YI value) in the high temperature region and a smaller residual stress with the substrate. In addition, it has also been found that a laminate comprising a polyimide film of a specific structure and an LTPS layer has no warpage when it is made into an organic EL (Electroluminescence) device, and the lighting test is also good, and the ash content after laser peeling Rarely, the present invention has been completed based on these knowledge findings. That is, the present invention is as described below. [1] A resin composition for a substrate of a low-temperature polysilicon TFT element, characterized in that it comprises a polyimide precursor obtained by polymerizing a diamine component and an acid dianhydride component, and a solvent, and the polyimide The amine precursor contains (a) the following general formula (1): [化1]
Figure 02_image005
The structure represented. [2] The resin composition for substrates of low-temperature polysilicon TFT devices as described in [1], wherein the polyimide precursor comprises the following general formula (2): [化2]
Figure 02_image007
The structure represented. [3] The resin composition for substrates of low-temperature polysilicon TFT devices as described in [1] or [2], wherein the weight average molecular weight of the polyimide precursor is 40,000 or more and 300,000 or less. [4] The resin composition for substrates of low-temperature polysilicon TFT devices as described in any one of [1] to [3], wherein the total weight of the solid components contained in the resin composition is set to 100 At mass%, the amount of molecules with a molecular weight of less than 1,000 contained in the solid component is less than 5 mass%. [5] The resin composition for a substrate of a low-temperature polysilicon TFT device as described in [4], wherein the amount of molecules with a molecular weight of less than 1,000 contained in the solid component is 1% by mass or less. [6] The resin composition for substrates of low-temperature polysilicon TFT devices as described in any one of [1] to [5], wherein the polyimide precursor is combined with the diamine component and the acid dianhydride component When the total mass of is set to 100% by mass, the following formula (3) is included: [化3]
Figure 02_image009
(In the formula, there are a plurality of R 3 and R 4 each independently being a monovalent organic group with 1 to 20 carbons, and h is an integer from 3 to 200) The content of the silicone diamine component of the structure represented Less than 6 mass%. [7] The resin composition for substrates of low-temperature polysilicon TFT devices as described in [6], wherein the content of the silicone diamine component is 5.9% by mass or less. [8] The resin composition for substrates of low-temperature polysilicon TFT devices as described in [7], wherein the content of the silicone diamine component is 3% by mass or less. [9] The resin composition for a substrate of a low-temperature polysilicon TFT device as described in any one of [1] to [8], wherein the polyimide precursor is used to set the total moles of the diamine component When it is 100 mol%, the following general formula (4) contained in the above-mentioned polyimide precursor: [化4]
Figure 02_image011
(In the formula, R 1 , R 2 , and R 3 each independently represent a monovalent organic group with 1 to 20 carbon atoms. n represents 0 or 1. And a, b, and c are integers from 0 to 4) The amount of diamine is 48 mol% or less. [10] The resin composition for substrates of low-temperature polysilicon TFT devices as described in [9], wherein the amount of the diamine represented by the general formula (4) contained in the polyimide precursor is less than 1 mole Ear%. [11] The resin composition for substrates of low-temperature polysilicon TFT devices as in [10], wherein the amount of the diamine represented by the general formula (4) contained in the polyimide precursor is 0.9 mol% or less . [12] The resin composition for substrates of low-temperature polysilicon TFT devices as described in [9], wherein the polyimide precursor contains 4-aminophenyl-4-aminobenzoate as the general formula (4) The diamine component shown in (4). [13] The resin composition for a substrate of a low-temperature polysilicon TFT device as described in any one of [1] to [12], wherein the polyimide precursor is used to set the total moles of the diamine component When it is 100 mol%, the content of the aforementioned 4-aminophenyl-4-aminobenzoate is 48 mol% or less. [14] The resin composition for substrates of low-temperature polysilicon TFT devices as described in [13], wherein the content of the 4-aminophenyl-4-aminobenzoate of the polyimide precursor is not Up to 1 mol%. [15] The resin composition for substrates of low-temperature polysilicon TFT devices as described in [14], wherein the content of the 4-aminophenyl-4-aminobenzoate of the polyimide precursor is not Up to 0.9 mol%. [16] The resin composition for a substrate of a low-temperature polysilicon TFT device as described in any one of [1] to [15], wherein the polyimide precursor contains diaminodiphenyl sulfide as the diamine Element. [17] The resin composition for substrates of low-temperature polysilicon TFT devices as described in [16], wherein the polyimide precursor is when the total moles of the diamine components are set to 100 mole%, The content of diaminodiphenyl sulfide is more than 90 mol%. [18] The resin composition for a substrate of a low-temperature polysilicon TFT device as described in any one of [1] to [17], wherein the polyimide precursor contains pyromellitic dianhydride as the acid dianhydride Element. [19] The resin composition for a substrate of a low-temperature polysilicon TFT device as described in [18], wherein the polyimide precursor, when the total mole of the acid dianhydride component is set to 100 mole%, The content of the above-mentioned pyromellitic dianhydride is 90 mol% or more. [20] The resin composition for substrates of low-temperature polysilicon TFT devices as described in any one of [1] to [19], wherein the above-mentioned resin composition is heated at 430°C for 1 hour to obtain a polyimide The yellowness of the film is 20 or less when the film thickness is 10 μm. [21] The resin composition for substrates of low-temperature polysilicon TFT devices as described in [20], wherein the polyimide film obtained by heating the above resin composition at 430°C for 1 hour has a yellowness of 10 It is 13 or less in μm. [22] The resin composition for substrates of low-temperature polysilicon TFT devices as described in any one of [1] to [21], wherein the above-mentioned resin composition is heated at 430°C for 1 hour to obtain a polyimide The glass transition temperature of the film is 360°C or higher. [23] The resin composition for substrates of low-temperature polysilicon TFT devices as described in [22], wherein the glass transition temperature of the polyimide film obtained by heating the above resin composition at 430°C for 1 hour is 470°C above. [24] The resin composition for substrates of low-temperature polysilicon TFT devices as described in any one of [1] to [23], wherein the above-mentioned resin composition is heated at 430°C for 1 hour to obtain a polyimide The retardation of the film is 1000 nm or less when the film thickness is 10 μm. [25] The resin composition for substrates of low-temperature polysilicon TFT devices as described in [24], wherein the polyimide film obtained by heating the above resin composition at 430°C for 1 hour has a retardation of 10 μm in thickness When it is below 140 nm. [26] A method for manufacturing a resin film, characterized by comprising the following steps: a step of coating the resin composition as described in any one of [1] to [25] on the surface of a support; A step of forming a polyimide resin film; and a step of peeling the polyimide resin film from the support. [27] The method for producing a resin film as described in claim 26, wherein the step of irradiating a laser from the side of the support is performed before the step of peeling the polyimide resin film from the support. [28] A method of manufacturing a display, which includes a method of manufacturing a resin film by the method described in technical solution [26] or [27]. [29] A method for manufacturing a laminate, comprising the steps of: coating the resin composition as described in any one of [1] to [25] on the surface of a support; and forming from the above resin composition The step of polyimide resin film; and the step of forming low-temperature polysilicon TFT on the polyimide resin film. [30] The method for producing a laminate as described in [29], which further includes the step of peeling the polyimide resin film from the support. [31] A method of manufacturing a flexible device, which includes the method of manufacturing a laminate as described in [29] or [30]. [32] A layered body characterized by comprising: Containing the following general formula (5): [化5]
Figure 02_image013
The polyimide layer of polyimide and the low-temperature polysilicon TFT layer are shown. [33] The laminate as described in [32], wherein the amount of molecules with a molecular weight of less than 1,000 contained in the polyimide layer is less than 5% by mass. [34] A polyimide film characterized in that when heated at 430°C, when the film thickness is 10 μm, the yellowness is 20 or less, the residual stress is 25 MPa or less, and the elongation is 15% or more. [Effects of the Invention] The polyimide film obtained from the resin composition of the present invention has a low yellowness (YI value) in the high-temperature region, low residual stress with the substrate, high glass transition temperature, and high Rth (retardation) ) Is lower. In addition, the laminated system including the polyimide film obtained from the resin composition of the present invention and the low-temperature polysilicon TFT has less warpage, lower haze, and good thermal cycle test results.

以下，對本發明之例示之實施形態(以下簡稱為「實施形態」)詳細地進行說明。再者，本發明並不限定於以下之實施形態，可於其主旨之範圍內進行各種變化而實施。又，本發明中所記載之特性值只要無特別記載，則意指利用[實施例]之項中所記載之方法或業者理解與其同等之方法而測定之值。 ＜樹脂組合物＞ 本發明之一態樣所提供之樹脂組合物含有(a)聚醯亞胺前驅體、及(b)有機溶劑。 以下，依序說明各成分。 [聚醯亞胺前驅體] 本實施形態中之聚醯亞胺前驅體係 (a)下述通式(1)： [化6]

Figure 02_image015
所表示之聚醯亞胺前驅體。 作為本實施形態之通式(1)中所使用之酸二酐，可例示均苯四甲酸二酐(以下亦記為PMDA)。 作為本實施形態之通式(1)中所使用之二胺，可例示4,4'-二胺基二苯基碸、3,3'-二胺基二苯基碸。 其中，就所獲得之聚醯亞胺膜之殘留應力、YI、玻璃轉移溫度、延遲Rth、伸長率、霧度之觀點而言，更佳為下述通式(2)所表示之使用4,4'-二胺基二苯基碸之結構。 [化7]
Figure 02_image017
本實施形態中之聚醯亞胺前驅體之重量平均分子量(Mw)較佳為10,000~300,000，尤佳為40,000~300,000。於重量平均分子量為40,000以上之情形時，尤其是伸長率、斷裂強度等機械特性優異，殘留應力變低，YI變低。若重量平均分子量小於300,000，則於聚醯胺酸之合成時變得容易控制重量平均分子量，可獲得適度之黏度之樹脂組合物，樹脂組合物之塗佈性變良好。於本發明中，重量平均分子量係使用凝膠滲透層析儀(以下亦稱為GPC)以標準聚苯乙烯換算值之形式所求出之值。 於將本實施形態之樹脂組合物中所含之固形物成分之總重量設為100質量%時，分子量未達1,000之分子之含量越少越佳。具體而言，相對於固形物成分之總重量，較佳為未達5質量%，較佳為4質量%以下，較佳為3質量%以下，較佳為2質量%以下，較佳為1質量%以下，較佳為0.5質量%以下，較佳為0.1質量%以下，較佳為0.05質量%以下，較佳為0.02質量%以下。 此種組合物係黏度穩定性與清漆塗佈性優異。又，由此種組合物所獲得之聚醯亞胺膜係殘留應力較低，YI較小，玻璃轉移溫度(Tg)較高，延遲Rth較低，伸長率較高而較佳。又，包含此種聚醯亞胺膜與低溫多晶矽TFT之積層體係翹曲較少，霧度較低，熱循環試驗之結果良好。分子量未達1,000之分子之含量可根據對樹脂組合物進行GPC測定所獲得之峰面積而算出。 於本實施形態中之聚醯亞胺前驅體中，除了均苯四甲酸二酐以外，可於不損及伸長率、強度、應力、及黃度等之範圍內使用其他酸二酐。 作為此種酸二酐，可例示：4,4'-(六氟亞異丙基)二鄰苯二甲酸酐、5-(2,5-二側氧四氫-3-呋喃基)-3-甲基-環己烯-1,2二羧酸酐、1,2,3,4-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、3,3',4,4'-聯苯四羧酸二酐、3,3',4,4'-二苯基碸四羧酸二酐、2,2',3,3'-聯苯四羧酸二酐、亞甲基-4,4'-二鄰苯二甲酸二酐、1,1-亞乙基-4,4'-二鄰苯二甲酸二酐、2,2-亞丙基-4,4'-二鄰苯二甲酸二酐、1,2-伸乙基-4,4'-二鄰苯二甲酸二酐、1,3-三亞甲基-4,4'-二鄰苯二甲酸二酐、1,4-四亞甲基-4,4'-二鄰苯二甲酸二酐、1,5-五亞甲基-4,4'-二鄰苯二甲酸二酐、4,4'-氧二鄰苯二甲酸二酐、對伸苯基雙(脫水偏苯三酸酯)、硫代-4,4'-二鄰苯二甲酸二酐、磺醯基-4,4'-二鄰苯二甲酸二酐、1,3-雙(3,4-二羧基苯基)苯二酐、1,3-雙(3,4-二羧基苯氧基)苯二酐、1,4-雙(3,4-二羧基苯氧基)苯二酐、1,3-雙[2-(3,4-二羧基苯基)-2-丙基]苯二酐、1,4-雙[2-(3,4-二羧基苯基)-2-丙基]苯二酐、雙[3-(3,4-二羧基苯氧基)苯基]甲烷二酐、雙[4-(3,4-二羧基苯氧基)苯基]甲烷二酐、2,2-雙[3-(3,4-二羧基苯氧基)苯基]丙烷二酐、2,2-雙[4-(3,4-二羧基苯氧基)苯基]丙烷二酐、雙(3,4-二羧基苯氧基)二甲基矽烷二酐、1,3-雙(3,4-二羧基苯基)-1,1,3,3-四甲基二矽氧烷二酐、2,3,6,7-萘四羧酸二酐、1,4,5,8-萘四羧酸二酐、1,2,5,6-萘四羧酸二酐、3,4,9,10-苝四羧酸二酐、2,3,6,7-蒽四羧酸二酐、1,2,7,8-菲四羧酸二酐等。 總酸二酐中之上述其他酸二酐之含量較佳為20莫耳%以下，更佳為10莫耳%以下，尤佳為0莫耳%。 總酸二酐中之均苯四甲酸二酐之含量較佳為90莫耳%以上，較佳為95莫耳%以上，較佳為98莫耳%以上，較佳為99莫耳%以下，較佳為99.5莫耳%以上。總酸二酐中之均苯四甲酸二酐之量越多，就YI、玻璃轉移溫度Tg、伸長率之觀點而言越佳。 於本實施形態中之聚醯亞胺前驅體中，除了4,4'-二胺基二苯基碸、3,3'-二胺基二苯基碸以外，可於不損及伸長率、強度、應力、及黃度等之範圍內使用其他二胺。 作為其他二胺，例如可列舉：對苯二胺、間苯二胺、4,4'-二胺基二苯硫醚、3,4'-二胺基二苯硫醚、3,3'-二胺基二苯硫醚、4,4'-二胺基聯苯、3,4'-二胺基聯苯、3,3'-二胺基聯苯、4,4'-二胺基二苯甲酮、3,4'-二胺基二苯甲酮、3,3'-二胺基二苯甲酮、4,4'-二胺基二苯甲烷、3,4'-二胺基二苯基甲烷、3,3'-二胺基二苯基甲烷、1,4-雙(4-胺基苯氧基)苯、1,3-雙(4-胺基苯氧基)苯、1,3-雙(3-胺基苯氧基)苯、雙[4-(4-胺基苯氧基)苯基]碸、4,4-雙(4-胺基苯氧基)聯苯、4,4-雙(3-胺基苯氧基)聯苯、雙[4-(4-胺基苯氧基)苯基]醚、雙[4-(3-胺基苯氧基)苯基]醚、1,4-雙(4-胺基苯基)苯、1,3-雙(4-胺基苯基)苯、9,10-雙(4-胺基苯基)蒽、2,2-雙(4-胺基苯基)丙烷、2,2-雙(4-胺基苯基)六氟丙烷、2,2-雙[4-(4-胺基苯氧基)苯基]丙烷、2,2-雙[4-(4-胺基苯氧基)苯基]六氟丙烷、1,4-雙(3-胺基丙基二甲基矽烷基)苯等，較佳為使用選自該等中之一種以上。 總二胺中之上述其他二胺之含量較佳為20莫耳%以下，更佳為10莫耳%以下，尤佳為0莫耳%。 總二胺中之二胺基二苯基碸之含量較佳為90莫耳%以上，較佳為95莫耳%以上，較佳為98莫耳%以上，較佳為99莫耳%以上，較佳為99.5莫耳%以上。二胺基二苯基碸之量越多，就殘留應力、YI、玻璃轉移溫度Tg、延遲Rth、伸長率之觀點而言越佳。作為二胺基二苯基碸，較佳為4,4'-二胺基二苯基碸。 聚醯亞胺前驅體較佳為於將二胺成分之總莫耳數設為100莫耳%時，聚醯亞胺前驅體所含之下述通式(4)所表示之二胺之量為48莫耳%以下。 [化8]
Figure 02_image019
(式中，R1 、R2 、R3 分別獨立地表示碳數1~20之一價之有機基。n表示0或1。而且a、b及c為0~4之整數) 作為通式(4)所表示之二胺，例如於n為0之情形時，可例示4-胺基苯基-4-胺基苯甲酸酯(APAB)、2-甲基-4-胺基苯基-4-胺基苯甲酸酯(ATAB)、4-胺基苯基-3-胺基苯甲酸酯(4,3-APAB)等。於n為1之情形時，可例示[4-(4-胺基苯甲醯基)苯氧基]4-胺基苯甲酸酯等。 尤其聚醯亞胺前驅體較佳為於將二胺成分之總莫耳數設為100莫耳%時，聚醯亞胺前驅體所含之作為上述通式(4)所表示之二胺成分的4-胺基苯基-4-胺基苯甲酸酯之含量為48莫耳%以下。可獲得YI變小、Tg變高、延遲變低、伸長率變高之效果。可含有4-胺基苯基-4-胺基苯甲酸酯，亦可不含。 通式(4)所表示之二胺之量越少，就YI、玻璃轉移溫度Tg、延遲Rth、伸長率之觀點而言越佳。 上述聚醯亞胺前驅體所含之上述通式(4)所表示之二胺之量較佳為30莫耳%以下，較佳為20莫耳%以下，較佳為10莫耳%以下，較佳為5莫耳%以下。 又，上述通式(4)所表示之二胺、尤其例如4-胺基苯基-4-胺基苯甲酸酯之量較佳為未達1莫耳%，較佳為0.9莫耳%以下，較佳為0.8莫耳%以下，較佳為0.6莫耳%以下，較佳為0.4莫耳%以下，較佳為0.2莫耳%以下，較佳為0.1莫耳%以下。 上述聚醯亞胺前驅體較佳為於將上述二胺成分與上述酸二酐成分之總質量設為100質量%時，包含 下述式(3)： [化9]
Figure 02_image021
(式中，存在複數個之R3 及R4 分別獨立地為碳數1~20之一價之有機基，而且h為3~200之整數) 所表示之結構之矽酮二胺成分之含量未達6質量%。 包含上述式(3)所表示之結構之矽酮二胺成分越少，則YI越變小，玻璃轉移溫度Tg越變大，延遲Rth越變小，故而較佳。包含上述式(3)所表示之結構之矽酮二胺成分之含量較佳為5.9質量%以下，5.5質量%以下，5.0質量%以下，4.0質量%以下，3.0質量%以下，2.0質量%以下，1.0質量%以下，0.5質量%以下，0.4質量%以下，0.3質量%以下，0.2質量%以下，0.1質量%以下，0.08質量%以下，0.06質量%以下，0.04質量%以下，0.02質量%以下。 實施態樣中之聚醯亞胺前驅體亦可藉由在不損及其性能之範圍內除了上述四羧酸二酐以外使用二羧酸，而製成聚醯胺醯亞胺前驅體。藉由使用此種前驅體，可對所獲得之膜進行機械伸長率之提高、玻璃轉移溫度之提高、黃度之降低等各種性能之調整。作為此種二羧酸，可列舉具有芳香環之二羧酸及脂環式二羧酸。尤佳為選自由碳數為8~36之芳香族二羧酸、及碳數為6~34之脂環式二羧酸所組成之群中之至少一種化合物。此處所述之碳數中亦包含羧基所含之碳之個數。 該等之中較佳為具有芳香環之二羧酸。 具體而言，例如可列舉：間苯二甲酸、對苯二甲酸、4,4'-聯苯二羧酸、3,4'-聯苯二羧酸、3,3'-聯苯二羧酸、1,4-萘二甲酸、2,3-萘二甲酸、1,5-萘二甲酸、2,6-萘二甲酸、4,4'-磺醯基雙苯甲酸、3,4'-磺醯基雙苯甲酸、3,3'-磺醯基雙苯甲酸、4,4'-氧基雙苯甲酸、3,4'-氧基雙苯甲酸、3,3'-氧基雙苯甲酸、2,2-雙(4-羧基苯基)丙烷、2,2-雙(3-羧基苯基)丙烷、2,2'-二甲基-4,4'-聯苯二羧酸、3,3'-二甲基-4,4'-聯苯二羧酸、2,2'-二甲基-3,3'-聯苯二羧酸、9,9-雙(4-(4-羧基苯氧基)苯基)茀、9,9-雙(4-(3-羧基苯氧基)苯基)茀、4,4'-雙(4-羧基苯氧基)聯苯、4,4'-雙(3-羧基苯氧基)聯苯、3,4'-雙(4-羧基苯氧基)聯苯、3,4'-雙(3-羧基苯氧基)聯苯、3,3'-雙(4-羧基苯氧基)聯苯、3,3'-雙(3-羧基苯氧基)聯苯、4,4'-雙(4-羧基苯氧基)-對聯三苯、4,4'-雙(4-羧基苯氧基)-間聯三苯、3,4'-雙(4-羧基苯氧基)-對聯三苯、3,3'-雙(4-羧基苯氧基)-對聯三苯、3,4'-雙(4-羧基苯氧基)-間聯三苯、3,3'-雙(4-羧基苯氧基)-間聯三苯、4,4'-雙(3-羧基苯氧基)-對聯三苯、4,4'-雙(3-羧基苯氧基)-間聯三苯、3,4'-雙(3-羧基苯氧基)-對聯三苯、3,3'-雙(3-羧基苯氧基)-對聯三苯、3,4'-雙(3-羧基苯氧基)-間聯三苯、3,3'-雙(3-羧基苯氧基)-間聯三苯、1,1-環丁烷二羧酸、1,4-環己烷二羧酸、1,2-環己烷二羧酸、4,4'-二苯甲酮二羧酸、1,3-伸苯基二乙酸、1,4-伸苯基二乙酸等；及國際公開第2005/068535號說明書中所記載之5-胺基間苯二甲酸衍生物等。於使該等二羧酸與聚合物實際共聚合之情形時，亦可以由亞硫醯氯等所衍生之醯氯體、活性酯體等之形式使用。 [聚醯亞胺前驅體之製造] 本發明之聚醯亞胺前驅體(聚醯胺酸)可藉由使均苯四甲酸二酐與上述通式(1)所表示之結構單元所使用之二胺(例如4,4'-二胺基二苯基碸)進行縮聚反應而合成。該反應較佳為於適當之溶劑中進行。具體而言，例如可列舉使特定量之4,4'-DAS溶解於溶劑中後，向所獲得之二胺溶液中添加特定量之均苯四甲酸二酐並進行攪拌之方法。 關於合成上述聚醯亞胺前驅體時之四羧酸二酐成分與二胺成分之比(莫耳比)，就將所獲得之樹脂膜之熱線膨脹率、殘留應力、伸長率、及黃度(以下亦稱為YI)控制於所需範圍之觀點而言，較佳為設為四羧酸二酐：二胺=100：90~100：110(相對於四羧酸二酐1莫耳份而二胺為0.90~1.10莫耳份)之範圍，進而較佳為設為100：95~100：105(相對於酸二酐1莫耳份而二胺為0.95~1.05莫耳份)之範圍。 於本實施態樣中，於合成作為較佳之聚醯亞胺前驅體之聚醯胺酸時，能夠藉由四羧酸二酐成分與二胺成分之比之調整、及封端劑之添加而控制分子量。酸二酐成分與二胺成分之比越接近1：1，及封端劑之使用量越少，越可增大聚醯胺酸之分子量。 作為四羧酸二酐成分及二胺成分，推薦使用高純度品。作為其純度，分別較佳為設為98質量%以上，更佳為設為99質量%以上，進而較佳為設為99.5質量%以上。於併用複數種酸二酐成分或二胺成分之情形時，只要酸二酐成分或二胺成分整體具有上述純度即足矣，較佳為所使用之所有種類之酸二酐成分及二胺成分分別具有上述純度。 作為反應之溶劑，只要為可將四羧酸二酐成分及二胺成分、以及所生成之聚醯胺酸溶解，可獲得高分子量之聚合物之溶劑，則無特別限制。作為此種溶劑之具體例，例如可列舉非質子性溶劑、酚系溶劑、醚及二醇系溶劑等。關於該等之具體例，作為上述非質子性溶劑，例如可列舉：N,N-二甲基甲醯胺(DMF)、N,N-二甲基乙醯胺(DMAc)、N-甲基-2-吡咯啶酮(NMP)、N-甲基己內醯胺、1,3-二甲基咪唑啶酮、四甲基脲、下述通式(7)： [化10]
Figure 02_image023
式中，R12 =甲基所表示之Equamide M100(商品名：出光興產公司製造)、及R12 =正丁基所表示之Equamide B100(商品名：出光興產公司製造)等醯胺系溶劑； γ-丁內酯、γ-戊內酯等內酯系溶劑； 六甲基磷醯胺、六甲基膦醯三胺等含磷系醯胺系溶劑； 二甲基碸、二甲基亞碸、環丁碸等含硫系溶劑； 環己酮、甲基環己酮等酮系溶劑； 甲基吡啶、吡啶等三級胺系溶劑； 乙酸(2-甲氧基-1-甲基乙基)酯等酯系溶劑等； 作為上述酚系溶劑，例如可列舉：苯酚、鄰甲酚、間甲酚、對甲酚、2,3-二甲苯酚、2,4-二甲苯酚、2,5-二甲苯酚、2,6-二甲苯酚、3,4-二甲苯酚、3,5-二甲苯酚等； 作為上述醚及二醇系溶劑，例如可列舉：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)乙基]醚、四氫呋喃、1,4-二㗁烷等。 聚醯胺酸之合成中所使用之溶劑之常壓下之沸點較佳為60~300℃，更佳為140~280℃，尤佳為170~270℃。若溶劑之沸點高於300℃，則乾燥步驟需要較長時間。另一方面若溶劑之沸點低於60℃，則有於乾燥步驟中引起樹脂膜之表面產生粗糙、樹脂膜中混入氣泡等，而無法獲得均勻之膜之情形。 如此，就溶解性及塗佈時邊緣收縮之觀點而言，使用較佳為沸點為170~270℃、更佳為20℃下之蒸汽壓為250 Pa以下之溶劑較佳。更具體而言，較佳為使用選自由N-甲基-2-吡咯啶酮、γ-丁內酯、及上述通式(5)所表示之化合物所組成之群中之一種以上。 溶劑中之水分含量較佳為3000質量ppm以下。 該等溶劑可單獨使用或亦可將兩種以上混合而使用。 本實施態樣中之樹脂組合物中較佳為分子量未達1,000之分子之含量未達5質量%。 可認為於樹脂組合物中存在該分子量未達1,000之分子之原因在於受到合成時所使用之溶劑或原料(酸二酐、二胺)之水分量之影響。即，可認為其原因在於：一部分酸二酐單體之酸酐基因水分而水解成為羧基，並未高分子量化而以低分子之狀態殘存。因此，上述聚合反應中所使用之溶劑之水分量以儘量較少為宜。該溶劑之水分量較佳為設為3,000質量ppm以下，更佳為設為1,000質量ppm以下。 關於原料中所含之水分量，亦較佳為設為3000質量ppm以下，更佳為設為1000質量ppm以下。 可認為溶劑之水分量受到所使用之溶劑之等級(脫水級、通用級等)、溶劑容器(瓶、18 L桶、儲罐等)、溶劑之保管狀態(稀有氣體封入之有無等)、自開封起至使用為止之時間(開封後立即使用，還是開封後經過一段時間後使用等)等之影響。又，可認為亦受到合成前之反應器之稀有氣體置換、合成中之稀有氣體流通之有無等之影響。因此，於(a)聚醯亞胺前驅體之合成時推薦採取如下措施：使用高純度品作為原料，使用水分量較少之溶劑，並且於反應前及反應中不於系統內混入源自環境之水分。 於使各單體成分溶解於溶劑中時，亦可視需要進行加熱。 (a)聚醯亞胺前驅體合成時之反應溫度較佳為設為0℃~120℃，更佳為40℃~100℃，進而較佳為60~100℃。藉由於該溫度下進行聚合反應，可獲得聚合度較高之聚醯亞胺前驅體。聚合時間較佳為設為1~100小時，更佳為設為2~10小時。藉由將聚合時間設為1小時以上而成為聚合度均勻之聚醯亞胺前驅體，藉由設為100小時以下而可獲得聚合度較高之聚醯亞胺前驅體。 本實施形態之聚醯亞胺前驅體可視需要於不損及本發明之所需性能之範圍內含有其他聚醯亞胺前驅體。 作為此種聚醯亞胺前驅體，例如可例示使上述其他酸二酐與其他二胺縮聚而獲得之聚醯亞胺前驅體。 本實施形態之其他聚醯亞胺前驅體之質量比率較佳為相對於(a)聚醯亞胺前驅體全部而為30質量%以下，就YI值及全光線透過率之氧依存性之降低之觀點而言，更佳為10質量%以下。 於本實施形態之較佳態樣中，(a)聚醯亞胺前驅體亦可一部分醯亞胺化。該情形之醯亞胺化率較佳為設為80%以下，更佳為設為50%以下。該部分醯亞胺化係藉由將上述(a)聚醯亞胺前驅體加熱進行脫水閉環而獲得。該加熱可於較佳為120~200℃、更佳為150~180℃之溫度下進行較佳為15分鐘~20小時、更佳為30分鐘~10小時。 又，於藉由上述反應而獲得之聚醯胺酸中添加N,N-二甲基甲醯胺二甲縮醛或N,N-二甲基甲醯胺二乙縮醛並進行加熱，將羧酸之一部分或全部酯化後，用作本實施形態中之(a)聚醯亞胺前驅體，藉此亦可獲得室溫保管時之黏度穩定性經提高之樹脂組合物。此外，該等酯改性聚醯胺酸亦可藉由以下方法獲得：使上述酸二酐成分與相對於酸酐基而為1當量之一元醇、及亞硫醯氯、二環己基碳二醯亞胺等脫水縮合劑依序反應後，與二胺成分進行縮合反應。 本實施形態之樹脂組合物中之(a)聚醯亞胺前驅體(較佳為聚醯胺酸)之比率就塗膜形成性之觀點而言，較佳為3~50質量%，進而較佳為5~40質量%，尤佳為10~30質量%。 作為本實施形態之第二態樣，可提供一種下述通式(1)所表示，重量平均分子量為4萬以上且30萬以下，並且重量平均分子量未達1000之分子之含量未達5質量%之聚醯亞胺前驅體。 [化11]
Figure 02_image025
實施態樣中之聚醯亞胺前驅體只要重量平均分子量為4萬以上且30萬以下，並且重量平均分子量未達1000之分子之含量未達5質量%，則並無限定。為了獲得此種聚醯亞胺前驅體，可藉由將溶劑或原料中之水分含量設為特定範圍以下，且藉由提高原料之純度，將酸二酐與二胺之莫耳比設為特定範圍內而達成。 具體而言，溶劑中之水分含量較佳為3000 ppm以下，更佳為1500 ppm以下，尤佳為500 ppm以下。 原料之純度較佳為98質量%以上，更佳為99質量%以上，尤佳為99.5質量%以上。 較佳為設為四羧酸二酐：二胺=100：90~100：110(二胺相對於四羧酸二酐1莫耳份而為0.90~1.10莫耳份)之範圍，進而較佳為設為100：95~100：105(二胺相對於酸二酐1莫耳份而為0.95~1.05莫耳份)之範圍。 上述聚醯亞胺前驅體就所獲得之聚醯亞胺膜之霧度及伸長率之觀點而言，較佳為下述通式(2)所表示之結構。 [化12]
Figure 02_image027
聚醯亞胺前驅體僅具有通式(1)(較佳為通式(2))所表示之結構之情況下，即便滿足黃度為20以下且殘留應力為25 MPa以下，亦無法提供進而滿足伸長率為15%以上之聚醯亞胺膜。於本實施形態中，藉由使用除了具有通式(1)所表示之結構以外，重量平均分子量為4萬以上且30萬以下，並且重量平均分子量未達1000之分子之含量未達5質量%的聚醯亞胺前驅體，可提供進而滿足伸長率之聚醯亞胺膜。具體而言，可提供於430℃下經加熱後之膜厚10微米時之黃度為20以下、殘留應力為25 MPa以下、伸長率為15%以上之聚醯亞胺膜。 ＜樹脂組合物＞ 本發明之另一態樣提供一種含有上述(a)聚醯亞胺前驅體及(b)有機溶劑之樹脂組合物。該樹脂組合物典型而言為清漆。 [(b)有機溶劑] 本實施形態中之(b)有機溶劑只要可將上述(a)聚醯亞胺前驅體及任意使用之其他成分溶解，則並無特別限制。作為此種(b)有機溶劑，可使用上文中作為(a)聚醯亞胺前驅體之合成時可使用之溶劑而描述者。較佳之有機溶劑亦與上述相同。本實施形態之樹脂組合物中之(b)有機溶劑可與(a)聚醯亞胺前驅體之合成中所使用之溶劑相同亦可不同。 (b)有機溶劑較佳為設為樹脂組合物之固形物成分濃度成為3~50質量%之量。又，較佳為以樹脂組合物之黏度(25℃)成為500 mPa・s~100,000 mPa・s之方式調整(b)有機溶劑之構成及量後添加。 [其他成分] 本實施形態之樹脂組合物亦可除了上述(a)及(b)成分以外，進而含有(c)界面活性劑、(d)烷氧基矽烷化合物等。 ((c)界面活性劑) 藉由在本實施形態之樹脂組合物中添加界面活性劑，可提高該樹脂組合物之塗佈性。具體而言，可防止塗佈膜之細紋之產生。 此種界面活性劑例如可列舉矽酮系界面活性劑、氟系界面活性劑、該等以外之非離子界面活性劑等。關於該等之例，作為矽酮系界面活性劑，例如可列舉：有機矽氧烷聚合物KF-640、642、643、KP341、X-70-092、X-70-093(以上為商品名，信越化學工業公司製造)，SH-28PA、SH-190、SH-193、SZ-6032、SF-8428、DC-57、DC-190(以上為商品名，東麗道康寧矽酮公司製造)，SILWET L-77、L-7001、FZ-2105、FZ-2120、FZ-2154、FZ-2164、FZ-2166、L-7604(以上為商品名，Nippon Unicar公司製造)，DBE-814、DBE-224、DBE-621、CMS-626、CMS-222、KF-352A、KF-354L、KF-355A、KF-6020、DBE-821、DBE-712(Gelest)，BYK-307、BYK-310、BYK-378、BYK-333(以上為商品名，BYK-Chemie Japan製造)，Glanol(商品名，共榮社化學公司製造)等； 作為氟系界面活性劑，例如可列舉：MEGAFAC F171、F173、R-08(大日本油墨化學工業股份有限公司製造，商品名)，Fluorad FC4430、FC4432(Sumitomo 3M股份有限公司，商品名)等； 作為該等以外之非離子界面活性劑，例如可列舉：聚氧乙烯月桂基醚、聚氧乙烯硬脂基醚、聚氧乙烯油基醚、聚氧乙烯辛基苯酚醚等。 於該等界面活性劑之中，就樹脂組合物之塗佈性(抑制細紋)之觀點而言，較佳為矽酮系界面活性劑、氟系界面活性劑，就固化步驟時之氧濃度對YI值及全光線透過率之影響之觀點而言，較佳為矽酮系界面活性劑。 於使用(c)界面活性劑之情形時，其調配量相對於樹脂組合物中之(a)聚醯亞胺前驅體100質量份而較佳為0.001~5質量份，更佳為0.01~3質量份。 (d)烷氧基矽烷化合物 為了使由本實施形態之樹脂組合物所獲得之樹脂膜於撓性器件等之製造製程中於與支持體之間顯示出充分之密接性，該樹脂組合物可相對於(a)聚醯亞胺前驅體100質量%而含有0.01~20質量%之烷氧基矽烷化合物。藉由烷氧基矽烷化合物相對於聚醯亞胺前驅體100質量%之含量為0.01質量%以上，可於與支持體之間獲得良好之密接性。又，烷氧基矽烷化合物之含量為20質量%以下就樹脂組合物之保存穩定性之觀點而言較佳。烷氧基矽烷化合物之含量更佳為相對於聚醯亞胺前驅體100質量份而為0.02~15質量%，進而較佳為0.05~10質量%，尤佳為0.1~8質量%。 藉由使用烷氧基矽烷化合物作為本實施形態之樹脂組合物之添加劑，除了上述密接性之提高以外，可進而提高樹脂組合物之塗佈性(抑制細紋不均)，並且使所獲得之硬化膜之YI值之固化時氧濃度依存性降低。 作為烷氧基矽烷化合物，例如可列舉：3-脲基丙基三乙氧基矽烷、雙(2-羥乙基)-3-胺基丙基三乙氧基矽烷、3-縮水甘油氧基丙基三甲氧基矽烷、γ-胺基丙基三甲氧基矽烷、γ-胺基丙基三丙氧基矽烷、γ-胺基丙基三丁氧基矽烷、γ-胺基乙基三乙氧基矽烷、γ-胺基乙基三丙氧基矽烷、γ-胺基乙基三丁氧基矽烷、γ-胺基丁基三乙氧基矽烷、γ-胺基丁基三甲氧基矽烷、γ-胺基丁基三丙氧基矽烷、γ-胺基丁基三丁氧基矽烷、苯基矽烷三醇、三甲氧基苯基矽烷、三甲氧基(對甲苯基)矽烷、二苯基矽烷二醇、二甲氧基二苯基矽烷、二乙氧基二苯基矽烷、二甲氧基二-對甲苯基矽烷、三苯基矽烷醇及下述結構各者所表示之烷氧基矽烷化合物等，較佳為使用選自該等中之一種以上。 [化13]
Figure 02_image029
本實施形態之樹脂組合物之製造方法並無特別限定。例如可採用以下方法。 於合成(a)聚醯亞胺前驅體時所使用之溶劑與(b)有機溶劑相同之情形時，可將所合成之聚醯亞胺前驅體溶液直接作為樹脂組合物。又，亦可視需要於室溫(25℃)~80℃之溫度範圍內，向聚醯亞胺前驅體中添加(b)有機溶劑及其他成分之一種以上並進行攪拌混合後，用作樹脂組合物。該攪拌混合可使用具備攪拌葉之三一馬達(新東化學股份有限公司製造)、自轉公轉混合機等適宜之裝置。又，亦可視需要施加40~100℃之熱。 另一方面，於合成(a)聚醯亞胺前驅體時所使用之溶劑與(b)有機溶劑不同之情形時，亦可藉由例如再沈澱、溶劑蒸餾去除等適宜之方法將所合成之聚醯亞胺前驅體溶液中之溶劑去除而將(a)聚醯亞胺前驅體單離後，於室溫~80℃之溫度範圍內添加(b)有機溶劑及視需要之其他成分，並進行攪拌混合，藉此製備樹脂組合物。 亦可於如上述般製備樹脂組合物後，將該組合物溶液於例如130~200℃下加熱例如5分鐘~2小時，藉此以聚合物不發生析出之程度使聚醯亞胺前驅體之一部分進行脫水醯亞胺化。此處，藉由控制加熱溫度及加熱時間，可控制醯亞胺化率。藉由使聚醯亞胺前驅體進行部分醯亞胺化，可提高樹脂組合物於室溫保管時之黏度穩定性。作為醯亞胺化率之範圍，就取得聚醯亞胺前驅體對樹脂組合物溶液之溶解性與溶液之保存穩定性之平衡的觀點而言，較佳為設為5%~70%。 本實施形態之樹脂組合物較佳為其水分量為3,000質量ppm以下。樹脂組合物之水分量就保存該樹脂組合物時之黏度穩定性之觀點而言，較佳為2500質量ppm以下，較佳為2000質量ppm以下，較佳為1500質量ppm以下，更佳為1,000質量ppm以下，進而較佳為500質量ppm以下，較佳為300質量ppm以下，較佳為100質量ppm以下。 本實施形態之樹脂組合物之溶液黏度於25℃下較佳為500~200,000 mPa・s，更佳為2,000~100,000 mPa・s，尤佳為3,000~30,000 mPa・s。該溶液黏度可使用E型黏度計(東機產業股份有限公司製造，VISCONICEHD)測定。若溶液黏度低於300 mPa・s，則有產生膜形成時之塗佈難以進行之問題之虞，若高於200,000 mPa・s，則有產生合成時之攪拌變困難之問題之虞。 即便於合成(a)聚醯亞胺前驅體時溶液為高黏度，亦可藉由於反應結束後添加溶劑並進行攪拌，而獲得操作性良好之黏度之樹脂組合物。 本實施形態之樹脂組合物於較佳態樣中具有以下特性。 將樹脂組合物塗佈於支持體之表面而形成塗膜後，於氮氣氛圍下(氧濃度2,000 ppm以下之氮氣中)於430℃將該塗膜加熱1小時，藉此使該聚醯亞胺前驅體進行醯亞胺化所獲得之聚醯亞胺膜較佳為10 μm膜厚時之黃度為20以下。10 μm膜厚時之黃度較佳為18以下，較佳為16以下，較佳為14以下，較佳為13以下，較佳為10以下，較佳為7以下。 又，如此所獲得之聚醯亞胺膜之殘留應力較佳為25 MPa以下。較佳之殘留應力為23 MPa以下，為20 MPa以下，為18 MPa以下，為16 MPa以下。 又，如此所獲得之聚醯亞胺膜之玻璃轉移溫度Tg較佳為360℃以上。較佳之玻璃轉移溫度Tg為470℃以上。 又，如此所獲得之聚醯亞胺膜之10 μm膜厚時之延遲Rth較佳為1000 nm以下。較佳之延遲Rth為800 nm以下，為700 nm以下，為500 nm以下，為300 nm以下，為200 nm以下，為140 nm以下，為100 nm以下。 又，如此所獲得之聚醯亞胺膜之10 μm膜厚時之拉伸伸長率較佳為15%以上。較佳之拉伸伸長率為20%以上，25%以上，30%以上，35%以上，40%以上。 本實施形態之樹脂組合物例如可合適地用於形成液晶顯示器、有機電致發光顯示器、場發射顯示器、電子紙等顯示裝置之透明基板。具體而言，可用於形成薄膜電晶體(TFT)之基板、彩色濾光片之基板、透明導電膜(ITO，Indium Thin Oxide)之基板等。 本實施形態之樹脂前驅體因可形成殘留應力為25 MPa以下般之聚醯亞胺膜，故而容易應用於在無色透明聚醯亞胺基板上具備TFT元件裝置之顯示器製造步驟。 ＜樹脂膜＞ 本發明之另一態樣提供一種由上述樹脂前驅體所形成之樹脂膜。 又，本發明之又一態樣提供一種由上述樹脂組合物製造樹脂膜之方法。 本實施形態中之樹脂膜之特徵在於包括如下步驟： 藉由於支持體之表面上塗佈上述樹脂組合物而形成塗膜之步驟(塗佈步驟)； 藉由將上述支持體及上述塗膜加熱而使該塗膜中所含之聚醯亞胺前驅體進行醯亞胺化，形成聚醯亞胺樹脂膜之步驟(加熱步驟)；及 將上述聚醯亞胺樹脂膜自該支持體剝離之步驟(剝離步驟)。 此處，支持體只要具有其後續步驟之加熱溫度下之耐熱性，且剝離性良好，則並無特別限定。例如可使用：玻璃(例如無鹼玻璃)基板； 矽晶圓； PET(聚對苯二甲酸乙二酯)、OPP(延伸聚丙烯)、聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯、聚碳酸酯、聚醯亞胺、聚醯胺醯亞胺、聚醚醯亞胺、聚醚醚酮、聚醚碸、聚苯碸、聚苯硫醚等樹脂基板； 不鏽鋼、氧化鋁、銅、鎳等金屬基板等。 於形成膜狀之聚醯亞胺成形體之情形時，例如較佳為玻璃基板、矽晶圓等，於形成薄膜狀或片狀之聚醯亞胺成形體之情形時，例如較佳為包含PET(聚對苯二甲酸乙二酯)、OPP(延伸聚丙烯)等之支持體。 作為塗佈方法，例如可應用：刮刀塗佈機、氣刀塗佈機、輥式塗佈機、旋轉塗佈機、流塗機、模嘴塗佈機、棒式塗佈機等之塗佈方法；旋轉塗佈、噴霧塗佈、浸漬塗佈等塗佈方法；網版印刷及凹版印刷等所代表之印刷技術等。 塗佈厚度應根據所需之樹脂膜之厚度與樹脂組合物中之聚醯亞胺前驅體之含量而適宜調整，較佳為1~1,000 μm左右。塗佈步驟於室溫下實施便足矣，但為了降低黏度而提高作業性，亦可於40~80℃之範圍內對樹脂組合物進行加溫而實施。 繼塗佈步驟後可進行乾燥步驟，或亦可省略乾燥步驟而直接進入後續之加熱步驟。該乾燥步驟係為了去除有機溶劑而進行。於進行乾燥步驟之情形時，例如可利用加熱板、箱形乾燥機、輸送帶型乾燥機等適宜之裝置。乾燥步驟較佳為於80~200℃下進行，更佳為於100~150℃下進行。乾燥步驟之實施時間較佳為設為1分鐘~10小時，更佳為設為3分鐘~1小時。 如上述般於支持體上形成含有聚醯亞胺前驅體之塗膜。 繼而進行加熱步驟。加熱步驟係進行於上述乾燥步驟中殘留於塗膜中之有機溶劑之去除，並且使塗膜中之聚醯亞胺前驅體進行醯亞胺化反應，獲得包含聚醯亞胺之膜的步驟。 該加熱步驟例如可使用惰性氣體烘箱、加熱板、箱形乾燥機、輸送帶型乾燥機等裝置進行。該步驟可與上述乾燥步驟同時進行，亦可逐次進行兩步驟。 加熱步驟亦可於空氣氛圍下進行，但就安全性與所獲得之聚醯亞胺膜之透明性及YI值之觀點而言，推薦於惰性氣體氛圍下進行。作為惰性氣體，例如可列舉氮氣、氬氣等。 加熱溫度亦可根據(b)有機溶劑之種類而適宜設定，較佳為250℃~550℃，更佳為300~450℃。若為250℃以上則醯亞胺化充分，若為550℃以下則不會產生所獲得之聚醯亞胺膜之透明性之降低、耐熱性之劣化等不良狀況。加熱時間較佳為設為0.5~3小時左右。 於本實施形態中，上述加熱步驟中之周圍氛圍之氧濃度就所獲得之聚醯亞胺膜之透明性及YI值之觀點而言，較佳為2,000質量ppm以下，更佳為100質量ppm以下，進而較佳為10質量ppm以下。藉由在氧濃度為2,000質量ppm以下之氛圍中進行加熱，可使所獲得之聚醯亞胺膜之YI值為30以下。 根據聚醯亞胺樹脂膜之使用用途、目的不同，有時於上述加熱步驟之後需要自支持體剝離樹脂膜之剝離步驟。該剝離步驟較佳為於將支持體上之樹脂膜冷卻至室溫~50℃左右後實施。 作為該剝離步驟，例如可列舉下述(1)~(4)之態樣。 (1)於藉由上述方法製作包含聚醯亞胺樹脂膜/支持體之構成體後，自該結構體之支持體側照射雷射，對支持體與聚醯亞胺樹脂膜之界面進行剝蝕加工，藉此剝離聚醯亞胺樹脂之方法。作為雷射之種類，可列舉固體(YAG)雷射、氣體(UV準分子)雷射等。較佳為使用波長308 nm等之光譜(參照日本專利特表2007-512568公報、日本專利特表2012‐511173公報等)。 (2)於支持體上塗佈樹脂組合物之前，於支持體上形成剝離層，其後獲得包含聚醯亞胺樹脂膜/剝離層/支持體之構成體，並剝離聚醯亞胺樹脂膜之方法。可列舉：使用帕利靈(註冊商標，日本帕利靈有限公司製造)、氧化鎢作為剝離層之方法；使用植物油系、矽酮系、氟系、醇酸系等之脫模劑之方法等(參照日本專利特開2010-67957公報、日本專利特開2013-179306公報等)。 亦可將該方法(2)與上述(1)之雷射照射併用。 (3)使用可蝕刻金屬基板作為支持體，於獲得包含聚醯亞胺樹脂膜/支持體之構成體後，利用蝕刻劑對金屬進行蝕刻，藉此獲得聚醯亞胺樹脂膜之方法。作為金屬，例如可使用銅(作為具體例，為三井金屬礦業股份有限公司製造之電解銅箔「DFF」)、鋁等。作為蝕刻劑，對於銅可使用氯化鐵等，對於鋁可使用稀鹽酸等。 (4)於藉由上述方法獲得包含聚醯亞胺樹脂膜/支持體之構成體後，於聚醯亞胺樹脂膜表面上貼附黏著膜，自支持體分離黏著膜/聚醯亞胺樹脂膜，其後自黏著膜分離聚醯亞胺樹脂膜之方法。 於該等剝離方法之中，就所獲得之聚醯亞胺樹脂膜之正面與背面之折射率差、YI值、及伸長率之觀點而言，方法(1)或(2)恰當，就所獲得之聚醯亞胺樹脂膜之正面與背面之折射率差之觀點而言，方法(1)更為恰當。 再者，於方法(3)中，於使用銅作為支持體之情形時，可見所獲得之聚醯亞胺樹脂膜之YI值變大，伸長率變小之傾向。可認為其係銅離子之影響。 藉由上述方法所獲得之樹脂膜之厚度無特別限定，較佳為1~200 μm之範圍，更佳為5~100 μm。 本實施形態之樹脂膜可為10 μm膜厚時之黃度YI為20以下。此種特性例如可藉由在氮氣氛圍下(例如氧濃度2,000 ppm以下之氮氣中)，於較佳為400℃~550℃、更佳為400℃~450℃下使本發明之樹脂前驅體進行醯亞胺化而良好地實現。 本實施形態之樹脂膜進而可為拉伸伸長率為15%以上。樹脂膜之拉伸伸長率進而可為20%以上，尤其可為30%以上。藉此，本實施形態之樹脂膜於操作撓性基板時之斷裂強度優異，因此可提高製造撓性顯示器時之良率。該拉伸伸長率可將10 μm膜厚之樹脂膜作為試樣，使用市售之拉伸試驗機進行測定。 ＜積層體＞ 本發明之另一態樣提供一種積層體，其包含支持體與於該支持體之表面上由上述樹脂組合物所形成之聚醯亞胺樹脂膜。 又，本發明之又一態樣提供一種上述積層體之製造方法。 本實施形態中之積層體可藉由包括如下步驟之積層體之製造方法而獲得：藉由在支持體之表面上塗佈上述樹脂組合物而形成塗膜之步驟(塗佈步驟)；及藉由將上述支持體及上述塗膜加熱而使該塗膜中所含之聚醯亞胺前驅體進行醯亞胺化，形成聚醯亞胺樹脂膜之步驟(加熱步驟)。 上述積層體之製造方法例如除了不進行剝離步驟以外，可與上述樹脂膜之製造方法同樣地實施。 該積層體例如可合適地用於撓性器件之製造。 如下所述般更詳細地進行說明。 於形成撓性顯示器之情形時，使用玻璃基板作為支持體，於其上形成撓性基板，進而於其上進行TFT等之形成。於撓性基板上形成TFT等之步驟典型而言係於150~650℃之較廣範圍之溫度下實施。然而，於形成LTPS作為TFT之情形時，與非晶矽(250℃)或IGZO(350℃)相比較，需要極高之溫度，需要400℃~550℃左右之加熱。 另一方面，由於該等熱歷程，聚醯亞胺膜之各物性(尤其是黃度或伸長率)存在降低之傾向，若超過400℃，則尤其黃度或伸長率降低。然而，由本發明之聚醯亞胺前驅體所獲得之聚醯亞胺膜即便於400℃以上之高溫區域中，黃度或伸長率之降低亦極少，可良好地用於該區域。 對於本實施形態之聚醯亞胺膜而言，與形成於IGZO上之情形相比，於形成於LTPS上之情形時可獲得良好之熱循環試驗結果。因此，本實施形態之聚醯亞胺膜可合適地用於TFT之器件類型為LTPS之情形。 進而，於本實施形態中，可提供一種包括包含下述通式(5)所表示之聚醯亞胺之聚醯亞胺膜層與LTPS層之積層體。 [化14]
Figure 02_image031
作為該積層體之製造方法，於製造包含上述支持體與於該支持體之表面上由上述樹脂組合物所形成之聚醯亞胺樹脂膜的積層體後，形成非晶矽層，於400~450℃下進行0.5~3小時左右脫氫退火後，利用準分子雷射等進行結晶化，藉此可形成低溫多晶矽層。 其後，藉由雷射剝離等將玻璃與聚醯亞胺膜剝離，藉此可獲得上述積層體。 又，亦可視需要於聚醯亞胺膜上形成SiO2 或SiN等無機膜後形成LTPS層。 作為上述聚醯亞胺膜層，就霧度及伸長率之觀點而言更佳為下述通式(6)。 [化15]
Figure 02_image033
此時，玻璃基板與聚醯亞胺樹脂膜中所產生之殘留應力越高，則於包含兩者之積層體於高溫之TFT形成步驟中膨脹後，於常溫冷卻時收縮時，越可能產生玻璃基板之翹曲及破損、撓性基板自玻璃基板剝離等問題。一般而言，玻璃基板之熱膨脹係數與樹脂相比而較小，故而於該玻璃基板與撓性基板之間產生殘留應力。如上所述，本實施形態之樹脂膜可將與玻璃基板之間所產生之殘留應力設為25 MPa以下，故而可合適地用於撓性顯示器之形成。 進而，本實施形態之聚醯亞胺膜可將於430度下將聚醯亞胺膜加熱時之10 μm膜厚時之黃度YI設為20以下，且可將拉伸伸長率設為15%以上。藉此，本實施形態之樹脂膜於操作撓性基板時之斷裂強度優異，因此可提高製造撓性顯示器時之良率。 上述態樣係撓性顯示器用LTPS-TFT基板製作之實施形態之說明，以下對作為顯示器器件之實施態樣進行記載。 作為撓性顯示器，例如可列舉有機EL顯示器。 有機EL顯示器係顯示部分可柔軟地變形(具有撓性)之所謂撓性顯示器。圖1係表示有機EL結構部25之構成之一部分之圖。有機EL結構部25係形成於包含玻璃基板21、光熱交換膜22、透明樹脂層23及底塗層24之下部基板2a上，包含與構成一般之有機EL顯示器之構件相同之構成構件，例如將發出紅色光之有機EL元件250a、發出綠色光之有機EL元件250b及發出藍色光之有機EL元件250c作為1個單位而排列成矩陣狀，藉由隔離壁(堤)251劃分各有機EL元件之發光區域。各有機EL元件包含下部電極(陽極)252、電洞傳輸層253、發光層254、上部電極(陰極)255。又，於下部基板2a上設置有複數個用以驅動有機EL元件之TFT256(a-Si、p-Si、氧化物半導體)。 (有機EL顯示器之製造方法) 該有機EL顯示器20之製造步驟中包括有機EL基板製造步驟、密封基板製造步驟、貼合兩基板之組裝步驟、及剝離玻璃基板21、29之剝離步驟。 有機EL基板製造步驟、密封基板製造步驟、及組裝步驟可應用周知之製造步驟。以下列舉其一例，但不限定於此。又，剝離步驟與上述聚醯亞胺膜之剝離步驟相同。 例如，首先於藉由上述方法製作撓性顯示器用LTPS-TFT基板後，利用感光性丙烯酸系樹脂等形成具備接觸孔之層間絕緣膜。藉由濺鍍法等而成膜ITO膜，以與TFT成對之方式形成下部電極。 其次，於利用感光性聚醯亞胺等形成隔離壁後，於由隔離壁所劃分之各空間內形成電洞傳輸層、發光層。又，以覆蓋發光層及隔離壁之方式形成上部電極。藉由上述步驟而製作有機EL基板，並利用密封膜等進行密封，藉此製作頂部發光型撓性有機EL顯示器。亦可藉由公知之方法製作底部發光型撓性有機EL顯示器。 又，於製作上述LTPS-TFT基板後，製作具備無色透明聚醯亞胺之彩色濾光玻璃基板，於TFT基板及CF基板之一者上，藉由網版印刷將包含熱硬化性環氧樹脂等之密封材料塗佈為缺少液晶注入口之部分之框狀圖案，於另一基板上散佈具有相當於液晶層之厚度之直徑、包含塑膠或二氧化矽之球狀間隔件。 繼而，貼合TFT基板與CF基板，使密封材料硬化。 最後，於由TFT基板及CF基板以及密封材料所包圍之空間中，藉由減壓法注入液晶材料後，於液晶注入口塗佈熱硬化樹脂，藉由加熱將液晶材料密封，藉此形成液晶層。最後，利用雷射剝離法等將CF側之玻璃基板與TFT側之玻璃基板剝離，藉此可製作撓性液晶顯示器。 因此，本發明之另一態樣提供一種顯示器基板。 又，本發明之又一態樣提供一種製造上述顯示器基板之方法。 本實施形態中之顯示器基板之製造方法之特徵在於包括如下步驟： 藉由在支持體之表面上塗佈上述樹脂組合物而形成塗膜之步驟(塗佈步驟)； 藉由將上述支持體及上述塗膜加熱而使該塗膜中所含之聚醯亞胺前驅體進行醯亞胺化，形成聚醯亞胺樹脂膜之步驟(加熱步驟)； 於上述聚醯亞胺樹脂膜上形成元件或電路之步驟(元件、電路形成步驟)；及 將形成有上述元件或電路之聚醯亞胺樹脂膜自上述支持體剝離之步驟(剝離步驟)。 於上述方法中，塗佈步驟、加熱步驟、及剝離步驟分別可與上述樹脂膜之製造方法同樣地進行。 元件、電路形成步驟可藉由業者公知之方法實施。 滿足上述物性之本實施形態之樹脂膜可合適地用於因現有之聚醯亞胺膜所具有之黃色而使用受限制之用途，尤其可合適地用於撓性顯示器用無色透明基板、彩色濾光片用保護膜等用途。進而例如亦可用於保護膜、TFT-LCD等中之散光片及塗膜(例如TFT-LCD之中間層、閘極絕緣膜、液晶配向膜等)、觸控面板用ITO基板、智慧型手機用蓋玻璃代替樹脂基板等要求無色透明性且低雙折射之領域。 本實施形態之聚醯亞胺前驅體、使用樹脂前驅體所製造之樹脂膜及積層體例如可作為半導體絕緣膜、TFT-LCD絕緣膜、電極保護膜等而應用，此外可於撓性器件之製造中尤其合適地用作基板。此處，作為可應用本實施形態之樹脂膜及積層體之撓性器件，例如可列舉撓性顯示器、撓性太陽電池、撓性觸控面板電極基板、撓性照明、撓性電池等。 [實施例] 以下，根據實施例進而對本發明進行詳述，但該等係為了說明而記載者，且本發明之範圍不限定於下述實施例。 實施例及比較例中之各種評價係按照如下方式進行。 ＜重量平均分子量之測定＞ 重量平均分子量(Mw)及數量平均分子量(Mn)係利用凝膠滲透層析儀(GPC)藉由下述條件測定。 作為溶劑，使用NMP(和光純藥工業公司製造，高效液相層析用，於即將測定之前添加24.8 mmol/L之溴化鋰一水合物(和光純藥工業公司製造，純度99.5%)及63.2 mmol/L之磷酸(和光純藥工業公司製造，高效液相層析用)並加以溶解而成者)。用以算出重量平均分子量之校準曲線係使用標準聚苯乙烯(Tosoh公司製造)製作。 管柱：Shodex KD-806M(昭和電工公司製造) 流速：1.0 mL/min 管柱溫度：40℃ 泵：PU-2080Plus(JASCO公司製造) 檢測器：RI-2031Plus(RI：示差折射計，JASCO公司製造)及UV-2075Plus(UV-VIS：紫外可見吸光計，JASCO公司製造) ＜分子量未達1,000之分子之含量(低分子聚物含量)之評價＞ 樹脂中之分子量未達1,000之分子之含量係使用上述所獲得之GPC之測定結果，以分子量未達1,000之成分所占之峰面積於分子量分佈總體之峰面積中所占的比率(百分率)之形式算出。 ＜水分量之評價＞ 合成溶劑及樹脂組合物(清漆)之水分量係使用卡氏水分測定裝置(微量水分測定裝置AQ-300，平沼產業公司製造)進行測定。 ＜樹脂組合物之黏度穩定性之評價＞ 對於各實施例及比較例中製備之樹脂組合物，將製備後於室溫下靜置3天之樣本作為製備後之樣本進行23℃下之黏度測定； 其後將進而於室溫下靜置2週之樣本作為2週後之樣本，再次進行23℃下之黏度測定。該等黏度測定係使用附調溫機之黏度計(東機產業公司製造TV-22)進行。 使用上述測定值，藉由下述數式算出室溫2週黏度變化率。 室溫2週黏度變化率(%)=[(2週後之樣本之黏度)-(製備後之樣本之黏度)]/(製備後之樣本之黏度)×100 室溫2週黏度變化率係按下述基準進行評價。 ◎：黏度變化率為5%以下(保存穩定性「優良」) ○：黏度變化率超過5且為10%以下(保存穩定性「良好」) ×：黏度變化率超過10%(保存穩定性「不良」) ＜清漆塗佈性之評價＞ 使用棒式塗佈機以固化後膜厚成為15 μm之方式將各實施例及比較例中製備之樹脂組合物塗佈於無鹼玻璃基板(尺寸37×47 mm、厚度0.7 mm)上後，於140℃下預烘烤60分鐘。 使用輪廓儀(Tencor公司製造，型號名P-15)測定塗膜表面之階差而對清漆之塗佈性進行評價。 ◎：表面之階差為0.1 μm以下(塗佈性「優良」) ○：表面之階差超過0.1且為0.5 μm以下(塗佈性「良好」) ×：表面之階差超過0.5 μm(塗佈性「不良」) ＜殘留應力之評價＞ 藉由旋轉塗佈機將各樹脂組合物塗佈於已預先測定「翹曲量」之厚度625 μm±25 μm之6吋矽晶圓上，於100℃下預烘烤7分鐘。其後，使用立式固化爐(Koyo Lindberg公司製造，型號名VF-2000B)以庫內之氧濃度成為10質量ppm以下之方式進行調整，於430℃下實施1小時之加熱硬化處理(固化處理)，而製作附有硬化後膜厚10 μm之聚醯亞胺樹脂膜之矽晶圓。 使用殘留應力測定裝置(Tencor公司製造，型號名FLX-2320)測定該晶圓之翹曲量，對矽晶圓與樹脂膜之間產生之殘留應力進行評價。 ＜黃度(YI值)之評價＞ 以硬化後膜厚成為10 μm之方式將各實施例及比較例中製備之樹脂組合物旋轉塗佈於表面上設置有鋁蒸鍍層之6吋矽晶圓基板上，於100℃下預烘烤7分鐘。其後，使用立式固化爐(Koyo Lindberg公司製造，型號名VF-2000B)以庫內之氧濃度成為10質量ppm以下之方式進行調整，於430℃下實施1小時之加熱硬化處理，而製作形成有聚醯亞胺樹脂膜之晶圓。 將上述所獲得之積層體晶圓浸漬於稀鹽酸水溶液中，將聚醯亞胺膜自晶圓剝離，藉此獲得於表面形成有無機膜之聚醯亞胺膜之樣本。 對於所獲得之聚醯亞胺樹脂膜，藉由日本電色工業(股)製造之(Spectrophotometer：SE600)使用D65光源測定YI值(膜厚10 μm換算)。 ＜伸長率及斷裂強度之評價＞ 與上述＜黃度之評價＞同樣地製作晶圓。使用晶圓切割機(DISCO股份有限公司製造之DAD 3350)於該晶圓之聚醯亞胺樹脂膜中切入寬度3 mm之切口後，於稀鹽酸水溶液中浸漬一夜，剝離樹脂膜片並使其乾燥。將其切割為長度50 mm而製成樣本。 對於上述樣本，使用TENSILON(Orientec公司製造之UTM-II-20)以試驗速度40 mm/min、初始負荷0.5 fs測定伸長率及斷裂強度。 [合成例1] 於具備油浴之附攪拌棒之3 L可分離式燒瓶中，一面導入氮氣一面添加NMP1(1065 g)，一面攪拌一面添加4,4'-二胺基二苯基碸(248.3 g)作為二胺，繼而添加PMDA(218.12 g)作為酸二酐並於室溫下攪拌30分鐘。將其升溫至50℃並攪拌12小時後，去掉油浴而回到室溫，獲得透明之聚醯胺酸之NMP溶液(以下亦記為清漆)(清漆P-1)。將此處之組成及所獲得之聚醯胺酸之重量平均分子量(Mw)分別示於表1。又，將經430℃固化之膜之試驗結果示於表2。 [實施例1] 於具備油浴之附攪拌棒之3 L可分離式燒瓶中，一面導入氮氣一面添加NMP2(1065 g)，一面攪拌一面添加4,4'-二胺基二苯基碸(248.3 g)作為二胺，繼而添加PMDA(218.12 g)作為酸二酐並於室溫下攪拌30分鐘。將其升溫至80℃並攪拌3小時後，去掉油浴而回到室溫，獲得透明之聚醯胺酸之NMP溶液(以下亦記為清漆)(清漆P-2)。將此處之組成及所獲得之聚醯胺酸之重量平均分子量(Mw)分別示於表1。又，將經430℃固化之膜之試驗結果示於表2。 [實施例2] 除了將NMP2變更為NMP3以外，利用與實施例1相同之方法進行合成(清漆P-3)。將結果示於表1及2。 [實施例3] 除了於胺中以莫耳比成為99.33：0.67之方式添加作為第1二胺之4,4'-二胺基二苯基碸、與作為第2二胺之兩末端胺改性甲基苯基矽酮油以外，利用與實施例2相同之方法進行合成(清漆P-4)。將結果示於表1及表2。 [實施例4~實施例13] 除了於胺中如表1所示般變更第1二胺與第2二胺之種類及莫耳比以外，利用與實施例3相同之方法進行合成(清漆P-5~P-14)。將結果示於表1及表2。 [實施例14] 除了於酸二酐中以莫耳比成為80：20之方式添加作為第1酸二酐之均苯四甲酸二酐、與作為第2酸二酐之聯苯四羧酸二酐以外，利用與實施例2相同之方法進行合成(清漆P-15)。將結果示於表1及表2。 [實施例15~實施例17] 除了於酸二酐中如表1所示般變更第1酸二酐與第2酸二酐之莫耳比以外，利用與實施例2相同之方法進行合成(清漆P-16~P-18)。將結果示於表1及表2。 [實施例18] 除了於二胺中將4,4'-二胺基二苯基碸變更為3,3'-二胺基二苯基碸以外，利用與實施例2相同之方法進行合成(清漆P-19)。 [比較例1~比較例6] 除了如表1般變更酸二酐與二胺以外，利用與實施例2相同之方法進行合成(清漆P-20~清漆P-25)。 將以上各實施例及比較例中之組成及所獲得之聚醯胺酸之重量平均分子量(Mw)分別示於表1。又，將經430℃固化之膜之試驗結果示於表2。 [表1]
Figure 106129267-A0304-0001
 表中之各成分之簡稱分別為以下含義。 PMDA：均苯四甲酸二酐 BPDA：聯苯四羧酸二酐 4,4'-DAS：4,4'-二胺基二苯基碸 3,3'-DAS：3,3'-二胺基二苯基碸 APAB：4-胺基苯基-4-胺基苯甲酸酯 p-PD：對苯二胺 6FDA：4,4'-(六氟亞異丙基)二鄰苯二甲酸酐 CHDA：1,4-環己烷二胺 DSDA：3,3',4,4'-二苯基碸四羧酸二酐 HPMDA：1,2,4,5-環己烷四羧酸二酐 TFMB：2,2'-雙(三氟甲基)聯苯胺 X-22-1660B-3：兩末端胺改性甲基苯基矽酮油(信越化學公司製造) NMP1：將500 ml瓶裝品開封後放置一個月所得者，水分量3,070 ppm NMP2：將500 ml瓶裝品開封後放置一週所得者，水分量1500 ppm NMP3：18 L桶剛開封後者，水分量250 ppm [表2]
Figure 106129267-A0304-0002
 如由表1及表2所表明，可知具有通式(1)所表示之結構之合成例1、實施例1~18之樹脂組合物與比較例1~6之樹脂組合物相比較，殘留應力較小，黃度較低，伸長率較高。 尤其於聚醯亞胺前驅體之重量平均分子量為4萬以上且30萬以下，並且重量平均分子量未達1,000之分子之含量未達5質量%之實施例1~18中，與合成例1相比伸長率較大，可獲得尤其良好之結果。具體而言，可獲得殘留應力為25 MPa以下，黃度YI為20以下，伸長率為15%以上之樹脂膜。 又，將合成例1與實施例1、2比較可知聚合反應中所使用之溶劑之水分量越少，則分子量未達1,000之分子之含量越變少。 [合成例、實施例1~18、比較例1~6] 製作圖1所示般之有機EL基板。 使用棒式塗佈機以固化後膜厚成為10 μm之方式將合成例1、及實施例、比較例之聚醯亞胺前驅體清漆塗佈於素玻璃基板(厚度0.7 mm)上後，於140℃下預烘烤60分鐘。繼而使用立式固化爐(Koyo Lindberg公司製造，型號名VF-2000B)以庫內之氧濃度成為10質量ppm以下之方式進行調整，於430℃下實施1小時之加熱硬化處理，製作形成有聚醯亞胺樹脂膜之玻璃基板。 繼而藉由CVD(Chemical Vapor Deposition，化學氣相沈積)法以厚度100 nm成膜SiN層。 繼而藉由濺鍍法成膜鈦，其後藉由光微影法進行圖案化，形成掃描信號線。 其次，於形成有掃描信號線之玻璃基板整體上藉由CVD法以厚度100 nm成膜SiN層。(至此為止設為下部基板2a) 繼而於下部基板2a上形成非晶矽層256，於430℃下進行1小時脫氫退火，繼而照射準分子雷射，藉此形成LTPS層。 其後藉由旋轉塗佈法於下部基板2a之整個面上塗佈感光性丙烯酸系樹脂，藉由光微影法進行曝光、顯影而形成具備複數個接觸孔257之層間絕緣膜258。藉由該接觸孔257而製成各LTPS256之一部分露出之狀態。 其次藉由濺鍍法於形成有層間絕緣膜258之下部基板2a之整個面上成膜ITO膜，藉由光微影法進行曝光、顯影，並藉由蝕刻法進行圖案化，以與各LTPS成對之方式形成下部電極259。 再者，於各接觸孔257中，將貫通層間絕緣膜258之下部電極252與LTPS256電性連接。 其次於形成隔離壁251後，於由隔離壁251所劃分之各空間內形成電洞傳輸層253、發光層254。又，以覆蓋發光層254及隔離壁251之方式形成上部電極255。藉由上述步驟而製作有機EL基板。 其次，於依序形成有玻璃基板、本實施形態之聚醯亞胺膜及SiN層的密封基板2b之周邊塗佈紫外線硬化樹脂，於氬氣氛圍中使密封基板2b與有機EL基板接著，藉此封入有機EL元件。藉此，於各有機EL元件與密封基板2b之間形成中空部261。 自如此所形成之積層體之下部基板2a側、及密封基板2b側照射準分子雷射(波長308 nm，重複頻率300 Hz)，以剝離整個面所需之最小能量進行剝離。 對該積層體進行剝離後之基板翹曲、點亮試驗、積層體之白濁評價之有無評價。又，亦實施熱循環試驗。將結果示於表3。 ＜基板翹曲＞ ◎：無翹曲 ○：僅有稍許翹曲 Δ：因翹曲而捲起 ＜點亮試驗＞ ○：點亮 ×：未點亮 ＜積層體白濁評價＞ 於形成積層體後，藉由目測進行觀察，將器件整體透明者視為○，稍有白濁者視為Δ，白濁者視為×。 ＜熱循環試驗＞ 使用愛斯佩克製造之熱循環試驗機，分別於-5℃與60℃下30分鐘(槽之移動時間1分鐘)而進行1000次循環試驗後，進行外觀觀察。 將無剝離或鼓起者視為○，將於試驗後觀察到極少一部分剝離或鼓起者視為Δ，將於試驗後整個面觀察到剝離或鼓起者視為×。 [表3]
Figure 106129267-A0304-0003
 如由表3所表明，於使用清漆P-2~P-19之實施例1~18中，可獲得基板無翹曲、點亮試驗亦良好、亦無白濁、具有良好之熱循環特性之積層體。此種積層體可合適地用作低溫多晶矽TFT元件基板，例如有機EL顯示器之透明撓性基板。 本發明不限定於上述實施形態，可於不脫離發明之主旨之範圍內進行各種變化而實施。 [產業上之可利用性] 藉由使用本發明之聚醯亞胺前驅體、及樹脂組合物，可獲得殘留應力為25 MPa以下、黃度YI為20以下、伸長率為15%以上之樹脂膜。此種樹脂膜除了可應用於例如半導體絕緣膜、TFT-LCD絕緣膜、電極保護膜等以外，亦可於撓性顯示器之製造、觸控面板ITO電極用基板等中尤其合適地用作基板。Hereinafter, an exemplary embodiment of the present invention (hereinafter simply referred to as "embodiment") will be described in detail. In addition, the present invention is not limited to the following embodiments, and can be implemented with various changes within the scope of the gist. In addition, the characteristic value described in the present invention means a value measured by the method described in the item of [Examples] or a method equivalent to it understood by the industry, unless otherwise stated. <Resin composition> The resin composition provided by one aspect of the present invention contains (a) a polyimide precursor, and (b) an organic solvent. Hereinafter, each component will be described in order. [Polyimine precursor] The polyimide precursor system (a) in this embodiment is the following general formula (1): [化6]
Figure 02_image015
Said polyimide precursor. As the acid dianhydride used in the general formula (1) of this embodiment, pyromellitic dianhydride (hereinafter also referred to as PMDA) can be exemplified. As the diamine used in the general formula (1) of this embodiment, 4,4'-diaminodiphenyl sulfonium and 3,3'-diaminodiphenyl sulfonium can be exemplified. Among them, from the viewpoints of the residual stress, YI, glass transition temperature, retardation Rth, elongation, and haze of the obtained polyimide film, the use represented by the following general formula (2) 4, The structure of 4'-diaminodiphenyl sulfide. [化7]
Figure 02_image017
The weight average molecular weight (Mw) of the polyimide precursor in this embodiment is preferably 10,000 to 300,000, and particularly preferably 40,000 to 300,000. When the weight average molecular weight is 40,000 or more, the mechanical properties such as elongation and breaking strength are particularly excellent, the residual stress becomes low, and the YI becomes low. If the weight average molecular weight is less than 300,000, it becomes easier to control the weight average molecular weight during the synthesis of polyamide acid, a resin composition with a moderate viscosity can be obtained, and the coating property of the resin composition becomes good. In the present invention, the weight average molecular weight is a value obtained as a standard polystyrene conversion value using a gel permeation chromatograph (hereinafter also referred to as GPC). When the total weight of the solid components contained in the resin composition of the present embodiment is set to 100% by mass, the smaller the content of molecules with a molecular weight of less than 1,000, the better. Specifically, relative to the total weight of the solid content, it is preferably less than 5% by mass, more preferably 4% by mass or less, preferably 3% by mass or less, preferably 2% by mass or less, and preferably 1 % By mass or less, preferably 0.5% by mass or less, preferably 0.1% by mass or less, preferably 0.05% by mass or less, preferably 0.02% by mass or less. Such a composition is excellent in viscosity stability and varnish coatability. In addition, the polyimide film obtained from this composition has lower residual stress, lower YI, higher glass transition temperature (Tg), lower retardation Rth, and higher elongation, which is better. In addition, the laminated system including such a polyimide film and low-temperature polysilicon TFT has less warpage, lower haze, and good thermal cycle test results. The content of molecules with a molecular weight of less than 1,000 can be calculated based on the peak area obtained by GPC measurement of the resin composition. In the polyimide precursor in this embodiment, in addition to pyromellitic dianhydride, other acid dianhydrides can be used within a range that does not impair elongation, strength, stress, and yellowness. As such an acid dianhydride, 4,4'-(hexafluoroisopropylidene) diphthalic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3 -Methyl-cyclohexene-1,2 dicarboxylic acid anhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl Base tetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, methylene-4,4'-diphthalic dianhydride, 1,1-ethylene -4,4'-diphthalic dianhydride, 2,2-propylene-4,4'-diphthalic dianhydride, 1,2-ethylene-4,4'-diphthalic anhydride Phthalic acid dianhydride, 1,3-trimethylene-4,4'-diphthalic dianhydride, 1,4-tetramethylene-4,4'-diphthalic dianhydride, 1 ,5-Pentamethylene-4,4'-diphthalic dianhydride, 4,4'-oxydiphthalic dianhydride, p-phenylene bis (dehydrated trimellitate), sulfur -4,4'-diphthalic dianhydride, sulfonyl-4,4'-diphthalic dianhydride, 1,3-bis(3,4-dicarboxyphenyl)phthalic anhydride , 1,3-bis(3,4-dicarboxyphenoxy)phthalic anhydride, 1,4-bis(3,4-dicarboxyphenoxy)phthalic anhydride, 1,3-bis[2-( 3,4-Dicarboxyphenyl)-2-propyl]phthalic anhydride, 1,4-bis[2-(3,4-dicarboxyphenyl)-2-propyl]phthalic anhydride, bis[3 -(3,4-Dicarboxyphenoxy)phenyl]methane dianhydride, bis[4-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride, 2,2-bis[3-( 3,4-Dicarboxyphenoxy)phenyl]propane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, bis(3,4-di Carboxyphenoxy) dimethyl silane dianhydride, 1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldisiloxane dianhydride, 2,3, 6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylene Tetracarboxylic dianhydride, 2,3,6,7-anthracene tetracarboxylic dianhydride, 1,2,7,8-phenanthrene tetracarboxylic dianhydride, etc. The content of the above-mentioned other acid dianhydrides in the total acid dianhydride is preferably 20 mol% or less, more preferably 10 mol% or less, and particularly preferably 0 mol%. The content of pyromellitic dianhydride in the total acid dianhydride is preferably 90 mol% or more, preferably 95 mol% or more, preferably 98 mol% or more, and preferably 99 mol% or less, Preferably it is 99.5 mol% or more. The greater the amount of pyromellitic dianhydride in the total acid dianhydride, the better from the viewpoints of YI, glass transition temperature Tg, and elongation. In the polyimide precursor in this embodiment, in addition to 4,4'-diaminodiphenyl sulfite, 3,3'-diaminodiphenyl sulfite, it can be used without compromising elongation, Other diamines are used within the range of strength, stress, and yellowness. As other diamines, for example, p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'- Diaminodiphenyl sulfide, 4,4'-diaminodiphenyl, 3,4'-diaminodiphenyl, 3,3'-diaminodiphenyl, 4,4'-diaminodiphenyl Benzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diamino Diphenylmethane, 3,3'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-Bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfonate, 4,4-bis(4-aminophenoxy)biphenyl , 4,4-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)benzene Base) ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2 ,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl ]Propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, etc., preferably To use one or more selected from these. The content of the above-mentioned other diamines in the total diamine is preferably 20 mol% or less, more preferably 10 mol% or less, and particularly preferably 0 mol%. The content of diaminodiphenyl sulfide in the total diamine is preferably 90 mol% or more, preferably 95 mol% or more, preferably 98 mol% or more, preferably 99 mol% or more, Preferably it is 99.5 mol% or more. The greater the amount of diaminodiphenyl sulfide, the better from the viewpoints of residual stress, YI, glass transition temperature Tg, retardation Rth, and elongation. As the diamino diphenyl sulfide, 4,4'-diamino diphenyl sulfide is preferred. The polyimide precursor is preferably the amount of the diamine represented by the following general formula (4) contained in the polyimide precursor when the total moles of the diamine components are set to 100 mole% It is less than 48 mol%. [化8]
Figure 02_image019
(In the formula, R 1 , R 2 , and R 3 each independently represent a monovalent organic group with 1 to 20 carbon atoms. n represents 0 or 1. And a, b, and c are integers from 0 to 4) As a general formula (4) The diamine represented by (4), for example, when n is 0, 4-aminophenyl-4-aminobenzoate (APAB), 2-methyl-4-aminophenyl can be exemplified -4-aminobenzoate (ATAB), 4-aminophenyl-3-aminobenzoate (4,3-APAB), etc. When n is 1, [4-(4-aminobenzyl)phenoxy]4-aminobenzoate and the like can be exemplified. In particular, the polyimide precursor is preferably the diamine component represented by the general formula (4) when the total mole of the diamine component is set to 100 mole%. The content of 4-aminophenyl-4-aminobenzoate is 48 mol% or less. The YI becomes smaller, the Tg becomes higher, the retardation becomes lower, and the elongation becomes higher. It may contain 4-aminophenyl-4-aminobenzoate or not. The smaller the amount of diamine represented by the general formula (4), the better from the viewpoints of YI, glass transition temperature Tg, retardation Rth, and elongation. The amount of the diamine represented by the general formula (4) contained in the polyimide precursor is preferably 30 mol% or less, preferably 20 mol% or less, and preferably 10 mol% or less, Preferably it is 5 mol% or less. In addition, the amount of the diamine represented by the general formula (4), especially 4-aminophenyl-4-aminobenzoate, is preferably less than 1 mol%, preferably 0.9 mol% Below, it is preferably 0.8 mol% or less, preferably 0.6 mol% or less, preferably 0.4 mol% or less, preferably 0.2 mol% or less, and preferably 0.1 mol% or less. The polyimide precursor preferably includes the following formula (3) when the total mass of the diamine component and the acid dianhydride component is 100% by mass: [化9]
Figure 02_image021
(In the formula, there are a plurality of R 3 and R 4 each independently being a monovalent organic group with 1 to 20 carbons, and h is an integer from 3 to 200) The content of the silicone diamine component of the structure represented Less than 6 mass%. The smaller the silicone diamine component including the structure represented by the above formula (3), the smaller the YI, the larger the glass transition temperature Tg, and the smaller the retardation Rth, which is preferable. The content of the silicone diamine component containing the structure represented by the above formula (3) is preferably 5.9% by mass or less, 5.5% by mass or less, 5.0% by mass or less, 4.0% by mass or less, 3.0% by mass or less, and 2.0% by mass or less , 1.0 mass% or less, 0.5 mass% or less, 0.4 mass% or less, 0.3 mass% or less, 0.2 mass% or less, 0.1 mass% or less, 0.08 mass% or less, 0.06 mass% or less, 0.04 mass% or less, 0.02 mass% or less . The polyimide precursor in the embodiment can also be made into a polyimide imine precursor by using dicarboxylic acid in addition to the above-mentioned tetracarboxylic dianhydride within the range of not impairing its performance. By using such a precursor, various properties of the obtained film can be adjusted such as increase in mechanical elongation, increase in glass transition temperature, and decrease in yellowness. Examples of such dicarboxylic acids include dicarboxylic acids having an aromatic ring and alicyclic dicarboxylic acids. Particularly preferred is at least one compound selected from the group consisting of aromatic dicarboxylic acids having 8 to 36 carbon atoms and alicyclic dicarboxylic acids having 6 to 34 carbon atoms. The number of carbons mentioned here also includes the number of carbons contained in the carboxyl group. Among these, dicarboxylic acid having an aromatic ring is preferred. Specifically, for example, isophthalic acid, terephthalic acid, 4,4'-biphenyldicarboxylic acid, 3,4'-biphenyldicarboxylic acid, 3,3'-biphenyldicarboxylic acid , 1,4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-sulfonyl dibenzoic acid, 3,4'- Sulfonyl dibenzoic acid, 3,3'-sulfonyl dibenzoic acid, 4,4'-oxy dibenzoic acid, 3,4'-oxy dibenzoic acid, 3,3'-oxy diphenyl Formic acid, 2,2-bis(4-carboxyphenyl)propane, 2,2-bis(3-carboxyphenyl)propane, 2,2'-dimethyl-4,4'-biphenyl dicarboxylic acid, 3,3'-dimethyl-4,4'-biphenyl dicarboxylic acid, 2,2'-dimethyl-3,3'-biphenyl dicarboxylic acid, 9,9-bis(4-(4 -Carboxyphenoxy)phenyl)pyridium, 9,9-bis(4-(3-carboxyphenoxy)phenyl)pyridium, 4,4'-bis(4-carboxyphenoxy)biphenyl, 4 ,4'-bis(3-carboxyphenoxy)biphenyl, 3,4'-bis(4-carboxyphenoxy)biphenyl, 3,4'-bis(3-carboxyphenoxy)biphenyl, 3,3'-bis(4-carboxyphenoxy)biphenyl, 3,3'-bis(3-carboxyphenoxy)biphenyl, 4,4'-bis(4-carboxyphenoxy)-pair Triphenyl, 4,4'-bis(4-carboxyphenoxy)-terphenyl, 3,4'-bis(4-carboxyphenoxy)-pterphenyl, 3,3'-bis(4 -Carboxyphenoxy)-terphenyl, 3,4'-bis(4-carboxyphenoxy)-triphenyl, 3,3'-bis(4-carboxyphenoxy)-triphenyl , 4,4'-bis(3-carboxyphenoxy)-terphenyl, 4,4'-bis(3-carboxyphenoxy)-triphenyl, 3,4'-bis(3-carboxy Phenoxy)-terphenyl, 3,3'-bis(3-carboxyphenoxy)-terphenyl, 3,4'-bis(3-carboxyphenoxy)-terphenyl, 3, 3'-bis(3-carboxyphenoxy)-terphenyl, 1,1-cyclobutanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid , 4,4'-benzophenone dicarboxylic acid, 1,3-phenylene diacetic acid, 1,4-phenylene diacetic acid, etc.; and the 5- Amino isophthalic acid derivatives, etc. In the case of actual copolymerization of these dicarboxylic acids and polymers, they can also be used in the form of chloroforms, active esters, etc. derived from sulfite chloride. [Production of polyimide precursor] The polyimide precursor (polyimide acid) of the present invention can be used by combining pyromellitic dianhydride with the structural unit represented by the above general formula (1) Diamine (for example, 4,4'-diaminodiphenyl sulfonium) is synthesized by polycondensation reaction. This reaction is preferably carried out in a suitable solvent. Specifically, for example, a method of dissolving a specific amount of 4,4'-DAS in a solvent, adding a specific amount of pyromellitic dianhydride to the obtained diamine solution, and stirring it. Regarding the ratio (mole ratio) of the tetracarboxylic dianhydride component to the diamine component when synthesizing the above-mentioned polyimide precursor, the thermal linear expansion rate, residual stress, elongation, and yellowness of the obtained resin film (Hereinafter also referred to as YI) From the viewpoint of controlling within the required range, it is preferable to set it as tetracarboxylic dianhydride: diamine=100:90~100:110 (relative to 1 mole part of tetracarboxylic dianhydride) The diamine is in the range of 0.90~1.10 mole parts), and is more preferably set to the range of 100:95~100:105 (relative to 1 mole part of acid dianhydride and 0.95~1.05 mole part of diamine) . In this embodiment, when synthesizing polyimide as a preferred polyimide precursor, it can be adjusted by adjusting the ratio of the tetracarboxylic dianhydride component to the diamine component and adding a blocking agent Control molecular weight. The closer the ratio of the acid dianhydride component to the diamine component is 1:1, and the less the amount of capping agent used is, the more the molecular weight of the polyamide acid can be increased. As the tetracarboxylic dianhydride component and diamine component, high-purity products are recommended. The purity is preferably 98% by mass or more, more preferably 99% by mass or more, and still more preferably 99.5% by mass or more. When multiple types of acid dianhydride components or diamine components are used in combination, it is sufficient as long as the acid dianhydride component or diamine component as a whole has the above-mentioned purity, preferably all types of acid dianhydride components and diamine components used Each has the above-mentioned purity. The solvent for the reaction is not particularly limited as long as it can dissolve the tetracarboxylic dianhydride component, the diamine component, and the produced polyamide acid to obtain a high-molecular-weight polymer. As specific examples of such solvents, for example, aprotic solvents, phenolic solvents, ether and glycol solvents, etc. can be cited. Regarding these specific examples, as the aforementioned aprotic solvents, for example, N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methyl -2-pyrrolidone (NMP), N-methylcaprolactam, 1,3-dimethylimidazolidone, tetramethylurea, the following general formula (7): [化 10]
Figure 02_image023
In the formula, R 12 = Equamide M100 represented by methyl group (trade name: manufactured by Idemitsu Kosan Co., Ltd.), and R 12 = Equamide B100 represented by n-butyl group (trade name: manufactured by Idemitsu Kosan Co., Ltd.), etc. Solvents; Lactone-based solvents such as γ-butyrolactone and γ-valerolactone; Phosphorus-containing amine-based solvents such as hexamethylphosphatidamide and hexamethylphosphatidylamine; Sulfur-containing solvents such as sulfite and cyclobutyl; ketone solvents such as cyclohexanone and methylcyclohexanone; tertiary amine solvents such as picoline and pyridine; acetic acid (2-methoxy-1-methyl Ester-based solvents such as ethyl) ester; Examples of the above-mentioned phenol-based solvents include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, etc.; as the above-mentioned ether and glycol solvents, for example, 1,2- Dimethoxyethane, bis(2-methoxyethyl) ether, 1,2-bis(2-methoxyethoxy)ethane, bis[2-(2-methoxyethoxy) ) Ethyl] ether, tetrahydrofuran, 1,4-dioxane, etc. The boiling point of the solvent used in the synthesis of polyamide acid is preferably 60~300°C, more preferably 140~280°C, and particularly preferably 170~270°C under normal pressure. If the boiling point of the solvent is higher than 300°C, the drying step requires a longer time. On the other hand, if the boiling point of the solvent is lower than 60°C, the surface of the resin film may be rough during the drying step, and air bubbles may be mixed in the resin film, and a uniform film may not be obtained. Thus, from the viewpoint of solubility and edge shrinkage during coating, it is preferable to use a solvent having a boiling point of 170 to 270°C, and more preferably a vapor pressure of 250 Pa or less at 20°C. More specifically, it is preferable to use at least one selected from the group consisting of N-methyl-2-pyrrolidone, γ-butyrolactone, and the compound represented by the general formula (5). The moisture content in the solvent is preferably 3000 mass ppm or less. These solvents may be used alone or in combination of two or more kinds. In the resin composition in this embodiment, it is preferable that the content of molecules with a molecular weight of less than 1,000 is less than 5% by mass. It is believed that the reason for the presence of molecules with a molecular weight of less than 1,000 in the resin composition is affected by the amount of water in the solvent or raw materials (acid dianhydride, diamine) used in the synthesis. That is, it is considered that the cause is that a part of the acid anhydride gene of the acid dianhydride monomer is hydrolyzed into a carboxyl group due to moisture, and it remains in a low-molecular state without being a high molecular weight. Therefore, the water content of the solvent used in the above-mentioned polymerization reaction is preferably as small as possible. The water content of the solvent is preferably 3,000 ppm by mass or less, and more preferably 1,000 ppm by mass or less. Regarding the amount of water contained in the raw material, it is also preferable to set it to 3000 mass ppm or less, and more preferably to be 1000 mass ppm or less. It can be considered that the water content of the solvent is affected by the grade of the solvent used (dehydration grade, general-purpose grade, etc.), solvent container (bottle, 18 L drum, storage tank, etc.), the storage state of the solvent (whether rare gas is enclosed, etc.), The time from opening to use (use immediately after opening, or use after a period of time after opening, etc.), etc. In addition, it can be considered that it is also affected by the replacement of the rare gas in the reactor before the synthesis, the presence or absence of the circulation of the rare gas during the synthesis, and so on. Therefore, the following measures are recommended for the synthesis of (a) polyimide precursors: use high-purity products as raw materials, use solvents with less water content, and avoid mixing in the system before and during the reaction. Of water. When dissolving each monomer component in a solvent, heating may be performed as needed. (a) The reaction temperature during the synthesis of the polyimide precursor is preferably set to 0°C to 120°C, more preferably 40°C to 100°C, and even more preferably 60 to 100°C. By carrying out the polymerization reaction at this temperature, a polyimide precursor with a higher degree of polymerization can be obtained. The polymerization time is preferably set to 1 to 100 hours, more preferably set to 2 to 10 hours. By setting the polymerization time to 1 hour or more, a polyimide precursor with a uniform degree of polymerization can be obtained, and by setting the polymerization time to 100 hours or less, a polyimide precursor with a higher degree of polymerization can be obtained. The polyimide precursor of this embodiment may optionally contain other polyimine precursors within a range that does not impair the required performance of the present invention. As such a polyimide precursor, for example, a polyimide precursor obtained by polycondensing the above-mentioned other acid dianhydrides and other diamines can be exemplified. The mass ratio of other polyimide precursors of this embodiment is preferably 30% by mass or less with respect to all of the polyimide precursors (a), and the YI value and total light transmittance of oxygen dependence are reduced. From a standpoint, it is more preferably 10% by mass or less. In a preferred aspect of this embodiment, (a) the polyimide precursor may also be partially imidized. In this case, the imidization rate is preferably set to 80% or less, and more preferably set to 50% or less. This partial imidization is obtained by heating the polyimide precursor (a) to perform dehydration and ring closure. The heating can be performed at a temperature of preferably 120 to 200°C, more preferably 150 to 180°C, preferably 15 minutes to 20 hours, more preferably 30 minutes to 10 hours. In addition, N,N-dimethylformamide dimethyl acetal or N,N-dimethylformamide diethyl acetal is added to the polyamic acid obtained by the above reaction and heated, After part or all of the carboxylic acid is esterified, it is used as the (a) polyimide precursor in this embodiment, so that a resin composition with improved viscosity stability during storage at room temperature can also be obtained. In addition, these ester-modified polyamide acids can also be obtained by the following method: the above-mentioned acid dianhydride component is combined with 1 equivalent of monohydric alcohol relative to the acid anhydride group, sulfite chloride, and dicyclohexyl carbodiamide. After the dehydration condensing agent such as imine reacts sequentially, it undergoes a condensation reaction with the diamine component. The ratio of the (a) polyimide precursor (preferably polyamide acid) in the resin composition of the present embodiment is preferably 3-50% by mass from the viewpoint of coating film formability, and more It is preferably 5-40% by mass, and particularly preferably 10-30% by mass. As a second aspect of this embodiment, a formula (1) represented by the following general formula (1) can be provided, wherein the weight average molecular weight is 40,000 or more and 300,000 or less, and the content of molecules with a weight average molecular weight of less than 1,000 is less than 5 mass % Of polyimide precursor. [化11]
Figure 02_image025
The polyimide precursor in the embodiment is not limited as long as the weight average molecular weight is more than 40,000 and less than 300,000, and the content of molecules with a weight average molecular weight of less than 1,000 is less than 5% by mass. In order to obtain such a polyimide precursor, the water content in the solvent or raw material can be set below a specific range, and by improving the purity of the raw material, the molar ratio of the acid dianhydride to the diamine can be set to a specific range. Achieved within the scope. Specifically, the water content in the solvent is preferably 3000 ppm or less, more preferably 1500 ppm or less, and particularly preferably 500 ppm or less. The purity of the raw material is preferably 98% by mass or more, more preferably 99% by mass or more, and particularly preferably 99.5% by mass or more. Preferably, it is set to the range of tetracarboxylic dianhydride: diamine=100:90~100:110 (diamine is 0.90~1.10 mol parts with respect to 1 mol part of tetracarboxylic dianhydride), and more preferably It is set as the range of 100:95-100:105 (diamine is 0.95~1.05 mol part with respect to 1 mol part of acid dianhydride). The above-mentioned polyimide precursor preferably has a structure represented by the following general formula (2) from the viewpoint of the haze and elongation of the obtained polyimide film. [化12]
Figure 02_image027
When the polyimide precursor has only the structure represented by the general formula (1) (preferably the general formula (2)), even if the yellowness is 20 or less and the residual stress is 25 MPa or less, it cannot be provided. Meet the polyimide film with an elongation of 15% or more. In this embodiment, in addition to the structure represented by the general formula (1), the content of molecules with a weight average molecular weight of 40,000 or more and 300,000 or less, and a weight average molecular weight of less than 1,000, is less than 5% by mass. The polyimide precursor can provide a polyimide film that satisfies the elongation rate. Specifically, it can provide a polyimide film with a yellowness of 20 or less, a residual stress of 25 MPa or less, and an elongation of 15% or more when the film thickness is 10 microns after heating at 430°C. <Resin composition> Another aspect of the present invention provides a resin composition containing the aforementioned (a) polyimide precursor and (b) an organic solvent. The resin composition is typically a varnish. [(b) Organic solvent] The (b) organic solvent in this embodiment is not particularly limited as long as it can dissolve the (a) polyimide precursor and any other components used. As such (b) organic solvent, the solvent described above as the solvent that can be used in the synthesis of (a) polyimide precursor can be used. The preferred organic solvent is also the same as described above. The (b) organic solvent in the resin composition of this embodiment may be the same as or different from the solvent used in the synthesis of (a) the polyimide precursor. (b) The organic solvent is preferably set so that the solid content concentration of the resin composition becomes 3 to 50% by mass. Moreover, it is preferable to adjust the composition and amount of (b) the organic solvent so that the viscosity (25° C.) of the resin composition becomes 500 mPa·s to 100,000 mPa·s before adding. [Other components] The resin composition of the present embodiment may further contain (c) a surfactant, (d) an alkoxysilane compound, etc., in addition to the above-mentioned (a) and (b) components. ((c) Surfactant) By adding a surfactant to the resin composition of this embodiment, the coatability of the resin composition can be improved. Specifically, it can prevent the generation of fine lines in the coating film. Examples of such surfactants include silicone-based surfactants, fluorine-based surfactants, and nonionic surfactants other than these. Regarding these examples, as silicone-based surfactants, for example, organosiloxane polymers KF-640, 642, 643, KP341, X-70-092, X-70-093 (the above are trade names , Shin-Etsu Chemical Industry Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC-190 (the above are trade names, manufactured by Toray Dow Corning Silicone Co., Ltd.), SILWET L-77, L-7001, FZ-2105, FZ-2120, FZ-2154, FZ-2164, FZ-2166, L-7604 (the above are trade names, manufactured by Nippon Unicar), DBE-814, DBE- 224, DBE-621, CMS-626, CMS-222, KF-352A, KF-354L, KF-355A, KF-6020, DBE-821, DBE-712 (Gelest), BYK-307, BYK-310, BYK -378, BYK-333 (the above are trade names, manufactured by BYK-Chemie Japan), Glanol (trade names, manufactured by Kyoeisha Chemical Co., Ltd.), etc.; Examples of fluorine-based surfactants include: MEGAFAC F171, F173, R -08 (manufactured by Dainippon Ink Chemical Industry Co., Ltd., trade name), Fluorad FC4430, FC4432 (Sumitomo 3M Co., Ltd., trade name), etc.; as non-ionic surfactants other than these, for example, polyoxygen Ethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether, etc. Among these surfactants, from the viewpoint of the coating properties (inhibition of fine lines) of the resin composition, silicone-based surfactants and fluorine-based surfactants are preferred. Regarding the oxygen concentration in the curing step, From the viewpoint of the influence of YI value and total light transmittance, a silicone-based surfactant is preferable. In the case of using (c) surfactant, the blending amount is preferably 0.001 to 5 parts by mass, more preferably 0.01 to 3 relative to 100 parts by mass of the (a) polyimide precursor in the resin composition Mass parts. (d) Alkoxysilane compound In order for the resin film obtained from the resin composition of this embodiment to exhibit sufficient adhesion with the support during the manufacturing process of flexible devices, etc., the resin composition can be opposed to (A) 100% by mass of the polyimide precursor contains 0.01-20% by mass of alkoxysilane compound. When the content of the alkoxysilane compound relative to 100% by mass of the polyimide precursor is 0.01% by mass or more, good adhesion to the support can be obtained. In addition, the content of the alkoxysilane compound is preferably 20% by mass or less from the viewpoint of the storage stability of the resin composition. The content of the alkoxysilane compound is more preferably 0.02 to 15% by mass relative to 100 parts by mass of the polyimide precursor, more preferably 0.05 to 10% by mass, and particularly preferably 0.1 to 8% by mass. By using an alkoxysilane compound as an additive of the resin composition of this embodiment, in addition to the improvement of the above-mentioned adhesion, the coating property of the resin composition (suppression of unevenness in fine lines) can be further improved, and the obtained The YI value of the cured film is less dependent on the oxygen concentration during curing. Examples of alkoxysilane compounds include 3-ureidopropyltriethoxysilane, bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, and 3-glycidoxysilane. Propyl trimethoxysilane, γ-aminopropyl trimethoxysilane, γ-aminopropyl tripropoxysilane, γ-aminopropyl tributoxysilane, γ-aminoethyl triethyl Oxysilane, γ-aminoethyltripropoxysilane, γ-aminoethyltributoxysilane, γ-aminobutyltriethoxysilane, γ-aminobutyltrimethoxysilane , Γ-aminobutyltripropoxysilane, γ-aminobutyltributoxysilane, phenylsilantriol, trimethoxyphenylsilane, trimethoxy(p-tolyl)silane, diphenyl Silanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, triphenylsilanol and alkoxy represented by each of the following structures It is preferable to use at least one selected from the group consisting of silane compounds and the like. [化13]
Figure 02_image029
The manufacturing method of the resin composition of this embodiment is not specifically limited. For example, the following method can be used. When the solvent used in the synthesis of (a) the polyimide precursor is the same as the (b) organic solvent, the synthesized polyimide precursor solution can be directly used as the resin composition. In addition, it is also possible to add (b) organic solvent and one or more other components to the polyimide precursor at room temperature (25°C) to 80°C as needed, and stir and mix them for use as a resin combination Things. For this stirring and mixing, suitable devices such as a Trinity Motor (manufactured by Shinto Chemical Co., Ltd.) and a rotation and revolution mixer with stirring blades can be used. In addition, heat of 40~100°C may be applied as needed. On the other hand, when the solvent used in the synthesis of (a) polyimide precursor is different from (b) the organic solvent, the synthesized compound can also be synthesized by suitable methods such as reprecipitation and solvent distillation. After removing the solvent in the polyimide precursor solution and separating (a) the polyimide precursor, add (b) organic solvent and other ingredients as needed in the temperature range of room temperature to 80℃, and Stir and mix, thereby preparing a resin composition. After the resin composition is prepared as described above, the composition solution may be heated at, for example, 130 to 200° C., for example, 5 minutes to 2 hours, so that the polyimide precursor can be made to the extent that the polymer does not precipitate. A part is dehydrated and imidized. Here, by controlling the heating temperature and heating time, the imidization rate can be controlled. By partially imidizing the polyimide precursor, the viscosity stability of the resin composition during storage at room temperature can be improved. As the range of the imidization rate, from the viewpoint of achieving a balance between the solubility of the polyimide precursor to the resin composition solution and the storage stability of the solution, it is preferably set to 5% to 70%. The resin composition of this embodiment preferably has a moisture content of 3,000 ppm by mass or less. The moisture content of the resin composition is preferably 2500 mass ppm or less, preferably 2000 mass ppm or less, preferably 1500 mass ppm or less, more preferably 1,000 mass ppm from the viewpoint of viscosity stability when the resin composition is stored. Mass ppm or less, more preferably 500 mass ppm or less, preferably 300 mass ppm or less, and more preferably 100 mass ppm or less. The solution viscosity of the resin composition of this embodiment is preferably 500 to 200,000 mPa·s at 25° C., more preferably 2,000 to 100,000 mPa·s, and particularly preferably 3,000 to 30,000 mPa·s. The viscosity of the solution can be measured using an E-type viscometer (manufactured by Toki Industrial Co., Ltd., VISCONICEHD). If the viscosity of the solution is less than 300 mPa·s, it may be difficult to apply coating during film formation, and if it is higher than 200,000 mPa·s, it may become difficult to stir during synthesis. Even if the solution has a high viscosity during the synthesis of (a) the polyimide precursor, a resin composition with good viscosity can be obtained by adding a solvent after the reaction is completed and stirring. The resin composition of this embodiment has the following characteristics in a preferable aspect. After coating the resin composition on the surface of the support to form a coating film, the coating film is heated at 430°C for 1 hour under a nitrogen atmosphere (in nitrogen with an oxygen concentration of 2,000 ppm or less), thereby making the polyimide The polyimide film obtained by imidizing the precursor preferably has a yellowness of 20 or less when the film thickness is 10 μm. The yellowness at a film thickness of 10 μm is preferably 18 or less, preferably 16 or less, preferably 14 or less, preferably 13 or less, preferably 10 or less, and preferably 7 or less. In addition, the residual stress of the polyimide film thus obtained is preferably 25 MPa or less. Preferably, the residual stress is 23 MPa or less, 20 MPa or less, 18 MPa or less, and 16 MPa or less. In addition, the glass transition temperature Tg of the polyimide film thus obtained is preferably 360°C or higher. The preferred glass transition temperature Tg is 470°C or higher. In addition, the retardation Rth of the polyimide film obtained in this way at a film thickness of 10 μm is preferably 1000 nm or less. Preferably, the retardation Rth is 800 nm or less, 700 nm or less, 500 nm or less, 300 nm or less, 200 nm or less, 140 nm or less, and 100 nm or less. In addition, the tensile elongation at a thickness of 10 μm of the polyimide film thus obtained is preferably 15% or more. Preferably, the tensile elongation is 20% or more, 25% or more, 30% or more, 35% or more, and 40% or more. The resin composition of this embodiment can be suitably used for forming transparent substrates of display devices such as liquid crystal displays, organic electroluminescence displays, field emission displays, and electronic paper, for example. Specifically, it can be used to form thin film transistor (TFT) substrates, color filter substrates, transparent conductive film (ITO, Indium Thin Oxide) substrates, etc. Since the resin precursor of this embodiment can form a polyimide film with a residual stress of 25 MPa or less, it is easy to apply to a display manufacturing process with a TFT device on a colorless transparent polyimide substrate. <Resin film> Another aspect of the present invention provides a resin film formed from the above-mentioned resin precursor. Furthermore, another aspect of the present invention provides a method of manufacturing a resin film from the above-mentioned resin composition. The resin film in this embodiment is characterized by including the following steps: a step of forming a coating film by coating the above-mentioned resin composition on the surface of the support (coating step); by heating the above-mentioned support and the above-mentioned coating film And the step of imidizing the polyimide precursor contained in the coating film to form a polyimide resin film (heating step); and peeling off the polyimide resin film from the support Step (Peeling Step). Here, the support is not particularly limited as long as it has heat resistance at the heating temperature of the subsequent step and has good peelability. For example, it can be used: glass (such as alkali-free glass) substrate; silicon wafer; PET (polyethylene terephthalate), OPP (extended polypropylene), polyethylene terephthalate, polyethylene naphthalate Resin substrates such as diester, polycarbonate, polyimide, polyimide imine, polyetherimide, polyether ether ketone, polyether sulfide, polyphenylene sulfide, polyphenylene sulfide, etc.; stainless steel, alumina , Copper, nickel and other metal substrates. In the case of forming a film-shaped polyimide molded body, for example, a glass substrate, a silicon wafer, etc. are preferably formed, and in the case of forming a film-shaped or sheet-shaped polyimide molded body, for example, it is preferable to include Supports such as PET (polyethylene terephthalate), OPP (extended polypropylene), etc. As the coating method, for example, it can be applied: knife coater, air knife coater, roll coater, spin coater, flow coater, die nozzle coater, bar coater, etc. Methods; coating methods such as spin coating, spray coating, and dip coating; printing techniques represented by screen printing and gravure printing, etc. The coating thickness should be appropriately adjusted according to the required thickness of the resin film and the content of the polyimide precursor in the resin composition, preferably about 1 to 1,000 μm. It is sufficient to perform the coating step at room temperature, but in order to reduce the viscosity and improve the workability, the resin composition can also be heated in the range of 40 to 80°C. A drying step can be performed after the coating step, or the drying step can be omitted and the subsequent heating step can be directly entered. This drying step is performed in order to remove the organic solvent. In the case of the drying step, suitable devices such as hot plates, box dryers, and conveyor belt dryers can be used, for example. The drying step is preferably carried out at 80-200°C, more preferably at 100-150°C. The implementation time of the drying step is preferably set to 1 minute to 10 hours, more preferably set to 3 minutes to 1 hour. A coating film containing a polyimide precursor is formed on the support as described above. Then the heating step is carried out. The heating step is a step of removing the organic solvent remaining in the coating film in the above drying step, and subjecting the polyimide precursor in the coating film to an imidization reaction to obtain a polyimide-containing film. This heating step can be performed using, for example, an inert gas oven, a hot plate, a box dryer, and a conveyor belt dryer. This step can be carried out simultaneously with the above drying step, or two steps can be carried out one after the other. The heating step can also be carried out in an air atmosphere, but in terms of safety and the transparency and YI value of the obtained polyimide film, it is recommended to carry out in an inert gas atmosphere. As an inert gas, nitrogen gas, argon gas, etc. are mentioned, for example. The heating temperature can also be appropriately set according to (b) the type of organic solvent, preferably 250°C to 550°C, more preferably 300 to 450°C. If the temperature is 250°C or higher, the imidization is sufficient, and if the temperature is 550°C or lower, the obtained polyimide film will not suffer from the deterioration of the transparency or the deterioration of the heat resistance. The heating time is preferably set to about 0.5 to 3 hours. In this embodiment, the oxygen concentration of the surrounding atmosphere in the heating step is preferably 2,000 ppm by mass or less, more preferably 100 ppm by mass from the viewpoint of the transparency and YI value of the obtained polyimide film Hereinafter, it is more preferably 10 mass ppm or less. By heating in an atmosphere with an oxygen concentration of 2,000 mass ppm or less, the YI value of the obtained polyimide film can be 30 or less. Depending on the use and purpose of the polyimide resin film, a peeling step of peeling the resin film from the support may be necessary after the above heating step. The peeling step is preferably performed after cooling the resin film on the support to about room temperature to 50°C. As this peeling step, the following aspects (1) to (4) are mentioned, for example. (1) After the structure containing the polyimide resin film/support is produced by the above method, the laser is irradiated from the support side of the structure to ablate the interface between the support and the polyimide resin film Process to peel off the polyimide resin. As the type of laser, solid (YAG) laser, gas (UV excimer) laser, etc. can be cited. It is preferable to use a spectrum with a wavelength of 308 nm or the like (refer to Japanese Patent Application Publication No. 2007-512568, Japanese Patent Application Publication No. 2012-511173, etc.). (2) Before coating the resin composition on the support, a release layer is formed on the support, and then a structure comprising polyimide resin film/release layer/support is obtained, and the polyimide resin film is peeled off的方法。 The method. Examples include: using Parylene (registered trademark, manufactured by Japan Parylene Co., Ltd.) and tungsten oxide as the release layer; methods using vegetable oil, silicone, fluorine, alkyd, etc. mold release agents, etc. (Refer to Japanese Patent Laid-Open No. 2010-67957, Japanese Patent Laid-Open No. 2013-179306, etc.). The method (2) can also be used in combination with the laser irradiation of (1) above. (3) A method of using an etchable metal substrate as a support, and after obtaining a structure containing a polyimide resin film/support, using an etchant to etch the metal, thereby obtaining a polyimide resin film. As the metal, for example, copper (as a specific example, electrolytic copper foil "DFF" manufactured by Mitsui Metal Mining Co., Ltd.), aluminum, and the like can be used. As the etchant, ferric chloride or the like can be used for copper, and dilute hydrochloric acid or the like can be used for aluminum. (4) After obtaining the structure containing the polyimide resin film/support by the above method, stick the adhesive film on the surface of the polyimide resin film, and separate the adhesive film/polyimide resin from the support A method of separating the polyimide resin film from the adhesive film afterwards. Among these peeling methods, in terms of the refractive index difference, YI value, and elongation between the front and back surfaces of the obtained polyimide resin film, the method (1) or (2) is appropriate. From the viewpoint of the refractive index difference between the front surface and the back surface of the obtained polyimide resin film, the method (1) is more appropriate. Furthermore, in the method (3), when copper is used as a support, it can be seen that the YI value of the obtained polyimide resin film becomes larger, and the elongation tends to decrease. It can be considered as the influence of copper ions. The thickness of the resin film obtained by the above method is not particularly limited, but is preferably in the range of 1 to 200 μm, more preferably 5 to 100 μm. The resin film of this embodiment may have a yellowness YI of 20 or less when the film thickness is 10 μm. Such characteristics can be achieved, for example, by performing the resin precursor of the present invention under a nitrogen atmosphere (for example, in nitrogen with an oxygen concentration of 2,000 ppm or less), preferably at 400°C to 550°C, more preferably 400°C to 450°C. The imidization is well achieved. The resin film of this embodiment may further have a tensile elongation of 15% or more. The tensile elongation of the resin film may further be 20% or more, especially 30% or more. Thereby, the resin film of the present embodiment has excellent breaking strength when handling a flexible substrate, and therefore can improve the yield when manufacturing a flexible display. The tensile elongation can be measured by using a resin film with a thickness of 10 μm as a sample and using a commercially available tensile testing machine. <Laminate> Another aspect of the present invention provides a laminate including a support and a polyimide resin film formed of the above-mentioned resin composition on the surface of the support. Furthermore, another aspect of the present invention provides a method of manufacturing the above-mentioned laminated body. The laminate in this embodiment can be obtained by a method of manufacturing a laminate including the steps of: forming a coating film by coating the above-mentioned resin composition on the surface of the support (coating step); and by The step of forming a polyimide resin film by heating the support and the coating film to the polyimide precursor contained in the coating film (heating step). The manufacturing method of the said laminated body can be implemented similarly to the manufacturing method of the said resin film, for example except that a peeling process is not performed. This laminated body can be suitably used for the manufacture of a flexible device, for example. It will be explained in more detail as follows. In the case of forming a flexible display, a glass substrate is used as a support, a flexible substrate is formed thereon, and TFT and the like are formed thereon. The steps of forming TFTs on the flexible substrate are typically performed at a temperature in a wide range of 150 to 650°C. However, in the case of forming LTPS as TFT, compared with amorphous silicon (250°C) or IGZO (350°C), extremely high temperature is required, and heating of about 400°C to 550°C is required. On the other hand, due to the thermal history, the physical properties (especially yellowness or elongation) of the polyimide film tend to decrease. If it exceeds 400°C, the yellowness or elongation in particular decreases. However, the polyimide film obtained from the polyimide precursor of the present invention has very little reduction in yellowness or elongation even in a high temperature region above 400° C., and can be used well in this region. For the polyimide film of this embodiment, compared to the case formed on IGZO, good thermal cycle test results can be obtained when formed on LTPS. Therefore, the polyimide film of this embodiment can be suitably used when the device type of TFT is LTPS. Furthermore, in this embodiment, it is possible to provide a laminated body including a polyimide film layer including a polyimide represented by the following general formula (5) and an LTPS layer. [化14]
Figure 02_image031
As a method of manufacturing the laminate, after manufacturing a laminate comprising the support and a polyimide resin film formed from the resin composition on the surface of the support, an amorphous silicon layer is formed at 400~ After dehydrogenation annealing at 450°C for about 0.5 to 3 hours, it is then crystallized using an excimer laser or the like to form a low-temperature polysilicon layer. Thereafter, the glass and the polyimide film are peeled off by laser peeling or the like to obtain the above-mentioned laminate. In addition, an LTPS layer may be formed after an inorganic film such as SiO 2 or SiN is formed on the polyimide film if necessary. As the above-mentioned polyimide film layer, the following general formula (6) is more preferable from the viewpoint of haze and elongation. [化15]
Figure 02_image033
At this time, the higher the residual stress generated in the glass substrate and the polyimide resin film, the more likely it is that glass will be produced when the laminate comprising the two expands in the TFT formation step at high temperature and then shrinks during cooling at room temperature. Problems such as warpage and damage of the substrate, peeling of the flexible substrate from the glass substrate, etc. Generally speaking, the thermal expansion coefficient of the glass substrate is smaller than that of the resin, so residual stress is generated between the glass substrate and the flexible substrate. As described above, the resin film of this embodiment can set the residual stress generated between the glass substrate and the glass substrate to 25 MPa or less, so it can be suitably used for the formation of flexible displays. Furthermore, in the polyimide film of this embodiment, the yellowness YI at the film thickness of 10 μm when the polyimide film is heated at 430 degrees can be set to 20 or less, and the tensile elongation can be set to 15 %above. Thereby, the resin film of the present embodiment has excellent breaking strength when handling a flexible substrate, and therefore can improve the yield when manufacturing a flexible display. The above-mentioned aspect is an explanation of an embodiment of the production of an LTPS-TFT substrate for a flexible display, and an embodiment as a display device is described below. As a flexible display, an organic EL display can be mentioned, for example. The organic EL display is a so-called flexible display in which the display portion can be flexibly deformed (with flexibility). FIG. 1 is a diagram showing a part of the structure of the organic EL structure part 25. As shown in FIG. The organic EL structure 25 is formed on the lower substrate 2a including the glass substrate 21, the light-heat exchange film 22, the transparent resin layer 23, and the undercoat layer 24, and includes the same structural members as those constituting a general organic EL display, such as The organic EL element 250a that emits red light, the organic EL element 250b that emits green light, and the organic EL element 250c that emits blue light are arranged in a matrix as a unit, and each organic EL element is divided by a partition (bank) 251 Luminous area. Each organic EL element includes a lower electrode (anode) 252, a hole transport layer 253, a light emitting layer 254, and an upper electrode (cathode) 255. In addition, a plurality of TFTs 256 (a-Si, p-Si, oxide semiconductor) for driving organic EL elements are provided on the lower substrate 2a. (Manufacturing method of organic EL display) The manufacturing steps of the organic EL display 20 include an organic EL substrate manufacturing step, a sealing substrate manufacturing step, an assembly step of bonding two substrates, and a peeling step of peeling off the glass substrates 21 and 29. The organic EL substrate manufacturing step, the sealing substrate manufacturing step, and the assembly step can apply well-known manufacturing steps. One example is given below, but it is not limited to this. In addition, the peeling step is the same as the peeling step of the polyimide film described above. For example, first, after an LTPS-TFT substrate for a flexible display is produced by the above-mentioned method, an interlayer insulating film provided with contact holes is formed using a photosensitive acrylic resin or the like. An ITO film is formed by a sputtering method or the like, and the lower electrode is formed in a pair with the TFT. Next, after forming the partition wall using photosensitive polyimide or the like, a hole transport layer and a light-emitting layer are formed in each space partitioned by the partition wall. In addition, the upper electrode is formed so as to cover the light-emitting layer and the partition wall. The organic EL substrate is produced through the above steps, and is sealed with a sealing film or the like, thereby producing a top emission type flexible organic EL display. The bottom emission type flexible organic EL display can also be manufactured by a well-known method. In addition, after the above-mentioned LTPS-TFT substrate is produced, a color filter glass substrate with colorless and transparent polyimide is produced. On one of the TFT substrate and the CF substrate, a thermosetting epoxy resin is included by screen printing. The sealing material is coated with a frame-like pattern in the part lacking the liquid crystal injection port, and spherical spacers containing plastic or silicon dioxide, which have a diameter equivalent to the thickness of the liquid crystal layer, are spread on another substrate. Then, the TFT substrate and the CF substrate are bonded together to harden the sealing material. Finally, in the space surrounded by the TFT substrate and the CF substrate and the sealing material, the liquid crystal material is injected by the pressure reduction method, and then a thermosetting resin is applied to the liquid crystal injection port, and the liquid crystal material is sealed by heating, thereby forming a liquid crystal Floor. Finally, the glass substrate on the CF side and the glass substrate on the TFT side are peeled off by a laser peeling method, etc., thereby making a flexible liquid crystal display. Therefore, another aspect of the present invention provides a display substrate. Furthermore, another aspect of the present invention provides a method of manufacturing the above-mentioned display substrate. The manufacturing method of the display substrate in this embodiment is characterized by including the following steps: a step of forming a coating film by coating the above-mentioned resin composition on the surface of the support (coating step); The step of heating the coating film to imidize the polyimide precursor contained in the coating film to form a polyimide resin film (heating step); forming an element on the polyimide resin film Or a step of circuit formation (element and circuit formation step); and a step of peeling the polyimide resin film on which the aforementioned element or circuit is formed from the above-mentioned support (peeling step). In the above-mentioned method, the coating step, the heating step, and the peeling step can be performed in the same manner as the above-mentioned method of manufacturing the resin film, respectively. The steps of forming components and circuits can be implemented by methods known to the industry. The resin film of this embodiment that satisfies the above-mentioned physical properties can be suitably used for applications whose use is restricted due to the yellow color of existing polyimide films, and can be particularly suitably used for colorless transparent substrates and color filters for flexible displays. Uses such as protective film for optical sheets. Further, for example, it can also be used in protective films, TFT-LCDs, etc., as diffuse films and coating films (such as TFT-LCD intermediate layers, gate insulating films, liquid crystal alignment films, etc.), ITO substrates for touch panels, and smartphones Cover glass replaces resin substrates and other fields that require colorless transparency and low birefringence. The polyimide precursor of this embodiment, the resin film and the laminate produced using the resin precursor can be used as semiconductor insulating films, TFT-LCD insulating films, electrode protection films, etc., and can also be used in flexible devices. Especially suitable for use as a substrate in manufacturing. Here, examples of flexible devices to which the resin film and laminate of the present embodiment can be applied include flexible displays, flexible solar cells, flexible touch panel electrode substrates, flexible lighting, and flexible batteries. [Examples] Hereinafter, the present invention will be further described in detail based on examples, but these are described for the purpose of explanation, and the scope of the present invention is not limited to the following examples. Various evaluations in the examples and comparative examples were performed as follows. <Measurement of weight average molecular weight> The weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured under the following conditions using a gel permeation chromatography (GPC). As a solvent, NMP (manufactured by Wako Pure Chemical Industries, Ltd., used for high performance liquid chromatography, added 24.8 mmol/L of lithium bromide monohydrate (manufactured by Wako Pure Chemical Industries, 99.5% purity) and 63.2 mmol/L immediately before the measurement. Phosphoric acid of L (manufactured by Wako Pure Chemical Industries, Ltd., used for high performance liquid chromatography) and dissolved). The calibration curve for calculating the weight average molecular weight was prepared using standard polystyrene (manufactured by Tosoh Corporation). Column: Shodex KD-806M (manufactured by Showa Denko) Flow rate: 1.0 mL/min Column temperature: 40°C Pump: PU-2080Plus (manufactured by JASCO) Detector: RI-2031Plus (RI: differential refractometer, JASCO) Manufacturing) and UV-2075Plus (UV-VIS: UV-Vis Absorbance Meter, manufactured by JASCO) <Evaluation of the content of molecules with a molecular weight of less than 1,000 (low-molecular polymer content)> The content of molecules with a molecular weight of less than 1,000 in the resin It is calculated as the ratio (percentage) of the peak area of the component with a molecular weight of less than 1,000 to the peak area of the total molecular weight distribution using the GPC measurement result obtained above. <Evaluation of Moisture Content> The moisture content of the synthetic solvent and the resin composition (varnish) was measured using a Kafka moisture measuring device (micro-moisture measuring device AQ-300, manufactured by Hiranuma Sangyo Co., Ltd.). <Evaluation of the viscosity stability of the resin composition> For the resin composition prepared in each of the Examples and Comparative Examples, the prepared sample was left standing at room temperature for 3 days as the prepared sample and the viscosity was measured at 23°C ; After that, the sample that was left to stand at room temperature for 2 weeks was used as the sample after 2 weeks, and the viscosity measurement at 23°C was performed again. These viscosity measurements were performed using a viscometer (TV-22 manufactured by Toki Sangyo Co., Ltd.) with a temperature regulator. Using the above-mentioned measured values, the rate of change in viscosity in 2 weeks at room temperature was calculated by the following formula. Viscosity change rate in 2 weeks at room temperature (%)=[(Viscosity of sample after 2 weeks)-(Viscosity of sample after preparation)]/(Viscosity of sample after preparation)×100 Viscosity change rate in 2 weeks at room temperature The evaluation was performed according to the following criteria. ◎: Viscosity change rate is 5% or less (storage stability "good") ○: Viscosity change rate is more than 5 and less than 10% (storage stability "good") ×: Viscosity change rate is more than 10% (storage stability "Poor")<Evaluation of varnish coating properties> The resin composition prepared in each of the Examples and Comparative Examples was coated on an alkali-free glass substrate (size 37 ×47 mm, thickness 0.7 mm) after mounting, pre-baking at 140 ℃ for 60 minutes. A profiler (manufactured by Tencor, model name P-15) was used to measure the step difference on the surface of the coating film to evaluate the coatability of the varnish. ◎: The level difference on the surface is 0.1 μm or less ("good coatability") ○: The level difference on the surface exceeds 0.1 and less than 0.5 μm (the coatability is "good") ×: The level difference on the surface exceeds 0.5 μm (paint "Poor fabric properties") <Evaluation of residual stress> Apply each resin composition by a spin coater on a 6-inch silicon wafer with a thickness of 625 μm±25 μm whose "warpage" has been measured in advance. Pre-bake at 100°C for 7 minutes. After that, a vertical curing furnace (manufactured by Koyo Lindberg, model name VF-2000B) was used to adjust so that the oxygen concentration in the library became 10 mass ppm or less, and heat curing treatment (curing treatment) was performed at 430°C for 1 hour. ), and fabricate a silicon wafer with a polyimide resin film with a thickness of 10 μm after curing. A residual stress measuring device (manufactured by Tencor, model name FLX-2320) was used to measure the amount of warpage of the wafer, and to evaluate the residual stress generated between the silicon wafer and the resin film. <Evaluation of yellowness (YI value)> The resin composition prepared in each example and comparative example was spin-coated on a 6-inch silicon wafer with an aluminum vapor deposition layer on the surface so that the film thickness after curing became 10 μm On the substrate, pre-baked at 100°C for 7 minutes. Thereafter, a vertical curing furnace (manufactured by Koyo Lindberg, model name VF-2000B) was used to adjust so that the oxygen concentration in the library became 10 mass ppm or less, and heat and hardened at 430°C for 1 hour to produce Wafer formed with polyimide resin film. The laminate wafer obtained above was immersed in a dilute hydrochloric acid aqueous solution, and the polyimide film was peeled from the wafer, thereby obtaining a sample of the polyimide film with an inorganic film formed on the surface. For the obtained polyimide resin film, the YI value (converted to a film thickness of 10 μm) was measured using a D65 light source (Spectrophotometer: SE600) manufactured by Nippon Denshoku Industries Co., Ltd. <Evaluation of elongation and breaking strength> Wafers were produced in the same manner as in the above-mentioned <Evaluation of yellowness>. Use a wafer dicing machine (DAD 3350 manufactured by DISCO Co., Ltd.) to cut a 3 mm width cut into the polyimide resin film of the wafer, and immerse it in a dilute hydrochloric acid aqueous solution overnight, peel off the resin film and make it dry. Cut it to a length of 50 mm to make a sample. For the above samples, the elongation and breaking strength were measured using TENSILON (UTM-II-20 manufactured by Orientec) at a test speed of 40 mm/min and an initial load of 0.5 fs. [Synthesis example 1] In a 3 L separable flask with a stir bar equipped with an oil bath, NMP1 (1065 g) was added while nitrogen was introduced, and 4,4'-diaminodiphenyl sulfide was added while stirring ( 248.3 g) as the diamine, then PMDA (218.12 g) as the acid dianhydride was added and stirred at room temperature for 30 minutes. After raising the temperature to 50°C and stirring for 12 hours, the oil bath was removed and returned to room temperature to obtain a transparent polyamide acid NMP solution (hereinafter also referred to as varnish) (varnish P-1). The composition here and the weight average molecular weight (Mw) of the obtained polyamide acid are shown in Table 1, respectively. In addition, the test results of the film cured at 430°C are shown in Table 2. [Example 1] In a 3 L separable flask with a stir bar equipped with an oil bath, NMP2 (1065 g) was added while introducing nitrogen gas, and 4,4'-diaminodiphenyl sulfide was added while stirring ( 248.3 g) as the diamine, then PMDA (218.12 g) as the acid dianhydride was added and stirred at room temperature for 30 minutes. After raising the temperature to 80°C and stirring for 3 hours, the oil bath was removed and returned to room temperature to obtain a transparent polyamide acid NMP solution (hereinafter also referred to as varnish) (varnish P-2). The composition here and the weight average molecular weight (Mw) of the obtained polyamide acid are shown in Table 1, respectively. In addition, the test results of the film cured at 430°C are shown in Table 2. [Example 2] Except that NMP2 was changed to NMP3, it was synthesized by the same method as Example 1 (varnish P-3). The results are shown in Tables 1 and 2. [Example 3] Except for adding 4,4'-diaminodiphenyl chloride as the first diamine to the amine so that the molar ratio becomes 99.33:0.67, and the modification of both terminal amines as the second diamine It was synthesized by the same method as in Example 2 except for the methyl phenyl silicone oil (Varnish P-4). The results are shown in Table 1 and Table 2. [Example 4 to Example 13] Except that the types and molar ratios of the first diamine and the second diamine were changed as shown in Table 1 in the amine, the synthesis was carried out in the same manner as in Example 3 (Varnish P -5~P-14). The results are shown in Table 1 and Table 2. [Example 14] In addition to adding pyromellitic dianhydride as the first acid dianhydride and biphenyltetracarboxylic dianhydride as the second acid dianhydride to the acid dianhydride so that the molar ratio becomes 80:20 Except for the anhydride, it was synthesized by the same method as in Example 2 (varnish P-15). The results are shown in Table 1 and Table 2. [Example 15 to Example 17] In the acid dianhydride, except that the molar ratio of the first acid dianhydride and the second acid dianhydride was changed as shown in Table 1, the synthesis was carried out by the same method as in Example 2 ( Varnishes P-16~P-18). The results are shown in Table 1 and Table 2. [Example 18] It was synthesized by the same method as in Example 2 except that 4,4'-diaminodiphenyl sulfide was changed to 3,3'-diaminodiphenyl sulfide in the diamine ( Varnish P-19). [Comparative Example 1 to Comparative Example 6] Except that the acid dianhydride and diamine were changed as in Table 1, it was synthesized by the same method as in Example 2 (varnish P-20 to varnish P-25). The composition in the above examples and comparative examples and the weight average molecular weight (Mw) of the obtained polyamide acid are shown in Table 1, respectively. In addition, the test results of the film cured at 430°C are shown in Table 2. [Table 1]
Figure 106129267-A0304-0001
 The abbreviations of the components in the table have the following meanings. PMDA: Pyromellitic dianhydride BPDA: Biphenyl tetracarboxylic dianhydride 4,4'-DAS: 4,4'-diaminodiphenyl sulfide 3,3'-DAS: 3,3'-diamine APAB: 4-aminophenyl-4-aminobenzoate p-PD: p-phenylenediamine 6FDA: 4,4'-(hexafluoroisopropylidene) diphthalate Anhydride CHDA: 1,4-cyclohexanediamine DSDA: 3,3',4,4'-diphenyl tetracarboxylic dianhydride HPMDA: 1,2,4,5-cyclohexane tetracarboxylic dianhydride Anhydride TFMB: 2,2'-bis(trifluoromethyl)benzidine X-22-1660B-3: Two-terminal amine modified methyl phenyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd.) NMP1: 500 ml bottled product One month after opening, the moisture content is 3,070 ppm NMP2: After opening the 500 ml bottle and leaving it for one week, the moisture content is 1500 ppm. NMP3: The 18 L barrel has just opened the latter, and the moisture content is 250 ppm [Table 2]
Figure 106129267-A0304-0002
 As shown in Table 1 and Table 2, it can be seen that the resin composition of Synthetic Example 1, the resin composition of Examples 1 to 18 and the resin composition of Comparative Examples 1 to 6 having the structure represented by the general formula (1) have residual stress Smaller, lower yellowness, higher elongation. Especially in Examples 1-18 where the weight average molecular weight of the polyimide precursor is 40,000 or more and 300,000 or less, and the content of molecules with a weight average molecular weight of less than 1,000 is less than 5% by mass, it is similar to Synthesis Example 1. The specific elongation is larger, and particularly good results can be obtained. Specifically, a resin film with residual stress of 25 MPa or less, yellowness YI of 20 or less, and elongation of 15% or more can be obtained. In addition, comparing Synthesis Example 1 with Examples 1 and 2, it can be seen that the smaller the water content of the solvent used in the polymerization reaction, the smaller the content of molecules with a molecular weight of less than 1,000. [Synthesis Examples, Examples 1 to 18, Comparative Examples 1 to 6] An organic EL substrate as shown in FIG. 1 was produced. Use a bar coater to coat the polyimide precursor varnish of Synthesis Example 1, Examples, and Comparative Examples on a plain glass substrate (thickness 0.7 mm) so that the film thickness after curing becomes 10 μm. Pre-bake at 140°C for 60 minutes. Then use a vertical curing furnace (manufactured by Koyo Lindberg, model name VF-2000B) to adjust the oxygen concentration in the library to be 10 mass ppm or less, and heat and harden at 430°C for 1 hour to produce a polymer A glass substrate of imide resin film. Then, a SiN layer was formed with a thickness of 100 nm by a CVD (Chemical Vapor Deposition) method. Then, a titanium film is formed by a sputtering method, and then patterned by a photolithography method to form a scanning signal line. Next, a SiN layer was formed with a thickness of 100 nm by the CVD method on the entire glass substrate on which the scanning signal lines were formed. (So far, set as the lower substrate 2a) Next, an amorphous silicon layer 256 is formed on the lower substrate 2a, dehydrogenation annealing is performed at 430° C. for 1 hour, and then an excimer laser is irradiated to form an LTPS layer. After that, a photosensitive acrylic resin is coated on the entire surface of the lower substrate 2a by a spin coating method, and exposed and developed by a photolithography method to form an interlayer insulating film 258 having a plurality of contact holes 257. Through the contact hole 257, a part of each LTPS 256 is exposed. Next, an ITO film is formed on the entire surface of the lower substrate 2a where the interlayer insulating film 258 is formed by a sputtering method, exposed and developed by a photolithography method, and patterned by an etching method to be compatible with each LTPS The lower electrodes 259 are formed in pairs. Furthermore, in each contact hole 257, the lower electrode 252 of the penetrating interlayer insulating film 258 is electrically connected to the LTPS256. Next, after the partition wall 251 is formed, a hole transport layer 253 and a light-emitting layer 254 are formed in each space divided by the partition wall 251. In addition, the upper electrode 255 is formed so as to cover the light-emitting layer 254 and the partition wall 251. Through the above steps, an organic EL substrate is produced. Next, an ultraviolet curable resin is applied to the periphery of the sealing substrate 2b on which the glass substrate, the polyimide film of this embodiment, and the SiN layer are sequentially formed, and the sealing substrate 2b and the organic EL substrate are bonded in an argon atmosphere. This encapsulates the organic EL element. Thereby, a hollow portion 261 is formed between each organic EL element and the sealing substrate 2b. Excimer lasers (wavelength 308 nm, repetition frequency 300 Hz) are irradiated from the lower substrate 2a side and the sealing substrate 2b side of the laminate thus formed, and peeling is performed with the minimum energy required for peeling the entire surface. Evaluation of the presence or absence of substrate warpage, lighting test, and evaluation of white turbidity of the laminate after peeling off the laminate. In addition, a thermal cycle test was also carried out. The results are shown in Table 3. <Substrate warpage> ◎: No warpage ○: Slight warpage Δ: Rolled up due to warpage <Lighting test> ○: Lighted ×: Not lighted <Evaluation of white turbidity of the laminate> After forming the laminate , By visual observation, the device with overall transparency is regarded as ○, the one with a little white turbidity is regarded as Δ, and the one with white turbidity is regarded as ×. <Thermal cycle test> Using the thermal cycle tester manufactured by Espec, the cycle test was performed 1000 times at -5°C and 60°C for 30 minutes (the tank moving time is 1 minute), and then the appearance was observed. If there is no peeling or bulging, it is regarded as ○, after the test, where a very small part of peeling or bulging is observed, it is regarded as Δ, and when peeling or bulging is observed on the entire surface after the test, it is regarded as x. [table 3]
Figure 106129267-A0304-0003
 As shown in Table 3, in Examples 1-18 using varnishes P-2~P-19, a laminate with no warpage of the substrate, good lighting test, no white turbidity, and good thermal cycle characteristics can be obtained. body. Such a laminate can be suitably used as a low-temperature polysilicon TFT element substrate, such as a transparent flexible substrate of an organic EL display. The present invention is not limited to the above-mentioned embodiment, and can be implemented with various changes without departing from the gist of the invention. [Industrial Applicability] By using the polyimide precursor and resin composition of the present invention, a resin with residual stress of 25 MPa or less, yellowness YI of 20 or less, and elongation of 15% or more can be obtained membrane. Such a resin film can be applied to, for example, semiconductor insulating films, TFT-LCD insulating films, electrode protection films, etc., and can also be particularly suitably used as a substrate in the manufacture of flexible displays, substrates for touch panel ITO electrodes, and the like.

2a‧‧‧下部基板2b‧‧‧密封基板20‧‧‧有機EL顯示器21‧‧‧玻璃基板22‧‧‧光熱交換膜23‧‧‧透明樹脂層24‧‧‧底塗層25‧‧‧有機EL結構部29‧‧‧玻璃基板250a‧‧‧發出紅色光之有機EL元件250b‧‧‧發出綠色光之有機EL元件250c‧‧‧發出藍色光之有機EL元件251‧‧‧隔離壁(堤)252‧‧‧下部電極(陽極)253‧‧‧電洞傳輸層254‧‧‧發光層255‧‧‧上部電極(陰極)256‧‧‧LTPS257‧‧‧接觸孔258‧‧‧層間絕緣膜259‧‧‧下部電極261‧‧‧中空部2a‧‧‧Lower substrate 2b‧‧‧Sealing substrate 20‧‧‧Organic EL display 21‧‧‧Glass substrate 22‧‧‧Light heat exchange film 23‧‧‧Transparent resin layer 24‧‧‧Undercoating 25‧‧‧ Organic EL structure 29‧‧‧Glass substrate 250a‧‧‧Red light-emitting organic EL element 250b‧‧‧Green light-emitting organic EL element 250c‧‧‧Blue light-emitting organic EL element 251‧‧‧Partition wall ( Embankment) 252‧‧‧Lower electrode (anode) 253‧‧‧Hole transport layer 254‧‧‧Light-emitting layer 255‧‧‧Upper electrode (cathode) 256‧‧‧LTPS257 Membrane 259‧‧‧Lower electrode 261‧‧‧Hollow part

圖1係表示將本發明應用於有機EL基板之有機EL結構之圖。Fig. 1 is a diagram showing an organic EL structure in which the present invention is applied to an organic EL substrate.

Figure 106129267-A0101-11-0001-2
Figure 106129267-A0101-11-0001-2

Claims (48)

一種低溫多晶矽TFT元件之基板用之樹脂組合物，其特徵在於：其包含使二胺成分與酸二酐成分聚合而獲得之聚醯亞胺前驅體、及溶劑，並且上述聚醯亞胺前驅體包含(a)下述通式(1)：
Figure 106129267-A0305-02-0055-1
 所表示之結構，且上述聚醯亞胺前驅體於將上述二胺成分與上述酸二酐成分之總質量設為100質量%時，包含下述式(3)：
Figure 106129267-A0305-02-0055-2
 (式中，存在複數個之R3及R4分別獨立地為碳數1~20之一價之有機基，而且h為3~200之整數)所表示之結構之矽酮二胺成分，且該矽酮二胺成分之含量未達6質量%。 A resin composition for a substrate of a low-temperature polysilicon TFT element, characterized in that it comprises a polyimide precursor obtained by polymerizing a diamine component and an acid dianhydride component, and a solvent, and the polyimide precursor Contains (a) the following general formula (1):
Figure 106129267-A0305-02-0055-1
 The structure shown, and the polyimide precursor, when the total mass of the diamine component and the acid dianhydride component is 100% by mass, includes the following formula (3):
Figure 106129267-A0305-02-0055-2
 (In the formula, there are a plurality of R 3 and R 4 each independently being a monovalent organic group with 1 to 20 carbons, and h is an integer from 3 to 200) The silicone diamine component of the structure represented, and The content of the silicone diamine component is less than 6% by mass. 如請求項1之低溫多晶矽TFT元件之基板用之樹脂組合物，其中上述聚醯亞胺前驅體包含下述通式(2)：
Figure 106129267-A0305-02-0056-3
 所表示之結構。 According to claim 1, the resin composition for substrates of low-temperature polysilicon TFT devices, wherein the polyimide precursor comprises the following general formula (2):
Figure 106129267-A0305-02-0056-3
 The structure represented. 如請求項1或2之低溫多晶矽TFT元件之基板用之樹脂組合物，其中上述聚醯亞胺前驅體之重量平均分子量為4萬以上且30萬以下。 The resin composition for substrates of low-temperature polysilicon TFT devices of claim 1 or 2, wherein the weight average molecular weight of the polyimide precursor is 40,000 or more and 300,000 or less. 如請求項1之低溫多晶矽TFT元件之基板用之樹脂組合物，其中於將上述樹脂組合物中所含之固形物成分之總重量設為100質量%時，該固形物成分中所含有之分子量未達1,000之分子之量未達5質量%。 The resin composition for a substrate of a low-temperature polysilicon TFT element of claim 1, wherein when the total weight of the solid content contained in the resin composition is set to 100% by mass, the molecular weight contained in the solid content The amount of molecules less than 1,000 is less than 5% by mass. 如請求項4之低溫多晶矽TFT元件之基板用之樹脂組合物，其中上述固形物成分中所含有之上述分子量未達1,000之分子之量為1質量%以下。 The resin composition for a substrate of a low-temperature polysilicon TFT element according to claim 4, wherein the amount of molecules with a molecular weight of less than 1,000 contained in the solid component is 1% by mass or less. 如請求項1之低溫多晶矽TFT元件之基板用之樹脂組合物，其中上述矽酮二胺成分之含量為5.9質量%以下。 The resin composition for a substrate of a low-temperature polysilicon TFT element of claim 1, wherein the content of the silicone diamine component is 5.9% by mass or less. 如請求項6之低溫多晶矽TFT元件之基板用之樹脂組合物，其中上述矽酮二胺成分之含量為3質量%以下。 The resin composition for substrates of low-temperature polysilicon TFT devices of claim 6, wherein the content of the silicone diamine component is 3% by mass or less. 如請求項1或2之低溫多晶矽TFT元件之基板用之樹脂組合物，其中上述聚醯亞胺前驅體於將上述二胺成分之總莫耳數設為100莫耳%時，上述聚醯亞胺前驅體所含之下述通式(4)：
Figure 106129267-A0305-02-0057-4
 (式中，R1、R2、R3分別獨立地表示碳數1~20之一價之有機基；n表示0或1；而且a、b及c為0~4之整數)所表示之二胺之量為48莫耳%以下。 For example, the resin composition for substrates of low-temperature polysilicon TFT devices of claim 1 or 2, wherein the polyimide precursor is set to 100 mol% when the total molar number of the diamine component is set to 100 mol%. The following general formula (4) contained in the amine precursor:
Figure 106129267-A0305-02-0057-4
 (In the formula, R 1 , R 2 , R 3 each independently represent a monovalent organic group with 1 to 20 carbon atoms; n represents 0 or 1; and a, b, and c are integers from 0 to 4) The amount of diamine is 48 mol% or less. 如請求項8之低溫多晶矽TFT元件之基板用之樹脂組合物，其中上述聚醯亞胺前驅體所含之上述通式(4)所表示之二胺之量未達1莫耳%。 The resin composition for a substrate of a low-temperature polysilicon TFT device of claim 8, wherein the amount of the diamine represented by the general formula (4) contained in the polyimide precursor is less than 1 mol%. 如請求項9之低溫多晶矽TFT元件之基板用之樹脂組合物，其中上述聚醯亞胺前驅體所含之上述通式(4)所表示之二胺之量為0.9莫耳%以下。 The resin composition for a substrate of a low-temperature polysilicon TFT device according to claim 9, wherein the amount of the diamine represented by the general formula (4) contained in the polyimide precursor is 0.9 mol% or less. 如請求項8之低溫多晶矽TFT元件之基板用之樹脂組合物，其中上述聚醯亞胺前驅體包含4-胺基苯基-4-胺基苯甲酸酯作為上述通式(4)所表示之二胺成分。 The resin composition for a substrate of a low-temperature polysilicon TFT element according to claim 8, wherein the polyimide precursor includes 4-aminophenyl-4-aminobenzoate as represented by the general formula (4) The diamine component. 如請求項11之低溫多晶矽TFT元件之基板用之樹脂組合物，其中上述聚醯亞胺前驅體於將上述二胺成分之總莫耳數設為100莫耳%時，上述4-胺基苯基-4-胺基苯甲酸酯之含量為48莫耳%以下。 For example, the resin composition for substrates of low-temperature polysilicon TFT devices of claim 11, wherein the polyimide precursor, when the total moles of the diamine components are set to 100 mole%, the 4-aminobenzene The content of 4-aminobenzoic acid ester is 48 mol% or less. 如請求項12之低溫多晶矽TFT元件之基板用之樹脂組合物，其中上述聚醯亞胺前驅體中上述4-胺基苯基-4-胺基苯甲酸酯之含量未達1莫耳%。 The resin composition for substrates of low-temperature polysilicon TFT devices of claim 12, wherein the content of the 4-aminophenyl-4-aminobenzoate in the polyimide precursor is less than 1 mol% . 如請求項13之低溫多晶矽TFT元件之基板用之樹脂組合物，其中上述聚醯亞胺前驅體中上述4-胺基苯基-4-胺基苯甲酸酯之含量未達0.9莫耳%。 The resin composition for substrates of low-temperature polysilicon TFT devices of claim 13, wherein the content of the 4-aminophenyl-4-aminobenzoate in the polyimide precursor is less than 0.9 mol% . 如請求項1或2之低溫多晶矽TFT元件之基板用之樹脂組合物，其中上述聚醯亞胺前驅體包含二胺基二苯基碸作為上述二胺成分。 The resin composition for a substrate of a low-temperature polysilicon TFT device of claim 1 or 2, wherein the polyimide precursor contains diaminodiphenyl sulfide as the diamine component. 如請求項15之低溫多晶矽TFT元件之基板用之樹脂組合物，其中上述聚醯亞胺前驅體於將上述二胺成分之總莫耳數設為100莫耳%時，上述二胺基二苯基碸之含量為90莫耳%以上。 Such as the resin composition for substrates of low-temperature polysilicon TFT devices of claim 15, wherein the polyimide precursor, when the total moles of the diamine components are set to 100 mole%, the diaminodiphenyl The content of base waste is more than 90 mol%. 如請求項1或2之低溫多晶矽TFT元件之基板用之樹脂組合物，其中上述聚醯亞胺前驅體包含均苯四甲酸二酐作為上述酸二酐成分。 The resin composition for substrates of low-temperature polysilicon TFT devices of claim 1 or 2, wherein the polyimide precursor contains pyromellitic dianhydride as the acid dianhydride component. 如請求項17之低溫多晶矽TFT元件之基板用之樹脂組合物，其中上述聚醯亞胺前驅體於將上述酸二酐成分之總莫耳數設為100莫耳%時，上述均苯四甲酸二酐之含量為90莫耳%以上。 Such as the resin composition for substrates of low-temperature polysilicon TFT devices of claim 17, wherein the polyimide precursor, when the total moles of the acid dianhydride components are set to 100 mole%, the pyromellitic acid The content of dianhydride is more than 90 mol%. 如請求項1或2之低溫多晶矽TFT元件之基板用之樹脂組合物，其中將上述樹脂組合物於430℃下加熱1小時而獲得之聚醯亞胺膜之黃度於膜厚10μm時為20以下。 The resin composition for substrates of low-temperature polysilicon TFT devices of claim 1 or 2, wherein the polyimide film obtained by heating the above resin composition at 430°C for 1 hour has a yellowness of 20 when the film thickness is 10 μm the following. 如請求項19之低溫多晶矽TFT元件之基板用之樹脂組合物，其中將上述樹脂組合物於430℃下加熱1小時而獲得之聚醯亞胺膜之黃度於膜厚10μm時為13以下。 The resin composition for a substrate of a low-temperature polysilicon TFT element according to claim 19, wherein the yellowness of the polyimide film obtained by heating the above-mentioned resin composition at 430° C. for 1 hour is 13 or less when the film thickness is 10 μm. 如請求項1或2之低溫多晶矽TFT元件之基板用之樹脂組合物，其中將上述樹脂組合物於430℃下加熱1小時而獲得之聚醯亞胺膜之玻璃轉移溫度為360℃以上。 The resin composition for substrates of low-temperature polysilicon TFT devices of claim 1 or 2, wherein the glass transition temperature of the polyimide film obtained by heating the above-mentioned resin composition at 430°C for 1 hour is 360°C or higher. 如請求項21之低溫多晶矽TFT元件之基板用之樹脂組合物，其中將上述樹脂組合物於430℃下加熱1小時而獲得之聚醯亞胺膜之玻璃轉移溫度為470℃以上。 The resin composition for a substrate of a low-temperature polysilicon TFT element according to claim 21, wherein the glass transition temperature of the polyimide film obtained by heating the above-mentioned resin composition at 430°C for 1 hour is 470°C or higher. 如請求項1或2之低溫多晶矽TFT元件之基板用之樹脂組合物，其中將上述樹脂組合物於430℃下加熱1小時而獲得之聚醯亞胺膜之延遲於膜厚10μm時為1000nm以下。 The resin composition for substrates of low-temperature polysilicon TFT devices of claim 1 or 2, wherein the polyimide film obtained by heating the above resin composition at 430°C for 1 hour has a retardation of 1000 nm or less when the film thickness is 10 μm . 如請求項23之低溫多晶矽TFT元件之基板用之樹脂組合物，其中將上述樹脂組合物於430℃下加熱1小時而獲得之聚醯亞胺膜之延遲於膜厚10μm時為140nm以下。 The resin composition for a substrate of a low-temperature polysilicon TFT element according to claim 23, wherein the polyimide film obtained by heating the above-mentioned resin composition at 430° C. for 1 hour has a retardation of 140 nm or less when the film thickness is 10 μm. 一種樹脂膜之製造方法，其特徵在於包括如下步驟：於支持體之表面上塗佈如請求項1至24中任一項之樹脂組合物之步驟；由上述樹脂組合物形成聚醯亞胺樹脂膜之步驟；及將上述聚醯亞胺樹脂膜自上述支持體剝離之步驟。 A method for manufacturing a resin film, characterized by comprising the steps of: coating a resin composition as claimed in any one of claims 1 to 24 on the surface of a support; forming a polyimide resin from the above resin composition The step of filming; and the step of peeling the polyimide resin film from the support. 如請求項25之樹脂膜之製造方法，其中於將上述聚醯亞胺樹脂膜自上述支持體剝離之步驟之前，進行自上述支持體側照射雷射之步驟。 The method for manufacturing a resin film according to claim 25, wherein the step of irradiating a laser from the side of the support is performed before the step of peeling the polyimide resin film from the support. 一種顯示器之製造方法，其包括藉由如請求項25或26之方法而製造樹脂膜之方法。 A method of manufacturing a display, which includes a method of manufacturing a resin film by the method of claim 25 or 26. 一種積層體之製造方法，其包括如下步驟：於支持體之表面上塗佈如請求項1至24中任一項之樹脂組合物之步驟；由上述樹脂組合物形成聚醯亞胺樹脂膜之步驟；及於上述聚醯亞胺樹脂膜上形成低溫多晶矽TFT之步驟。 A method for manufacturing a laminate, comprising the steps of: coating the resin composition of any one of claims 1 to 24 on the surface of a support; forming a polyimide resin film from the resin composition Step; and the step of forming a low-temperature polysilicon TFT on the above-mentioned polyimide resin film. 如請求項28之積層體之製造方法，其進而包括將上述聚醯亞胺樹脂膜自上述支持體剝離之步驟。 The method for manufacturing a laminate of claim 28, which further includes the step of peeling the polyimide resin film from the support. 一種撓性器件之製造方法，其包括如請求項28或29之積層體之製造 方法。 A method for manufacturing a flexible device, which includes the manufacturing of a laminate as claimed in claim 28 or 29 method. 一種低溫多晶矽TFT元件之基板用之聚醯亞胺樹脂，其特徵在於：其包含源自二胺成分與酸二酐成分之下述通式(5)所表示之聚醯亞胺成分：
Figure 106129267-A0305-02-0061-7
，以及 包含源自矽酮二胺成分之下述通式(3)所表示之結構
Figure 106129267-A0305-02-0061-5
 (式中，存在複數個之R3及R4分別獨立地為碳數1~20之一價之有機基，而且h為3~200之整數)，並且於上述聚醯亞胺樹脂中，於將上述二胺成分與上述酸二酐成分之總質量設為100質量%時，上述矽酮二胺成分之含量未達6質量%。 A polyimide resin used for the substrate of a low-temperature polysilicon TFT element, characterized in that it contains a polyimide component represented by the following general formula (5) derived from a diamine component and an acid dianhydride component:
Figure 106129267-A0305-02-0061-7
, And the structure represented by the following general formula (3) containing components derived from silicone diamine
Figure 106129267-A0305-02-0061-5
 (In the formula, there are a plurality of R 3 and R 4 each independently being a monovalent organic group with 1 to 20 carbons, and h is an integer from 3 to 200), and in the above polyimide resin, in When the total mass of the diamine component and the acid dianhydride component is 100% by mass, the content of the silicone diamine component is less than 6% by mass. 如請求項31之低溫多晶矽TFT元件之基板用之聚醯亞胺樹脂，其中上述聚醯亞胺樹脂包含下述通式(6)：
Figure 106129267-A0305-02-0061-6
 所表示之結構。 The polyimide resin used for the substrate of the low-temperature polysilicon TFT element of claim 31, wherein the polyimide resin comprises the following general formula (6):
Figure 106129267-A0305-02-0061-6
 The structure represented. 如請求項31之低溫多晶矽TFT元件之基板用之聚醯亞胺樹脂，其重量平均分子量為4萬以上且30萬以下。 For example, the polyimide resin used for the substrate of the low-temperature polysilicon TFT element of claim 31 has a weight average molecular weight of 40,000 or more and 300,000 or less. 如請求項31之低溫多晶矽TFT元件之基板用之聚醯亞胺樹脂，其中於將上述聚醯亞胺樹脂中所含之固形物成分之總重量設為100質量%時，該固形物成分中所含有之分子量未達1,000之分子之量未達5質量%。 For the polyimide resin used for the substrate of the low-temperature polysilicon TFT element of claim 31, when the total weight of the solid content contained in the polyimide resin is set to 100% by mass, the solid content is The amount of molecules with a molecular weight of less than 1,000 is less than 5% by mass. 如請求項34之低溫多晶矽TFT元件之基板用之聚醯亞胺樹脂，其中上述固形物成分中所含有之上述分子量未達1,000之分子之量為1質量%以下。 For the polyimide resin used for the substrate of the low-temperature polysilicon TFT element of claim 34, the amount of the above-mentioned molecular weight less than 1,000 contained in the above-mentioned solid component is 1% by mass or less. 如請求項31之低溫多晶矽TFT元件之基板用之聚醯亞胺樹脂，其中上述矽酮二胺成分之含量為5.9質量%以下。 For the polyimide resin used for the substrate of the low-temperature polysilicon TFT element of claim 31, the content of the above-mentioned silicone diamine component is 5.9% by mass or less. 如請求項36之低溫多晶矽TFT元件之基板用之聚醯亞胺樹脂，其中上述矽酮二胺成分之含量為3質量%以下。 For example, the polyimide resin used for the substrate of the low-temperature polysilicon TFT element of claim 36, wherein the content of the above-mentioned silicone diamine component is 3% by mass or less. 如請求項31之低溫多晶矽TFT元件之基板用之聚醯亞胺樹脂，其中上述聚醯亞胺樹脂於將上述二胺成分之總莫耳數設為100莫耳%時，上述聚醯亞胺樹脂所含之下述通式(4)：[化4]
Figure 106129267-A0305-02-0063-8
 (式中，R1、R2、R3分別獨立地表示碳數1~20之一價之有機基；n表示0或1；而且a、b及c為0~4之整數)所表示之二胺之量為48莫耳%以下。 For example, the polyimide resin used for the substrate of the low-temperature polysilicon TFT element of claim 31, wherein the polyimide resin when the total mole of the diamine component is set to 100 mole%, the polyimide resin The following general formula (4) contained in the resin: [化4]
Figure 106129267-A0305-02-0063-8
 (In the formula, R 1 , R 2 , R 3 each independently represent a monovalent organic group with 1 to 20 carbon atoms; n represents 0 or 1; and a, b, and c are integers from 0 to 4) The amount of diamine is 48 mol% or less. 如請求項38之低溫多晶矽TFT元件之基板用之聚醯亞胺樹脂，其中上述聚醯亞胺樹脂所含之上述通式(4)所表示之二胺之量未達1莫耳%。 The polyimide resin used for the substrate of the low-temperature polysilicon TFT device of claim 38, wherein the polyimide resin contains the diamine represented by the general formula (4) in an amount less than 1 mol%. 如請求項39之低溫多晶矽TFT元件之基板用之聚醯亞胺樹脂，其中上述聚醯亞胺樹脂所含之上述通式(4)所表示之二胺之量為0.9莫耳%以下。 The polyimide resin used for the substrate of the low-temperature polysilicon TFT element of claim 39, wherein the amount of the diamine represented by the general formula (4) contained in the polyimide resin is 0.9 mol% or less. 如請求項38之低溫多晶矽TFT元件之基板用之聚醯亞胺樹脂，其中上述聚醯亞胺樹脂包含4-胺基苯基-4-胺基苯甲酸酯作為上述通式(4)所表示之二胺成分。 The polyimide resin used for the substrate of the low-temperature polysilicon TFT element of claim 38, wherein the polyimide resin contains 4-aminophenyl-4-aminobenzoate as the formula (4) Represents the diamine component. 如請求項41之低溫多晶矽TFT元件之基板用之聚醯亞胺樹脂，其中上述聚醯亞胺樹脂於將上述二胺成分之總莫耳數設為100莫耳%時，上述4-胺基苯基-4-胺基苯甲酸酯之含量為48莫耳%以下。 For example, the polyimide resin used for the substrate of the low-temperature polysilicon TFT element of claim 41, wherein the polyimide resin, when the total moles of the diamine components are set to 100 mole%, the 4-amino group The content of phenyl-4-aminobenzoate is 48 mol% or less. 如請求項42之低溫多晶矽TFT元件之基板用之聚醯亞胺樹脂，其中上述聚醯亞胺樹脂中上述4-胺基苯基-4-胺基苯甲酸酯之含量未達1莫耳 %。 Such as the polyimide resin used for the substrate of the low-temperature polysilicon TFT element of claim 42, wherein the content of the 4-aminophenyl-4-aminobenzoate in the polyimide resin is less than 1 mol %. 如請求項43之低溫多晶矽TFT元件之基板用之聚醯亞胺樹脂，其中上述聚醯亞胺樹脂中上述4-胺基苯基-4-胺基苯甲酸酯之含量未達0.9莫耳%。 For example, the polyimide resin used for the substrate of the low-temperature polysilicon TFT element of claim 43, wherein the content of the 4-aminophenyl-4-aminobenzoate in the polyimide resin is less than 0.9 mol %. 如請求項31之低溫多晶矽TFT元件之基板用之聚醯亞胺樹脂，其中上述聚醯亞胺樹脂包含二胺基二苯基碸作為上述二胺成分。 According to claim 31, the polyimide resin used for the substrate of the low-temperature polysilicon TFT device, wherein the polyimide resin contains diaminodiphenyl sulfide as the diamine component. 如請求項45之低溫多晶矽TFT元件之基板用之聚醯亞胺樹脂，其中上述聚醯亞胺樹脂於將上述二胺成分之總莫耳數設為100莫耳%時，上述二胺基二苯基碸之含量為90莫耳%以上。 For example, the polyimide resin used for the substrate of the low-temperature polysilicon TFT element of claim 45, wherein when the total mole of the diamine component is set to 100 mole%, the polyimide resin is The content of phenyl sulfide is more than 90 mol%. 如請求項31之低溫多晶矽TFT元件之基板用之聚醯亞胺樹脂，其中上述聚醯亞胺樹脂包含均苯四甲酸二酐作為上述酸二酐成分。 According to claim 31, the polyimide resin for substrates of low-temperature polysilicon TFT devices, wherein the polyimide resin contains pyromellitic dianhydride as the acid dianhydride component. 如請求項47之低溫多晶矽TFT元件之基板用之聚醯亞胺樹脂，其中上述聚醯亞胺樹脂於將上述酸二酐成分之總莫耳數設為100莫耳%時，上述均苯四甲酸二酐之含量為90莫耳%以上。 For example, the polyimide resin used for the substrate of the low-temperature polysilicon TFT element of claim 47, wherein the polyimide resin when the total moles of the acid dianhydride components are set to 100 mole%, the pyromellitic resin The content of formic dianhydride is 90 mol% or more.
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