TW200525297A - Radiation-sensitive resin composition for forming a spacer, production of the spacer and liquid crystal display element - Google Patents

Radiation-sensitive resin composition for forming a spacer, production of the spacer and liquid crystal display element Download PDF

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TW200525297A
TW200525297A TW094100634A TW94100634A TW200525297A TW 200525297 A TW200525297 A TW 200525297A TW 094100634 A TW094100634 A TW 094100634A TW 94100634 A TW94100634 A TW 94100634A TW 200525297 A TW200525297 A TW 200525297A
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spacer
radiation
compound
weight
resin composition
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TW094100634A
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Chinese (zh)
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TWI371655B (en
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Daigo Ichinohe
Yoshitaka Yamada
Tomoko Iwabuchi
Toshihiro Nishio
Michinori Nishikawa
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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
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/72—Benzo[c]thiophenes; Hydrogenated benzo[c]thiophenes
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C09D201/06—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
    • C09D201/08—Carboxyl groups
    • 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
    • G03F7/038—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
    • 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

Abstract

The present invention provides a radiation-sensitive resin composition for forming a spacer, which easily forms a spacer with high resolution, high sensitivity, and good properties of pattern shape, press strength, rubbing resistence, and coherency with the transparent substrate, even explored by a radiation substantially without less than 350 nm wavelength. Said radiation-sensitive resin composition for forming a spacer comprises (A) a copolymer consisted of (a1) unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrate and (a2) epoxy-containing unsaturated compound and (a3) other unsaturated compound; (B) polymerable unsaturated compound; (C) biimidazole compound; (D) radiation-sensitive polymerable inducer with carbonyl group, and dialkylamino group-containing compound and/or [F] thiol compound.

Description

200525297 麄 · 九、發明說明： [發明所屬之技術領域] 本發明涉及一種形成間隔物用感放射線性樹脂組成 物、間隔物及其形成方法以及液晶顯示元件，進而詳細地， 涉及實質上即使使用不含3 5 0nm以下波長的放射線進行曝 光’也可形成間隔物的感放射線性樹脂組成物、由它形成 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] 對於液晶顯示元件，以往，爲了將2個透明基板間的 間隔保持一定，使用具有特定的粒徑的玻璃珠、塑膠珠等 的間隔物粒子，但由於這些間隔物粒子無規地散佈在玻璃 基板等的透明基板上，所以在形成畫素領域存在間隔物粒 子時，則產生間隔物粒子寫入現象，入射光受到散射，液 晶顯示元件的對比度降低的問題。 因此，爲了解決這些問題，採用光刻法形成間隔物的 方法。該方法是將感放射線性樹脂組成物塗覆在基板上通 過規定的光罩曝光紫外線後顯影，形成點狀或條紋狀的間 隔物，僅在畫素形成領域以外的規定部位形成間隔物，基 本上解決了上述問題。 可是，光刻法的光源使用的水銀燈的放射線，通常在 4 3 6 n m附近（g線）、4 0 4 n m附近（h線）、3 6 5 n m附近（i線）、 3 35nm附近、315nm附近（j線）、3 03 nm附近等顯示強度高 的光譜，所以作爲感放射線性樹脂組成物的構成成份的感 放射線性聚合引發劑，通常選擇使用在這些強度高的光譜 200525297 ^ 波長領域上具有最大吸收波長者，在幾乎所有場合，從透 明性的觀點看，使用波長在i線以下的領域具有最大吸收 波長的感放射線性聚合引發劑，（例如，參照專利文獻1。）。 若使用波長比i線長的g線、h線附近具有最大吸收波長的 感放射線性聚合引發劑時，由於該感放射線性聚合引發劑 在接近可見光線的波長領域具有吸收，所以使含有此劑的 感放射線性樹脂組成物著色而形成的薄膜的透明性降低。 若薄膜的透明性降低，在曝光時，在膜表面進行固化反應， 在薄膜的深度方向的固化反應不充分，結果，顯影後得到 的間隔物的形狀成爲倒錐形（作爲剖面形狀，膜表面的邊比 基板側的邊長的倒三角形狀），在以後的配向膜的硏磨處理 時成爲間隔物剝離的原因。 [專利文獻1]特開200 1 — 26 1 76 1號公報 另一方面，在實際的形成間隔物加工中，例如在用於 彩色濾光器等的透明基板上用光刻法形成間隔物時，大多 使用趨近曝光機，但近年爲了提高趨近曝光機的光通量， 一般使用照度高的水銀燈。此時，在提高光通量上雖然有 效果，但直接使用時，使得用於曝光機的反射鏡的壽命降 低，所以大多是用濾光器將具有高能量的波長3 5 0nm以下 的短波長放射線切斷後使用。可是，以往的感放射線性聚 合引發劑幾乎都是在3 5 0 n m以下時具有最大吸收波長，所 以若切斷波長3 5 0 n m以下的放射線時，則不能充分發生對 於感放射線性樹脂組成物的固化所必要的自由基等的活性 種，而使固化反應不充分，難以得到可滿足的間隔物的尺 寸或形狀。 200525297 ▲ .200525297 麄 · IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to a radiation-sensitive resin composition for forming a spacer, a spacer and a method for forming the same, and a liquid crystal display element. A radiation-sensitive resin composition that can form a spacer without exposure to radiation having a wavelength of less than 350 nm, a spacer formed therefrom, a method for forming the same, and a liquid crystal display element having the spacer. [Prior Art] Conventionally, in order to maintain a constant distance between two transparent substrates, spacer particles such as glass beads and plastic beads having a specific particle diameter have been used. However, these spacer particles are random Scattered on transparent substrates such as glass substrates. When spacer particles are formed in the pixel area, the phenomenon of writing spacer particles occurs, incident light is scattered, and the contrast of the liquid crystal display element is reduced. Therefore, in order to solve these problems, a method of forming a spacer using a photolithography method is adopted. In this method, a radiation-sensitive resin composition is coated on a substrate and exposed to ultraviolet light through a predetermined photomask to develop dots or stripes. The spacers are formed only at predetermined locations outside the pixel formation field. Basically, The above problem is solved. However, the radiation of a mercury lamp used as a light source for photolithography is usually around 4 3 6 nm (g-line), 40 4 nm (h-line), 3 6 5 nm (i-line), 3 35 nm, 315 nm. Nearby (j-line), near 3 03 nm, etc. show high-intensity spectra, so radiation-sensitive polymerization initiators, which are constituents of radiation-sensitive resin compositions, are usually selected for use in these high-intensity spectra 200525297 ^ wavelength range A person having a maximum absorption wavelength uses a radiation-sensitive polymerization initiator having a maximum absorption wavelength in a region below the i-line in almost all cases from the viewpoint of transparency (for example, refer to Patent Document 1). If a radiation-sensitive polymerization initiator with a maximum absorption wavelength near the g-line and the h-line is used, the radiation-sensitive polymerization initiator has absorption in a wavelength region close to visible light. The transparency of a thin film formed by coloring the radiation-sensitive resin composition decreases. If the transparency of the film is reduced, a curing reaction proceeds on the film surface during exposure, and the curing reaction in the depth direction of the film is insufficient. As a result, the shape of the spacer obtained after development becomes an inverted cone shape (as a cross-sectional shape, the film surface Inverted triangle shape whose side is longer than the side on the substrate side) causes the spacer to peel off during the subsequent honing process of the alignment film. [Patent Document 1] Japanese Patent Application Laid-Open No. 200 1-26 1 76 On the other hand, in the actual process of forming a spacer, for example, when forming a spacer by photolithography on a transparent substrate used for a color filter or the like Most of them use approaching exposure machines, but in recent years, in order to improve the luminous flux of approaching exposure machines, mercury lamps with high illumination are generally used. At this time, although there is an effect in increasing the luminous flux, when used directly, the life of the reflector used in the exposure machine is reduced, so most of the filters are used to cut short-wavelength radiation with a high energy wavelength below 350 nm. Use after breaking. However, almost all conventional radiation-sensitive polymerization initiators have a maximum absorption wavelength below 350 nm. Therefore, when radiation with a wavelength below 350 nm is cut, the radiation-sensitive resin composition cannot sufficiently occur. Active species, such as radicals, necessary for curing, make the curing reaction insufficient, and make it difficult to obtain a satisfactory size or shape of the spacer. 200525297 ▲.

[發明內容] 本發明的課題在於提供一種間隔物用感放射線性樹脂 組成物，即使實質上使用不含有3 5 Onm以下波長的放射線 的曝光，也可容易地形成高解析度、高靈敏度，且圖形形 狀、壓縮強度、硏磨耐性、與透明基板的密著性等的諸性 能優良的間隔物；以及提供由該樹脂組成物形成的間隔物 及其形成方法及具有該間隔物的液晶顯示元件。 本發明第一爲一種形成間隔物用感放射線性樹脂組成 物，其特徵爲含有以下組成： [A] (al)不飽和羧酸及/或不飽和羧酸酐及、（a2)含有環 氧基不飽和化合物及、（a3)其他的不飽和化合物的共聚物、 [B] 聚合性不飽和化合物、 [C] 雙咪唑系化合物、 [D] 具有羰基的感放射線性聚合引發劑，以及 [E] 具有二烷胺基的化合物及/或[F]硫醇系化合物。. 在本發明中所說的“放射線”是指包括紫外線、遠紫 外線、X線、電子線、分子線、9"線、同步加速器放射線、 質子束放射線等的射線。 本發明第二爲一種間隔物，是由上述形成間隔物用感 放射線性樹脂組成物所形成。 本發明第三爲間隔物的形成方法，其特徵至少含有下 述（1)〜（4)的步驟： (1) 在基板上形成申請專利範圍第1或2項所述之形成 間隔物用感放射線性樹脂組成物的薄膜的步驟、 (2) 在該薄膜的至少一部分上曝光實質上不含有3 5〇nm 200525297 » · 以下波長的放射線的步驟、 (3) 對曝光後的薄膜進行顯影的步驟、 (4) 對顯影後的薄膜進行加熱的步驟。 本發明第四爲具有上述間隔物的液晶顯示元件。 [實施方式] 以下，對本發明進行詳細說明。 Μ隔物用感放射線件樹脂細成物 以下’對於本發明的間隔物用感放射線性樹脂組成物 (以下簡稱爲“感放射線性樹脂組成物”）的各成份詳細說 明。 [Α]共聚物 本發明的感放射線性樹脂組成物的[Α]成份係由（a 1)不 飽和羧酸及/或不飽和羧酸酐（以下，將其歸v納稱爲“化合 物U1)”）、（a2)含有環氧基之飽和化合物（以下，稱爲“化 合物U2)”）及（a3)其他的不飽和化合物（以下，稱爲“化合 物U3)”）的共聚物（以下，稱爲“[A]共聚物”）構成。 化合物（a 1)例如可舉出丙烯酸、甲基丙烯酸、丁烯酸、 單（2 -丙烯醯氧乙基）丁二酸、單（2-甲基丙烯醯氧乙基） 丁二酸、單（2 —丙烯醯氧乙基）六氫鄰苯二甲酸、單（2—甲 基丙烯醯氧乙基）六氫鄰苯二甲酸等的一元羧酸類；馬來 酸、富馬酸、檸康酸、甲基富馬酸、衣康酸等的二羧酸類； 這些的二羧酸酐類等。 在這些化合物（a 1)中，從共聚反應性及容易得到看，較 佳的是丙烯酸、甲基丙烯酸、馬來酸酐等。 上述化合物（a 1)可以單獨或2種以上混合使用。 200525297 邋 » 在[A]共聚物中，從化合物（a 1)衍生的構成單元的含有 率，較佳的是5〜5 0重量％、特佳的是1 〇〜4 0重量％。此時， 若該構成單元的含有率不足5重量％，得到的間隔物的壓縮 強度、耐熱性及耐藥品性有降低的趨勢，另一方面，若超 過5 0重量％，感放射線性樹脂組成物的保存穩定性有降低 的趨勢。 另外，作爲化合物U2)，例如可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 - η—丙基丙嫌酸縮水甘油酯、α — η- 丁基丙儲酸縮水 甘油酯、丙烯酸3，4 一環氧丁酯、甲基丙烯酸3，4 一環氧丁 酯、α —乙基丙烯酸3,4 —環氧丁酯、丙烯酸6，7 —環氧庚 酯、甲基丙烯酸6,7-環氧庚酯、α —乙基丙烯酸6,7-環 氧庚酯、丙烯酸/3 -甲基縮水甘油酯、甲基丙烯酸Θ —甲 基縮水甘油酯、丙烯酸/3 —乙基縮水甘油酯、甲基丙烯酸 石一乙基縮水甘油酯、丙烯酸^ 一 η -丙基縮水甘油酯、甲 基丙烯酸/3 — η—丙基縮水甘油酯、丙烯酸3，4 一環氧基環 己酯、甲基丙烯酸3,4 一環氧基環己酯等的羧酸酯類；〇 — 乙烯基苄基縮水甘油基醚、m-乙烯基苄基縮水甘油基醚、 p -乙烯基苄基縮水甘油基醚等的醚類。 在這些化合物（a2)中，從提高共聚反應性及得到的間隔 物的強度看，較佳的是甲基丙烯酸縮水甘油酯、甲基丙烯 酸6，7—環氧基庚酯、甲基丙烯酸3，4 一環氧基環己酯、甲 基丙烯酸Θ -甲基縮水甘油酯、〇 -乙烯基苄基縮水甘油基 醚、m -乙烯基苄基縮水甘油基醚、p -乙烯基苄基縮水甘 油基醚等。 -10- 200525297 上述化合物（a2)可以單獨或2種以上混合使用。 在[A]共聚物中，從化合物（a2)衍生的構成單元的含有 率，較佳的是10〜70重量％、特佳的是20〜60重量％。此時， 若該構成單元的含有率不足1 〇重量％時，得到的間隔物的 壓縮強度、耐熱性及耐藥品性有降低的趨勢，另一方面， 若超過70重量％，感放射線性樹脂組成物的保存穩定性有 降低的趨勢。 另外，作爲化合物U3)，例如可舉出丙烯酸甲酯、丙烯 酸乙酯、丙烯η—丙酯、丙烯酸i —丙酯、丙烯酸n— 丁酯、 丙烯酸i-丁酯、丙烯酸第二丁酯、丙烯酸第三丁酯等的丙 烯酸烷基酯類；甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基 丙烯酸η—丙酯、甲基丙烯酸i一丙酯、甲基丙烯酸η-丁 酯、甲基丙烯酸i一丁酯、甲基丙烯酸第二丁酯、甲基丙烯 酸第三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、三環[5.2.1.02’6]癸烷一 8 —基丙烯酸 酯（以下，將“三環[5·2·1.02’6]癸烷—8—基”稱爲“二環戊 基” 。）、2—二環戊基氧乙基丙烯酸酯、異冰片基丙烯酸 酯、四氫呋喃基丙烯酸酯等的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、2 —二環戊基氧乙基甲基丙烯酸酯、異冰片基甲 基丙烯酸酯、四氫呋喃基甲基丙烯酸酯等的甲基丙烯酸的 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曱基丙烯酸芳 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 —羥基乙酯、丙烯酸2 —羥基丙 200525297 擁 參 酯等的丙烯酸羥基烷基酯類；甲基丙烯酸2 -羥基乙酯、 甲基丙烯酸2 -羥基丙酯等的甲基丙烯酸羥基烷基酯類； 苯乙烯、α —甲基苯乙烯、m —甲基苯乙烯、p—甲基苯乙 烯、p -甲氧基苯乙燒等的芳香族乙燒基化合物及、丙嫌 腈、甲基丙烯腈、氯乙烯、亞氯乙烯、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、N-環己基馬來醯亞胺、N —苯基馬來醯亞 胺、N -苄基馬來醯亞胺、N -琥珀醯亞胺基一 3 -馬來醯 亞胺苯甲酸酯、N —琥珀醯亞胺基- 4 -馬來醯亞胺丁酸 酯、N —琥珀醯亞胺基一 6 —馬來醯亞胺己酸酯、N —琥珀 醯亞胺基一 3—馬來醯亞胺丙酸酯、N—（9 一吖啶基）馬來醯 亞胺等。 這些化合物U3)中，從共聚反應性看，較佳的是丙烯酸 2—甲基環己酯、甲基丙烯酸t 一丁酯、甲基丙烯酸二環戊 酯、苯乙烯、p一甲氧基苯乙烯、1,3 — 丁二烯等。 上述化合物（a3)可以單獨或2種以上混合使用。 在[A]共聚物中，從化合物（a3)衍生的構成單元的含有 率較佳的是10〜80重量％、特佳的是20〜60重量％。此時， 若該構成單元的含有率不足1 〇重量％，則感放射線性樹脂 組成物的保存穩定性可能降低，另一方面，若超過8 0重量 %，則顯影性可能降低。 [A]共聚物之以凝膠滲透色譜（GpC)測定換算成聚苯乙 烯重量平均分子量（以下，稱爲“Mw” 。），通常爲2x1 03〜5 xlO5’較佳的是5xl03〜1χ1〇5。此時，若[A]共聚物的Mw不 足2x 1 〇3時，得到的間隔物的壓縮強度及耐熱性有降低的趨 -12- 200525297 勢，另一方面，若超過5χ 1 Ο5，有顯影性降低的趨勢。 在本發明中，[Α]共聚物可以單獨或2種以上混合使用。 [Α]共聚物，例如可在溶劑中、聚合引發劑存在下通過 自由基聚合化合物（al)、化合物（a2)及化合物U3)來製造。 用於製造[A]共聚物的溶劑，例如可舉出甲醇、乙醇等 的醇類；四氫呋喃等的醚類；乙二醇單甲基醚、乙二醇單 乙基醚等的乙二醇醚類；乙二醇甲基醚乙酸酯、乙二醇乙 基醚乙酸酯等的乙二醇烷基醚乙酸酯類；二乙二醇單甲基 醚、二乙二醇單乙基醚、二乙二醇二甲基醚、二乙二醇二 乙基醚、二乙二醇乙基甲基醚等的二乙二醇醚類；丙二醇 甲基醚、丙二醇乙基醚、丙二醇一 η—丙基醚、丙二醇一 η -丁基醚等的丙二醇醚類；丙二醇甲基醚乙酸酯、丙二醇 乙基醚乙酸酯、丙二醇一 η—丙基醚乙酸酯、丙二醇一 η — 丁基醚乙酸酯等的丙二醇烷基醚乙酸酯類；丙二醇甲基醚 丙酸酯、丙二醇乙基醚丙酸酯、丙二醇一 η—丙基醚丙酸 酯、丙二醇一 η —丁基醚丙酸酯等的丙二醇烷基醚丙酸酯 類；甲苯、二甲苯等的芳香族烴類；甲基乙基酮、環己酮、 4一羥基—4 —甲基一 2 —戊酮的酮類； 醋酸甲酯、醋酸乙酯、醋酸正丙酯、醋酸正丁酯、羥 基醋酸甲酯、羥基醋酸乙酯、羥基醋酸正丙酯、羥基醋酸 正丁酯、乳酸甲酯、乳酸乙酯、乳酸正丙酯、乳酸正丁酯、 3 一羥基丙酸甲酯、3 -羥基丙酸乙酯、3 —羥基丙酸正丙 酯、3 —羥基丙酸正丁酯、2 -羥基一 2 —甲基丙酸甲酯、2 一羥基一 2—甲基丙酸乙酯、2—羥基一 3—甲基丁酸甲酯、 甲氧基醋酸甲酯、甲氧基醋酸乙酯、甲氧基醋酸正丙酯、 -13- 200525297 » * 甲氧基醋酸正丁酯、乙氧基醋酸甲酯、乙氧基醋酸乙酯、 乙氧基醋酸正丙酯、乙氧基醋酸正丁酯、正丙氧基醋酸甲 酯、正丙氧基醋酸乙酯、正丙氧基醋酸正丙酯、正丙氧基 醋酸正丁酯、正丁氧基醋酸甲酯、正丁氧基醋酸乙酯、正 丁氧基醋酸正丙酯、正丁氧基醋酸正丁酯、2—甲氧基丙酸 甲酯、2—甲氧基丙酸乙酯、2—甲氧基丙酸正丙酯、2—甲 氧基丙酸正丁酯、2—乙氧基丙酸甲酯、2—乙氧基丙酸乙 酯、2—乙氧基丙酸正丙酯、2—乙氧基丙酸正丁酯、正丙 氧基丙酸甲酯、正丙氧基丙酸乙酯、正丙氧基丙酸正丙酯、 正丙氧基丙酸正丁酯、2-正丁氧基丙酸甲酯、2 -正丁氧 基丙酸乙酯、2—正丁氧基丙酸正丙酯、2 -正丁氧基丙酸 正丁酯、3—甲氧基丙酸甲酯、3—甲氧基丙酸乙酯、3—甲 氧基丙酸正丙酯、3 —甲氧基丙酸正丁酯、3 -乙氧基丙酸 甲酯、3 —乙氧基丙酸乙酯、3—乙氧基丙酸正丙酯、3—乙 氧基丙酸正丁酯、3—正丙氧基丙酸甲酯、3-正丙氧基丙 酸乙酯、3-正丙氧基丙酸正丙酯、3-正丙氧基丙酸正丁 酯、3 —正丁氧基丙酸甲酯、3—正丁氧基丙酸乙酯、3—正 丁氧基丙酸正丙酯、3-正丁氧基丙酸正丁酯等的其他酯類 等。 另外，[A]共聚物製造所用的聚合引發劑，一般，可使 用已知的自由基聚合引發劑，例如可舉出2,2’ 一偶氮雙異 丁腈、2,2’ 一偶氮雙—（2,4 一二甲基戊腈）、2,2’ 一偶氮一 (4 一甲氧基一 2,4 一二甲基戊腈）、4,4’ 一偶氮雙（4 一氰基戊 酸）、二甲基一 2,2’ 一偶氮雙（2—甲基丙酸酯）、2,2， 一偶 氮雙（4 一甲氧基一 2，4 一二甲基戊腈）等的偶氮化合物；苯甲 -14 - 200525297 « * 醯過氧化物、月桂醯過氧化物、第三丁基過氧新戊酸酯、 1，1’ 一雙-（第三丁基過氧基）環己烷等的有機過氧化物； 過氧化氫等。作爲自由基聚合引發劑使用過氧化物時，作 爲氧化還原型引發劑，也可以並用還原劑。 [B ]聚合性不飽和化合物 作爲本發明的感放射線性樹脂組成物的聚合性不飽和 化合物’較佳的是2官能以上的丙烯酸酯及甲基丙烯酸酯 (以下，稱爲“（甲基）丙烯酸酯”）。 作爲2官能的（甲基）丙烯酸酯，例如可舉出乙二醇丙 烯酸酯、乙二醇甲基丙烯酸酯、1,6 —己二醇二丙烯酸酯、 1，6-己二醇二甲基丙烯酸酯、1，9 一壬二醇二丙烯酸酯、1，9 一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、雙苯氧乙醇芴二丙烯酸酯、雙苯氧乙醇芴二 甲基丙烯酸酯等。 另外，作爲2官能的（甲基）丙烯酸酯的市售品，例如 可舉出 ARONIX M— 210、ARONIX M— 240、ARONIX M — 6200(以上，東亞合成（株）製）、KAYARAD HDDA、KAYARAD HX - 220、KAYARAD R— 604、UX— 220 1、UX — 230 1、UX 一 3204、UX - 33(H、UX - 410卜 UX-61(H、UX-7101、UX —8101、MU— 2100、MU— 4001(以上，日本化藥（株）製）、 硬化型黏著齊 11 (VISC 〇 AT) 260、VISC 〇 AT 312、 VISCOAT 335HP(以上，大阪有機化學工業（株）製）等。 作爲3官能以上的（甲基）丙烯酸酯，例如可舉出三羥 甲基丙烷三丙烯酸酯、三羥甲基丙烷三甲基丙烯酸酯、季 -15- 200525297 鼻 * 戊四醇二丙條酸酯、季戊四醇三甲基丙燦酸酯、季戊四醇 四丙烯酸酯、季戊四醇四甲基丙烯酸酯、二季戊四醇五丙 綠酸酯、二季戊四醇五甲基丙儲酸酯、二季戊四醇六丙儲 酸酯、二季戊四醇六甲基丙烯酸酯、三（2 一丙烯醯氧乙基） 磷酸酯、三（2 -甲基丙烯醯氧乙基）磷酸酯，作爲9官能以 上的（甲基）丙烯酸酯，可舉出將具有直鏈亞烷基及脂環式 結構，且具有2個以上的異氰酸酯基的化合物及在分子中 具有1個以上的羥基，且具有3個、4個或者5個丙烯醯氧 基及/或甲基丙烯醯氧基的化合物進行反應得到的胺甲酸 乙酯丙烯酸酯系化合物等。 另外，作爲3官能以上的（甲基）丙烯酸酯的市售品， 例如可舉出 ARONIXM — 309、ARONIX — 400、ARONIX -402、ARONIX — 405、ARONIX — 450、AR〇NIX_ 1310、ARONIX 一 1 600、ARONIX— 1 960、ARONIX — 7100、ARONIX — 8 0 3 0、 ARONIX — 8060、ARONIX — 8100、ARONIX — 8530、ARONIX 一 8560、ARONIX — 9050、ARONIX TO— 1450(以上，東亞合 成（株）製）、KAYARAD TMPTA、KAYARAD DPHA、KAYARAD DPCA— 20、KAYARAD DPCA — 30、KAYARAD DPCA - 60、 KAYARAD DPCA - 120、KAYARAD MAX — 3510(以上，曰本 化藥（株）製）、VISCOAT 295、VISCOAT 300、VISCOAT 360、 VISCOAT GPT、 VISCOAT 3PA、VIS C 〇 A T 4 0 0 (以上’大阪 有機化學工業（株）製）及、作爲胺甲酸乙酯丙烯酸酯系化合 物，可舉出NEWFRONTIERR — 1150(第一工業製藥（株） 製）、KAYARADDPHA — 40H(曰本化藥（株）製）等。 在本發明中，聚合性不飽和化合物可以單獨或2種以 -16- 200525297 論 參 上混合使用。 在本發明的感放射線性樹脂組成物中’聚合物不飽和 化合物的使用量，相對於[A]共聚物100重量份，較佳的是 30〜200重量份、特佳的是50〜140重量份。此時’如果聚合 物不飽和化合物的使用量低於3 0重量份時，則得到的間隔 物的膜邊性及強度有容易降低的趨勢，另一方面，若超過 2 00重量份，可能得到的間隔物的密著性不足。 [C]雙咪唑系化合物 作爲本發明所用的雙咪唑系化合物，例如可舉出用下述 通式（1)表示的化合物（以下，稱爲“雙咪唑系化合物 (C1)” ° )、用下述通式（2)表示的化合物（以下，稱爲“雙 咪唑系化合物（C2)。”等。[Disclosure of the Invention] An object of the present invention is to provide a radiation-sensitive resin composition for a spacer, which can easily form a high resolution and a high sensitivity even if the exposure does not substantially include radiation having a wavelength of 3 5 Onm or less, and Spacer with excellent performances such as pattern shape, compressive strength, honing resistance, adhesion to a transparent substrate, and the like; and a spacer formed from the resin composition, a method for forming the same, and a liquid crystal display element having the spacer . The first of the present invention is a radiation-sensitive resin composition for forming a spacer, which is characterized by containing the following composition: [A] (al) an unsaturated carboxylic acid and / or an unsaturated carboxylic anhydride and (a2) an epoxy group Unsaturated compounds and (a3) copolymers of other unsaturated compounds, [B] polymerizable unsaturated compounds, [C] bisimidazole-based compounds, [D] radiation-sensitive polymerization initiators having a carbonyl group, and [E ] A compound having a dialkylamino group and / or a [F] thiol-based compound. In the present invention, "radiation" refers to radiation including ultraviolet rays, far ultraviolet rays, X-rays, electron rays, molecular rays, 9 " rays, synchrotron radiation, proton beam radiation, and the like. The second aspect of the present invention is a spacer formed of the above-mentioned radiation-sensitive resin composition for forming a spacer. The third method of the present invention is a method for forming a spacer, which is characterized by including at least the following steps (1) to (4): (1) forming a spacer-forming feeling as described in item 1 or 2 of the scope of patent application on a substrate; A step of a thin film of a radiation resin composition, (2) a step of exposing at least a part of the film to substantially not containing 350 nm 200525297 »· a step of the following wavelengths of radiation, (3) developing the exposed film Step (4) A step of heating the developed film. The fourth aspect of the present invention is a liquid crystal display element having the spacer. [Embodiment] Hereinafter, the present invention will be described in detail. Refined Radiation Sensitive Resin for M Spacer Hereinafter, each component of the radiation sensitive resin composition for spacers of the present invention (hereinafter referred to as "radiation sensitive resin composition") will be described in detail. [A] Copolymer The [A] component of 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 "compound U1") "), (A2) epoxy-containing saturated compounds (hereinafter, referred to as" compound U2) ") and (a3) other unsaturated compounds (hereinafter, referred to as" compound U3) ") (hereinafter, Called "[A] copolymer"). Examples of the compound (a 1) include acrylic acid, methacrylic acid, butenoic acid, mono (2-propenyloxyethyl) succinic acid, mono (2-methacryloxyethyl) succinic acid, and mono Monocarboxylic acids such as (2-propenyloxyethyl) hexahydrophthalic acid and mono (2-methacrylicoxyethyl) hexahydrophthalic acid; maleic acid, fumaric acid, citraconic acid Acid, methyl fumaric acid, itaconic acid and other dicarboxylic acids; these dicarboxylic anhydrides 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 compound (a 1) may be used alone or as a mixture of two or more. 200525297 邋 »In the [A] copolymer, the content of the structural unit derived from the compound (a 1) is preferably 5 to 50% by weight, and particularly preferably 10 to 40% by weight. At this time, if the content rate of the constituent unit is less than 5% by weight, the compressive strength, heat resistance, and chemical resistance of the obtained spacer tend to decrease. On the other hand, if it exceeds 50% by weight, the radiation-sensitive resin composition The storage stability of the material tends to decrease. Examples of the compound U2) include glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethylacrylate, glycidyl α-η-propylpropionate, and α-η-butyl Glycidyl glycidyl ester, 3,4-butylene oxide acrylate, 3,4-butylene oxide methacrylate, α-ethyl acrylate 3,4-butylene oxide, 6,7-ring Oxoheptyl, 6,7-epoxyheptyl methacrylate, α-ethylhexyl 6,7-epoxyheptyl acrylate, acrylic acid / 3-methyl glycidyl ester, methacrylic acid Θ-methyl glycidyl ester / 3 acrylic acid / 3-glycidyl methacrylate, monoethyl glycidyl methacrylate, ^ -η-propyl glycidyl acrylate, / 3-η-propyl glycidyl methacrylate, 3 acrylic acid, Carboxylic acid esters such as 4 monoepoxycyclohexyl, 3,4 monoepoxycyclohexyl; 0-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether And p-vinyl benzyl glycidyl ether. Among these compounds (a2), glycidyl methacrylate, 6,7-epoxyheptyl methacrylate, and methacrylic acid 3 are preferred from the viewpoint of improving the copolymerization reactivity and the strength of the obtained spacer. , 4-monoepoxycyclohexyl ester, Θ-methyl glycidyl methacrylate, 0-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl Glyceryl ether, etc. -10- 200525297 The compound (a2) can be used alone or as a mixture of two or more. In the [A] copolymer, the content of the structural unit derived from the compound (a2) is preferably 10 to 70% by weight, and particularly preferably 20 to 60% by weight. At this time, if the content of the constituent unit is less than 10% by weight, the compressive strength, heat resistance, and chemical resistance of the obtained spacer tend to decrease. On the other hand, if it exceeds 70% by weight, the radiation-sensitive resin The storage stability of the composition tends to decrease. Examples of compound U3) include methyl acrylate, ethyl acrylate, propylene n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, second butyl acrylate, and acrylic acid. Alkyl acrylates such as third butyl esters; methyl methacrylate, ethyl methacrylate, η-propyl methacrylate, i-propyl methacrylate, η-butyl methacrylate, methyl Alkyl methacrylates such as i-butyl acrylate, second butyl methacrylate, and third butyl methacrylate; cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclic [5.2. 1.02'6] decane-8-yl acrylate (hereinafter, "tricyclo [5 · 2 · 1.02'6] decane-8-yl" is referred to as "dicyclopentyl"), 2-bicyclo Cycloaliphatic esters of acrylic acid such as amyloxyethyl acrylate, isobornyl acrylate, tetrahydrofuryl acrylate; cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, dimethacrylate Cyclopentyl, 2-dicyclopentyloxyethyl methacrylate, isobornyl methacrylic acid , Tetrahydrofuryl methacrylate and other alicyclic esters of methacrylic acid; aryl acrylates such as phenyl acrylate and benzyl acrylate; fluorinated acrylic acids such as phenyl methacrylate and benzyl methacrylate Aryl esters; Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconic acid; 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate 200525297 Hydroxyalkyl acrylates such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate and other hydroxyalkyl methacrylates; styrene, α-methylstyrene, m-formyl Aromatic ethylenic compounds such as methylstyrene, p-methylstyrene, p-methoxystyrene, and propionitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methyl Allyl acrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, N-cyclohexylmaleimide, N-benzene Maleimide, N-benzylmaleimide, N-succinimide-imino-3 -maleimide benzoic acid , N-succinimide-4-maleimide butyrate, N-succinimide-6-maleimide hexanoate, N-succinimide-3-male Laimidine propionate, N- (9-acridinyl) maleimide and the like. Among these compounds U3), from the viewpoint of copolymerization reactivity, 2-methylcyclohexyl acrylate, t-butyl methacrylate, dicyclopentyl methacrylate, styrene, and p-methoxybenzene are preferred. Ethylene, 1,3-butadiene, etc. The said compound (a3) can be used individually or in mixture of 2 or more types. In the [A] copolymer, the content of the structural unit derived from the compound (a3) is preferably 10 to 80% by weight, and particularly preferably 20 to 60% by weight. At this time, if the content rate of the constituent unit is less than 10% by weight, the storage stability of the radiation-sensitive resin composition may decrease, and if it exceeds 80% by weight, the developability may decrease. [A] The copolymer is converted to polystyrene weight average molecular weight (hereinafter referred to as "Mw") by gel permeation chromatography (GpC) measurement, and is usually 2x1 03 ~ 5 xlO5 ', preferably 5xl03 ~ 1x1. 5. At this time, if the Mw of the [A] copolymer is less than 2x 1 〇3, the compressive strength and heat resistance of the obtained spacer tend to decrease -12-200525297. On the other hand, if it exceeds 5x 1 〇5, there is development Sexual decline. In this invention, [A] copolymer can be used individually or in mixture of 2 or more types. [A] The copolymer can be produced, for example, by radically polymerizing the compound (al), the compound (a2), and the compound U3) in a solvent in the presence of a polymerization initiator. Examples of the solvent for producing the [A] copolymer include alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; and glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether. Class; ethylene glycol alkyl ether acetates such as ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether , Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether and other diethylene glycol ethers; propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol mono-e -Propyl glycol ethers such as propyl ether, propylene glycol mono-n-butyl ether; propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono-n-butyl Propylene glycol alkyl ether acetates such as propyl ether acetate; propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol mono-n-propyl ether propionate, propylene glycol mono-n-butyl ether propionate Esters such as propylene glycol alkyl ether propionates; aromatic hydrocarbons such as toluene and xylene; methyl ethyl ketone, cyclohexanone, 4-monohydroxy —4 —Methyl-1 2-pentanone ketones; methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, methyl glycolate, ethyl glycolate, n-propyl glycolate, and glycolic acid N-butyl ester, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, 3-monohydroxypropionate, ethyl 3-hydroxypropionate, n-propyl 3-hydroxypropionate, 3-hydroxyl N-butyl propionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methyl butyrate, methyl methoxyacetate Esters, ethyl methoxyacetate, n-propyl methoxyacetate, -13- 200525297 »* n-butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, n-ethoxyacetate Propyl ester, n-butyl ethoxyacetate, methyl n-propoxyacetate, ethyl n-propoxyacetate, n-propyl propoxyacetate, n-butyl propoxyacetate, n-butoxyacetate Methyl ester, n-butoxy ethyl acetate, n-butoxy acetate n-propyl acetate, n-butoxy acetate n-butyl acetate, methyl 2-methoxypropionate, 2-methoxypropyl Ethyl ester, n-propyl 2-methoxypropionate, n-butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-ethoxy N-propyl propionate, n-butyl 2-ethoxypropionate, methyl n-propoxy propionate, ethyl n-propoxy propionate, n-propyl propoxy propionate, n-propoxy propionate Acid n-butyl ester, methyl 2-n-butoxypropionate, ethyl 2-n-butoxypropionate, n-propyl n-butoxypropionate, n-butyl n-butoxypropionate , Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, n-propyl 3-methoxypropionate, n-butyl 3-methoxypropionate, 3-ethoxypropionic acid Methyl ester, ethyl 3-ethoxypropionate, n-propyl 3-ethoxypropionate, n-butyl 3-ethoxypropionate, methyl 3-n-propoxypropionate, 3-n-propyl Ethoxy propionate, 3-n-propoxy propionate n-propyl ester, 3-n-propoxy propionate n-butyl ester, 3-n-butoxy propionate methyl ester, 3-n-butoxy propionate Other esters such as ethyl ester, n-propyl 3-n-butoxypropionate, n-butyl 3-n-butoxypropionate, and the like. In addition, as the polymerization initiator used in the production of the [A] copolymer, generally known radical polymerization initiators can be used, and examples thereof include 2,2'-azobisisobutyronitrile and 2,2'-azo. Bis- (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 4,4'-azobis (4 Monocyanovaleric acid), dimethyl-2,2'-azobis (2-methylpropionate), 2,2, azobis (4-methoxy-2,4,2-dimethyl Valeronitrile) and other azo compounds; benzyl-14-200525297 «* hydrazone peroxide, lauryl hydrazine peroxide, third butylperoxypivalate, 1,1 'bis- (third Organic peroxides such as butylperoxy) cyclohexane; hydrogen peroxide, etc. When a peroxide is used as a radical polymerization initiator, a reducing agent may be used in combination as a redox initiator. [B] Polymerizable unsaturated compound As the polymerizable unsaturated compound of the radiation-sensitive resin composition of the present invention, a bifunctional or higher acrylate and a methacrylate (hereinafter, referred to as "(meth)" are preferred Acrylate"). Examples of the bifunctional (meth) acrylate include ethylene glycol acrylate, ethylene glycol methacrylate, 1,6-hexanediol diacrylate, and 1,6-hexanediol dimethyl. Acrylate, 1,9-nonanediol diacrylate, 1,9-nonanediol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, polypropylene glycol diacrylate , Polypropylene glycol dimethacrylate, bisphenoxyethanol / dimethacrylate, bisphenoxyethanol / dimethacrylate, and the like. Examples of commercially available bifunctional (meth) acrylates include ARONIX M-210, ARONIX M-240, ARONIX M-6200 (above, manufactured by Toa Kosei Co., Ltd.), KAYARAD HDDA, and KAYARAD. HX-220, KAYARAD R- 604, UX- 220 1, UX- 230 1, UX- 3204, UX-33 (H, UX-410, UX-61 (H, UX-7101, UX-8101, MU-2100 , MU-4001 (above, manufactured by Nippon Kayaku Co., Ltd.), hardened adhesive 11 (VISC 〇AT) 260, VISC 〇AT 312, VISCOAT 335HP (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.), etc. Examples of trifunctional or higher (meth) acrylates include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, quaternary -15-200525297 nasal pentaerythritol dipropionate , Pentaerythritol trimethylpropionate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentapropionate, dipentaerythritol pentaerythritol pentaerythritol, dipentaerythritol hexapropionate, dipentaerythritol Hexamethacrylate, tris (2-propenyloxyethyl) Acid esters and tris (2-methacryloxyethyl) phosphate esters, as the (meth) acrylic acid ester having 9 or more functions, there may be a linear alkylene group and an alicyclic structure, and two Ethyl carbamate obtained by reacting the above isocyanate-based compound and a compound having one or more hydroxyl groups in the molecule and having three, four, or five acryloxy and / or methacryloxy Acrylate-based compounds, etc. Examples of commercially available trifunctional or higher (meth) acrylates include ARONIXM-309, ARONIX-400, ARONIX-402, ARONIX-405, ARONIX-450, and AR. NIX_ 1310, ARONIX-1 600, ARONIX— 1 960, ARONIX— 7100, ARONIX— 8 0 3 0, ARONIX — 8060, ARONIX — 8100, ARONIX — 8530, ARONIX 8560, ARONIX — 9050, ARONIX TO — 1450 (above , Manufactured by Toa Kosei Co., Ltd., KAYARAD TMPTA, KAYARAD DPHA, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120, KAYARAD MAX 3510 (above, manufactured by Japan Chemical Co., Ltd.) ), V ISCOAT 295, VISCOAT 300, VISCOAT 360, VISCOAT GPT, VISCOAT 3PA, VIS C 〇AT 4 0 (above 'Osaka Organic Chemical Industry Co., Ltd.) and urethane acrylate compounds include NEWFRONTIERR — 1150 (manufactured by Daiichi Kogyo Co., Ltd.), KAYARADDPHA — 40H (manufactured by Japan Chemical Co., Ltd.), etc. In the present invention, the polymerizable unsaturated compound may be used alone or in combination of two kinds. The amount of the polymer unsaturated compound used in the radiation-sensitive resin composition of the present invention is preferably 30 to 200 parts by weight, and particularly preferably 50 to 140 parts by weight relative to 100 parts by weight of the [A] copolymer. Serving. At this time, if the amount of the polymer unsaturated compound is less than 30 parts by weight, the film edge and strength of the obtained spacer tend to be easily reduced. On the other hand, if it exceeds 200 parts by weight, it may be obtained The spacer has insufficient adhesion. [C] Biimidazole-based compound As the biimidazole-based compound used in the present invention, for example, a compound represented by the following general formula (1) (hereinafter, referred to as a "bisimidazole-based compound (C1)"), A compound represented by the following general formula (2) (hereinafter, referred to as a "bisimidazole-based compound (C2)." And the like.

[式中，X表示氫原子、鹵原子、氰基、碳數丨〜4的烷基 或碳數6〜9的方基，a表示—COO— R(其中，]^表示碳數丄〜4 的烷基或碳數6〜9的芳基），n是丄〜3的整數，各①是丄〜3 的整數。] -17- 200525297[In the formula, X represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having a carbon number of 1 to 4 or a square group having a carbon number of 6 to 9, and a represents —COO—R (wherein,] ^ represents a carbon number 丄 to 4 Alkyl group or aryl group having 6 to 9 carbon atoms), n is an integer of 丄 to 3, and each ① is an integer of 丄 to 3; ] -17- 200525297

X3 (式中，X1、X2及X3相互獨立地表示氫原子、鹵原子、 氰基、碳數1〜4的烷基或碳數6〜9的芳基，但是，X1、X2 及X3的2個以上不能同時爲氫原子。） 作爲雙咪唑系化合物，例如可舉出2,2’ 一雙（2—氯苯 基）—4,4’ ，5,5’ —四苯基雙味哩、2,2’ —雙（2—氛苯基） 一 4,4’ ，5,5’ 一肆（4 —乙氧基羰基苯基）雙咪唑、2,2’ 一雙 (2-氯苯基）一 4,4’ ，5,5’ 一肆（4 一苯氧基鑛基苯基）雙味 唑、2,2’ 一雙（2,4—二氯苯基）—4,4’，5,5’ 一肆（4 一乙氧 基羰基苯基）雙咪唑、2,2’ 一雙（2,4 一二氯苯基）一 4,4’ ，5,5’ 一肆（4一苯氧基羰基苯基）雙咪唑、2,2’ 一雙 (2,4,6-三氯苯基）一 4,4’ ，5,5’ 一肆（4 一苯氧基羰基苯基） 雙咪哩、2,2’ 一雙（2,4,6 —三氯苯基）一 4,4’ ，5,5’ 一肆（4 一苯氧基羰基苯基）雙咪唑、2,2’ 一雙（2-氰基苯基）一 4,4’ ，5,5’ 一肆（4 一乙氧基羰基苯基）雙咪唑、2,2’ 一雙（2 一氰基苯基）—4,4’ ，5,5’ 一肆（4 一苯氧基羰基苯基）雙咪 唑、2,2’ 一雙（2—甲基苯基）一4,4’ ，5,5’ 一肆（4 —甲氧基 羰基苯基）雙咪唑、2,2’ 一雙（2—甲基苯基）一 4,4’ ，5,5’ -18- 200525297 a · 一肆（4 一乙氧基羰基苯基）雙咪唑、2,2’ 一雙（2-甲基苯基） 一 4,4’ ，5,5’ 一肆（4一苯氧基羰基苯基）雙咪唑、2,2’ 一雙 (2—乙基苯基）一 4,4’ ，5,5’ 一肆（4 一甲氧基羰基苯基）雙 咪唑、2,2’ 一雙（2—乙基苯基）一4,4’ ，5,5’ 一肆（4 一乙氧 基羰基苯基）雙咪唑、2,2’ 一雙（2—乙基苯基）一 4,4’ ，5,5’ 一肆（4 —苯氧基羰基苯基）雙咪唑、2,2’ 一雙（2 一苯基苯基）一 4,4’ ，5,5’ 一肆（4 一甲氧基羰基苯基）雙咪 唑、2,2’ 一雙（2—苯基苯基）—4,4’ ，5,5’ 一肆（4 一乙氧基 羰基苯基）雙咪唑、2,2’ 一雙（2 —苯基苯基）一 4,4’ ，5,5’ -肆（4-苯氧基羰基苯基）雙咪唑等的雙咪唑系化合物 (C1)； 2,2’ 一雙（2,4 一二氯苯基）一 4,4’ ，5,5’ —四苯基雙 咪唑、2,2’ 一雙（2,4,6-三氯苯基）一 4,4’ ，5,5’ 一四苯基 雙咪唑、2,2’ 一雙（2,4 一二溴苯基）一 4,4’ ，5,5’ 一四苯基 雙咪唑、2,2’ 一雙（2,4,6 —三溴苯基）一4,4’ ，5,5’ 一四苯 基雙咪唑、2,2’ 一雙（2,4一二氰基苯基）—4,4’ ，5,5’ 一四 苯基雙咪唑、2,2’ 一雙（2,4,6-三氰基苯基）一 4,4’ ，5,5’ 一四苯基雙咪唑、2,2’ 一雙（2,4 一二甲基苯基）一 4,4’ ，5,5’ 一四苯基雙咪唑、2,2’ 一雙（2，4,6—三甲基苯基） 一 4,4， ，5,5’ 一四苯基雙咪唑、2,2’ 一雙（2,4 一二乙基苯 基）一 4,4， ，5,5’ 一四苯基雙咪唑、2,2，一雙（2，4,6—三乙 基苯基）一 4,4’ ，5,5’ 一四苯基雙咪唑、2,2’ 一雙（2,4 一二 苯基苯基）一 4,4’ ，5,5’ —四苯基雙咪唑、2,2’ 一雙（2,4,6 一三苯基苯基）一 4,4’ ，5,5’ 一四苯基雙咪唑等的雙咪唑 系化合物（C2)等。 -19- 200525297 _ 身 這些雙咪唑系化合物中，特佳的是2,2， 一雙（2-氯苯 基）—4,4’ ，5,5’ 一四苯基雙咪唑、2,2’ 一雙（2 —氯苯基） 一 4,4 ,5,5 一肆（4 一乙氧基鑛基苯基）雙咪u坐、2,2’ 一雙 (2—溴苯基）一 4,4’ ，5,5’ 一肆（4 一乙氧基羰基苯基）雙咪 唑、2,2’ —雙（2,4 —二氯苯基）一 4,4’ ，5,5’ 一四苯基雙咪 唑、2,2’ 一雙（2,4 —二溴苯基）—4,4’ ，5,5， 一四苯基雙咪 唑、2,2’ —雙（2,4,6—三氯苯基）一 4,4’ ，5,5， 一四苯基雙 咪唑、2,2’ 一雙（2,4,6—三溴苯基）一 4,4’ ，5,5， 一四苯基 雙咪唑等。 雙咪唑系化合物（C1)及雙咪唑系化合物（C2)相對於溶 劑的溶解性優良，不生成未溶解物、析出物等的異物，且 靈敏度高，即使是切斷3 5 0nm以下的波長的放射線，用少 的能量的曝光也可充分進行固化反應，同時，可形成沒有 圖形的丟失、缺損或下旋的優良的間隔物。 在本發明中，雙咪唑系化合物可以單獨或2種以上混 合使用。 在本發明的感放射線性樹脂組成物中，雙咪唑系化合 物的使用量爲，相對於[A]共聚物100重量份，較佳的是 0 . 1〜5 0重量份、特佳的是1〜3 5重量份。此時，如果雙咪唑 系化合物的使用量不足0· 1重量份時，則得到的間隔物的 膜邊性及強度有容易降低的趨勢，另一方面，若超過5 0重 量份時，則有向液晶中增加溶出物而使電壓保持率容易降 低的趨勢。 [D]含有羰基之聚合引發劑 本發明的[D]成份，具有羰基的感放射線性聚合引發劑 -20- 200525297 (以下，稱爲[D ]含羰基聚合引發劑。），是具有調節形成間 隔物形狀的作用的成份。 作爲[D]含有羰基聚合引發劑，例如可舉出苄基、二乙 醯基等的α —二酮類；苯偶姻等的偶姻類；苯偶姻甲基醚、 苯偶姻乙基醜、苯偶姻異丙基酸等的偶姻釀類；嚷噸酮、 2，4 一二乙基噻噸酮、噻Β頓酮-4-擴酸、二苯甲酮、4，4， 一 雙（二甲基胺基）二苯甲酮、4,4’ 一雙（二乙基胺基）二苯甲 酮等的二苯甲酮類·，苯乙酮、4 一二甲基胺基苯乙酮、α， α’ 一二甲氧基乙醯氧基苯乙酮、2，2’ 一二甲氧基一 2 — 苯基苯乙酮、4 —甲氧基苯乙酮、2—甲基[4 一（甲硫基）苯基] 一 2 -嗎啉基一1—丙醒、2—千基—2 —二甲基氨基一 1 一（4 一嗎啉基苯基）一 丁酮一 1等的苯乙酮類；蒽醌、1，4 一萘醌 等的醌類；2,4,6—三甲基苯甲醯基二苯基膦氧化物、雙（2,6 一二甲氧基苯甲醯基）一 2,4,4 一三甲基戊基膦氧化物、雙 (2,4,6-三甲基苯甲醯基）苯基膦氧化物等的膦氧化物類 等。 另外，作爲[D]含羰基之聚合引發劑的市售品，例如可 舉出 IRGACURE - 124、IRGACURE - 149、IRGACURE - 184、 IRGACURE- 3 69、IRGACURE - 5 00、IRGACURE - 65 1、 IRGACURE - 819、IRGACURE - 907、IRGACURE — 1 700、 IRGACURE - 1 000、IRGACURE - 1 800、IRGACURE — 1 8 5 0、 IRGACURE— 2959、Darocur— 1173、Darocur— 1116、Darocur —1664、Darocur — 2959、Darocur — 4043(以上，Ciba Specialty Chemicals 社製）、KAYACURE — DETX、KAYACURE — MBP、 KAYACURE- DMBI、KAYACURE— EPA、KAYACURE—〇A(以 -21 - 200525297 < * 上，曰本化藥（株）製）、LUCIRINTP〇（BASFCo. LTD製）、 VICURE — 10、VICURE—55(以上，STAUFFER Co.LTD 製） 等。 在本發明中，[D]含羰基之聚合引發劑可以單獨或2種 以上混合使用。 在本發明的感放射線性樹脂組成物中，相對於[A]共聚 物1 0 0重量份，[D ]含鑛基聚合引發劑的使用量較佳的是 1〜5 0重量份、特佳的是3〜30重量份。此時，[D]含羰基之 聚合引發劑的使用量低於1重量份時，得到的間隔物的膜 邊性及圖形形狀容易產生不良的趨勢，另一方面，若超過 1 00重量份時，得到的圖形尺寸可能超過光罩圖形設計尺寸 容許範圍。 [E]具有二烷基胺基的化合物 本發明的感放射線性樹脂組成物中的具有二烷基胺基 的化合物，只要具有敏化[C ]雙咪唑系化合物的作用的就沒 有特別限制，較佳的化合物，例如可舉出4,4’ 一雙（二甲 基胺基）二苯甲酮、4，4’ 一雙（二乙基胺基）二苯甲酮、對二 甲基胺基苯甲酸乙酯、對二乙基胺基苯甲酸乙酯、對二甲 基胺基苯甲酸異戊酯、對二乙基胺基苯甲酸異戊酯等的芳 香族化合物。但是，如4,4’ 一雙（二甲基胺基）二苯甲酮或 4,4’ 一雙（二乙基胺基）二苯甲酮的情況那樣，具有二烷基 胺基的化合物屬於[D]含有羰基聚合引發劑的範圍時，要使 用與[D]成份不同的化合物。 這些具有二烷基胺基的化合物中，特佳的是4,4’ 一雙 (二乙基胺基）二苯甲酮。 -22- 200525297 « 鼻 在本發明中，具有二烷基胺基的化合物可以單獨或2 種以上混合使用。 在本發明的感放射線性樹脂組成物中，相對於[A]共聚 物1 00重量份具有二烷基胺基的化合物的使用量較佳的是 0.1〜50重量份、特佳的是1〜20重量份。此時，具有二烷基 胺基的化合物的使用量不足0.1重量份時，有得到的間隔 物的膜邊性及圖形形狀容易產生不良的趨勢，另一方面， 若超過50重量份時，有容易形成圖形形狀不良的趨勢。 [F]硫醇系化合物 本發明的感放射線性樹脂組成物中的硫醇系化合物是 具有對於[C]雙咪唑系化合物供給氫自由基作用的成份。 即，[C]雙咪唑系化合物通過[E]具有二烷基胺基的化合 物敏化，進行開裂產生咪唑基自由基，但此時，若不存在 硫醇系化合物時，就不可能表達高的自由基聚合能，往往 得到的間隔物是倒錐形狀的不理想形狀。可是，在[C]雙咪 唑系化合物及[E]具有二烷基胺基的化合物共存體系中，經 由添加硫醇系化合物，在咪唑自由基中供給氫自由基的結 果，將咪唑自由基變換成中性的咪唑的同時，產生具有聚 合引發能高的硫自由基的成份，由此，可將間隔物的形狀 作成更好的正錐形狀。 作爲硫醇系化合物，例如可舉出2 -疏基苯并噻哇、2 一锍基苯并噚唑、2 —锍基苯并咪唑、2 —锍基一 5 —甲氧基 苯并噻唑、2 -锍基- 5 -甲氧基苯并咪唑等的芳香族系化 合物；3 -锍基丙酸、3 -锍基丙酸甲酯、3 -锍基丙酸乙酯、 3 -毓基丙酸正辛酯等的脂肪族單硫醇系化合物；3，6 一二 -23- 200525297 • % 氧一 1，8 —辛烷二硫醇、季戊四醇四（酼基乙酸酯）、季戊四 醇四（3 —疏;基丙酸酯）等的脂肪族多元硫醇系化合物等。 在本發明的感放射線性樹脂組成物中，相對於[C]雙咪 唑系化合物1 0 0重量份硫醇系化合物的使用量較佳的是 0.1〜50重量份、特佳的是1〜20重量份。此時，硫醇系化合 物的使用量不足0 · 1重量份時，有得到的間隔物的膜邊性 及圖形形狀容易產生不良的趨勢，另一方面，若超過50重 量份時，有容易形成圖形形狀不良的趨勢。 任意添加劑 在本發明的感放射線性樹脂組成物中，根據需要，在 不損壞本發明的效果的範圍內，可配合上述以外的任意添 加劑’例如黏結助劑、界面活性劑、保存穩定劑、耐熱性 提高劑等。 上述黏結助劑是爲了提高形成的間隔物及基板的黏結 性而使用的成份。 作爲這樣的黏結助劑，較佳的是具有羧基、甲基丙烯 _基、乙烯基、異氰酸酯基、環氧基等的反應性官能基的 官能性矽烷偶合劑，作爲其例子可舉出三甲氧基甲矽烷基 苯甲酸、r 一甲基丙烯醯氧丙基三甲氧基矽烷、乙烯基三 乙酿氧基矽烷、乙烯基三甲氧基矽烷、r 一異氰酸酯丙基 三乙氧基矽烷、r 一縮水甘油氧基丙基三甲氧基矽烷、冷 (3,4 環興基環己基）乙基三甲氧基砂院等。 這些黏結助劑可以單獨或2種以上混合使用。 黏結助劑的調配量，相對於[A]共聚物丨00重量份較佳 的是20重量份以下、特佳的是1 〇重量份以下。此時，黏 -24 - 200525297 4 · 結助劑的g周配量超過20重量份時，有容易產生顯影殘缺的 趨勢。 上述的界面活性劑是爲了提高塗覆性而使用的成份。 作爲這樣的界面活性劑，例如較佳的是氟系界面活性 劑、有機矽系界面活性劑等。 上述的氟系界面活性劑，較佳的是在末端 '主鏈及側 鏈的至少一個部位具有氟烷基及/或氟伸烷基的化合物，作 爲其例子可舉出丨，丨，2，2,一四氟正辛基（1，12,2，—四氟正丙 基）醚、1，1，2,2,一四氟正辛基（正己基）醚、六乙二醇二 (1，1，2,2,3,3—六氟正戊基）醚、八乙二醇二（ι，ι，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、八丙二 醇二（1，1，2,2—四氟正丁基）醚、全氟正十二烷磺酸鈉、 1，1，2,2,3,3 - /、氯正癸院、1，1，2,2,8,8,9,9，10，10—十氯正十 二烷及、氟烷基苯磺酸鈉類、氟烷基磷酸鈉類、氟烷基羧 酸鈉類、二甘油肆（氟烷基聚氧乙烯基醚）類、氟烷基銨碘 化合物類、氟烷基甜菜鹼類、其他的氟烷基聚氧乙烯基醚 類、全氟烷基聚氧乙醇類、全氟烷基烷氧基酯類、羧酸氟 烷基酯類等。 作爲氟系界面活性劑的市售品，例如可舉出BM -1000、BM — 1100(以上，BMCHEMIE 社製）、MEGAFACE F142D、MEGAFACE F172、MEGAFACE F173、MEGAFACE F183、MEGAFACE F178、MEGAFACE F191 ' MEGAFACE F471、MEGAFACE F476(以上，大日本油墨化學工業（株）X3 (where X1, X2, and X3 independently represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 9 carbon atoms, but X1, X2, and X3 are 2 More than one cannot be a hydrogen atom at the same time.) Examples of the bisimidazole-based compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbismuth, 2,2 '—bis (2-aminophenyl) -1,4', 5,5'-1 (4-ethoxycarbonylphenyl) bisimidazole, 2,2'-bis (2-chlorophenyl) ) A 4,4 ', 5,5' one (4 -phenoxymine phenyl) bisamizole, 2,2 'one bis (2,4-dichlorophenyl)-4,4', 5,5 '1- (4-ethoxycarbonylphenyl) bisimidazole, 2,2' 1-bis (2,4-dichlorophenyl) -4,4 ', 5,5' 1- (4-1 Phenoxycarbonylphenyl) bisimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-methyl (4-monophenoxycarbonylphenyl) Bisimide, 2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-one (4-monophenoxycarbonylphenyl) bisimidazole, 2,2 'One bis (2-cyanophenyl) -4,4', 5,5 'one branch (4-monoethoxycarbonylphenyl) bisimidazole, 2,2' one bis (2-monocyanophenyl)-4,4 ', 5,5' one branch (4-monophenoxy) Carbonylcarbonylphenyl) bisimidazole, 2,2'-bis (2-methylphenyl) -4,4 ', 5,5'-iso (4-methoxycarbonylphenyl) bisimidazole, 2,2 'One bis (2-methylphenyl) -4,4', 5,5 '-18- 200525297 a · 1- (4-ethoxycarbonylphenyl) bisimidazole, 2,2' one bis (2 -Methylphenyl) -4,4 ', 5,5'-(4-phenoxycarbonylphenyl) bisimidazole, 2,2'-bis (2-ethylphenyl) -4,4 ' , 5,5 '1- (4-methoxycarbonylphenyl) bisimidazole, 2,2' 1-bis (2-ethylphenyl) -4,4 ', 5,5'-4 (4-ethyl) Oxycarbonylphenyl) bisimidazole, 2,2'-bis (2-ethylphenyl) -4,4 ', 5,5'-iso (4-phenoxycarbonylphenyl) bisimidazole, 2 ,, 2 'bis (2 phenylphenyl) -4,4', 5,5 '1- (4-methoxycarbonylphenyl) bisimidazole, 2,2' bis (2-phenylphenyl) ) —4,4 ', 5,5' (4, 1) Carbonylcarbonylphenyl) bisimidazole, 2,2'-bis (2-phenylphenyl) -4,4 ', 5,5'-(4-phenoxycarbonylphenyl) bisimidazole, etc. Compounds (C1); 2,2 'one bis (2,4 dichlorophenyl) one 4,4', 5,5'-tetraphenylbisimidazole, 2,2 'one bis (2,4, 6-trichlorophenyl) -4,4 ', 5,5'-tetraphenylbisimidazole, 2,2'-bis (2,4-dibromophenyl) -4,4', 5,5 ' Tetraphenylbisimidazole, 2,2 'monobis (2,4,6-tribromophenyl) -4,4', 5,5'tetraphenylbisimidazole, 2,2 'monobis (2 , 4-dicyanophenyl) -4,4 ', 5,5'-tetraphenylbisimidazole, 2,2'-bis (2,4,6-tricyanophenyl) -4,4' , 5,5'-tetraphenylbisimidazole, 2,2'-bis (2,4-dimethylphenyl) -4,4 ', 5,5'-tetraphenylbisimidazole, 2,2' One bis (2,4,6-trimethylphenyl) One 4,4,5,5'5 Tetraphenylbisimidazole, 2,2 'One bis (2,4 Diethylphenyl) One 4,4,, 5,5'-tetraphenylbisimidazole, 2,2,1-bis (2,4,6-triethylphenyl) -4,4 ', 5,5' Tetraphenylbisimidazole, 2,2 'monobis (2,4 diphenylphenyl) -4,4', 5,5'-tetraphenylbisimidazole, 2,2 'monobis (2, 4,6 triphenylphenyl), 4,4 ', 5,5' tetraphenylbisimidazole and other bisimidazole compounds (C2) and the like. -19- 200525297 _ Among these bisimidazole compounds, 2,2,1-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbisimidazole, 2,2 'One bis (2-chlorophenyl) one 4,4,5,5 one (4 -ethoxyloxyphenyl) bisamidol, 2,2' one bis (2-bromophenyl) one 4,4 ', 5,5' 1- (4-ethoxycarbonylphenyl) bisimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5' Tetraphenylbisimidazole, 2,2 'bis (2,4-dibromophenyl) -4,4', 5,5, Tetraphenylbisimidazole, 2,2'-bis (2,4 , 6-trichlorophenyl) -4,4 ', 5,5, tetraphenylbisimidazole, 2,2'-bis (2,4,6-tribromophenyl) -4,4', 5 , 5, tetraphenylbisimidazole and so on. The bisimidazole-based compound (C1) and the bisimidazole-based compound (C2) have excellent solubility in a solvent, do not generate foreign matters such as undissolved matter and precipitates, and have high sensitivity. The radiation and the exposure with a small amount of energy can sufficiently perform the curing reaction, and at the same time, it can form an excellent spacer without pattern loss, defects or downspin. In the present invention, the bisimidazole-based compound may be used alone or as a mixture of two or more. In the radiation-sensitive resin composition of the present invention, the used amount of the bisimidazole-based compound is preferably 0.1 to 50 parts by weight, and particularly preferably 1 to 100 parts by weight of the [A] copolymer. ~ 3 5 parts by weight. At this time, when the amount of the bisimidazole-based compound is less than 0.1 part by weight, the film edge and strength of the obtained spacer tends to be easily reduced. On the other hand, when it exceeds 50 parts by weight, Increasing eluted matter into the liquid crystal tends to decrease the voltage holding ratio. [D] Carbonyl-containing Polymerization Initiator The component [D] of the present invention has a carbonyl-containing radiation-sensitive polymerization initiator-20-200525297 (hereinafter, referred to as [D] a carbonyl-containing polymerization initiator.), Which has a regulated formation Spacer-shaped functioning ingredients. Examples of the [D] carbonyl-containing polymerization initiator include α-diketones such as benzyl, diethylfluorenyl, and the like; benzoin and other benzoin; benzoin and methyl ether and benzoin and ethyl Ugly, benzoin isopropyl acid, etc .; xanthones, 2,4-diethylthioxanthone, thiobentonone-4-propanoic acid, benzophenone, 4, 4, One bis (dimethylamino) benzophenone, 4,4 'One bis (diethylamino) benzophenone, benzophenones, etc., acetophenone, 4-dimethylamine Acetophenone, α, α'-dimethoxyethoxylated acetophenone, 2,2'-dimethoxy-2-2-phenylacetophenone, 4-methoxyacetophenone, 2 —Methyl [4-mono (methylthio) phenyl] —2-morpholinyl—1-propanyl, 2-kiloyl-2-dimethylamino—1— (4-morpholinylphenyl) — Acetophenones such as methyl ethyl ketone-1; anthraquinones, quinones such as 1,4-naphthoquinone; 2,4,6-trimethylbenzylidene diphenylphosphine oxide, bis (2,6 Mono-dimethoxybenzyl), 2,4,4 trimethylpentylphosphine oxide, bis (2,4,6-trimethylbenzyl) phenylphosphine oxide, etc. Phosphine oxide and the like. Examples of commercially available products of the [D] carbonyl-containing polymerization initiator include IRGACURE-124, IRGACURE-149, IRGACURE-184, IRGACURE-3 69, IRGACURE-5 00, IRGACURE-65 1, and IRGACURE- 819, IRGACURE-907, IRGACURE — 1 700, IRGACURE-1 000, IRGACURE-1 800, IRGACURE-1 8 5 0, IRGACURE — 2959, Darocur — 1173, Darocur — 1116, Darocur — 1664, Darocur — 2959, Darocur — 4043 (above, manufactured by Ciba Specialty Chemicals), KAYACURE-DETX, KAYACURE-MBP, KAYACURE- DMBI, KAYACURE- EPA, KAYACURE-〇A (from -21-200525297 < * above, manufactured by Japan Chemical Co., Ltd.) ), LUCIRINTP0 (manufactured by BASFCo. LTD), VICURE-10, VICURE-55 (above, manufactured by STAUFFER Co.LTD), etc. In the present invention, the [D] carbonyl group-containing polymerization initiator may be used alone or as a mixture of two or more. In the radiation-sensitive resin composition of the present invention, the use amount of the [D] mineral-based polymerization initiator is preferably 1 to 50 parts by weight, particularly preferably, based on 100 parts by weight of the [A] copolymer. It is 3 to 30 parts by weight. At this time, when the use amount of the [D] carbonyl-containing polymerization initiator is less than 1 part by weight, the edge and film shape of the obtained spacer tend to be defective. On the other hand, when it exceeds 100 parts by weight The obtained graphic size may exceed the allowable range of the graphic design size of the mask. [E] Compound having a dialkylamine group The compound having a dialkylamine group in the radiation-sensitive resin composition of the present invention is not particularly limited as long as it has a function of sensitizing the [C] bisimidazole-based compound, Preferred compounds include, for example, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, and p-dimethylamine Aromatic compounds such as ethyl benzoate, ethyl p-diethylaminobenzoate, isoamyl p-dimethylaminobenzoate, isoamyl p-diethylaminobenzoate, and the like. However, as in the case of 4,4'-bis (dimethylamino) benzophenone or 4,4'-bis (diethylamino) benzophenone, a compound having a dialkylamino group In the case where [D] contains a carbonyl polymerization initiator, a compound different from the component [D] is used. Among these compounds having a dialkylamino group, 4,4'-bis (diethylamino) benzophenone is particularly preferred. -22- 200525297 «Nasal In the present invention, a compound having a dialkylamine group can be used alone or as a mixture of two or more. In the radiation-sensitive resin composition of the present invention, the use amount of the compound having a dialkylamine group with respect to 100 parts by weight of the [A] copolymer is preferably 0.1 to 50 parts by weight, particularly preferably 1 to 20 parts by weight. In this case, when the amount of the compound having a dialkylamine group is less than 0.1 part by weight, the film edge and shape of the obtained spacer tend to be defective. On the other hand, when it exceeds 50 parts by weight, It is easy to form a tendency of a bad shape of a figure. [F] Thiol-based compound The thiol-based compound in the radiation-sensitive resin composition of the present invention is a component having a function of supplying a hydrogen radical to the [C] bisimidazole-based compound. That is, the [C] bisimidazole-based compound is sensitized by a compound having a dialkylamine group in [E] to generate an imidazolyl radical by cleavage. However, at this time, if a thiol-based compound is not present, it is impossible to express high The free radical polymerization energy often results in spacers that are not ideal in the shape of an inverted cone. However, in the coexistence system of the [C] bisimidazole-based compound and the [E] compound having a dialkylamine group, the imidazole radical is converted as a result of supplying a hydrogen radical to the imidazole radical by adding a thiol-based compound. At the same time as neutral imidazole, a component having a sulfur radical having a high polymerization initiation capacity is generated, whereby the shape of the spacer can be made into a better forward cone shape. Examples of the thiol-based compound include 2-mercaptobenzothiazole, 2-monofluorenylbenzoxazole, 2-fluorenylbenzimidazole, 2-fluorenyl-5-methoxybenzothiazole, Aromatic compounds such as 2-fluorenyl-5 -methoxybenzimidazole; 3-fluorenylpropanoic acid, methyl 3-fluorenylpropionate, ethyl 3-fluorenylpropionate, 3-propenylpropionate Aliphatic monothiol compounds such as n-octyl acid; 3,6 di-23-23 200525297 •% oxygen-1,8-octane dithiol, pentaerythritol tetra (fluorenyl acetate), pentaerythritol tetra ( 3-Polyurethane, etc.). In the radiation-sensitive resin composition of the present invention, the used amount of 100 parts by weight of the thioimide-based compound with respect to the [C] bisimidazole-based compound is preferably 0.1 to 50 parts by weight, and particularly preferably 1 to 20 Parts by weight. At this time, when the amount of the thiol-based compound is less than 0.1 parts by weight, there is a tendency that the obtained film has poor edge and pattern shape, and when it exceeds 50 parts by weight, it tends to be easily formed. Graphic bad shape trend. Any additive may be added to the radiation-sensitive resin composition of the present invention, if necessary, within a range that does not impair the effects of the present invention, such as a bonding aid, a surfactant, a storage stabilizer, and heat resistance Sex improver and so on. The above-mentioned adhesion promoter is a component used to improve the adhesion of the formed spacer and the substrate. As such a bonding aid, a functional silane coupling agent having a reactive functional group such as a carboxyl group, a methacryl group, a vinyl group, an isocyanate group, or an epoxy group is preferable, and trimethoxy group is mentioned as an example thereof. Methylsilylbenzoic acid, r monomethacryloxypropyltrimethoxysilane, vinyltriethyloxysilane, vinyltrimethoxysilane, r-isocyanatepropyltriethoxysilane, r- Glycidyloxypropyltrimethoxysilane, cold (3,4 cyclohexylcyclohexyl) ethyltrimethoxy ash, etc. 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, and particularly preferably 10 parts by weight or less, based on 00 parts by weight of the [A] copolymer. At this time, if the g-week compounding amount of the bonding aid exceeds 20 parts by weight, there is a tendency that development defects are liable to occur. The above-mentioned surfactant is a component used for improving coating properties. Examples of such a surfactant include a fluorine-based surfactant and a silicone-based surfactant. The above-mentioned fluorine-based surfactant is preferably a compound having a fluoroalkyl group and / or a fluoroalkylene group in at least one portion of the terminal 'main chain and side chain, and examples thereof include 丨, 丨, 2, 2,1-tetrafluoro-n-octyl (1,12,2, -tetrafluoro-n-propyl) ether, 1,1,2,2,1-tetrafluoro-n-octyl (n-hexyl) ether, hexaethylene glycol di ( 1,1,2,2,3,3-hexafluoron-pentyl) ether, octaethylene glycol di (ι, ι, 2,2-tetrafluoron-butyl) ether, hexapropylene glycol di (1,1, 2,2,3,3-hexafluoro-n-pentyl) ether, octapropylene glycol di (1,1,2,2-tetrafluoro-n-butyl) ether, sodium perfluoro-n-dodecanesulfonate, 1, 1, 2,2,3,3-/, chloro-n-decane, 1,1,2,2,8,8,9,9,10,10-decachloro-n-dodecane and sodium fluoroalkylbenzenesulfonate Type, sodium fluoroalkyl phosphates, sodium fluoroalkyl carboxylates, diglycerol (fluoroalkyl polyoxyvinyl ether), fluoroalkyl ammonium iodine compounds, fluoroalkyl betaines, other fluorine Alkyl polyoxy vinyl ethers, perfluoroalkyl polyoxyethanols, perfluoroalkyl alkoxy esters, carboxylic acid fluoroalkyl esters, and the like. Examples of commercially available fluorine-based surfactants include BM-1000, BM-1100 (above, manufactured by BMCHEMIE), MEGAFACE F142D, MEGAFACE F172, MEGAFACE F173, MEGAFACE F183, MEGAFACE F178, MEGAFACE F191 'MEGAFACE F471 MEGAFACE F476 (above, Dainippon Ink Chemical Industry Co., Ltd.)

製）、FLU〇RAD FC — 170C、FLU〇RAD FC — 171、FLU〇RAD FC —430、FLU〇RAD FC — 431(以上，住友 3M (株）製）、SURFL〇N -25- 200525297 S — 112、SURFLON S — 113、SURFLON S — 131、SURFLON S —141、SURFLON S — 145、SURFLON S — 382、SURFLON SC 一 101、 SURFLON SC — 102、 SURFLON SC — 103、 SURFLON SC — 104、SURFLON SC — 105、SURFLON SC — 106(以上， 旭石肖子（株）製）、EPTOP EF301、EPTOP EF 303、EPTOP EF 3 5 2(以上，新秋田化成（株）制）、FTERGENTFT—100、 FTERGENT FT- 110、FTERGENT FT - 140A、FTERGENT FT 一 150、FTERGENT FT — 250、FTERGENT FT— 251、 FTERGENT FT — 300、FTERGENT FT- 310、FTERGENT FT 一 400S、FTERGENT FTX - 218、FTERGENT FTX — 251(以 上，（株）NEOS製）等。 作爲上述有機矽係界面活性劑，例如可舉出用 TORAYSILICON DC3PA、TOR A YSILICON DC7PA、 TORAYSIUCON SHI 1PA、TORAYSILICON SH2 1 PA、 TORAYSILICON SH28PA ' TORAYSILICON SH29PA ^ TORAYSILICON SH30PA ^ TORAYSILICON SH- 190 ' TORAYSILICON SH— 193、TORAYSILICON SZ — 603 2、 TORAYSILICON SF— 8 42 8、 TOR A YSILICON DC — 57、 TORAYSILICON DC— 190(以上、DOW CORNNING TORAY SILICON(株）製），TSF — 4440、TSF — 4300、TSF — 4445、TSF —4446、TSF— 4460、TSF - 4452(以上，GE 東芝 SILICON(株） 製）等的商品名市售的。 另外，作爲上述以外的界面活性剂，可舉出聚氧化乙 烯月桂基醚、聚氧化乙烯硬脂基醚、聚氧化乙烯油基醚等 的聚氧化乙烯烷基醚類；聚氧化乙烯正辛基苯基醚、聚氧 -26- 200525297 化乙烯正壬基苯基醚等的聚氧化乙烯芳基醚類；聚氧化乙 烯二月桂酸酯、聚氧化乙烯二硬脂酸酯等的聚氧化乙烯二 烷基酯等的非離子系界面活性劑或有機矽氧烷聚合物 ΚΡ341(信越化学工業（株）製）、（甲基）丙烯酸系共聚物 P〇LYFLU〇 No.57、POLYFLUO Νο·95(以上，共榮示土化學（株） 製）等。 這些界面活性劑可以單獨或2種以上混合使用。 界面活性劑的調配量相對於[A ]共聚物1 0 0重量份較佳 的是1 · 0重量份以下、更佳的是0 · 5重量份以下。此時，界 面活性劑的調配量超過1 · 0重量份時，有容易生成膜斑的 趨勢。 作爲上述保存穩定劑，例如可舉出硫、醌類、羥基酮 類、聚氧化合物、胺類、硝基亞硝基化合物等，更具體地 可舉出4 一甲氧基苯酚、N—亞硝基一 N—苯基羥基胺鋁等。 這些保存穩定劑可以單獨或2種以上混合使用。 保存穩定劑的調配量相對於[A]共聚物1 〇〇重量份較佳 的是3.0重量份以下、更佳的是〇 · 5重量份以下。此時，保 存穩定劑的調配量超過3 · 0重量份時，可能靈敏度降低圖 形形狀劣化。 作爲上述耐熱性提高劑’例如可舉出N〜（烷氧基甲基） 乙炔脲化合物、N—（烷氧基甲基）蜜胺化合物、具有2個以 上環氧基的化合物等。(Manufactured), FLU〇RAD FC — 170C, FLU —RAD FC — 171, FLU —RAD FC —430, FLU —RAD FC — 431 (above, manufactured by Sumitomo 3M Co., Ltd.), SURFLONN -25- 200525297 S — 112, SURFLON S — 113, SURFLON S — 131, SURFLON S — 141, SURFLON S — 145, SURFLON S — 382, SURFLON SC — 101, SURFLON SC — 102, SURFLON SC — 103, SURFLON SC — 104, SURFLON SC — 105, SURFLON SC — 106 (above, manufactured by Asahi Ishiko Co., Ltd.), EPTOP EF301, EPTOP EF 303, EPTOP EF 3 5 2 (above, manufactured by Shin Akita Chemical Co., Ltd.), FTERGENTFT-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 — 251 (above, (strains ) NEOS) etc. Examples of the organosilicon surfactant include TORAYSILICON DC3PA, TOR A YSILICON DC7PA, TORAYSIUCON SHI 1PA, TORAYSILICON SH2 1 PA, TORAYSILICON SH28PA 'TORAYSILICON SH29PA ^ TORAYSILICON SH30PA ^ TORAYSILICON SH- 190' TORAYSILICON TORAYSILICON SZ — 603 2, TORAYSILICON SF — 8 42 8, TOR A YSILICON DC — 57, TORAYSILICON DC — 190 (above, manufactured by DOW CORNNING TORAY SILICON Co., Ltd.), TSF — 4440, TSF — 4300, TSF — 4445, TSF — 4446, TSF — 4460, TSF-4452 (above, manufactured by GE Toshiba SILICON Co., Ltd.) and other commercial products. Examples of the surfactant other than the above include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene n-octyl Phenyl ether, polyoxy-26-200525297 polyoxyethylene aryl ethers such as ethylene n-nonylphenyl ether; polyoxyethylene dilaurate, polyoxyethylene distearate, etc. Non-ionic surfactants such as alkyl esters, or organosilicon polymer KK341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic copolymer POLYFLU〇No.57, POLYFLUO NO.95 ( Above, Gongrong Shito Chemical Co., Ltd.). These surfactants can be used alone or in combination of two or more. The amount of the surfactant to be blended is preferably 100 parts by weight or less, and more preferably 0.5 parts by weight or less based on 100 parts by weight of the [A] copolymer. At this time, if the blending amount of the surfactant is more than 1.0 part by weight, there is a tendency that a film spot is easily generated. Examples of the storage stabilizer include sulfur, quinones, hydroxy ketones, polyoxy compounds, amines, and nitroso compounds, and more specifically, 4-monomethoxyphenol and N-quinone Nitro-N-phenylhydroxylamine and the like. These storage stabilizers can be used alone or in combination of two or more. The blending amount of the storage stabilizer is preferably 3.0 parts by weight or less, and more preferably 0.5 parts by weight or less based on 1,000 parts by weight of the [A] copolymer. In this case, if the compounding amount of the storage stabilizer exceeds 3.0 parts by weight, the sensitivity may be reduced and the shape of the graph may be deteriorated. Examples of the heat resistance improving agent 'include N ~ (alkoxymethyl) acetylene urea compounds, N- (alkoxymethyl) melamine compounds, compounds having two or more epoxy groups, and the like.

作爲上述N -（烷氧基甲基）乙炔脲化合物，例如可舉出 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 -27- 200525297 —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（第三丁氧基甲基）乙炔脲等。 這些N —（烷氧基甲基）乙炔脲化合物中，較佳的是 Ν,Ν,Ν,Ν—四（甲氧基甲基）乙炔脲。 作爲上述Ν -（烷氧基甲基）蜜胺化合物，例如可舉出 Ν，Ν，Ν，Ν，Ν，Ν —六（甲氧基甲基）蜜胺、Ν，Ν，Ν，Ν，Ν，Ν —六（乙 氧基甲基）蜜胺、Ν，Ν，Ν，Ν，Ν，Ν—六（正丙氧基甲基）蜜胺、 Ν，Ν，Ν，Ν，Ν，Ν —六（異丙氧基甲基）蜜胺、Ν，Ν，Ν，Ν，Ν，Ν —六 (正丁氧基甲基）蜜胺、Ν，Ν，Ν，Ν，Ν，Ν —六（第三丁氧基甲基） 蜜胺等。 這些Ν -（烷氧基甲基）蜜胺化合物中，較佳的是 Ν，Ν，Ν，Ν，Ν，Ν—六（甲氧基甲基）蜜胺，作爲其市售品，例如 可舉出 NIKALAC Ν — 2702、NIKALAC MW — 30Μ(以上，三 和化學（株）製）等。 作爲具有上述2個以上的環氧基的化合物，例如可舉 出乙二醇二縮水甘油基醚、二甘醇二縮水甘油基醚、三甘 醇二縮水甘油基醚、聚乙二醇二縮水甘油基醚、丙二醇二 縮水甘油基醚、一縮二丙二醇二縮水甘油基醚、二縮三丙 二醇二縮水甘油基醚、聚丙二醇二縮水甘油基醚、季戊二 醇二縮水甘油基醚、1，6—己二醇二縮水甘油基醚、甘油二 縮水甘油基醚、三羥甲基丙烷三縮水甘油基醚、加氫雙酚 Α二縮水甘油基醚、雙酚Α二縮水甘油基醚等。Examples of the N- (alkoxymethyl) acetylene urea compound include N, N, N, N-tetrakis (methoxymethyl) acetyleneurea, N, N, N, N ~ tetrakis (ethoxy) Methyl) acetylene urea, N, N, N, N — tetra (n-propoxymethyl) acetylene urea, n, N, N, N -27- 200525297 — tetra (isopropoxymethyl) acetylene urea , N, N, N, N-tetrakis (n-butoxymethyl) acetylene urea, N, N, N, N-tetrakis (third butoxymethyl) acetylene urea and the like. Among these N- (alkoxymethyl) acetylene urea compounds, N, N, N, N-tetrakis (methoxymethyl) acetylene urea is preferred. Examples of the N- (alkoxymethyl) melamine compound include N, N, N, N, N, N, N-hexa (methoxymethyl) melamine, N, N, N, N, Ν, Ν—Hexa (ethoxymethyl) melamine, N, N, N, N, N, N, N—Hexa (n-propoxymethyl) melamine, 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 —H (Third butoxymethyl) melamine and the like. Among these N- (alkoxymethyl) melamine compounds, N, N, N, N, N, N, N-hexa (methoxymethyl) melamine is preferred. As a commercially available product, for example, Examples include NIKALAC N-2702 and NIKALAC MW-30M (above, manufactured by Sanwa Chemical Co., Ltd.). Examples of the compound having two or more epoxy groups include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, and polyethylene glycol diglycidyl. Glyceryl ether, propylene glycol diglycidyl ether, diglycidyl glycol diglycidyl ether, diglycidyl glycol diglycidyl ether, polypropylene glycol diglycidyl ether, pentaerythrylene glycol diglycidyl ether, 1 , 6-hexanediol diglycidyl ether, glycerol diglycidyl ether, trimethylolpropane triglycidyl ether, hydrogenated bisphenol A diglycidyl ether, bisphenol A diglycidyl ether, etc. .

另外，作爲具有2個以上的環氧基的化合物的市售 品，例如可舉出 EHDG-L 40E、EHDG-L 100E、EHDG-L 200E、 EHDG-L 70P、EHDG-L 200P、EHDG-L 400P、EHDG-L -28- 200525297 1 500NP、EHDG-L 80MF、EHDG-L 100MF、EHDG-L 1 600、 EHDG-L 3002、EHDG-L 4000(以上，共榮社化學（株）製）等。 這些耐熱性提高劑可以單獨或2種以上混合使用。 本發明間隔物用感放射線性樹脂組成物，較佳的是使 用溶解在適當溶劑中的組成物溶液。 作爲上述溶劑，最好使用可均一地溶解本發明的感放 射線性樹脂組成物的各必須成份及任意添加劑成份，而且 不與各成份反應者。 這樣的溶劑，例如可舉出： 甲醇、乙醇等的醇類；四氫呋喃等的醚類；乙二醇單 甲基醚、乙二醇單乙基醚等的乙二醇醚類；乙二醇甲基醚 乙酸酯、乙二醇乙基醚乙酸酯等的乙二醇烷基醚乙酸酯 類；二甘醇單甲基醚、二甘醇單乙基醚、二甘醇二甲基醚、Examples of commercially available compounds having two or more epoxy groups include EHDG-L 40E, EHDG-L 100E, EHDG-L 200E, EHDG-L 70P, EHDG-L 200P, and EHDG-L. 400P, EHDG-L -28- 200525297 1 500NP, EHDG-L 80MF, EHDG-L 100MF, EHDG-L 1 600, EHDG-L 3002, EHDG-L 4000 (above, manufactured by Kyoeisha Chemical Co., Ltd.), etc. . These heat resistance improvers can be used alone or as a mixture of two or more. The radiation-sensitive resin composition for a spacer of the present invention is preferably a composition solution dissolved in an appropriate solvent. As the above-mentioned solvent, it is preferable to use those which can dissolve each necessary component and any additive component of the radiation-sensitive resin composition of the present invention uniformly and do not react with each component. Examples of such solvents include alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; and ethylene glycol methyl ester Glycol ether ether acetates such as ethyl ether acetate, ethylene glycol ethyl ether acetate; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether ,

丙二醇甲基醚、丙二醇乙基醚、丙二醇正丙基醚、丙 二醇正丁基醚等的丙二醇醚類；丙二醇甲基醚乙酸酯、丙 二醇乙基醚乙酸酯、丙二醇正丙基醚乙酸酯、丙二醇正丁 基醚乙酸酯等的丙二醇烷基醚乙酸酯類；丙二醇甲基醚丙 酸酯、丙二醇乙基醚丙酸酯、丙二醇正丙基醚丙酸酯、丙 二醇正丁基醚丙酸酯等的丙二醇烷基醚丙酸酯類； 甲苯、二甲苯等的芳香族烴類；甲乙酮、環己酮、4 一羥基一 4 一甲基一 2—戊酮等的酮類；醋酸甲酯、醋酸乙 酯、醋酸正丙酯、醋酸正丁酯、2 —羥基-2 —甲基丙酸甲 酯、2 -羥基一 2 —甲基丙酸乙酯、羥基醋酸甲酯、羥基醋 酸乙酯、羥基醋酸正丙酯、羥基醋酸正丁酯、乳酸甲酯、 -29- 200525297 » 参 乳酸乙酯、乳酸正丙酯、乳酸正丁酯、3 -羥基丙酸甲酯、 3 —羥基丙酸乙酯、3 —羥基丙酸正丙酯、3 -羥基丙酸正丁 酯、3 — 丁氧基丙酸甲酯、3—丁氧基丙酸乙酯、3- 丁氧基 丙酸正丙酯、3 —丁氧基丙酸正丁酯等其他的酯類等。 這些溶劑中，從溶解性' 與各成份的反應性及塗膜形 成的容易性看，較佳的是乙二醇醚類、乙二醇烷基醚乙酸 酯類、二甘醇醚類及其他的酯類。 上述溶劑可以單獨地或者2種以上混合使用。 在本發明中’上述溶劑中也可進一步並用高沸點溶劑。 作爲上述高沸點溶劑，例如可舉出N -甲基甲醯胺、 N，N —二甲基甲醯胺、N —甲基甲醯苯胺、N —甲基乙醯胺、 N，N—二甲基乙醯胺、n —甲基吡咯烷酮、二甲基亞颯、苄 基乙基醚、二己基醚、丙酮基丙酮、異佛爾酮、己酸、辛 酸、1一辛醇、1 一壬醇、苄基醇、醋酸苄酯、苯甲酸乙酯、 草酸二乙酯、馬來酸二乙酯、r 一丁內酯、碳酸乙烯酯、 碳酸丙嫌酯、苯基溶纖素乙酸酯等。 這些高沸點溶劑可以單獨或2種以上混合使用。 另外’上述調製的組成物溶液也可用孔徑〇. 5 V m左右 的微孔篩檢程式等過濾後使用。 MJft物的形成方户 M T ’對於使用本發明的感放射線性樹脂組成物形成 本發明的間隔物的方法進行說明。 本：#明的形成間隔物方法是至少包括下述（i)〜（iv)的步 驟。 (0¾ S 15 i：形成本發明的感放射線性樹脂組成物薄膜 -30- 200525297 ， · 的步驟。 (ii)在該薄膜的至少一部分曝光不含有低於3 50nm波 長的放射線的步驟。 (in)顯影曝光後的薄膜的步驟。 (iv)加熱顯影後的薄膜的步驟。 以下’對於這些各步驟依次說明。 (i) 步驟 在透明基板的一面上形成透明導電膜，在該透明導« 膜上塗覆本發明的感放射線性樹脂組成物的組成物溶液 後，加熱塗覆面（烘烤）形成薄膜。 用於形成間隔物的透明基板，例如可舉出玻璃基板' 樹脂基板等。更具體地可舉出鈉鹼玻璃、無鹼玻璃等的玻 璃基板；聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚 醚颯、聚碳酸酯、聚醯亞胺等的塑膠構成的樹脂基板。 作爲在透明基板的一面上設置的透明導電膜，可舉出 由氧化錫（Sn〇2)構成的NESA膜（美國PPG公司的註冊商 標）、氧化銦一氧化錫（In2〇3 — Sn〇2)構成的ITO膜等。 作爲組成物溶液的塗覆方法，例如可採用噴射法、輥 塗法、旋轉塗覆法等適宜的方法。 另外，烘烤的條件，根據各成份的種類、調配比例等 也不同，但通常在70〜120 °C下，1〜15分鐘左右。 (ii) 步驟 接著，在形成的薄膜的至少一部分上曝光實質上不含 有低於3 5 Onm波長的放射線。此時，在薄膜的一部分上曝 光時，通過設定的圖形光罩曝光。在本發明中，由於切掉 -31 - 200525297 • · 具有高能量的3 5 Onm波長以下的放射線，可有效地抑制用 於曝光機的反射鏡壽命的降低。 用於曝光的放射線可使用可見光線、紫外線、遠紫外 線等，但較佳的是從波長190〜450nm的範圍的放射線切掉 低於3 5 0 n m的反射線。 曝光量是通過照度計（〇AI model 356、〇AI Optical A s s o c i a t e s I n c ·製）測定曝光的放射線的波長3 6 5 n m的強度 的値來計算，通常是100〜1〇,〇〇〇 J/m2、較佳的是1，5〇〇〜3,000 J/m2 〇 作爲切掉放射線低於3 5 Onm的波長的手段沒有特別限 制，例如可採用使用濾光器的方法。 作爲上述濾光器，例如可採用東芝玻璃（株）製之透過 紫外線濾光器“ UV — 35” 。 第1圖表示使透過紫外線濾光器“ UV - 3 5 ”透過的水 銀燈的發光光譜（粗線）及不透過的水銀燈的發光光譜（細 線。但3 5 Onm以上的發光光譜部分地與粗線重疊。）。第1 圖的發光光譜（粗線）上包括若干3 50nm以下的波長，但其 相對強度及累積面積十分小，對於用於曝光機的反射鏡的 壽命不會給予負面影響。 (iii)步驟 接著，通過顯影曝光後的薄膜，除去不要的部分形成 設定的圖形。 作爲用於顯影的顯影液，例如可使用氫氧化鈉、氫氧 化鉀、碳酸鈉、矽酸鈉、甲基矽酸鈉、氨等的無機鹼類； 乙胺、正丙胺等的脂肪族1級胺類；二乙胺、二正丙胺等 -32- 200525297 » * 的脂肪族2級胺類；三甲胺、甲基二乙胺、二甲基乙胺、 三乙胺等的脂肪族3級胺類；吡咯、哌啶、N —甲基哌啶、 N—甲基吡啶、1，8—二氮雜二環[5.4.0] - 7—（十一）碳烯、 1，5 —二氮雜二環[4.3.0] — 5 —壬烯等的脂環族3級胺類；吡 啶、三甲基吡啶、二甲基吡啶、喹啉等的芳香族3級胺類； 二甲基乙醇胺、甲基二乙醇胺、三乙醇胺等的烷醇胺類； 四甲基氫氧化銨、四乙基氫氧化銨等的4級銨鹽等的鹼性 化合物的水溶液。 另外，在上述鹼性化合物的水溶液中也可適當添加甲 醇、乙醇等的水溶性有機溶劑及/或界面活性劑後使用。 作爲顯影方法，也可以是冒液法、浸漬法、噴淋法等 的任意一種方法，顯影時間通常在常温下是10〜180秒左右。 顯影後，例如進行流水洗滌30〜90秒後，通過壓縮空 氣或壓縮氮氣風乾形成所希望的圖形。 (iv)步驟 接著，將得到的圖形例如通過熱板、烘箱等的加熱裝 置加熱（後焙烤）到規定溫度，例如100〜160°C，特定時間， 例如對於熱板上是5〜30分鐘、對於烘箱中是30〜180分鐘， 可得到特定的間隔物。 以往用於形成間隔物的感放射線性樹脂組成物，如果 不進行180〜200°C左右以上溫度加熱處理，則得到的間隔物 不能發揮充分的性能，但本發明的感放射線性樹脂組成 物，可將加熱溫度作成比以往低的溫度，其結果，不會引 起樹脂基板的變黃或變形，可得到壓縮強度、液晶配向時 的硏磨耐性、與透明基板的密著性等諸性能優良的間隔物。 -33- 200525297 τ 雒 液_晶顯示元件 以下，對於本發明的液晶顯示元件進行說明。 本發明的液晶顯示元件具有如上述形成的間隔物。 對於液晶顯示元件的結構沒有特別限制，但例如第2 圖所示，可舉出在透明基板上形成彩色濾光層及本發明的 間隔物，夾住液晶層配置的2個配向膜、對置的透明電極、 對置的透明基板等的結構。另外，也如第2圖所示，根據 需要，也可在彩色濾光層上設置保護膜。 進而，如第3圖所示，在透明基板上形成彩色濾光層 及本發明的間隔物，通過配向膜及液晶層，與薄膜電晶體 (TFT)陣列對向，也可作成ΤΝ - TFT型的液晶顯示元件。此 時，根據需要，可在偏光扳或彩色濾光層上設置保護膜。 本發明的形成間隔物用感放射線性樹脂組成物，即使 是用實質上不含有350nm以下的波長的放射線曝光，也可 容易形成高解析度、高靈敏度，且圖形形狀、壓縮強度、 硏磨耐性、與透明基板的密著性等諸性能優良的間隔物， 另外，在形成間隔物時，可降低顯影後的加熱溫度，不會 引起樹脂基板的變黃或變形。 本發明的液晶顯示元件是具有在圖形形狀、壓縮強 度、硏磨耐性、與透明基板的密著性等諸性能優良的間隔 物，可實現長期的高可靠性。 實施例 以下，用實施例進而具體地說明本發明的實施方式。 合成例 1 在具備冷卻管、攪拌機的燒瓶中加入2,2’ 一偶氮雙 -34- 200525297 (2,4 一二甲基戊腈）5重量份及二乙二醇甲基乙基醚250重 量份，接著，加入苯乙烯20重量份、甲基丙烯酸17重量 份、二環伸戊基甲基丙烯酸酯1 8重量份及甲基丙烯酸縮水 甘油酯45重量份，進行氮氣置換後，慢慢攪拌且將反應溶 液的溫度上升到70°C，將該溫度保持4小時進行聚合，得 到含有[A]共聚物的樹脂溶液。該樹脂溶液的固形分濃度是 28.4重量％，得到的[A]共聚物的的Mw是1 6,000。將該[A] 共聚物作爲“共聚物（A - 1)” 。 共聚物（A — 1)及下述的共聚物（A — 2)的Mw，使用 GPC (凝膠滲透色譜）HLC — 8020 (TOSOH(株）製）測定。 合成例2 在具備冷卻管、攪拌機的燒瓶中加入2,2’ -偶氮雙 (2,4-二甲基戊腈）4重量份及二乙二醇甲基乙基醚250重 量份，接著，加入苯乙烯5重量份、甲基丙烯酸16重量份、 二環伸戊基甲基丙烯酸酯34重量份及甲基丙烯酸縮水甘 油酯40重量份，進行氮氣置換後，進而加入1，3 — 丁二烯 5重量份，慢慢攪拌且將反應溶液的溫度上升到7 0 °C，將 該溫度保持4小時進行聚合，得到含有[A]共聚物的樹脂溶 液。該樹脂溶液的固形分濃度是28.6重量％，得到的[A]共 聚物的Mw是1 5,000。將該[A]共聚物作爲“共聚物（A — 2)” 。 實施例1 (I)放射線敏感性樹脂组合物的調製 作爲（A)成份的由合成例1得到的樹脂溶液作成共聚物 (A — 1)100重量份（固形分）中混合作爲[B]成份的二季戊四 -35- 200525297 醇六丙烯酸酯（商品名KAY ARAD DPH A、日本化藥（株）製）8〇 重量份、作爲[C]成份的2,2’ 一雙（2,4 —二氯苯基）一 4,4’ ，5,5’ —四苯基雙咪唑10重量份、作爲[D]成份的2 一甲基[4一（甲硫基）苯基]一 2—嗎啉一 1—丙酮（商品名 IRGACURE 907、Ciba Specialty Chemicals 社製）15 重量份、 作爲[E]成份的4,4’ -雙（二甲基胺基）二苯甲酮1〇重量 份、作爲[F]成份的2 —锍基苯并噻唑5重量份、作爲黏结 助劑的r 一環氧丙氧丙基三甲氧基矽烷5重量份、作爲表 面活性劑的FTX — 218(商品名、（株）NE〇S製）0.5重量份、 作爲保存穩定劑的4 一甲氧基苯酣〇 · 5重量份，溶解到丙二 醇單甲基醚乙酸酯中，使其固形分濃度成爲30重量％，然 後用孔徑0 · 5 /z m的微孔過濾器過濾，調製組合物溶液。 (II) 間隔物的形成 在無鹼玻璃基板上使用旋轉噴射器塗覆上述組成物溶 液後，在90 °C的熱板上預焙烤3分鐘形成膜厚6.0 # m的薄 膜。 接著’在得到的薄膜上通過殘留1 〇 # m X 1 0 // m圖形的 光罩，以365nm的強度250W/m2、透過東芝玻璃（株）製紫外 透過濾光器“ UV — 3 5 ”的紫外線曝光1 〇秒鐘。然後，用氫 氧化鉀的0.05重量％水溶液在25 °C下顯影60秒後，用純水 洗滌1分鐘。然後，在烘箱中在1 5 〇 °C下後焙烤1 2 0分鐘， 形成特定圖形的間隔物。 (III) 解析度的評價 在上述（II)形成圖形時，殘留圖形可以分辨時作爲良好 (〇），不可以分辨時作爲不良（X)進行評價。評價的結果表示 -36- 200525297 在表2。 (IV) 靈敏度的評價 對於上述（II)得到的圖形，顯影後的殘膜率（顯影後的 膜厚X 1 〇 〇 /初期膜厚）是9 0 %以上作爲良好（〇 )、低於9 0 %時， 作爲不良（X)進行評價。評價的結果表示在表2。 (V) 圖形形狀的評價 用掃描型電子顯微鏡觀察上述（II)得到的圖形的剖面 形狀，是否符合於第4圖所示的A〜D進行評價。此時，像 A或者B那樣，圖形的邊緣是正錐形或者垂直狀時，作爲 間隔物的圖形形狀可以說是良好的。與此相反，如C那樣 靈敏度不充分，殘膜率低，剖面尺寸比A及B小，在剖面 的形狀中，底面是平面的半凸透鏡狀時，作爲間隔物的圖 形是不良的，或者如D所示的那樣，剖面的形狀是倒錐體 形時，則在後期硏磨處理時由於圖形可能剝落，所以作爲 間隔物圖形的形狀是不良的。評價結果表示在表2。 (VI) 壓縮強度的評價 對於上述（II)得到的圖形，用微小壓縮試驗機（MCTM — 200、（株）島津製作所），在測定溫度23 °C下，用直徑50 # m 的平面壓子，測定加入1 〇mN的負荷時的變形量。該値在 0.5以下時，表示壓縮強度良好。評價結果表示在表2。 (VII) 硏磨耐性的評價 用液晶配向膜塗覆用印刷機將液晶配向劑的 AL3046(商品名，JSR(株）製）塗覆在形成有上述（II)得到的圖 形的基板上後，在1 8 0 °C下乾燥1小時，形成乾燥膜厚0 · 〇 5 y m的配向劑的塗膜。而後，在該塗膜上，使用具有捲繞 -37- 200525297 > · 聚醯胺製布的輥的硏磨機進行硏磨處理，輥的轉速是 5 OOrpm、載物台的移動速度是lcm/秒。此時評價圖形有無 被切削或者剝離。評價結果表示在表2。 (VIII)密著性的評價 除了不使用殘留圖形的光罩外，與上述（Π)相同地實 施，形成固化膜。而後，根據JIS K - 5400( 1 900)8.5的黏著 性試驗中的8.5.2的棋盤格法進行評價。此時100個的棋盤 格中殘留的棋盤格的數表示在表2中。 實施例2〜1 4 除了作爲[A]〜[F]成份使用表1 一 1所示的成份外’與實 施例1相同地配製各個組成物溶液進行評價。評價結果表 示在表2。 比較例1〜9 除了作爲[A]〜[F]成份使用表1—2所示的成份外’與實 施例1相同地配製各個組成物溶液進行評價。評價結果表 示在表2。 在表1— 1及表1— 2中，共聚物（A— 1)及共聚物（A — 2)以外的各個成份如下。 [B] 成份 B — 1 ••二季戊四醇六丙烯酸酯 [C] 成份 C—1 : 2,2，一雙（2,4一二氯苯基）—4,4’ ，5,5’ —四 苯基雙咪唑 C一 2 : 2,2，一雙（2 —氯苯基）一 4,4，，5,5’ 一 四苯基 -38- 200525297 [D]成份 D - 1 : 丙酮 2—甲基[4 一（甲硫基）苯基]一 2—嗎啉基一 1 — D - 2 : 2 —苄基一 2 -二甲基胺基—1 一（4 一嗎啉基苯 基）一丁酮—1 [E] 成份 E— 1:4,4’ 一雙（二甲基胺基）二苯甲酮 [F] 成份 F- 1 : 2 -酼基苯并噻唑 F- 2 : 季戊四醇四（锍基乙酸酯） -39- 200525297 表1 — 1 [A滅份 (重量份） [B诚份 (重量份） [C滅份 (重量份） [D诚份 (重量份） [E诚份 (重量份） [F滅份 (重量份） 實施例1 A-1 (100) B-1 (80) C-1 (10) D-1 (15) E-1 (10) F-l (5) 實施例2 A-1 (100) B-1 (80) C-1 (10) D-2 (10) E-1 (10) F-l (5) 實施例3 A-1 (100) B-1 (80) C-1 (10) D-1 (15) D-2 (05) E-1 (10) F-l (5) 實施例4 A-1 (100) B-1 (80) C-1 (10) D-1 (15) D-2 (05) E-1 (10) F-2⑸ 實施例5 A-1 (100) B-1 (80) C-2 (10) D-1 (15) D-2 (05) E-1 (10) F-l (5) 實施例6 A-1 (100) B-1 (80) C-1 (10) D-1 (15) D-2 (05) E-1 (10) — 實施例7 A-1 (100) B-1 (80) c-i(i〇). D-1 (15) D-2 (05) 一 F-l (5) 實施例8 A-2 (100) B-1 (80) C-1 (10) D-1 (15) E-1 (10) F-l (5) 實施例9 A-2 (100) B-1 (80) C4 (10) D-2 (10) E-1 (10) F-l (5) 實施例10 A-2 (100) B-1 (80) C-1 (10) D-1 (15) D-2 (05) Ε·1 (10) F-l (5) 實施例11 A-2 (100) B-1 (80) C-1 (10) D-1 (15) D-2 (05) E-1 (10) F-2(5) 實施例12 A-2 (100) B-1 (80) C-2 (10) D-1 (15) D-2 (05) E-1 (10) F-l (5) 實施例13 A-2 (100) B-1 (80) C-1 (10) D-1 (15) D-2 (05) E-1 (10) 一 實施例14 A-2 (100) B-1 (80) C-1 (10) D-1 (15) D-2 (05) — F-l (5) -40- 200525297 表1 — 2 [A]成份 (重量份） [B诚份 (重量份） [C滅份 (重量份） [D诚份 (重量份） DE滅份 (重量份） [F诚份 (重量份） 比較例1 A-1 (100) B-1 (80) C-1 (10) 一 E-1 (10) F-1 (5) 比較例2 A-2 (100) B-1 (80) C-1 (10) — E-1 (10) F-1 (5) 比較例3 A-1 (100) B-1 (80) C-2 (10) 一 E-1 (10) F-1 (5) 比較例4 A-2 (100) B-1 (80) C-2 (10) — E-1 (10) F-1 (5) 比較例5 A-1 (100) B-1 (80) — D-1 (15) D-2 (05) E-1 (10) F-1 (5) 比較例6 A-2 (100) B-1 (80) — D-1 (15) D-2 (05) E-1 (10) F-1 (5) 比較例7 A-1 (100) B-1 (80) C-1 (10) D-1 (15) D-2 (05) 一 — 比較例8 A-2 (100) B-1 (80) C-1 (10) D-1 (15) D-2 (05) — — 比較例9 A-1 (100) B-1 (80) C-2 (10) D-1 (15) D-2 (05) — — -41- 200525297 表2 解析度 靈敏度 圖形形狀 壓縮強度 (//m) 硏磨耐性 密著性 實施例1 〇 〇 B 0.29 Μ j\ \\ 100 實施例2 〇 〇 A 0.28 Μ y\\\ 100 實施例3 〇 〇 A 0.32 Μ j\\\ 100 實施例4 〇 〇 A 0.27 Μ /1 \\ 100 實施例5 〇 〇 A 0.28 Μ J 100 實施例6 〇 〇 B 0.39 Μ j\\\ 100 實施例7 〇 〇 B 0.34 Μ j \ \\ 100 實施例8 〇 〇 B 0.29 Μ j \ \\ 100 實施例9 〇 〇 A 0.28 te j \\\ 100 實施例10 〇 〇 A 0.31 Μ j \ \\ 100 實施例11 〇 〇 A 0.28 Μ j\ \\ 100 實施例12 〇 〇 A 0.28 ίΕΕ 100 實施例13 〇 〇 B 0.39 te jw\ 100 實施例14 〇 〇 B 0.35 te j\w 100 比較例1 〇 〇 D 0.41 有 100 比較例2 〇 〇 D 0.42 有 100 比較例3 〇 〇 D 0.39 有 100 比較例4 〇 〇 D 0.43 有 100 比較例5 〇 X C 0.43 有 100 比較例6 〇 X C 0.45 有 100 比較例7 〇 X C 0.43 有 100 比較例8 〇 X C 0.45 有 100 比較例9 〇 X C 0.43 有 100 -42- 200525297 ί · [圖式簡單說明] 第1圖是表示透過紫外線透過濾膜“ UV -燈的發光譜（粗線）及不透過紫外線透過濾膜的 光譜（細線）的圖。 第2圖是表示液晶顯示元件的結構的一例 第3圖是表示液晶顯示元件的結構的其他 圖。 第4圖是表示間隔物剖面形狀的模式圖。 -3 5 ”的水銀 水銀燈的發 的模式圖。 例的模式 -43 -Propylene glycol ethers such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol n-propyl ether, propylene glycol n-butyl ether; propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol n-propyl ether acetate Propylene glycol alkyl ether acetates such as esters, propylene glycol n-butyl ether acetate; propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol n-propyl ether propionate, propylene glycol n-butyl ether Propylene glycol alkyl ether propionates such as propionate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone, cyclohexanone, 4-monohydroxy-4 4-methyl 2-pentanone; acetic acid Methyl ester, ethyl acetate, n-propyl acetate, n-butyl acetate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methyl propionate, methyl glycolate, glycolic acid Ethyl ester, n-propyl glycolate, n-butyl glycolate, methyl lactate, -29- 200525297 »Ginseng ethyl lactate, n-propyl lactate, n-butyl lactate, 3-hydroxypropionate, 3-hydroxyl Ethyl propionate, n-propyl 3-hydroxypropionate, n-butyl 3-hydroxypropionate, 3 — Other esters such as methyl butoxypropionate, ethyl 3-butoxypropionate, n-propyl 3-butoxypropionate, n-butyl 3-butoxypropionate, and the like. Among these solvents, glycol ethers, glycol alkyl ether acetates, diethylene glycol ethers, and others are preferred in terms of solubility, reactivity with each component, and ease of coating film formation. Of esters. These solvents may be used alone or as a mixture of two or more. In the present invention, a solvent having a high boiling point may be used in combination with the above-mentioned solvent. Examples of the high boiling point solvent include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, and N, N-diamine Methylacetamide, n-methylpyrrolidone, dimethylsulfenyl, benzylethyl ether, dihexyl ether, acetone acetone, isophorone, hexanoic acid, caprylic acid, 1-octanol, 1-nonyl Alcohol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, r-butyrolactone, vinyl carbonate, propyl carbonate, phenylcelluinoacetate Wait. These high-boiling-point solvents can be used individually or in mixture of 2 or more types. In addition, the composition solution prepared as described above may be used after being filtered by a micropore screening program having a pore size of about 0.5 V m. The formation method of the MJft object M T 'is a method for forming the spacer of the present invention using the radiation-sensitive resin composition of the present invention. Ben: The method for forming a spacer is to include at least the following steps (i) to (iv). (0¾ S 15 i: a step of forming the radiation-sensitive resin composition film -30-200525297 of the present invention. (Ii) a step of exposing at least a part of the film to a radiation that does not contain a wavelength lower than 3 50 nm. (In ) The step of developing the exposed film. (Iv) The step of heating the developed film. The steps are described below in order. (I) The step forms a transparent conductive film on one side of the transparent substrate, and the transparent conductive film After the composition solution of the radiation-sensitive resin composition of the present invention is applied thereon, the coated surface is heated (baked) to form a thin film. Transparent substrates for forming the spacer include, for example, glass substrates, resin substrates, and the like. More specifically, Examples include glass substrates such as soda-alkali glass and alkali-free glass; plastics such as polyethylene terephthalate, polybutylene terephthalate, polyether fluorene, polycarbonate, and polyimide. Resin substrate. Examples of the transparent conductive film provided on one surface of the transparent substrate include a NESA film (registered trademark of the United States PPG Corporation) composed of tin oxide (SnO2), and indium oxide (In2O3). — ITO film composed of SnO2), etc. As a coating method of the composition solution, for example, a suitable method such as a spray method, a roll coating method, or a spin coating method can be used. In addition, the baking conditions depend on the composition of each component. Kinds, blending ratios, etc. are also different, but they are usually about 1 to 15 minutes at 70 to 120 ° C. (Ii) Step Next, at least a part of the formed film is exposed without substantially containing wavelengths below 3 5 Onm. Radiation. At this time, when exposing on a part of the film, it is exposed through a set pattern mask. In the present invention, since -31-200525297 is cut off, · High-energy radiation with a wavelength below 3 5 Onm can be effectively Suppresses the reduction of the life of the mirror used in the exposure machine. The radiation used for the exposure can be visible light, ultraviolet rays, far ultraviolet rays, etc., but it is preferable to cut off the radiation with a wavelength in the range of 190 to 450 nm below 3 50 nm. The amount of exposure is calculated by measuring the intensity of the exposed radiation at a wavelength of 3 6 5 nm with an illuminance meter (〇AI model 356, 〇AI Optical A ssociates I nc), usually, It is 100 to 10,000,000 J / m2, and preferably 1,500 to 3,000 J / m2. There is no particular limitation on the means for cutting off wavelengths below 3 5 Onm. For example, a filter can be used. The method of the optical filter. As the filter, for example, a transmission ultraviolet filter "UV-35" manufactured by Toshiba Glass Co., Ltd. can be used. Fig. 1 shows a transmission through the transmission ultraviolet filter "UV-3 5". Luminescence spectrum (thick line) of mercury lamp and light spectrum (thin line) of impermeable mercury lamp. However, the emission spectrum above 3 5 Onm partially overlaps with the thick line. ). The emission spectrum (thick line) in Figure 1 includes several wavelengths below 3 50 nm, but its relative intensity and cumulative area are very small, and it will not adversely affect the life of the reflector used in the exposure machine. (iii) Step Next, the exposed film is developed, and unnecessary portions are removed to form a set pattern. As the developing solution used for development, for example, inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium methyl silicate, ammonia, and the like can be used; and aliphatic class 1 such as ethylamine and n-propylamine Amines; diethylamine, di-n-propylamine, etc. -32- 200525297 »* aliphatic secondary amines; trimethylamine, methyldiethylamine, dimethylethylamine, triethylamine, etc. Class; pyrrole, piperidine, N-methylpiperidine, N-methylpyridine, 1,8-diazabicyclo [5.4.0]-7- (unde) carbene, 1,5-diazine Heterobicyclo [4.3.0] — 5-Nonene and other alicyclic tertiary amines; pyridine, trimethylpyridine, dimethylpyridine, quinoline and other aromatic tertiary amines; dimethylethanolamine , Alkanolamines such as methyldiethanolamine, triethanolamine, etc .; aqueous solutions of basic compounds such as quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. Further, a water-soluble organic solvent such as methanol and ethanol and / or a surfactant may be appropriately added to the aqueous solution of the basic compound and used. The developing method may be any method such as a flooding method, a dipping method, or a shower method. The developing time is usually about 10 to 180 seconds at normal temperature. After development, for example, washing with running water for 30 to 90 seconds, and then drying with compressed air or compressed nitrogen to form a desired pattern. (iv) Step Next, the obtained pattern is heated (post-baked), for example, by a heating device such as a hot plate or an oven to a predetermined temperature, for example, 100 to 160 ° C, for a specific time, for example, 5 to 30 minutes for the hot plate, For an oven of 30 to 180 minutes, specific spacers can be obtained. Conventionally, the radiation-sensitive resin composition used to form a spacer does not exhibit sufficient performance unless the heat treatment is performed at a temperature of about 180 to 200 ° C or more. However, the radiation-sensitive resin composition of the present invention, The heating temperature can be made lower than in the past. As a result, the resin substrate does not cause yellowing or deformation, and excellent properties such as compressive strength, honing resistance during liquid crystal alignment, and adhesion to a transparent substrate can be obtained. Spacer. -33- 200525297 τ 液 Liquid crystal display element Hereinafter, the liquid crystal display element of the present invention will be described. The liquid crystal display element of the present invention includes the spacer formed as described above. The structure of the liquid crystal display element is not particularly limited, but for example, as shown in FIG. 2, a color filter layer and a spacer of the present invention may be formed on a transparent substrate, and two alignment films arranged on the liquid crystal layer may be opposed to each other. Structures such as transparent electrodes and transparent substrates facing each other. As shown in FIG. 2, a protective film may be provided on the color filter layer as necessary. Further, as shown in FIG. 3, a color filter layer and a spacer of the present invention are formed on a transparent substrate, and an alignment film and a liquid crystal layer are opposed to a thin film transistor (TFT) array, and can also be made 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 layer as required. The radiation-sensitive resin composition for forming a spacer of the present invention can easily form a high resolution, high sensitivity, pattern shape, compressive strength, and honing resistance even when exposed to radiation that does not substantially contain a wavelength of 350 nm or less. A spacer with excellent properties such as adhesion to a transparent substrate. In addition, when the spacer is formed, the heating temperature after development can be reduced without causing yellowing or deformation of the resin substrate. The liquid crystal display element of the present invention is a spacer having excellent properties such as pattern shape, compressive strength, honing resistance, and adhesion to a transparent substrate, and can achieve long-term high reliability. Examples Hereinafter, examples of the present invention will be specifically described using examples. Synthesis Example 1 In a flask equipped with a cooling tube and a stirrer, 2,2'-azobis-34- 200525297 (2,4 dimethylvaleronitrile) 5 parts by weight and diethylene glycol methyl ethyl ether 250 were added. Part by weight. Next, 20 parts by weight of styrene, 17 parts by weight of methacrylic acid, 18 parts by weight of dicyclopentyl methacrylate, and 45 parts by weight of glycidyl methacrylate were added. After nitrogen substitution, slowly The temperature of the reaction solution was raised to 70 ° C. with stirring, and the temperature was maintained for 4 hours for polymerization to obtain a resin solution containing the [A] copolymer. The solid content concentration of this resin solution was 28.4% by weight, and the Mw of the obtained [A] copolymer was 1 6,000. This [A] copolymer is referred to as "copolymer (A-1)". The Mw of the copolymer (A-1) and the following copolymer (A-2) was measured using GPC (gel permeation chromatography) HLC-8020 (manufactured by TOSOH Co., Ltd.). Synthesis Example 2 In a flask equipped with a cooling tube and a stirrer, 4 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 250 parts by weight of diethylene glycol methyl ethyl ether were added, and then 5 parts by weight of styrene, 16 parts by weight of methacrylic acid, 34 parts by weight of dicyclopentyl methacrylate, and 40 parts by weight of glycidyl methacrylate were added. After nitrogen substitution, 1,3-butane was further added. 5 parts by weight of diene was slowly stirred, and the temperature of the reaction solution was raised to 70 ° C., and the temperature was maintained for 4 hours to perform polymerization to obtain a resin solution containing a [A] copolymer. The solid content concentration of this resin solution was 28.6% by weight, and the Mw of the obtained [A] copolymer was 15,000. This [A] copolymer is referred to as "copolymer (A-2)". Example 1 (I) Preparation of radiation-sensitive resin composition As component (A), 100 parts by weight (solid content) of the copolymer (A-1) prepared from the resin solution obtained in Synthesis Example 1 was mixed as the component [B] 80 parts by weight of dipentaerythritol-35- 200525297 melamine hexaacrylate (trade name KAY ARAD DPH A, manufactured by Nippon Kayaku Co., Ltd.) as a component [C] of 2,2 '(2,4 — 10 parts by weight of 4,4 ', 5,5'-tetraphenylbisimidazole, 2-methyl [4- (methylthio) phenyl]-2 as the [D] component 15-parts by weight of 1-acetone (trade name IRGACURE 907, manufactured by Ciba Specialty Chemicals), 10 parts by weight of 4,4'-bis (dimethylamino) benzophenone as the [E] component, as [F] 5 parts by weight of 2-fluorenylbenzothiazole, 5 parts by weight of r-glycidoxypropyltrimethoxysilane as a bonding aid, and FTX-218 (trade name, ( (Manufactured by NEOS) 0.5 parts by weight of 4-methoxymethoxybenzene as a storage stabilizer, 0.5 part by weight was dissolved in propylene glycol monomethyl ether acetate to make it solid The concentration was 30% by weight, and the solution was filtered through a microporous filter having a pore size of 0.5 / z m to prepare a composition solution. (II) Formation of spacers After the above composition solution was applied on a non-alkali glass substrate using a rotary sprayer, it was prebaked on a hot plate at 90 ° C for 3 minutes to form a thin film with a thickness of 6.0 #m. Next, a “10 # m X 1 0 // m patterned photomask was passed on the obtained film, and passed through a UV filter“ UV — 3 5 ”manufactured by Toshiba Glass Co., Ltd. at an intensity of 250W / m2 at 365 nm. UV exposure for 10 seconds. Then, it was developed with a 0.05% by weight aqueous solution of potassium hydroxide at 25 ° C for 60 seconds, and then washed with pure water for 1 minute. Then, post-bake at 150 ° C. for 120 minutes in an oven to form a spacer with a specific pattern. (III) Evaluation of resolution When the pattern is formed in the above (II), the residual pattern can be evaluated as good (0) when it can be resolved, and can be evaluated as poor (X) when it cannot be resolved. The results of the evaluation are shown in Table 2 -36- 200525297. (IV) Evaluation of sensitivity For the pattern obtained in the above (II), the residual film rate after development (film thickness after development X 100 / initial film thickness) is 90% or more. At 0%, it was evaluated as defective (X). The evaluation results are shown in Table 2. (V) Evaluation of the shape of the pattern The scanning electron microscope was used to observe whether the cross-sectional shape of the pattern obtained in the above (II) conformed to A to D shown in Fig. 4 and evaluated. In this case, when the edges of the pattern are forward-tapered or vertical like A or B, the shape of the pattern as a spacer can be said to be good. On the contrary, if the sensitivity is insufficient as C, the residual film rate is low, and the cross-sectional size is smaller than A and B. In the shape of the cross-section, when the bottom surface is a flat semi-convex lens, the pattern as a spacer is not good, or if As shown in D, when the shape of the cross section is an inverted cone shape, the shape may be defective as a spacer pattern because the pattern may be peeled off during the later honing process. The evaluation results are shown in Table 2. (VI) Evaluation of compressive strength For the pattern obtained in (II) above, a micro compression tester (MCTM-200, Shimadzu Corporation) was used at a measurement temperature of 23 ° C with a flat indenter with a diameter of 50 # m. , Measure the amount of deformation when a load of 10 mN is added. When the ratio is 0.5 or less, it means that the compressive strength is good. The evaluation results are shown in Table 2. (VII) Evaluation of honing resistance Liquid crystal alignment film coating printer A liquid crystal alignment agent AL3046 (trade name, manufactured by JSR Corporation) was applied to a substrate on which the pattern obtained in (II) was formed, Drying was performed at 180 ° C. for 1 hour to form a coating film of an alignment agent having a dry film thickness of 0. 05 μm. Then, on this coating film, the honing process was performed using a honing machine having a roll of -37- 200525297 > Polyamide cloth roll. The rotation speed of the roll was 500 rpm, and the moving speed of the stage was 1 cm. /second. At this time, it was evaluated whether the pattern was cut or peeled. The evaluation results are shown in Table 2. (VIII) Evaluation of Adhesiveness A cured film was formed in the same manner as in (Π) above, except that a photomask with no residual pattern was used. Then, the evaluation was performed according to the checkerboard method of 8.5.2 in the adhesion test of JIS K-5400 (1 900) 8.5. The number of checkerboards remaining in the 100 checkerboards at this time is shown in Table 2. Examples 2 to 1 4 Except that the components shown in Tables 1 to 1 were used as the components [A] to [F], each composition solution was prepared and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2. Comparative Examples 1 to 9 Each component solution was prepared and evaluated in the same manner as in Example 1 except that the components shown in Table 1-2 were used as the components [A] to [F]. The evaluation results are shown in Table 2. In Tables 1-1 and 1-2, the components other than the copolymer (A-1) and the copolymer (A-2) are as follows. [B] Ingredient B — 1 •• Dipentaerythritol hexaacrylate [C] Ingredient C-1: 2,2, a bis (2,4-dichlorophenyl) -4,4 ', 5,5' —tetra Phenylbisimidazole C-2: 2,2,2-bis (2-chlorophenyl) -4,4,5,5'-tetraphenyl-38- 200525297 [D] component D-1: acetone 2— Methyl [4-mono (methylthio) phenyl]-2-morpholinyl- 1-D-2: 2 -benzyl-2 -dimethylamino-1 -1 (4-morpholinylphenyl) Monobutyl ketone — 1 [E] Component E — 1: 4,4 'Monobis (dimethylamino) benzophenone [F] Component F- 1: 2 -fluorenylbenzothiazole F- 2: Pentaerythritol Tetrakis (fluorenyl acetate) -39- 200525297 Table 1 — 1 [A parts by weight (parts by weight) [B parts by weight (parts by weight) [C parts by weight (parts by weight) [D parts by weight (parts by weight) [E Parts (parts by weight) [F parts (parts by weight) Example 1 A-1 (100) B-1 (80) C-1 (10) D-1 (15) E-1 (10) Fl (5 ) Example 2 A-1 (100) B-1 (80) C-1 (10) D-2 (10) E-1 (10) Fl (5) Example 3 A-1 (100) B-1 (80) C-1 (10) D-1 (15) D-2 (05) E-1 (10) Fl (5) Example 4 A-1 (100) B-1 (80) C-1 ( 10) D-1 (15) D-2 ( 05) E-1 (10) F-2⑸ Example 5 A-1 (100) B-1 (80) C-2 (10) D-1 (15) D-2 (05) E-1 (10) Fl (5) Example 6 A-1 (100) B-1 (80) C-1 (10) D-1 (15) D-2 (05) E-1 (10) — Example 7 A-1 (100) B-1 (80) ci (i〇). D-1 (15) D-2 (05)-Fl (5) Example 8 A-2 (100) B-1 (80) C-1 (10) D-1 (15) E-1 (10) Fl (5) Example 9 A-2 (100) B-1 (80) C4 (10) D-2 (10) E-1 (10) Fl (5) Example 10 A-2 (100) B-1 (80) C-1 (10) D-1 (15) D-2 (05) E · 1 (10) Fl (5) Example 11 A-2 (100) B-1 (80) C-1 (10) D-1 (15) D-2 (05) E-1 (10) F-2 (5) Example 12 A-2 (100 ) B-1 (80) C-2 (10) D-1 (15) D-2 (05) E-1 (10) Fl (5) Example 13 A-2 (100) B-1 (80) C-1 (10) D-1 (15) D-2 (05) E-1 (10) Example 14 A-2 (100) B-1 (80) C-1 (10) D-1 ( 15) D-2 (05) — Fl (5) -40- 200525297 Table 1 — 2 [A] ingredients (parts by weight) [B since parts (parts by weight) [C since parts (parts by weight) [D since parts ( Parts by weight) DE parts by weight (parts by weight) [F parts (parts by weight) Comparative Example 1 A-1 (100) B-1 (80) C-1 (10) One E-1 (10) F-1 ( 5) Comparative Example 2 A-2 (100) B-1 (80) C-1 (10) — E-1 (10) F-1 (5) Comparative Example 3 A-1 (100) B-1 (80) C-2 (10) One E-1 (10) F-1 (5) Comparative example 4 A-2 (100) B-1 (80) C-2 (10) — E-1 (10) F-1 (5) Comparative example 5 A-1 (100) B-1 ( 80) — D-1 (15) D-2 (05) E-1 (10) F-1 (5) Comparative Example 6 A-2 (100) B-1 (80) — D-1 (15) D -2 (05) E-1 (10) F-1 (5) Comparative example 7 A-1 (100) B-1 (80) C-1 (10) D-1 (15) D-2 (05) I—Comparative Example 8 A-2 (100) B-1 (80) C-1 (10) D-1 (15) D-2 (05) — — Comparative Example 9 A-1 (100) B-1 ( 80) C-2 (10) D-1 (15) D-2 (05) — — -41- 200525297 Table 2 Resolution Sensitivity Shape Shape Compression Strength (// m) Honing Resistance Adhesion Example 1 〇 〇B 0.29 Μ j \\\ 100 Example 2 〇A 0.28 Μ y \\\ 100 Example 3 〇A 0.32 Μ j \\\ 100 Example 4 〇A 0.27 Μ / 1 \\ 100 Example 500A 0.28M J 100 Example 6 0.00B 0.39M j \\\ 100 Example 7 0.00B 0.34 Mj \ \\ 100 Example 8 0.00B 0.29 Mj \ \\ 100 Example 9 〇〇A 0.28 te j \\\ 100 Example 10 〇〇 0.31 Μ j \ \\ 100 Example 11 〇A 0.28 Mj \\\ 100 Example 12 〇A 0.28 ΕΕ 100 Example 13 〇〇B 0.39 te jw \ 100 Example 14 〇B 0.35 te j \ w 100 Comparative Example 1 〇〇D 0.41 100 Comparative example 2 00D 0.42 100% Comparative example 3 0D 0.39 100% Comparative example 4 0D 0.43 100% Comparative example 5 0XC 0.43 100% Comparative example 6 0XC 0.45 100% Comparative example 7 0XC 0.43 yes 100 Comparative Example 8 〇XC 0.45 Yes 100 Comparative Example 9 〇XC 0.43 Yes 100 -42- 200525297 ί [Simplified Illustration] Figure 1 shows the emission spectrum (thick line) of UV-lamps that pass through a UV-transmitting filter. And a spectrum (thin line) of a filter that does not transmit ultraviolet rays. Fig. 2 is an example showing the structure of a liquid crystal display element. Fig. 3 is another view showing the structure of a liquid crystal display element. FIG. 4 is a schematic view showing a cross-sectional shape of a spacer. -3 5 ”Mercury Mercury lamp pattern diagram. Example pattern -43-

Claims (1)

200525297 t 十、申請專利範圍： 1 . 一種形成間隔物用感放射線性樹脂組成物，其特徵爲含 有以下成份： [A] (al)不飽和羧酸及/或不飽和羧酸酐及、（a2)含有環 氧基不飽和化合物及、（a 3 )其他的不飽和化合物的共聚 物； [B] 聚合性不飽和化合物； [C ]雙咪唑系化合物； [D] 具有羰基的感放射線性聚合引發劑；以及 [E] 具有二烷基胺基的化合物及/或[F]硫醇系化合物。 2.如申請專利範圍第1項之形成間隔物用感放射線性樹脂 組成物，其特徵爲[C]雙咪唑系化合物是用下述通式（1) 或者通式（2)表示的化合物，200525297 t X. Scope of patent application: 1. A radiation-sensitive resin composition for forming a spacer, which is characterized by containing the following components: [A] (al) unsaturated carboxylic acid and / or unsaturated carboxylic anhydride, and (a2 ) A copolymer containing an epoxy-based unsaturated compound and (a 3) other unsaturated compounds; [B] a polymerizable unsaturated compound; [C] a bisimidazole-based compound; [D] a radiation-sensitive polymerization having a carbonyl group An initiator; and [E] a compound having a dialkylamino group and / or [F] a thiol-based compound. 2. The radiation-sensitive resin composition for forming a spacer according to item 1 of the patent application, characterized in that the [C] bisimidazole-based compound is a compound represented by the following general formula (1) or (2), [式中，X表不氫原子、鹵原子、氧基、碳數1〜4的院 基或碳數6〜9的芳基，A表示—C〇〇一R(其中，R表示碳 數1〜4的院基或碳數6〜9的芳基）’η是1〜3的整數，各m -44- 200525297 * * 是1〜3的整數][In the formula, X represents a hydrogen atom, a halogen atom, an oxy group, an academic group having 1 to 4 carbon atoms or an aryl group having 6 to 9 carbon atoms, and A represents -C00-R (wherein, R represents carbon number 1) 44 or aryl group with 6 to 9 carbons) 'η is an integer of 1 to 3, each m -44- 200525297 * * is an integer of 1 to 3] X3 (式中，X1、X2及X3相互獨立地表示氫原子、鹵原子、 氰基、碳數1〜4的烷基或碳數6〜9的芳基，但是，X1、 X2及X3的2個以上不能同時作爲氫原子）。 3. —種間隔物，係由如申請專利範圍第1或2項之形成間 隔物用感放射線性樹脂組成物所形成。 4. 一種間隔物的形成方法，其特徵爲至少含有下述（1)〜（4) 的步驟： (1) 在基板上形成如申請專利範圍第1或2項之形成間 隔物用感放射線性樹脂組成物的薄膜的步驟； (2) 在該薄膜的至少一部分上曝光實質上不含有低於 3 5 Onm波長的放射線的步驟； (3) 對曝光後的薄膜進行顯影的步驟； (4) 對顯影後的薄膜進行加熱的步驟。 5 · —種液晶顯示元件，其具有申請專利範圍第3項之間隔 物。 -45-X3 (In the formula, X1, X2, and X3 independently represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 9 carbon atoms. However, X1, X2, and X3 have 2 More than one cannot be hydrogen atoms at the same time). 3. A spacer made of a radiation-sensitive resin composition for forming a spacer as described in item 1 or 2 of the scope of patent application. 4. A method for forming a spacer, characterized in that it comprises at least the following steps (1) to (4): (1) forming a spacer on the substrate as described in Patent Application Scope No. 1 or 2 for radiation sensitivity A step of a thin film of a resin composition; (2) a step of exposing at least a part of the film to substantially no radiation having a wavelength below 3 5 Onm; (3) a step of developing the exposed film; (4) A step of heating the developed film. 5-A liquid crystal display device having a spacer in the third item of the patent application. -45-
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