201107884 六、發明說明： 【發明所屬之技術領域】 本發明涉及適合作爲用於形成液晶顯示元件（LCD)的 保護膜和層間絕緣膜的材料的感放射線性組成物，由該組 成物形成的保護膜和層間絕緣膜，以及該保護膜和層間絕 緣膜的形成方法。 【先前技術】 液晶顯示元件等在其製造步驟中，藉由溶劑、酸或鹼 溶液等進行浸漬處理。另外，這種液晶顯示元件在藉由濺 射法形成佈線電極層時，元件表面的局部暴露在高溫中。 因此，爲了防止這種藉由溶劑等進行浸漬處理或高溫處 理’導致液晶顯示元件惡化或損傷，而實施在元件的表面 設置對這些處理具有耐受性的保護膜。 這種保護膜要求有對應當形成該保護膜的基板或下 層、以及在保護膜上形成的層的密合性高；膜自身平滑且 強韌；具有透明性：即使在高溫條件下也不會變色，可以 保持透明性；表面硬度足夠；耐磨損性優異等性能。作爲 用於形成滿足這些各種性質的保護膜的材料，已知的有例 如包含具有縮水甘油基的聚合物的負型感放射線性組成物 (參照日本特開平5 -7 845 3號公報）。一般來說，作爲保護膜 形成用的感放射線性組成物，與正型感放射線性組成物相 比，由於在成本上更有利，所以廣泛使用的是具有負型感 放射線性的感放射線性組成物。 201107884 另外，作爲形成保護膜使用的感放射線性組成物的成 分，主要使用丙烯酸類樹脂。相對於此，還嘗試使用耐熱 性和透明性比丙烯酸類樹脂更優異的聚矽氧烷類材料作爲 感放射線性組成物的成分（參照日本特開2000- 1 648號公 報 '日本特開2 006-178436號公報）。然而，聚矽氧烷類材 料和ITO(銦錫氧化物）透明導電膜的密合性不足，所以容易 在固化膜上產生皸裂（裂口），所以存在不適合作爲保護膜 的問題。此外，在作爲液晶顯示元件中的佈線的鉬佈線上， 密合性不足時，以鉬佈線爲起點，保護膜有可能容易產生 皸裂或剝落。因此，希望開發出耐熱性和透明性優異，同 時可以改善和ITO透明導電膜以及鉬佈線的密合性的聚矽 氧烷類感放射線性組成物。 另一方面，層間絕緣膜設置在液晶顯示元件等中，一 般用於使層狀配置的佈線之間絕緣。該液晶顯示元件的層 間絕緣膜必須形成佈線用接觸孔的圖案。作爲液晶顯示元 件的層間絕緣膜的形成用材料雖然開發出了成本上有利的 負型感放射線性組成物（參照日本特開2000- 162769號公 報）’但是這種負型組成物難以形成具有可以實際使用水準 的孔徑的接觸孔。因此’目前爲止，從形成接觸孔的優越 性的觀點出發，爲了形成液晶顯示元件的層間絕緣膜，廣 泛使用正型感放射線性固化性組成物（參照日本特開 2001 -354822 號公報）。 在製造這樣的液晶顯示兀件等時，根據其目的和步 201107884 驟，可以使用多種感放射線性組成物。最近，從削減成本 的觀點出發，嘗試將感放射線性組成物的種類統一化，希 望可以用一種感放射線性組成物形成耐熱性、透明性、平 坦性等要求性質重複的保護膜和層間絕緣膜。因此，要求 開發出一種感放射線性組成物，該組成物具備作爲保護膜 的形成材料，具有一般常用的負型感放射線性，滿足上述 要求的所有性質，同時具有作爲層間絕緣膜的形成材料所 必需的接觸孔形成能力。 具體而言，強烈希望開發出一種聚矽氧烷類負型感放 射線性組成物，該組成物可以簡單地形成平坦性、透明性、 耐熱性、密合性、耐皸裂、表面硬度和耐磨損性優異的保 護膜和層間絕緣膜，而且顯現出可以形成能夠實際使用的 接觸孔的解析度，而且具有高的保存穩定性。 [現有技術文獻] [專利文獻] [專利文獻1 ]日本特開平5 -7845 3號公報 [專利文獻2 ]日本特開2000-001 648號公報 [專利文獻3 ]日本特開2006- 1 7 8436號公報 [專利文獻4 ]日本特開2000-162769號公報 [專利文獻5 ]曰本特開2001-354822號公報 【發明內容】 本發明是基於以上問題提出的，其目的在於提供一種 聚矽氧院類負型感放射線性組成物，該組成物適合用於形 201107884 成平坦性、透明性、耐熱性（耐熱透明性）、表面硬度和耐 磨損性優異，同時對ITO透明導電膜的密合性以及耐皸裂 高的保護膜和層間絕緣膜，而且具有足夠的解析度和保存 穩定性；由該組成物形成的保護膜和層間絕緣膜，以及該 保護膜和層間絕緣膜的形成方法。 爲了解決上述問題的本發明是一種感放射線性組成 物，其包括： [A] 矽氧烷聚合物， [B] 選自由下式（1)和（3)分別表示的化合物構成的群組 中的至少一種矽烷化合物，以及 [C] 感放射線性酸產生劑或感放射線性鹼產生劑。 (R10)3Si—R2—Si(OR3)3 (1) (2)BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a radiation-sensitive composition suitable as a material for forming a protective film and an interlayer insulating film for a liquid crystal display element (LCD), and the protection formed by the composition a film and an interlayer insulating film, and a method of forming the protective film and the interlayer insulating film. [Prior Art] The liquid crystal display element or the like is subjected to an immersion treatment by a solvent, an acid or an alkali solution or the like in the production step thereof. Further, when such a liquid crystal display element is formed into a wiring electrode layer by a sputtering method, a part of the surface of the element is exposed to a high temperature. Therefore, in order to prevent the liquid crystal display element from being deteriorated or damaged by the immersion treatment or the high temperature treatment by the solvent or the like, a protective film having resistance to these treatments is provided on the surface of the element. Such a protective film is required to have high adhesion to a substrate or a lower layer on which the protective film should be formed, and a layer formed on the protective film; the film itself is smooth and strong; and has transparency: even under high temperature conditions Discoloration, can maintain transparency; surface hardness is sufficient; excellent wear resistance and other properties. As a material for forming a protective film which satisfies these various properties, for example, a negative-type radiation-sensitive composition containing a polymer having a glycidyl group is known (refer to Japanese Laid-Open Patent Publication No. Hei 5-7845-3). In general, as a radiation-sensitive linear composition for forming a protective film, since it is more advantageous in cost than a positive-type radiation-sensitive linear composition, a radiation-induced linear composition having a negative-type radiation is widely used. Things. 201107884 Further, as a component of the radiation sensitive composition used for forming the protective film, an acrylic resin is mainly used. On the other hand, it has been attempted to use a polyoxyalkylene-based material which is more excellent in heat resistance and transparency than an acrylic resin as a component of a radiation-sensitive composition (refer to Japanese Laid-Open Patent Publication No. 2000-1648) -178436). However, since the adhesion between the polyoxyalkylene-based material and the ITO (indium tin oxide) transparent conductive film is insufficient, cracking (cracking) is likely to occur in the cured film, so that it is not suitable as a protective film. Further, when the adhesion is insufficient in the molybdenum wiring which is the wiring in the liquid crystal display element, the protective film may be easily cleaved or peeled off from the molybdenum wiring. Therefore, it has been desired to develop a polyoxyalkylene-based radiation-sensitive linear composition which is excellent in heat resistance and transparency and which can improve adhesion to an ITO transparent conductive film and a molybdenum wiring. On the other hand, the interlayer insulating film is provided in a liquid crystal display element or the like, and is generally used to insulate between wirings arranged in a layer. The interlayer insulating film of the liquid crystal display element must form a pattern of contact holes for wiring. As a material for forming an interlayer insulating film of a liquid crystal display device, a negative-type radiation-sensitive composition which is advantageous in terms of cost has been developed (refer to Japanese Laid-Open Patent Publication No. 2000-162769), but such a negative-type composition is difficult to form. The contact hole of the aperture of the level is actually used. Therefore, in order to form an interlayer insulating film of a liquid crystal display device, a positive-type radiation-curable composition has been widely used (see JP-A-2001-354822). When manufacturing such a liquid crystal display element or the like, a plurality of radiation sensitive compositions can be used according to the purpose and step 201107884. Recently, from the viewpoint of cost reduction, attempts have been made to unify the types of radiation-sensitive components, and it is desirable to form a protective film and an interlayer insulating film having repeated properties such as heat resistance, transparency, and flatness by using a radiation-sensitive composition. . Therefore, it has been demanded to develop a radiation-sensitive linear composition which is provided as a protective film forming material, has a generally used negative-type radiation linearity, and satisfies all of the above-mentioned requirements, and has a material for forming an interlayer insulating film. The necessary contact hole forming ability. In particular, it is strongly desired to develop a polyoxane type negative-type radiation linear composition which can easily form flatness, transparency, heat resistance, adhesion, crack resistance, surface hardness and abrasion resistance. The protective film and the interlayer insulating film which are excellent in damage have a resolution which can form a contact hole which can be actually used, and have high storage stability. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. JP-A No. 2000-001 No. PCT Publication No. JP-A No. 2000-001 No. [Patent Document 4] Japanese Laid-Open Patent Publication No. 2000-162769 [Patent Document 5] JP-A-2001-354822 SUMMARY OF THE INVENTION The present invention has been made based on the above problems, and an object thereof is to provide a polyoxyl A negative-type radiation linear composition of the hospital type, which is suitable for the shape, transparency, heat resistance (heat-resistant transparency), surface hardness and abrasion resistance of the shape 201107884, and is dense to the ITO transparent conductive film. A protective film and an interlayer insulating film which are high in resistance and high in crack resistance, and have sufficient resolution and storage stability; a protective film and an interlayer insulating film formed of the composition, and a method of forming the protective film and the interlayer insulating film. The present invention to solve the above problems is a radiation sensitive composition comprising: [A] a siloxane polymer, [B] selected from the group consisting of compounds represented by the following formulas (1) and (3), respectively. At least one decane compound, and [C] a radioactive acid generator or a radiation-sensitive base generator. (R10)3Si—R2—Si(OR3)3 (1) (2)
Si(OR4)： (CH2)bSi(OR4): (CH2)b
(式（1)中，R1和R3各自獨立地是碳原子數爲卜4的烷 基，R2是碳原子數爲1~6的伸烷基、伸苯基或式（2)所示的 基團，式（2)中，a是1〜4的整數。式（3)中，R4、R5和R6各 自獨立地是碳原子數爲1~4的烷基’ b、c和d各自獨立地 是1〜6的整數。） 201107884 該感放射線性組成物由於具有負型的感放射線性，除 了上述[A]和[C]成分以外，還包含具有特定結構的矽烷化 合物[B]成分，所以可以形成一種液晶顯示元件用保護膜和 層間絕緣膜，該液晶顯示元件用保護和層間絕緣膜均衡性 良好地滿足平坦性、透明性、耐熱性（耐熱透明性）、表面 硬度和耐磨損性這樣一般要求的性質，同時還改善對ITO 透明導電膜的密合性和耐皸裂。另外，該感放射線性組成 物顯現出可以形成接觸孔的解析度，同時具有優異的保存 穩定性。由該感放射線性組成物得到的保護膜或層間絕緣 膜由於像這樣各種性質優異，所以特別適合在液晶顯示元 件中使用。 該感放射線性組成物的[A]矽氧烷聚合物較佳爲下式 (4)所示的水解性矽烷化合物的水解縮合物。 (R7)q—Si一(〇R8)4-q (4) (式（4)中，R7是碳原子數爲1〜20的非水解性的有機基 團，R8是碳原子數爲1~4的烷基，q是0~3的整數。） 在該感放射線性組成物中，藉由將作爲[A]矽氧烷聚合 物的上式（4)所示的水解性矽烷化合物的水解縮合物和上 述[B]成分一起使用，可以進一步改善形成的保護膜和層間 絕緣膜對ITO透明導電膜的密合性以及耐皸裂，同時胃以^ 得到更高的解析度。 該感放射線性組成物較佳爲進一步含有[D ]脫I水齊[(。像 ia樣’藉由進一步含有脫水劑’可以進一步提高該感放射 201107884 線性組成物的保存穩定性。(In the formula (1), R1 and R3 are each independently an alkyl group having a carbon number of 4, and R2 is an alkylene group having 1 to 6 carbon atoms, a phenyl group or a group represented by the formula (2). In the formula (2), a is an integer of 1 to 4. In the formula (3), R4, R5 and R6 are each independently an alkyl group having a carbon number of 1 to 4, and b and d are each independently It is an integer of 1 to 6.) 201107884 The radiation-sensitive linear composition has a negative radiation, and includes a decane compound [B] having a specific structure in addition to the above [A] and [C] components. It is possible to form a protective film for a liquid crystal display element and an interlayer insulating film which satisfactorily conforms to flatness, transparency, heat resistance (heat-resistant transparency), surface hardness, and abrasion resistance with the protection of the liquid crystal display element and the interlayer insulating film. Such generally required properties also improve the adhesion to the ITO transparent conductive film and resistance to cracking. Further, the radiation-sensitive composition exhibits a resolution in which contact holes can be formed while having excellent storage stability. Since the protective film or the interlayer insulating film obtained from the radiation-sensitive composition is excellent in various properties as described above, it is particularly suitable for use in a liquid crystal display device. The [A]nonane polymer of the radiation-sensitive composition is preferably a hydrolysis-condensation product of the hydrolyzable decane compound represented by the following formula (4). (R7)q—Si—(〇R8)4-q (4) (In the formula (4), R7 is a non-hydrolyzable organic group having 1 to 20 carbon atoms, and R8 is a carbon atom of 1~ The alkyl group of 4, q is an integer of 0 to 3.) In the radiation sensitive composition, hydrolysis of the hydrolyzable decane compound represented by the above formula (4) as the [A] siloxane polymer When the condensate is used together with the above-mentioned [B] component, the adhesion between the formed protective film and the interlayer insulating film to the ITO transparent conductive film and the crack resistance can be further improved, and the stomach can be further improved in resolution. The radiation sensitive composition preferably further contains [D] dehydrated water [(. Like ia-like] by further containing a dehydrating agent], the storage stability of the sensitized radiation 201107884 linear composition can be further improved.
該感放射線性組成物的[c ]感放射線性酸產生劑較佳 爲選自由三苯基銃鹽和四氫噻吩鎗鹽構成的群組中的至少 一種。另外，該yif 組成物的[c]感放射線性鹼產生 （X 劑較佳爲選自由2-硝基苄基環己基胺基甲酸酯和〇-胺基甲 醯基羥基醯胺構成的群組中的至少一種。藉由使用這些化 合物作爲感放射線性酸產生劑或感放射線性鹼產生劑’可 以進一步提高感放射線性組成物的解析度° 另外，本發明的液晶顯示元件用保護膜或層間絕緣膜 的形成方法包括： (1) 在基板上形成該感放射線性組成物的塗膜的步驟’ (2) 對步驟（1)形成的塗膜的至少一部分照射放射線的 步驟， (3) 將步驟（2)中照射放射線的塗膜顯影的步驟’以及 (4) 將步驟（3)顯影的塗膜加熱的步驟。 在該方法中，使用顯現出優異的解析度的上述感放射 線性組成物，利用感放射線性，藉由曝光、顯影’形成圖 案，從而可以容易地形成具有微細且精巧的圖案的液晶顯 示元件用保護膜或層間絕緣膜。而且，這樣形成的保護膜 和層間絕緣膜，對這些膜所要求的一般性質，也就是平坦 性、透明性、耐熱性（耐熱透明性）、表面硬度和耐磨損性’ 以及對ITO透明導電膜的密合性以及耐皸裂全部都平衡性 良好而優異。 201107884 如上述說明所示，本發明的感放射線性組成物藉由含 有上述[A]、[B]和[C]成分，可以形成能夠更加均衡地滿足 平坦性、透明性、耐熱性、耐熱透明性、表面硬度和耐磨 損性這樣一般要求的性質，此外還可以改善對ITO透明導 電膜的密合性以及耐皸裂的液晶顯示元件用保護膜和層間 絕緣膜。這樣形成的保護膜或層間絕緣膜特別適合在液晶 顯示元件中使用。另外，該感放射線性組成物顯現出可以 形成接觸孔程度的足夠的解析度，而且保存穩定性優異。 此外’該感放射線性組成物爲具有負型感放射線性的組成 物，與現有的具有正型感放射線性的組成物相比’在成本 方面也更加有利。 【實施方式】 本發明的感放射線性組成物包含[A]矽氧烷聚合物、[B] 選自由上式（1)和（3)分別表示的化合物構成的群組的至少 一種矽烷化合物、[C]感放射線性酸產生劑或感放射線性鹼 產生劑、以及其他任意成分（[D]脫水劑等）。 [A]成分：矽氧烷聚合物 [A]成分的矽氧烷聚合物只要是具有矽氧烷鍵的化合 物的聚合物，就沒有特別的限定。該[A]成分藉由對含有該 成分的感放射線性組成物照射放射線，以由後述[C]感放射 線性酸產生劑或感放射線性鹼產生的酸（酸性活性種）或鹼 (鹼活性種）爲催化劑，和[B]成分的矽烷化合物一起縮合， 形成固化物。 -10- 201107884 作爲[A]成分的矽氧烷聚合物，較佳爲下式（4)所示的水 解性矽烷化合物的水解縮合物。 (R7)q—Si—(OR8)4.q (4) (式（4)中，R7是碳原子數爲1〜20的非水解性的有機基 團’ R8是碳原子數爲1〜4的烷基，q是〇~3的整數。） 本申請案中所述的水解性矽烷化合物的「水解性基 團」，通常是指藉由在無催化劑、過量的水的共存下，在 室溫（約25 1)~約100 °C的溫度範圍內加熱，可以水解生成 矽烷醇基的基團；或者可以形成矽氧烷縮合物的基團。相 對於此’所述的「非水解性基團」是指在這種水解條件下， 不會產生水解或縮合，穩定存在的基團。在上式（4)所示的 水解性矽烷化合物的水解反應中，一部分的水解性基團可 以以未水解的狀態殘留在生成的矽氧烷聚合物中。另外， 在該組成物中，一部分水解性矽烷化合物以其分子中的一 部分或全部的水解性基團未水解的狀態，而且不和其他水 解性矽烷化合物縮合，以單體的狀態殘留。這裏所述的「水 解性矽烷化合物的水解縮合物「是指水解的矽烷化合物的 一部分砂院醇基之間反應、縮合形成的水解縮合物。 作爲上述R7所示的碳原子數爲1~20的非水解性有機 基團，可以列舉出碳原子數爲1~12的未取代、或被乙嫌 基、（甲基）丙烯醯基或環氧基的1個以上取代的烷基、碳 原子數爲6〜12的芳基、碳原子數爲7~12的芳烷基等。它 們可以是直鏈狀、支鏈狀或環狀，在同一分子內存在多個 -11 - 201107884 R7時，可以是它們的組合。另外’ R7可以包含具有雜原子 的結構單元。作爲這種結構單元’可以列舉出例如醚、酯、 硫醚等。 作爲上述R8所示的碳原子數爲1~4的烷基的例子，可 以列舉出甲基、乙基、正丙基、異丙基、丁基等。這些R8 中，從水解的容易性的觀點出發，較佳爲甲基和乙基。另 外，下標q是0~3的整數，更佳爲0~2的整數，特佳爲0 或1，最佳爲l°q爲0〜2的整數時，水解、縮合反應更容 易進行，結果是[A]成分和[B]成分的固化反應的速度更 大，進而可以提高該組成物的解析度和形成的保護膜對基 板的密合性。 上式（4)所示的水解性矽烷化合物可以列舉出被4個水 解性基團取代的矽烷化合物、被1個非水解性基團和3個 水解性基團取代的矽烷化合物、被2個非水解性基團和2 個水解性基團取代的矽烷化合物、被3個非水解性基團和 1個水解性基團取代的砂院化合物、或者該等的混合物。 作爲這種上式（4)所示的水解性矽院化合物的具體例 子，可以分別列舉出： 作爲被4個水解性基團取代的砂院化合物是四甲氧基 矽烷、四乙氧基矽烷 '四丁氧基矽烷、四苯氧基矽烷、四 苄氧基矽烷、四正丙氧基矽烷、四異丙氧基矽烷等； 作爲被1個非水解性基團和3個水解性基團取代的矽 烷化合@，是甲基三甲氧基矽烷、甲基三乙氧基矽烷、甲 -12- 201107884 基三異丙氧基矽烷、甲基三丁氧基矽烷、乙基三甲氧基矽 烷、乙基三乙氧基矽烷、乙基三異丙氧基矽烷、乙基三丁 氧基砂院、丁基二甲氧基砍院、苯基二甲氧基砂院、苯基 三乙氧基矽烷、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽 烷 '乙烯基三正丙氧基矽烷、3-甲基丙烯醯氧基丙基三甲 氧基矽烷、3 -甲基丙烯醯氧基丙基三乙氧基矽烷、3 -丙烯 醯氧基丙基三甲氧基矽烷、3-丙烯醯氧基丙基三乙氧基矽 烷、r-縮水甘油氧基丙基三甲氧基矽烷、γ·縮水甘油氧 基丙基三乙氧基矽烷、/3 -(3,4-環氧環己基）乙基三甲氧基 矽烷等； 作爲被2個非水解性基團和2個水解性基團取代的矽 烷化合物’是二甲基二甲氧基矽烷、二苯基二甲氧基矽烷、 二丁基二甲氧基矽烷等； 作爲被3個非水解性基團和1個水解性基團取代的矽 烷化合物’是三丁基甲氧基矽烷、三甲基甲氧基矽烷、三 甲基乙氧基矽烷、三丁基乙氧基矽烷等。 這些上式（4)所示的水解性矽烷化合物中，較佳爲被4 個水解性基團取代的矽烷化合物以及被1個非水解性基團 和3個水解性基團取代的矽烷化合物，特佳爲被1個非水 解性基團和3個水解性基團取代的矽烷化合物。作爲較佳 的水解性矽烷化合物的具體例子，可以列舉出、四乙氧基 矽烷、甲基三甲氧基矽烷、甲基三乙氧基矽烷、甲基三異 丙氧基矽烷、甲基三丁氧基矽烷、苯基三甲氧基矽烷、乙 •13· 201107884 基三甲氧基矽院、乙基三乙氧基砂院、乙基三異丙氧基砂 院、乙基三丁氧基砂院、丁基三甲氧基砂院、γ -縮水甘油 氧基丙基三甲氧基矽烷、3 -甲基丙烯醯氧基丙—三甲氧基 矽烷、3 -甲基丙烯醯氧基丙基三乙氧基矽烷。這種水解性 矽烷化合物，可以單獨使用一種，也可以將兩種以上組合 使用。 使上式（4)所示的水解性矽烷化合物水解、縮合的條 件，只要是能將上式（4)所示的水解性矽烷化合物的至少一 部分水解，將水解性基團轉變爲矽烷醇基，產生縮合反應 的條件，就沒有特別的限定，舉出一個例子，可以如下實 施。 上述式（4)所示的水解性矽烷化合物的水解、縮合使用 的水，較佳爲使用藉由反滲透膜處理、離子交換處理、蒸 餾等方法精製的水。藉由使用這種精製水，可以抑制副反 應，提高水解的反應性。水的用量’相對於上式（4)所示的 水解性矽烷化合物的水解性基團（-OR2)總計1 mol，較佳爲 0.1~3mol，更佳爲〇.3~2mol，進一步較佳爲O.5〜1.5mol量。 藉由使用這種量的水，可以將水解、縮合的反應速度最優 化。 作爲可以在上式（4)所示的水解性矽烷化合物的水 解、縮合中使用的溶劑沒有特別的限定’通常可以使用與 用於製備後述的感放射線性組成物的溶劑相同的溶劑。作 爲這種溶劑的較佳的例子，可以列舉出乙二醇單烷基醚乙 -14- 201107884 酸酯、二甘醇二烷基醚、丙二醇單烷 醚乙酸酯、丙酸酯類。這些溶劑中， 醚、二甘醇乙基甲基醚、丙二醇單甲 醚、丙二醇單甲基醚乙酸酯或3-甲氧 上式（4)所示的水解性矽烷化合物 佳在酸催化劑（例如，鹽酸、硫酸、硝 酸、三氟乙酸、三氟甲磺酸、磷酸、 各種路易士酸）、鹼催化劑（例如，胺 類、三級胺類、吡啶等含氮化合物， 氫氧化鈉等氫氧化物，碳酸鉀等碳酸屋 各種路易士鹼）或烷氧化物（例如，烷 烷氧化鋁）等催化劑的存在下進行》例 可以使用三異丙氧基鋁。從促進水解 發’作爲催化劑的用量，相對於1 m〇l 單體，較佳爲0.2mol以下，更佳爲〇 上式（4)所示的水解性矽烷化合物 的反應溫度和反應時間可以適當設定 述條件。反應溫度較佳爲4 0 ~ 2 0 0。(：， 應時間較佳爲3 0分鐘〜2 4小時，更佳: 擇這種反應溫度和反應時間，可以最 合反應。在該水解、縮合反應中，可 系內添加水解性矽烷化合物、水和催 應：或者也可以將水解性矽烷化合物 基醚、丙二醇單烷基 特佳爲二甘醇二甲基 基醚' 丙二醇單乙基 基丙酸甲酯。 的水解、縮合反應較 酸、甲酸、草酸、乙 酸性離子交換樹脂、 、—級胺類、二級胺 鹼性離子交換樹脂， I’乙酸鈉等羧酸鹽， 氧化锆、烷氧化鈦、 如’作爲烷氧化鋁， 、縮合反應的觀點出 水解性矽烷化合物的 .00001 〜O.lmol。 的水解、縮合反應中 。例如，可以採用下 更佳爲50-150°C。反 爲1〜1 2小時。藉由選 有效地進行水解、縮 以一次性地在反應體 化劑，進行一階段反 、水和催化劑分幾次 -15- 201107884 添加到反應體系中，進行多階段的水解和縮合反應。另外， 水解、縮合反應後，藉由加入脫水劑，然後進行蒸發脫水， 可以從反應體系除去水和生成的醇。該階段使用的脫水 劑，通常將過量的水吸附或內含完全消耗掉脫水能力，或 者過量的水是藉由蒸發除去的，所以並不在感放射線性組 成物中添加的後述的[D]成分的脫水劑的範疇內。 上式（4)所示的水解性矽烷化合物的水解縮合物的分 子量可以使用以四氫呋喃爲移動相的GPC(凝膠滲透層析 儀法），測定聚苯乙烯換算的數量平均分子量。而且，水解 縮合物的數量平均分子量通常較佳爲500〜10000的範圍內 的値，更佳爲1 000〜5 000的範圍內的値。藉由使水解縮合 物的數量平均分子量的値爲500以上，可以改善感放射線 性組成物的塗膜的成膜性。另一方面，藉由使水解縮合物 的數量平均分子量的値爲10000以下，可以防止感放射線 性組成物的感放射線性低下。 [B]成分：矽烷化合物 [B]成分是選自由下式（1)和（3)各自所示的化合物構成 的群組的至少一種矽烷化合物。該[B]成分，藉由對含有該 成分的感放射線性組成物照射放射線，以後述[C]感放射線 性酸產生劑或感放射線性鹼產生的酸（酸性活性種）或鹼（鹼 活性種）作爲催化劑，和[A ]成分的较氧院聚合物（較佳爲上 式（4)所示的水解性矽烷化合物的水解縮合物）一起縮合，形 成固化物。 -16- 201107884 (R10)3Si—R2—Si(OR3)3 (1) (式（1)中，R1和R3各自獨立地是碳原子數爲1~4的烷 基’ R2是碳原子數爲1〜6的伸烷基、伸苯基或式（2)所示的 基團。） (式（2)中 是1~4的整數。The [c] sensitizing radioactive acid generator of the radiation sensitive composition is preferably at least one selected from the group consisting of triphenylsulfonium salts and tetrahydrothiophene salt. Further, the [c] sensitizing radioactive base of the yif composition (X agent is preferably selected from the group consisting of 2-nitrobenzylcyclohexyl carbazate and fluorenyl-aminomethyl hydroxy decyl amide) At least one of the group. The resolution of the radiation sensitive composition can be further improved by using these compounds as a radiation sensitive acid generator or a radiation sensitive alkali generator. Further, the protective film for a liquid crystal display element of the present invention or The method for forming an interlayer insulating film includes: (1) a step of forming a coating film of the radiation sensitive composition on a substrate; (2) a step of irradiating at least a part of the coating film formed in the step (1) with radiation, (3) a step of heating the coating film irradiated with radiation in the step (2) and (4) a step of heating the coating film developed in the step (3). In the method, the above-described radiation-sensitive composition exhibiting excellent resolution is used. The material is formed into a pattern by exposure and development by radiation, and a protective film for a liquid crystal display element or an interlayer insulating film having a fine and delicate pattern can be easily formed. Protective film and interlayer insulating film, the general properties required for these films, that is, flatness, transparency, heat resistance (heat-resistant transparency), surface hardness and abrasion resistance', and adhesion to ITO transparent conductive film And all of the crust resistance are excellent in balance and good. 201107884 As shown in the above description, the radiation sensitive composition of the present invention can be formed to be more evenly balanced by containing the above [A], [B], and [C] components. Generally required properties such as flatness, transparency, heat resistance, heat-resistant transparency, surface hardness, and abrasion resistance, and also improved adhesion to an ITO transparent conductive film and a crack-resistant protective film for a liquid crystal display element and The interlayer insulating film. The protective film or the interlayer insulating film thus formed is particularly suitable for use in a liquid crystal display device. Further, the radiation sensitive composition exhibits sufficient resolution to form a contact hole, and is excellent in storage stability. 'The radiation-linear composition is a composition having a negative-type radiation linearity, and has a composition with a positive-type radiation linearity. It is also more advantageous in terms of cost. [Embodiment] The radiation sensitive composition of the present invention comprises [A] a decane polymer, and [B] is selected from the compounds represented by the above formulas (1) and (3), respectively. At least one decane compound, [C] sensitizing radioactive acid generator or sensitizing linear base generator, and other optional components ([D] dehydrating agent, etc.) of the group formed. [A] component: siloxane polymer The siloxane polymer of the component [A] is not particularly limited as long as it is a polymer having a compound having a decane bond. The component [A] is irradiated with radiation to the radiation-sensitive composition containing the component. An acid (acid active species) or a base (alkali active species) produced by a [C] sensitizing radioactive acid generator or a sensitizing radioactive base described later is used as a catalyst, and is condensed together with a decane compound of the component [B] to form a cured product. -10-201107884 The oxime polymer of the component [A] is preferably a hydrolyzed condensate of a hydrolyzable decane compound represented by the following formula (4). (R7)q—Si—(OR8)4.q (4) (In the formula (4), R7 is a non-hydrolyzable organic group having 1 to 20 carbon atoms' R8 is a carbon number of 1 to 4 The alkyl group, q is an integer of 〇~3.) The "hydrolyzable group" of the hydrolyzable decane compound described in the present application generally means that it is in the room by the coexistence of no catalyst and excess water. Heating at a temperature ranging from about 25 1 to about 100 ° C, a group capable of hydrolyzing to form a stanol group; or a group capable of forming a oxirane condensate. The term "non-hydrolyzable group" as used herein refers to a group which does not hydrolyze or condense under such hydrolysis conditions and which is stably present. In the hydrolysis reaction of the hydrolyzable decane compound represented by the above formula (4), a part of the hydrolyzable group may remain in the unhydrolyzed state in the produced siloxane polymer. Further, in the composition, a part of the hydrolyzable decane compound is not hydrolyzed in a part or all of the hydrolyzable group in the molecule, and is not condensed with another hydrolyzable decane compound, and remains in a monomer state. The "hydrolyzed condensate of a hydrolyzable decane compound" as used herein means a hydrolysis condensate formed by reaction and condensation between a part of a sand-based alcohol group of a hydrolyzed decane compound. The number of carbon atoms represented by the above R7 is 1-20. Examples of the non-hydrolyzable organic group include an unsubstituted alkyl group having 1 to 12 carbon atoms, or an alkyl group or a carbon atom substituted with an alkyl group, a (meth) acryl fluorenyl group or an epoxy group. An aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, etc. They may be linear, branched or cyclic, and when a plurality of -11 - 201107884 R7 are present in the same molecule, Further, 'R7 may contain a structural unit having a hetero atom. Examples of such a structural unit' include ethers, esters, thioethers, etc. The number of carbon atoms represented by the above R8 is 1 to 4. Examples of the alkyl group include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a butyl group, etc. Among these R8, a methyl group and an ethyl group are preferable from the viewpoint of easiness of hydrolysis. The subscript q is an integer from 0 to 3, more preferably an integer from 0 to 2, and particularly preferably 0 or 1. When the optimum is 1 to q, the hydrolysis and condensation reactions are more easily carried out, and as a result, the curing reaction rate of the [A] component and the [B] component is greater, and the resolution of the composition can be improved. The adhesiveness of the formed protective film to the substrate. The hydrolyzable decane compound represented by the above formula (4) includes a decane compound substituted with four hydrolyzable groups, one non-hydrolyzable group, and three a hydrolyzable group-substituted decane compound, a decane compound substituted with two non-hydrolyzable groups and two hydrolyzable groups, a sand compound compound substituted with three non-hydrolyzable groups and one hydrolyzable group, In addition, as a specific example of the hydrolyzable brothel compound represented by the above formula (4), each of the sand compound compounds substituted with four hydrolyzable groups is tetramethoxy decane. , tetraethoxy decane 'tetrabutoxy decane, tetraphenoxy decane, tetrabenzyloxy decane, tetra-n-propoxy decane, tetraisopropoxy decane, etc.; as a non-hydrolyzable group and 3 hydrolyzable groups substituted decane compound @, is methyl trimethyl Base decane, methyl triethoxy decane, methyl-12-201107884-triisopropoxy decane, methyl tributoxy decane, ethyl trimethoxy decane, ethyl triethoxy decane, ethyl three Isopropoxydecane, ethyl tributoxylate, butyl dimethoxy chopping, phenyl dimethoxy sand, phenyl triethoxy decane, vinyl trimethoxy decane, vinyl Triethoxy decane 'vinyl tri-n-propoxy decane, 3-methyl propylene methoxy propyl trimethoxy decane, 3-methyl propylene methoxy propyl triethoxy decane, 3- propylene fluorene Oxypropyltrimethoxydecane, 3-propenyloxypropyltriethoxydecane, r-glycidoxypropyltrimethoxydecane, γ-glycidoxypropyltriethoxydecane, /3 -(3,4-epoxycyclohexyl)ethyltrimethoxydecane; etc.; as a decane compound substituted by two non-hydrolyzable groups and two hydrolyzable groups, is dimethyldimethoxy Decane, diphenyldimethoxydecane, dibutyldimethoxydecane, etc.; as a decane substituted by three non-hydrolyzable groups and one hydrolyzable group Compound 'tributyl methoxy Silane, trimethyl Silane methoxy, ethoxy trimethyl silicon chloride, tributyl-ethoxy Silane like. Among the hydrolyzable decane compounds represented by the above formula (4), a decane compound substituted with four hydrolyzable groups and a decane compound substituted with one non-hydrolyzable group and three hydrolyzable groups are preferable. Particularly preferred is a decane compound substituted with one non-hydrolyzable group and three hydrolyzable groups. Specific examples of the preferred hydrolyzable decane compound include tetraethoxy decane, methyl trimethoxy decane, methyl triethoxy decane, methyl triisopropoxy decane, and methyl tributyl. Oxydecane, phenyltrimethoxydecane, B•13·201107884 bistrimethoxy enamel, ethyl triethoxy sand, ethyl triisopropoxy sand, ethyl tributoxy sand , butyl trimethoxy sand, γ-glycidoxypropyltrimethoxydecane, 3-methylpropenyloxypropane-trimethoxydecane, 3-methylpropenyloxypropyltriethoxy Base decane. These hydrolyzable decane compounds may be used singly or in combination of two or more. The conditions for hydrolyzing and condensing the hydrolyzable decane compound represented by the above formula (4) are such that at least a part of the hydrolyzable decane compound represented by the above formula (4) can be hydrolyzed to convert the hydrolyzable group into a stanol group. The conditions for generating the condensation reaction are not particularly limited, and an example thereof can be carried out as follows. The water used for the hydrolysis and condensation of the hydrolyzable decane compound represented by the above formula (4) is preferably water purified by a method such as reverse osmosis membrane treatment, ion exchange treatment or distillation. By using such purified water, the side reaction can be suppressed and the reactivity of hydrolysis can be improved. The amount of water used is 1 mol, preferably 0.1 to 3 mol, more preferably 0.3 to 2 mol, more preferably the hydrolyzable group (-OR2) of the hydrolyzable decane compound represented by the above formula (4). It is an amount of O.5~1.5mol. By using this amount of water, the reaction rate of hydrolysis and condensation can be optimized. The solvent to be used for the hydrolysis or condensation of the hydrolyzable decane compound represented by the above formula (4) is not particularly limited. Usually, the same solvent as that used for the preparation of the radiation sensitive composition described later can be used. Preferable examples of such a solvent include ethylene glycol monoalkyl ether B14-201107884 acid ester, diethylene glycol dialkyl ether, propylene glycol monoalkyl ether acetate, and propionate. Among these solvents, ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate or 3-methoxyl hydrolyzable decane compound represented by the formula (4) is preferably used in an acid catalyst ( For example, hydrochloric acid, sulfuric acid, nitric acid, trifluoroacetic acid, trifluoromethanesulfonic acid, phosphoric acid, various Lewis acids, and alkali catalysts (for example, amines, tertiary amines, nitrogen-containing compounds such as pyridine, hydrogen such as sodium hydroxide) An aluminum triisopropoxide can be used in the presence of a catalyst such as an oxide, a potassium carbonate or the like, and a catalyst such as an alkoxide (for example, an alkane alumina). The amount of the catalyst for promoting hydrolysis is preferably 0.2 mol or less with respect to 1 m〇l of the monomer, more preferably the reaction temperature and reaction time of the hydrolyzable decane compound represented by the above formula (4). Set the conditions described. The reaction temperature is preferably from 40 to 20,000. (:, the time should preferably be 30 minutes to 2 4 hours, more preferably: the reaction temperature and the reaction time can be selected to be the most suitable reaction. In the hydrolysis and condensation reaction, a hydrolyzable decane compound can be added internally, Water and catalysis: Alternatively, the hydrolyzable decane compound ether or propylene glycol monoalkyl group is preferably diethylene glycol dimethyl ether 'propylene glycol monoethyl propyl propionate. The hydrolysis and condensation reaction are more acidic. Formic acid, oxalic acid, acetic acid ion exchange resin, -amine, secondary amine basic ion exchange resin, carboxylate such as I' sodium acetate, zirconia, titanium alkoxide, such as 'as alkane alumina, condensation The viewpoint of the reaction is in the hydrolysis and condensation reaction of .00001 to 0.1 mol of the hydrolyzable decane compound. For example, it may be more preferably 50 to 150 ° C. The reverse is 1 to 12 hours. The hydrolysis and condensation are carried out once in the reaction agent, and the first-stage reverse, water and catalyst are added to the reaction system several times -15-201107884 to carry out multi-stage hydrolysis and condensation reaction. In addition, hydrolysis and condensation reaction are carried out. Rear, Water and the resulting alcohol can be removed from the reaction system by adding a dehydrating agent and then performing evaporative dehydration. The dehydrating agent used in this stage usually absorbs excess water or absorbs the dehydration ability completely, or the excess water is borrowed. In the range of the dehydrating agent of the component [D] to be described later, which is added to the radiation-sensitive composition, the molecular weight of the hydrolyzed condensate of the hydrolyzable decane compound represented by the above formula (4) can be used. Tetrahydrofuran is a mobile phase GPC (gel permeation chromatography method), and the number average molecular weight in terms of polystyrene is measured. Further, the number average molecular weight of the hydrolysis condensate is usually preferably in the range of 500 to 10,000, more preferably The enthalpy in the range of from 1 000 to 5,000. By setting the enthalpy of the number average molecular weight of the hydrolysis condensate to 500 or more, the film formability of the coating film of the radiation sensitive composition can be improved. The hydrazone of the number average molecular weight of the hydrolysis-condensation product is 10,000 or less, and the radiation-induced linearity of the radiation-sensitive composition can be prevented. [B] Component: decane compound [B] The fraction is at least one decane compound selected from the group consisting of compounds represented by the following formulas (1) and (3). The component [B] is irradiated with radiation by a radiation-sensitive composition containing the component. An acid (acidic active species) or a base (alkali active species) produced by a [C] sensitizing radioactive acid generator or a sensitizing radioactive base will be described later as a catalyst, and an oxygenated polymer of the [A] component (preferably the above formula) (4) The hydrolyzed condensate of the hydrolyzable decane compound shown) is condensed together to form a cured product. -16- 201107884 (R10) 3Si-R2—Si(OR3)3 (1) (in the formula (1), R1 and R3 is each independently an alkyl group having 1 to 4 carbon atoms. R2 is an alkylene group having 1 to 6 carbon atoms, a phenyl group or a group represented by the formula (2). (Expression (2) is an integer from 1 to 4.
Si(〇R4)3 (CH2)b °γΝγ〇 (3) (R50)3Si-fCH2·)^ X V>v(CH2)j-Si(OR6)3 (式（3)中，R4、R5和R6各自獨立地是碳原子數爲1~4 的烷基，b、c和d各自獨立地是1~6的整數。） 作爲式（1)的R1和R3的較佳的具體例子，可以列舉出 甲基、乙基、丙基、丁基。這些烷基中，更佳爲甲基、乙 基。作爲式（1)的R2的較佳的具體例子，可以列舉出亞甲 基、伸乙基、伸丙基、環丙烷基、環丁烷基、環戊烷基、 環己烷基、伸苯基。這些基團中，更佳爲亞甲基、伸乙基、 伸苯基。另外，R2爲式（2)所示的基團時，作爲式（2)中的a 較佳爲1或2。藉由使用這種較佳爲結構的式（1)的矽烷化 合物作爲[B】成分，可以提高和[A]成分的反應性。 作爲式（3)的R4、R5和R6的較佳的具體例子，從和[A] 成分的反應性的觀點出發，可以列舉出甲基、乙基、丙基、 -17- 201107884 丁基。這些院基中，更佳爲甲基。另外’式（3)中的b' c 和d，從和[A]成分的反應性和相容性的觀點出發’較佳爲 1 ~3的整數。 在該感放射線性組成物中’ [B]成分可以單獨使用一 種，也可以將2種以上組合使用。式（1)和（3)的砂院化合物 中，更佳爲具有式（3)所示的異氰脲酸環的矽烷化合物。像 這樣，藉由使用在1分子中具有3個結合了三院氧基甲砂 烷基的異氰脲酸環的矽烷化合物’可以得到顯示出高的放 射線靈敏度的感放射線性組成物’同時可以提高由該組成 物形成的保護膜和層間絕緣膜的交聯度。此外’含有這種 含有異氰脲酸環的矽烷化合物的感放射線性組成物’平坦 性高，且密合性優異’可以形成適合液晶顯示元件使用的 保護膜和層間絕緣膜。 作爲式（1)和（3)所示的矽烷化合物的具體例子’可以歹IJ 舉出雙（三乙氧基甲矽烷基）乙烷、雙（三甲氧基甲矽烷基） 甲烷、雙（三乙氧基甲矽烷基）甲烷、雙-1，2-(三甲氧基甲砍 烷基）乙烷、雙-1,6-(三甲氧基甲矽烷基）己烷、雙-1，6-(三乙 氧基甲矽烷基）己烷、雙-1，4-(三甲氧基甲矽烷基）苯、雙 -1,4-(三乙氧基甲矽烷基）苯、1,4-雙（三甲氧基甲矽烷基甲 基）苯、1,4-雙（三甲氧基甲矽烷基乙基）苯、M-雙（三乙氧 基甲矽烷基甲基）苯、1,4-雙（三乙氧基甲矽烷基乙基）苯、 參（三甲氧基甲矽烷基甲基）異氰脲酸酯、參（三乙氧基甲砂 烷基甲基）異氰脲酸酯、參（2-三甲氧基甲矽烷基乙基）異氛 [ -18- 201107884 脲酸酯、參（2-三乙氧基甲矽烷基乙基）異氰脲酸酯、參（3· 三甲氧基甲矽烷基丙基）異氰脲酸酯、參（3-三乙氧基甲矽烷 基丙基）異氰脲酸酯、[雙（2-三甲氧基甲矽烷基乙基）-(3-三 乙氧基甲矽烷基丙基）]異氰脲酸酯、[三甲氧基甲矽烷基甲 基-(2-三甲氧基甲矽烷基乙基）-(3-三甲氧基甲矽烷基丙基）] 異氰脲酸酯等。它們之中，從提高放射線靈敏度、所得的 保護膜和層間絕緣膜的平坦性的觀點出發，特佳爲1，4·雙 (三甲氧基甲矽烷基甲基）苯、雙（三乙氧基甲矽烷基）乙烷、 參（2-三甲氧基甲矽烷基乙基）異氰脲酸酯、參（3-三甲氧基 甲矽烷基丙基）異氰脲酸酯、參（3-三乙氧基甲矽烷基丙基） 異氰脲酸酯。 相對於100質量份[Α]成分，該感放射線性組成物中的 [Β]成分的用量，較佳爲5質量份〜70質量份，更佳爲10質 量份~50質量份。藉由使[Β]成分的用量爲5質量份~70質 量份，可以得到放射線靈敏度以及所得的保護膜和層間絕 緣膜的平坦性更加均衡性優異的感放射線性組成物。 [C]成分：感放射線性酸產生劑、感放射線性鹼產生劑 [C]成分的感放射線性酸產生劑或感放射線性鹼產生 劑定義爲藉由照射放射線，使[Α]成分的矽氧烷聚合物（較 佳爲上式（4)所示的水解性矽烷化合物的水解縮合物）與[Β] 成分的矽烷化合物進行縮合、固化反應時，可以放出作爲 催化劑使用的酸性活性物質或鹼性活性物質的化合物。另 外，作爲照射用於使[C]成分分解，產生酸性活性物質或鹼 -19- 201107884 性活性物質的陽離子或陰離子等的放射線，可以列舉 見光線、紫外線、紅外線、X射線、α射線、Θ射線 射線等。這些放射線中，從具有一定的能量等級，可 現大的固化速度，而且照射裝置比較廉價且小型化， 爲使用紫外線。 另外’還較佳爲將[C]成分的感放射線性酸產生劑 &射線性鹼產生劑和後述的自由基聚合引發劑一起使 ώ自由基聚合引發劑產生的中性活性物質的自由基不 Mi解性矽烷化合物的縮合反應，但是在[Α]成分具有 S聚合性官能團時，可以促進該官能團的聚合。 作爲[C]成分的感放射線性酸產生劑，較佳爲二苯 m鹽、三苯基锍鹽和四氫唾吩鑰鹽，特佳爲三苯基鏡 噻吩鑰鹽。作爲二苯基碘鎗鹽的具體例子，可以 苯基碘鑰四氟硼酸鹽、二苯基碘鑰六氟磷酸鹽、 基W鑰六氟砷酸鹽、二苯基碘鑰三氟甲磺酸鹽、二苯 鐵三氟乙酸鹽、二苯基碘鎗-對甲苯磺酸鹽、二苯基碘 基參（2,6-二氟苯基）硼酸鹽、4-甲氧基苯基苯基碘鑰四 酸鹽 '雙（4-三級丁基苯基）碘鑰四氟硼酸鹽、雙（4-三 基苯基）碘鑰六氟砷酸鹽、雙（4-三級丁基苯基）碘鑰三 擴酸鹽、雙（4-三級丁基苯基）碘鑰三氟乙酸鹽、雙（4-T基苯基）碘鑰-對甲苯磺酸鹽、雙（4-三級丁基苯基）碘 腦磺酸鹽等。 作爲三苯基毓鹽的具體例子，可以列舉出三苯基 出可 、7 以實 較佳 或感 用。 會促 自由 基碘 鹽和 列舉 二苯 基碘 鎗丁 氟硼 級丁 氟甲 三級 鑰樟 硫二 -20- 201107884 氟甲磺酸鹽、三苯基鏑樟腦磺酸鹽、三苯基鏑四氟硼酸鹽、 三苯基鏡三氟乙酸鹽、三苯基鏑-對甲苯磺酸鹽、三苯基鏑 丁基參（2,6-二氟笨基）硼酸鹽等。 作爲四氫噻吩鑰鹽的具體例子，可以列舉出1-(4-正丁 氧基萘-1-基）四氫噻吩鐵三氟甲磺酸鹽、1-(4-正丁氧基萘 -1-基）四氫噻吩鑰九氟正丁磺酸鹽、1-(4-正丁氧基萘-卜基） 四氫噻吩鑰-1，1，2,2-四氟代-2-(降萡烷-2-基）乙磺酸鹽、 1-(4-正丁氧基萘-1-基）四氫噻吩鑰- 2-(5-三級丁氧基醯氧基 二環[2.2.1]庚-2-基）-1，1，2,2-四氟代乙磺酸鹽、1-(4-正丁氧 基萘-1-基）四氫噻吩鑰-2-(6-三級丁氧基醯氧基二環[2.2.1] - 庚-2-基）-1，1，2,2-四氟代乙磺酸鹽、1-(4,7-二丁氧基-1-萘基） 四氫噻吩鎗三氟甲磺酸鹽等。 這些感放射線性酸產生劑中，從提高感放射線性組成 物的放射線靈敏度的觀點，特佳爲三苯基鏑三氟甲磺酸 鹽、三苯基鏑樟腦磺酸鹽、1-(4,7-二丁氧基-1-萘基）四氫噻 吩鑰三氟甲磺酸鹽。 作爲[C]成分的感放射線性鹼產生劑的例子，可以列舉 出2-硝基苄基環己基胺基甲酸酯、[〔（2,6·二硝基苄基）氧 基〕羰基]環己基胺、N-(2-硝基苄氧基羰基）吡咯啶、二[〔（2-硝基苄基）氧基〕羰基]己烷-1,6·二胺、三苯基甲醇、0-胺 基甲醯基羥基醯胺、0-胺基甲醯基肟、4-(甲基硫代苯甲醯 基）-1-甲基-1-味啉乙烷、（4·味啉苯甲醯基）-1-苄基-1-二甲 基胺基丙烷、2-苄基-2-二甲基胺基-1-(4-味啉苯基）-丁酮、 -21 - 201107884 六胺合鈷（III)參（三苯基甲基硼酸鹽）等。這些[C]成分的感 放射線性鹼產生劑中，從提高感放射線性組成物的放射線 靈敏度的觀點，特佳爲2-硝基苄基環己基胺基甲酸酯和0-胺基甲醯基羥基醯胺。 [C] 成分的感放射線性酸產生劑或感放射線性鹼產生 劑可以單獨使用一種，也可以將兩種以上混合使用。相對 於100質量份[A]成分，[C]成分的用量較佳爲0.1質量份~20 質量份，更佳爲1質量份〜10質量份。藉由使[C]成分的用 量爲0.1質量份~20質量份，可以得到放射線靈敏度、形成 的保護膜和層間絕緣膜的鉛筆硬度和耐熱性（耐熱透明性） 更加均衡性優異的感放射線性組成物。 [D]成分：脫水劑 [D] 成分的脫水劑定義爲可以藉由化學反應將水轉變 爲水以外的物質，或者藉由物理吸附或內含將水封閉住的 物質。藉由在該感放射線性組成物中任意含有[D ]脫水劑’ 可以減少從環境侵入的水分，或後述曝光照射步驟中’照 射放射線由[A]和[B]成分縮合產生的水分。因此’藉由使 用[D ]脫水劑，可以減少組成物中的水分’從而提高組成物 的保存穩定性。此外，認爲還可以提高[A]和[B]成分的縮 合的反應性，提高感放射線性組成物的放射線靈敏度。作 爲這種[D]脫水劑，較佳爲使用選自由羧酸酯、乙縮醛類（含 縮酮類）和羧酸酐構成的群組中的至少一種化合物。 作爲羧酸酯的較佳的例子，可以列舉出原羧酸酯 -22- 201107884 (orthocarboxylicacid)、殘酸甲砂院基酯等。作爲原殘酸酯 的具體例子，可以列舉出原甲酸甲酯、原甲酸乙酯、原甲 酸丙酯、原甲酸丁酯、原乙酸甲酯、原乙酸乙酯、原乙酸 丙酯、原乙酸丁酯、原丙酸甲酯、原丙酸乙酯等。另外， 這些原羧酸酯中，特佳爲原甲酸甲酯等原甲酸酯。作爲羧 酸甲矽烷基酯的具體例子，可以列舉出乙酸三甲基甲矽烷 基酯、乙酸三丁基甲矽烷基酯、甲酸三甲基甲矽烷基酯、 草酸三甲基甲矽烷基酯等。 作爲乙縮醛類的較佳的例子，可以列舉出酮類和醇的 反應物、酮類和二醇的反應物、烯酮甲矽烷基乙縮醛類。 作爲酮類和醇的反應物的具體例子，可以列舉出二甲基乙 縮醛、二乙基乙縮醛、二丙基乙縮醛等。 作爲羧酸酐的較佳的例子，可以列舉出甲酸酐、乙酸 酐、琥珀酸酐、馬來酸酐、鄰苯二甲酸酐、苯甲酸酐、乙 酸苯甲酸酐等。這些羧酸酐中，從脫水效果方面出發，較 佳爲乙酸酐和琥珀酸酐。 相對於100質量份[A]成分，使用[D]脫水劑時的量，較 佳爲0.1~50質量份，更佳爲0.5~30質量份，特佳爲l~l〇 質量份。藉由使[D]脫水劑的用量爲0.1〜50質量份，可以將 感放射線性組成物的保存穩定性最優化。 其他任意成分 本發明的感放射線性組成物除了上述[A]~[C]成分和 [D]成分（任意成分）以外，在不損害本發明的效果的範圍 -23- 201107884 內，根據需要可以含有[E]酸擴散控制劑、[F]自由基聚合引 發劑、[G]界面活性劑等其他任意成分。 在使用感放射線性酸產生劑作爲感放射線性組成物的 [C]成分時，[E]成分的酸擴散控制劑，具有下述作用，控制 照射放射線產生的酸性活性物質在組成物塗膜中的擴散， 抑制非曝光區域的固化反應。藉由將這種酸擴散控制劑和 [C]成分的感放射線性酸產生劑一起使用，可以進一步提高 感放射線性組成物的解析度（可以高精度地形成層間絕緣 膜的含接觸孔的所希望圖案的感放射線性質）。 作爲酸擴散抑制劑的例子，可以列舉出單烷基胺類、 二烷基胺類、三烷基胺類、芳香族胺類、烷醇胺類、脂肪 族胺類、含醯胺基的化合物、尿素化合物、咪唑類、吡啶 類、其他含氮雜環化合物等含氮化合物。 這些酸擴散抑制劑的具體例子’可以分別列舉出例如： 作爲單烷基胺類是正己基胺、正庚基胺、正辛基胺、 正壬基胺、正癸基胺等； 作爲二烷基胺類是二正丁基胺、二正戊基胺、二正己 基胺、二正庚基胺、二正辛基胺、二正壬基胺、二正癸基 胺等； 作爲三烷基胺類是三乙基胺、三正丙基胺、三正丁基 胺、三正戊基胺、三正己基胺、三正庚基胺、三正辛基胺、 三正壬基胺、三正癸基胺等； 作爲芳香族胺類是苯胺、N -甲基苯胺、N，N -二甲基苯 -24- .201107884 胺、2-甲基苯胺、3_甲基苯胺、4_甲基苯胺、4_硝基苯胺、 二苯基胺、三苯基胺、1-萘基胺、4，4’ -二胺基二苯基甲院、 4,4’ ·二胺基二苯基醚、4,4’ -二胺基二苯甲酮、44’ -二 胺基二苯基胺、2,2’ -雙（4-胺基苯基）丙烷、2-(3-胺基苯 基）-2-(4-胺基苯基）丙烷、2-(4-胺基苯基）-2-(3-羥基苯基） 丙烷、2-(4-胺基苯基）-2-(4-羥基苯基）丙烷、1，4-二[1-(4-胺基苯基）-1-甲基乙基]苯、丨，3_二[1-(4-胺基苯基）-i-甲基 乙基]苯等； 作爲烷醇胺類是乙醇胺、二乙醇胺、三乙醇胺等； 作爲脂肪族胺類是乙二胺、N，N，N’ ，N’ -四甲基乙二 胺、丁二胺、己二胺、Ν，Ν，Ν· ，N，-肆（2-羥基乙基）乙二胺、 N，N，N’ ，N’ -肆（2-羥基丙基）乙二胺、聚乙烯醯亞胺、聚稀 丙基胺、二甲基胺基乙基丙烯醯胺等； 作爲含醯胺基的化合物是甲醯胺、N-甲基甲醯胺、N，N-二甲基甲醯胺、乙醯胺、N-甲基乙醯胺、N，N-二甲基乙醯 胺、丙醯胺、苯甲醯胺、2 -吡咯啶酮、N -甲基吡咯啶酮等； 作爲尿素化合物是尿素、甲基腺、1,1-二甲基脲、1,3-二甲基脲、1，1，3,3·四甲基脲、1，3-二苯基脲、三丁基硫脲 等； 作爲咪唑類是咪唑 '苯並咪唑、2 -甲基咪唑、4 -甲基 咪唑、2-苯基咪唑、4-苯基咪唑、4-甲基-2-苯基咪唑等； 作爲吡啶類是吡啶、2-甲基吡啶、4-甲基吡啶、2-乙基 吡啶、4-乙基吡啶、2-苯基吡啶、4-苯基吡啶、3·甲基Μ α- 201107884 苯基吡啶、菸鹼、菸酸、菸酸醯胺、喹啉、8 -羥基喹啉 (8-oxyquinoline)、Iff 陡等： 作爲其他含氮雜環化合物是吡阱、吡唑、嘧啶、喹_ 啉、味啉、4-甲基味啉、哌哄、1.，4-二甲基哌阱、1,4-二氮 雜二環[2.2.2]辛烷' 2,4,6-參（2-吡啶基）-1,3,5-三畊等。 這些含氮化合物中，較佳爲三烷基胺類和吡啶類。作 爲特佳爲的三烷基胺類，可以列舉出三乙基胺、三正丁基 胺、三正戊基胺、三正己基胺、三正庚基胺、三正辛基胺。 另外，作爲特佳爲的吡啶類，可以列舉出2,4,6-參（2-吡啶 基）-1,3,5 -三畊、吡啶、2 -甲基吡啶、4 -甲基吡啶、2 -乙基 吡啶、4-乙基吡啶、2-苯基吡啶、4-苯基吡啶、3·甲基-4-苯基卩比陡、兹鹼、薛酸、兹酸醯胺、唾琳、8 -經基喹咐、 吖啶。這些酸擴散控制劑，可以單獨使用一種，或者也可 以將兩種以上混合使用。 相對於100質量份[A]成分，使用[E]酸擴散控制劑時的 量通常爲15質量份以下，較佳爲〇.〇〇 1~15質量份，更佳爲 0.005~5質量份》藉由使[E]酸擴散控制劑的用量爲0.001〜15 質量份’可以在抑制感放射線性組成物的放射性靈敏度低 下的同時’形成具有良好精度的圖案的保護膜或層間絕緣 膜。 在該感放射線性組成物中，可以混合[F ]自由基聚合引 發劑（自由基產生劑）和[C]成分的感放射線性酸產生劑或感 放射線性鹼產生劑一起使用。自由基聚合引發劑是具有接 -26- 201107884 受放射線分解，產生自由基，由該自由基引發自由基聚合 性官能團的聚合反應的功能的化合物。例如，在[A]成分是 式（1)中含有（甲基）丙烯醯氧基的化合物時，藉由使用[F]自 由基聚合引發劑，可以促進[A]成分之間聚合反應，提高固 化膜整體的交聯度。 作爲這種自由基聚合引發劑，可以列舉出例如苯乙 酮、苯乙酮苄基縮酮、蒽醌、1-(4-異丙基苯基）·2-羥基-2-甲基丙-1-酮、咔唑、咕噸酮、4 -氯代二苯甲酮、4，4’ -二 胺基二苯甲酮、1,1-二甲氧基去氧安息香、3,3’ -二甲基-4- 甲氧基二苯甲酮、噻噸酮系化合物、2-甲基-1-[4-(甲基硫代） 苯基]-2-味啉·丙-2-酮、2-(4-甲基苄基）-2-二甲基胺基-1-(4-味啉苯基）-丁 -1-酮、2-苄基-2-二甲基胺基-1-(4-味啉苯基）-丁 -1-酮、三苯基胺、氧化2，4,6-三甲基苯甲醯基二苯基膦、 氧化雙（2,6-二甲氧基苯甲醯基）-2,4,4-三甲基戊基膦、苄基 二甲基縮酮、1-羥基環己基苯基酮、2-羥基-2-甲基-1-苯基 丙烷-1-酮、莽酮、莽、苯甲醛、安息香乙基醚、安息香丙 基醚、二苯甲酮、二苯甲酮衍生物、米氏酮、3 -甲基苯乙 嗣、3,3’ ,4,4'-肆（過氧化三級丁基羰基）二苯甲酮、乙醇 -1-[9-乙基-6-(2-甲基苯甲醯基）-9Η-昨唑-3-基]-1-(0-乙醯 基肟）等。這種自由基產生劑可以單獨使用一種，也可以將 兩種以上組合使用。 相對於100質量份[Α]成分，使用[F]自由基聚合引發劑 時的量，較佳爲0.1〜30質量份，更佳爲1~20質量份。藉由 -27- 201107884 使感放射線性組成物中的[F]自由基聚合引發劑的用量爲 0.1〜30質量份，可以形成表面硬度、密合性和耐熱性等級 高且均衡性良好的優異的保護膜和層間絕緣膜。 [G]成分的界面活性劑可以添加以用於改善感放射線 性組成物的塗布性、降低塗布不均、改善放射線照射部的 顯影性。作爲較佳的界面活性劑的例子，可以列舉出非離 子性界面活性劑、含氟界面活性劑和有機矽界面活性劑。 作爲非離子性界面活性劑，可以列舉出例如聚氧乙烯 月桂基醚、聚氧乙烯十八烷基醚、聚氧乙烯油烯基醚等聚 氧乙烯烷基醚類；聚氧乙烯辛基苯基醚、聚氧乙烯壬基苯 基醚等聚氧乙烯芳基醚類；聚乙二醇二月桂酸酯、聚乙二 醇二硬脂酸酯等聚乙二醇二烷基酯類；（甲基）丙烯酸類共 聚物類等。作爲（甲基）丙烯酸類共聚物類的例子，可以列 舉出以市售的商品名表示的PolyfloNo.57、同No.95(共榮社 化學（股）製造）等。 作爲含氟界面活性劑，可以列舉出1，1，2,2 -四氟代辛基 (1,1,2,2-四氟代丙基）醚、1,1,2,2-四氟代辛基己基醚、八乙 二醇雙（1，1，2,2·四氟代丁基）醚、六乙二醇 戊基）醚、八丙二醇雙（1，1，2,2-四氟代丁基）醚、六丙二醇雙 (1，1，2,2,3,3 -六氟戊基）醚等氟代醚類；全氟十二烷基磺酸 鈉；1，1，2,2,8,8,9,9，10，10·十氟十二烷、ι，ι，2,2,3,3-六氟癸 院等氟代院基類；氟代院基苯擴酸鈉類；氟代院基氧化乙 烯醚類；氟代院基錢碘化物類：氟代院基聚氧乙稀醚類； -28- 201107884 全氟烷基聚氧乙醇類；全氟烷基烷氧化物類；含氟烷基酯 類等。 作爲這種含氟界面活性劑的商品，可以列舉出 EFTOPEF301、303、352(新秋田化成（股）製造）、 MEGAFACF171、1 7 2、1 7 3 (大日本油墨工業（股）製造）、 FRORAID FC430、431(住友 3M(股）製造）' Asahi Guard AG710、SurflonS- 3 82、SC-101、102、103、104、105、106(旭 硝子（股）製造）、FTX-218((股）NEOS製造）等。 作爲有機矽界面活性劑的例子，以銷售的商品名表 示，可以歹丨J 舉出 SH200-100cs、SH28PA、SH30PA、ST 89PA、 SH190(Toray Dow Corning Silicone(股）製造）、有機砂氧院 聚合物KP341(信越化學工業（股）製造）等。 相對於100質量份[Α]成分，使用[G]界面活性劑時的 量，較佳爲0.01~10質量份，更佳爲0.05〜5質量份。藉由 使[G]界面活性劑的用量爲0·01~10質量份，可以使感放射 線性組成物的塗布性最優化。 感放射線性組成物 本發明的感放射線性組成物可以藉由將上述[A ]成分 的矽氧烷聚合物、[B]成分的矽烷化合物和[C]成分的感放射 線性酸產生劑或感放射線性鹼產生劑、以及任意成分（[D] 成分的脫水劑等）混合製備。通常，感放射線性組成物較佳 爲以溶解或分散在適當的溶劑中的狀態製備、使用。例如， 在溶劑中，將[A]、[B]和[C]成分以及任意成分以規定的比 -29- 201107884 例混合，可以製備溶液或分散液狀態的感放射線性組成物。 作爲可以在該感放射線性組成物的製備中使用的溶 劑’適合使用各成分均勻地溶解或分散，不和各成分反應 的溶劑。作爲這種溶劑，可以列舉出例如醚類、二甘醇烷 基醚類、乙二醇烷基醚乙酸酯類、丙二醇單烷基醚類、丙 二醇單烷基醚乙酸酯類、丙二醇單烷基醚丙酸酯類、芳烴 類、酮類 '酯類等。 作爲溶劑，可以分別列舉出： 作爲醚類是例如四氫呋喃等； 作爲二甘醇烷基醚類是例如二甘醇單甲基醚、二甘醇 單乙基醚、二甘醇二甲基醚、二甘醇二乙基醚、二甘醇乙 基甲基醚等； 作爲乙二醇烷基醚乙酸酯類是例如甲基賽璐蘇乙酸 醋 '乙基賽璐蘇乙酸酯、乙二醇單丁基醚乙酸酯、乙二醇 單乙基醚乙酸酯等； 作爲丙二醇單烷基醚類是例如丙二醇單甲基醚、丙二 醇單乙基醚、丙二醇單丙基醚、丙二醇單丁基醚等； 作爲丙二醇單烷基醚乙酸酯類是例如丙二醇單甲基醚 乙酸醋、两二醇單乙基醚乙酸酯、丙二醇單丙基醚乙酸酯、 丙二醇單丁基醚乙酸酯等； 作爲丙二醇單烷基醚丙酸酯類是例如丙二醇單甲基醚 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； -30- 201107884 作爲芳烴類是例如甲苯、二甲苯等； 作爲酮類是例如甲基乙基酮、甲基異丁基酮、環己酮、 2-戊酮、4-羥基-4-甲基-2-戊酮等； 作爲酯類是例如乙酸甲酯、乙酸乙酯、乙酸丙酯、乙 酸異丙酯、乙酸丁酯、2-羥基丙酸乙酯、2-羥基-2-甲基丙 酸甲酯、2-羥基-2-甲基丙酸乙酯、羥基乙酸甲酯、羥基乙 酸乙酯、羥基乙酸丁酯、乳酸甲酯、乳酸乙酯、乳酸丙酯、 乳酸丁酯、3-羥基丙酸甲酯' 3-羥基丙酸乙酯、3-羥基丙酸 丙酯、3-羥基丙酸丁酯、2-羥基-3-甲基丁酸甲酯、甲氧基 乙酸甲酯、甲氧基乙酸乙酯、甲氧基乙酸丙酯、甲氧基乙 酸丁酯、乙氧基乙酸甲酯、乙氧基乙酸乙酯、乙氧基乙酸 丙酯、乙氧基乙酸丁酯、丙氧基乙酸甲基、丙氧基乙酸乙 酯、丙氧基乙酸丙酯、丙氧基乙酸丁酯、丁氧基乙酸甲酯、 丁氧基乙酸乙酯、丁氧基乙酸丙酯、丁氧基乙酸丁酯、2-甲氧基丙酸甲酯、2-甲氧基丙酸乙酯、2-甲氧基丙酸丙酯、 2-甲氧基丙酸丁酯、2-乙氧基丙酸甲酯、2-乙氧基丙酸乙酯 等。 這些溶劑中’從溶解性或分散性優異，和各成分是非 反應性的以及形成塗膜形成的容易性的觀點#發，較佳爲 二甘醇烷基醚類、乙二醇烷基醚乙酸酯類、丙二醇單烷基 醚類、丙二醇單烷基醚乙酸酯類、酮類和酯類，特佳爲二 甘醇二乙基醚、二甘醇乙基甲基醚、甲基賽璐蘇乙酸酯、 乙基賽璐蘇乙酸酯、丙二醇單甲基醚、丙二醇單乙基醚、 -31 - 201107884 丙二醇單甲基醚乙酸酯、丙二醇單乙基醚乙酸酯、環己酮、 乙酸丙酯、乙酸異丙酯、乙酸丁酯、2-羥基丙酸乙酯、2-羥基-2-甲基丙酸甲酯、2-羥基-2-甲基丙酸乙酯、乳酸甲 酯、乳酸乙酯、乳酸丙酯、乳酸丁酯、2-甲氧基丙酸甲酯' 2 -甲氧基丙酸乙酯。這些溶劑可以單獨或混合使用。 除了上述溶劑以外，此外根據需要，還可以和苄基乙 基醚、二己基醚、二甘醇單甲基醚、二甘醇單乙基醚、二 甘醇單丁基醚、丙酮基丙酮、異佛爾酮、己酸 '癸酸、1-辛醇、1-壬醇、苯甲醇、乙酸苄基酯、苯甲酸乙酯、草酸 二乙酯、馬來酸二乙酯、r-丁內酯、碳酸乙二酯、碳酸丙 二酯、苯基賽璐蘇乙酸酯、卡必醇乙酸酯等高沸點溶劑一 起使用。 將感放射線性組成物製備爲溶液或分散液狀態時，溶 液中占溶劑以外的成分（也就是，[A]、[B]和[C]成分、以及 其他任意成分的總量）的比例，可以根據使用目的和所希望 的膜厚等任意設定，較佳爲5〜50質量％，更佳爲10~40質 量％，進一步較佳爲15~35質量％。 保護膜或層間絕緣膜的形成 接著，對使用上述感放射線性組成物，在基板上形成 保護膜或層間絕緣膜的固化膜的方法進行說明。該方法包 含以下順序的步驟。 (1)在基板上形成本發明的感放射線性組成物的塗膜 的步驟， -32- •201107884 (2) 對步驟（1)形成的塗膜的至少一部分照射放射線的 步驟， (3) 將步驟（2)中照射放射線的塗膜顯影的步驟，以及 (4) 將步驟（3)顯影的塗膜加熱的步驟。 (1) 在基板上形成感放射線性組成物的塗膜的步驟 在上述（1)步驟中，在基板上塗布本發明的感放射線性 組成物的溶液或分散液後，較佳爲將塗布面加熱（預烘 焙），除去溶劑，形成塗膜。作爲可以使用的基板的例子， 可以列舉出玻璃、石英、矽、樹脂等。作爲樹脂的具體例 子，可以列舉出聚對苯二甲酸乙二酯、聚對苯二甲酸丁二 酯、聚醚颯、聚碳酸酯、聚醯亞胺、環狀烯烴的開環聚合 物及其氫化物等。 作爲組成物溶液或分散液的塗布方法沒有特別的限 定，可以採用例如噴霧法、輥塗法、旋轉塗布法（旋塗法）、 縫模塗布法、棒塗布法等適當的方法。這些塗布方法中， 特佳爲旋塗法或縫模塗布法。預烘焙的條件根據各成分的 種類、混合比例等的不同而不同，較佳在70〜12(TC下進行 1〜10分鐘左右。 (2) 對塗膜的至少一部分照射放射線的步驟 在上述（2)的步驟中，將形成的塗膜的至少一部分曝 光。在這種情況下，對塗膜的一部分曝光時，通常藉由具 有規定圖案的.光罩曝光。作爲曝光使用的放射線，可以使 用例如可見光線、紫外線、遠紫外線、電子束、X射線等。 -33- 201107884 這些放射線中，較佳爲波長在190~45 0nm的範圍的放射 線，特佳爲含有3 65 nm的紫外線的放射線。 該步驟中的曝光量是藉由照度計（OAI model 356，OAI Optical Associates Inc.製造）測定放射線的波長365nrii下的 強度得到的値，較佳爲 100~10,00〇j/m 2，更佳爲 500〜6,000J/m2 ° (3) 顯影步驟 在上述（3)的步驟中，藉由將曝光後的塗膜顯影，除去 不需要的部分（放射線的未照射部分），形成規定的圖案。 作爲顯影步驟中使用的顯影液，較佳爲鹼（鹼性化合物）的 水溶液。作爲鹼的例子，可以列舉出氫氧化鈉、氫氧化鉀、 碳酸鈉、矽酸鈉、偏矽酸鈉、氨等無機鹼，氫氧化四甲基 銨、氫氧化四乙基銨等四級銨鹽等。 另外，在這種鹼水溶液中，還可以適量添加甲醇、乙 醇等水溶性有機溶劑或界面活性劑。作爲顯影方法，可以 利用盛液法、浸漬法、震動浸漬法、淋浴法等適當的方法。 顯影時間根據感放射線性組成物的組成而異，較佳爲 10-180秒左右。在該顯影處理之後，例如進行30~90秒鐘 流水洗滌後，例如藉由壓縮空氣或壓縮氮氣風乾’可以形、 成所希望的圖案。 (4) 加熱步驟 在上述（4)的步驟中，使用加熱板、烘箱等加熱裝置， 對形成圖案的薄膜加熱，促進上述[A]和[B]成分的縮合反 -34- 201107884 應，可以得到真正的固化物。加熱溫度例如是120~25 0 °C。 加熱時間根據加熱設備的種類而異’例如在加熱板上進行 加熱步驟時，進行5~30分鐘；在烘箱中進行加熱步驟時， 是30~90分鐘。還可以使用進行兩次以上的加熱步驟的階 段性烘焙法等。這樣，可以在基板表面上形成對應於所需 要的保護膜或層間絕緣膜的圖案狀薄膜。 保護膜或層閭絕緣膜 這樣形成的保護膜或層間絕緣膜的膜厚較佳爲 0.1-8 μ m » 更佳爲 0.1~6/zm，進一步較佳爲 0.1~4/zm。 由本發明的感放射線性組成物形成的保護膜或層間絕 緣膜如下述實施例所表明，對基板的ITO密合性、表面硬 度、透明性、耐熱透明性、耐擦傷性、耐皸裂和平坦性的 各種性質優異，而且具有由高解析度的感放射線性組成物 形成的精度良好的圖案。因此，該保護膜或層間絕緣膜適 合在液晶顯示元件中使用。 [實施例] 以下所示合成例、實施例，對本發明進行更具體地說 明’但是本發明並不受到以下實施例的任何限定。 由以下的各合成例得到的水解性矽烷化合物的水解縮 合物的數量平均分子量（Μη)和重量平均分子量（Mw)藉由下 述方式的凝膠滲透層析儀法（GPC)測定。 裝置·· GPC-101(昭和電工（股）製造） 柱：組合 GPC-KF-801、GPC-KF-802、GPC-KF- 803 和· -35- 201107884 GPC-KF-8 04(昭和電工（股）製造）形成 移動相：四氫呋喃 [A]成分的水解性矽烷化合物的水解縮合物的合成例 [合成例1] 在帶攪拌器的容器內，加入25質量份丙二醇單甲基 醚，接著，加入30質量份甲基三甲氧基矽烷、23質量份苯 基三甲氧基矽烷和0.1質量份三異丙氧基鋁，加熱到溶液 溫度爲60°C。溶液溫度達到60°C後，加入18質量份離子 交換水，加熱到75 °C，保持3小時。接著，加入28質量份 原甲酸甲酯作爲脫水劑，攪拌1小時。然後，使溶液溫度 爲40°C，一邊保持溫度，一邊蒸發，將離子交換水和水解 縮合產生的甲醇除去。如上，得到水解縮合物（A-1)。水解 縮合物（A-1)的固體成分濃度爲40.5質量％，所得的水解縮 合物的數量平均分子量（Μη)爲1,500，分子量分佈（Mw/Mn) 爲2。 [合成例2] 在帶攪拌器的容器內，加入25質量份丙二醇單甲基 醚，接著，加入18質量份甲基三甲氧基矽烷、15質量份四 乙氧基矽烷、20質量份苯基三甲氧基矽烷和…丨質量份三 異丙氧基鋁，藉由和合成例1同樣的方法，得到水解縮合 物（A-2)。水解縮合物（A-2)的固體成分濃度爲40.8質量％， 所得的水解縮合物的數量平均分子量（Μη)爲1，200，分子量 分佈（Mw/Mn)爲2。 -36- 201107884 [合成例3] 在帶攪拌器的容器內，加入25質量份丙二醇單甲基 醚，接著，加入22質量份甲基三甲氧基矽烷、12質量份 7 -縮水甘油氧基丙基三甲氧基矽烷、20質量份苯基三甲氧 基矽烷和0.1質量份三異丙氧基鋁，藉由和合成例1同樣 的方法，得到水解縮合物（A-3)。水解縮合物（A-3)的固體成 分濃度爲39.8質量％，所得的水解縮合物的數量平均分子 量（Μη)爲1，600，分子量分佈（Mw/Mn)爲2。 [合成例4] 在帶攪拌器的容器內，加入25質量份丙二醇單甲基 醚，接著，加入22質量份甲基三甲氧基矽烷、12質量份 3-甲基丙烯醯氧基丙基三甲氧基矽烷、20質量份苯基三甲 氧基矽烷和0.1質量份三異丙氧基鋁，藉由和合成例1同 樣的方法，得到水解縮合物（A-4)。水解縮合物（A-4)的固體 成分濃度爲39.8質量％，所得的水解縮合物的數量平均分 子量（Μη)爲1,200，分子量分佈（Mw/Mn)爲2。 [合成例5] 在帶攪拌器的容器內，加入25質量份丙二醇單甲基 醚，接著，加入17質量份甲基三甲氧基矽烷、15質量份四 乙氧基矽烷、12質量份r-縮水甘油氧基丙基三甲氧基矽 烷、15質量份苯基三甲氧基矽烷和0.1質量份三異丙氧基 鋁’藉由和合成例1同樣的方法，得到水解縮合物（A-5) ° 水解縮合物（A-5)的固體成分濃度爲40.8質量％，所得的水Si(〇R4)3(CH2)b°γΝγ〇(3) (R50)3Si-fCH2·)^ X V>v(CH2)j-Si(OR6)3 (in formula (3), R4, R5 and R6 is each independently an alkyl group having 1 to 4 carbon atoms, and b, c and d are each independently an integer of 1 to 6. As a preferable specific example of R1 and R3 of the formula (1), Methyl, ethyl, propyl, butyl. Among these alkyl groups, a methyl group or an ethyl group is more preferred. Preferable specific examples of R2 of the formula (1) include a methylene group, an exoethyl group, a propyl group, a cyclopropyl group, a cyclobutane group, a cyclopentyl group, a cyclohexane group, and a benzene stretching group. base. Among these groups, a methylene group, an ethyl group, and a phenyl group are more preferred. Further, when R2 is a group represented by the formula (2), a in the formula (2) is preferably 1 or 2. By using the decane compound of the formula (1) which is preferably of such a structure as the component [B], the reactivity with the component [A] can be improved. Preferable specific examples of R4, R5 and R6 in the formula (3) include a methyl group, an ethyl group, a propyl group and a -17-201107884 butyl group from the viewpoint of reactivity with the component [A]. More preferably, these bases are methyl. Further, b' c and d in the formula (3) are preferably an integer of from 1 to 3 from the viewpoint of reactivity and compatibility with the component [A]. In the radiation-sensitive composition, the '[B] component may be used singly or in combination of two or more. Among the sand compound compounds of the formulae (1) and (3), a decane compound having an isocyanuric acid ring represented by the formula (3) is more preferable. By using a decane compound having three isocyanuric acid rings in which one molecule is combined with an isocyanuric acid ring in one molecule, a radiation-sensitive linear composition exhibiting high radiation sensitivity can be obtained at the same time. The degree of crosslinking of the protective film and the interlayer insulating film formed of the composition is increased. Further, the radiation sensitive composition containing such a decane compound containing an isocyanuric acid ring has high flatness and excellent adhesion, and a protective film and an interlayer insulating film suitable for use in a liquid crystal display device can be formed. Specific examples of the decane compound represented by the formulas (1) and (3) can be exemplified by bis(triethoxycarbenyl)ethane, bis(trimethoxyformamido)methane, and bis (three) Ethyl methoxymethyl) methane, bis-1,2-(trimethoxymethyl cetyl) ethane, bis-1,6-(trimethoxymethyl decyl) hexane, bis-1,6- (triethoxymethane alkyl) hexane, bis-1,4-(trimethoxymethyl decyl) benzene, bis-1,4-(triethoxymethane alkyl) benzene, 1,4-double (trimethoxycarbamidylmethyl)benzene, 1,4-bis(trimethoxycarbamidylethyl)benzene, M-bis(triethoxymethylmethylmethyl)benzene, 1,4-double (triethoxymethane alkylethyl)benzene, ginseng (trimethoxymethylmethylmethyl) isocyanurate, ginseng (triethoxymethylmethylmethyl) isocyanurate, ginseng (2-trimethoxymethyl sulfonylethyl) aliquot [ -18- 201107884 Urea, ginseng (2-triethoxymethyl sulfonyl ethyl) isocyanurate, ginseng (3·trimethoxy) Mercaptopropyl propyl) isocyanurate, ginseng (3-triethoxymethane alkyl propyl) isocyanuric acid Ester, [bis(2-trimethoxycarbamidylethyl)-(3-triethoxycarbamidylpropyl)]isocyanurate, [trimethoxycarbamidylmethyl-(2- Trimethoxymethyl decyl ethyl)-(3-trimethoxycarbamidylpropyl)]isocyanurate or the like. Among them, from the viewpoint of improving the radiation sensitivity, the flatness of the obtained protective film and the interlayer insulating film, it is particularly preferably 1,4·bis(trimethoxymethylmethylmethyl)benzene or bis(triethoxy). Methionyl)ethane, ginseng (2-trimethoxycarbamidylethyl)isocyanurate, ginseng (3-trimethoxyformamidopropyl)isocyanurate, ginseng (3-three Ethoxymethoxyalkyl propyl) isocyanurate. The amount of the [Β] component in the radiation sensitive composition is preferably 5 parts by mass to 70 parts by mass, more preferably 10 parts by mass to 50 parts by mass, per 100 parts by mass of the [Α] component. By using the amount of the [Β] component in an amount of from 5 parts by mass to 70 parts by mass, it is possible to obtain a radiation-sensitive composition having excellent radiation sensitivity and a flatness of the obtained protective film and the interlayer insulating film. [C] component: a radiation sensitive acid generator or a radiation sensitive linear generator which is a radioactive linear acid generator or a radiation sensitive linear generator [C] is defined as a ruthenium of a [Α] component by irradiation with radiation. When the oxyalkylene polymer (preferably, the hydrolysis condensate of the hydrolyzable decane compound represented by the above formula (4)) is condensed and solidified with the decane compound of the [Β] component, the acidic active material used as a catalyst or A compound of an alkaline active substance. In addition, as radiation for cations or anions which generate an acidic active material or a base -19-201107884 active material, the light, ultraviolet ray, infrared ray, X ray, α ray, Θ can be exemplified. Ray rays, etc. Among these radiations, a certain energy level is obtained, a large curing speed can be obtained, and the irradiation device is relatively inexpensive and miniaturized, and ultraviolet rays are used. Further, it is preferable that the radical active agent of the [C] component and the radioactive base generator together with the radical polymerization initiator described later cause the radical of the neutral active material generated by the ruthenium radical polymerization initiator. The condensation reaction of the undecyclable decane compound is not carried out, but when the [Α] component has an S polymerizable functional group, the polymerization of the functional group can be promoted. The radiation-sensitive acid generator as the component [C] is preferably a diphenylmium salt, a triphenylsulfonium salt or a tetrahydrostilbene salt, and particularly preferably a triphenylthiophene key salt. As a specific example of the diphenyl iodine salt, phenyl iodide tetrafluoroborate, diphenyl iodine hexafluorophosphate, keyl hexafluoroarsenate, diphenyl iodine trifluoromethanesulfonic acid Salt, diphenyl iron trifluoroacetate, diphenyl iodine gun-p-toluenesulfonate, diphenyliodonyl ginseng (2,6-difluorophenyl) borate, 4-methoxyphenyl phenyl Iodine tetrakisate 'bis(4-tris-butylphenyl) iodine tetrafluoroborate, bis(4-triphenylphenyl)iodonium hexafluoroarsenate, bis(4-tert-butylbenzene) Iodine octarate, bis(4-tert-butylphenyl) iodine trifluoroacetate, bis(4-T-phenyl) iodine-p-toluenesulfonate, bis(4-tri Grade butylphenyl) iodosulfonate and the like. Specific examples of the triphenylphosphonium salt include a triphenyl group and a preferred or inductive method. Will promote free radical iodized salt and enumerate diphenyl iodine gun butyl fluoride boron butyl fluorocarbon tertiary sulfonium disulfide -20- 201107884 fluoromethanesulfonate, triphenyl camphorsulfonate, triphenyl sulfonium tetra Fluoroborate, triphenyl mirror trifluoroacetate, triphenylsulfonium-p-toluenesulfonate, triphenylphosphonium butyl (2,6-difluorophenyl)borate, and the like. Specific examples of the tetrahydrothiophene key salt include 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophene iron trifluoromethanesulfonate and 1-(4-n-butoxynaphthalene- 1-yl)tetrahydrothiophene-n-hexafluoro-n-butanesulfonate, 1-(4-n-butoxynaphthalene-buyl)tetrahydrothiophene-1,1,2,2-tetrafluoro-2-( Cyclodecane-2-yl)ethanesulfonate, 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophene- 2-(5-tris-butoxycarbonyloxybicyclo[2] . 2. 1]hept-2-yl)-1,1,2,2-tetrafluoroethanesulfonate, 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophene-2-(6- Tertiary butoxy oxybicyclo[2. 2. 1] -hept-2-yl)-1,1,2,2-tetrafluoroethanesulfonate, 1-(4,7-dibutoxy-1-naphthalenyl) tetrahydrothiophene trifluoromethyl Sulfonate and the like. Among these radiation-sensitive acid generators, triphenylsulfonium trifluoromethanesulfonate, triphenyl camphorsulfonate, and 1-(4, are particularly preferable from the viewpoint of improving the radiation sensitivity of the radiation sensitive composition. 7-Dibutoxy-1-naphthyl)tetrahydrothiophene triflate. Examples of the radiation-sensitive alkali generating agent as the component [C] include 2-nitrobenzylcyclohexylaminoformate and [[(2,6·dinitrobenzyl)oxy]carbonyl]. Cyclohexylamine, N-(2-nitrobenzyloxycarbonyl)pyrrolidine, bis[[(2-nitrobenzyl)oxy]carbonyl]hexane-1,6.diamine, triphenylmethanol, 0-Aminomethylhydrazine hydroxy decylamine, 0-aminomethylguanidinium hydride, 4-(methylthiobenzimidyl)-1-methyl-1-tyrosine ethane, (4. Benzyl hydrazino)-1-benzyl-1-dimethylaminopropane, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, -21 - 201107884 Hexaamine cobalt (III) ginseng (triphenylmethylborate) and the like. Among these radiation-sensitive alkali generating agents of the component [C], from the viewpoint of improving the radiation sensitivity of the radiation sensitive composition, 2-nitrobenzylcyclohexylcarbamate and 0-aminoformamidine are particularly preferred. Hydroxy guanamine. The radiation-sensitive linear acid generator or the radiation-sensitive linear base generator of the component [C] may be used singly or in combination of two or more. The amount of the [C] component is preferably 0% with respect to 100 parts by mass of the component [A]. 1 part by mass to 20 parts by mass, more preferably 1 part by mass to 10 parts by mass. By making the amount of [C] component 0. From 1 part by mass to 20 parts by mass, it is possible to obtain a radiation sensitive composition having a radiation sensitivity, a pencil hardness and a heat resistance (heat-resistant transparency) of the formed protective film and the interlayer insulating film, which are more balanced. [D] component: dehydrating agent [D] The dehydrating agent of the component is defined as a substance which can be converted into water other than water by a chemical reaction, or a substance which is closed by water by physical adsorption or inclusion. By containing the [D] dehydrating agent arbitrarily in the radiation-sensitive composition, it is possible to reduce moisture intruding from the environment, or water which is condensed by the radiation of the [A] and [B] components in the exposure irradiation step described later. Therefore, by using the [D] dehydrating agent, the moisture in the composition can be reduced to improve the storage stability of the composition. Further, it is considered that the reactivity of the shrinkage of the components [A] and [B] can be improved, and the radiation sensitivity of the radiation sensitive composition can be improved. As such [D] dehydrating agent, at least one compound selected from the group consisting of a carboxylate, an acetal (containing a ketal) and a carboxylic anhydride is preferably used. Preferable examples of the carboxylic acid ester include an orthocarboxylic acid ester -22-201107884 (orthocarboxylic acid), a residual acid methadone ester, and the like. Specific examples of the original residue include methyl orthoformate, ethyl orthoformate, propyl orthoformate, butyl orthoformate, methyl orthoacetate, ethyl acetate, propyl orthoacetate, and butyl phthalate. Ester, methyl orthopropionate, ethyl orthopropionate, and the like. Further, among these orthocarboxylic acid esters, an orthoformate such as methyl orthoformate is particularly preferred. Specific examples of the mercaptocarboxylic acid carboxylate include trimethylmethanecarboxylate acetate, tributylcarbamyl acetate, trimethylformamidinecarboxylate, and trimethylformamidate oxalate. Preferable examples of the acetal include a reaction product of a ketone and an alcohol, a reaction product of a ketone and a diol, and a ketene alkyl acetal. Specific examples of the reactant of the ketone and the alcohol include dimethyl acetal, diethyl acetal, dipropyl acetal and the like. Preferable examples of the carboxylic acid anhydride include acetic anhydride, acetic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, and benzoic acid anhydride. Among these carboxylic anhydrides, acetic anhydride and succinic anhydride are preferred from the viewpoint of dehydration effect. The amount when the [D] dehydrating agent is used is preferably 0% with respect to 100 parts by mass of the component [A]. 1 to 50 parts by mass, more preferably 0. 5~30 parts by mass, especially good for l~l〇 parts by mass. By using [D] dehydrating agent in an amount of 0. 1 to 50 parts by mass can optimize the storage stability of the radiation sensitive composition. Other optional components The radiation sensitive composition of the present invention may be in the range of -23-201107884, which does not impair the effects of the present invention, in addition to the above [A] to [C] components and [D] components (optional components), as needed. It contains other components such as [E] acid diffusion controlling agent, [F] radical polymerization initiator, and [G] surfactant. When a radiation sensitive acid generator is used as the [C] component of the radiation sensitive composition, the acid diffusion controlling agent of the [E] component has the following effects, and controls the acidic active material generated by the irradiation of radiation in the composition coating film. The diffusion inhibits the curing reaction in the non-exposed areas. By using such an acid diffusion controlling agent together with a radiation-sensitive acid generator of the [C] component, the resolution of the radiation sensitive composition can be further improved (the contact hole-containing layer of the interlayer insulating film can be formed with high precision) I want the radiation-sensitive properties of the pattern). Examples of the acid diffusion inhibitor include monoalkylamines, dialkylamines, trialkylamines, aromatic amines, alkanolamines, aliphatic amines, and guanamine-containing compounds. Nitrogen-containing compounds such as urea compounds, imidazoles, pyridines, and other nitrogen-containing heterocyclic compounds. Specific examples of these acid diffusion inhibitors may be exemplified by, for example, a monoalkylamine such as n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-decylamine or the like; The amines are di-n-butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-decylamine, di-n-decylamine, etc.; The amines are triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-decylamine, three N-decylamine, etc.; as aromatic amines are aniline, N-methylaniline, N,N-dimethylbenzene-24-. 201107884 Amine, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline, diphenylamine, triphenylamine, 1-naphthylamine, 4,4'-diamine Diphenylphenyl, 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 44'-diaminodiphenylamine, 2,2'-double (4-Aminophenyl)propane, 2-(3-aminophenyl)-2-(4-aminophenyl)propane, 2-(4-aminophenyl)-2-(3-hydroxyl Phenyl) propane, 2-(4-aminophenyl)-2-(4-hydroxyphenyl)propane, 1,4-bis[1-(4-aminophenyl)-1-methylethyl Benzene, anthracene, 3_bis[1-(4-aminophenyl)-i-methylethyl]benzene, etc.; as an alkanolamine, ethanolamine, diethanolamine, triethanolamine, etc.; as an aliphatic amine Is ethylenediamine, N,N,N',N'-tetramethylethylenediamine, butanediamine, hexamethylenediamine, hydrazine, hydrazine, hydrazine, N,-肆(2-hydroxyethyl)ethylene Amine, N, N, N', N'-indole (2-hydroxypropyl) ethylenediamine, polyvinylimine, polypropylamine, dimethylaminoethyl acrylamide, etc.; The guanamine-based compound is formamide, N-methylformamide, N , N-dimethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, acetamide, benzamide, 2-pyrrolidone, N- Methyl pyrrolidone or the like; as a urea compound, urea, methyl gland, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3·tetramethylurea, 1, 3-diphenylurea, tributylthiourea, etc.; as imidazoles are imidazole 'benzimidazole, 2-methylimidazole, 4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 4- Methyl-2-phenylimidazole or the like; as pyridine, pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenyl Pyridine, 3·methylhydrazine α- 201107884 Phenylpyridine, nicotine, nicotinic acid, decylamine nicotamine, quinoline, 8-oxyquinoline, Iff steep, etc.: as other nitrogen-containing heterocyclic compounds Is a pyr trap, pyrazole, pyrimidine, quinoxaline, porphyrin, 4-methyl morpholine, piperidine, 1. , 4-dimethylpiperane, 1,4-diazabicyclo[2. 2. 2] Octane '2,4,6-gin(2-pyridyl)-1,3,5-three tillage, and the like. Among these nitrogen-containing compounds, preferred are trialkylamines and pyridines. The trialkylamines which are particularly preferred are triethylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine and tri-n-octylamine. Further, examples of the particularly preferred pyridines include 2,4,6-cis(2-pyridyl)-1,3,5-three tillage, pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, 3-methyl-4-phenylindole ratio steep, sulphuric acid, sulphuric acid, decyl amide, salicin , 8 - via quinoxaline, acridine. These acid diffusion controlling agents may be used singly or in combination of two or more. The amount of the [E] acid diffusion controlling agent used is usually 15 parts by mass or less, preferably 〇., per 100 parts by mass of the [A] component. 〇〇 1~15 parts by mass, more preferably 0. 005~5 parts by mass" by using the [E] acid diffusion controlling agent to be 0. 001 to 15 parts by mass can form a protective film or an interlayer insulating film having a pattern with good precision while suppressing the low radioactivity sensitivity of the radiation sensitive composition. In the radiation sensitive linear composition, a [F] radical polymerization initiator (radical generator) may be mixed with a radiation sensitive acid generator or a radiation sensitive alkali generator of the [C] component. The radical polymerization initiator is a compound having a function of decomposing by radiation, generating a radical, and initiating a polymerization reaction of a radical polymerizable functional group by the radical. For example, when the component [A] is a compound containing a (meth)acryloxy group in the formula (1), the polymerization reaction between the components [A] can be promoted by using the [F] radical polymerization initiator. The degree of crosslinking of the cured film as a whole. As such a radical polymerization initiator, for example, acetophenone, acetophenone benzyl ketal, anthracene, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropene- 1-ketone, carbazole, xanthone, 4-chlorobenzophenone, 4,4'-diaminobenzophenone, 1,1-dimethoxy deoxybenzoin, 3,3' - Dimethyl-4-methoxybenzophenone, thioxanthone-based compound, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholine·propan-2-one , 2-(4-methylbenzyl)-2-dimethylamino-1-(4-morpholinylphenyl)-butan-1-one, 2-benzyl-2-dimethylamino- 1-(4-morpholinephenyl)-butan-1-one, triphenylamine, 2,4,6-trimethylbenzhydryldiphenylphosphine oxide, bis(2,6-dimethylene oxide) Oxylbenzylidene)-2,4,4-trimethylpentylphosphine, benzyldimethylketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-benzene Propane-1-one, anthrone, anthracene, benzaldehyde, benzoin ethyl ether, benzoin propyl ether, benzophenone, benzophenone derivative, Michler's ketone, 3-methylphenidene, 3 , 3' , 4, 4'-肆 (tris-butyl carbonyl peroxide) benzophenone, ethanol-1-[9-ethyl-6- (2-Methylbenzylidene)-9Η-predomazol-3-yl]-1-(0-ethylindenyl) and the like. These radical generating agents may be used singly or in combination of two or more. The amount when the [F] radical polymerization initiator is used is preferably 0% with respect to 100 parts by mass of the [Α] component. 1 to 30 parts by mass, more preferably 1 to 20 parts by mass. By using -27-201107884, the amount of [F] radical polymerization initiator in the radiation sensitive composition is 0. 1 to 30 parts by mass, an excellent protective film and an interlayer insulating film having high surface hardness, adhesion, and heat resistance and high balance can be formed. The surfactant of the component [G] can be added for improving the coatability of the radiation sensitive composition, reducing coating unevenness, and improving the developability of the radiation irradiated portion. As a preferable example of the surfactant, a nonionic surfactant, a fluorine-containing surfactant, and an organic phosphonium surfactant can be given. Examples of the nonionic surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; and polyoxyethylene octylbenzene; a polyoxyethylene aryl ether such as a polyether or a polyoxyethylene nonylphenyl ether; a polyethylene glycol dialkyl ester such as polyethylene glycol dilaurate or polyethylene glycol distearate; Methyl)acrylic copolymers and the like. Examples of the (meth)acrylic copolymers include Polyflo No. which is represented by a commercially available trade name. 57, the same No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), etc. Examples of the fluorine-containing surfactant include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether and 1,1,2,2-tetrafluoro. Dioctyl hexyl ether, octaethylene glycol bis(1,1,2,2·tetrafluorobutyl)ether, hexaethylene glycol pentyl)ether, octapropylene glycol bis (1,1,2,2-four Fluorinated ethers such as fluorobutyl)ether, hexapropylene glycol bis(1,1,2,2,3,3-hexafluoropentyl)ether; sodium perfluorododecylsulfonate; 1,1,2 , 2,8,8,9,9,10,10·decafluorododecane, ι,ι,2,2,3,3-hexafluorophthalate and other fluorinated hospital bases; Sodium sulphate; fluoro-based oxyethylene ethers; fluorinated-based iodide: fluorinated polyoxyethylene ethers; -28- 201107884 perfluoroalkyl polyoxyethylenes; perfluoroalkyl Alkoxides; fluorine-containing alkyl esters, etc. As a commercial product of such a fluorine-containing surfactant, EFTOPEF301, 303, 352 (manufactured by New Akita Chemicals Co., Ltd.), MEGAFACF 171, 177, 177 (manufactured by Dainippon Ink Co., Ltd.), FRORAID can be cited. FC430, 431 (manufactured by Sumitomo 3M Co., Ltd.) 'Asahi Guard AG710, Surflon S- 3 82, SC-101, 102, 103, 104, 105, 106 (made by Asahi Glass Co., Ltd.), FTX-218 ((share) NEOS Manufacturing) and so on. As an example of the organic ruthenium surfactant, it is represented by the brand name of the product, and SH200-100cs, SH28PA, SH30PA, ST 89PA, SH190 (made by Toray Dow Corning Silicone), and organic sand oxide polymerization can be cited. KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like. The amount of the [G] surfactant used is preferably 0% with respect to 100 parts by mass of the [Α] component. 01~10 parts by mass, more preferably 0. 05 to 5 parts by mass. By using the amount of the [G] surfactant in an amount of from 0.01 to 10 parts by mass, the coating property of the radiation sensitive linear composition can be optimized. Radiation-sensitive composition The radiation-sensitive composition of the present invention can be obtained by using a radioactive acid generator or a sensitizing agent of the above-mentioned [A] component, a decane compound, a [B] component, a decane compound, and a [C] component. A radioactive linear base generator and an optional component (a dehydrating agent of the [D] component) are mixed and prepared. Usually, the radiation sensitive composition is preferably prepared and used in a state of being dissolved or dispersed in a suitable solvent. For example, in the solvent, the [A], [B], and [C] components and optional components are mixed in a predetermined ratio of -29 to 201107884 to prepare a radiation sensitive composition in a solution or dispersion state. The solvent which can be used in the preparation of the radiation-sensitive composition is suitably used as a solvent which is uniformly dissolved or dispersed in each component and does not react with each component. Examples of such a solvent include ethers, diethylene glycol alkyl ethers, ethylene glycol alkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, and propylene glycol monoalkyl groups. Ether propionates, aromatic hydrocarbons, ketones, esters, and the like. The solvent may, for example, be an ether such as tetrahydrofuran or the like; and the diethylene glycol alkyl ether may be, for example, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether or diethylene glycol dimethyl ether. Diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, etc.; as ethylene glycol alkyl ether acetates, for example, methyl cyproterone acetate vinegar ethyl acesulfame acetate, ethylene glycol Monobutyl ether acetate, ethylene glycol monoethyl ether acetate, etc.; as propylene glycol monoalkyl ethers are, for example, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl As the propylene glycol monoalkyl ether acetate, for example, propylene glycol monomethyl ether acetate vinegar, di diol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate Esters and the like; as the propylene glycol monoalkyl ether propionate, for example, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate propylene glycol monopropyl ether propionate, propylene glycol monobutyl ether propionate Et al; -30- 201107884 as aromatic hydrocarbons such as toluene, xylene, etc.; as a ketone For example, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-pentanone, 4-hydroxy-4-methyl-2-pentanone, etc.; as an ester, for example, methyl acetate, ethyl acetate Ester, propyl acetate, isopropyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropanoate, ethyl 2-hydroxy-2-methylpropionate, hydroxyl Methyl acetate, ethyl hydroxyacetate, butyl glycolate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate 3-ethyl 3-hydroxypropionate, 3-hydroxypropane Acid propyl ester, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, methoxyacetic acid Butyl ester, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propoxyacetic acid Ester, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxide, propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, 2-methyl Ethyl oxypropionate, 2-methoxypropane Propyl 2-methoxy propionate, butyl 2-ethoxy-methyl, 2-ethoxy ethyl propionate. Among these solvents, 'is excellent in solubility or dispersibility, and each component is non-reactive and easy to form a coating film. Preferably, diethylene glycol alkyl ethers, ethylene glycol alkyl ether acetates Esters, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, ketones and esters, particularly preferably diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, methyl cyanisol Acetate, ethyl cyproterone acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, -31 - 201107884 propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone , propyl acetate, isopropyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, lactate Ester, ethyl lactate, propyl lactate, butyl lactate, methyl 2-methoxypropionate '2-methoxypropionic acid ethyl ester. These solvents may be used singly or in combination. In addition to the above solvents, in addition to benzyl ethyl ether, dihexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, acetone acetone, Isophorone, caproic acid 'capric acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, r-butane A high boiling point solvent such as an ester, ethylene carbonate, propylene carbonate, phenyl cyanoacetate or carbitol acetate is used together. When the radiation sensitive composition is prepared into a solution or dispersion state, the ratio of the components other than the solvent (that is, the total amount of [A], [B], and [C] components, and other optional components) in the solution, It can be arbitrarily set depending on the purpose of use, the desired film thickness, and the like, and is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, still more preferably 15 to 35% by mass. Formation of Protective Film or Interlayer Insulating Film Next, a method of forming a cured film of a protective film or an interlayer insulating film on a substrate using the above-described radiation sensitive composition will be described. This method contains the steps in the following sequence. (1) a step of forming a coating film of the radiation sensitive composition of the present invention on a substrate, -32- • 201107884 (2) a step of irradiating at least a part of the coating film formed in the step (1) with radiation, (3) The step of developing the coating film irradiated with radiation in the step (2), and (4) the step of heating the coating film developed in the step (3). (1) Step of Forming Coating Film of Radiation-Sensitive Composition on Substrate In the above step (1), after applying the solution or dispersion of the radiation-sensitive composition of the present invention on the substrate, it is preferred to apply the coated surface. Heating (prebaking), removing the solvent to form a coating film. Examples of the substrate that can be used include glass, quartz, rhodium, and resin. Specific examples of the resin include open-loop polymers of polyethylene terephthalate, polybutylene terephthalate, polyether oxime, polycarbonate, polyimine, and cyclic olefin. Hydride, etc. The coating method of the composition solution or the dispersion liquid is not particularly limited, and an appropriate method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, or a bar coating method can be employed. Among these coating methods, a spin coating method or a slit die coating method is particularly preferred. The pre-baking conditions vary depending on the type of each component, the mixing ratio, etc., and are preferably from 70 to 12 (about 1 to 10 minutes under TC.) (2) The step of irradiating at least a part of the coating film with radiation is as described above ( In the step of 2), at least a part of the formed coating film is exposed. In this case, when a part of the coating film is exposed, it usually has a prescribed pattern. The mask is exposed. As the radiation to be used for exposure, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like can be used. -33- 201107884 Among these radiations, radiation having a wavelength in the range of 190 to 45 nm is preferable, and radiation containing ultraviolet rays of 3 65 nm is particularly preferable. The amount of exposure in this step is by illuminance meter (OAI model 356, OAI Optical Associates Inc. Manufactured) The enthalpy obtained by measuring the intensity at a wavelength of 365 nrii of radiation, preferably 100 to 10,00 〇j/m 2 , more preferably 500 to 6,000 J/m 2 ° (3) Development step in the above step (3) In the meantime, by developing the exposed coating film, unnecessary portions (unirradiated portions of the radiation) are removed to form a predetermined pattern. As the developing solution used in the developing step, an aqueous solution of an alkali (basic compound) is preferred. Examples of the base include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, and ammonia, and tetrabasic ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. Salt and so on. Further, in such an aqueous alkali solution, a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added in an appropriate amount. As the developing method, an appropriate method such as a liquid-filling method, a dipping method, a vibration dipping method, or a shower method can be used. The development time varies depending on the composition of the radiation sensitive composition, and is preferably about 10 to 180 seconds. After the development treatment, for example, after 30 to 90 seconds of running water washing, for example, air-dried by compressed air or compressed nitrogen, the desired pattern can be formed. (4) Heating step In the step (4) above, heating the patterned film using a heating means such as a hot plate or an oven to promote the condensation of the above [A] and [B] components, anti-34-201107884 Get a real cured product. The heating temperature is, for example, 120 to 250 °C. The heating time varies depending on the type of the heating device. For example, when the heating step is performed on the hot plate, it is carried out for 5 to 30 minutes, and when the heating step is performed in the oven, it is 30 to 90 minutes. It is also possible to use a stepwise baking method or the like which performs two or more heating steps. Thus, a pattern-like film corresponding to a desired protective film or interlayer insulating film can be formed on the surface of the substrate. Protective film or layer insulating film The film thickness of the protective film or interlayer insulating film thus formed is preferably 0. 1-8 μ m » More preferably 0. 1~6/zm, further preferably 0. 1~4/zm. The protective film or interlayer insulating film formed by the radiation sensitive composition of the present invention is as shown in the following examples, and has excellent ITO adhesion, surface hardness, transparency, heat-resistant transparency, scratch resistance, crinkle resistance and flatness to the substrate. It is excellent in various properties and has a highly accurate pattern formed of a high-resolution radiation-sensitive composition. Therefore, the protective film or interlayer insulating film is suitable for use in a liquid crystal display element. [Examples] The present invention will be more specifically described in the following Synthesis Examples and Examples, but the present invention is not limited by the following examples. The number average molecular weight (??) and the weight average molecular weight (Mw) of the hydrolysis condensate of the hydrolyzable decane compound obtained in each of the following Synthesis Examples were measured by a gel permeation chromatography (GPC) method as described below. Device·· GPC-101 (manufactured by Showa Denko Co., Ltd.) Column: Combination GPC-KF-801, GPC-KF-802, GPC-KF-803 and · -35- 201107884 GPC-KF-8 04 (Showa Electric ( (Production) Production of a mobile phase: Synthesis of a hydrolysis condensate of a hydrolyzable decane compound of a tetrahydrofuran [A] component [Synthesis Example 1] 25 parts by mass of propylene glycol monomethyl ether was added to a vessel equipped with a stirrer, followed by 30 parts by mass of methyltrimethoxydecane, 23 parts by mass of phenyltrimethoxydecane and 0. 1 part by mass of aluminum triisopropoxide was heated to a solution temperature of 60 °C. After the solution temperature reached 60 ° C, 18 parts by mass of ion-exchanged water was added and heated to 75 ° C for 3 hours. Next, 28 parts by mass of methyl orthoformate was added as a dehydrating agent, and the mixture was stirred for 1 hour. Then, the solution was allowed to evaporate while maintaining the temperature while maintaining the temperature at 40 ° C, and the methanol produced by the hydrolyzed condensation was removed. As described above, the hydrolysis condensate (A-1) was obtained. The solid content concentration of the hydrolysis condensate (A-1) is 40. 5 mass%, the obtained hydrolysis condensate had a number average molecular weight (?n) of 1,500 and a molecular weight distribution (Mw/Mn) of 2. [Synthesis Example 2] In a container equipped with a stirrer, 25 parts by mass of propylene glycol monomethyl ether was added, followed by 18 parts by mass of methyltrimethoxydecane, 15 parts by mass of tetraethoxydecane, and 20 parts by mass of phenyl group. The hydrolysis condensate (A-2) was obtained in the same manner as in Synthesis Example 1 except for trimethoxysilane and hydrazine triisopropoxide. The solid content concentration of the hydrolysis condensate (A-2) is 40. The obtained hydrolysis-condensation product had a number average molecular weight (??) of 1,200 and a molecular weight distribution (Mw/Mn) of 2, in an amount of 8% by mass. -36-201107884 [Synthesis Example 3] In a container with a stirrer, 25 parts by mass of propylene glycol monomethyl ether was added, followed by 22 parts by mass of methyltrimethoxydecane and 12 parts by mass of 7-glycidoxypropane. Trimethoxy decane, 20 parts by mass of phenyl trimethoxy decane and 0. The hydrolysis-condensation product (A-3) was obtained in the same manner as in Synthesis Example 1 by using 1 part by mass of aluminum triisopropoxide. The solid content concentration of the hydrolysis condensate (A-3) was 39. The amount of the obtained hydrolysis condensate was 1,600% by mass, and the molecular weight distribution (Mw/Mn) was 2. [Synthesis Example 4] In a container with a stirrer, 25 parts by mass of propylene glycol monomethyl ether was added, followed by 22 parts by mass of methyltrimethoxydecane and 12 parts by mass of 3-methylpropenyloxypropyltrimethyl Oxydecane, 20 parts by mass of phenyltrimethoxydecane and 0. The hydrolysis-condensation product (A-4) was obtained by the same method as in Synthesis Example 1 in an amount of 1 part by mass of aluminum triisopropoxide. The solid content concentration of the hydrolysis condensate (A-4) was 39. The amount of the obtained hydrolysis-condensation product was 8% by mass, and the obtained molecular weight distribution (Mw/Mn) was 2. [Synthesis Example 5] 25 parts by mass of propylene glycol monomethyl ether was added to a vessel equipped with a stirrer, followed by addition of 17 parts by mass of methyltrimethoxydecane, 15 parts by mass of tetraethoxydecane, and 12 parts by mass of r- Glycidoxypropyltrimethoxydecane, 15 parts by mass of phenyltrimethoxydecane and 0. 1 part by mass of triisopropoxy aluminum. By the same method as in Synthesis Example 1, the hydrolyzed condensate (A-5) ° hydrolysis condensate (A-5) had a solid concentration of 40. 8% by mass, the water obtained
[S -37- 201107884 解縮合物的數量平均分子量（Mn)爲^00,分子量分佈 (Mw/Mn)爲 2。 [合成例6] 在帶攪拌器的容器內，加入25質量份丙二醇單甲棊 醚’接著’加入17質量份甲基三甲氧基矽烷、15質量份四 乙氧基砂烷、12質量份3_甲基丙烯醯氧基丙基三甲氧基矽 烷、15質量份苯基三甲氧基矽烷和ο」質量份三異丙氧墓 鋁，藉由和合成例丨同樣的方法，得到水解縮合物（A_6)。 水解縮合物（A-6)的固體成分濃度爲40.8質量％，所得的水 解縮合物的數量平均分子量（Μη)爲1,600，分子量分佈 (Mw/Mn)爲 2。 感放射線性組成物的製備和保護膜、層間絕緣膜的形成 [實施例1] 在合成例1得到的含有水解縮合物（A-1)的溶液（相當 於100質量份水解縮合物（A-1)(固體成分）的量）中，加入15 質量份作爲[B]成分的（B-l)l，4-雙（三甲氧基甲矽烷基甲基） 苯、2質量份作爲[C]成分的（C-l)l-(4,7·二丁氧基-1-萘基） 四氫噻吩鏺三氟甲磺酸鹽、3質量份作爲[D]成分的原甲酸 甲酯、0.05質量份作爲[E]成分的（E-1)三乙胺、0.1質量份 作爲[G]成分的（G-1)含氟界面活性劑（（股）NEOS製造的 「FTX-218」），添加丙二醇單甲基醚以使固體成分濃度爲 25質量％，製備感放射線性組成物。使用旋塗器將該感故 射線性組成物塗布到SiCh浸漬玻璃基板上後，在加熱披 -38- 201107884 上，在90°C下預烘焙2分鐘，形成塗膜（在後述的ITO密合 性評價中，使用帶ΙΤΟ的基板’在平坦化性能評價中’使 用形成了濾光片的Si〇2浸漬玻璃基板）》接著，對所得的塗 膜，以5,OOOJ/m2的曝光量，曝光紫外線。接著，藉由2.38 質量％的氫氧化四甲基銨水溶液，在25 °C下顯影80秒後， 純水洗漉1分鐘，然後在230 °C的烘箱中，加熱60分鐘， 形成膜厚2.的保護膜。另外’調節形成塗膜時的旋塗 器的轉數，以使加熱後的膜厚爲3.0//m，除了藉由具有 20//m> 30/zm、40/zm、50/zm的尺寸的接觸孔圖案的光 罩，以150 # m的曝光狹縫（基板和光罩的間隔）曝光以外， 和上述形成保護膜同樣地，形成層間絕緣膜。 [實施例2〜17和比較例1~6] 除了各成分的種類和量如表1所記載以外，和實施例 1同樣地，製備感放射線性組成物。接著，使用像這樣製 .備的感放射線性組成物，和實施例1同樣地形成保護膜和 層間絕緣膜。 物性評價 實施例1 ~ 1 7、比較例1〜6形成的保護膜的透明性、耐 熱透明性、表面硬度、耐磨損性、耐皸裂、IT0密合性和 平坦性、以及感放射線性組成物的解析度（層間絕緣膜的清 晰度）和保存穩定性的評價方法如下所示。感放射線性組成 物的「解析度」是對組成物能夠形成層間絕緣膜的精密的 接觸孔的性能的評價，同時提供作爲層間絕緣膜的「清晰 -39- 201107884 度」的評價。 (1) 保護膜的透明性的評價 對各實施例和比較例中，如上形成的具有保護膜的基 板，使用分光光度計（日立製作所（股）製造的 1 50-20型 Double-Beam)，測定波長400~800nm的光線透過率（％)。將 波長400~800nm的光線透過率（％)的最小値作爲透明性的 評價，在表1中表示。該値爲95 %以上時，可以認爲保護 膜的透明性是良好的。在針對層間絕緣膜進行時，只是膜 厚（3.0 # m)和保護膜不同，所以層間絕緣膜的透明性的評價 和保護膜的透明性的評價同樣地判斷。 (2) 保護膜的耐熱透明性的評價 對各實施例和比較例中，如上形成的具有保護膜的基 板，在清潔烘箱中，在250°C下加熱1小時，根據上式（1) 「保護膜的透明性評價」中記載的方法，測定加熱前後的 光線透過率。根據下式算出的耐熱透明性（％)如表1所示。 該値爲4%以下時，可以認爲保護膜的耐熱透明性良好。 耐熱透明性（％)==加熱前的光線透過率（％)-加熱後的 光線透過率（％) (3) 保護膜的鉛筆硬度（表面硬度）的測定 對各實施例和比較例中，如上形成的具有保護膜的基 板，藉由JIS-K-5400-1990的8.4,1鉛筆刮擦實驗，測定保 護膜的鉛筆硬度（表面硬度），結果如表1所示。該値爲4H 或更大時，認爲保護膜的表面硬度良好。在針對層間絕緣 -40- 201107884 膜進行時，只是膜厚（3.0 jt/ m)和保護膜不同，所以層間絕緣 膜的鉛筆硬度的評價和保護膜的鉛筆硬度的評價同樣地判 斷。 (4) 保護膜的耐磨損性的評價 對各實施例和比較例中，如上形成的具有保護膜的基 板，使用學振型摩耗試驗機，在鋼絲網#0000上負載200g 的負重’重複1 0次。用肉眼根據以下判斷基準評價磨損情 況，結果如表1所示。 判斷基準 ◎:完全沒有損傷 〇：有1〜3根傷痕 △:有4〜10根傷痕 X :有10根以上的傷痕 只要是◎或〇，就認爲具有良好的耐磨損性。在針對 層間絕緣膜進行時，只是膜厚（3.0/z m)和保護膜不同，所以 層間絕緣膜的耐磨損性的評價和保護膜的耐磨損性的評價 同樣地判斷。 (5) 確認有無皸裂產生（耐皸裂的評價） 對各實施例和比較例中，如上形成的具有保護膜的基 板’在23 °C下放置24小時’其保護膜表面產生皸裂，或者 使用鐳射顯微鏡（Keyence製造的VK-8500)確認。根據以下 的判斷基準進行評價，結果如表1所示。 -41 - 201107884 判斷基準 ◎:完全沒有皸裂 〇：有1〜3個皸裂 △:有4〜10個皸裂 X:有10個以上的皸裂 只要是◎或〇，就認爲確認有無皸裂產生的結果是良 好的。 (6) 保護膜的ITO(銦錫氧化物）密合性評價 除了使用帶有ITO的基板以外，藉由各實施例和比較 例，如上形成保護膜，進行壓力鍋試驗（120°C，濕度1〇〇%， 4小時）。之後，JIS K-5400-1990的8.5.3的黏附性棋盤格 膠帶法，求得100個棋盤格中殘留的棋盤格的數量，評價 保護膜的ITO密合性。結果如表1所示》100個棋盤格中 殘留的棋盤格的數量爲80個以下時，認爲ITO密合性不 好。在針對層間絕緣膜進行時，只是膜厚（3.0从m)和保護膜 不同，所以判斷爲層間絕緣膜的ITO密合性的評價和保護 膜的ITO密合性的評價同樣。 (7) 保護膜的平坦化能力（平坦性）的評價 在 SiCh浸漬玻璃基板上，使用顔料類彩色光阻劑 (JSR(股）製造「JCRRED 689」、「JCR GREEN 706」和「CR 8 200B」）’如下，形成紅、綠和藍3種顏色的條狀濾色片。 也就是，使用旋塗器，將上述彩色光阻劑的1種顏色，塗 布到SiCb浸漬玻璃基板上，在加熱板上，在90 °C下預烘焙 -42- 201107884 150秒鐘，形成塗膜。之後，使用曝光機Can()n PLA501F(Canon(股）製造）’藉由規定圖案的掩膜，照射ghi 線（波長 43611111、405111]1、36511111 的強度比二2.7:2.5:4.8)，換 算爲i線，曝光量爲2,OOOJ/m2，接著，使用〇.〇5質量％的 氫氧化鉀水溶液顯影，用超純水，沖洗60秒鐘。接著，再 在烘箱中，在23 0°C下加熱處理30分鐘，形成單色的條狀 濾色片。重複進行形成3種顏色的該操作，形成紅、綠和 藍這3種顏色的條狀濾色片（條寬200 /z m)。 對測定長度2,000 /z m、測定範圍2,000 // m的方形，選 取紅、綠、藍方向的帶狀線短軸方向和紅-紅、綠-綠、藍_ 藍的相同顏色的帶狀線的長軸方向這2個方向作爲測定方 向，對各方向，選取測定點數n = 5(總計η的數量爲10)，使 用接觸式膜厚測定裝置（KLATENCOR(股）製造的「a-Step」） 測定形成濾色片的基板表面的凹凸時，爲l.Oym。使用旋 塗器在該形成濾色片的基板上，塗布各個感放射線性組成 物後，在加熱板上，在90°C下，預烘焙5分鐘，形成塗膜 後，再在清潔烘箱中，在230°C下後烘焙60分鐘，在濾色 片上面形成膜厚約2.Oym的保護膜。 對在這樣形成的濾色片上具有保護膜的基板，使用接 觸式膜厚測定裝置（KLATENCOR(股）製造的「a -Step」）測 定保護膜表面的凹凸。該測定是對測定長度2,000 V m、測 定範圍2,OOO/zm的方形，選取紅、綠、藍方向的帶狀線短 軸方向和紅-紅、綠-綠、藍-藍的相同顏色的帶狀線的長軸 -43- .201107884 方向這兩個方向作爲測定方向，對各方向，選取測定點數 n = 5(總計η的數量爲10)進行’求得每次測定的最高部和最 底部的高低差（nm)共10次的平均値，作爲保護膜的平坦化 性能（平坦性）的評價’在表1中表示。該値在200nm以下 時，認爲保護膜的平坦化性能良好。 (8) 感放射線性組成物的解析度（層間絕緣膜的清晰度） 的評價 在形成各實施例和比較例中的上述層間絕緣膜時，只 要能顯現出3 0 μ m以下的接觸孔圖案，則可以認爲解析度 良好。可以現象的接觸孔圖案的大小如表1所示。 (9) 感放射線性組成物的保存安定性的評價 使用黏度計（東京計器（股）製造的「ELD型黏度計」）， 測定25 °C下的感放射線性組成物的黏度。之後，將該組成 物在2 5 °C下靜置，同時每隔2 4小時測定2 5 °C的黏度。以 剛製備後的感放射線性組成物的黏度爲基準，求得黏度增 加5 %所需要的天數’將該天數作爲保存穩定性的評價，在 表1中表示。該天數爲1 5天以上時，認爲感放射線性組成 物的保存穩定性良好。 另外’在表1中，[B]矽烷化合物' [C]感放射線性酸產 生劑或感放射線性鹼產生劑、[D ]脫水劑、[E]酸擴散控制 劑、[F]自由基聚合引發劑、以及[G]界面活性劑的簡稱分別 表示下述物質》 -44- 201107884 B-l: 1，4-雙（三甲氧基甲矽烷基甲基）苯 B-2:雙（三乙氧基甲矽烷基）乙烷 B-3:參（3-三甲氧基甲矽烷基丙基）異氰脲酸酯 C-l: 1-(4,7-二丁氧基-1-萘基）四氫噻吩鑰三氟甲磺酸鹽 C-2 :三苯基銃三氟甲磺酸鹽 C-3 : 2-硝基苄基環己基胺基甲酸酯 C-4 : 0-胺基甲醯基羥基醯胺 D-1 :原甲酸甲基 E-1 :三乙基胺 E-2: 2,4,6-參（2-吡啶基）-1,3,5-三畊 F-1: 2-甲基-1-[4-(甲基硫代）苯基]-2-味啉-丙-2-酮 F-2:乙酮- l-〔9-乙基- 6-(2-甲基苯甲醯基）-9H-昨唑-3-基〕 -1-(0-乙醯基肟） G-1 :含氟界面活性劑（（股）NE〇S製造的「FTX-218」） Γ <-· L ά -45- 201107884 【I揪〕 比較例 v〇 8 cn VO Οϊ cn 寸 8 CS en 8 寸 cn Οί 8 CS cn 8 CS CO 實施例 8 vn s C4 CO ν〇 8 Ο s fS cn ι^-t 8 Ο s m 工 8 ο 寸 CO CO S in R CN cn cs S CM 二 8 (N cn Ο 8 CS m On S cs CO 〇〇 S m 卜 8 cs m VO 8 «-« CN m yr\ 8 04 m 寸 8 «ο r>4 c〇 c«-> 8 S <N CO CN 8 irj CS <-H 8 iO m A-l償量份） A-2償量份） A-3(質置份） Α·4(質量份） A-5(質置份） A-6(質置份） B-l(質量份） Β-2(質量份） B-3(質量份） C-l(質量份） C-2(質置份） C-3(質量份） CM(質量份） D-l(質量份） [A诚分 [B诚分 [c]成分 [D戚分 丨9寸— 201107884 s o 5 U~i on X X ο 〇 W"1 o 2 CM 〇\ SO X cs X X ο cs »rj s o o 3 00 σ\ 〇J X vn 〇 X ο cs S 〇 5 〇〇 〇\ <N 〇 X ο s CSJ 沄 o s o S 〇〇 〇\ CS X \n 〇 X ο cs o s o 3 ύΟ σ\ CO X \y\ 〇 X ο 沄 泛 o 爸 o cs S ε； 〇J NO ◎ ◎ S g s o o 2 On CO tn w-> ◎ ◎ 8 O 2 On ON V£) ◎ ◎ g 异 2 tn v〇 ◎ ◎ g oo o 2 〇\ ON — tr： VO ◎ ◎ g oo 8 O 3 Os ON ffi v〇 ◎ 〇 § § oo 8 c> 3 ON OS $ ◎ 〇 8 o 异 o 3 ON ffi Ό ◎ ◎ 8 o 沄 g o 3 ON ON v〇 ◎ ◎ 8 § s s o 3 a\ ON $ ◎ 〇 8 o oo S O 2 s D： Ό ◎ ◎ S g s o 3 Os ON r*H $ ◎ ◎ 8 g oo o 2 〇\ On 蜱 s VO 〇 ◎ 8 o s s o 2 ON 〇\ ffi o ◎ 8 g oo s o s Os On ^-1 ffi »/*% 〇 ◎ S i § oo s o S <N 〇 ◎ S g s o -—1 On <J\ 一 o ◎ 8 g oo i ¢1 ' Ξ § _ ώ i _ a £ i _ » ri ti § 囀 ft s g m s m * 1 m 班 m m s 酿 繼 @ <D i /—s i UA3 g 51 ! m m fK 逛 m 妝 m <k 链 g 堪 E 堪 g _z寸· r*f- s 201107884 從表1的結果表明，由含有[A]、[B]和[C]成分的實 施例1 ~ 1 7的感放射線性組成物形成的保護膜與由缺少 這些成分中的任意成分的比較例1~6的感放射線性組成 物形成的保護膜相比，在透明性、耐熱透明性、鉛筆硬 度、耐磨損性、耐皸裂、ITO密合性和平坦性能方面， 更加均衡且優異。另外，還可以知道實施例1〜17的感放 射線性組成物和比較例1〜6的感放射線性組成物相比， 形成層間絕緣膜的接觸孔的解析度更高（也就是，層間絕 緣膜的清晰度更優異）》此外，實施例1~17的感放射線 性組成物具有足夠的保存穩定性。 產業利用性 本發明的感放射線性組成物如上所述，可以形成平 坦性、透明性、耐熱性、耐熱透明性、表面硬度和耐磨 損性更加均衡地優異，以及可以形成對ITO基板的密合 性以及耐皸裂改善了的保護膜和層間絕緣膜。另外，該 感放射線性組成物顯現出可以形成接觸孔的這樣的足夠 的解析度，而且保存穩定性也優異。因此，該感放射線 性組成物適合用於形成液晶顯示元件使用的保護膜和層 間絕緣膜。 【圖式簡單說明】 Μ 。 【主要元件符號說明】 〇 •48-[S - 37 - 201107884 The number average molecular weight (Mn) of the decondensed product was 00, and the molecular weight distribution (Mw/Mn) was 2. [Synthesis Example 6] In a container with a stirrer, 25 parts by mass of propylene glycol monomethyl decyl ether was added, followed by 'addition of 17 parts by mass of methyltrimethoxydecane, 15 parts by mass of tetraethoxy sane, and 12 parts by mass. - methacryloxypropyltrimethoxydecane, 15 parts by mass of phenyltrimethoxydecane, and ο" parts by weight of triisopropoxyl toluene, a hydrolysis condensate obtained by the same method as in the synthesis example ( A_6). The solid content concentration of the hydrolysis-condensation product (A-6) was 40.8 mass%, and the obtained hydrolyzed condensate had a number average molecular weight (?η) of 1,600 and a molecular weight distribution (Mw/Mn) of 2. Preparation of a radiation sensitive composition and formation of a protective film and an interlayer insulating film [Example 1] A solution containing a hydrolysis condensate (A-1) obtained in Synthesis Example 1 (corresponding to 100 parts by mass of a hydrolysis condensate (A- 1) (amount of solid content), 15 parts by mass of (Bl) 1,4-bis(trimethoxymethylmethylmethyl)benzene as a component [B], and 2 parts by mass as a component [C] (Cl) 1-(4,7·dibutoxy-1-naphthyl)tetrahydrothiophene trifluoromethanesulfonate, 3 parts by mass of methyl orthoformate as the component [D], 0.05 parts by mass as [ (E-1) triethylamine as component E], 0.1 parts by mass of (G-1) fluorine-containing surfactant (GFT) fluorosurfactant ("FTX-218" manufactured by NEOS) as a component [G], and propylene glycol monomethyl group The radiation-sensitive composition was prepared so that the solid content concentration was 25% by mass. After applying the ray-sensitive composition to the SiCh-impregnated glass substrate using a spin coater, it was prebaked at 90 ° C for 2 minutes on a heated blister-38-201107884 to form a coating film (the ITO adhesion described later) In the evaluation, the substrate with ruthenium was used 'in the evaluation of the flattening performance', the Si 〇 2 immersed glass substrate on which the filter was formed was used.) Next, the obtained coating film was exposed at an amount of 5,000 J/m 2 . Exposure to ultraviolet light. Then, after developing at 25 ° C for 80 seconds by a 2.38 mass % aqueous solution of tetramethylammonium hydroxide, the mixture was washed with pure water for 1 minute, and then heated in an oven at 230 ° C for 60 minutes to form a film thickness of 2. Protective film. Further, 'the number of revolutions of the spin coater at the time of forming the coating film was adjusted so that the film thickness after heating was 3.0 / / m, except by having a size of 20 / / m > 30 / zm, 40 / zm, 50 / zm The reticle of the contact hole pattern is formed by exposing a 150 # m exposure slit (interval between the substrate and the reticle) in the same manner as the above-described protective film. [Examples 2 to 17 and Comparative Examples 1 to 6] A radiation sensitive composition was prepared in the same manner as in Example 1 except that the types and amounts of the respective components were as shown in Table 1. Then, a protective film and an interlayer insulating film were formed in the same manner as in Example 1 using the radiation sensitive composition prepared in this manner. Physical Properties The transparency, heat-resistant transparency, surface hardness, abrasion resistance, chopping resistance, IT0 adhesion and flatness, and radiation-induced linear composition of the protective film formed in Examples 1 to 17 and Comparative Examples 1 to 6 were evaluated. The resolution of the object (the sharpness of the interlayer insulating film) and the evaluation method of the storage stability are as follows. The "resolution" of the radiation-sensitive composition is an evaluation of the performance of a precise contact hole in which the composition can form an interlayer insulating film, and provides an evaluation of "clear-39-201107884 degree" as an interlayer insulating film. (1) Evaluation of the transparency of the protective film In each of the examples and the comparative examples, the substrate having the protective film formed as described above was subjected to a spectrophotometer (1 50-20 type Double-Beam manufactured by Hitachi, Ltd.). The light transmittance (%) at a wavelength of 400 to 800 nm was measured. The evaluation of the minimum 光线 of the light transmittance (%) at a wavelength of 400 to 800 nm as transparency is shown in Table 1. When the enthalpy is 95% or more, the transparency of the protective film is considered to be good. When the interlayer insulating film was used, the film thickness (3.0 #m) and the protective film were different. Therefore, the evaluation of the transparency of the interlayer insulating film was evaluated in the same manner as the evaluation of the transparency of the protective film. (2) Evaluation of heat-resistant transparency of the protective film In each of the examples and the comparative examples, the substrate having the protective film formed as described above was heated at 250 ° C for 1 hour in a cleaning oven according to the above formula (1). The method described in "Evaluation of Transparency of Protective Film" measures the light transmittance before and after heating. The heat-resistant transparency (%) calculated according to the following formula is shown in Table 1. When the enthalpy is 4% or less, it is considered that the heat-resistant transparency of the protective film is good. Heat-resistant transparency (%) == light transmittance before heating (%) - light transmittance after heating (%) (3) Measurement of pencil hardness (surface hardness) of protective film For each of Examples and Comparative Examples, The substrate having the protective film formed as described above was subjected to a pencil scratch test of 8.4, 1 by JIS-K-5400-1990, and the pencil hardness (surface hardness) of the protective film was measured. The results are shown in Table 1. When the 値 is 4H or more, the surface hardness of the protective film is considered to be good. When the film was applied to the interlayer insulating film -40 - 201107884, the film thickness (3.0 jt/m) was different from that of the protective film. Therefore, the evaluation of the pencil hardness of the interlayer insulating film and the evaluation of the pencil hardness of the protective film were similarly determined. (4) Evaluation of abrasion resistance of the protective film In each of the examples and the comparative examples, the substrate having the protective film formed as described above was loaded with a load of 200 g on the wire mesh #0000 using a vibration-type tester. 10 times. The wear was evaluated by the naked eye according to the following criteria, and the results are shown in Table 1. Judgment criteria ◎: No damage at all 〇: There are 1 to 3 scratches △: 4 to 10 scratches X: 10 or more scratches If it is ◎ or 〇, it is considered to have good abrasion resistance. When the interlayer insulating film was used, the film thickness (3.0/z m) was different from that of the protective film. Therefore, the evaluation of the abrasion resistance of the interlayer insulating film and the evaluation of the abrasion resistance of the protective film were similarly determined. (5) Confirmation of the presence or absence of splitting (evaluation of crack resistance) For each of the examples and the comparative examples, the substrate 'with the protective film formed as described above was left at 23 ° C for 24 hours', and the surface of the protective film was cleaved, or laser was used. The microscope (VK-8500 manufactured by Keyence) was confirmed. The evaluation was carried out based on the following criteria, and the results are shown in Table 1. -41 - 201107884 Judgment criteria ◎: There is no splitting at all: There are 1 to 3 splits △: There are 4 to 10 splits X: If there are more than 10 splits, as long as it is ◎ or 〇, it is considered that the result of cracking is confirmed. It is good. (6) Evaluation of ITO (Indium Tin Oxide) adhesion of the protective film In addition to the use of the substrate with ITO, the protective film was formed as described above by each of the examples and the comparative examples, and the pressure cooker test was performed (120 ° C, humidity 1). 〇〇%, 4 hours). Then, in the adhesion checkerboard tape method of 8.5.3 of JIS K-5400-1990, the number of checkerboards remaining in 100 checkerboards was obtained, and the ITO adhesion of the protective film was evaluated. As a result, as shown in Table 1, when the number of the remaining checkerboards in the 100 checkerboards was 80 or less, the ITO adhesion was considered to be poor. When the interlayer insulating film was used, the film thickness (3.0 from m) was different from that of the protective film. Therefore, it was judged that the evaluation of the ITO adhesion of the interlayer insulating film was the same as the evaluation of the ITO adhesion of the protective film. (7) Evaluation of the flattening ability (flatness) of the protective film. Using a pigment-based color resist (JSRRED 689, JCR GREEN 706, and CR 8 200B) on a SiCh-impregnated glass substrate ")" As follows, a strip of color filters of three colors of red, green and blue is formed. That is, a color of the above-mentioned color photoresist is applied onto a SiCb-impregnated glass substrate using a spin coater, and pre-baked at 40 ° C for -42 to 201107884 for 150 seconds on a hot plate to form a coating film. . Then, using the exposure machine Can() n PLA501F (manufactured by Canon), the intensity ratio of the ghi line (wavelengths 43611111, 405111] 1, 36511111 is 2.7:2.5:4.8 by the mask of the predetermined pattern. For the i-line, the exposure amount was 2,OOJ/m2, and then, it was developed with a 5% by mass aqueous solution of potassium hydroxide, and washed with ultrapure water for 60 seconds. Then, it was heat-treated at 23 ° C for 30 minutes in an oven to form a monochromatic strip filter. This operation of forming three colors was repeated to form strip-shaped color filters (bar width 200 / z m) of three colors of red, green, and blue. For a square measuring 2,000 /zm in length and measuring range 2,000 // m, select the strip line of the same color in the red, green and blue directions and the strip line of the same color of red-red, green-green and blue_blue. The two directions of the long axis direction are the measurement directions, and the number of measurement points n = 5 (the total number of η is 10) is selected for each direction, and the contact type film thickness measuring device ("A-Step" manufactured by KLATENCOR) is used. When the unevenness of the surface of the substrate on which the color filter is formed is measured, it is 1.0 μm. Applying each of the radiation sensitive compositions on the color filter substrate using a spin coater, prebaking at 90 ° C for 5 minutes on a hot plate to form a coating film, and then in a cleaning oven. After baking at 230 ° C for 60 minutes, a protective film having a film thickness of about 2.Oym was formed on the color filter. To the substrate having the protective film formed on the color filter thus formed, the unevenness of the surface of the protective film was measured using a contact type film thickness measuring device ("a-step" manufactured by KLATENCOR Co., Ltd.). The measurement is for a square measuring 2,000 V m in length and measuring range of 2,OO/zm, and selecting the short-axis direction of the strip line in the red, green, and blue directions and the same color of red-red, green-green, and blue-blue. The long axis of the strip line -43-.201107884 The two directions are used as the measurement direction. For each direction, the number of measurement points n = 5 (the total number of η is 10) is selected to obtain the highest part of each measurement. The average enthalpy of the lowest height difference (nm) of 10 times at the bottom is evaluated as the evaluation of the flattening performance (flatness) of the protective film. When the ruthenium is 200 nm or less, the planarization performance of the protective film is considered to be good. (8) Evaluation of the resolution of the radiation sensitive composition (sharpness of the interlayer insulating film) When the interlayer insulating film in each of the examples and the comparative examples is formed, a contact hole pattern of 30 μm or less can be exhibited. , you can think that the resolution is good. The size of the contact hole pattern that can be observed is shown in Table 1. (9) Evaluation of the storage stability of the radiation-sensitive composition The viscosity of the radiation-sensitive composition at 25 ° C was measured using a viscometer ("ELD-type viscometer" manufactured by Tokyo Keiki Co., Ltd.). Thereafter, the composition was allowed to stand at 25 ° C while measuring the viscosity at 25 ° C every 24 hours. The number of days required to obtain a viscosity increase of 5% was determined based on the viscosity of the radiation-sensitive linear composition immediately after preparation. The number of days was evaluated as the storage stability, and is shown in Table 1. When the number of days is 15 or more, the storage stability of the radiation sensitive composition is considered to be good. In addition, in Table 1, [B] decane compound '[C] sensitizing radioactive acid generator or sensitizing radiobase generator, [D] dehydrating agent, [E] acid diffusion controlling agent, [F] radical polymerization The abbreviations of the initiator and the [G] surfactant are respectively represented by the following substances: -44- 201107884 Bl: 1,4-bis(trimethoxymethylmethylmethyl)benzene B-2: bis(triethoxy) Methanealkyl)ethane B-3: cis (3-trimethoxycarbamidylpropyl) isocyanurate Cl: 1-(4,7-dibutoxy-1-naphthalenyl)tetrahydrothiophene Key triflate C-2 : triphenylsulfonium trifluoromethanesulfonate C-3 : 2-nitrobenzylcyclohexylcarbamate C-4 : 0-aminocarbamidohydroxyl Indoleamine D-1 : orthoformic acid methyl E-1 : triethylamine E-2: 2,4,6-gin (2-pyridyl)-1,3,5-three tillage F-1: 2- Methyl-1-[4-(methylthio)phenyl]-2-sodium-propan-2-one F-2: ethyl ketone-l-[9-ethyl-6-(2-methyl Benzyl hydrazino)-9H-n-oxazol-3-yl]-1-(0-acetamido fluorene) G-1 : fluorinated surfactant ("FTX-218" manufactured by NE〇S) Γ <-· L ά -45- 201107884 [I揪] Comparative example v〇8 cn VO Ο Cn cn inch 8 CS en 8 inch cn Οί 8 CS cn 8 CS CO Example 8 vn s C4 CO ν〇8 Ο s fS cn ι^-t 8 Ο sm 8 ο inch CO CO S in R CN cn cs S CM 2 8 (N cn Ο 8 CS m On S cs CO 〇〇S m 卜 8 cs m VO 8 «-« CN m yr\ 8 04 m inch 8 «ο r>4 c〇c«-> 8 S <N CO CN 8 irj CS <-H 8 iO m Al reimbursement) A-2 reimbursement) A-3 (mass fraction) Α·4 (mass) A-5 (mass fraction) A-6 (mass fraction) Bl (parts by mass) Β-2 (parts by mass) B-3 (parts by mass) Cl (parts by mass) C-2 (mass parts) C-3 (mass parts) CM (mass) Share) Dl (mass) [A credit [B Cheng cent [c] ingredients [D戚 分丨 9 inch — 201107884 so 5 U~i on XX ο 〇W"1 o 2 CM 〇\ SO X cs XX ο Cs »rj soo 3 00 σ\ 〇JX vn 〇X ο cs S 〇5 〇〇〇\ <N X ο s CSJ 沄oso S 〇〇〇\ CS X \n 〇X ο cs oso 3 ύΟ σ\ CO X \y\ 〇X ο 沄泛o da dao o cs S ε; 〇J NO ◎ ◎ S gsoo 2 On CO tn w-> ◎ ◎ 8 O 2 On ON V£) ◎ ◎ g 2 2 tn v〇 ◎ ◎ g oo o 2 〇 \ ON — tr: VO ◎ ◎ g oo 8 O 3 Os ON ffi v〇 ◎ 〇§ § oo 8 c> 3 ON OS $ ◎ 〇8 o different o 3 ON ffi Ό ◎ ◎ 8 o 沄go 3 ON ON v〇◎ ◎ 8 § sso 3 a\ ON $ ◎ 〇8 o oo SO 2 s D: Ό ◎ ◎ S gso 3 Os ON r*H $ ◎ ◎ 8 g oo o 2 〇\ On 蜱s VO 〇 ◎ 8 osso 2 ON 〇\ ffi o ◎ 8 g oo sos Os On ^-1 ffi »/ *% 〇◎ S i § oo so S <N 〇◎ S gso -1 On <J\ a o ◎ 8 g oo i ¢1 ' Ξ § _ ώ i _ a £ i _ » ri ti § 啭Ft sgmsm * 1 m class mms brewed following @ <D i /—si UA3 g 51 ! mm fK w m makeup m <k chain g kan E _g inch · r*f- s 201107884 Results from Table 1 Indicates that it contains [A], [B] The protective film formed of the radiation sensitive composition of Examples 1 to 17 of the component [C] was compared with the protective film formed of the radiation sensitive composition of Comparative Examples 1 to 6 which lacked any of these components. It is more balanced and excellent in transparency, heat-resistant transparency, pencil hardness, abrasion resistance, chopping resistance, ITO adhesion, and flatness. Further, it is also known that the radiation sensitive compositions of Examples 1 to 17 have higher resolution of the contact holes forming the interlayer insulating film than the radiation sensitive compositions of Comparative Examples 1 to 6 (that is, the interlayer insulating film). The sharpness of the film is more excellent.) Further, the radiation sensitive compositions of Examples 1 to 17 have sufficient storage stability. INDUSTRIAL APPLICABILITY As described above, the radiation-sensitive linear composition of the present invention can form flatness, transparency, heat resistance, heat-resistant transparency, surface hardness, and abrasion resistance more uniformly, and can form a dense ITO substrate. A protective film and an interlayer insulating film which are improved in properties and resistance to cracking. Further, the radiation sensitive composition exhibits such sufficient resolution that a contact hole can be formed, and is excellent in storage stability. Therefore, the radiation sensitive composition is suitable for use in forming a protective film and an interlayer insulating film used for a liquid crystal display element. [Simple description of the diagram] Μ . [Main component symbol description] 〇 • 48-