TW200537168A - Radiation sensitive resin composition for forming spacer, spacer and the forming method thereof, and liquid crystal display element - Google Patents

Radiation sensitive resin composition for forming spacer, spacer and the forming method thereof, and liquid crystal display element Download PDF

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TW200537168A
TW200537168A TW094104389A TW94104389A TW200537168A TW 200537168 A TW200537168 A TW 200537168A TW 094104389 A TW094104389 A TW 094104389A TW 94104389 A TW94104389 A TW 94104389A TW 200537168 A TW200537168 A TW 200537168A
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radiation
weight
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TW094104389A
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TWI380065B (en
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Daigo Ichinohe
Tomoko Iwabuchi
Toshihiro Nishio
Toru Kajita
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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
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
    • 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
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • 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
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • 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
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
    • 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
    • G03F7/075—Silicon-containing compounds
    • G03F7/0755—Non-macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • 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
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials For Photolithography (AREA)
  • Polymerisation Methods In General (AREA)
  • Graft Or Block Polymers (AREA)
  • Liquid Crystal (AREA)

Abstract

This invention provides a radiation sensitive composition capable of forming spacers, the said composition can inhibit the pollution of photomasking and the like result from the sublimation of radiation sensitive polymerization initiator, and does not produce foreign body in the solution, has excellent in sensitivity, resolution, sectional shape, compressive strength, rubbing resistance, and satisfactory adhesion to transparent substrate. Radiation sensitive resin composition for forming spacer comprises [A] unsaturated carboxylic acid (anhydride) and epoxy-containing unsaturated compound and copolymer containing another unsaturated compounds, [B] a polymerable unsaturated compound, and [C] a radiation sensitive polymerization initiator as shown in following formula (1) of compound as the necessary component, (R1 is alkyl, R2 and R3 are hydrogen, alkyl or benzyl, R4, R5, R7 and R8 are hydrogen, halogen, alkyl or alkoxy, R6 is halogen, alkyl, alkoxy etc.).

Description

200537168 九、發明說明： 【發明所屬之技術領域】 本發明係關於間隔物形成用放射線敏感性樹脂組合物、 間隔物及其形成方法和液晶顯示元件，更具體而言，本發 明係關於適合用來作爲形成液晶顯示面板或觸摸式面板等 顯示面板中使用的間隔物用的放射線敏感性樹脂組合物、 由該組合物形成的間隔物及其形成方法、以及具有該間隔 物的液晶顯示元件。 【先前技術】 B 以往，爲了使兩片透明基板之間的間隔（胞間隙）保持一 定，在液晶顯示元件中使用具有規定粒徑的玻璃微珠或塑 膠微珠等間隔物粒子，但是，由於這些間隔物粒子是隨機 地散佈在玻璃基板等透明基板上，因而當圖元形成區域中 存在間隔物粒子時，就會發生間隔物粒子被寫入的現象， 或者入射光發生散射，使液晶顯示元件的對比度降低等問 題。 爲了解決這些問題，人們採用光刻形成間隔物的方法。 • 這種方法是，在基板上形成放射線敏感性樹脂組合物的被 膜，通過規定的掩模進行紫外線曝光，然後顯影，形成點 狀或條紋狀的間隔物，由於可以只在圖元形成區域以外的 規定部位形成間隔物，因而基本上解決了上述的問題。 可是，在實際形成間隔物的過程中’例如採用光刻在濾 色片等中所使用的透明基板上形成間隔物的場合，往往使 用接近式曝光機。在進行這種接近式曝光時’比較理想的 方法是，在曝光所用掩模與形成了放射線敏感性樹脂組合 200537168 . 物被膜的基板之間設置一定的間隔後進行曝光，這樣就可 以按照掩模的圖案進行曝光。然而，由於在該間隔中充滿 了空氣或氮氣，使得透過掩模的開口部（透明部）的光線在 該間隙中擴散而變寬，因而出現所謂曝光比掩模圖案的設 計尺寸要寬等的問題。 爲了解決這一問題，本申請人發現並在專利文獻1中指 出，通過使用1，2-辛二酮-1-[4-(苯硫基）苯基]-2-(0-苯甲 醯基肟）作爲放射線敏感性樹脂組合物的放射線敏感性聚 φ 合引發劑，即使是進行接近式曝光，也可以忠實地再現掩 模圖案的設計尺寸，此外，可以形成強度和耐熱性等均優 異的顯示面板用間隔物。 專利文獻1 :特開200卜26 1 76 1號公報 另外，近年來，隨著液晶顯示元件的大面積化和生產率 的提高，母體玻璃基板的尺寸已從過去的680x880 mm左右 增大至l，500xl，800 mm左右。在間隔物的形成步驟中，通 常是將間隔物形成用放射線敏感性樹脂組合物塗布在透明 φ 基板上，在熱板上通過燒成來除去溶劑，然後進行曝光和 顯影，從而形成間隔物。然而，伴隨這基板的大型化，在 間隔物的形成過程中，由於放射線敏感性樹脂組合物中的 放射線敏感性聚合引發劑成分發生昇華，導致燒成爐或光 掩模受污染的問題，並引起生產節拍的降低和生產成本的 上升，因此令人擔心。 進而，本申請人在專利文獻2中指出，通過使用1-(2-溴 -4-嗎啉并苯基）-2-苄基-2-二甲胺基丁烷-1-酮或i-(3-溴-4_ 嗎咐并苯基）-2-节基-2-一甲胺基丁院-1-酮等的溴取代苯乙 200537168 ^ 酮系化合物作爲放射線敏感性樹脂組合物的放射線敏感性 聚合引發劑’可以減輕由於放射線敏感性聚合引發劑成分 的昇華所造成的燒成爐或排氣管道的污染，並能減輕在反 覆使用顯影液時所造成的設置在顯影生產線中的過濾器的 堵塞等。 專利文獻2:特開200 1 -2356 1 7號公報 可用於形成間隔物的放射線敏感性樹脂組合物通常含有 (甲基）丙烯酸酯等的聚合性不飽和化合物或具有環氧基等 φ 熱交聯性基團的化合物，因此，爲了防止在保存時發生的 聚合或交聯反應，在多數情況下都是將其作爲組合物溶液 在低於室溫的溫度下保存。然而，在專利文獻2中記載的 溴取代苯乙酮系化合物在較低溫度下保存時往往會由於再 結晶而析出，又，溴取代的苯乙酮系化合物再結晶化之組 合物溶液之溫度即使升高到室溫以上，也難以使再結晶化 之成分再溶解，它在間隔物的形成步驟中就作爲液體中的 異物而殘存下來，因此使得在塗布到基板上時引起條紋不 I 均勻或靈敏度降低等現象的可能性非常高。 然而，專利文獻1和專利文獻2中記載的化合物包括在 內，以往在形成間隔物時使用的放射線敏感性樹脂組合 物，在防止由於放射線敏感性聚合引發劑成分的昇華所造 成的燒成爐或光掩模等的污染和液體中異物的發生等方面 不夠好，因此人們強烈希望開發同時具有這些特性的放射 線敏感性樹脂組合物。 【發明內容】 本發明的任務在於提供一種間隔物用放射線敏感性樹脂 200537168 組合物，該組合物能夠抑製由於放射線敏感性聚合引發劑 成分的昇華所引起的燒成爐或光掩模等的污染、不會產生 液體中的異物，而且可以容易地形成一種具有高靈敏度和 高的圖像解析度、同時在斷面形狀、抗壓強度、耐摩擦性、 與透明基板的黏附性等各種性能均優良的間隔物；本發明 的任務還在於提供一種由上述的樹脂組合物形成的間隔物 及其形成方法、以及具有該間隔物的液晶顯示元件。 本發明的第一方面是一種間隔物形成用放射線敏感性樹 脂組合物，其特徵在於，該組合物含有： [A] (al)不飽和羧酸和/或不飽和羧酸酐、（a2)含有環氧基 的不飽和化合物與U3)其他不飽和化合物的共聚物； [B] 聚合性不飽和化合物；以及 [C] 以由下列一般式（1)表示的化合物作爲必要成分的放 射線敏感性聚合引發劑；200537168 IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to a radiation-sensitive resin composition for spacer formation, a spacer and a method for forming the same, and a liquid crystal display element. More specifically, the present invention relates to a suitable A radiation-sensitive resin composition for forming a spacer used in a display panel such as a liquid crystal display panel or a touch panel, a spacer formed from the composition, a method for forming the same, and a liquid crystal display element having the spacer. [Prior art] B In the past, in order to maintain a constant interval (cell gap) between two transparent substrates, spacer particles such as glass microspheres or plastic microspheres having a predetermined particle diameter have been used in liquid crystal display elements. These spacer particles are randomly scattered on a transparent substrate such as a glass substrate. Therefore, when the spacer particles are present in the element formation area, the phenomenon that the spacer particles are written or the incident light is scattered causes the liquid crystal display to occur. Problems such as a decrease in the contrast of the device. To solve these problems, a method of forming spacers by photolithography is used. • In this method, a coating of a radiation-sensitive resin composition is formed on a substrate, and then exposed to ultraviolet rays through a predetermined mask, followed by development, to form a dot-like or striped spacer, since it can be located only outside the element formation area. The spacers are formed at predetermined locations, and thus the above-mentioned problems are basically solved. However, when the spacer is actually formed, for example, when a spacer is formed on a transparent substrate used in a color filter or the like by photolithography, a proximity exposure machine is often used. When performing this type of proximity exposure, a more ideal method is to set a certain interval between the mask used for the exposure and the substrate on which the radiation-sensitive resin combination is formed. 200537168. The exposure can be performed according to the mask. Pattern for exposure. However, since the space is filled with air or nitrogen, the light passing through the opening (transparent part) of the mask is diffused and widened in the gap. Therefore, the so-called exposure is wider than the design size of the mask pattern. problem. In order to solve this problem, the applicant has discovered and pointed out in Patent Document 1 that by using 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (0-benzidine Oxime) As a radiation-sensitive poly (phi) initiator in a radiation-sensitive resin composition, it is possible to faithfully reproduce the design size of a mask pattern even in proximity exposure. In addition, it has excellent strength and heat resistance. Spacer for display panel. Patent Document 1: Japanese Unexamined Patent Publication No. 26 1 76 1 In addition, in recent years, as the area of liquid crystal display elements has increased and productivity has increased, the size of the mother glass substrate has increased from about 680x880 mm to 1 in the past. 500xl, about 800 mm. In the step of forming the spacer, a radiation-sensitive resin composition for spacer formation is usually coated on a transparent φ substrate, the solvent is removed by firing on a hot plate, and then exposure and development are performed to form the spacer. However, with the increase in the size of the substrate, during the formation of the spacer, the radiation-sensitive polymerization initiator component in the radiation-sensitive resin composition sublimes, leading to the problem of contamination of the firing furnace or photomask. It is worrying because it reduces the production cycle and increases the production cost. Furthermore, the applicant has pointed out in Patent Document 2 that by using 1- (2-bromo-4-morpholinophenyl) -2-benzyl-2-dimethylaminobutane-1-one or i- (3-Bromo-4_? Benzophenyl) -2-benzyl-2-monomethylaminobutan-1-one and other bromine-substituted phenethyl groups 200537168 ^ Ketone-based compounds as radiation of a radiation-sensitive resin composition Sensitive polymerization initiator 'can reduce the pollution of the firing furnace or the exhaust pipe caused by the sublimation of the radiation-sensitive polymerization initiator component, and can reduce the filtering installed in the development line when the developer is used repeatedly. Blockage of the device. Patent Document 2: Japanese Patent Application Laid-Open No. 200 1-2356 1 7 The radiation-sensitive resin composition that can be used to form a spacer generally contains a polymerizable unsaturated compound such as (meth) acrylate or has a φ thermal crosslink such as an epoxy group. A compound having a crosslinkable group is stored as a composition solution at a temperature lower than room temperature in most cases in order to prevent a polymerization or a crosslinking reaction that occurs during storage. However, the bromine-substituted acetophenone-based compound described in Patent Document 2 often precipitates due to recrystallization when stored at a low temperature, and the temperature of the composition solution of the bromine-substituted acetophenone-based compound is recrystallized. It is difficult to re-dissolve the recrystallized component even if it is elevated above room temperature, and it remains as a foreign substance in the liquid during the formation step of the spacer, so that it causes unevenness of streaks when applied to a substrate There is a high possibility of phenomena such as reduced sensitivity. However, the compounds described in Patent Documents 1 and 2 are included. The radiation-sensitive resin composition conventionally used for forming a spacer prevents a firing furnace caused by sublimation of a radiation-sensitive polymerization initiator component. Pollution such as photomasks and the generation of foreign matter in liquids are not good enough. Therefore, development of a radiation-sensitive resin composition having these characteristics is strongly desired. SUMMARY OF THE INVENTION The object of the present invention is to provide a radiation-sensitive resin 200537168 composition for a spacer, which can suppress the contamination of a firing furnace or a photomask caused by sublimation of a radiation-sensitive polymerization initiator component. No foreign matter in the liquid is generated, and it can easily form a variety of properties with high sensitivity and high image resolution, at the same time in cross-sectional shape, compressive strength, friction resistance, adhesion to transparent substrates, etc. An excellent spacer; the object of the present invention is also to provide a spacer formed from the above-mentioned resin composition, a method for forming the same, and a liquid crystal display element having the spacer. A first aspect of the present invention is a radiation-sensitive resin composition for forming a spacer, characterized in that the composition contains: [A] (al) an unsaturated carboxylic acid and / or an unsaturated carboxylic anhydride, and (a2) containing Copolymers of epoxy-based unsaturated compounds and U3) other unsaturated compounds; [B] polymerizable unsaturated compounds; and [C] radiation-sensitive polymerization using a compound represented by the following general formula (1) as an essential component Initiator

在（1)式中，R1表示碳原子數1-12的直鏈、支鏈或環狀的 烷基；R2和R3彼此獨立地表示氫原子，碳原子數1-12的 直鏈、支鏈或環狀的烷基或苄基；R4、R5、R7和R8彼此獨 立地表示氫原子；鹵素原子，碳原子數1-12的直鏈、支鏈 或環狀的烷基或者碳原子數1-4的直鏈或支鏈狀的烷氧 200537168 ^ 基；R6表示鹵素原子，碳原子數1-12的直鏈、支鏈或環狀 的烷基，經選自羥基和碳原子數1 -4的直鏈或支鏈狀的烷 氧基組成之群的取代基所取代的碳原子數1 -1 2的直鏈、支 鏈或環狀的烷基，碳原子數1-4的直鏈或支鏈狀的烷氧基， 或者經選自羥基和碳原子數1-4的直鏈或支鏈狀的烷氧基 組成之群的取代基所取代的碳原子數2-4的直鏈或支鏈狀 的烷氧基。 本發明中所謂之“放射線”是指包括紫外線、遠紫外 0 線、X射線、電子射線、分子射線、7射線、同步加速器 輻射線、質子束射線等在內的各種射線。 本發明的第二方面是由上述的間隔物形成用放射線敏感 性樹脂組合物形成的間隔物構成。 本發明的第三方面是由間隔物的形成方法構成，其特徵 在於，該方法至少包含下述（1)〜（4)的步驟： (1)在基板上形成申請專利範圍第1項中記載的間隔物形 成用放射線敏感性樹脂組合物的被膜的步驟； $ (2)對該被膜的至少一部分用放射線進行曝光的步驟； (3) 將曝光後的上述被膜顯影的步驟； (4) 將顯影後的上述被膜加熱的步驟。 本發明的第四方面是由具有上述間隔物的液晶顯示元件 構成。 【實施方式】 <間隔物用放射線敏感性樹脂組合物> 下面對本發明的間隔物用放射線敏感性樹脂組合物（以 下簡稱“放射線敏感性樹脂組合物”）進行詳細描述。 -10- 200537168 共聚物[A ] 在本發明的放射線敏感性樹脂組合物中的[A ]成分，是由 (a 1)不飽和羧酸和/或不飽和羧酸酐（以下簡稱“化合物 (a 1) ” ）、（ a 2)含有環氧基的不飽和化合物（以下簡稱“不飽 和化合物（a2)” ）和（a3)其他的不飽和化合物（以下簡稱“化 合物（a 3 ) ” ）形成的共聚物（以下簡稱“共聚物[a ] ” ）所組 成。 作爲化合物（a 1 )，例如可以舉出：丙烯酸、甲基丙烯酸、 • 巴豆酸、琥珀酸一（2-丙烯醯氧基乙酯）、琥珀酸一（2-甲基In formula (1), R1 represents a straight-chain, branched-chain or cyclic alkyl group having 1 to 12 carbon atoms; R2 and R3 independently represent a hydrogen atom, and straight-chain or branched chain of 1-12 carbon atoms Or cyclic alkyl or benzyl; R4, R5, R7, and R8 each independently represent a hydrogen atom; a halogen atom, a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms or a carbon number of 1 -4 linear or branched alkoxy group 200537168 ^; R6 represents a halogen atom, a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, and is selected from a hydroxyl group and a carbon number 1 to- 4 linear or branched alkoxy groups of substituents substituted by a linear, branched or cyclic alkyl group having 1 to 2 carbon atoms, a straight chain having 1 to 4 carbon atoms Or a branched alkoxy group, or a straight chain of 2-4 carbon atoms substituted with a substituent selected from the group consisting of a hydroxyl group and a linear or branched alkoxy group of 1-4 carbon atoms Or branched alkoxy. The "radiation" as used in the present invention refers to various rays including ultraviolet rays, extreme ultraviolet rays, X-rays, electron rays, molecular rays, 7 rays, synchrotron radiation rays, proton beam rays, and the like. A second aspect of the present invention is a spacer formed of the radiation-sensitive resin composition for spacer formation described above. A third aspect of the present invention is a method for forming a spacer, which is characterized in that the method includes at least the following steps (1) to (4): (1) Forming on the substrate described in item 1 of the scope of patent application A step of forming a film of the radiation-sensitive resin composition for spacers; (2) a step of exposing at least a part of the film to radiation; (3) a step of developing the above-mentioned film after exposure; (4) a step of A step of heating the film after the development. A fourth aspect of the present invention is a liquid crystal display element including the spacer. [Embodiment] < Radiation-sensitive resin composition for spacers > The radiation-sensitive resin composition for spacers of the present invention (hereinafter referred to as "radiation-sensitive resin composition") will be described in detail below. -10- 200537168 Copolymer [A] The component [A] in the radiation-sensitive resin composition of the present invention is (a 1) an unsaturated carboxylic acid and / or an unsaturated carboxylic anhydride (hereinafter referred to as "the compound (a 1) "), (a 2) unsaturated compounds containing epoxy groups (hereinafter referred to as" unsaturated compounds (a2) ") and (a3) other unsaturated compounds (hereinafter referred to as" compounds (a 3) ") Copolymer (hereinafter referred to as "copolymer [a]"). Examples of the compound (a 1) include acrylic acid, methacrylic acid, crotonic acid, succinic acid mono (2-propenyloxyethyl), and succinic acid mono (2-methyl)

W 丙烯醯氧基乙酯）、六氫鄰苯二甲酸一（2 -丙烯醯氧基乙 酯）、六氫鄰苯二甲酸一（2-甲基丙烯醯氧基乙酯）等一元羧 酸類；馬來酸、富馬酸、檸康酸、中康酸、衣康酸等二元 羧酸類；上述二元羧酸的酐類等。 在這些化合物（a 1)中，從共聚合反應性和容易得到的角度 考慮，較佳爲丙烯酸、甲基丙烯酸、馬來酸酐等。 上述的化合物（a 1)可以單獨使用或者2種以上混合使用。 在共聚物[A]中，來自化合物（al)之構成單元的含有率較 ^ 佳爲5-50重量％，更佳爲10-40重量％。當該構成單元的含 有率低於5重量％時，所獲間隔物的抗壓強度、耐熱性或耐 藥品性有降低的傾向，反之，超過50重量％時，放射線敏 感性樹脂組合物的保存穩定性有可能降低。 另外，作爲化合物U2)，例如可以舉出：丙烯酸縮水甘油 酯、甲基丙烯酸縮水甘油酯、α -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、丙烯酸3,4-環氧基丁酯、甲基丙烯酸3，4-環氧基丁酯、 -11- 200537168 ^ α-乙基丙烯酸3，4 -環氧基丁酯、丙烯酸6,7-甲基丙烯酸6,7-環氧基庚酯、α-乙基丙烯酸 酯、丙烯酸β -甲基縮水甘油酯、甲基丙烯酸 油酯、丙烯酸β-乙基縮水甘油酯、甲基丙烯 甘油酯、丙烯酸β-正丙基縮水甘油酯、甲基 基縮水甘油酯、丙烯酸3,4·環氧基環己酯、甲 環氧基環己酯等羧酸酯類；鄰乙烯基苄基縮 乙烯基苄基縮水甘油醚、對乙烯基苄基縮水 ρ 類等。 在這些化合物（a2)中，從提高共聚合反應性 強度的角度考慮，較佳爲甲基丙烯酸縮水甘 烯酸6,7-環氧基庚酯、甲基丙烯酸β-甲基縮 基丙烯酸3,4-環氧基環己酯、鄰乙烯基苄基 間乙烯基苄基縮水甘油醚、對乙烯基苄基縮: 上述化合物U2)可以單獨使用或者2種以_t 在共聚物[A]中，來自化合物（a2)的構成單 ^ 佳爲10-70重量％，更佳爲20-60重量％。在 該構成單元的含有率低於1 〇重量％時，所得 抗壓強度、耐熱性或耐藥品性有降低的傾向 70重量％時，放射線敏感性樹脂組合物的保 低的傾向。 此外，作爲化合物（a 3 )，例如可以舉出丙烯 酸乙酯、丙烯酸正丙酯、丙烯酸異丙酯、丙 丙烯酸異丁酯、丙烯酸仲丁酯、丙烯酸三級 酸烷基酯類；甲基丙烯酸甲酯、甲基丙烯酸 環氧基庚酯、 6,7-環氧基庚 β -甲基縮水甘 酸β-乙基縮水 丙烯酸β-正丙 基丙烯酸3,4-水甘油醚、間 甘油醚等的醚 和所獲間隔物 油酯、甲基丙 水甘油酯、甲 縮水甘油醚、 水甘油醚等。 二混合使用。 元的含有率較 此情況下，當 到的間隔物的 ，反之，超過 存穩定性有降 酸甲酯、丙烯 嫌酸正丁酯、 丁酯等的丙烯 乙酯、甲基丙 -12- 200537168 ^ 烯酸正丙酯、甲基丙烯酸異丙酯、甲基丙烯酸正丁酯、甲 基丙烯酸異丁酯、甲基丙烯酸仲丁酯、甲基丙烯酸三級丁 酯等的甲基丙烯酸烷基酯類；丙烯酸環己酯、丙烯酸2-甲 基環己酯、丙烯酸三環[5.2.1.02,6]癸烷-8-基酯（以下將“三 環[5.2.1.02’6]癸烷-8-基”稱爲“二環戊基”）、丙烯酸2-二 環戊氧基乙基酯、丙烯酸異冰片基酯、丙烯酸四氫呋喃基 酯等丙烯酸的脂環族酯類；甲基丙烯酸環己酯、甲基丙烯 酸2-甲基環己酯、甲基丙烯酸二環戊酯、甲基丙烯酸2-二 φ 環戊氧基乙酯、甲基丙烯酸異冰片基酯、甲基丙烯酸四氫 呋喃基酯等甲基丙烯酸的脂環族酯類；丙烯酸苯酯、丙烯 酸苄酯等的丙烯酸芳基酯類；甲基丙烯酸苯酯、甲基丙烯 酸苄酯等的甲基丙烯酸芳基酯類； 馬來酸二乙酯、富馬酸二乙酯、衣康酸二乙酯等的二羧 酸二酯類；丙烯酸2-羥乙酯、丙烯酸2-羥丙酯等的丙烯酸 羥烷基酯類；甲基丙烯酸2-羥乙酯、甲基丙烯酸2-羥丙酯 等的甲基丙烯酸羥烷基酯類；苯乙烯、α -甲基苯乙烯、間 ^ 甲基苯乙烯、對甲基苯乙烯、對甲氧基苯乙烯等芳香族乙 烯基化合物；或者丙烯腈、甲基丙烯腈、氯乙烯、偏氯乙 烯、丙烯醯胺、甲基丙烯醯胺、醋酸乙烯、1，3-丁二烯、異 戊二烯、2,3-二甲基-1，3-丁二烯、Ν-環己基馬來醯亞胺、 Ν-苯基馬來醯亞胺、Ν-苄基馬來醯亞胺、Ν-琥珀醯亞胺基 -3 -馬來醯亞胺基苯甲酸酯、Ν-琥珀醯亞胺基-4-馬來醯亞胺 基丁酸酯、Ν-琥珀醯亞胺基-6-馬來醯亞胺基己酸酯、Ν-琥 珀醯亞胺基-3-馬來醯亞胺基丙酸酯、Ν-(9-吖啶基）馬來醯 亞胺等。 -13- 200537168 在這些化合物U3)中，從共聚合反應性方面考慮，較佳爲 丙烯酸2-甲基環己酯、甲基丙烯酸三級丁酯、甲基丙嫌酸 二環戊酯、甲基丙烯酸四氫呋喃基酯、苯乙傭、對甲氧基 苯乙烯、丁二烯等。 上述化合物U3)可以單獨使用或者2種以上混合使用。 在共聚物[A]中，來自化合物（a3)的構成單元的含有率較 佳爲10-80重量％，更佳爲20-60重量％。在此情況下，上 述構成單元的含有率低於1 0重量％時，放射線敏感性樹脂 組合物的保存穩定性有可能降低，反之，超過80重量％時， _ 顯影性有可能降低。 採用凝膠滲透色譜法（GPC)測得的共聚物[A]的聚苯乙烯 換算重均分子量（以下簡稱“Mw”）通常爲2xl03-5xl05,較 佳爲5xl〇Mxl〇5。在此情況下，共聚物[A]的Mw小於2xl03 時，所獲間隔物的抗壓強度或耐熱性有降低的傾向，反之， 在超過5x1 05時，顯影性有降低的傾向。 在本發明中，共聚物[A]可以單獨使用或者2種以上混合 使用。 W 共聚物[A]例如可以通過將化合物（al)、化合物（a2)和化 合物（a3)在溶劑中和在聚合引發劑的存在下進行自由基聚 合來製造。 作爲在製造共聚物[A]時使用的溶劑，例如可以舉出： 甲醇、乙醇、正丙醇、異丙醇、苄醇、2-苯基乙醇、3-苯基-1·丙醇等醇類； 四氫呋喃、二曙烷等醚類； 二乙二醇一甲醚、二乙二醇一乙醚、二乙二醇一正丙基 -14- 200537168 、 醚、二乙二醇一正丁基醚等二乙二醇一烷基醚類； 二乙二醇一甲醚乙酸酯、二乙二醇一乙醚乙酸酯、二乙 二醇一正丙基醚乙酸酯、二乙二醇一正丁基醚乙酸酯等二 乙二醇一烷基醚乙酸酯類； 二乙二醇一甲醚乙酸酯、二乙二醇一乙醚乙酸酯等二乙 二醇一烷基醚乙酸酯類； 二乙二醇一甲醚丙酸酯、二乙二醇一乙醚丙酸酯、二乙 二醇一正丙基醚丙酸酯、二乙二醇一正丁基醚丙酸酯等二 _ 乙二醇一烷基醚丙酸酯類； 二乙二醇一甲醚、二乙二醇一乙醚、二乙二醇二甲醚、 二乙二醇二乙醚、二乙二醇乙基甲基醚等二乙二醇烷基醚 類； 丙二醇一甲醚、丙二醇一乙醚、丙二醇一正丙基醚、丙 二醇一正丁基醚等丙二醇一烷基醚類； 丙二醇一甲醚乙酸酯、丙二醇一乙醚乙酸酯、丙二醇一 正丙基醚乙酸酯、丙二醇一正丁基醚乙酸酯等丙二醇一烷 ^ 基醚乙酸酯類； 丙二醇一甲醚丙酸酯、丙二醇一乙醚丙酸酯、丙二醇一 正丙基醚丙酸酯、丙二醇一正丁基醚丙酸酯等丙二醇一烷 基醚丙酸酯類； 甲苯、二甲苯等芳香族烴類； 丁酮、2-戊酮、3-戊酮、環己酮、4-羥基-4-甲基-2-戊酮 等酮類； 2-甲氧基丙酸甲酯、2-甲氧基丙酸乙酯、2-甲氧基丙酸正 丙基酯、2-甲氧基丙酸正丁基酯、2-乙氧基丙酸甲酯、2- -15-W Acrylic acid ethoxylate), hexahydrophthalic acid mono (2-propene ethoxyethyl), hexahydrophthalic acid mono (2-methacrylic ethoxyethyl), and other monocarboxylic acids ; Dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid; the anhydrides of the aforementioned dicarboxylic acids, and the like. Among these compounds (a 1), acrylic acid, methacrylic acid, maleic anhydride and the like are preferred from the viewpoint of copolymerization reactivity and availability. The above-mentioned compound (a 1) can be used singly or in combination of two or more kinds. In the copolymer [A], the content rate of the constituent units derived from the compound (al) is preferably from 5 to 50% by weight, more preferably from 10 to 40% by weight. When the content rate of the constituent unit is less than 5% by weight, the compressive strength, heat resistance, or chemical resistance of the obtained spacer tends to decrease. Conversely, when it exceeds 50% by weight, the radiation-sensitive resin composition is stored. Stability may decrease. Examples of the compound U2) include glycidyl acrylate, glycidyl methacrylate, α-ethyl glycidyl ester, α-n-propyl glycidyl acrylate, and α-n-butyl acrylic acid. Glyceride, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, -11- 200537168 ^ α-ethyl acrylate 3,4-epoxybutyl acrylate, 6, 7-methacrylic acid 6,7-epoxyheptyl, α-ethyl acrylate, β-methyl glycidyl acrylate, oleyl methacrylate, β-ethyl glycidyl acrylate, methacrylic acid Carboxylic acid esters such as esters, β-n-propyl glycidyl acrylate, methyl glycidyl ester, 3,4 · epoxy cyclohexyl acrylate, and methyl epoxy cyclohexyl acrylate; o-vinyl benzyl glycid Vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl group and the like. Among these compounds (a2), from the viewpoint of improving the copolymerization reactivity strength, preferred are glycidyl methacrylate 6,7-epoxyheptyl methacrylate and β-methacrylic methacrylate 3 , 4-epoxycyclohexyl ester, o-vinyl benzyl m-vinyl benzyl glycidyl ether, p-vinyl benzyl condensation: the above-mentioned compound U2) can be used alone or two kinds of _t in the copolymer [A] In addition, the constitutional unit derived from the compound (a2) is preferably 10 to 70% by weight, and more preferably 20 to 60% by weight. When the content of the constituent unit is less than 10% by weight, the resulting compressive strength, heat resistance, or chemical resistance tends to decrease. At 70% by weight, the radiation-sensitive resin composition tends to be kept low. Examples of the compound (a 3) include ethyl acrylate, n-propyl acrylate, isopropyl acrylate, isobutyl acrylate, sec-butyl acrylate, and tertiary acid alkyl esters; methacrylic acid Methyl ester, epoxyheptyl methacrylate, 6,7-epoxyheptyl β-methylglycidyl β-ethylglycidyl β-n-propylacrylic acid 3,4-water glyceryl ether, m-glyceryl ether, etc. Ethers and the obtained spacer oil esters, methyl glycidyl esters, methyl glycidyl ethers, water glyceryl ethers, and the like. Two mixed use. The content rate of yuan is higher than that in this case. When the spacer is reached, on the contrary, the storage stability exceeds the storage stability of methyl propionate, methyl propionate, n-butyl propionate, butyl ester such as butyl ester, and methyl propyl-12-200537168. ^ N-propyl acrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tertiary butyl methacrylate, etc. Class; cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.02,6] decane-8-yl acrylate (hereinafter "tricyclo [5.2.1.02'6] decane-8 -Based "is called" dicyclopentyl "), cycloaliphatic esters of acrylic acid such as 2-dicyclopentyloxyethyl acrylate, isobornyl acrylate, tetrahydrofuryl acrylate; cyclohexyl methacrylate , 2-methylcyclohexyl methacrylate, dicyclopentyl methacrylate, 2-diφcyclopentyloxyethyl methacrylate, isobornyl methacrylate, tetrahydrofuryl methacrylate, etc. Cycloaliphatic esters of acrylic acid; aryl acrylates such as phenyl acrylate and benzyl acrylate; methacrylic acid Aryl methacrylates such as phenyl acid esters, benzyl methacrylate, etc .; dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconic acid; acrylic acid 2 -Hydroxyalkyl acrylates such as hydroxyethyl acrylate and 2-hydroxypropyl acrylate; hydroxyalkyl methacrylates such as 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate; styrene , Α-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene and other aromatic vinyl compounds; or acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, Acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, N-cyclohexylmalene Amine, N-phenylmaleimide, N-benzylmaleimide, N-succinimide-3 -maleimide benzoate, N-succinimide -4-maleimide iminobutyrate, N-succinimide imino-6-maleimide iminohexanoate, N-succinimide imino-3-maleimide propyl Acid ester, N- (9-acridyl) maleimide and the like. -13- 200537168 Among these compounds U3), from the viewpoint of copolymerization reactivity, 2-methylcyclohexyl acrylate, tertiary butyl methacrylate, dicyclopentyl methacrylic acid, and formazan are preferred. Tetrahydrofuranyl acrylate, styrene ethyl methoxide, p-methoxystyrene, butadiene and the like. The compound U3) can be used alone or in combination of two or more. In the copolymer [A], the content rate of the constituent units derived from the compound (a3) is preferably 10 to 80% by weight, and more preferably 20 to 60% by weight. In this case, when the content rate of the above-mentioned constituent unit is less than 10% by weight, the storage stability of the radiation-sensitive resin composition may be reduced. On the other hand, when it exceeds 80% by weight, the developability may be reduced. The polystyrene-equivalent weight average molecular weight (hereinafter referred to as "Mw") of the copolymer [A] measured by gel permeation chromatography (GPC) is usually 2x103-5x105, and more preferably 5x10Mx105. In this case, when the Mw of the copolymer [A] is less than 2 × 103, the compressive strength or heat resistance of the obtained spacer tends to decrease, and conversely, when it exceeds 5 × 105, the developability tends to decrease. In the present invention, the copolymer [A] can be used alone or in combination of two or more. The W copolymer [A] can be produced, for example, by radical polymerization of the compound (al), the compound (a2), and the compound (a3) in a solvent and in the presence of a polymerization initiator. Examples of the solvent used in producing the copolymer [A] include alcohols such as methanol, ethanol, n-propanol, isopropanol, benzyl alcohol, 2-phenylethanol, and 3-phenyl-1 · propanol. Type; Tetrahydrofuran, dioxane and other ethers; Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl-14-200537168, ether, diethylene glycol mono-n-butyl ether Diethylene glycol monoalkyl ethers; diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-propyl ether acetate, diethylene glycol mono Diethylene glycol monoalkyl ether acetates such as n-butyl ether acetate; Diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate Esters; diethylene glycol monomethyl ether propionate, diethylene glycol monoethyl ether propionate, diethylene glycol mono-n-propyl ether propionate, diethylene glycol mono-n-butyl ether propionate, etc. Diethylene glycol monoalkyl ether propionates; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl ester Diethylene glycol alkyl ethers such as methyl ether Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether Propylene glycol monoalkyl ether acetates such as ether acetate, propylene glycol mono-n-butyl ether acetate; propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol mono-n-propyl ether propionate, Propylene glycol monoalkyl ether propionates such as propylene glycol mono-n-butyl ether propionate; Aromatic hydrocarbons such as toluene and xylene; methyl ethyl ketone, 2-pentanone, 3-pentanone, cyclohexanone, 4-hydroxyl Ketones such as 4-methyl-2-pentanone; methyl 2-methoxypropionate, ethyl 2-methoxypropionate, n-propyl 2-methoxypropionate, 2-methoxy N-butyl propionate, methyl 2-ethoxypropionate, 2--15-

200537168 乙氧基丙酸乙酯、2-乙氧基丙酸正丙基酯、 正丁基酯、2 -正丙氧基丙酸甲酯、2 -正丙氧_ 正丙氧基丙酸正丙基酯、2-正丙氧基丙酸正 丁氧基丙酸甲酯、2-正丁氧基丙酸乙酯、2-正丙基酯、2-正丁氧基丙酸正丁基酯、3 -甲氧 3 -甲氧基丙酸乙酯、3 -甲氧基丙酸正丙基酯、 正丁基酯、3-乙氧基丙酸甲酯、3-乙氧基丙醆 基丙酸正丙基酯、3 -乙氧基丙酸正丁基酯、 酸甲酯、3 -正丙氧基丙酸乙酯、3 -正丙氧基丙 3 -正丙氧基丙酸正丁基酯、3 -正丁氧基丙酸年 基丙酸乙酯、3 -正丁氧基丙酸正丙基酯、3-正丁基酯等烷氧基丙酸烷基酯類； 乙酸甲酯、乙酸乙酯、乙酸正丙酯、乙酸 乙酸甲酯、羥基乙酸乙酯、羥基乙酸正丙酯 丁酯、乳酸甲酯、乳酸乙酯、乳酸正丙酯、 2-羥基-2-甲基丙酸甲酯、2-羥基-2-甲基丙酸 丙酸甲酯、3-羥基丙酸乙酯、3-羥基丙酸正丙 酸正丁酯、2-羥基-3-甲基丁酸甲酯、甲氧基 氧基乙酸乙酯、甲氧基乙酸正丙酯、甲氧基 乙氧基乙酸甲酯、乙氧基乙酸乙酯、乙氧基 乙氧基乙酸正丁酯、正丙氧基乙酸甲酯、正 酯、正丙氧基乙酸正丙酯、正丙氧基乙酸正 基乙酸甲酯、正丁氧基乙酸乙酯、正丁氧基 正丁氧基乙酸正丁酯等其他的酯類。 在這些溶劑中，較佳爲二乙二醇烷基醚類 2- 乙氧基丙酸 ^丙酸乙酯、2- 丁基酯、2-正 正丁氧基丙酸 ,基丙酸甲酯、 3- 甲氧基丙酸 ^乙酯、3-乙氧 3-正丙氧基丙 酸正丙基酯、 ί酯、3-正丁氧 正丁氧基丙酸 正丁酯、羥基 、羥基乙酸正 乳酸正丁酯、 乙酯、3-羥基 ‘酯、3-羥基丙 乙酸甲酯、甲 乙酸正丁酯、 乙酸正丙酯、 丙氧基乙酸乙 丁酯、正丁氧 乙酸正丙酯、 、丙二醇一烷 -16- 200537168 . 基醚乙酸酯類、烷氧基丙酸烷基酯類等。 上述溶劑可以單獨使用或者2種以上混合使用。 另外，作爲在製造共聚物[A]時使用的聚合引發劑，可以 使用那些通常已知可作爲自由基聚合引發劑使用的引發 劑，例如可以舉出2,2、偶氮二異丁腈、2,2’-偶氮二（2,4-二 甲基戊腈）、2,2’-偶氮二（4-甲氧基-2,4-二甲基戊腈）、4,4’-偶氮二（4-氰基戊酸）、二甲基-2,2’-偶氮二（2-甲基丙酸酯）、 2,2’-偶氮二（4-甲氧基-2,4-二甲基戊腈）等偶氮化合物；過氧 p 化苯甲醯、過氧化月桂醯、三級丁基過氧化新戊酸酯、1，1 -二（三級丁基過氧化）環己烷等有機過氧化物；以及過氧化 氫等。在使用過氧化物作爲自由基聚合引發劑的場合，也 可以倂用還原劑作爲氧化還原型引發劑。 這些自由基聚合引發劑可以單獨使用或者2種以上混合 使用。 聚合性不飽和化合物[B] 在本發明的放射線敏感性樹脂組合物中，作爲聚合性不 g 飽和化合物，較佳爲雙官能以上的丙烯酸酯類和甲基丙嫌 酸酯類（以下將它們統稱爲“（甲基）丙烯酸酯類”）。 作爲雙官能的（甲基）丙烯酸酯類，例如可以舉出：丙嫌 酸二乙二醇酯、甲基丙烯酸二乙二醇酯、丨，^己二醇二丙嫌 酸酯、1，6 -己二醇二甲基丙烯酸酯、1，9 -壬二醇二丙烯酸 酯、1，9·壬二醇二甲基丙烯酸酯、四乙二醇二丙烯酸酯、四 乙二醇二甲基丙烯酸酯、聚丙二醇二丙烯酸酯、聚丙二醇 二甲基丙烯酸酯、雙（苯氧基乙醇）芴二丙烯酸酯、雙（苯氧 基乙醇）芴二甲基丙烯酸酯等。 -17- 200537168200537168 ethyl ethoxypropionate, n-propyl 2-ethoxypropionate, n-butyl ester, methyl 2-n-propoxypropionate, 2-n-propoxy-n-propoxypropionate Propyl ester, methyl 2-n-propoxypropionate, methyl n-butoxypropionate, ethyl 2-n-butoxypropionate, 2-n-propyl ester, n-butyl 2-n-butoxypropionate Ester, 3-methoxy 3-methoxypropionate ethyl ester, 3-methoxypropionate n-propyl ester, n-butyl ester, 3-ethoxypropionate methyl ester, 3-ethoxypropionate N-propyl propionate, n-butyl 3-ethoxypropionate, methyl esters, ethyl 3-n-propoxypropionate, 3-n-propoxypropion 3-n-propoxypropionate Alkyl alkoxy propionates such as n-butyl ester, ethyl 3-n-butoxypropionate, ethyl n-propyl propionate, 3-n-butoxy propionate, 3-n-butyl ester; Methyl acetate, ethyl acetate, n-propyl acetate, methyl acetate, ethyl hydroxyacetate, butyl n-propyl glycolate, methyl lactate, ethyl lactate, n-propyl lactate, 2-hydroxy-2- Methyl methylpropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 3-hydroxypropionate, n-butyl 3-hydroxypropionate Methyl 2-hydroxy-3-methylbutanoate, ethyl methoxyoxyacetate, n-propyl methoxyacetate, methyl methoxyethoxyacetate, ethyl ethoxyacetate, ethoxy N-butyl ethoxyacetate, methyl n-propoxyacetate, n-esters, n-propyl n-propoxyacetate, n-propyl n-propoxyacetate, ethyl n-butoxyacetate, n-butoxy Other esters such as n-butoxy acetate and n-butyl acetate. Among these solvents, diethylene glycol alkyl ethers, 2-ethoxypropionic acid, ethyl propionate, 2-butyl ester, 2-n-butoxypropionic acid, and methyl propionate are preferred. , 3-methoxypropionic acid ^ ethyl ester, 3-ethoxy3-n-propoxypropionic acid n-propyl ester, ί ester, 3-n-butoxy-n-butoxypropionic acid n-butyl ester, hydroxyl, hydroxyl N-butyl acetate, ethyl ester, 3-hydroxy 'ester, methyl 3-hydroxypropionate, n-butyl methoacetate, n-propyl acetate, ethyl butyl propoxyacetate, n-propyl n-butoxyacetate , Propylene glycol monoalkane-16-200537168. Ether acetates, alkoxy propionate alkyl esters, etc. These solvents can be used alone or in combination of two or more. In addition, as the polymerization initiator used in the production of the copolymer [A], those generally known as a radical polymerization initiator can be used, and examples thereof include 2,2, azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 4,4 ' -Azobis (4-cyanovaleric acid), dimethyl-2,2'-azobis (2-methylpropionate), 2,2'-azobis (4-methoxy- 2,4-dimethylvaleronitrile) and other azo compounds; peroxy p-benzidine, lauryl peroxide, tert-butyl peroxypivalate, 1,1-di (tert-butyl peroxy) (Oxidation) organic peroxides such as cyclohexane; and hydrogen peroxide. When a peroxide is used as a radical polymerization initiator, a reducing agent may be used as a redox type initiator. These radical polymerization initiators can be used alone or in combination of two or more. Polymerizable unsaturated compound [B] In the radiation-sensitive resin composition of the present invention, as the polymerizable unsaturated saturable compound, bifunctional or higher acrylates and methacrylic acid esters are preferred (these are hereinafter described) (Collectively "(meth) acrylates"). Examples of the bifunctional (meth) acrylates include diethylene glycol propionate, diethylene glycol methacrylate, hexamethylene glycol dipropionate, and 1,6 -Hexanediol dimethacrylate, 1,9-nonanediol diacrylate, 1,9 · nonanediol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate Esters, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, bis (phenoxyethanol) 乙醇 diacrylate, bis (phenoxyethanol) 芴 dimethacrylate, and the like. -17- 200537168

作爲雙官能（甲基）丙烯酸酯類的市售商品，例如可以舉 出：ARONIX M-201、ARONIX M-240、ARONIX M-6200(以 上產品爲東亞合成（股）製造）；KAYARAD HDDA、KAYARAD HX-220、KAYARAD R-604、KAYARAD UX-22(H、KAYARAD UX-230 1 、KAYARAD UX-3204、KAYARAD UX-3 30 1、 KAYARAD UX-4101 、 KAYARAD UX-6101 、 KAY ARAD UX-7101 、KAYARAD UX-8101、KAYARAD MU-2100、 KAYARAD MU-400 1 (以上產品爲日本化藥（股）製造）； VISCOAT260、VISCOAT312、VISCOAT3 3 5 HP(以上產口口口爲大 阪有機化學工業（股）製造）等。 作爲三官能以上的（甲基）丙烯酸酯類，例如可以舉出： 三羥甲基丙烷三丙烯酸酯、三羥甲基丙烷三甲基丙烯酸 酯、四級戊四醇三丙烯酸酯、四級戊四醇三甲基丙烯酸酯、 四級戊四醇四丙烯酸酯、四級戊四醇四甲基丙烯酸酯、二 四級戊四醇五丙烯酸酯、二四級戊四醇五甲基丙烯酸酯、 二四級戊四醇六丙烯酸酯、二四級戊四醇六甲基丙烯酸 酯、三（2-丙烯醯氧基乙基）磷酸酯、三（2-甲基丙烯醯氧基 乙基）磷酸酯。作爲9官能以上的（甲基）丙烯酸酯類，可以 舉出使具有直鏈亞烷基和脂環式結構且含有2個以上異氰 酸酯基的化合物與分子內具有1個以上羥基且含有3個、4 個或5個丙烯醯氧基和/或甲基丙烯醯氧基的化合物反應而 得到的尿烷丙烯酸酯類化合物等。 另外，作爲3官能以上的（甲基）丙烯酸酯類的市售商品， 例如可以歹!J 舉：ARONIX M-309、 ARONIX M-400、 ARONIX M-402、ARONIX M-405、ARONIX M-450、ARONIX M-1310、 -18- 200537168 • ARONIX Μ- 1 600 、 ARONIX Μ- 1 960 、 ARONIX M-7100 、 ARONIX M- 8030 、 ARONIX M-8060 、 ARONIX M-8100 、 ARONIX M- 8 5 3 0 、 ARONIX M- 85 60 、 ARONIX M-905 0 、 ARONIX T〇- 1 450(以上產品爲東亞合成（股）製造）； KAYARAD TMPTA、KAYARAD DPHA、KAYARAD DPCA-20、 KAYARAD DPCA-30、KAYARAD DPCA-60、KAYARAD DPCA-120、KAYARAD MAX-35 1 0(以上產品爲日本化藥 (股）製造）；VISCOAT295、VISCOAT300、VISCOAT360、 • VISCOATGPT、 VISCOAT3PA、 VISCO AT400(以上產品爲大 阪有機化學工業（股）製造）；作爲含有尿烷丙烯酸酯類化合 物的市售商品，可以列舉New Frontier R-1150(第一工業製 藥（股）製造）、KAYARAD DPHA-40H(日本化藥（股）製造）等。 在本發明中，聚合性不飽和化合物可以單獨使用或者2 種以上混合使用。 在本發明的放射線敏感性樹脂組合物中，相對於1 00重 量份的共聚物[A]，聚合性不飽和化合物的用量較佳爲 0 30-200重量份，更佳爲50- 1 40重量份。在此情況下，聚合 性不飽和化合物的用量不到30重量份時，所獲間隔物容易 發生膜減少或強度的降低，反之，其用量超過200重量份 時，所得間隔物的黏附性往往不夠好。 放射線敏感性聚合引發劑[C] 本發明的放射線敏感性樹脂組合物中的放射線敏感性聚 合引發劑是以上述一般式（1)表示的化合物（以下稱爲“化 合物（1)”）作爲必要成分的引發劑。 在一般式（1)中，作爲 R1、R2、R3、R4、R5、R6、R7 和 R8 -19- 200537168 . 的碳原子數1 -1 2的直鏈、支鏈或環狀的烷基，例如可以舉 出甲基、乙基、正丙基、異丙基、正丁基、異丁基、仲丁 基、三級丁基、正戊基、正己基、正庚基、正辛基、正壬 基、正癸基、正十一烷基、正十二烷基、環戊基、環己基 等。 另外，作爲R4、R5、R6、R7和R8的鹵素原子，例如可以 舉出氟原子、氯原子、溴原子等。 另外，作爲R4、R5、R6、R7和R8的碳原子數1-4的直鏈、 _ 支鏈或環狀的烷氧基，例如可以舉出甲氧基、乙氧基、正 丙氧基、異丙氧基、正丁氧基、異丁氧基、仲丁氧基、三 級丁氧基等。 另外，在R6之經選自羥基和碳原子數1-4的直鏈或支鏈 狀的烷氧基中的取代基所取代的碳原子數1 -1 2的直鏈、支 鏈或環狀的烷基中，作爲碳原子數1-4的直鏈或支鏈狀的 烷氧基，例如可以舉出那些與上述R4、R5、R6、R7和R8的 碳原子數1 -4的直鏈或支鏈狀的烷氧基中所例示的同樣的 基團。 ^ 相對於R6之經取代的碳原子數1 -1 2的直鏈、支鏈或環狀 的烷基，作爲取代基，例如較佳爲羥基、甲氧基等。 在R6之經取代的碳原子數1 -1 2的直鏈、支鏈或環狀的烷 基，例如可以舉出那些與上述 R1、R2、R3、R4、R5、R6、 R7和R8的碳原子數1-12的直鏈、支鏈或環狀的烷基中所 例示的同樣的基團。 在R6之經取代的碳原子數1-12的直鏈、支鏈或環狀的烷 基中，可以存在1種以上或1個以上的取代基。 -20- 200537168 ， 另外，在R6之經選自羥基和碳原子數卜4的 狀的烷氧基之取代基所取代的碳原子數2-4的 狀的烷氧基中，作爲碳原子數1-4的直鏈或支 基，例如可以舉出那些與上述R4、R5、R6、R7 ; 子數1 -4的直鏈或支鏈狀的烷氧基中所例示的 對於R6之經取代的碳原子數2-4的直鏈或支 基，作爲取代基，例如較佳爲羥基、甲氧基等 在R6之經取代的碳原子數2-4的直鏈或支 I 基，例如可以舉出乙氧基、正丙氧基、異丙氧 基、異丁氧基、仲丁氧基、三級丁氧基等。 在R6之經取代的碳原子數2-4的直鏈或支鏈 中，可以存在1種以上或1個以上的取代基。 在一般式（1)中，作爲R1，較佳爲甲基、乙基 異丙基、正丁基、異丁基、仲丁基、三級丁基 正己基等。 另外，作爲R2和R3，較佳爲甲基、乙基、正 基、正丁基、異丁基、仲丁基、三級丁基、正 ®基、正庚基、正辛基等。 • 另外，作爲R4、R5、R7和R8，較佳爲氫原子 基等。 進而，作爲R6，較佳爲甲基、乙基、正丙基 正丁基、異丁基、仲丁基、三級丁基、正戊基 正庚基、正辛基、正癸基、正十二烷基、經甲 基、甲氧甲基、2 -甲氧乙基、甲氧基、乙氧基、 異丙氧基、正丁氧基、羥基甲氧基、2_經基乙 直鏈或支鏈 直鏈或支鏈 鏈狀的院氧 和R8的碳原 男樣的基團。 鏈狀的烷氧 〇 鏈狀的烷氧 基、正丁氧 狀的烷氧基 丨、正丙基、 、正戊基、 丙基、異丙 戊基、正己 、甲基、乙 、異丙基、 、正己基、 基、2-羥乙 正丙氧基、 氧基、甲氧 -21- 200537168 . 甲氧基、2-甲氧乙氧基等。 在本發明中較佳化合物（1)之具體例，可以舉出： 2-(4 -甲基苄基）-2-(二甲胺基）-1-(4-嗎啉并苯基）丁烷-卜 酮、 2-(4-乙基苄基）-2-(二甲胺基）-1-(4-嗎啉并苯基）丁烷-1-酮、 2-(4-異丙基苄基）-2-(二甲胺基）-1-(4-嗎啉并苯基）丁烷 -1-酮、 g 2-(4·正丁基苄基）-2-(二甲胺基）-1-(4-嗎啉并苯基）丁烷 -1-酮、 2-(4-異丁基苄基）-2-(二甲胺基）-1-(4-嗎啉并苯基）丁烷 -1-酮、 2-(4-正十二烷基苄基）-2-(二甲胺基）-1-(4-嗎啉并苯基） 丁烷-1-酮、 2-(3,4-二甲基苄基）-2-(二甲胺基）-1-(4-嗎啉并苯基）丁烷 -1-酮、 2-(4-甲氧基苄基）-2-(二甲胺基）-1-(4-嗎啉并苯基）丁烷 ® -1-酮、 2-(4 -乙氧基苄基）-2-(二甲胺基）-1-(4-嗎啉并苯基）丁烷 -1 -酮、 2-(4-羥甲基苄基）-2-(二甲胺基）-1-(4-嗎啉并苯基）丁烷 -1-酮、 2-[4-(2-羥基乙氧基）苄基]-2-(二甲胺基）-1-(4-嗎啉并苯 基）丁烷-1-酮、 2-[4-(2-甲氧基乙氧基）苄基]-2-(二甲胺基）-1-(4-嗎啉并 -22- 200537168 . 苯基）丁烷-1-酮、 2-(4-異丙基苄基）-2-[(正丁基）（甲基）胺基嗎啉并 苯基）丁烷-1-酮、 2-(4-正丁基苄基）_2_[(正丁基）（甲基）胺基嗎啉并 苯基）丁烷-1-酮、 2-(4-異丙基苄基）_2_(二甲胺基）4-(4-嗎啉并苯基）戊烷 -1·酮、 2-(4-異丁基苄基卜2_[(正丁基）（甲基）胺基卜丨““嗎啉并 | 苯基）戊院-1-酮、 2-(4-正丁氧基苄基）_2-[(正丁基）（甲基）胺基]_1-(4-嗎啉 并苯基）戊烷-1·酮、 2-(4-甲基苄基）_2·[二（正辛基）胺基]-1-(4-嗎啉并苯基）己 院-1 -酮、 2-(4-正十二烷基苄基）_2_(二甲胺基M_(4_嗎啉并苯基） 辛烷-1-酮等。 在這些化合物（1)中，特別較佳爲2-(4-甲基苄基）-2-(二甲 0 胺基）-1-(4-嗎啉并苯基）丁烷-酮、2-(4-乙基苄基）-2-(二甲 胺基）-1-(4-嗎啉并苯基）丁烷-丨_酮、2-(4-異丙基苄基）-2-(二 甲胺基）-1-(4-嗎啉并苯基）丁烷-1-酮等。 化合物（1)是一種能夠形成優良間隔物的成分，它在溶劑 中的溶解性優良，不會產生未溶解物、析出物等的異物， 同時不會由於昇華而導致燒成爐或光掩模等的污染，而且 不會造成圖案的遺漏和缺損。 在本發明中，化合物（1)可以單獨使用或者2種以上混合 使用。 -23- 200537168 . 在本發明的放射線敏感性樹脂組合物中，相對於1 00重 量份的共聚物[A ]，化合物（1)的使用量較佳爲5〜5 0重量 份，更佳爲5〜3 0重量份。在此情況下，當化合物（1)的使 用量小於5重量份時，殘膜率有降低的傾向，反之，當超 過5 0重量份時，未曝光部分在鹼性顯影液中的溶解性有降 低的傾向。 另外，在本發明的放射線敏感性樹脂組合物中，化合物 (1)可以與至少1種其他的放射線敏感性聚合引發劑合倂使 • 用。 作爲上述其他的放射線敏感性聚合引發劑，例如可以舉 出：0 -醯基肟型化合物、苯乙酮類化合物、雙咪唑類化合 物、苯偶姻類化合物、二苯甲酮類化合物、α -二酮類化合 物、多核醌類化合物、咕噸酮類化合物、膦類化合物、三 阱類化合物等。 在這些其他的放射線敏感性聚合引發劑中，較佳爲0-醯 基肟型化合物、苯乙酮類化合物、雙咪唑類化合物。 • 上述的〇 -醯基肟型化合物是一類具有進一步提高靈敏度 作用的成分。 作爲0-醯基肟型化合物的具體例，可以舉出1-(9-乙基-6-苯甲醯基-9.H，咔唑-3-基）壬烷- i，2-壬烷-2 -肟苯甲酸 酯、1-(9 -乙基-6-苯甲醯基- 9.H· -咔唑-3-基）壬烷-1，2 -壬烷- 2-肟-0·乙酸酯、1-(9-乙基-6-苯甲醯基-9.H·-咔唑-3-基）戊烷 -1，2-戊烷-2-肟_〇-乙酸酯、1-(9_乙基-6-苯甲醯基- 9Η-咔唑 -3-基）辛烷-1-酮肟-〇-乙酸酯、^[9·乙基- 6- (2 -甲基苯甲醯 基）-9·Η· -咔π坐-3-基]乙院-1-酮時·〇·苯甲酸酯、丨_[9_乙基 -24 - 200537168 -6-(2-甲基苯甲醯基）-9.Η.-咔唑-3-基]乙烷-1-酮肟-〇_乙酸 酯、1·[9 -乙基·6-(1，3,5 -三甲基苯甲醯基）-9·Η· -咔唑-3-基] 乙烷-1-酮肟·〇-苯甲酸酯、1-[9-正丁基-6-(2-乙基苯甲醯 基）-9·Η· -味哇-3-基]乙院-1-酮勝-〇·苯甲酸酯、ι，2_辛二酮 小[4-(苯硫基）苯基]-2-(0 -苯甲醯基聘）、1,2 - 丁二酮 -1-[4-(苯硫基）苯基]·2-(〇-苯甲醯基肟）、1，2-丁二酮 -1-[4-(苯硫基）苯基]-2-(〇-乙醯基肟）、ι，2-辛二酮·ΐ-[4_(甲 硫基）苯基]-2-(0 -苯甲醯基肟）、ι，2 -辛二酮- ΐ- [4-(苯硫基） 苯基]-2-[0-(4 -甲基苯甲醯基聘）]等。 在這些0-醯基肟型化合物中，較佳爲M9-乙基-6-(2_甲 基本甲釀基）-9·Η· -昨卩坐-3_基]乙院-1-嗣胎-〇-乙酸醋、ι，2· 辛二酮-1-[4-(苯硫基）苯基]-2-(〇-苯甲醯基肟）等。 上述的0-醯基肟型化合物可以單獨使用或者2種以上混 合使用。 相對於共聚物[A] 100重量份，〇-醯基肟型化合物的使用 量較佳爲3 0重量份以下，更佳爲2 0重量份以下。在此情 況下，當0 -醯基肟型化合物的使用量超過3 0重量份時， 未曝光部分在鹼性顯影液中的溶解性有降低的傾向，而且 由於0-醯基肟型化合物的昇華所導致的燒成爐或光掩模等 的污染有增高的傾向。另外，當〇 -醯基肟型化合物的使用 量小於5重量份時，殘膜率有可能降低。 上述的苯乙酮類化合物是對形成的間隔物的形狀具有調 節作用的成分。 作爲苯乙酮類化合物，例如可以舉出α -羥基酮類化合 物、α -胺基酮類化合物等。 -25- 200537168 作爲上述^ -羥基酮類化合物的具體例’可以舉出卜苯基 -2-羥基-2-甲基丙烷-1-酮、1-(4-異丙基苯基）-2-羥基-2-甲基 丙烷-1-酮、4-(2-羥基乙氧基）苯基-(2-經基-2-丙基）酮、 羥基環己基苯基酮等；作爲上述α -胺基酮類化合物的具體 例，可以舉出2 ·甲基-1 - [ 4 -(甲硫基）苯基卜2 -嗎啉并丙院-1 -酮、2-苄基- 2-(二甲胺基）-1-(4-嗎啉并苯基）丁烷-卜酮、1-(2-溴-4-嗎啉并苯基）-2-苄基-2-二甲胺基丁烷-1-酮、2-(2-溴节 基）-2-(二甲胺基）-1-(4-嗎啉并苯基）丁烷-1-酮、2-(4-溴苄 基）-2·(二甲胺基）-1-(4-嗎啉并苯基）丁烷-1-酮等。作爲這些 化合物以外的苯乙酮類化合物的具體例’可以舉出2,2-二 甲氧基苯乙酮、2,2-二乙氧基苯乙酮、2,2-二甲氧基-2-苯基 苯乙酮等。 在這些苯乙酮類化合物中，較佳爲2-甲基甲硫基） 苯基]-2-嗎啉并丙烷-1-酮、2-苄基-2-(二甲胺基）-1-(4-嗎啉 并苯基）丁烷-1-酮、1-(2-溴-4-嗎啉并苯基）-2-苄基-2-二甲 胺基丁烷-1-酮、2-(4-溴苄基）-2-(二甲胺基）-1-(4-嗎啉并苯 基）丁烷-1-酮等。 上述的苯乙酮類化合物可以單獨使用或者2種以上混合 使用。 相對於共聚物[A] 100重量份，苯乙酮類化合物的使用量 較佳爲30重量份以下，更佳爲20重量份以下。在此情況 下，當苯乙酮類化合物的使用量超過30重量份時，由於苯 乙酮類化合物的昇華所導致的燒成爐或光掩模等的污染和 液體中異物的產生有增高的傾向。另外，當苯乙酮類化合 物的使用量小於1重量份時，顯影時的殘膜率有可能降低。 -26- 200537168 上述的雙咪唑類化合物是一種對形成的間隔物的形狀具 有調節作用，而且能夠起到進一步提高靈敏度、圖像解析 度或與基板的黏附性的作用的成分。 作爲雙咪唑類化合物的具體例，可以舉出：2,2’-二（2-氯 苯基）-4,4’，5,5’-四（4-乙氧羰基苯基）-1，2’-雙咪唑、2,2’-二 (2-溴苯基）-4,4’，5,5’-四（4-乙氧羰基苯基）-1，2’-雙咪唑、 2,2’-二（2-氯苯基）-4,4’，5,5’-四苯基-1，2’-雙咪唑、2,2’-二 (2,4-二氯苯基）-4,4’，5,5’-四苯基-1，2’-雙咪唑、2,2’-二 _ (2,4,6-三氯苯基）-4,4’，5,5’-四苯基-1，2’-雙咪唑、2,2’-二（2- 溴苯基）-4,4’，5,5’-四苯基-1，2’-雙咪唑、2,2’-二（2,4-二溴苯 基）-4,4，，5,5，-四苯基-1，2，-雙咪唑、2,2’-二（2,4,6-三溴苯 基）-4,4’，5,5’-四苯基-1，2’-雙咪唑等。 在這些雙咪唑類化合物中，較佳爲 2,2’-二（2-氯苯 基）-4,4’，5,5’-四苯基-1，2’-雙咪唑、2,2’·二（2,4-二氯苯 基）-4,4，，5,5、四苯基-1,2，-雙咪唑、2,2’-二（2,4,6-三氯苯 基）-4,4’，5,5’·四苯基-1，2’·雙咪唑等，特別較佳爲 2,2’-二 (2,4-二氯苯基）-4,4’，5,5’-四苯基-1，2’-雙咪唑。 ^ 上述的雙咪唑類化合物，可以單獨使用或者2種以上混 合使用。 相對於共聚物[A] 100重量份，雙咪唑類化合物的使用量 較佳爲50重量份以下，更佳爲35重量份以下。在此情況 下，當雙咪唑類化合物的使用量超過5 0重量份時，向液晶 中的溶出物增加，使得電壓保持率容易降低，同時由於雙 咪唑類化合物的昇華所導致的燒成爐或光掩模等的污染有 增高的傾向。反之，當雙咪唑類化合物的使用量小於〇. i -27- 200537168 β 重量份時，殘膜率有可能降低。 在本發明的放射線敏感性樹脂組合物中，當使用雙咪唑 類化合物作爲放射線敏感性聚合引發劑成分的場合，較佳 爲合倂使用那些對雙咪唑類化合物具有增敏感作用的含有 二烷基胺基的化合物。 作爲這類含有二烷基胺基的化合物，較佳爲例如含有二 烷基胺基的二苯甲酮衍生物和含有二烷基胺基的苯甲酸酯 類，更具體地可以舉出，例如，4,4’-雙（二甲胺基）二苯甲 _ 酮、4,4’-雙（二乙胺基）二苯甲酮、對二甲胺基苯甲酸乙酯、 對二乙胺基苯甲酸乙酯、對二甲胺基苯甲酸異戊酯、對二 乙胺基苯甲酸異戊酯等。 在這些含有二烷基胺基的化合物中，特佳爲4,4’-雙（二乙 胺基）二苯甲酮。 上述含有二烷基胺基的化合物可以單獨使用或者2種以 上混合使用。 在並用雙咪唑類化合物和含有二烷基胺基的化合物的場 合，相對於共聚物[Α] 100重量份，含有二烷基胺基的化合 ® 物的使用量較佳爲〇· 1-50重量份，更佳爲1-20重量份。在 此情況下，當含有二烷基胺基的化合物的使用量小於0.1 重量份時，所獲間隔物容易發生膜減少或者間隔物的形狀 不良，反之，在超過5 0重量份時，間隔物的形狀受損，同 時，由於含有二烷基胺基的化合物的昇華所導致的燒成爐 或光掩模等的污染有增高的傾向。 進而，在本發明的放射線敏感性樹脂組合物中，當並用 雙咪唑類化合物與含有二烷基胺基的化合物作爲放射線敏 •28- 200537168 感性聚合引發劑成分的場合，較佳爲添加一種對雙咪唑類 化合物具有能夠供給氫自由基的作用的硫醇類化合物。雙 咪唑類化合物會由於被含有二烷基胺基的化合物增敏感而 開裂，產生咪唑自由基，但此時如果不存在硫醇類化合物， 則不能產生高的自由基聚合引發能力，所獲間隔物大多形 成如倒錐形那樣的不理想的形狀。然而，通過向雙咪唑類 化合物與含有二烷基胺基的化合物共存的體系中添加硫醇 類化合物，就能向咪唑自由基供給氫自由基，結果使得咪 唑自由基轉變成中性的咪唑，同時產生了具有聚合引發能 ® 力高的硫自由基，從而使間隔物的形狀成爲比較理想的正 錐形。 作爲上述的硫醇化合物，例如可以舉出：2-酼基苯并噻 唑、2-毓基苯并曙唑、2-锍基苯并咪唑、2-锍基-5-甲氧基 苯并噻唑、2-毓基-5-甲氧基苯并咪唑等芳香族化合物；3-毓基丙酸、3-酼基丙酸甲酯、3-巯基丙酸乙酯、3-锍基丙酸 辛酯等的脂肪族類一硫醇；3,6-二噚-1，8·辛烷二硫醇、四級 戊四醇四（锍基乙酸酯）、四級戊四醇四（3-锍基丙酸酯）等的 ®脂肪族多硫醇類化合物等。 這些硫醇化合物可以單獨使用或者2種以上混合使用。 在將雙咪唑類化合物、含有二烷基胺基的化合物和硫醇 類化合物組合使用的場合’相對於共聚物[Α] 100重量份， 硫醇類化合物的使用量較佳爲0·1·50重量份’更佳爲1-20 重量份。在此情況下’當硫醇類化合物的使用量小於〇 · 1 重量份時，所獲間隔物存在容易發生膜減少或形狀不良的 傾向，反之，當超過50重量份時’間隔物的形狀可能受損， -29- 200537168 同時，由於硫醇類化合物的昇華，使得燒成爐或光掩模等 受污染的可能性有增高的傾向。 在本發明的放射線敏感性樹脂組合物中，相對於全部放 射線敏感性聚合引發劑1 00重量份，其他放射線敏感性聚 合引發劑的使用比例較佳爲1 00重量份以下，更佳爲80重 量份以下，特別較佳爲60重量份以下。在此情況下，當其 他的放射線敏感性聚合引發劑的使用比例超過1 00重量份 時，有可能損害本發明所期望的效果。 一任意添加劑一 ® 在本發明的放射線敏感性樹脂組合物中，可以根據需 要，在不損害本發明效果的範圍內混合上述成分以外的任 意添加劑，例如表面活性劑、黏結助劑、保存穩定劑、耐 熱性提高劑等。 上述表面活性劑是用來提高塗布性能的混合成分，較佳 爲氟類表面活性劑以及矽氧烷類表面活性劑。 作爲上述的氟類表面活性劑，較佳爲在末端、主鏈和側 鏈中的至少一個部位上具有氟烷基和/或伸氟烷基的化合 ^ 物，作爲其例子，可以舉出：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、八乙二 醇二（1，1，2,2-四氟-正丁基）醚、六甘醇（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、六丙二醇 二（1，1，2,2,3,3-六氟-正戊基）醚、1，1，2,2,3,3-六氟正癸烷、 1，1，2,2,8,8,9,9，10，10-十氟正十二烷、全氟正十二烷磺酸 鈉，以及氟烷基苯磺酸鈉類、氟烷基膦酸鈉類、氟烷基羧 酸鈉類、氟烷基聚氧乙烯醚類、二丙三醇四（氟烷基聚氧乙 -30- 200537168 烯醚）類、氟烷基碘化銨類、氟烷基甜菜鹼類、氟烷基聚氧 乙烯醚類、全氟烷基聚氧乙醇類、全氟烷基烷氧基酯類、 氟系烷基酯類等。 另外，作爲氟類表面活性劑的市售商品，例如可以列舉： BM- 1 000、BM-1 100(以上產品爲 B M C H EM IE公司製造）， MEGAFACE F142D、MEGAFACE F172、MEGAFACE F173、As commercially available products of bifunctional (meth) acrylates, for example: ARONIX M-201, ARONIX M-240, ARONIX M-6200 (the above products are manufactured by East Asia Synthesis Co., Ltd.); KAYARAD HDDA, KAYARAD HX-220, KAYARAD R-604, KAYARAD UX-22 (H, KAYARAD UX-230 1, KAYARAD UX-3204, KAYARAD UX-3 30 1, KAYARAD UX-4101, KAYARAD UX-6101, KAY ARAD UX-7101, KAYARAD UX-8101, KAYARAD MU-2100, KAYARAD MU-400 1 (The above products are manufactured by Nippon Kayaku Co., Ltd.); VISCOAT260, VISCOAT312, VISCOAT3 3 5 HP (The above products are imported from Osaka Organic Chemical Industry Co., Ltd.) (Manufactured), etc. Examples of the trifunctional or higher (meth) acrylates include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, and tetrapentaerythritol triacrylate , Tetrapentaerythritol trimethacrylate, tetrapentaerythritol tetraacrylate, tetrapentaerythritol tetramethacrylate, secondary tetrapentaerythritol pentaacrylate, secondary tetrapentaerythritol pentamethyl Acrylate, quaternary pentaerythritol hexaacrylate, quaternary Pentaerythritol hexamethacrylate, tris (2-propenyloxyethyl) phosphate, tris (2-methacryloxyethyl) phosphate. (Meth) acrylates with more than 9 functions Examples include a compound having a linear alkylene group and an alicyclic structure and containing two or more isocyanate groups, a compound having one or more hydroxyl groups in the molecule, and containing three, four, or five acryloxy groups and / Or urethane acrylate compounds obtained by reacting methacryloxy compounds. In addition, as commercially available products of trifunctional or higher (meth) acrylates, for example, J: ARONIX M- 309, ARONIX M-400, ARONIX M-402, ARONIX M-405, ARONIX M-450, ARONIX M-1310, -18- 200537168 • ARONIX M-1600, ARONIX M-1960, ARONIX M-7100, ARONIX M- 8030 、 ARONIX M-8060 、 ARONIX M-8100 、 ARONIX M- 8 5 3 0 、 ARONIX M- 85 60 、 ARONIX M-905 0 、 ARONIX T〇- 1 450 (The above products are manufactured by Toa Synthesis (Stock) ); KAYARAD TMPTA, KAYARAD DPHA, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60 KAYARAD DPCA-120, KAYARAD MAX-35 1 0 (The above products are manufactured by Nippon Kayaku Co., Ltd.); VISCOAT295, VISCOAT300, VISCOAT360, • VISCOATGPT, VISCOAT3PA, VISCO AT400 (The above products are manufactured by Osaka Organic Chemical Industry (Stock)) ; As commercially available products containing a urethane acrylate compound, New Frontier R-1150 (manufactured by Daiichi Kogyo Co., Ltd.), KAYARAD DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), and the like can be cited. In the present invention, the polymerizable unsaturated compound may be used alone or as a mixture of two or more. In the radiation-sensitive resin composition of the present invention, the amount of the polymerizable unsaturated compound is preferably 0 to 30 to 200 parts by weight, and more preferably 50 to 1 40 parts by weight based on 100 parts by weight of the copolymer [A]. Serving. In this case, when the amount of the polymerizable unsaturated compound is less than 30 parts by weight, the obtained spacer is liable to reduce the film or the strength. On the other hand, when the amount exceeds 200 parts by weight, the adhesiveness of the obtained spacer is often insufficient. it is good. Radiation-sensitive polymerization initiator [C] The radiation-sensitive polymerization initiator in the radiation-sensitive resin composition of the present invention requires the compound represented by the general formula (1) (hereinafter referred to as "compound (1)") as a necessity Ingredient initiator. In the general formula (1), as R1, R2, R3, R4, R5, R6, R7, and R8-19-200537168. A straight-chain, branched-chain, or cyclic alkyl group having 1 to 12 carbon atoms, Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, N-nonyl, n-decyl, n-undecyl, n-dodecyl, cyclopentyl, cyclohexyl and the like. Examples of the halogen atom for R4, R5, R6, R7, and R8 include a fluorine atom, a chlorine atom, and a bromine atom. Examples of the linear, branched or cyclic alkoxy group having 1 to 4 carbon atoms in R4, R5, R6, R7, and R8 include methoxy, ethoxy, and n-propoxy groups. , Isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tertiary butoxy and the like. In addition, R6 is a linear, branched, or cyclic carbon number of 1 to 12 substituted by a substituent selected from a hydroxyl group and a linear or branched alkoxy group having 1 to 4 carbon atoms. Examples of the straight-chain or branched-chain alkoxy group having 1 to 4 carbon atoms in the alkyl group include straight chains having 1 to 4 carbon atoms as described above for R4, R5, R6, R7, and R8. Or the same group as exemplified in the branched alkoxy group. ^ As a substituent, a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms substituted with respect to R6 is preferably a hydroxy group, a methoxy group, or the like. The substituted, straight-chain, branched-chain or cyclic alkyl group having 1 to 12 carbon atoms at R6 includes, for example, those carbons which are similar to those of R1, R2, R3, R4, R5, R6, R7, and R8. The same groups as exemplified in the straight-chain, branched-chain, or cyclic alkyl group having 1 to 12 atoms. In a substituted linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, R6 may have one or more kinds of substituents. -20-200537168, In addition, the number of carbon atoms in the alkoxy group of carbon number 2-4 substituted by R6 by a substituent selected from a hydroxyl group and an alkoxy group of carbon number 4 Examples of the straight or branched chain of 1-4 include those substituted for R6 exemplified in the straight or branched alkoxy group having the number of members as described above for R4, R5, R6, and R7; As the substituent, for example, a straight chain or branched group having 2 to 4 carbon atoms and a substituted carbon group having 2 to 4 carbon atoms such as a hydroxyl group and a methoxy group are preferred. Examples include ethoxy, n-propoxy, isopropoxy, isobutoxy, sec-butoxy, tertiary butoxy, and the like. R6 may have one or more substituents in a straight or branched chain having 2 to 4 carbon atoms. In the general formula (1), R1 is preferably methyl, ethylisopropyl, n-butyl, isobutyl, sec-butyl, tertiary-butyl n-hexyl, or the like. In addition, as R2 and R3, methyl, ethyl, n-butyl, n-butyl, isobutyl, sec-butyl, tertiary butyl, n-yl, n-heptyl, n-octyl and the like are preferred. • In addition, as R4, R5, R7, and R8, a hydrogen atom group or the like is preferable. Furthermore, as R6, methyl, ethyl, n-propyl n-butyl, isobutyl, sec-butyl, tertiary butyl, n-pentyl n-heptyl, n-octyl, n-decyl, n- Dodecyl, transmethyl, methoxymethyl, 2-methoxyethyl, methoxy, ethoxy, isopropoxy, n-butoxy, hydroxymethoxy, 2-methoxyethyl Chain or branched linear or branched chain oxygen and R8 carbon male-like groups. Chain alkoxy, chain alkoxy, n-butoxy alkoxy, n-propyl,, n-pentyl, propyl, isopropylamyl, n-hexyl, methyl, ethyl, isopropyl ,, N-hexyl, radical, 2-hydroxyethyl-n-propoxy, oxy, methoxy-21-200537168. Methoxy, 2-methoxyethoxy, etc. Specific examples of the preferred compound (1) in the present invention include: 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butyl Alkane-butanone, 2- (4-ethylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butane-1-one, 2- (4-isopropyl Benzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butane-1-one, g 2- (4 · n-butylbenzyl) -2- (dimethyl Amino) -1- (4-morpholinophenyl) butane-1-one, 2- (4-isobutylbenzyl) -2- (dimethylamino) -1- (4-morpholine Phenyl) butane-1-one, 2- (4-n-dodecylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butane-1- Ketone, 2- (3,4-dimethylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butane-1-one, 2- (4-methoxy Benzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butane®-1-one, 2- (4-ethoxybenzyl) -2- (dimethyl Amino) -1- (4-morpholinophenyl) butane-1-one, 2- (4-hydroxymethylbenzyl) -2- (dimethylamino) -1- (4-morpholine Phenyl) butane-1-one, 2- [4- (2-hydroxyethoxy) benzyl] -2- (dimethylamino) -1- (4-morpholinophenyl) butane -1-one, 2- [4- (2-methoxyethoxy) benzyl] -2- (dimethylamino) -1- (4-morpholino-22- 200537168. Phenyl) butane-1-one , 2- (4-isopropylbenzyl) -2-[(n-butyl) (methyl) aminomorpholinophenyl) butane-1-one, 2- (4-n-butylbenzyl ) _2 _ [(n-butyl) (methyl) aminomorpholinophenyl) butane-1-one, 2- (4-isopropylbenzyl) _2_ (dimethylamino) 4- (4- Morpholinophenyl) pentane-1 · ketone, 2- (4-isobutylbenzylbenzene 2 _ [(n-butyl) (methyl) amino group 丨 "morpholino | phenyl) pentan -1-one, 2- (4-n-butoxybenzyl) _2-[(n-butyl) (methyl) amino] _1- (4-morpholinophenyl) pentane-1 · one, 2- (4-methylbenzyl) _2 · [di (n-octyl) amino] -1- (4-morpholinophenyl) hexan-1-one, 2- (4-n-dodecane Benzyl) _2_ (dimethylamino M_ (4-morpholinophenyl) octane-1-one, etc. Among these compounds (1), 2- (4-methylbenzyl) is particularly preferred 2- (dimethylamino) -1- (4-morpholinophenyl) butane-one, 2- (4-ethylbenzyl) -2- (dimethylamino) -1- ( 4-morpholinophenyl) butane- 丨 _one, 2- (4-isopropylbenzyl)- 2- (dimethylamino) -1- (4-morpholinophenyl) butane-1-one, etc. Compound (1) is a component capable of forming an excellent spacer, and has excellent solubility in a solvent No foreign matter such as undissolved matter, precipitates, etc., and no contamination of the firing furnace or photomask due to sublimation, and no omission or defect of the pattern. In the present invention, the compound (1) can be used singly or in combination of two or more kinds. -23- 200537168. In the radiation-sensitive resin composition of the present invention, the use amount of the compound (1) is preferably 5 to 50 parts by weight, and more preferably 100 parts by weight of the copolymer [A]. 5 to 30 parts by weight. In this case, when the used amount of the compound (1) is less than 5 parts by weight, the residual film rate tends to decrease. On the other hand, when it exceeds 50 parts by weight, the solubility of the unexposed portion in the alkaline developing solution may be reduced. Reduced tendency. In the radiation-sensitive resin composition of the present invention, the compound (1) can be used in combination with at least one other radiation-sensitive polymerization initiator. Examples of the other radiation-sensitive polymerization initiator include 0-fluorenyl oxime-type compounds, acetophenone-based compounds, bisimidazole-based compounds, benzoin-based compounds, benzophenone-based compounds, and α- Diketone compounds, polynuclear quinone compounds, gurtanone compounds, phosphine compounds, triple well compounds, and the like. Among these other radiation-sensitive polymerization initiators, 0-fluorenyl oxime-type compounds, acetophenone-based compounds, and bisimidazole-based compounds are preferred. • The above-mentioned fluorenyl oxime compounds are a class of components which further enhance the sensitivity. Specific examples of the 0-fluorenyl oxime type compound include 1- (9-ethyl-6-benzylidene-9.H, carbazol-3-yl) nonane-i, 2-nonane -2 -oxime benzoate, 1- (9-ethyl-6-benzylidene-9.H · -carbazol-3-yl) nonane-1,2-nonane-2-oxime- 0 · acetate, 1- (9-ethyl-6-benzylidene-9.H · -carbazol-3-yl) pentane-1,2-pentane-2-oxime_〇-ethyl Acid ester, 1- (9_ethyl-6-benzylidene-9'-carbazol-3-yl) octane-1-one oxime-0-acetate, ^ [9 · ethyl-6- (2-methylbenzylidene) -9 · Η · -carbothio-3-yl] Oto-1-one · benzoate, 丨 [9_ethyl-24-200537168 -6- (2-methylbenzylidene) -9.Η.-carbazol-3-yl] ethane-1-one oxime-〇_acetate, 1 · [9 -ethyl · 6- (1,3,5-trimethylbenzylidene) -9 · Η · -carbazol-3-yl] ethane-1-ketooxime · -benzoate, 1- [9-n-butyl -6- (2-ethylbenzyl) -9 · Η · -weiwa-3-yl] Ethyl-1-keto-benzoate, ι, 2-octanedione [4- (phenylthio) phenyl] -2- (0-benzylidene), 1,2-butanedione-1- [4- (phenylthio) phenyl] · 2- (〇 -Benzylidene oxime), 1,2-butanedione-1- [4- (phenylthio) phenyl] -2- (〇-ethylfluorenyloxime), ι, 2-octanedione · fluorene- [4- (methylthio) phenyl] -2- (0-benzene Formamidine oxime), ι, 2-octanedione-fluorene- [4- (phenylthio) phenyl] -2- [0- (4-methylbenzylhydrazone)] and the like. Among these 0-fluorenyl oxime-type compounds, M9-ethyl-6- (2-methylbenzylmethyl) -9 · Η · -yesterday 卩 -3_yl] 院 院 -1- 嗣Feto-o-acetic acid vinegar, ι, 2 · octanedione-1- [4- (phenylthio) phenyl] -2- (〇-benzylideneoxime), and the like. The above-mentioned 0-fluorenyl oxime type compounds can be used alone or in combination of two or more. The use amount of the o-fluorenyl oxime type compound is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, based on 100 parts by weight of the copolymer [A]. In this case, when the amount of the 0-fluorenyl oxime type compound exceeds 30 parts by weight, the solubility of the unexposed portion in the alkaline developer tends to decrease, and because of the Contamination by a sublimation furnace or a photomask tends to increase. In addition, when the amount of the o-fluorenyl oxime-type compound used is less than 5 parts by weight, the residual film rate may decrease. The aforementioned acetophenone-based compound is a component having an effect of adjusting the shape of the formed spacer. Examples of the acetophenone-based compound include α-hydroxyketone-based compounds and α-aminoketone-based compounds. -25- 200537168 As specific examples of the above-mentioned hydroxy ketone compounds, p-phenyl-2-hydroxy-2-methylpropane-1-one, 1- (4-isopropylphenyl) -2 -Hydroxy-2-methylpropane-1-one, 4- (2-hydroxyethoxy) phenyl- (2-meryl-2-propyl) one, hydroxycyclohexylphenyl ketone, etc .; as the above-mentioned α Specific examples of -amino ketone compounds include 2-methyl-1-[4- (methylthio) phenylphenyl 2-morpholinopropan-1-one, 2-benzyl-2- 2- (Dimethylamino) -1- (4-morpholinophenyl) butane-butanone, 1- (2-bromo-4-morpholinophenyl) -2-benzyl-2-dimethylamine Butane-1-one, 2- (2-bromobenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butane-1-one, 2- (4- Bromobenzyl) -2 · (dimethylamino) -1- (4-morpholinophenyl) butane-1-one and the like. Specific examples of the acetophenone-based compounds other than these compounds include 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, and 2,2-dimethoxy- 2-phenylacetophenone and the like. Among these acetophenone compounds, 2-methylmethylthio) phenyl] -2-morpholinopropane-1-one and 2-benzyl-2- (dimethylamino) -1 are preferred. -(4-morpholinophenyl) butane-1-one, 1- (2-bromo-4-morpholinophenyl) -2-benzyl-2-dimethylaminobutane-1-one , 2- (4-bromobenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butane-1-one, and the like. The aforementioned acetophenone compounds may be used alone or in combination of two or more. The use amount of the acetophenone-based compound is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, based on 100 parts by weight of the copolymer [A]. In this case, when the amount of the acetophenone-based compound exceeds 30 parts by weight, the contamination of the firing furnace or the photomask caused by the sublimation of the acetophenone-based compound and the generation of foreign matter in the liquid are increased. tendency. When the amount of the acetophenone-based compound is less than 1 part by weight, the residual film rate during development may be reduced. -26- 200537168 The above-mentioned bisimidazole compound is a component that can adjust the shape of the formed spacer and can further improve the sensitivity, image resolution, or adhesion to the substrate. Specific examples of the bisimidazole-based compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1, 2'-bisimidazole, 2,2'-bis (2-bromophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-bisimidazole, 2 , 2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-bisimidazole, 2,2'-bis (2,4-dichlorophenyl) ) -4,4 ', 5,5'-tetraphenyl-1,2'-bisimidazole, 2,2'-bis- (2,4,6-trichlorophenyl) -4,4', 5 , 5'-tetraphenyl-1,2'-bisimidazole, 2,2'-bis (2-bromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-bis Imidazole, 2,2'-bis (2,4-dibromophenyl) -4,4,5,5,5-tetraphenyl-1,2, -bisimidazole, 2,2'-bis (2, 4,6-tribromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-bisimidazole and the like. Among these bisimidazole compounds, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-bisimidazole, 2,2 '· Bis (2,4-dichlorophenyl) -4,4,5,5, tetraphenyl-1,2, -bisimidazole, 2,2'-bis (2,4,6-trichloro Phenyl) -4,4 ', 5,5' · tetraphenyl-1,2 '· bisimidazole, etc., and particularly preferably 2,2'-bis (2,4-dichlorophenyl) -4, 4 ', 5,5'-tetraphenyl-1,2'-bisimidazole. ^ The above bisimidazole compounds can be used alone or in combination of two or more. The use amount of the bisimidazole-based compound is preferably 50 parts by weight or less, more preferably 35 parts by weight or less, based on 100 parts by weight of the copolymer [A]. In this case, when the amount of the bisimidazole-based compound exceeds 50 parts by weight, the amount of the eluted substance in the liquid crystal increases, which makes it easy to reduce the voltage retention rate. At the same time, the firing furnace or the Contamination such as photomasks tends to increase. Conversely, when the amount of bisimidazole-based compound used is less than 0.1-27 parts by weight, the residual film rate may decrease. In the radiation-sensitive resin composition of the present invention, when a bisimidazole-based compound is used as a radiation-sensitive polymerization initiator component, it is preferable to use a dialkyl-containing compound having a sensitizing effect on the bisimidazole-based compound in combination. Amine-based compounds. As such a compound containing a dialkylamino group, for example, a benzophenone derivative containing a dialkylamino group and a benzoate containing a dialkylamino group are more preferable, and examples thereof include, for example, , 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, p-dimethylaminobenzoate, p-diethylamine Ethyl benzoate, isoamyl p-dimethylaminobenzoate, isoamyl p-diethylaminobenzoate, and the like. Among these dialkylamino group-containing compounds, 4,4'-bis (diethylamino) benzophenone is particularly preferred. The dialkylamino group-containing compound may be used singly or as a mixture of two or more kinds. When a bisimidazole compound and a dialkylamino group-containing compound are used in combination, the amount of the compound containing a dialkylamine group is preferably 0.1 to 100 parts by weight of the copolymer [A]. 50 parts by weight, more preferably 1-20 parts by weight. In this case, when the amount of the dialkylamine-containing compound used is less than 0.1 part by weight, the obtained spacer is liable to cause film reduction or poor shape of the spacer. On the contrary, when it exceeds 50 parts by weight, the spacer At the same time, contamination of the firing furnace or photomask due to sublimation of the compound containing a dialkylamine group tends to increase. Furthermore, in the radiation-sensitive resin composition of the present invention, when a bisimidazole-based compound and a compound containing a dialkylamine group are used as radiation-sensitive components, it is preferable to add one A thiol compound capable of supplying a hydrogen radical to a bisimidazole compound. Diimidazole compounds will be cracked due to sensitization by dialkylamine-containing compounds and generate imidazole radicals. However, if no thiol compounds are present at this time, high radical polymerization initiation ability cannot be obtained. Objects often form undesirable shapes such as inverted cones. However, by adding a thiol compound to a system in which a biimidazole compound and a compound containing a dialkylamine group coexist, a hydrogen radical can be supplied to the imidazole radical, and as a result, the imidazole radical is converted into a neutral imidazole. At the same time, sulfur radicals with high polymerization initiation energy are generated, so that the shape of the spacer becomes an ideal forward tapered shape. Examples of the thiol compound include 2-fluorenylbenzothiazole, 2-fluorenylbenzoxazole, 2-fluorenylbenzimidazole, and 2-fluorenyl-5-methoxybenzothiazole. And 2-aromatic-5-methoxybenzimidazole and other aromatic compounds; 3-adenoylpropionic acid, methyl 3-fluorenylpropionate, ethyl 3-mercaptopropionate, and octyl 3-fluorenylpropionate And other aliphatic monothiols; 3,6-difluorene-1,8 · octane dithiol, tetrapentaerythritol tetra (fluorenyl acetate), tetrapentaerythritol tetra (3-fluorene Propionate) and other aliphatic polythiol compounds. These thiol compounds can be used individually or in mixture of 2 or more types. When a bisimidazole compound, a dialkylamino group-containing compound, and a thiol compound are used in combination, 'the amount of the thiol compound is preferably 0 · 1 · relative to 100 parts by weight of the copolymer [A]. 50 parts by weight 'is more preferably 1-20 parts by weight. In this case, 'When the used amount of the thiol compound is less than 0.1 parts by weight, there is a tendency that the obtained spacer tends to have a reduced film or a poor shape. On the contrary, when it exceeds 50 parts by weight, the shape of the spacer may be Damage, -29- 200537168 At the same time, because of the sublimation of thiol compounds, the possibility of contamination such as firing furnaces or photomasks tends to increase. In the radiation-sensitive resin composition of the present invention, the use ratio of other radiation-sensitive polymerization initiators is preferably 100 parts by weight or less, and more preferably 80 weight parts with respect to 100 parts by weight of the entire radiation-sensitive polymerization initiator. It is particularly preferably 60 parts by weight or less. In this case, when the use ratio of the other radiation-sensitive polymerization initiator exceeds 100 parts by weight, the desired effect of the present invention may be impaired. One optional additive 1 In the radiation-sensitive resin composition of the present invention, any additive other than the above components can be mixed as needed, such as a surfactant, a bonding aid, and a storage stabilizer, as long as the effect of the present invention is not impaired. , Heat resistance improver, etc. The surfactant is a mixed component for improving coating performance, and a fluorine-based surfactant and a siloxane-based surfactant are preferred. As the above-mentioned fluorine-based surfactant, a compound having a fluoroalkyl group and / or a fluorinated alkyl group at at least one of the terminal, the main chain, and the side chain is preferable, and examples thereof include: 1,1,2,2-tetrafluoro-n-octyl (1,1,2,2-tetrafluoro-n-propyl) ether, 1,1,2,2-tetrafluoro-n-octyl (n-hexyl) Ether, octaethylene glycol di (1,1,2,2-tetrafluoro-n-butyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoro-n-pentyl) ether, Octapropylene glycol di (1,1,2,2-tetrafluoro-n-butyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoro-n-pentyl) ether, 1,1, 2,2,3,3-hexafluoro-n-decane, 1,1,2,2,8,8,9,9,10,10-decafluoro-n-dodecane, sodium perfluoro-n-dodecanesulfonate And sodium fluoroalkylbenzene sulfonates, sodium fluoroalkyl phosphonates, sodium fluoroalkyl carboxylates, fluoroalkyl polyoxyethylene ethers, diglycerol tetrakis (fluoroalkyl polyoxyethylene-30) -200537168 ene ether), fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl polyoxyethylene ether, perfluoroalkyl polyoxyethanol, perfluoroalkyl alkoxy ester, Fluorine-based alkyl esters and the like. In addition, as commercially available products of fluorine-based surfactants, for example, BM-1 000, BM-1 100 (the above products are manufactured by B M C H EM IE), MEGAFACE F142D, MEGAFACE F172, MEGAFACE F173,

MEGAFACE F178、MEGAFACE F183、MEGAFACE F191、 MEGA FA CE F471、MEGA FACE F4 76(以上產品爲大日本油墨 化學工業（股）製造），FLUORAD FC-170C 、 FLUORAD FC-17 1、FLUORAD FC-43 0、FLUORAD FC - 4 3 1 (以上產口口口爲 住友 3M(股）製造），SURFLON S-112、 SURFLON S-113、 SURFLON S-131 、 SURFLON S -1 41 、 SURFL〇N S -1 45 、 SURFLON S- 3 82、SURFLON SC-101、SURFLON SC-102、 SURFLON SC-103、 SURFLON SC-104、 SURFLON SC-105、 SURFLON SC-106(以上產品爲旭硝子（股）製造），EFTQP EF301、EFTOP EF3 03、EFTOP EF352(以上產口口口爲新秋田化 成（股）製造），FTERGENT FT-100、FTERGENT FT-110、MEGAFACE F178, MEGAFACE F183, MEGAFACE F191, MEGA FA CE F471, MEGA FACE F4 76 (the above products are manufactured by Dainippon Ink Chemical Industry (stock)), FLUORAD FC-170C, FLUORAD FC-17 1, FLUORAD FC-43 0, FLUORAD FC-4 3 1 (The above products are manufactured by Sumitomo 3M Co., Ltd.), SURFLON S-112, SURFLON S-113, SURFLON S-131, SURFLON S -1 41, SURFL〇NS -1 45, SURFLON S-82, SURFLON SC-101, SURFLON SC-102, SURFLON SC-103, SURFLON SC-104, SURFLON SC-105, SURFLON SC-106 (the above products are manufactured by Asahi Glass), EFTQP EF301, EFTOP EF3 03. EFTOP EF352 (the above-mentioned products are manufactured by Shin Akita Chemical Co., Ltd.), FTERGENT FT-100, 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-25 1(以上產品爲耐歐斯（股）製造）等。 作爲上述的硅氧烷類表面活性劑，例如可以列舉以下列 商品名銷售的產品：Toray Silicone DC3PA、Toray Silicone DC7PA、Tor ay Silicone SH 1 1 PA、Toray Silicone SH2 1 PA、 Tor ay Silicone SH28PA、Toray Silicone SH29PA、Toray -31- 200537168FTERGENT FT-140A, FTERGENT FT-150, FTERGENT FT-250, FTERGENT FT-21, FTERGENT FT-300, FTERGENT FT-310, FTERGENT FT-400S, FTERGENT FTX-218, FTERGENT FTX-25 1 Oss (stock) manufacturing) and so on. Examples of the silicone-based surfactants include products sold under the following trade names: Toray Silicone DC3PA, Toray Silicone DC7PA, Tor ay Silicone SH 1 1 PA, Toray Silicone SH2 1 PA, Tor ay Silicone SH28PA, Toray Silicone SH29PA, Toray -31- 200537168

Silicone SH30PA、Tor ay Silicone SH-190、To ray Silicone SH-193、To ray Silicone SZ-6032、To ray Silicone SF-8428、 Tor ay Silicone DC-57、Toray Silicone DC-190(以上產品爲 Toray Dow Corning Silicon (股）製造），TSF-4440、 TSF-4300、TSF-4445、TSF-4446、TSF-4460、TSF-4452(以 上產品爲GE東芝Silicon(股）製造）。 此外，作爲上述以外的表面活性劑，例如可以列舉：聚 氧乙烯十二烷基醚、聚氧乙烯十八烷基醚、聚氧乙烯油基 醚等聚氧乙烯烷基醚類；聚氧乙烯正辛基苯基醚、聚氧乙 烯正壬基苯基醚等聚氧乙烯芳基醚類；聚氧乙烯二月桂酸 酯、聚氧乙烯二硬脂酸酯等聚氧乙烯二烷基酯類等非離子 型表面活性劑；作爲市售的商品可以列舉KP34 1 (信越化學 工業（股）製造）、水° U 7 口-No.5 7、水° U 7 口-Νο·95(以上產 品爲共榮社化學（股）製造）等。 這些表面活性劑可以單獨使用或者2種以上混合使用。 相對於100重量份的共聚物[Α]，表面活性劑的混合量較 佳爲5重量份以下，更佳爲2重量份以下。在此情況下， 表面活性劑的混合量超過5重量份時，塗布時往往容易產 生塗膜粗糙。 上述的黏結助劑是用來進一步提高與基板的黏附性的混 合成分。 作爲如此的黏結助劑，較佳爲官能性矽烷偶聯劑，作爲 其例子，可以舉出：具有羧基、甲基丙烯醯基、乙烯基、 異氰酸酯基、環氧基等反應性官能基的矽烷偶聯劑，更具 體而言，可以舉出三甲氧基甲矽烷基苯甲酸、r-甲基丙烯 -32- 200537168 > 醯氧基丙基三甲氧基矽烷、乙烯基三乙醯氧基矽烷、乙烯 基三甲氧基矽烷、r-異氰酸酯基丙基三乙氧基矽烷、r-環氧丙氧基丙基三甲氧基矽烷、2-(3，4-環氧基環己基）乙基 三甲氧基矽烷等。 這些黏結助劑可以單獨使用或者2種以上混合使用。 相對於100重量份的4共聚物[A]，黏結助劑的混合量較佳 爲20重量份以下，更佳爲10重量份以下。黏結助劑的混 合量如果超過20重量份，則往往容易產生顯影殘餘。 作爲上述的保存穩定劑，例如可以舉出：硫、醌類、氫 醌類、聚氧化合物、胺類、硝基亞硝基化合物等，作爲其 例子，可以舉出4-甲氧基苯酚、N_亞硝基-N-苯基羥基胺鋁 等。 相對於100重量份的共聚物[A]，保存穩定劑的使用量較 佳爲3.0重量份以下，更佳爲0.5重量份以下。在此情況下， 保存穩定劑的使用量超過3.0重量份時，靈敏度降低，所 得間隔物的形狀可能受到損害。 作爲上述的耐熱性提高劑，例如可以舉出N-(烷氧基甲基） ® 乙炔脲化合物、N-(烷氧基甲基）三聚氰胺化合物、具有2 個以上環氧基的化合物等。 作爲上述的N-(烷氧基甲基）乙炔脲化合物，例如可以舉 出：N，N，N，N-四（甲氧基甲基）乙炔脲、N，N，N，N-四（乙氧基 甲基）乙炔脲、N，N，N，N-四（正丙氧基甲基）乙炔脲、N，N，N,N-四（異丙氧基甲基）乙炔脲、N，N，N，N-四（正丁氧基甲基）乙炔 脲、N，N，N，N-四（三級丁氧基甲基）乙炔脲等。 在這些 N-(烷氧基甲基）乙炔脲化合物中，較佳爲 -33- 200537168 . 叱1^,心.四（甲氧基甲基）乙炔脲。 作爲上述的N-(烷氧基甲基）三聚氰胺化合物，例如可以 舉出：1叱^1^六（甲氧基甲基）三聚氰胺、叱叱叱叱叱1^-六（乙氧基甲基）三聚氰胺、N，N，N，N，N，N-六（正丙氧基甲基） 三聚氰胺、N，N，N，N，N，N-六（異丙氧基甲基）三聚氰胺、 N，N，N，N，N，N-六（正丁氧基甲基）三聚氰胺、N，N，N，N，N，N-六 (三級丁氧基甲基）三聚氰胺等。 於此等 N-(烷氧基甲基）三聚氰胺化合物中，優先用 g N，N，N，N，N，N-六（甲氧基甲基）三聚氰胺，作爲其市售商 品，例女口 可以歹(1舉 NIKALAC N-2702、NIKALAC MW-30M(以 上產品爲三和化學（股）製造）等。 作爲上述具有 2個以上環氧基的化合物，例如可以舉 出：乙二醇二縮水甘油醚、二乙二醇二縮水甘油醚、聚乙 二醇二縮水甘油醚、丙二醇二縮水甘油醚、三丙二醇二縮 水甘油醚、聚丙二醇二縮水甘油醚、新戊二醇二縮水甘油 醚、1，6-己二醇二縮水甘油醚、丙三醇二縮水甘油醚、三羥 $ 甲基丙烷三縮水甘油醚、加氫雙酚A二縮水甘油醚、雙酚 A二縮水甘油醚等。 另外，作爲具有2個以上環氧基的化合物的市售商品， 例如可以列舉伊波拉托40E、伊波拉托100E、伊波拉托 200E、伊波拉托70P、伊波拉托200P、伊波拉托400P、伊 波拉托1 500NP、伊波拉托1 600、伊波拉托80MF、伊波拉 托100MF、伊波拉托3002、伊波拉托4000(以上產品爲共榮 社化學（股）製造）等。 這些耐熱性提高劑可以單獨使用或者2種以上混合使 -34- 200537168 月。 本發明的放射線敏感性樹脂組合物，較佳爲將其溶 $菌當的溶劑中，製成組合物溶液後使用。 作爲上述的溶劑，可以使用那些能均勻溶解構成放 μ感性樹脂組合物的各成分、不與各成分反應並且具 胃揮發性的溶劑。 作爲這樣的溶劑的例子，可以舉出與關於製造共聚! 白勺聚合技術中所例示的同樣的溶劑。 Φ 在這些溶劑中，從各成分的溶解能力、與各成分的 性和易於形成被膜等角度考慮，較佳爲醇類、二乙二 院基醚乙酸酯類、二乙二醇一烷基醚乙酸酯類、二乙 火完基醚類、丙二醇一烷基醚乙酸酯類、烷氧基丙酸烷 類等’更佳爲苯甲醇、2 -苯乙醇、3 -苯基-1-丙醇、乙 一正丁基醚乙酸酯、二乙二醇一乙基醚乙酸酯、二乙 二甲醚、二乙二醇二乙醚、二乙二醇乙基甲基醚、丙 一甲基醚乙酸酯、丙二醇一乙基醚乙酸酯等。 | 上述溶劑可以單獨使用或者2種以上混合使用。 此外’在本發明中，還可以將上述溶劑與高沸點溶 起並用。 作爲上述的高沸點溶劑，例如可以舉出：Ν-甲基甲酸 Ν，Ν-二甲基甲醯胺、Ν-甲基甲醯苯胺、Ν_甲基乙醯胺、 二甲基乙醯胺、Ν-甲基吡咯烷酮、二甲亞颯、苄基乙基 二己基醚、丙酮基丙酮、異佛爾酮、己酸、辛酸、丨_辛 1-壬醇、乙酸苄酯、苯甲酸乙酯、草酸二乙酯、馬來 乙酯、r -丁內酯、碳酸亞乙酯、碳酸亞丙酯、苯基溶 解於 射線 有適 勿[A] 反應 醇一 二醇 基酯 二醇 二醇 二醇 劑一 胺、 N，N- 醚、 醇、 酸二 纖劑 -35- 200537168 乙酸酯等。 這些高沸點溶劑可以單獨使用或者2種以上混合使用。 這樣製備的組合物溶液，還可以用孔徑〇. 5 // m左右的微 孔過濾器過濾後使用。 間隔物的形成方法 下面說明使用本發明的放射線敏感性樹脂組合物來形成 本發明的間隔物的方法。 形成本發明的間隔物的方法至少包含下述U)〜（4)的步 驟。 (1) 在基板上形成本發明的放射線敏感性樹脂組合物的 被膜的步驟； (2) 對該被膜的至少一部分用放射線進行曝光的步驟； (3) 將曝光後的上述被膜顯影的步驟； (4) 將顯影後的上述被膜加熱的步驟。 下面依次而言明上述的各步驟。 一步驟（1) 一 在透明基板的一個側面上形成透明導電膜，在該透明導 ® 電膜上塗布本發明的放射線敏感性樹脂組合物的組合物溶 液，然後通過將該塗布面加熱（預烘焙）來形成被膜。 作爲在形成間隔物時使用的透明基板，例如可以舉出玻 璃基板、樹脂基板等，更具體地可以舉出鹼石灰玻璃、無 鹼玻璃等的玻璃基板；由聚對苯二甲酸二乙二醇酯、聚對 苯二甲酸丁二醇酯、聚醚颯、聚碳酸酯、聚醯亞胺等的塑 膠製成的樹脂基板。 作爲設置在透明基板的一個側面上的透明導電膜，例如 -36- 200537168 可以舉出由氧化錫（Sn〇2)形成的NESA膜（美國PPG公司注 冊商標）、由氧化銦·氧化錫（In2〇3-Sn〇2)形成的ITO膜等。 作爲組合物溶液的塗布方法，例如可以採用噴塗法、輥 塗法、旋轉塗法、狹縫模塗法、刮條塗法、噴墨塗法等適 宜的方法，較佳爲旋轉塗法、狹縫模塗法。 另外，預烘焙的條件隨各成分的種類、混合比例等的不 同而異，但通常是在70〜120 °C的溫度下進行1〜15分鐘左 右。 一步驟（2) — 進而，對已形成的被膜的至少一部分用放射線進行曝 光。在此情況下，在對被膜的一部分進行曝光時，一般是 通過一種具有規定的圖案的光掩模進行曝光。 作爲適用的放射線，可以使用可見光線、紫外線、遠紫 外線、電子射線、X射線等，但較佳爲波長在190〜45Onm 範圍內的放射線，特別是含有波長爲365nm的紫外線的放 射線爲宜。 以使用照度計（〇AI model 365，OAI Optical Associates 公 ® 司製）測定的曝光放射線的波長爲365nm的光強度作爲曝 光量的値，該曝光量通常爲100〜10,000J/m2，較佳爲500 〜3,000J/m2。 一步驟（3) — 進而通過將曝光後的被膜顯影來除去不需要的部分，從 而形成預定的圖案。 作爲適用於顯影的顯影液，例如可以使用氫氧化鈉、氫 氧化鉀、碳酸鈉、矽酸鈉、偏矽酸鈉、氨等的無機鹼類； -37- 200537168 ， 乙胺、正丙胺等的脂肪族一級胺類；二乙胺、二 的脂肪族二級胺類；三甲胺、甲基二乙基胺、二 胺、三乙胺等的脂肪族三級胺類；吡咯、呱嗪、 嗪、N-甲基吡咯烷、1，8-二氮雜雙環[5.4.0]-7-十 1，5-二氮雜雙環[4·3·0]-5-壬烯等的脂環族三級 啶、三甲基吡啶、二甲基吡啶、喹啉等的芳香族三 二甲基乙醇胺、甲基二乙醇胺、三乙醇胺等的烷 氫氧化四甲銨、氫氧化四乙銨等四級銨鹽等的鹼 | 的水溶液。 另外，也可以向上述的鹼性化合物的水溶液中 量的甲醇、乙醇等的水溶性有機溶劑和/或表面活 用。 顯影的方法可以是流液法、浸漬法、噴淋法等 種，顯影的時間通常是在常溫下1 0〜1 8 0秒。 顯影後，例如進行30〜90秒鐘的流水沖洗，然 壓縮空氣或壓縮氮氣進行風乾，從而形成所需的 一步驟（4) — ® 進而，使用電熱板或烘箱等加熱裝置，將所獲 規定的溫度例如100〜160°C下加熱規定的時間， 熱板上加熱5〜30分鐘，在烘箱中加熱30〜180 此進行加熱（後烘焙），從而獲得所需的間隔物。 以往在形成間隔物時使用的放射線敏感性樹脂 果不在180〜200°C左右以上的溫度進行加熱處理 間隔物就不能獲得充分的性能，但是本發明的放 性樹脂組合物可使用比以往低的加熱溫度，其結 正丙胺等 甲基乙基 N -甲基呱 一碳烯、 胺類；吡 :級胺類； 醇胺類； 性化合物 添加適當 性劑後使 中的任一 後例如用 圖案。 的圖案在 例如在電 分鐘，如 組合物如 ，所獲的 射線敏感 果不會導 -38- 200537168 _ 致樹脂基板的變黃或變形，並能獲得抗壓強度、液晶配向 時的耐摩擦性、與透明基板的黏附性等的各種性能均優良 的間隔物。 液晶顯示元件 本發明的液晶顯示元件具有如上述那樣形成的本發明的 間隔物。 作爲液晶顯示元件的結構沒有特殊限定，但是可以舉出 如第1圖所示那樣的結構，該結構是在透明基板上形成彩 g 色濾光片和本發明的間隔物，並具有通過液晶層配置的兩 片配向膜、相互對向的透明電極、相互對向的透明基板等 而形成的結構。另外，如第1圖所示，也可以根據需要， 在偏光板或彩色濾光片上設置保護膜。 如第2圖所示，在透明基板上形成彩色濾光片和本發明 的間隔物，並通過配向膜和液晶層而與薄膜電晶體（TFT)陣 列對向，這樣也可以構成TN-TFT型的液晶顯示元件。在此 情況下，也可以根據需要，在偏光板或在彩色濾光片上設 置保護膜。 ^ 本發明的間隔物形成用放射線敏感性樹脂組合物可以抑 製由於放射線敏感性聚合引發劑成分的昇華所造成的燒成 爐或光掩模等的污染，不會產生液體中的異物，而且具有 高的靈敏度和高的圖像解析度，同時能夠容易地形成一種 斷面形狀、抗壓強度、耐摩擦性、與透明基板的黏附性等 各種性能均優良的間隔物，並且在形成間隔物時可以降低 後烘焙的溫度，不會導致樹脂基板的變黃或變形。 本發明的液晶顯示元件由於具有一種斷面形狀、抗壓強 39- 200537168 ^ 度、耐摩擦性、與透明基板的黏附性等各種性能均優良的 間隔物，因此可以長期地確保高的可靠性。 【實施方式】 下面舉出實施例來更具體而言明本發明的實施方式。 合成例1 在帶有冷卻管和攪拌器的燒瓶中裝入2,2’-偶氮二（2,4-二甲基戊腈）5重量份和二乙二醇乙基甲基醚250重量份， 接著裝入甲基丙烯酸17重量份、甲基丙烯酸縮水甘油酯45 ^ 重量份、苯乙烯20重量份和甲基丙烯酸二環戊酯18重量 份，用氮氣置換後，一面緩慢地攪拌，一面使溶液的溫度 上升至70°C，保持這一溫度4小時使之聚合，得到含共聚 物[A]的樹脂溶液（固體成分濃度=28.4重量％)。該共聚物 [A]的 Mw 爲 1 6,000。 將該共聚物[A]稱爲“共聚物（Α·1)” 。 使用 GPC(凝膠滲透色譜）HLC-8020(東梭（股）製（TOSOH)) 測定共聚物（A -1)和下述聚合物（A - 2)的M w。 合成例2 ^ 在帶有冷卻管和攪拌器的燒瓶中裝入2,2’-偶氮二（2,4-二甲基戊腈）7重量份和二乙二醇乙基甲基醚250重量份， 接著裝入甲基丙烯酸18重量份、甲基丙烯酸縮水甘油酯20 重量份、苯乙烯5重量份、甲基丙烯酸二環戊酯32重量份 和甲基丙烯酸四氫糠酯25重量份，用氮氣置換後一面緩慢 地攪拌，一面使溶液的溫度上升至7(TC，保持這一溫度4 小時使之聚合，得到含有共聚物[A]的樹脂溶液（固體成分 濃度= 28.8重量％)。該共聚物[A]的Mw是11，000。 -40 - 200537168 ^ 將該共聚物[A]稱爲“共聚物（A-2)” 。 實施例1 一組合物溶液之製備一 將作爲[A]成分而在合成例1中獲得的樹脂溶液作爲共聚 物（A-1)，以其加入量作爲1〇〇重量份（固體成分）、作爲[B] 成分的二四級戊四醇六丙烯酸酯（商品名 KAYARAD DPHA、日本化藥（股）製造）80重量份以及作爲[C]成分的 2-(4-甲基苄基）-2-(二甲胺基）-1-(4-嗎啉并苯基）丁烷-1-酮 $ (商品名IRGACURE 379,汽巴精業化學公司製）40重量份、 作爲黏结助劑的7 -環氧丙氧基丙基三甲氧基硅烷5重量 份、作爲表面活性劑的丁二烯FTX-218產品0.5重量份、 作爲保存劑的4-甲氧基苯酚0.5重量份混合，按固體成分 濃度成爲3 0重量％的比例溶解於丙二醇甲基醚乙酸酯中， 然後用孔徑0.5 v m的微孔過濾器過濾，製成組合物溶液。 一形成間隔物一 使用離心塗布機在無鹼玻璃基板上塗布上述組合物溶 液，然後在電熱板上於80 °C下預烘焙3分鐘，形成膜厚6.0 • m的被膜。 接著，通過具有10//m正方形殘留圖案的光掩模，使用 波長爲3 65nm、曝光強度爲250W/m2的紫外線對所得被膜 進行1 0秒鐘的曝光。然後用0 · 0 5重量％的氫氧化鉀水溶液 在25 °C下顯影60秒，用純水洗滌1分鐘。然後將其放入烘 箱中，在150°C下進行120分鐘的後烘焙，形成規定圖案的 間隔物。 然後按下述（I)〜（VIII)的順序進行評價，評價結果示於表 -41- 200537168 ^ 2-1 中。 (I) 靈敏度的評價 在形成間隔物時，以顯影後的殘膜率（顯影後的膜厚xlOO/ 初始膜厚，以下相同）達到9 0 %的曝光量作爲靈敏度。以該 曝光量爲1,500 〗/m2以下時的靈敏度爲良好。 (II) 圖像解析度的評價 在形成間隔物時，根據顯影後殘膜率爲90 %以上的曝光 量按照最小圖案尺寸法進行評價。 φ (III)間隔物斷面形狀的評價 使用掃描電子顯微鏡觀察所得間隔物的斷面形狀，根據 其形狀相當於第3圖中所示的A-D中的某一種進行評價。 此時，如A或B所示，圖案邊緣爲正錐形或垂直狀，這兩 種情況均表示斷面形狀良好。與此相反，如C所示，靈敏 度不夠好、殘膜率低、斷面尺寸比A和B小、其形狀爲底 面呈平面的半凸透鏡狀，這一情況表示斷面形狀不良。另 外，如D所示，圖案邊緣爲倒錐形（在斷面形狀中，膜表面 的邊比基板一側的邊還長的倒三角形），這一情況在後續的 ® 摩擦處理時圖案被剝離的可能性非常高，因而斷面形狀不 良。 (IV)抗壓強度的評價 使用微型抗壓試驗機（商品名MCTM-200、島津製作所（股） 製造）測定所得間隔物的抗壓強度，具體而言，在23。<：的溫 度下使用直徑5 0 // m的平面壓頭施加1 〇 m N的載荷，測定 此時的變形量，當該値在〇 · 5 // m以下時，表明抗壓強度良 好。 -42- 200537168 , (V)耐摩擦性的評價 使用液晶配向膜塗布用印刷機在形成了間隔物的基板上 塗布AL3046(商品名、：[SR(股）製造）作爲液晶取向劑，然後 在1 8 0 °C下乾燥1小時，形成膜厚0 · 〇 5 // m的液晶取向劑的 塗膜。 然後，使用具有纒繞聚醯胺製的布的輥的摩擦機，在輥 轉速500 rpm、載物台移動速度lcm/秒的條件下，對該塗 膜進行摩擦處理。這時，根據圖案是否被削去或剝離進行 φ 評價。 (VI) 黏附性的評價 除了不使用光掩模之外，與上述形成間隔物的場合同樣 操作，形成硬化膜。然後，在nS Κ·5400( 1 900)8.5的附著 性試驗中，按8·5·2的劃格膠帶法進行評價。這時，在表2 中示出了每100個格子中殘留的格子數。 (VII) 昇華性的評價 將上述組合物溶液塗布在基板上，然後將其乾燥，形成 了膜厚6.0/zm的被膜。使用正辛烷（比重= 0.701，注入量 ® = 〇·〇2μ 1)作爲標準物質，以100°C /10分鐘作爲清潔（purge) 條件，對上述被膜進行頂空氣相色譜法/品質分析（頂空取 樣器爲日本分析工業（股）製的JHS-100A ;氣相色譜/品質分 析裝置爲日本分析工業（股）製的JEOL JMS-AX505W型品質 分析計），求出來自放射線敏感性聚合引發劑的峰的面積 A，按下述計算式算出按正辛烷換算的揮發量。該揮發量越 大，表明其昇華性越大。 按正辛烷換算的揮發量的計算式 揮發量（/z g)= Αχ(正辛烷的量）（// g)/(正辛烷的峰面積） -43- 200537168 (VIII)液體中異物的評價 將上述組合物溶液在· 1 5 °C的溫度下保存7天，然後用目 視法觀察其中是否出現放射線敏感性聚合引發劑成分的再 結晶產物。進而，將保存過的上述組合物溶液的液溫由—1 5 °C升高至23 °C時，用光散射式液中粒子檢測器（商品名 K S - 2 8 B，RIΟ N (股）製造）測定在每1 # 1中的組合物溶液中 沒有再溶解而殘存下來的0.5 " m以上大小的固體物（殘存 異物）的數目。 實施例2-23 ® 除了使用表1-1中所示各成分作爲[A]成分、[B]成分和[C] 成分之外，其餘與實施例1同樣操作，配製各組合物溶液， 形成間隔物，進行各種評價。評價結果示於表2-1中。 實施例24 將與實施例1同樣的各成分溶解在二乙二醇乙基甲基醚 中，使固體成分濃度成爲1 7 · 5重量％，然後用孔徑〇. 5 // m 的微孔過濾器過濾，製成組合物溶液。除此之外，與實施 例1同樣操作，形成間隔物，進行各種評價，評價結果示 φ 於表2 -1中。 比較例1〜8 除了使用表1-2中所不各成分作爲[A]成分、[B]成分和放 射線敏感性聚合引發劑之外，其餘與實施例1同樣操作， 配製各組合物溶液，形成間隔物，進行各種評價。評價結 果示於表2-2中。 在表1-1和表1-2中，[A]成分以外的各種成分如下面所 述。 B-1:二四級戊四醇六丙烯酸酯； -44- 200537168 B-2:商品名KAYARADDPHA-40H(日本化藥（股）製造）； C-l: 2-(4 -甲基苄基）-2-(二甲胺基）-1-(4 -嗎啉并苯基）丁 烷-1 -酮； D-l: 1-[9-乙基- 6-(2-甲基苯甲醯基咔唑-3-基]-乙 烷-1-酮肟-〇·乙酸酯（商品名CGI-242,汽巴精業化學公司製 造） E -1: 2 -甲基-1 - [ 4 -(甲硫基）苯基]-2 -嗎啉并丙烷-1 -酮（商品 名IRG A CURE 9 07，汽巴精業化學公司製造）； E-2: 2-节基- 2- (一甲胺基）-1-(4-嗎琳并苯基）丁院-1_酮（商 ® 品名IRGACURE 3 69，汽巴精業化學公司製造）； E - 3 : 1 - (2 -溴-4 -嗎啉并苯基）-2 -节基-2 -甲胺基-丁院-1 _酮； F-1: 2,2’-雙（2,4-二氯苯基）-4,4’，5,5、四苯基_1，2，-雙咪 唑； F-2: 4,4’-雙（二乙胺基）二苯甲酮； F-3 : 2-毓基苯并噻唑。Silicone SH30PA, Tor ay Silicone SH-190, To ray Silicone SH-193, To ray Silicone SZ-6032, To ray Silicone SF-8428, Tor ay Silicone DC-57, Toray Silicone DC-190 (The above products are Toray Dow Corning (Manufactured by Silicon), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 (The above products are manufactured by GE Toshiba Silicon). Examples of the surfactant other than the above include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene octadecyl ether, and polyoxyethylene oleyl ether; and polyoxyethylene Polyoxyethylene aryl ethers such as n-octylphenyl ether and polyoxyethylene n-nonylphenyl ether; polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate Non-ionic surfactants; commercially available products include KP34 1 (made by Shin-Etsu Chemical Industry Co., Ltd.), water ° U 7 port-No. 5 7, water ° U 7 port-Νο · 95 (above products) Manufactured by Kyoeisha Chemical Co., Ltd.). These surfactants can be used alone or in combination of two or more. The blending amount of the surfactant is preferably 5 parts by weight or less, and more preferably 2 parts by weight or less, based on 100 parts by weight of the copolymer [A]. In this case, if the blending amount of the surfactant exceeds 5 parts by weight, the coating film tends to be roughened during coating. The above-mentioned adhesion promoter is a mixed component for further improving the adhesion to the substrate. As such a bonding aid, a functional silane coupling agent is preferred, and examples thereof include silanes having reactive functional groups such as a carboxyl group, a methacryl group, a vinyl group, an isocyanate group, and an epoxy group. Examples of the coupling agent include trimethoxysilylbenzoic acid, r-methacryl-32-200537168 > methoxypropyltrimethoxysilane, vinyltriethoxysilane , Vinyltrimethoxysilane, r-isocyanatepropyltriethoxysilane, r-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethyl Oxysilane and so on. These adhesion promoters can be used individually or in mixture of 2 or more types. The blending amount of the bonding aid is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, based on 100 parts by weight of the 4 copolymer [A]. When the compounding amount of the bonding aid exceeds 20 parts by weight, development residue tends to occur easily. Examples of the above-mentioned storage stabilizers include sulfur, quinones, hydroquinones, polyoxy compounds, amines, and nitroso compounds. Examples thereof include 4-methoxyphenol, N_nitroso-N-phenylhydroxylamine and the like. The amount of the storage stabilizer used is preferably 3.0 parts by weight or less, more preferably 0.5 parts by weight or less, based on 100 parts by weight of the copolymer [A]. In this case, when the amount of the storage stabilizer used exceeds 3.0 parts by weight, the sensitivity is lowered, and the shape of the obtained spacer may be damaged. Examples of the heat resistance improver include N- (alkoxymethyl) ® acetylene urea compounds, N- (alkoxymethyl) melamine compounds, and compounds having two or more epoxy groups. Examples of the N- (alkoxymethyl) acetylene urea compound include N, N, N, N-tetrakis (methoxymethyl) acetyleneurea, and N, N, N, N-tetrakis ( Ethoxymethyl) acetylene urea, N, N, N, N-tetra (n-propoxymethyl) acetylene urea, N, N, N, N-tetrakis (isopropoxymethyl) acetylene urea, N , N, N, N-tetra (n-butoxymethyl) acetylene urea, N, N, N, N-tetrakis (tertiary butoxymethyl) acetylene urea and the like. Among these N- (alkoxymethyl) acetylene urea compounds, -33-200537168 is preferred. 叱 1 ^, Xin. Tetra (methoxymethyl) acetylene urea. Examples of the N- (alkoxymethyl) melamine compound include 1 叱 ^ 1 ^ hexa (methoxymethyl) melamine and 叱 叱 叱 叱 叱 1 ^ -hexa (ethoxymethyl) ) Melamine, N, N, N, N, N, N-hexa (n-propoxymethyl) Melamine, N, N, N, N, N, N, N-hexa (isopropoxymethyl) melamine, N , N, N, N, N, N-hexa (n-butoxymethyl) melamine, N, N, N, N, N, N-hexa (tertiary butoxymethyl) melamine and the like. Among these N- (alkoxymethyl) melamine compounds, g N, N, N, N, N, N, N-hexa (methoxymethyl) melamine is preferably used as a commercially available product, such as a female (1) NIKALAC N-2702, NIKALAC MW-30M (the above products are manufactured by Sanwa Chemical Co., Ltd.), etc. Examples of the compound having two or more epoxy groups include ethylene glycol dishrinking. Glyceryl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, trimethylol methyl propane triglycidyl ether, hydrogenated bisphenol A diglycidyl ether, bisphenol A diglycidyl ether, and the like. In addition, as commercially available products of a compound having two or more epoxy groups, for example, Ibolato 40E, Ibolato 100E, Ibolato 200E, Ibolato 70P, Ibolato 200P, Ibolato 400P, Ibolato 1 500NP, Ibolato 1 600, Ibola 80MF, Ibolato 100MF, Ibolato 3002, Ibolato 4000 (the above products are manufactured by Kyoeisha Chemical Co., Ltd.), etc. These heat resistance improvers can be used alone or in combination of two or more. -34- 200537168 The radiation-sensitive resin composition of the present invention is preferably used after being made into a composition solution in a solvent in which the bacteria are dissolved. As the above-mentioned solvent, those which can be uniformly dissolved to form a μ-sensitive resin composition can be used. Each of the components is a solvent that does not react with each component and has gastric volatility. Examples of such solvents include the same solvents as those exemplified in the production of copolymerization! Φ Among these solvents, From the viewpoints of the solubility of each component, the properties of each component, and the ease of forming a film, alcohols, diethylene glycol ether acetates, diethylene glycol monoalkyl ether acetates, and diethyl ether are preferred. Phenyl ethers, propylene glycol monoalkyl ether acetates, alkoxy propanoic acid alkyls, etc. are more preferably benzyl alcohol, 2-phenylethanol, 3-phenyl-1-propanol, ethylene n-butyl ether Acetate, Di Glycol monoethyl ether acetate, diethylene glycol ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene methyl ether acetate, propylene glycol monoethyl ether acetate The above solvents may be used alone or in combination of two or more kinds. In addition, in the present invention, the above solvents may be dissolved and used in combination with a high boiling point. Examples of the high boiling point solvent include: N-methyl N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, dimethylacetamide, N-methylpyrrolidone, dimethylmethylene, benzylethyl Dihexyl ether, acetone acetone, isophorone, hexanoic acid, caprylic acid, octyl 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, maleate, r-butyrolactone , Ethylene carbonate, propylene carbonate, and phenyl are soluble in the rays. [A] Reactive alcohol, monoglycol, diol, glycol, diol, monoamine, N, N-ether, alcohol, and acid. Agent-35-200537168 acetate and so on. These high-boiling-point solvents can be used individually or in mixture of 2 or more types. The composition solution thus prepared can also be used after filtering through a microporous filter having a pore size of about 0.5 // m. Method for Forming Spacer Next, a method for forming the spacer of the present invention using the radiation-sensitive resin composition of the present invention will be described. The method for forming the spacer of the present invention includes at least the following steps U) to (4). (1) a step of forming a film of the radiation-sensitive resin composition of the present invention on a substrate; (2) a step of exposing at least a part of the film with radiation; (3) a step of developing the above-mentioned film after exposure; (4) a step of heating the film after the development. The above steps will be described in order below. One step (1) A transparent conductive film is formed on one side of a transparent substrate, the transparent conductive film is coated with the composition solution of the radiation-sensitive resin composition of the present invention, and the coated surface is heated (preliminarily) Baking) to form a coating. Examples of the transparent substrate used in forming the spacer include glass substrates, resin substrates, and more specifically, glass substrates such as soda-lime glass and alkali-free glass. Polyethylene terephthalate Resin substrates made of plastics such as esters, polybutylene terephthalate, polyether fluorene, polycarbonate, and polyfluorene. As the transparent conductive film provided on one side of the transparent substrate, for example, -36-200537168 includes a NESA film (registered trademark of the United States PPG Corporation) formed of tin oxide (SnO2), and indium oxide · tin oxide (In2 〇3-Sn〇2). As a method for applying the composition solution, for example, a suitable method such as a spray coating method, a roll coating method, a spin coating method, a slit die coating method, a doctor blade coating method, or an inkjet coating method may be adopted, and the spin coating method and the narrow coating method are preferred. Slot die coating. In addition, the pre-baking conditions vary depending on the types of ingredients, mixing ratios, etc., but they are usually carried out at a temperature of 70 to 120 ° C for about 1 to 15 minutes. Step (2) — Furthermore, at least a part of the formed film is exposed to radiation. In this case, when a part of the film is exposed, the exposure is generally performed through a photomask having a predetermined pattern. Applicable radiation may be visible light, ultraviolet rays, far ultraviolet rays, electron rays, X-rays, etc., but radiation having a wavelength in the range of 190 to 45 nm is preferable, and particularly radiation containing ultraviolet rays having a wavelength of 365 nm is suitable. The light intensity of the exposure radiation having a wavelength of 365 nm measured using an illuminance meter (〇AI model 365, manufactured by OAI Optical Associates®) is used as the chirp of the exposure amount, and the exposure amount is usually 100 to 10,000 J / m2, preferably 500 to 3,000 J / m2. Step (3) — The undesired portions are removed by developing the exposed film to form a predetermined pattern. As a developing solution suitable for development, for example, inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia can be used; -37- 200537168, ethylamine, n-propylamine, and the like Aliphatic primary amines; diethylamine, dialiphatic secondary amines; trimethylamine, methyldiethylamine, diamine, triethylamine and other aliphatic tertiary amines; pyrrole, verazine, hydrazine , N-methylpyrrolidine, 1,8-diazabicyclo [5.4.0] -7-deca-1,5-diazabicyclo [4 · 3 · 0] -5-nonene, etc. Tertiary pyridine, trimethylpyridine, dimethylpyridine, quinoline and other aromatic tridimethylethanolamine, methyldiethanolamine, triethanolamine and other quaternary tetramethylammonium hydroxide and tetraethylammonium hydroxide Ammonium salts and other alkali | Alternatively, it may be used in a water-soluble organic solvent such as methanol, ethanol, and / or the surface in an amount of the above-mentioned aqueous solution of the basic compound. The developing method may be a flow method, a dipping method, a spray method, or the like, and the developing time is usually 10 to 180 seconds at a normal temperature. After development, for example, rinse with running water for 30 to 90 seconds, and then air-dry with compressed air or compressed nitrogen to form the required step (4) — ® Furthermore, use a heating device such as a hot plate or an oven to set the obtained requirements The temperature is, for example, 100 to 160 ° C for a predetermined time, heating on a hot plate for 5 to 30 minutes, and heating in an oven for 30 to 180 times (post-baking) to obtain a desired spacer. Conventionally, radiation-sensitive resins used in the formation of spacers cannot achieve sufficient performance if the spacers are not heat-treated at a temperature of about 180 to 200 ° C or higher. However, the radioactive resin composition of the present invention can use lower Heating temperature, which results in methyl ethyl N-methyl fluorene monocarbene and amines such as n-propylamine; pyridine: tertiary amines; alcohol amines; after adding any suitable agent to the sexual compound, for example, using a pattern . For example, in the electrical minutes, such as the composition, the obtained radiation-sensitive fruits will not lead -38- 200537168 _ causing yellowing or deformation of the resin substrate, and can obtain compressive strength, abrasion resistance during liquid crystal alignment Spacer with excellent properties such as adhesion to transparent substrates. Liquid crystal display element The liquid crystal display element of the present invention includes the spacer of the present invention formed as described above. The structure of the liquid crystal display element is not particularly limited, but it may include a structure as shown in FIG. 1. The structure includes forming a color filter and a spacer of the present invention on a transparent substrate and having a liquid crystal layer passing therethrough. A structure formed by two arranged alignment films, transparent electrodes facing each other, transparent substrates facing each other, and the like. In addition, as shown in FIG. 1, a protective film may be provided on a polarizing plate or a color filter as necessary. As shown in FIG. 2, a color filter and a spacer of the present invention are formed on a transparent substrate, and are aligned with a thin film transistor (TFT) array through an alignment film and a liquid crystal layer. This can also constitute a TN-TFT type. Liquid crystal display element. In this case, a protective film may be provided on the polarizing plate or the color filter as required. ^ The radiation-sensitive resin composition for spacer formation of the present invention can suppress contamination of a firing furnace or a photomask caused by sublimation of a radiation-sensitive polymerization initiator component, and does not generate a foreign substance in a liquid. High sensitivity and high image resolution. At the same time, it can easily form a spacer with various properties such as cross-sectional shape, compressive strength, abrasion resistance, and adhesion to a transparent substrate. The post-baking temperature can be reduced without causing yellowing or deformation of the resin substrate. Since the liquid crystal display element of the present invention has a spacer having various properties such as a cross-sectional shape, a pressure resistance of 39-200537168, abrasion resistance, and adhesion to a transparent substrate, it can ensure high reliability for a long period of time. . [Embodiments] Examples are given below to more specifically describe the embodiments of the present invention. Synthesis Example 1 A flask equipped with a cooling pipe and a stirrer was charged with 5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 250 parts by weight of diethylene glycol ethyl methyl ether. 17 parts by weight of methacrylic acid, 45 ^ parts by weight of glycidyl methacrylate, 20 parts by weight of styrene, and 18 parts by weight of dicyclopentyl methacrylate. After replacing with nitrogen, slowly stir, While the temperature of the solution was raised to 70 ° C., the temperature was maintained for 4 hours to polymerize to obtain a resin solution (solid content concentration = 28.4% by weight) containing the copolymer [A]. The copolymer [A] had an Mw of 1 6,000. This copolymer [A] is called "copolymer (A · 1)". The M w of the copolymer (A -1) and the following polymer (A-2) was measured using GPC (gel permeation chromatography) HLC-8020 (TOSOH). Synthesis Example 2 ^ A flask with a cooling tube and a stirrer was charged with 2,2'-azobis (2,4-dimethylvaleronitrile), 7 parts by weight, and diethylene glycol ethyl methyl ether 250. Part by weight, followed by 18 parts by weight of methacrylic acid, 20 parts by weight of glycidyl methacrylate, 5 parts by weight of styrene, 32 parts by weight of dicyclopentyl methacrylate, and 25 parts by weight of tetrahydrofurfuryl methacrylate After being replaced with nitrogen, the solution was stirred slowly, and the temperature of the solution was raised to 7 (TC, and the temperature was maintained for 4 hours to polymerize to obtain a resin solution containing the copolymer [A] (solid content concentration = 28.8% by weight)). The Mw of the copolymer [A] is 11,000. -40-200537168 ^ The copolymer [A] is referred to as "copolymer (A-2)". Example 1 Preparation of a composition solution will be used as [A] Component and the resin solution obtained in Synthesis Example 1 was used as the copolymer (A-1), and the added amount thereof was 100 parts by weight (solid content), and the quaternary pentaerythritol as the [B] component 80 parts by weight of hexaacrylate (trade name: KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) and 2- (4-methyl) as the [C] component Group) 40-parts by weight of 2- (dimethylamino) -1- (4-morpholinophenyl) butane-1-one (trade name IRGACURE 379, manufactured by Ciba Fine Chemical Co., Ltd.) 5 parts by weight of 7-glycidoxypropyltrimethoxysilane as an auxiliary, 0.5 parts by weight of butadiene FTX-218 product as a surfactant, and 0.5 parts by weight of 4-methoxyphenol as a preservative are mixed , Dissolved in propylene glycol methyl ether acetate so that the solid content concentration becomes 30% by weight, and then filtered through a microporous filter with a pore size of 0.5 vm to prepare a composition solution. One uses a centrifugal coater to form a spacer. An alkali-free glass substrate was coated with the above composition solution, and then pre-baked on a hot plate at 80 ° C for 3 minutes to form a film having a thickness of 6.0 • m. Next, a photomask with a 10 // m square residual pattern was passed The resulting film was exposed for 10 seconds using ultraviolet light having a wavelength of 3 65 nm and an exposure intensity of 250 W / m2. Then, it was developed with a 0.5% by weight potassium hydroxide aqueous solution at 25 ° C for 60 seconds, and Wash with pure water for 1 minute. Then put it in the oven and proceed at 150 ° C for 120 minutes After baking, a spacer with a predetermined pattern is formed. Then, the evaluation is performed in the order of (I) to (VIII) below, and the evaluation results are shown in Table-41-200537168 ^ 2-1. (I) Evaluation of sensitivity is in progress In the case of a spacer, the sensitivity after exposure is 90% with the residual film rate after development (film thickness after development x 100 / initial film thickness, the same below) as the sensitivity. The sensitivity when the exposure amount is 1,500 □ / m2 or less is good. (II) Evaluation of image resolution When the spacer is formed, it is evaluated according to the minimum pattern size method based on the exposure amount at which the residual film rate after development is 90% or more. φ (III) Evaluation of the cross-sectional shape of the spacer The cross-sectional shape of the obtained spacer was observed with a scanning electron microscope, and the evaluation was performed based on the shape corresponding to one of A-D shown in FIG. 3. At this time, as shown in A or B, the pattern edge is forward-tapered or vertical. In both cases, the cross-sectional shape is good. In contrast, as shown by C, the sensitivity is not good enough, the residual film rate is low, the cross-sectional size is smaller than that of A and B, and its shape is a semi-convex lens shape with a flat bottom surface. This indicates that the cross-sectional shape is poor. In addition, as shown in D, the pattern edge is an inverted cone (in the shape of a cross section, the side of the film surface is longer than the side of the substrate). In this case, the pattern is peeled off during subsequent ® rubbing treatment. The probability is very high, so the cross-sectional shape is not good. (IV) Evaluation of compressive strength The compressive strength of the obtained spacer was measured using a miniature compressive tester (trade name MCTM-200, manufactured by Shimadzu Corporation), specifically, 23. <: A flat indenter with a diameter of 5 0 // m is used to apply a load of 10 m N at a temperature, and the amount of deformation at this time is measured. When the 値 is below 0.5 5 m, the compressive strength is good. . -42- 200537168, (V) Evaluation of abrasion resistance Using a liquid crystal alignment film coating printer, AL3046 (trade name, [made by SR (share))) was applied as a liquid crystal alignment agent on a substrate on which a spacer was formed, and then After drying at 180 ° C for 1 hour, a coating film of a liquid crystal aligning agent having a film thickness of 0 · 〇5 // m was formed. Then, this coating film was subjected to a rubbing treatment using a friction machine having a roll around which a cloth made of polyamide was wound under the conditions of a roll rotation speed of 500 rpm and a stage moving speed of 1 cm / sec. At this time, φ evaluation is performed based on whether the pattern is cut off or peeled off. (VI) Evaluation of adhesiveness A cured film was formed in the same manner as in the case of forming a spacer except that a photomask was not used. Then, in the adhesion test of nS K · 5400 (1 900) 8.5, the evaluation was carried out by the cross-cut tape method of 8 · 5 · 2. At this time, Table 2 shows the number of grids remaining per 100 grids. (VII) Evaluation of sublimability The above-mentioned composition solution was applied to a substrate and then dried to form a film having a film thickness of 6.0 / zm. Using n-octane (specific gravity = 0.701, injection volume ® = 〇 · 〇2μ 1) as a standard substance, and 100 ° C / 10 minutes as the purge condition, the above film was subjected to headspace gas chromatography / quality analysis ( The headspace sampler is JHS-100A manufactured by Japan Analytical Industry Co., Ltd .; the gas chromatograph / mass analyzer is JEOL JMS-AX505W type mass analyzer manufactured by Japan Analytical Industry Co., Ltd.). The area A of the peak of the initiator was calculated from the amount of volatilization in terms of n-octane by the following calculation formula. The larger the volatile amount, the greater the sublimability. Calculation formula of volatility based on n-octane Volatility (/ zg) = Αχ (amount of n-octane) (// g) / (peak area of n-octane) -43- 200537168 (VIII) Foreign matter in liquid Evaluation of the composition The solution of the above composition was stored at a temperature of 15 ° C for 7 days, and then visually observed whether a recrystallization product of a radiation-sensitive polymerization initiator component appeared therein. Furthermore, when the liquid temperature of the stored solution of the above composition was raised from -1 5 ° C to 23 ° C, a light scattering liquid particle detector (trade name KS-2 8 B, RIΟ N (strand)) was used. (Manufacturing) The number of solid objects (residual foreign matter) of 0.5 " m or more remaining without being re-dissolved in the composition solution per 1 # 1 was measured. Example 2-23 ® Except that the components shown in Table 1-1 were used as the [A] component, the [B] component, and the [C] component, the same operations as in Example 1 were performed to prepare each composition solution to form The spacer was subjected to various evaluations. The evaluation results are shown in Table 2-1. Example 24 The same components as in Example 1 were dissolved in diethylene glycol ethyl methyl ether so that the solid content concentration became 17 · 5% by weight, and then filtered through a micropore having a pore size of 0.5 // m Filter to make a composition solution. Other than that, a spacer was formed in the same manner as in Example 1 and various evaluations were performed. The evaluation results are shown in Table 2-1. Comparative Examples 1 to 8 In the same manner as in Example 1 except that the components shown in Table 1-2 were used as the [A] component, the [B] component, and the radiation-sensitive polymerization initiator, each composition solution was prepared. Spacers were formed and various evaluations were performed. The evaluation results are shown in Table 2-2. In Tables 1-1 and 1-2, various components other than the [A] component are as described below. B-1: Dipentaerythritol hexaacrylate; -44- 200537168 B-2: Trade name KAYARADDPHA-40H (manufactured by Nippon Kayaku Co., Ltd.); Cl: 2- (4-methylbenzyl)- 2- (dimethylamino) -1- (4-morpholinophenyl) butane-1 -one; Dl: 1- [9-ethyl-6- (2-methylbenzylidenecarbazole) -3-yl] -ethane-1-one oxime-〇 · acetate (trade name CGI-242, manufactured by Ciba Fine Chemical Co., Ltd.) E -1: 2 -methyl-1-[4-(methyl Thio) phenyl] -2 -morpholinopropane-1 -one (trade name IRG A CURE 9 07, manufactured by Ciba Fine Chemical Co., Ltd.); E-2: 2-benzyl-2-(monomethylamine Base) -1- (4-morpholinophenyl) butan-1_one (Shang ® brand name IRGACURE 3 69, manufactured by Ciba Jingye Chemical Co., Ltd.); E-3: 1-(2-bromo-4- Morpholinophenyl) -2 -benzyl-2 -methylamino-butan-1 _one; F-1: 2,2'-bis (2,4-dichlorophenyl) -4,4 ' , 5,5, tetraphenyl-1,2, -bisimidazole; F-2: 4,4'-bis (diethylamino) benzophenone; F-3: 2-fluorenylbenzothiazole.

45- 20053716845- 200537168

表1-1 [A诚分 (重量份） [B诚分 (重量份） [C]成分 (重量份） 實施例1 A-1 (100) B-1(80) C-1 (30) — 實施例2 A-1 (100) B-1 (80) C-1 (15) D-1 (10) 實施例3 A-1 (100) B-1 (80) C-1 (25) E-1 (10) 實施例4 A-1 (100) B-1 (80) C-1 (25) F-1/F-2/F-3 (10/10/5) 實施例5 A-1 (100) B-1 (80) C-1 (15) E-1 (10) F-1/F-2/F-3 (10/10/5) 實施例6 A-1 (100) B-1 (80) C-1 (20) D-1 (10) E-1 (10) 實施例7 A-1 (100) B-1 (80) C-1 (10) D-1 (10) E-1 (10) F-1/F-2/F-3 (10/10/5) 實施例8 A-1 (100) B-1/B-2 (90/10) C-1 (30) — 實施例9 A-1 (100) B-1/B-2 (90/10) C-1 (15) D-1 (10) 實施例10 A-1(100) B-1/B-2 (90/10) C-1 (25) E-1 (10) 實施例11 A-1 (100) B-1/B-2 (90/10) C-1 (25) F-1/F-2/F-3 (10/10/5) 實施例12 A-1(100) B-1/B-2 (90/10) C-1 (15) E-1 (10) F-1/F-2/F-3 (10/10/5) 實施例13 A-1 (100) B-1/B-2 (90/10) C-1 (20) D-1 (10) E-1 (10) 實施例Η A-1 (100) B-1/B-2 (90/10) C-1 (10) D-1 (10) E-1 (10) F-1/F-2/F-3 (10/10/5) 實施例15 A-2 (100) B-1/B-2 (80/20) C-1 (30) — 實施例16 A-2 (100) B-1/B-2 (80/20) C-1 (15) D-1 (10) 實施例17 A-2 (100) B-1/B-2 (80/20) C-1 (25) E-1 (10) 實施例18 A-2 (100) B-1/B-2 (80/20) C-1 (25) F-1/F-2/F-3 (10/10/5) 實施例19 A-2 (100) B-1/B-2 (80/20) C-1 (15) E-1 (10) F-1/F-2/F-3 (10/10/5) 實施例20 A-2 (100) B-1/B-2 (80/20) C-1 (20) D-1 (10) E-1 (10) 實施例21 A-2 (100) B-1/B-2 (80/20) C-1 (10) D-1 (10) E-1 (10) F-1/F-2/F-3 (10/10/5) 實施例22 A-1 (100) B-1 (80) C-1 (10) E-1/E-2 (10/10) F-1/F-2/F-3 (10/10/5) 實施例23 A-1 (100) B-1 (80) C-1 (15) D-1 (10) E-1/E-2 (10/10) 實施例24 A-1 (100) B-1 (80) C-1 (30) — -46- 200537168Table 1-1 [A content (parts by weight) [B content (parts by weight) [C] component (parts by weight) Example 1 A-1 (100) B-1 (80) C-1 (30) — Example 2 A-1 (100) B-1 (80) C-1 (15) D-1 (10) Example 3 A-1 (100) B-1 (80) C-1 (25) E- 1 (10) Example 4 A-1 (100) B-1 (80) C-1 (25) F-1 / F-2 / F-3 (10/10/5) Example 5 A-1 ( 100) B-1 (80) C-1 (15) E-1 (10) F-1 / F-2 / F-3 (10/10/5) Example 6 A-1 (100) B-1 (80) C-1 (20) D-1 (10) E-1 (10) Example 7 A-1 (100) B-1 (80) C-1 (10) D-1 (10) E- 1 (10) F-1 / F-2 / F-3 (10/10/5) Example 8 A-1 (100) B-1 / B-2 (90/10) C-1 (30) — Example 9 A-1 (100) B-1 / B-2 (90/10) C-1 (15) D-1 (10) Example 10 A-1 (100) B-1 / B-2 ( 90/10) C-1 (25) E-1 (10) Example 11 A-1 (100) B-1 / B-2 (90/10) C-1 (25) F-1 / F-2 / F-3 (10/10/5) Example 12 A-1 (100) B-1 / B-2 (90/10) C-1 (15) E-1 (10) F-1 / F- 2 / F-3 (10/10/5) Example 13 A-1 (100) B-1 / B-2 (90/10) C-1 (20) D-1 (10) E-1 (10 ) Example Η A-1 (100) B-1 / B-2 (90/10) C-1 (10) D-1 (10) E-1 (10) F-1 / F-2 / F- 3 (10/10/5) Example 15 A-2 (100) B-1 / B-2 (80/20) C-1 (30) — Example 16 A-2 (100) B-1 / B-2 (80/20) C-1 (15) D-1 (10) Example 17 A-2 (100) B-1 / B-2 (80/20) C-1 (25) E-1 (10) Example 18 A-2 (100) B-1 / B-2 (80/20) C-1 (25) F-1 / F-2 / F-3 (10/10/5) Example 19 A-2 (100) B-1 / B-2 (80/20) C-1 (15) E-1 (10) F- 1 / F-2 / F-3 (10/10/5) Example 20 A-2 (100) B-1 / B-2 (80/20) C-1 (20) D-1 (10) E -1 (10) Example 21 A-2 (100) B-1 / B-2 (80/20) C-1 (10) D-1 (10) E-1 (10) F-1 / F- 2 / F-3 (10/10/5) Example 22 A-1 (100) B-1 (80) C-1 (10) E-1 / E-2 (10/10) F-1 / F -2 / F-3 (10/10/5) Example 23 A-1 (100) B-1 (80) C-1 (15) D-1 (10) E-1 / E-2 (10 / 10) Example 24 A-1 (100) B-1 (80) C-1 (30) — -46- 200537168

表1-2 [A]成分 (重量份） [B诚分 (重量份） 放射線敏感性聚合引發劑 (重量份） 比較例1 A-1(100) B-1 (80) 一 E-1 (30) 比較例2 A-1(100) B-1 (80) — E-1 (10) 比較例3 A-1 (100) B-1 (80) — E-1 (30) F-1/F-2/F-3 (5/5/2.5) 比較例4 A-1 (100) B-1 (100) — D-1 (5) E-1 (30) 比較例5 A-1 (100) B-1 (80) — D-1 (5) E-1 (30) F-1/F-2/F-3 (5/5/2.5) 比較例6 A-1 (100) B-1/B-2 (90/10) — D-1 (5) E-1 (30) F-1/F-2/F-3 (5/5/2.5) 比較例7 A-1 (100) B-1 (80) — E-2 (30) 比較例8 A-1 (100) B-1 (80) — E-3 (30) -47- 200537168 表2-1Table 1-2 [A] Ingredients (parts by weight) [B Since (parts by weight) Radiation-sensitive polymerization initiator (parts by weight) Comparative Example 1 A-1 (100) B-1 (80) -E-1 ( 30) Comparative Example 2 A-1 (100) B-1 (80) — E-1 (10) Comparative Example 3 A-1 (100) B-1 (80) — E-1 (30) F-1 / F-2 / F-3 (5/5 / 2.5) Comparative Example 4 A-1 (100) B-1 (100) — D-1 (5) E-1 (30) Comparative Example 5 A-1 (100 ) B-1 (80) — D-1 (5) E-1 (30) F-1 / F-2 / F-3 (5/5 / 2.5) Comparative Example 6 A-1 (100) B-1 / B-2 (90/10) — D-1 (5) E-1 (30) F-1 / F-2 / F-3 (5/5 / 2.5) Comparative example 7 A-1 (100) B -1 (80) — E-2 (30) Comparative Example 8 A-1 (100) B-1 (80) — E-3 (30) -47- 200537168 Table 2-1

靈敏度 (J/m2) 圖像 解析度 (μπι) 斷面 形狀 抗壓 強度 耐摩 擦性 黏附性 昇華性 ㈣ 液中異物 再結晶化物 殘存異物 的數目 實施例1 3,000 12 A 0.29 Μ 100 0 J\\\ 0 實施例2 1,3〇〇 8 A 0.30 Λ j\\\ 100 0 Μ J\\\ 0 實施例3 2,800 10 B 0.47 dnc 100 0 4ττΤ. 無 0 實施例4 2,000 8 B 0.45 無 100 0 ίκ J\\\ 0 實施例5 1,500 10 B 0.52 無 100 0 Μ 0 實施例6 1,100 8 A 0.32 無 100 0 4ττΐ- 無 0 實施例7 1,000 8 A 0.25 dnXL ΤΓΤΙ. 100 0 4τγγ 無 0 實施例8 2,700 12 A 0.27 無 100 0 Λτχτ. 無 0 實施例9 1,100 8 A 0.28 無 100 0 4ττνι m 0 實施例10 2,500 12 B 0.48 Arrf Μ 100 0 0 實施例11 1,800 10 B 0.47 無 100 0 無 0 實施例12 1,400 10 B 0.45 無 100 0 Λττ. /fv? 0 實施例13 1,000 8 A 0.26 Μ j\\\ 100 0 4rrt. Ws 0 實施例Η 800 8 A 0.28 4nf 無 100 0 4rrr Mill J\\\ 0 實施例15 2,500 10 A 0.27 無 100 0 4nC 挑 0 實施例16 1,000 8 A 0.25 Μ j\\\ 100 0 無 0 實施例Π 2,200 8 A 0.26 Μ j\\\ 100 0 daSL 0 實施例18 1,600 8 A 0.26 Αϊλ ρ 100 0 m 0 實施例19 1,000 8 A 0.25 ίΕΕ J\\\ 100 0 dnt m 0 實施例20 .700 8 A 0.28 Μ 100 0 4ml 無 0 實施例21 600 8 A 0.25 >fnT 100 0 ^frrf 無 0 實施例22 1,300 10 A 0.32 4τττ ΙΊΤΓ J\\\ 100 0 4rrt 0 實施例23 900 8 A 0.26 4ττγ. ΎΠΓ. J\\\ 100 0 te j\\\ 0 實施例24 3,000 11 A 0.30 Μ 100 0 無 0 -48- 200537168 表2-2 靈敏度 (J/m2) 圖像 解析度 (μηι) 斷面 形狀 抗壓 強度 耐摩 擦性 黏附性 昇華性 ㈣ 液中異物 再結晶化物 殘存異物 的數目 比較例1 3,000 12 C 0.77 有 80 1.2 Μ j \\\ 0 比較例2 4,000 12 C 0.91 有 60 0 Μ y\\\ 0 比較例3 2,700 10 A 0.36 無 100 1.2 ArcL Μ 0 比較例4 2,500 8 D 0.32 有 80 1.1 /fnT Till： 0 比較例5 800 8 B 0.51 Μ j\\\ 100 1.1 4πτ ΙιΙι J \\\ 0 比較例6 800 8 B 0.56 Μ 100 1.1 迦 j\\\ 0 比較例7 2,900 12 A 0.31 並 j\\\ 100 0 有 300 比較例8 5,200 12 A 0.34 Μ j\\\ 100 0 有 450Sensitivity (J / m2) Image resolution (μπι) Sectional shape Compressive strength Friction resistance Adhesion sublimation ㈣ Number of foreign bodies recrystallized in liquid Example 1 3,000 12 A 0.29 Μ 100 0 J \ 0 Example 2 1, 3〇〇 A 0.30 Λ j \\\ 100 0 Μ J \\\ 0 Example 3 2,800 10 B 0.47 dnc 100 0 4τττ. None 0 Example 4 2,000 8 B 0.45 No 100 0 ίκ J \\\ 0 Example 5 1,500 10 B 0.52 No 100 0 Μ 0 Example 6 1,100 8 A 0.32 No 100 0 4ττΐ- No 0 Example 7 1,000 8 A 0.25 dnXL ΤΓΤΙ. 100 0 4τγγ No 0 Example 8 2,700 12 A 0.27 No 100 0 Δτχτ. No 0 Example 9 1,100 8 A 0.28 No 100 0 4ττνm m 0 Example 10 2,500 12 B 0.48 Arrf M 100 0 0 Example 11 1,800 10 B 0.47 No 100 0 No 0 Example 12 1,400 10 B 0.45 No 100 0 Λττ. / Fv? 0 Example 13 1,000 8 A 0.26 Μ j \\\ 100 0 4rrt. Ws 0 Example Η 800 8 A 0.28 4nf No 100 0 4rrr Mill J \\\ 0 Example 15 2,500 10 A 0.27 No 100 0 4nC Pick 0 Example 16 1,000 8 A 0.25 μj \\\ 100 0 No 0 Example Π 2,200 8 A 0.26 Μ j \\\ 100 0 daSL 0 Example 18 1,600 8 A 0.26 Αϊλ ρ 100 0 m 0 Example 19 1,000 8 A 0.25 ΕΕ J \\\ 100 0 dnt m 0 Example 20 .700 8 A 0.28 Μ 100 0 4ml No 0 Example 21 600 8 A 0.25 > fnT 100 0 ^ frrf No 0 Example 22 1,300 10 A 0.32 4τττ ΙτΓ J \\\ 100 0 4rrt 0 Example 23 900 8 A 0.26 4ττγ. ΎΠΓ. J \ \\ 100 0 te j \\\ 0 Example 24 3,000 11 A 0.30 Μ 100 0 None 0 -48- 200537168 Table 2-2 Sensitivity (J / m2) Image resolution (μηι) Compression strength of section shape Friction, adhesion, sublimation, 异 Number of foreign substances recrystallized in liquid Comparative example 1 3,000 12 C 0.77 Yes 80 1.2 Μ j \\\ 0 Comparative example 2 4,000 12 C 0.91 Yes 60 0 Μ y \\\ 0 Compare Example 3 2,700 10 A 0.36 No 100 1.2 ArcL Μ 0 Comparative Example 4 2,500 8 D 0.32 Yes 80 1.1 / fnT Till: 0 Comparative Example 5 800 8 B 0.51 Μ j \\\ 100 1.1 4πτ ΙιΙι J \\\ 0 Comparative Example 6 800 8 B 0.56 Μ 100 1.1 g j \\\ 0 Comparative Example 7 2,900 12 A 0.31 and j \\\ 100 0 Yes 300 Comparative Example 8 5,200 12 A 0.34 Μ j \\\ 100 0 Yes 450

【圖式之簡單說明】 第1圖是表示液晶顯示元件結構一例的模式圖。 第2圖是表示液晶器件結構另一例的模式圖。 第3圖是例示間隔物的斷面形狀的模式圖。 【主要元件符號說明】[Brief Description of the Drawings] FIG. 1 is a schematic diagram showing an example of the structure of a liquid crystal display element. Fig. 2 is a schematic diagram showing another example of the structure of a liquid crystal device. FIG. 3 is a schematic view illustrating a sectional shape of a spacer. [Description of main component symbols]

-49--49-

Claims (1)

200537168200537168 十、申請專利範圍： 1 · 一種間隔物形成用放射線敏感性樹脂組合物，其特徵在 於，該組合物含有： [A] (a 1)不飽和羧酸和/或不飽和羧酸酐、（a2)含有環氧 基的不飽和化合物與U3)其他不飽和化合物的共聚物； [B] 聚合性不飽和化合物；以及 [C] 以由下列一般式（1)表示的化合物作爲必要成分的 放射線敏感性聚合引發劑；X. Patent application scope: 1. A radiation-sensitive resin composition for spacer formation, characterized in that the composition contains: [A] (a 1) unsaturated carboxylic acid and / or unsaturated carboxylic anhydride, (a2 ) A copolymer of an unsaturated compound containing an epoxy group and U3) other unsaturated compounds; [B] a polymerizable unsaturated compound; and [C] a radiation-sensitive compound containing a compound represented by the following general formula (1) as an essential component Polymerization initiator 在一般式（1)中，R1表示碳原子數1-12的直鏈、支鏈或 環狀的烷基；R2和R3彼此獨立地表示氫原子，碳原子數 1-12的直鏈、支鏈或環狀的烷基或苄基；R4、R5、R7和 R8彼此獨立地表示氫原子，鹵素原子，碳原子數1-12的 直鏈、支鏈或環狀的烷基或者碳原子數1-4的直鏈或支 鏈狀的烷氧基；R6表示鹵素原子，碳原子數1-12的直鏈、 支鏈或環狀的烷基，經選自羥基和碳原子數1-4的直鏈 或支鏈狀的烷氧基組成之群的取代基所取代的碳原子數 1-12的直鏈、支鏈或環狀的烷基，碳原子數1-4的直鏈 或支鏈狀的烷氧基，或者經選自羥基和碳原子數1-4的 直鏈或支鏈狀的烷氧基組成之群的取代基所取代的碳原 -50- 200537168 子數2-4的直鏈或支鏈狀的烷氧基。 2.—種間隔物，其由申請專利範圍第1項之間隔物形成用 放射線敏感性樹脂組合物所形成。 3 —種間隔物之形成方法，其特徵在於，該方法至少包含 下述（1)〜（4)之步驟： (1) 在基板上形成申請專利範圍第1項之間隔物形成 用放射線敏感性樹脂組合物的被膜之步驟； (2) 對該被膜之至少一部分用放射線進行曝光的步In the general formula (1), R1 represents a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms; R2 and R3 independently represent a hydrogen atom, and a linear or branched chain having 1 to 12 carbon atoms Chain or cyclic alkyl or benzyl; R4, R5, R7, and R8 independently of each other represent a hydrogen atom, a halogen atom, a linear, branched, or cyclic alkyl or carbon atom having 1 to 12 carbon atoms 1-4 linear or branched alkoxy groups; R6 represents a halogen atom, a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, selected from a hydroxyl group and a carbon number of 1-4 A linear or branched alkoxy group of substituents is substituted by a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, and a linear or branched chain having 1 to 4 carbon atoms. Carbon alkoxy, or a carbon atom substituted with a substituent selected from the group consisting of a hydroxyl group and a linear or branched alkoxy group having 1-4 carbon atoms -50- 200537168 Number of members 2-4 Straight or branched alkoxy. 2. A spacer formed of the radiation-sensitive resin composition for forming a spacer in the first patent application. 3—A method for forming a spacer, characterized in that the method includes at least the following steps (1) to (4): (1) forming a radiation sensitivity for forming a spacer on the substrate in the first scope of the patent application A step of coating the resin composition; (2) a step of exposing at least a part of the film to radiation (3) 將曝光後之上述被膜顯影的步驟； (4) 將顯影後之上述被膜加熱的步驟。 4.一種液晶顯示元件’其具備申請專利範圍第2項之間隔 物0 -51-(3) a step of developing the above-mentioned film after exposure; (4) a step of heating the above-mentioned film after development. 4. A liquid crystal display element 'having a spacer 0-51-
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