TW201202844A

TW201202844A - Radiation sensitive resin composition, cured film, method for forming cured film, and display element

Info

Publication number: TW201202844A
Application number: TW100119335A
Authority: TW
Inventors: Eiji Yoneda; Nobuhiro Nishi; Seiichirou Kodama; Katsumi Inomata
Original assignee: Jsr Corp
Priority date: 2010-06-03
Filing date: 2011-06-02
Publication date: 2012-01-16
Also published as: KR20110132984A; KR101853729B1; CN102269932B; JP5471851B2; JP2011253110A; CN102269932A

Abstract

Provided are radiation sensitive resin composition, cured film, method for forming cured film, and display element. Said radiation sensitive resin composition has outstanding preserving stability while firing at low temperature, and sufficient radiation sensitivity. Said cured film has outstanding properties required as being cured film, such as heat-resisting property, chemical resisting property, transmittance, flatness, voltage retention, and so on. Said radiation sensitive resin composition, characterized in containing [A] polymer having epoxy group(s), [B] polymerizing compound having ethylene unsaturated bond(s), [C] radiation sensitive polymerization primer, and [D] at last one compound chosen from the following formulas (1) to (3).

Description

201202844 六、發明說明：【發明所屬之技術領域】本發明涉及適合作為層間絕緣膜、保護膜或間隔物等硬化膜的形成材料的感放射線性樹脂組成物、由該組成物形成的硬化膜、硬化膜的形成方法以及顯示元件^ 【先前技術】薄膜電晶體（TFT)型液晶顯示元件等電子部件中一般設置層間絕緣膜以使層狀配置的佈線間絕緣。例如， TFT型液晶顯示元件經過在層間絕緣膜上形成透明電極膜，然後在其上形成液晶配向膜的步驟製造。因該層間絕緣膜在透明電極膜的形成步驟中暴露在高溫條件下，或者暴露在形成電極圖案時使用的抗蝕層剝離液中所以必〃員要有針對匕們的足夠的财熱性和财化學藥品性。另外’形成這種硬化膜時使用的感放射線性樹脂組成物要求縮短反射線的照射時間（也就是，高的放射線感度）以及良好的保存穩定性。此外，近年來，應用TFT技術的輕量小型的撓性顯不裔正逐漸普及。作為撓性顯示器的基板研究考慮聚碳酸醋等塑膠基板。塑膠基板會由於受熱伸張、收縮，所以具有阻礙顯示器功能的問題。因此’正在研究製造撓性顯不器的加熱步驟的低溫化。例如，在日本特開 2009-4394號公報中揭示了含有即使低溫燒製也可以硬化的聚醯亞胺前驅物的撓性顯示器用閘門絕緣膜用塗布液。但是，該塗布液由於沒有曝光顯影形成圖案的能力，所以無法形成微細圖案。此外，還導致硬化反應進行的 201202844 不充分’或者得到的硬化膜 J 1 联I* 了耐熱性、耐學口以外，還無法滿足透光率、 ’、如性 ,, 疋达尤早千整性、電壓保持率、耐埶線性膨脹性等。 7熱 —因此’遇研究了通過添加即使在低溫下也能作為氧類材料的硬化劑使用的脸化人私^、f ^ ^ d便用的胺化合物以進行交聯反應的策 4疋添加一般的胺化合物會引起與組成物中存在的環氧基的隨時間變化的反應，保存穩定性會降低。基於這種情況’希望開發出保存穩定性和低溫燒製均優異，而且具有足夠的放射線感度的硬化膜形成用感放射線性樹脂組成物，以及作為硬化膜所要求的性質的耐熱性、耐化學藥品性、透光率、平整性、電壓保持率、耐熱線性％脹性等優異的硬化膜。現有技術文獻專利文獻專利文獻1日本特開2009_4394號公報【發明内容】 [發明所欲解決之課題] 本發明是基於上述這些問題提出的，其目的在於提供保存穩定性和低溫燒製均優異’而且具有足夠的放射線感度的硬化膜形成用感放射線性樹脂組成物，以及作為硬化膜所要求的性質的财熱性、耐化學藥品性、透光率、平整性、電壓保持率、封熱線性膨脹性等優異的硬化膜、硬化膜的形成方法以及顯示元件。 [解決課題之手段] 為了解決上述問題而提出的本發明是一種感放射線性樹脂組成物’其特徵在於，包含： 201202844 [A] 具有環氧基的聚合物物」），、卜也稱作「[A]聚合 [B] 具有乙烯性不飽和鍵的聚合性化合物稱作「[B]聚合性化合物」）， σ ’也 [C ]感放射線性聚合引發劍（以下引發劑劑」），以及發推下，也稱作「[C]聚合 [D]選自下述式⑴〜(3)所示的化合物(以下「[D]化合物」）的至少一種化合物。％作 Ο201202844 6. EMBODIMENT OF THE INVENTION The present invention relates to a radiation-sensitive resin composition suitable as a material for forming a cured film such as an interlayer insulating film, a protective film or a spacer, and a cured film formed of the composition. Method of Forming Cured Film and Display Element ^ [Prior Art] An interlayer insulating film is generally provided in an electronic component such as a thin film transistor (TFT) type liquid crystal display element to insulate between wirings arranged in a layer. For example, a TFT type liquid crystal display element is manufactured by a step of forming a transparent electrode film on an interlayer insulating film and then forming a liquid crystal alignment film thereon. Since the interlayer insulating film is exposed to a high temperature condition in the formation step of the transparent electrode film, or is exposed to the resist stripping liquid used in forming the electrode pattern, it is necessary to have sufficient finernity and wealth for us. Chemical properties. Further, the radiation-sensitive resin composition used in forming such a cured film is required to shorten the irradiation time of the reflection line (that is, high radiation sensitivity) and good storage stability. In addition, in recent years, lightweight and compact flexible people using TFT technology are gradually spreading. As a substrate for a flexible display, a plastic substrate such as polycarbonate or vinegar is considered. The plastic substrate may be stretched and shrunk due to heat, so that it has a problem of hindering the function of the display. Therefore, the lowering of the heating step of manufacturing the flexible display is being studied. For example, Japanese Laid-Open Patent Publication No. 2009-4394 discloses a coating liquid for a gate insulating film for a flexible display which contains a polyimide precursor which can be hardened even at a low temperature. However, since this coating liquid has no ability to form a pattern by exposure and development, it is impossible to form a fine pattern. In addition, the 201202844 which is caused by the hardening reaction is not sufficient' or the obtained cured film J 1 is combined with heat resistance and resistance to the mouth of the school, and the light transmittance, ', for example, is not satisfied. Sex, voltage retention, resistance to linear expansion, etc. 7 heat - therefore, it has been studied by adding an amine compound which can be used as a hardener for an oxygen-based material even at a low temperature to carry out a crosslinking reaction. A general amine compound causes a time-dependent reaction with an epoxy group present in the composition, and storage stability is lowered. Based on this situation, it is desired to develop a radiation-sensitive resin composition for forming a cured film which is excellent in storage stability and low-temperature firing, and which has sufficient radiation sensitivity, and heat resistance and chemical resistance which are required properties as a cured film. A cured film excellent in chemical properties, light transmittance, flatness, voltage holding ratio, heat resistance linear % expansion, and the like. [Problem to be Solved by the Invention] The present invention has been made based on the above problems, and an object thereof is to provide excellent storage stability and low-temperature firing. Moreover, the radiation-sensitive resin composition for forming a cured film having sufficient radiation sensitivity, and the properties required for the cured film, such as heat, chemical resistance, light transmittance, flatness, voltage holding ratio, and thermal expansion of heat sealing. A cured film excellent in properties, a method of forming a cured film, and a display element. [Means for Solving the Problem] The present invention has been made in order to solve the above problems, and is a radiation sensitive resin composition characterized by comprising: 201202844 [A] a polymer having an epoxy group"), "[A] polymerized [B] a polymerizable compound having an ethylenically unsaturated bond is referred to as "[B] polymerizable compound"), and σ 'also [C] a radiation-induced linear polymerization-initiated sword (the following initiator)), And the "C" polymerization [D] is at least one compound selected from the compounds represented by the following formulas (1) to (3) (hereinafter, the "[D] compound"). %作Ο

RV c、 Η Ο 、R2 cRV c, Η Ο , R2 c

〇 II Ά I H (1) /R4 、N， i H H H (2) ^ H 〇 (3) :(1)中’ Rl、R2各自獨立地表示氫原子、碳屌數為 1 〜12 。 i 的烷基、環己基、苯基、萘基、乙烯基、〇 _者可以被碳原子數為1〜ό的烷基、鹵辛、、, 基、羧基、r Μ β ^ — 酿基取代的碳原子數為1〜12的烷基、笨其奈基。您式（2) φ q Λ ’ R、R各自獨立地表示氫原子、碳原子為 1〜12的h 、境基、環己基’A表示亞甲基、碳原子數） 2〜12的伸泸甘心基、伸苯基、伸萘基、伸乙烯基，或者可ΐ 201202844 被石反原子數為丨〜6的烷基、鹵素取代的亞曱基、碳原子數為2〜12的伸烷基、伸苯基、伸萘基。式（3 )中，R5、R6各自獨立地表示氫原子、碳原子數為1〜丨2的烷基、環己基，A表示亞曱基、碳原子數為 2〜1 2的伸烷基、伸苯基、伸萘基伸乙烯基，或者可以被碳原子數為1〜6的烷基 '鹵素取代的亞曱基、碳原子數為2〜1 2的伸烷基、伸苯基、伸萘基。）一種感放射線性樹脂組成物，該組成物之進一步特徵在於：[A]具有環氧基的聚合物是進一步具有羧基的共聚物（以下，也稱作「[ A]共聚物」）。含有作為鹼可溶性樹脂的[A]聚合物、[B]聚合性化合物、[C]聚合引發劑以及[D]化合物。作為感光性材料的該組成物通過利用感放射線性的曝光、顯影，可以容易地形成U細且精巧的圖案，而且具有足夠的放射線感度。另外，該組成物包含上述式（1)〜（3)所示在分子内具有醯胺基的[D]化合物。該組成物通過含有[D]化合物，可以同時貫現保存穩定性和低溫燒製。[D]化合物是具有一級或二級醯胺基的化合物，這種化合物和具有一級、二級胺基的化合物相比，對環氧基的親核性更低，在室溫下也幾乎無法進行環氧基的硬化反應。因此，該組成另一方面，如果將該組成物加熱物的保存穩定性優異到規疋孤度以上’則[D]化合物促進含有環氧基的樹脂的硬化反應，發揮作為環氧基的硬化促進劑的功能。上述[C]聚合弓丨發劑較佳為由乙醯苯化合物和〇_醯基肟化合物構成的群組中選出的至少-種。作為[C]聚合 201202844 引發劑通過使用上述特定的化合物，即使在低曝光量的情況下，也可以進一步提高耐熱性等作為硬化膜所要求的性質。本發明的硬化膜的形成方法包括： (1) 在基板上形成該組成物的塗膜的步驟， (2) 對步驟（1)形成的塗膜的至少一部分照射放射線的步驟， (3) 將步驟（2)中照射過放射線的塗膜顯影的步驟，以及 (4) 燒製步驟（3)中顯影後的盡膜的步驟。通過使用該組成物的本發明的形成方法，可以形成均衡性良好地滿足耐熱性、耐化學藥品性、透光率、平整性、電壓保持率、耐熱性線性膨脹性等要求性質的硬化膜β 上述步驟（4)的燒製溫度較佳為2〇〇 t以下。該組成物如上所述由於含有[D]化合物，所以像這樣，實現低溫燒製的同時保存穩定性也優異，而且具有足夠的放射線感度。因此，該組成物適合作為在希望低溫燒製的撓性顯示器等中使用的層間絕緣膜、保護膜和間隔物等硬化膜的形成材料而使用。保護膜或間隔 ’具有該硬化由該組成物形成的作為層間絕緣膜、物的硬化膜也適合包含在本發明中。另外膜的顯示元件也適合包含在本發明中。燒製」是指加熱到得到等硬化膜所要求的表面硬另外，本說明書中所述的層間絕緣膜、保護膜和間隔物 201202844 度的含義。所述的「感放射線佳樹脂組成物」的「放射線」是包含可見光線、紫外線、遠紫外線、X射線、帶電粒子束等的概念。 [發明之功效] 如上說明所述，本發明的感放射線性樹脂組成物可以容易地形成微細且精巧的圖案，保存穩定性和低溫燒製均優異’而且具有足夠的放射線感度。另外，由該組成物形成的硬化膜作為其要求性質的耐熱性、耐化學藥品性、透光率、平整性、電壓保持率、耐熱線性膨脹性等優異。因此，該組成物適合作為在希望低溫燒製的撓性顯示器等中使用的層間絕緣膜、保護膜和間隔物等硬化膜的形成材料使用。【實施方式] 以下，對本發明的實施方案進行詳細描述。 <感放射線性樹脂組成物> [B]聚^生感放射線性樹脂組成物含有[A]聚合物、利用感放射二二：光作為感光性材料的該組成物通過精巧的圖案，而且：有5顯影，可以容易地形成微細且成物通過含有[D]化合物夠的㈣線感m卜，該組溫燒製。以下，對久槐可以同時貫現保存穩定性和低，]具有環氧基的化素進行詳細描述。本發明中的[八]1右m [A]聚合物）是在分子氧基的化合物（以下，也稱作 3,4-環氧環己基的聚合|有兩個以上的縮水甘油基或者 201202844 作聚乙二醇的聚族多元醇的脂脂等苯脂；多鏈二元類；環内具有清漆型為具有醇二縮縮水甘醇加成肪族聚酚酚醛酚型環酸的二氧化大兩個以環氧樹 1裒氧基水甘油油喊類一種或縮水甘清漆型氧樹脂縮水甘豆油、上的環脂以及的聚合醚、聚 :對乙兩種以油醚類環氧樹 ;環狀油酯類環氧化氧基的多酚型物的具體丙.二醇二二醇、丙上的氧化 ;雙酚A 脂；曱紛脂肪族環，而級脂亞麻子油化合物中環氧樹脂例子，可以縮水甘油醚二醇、甘油烯得到的聚酚醛清漆型酚醛清漆型氧樹脂；脂肪酸的縮水等。在這些 ’較佳為苯等多元等脂肪鲢多元環氣樹環氧樹肪族長甘油酯在分子酉分S分醒· 本發明進一步希望[A]具有環氧基的聚合物是進一步具有羧基的共聚物（以下’也稱作「[A]共聚物」）。 [A]共聚物具有（al)含叛基的結構單元和含環氧基的結構單元。作為得到[A]共聚物的方法例如可以通過將提供（al)含羧基的結構單元（羧基還包括酸酐基）的不飽和缓酸和/或不飽和叛酸針（以下，也稱作「化人物（丨））和提供（a2)含環氧基的結構單元的具有環氧基的自由基聚合性化合物（以下’也稱作「化合物（ii)j )在溶劑中，使用聚合引發劑共聚得到。另外，根據需要，還可以將作為（a3)的（曱基）丙烯酸烷基酯等自由基聚合性化合物 (以下’也稱作「化合物（iii)」）和上述化合物（i)、化合物 (ii)同時含有來進行共聚，形成[A]共聚物。作為化合物（i)，可以列舉出例如 -10- 201202844 丙烯酸、甲基丙烯酸、琥珀酸、2-甲基丙烯醯氧基乙基六氫鄰苯二甲酸、2-甲酸等一元敌酸；巴豆酸、2 -丙烯醯氧基乙其乙基琥珀酸、2-丙烯醯氧基基丙稀酿氧基六氣鄰苯二甲馬來馱、虽馬g曼、擰康酸等二元羧酸；馬來酸酐等二元羧酸針。它們之中，你μ s «共聚反應性以及得到的共聚物對驗影液的露解性的德妈；& . 肝r扪硯點而s，較佳為丙烯酸、甲基丙烯酸、 2-丙烯醯氧基琥珀酸、2•曱基丙烯醯氧基琥珀酸、酸酐。在[A]共聚物中’化合物⑴可以單獨或混合兩種以上使用。在[A]共聚物中’作為化合物⑴的含有率較佳為丄質量％〜40質量％，更佳為7質量％〜30質量％，特佳為8 質量％〜25質量％。通過使化合物⑴的含有率為1質量 °/〇〜40質量％，可以得到放射線感度、顯影性以及保存穩定性等性質更高等級地最優化的感放射線性樹脂級成物。作為化合物（ii)可以列舉出具有環氧基（環氡乙产基、環氧丙烷基）等的自由基聚合性化合物。作為具有澤氧乙烧基的自由基聚合性化合物，可以列舉出例如：丙烯酸縮水甘油酯、丙烯酸2 -甲基縮水甘油酯、丙烯酸3，4 -環氧丁醋、丙烯酸6,7 -環氧庚醋、丙缔酸3 4 環氧環己酯、丙烯酸-3，4·環氧環己基甲酯等丙烯酸環氣烷基酯； 201202844 甲基丙烯酸縮水甘油酯、甲基丙烯酸2-甲基縮水甘油酯、甲基丙烯酸3,4-環氧丁酯、甲基丙烯酸6,7-環氧庚酯、甲基丙烯酸3,4-環氧環己酯、甲基丙烯酸-3,4-環氧環己基甲酯等甲基丙烯酸環氧烷基酯； α -乙基丙浠酸縮水甘油酯、α -正丙基丙烯酸縮水甘油S旨、α -正丁基丙稀酸縮水甘油醋、α -乙基丙埽酸6，7 -環氧庚酯等α-烷基丙烯酸環氧烷酯；鄰乙烯基苄基縮水甘油醚、間乙烯基节基縮水甘油鍵、對乙烯基苄基縮水甘油醚等縮水甘油_。作為具有環氧丙烷基的自由基聚合性化合物，可以列舉出例如3-(甲基丙烯醯氧基甲基）環氧丙烷、3 (甲某 =醯氧基甲基)-3-乙基環氧丙烧、3_(甲基丙稀酿氧：土)广曱基環氧丙烧、3·(甲基丙烯酿氧基乙基)環氧丙 ::3-(甲基丙烯酼氧基乙基)_3乙基環氧丙⑮、2-乙基 =甲基丙稀酿氧基乙基)環氧丙院、3例醯氧基农氧丙烷、3-(丙烯醯氧基甲基）_3_乙基烯醯氧基甲美衣氣丙炫、3-(丙 :基甲基)-2-f基壤氧丙烧、3_(兩烯酿氧基产氧丙烷、3-(丙烯醯氧基乙基）_3_乙基产 ^ 一3-(肉稀醯氧基乙基）環氧丙烧、衣丙院、2_乙基環氧丙烷、2_甲美. 基兩烯醯氧基甲基）沉甲基-2-(曱基丙烯醯氧基甲其、浮^ 3-甲基-2-(甲基丙烯醯氧基甲基)環山氧丙烷、基丙稀酿氧基甲基)環氧丙貌、垸、4_甲基_2-(甲乙基-甲基丙烯酸酯、2_(2_(3_甲基产/基環氧丙烷基））基丙烯酸酿、2-(甲基丙烯醯氧二：丙烷基))乙基-甲烷、2·(甲基丙烯醯氧基乙基) ：)_2_甲基環氧丙 Τ基龟氧丙烷、2-(丙烯 •12· 201202844 醯氧基曱基）環氧丙烷、2-曱基丙烷、3-甲美2 & (丙烯醯氧基甲基）環氣 r基-2-(丙烯醯氧基甲）衣氧 -2-(丙烯醯氧基曱基）衣虱丙烷、4_甲基基））乙基_曱芙丙# 儿2-(2-(2-曱基環氧丙烷 τ丞内烯酸酯、 -曱基丙烯基Ο乙 2_(丙烯醯氡基乙基）_4 A 曱基％軋丙烷、它們之中，甲其氧丙燒等(甲基)丙稀酸顆。甲基端h 丙烯酸縮水甘油酷、甲基丙烯酸2 :基縮水甘油酯、曱基丙烯酸M_環氧丁 _、氧基甲基）環氧丙烷、 _ 醯烷、…盆一（曱基丙烯醯氧基曱基）環氧丙 3_(甲基丙烯醒氧基甲基)_3_乙基環氧丙烷' 丙稀酿氧基曱基）環氧丙烧，從得到的層間絕緣膜、保^ 膜和間隔物等硬化膜對基板的密合性高、具有高的耐熱性、進而提高顯示元件的可靠性方面是較佳的。、、在[Α]共聚物中，化合物（ii)可以單獨或混合兩種以上使用。[A]共聚物中，作為化合物（丨丨）的含有率較佳為1 吳里/〇~70質量％，更佳為丨5質量％〜65質量％。通過使化合物（ii)的含有率為1質量％〜7〇質量％，容易控制共聚物的分子量’可以得到顯影性、感度等更高等級地最優化的感放射線性樹脂組成物。作為化合物（iii)，可以列舉出（甲基）丙烯酸烷基酯、 (曱基）丙浠酸脂環酯、含氧原子的不飽和雜五員環和六員環的（甲基）丙烯酸酯、具有羥基的（甲基）丙烯酸酯、（甲基）丙烯酸芳酯、不飽和二元羧酸二酯、馬來醯亞胺化合物、（曱基）丙稀酸的經基烧基酿、苯乙稀、α-甲基苯乙稀、 1，3-丁二烯。 -13- 201202844 作為（甲基）丙烯酸烷基酯，可以列舉出例如曱基丙烯酸曱酯、曱基丙烯酸乙酯、甲基丙烯酸正丁酯、曱基丙稀酸二級丁酯、曱基丙烯酸三級丁酯、丙烯酸曱酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸二級丁酯、丙烯酸三級丁酯等。作為（曱基）丙烯酸脂環式烷基酯，可以列舉出例如曱基丙烯酸環戊酯、甲基丙烯酸環己酯、甲基丙烯酸-2-曱基環己酯、曱基丙烯酸三環二環戊酯、曱基丙烯酸-2-二環戊基氧基乙酯、曱基丙烯酸異楛基酯、丙烯酸環戊酯、丙烯酸環己酯、丙烯酸-2-甲基環己酯、丙烯酸三環二環戊酯、丙烯酸-2 -二環戊基氧基乙酯、丙烯酸異葙基酯等。作為含氧原子的不飽和雜五員環和六員環的曱基丙烯酸酯，可以列舉出例如： (甲基）丙烯酸四氫糠基酯、2-甲基丙烯醯氧基-丙酸四鼠糖基自旨、3-(曱基）丙稀酿氧基四氮。夫喃-2 -嗣等含有四氫呋喃骨架的不飽和化合物； 2 -曱基-5-(3-呋喃基）-1-戊烯-3-酮、（曱基）丙烯酸糠基S旨、1 - °夫喊-2 -丁 - 3-稀-2 -嗣、1 -α夫喃-2 - 丁基-3 -曱乳基 -3 -稀-2 -嗣、6_ (2 -α夫喃基）-2 -甲基-1 -己；fcfp - 3 -嗣、6 - °夫喃-2 -基-己-1 -細-3 -嗣、丙稀酸-2」°夫喃-2 -基-1 -曱基-乙S旨、6-(2_ 。夫喃基）-6 -曱基-1-庚稀-3-酮等含有D夫喃骨架的不飽和化合物；曱基丙烯酸（四氫吡喃-2-基）甲酯、2,6-二甲基-8 -(四鼠°比喃-2 -基氧基）-辛-1 -炸-3-S同、2-甲基丙稀酸四鼠 -14- 201202844 吼喃-2_基酯、1-(四氫吡喃-2-氧基）-丁基-3-烯-2-酮等含有四氫°比喃骨架的不飽和化合物； 4-U，4-二氧雜-5·氧代-6_庚烯基）-6_曱基-2-吡喃、二氧雜_6氧代-7_辛烯基）_6_甲基_2_0比喃等含有〇比鳴骨架的不飽和化合物。作為具有羥基的（甲基）丙烯酸酯，可以列舉出（甲基）丙稀酸羥基乙酯、（曱基）丙烯酸-2-羥基丙酯 '(甲基）丙浠酸-3-羥基丙酯、（曱基）丙烯酸-2,3-二羥基丙酯等。作為（甲基）丙烯酸芳酯，可以列舉出例如（甲基）丙稀酸苯醋、（曱基）丙烯酸苄酯等。作為不飽和二元緩酸二酯，可以列舉出例如馬來酸二乙酯、富馬酸二乙酯、衣康酸二乙酯等。作為馬來醯亞胺化合物，可以列舉出例如N -苯基馬來酿亞胺、N-環己基馬來醯亞胺、N_节基馬來醯亞胺、 Ν-(4·羥基苯基）馬來醯亞胺、基苄基）馬來醯亞胺、N-琥轴醯亞胺基_3_馬來醯亞胺苯甲酸醋、N_琥珀醯亞胺基-4-馬來醯亞胺丁酸酯、N_琥珀醯亞胺基_6_馬來醯亞胺己酸醋、N-琥站醯亞胺基_3_馬來醯亞胺丙酸略、 N-(9-吖啶基）馬來醢亞胺等；在[A]共聚物中，作為化合物（Hi)的含有率較佳質量％〜70質量％，更佳為15質量％〜65質量％。通過化合物（ih)的含有率為1〇 f量％〜7()質量％，容易聚物的分子量’可以得到顯影性、感度 '密合性二：等級地最優化的感放射線性樹脂組成物。円 -15- 201202844 < [A ]共聚物的合成方法> [A]共聚物例如可以通過將化合物（i)、化合物（ii)以及根據需要使用的化合物（iii)在溶劑中，使用自由基聚合引發劑聚合合成。作為在製造[A ]共聚物的聚合反應中使用的溶劑，可以列舉出例如醇類、醚類、二醇醚、乙二醇烷基醚乙酸酯、二甘醇烷基醚、丙二醇單烷基醚、丙二醇單烷基醚乙酸酯、丙二醇單烷基醚丙酸酯、芳烴類、酮類、其他酯類等。作為醇類，可以列舉出例如甲醇、乙醇、苯曱醇、 2 -苯乙醇、3 -苯基-1-丙醇等。作為醚類，可以列舉出環狀醚、二醇醚、乙二醇烷基醚乙酸酯、二甘醇烷基醚、丙二醇單烷基醚、丙二醇單烷基醚乙酸酯、丙二醇單烷基醚丙酸酯等。作為環狀醚可以列舉出例如四氫呋喃等。作為二醇醚，可以列舉出例如乙二醇單甲醚、乙二醇單乙醚等。作為乙二醇烷基醚乙酸酯，可以列舉出例如甲基賽路蘇乙酸酯、乙基賽路蘇乙酸酯、乙二醇單丁醚乙酸酯、乙二醇單乙醚乙酸酯等。作為二甘醇烷基醚，可以列舉出例如二甘醇單曱謎、二甘醇單乙醚、二甘醇二甲醚、二甘醇二乙⑽、二甘醇曱基乙基醚等。作為丙二醇單烷基醚，可以列舉出例如丙二醇單曱醚、丙二醇單乙醚、丙二醇單丙醚、丙二醇單丁醚等。 -16 - 201202844 作為丙二醇單烷基醚乙酸酯，可以列舉出例如丙二醇單曱醚乙酸酯、丙二醇單乙醚乙酸酯、丙二醇單丙醚乙酸酯、丙二醇單丁醚乙酸酯等。作為丙二醇單烧基醚丙酸醋，可以列舉出例如丙二醇單甲醚丙酸酯、丙二醇單乙醚丙酸酯、丙二醇單丙醚丙酸酯、丙二醇單丁醚丙酸酯等。作為芳香族烴類，可以列舉出例如曱苯、二甲苯等。作為酮類，可以列舉出例如甲基乙基酮、環己酮、 4-羥基-4-甲基-2-戊酮等。作為其他酯類，可以列舉出例如乙酸曱酯、乙酸乙酯、乙酸丙酯、乙酸丁酯、2 -羥基丙酸乙酯、2 -羥基-2 -曱基丙酸甲酯、2 -羥基-2 -曱基丙酸乙酯、羥基乙酸曱酯、羥基乙酸乙酯、羥基乙酸丁酯、乳酸曱酯、乳酸乙酯、乳酸丙酯、乳酸丁酯、3 -羥基丙酸甲酯、3 -羥基丙酸乙酯、3 -羥基丙酸丙酯、3 -羥基丙酸丁酯、2 -羥基-3 -曱基丁酸甲酯、甲氧基乙酸曱酯、甲氧基乙酸乙酯、曱氧基乙酸丙酯、曱氧基乙酸丁酯、乙氧基乙酸曱酯、乙氧基乙酸乙酯、乙氧基乙酸丙酯、乙氧基乙酸丁酯、丙氧基乙酸曱酯、丙氧基乙酸乙酯、丙氧基乙酸丙酯、丙氧基乙酸丁酯、丁氧基乙酸曱酯、丁氧基乙酸乙酯、丁氧基乙酸丙酯、丁氧基乙酸丁酯、2-甲氧基丙酸甲酯、2-曱氧基丙酸乙酯、2-甲氧基丙酸丙酯、2-曱氧基丙酸丁酯、 2-乙氧基丙酸曱酯、2-乙氧基丙酸乙酯、2-乙氧基丙酸丙酯、2-乙氧基丙酸丁酯、2-丁氧基丙酸曱酯、2-丁氧基丙酸乙酯、2-丁氧基丙酸丙酯、2-丁氧基丙酸丁酯、3-曱氧 -17- 201202844 基丙酸甲酯、3 -曱氧基丙酸乙酯、3 -曱氧基丙酸丙酯、 3 -曱氧基丙酸丁酯、3 -乙氧基丙酸甲酯、3 -乙氧基丙酸乙酯、3 -乙氧基丙酸丙酯、3 -乙氧基丙酸丁酯、3 -丙氧基丙酸甲酯、3 -丙氧基丙酸乙酯、3 -丙氧基丙酸丙酯、3 -丙氧基丙酸丁酯、3 -丁氧基丙酸甲酯、3 -丁氧基丙酸乙酯、 3 -丁氧基丙酸丙酯、3 -丁氧基丙酸丁酯等。作為上述自由基聚合引發劑，可以列舉出例如2,2’-偶氮雙異丁腈、2,2’-偶氮雙（2,4-二曱基戊腈）、2,2'-偶氮雙（4-甲氧基-2,4-二甲基戊腈）、4,4’-偶氮雙（4-氰基戊酸）、二甲基-2,2M禺氮雙（2-曱基丙酸酯）、2,2’-偶氮雙（4-甲氧基-2,4-二甲基戊腈）等。它們之中較佳為2,2’-偶氮雙異丁腈、2,2’-偶氮雙 (2,4-二曱基戊腈）。自由基聚合引發劑可以單獨或混合兩種以上使用。作為自由基聚合引發劑的用量，相對於化合物（i)、化合物（ii)和化合物（iii)總計100質量％，通常較佳為0.1質量％〜50質量％，更佳為0.1質量％〜20質量％。另外，在上述聚合反應中，可以使用用於調節分子量的分子量調節劑。作為分子量調節劑，可以列舉出例如：氣仿、四溴化碳等齒代烴類；正己基硫醇、正辛基硫醇、正十二烷基硫醇、三級十二烷基硫醇、毓基乙酸等硫醇類；硫化二甲基黃原酸酯、二硫化二異丙基黃原酸酯等黃原酸酯類； -18- 201202844 1，4(8)-對蓋二烯〇6巧111〇161^)、〇1-曱基苯乙烯二聚物等。作為分子量調節劑的用量’相對於化合物（丨）、化A 物（ii)和化合物（ιΠ)總計1 00質量％，通常為〇.丨質量％〜5〇質量％ ’較佳為0.2質量％〜16質量％，更佳為〇 4質量 %〜8質量％。聚合溫度通常為〇°C〜150。(：，較佳為5〇t：〜120°C。聚合時間通常為10分鐘〜20小時，較佳為3〇分鐘〜6小時。作為[A]共聚物的聚苯乙烯換算的重量平均分子量 (Mw)較佳為 2.0M03〜ι·〇χ1〇5，更佳為 5·〇χ1〇3〜5 〇m〇4 通過使[A]共聚物的Mw是2.0 xlO3以上，在感放射線性樹脂組成物得到足夠的顯影界限的同時，可以防止形成的塗膜的殘膜率（圖案狀薄膜適當殘留的比例）降低，進而良好地確保得到的絕緣膜的圖案形狀以及财熱性等。另一方面’通過使[Α]共聚物的Mw為l.oxio5以下，可以保持很高的放射線感度，得到良好的圖案形狀。另外，作為[A]共聚物的分子量分佈（Mw/Mn)較佳為5.0以下，更佳為3 ·〇以下》通過使[a]共聚物的Mw/Mn為5 .〇以下’可以良好地確保得到的絕緣的圖案形狀。另外，包含具有上述這種較佳的範圍的Mw和Mw/Mn的[A]共聚物的感放射線性樹脂組成物，具有很高的顯影性，所以在顯影步驟中，不會產生顯影殘留，可以容易地形成規定的圖案形狀。 < [B ]聚合性化合物> [B ]聚合性化合物是具有乙烯性不飽和鍵的聚合性化合物。作為該組成物中含有的[B]聚合性化合物，可以 -19- 201202844 列舉出例如ω-羧基聚己内s旨單（甲基）丙烯酸醋、乙二醇 (曱基）丙稀酸醋' 1，6-己二醇二（甲基）丙烯酸酯、丨，9-壬二醇甲基）丙烯酸8旨、四乙二醇二（曱基）丙稀酸_、聚乙二醇二（曱基）丙烯酸酯、聚丙二醇二（甲基）丙烯酸酯、一苯氧基乙醇芴二（甲基）丙烯酸酯、二羥曱基三環癸烷一（曱基）丙烯酸酯、2-羥基(甲基）丙烯醯氧基丙基甲基丙烯酸醋、2-(2，-乙烯氧基乙氧基）乙基（甲基）丙烯酸§旨、二羥甲基丙烷三（曱基）丙烯酸酯 '新戊四醇三（甲基）丙烯酸酯、新戊四醇四（曱基）丙烯酸酯、二新戊四醇五（甲基）丙烯酸醋、二新戊四醇六（甲基）丙烯酸酯、三（2 (甲基）丙稀酿氧基乙基）磷酸酯、環氧乙烷改質的二新戊四醇六丙烯酸醋、琥ίό酸改質的新戊四醇三丙烯酸酯等；以及將具有直鏈伸烷基和脂環結構且具有兩個以上的異氰酸酿基的化合物，與分子内具有一個以上的羥基且具有三個〜五個（甲基）丙烯醯氧基的化合物反應得到的胺基曱酸乙自旨（甲基）丙稀酸I旨化合物等。作為上述（Β)聚合性化合物的市售品，可以列舉出例如 ARONIX Μ-400、ARONIX Μ-402、ARONIX Μ-405、 ARONIX Μ-450、ARONIX Μ-1310、ARONIX Μ-1600、 ARONIX Μ-1960、ARONIX Μ-7100、ARONIX Μ-8030、 ARONIX M-8060、ARONIX M-8100、ARONIX M-8530、 ARONIX M-8560、ARONIX M-9050、ARONIX TO-1450、 ARONIX TO- 1 3 82(以上，東亞合成公司）； -20- 201202844 KAYARAD DPHA、KAYARAD DPCA-20、KAYARAD DPCA-30、KAYARAD DPCA-60、KAYARAD DPCA-120、 KAYARAD MAX-35 10(以上，日本化藥公司）； VISCOTE 295、VISCOTE 300、VISCOTE 360、 VISCOTE GPT、VISCOTE 3PA、VISCOTE 400(以上，大阪有機化學工業公司）作為胺基曱酸乙酯丙烯酸酯系化合物是 NEWFRONTIER R-1150(第一工業製藥公司）； KAYARAD DPHA-40H、UX-5000(以上，日本化藥公司）； UN-9000H(根上工業公司）；〇 II Ά I H (1) / R4 , N, i H H H (2) ^ H 〇 (3) : (1) where R1 and R2 each independently represent a hydrogen atom and have a carbon number of 1 to 12. The alkyl group, cyclohexyl group, phenyl group, naphthyl group, vinyl group, and oxime of i may be substituted by an alkyl group having 1 to 碳, a halogen group, a group, a carboxyl group, and an arthyl group. The alkyl group having 1 to 12 carbon atoms and stupid base. (2) φ q Λ ' R, R each independently represents a hydrogen atom, a carbon atom of 1 to 12 h, a cycline, a cyclohexyl group 'A represents a methylene group, and the number of carbon atoms is 2 to 12 Ganxin, phenyl, naphthyl, vinyl, or oxime 201202844 An alkyl group having a reverse atomic number of 丨~6, a halogen-substituted fluorenylene group, and an alkylene group having 2 to 12 carbon atoms. , stretching phenyl, stretching naphthyl. In the formula (3), R5 and R6 each independently represent a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, a cyclohexyl group, and A represents an anthracene group and an alkylene group having 2 to 12 carbon atoms. a phenyl group, a naphthyl group, or a fluorenylene group substituted with an alkyl group having 1 to 6 carbon atoms; an alkyl group having 2 to 12 carbon atoms; a phenyl group; base. A radiation sensitive resin composition further characterized in that [A] the epoxy group-containing polymer is a copolymer further having a carboxyl group (hereinafter also referred to as "[A] copolymer"). The [A] polymer, the [B] polymerizable compound, the [C] polymerization initiator, and the [D] compound are contained as an alkali-soluble resin. This composition as a photosensitive material can easily form a U fine and delicate pattern by utilizing radiation-sensitive exposure and development, and has sufficient radiation sensitivity. Further, the composition contains the [D] compound having a guanamine group in the molecule represented by the above formulas (1) to (3). By containing the [D] compound, the composition can simultaneously exhibit storage stability and low-temperature firing. The compound [D] is a compound having a primary or secondary guanamine group, which has a lower nucleophilicity to an epoxy group than a compound having a primary or secondary amine group, and is hardly able to be at room temperature. The hardening reaction of the epoxy group is carried out. Therefore, in this case, when the storage stability of the heating composition of the composition is excellent to the degree of regularity or more, the [D] compound promotes the hardening reaction of the epoxy group-containing resin and exhibits hardening as an epoxy group. The function of the accelerator. The above [C] polymeric hair styling agent is preferably at least one selected from the group consisting of an acetophenone compound and a 〇_醯肟 compound. As the [C] polymerization 201202844 initiator, by using the specific compound described above, it is possible to further improve the properties required as a cured film, such as heat resistance, even in the case of a low exposure amount. The method for forming a cured film of the present invention comprises: (1) a step of forming a coating film of the composition on a substrate, (2) a step of irradiating at least a part of the coating film formed in the step (1) with radiation, (3) The step of developing the coating film irradiated with radiation in the step (2), and (4) the step of extruding the film after development in the step (3). By the formation method of the present invention using the composition, it is possible to form a cured film β which satisfactorily satisfies the required properties such as heat resistance, chemical resistance, light transmittance, flatness, voltage holding ratio, and heat linear expansion property. The firing temperature in the above step (4) is preferably 2 Torr or less. Since the composition contains the [D] compound as described above, it is excellent in storage stability while achieving low-temperature firing, and has sufficient radiation sensitivity. Therefore, the composition is suitably used as a material for forming a cured film such as an interlayer insulating film, a protective film, and a spacer which are used in a flexible display or the like which is desired to be fired at a low temperature. The protective film or the spacer ‘having the hardening film formed of the composition as an interlayer insulating film or the like is also suitable for inclusion in the present invention. Further, display elements of the film are also suitable for inclusion in the present invention. "Burning" means that the surface required for heating to obtain a cured film is hard. In addition, the meaning of the interlayer insulating film, the protective film and the spacer described in the present specification is 201202844 degrees. The "radiation" of the "radiation-sensitive resin composition" is a concept including visible light rays, ultraviolet rays, far ultraviolet rays, X-rays, charged particle beams, and the like. [Effects of the Invention] As described above, the radiation-sensitive resin composition of the present invention can easily form a fine and delicate pattern, and is excellent in storage stability and low-temperature firing, and has sufficient radiation sensitivity. Further, the cured film formed of the composition is excellent in heat resistance, chemical resistance, light transmittance, flatness, voltage holding ratio, heat-resistant linear expansion property, and the like which are required properties. Therefore, the composition is suitably used as a material for forming a hard film such as an interlayer insulating film, a protective film, or a spacer which is used in a flexible display or the like which is desired to be fired at a low temperature. [Embodiment] Hereinafter, embodiments of the invention will be described in detail. <Radiation-sensitive linear resin composition> [B] The polymerizable radiation-linear resin composition contains [A] polymer, and the composition using the sensitizing radiation 22: light as a photosensitive material passes through a delicate pattern, and : There are 5 developments, and it is easy to form fine and the object is heated by the (4) line sensation containing the [D] compound. Hereinafter, a chemical element having an epoxy group can be described in detail for a long-term storage stability and low. In the present invention, [eight] 1 right m [A] polymer) is a compound having a molecular oxy group (hereinafter, also referred to as polymerization of 3,4-epoxycyclohexyl group; having two or more glycidyl groups or 201202844 a phenolic fat such as a lipopolysaccharide of a polyglycol of polyethylene glycol; a multi-chain binary type; a varnish type in the ring is a dioxide having an alcohol diglycidol-added aliphatic polyphenol phenolic phenolic cyclic acid Large two of the epoxy tree 1 methoxy glycerin oil screams a type or a shrinkage varnish-type oxyresin shrinking glycerol oil, a ring of lipids and a polymeric ether, poly: two kinds of Ether Epoxy resin a specific poly-phenolic form of a cyclic oil ester epoxidized oxy group, a specific propylene glycol didiol, an oxidation on a propylene; a bisphenol A lipid; an aliphatic ring, and a linseed oil compound ring Examples of the oxy resin are polyphenol novolak type novolac type oxyresin which can be obtained by glycidyl ether diol or glycerene; shrinkage of a fatty acid, etc. These are preferably benzene, etc., such as benzene, etc. The patriline glyceride is awakened in the molecular group S The present invention further contemplates that [A] a polymer having an epoxy group is a copolymer further having a carboxyl group (hereinafter also referred to as "[A] copolymer"). [A] a copolymer having (al) a mercapto-containing structure a unit and an epoxy group-containing structural unit. As a method for obtaining the [A] copolymer, for example, an unsaturated acid and/or unsaturated rebel which will provide (al) a carboxyl group-containing structural unit (carboxy group further including an acid anhydride group) Acid needle (hereinafter also referred to as "chemical person") and a radical polymerizable compound having an epoxy group which provides (a2) an epoxy group-containing structural unit (hereinafter referred to as "compound (ii) j The solvent is obtained by copolymerization using a polymerization initiator. Further, if necessary, a radically polymerizable compound such as (alkyl)alkyl (a) can be used (hereinafter, also referred to as "compound (iii)). The compound (i) and the compound (ii) are simultaneously copolymerized to form the [A] copolymer. Examples of the compound (i) include, for example, -10-201202844 acrylic acid, methacrylic acid, succinic acid, and 2 -Methyl propylene oxiranyl ethyl six Hydrogen phthalic acid, 2-carboxylic acid, etc.; monobasic acid; crotonic acid, 2-propenyloxyethyl ethyl succinic acid, 2-propenyl methoxy propylene oxide, hexaethylene phthalate Dicarboxylic acid, such as gamma, konconic acid, etc.; dicarboxylic acid needles such as maleic anhydride. Among them, you μ s «copolymerization reactivity and the copolymer's revealability to the test solution Dema; & . Liver r 而, s, preferably acrylic acid, methacrylic acid, 2-propenyl methoxy succinic acid, 2 • mercapto propylene oxy succinic acid, anhydride. [A] In the copolymer, the compound (1) may be used singly or in combination of two or more. The content of the compound (1) in the [A] copolymer is preferably from 丄% by mass to 40% by mass, more preferably from 7% by mass to 30% by mass, even more preferably from 8% by mass to 25% by mass. By setting the content of the compound (1) to 1 mass% to 40% by mass, it is possible to obtain a radiation-sensitive resin-grade resin having a higher level of properties such as radiation sensitivity, developability, and storage stability. The compound (ii) may be a radically polymerizable compound having an epoxy group (cyclic oxime group, propylene oxide group) or the like. Examples of the radically polymerizable compound having an oxymethane group include glycidyl acrylate, 2-methylglycidyl acrylate, 3,4-epoxybutyl acrylate, and 6,7-epoxy acrylate. Cyclohexyl acrylate such as heptanoic acid, propionic acid 3 4 epoxy cyclohexyl ester, acrylic acid-3,4·epoxycyclohexyl methyl ester; 201202844 glycidyl methacrylate, 2-methyl shrinkage of methacrylic acid Glyceride, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl methacrylate, 3,4-epoxycyclohexyl methacrylate, methacrylic acid-3,4-epoxy Epoxyalkyl methacrylate such as cyclohexyl methyl ester; glycidyl α-ethylpropionate, glycidyl α-n-propyl acrylate, α-n-butyl acrylate glycidol, α - Alpha-alkyl acrylate alkyl acrylate such as ethyl propionate 6,7-epoxyheptyl ester; o-vinyl benzyl glycidyl ether, m-vinyl glycidyl bond, p-vinylbenzyl glycidyl ether Such as glycidol _. Examples of the radically polymerizable compound having an oxypropylene group include 3-(methacryloxymethyl) propylene oxide and 3 (methyl methoxycarbonyl)-3-ethyl ring. Oxypropyl propylene oxide, 3_(methyl propylene oxide oxygen: soil) 曱曱环氧环氧、, · (methacryloyloxyethyl) epoxide:: 3-(methacryloxy ethoxylate _3 ethyl epoxide 150, 2-ethyl = methyl propylene oxyethyl) epoxide, 3 cases of methoxyoxypropane, 3-(propylene methoxymethyl) _3 _ Ethyl olefin methoxymethyl melamine, 3-(propyl: yl)-2-f oxypropyl propyl ketone, 3 _ (alkenyloxy oxypropane, 3-(acryloxy) Ethyl)_3_ethyl produced ^ 3-(meat oxime oxyethyl) epoxide, propylene, 2-ethyl propylene oxide, 2-methyl ketone Base) methyl-2-(mercaptopropenyloxymethyl, float-3-methyl-2-(methacryloxymethyl)cyclopropane, propyloxymethyl) Epoxy propylene, hydrazine, 4_methyl 2 - (methyl ethyl methacrylate, 2 - (2 - (3 - methyl) / propylene oxide)) acrylic, 2- (methacryl Oxygen 2: propane group)) ethyl-methane, 2·(methacryloxyethyl) :)_2_methylepoxypropyl sulfonamide, 2-(propylene•12· 201202844 醯oxy 曱Propylene oxide, 2-mercaptopropane, 3-methylamide 2 & (propylene methoxymethyl) cyclohexane r-yl-2-(acryloxymethyl)oxy-2-(propylene oxide)曱 ) ) 虱、、 4 4 4 4 4 4 2- ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 2_(propylene decylethyl)_4 A fluorenyl% rolled propane, among them (meth)acrylic acid such as acetophenone. Methyl end h Acrylic acid glycidyl cool, methacrylic acid 2 : Glycidyl methacrylate, methacrylic acid M_epoxybutyl _, oxymethyl) propylene oxide, _ decane, ... pot one (mercapto propylene oxime oxime) propylene propylene 3 _ (methacryl awake Oxymethyl)_3_ethyl propylene oxide 'propylene oxy oxime) propylene propylene oxide, and the cured film obtained from the obtained interlayer insulating film, the protective film, and the spacer has high adhesion to the substrate. It has higher heat resistance and thus improved reliability of display elements. of. In the [Α] copolymer, the compound (ii) may be used singly or in combination of two or more. In the [A] copolymer, the content of the compound (丨丨) is preferably from 1 ng / 〇 to 70% by mass, more preferably from 5% by mass to 65% by mass. When the content of the compound (ii) is from 1% by mass to 7% by mass, the molecular weight of the copolymer can be easily controlled, and a radiation-sensitive resin composition having a higher level of developability and sensitivity can be obtained. Examples of the compound (iii) include (meth)acrylic acid alkyl ester, (fluorenyl)propionic acid alicyclic ester, oxygen atom-containing unsaturated heteropentacyclic ring, and six-membered ring (meth) acrylate. , (meth) acrylate having a hydroxyl group, aryl (meth) acrylate, unsaturated dicarboxylic acid diester, maleimide compound, (mercapto) acrylic acid, base benzene, benzene Ethylene, α-methylstyrene, 1,3-butadiene. -13- 201202844 As the alkyl (meth)acrylate, for example, decyl methacrylate, ethyl methacrylate, n-butyl methacrylate, dimethyl acrylate non-butyl acrylate, methacrylic acid Tertiary butyl ester, decyl acrylate, ethyl acrylate, n-butyl acrylate, secondary butyl acrylate, tertiary butyl acrylate, and the like. The (fluorenyl) acrylate cyclic alkyl ester may, for example, be cyclopentyl methacrylate, cyclohexyl methacrylate, 2-mercaptocyclohexyl methacrylate or trimethylcyclohexyl methacrylate. Amyl ester, 2-dicyclopentyloxyethyl methacrylate, isodecyl methacrylate, cyclopentyl acrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclohexyl acrylate Cyclopentyl ester, 2-dicyclopentyloxyethyl acrylate, isodecyl acrylate, and the like. Examples of the unsaturated heteroquinone ring and the six-membered ring thiol acrylate having an oxygen atom include tetrahydrofurfuryl (meth) acrylate and 2-methyl propylene oxy oxy-propionic acid. Glycosyl-based, 3-(indenyl) propylene nitrite. An unsaturated compound containing a tetrahydrofuran skeleton, such as 2-anthracene-2-anthracene; 2-mercapto-5-(3-furyl)-1-penten-3-one, (mercapto)acrylic acid sulfhydryl group, 1 - °夫叫-2 -丁- 3-稀-2 -嗣,1 -α夫喃-2 - butyl-3 -anthracene-3 -rath-2 -嗣,6_(2 -α-furanyl) -2 -Methyl-1 -hexyl;fcfp - 3 -嗣,6- °furan-2-yl-hexyl-1 -fine-3 -indole,acrylic acid-2"°夫喃-2 -yl- An unsaturated compound containing a D-flan skeleton such as 1 - mercapto-ethyl S, 6-(2_.fufenyl)-6-mercapto-1-heptan-3-one; methacrylic acid (tetrahydropyridyl) Methyl-2-yl)methyl, 2,6-dimethyl-8-(tetra-m-pyran-2-yloxy)-oct-1-expansion-3-S, 2-methyl propylene Acid four mouse-14- 201202844 吼 -2 -2 - yl ester, 1-(tetrahydropyran-2-yloxy)-butyl-3- ene-2-one and other unsaturated containing tetrahydropyranyl skeleton Compound; 4-U,4-dioxa-5.oxo-6-heptenyl)-6-mercapto-2-pyran, dioxa-6-oxo-7-octenyl)_6_ An unsaturated compound containing a fluorene ring or the like, such as methyl-2_0. As the (meth) acrylate having a hydroxyl group, hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate can be exemplified as 3-hydroxypropyl (meth) acrylate. , (fluorenyl) 2,3-dihydroxypropyl acrylate, and the like. The (meth)acrylic acid aryl ester may, for example, be (meth)acrylic acid phenylacetic acid or (mercapto)acrylic acid benzyl ester. Examples of the unsaturated dibasic acid-lower diester include diethyl maleate, diethyl fumarate, and diethyl itaconate. Examples of the maleinimide compound include N-phenyl maleimide, N-cyclohexylmaleimide, N-based mercapine, and Ν-(4. hydroxyphenyl). ) maleimide, benzylidene) maleimide, N-succinimide _3_maleimide benzoic acid vinegar, N_amber quinone imine-4-malay Iminobutyrate, N_amber succinimide _6_maleimide caproic acid vinegar, N- sulphate quinone imine _3_maleimide propionic acid slightly, N-(9- The content of the compound (Hi) in the [A] copolymer is preferably from 7% by mass to 70% by mass, more preferably from 15% by mass to 65% by mass. The content of the compound (ih) is 1 〇f % to 7 (% by mass), and the molecular weight of the easy polymer can be obtained as developability and sensitivity 'adhesion 2: a gradedly optimized radiation sensitive resin composition .円-15-201202844 <Synthesis method of [A] copolymer> [A] The copolymer can be used, for example, by using the compound (i), the compound (ii), and the compound (iii) used as needed in a solvent. The base polymerization initiator is polymerized and synthesized. Examples of the solvent used in the polymerization reaction for producing the [A] copolymer include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol alkyl ethers, and propylene glycol monoalkanes. Alkyl ether, propylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether propionate, aromatic hydrocarbons, ketones, other esters, and the like. Examples of the alcohol include methanol, ethanol, benzofuran, 2-phenylethyl alcohol, and 3-phenyl-1-propanol. Examples of the ethers include a cyclic ether, a glycol ether, an ethylene glycol alkyl ether acetate, a diethylene glycol alkyl ether, a propylene glycol monoalkyl ether, a propylene glycol monoalkyl ether acetate, and a propylene glycol monoalkane. Ethyl ether propionate and the like. Examples of the cyclic ether include tetrahydrofuran and the like. The glycol ether may, for example, be ethylene glycol monomethyl ether or ethylene glycol monoethyl ether. Examples of the ethylene glycol alkyl ether acetate include, for example, methyl stilbene acetate, ethyl stilbene acetate, ethylene glycol monobutyl ether acetate, and ethylene glycol monoethyl ether acetate. Ester and the like. The diethylene glycol alkyl ether may, for example, be diethylene glycol monoterpene, diethylene glycol monoethyl ether, diglyme, diethylene glycol di(10) or diethylene glycol decyl ethyl ether. Examples of the propylene glycol monoalkyl ether include propylene glycol monoterpene ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether. -16 - 201202844 Examples of the propylene glycol monoalkyl ether acetate include propylene glycol monoterpene ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and propylene glycol monobutyl ether acetate. Examples of the propylene glycol monoalkyl ether propionic acid vinegar include propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol monopropyl ether propionate, and propylene glycol monobutyl ether propionate. Examples of the aromatic hydrocarbons include toluene, xylene, and the like. Examples of the ketones include methyl ethyl ketone, cyclohexanone, and 4-hydroxy-4-methyl-2-pentanone. Examples of the other esters include decyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-mercaptopropionate, and 2-hydroxy- 2 - mercaptopropionate, hydroxyacetate, ethyl hydroxyacetate, butyl glycolate, decyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, 3 - Ethyl hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-mercaptobutyrate, decyl methoxyacetate, ethyl methoxyacetate, hydrazine Propyl oxyacetate, butyl oxyacetate, decyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, decyl propyl acetate, propoxy Ethyl acetate, propyl propyl acetate, butyl propoxy acetate, decyl butoxyacetate, ethyl butoxide, butyl butoxyacetate, butyl butoxyacetate, 2-methyl Methyl oxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, decyl 2-ethoxypropionate, 2-B Ethyl oxypropionate, 2 -propyl ethoxypropionate, butyl 2-ethoxypropionate, decyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, 2 -butyl butoxypropionate, 3-oxime-17- 201202844 methyl propyl propionate, ethyl 3-methoxyoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionic acid Butyl ester, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, 3-propoxypropionic acid Methyl ester, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, 3-butoxypropionic acid Ethyl ester, propyl 3-butoxypropionate, butyl 3-butoxypropionate, and the like. Examples of the radical polymerization initiator include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimercaptophthalonitrile), and 2,2'-couple. Nitrogen bis(4-methoxy-2,4-dimethylvaleronitrile), 4,4'-azobis(4-cyanovaleric acid), dimethyl-2,2M fluorene double (2- Mercaptopropionate, 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), and the like. Among them, preferred is 2,2'-azobisisobutyronitrile and 2,2'-azobis(2,4-dicinylvaleronitrile). The radical polymerization initiator may be used singly or in combination of two or more. The amount of the radical polymerization initiator to be used is 100% by mass based on the total of the compound (i), the compound (ii) and the compound (iii), and is usually preferably 0.1% by mass to 50% by mass, more preferably 0.1% by mass to 20% by mass. quality%. Further, in the above polymerization reaction, a molecular weight modifier for adjusting the molecular weight can be used. Examples of the molecular weight modifier include a toothed hydrocarbon such as a gas-like or carbon tetrabromide; n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, and tertiary dodecyl mercaptan. Mercaptans such as thioglycolic acid; xanthates such as dimethyl xanthate sulfide and diisopropyl xanthate disulfide; -18- 201202844 1,4(8)-pateadiene 〇6巧111〇161^), 〇1-mercaptostyrene dimer, and the like. The amount of the molecular weight modifier is '100% by mass based on the compound (丨), the chemical A (ii) and the compound (ι), and is usually 〇.丨% by mass to 5% by mass%, preferably 0.2% by mass. ～16% by mass, more preferably 〇4% by mass to 8% by mass. The polymerization temperature is usually from 〇 ° C to 150 °. (:, preferably 5 〇 t: ～120 ° C. The polymerization time is usually from 10 minutes to 20 hours, preferably from 3 minutes to 6 hours. The polystyrene-equivalent weight average molecular weight of the [A] copolymer (Mw) is preferably 2.0M03 to ι·〇χ1〇5, more preferably 5·〇χ1〇3~5 〇m〇4 by making the Mw of the [A] copolymer 2.0xlO3 or more, in the radiation sensitive resin When the composition has a sufficient development limit, it is possible to prevent the residual film ratio of the formed coating film (the ratio of the pattern-form film remaining as appropriate) from being lowered, and to secure the pattern shape and the heat recovery property of the obtained insulating film. By setting the Mw of the [Α] copolymer to 1.oxio5 or less, a high radiation sensitivity can be maintained, and a good pattern shape can be obtained. Further, the molecular weight distribution (Mw/Mn) of the [A] copolymer is preferably 5.0. In the following, it is more preferable that the Mw/Mn of the [a] copolymer is 5 Å or less, and the obtained insulating pattern shape can be satisfactorily ensured. Further, the above-described preferred range is included. a radiation sensitive resin composition of the [A] copolymer of Mw and Mw/Mn, Since it has high developability, development residue does not occur in the development step, and a predetermined pattern shape can be easily formed. [B] Polymerizable compound > [B] The polymerizable compound has an ethylenically unsaturated bond. Polymerizable compound. As the [B] polymerizable compound contained in the composition, for example, -19-201202844, for example, ω-carboxypolyhexene s, mono (meth) acrylate, ethylene glycol (mercapto) propylene Dilute vinegar '1,6-hexanediol di(meth)acrylate, hydrazine, 9-nonanediol methyl)acrylic acid, tetraethylene glycol bis(indenyl)propionic acid _, polyethylene Alcohol bis(mercapto) acrylate, polypropylene glycol di(meth) acrylate, monophenoxyethanol hydrazine di(meth) acrylate, dihydroxy decyl tricyclodecane mono(indenyl) acrylate, 2 -hydroxy(meth)acryloxypropyl methacrylate, 2-(2,-vinyloxyethoxy)ethyl(meth)acrylic acid, dimethylolpropane tris(decyl) Acrylate 'neopentitol tris(meth)acrylate, pentaerythritol tetrakis(meth)acrylate, dipentaerythritol Alcohol penta(methyl) acrylate vinegar, dipentaerythritol hexa(meth) acrylate, tris(2(methyl) propylene oxyethyl) phosphate, ethylene oxide modified dioxane a tetraol hexaacrylate vinegar, a succinic acid modified neopentyl alcohol triacrylate, etc.; and a compound having a linear alkyl group and an alicyclic structure and having two or more isocyanate olefinic groups, and intramolecular An amino phthalic acid obtained by reacting a compound having one or more hydroxyl groups and having three to five (meth) acryloxy groups is a compound of (meth) acrylic acid I. The commercially available product of the above (Β) polymerizable compound may, for example, be ARONIX®-400, ARONIX®-402, ARONIX®-405, ARONIX®-450, ARONIX®-1310, ARONIX®-1600, ARONIX®- 1960, ARONIX Μ-7100, ARONIX Μ-8030, ARONIX M-8060, ARONIX M-8100, ARONIX M-8530, ARONIX M-8560, ARONIX M-9050, ARONIX TO-1450, ARONIX TO- 1 3 82 (above) , East Asia Synthetic Company); -20- 201202844 KAYARAD DPHA, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120, KAYARAD MAX-35 10 (above, Nippon Chemical Co., Ltd.); VISCOTE 295, VISCOTE 300, VISCOTE 360, VISCOTE GPT, VISCOTE 3PA, VISCOTE 400 (above, Osaka Organic Chemical Industry Co., Ltd.) as an amino phthalate acrylate compound is NEWFRONTIER R-1150 (First Industrial Pharmaceutical Company); KAYARAD DPHA- 40H, UX-5000 (above, Nippon Kayaku Co., Ltd.); UN-9000H (Keeda Industrial Co., Ltd.);

ARONIX M-5300、ARONIX M-5600、ARONIX M-5700、ARONIX M-210、ARONIX Μ·220、ARONIXARONIX M-5300, ARONIX M-5600, ARONIX M-5700, ARONIX M-210, ARONIX Μ·220, ARONIX

Μ-240、ARONIX Μ-270、ARONIX Μ-6200、ARONIX M-305 、ARONIX M-309、ARONIX M-310、ARONIX M-3 15(以上，東亞合成公司）； KAYARAD HDDA、KAYARAD HX-220、KAYARAD HX-620'KAYARAD R-5 26' KAY ARAD R-1 67 ' KAYARAD R-604、KAYARAD R-684、KAYARAD R-55 卜 KAYARAD R-712、UX-2201、UX-2301、UX-3204、UX-3301、 UX-4101、UX-6101、UX-7101、UX-8101、UX-0937、 MU-2100、MU-4001(以上，日本化藥公司）； art resin UN-9000PEP、art resin UN-9200A、art resin UN-7600、art resin UN-333、art resin UN-1003、art resin UN- 1 25 5、art resin UN-6060PTM、art resin UN-6060P(以上，根上工業公司）； -21- 201202844 SH-500B VISCOTE 260、VISCOTE 312、VISCOTE 3 3 5HP(以上，大阪有機化學工業公司）等。 [B]聚合性化合物可以單獨或混合兩種以上使用。作為該組成物中的[B]聚合性化合物的含有比例，相對於 100質量份[A]聚合物或[A]共聚物，較佳為20質量份〜200質量份，更佳為40質量份〜160質量份。通過使聚合性化合物的含有比例為上述範圍，該組成物密合性也優異’即使在低曝光量下，也可以得到具有足夠的硬度的層間絕緣膜、保護膜和間隔物等硬化膜。 <[C]聚合引發劑> 該組成物中含有的[c]聚合引發劑是感應放射線而產生能夠引發[B]聚合性化合物的聚合的活性種的成分。[C]聚合引發劑較佳為含有由〇_醯基肟化合物和乙醢笨化合物構成的群組中選出的至少一種。作為0-醯基肟化合物，可以列舉出例如丨，2_辛二醇苯基硫代）-2-(匕笨甲醯基肟）]、乙酮乙基 -6-(2-曱基苯甲醯基）_9H_咔唑_3基]小（〇_乙醯基肟/ 1-[9 -乙基-6-苯曱酿基_9h咔唑_3_基]辛_卜酮杇乙酸酯、1-[9-乙基-6-(2-曱基苯曱醯基）_9Η·_咔唑、3_基]_ 乙_1_酮肟-〇-苯曱酸鲳、1-[9-正丁基-6-(2-乙基笨曱醯基）-9·Η·-咔唑-3-基]-乙酮肟苯甲酸酯、乙鲷乙基-6-(2-甲基-4-四氣呋喃基苯甲醯基）_9·Η·-咔唑_3. 基]_1-(〇-乙醯基肟）、乙酮-1-[9-乙基-6-(2-甲基、4_四氫吡喃基苯甲醯基）_9.Η·-咔唑_3_基]乙醯基肟）、乙酮 -1-[9-乙基-6-(2-甲基_5、四氫呋喃基苯甲醯基）_9 Η _咔 -22- 201202844 。坐-3 -基]-1-(0 -乙酿基月亏）、乙嗣-1 - [9-乙基-6- {2-甲基 -4-(2,2-二曱基-1，3-二氧戊環基）曱氧基苯甲醯基}-9.11.-咔唑-3-基]-1-(0-乙醯基肟）等。它們之中，較佳為 1,2-辛二醇-1-[4-(苯基硫代）-2-(0-苯甲醯基肟）]、乙酮-l-[9 -乙基- 6- (2 -甲基苯曱醯基）-9H-咔唑-3-基]-1-(0 -乙醯基肟）、乙酮- l-[9 -乙基 -6-(2-甲基-4-四氫呋喃基曱氧基苯曱醯基）-9.H.-咔唑-3-基]-1-(0-乙醯基肟）或乙酮-l-[9 -乙基- 6-{2 -甲基- 4-(2,2-二曱基-1，3-二氧戊環基）曱氧基苯曱醯基}-9.11.-咔唑-3-基]-1 - (Ο -乙醯基肟）。作為乙醯苯化合物，可以列舉出例如α -胺基酮化合物、α -經基酮化合物。. 作為 α-胺基酮化合物，可以列舉出例如 2-苄基-2-二曱基胺基-1-(4 -味琳代本基）-丁 -1-嗣、2-二曱基胺基 -2-(4-甲基苄基）-1-(4-咪啉-4-基-苯基）-丁 -1-酮、2-曱基 -1-(4-曱硫基苯棊）-2-咮啉代丙-1-酮等。作為 α-羥基酮化合物，可以列舉出例如 1 -苯基-2-羥基-2-甲基丙-1-酮、1-(4-異丙基苯基）-2-羥基-2-甲基丙 -1 - 3同、4 - (2 -經基乙氧基）本基-(2 -經基-2 -丙基）嗣、1 -經基環己基苯基酮等。它們之中，較佳為α -胺基酮化合物，更佳為2 -苄基 -2-二甲基胺基-1-(4-味琳代苯基）-丁-1-嗣、2-二曱基胺基 -2-(4-曱基苄基）-1-(4-咮啉-4-基-苯基）-丁 -1-酮、2-曱基 -1 - [ 4 -曱硫基苯基]-2 -味琳代丙-1 - S同。 -23- 201202844 [c]聚合引發劑可以單獨或混合兩種從u上使用。作為 [C]聚合引發劑通過使用上述特定化合物， g卩使在低曝光量的情況下，也可以進一步提高耐熱性耸寻作為硬化膜所要求的性質。作為該組成物中的[C]聚合引發劑的今士， J 3有比例，相對於100質量份[A]聚合物或[A]共聚物，軔杜4 隹為1質量份〜40質量份，更佳為5質量份〜30質量份。、s、η 里物。通過使[C]聚合引發劑的含有比例為1質量份〜4〇質|八 0也各負里份，該組成物即使在低曝光量的情況下，也可以形成 —人u取具有南的硬度和岔合性的層間絕緣膜、保護膜和間隔物等硬化膜。 <[〇]通式（1)〜（3)所示的化合物〉、 δ玄組成物通過含有呈右卜抽〔式丨1、,，、脸… ⑴〜()所示的具有醯胺基的化5物（以下’也稱作[ D1化人抽J、 __ )’可以同時實現保存穩疋性和低溫燒製。絲上述式⑴所示的化合物是在分子内具有-個醯胺的化合物。作為其具體例子，可以列舉 -甲基乙酿胺、…乙酿胺、Ν·正丙基乙酿=異，基乙醯胺、Ν_正丁基乙醯胺、Ν•異丁基乙醯胺、Ν_三 =丁基乙醯胺、Ν•正己基乙醯胺、1正辛基乙醯胺、Ν_ 正十一烷基乙醯胺、丙醯胺、丁醯胺、戊醯胺、異戊醯 =、辛醯胺、乙醯苯胺、乙醯基乙醯苯胺、鄰乙醯胺基苯甲敲、間乙醯胺基苯甲酸、對乙醯胺基苯甲酸、鄰乙醯胺基苯酚、間乙醯胺基笨酚、對乙醯胺基苯酚、乙醯胺基萘、鄰苯二甲醢胺酸、丙烯醯胺、笨甲醯胺、萘醯胺私驗酿胺、異於驗酿胺等。 -24- 201202844 它們之中，在使用乙醯胺、N-曱基乙醯胺、鄰苯二曱醯胺酸時，該組成物在室溫下的保存穩定性更優異，而且可以提高得到的硬化膜的耐熱性、電壓保持率等。上述式（2)和（3)所示的化合物是在分子内具有兩個醯胺鍵的化合物。作為其具體例子，可以列舉出例如鄰苯二曱醯胺、間苯二曱醯胺、對苯二甲醯胺、丙二醯胺、水楊酸醯胺、戊二醯胺、己二醯胺、庚二醯胺、辛二醯胺、壬二醯胺、癸二醯胺、馬來醯胺、富馬醯胺、N，N‘-二曱基-鄰苯二甲醯胺、N，N‘-二甲基-間苯二曱醯胺、 N，N‘-二甲基-對苯二甲醯胺、N,N‘-二乙醯基-鄰伸苯基二胺、N，N‘-二乙醯基-間伸苯基二胺、N,N‘-二乙醢基-對伸苯基二胺、N，N‘-二丙醯基-鄰伸苯基二胺、N,N‘-二丙醯基-間伸苯基二胺、N,N‘-二丙醯基-對伸苯基二胺、N,N‘-二乙醯基-乙二胺、N,N‘-二乙醯基-丙二胺、N，N‘-二乙醯基-丁二胺、N,N‘-二乙醯基-1,6 -己二胺、N，N‘-二乙醯基 -1，12-十二烷二胺、N,N‘-二苯曱醯基-乙二胺、N,N‘-二苯甲醯基-丙二胺、N,N‘-二苯曱醯基-丁二胺、N,N‘-二苯甲醯基-1，6 -己二胺、N,N‘-二苯曱醯基-1,12-十二烷二胺、N，N‘-二萘基-乙二胺、N,N‘-二萘基-丙二胺、N,N‘-二萘基-丁二胺、N，N‘-二萘基-1,6-二胺、N,N‘-二萘基 -1，12-十二烷二胺等。從高等級地同時實現組成物的保存穩定性和促進硬化的觀點而言，較佳為間苯二曱醯胺、己二醯胺、Ν,Ν'-二乙醯基-對伸苯基二胺、Ν，Ν’-二乙醯基·1，6-己二胺。 -25- 201202844 上述具有醯胺基的化合物提高該組成物在室溫下的保存穩定性。另外，由於和環氧基的反應性優異，所以有助於200°C以下的低溫硬化。作為該組成物中的上述[D]通式（1)〜（3)所示的化合物的含有比例，相對於1 00質量份[A]聚合物和[A]共聚物’較佳為0.01質量份〜10質量份，更佳為〇〇5質量份〜5質量份。通過使[D]化合物的含有比例為〇〇ι質量份〜10質量份，可以更高等級地同時實現該組成物的保存穩定性和促進硬化膜的硬化’進而可以更高等級地保持得到的具有保護膜、層間絕緣膜、間隔物等硬化膜的顯示元件的電壓保持率。 <任意成分> 該組成物除了上述[A]聚合物或[A]共聚物、[B]聚合性化合物、[C]聚合引發劑以及[D]化合物以外在益損所希望的效果的範圍内，根據需要可以含有[E]在i ^子中具有兩個以上的環氧乙烷基的化合物、[F]黏合助劑、 [G]表面活性劑、[H]保存穩定劑以及⑴耐熱性提高劑等任思成刀。這些各種任意成分可以單獨使用，也可以混合兩種以上使用。以下，依次詳細描述。 ⑽在1分子中具有兩個以上環氧乙烷基的化合物] [E]在1分子中具有兩個以上的環氧乙烷基的化合物 (以下’也稱作「[E]化合物」），可以用於進—步提高得到的硬化膜的硬度而添加。作為這種[e]化合物，可以列舉出例如在1分子内具有兩個以上的3,4-環氧環己基的化合物以及其他[E]化合物，但是不包括[a]聚合物或⑷ -26- 201202844 作為上述在1分子内具有兩個以上的3，4_環氡環己基的化合物，可以列舉出例如3,4-環氧環己基甲基-3,，4，-環氧環己烷曱酸酯、2-(3,4-環氧環己基- 5,5-螺-3，4-環氧）環己烧-間二噚烷、二（3,4·環氧環己基曱基）己二酸酯、二（3,4-環氧_6 -曱基環己基甲基）己二酸酯、3,4_環氧-6_ 甲基環己基-3，，4，-環氧-6，-甲基環己烷曱酸酯、亞甲基二 (3,4-環氧環己烷）、二環氡化二環戊二烯、乙二醇的二 (3,4-環氧環己基曱基）醚、伸乙基二（3,4-環氧環己烷甲酸醋）、己内酯改質的3,4-環氧環己基曱基-3，，4，-環氧環己烷甲酸酯等。作為上述其他[E]化合物，可以列舉出例如：雙酿A二縮水甘油醚、雙酚ρ二縮水甘油醚、雙酚 S二縮水甘油醚、氫化雙酚a二縮水甘油醚、氫化雙酚 F二縮水甘油醚、氫化雙酚ad二縮水甘油醚、溴化雙酚 A二縮水甘油醚、溴化雙酚ρ二縮水甘油醚 '溴化雙酚 S二縮水甘油醚等雙酚化合物的二縮水甘油醚；作為上述[E]化合物的用量，相對於i〇〇質量份[a] 聚合物或[A ]共聚物，較佳為5 〇質量份以下，更佳為2 質置份〜50質量份’特佳為5質量份〜30質量份。通過使 [E]化合物的用量為上述範圍可以無損顯影性，進一步提咼層間絕緣膜、間隔物或保護膜等硬化膜的硬度。 [[F]黏合助劑] [F]黏合助劑用於進一步提高隔物或保護膜等硬化膜和基板的黏入的層間絕緣膜、間合助劑，較佳為具有羧基、甲 σ丨生。作為這種[F]黏㈣臨氣基、乙稀基、 -27- 201202844 異氰酸醋基、環童7 & 衣氧乙烷基等反應性官能基團的 …聯齊彳，可以列舉出例如三甲氧 d 酸Ή W氧基丙基三甲氧基找、乙甲醯氧基石夕烧、乙浠基三甲氧基石夕烧”·異：：：三乙氧…、γ'缩水甘油氧基丙基三甲氧基基 β-(3,4-環氧環己基）乙基三甲氧基矽烷等。 ^ 作為[F]黏合助劑的用量，相對於1〇〇質量份 ί:或[A]共聚物，較佳為2〇質量份以下，更佳為15 Ϊ 里知以下。如果[F]黏合助劑的用量超過2〇質量貝具有容易產生顯影殘留的傾向。 …則 [[G ]表面活性劑] [G]表面活性劑用於進一步提高該組成物的塗膜成丨生。作為[G]表面活性劑，可以列舉出例如含氟表面舌生劑、有機矽類表面活性劑以及其他表面活性劑。作= 上述含氟表面活性劑，較佳為在末端、主鏈和側鏈的至 ^任一部位具有氟烷基和/或氟伸烷基的化合與山以列出例如M，2,2-四氟正辛基（^,2,2-四氟正丙基）喊、 l1，2,2-四氟正辛基（正己基）醚、六乙二醇二（1,丨，2 2 3 3 〇敦正戊基）醚、八乙二醇二（丨，^，、四氟正丁基）驗、六丙一醇一（1，1,2,2,3,3 -六I正戊基）醚、八丙二醇_ (Μ，2,2 -四氟正丁基）醚、全氟正十二烷基磺酸鈉、六氟正癸烷、8,9,9,10，1〇_十氟正十一燒’以及氟烷基苯磺酸鈉、氟烷基磷酸鈉、氟烧基叛酸納、二甘油四（氟烷基聚氧乙烯醚）、碘化氣烷基錄、氣燒基甜菜鹼、其他氟烷基聚氧乙烯醚、全氟烷基聚氧乙醇、全氟烷基烷氧化物、羧酸氟烷基酯等。 -28- 201202844 作為含氟表面活性劑的市售品，可以列舉出例如 BM-1000、BM-1100(以上，BM CHEMIE 公司），MEGAFAC F142D、MEGAFAC F172、MEGAFAC F173、MEGAFAC F183、MEGAFAC F178、MEGAFAC F191、MEGAFAC F471、MEGAFAC F476(以上，大日本油墨化學工業公司）， FLUORAD FC-170C、FLUORAD -171、FLUORAD -430、 FLUORAD -43 1(以上，住友 3M 公司），Surflon S-112、 Surflon -113、Surflon -131、Surflon -141、Surflon -145、 Surflon -382、Surflon SC-101、Surflon -102、Surflon -103、Surflon -104、Surflon -105、Surflon -106(以上，旭硝子公司），EFTOP EF301、EFTOP 303、EFTOP 352(以上，新秋田化成公司）、FTERGENT FT-100、FTERGENT -110、FTERGENT -140A、FTERGENT -150、FTERGENT -250、FTERGENT -25 1、FTERGENT -300、FTERGENT -3 10 、 FTERGENT -400S ' FTERGENT FTX-218 、 FTERGENT -25 1(以上，（股）NEOS 公司）等。作為有機矽類表面活性劑的市售品，可以列舉出例如 Toray Silicone DC3PA、Toray Silicone DC7PA、Toray Silicone SH11PA、Toray Silicone SH21PA、Toray Silicone SH28PA、Toray Silicone SH29PA、Toray Silicone SH30PA、Toray Silicone SH-190、Toray Silicone SH-193、 Toray Silicone SZ-6032、Toray Silicone SF-8428、Toray Silicone DC-5 7、Toray Silicone DC-190(以上，Toray Dow Corning Silicone 公司），TSF-4440、TSF-4300、TSF-4445、 TSF-4446、TSF-4460、TSF-4452(以上、GE Toshiba -29- 201202844Μ-240, ARONIX Μ-270, ARONIX Μ-6200, ARONIX M-305, ARONIX M-309, ARONIX M-310, ARONIX M-3 15 (above, East Asia Synthetic Company); KAYARAD HDDA, KAYARAD HX-220, KAYARAD HX-620'KAYARAD R-5 26' KAY ARAD R-1 67 ' KAYARAD R-604, KAYARAD R-684, KAYARAD R-55 BU KAYARAD R-712, UX-2201, UX-2301, UX-3204, UX-3301, UX-4101, UX-6101, UX-7101, UX-8101, UX-0937, MU-2100, MU-4001 (above, Nippon Kayaku Co., Ltd.); art resin UN-9000PEP, art resin UN- 9200A, art resin UN-7600, art resin UN-333, art resin UN-1003, art resin UN- 1 25 5, art resin UN-6060PTM, art resin UN-6060P (above, root industrial company); -21- 201202844 SH-500B VISCOTE 260, VISCOTE 312, VISCOTE 3 3 5HP (above, Osaka Organic Chemical Industry Co., Ltd.). [B] The polymerizable compound may be used singly or in combination of two or more. The content ratio of the [B] polymerizable compound in the composition is preferably 20 parts by mass to 200 parts by mass, more preferably 40 parts by mass, per 100 parts by mass of the [A] polymer or the [A] copolymer. ~ 160 parts by mass. When the content ratio of the polymerizable compound is in the above range, the composition is excellent in adhesion. Even at a low exposure amount, a cured film such as an interlayer insulating film, a protective film, and a spacer having sufficient hardness can be obtained. <[C] Polymerization Initiator> The [c] polymerization initiator contained in the composition is a component which induces radiation to generate an active species capable of initiating polymerization of the [B] polymerizable compound. The [C] polymerization initiator preferably contains at least one selected from the group consisting of ruthenium ruthenium ruthenium compound and acetophenone compound. Examples of the 0-fluorenyl hydrazine compound include hydrazine, 2 octyl diol phenyl thio)-2-(anthracene fluorenyl hydrazide), and ethyl ketone ethyl-6-(2-mercaptobenzene). Methyl hydrazide) _9H_carbazole _3 base] small (〇_乙醯基肟 / 1-[9-ethyl-6-benzoquinone-based -9h-carbazole _3_yl] octyl ketone oxime Acid ester, 1-[9-ethyl-6-(2-mercaptobenzoyl)_9Η·_carbazole, 3_yl]_ethyl-1-ketone-indole-benzoic acid hydrazine, 1- [9-n-Butyl-6-(2-ethyl adenyl)-9·Η·-oxazol-3-yl]-ethanone benzoate, acetamylethyl-6-(2 -Methyl-4-tetrafurfurylbenzylidene)_9·Η·-carbazole_3. Group]_1-(〇-acetamido), ethyl ketone-1-[9-ethyl-6 -(2-methyl, 4_tetrahydropyranylbenzylidene)_9.Η·-carbazole_3_yl]ethinyl), ethyl ketone-1-[9-ethyl-6- (2-methyl_5, tetrahydrofuranylbenzimidyl)_9 Η _咔-22- 201202844. Sit-3 -yl]-1-(0-ethyl-based base-depleted), acetam-1 - [9-ethyl-6- {2-methyl-4-(2,2-dimercapto-1) , 3-dioxolanyl) decyloxybenzimidyl}-9.11.-carbazol-3-yl]-1-(0-ethenylhydrazine) and the like. Among them, preferred is 1,2-octanediol-1-[4-(phenylthio)-2-(0-benzylidenehydrazine)], and ethyl ketone-l-[9-ethyl - 6-(2-Methylphenylhydrazino)-9H-carbazol-3-yl]-1-(0-acetamidopurine), ethyl ketone-l-[9-ethyl-6-(2 -Methyl-4-tetrahydrofuranyloxyphenyl fluorenyl)-9.H.-carbazol-3-yl]-1-(0-ethylhydrazinium) or ethyl ketone-l-[9-B -6-{2-methyl-4-(2,2-dimercapto-1,3-dioxolanyl)nonyloxyphenylhydrazino}-9.11.-carbazol-3-yl] -1 - (Ο-乙醯基肟). The acetophenone compound may, for example, be an α-amino ketone compound or an α-pyridyl ketone compound. As the α-amino ketone compound, for example, 2-benzyl-2-didecylamino-1-(4-isolinyl)-butan-1-indole, 2-didecylamine can be exemplified. 2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, 2-mercapto-1-(4-indolethiophenylhydrazine -2- porphyrin-propan-1-one and the like. The α-hydroxyketone compound may, for example, be 1-phenyl-2-hydroxy-2-methylpropan-1-one or 1-(4-isopropylphenyl)-2-hydroxy-2-methyl. C-1,3-3, 4-(2-propylethoxy)benyl-(2-hydrazino-2-propyl)anthracene, 1-cyclohexylphenylene ketone, and the like. Among them, an α-amino ketone compound is preferred, and more preferred is 2-benzyl-2-dimethylamino-1-(4-terinylphenyl)-butan-1-anthracene, 2- Dimercaptoamino-2-(4-mercaptobenzyl)-1-(4-indololin-4-yl-phenyl)-butan-1-one, 2-mercapto-1 - [ 4 -曱Thiophenyl]-2 - taste Lin Dai C-1 - S with. -23- 201202844 [c] The polymerization initiator can be used alone or in combination from u. As the [C] polymerization initiator, by using the above specific compound, g 卩 makes it possible to further improve the heat resistance as a property required for the cured film at a low exposure amount. As a polymerization initiator of the [C] in the composition, J 3 has a ratio of 1 part by mass to 40 parts by mass relative to 100 parts by mass of the [A] polymer or [A] copolymer. More preferably, it is 5 parts by mass to 30 parts by mass. , s, η 物. By making the content ratio of the [C] polymerization initiator to 1 part by mass to 4 〇 | 八八八八八八八八八八八八八八八八八八八八八八八八八八八八八八八八八八八八八八A hardened film such as an interlayer insulating film, a protective film, and a spacer having hardness and compatibility. <[〇] The compound represented by the general formulae (1) to (3)> and the δ mysterious composition have the indoleamine represented by the formula (1) to ((), which is represented by the formula (1) to (). The base 5 (hereinafter referred to as [D1 humanized J, __)" can simultaneously achieve storage stability and low temperature firing. The compound represented by the above formula (1) is a compound having one indoleamine in the molecule. As specific examples thereof, there may be mentioned - methyl ethanoamine, ethylamine, hydrazine, propyl propyl amide, isobutyl phthalamide, hydrazine butyl phthalamide, hydrazine isobutyl hydrazine. Amine, Ν_three = butyl acetamide, Ν-n-hexyl acetamide, 1 n-octyl acetamide, Ν n-undecyl acetamide, acetamide, butylamine, amylamine, Isovalerin =, octylamine, acetophenone, ethenyl aniline, o-acetamidophene, m-decylaminobenzoic acid, p-acetamidobenzoic acid, o-acetamido Phenol, m-amylamine phenol, p-acetamido phenol, acetaminophen, phthalic acid, acrylamide, benzoguanamine, naphthylamine, sulphuric amine, different Amine amine and so on. -24- 201202844 Among them, when acetamide, N-mercaptoacetamide, or phthalic acid is used, the composition is more excellent in storage stability at room temperature, and can be improved. Heat resistance, voltage retention rate, etc. of the cured film. The compounds represented by the above formulas (2) and (3) are compounds having two guanamine bonds in the molecule. Specific examples thereof include, for example, phthalamide, isophthalamide, terephthalamide, propionamide, decyl salicylamine, pentaneamine, and hexamethylenediamine. , glyoxime, octylamine, decylamine, decylamine, maleic amine, fumarine, N,N'-dimercapto-phthalimin, N, N '-Dimethyl-m-phenylenediamine, N,N'-dimethyl-p-xylyleneamine, N,N'-diethylindenyl-o-phenylenediamine, N,N' -diethylhydrazine-m-phenylenediamine, N,N'-diethylene-p-phenylenediamine, N,N'-dipropionyl-o-phenylenediamine, N,N '-Dipropenyl-inter-phenylenediamine, N,N'-dipropenyl-p-phenylenediamine, N,N'-diethylindenyl-ethylenediamine, N,N'- Diethyl decyl-propylenediamine, N,N'-diethylindenyl-butanediamine, N,N'-diethylindenyl-1,6-hexanediamine, N,N'-diethylhydrazine -1,12-dodecanediamine, N,N'-diphenylmethyl-ethylenediamine, N,N'-dibenyl-propanediamine, N,N'-diphenylhydrazine -butanediamine, N,N'-dibenyl-1,6-hexanediamine, N,N'-diphenylhydrazine-1,12- Dialkyldiamine, N,N'-dinaphthyl-ethylenediamine, N,N'-dinaphthyl-propylenediamine, N,N'-dinaphthyl-butanediamine, N,N'-di Naphthyl-1,6-diamine, N,N'-dinaphthyl-1,12-dodecanediamine, and the like. From the viewpoint of simultaneously achieving high storage stability of the composition and promoting hardening, it is preferably m-benzoic acid, hexamethylenediamine, hydrazine, Ν'-diethyl fluorenyl-p-phenylene Amine, hydrazine, Ν'-diethylhydrazine·1,6-hexanediamine. -25- 201202844 The above compound having a guanamine group enhances the storage stability of the composition at room temperature. Further, since it has excellent reactivity with an epoxy group, it contributes to low-temperature curing at 200 ° C or lower. The content ratio of the compound represented by the above formula (1) to (3) in the composition is preferably 0.01 by mass based on 100 parts by mass of the [A] polymer and the [A] copolymer. It is preferably 10 parts by mass, more preferably 5 parts by mass to 5 parts by mass. When the content ratio of the [D] compound is from 10 parts by mass to 10 parts by mass, the storage stability of the composition and the hardening of the cured film can be simultaneously achieved at a higher level, and the obtained film can be maintained at a higher level. The voltage holding ratio of a display element having a cured film such as a protective film, an interlayer insulating film, or a spacer. <Optional component> The desired effect of the composition in addition to the above [A] polymer or [A] copolymer, [B] polymerizable compound, [C] polymerization initiator, and [D] compound In the range, if necessary, [E] a compound having two or more oxirane groups in i^, [F] an adhesion aid, [G] surfactant, [H] storage stabilizer, and (1) Heat resistance improver, etc. These various optional components may be used singly or in combination of two or more. Hereinafter, the details will be described in order. (10) a compound having two or more oxirane groups in one molecule] [E] a compound having two or more oxirane groups in one molecule (hereinafter, also referred to as "[E] compound"), It can be used to further increase the hardness of the obtained cured film. As such a compound [e], for example, a compound having two or more 3,4-epoxycyclohexyl groups in one molecule and other [E] compounds may be mentioned, but not including [a] polymer or (4) -26. - 201202844 The compound having two or more 3,4-cyclononcyclohexyl groups in one molecule may, for example, be 3,4-epoxycyclohexylmethyl-3,4,-epoxycyclohexane. Phthalate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-m-dioxane, bis(3,4·epoxycyclohexylfluorenyl) Adipate, bis(3,4-epoxy-6-fluorenylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3,,4,-epoxy -6,-Methylcyclohexane decanoate, methylene bis(3,4-epoxycyclohexane), bicyclodeuterated dicyclopentadiene, di(3,4-ring) of ethylene glycol Oxycyclohexyldecyl)ether, ethyl bis(3,4-epoxycyclohexanecarboxylic acid vinegar), caprolactone modified 3,4-epoxycyclohexyldecyl-3,,4,-ring Oxycyclohexane formate and the like. Examples of the other [E] compound include di-brown A diglycidyl ether, bisphenol ρ diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol a diglycidyl ether, and hydrogenated bisphenol F. Dihydrate of bisphenol compounds such as diglycidyl ether, hydrogenated bisphenol ad diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol ρ diglycidyl ether 'brominated bisphenol S diglycidyl ether The glycerol ether; the amount of the above [E] compound is preferably 5 parts by mass or less, more preferably 2 parts by mass to 50 parts by mass relative to the mass of the [a] polymer or [A] copolymer. The portion is particularly preferably 5 parts by mass to 30 parts by mass. When the amount of the compound [E] is in the above range, the developability can be prevented, and the hardness of the cured film such as the interlayer insulating film, the spacer or the protective film can be further improved. [[F] Adhesive Aid] [F] Adhesive Aid is used to further improve the adhesion of the hardened film such as a separator or a protective film to the substrate, and the intervening auxiliary agent, preferably having a carboxyl group and a σ 丨Health. As such a reactive group of [F] viscous (tetra) olefinic group, ethylene group, -27-201202844 isocyanate group, ring boy 7 & ethene group, etc., it can be enumerated For example, trimethoxy ruthenium sulphate, methoxy propyl trimethoxy hydride, ethylene methoxy oxime, acetonitrile trimethoxy sulphur, singular::: triethoxy..., γ-glycidoxy Propyltrimethoxy-β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, etc. ^ As the amount of [F] adhesion aid, relative to 1 part by mass of ί: or [A] The copolymer is preferably 2 parts by mass or less, more preferably 15 Å or less. If the amount of the [F] bonding aid exceeds 2 Å, it tends to cause development residue. ...[[G] surface The active agent] [G] surfactant is used to further improve the coating film formation of the composition. As the [G] surfactant, for example, a fluorine-containing surface blushing agent, an organic quinone surfactant, and the like may be mentioned. Surfactant. For the above fluorosurfactant, it is preferred to have a fluoroalkyl group and/or a fluorine at any end of the terminal, main chain and side chain. The combination of alkyl groups and mountains to list, for example, M,2,2-tetrafluoro-n-octyl (^, 2,2-tetrafluoro-n-propyl), l1,2,2-tetrafluoro-n-octyl (n-hexyl) Ether, hexaethylene glycol di(1, hydrazine, 2 2 3 3 hydrazine n-pentyl) ether, octaethylene glycol bis(indolyl, ^, tetrafluoro-n-butyl), hexa-propanol- 1 (1) , 1,2,2,3,3-hexa-n-pentyl)ether, octapropylene glycol _ (Μ,2,2-tetrafluoro-n-butyl)ether, sodium perfluoro-n-dodecylsulfonate, hexafluoro N-decane, 8, 9, 9, 10, 1 〇 _ 氟正十一十一 ' ' and sodium fluoroalkyl benzene sulfonate, sodium fluoroalkyl phosphate, sodium fluorocarbonate, diglycerol tetra (fluoroalkane Polyoxyethylene ether), alkyl iodide, gas-fired betaine, other fluoroalkyl polyoxyethylene ether, perfluoroalkyl polyoxyethylene, perfluoroalkyl alkoxide, fluoroalkyl carboxylate Ester, etc. -28- 201202844 Commercial products of fluorinated surfactants include, for example, BM-1000, BM-1100 (above, BM CHEMIE), MEGAFAC F142D, MEGAFAC F172, MEGAFAC F173, MEGAFAC F183, MEGAFAC. F178, MEGAFAC F191, MEGAFAC F471, MEGAFAC F476 (above, Dainippon Ink Industrial company), FLUORAD FC-170C, FLUORAD-171, FLUORAD-430, FLUORAD-43 1 (above, Sumitomo 3M), Surflon S-112, Surflon-113, Surflon-131, Surflon-141, Surflon-145, Surflon -382, Surflon SC-101, Surflon -102, Surflon -103, Surflon -104, Surflon -105, Surflon -106 (above, Asahi Glass), EFTOP EF301, EFTOP 303, EFTOP 352 (above, New Akita Chemicals Co., Ltd. ), FTERGENT FT-100, FTERGENT -110, FTERGENT -140A, FTERGENT -150, FTERGENT -250, FTERGENT -25 1, FTERGENT -300, FTERGENT -3 10, FTERGENT -400S ' FTERGENT FTX-218 , FTERGENT -25 1 (above, (shares) NEOS company) and so on. As a commercial item of an organic terpene surfactant, for example, Toray Silicone DC3PA, Toray Silicone DC7PA, Toray Silicone SH11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH-190, Toray Silicone SH-193, Toray Silicone SZ-6032, Toray Silicone SF-8428, Toray Silicone DC-5 7, Toray Silicone DC-190 (above, Toray Dow Corning Silicone), TSF-4440, TSF-4300, TSF- 4445, TSF-4446, TSF-4460, TSF-4452 (above, GE Toshiba -29- 201202844

Silicones 公司），Organo Siloxane Polymer ΚΡ341(信越 4匕學工業公司）等。作為其他表面活性劑，可以列舉出例如聚氧乙烯月桂醚、聚氡乙烯十八烷基醚、聚氧乙烯油烯基醚 (polyoxyethylene 〇 ley 1 ether)等聚氧乙烯烷基醚；聚氧乙烯正辛基苯基醚、聚氧乙烯正壬基苯基醚等聚氧乙烯芳基醚；聚氧乙烯二月桂酸酯、聚氧乙烯二硬脂酸酯等聚氧乙烯一烧基S旨等的非離子表面活性劑，（曱基）丙烯酸系共聚物 Polyflow Νο·57、No.95(以上，Kyoeisha Chemical 公司）等。作為[G]表面活性劑的用量，相對於i〇()質量份[A] 聚合物或[A ]共聚物，較佳為1 〇質量份以下，更佳為〇 5 質量份以下。如果[G]表面活性劑的用量超過1 ·〇質量份’則容易產生薄膜不均。 [[H]保存穩定劑] 作為[H]保存穩定劑，可以列舉出例如硫、醌類 '氫西昆類、聚氧化合物、胺、硝基亞硝基化合物等，更具體地’可以列舉出4-曱氧基苯酚、N_亞硝基-N_苯基羥基銨鋁等。作為[H]保存穩定劑的用量，相對於1〇〇質量份[a] 聚合物或[A]共聚物，較佳為3 · 〇質量份以下，更佳為〇 5 質量份以下。[H]保存穩定劑的混合量如果超過3 〇質量份’則該組成物的感度降低，圖案形狀可能變差。 [[I]耐熱性提高劑] 作為[I]耐熱性提高劑，可以列舉出例如N-(烷氧基曱基）甘腺化合物、N-(烷氧基曱基）三聚氰胺化合物等。 -30- 201202844 作為N (烷氧基甲基）甘脲化合物，可以列舉出例如 N’N’N ’N四（甲氧基甲基）甘脲、N，N，N，，N，-四（乙氧基甲基）甘脲、N，N，N，，N，-四（正丙氧基甲基）甘脲、N，N，N，，N，- 四（異丙氧基甲基）甘脲、n，n，n，，n，_四（正丁氧基甲基）甘腺、：^’，『，：^’’’-四（三級丁氧基甲基）甘脲等。它們之中，較佳為N，N，N，，N，-四（甲氧基曱基）甘脲。作為N-(烷氧基曱基）三聚氰胺化合物可以列舉出例如N，N，N’，N’，N，，，N，，-六（甲氧基曱基）三聚氰胺、 N，N，N’，N’，N”，N”_六（乙氧基曱基）三聚氰胺、 n，n，n’，n’，n”，n’，_六（正丙氧基甲基）三聚氰胺、 n，n，n’，n’，n”，n’’-六（異丙氧基甲基）三聚氰胺、 n，n，n’，n’，n’’，n’’_六（正丁氧基曱基）三聚氰、 n’n，n’，n’，n”，n”_六（三級丁氧基甲基）三聚氰胺等。它們之中’較佳為^化…’山”’:^”-六^氧基甲基女三聚氰胺’作為市售品，可以列舉出例如NIKALAC N-2702、 NIKALAC MW-30M(以上，Sanwa Chemical 公司）等。作為[I]耐熱性提高劑的用量，相對於丨〇〇質量份[A] 聚合物或[A ]共聚物，較佳為5 0質量份以下，更佳為3 〇質量份以下。[I ]耐熱性提高劑的混合量如果超過5 〇質量份’則該組成物的感度低下，圖案形狀可能變差。 <感放射線性樹脂組成物的製備> 本發明的感放射線性樹脂組成物可以通過將[A]聚合物或[A]共聚物、[B]聚合性化合物、[C]聚合引發劑以及[D ]化合物，再加上在不損害所希望的效果的範圍内，根據需要添加的任意成分，以規定比例混合製備。該咸 -31 - 201202844 放射線性樹脂組成物較佳為溶解到適#的溶一液狀態使用。 ’在溶作為用於製備該組成物的溶劑，可以使用能夠h _ 地溶解或分散[A]聚合物或[A]共聚物、[B]聚合性物、[C]聚合引發劑、[D]化合物以及任意， . 习而且不 ° 成分反應的溶劑。作為這種溶劑可以列舉出作可以用於合成上述[Α]共聚物而例示的溶劑相同的那些’較佳為含有由醇類溶劑和醚類溶劑構成的卞、’’甲選出的至少—種溶劑。可以認為在該組成物中，由於共存的[A]共聚物中的羧基和[D]化合物的相互作用，抑制包接的崩解，所以可以使用極性溶劑。此外，可以認為由於上述相互作用，[D]化合物還發揮促進[A]共聚物中的環氧基的硬化反應的相乘效果。溶劑可以單獨或混合兩種以上使用。從各成分的溶解性與各成分的反應性、塗膜形成的容易性等觀點而言，較佳為醇類、二醇醚、乙二醇單境基醚乙酸酯、酯類、二乙二醇單烷基醚乙酸酯、二乙二醇二烷基醚、二丙二醇二炫•基醚、丙二醇單烷基醚、内二醇單烷基醚乙酸酯。它們之中’更佳為苯曱醇、2-笨基乙醇、3 -苯基-1-丙醇、乙二醇單丁基醚乙酸酯、二乙一醇單乙謎乙酸S旨、二乙·一醇一乙鍵、二乙二醇乙基曱醚、二乙二醇二曱醚、二丙一醇二甲謎、丙二醇單曱轉、丙二醇單曱醚乙酸酯、2-甲氧基丙酸曱酯或3-甲氧基而酸甲酯、2-乙氧基丙酸乙酯或3_乙氧基丙酸乙酯。 -32- 201202844 溶劑和高彿點溶劑一起使用二……上述基喊、二= 酮、Μ·二甲基乙醯胺、节基乙节t — 土 .、丙酮基丙酮、1-辛醇、1-壬醇、醋酸二、：甲酸乙醋、草酸二乙醋、馬來酸二乙醋”-丁内S曰、碳酸丙二酯笪 , 。匕們之中，較佳為N -曱基吡咯啶 —°、γ-丁内醋或n，n-二甲基乙醯胺。卜為了提尚膜厚在面内的均勻性，可心金4 一· ^ * 砵」？。亥組成物的溶劑，在和高沸點溶劑-起使用下 “用置相對於全部溶劑量，較佳為5 0質量％以二更佳為40質量％以下’特佳為3〇質量％以下。高沸點〉谷劑的用旦达、用里為50質量％以下時，塗膜的膜厚均勻性、感度和殘臈率良好。 ' Λ、’’且成物製備為溶液狀態時，固體含量濃度（組成物溶液中佔據的溶劑以外的成分）根據使用的目的以 =:希望的膜厚的值等，可以設定為任意濃度（例如，$ 質量％〜50質量％)。作為更佳的固體含量濃度根據往基板上形成覆膜的方法而異，對其如後所述。對這樣製備的成物洛液’使用孔徑〇 · 5 μ m左右的微孔筛檢程式等過濾後，再使用。 <硬化膜的形成方法> 以下’使用該組成物，對形成層間絕緣膜、保護膜或間隔物等硬化膜的方法進行說明。本發明的硬化膜的形成方法至少包含以下順序記載的下述步驟（1)〜（4)。 U )在基板上形成該組成物的塗膜的步驟， -33- 201202844 (2) 對步驟（1)形成的塗膜的至少—部分的步驟， (3) 將步驟（2)中照射過放射線的塗膜顯% 及 (4) 燒製在步驟（3)顯影後的塗膜的步驟。通過使用該組成物的本發明的形成方法均衡性良好地滿足耐熱性、耐化學藥品性、整性、電壓保持率、耐熱性線性膨脹性等要硬化膜。以下’對這些步驟進行詳細描述。 [(1)在基板上形成該組成物的塗膜的步驟] 在透明基板的一面上形成透明導電膜，電膜上形成感放射線性樹脂組成物的覆膜。板，可以列舉出例如鈉弼玻璃、無驗玻璃等由聚對苯二甲酸乙二酯、聚對苯二甲酸丁二g 聚碳酸酯、聚醯亞胺等塑膠形成的樹脂基板作為在透明基板的一面上設置的透明導列舉出由氧化錫（Sn〇2)形成的NESa膜（美國注冊商標）、由氧化銦_氧化錫（In2〇3_Sn〇2)形等。 ‘ 通過塗布法形成覆膜時，可以在上述透塗布该組成物的溶液後，較佳為通過加熱3 焙）’形成覆膜。作為塗布法中使用的組成物含3：濃度，較佳為5質量％〜5〇質量％，更^ %〜40質量。/〇，特佳為15質量％〜35質量。/〇。物溶液的塗布方法，可以採用例如噴塗法、照射放射線》的步驟，以，可以形成透光率、平求的性質的在該透明導作為透明基玻璃基板， I旨、聚&ϊ!ΐ石風、等。電膜，可以 PPG公司的成的ITO膜明導電膜上 t布面（預烘溶液的固體 t為10質量作為該組成輥塗法 '旋 -.34- 201202844 轉塗布法（旋塗）、狹縫塗布法（縫模塗布法）、棒塗法、喷墨塗布法等搞a 项虽的方法。它們之中，較佳為旋塗法或狹縫塗布法。 ^乍為上述預供焙的條件’根據各成分的種類、混合比例等而異，較佳為70°C〜120°C，進行1~15分鐘左右。覆膜預纟共培後的膜厚較佳為0_5μηι〜ΙΟμιη ,更佳為 Ι.Ομιη〜7,〇μηι 左右。 [(2)對步驟⑴形成的塗膜的至少—部分照射放射線的步驟] 接著，對形成的覆膜的至少一部分照射放射線。此時，只對覆膜的一部分照射時，可以通過例如插入具有規定圖案的光罩照射的方法進行。作為照射使用的放射線’可以列舉出可見光線、紫外線、遠紫外線等。其中’較佳為波長25〇nnl〜55〇nnl的 I巳圍内的放射線，更佳為含有3 6 5 n m的紫外線的放射線。放射線照射量（曝光量）是通過照度計（OAi m〇del 3 5 6 ’ 0 p t i c a 1 A s s 〇 c i a t e s I n c ·製造）測定照射的放射線的波長 3 6 5nm 下的強度得到的值，較佳為 100J/m2~5,000J/m2，更佳為 200J/m2〜3,〇〇〇j/m2。該組成物與現有已知的組成物相比，具有下述優點：放射線感度更高，即使上述放射線照射量為700J/m2 以下，進而是600J/m2以下’也可以得到所希望的膜厚、良好的形狀、優異的密合性以及高硬度的層間絕緣膜、保護膜或間隔物等硬化膜。 -35- 201202844 [()::驟(2)中照射放射線的塗膜顯影的步驟通過將放射線照射後的覆膜& 要的部分’形成規定的圖案。衫’ 作為顯影中使用的顯影液，可納、氫氣彳卜& 例 ^ 鉀、碳酸鈉等無機鹼，氫氧化四甲乳化四乙基銨等四級銨鹽等鹼性化述鹼性化合杉）& , + +丄 m ； ^ ^ 物的水溶液中，還可以適量添加甲 4水冷性有機溶劑和/或表面活性劑。 * :為_影方法可以是液體堆積法、浸潰法等任一方法，顯影時間較佳為在常溫下進行1 〇 t/ 4s左右在顯影處理之後，例如進行3 〇秒驾流水洗滌& ’通過以壓縮空氣或壓縮氮氣風乾3 到所希望的圖案。 [(4)燒製步驟（3)顯影的塗膜的步驟] 接著，將得到的圖案狀覆膜通過熱板、烤的加熱裝置燒製（後烘焙），得到硬化膜。作為較佳為loot：〜20(TC，更佳為15〇〇c〜18〇C)c。作間例如在熱板上較佳為5分鐘〜3〇分鐘，在烤為3 0刀鐘〜1 8 〇分鐘。該組成物如上所述由於/ 合物，所以像這樣，可以實現低溫燒製同時保也優異，而且具有足夠的放射線感度。因此，適合作為在希望低溫燒製的撓性顯示器等中使絕緣膜、保護膜和間隔物等的硬化膜的形成材 <顯示元件> 本發明的顯示元件例如可以通過下述方法除去不需如氫氧化基錄、氫液。在上醇、乙醇、淋浴法秒鐘〜1 8 〇 [~90秒鐘，可以得相專適當燒製溫度為燒製時箱中較佳 b有[D]化存穩定性該組成物用的層間料使用。製造。 -36- 201202844 首先’準備一對（兩塊）在一面上具有透明導電膜（電極）的透明基板，在其中一塊基板的透明導電膜上使用該組成物’根據上述方法’形成間隔物或保護膜或者其兩者。接著’在這些基板的透明導電膜和間隔物或保護膜上形成具有液晶配向能的配向膜。以形成該配向膜側的面為内側’插入一定間隙（胞間隙）將這些基板對向配置’以使各配向膜的液晶配向方向正交或逆平行，在通過基板的表面（配向膜）和間隔物區分的胞間隙内填充液曰曰’抗封填充孔’構成液晶胞。然後，在液晶胞的兩外表面，貼合偏光板，以使其偏光方向和該基板的一面上开/成的配向膜的液晶配向方向一致或正交，從而得到本發明的顯示元件。作為其他方法，準備一對和上述方法同樣地，形成透明導電膜與層間絕緣膜、保護膜或間隔物或者兩者以及配向膜的透明基板。之後，沿著一個基板的端部，使用I '主器塗布紫外線硬化型密封劑，4妾著，4吏用液晶分 =器，滴加微小液滴形狀的液晶，在真空下將兩基板貼 S j後，對上述密封劑部使用高壓水銀燈，照射紫外良密封兩基板。最後，在液晶胞的兩外表面貼合偏光板’得到本發明的顯示元件。乍為上述各方法中使用的液晶，可以列舉出例如向 ^型液晶、層列型液晶等。另外，作為在液晶胞外側使的偏光板，可以列舉出-邊將聚乙烯醇延展配向，一、用酸纖維素保護膜夾住吸收碘的稱作「Η膜」的偏光膜形成的偏光板，或由Η膜本身形成的偏光板等。 -37- 201202844 [實施例]. 以下，基於實施例，對本發明進行詳細描述，該實施例並不是對本發明的限定解釋。在以下的合成例中，共聚物的重量平均分子量（Mw) 是以下述裝置和條件為基礎，通過凝膠滲透層析法（GPC) 測定。裝置：GPC-101(昭和電工公司製造）管柱：組合 GPC-KF-801、GPC-KF-802、GPC-KF-803 和 GPC-KF-804 移動相：四氫呋喃 <[A]共聚物的合成> [合成例1] 在具有冷凝管和攪拌器的燒瓶中，加入5質量份 2,2’-偶氮雙（2,4-二曱基戊腈）和220質量份二乙二醇曱基乙基醚。接著，加入20質量份苯乙烯、12質量份甲基丙烯酸、28質量份曱基丙烯酸二環戊酯和4〇質量份甲基丙烯酸縮水甘油酯，氮氣置換，邊缓慢攪拌，邊將洛液的溫度升高到7(TC ’保持該溫度5小時進行聚合，知到έ有共聚物（A -1)的溶液。得到的共聚物溶液的固體 3 5·/辰度疋31.30/〇，共聚物（八_1)的Mw是12,〇〇〇。另外，固體含量濃度是指共聚物質量占共聚物溶液的全部質量的比例。 [合成例2 ] 在具有冷凝管和攪拌器的燒瓶中，加入5質量份 2,2’_偶氮雙（2,4-二曱基戊腈）和22〇質量份二乙二醇曱 -38- 201202844 基乙基醚。接著’加入10質量份苯乙烯、12質量份甲基丙烯酸、23質量份曱基丙稀酸三環二環戊酯和20質量份曱基丙烯酸縮水甘油酯、20質量份曱基丙烯酸2-曱基縮水甘油酯、1 0質量份曱基丙烯酸四氫糠基酯，氮氣置換後’進一步加入5質量份1，3 -丁二烯，邊緩慢攪拌，邊將溶液的溫度升高到7 〇 °C，保持該溫度5小時，進行聚合，得到含有共聚物（A_2)的溶液。得到的共聚物溶液的固體含量濃度是31.5%，共聚物（A-2)的Mw是 10，100 。 [合成例3 ] 在具有冷凝管和攪拌器的燒瓶中，加入5質量份 2,2’-偶氮雙（異丁腈）和22〇質量份二乙二醇曱基乙基喊。接著’加入15質量份苯乙烯、30質量份甲基丙烯酸正丁醋、3 0質量份甲基丙烯酸苄酯和2 5質量份甲基丙稀酸縮水甘油酯，邊緩慢攪拌，邊將溶液的溫度升高到8 0 C ’保持該溫度5小時進行聚合，得到含有共聚物 (A-3)的溶液，得到的共聚物溶液的固體含量濃度是 31.0%’ 共聚物（A_3)的 Mw 是 1〇,〇〇〇。 <硬化膜形成用感放射線性樹脂組成物的製備> [貫施例1〜1 4和比較例！〜斗] 按表1所示的種類、量，將[A]聚合物或共聚物、 [B]聚合性化合物、[C]聚合引發劑以及[D]化合物混合，然後混合5質量份作為[F]黏合助劑的γ-縮水甘油氧基丙基三甲氧基矽烷、〇_5質量份[G]表面活性劑（FTX-218、 -39- 201202844 NEOS公司）和〇·5質量份作為[Η]保存穩定劑的4·甲氧基苯紛，分別加入丙二醇單曱醚乙酸酿，以使固體含量濃度為3 〇質量％後，通過孔徑〇 ·5 μηι的微孔篩檢程式過遽後，製備感放射線性樹脂組成物’分別為實施例1〜14和比較例1〜4。另外’欄中的「-」表示不使用該成分。構成該感放射線性組成物的[Β]聚合性化合物、[C] 聚合引發劑以及[D]化合物的詳細情況如下所示。 ([Α]聚合物、共聚物） (Α-1)合成例1得到的共聚物 (Α-2)合成例2得到的共聚物 (Α-3)合成例3得到的共聚物 (Α-4)苯酚酚醛清漆型環氧樹脂（Japan Epoxy Resin(股）製造的「EPIKOTE 152」） ([B]聚合性化合物） (Β -1)二新戊四醇五丙稀酸酯和二新戊四醇六丙烯酸醋的混合物（KAYARAD DPHA(日本化藥公司） (B-2)KAYARAD DPHA-40H(曰本化藥公司） (B-3)l，9 -壬二醇二丙烯酸酯 (B-4)新戊四醇四丙烯酸酯 (B-5)三羥曱基丙烷三丙烯酸酯 (Β-6)ω-羧基聚己内酯單丙烯酸酯（ARONIX Μ-5300、東亞合成公司） (Β-7)琥珀酸改質的新戊四醇三丙烯酸酯（ARONIX TO-756、東亞合成公司） -40- 201202844 (B-8)環氧乙烧改質的二新戊四醇六丙烯酸酯 ([C]聚合引發劑） (C-l)l，2-辛二醇-1-[4-(苯基硫代）-2-(0-苯曱醯基肟）](IRGACURE OXEOl、Ciba · Specialty · Chemicals 公司） (C-2)乙酮- l-[9 -乙基- 6-(2-曱基苯甲醯基）-9H-咔唑 -3-基]-1-(0-乙醯基肟）（IRGACURE OXE02、Ciba · Specialty · Chemicals 公司） (C-3 )2-甲基-1-(4-甲硫基苯基）-2-咪啉代丙-1-酮 (IRGACURE 907、Ciba · Specialty · Chemicals 公司） (C-4)2-二甲基胺基-2-(4 -甲基苄基）-1-(4-咮啉-4-基- 本基）-丁-l-酮（IRGACURE379、Ciba·Specialty· Chemicals 公司） ([D]化合物） (D-1)乙醯胺 (D-2)N-曱基乙醯胺 (D-3)鄰苯二曱醯胺酸 (D-4)間苯二曱醯胺 (D - 5)己二醯胺 (D-6)N、N -二乙醯基-對伸苯基二胺 (D-7)N、N，-二乙醯基」，。己二胺比較例胺化合物（d-Ι)三乙胺 201202844 [表i] [Α]聚合物、共聚物 [Β]聚合性化合物 [C]聚合引發劑 [D]化合物種類質量種類質量份種類質量種類質量份份份實施例1 (Α-4) 100 (Β-1) 100 (C-1) 15 (D-l) 0.1 實施例2 (Α-4) 100 (Β-1) 100 (C-l) 15 (D-2) 0.1 實施例3 (Α-1) 100 (Β-1)/(Β-3) 90/10 (C-2) 10 (D-3) 0.1 實施例4 (Α-1) 100 (Β-1)/(Β-3) 90/10 (C-2) 10 (D-4) 0.1 實施例5 (Α-1) 100 (Β-1)/(Β-4) 80/20 (C-2) 10 (D-5) 0.1 實施例6 (Α-1) 100 (Β-1)/(Β-4) 80/20 (C-3) 25 (D-6) 0.1 實施例7 (Α-1) 100 (Β-1)/(Β-2)/(Β-6) 60/40/10 (C-3) 25 (D-7) 0.1 實施例8 (Α-2) 100 (Β-4)/(Β-5) 50/50 (C-4) 25 (D-l) 0.2 實施例9 (Α-2) 100 (Β-1) 100 (C-4) 20 (D-2) 0.2 實施例10 (Α-2) 100 (Β-8) 100 (C-l)/(C-3) 5/15 (D-3) 0.2 實施例11 (Α-2) 100 (Β-1) 100 (C-2) 10 (D-4) 0.2 實施例12 (Α-2) 100 (Β-7)/(Β-2) 80/20 (C-l)/(C-3)/(C-4) 5/5/5 (D-5) 0.2 實施例13 (Α-3) 100 (Β-3)/(Β-4)/(Β-5) 30/30/40 (C-l)/(C-3) 5/15 (D-6) 0.2 實施例14 (Α-3) 100 (Β-3)/(Β-4)/(Β-5) 40/40/20 (C-2)/(C-4) 5/15 (D-7) 0.2 比較例1 (Α-1) 100 (Β-1) 100 (C-4) 20 (d-l) 0.1 比較例2 (Α-1) 100 (Β-1) 100 (C-4) 20 - - 比較例3 (Α-4) 100 (Β-1) 100 (C-l) 15 (d-l) 0.1 比較例4 (Α-4) 100 (Β-1) 100 (C-l) 20 - - 表中，「-」表示沒有添加。 <評價> 對該感放射線性樹脂組成物如下進行評價。結果在表2中表示。 [保存穩定性（％)的測定] 將該感放射線性樹脂組成物在40°C的烤箱中放置1 周，測定放入烤箱前後的黏度，求得黏度變化率。此時，黏度變化率為 5 %以下時，認為保存穩定性良好，超過 5 %時，認為保存穩定性不好。黏度使用 E型黏度計 (VISCONIC ELD.R，東機產業公司），在25°C下測定。 [感度（J/m2)的測定] 在無驗玻璃基板上*分別通過旋塗器塗布該感放射線性樹脂組成物後，在1 00°C的熱板上預烘焙2分鐘，形成膜厚4.0μιη的塗膜。 -42- 201202844 接著，在得到的塗膜上通過具有殘留了直徑 8μηι 15μηι @ 圍的不同大小的多㈤圓形的圖案的光使用门£水銀燈，將曝光量在心2的範圍内欠化，照射放射線。之後，使用0.40質量％氫氧化四甲基錄水溶液，在饥下以顯影時間為變數通過液體堆積法顯影後，純水洗滌1分鐘。然|，在烤箱中，下進行6 0分鐘預烘焙，形成具有剩餘有圓形的圖案的硬化獏。使用罈射顯微鏡（VK-85〇〇，Keyence公司）測定殘留圓形的圖案顯影前和顯影後的高度。由該值和下述式求得殘膜率（％)。殘膜率（％) = (顯影後的高度/顯影前的高度將該殘膜率$ 90%以上的曝光量作為感度。曝光量為800J/m2以下時，認為感度良好。 [耐熱性（％)的測定] 在上述硬化膜形成步驟中，不插入光罩，以7〇〇j/m2 的曝光量曝光，然後’在烤箱中，在18〇。。下後烘焙分鐘，對得到的塗膜進-步在烤箱中，在23代下㈣ 20分鐘，對加熱前後的膜厚通過觸針式膜厚測定儀 (Alpha Step IQ，KLATENCOR 公司 ν'目〜， A J )測疋，算出殘膜率（處理後膜厚/處理前膜厚><_ ’將該殘膜率作為耐熱性。 [耐化學藥品性（％)的測定] 在上述硬化膜形成步驟的曝光量曝光，然後，在烤分鐘，對得到的塗膜進一步中’不插入光罩，以7〇〇J/m2 箱中在18(TC下後烘焙6〇在烤箱中在加熱到60。(：的配 -43- 201202844 向膜剝離液CHEMICLEAN TS-204(三洋化成工業公司）中浸潰15分鐘，水洗後’再在烤箱中，在12〇它下乾燥 1 5分鐘。該處理前後的膜厚通過觸針式膜厚測定儀 (Alpha Step IQ’ KLATENCOR公司）測定，算出殘膜率（處理後膜厚/處理前膜厚X 1 0 0)’將該殘膜率作為耐化學藥品性。 [透光率（％)的測定] 在上述硬化膜形成步驟中，不插入光罩，以7〇〇J/m2 的曝光量曝光，然後’在烤箱中，在1 8 〇下後烘培6 〇分鐘，對得到的覆膜使用分光光度計（15〇_2〇型Double Beam、曰立製作所公司）測定波長4〇〇nm下的透光率。此時，在透光率不足9 0 %時，透明性不良。 [平整性（nm)的測定] 在si〇2浸潰的玻璃基板上，使用顏料類防染（c〇1〇r resist)(JCR RED 689、JCR GREEN 706 以及 CR 8200B、以上JSR公司），如下形成紅、綠和藍3種顏色的條紋狀濾光片。具體地，使用旋塗器，將上述防染的丨種顏色塗布到si〇2浸潰玻璃基板上，在熱板上，在9(rc下預烘焙150秒鐘，形成塗膜。之後，使用曝光機（Can〇n PLA501F、Canon公司），通過規定圖案罩，以換算為i 線是2,000J/m2的曝光量，照射ghi線（波長436nrn、 40 5nm、3 65nm的強度比=2 7 : 2 5 : 4 8)，接著，使用 0.05質量％氫氧化鉀水溶液進行顯影，通過超純水沖洗 60秒鐘。接著’進一步在烤箱中，在230。〇下加熱處理 3 0分鐘，形成單色的條紋狀濾光片。對3種顏色重複該 -44- 201202844 操作，形成紅、綠和藍3種顏色的條紋狀濾光片（條紋寬 200μπι) °Silicones), Organo Siloxane Polymer ΚΡ 341 (Shin-Etsu 4 Industrial Co., Ltd.) and so on. Examples of the other surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, poly(vinylidene stearyl ether), and polyoxyethylene olefinic ether (polyoxyethylene 〇ley 1 ether); polyoxyethylene; a polyoxyethylene aryl ether such as n-octyl phenyl ether or polyoxyethylene n-decyl phenyl ether; a polyoxyethylene sulphate such as polyoxyethylene dilaurate or polyoxyethylene distearate Nonionic surfactant, (fluorenyl) acrylic copolymer Polyflow Νο. 57, No. 95 (above, Kyoeisha Chemical Co., Ltd.) and the like. The amount of the [G] surfactant to be used is preferably 1 part by mass or less, more preferably 5 parts by mass or less based on the mass of the [A] polymer or the [A] copolymer. If the amount of the [G] surfactant exceeds 1 · 〇 by mass, then film unevenness is likely to occur. [[H] Storage Stabilizer] Examples of the [H] storage stabilizer include sulfur, anthracene 'hydroquinone, a polyoxy compound, an amine, a nitronitroso compound, and the like, and more specifically 4-methoxyphenol, N-nitroso-N-phenylhydroxyammonium aluminum, and the like. The amount of the [H] storage stabilizer is preferably 3 〇 by mass or less, more preferably 〇 5 parts by mass or less per 1 part by mass of the [a] polymer or the [A] copolymer. When the mixing amount of the [H] storage stabilizer exceeds 3 Å by mass, the sensitivity of the composition is lowered, and the pattern shape may be deteriorated. [[I] Heat resistance improving agent] Examples of the [I] heat resistance improving agent include an N-(alkoxyfluorenyl)glycine compound and an N-(alkoxyfluorenyl)melamine compound. -30- 201202844 As the N (alkoxymethyl) glycoluril compound, for example, N'N'N 'N tetrakis (methoxymethyl) glycoluril, N, N, N, N, - 4 (ethoxymethyl)glycoluril, N,N,N,,N,-tetra(n-propoxymethyl)glycoluril, N,N,N,,N,-tetrakis(isopropoxymethyl Glycoluril, n, n, n, n, _ tetra (n-butoxymethyl) gland, :^', 『,:^'''-tetra (tris-butoxymethyl) glycoluril Wait. Among them, preferred are N, N, N, N,-tetrakis(methoxyindenyl) glycoluril. As the N-(alkoxymethyl) melamine compound, for example, N,N,N',N',N,,,N,,-hexa(methoxyindenyl)melamine, N,N,N' may be mentioned. , N', N", N"_hexa(ethoxycarbonyl) melamine, n, n, n', n', n", n', _hexa(n-propoxymethyl) melamine, n, n,n',n',n",n''-hexa(isopropoxymethyl)melamine, n,n,n',n',n'',n''_hexa(n-butoxy Mercapto) melamine, n'n, n', n', n", n"_hexa(tris-butoxymethyl) melamine, and the like. Among them, 'preferably ^^..." ":^"-hexamethoxymethyl melamine' is commercially available as, for example, NIKALAC N-2702, NIKALAC MW-30M (above, Sanwa Chemical) Company) and so on. The amount of the heat resistance improving agent [I] is preferably 50 parts by mass or less, more preferably 3 parts by mass or less based on the mass of the [A] polymer or the [A] copolymer. When the mixing amount of the heat resistance improving agent exceeds 5 Å by mass, the sensitivity of the composition is lowered, and the pattern shape may be deteriorated. <Preparation of Radiation-sensitive Resin Composition> The radiation-sensitive resin composition of the present invention can be obtained by using [A] polymer or [A] copolymer, [B] polymerizable compound, [C] polymerization initiator, and The [D] compound is added in an amount which is added in a predetermined ratio, as needed, in an amount which does not impair the desired effect. The salty -31 - 201202844 radiation-linear resin composition is preferably used in a dissolved state of the solution. 'In the solvent used for the preparation of the composition, it is possible to dissolve or disperse [A] polymer or [A] copolymer, [B] polymerizable substance, [C] polymerization initiator, [D] a compound and a solvent which is arbitrarily and not reacted. As such a solvent, those which are exemplified as the solvent which can be used for the synthesis of the above [Α] copolymer are preferably 'at least one selected from the group consisting of an alcohol solvent and an ether solvent, and '' Solvent. In the composition, it is considered that a polar solvent can be used because the interaction between the carboxyl group and the [D] compound in the coexisting [A] copolymer suppresses the disintegration of the inclusion. Further, it is considered that the compound [D] exhibits a synergistic effect of promoting the hardening reaction of the epoxy group in the [A] copolymer due to the above interaction. The solvent may be used singly or in combination of two or more. From the viewpoints of solubility of each component, reactivity of each component, easiness of formation of a coating film, etc., alcohol, glycol ether, ethylene glycol single-state ether acetate, ester, and diethyl ether are preferable. Glycol monoalkyl ether acetate, diethylene glycol dialkyl ether, dipropylene glycol dihydroether ether, propylene glycol monoalkyl ether, internal glycol monoalkyl ether acetate. Among them, 'preferably phenyl sterol, 2-phenylethanol, 3-phenyl-1-propanol, ethylene glycol monobutyl ether acetate, diethyl succinyl acetate, S, and diethyl ·Alcohol-B-bond, diethylene glycol ethyl oxime ether, diethylene glycol dioxime ether, dipropanol dimer, propylene glycol monoterpene, propylene glycol monoterpene ether acetate, 2-methoxy Ethyl propionate or methyl 3-methoxyl, ethyl 2-ethoxypropionate or ethyl 3-ethoxypropionate. -32- 201202844 The solvent is used together with the high-fossil solvent. The above-mentioned base, bis-ketone, dimethyl dimethyl acetamide, ketone t-soil, acetonyl acetone, 1-octanol, 1-nonanol, acetic acid II: ethyl formate, oxalic acid diethyl acetonate, maleic acid diethyl acetonate--butylene sulfonate, propylene carbonate bismuth phthalate, among them, preferably N-fluorenyl Pyrrolidine-°, γ-butyrolactone or n,n-dimethylacetamide. In order to improve the uniformity of the film thickness in the in-plane, can the heart be 4·· * * 砵? . The solvent of the composition of the sea is preferably used in an amount of more than 50% by mass, more preferably 40% by mass or less, and more preferably 3% by mass or less, based on the total amount of the solvent. When the high-boiling point-> granules are used in an amount of 50% by mass or less, the film thickness uniformity, sensitivity, and residual rate of the coating film are good. 'Λ, '' and the solid content is prepared as a solution state. The concentration (component other than the solvent occupied in the composition solution) can be set to an arbitrary concentration (for example, % by mass to 50% by mass) according to the purpose of use: a value of a desired film thickness, etc., as a better solid. The content concentration varies depending on the method of forming a film on the substrate, and will be described later. The thus prepared liquid solution is filtered using a micropore screening method having a pore diameter of about 5 μm, and then used. <Method of Forming Cured Film> The method of forming a cured film such as an interlayer insulating film, a protective film or a spacer using the composition will be described below. The method for forming a cured film of the present invention includes at least the following procedures. Following steps (1)~(4). U) a step of forming a coating film of the composition on the substrate, -33-201202844 (2) a step of at least a part of the coating film formed in the step (1), (3) Step (2) of the coating film irradiated with radiation and (4) a step of firing the coating film after the development in the step (3). The formation method of the present invention using the composition satisfies the heat resistance well. The film is cured by chemical resistance, integrability, voltage retention, heat resistance, linear expansion, etc. These steps are described in detail below. [(1) Step of forming a coating film of the composition on a substrate] A transparent conductive film is formed on one surface of the transparent substrate, and a film of a radiation-sensitive resin composition is formed on the electric film. Examples of the plate include polyethylene terephthalate, polyacetate, and the like. A resin substrate formed of a plastic such as polycarbonate or polyimine, and a transparent substrate provided on one surface of a transparent substrate, a NEsa film formed of tin oxide (Sn〇2) (US registered trademark) By indium oxide_tin oxide (In2〇3_Sn〇2) When the film is formed by a coating method, it is possible to form a film after the solution of the composition is overcoated, preferably by heating 3 to form a film. The composition used in the coating method contains a concentration of 3: Preferably, it is 5 mass% to 5 〇 mass%, more ^% to 40 mass%. / 〇, particularly preferably 15 mass% to 35 mass. / 〇. The coating method of the solution can be, for example, spray coating, irradiation of radiation. In the step, the transparent light guide can be formed as a transparent base glass substrate, I, poly & ϊ ΐ ΐ 风 wind, etc. Electro-film, can be formed by PPG company ITO film The t-coat surface on the conductive film (the solid t of the pre-baked solution is 10 mass as the composition roll coating method)--34-201202844 transfer coating method (spin coating), slit coating method (slot die coating method), rod The method of applying a method such as coating method or inkjet coating method. Among them, a spin coating method or a slit coating method is preferred. The condition of the above-mentioned pre-baked baking ' varies depending on the type of each component, the mixing ratio, and the like, and is preferably from 70 ° C to 120 ° C for about 1 to 15 minutes. The film thickness after pre-coating of the film is preferably 0_5μηι~ΙΟμιη, more preferably Ι.Ομιη~7, 〇μηι. [(2) Step of irradiating at least a part of the coating film formed in the step (1) with radiation] Next, at least a part of the formed coating film is irradiated with radiation. In this case, when only a part of the film is irradiated, it can be carried out by, for example, a method of irradiating a mask having a predetermined pattern. Examples of the radiation used for irradiation include visible light rays, ultraviolet rays, and far ultraviolet rays. Among them, the radiation in the range of the wavelength of 25 〇 nn to 55 〇 nn is preferably a radiation containing ultraviolet rays of 3 6 5 n m. The radiation exposure amount (exposure amount) is a value obtained by measuring the intensity at a wavelength of 3 6 5 nm of the irradiated radiation by an illuminometer (OAi m〇del 3 5 6 '0 ptica 1 A ss 〇ciates I nc · manufactured), preferably It is 100 J/m 2 to 5,000 J/m 2 , more preferably 200 J/m 2 to 3, 〇〇〇 j/m 2 . This composition has an advantage that the radiation sensitivity is higher than that of the conventionally known composition, and the desired film thickness can be obtained even if the radiation irradiation amount is 700 J/m 2 or less and further 600 J/m 2 or less. A cured film such as a good shape, excellent adhesion, and a high-hardness interlayer insulating film, protective film, or spacer. -35-201202844 [(): Step of developing a coating film for irradiating radiation in the step (2) A predetermined pattern is formed by applying a portion of the film & The shirt's use as a developing solution for development, such as sodium, hydrogen, etc., such as potassium, sodium carbonate, and other inorganic bases, tetramethylammonium hydroxide, tetraethylammonium, etc. In the aqueous solution of the genus &, + + 丄m ; ^ ^, a water-cooling organic solvent and/or a surfactant may be added in an appropriate amount. * : The _ shadow method may be any one of a liquid deposition method, a dipping method, and the development time is preferably performed at a normal temperature for about 1 〇 t / 4 s after the development treatment, for example, 3 〇驾驾驾驾'Boil air 3 by compressed air or compressed nitrogen to the desired pattern. [(4) Step of firing step (3) development of coating film] Next, the obtained pattern-like coating film is fired (post-baking) by a hot plate and a baking heating device to obtain a cured film. Preferably, it is loot: ~20 (TC, more preferably 15〇〇c~18〇C)c. For example, on a hot plate, it is preferably 5 minutes to 3 minutes, and it is baked for 30 knives to 1 8 minutes. Since the composition is a compound as described above, it is possible to achieve low-temperature firing while maintaining excellent temperature and sufficient radiation sensitivity. Therefore, it is suitable as a material for forming a cured film of an insulating film, a protective film, a spacer, or the like in a flexible display or the like which is desired to be fired at a low temperature. <Display Element> The display element of the present invention can be removed, for example, by the following method. It needs to be recorded as hydrogen hydroxide or hydrogen. In the case of alcohol, ethanol, shower method ~ 18 〇 [~90 seconds, you can get the appropriate firing temperature for the firing of the box, preferably b [D] stability of the composition for the composition The interlayer material is used. Manufacturing. -36- 201202844 First, prepare a pair of (two pieces) transparent substrates having transparent conductive films (electrodes) on one side, and use the composition 'on the transparent conductive film of one of the substrates' to form spacers or protect according to the above method. Membrane or both. Next, an alignment film having a liquid crystal alignment energy is formed on the transparent conductive film of these substrates and the spacer or the protective film. The surfaces on the side of the alignment film are inserted "with a certain gap (cell gap) to align the substrates in such a manner that the liquid crystal alignment directions of the respective alignment films are orthogonal or antiparallel, on the surface (alignment film) passing through the substrate and The filling liquid 曰曰 'anti-sealed filling hole' in the interstitial space defined by the spacer constitutes a liquid crystal cell. Then, the polarizing plate is bonded to both outer surfaces of the liquid crystal cell so that the polarizing direction thereof coincides with or is orthogonal to the liquid crystal alignment direction of the alignment film formed on one surface of the substrate, whereby the display element of the present invention is obtained. As another method, a pair of transparent substrates in which a transparent conductive film, an interlayer insulating film, a protective film or a spacer, or both and an alignment film are formed in the same manner as the above method are prepared. After that, along the end of one of the substrates, the UV-curable sealant is applied by using the I' main unit, 4 妾, 4 吏 using a liquid crystal sub-device, and a liquid droplet of a droplet shape is dropped, and the two substrates are attached under vacuum. After S j , a high-pressure mercury lamp is used for the above-mentioned sealant portion, and the two substrates are sealed by irradiation with ultraviolet rays. Finally, the polarizing plate is attached to both outer surfaces of the liquid crystal cell to obtain the display element of the present invention. The liquid crystal used in each of the above methods may, for example, be a liquid crystal or a smectic liquid crystal. In addition, as a polarizing plate which is formed on the outer side of the liquid crystal cell, a polarizing plate which is formed by a polarizing film called a "ruthenium film" which sandwiches an iodine protective film with an acid cellulose protective film is used. Or a polarizing plate formed by the diaphragm itself or the like. [37] [Embodiment] The present invention is described in detail below based on the embodiments, which are not intended to limit the invention. In the following synthesis examples, the weight average molecular weight (Mw) of the copolymer was determined by gel permeation chromatography (GPC) based on the following apparatus and conditions. Device: GPC-101 (manufactured by Showa Denko Co., Ltd.) Column: Combination of GPC-KF-801, GPC-KF-802, GPC-KF-803, and GPC-KF-804 Mobile phase: tetrahydrofuran <[A] copolymer Synthesis > [Synthesis Example 1] In a flask having a condenser and a stirrer, 5 parts by mass of 2,2'-azobis(2,4-dimercaptophthalonitrile) and 220 parts by mass of diethylene glycol were added. Mercaptoethyl ether. Next, 20 parts by mass of styrene, 12 parts by mass of methacrylic acid, 28 parts by mass of dicyclopentanyl methacrylate, and 4 parts by mass of glycidyl methacrylate were added, and the mixture was slowly stirred while stirring. The temperature was raised to 7 (TC' was maintained at this temperature for 5 hours to carry out polymerization, and it was found that the solution of the copolymer (A-1) was obtained. The obtained copolymer solution had a solid content of 3 5 · / 疋 31.30 / 〇, copolymer The Mw of (eight_1) is 12, 〇〇〇. In addition, the solid content concentration means the ratio of the mass of the copolymer to the total mass of the copolymer solution. [Synthesis Example 2] In a flask having a condenser and a stirrer, 5 parts by mass of 2,2'-azobis(2,4-dioxyl valeronitrile) and 22 parts by mass of diethylene glycol oxime-38-201202844-ethyl ether were added, followed by 'addition of 10 parts by mass of styrene 12 parts by mass of methacrylic acid, 23 parts by mass of tricyclodicyclopentanyl decyl acrylate, 20 parts by mass of glycidyl methacrylate, 20 parts by mass of 2-mercapto glycidyl methacrylate, 10 mass Part of tetrahydrofurfuryl methacrylate, after nitrogen replacement, further adding 5 parts by mass of 1,3 - butyl While slowly stirring, the temperature of the solution was raised to 7 〇 ° C, and the temperature was maintained for 5 hours, and polymerization was carried out to obtain a solution containing the copolymer (A 2 ). The obtained copolymer solution had a solid content concentration of 31.5%. The Mw of the copolymer (A-2) was 10,100. [Synthesis Example 3] In a flask having a condenser and a stirrer, 5 parts by mass of 2,2'-azobis(isobutyronitrile) and 22〇 were added. Parts by mass of diethylene glycol decyl ethyl group. Then 'add 15 parts by mass of styrene, 30 parts by mass of n-butyl methacrylate, 30 parts by mass of benzyl methacrylate and 25 parts by mass of methyl acrylate The glycidyl ester was stirred while stirring, and the temperature of the solution was raised to 80 ° C. The temperature was maintained for 5 hours to carry out polymerization to obtain a solution containing the copolymer (A-3), and the solid content concentration of the obtained copolymer solution was The Mw of the 31.0%' copolymer (A_3) is 1 Å, 〇〇〇. [Preparation of a radiation-sensitive resin composition for forming a cured film > [Examples 1 to 14 and Comparative Examples! The kind and amount shown in Table 1 are caused by polymerization of [A] polymer or copolymer, [B] polymerizable compound, and [C] And [D] compound is mixed, and then 5 parts by mass of γ-glycidoxypropyltrimethoxydecane as a [F] adhesion aid, 〇5 parts by mass of [G] surfactant (FTX-218, - </ br> After the micropore screening procedure of the aperture 〇·5 μηι was carried out, the radiation sensitive resin composition was prepared as Examples 1 to 14 and Comparative Examples 1 to 4, respectively. In addition, the "-" in the column indicates that the component is not used. The details of the [Β] polymerizable compound, the [C] polymerization initiator, and the [D] compound constituting the radiation sensitive composition are as follows. ([Α] polymer, copolymer) (Α-1) copolymer obtained in Synthesis Example 1 (Α-2) The copolymer obtained in Synthesis Example 2 (Α-3) The copolymer obtained in Synthesis Example 3 (Α-4) Phenolic novolac type epoxy resin ("EPIKOTE 152" manufactured by Japan Epoxy Resin Co., Ltd.) ([B] polymerizable compound) (Β-1) dipentaerythritol pentapropionate and dipentaerythritol Mixture of alcohol hexaacrylate vinegar (KAYARAD DPHA (Japan Chemical Pharmaceutical Co., Ltd.) (B-2) KAYARAD DPHA-40H (Sakamoto Chemical Co., Ltd.) (B-3) 1,9-decanediol diacrylate (B-4 Pentaerythritol tetraacrylate (B-5) trihydroxydecylpropane triacrylate (Β-6) ω-carboxypolycaprolactone monoacrylate (ARONIX Μ-5300, East Asia Synthetic Company) (Β-7 Succinic acid-modified pentaerythritol triacrylate (ARONIX TO-756, East Asia Synthetic Co., Ltd.) -40- 201202844 (B-8) Ethylene oxide-modified dipentaerythritol hexaacrylate ([C Polymerization initiator) (Cl) 1,2-octanediol-1-[4-(phenylthio)-2-(0-phenylhydrazinyl)] (IRGACURE OXEOl, Ciba · Specialty · Chemicals (C-2) Ethylketone-l-[9-ethyl-6-(2-mercaptobenzylidene)-9H-indazol-3-yl] -1-(0-ethyl fluorenyl) (IRGACURE OXE02, Ciba · Specialty · Chemicals) (C-3) 2-methyl-1-(4-methylthiophenyl)-2- morpholino 1-ketone (IRGACURE 907, Ciba · Specialty · Chemicals) (C-4) 2-Dimethylamino-2-(4-methylbenzyl)-1-(4-indololin-4-yl - Benzo)-butyl-ketone (IRGACURE 379, Ciba·Specialty·Chemicals) ([D] compound) (D-1) acetamide (D-2) N-mercaptoacetamide (D-3 O-phthalic acid (D-4) m-benzoic acid amine (D-5) hexamethylenediamine (D-6) N, N-diethyl fluorenyl-p-phenylenediamine (D -7) N, N, -diethylhydrazine, hexamethylenediamine comparative example amine compound (d-oxime) triethylamine 201202844 [Table i] [Α] polymer, copolymer [Β] polymerizable compound [ C] Polymerization Initiator [D] Compound Species Mass Species Parts by Mass Mass Species Partitions Example 1 (Α-4) 100 (Β-1) 100 (C-1) 15 (Dl) 0.1 Example 2 ( Α-4) 100 (Β-1) 100 (Cl) 15 (D-2) 0.1 Example 3 (Α-1) 100 (Β-1)/(Β-3) 90/10 (C-2) 10 (D-3) 0.1 Example 4 (Α-1) 100 (Β-1)/(Β-3) 90/10 (C-2) 10 (D-4) 0.1 Example 5 (Α-1) 100 (Β-1)/(Β-4) 80/20 (C-2) 10 (D-5) 0.1 Example 6 (Α-1) 100 (Β-1)/ (Β-4) 80/20 (C-3) 25 (D-6) 0.1 Example 7 (Α-1) 100 (Β-1)/(Β-2)/(Β-6) 60/40/ 10 (C-3) 25 (D-7) 0.1 Example 8 (Α-2) 100 (Β-4)/(Β-5) 50/50 (C-4) 25 (Dl) 0.2 Example 9 ( Α-2) 100 (Β-1) 100 (C-4) 20 (D-2) 0.2 Example 10 (Α-2) 100 (Β-8) 100 (Cl)/(C-3) 5/15 (D-3) 0.2 Example 11 (Α-2) 100 (Β-1) 100 (C-2) 10 (D-4) 0.2 Example 12 (Α-2) 100 (Β-7)/(Β -2) 80/20 (Cl)/(C-3)/(C-4) 5/5/5 (D-5) 0.2 Example 13 (Α-3) 100 (Β-3)/(Β- 4) / (Β-5) 30/30/40 (Cl) / (C-3) 5 / 15 (D-6) 0.2 Example 14 (Α-3) 100 (Β-3) / (Β-4 )/(Β-5) 40/40/20 (C-2)/(C-4) 5/15 (D-7) 0.2 Comparative Example 1 (Α-1) 100 (Β-1) 100 (C- 4) 20 (dl) 0.1 Comparative Example 2 (Α-1) 100 (Β-1) 100 (C-4) 20 - - Comparative Example 3 (Α-4) 100 (Β-1) 100 (Cl) 15 ( Dl) 0.1 Comparative Example 4 (Α-4) 100 (Β-1) 100 (Cl) 20 - - In the table, "-" indicates no addition. <Evaluation> The radiation sensitive resin composition was evaluated as follows. The results are shown in Table 2. [Measurement of Storage Stability (%)] The radiation-sensitive resin composition was allowed to stand in an oven at 40 ° C for one week, and the viscosity before and after being placed in the oven was measured to determine the viscosity change rate. In this case, when the viscosity change rate is 5% or less, the storage stability is considered to be good, and when it exceeds 5%, the storage stability is considered to be poor. The viscosity was measured at 25 ° C using an E-type viscometer (VISCONIC ELD.R, Toki Sangyo Co., Ltd.). [Measurement of Sensitivity (J/m2)] The radiation-sensitive resin composition was applied onto a non-glass glass substrate by a spin coater, and then prebaked on a hot plate at 100 ° C for 2 minutes to form a film thickness of 4.0. The coating of μιη. -42- 201202844 Next, on the obtained coating film, the light having a multi-(five) circular pattern of different sizes with a diameter of 8 μm 15 15 μη @ @ is used, and the exposure amount is reduced in the range of the core 2 by irradiation with a mercury lamp. radiation. Thereafter, a 0.40 mass% aqueous solution of tetramethylammonium hydroxide was used, and development was carried out by a liquid deposition method under the hunger, and the pure water was washed for 1 minute. However, in the oven, pre-baking is carried out for 60 minutes to form a hardened crucible having a pattern with a remaining circle. The height of the residual circular pattern before and after development was measured using an alchromatic microscope (VK-85, Keyence). From this value and the following formula, the residual film ratio (%) was obtained. Residual film rate (%) = (the height after development/the height before development is the sensitivity of the residual film rate of 90% or more as the sensitivity. When the exposure amount is 800 J/m2 or less, the sensitivity is considered to be good. [Heat resistance (%) Determination] In the above-mentioned cured film forming step, the mask is not inserted, exposed at an exposure amount of 7〇〇j/m 2 , and then 'in the oven, at 18 〇. After baking for a minute, the obtained coating film In the oven, under the 23rd generation (four) for 20 minutes, the film thickness before and after heating was measured by a stylus film thickness meter (Alpha Step IQ, KLATENCOR company ν'm~, AJ) to calculate the residual film rate. (The film thickness after the treatment/the film thickness before the treatment><_' is used as the heat resistance. [Measurement of chemical resistance (%)] The exposure amount in the above-mentioned cured film formation step is exposed, and then, Bake the minute, the resulting coating film is further 'not inserted into the reticle, in a 7 〇〇J/m2 box at 18 (after TC baking 6 〇 in the oven during heating to 60. (: with -43- 201202844 Dip into the membrane stripping solution CHEMICLEAN TS-204 (Sanyo Chemical Industry Co., Ltd.) for 15 minutes, after washing, 'in the oven again, The film was dried for 15 minutes under 12 Torr. The film thickness before and after the treatment was measured by a stylus film thickness meter (Alpha Step IQ' KLATENCOR Co., Ltd.), and the residual film ratio (film thickness after treatment/film thickness before treatment X 1) was calculated. 0 0) 'The residual film rate is used as the chemical resistance. [Measurement of light transmittance (%)] In the above-described cured film forming step, the mask is not inserted, and exposure is performed at an exposure amount of 7 〇〇 J/m 2 . Then, in the oven, after baking at 18 〇 for 6 〇 minutes, the obtained film was measured at a wavelength of 4 〇〇 nm using a spectrophotometer (15 〇 2 Do type Double Beam, manufactured by 曰立株式会社). In this case, when the light transmittance is less than 90%, the transparency is poor. [Measurement of flatness (nm)] Pigment-based dyeing is applied to a glass substrate impregnated with si〇2 (c〇1) 〇r resist) (JCR RED 689, JCR GREEN 706, CR 8200B, and JSR, Inc.), which form stripe-shaped filters of three colors of red, green, and blue as follows. Specifically, the above-mentioned anti-staining is performed using a spin coater. The color of the cockroach was applied to a si〇2 impregnated glass substrate, and pre-baked on a hot plate at 9 (rc for 150 seconds to form a coating). Then, using an exposure machine (Can〇n PLA501F, Canon), the ghi line (intensity ratio of wavelengths of 436nrn, 40 5nm, and 3 65nm) is irradiated by an exposure amount converted to an i-line of 2,000 J/m2 by a predetermined pattern cover. = 2 7 : 2 5 : 4 8) Next, development was carried out using a 0.05 mass% potassium hydroxide aqueous solution, and the mixture was rinsed with ultrapure water for 60 seconds. Then 'further in the oven, at 230. The underarm heat treatment was carried out for 30 minutes to form a monochromatic striped filter. Repeat the -44-201202844 operation for 3 colors to form stripe-shaped filters of 3 colors of red, green and blue (strip width 200μπι) °

選、】疋長度2,000μπι、測定範圍2,〇〇〇μιη的方形，測定方向是紅、綠、藍方向的條紋線的短軸方向以及紅· 紅、綠-綠、藍-藍的同一顏色的條紋線長軸方向的兩個方向，對各方向以測定點數η = 5(總計的η數是1〇)，通匕接觸式膜厚測定裝置測定（Alpha_Step、· TENc：C)R 公司）濾光片基板的表面凹凸時，是1〇μιη。通過旋塗器，在升^成。$ 光片的基板上塗布各個熱硬後，在熱板上，在㈣下預供培5分鐘，形成塗膜：物然後在潔淨烤箱中’在180t下後烘焙6〇分鐘在濾光片的上面升> 成膜厚約2 . 〇 pm的保護膜。這樣形成的在渡光片上具有保護膜的基板，使用接觸式膜厚測定裝置⑷pha_step ' KLA · tenc〇r公司），測定保護膜表面的凹ώ 。該測定是選取測定長度 2,〇〇〇μηι、測定範圍2,〇〇〇μηχ的方形，測定方向是紅^ 藍方向的條紋線的短軸方向以及紅_紅、綠綠、藍-藍的同—顏色的條紋線長軸方向的兩個方向，對各方向以測定點數η = 5(總計的η數是10)進行，求得各測定的最高部和最底部的高低差（nm)的Μ0次的平均值，作為保護膜的平整化性能(平整性）’在表2中表示。該值為200nm 以下時’認為保護膜的平整化性能良好。 [線性熱膨脹係數（p p m / °C )的測定] 在上述硬化膜形成步驟中，不插入光罩，在7〇〇j/m2 的曝光量下曝光，形成塗膜。之後，在烤箱中在 -45- 201202844Select, 疋 length 2,000μπι, measurement range 2, 〇〇〇μιη square, the direction of the measurement is the short-axis direction of the red, green, blue direction of the stripe line and the same color of red, red, green-green, blue-blue In the two directions of the long-axis direction of the stripe line, the number of measurement points η = 5 for each direction (the total number of η is 1 〇) is measured by the contact-type film thickness measuring device (Alpha_Step, · TENc: C)R When the surface of the filter substrate is uneven, it is 1 μm. Through the spinner, it is raised. After coating each of the hot hard plates on the substrate of the light sheet, pre-supplied for 5 minutes on the hot plate under (4) to form a coating film: then baked in a clean oven at 180t for 6 minutes in the filter. Above the rise > film thickness of about 2. 〇 pm protective film. The thus formed substrate having a protective film on the light-receiving sheet was measured for the concave surface of the surface of the protective film by using a contact-type film thickness measuring device (4) pha_step 'KLA · tenc〇r company). The measurement is to select a square of measurement length 2, 〇〇〇μηι, measurement range 2, 〇〇〇μηχ, and the measurement direction is the short-axis direction of the stripe line in the red-blue direction and the red-green, green-green, and blue-blue - The two directions of the long-axis direction of the stripe line of the color are measured for each direction by the number of measurement points η = 5 (the total number of η is 10), and the height difference (nm) between the highest part and the bottom part of each measurement is obtained. The average value of Μ0 times is shown in Table 2 as the flattening performance (flatness) of the protective film. When the value is 200 nm or less, it is considered that the planarization performance of the protective film is good. [Measurement of Linear Thermal Expansion Coefficient (p p m / °C)] In the above-described cured film forming step, the mask was formed without exposure by inserting a photomask at an exposure amount of 7 〇〇 j/m 2 . After that, in the oven at -45- 201202844

°C下加熱處理60分鐘硬化，製造測定用塗膜。接著，對該塗膜通過設置了溫度可變裝置的橢率計（DVA-36LH、溝尻光學工業所公司），在氮氣氛下，以測定時的升溫速度為l〇°C /分鐘，測定溫度範圍是20°C〜20CTC，測定各測定溫度下的膜厚的變化量，對該溫度繪圖，從其近似直線求得斜率b ’通過下述式求得線性熱膨脹係數a ^ T 表示初期膜厚。 a = b/T 可以判斷線性熱膨脹係數為200ppm/°C以下時，線性熱膨脹係數較低，即使是1 8 〇 °c的後烘焙，也可以製造具有足夠的硬化性的硬化膜。 [電壓保持率（％)的測定] 在表面形成防止鈉離子溶出的Si〇2膜，然後在將 ITO(姻-氧化錫合金）電極蒸鍍為規定形狀的鈉玻璃上，旋塗該.感放射線性樹脂組成物後，在90 〇C的清潔烤箱内’預烘培1 0分鐘，形成膜厚2. 〇 μηι的塗膜。接著’不插入光罩，以5〇〇J/in2的曝光量對塗膜曝光。之後’將該基板在2 3 °C的由〇 · 〇 4質量％氫氧化鉀水溶液形成的顯影液浸潰1分鐘，顯影後’通過超純水洗滌’風乾’然後’在1 8〇。(：下後;烘焙60分鐘，使塗膜硬化，形成永久性硬化膜。接著’形成該圖元的基板和只將IT〇電極蒸鍍為規定形狀的基板，通過混合了〇.8mm的玻璃珠的密封劑貼合後’注入Merck製造的液晶（MLC6608)，製造液晶胞。 -46- 201202844 接著，將液晶胞放入60°C的恆溫槽，通過液晶電壓保持率測定系統（VHR-1 A型、TOYO Technica公司）測定液晶胞的電壓保持率。此時的施加電壓是5.5 V的方形波，測定頻率是60Hz。這裏所述的電壓保持率是（16.7 毫秒後的液晶胞的電位差/ 0毫秒時施加的電壓）的值。如果液晶胞的電壓保持率為90%以下，則意味著液晶胞在 1 6.7毫秒的時間無法將施加電壓保持為規定等級，無法使液晶充分配向，產生殘影等「燒入」的可能性高。 [表2] 保存穩定性 (%) 感度 (J/m2) 耐熱性 (%) 耐化學腐触性 (%) 透光率 (%) 平整性 (nm) 耐熱線性膨脹係數 (ppm/°C) 電壓保持率 (%) 實施例1 4 700 97 98 95 200 190 96 實施例2 4 700 97 98 95 200 180 96 實施例3 4 600 98 98 96 180 200 97 實施例4 4 600 98 98 95 160 190 97 實施例5 4 700 98 98 90 180 180 96 實施例6 4 700 98 98 94 180 180 97 實施例7 4 700 98 98 97 180 190 97 實施例8 4 700 98 98 94 180 190 97 實施例9 3 600 98 98 96 180 190 96 實施例10 4 700 98 98 97 180 190 96 實施例11 4 700 98 98 94 180 180 97 實施例12 4 700 98 98 94 180 180 97 實施例13 3 700 99 98 97 180 190 97 實施例14 4 500 97 98 95 180 190 98 比較例1 8 800 95 95 85 200 220 80 比較例2 4 700 96 95 94 210 240 98 比較例3 10 800 96 95 94 210 220 82 比較例4 5 700 94 93 90 250 250 95 從表2的結果可以知道實施例1〜1 4的該組成物與比較例1〜4的組成物相比，具有良好的保存穩定性和放射性敏感度。另外，還可以知道由實施例1〜1 4的該組成物形成的硬化膜即使在200°C以下低溫燒製形成，耐熱性、耐化學藥品性、透光率、平整性、耐熱線性膨脹性等也優異。此外，具有該硬化膜的顯示元件的電壓保持率也良好。 -47- 201202844 [產業上之利用可能性] 本發明的感放射線性樹脂組成物可以容易地形成微細且精巧的圖案，可以同時實現保存穩定性和低溫燒製，而且具有足夠的放射線感度。另外，由該組成物形成的硬化膜作為其要求的性質的耐熱性、耐化學藥品性、透光率、平整性、電壓保持率、耐熱線性膨脹性等優異。因此，該組成物適合作為在希望低溫燒製的撓性顯示器等中使用的層間絕緣膜、保護膜和間隔物等的硬化膜的形成材料使用。【圖式簡單說明】無。【主要元件符號說明】無。 -48-The film was cured by heat treatment at ° C for 60 minutes to prepare a coating film for measurement. Then, the coating film was passed through an ellipsometer (DVA-36LH, Gully Optical Industry Co., Ltd.) equipped with a temperature-variable device, and the temperature was measured at a temperature increase rate of 10 ° C /min under a nitrogen atmosphere. The range is 20 ° C to 20 CTC, and the amount of change in film thickness at each measurement temperature is measured. The temperature is plotted, and the slope b ' is obtained from the approximate straight line. The linear thermal expansion coefficient a ^ T is obtained by the following formula to indicate the initial film thickness. . a = b/T When the linear thermal expansion coefficient is 200 ppm/°C or less, the linear thermal expansion coefficient is low. Even after post-baking at 18 °C, a hardened film having sufficient hardenability can be produced. [Measurement of Voltage Retention Rate (%)] A Si〇2 film that prevents sodium ions from eluting is formed on the surface, and then the ITO (gum-tin oxide alloy) electrode is vapor-deposited on a soda glass having a predetermined shape, and the feeling is spin-coated. After the linear resin composition was irradiated, it was prebaked for 10 minutes in a 90 ° C cleaning oven to form a film having a film thickness of 2. 〇μηι. Then, the mask was exposed without exposure to a mask at an exposure amount of 5 〇〇J/in2. Thereafter, the substrate was immersed in a developer solution of a 质量·〇 4 mass% potassium hydroxide aqueous solution at 23 ° C for 1 minute, and after development, it was washed by ultrapure water, air-dried, and then at 18 Torr. (: after the next; baking for 60 minutes, the coating film is cured to form a permanent cured film. Next, the substrate on which the element is formed and the substrate on which only the IT electrode is vapor-deposited into a predetermined shape are mixed with 〇.8 mm glass. After the sealing agent of the bead is bonded, liquid crystal (MLC6608) manufactured by Merck is injected to produce a liquid crystal cell. -46- 201202844 Next, the liquid crystal cell is placed in a thermostat at 60 ° C, and passed through a liquid crystal voltage retention ratio measuring system (VHR-1). A type, TOYO Technica company) measures the voltage holding ratio of the liquid crystal cell. The applied voltage at this time is a square wave of 5.5 V, and the measurement frequency is 60 Hz. The voltage holding ratio described here is (potential difference of the liquid crystal cell after 16.7 milliseconds / When the voltage holding ratio of the liquid crystal cell is 90% or less, it means that the liquid crystal cell cannot maintain the applied voltage at a predetermined level for a period of 16.7 milliseconds, and the liquid crystal cannot be sufficiently aligned, resulting in a residual The possibility of "burning in" is high. [Table 2] Storage stability (%) Sensitivity (J/m2) Heat resistance (%) Chemical corrosion resistance (%) Light transmittance (%) Flatness (nm ) Thermal linear expansion coefficient (ppm/°C) Pressure retention (%) Example 1 4 700 97 98 95 200 190 96 Example 2 4 700 97 98 95 200 180 96 Example 3 4 600 98 98 96 180 200 97 Example 4 4 600 98 98 95 160 190 97 Example 5 4 700 98 98 90 180 180 96 Example 6 4 700 98 98 94 180 180 97 Example 7 4 700 98 98 97 180 190 97 Example 8 4 700 98 98 94 180 190 97 Example 9 3 600 98 98 96 180 190 96 Example 10 4 700 98 98 97 180 190 96 Example 11 4 700 98 98 94 180 180 97 Example 12 4 700 98 98 94 180 180 97 Example 13 3 700 99 98 97 180 190 97 Implementation Example 14 4 500 97 98 95 180 190 98 Comparative Example 1 8 800 95 95 85 200 220 80 Comparative Example 2 4 700 96 95 94 210 240 98 Comparative Example 3 10 800 96 95 94 210 220 82 Comparative Example 4 5 700 94 93 90 250 250 95 It is understood from the results of Table 2 that the compositions of Examples 1 to 14 have good storage stability and radioactivity sensitivity as compared with the compositions of Comparative Examples 1 to 4. Further, it is also known that the cured film formed of the composition of Examples 1 to 14 is formed by firing at a low temperature of 200 ° C or lower, and has heat resistance, chemical resistance, light transmittance, flatness, and heat-resistant linear expansion property. It is also excellent. Further, the voltage holding ratio of the display element having the cured film was also good. -47-201202844 [Industrial Applicability] The radiation-sensitive resin composition of the present invention can easily form a fine and delicate pattern, can simultaneously achieve storage stability and low-temperature firing, and has sufficient radiation sensitivity. Further, the cured film formed of the composition is excellent in heat resistance, chemical resistance, light transmittance, flatness, voltage holding ratio, heat-resistant linear expansion property, and the like as required properties. Therefore, the composition is suitably used as a material for forming a hard film such as an interlayer insulating film, a protective film, and a spacer which are used in a flexible display or the like which is desired to be fired at a low temperature. [Simple description of the diagram] None. [Main component symbol description] None. -48-

Claims

201202844 VII. A patent scope: L A radiation sensitive resin composition characterized by comprising: [A] a polymer having an epoxy group, and a polymerizable compound having an ethylavalent unsaturated bond, [C a radiation-sensitive linear polymerization initiator, and at least one of the compounds of [D] selected from the group consisting of the following formulas (1) to η a compound, N XR2 Η Q ο II (1)

The number /1) of the ^ and the ruler independently represent a hydrogen atom, a carbon/=12 alkyl group, a cyclohexyl group, a phenyl group, a decyl group, an ethylene group, or a carbon atom number of 1 to 6. The number of carbon atoms substituted by an alkyl group, iH::, carboxyl group or ethyl fluorenyl group is! ~ Alkane; a base, a naphthyl group, a number / a cut) 'R'R4 each independently represents a hydrogen atom, an alkyl group of a carbon force ', a cyclohexyl group, and A represents a methylene group and a carbon atom. , stretching phenyl, stretching Caiji, stretching ethylene base, ▲ broken; number of 1 1 to 6 alkyl, self-substituted sub-" ', number 2 to 12 alkyl, phenyl, -49 - 201202844 In the formula (3), R5 and R6 each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclohexyl group, and A represents an anthracene group and an alkylene group having 2 to 12 carbon atoms. a phenyl group, a naphthyl group, a vinyl group, or an alkyl group having 1 to 6 carbon atoms, a methylene group substituted by a halogen, a stretching group having 2 to 12 carbon atoms, a stretching base, and a stretching The naphthyl group according to the invention of claim 2, wherein the polymer having an epoxy group is a polymer further having a rebel group. a radiation-sensitive linear resin composition of the above, wherein the above [C] radiation-sensitive polymerization initiator is composed of an acetophenone compound and a ruthenium-quinone ruthenium compound. At least one selected from the group. 4_ A method for forming a cured film, the method comprising: 1 to 3 senses of a part of the radiation (1) forming a coating film of the patented range of the radioactive resin composition on the substrate a step of (2) a step of at least a line of the coating film formed in the step (1), (3) a step of developing the step (2), and a step of developing the coating film irradiated with the radiation. wherein the above step (4) (4) The method for forming the coating film after the development in the firing step (3), as in the method of forming the fourth item of the patent application, has a firing temperature of 20 (Tc or less. *·""πβ-堉堉范围范围第第第第Resin composition to 3 spacers. β Μ 'Protection neck 7. — Display element film 0 It has the hardening of the scope of the patent scope. -50-201202844 IV. Designated representative figure: (1) Representative representative figure of the case For: No. (2) The symbol of the symbol of this representative figure is simple: Benefit. < * », 5. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: