TW201207558A

TW201207558A - Radiation-sensitive resin composition for forming cured film, method for producing radiation-sensitive resin composition fro forming cured film, cured film, method for forming cured film and display element

Info

Publication number: TW201207558A
Application number: TW100118398A
Authority: TW
Inventors: Eiji Yoneda; Nobuhiro Nishi; Seiichirou Kodama; Katsumi Inomata
Original assignee: Jsr Corp
Priority date: 2010-05-27
Filing date: 2011-05-26
Publication date: 2012-02-16
Also published as: JP5765049B2; TWI493284B; JP2012008537A

Abstract

Provided are a radiation-sensitive resin composition for forming cured film which has storage stability and low-temperature-firing and sufficient radiation sensitivity, a cured film which is excellent in heat resistance, chemical resistance, transmission, degree of flatness and linear thermal expansion resistance, and display element which is excellent in high voltage holding ratio. The present invention is a radiation-sensitive resin composition for forming cured film which has a viscosity at 25 DEG C of between 1.0 mPa.s to 50 mPa.s inclusive and comprises [A] a copolymer with (a1) a structure unit containing carboxyl and (a2) a structure unit containing epoxy, [B] a polymerizable compound with an ethylenically unsaturated bond, [C] a radiation-sensitive polymerization initiator, [D] a compound with hydroxyl or carboxyl, [E] an amine compound.

Description

201207558 六、發明說明：【發明所屬之技術領域】本發明涉及硬化膜形成用感放射線性樹脂組成物、硬化膜形成用感放射線性樹脂組成物的製造方法、硬化膜、硬化膜的形成方法及顯示元件。【先前技術】作為薄膜電晶體（TFT)型液晶顯示元件等電子部件為了般在配置成層狀的配線之間絕緣而設置層間絕緣膜例如TFT型液晶顯示元件就是藉由在層間絕緣膜上形成透明電極膜，再於其上形成液晶配向膜的步驟而製造的。作為所述層間絕緣膜，由於要曝露於透明電極膜的形成步驟中的高溫條件下、以及電極的圖案形成中使用的光阻劑的剝離液中’要求對這些條件有足夠的耐熱性及耐化學試劑性。另外’對於用來形成這種硬化膜的感放射線性樹脂組成物，也需要能縮短放射線照射時間（即’高放射線敏感度）及具有良好的貯存穩定性。向且採用TFT技術的輕量小型柔性顯示正在^及。作為柔性顯不器的基板，已研究了聚碳酸醋等塑膠基板。塑膠基板因加熱而伸展、收縮，結果就存在著損害顯示器功能的不好情況。因此正在研究使柔性顯不器製造中的加熱步驟低溫化。例如日本特開 2009-4394號公報中公開了含有即使進行低溫燒製也：硬化的聚醯亞胺前驅物的柔性顯示器上使用的柵絕緣膜用k布:¾ <_疋，冑塗布液並不具備肖由曝&顯影形成圖案的能力，因此不可能形成精細的圖案。而且，由於 -4 - 201207558 硬化反應進行的不充分，得到的硬化膜除耐熱性、耐化學試劑性外，並沒有達到滿^透光率、平坦性、耐線性熱膨脹性等的良好水準。因此還考慮了藉由添加低溫下也能用作環氧類材料的硬化劑的胺化合物來進行交聯反應的策略。但是，添加一般的胺化合物時，會導致隨時間經過而與組成物中存在的環氧基進行反應，可能會使貯存穩定性變差。由於這種情況，還期待開發出同時滿足貯存穩定性和低溫燒製，並且具有足夠的放射線敏感度的硬化犋形成用感放射線性樹脂組成物；作為硬化膜所需特性的耐熱性、耐化學試劑性、透光率、平坦性、耐線性熱膨脹性等性能優異的硬化膜。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】本發明是基於以上這種情況做出的，其目的在於提供同時滿足貯存穩定性和低溫燒製，並且具有足夠的感放射線性的硬化膜形成用感放射線性樹脂組成物；耐熱性、耐化學試劑性、透光率、平坦性及耐線性熱膨脹性等性此優異的硬化膜以及電壓保持率優異的顯示元件。用於解決上述問題的發明為：硬化膜形成用感放射線性樹脂組成物，其含有： [A]具有（a 1)含羧基的結構單元及（a2)含環氧基的結構單元的共聚物（以下也稱為「[A]共聚物」）、 -5- 201207558 [B] 具有乙烯性不飽和鍵的聚合性化合物（以下，也稱為「[B]聚合性化合物」）、 [C] 感放射線性聚合引發劑、 [D] 具有羥基或羧基的化合物（以下，也稱為「[D]化合物」）、及 [E] 胺化合物；並且25C下的黏度為l.OmPa· s以上50mPa· s以下。該感放射線性樹脂組成物含有作為驗可溶性樹脂的 [A]共聚物、[B]聚合性化合物及[C]感放射線性聚合引發劑。作為感光性材料的該感放射線性樹脂組成物可以藉由利用了感放射線性的曝光、顯影容易地形成精細而精巧的圖案’並且具有足夠的感放射線性。另外，由於含有[D]化合物及[E]胺化合物，該感放射線性樹脂組成物在25°C下的黏度可以被控制在1 .〇mPa · s以上50mPa · s 以下’能夠同時滿足貯存穩定性和低溫燒製。 [E]胺化合物較佳為可以被包合於[d]化合物中。藉由形成可以將[E]胺化合物包合於[D]化合物中的胺化合物，至少一部分形成了晶籠化合物，該感放射線性樹脂組成物可以含有晶籠化合物，能夠同時滿足貯存穩定性和低溫燒製。即’在室溫下促進硬化的[E]胺化合物被晶龍的狀態下，幾乎不進行環氧基的硬化反應，不會使組成物溶液的黏度增加。因此該感放射線性樹脂組成物是貯存穩定性優異的組成物。另一方面，如果將該感放射線性樹脂組成物加熱到規定的溫度以上，則晶籠崩解而 -6- 201207558 釋放出[E]胺化合物，含環氧基的樹脂發生交聯，促進了硬化反應。另外，通常該感放射線性樹脂組成物在溶液狀態下使用時，為了確保溶解性，較佳為使用極性溶劑。另一方面，晶籠化合物一般為固體粉末狀，如果溶解在醇類溶劑、鱗類溶劑等極性溶劑中，則晶籠可能會崩解，因此被認為要分散在組成物溶液等中進行使用。但是，對於该感放射線性樹脂組成物，可認為共存的[A ]共聚物中的羧基和晶籠化合物之間的相互作用抑制了晶籠的崩解，可以使用極性溶劑。而且，可以想到由於上述相互作用，羧基的質子加成到咪唑上，羧基發生陰離子化，生成了碳負離子。可以認為因為該碳負離子還具有高親核性，於是也可以達到晶籠化合物促進[A]共聚物中的環氧基的硬化反應的協同作用。 [D]化合物是由下述式⑴及式⑺分別表示的化合物構成的群組中選出的至少一種化合物，_化合物較佳[Technical Field] The present invention relates to a radiation-sensitive resin composition for forming a cured film, a method for producing a radiation-sensitive resin composition for forming a cured film, a method for forming a cured film, and a cured film, and Display component. [Prior Art] As an electronic component such as a thin film transistor (TFT) liquid crystal display device, an interlayer insulating film such as a TFT liquid crystal display element is formed by insulating a wiring arranged in a layer shape, for example, by forming an interlayer insulating film. The transparent electrode film is produced by the step of forming a liquid crystal alignment film thereon. As the interlayer insulating film, it is required to have sufficient heat resistance and resistance to these conditions due to the high temperature conditions to be exposed in the formation step of the transparent electrode film and the stripping liquid of the photoresist used in the pattern formation of the electrode. Chemically reactive. Further, it is also required to shorten the radiation irradiation time (i.e., 'high radiation sensitivity') and to have good storage stability for the radiation sensitive resin composition for forming such a cured film. Lightweight and compact display using TFT technology is being used. As a substrate of a flexible display, a plastic substrate such as polycarbonate or the like has been studied. The plastic substrate stretches and contracts due to heating, and as a result, there is a bad condition that impairs the function of the display. Therefore, research is being conducted to lower the heating step in the manufacture of the flexible display. For example, Japanese Laid-Open Patent Publication No. 2009-4394 discloses a k-cloth for a gate insulating film which is used for a flexible display including a hardened polyimide precursor which is cured at a low temperature: 3⁄4 <_疋, 胄 coating liquid It does not have the ability to form a pattern by exposure and development, and thus it is impossible to form a fine pattern. Further, since -4 - 201207558 is insufficient in the hardening reaction, the obtained cured film does not have a good level of light transmittance, flatness, linear thermal expansion resistance, and the like in addition to heat resistance and chemical resistance. Therefore, a strategy of performing a crosslinking reaction by adding an amine compound which can also be used as a hardener of an epoxy-based material at a low temperature is also considered. However, when a general amine compound is added, it may cause a reaction with an epoxy group present in the composition over time, which may deteriorate storage stability. In view of such a situation, it is also expected to develop a radiation-sensitive resin composition for hardening enamel formation which satisfies both storage stability and low-temperature firing, and has sufficient radiation sensitivity; heat resistance and chemical resistance as characteristics required for the cured film A cured film excellent in properties such as reagent properties, light transmittance, flatness, and linear thermal expansion resistance. CITATION LIST Patent Literature PTL 1 JP-A-2009-4394 SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object thereof is to provide storage stability and low-temperature firing simultaneously, and have sufficient A radiation-sensitive resin composition for forming a cured film having a radiation sensitivity; a cured film excellent in heat resistance, chemical resistance, light transmittance, flatness, and linear thermal expansion resistance, and a display element excellent in voltage holding ratio. The invention for solving the above problems is: a radiation sensitive resin composition for forming a cured film, comprising: [A] a copolymer having (a1) a carboxyl group-containing structural unit and (a2) an epoxy group-containing structural unit (hereinafter also referred to as "[A] copolymer"), -5-201207558 [B] A polymerizable compound having an ethylenically unsaturated bond (hereinafter also referred to as "[B] polymerizable compound"), [C] a radiation-sensitive linear polymerization initiator, [D] a compound having a hydroxyl group or a carboxyl group (hereinafter, also referred to as "[D] compound"), and an [E] amine compound; and a viscosity at 25 C of 1.0 mPa·s or more and 50 mPa · s below. The radiation sensitive resin composition contains a [A] copolymer, a [B] polymerizable compound, and a [C] radiation sensitive polymerization initiator as a solvent-soluble resin. The radiation-sensitive resin composition as a photosensitive material can easily form a fine and delicate pattern by utilizing radiation-sensitive exposure and development, and has sufficient radiation sensitivity. In addition, since the [D] compound and the [E] amine compound are contained, the viscosity of the radiation sensitive resin composition at 25 ° C can be controlled to be less than 1. 〇mPa · s above 50 mPa · s, which can simultaneously satisfy storage stability. Sex and low temperature firing. The [E] amine compound is preferably encapsulated in the [d] compound. By forming an amine compound which can encapsulate the [E] amine compound in the [D] compound, at least a part of the crystal cage compound is formed, and the radiation sensitive resin composition can contain a crystal cage compound, which can simultaneously satisfy storage stability and Low temperature firing. Namely, in the state in which the [E] amine compound which promotes hardening at room temperature is in the form of a crystal dragon, the epoxy group hardening reaction hardly proceeds, and the viscosity of the composition solution is not increased. Therefore, the radiation sensitive resin composition is a composition excellent in storage stability. On the other hand, if the radiation sensitive resin composition is heated to a predetermined temperature or higher, the crystal cage disintegrates and the [E] amine compound is released from -6 to 201207558, and the epoxy group-containing resin crosslinks to promote hardening. reaction. Further, in general, when the radiation sensitive resin composition is used in a solution state, in order to ensure solubility, a polar solvent is preferably used. On the other hand, the crystal cage compound is generally in the form of a solid powder. If it is dissolved in a polar solvent such as an alcohol solvent or a scaly solvent, the crystal cage may be disintegrated. Therefore, it is considered to be dispersed in a composition solution or the like and used. However, in the radiation-sensitive resin composition, it is considered that the interaction between the carboxyl group and the cage compound in the coexisting [A] copolymer suppresses the disintegration of the cage, and a polar solvent can be used. Further, it is conceivable that the protons of the carboxyl group are added to the imidazole due to the above interaction, and the carboxyl group is anionized to form a carbanion. It is considered that since the carbanion also has high nucleophilicity, it is also possible to achieve a synergistic effect of the cage compound promoting the hardening reaction of the epoxy group in the [A] copolymer. The compound [D] is at least one compound selected from the group consisting of compounds represented by the following formulas (1) and (7), and the compound is preferably a compound.

(2) 1) 201207558 (式⑴中，x為單鍵、亞甲基或碳原子數為2〜6的伸烷基。R1〜R«各自獨立地為氫原？、碳原子數為“2的烧基、齒素原子、碳原子㈣1〜12的院氧基或可以具有取代基的苯基。式（2)十，R9為碳原子數為1〜12的的烷基、碳原子數為1〜12的烷氧基、硝基或羥基。）藉由將[D]化合物及[E]胺化合物分別設定為上述特定化合物，可以有效地形成晶蘢化合物。上述式（1)表示的化合物，較佳為下述式（11)表示的化合物。 R1 R2(2) 1) 201207558 (in the formula (1), x is a single bond, a methylene group or an alkylene group having 2 to 6 carbon atoms. R1 to R« are each independently a hydrogen atom, and the number of carbon atoms is "2" a base group, a dentate atom, a carbon atom (tetra) 1 to 12 or a phenyl group which may have a substituent. Formula (2) X, R9 is an alkyl group having 1 to 12 carbon atoms, and the number of carbon atoms is Alkoxy group, nitro group or hydroxy group of 1 to 12.) By setting the [D] compound and the [E] amine compound to the above specific compounds, respectively, a crystalline germanium compound can be formed. The compound represented by the above formula (1) Preferably, it is a compound represented by the following formula (11). R1 R2

OH R3OH R3

(式（1-1)中，X及R1〜R8與上述式（1)中含義相同。）藉由將上述式（1)表示的化合物設定為上述式表示的化合物’可以進一步提高貯存穩定性，也能促進低溫時的硬化。對於該感放射線性樹脂組成物，較佳為[E]胺化合物的至少一部分被包合於[D]化合物中。藉由使在該感放射線性樹脂組成物中[E]胺化合物的至少一部分被包合於 [D]化合物中而形成晶籠化合物’可以同時滿足貯存穩定性和低溫燒製。 -8 201207558 [c]感放射線性聚合引發劑，較佳為由笨乙酮化及0-醯基肟化合物構成的群組中選出的至少—種。：使用上述特定化合物作為[c]感放射線性聚合引發劑：使在低曝光量的情況下也可以進一步提高耐硬化膜的所需特性。 F兩該感放射線性樹脂組成物，較佳為還含有由醇類溶劑及鱗類溶劑的至少一種溶劑。藉由含有上述極性溶劑，可以使該感放射線性樹脂組成物容易溶解，並且可以認為對於本發明，如上所述即使在使用極性溶劑的情況下也了以藉由與晶籠化合物的相互作用抑制晶籠的崩解0 對於25 c下黏度為1 .〇mpa · s以上50mPa . s以下的忒感放射線性樹脂組成物，較佳為將[D ]化合物中包合 [E]胺化合物而得到的晶籠化合物混入[A]共聚物、[B]聚合性化合物及[C]感放射線性聚合引發劑中進行配製。如果利用上述步驟，就可以有效地製造含有晶籠化合物的該感放射線性樹脂組成物。本發明的硬化膜形成方法具備： (1) 在基板上形成該感放射線性樹脂組成物塗膜的步驟； (2) 對上述塗膜的至少一部分照射放射線的步驟； (3) 使經過上述放射線照射的塗膜顯影的步驟；及 (4) 對經過上述顯影的塗膜進行燒製的步驟。根據使用該感放射線性樹脂組成物的本發明的形成方法’可以形成耐熱性、耐化學試劑性、透光率、平坦性及耐線性熱膨脹性得到很均衡地滿足的硬化膜。 -9 - 201207558 上述步驟（4)的燒製溫度較佳為2〇(rc以下。作為該感放射線性;14+ Bt , ’T月5組成物，在實現如上所述的低溫燒製的同時也簽目φ(In the formula (1-1), X and R1 to R8 have the same meanings as in the above formula (1).) By setting the compound represented by the above formula (1) to the compound represented by the above formula, storage stability can be further improved. It also promotes hardening at low temperatures. For the radiation sensitive resin composition, at least a part of the [E] amine compound is preferably contained in the [D] compound. The crystal cage compound is formed by allowing at least a part of the [E] amine compound to be contained in the [D] compound in the radiation sensitive resin composition to satisfy both storage stability and low-temperature firing. -8 201207558 [c] A radiation-sensitive polymerization initiator, preferably at least one selected from the group consisting of phenethyl ketone and 0-fluorenyl ruthenium compounds. : The above specific compound is used as the [c] radiation-sensitive polymerization initiator: The desired properties of the cured film can be further improved in the case of a low exposure amount. F. The radiation-sensitive linear resin composition preferably further contains at least one solvent selected from the group consisting of an alcohol solvent and a scaly solvent. By containing the above polar solvent, the radiation sensitive resin composition can be easily dissolved, and it can be considered that, for the present invention, as described above, even when a polar solvent is used, the interaction with the cage compound is suppressed. The disintegration of the cage is 0. For a 忒〇 a a 以下 a a a a a a a 50 50 50 50 50 50 50 50 50 50 50 以下以下以下以下以下以下以下以下以下以下以下以下以下以下以下以下以下以下以下以下以下以下以下以下以下The crystal cage compound is prepared by mixing the [A] copolymer, the [B] polymerizable compound, and the [C] radiation sensitive polymerization initiator. If the above steps are utilized, the radiation sensitive resin composition containing the crystal cage compound can be efficiently produced. The method for forming a cured film of the present invention comprises: (1) a step of forming a coating film of the radiation sensitive resin composition on a substrate; (2) a step of irradiating at least a part of the coating film with radiation; (3) passing the radiation a step of developing a coating film to be irradiated; and (4) a step of firing the coating film subjected to the above development. According to the formation method of the present invention using the radiation-sensitive resin composition, a cured film having uniform heat resistance, chemical resistance, light transmittance, flatness, and linear thermal expansion resistance can be formed. -9 - 201207558 The firing temperature in the above step (4) is preferably 2 〇 (rc or less. As the sensitizing radiation; 14+ Bt, 'T yue 5 composition, while achieving the low-temperature firing as described above Also sign φ

、7存穩定性，並且具有足夠的放射線敏感度。因此，兮合rV 邊感放射線性樹脂組成物適宜用作希望進行低《L &製的柔性顯示器等中使用的層間絕緣膜、保護膜及隔離物等硬化膜的形成材料。本發明也較佳為包含由該感放射線性樹脂組成物形成的作為層間絕緣膜、保護膜或隔離物的硬化膜。另外，本發明也較佳為包含具備該硬化膜的顯示元件，可以實現優異的電壓保持率。還有’本說明書中所謂「燒製」是指將層間絕緣膜、保護膜及隔離物等硬化膜加熱到所需要的表面硬度。另外’「晶籠化合物」是指另一個客體分子按分子單位被包嵌於主分子形成的空間中而形成的化合物。「感放射線性樹脂組成物」中的「放射線」是包括可見光、紫外線、遠紫外線、X線、帶電粒子束等的概念。另外，上述黏度是使用E型黏度計（東機產業製，VISCONIC ELD.R)，測定25°C下該組成物的黏度（mPa · s)。通常，胺化合物已知是作為促進環氧化合物的交聯反應的硬化促進劑。在該組成物中[E]胺化合物也對[A]成分中的環氧基起作用，促進其交聯反應。在這種情況下，組成物溶液的黏度增加。如果達到5 0 m P a · s以上，則塗布時控制膜厚會不容易，變得不適合用作硬化膜形成用感放射線性樹脂組成物。 -10- 201207558 對於本申請的組成物，由於含有[D]化合物及[e]胺化合物，可以將該感放射線性樹脂組成物在25t：下的黏度控制在l.OmPa . s以± 50mPa · s以下，能夠同時滿足貯存穩定性和低溫燒製。 [發明效果] 如以上說明’本發明的硬化膜形成用感放射線性樹脂組成物可以容易地形成精細而精巧的圖案，同時滿足了貯存穩定性和低溫燒製’並且具有足夠的感放射線 ^ 另外由6亥感放射線性樹脂組成物形成的硬化膜在耐熱性、耐化學試劑性、透光率、平坦性及耐線性熱膨服性方面優異。因此，該感放射線性樹脂組成物適宜用作希望進行低溫燒製的柔性顯示器等中使用的層間絕緣膜、保護膜及隔離物等硬化膜的形成材料。另外，本發明也較佳為包含具備該硬化膜的顯示元件，可以實現優異的電壓保持率。【實施方式】 <硬化膜形成用感放射線性樹脂組成物> 本發明的硬化膜形成用感放射線性樹脂組成物含有 [A]共聚物、[B]聚合性化合物、[c]感放射線性聚合引發劑、[D]化合物及[E]胺化合物，25。(：下的黏度為l.OmPa· s以上50mPa · s以下。另外，作為該感放射線性樹脂組成物’只要不損害本發明的效果，還可以含有任意成分。以下對各成分進行詳細說明。 -11- 201207558 < [A]共聚物〉該感放射線性樹脂組成物中含有的[A]共聚物具有 (a 1)含羧基的結構單元及（a2)含環氧基的結構單元。作為獲得[A]共聚物的方法’例如使用聚合引發劑，使提供（al) 含叛基的結構單元（敌基也包括酸肝基）的不飽和敌酸和/ 或不飽和羧酸酐（以下，也稱為「化合物（i)」）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’也稱為「化合物（ii)」）在溶劑中進行共聚而得到的。另外’根據需要，作為也可以在使用上述化合物 (i)、化合物（ii)的同時含有（曱基）丙烯酸烷基酯等自由基聚合性化合物（以下’也稱為「化合物（iii)」）作為（a3)進行共聚，形成[A]共聚物。作為化合物（i) ’可以列舉例如丙烯酸、甲基丙烯酸、巴豆酸、琥珀酸2-丙烯醯氧基乙酯、琥珀酸2-曱基丙烯酿氧基乙酯、六氫鄰苯二曱酸2-丙烯醯氧基乙酯、六氫鄰苯二曱酸2-甲基丙烯醯氧基乙酯等單羧酸；馬來酸、富馬酸、檸康酸等二羧酸；馬來酸酐等二羧酸酐。在這些化合物中，從共聚反應性及得到的共聚物對驗性顯影液的溶解性方面考慮，較佳為丙烯酸、甲基丙稀酸、琥珀酸2-丙烯醯氧基乙酯、琥珀酸2-甲基丙烯醯氧基乙酯、馬來酸酐。對於[A]共聚物，化合物⑴可以單獨使用一種或混合使用兩種以上。在[A]共聚物中，作為化合物⑴的含有率’較佳為5質量％〜40質量％，更佳為7質量％〜30質量％，特佳為8質量％〜25質量％。藉由使化合物（i)的含 -12- 201207558 有率處於5質量％〜4〇質量％，可以得到放射線敏感度、顯影性及貯存穩定性等特性以更高水準達到最佳化的感放射線性樹脂組成物。作為化合物（ii)，可以列舉具有環氧基（環氧乙烷基、氧雜環丁烷基）等的自由基聚合性化合物。作為具有垓氧乙烷基的自由基聚合性化合物，可以列舉例如：丙烯酸縮水甘油酯、丙烯酸2_甲基縮水甘油酯、丙 ^酸3,4_環氧了 ^旨 '丙烯酸6,7_環氧庚自旨、丙烯酸3,4_ 環氧環己醋、丙烯酸_3,4_環氧環己基曱醋等丙烯酸環氧甲基丙烯酸縮水甘油酯、甲基丙烯酸2-甲美縮水甘 =、甲基丙料3,4•環氧丁目旨、曱基㈣酸^環氧 =、甲基丙稀酸3,4_環氧環以旨、f基丙稀酸Μ-環氧衣己基甲酯等甲基丙烯酸環氧烷基酯； ▼ , r «"«人π曰个 Η /坩Η日、α _止i5Fi 並工油酯、„ T：丁 1 丙基丙烯酸縮水甘環氧庚缩水甘油醋、乙基丙稀酸6,7· 庚知等α-烷基丙烯酸環氧烷基酯；鄰乙烯基苄基縮水甘油醚、醚、對乙Μ其—1 Ί G埤基：V基縮水甘油于乙烯基卞基縮水甘油醚等縮水甘油醚。作為具有氧雜環丁烷基的自由基以列舉例如3-(曱基丙烯醯氧基氧化“勿’可基丙稀酿氧基甲基)·3_乙基氧雜環;):雜:晨U(甲氧基甲基)-2-甲基氧雜環丁烷：-(甲基丙烯醯氧雜環丁炫、3-(甲基丙稀酿氧基丙婦酿氧基乙基) 炫、2-乙基_3·Γ甲其土-乙基氧雜環丁7, stable, and has sufficient radiation sensitivity. Therefore, the conjugated rV sensitized radiation-based resin composition is suitably used as a material for forming a cured film such as an interlayer insulating film, a protective film, and a separator which are used in a flexible display made of L & The present invention is also preferably a cured film comprising an interlayer insulating film, a protective film or a separator formed of the radiation sensitive resin composition. Further, the present invention also preferably includes a display element provided with the cured film, and an excellent voltage holding ratio can be achieved. In the present specification, "firing" means heating a cured film such as an interlayer insulating film, a protective film, and a separator to a desired surface hardness. Further, "cage compound" means a compound in which another guest molecule is encapsulated in a space formed by a host molecule in a molecular unit. The "radiation" in the "radiation-sensitive resin composition" is a concept including visible light, ultraviolet light, far ultraviolet light, X-ray, charged particle beam, and the like. Further, the above viscosity was measured by using an E-type viscometer (VISCONIC ELD.R, manufactured by Toki Sangyo Co., Ltd.), and the viscosity (mPa · s) of the composition at 25 ° C was measured. Generally, an amine compound is known as a hardening accelerator which promotes a crosslinking reaction of an epoxy compound. In the composition, the [E] amine compound also acts on the epoxy group in the [A] component to promote the crosslinking reaction. In this case, the viscosity of the composition solution increases. When it is at least 50 m P a · s or more, it is not easy to control the film thickness at the time of coating, and it is not suitable as a radiation-sensitive resin composition for forming a cured film. -10- 201207558 For the composition of the present application, since the [D] compound and the [e] amine compound are contained, the viscosity of the radiation sensitive resin composition at 25 t: can be controlled to 1.0 mPa.s at ± 50 mPa. Below s, storage stability and low-temperature firing can be satisfied at the same time. [Effect of the Invention] As described above, the sensitized radiation resin composition for forming a cured film of the present invention can easily form a fine and delicate pattern while satisfying storage stability and low-temperature firing and having sufficient sensitization radiation. The cured film formed of the 6-ray radiation-linear resin composition is excellent in heat resistance, chemical resistance, light transmittance, flatness, and linear thermal expansion resistance. Therefore, the radiation sensitive resin composition is suitably used as a material for forming a cured film such as an interlayer insulating film, a protective film, and a separator which are used in a flexible display or the like which is desired to be fired at a low temperature. Further, the present invention also preferably includes a display element having the cured film, and an excellent voltage holding ratio can be realized. [Embodiment] <The radiation-sensitive resin composition for forming a cured film> The radiation-sensitive resin composition for forming a cured film of the present invention contains [A] copolymer, [B] polymerizable compound, and [c] radiation sensitive Polymerization initiator, [D] compound and [E] amine compound, 25. (The viscosity in the lower part is not more than 50 mPa·s.) The radiation-sensitive resin composition of the present invention may contain any component as long as the effect of the present invention is not impaired. Hereinafter, each component will be described in detail. -11-201207558 < [A] Copolymer> The [A] copolymer contained in the radiation sensitive resin composition has (a1) a carboxyl group-containing structural unit and (a2) an epoxy group-containing structural unit. The method for obtaining the [A] copolymer, for example, using a polymerization initiator, provides an unsaturated dicarboxylic acid and/or an unsaturated carboxylic anhydride which provides (al) a tether-containing structural unit (the enemy group also includes an acid liver group) (hereinafter, Also known as "compound (i)") and a radically polymerizable compound having an epoxy group (hereinafter referred to as "compound (ii)"), which provides (a2) an epoxy group-containing structural unit, is carried out in a solvent. In addition, as the above-mentioned compound (i) and the compound (ii), a radically polymerizable compound such as an alkyl (meth) acrylate may be contained as needed (hereinafter, also referred to as "a compound" (iii)") as (a 3) Copolymerization to form [A] copolymer. As the compound (i) ', for example, acrylic acid, methacrylic acid, crotonic acid, 2-propenyloxyethyl succinate, 2-mercaptopropene succinic acid can be cited. a monocarboxylic acid such as ethyl ester, hexahydrophthalic acid 2-propenyloxyethyl ester or hexahydrophthalic acid 2-methylpropenyloxyethyl ester; maleic acid, fumaric acid, a dicarboxylic acid such as citraconic acid or a dicarboxylic acid anhydride such as maleic anhydride. Among these compounds, acrylic acid and methyl propylene are preferred from the viewpoints of copolymerization reactivity and solubility of the obtained copolymer to the developer. Acid, 2-propenyl methoxyethyl succinate, 2-methyl propylene methoxyethyl succinate, and maleic anhydride. The compound (1) may be used alone or in combination of two or more kinds for the [A] copolymer. In the [A] copolymer, the content of the compound (1) is preferably 5% by mass to 40% by mass, more preferably 7% by mass to 30% by mass, even more preferably 8% by mass to 25% by mass. Radiation sensitivity can be obtained by making the compound (i) having a -12-201207558 rate of 5 mass% to 4 mass% A radiation-sensitive resin composition which is optimized to a higher level, such as degree, developability, and storage stability. As the compound (ii), an epoxy group (oxiranyl group, oxetane) may be mentioned. The radical polymerizable compound having a oxime oxy group, etc., examples thereof include glycidyl acrylate, 2-methylglycidyl acrylate, and propylene glycol 3,4_ ring. Oxygen has the meaning of 'Acrylic 6,7_epoxy Gum, acrylic 3,4_ epoxy cyclohexanone, acrylic _3,4_epoxycyclohexyl vinegar, etc. Acrylic epoxy methacrylate glycidyl ester, A 2-Acetyl acrylate = methyl propylene, 3, 4 epoxide, thiol (tetra) acid ^ epoxy = methyl methacrylate 3, 4 epoxide ring, f-propyl Epoxyalkyl methacrylate such as dilute bismuth-epoxyhexyl methyl ester; ▼ , r «"«人π曰一Η /坩Η日,α _止i5Fi and oleyl ester, „T: 丁1 propyl acrylate glycidyl epoxide glycidyl vinegar, ethyl acrylate acid 6,7 · Gengzhi and other α-alkyl acrylate alkyl alkyl ester; o-vinyl benzyl Ether, ether, ethyl Μ which Pi -1 Ί G group: V based on vinyl glycidyl ether glycidyl ether Bian. The radical having an oxetane group is exemplified by, for example, 3-(mercapto propylene oxy oxy oxidizing "Doubly acrylonitrile oxymethyl group" 3-ethyloxy heterocycle;): hetero: Morning U (methoxymethyl)-2-methyloxetane: -(methacrylofluorene oxirane, 3-(methyl propylene oxide oxypropyl oxyethyl) Hyun, 2-ethyl_3· Γ甲土-ethyl oxetane

(f基丙烯醯氧基乙基)氧雜iTO 土 J虱雜％丁烷、3(丙 201207558 烯醯氧基尹基）氧雜環丁氧雜私丁炫、3-(丙稀醯氧基尹乳基，基）-3_乙基 3_(丙烯醯氧基乙基)氧雜環丁二〒基氧雜環丁烷、乙基氧雜環丁烷、2•乙 /、_(丙烯醯氧基乙基俨、7，田龙基（丙婦酿氧基？ I、备）凡（f基丙婦酿氧基T基）氧雜产丁科土）氧雜環丁基丙烯醯氧基尹基)氧雜環丁燒二其元、2-，基·2_(尹氧基f基）氧雜環丁烷、扣尹義2 土·2-(尹基丙稀醯氧雜環丁烧、甲基丙烯酸心;(基丙烯酿氧基歹基）乙酯、甲基丙烯酸2_(2 /基氧雜環丁烷基）） 2- (甲基丙稀酿氧基基氧雜環丁燒基))乙醋、稀嶋乙基)·”基氧雜:;丁基，雜2…、Η甲基丙氧雜環丁烧、2_甲基·2_(丙稀酿：基甲=…基） 3- 甲基丙稀醯氧基甲基：氧雜％丁燒' 環丁烧基））乙醋、甲基丙稀酸2_( (二甲基氧雜乙醋、2·(丙婦醯氧基土 _雜環丁燒基））醯氧基乙基^基氧雜環)丁二基=;7二、2·(丙稀在這些化合物中，甲基丙烯酸 :“曰。稀酸2-甲基縮水甘油酯、甲基丙稀们油酉曰、甲基丙烯醯氧基甲基)氧雜環丁烧、丙：氧丁基、3-(丙雜環丁烧'…基丙烯酿氧二烧、2-(曱基丙婦酿氧基甲基）氧二乳雜& 丁 ::保護膜及隔離物等硬化膜對基板:::：：間：：门耐熱1±而且提高了顯示元件的的。 F 因此是較佳 201207558 _對於[A]共聚物，化合物（Η)可以單獨使用—種或混合使用兩m。在[A]共聚物中，作為化合物⑴）的含有:。，車又佳為10質量％〜質量％，更佳為15質量％〜65 =量％。藉由使用化合物（ii)的含有率處於10質量％〜7〇質量％ ’共聚物的分子量容易控制，可以得到顯影性、敏感度等以更高水準達到最佳化的感放射線性樹脂組成物0 作為化合物（iii)，可以列舉（甲基）丙烯酸烷基酯、（曱基）_丙烯酸脂環式醋、含氧原子的不飽和五員雜環及六員雜環（甲基）丙烯酸醋、具有羥基的（曱基）丙烯酸醋、（曱基）丙烯酸芳基酯、不飽和二鲮酸二酯、馬來醯亞胺化合物、（甲基）丙烯酸的經烧基酯、苯乙烯、α_甲基苯乙烯、 1，3-丁二烯。作為（曱基）丙烯酸烧基酯，可以列舉例如曱基丙稀酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丁酯、曱基丙烯酸二級丁酯、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）丙烯酸脂環式烧基酯，可以列舉例如曱基丙烯酸環戊酯、曱基丙烯酸二環戊基酯、甲基丙烯酸環己酯、甲基丙嫦酸2 -甲基環己酯、曱基丙烯酸三環二 %1戍基自旨、甲基丙稀酸2 - 一續戊氧基乙自旨、甲基丙稀酸異花酯、丙烯酸環戊酯、丙烯酸環己酯、丙烯酸2 -甲基環己酯、丙烯酸三環二環戊基酯、丙烯酸2 -二環戊氧基乙酯、丙烯酸異萡酯等。 -15- 201207558 作為含氧原子的不飽和五旨她ώ 株祕此員雜展及六員雜環甲基丙埤酸酯，可以列舉例如： (曱基）丙烯酸四氫糠酯、）急 △甲基丙烯醯氧基-丙酸四虱槺酯、3-(曱基）丙烯醯氧基四虱呋喃_2~酮等含有四氫天喃骨架的不飽和化合物； 2-曱基-5-(3-呋喃基）-1-办铋1加 , 戍烯-3-_、（曱基）丙烯酸糠 Θ曰、1-呋喃-2-丁基-3-烯-2-蜩、彳& Α Λ ,^ L呋喃·2-丁基_3-甲氧基 •烯_2-酮、6-(2-呋喃基）-2-甲其q ， τ|-1-己烯_3 -酮、6 -呋喃-2- =己小稀·3_酮、丙稀酸2_。夫喃·2_基小甲基·乙基醋、 -吱喃基）·6_曱基-^3.酮等含有吱喃骨架的不飽和化合物；甲基丙烯酸（四氫口比喃_2_基）甲醋、2,6_二甲基冬（四氣比喃-2 -基氧）_辛-1-烯-3_酮、2甲其系1 甘』甲基丙烯酸四氫吡喃-2- ^加W四氫终2-氧）_ 丁基领_2_酮等含有四氣。比 @月木的不飽和化合物； 4-(1，4_二氧雜_5_側氧_6•庚烯）_6曱基_2·吡喃、 _U，5-二氧雜_6_側氧_7_辛烯）_6甲基_2•吡喃等含有吡喃月架的不飽和化合物。作為具有羥基的（曱基）丙烯酸酯，丙稀酸2,基乙醋、(甲基)丙…經基丙::舉((曱甲；丙埽酸3-經基丙醋、（曱基）丙烯酸2,3_二經基丙醋。作為（甲基）丙烯酸芳基醋，可以列舉例如（曱基酸苯賴、（曱基）丙烯酸苄酯等。 t作為不飽和二羧酸二酯，可以列舉例如馬來酸二乙 S曰、富馬酸二乙酯、衣康酸二乙酯等。 -16- 201207558 作為馬來醯亞胺化合物，可以列舉例如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、n-(4-經基苯基）馬來醯亞胺、N-(4-羥基苄基）馬來醯亞胺、N-琥拍醯亞胺基-3 -馬來醯亞胺苯甲酸酯、N_琥珀醯亞胺基 -4-馬來醒亞胺丁酸酯、N_琥珀醯亞胺基-6_馬來醯亞胺己酸醋、N-琥轴醯亞胺基_3-馬來醯亞胺丙酸酯、n-(9-吖啶基）馬來醯亞胺等。在[A]共聚物中，作為化合物（iii)的含有率，較佳為 10質量％〜70質量％ ’更佳為15質量％〜65質量％。藉由使化合物（iii)的共聚比例處於1〇質量％〜7〇質量％，共聚物的分子量容易控制’可以得到顯影性、敏感度、黏合性等以更尚水準達到最佳化的感放射線性樹脂組成物。 < [A]共聚物的合成方法> [A ]共聚物可以藉由例如在溶劑中使用自由基聚合引發劑使化合物（i)、化合物（ii)及必要時使用的化合物 (iii)進行聚合來合成。作為用於製造[A]共聚物的聚合反應中使用的溶劑，可以列舉例如醇類、醚類、乙二醇醚、乙二醇烧基醚醋酸酯、一乙二醇烷基醚、丙二醇單烷基醚、丙二醇單说基醚醋酸醋、丙二醇單烷基醚丙酸酯、芳香族煙類、酮類、其他酯類等。作為醇類’可以列舉例如甲醇、乙醇、苄臬醇、2_ 苯基乙基醇、3-苯基-1-丙醇等。作爲醚類，可以列舉例如環狀醚、二醇趟、乙二醇烷基醚醋酸酯、二乙二醇烷基醚、丙二醇單烷基醚、丙二醇單烷基醚醋酸酯、丙二醇單烷基醚丙酸酯等。 201207558 作為環狀醚，可以列舉例如四氫呋喃等。作為乙二醇醚，可以列舉例如乙二醇單曱基醚、乙二醇單乙基醚等。作為乙二醇烷基醚醋酸酯，可以列舉例如曱基賽璐蘇醋酸酯、乙基賽璐蘇醋酸酯、乙二醇單丁基醚醋酸酯、乙二醇單乙基醚醋酸酯等。作為二乙二醇烷基醚，可以列舉例如二乙二醇單曱基醚、二乙二醇單乙基醚、二乙二醇二曱基醚、二乙二醇二乙基醚、二乙二醇乙基曱基醚等。作為丙二醇單烷基醚，可以列舉例如丙二醇單曱基醚、丙二醇單乙基醚、丙二醇單丙基醚、丙二醇單丁基醚等。作為丙二醇單烷基醚醋酸酯，可以列舉例如丙二醇單甲基醚醋酸酯、丙二醇單乙基醚醋酸酯、丙二醇單丙基醚醋酸酯、丙二醇單丁基醚醋酸酯等。作為丙二醇單烷基醚丙酸酯，可以列舉例如丙二醇單曱基醚丙酸酯、丙二醇單乙基醚丙酸酯、丙二醇單丙基醚丙酸酯、丙二醇單丁基醚丙酸酯等。作為芳香族烴類，可以列舉例如曱苯、二曱苯等。作為酮類，可以列舉例如甲基乙基酮、環己酮、4-羥基-4-曱基-2-戊酮等。作為其他酯類，可以列舉例如醋酸曱酯、醋酸乙酯、醋酸丙酯、醋酸丁酯、2-羥基丙酸乙酯、2-羥基-2-曱基丙酸曱酯、2-羥基-2-曱基丙酸乙酯、羥基醋酸曱酯、羥基醋酸乙酯、羥基醋酸丁酯、乳酸曱酯、乳酸乙酯、乳 -18- 201207558 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 -曱基丁烷酸曱酯、甲氧基醋酸曱酯、曱氧基醋酸乙酯、甲氧基醋酸丙酯、曱氧基醋酸丁酯、乙氧基醋酸甲酯、乙氧基醋酸乙酯、乙氧基醋酸丙酯、乙氧基醋酸丁酯、丙氧基醋酸甲酯、丙氧基醋酸乙酯、丙氧基醋酸丙酯、丙氧基醋酸丁酯、丁氧基醋酸甲酯、丁氧基醋酸乙酯、丁氧基醋酸丙酯、丁氧基醋酸丁酯、2 -甲氧基丙酸曱酯、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 -甲氧基丙酸甲酯、3 -曱氧基丙酸乙酯、3 -曱氧基丙酸丙酯、 3 -甲氧基丙酸丁酯、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 -丁氧基丙酸曱酯、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，可以列舉例如2,2’-偶氮二異丁腈、2,2’-偶氮雙（2,4-二甲基戊腈）、2,2’-偶氮雙 (4-甲氧基-2,4-二曱基戊腈）、4,4’-偶氮雙（4-氰基戊酸）、二曱基-2,2’-偶氮雙（2-曱基丙酸酯）、2,2’-偶氮雙（4-曱氧基-2,4-二曱基戊腈）等。 -19- 201207558 自由基聚合引發劑可以單獨使用一種或混合使用兩種以上。作為自由基聚合引發劑的使用量，相對於化合物（1)、化合物（Π)及化合物（iii)的合計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蓋的刀子量調節劑。作為分子量調節劑，可以列舉例如：鼠仿、硫醇、正十等硫醇類；專黃原精類四溴化碳等_化烴類；正己基硫醇、正辛基二貌基硫醇、三級十二烧基硫醇、酼基乙酸二曱基硫代黃原精、二異丙基二硫代黃原精 ;異松油烯、α·甲基苯乙烯二聚體等。作為分子量調節劑的使用量，相對於化合物（i)、化合物（11)及化合物（出）的合計100質量％，通常為0.1質里/〇 5 〇質$ 〇/〇，較佳為〇. 2質量％〜16質量％，更佳為〇. 4 資里％〜8質量。/〇。作為聚合溫度，通常為（TC〜15(TC，較佳為50 C〜12〇。〇。作為聚合時間，通常為1〇分鐘〜2〇小時’較佳為30分鐘〜6小時。作為[A]共聚物的聚苯乙烯換算重量平均分子量 (Mw)’較佳為2χ1〇3〜ΐχΐ〇5,更佳為5心3〜“Μ。藉由使[Α]'聚物的Mw處於2χΐ〇3以上，在感放射線性樹脂、：成物得到足夠的顯影裕度的同時可以防止所形成塗膜的膜殘留率(圖案狀薄膜適當殘留的比率)過低，而且可使得到的絕緣膜保持良好的圖案形狀及财熱性等。另方面藉由使[Α]共聚物的Mw處於1 χ 1 〇5以下，可以保持高度的感放射線性，得到良好的圖案形狀。另外， -20- 201207558 作為[A]共聚物的分子量分布（MW/Mn)，較佳為5.0以下’更佳為3.0以下。藉由使[A]共聚物的Mw/Mn為$ 〇以下’可以使得到的絕緣膜保持良好的圖案形狀。另外，包含具有如上所述較佳為範圍的Mw及Mw/Mn的[A]共聚物的感放射線性樹脂組成物，具有高度的顯影性，因此在顯影步驟中，不會產生顯影殘留，可以容易地形成規定的圖案形狀。共聚物的重量平均分子量（Mw)是基於下述裝置及條件，藉由凝膠滲透層析（GPC)測定的。裝置.GPC-101(昭和電工公司）柱：連接 GPC-KF-801、GPC-KF-802、GPC-KF-803 及 GPC-KF-804 流動相：四氫咬喃 < [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[B]聚合性化合物，如果是具有乙烯性不飽和鍵的聚合性化合物’就沒有特別的限制，可以列舉例如ω -羧基聚己内酯單（曱基）丙烯酸酯、乙二醇（甲基）丙烯酸酯、1，6 -己二醇二（甲基）丙烯酸酯、ι，9-壬二醇二（甲基）丙烯酸酯、四乙二醇二（曱基）丙烯酸酯、聚乙二醇二 (甲基）丙烯酸酯、聚丙二醇二（甲基）丙烯酸酯、二苯氧基乙醇第二（曱基）丙烯酸酯、二羥曱基三環癸烷二（曱基）兩烯酸酯、曱基丙烯酸2 -羥基_3-(曱基）丙烯醯氧丙酯、 2-(2’-乙烯氧基乙氧基）乙基（甲基）丙烯酸酯、三羥甲基丙燒三（甲基）丙稀酸酯、新戊四醇三（甲基）丙烯酸酯、新戊 -21 - 201207558 四醇四（甲基）丙稀酸酯、二新戊四醇五（曱基）丙稀酸酯、二新戊四醇六（甲基）丙烯酸酯、三（2 _(曱基）丙烯醯氧乙基）填酸酯、環氧乙烷改性二新戊四醇六丙烯酸酯、琥珀酸改性新戊四醇三丙烯酸酯等，另外還可列舉使具有直鏈伸烷基及脂環式構造’且具有2個以上異氰酸酯基的化合物和分子内具有1個以上羥基，且具有3〜5個（甲基）丙烯酿氧基的化合物反應得到的胺基甲酸酯（曱基）丙烯酸酯化合物等。作為上述[B ]聚合性化合物的市售製品，可以列舉例如(f-based acryloxyethyl) oxa iTO soil J 虱% butane, 3 (C-201207558 olefinic fluorenyl) oxequid oxetane, D-Xing, 3-(acrylic acid oxy) Yin milk base, base) -3 - ethyl 3 - (propylene oxyethyl) oxetanyl oxetane, ethyl oxetane, 2 · B /, _ (acrylic hydrazine Oxyethyl hydrazine, 7, ternalyl (acrylic acid oxy? I, preparation) 凡 (f-propyl ethoxylate T-based) oxy-protonate Oxetane calcined divalent, 2-, yl-2-((indolyloxy) oxetane, yinyiyi 2 soil·2-(Yinji propylene oxirane, A Acrylic acid; (acrylic ethoxylated oxime) ethyl ester, methacrylic acid 2_(2 /yloxetanyl)) 2-(methylpropenyloxy oxetanyl) Ethyl vinegar, dilute oxime ethyl)·”oxyxylene:; butyl, hetero 2..., hydrazine methyl propoxy butyl ketone, 2 _methyl·2 _ (acrylic: base = base) 3-Methyl propyl decyloxymethyl group: oxax% butyl sulphide 'cyclobutanyl group)) ethyl acetonate, methyl acrylate acid 2 _ ((dimethyl oxaacetate, 2 · _ 杂环杂环 ) ) ) ) ) ) ) ) ) 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 在在在在在在在在在在Glycidyl methacrylate, methyl propyl sulfonate, methacryloxymethyloxy) oxetane, propylene: oxybutyl, 3-(propylidene succinyl) Baked, 2-(mercapto-propyl oxymethyl) oxydiester & D:: cured film and separator, etc. on the substrate::::::: The door is heat-resistant 1± and the display is improved The F of the component is therefore preferably 201207558. For the [A] copolymer, the compound (Η) may be used alone or in combination of two m. In the [A] copolymer, the compound (1)) contains: The car is preferably 10% by mass to mass%, more preferably 15% by mass to 65% by volume. By using the compound (ii) in a content ratio of 10% by mass to 7% by mass, the molecular weight of the copolymer can be easily controlled, and a radiation-sensitive resin composition which is optimized to a higher level such as developability and sensitivity can be obtained. 0 As the compound (iii), an alkyl (meth)acrylate, a (fluorenyl)-acrylate alicyclic vinegar, an unsaturated five-membered heterocyclic ring containing an oxygen atom, and a six-membered heterocyclic (meth)acrylic acid vinegar may be mentioned. , (hydroxy) acrylate with hydroxyl group, aryl (mercapto) acrylate, unsaturated didecanoic acid diester, maleimide compound, alkyl (meth) acrylate, styrene, α _methylstyrene, 1,3-butadiene. Examples of the (mercapto)acrylic acid alkyl ester include methyl mercapto acrylate, ethyl methacrylate, n-butyl methacrylate, butyl methacrylate, and tertiary butyl methacrylate. Ethyl acrylate, ethyl acrylate, n-butyl acrylate, secondary butyl acrylate, tertiary butyl acrylate, and the like. Examples of the (fluorenyl) acrylate cyclic alkyl ester include cyclopentyl methacrylate, dicyclopentyl decyl acrylate, cyclohexyl methacrylate, and 2-methylcyclohexane methacrylate. Ester, methacrylic acid tricyclic bisindolyl, methyl methic acid 2- hydrazine pentyl methacrylate, propyl isopropyl acrylate, cyclopentyl acrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclodicyclopentyl acrylate, 2-dicyclopentyloxyethyl acrylate, isodecyl acrylate, and the like. -15- 201207558 As an unsaturated atom of oxygen atom, she is a member of this class and a six-membered heterocyclic methylpropionate. For example, (fluorenyl) tetrahydrofurfuryl acrylate, △ An unsaturated compound containing tetrahydronaphthyl skeleton, such as tetramethyl methacrylate, tetradecyl propionate, 3-(indenyl) propylene oxime tetrahydrofuran-2 ketone; 2-indolyl-5- (3-furyl)-1-indole 1 addition, terpene-3-_, (indenyl) hydrazide, 1-furan-2-butyl-3-ene-2-indole, hydrazine & Α Λ , ^ L furan · 2-butyl 3-methoxy-1-en-2-one, 6-(2-furyl)-2-methylq, τ|-1-hexene-3-enone , 6 - furan-2- = hexamethylene ketone, acrylic acid 2 _. Unsaturated compound containing a ruthenium skeleton such as fumon·2_yl-small methyl ethyl acetoacetate, -furanyl group, 6-fluorenyl-(3) ketone, etc.; methacrylic acid (tetrahydrogen pentyl bromide) _ base) methyl vinegar, 2,6-dimethyl winter (four gas pyran-2-yloxy) octyl-1-ene-3 ketone, 2 methyl ketone 1 gan 』 tetrahydropyran methacrylate -2- ^ plus W tetrahydrogen terminal 2-oxo) butyl butyl 2-ketone and the like contain four gases. Unsaturated compound than @月木; 4-(1,4_dioxa_5_side oxygen_6•heptene)_6曱yl_2·pyran, _U,5-dioxene_6_ side An unsaturated compound containing a pyranol frame such as oxygen-7-octene)-6 methyl-2-pyran. As a (fluorenyl) acrylate having a hydroxyl group, acrylic acid 2, ethyl acetonate, (meth) propyl ... by propyl group:: (( armor; propionate 3- propyl acetonate, 2. Acrylic acid 2,3_di-propyl propyl vinegar. Examples of the (meth)acrylic aryl vinegar include (benzyl phthalate, benzyl (meth) acrylate, etc. t as an unsaturated dicarboxylic acid diester For example, diethyl sulfonium maleate, diethyl fumarate, diethyl itaconate, etc. may be mentioned. -16-201207558 As the maleimide compound, for example, N-phenyl mala Amine, N-cyclohexylmaleimide, N-membered maleimide, n-(4-phenylphenyl)maleimide, N-(4-hydroxybenzyl)malanium Imine, N-sodium bromide, imino-3, maleimide benzoate, N-succinimide-4-maleimide butyrate, N-succinimide -6_Malayimide caproic acid vinegar, N-succinimide imino group _3-maleimide propionate, n-(9-acridinyl)maleimide, etc. In the copolymer, the content of the compound (iii) is preferably 10% by mass to 70% by mass, and more preferably 15% by mass. % to 65% by mass. By making the copolymerization ratio of the compound (iii) at 1% by mass to 7% by mass, the molecular weight of the copolymer can be easily controlled to obtain developability, sensitivity, adhesion, etc., to a higher level. Optimized radiation sensitive resin composition. [A] Synthesis method of copolymer [A] copolymer The compound (i), compound (ii) can be obtained by, for example, using a radical polymerization initiator in a solvent. And the compound (iii) used as needed to carry out polymerization and synthesis. The solvent used for the polymerization reaction for producing the [A] copolymer may, for example, be an alcohol, an ether, a glycol ether or an ethylene glycol. Ethyl ether acetate, monoethylene glycol alkyl ether, propylene glycol monoalkyl ether, propylene glycol monoethyl ether acetate, propylene glycol monoalkyl ether propionate, aromatic tobacco, ketones, other esters, etc. Examples of the alcohols include methanol, ethanol, benzamethylene alcohol, 2-phenylethyl alcohol, and 3-phenyl-1-propanol. Examples of the ethers include cyclic ethers, glycol oximes, and ethylene glycols. Alkyl ether acetate, diethylene glycol alkyl ether, propylene glycol Monoalkyl ether, propylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether propionate, etc. 201207558 The cyclic ether may, for example, be tetrahydrofuran. Examples of the glycol ether include ethylene glycol monothiol. Ether, ethylene glycol monoethyl ether, etc. Examples of the ethylene glycol alkyl ether acetate include decyl cyproterone acetate, ethyl cyproterone acetate, and ethylene glycol monobutyl ether acetate. Ethylene glycol monoethyl ether acetate, etc. Examples of the diethylene glycol alkyl ether include diethylene glycol monodecyl ether, diethylene glycol monoethyl ether, and diethylene glycol didecyl ether. Diethylene glycol diethyl ether, diethylene glycol ethyl decyl ether, etc. Examples of the propylene glycol monoalkyl ether include propylene glycol monodecyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol single. Butyl ether and the like. Examples of the propylene glycol monoalkyl ether acetate include propylene glycol monomethyl 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 propionate include propylene glycol monodecyl 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 and quinone. Examples of the ketones include methyl ethyl ketone, cyclohexanone, and 4-hydroxy-4-mercapto-2-pentanone. Examples of the other esters include decyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, decyl 2-hydroxy-2-mercaptopropionate, and 2-hydroxy-2. - mercaptopropionate, hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, decyl lactate, ethyl lactate, milk-18-201207558 propyl acrylate, butyl lactate, 3-hydroxypropionic acid Ester, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, decyl 2-hydroxy-3-mercaptobutanoate, decyl methoxyacetate, decyloxy Ethyl acetate, propyl methoxyacetate, butyl oxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, propoxyacetic acid Methyl ester, ethyl propoxyacetate, propyl propoxyacetate, butyl propyl acetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butoxyacetate Ester, decyl 2-methoxypropionate, ethyl 2-methoxyoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, bismuth 2-ethoxypropionate Ester, 2-ethoxyl Ethyl acetate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, decyl 2-butoxypropionate, ethyl 2-butoxypropionate, 2-butoxypropane Butyl acrylate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxyoxypropionate, propyl 3-methoxypropionate, 3-methoxypropane Butyl acrylate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, 3-propoxypropane Methyl ester, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, decyl 3-butoxypropionate, 3-butoxypropane Ethyl acetate, propyl 3-butoxypropionate, butyl 3-butoxypropionate, and the like. Examples of the radical polymerization initiator include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azo. Bis(4-methoxy-2,4-dimercaptophthalonitrile), 4,4'-azobis(4-cyanovaleric acid), dimercapto-2,2'-azobis (2 - mercaptopropionate), 2,2'-azobis(4-decyloxy-2,4-dimercaptophthalonitrile), and the like. -19- 201207558 The radical polymerization initiator may be used alone or in combination of two or more. The amount of use of the radical polymerization initiator is usually preferably from 0.1% by mass to 50% by mass, more preferably from 0.1% by mass to 50% by mass based on 100% by mass of the total of the compound (1), the compound (Π) and the compound (iii). Mass%~20% by mass. Further, in the above polymerization reaction, a knife amount adjusting agent for adjusting the molecular cap can be used. Examples of the molecular weight modifier include, for example, a morphine, a thiol, a thiol, etc.; a phthalocyanine such as tetramethyl bromide; a hexyl thiol, an n-octyl dimethyl thiol; , tertiary didecyl mercaptan, thioglycolic acid dimercapto thioxanthogen, diisopropyl dithioxanthine; terpinolene, α·methyl styrene dimer, and the like. The amount of the molecular weight modifier to be used is usually 0.1% by mass/〇5 〇 $ 〇/〇, preferably 〇, based on 100% by mass of the total of the compound (i), the compound (11) and the compound (out). 2% by mass to 16% by mass, more preferably 〇. 4 cc%~8 mass. /〇. The polymerization temperature is usually (TC 15 15 (TC, preferably 50 C to 12 Torr. 〇. As the polymerization time, usually 1 Torr to 2 Torr hours is preferably 30 minutes to 6 hours). The polystyrene-equivalent weight average molecular weight (Mw) of the copolymer is preferably 2χ1〇3~ΐχΐ〇5, more preferably 5 cores 3~“Μ. By making the Mw of the [Α]' polymer at 2χΐ〇 3 or more, in the radiation sensitive resin, the product can obtain a sufficient development margin, and the film residual ratio of the formed coating film (the ratio of the pattern film remaining properly) can be prevented from being too low, and the obtained insulating film can be maintained. Good pattern shape, heat retention, etc. In addition, by making the Mw of the [Α] copolymer at 1 χ 1 〇 5 or less, it is possible to maintain a high degree of sensibility of radiation and obtain a good pattern shape. In addition, -20-201207558 [A] The molecular weight distribution (MW/Mn) of the copolymer is preferably 5.0 or less, and more preferably 3.0 or less. The insulating film can be maintained by making the Mw/Mn of the [A] copolymer less than or equal to '. Good pattern shape. In addition, [M] having Mw and Mw/Mn having a preferred range as described above The radiation-sensitive resin composition of the polymer has high developability, so that development residue does not occur in the development step, and a predetermined pattern shape can be easily formed. The weight average molecular weight (Mw) of the copolymer is based on the following The device and conditions were determined by gel permeation chromatography (GPC). Device. GPC-101 (Showa Denko Co., Ltd.) Column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC- KF-804 Mobile phase: tetrahydroanthracene <[B] polymerizable compound> [B] The polymerizable compound is a polymerizable compound having an ethylenically unsaturated bond. As the [B] polymerizable compound, if it is ethylenic The polymerizable compound having an unsaturated bond is not particularly limited, and examples thereof include ω-carboxypolycaprolactone mono(indenyl)acrylate, ethylene glycol (meth)acrylate, and 1,6-hexanediol. (Meth) acrylate, iota, 9-nonanediol di(meth) acrylate, tetraethylene glycol di(meth) acrylate, polyethylene glycol di(meth) acrylate, polypropylene glycol bis ( Methyl) acrylate, diphenoxyethanol second (曱) Acrylate, dihydroxyindenyl tricyclodecane bis(indenyl) adienoate, 2-hydroxy-3-(indenyl)propenyl isopropyl acrylate, 2-(2'-ethyleneoxy) Ethoxy)ethyl (meth) acrylate, trimethylolpropane tris(methyl) acrylate, neopentyl alcohol tri(meth) acrylate, neopenta-21 - 201207558 tetraol (Methyl) acrylate, dipentaerythritol penta(indenyl) acrylate, dipentaerythritol hexa(meth) acrylate, tris(2 _(fluorenyl) propylene oxyethyl Filler, ethylene oxide modified dipentaerythritol hexaacrylate, succinic acid modified neopentyl alcohol triacrylate, etc., and also have a linear alkyl group and an alicyclic structure. a compound having two or more isocyanate groups and a urethane (mercapto) acrylate compound obtained by reacting a compound having one or more hydroxyl groups in the molecule and having 3 to 5 (meth)acryloxy groups. . As a commercially available product of the above [B] polymerizable compound, for example, for example,

Aronix M-400、Aronix M-402、Aronix M-405、Aronix M-450、Aronix M-1310、Aronix M-1600、Aronix M-1960、 Aronix M-7100、Aronix M-8030、Aronix M-8060、Aronix M-8100、Aronix M-8530、Aronix M-8560、Aronix M-9050、Aronix TO- 1450、Aronix TO- 1 3 82、Aronix TO-756(以上，東亞合成公司）； KAYARAD DPHA、KAYARAD DPCA-20、KAYARAD DPCA-30、KAYARAD DPCA-60、KAYARAD DPCA-120、 KAYARAD MAX-3 5 10(以上，日本化藥公司）；Aronix M-400, Aronix M-402, Aronix M-405, Aronix M-450, Aronix M-1310, Aronix M-1600, Aronix M-1960, Aronix M-7100, Aronix M-8030, Aronix M-8060, Aronix M-8100, Aronix M-8530, Aronix M-8560, Aronix M-9050, Aronix TO-1450, Aronix TO- 1 3 82, Aronix TO-756 (above, East Asia Synthesis); KAYARAD DPHA, KAYARAD DPCA- 20. KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120, KAYARAD MAX-3 5 10 (above, Nippon Kayaku Co., Ltd.);

Viscoat 295、Viscoat 300、Viscoat 360、Viscoat GPT、Viscoat 3PA、Viscoat 400(以上，大阪有機化學工業公司）作為胺基甲酸酯丙烯酸酯系化合物的New Frontier R-1150(第一工業製藥公司）； KAYARAD DPHA-40H、UX-5000(以上，日本化藥公司）； -22- 201207558 UN-9000H(根上工業公司）、Viscoat 295, Viscoat 300, Viscoat 360, Viscoat GPT, Viscoat 3PA, Viscoat 400 (above, Osaka Organic Chemical Industry Co., Ltd.) New Frontier R-1150 (First Industrial Pharmaceutical Company) as a urethane acrylate compound; KAYARAD DPHA-40H, UX-5000 (above, Nippon Kayaku Co., Ltd.); -22- 201207558 UN-9000H (Kyosho Industrial Co., Ltd.),

Aronix M-5300、Aronix M-5600、Aronix M-5700、 M-210、Aronix M-220、Aronix M-240、Aronix M-270、 Aronix M-6200、Aronix M-305、Aronix M-309、Aronix M-3 10、Aronix M-315(以上，東亞合成公司）； KAYARAD HDDA、KAYARAD HX-220、KAYARAD HX-620、KAYARAD R-526、KAYARAD R-167、KAYARAD R-604、KAYARAD R-684、KAYARAD R-551、KAYARAD R-712、UX-2201、UX-2301、UX-3204、UX-330 1、 UX-4101、UX-6101、UX-7101、UX-8101、UX-0937 ' MU-21 00、MU-400 1(以上，日本化藥公司）；Aronix M-5300, Aronix M-5600, Aronix M-5700, M-210, Aronix M-220, Aronix M-240, Aronix M-270, Aronix M-6200, Aronix M-305, Aronix M-309, Aronix M-3 10, Aronix M-315 (above, East Asia Synthetic Company); KAYARAD HDDA, KAYARAD HX-220, KAYARAD HX-620, KAYARAD R-526, KAYARAD R-167, KAYARAD R-604, KAYARAD R-684, KAYARAD R-551, KAYARAD R-712, UX-2201, UX-2301, UX-3204, UX-330 1, UX-4101, UX-6101, UX-7101, UX-8101, UX-0937 'MU-21 00, MU-400 1 (above, Nippon Chemical Co., Ltd.);

Art resinUN-9000PEP、Art resinUN-9200A ' Art resinUN-7600、Art resinUN-333、Art resinUN-1003、Art resinUN- 1 255 、 Art resinUN-6060PTM 、 Art resinUN-6060P(以上，根上工業公司）； SH-500B Viscoat 260 、Viscoat 312、Viscoat 33 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使用一種或混合使用兩種以上。作為該感放射線性樹脂組成物中[B]聚合性化合物的含量’相對於[A]共聚物1〇〇質量份，較佳為20質量份〜200質量份’更佳為40質量份〜160質量份。藉由使[B]聚合性化合物的含量處於上述特定範圍，該感放射線性樹脂組成物的黏合性優異，即使在低曝光量下也可以得到具有足夠硬度的層間絕緣膜、保護膜及隔離物等硬化膜。 -23- 201207558 < [c]感放射線性聚合引發劑〉該感放射線性樹脂組成物中含有的[c]感放射線性聚合引發劑是對放射線敏感’能夠引發[B]聚合性化合物的聚合的產生活性種的成分。[c]感放射線性聚合引發劑較佳為由苯乙酮化合物及〇 -酿基肪化合物構成的群組中選出的至少一種物質。藉由使用上述特定化合物作為[c] 感放射線性聚合引發劑，即使在低曝光量情j:兄下也可以提高耐熱性等作為硬化膜的所需特性。作為苯乙酮化合物，可以列舉例如α-胺基綱化人物、α-羥基酮化合物等。作為α-胺基酮化合物，可以列舉例如2-苄基_ 二· 一甲基胺基-1_(4-咪啉基苯基）_ 丁-1_酮、2-二曱基胺基_2 (4 曱基苄基）-1-(4-咪啉-4-基-苯基）_丁 -1-酮、2-曱基甲硫基笨基）-2 -咪淋基丙·ι_嗣等。作為α-羥基酮化合物，可以列舉例如丨_笨基_2__夷 -2-曱基丙-1-酮、1-(4-異丙基苯基）_2_羥基·2-曱基丙< 酮、4-(2-羥基乙氧基）苯基_(2·羥基·2_丙基）酮、丨·羥基環己基苯基酮等。在這些化合物中，較佳為α-胺基酮化合物，更佳為 2-卞基·2-二曱基胺基- Κ(4_味啉基苯基）_丁 j酮、2二甲基胺基-2-(4-甲基苄基）_κ(4_味啉_4_基-苯基卜丁 _丨_酮、 2_甲基-1-(4-曱硫基苯基），2_咪啉基丙_卜酮。作為0-醯基肟化合物，可以列舉例如 Λ r . 5 T 一 _ • 苯硫基）-2-(〇-笨甲醯肟）]、乙酵-l-[9-乙基-6 _ 甲基笨甲醯基）-9Η-咔唑_3_基]_1(〇乙醯肟）、“[9乙美 -24- 201207558 -6-苯甲酿基-9H -味唾-3 -基]-辛烧-l-_將-〇-醋酸g旨、 1-[9-乙基-6-(2-甲基苯曱醯基）-91^-咔唑-3-基]-乙烷-1-酮肟-0-苯曱酸酯、1-[9-正丁基-6-(2-乙基苯曱醯基）-9H-咔唑-3-基]-乙烷-l-酮肟-0-苯曱酸酯、乙醇_l_[9-乙基 -6-(2-曱基-4-四氫呋喃基苯甲醯基）_9Η·咔唑-3-基]-1-(0 -乙醯躬·）、乙醇-1-[9 -乙基-6-(2 -甲基-4 -四氫0比喃基苯甲醯基）-9H-0卡嗤-3-基]-1-(0 -乙酿肪）、乙醇- l- [9-乙基-6-(2-曱基-5 -四氫0夫喊基苯甲酿基）-9H -叶·唾-3-基]-1-(0-乙醯肟）、乙醇- l-[9-乙基-6·{2-甲基-4-(2,2-二曱基-l，3-二氧戊烷基）甲氧基苯甲酿基}_9H-咔唑-3-基]-l-(0-乙醯肟）等。在這些化合物中，較佳為1，2 -辛二酮-1 - [ 4 -(苯硫基）-2-(〇-苯甲醯肟）]、乙醇_1_[9-乙基-6-(2-甲基苯甲醯基）-9H-咔唑-3-基]-l-(〇-乙醯肟）、乙醇-bp-乙基-6-(2-甲基-4-四氫呋喃基曱氧基苯甲醯基）_9H_咔唑-3_ 基]-1-(0-乙醯肟）、乙醇_1_[9 -乙基-6- { 2-甲基-4-(2,2- 二甲基-l，3-二氧戊烷基）甲氧基苯甲醯基}_9H-咔唑-3- 基l·l-(0-乙醯肟）。 [C]感放射線性聚合引發劑可以單獨使用一種或混合使用兩種以上。作為該感放射線性樹脂組成物中的[c] 感放射線性聚合引發劑的含量，相對於[A]共聚物丨〇〇質置份’較佳為1質量份〜40質量份，更佳為5質量份〜3〇質里份。藉由使[C]感放射線性聚合引發劑的含量處於上述特定範圍内，即使在低曝光量的情況下，該感放射線性樹脂組成物也可以形成具有高硬度及黏合性的層間絕緣膜、保護膜及隔離物等硬化膜。 -25- 201207558 < [D]化合物> 作為[D]化合物，如果是具有經基就沒有特別的限制。作A 一竣土的化合物，別作為[D]化合物，較佳為胺化合物的化合物，從、奋杏仏π A”么、 b多勺匕合[Ε] 面考慮，較佳為由上辻犬二： < 述的曰曰氣化合物方成的群組中選出至少-種的化合物。物構上述式(1)中’ χ為單鍵、亞甲基或碳的伸院基〜各自獨立地為氣原子、碳原子數為二6 的烧基、鹵素原子、4 1& 1 2 有取代基的苯基原子數為1〜12的燒氧基…具作為上述χ表示的碳原子數為2〜6的伸列舉例如伸乙基、伸丙基等。作為上述R1〜R ^ 的烧基，可以列舉例如曱基、二示丙基、丁基等。作為上述R18 土、 1〜12的烧氧基，可以列兴…田R表不的碳原子數為等。了以列舉例如甲氧基、乙氧基、丙氣基上述式⑴表示的化合物較佳為上化合物。藉由將上述式⑴表示不的表示的化合物，可以進°物作為上述式（1-1) 進低溫硬化。纟一存穩定性，也可以促作為上述式U-D表示的化合 1，1，2,2_肆（4.經基||化11以列舉例如笨基)乙烷、i山2,2•肆(3,5 、，肆(3_甲基-4,基 1 ! 2 2 Λ n « 甲基·4-羥基苯基）乙烷、，，2,2-肆（3-亂_4，基苯基）乙燒' u 2 衫 •4-羥基苯基）乙烷、i i 2 ，，’肆（3,5-一虱以，2,2·肆(3，-4,基苯基)乙烧、 -26- 201207558 U，2,2-肆(3,5_二漠-4_羥基笨基)乙烷、1，1，2,2-肆(3-三級丁基-4-經基苯基)乙烷、Art resinUN-9000PEP, Art resinUN-9200A 'Art resinUN-7600, Art resinUN-333, Art resinUN-1003, Art resinUN-1 255, Art resinUN-6060PTM, Art resinUN-6060P (above, Roots Industrial Co., Ltd.); SH- 500B Viscoat 260, Viscoat 312, Viscoat 33 5HP (above, Osaka Organic Chemical Industry Co., Ltd.), etc. [B] The polymerizable compound may be used alone or in combination of two or more. The content of the [B] polymerizable compound in the radiation-sensitive resin composition is preferably 20 parts by mass to 200 parts by mass with respect to 1 part by mass of the [A] copolymer, more preferably 40 parts by mass to 160 parts by mass. Parts by mass. When the content of the [B] polymerizable compound is in the above specific range, the radiation-sensitive resin composition is excellent in adhesion, and an interlayer insulating film, a protective film, and a separator having sufficient hardness can be obtained even at a low exposure amount. Such as hardened film. -23- 201207558 < [c] Radiation-Temperature Polymerization Initiator> The [c] radiation-sensitive polymerization initiator contained in the radiation-sensitive linear resin composition is radiation-sensitive' capable of initiating polymerization of [B] polymerizable compound The component that produces the active species. [c] Radiation-sensing polymerization initiator It is preferably at least one selected from the group consisting of an acetophenone compound and a ruthenium-based fat compound. By using the above specific compound as the [c] radiation-sensitive polymerization initiator, heat resistance and the like as a cured film can be improved even at a low exposure amount. The acetophenone compound may, for example, be an α-amino group-formed human or an α-hydroxyketone compound. The α-amino ketone compound may, for example, be 2-benzyl-di-monomethylamino-1-(4-morpholinylphenyl)-but-1-one or 2-didecylamino-2. (4-Mercaptobenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, 2-mercaptomethylthiophenyl]-2-imidylpropyl·ι_ Hey. Examples of the α-hydroxyketone compound include, for example, 丨_笨基_2__-2--2-ylpropan-1-one, 1-(4-isopropylphenyl)_2-hydroxy-2-indolyl-lt Ketone, 4-(2-hydroxyethoxy)phenyl-(2.hydroxy-2-indol)one, hydrazine-hydroxycyclohexyl phenyl ketone, and the like. Among these compounds, an α-amino ketone compound is preferred, and more preferred is 2-mercapto-2-didecylamino-indole (4-tyrosylphenyl)-butanone, 2-dimethyl group. Amino-2-(4-methylbenzyl)-kappa (4-tyrosine-4-yl-phenyl-butyrene-ketone, 2-methyl-1-(4-sulfonylphenyl), 2_ morpholinylpropanone. As the 0-fluorenyl hydrazine compound, for example, Λ r . 5 T a _ • phenylthio)-2-(anthracene-phenylidene)], ethyl yeast-l -[9-ethyl-6 _methyl benzylamino)-9Η-carbazole _3_yl]_1(〇乙醯肟), "[9乙美-24- 201207558 -6-benzamide -9H-flavored salino-3-yl]-octyl-l--p-indole-acetic acid g, 1-[9-ethyl-6-(2-methylbenzoinyl)-91^-咔Zyrid-3-yl]-ethane-1-one oxime-0-benzoate, 1-[9-n-butyl-6-(2-ethylbenzoinyl)-9H-carbazole-3 -yl]-ethane-l-ketooxime-0-benzoate, ethanol_l_[9-ethyl-6-(2-mercapto-4-tetrahydrofuranylbenzylidene)_9Η·carbazole- 3-yl]-1-(0-acetamidine·), ethanol-1-[9-ethyl-6-(2-methyl-4tetrahydro-2-pyridylbenzylidene)-9H- 0 card-3-yl]-1-(0-ethyl fat), ethanol-l- [9-ethyl-6-(2-mercapto-5-tetrahydro 0基基苯甲基基)-9H-叶·Sial-3-yl]-1-(0-acetamidine), ethanol-l-[9-ethyl-6·{2-methyl-4-( 2,2-Dimercapto-l,3-dioxolanyl)methoxybenzoyl}_9H-carbazol-3-yl]-l-(0-acetamidine), etc. In these compounds Preferably, 1,2-octanedione-1 -[4-(phenylthio)-2-(indolyl-benzamide)], ethanol_1_[9-ethyl-6-(2- Methylbenzylidene)-9H-carbazol-3-yl]-l-(〇-acetamidine), ethanol-bp-ethyl-6-(2-methyl-4-tetrahydrofuranyloxyl Benzyl hydrazino)_9H_carbazole-3_yl]-1-(0-acetamidine), ethanol_1_[9-ethyl-6- { 2-methyl-4-(2,2-dimethyl --l,3-dioxolanyl)methoxybenzylidenyl}_9H-carbazole-3-yl l·l-(0-acetamidine) [C] Radiation-sensitive polymerization initiator One type may be used alone or in combination of two or more. The content of the [c] radiation-sensitive polymerization initiator in the radiation-sensitive resin composition is preferably 1 in terms of the [A] copolymer tantalum portion. The mass fraction is preferably 40 parts by mass, more preferably 5 parts by mass to 3 parts by mass. By making the content of the [C] radiation-sensitive polymerization initiator in the above-mentioned special Within a range, even in low exposure amount, the radiation-sensitive resin composition may be formed to have a high hardness and adhesion of the inter-layer insulating film, a protective film and cured film separator, and the like. -25-201207558 < [D] Compound> As the [D] compound, there is no particular limitation if it has a mercapto group. As a compound of A-alumina, it is preferably a compound of [D], preferably an amine compound, from the side of 奋仏仏 A 、、、、 b b b b b b b b b b b b b b Canine 2: < The compound of the group of helium compounds described above is selected from at least one species. In the above formula (1), 'χ is a single bond, methylene or carbon. The ground is a gas atom, a carbon atom having a carbon number of 2, a halogen atom, a 4 1 & 1 2 substituted phenyl group having a phenyl group number of 1 to 12, and the number of carbon atoms represented by the above χ is Examples of the extension of 2 to 6 include an ethyl group and a propyl group. Examples of the group of the above R1 to R^ include a mercapto group, a dipropyl group, a butyl group, etc., as the above R18 soil, 1 to 12 The alkoxy group may be a compound of the formula (1), for example, a methoxy group, an ethoxy group or a propylene group, and the above compound is preferably an upper compound. The formula (1) represents a compound which is not represented, and can be subjected to low temperature hardening as the above formula (1-1). The compound represented by the above formula UD is 1,1,2,2_肆 (4. via the base ||11 to exemplify, for example, stupid) ethane, i-mount 2, 2 • 肆 (3, 5, 肆 (3) _Methyl-4, group 1 ! 2 2 Λ n « methyl 4-hydroxyphenyl) ethane, ,, 2,2-indole (3-chaos _4, phenyl) acetonitrile 'u 2 blouse • 4-hydroxyphenyl)ethane, ii 2 ,, '肆 (3,5-one, 2,2·肆(3,-4,ylphenyl)ethene, -26-201207558 U,2 , 2-肆(3,5_二漠-4_hydroxyphenyl)ethane, 1,1,2,2-indole (3-tert-butyl-4-phenylphenyl)ethane,

基苯基）乙烧、l，l，2 2-iti^ g I ’肆（3-鼠-4-羥基苯基）乙烷、^2,2- 肆(3,5_二氟_4,基苯基)乙烷、1，1，2,2-肆(3_甲氧基-4- 經基苯基）乙烧、认仏肆㈠义二甲氧基冬幾基苯基）乙烷、1’1,2,2肆(3-氯_5_曱基_4·羥基苯基)乙烷、以二厂肆（3 /臭5甲基-4-½基笨基）乙烧、m2·肆（3甲氧基 _5_甲基-4,基笨基)乙烧、^2，肆(3_三級丁基_5_甲基4红基苯基）乙貌、l1，2,2-肆（3·氯-5-漠-4-經基苯基）乙貌、M，2,2-肆（3_氯_5_苯基_4_經基笨基）乙烧、四Μ經基-3-苯基）苯基]乙烧、^从肆⑷經基苯基）丙烷1’1,3’3_肆(3_甲基_4_羥基笨基)丙烷、1，1，3,3-肆 (3,5-一曱基-4-沒基苯基）丙烷、肆氣·4經基苯基）丙烷1，1，3,3-肆（3,5_二氣_4_經基苯基）丙烧、肆（3备4·經基笨基）丙烧、肆（3,5-二漠-4-經基苯土）丙烧|，1，3,3-肆（3-苯基_4_經基笨基）丙烷、113,3_ 肆（3,5~二苯基基苯基）丙烧、1，1’3,3-肆（3_曱氧基-4· Μ基苯基、m3·肆（3,5_二曱氧基_4經基苯基）丙烷、1，1，_3,3-肆（3-三級丁基_4_經基苯基）丙烷、肆（，_ 、及丁基_4_备基苯基）丙院、1，1，4,4 -肆（4 -經基苯基）丁烷、1，1，4,4_肆（3_曱基_4_經基苯基）丁烷、Ι,Μ〆· 肆（3,5-二甲基-4-_其^其、丁 & 1 — 左基本基）丁烷、込1，4,心肆（3-氯-扣羥美本基）丁烷、U，4,4-肆（3,5_二氯_4_羥基苯基）丁土肆（34氧基_4_歸苯基）丁貌、】，Μ，=、二甲氧基I經基苯基）丁烧' 】山4,4_肆（m經基(苯^ -27- 201207558 丁烧、1，1，4,4-肆（3,5-二演-4-經基苯基）丁烷、肆 (3-三級丁基-4-經基苯基）丁烷、肆（3,5•二三級丁基-4-羥基苯基）丁烷等。在這些化合物中，在形成後述的晶籠化合物時，從該感放射線性樹脂、组成物纟室溫下的貯存穩定性更為優異，並且加熱時容易釋放出硬化促進劑方面考慮，較佳為1，1，2,2 -肆（4 -經基苯基）乙烧。作為上述式（2)表示的化合物，可以列舉例如5_石肖基間苯二甲酸、5-羥基間苯二甲酸' 5甲基間苯二甲酸： 5-曱氧基間苯二曱酸、4_硝基間苯二甲酸、4·羥基間苯二甲酸、4-曱基間苯二甲酸、4·甲氧基間苯二甲酸等。在這些化合物中，較佳為5_硝基間苯二甲酸、5經基二甲酸。 [D]化合物可以單獨使用一種或混合使用兩種以上。作為該感放射線性樹脂組成物中[D]化合物的含量，相對於[A]共聚物100質量份，較佳為〇」質量份〜1〇質量份’更佳為0.2質量份〜5 f量份，並且較佳為相對於後述的[E]胺化合物為1倍〜2倍左右。 < [E ]胺化合物〉作為[E]胺化合物，沒有特別的限制，但較佳為能夠包合在[D]化合物中的胺化合物，更佳為❹化合物或苯并味唾化合物。在這些化合物中，味唾化合物容易被包合在[D]化合物中，提高了該感放射線性樹脂組成物在室溫下的貯存穩定性。另外’味唾化合物與環氧基的反應性優異，因此促成了 20(rc以下的低溫硬化。 -28- 201207558 作為咪唑化合物，可以列舉例如下述式（3)表示的化合物等。Ethylphenyl)ethene, l,l,2 2-iti^ g I '肆(3-murox-4-hydroxyphenyl)ethane, ^2,2-肆(3,5_difluoro- 4, Ethylphenyl)ethane, 1,1,2,2-anthracene (3-methoxy-4-phenylphenyl)ethene, hydrazine (mono)dimethoxyoxybutyrylphenyl)ethane , 1'1,2,2肆(3-chloro-5-indolyl_4.hydroxyphenyl)ethane, bismuth (3/odor 5 methyl-4-1⁄2 base) M2·肆(3methoxy_5_methyl-4, phenyl group), Ethylene, ^2, 肆 (3_tert-butyl _5-methyl 4-erythrylphenyl), appearance, l1, 2,2-肆(3·Chloro-5-indol-4-pyridylphenyl) Ethyl, M,2,2-indole (3_chloro-5_phenyl_4_pyridyl) , tetrakisyl-3-phenyl)phenyl]ethene, from hydrazine (4) via phenyl) propane 1'1,3'3_肆(3_methyl_4_hydroxyphenyl)propane, 1,1,3,3-anthracene (3,5-monodecyl-4-diphenyl)propane, helium, 4-phenylphenyl)propane 1,1,3,3-anthracene (3,5 _二气_4_Phenylphenyl)propane, 肆(3 备4·经基笨基), 烧, 肆(3,5-二漠-4-base benzophenone)-propane burning|,1, 3,3-肆(3-phenyl_4_pyridyl)propane, 113,3_ 肆(3,5-diphenylphenyl)propene , 1,1'3,3-indole (3_decyloxy-4·nonylphenyl, m3·肆(3,5-dimethoxy-4-tetraphenyl)propane, 1,1, _3,3-肆(3-tert-butyl-4-yl-p-phenyl)propane, hydrazine (, _, and butyl _4_predylphenyl) propyl, 1,1,4,4 -肆(4-Phenylphenyl)butane, 1,1,4,4_肆(3_fluorenyl-4-ylphenyl)butane, hydrazine, hydrazine, hydrazine (3,5-dimethyl -4-_其^其,丁& 1 — left basic base) butane, 込1,4, palpitary (3-chloro-dehydroxyxybenyl) butane, U, 4,4-肆 (3 ,5_Dichloro_4_hydroxyphenyl)butadiene oxime (34 oxy_4_decylphenyl) butyl morphine,], hydrazine, =, dimethoxyl phenyl group) butyl burning ' 】 mountain 4,4_肆(m-based group (benzene ^ -27- 201207558 butyl, 1,1,4,4-anthracene (3,5-di--4-phenylphenyl)butane, hydrazine (3- Tertiary butyl-4-phenylphenyl)butane, anthracene (3,5•ditributyl-4-hydroxyphenyl)butane, etc. Among these compounds, in the formation of a cage compound described later From the radiation-sensitive resin and the composition, the storage stability at room temperature is more excellent, and the hardening promotion is easily released upon heating. In view of the above, it is preferably 1,1,2,2-indole (4-p-phenylene)-ethyl bromide. Examples of the compound represented by the above formula (2) include, for example, 5-stone-isophthalic acid, 5-hydroxyl group. Isophthalic acid '5-methyl isophthalic acid: 5-decyloxyisophthalic acid, 4-nitroisophthalic acid, 4·hydroxyisophthalic acid, 4-mercaptoisophthalic acid, 4. Methoxy isophthalic acid and the like. Among these compounds, 5-nitroisophthalic acid and 5-based dicarboxylic acid are preferred. The [D] compounds may be used alone or in combination of two or more. The content of the [D] compound in the radiation sensitive resin composition is preferably 〇" parts by mass to 1 part by mass", more preferably 0.2 parts by mass to 5 parts by mass based on 100 parts by mass of the [A] copolymer. It is preferably about 1 to 2 times the amount of the [E] amine compound to be described later. < [E] Amine compound> The [E] amine compound is not particularly limited, but is preferably an amine compound which can be contained in the [D] compound, more preferably an anthracene compound or a benzo-salt compound. Among these compounds, the salivary compound is easily incorporated into the [D] compound, and the storage stability of the radiation-sensitive resin composition at room temperature is improved. In addition, it is excellent in the reactivity of the taste compound and the epoxy group, and it is a low-temperature hardening of 20 or less. -28-201207558 The imidazole compound is, for example, a compound represented by the following formula (3).

上述式（3)’中，R10〜R13各自獨立地為氫原子、碳原子數為1〜6的烷基、萘基、蒽基、菲基、9-苐基、鹵素原子、碳原子數為1〜6的烷基、苯基或可以被鹵素原子取代的苯基。作為味坐化合物，可以列舉例如°米α坐、2 -曱基°米。坐、 2-乙基°米。坐、2 -異丙基。米α坐、2 -正丙基°米。坐、2 -十一烧基 -1Η-咪唑、2-十七烷基-1Η-咪唑、1，2-二甲基咪唑、2-乙基-4 -曱基咪唑、2-苯基-1Η-咪唑、4 -甲基-2-苯基-1Η-咪唑、2-苯基-4-甲基咪唑、1-苄基-2-曱基咪唑、1-氰基乙基-2-甲基咪唑、1-氰基乙基-2-乙基-4-曱基咪唑、1-氰基乙基-2-十一烷基咪唑、1-氰基乙基-2-苯基咪唑、1-氰基乙基-2-乙基-4-曱基咪唑鏽偏苯三酸鹽、1-氰基乙基-2-十一烷基咪唑鑌偏苯三酸鹽、1 -氰基乙基-2-笨基咪唑鑌偏苯三酸鹽、2,4-二胺基-6-[2’-曱基咪唑基-(1’）]-乙基-8-二11井、2,4-二胺基-6-(2’-十一烧基°米。圭基-)-乙基-8-二口井、2，4 - 一胺基-6-[2’ -乙基-4-°米。坐基-(1 ’）]-乙基-s -二畊、2,4-二胺基-6-[2’ -曱基咪唑基-(Γ)]-乙基-s-三啩異氰脲酸加成物、2-苯基咪唑異氰脲酸加成物、2-甲基咪唑異氰脲酸加成物、2-苯基-4,5-二羥基甲基咪唑、2-苯基 -4-甲基-5-羥基甲基咪唑、1-氰基乙基-2-苯基-4,5-雙（2- -29- 201207558 氰基乙氧基）曱基咪唑、咪唑鏽、1_苄基_2、一烷基_2-甲基-3-苄基氣化In the above formula (3)', R10 to R13 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a naphthyl group, an anthracenyl group, a phenanthryl group, a 9-fluorenyl group, a halogen atom, and a carbon number. An alkyl group of 1 to 6, a phenyl group or a phenyl group which may be substituted by a halogen atom. Examples of the taste-supplementing compound include, for example, a meter of a square sitting and a square of 2 - fluorene. Sit, 2-ethyl ° meter. Sitting, 2-isopropyl. Rice α sitting, 2-n-propyl ° meter. Sit, 2 -11-alkyl-l-imidazole, 2-heptadecyl-1Η-imidazole, 1,2-dimethylimidazole, 2-ethyl-4-mercaptoimidazole, 2-phenyl-1Η -imidazole, 4-methyl-2-phenyl-1-indole-imidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-mercaptoimidazole, 1-cyanoethyl-2-methyl Imidazole, 1-cyanoethyl-2-ethyl-4-mercaptoimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- Cyanoethyl-2-ethyl-4-mercaptoimidazole rust trimellitate, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl- 2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-mercaptoimidazolyl-(1')]-ethyl-8-di-11 well, 2,4- Diamino-6-(2'- eleven alkyl group. Kumiki-)-ethyl-8-two wells, 2,4-amino--6-[2'-ethyl-4- ° meters. Sodium-(1 ')]-ethyl-s-two-pill, 2,4-diamino-6-[2'-mercaptoimidazolyl-(indenyl)]-ethyl-s-tris-isocyano Urea acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-methylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-benzene 4-methyl-5-hydroxymethylimidazole, 1-cyanoethyl-2-phenyl-4,5-bis(2- -29-201207558 cyanoethoxy)nonyl imidazole, imidazole rust , 1-benzyl-2, monoalkyl-2-methyl-3-benzyl gasification

_ 來基咪0坐鹽酸踏、T 鑷偏苯三酸鹽等。 | U苄基-2-苯基咪唑在這些化合物φ 干’較佳為具有1柄 1〜6的取代基的咪個以上碳原子數為災化合物。這種畔Λ 定地包合，因此不會 ’、坐化合物可以被穩穩定性造成不好影鄉树知組成物的貯存 *、·"導，並且立體障礙，丨、 + 異，晶籠崩解時可Ik 軍礙小，因此反應性優、發揮出低溫硬化性。作為上述具有〗另1個以上碳原子數為1 咪唑化合物，可以π a 数马1〜ό的取代基的列舉例如2-曱基味唑、2-苯基咪唑等具有1個碳原子备去料數4 1〜6的取代基的咪唑化合物；2_乙基-4-甲基α米β坐、，-二甲基咪唑、2-苯基-4 -曱基-5-羥基甲基°米。坐笼_Η七_ 寻八有兩個碳原子數為丨〜6的取代基的咪唑化合物等。作為笨并咪唑化合物，可以列舉例如下述式（4)表示的化合物等。 (r14CcIVr15 (4)_ Come to Kimi 0 to take hydrochloric acid step, T 镊 trimellitate and so on. U benzyl-2-phenylimidazole In these compounds φ dry' is preferably a substituent having 1 to 6 substituents, and the number of carbon atoms or more is a disaster compound. This kind of banker is bound to be grounded, so it will not be, and the compound can be stabilized and stabilized, resulting in the storage of the composition. *,···, and steric obstacles, 丨, +, different cages When disintegrating, Ik is less obstructive, so it has excellent reactivity and exhibits low-temperature hardenability. Examples of the substituent having one or more carbon atoms of 1 imidazole compound and having a π a number of 1 to fluorene include, for example, 2-indolyl azole and 2-phenylimidazole having one carbon atom. Imidazole compound having a substituent of 4 1 to 6; 2 -ethyl-4-methyl α m β sit, , -dimethylimidazole, 2-phenyl-4-indenyl-5-hydroxymethyl Meter. The cage _ Η _ _ 八八八八八八八八八八八八八八八八八八八八八八八八The compound represented by the following formula (4), etc. are mentioned as a stupid imidazole compound, for example. (r14CcIVr15 (4)

I R16 上述式（4)中，R!4〜R!6各自獨立地為氫原子、碳原子數為1〜6的烷基、萘基、蒽基、菲基、9-苐基、鹵素原子、碳原子數為丨〜6的烷基、苯基或可以被鹵素原子取代的苯基》爪為〇〜4的整數。但是，存在多個Rl4時，多個R14可以相同也可以不同。 -30· 201207558 作為笨并味哇唑、4-甲美策 '，丄&物，可以列舉例如2-甲基笨并味土开咪唑、5_甲基苯并，、 7-甲基笨并咪唑、卞坐δ甲基本开咪唑、基苯并，唾、2-甲美6_甲基笨并咪啥、2_甲基-6-甲并咪。坐、2-乙基二5_甲基苯并唯°坐、2-甲基_5-甲基笨 .〇土 _甲基苯并咪唑、2-曱基_6_乙美# & 唑、2-乙基·5_甲其分、，土 G基本并咪在這些化合Γ中开…-甲基…苯并味唾等。 ,. 中，較佳為具有1個以上碳；f+u· 4 1〜6的取代基的庆原子數為被穩定地包合，因;、：匕口物。攻種咪唑化合物可以此不會對該感放射線貯存穩定性造成不 &線㈣月曰組成物的性優昱曰拉景/響，並且立體障礙小，因此反Α 陡優/、’日日蘢朋解時可發揮出低溫硬化性。心 :為上达具有i個以上碳原子數為Η的取代基的 ' °，、唑化合物’可以列舉例如2-甲基苯并咪唑等： 1個碳原子數…的取代基的笨…化合物;= -:甲基苯并味唾、2_甲基_5甲基苯并咪唾等具有兩個：原子數為1〜6的取代基的苯并咪唑化合物等。剛化合物可以單獨使用1種或混合使用兩種以上。作為該感放射線性樹脂組成物中[Ε]化合物的含量，相對於[Α]共聚物100質量份，較佳為〇〇5質量份〜5質量份’更佳為0.1質量份〜2.5質量份，並且較佳為相對於[D]化合物為0.5倍〜1倍左右。 <晶蘢化合物> 對於該感放射線性樹脂組成物，較佳為[Ε]胺化合物的至少一部分被包合在[D]化合物中。對於該感放射線性樹脂組成物，藉由使[Ε]胺化合物的至少一部分包合在[D] 201207558 化合物中而形成晶籠化合物’能夠同時滿足貯存穩定性和低溫燒製。作為用[D]化合物包合[E]胺化合物的方法，沒有特別的限制，可以列舉例如曰本特開平丨丨_07丨449號公報中記載的方法等。對於25。(：下的黏度為l.OmPa . s以上 5 0mPa · s以下的該感放射線性樹脂組成物，較佳為將在 [D]化合物中包合[E]胺化合物所形成的晶籠化合物與 [A]共聚物、[B]聚合性化合物及[C]感放射線性聚合引發劑進行混合’從而進行配製。藉由上述步驟，可以有效地製造含有晶籠化合物的該感放射線性樹脂組成物。預先形成晶籠化合物’並包含在該感放射線性樹脂組成物中時，作為該感放射線性樹脂組成物中的晶籠化合物的含量，相對於[A]共聚物100質量份，較佳為〇1 質量份〜10質量份，更佳為0.2質量份〜5質量份。藉由將晶籠化合物的含有比例設定為0 · 1質量份〜1 〇質量份’可以使該感放射線性樹脂組成物以高水準同時滿足貯存穩定性和硬化膜的硬化促進，而且使具備得到的保護膜、層間絕緣膜、隔離物等硬化膜的顯示元件的電壓保持率保持在高水準上。 <任意成分> 作為該感放射線性樹脂組成物，除了上述[A]共聚物、[B]聚合性化合物、[C]感放射線性聚合弓丨發劑、[d] 化合物及[E]胺化合物外，必要時還可以在卜他+扣害預期效果的範圍内含有每分子中含有兩個以上環氧仅礼乙烧基的化合物、黏接助劑、界面活性劑、貯存穩定劑、耐熱性提 -32- 201207558 高劑等任意成分。這些任意成分可以單獨使用一種，也可以混合使用兩種以上。以下對各種成分進行詳細說明。 [每分子中含有兩個以上環氧乙烷基的化合物] 每分子中含有兩個以上環氧乙烷基的化合物可以為了進一步提高得到的硬化膜的硬度而添加。作為這種化合物，可以列舉例如每分子内含有兩個以上3,4-環氧環己基的化合物等。作為每分子内含有兩個以上3,4-環氧環己基的化合物，可以列舉例如3,4-環氧環己基甲基-3，，4’-環氧環己烷羧酸酯、2-(3,4-環氧環己基-5,5-螺-3,4-環氧）環己烷-間嘮4、雙（3,4-環氧環己基曱基）己二酸酯、雙（3，4-環氧 -6-曱基環己基曱基）己二酸酯、3,4-環氧-6-曱基環己基 -3’，4’-環氧-6’ -甲基環己烷羧酸酯、亞曱基雙（3,4-環氧環己烷）、二環氧化二環戊二烯、乙二醇的雙（3,4-環氧環己基曱基）醚、伸乙基雙（3,4-環氧環己烷羧酸酯）、内酯改性3，4-環氧環己基曱基-3’，4’-環氧環己烷羧酸酯等。作為其他化合物，可以列舉例如雙酚A二縮水甘油醚、雙紛F二縮水甘油轉、雙紛S二縮水甘油醚、氫化雙盼A二縮水甘油謎、氫化雙盼F二縮水甘油、氫化雙紛AD二縮水甘油醚、漠化雙紛Α二縮水甘油醚、漠化雙酌· F二縮水甘油醚、演化雙盼S二縮水甘油鱗等雙紛化令物的二縮水甘油醚； 1，4-丁二醇二縮水甘油醚、1,6-己二醇二縮水甘油醚、甘油三縮水甘油醚、三經甲基丙烧三縮水甘油醚、 -33- 201207558 聚乙二醇二縮水甘油醚、聚丙二醇二縮水甘油醚等多元醇的多縮水甘油醚；藉由在乙二醇、丙二醇、甘油等脂肪族多元醇上加成1種或兩種以上環氧烷烴而得到的聚醚多元醇的多縮水甘油醚；苯酚酚醛清漆型環氧樹脂；甲酚酚醛清漆型環氧樹脂；多酚型環氧樹脂；環狀脂肪族環氧樹脂；脂肪族長鏈二元酸的二縮水甘油酯；高級脂肪酸的縮水甘油酯；環氧化大豆油、環氧化亞麻子油等。在這些化合物中’較佳為苯酚酚醛清漆型環氧樹脂及多酚型環氧樹脂。作為這些物質的市售製品，可以列舉例如作為雙酚 A型環氧樹脂的 EPICOTE1001、 EPICOTE1002 、 EPICOTE1003 、 EPICOTE1004 、 EPICOTE1007、EPICOTE1009、EPICOTE1010、 EPICOTE828(以上 ’ Japan Epoxy Resin 公司）等；作為雙酚F型環氧樹脂的EPICOTE807(Japan Epoxy Resin公司）等；作為苯酚酚醛清漆型環氧樹脂的 EPICOTE152、 EPICOTE154、EPICOTE157S65(以上，Japan Epoxy Resin 公司）、EPPN201、EPPN 202(以上，曰本化藥公司）等；作為曱酚酚醛清漆型環氧樹脂的 EOCN102、 EOCN103S、EOCN104S ' 1020、1025、1027(以上，日本化藥公司）、EPICOTE 180S75(Japan Epoxy Resin 公司）等； -34- 201207558 作為多酚型環氧樹脂的 EPICOTE1032H60、 EPICOTEXY-4000(以上，Japan Epoxy Resin 公司）等；作為環狀脂肪族環氧樹脂的 CY-175、CY-177、 CY-179 ' Araldite CY-182 ' Araldite CY-192 ' Araldite CY-184(以上，Ciba Specialty Chemicals 公司）、 ERL-4234、ERL-4299、ERL-422 卜 ERL-4206(以上，U.C.C 公司）、Shodyne509(日召和電工公司）、EPICLON 200、 EPICLON 400(以上，大日本油墨公司）、EPICOTE871、 EPICOTE872(以上，Japan Epoxy Resin 公司）、ED-5661、 ED-5662(以上，Celanese coating 公司）等；作為脂肪族多縮水甘油醚的 EPOLIGHT 100MF(共榮公司化學公司）、EPIOL TMP(日本油脂公司）等。作為每分子中含有兩個以上環氧乙烷基的化合物的使用量，相對於[A]共聚物1 〇〇質量份，較佳為50質量份以下，更佳為2質量份〜50質量份，特佳為5質量份〜3〇質量份。藉由使每分子中含有兩個以上環氧乙烷基的化合物的使用量處於上述特定範圍内，可以在不損害顯影性的情況下進一步提高層間絕緣膜、隔離物或保護膜等硬化膜的硬度。 [黏接助劑] 黏接助劑為是了進一步提高得到的層間絕緣膜、隔離物或保護膜等硬化膜與基板的黏接性而使用的。作為這種黏接助劑，較佳為具有羧基、曱基丙烯醯基、乙烯基、異氰酸酯基、環氧乙烷基等反應性官能圑的官能性石夕烧偶聯劑，例如可以列舉三曱氧基曱矽烷基安息香 -35- 201207558 酸、τ -甲基丙烯醯氧基丙基三甲氧基矽烷、乙烯基三乙酿氧基石夕燒、乙烯基三曱氧基矽烷、r -異氰酸酯丙基三乙氧基石夕烷、r-環氧丙氧基丙基三甲氧基矽烷、冷_(3,4_ 環氧環己基）乙基三甲氧基矽烷等。作為點接助劑的使用量，相對於[A]共聚物1 〇〇質量伤較佳為2 0質量份以下，更佳為15質量份以下。如果黏接助劑的使用量超過2〇質量份，則容易產生顯影殘留。 [界面活性劑] 界面活性劑是為了進一步提高該感放射線性樹脂組成物的塗膜形成性而使用的。作為界面活性劑，可以列舉例如氟類界面活性劑、有機矽樹脂類界面活性劑、其他界面活性劑等。作為氟類界面活性劑’較佳為末端、主鏈及側鏈中的至少一個部位上具有氟烷基和/或氟伸烷基的化合物，可以列舉例如1，1，2,2-四氟-正辛基（ι，ι，2,2-四氟-正丙基）趟、m2·四氟-正辛基（正己基）醚、六乙二醇雙 (1，丨，2，〗，〗，3-六氟-正戊基）醚、八乙二醇二（mi四氟_ 正丁基）喊、六丙二醇雙（1，1，2,2,3,3-六氟-正戊基）醚、八丙一醇雙（1，1，2,2 -四氟-正丁基）醚、全氟_正十二烷磺酸鈉 1，1，2,2,3,3_六氟正癸烷、1，1,2,2,8,8,9,9,10,10-十氟正十一烷、及氟烷基苯磺酸鈉、氟烷基磷酸鈉、氟烷基羧酸鈉、二甘油四（氟烷基聚氧乙烯醚）、氟烷基碘化銨、氟烷基甜菜鹼、其他氟烷基聚氧乙烯醚、全氟烷基聚羥基乙醇、全氟烷基烷氧化物、羧酸氟烷基酯等。 -36- 201207558 作為氟類界面活性劑的市售製品，可以列舉例如 BM-10 00、BM-1100(以上，BM CHEMIE 公司）、MEGAFAC F142D、MEGAFAC F 1 7 2、MEG AFAC F 1 7 3、MEG AFAC F183、MEGAFAC F178、MEGAFAC F191、MEGAFAC F471、MEGAFAC F476(以上，大曰本油墨化學工業公司）、FRORAID FC-170C、FRORAID FC-171、FRORAID FC-43 0、FRORAID FC-431(以上，住友 3M 公司）、Surflon S-112、Surflon S-113、Surflon S-131、Surflon S-141、 Surflon S-145、Surflon S-382、Surflon SC-101 ' Surflon SC-102、Surflon SC-103、Surflon SC-104、Surflon SC-105、Surflon SC-106(以上，旭硝子公司）、EFTOP EF301、EFTOP EF 303、EFTOP EF 352(以上，新秋田化成公司）、FTERGENT FT-100、FTERGENT FT-110、 FTERGENT FT-140A、FTERGENT FT-1 50 ' FTERGENT FT-250、FTERGENT FT-251、FTERGENT FT-300、 FTERGENT FT-310、FTERGENT FT-400S、FTERGENT FTX-218、FTERGENT FTX-251(以上，NEOS 公司）等。作為有機矽樹脂類界面活性劑的市售製品，可以列舉例如 Toray SiliconeDC3PA、Toray SiliconeDC7PA、 Toray SiliconeSH 11 PA、Toray SiliconeSH21 PA、Toray SiliconeSH28PA 、 Toray SiliconeSH29PA 、 TorayI R16 In the above formula (4), R!4 to R!6 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a naphthyl group, an anthracenyl group, a phenanthryl group, a 9-fluorenyl group, and a halogen atom. An alkyl group having a carbon number of 丨~6, a phenyl group or a phenyl group which may be substituted by a halogen atom is an integer of 〇~4. However, when there are a plurality of R14, a plurality of R14s may be the same or different. -30· 201207558 As a stupid and savory sulphate, 4-methyl melamine, 丄 & amps, for example, 2-methyl benzoic acid imidazol, 5-methylbenzo, 7-methyl stupid And imidazole, sputum δ methyl benzimidazole, phenyl benzo, saliva, 2-methyl 6-methyl benzopyrene, 2-methyl-6-methyl mercapto. Sit, 2-ethyldi-5-methylbenzo-indolence, 2-methyl-5-methyl stupid. 〇-_-methylbenzimidazole, 2-mercapto _6_ 乙美# & azole , 2-ethyl·5_methine, and the basic G of the earth is opened in these compounds...-methyl...benzoic and so on. In the middle, it is preferable to have one or more carbons; the number of atoms of the substituent of f+u·4 1 to 6 is stably contained, because: a mouthwash. The imidazole compound can be used to prevent the radiation storage stability from being unsatisfactory. The line (four) moon 曰 composition is superior to the scent and the steric obstacle is small, so the Α 陡 steepness is excellent, and the day is It can be used at low temperature and hardenability. Heart: ' °, the azole compound having a substituent having i or more carbon atoms is exemplified, for example, 2-methylbenzimidazole or the like: a compound having a substituent of one carbon atom... ;= -: a benzzimidazole compound having two substituents: a substituent having an atomic number of 1 to 6, and the like. The rigid compound may be used alone or in combination of two or more. The content of the [Ε] compound in the radiation-sensitive resin composition is preferably 质量5 parts by mass to 5 parts by mass, more preferably 0.1 parts by mass to 2.5 parts by mass, per 100 parts by mass of the [Α] copolymer. And it is preferably about 0.5 to about 1 time with respect to the [D] compound. <Crystalline compound> For the radiation sensitive resin composition, at least a part of the [Ε]amine compound is preferably contained in the [D] compound. With respect to the radiation sensitive resin composition, the crystal cage compound can be formed by simultaneously including at least a part of the [Ε] amine compound in the compound [D] 201207558 to satisfy both storage stability and low-temperature firing. The method of encapsulating the [E] amine compound with the [D] compound is not particularly limited, and examples thereof include those described in JP-A-H07-449. For 25. (The lower viscosity is 1.0 MPaPa. s or more of 50 ÅPa·s or less of the radiation sensitive resin composition, preferably the crystal cage compound formed by encapsulating the [E] amine compound in the [D] compound and The [A] copolymer, the [B] polymerizable compound, and the [C] radiation-sensitive polymerization initiator are mixed and prepared. By the above steps, the radiation-sensitive resin composition containing the crystal cage compound can be efficiently produced. When the crystal cage compound is formed in advance and is contained in the radiation sensitive resin composition, the content of the cage compound in the radiation sensitive resin composition is preferably 100 parts by mass based on 100 parts by mass of the [A] copolymer. 〇1 parts by mass to 10 parts by mass, more preferably 0.2 parts by mass to 5 parts by mass. The radiation-sensitive resin composition can be made by setting the content ratio of the crystal cage compound to 0 · 1 part by mass to 1 〇 by mass The material satisfies the storage stability and the hardening promotion of the cured film at a high level, and maintains the voltage holding ratio of the display element having the obtained cured film such as a protective film, an interlayer insulating film, and a separator at a high level. Component > As the radiation sensitive resin composition, in addition to the above [A] copolymer, [B] polymerizable compound, [C] radiation sensitive polymeric hairpin, [d] compound, and [E] amine compound If necessary, it may contain a compound containing two or more epoxy groups, an adhesion promoter, a surfactant, a storage stabilizer, and a heat resistance in the range of the expected effect of the catalysis + deduction. -32- 201207558 Any component such as a high dose. These optional components may be used singly or in combination of two or more. The various components are described in detail below. [Compounds containing two or more oxirane groups per molecule] The compound containing two or more oxirane groups per molecule may be added in order to further increase the hardness of the obtained cured film. Examples of such a compound include two or more 3,4-epoxycyclohexyl groups per molecule. Examples of the compound containing two or more 3,4-epoxycyclohexyl groups per molecule include, for example, 3,4-epoxycyclohexylmethyl-3,4'-epoxycyclohexanecarboxylic acid. Ester, 2-(3 , 4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-m-oxime 4, bis(3,4-epoxycyclohexyldecyl) adipate, bis (3 , 4-epoxy-6-fluorenylcyclohexyldecyl) adipate, 3,4-epoxy-6-fluorenylcyclohexyl-3',4'-epoxy-6'-methylcyclohexane Alkyl carboxylate, fluorenylene bis(3,4-epoxycyclohexane), dicyclopentadienyl dicyclopentadiene, bis(3,4-epoxycyclohexyldecyl)ether of ethylene glycol, extension Ethyl bis(3,4-epoxycyclohexanecarboxylate), lactone-modified 3,4-epoxycyclohexyldecyl-3',4'-epoxycyclohexanecarboxylate, etc. Other compounds may, for example, be bisphenol A diglycidyl ether, bis-F diglycidyl, bis-S-diglycidyl ether, hydrogenated double-presence A diglycidoliar, hydrogenated double-pregine F diglycidyl, hydrogenated double Diglycidyl ether of AD diglycidyl ether, desertified double diglycidyl diglycidyl ether, desertification double F · diglycidyl ether, evolution double hope S diglycidyl scale, etc.; 1,4 - Butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol triglycidyl ether, trimethyl methacrylate Triglycidyl ether, -33- 201207558 polyglycidyl ether of a polyhydric alcohol such as polyethylene glycol diglycidyl ether or polypropylene glycol diglycidyl ether; by adding an aliphatic polyol such as ethylene glycol, propylene glycol or glycerin Polyglycidyl ether of polyether polyol obtained by forming one or two or more alkylene oxides; phenol novolak type epoxy resin; cresol novolak type epoxy resin; polyphenol type epoxy resin; Group epoxy resin; diglycidyl ester of aliphatic long-chain dibasic acid; glycidyl ester of higher fatty acid; epoxidized soybean oil, epoxidized linseed oil, and the like. Among these compounds, phenol novolac type epoxy resin and polyphenol type epoxy resin are preferred. As a commercially available product of these materials, for example, EPICOTE 1001, EPICOTE 1002, EPICOTE 1003, EPICOTE 1004, EPICOTE 1007, EPICOTE 1009, EPICOTE 1010, EPICOTE 828 (above 'Japan Epoxy Resin Co., Ltd.), etc., as a bisphenol A type epoxy resin; EPICOTE 807 (Japan Epoxy Resin Co., Ltd.) of epoxy resin; EPICOTE 152, EPICOTE 154, EPICOTE 157S65 (above, Japan Epoxy Resin Co., Ltd.), EPPN201, EPPN 202 (above, Sakamoto Chemical Co., Ltd.) as a phenol novolak type epoxy resin, etc. EOCN102, EOCN103S, EOCN104S '1020, 1025, 1027 (above, Nippon Chemical Co., Ltd.), EPICOTE 180S75 (Japan Epoxy Resin Co., Ltd.), etc., as a nonphenolic novolak type epoxy resin; -34-201207558 OPICOTE1032H60, EPICOTEXY-4000 (above, Japan Epoxy Resin), etc.; CY-175, CY-177, CY-179 'Araldite CY-182 'Araldite CY-192 ' Araldite as a cyclic aliphatic epoxy resin CY-184 (above, Ciba Specialty Chemicals), ERL-4234, ERL-4299, ERL-422 ERL-4206 (above, UCC), Shodyne509 (Risic and Electric Company), EPICLON 200, EPICLON 400 (above, Dainippon Ink), EPICOTE871, EPICOTE872 (above, Japan Epoxy Resin), ED-5661, ED -5662 (above, Celanese coating Co., Ltd.); EPOLIGHT 100MF (Kyoei Chemical Co., Ltd.) and EPIOL TMP (Nippon Oil Co., Ltd.) as aliphatic polyglycidyl ether. The amount of the compound containing two or more oxirane groups per molecule is preferably 50 parts by mass or less, more preferably 2 parts by mass to 50 parts by mass, per part by mass of the [A] copolymer. , particularly preferably 5 parts by mass to 3 parts by mass. By using the compound having two or more oxirane groups per molecule in the above specific range, it is possible to further improve the cured film such as the interlayer insulating film, the separator or the protective film without impairing the developability. hardness. [Adhesive Aid] The adhesion aid is used to further improve the adhesion between the obtained interlayer insulating film, the cured film such as a separator or a protective film, and the substrate. As such an adhesion aid, a functional rheumatoid coupling agent having a reactive functional group such as a carboxyl group, a mercaptopropenyl group, a vinyl group, an isocyanate group or an oxirane group is preferred, and for example, three曱曱矽曱矽 alkyl benzoin -35- 201207558 acid, tau-methacryloxypropyltrimethoxydecane, vinyl triethyl ethoxylate, vinyl trimethoxy decane, r-isocyanate Triethoxy oxetane, r-glycidoxypropyltrimethoxydecane, cold _(3,4-epoxycyclohexyl)ethyltrimethoxydecane, and the like. The amount of use as the spotting aid is preferably 20 parts by mass or less, more preferably 15 parts by mass or less based on 1 〇〇 mass loss of the [A] copolymer. If the amount of the adhesion aid used exceeds 2 parts by mass, development residue is liable to occur. [Surfactant] The surfactant is used to further improve the coating film formability of the radiation-sensitive resin composition. As the surfactant, for example, a fluorine-based surfactant, an organic silicone resin surfactant, another surfactant, or the like can be listed. The fluorine-based surfactant is preferably a compound having a fluoroalkyl group and/or a fluorine-extended alkyl group in at least one of a terminal, a main chain and a side chain, and examples thereof include 1,1,2,2-tetrafluoro. - n-octyl (ι,ι,2,2-tetrafluoro-n-propyl) oxime, m2·tetrafluoro-n-octyl (n-hexyl)ether, hexaethylene glycol bis (1, 丨, 2, 〗, , 3-hexafluoro-n-pentyl)ether, octaethylene glycol di(mi tetrafluoro-n-butyl) shout, six-propylene glycol bis(1,1,2,2,3,3-hexafluoro-n-pentane Ether, octapropanol bis(1,1,2,2-tetrafluoro-n-butyl)ether, sodium perfluoro-n-dodecane sulfonate 1,1,2,2,3,3_6 Fluorane-n-decane, 1,1,2,2,8,8,9,9,10,10-decafluoro n-undecane, and sodium fluoroalkylbenzenesulfonate, sodium fluoroalkylphosphate, fluoroalkyl Sodium carboxylate, diglycerol tetrakis(fluoroalkyl polyoxyethylene ether), fluoroalkyl ammonium iodide, fluoroalkyl betaine, other fluoroalkyl polyoxyethylene ether, perfluoroalkyl polyhydroxyethanol, perfluoroalkane An alkyl alkoxide, a fluoroalkyl carboxylate or the like. -36-201207558 Commercially available products of a fluorine-based surfactant include, for example, BM-10 00, BM-1100 (above, BM CHEMIE), MEGAFAC F142D, MEGAFAC F 1 7 2, MEG AFAC F 1 7 3, MEG AFAC F183, MEGAFAC F178, MEGAFAC F191, MEGAFAC F471, MEGAFAC F476 (above, Otsuka Ink Chemical Industry Co., Ltd.), FRORAID FC-170C, FRORAID FC-171, FRORAID FC-43 0, FRORAID FC-431 (above, Sumitomo 3M Company), Surflon S-112, Surflon S-113, Surflon S-131, Surflon S-141, Surflon S-145, Surflon S-382, Surflon SC-101 ' Surflon SC-102, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-106 (above, Asahi Glass), EFTOP EF301, EFTOP EF 303, EFTOP EF 352 (above, New Akita Chemical Co., Ltd.), FTERGENT FT-100, FTERGENT FT-110, FTERGENT FT-140A, FTERGENT FT-1 50 'FTERGENT FT-250, FTERGENT FT-251, FTERGENT FT-300, FTERGENT FT-310, FTERGENT FT-400S, FTERGENT FTX-218, FTERGENT FTX-251 (above, NEOS )Wait. Commercially available products as organic silicone resin surfactants can be exemplified by Toray Silicone DC3PA, Toray Silicone DC7PA, Toray Silicone SH 11 PA, Toray Silicone SH21 PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray

SiliconeSH30PA 、 Toray SiliconeSH-190 、 ToraySiliconeSH30PA, Toray SiliconeSH-190, Toray

SiliconeSH-193 、 Toray SiliconeS Z -6032 、 ToraySiliconeSH-193, Toray SiliconeS Z -6032, Toray

SiliconeSF-8428 、 Toray Silicon. eDC-57 、 ToraySiliconeSF-8428, Toray Silicon. eDC-57, Toray

SiliconeDC-190(以上，Toray · Dow Corning · Silicone -37- 201207558 公司）、TSF-4440 、 TSF-4300 、 TSF-4445 、 TSF-4446 、 TSF_4460、TSF-4452(以上，GE東芝有機矽樹脂公司）、有機矽氧烷聚合物KP341(信越化學工業公司）等。作為其他界面活性劑，可以列舉例如聚氧乙烯月桂基趟、聚氧乙烯硬脂基醚、聚氧乙烯油基喊等聚氧乙烯烷基醚·’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、聚氧乙稀二硬脂酸酯等聚氧乙烯二烷基酯等非離子系界面活性劑、（曱基）丙烯酸系共聚物P〇lyfl〇N〇.57 、 P〇lyfloN〇.95(以上’共榮公司化學公司）等。作為界面活性劑的使用量，相對於[A]共聚物丨〇〇質量伤較佳為1·〇質里份以下，更佳為〇·5質量份以下。如果界面活性劑的使用量超過丨〇質量份，則容易導致膜的不均勻。 [貯存穩定劑] 作為貯存穩定劑’可以列舉例如硫、醌類、氫醌類、聚氧（polyoxy)化合物、胺、硝基亞硝基化合物等，更具體來說可列舉4-曱氧基苯酚、N-亞硝基_N_苯基羥基胺鋁等。作為貯存穩定劑的使用量，相對於[A ]共聚物丨〇〇質昼伤較佳為3 · 0質量份以下，更佳為〇 5質量份以下。如果射存穩定劑的摻合量超過3 ·0質量份，則該感放射線性樹脂組成物的敏感度變差，可能導致圖案形狀的劣化。 -38- 201207558 [耐熱性提高劑] 作為耐熱性提高劑，可以列舉例如N_(烷氧旯甘腺化合物、N_(烧氧基甲基）三聚氰胺化合物等? 土作為N·(烧氧基曱基）甘腺化合物，可以列舉例如 N，N，N’，N’-肆（甲氧基甲基）甘脲、N，N，N，，N，_肆（乙氧基甲基）甘脲、N，N，N，，N，_肆（正丙氧基甲基）甘脲、n，n，n^n，_ 肆（異丙氧基甲基）甘脲、N，N，n，，n，·肆（正丁氧基甲基）甘脲、圪化，；^，，1^，，-肆（三級丁氧基曱基）甘脲等。在這些化合物中，較佳為N，N，N，，N，·肆（曱氧基甲基）甘脲。作為N -(院氧基甲基）二聚氰胺化合物，可以列舉例如n，n，n’，n，，n’，，n，’_陸（甲氧基甲基）三聚氰胺、 n，n，n’，n’，n’’，n’’-陸（乙氧基甲基）三聚氰胺、 n，n，n’，n’，n’’，n’’_陸（正丙氧基甲基）三聚氰胺、 N’N，N’，N’，N’’，N’’-陸（異丙氧基曱基）三聚氰胺、 N，N，N’，N’，N’’，N’，-陸（正丁氧基甲基）三聚氰胺、 >1，:^，:^’，:^’，:^’’，>}’’-陸（三級丁氧基甲基）三聚氰胺等。在這些化合物中，較佳為n，n，n，，n，，n’，，n，’-陸（曱氧基曱基）三聚氰胺。作為市售製品，可以列舉例如 NIKALACN-2702 、NIKALACMW-30M(以上，Sanwa Chemical 公司）等〇作為耐熱性提高劑的使用量，相對於[A]共聚物1 〇〇質量份’較佳為5 0質量份以下，更佳為3 0質量份以下。如果耐熱性提高劑的摻合量超過50質量份，則該感放射線性樹脂組成物的敏感度變差，可能導致圖案形狀的劣化0 -39- 201207558 <感放射線性樹脂組成物的配製方法> 作為本發明的硬化膜形成用感放射線性樹脂組成物’除了 [A]共聚物、[B]聚合性化合物、[c]感放射線性聚合引發劑、[D]化合物及[E]胺化合物外，必要時可以在不4貝害預期效果的範圍内按規定比例混合任音成分，從而進行配製。25°C下的黏度為1.0mPa . 8以上50mPa · s以下的该感放射線性樹脂組成物，較佳為是藉由將在 [D]化合物中包合[E]胺化合物而形成的晶籠化合物與 [A]共聚物、[B]聚合性化合物及[C]感放射線性聚合引發劑進行混合而配製。作為該感放射線性樹脂組成物的配製中使用的溶劑’可以使用均勻地溶解或分散各種成分，並且不與各種成分反應的溶劑。作為這種溶劑，適用作為可用於合成上述[A ]共聚物的溶劑而例示的溶劑。作為溶劑，較佳為含有選自醇類溶劑及醚類溶劑的至少一種溶劑。可以認為，藉由含有上述極性溶劑，可以容易地溶解該感放射線性樹脂組成物，並且對於本發明來說’如上所述即使在使用極性溶劑的情況下，也可以藉由晶籠化合物的相互作用抑制晶籠的崩解。溶劑可以早獨使用·一種或》扣合使用兩種以上。Silicone DC-190 (above, Toray · Dow Corning · Silicone -37-201207558), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF_4460, TSF-4452 (above, GE Toshiba Organic Silicone Resin) , organic siloxane polymer KP341 (Shin-Etsu Chemical Industry Co., Ltd.) and the like. Examples of the other surfactants include polyoxyethylene lauryl hydrazine, polyoxyethylene stearyl ether, polyoxyethylene oil-based polyoxyethylene alkyl ether, polyoxyethylene-n-octyl phenyl ether, and the like. a polyoxyethylene aryl ether such as polyoxyethylene_n-nonylphenyl ether; a nonionic surfactant such as polyoxyethylene dialkyl ester such as polyoxyethylene dilaurate or polyoxyethylene distearate , (fluorenyl) acrylic copolymer P〇lyfl〇N〇.57, P〇lyfloN〇.95 (above 'Kongrong Chemical Co., Ltd.) and the like. The amount of the surfactant to be used is preferably 1 or less, more preferably 5 parts by mass or less based on the mass loss of the [A] copolymer. If the amount of the surfactant used exceeds 丨〇 by mass, it tends to cause unevenness of the film. [Storage Stabilizer] Examples of the storage stabilizer include sulfur, anthraquinone, hydroquinone, a polyoxy compound, an amine, a nitronitroso compound, and the like, and more specifically, a 4-decyloxy group. Phenol, N-nitroso-N-phenylhydroxylamine aluminum, and the like. The amount of the storage stabilizer to be used is preferably 3.0 parts by mass or less, more preferably 5 parts by mass or less, based on the [A] copolymer 〇昼昼. If the blending amount of the shot stabilizer exceeds 3.0 parts by mass, the sensitivity of the radiation sensitive resin composition is deteriorated, which may cause deterioration of the pattern shape. -38-201207558 [Heat resistance improving agent] Examples of the heat resistance improving agent include N_(alkoxyglycine compound, N_(alkoxymethyl) melamine compound, etc.; The gland compound, for example, N, N, N', N'-fluorene (methoxymethyl) glycoluril, N, N, N, N, 肆 (ethoxymethyl) glycoluril, N,N,N,,N,_肆(n-propoxymethyl)glycoluril, n,n,n^n,_肆(isopropoxymethyl)glycoluril, N,N,n,, n, · 肆 (n-butoxymethyl) glycoluril, deuterated, ^,, 1 ^,, - 肆 (tertiary butoxy fluorenyl) glycoluril, etc. Among these compounds, preferably N , N, N,, N, · 肆 (decyloxymethyl) glycoluril. As the N - (homoyloxymethyl) melamine compound, for example, n, n, n', n, n ',,n,'_L (methoxymethyl)melamine, n,n,n',n',n'',n''-lu (ethoxymethyl)melamine, n,n,n ',n',n'',n''_Lu (n-propoxymethyl)melamine, N'N,N',N',N' ',N''-L (isopropoxy fluorenyl) melamine, N, N, N', N', N'', N', - (n-butoxymethyl) melamine, >1, :^,:^',:^',:^'',>}''-Lu (tertiary butoxymethyl) melamine, etc. Among these compounds, n, n, n, n,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, The amount of use is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, based on 1 part by mass of the [A] copolymer. If the blending amount of the heat resistance improving agent exceeds 50 parts by mass, The sensitivity of the radiation-sensitive resin composition is deteriorated, which may cause deterioration of the pattern shape. 0 - 39 - 201207558 <Preparation method of radiation sensitive resin composition> As a radiation-sensitive resin composition for forming a cured film of the present invention ' except for [A] copolymer, [B] polymerizable compound, [c] radiation sensitive polymerization initiator, [D] compound and [E] In addition to the compound, if necessary, the content of the sound component may be mixed in a predetermined ratio within a range of not expected to be harmful. The viscosity at 25 ° C is 1.0 mPa. The radiation sensitive resin of 8 or more and 50 mPa · s or less The composition is preferably a radiation-linear polymerization of a cage compound formed by encapsulating an [E] amine compound in the [D] compound with [A] copolymer, [B] a polymerizable compound, and [C] The initiator is prepared by mixing. As the solvent used in the preparation of the radiation-sensitive resin composition, a solvent which uniformly dissolves or disperses various components and does not react with various components can be used. As such a solvent, a solvent exemplified as a solvent which can be used for synthesizing the above [A] copolymer is used. The solvent preferably contains at least one solvent selected from the group consisting of an alcohol solvent and an ether solvent. It is considered that the radiation sensitive resin composition can be easily dissolved by containing the above polar solvent, and for the present invention, as described above, even in the case of using a polar solvent, the crystal cage compounds can be mutually The action inhibits the disintegration of the cage. Solvents can be used alone or in combination with one or two types.

安息香酸乙醋、草酸二乙S旨 ’為了提高膜厚在面内。作為尚彿點溶劑，可 -T吞醞胺、节基 I、1 -壬醇、酷酸苄馬來酸二乙酯、 -40- 201207558 丁内酯、碳酸亞丙酯等。在這些溶劑中，較佳為吼略咬嗣、r -丁内酯、N，N_:甲基乙醯胺。作為該感放射線性樹脂組成物的溶劑，在並點溶劑的情況下作為其使用量，相對於總溶劑量為50質量％以下，更佳為40質量％以下，特佳^ 量％以下。高沸點溶劑的使用量為5 〇質量％以下膜的膜厚均勻性、敏感度及膜殘留率良好。將該感放射線性樹脂組成物配製為溶液狀，雖為固體成分濃度（組成物溶液中存在的溶劑以分），可以根據使用目的或預期膜厚的值等設定為度（例如5質量％〜50質量％)。作為更佳為的固體度，根據在基板上形成塗膜的方法而變化，對此進行說明。對於這樣配製的組成物溶液，可以使 0.5 μπι左右的微孔濾器等過濾後，進行使用。 <硬化膜的形成方法〉本發明還較佳為包含由該感放射線性樹脂組成的作為層間絕緣膜、保護膜或隔離物的硬化膜明的硬化膜的形成方法具備： (1) 在基板上形成該感放射線性樹脂組成物步驟； (2) 對上述塗膜的至少一部分照射放射線的步 (3) 使經過上述放射線照射的塗膜顯影的步辩 (4) 對經過上述顯影的塗膜進行燒製的步驟。根據使用該感放射線性樹脂組成物的本發明方法’可以形成耐熱性、耐化學試劑性、透光率 Ν-甲基用高沸，較佳 b 30質時，塗時，作外的成任意濃成分濃在後文用孔徑成物形。本發塗膜的驟； •，及的形成、平坦 -41 - 201207558 性及耐線性熱膨脹性得到很均衡地滿足的硬化膜。以下對各步驟進行詳細說明。 [步驟（1)] 本步驟是在透明基板的單面上形成透明導電膜，在該透明導電膜上形成感放射線性樹脂組成物的塗膜。作為透明基板’可以列舉例如鹼石灰玻璃、無驗玻璃等玻璃基板、由選自聚對苯二曱酸乙二酯、聚對苯二甲酸丁二酯、聚醚颯、聚碳酸酯、聚醯亞胺等塑膠組成的樹脂基板等。作為设置於透明基板單面上的透明導電膜，可以列舉由氧化錫（Sn〇2)組成的NESA膜（PPG公司，注冊商標）、由氧化銦-氧化錫（In2〇3_Sn〇2)組成的ιτο膜等。藉由塗布法形成塗膜時，在上述透明導電膜上塗布該感放射線性樹脂組成物的溶液後，較佳為對塗布面進行預烘烤，從而可以形成塗膜。作為塗布法中使用的組成物溶液的固體成分濃度，較佳為5質量％〜5〇質量％，更佳為10質量％〜40質量％，特佳為is質量％〜35質°量 %。作為塗布方法’可以列舉例如喷塗法、輥塗法、= 轉塗布法（旋塗法）、狹縫塗布法（縫模塗布法）、刮條塗^ 法、噴墨塗布法等。在這些方法中，較佳為旋塗法、狹縫塗布法。作為預烘烤的條件，根據各種成分的種類、摻合比例等變化，較佳為70t〜12〇t ,更佳為丨〜15分鐘左°右。塗膜預烘烤後的膜厚較佳為0.5μηι〜10μιη，更佳為 1 · 0 μιη〜7 · 0 μηι 〇 -42- 201207558 [步驟（2)] 本步驟是對形成的塗膜的至少一部分照射放射線。此時，僅對塗膜的一部分進行照射時，玎以採用例如透過具有規定圖案的光罩進行照射的方法。作為照射時使用的放射線’可以列舉例如可見光、紫外線、遠紫外線等。其中較佳為波長在250nm〜550nm範圍内的放射線，更佳為包含3 6 5 n m的紫外線的放射線。對於放射線照射量（曝光量），作為用照度計（Ο AI model 356、Optical Associates Inc·公司）測定照射放射線波長為365nm時的強度值，較佳為100J/m2〜5,000J/m2，更佳為 200J/m2〜3,〇〇〇j/m2。與以往已知的組成物相比，該感放射線性樹脂組成物具有以下優點：放射線敏感度高，即使上述放射線照射1為700J/m2以下’甚至為6〇〇j/m2以下，也可以得到具有預期膜厚、良好形狀、優異的密著性及高硬度的層間絕緣膜、保護膜或隔離物等硬化膜。 [步驟（3)] 本步驟疋使經過上述放射線照射的塗膜顯影，除去不需要的部分’形成規定圖案。作為顯影時使用的顯影液，可以列舉例如氫氧化鈉、氫氧化鉀、碳酸鈉等無機鹼、四曱基氫氧化銨、四乙基氫氧化銨等季銨鹽等鹼性化合物的水溶液等。還可、在上述鹼性化合物的水溶液中適量添加甲醇、乙醇等 ’谷丨生有機溶劑和/或界面活性劑進行使用。 -43- 201207558 沐、i ,為顯影方法，可以列舉例如液盛法（Paddle)、浸泡私^、淋法等。作為顯影時間，較佳為常溫下10秒〜180 二二。顯影處理後著例如進行流水洗滌30秒〜90 、'、後藉由壓縮空氣或屢縮1氣風乾得到預期圖案。 L步驟（4)] 本步驟藉由加轨杯、々々楚 …板烘相專適§的加熱裝置對得到立八。狀塗膜進行燒製（後供烤Η乍為燒製溫度，較佳為 100〇C 〜2〇〇°γ ，φ 乂土 i 〇 Λ 〇C更佳為15〇C〜180t。該感放射線性樹 ::成物在實現如上所述低溫燒製的同時，兼具貯存穩並具有足夠的放射線敏感度。因此，該感放射 ^树脂組成物適宜用作希望進行低溫燒製的柔性顯示益使用的層間絕緣膜、保護膜及隔離物等硬化膜的形 ^材料。作為燒製時間，例如較佳在加熱板上時為5分鐘〜3〇分鐘，在烘箱中時為30分鐘〜180分鐘。 <顯示元件的製造方法> …本發明較佳為包含具備該硬化膜的顯示元件。該顯示元件可以實現優異的電壓保持率。作為顯示元件的製造方法，首先準備一對（兩片）單面上具有透明導電膜（電極）的透明基板，在其中一片基板的透明導電膜上，使用該感放射線性樹脂組成物按照上述方法形成隔離物或保護膜或這兩者。接著，在這些基板上的透明導電膜及隔離物或保護膜上形成具有液晶配向能力的配向膜。使這些基板以下述方式相對配置，按照使形成該配向膜一側的表面朝向内側，各配向膜的液晶配向方向達到正交或逆平行的方式並且間隔一 -44- 201207558 定間隙（胞間隙）地進行相對配置，在由基板表面（配向膜: 及隔離物劃又的胞間隙内填充液晶，密封填充孔從而構成液晶胞。藉由在液晶胞的兩個外表面上按照使偏光板的偏光方向與形成於該基板一個面上的配向膜的液晶配 °方向致或正父的方式貼合偏光板’可以得到本發明的顯示元件。马具他方法，與 Τ —蚵形成了透明導電臈、層間絕緣膜、保護膜或隔離 ::向膜的透明基板。沿著該後一個基板端部=二益塗布紫外線硬化型密封劑，然後使用液晶分布器以微 2ΓΓ滴加液晶，在^下使兩基板黏合。對於上述 :1部分，使用高壓水銀燈照射紫外線，密封兩個基 1後在液晶胞的兩個外表 $1, , 〇工刹貼偈先板，從而得到本發明的顯示元件。作為上述各種方法令使帛的n 列型液晶、近晶型液曰$ U 列舉例如向用的偏光板，可以列|肱氣及日日胞外側使向，-邊… 對聚乙稀醇進行拉伸配邊吸收碘而形成的被稱為「H膜」 :醋酸纖維素保護膜中得到的偏光板、或由成的偏光板等。 Η膜本身組實施f列 ^ 1 签π 1她例斟*欲00 但該實 J奵本發明進行詳施例並不是對本發明疋仃限疋性的解釋 -45- 201207558 < [A]共聚物的合成> [合成例1] 在戈·裝了冷凝管及攪拌器的燒瓶中，加入5質量份 2,2-偶氣雙（2,4_二甲基戊腈）及220質量份二乙二醇曱基乙基謎。接著加入20質量份苯乙烯、12質量份曱基丙稀酸、28質量份甲基丙烯酸二環戊基酯及4〇質量份甲基丙烯酸縮水甘油酯，用氮氣置換，一邊緩慢攪拌，邊將谷液的溫度升高到7(TC，將該溫度保持5小時進行聚合’從而得到含有共聚物（A-1)的溶液。得到的共聚物溶液的固體成分濃度為3 1.3 %，共聚物（A-1)的Mw為 12,〇〇〇。還有’固體成分濃度是指共聚物佔共聚物溶液總質量的比例。 [合成例2] 在安裝了冷凝管及攪拌器的燒瓶中，加入5質量份 2,2’-偶氮雙（2,4-二甲基戊腈）及220質量份二乙二醇甲基乙基醚。接著加入1〇質量份苯乙烯、12質量份曱基丙烯酸、23質量份曱基丙烯酸三環二環戊基酯及2〇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酯，用氮氣置換後’再加入5質量份1，3 - 丁二烯，一邊緩慢攪拌， —邊將溶液的溫度升高到7(TC，將該溫度保持5小時進行聚合，從而得到含有共聚物（A - 2)的溶液。得到的共聚物溶液的固體成分濃度為31.5%，共聚物（A-2)的Mw為 1〇，10〇〇 -46- 201207558 [合成例3 ] 在安裝了冷凝管及攪拌器的燒瓶中，加入5質量份 2，2’-偶氮雙（異丁腈）及220質量份二乙二醇甲基乙基醚。接著加入15質量份苯乙烯、30質量份甲基丙烯酸正丁醋、30質量份甲基丙烯酸苄酯及25質量份甲基丙烯酸縮水甘油酯，一邊緩慢攪拌，一邊將溶液的溫度升高到80°C，將該溫度保持5小時進行聚合，從而得到含有共聚物（A-3)的溶液。得到的共聚物溶液的固體成分濃度為31.0%，共聚物（Α·3)的Mw為1〇,〇〇〇。 <硬化膜形成用感放射線性樹脂組成物的配製> 各感放射線性樹脂組成物的配製中使用的各種成分的細節如以下所示。 [B ]聚合性化合物 B-1:二新戊四醇五丙稀酸酯和二新戊四醇六丙稀酸酯的混合物（KAYARAD DPHA，日本化藥公司） B-2 :多官能丙烯酸酯化合物的混合物（KayaRAD DPHA-40H，曰本化藥公司） B-3: 1，9 -壬二醇二丙婦酸g旨 B - 4 :新戊四醇四丙烯酸酯 B-5 :三羥甲基丙烷三丙烯酸酯 B-6. 叛基聚己内自旨單丙烯酸醋 (ARONIXM-5300、東亞合成公司） B - 7 :破珀酸改性新戊四醇三丙烯酸酯 (ARONIXTO-756、東亞合成公司） B - 8 :環氧乙烧改性二新戊四醇六丙浠酸酯 -47- 201207558 [c]感放射線性聚合引發劑 C-l : 1，2-辛二酮-1-[4-(苯硫基）-2-(0-苯曱醯肟）](IRGACURE OXEOl，Ciba Specialty Chemicals 公司） C-2 :乙醇- l-[9-乙基-6-(2-曱基苯曱醯基）-9H-咔唑 -3-基]-1-(0-乙醯肟）（IRGACURE OXE02，Ciba Specialty Chemicals 公司） C - 3 : 2 -曱基-1 - (4 -甲硫基本基）-2 -味琳基丙-1 -銅 (IRGACURE 907，Ciba Specialty Chemicals 公司） C-4 : 2-二曱基胺基-2-(4-甲基苄基）-1-(4-咪啉-4-基-苯基）-丁 -1-酮（IRGACURE 379 ’Ciba Specialty Chemicals 公司 [D ]化合物 D-l:下述式表示的5-硝基間苯二甲酸The benzoic acid ethyl vinegar and the oxalic acid diethyl s s are intended to increase the film thickness in the surface. As a solvent, it is possible to use -T guanamine, a sulfhydryl group 1, a decyl alcohol, diethyl benzyl maleate, -40-201207558 butyrolactone, propylene carbonate and the like. Among these solvents, ruthenium, r-butyrolactone, and N,N_:methylacetamide are preferred. The solvent used as the radiation-sensitive resin composition is used in an amount of 50% by mass or less, more preferably 40% by mass or less, and particularly preferably not more than the total amount of the solvent. The amount of the high-boiling solvent to be used is 5 〇 mass% or less. The film thickness uniformity, sensitivity, and film residual ratio are good. The radiation-sensitive resin composition is prepared in a solution form, and is a solid content concentration (a solvent present in the composition solution), and can be set to a degree (for example, 5% by mass) depending on the purpose of use or the value of the desired film thickness. 50% by mass). The more preferable solidity varies depending on the method of forming a coating film on the substrate, and this will be described. The composition solution thus prepared can be used by filtering a micropore filter of about 0.5 μπι or the like. <Method for Forming Cured Film> The present invention is also preferably a method for forming a cured film comprising a cured film as an interlayer insulating film, a protective film or a separator, which is composed of the radiation sensitive resin, and the like: (1) on a substrate a step of forming the radiation-sensitive resin composition thereon; (2) a step (4) of irradiating at least a part of the coating film with radiation; and a step of developing the coating film irradiated with the radiation (4) on the developed film The step of firing. According to the method of the present invention using the radiation-sensitive resin composition, heat resistance, chemical resistance, and light transmittance can be formed. The methyl group is high-boiling, and when it is preferably b 30-mass, when it is applied, it can be formed into an arbitrary form. The concentrated component is concentrated in the shape of the pores. The film of the present invention; •, and the formation of a flat, -41 - 201207558 properties and linear thermal expansion resistance are obtained in a well-balanced cured film. The steps are described in detail below. [Step (1)] In this step, a transparent conductive film is formed on one surface of a transparent substrate, and a coating film of a radiation-sensitive resin composition is formed on the transparent conductive film. Examples of the transparent substrate include a glass substrate such as soda lime glass or non-glass, and a material selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate, polyether oxime, polycarbonate, and polyfluorene. A resin substrate composed of a plastic such as an imide. Examples of the transparent conductive film provided on one surface of the transparent substrate include a NESA film composed of tin oxide (Sn〇2) (registered trademark of PPG Corporation) and an indium oxide-tin oxide (In2〇3_Sn〇2). Ιτο膜等. When a coating film is formed by a coating method, after applying a solution of the radiation sensitive resin composition onto the transparent conductive film, it is preferred to pre-baking the coated surface to form a coating film. The solid content concentration of the composition solution used in the coating method is preferably 5% by mass to 5% by mass, more preferably 10% by mass to 40% by mass, and particularly preferably is% by mass to 35% by mass. The coating method is, for example, a spray coating method, a roll coating method, a = transfer coating method (spin coating method), a slit coating method (slot die coating method), a bar coating method, an inkjet coating method, or the like. Among these methods, a spin coating method or a slit coating method is preferred. The prebaking conditions are preferably 70t to 12〇t, more preferably 丨15 minutes left to right, depending on the type of the various components, the blending ratio, and the like. The film thickness after pre-baking of the coating film is preferably 0.5 μm to 10 μmη, more preferably 1·0 μιη to 7 · 0 μηι 〇-42-201207558 [Step (2)] This step is at least for the formed coating film. A part of the radiation is irradiated. In this case, when only a part of the coating film is irradiated, the enamel is irradiated by, for example, a reticle having a predetermined pattern. Examples of the radiation used during the irradiation include visible light, ultraviolet light, and far ultraviolet light. Among them, radiation having a wavelength in the range of 250 nm to 550 nm is preferable, and radiation containing ultraviolet rays of 3 6 5 n m is more preferable. The radiation exposure amount (exposure amount) is preferably 100 J/m 2 to 5,000 J/m 2 as the intensity value when the irradiation radiation wavelength is 365 nm measured by an illuminometer (Ο AI model 356, Optical Associates Inc.). It is 200J/m2~3, 〇〇〇j/m2. The radiation sensitive linear resin composition has the following advantages as compared with the conventionally known composition: radiation sensitivity is high, and even if the radiation irradiation 1 is 700 J/m 2 or less or even 6 〇〇 j/m 2 or less, it is possible to obtain A cured film such as an interlayer insulating film, a protective film or a separator having a desired film thickness, a good shape, excellent adhesion, and high hardness. [Step (3)] In this step, the coating film irradiated with the above-described radiation is developed to remove the unnecessary portion' to form a predetermined pattern. The developing solution to be used for the development may, for example, be an aqueous solution of a basic compound such as an inorganic base such as sodium hydroxide, potassium hydroxide or sodium carbonate, or a quaternary ammonium salt such as tetrakisyl ammonium hydroxide or tetraethylammonium hydroxide. Further, an appropriate amount of an organic solvent such as methanol or ethanol and/or a surfactant may be added to an aqueous solution of the above basic compound. -43- 201207558 Mu, i, for the development method, for example, Paddle, soaking, and dripping. As the development time, it is preferably 10 seconds to 180 seconds at normal temperature. After the development treatment, for example, water washing is performed for 30 seconds to 90°, and then the air is dried by compressed air or airtight to obtain a desired pattern. L Step (4)] This step is obtained by adding a rail cup, a sizzling plate, and a heating device suitable for the §. The coating film is fired (after the baking is used for the firing temperature, preferably 100 〇C 〜2 〇〇 ° γ, φ 乂 i i 更 C is preferably 15 〇 C 〜 180 ts. Sexual tree: The finished product has both storage stability and sufficient radiation sensitivity while achieving low-temperature firing as described above. Therefore, the sensitizing radiation resin composition is suitable for use as a flexible display benefit for low-temperature firing. The shape of the cured film such as the interlayer insulating film, the protective film, and the separator used. The firing time is, for example, preferably 5 minutes to 3 minutes on a hot plate, and 30 minutes to 180 minutes in an oven. <Manufacturing Method of Display Element> The present invention preferably includes a display element including the cured film. The display element can achieve excellent voltage holding ratio. As a manufacturing method of the display element, first prepare a pair (two pieces) a transparent substrate having a transparent conductive film (electrode) on one surface, and a spacer or a protective film or both are formed on the transparent conductive film of one of the substrates by using the radiation-sensitive resin composition as described above. An alignment film having a liquid crystal alignment ability is formed on the transparent conductive film and the spacer or the protective film on the substrate. The substrates are arranged to face each other in such a manner that the surface of the alignment film faces the inner side, and the liquid crystal of each alignment film The alignment direction is orthogonal or anti-parallel, and the relative arrangement is performed at a spacing of -44 - 201207558 fixed gap (cell gap), and the liquid crystal is filled in the interstitial space of the substrate (the alignment film and the spacer). The holes constitute a liquid crystal cell, and the polarizing plate is attached to the two outer surfaces of the liquid crystal cell in such a manner that the polarizing direction of the polarizing plate and the liquid crystal of the alignment film formed on one surface of the substrate are oriented or positively oriented. 'The display element of the present invention can be obtained. The method of forming a transparent conductive crucible, an interlayer insulating film, a protective film or an isolation: a transparent substrate to the film. along the end of the latter substrate = two Apply UV curing type sealant, then use liquid crystal distributor to add liquid crystal by micro 2 ,, and bond the two substrates under the above. For the above: 1 part, The high-performance mercury lamp is used to illuminate the ultraviolet ray, and after sealing the two bases 1, the two outer surfaces of the liquid crystal cell are placed on the front surface of the liquid crystal cell, thereby obtaining the display element of the present invention. The n-type liquid crystal of the present invention is obtained by the above various methods. The smectic liquid 曰 $ U exemplifies, for example, a polarizing plate to be used, which can be classified into a helium gas and a Japanese outer side, and a side is formed by stretching and absorbing iodine on the polyethylene glycol. "H film": a polarizing plate obtained from a cellulose acetate protective film, or a polarizing plate made of the same. The ruthenium film itself is subjected to f column ^ 1 π π 1 her case 欲 * 00 but the actual J 奵 the present invention The detailed application is not an explanation for the limitation of the present invention-45-201207558 <[A] Synthesis of Copolymer> [Synthesis Example 1] In a flask equipped with a condenser and a stirrer, 5 was added. Parts by mass of 2,2-alcoholic bis(2,4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol fluorenylethyl. Next, 20 parts by mass of styrene, 12 parts by mass of mercaptopropyl acid, 28 parts by mass of dicyclopentyl methacrylate, and 4 parts by mass of glycidyl methacrylate were added, and the mixture was slowly stirred with nitrogen while stirring. The temperature of the gluten solution was raised to 7 (TC, and the temperature was maintained for 5 hours to carry out polymerization) to obtain a solution containing the copolymer (A-1). The obtained copolymer solution had a solid content concentration of 31.3%, and the copolymer ( A-1) has a Mw of 12, 〇〇〇. Also, 'solid content concentration means a ratio of the copolymer to the total mass of the copolymer solution. [Synthesis Example 2] In a flask equipped with a condenser and a stirrer, 5 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol methyl ethyl ether, followed by addition of 1 part by mass of styrene and 12 parts by mass of fluorenyl group Acrylic acid, 23 parts by mass of tricyclodicyclopentyl methacrylate, 2 parts by mass of glycidyl methacrylate, 20 parts by mass of 2-mercapto glycidyl methacrylate, and 10 parts by mass of tetrahydro methacrylate糠 ester, after replacing with nitrogen, 'add 5 parts by mass of 1,3-butadiene, while slowly Mixing, while raising the temperature of the solution to 7 (TC, maintaining the temperature for 5 hours to carry out polymerization, thereby obtaining a solution containing the copolymer (A-2). The obtained copolymer solution has a solid concentration of 31.5%. The Mw of the copolymer (A-2) was 1 Torr, 10 〇〇 - 46 - 201207558 [Synthesis Example 3] 5 parts by mass of 2,2'-azobis (in the flask equipped with a condenser and a stirrer) was added. Isobutyronitrile) and 220 parts by mass of diethylene glycol methyl ethyl ether, followed by 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 Glycidyl acrylate was stirred while stirring, and the temperature of the solution was raised to 80 ° C, and the temperature was maintained for 5 hours to carry out polymerization to obtain a solution containing the copolymer (A-3). The component concentration was 31.0%, and the Mw of the copolymer (Α·3) was 1 〇, 〇〇〇. <Preparation of a radiation-sensitive resin composition for forming a cured film> The details of the various components are as follows: [B] Polymeric Compound B- 1: Mixture of dipentaerythritol pentapropionate and dipentaerythritol hexaacrylate (KAYARAD DPHA, Nippon Kayaku Co., Ltd.) B-2: Mixture of multifunctional acrylate compounds (KayaRAD DPHA-40H , Sakamoto Chemical Co., Ltd.) B-3: 1,9-decanediol dipropanyl acid g-B-4: pentaerythritol tetraacrylate B-5: trimethylolpropane triacrylate B-6 Rebel-based self-promoting monoacrylic acid vinegar (ARONIXM-5300, East Asia Synthetic Company) B-7: Spearic acid-modified neopentyl alcohol triacrylate (ARONIXTO-756, East Asia Synthetic Company) B - 8 : Ring Oxygen bromide modified dipentaerythritol hexamethylene phthalate-47- 201207558 [c] Radiation-sensitive linear polymerization initiator Cl : 1,2-octanedione-1-[4-(phenylthio)-2 -(0-benzoquinone)](IRGACURE OXEOl, Ciba Specialty Chemicals) C-2: Ethanol-l-[9-ethyl-6-(2-mercaptophenylhydrazino)-9H-carbazole -3-yl]-1-(0-acetamidine) (IRGACURE OXE02, Ciba Specialty Chemicals) C - 3 : 2 -mercapto-1 - (4-methylsulfanyl)-2 - mistinyl -1 - Copper (IRGACURE 907, Ciba Specialty Chemicals) C-4 : 2-Dimercaptoamino-2-(4- Methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one (IRGACURE 379 'Ciba Specialty Chemicals, Inc. [D] Compound D1: 5-nitro group represented by the following formula Interphthalic acid

COOHCOOH

02N02N

COOH D_2:下述式表示的5-經基間苯二甲酸COOH D_2: 5-aminoisophthalic acid represented by the following formula

COOHCOOH

-48- 201207558 [E]胺化合物 E-l : 2-苯基-4-曱基-5-羥基曱基咪唑 E-2 : 2-曱基咪唑 E-3 : 2-乙基-4-曱基咪唑 E-4 : 2-曱基苯并咪唑晶籠化合物作為下述所示晶籠化合物的F-1〜F-1 0是在分別作為主化合物上述[D ]化合物中包合[E ]胺化合物而形成的化合物。 F-1 : 0.67質量份的D-1和0.33質量份的E-l (2:1) F-2: 0.67質量份的D-2和0.33質量份的E-1 (2:1) F-3 : 0.67質量份的D-3和0.33質量份的E-1 (2:1) F-4: 0.67質量份的D-1和0.33質量份的E-2 (2:1) F-5 : 0_67質量份的D-2和0.33質量份的E-2 (2:1) F-6: 0.67質量份的D-3和0.33質量份的E-2(2:l) F-7 : 0.67質量份的D-1和0.33質量份的E-3 (2:1) F-8 : 0.67質量份的D-2和0.33質量份的E-3 (2:1) F-9 : 0.67質量份的D-3和0.33質量份的E-3 (2:1) F-10 : 0.50質量份的D-3和0.50質量份的E-4 (1:1) 溶劑 S -1 :丙二醇單曱基醚醋酸酯 S-2 :丙二醇單甲基醚 [實施例1〜15及比較例1〜4] 混合表1所示種類和使用量的[A]共聚物、[B]聚合性化合物、[C]聚合引發劑及晶籠化合物或[E]胺化合物， -49- 201207558 再混合作為任意成分的5質量份黏接助劑（r -環氧丙氧基丙基三曱氧基石夕烧）、〇.5質量份界面活性劑（FTX-218 NEOS公司）及0.5質量份貯存穩定劑（4-曱氧基苯酚）’添加溶劑（S-1)後，用孔徑0.5μιη的微孔濾器過濾，從而配製成各感放射線性樹脂組成物，黏度為1 6mPa· s。還有，欄中的「一」表示不使用該成分。另外，將各感放射線性樹脂組成物在25。(：下的黏度測定結果匯總列出。 <評價> 使用該感放射線性樹脂組成物進行以下評價。結果示於表2。 [貯存穩定性（％)] 將各感放射線性樹脂組成物在4 0 °C的烘箱中放置1 周，測疋放入供箱前後的黏度，求出黏度變化率（％ )，作為貯存穩定性（％)。貯存穩定性為5%以下時，判定為貯存穩定性為良好，超過5%時判定為貯存穩定性不好。還有，黏度是使用E型黏度計（VISC0NIC ELD R，東機產業公司）在25°C下測定的。 [敏感度（J/m2)] 在無驗玻璃基板上’藉由旋塗器塗布各感放射線性樹脂組成物’然後在10(rc的加熱板上預#烤2分鐘，從而形成膜厚的覆膜。接著，對於得到的覆膜，透過具有多個直徑纟8μιη〜15μπι &圍内#不 ' 形殘留圖案的光罩，用高壓水銀、使曝光量作為 200J/m ^OOOJ/m2範圍内的變數照射放射線。 0.40質量％四甲基氫氧化銨水溶 I、你〇 C下將顯影時間 -50- 201207558 作為變數’藉由液盛法顯影後，用純水洗滌1分鐘◊再在供箱中於1 80°c下後烘烤60分鐘，從而形成具有圓形殘留圖案的硬化骐。用鐳射顯微鏡（VK_85〇〇，Keyence 公司）測定圓形殘留圖案在顯影前和顯影後的高度。由該值和下述式求出膜殘留率（％)。膜殘留率（％)==(顯影後的高度/顯影前的高度）χ1 〇〇將膜殘留率為90%以上的曝光量作為敏感度 (J/m2)。曝光量為75〇J/m2以下時，判定為敏感度良好。還有’比較例4中不能形成圖案（表2中表示為「—」）。 [耐熱性（％)] 在上述硬化膜形成步驟中，對於不透過光罩而在 700J/m2的曝光量下曝光得到的塗膜，進一步在烘箱中於 230°C下加熱20分，用觸針式膜厚測定機（Alpha_Step IQ ’ KLATencor公司）測定加熱前後的膜厚。由該值和下述式求出膜殘留率（％)，作為耐熱性（％)。耐熱性（％)=(處理後膜厚/處理前膜厚）xl0〇 [耐化學試劑性（％)] 在上述的硬化膜形成步驟中，對於不透過光罩而在 700J/m2的曝光量丁曝光得到的塗膜，在加熱到6(rc的配向膜剝離液CHEMICLEANTS-204(三洋化成工業公司）中浸潰1 5分鐘，水洗後，再在烘箱中於} 2〇°C下乾燥1 5 分鐘。用觸針式膜厚測定機（Alpha-Step IQ，KLATencor 公司）測定該處理前後的膜厚，算出上述膜殘留率（％)，將其作為耐化學試劑性（％)。 -5 1- 201207558 [透光率（％)] 在上述的硬化膜形成步驟中，對於不透過光罩而在 700J/m2的曝光量下曝光得到的塗膜，使用分光光度計 (1 50-20型雙光束，日立製作所公司）測定波長4〇〇nm下的透光率（％)。該值為90%以上時’判定為透明性（％)良好0 [平坦性（nm)] 在Si〇2浸潰的玻璃基板上’使用顏料類彩色光阻劑-48- 201207558 [E]amine compound El: 2-phenyl-4-mercapto-5-hydroxyindenyl imidazole E-2 : 2-mercaptoimidazole E-3 : 2-ethyl-4-mercaptoimidazole E-4 : 2-mercaptobenzimidazole cage compound as F-1~F-1 0 of the crystal cage compound shown below is an inclusion of [E] amine compound in the above compound [D] as a main compound, respectively. And the compound formed. F-1 : 0.67 parts by mass of D-1 and 0.33 parts by mass of El (2:1) F-2: 0.67 parts by mass of D-2 and 0.33 parts by mass of E-1 (2:1) F-3: 0.67 parts by mass of D-3 and 0.33 parts by mass of E-1 (2:1) F-4: 0.67 parts by mass of D-1 and 0.33 parts by mass of E-2 (2:1) F-5 : 0_67 mass D-2 and 0.33 parts by mass of E-2 (2:1) F-6: 0.67 parts by mass of D-3 and 0.33 parts by mass of E-2 (2:1) F-7: 0.67 parts by mass D-1 and 0.33 parts by mass of E-3 (2:1) F-8 : 0.67 parts by mass of D-2 and 0.33 parts by mass of E-3 (2:1) F-9 : 0.67 parts by mass of D- 3 and 0.33 parts by mass of E-3 (2:1) F-10 : 0.50 parts by mass of D-3 and 0.50 parts by mass of E-4 (1:1) solvent S -1 : propylene glycol monodecyl ether acetate S-2: propylene glycol monomethyl ether [Examples 1 to 15 and Comparative Examples 1 to 4] The type and amount of [A] copolymer, [B] polymerizable compound, and [C] polymerization initiator shown in Table 1 were mixed. Agent and cage compound or [E]amine compound, -49- 201207558 and 5 parts by mass of adhesion aid (r-glycidoxypropyltrioxetane), 〇.5 Mass parts of surfactant (FTX-218 NEOS) and 0.5 parts by mass of storage stabilizer (4-methoxybenzene) After adding a solvent (S-1) to a phenol), it was filtered through a millipore filter having a pore size of 0.5 μm to prepare a radiation-sensitive resin composition having a viscosity of 16 mPa·s. Also, "one" in the column indicates that the component is not used. Further, each of the radiation sensitive resin compositions was at 25. (The viscosity measurement results are summarized below. <Evaluation> The following evaluation was carried out using the radiation-sensitive resin composition. The results are shown in Table 2. [Storage stability (%)] Each of the radiation-sensitive resin compositions After being placed in an oven at 40 ° C for 1 week, the viscosity before and after the tank was placed in the tank, and the viscosity change rate (%) was determined as the storage stability (%). When the storage stability was 5% or less, it was judged as The storage stability was good, and it was judged that the storage stability was not good when it exceeded 5%. Also, the viscosity was measured at 25 ° C using an E-type viscometer (VISC0NIC ELD R, Toki Sangyo Co., Ltd.). J/m2)] On each of the glass substrates, 'the respective radiation-sensitive resin compositions were coated by a spin coater' and then baked for 2 minutes on a hot plate of 10 (rc) to form a film having a film thickness. For the obtained film, a reticle having a plurality of residual patterns of 纟8 μm to 15 μm in the range of 不8 μm to 15 μm is used, and the exposure amount is irradiated as a variable in the range of 200 J/m ^OO J/m 2 with high-pressure mercury. Radiation 0.40% by mass of tetramethylammonium hydroxide water soluble I, 〇C, the development time -50 - 201207558 as a variable 'developed by liquid enrichment method, washed with pure water for 1 minute, then baked in the box at 180 ° C for 60 minutes, thus forming a circle Hardening 残留 of the residual pattern. The height of the circular residual pattern before and after development was measured with a laser microscope (VK_85〇〇, Keyence Corporation). The film residual ratio (%) was determined from the value and the following formula. (%) == (height after development/height before development) χ1 〇〇 The exposure amount of the film residual ratio of 90% or more is taken as the sensitivity (J/m2). When the exposure amount is 75 〇J/m2 or less, It was judged that the sensitivity was good. Further, in Comparative Example 4, the pattern could not be formed (indicated as "-" in Table 2). [Heat resistance (%)] In the above-mentioned cured film forming step, the 700 J was not passed through the mask. The coating film obtained by exposure at an exposure amount of /m2 was further heated in an oven at 230 ° C for 20 minutes, and the film thickness before and after heating was measured by a stylus type film thickness measuring machine (Alpha_Step IQ 'KLATencor Co., Ltd.). The film residual ratio (%) was determined as the heat resistance (%) by the following formula. (%) = (film thickness after treatment / film thickness before treatment) xl0 〇 [chemical resistance (%)] In the above-described cured film forming step, exposure at 700 J/m 2 is not transmitted through the reticle The obtained coating film was immersed in a 6 (rc aligning film peeling liquid CHEMICLEANTS-204 (Sanyo Chemical Industry Co., Ltd.) for 15 minutes, washed with water, and then dried in an oven at 1 2 ° C for 15 minutes. The film thickness before and after the treatment was measured by a stylus type film thickness measuring machine (Alpha-Step IQ, KLATencor Co., Ltd.), and the film residual ratio (%) was calculated and used as chemical resistance (%). -5 1-201207558 [Light transmittance (%)] In the above-described cured film forming step, a coating film obtained by exposure at an exposure amount of 700 J/m 2 without passing through a photomask was used with a spectrophotometer (1 50- The 20-type double beam, Hitachi, Ltd.) measures the light transmittance (%) at a wavelength of 4 〇〇 nm. When the value is 90% or more, it is judged that the transparency (%) is good. 0 [Flatness (nm)] On a glass substrate impregnated with Si〇2, a pigment-based color resist is used.

(JCR RED 689、JCR GREEN 706 及 CR 8200B，以上 JSR 公司）’按如下方式形成紅、綠及藍3色的條狀彩色濾光片。具體來說’使用旋塗器在Si〇2浸潰的玻璃基板上塗布上述彩色光阻劑中的1種顏色，在加熱板上於9〇〇c下預烘烤150秒’形成塗膜。然後使用曝光機（Can〇n PLA501F，canon公司），透過規定圖案的光罩，按換算成i線為2,000J/m2的曝光量照射ghi線（波長436nm、 405nm、3 65nm 的強度比=2.7 ·· 2.5 : 4.8)，然後使用 0.05 質量％氫氧化鉀水溶液進行顯影，並用超純水沖洗6〇秒。接著’再在烘箱中於230。(：下熱處理30分鐘，從而形成單色的條狀彩色濾光片。按3種顏色重複進行該操作，從而形成紅、綠及藍3色的條狀彩色濾光片（條寬 200μπι)。按照測定長度2,000μιη、測定範圍2,000μηι邊長的方形、測定方向為紅、綠、藍方向的條帶線短軸方向及紅•紅、綠•綠、藍·藍的同色條帶線長軸方向這兩個方向、各個方向的測定點數5(合計η數為1〇)，利用接觸式膜厚測定裝置（Alpha-Step KLA Tencor公司） -52- 201207558 測定彩色濾光片基板的表面凹凸時，為丨〇 μιη。在形成了彩色慮光片的基板上，用旋塗器塗布各熱硬化性樹脂組成物’然後在加熱板上於9 0 °c預供烤5分鐘形成塗膜後’再在清潔烘箱中於1 80°C下後烘烤60分鐘，從而形成相對於彩色濾光片上表面來說膜厚約2.0μιη的保護膜。對於這樣形成的彩色濾光片上具有保護膜的基板，利用接觸式膜厚測定裝置（Alpha-StepKLATencor公司）測定保護膜的表面凹凸。該測定是按照測定長度 2,000μιη、測定範圍2,000μιη邊長的方形、測定方向為紅、綠、藍方向的條帶線短軸方向及紅•紅、綠•綠、藍· 藍的同色條帶線長軸方向這兩個方向，各個方向的測定點數η=5(合計η數為10)進行實施，求出各個測定的最向部分和最底部分的高低差值（nm)的1 〇次的平均值，作為平坦性（nm)。該值為200nm以下時，判定為平坦性良好。 [線熱膨脹係數（ppm/°C )] 在上述的硬化膜形成步驟中，不透過光掩膜而在 7〇〇:/m2的曝光量下曝光’形成塗膜。然後在烘箱中於 1 8〇 C下熱處理60分鐘進行硬化，從而形成測定用塗膜 '然後’對於該塗膜’利用設置有溫度改變裝置的擴圓偏振計（DVA-36LH，溝尻光學工業所公司），在氮氣氛下：使測定時的升溫速度為分、使測定溫度範圍為 2〇 C〜200。。，測定在各個測定溫度下膜厚的變化量，對溫度作圖，由其近似直線求出斜率b，藉由下述式求出線熱膨脹係數a (ppm/°C )。τ表示初始膜厚。 *53* 201207558(JCR RED 689, JCR GREEN 706 and CR 8200B, the above JSR company) A strip color filter of three colors of red, green and blue was formed as follows. Specifically, one of the above-mentioned color resists was applied onto a glass substrate impregnated with Si 2 using a spin coater, and pre-baked on a hot plate at 9 ° C for 150 seconds to form a coating film. Then, using an exposure machine (Can〇n PLA501F, canon), the ghi line was irradiated with an exposure amount of 2,000 J/m2 converted into an i-line through a mask of a predetermined pattern (intensity ratio of wavelengths of 436 nm, 405 nm, and 3 65 nm = 2.7) ·· 2.5 : 4.8), and then developing with a 0.05% by mass aqueous potassium hydroxide solution, and rinsing with ultrapure water for 6 sec. Then ' again in the oven at 230. (: The heat treatment was performed for 30 minutes to form a monochromatic strip-shaped color filter. This operation was repeated in three colors to form strip-shaped color filters of red, green, and blue colors (bar width: 200 μm). According to the measurement of the length of 2,000 μm, the measurement range of 2,000 μηι side length square, the measurement direction of the red, green, blue direction of the strip line short axis direction and the red, red, green, green, blue and blue color of the same color strip line long axis The number of measurement points in the two directions and in each direction is 5 (the total number of η is 1 〇), and the surface unevenness of the color filter substrate is measured by a contact type film thickness measuring device (Alpha-Step KLA Tencor) -52 - 201207558 In the case of 丨〇μιη, on the substrate on which the color filter is formed, each thermosetting resin composition is coated with a spin coater and then pre-baked on a hot plate at 90 ° C for 5 minutes to form a coating film. 'Bake it again in a cleaning oven at 180 ° C for 60 minutes to form a protective film with a film thickness of about 2.0 μm relative to the upper surface of the color filter. Protect the color filter thus formed. Membrane substrate, using contact film thickness The device (Alpha-Step KLATencor Co., Ltd.) measures the surface unevenness of the protective film. The measurement is performed in a square shape with a length of 2,000 μm and a measurement range of 2,000 μm, and a short axis direction of the strip line in the measurement direction of red, green, and blue. Red, red, green, green, blue, and blue are in the two directions of the long-axis direction of the same color strip line. The number of measurement points in each direction η=5 (the total number of η is 10) is calculated, and the most normal direction of each measurement is obtained. The average value of the first half of the height difference (nm) of the partial and the bottom part is regarded as flatness (nm). When the value is 200 nm or less, it is judged that the flatness is good. [Line thermal expansion coefficient (ppm/°C) In the above-described cured film forming step, the coating film is formed by exposure at a light exposure amount of 7 〇〇:/m 2 without being transmitted through a photomask, and then heat-treated at 18 ° C for 60 minutes in an oven to be hardened. A coating film for measurement is formed, and then a circular polarization meter (DVA-36LH, Gully Optical Industries Co., Ltd.) provided with a temperature changing device is used for the coating film, and in a nitrogen atmosphere, the temperature increase rate during the measurement is divided into Make the measurement temperature range 2〇 C to 200. The amount of change in film thickness at each measurement temperature was measured, and the temperature was plotted, and the slope b was obtained from the approximate straight line, and the linear thermal expansion coefficient a (ppm/° C.) was obtained by the following formula. τ represents the initial film thickness. *53* 201207558

a= b/T 線熱膨脹係數為200ppm/°c以下時，可判定為線熱膨脹係數低，即使進行丨8〇〇c的後烘烤也能形成具有足夠硬化性的硬化膜。 [電壓保持率（％)] 在表面形成了防止鈉離子析出的si〇2膜，而且按規疋形狀洛鑛了 ITO(銦-氧化錫合金）電極的鈉玻璃基板上，旋塗各感放射線性樹脂組成物後，在9〇〇c的清潔烘相内進行10分鐘的預烘烤’形成膜厚2 〇μϊη的塗膜。然後，不透過光罩按500J/m2的曝光量對塗膜曝光。然後，將該基板在23。(：的由0.04質量％的氫氧化鉀水溶液組成的顯影液中浸潰1分鐘，I頁影後，用超純水洗滌風乾，再在1 80 C下後烘烤60分鐘，使塗膜硬化，形成永久硬化膜。然後，將該形成了像素的基板和僅按規定形狀蒸鍍了 ITO電極的基板，用混入了的玻璃珠的密封劑進行點合，然後注入Merck製液晶（MLC66〇8)，製作液晶胞。然後，將液晶胞放入6〇它的恒溫層中，用液晶電壓保持率測定系統（VHR_1A型，T〇Y〇 Technica公司）When the coefficient of thermal expansion of the a=b/T line is 200 ppm/°c or less, it can be judged that the linear thermal expansion coefficient is low, and a cured film having sufficient hardenability can be formed even after post-baking of 丨8〇〇c. [Voltage retention ratio (%)] A Si〇2 film that prevents the precipitation of sodium ions is formed on the surface, and the radiation is coated on the soda glass substrate of the ITO (indium-tin oxide alloy) electrode in a regular shape. After the resin composition, it was prebaked in a clean baking phase of 9 〇〇c for 10 minutes to form a coating film having a film thickness of 2 〇μϊη. Then, the coating film was exposed to an exposure amount of 500 J/m 2 without passing through a photomask. Then, the substrate is at 23. (: The solution consisting of 0.04% by mass aqueous potassium hydroxide solution was immersed for 1 minute, after I page shadow, it was air-dried with ultrapure water, and then baked at 180 C for 60 minutes to harden the coating film. Then, a permanent cured film is formed, and then the substrate on which the pixel is formed and the substrate on which the ITO electrode is deposited only in a predetermined shape are bonded with a sealing agent of the mixed glass beads, and then injected into a liquid crystal of Merck (MLC66〇8) ), the liquid crystal cell is produced. Then, the liquid crystal cell is placed in a constant temperature layer of 6 ,, and the liquid crystal voltage retention rate measuring system (VHR_1A type, T〇Y〇Technica company) is used.

測定液晶胞的電壓保持率（％)。此時施加的電壓為5 5V 的方形波、測定頻率為60HZ。電壓保持率由下述式求出。電壓保持率（％)=(16·7毫秒、後的液晶胞電位差/0毫秒時施加的電壓）x i 0 0 電壓保持率為9〇%以下時，意味著液晶胞經過16.7 f秒的時間不能將施加電壓保持在規定水準，不能使液晶充分配向，引起殘留影像等「烙印」的可能性大。 -54- 201207558 由表2的結果可知’實施例1〜1 5的該感放射線性樹脂組成物與比較例1〜4的組成物相比，具有良好的貯存穩定性和放射線敏感度。另外可知’由該感放射線性樹脂組成物形成的硬化膜即使是藉由2 0 〇 °c以下的低溫燒製形成’也具有優異的耐熱性、耐化學試劑性、透光率、平坦性及耐線性熱膨脹性。而且可知，具備該硬化膜的顯示元件的電壓保持率也是良好的。工業實用性本發明的硬化膜形成用感放射線性樹脂組成物可以容易地形成精細而精巧的圖案，同時滿足了貯存穩定性和低溫燒製’並且具有足夠的放射線敏感度。另外，由該感放射線性樹脂組成物形成的硬化膜的耐熱性、耐化學试劑性、透光率、平坦性及耐線性熱膨脹性優異。因此，該感放射線性樹脂組成物適宜用作希望進行低溫燒製的柔性顯不器等中使用的層間絕緣膜、保護膜及隔離物等硬化膜的形成材料。另外，具備該硬化膜的顯示元件也較佳為包含在本發明中，可以實現優異的電壓保持率。 -55- 201207558 表1 [A]共聚物 [B]聚合性化合物 [c]聚合引發劑晶籠化合物或[E]胺化合物溶劑黏度 (mPa.s) 種類使用量 (質量份）種類使用量 (質量份）種類使用量 (質量份）種類使用量 (質量份）實施例1 A-1 100 B-1 100 C-1 15 F-1 1 S-1 16 實施例2 A-1 100 B-1 100 C-1 15 F-2 1 S-1 16 實施例3 A-1 100 B-1/B-3 90/10 C-2 10 F-3 1 S-1 17 實施例4 A-1 100 B-1/B-3 90/10 C-2 10 F-4 1 S-1 16 實施例5 Α·1 100 B-1/B-4 80/20 C-2 10 F-5 1 S-2 16 實施例6 A-1 100 B-1/B-4 80/20 C-3 25 F-6 1 S-2 17 實施例7 A-1 100 B-1/B-2/B-6 60/40/10 C-3 25 F-7 1 S-2 16 實施例8 A-2 100 B-4/B-5 50/50 C-4 25 F-8 1 S-2 16 實施例9 A-2 100 B-1 100 C-4 25 F-9 1 S-2 16 實施例10 A-2 100 B-8 100 C-1/C-3 5/15 F-10 1 S-2 17 實施例11 A-2 100 B-1 100 C-2 10 F-3 0.5 S-1 15 實施例12 A-2 100 B-8/B-2 80/20 C-1/C-3/C-4 5/5/5 F-6 0.5 S-1 15 實施例13 A-2 100 B-3/B-4/B-5 30/30/40 C-1/C-3 5/15 F-9 0.5 S-1 15 實施例14 A-2 100 B-3/B-4/B-5 40/40/20 C-2/C-4 5/15 F-9 3 S-1 18 實施例15 A-2 100 B-1/B-2/B-8 30/30/40 C-1/C-3 5/15 F-10 2 S-1 17 比較例1 A-1 100 B-1 100 C-4 25 E-3 S-1 25 比較例2 A-1 100 B-1 100 C-4 25 E-4 1 S-2 25 比較例3 A-1 100 B-1 100 C-4 25 S-1 14 比較例4 A-3 100 B-1 100 C-4 25 • - S-1 14 表2 貯存穩定性 (%) 敏感度 (J/m2) 对熱性 (%) 耐化學試劑性 (%) 透光率 (%) 平坦性 (nm) 線熱膨脹係數 (ppm/°C) 電壓保持率 (%) 實施例1 5 600 98 99 96 180 190 98 實施例2 4 600 97 99 97 200 180 97 實施例3 5 700 98 98 96 180 200 97 實施例4 5 600 98 99 95 160 190 97 實施例5 4 700 98 98 90 180 180 96 實施例6 5 700 98 99 94 180 180 97 實施例7 4 700 98 99 97 180 200 97 實施例8 4 700 98 99 94 180 190 97 實施例9 3 600 98 99 96 180 190 96 實施例10 4 700 98 99 97 180 190 96 實施例11 4 700 98 99 94 180 200 97 實施例12 4 700 98 99 94 180 180 97 實施例13 3 700 99 99 97 180 190 97 實施例14 4 500 97 98 95 180 190 98 實施例15 4 500 99 99 95 180 190 97 比較例1 12 800 95 95 92 200 250 85 比較例2 10 800 96 95 88 210 240 87 比較例3 8 800 96 95 95 210 340 95 比較例4 20 - 94 94 82 350 240 65 -56- 201207558 【圖示簡單說明】無。【主要元件符號說明益〇 iThe voltage holding ratio (%) of the liquid crystal cell was measured. The voltage applied at this time was a square wave of 5 5 V, and the measurement frequency was 60 Hz. The voltage holding ratio was obtained by the following formula. Voltage holding ratio (%) = (16. 7 msec, liquid crystal cell potential difference / voltage applied at 0 msec) xi 0 0 When the voltage holding ratio is 9 〇 or less, it means that the liquid crystal cell cannot pass for 16.7 f seconds. Keeping the applied voltage at a predetermined level does not allow sufficient alignment of the liquid crystal, which is likely to cause "burn in" of residual images. -54-201207558 It is understood from the results of Table 2 that the radiation sensitive resin compositions of Examples 1 to 15 have better storage stability and radiation sensitivity than the compositions of Comparative Examples 1 to 4. In addition, it is understood that the cured film formed of the radiation-sensitive resin composition has excellent heat resistance, chemical resistance, light transmittance, and flatness even when it is formed by firing at a low temperature of 20 ° C or lower. Resistance to linear thermal expansion. Further, it is understood that the voltage holding ratio of the display element including the cured film is also good. Industrial Applicability The radiation-sensitive resin composition for forming a cured film of the present invention can easily form a fine and delicate pattern while satisfying storage stability and low-temperature firing' and having sufficient radiation sensitivity. Further, the cured film formed of the radiation sensitive resin composition is excellent in heat resistance, chemical resistance, light transmittance, flatness, and linear thermal expansion resistance. Therefore, the radiation sensitive resin composition is suitably used as a material for forming a cured film such as an interlayer insulating film, a protective film, and a separator which are used in a flexible display or the like which is desired to be fired at a low temperature. Further, a display element having the cured film is also preferably included in the present invention, and an excellent voltage holding ratio can be achieved. -55- 201207558 Table 1 [A] Copolymer [B] Polymerizable compound [c] Polymerization initiator Crystal cage compound or [E] Amine compound Solvent viscosity (mPa.s) Type of use (parts by mass) Type of use ( Parts by mass) Type of use (parts by mass) Type of use (parts by mass) Example 1 A-1 100 B-1 100 C-1 15 F-1 1 S-1 16 Example 2 A-1 100 B-1 100 C-1 15 F-2 1 S-1 16 Example 3 A-1 100 B-1/B-3 90/10 C-2 10 F-3 1 S-1 17 Example 4 A-1 100 B -1/B-3 90/10 C-2 10 F-4 1 S-1 16 Example 5 Α·1 100 B-1/B-4 80/20 C-2 10 F-5 1 S-2 16 Example 6 A-1 100 B-1/B-4 80/20 C-3 25 F-6 1 S-2 17 Example 7 A-1 100 B-1/B-2/B-6 60/40 /10 C-3 25 F-7 1 S-2 16 Example 8 A-2 100 B-4/B-5 50/50 C-4 25 F-8 1 S-2 16 Example 9 A-2 100 B-1 100 C-4 25 F-9 1 S-2 16 Example 10 A-2 100 B-8 100 C-1/C-3 5/15 F-10 1 S-2 17 Example 11 A- 2 100 B-1 100 C-2 10 F-3 0.5 S-1 15 Example 12 A-2 100 B-8/B-2 80/20 C-1/C-3/C-4 5/5/ 5 F-6 0.5 S-1 15 Example 13 A-2 100 B-3/B-4/B-5 30/30/40 C-1/C-3 5/15 F-9 0.5 S-1 15 Example 14 A-2 100 B -3/B-4/B-5 40/40/20 C-2/C-4 5/15 F-9 3 S-1 18 Example 15 A-2 100 B-1/B-2/B- 8 30/30/40 C-1/C-3 5/15 F-10 2 S-1 17 Comparative Example 1 A-1 100 B-1 100 C-4 25 E-3 S-1 25 Comparative Example 2 A -1 100 B-1 100 C-4 25 E-4 1 S-2 25 Comparative Example 3 A-1 100 B-1 100 C-4 25 S-1 14 Comparative Example 4 A-3 100 B-1 100 C -4 25 • - S-1 14 Table 2 Storage stability (%) Sensitivity (J/m2) Thermal (%) Chemical resistance (%) Transmittance (%) Flatness (nm) Linear thermal expansion coefficient (ppm/°C) Voltage Holding Ratio (%) Example 1 5 600 98 99 96 180 190 98 Example 2 4 600 97 99 97 200 180 97 Example 3 5 700 98 98 96 180 200 97 Example 4 5 600 98 99 95 160 190 97 Example 5 4 700 98 98 90 180 180 96 Example 6 5 700 98 99 94 180 180 97 Example 7 4 700 98 99 97 180 200 97 Example 8 4 700 98 99 94 180 190 97 Example 9 3 600 98 99 96 180 190 96 Example 10 4 700 98 99 97 180 190 96 Example 11 4 700 98 99 94 180 200 97 Example 12 4 700 98 99 94 180 180 97 Example 13 3 700 99 99 97 180 190 97 Example 14 4 500 97 98 95 180 190 98 Example 15 4 500 99 99 95 180 190 97 Comparative Example 1 12 800 95 95 92 200 250 85 Comparative Example 2 10 800 96 95 88 210 240 87 Comparative Example 3 8 800 96 95 95 210 340 95 Comparative Example 4 20 - 94 94 82 350 240 65 -56- 201207558 [Simple description] None. [Main component symbol description 益〇 i

Claims

201207558 VII. Patent application scope: 1. A radiation sensitive resin composition for forming a cured film, comprising: [A] a copolymer having (al) a carboxyl group-containing structural unit and (a2) an epoxy group-containing structural unit; , [B] a polymerizable compound having a ethylenically unsaturated bond, [C] a radiation-sensitive polymerization initiator, [D] a compound having a hydroxyl group or a carboxyl group, and an [E] amine compound; and at 25 ° C The viscosity is below 1.0 mmPa·s and below 50 mPa.s. 2. The radiation sensitive resin composition for forming a cured film according to claim 1, wherein the [E] amine compound may be contained in the [D] compound. 3. The radiation sensitive resin composition for forming a cured film according to the second aspect of the invention, wherein the [D] compound is selected from the group consisting of compounds represented by the following formulas (1) and (2), respectively. At least one compound, the [E] amine compound is a microphone. Sit compound or benzoh. Sitting on the compound,

R9 人, =^C〇〇H -58- 201207558 In the formula (1), X is a single bond, a methylene group or an alkylene group having 2 to 6 carbon atoms, and R1 to R8 are each independently a hydrogen atom. An alkyl group having a carbon number of 丨~12, a halogen atom, an alkoxy group having 1 to 12 carbon atoms or a phenyl group which may have a substituent; wherein R9 is a carbon number of 1 to 12 in the formula (2) An alkyl group, an alkoxy group having 1 to 12 carbon atoms, a nitro group or a hydroxyl group. 4. The radiation sensitive resin composition for forming a cured film according to the third aspect of the invention, wherein the compound represented by the above formula (1) is a compound represented by the following formula (1_",

In the formula G-1), X and R1 to R8 have the same meanings as in the above formula (1). 5. The radiation sensitive resin composition for forming a cured film according to any one of claims 4 to 4, wherein at least a part of [the amine compound is contained in the [D] compound. 6. The radiation sensitive resin composition for forming a cured film according to any one of claims 4 to 4, wherein the [c] radiation-sensitive polymerization initiator comprises an acetophenone compound and a ruthenium-based ruthenium compound. At least one of the selected groups. The radiation sensitive resin composition for forming a cured film according to any one of claims 1 to 4, further comprising at least one solvent selected from the group consisting of an alcohol solvent and a surface solvent. -59-201207558. The radiation-sensitive resin composition for forming a cured film according to any one of claims 1 to 4, which comprises the [E] amine compound in the [D] compound. The crystal cage compound is mixed into the [A] copolymer, the [B] polymerizable compound, and the [C] radiation sensitive polymerization initiator, and is obtained by setting the viscosity at 25 C to 1.0 mPa·s or more and 50 mPa·s or less. A method for producing a radiation sensitive resin composition for forming a cured film, which comprises mixing a crystal dragon compound obtained by encapsulating a [E] amine compound into a [D] compound, and [B] a polymerizable compound. And [c] the radiation-sensitive linear polymerization initiator is prepared by the step of setting the viscosity at 25t to be 1. 〇mPa · s or more and 50 mPa · s or less. A method of forming a cured film, comprising: (1) a step of forming a coating film of a radiation sensitive resin composition for forming a cured film according to any one of claims 1 to 8 on a substrate; (2) a step of irradiating at least a part of the coating film with radiation; (3) a step of developing a coating film irradiated with the radiation; and (4) a step of firing the coating film subjected to the development. 11. The method of forming the method of claim 10, wherein the firing temperature in the above step (4) is 200 eC or less. A cured film formed of a radiation sensitive resin composition for forming a cured film according to any one of claims 1 to 8 as an interlayer insulating film, a protective film or a separator. 13. Display element having a cured film as claimed in Item No. 12 of the patent application. -60-201207558 IV. Designation of representative drawings: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: Jwl 〇 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: