TW201027249A - Radiation-sensitive resin composition, spacer and protective film of liquid crystal element, and method for manufacturing the same - Google Patents

Radiation-sensitive resin composition, spacer and protective film of liquid crystal element, and method for manufacturing the same Download PDF

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TW201027249A
TW201027249A TW098140532A TW98140532A TW201027249A TW 201027249 A TW201027249 A TW 201027249A TW 098140532 A TW098140532 A TW 098140532A TW 98140532 A TW98140532 A TW 98140532A TW 201027249 A TW201027249 A TW 201027249A
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Taiwan
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radiation
compound
resin composition
mass
sensitive resin
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TW098140532A
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Chinese (zh)
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Toshihiro Nishio
Takahiro Sakai
Yuka Sano
Tsuyoshi Nakagawa
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Jsr Corp
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor

Abstract

The present invention relates to a radiation-sensitive resin composition, a spacer and protective film of liquid crystal element, and method for manufacturing them. The purpose of the present invention is to provide a radiation-sensitive resin composition, which has high radiation sensibility; also can be used to manufacture a pattern-like film having desired pattern size and excellent intensity even in the lower exposure amount; besides, can be developed on short time. The said radiation-sensitive resin composition comprises (A) alkali solubility resin, (B) polymerization unsaturated compound, and (C) radiation-sensitive polymeric initiator, in which the said (B) polymerization unsaturated compound is at least one (meth)acrylate compound selected from the group consisting of the compound represented by the following formula (1). In the formula (1), X each indenpendently represents anyone of hydrogen atom, acryloyl group, methacryloyl group, and at least one thereof is acryloyl group or methacryloyl group; furthermore, a to f are integers, and sum total of a to f are 6 to 24.

Description

201027249 六、發明說明： 【發明所屬之技術領域】 本發明係關於感放射線性樹脂組成物、液晶顯示元件之 間隙子和保護膜及其形成方法。 【先前技術】 在液晶顯示元件中使用的部件之中，間隙子、保護膜 等大多是通過光刻法形成的（例如，關於間隙子請參照日本 特開2001— 261761號公報）。近年來，由於液晶顯示面板的 普及和大型化的快速發展，從降低成本和縮短步驟時間的 角度出發，在光刻步驟中，特別需要縮短顯影時間。並且， 迫切需要開發能夠同時實現放射線照射時間（以下稱爲曝光 時間）的縮短和顯影時間的縮短的材料。 爲了縮短顯影時間，通常係通過提高感放射線性樹脂 組成物中所含的鹼可溶性樹脂的酸價而實行。但是，由於 此時照射放射線的部分（以下稱爲曝光部分）的顯影性也有 0 提高，因而使圖案的線寬減小，從而必須延長曝光時間， 因此難以同時實現顯影時間的縮短和曝光時間的縮短。 另外，爲了縮短顯影時間，除了提高感放射線性樹脂 組成物中所含的共聚物的酸價以外，還經常添加親水性高 的低分子化合物（參照例如日本特開2〇07 - 9 1 64號公報）。 但是，在該方法中，由於曝光部分的顯影性也有提高，因 而也難以同時實現顯影時間的縮短和曝光時間的縮短。 爲了同時滿足顯影時間的縮短和曝光時間的縮短這兩 個要求，需要通過提高鹼可溶性樹脂的酸價，或者添加親 .201027249 水性高的低分子化合物，來縮短未曝光部分的顯影時間， 並且還需要提高曝光部分的反應性。作爲提高曝光部分的 反應性的方法，一般是增加聚合性不飽和化合物或者感放 射線性聚合引發劑的使用比率。但是，以往通常使用的聚 合性不飽和化合物’其疏水性很大，因而若增加其使用比 率，則會出現顯影時間延長的問題。 另外，感放射線性聚合引發劑一般爲固體，若增加其 使用比率，則會出現抗蝕劑中析出感放射線性聚合引發劑 〇 的問題而難以應用。並且，感放射線性聚合引發劑一般比 較昂貴，若增加其使用比率，則存在成本增加的問題。 此外，由於間隙子和保護膜是保存在液晶顯示元件內 的“永久膜”，因而要求不會由其析出雜質至元件中。但 是，具有由以前已知的感放射線性樹脂組成物形成的保護 膜、間隙子的液晶顯示元件，會發生估計是由於析出雜質 的原因而導致的“燒屏”，因而成爲問題。感放射線性聚 Q 合引發劑由於被認爲是使這種“燒屏”惡化的原因之一， 因而增強其使用比率，從“燒屏”的角度出發也是不期望 的。 因此，近年來，對於用於形成液晶顯示元件之間隙子和 保護膜的感放射線性樹脂組成物，要求具有高的放射線靈 敏度，即使是低曝光量，也能夠按照所需的圖案尺寸形成 強度優良的圖案狀薄膜，並且，在通過顯影除去未曝光區 域時，能夠在短時間內進行顯影。 專利文獻1 日本特開2001-261761號公報 201027249 專利文獻2 日本特開2007 — 9 1 64號公報 【發明內容】 發明所欲解決之課題 本發明是鑒於上述情況而作出的，其目的是提供一種 感放射線性樹脂組成物，其具有高的放射線靈敏度，即使 是低曝光量，也能夠製得具有所需的圖案尺寸、並且強度 優良的圖案狀薄膜，在顯影步驟和打磨步驟中，圖案不會· 脫落，液晶配向膜對於剝離液的耐久性（耐化學試劑性）優 ❹ 良，當用於液晶顯示元件時，能夠形成不會發生“燒屏” 的間隙子和保護膜，並且能夠在短時間內進行顯影。 本發明的另一目的係提供採用上述感放射線性樹脂組 成物形成液晶顯示元件之間隙子或保護膜的方法。本發明的 又一目的係提供由上述感放射線性樹脂組成物形成的液晶 顯示元件之間隙子或保護膜，以及提供長期可靠性優良的液 晶顯示元件。 n 解決課題之手段 爲解決上述問題而作出的發明，是一種感放射線性樹 脂組成物，其特徵在於，在包含（A)鹼可溶性樹脂、（B)聚合 性不飽和化合物和（C)感放射線性聚合引發劑的感放射線性 樹脂組成物中，作爲（B)聚合性不飽和化合物係含有選自下 述通式（1)表示的化合物群中的至少一種（甲基）丙烯酸酯化 合物。 201027249 O-^CHzCHzO^-X 0-^CH2〇l2〇^-X CHa CHz X-^OH^Htcj—O—C—C — CZ—O— C —C — 〇2— O—^CHzCHzO^-X (1)[Technical Field] The present invention relates to a radiation sensitive resin composition, a spacer for a liquid crystal display element, a protective film, and a method of forming the same. [Prior Art] Among the members used in the liquid crystal display device, a spacer, a protective film, and the like are often formed by photolithography (for example, refer to Japanese Laid-Open Patent Publication No. 2001-261761). In recent years, due to the spread of liquid crystal display panels and rapid development of large-scale, it is particularly necessary to shorten the development time in the photolithography step from the viewpoint of cost reduction and step time reduction. Further, there is an urgent need to develop a material capable of simultaneously shortening the radiation irradiation time (hereinafter referred to as exposure time) and shortening the development time. In order to shorten the development time, it is usually carried out by increasing the acid value of the alkali-soluble resin contained in the radiation-sensitive resin composition. However, since the developability of the portion irradiated with radiation (hereinafter referred to as the exposed portion) is also increased by 0, the line width of the pattern is reduced, and the exposure time must be prolonged, so that it is difficult to simultaneously achieve the shortening of the development time and the exposure time. shorten. In addition, in order to shorten the development time, in addition to the acid value of the copolymer contained in the radiation sensitive resin composition, a low molecular weight compound having high hydrophilicity is often added (see, for example, JP-A No. 2 - 07 - 9 1 64) Bulletin). However, in this method, since the developability of the exposed portion is also improved, it is also difficult to simultaneously achieve shortening of the development time and shortening of the exposure time. In order to satisfy both the shortening of the development time and the shortening of the exposure time, it is necessary to shorten the development time of the unexposed portion by increasing the acid value of the alkali-soluble resin or adding the low molecular compound having a high water content of 201027249, and also It is necessary to increase the reactivity of the exposed portion. As a method of increasing the reactivity of the exposed portion, the use ratio of the polymerizable unsaturated compound or the radiation-sensitive polymerization initiator is generally increased. However, the polymerizable unsaturated compound which has been conventionally used has a large hydrophobicity. Therefore, if the use ratio is increased, the development time is prolonged. Further, the radiation-sensitive polymerization initiator is generally a solid, and if the use ratio is increased, there is a problem that the radiation-inducing linear polymerization initiator 析 is precipitated in the resist, which is difficult to apply. Further, the radiation-sensitive polymerization initiator is generally expensive, and if the usage ratio is increased, there is a problem that the cost increases. Further, since the spacer and the protective film are "permanent films" held in the liquid crystal display element, it is required that impurities are not precipitated into the element. However, a liquid crystal display element having a protective film or a spacer formed of a radiation sensitive linear resin composition known in the prior art causes "burning" which is estimated to be caused by precipitation of impurities, and thus becomes a problem. The radiation-sensitive linear Q-initiator is considered to be one of the causes of deterioration of such "burning screen", and thus its use ratio is also unfavorable from the viewpoint of "burning screen". Therefore, in recent years, the radiation sensitive resin composition for forming the spacer and the protective film of the liquid crystal display element is required to have high radiation sensitivity, and it is possible to form the strength in accordance with the desired pattern size even at a low exposure amount. The pattern-like film can be developed in a short time when the unexposed area is removed by development. OBJECTS OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION The present invention has been made in view of the above circumstances, and an object thereof is to provide a A radiation-sensitive linear resin composition having high radiation sensitivity, and even a low exposure amount, a pattern-like film having a desired pattern size and excellent strength can be obtained, and the pattern is not formed in the developing step and the polishing step. · Dropping, the liquid crystal alignment film is excellent in durability (chemical resistance) of the peeling liquid, and when used in a liquid crystal display element, it is possible to form a spacer and a protective film which do not "burn", and can be short Development is carried out in time. Another object of the present invention is to provide a method of forming a spacer or a protective film of a liquid crystal display element using the above-described radiation sensitive resin composition. Still another object of the present invention is to provide a spacer or a protective film of a liquid crystal display element formed of the above-described radiation sensitive resin composition, and a liquid crystal display element excellent in long-term reliability. n. Solution to Problem The invention made to solve the above problems is a radiation sensitive resin composition comprising (A) an alkali-soluble resin, (B) a polymerizable unsaturated compound, and (C) radiation. In the radiation-sensitive resin composition of the polymerization initiator, the (B) polymerizable unsaturated compound contains at least one (meth) acrylate compound selected from the group of compounds represented by the following formula (1). 201027249 O-^CHzCHzO^-X 0-^CH2〇l2〇^-X CHa CHz X-^OH^Htcj—O—C—C — CZ—O— C—C — 〇2—O—^CHzCHzO^- X (1)

CH2CH2CH2CH2

式（1)中，X各自獨立地表示氫原子、丙烯醯基、甲基 丙烯醯基中的任一者，且至少其中之一爲丙烯醯基或甲基 丙烯醯基。又，a〜f爲整數，且a至f的總和爲6〜24。 根據本發明，可以獲得高放射線靈敏度和優良的顯影 性兩者兼備的感放射線性樹脂組成物。並且，通過採用該 感放射線性樹脂組成物，能夠形成強度和耐久性（耐化學試 劑性）等各種性能優良，同時不會產生“燒屏”的問題的間 隙子或保護膜。 該感放射線性樹脂組成物中所包含的通式（1)化合物的 使用比率，只要相對於100質量份（A)鹼可溶性樹脂爲5〜75 φ 質量份即可。通過以這種比率使用通式（1)化合物，可以獲 得放射線靈敏度、顯影性和壓縮性能等各種性能更高水準 地均衡的感放射線性樹脂組成物。 作爲該感放射線性樹脂組成物中所包含的（B)聚合性不 飽和化合物，也可以與通式（1)化合物同時使用不具有環氧 乙烷骨架的5官能以上的（甲基）丙烯酸酯（B—I)。通過將通 式（1)化合物與不具有環氧乙烷骨架的5官能以上的（甲基） 丙烯酸酯（B - I)進行倂用，可以獲得放射線靈敏度和顯影性 等各種性能更加優良的感放射線性樹脂組成物。另外，當 201027249 將這些化合物進行倂用時，通式（1)化合物的使用比率，相 對於100質量份（A)鹼可溶性樹脂，爲5~75質量份，並且， 不具有環氧乙烷骨架的5官能以上的（甲基）丙烯酸酯（B-I) 的使用比率爲50-150質量份即可。通過採用這種比率，能 夠有效地提高放射線靈敏度和顯影性等各種性能。 該感放射線性樹脂組成物可以用於形成液晶顯示元件 之間隙子或保護膜。另外，液晶顯示元件之間隙子或保護膜 可以通過 ® (υ在基板上形成上述感放射線性樹脂組成物塗膜的步 驟， (2) 對該塗膜的至少一部分照射放射線的步驟， (3) 將照射放射線後的塗膜進行顯影的步驟，和 (4) 將顯影後的塗膜進行加熱的步驟 的各個步驟進行製造。由該感放射線性樹脂組成物形 成之間隙子或保護膜，由於尺寸精度、強度、耐久性（耐化 φ 學試劑性）等各種性能優良，因而可以適用於液晶顯示元 件。並且，具有這種間隙子或保護膜的液晶顯示元件不會 產生“燒屏”的問題。 發明之效果 本發明的感放射線性樹脂組成物，具有高的放射線靈 敏度，即使是低曝光量，也能夠容易地以所需的圖案尺寸 形成在顯影步驟中圖案不會脫落、強度優良的圖案狀薄 膜，並且能夠在短的顯影時間內進行顯影。因此’該感放 射線性樹脂組成物可特別適用於形成液晶顯示元件之間隙 201027249 子或保護膜。 ❹In the formula (1), X each independently represents any one of a hydrogen atom, an acryloyl group, and a methacryl group, and at least one of them is an acryloyl group or a methacryl group. Further, a to f are integers, and the sum of a to f is 6 to 24. According to the present invention, a radiation-sensitive resin composition having both high radiation sensitivity and excellent developability can be obtained. Further, by using the radiation-sensitive resin composition, it is possible to form a gap or a protective film which is excellent in various properties such as strength and durability (chemical resistance) and which does not cause a problem of "burning". The use ratio of the compound of the formula (1) contained in the radiation-sensitive resin composition may be 5 to 75 φ parts by mass based on 100 parts by mass of the (A) alkali-soluble resin. By using the compound of the formula (1) in such a ratio, it is possible to obtain a radiation-sensitive resin composition having a higher level of balance, such as radiation sensitivity, developability, and compression performance. As the (B) polymerizable unsaturated compound contained in the radiation sensitive resin composition, a 5-functional or higher (meth) acrylate having no oxirane skeleton may be used together with the compound of the formula (1). (B-I). By using a compound of the formula (1) and a pentafunctional or higher (meth) acrylate (B - I) having no ethylene oxide skeleton, it is possible to obtain various sensitivities such as radiation sensitivity and developability. A linear resin composition. Further, when these compounds are used in 201027249, the use ratio of the compound of the formula (1) is 5 to 75 parts by mass relative to 100 parts by mass of the (A) alkali-soluble resin, and does not have an ethylene oxide skeleton. The use ratio of the 5-functional or higher (meth) acrylate (BI) may be 50-150 parts by mass. By adopting such a ratio, various properties such as radiation sensitivity and developability can be effectively improved. The radiation sensitive resin composition can be used to form a spacer or a protective film of a liquid crystal display element. Further, the spacer or the protective film of the liquid crystal display element may pass through a step of forming a coating film of the above-mentioned radiation-sensitive resin composition on the substrate, (2) a step of irradiating at least a part of the coating film with radiation, (3) The step of developing the coating film after irradiation with radiation, and (4) the steps of the step of heating the developed coating film, the spacer or the protective film formed of the radiation-sensitive resin composition, due to the size It is excellent in various properties such as accuracy, strength, durability (resistance to chemical resistance), and thus can be applied to liquid crystal display elements. Moreover, liquid crystal display elements having such a spacer or a protective film do not cause "burning" problems. Advantageous Effects of Invention The radiation sensitive resin composition of the present invention has high radiation sensitivity, and even in a low exposure amount, it is possible to easily form a pattern having a pattern that does not fall off and has excellent strength in a development step in a desired pattern size. a film, and can be developed in a short development time. Therefore, the radiation-sensitive resin composition can be particularly suitable. Forming a gap in the liquid crystal display element of the promoter or a protective film 201,027,249. ❹

G 由該感放射線性樹脂組成物形成之間隙子或保護膜， 其尺寸精度、強度等各種性能優良，可適用於液晶顯示元 件。並且，該間隙子或保護膜，由於對液晶配向膜的剝離 液的耐久性（耐化學試劑性）也優良，因而可以提高基板再 製造步驟中的產品成品率。而且，該間隙子在液晶配向膜 的打磨步驟中不會發生圖案脫落。具有這種間隙子或保護 膜的液晶顯示元件，可以抑制“燒屏”的發生，長期可靠 性優良。 【實施方式】 實施發明之最佳形態 <感放射線性樹脂組成物> 以下，對本發明感放射線性樹脂組成物的各成分進行 詳細說明。 (A)鹼可溶性樹脂 作爲本發明感放射線性樹脂組成物中所含的（A)鹼可溶 性樹脂，只要是對於在含有該成分的感放射線性樹脂組成 物的顯影處理步驟中所用的鹼性顯影液具有可溶性，則沒 有特別的限制。作爲這種鹼可溶性樹脂，較佳係具有羧基 的鹼可溶性樹脂，特別較佳係（a 1)選自不飽和羧酸和不飽和 羧酸酐構成的群組中的至少一種（以下稱爲“化合物（a 1) ” 與（a2)(al)以外的不飽和化合物（以下稱爲“化合物（a2)”） 的共聚物。作爲（A)鹼可溶性樹脂，較佳係選自[A 1]使化合 物（a 1)與1分子中具有至少一個羥基的不飽和化合物（以下 -10- 201027249 稱爲“化合物（a2 — 1)”）的共聚物（以下稱爲“共聚物 [α]”）與不飽和異氰酸酯化合物反應而製得的化合物（以 下稱爲“共聚物[Α]”），和[Α2]化合物（al)與具有環氧基的 不飽和化合物（以下稱爲“化合物（a2 - 2)”）的共聚物（以下 稱爲“共聚物[/3 ]”）構成的群組中的至少一種。 作爲化合物（al )，可以列舉例如丙烯酸、甲基丙烯酸、 巴豆酸、2-丙烯醯氧基乙基琥珀酸酯、2-甲基丙烯醯氧基乙 基琥珀酸酯、2-丙烯醯氧基乙基六氫鄰苯二甲酸酯、2-甲基 e 丙烯醯氧基乙基六氫鄰苯二甲酸酯等單羧酸；馬來酸、富 馬酸、檸康酸等二羧酸；上述二羧酸的酸酐等。 這些化合物（al)中，從共聚反應性、所得聚合物或聚合 物對鹼性顯影液的溶解性的角度出發，較佳爲丙烯酸、甲 基丙烯酸、2-丙烯醯氧基乙基琥珀酸酯、2-甲基丙烯醯氧基 乙基琥珀酸酯、馬來酸酐等。 在共聚物[α]和共聚物[/3]中，化合物（al)可以單獨或 φ 者將兩種以上混合使用。在共聚物[α]和共聚物[yS]中，來 自於化合物（al)的重複單元的含有比率，較佳爲5〜60質量 %，更佳爲7〜50質量％，特佳爲8〜40質量％。當來自於化 合物（al)的重複單元的含有比率爲5〜60質量％時，可以獲 得放射線靈敏度、顯影性和感放射線性樹脂組成物的保存 穩定性等各種性能更高水準地均衡的感放射線性樹脂組成 物。 另外，作爲化合物（a2 - 1 )，可以列舉例如（甲基）丙烯 酸2-羥基乙酯、（甲基）丙烯酸3-羥基丙酯、（甲基）丙烯酸 201027249 4-羥基丁酯、（甲基）丙烯酸5_羥基戊酯、（甲基）丙烯酸6-羥基己酯；以及（甲基）丙烯酸4-羥基-環己基酯、（甲基）丙 烯酸4-羥甲基-環己基甲基酯、（甲基）丙烯酸4_羥乙基-環己 基乙基酯等具有脂環式結構的（甲基）丙烯酸羥基烷基酯； (甲基）丙烯酸1，2-二羥基乙基酯、（甲基）丙烯酸2,3_二 羥基丙基酯、（甲基）丙烯酸1,3-二羥基丙基酯、（甲基）丙烯 酸3,4-二羥基丁基酯等（甲基）丙烯酸二羥基烷基酯； ^ 丙烯酸2-(6-羥基己醯氧基）乙酯、丙烯酸3-(6-羥基己 醯氧基）丙酯、丙烯酸4-(6-羥基己醯氧基）丁酯等丙烯酸（6-羥基己醯氧基）烷基酯； 甲基丙烯酸2-(6-羥基己醯氧基）乙酯、甲基丙烯酸3-(6-羥基己醯氧基）丙酯、甲基丙烯酸4-(6-羥基己醯氧基）丁酯 等甲基丙烯酸（6-羥基己醯氧基）烷基酯。 這些化合物（a2 - 1)中，從共聚反應性以及與異氰酸酯 化合物的反應性的角度出發，較佳係丙烯酸2-羥基乙酯、 〇 丙烯酸3-羥基丙酯、丙烯酸4-羥基丁酯、甲基丙烯酸2-羥 基乙酯、甲基丙烯酸3-羥基丙酯、甲基丙烯酸4-羥基丁酯、 丙烯酸4-羥甲基-環己基甲基酯、甲基丙烯酸4-羥甲基-環 己基甲基酯、丙烯酸2,3-二羥基丙基酯、甲基丙烯酸2，3-二羥基丙基酯、上述（甲基）丙烯酸（6-羥基己醯氧基）烷基酯 類等。 另外，化合物（a2 - 1)中，從顯影性的提高方面和所得 間隙子的壓縮性能提高的角度出發，特別較佳係上述（甲基） 丙烯酸（6-羥基己醯氧基）烷基酯類。上述（甲基）丙烯酸（6- -12- 201027249 羥基己醯氧基）烷基酯類中’特別較佳係丙烯酸2-(6-羥基己 醯氧基）乙酯、甲基丙烯酸2-(6-羥基己醯氧基）乙酯。作爲 甲基丙烯酸2-(6-羥基己醯氧基）乙酯與甲基丙烯酸2-羥基 乙酯的混合物的市售品，可以列舉PLACCELFM1D、 FM2D(商品名，戴西爾化學工業（股）生產）等。 在共聚物[α ]中，化合物（a2 - 1)可以單獨或者將兩種 以上混合使用。在共聚物[α ]中，來自於化合物（a2 — 1)的 重複單元的含有比率，較佳爲1〜50質量％，更佳爲3〜40質 量％，特佳爲5~30質量％。當來自於化合物（a2— 1)的重複 單元的含有比率爲1〜5 0質量％時，由其與不飽和異氰酸酯 化合物反應所製得的共聚物的保存穩定性良好。 另外，作爲在共聚物[Θ ]中的化合物（a2 — 2)，可以列 舉例如（甲基）丙烯酸縮水甘油酯、（甲基）丙烯酸2-甲基縮水 甘油酯、4-羥基丁基（甲基）丙烯酸酯縮水甘油醚、（甲基）丙 烯酸3，4-環氧基丁基酯、（甲基）丙烯酸6,7-環氧基庚基酯、 f) (甲基）丙烯酸3,4-環氧基環己基酯、（甲基）丙烯酸3,4-環氧 基環己基甲基酯等（甲基）丙烯酸環氧基（環）烷基酯； 〇：-乙基丙烯酸縮水甘油酯、α-正丙基丙烯酸縮水甘油 酯、α-正丁基丙烯酸縮水甘油酯、α-乙基丙烯酸6,7-環氧 基庚基酯、α-乙基丙烯酸3,4-環氧基環己基酯等其他α-烷基丙烯酸環氧基（環）烷基酯； 鄰乙烯基苄基縮水甘油基醚、間乙烯基苄基縮水甘油 基醚、對乙烯基苄基縮水甘油基醚等縮水甘油基醚。 3-(甲基丙烯醯氧基甲基）氧雜環丁烷、3-(甲基丙烯醯氧 -13- 201027249 基甲基）-3-乙基氧雜環丁烷、3-(甲基丙烯醯氧基甲基）-2-甲 基氧雜環丁烷、3-(甲基丙烯醯氧基乙基）-3-乙基氧雜環丁 烷、2-乙基- 3-(甲基丙烯醯氧基乙基）氧雜環丁烷、3-甲基- 3-甲基丙烯醯氧基甲基氧雜環丁烷、3-乙基-3-甲基丙烯醯氧 基甲基氧雜環丁烷等甲基丙烯酸酯； 3-(丙烯醯氧基甲基）氧雜環丁烷、3-(丙烯醯氧基甲 基）-3-乙基氧雜環丁烷、3-(丙烯醯氧基甲基）-2-甲基氧雜環 丁烷、3-(丙烯醯氧基乙基）-3-乙基氧雜環丁烷、2-乙基 ® -3-(丙烯醯氧基乙基）氧雜環丁烷等丙烯酸酯。 其中，從聚合性角度出發’特別較佳係甲基丙烯酸縮 水甘油酯、甲基丙烯酸2-甲基縮水甘油酯、甲基丙烯酸3,4-環氧基環己基酯、甲基丙烯酸3，4-環氧基環己基甲基酯、3-甲基-3-甲基丙烯醯氧基甲基氧雜環丁烷、3-乙基-3-甲基丙 嫌酿氧基甲基氧雑環丁院等。 在共聚物[6]中，化合物（a2_2)可以單獨或者將兩種 φ 以上混合使用。在共聚物[)3]中，來自於化合物（a2 — 2)的 重複單元的含有比率，較佳爲〇.5~70質量％，更佳爲1〜60 質量％，特佳爲3~50質量％。當來自於化合物（a2—2)的重 複單元的含有比率爲〇.5〜70質量％時’可以獲得共聚物的 耐熱性、共聚物和感放射線性樹脂組成物的保存穩定性等 更高水準地均衡的感放射線性樹脂組成物。 另外，在共聚物[α]和共聚物[A]中，還可以將化合物 (a2- 1)和化合物（a2 — 2)以外的化合物（a2)(以下稱爲“化 合物（a2- 3)”）作爲共聚物的成分使用。 -14- .201027249 作爲化合物（a2 - 3)的具體例子，可以列舉例如丙烯酸 甲酯、丙烯酸正丙酯、丙烯酸異丙酯、丙烯酸正丁酯、丙 烯酸二級丁酯、丙烯酸三級丁酯等丙烯酸烷基酯； 甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丙 酯、甲基丙烯酸異丙酯、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甲基丙烯酸烷基酯； 丙烯酸環己基酯、丙烯酸2-甲基環己基酯、丙烯酸三 環[5.2.1.02,6]癸烷-8-基酯、丙烯酸2-(三環[5.2.1.02,6]癸烷 ❹ -8-基氧基）乙酯、丙烯酸異冰片基酯等丙烯酸脂環式酯； 甲基丙烯酸環己基酯、甲基丙烯酸2-甲基環己基酯、 甲基丙烯酸三環[5.2.1.02’6]癸烷-8-基酯、甲基丙烯酸2-(三 環[5.2.1.02’6]癸烷-8-基氧基）乙酯、甲基丙烯酸異冰片基酯 等甲基丙烯酸脂環式酯； 丙烯酸苯酯、丙烯酸苄酯等丙烯酸的芳基酯或芳烷基 酯； Q 甲基丙烯酸苯酯、甲基丙烯酸苄酯等甲基丙烯酸的芳 基酯或芳烷基酯； 馬來酸二乙酯、富馬酸二乙酯等不飽和二羧酸的二烷 基酯； 丙烯酸四氫呋喃-2-基酯、丙烯酸四氫吡喃-2 -基酯、丙 嫌酸2 -甲基四氬啦喃-2-基醋等.具有含氧五元雜環或含氧六 元雜環的丙烯酸酯； 甲基丙烯酸四氫呋喃-2-基酯、甲基丙烯酸四氫吡喃- 2-基酯、甲基丙烯酸2 -甲基四氫吡喃-2-基酯等具有含氧五元 -15- 201027249 雜環或含氧六元雜環的甲基丙烯酸酯； 苯乙烯、α -甲基苯乙烯等乙烯基芳香族化合物； 1，3-丁二烯、異戊二烯等共軛二烯類化合物； 除此以外，還可以列舉丙烯腈、甲基丙烯腈、丙烯醯 胺、甲基丙烯醯胺等。 這些化合物（a2 — 3)中，從共聚反應性的角度出發，較 佳係甲基丙烯酸正丁基酯、甲基丙烯酸2-甲基縮水甘油 酯、甲基丙烯酸苄酯、甲基丙烯酸三環[5·2.1·〇2’6]癸烷-8-^ 基酯、苯乙烯、對甲氧基苯乙烯、甲基丙烯酸四氫呋喃- 2-基酯、1,3-丁二烯等。 在共聚物[α ]和共聚物[/3 ]中，化合物（a2— 3)可以單獨 或者將兩種以上混合使用。在共聚物[α]和共聚物[yS]中， 來自於化合物（a2- 3)的重複單元的含有比率，較佳爲1〇~70 質量％，更佳爲20〜50質量％，特佳爲30〜50質量％。當來 自於化合物（a2 — 3)的重複單元的含有比率爲10~70質量％ φ 時，可以獲得共聚物分子量容易控制，顯影性、放射線靈 敏度等更高水準地均衡的感放射線性樹脂組成物。 共聚物[α]和共聚物[yS]可以通過在適當的溶劑中，在 自由基聚合引發劑的存在下，使構成成分的單體進行聚合 而製備。作爲上述聚合物中所用的溶劑，較佳係乙二醇烷 基醚、丙二醇單烷基醚乙酸酯、烷氧基丙酸烷基酯、乙酸 酯等。這些溶劑可以單獨或將兩種以上混合使用。 另外’作爲上述自由基聚合引發劑，沒有特別的限制， 可以列舉例如2,2’-偶氮二異丁腈、2,2’-偶氮二-(2,4-二甲基 -16- 201027249 戊腈）、2,2’-偶氮二-(4-甲氧基-2,4-一甲基戊腈）、4,4’-偶氮 二（4_氰基戊酸）、二甲基-2,2’-偶氮二（2-甲基丙酸甲醋）等偶 氮化合物。這些自由基聚合引發劑可以單獨或將兩種以上 混合使用。 共聚物[α]和共聚物[冷]的由凝膠滲透色譜（GPC)測定 的聚苯乙烯換算的重量平均分子量（以下稱爲“ Mw”）’較 佳爲2000〜100000，更佳爲5000~50000。當共聚物[α ]和共 聚物[/3]的Mw爲2000~100000時’可以獲得耐熱性、顯影 〇 性、放射線靈敏度等更高水準地均衡的感放射線性樹脂組 成物。 如上製得的共聚物[α ]，可以將其溶液直接供給聚合物 [Α]的製備，並且也可以先從溶液中分離出來後再供給聚合 物[Α]的製備。聚合物[Α]可以通過使共聚物[α]與不飽和異 氰酸酯化合物反應而製得。 作爲不飽和異氰酸酯，可以列舉例如2-丙烯醯氧基乙 Q 基異氰酸酯、3-丙烯醯氧基丙基異氰酸酯、4-丙烯醯氧基丁 基異氰酸酯、6-丙烯醯氧基己基異氰酸酯、8-丙烯醯氧基辛 基異氰酸酯、10-丙烯醯氧基癸基異氰酸酯、丙烯酸2-(2_ 異氰酸酯基乙氧基）乙酯、丙烯酸2-[2-(2-異氰酸酯基乙氧 基）乙氧基]乙基酯、丙烯酸2-{2-[2-(2-異氰酸酯基乙氧基） 乙氧基]乙氧基}乙基酯、丙烯酸2-(2-異氰酸酯基丙氧基） 乙基酯、丙烯酸2-[2-(2-異氰酸酯基丙氧基）丙氧基]乙基酯 等丙烯酸衍生物； 2-甲基丙烯醯氧基乙基異氰酸酯、3-甲基丙烯醯氧基丙 -17- 201027249 基異氰酸酯、4-甲基丙烯醯氧基丁基異氰酸酯、6-甲基丙烯 醯氧基己基異氰酸酯、甲基丙烯酸2-(2-異氰酸酯基乙氧基） 乙酯、甲基丙烯酸2-[2-(2-異氰酸酯基乙氧基）乙氧基]乙基 酯、甲基丙烯酸2-{2-[2-(2-異氰酸酯基乙氧基）乙氧基]乙氧 基}乙基酯、甲基丙烯酸2-(2-異氰酸酯基丙氧基）乙基酯、 甲基丙烯酸2-[2-(2-異氰酸酯基丙氧基）丙氧基]乙基酯等甲 基丙烯酸衍生物； 作爲2-丙烯醯氧基乙基異氰酸酯的市售品，可以列舉 KARENZ AOI(昭和電工（股）生產），作爲2-甲基丙烯醯氧基 乙基異氰酸酯的市售品，可以列舉KARENZ MOI(昭和電工 (股）生產），作爲甲基丙烯酸2-(2-異氰酸酯基乙氧基）乙基酯 的市售品，可以列舉KARENZ MOI — EG(昭和電工（股）生 產）。 這些不飽和異氰酸酯化合物中，從與共聚物[α ]的反應 性角度考慮，較佳係2-丙烯醯氧基乙基異氰酸酯、2-甲基 Q 丙烯醯氧基乙基異氰酸酯、4_甲基丙烯醯氧基丁基異氰酸 酯、甲基丙烯酸2-(2-異氰酸酯基乙氧基）乙基酯等。 在聚合物[A]中，不飽和異氰酸酯化合物可以單獨或將 兩種以上混合使用。共聚物[α ]與不飽和異氰酸酯化合物的 反應，可以通過例如在室溫或升溫的條件下，在攪拌的同 時，向含二月桂酸二正丁基錫（IV)等催化劑或對甲氧基酚等 聚合抑制劑的共聚物[α]溶液中’加入不飽和異氰酸酯化合 物而進行。 製備聚合物[Α]時不飽和異氰酸酯化合物的用量，相對 -18- 201027249 於共聚物[〇：]中的化合物（a2 — 1)的1莫耳羥基，較佳爲 0.1〜95莫耳％，更佳爲1.0~80莫耳％，特佳爲5.0〜75莫耳 %。當不飽和異氰酸酯化合物的用量爲〇.1~95莫耳％時’會 有提高與共聚物[α ]的反應性、感放射線性樹脂組成物的耐 熱性以及彈性特性的傾向。 共聚物[Α]和共聚物[；S]，各自可以單獨使用，而在可 以使所得感放射線性樹脂組成物的保存穩定性以及間隙子 的強度和耐熱性進一步提高的方面，更佳係將共聚物[A]與 ❹ 共聚物[沒]進行倂用。當將聚合物[A]與共聚物[yS ]倂用時， 共聚物[/3 ]的用量，相對於100質量份聚合物[A]，較佳爲 0.5〜50質量份，更佳爲1〜40質量份，特佳爲3〜30質量份。 當共聚物[卢]的用量爲0.5〜50質量份時，可以獲得感放射 線性樹脂組成物的保存穩定性與耐熱性更高水準地均衡的 感放射線性樹脂組成物。 (B)聚合性不飽和化合物 Q 本發明的感放射線性樹脂組成物中，作爲（B)聚合性不 飽和化合物’含有上述通式（1)表示的（甲基）丙烯酸酯化合 '物。在通式（1)中，X各自獨立地表示丙烯醯基、甲基丙烯 醯基中的任一者。又’ a〜f爲整數，且a至f的總和爲6〜24， 更佳爲6〜18。感放射線性樹脂組成物中通式（1)化合物的使 用比率，相對於100質量份（A)鹼可溶性樹脂，較佳爲5〜75 質量份。 上述通式（1)化合物’可以通過以前已知的方法製備。 例如可以列舉由使二季戊四醇通過與環氧乙烷進行開環加 -19- 201027249 成反應而連接開環骨架的步驟和使開環骨架的末端羥基與 (甲基）丙烯醯氯或（甲基）丙烯酸反應而引入（甲基）丙烯醯基 的步驟構成的方法，以及使（甲基）丙烯酸通過與環氧乙烷進 行開環加成反應以連接開環骨架而合成環氧乙烷改性的（甲 基）丙烯酸後，使其與二季戊四醇進行酯化反應的方法等。 本發明的感放射線性樹脂組成物，也可以同時含有通 式（1)化合物和不具有環氧乙烷骨架的5官能以上的（甲基） 丙烯酸酯。此時，通式（1)化合物的使用比率，相對於100 質量份（A)鹼可溶性樹脂，較佳爲5〜75質量份，並且，不具 有環氧乙烷骨架的5官能以上的（甲基）丙烯酸酯（B — I)(以 下稱爲“聚合性不飽和化合物（B-I)”）的使用比率爲 5 0〜150質量份。 作爲5官能以上的（甲基）丙烯酸酯，可以列舉例如二季 戊四醇五丙烯酸酯、二季戊四醇五甲基丙烯酸酯、二季戊 四醇六丙烯酸酯、二季戊四醇六甲基丙烯酸酯、三（2-丙烯 ❹ 醯氧基乙基）磷酸酯、三（2-甲基丙烯醯氧基乙基）磷酸酯等。 另外，還可以列舉使具有伸烷基直鏈和脂環結構的、 含2個以上異氰酸酯基的化合物與分子內具有1個以上羥 基的3官能、4官能和5官能的（甲基）丙烯酸酯化合物反應 而製得的多官能胺基甲酸酯丙烯酸酯化合物。 作爲5官能以上的（甲基）丙烯酸酯的市售品，可以列舉 例如KAYARAD DPHA(日本化藥（股）生產），作爲多官能胺 基甲酸酯丙烯酸酯的市售品，可以列舉例如KAYARAD DPHA — 40H(以上由曰本化藥（股）生產）等。 -20- .201027249 另外’（B)聚合性不飽和化合物，還可以含有其他聚合 性不飽和化合物（以下稱爲“聚合性不飽和化合物（B _ II)’’）。作爲聚合性不飽和化合物（B — II)，較佳爲一分子中 具有個聚合性不飽和鍵的化合物。 作爲這種聚合性不飽和化合物（B - 11 )，可以列舉例如 季戊四醇四（甲基）丙烯酸酯、三（2-(甲基）丙烯醯氧基乙基） 磷酸酯、ω-羧基聚己內酯單（甲基）丙烯酸酯、乙二醇（甲基） 丙烯酸酯、1,6-己二醇二（甲基）丙烯酸酯、1,9-壬二醇二（甲 〇 基）丙烯酸酯、四乙二醇二（甲基）丙烯酸酯、聚乙二醇二（甲 基）丙烯酸酯、聚丙二醇二（甲基）丙烯酸酯、雙（苯氧基乙醇） 蒔二（甲基）丙烯酸酯、二羥甲基三環癸烷二（甲基）丙烯酸 酯、2-羥基- 3-(甲基）丙烯醯氧基丙基甲基丙烯酸酯、2-(2 乙烯氧基乙氧基）乙基（甲基）丙烯酸酯、三羥甲基丙烷三（甲 基）丙烯酸酯、季戊四醇三（甲基）丙烯酸酯等。 作爲聚合性不飽和化合物（B — II)的市售品，可以列舉 ❹ 例如 ARONIX M — 450、ARONIX M- 1310、ARONIX Μ - 1600、 ARONIX Μ— 5300、ARONIX Μ- 5600、ARONIX Μ- 5700、 ARONIX Μ— 210、ARONIX Μ- 220、ARONIX Μ- 240、 ARONIX Μ- 270、ARONIX Μ— 6200、ARONIX Μ- 305、 ARONIX Μ — 309 ' ARONIX Μ - 310、ARONIX Μ — 315(以上 由東亞合成（股）生產）；VISCOTE 295、VISCOTE 300、 VISCOTE 360 'VISCOTE GPT 'VISCOTE 3PA 'YISCOTE 400 ' VISCOTE SH— 5 00B、VISCOTE 260、VISCOTE 312、 VISCOTE 335HP(以上由大阪有機化學工業（股）生產）； -21 - 201027249 KAYARAD HDDA、KAYARAD HX- 220、KAYARAD HX-620、KAYARAD R — 526、KAYARAD R- 167、KAYARAD R —604、KAYARAD R- 684、KAYARAD R- 551、KAYARAD R- 712、UX- 220 1、UX- 23 0 1、UX — 3204、UX— 3 3 0 1、 UX - 4101、UX— 6101、UX - 7101、UX - 8101、UX — 0937、 MU—2100、MU— 4001(以上由曰本化藥（股）生產）；UN — 9000H、ArtResin UN - 9000PEP、ArtResin UN — 9200A、 ArtResin UN— 7600 'ArtResin UN— 3 3 3 'ArtResin UN— 1 003 ' eG A spacer or a protective film formed of the radiation-sensitive resin composition is excellent in various properties such as dimensional accuracy and strength, and is applicable to liquid crystal display elements. Further, since the spacer or the protective film is excellent in durability (chemical resistance) to the peeling liquid of the liquid crystal alignment film, the product yield in the substrate remanufacturing step can be improved. Further, the spacer does not cause pattern peeling during the polishing step of the liquid crystal alignment film. A liquid crystal display element having such a spacer or a protective film can suppress the occurrence of "burning" and has excellent long-term reliability. [Embodiment] The best mode for carrying out the invention <Sense Radiation Resin Composition> Hereinafter, each component of the radiation sensitive resin composition of the present invention will be described in detail. (A) Alkali-soluble resin (A) an alkali-soluble resin contained in the radiation sensitive resin composition of the present invention, as long as it is an alkali development used in a development treatment step of a radiation-sensitive resin composition containing the component The liquid is soluble, and there is no particular limitation. The alkali-soluble resin is preferably an alkali-soluble resin having a carboxyl group, and particularly preferably (a1) is at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride (hereinafter referred to as "a compound" (a 1) a copolymer of an unsaturated compound other than (a2) (al) (hereinafter referred to as "compound (a2)"). The (A) alkali-soluble resin is preferably selected from [A1]. a copolymer of the compound (a 1) and an unsaturated compound having at least one hydroxyl group in one molecule (hereinafter referred to as "compound (a2 - 1)") (hereinafter referred to as "compound [α]")) a compound obtained by reacting an unsaturated isocyanate compound (hereinafter referred to as "copolymer [Α]"), and [Α2] a compound (al) and an unsaturated compound having an epoxy group (hereinafter referred to as "a compound (a2 - 2) At least one of the group consisting of a copolymer (hereinafter referred to as "copolymer [/3]"). As the compound (al), for example, acrylic acid, methacrylic acid, crotonic acid, 2-propene oxime may be mentioned. Oxyethyl succinate, 2-methyl propylene oxy ethoxylate a monocarboxylic acid such as succinate, 2-propenyloxyethylhexahydrophthalate or 2-methylepropenyloxyethylhexahydrophthalate; maleic acid, rich a dicarboxylic acid such as horse acid or citraconic acid; an acid anhydride of the above dicarboxylic acid; etc. Among these compounds (al), from the viewpoint of copolymerization reactivity, solubility of the obtained polymer or polymer to an alkaline developer, Preferred are acrylic acid, methacrylic acid, 2-propenyloxyethyl succinate, 2-methacryloxyethyl succinate, maleic anhydride, etc. in copolymer [α] and copolymer [/ In the above, the compound (al) may be used singly or in combination of two or more. In the copolymer [α] and the copolymer [yS], the content of the repeating unit derived from the compound (al) is preferably 5 to 60% by mass, more preferably 7 to 50% by mass, particularly preferably 8 to 40% by mass. When the content ratio of the repeating unit derived from the compound (al) is 5 to 60% by mass, radiation sensitivity can be obtained, a highly sensitive and balanced radiation-sensitive tree with various properties such as developability and storage stability of the radiation-sensitive resin composition Further, examples of the compound (a2 - 1 ) include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and (meth)acrylic acid 201027249 4-hydroxybutyl ester. 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate; and 4-hydroxy-cyclohexyl (meth)acrylate, 4-hydroxymethyl-cyclohexyl (meth)acrylate a hydroxyalkyl (meth) acrylate having an alicyclic structure such as a 4-ester or a 4-hydroxyethyl-cyclohexylethyl (meth)acrylate; 1,2-dihydroxyethyl (meth)acrylate , 2,3-dihydroxypropyl (meth)acrylate, 1,3-dihydroxypropyl (meth)acrylate, 3,4-dihydroxybutyl (meth)acrylate, etc. (methyl) Dihydroxyalkyl acrylate; ^ 2-(6-hydroxyhexyloxy)ethyl acrylate, 3-(6-hydroxyhexyloxy) propyl acrylate, 4-(6-hydroxyhexyloxy) acrylate (6-Hydroxyhexyloxy)alkyl acrylate such as butyl ester; 2-(6-hydroxyhexyloxy)ethyl methacrylate, 3-(6-hydroxyhexyloxy) methacrylate Propyl methacrylate, 4- (6-hydroxy-hexyl acyl group) butyl methacrylate, (6-hydroxy-hexyl acyl oxy) alkyl esters. Among these compounds (a2 - 1), 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, and A are preferred from the viewpoints of copolymerization reactivity and reactivity with an isocyanate compound. 2-hydroxyethyl acrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 4-hydroxymethyl-cyclohexylmethyl acrylate, 4-hydroxymethyl-cyclohexyl methacrylate Methyl ester, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, (6-hydroxyhexyloxy)alkyl (meth) acrylate, and the like. Further, in the compound (a2-1), the above (meth)acrylic acid (6-hydroxyhexyloxy)alkyl ester is particularly preferable from the viewpoint of improvement in developability and improvement in compression properties of the obtained spacer. class. Among the above (meth)acrylic acid (6--12-201027249 hydroxyhexyloxy)alkyl esters, 'particularly preferred is 2-(6-hydroxyhexyloxy)ethyl acrylate, 2-methacrylic acid methacrylate 6-Hydroxyhexyloxy)ethyl ester. As a commercial product of a mixture of 2-(6-hydroxyhexyloxy)ethyl methacrylate and 2-hydroxyethyl methacrylate, PLACCELFM1D, FM2D (trade name, Daisy Chemical Industry Co., Ltd.) can be cited. Production) and so on. In the copolymer [α ], the compound (a2 - 1) may be used singly or in combination of two or more. In the copolymer [α ], the content ratio of the repeating unit derived from the compound (a2 - 1) is preferably from 1 to 50% by mass, more preferably from 3 to 40% by mass, particularly preferably from 5 to 30% by mass. When the content ratio of the repeating unit derived from the compound (a2-1) is from 1 to 50% by mass, the copolymer obtained by the reaction with the unsaturated isocyanate compound has good storage stability. Further, examples of the compound (a2-2) in the copolymer [Θ] include glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, and 4-hydroxybutyl (A). Acrylate glycidyl ether, 3,4-epoxybutyl (meth)acrylate, 6,7-epoxyheptyl (meth)acrylate, f) (meth)acrylic acid 3,4 - an epoxy (cyclo)alkyl (meth) acrylate such as an epoxycyclohexyl ester or a 3,4-epoxycyclohexylmethyl (meth)acrylate; 〇:-glycidyl methacrylate , glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, 6,7-epoxyheptyl α-ethyl acrylate, 3,4-epoxy ring of α-ethyl acrylate Other α-alkyl acrylate epoxy (cyclo)alkyl esters such as hexyl ester; o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, etc. Glyceryl ether. 3-(methacryloxymethyl)oxetane, 3-(methacrylofluorene-13- 201027249 methyl)-3-ethyloxetane, 3-(methyl Propylene methoxymethyl)-2-methyloxetane, 3-(methacryloxyethyl)-3-ethyloxetane, 2-ethyl-3-(A Acryloxyethyl)oxetane, 3-methyl-3-methylpropenyloxymethyloxetane, 3-ethyl-3-methylpropenyloxymethyl Methacrylate such as oxetane; 3-(acryloxymethyl)oxetane, 3-(acryloxymethyl)-3-ethyloxetane, 3- (Acryloxymethyl)-2-methyloxetane, 3-(acryloxyethyl)-3-ethyloxetane, 2-ethyl®-3-(propylene Acrylate such as decyloxyethyl)oxetane. Among them, from the viewpoint of polymerizability, "glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, methacrylic acid 3,4 are particularly preferable. - Epoxycyclohexylmethyl ester, 3-methyl-3-methylpropenyloxymethyloxetane, 3-ethyl-3-methylpropanoid oxymethyloxanium ring Ding Yuan and so on. In the copolymer [6], the compound (a2_2) may be used singly or in combination of two or more kinds of φ or more. In the copolymer [)3], the content ratio of the repeating unit derived from the compound (a2-2) is preferably 〇5 to 70% by mass, more preferably 1 to 60% by mass, particularly preferably 3 to 50%. quality%. When the content ratio of the repeating unit derived from the compound (a2-2) is 〇.5 to 70% by mass, the heat resistance of the copolymer, the storage stability of the copolymer and the radiation-sensitive resin composition, and the like can be obtained to a higher level. A well-balanced radiation sensitive resin composition. Further, in the copolymer [α] and the copolymer [A], the compound (a2) and the compound (a2) other than the compound (a2-2) (hereinafter referred to as "compound (a2-3)") may also be used. ) used as a component of the copolymer. -14-.201027249 Specific examples of the compound (a2 - 3) include methyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, secondary butyl acrylate, and tertiary butyl acrylate. Alkyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, butyl methacrylate, methacrylic acid Alkyl methacrylate such as butyl acrylate; cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo[5.2.1.02,6]decane-8-yl acrylate, 2-(tricyclo[2-[ 5.2.1.02,6]decane -8-yloxy)ethyl ester, isobornyl acrylate, etc.; Cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, A Tricyclo[5.1.00.2'6]decane-8-yl acrylate, 2-(tricyclo[5.2.1.02'6]decane-8-yloxy)ethyl methacrylate, methacrylic acid a methacrylate alicyclic ester such as borneol ester; an aryl or aralkyl ester of acrylic acid such as phenyl acrylate or benzyl acrylate; Q aryl or aralkyl ester of methacrylic acid such as phenyl methacrylate or benzyl methacrylate; dialkyl ester of unsaturated dicarboxylic acid such as diethyl maleate or diethyl fumarate ; tetrahydrofuran-2-yl acrylate, tetrahydropyran-2-yl acrylate, 2-methyltetrahydropyran-2-yl vinegar, etc. with oxygen-containing five-membered heterocyclic ring or oxygen-containing six-membered Heterocyclic acrylate; tetrahydrofuran-2-yl methacrylate, tetrahydropyran-2-yl methacrylate, 2-methyltetrahydropyran-2-yl methacrylate, etc. -15-201027249 Heterocyclic or oxygenated six-membered heterocyclic methacrylate; vinyl aromatic compound such as styrene or α-methylstyrene; 1,3-butadiene, isoprene, etc. The conjugated diene compound may be exemplified by acrylonitrile, methacrylonitrile, acrylamide, methacrylamide or the like. Among these compounds (a2 - 3), from the viewpoint of copolymerization reactivity, n-butyl methacrylate, 2-methyl glycidyl methacrylate, benzyl methacrylate, and trimethyl methacrylate are preferred. [5·2.1·〇2'6] decane-8-^ group ester, styrene, p-methoxystyrene, tetrahydrofuran-2-yl methacrylate, 1,3-butadiene, and the like. In the copolymer [α ] and the copolymer [/3 ], the compound (a2-3) may be used singly or in combination of two or more. In the copolymer [α] and the copolymer [yS], the content ratio of the repeating unit derived from the compound (a2-3) is preferably from 1 to 70% by mass, more preferably from 20 to 50% by mass, particularly preferably It is 30 to 50% by mass. When the content ratio of the repeating unit derived from the compound (a2-3) is 10 to 70% by mass φ, it is possible to obtain a radiation-sensitive resin composition in which the molecular weight of the copolymer is easily controlled, and the developing property and the radiation sensitivity are balanced at a higher level. . The copolymer [α] and the copolymer [yS] can be produced by polymerizing a monomer constituting the component in the presence of a radical polymerization initiator in a suitable solvent. The solvent used in the above polymer is preferably ethylene glycol alkyl ether, propylene glycol monoalkyl ether acetate, alkyl alkoxypropionate, acetate or the like. These solvents may be used singly or in combination of two or more. Further, 'the radical polymerization initiator is not particularly limited, and examples thereof include 2,2'-azobisisobutyronitrile and 2,2'-azobis-(2,4-dimethyl-16-). 201027249 valeronitrile), 2,2'-azobis-(4-methoxy-2,4-methylvaleronitrile), 4,4'-azobis(4-cyanovaleric acid), two An azo compound such as methyl-2,2'-azobis(2-methylpropionic acid methyl vinegar). These radical polymerization initiators may be used singly or in combination of two or more. The polystyrene-equivalent weight average molecular weight (hereinafter referred to as "Mw") as determined by gel permeation chromatography (GPC) of the copolymer [α] and the copolymer [cold] is preferably from 2,000 to 100,000, more preferably 5,000. ~50000. When the Mw of the copolymer [α ] and the copolymer [/3] is from 2,000 to 100,000, a radiation level linear resin composition having higher level of equilibration such as heat resistance, development enthalpy, and radiation sensitivity can be obtained. The copolymer [α] obtained as above can be directly supplied to the preparation of the polymer [Α], and can also be separated from the solution before being supplied to the preparation of the polymer [Α]. The polymer [Α] can be obtained by reacting the copolymer [α] with an unsaturated isocyanate compound. The unsaturated isocyanate may, for example, be 2-propenyloxyethyl Q-isocyanate, 3-propenylmethoxypropyl isocyanate, 4-propenyloxybutyl isocyanate, 6-propenyloxyhexyl isocyanate, 8- Propylene oxime octyl isocyanate, 10-propylene decyl decyl isocyanate, 2-(2-Isocyanate ethoxy)ethyl acrylate, 2-[2-(2-isocyanate ethoxy) acrylate Ethyl ester, 2-{2-[2-(2-isocyanatoethoxy)ethoxy]ethoxy}ethyl acrylate, 2-(2-isocyanatepropoxy)ethyl acrylate Acrylic acid derivative such as 2-[2-(2-isocyanatepropoxy)propoxy]ethyl acrylate; 2-methylpropenyloxyethyl isocyanate, 3-methylpropenyloxypropane- 17- 201027249 Benzyl isocyanate, 4-methacryloxy butyl butyl isocyanate, 6-methyl propylene methoxy hexyl isocyanate, 2-(2-isocyanate ethoxy) ethyl methacrylate, methacrylic acid 2 -[2-(2-Isocyanate ethoxy)ethoxy]ethyl ester, 2-{2-[2-(2-isocyanate ethoxy) methacrylate Oxy]ethoxy}ethyl ester, 2-(2-isocyanatopropyloxy)ethyl methacrylate, 2-[2-(2-isocyanatepropyloxy)propoxy methacrylate] A methacrylic acid derivative such as an ethyl ester; a commercially available product of 2-propenyloxyethyl isocyanate, which is exemplified by KARENZ AOI (produced by Showa Denko), as 2-methylpropenyloxyethyl isocyanate Commercial products of KARENZ MOI (produced by Showa Denko) are commercially available as 2-(2-isocyanate ethoxy)ethyl methacrylate, and KARENZ MOI — EG (Showa Denko) (share) production). Among these unsaturated isocyanate compounds, from the viewpoint of reactivity with the copolymer [α ], 2-propylene methoxyethyl isocyanate, 2-methyl Q propylene methoxyethyl isocyanate, and 4-methyl group are preferred. Propylene methoxy butyl isocyanate, 2-(2-isocyanate ethoxy) ethyl methacrylate, and the like. In the polymer [A], the unsaturated isocyanate compounds may be used singly or in combination of two or more. The reaction of the copolymer [α ] with the unsaturated isocyanate compound can be carried out, for example, at room temperature or elevated temperature, while stirring, to a catalyst such as di-n-butyltin dilaurate (IV) or p-methoxyphenol. The copolymer [α] solution of the polymerization inhibitor is carried out by adding an unsaturated isocyanate compound. The amount of the unsaturated isocyanate compound to be used in the preparation of the polymer [Α] is preferably from 0.1 to 95 mol%, based on 1 mol% of the compound (a2 - 1) in the copolymer [〇:], from -18 to 201027249. More preferably, it is 1.0 to 80 mol%, and particularly preferably 5.0 to 75 mol%. When the amount of the unsaturated isocyanate compound is from 0.1 to 95 mol%, the reactivity with the copolymer [α] and the heat resistance and elastic properties of the radiation-sensitive resin composition tend to be improved. The copolymer [Α] and the copolymer [;S] may each be used singly, and it is more preferable that the storage stability of the obtained radiation sensitive resin composition and the strength and heat resistance of the spacer are further improved. The copolymer [A] was used in combination with the ruthenium copolymer [none]. When the polymer [A] and the copolymer [yS] are used, the amount of the copolymer [/3] is preferably 0.5 to 50 parts by mass, more preferably 1 to 100 parts by mass of the polymer [A]. ~40 parts by mass, particularly preferably 3 to 30 parts by mass. When the amount of the copolymer [L] is from 0.5 to 50 parts by mass, a radiation-sensitive resin composition having a higher level of storage stability and heat resistance of the radiation-sensitive linear resin composition can be obtained. (B) Polymerizable unsaturated compound Q The (B) polymerizable unsaturated compound (B) contains the (meth) acrylate compound represented by the above formula (1). In the formula (1), X each independently represents any one of an acryloyl group and a methacryloyl group. Further, 'a to f are integers, and the sum of a to f is 6 to 24, more preferably 6 to 18. The use ratio of the compound of the formula (1) in the radiation-sensitive resin composition is preferably 5 to 75 parts by mass based on 100 parts by mass of the (A) alkali-soluble resin. The above compound (1) can be produced by a previously known method. For example, a step of linking the dipentaerythritol to the ring-opening skeleton by ring-opening plus -19-201027249 with ethylene oxide and a terminal hydroxyl group of the ring-opening skeleton with (meth)acrylofluorene or (methyl) may be mentioned. a method consisting of a step of introducing a (meth) acrylonitrile group by an acrylic acid reaction, and synthesizing an ethylene oxide by subjecting (meth)acrylic acid to a ring-opening addition reaction with ethylene oxide to join a ring-opening skeleton. After the (meth)acrylic acid, a method of esterifying the dipentaerythritol with the like is carried out. The radiation sensitive resin composition of the present invention may contain both a compound of the formula (1) and a pentafunctional or higher functional (meth) acrylate having no ethylene oxide skeleton. In this case, the use ratio of the compound of the formula (1) is preferably 5 to 75 parts by mass based on 100 parts by mass of the (A) alkali-soluble resin, and 5 or more functional groups having no ethylene oxide skeleton (A) The use ratio of the acrylate (B-I) (hereinafter referred to as "polymerizable unsaturated compound (BI)") is from 50 to 150 parts by mass. Examples of the 5-functional or higher (meth) acrylate include dipentaerythritol pentaacrylate, dipentaerythritol penta methacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, and tris(2-propene fluorene oxime). Oxyethyl) phosphate, tris(2-methylpropenyloxyethyl) phosphate, and the like. Further, a compound having two or more isocyanate groups having an alkyl straight chain and an alicyclic structure and a trifunctional, tetrafunctional and pentafunctional (meth) acrylate having one or more hydroxyl groups in the molecule may also be mentioned. A polyfunctional urethane acrylate compound obtained by reacting a compound. For example, KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.), which is a commercially available product of a 5-functional or higher (meth) acrylate, may be mentioned as a commercially available product of a polyfunctional urethane acrylate, for example, KAYARAD. DPHA — 40H (above produced by 曰本化药(股)). -20- .201027249 Further, '(B) a polymerizable unsaturated compound may further contain another polymerizable unsaturated compound (hereinafter referred to as "polymerizable unsaturated compound (B _ II)'') as a polymerizable unsaturated compound. (B - II) is preferably a compound having a polymerizable unsaturated bond in one molecule. Examples of such a polymerizable unsaturated compound (B-11) include pentaerythritol tetra(meth)acrylate, and three ( 2-(Methyl)acryloxyethyl) phosphate, ω-carboxypolycaprolactone mono(meth)acrylate, ethylene glycol (meth) acrylate, 1,6-hexanediol II ( Methyl) acrylate, 1,9-nonanediol bis(methyl decyl) acrylate, tetraethylene glycol di(meth) acrylate, polyethylene glycol di(meth) acrylate, polypropylene glycol bis ( Methyl) acrylate, bis(phenoxyethanol) quinone di(meth) acrylate, dimethylol tricyclodecane di(meth) acrylate, 2-hydroxy-3-(methyl) propylene oxime Oxypropyl methacrylate, 2-(2 vinyloxyethoxy)ethyl (meth)acrylic acid Ester, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, etc. As a commercial product of the polymerizable unsaturated compound (B-II), for example, ARONIX M-450, ARONIX M- 1310, ARONIX Μ - 1600, ARONIX Μ - 5300, ARONIX Μ - 5600, ARONIX Μ - 5700, ARONIX Μ - 210, ARONIX Μ - 220, ARONIX Μ - 240, ARONIX Μ - 270, ARONIX Μ - 6200, ARONIX Μ-305, ARONIX Μ — 309 ' ARONIX Μ - 310, ARONIX Μ — 315 (above produced by East Asia Synthetic Co., Ltd.); VISCOTE 295, VISCOTE 300, VISCOTE 360 'VISCOTE GPT 'VISCOTE 3PA 'YISCOTE 400 ' VISCOTE SH — 5 00B, VISCOTE 260, VISCOTE 312, VISCOTE 335HP (above produced by Osaka Organic Chemical Industry Co., Ltd.); -21 - 201027249 KAYARAD HDDA, KAYARAD HX-220, KAYARAD HX-620, KAYARAD R — 526, KAYARAD R- 167, KAYARAD R — 604, KAYARAD R-684, KAYARAD R- 551, KAYARAD R-712, UX-220 1, UX- 23 0 1, UX — 3204, UX — 3 3 0 1, UX — 4101, UX — 6101, UX-7101, UX-8101, UX — 0937, MU-2100, MU-4001 (above produced by 曰本化药(股)); UN — 9000H, ArtResin UN - 9000PEP, ArtResin UN — 9200A, ArtResin UN— 7600 'ArtResin UN— 3 3 3 'ArtResin UN-1 003 ' e

ArtResin UN— 1 255、ArtResin UN— 6060PTM、ArtResin UN - 6060P(以上由根上工業（股）生產）等。 (C)感放射線性聚合引發劑 本發明感放射線性樹脂組成物中所含的（C)感放射線性 聚合引發劑，是通過感應放射線而產生能夠引發（B)聚合性 不飽和化合物的聚合的活性物質的成分。作爲這種（C)感放 射線性聚合引發劑，可以列舉〇-醯基肟化合物、苯乙酮化 0 合物、聯二咪唑化合物、二苯酮化合物等。 作爲上述〇-醯基肟化合物的具體例子，可以列舉例如 乙酮- l-[9-乙基- 6-(2-甲基苯甲醯基）-9H-咔唑-3-基]-l-(0-乙醯基肟）、l-[9-乙基-6-苯甲醯基-9.H.-昨唑-3-基]-辛-1-酮肟-〇-乙酸酯、1-[9-乙基-6-(2-甲基苯甲醯基）-9·Η·-咔唑 -3-基]-乙-1-酮肟-〇-苯甲酸酯、1-[9-正丁基-6-(2-乙基苯甲 醯基）-9.Η·-咔唑_3_基]-乙-1-酮肟-0-苯甲酸酯、乙酮-l-[9-乙基- 6-(2-甲基-4-四氫呋喃基苯甲醯基）-9.Η.-咔唑- 3-基]-1-(〇-乙醯基肟）、乙酮-1-[9-乙基- 6-(2-甲基-4-四氫吡喃 -22- 201027249 基苯甲醯基）-9.11.-昨唑-3-基]-1-(0-乙醯基肟）、乙酮-1-[9-乙基- 6- (2 -甲基_5_四氮呋喃基苯甲醯基）-9.Η. -咔唑- 3-基]-1-(〇-乙醯基肟）、乙酮-1-[9-乙基-6-{2-甲基-4-(2,2-二 甲基-1,3-二氧雜環戊基）甲氧基苯甲醯基}-9.11.-咔唑- 3-基]-1-(0-乙醯基肟）等。 它們當中，作爲較佳的0-醯基肟化合物，可以列舉乙 酮- l-[9-乙基- 6-(2-甲基苯甲醯基）-9H-咔唑-3-基]-1-(0-乙 醯基肟）、乙酮- l- [9 -乙基- 6- (2 -甲基-4-四氫呋喃基甲氧基苯 〇 甲醯基）-9.Η·-咔唑-3-基]-l-(0-乙醯基肟）或乙酮- l-[9-乙基 -6-{2-甲基-4-(2，2-二甲基-1,3-二氧雜環戊基）甲氧基苯甲 醯基}-9·Η·-咔唑-3-基]-1-(0-乙醯基肟）。這些0-醯基肟化 合物可以單獨或將兩種以上混合使用。 作爲上述苯乙酮化合物，可以列舉例如α -胺基酮化合 物、α -羥基酮化合物。 作爲α -胺基酮類化合物的具體例子，可以列舉2-苄基 〇 -2-二甲基胺基-1-(4-嗎啉基苯基）-丁 -1-酮、2-二甲基胺基 -2-(4-甲基苄基）-1-(4-嗎啉-4-基-苯基）-丁 -1-酮、2-甲基 -1-(4-甲硫基苯基）-2-嗎啉基丙-1-酮等。 作爲α -羥基酮化合物的具體例子，可以列舉1-苯基-2-羥基-2-甲基丙-1-酮、1-(4-異丙基苯基）-2-羥基-2-甲基丙-1-酮、4-(2-羥基乙氧基）苯基-(2-羥基-2-丙基）酮、1-羥基環己 基苯基嗣等。 這些苯乙酮化合物中，較佳係α -胺基酮化合物，特別 較佳係2_苄基-2-二甲基胺基-1-(4 -嗎啉基苯基）-丁 -1-酮或 -23- 201027249 2-二甲基胺基-2-(4-甲基苄基）-1-(4-嗎啉-4-基-苯基）-丁 -1-酮。 作爲上述聯二咪嗖化合物的具體例子，可以列舉2,2’-二（2-氯苯基）-4,4’，5,5’-四（4-乙氧羰基苯基）-1,2’·聯二咪 唑、2,2’-二（2-氯苯基）-4,4’，5,5’-四苯基-1,2’-聯二咪唑、 2,2’-二（2,4-二氯苯基）-4,4’，5,5’-四苯基-1，2’-聯二咪唑、 2,2’-二（2,4,6-三氯苯基）-4,4’，5,5’-四苯基-1，2’-聯二咪唑 等。 〇 這些聯二咪唑化合物中，較佳係2,2’-二（2-氯苯 基）-4,4’，5,5’-四苯基-1，2’-聯二咪唑、2,2’-二（2,4-二氯苯 基）-4,4，，5,5，-四苯基-1,2’-聯二咪唑或 2,2’-二（2,4,6-三氯 苯基）-4,4’，5,5’-四苯基-1,2’-聯二咪唑，特別較佳係2，2’-二（2,4-二氯苯基）-4,4’，5,5’-四苯基-1,2’-聯二咪唑。 在本發明的感放射線性樹脂組成物中，當使用聯二咪 唑化合物作爲（C)感放射線性聚合引發劑時，爲了使增敏， 0 可以添加具有二烷基胺基的脂肪族或芳香族化合物（以下， 稱爲“胺基系增敏劑”）。 作爲這種胺基系增敏劑，可以列舉例如4,4’-二（二甲基 胺基）二苯酮、4,4’-二（二乙基胺基）二苯酮等。這些胺基系 增敏劑中，特別較佳係4,4’-二（二乙基胺基）二苯酮。上述 胺基系增敏劑可以單獨或將兩種以上混合使用。 另外，在本發明的感放射線性樹脂組成物中，當將聯 二咪，唑化合物與胺基系增敏劑倂用時，可以添加作爲氫自 由基供體的硫醇化合物。聯二咪唑化合物由胺基系增敏劑 -24- 201027249 增敏而斷裂，產生咪唑自由基，但是其本身並不表現出高 的聚合引發能’會出現所得液晶顯示元件的間隙子成爲倒 錐形的不理想形狀的情況。然而，通過在聯二咪唑化合物 與胺基系增敏劑的共存體系中添加硫醇化合物，由硫醇化 合物向咪唑自由基提供氫自由基。結果，咪唑自由基轉化 爲中性的咪唑，同時，產生具有聚合引發能高的硫自由基 的成分，這樣可以使間隙子的形狀成爲更佳係的正錐形。 作爲這種硫醇化合物，可以列舉例如2-锍基苯并噻 ❹ 唑、2 -锍基苯并噁唑、2 -锍基苯并咪唑、2 -锍基-5-甲氧基苯 并噻唑等芳香族硫醇化合物；3-锍基丙酸、3-锍基丙酸甲酯 等脂肪族單硫.醇化合物；季戊四醇四（锍基乙酸酯）、季戊四 醇四（3-锍基丙酸酯）等2官能以上的脂肪族硫醇化合物。這 些硫醇化合物中，特別較佳係2-锍基苯并噻唑。 當將聯二咪唑化合物與胺基系增敏劑倂用時，胺基系 增敏劑的添加量，相對於1〇〇質量份聯二咪唑化合物，較 Q 佳爲0.1〜50質量份，更佳爲1~2 0質量份。當胺基系增敏劑 的添加量爲0.1〜50質量份時，可以使所得間隙子的性質良 好。 另外，當將聯二咪唑化合物和胺基系增敏劑與硫醇化 合物倂用時，作爲硫醇化合物的添加量，相對於1〇〇質量 份聯二咪唑化合物，較佳爲0.1〜50質量份，更佳係1〜2〇 質量份。當硫醇化合物的添加量爲〇·1〜50質量份時’可以 使間隙子的性質、黏附性達到最佳。 本發明感放射線性樹脂組成物中所含的（c )感放射線性 -25- 201027249 聚合引發劑’較佳係含有選自〇 -醯基肟化合物和苯乙酮化 合物構成的群組中的至少一種，更佳係含有選自〇-醯基肟 化合物和苯乙酮化合物構成的群組中的至少一種以及聯二 咪唑化合物。 作爲（C)感放射線性聚合引發劑中〇-醯基肟化合物和 苯乙酮化合物的比率，其合計量相對於（C)感放射線性聚合 引發劑的總量，較佳爲40質量％以上，更佳爲45質量％以 上，特佳爲50質量％以上。通過以這種比率使用（C)感放射 線性聚合引發劑，可以使本發明的感放射線性樹脂組成物 即使在低曝光量的情況下也以高的靈敏度形成具有更高強 度和黏附性的間隙子或保護膜。 [添加劑] 本發明的感放射線性樹脂組成物，除了上述成分以 外，在不損害預期效果的情況下，根據需要，還可以摻混 界面活性劑、黏合助劑、耐熱性提高劑等添加劑。 Φ 黏合助劑可以爲了進一步提高所得間隙子或保護膜與 基板的黏附性而使用。作爲這種黏合助劑，較佳係具有羧 酸基、甲基丙烯醯基、乙烯基、異氰酸酯基、環氧乙烷基 等反應性官能團的官能性矽烷偶合劑。作爲黏合助劑的具 體例子，可以r-甲基丙烯醯氧基丙基三甲氧基矽烷、τ-異氰酸酯丙基三乙氧基矽烷、7-環氧丙氧基丙基三甲氧基 矽烷、々-(3,4-環氧環己基）乙基三甲氧基矽烷等。 這種黏合助劑可以單獨或者將兩種以上混合使用。黏 合助劑的用量，相對於100質量份（A)鹼可溶性樹脂，較佳 -26- 201027249 爲0.1〜2 0質量份，更佳爲0.5〜10質量份。當黏合助劑的用 量爲0.1〜20質量份時，對於間隙子或保護膜，可以使其黏 附性達到最佳。 . 界面活性劑可以爲了進一步提高感放射線性樹脂組成 物的塗膜形成性而使用。作爲這種界面活性劑，可以列舉 例如氟類界面活性劑、聚矽氧烷類界面活性劑和其他界面 活性劑。 ^ 作爲氟類界面活性劑，較佳係末端、主鏈和側鏈的至 〇 少任一部位具有氟代烷基及/或氟代伸烷基的化合物。作爲 氟類界面活性劑的例子，可以列舉1，1,2,2-四氟正辛基 (1，1，2,2-四氟正丙基）醚、1，1，2,2-四氟正辛基（正己基）醚、 六甘醇二（1，1，2,2,3,3-六氟正戊基）醚、八甘醇二（1，1，2,2-四 氟丁基）醚、六丙二醇二（1,1，2,2,3,3 -六氟正戊基）醚、八丙 二醇二（1，1,2,2_四氟正丁基）醚、全氟正十二烷基磺酸鈉、 1，1,2,2,3,3-六氟正十二烷、1，1，2,2,3,3,9,9,10,10-十氟正十 Q 二烷、氟代烷基苯磺酸鈉、氟代烷基磷酸鈉、氟代烷基羧 酸鈉、雙甘油四（氟代烷基聚氧乙烯醚）、碘化氟代烷基銨、 氟代烷基甜菜城、其他氟代烷基聚氧乙烯醚、全氟代烷基 聚氧乙醇、全氟代烷基烷氧化物、羧酸氟代烷基酯等。 作爲氟類界面活性劑的市售品，可以列舉例如BM -1000、BM — 1100(以上，由 BMCHEMIE 公司生產）、 MEGAFAC F142D、MEGAFAC F172、MEGAFAC F173、 MEGAFAC F183、MEGAFAC F178、MEGAFAC F191、 MEGAFAC F471、MEGAFAC F476(以上，由大日本油墨化 -27- 201027249 學工業（股）生產）、FRORAID FC — 170C、FC — 171、FC — 430、 FC — 431(以上由住友 3M(股）生產）、SURFLONS—112、 SURFLON S — 1 1 3、SURFLON S - 1 3 1、SURFLON S - 14 1 ' SURFLON S — 145、SURFLON S - 382、SURFLON SC - 101、 SURFLON SC — 1 02、SURFLON SC- 103 ' SURFLON SC- 104、SURFLON SC — 105、SURFLON SC — 106(以上由旭硝 子（股）生產）、EFTOP EF 301、EFTOP EF 303、EFTOP EF 352(以上由新秋田化成（股）生產）、FT ER GENT FT — 100、 ❹ FTERGENT FT - 110、FTERGENT FT - 140A、FTERGENT FT 一 150、FTERGENT FT- 250、FTERGENT FT- 251、 FTERGENT FT- 300、FTERGENT FT— 310、FTERGENT FT -400S、FTERGENT FTX- 218、FTERGENT FTX — 251(以 上由（股）NEOS生產）等。 作爲聚矽氧烷類界面活性劑，可以列舉例如Tor ay Silicone DC 3 PA、Toray Silicone DC7PA ' To ray SiliconeArtResin UN-1 255, ArtResin UN-6060PTM, ArtResin UN-6060P (above produced by Gensei Industries Co., Ltd.), etc. (C) Inductive Radiation-Terminal Polymerization Initiator The (C) radiation-sensitive polymerization initiator contained in the radiation-sensitive resin composition of the present invention is produced by inducing radiation to cause polymerization of (B) a polymerizable unsaturated compound. The composition of the active substance. Examples of the (C) radiation-sensitive polymerization initiator include an anthracene-fluorenyl compound, an acetophenone compound, a biimidazole compound, and a benzophenone compound. Specific examples of the above fluorene-fluorenyl hydrazine compound include, for example, ethyl ketone-l-[9-ethyl-6-(2-methylbenzomethyl)-9H-carbazol-3-yl]-l -(0-ethylhydrazine), l-[9-ethyl-6-benzylidene-9.H.-r-oxazol-3-yl]-oct-1-one oxime-indole-acetate , 1-[9-ethyl-6-(2-methylbenzylidenyl)-9·Η·-oxazol-3-yl]-ethan-1-one oxime-indole-benzoate, 1 -[9-n-butyl-6-(2-ethylbenzylidene)-9.Η·-carbazole_3_yl]-ethan-1-one oxime-0-benzoate, ethyl ketone -l-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylbenzylidene)-9.Η.-carbazole-3-yl]-1-(indolyl-indenyl) Ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyran-22-201027249 benzoyl fluorenyl)-9.11.-n-oxazol-3-yl]-1- (0-ethylhydrazine), ethyl ketone-1-[9-ethyl-6-(2-methyl-5-tetrazofurylbenzopyridinyl)-9.Η.-carbazole-3- ]]-1-(〇-acetylhydrazine), ethyl ketone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxo Heterocyclic amyl)methoxybenzylidene}-9.11.-carbazole-3-yl]-1-(0-ethylindenyl) and the like. Among them, as a preferred 0-fluorenyl hydrazine compound, ethyl ketone-l-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]- 1-(0-acetamidopurine), ethyl ketone-l-[9-ethyl-6-(2-methyl-4-tetrahydrofurylmethoxybenzoquinone)-9.Η·-咔Zyrid-3-yl]-l-(0-acetamidoxime) or ethyl ketone-l-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1, 3-Dioxolyl)methoxybenzylidene}-9·Η·-oxazol-3-yl]-1-(0-ethenyl). These 0-fluorenyl ruthenium compounds may be used singly or in combination of two or more. The acetophenone compound may, for example, be an α-amino ketone compound or an α-hydroxyketone compound. Specific examples of the α-amino ketone compound include 2-benzyl hydrazine-2-dimethylamino-1-(4-morpholinylphenyl)-butan-1-one and 2-dimethyl Amino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, 2-methyl-1-(4-methylthio) Phenyl)-2-morpholinylpropan-1-one and the like. Specific examples of the α-hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropan-1-one and 1-(4-isopropylphenyl)-2-hydroxy-2-methyl. Propyl-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenyl hydrazine, and the like. Among these acetophenone compounds, α-amino ketone compounds are preferred, and 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butene-1- is particularly preferred. Ketone or -23- 201027249 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one. Specific examples of the above-mentioned diimide compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1. 2'-biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-di (2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorobenzene Base 4,4',5,5'-tetraphenyl-1,2'-biimidazole, and the like. Among these biimidazole compounds, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2, is preferred. 2'-bis(2,4-dichlorophenyl)-4,4,5,5,-tetraphenyl-1,2'-biimidazole or 2,2'-di(2,4,6 -trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, particularly preferably 2,2'-bis(2,4-dichlorophenyl) -4,4',5,5'-tetraphenyl-1,2'-biimidazole. In the radiation sensitive resin composition of the present invention, when a bisimidazole compound is used as the (C) radiation sensitive polymerization initiator, in order to enhance the sensitivity, 0 may be added with an aliphatic or aromatic group having a dialkylamine group. A compound (hereinafter referred to as "amine-based sensitizer"). Examples of such an amine-based sensitizer include 4,4'-bis(dimethylamino)benzophenone and 4,4'-di(diethylamino)benzophenone. Among these amine-based sensitizers, 4,4'-bis(diethylamino)benzophenone is particularly preferred. The above amine-based sensitizers may be used singly or in combination of two or more. Further, in the radiation sensitive resin composition of the present invention, when a bisimide, an azole compound and an amine sensitizer are used, a thiol compound as a hydrogen radical donor may be added. The biimidazole compound is sensitized by the amine-based sensitizer-24-201027249 to cleave, and the imidazole radical is generated, but does not exhibit high polymerization initiation energy by itself, and the spacer of the obtained liquid crystal display element becomes an inverted cone. The case of a shape that is not ideal. However, by adding a thiol compound to the coexistence system of the bisimidazole compound and the amine sensitizer, a hydrogen radical is supplied from the thiol compound to the imidazole radical. As a result, the imidazole radical is converted into a neutral imidazole, and at the same time, a component having a sulfur radical having a high polymerization initiation energy is produced, so that the shape of the spacer can be made into a more positive conical shape. As such a thiol compound, for example, 2-mercaptobenzothiazolidine, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole can be mentioned. An aromatic thiol compound; an aliphatic monosulfide alcohol compound such as 3-mercaptopropionic acid or methyl 3-mercaptopropionate; pentaerythritol tetrakis(mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionic acid) A bifunctional or higher aliphatic thiol compound such as an ester). Among these thiol compounds, 2-mercaptobenzothiazole is particularly preferred. When the biimidazole compound and the amine sensitizer are used, the amount of the amine sensitizer added is 0.1 to 50 parts by mass, more preferably 0.1 to 50 parts by mass, based on 1 part by mass of the bisimidazole compound. Good is 1~20 0 parts by mass. When the amount of the amine-based sensitizer added is 0.1 to 50 parts by mass, the properties of the resulting spacer can be made good. Further, when the biimidazole compound and the amine sensitizer are used together with the thiol compound, the amount of the thiol compound added is preferably 0.1 to 50 by mass based on 1 part by mass of the biimidazole compound. Parts, more preferably 1 to 2 parts by mass. When the amount of the thiol compound added is from 1 to 50 parts by mass, the properties and adhesion of the spacer can be optimized. The (c) radiation-sensitive-25-201027249 polymerization initiator contained in the radiation sensitive resin composition of the present invention preferably contains at least a group selected from the group consisting of a ruthenium-fluorenyl ruthenium compound and an acetophenone compound. More preferably, it contains at least one selected from the group consisting of a fluorene-fluorenyl compound and an acetophenone compound, and a biimidazole compound. The ratio of the ruthenium-indenyl ruthenium compound and the acetophenone compound in the (C) radiation-sensitive polymerization initiator is preferably 40% by mass or more based on the total amount of the (C) radiation-sensitive polymerization initiator. More preferably, it is 45 mass% or more, and particularly preferably 50 mass% or more. By using (C) a radiation-sensitive polymerization initiator at such a ratio, the radiation-sensitive resin composition of the present invention can form a gap having higher strength and adhesion with high sensitivity even at a low exposure amount. Sub or protective film. [Additive] The radiation sensitive resin composition of the present invention may contain an additive such as a surfactant, an adhesion aid, or a heat resistance improver, if necessary, in addition to the above components, without impairing the intended effect. The Φ adhesion aid can be used to further improve the adhesion of the resulting spacer or the protective film to the substrate. As such an adhesion aid, a functional decane coupling agent having a reactive functional group such as a carboxylic acid group, a methacryl fluorenyl group, a vinyl group, an isocyanate group or an oxiran group is preferable. Specific examples of the adhesion aid include r-methacryloxypropyltrimethoxydecane, τ-isocyanatepropyltriethoxydecane, 7-glycidoxypropyltrimethoxydecane, and ruthenium. -(3,4-epoxycyclohexyl)ethyltrimethoxydecane, and the like. Such an adhesion aid may be used singly or in combination of two or more. The amount of the adhesion aid is 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the (A) alkali-soluble resin, preferably -26 to 201027249. When the amount of the binder is 0.1 to 20 parts by mass, the adhesion can be optimized for the spacer or the protective film. The surfactant can be used to further improve the coating film formability of the radiation sensitive resin composition. As such a surfactant, for example, a fluorine-based surfactant, a polyoxyalkylene surfactant, and other surfactants may be mentioned. As the fluorine-based surfactant, a compound having a fluoroalkyl group and/or a fluoroalkylene group at any of the terminal, main chain and side chain is preferred. Examples of the fluorine-based surfactant include 1,1,2,2-tetrafluoro-n-octyl (1,1,2,2-tetrafluoro-n-propyl)ether, 1,1,2,2-tetra. Fluoryl-n-octyl (n-hexyl) ether, hexaethylene glycol di(1,1,2,2,3,3-hexafluoro-n-pentyl) ether, octaethylene glycol di(1,1,2,2-tetrafluoro Butyl)ether, hexapropanediol bis(1,1,2,2,3,3-hexafluoro-n-pentyl)ether, octapropylene glycol bis(1,1,2,2-tetrafluoro-n-butyl)ether, all Sodium fluorododecyl sulfonate, 1,1,2,2,3,3-hexafluoro-n-dodecane, 1,1,2,2,3,3,9,9,10,10- Fluorine-n-Q-dioxane, sodium fluoroalkylbenzenesulfonate, sodium fluoroalkylphosphate, sodium fluoroalkylcarboxylate, diglycerol tetra(fluoroalkylpolyoxyethylene ether), fluoroalkyl halide Alkyl ammonium, fluoroalkyl beet city, other fluoroalkyl polyoxyethylene ether, perfluoroalkyl polyoxyethylene, perfluoroalkyl alkoxide, fluoroalkyl carboxylate, and the like. Commercial products of a fluorine-based surfactant include, for example, BM-1000, BM-1100 (above, manufactured by BMCHEMIE), MEGAFAC F142D, MEGAFAC F172, MEGAFAC F173, MEGAFAC F183, MEGAFAC F178, MEGAFAC F191, MEGAFAC F471. , MEGAFAC F476 (above, produced by Dainippon Ink -27- 201027249 Industrial (share)), FRORAID FC — 170C, FC — 171, FC — 430, FC — 431 (above produced by Sumitomo 3M (shares)), SURFLONS—112, SURFLON S — 1 1 3, SURFLON S - 1 3 1, SURFLON S - 14 1 'SURFLON S — 145, SURFLON S - 382, SURFLON SC - 101, SURFLON SC — 1 02, SURFLON SC- 103 ' SURFLON SC-104, SURFLON SC — 105, SURFLON SC — 106 (above produced by Asahi Glass Co., Ltd.), EFTOP EF 301, EFTOP EF 303, EFTOP EF 352 (above produced by New Akita Chemicals Co., Ltd.), FT ER GENT FT — 100, ❹ FTERGENT FT - 110, FTERGENT FT - 140A, FTERGENT FT 150, FTERGENT FT- 250, FTERGENT FT-251, FTERGENT FT-300, FTERGENT FT-310, FTERGENT FT-400S, FTERGENT FTX-218, FTERGENT FTX — 251 (produced by (NE) NEOS) and so on. As the polyoxyalkylene type surfactant, for example, Tor ay Silicone DC 3 PA, Toray Silicone DC7PA 'To ray Silicone

SHI 1PA、Toray Silicone SH21PA、Toray Silicone SH28PA、 Toray Silicone SH29PA、Toray Silicone SH30PA、Toray Silicone SH — 190、Toray Silicone SH— 193、Toray Silicone SZ— 603 2Toray Silicone SF— 8428、Toray Silicone DC— 57、 Toray Silicone DC — 1 90(以上，由 Toray Dow Corning Silicone (股）生產）、TSF — 4440、TSF — 4300、TSF- 4445、 TSF — 4446、TSF — 4460、TSF - 4452(以上由 GE 東芝 Silicone (股）生產）、有機矽氧烷聚合物KP341(信越化學工業（股）生 產）等。 -28- 201027249 這些界面活性劑可以單獨或者將兩種以上混合使用。 界面活性劑的用量，相對於1 0 0質量份（A)鹼可溶性樹脂， 較佳爲0.1〜5質量份，更佳爲0.1 5~3質量份。當界面活性 劑的用量爲0.1〜5質量份時，可以減少塗膜不勻。 作爲耐熱性提高劑，可以列舉例如N-(烷氧基甲基）甘 脲化合物、N-(烷氧基曱基）三聚氰胺化合物等。作爲耐熱性 提高劑的較佳具體例子，可以列舉Ν,Ν,Ν’，Ν’-四（甲氧基甲 基）甘脲、^\’，：^’，『’少’’-六（甲氧基甲基）三聚氰胺。作 爲耐熱性提高劑的市售品，可以列舉例如NIKALAC N-2702、NIKALAC MW-30M(以上由（股）三和化學生產）等。 這些耐熱性提高劑，可以單獨或將兩種以上混合使 用。耐熱性提高劑的用量，相對於1 〇〇質量份（A)鹼可溶性 樹脂，較佳爲2 0質量份以下，更佳爲1 0質量份以下。當 耐熱性提高劑的用量爲20質量份以下時，具有改善感放射 線性樹脂組成物的耐熱性的傾向。 φ <感放射線性樹脂組成物的調製> 本發明的感放射線性樹脂組成物可以通過將上述（A)鹼 可溶性樹脂、（B)聚合性不飽和化合物和（C)感放射線性聚合 引發劑以及如上所述任選添加的其他成分均勻地混合而調 製。該感放射線性樹脂組成物較佳係以溶於適當的溶劑中 的溶液狀態使用。例如，可以通過將（A)鹼可溶性樹脂、（B) 聚合性不飽和化合物和（C)感放射線性聚合引發劑以及任選 添加的其他成分在溶劑中以一定的比率混合，調製出溶液 狀態的感放射線性樹脂組成物。 -29- 201027249 作爲本發明感放射線性樹脂組成物的調製中可以使用 的溶劑，使用能夠均勻地溶解（A)鹼可溶性樹脂、（B)聚合性 不飽和化合物和（C)感放射線性聚合引發劑以及任選添加的 其他成分中的各成分，並且不與各成分反應的溶劑。作爲 這樣的溶劑，可以列舉與上述作爲可以用於製備（A)鹼可溶 性樹脂的溶劑而例示的相同溶劑。 在這種溶劑中，從各成分的溶解性、與各成分的反應 性、形成塗膜的容易性等角度考慮，可特別較佳係使用例 如二甘醇單乙醚乙酸酯、二甘醇二乙醚、二甘醇乙基甲基 醚、二甘醇二甲醚、丙二醇單甲醚、乙二醇單丁醚乙酸酯、 丙二醇單甲醚乙酸酯、二丙二醇單甲醚乙酸酯、3-甲氧基丁 基乙酸酯、環己醇乙酸酯、苄基醇、3 -甲氧基丁醇。這些溶 劑可以一種單獨使用，也可以將兩種以上混合使用。 此外，爲提高膜厚的面內均勻性，還可以與上述溶劑 一起倂用高沸點溶劑。作爲可以倂用的高沸點溶劑，可以 φ 列舉例如N-甲基吡咯烷酮、N，N-二甲基乙醯胺、苄基乙基 醚、二己基醚、丙酮基丙酮、1-辛醇、1-壬醇、醋酸苄基酯、 苯甲酸乙酯、草酸二乙酯、馬來酸二乙酯、r-丁內酯、碳 酸丙二酯等。其中，較佳係N-甲基吡咯烷酮、r-丁內酯或 Ν,Ν-二甲基乙醯胺。 作爲本發明感放射線性樹脂組成物的溶劑，當倂用高 沸點溶劑時，其用量相對於全部溶劑，可以爲5 0質量％以 下，較佳係40質量％以下，更佳爲30質量％以下。當高沸 點溶劑的用量爲50質量。/。以下時，可使厚度均勻性、靈敏 -30- .201027249 度和殘膜率成爲良好。 當將本發明的感放射線性樹脂組成物配製成溶液狀態 時’固體成分濃度（溶劑以外的成分，即（A)成分、（B)成分 和（C)成分以及任選添加的其他成分的合計量在組成物溶液 中所占的比率），可以根據使用目的和所需的膜厚度値等而 設定爲任意濃度（例如5〜50質量％)。更佳係的固體含量濃 度，根據在基板上形成塗膜的方法而不同，以下將對此進 行說明。如此調製的組成物溶液還可以在用孔徑爲0.5/zm ❹ 左右的微孔濾器等過濾後再供給使用。 <間隙子或保護膜的形成方法> 接著，對用本發明感放射線性樹脂組成物形成間隙子 或保護膜的方法進行說明。 本發明間隙子或保護膜的形成方法至少按照下述順序 包括以下步驟（1 )〜（4 )。 (1) 在基板上形成本發明感放射線性樹脂組成物塗膜的 ❹ 步驟。 (2) 對該塗膜的至少一部分照射放射線的步驟。 (3) 將照射放射線後的塗膜進行顯影的步驟。 (4) 將顯影後的塗膜進行加熱的步驟。 以下，依次對這些各步驟進行說明。 (1)在基板上形成本發明感放射線性樹脂組成物塗膜的 步驟 在透明基板的一面上形成透明導電膜，再在該透明導 電膜上形成感放射線性樹脂組成物塗膜。作爲這裏所用的 -31 - 201027249 透明基板，可以列舉例如玻璃基板、樹脂基板等。更具體 地說，可以列舉例如鈉鈣玻璃、無鹼玻璃等玻璃基板；聚 對苯二甲酸乙二醇酯、聚對苯二甲酸丁二醇酯、聚醚砸、 聚碳酸酯、聚醯亞胺等塑膠製樹脂基板。 作爲透明基板一面上設置的透明導電膜，可以使用氧 化錫（Sn02)製的NESA膜（美國PPG公司註冊商標）、氧化銦 一氧化錫（Ιη203 — Sn02)製的ITO膜等。 在採用塗布法形成塗膜時，可以通過在上述透明導電 ❹ 膜上塗布感放射線性樹脂組成物溶液後，較佳係加熱塗布 面（預烘焙）而形成塗膜。塗布法中使用的組成物溶液的固體 含量濃度較佳爲5〜5〇質量％，更佳爲1〇〜40質量％，進一 步較佳爲1 5〜3 5質量％。作爲組成物溶液的塗布方法，沒有 特別的限制，可以採用例如噴塗法、輥塗法、旋轉塗布法（旋 塗法）、縫模塗布法、棒塗法、噴墨塗布法等適當的方法。 這些塗布方法中，特別較佳係旋塗法或縫模塗布法。 Q 採用上述方法形成的塗膜，較佳係接著進行預烘焙。 預烘焙條件根據各成分的種類、配合比率等而不同，較佳 係在70~ 120°C下進行1〜15分鐘左右。塗膜預烘焙後的厚 度，較佳爲0.5~10/zm，更佳爲l.〇~7.0ym。 (2)對該塗膜的至少一部分照射放射線的步驟 接著，對所形成的塗膜的至少一部分照射放射線。此 時’在僅對塗膜的一部分進行照射時，通常採用通過具有 預定圖案的光罩進行照射的方法。 作爲照射時使用的放射線，可以使用可見光、紫外線、 -32- 201027249 遠紫外線等。較佳係波長處於2 5 0〜5 5 Onm範圍的放射線， 特別較佳係含3 65nm紫外線的放射線。 放射線照射量（曝光量），作爲照射的放射線波長爲 365nm時的強度採用照度計（OAI 356型，Optical Associates Inc.製造）測定的値，較佳爲100〜5000 J/m2,更佳爲200~3000 J/m2。 本發明感放射線性樹脂組成物，與以前已知的組成物 相比，具有放射線敏感性高，即使放射線照射量爲700J/m2 ❿ 以下，甚至是600J/m2以下，也能夠獲得具有預期膜厚、良 好形狀、優良的黏附性和高硬度的間隙子或保護膜的優點。 (3) 將照射放射線後的塗膜進行顯影的步驟 接著，通過對照射放射線後的塗膜進行顯影，除去不 要的部分，形成預定的圖案。 作爲顯影時使用的顯影液，可以使用例如氫氧化鈉、 氫氧化鉀、碳酸鈉等無機鹼；氫氧化四甲基銨、氫氧化四 Q 乙基銨等四級銨鹽等鹼性化合物的水溶液。上述鹼性化合 物的水溶液中還可以添加適量的甲醇、乙醇等水溶性有機 溶劑及/或界面活性劑而使用。 作爲顯影方法、盛液法、浸漬法、沖洗法等任意一者 均可，較佳係常溫下爲10〜180秒鐘。繼顯影處理之後，通 過例如進行30〜90秒的流水沖洗後，採用壓縮空氣或壓縮 氮氣進行風乾，獲得所需的圖案。 (4) 將顯影後的塗膜進行加熱的步驟。 接著，通過採用加熱板、烘箱等適當的加熱裝置，在 -33- 201027249 預定的溫度如100〜250°c下，對所得圖案狀塗膜加熱（後烘 焙）預定的時間’例如，在加熱板上進行5〜3 〇分鐘，而在烘 箱中則進行30〜180分鐘，即可製得所需的間隙子或保護膜。 如上進行操作’可以以所需的尺寸獲得壓縮強度、對 液晶配向膜的打磨步驟的耐受性、與基板的黏附性等各種 性能優良的間隙子或保護膜。 <液晶顯示元件> 本發明的液晶顯示元件可以通過例如以下的方法（3)或SHI 1PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH - 190, Toray Silicone SH-193, Toray Silicone SZ-603 2Toray Silicone SF-8428, Toray Silicone DC-57, Toray Silicone DC — 1 90 (above, produced by Toray Dow Corning Silicone), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 (above by GE Toshiba Silicone) Production), organic siloxane polymer KP341 (Shin-Etsu Chemical Co., Ltd. production) and so on. -28- 201027249 These surfactants may be used singly or in combination of two or more. The amount of the surfactant used is preferably 0.1 to 5 parts by mass, more preferably 0.15 to 3 parts by mass, per 100 parts by mass of the (A) alkali-soluble resin. When the amount of the surfactant is 0.1 to 5 parts by mass, the unevenness of the coating film can be reduced. The heat resistance improving agent may, for example, be an N-(alkoxymethyl)glycol compound or an N-(alkoxymethyl)melamine compound. As a preferable specific example of the heat resistance improving agent, Ν, Ν, Ν', Ν'-tetrakis(methoxymethyl) glycoluril, ^\', :^', "'less''-six" Methoxymethyl) melamine. As a commercial item of the heat resistance improving agent, for example, NIKALAC N-2702, NIKALAC MW-30M (the above is produced by Chemicals Co., Ltd.), and the like can be mentioned. These heat resistance improvers may be used singly or in combination of two or more. The amount of the heat-resistant improver is preferably 20 parts by mass or less, more preferably 10 parts by mass or less based on 1 part by mass of the (A) alkali-soluble resin. When the amount of the heat resistance improving agent is 20 parts by mass or less, the heat resistance of the radiation sensitive linear resin composition tends to be improved. φ <Preparation of Radiation-sensitive Resin Composition> The radiation-sensitive resin composition of the present invention can be initiated by the above-mentioned (A) alkali-soluble resin, (B) polymerizable unsaturated compound, and (C) radiation-sensitive polymerization. The agent and other components optionally added as described above are uniformly mixed and prepared. The radiation sensitive resin composition is preferably used in the form of a solution dissolved in a suitable solvent. For example, the solution state can be prepared by mixing (A) an alkali-soluble resin, (B) a polymerizable unsaturated compound, and (C) a radiation-sensitive polymerization initiator and optionally other components in a solvent at a certain ratio. A radiation sensitive resin composition. -29- 201027249 As a solvent which can be used for preparation of the radiation sensitive resin composition of the present invention, it is possible to uniformly dissolve (A) an alkali-soluble resin, (B) a polymerizable unsaturated compound, and (C) a radiation-induced polymerization. a solvent and a solvent which does not react with each component of the other components which are optionally added. As such a solvent, the same solvent as exemplified above as a solvent which can be used for the preparation of the (A) alkali-soluble resin can be mentioned. In such a solvent, it is particularly preferable to use, for example, diethylene glycol monoethyl ether acetate or diethylene glycol from the viewpoints of solubility of each component, reactivity with each component, easiness of formation of a coating film, and the like. Ether, diethylene glycol ethyl methyl ether, diglyme, propylene glycol monomethyl ether, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, cyclohexanol acetate, benzyl alcohol, 3-methoxybutanol. These solvents may be used singly or in combination of two or more. Further, in order to increase the in-plane uniformity of the film thickness, a high boiling point solvent may be used together with the above solvent. As a high-boiling solvent which can be used, for example, N-methylpyrrolidone, N,N-dimethylacetamide, benzylethyl ether, dihexyl ether, acetonylacetone, 1-octanol, 1 can be enumerated. - decyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, r-butyrolactone, propylene carbonate, and the like. Among them, preferred are N-methylpyrrolidone, r-butyrolactone or hydrazine, hydrazine-dimethylacetamide. When the high-boiling solvent is used as the solvent of the radiation-sensitive resin composition of the present invention, the amount thereof may be 50% by mass or less, preferably 40% by mass or less, and more preferably 30% by mass or less based on the total of the solvent. . When the amount of the high boiling point solvent is 50 mass. /. In the following, thickness uniformity, sensitivity -30-.201027249 degrees, and residual film ratio can be made good. When the radiation sensitive resin composition of the present invention is formulated into a solution state, the solid content concentration (components other than the solvent, that is, the components (A), (B), and (C), and optionally other components are added. The ratio of the total amount in the composition solution can be set to an arbitrary concentration (for example, 5 to 50% by mass) depending on the purpose of use, the desired film thickness, and the like. A more preferable solid content concentration differs depending on the method of forming a coating film on the substrate, which will be described below. The composition solution thus prepared can also be used after being filtered by a micropore filter having a pore diameter of about 0.5/zm Torr or the like. <Method of Forming Gap or Protective Film> Next, a method of forming a gap or a protective film using the radiation sensitive resin composition of the present invention will be described. The method of forming the spacer or the protective film of the present invention includes the following steps (1) to (4) at least in the following order. (1) A step of forming a coating film of the radiation sensitive resin composition of the present invention on a substrate. (2) A step of irradiating at least a part of the coating film with radiation. (3) A step of developing a coating film after irradiation with radiation. (4) A step of heating the developed coating film. Hereinafter, each of these steps will be described in order. (1) Step of forming a coating film of the radiation sensitive resin composition of the present invention on a substrate A transparent conductive film is formed on one surface of a transparent substrate, and a radiation-sensitive resin composition coating film is formed on the transparent conductive film. The -31 - 201027249 transparent substrate used herein may, for example, be a glass substrate or a resin substrate. More specifically, a glass substrate such as soda lime glass or alkali-free glass; polyethylene terephthalate, polybutylene terephthalate, polyether oxime, polycarbonate, poly phthalate A plastic resin substrate such as an amine. As the transparent conductive film provided on one surface of the transparent substrate, a NESA film made of tin oxide (Sn02) (registered trademark of PPG, USA), an ITO film made of indium tin oxide (Mn 203-Sn02), or the like can be used. When the coating film is formed by the coating method, the coating film can be formed by applying a radiation-sensitive resin composition solution to the transparent conductive film, preferably by heating the coating surface (prebaking). The solid content concentration of the composition solution used in the coating method is preferably from 5 to 5 % by mass, more preferably from 1 to 40% by mass, still more preferably from 1 5 to 35% by mass. The coating method of the composition solution is not particularly limited, and an appropriate method such as a spray coating method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, or an inkjet coating method can be employed. Among these coating methods, a spin coating method or a slit die coating method is particularly preferable. Q The coating film formed by the above method is preferably subjected to prebaking. The prebaking conditions vary depending on the type of each component, the blending ratio, etc., and are preferably carried out at 70 to 120 ° C for about 1 to 15 minutes. The thickness of the coating film after prebaking is preferably 0.5 to 10/zm, more preferably 1.1 to 7.0 ym. (2) Step of irradiating at least a part of the coating film with radiation Next, at least a part of the formed coating film is irradiated with radiation. At this time, when only a part of the coating film is irradiated, a method of irradiating with a mask having a predetermined pattern is usually employed. As the radiation used for the irradiation, visible light, ultraviolet light, -32-201027249 far ultraviolet ray or the like can be used. Radiation having a wavelength in the range of 2 5 0 to 5 5 Onm is preferable, and radiation having ultraviolet rays of 3 65 nm is particularly preferable. The amount of radiation (exposure amount) is 値 measured by an illuminometer (Model OAI 356, manufactured by Optical Associates Inc.) as the intensity at which the radiation wavelength of the irradiation is 365 nm, preferably 100 to 5000 J/m2, more preferably 200. ~3000 J/m2. The radiation sensitive resin composition of the present invention has high radiation sensitivity as compared with the conventionally known composition, and can have an expected film thickness even when the radiation irradiation amount is 700 J/m 2 ❿ or less, or even 600 J/m 2 or less. Good shape, excellent adhesion and high hardness of the gap or protective film. (3) Step of developing the coating film after irradiation with radiation Next, the coating film after irradiation with radiation is developed to remove unnecessary portions, thereby forming a predetermined pattern. As the developing solution used for development, for example, an inorganic base such as sodium hydroxide, potassium hydroxide or sodium carbonate; or an aqueous solution of a basic compound such as a tetrabasic ammonium salt such as tetramethylammonium hydroxide or tetrakis(ethylammonium hydroxide); . An aqueous solution of the above basic compound may be added with an appropriate amount of a water-soluble organic solvent such as methanol or ethanol and/or a surfactant. Any one of the development method, the liquid-filling method, the dipping method, and the rinsing method may be used, and it is preferably 10 to 180 seconds at normal temperature. After the development treatment, it is subjected to running water washing for, for example, 30 to 90 seconds, and then air-dried with compressed air or compressed nitrogen gas to obtain a desired pattern. (4) A step of heating the developed coating film. Next, the obtained pattern-like coating film is heated (post-baked) for a predetermined time by a suitable heating means such as a hot plate, an oven, or the like at a predetermined temperature of -33 to 201027249, for example, 100 to 250 ° C. The above is carried out for 5 to 3 minutes, and in the oven for 30 to 180 minutes, the desired gap or protective film can be obtained. As described above, it is possible to obtain a spacer or a protective film excellent in various properties such as compressive strength, resistance to the polishing step of the liquid crystal alignment film, and adhesion to a substrate in a desired size. <Liquid Crystal Display Element> The liquid crystal display element of the present invention can be, for example, the following method (3) or

G (b)製作。 (a) 首先，準備一對（兩塊）單面上具有透明導電膜（電極） 的透明基板，在其中一塊基板的透明導電膜上，採用本發 明的感放射線性樹脂組成物，按照上述方法形成間隙子或 保護膜或者兩者。接著在這些基板的透明導電膜和間隙子 或保護膜上形成具有液晶配向能的配向膜。以其形成配向 膜的一側面作爲內側’將這些基板通過一定的間隙（晶胞間 Q 隙）相對地設置，使各自配向膜的液晶配向方向相互垂直或 逆平行，向由基板表面（配向膜）和間隙子圍成的晶胞間隙內 塡充液晶，密封塡充孔，以構成液晶胞。然後，在液晶胞 的兩外表面上貼合偏光板，使其偏光方向與該基板一面上 形成的配向膜的液晶配向方向一致或者垂直，即可製得本 發明的液晶顯示元件。 (b) 首先，預製一對與上述方法（a)同樣地形成了透明導 電膜、間隙子或保護膜或兩者、以及配向膜的透明基板。 然後沿一塊基板的端部’用分配器塗布紫外線硬化型密封 -34- 201027249 劑’然後用液晶分配器滴下微小液滴狀的液晶，在真空下 進行兩基板的貼合。然後採用高壓汞燈對上述密封劑部位 照射紫外線，將兩塊基板封閉。最後，在液晶胞的兩外表 面上貼合偏光板，即可製得本發明的液晶顯示元件。 作爲上述各方法中使用的液晶，可以列舉例如向列型 液晶、碟狀型液晶。另外，作爲液晶胞外側使用的偏光板， 可以列舉將聚乙烯醇延伸配向同時吸收碘的稱作爲“ Η 膜”的偏光膜夾在醋酸纖維保護膜中而製成的偏光板或者 ❹ Η膜自身製成的偏光板等。 實施例 以下，例示製備例、合成例、實施例來對本發明進行 更具體的說明，但是本發明並不局限於以下的記載內容。 在以下的合成例中，共聚物重量平均分子量Mw的測定 是採用下述裝置和條件，採用凝膠滲透色譜（GPC)進行的。 裝置：GPC — 101(昭和電工（股）製造） .柱：結合 GPC — KF— 801、GPC — KF— 802、GPC—KF —803 和 GPC - KF - 804。 流動相：四氫呋喃 <(A)鹼可溶性樹脂（共聚物）的合成例> 合成例1 向裝有冷凝管和攪拌器的燒瓶中，加入6質量份2,2’-偶氮二（2,4-二甲基戊腈）和220質量份二甘醇甲基乙基醚。 繼續加入12質量份甲基丙嫌酸、5質量份苯乙烯、38質量 份甲基丙烯酸三環[5·2·1·〇2,6]癸烷-8-基酯和4〇質量份甲基 -35- 201027249 丙烯酸縮水甘油酯，用氮氣置換。再向其中加入5質量份 1,3-丁二烯，邊緩慢攪拌，邊使溶液的溫度升至70°C，保持 該溫度5小時進行聚合，得到含共聚物（A - 1 )的溶液。所得 共聚物溶液的固體含量濃度（共聚物的重量占聚合物溶液總 重量的比率）爲31.1%，共聚物（A—1)的重量平均分子量Mw 爲 8500 。 合成例2 向裝有冷凝管和攪拌器的燒瓶中，加入6質量份2,2’- 〇 偶氮二（2,4-二甲基戊腈）和220質量份3-甲氧基丙酸甲酯。 繼續加入10質量份甲基丙烯酸、5質量份苯乙烯、15質量 份甲基丙烯酸三環[5.2.1 ·02’6]癸烷-8-基酯、40質量份甲基 丙烯酸縮水甘油酯、25質量份甲基丙烯酸四氫糠基酯和2 質量份季戊四醇四（3-锍基丙酸酯），用氮氣置換。然後，向 其中加入5質量份1,3-丁二烯，邊緩慢攪拌，邊使溶液的溫 度升至7(TC，保持該溫度5小時進行聚合，得到含共聚物 Q (A- 2)的溶液。所得共聚物溶液的固體含量濃度（共聚物的 重量占聚合物溶液總重量的比率）爲31.6%，共聚物（A — W 的重量平均分子量Mw爲9600。 合成例3 向裝有冷凝管和攪拌器的燒瓶中，加入5質量份2, 偶氮二（異丁腈）和250質量份醋酸3-甲氧基丁基酯，繼續加 入18質量份甲基丙烯酸、25質量份甲基丙烯酸三環 [5.2.1.02’6]癸烷-8-基酯、5質量份苯乙烯、30質量份甲基 丙烯酸2-羥基乙基酯和22質量份甲基丙烯酸苄基酯’用氣 -36- 201027249 氣置換。接著，邊緩慢攪拌，邊使溶液的溫度升至70°c ’ 保持該溫度5小時進行聚合，得到固體含量濃度爲28· 8%的 共聚物[α — 1]的溶液。對所得共聚物[α — 1]通過GPC(凝 膠滲透色譜）HLC— 8020(商品名，TOSOH(股）製造）測定 Mw，爲 1 3000。 然後，向共聚物[α—l]溶液中，加入12質量份3 -甲基 丙烯醯氧基乙基異氰酸酯KARENZ ΜΟΙ(商品名’由昭和電 工（股）生產）和0.1質量份4-甲氧基苯酚後，在下攪拌 ❹ π .1小時，再在60°C下攪拌2小時使其進行反應。採用IR(紅 外線吸收）光譜確認來自於3-甲基丙烯醯氧基乙基異氰酸酯 的異氰酸酯基與來自於共聚物[α -1]的羥基的反應的進 行。在共聚物溶液[α - 1]、反應1小時後的溶液以及在40 t下反應1小時後再在60 °C下反應了 2小時的溶液的各自 的IR光譜中，確認了來自於3-甲基丙烯醯氧基乙基異氰酸 酯的異氰酸酯基的22 7 0cm·1附近的波峰減少。經上述反應 Q 完成後，得到固體含量濃度爲31.0%的聚合物[A]的溶液。 這裏所得的聚合物[A]作爲聚合物[A- 3] 實施例1〜9、比較例1〜6 <感放射線性樹脂組成物的調製> 將表1中所示種類和用量的（A)鹼可溶性樹脂（共聚 物）、（B)聚合性不飽和化合物、（C)感放射線性聚合引發劑 進行混合，再混合作爲黏合助劑的2.5質量份r -環氧丙氧 基丙基三甲氧基矽烷、作爲界面活性劑的0.3質量份FTX —218(商品名，（股）NE〇S生產），向其中加入丙二醇單甲醚 -37- 201027249 乙酸酯，使固體含量濃度爲30質量％，然後用孔徑爲0.5 V m 的微孔濾器過濾，分別調製出感放射線性樹脂組成物溶 液。另外，（A)鹼可溶性樹脂以含有表1中所示的共聚物或 共聚物的溶液（上述合成例1〜3中任一者中製得的）的形式 添加，其所含的共聚物或聚合物的量爲表1中所示的量。 <感放射線性樹脂組成物溶液的評價> 如上調製的感放射線性樹脂組成物的評價如下進行。 評價結果列於表2。 〇 (I) 顯影性評價 在無鹼玻璃基板上通過分別通過旋塗法塗布感放射線 性樹脂組成物的溶液，在8 0 °C的加熱板上預烘焙3分鐘， 形成感放射線性樹脂組成物的塗膜（膜厚4.0// m)。在所得 塗膜上，設置各自具有多個直徑爲8〜25 m範圍的大小不 同的圓形殘存圖案的光罩。此時，在塗膜表面與光罩之間 設置預定的間隙（曝光間隙）。接著，採用高壓汞燈以 φ 1 000J/m2的曝光量通過上述光罩對塗膜進行放射線照射。 然後’用濃度爲0.05質量％的氫氧化鉀水溶液通過沖洗法 在25 °C下顯影20秒鐘後，用純水進行1分鐘清洗，再在烘 箱中於23 0°C下後烘焙20分鐘，形成圖案狀薄膜。此時， 當形成的圓形圖案以外的部分沒有殘留顯影殘渣時，顯影 性評價爲良好（〇）’殘留了顯影殘渣時，顯影性評價爲不良 (X) ° (II) 靈敏度的評價 通過具有多個直徑爲15；czm的圓形.圖案的光罩，除了 -38- 201027249 以曝光時間作爲變數以外，與上述“π)顯影性評價”同樣 地在基板上形成圓形殘存圖案。採用鐳射顯微鏡（KEYENCE 製造的VK — 8 500)測定該殘存圖案的顯影前後的高度。將這 些値應用於下述式中，求出殘膜率（％)。 殘膜率（％) =(顯影後高度/顯影前高度）xl〇〇 以殘膜率爲90%以上的曝光量作爲靈敏度。當曝光量爲 700J/m2以下時，靈敏度可評爲良好。 (III) 壓縮性能的評價 〇 與上述“（II)靈敏度的評價”同樣地，以使殘膜率爲 90%以上的曝光量在基板上形成圓形殘存圖案。採用Fischer Scope H100C(Fischer Instruments 製造），使用邊長 50仁 m 的正方形平面壓頭，通過5 OmN的負重對該圖案狀薄膜進行 壓縮試驗，測定壓縮變形量。若壓縮變形量的値爲0.5/zm 以下，則可認爲圖案狀薄膜具有高硬度，因而壓縮性能評 價爲良好（〇），另一方面，若壓縮變形量的値大於0.5 ym， Φ 則壓縮性能評價爲不良（X)。 (IV) 黏附性評價 除了不使用殘存圖案的遮罩以外，與上述“（I)顯影性 評價”同樣地形成硬化膜。然後，採用JIS K -5400(1900)8.5的黏附性試驗中的8.5·2棋盤網格帶法進行 評價。此時，100個棋盤網格中殘留的棋盤網格數目如表2 中所示。 (V) 耐化學試劑性的評價 除了不使用殘存圖案的遮罩以外，與上述“（I)顯影性 -39- 201027249 評價”同樣地形成硬化膜。採用觸針式膜厚測定機 (Alpha-Step IQ，KLA TENCOR社製造）測定該薄膜的厚度 (浸漬前的厚度），然後將帶有該薄膜的基板在升溫至6〇°C 的配向膜剝離液（三洋化成工業（股）生產的“ ChemiClean TS— 204”）中浸漬15分鐘，用水洗滌後，在烘箱中於120 °C下乾燥1 5分鐘後，測定膜厚（浸漬後的膜厚），將兩種進 行比較。將由下述式求出膜厚變化率作爲耐化學試劑性的 値。 ® 膜厚變化率（％)=(浸漬後的膜厚/浸漬前的膜厚）xl〇〇 (VI)耐打磨性的評價 除了顯影時間爲60秒以外，與上述“（I)顯影性評價” 同樣地在基板上形成圓形圖案。採用液晶配向膜塗布用印 刷機將作爲液晶配向劑的AL 3046(商品名，JSR(股）生產） 塗布在該圖案上後，在180 °C下加熱1小時，形成膜厚爲 0.05 的液晶配向劑的塗膜。然後，採用裝有纏繞了聚醯 胺製的布的輥的打磨機，以輥的回轉速爲500rpm，操作臺 ® 移動速率爲1 cm/秒的條件，對該液晶配向劑塗膜進行打磨 處理。此時，對由15/zm圓形殘存圖案形成的圖案，調査 有無圖案的脫落或削除。 ‘（VII)電壓保持率的評價 採用旋塗機分別將感放射線性樹脂組成物溶液塗布在 表面上形成了防止鈉離子溶出的Si02膜、並且以規定形狀 蒸鍍了 ITO(銦-氧化錫合金）電極的鈉鈣玻璃基板上後，在 9 〇°C的潔淨烘箱中進行丨〇分鐘預烘焙，形成感放射線性樹 脂組成物塗膜（膜厚爲2.0 # m)。不使用光罩，對該塗膜以 -40- 201027249 100】/m2的曝光量放射線照射。然後，用0.04質量％氫氧化 鉀水溶液通過浸漬法在23 °C下進行1分鐘顯影後，用純水 進行1分鐘洗滌，再在烘箱中於230 °C下進行30分鐘後烘 焙，形成硬化膜。 採用混合了 〇.8mm玻璃珠的密封劑，使硬化膜與ITO 膜相對向，將具有該硬化膜的基板與僅僅形成了 Si02膜和 ITO電極的基板進行貼合，然後向其間隙中注入液晶MLC 6608(商品名，MERCK生產），製作出液晶胞。將該液晶胞 © 置入6 0 °C的恆溫層中，採用液晶電壓保持率測定系統 “ VHR — 1 A型”（商品名，東陽TECHNICA(股）製造）測定液 晶胞的電壓保持率。此時施加的電壓爲5.5 V的方形波，測 定頻率爲60Hz。這裏，電壓保持率以由下述式計算的値而 測定。 電壓保持率（％)= (16.7毫秒後的液晶胞電位差/0毫秒 時施加的電壓）xi〇〇。 若液晶胞的電壓保持率爲90%以下，則液晶胞不能使所 ® 施加的電壓在預定水準下保持1 6 · 7毫秒，因而不能使液晶 充分地配向，產生殘像等“燒屏”的可能性大。 (VIII)保持穩定性的評價 調製出感放射線性樹脂組成物溶液後，測定各溶液在 2 5 °C下的黏度。在將感放射線性樹脂組成物溶液於25 °C下 保存時，每天測定黏度（測定溫度爲25 °C )，觀測相對於起 初測定的黏度，黏度增加率超過時所需要的天數。當黏 度增加率超過5%時需要20天以上時，保存穩定性可評價爲 良好。 -41 - 201027249 表1G (b) production. (a) First, a pair of (two) transparent substrates having a transparent conductive film (electrode) on one side are prepared, and on the transparent conductive film of one of the substrates, the radiation sensitive resin composition of the present invention is used, according to the above method A gap or a protective film or both is formed. Next, an alignment film having a liquid crystal alignment energy is formed on the transparent conductive film and the spacer or the protective film of these substrates. The substrate is formed on one side of the alignment film as a medial portion. The substrates are disposed oppositely through a certain gap (inter-cell Q gap) such that the liquid crystal alignment directions of the respective alignment films are perpendicular or antiparallel to each other, toward the surface of the substrate (alignment film). And the cell gap formed by the gap is filled with liquid crystal, and the hole is sealed to form a liquid crystal cell. Then, a polarizing plate is bonded to both outer surfaces of the liquid crystal cell so that the polarizing direction thereof coincides with or perpendicular to the liquid crystal alignment direction of the alignment film formed on one side of the substrate, whereby the liquid crystal display element of the present invention can be obtained. (b) First, a pair of transparent substrates in which a transparent conductive film, a spacer or a protective film or both, and an alignment film are formed in the same manner as in the above method (a) are preformed. Then, the ultraviolet curable seal -34 - 201027249 was applied to the end portion of one of the substrates by a dispenser, and then the liquid droplets were dropped by a liquid crystal dispenser, and the bonding of the two substrates was carried out under vacuum. Then, the above-mentioned sealant portion is irradiated with ultraviolet rays using a high-pressure mercury lamp to close the two substrates. Finally, the liquid crystal display element of the present invention can be obtained by laminating a polarizing plate on both outer surfaces of the liquid crystal cell. The liquid crystal used in each of the above methods may, for example, be a nematic liquid crystal or a disk-shaped liquid crystal. In addition, as a polarizing plate to be used for the outer side of the liquid crystal cell, a polarizing film called a "ruthenium film" in which polyvinyl alcohol is extended to simultaneously absorb iodine, which is sandwiched between a cellulose acetate protective film, or a bismuth film itself may be used. A polarizing plate or the like is produced. EXAMPLES Hereinafter, the present invention will be specifically described by way of Preparation Examples, Synthesis Examples and Examples, but the present invention is not limited to the following description. In the following synthesis examples, the measurement of the weight average molecular weight Mw of the copolymer was carried out by gel permeation chromatography (GPC) using the following apparatus and conditions. Device: GPC — 101 (made by Showa Denko). Column: Combines GPC — KF — 801, GPC — KF — 802, GPC — KF — 803 and GPC - KF - 804. Mobile phase: tetrahydrofuran <(A) Synthesis example of alkali-soluble resin (copolymer)> Synthesis Example 1 To a flask equipped with a condenser and a stirrer, 6 parts by mass of 2,2'-azobis (2) was added. , 4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol methyl ethyl ether. Continue to add 12 parts by mass of methacrylic acid, 5 parts by mass of styrene, 38 parts by mass of tricyclo[5·2·1·〇2,6]decane-8-yl methacrylate and 4 parts by mass of A Base-35- 201027249 Glycidyl acrylate, replaced with nitrogen. Further, 5 parts by mass of 1,3-butadiene was added thereto, and the temperature of the solution was raised to 70 ° C while stirring slowly, and the temperature was maintained for 5 hours to carry out polymerization to obtain a solution containing the copolymer (A - 1 ). The solid content concentration (ratio of the weight of the copolymer to the total weight of the polymer solution) of the obtained copolymer solution was 31.1%, and the weight average molecular weight Mw of the copolymer (A-1) was 8,500. Synthesis Example 2 To a flask equipped with a condenser and a stirrer, 6 parts by mass of 2,2'-fluorenyl azobis(2,4-dimethylvaleronitrile) and 220 parts by mass of 3-methoxypropionic acid were placed. Methyl ester. 10 parts by mass of methacrylic acid, 5 parts by mass of styrene, 15 parts by mass of tricyclo[5.2.1 ·02'6]nonane-8-yl methacrylate, and 40 parts by mass of glycidyl methacrylate, 25 parts by mass of tetrahydrofurfuryl methacrylate and 2 parts by mass of pentaerythritol tetrakis(3-mercaptopropionate) were replaced with nitrogen. Then, 5 parts by mass of 1,3-butadiene was added thereto, and the temperature of the solution was raised to 7 (TC while stirring slowly, and polymerization was carried out for 5 hours to obtain a copolymer Q (A-2). The solution had a solid content concentration (ratio of the copolymer to the total weight of the polymer solution) of 31.6%, and the copolymer (A - W had a weight average molecular weight Mw of 9,600. Synthesis Example 3 was supplied with a condenser tube) In a flask with a stirrer, 5 parts by mass of 2, azobis(isobutyronitrile) and 250 parts by mass of 3-methoxybutyl acetate were added, and 18 parts by mass of methacrylic acid and 25 parts by mass of methacrylic acid were further added. Tricyclo[5.2.1.02'6]decane-8-yl ester, 5 parts by mass of styrene, 30 parts by mass of 2-hydroxyethyl methacrylate and 22 parts by mass of benzyl methacrylate' gas-36 - 201027249 Gas replacement. Then, while slowly stirring, the temperature of the solution was raised to 70 ° C. The temperature was maintained for 5 hours to carry out polymerization, and a solution of the copolymer [α-1] having a solid content concentration of 28.8% was obtained. The obtained copolymer [α-1] was passed through GPC (gel permeation chromatography) HLC-8020 (trade name, TOSO) H (manufactured by H) was measured for Mw as 1 3000. Then, to the copolymer [α-1] solution, 12 parts by mass of 3-methylpropenyloxyethyl isocyanate KARENZ® (trade name 'by Showa Denko” was added. (produced) and 0.1 part by mass of 4-methoxyphenol, stirred under π π. 1 hour, and further stirred at 60 ° C for 2 hours to carry out a reaction. It was confirmed by IR (infrared absorption) spectrum from 3 - the reaction of the isocyanate group of methacryloxyethyl isocyanate with the hydroxyl group derived from the copolymer [α -1]. In the copolymer solution [α - 1], the solution after 1 hour of reaction, and at 40 t In the respective IR spectra of the solution which was further reacted at 60 ° C for 2 hours after the reaction for 1 hour, it was confirmed that the isocyanate group derived from 3-methylpropenyloxyethyl isocyanate was in the vicinity of 22 7 0 cm·1. The peak was reduced. After completion of the above reaction Q, a solution of the polymer [A] having a solid content concentration of 31.0% was obtained. The polymer [A] obtained herein was used as the polymer [A-3] Examples 1 to 9 and Comparative Examples 1 to 6 <Modulation of Radiation-sensitive Resin Composition> The types shown in Table 1 Mixing with (A) an alkali-soluble resin (copolymer), (B) a polymerizable unsaturated compound, and (C) a radiation-sensitive polymerization initiator, and mixing 2.5 parts by mass of r-glycidylene as an adhesion aid Oxypropyltrimethoxydecane, 0.3 parts by mass of FTX-218 (trade name, manufactured by NE〇S) as a surfactant, to which propylene glycol monomethyl ether-37-201027249 acetate was added to make a solid The content concentration was 30% by mass, and then filtered with a micropore filter having a pore diameter of 0.5 V m to prepare a radiation-sensitive resin composition solution. Further, (A) the alkali-soluble resin is added in the form of a solution containing the copolymer or copolymer shown in Table 1 (manufactured in any of the above Synthesis Examples 1 to 3), and the copolymer or the copolymer thereof The amount of the polymer was the amount shown in Table 1. <Evaluation of Radiation-sensitive Resin Composition Solution> The evaluation of the radiation-sensitive resin composition prepared as above was carried out as follows. The evaluation results are shown in Table 2. 〇(I) Evaluation of developability The solution of the radiation-sensitive resin composition was applied onto the alkali-free glass substrate by spin coating, and prebaked on a hot plate at 80 ° C for 3 minutes to form a radiation-sensitive resin composition. Coating film (film thickness 4.0 / / m). On the resulting coating film, a reticle having a plurality of circular residual patterns each having a diameter ranging from 8 to 25 m was provided. At this time, a predetermined gap (exposure gap) is provided between the surface of the coating film and the reticle. Next, the coating film was irradiated with radiation by the above-mentioned reticle with a high pressure mercury lamp at an exposure amount of φ 1 000 J/m 2 . Then, after developing with a potassium hydroxide aqueous solution having a concentration of 0.05% by mass at 25 ° C for 20 seconds, it was washed with pure water for 1 minute, and then post-baked in an oven at 23 ° C for 20 minutes. A patterned film is formed. In this case, when the development residue is not left in the portion other than the circular pattern formed, the developability is evaluated as good (〇). When the development residue remains, the developability is evaluated as defective (X) ° (II) The sensitivity is evaluated by having A plurality of masks having a circular pattern of a diameter of 15; czm, except for the exposure time as a variable, a circular residual pattern was formed on the substrate in the same manner as the "π) developability evaluation described above. The height before and after development of the remaining pattern was measured using a laser microscope (VK-8500 manufactured by KEYENCE). These hydrazines were applied to the following formula to determine the residual film ratio (%). Residual film rate (%) = (post-development height / height before development) xl 曝光 The exposure amount of the residual film rate of 90% or more was used as the sensitivity. When the exposure amount is 700 J/m2 or less, the sensitivity can be rated as good. (III) Evaluation of compression performance 同样 In the same manner as in the above "(II) evaluation of sensitivity", a circular residual pattern was formed on the substrate with an exposure amount of a residual film ratio of 90% or more. The patterned film was subjected to a compression test using a Fischer Scope H100C (manufactured by Fischer Instruments) using a square flat head having a side length of 50 lm, and a compressive deformation was measured by a load of 5 OmN. When the enthalpy of the amount of compression deformation is 0.5/zm or less, it is considered that the pattern-like film has high hardness, and thus the compression performance is evaluated as good (〇). On the other hand, if the 压缩 of the compressive deformation amount is more than 0.5 ym, Φ is compressed. The performance was evaluated as poor (X). (IV) Adhesive evaluation A cured film was formed in the same manner as in the above-mentioned "(I) developability evaluation" except that the mask of the residual pattern was not used. Then, the evaluation was carried out by the 8.5·2 checkerboard grid method in the adhesion test of JIS K-5400 (1900) 8.5. At this time, the number of checkerboard grids remaining in the 100 checkerboard grids is as shown in Table 2. (V) Evaluation of chemical resistance The cured film was formed in the same manner as in the above-mentioned "(I) developability - 39 - 201027249 evaluation" except that the mask of the residual pattern was not used. The thickness of the film (thickness before immersion) was measured by a stylus type film thickness measuring machine (Alpha-Step IQ, manufactured by KLA TENCOR Co., Ltd.), and then the substrate with the film was peeled off at an elevated temperature of 6 ° C. The liquid ("ChemiClean TS-204" produced by Sanyo Chemical Industries Co., Ltd.) was immersed for 15 minutes, washed with water, and dried in an oven at 120 ° C for 15 minutes, and then the film thickness (film thickness after immersion) was measured. , compare the two. The film thickness change rate was determined by the following formula as a chemical resistance. ® Film thickness change rate (%) = (film thickness after immersion / film thickness before immersion) xl 〇〇 (VI) Evaluation of abrasion resistance In addition to the development time of 60 seconds, the above "(I) developability evaluation Similarly, a circular pattern is formed on the substrate. After applying AL 3046 (trade name, manufactured by JSR Co., Ltd.) as a liquid crystal alignment agent to the pattern by a printer for liquid crystal alignment film coating, the film was heated at 180 ° C for 1 hour to form a liquid crystal alignment having a film thickness of 0.05. Coating film of the agent. Then, the liquid crystal alignment agent coating film was polished by using a sanding machine equipped with a roll of a cloth made of polyamidamide at a roll rotation speed of 500 rpm and a table movement rate of 1 cm/sec. . At this time, the pattern formed by the 15/zm circular residual pattern was examined for the presence or absence of pattern detachment or removal. '(VII) Evaluation of Voltage Retention Rate Each of the sensitized linear resin composition solution was coated on the surface by a spin coater to form a SiO 2 film for preventing sodium ion elution, and ITO was deposited in a predetermined shape (indium-tin oxide alloy) After the electrode was placed on a soda lime glass substrate, it was prebaked in a clean oven at 9 ° C for a minute to form a film of a radiation sensitive resin composition (film thickness: 2.0 #m). The coating film was irradiated with radiation at an exposure amount of -40 to 201027249 100 Å/m2 without using a photomask. Then, it was developed by a dipping method at 23 ° C for 1 minute with a 0.04% by mass aqueous potassium hydroxide solution, and then washed with pure water for 1 minute, and then baked in an oven at 230 ° C for 30 minutes to form a cured film. . The sealing agent mixed with 〇.8 mm glass beads is used to make the cured film face the ITO film, and the substrate having the cured film is bonded to the substrate on which only the SiO 2 film and the ITO electrode are formed, and then liquid crystal is injected into the gap. MLC 6608 (trade name, manufactured by MERCK), and produced a liquid crystal cell. The liquid crystal cell was placed in a constant temperature layer at 60 ° C, and the liquid crystal cell retention rate measurement system "VHR - 1 A type" (trade name, manufactured by Toyo TECHNICA Co., Ltd.) was used to measure the voltage holding ratio of the liquid cell. The voltage applied at this time was a square wave of 5.5 V, and the measurement frequency was 60 Hz. Here, the voltage holding ratio is measured by enthalpy calculated by the following formula. Voltage holding ratio (%) = (liquid crystal cell potential difference after 16.7 ms / voltage applied at 0 msec) xi 〇〇. If the voltage holding ratio of the liquid crystal cell is 90% or less, the liquid crystal cell cannot maintain the voltage applied by the ® at a predetermined level for 16 7 ms, and thus the liquid crystal cannot be sufficiently aligned, resulting in "burning" of the afterimage or the like. The possibility is great. (VIII) Evaluation of retention stability After the radiation sensitive resin composition solution was prepared, the viscosity of each solution at 25 ° C was measured. When the radiation sensitive resin composition solution was stored at 25 ° C, the viscosity was measured every day (measurement temperature was 25 ° C), and the number of days required for the viscosity increase rate to exceed the viscosity measured at the beginning was observed. When it takes more than 20 days when the viscosity increase rate exceeds 5%, the storage stability can be evaluated as good. -41 - 201027249 Table 1

組成物 種類 m 鹼可i 1 KA) 容性樹 旨 成分(B) 聚合彳生不飽和化合物 成分(C) 感放射線性聚合引發劑 種 類 重量 份 種類 重量份 種類 重量份 實施 例1 S-1 A-1 100 B-2+B-6 8+120 C-1+C-2 5+10 實施 例2 S-2 A-1 100 B-3+B-6 8+120 C-1+C-2 5+10 實施 例3 S-3 A-1 100 B-4+B-6 8+120 C-1+C-2 5+10 實施 例4 S-4 A-1 100 B-3+B-6+B-7 30+80+20 C-1+C-2+C-5 10+3+1 實施 例5 S-5 A-2 100 B-3+B-6+B-8 10+105+15 C-1+C-3+C-4+C-5 10+3+1+1 實施 例6 S-6 A-3 100 B-3+B-6+B-9 12+135+7 C-1+C-3+C-5 10+3+2 實施 例7 S-7 A-1 100 B-10+B-6 8+120 C-1+C-2 5+10 實施 例8 S-8 A-1 100 B-2 70 C-1+C-2 7+20 實施 例9 S-9 A-1 100 B-2+B-12+B-6 4+4+120 C-1+C-2 5+10 比較 例1 s-1 A-1 100 B-1+B-6 8+120 C-1+C-2 5+10 比較 例2 s-2 A-1 100 B-5+B-6 8+120 C-1+C-2 5+10 比較 例3 s-3 A-1 100 B-6 128 C-1+C-2 5+10 比較 例4 s-4 A-1 100 B-11+B-6 8+120 C-1+C-2 5+10 比較 例5 s-5 A-1 100 B-12+B-6 8+120 C-1+C-2 5+10 比較 例6 s-6 A-1 100 B-13+B-6 8+120 C-1+C-2 5+10 表1中，成分（B)和（C)的簡稱分別表示以下的化合物。 (B)聚合性不飽和化合物： -42- 201027249 B_1·環氧乙烷改性的二季戊四醇六丙烯酸酯（使1莫 耳由1莫耳二季戊四醇與5莫耳環氧乙烷反應所得的化合 物’與6莫耳丙烯酸進行酯化反應而得到的化合物） Χ·丙烯酶基 ’ a+b+c+d+e+f=5 B— 2:環氧乙烷改性的二季戊四醇六丙烯酸酯（使1莫 耳由1旲耳二季戊四醇與6莫耳環氧乙烷反應所得的化合 物’與6莫耳丙烯酸進行酯化反應而得到的化合物） Χ·丙燦醯基，a+b+c+d+e+f=6 B 一 環氧乙烷改性的二季戊四醇六丙烯酸酯（使1莫 耳由1旲耳〜季戊四醇與12莫耳環氧乙院反應所得的化合 物’與6莫耳丙烯酸進行酯化反應而得到的化合物） X:丙烯醯基，a+b+c+d+e+f=12 B_4:環氧乙烷改性的二季戊四醇六丙烯酸酯（使1莫 耳由1莫耳二季戊四醇與24莫耳環氧乙烷反應所得的化合 物’與6莫耳丙烯酸進行酯化反應而得到的化合物） Q X:丙烯醯基，a+b+c+d+e+f=24 B — 5:環氧乙烷改性的二季戊四醇六丙烯酸酯（使1莫 耳由1莫耳二季戊四醇與25莫耳環氧乙烷反應所得的化合 物’與6莫耳丙烯酸進行酯化反應而得到的化合物） X -丙稀酿基，a+b+c+d+e+f=25 B— 6:二季戊四醇六丙烯酸酯（日本化藥（股）生產的 “ KAYARAD DPHA” ) B — 7: 1,9-壬二醇二丙烯酸酯（共榮社化學（股）生產的 “ LIGHT ACRYLATE 1.9 ND— A” ) -43- 201027249 B— 8:琥珀酸改性的季戊四醇三丙烯酸酯（東亞合成（股） 生產的 “ARONIXTO — 756” ) B— 9: ω-羧基聚己內酯的單丙烯酸酯（東亞合成（股）生 產的 “ARONIXM— 5300” ) Β — 10:環氧乙烷改性的二季戊四醇六甲基丙烯酸酯 (使1莫耳由1莫耳二季戊四醇與6莫耳環氧乙烷反應所得 的化合物，與6莫耳甲基丙烯酸進行酯化反應而得到的化 合物） 〇 X·甲基丙焴醯基，a+b+c+d+e+f=6 B — 11:環氧丙烷改性的二季戊四醇六丙烯酸酯（使1 莫耳由1莫耳二季戊四醇與6莫耳環氧丙烷反應所得的化 合物’與6莫耳丙烯酸進行酯化反應而得到的化合物） B — 12:環氧乙烷改性的二季戊四醇五丙烯酸酯（使1 莫耳由1莫耳二季戊四醇與6莫耳環氧乙烷反應所得的化 合物’與5莫耳丙烯酸進行酯化反應而得到的化合物） X·丙嫌醯基，a+b+c+d+e+f=6 B — 13:環氧乙烷改性的季戊四醇四丙烯酸酯（使1莫 耳由1莫耳季戊四醇與4莫耳環氧乙烷反應所得的化合 物’與4莫耳丙烯酸進行酯化反應而得到的化合物） (C)感射線性聚合引發劑 C 一 1:乙酮_ι_[9-乙基_6_(2_甲基苯甲醯基）_9H-咔唑- 3-基]-l-(0-乙酿基 gg)(Ciba Specialty Chemicals 社生產的 “IRGACUREOXE02” ) C一 2 : 2-二甲胺基_2-(4-甲基苄基）-1-(4 -嗎啉-4 -基苯 -44 - 201027249 基）-丁 -1-酮（Ciba Specialty Chemicals 公司生產的 “IRGACURE379” ) C— 3:2,2’-二（2-氯苯基）-4,4’，5,5’-四苯基-1，2’-聯二咪 唑 C 一 4 : 4,4’-二（二乙基胺基）二苯酮（胺基系增敏劑） C 一 5 : 2-锍基苯并噻唑（硫醇化合物）Composition type m alkali can be i 1 KA) Capacitive component (B) Polymerized unsaturated unsaturated compound component (C) Radiation-type linear polymerization initiator type Weight part type Weight parts Type by weight Example 1 S-1 A -1 100 B-2+B-6 8+120 C-1+C-2 5+10 Example 2 S-2 A-1 100 B-3+B-6 8+120 C-1+C-2 5+10 Example 3 S-3 A-1 100 B-4+B-6 8+120 C-1+C-2 5+10 Example 4 S-4 A-1 100 B-3+B-6 +B-7 30+80+20 C-1+C-2+C-5 10+3+1 Example 5 S-5 A-2 100 B-3+B-6+B-8 10+105+ 15 C-1+C-3+C-4+C-5 10+3+1+1 Example 6 S-6 A-3 100 B-3+B-6+B-9 12+135+7 C -1+C-3+C-5 10+3+2 Example 7 S-7 A-1 100 B-10+B-6 8+120 C-1+C-2 5+10 Example 8 S- 8 A-1 100 B-2 70 C-1+C-2 7+20 Example 9 S-9 A-1 100 B-2+B-12+B-6 4+4+120 C-1+C -2 5+10 Comparative Example 1 s-1 A-1 100 B-1+B-6 8+120 C-1+C-2 5+10 Comparative Example 2 s-2 A-1 100 B-5+B -6 8+120 C-1+C-2 5+10 Comparative Example 3 s-3 A-1 100 B-6 128 C-1+C-2 5+10 Comparative Example 4 s-4 A-1 100 B -11+B-6 8+120 C-1+C-2 5+10 Comparative Example 5 s-5 A-1 100 B-12+B-6 8+120 C-1+C-2 5+10 Comparison Example 6 s-6 A-1 100 B-13+B-6 8+1 20 C-1+C-2 5+10 In Table 1, the abbreviations of the components (B) and (C) respectively represent the following compounds. (B) Polymerizable unsaturated compound: -42- 201027249 B_1·Ethylene oxide-modified dipentaerythritol hexaacrylate (a compound obtained by reacting 1 mol of 1 mol of dipentaerythritol with 5 mol of ethylene oxide) a compound obtained by esterification with 6 moles of acrylic acid) Χ·propenyl group ' a+b+c+d+e+f=5 B— 2: ethylene oxide-modified dipentaerythritol hexaacrylate ( a compound obtained by reacting 1 mol of a compound obtained by reacting 1 mol of dipentaerythritol with 6 mol of ethylene oxide with 6 mol of acrylic acid) Χ·propylcansyl, a+b+c+d +e+f=6 B-Ethylene oxide-modified dipentaerythritol hexaacrylate (compound of 1 mol of compound obtained by reacting 1 mol of pentaerythritol with 12 mol of epoxy epoxide) with 6 mol of acrylic acid Compound obtained by the reaction) X: propylene fluorenyl group, a+b+c+d+e+f=12 B_4: ethylene oxide-modified dipentaerythritol hexaacrylate (making 1 mol by 1 mol 2 a compound obtained by reacting pentaerythritol with 24 mol of ethylene oxide to obtain a compound obtained by esterification reaction with 6 mol of acrylic acid) QX: an acrylonitrile group, a+b+c+d+e+f=24 B — 5: ethylene oxide-modified dipentaerythritol hexaacrylate (1 molar obtained by reacting 1 mol of dipentaerythritol with 25 mol of ethylene oxide) a compound obtained by esterification of 6 moles of acrylic acid) X-propanol, a+b+c+d+e+f=25 B-6: dipentaerythritol hexaacrylate (Japanese medicine ( "KAYARAD DPHA" produced by the company) B — 7: 1,9-decanediol diacrylate (“LIGHT ACRYLATE 1.9 ND—A” by Kyoeisha Chemical Co., Ltd.) -43- 201027249 B— 8: Succinic acid-modified pentaerythritol triacrylate ("ARONIXTO-756" produced by East Asia Synthetic Co., Ltd.) B-9: Monoacrylate of ω-carboxypolycaprolactone (ARONIXM-5300 produced by East Asia Synthetic Co., Ltd.) ) 10 10: Ethylene oxide-modified dipentaerythritol hexamethacrylate (a compound obtained by reacting 1 mol of 1 mol of dipentaerythritol with 6 mol of ethylene oxide, with 6 mol of methacrylic acid) a compound obtained by an esterification reaction) 〇X·methylpropyl fluorenyl, a+b+c+d+e+f=6 B — 11: propylene oxide-modified di-penta Alcohol hexaacrylate (a compound obtained by esterifying a compound obtained by reacting 1 mol of 1 mol of dipentaerythritol with 6 mol of propylene oxide) with 6 mol of acrylic acid) B-12: Ethylene oxide modification Dipentaerythritol pentaacrylate (a compound obtained by esterifying a compound obtained by reacting 1 mol of 1 molar dipentaerythritol with 6 mol of ethylene oxide with 5 mol of acrylic acid) X·c. a+b+c+d+e+f=6 B—13: ethylene oxide-modified pentaerythritol tetraacrylate (a compound obtained by reacting 1 mol of 1 molerpentaerythritol with 4 mol of ethylene oxide) (Compound obtained by esterification reaction with 4 mol acrylic acid) (C) Radiation-initiating polymerization initiator C-1: Ethylketone_ι_[9-ethyl_6_(2-methylbenzylidene)_9H- Carbazole-3-yl]-l-(0-ethyl-branched gg) ("IRGACUREOXE02" by Ciba Specialty Chemicals) C-2: 2-dimethylamino 2-(4-methylbenzyl) 1-(4-morpholine-4-ylbenzene-44 - 201027249)-butan-1-one ("IRGACURE 379" by Ciba Specialty Chemicals) C-3:2,2'-bis(2-chloro Phenyl -4,4',5,5'-tetraphenyl-1,2'-biimidazole C-4:4,4'-bis(diethylamino)benzophenone (amine-based sensitizer) C-5: 2-mercaptobenzothiazole (thiol compound)

-45 - .201027249 表2 組成 物 種類 顯影 性 靈敏 度 (J/m2) 壓 縮 性 能 黏附 性 (/100) 電壓保持率 (%) 膜厚變化率 (%) 打磨試驗中有 無脫落 保存穩定性 (25〇C) 實施例 1 S-1 〇 600 〇 100 97 >99 /firr IMI. 20天以上 實施例 2 S — 2 〇 600 〇 100 97 >99 ΤττΓ J \ \\ 20天以上 實施例 3 S-3 〇 600 〇 100 97 >99 20天以上 實施例 4 S-4 〇 600 〇 100 97 >99 >fnr Mil: j \ \\ 20天以上 實施例 5 S-5 〇 600 〇 100 97 >99 Ant. utr j\\\ 20天以上 實施例 6 S-6 〇 700 〇 100 97 >99 frrr. ttrr 20天以上 實施例 7 S — 7 〇 600 〇 100 97 >99 >fnrr ntn y i、、 20天以上 實施例 8 S-8 〇 600 〇 100 97 >99 /fnT 1111. 20天以上 實施例 9 S-9 〇 700 〇 100 97 >99 /frrr TtTT J » 20天以上 比較例 1 s—1 X 600 〇 100 97 >99 >frrf Ttrr /\\\ 20天以上 比較例 2 s—2 〇 1000 〇 100 97 >99 4nn 1IM: / *、、 20天以上 比較例 3 s —3 X 600 〇 100 97 >99 ΛντΤ TTTt? i\\\ 20天以上 比較例 4 s—4 X 600 〇 100 97 >99 ixrr Ttrr 20天以上 比較例 5 s-5 X 700 〇 100 97 >99 llll: 20天以上 比較例 6 s—6 X 800 〇 100 97 >99 /frrr Trrr j 20天以上 由表2所示的結果可知，根據本發明的含有具有特定 結構的（B)聚合性不飽和化合物的感放射線性樹脂組成物， 具有高的放射線靈敏度，能夠容易地形成強度優良的圖案 -46- .201027249 狀薄膜，同時，能夠在短的顯影時間內進行顯影。並且， 由該感放射線性樹脂組成物形成的間隙子或保護膜，對液 晶配向膜剝離液的耐久性（耐化學試劑性）、對基板的黏附 性、作爲“燒屏”指標的電壓保持率、在打磨步驟中的耐 剝離性、保存穩定性的各種性能均優良。 參考例1、2 除了使用3質量份化合物B— 3、125質量份化合物B - 6作爲（B)聚合性不飽和化合物以外，與實施例2同樣地 操作，分別調製出感放射線性樹脂組成物溶液，進行上述 (I)~(VII)各項的性能試驗（參考例1)。另外，除了使用77 質量份化合物B— 3、51質量份化合物B— 6作爲（B)聚合性 不飽和化合物以外，實施例2同樣地操作，分別調製出感 ' 放射線性樹脂組成物溶液，進行上述（I)~(VII)各項的性能試 驗（參考例2)。結果，在參考例1中，與實施例2相比，可 知顯影性稍差。另外，在參考例2中，與實施例2相比， Q 可靈敏度和壓縮性能稍差。 產業上的可應用性 本發明的感放射線性樹脂組成物，由於具有高的放射線靈 敏度，即使是低曝光量，也能夠容易地以所需的圖案尺寸 形成在顯影步驟中圖案不會脫落、強度優良的圖案狀薄 膜，並且能夠在短的顯影時間內進行顯影，因而可特別適 用於形成液晶顯示元件之間隙子或保護膜。由該感放射線 性樹脂組成物形成的間隙子或保護膜’尺寸精度、強度等 各種性能優良，可適用於液晶顯示元件。 -47- 201027249 【圖式簡單說明】 Μ 〇 【主要元件符號說明】 〇 ^\\\-45 - .201027249 Table 2 Composition Type Sensitivity (J/m2) Compressibility Adhesion (/100) Voltage Retention (%) Film Thickness Change Rate (%) Whether there is any loss of storage stability in the sanding test (25〇 C) Example 1 S-1 〇600 〇100 97 >99 /firr IMI. 20 days or more Example 2 S — 2 〇600 〇100 97 >99 ΤττΓ J \ \\ 20 days or more Example 3 S- 3 〇600 〇100 97 >99 20 days or more Example 4 S-4 〇600 〇100 97 >99 >fnr Mil: j \ \\ 20 days or more Example 5 S-5 〇600 〇100 97 &gt 99 Ant. utr j\\\ 20 days or more Example 6 S-6 〇700 〇100 97 >99 frrr. ttrr 20 days or more Example 7 S — 7 〇600 〇100 97 >99 >fnrr ntn Yi, 20 days or more Example 8 S-8 〇600 〇100 97 >99 /fnT 1111. 20 days or more Example 9 S-9 〇700 〇100 97 >99 /frrr TtTT J » More than 20 days comparison Example 1 s-1 X 600 〇100 97 >99 >frrf Ttrr /\\\ 20 days or more Comparative Example 2 s-2 〇1000 〇100 97 >99 4nn 1IM: / *,, 20 days or more Comparative example 3 s —3 X 600 〇100 97 >99 ΛντΤ TTTt? i\\\ 20 days or more Comparative Example 4 s—4 X 600 〇100 97 >99 ixrr Ttrr 20 days or more Comparative Example 5 s-5 X 700 〇100 97 >99 llll: 20 days or more Comparative Example 6 s-6 X 800 〇100 97 >99 /frrr Trrr j 20 days or more From the results shown in Table 2, it is understood that the (B) having a specific structure according to the present invention is contained. The radiation sensitive linear resin composition of the polymerizable unsaturated compound has high radiation sensitivity, and can easily form a pattern of excellent strength - 46, 201027249, and can be developed in a short development time. Further, the durability or chemical resistance of the spacer or the protective film formed of the radiation-sensitive resin composition, the adhesion to the liquid crystal alignment film peeling liquid, the adhesion to the substrate, and the voltage retention rate as an indicator of "burning" It is excellent in various properties such as peeling resistance and storage stability in the polishing step. Reference Example 1 and 2 A radiation sensitive resin composition was prepared in the same manner as in Example 2, except that 3 parts by mass of the compound B-3 and 125 parts by mass of the compound B-6 were used as the (B) polymerizable unsaturated compound. The solution was subjected to the performance test of each of the above (I) to (VII) (Reference Example 1). Further, in the same manner as in Example 2 except that 77 parts by mass of the compound B-3 and 51 parts by mass of the compound B-6 were used as the (B) polymerizable unsaturated compound, the sensible 'radioactive resin composition solution was prepared and carried out. Performance test of each of the above (I) to (VII) (Reference Example 2). As a result, in Reference Example 1, as compared with Example 2, it was found that the developability was slightly inferior. Further, in Reference Example 2, Q was slightly inferior in sensitivity and compression performance as compared with Example 2. Industrial Applicability The radiation sensitive resin composition of the present invention has high radiation sensitivity, and can be easily formed in a desired pattern size even in a low-exposure amount, and the pattern does not fall off during the development step. It is an excellent pattern-like film and can be developed in a short development time, and thus can be particularly suitably used for forming a spacer or a protective film of a liquid crystal display element. The spacer or the protective film formed of the radiation-sensitive resin composition is excellent in various properties such as dimensional accuracy and strength, and is applicable to a liquid crystal display device. -47- 201027249 [Simple description of the diagram] Μ 〇 [Main component symbol description] 〇 ^\\\

-48-48

Claims (1)

.201027249 七、申請專利範圍： 1 · 一種感放射線性樹脂組成物’其特徵係在包含（A)驗可溶 性樹脂、（B)聚合性不飽和化合物和（c)感放射線性聚合引 發劑的感放射線性樹脂組成物中，作爲（B )聚合性不飽和 化合物係含有選自下述通式（1)表示的化合物群中的至少 一種（甲基）丙烯酸酯化合物，.201027249 VII. Patent Application Range: 1 · A radiation sensitive resin composition' is characterized by containing (A) a soluble resin, (B) a polymerizable unsaturated compound, and (c) a radiation-sensitive polymerization initiator. In the radiation-based resin composition, the (B) polymerizable unsaturated compound contains at least one (meth) acrylate compound selected from the group of compounds represented by the following formula (1). (式（1)中，X各自獨立地表示氫原子、丙烯醯基、甲基丙 燒醯基中的任一者’且至少其中之一爲丙烯醯基或甲基丙 烯醯基；又，a~f爲整數，且&至f的總和爲6〜2 4)。 2 .如申請專利範圍第1項之感放射線性樹脂組成物，其中相 〇 對於100質量份的（A)鹼可溶性樹脂，通式（1)化合物的使 用比率爲5〜75質量份。 3 .如申請專利範圍第1或2項之感放射線性樹脂組成物，其 中作爲（B)聚合性不飽和化合物係至少使用通式（1)化合 物’以及不具有環氧乙烷骨架的5官能以上的（甲基）丙烯 酸酯（B — I)。 4·如申請專利範圍第3項之感放射線性樹脂組成物，其中相 對於100質量份的（A)鹼可溶性樹脂，通式（1)化合物的使 用比率爲5〜7 5質量份，並且不具有環氧乙烷骨架的5官 -49- .201027249 能以上的（甲基）丙烯酸酯（B — I)的使用比率爲50〜150質 量份。 5. 如申請專利範圍第1至4項中任一項之感放射線性樹脂組 成物，其係用於形成液晶顯示元件之間隙子或保護膜。 6. —種液晶顯示元件之間隙子或保護膜之形成方法，其係包 括： (1) 在基板上形成如申請專利範圍第1至4項中任一項之 感放射線性樹脂組成物的塗膜的步驟， 〇 (2) 對該塗膜的至少一部分照射放射線的步驟， (3) 將照射放射線後的塗膜進行顯影的步驟，和 (4) 將顯影後的塗膜進行加熱的步驟。 7 · —種液晶顯示元件之間隙子或保護膜，其係由如申請專利 範圍第6項之方法所形成的。 8 . —種液晶顯示元件，其係具有如申請專利範圍第7項之間 隙子或保護膜。 ❹ -50- 201027249 四、指定代表圖： (一) 本案指定代表圖為：無。 (二) 本代表圖之元件符號簡單說明： 〇 五、本案若有化學式時，請揭示最能顯示發明特徵的化學式：(In the formula (1), X each independently represents any one of a hydrogen atom, an acryloyl group, and a methyl propyl group; and at least one of them is an acryl fluorenyl group or a methacryl fluorenyl group; ~f is an integer, and the sum of & to f is 6~2 4). 2. The radiation sensitive resin composition of claim 1, wherein the compound of the formula (1) is used in an amount of 5 to 75 parts by mass based on 100 parts by mass of the (A) alkali-soluble resin. 3. The radiation sensitive resin composition according to claim 1 or 2, wherein (B) the polymerizable unsaturated compound is at least a compound of the formula (1) and a 5-member having no ethylene oxide skeleton The above (meth) acrylate (B - I). 4. The radiation-sensitive resin composition of claim 3, wherein the use ratio of the compound of the formula (1) is from 5 to 75 parts by mass relative to 100 parts by mass of the (A) alkali-soluble resin, and The use ratio of the (5)-49-.201027249 having an ethylene oxide skeleton to the above (meth) acrylate (B-I) is 50 to 150 parts by mass. 5. The radiation sensitive resin composition according to any one of claims 1 to 4, which is used for forming a spacer or a protective film of a liquid crystal display element. 6. A method of forming a spacer or a protective film for a liquid crystal display element, comprising: (1) forming a coating of a radiation sensitive resin composition according to any one of claims 1 to 4 on a substrate. The step of filming, (2) a step of irradiating at least a part of the coating film with radiation, (3) a step of developing a coating film irradiated with radiation, and (4) a step of heating the coating film after development. A spacer or a protective film of a liquid crystal display element formed by the method of claim 6 of the patent application. 8. A liquid crystal display element having a gap or a protective film as in the seventh aspect of the patent application. ❹ -50- 201027249 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: 〇 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention:
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