200842162 九、發明說明 【發明所屬之技術領域】 本發明係有關敏輻射線性樹脂組成物，間隔器與其製 造方法及液晶顯示元件。詳言之，係有關適合作爲用於形 成液晶顯示面板或觸控面板等顯示元件所使用之間隔器的 材料之敏輻射線性樹脂組成物，由該組成物所形成之顯示 元件用間隔器，及具備該間隔器所成的液晶顯示元件。 【先前技術】 液晶顯示元件中，習知，爲了在2片基板間保有一定 的間隔（細胞間隙），使用具有設定粒徑的玻璃珠，塑膠珠 等的間隔器粒子，但由於該等間隔器粒子不規則的散佈在 玻璃基板等的透明基板上，在像素形成區域中，若存在有 間隔器粒子時，將會產生間隔器粒子的炫光（glare)現象， 入射光受到散射，液晶面板的對比將有降低的問題。 因此’爲了解決該等問題，已經開始採用由平版印刷 光微影法形成間隔器的方法。該方法係將敏輻射線性樹脂 組成物塗佈於基板上，介由設定之光罩使紫外線曝光後顯 影’形成點狀或條帶狀的間隔器，由於可僅於像素形成區 域以外之設定場所形成間隔器，故前述問題可獲得基本的 解決。由於此種間隔器形成用敏輻射線性樹脂組成物所形 成的間隔益’必須滿足間隔器所要求的功能，故與習知之 例如層間絕緣膜形成用的組成物相異，而具有用於形成間 隔器之特化的成分或組成。 -4- 200842162 但是，近年來，即使採用相關之新的敏輻射線性樹脂 組成物，就減低製造成本的觀點而言，使用與習知使用的 材料相同之步驟的案例漸漸增加。在此情形下，間隔器用 敏輻射線性樹脂組成物以自最適步驟條件偏離的條件使用 之情形爲多，特別是預烘烤溫度自最適條件偏離時，會產 生無法獲得充分的解像度，或圖型剝離的問題。又伴隨著 基板大型化，即使在同一基板上，因烘烤溫度的分布產 生，在近似烘烤（proximity baking)時，基板的翹曲有更顯 著的傾向，因此，有必要具有更寬廣製程界線（process margin)之間隔器用敏輻射線性樹脂組成物。 因此，爲了解決該問題，本案申請人已經在日本特開 200 1 -3 027 1 2號公報中，表明具有可對應步驟條件變化之 寬廣的製程界線，且可賦予作爲間隔器之必要的兼具耐熱 性，耐藥品性，透明性及硬度之圖型狀硬化物的敏輻射線 性樹脂組成物。 另外，近年來，就提高生產性的觀點而言，有在液晶 顯示元件的製造中’於貼合液晶面板的玻璃前面，將液晶 材料滴在玻璃表面的步驟技術，即所謂〇 D F (—滴充塡 One Drop Fill)法被導入。藉由該方法，可大幅縮短製造 fe晶顯不兀件所需要的時間。例如，以習知的方法塡充 3 〇英吋面板用液晶時，需要約5天的時間，若導入〇 D F 法，則只要2小時即可完成，可大幅提高生產性。 習知的貼合方式中，於貼合TF T陣列與濾色片時， 由於施加負荷，因負荷使得間隔器被平均地壓著，可保有 200842162 間隔器高度的均一性。但是’在〇df法中’最初因只以 基板重量的負荷與大氣壓貼合，與習知法相較’初期貼合 的負荷小。因此’即使以小的負荷壓著間隔器’在平均地 壓著下，亦能顯現高度的均一性，此點甚爲重要。因此， 間隔器有必要具備柔軟性，同時具備高度的彈性回復率。 間隔器的高度若不平均，不能保有細胞間隙的平均性，細 胞內產生空隙，將導致顯示不均。但是，習知的間隔器 中，具柔軟性者’在壓縮負荷試驗中，雖然顯現出高的彈 性變形量，但有彈性回復率低的傾向。 爲了柔軟性與高彈性回復率並存，日本特開2 0 0 2 -1 748 1 2號公報中’提案使用具有多環式立體構造的脂環 式化合物’所獲得之含樹脂的敏輻射線性樹脂組成物。但 是，在此情形下’由於樹脂中具多環式立體構造，組成物 的被膜對鹼顯影液的顯影性顯著降低。 進而，近年中’就製造成本的減低或節省能量的觀點 而言，強烈期望敏輻射線性樹脂組成物的曝光量能盡量減 少〇 【發明內容】 發明揭示 因此’本發明的目的係提供在少量的曝光量，例如即 使在1，5 0 0 J7 m 2以下的曝光量下，亦能形成密接性，硏磨 耐性及耐熱性優異，進而具有柔軟性與高彈性回復率，對 驗顯影液具優異顯影性的液晶顯示元件間隔器的敏輻射線 -6- 200842162 性樹脂組成物° 本發明的其他目的’係提供密接性，硏磨耐性及耐熱 性優異，兼具柔軟性與高彈性回復率的間隔器及其製造 法，以及具備相關間隔器的液晶顯示元件。 由以下的說明’本發明的其他目的及優點即可自明。 根據本發明’本發明的上述目的及優點第1爲可藉由 含有[A](al)選自不飽和竣酸及不飽和殘酸酐所成群之至 少1種（以下，稱爲「化合物（al)」）， (a2)下述式（1)BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a radiation sensitive linear resin composition, a spacer, a method of manufacturing the same, and a liquid crystal display element. More specifically, it relates to a radiation sensitive linear resin composition suitable as a material for forming a spacer used for a display element such as a liquid crystal display panel or a touch panel, and a spacer for a display element formed of the composition, and A liquid crystal display element formed by the spacer is provided. [Prior Art] In the liquid crystal display device, it is conventional to use spacer particles such as glass beads or plastic beads having a predetermined particle diameter in order to maintain a certain interval (cell gap) between the two substrates, but these spacers are used. The particles are irregularly dispersed on a transparent substrate such as a glass substrate. If spacer particles are present in the pixel formation region, glare phenomenon of the spacer particles is generated, and the incident light is scattered, and the liquid crystal panel is scattered. Contrast will have a problem of reduction. Therefore, in order to solve such problems, a method of forming a spacer by lithographic photolithography has been started. In the method, the sensitive radiation linear resin composition is applied onto a substrate, and the ultraviolet ray is exposed and developed by a reticle to form a dot or strip-shaped spacer, since it can be set only outside the pixel formation region. The spacer is formed, so that the aforementioned problems can be basically solved. Since the spacer formed by the spacer-forming radiation-sensitive linear resin composition must satisfy the functions required for the spacer, it is different from the conventional composition for forming an interlayer insulating film, and has a space for forming spacers. Specialized composition or composition of the device. -4- 200842162 However, in recent years, even with the related new sensitive radiation linear resin composition, the use of the same steps as the conventionally used materials has gradually increased from the viewpoint of reducing the manufacturing cost. In this case, the spacer is used with the sensitive radiation linear resin composition in a condition that deviates from the optimum step condition, and in particular, when the prebaking temperature deviates from the optimum condition, sufficient resolution, or pattern, may not be obtained. The problem of stripping. Further, as the substrate is enlarged, even on the same substrate, due to the distribution of the baking temperature, the warpage of the substrate tends to be more pronounced in the case of proximity baking, and therefore it is necessary to have a wider process boundary. The spacer of the process margin is made of a sensitive radiation linear resin composition. Therefore, in order to solve this problem, the applicant of the present application has disclosed in Japanese Laid-Open Patent Publication No. 2001- 0271-2, that it has a wide process boundary that can correspond to changes in step conditions, and can be provided as a necessary combination for the spacer. A radiation-sensitive linear resin composition of heat-resistant, chemical-resistant, transparent, and hard-cured graph-like cured product. In addition, in recent years, from the viewpoint of improving productivity, there is a step technique of dropping a liquid crystal material on a glass surface in front of a glass in which a liquid crystal panel is bonded in the manufacture of a liquid crystal display element, that is, a so-called 〇DF (-drop) The One Drop Fill method was introduced. By this method, the time required to manufacture the feminine display member can be greatly shortened. For example, when a liquid crystal panel for a panel of 3 inches is filled by a conventional method, it takes about 5 days, and if the 〇 D F method is introduced, it can be completed in 2 hours, and the productivity can be greatly improved. In the conventional bonding method, when the TF T array and the color filter are attached, the spacer is uniformly pressed by the load due to the application of the load, and the uniformity of the height of the spacer of 200842162 can be maintained. However, in the 〇df method, the load is initially applied to the atmospheric pressure only by the load of the substrate weight, and the load at the initial stage is smaller than that of the conventional method. Therefore, it is important to show a high degree of uniformity even if the spacer is pressed under a small load with an average pressure. Therefore, it is necessary for the spacer to have flexibility and a high elastic recovery rate. If the height of the spacer is not uniform, the average of the cell gap cannot be maintained, and voids are generated in the cells, resulting in uneven display. However, in the conventional spacer, the flexible one has a tendency to exhibit a high elastic deformation amount in the compression load test, but has a low elastic recovery rate. In order to coexist with softness and high elastic recovery rate, the resin-containing radiation sensitive linear resin obtained by the 'Proposal using an alicyclic compound having a multi-ring stereo structure' is proposed in Japanese Patent Laid-Open Publication No. 2000-127144 Composition. However, in this case, since the resin has a multi-ringed three-dimensional structure, the developability of the film of the composition to the alkali developer is remarkably lowered. Further, in recent years, from the viewpoint of reduction in manufacturing cost or energy saving, it is strongly desired that the exposure amount of the linear radiation-sensitive resin composition can be minimized. [Inventive content] Accordingly, the object of the present invention is to provide a small amount. The exposure amount, for example, can be excellent in honing resistance and heat resistance even at an exposure amount of 1,500 Å J7 m 2 or less, and further has flexibility and high elastic recovery rate, and is excellent for the developer. The sensitive radiation of the developable liquid crystal display element spacer -6- 200842162 resin composition ° The other object of the present invention is to provide adhesion, excellent honing resistance and heat resistance, and flexibility and high elastic recovery rate. a spacer and a method of manufacturing the same, and a liquid crystal display element having an associated spacer. Other objects and advantages of the present invention will be apparent from the following description. According to the present invention, the above objects and advantages of the present invention are at least one of the group consisting of [A](al) selected from the group consisting of unsaturated decanoic acid and unsaturated residual acid anhydride (hereinafter referred to as "compound ( Al)"), (a2) following formula (1)
(式（1)中，R1，R2示各自獨立的氫原子或1價的有機基， R3示氫原子或甲基，X示2價有機基）所示之不飽和化合 物（以下，稱爲「化合物（a2)」），以及 (a3)選自丙烯酸烷酯，甲基丙烯酸烷酯，丙烯酸脂環 式酯’甲基丙烯酸脂環式酯，丙烯酸芳基酯，丙烯酸芳烷 酯，曱基丙烯酸芳基酯，甲基丙烯酸芳烷酯，二羧酸二烷 基酯，甲基丙烯酸羥基烷基酯，含氧1原子的不飽和5或 6員環之甲基丙烯酸酯，丙烯酸環氧基烷基酯，甲基丙烯 -7- 200842162 酸環氧基院基酯，α -院基丙儲酸環氧基院基酯，具有不飽 和鍵的縮水甘油基醚，乙烯芳香族化合物，二羰基醯亞胺 衍生物，共軛二烯以及丙烯腈’甲基丙烯腈，丙烯醯胺， 甲基丙烯醯胺，氯化乙烯，氯化亞乙烯及乙酸乙烯酯所成 群之至少1種的不飽和化合物（以下，稱爲「化合物（a 3)」） 之共聚物（以下，稱爲「共聚物[A]」）， [B] 聚合性不飽和化合物，以及 [C] 敏輻射線性聚合引發劑 的敏輻射線性樹脂組成物而達成。該敏輻射線性樹脂 組成物適合作爲形成液晶顯示元件用間隔器。 本發明的上述目的及優點第2爲可藉由自上述敏輻射 線性樹脂組成物所形成之液晶顯示元件用間隔器，及具備 該等的液晶顯示元件而達成。 本發明的上述目的及優點第3爲 可藉由以至少依序含有下述記載之步驟爲特徵之液晶 顯示元件用間隔器的形成方法而達成。 (1) 於基板上形成上述敏輻射線性樹脂組成物的被膜 之形成步驟， (2) 將該被膜的至少一部份曝光的步驟， (3) 將曝光後的被膜顯影的步驟，及 (4) 將顯影後的被膜加熱的步驟。 本發明的上述目的及優點第4爲可藉由上述共聚物[A] 而達成。 -8- 200842162 實施發明之最佳形態 關於本發明詳細說明如下。 敏輻射線性樹脂組成物 本發明的敏輻射線性樹脂組成物至少含有共聚物 [A]，[B]聚合性不飽和化合物及[C]敏輻射線性聚合引發 劑。 -共聚物[A]- 共聚物[A]，可藉由將化合物（al)，化合物（a2)及化合 物（a3 )的混合物，較佳爲在溶劑中，聚合引發劑的存在 下，進行自由基聚合而製造。 製造共聚物〔A〕所使用之化合物（al)，係選自不飽 和羧酸及不飽和羧酸酐所成群之至少1種。 相關的化合物（al)方面，可例舉丙烯酸，甲基丙烯 酸’巴豆酸，2-甲基丙烯醯氧乙基琥珀酸，2-甲基丙烯醯 氧乙基六氫酞酸等的單羧酸； 順丁烯二酸，反丁烯二酸，檸康酸，中康酸，伊康酸 等的二羧酸； 該二羧酸的酐等。 該等化合物（a 1)中，就共聚合反應性，對所得共聚物 之鹼水溶液的溶解性，及取得容易的觀點而言，以丙烯 酸，甲基丙烯酸，順丁烯二酸酐，或2-甲基丙烯醯氧乙 基六氫酞酸爲佳。 * 9 - 200842162 化合物（a 1 )，可單獨使用或混合2種以上使用。 共聚物〔A〕中，由化合物（al)而來之重覆單位的含 有率，較佳爲5〜50重量％，更佳爲10〜4〇重量％，最佳 爲1.5〜30重量％。由化合物U1)而來之重覆單位的含有率 若不足5重量％時，對鹼水溶液的溶解性不足’另一方 面，若超過5 0重量％時’對鹼水溶液的溶解性有過大的 疑慮。 用於製造共聚物〔A〕所使用之化合物（a2) ’爲上述 式（1)所示之化合物。 上述式（1)中，R1及R2的1價有機基方面’可例舉碳 數1〜6的烷基等，其具體例方面，可例舉甲基，乙基， 異丁基等。 上述式（1)中，X的2價有機基方面，可例舉亞甲 基，碳數2〜6的烷撐基等。碳數2〜6的烷撐基之具體例 方面，可例舉乙烯基，1，3-丙烯基，1，4-丁烯基等。 化合物（a2)的具體例方面，可例舉4-丙烯醯基氧甲 基-2,2-二甲基-1，3-二噁戊烷（(1丨(^〇：^1^)，4_丙烯醯基氧甲 基-2-甲基-2-乙基-1，3-二噁戊烷，4-丙烯醯基氧甲基-2,2-二乙基-1，3-二噁戊烷，4-丙烯醯基氧甲基-2-甲基-2-異丁 基-1，3-二噁戊烷，4-丙烯醯基氧甲基-2-環戊基-1，3-二噁 戊烷，4-丙烯醯基氧甲基-2-環己基-1，3-二噁戊烷，4-丙 烯醯基氧乙基-2·甲基-2-乙基-1，3_二噁戊烷，4 -丙烯醯基 氧丙基-2-甲基-2-乙基-1，3-二噁戊烷，4-甲基丙烯醯基氧 丁基-2 -甲基-2 -乙基-1，3 -二B惡戊焼等的丙烯酸衍生物； -10- 200842162 4 -甲基丙烯醯基氧甲基-2,2 -二甲基-1，3-二噁戊烷，4-甲基丙嫌醯基氧甲基-2 -甲基-2-乙基·1，3 -二B惡戊院，4 -甲 基丙烯醯基氧甲基-2,2-二乙基-l，3-二噁戊烷，4-甲基丙烯 醯基氧甲基-2-甲基-2-異丁基-1，3-二噁戊烷，4 -甲基丙烯 醯基氧甲基-2-環戊基-1，3 -二Π惡戊院，4 -甲基丙烯醯基氧 甲基-2 -環己基-1，3 -二D惡戊院，4 -甲基丙燃醯基氧乙基- 2-甲基-2-乙基-1，3-二噁戊烷，4 -甲基丙烯醯基氧丙基-2 -甲 基-2-乙基-1，3-二噁戊烷，4-甲基丙烯醯基氧丁基-2-甲基-2 -乙基-1，3 -二D惡戊院等的甲基丙烯酸衍生物等。 該等之中，就聚合性優異的觀點，就所得敏輻射線性 樹脂組成物對鹼顯影液之顯影性優異的觀點，以及就所得 間隔器兼具高柔軟性及高彈性回復率的觀點而言，以使用 4 -丙烯醯基氧甲基-2 -甲基-2-乙基-1，3-二噁戊烷，4 -丙烯 酸基氧甲基-2-甲基-2 -異丁基-1，3 -二Π惡戊院，4 -丙嫌釀基 氧甲基-2-環己基-1，3-二噁戊烷，4-甲基丙烯醯基氧甲基-2-甲基-2-乙基-1，3-二噁戊烷，4-甲基丙烯醯基氧甲基-2-甲基-2-異丁基-1，3-二噁戊烷或4-甲基丙烯醯基氧甲基- 2-環己基-1，3 -二噁戊烷爲佳。 化合物（a2)，可單獨使用或混合2種以上使用。 共聚物〔A〕中，由化合物（a2)而來之重覆單位的含 有率，較佳爲1〜7 0重量％，特佳爲3〜5 0重量％。由化 合物（a2)而來之重覆單位的含有率若不足1重量％時，所 得敏輻射線性樹脂組成物之對鹼顯影液的顯影性有不足的 傾向，另一方面，若超過70重量％時，顯影性過高，對 -11 - 200842162 放射線的感度不足，有損於所得圖型的形狀。 用於製造共聚物〔A〕所使用之化合物（a3)爲選自丙 烯酸烷基酯，甲基丙烯酸烷基酯，丙烯酸脂環式酯，甲基 丙烯酸脂環式酯，丙烯酸芳基酯，丙烯酸芳烷酯，甲基丙 烯酸芳基酯，甲基丙烯酸芳烷酯，二羧酸二烷基酯，甲基 丙烯酸羥基烷基酯，含氧1原子之不飽和5或6員環的甲 基丙烯酸酯，丙烯酸環氧基烷基酯，甲基丙烯酸環氧基烷 基酯，烷基丙烯酸環氧基烷基酯，具有不飽和鍵之縮水 甘油基醚，乙烯芳香族化合物，二羰基醯亞胺衍生物，共 軛二烯以及丙烯腈，甲基丙烯腈，丙烯醯胺，甲基丙烯醯 胺，氯化乙烯，氯化亞乙烯及乙酸乙烯酯所成群之至少1 種的不飽和化合物。 上述之中，包括以名稱表示之化合物（a3)的具體例方 面，丙烯酸烷基酯方面，可例舉丙烯酸甲酯，丙烯酸i-丙 酯等； 甲基丙烯酸烷基酯方面，可例舉甲基丙烯酸甲酯，甲 基丙烯酸乙酯，甲基丙烯酸正丁酯，甲基丙烯酸二級丁 酯，甲基丙烯酸三級丁酯等； 丙烯酸脂環式酯方面，可例舉丙烯酸環己酯，丙烯酸 2-甲基環己酯，丙烯酸三環[5.2.1.02’6]癸烷-8-基酯，丙烯 酸2-(三環[5.2·1·〇2,6]癸烷基氧）乙酯，丙烯酸異萡基酯 等； 甲基丙烯酸脂環式酯方面，可例舉甲基丙烯酸環己 酯’甲基丙烯酸 2-甲基環己酯，甲基丙烯酸三環 -12- 200842162 [5.2.1.02，6]癸院-8-基酯，甲基丙儀酸2-(三環[5.2.1.02,6] 癸烷-8-基氧）乙基酯，甲基丙烯酸異萡基酯等； 丙細酸芳基酯方面，可例舉丙;(：希酸苯酯等； 丙烯酸芳烷酯方面，可例舉丙烯酸节酯等； 甲基丙烯酸芳基酯方面，可例舉甲基丙烯酸苯酯等； 甲基丙烯酸芳烷酯方面，可例舉甲基丙烯酸苄酯等； 二羧酸二烷基酯方面，可例舉順丁烯二酸二乙酯，反 丁烯二酸二乙酯，伊康酸二乙酯等； 甲基丙烯酸羥基烷基酯方面，可例舉甲基丙烯酸2 -羥基乙酯，甲基丙烯酸2 -羥基丙酯，甲基丙烯酸2 - (6 -羥 基乙基己醯氧）乙基酯等； 含氧1原子之不飽和5或6員環的甲基丙烯酸酯方 面，可例舉甲基丙烯酸四氫糠酯，甲基丙烯酸四氫呋喃 酯，甲基丙烯酸四氫哌喃-2-甲酯等； 丙烯酸環氧基烷基酯方面，可例舉丙烯酸環氧丙酯， 丙烯酸2-甲基環氧丙酯，丙烯酸3,4-環氧基丁酯，丙烯酸 6,7-環氧基庚酯，丙烯酸3,4-環氧基環己酯等；甲基丙烯 酸環氧基烷基酯方面，可例舉甲基丙烯酸環氧丙酯，甲基 丙烯酸2-甲基環氧丙酯，甲基丙烯酸3,4-環氧基丁酯，甲 基丙烯酸6,7-環氧基庚酯，甲基丙烯酸3,4-環氧基環己酯 等；α-院基丙嫌酸環氧基院基酯方面，可例舉α -乙基丙 烯酸環氧丙酯，α-正丙基丙烯酸環氧丙酯，α-正丁基丙烯 酸環氧丙酯，α-乙基丙烯酸6,7-環氧基庚酯等；具有不飽 和鍵的縮水甘油基醚方面，可例舉鄰乙烯苄基縮水甘油基 -13- 200842162 醚，間乙烯苄基縮水甘油基醚，對乙烯苄基縮水甘油基醚 等； 乙烯芳香族化合物方面，可例舉苯乙烯，α -甲基苯 乙烯，間甲基苯乙烯，對甲基苯乙烯，對甲氧基苯乙烯 等； 二羰基醯亞胺衍生物方面，可例舉苯基順丁烯二醯亞 胺，環己基順丁烯二醯亞胺，苄基順丁烯二醯亞胺，Ν-琥 珀醯亞胺基-3-順丁烯二醯亞胺苯甲酸酯，Ν-琥珀醯亞胺 基-4-順丁烯二醯亞胺丁酸酯，Ν_琥珀醯亞胺基順丁烯 二醯亞胺己酸酯，Ν-琥珀醯亞胺基-3-順丁烯二醯亞胺丙 酸酯，Ν - ( 9 -吖啶）順丁烯二醯亞胺等； 共軛二烯方面，可例舉1，3-丁二烯，異戊二烯，2,3-二甲基-1，3·丁二烯等。 該等之中，就共聚反應性及所得共聚物對鹼水溶液的 溶解性之觀點而言，以丙烯酸2-甲基環己酯，甲基丙烯 酸2-羥基乙酯，苯乙烯，甲基丙烯酸環氧丙酯，甲基丙 烯酸四氫糠酯，1，3-丁二烯或甲基丙烯酸2-(6-羥基乙基己 釀氧）乙基酯爲佳。 化合物（a3 )，可單獨使用或混合2種以上使用。 共聚物〔A〕中，由化合物（a3)而來之重覆單位的含 有率，較佳爲1 0〜7 0重量％，更佳爲2 0〜5 0重量％，最 佳爲30〜50重量％。由化合物（a3)而來之重覆單位的含有 率若不足1 0重量％時，所得敏輻射線性樹脂組成物的保 存穩定性降低，另一方面若超過70重量％時，敏輻射線 -14- 200842162 性樹脂組成物的鹼顯影性不足。 製造共聚物[A]所使用之溶劑方面，可例舉醇，醚， 乙二醇醚，乙二醇烷基醚乙酸酯，二乙二醇，二丙二醇， 丙二醇單烷基醚，丙二醇烷基醚乙酸酯，丙二醇烷基醚丙 酸酯，芳香族烴，酮 ，酯等。 該等具體例方面 ，醇方面，可例舉甲醇，乙醇，苄基 醇，2-苯基乙基醇，2 i-苯基-1-丙醇等； 醚方面，可例舉四氫呋喃等 乙二醇醚方面， 基醚等； 可例舉乙二醇單甲基醚，乙二醇單乙 乙二醇烷基醚乙酸酯方面，可例舉甲基溶纖劑乙酸 酯，乙基溶纖劑乙酸酯，乙二醇單丁基醚乙酸酯，乙二醇 單乙基醚乙酸酯等； 二乙二醇方面，’ 可例舉二乙二醇單甲基醚，二乙二醇 單乙基醚，二乙二醇. 二醇乙基甲基醚等； 二甲基醚，二乙二醇二乙基醚，二乙 丙二醇方面，可例舉二丙二醇單甲基醚，二丙二醇 單乙基醚，二丙二醇. 二醇乙基甲基醚等； 二甲基醚，二丙二醇二乙基醚，二丙 丙二醇單烷基醚方面，可例舉丙二醇單甲基醚，丙二 醇單乙基醚，丙二醇單丙基醚，丙二醇單丁基醚等； 丙二醇烷基醚丙酸酯方面，可例舉丙二醇甲基醚乙酸 酯，丙二醇乙基醚乙酸酯，丙二醇丙基醚乙酸酯，丙二醇 丁基醚乙酸酯等； -15- 200842162 丙二醇烷基醚乙酸酯方面，可例舉丙二醇甲基醚丙酸 酯，丙二醇乙基醚丙酸酯，丙二醇丙基醚丙酸酯，丙二醇 丁基醚丙酸酯等； 芳香族烴方面，可例舉甲苯，二甲苯等； 酮方面，可例舉甲基乙基酮，環己酮，4-羥基-4-甲 基-2-戊酮等； 酯方面，可例舉乙酸甲酯，乙酸乙酯，乙酸丙酯，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-甲基丁烷酸甲酯，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，丙氧基乙酸甲酯，丙氧基乙酸乙 酯，丙氧基乙酸丙酯，丙氧基乙酸丁酯，丁氧基乙酸甲 酯，丁氧基乙酸乙酯，丁氧基乙酸丙酯，丁氧基乙酸丁 酯，乙酸3 -甲氧基丁酯，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，2_乙氧基丙酸丙酯，2-乙氧基丙酸丁酯，2 -丁氧基丙酸甲酯，2 -丁氧基丙酸乙 酯，2 -丁氧基丙酸丙酯，2 -丁氧基丙酸丁酯，3 -甲氧基丙 酸甲酯，3 -甲氧基丙酸乙酯，3 -甲氧基丙酸丙酯，3 -甲氧 基丙酸丁酯，3 -乙氧基丙酸甲酯，3 -乙氧基丙酸乙酯，3- -16- 200842162 乙氧基丙酸丙酯，3 -乙氧基丙酸丁酯，3 -丙氧基丙酸甲 酯，3_丙氧基丙酸乙酯，3 -丙氧基丙酸丙酯，3 -丙氧基丙 酸丁酯，3 -丁氧基丙酸甲酯’ 3 -丁氧基丙酸乙酯’ 3 -丁氧 基丙酸丙酯，3 -丁氧基丙酸丁酯等的酯。 該等之中，以乙二醇烷基醚乙酸酯，二乙二醇，二丙 二醇，丙二醇單烷基醚，丙二醇烷基醚乙酸酯爲佳，特別 以二乙二醇二甲基醚，二乙二醇乙基甲基醚，二丙二醇二 甲基醚，二丙二醇乙基甲基醚，丙二醇甲基醚，丙二醇甲 基醚乙酸酯或乙酸3 -甲氧基丁酯爲佳。 該溶劑可單獨使用或混合2種以上使用。 製造共聚物[A]所使用的聚合引發劑方面，並無特別 限定，可例舉2,2’-偶氮雙異丁腈，2,2'-偶氮雙-(2,4-二甲 基戊腈），2,2'-偶氮雙-(4-甲氧基-2,4-二甲基戊腈），4,4f_ 偶氮雙（4-氰戊酸），二甲基2,2’-偶氮雙（2-甲基丙酸酯）， 2，2’-偶氮雙（4-甲氧基-2,4-二甲基戊腈）等的偶氮化合物； 苯醯基過氧化物，月桂醯過氧化物，三級丁基過氧三甲基 乙酸酯，1，1 -雙（三級丁基過氧）環己烷等的有機過氧化 物；過氧化氫等。聚合引發劑方面，若使用過氧化物時， 亦可倂用該等與還原劑，作爲氧化還原型引發劑。 該等聚合引發劑，可單獨使用或混合2種以上使用。 共聚物〔A〕的凝膠滲透層析術（GPC)所致換算聚苯 乙烯的重量平均分子量（以下稱爲「Mw」）較佳爲2,000〜 1 00,000，更佳爲 5,〇〇〇 〜50,000。Mw 若不足 2,000 時， 所得被膜的顯影性，殘膜率等降低，又恐有損於圖型形 -17- 200842162 狀，耐熱性等，另—方面，若超過1 00,000時，解像度降 低’恐有損於圖型形狀。 如上述所製造的共聚物[A]，具有選自由化合物（al) 而來之竣基及羧酸酐基所成群之至少丨種的基與由化合物 (a2)而來之二噁戊烷構造，對鹼顯影液具有適當的溶解 性’同時’具有即使不使用特別的硬化劑，藉由加熱亦可 容易硬化的優點。 如上述作法所得之共聚物[A]，可依溶液狀態的原 樣，供調製敏輻射線性樹脂組成物，或亦可自溶液單離供 調製敏輻射線性樹脂組成物。 此外，本發明中，與共聚物[A]可同時倂用其他的聚 合物。相關之其他的聚合物方面，以將上述化合物（a 1)及 (a 3 )共聚所成的鹼可溶性共聚物爲佳。該鹼可溶性共聚物 中，由化合物（al)而來之重覆單位的含有率，較佳爲 4 0重量％，更佳爲8〜3 0重量％。鹼可溶性共聚物的 Mw，較佳爲1，000〜50,000，更佳爲3,000〜3〇,〇〇〇。相 關的鹼可溶性共聚物’可使用化合物（al)及（a3)的混合 物，準照共聚物[A]的製造方法而製造。 本發明中，倂用共聚物[A]與其他的聚合物時，其他 聚合物的使用比率方面’相對於共聚物[A ]與其他聚合物 的合計，以8 0重量°/。以下爲佳’ 6 〇重量°/〇以下更佳，5 〇 重量％以下爲最佳。 _[B]聚合性不飽和化合物_ -18- 200842162 本發明的敏輻射線性樹脂組成物月 不飽和化合物，較佳爲具有乙烯性不飽 物。 [B ]聚合性不飽和化合物方面，只； 和鍵，能夠聚合的話，並無特別限定， 可提高所得間隔器強度的觀點而言，以 3官能以上的（甲基）丙烯酸酯爲佳。 該單官能（甲基）丙烯酸酯方面，可ί 烯酸酯，2-羥基乙基甲基丙烯酸酯，二 烯酸酯，二乙二醇單乙基醚甲基丙烯酸 酯，異萡基甲基丙烯酸酯，3-甲氧基丁 氧基丁基甲基丙烯酸酯，2-丙烯醯基章 鄰苯二酸酯，2-甲基丙烯甲基丙烯醯_ 基鄰苯二酸酯，ω-羧基聚己內酯單丙） 品方面，可例舉aronix Μ-101，同Μ-1 M-5 3 00(東亞合成公司製）；KAYARAD 120S(日本化藥公司製）；bisuko-tol58， 化學工業公司製）等。 該2官能（甲基）丙烯酸酯方面，可 酸酯，乙二醇二甲基丙烯酸酯，二乙二 乙二醇二甲基丙烯酸酯，四乙二醇二丙 二甲基丙烯酸酯，1，6 -己烷二醇二丙烯 醇二甲基丙烯酸酯，1，9 -壬二醇二丙烯 二甲基丙烯酸酯，雙苯氧基乙醇荛二丙 f含有的[B]聚合性 和鍵的聚合性化合 g具有乙烯性不飽 但就聚合性良好， 單官能，2官能或 可舉2-羥基乙基丙 乙二醇單乙基醚丙 酯，異Μ基丙烯酸 基丙烯酸酯，3 -甲 :乙基-2-羥基丙基 ;氧乙基-2-羥基丙 希酸酯等，又市售 11，同 Μ-114，同 TC-110S，同 TC-同2 3 1 1 (大阪有機 例舉乙二醇二丙烯 醇二丙烯酸酯，二 烯酸酯，四乙二醇 酸酯，1，6-己烷二 酸酯，1，9 -壬二醇 烯酸酯，雙苯氧基 -19- 200842162 乙醇莽一甲基丙燒酸酯等，又市售品方面，可例舉aronix M-210，同 M-240，同 M-6200(東亞合成公司製）， KAYARAD HDDA，同 HX-220，同 R-604(日本化藥公司 製），bisuko-to260，同312，同3 3 5 HP(大阪有機化學工業 公司製）等。 該3官能以上的（甲基）丙烯酸酯方面，除了可例舉三 羥甲基丙烷三丙烯酸酯，三羥甲基丙烷三甲基丙烯酸酯， 新戊四醇三丙烯酸酯，新戊四醇三甲基丙烯酸酯，新戊四 醇四丙烯酸酯，新戊四醇四甲基丙烯酸酯，二新戊四醇五 丙烯酸酯，二新戊四醇五甲基丙烯酸酯，二新戊四醇六丙 烯酸酯，二新戊四醇六甲基丙烯酸酯，三（2 -丙烯醯基氧 乙基）磷酸酯，三（2-甲基丙烯甲基丙烯醯基氧乙基）磷酸酯 等以外’可例舉使分子內具有烷撐基直鏈構造及脂環構造 以及2個以上異氰酸酯基的化合物，與分子內含有丨個以 上的羥基之3官能，4官能或5官能的（甲基）丙烯酸酯化 合物反應所得的胺甲酸乙酯丙烯酸酯化合物。該等的市售 品方面，可例舉aronix M-309，同M-400，同M-405，同 M-450，同 M-7100，同 M- 8 03 0，同 M- 8060，同 TO-1 450(東亞合成公司製），KAYARAD TMPTA，同 DPHA， 同 DPCA-20，同 DPCA-30，同 DPCA-60，同 DPCA-120(日本化藥公司製），bisuko-to 295，同300，同360， 同GPT，同3PA，同400(大阪有機化學工業公司製），new frontier R-1150(第一工業製藥公司製），KAYARAD DPHA-40H(日本化樂公司製）等。 -20- 200842162 該等單官能，2官能或3官能以上的（甲基）丙烯酸酯 之中，以3官能以上的（甲基）丙烯酸酯爲更佳’以三羥甲 基丙烷三丙烯酸酯’新戊四醇三丙烯酸酯，新戊四醇四丙 烯酸酯，二新戊四醇五丙烯酸酯或二新戊四醇六丙烯酸酯 爲特佳。 該單官能，2官能或3官能以上的（甲基）丙烯酸酯， 可單獨使用或組合2種以上使用。 本發明的敏輻射線性樹脂組成物中，[B]聚合性不飽 和化合物的使用比率係指，相對於聚合物的全量（稱爲共 聚物[A]與其他聚合物的合計量。以下相同。相對於100 重量份，較佳爲 50〜200重量份，更佳爲 60〜150重量 份。[B]聚合性不飽和化合物的使用比率若不足50重量份 時，顯影時恐怕會有顯影殘留的問題，另一方面，若超過 2 00重量份時，所得間隔器的密接性有降低的情形。 -[C]敏輻射線性聚合引發劑- 本發明的敏輻射線性樹脂組成物所含有的[C]敏輻射 線性聚合引發劑係，藉由可視光線，紫外線，遠紫外線， 帶電粒子線，X線等的放射線曝光，以使上述[B]聚合性 不飽和化合物開始聚合，產生活性種的成分所成。此種[C] 敏輻射線性聚合引發劑方面，以使用肟化合物，聯咪唑化 合物，安息香化合物，乙醯苯化合物，二苯基酮化合物， α-二酮化合物，敏輻射線性陽離子聚合引發劑等爲佳。 上述肟化合物方面，可例舉咔唑化合物，其他的肟化 -21 - 200842162 合物。 上述咔唑化合物方面，以具有9 . Η.-咔唑構造的〇 -醯 基肟型聚合引發劑爲佳。其具體例方面，可例舉1 -〔 9-乙 基-6-苯醯基·9·Η· -咔唑-3-基〕-壬烷-1，2 -壬烷-2-肟-0-苯 甲酸酯，1-〔9-乙基-6-苯醯基-9·Η·-咔唑-3-基〕-壬烷-1，2-壬烷-2-肟-0-乙酸鹽，1-〔 9-乙基-6-苯醯基-9.Η.-咔 唑-3-基〕-戊烷-1，2-戊烷-2-肟-0-乙酸鹽，1-〔 9-乙基- 6-苯醯基- 9.Η.-咔唑-3-基〕-辛烷-1-酮肟-0-乙酸鹽，1-〔 9-乙基-6- (2_甲基苯醯基）-9.Η. -咔唑-3-基〕-乙烷-卜酮肟- 0-苯甲酸酯，1-〔9-乙基-6-(1,3,5-三甲基苯醯基）-9.11.-咔 唑-3-基〕-乙烷-1-酮肟-〇-苯甲酸酯，1-〔 9-丁基- 6-(2-乙 基苯醯基）-9·Η·-咔唑-3-基〕-乙烷-1-酮肟-0-苯甲酸酯， 乙酮（ethanone)，1-[9·乙基- 6-(2 -甲基苯醯基）-9.H.-咔唑-3-基]-，1-(0-乙醯基氧肟），乙酮（ethanone)，1-[9-乙基-6-[2-甲基-4-(2,2-二甲基-1，3-二氧雜環戊烷基）甲氧基苯醯 基]-9. Η ·-咔唑-3-基]-，1-(0-乙醯基氧肟），乙酮 (ethanone)，：l-[9 -乙基-6-(2-甲基苯醯基）-9·Η· -咔唑-3-基]-，1-(0-乙醯基氧肟）等，該等之中，以乙酮 (ethanone)，1-[9·乙基-6-(2-甲基苯醯基）-9.H·-咔唑-3-基]-，1-(0-乙醯基氧肟）或乙酮（ethanone)，1-[9-乙基-6-[2-甲基- 4-(2，2-二甲基-1，3-二氧雜環戊烷基）甲氧基苯醯 基]-9.H·-咔唑-3-基]-，1-(0-乙醯基氧肟）爲特佳。 該等咔唑化合物，可單獨使用或混合2種以上使用。 上述其他的肟化合物方面，可例舉1，2 -辛二酮-1 - [ 4 - -22- 200842162 (苯基硫代）苯基]-2-(0-苯醯基氧肟），1，2-丁烷二酮-1-[4-(苯基硫代）苯基]-2-(0-苯醯基氧肟），1，2-丁烷二酮-1-[4-(苯基硫代）苯基]-2_(0 -乙薩基氧胎）’ 1，2-辛二醒-1-[4-(甲 基硫代）苯基]-2-(0-苯醯基氧肟），1，2-辛二酮-1-[4-(苯基 硫代）苯基]-2-(0-(4-甲基苯醯基氧肟）)等。該等之中，以 1，2-辛二酮-1-[4-(苯基硫代）苯基]-2-(0-苯醯基氧肟）爲特 佳。 上述聯咪唑化合物方面，可例舉2，2 ’ -雙（2 -氯苯基）-4,4’，5,5’-四個 （4-乙氧基 羰苯基 ）-1，2’-聯 咪唑， 2,2，-雙 （2-溴苯基）-4,4’，5,5f -四個（4-乙氧基羰苯基）-1，2’-聯咪唑， 2,2’ -雙（2 -氯苯基）-4,4’，5,5’ -四苯基-1，2，-聯咪唑，2,2，-雙 (2,4-二氯苯基）-4,4'，5,5’-四苯基·1，2，·聯咪唑，2,2’-雙 (2,4,6-三氯苯基）-4,4’，5,5，-四苯基-1，2，-聯咪唑，2,2、雙 (2-溴）-4,4’，5,5·-四苯基·ι，2，·聯咪唑，2,2、雙（2,4_二溴苯 基）-4,4’，5,5’-四苯基-1，2，-聯咪唑，2,2’-雙（2,4,6-三溴苯 基）_4,4’，5,5’-四苯基-ΐ，2，-聯咪唑等，該等之中，以 2,2，-雙（2-氯苯基）-4,4’，5,5，-四苯基-1,2，-聯咪唑，2,2，-雙（2,4-二氯苯基）-4,4’，5,5’-四苯基-152’_聯咪唑或2,2’_雙（2,4,6_ 三氯苯基）-4,4’，5,5’_四苯基β1,2，_聯咪唑爲佳，較佳爲， 2,2’-雙（2,4-二氯苯基）-4,4，，5,5，-四苯基-1，2，-聯咪唑。 該聯咪嗤化合物，可單獨使用或混合2種以上使用。 藉由使用該等的聯咪唑化合物，所得的敏輻射線性樹 脂組成物的感度，解像度及密接性可更良好。 本發明的敏幅射線性樹脂組成物中，[C]敏輻射線性 -23- 200842162 聚合引發劑方面，若使用聯咪唑化合物時，爲了使其增 感，可倂用具有二烷基胺基的芳香族化合物（以下，稱爲 「二烷基胺基增感劑」）。相關的二烷基胺基增感劑方 面，可例舉4,4’·雙（二甲基胺基）二苯基酮，4,4’-雙（二乙 基胺基）二苯基酮，對二甲基胺基苯甲酸乙基，對二乙基 胺基苯甲酸乙基，對二甲基胺基苯甲酸異戊酯，對二乙基 胺基苯甲酸異戊酯等，該等之中，以4,4f-雙（二乙基胺基） 二苯基酮爲佳。該等二烷基胺基增感劑，可單獨使用或混 合2種以上使用。 進而，在倂用聯咪唑化合物與二烷基胺基增感劑時， 氫供予化合物方面，可添加硫醇化合物。聯咪唑化合物係 藉由二烷基胺基增感劑而增感裂開，產生咪唑自由基，但 此時並非可馬上發現高的開始聚合能量，亦有所得間隔器 成爲如倒錐狀之不佳形狀的情形。在聯咪唑化合物與二烷 基胺基增感劑共存的系內，此問題可藉由添加硫醇化合物 來解決。亦即，在咪唑自由基中，藉由自硫醇化合物供給 氫自由基，使咪唑自由基成爲中性的咪唑，結果由於產生 具有高的開始聚合能量的硫自由基之成分，故間隔器形狀 成爲較佳的順錐狀。 上述硫醇化合物方面，可例舉2 -氫硫基苯并噻唑，2 -氫硫基苯并噁唑，2-氫硫基苯并咪唑，2-氫硫基-5-甲氧基 苯并噻唑，2-氫硫基-5-甲氧基苯并咪唑等的芳香族系硫 醇，3 -氫硫基丙酸，3 -氫硫基丙酸甲酯，3 -氫硫基丙酸乙 酯，3 -氫硫基丙酸辛酯等的脂肪族系單硫醇； -24- 200842162 3,6-二氧雜-1，8-辛烷二硫醇，異戊四醇四（氫硫基乙 酸酯），異戊四醇四（3-氫硫基丙酸酯）等的2官能以上的脂 肪族硫醇等。該等的硫醇化合物，可單獨或混合2種類以 上使用。 上述安息香化合物方面，可例舉安息香，安息香甲基 醚，安息香乙基醚，安息香異丙基醚，安息香異丁基醚， 2-苯醯基苯甲酸甲基等。 上述乙醯苯化合物方面，可例舉α -羥基酮化合物， α-胺基酮化合物，該等以外的化合物。 上述α -羥基酮化合物的具體例方面，可例舉1-苯基-2-羥基-2-甲基丙烷-1-酮，1-(4-異丙基苯基）-2-羥基-2-甲 基丙烷-1-酮，4-(2-羥基乙氧基）苯基-(2-羥基-2-丙基）酮， 1-羥基環己基苯基酮等； 上述α-胺基酮化合物的具體例方面，可例舉2-甲基-1-[4-(甲基硫代）本基]-2 -嗎琳基（morpholino)丙院-1-酬， 2 -卞基-2- 一^甲基胺基-1-(4 -嗎咐基苯基）-丁 -1-嗣％。 該等的乙醯苯化合物，可單獨使用或混合2種以上使 用。 本發明中，[C]敏輻射線性聚合引發劑方面，藉由使 用乙醯苯化合物，可進而改善所得敏輻射線性樹脂組成物 的感度，所得間隔器的形狀或壓縮強度等。 上述二苯基酮化合物方面，可例舉4,4’-雙（二甲基胺 基）二苯基酮，4,4^雙（二乙基胺基）二苯基酮等。 上述α-二酮化合物方面，可例舉二乙醯基，二苯醯 -25- 200842162 基，甲基苯醯基甲酸酯等。 上述敏輻射線性陽離子聚合引發劑方面，可例舉鐵 鹽，芳環烯金屬衍生物（metallocene)化合物等。 上述鎗鹽的具體例方面，可例舉苯基偶氮鐵四氟硼酸 酯，苯基偶氮鑰六氟膦酸酯，苯基偶氮鑰六氟砷酸鹽，苯 基偶氮鑰三氟甲烷磺酸鹽，苯基偶氮鑰三氟乙酸酯，苯基 偶氮鑰-對甲苯磺酸鹽，4-甲氧基苯基偶氮鑰四氟硼酸 酯，4-甲氧基苯基偶氮鑰六氟膦酸酯，4-甲氧基苯基偶氮 鑰六氟砷酸鹽，4-甲氧基苯基偶氮鑰三氟甲烷磺酸鹽，4-甲氧基苯基偶氮鑰三氟乙酸酯，4-甲氧基苯基偶氮鏺-對 甲苯磺酸鹽，4-三級丁基苯基偶氮鎩四氟硼酸酯，4-三級 丁基苯基偶氮鑰六氟鱗酸酯’ 4-三級丁基苯基偶氮鑰六氟 砷酸鹽，4-三級丁基苯基偶氮鑰三氟甲烷磺酸鹽，4-三級 丁基苯基偶氮鑰三氟乙酸酯，4-三級丁基苯基偶氮鑰-對 甲苯磺酸鹽等的偶氮鑰鹽； 三苯基鎏四氟硼酸酯，三苯基鎏六氟膦酸酯，三苯基 鎏六氟砷酸鹽，三苯基鎏三氟甲烷磺酸鹽’三苯基鎏三氟 乙酸酯，三苯基鎏-對甲苯磺酸鹽，4 -甲氧基苯基二苯基 鎏四氟硼酸酯，4 -甲氧基苯基二苯基鎏六氟膦酸酯’ 4 -甲 氧基苯基二苯基鎏六氟砷酸鹽，4 -甲氧基苯基二苯基鎏三 氟甲烷磺酸鹽，4-甲氧基苯基二苯基鎏三氟乙酸酯，4-甲 氧基苯基二苯基鎏-對甲苯磺酸鹽’ 4-苯基噻吩二苯基四 氟硼酸酯，4 -苯基噻吩二苯基六氟膦酸酯，4 -苯基噻吩二 苯基六氟砷酸鹽，4-苯基噻吩二苯基三氟甲烷磺酸鹽，4_ -26- 200842162 苯基噻吩二苯基三氟乙酸酯，4 -苯基噻吩二苯基-對甲苯 磺酸鹽等的鎏鹽等。 上述芳環稀金屬衍生物（metallocene)化合物方面，可 例舉（l-6-η -枯烯）（η-環戊二嫌基）鐵（1+)六氟化磷酸（1-) 等。 該等敏輻射線聚合引發劑的市售品方面，可例舉爲偶 氮鐵鹽之Adecaultra set ΡΡ-33(公司ADEKA製），爲鎏鹽 之 OPTOMER SP-150，同-170(公司 ADEKA 製），爲芳環 烯金屬衍生物（11161&11〇〇6116)化合物之11&(：11^261(千葉特 用化學品公司製）等。 本發明中，[C]敏輻射線性聚合引發劑，可單獨使用 或混合2種類以上使用。 本發明中，[C]敏輻射線性聚合引發劑方面，以使用 上述的肟化合物爲佳，特別以倂用咔唑化合物與其他的肟 化合物爲佳。[C]敏輻射線性聚合引發劑方面，藉由倂用 咔唑化合物與其他的肟化合物，可更提高所得敏輻射線性 樹脂組成物對放射線之感度，例如即使在1，5 00 J/m2以下 曝光量的情形下，可形成與基板密接性優異的顯示面板用 間隔器。 本發明的敏輻射線性樹脂組成物中，[C]敏輻射線性 聚合引發劑的使用比率，相對於[B]聚合性不飽和化合物 1〇〇重量份，較佳爲1〜30重量份，更佳爲2〜20重量 份。[C]敏輻射線性聚合引發劑的使用量若不足丨重量份 時，顯影時的殘膜率有不足的情形，另一方面，若超過 -27- 200842162 3 〇重量份時’顯影時未曝光部對鹼性顯影液的溶解性不 足。 本發明的敏輻射線性樹脂組成物中所使用的[C]敏輻 射線性聚合引發劑中，肟化合物的佔有比率，相對於[C] 敏輻射線性聚合引發劑的全量，較佳爲2 0重量％以上， 更佳爲40重量％以上。在此，肟化合物的佔有比率若不 足2 0重量％時，難以發現本發明所期待的效果。肟化合 物中，咔唑化合物的佔有比率，相對於肟化合物的全量， 較佳爲30重量％以上，更佳爲50重量％以上。 本發明的敏輻射線性樹脂組成物中，[C]敏輻射線性 聚合引發劑方面，係使用聯咪唑化合物，在倂用該等與二 烷基胺基增感劑之情形時之，二烷基胺基增感劑的使用比 率，相對於聚合物的全量100重量份，較佳爲〇·1〜5〇重 量份，更佳爲1〜20重量份。二烷基胺基增感劑的使用量 若不足0· 1重量份時，所得間隔器恐會產生膜變薄’有損 於圖型的形狀，另一方面，若超過5 0重量份時’恐有損 於間隔器的圖型形狀。進而，[C]敏輻射線性聚合引發劑 方面，係使用聯咪唑化合物，使用該等與二烷基胺基增感 劑及硫醇化合物時，硫醇化合物的使用比率，相對於聚合 物的全量100重量份，較佳爲〇.1〜50重量份，更佳爲1 〜20重量份。硫醇化合物的使用比率若不足〇· 1重量份 時，所得間隔器將會產生膜變薄或圖型形狀的不良’另一 方面，若超過5 0重量份時’恐有損於間隔器的圖型形 狀。 -28- 200842162 -其他的添加劑- 本發明的敏輻射線性樹脂組成物，含有上述共聚物 [A] ’ [B]聚合性不飽和化合物及[C]敏輻射線性重合引發 劑的必須成分，但在無損於本發明所期待效果的範圍內， 可因應需要含有其他的添加劑。 相關的其他添加劑方面，可例舉界面活性劑，黏接助 劑，保存穩定劑，耐熱性提高劑等。 爲了提高所得敏輻射線性樹脂組成物的塗佈性，可使 用上述界面活性劑。相關的界面活性劑方面，可例舉氟系 界面活性劑，聚矽氧系界面活性劑及其他的界面活性劑。 上述氟系界面活性劑方面，以使用末端，主鏈及側鏈 中至少一個部位具有氟烷基或氟烷撐基的化合物爲佳。其 具體例方面，可例舉1，1，2,2-四氟辛基（1,1,2,2-四氟丙基） 醚，1，1，2,2-四氟辛基己基醚，八乙二醇二（1，1，2,2-四氟 丁基）醚，六乙二醇（1，1，2,2,3,3-六氟戊基）醚，八丙二醇 二（1，1，2,2-四氟丁基）醚，六丙二醇二（1，1，2,2,3,3-六氟戊 基）醚，全氟十二基颯酸鈉，1，1，2,2,3,3,9,9，10，10_十氟十 二烷，1，1，2,2，3，3 -六氟癸烷，氟烷基苯颯酸鈉，氟烷基膦 酸鈉，氟烷基羧酸鈉，氟烷基聚氧乙烯醚，二甘油四個 (氟烷基聚氧乙烯醚），氟烷基銨碘化物，氟烷基甜菜鹼’ 氟烷基聚氧乙烯醚’全氟烷基聚氧乙醇’全氟烷基烷氧化 物，氟系烷基酯等，該等的市售品方面，可例舉BM-1000，BM-1 1 00(BM CHEMIE 公司製），megafuck F142D， -29- 200842162(In the formula (1), R1 and R2 each represent an independent hydrogen atom or a monovalent organic group, R3 represents a hydrogen atom or a methyl group, and X represents a divalent organic group) (hereinafter referred to as " Compound (a2)"), and (a3) are selected from the group consisting of alkyl acrylate, alkyl methacrylate, acrylate alicyclic ester, methacrylate alicyclic ester, aryl acrylate, aryl acrylate, methacrylic acid Aryl ester, arylalkyl methacrylate, dialkyl dicarboxylate, hydroxyalkyl methacrylate, unsaturated 5- or 6-membered ring methacrylate containing 1 atom of oxygen, epoxy acrylate Ester, methacryl-7-200842162 acid epoxy ester, α-hospital acid storage acid epoxy ester, glycidyl ether with unsaturated bond, ethylene aromatic compound, dicarbonyl ruthenium Imine derivatives, conjugated dienes and at least one unsaturated group of acrylonitrile 'methacrylonitrile, acrylamide, methacrylamide, vinyl chloride, vinylidene chloride and vinyl acetate a copolymer of a compound (hereinafter referred to as "compound (a 3)") (hereinafter referred to as "a total The polymer [A]"), [B] a polymerizable unsaturated compound, and [C] a radiation-sensitive linear polymerization initiator are obtained by a radiation-sensitive linear resin composition. The radiation sensitive linear resin composition is suitable as a spacer for forming a liquid crystal display element. The above objects and advantages of the present invention are attained by a spacer for a liquid crystal display element formed from the above-mentioned sensitive radiation linear resin composition, and a liquid crystal display element comprising the same. The above objects and advantages of the present invention are achieved by the method of forming a spacer for a liquid crystal display device characterized by including at least the steps described below. (1) a step of forming a film of the above-mentioned radiation-sensitive linear resin composition on a substrate, (2) a step of exposing at least a portion of the film, (3) a step of developing the film after exposure, and (4) The step of heating the developed film. The above objects and advantages of the present invention are attained by the above copolymer [A]. -8- 200842162 BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. Sensitive Radiation Linear Resin Composition The radiation sensitive linear resin composition of the present invention contains at least a copolymer [A], [B] a polymerizable unsaturated compound and [C] a radiation-sensitive linear polymerization initiator. Copolymer [A]-copolymer [A] can be freely obtained by mixing a compound (al), a compound (a2) and a compound (a3), preferably in a solvent, in the presence of a polymerization initiator. It is produced by polymerization. The compound (al) used in the production of the copolymer [A] is at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides. The related compound (al) may, for example, be a monocarboxylic acid such as acrylic acid, methacrylic acid 'crotonic acid, 2-methylpropenyloxyethyl succinic acid or 2-methylpropenyloxyethyl hexahydrophthalic acid. a dicarboxylic acid such as maleic acid, fumaric acid, citraconic acid, mesaconic acid or itaconic acid; an anhydride of the dicarboxylic acid or the like. Among these compounds (a1), acrylic acid, methacrylic acid, maleic anhydride, or 2-position is used in terms of copolymerization reactivity, solubility in an aqueous alkali solution of the obtained copolymer, and ease of availability. Methyl propylene oxiranyl hexahydrophthalic acid is preferred. * 9 - 200842162 The compound (a 1 ) may be used singly or in combination of two or more. In the copolymer [A], the content of the repeating unit derived from the compound (al) is preferably 5 to 50% by weight, more preferably 10 to 4% by weight, most preferably 1. 5 to 30% by weight. When the content of the repeating unit derived from the compound U1) is less than 5% by weight, the solubility in the aqueous alkali solution is insufficient. On the other hand, when the content exceeds 50% by weight, the solubility in the aqueous alkali solution is excessively high. . The compound (a2) ' used for the production of the copolymer [A] is a compound represented by the above formula (1). In the above formula (1), the monovalent organic group of R1 and R2 may, for example, be an alkyl group having 1 to 6 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, an isobutyl group and the like. In the above formula (1), the divalent organic group of X may, for example, be a methylene group or an alkylene group having 2 to 6 carbon atoms. Specific examples of the alkylene group having 2 to 6 carbon atoms include a vinyl group, a 1,3-propenyl group, and a 1,4-butenyl group. Specific examples of the compound (a2) include 4-acryloyloxymethyl-2,2-dimethyl-1,3-dioxolane ((1丨(^〇:^1^), 4_Acetyl methoxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-propenyl methoxymethyl-2,2-diethyl-1,3-di Ethylpentane, 4-propenyl methoxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4-propenyl methoxymethyl-2-cyclopentyl-1, 3-dioxapentane, 4-propenyloxymethyl-2-cyclohexyl-1,3-dioxolane, 4-propenyloxyethyl-2·methyl-2-ethyl-1 , 3_dioxapentane, 4-propenyloxypropyl-2-methyl-2-ethyl-1,3-dioxolane, 4-methylpropenyloxybutyl-2 - A Acrylic acid derivative of keto-2-ethyl-1,3-diB-oxonium; etc.; -10- 200842162 4 -methacryloyloxymethyl-2,2-dimethyl-1,3-di Ethylpentane, 4-methylpropanoid, decyloxymethyl-2-methyl-2-ethyl, 1,3,2-B, Ethyl, 4-methylpropenyloxymethyl-2,2 -diethyl-l,3-dioxapentane, 4-methylpropenyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4-methylpropene Mercaptooxymethyl-2-cyclopentyl-1 3 - Π Π 戊 ,, 4 -Methyl propylene decyl oxymethyl-2 -cyclohexyl-1,3 - di D pentylene, 4-methyl propyl oxime oxyethyl 2-methyl 2-ethyl-1,3-dioxolane, 4-methylpropenyloxypropyl-2-methyl-2-ethyl-1,3-dioxolane, 4-methylpropene a methacrylic acid derivative such as decyloxybutyl-2-methyl-2-ethyl-1,3-di D, and the like. Among these, the sensitive radiation is obtained from the viewpoint of excellent polymerizability. The viewpoint that the linear resin composition is excellent in developability of the alkali developing solution, and the viewpoint that the obtained spacer has both high flexibility and high elastic recovery ratio is 4-acryloyloxymethyl-2-methyl -2-ethyl-1,3-dioxolane, 4-acryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxazone, 4-propanol Oxymethyl-2-cyclohexyl-1,3-dioxolane, 4-methylpropenyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4- Methyl propylene decyl oxymethyl-2-methyl-2-isobutyl-1,3-dioxolane or 4-methylpropenyl oxymethyl 2- 2-cyclohexyl-1,3 - Ethylpentane is preferred. Compound (a2) can be used alone In the copolymer [A], the content of the repeating unit derived from the compound (a2) is preferably from 1 to 70% by weight, particularly preferably from 3 to 50% by weight. When the content of the repeating unit derived from the compound (a2) is less than 1% by weight, the linearity of the linear radiation-sensitive resin composition tends to be insufficient for the developability of the alkali developing solution. On the other hand, if it exceeds 70% by weight When the developability is too high, the sensitivity to the radiation of -11 - 200842162 is insufficient, which detracts from the shape of the obtained pattern. The compound (a3) used for the production of the copolymer [A] is selected from the group consisting of alkyl acrylates, alkyl methacrylates, acrylate cyclic esters, methacrylate alicyclic esters, aryl acrylates, acrylic acid. Aralkyl ester, aryl methacrylate, arylalkyl methacrylate, dialkyl dicarboxylate, hydroxyalkyl methacrylate, unsaturated 1 or 6 ring methacrylic acid containing 1 atom of oxygen Ester, epoxy acrylate alkyl ester, epoxy methacrylate alkyl ester, alkyl acrylate alkyl acrylate, glycidyl ether with unsaturated bond, vinyl aromatic compound, dicarbonyl ruthenium imine a derivative, a conjugated diene, and at least one unsaturated compound of a group of acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl chloride, vinylidene chloride and vinyl acetate. In the above, specific examples of the compound (a3) represented by the name include alkyl acrylate and i-propyl acrylate. The alkyl methacrylate may, for example, be a Methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, butyl methacrylate, butyl methacrylate, etc.; in terms of acrylate cyclic ester, cyclohexyl acrylate can be exemplified. 2-methylcyclohexyl acrylate, tricyclohexyl acrylate [5. 2. 1. 02'6] decane-8-yl ester, acrylic acid 2-(tricyclic [5. 2·1·〇2,6]decyloxy)ethyl ester, isodecyl acrylate, etc.; methacrylate alicyclic ester, Cyclohexyl methacrylate 2-methyl methacrylate Cyclohexyl ester, tricyclo-12-methacrylate-200842162 [5. 2. 1. 02,6] 癸院-8-yl ester, methyl propyl acid 2- (tricyclic [5. 2. 1. 02,6] decane-8-yloxy)ethyl ester, isodecyl methacrylate, etc.; in terms of aryl acrylate, exemplified by propylene; (: phenyl choate; aryl acrylate) The aryl methacrylate may, for example, be phenyl methacrylate or the like; the aryl methacrylate may, for example, be benzyl methacrylate or the like; The alkyl ester may, for example, be diethyl maleate, diethyl fumarate or diethyl ikonate; and the hydroxyalkyl methacrylate may, for example, be methacrylic acid 2 -hydroxyethyl ester, 2-hydroxypropyl methacrylate, 2-(6-hydroxyethylhexyloxy)ethyl methacrylate, etc.; Oxygen containing 1 atom of unsaturated 5 or 6 membered ring of methacrylic acid The ester side may, for example, be tetrahydrofurfuryl methacrylate, tetrahydrofuran methacrylate or tetrahydropyran-2-methyl methacrylate; and the epoxy acrylate of acrylic acid may be exemplified by acrylic acrylate. Ester, 2-methylglycidyl acrylate, 3,4-epoxybutyl acrylate, 6,7-epoxyheptyl acrylate, 3,4-epoxy acrylate The hexyl ester or the like; the epoxy methacrylate, exemplified by glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxybutyl methacrylate , 6,7-epoxyheptyl methacrylate, 3,4-epoxycyclohexyl methacrylate, etc.; α-homo-based propylene succinic acid epoxy ester, exemplified α-B Glycidyl acrylate, g-propyl acrylate of α-n-propyl acrylate, glycidyl α-n-butyl acrylate, 6,7-epoxyheptyl α-ethyl acrylate, etc.; Examples of the glycidyl ether include o-vinylbenzyl glycidyl-13-200842162 ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and the like; Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, etc.; dicarbonyl quinone imine derivatives, phenyl cis-butenylene Amine, cyclohexyl maleimide, benzyl maleimide, anthracene-succinimide-3-butyleneimine benzoate, Ν-hu醯imino-4-butylindoleimine butyrate, Ν_amber quinone imindolimine hexanoate hexanoate, Ν-amber 醯imino-3-pentene醯iminopropionate, Ν-(9-acridine) maleimide, etc.; conjugated diene, 1,3-butadiene, isoprene, 2,3- Dimethyl-1,3.butadiene, etc. Among these, 2-methylcyclohexyl acrylate, methacrylic acid is used in view of copolymerization reactivity and solubility of the obtained copolymer in an aqueous alkali solution. 2-hydroxyethyl ester, styrene, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, 1,3-butadiene or 2-(6-hydroxyethylhexyloxy)ethyl methacrylate The compound (a3) may be used singly or in combination of two or more. In the copolymer [A], the content of the repeating unit derived from the compound (a3) is preferably from 10 to 70% by weight, more preferably from 2 to 50% by weight, most preferably from 30 to 50% by weight. weight%. When the content of the repeating unit derived from the compound (a3) is less than 10% by weight, the storage stability of the obtained radiation sensitive linear resin composition is lowered, and on the other hand, if it exceeds 70% by weight, the radiation ray-14 is - 200842162 The resin composition has insufficient alkali developability. The solvent used in the production of the copolymer [A] may, for example, be an alcohol, an ether, a glycol ether, an ethylene glycol alkyl ether acetate, a diethylene glycol, a dipropylene glycol, a propylene glycol monoalkyl ether or a propylene glycol alkane. Ethyl ether acetate, propylene glycol alkyl ether propionate, aromatic hydrocarbon, ketone, ester, and the like. In terms of the specific examples, the alcohol may, for example, be methanol, ethanol, benzyl alcohol, 2-phenylethyl alcohol or 2 i-phenyl-1-propanol; and the ether may, for example, be tetrahydrofuran or the like. The alcohol ether, the ether, etc.; may be exemplified by ethylene glycol monomethyl ether, ethylene glycol monoethyl glycol alkyl ether acetate, and may be exemplified by methyl cellosolve acetate, ethyl ester. Fibrous acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoethyl ether acetate, etc.; in terms of diethylene glycol, 'diethylene glycol monomethyl ether, diethyl Glycol monoethyl ether, diethylene glycol. The diol ethyl methyl ether or the like; dimethyl ether, diethylene glycol diethyl ether, diethylene glycol, and the like, may be exemplified by dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol. Glycol ethyl methyl ether or the like; dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol monoalkyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether , propylene glycol monobutyl ether, etc.; propylene glycol alkyl ether propionate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetic acid Ester and the like; -15- 200842162 propylene glycol alkyl ether acetate, propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate The aromatic hydrocarbon may, for example, be toluene or xylene; and the ketone may, for example, be methyl ethyl ketone, cyclohexanone or 4-hydroxy-4-methyl-2-pentanone; Ethyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2-methylpropionic acid Ethyl ester, methyl hydroxyacetate, ethyl hydroxyacetate, butyl glycolate, methyl lactate, ethyl lactate, propyl lactate, lactic acid Ester, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methoxy Methyl acetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxylate, propyl ethoxyacetate, ethoxylate Butyl acetate, methyl propoxyacetate, ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, butoxyacetic acid Propyl ester, butyl butoxyacetate, 3-methoxybutyl acetate, methyl 2-methoxypropionate 2-methoxypropionic acid ethyl ester, 2-methoxypropionic acid propyl ester, 2- Butyl methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, 2 - Methyl butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, 3- Ethyl methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 3-ethoxy Methyl propionate, ethyl 3-ethoxypropionate, 3--16-200842162 propyl ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, 3 Ethyl propyl propionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate 'ethyl 3-butoxypropionate' 3 An ester of propyl butoxypropionate, butyl 3-butoxypropionate or the like. Among these, ethylene glycol alkyl ether acetate, diethylene glycol, dipropylene glycol, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate are preferred, especially diethylene glycol dimethyl ether Preferably, diethylene glycol ethyl methyl ether, dipropylene glycol dimethyl ether, dipropylene glycol ethyl methyl ether, propylene glycol methyl ether, propylene glycol methyl ether acetate or 3-methoxybutyl acetate. These solvents may be used singly or in combination of two or more. The polymerization initiator used in the production of the copolymer [A] is not particularly limited, and may, for example, be 2,2'-azobisisobutyronitrile or 2,2'-azobis-(2,4-dimethyl Valeronitrile, 2,2'-azobis-(4-methoxy-2,4-dimethylvaleronitrile), 4,4f_azobis(4-cyanovaleric acid), dimethyl 2 An azo compound such as 2'-azobis(2-methylpropionate), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile); Organic peroxides such as base peroxide, lauryl peroxide, tertiary butyl peroxytrimethyl acetate, 1,1 - bis (tertiary butyl peroxy) cyclohexane; hydrogen peroxide Wait. In the case of a polymerization initiator, when a peroxide is used, these and a reducing agent can also be used as a redox type initiator. These polymerization initiators may be used alone or in combination of two or more. The weight average molecular weight (hereinafter referred to as "Mw") of the converted polystyrene by gel permeation chromatography (GPC) of the copolymer [A] is preferably 2,000 to 10,000,000, more preferably 5, 〇〇〇~ 50,000. When the Mw is less than 2,000, the developability of the obtained film, the residual film ratio, and the like are lowered, which may impair the shape of the pattern -17-200842162, heat resistance, etc., and if it exceeds 100,000, the resolution is lowered. Detrimental to the shape of the figure. The copolymer [A] produced as described above has at least a group selected from the group consisting of a sulfhydryl group and a carboxylic anhydride group derived from the compound (al) and a dioxolane structure derived from the compound (a2). It has an appropriate solubility to the alkali developer 'at the same time' and has the advantage of being easily hardened by heating even without using a special hardener. The copolymer [A] obtained by the above-mentioned method may be used as a linear resin composition for modulating the radiation sensitive agent depending on the state of the solution, or may be used to modulate the radiation-sensitive linear resin composition from the solution. Further, in the present invention, other polymers may be used together with the copolymer [A]. As the other polymer, an alkali-soluble copolymer obtained by copolymerizing the above compounds (a1) and (a3) is preferred. In the alkali-soluble copolymer, the content of the repeating unit derived from the compound (al) is preferably 40% by weight, more preferably 8 to 30% by weight. The Mw of the alkali-soluble copolymer is preferably from 1,000 to 50,000, more preferably from 3,000 to 3 Torr. The related alkali-soluble copolymer ' can be produced by using a mixture of the compounds (al) and (a3) and the method for producing the reference copolymer [A]. In the present invention, when the copolymer [A] and the other polymer are used, the ratio of use of the other polymer is < 80 weight% with respect to the total of the copolymer [A] and the other polymer. The following is better than 6 〇 weight ° / 〇 below, 5 〇 weight % or less is the best. _[B] Polymerizable unsaturated compound _ -18- 200842162 The radiation sensitive linear resin composition of the present invention is a monthly unsaturated compound, preferably having an ethylenic unsaturated. [B] The polymerizable unsaturated compound is not particularly limited as long as it can be polymerized, and it is preferable to use a trifunctional or higher (meth)acrylate from the viewpoint of improving the strength of the obtained spacer. In terms of the monofunctional (meth) acrylate, a carboxylic acid ester, a 2-hydroxyethyl methacrylate, a dibasic acid ester, a diethylene glycol monoethyl ether methacrylate, an isodecyl methyl group Acrylate, 3-methoxybutoxybutyl methacrylate, 2-propenyl phthalic acid phthalate, 2-methyl propylene methacryl oxime phthalate, ω-carboxy condensate For the lactone monopropyl), aronix Μ-101, Μ-1 M-5 3 00 (manufactured by Toagosei Co., Ltd.); KAYARAD 120S (manufactured by Nippon Kayaku Co., Ltd.); bisuko-tol58, manufactured by Chemical Industry Co., Ltd. )Wait. The bifunctional (meth) acrylate aspect, an acid ester, ethylene glycol dimethacrylate, diethylene glycol ethylene dimethacrylate, tetraethylene glycol dipropylene dimethacrylate, 1, 6-hexanediol dipropenyl alcohol dimethacrylate, 1,9-nonanediol dipropylene dimethacrylate, bisphenoxyethanol hydrazine dipropylene f [B] polymerizability and bond polymerization The compound g has an ethylenic unsaturated but good polymerizability, monofunctional, bifunctional or 2-hydroxyethyl propylene glycol monoethyl ether propyl ester, isodecyl acrylate acrylate, 3-methyl group: Ethyl-2-hydroxypropyl; oxyethyl-2-hydroxypropionate, etc., also commercially available, 11 with the same Μ-114, with TC-110S, with TC- the same 2 3 1 1 (Osaka organic example Ethylene glycol dipropenol diacrylate, dimorphate, tetraglycolate, 1,6-hexanedicarboxylate, 1,9-nonanediol enoate, bisphenoxy-19- 200842162 Ethyl alcohol, monomethyl propionate, etc., and commercially available products, such as aronix M-210, M-240, M-6200 (manufactured by Toagosei Co., Ltd.), KAYARAD HDDA, and HX-220, Same as R-604 (day本uko-to260, the same as 312, the same as 3 3 5 HP (manufactured by Osaka Organic Chemical Industry Co., Ltd.), etc. The trifunctional or higher (meth) acrylate is exemplified by trimethylol Propane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate Ester, dipentaerythritol pentaacrylate, dipentaerythritol pentamethyl acrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, tris(2-propenyl fluorenyloxy) Ethyl) phosphate, tris(2-methylpropenylmethyl decyloxyethyl) phosphate, etc., may be exemplified by having a linear structure of an alkylene group, an alicyclic structure, and two or more isocyanate groups in the molecule. The urethane acrylate compound obtained by reacting a compound with a trifunctional or tetrafunctional or 5-functional (meth) acrylate compound having more than one hydroxy group in the molecule, and examples of such commercially available products. Raise aronix M-309, with M-400, with M-405, with M- 450, with M-7100, same as M-8 0 0 0, with M-8060, with TO-1 450 (manufactured by Toagosei Co., Ltd.), KAYARAD TMPTA, with DPHA, with DPCA-20, with DPCA-30, with DPCA- 60, with DPCA-120 (manufactured by Nippon Kayaku Co., Ltd.), bisuko-to 295, same as 300, with 360, with GPT, with 3PA, with 400 (made by Osaka Organic Chemical Industry Co., Ltd.), new frontier R-1150 (first Manufactured by an industrial pharmaceutical company, KAYARAD DPHA-40H (manufactured by Nippon Chemical Co., Ltd.). -20- 200842162 Among these monofunctional, bifunctional or trifunctional or higher (meth) acrylates, a trifunctional or higher (meth) acrylate is more preferable as 'trimethylolpropane triacrylate' Neopentyl alcohol triacrylate, neopentyl alcohol tetraacrylate, dipentaerythritol pentaacrylate or dipentaerythritol hexaacrylate is particularly preferred. The monofunctional, bifunctional or trifunctional or higher functional (meth) acrylate may be used singly or in combination of two or more. In the radiation sensitive linear resin composition of the present invention, the use ratio of the [B] polymerizable unsaturated compound means the total amount of the polymer (referred to as the total amount of the copolymer [A] and other polymers. The same applies hereinafter. It is preferably 50 to 200 parts by weight, more preferably 60 to 150 parts by weight, based on 100 parts by weight. [B] If the use ratio of the polymerizable unsaturated compound is less than 50 parts by weight, there may be development residue during development. On the other hand, if it exceeds 200 parts by weight, the adhesion of the resulting spacer may be lowered. - [C] Sensitive radiation linear polymerization initiator - [C contained in the radiation sensitive linear resin composition of the present invention] The radiation-sensitive linear polymerization initiator is irradiated with visible light, ultraviolet rays, far ultraviolet rays, charged particle rays, X-rays, etc., so that the above-mentioned [B] polymerizable unsaturated compound starts to polymerize, and the active species are produced. Such [C] sensitive radiation linear polymerization initiator, using hydrazine compound, biimidazole compound, benzoin compound, acetophenone compound, diphenyl ketone compound, α-diketone compound, sensitive Ray cation polymerization initiator preferably above aspect oxime compounds, carbazole compounds include, other oximation -21--. 200842162 carbazole compound thereof above aspect, having 9. Hey. The oxime-quinone-type polymerization initiator of the carbazole structure is preferred. Specific examples thereof include 1-[9-ethyl-6-phenylindenyl 9-indolyl-3-yl]-decane-1,2-decane-2-indole-0. -benzoate, 1-[9-ethyl-6-benzoin-9-indole-oxazol-3-yl]-nonane-1,2-decane-2-indole-0-acetic acid Salt, 1-[9-ethyl-6-benzoinyl-9. Hey. - oxazol-3-yl]-pentane-1,2-pentane-2-indole-0-acetate, 1-[9-ethyl-6-benzoinyl- 9. Hey. -oxazol-3-yl]-octane-1-one oxime-0-acetate, 1-[9-ethyl-6-(2-methylphenylhydrazino)-9. Hey. -oxazol-3-yl]-ethane-buxanthene- 0-benzoate, 1-[9-ethyl-6-(1,3,5-trimethylphenylhydrazino)-9. 11. -oxazol-3-yl]-ethane-1-one oxime-indole-benzoate, 1-[9-butyl-6-(2-ethylbenzoinyl)-9·Η·-咔Zyrid-3-yl]-ethane-1-one oxime-0-benzoate, ethanone, 1-[9·ethyl-6-(2-methylphenylhydrazino)-9. H. -oxazol-3-yl]-, 1-(0-ethenyloxyindole), ethanone, 1-[9-ethyl-6-[2-methyl-4-(2,2 -Dimethyl-1,3-dioxolyl)methoxybenzoinyl-9. Η ·-carbazol-3-yl]-, 1-(0-ethenyloxyhydrazine), ethanone, l-[9-ethyl-6-(2-methylphenylhydrazino) -9·Η·-carbazol-3-yl]-, 1-(0-ethenyloxyindole), etc. Among these, ethanone, 1-[9·ethyl-6- (2-methylphenyl fluorenyl)-9. H.-carbazol-3-yl]-, 1-(0-ethenyloxypurine) or ethanone, 1-[9-ethyl-6-[2-methyl- 4-(2) ,2-dimethyl-1,3-dioxolyl)methoxybenzoinyl]-9. H·-carbazol-3-yl]-, 1-(0-ethenyloxyhydrazine) is particularly preferred. These carbazole compounds may be used singly or in combination of two or more. The other ruthenium compound may, for example, be 1,2-octanedione-1 - [ 4 - -22- 200842162 (phenylthio)phenyl]-2-(0-benzofluorenyloxy), 1 , 2-butanedione-1-[4-(phenylthio)phenyl]-2-(0-phenylhydrazinyloxy), 1,2-butanedione-1-[4-( Phenylthio)phenyl]-2_(0-ethazyloxy)' 1,2-octyl-anther-1-[4-(methylthio)phenyl]-2-(0-phenylhydrazine) Base oxindole), 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(0-(4-methylbenzohydrazino)). Among these, 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(0-benzofluorenyloxyindole) is particularly preferred. In the above biimidazole compound, 2,2 '-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2' can be exemplified. -biimidazole, 2,2,-bis(2-bromophenyl)-4,4',5,5f-tetrakis(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2, 2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2,-biimidazole, 2,2,-bis(2,4-dichlorophenyl) -4,4',5,5'-tetraphenyl·1,2,·biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5 ,-Tetraphenyl-1,2,-biimidazole, 2,2, bis(2-bromo)-4,4',5,5--tetraphenyl·ι,2,·biimidazole, 2,2 , bis(2,4-dibromophenyl)-4,4',5,5'-tetraphenyl-1,2,-biimidazole, 2,2'-bis(2,4,6-tribromo Phenyl)_4,4',5,5'-tetraphenyl-indole, 2,-biimidazole, etc. Among these, 2,2,-bis(2-chlorophenyl)-4,4' ,5,5,-Tetraphenyl-1,2,-biimidazole, 2,2,-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-152 '_Biimidazole or 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl β1,2,-biimidazole is preferred, preferably, 2,2' - bis(2,4-dichlorophenyl)-4,4,5,5,-tetraphenyl-1,2,-biimidazole. These hydrazine compounds may be used singly or in combination of two or more. By using these biimidazole compounds, the sensitivity, resolution and adhesion of the resulting radiation sensitive linear resin composition can be further improved. In the radiation sensitive resin composition of the present invention, in the case of [C] sensitive radiation linear-23-200842162 polymerization initiator, when a biimidazole compound is used, in order to sensitize it, a dialkylamine group may be used. An aromatic compound (hereinafter referred to as "dialkylamine based sensitizer"). As the related dialkylamine-based sensitizer, 4,4'-bis(dimethylamino)diphenyl ketone and 4,4'-bis(diethylamino)diphenyl ketone can be exemplified. , p-dimethylaminobenzoic acid ethyl, p-diethylaminobenzoic acid ethyl, p-dimethylaminobenzoic acid isoamyl ester, p-diethylaminobenzoic acid isoamyl ester, etc. Among them, 4,4f-bis(diethylamino)diphenyl ketone is preferred. These dialkylamine-based sensitizers may be used singly or in combination of two or more. Further, in the case of using a biimidazole compound and a dialkylamine-based sensitizer, a thiol compound may be added to the hydrogen supply compound. The biimidazole compound is sensitized and cleaved by a dialkylamine-based sensitizer to produce an imidazole radical, but at this time, a high initial polymerization energy is not immediately found, and the resulting spacer is not inverted. The case of a good shape. In the system in which the biimidazole compound and the dialkylamine-based sensitizer coexist, this problem can be solved by adding a thiol compound. That is, in the imidazole radical, the imidazole radical is made neutral imidazole by supplying a hydrogen radical from the thiol compound, and as a result, a spacer shape is produced due to a component of a sulfur radical having a high initial polymerization energy. It becomes a better straight cone shape. The above thiol compound may, for example, be 2-hydrothiobenzothiazole, 2-hydrothiobenzoxazole, 2-hydrothiobenzimidazole or 2-hydrothio-5-methoxybenzo Aromatic thiol such as thiazole, 2-hydrothio-5-methoxybenzimidazole, 3-hydrothiopropylpropionic acid, methyl 3-hydroxythiopropionate, 3-hydroxythiopropionic acid Aliphatic monothiol such as ester, octyl 3-hydrothiopropionate; -24- 200842162 3,6-dioxa-1,8-octanedithiol, isopentanol tetra(hydrogenthio) Acetate), a bifunctional or higher aliphatic thiol such as pentaerythritol tetrakis(3-hydrothiopropionate). These thiol compounds may be used singly or in combination of two or more types. The benzoin compound may, for example, be benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2-phenylmercaptobenzoic acid methyl group or the like. The acetonitrile compound may, for example, be an α-hydroxyketone compound, an α-amino ketone compound or a compound other than these. Specific examples of the above α-hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropan-1-one and 1-(4-isopropylphenyl)-2-hydroxy-2. -methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)one, 1-hydroxycyclohexyl phenyl ketone, etc.; the above α-amino ketone Specific examples of the compound may, for example, be 2-methyl-1-[4-(methylthio)benzyl]-2-morphinyl (morpholino) gamma-1, 2 -mercapto-2 - a methylamino-1-(4-mercaptophenyl)-butan-1-indole. These acetophenone compounds may be used singly or in combination of two or more. In the present invention, in terms of the [C] radiation-sensitive linear polymerization initiator, the sensitivity of the obtained radiation sensitive linear resin composition, the shape of the obtained spacer, the compressive strength, and the like can be further improved by using an acetophenone compound. The diphenyl ketone compound may, for example, be 4,4'-bis(dimethylamino)diphenyl ketone or 4,4 bis(diethylamino)diphenyl ketone. The α-diketone compound may, for example, be a diethylidene group, a diphenylfluorene-25-200842162 group or a methylphenyl fluorenylcarboxylate. The above-mentioned radiation-sensitive linear cationic polymerization initiator may, for example, be an iron salt, a metallocene compound or the like. Specific examples of the above gun salt include phenyl azo-iron tetrafluoroborate, phenyl azo-hexafluorophosphonate, phenyl azo-hexafluoroarsenate, and phenyl azo-three. Fluoromethanesulfonate, phenyl azo-trifluoroacetate, phenyl azo-p-toluenesulfonate, 4-methoxyphenyl azo-tetrafluoroborate, 4-methoxy Phenylazo-hexafluorophosphonate, 4-methoxyphenylazo-hexafluoroarsenate, 4-methoxyphenylazo-trifluoromethanesulfonate, 4-methoxybenzene Azo-l-trifluoroacetate, 4-methoxyphenyl arsenazo-p-toluenesulfonate, 4-tert-butylphenyl arsenazotetrafluoroborate, 4-tertiary butyl Phenyl azo-hexafluoro squarate ' 4-tris-butylphenyl azo-hexafluoroarsenate, 4-tert-butylphenyl azo-trifluoromethane sulfonate, 4-tertiary Butyl phenyl azo-trifluoroacetate, azo key salt of 4-tris-butylphenyl azo-p-toluenesulfonate, etc.; triphenylsulfonium tetrafluoroborate, triphenyl Hexafluorophosphonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate , triphenylsulfonium-p-toluenesulfonate, 4-methoxyphenyldiphenylphosphonium tetrafluoroborate, 4-methoxyphenyldiphenylphosphonium hexafluorophosphonate 4- 4-methoxy Phenyldiphenylphosphonium hexafluoroarsenate, 4-methoxyphenyldiphenylphosphonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylphosphonium trifluoroacetate, 4- Methoxyphenyldiphenylphosphonium-p-toluenesulfonate 4- 4-phenylthiophene diphenyltetrafluoroborate, 4-phenylthiophene diphenyl hexafluorophosphonate, 4-phenylthiophene Phenyl hexafluoroarsenate, 4-phenylthiophene diphenyl trifluoromethanesulfonate, 4_ -26- 200842162 Phenylthiophene diphenyl trifluoroacetate, 4-phenylthiophene diphenyl-p- An onium salt such as a tosylate or the like. The above-mentioned metallocene compound may, for example, be (l-6-η-cumene) (η-cyclopentadienyl) iron (1+) hexafluorophosphoric acid (1-) or the like. The commercially available product of the sensitizing radiation polymerization initiator may, for example, be Adecaultra set ΡΡ-33 (manufactured by ADEKA) of azo-iron salt, OPTOMER SP-150 of bismuth salt, and -170 (manufactured by ADEKA Corporation) In the present invention, 11C (11161 & 11〇〇6116) compound 11 & (: 11^261 (manufactured by Chiba Specialty Chemicals Co., Ltd.), etc. In the present invention, [C] sensitive radiation linear polymerization initiator In the present invention, it is preferred to use the above-mentioned hydrazine compound for the [C] radiation-sensitive linear polymerization initiator, and it is particularly preferred to use the carbazole compound and other hydrazine compounds. [C] In terms of a linear radiation polymerization initiator, the sensitivity of the radiation-sensitive linear resin composition to radiation can be further improved by using an oxazole compound and other ruthenium compounds, for example, even below 1,500 J/m2. In the case of the amount of exposure, a spacer for a display panel having excellent adhesion to a substrate can be formed. In the radiation sensitive linear resin composition of the present invention, the ratio of use of the [C] radiation-sensitive linear polymerization initiator is relative to [B] polymerization. Sexual desaturation 1 parts by weight, preferably 1 to 30 parts by weight, more preferably 2 to 20 parts by weight. [C] The residual film rate during development if the amount of the linear radiation polymerization initiator used is less than 丨 by weight On the other hand, if it exceeds -27-200842162 3 parts by weight, the solubility of the unexposed portion to the alkaline developing solution at the time of development is insufficient. The photosensitive radiation-based resin composition of the present invention is used [ In the direct radiation polymerization initiator, the ratio of the ruthenium compound to the total amount of the [C] radiation-sensitive linear polymerization initiator is preferably 20% by weight or more, more preferably 40% by weight or more. When the ratio of the ruthenium compound is less than 20% by weight, the effect expected by the present invention is hardly found. Among the ruthenium compounds, the ratio of the carbazole compound is preferably 30% by weight or more, more preferably 30% by weight or more based on the total amount of the ruthenium compound. 50% by weight or more. In the radiation sensitive linear resin composition of the present invention, in the case of the [C] radiation-sensitive linear polymerization initiator, a biimidazole compound is used, and in the case of using the dialkylamine-based sensitizer Dialkyl The use ratio of the amine-based sensitizer is preferably from 1 to 5 parts by weight, more preferably from 1 to 20 parts by weight, based on 100 parts by weight of the total amount of the polymer. Use of a dialkylamine-based sensitizer If the amount is less than 0.1 part by weight, the resulting spacer may cause film thinning to impair the shape of the pattern. On the other hand, if it exceeds 50 parts by weight, it may be detrimental to the pattern shape of the spacer. Further, in the case of the [C] radiation-sensitive linear polymerization initiator, a biimidazole compound is used, and when the dialkylamine-based sensitizer and the thiol compound are used, the use ratio of the thiol compound is relative to the polymer. The total amount is 100 parts by weight, preferably 〇. 1 to 50 parts by weight, more preferably 1 to 20 parts by weight. When the use ratio of the thiol compound is less than 1 part by weight, the resulting spacer may cause film thinning or poor shape of the pattern. On the other hand, if it exceeds 50 parts by weight, it may be detrimental to the spacer. Graphic shape. -28- 200842162 - Other Additives - The radiation sensitive linear resin composition of the present invention contains the above-mentioned copolymer [A] '[B] a polymerizable unsaturated compound and an essential component of the [C] radiation radiation linear combination initiator, but In the range which does not impair the effect expected by the present invention, other additives may be contained as needed. As the other additives, a surfactant, an adhesion aid, a storage stabilizer, a heat resistance improving agent, and the like can be exemplified. In order to improve the coatability of the resulting radiation-sensitive linear resin composition, the above surfactant may be used. As the related surfactant, a fluorine-based surfactant, a polysiloxane surfactant, and other surfactants can be exemplified. In the above-mentioned fluorine-based surfactant, a compound having a fluoroalkyl group or a fluoroalkylene group in at least one of a main chain and a side chain is preferably used. Specific examples thereof include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl)ether, 1,1,2,2-tetrafluorooctylhexyl ether. , octaethylene glycol di(1,1,2,2-tetrafluorobutyl)ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl)ether, octapropylene glycol di 1,1,2,2-tetrafluorobutyl)ether, hexapropanediol bis(1,1,2,2,3,3-hexafluoropentyl)ether, sodium perfluorododecyl citrate, 1,1 , 2,2,3,3,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, sodium fluoroalkyl benzoate, halothane Sodium phosphinate, sodium fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, diglycerol four (fluoroalkyl polyoxyethylene ether), fluoroalkyl ammonium iodide, fluoroalkyl betaine 'fluoroalkyl Polyoxyethylene ether 'perfluoroalkyl polyoxyethanol' perfluoroalkyl alkoxide, fluoroalkyl alkoxide, etc., and such commercially available products, BM-1000, BM-1 1 00 (BM) CHEMIE company), megafuck F142D, -29- 200842162
同 F172，同 F173，同 F183，同 F178，同 F191，同 F471，同F476(大日本油墨化學工業公司製）’ Fluorad FC 170C，FC-171，FC-430，FC-431(住友 3M 公司製）， Safron S-112，同 S-113，同 S-131 ’ 同 S-141 ’ 问 S-145，同 S-3 82，同 SC-101，同 SC-102，同 SC-103，同 SC-104，同 SC-105，同 SC-106(旭硝子公司製），f-top EF301，同 3 03，同 3 52(新秋田化成公司製），Futazient FT-1 00，同 FT-1 1 0，同 FT-1 40 A，同 FT-1 50，同 FT-250 ，同 FT-251 ，同 FTX-251 ，同 FTX-218 ，同 FT-300 ， 同 FT-310，同 FT-400S(Neos 公司製）等。 上述聚矽氧系界面活性劑方面，可例舉商品名 Tor ay 聚矽氧 DC3PA，同 DC7PA，同 SH11PA，同 SH21PA，同 SH28PA，同 SH29PA，同 SH30PA，同 SH-190，同 SH-193，同 SZ-603 2，同 SF-8428，同 DC-57，同 DC-190(Toray· Dow Corning·聚砂氧公司製），TSF-4440， TSF-43 00 ， TSF-4445 ， TSF-4446 ， TSF-4460 ， TSF- 4 4 5 2 (Μ 〇 m e n t i v e Performance Materials Japan 合同會公司 製）等的市售品。 上述其他的界面活性劑方面，可例舉聚氧乙烯月桂基 醚，聚氧乙烯硬脂醯基醚，聚氧乙烯油基醚等的聚氧乙烯 院基釀； 聚氧乙烯正辛基苯基醚，聚氧乙烯正壬基苯基醚等的 聚氧乙嫌芳基醚；聚氧乙Μ二月桂酸酯，聚氧乙烯二硬脂 酸酯等的聚氧乙烯二烷基酯等的非離子系界面活性劑，或 -30- 200842162 市售品的 ΚΡ341(信越化學工業公司製），Polyflow No.57，95(共榮公司化學公司製）等。 該等界面活性劑，可單獨使用或混合2種以上使用。 界面活性劑的配合量，相對於聚合物的全量1 0 0重量 份，較佳爲5重量份以下，更佳爲2重量份以下。界面活 性劑的配合量若超過5重量份時，塗佈時易產生膜破裂。 爲了進而提高所得間隔器與基體的密接性，可使用上 述的黏接助劑。 相關的黏接助劑方面，以官能性矽烷偶合劑爲佳，可 例舉羧基，甲基丙烯醯基，異氰酸酯基，環氧基等具有反 應性官能基的矽烷偶合劑。更具體言之，可例舉三甲氧基 矽烷基苯甲酸，r -甲基丙烯醯基氧丙基三甲氧基矽烷， 乙烯三乙醯氧基矽烷，乙烯三甲氧基矽烷，γ-異氰酸酯丙 基三乙氧基矽烷，γ-環氧丙基丙基三甲氧基矽烷，2-(3,4-環氧基環己基）乙基三甲氧基矽烷等。 該等黏接助劑，可單獨使用或混合2種以上使用。 黏接助劑的配合量，相對於聚合物的全量1 0 0重量 份，較佳爲20重量份以下，更佳爲10重量份以下。黏接 助劑的配合量若超過20重量份時，易有顯影殘留的情 形。 在以提高所得敏輻射線性樹脂組成物的保存穩定性爲 目的下，可使用上述的保存穩定劑。相關的保存穩定劑方 面，可例舉硫，醌化合物，氫醌化合物，聚氧化合物， 胺，硝基亞硝基化合物等。其具體例可例舉4 -甲氧基苯 -31 - 200842162 酚，N-亞硝基-N-苯基羥基胺鋁等。該等相對於聚合物的 全量1〇〇重量份，較佳爲使用3.0重量份以下，更佳爲使 用0.001〜0.5重量份。保存穩定劑的使用量若超過3.0重 量份時，敏輻射線性樹脂組成物的放射線感度不充分，所 得間隔器的圖型形狀將會惡化。 爲了更提高所得間隔器的耐熱性，可使用上述的耐熱 性提高劑。相關的耐熱性提高劑方面，可例舉N-(烷氧基 甲基）乙炔脲化合物，N-(烷氧基甲基）三聚氰胺化合物，1 分子中具有2官能以上環氧基的化合物等。 上述N_ (烷氧基甲基）乙炔脲化合物的具體例方面，可 例舉Ν,Ν,Ν’，Ν’·四（甲氧基甲基）乙炔脲，N，N，N’，N’-四（乙 氧基甲基）乙炔脲，N,N，N、Nf -四（正丙氧基甲基）乙炔脲， N，N，N’，N、四（異丙氧基甲基）乙炔脲，N，N,N’，N’-四（正丁 氧基甲基）乙炔脲，N，N，N’，N’-四（三級丁氧基甲基）乙炔脲 等。該等之中，特別以N,N，N’，N'-四（甲氧基甲基）乙炔脲 爲佳。 上述N-(烷氧基甲基）三聚氰胺化合物的具體例方面， 可例舉1^川，>^，化，>^，，>^，-六（甲氧基甲基）三聚氰胺， N，N，N’，Nl，N’’，N’’-六（乙氧基甲基）三聚氰胺， N，N，N’，Nf，N"，N"-六正丙氧基甲基）三聚氰胺， N，N，N’，N’，N"，N’’-六（異丙氧基甲基）三聚氰胺， N，N，N'，N’，N，，，N，，-六（正丁氧基甲基）三聚氰胺， >1，>^，!^’5>^，>^"，!^"-六（三級丁氧基甲基）三聚氰胺等。該等 之中，以N，N，N’，N’，N'，，N"-六（甲氧基甲基）三聚氰胺爲特 -32- 200842162 佳。該等的市售品方面，可例舉 NIKALAC N-2702， MW-30M(三和化學公司製）等。 上述1分子中具有2官能以上環氧基的化合物方面， 可例舉乙二醇二縮水甘油基醚，二乙二醇二縮水甘油基 醚，聚乙二醇二縮水甘油基醚，丙二醇二縮水甘油基醚， 三丙二醇二縮水甘油基醚，聚丙二醇二縮水甘油基醚，新 戊二醇二縮水甘油基醚，1，6-己烷二醇二縮水甘油基醚， 甘油二縮水甘油基醚，三羥甲基丙烷三縮水甘油基醚，氫 化雙酚A二縮水甘油基醚，雙酚A二縮水甘油基醚，苯 酚酚醛清漆型環氧基樹脂等。該等的市售品方面，可例舉 Epolight 40E，Epolight 100E，Epolight 200E，Epolight 7 0 P，Epolight 2 0 0 P，Epolight 4 0 0 P，Epolight 4 0 0 E， Epolight 1 5 00NP ， Epolight 1 600 ， Epolight 80MF ，Same as F172, same as F173, same as F183, same as F178, same as F191, same as F471, with F476 (made by Dainippon Ink and Chemicals Co., Ltd.) Fluorad FC 170C, FC-171, FC-430, FC-431 (manufactured by Sumitomo 3M Co., Ltd.) ), Safron S-112, same as S-113, same as S-131 'same S-141 ' Q S-145, same as S-3 82, same as SC-101, same SC-102, same SC-103, same SC -104, same as SC-105, same as SC-106 (made by Asahi Glass Co., Ltd.), f-top EF301, same as 3 03, same as 3 52 (made by New Akita Chemical Co., Ltd.), Futazient FT-1 00, with FT-1 1 0 , with FT-1 40 A, with FT-1 50, with FT-250, with FT-251, with FTX-251, with FTX-218, with FT-300, with FT-310, with FT-400S (Neos Company system) and so on. The polyoxo-based surfactant may, for example, be a trade name of Tor ay polyoxyl DC3PA, the same as DC7PA, the same SH11PA, the same SH21PA, the same SH28PA, the same SH29PA, the same SH30PA, the same SH-190, the same SH-193, Same as SZ-603 2, same as SF-8428, same as DC-57, with DC-190 (made by Toray·Dow Corning·Sand Co., Ltd.), TSF-4440, TSF-43 00, TSF-4445, TSF-4446, Commercial products such as TSF-4460 and TSF-4 4 5 2 (manufactured by Performance 〇 mentive Performance Materials Japan Co., Ltd.). The above other surfactants may, for example, be polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, etc.; polyoxyethylene n-octylphenyl; a polyoxyethylene diaryl ether such as an ether or a polyoxyethylene n-decylphenyl ether; a polyoxyethylene dialkyl ester such as polyoxyethylene dilaurate or polyoxyethylene distearate; An ionic surfactant, or ΚΡ 341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 57, 95 (manufactured by Kyoei Chemical Co., Ltd.), -30-200842162. These surfactants may be used singly or in combination of two or more. The blending amount of the surfactant is preferably 5 parts by weight or less, more preferably 2 parts by weight or less based on 100 parts by weight of the total amount of the polymer. When the amount of the surfactant is more than 5 parts by weight, film breakage is likely to occur during coating. In order to further improve the adhesion between the resulting spacer and the substrate, the above-mentioned adhesion aid can be used. The functional decane coupling agent is preferably a functional decane coupling agent, and examples thereof include a decane coupling agent having a reactive functional group such as a carboxyl group, a methacryl oxime group, an isocyanate group or an epoxy group. More specifically, trimethoxydecyl benzoic acid, r -methyl propylene methoxy propyl trimethoxy decane, ethylene triethoxy decane, ethylene trimethoxy decane, γ-isocyanate propyl may, for example, be mentioned. Triethoxy decane, γ-glycidylpropyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, and the like. These adhesion aids may be used singly or in combination of two or more. The compounding amount of the adhesion aid is preferably 20 parts by weight or less, more preferably 10 parts by weight or less based on 100 parts by weight of the total amount of the polymer. When the amount of the adhesion aid is more than 20 parts by weight, the development remains liable. The above-mentioned storage stabilizer can be used for the purpose of improving the storage stability of the obtained radiation sensitive linear resin composition. The related storage stabilizers may, for example, be sulfur, a hydrazine compound, a hydroquinone compound, a polyoxygen compound, an amine, a nitronitroso compound or the like. Specific examples thereof include 4-methoxybenzene-31 - 200842162 phenol, N-nitroso-N-phenylhydroxylamine aluminum, and the like. The amount is preferably 3.0 parts by weight or less, more preferably 0.001 to 0.5 parts by weight, based on the total amount of the polymer. When the amount of the storage stabilizer used exceeds 3.0 parts by weight, the radiation sensitivity of the radiation sensitive linear resin composition is insufficient, and the pattern shape of the spacer is deteriorated. In order to further improve the heat resistance of the resulting spacer, the above heat resistance improving agent can be used. The related heat resistance improving agent may, for example, be an N-(alkoxymethyl)acetylene urea compound, an N-(alkoxymethyl)melamine compound, or a compound having a bifunctional or higher epoxy group in one molecule. Specific examples of the above N_(alkoxymethyl)acetylene urea compound may, for example, be Ν, Ν, Ν', Ν'·tetrakis(methoxymethyl)acetylene urea, N, N, N', N' -tetrakis(ethoxymethyl)acetylene urea, N,N,N,Nf-tetrakis(n-propoxymethyl)acetylene urea, N,N,N',N,tetrakis(isopropoxymethyl) Acetylene urea, N, N, N', N'-tetrakis (n-butoxymethyl) acetylene urea, N, N, N', N'-tetrakis (tertiary butoxymethyl) acetylene urea, and the like. Among these, N, N, N', N'-tetrakis(methoxymethyl)acetylene urea is particularly preferred. Specific examples of the above N-(alkoxymethyl)melamine compound include, for example, 1^chuan, >^, and, ^, ^, >^,-hexa(methoxymethyl)melamine, N,N,N',Nl,N'',N''-hexa(ethoxymethyl)melamine, N,N,N',Nf,N",N"-hexa-n-propyloxymethyl) Melamine, N, N, N', N', N", N''-hexa(isopropoxymethyl) melamine, N, N, N', N', N,,, N,, - six ( N-butoxymethyl)melamine, >1,>^,!^'5>^,>^",!^"-hexa(tris-butoxymethyl)melamine. Among these, N, N, N', N', N', and N"-hexa(methoxymethyl) melamine are particularly preferred from -32 to 200842162. For the above-mentioned commercial products, NIKALAC N-2702, MW-30M (manufactured by Sanwa Chemical Co., Ltd.), and the like can be exemplified. The compound having a bifunctional or higher epoxy group in one molecule may, for example, be ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether or propylene glycol dihydrate. Glyceryl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether , trimethylolpropane triglycidyl ether, hydrogenated bisphenol A diglycidyl ether, bisphenol A diglycidyl ether, phenol novolac type epoxy resin, and the like. For such commercial products, Epolight 40E, Epolight 100E, Epolight 200E, Epolight 7 0 P, Epolight 2 0 0 P, Epolight 4 0 0 P, Epolight 4 0 0 E, Epolight 1 5 00NP, Epolight 1 600 , Epolight 80MF ,
Epolight 100MF，Epolight 4000 » E p o 1 i g h t 3 0 0 2 (共榮社化 學公司製），epitoke 15 2(日本環氧基樹脂公司製）等。該等 可單獨使用或組合2種以上使用。 此種耐熱性提高劑的使用比率，相對於聚合物的全量 1〇〇重量份，較佳爲30重量份以下，更佳爲1〜20重量 份。 -溶劑- 本發明的敏輻射線性樹脂組成物，較佳爲將上述共聚 物[A]，[B]聚合性不飽和化合物及[C]敏輻射線性聚合引 發劑’以及任意使用之其他的添加劑，溶解於適當的溶劑 -33- 200842162 中，調製爲組成物溶液。 調製本發明敏輻射線性樹脂組成物溶液所使用的溶劑 方面’可使用能平均溶解構成敏輻射線性樹脂組成物的各 成分’且與各成分不產生反應之物。 此種丨谷劑方面’可例舉同於用於製造上述共聚物[A] 所使用的溶劑所例示之物。 此種溶劑中，就各成分的溶解性，與各成分的反應 性，易形成被膜等的觀點而言，以使用例如醇，乙二醇 醚，乙二醇烷基醚乙酸酯，酯及二乙二醇爲佳。該等中， 以使用卞基醇’ 2-苯基乙基醇，3 -苯基-1-丙醇，乙二醇單 丁基醚乙酸酯，二乙二醇單乙基醚乙酸酯，二乙二醇二乙 基醚，二乙二醇乙基甲基醚，二乙二醇二甲基醚，丙二醇 單甲基醚，丙二醇單甲基醚乙酸酯，甲氧基丙酸甲基，乙 氧基丙酸乙基，乙酸-3甲氧基丁基爲特佳。 進而該溶劑，爲了同時提高膜厚面內的均一性，可倂 用高沸點溶劑。可倂用的高沸點溶劑方面，可例舉N -甲 基甲醯胺，Ν,Ν-二甲基甲醯胺，N -甲基N -甲醯苯胺，N-甲基乙醯胺，Ν，Ν -二甲基乙醯胺，Ν -甲基吡咯啶酮，二甲 基亞颯，苄基乙基醚，二己基醚，丙酮基丙酮，異佛爾 酮，己酸，辛酸，1 -辛醇，1 -壬醇，乙酸苄酯，苯甲酸乙 酯，草酸二乙酯，順丁烯二酸二乙酯，γ - 丁內酯，碳酸乙 烯酯，碳酸丙烯酯，苯基溶纖劑乙酸酯等。該等之中，以 Ν-甲基吡咯啶酮’ γ-丁內酯，Ν，Ν-二甲基乙醯胺爲佳。 溶劑的使用量方面，敏輻射線性樹脂組成物的固形成 -34- 200842162 分濃度（去除敏輻射線性樹脂組成物的溶劑之成分的合計 重量，佔敏輻射線性樹脂組成物的全部重量之比率）以10 〜8 0重量％的量爲佳，以 1 5〜7 0重量％的量爲更佳。較 佳的固形成分濃度因在基板上形成本發明敏輻射線性樹脂 組成物的被膜之際所採用的方法而異，該等詳如後述。 如此一來所調製的敏輻射線性樹脂組成物之溶液，可 因應需要，藉由自孔徑例如0 · 2〜0.5 μηι左右的微孔過濾 器等過濾後供使用。 本發明的敏輻射線性樹脂組成物，特別適合用於形成 液晶面板或觸控面板等之液晶顯示元件用間隔器。 <、)仪晶顯不兀件用間隔器的形成方法> 若使用本發明的敏輻射線性樹脂組成物形成液晶顯示 元件用間隔器時，例如可藉由至少依下列記載的順序含有 以下步驟的方法而達成。 (1) 於基板上形成本發明敏輻射線性樹脂組成物的被 月吴之步驟， (2) 將該被膜的至少一部份曝光的步驟， (3) 將曝光後的被膜顯影的步驟，及 (4) 將顯影後的被膜加熱的步驟。 以下說明關於形成本發明液晶顯示元件用間隔器之方 法的各步驟。 (1)於基板上形成本發明敏輻射線性樹脂組成物之被 膜的步驟 -35- 200842162 若使用本發明的敏輻射線性樹脂組成物形成液晶顯示 元件用間隔器時，首先，於基板上形成本發明敏輻射線性 樹脂組成物的被膜。 在此所形成被膜的膜厚，較佳爲〇·5〜6.0 μιη，更佳爲 1 . 5 ~ 4.5 μιη 。 在此所使用的基板方面，以單面形成透明導電膜的透 明基板爲佳。 構成透明基板的材料方面，可例舉玻璃，樹脂等。上 述玻璃方面，可例舉鹼石灰玻璃，無鹼玻璃等；樹脂方 面，可例舉聚對酞酸乙二酯，聚對苯二甲酸丁二醇酯 (ΡΒΤ)，聚醚颯，聚碳酸酯，聚醯亞胺等。 上述透明導電膜方面，可例舉由氧化錫（Sn02)所成的 NESA膜（美國 PPG公司的登錄商標），由氧化銦-氧化錫 (In203 -Sn〇2)所成的 ITO 膜等。 於基板上形成本發明敏輻射線性樹脂組成物的被膜之 方法方面，可藉由以例如（i)塗佈法或（Π)乾薄膜法而達 成。 (i)使用塗佈法時’可於基板上塗佈本發明的敏輻射線 性樹脂組成物的溶液之後，藉由加熱塗佈面（預烘烤）’形 成被膜。 使用塗佈法時’其中組成物溶液的固形成分濃度’較 佳爲10〜50重量％ ’更佳爲15〜40重量％。 組成物溶液的塗佈方法方面，並無特別限定，可採用 適當的方法如噴灑法，輥塗佈法，旋轉塗佈法（sPin -36- 200842162 coating)，縫模塗佈法，棒塗佈法，噴墨塗佈法等，特別 以旋轉塗佈法或縫模塗佈法爲佳。 預烘烤的條件，依照敏輻射線性樹脂組成物所含有之 各成分的種類，配合比率等而有所不同，較佳爲在70〜 1 1 〇 °C下預烘烤1〜1 5分鐘。 另一方面，使用（ii)乾薄膜法形成被膜時，該乾薄 膜，係在基質薄膜上，較佳爲可撓性的基質薄膜上，層合 由本發明的敏輻射線性樹脂組成物所成的感光性層所成者 (以下，稱爲「感光性乾薄膜」）。 上述感光性乾薄膜，可藉由於基質薄膜上，將本發明 的敏輻射線性樹脂組成物較佳爲作爲溶液組成物塗佈之 後，去除溶劑，層合感光性層而製造。感光性乾薄膜的基 質薄膜方面，可使用如聚對酞酸乙二酯（PET)，聚乙烯， 聚丙烯，聚碳酸酯，聚氯化乙烯等合成樹脂的薄膜。基質 薄膜的厚度以1 5〜1 2 5 μηι的範圍爲適當。所得感光性層 的厚度以1〜30μπι左右爲佳。 基質薄膜上所塗佈的敏輻射線性樹脂組成物的固形成 分濃度，較佳爲3 0〜8 0重量％，更佳爲4 0〜7 0重量％。 基質薄膜上組成物溶液的塗佈方法方面，例如可使用 塗佈器的方法，凹版印刷（g r a v u r e )法，c 〇 m m a法等，該等 之中，以使用塗佈器的方法，或凹版印刷（gravure)法爲 佳。 溶劑的去除，例如可藉由在8 0〜1 1 〇 °C下加熱處理1 〜10分鐘左右而達成。 -37- 200842162 感光性乾薄膜，若未使用時，可於其感光性層上進而 層合外覆薄膜而作保存的準備。爲了使該外覆薄膜，於未 使用時不剝離，而於使用時容易剝離，必須具備適度的脫 模性。滿足此種條件的外覆薄膜方面，例如可使用在P E T 薄膜，聚丙烯薄膜，聚乙烯薄膜，聚氯化乙烯薄膜，聚胺 甲酸乙酯薄膜等合成樹脂薄膜的表面上，塗佈聚矽氧系脫 模劑或烘烤薄膜。外覆薄膜的厚度通常以5〜3 0 μιη左右 爲佳。外覆薄膜，可因應需要成爲2層或者3層層合狀的 外覆薄膜。 使用如上述的感光性乾薄膜於基板上形成本發明敏輻 射線性樹脂組成物的被膜時，可使用如貼合法的方法。 (2)將該被膜的至少一部份曝光的步驟 接著，將如上述的作法形成之被膜的至少一部份照射 放射線，予以曝光。曝光所使用的放射線方面，可適當的 選擇可視光線，紫外線，遠紫外線，帶電粒子線，X線 等’但以波長在190〜45 Onm範圍內的放射線爲佳。僅被 月吴的一部份曝光時’例如可介由設定圖型的光罩進行放射 線照射的方法等。 在此，曝光量方面’以400〜2,〇〇〇 j/m2爲佳，以 5 00 〜1，5 00 J/m2 爲更佳。 此外’習知的間隔器形成用敏輻射線性樹脂組成物， 最少必須有超過2,000 J/m2的曝光量，但本發明的敏輻射 線性樹脂組成物，即使在1，5 00 J/m2以下，進而ι，2〇〇 J/m2以下的曝光量中，亦可形成具有期望圖型之適當的間 -38- 200842162 隔器’具有助於縮短步驟時間及削減製造成本的優點。 (3)將曝光後的被膜顯影的步驟 接著，提供顯影曝光後之被膜的步驟。 顯影方法，可爲例如，盛液法，浸漬法，沖洗法等的 任一種，顯影時間，較佳爲3 0〜1 8 0秒。 顯影所使用之顯影液方面，可使用如氫氧化鈉，氫氧 化鉀，碳酸鈉，矽酸鈉，偏矽酸鈉，氨等的無機鹼； 乙基胺，正丙基胺等的1級胺； 二乙基胺，二-正丙基胺等的2級胺； 三甲基胺，甲基二乙基胺，乙基二甲基胺，三乙基胺 等的3級胺； 二甲基乙醇胺，甲基二乙醇胺，三乙醇胺等的3級烷 醇胺； 吡咯吡咯，哌啶，N -甲基哌啶，N -甲基吡咯啶’ 1，8 -二氮雜二環[5·4.0]-7-十一烯 ’ 1,5-二氮雜二環[4·3·0]-5-壬 烯等的脂環族3級胺； ρ比卩定，三甲基吡啶（Collidine)，喹啉等的芳香族3級 胺； 氫氧化四甲基錶，氫氧化四乙基錢等的4級I女鹽 等的鹼性化合物水溶液等。 上述鹼性化合物的水溶液中，可適當添加選自甲醇’ 乙醇等的水溶性有機溶劑及界面活性劑所成群的至少1種 而使用。 顯影後，可藉由如流水洗淨等，如30〜90秒洗淨去 -39- 200842162 除不要的部份後，吹以壓縮空氣或壓縮氮使其乾燥，可形 成設定之圖型。 (4)將顯影後的被膜加熱的步驟 接著，藉由將如上述所形成之圖型，使用熱板，烤箱 等適宜的加熱裝置加熱（事後烘烤），可於基板上形成液晶 顯示元件用的間隔器。該事後烘烤的加熱溫度較佳爲1 5 0 〜2 5 0 °C，較佳的加熱時間依照加熱所使用的裝置而有所 不同。例如使用熱板的加熱裝置時，較佳的加熱時間爲5 〜3 0分鐘，使用烤箱時，較佳的加熱時間爲3 0〜9 0分 鐘。 <間隔器> 如上述的作法’由本發明敏輻射線性樹脂組成物所形 成之間1½益，由後述的貫施例可明瞭，與基板的密接性， 硏磨耐丨生及耐熱丨生優異，進而同時具有柔軟性與高的彈性 回復率’可適合使用於液晶顯示面板或觸控面板等的顯示 元件。 <液晶顯示元件> 本發明的液晶顯示元件，具備如上述的作法所形成的 間隔器。 本發明的液晶顯示元件，具有即使自外部施加壓力 日寸’亦難以產生顯不不均的優點。 - 40- 200842162 【實施方式】 實施例 以下例示實施例及比較例’進而具體說明本發明，但 本發明並不限定於該等實施例。 下列當中，聚合物的重量平均分子量係全部使用凝膠 滲透層析術（GPC Shodex GPC-101(昭和電工公司製））測定 的換算聚苯乙烯分子量。 合成例1(共聚物[A]的合成（1)) 在備有冷卻管，攪拌機的燒瓶內，放入2,2，-偶氮雙 (2,4 -二甲基戊腈）4重量份及乙酸3 -甲氧基丁酯25〇重量 份。接著，放入苯乙烯5重量份，甲基丙烯酸1 〇重量 份，4 -丙嫌醯基氧甲基-2-甲基-2-乙基- 二[|惡戊院40重 量份，甲基丙烯酸2-甲基環氧丙酯25重量份及甲基丙烯 酸节酯2 〇重量份，氮取代後，開始慢慢攪拌。使溶液溫 度上升至7 〇 C ’保持該溫度4小時’獲得含有共聚物[a _ 1 ] 的聚合物溶液。所得聚合物溶液的固形$ #濃度爲27.9 重量％，聚合物的重量平均分子量爲2 6 5 〇 Q〇。 合成例2(共聚物[A]的合成（2)) 在備有冷卻管，攪拌機的燒瓶內，放人2，2，-偶氮雙 (2,4 -二甲基戊腈）4重量份及丙二醇單甲基醚乙酸酯25〇 重量份。接著’放入苯乙烯5重量份，甲基丙烯酸8重量 份’ 4 -丙嫌釀基氧甲基-2-甲基-2-乙基-1，3_一[|惡戊院45重 -41 - 200842162 量份，甲基丙烯酸環氧丙酯20重量份及甲基丙烯酸苄酯 2 2重量份，氮取代後，開始慢慢攪拌。使溶液溫度上升 至70°C ’保持該溫度4小時，獲得含有共聚物[A_2]的聚 合物溶液。所得聚合物溶液的固形成分濃度爲2 8 · 5重量 %，聚合物的重量平均分子量爲25，000。 合成例3(共聚物[A]的合成（3)) 在備有冷卻管，攪拌機的燒瓶內，放入2，2，-偶氮雙 異丁腈7重量份及乙酸3 -甲氧基丁酯250重量份，接 著，放入苯乙烯5重量份，甲基丙烯酸1〇重量份，4-丙 烯醯基氧甲基-2-甲基-2-乙基-1，3-二噁戊烷40重量份， 甲基丙烯酸三環[5.2.1.02,6]癸烷-8_基酯（三環癸基甲基丙 烯酸酯）1〇重量份，甲基丙烯酸2-羥基乙酯15重量份及 甲基丙烯酸苄酯20重量份，氮取代後，開始慢慢攪拌。 使溶液溫度上升至70 °C，保持該溫度4小時，獲得含有共 聚物[A-3 ]的聚合物溶液。所得聚合物溶液的固形成分濃 度爲28.0重量％，聚合物的重量平均分子量爲22,000。 合成例4 (其他共聚物的合成） 在備有冷卻管，攪拌機的燒瓶內，放入2,2f-偶氮雙 異丁腈7重量份及丙二醇單甲基醚乙酸酯250重量份。接 著，放入苯乙烯5重量份，甲基丙烯酸15重量份，甲基 丙烯酸三環[5·2 ·1.02,6]癸烷-8-基酯（三環癸基甲基丙烯酸 酯）35重量份及甲基丙烯酸苄酯45重量份，氮取代後， -42- 200842162Epolight 100MF, Epolight 4000 » E p o 1 i g h t 3 0 0 2 (manufactured by Kyoei Seiki Co., Ltd.), epitoke 15 2 (manufactured by Nippon Epoxy Resin Co., Ltd.). These may be used alone or in combination of two or more. The use ratio of the heat resistance improving agent is preferably 30 parts by weight or less, more preferably 1 to 20 parts by weight, based on 1 part by weight of the total amount of the polymer. - Solvent - The radiation sensitive linear resin composition of the present invention, preferably the above copolymer [A], [B] polymerizable unsaturated compound and [C] radiation sensitive linear polymerization initiator" and other additives used arbitrarily , dissolved in a suitable solvent -33- 200842162, prepared as a composition solution. The solvent used for preparing the solution of the radiation-sensitive linear resin composition of the present invention can be used as an article which can dissolve the components constituting the linear composition of the radiation sensitive resin on average and which does not react with each component. Such a glutinous agent aspect can be exemplified as the one exemplified for the solvent used for the production of the above copolymer [A]. In such a solvent, for example, an alcohol, a glycol ether, an ethylene glycol alkyl ether acetate, an ester, and the like are used in view of solubility of each component, reactivity with each component, and formation of a film. Diethylene glycol is preferred. In the above, the use of mercapto alcohol '2-phenylethyl alcohol, 3-phenyl-1-propanol, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate , diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methoxy propionate The base, ethyl ethoxypropionate, and 3-methoxybutyl acetate are particularly preferred. Further, in order to simultaneously improve the uniformity in the thickness of the film, the solvent can be used in a high boiling point solvent. As the high-boiling solvent which can be used, N-methylformamide, hydrazine, hydrazine-dimethylformamide, N-methyl N-methylanilide, N-methylacetamide, hydrazine can be exemplified. , Ν-dimethylacetamide, Ν-methylpyrrolidone, dimethyl hydrazine, benzyl ethyl ether, dihexyl ether, acetone acetone, isophorone, hexanoic acid, octanoic acid, 1- Octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve Acetate and the like. Among these, Ν-methylpyrrolidone y-butyrolactone, hydrazine, hydrazine-dimethylacetamide is preferred. In terms of the amount of solvent used, the solid-state linear resin composition is solid-formed at a concentration of -34 - 200842162 (the total weight of the components of the solvent of the linear resin composition from which the radiation is removed, and the ratio of the total weight of the linear radiation-sensitive resin composition) The amount is preferably from 10 to 80% by weight, more preferably from 1 5 to 70% by weight. The preferred solid content concentration varies depending on the method used to form the film of the radiation sensitive linear resin composition of the present invention on the substrate, and the details thereof will be described later. The solution of the linear radiation-sensitive resin composition prepared in this manner can be used by filtering from a micropore filter having a pore size of, for example, about 0·2 to 0.5 μηι, if necessary. The radiation sensitive linear resin composition of the present invention is particularly suitably used for forming a spacer for a liquid crystal display element such as a liquid crystal panel or a touch panel. <<>> When the spacer for the liquid crystal display element is formed using the radiation sensitive linear resin composition of the present invention, for example, the following may be included in the following order, for example The method of the steps is achieved. (1) a step of forming a radiation-sensitive linear resin composition of the present invention on a substrate, (2) a step of exposing at least a portion of the film, (3) a step of developing the film after exposure, and (4) A step of heating the developed film. The respective steps of the method of forming the spacer for a liquid crystal display element of the present invention will be described below. (1) Step of forming a film of the radiation sensitive linear resin composition of the present invention on a substrate - 35 - 200842162 When forming a spacer for a liquid crystal display element using the radiation sensitive linear resin composition of the present invention, first, a substrate is formed on the substrate A film of a radiation sensitive linear resin composition is invented. The film thickness of the film formed here is preferably from 〜5 to 6.0 μηη, more preferably from 1.5 to 4.5 μηη. As the substrate to be used herein, a transparent substrate in which a transparent conductive film is formed on one side is preferable. The material constituting the transparent substrate may, for example, be glass, resin or the like. Examples of the glass include soda lime glass, alkali-free glass, and the like; and examples of the resin include polyethylene terephthalate, polybutylene terephthalate, polyether oxime, and polycarbonate. , polyimine and the like. The transparent conductive film may, for example, be an NESA film made of tin oxide (Sn02) (registered trademark of PPG Corporation of the United States), an ITO film made of indium oxide-tin oxide (In203-Sn〇2), or the like. The method of forming the film of the radiation sensitive linear resin composition of the present invention on the substrate can be achieved by, for example, (i) coating method or (Π) dry film method. (i) When a coating method is used, a solution of the radiation sensitive resin composition of the present invention can be applied onto a substrate, and then a coating film is formed by heating the coated surface (prebaking). When the coating method is used, the solid content concentration of the composition solution is preferably from 10 to 50% by weight, more preferably from 15 to 40% by weight. The coating method of the composition solution is not particularly limited, and an appropriate method such as a spray method, a roll coating method, a spin coating method (sPin-36-200842162 coating), a slit die coating method, and a bar coating method can be employed. The method, the inkjet coating method, and the like are particularly preferably a spin coating method or a slit die coating method. The prebaking conditions vary depending on the type of the components contained in the linear radiation-sensitive resin composition, the blending ratio, etc., and are preferably pre-baked at 70 to 1 1 〇 ° C for 1 to 15 minutes. On the other hand, when the film is formed by the (ii) dry film method, the dry film is laminated on a substrate film, preferably a flexible substrate film, and laminated with the radiation sensitive linear resin composition of the present invention. The photosensitive layer is formed (hereinafter referred to as "photosensitive dry film"). The photosensitive dry film can be produced by coating the photosensitive radiation linear resin composition of the present invention as a solution composition on a substrate film, removing the solvent, and laminating the photosensitive layer. As the base film of the photosensitive dry film, a film of a synthetic resin such as polyethylene terephthalate (PET), polyethylene, polypropylene, polycarbonate, or polyvinyl chloride can be used. The thickness of the matrix film is suitably in the range of 15 to 1 2 5 μη. The thickness of the photosensitive layer obtained is preferably from about 1 to 30 μm. The solid concentration of the radiation sensitive linear resin composition coated on the substrate film is preferably from 30 to 80% by weight, more preferably from 40 to 70% by weight. As for the coating method of the composition solution on the substrate film, for example, an applicator method, a gravure method, a c 〇mma method, or the like can be used, among which a method using an applicator or gravure printing is used. The (gravure) method is better. The removal of the solvent can be achieved, for example, by heat treatment at 80 to 1 1 ° C for about 1 to 10 minutes. -37- 200842162 Photosensitive dry film, if not used, can be laminated on the photosensitive layer to prepare for storage. In order to prevent the outer film from being peeled off when it is not used, it is easy to peel off during use, and it is necessary to have appropriate mold release property. For the outer cover film which satisfies such conditions, for example, it can be coated on the surface of a synthetic resin film such as a PET film, a polypropylene film, a polyethylene film, a polyvinyl chloride film or a polyurethane film, and coated with polyoxyl It is a release agent or a baking film. The thickness of the overcoat film is usually about 5 to 30 μm. The outer cover film can be a two-layer or three-layer laminated outer cover film as needed. When the film of the radiation sensitive resin composition of the present invention is formed on the substrate by using the photosensitive dry film as described above, a method such as a bonding method can be used. (2) Step of exposing at least a portion of the film Next, at least a portion of the film formed as described above is irradiated with radiation to be exposed. For the radiation used for exposure, visible light, ultraviolet light, far ultraviolet light, charged particle beam, X-ray, etc. can be appropriately selected, but radiation having a wavelength in the range of 190 to 45 Onm is preferred. When only a part of the moon is exposed, for example, a method of irradiating radiation through a mask of a setting pattern or the like can be employed. Here, the exposure amount is preferably 400 to 2, 〇〇〇 j/m 2 , and more preferably 5 00 to 1, 5 00 J/m 2 . Further, the conventional spacer-forming photosensitive radiation linear resin composition must have an exposure amount of at least 2,000 J/m 2 at least, but the sensitive radiation linear resin composition of the present invention, even if it is below 1,500 J/m 2 , Further, in the exposure amount of ι, 2 〇〇 J/m2 or less, it is also possible to form an appropriate inter-38-200842162 spacer having a desired pattern, which has the advantage of shortening the step time and reducing the manufacturing cost. (3) Step of Developing the Film After Exposure Next, a step of developing the film after exposure is provided. The developing method may be, for example, any one of a liquid-filling method, a dipping method, a rinsing method, and the like, and the developing time is preferably from 30 to 180 seconds. For the developer used for development, an inorganic base such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, ammonia or the like; an amine of a standard such as ethylamine or n-propylamine; ; a 2- to amine such as diethylamine or di-n-propylamine; a tertiary amine such as trimethylamine, methyldiethylamine, ethyldimethylamine or triethylamine; a tertiary alkanolamine such as ethanolamine, methyldiethanolamine or triethanolamine; pyrrolopyrrole, piperidine, N-methylpiperidine, N-methylpyrrolidine' 1,8-diazabicyclo[5.4.0 An alicyclic tertiary amine such as 7-undecene ' 1,5-diazabicyclo[4·3·0]-5-decene; ρ 比卩定,Trimethylpyridine (Collidine) An aromatic tertiary amine such as quinoline; an aqueous solution of a basic compound such as a tetramethylamine hydroxide or a tetrabasic I salt such as tetraethylammonium hydroxide; In the aqueous solution of the above-mentioned basic compound, at least one selected from the group consisting of a water-soluble organic solvent such as methanol' ethanol and a surfactant can be appropriately added. After development, it can be washed by running water, for example, 30~90 seconds to remove the unnecessary part, and then blow it with compressed air or compressed nitrogen to dry it to form a set pattern. (4) The step of heating the film after development is followed by heating (post-baking) using a suitable heating means such as a hot plate or an oven by using the pattern formed as described above, thereby forming a liquid crystal display element on the substrate. Spacer. The heating temperature for the post-baking is preferably from 150 to 250 ° C, and the preferred heating time varies depending on the apparatus used for heating. For example, when a heating device for a hot plate is used, a preferred heating time is 5 to 30 minutes, and when an oven is used, a preferred heating time is 30 to 90 minutes. <Spacer> The above-described method 'is formed by the radiation sensitive linear resin composition of the present invention, and is understood from the following examples, the adhesion to the substrate, the honing resistance and the heat-resistant growth Excellent, and at the same time, it has flexibility and high elastic recovery rate', which can be suitably used for display elements such as liquid crystal display panels or touch panels. <Liquid Crystal Display Element> The liquid crystal display element of the present invention includes the spacer formed by the above-described method. The liquid crystal display element of the present invention has an advantage that it is difficult to cause unevenness even if pressure is applied from the outside. [Embodiment] EXAMPLES Hereinafter, the present invention will be specifically described by way of examples and comparative examples, but the present invention is not limited to the examples. In the following, the weight average molecular weight of the polymer is the converted polystyrene molecular weight measured by gel permeation chromatography (GPC Shodex GPC-101 (manufactured by Showa Denko)). Synthesis Example 1 (Synthesis (1) of Copolymer [A]) 4 parts by weight of 2,2,-azobis(2,4-dimethylvaleronitrile) was placed in a flask equipped with a cooling tube and a stirrer And 25 parts by weight of 3-methoxybutyl acetate. Next, 5 parts by weight of styrene, 1 part by weight of methacrylic acid, 4 - propyl decyloxymethyl-2-methyl-2-ethyl- bis [| oxime 40 parts by weight, methyl group 25 parts by weight of 2-methylglycidyl acrylate and 2 parts by weight of methacrylic acid ester, and after nitrogen substitution, stirring was started slowly. The temperature of the solution was raised to 7 〇 C ' to maintain the temperature for 4 hours' to obtain a polymer solution containing the copolymer [a _ 1 ]. The solid solution of the obtained polymer solution had a solid concentration of 27.9% by weight, and the weight average molecular weight of the polymer was 2 6 5 〇 Q〇. Synthesis Example 2 (Synthesis (2) of Copolymer [A]) 4 parts by weight of 2,2,-azobis(2,4-dimethylvaleronitrile) was placed in a flask equipped with a cooling tube and a stirrer And propylene glycol monomethyl ether acetate 25 parts by weight. Then 'put 5 parts by weight of styrene, 8 parts by weight of methacrylic acid '4-propanyloxymethyl-2-methyl-2-ethyl-1,3_a[| 41 - 200842162 parts, 20 parts by weight of glycidyl methacrylate and 22 parts by weight of benzyl methacrylate. After nitrogen substitution, stirring was started slowly. The temperature of the solution was raised to 70 ° C to maintain the temperature for 4 hours to obtain a polymer solution containing the copolymer [A_2]. The obtained polymer solution had a solid content concentration of 28.5% by weight and a polymer having a weight average molecular weight of 25,000. Synthesis Example 3 (Synthesis (3) of Copolymer [A]) In a flask equipped with a cooling tube and a stirrer, 7 parts by weight of 2,2,-azobisisobutyronitrile and 3-methoxybutyl acetate were placed. 250 parts by weight of the ester, followed by 5 parts by weight of styrene, 1 part by weight of methacrylic acid, 4-propenyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane 40 parts by weight, tricyclo [5.2.1.02,6]decane-8-yl methacrylate (tricyclodecyl methacrylate) 1 part by weight, 15 parts by weight of 2-hydroxyethyl methacrylate and 20 parts by weight of benzyl methacrylate was added, and after nitrogen substitution, stirring was started slowly. The temperature of the solution was raised to 70 ° C, and the temperature was maintained for 4 hours to obtain a polymer solution containing the copolymer [A-3 ]. The solid solution concentration of the obtained polymer solution was 28.0% by weight, and the weight average molecular weight of the polymer was 22,000. Synthesis Example 4 (Synthesis of Other Copolymer) In a flask equipped with a cooling tube and a stirrer, 7 parts by weight of 2,2f-azobisisobutyronitrile and 250 parts by weight of propylene glycol monomethyl ether acetate were placed. Next, 5 parts by weight of styrene, 15 parts by weight of methacrylic acid, 35 parts by weight of tricyclo[5·2 ·1.02,6]decane-8-yl methacrylate (tricyclodecyl methacrylate) And 45 parts by weight of benzyl methacrylate, after nitrogen substitution, -42- 200842162
η y，保持該溫度5小 開始慢慢攪拌。使溶液溫度上升至70 C 時，獲得含有共聚物[a-1 ]的聚合物溶液。所# ^ 口物沿液 的固形成分濃度爲29.0重量％，聚合物的重里平均分子里 爲 28,000 。 實施例1 <敏輻射線性樹脂組成物的調製> 共聚物[A]爲將以上述合成例1獲得的含有共聚物[A-1]之聚合物溶液，換算成相當於共聚物[A-1]1 00重量份 (固形成分）的量，[B]聚合性不飽和化合物爲將KAYARAD DPHA(商品名，曰本化藥公司製）100重量份，以及[C]敏 輻射線性聚合引發劑的乙酮（e t h a η ο n e)，1 - [ 9 _乙基-6 - (2 -甲基苯醯基）-9·Η-咔唑-3-基卜，1-(0-乙醯基氧肟）（千葉特 用化學品公司製，商品名「Irgacure 0X02」）5重量份， 及2 - —*甲基胺基- 2- (4 -甲基-节基）-1-(4 -嗎B林-4-基-苯基）_ 丁烷-1-酮（千葉特用化學品公司製，商品名 「Irgacure3 79」）10重量份，使固形成分濃度成爲3〇重 量％的方式，溶解於丙二醇單甲基醚乙酸酯後，藉由以孔 徑0.2 μ m的微孔過濾器過濾，調製敏轄射線性樹脂組成物 溶液（S -1 )’準照以下的方法進行各種評價。結果如表2 所示。 <間隔器的形成及評價> ⑴感度的評價 -43- 200842162 於無鹼玻璃基板上，以旋轉塗佈法塗佈敏輻射線性樹 脂組成物溶液（s -1)之後，藉由於熱板上8 0 °c中3分鐘的 預烘烤，形成膜厚3·5 μιη的被膜（塗膜）。 在上述所得之塗膜上，介由具有殘留15μηι圓形圖型 的光罩，曝光間隙爲150μιη，以曝光量爲變量進行曝光。 接著，藉由使用氫氧化鉀〇 . 0 5重量％的水溶液，以沖洗法 在2 5 °C下顯影1分鐘後，以純水沖洗1分鐘。進而，在烤 箱中，以23 0 °C下加熱30分鐘（事後烘烤），形成間隔器。 此時’顯影後的殘膜率（（事後烘烤後的膜厚/曝光後 (顯影前）膜厚）X 1 〇 〇 )係以9 0 %以上最小曝光量作爲感度。 (II) 顯影性的評價 上述（I)中’使曝光量作爲上述（I)所調查之感度的値 予以曝光後，以顯影時間作爲變量，實施顯影時，以在未 曝光部無殘渣（殘留顯影），且可形成圖型之最短顯影時間 作爲顯影性。該時間愈短表示顯影性愈良好。 (III) 間隔器的形成 i：述（I)中’除了使曝光量作爲以上述⑴調查之感度 的値’使顯影時間作爲上述（11)所調查之顯影性的時間之 外’其他與上述（I)同樣，於基板上形成間隔器。 以該曝光量及顯影時間進行以下的評價。 (IV) 硏磨耐性的評價 在如上述（111)的作法，形成間隔器的基板上，以液晶 配向膜塗佈用印刷機，塗佈作爲液晶配向劑的AL 3 046(商 品名’ J S R公司製），在1 8 〇 〇c下加熱1小時，形成膜厚 - 44- 200842162 0.0 5 μπι的配向劑塗膜。 使用具纏繞有耐綸製的布之輥的硏磨機器，以輥旋轉 數5 00rpm，階段性移動速度lcm/秒對該塗膜進行硏磨處 理。檢查此時間隔器圖型有無脫落或剝離。 (V) 密接性的評價 上述（ΙΠ)中，除了不使用圖型光罩之外，以與上述 (III)同樣的方法進行，於基板上形成無圖型的硬化膜。關 於該硬化膜，在 JIS K-5 400( 1 900)8.5的附著性試驗中， 以8.5 · 2的棋盤眼正交帶法（crosscut taping method)進行 密接性試驗。此時，檢查100個（10x10個）棋盤眼中，殘 留棋盤眼的數目。棋盤眼的數目1 00個中，完全殘留時， 表示密接性良好。 (VI) 耐熱穩定性的評價 測定如上述（III)的作法所形成間隔器的高度，進而， 測定在烤箱中，23 0°C下追加加熱30分鐘後間隔器的高 度。此時，高度的維持率以下述式 維持率（％) =(追加加熱後的高度/追加加熱前的高 度）χ 100求得。此高度的維持率若在99%以上，表示耐熱 穩定性良好。 (VII) 彈性回復率的評價 關於如上述（III)的作法所形成的間隔器，使用微小壓 縮試驗機（島津製作所公司製，商品名「DUH-201」），以 直徑50μιη的平面壓痕，負荷速度及除荷速度同爲2.6mN/ 秒，施加負荷量5 0 m N爲止的負荷5秒之後除荷，作成負 -45- 200842162 荷時的負荷-變形量曲線及除荷時的負荷-變形量曲線。此 時，如第1圖所示，以負荷時負荷50mN下的變形量與負 荷5mN下的變形量之差爲L1，以除荷時負荷50mN下的 變形量與負荷5mN下的變形量之差爲L2，以下述式 彈性回復率（％) = L2x 100/L1 計算出彈性回復率。 實施例2〜1 0及比較例1，2 實施例1中，除了敏輻射線性樹脂組成物所含有之各 成分的種類及量如表1記載之外，其他與實施例1 一樣的 作法，各自調製敏輻射線性樹脂組成物溶液（S-2)〜（S-l〇) 以及（s-1)及（s-2)，使用各敏輻射線性樹脂組成物溶液， 與實施例1 一樣，進行各種評價。評價結果如表2所示。 此外，實施例9及比較例2中，除了共聚物[A]，[B] 聚合性不飽和化合物及[C]敏輻射線性聚合引發劑之外， 其他苯酚酚醛清漆型環氧基樹脂（日本環氧基樹脂公司 製，商品名「epitokel52」）僅添加表1記載的量。 又，實施例10中，倂用共聚物[A]與其他的聚合物。 實施例1 1 <敏輻射線性樹脂組成物的調製> 實施例1中，敏輻射線性樹脂組成物所含有之各成分 的種類及量如表1記載，除了組成物溶液的固形成分濃度 爲5 0重量％之外，其他與實施例1 一樣，調製敏輻射線 -46- 200842162 性樹脂組成物溶液（s -1 1)。 實施例1 1中，倂用共聚物[A]與其他的聚合物。 <間隔器的形成及評價> 實施例1中，於基板上形成被膜的方法方面，除了採 用以乾薄0吴法轉印取代旋轉塗佈法塗佈之外，其他與實施 例1 一樣進行各種評價。結果如表2所示。 以下述的方法進行乾薄膜的製造及基板上敏輻射線性 層的轉印。 在厚度3 8 μπι的聚對酞酸乙二酯薄膜上，藉由使用塗 佈器’塗佈敏輻射線性樹脂組成物的液狀組成物（s_ i υ， 將該塗膜於100 °C下加熱5分鐘，製造具有厚度4μιη敏輻 射線性層的敏輻射線性乾薄膜。接著，於無鹼玻璃基板的 表面上，使敏輻射線性轉印層的表面抵接的方式，疊合 (registration)敏輻射線性乾薄膜，以熱壓著法於基板上轉 印敏輻射線性層。 觀察上述轉印的敏輻射線性層，敏輻射線性層可在基 板上均一地轉印時爲「〇」，底層薄膜上有部份乾薄膜殘 留，基板上乾薄膜無法密接等，玻璃基板上乾薄膜不能均 一地轉印時爲「X」。結果如表2所示。 比較例3 實施例1 1中’除了敏輻射線性樹脂組成物所含有各 成分的種類及量如表1記載之外，其他與實施例11 一 -47- 200842162 樣，調製敏輻射線性樹脂組成物溶液（S _ 3 )，使用該等’與 實施例1 1 一樣，製造敏輻射線性乾薄膜，進行各種評 價。評價結果如表2所示。 表1中，成分的簡稱表示下列的化合物。 (B-1):二新戊四醇六丙烯酸酯（日本化藥公司製’商 品名「KAYARADDPHA」） (B-2):含有多官能胺甲酸乙酯丙烯酸酯系化合物@ 市售品（商品名KAYARAD DPHA-40H) (B-3):異戊四醇四丙烯酸酯（東亞合成公司製，商品 名「aronix M-45 0」） (B-4) : ω-羧基聚己內酯單丙烯酸酯（（東亞合成公司 製，商品名「aronix Μ-5300」」 (B-5) : 1，9-壬烷二丙烯酸酯（共榮社化學公司製’商 品名「light丙烯酸酯1，9-NDA」） (C-1):乙酮（ethanone)，l-[9-乙基-6-(2-甲基苯醯 基）-9· H.-咔唑-3-基]-，1-(0-乙醯基氧肟）（千葉特用化學品 公司製，商品名「Irgacure 0X02」） (C-2):乙酮（ethanone)，1-[9·乙基- 6_[2 -甲基- 4-(2，2· 二甲基-1，3-二氧雜環戊烷基）甲氧基苯醯基]-9.Η.-咔唑- 3-基]-，1-(0-乙醯基氧肟）（公司 ADEKA製，商品名「N· 1919」） (C-3) ·· 2-二甲基胺基- 2-(4 -甲基-苄基）-卜（4-嗎啉·4-基-苯基）-丁烷-1 _酮（千葉特用化學品公司製，商品名 「Irgacure379」） -48- 200842162 (C-4) : 2,2·-雙（2-氯苯基）-4,4’，Ύ_四本基-1，2 -聯咪 唑 (C-5): 4,4，-雙（二乙基肢基）二苯基酮 (C-6): 2 -氫硫基苯并噻唑 (C-7): 2 -节基_2-二甲基胺基“"Ή-嗎啉代苯基）-丁 酮-ι(千葉特用化學品公司製，商品名「Irgacure3 69」） (C-8): 2-甲基-1-(4-甲基噻吩）-2-嗎啉基（morpholino) 丙烷-1-酮（千葉特用化學品公司製’商品名 「Irgacure907」） (D-1):苯酚酚醛清漆型環氧基樹脂（日本環氧基樹脂 公司製，商品名「epitokel52」） 表1中，「-」符號表示該欄中無添加該成分。 【圖式簡單說明】 第1圖係彈性回復率的評價中，負荷時及除負荷時的 負荷-變形量曲線之例示圖。 -49- 200842162 1—I谳 其他添加劑 重量份 1 1 1 1 1 1 1 1 ¢=5 1 1 1 寸 1 m ^vtS tlrnll P 1 1 1 1 1 1 1 1 1 1 1 丄 1 [_c]敏輻射線性聚合引發劑 重量份 C=5 s 5/2/2/1/5 5/2/2/1/5 G5 〇> s 5/2/2/1/5 s 5/2/2/1/5 C=5 s 5/2/2/1/5 s 寸 C<J 5/2/2/1/5 m ^T\rS w C-l/C-3 C-1/C-4/C-5/C-6/C-8 C-2/C-4/C-5/C_6/C_8 C-l/C-3 C-l/C-3 C-l/C-3 C-1/C-4/C-5/C-6/C-8 C-l/C-3 C-1/C-4/C-5/C-6/C-8 C-l/C-3 C-1/C-4/C-5/C-6/C-8 C-l/C-3 t>- C-1/C-4/C-5/C-6/C-8 [B]聚合性不飽和化合物 重量份 g 80/60/5 80/60/5 50/50 100/10 g 80/60/5 100/10 80/60/5 100/10 g g g g m >IvN i1ml1 腰1 r H PQ B-l/B-2/B-4 B-1/B-2/B-4 B-l/B-3 B-l/B-5 Ξ B-l/B_2/B-4 B-l/B-5 B-1/B-2/B-4 B-l/B-5 1 ψ H 1 PQ r-H ώ v—H PQ i 1 4 PQ 共聚物[A] 重量份 g g g g g g g g g 50/50 15/85 g g g 種類 f < f H ψ i r·· H C^J C^l CO A-1/a-l A-1/a-l I H 1 cd 1 i r-H 1 CO (N1 1 CO 1 CO 寸 1 ΙΩ 1 1 m 卜 1 • ίί) 00 1 01 1 〇 r-H 1 r—1 t-H 1 CO r-H 1 C/3 C\1 1 CO CO 1 in 實施例1 實施例2 實施例3 實施例4 實施例5 實施例6 實施例7 實施例8 實施例9 實施例10 實施例11 比較例1 比較例2 比較例3 -50- 200842162 CNa谳 乾薄膜 轉印性 1 1 1 1 1 1 1 1 1 1 〇 1 1 X 壓縮特性 變形量L1 (Mm) LTD LO C5 LO <〇 寸 LO <=5 oo LTD c=5 1 H CO <〇 LTD 寸 C=5 in LTD <d> LO 寸 <=5 CO LO CD c=5 CD CO C5 CD 彈性回復率 (%) C<3 CO LT3 CO CO LO ① LO CO co LO LO ς〇 § 呀 LTD CNJ LO CV3 CO 努A σ^> cn σ^> CT5 crs CT5 CT5 CTi cn CTi CO oo 密接性 (個/100働 g g g g g g g g g g g § g 硏磨耐性剝 離之有無 壊 媒 樣 壊 壊 繼 壊 壊 壊 擗 顯影性 (秒） LTD 寸 LO LO 寸 LO 寸 s LO LO CO LO CO LO CO 感度 (J/m2) 1，200 1, 000 1, 000 1, 000 1,000 g C^I » H g ci> t—H 1, 000 g y--< 零 ^ g f H H g 0〇 g oo f H g cr> C^J g oo rH 1 CM 1 CO 00 1 (f) 寸 1 (Ω LO 1 CO CD 1 in 卜 1 ίί) 00 1 ίί) 1 (Ω 〇 t-H 1 (7) rH t-H 1 C^) rH 1 (/) (N1 1 c/i oo 1 m 實施例1 實施例2 實施例3 實施例4 實施例5 實施例6 實施例7 實施例8 實施例9 實施例10 實施例11 比較例1 比較例2 比較例3η y, keep the temperature at 5 small and start stirring slowly. When the temperature of the solution was raised to 70 C, a polymer solution containing the copolymer [a-1 ] was obtained. The concentration of the solid component of the mouth fluid was 29.0% by weight, and the average molecular weight of the polymer was 28,000. Example 1 <Preparation of a radiation sensitive linear resin composition> The copolymer [A] is a polymer solution containing the copolymer [A-1] obtained in the above Synthesis Example 1, and is converted into a copolymer [A]. -1] the amount of 100 parts by weight (solid component), [B] the polymerizable unsaturated compound is 100 parts by weight of KAYARAD DPHA (trade name, manufactured by Sakamoto Chemical Co., Ltd.), and [C] linear polymerization of sensitive radiation Ethyl ketone (etha η ο ne), 1-[9-ethyl-6-(2-methylphenylhydrazinyl)-9-indole-indazole-3-yl b, 1-(0-acetamidine 5-oxopurine (manufactured by Chiba Specialty Chemicals Co., Ltd., trade name "Irgacure 0X02") 5 parts by weight, and 2 -*methylamino 2-(4-methyl-succinyl)-1-(4) -B-Bin-4-yl-phenyl)-butan-1-one (manufactured by Chiba Specialty Chemicals Co., Ltd., trade name "Irgacure 3 79") 10 parts by weight, and the solid content concentration is 3 〇 by weight After being dissolved in propylene glycol monomethyl ether acetate, the solution was prepared by filtering with a micropore filter having a pore size of 0.2 μm to prepare a solution of the sensitive radioactive resin composition (S -1 ). . The results are shown in Table 2. <Formation and Evaluation of Spacer> (1) Evaluation of Sensitivity - 43- 200842162 After coating the radiation sensitive linear resin composition solution (s-1) on a non-alkali glass substrate by spin coating, by means of a hot plate Pre-baking at 80 °c for 3 minutes to form a film (coating film) having a film thickness of 3·5 μm. On the coating film obtained above, the exposure gap was 150 μm through a mask having a circular pattern of 15 μm, and the exposure amount was used as a variable. Subsequently, it was developed by using a potassium hydroxide 〇0.5 wt% aqueous solution at a temperature of 25 ° C for 1 minute by a rinse method, and then rinsed with pure water for 1 minute. Further, in a baking box, it was heated at 23 ° C for 30 minutes (after baking) to form a spacer. At this time, the residual film ratio after development ((thickness after baking/film thickness after exposure (before development) X 1 〇 〇 ) is a sensitivity of 90% or more of minimum exposure amount. (II) Evaluation of developability In the above (I), the amount of exposure was measured as the sensitivity of the above-mentioned (I), and then the development time was used as a variable, and when development was performed, no residue was left in the unexposed portion (residual Development), and the shortest development time of the pattern can be formed as developability. The shorter the time, the better the developability. (III) Formation of the spacer: In the above (I), except for the time when the exposure amount is used as the sensitivity of the investigation (1), and the development time is the development property investigated in the above (11), (I) Similarly, a spacer is formed on the substrate. The following evaluation was performed by the exposure amount and the development time. (IV) Evaluation of honing resistance In the method of the above (111), a substrate for forming a spacer was coated with a liquid crystal alignment film coating machine and coated with AL 3 046 as a liquid crystal alignment agent (trade name 'JSR Corporation> The system was heated at 1 8 〇〇c for 1 hour to form an alignment agent coating film having a film thickness of -44-200842162 0.0 5 μm. The coating film was honed by a honing machine having a roll wound with a nylon fabric at a roller rotation number of 500 rpm and a stepwise moving speed of 1 cm/sec. Check if the spacer pattern is detached or peeled off at this time. (V) Evaluation of Adhesiveness In the above (ΙΠ), a pattern-free cured film was formed on the substrate in the same manner as in the above (III) except that the pattern mask was not used. With respect to the cured film, in the adhesion test of JIS K-5 400 (1900) 8.5, the adhesion test was carried out by a crosscut taping method of 8.5 · 2 . At this time, the number of remaining checkerboard eyes is checked in 100 (10x10) checkerboard eyes. When the number of checkerboard eyes is 100, when it is completely left, it indicates that the adhesion is good. (VI) Evaluation of heat resistance stability The height of the spacer formed by the above method (III) was measured, and the height of the spacer after additional heating at 30 ° C for 30 minutes in an oven was measured. At this time, the maintenance rate of the height is obtained by the following formula retention rate (%) = (the height after the additional heating/the height before the additional heating) χ 100. When the maintenance rate of this height is 99% or more, the heat resistance stability is good. (VII) Evaluation of the elastic recovery rate The spacer formed by the method of the above (III) is a flat indentation having a diameter of 50 μm using a micro compression tester (product name "DUH-201" manufactured by Shimadzu Corporation). The load speed and the load-removal speed are both 2.6 mN/s, and the load is applied after the load of 5 0 m N for 5 seconds, and the load-deformation curve and the load at the time of the load are generated as negative-45-200842162. Deformation curve. At this time, as shown in Fig. 1, the difference between the amount of deformation at a load of 50 mN and the amount of deformation at a load of 5 mN is L1, and the difference between the amount of deformation at a load of 50 mN and the amount of deformation at a load of 5 mN. For L2, the elastic recovery rate was calculated by the following elastic recovery rate (%) = L2x 100/L1. Examples 2 to 10 and Comparative Examples 1 and 2 In Example 1, except that the types and amounts of the respective components contained in the radiation-sensitive linear resin composition are as shown in Table 1, the same procedures as in Example 1 were carried out. Modulation of the radiation-sensitive linear resin composition solutions (S-2) to (S1) and (s-1) and (s-2), using various sensitive radiation linear resin composition solutions, and performing various evaluations as in Example 1. . The evaluation results are shown in Table 2. Further, in Example 9 and Comparative Example 2, in addition to the copolymer [A], [B] a polymerizable unsaturated compound and [C] a radiation-sensitive linear polymerization initiator, other phenol novolac type epoxy resins (Japan) Only the amount described in Table 1 was added to the brand name "epitokel 52" manufactured by Epoxy Resin Co., Ltd. Further, in Example 10, the copolymer [A] and other polymers were used. Example 1 1 <Preparation of Sensitive Radiation Linear Resin Composition> In Example 1, the types and amounts of the respective components contained in the radiation sensitive linear resin composition are as shown in Table 1, except that the solid content concentration of the composition solution was The solution of the sensitive radiation -46-200842162 resin composition (s -1 1) was prepared in the same manner as in Example 1 except for 50% by weight. In Example 1 1, the copolymer [A] and other polymers were used. <Formation and Evaluation of Spacer> In the first embodiment, the method of forming a film on a substrate is the same as in the first embodiment except that it is applied by dry-coating instead of spin coating. Conduct various evaluations. The results are shown in Table 2. The production of the dry film and the transfer of the linear layer of the sensitive radiation on the substrate were carried out in the following manner. On a polyethylene terephthalate film having a thickness of 3 8 μm, the liquid composition (s_i υ of the sensitive radiation linear resin composition is coated by using an applicator, and the coating film is applied at 100 ° C Heating for 5 minutes to produce a linear radiation film of sensitive radiation having a linear layer of sensitive radiation of 4 μm. Next, on the surface of the alkali-free glass substrate, the surface of the sensitive radiation transfer layer is abutted, registration sensitivity Radiation linear dry film, which transfers the linear layer of sensitive radiation on the substrate by hot pressing. Observing the linear layer of sensitive radiation transferred above, the linear layer of sensitive radiation can be uniformly transferred on the substrate, and the underlying film There is a part of the dry film remaining, the dry film on the substrate cannot be closely adhered, etc., and the dry film on the glass substrate cannot be uniformly transferred as "X". The results are shown in Table 2. Comparative Example 3 Example 1 The type and amount of each component contained in the radiation-linear resin composition are as shown in Table 1, and other examples are as shown in Example 11-47-200842162, and a radiation-sensitive linear resin composition solution (S _ 3 ) is prepared, and these are used. Same as in embodiment 1 The radiation-sensitive linear dry film was produced and subjected to various evaluations. The evaluation results are shown in Table 2. In Table 1, the abbreviations of the components indicate the following compounds: (B-1): dipentaerythritol hexaacrylate (Japanese medicine) Company's 'product name' KAYARADDPHA') (B-2): Contains polyfunctional urethane acrylate compound @ commercial (trade name KAYARAD DPHA-40H) (B-3): isovaerythritol tetraacrylate Ester (trade name "aronix M-45 0", manufactured by Toagosei Co., Ltd.) (B-4) : ω-carboxypolycaprolactone monoacrylate (manufactured by Toagosei Co., Ltd., trade name "aronix Μ-5300"" ( B-5) : 1,9-decane diacrylate (trade name "light acrylate 1,9-NDA" manufactured by Kyoeisha Chemical Co., Ltd.) (C-1): ethanone, l-[ 9-Ethyl-6-(2-methylphenylindenyl)-9·H.-carbazol-3-yl]-, 1-(0-ethenyloxyhydrazine) (Kaiye Special Chemicals Co., Ltd. , trade name "Irgacure 0X02") (C-2): Ethanone, 1-[9·ethyl-6-[2-methyl-4-(2,2·dimethyl-1,3-) Dioxolyl)methoxybenzoinyl]-9.Η.-carbazole-3-yl]-,1-(0-ethenyloxyhydrazine) (Company made by ADEKA, trade name "N·1919") (C-3) ·· 2-Dimethylamino 2-(4-methyl-benzyl)-bu (4-morpholine·4-yl) -Phenyl)-butane-1 ketone (manufactured by Chiba Specialty Chemicals, trade name "Irgacure379") -48- 200842162 (C-4) : 2,2·-bis(2-chlorophenyl)- 4,4',Ύ_tetrabenyl-1,2-diimidazole (C-5): 4,4,-bis(diethyl)diphenyl ketone (C-6): 2 -hydrogen sulfide Benzothiazole (C-7): 2-phenylene-2-dimethylamino ""Ή-morpholinophenyl)-butanone-ι (manufactured by Chiba Specialty Chemicals Co., Ltd., trade name " Irgacure 3 69") (C-8): 2-methyl-1-(4-methylthiophene)-2-morpholino propan-1-one (product name "made by Chiba Specialty Chemicals Co., Ltd." Irgacure 907") (D-1): Phenolic novolac type epoxy resin (manufactured by Nippon Epoxy Resin Co., Ltd., trade name "epitokel 52") In Table 1, the "-" symbol indicates that the component is not added in the column. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing an example of a load-deformation amount curve at the time of load and during load removal in the evaluation of the elastic recovery rate. -49- 200842162 1—I谳Other additives parts by weight 1 1 1 1 1 1 1 1 ¢=5 1 1 1 inch 1 m ^vtS tlrnll P 1 1 1 1 1 1 1 1 1 1 1 丄1 [_c]min Radiation linear polymerization initiator parts by weight C=5 s 5/2/2/1/5 5/2/2/1/5 G5 〇> s 5/2/2/1/5 s 5/2/2/ 1/5 C=5 s 5/2/2/1/5 s inch C<J 5/2/2/1/5 m ^T\rS w Cl/C-3 C-1/C-4/C -5/C-6/C-8 C-2/C-4/C-5/C_6/C_8 Cl/C-3 Cl/C-3 Cl/C-3 C-1/C-4/C- 5/C-6/C-8 Cl/C-3 C-1/C-4/C-5/C-6/C-8 Cl/C-3 C-1/C-4/C-5/ C-6/C-8 Cl/C-3 t>- C-1/C-4/C-5/C-6/C-8 [B] Polymeric unsaturated compound parts by weight g 80/60/5 80/60/5 50/50 100/10 g 80/60/5 100/10 80/60/5 100/10 ggggm >IvN i1ml1 waist 1 r H PQ Bl/B-2/B-4 B-1 /B-2/B-4 Bl/B-3 Bl/B-5 Ξ Bl/B_2/B-4 Bl/B-5 B-1/B-2/B-4 Bl/B-5 1 ψ H 1 PQ rH ώ v—H PQ i 1 4 PQ Copolymer [A] Parts by weight ggggggggg 50/50 15/85 ggg Type f < f H ψ ir·· HC^JC^l CO A-1/al A- 1/al IH 1 cd 1 i rH 1 CO (N1 1 CO 1 CO inch 1 Ι Ω 1 1 m 卜 1 • ίί) 00 1 01 1 〇rH 1 r—1 tH 1 CO rH 1 C/3 C\1 1 CO CO 1 in Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Comparative Example 1 Comparative Example 2 Comparative Example 3 -50- 200842162 CNa dry film transferability 1 1 1 1 1 1 1 1 1 1 〇1 1 X Compression characteristic deformation amount L1 (Mm) LTD LO C5 LO <〇 inch LO <=5 oo LTD c=5 1 H CO <〇LTD inch C= 5 in LTD <d> LO inch<=5 CO LO CD c=5 CD CO C5 CD elastic recovery rate (%) C<3 CO LT3 CO CO LO 1 LO CO co LO LO ς〇§ 呀LTD CNJ LO CV3 CO Nu A σ^> cn σ^> CT5 crs CT5 CT5 CTi cn CTi CO oo Adhesiveness (a/100働ggggggggggg § g honing resistance peeling with or without sputum (seconds) LTD inch LO LO inch LO inch s LO LO CO LO CO LO CO sensitivity (J/m2) 1,200 1, 000 1, 000 1, 000 1,000 g C^I » H g ci> t-H 1 , 000 g y--< 0^gf HH g 0〇g oo f H g cr> C^J g oo rH 1 CM 1 CO 00 1 (f) inch 1 (Ω LO 1 CO CD 1 in 卜 1 ίί ) 00 1 ίί) 1 (Ω 〇tH 1 (7) rH tH 1 C^) rH 1 (/) (N1 1 c/i Oo 1 m Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Comparative Example 1 Comparative Example 3 Comparative Example 3