TW200903150A - Radiation sensitive resin composition, space body for liquid crystal display element and manufacturing method thereof - Google Patents

Radiation sensitive resin composition, space body for liquid crystal display element and manufacturing method thereof Download PDF

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TW200903150A
TW200903150A TW097109643A TW97109643A TW200903150A TW 200903150 A TW200903150 A TW 200903150A TW 097109643 A TW097109643 A TW 097109643A TW 97109643 A TW97109643 A TW 97109643A TW 200903150 A TW200903150 A TW 200903150A
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weight
film
resin composition
radiation
acrylate
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TW097109643A
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Chinese (zh)
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TWI427409B (en
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Daigo Ichinohe
Ryuji Sugi
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Jsr Corp
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0755—Non-macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials For Photolithography (AREA)
  • Liquid Crystal (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention includes a polymer obtained from the reaction between a copolymer of at least one selected from unsaturated carboxylic acid and unsaturated carboxylic acid anhydride and a unsaturated compound containing at least one hydroxyl included in one molecule, and a w-(methyl) propenyl acyloxy alkyl isocyanate. The invention further includes at least one selected from unsaturated carboxylic acid and unsaturated carboxylic acid anhydride and (a3) radiation sensitive resin composite provided with copolymer of unsaturated compound of epoxy ethyl or oxa- cyclobutyl.; The invention provides a radiation sensitive resin composite of space body for the liquid crystal display element with rough surface but no concavo-convex shape on the obtained pattern surface, which is provided with high sensitivity with a full space body shape even if in a light exposure below 1000 J/m(sup)2(/sup) and is able to form excellent properties, such as elasticity recoverability, friction tolerance, adhesiveness of transparent substrate, and heat resistance, and excellent develop property.

Description

200903150 九、發明說明 【發明所屬之技術領域】 本發明係有關極適合形成液晶顯示元件之間隔物之含 有側鏈不飽和聚合物的敏輻射線性樹脂組成物、間隔物及 液晶顯示元件。 【先前技術】 以往液晶顯示元件爲了使2片基板間之間隔（晶胞間 隙）保持一定，而使用具有所定粒徑之玻璃珠、塑膠珠等 之間隔物。這些間隔物係散布於玻璃基板等透明基板上， 因此在像素形成區域含有間隔物時，會產生間隔物之映入 現象或入射光散射’造成液晶顯示元件之對比降低的問題 〇 因此’爲了解決這些問題，而採用藉由光蝕刻來形成 間隔物的方法。此方法係將敏輻射線性樹脂組成物塗佈於 基板上’經由所定之光罩以紫外線曝光後顯像，形成點狀 或條帶狀之間隔物者，因僅在像素形成區域以外之所定場 所可形成間隔物，因此基本上解決如前述的問題。 但是近年，從液晶顯示元件之大面積化及提高生產性 等的觀點，母玻璃基板正朝大型化，例如， l，500 xl,800mm，甚至 1,870 x2,200mm 程度邁進。但是以 來之基板尺寸係因基板尺寸比光罩尺寸還小，因此可用一 次性曝光方式，但對於大型基板時，製作與其相同程度之 光罩尺寸幾乎是不可能，很難使用一次性曝光方式。 -4- 200903150 因此’可對應大型基板之曝光方式，例如提倡採用步 進式曝光方式。然而，步進式曝光方式係對於一片基板進 行數次曝光，每次曝光時，核對位置及步進移動需要時間 ’因此相較於一次性曝光方式，會降低生產量，爲了彌補 此缺點而需要提高敏輻射線性樹脂組成物的感度。 另外’一次性曝光方式其曝光量可爲3,OOOJ/m2程度 ，然而步進式曝光方式需要降低每一次之曝光量，以往用 於形成間隔物之敏輻射線性樹脂組成物在1，0 〇 〇 J/m2以下 之曝光量很難達成充分之間隔物形狀及膜厚。 隨著基板之大型化步驟產生不良時，必須將彩色濾光 片上所形成之配向膜剝離，再利用。配向膜之剝離係使用 鹼水溶液系之剝離液，但是間隔物必須對此剝離液具有耐 剝離液性。換言之，配向膜之剝離時，下層之間隔物不會 因膨潤或溶解產生膜厚變化較佳，而且彈性特性等之物理 性質也必須顯示與剝離前相同的性質。 日本特開2000-105456号公報、特開2000-171804号 公報及特開2000-298 3 3 9号公報係感光性樹脂組成物中使 用（甲基）丙烯醯氧基烷基異氰酸酯化合物與具有羥基之 共聚性樹脂反應之具有光聚合性官能基爲構成單位的共聚 合性樹脂，可達成高感度化、耐藥品性等之間隔物或提高 保護膜之性能。爲了提高間隔物或保護膜之耐熱性、與基 板之密著性、耐藥品性，特別是配向膜對剝離液或鹼水溶 液之耐性，而使用分子内具有2個以上之環氧基之酚醛型 環氧樹脂。但是添加此環氧樹脂可能造成感光性樹脂組成 -5- 200903150 物對顯像液之溶解性降低。 丙烯酸型樹脂系與酚醛型環氧樹脂彼此之分子結構差 異大，因此樹脂間之相溶性低，形成之間隔物表面有時壞 產生凹凸狀之表面粗糙的情形。間隔物表面產生凹凸狀之 表面粗糙時，間隙之嚴密的控制困難，結果可能造成液晶 顯示元件之品質降低的原因。 如上述，以往之敏輻射線性樹脂組成物藉由添加酚醛 型環氧樹脂化合物，雖可提高與基板之密著性、耐藥品性 ，例如配向膜對剝離液耐性，但是對於顯像液之溶解性或 圖型之表面粗糙會產生問題。 【發明內容】 發明之揭示 本發明之目的係提供高感度，且即使在l,000J/m2以 下之曝光量也可得到充分的間隔物形狀，可形成彈性回復 性、耐摩擦性、與透明基板之密著性、耐熱性等優異，而 且顯像性優’製得之圖型表面無凹凸狀之表面粗糙的液晶 顯示元件用間隔物的敏輻射線性樹脂組成物。 本發明之其他目的係提供一種由敏輻射線性樹脂組成 物形成所成之液晶顯示元件用間隔物及具備該間隔物之液 晶顯示元件。 本發明之其他目的係提供一種液晶顯示元件用間隔物 之形成方法。 本發明之其他目的及優點如以下說明得知。 -6- 200903150 依據本發明時，本發明之上述目的及優點，第一可藉 由下述敏輻射線性樹脂組成物來達成，該敏輻射線性樹脂 組成物，其特徵係含有[A1]使下述式（1)表示之含異氰 酸酯基之不飽和化合物' (al)選自不飽和羧酸及不飽和 羧酸酐所成群之至少一種與（a2) 1分子中含有至少1個 羥基之不飽和化合物之共聚物反應所得之聚合物及 H2C=C一C—Ο-i~CH2i-N=C=0 II \ / η 0 (1) (式中，R1係氫原子或甲基，η係1〜12之整數）。 [A2] ( al )選自不飽和羧酸及不飽和羧酸酐所成群之 至少一種與（a3)具有氧環乙基或氧環丁基之不飽和化合 物的共聚物。 其中該[A1]之（a2)成份爲下述式（2)表示的不飽 和化合物較佳。 R2 I H2〇=C—C—〇 ΟBACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a radiation sensitive linear resin composition, a spacer, and a liquid crystal display element comprising a side chain unsaturated polymer which is highly suitable for forming a spacer of a liquid crystal display element. [Prior Art] Conventionally, a liquid crystal display element uses a spacer such as a glass bead or a plastic bead having a predetermined particle size in order to keep a space (cell gap) between two substrates constant. Since these spacers are spread on a transparent substrate such as a glass substrate, when a spacer is formed in the pixel formation region, a phenomenon of reflection of a spacer or scattering of incident light causes a problem that the contrast of the liquid crystal display element is lowered. These problems are the use of a method of forming spacers by photo etching. In this method, the sensitive radiation linear resin composition is applied onto a substrate and is developed by ultraviolet light exposure through a predetermined mask to form a dot-like or strip-shaped spacer, because the predetermined area is only outside the pixel formation region. Spacers can be formed, thus substantially solving the problems as described above. However, in recent years, from the viewpoint of increasing the area of liquid crystal display elements and improving productivity, the mother glass substrate is being enlarged, for example, l, 500 x l, 800 mm, or even 1,870 x 2, 200 mm. However, since the substrate size is smaller than the size of the mask, a one-time exposure method can be used, but for a large substrate, it is almost impossible to manufacture a mask size of the same degree, and it is difficult to use the one-time exposure method. -4- 200903150 Therefore, the exposure method for large substrates can be used, for example, the stepwise exposure method is advocated. However, the stepwise exposure method is to perform several exposures on one substrate. It takes time to check the position and step movement for each exposure. Therefore, compared with the one-time exposure method, the production amount is reduced, and it is necessary to make up for this disadvantage. Improve the sensitivity of the sensitive radiation linear resin composition. In addition, the exposure amount of the 'one-time exposure method can be about 3,000 J/m2. However, the stepwise exposure method needs to reduce the exposure amount per time. The linear composition of the sensitive radiation used to form the spacer is at 1,0 〇. It is difficult to achieve a sufficient spacer shape and film thickness for the exposure amount of 〇J/m2 or less. When the substrate is enlarged in size, the alignment film formed on the color filter must be peeled off and reused. The peeling of the alignment film is carried out using a stripping solution of an aqueous alkali solution, but the separator must have peeling resistance to the peeling liquid. In other words, when the alignment film is peeled off, the spacer of the lower layer is not preferably changed in thickness due to swelling or dissolution, and the physical properties such as elastic properties must also exhibit the same properties as those before peeling. JP-A-2000-105456, JP-A-2000-171804, JP-A-2000-298, No. 2000-298 No. 2000-298 discloses a (meth) propylene oxyalkylene isocyanate compound and a hydroxyl group in a photosensitive resin composition. The copolymerizable resin having a photopolymerizable functional group as a constituent unit of the copolymerizable resin can achieve a spacer having high sensitivity and chemical resistance, or can improve the performance of the protective film. In order to improve the heat resistance of the separator or the protective film, the adhesion to the substrate, and the chemical resistance, in particular, the resistance of the alignment film to the stripping solution or the aqueous alkali solution, a phenolic type having two or more epoxy groups in the molecule is used. Epoxy resin. However, the addition of this epoxy resin may result in a decrease in the solubility of the photosensitive resin composition -5-200903150 to the developing solution. Since the acrylic resin type and the novolac type epoxy resin have a large difference in molecular structure, the compatibility between the resins is low, and the surface of the formed spacer may be rough or uneven. When the surface of the spacer is roughened, the tight control of the gap is difficult, and as a result, the quality of the liquid crystal display element may be lowered. As described above, the conventional sensitized radiation linear resin composition can improve the adhesion to the substrate and the chemical resistance by adding a phenolic epoxy resin compound, for example, the alignment film is resistant to the peeling liquid, but is dissolved in the developing solution. Surface roughness of the sex or pattern can cause problems. DISCLOSURE OF THE INVENTION The object of the present invention is to provide high sensitivity, and a sufficient spacer shape can be obtained even at an exposure amount of 1,000 J/m 2 or less, and elastic recovery, abrasion resistance, and transparent substrate can be formed. The radiation sensitive linear resin composition of the spacer for liquid crystal display elements having excellent surface properties, excellent heat resistance, and the like. Another object of the present invention is to provide a spacer for a liquid crystal display element formed of a radiation sensitive linear resin composition and a liquid crystal display element comprising the spacer. Another object of the present invention is to provide a method of forming a spacer for a liquid crystal display element. Other objects and advantages of the invention will be apparent from the description below. -6- 200903150 According to the present invention, the above objects and advantages of the present invention can be attained by the following sensitive radiation linear resin composition characterized in that it contains [A1] The isocyanate group-containing unsaturated compound '(al) represented by the formula (1) is selected from at least one of a group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride, and an unsaturated group containing at least one hydroxyl group in the (a2) 1 molecule. The polymer obtained by the reaction of the copolymer of the compound and H2C=C-C-Ο-i~CH2i-N=C=0 II \ / η 0 (1) (wherein R1 is a hydrogen atom or a methyl group, η is 1 An integer of ~12). [A2] (al) a copolymer selected from the group consisting of at least one of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride and (a3) an unsaturated compound having an oxocycloethyl group or an oxocyclobutyl group. Among them, the component (a2) of [A1] is preferably an unsaturated compound represented by the following formula (2). R2 I H2〇=C—C—〇 Ο

200903150 由下述液晶顯示元件用間隔物用敏輻射線性樹脂組成物來 達成。 液晶顯示元件用間隔物用敏輻射線性樹脂組成物爲上 述敏輻射線性樹脂組成物尙含有[B]重合性不飽和化合物 與[C]敏輻射線性聚合引發劑之敏輻射線性樹脂組成物（ 以下稱爲「液晶顯示元件用間隔物用敏輻射線性樹脂組成 物」）。 依據本發明時，本發明之上述目的及優點，第三可藉 由上述各敏輻射線性樹脂組成物形成所成之液晶顯示元件 用間隔物來達成。 依據本發明時，本發明之上述目的及優點，第四可藉 由液晶顯示元件用間隔物之形成方法來達成。該液晶顯示 元件用間隔物之形成方法，其特徵係至少含有以下記載之 順序之以下的步驟， (甲）在基板上形成上述液晶顯示元件用間隔物用敏 輻射線性樹脂組成物之被膜的步驟， (乙）對該被膜之至少一部份進行曝光的步驟， (丙）曝光後之該被膜進行顯像的步驟，及 (丁）顯像後之該被膜進行加熱的步驟。 依據本發明時’本發明之上述目的及優點，第五可藉 由具備上述液晶顯示元件用間隔物之液晶顯示元件來達成 實施發明之最佳形態 _ 8 - 200903150 以下詳細說明本發明。 -〔A〕聚合物_ 本發明之組成物係由[A1]使上述式（1)表示之異氰 酸酯基化合物（以下稱爲「不飽和異氰酸酯化合物（1 ) j )與（al)選自不飽和羧酸及不飽和羧酸酐所成群之至 少一種與（a2 ) 1分子中含有至少1個羥基之不飽和化合 物之共聚物（以下稱爲「共聚物〔α〕」）反應所得之聚 合物（以下稱爲「[Α]聚合物」）及 [Α2] (al)選自不飽和羧酸及不飽和羧酸酐所成群之 至少一種與（a3)具有氧環乙基或氧環丁基之不飽和化合 物的共聚物（以下稱爲「共聚物〔β〕」）所構成。 構成共聚物〔α〕及共聚物〔β〕之各成份中，羧酸、 不飽和羧酸酐（以下統稱爲「（ a 1 )不飽和羧酸化合物」 )例如有丙烯酸、甲基丙烯酸、巴豆酸、2 -丙烯醯氧基乙 基琥珀酸、2-甲基丙烯醯氧基乙基琥珀酸、2-丙烯醯氧基 乙基六氫鄰苯二甲酸、2 -甲基丙烯醯氧基乙基六氫鄰苯二 甲酸等之單羧酸； 順丁烯二酸、反丁烯二酸、檸康酸、中康酸、衣康酸 等之二羧酸； 前述二羧酸之酸酐等。 這些（a 1 )之不飽和竣酸化合物中，從共聚反應性、 所得之聚合物及共聚物對鹼顯像液之溶解性及易於取得的 觀點，較佳爲丙烯酸、甲基丙烯酸、順丁嫌二酸酐等。 -9- 200903150 共聚物〔α〕及共聚物〔β〕之（al)不飽和羧酸化合 物可單獨使用或混合2種以上使用。 共聚物〔α〕及共聚物〔β〕中，來自（al)不飽和竣 酸化合物之重複單位之含有率較佳爲5〜50重量％，更佳 爲 10〜40重量％，特佳爲 15〜30重量％。來自（al)不 飽和羧酸化合物之重複單位之含有率未達5重量％時，與 不飽和異氰酸酯化合物（1 )反應所得之聚合物對鹼顯像 液之溶解性有降低的傾向，而超過50重量％時，該聚合物 對鹼顯像液之溶解性可能過大。 又，（a2 ) 1分子中至少含有1個羥基的不飽和化合 物，例如有丙烯酸2-羥基乙酯、丙烯酸3-羥基丙酯、丙烯 酸4-羥基丁酯、丙烯酸5-羥基戊酯、丙烯酸6-羥基己酯 、丙烯酸7-羥基庚酯、丙烯酸8-羥基辛酯、丙烯酸9-羥 基壬酯、丙烯酸10-羥基癸酯、丙烯酸11-羥基十一酯、丙 烯酸12-羥基十二酯之丙烯酸羥基烷酯； 甲基丙烯酸2-羥基乙酯、甲基丙烯酸3-羥基丙酯、甲 基丙烯酸4 -羥基丁酯、甲基丙烯酸5 -羥基戊酯、甲基丙烯 酸6 -羥基己酯、甲基丙烯酸7 -羥基庚酯、甲基丙烯酸8_ 羥基辛酯、甲基丙烯酸9-羥基壬酯、甲基丙烯酸1〇_羥基 癸酯、甲基丙烯酸11-羥基十一酯、甲基丙烯酸12-羥基十 二酯之甲基丙烯酸羥基烷酯； 丙烯酸4-羥基-環己酯、丙烯酸4 -羥基甲基-環己基甲 酯、丙烯酸4-羥基乙基-環己基乙酯、丙烯酸3-羥基-雙環 [2.2.1]庚-5-烯-2-基酯、丙烯酸3-羥基甲基-雙環[2.2.1] -10- 200903150 庚_5_烯_2_基甲酯、丙烯酸3-羥基乙基-雙環[2.2.1]庚-5-烯_2_基乙酯、丙烯酸8-羥基-雙環[2.2.1]庚-5-烯-2-基酯、 丙烯酸2_羥基-八氫- 4,7 -甲-節_5_基酯、丙烯酸2-羥基甲 基-八氫-4,7 -甲-茚- :5 -基甲酯、丙烯酸2_羥基乙基-八氫_ 4,7 -甲-茚-5-基乙酯、丙烯酸3_羥基-金剛烷基酯、丙烯 酸3-羥基甲基-金剛烷-i_基甲酯、丙烯酸3 -羥基乙基-金 剛烷-1 -基乙酯之具有脂環族結構之丙烯酸羥基烷酯； 甲基丙烯酸4-羥基-環己酯、甲基丙烯酸4-羥基甲基_ 環己基甲酯、甲基丙烯酸4 -羥基乙基-環己基乙酯、甲基 丙烯酸3-羥基-雙環[2.2.1]庚-5-烯-2-基酯、甲基丙烯酸3_ 羥基甲基-雙環[2.2.1]庚-5-烯-2-基甲基酯、甲基丙烯酸3-羥基乙基-雙環[2.2.1]庚-5-烯-2-基乙基酯、甲基丙烯酸8-羥基-雙環[2.2.1]庚-5-烯-2-基酯、甲基丙烯酸2-羥基-八 氫-4,7-甲-茚-5-基酯、甲基丙烯酸2_羥基甲基-八氫-4,7-甲-印-5-基甲醋 '甲基丙嫌酸2-經基乙基-八氫- 4,7 -甲-節· 5-基乙酯、甲基丙烯酸3-羥基-金剛烷-卜基酯、甲基丙烯 酸3 -羥基甲基-金剛烷-1 -基甲酯、甲基丙烯酸3 -羥基乙 基-金剛烷-1-基乙酯之具有脂環族結構之甲基丙烯酸羥基 烷酯； 丙烯酸1,2-二羥基乙酯、丙烯酸2,3-二羥基丙酯、丙 烯酸1,3-二羥基丙酯、丙烯酸3,4-二羥基丁酯、丙烯酸3-[3- ( 2,3 -二羥基丙氧基）-2 -羥基丙氧基]-2 -羥基丙酯等之 丙烯酸二羥基烷酯； 甲基丙烯酸1，2-二羥基乙酯、甲基丙烯酸2,3-二羥基 -11 - 200903150 丙酯、甲基丙烯酸1，3-二羥基丙酯、甲基丙烯酸3，4 -二羥 基丁酯、甲基丙烯酸3-[3- ( 2,3-二羥基丙氧基）-2-羥基 丙氧基]-2-羥基丙酯等之甲基丙烯酸二羥基烷酯等。 這些1分子中至少含有1個羥基的不飽和化合物中， 從共聚反應性及與異氰酸酯化合物之反應性的觀點，較佳 爲丙烯酸2-羥基乙酯、丙烯酸3-羥基丙酯、丙烯酸4-羥 基丁酯、甲基丙烯酸2 -羥基乙酯、甲基丙烯酸3 -羥基丙酯 、甲基丙烯酸4-羥基丁酯、丙烯酸4-羥基甲基·環己基甲 酯、甲基丙烯酸4 -羥基甲基-環己基甲酯、丙烯酸2,3 -二 羥基丙酯、甲基丙烯酸2,3 -二羥基丙酯等。 (a2)成份中，上述式（2)表示之具有羥基的不飽 和化合物，從提高顯像性的觀點’或提高製得之間隔物之 壓縮性能的觀點特佳。 其具體例有丙烯酸2- ( 6·羥基己醯氧基）乙酯、丙烯 酸3- (6 -羥基己醯氧基）丙酯、丙烯酸4- (6 -羥基己醯氧 基）丁醋、丙稀酸5-(6 -羥基己酿氧基）戊酯、丙烯酸6-(6-羥基己醯氧基）己酯之丙烯酸（6-羥基己醯氧基）烷 酯； 甲基丙烯酸2- ( 6-羥基己醯氧基）乙酯、甲基丙烯酸 3-(6-羥基己醯氧基）丙酯、甲基丙烯酸4-(6-羥基己醯 氧基）丁酯、甲基丙烯酸5- (6-羥基乙基己醯氧基）戊酯 、甲基丙烯酸6- ( 6-羥基己醯氧基）己酯之甲基丙烯酸（ 6-羥基己醯氧基）烷酯； 這些當中，特佳爲丙烯酸2· ( 6-羥基己醯氧基）乙酯 -12- 200903150 、甲基丙烯酸2- ( 6-羥基己醯氧基）乙酯，而甲基丙烯酸 2- (6-羥基己醯氧基）乙酯與甲基丙烯酸2-羥基乙酯之混 合物的市售品，例如有商品名爲PLACCEL FM1D、FM2D (Daicel化學工業（股）製）等。 共聚物〔α〕中，（a2) 1分子中含有至少1個經基之 不飽和化合物可單獨或混合2種以上使用。 共聚物〔α〕中，來自（a2) 1分子中含有至少1個羥 基之不飽和化合物之重複單位的含有率，較佳爲1〜5 0重 量％，更佳爲3〜4 0重量％，特佳爲5〜3 0重量％。來自（ a2) 1分子中含有至少1個羥基之不飽和化合物之重複單 位的含有率未達1重量％時，不飽和異氰酸酯化合物（1 ) 對聚合物之導入率降低，且有感度降低的傾向，超過50 重量％時，與不飽和異氰酸酯化合物（1 )反應所得之聚合 物的保存安定性有降低的傾向。 共聚物〔/3〕之（a3)之具有氧環乙基或氧環丁基之 不飽和化合物例如有丙烯酸縮水甘油酯、丙烯酸2-甲基縮 水甘油酯、4-羥基丁基丙烯酸酯縮水甘油醚、丙烯酸3，4-環氧丁酯、丙烯酸6,7-環氧基庚酯、丙烯酸3,4-環氧基環 己酯等之丙烯酸環氧基（環）烷酯； 甲基丙烯酸縮水甘油酯、甲基丙烯酸2-甲基縮水甘油 酯、甲基丙烯酸3,4-環氧基丁酯、甲基丙烯酸6,7-環氧基 庚酯、甲基丙烯酸3,4-環氧基環己酯、甲基丙烯酸3,4-環 氧基環己基甲基等之甲基丙烯酸環氧基（環）烷酯； α-乙基丙烯酸縮水甘油酯、丙基丙烯酸縮水甘油 -13- 200903150 酯、α-η-丁基丙烯酸縮水甘油酯、α_乙基丙烯酸6,7_環氧 基庚酯、α-乙基丙烯酸3,4-環氧基環己酯等之其他之α-烷 基丙烯酸環氧基（環）烷酯； 〇 -乙烯基苄基縮水甘油醚、m -乙烯基苄基縮水甘油醚 、P-乙烯基苄基縮水甘油醚等縮水甘油醚。 3-(甲基丙烯醯氧基甲基）氧雜環丁烷、3-(甲基丙 烯醯氧基甲基）-3-乙基氧雜環丁烷、3-(甲基丙烯醯氧基 甲基）-2-甲基氧雜環丁烷、3-(甲基丙烯醯氧基甲基）- 2- 三氟甲基氧雜環丁烷、3-(甲基丙烯醯氧基甲基）-2-五 氟乙基氧雜環丁烷、3-(甲基丙烯醯氧基甲基）-2-苯基氧 雜環丁烷、3-(甲基丙烯醯氧基甲基）-2,2-二氟氧雜環丁 烷、3-(甲基丙烯醯氧基甲基）-2,2,4-三氟氧雜環丁烷、 3- (甲基丙烯醯氧基甲基）-2,2，4,4-四氟氧雜環丁烷、3-(甲基丙烯醯氧基乙基）氧雜環丁烷、3·(甲基丙烯醯氧 基乙基）-3-乙基氧雜環丁烷、2-乙基- 3-(甲基丙烯醯氧 基乙基）氧雜環丁烷、3-(甲基丙烯醯氧基乙基）-2-三氟 甲基氧雜環丁烷、3-(甲基丙烯醯氧基乙基）-2 -五氟乙基 氧雜環丁烷、3-(甲基丙烯醯氧基乙基）-2 -苯基氧雜環丁 烷、2,2-二氟- 3-(甲基丙烯醯氧基乙基）氧雜環丁烷、3_ (甲基丙烯醯氧乙基）_2,2，4-三氟氧雜環丁烷、3_ (甲基 丙烯醯氧基乙基）-2,2,4,4-四氟氧雜環丁烷等之甲基丙嫌 酸酯； 3-(丙烯醯氧基甲基）氧雜環丁院、3_(丙嫌醯氧基 甲基）-3-乙基氧雜環丁烷、3-(丙烯醒氧基甲基）_2-甲 -14- 200903150 基氧雜環丁烷、3-(丙烯醯氧基甲基）-2_三氟甲基氧雜環 丁烷、3-(丙烯醯氧基甲基）-2-五氟乙基氧雜環丁烷、3-(丙烯醯氧基甲基）-2-苯基氧雜環丁烷、3-(丙烯醯氧基 甲基）-2,2 -二氟氧雜環丁烷、3_ (丙烯醯氧基甲基）. 2,2,4-三氟氧雜環丁烷、3 -(丙烯醯氧基甲基）-2,2,4,4·四 氟氧雜環丁烷、3-(丙烯醯氧基乙基）氧雜環丁烷、3_( 丙烯醯氧基乙基）-3 -乙基氧雜環丁烷、2 -乙基- 3-(丙烯 醯氧基乙基）氧雜環丁烷、3-(丙烯醯氧基乙基）_2_三氟 甲基氧雜環丁院、3-(丙烯醯氧基乙基）-2 -五氟乙基氧雜 環丁烷、3-(丙烯醯氧基乙基）_2_苯基氧雜環丁烷、2,2_ 二氟- 3-(丙燦醢氧基乙基）氧雜環丁烷、3_ (丙烯醯氧基 乙基）-2,2,4-三氟氧雜環丁烷、3_(丙烯醯氧基乙基）· 2,2,4,4 -四氟< 氧雜環丁院等之丙嫌酸酯。 其中從聚合性的觀點，特佳爲甲基丙烯酸縮水甘油酯 、甲基丙烧酸2 -甲基縮水甘油酯、甲基丙烯酸3,4_環氧基 環己基甲醋、3-甲基_3_ (甲基）丙烯醯氧基甲基氧雜環丁 院、3 -乙基-3-(甲基）丙烯醯氧基甲基氧雜環丁烷、 甲基丙烯醯氧基甲基）-3 -乙基氧雜環丁院等。 共聚物〔β〕中’ （a3)可單獨或混合2種以上使用 〇 共聚物〔β〕中’來自（a3)之重複單位的含有率， 較佳爲0 · 5〜7 0重量％，更佳爲丨〜6 〇重量％，特佳爲3〜 50重量％。來自（a3)之重複單位的含有率未達〇.5重量 %時’製得之共聚物的耐熱性有降低的傾向，超過7 〇重量 -15- 200903150 %時，共聚物之保存安定性有降低的傾向。 又，共聚物〔α〕及共聚物〔β〕中，與（ai) 、（a2 )及（a3 )不同之其他的不飽和化合物可作爲共聚物的成 份使用。其具體例有丙烯酸甲酯、丙烯酸η -丙酯、丙烯酸 i-丙酯、丙烯酸η-丁酯、丙烯酸sec-丁酯、丙烯酸t-丁酯 等之丙烯酸烷酯； 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-丙酯、甲基丙烯酸η-丁酯、甲基丙烯酸 sec-丁酯、甲基丙烯酸t-丁酯等之甲基丙烯酸烷酯； 丙烯酸環己酯、丙烯酸2-甲基環己酯、丙烯酸三環 [5.2.1.02’6]癸烷-8-酯、丙烯酸2-(三環[5.2.1.02’6]癸烷-8 -基氧基）乙酯、丙烯酸異冰片酯等之丙烯酸脂環族酯； 甲基丙烯酸環己酯、甲基丙烯酸2-甲基環己酯、甲基 丙烯酸三環[5.2.1.02,6]癸烷-8-酯、甲基丙烯酸2-(三環 [5.2.1.02,6]癸烷-8-基氧基）乙酯、甲基丙烯酸異冰片酯等 之甲基丙烯酸脂環族酯； 丙烯酸苯酯、丙烯酸苄酯等之丙烯酸之芳酯或芳烷酯 » 甲基丙烯酸苯酯、甲基丙烯酸苄酯等之甲基丙烯酸之 芳酯或芳烷酯； 順丁烯二酸二乙酯、反丁烯二酸二乙酯、衣康酸二乙 酯等之不飽和二羧酸二烷酯； 丙烯酸四氫呋喃-2 -酯、丙烯酸四氫吡喃-2 -酯、丙烯 酸2-甲基四氫吡喃·2·酯等之具有含氧雜5員環或含氧雜6 -16- 200903150 員環之丙烯酸酯； 甲基丙烯酸四氫呋喃-2-酯、甲基丙烯酸四氫吡喃-2 _ 酯、甲基丙烯酸2-甲基四氫吡喃-2_酯等之具有含氧雜5 員環或含氧雜6員環之甲基丙稀酸酯； 苯乙烯、α-甲基苯乙烯、間-甲基苯乙烯、對·甲基苯 乙烯、對-甲氧基苯乙嫌等之乙靖基芳香族化合物； 1,3-丁二烯、異戊二烯、2,3-二甲基-1,3-丁二烯等共 軛二烯系化合物；及丙烯腈、甲基丙烯腈、丙烯醯胺、甲 基丙烯醯胺、氯乙烯、偏氯乙烯、乙酸乙烯酯等。 這些中’從共聚反應性的觀點，較佳爲甲基丙烯酸正 丁酯、丙烯酸2-甲基縮水甘油酯 '甲基丙烯酸苄酯 '甲基 丙烯酸三環〔5_2.1_02’6〕癸烷-8-酯、苯乙烯、對-甲氧基 苯乙烯、甲基丙烯酸四氫呋喃-2-酯、1,3 -丁二烯等。 共聚物〔α〕及共聚物〔β〕中，與（al) 、（a2)及 (a3 )不同之其他的不飽和化合物可單獨或混合2種以上 使用。 共聚物〔α〕及共聚物〔β〕中，來自與（al) 、 ( a2 )及（a3 )不同之其他的不飽和化合物之重複單位之含有 率較佳爲1 〇〜7 0重量％ ’更佳爲2 0〜5 0重量％，特佳爲 3 0〜5 0重量％。此重複單位之含有率未達1 〇重量％時，共 聚物之分子量有降低的傾向，而超過重量％時，（al ) 、（a2 )及（a3 )成份的效果降低。 共聚物〔α〕及共聚物〔β〕係在適當溶劑中，且自由 基聚合引發劑存在下，進行聚合來製造。 -17- 200903150 前述聚合用之溶劑例如有 甲醇、乙醇、正丙醇、異丙醇等醇類； 四氫呋喃、二噁烷等醚類； 乙二醇單甲醚、乙二醇單乙醚、乙二醇單正丙醚、乙 二醇單正丁醚等乙二醇單烷基醚； 乙二醇單甲醚乙酸酯、乙二醇單乙醚乙酸酯、乙二醇 單正丙醚乙酸酯、乙二醇單正丁醚乙酸酯等乙二醇單烷醚 乙酸酯； 乙二醇單甲醚丙酸酯、乙二醇單乙醚丙酸酯、乙二醇 單正丙醚丙酸酯、乙二醇單正丁醚丙酸酯等乙二醇單烷醚 丙酸酯； 二乙二醇單甲醚、二乙二醇單乙醚、二乙二醇二甲醚 、二乙二醇二乙醚、二乙二醇甲基乙醚等二乙二醇烷醚； 丙二醇單甲醚、丙二醇單乙醚、丙二醇單正丙醚、丙 二醇單正丁醚等丙二醇單烷醚； 二丙二醇單甲醚、二丙二醇單乙醚、二丙二醇二甲醚 、二丙二醇二乙醚、二丙二醇甲基乙醚等二丙二醇烷醚； 丙二醇單甲醚乙酸酯、丙二醇單乙醚乙酸酯、丙二醇 單正丙醚乙酸酯、丙二醇單正丁醚乙酸酯等丙二醇單烷醚 乙酸酯； 丙二醇單甲醚丙酸酯、丙二醇單乙醚丙酸酯、丙二醇 單正丙醚丙酸酯、丙二醇單正丁醚丙酸酯等丙二醇單烷醚 丙酸酿， 甲苯、二甲苯等芳香族烴； -18- 200903150 甲基乙基酮、2 -戊酮、3 -戊酮、環己酮、4 -羥基-4-甲 基-2-戊酮等酮類； 2 -甲氧基丙酸甲酯、2 -甲氧基丙酸乙酯、2 -甲氧基丙 酸正丙酯、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、2-正丙氧基丙酸甲酯、2-正丙氧基丙酸乙酯、2-正 丙氧基丙酸正丙酯、2-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烷氧基 丙酸烷酯；及 乙酸甲酯、乙酸乙酯、乙酸正丙酯、乙酸正丁酯、羥 基乙酸乙酯、羥基乙酸正丙酯、羥基乙酸正丁酯、乙酸4-甲氧基丁酯、乙酸3-甲氧基丁酯、乙酸2-甲氧基丁酯、乙 酸3-乙氧基丁酯、乙酸3-丙氧基丁酯、 乳酸甲酯、乳酸乙酯、乳酸正丙酯、乳酸正丁酯、2-羥基-2-甲基丙酸甲酯、2-羥基-2-甲基丙酸乙酯、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、2-羥基-3-甲基丁酸甲酯、甲氧基乙酸甲酯、 -19- 200903150 甲氧基乙酸乙酯、甲氧基乙酸正丙酯、甲氧基乙酸正丁酯 、乙氧基乙酸甲酯、乙氧基乙酸乙酯、乙氧基乙酸正丙酯 、乙氧基乙酸正丁酯、正丙氧基乙酸甲酯、正丙氧基乙酸 乙酯、正丙氧基乙酸正丙酯、正丙氧基乙酸正丁酯、正丁 氧基乙酸甲酯、正丁氧基乙酸乙酯、正丁氧基正丙酯、正 丁氧基乙酸正丁酯等其他酯等。 這些溶劑中’較佳爲二乙二醇烷醚、丙二醇單烷醚乙 酸酯、烷氧基丙酸烷酯等。 前述溶劑可單獨或混合2種以上使用。 又，自由基聚合引發劑無特別限制，例如2,2’-偶氮雙 異丁腈、2,2’-偶氮雙-(2,4-二甲基戊腈）、2,2'-偶氮雙-(4 -甲氧基-2,4-二甲基戊腈）、4,V-偶氮雙（4-氰基戊酸 )、二甲基_2,2'-偶氮雙（2-甲基丙酸酯）、2,2'-偶氮雙（ 4 -甲氧基-2,4 -二甲基戊腈）等偶氮化合物；過氧化苯醯、 過氧化月桂酿、第三丁基過氧化三甲基乙酸酯、1，1-雙（ 第三丁基過氧）環己烷等有機過氧化物；過氧化氫等。 自由基聚合引發劑使用過氧化物時，也可倂用還原劑 ，作爲氧化還原型引發劑。 這些自由基聚合引發劑可單獨或混合2以上使用。 上述所得之共聚物〔α〕可爲溶液狀態供給〔A〕聚合 物之製造成用’或由溶液中分離後再供給〔A〕聚合物之 製造用。 共聚物〔（X〕及共聚物〔β〕之凝膠滲透色譜法（G P C )之聚苯乙燦換算重量平均分子量（以下稱爲「Mw」） -20- 200903150 較佳爲2,000〜100,000’更佳爲5,000〜50,000。此時， Mw未達2，000時，所得之被膜之鹼顯像性、殘膜率等會 降低’或可能損及圖型形狀、耐熱性等，而超過1〇〇,〇〇〇 時，解像度降低或可能損及圖型形狀。 本發明之〔A〕聚合物係將不飽和異氰酸酯化合物（1 )與共聚物〔α〕反應製得。 不飽和異氰酸酯化合物（1 )例如有 2-丙烯醯氧基乙基異氰酸酯、3-丙烯醯氧基丙基異氰 酸酯、4-丙烯醯氧基丁基異氰酸酯、6-丙烯醯氧基己基異 氰酸酯、8-丙烯醯氧基辛基異氰酸酯、ίο-丙烯醯氧基癸基 異氰酸酯等之丙烯酸衍生物； 2 -甲基丙烯醯氧基乙基異氰酸酯、3 -甲基丙烯醯氧基 丙基異氰酸酯、4-甲基丙烯醯氧基丁基異氰酸酯、6_甲基 丙烯醯氧基己基異氰酸酯、8 -甲基丙烯醯氧基辛基異氰酸 酯、10-甲基丙烯醯氧基癸基異氰酸酯等之甲基丙烯酸衍 生物。 又，2-丙烯醯氧基乙基異氰酸酯之市售品，其商品名 爲karenz ΑΟΙ (昭和電工（股）製）、2-甲基丙烯醯氧基 乙基異氰酸酯之市售品，其商品名爲karenzMOI (昭和電 工（股）製）。 這些之不飽和異氰酸酯化合物（1)中，從與共聚物 〔α〕之反應性的觀點，較佳爲2-丙烯醯氧基乙基異氰酸 酯、2-甲基丙烯醯氧基乙基異氰酸酯、4-甲基丙烯醯氧基 丁基異氰酸酯等。 -21 - 200903150 〔A〕聚合物中，不飽和異氰酸酯化合物（1)可單獨 或混合2種以上使用。 本發明中，共聚物〔〇〇與不飽和異氰酸酯化合物（1 )之反應係例如在含有二月桂酸二-正丁基錫（IV)等之 觸媒或對-甲氧基苯酚等聚合停止劑之共聚物〔α〕溶液中 ，室溫或加熱下，攪拌狀態下，投入不飽和異氰酸酯化合 物（1 )進行反應。 製造〔A〕聚合物時之不飽和異氰酸酯化合物（1)之 使用量係對於共聚物〔α〕中之（a2) 1分子中至少含有1 個羥基之不飽和化合物的羥基1當量，較佳爲0. 1〜9 5莫 耳％、更佳爲1 0〜8 0莫耳％，特佳爲1 5〜7 5莫耳％。不飽 和異氰酸酯化合物（1 )之使用量未達〇. i莫耳％時，感度 、耐熱性之提昇及彈性特性提昇的效果低，而超過9 5莫 耳％時，未反應之不飽和異氰酸酯化合物（1 )會殘留，製 得之聚合物溶液及敏輻射線性樹脂組成物之保存安定性有 降低的傾向。 〔A〕聚合物係具有羧基及/或羧酸酐基、聚合性不飽 和鍵，對於鹼顯像液具有適度的溶解性，同時藉由曝光及 加熱可容易硬化者，另外，與具有環氧基之丙烯酸型共聚 物〔β〕倂用時，可與〔A〕聚合物不會產生相分離，且相 溶，不會產生圖型表面粗糙，具有優異的顯像性，可提高 間隔物的強度。含有〔A〕聚合物與共聚物〔β〕之敏輻射 線性樹脂組成物係顯像時，不會產生顯像殘留及膜減少， 容易形成所定形狀之間隔物。 -22- 200903150 對於〔A〕聚合物100重量份，共聚物〔β〕之使用量 係較佳爲0.5〜50重量份，更佳爲1〜40重量份，特佳爲 3〜30重量份。共聚物〔β〕之使用量未達0.5重量份時， 提昇間隔物之強度或耐熱性的效果較小，而超過5 0重量 份時，敏輻射線性樹脂組成物之保存安定性有降低的傾向 -敏輻射線性樹脂組成物- 本發明之敏輻射線性樹脂組成物係如上述含有〔A〕 聚合物與共聚物〔β〕，較佳爲可含有〔Β〕聚合性不飽和 化合物及〔C〕感放射線性聚合引發劑。 -〔Β〕聚合性不飽和化合物- 〔Β〕聚合性不飽和化合物係由敏輻射線性聚合引發 劑之存在下，以輻射線曝光產生聚合之不飽和化合物所構 成。 這種〔Β〕聚合性不飽和化合物無特別限制，但從共 聚性良好，提高製得之間隔物之強度的觀點，較佳爲單官 能、2官能及3官能以上之（甲基）丙烯酸酯。 前述單官能（甲基）丙烯酸酯，例如有2-羥乙基丙烯 酸酯、2 -羥乙基甲基丙烯酸酯、二乙二醇單乙醚丙烯酸酯 、二乙二醇單乙醚甲基丙烯酸酯、丙烯酸異冰片酯、甲基 丙烯酸異冰片酯、3 -甲氧基丁基丙烯酸酯、3_甲氧基丁基 甲基丙烯酸酯、（2_丙烯醯氧基乙基）（2-羥丙基）苯二 -23- 200903150 甲酸酯、（2 -甲基丙烯醯氧基乙基）（2-羥丙基）苯二甲 酸酯、ω_羧基聚己內酯單丙烯酸酯等。市售品例如商品 名 Aronix Μ-101、同 Μ-111、同 Μ-114、同 Μ- 5 3 00 (以 上爲東亞合成（股）製）；KAYARAD TC-110S、TC-120S (以上爲日本化藥（股）製）；Viscoat 158、同2311 ( 以上爲大阪有機化學工業（股）製）。 前述2官能（甲基）丙烯酸酯例如有乙二醇二丙烯酸 酯、乙二醇二甲基丙烯酸酯、二乙二醇二丙烯酸酯、二乙 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、1,6 -己二醇二丙烯酸酯、ι,6_己二醇二甲 基丙烯酸酯、1,9 -壬二醇二丙烯酸酯、丨，9_壬二醇二甲基 丙烯酸酯、雙苯氧基乙醇芴二丙烯酸酯、雙苯氧基乙醇芴 二甲基丙烯酸酯等。市售品例如有Aronix M_21〇、同M-240、同M-6200 (以上東亞合成（股）製）、KAYARAD HDDA、同HX-220、同R-604 (以上日本化藥（股）製） 、Viscoat 260、同312、同3 3 5 HP (以上大阪有機化學工 業（股）製）、light丙烯酸酯l，9-NDA(共榮社（股）製 )等。 上述3官能以上之（甲基）丙烯酸酯，例如有三羥甲 基丙烷三丙烯酸酯、三羥甲基丙烷三甲基丙烯酸酯、季戊 四醇二丙稀酸醋、季戊四醇三甲基丙丨希酸酯、季戊四醇四 丙稀酸酯、季戊四醇四甲基丙烯酸酯、二季戊四醇五丙烯 酸酯、二季戊四醇五甲基丙烯酸酯、二季戊四醇六丙烯酸 醋、一季戊四醇六甲基丙烯酸酯、三（2 -丙烯醯氧基乙基 -24- 200903150 )磷酸酯、三（2-甲基丙烯醯氧基乙基）磷酸酯，或9官 能以上之（甲基）丙烯酸酯係使具有直鏈伸烷基及脂環構 造，且具有2個以上之異氰酸酯基的化合物與分子內具有 1個以上之羥基，且具有3個、4個或5個之丙烯醯氧基 及/或甲基丙烯醯氧基的化合物產生反應所得之多官能胺 基甲酸乙酯丙烯酸酯化合物等。 3官能以上之（甲基）丙烯酸酯之市售品，其商品名 例如有市售品例如商品名 Aronix M-309、同 M-400、同 M-405、同 M-4 5 0、同 M-7100、同 M- 803 0、同 M- 8060、 同 TO- 1 450 (以上爲東亞合成（股）製）；KAYARAD TMPTA、同 DPHA、同 DPCA-20、同 DPCA-30、同 PDCA-60、同DPCA-120(以上爲日本化藥（股）製）；ViSC〇at 295、300、360、同GPT、同3PA、同400 (以上爲大阪有 機化學工業（股）製）或含有多官能胺基甲酸乙酯丙烯酸 醋系化合物之市售品：New frontier R-1150 (第一工業製 藥（股）製）、KAYARAD DPHA-40H (日本化藥（股） 製）等。 這些單官能、2官能或3官能以上之（甲基）丙烯酸 酯中’較佳爲3官能以上之（甲基）丙烯酸酯，特佳爲三 羥甲基丙烷三丙烯酸酯、季戊四醇三丙烯酸酯、季戊四醇 四丙烯酸酯、二季四醇五丙烯酸酯、二季戊四醇六丙烯酸 酯或含有多官能胺基甲酸乙酯丙烯酸酯系化合物之市售品 等。 前述單官能、2官能及3官能以上之（甲基）丙烯酸 -25- 200903150 酯可單獨或混合2種以上使用。 本發明之敏輻射線性樹脂組成物中，〔B〕聚合性不 飽和化合物之使用量係對於〔A〕聚合物1 〇〇重份時，使 用量較佳爲1〜120重量份，更佳爲3〜100重量份。〔b 〕聚合性不飽和化合物之使用量未達1重量份時，在顯像 時可能產生顯像殘留，而超過1 2 0重量份時，與所得之間 隔物之基板的密著性有降低的傾向。 -〔C〕敏輻射線性聚合引發劑_ 〔C〕敏輻射線性聚合引發劑係由以可見光、紫外線 、遠紫外線、荷電粒子線、X射線等輻射線曝光，產生可 使〔B〕聚合性不飽和化合物開始聚合之活性種的成份所 構成。 這種〔C〕敏輻射線性聚合引發劑，較佳例如有〇 _醯 基膀系化合物、乙醯苯系化合物、聯咪哩系化合物、苯偶 因系化合物、二苯甲酮系化合物、α -二酮系化合物、多核 醌系化合物、咕噸酮系化合物、膦系化合物、三曉系化合 物等。 〇 -醯基Η弓系化合物較佳爲9.Η.-咔唑系之〇_醯基膀型 聚合引發劑。例如有1-〔 9 -乙基-6-苯醯- 9.Η. -味哩·3·基 〕-壬院- 〗，2 -壬院-2·聘-〇-苯甲酸酯' ΐ-〔9_乙基_6_苯醯_ 9.Η.-咔唑-3-基〕-壬烷- ΐ，2-壬烷-2-肟·〇_乙酸酯、丨·〔 9_ 乙基-6-苯醯-9.Η. -咔唑-3-基〕-戊烷-1]·戊烷-2_肟_〇_乙 酸酯、1-〔9 -乙基-6-苯醯- 9.Η. -咔唑-3-基〕-辛烷-；1_酮膀_ -26 - 200903150 〇-乙酸酯、1-〔9-乙基-6-(2-甲基苯醯）-9.11.-咔唑-3-基 〕-乙烷-卜酮肟-〇-苯甲酸酯、1-〔 9-乙基-6- (2-甲基苯醯 )-9.Η.-咔唑-3-基〕-乙烷-1-酮肟-0-乙酸酯、1-〔9-乙基· 6-(1,3,5-三甲基苯醯）-9.11.-咔唑-3-基〕-乙烷-1-酮肟-0-苯甲酸酯、1-[9-丁基-6-(2-乙基苯醯）-9.：«-咔唑-3-基 ]-乙烷-1-酮肟-〇-苯甲酸酯、卜〔9-乙基-6- ( 2-甲基-4-四 氫吡喃甲氧基苯醯）-9.Η.-咔唑-3-基〕-乙烷-1-酮肟-0-乙 酸酯、1-〔 9 -乙基-6- (2 -甲基-4 -四氫呋喃甲氧基苯醯）-9.Η.-咔唑-3-基〕-乙烷-1-酮肟-0-乙酸酯、乙酮-1-〔9-乙 基-6- (2 -甲基-4 -四氫吡喃甲氧基苯醯）-9.Η.-咔唑-3-基 〕-1-(0-乙醯基肟）、乙酮- l-〔9-乙基- 6-{2-甲基- 4-( 2,2-二甲基-1，3-二氧雜環戊基）甲氧基苯醯}-9.：«.-咔唑-3-基〕-1- ( 〇-乙醯基肟）等。 追些0 -酸基胎化合物中’較佳爲1-〔 9 -乙基- 6-( 2· 甲基苯醯）-味唑-3-基〕-乙烷-1-酮肟-0-乙酸酯、1-〔9 -乙基-6- (2 -甲基-4-四氫毗喃甲氧基苯醯）_唑-3-基〕-乙烷-1-酮肟-0-乙酸酯、乙酮-l-〔9-乙基-6-{2-甲 基-4- (2,2-二甲基-1,3-二氧雜環戊基）甲氧基苯醯}-9.Η·-咔唑-3-基〕-1- ( 0-乙醯基肟）。 前述〇-醯基肟化合物可單獨或混合2種以上使用。 本發明中，藉由使用之 〇-醯基肟化合物，即使在 l,000J/m2以下之曝光量也可得到具有充分的感度、密著 性之間隔物。 前述乙醯苯系化合物例如有α-羥基酮系化合物、α-胺 -27- 200903150 基酮化合物等。 前述α -羥基酮系化合物例如有1-苯基-2-羥基-2-甲基 丙烷-1-酮、1-(4-異丙基苯基）-2-羥基-2-甲基丙烷-1-酮 、4- (2-羥基乙氧基）苯基-(2-羥基-2-丙基）酮、1-羥基 環己基苯基酮等，前述α-胺基酮系化合物例如有2-甲基-卜（4-甲基苯硫基）-2-嗎啉基丙烷-1-酮、2-苄基-2_二甲 基胺基-1-(4-嗎啉基苯基）-丁烷-1-酮、2- (4-甲基苯醯 )-2-(二甲基胺基）-1- ( 4-嗎啉基苯基）-丁烷-1-酮等， 這些以外之化合物例如有2,2-二甲氧基乙醯苯、2,2-二乙 氧基乙醯苯、2,2-二甲氧基-2-苯基乙醯苯等。 上述乙醯苯系化合物中，特佳爲2 -甲基-1-(4-甲基 苯硫基）-2-嗎啉基丙烷-1-酮、2-(4-甲基苯醯）-2-(二 甲基胺基）-卜（4-嗎啉基苯基）-丁烷-1-酮。 本發明中，倂用乙醯苯系化合物可進一步改善感度、 間隔物之形狀及壓縮強度。 又，上述二咪唑系化合物例如有2,2'-雙（2-氯苯基 )-4,4',5,5’-四（4-乙氧基羰基苯基）-1,2'-聯咪唑、2,2'-雙（2 -溴苯基）-4,4’，5,5'_四（4 -乙氧基羰基苯基）-1,2'-聯咪唑、2,2'-雙（2 -氯苯基）-4,4',5,5'-四苯基-1,2' -聯咪 唑、2,2’ -雙（2,4 -二氯苯基）-4，4'，5,5' -四苯基-1,2' -聯咪 唑、2,2'-雙（2,4,6 -三氯苯基）-4,4',5,5'-四苯基-1，2'-聯咪 唑、2，2 ' _雙（2 _溴苯基）-4，4 ’，5 , 5 '-四苯基-1 , 2 ’ -聯咪唑、 2,2'-雙（2,4-二溴苯基）-4,4'，5,5’-四苯基-1，2’-聯咪唑、 2,2、雙（2,4,6-三溴苯基）-4,4'，5,5’-四苯基-1,2'-聯咪唑等 -28- 200903150 适些聯咪哇系化合物中，較佳爲2,2，_雙（2_氯苯基 )-4,4'，5,5’-四苯基_1，2、聯咪唑、2,2，_雙（2,4-二氯苯基 )-4,4'，5,5'-四苯基-1，2，_聯咪唑、2,2，_雙（2,4,6_三氯苯基 )-4,4’，5,5'-四苯基-1，2，-聯咪唑等，特佳爲2,2，_雙（2,4_ 一氯本基）-4,4’，5,5’ -四苯基_i，2，_聯咪哩。 本發明中’倂用聯咪唑系化合物，可進—步改善感度 、解像度或所得之間隔物與基板的密著性。 倂用聯咪唑系化合物時，爲了增加感度，可添加具有 二院基胺基之脂肪族系或芳香族系之化合物（以下稱爲「 胺基系增感劑」）。 胺基系增感劑例如有N -甲基二乙醇胺、4,4'-雙（二甲 基胺基）二苯甲酮、4，4'-雙（二乙基胺基）二苯甲酮、 對-二甲基胺基苯甲酸乙酯、對-二甲基胺基苯甲酸異戊酯 等。 這些胺基系增感劑中，特佳爲4,4'-雙（二乙基胺基） 二苯甲酮。 上述胺基系增感劑可單獨或混合2種以上使用。 又，倂用聯咪唑系化合物與胺基系增感劑時，可添加 供給氫之化合物的硫醇系化合物。聯咪唑系化合物係因前 述胺基系增感劑增感而開裂，產生咪唑自由基，但是此狀 態下無法得到較高之聚合引發能，所得之間隔物大部份爲 逆錐形狀之不良形狀。但是同時含有聯咪唑系化合物與月安 基系增感劑之體系中添加硫醇系化合物時，由硫醇系化合 -29- 200903150 物將氫自由基供給咪唑自由基的結果，咪唑自由基 中性之咪唑’同時產生具有較高聚合引發能之硫自 成份，藉此間隔物形狀可形成較佳之錐狀。 該硫醇化合物例如有2 -锍基苯并噻唑、2 -毓基 唑、2 -锍基苯并咪唑、2 -锍基-5-甲氧基苯并噻唑 基-5 -甲氧基苯并咪唑等芳香族化合物；3 -锍基丙酸 基丙酸甲酯、3 -锍基丙酸乙酯、3-锍基丙酸辛酯等 單硫醇；3，6 -二噁-1 , 8 -辛烷二硫醇、季戊四醇四（ 酸酯）、季戊四醇四（3-巯基丙酸酯）等2官能以 肪族系硫醇。 這些硫醇化合物中，特佳爲2 -锍基苯并噻唑。 本發明之敏輻射線性樹脂組成物中，其他敏輻 聚合引發劑之使用比例係對於全部敏輻射線性聚合 100重量份’較佳爲100重量份以下，更佳爲80重 下’特佳爲60重量份以下。其他敏輻射線性聚合 之使用比例超過1 00重量份時，可能會影響本發明 的效果。 又’併用聯咪唑化合物與胺基系增感劑時，胺 感劑之添加量係對於二咪唑系化合物1 0 0重量份時 爲0.1〜50重量份，更佳爲i〜20重量份。胺基系 之添加量未達0 · 1重量份時，感度、解像度及密著 善效果有降低的傾向，又，超過5 0重量份時，可 及製得之間隔物的形狀。 倂用聯咪唑化合物及胺基系增感劑時，硫醇系 轉變成 由基的 苯并噁 、2-锍 、3-锍 脂肪族 锍基乙 上之脂 射線性 引發劑 量份以 引發劑 所預期 基系增 ，較佳 增感劑 性之改 能會損 化合物 -30- 200903150 之添加量係對於聯咪唑系化合物1 00重量份時，較佳爲 0 · 1〜5 0重量份’更佳爲1〜2 0重量份。硫醇系化合物之 添加量未達〇. 1重量份時，間隔物形狀之改善效果降低， 或有容易產生膜減少的傾向，又，超過50重量份時，可 能損及製得之間隔物的形狀。 -添加劑- 本發明之敏輻射線性樹脂組成物，在不影響本發明所 預期之效果的範圍內，必要時，除了上述成份外，可添加 界面活性劑、接著助劑、保存安定劑、耐熱性提昇劑等之 添加劑。 前述界面活性劑爲具有改善塗佈性之作用的成份，較 佳爲氟系界面活性劑、聚矽氧系界面活性劑。 前述氟系界面活性劑較佳爲末端、主鏈及側鏈中至少 一部位具有氟烷基或氟伸烷基之化合物，其具體例爲 1,1，2,2-四氟辛基（1，1，2,2-四氟-正丙基）醚、1，1,2,2-四 氟-正辛基（正己基）醚、八乙二醇二（1，1，2,2_四氟-正丁 基）醚、六乙二醇（1，1，2,2,3,3-六氟-正戊基）醚、八丙 二醇二（1，1，2,2 -四氟-正丁基）醚、六丙二醇二（ 1，1，2,2,3,3 -六氟·正戊基）醚、；1,12,2,3,3 -六氟_正癸烷、 1，1，2,2,8,8,9,9，10，10-十氟·正十二烷、全氟-正十二烷基磺 酸鈉，或氟烷基苯磺酸鈉、氟烷基膦酸鈉、氟烷基羧酸鈉 、氟院基聚氧乙烯醚、二甘油四（氟烷基聚氧乙烯醚）、 氟i：兀基姚化銨、氟烷基甜菜鹼、氟烷基聚氧乙烯醚、全氟 -31 - 200903150 烷基聚氧乙醇、全氟烷基烷氧化物、氟系烷基酯等。 又’氟系界面活性劑之市售品如，商品名表示例如有 BM- 1 000、同·1 1〇〇 (以上爲 BM CHEMIE 公司製）； MEGAFAC F142D、同 F 1 7 2、同 F 1 7 3、同 F 1 8 3、同 F 1 7 8 、同F191、同F4 71、同F4 76(以上爲大日本油墨化學工 業（股）製）；Fluorad FC-170C、同 FC-171、同 FC-430 、同 FC-431 (以上爲住友 3M (股）製）；SurflonS-112 、同 S-113、同 S-131、同 S-141、同 S-145、同 S-382、 同 SC-101、同 SC-102、同 SC-103、同 SC-104、同 SC-105、同SC-106(以上爲旭硝子（股）製）；FTOP EF301 、同EF 3 03、同EF3 52 (以上爲新秋田化成（股）製）； FTERGENT FT-100、同 FT-110、同 FT-140A、同 FT-150 、同 FT-25 0、同 FT-251、同 FTX-251、同 FTX-218、同 FT-300、同 FT-310、同 FT-400S(以上爲 Neos (股）製 )等。 上述聚矽氧系界面活性劑之市售品，其商品名例如有 東麗 silicone DC3PA、同 DC7PA、同 SH11PA、同 SH21PA、同 SH28PA、同 SH29PA、同 SH30PA、同 SH-190、同 SH-193、同 SZ-603 2、同 SF- 842 8、同 DC-57、同 DC-190(以上爲東麗 Dowchemical silicone (股）製）； TSF-4440 、同-4300 、同-4445 、同-4446 、同-4460 、同-4452(以上爲GE東芝silicone (股）製）等。 上述以外之界面活性劑例如有聚氧乙烯月桂醚、聚氧 乙烯硬脂醚、聚氧乙烯油醚等聚氧乙烯烷醚；聚氧乙烯正 -32- 200903150 辛基苯醚、聚氧乙烯正壬基苯醚等聚氧乙烯芳醚；聚氧乙 烯二月桂酸酯、聚氧乙烯二硬脂酸酯等聚氧乙嫌二院醚等 非離子系界面活性劑；或市售品之商名例如有KP34丨（信 越化學工業（股）製）、P〇lyfl〇wNo.57、Ν〇·95 (共榮社 (股）製）等。 這些界面活性劑可單獨或混合2種以上使用。 界面活性劑之添加量係對於〔A〕聚合物1 〇 〇重量份 時’較佳爲5重量份以下’更佳爲2重量份以下。界面活 性劑之添加量超過5重量份時’在塗佈時易產生膜粗糙的 傾向。 上述接著助劑爲具有更進一步改善間隔物與基體之密 著性之作用的成份，較佳爲官能性矽烷偶合劑。 前述官能性砂院偶合劑’例如具有殘基、甲基丙烯酿 基、乙烯基、異氰酸酯基、環氧基等反應性官能基的化合 物。具體而言，例如有三甲氧基甲砂院基苯甲酸、γ_甲基 丙烯醯氧基丙基三甲氧基矽烷 '乙烯基三乙醯氧基矽烷、 乙烯基三甲氧基矽烷、γ -異氰酸酯丙基三乙氧基矽烷、γ-環氧丙氧基丙基三甲氧基矽烷、2- (3,4 -環氧環己基）乙 基三甲氧基矽烷等。 這些接著助劑可單獨或混合2種以上使用。 接著助劑之添加量係對於〔A〕聚合物1 0 0重量份時 ，較佳爲2 0重量份以下，更佳爲1 〇重量份以下。接著助 劑之添加量超過2 0重量份時’有容易產生顯像殘留的傾 向。 -33- 200903150 上述保存安定劑例如有硫、醌類、氫醌類、聚羥基化 合物、胺、硝基亞硝基化合物等，更具體例如有4-甲氧基 苯酚、N-亞硝基-N-苯基羥基胺鋁等。 這些保存安定劑可單獨或混合2種以上使用。 保存安定劑之添加量係對於〔A〕聚合物100重量份 時，較佳爲3重量份以下，更佳爲o.ooi〜〇,5重量份。保 存安定劑之添加量超過3重量份時，感度降低，可能損及 圖型形狀。 上述耐熱性提昇劑例如有N-(烷氧基甲基）甘脲化 合物、N-(烷氧基甲基）三聚氰胺化合物。 前述 N-(烷氧基甲基）甘脲化合物例如有 N,N，N，，N’-四（甲氧基甲基）甘脲、Ν,Ν,Ν’，Ν，-四（乙氧 基甲基）甘脲、Ν，Ν，Ν’，Ν’ -四（正丙氧基甲基）甘脲、 Ν，Ν，Ν，，Ν’-四（異丙氧基甲基）甘脲、Ν,Ν,Ν’，Ν，-四（正 丁氧基甲基）甘脲、Ν，Ν，Ν’，Ν’-四（第三丁氧基甲基）甘 脲等。 這些Ν-(烷氧基甲基）甘脲化合物中，特佳爲 ν，ν，ν’，ν’-四（甲氧基甲基）甘脲。 上述Ν-(烷氧基甲基）三聚氰胺化合物例如有 ν，ν,ν，，ν’，ν’’，ν’’-六（甲氧基甲基）三聚氰胺、 ν,ν,ν，，ν，，ν’’，ν’’-六（乙氧基甲基）三聚氰胺、 ν，ν,ν，，ν，，ν，，，ν’’-六（正丙氧基甲基）三聚氰胺' ν,ν，ν，，ν，，ν，，，ν，’-六（異丙氧基甲基）三聚氣胺' Ν,Ν，Ν，，Ν，，Ν，’，Ν’’-六（正丁氧基甲基）三聚氰胺、 -34- 200903150 N，N，N’，N’，N’’，N’’-六（第三丁氧基甲基）三聚氰胺等。 這些N-(烷氧基甲基）三聚氰胺化合物中，特佳爲 沐叱^4’，>^，>^’，1^’-六（甲氧基甲基）三聚氰胺，其市售品 之商品名例如有Nikalac N-2 702、同MW-30M (以上爲三 和化學（股）製）等。 前述耐熱性提昇劑可單獨或混合2種以上使用。 耐熱性提昇劑之添加量係對於〔A〕聚合物1 00重量 份，較佳爲30重量份以下，更佳爲20重量份以下。耐熱 性提昇劑之添加量超過3 0重量份時，敏輻射線性樹脂組 成物之保存安定性有降低的傾向。 本發明之敏輻射線性樹脂組成物係以溶解於適當溶劑 之組成物溶液的形態來使用較佳。 前述溶劑係使用均勻溶解構成敏輻射線性樹脂組成物 之各成份，且不與各成份反應，具有適度揮發性者，但是 從各成份之溶解能、與各成份之反應性及塗膜形成之容易 性的觀點，較佳爲醇、乙二醇單烷醚乙酸酯、二乙二醇單 烷醚乙酸酯、二乙二醇烷醚、丙二醇單烷醚乙酸酯、二丙 二醇烷醚、烷氧基丙酸烷酯、乙酸酯等，特佳爲苄醇、2-苯基乙醇、3-苯基-卜丙醇、乙二醇單正丁醚乙酸酯、二乙 二醇單乙醚乙酸酯、二乙二醇二甲醚、二乙二醇二乙醚、 二乙二醇乙基甲醚、丙二醇單甲醚乙酸酯、丙二醇單乙醚 乙酸酯、二丙二醇二甲醚、乙酸3 -甲氧基丁酯、乙酸2 -甲 氧基乙酯等。 這些溶劑可單獨或混合2種以上使用。 -35- 200903150 本發明中，尙可倂用前述溶劑及高沸點溶劑。 前述高沸點溶劑例如有N_甲基甲醯胺、ν,ν·二甲基 甲醯胺、Ν-甲基甲醯苯胺、Ν_甲基乙醯胺、Ν，Ν_:甲基乙 醯胺、Ν-甲基吡咯烷酮、二甲基亞、苄基乙醚、二-η-己 醚、丙酮基丙酮、異氟爾酮、己酸、辛酸、1-辛醇、1-壬 醇、苄醇、乙酸苄酯、苯甲酸乙酯、草酸二乙酯、順丁烯 一酸一乙醋、γ· 丁內酯、碳酸乙嫌酯、碳酸丙燒酯、乙二 醇單苯醚乙酸酯等。 這些高沸點溶劑可單獨或混合2種以上使用。 又’如上述調製之組成物溶液係使用孔徑0.5 μιη之微 孔過濾器等過濾後再供使用。 本發明之敏輻射線性樹脂組成物特別適用於形成液晶 顯示元件用之間隔物。 間隔物之形成方法 以下使用本發明之敏輻射線性樹脂組成物說明形成本 發明之液晶顯示元件用間隔物的方法。 本發明之液晶顯示元件用間隔物之形成方法，其係至 少含有依下述順序之以下步驟。 (甲）在基板上形成本發明之敏輻射線性樹脂組成物 之被膜的步驟， (乙）對該被膜之至少一部份進行曝光的步驟， (丙）曝光後之被膜進行顯像的步驟及 (丁）對顯像後之被膜進行加熱之步驟。 -36- 200903150 以下依序說明這些各步驟。 -(甲）步驟- 在透明基板之單面上形成透明導電膜，將敏輻射線性 樹脂組成物較佳爲形成組成物溶液塗佈於該透明導電膜上 後，塗佈面經加熱，即預烘烤形成被膜。 間隔物形成用之透明基板，例如有玻璃基板、樹脂基 板等’更具體例有鹼石灰玻璃、無鹼玻璃等玻璃基板；聚 對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚醚、聚碳 酸酯、聚醯亞胺等塑料所構成之樹脂基板。 設置於透明基板之一面的透明導電膜可使用由氧化錫 (Sn02 )所構成之NESA膜（美國PPG公司註冊商標）、 由氧化銦-氧化錫（In203-Sn02 )所構成之ITO膜等。 組成物溶液之塗佈方法係形成本發明之敏輻射線性樹 脂之被膜的方法，例如可使用（1 )塗佈法、（2 )乾薄膜 法。 組成物溶液之塗佈方法可採用噴霧法、輥塗佈法、旋 轉塗佈法（旋塗法）、縫模塗佈法、棒塗佈法、噴墨塗佈 法等適當方法，特佳爲旋塗法、縫模塗佈法。 形成本發明之敏輻射線性樹脂組成物之被膜，採用（ 2 )乾薄膜法時，該乾薄膜較佳爲將本發明之敏輻射線性 樹脂組成物所構成之敏輻射線性層層合於基礎薄膜，較佳 爲可撓性之基礎薄膜上所構成者（以下稱爲「敏輻射線性 乾薄膜」）。 -37- 200903150 ±述敏輻射線性乾薄膜係將本發明之敏輻射線性樹脂 組成物’或液狀組成物塗佈於基礎薄膜上後，經乾燥層合 敏輻射線性層來形成的。敏輻射線性乾薄膜之基礎薄膜例 如可使用聚對苯二甲酸乙二醇酯（PET)、聚乙烯、聚丙 烯、聚碳酸酯、聚氯乙烯等之合成樹脂薄膜。基礎薄膜之 厚度理想爲1 5〜1 25 μπα。所得之敏輻射線性層之厚度較佳 爲 1 〜3 0 μηι 〇 敏輻射線性乾薄膜在不使用時，敏輻射線性層上可層 合保護薄膜來保存。此保護薄膜在不使用時，不會剝離， 使用時容易剝離。滿足這種條件之保護薄膜可使用例如 PET薄膜、聚丙烯薄膜、聚乙烯薄膜、聚氯乙烯等之合成 樹脂薄膜之表面塗佈或烘烤聚矽氧系離型劑的薄膜。保護 薄膜之厚度通常爲25 μιη。 預烘烤之條件係因各成份之種類、使用比例等而異， 通常爲70〜120 °C，1〜15分鐘。 -(乙）步驟- 其次，將形成之被膜之至少一部份曝光。此時，被膜 之一部份曝光時’通常經由具有所定圖型之光罩進行曝光 〇 曝光用之輻射射線例如可使用可見光、紫外線、遠紫 外線、電子線、X射線等，但以波長1 9 0〜4 5 0nm之輻射 線較佳，特佳爲含3 6 5 n m紫外線之輻射線。 曝光量係以照度計（OAI model 356、OAI Optical -38- 200903150200903150 The following spacer for liquid crystal display elements is obtained by using a radiation sensitive linear resin composition. The sensitive radiation linear resin composition for a spacer for a liquid crystal display element is the above-mentioned radiation sensitive linear resin composition, and a sensitive radiation linear resin composition containing a [B] superabsorbent unsaturated compound and a [C] radiation sensitive linear polymerization initiator (hereinafter It is called "sensitive radiation linear resin composition for spacers for liquid crystal display elements"). According to the present invention, the above objects and advantages of the present invention can be attained by forming a spacer for a liquid crystal display element formed by the above-mentioned respective radiation-sensitive linear resin compositions. According to the present invention, the above objects and advantages of the present invention can be attained by the method for forming a spacer for a liquid crystal display element. The method for forming a spacer for a liquid crystal display device, comprising the steps of at least the following steps, and (a) forming a film of the photosensitive radiation linear resin composition for a spacer for a liquid crystal display device on a substrate (b) a step of exposing at least a portion of the film, (c) a step of developing the film after exposure, and a step of heating the film after (d) development. According to the present invention, the above object and advantages of the present invention can be achieved by the liquid crystal display device including the spacer for a liquid crystal display device. The present invention will be described in detail below. _ 8 - 200903150 The present invention will be described in detail below. - [A] Polymer _ The composition of the present invention is an isocyanate group compound represented by the above formula (1) (hereinafter referred to as "unsaturated isocyanate compound (1) j ) and (al) is selected from the group consisting of [A1]. a polymer obtained by reacting at least one of a group of a carboxylic acid and an unsaturated carboxylic anhydride with a copolymer of an unsaturated compound containing at least one hydroxyl group in (a2) 1 molecule (hereinafter referred to as "copolymer [α]") ( Hereinafter, "[Α] polymer") and [Α2] (al) are selected from at least one of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride group, and (a3) has an oxocycloethyl group or an oxocyclobutyl group. A copolymer of an unsaturated compound (hereinafter referred to as "copolymer [β]"). Among the components constituting the copolymer [α] and the copolymer [β], a carboxylic acid or an unsaturated carboxylic anhydride (hereinafter collectively referred to as "(a 1 ) unsaturated carboxylic acid compound") is, for example, acrylic acid, methacrylic acid or crotonic acid. , 2-propenyloxyethyl succinic acid, 2-methylpropenyloxyethyl succinic acid, 2-propenyloxyethylhexahydrophthalic acid, 2-methylpropenyloxyethyl a monocarboxylic acid such as hexahydrophthalic acid; a dicarboxylic acid such as maleic acid, fumaric acid, citraconic acid, mesaconic acid or itaconic acid; an acid anhydride of the above dicarboxylic acid; Among these (a1) unsaturated phthalic acid compounds, acrylic acid, methacrylic acid, and cis-butylene are preferred from the viewpoints of copolymerization reactivity, solubility of the obtained polymer and copolymer to an alkali developing solution, and ease of availability. Aqueous dianhydride and the like. -9- 200903150 The (al) unsaturated carboxylic acid compound of the copolymer [α] and the copolymer [β] may be used singly or in combination of two or more. In the copolymer [α] and the copolymer [β], the content of the repeating unit derived from the (al) unsaturated citric acid compound is preferably 5 to 50% by weight, more preferably 10 to 40% by weight, particularly preferably 15 ~30% by weight. When the content of the repeating unit derived from the (al) unsaturated carboxylic acid compound is less than 5% by weight, the solubility of the polymer obtained by the reaction with the unsaturated isocyanate compound (1) tends to decrease in the solubility of the alkali developing solution, and exceeds At 50% by weight, the solubility of the polymer in the alkali imaging solution may be excessive. Further, (a2) an unsaturated compound containing at least one hydroxyl group in one molecule, for example, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, acrylic acid 6 -Hydroxyhexyl ester, 7-hydroxyheptyl acrylate, 8-hydroxyoctyl acrylate, 9-hydroxydecyl acrylate, 10-hydroxydecyl acrylate, 11-hydroxyundecyl acrylate, 12-hydroxydodecan acrylate Hydroxyalkyl ester; 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 6-hydroxyhexyl methacrylate, A 7-hydroxyheptyl acrylate, 8_ hydroxyoctyl methacrylate, 9-hydroxy decyl methacrylate, 1 癸 hydroxy hydroxy methacrylate, 11-hydroxyundecyl methacrylate, methacrylic acid 12- Hydroxydodecanyl hydroxyalkyl methacrylate; 4-hydroxy-cyclohexyl acrylate, 4-hydroxymethyl-cyclohexylmethyl acrylate, 4-hydroxyethyl-cyclohexylethyl acrylate, 3-hydroxy-acrylic acid Bicyclo[2.2.1]hept-5-en-2-yl ester, 3-hydroxymethyl acrylate- Bicyclo[2.2.1] -10- 200903150 Glysyl-5-en-2-ylmethyl ester, 3-hydroxyethyl-bicyclo[2.2.1]hept-5-ene-2-ylethyl acrylate, acrylic acid 8- Hydroxy-bicyclo[2.2.1]hept-5-en-2-yl ester, 2-hydroxy-octahydro- 4,7-methyl-p-5-yl acrylate, 2-hydroxymethyl-octahydro acrylate 4,7-A-indole-: 5-methyl ester, 2-hydroxyethyl-octahydro- 4,7-methyl-indol-5-ylethyl acrylate, 3-hydroxy-adamantyl acrylate, acrylic acid 3-hydroxymethyl-adamantane-i-methyl ester, 3-hydroxyethyl-adamantane-1-ethyl acrylate, hydroxyalkyl acrylate having an alicyclic structure; 4-hydroxy-cyclomethacrylate Hexyl ester, 4-hydroxymethyl _ cyclohexyl methyl methacrylate, 4-hydroxyethyl-cyclohexyl methacrylate, 3-hydroxy-bicyclo[2.2.1]hept-5-ene methacrylate 2-Based ester, 3-hydroxymethyl-bicyclo[2.2.1]hept-5-en-2-ylmethyl methacrylate, 3-hydroxyethyl-bicyclo[2.2.1]hept-5 -al-2-ylethyl ester, 8-hydroxy-bicyclo[2.2.1]hept-5-en-2-yl methacrylate, 2-hydroxy-octahydro-4,7-methyl methacrylate茚-5-yl ester, 2-hydroxymethyl methacrylate - Octahydro-4,7-methyl-indo-5-ylacetoacetate 'methylpropane acid 2-transethylethyl-octahydro-4,7-methyl-knot 5-ethyl ester, methacrylic acid 3 -hydroxy-adamantane-bupropion ester, 3-hydroxymethyl-adamantane-1 -ylmethyl methacrylate, 3-hydroxyethyl-adamantane-1-ylethyl methacrylate having an alicyclic group Structure of hydroxyalkyl methacrylate; 1,2-dihydroxyethyl acrylate, 2,3-dihydroxypropyl acrylate, 1,3-dihydroxypropyl acrylate, 3,4-dihydroxybutyl acrylate, acrylic acid Dihydroxyalkyl acrylate such as 3-[3-( 2,3 -dihydroxypropoxy)-2-hydroxypropyloxy]-2-hydroxypropyl ester; 1,2-dihydroxyethyl methacrylate, 2,3-dihydroxy-11 - 200903150 methacrylate, 1,3-dihydroxypropyl methacrylate, 3,4-dihydroxybutyl methacrylate, 3-[3- ( 2 A dihydroxyalkyl methacrylate or the like such as 3-hydroxypropyloxy-2-hydroxypropoxy]-2-hydroxypropyl ester. Among the unsaturated compounds having at least one hydroxyl group in one molecule, from the viewpoints of copolymerization reactivity and reactivity with an isocyanate compound, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, and 4-hydroxy acrylate are preferable. Butyl ester, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 4-hydroxymethylcyclohexyl methyl acrylate, 4-hydroxymethyl methacrylate - cyclohexylmethyl ester, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, and the like. In the component (a2), the unsaturated compound having a hydroxyl group represented by the above formula (2) is particularly preferable from the viewpoint of improving the development performance or improving the compression properties of the obtained spacer. Specific examples thereof are 2-(6.hydroxyhexyloxy)ethyl acrylate, 3-(6-hydroxyhexyloxy)propyl acrylate, 4-(6-hydroxyhexyloxy)butyl acrylate, and C. 5-(6-hydroxyhexyloxy)pentyl dilute acid, 6-(6-hydroxyhexyloxy)hexyl acrylate, 6-hydroxyhexyloxyalkyl acrylate; 2-(methacrylic acid) 6-Hydroxyhexyloxy)ethyl ester, 3-(6-hydroxyhexyloxy)propyl methacrylate, 4-(6-hydroxyhexyloxy)butyl methacrylate, methacrylic acid 5- (6-Hydroxyethylhexyloxy)pentyl ester, 6-(6-hydroxyhexyloxy)hexyl methacrylate (6-hydroxyhexyloxy) alkyl methacrylate; among these, Acrylic acid 2·(6-hydroxyhexyloxy)ethyl ester-12- 200903150, 2-(6-hydroxyhexyloxy)ethyl methacrylate, and 2-(6-hydroxyhexanyl methacrylate) Commercially available products of a mixture of oxy)ethyl ester and 2-hydroxyethyl methacrylate are available, for example, under the trade names of PLACCEL FM1D, FM2D (manufactured by Daicel Chemical Industry Co., Ltd.). In the copolymer [α], (a2) one or more kinds of the unsaturated compounds having at least one of the groups may be used alone or in combination of two or more. In the copolymer [α], the content of the repeating unit derived from the unsaturated compound containing at least one hydroxyl group in the (a2) molecule is preferably from 1 to 50% by weight, more preferably from 3 to 40% by weight, Particularly preferred is 5 to 30% by weight. When the content of the repeating unit derived from the unsaturated component of at least one hydroxyl group in the (a2) molecule is less than 1% by weight, the introduction ratio of the unsaturated isocyanate compound (1) to the polymer is lowered, and the sensitivity tends to decrease. When the amount is more than 50% by weight, the storage stability of the polymer obtained by the reaction with the unsaturated isocyanate compound (1) tends to be lowered. The unsaturated compound having an oxocycloethyl group or an oxocyclobutyl group of (a3) of the copolymer [/3] is, for example, glycidyl acrylate, 2-methylglycidyl acrylate, 4-hydroxybutyl acrylate glycidol. Ethylene acrylate (cyclo)alkyl ester of ether, 3,4-epoxybutyl acrylate, 6,7-epoxyheptyl acrylate, 3,4-epoxycyclohexyl acrylate, etc.; methacrylic acid shrinkage Glyceride, 2-methylglycidyl methacrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl methacrylate, 3,4-epoxy methacrylate Cyclohexyl ester, 3,4-epoxycyclohexylmethyl methacrylate, etc., methacrylic acid epoxy (cyclo)alkyl ester; α-ethyl methacrylate glycidyl ester, propyl acrylic acid glycidyl-13 - 200903150 Ester, α-η-butyl glycidyl acrylate, α-ethyl acrylate 6,7-epoxyheptyl ester, α-ethyl acrylate 3,4-epoxycyclohexyl ester, etc. Cycloalkyl (cyclo)alkyl acrylate; 〇-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, P-vinyl benzyl glycidyl ether, etc. Glycerol ethers. 3-(methacryloxymethyl)oxetane, 3-(methacryloxymethyl)-3-ethyloxetane, 3-(methacryloxyloxy) Methyl)-2-methyloxetane, 3-(methacryloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloxymethyl) --2-pentafluoroethyloxetane, 3-(methacryloxymethyl)-2-phenyloxetane, 3-(methacryloxymethyl)- 2,2-difluorooxetane, 3-(methacryloxymethyl)-2,2,4-trifluorooxetane, 3-(methacryloxymethyl) )-2,2,4,4-tetrafluorooxetane, 3-(methacryloxyethyl)oxetane, 3·(methacryloxyethyl)-3 -ethyloxetane, 2-ethyl-3-(methacryloxyethyl)oxetane, 3-(methacryloxyethyl)-2-trifluoromethyl Oxycyclobutane, 3-(methacryloxyethyl)-2-pentafluoroethyloxetane, 3-(methacryloxyethyl)-2-phenyloxy Heterocyclobutane, 2,2-difluoro-3-(methacryloxyethyl)oxetane 3_(Methethyloxyethyl)_2,2,4-trifluorooxetane, 3-(methacryloxyethyl)-2,2,4,4-tetrafluorooxetane Methyl propyl amide such as alkane; 3-(acryloxymethyl) oxetane, 3-(propyl decyloxymethyl)-3-ethyloxetane, 3-( Propylene oxime oxymethyl) 2 - methyl-14- 200903150 oxetane, 3-(acryloxymethyl)-2-trifluoromethyl oxetane, 3-(propylene oxime Methyl)-2-pentafluoroethyl oxetane, 3-(propylene methoxymethyl)-2-phenyl oxetane, 3-(acryloxymethyl)-2 ,2-difluorooxetane, 3-(propenyloxymethyl). 2,2,4-trifluorooxetane, 3-(propyleneoxymethyl)-2,2, 4,4·tetrafluorooxetane, 3-(acryloxyethyl)oxetane, 3-((acryloyloxyethyl)-3-ethyloxetane, 2 - Ethyl 3-(propenyloxyethyl)oxetane, 3-(acryloxyethyl)_2-trifluoromethyloxetane, 3-(acryloxyethyl) -2 - pentafluoroethyl oxetane, 3-(acryloxyethyl)_2_benzene Oxetane, 2,2-difluoro-3-(propylcanthoxyethyl)oxetane, 3-(propenyloxyethyl)-2,2,4-trifluorooxocycle Butane, 3_(acryloxyethyl)·2,2,4,4-tetrafluoro < Aroprofen such as oxetane. Among them, from the viewpoint of polymerizability, it is particularly preferably glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, 3-methyl _ 3_ (Meth) propylene methoxymethyl oxetane, 3-ethyl-3-(methyl) propylene methoxymethyl oxetane, methacryloxymethyl)- 3-Ethyloxetane and the like. In the copolymer [β], (a3) may be used singly or in combination of two or more kinds, and the content of the repeating unit derived from (a3) in the ruthenium copolymer [β] is preferably 0·5 to 70% by weight, more preferably Good for 丨~6 〇% by weight, especially preferably 3 to 50% by weight. The content of the repeating unit from (a3) is not up to 〇. The heat resistance of the copolymer obtained at 5% by weight tends to decrease, and when it exceeds 7 〇 by weight -15 to 200903150%, the storage stability of the copolymer tends to decrease. Further, among the copolymer [α] and the copolymer [β], other unsaturated compounds different from (ai), (a2) and (a3) can be used as a component of the copolymer. Specific examples thereof include alkyl acrylate such as methyl acrylate, η-propyl acrylate, i-propyl acrylate, η-butyl acrylate, sec-butyl acrylate, and t-butyl acrylate; methyl methacrylate, Ethyl methacrylate, η-propyl methacrylate, i-propyl methacrylate, η-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, etc. Ester; cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclohexyl acrylate [5. 2. 1. 02'6] decane-8-ester, 2-(tricyclo[5. 2. 1. 02'6] decyl-8-yloxy)ethyl ester, isopropyl acrylate such as isobornyl acrylate; cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, methacrylic acid Ring [5. 2. 1. 02,6] decane-8-ester, 2-(tricyclic) methacrylate [5. 2. 1. 02,6] decyl-8-yloxy)ethyl ester, isobornyl methacrylate, etc.; aryl or arylalkyl acrylate of phenyl acrylate, benzyl acrylate, etc. » An aryl or aralkyl ester of methacrylic acid such as phenyl methacrylate or benzyl methacrylate; diethyl maleate, diethyl fumarate, diethyl itaconate, etc. Unsaturated dicarboxylic acid dialkyl ester; tetrahydrofuran-2-enyl acrylate, tetrahydropyran-2-yl acrylate, 2-methyltetrahydropyran-2-enyl acrylate, etc. Oxide 6 -16- 200903150 acrylate of the ring; tetrahydrofuran-2-methacrylate, tetrahydropyran-2 _ methacrylate, 2-methyltetrahydropyran-2- methacrylate, etc. a methyl acrylate having an oxygen-containing heterocyclic ring or an oxygen-containing heterocyclic ring; styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, p-甲a acetylene-based aromatic compound such as oxyphenylene; a conjugated diene compound such as 1,3-butadiene, isoprene or 2,3-dimethyl-1,3-butadiene; Acrylonitrile, methacryl , Acrylamide, methyl acrylamide, vinyl chloride, vinylidene chloride, vinyl acetate and the like. Among these, from the viewpoint of copolymerization reactivity, n-butyl methacrylate, 2-methyl glycidyl acrylate, benzyl methacrylate, methacrylic acid tricyclo[5_2. 1_02'6] decane-8-ester, styrene, p-methoxystyrene, tetrahydrofuran-2-methacrylate, 1,3-butadiene, and the like. In the copolymer [α] and the copolymer [β], other unsaturated compounds different from (al), (a2) and (a3) may be used alone or in combination of two or more. In the copolymer [α] and the copolymer [β], the content of the repeating unit derived from other unsaturated compounds different from (al), (a2) and (a3) is preferably from 1 7 to 70% by weight. More preferably, it is from 2 0 to 50% by weight, particularly preferably from 3 to 50% by weight. When the content of the repeating unit is less than 1% by weight, the molecular weight of the copolymer tends to decrease, and when it exceeds % by weight, the effects of the components (al), (a2) and (a3) are lowered. The copolymer [α] and the copolymer [β] are produced by polymerization in the presence of a free radical polymerization initiator in a suitable solvent. -17- 200903150 The solvent for the polymerization is, for example, an alcohol such as methanol, ethanol, n-propanol or isopropanol; an ether such as tetrahydrofuran or dioxane; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether or ethylene glycol; Ethylene glycol monoalkyl ether such as alcohol mono-n-propyl ether or ethylene glycol mono-n-butyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate Ethylene glycol monoalkyl ether acetate such as ester, ethylene glycol mono-n-butyl ether acetate; ethylene glycol monomethyl ether propionate, ethylene glycol monoethyl ether propionate, ethylene glycol mono-n-propyl ether Ethylene glycol monoalkyl ether propionate such as ester, ethylene glycol mono-n-butyl ether propionate; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol Diethylene glycol alkyl ether such as alcohol diethyl ether or diethylene glycol methyl ether; propylene glycol monomethyl ether such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether; dipropylene glycol monomethyl ether Dipropylene glycol alkyl ether such as dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol methyl ether; propylene glycol monomethyl ether Propylene glycol monoalkyl ether acetate such as ester, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono-n-butyl ether acetate; propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, Propylene glycol mono-n-propyl ether propionate, propylene glycol mono-n-butyl ether propionate and other propylene glycol monoalkyl ether propionic acid, aromatic hydrocarbons such as toluene and xylene; -18- 200903150 methyl ethyl ketone, 2-pentanone, Ketones such as 3-pentanone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone; methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxy N-propyl propyl propionate, n-butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, n-propyl 2-ethoxypropionate, 2 · n-butyl ethoxypropionate, methyl 2-n-propoxypropionate, ethyl 2-n-propoxypropionate, n-propyl 2-n-propoxypropionate, 2-n-propoxy N-butyl propionate, methyl 2-n-butoxypropionate, ethyl 2-n-butoxypropionate, n-propyl 2-n-butoxypropionate, n-butyl 2-n-butoxypropionate Ester, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, n-propyl 3-methoxypropionate n-Butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, n-propyl 3-ethoxypropionate, 3-ethoxypropionic acid Butyl ester, methyl 3-n-propoxypropionate, ethyl 3-n-propoxypropionate, n-propyl 3-n-propoxypropionate, n-butyl 3-n-propoxypropionate, 3 - alkoxypropionic acid such as methyl n-butoxypropionate, ethyl 3-n-butoxypropionate, n-propyl 3-n-butoxypropionate, n-butyl 3-n-butoxypropionate Alkyl ester; and methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, ethyl hydroxyacetate, n-propyl glycolate, n-butyl glycolate, 4-methoxybutyl acetate, acetic acid 3 -Methoxybutyl ester, 2-methoxybutyl acetate, 3-ethoxybutyl acetate, 3-propoxybutyl acetate, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate Ester, methyl 2-hydroxy-2-methylpropanoate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, 3-hydroxypropionic acid Propyl ester, n-butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, -19- 200903150 methoxy Ethyl acetate, n-propyl methoxyacetate, n-butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, n-propyl ethoxyacetate, n-butyl ethoxyacetate , n-propoxyacetic acid methyl ester, n-propoxyacetic acid ethyl acetate, n-propoxy-n-propyl acetate, n-butyl n-propoxyacetate, methyl n-butoxyacetate, ethyl n-butoxyacetate Other esters such as n-butoxy n-propyl ester and n-butyl n-butoxyacetate. Among these solvents, 'diethylene glycol alkyl ether, propylene glycol monoalkyl ether acetate, alkyl alkoxy propionate and the like are preferred. These solvents may be used alone or in combination of two or more. Further, the radical polymerization initiator is not particularly limited, and is, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis-(2,4-dimethylvaleronitrile), 2,2'- Azobis-(4-methoxy-2,4-dimethylvaleronitrile), 4,V-azobis(4-cyanovaleric acid), dimethyl-2,2'-azobis An azo compound such as (2-methylpropionate) or 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile); benzoquinone peroxide, peroxidized laurel, An organic peroxide such as a third butyl peroxy trimethyl acetate or a 1,1-bis(t-butylperoxy)cyclohexane; hydrogen peroxide or the like. When a peroxide is used as the radical polymerization initiator, a reducing agent may be used as a redox type initiator. These radical polymerization initiators can be used singly or in combination of two or more. The copolymer [α] obtained above may be used for the production of the polymer [A] in a solution state or by the separation of the solution and then the supply of the polymer [A]. The polyphenylene oxide-based weight average molecular weight of the copolymer [(X] and the copolymer [β] by gel permeation chromatography (GPC) (hereinafter referred to as "Mw") -20-200903150 is preferably 2,000 to 100,000' It is preferably 5,000 to 50,000. In this case, when the Mw is less than 2,000, the alkali imageability and residual film ratio of the obtained film may be lowered, or the shape and heat resistance may be impaired, and more than 1 〇〇 may be caused. In the case of hydrazine, the resolution is lowered or the shape of the pattern may be impaired. The polymer [A] of the present invention is obtained by reacting an unsaturated isocyanate compound (1) with a copolymer [α]. Unsaturated isocyanate compound (1) For example, 2-propenyloxyethyl isocyanate, 3-propenylmethoxypropyl isocyanate, 4-propenyloxybutyl isocyanate, 6-propenyloxyhexyl isocyanate, 8-propenyloxyoctyl isocyanate , ίο-acrylic acid derivative such as propylene decyl decyl isocyanate; 2-methyl propylene methoxyethyl isocyanate, 3-methyl propylene methoxy propyl isocyanate, 4-methyl propylene oxy butyl Isocyanate, 6-methacryloxyl hexyl a methacrylic acid derivative such as a cyanate ester, 8-methylpropenyloxyoctyl isocyanate or 10-methylpropenyloxydecyl isocyanate. Further, a commercially available product of 2-propenyloxyethyl isocyanate It is marketed as karenz ΑΟΙ (made by Showa Denko Co., Ltd.) and 2-methyl propylene methoxyethyl isocyanate, and its trade name is karenzMOI (made by Showa Denko Co., Ltd.). The isocyanate compound (1) is preferably 2-propenyloxyethyl isocyanate, 2-methylpropenyloxyethyl isocyanate or 4-methylpropene from the viewpoint of reactivity with the copolymer [α]. In the polymer [A], the unsaturated isocyanate compound (1) may be used singly or in combination of two or more. In the present invention, the copolymer [〇〇 and an unsaturated isocyanate compound ( 1) The reaction is, for example, in a copolymer [α] solution containing a catalyst such as di-n-butyltin dilaurate (IV) or a polymerization stopper such as p-methoxyphenol, stirred at room temperature or under heating. Under, input unsaturated isocyanate The ester compound (1) is reacted. The unsaturated isocyanate compound (1) used in the production of the polymer [A] is used as an unsaturated compound having at least one hydroxyl group in the (a2) 1 molecule of the copolymer [α]. The hydroxyl group is 1 equivalent, preferably 0.  1 to 9 5 Mo %, more preferably 1 0 to 8 0 Mo %, especially preferably 1 5 to 7 5 Mo %. The amount of unsaturated isocyanate compound (1) is not used.  When i mol%, the effect of improvement in sensitivity, heat resistance and elastic properties is low, and when it exceeds 95 mol%, the unreacted unsaturated isocyanate compound (1) remains, and the obtained polymer solution and sensitivity are obtained. The storage stability of the radiation linear resin composition tends to decrease. [A] The polymer has a carboxyl group and/or a carboxylic acid anhydride group, a polymerizable unsaturated bond, has an appropriate solubility to an alkali developing solution, and is easily hardened by exposure and heating, and has an epoxy group. When the acrylic copolymer [β] is used, it can be phase-separated from the [A] polymer, and is compatible, and does not cause surface roughness of the pattern, has excellent developability, and can improve the strength of the spacer. . When the linear resin composition containing the sensitive radiation of [A] polymer and copolymer [β] is developed, no development residue or film reduction occurs, and a spacer having a predetermined shape is easily formed. -22- 200903150 For 100 parts by weight of the [A] polymer, the copolymer [β] is preferably used in an amount of 0. 5 to 50 parts by weight, more preferably 1 to 40 parts by weight, particularly preferably 3 to 30 parts by weight. The copolymer [β] is used in an amount of less than 0. 5 parts by weight, the effect of improving the strength or heat resistance of the spacer is small, and when it exceeds 50 parts by weight, the storage stability of the radiation sensitive linear resin composition tends to decrease - the sensitive radiation linear resin composition - the present invention The sensitized radiation linear resin composition contains the polymer [A] and the copolymer [β] as described above, and preferably contains a [Β] polymerizable unsaturated compound and a [C] sensitizing radiation polymerization initiator. - [Β] Polymerizable unsaturated compound - [Β] The polymerizable unsaturated compound is formed by radiation exposure to produce a polymerized unsaturated compound in the presence of a radiation-sensitive linear polymerization initiator. The polymerizable unsaturated compound is not particularly limited, but is preferably a monofunctional, a bifunctional or a trifunctional or higher functional (meth) acrylate from the viewpoint of good copolymerizability and improvement of the strength of the obtained spacer. . The aforementioned monofunctional (meth) acrylate, for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, diethylene glycol monoethyl acrylate, diethylene glycol monoethyl methacrylate, Isobornyl acrylate, isobornyl methacrylate, 3-methoxybutyl acrylate, 3-methoxybutyl methacrylate, (2-propylene methoxyethyl) (2-hydroxypropyl) benzene 2-23- 200903150 Formate, (2-methacryloxyethyl) (2-hydroxypropyl) phthalate, ω-carboxypolycaprolactone monoacrylate, and the like. Commercial products such as trade name Aronix Μ-101, Μ-111, Μ-114, Μ- 5 3 00 (above is East Asia Synthetic (stock) system); KAYARAD TC-110S, TC-120S (above is Japan) Chemicals (stock) system; Viscoat 158, with 2311 (above is Osaka Organic Chemical Industry Co., Ltd.). The aforementioned bifunctional (meth) acrylate is, for example, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, tetraethylene glycol II. Acrylate, tetraethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, iota, 6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, hydrazine, 9_decanediol dimethacrylate, bisphenoxyethanol hydrazine diacrylate, bisphenoxyethanol hydrazine dimethacrylate, and the like. Commercial products include, for example, Aronix M_21〇, M-240, M-6200 (above East Asia Synthetic Co., Ltd.), KAYARAD HDDA, HX-220, and R-604 (manufactured by Nippon Kayaku Co., Ltd.) , Viscoat 260, 312, and 3 3 5 HP (manufactured by Osaka Organic Chemical Industry Co., Ltd.), light acrylate 1,9-NDA (manufactured by Kyoeisha Co., Ltd.), and the like. The above-mentioned trifunctional or higher (meth) acrylate may, for example, be trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol diacrylic acid vinegar, pentaerythritol trimethylpropionate, or the like. Pentaerythritol tetrapropyl acrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol penta methacrylate, dipentaerythritol hexaacrylate, pentaerythritol hexamethacrylate, tris(2-propenyloxy) Ethyl-24-200903150) Phosphate ester, tris(2-methylpropenyloxyethyl) phosphate, or hexa- or higher-functional (meth) acrylate having a linear alkyl group and an alicyclic structure. Further, a compound having two or more isocyanate groups and a compound having one or more hydroxyl groups in the molecule and having three, four or five acryloxy groups and/or methacryloxy groups are reacted. A polyfunctional urethane acrylate compound or the like. A commercial product of a trifunctional or higher (meth) acrylate, such as a commercial product, for example, a commercial product such as Aronix M-309, the same M-400, the same M-405, the same M-4 50, the same M. -7100, same as M-803 0, same as M-8060, same as TO- 1 450 (above is East Asia Synthetic (stock) system); KAYARAD TMPTA, same DPHA, same DPCA-20, same DPCA-30, same PDCA-60 , with DPCA-120 (above is Nippon Chemical Co., Ltd.); ViSC〇at 295, 300, 360, with GPT, with 3PA, with 400 (above is Osaka Organic Chemical Industry Co., Ltd.) or containing multi-functional Commercial products of urethane acrylate vinegar compound: New frontier R-1150 (manufactured by Daiichi Kogyo Co., Ltd.), KAYARAD DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), and the like. Among these monofunctional, bifunctional or trifunctional or higher functional (meth) acrylates, 'preferably a trifunctional or higher (meth) acrylate, particularly preferably trimethylolpropane triacrylate, pentaerythritol triacrylate, Pentaerythritol tetraacrylate, diquaternol pentaacrylate, dipentaerythritol hexaacrylate or a commercially available product containing a polyfunctional urethane acrylate compound. The above-mentioned monofunctional, bifunctional or trifunctional or higher (meth)acrylic acid -25-200903150 ester may be used singly or in combination of two or more. In the sensitive radiation linear resin composition of the present invention, the amount of the (B) polymerizable unsaturated compound used is preferably from 1 to 120 parts by weight, more preferably from 1 to 120 parts by weight, based on 1 part by weight of the polymer [A]. 3 to 100 parts by weight. [b] When the amount of the polymerizable unsaturated compound used is less than 1 part by weight, development residue may occur during development, and when it exceeds 120 parts by weight, the adhesion to the substrate of the obtained spacer is lowered. Propensity. - [C] sensitive radiation linear polymerization initiator _ [C] sensitive radiation linear polymerization initiator is exposed to visible light, ultraviolet light, far ultraviolet light, charged particle beam, X-ray radiation, etc., resulting in [B] polymerizable The composition of the active species in which the saturated compound begins to polymerize. The linear radiation polymerization initiator [C] is preferably, for example, a ruthenium-based compound, an acetophenone compound, a bismuth-based compound, a benzoin-based compound, a benzophenone-based compound, or a a diketone compound, a polynuclear oxime compound, a xanthone compound, a phosphine compound, a tricholine compound, or the like. The 〇-mercaptopyrimidine compound is preferably 9. Hey. - carbazole type 〇 醯 base type polymerization initiator. For example, there is 1-[9-ethyl-6-benzoquinone- 9. Hey.  -Miso·3·基 〕-壬院- 〗, 2 - 壬院-2·聘-〇-benzoate' ΐ-[9_ethyl_6_benzoquinone_ 9. Hey. -oxazol-3-yl]-decane-indole, 2-decane-2-indene-acetate, hydrazine-[9-ethyl-6-benzoquinone-9. Hey.  -oxazol-3-yl]-pentane-1]-pentane-2_肟_〇_acetate, 1-[9-ethyl-6-benzoquinone- 9. Hey.  - oxazol-3-yl]-octane-; 1 ketone _ -26 - 200903150 〇-acetate, 1-[9-ethyl-6-(2-methylphenylhydrazine)-9. 11. -oxazol-3-yl]-ethane-buxanthene-indole-benzoate, 1-[9-ethyl-6-(2-methylphenylhydrazine)-9. Hey. -oxazol-3-yl]-ethane-1-one oxime-0-acetate, 1-[9-ethyl-6-(1,3,5-trimethylphenylhydrazine)-9. 11. -oxazol-3-yl]-ethane-1-one oxime-0-benzoate, 1-[9-butyl-6-(2-ethylphenylhydrazine)-9. : «-oxazol-3-yl]-ethane-1-one oxime-indole-benzoate, [9-ethyl-6-(2-methyl-4-tetrahydropyranylmethoxy) Benzoquinone)-9. Hey. -oxazol-3-yl]-ethane-1-one oxime-0-acetate, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranmethoxybenzoquinone)-9 . Hey. -oxazol-3-yl]-ethane-1-one oxime-0-acetate, ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylmethoxy) Benzoquinone)-9. Hey. -oxazol-3-yl]-1-(0-acetamidoxime), ethyl ketone-l-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-) 1,3-dioxolyl methoxybenzoquinone}-9. :«. -oxazol-3-yl]-1-(indo-ethenylhydrazine) and the like. In the 0-acid-based compound, it is preferred that 1-[9-ethyl-6-(2-methylphenylhydrazine)-isoxazole-3-yl]-ethane-1-one oxime-0- Acetate, 1-[9-ethyl-6-(2-methyl-4-tetrahydropyranyloxyphenylhydrazine)-oxazol-3-yl]-ethane-1-one oxime-0- Acetate, ethyl ketone-l-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzoquinone }-9. Η·-carbazol-3-yl]-1-(0-ethylindenyl). The above-mentioned fluorene-indenyl hydrazine compound may be used singly or in combination of two or more. In the present invention, by using the ruthenium-iridium ruthenium compound, a spacer having sufficient sensitivity and adhesion can be obtained even at an exposure amount of 1,500 J/m2 or less. The acetaminophen compound may, for example, be an α-hydroxyketone compound or an α-amine -27-200903150 ketone compound. The aforementioned α-hydroxyketone-based compound is, for example, 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane- 1-keto, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, etc., and the aforementioned α-amino ketone compound has, for example, 2 -methyl-bu (4-methylphenylthio)-2-morpholinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl) -butan-1-one, 2-(4-methylphenylhydrazine)-2-(dimethylamino)-1-(4-morpholinylphenyl)-butan-1-one, etc. Other compounds include, for example, 2,2-dimethoxyacetamidine, 2,2-diethoxyethyl benzene, 2,2-dimethoxy-2-phenyl ethene benzene, and the like. Among the above acetylbenzene compounds, particularly preferred are 2-methyl-1-(4-methylphenylthio)-2-morpholinylpropan-1-one and 2-(4-methylphenylhydrazine)- 2-(Dimethylamino)-bu(4-morpholinylphenyl)-butan-1-one. In the present invention, the acetophenone-based compound can further improve the sensitivity, the shape of the spacer, and the compressive strength. Further, the above diimidazole-based compound is, for example, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'- Biimidazole, 2,2'-bis(2-bromophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2 '-Bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)- 4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5' -tetraphenyl-1,2'-biimidazole, 2,2'-bis(2-bromophenyl)-4,4',5,5'-tetraphenyl-1, 2'-biimidazole, 2 , 2'-bis(2,4-dibromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2, bis(2,4,6- Tribromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, etc. -28- 200903150 Among the compounds, preferably 2, 2, _ double (2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2,biimidazole, 2,2,_bis(2,4-dichlorophenyl)-4,4' ,5,5'-tetraphenyl-1,2,-biimidazole, 2,2,_bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl -1,2,-biimidazole, etc., especially preferably 2,2,_double (2,4_ one chlorine ) -4,4 ', 5,5' - tetraphenyl _i, 2, _ Mi linked miles. In the present invention, the biimidazole-based compound can be used to further improve the sensitivity, the resolution, or the adhesion of the resulting spacer to the substrate. When a biimidazole-based compound is used, an aliphatic or aromatic compound having a divalent amine group (hereinafter referred to as "amino-based sensitizer") may be added in order to increase the sensitivity. Amine-based sensitizers are, for example, N-methyldiethanolamine, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone , p-Dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid isoamyl ester, and the like. Among these amine-based sensitizers, particularly preferred is 4,4'-bis(diethylamino)benzophenone. These amine-based sensitizers may be used alone or in combination of two or more. Further, when a biimidazole-based compound and an amine-based sensitizer are used, a thiol-based compound which supplies a hydrogen compound can be added. The biimidazole-based compound is cleavable by the sensitization of the amine-based sensitizer, and an imidazole radical is generated. However, in this state, a high polymerization initiation energy cannot be obtained, and most of the obtained spacer has a bad shape of a reverse cone shape. . However, when a thiol-based compound is added to a system containing a biimidazole-based compound and a serotonin-based sensitizer, the thiol-based compound -29-200903150 supplies a hydrogen radical to the imidazole radical, and the imidazole radical is The imidazole' simultaneously produces a sulfur self-ingredient having a higher polymerization initiating energy, whereby the spacer shape can form a preferred cone shape. The thiol compound is, for example, 2-mercaptobenzothiazole, 2-mercaptozolyl, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazolyl-5-methoxybenzo An aromatic compound such as imidazole; a monothiol such as methyl 3-mercaptopropionyl propionate, ethyl 3-mercaptopropionate or octyl 3-mercaptopropionate; 3,6-dioxin-1,8- A difunctional thiol is exemplified by octane dithiol, pentaerythritol tetra(ester), pentaerythritol tetrakis(3-mercaptopropionate). Among these thiol compounds, particularly preferred is 2-mercaptobenzothiazole. In the sensitive radiation linear resin composition of the present invention, the other sensitive polymerization initiator is used in a ratio of 100 parts by weight for all linear radiation polymerization, preferably 100 parts by weight or less, more preferably 80 parts by weight, and particularly preferably 60. Parts by weight or less. When the ratio of use of other sensitive radiation linear polymerization exceeds 100 parts by weight, the effects of the present invention may be affected. Further, when the biimidazole compound and the amine-based sensitizer are used in combination, the amount of the amine sensitizer added is 0% by weight based on 100 parts by weight of the diimidazole-based compound. 1 to 50 parts by weight, more preferably i to 20 parts by weight. When the amount of the amine group added is less than 0.1 part by weight, the sensitivity, the resolution, and the adhesion-preventing effect tend to be lowered, and when it exceeds 50 parts by weight, the shape of the obtained spacer can be obtained. When a biimidazole compound and an amine-based sensitizer are used, the thiol is converted into a lipid ray-initiating dose of the base benzoxanthene, 2-anthracene, 3-indole aliphatic thiol group as an initiator. It is expected that the basis weight is increased, and the preferred sensitizing agent is modified to impair the amount of the compound -30-200903150. When the amount of the biimidazole compound is 100 parts by weight, it is preferably 0. 1 to 50 parts by weight. It is 1 to 20 parts by weight. The amount of thiol compound added is less than 〇.  When the amount is 1 part by weight, the effect of improving the shape of the spacer is lowered, or the film tends to be reduced, and when it exceeds 50 parts by weight, the shape of the obtained spacer may be impaired. -Additive - The radiation sensitive linear resin composition of the present invention may contain a surfactant, a bonding aid, a storage stabilizer, and heat resistance in addition to the above components, within a range not affecting the effects expected by the present invention. Additives such as lifters. The surfactant is a component having an effect of improving coatability, and is preferably a fluorine-based surfactant or a polyoxyn-based surfactant. The fluorine-based surfactant is preferably a compound having a fluoroalkyl group or a fluoroalkyl group in at least one of a terminal group, a main chain and a side chain, and a specific example thereof is 1,1,2,2-tetrafluorooctyl group (1). , 1,2,2-tetrafluoro-n-propyl)ether, 1,1,2,2-tetrafluoro-n-octyl (n-hexyl)ether, octaethylene glycol di(1,1,2,2_ Tetrafluoro-n-butyl)ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoro-n-pentyl)ether, octapropylene glycol bis(1,1,2,2-tetrafluoro- N-butyl)ether, hexapropylene glycol bis(1,1,2,2,3,3-hexafluoro-n-pentyl)ether; 1,12,2,3,3-hexafluoro-n-decane, 1 1,1,2,2,8,8,9,9,10,10-decafluoro.n-dodecane, sodium perfluoro-n-dodecylsulfonate, or sodium fluoroalkylbenzenesulfonate, halothane Sodium phosphinate, sodium fluoroalkylcarboxylate, fluorine-based polyoxyethylene ether, diglycerol tetrakis(fluoroalkylpolyoxyethylene ether), fluorine i: mercapto-methylamine, fluoroalkyl betaine, halothane Polyoxyethylene ether, perfluoro-31 - 200903150 alkyl polyoxyethylene, perfluoroalkyl alkoxide, fluoroalkyl ester, and the like. Further, the commercial product of the fluorine-based surfactant is, for example, BM-1 000, the same 1 〇〇 (the above is BM CHEMIE company); MEGAFAC F142D, the same F 1 7 2, the same F 1 7 3. Same as F 1 8 3, same as F 1 7 8 , same as F191, same as F4 71, same as F4 76 (above is made by Dainippon Ink Chemical Industry Co., Ltd.); Fluorad FC-170C, with FC-171, same FC-430, same as FC-431 (above Sumitomo 3M (share) system); SurfllonS-112, same S-113, same S-131, same S-141, same S-145, same S-382, same SC -101, the same SC-102, the same SC-103, the same SC-104, the same SC-105, the same SC-106 (the above is the Asahi Glass Co., Ltd.); FTOP EF301, the same EF 3 03, the same EF3 52 (above) For the new Akita Chemicals Co., Ltd.); FTERGENT FT-100, with FT-110, with FT-140A, with FT-150, with FT-25 0, with FT-251, with FTX-251, with FTX-218 , with FT-300, with FT-310, with FT-400S (above is Neos (share) system). Commercially available products of the above polyoxo-based surfactants include, for example, Toray Silicon DC3PA, DC7PA, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, and SH-193. , with SZ-603 2, with SF-842 8, with DC-57, with DC-190 (above is Toray Chemical silicone (share) system); TSF-4440, with -4300, with -4445, with -4446 , with -46060, with -4452 (above is GE Toshiba silicone (share) system). The surfactant other than the above is, for example, polyoxyethylene alkyl ether such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether or polyoxyethylene oleyl ether; polyoxyethylene positive-32-200903150 octyl phenyl ether, polyoxyethylene a polyoxyethylene aryl ether such as nonyl phenyl ether; a nonionic surfactant such as polyoxyethylene dilaurate or polyoxyethylene distearate; or a commercial name such as a commercial product; For example, there are KP34丨 (Shin-Etsu Chemical Industry Co., Ltd.), P〇lyfl〇wNo. 57, Ν〇·95 (Common Society (share) system) and so on. These surfactants can be used individually or in mixture of 2 or more types. The amount of the surfactant added is preferably '5 parts by weight or less' to more preferably 2 parts by weight or less based on 1 part by weight of the polymer [A]. When the amount of the surfactant to be added exceeds 5 parts by weight, the film tends to be rough at the time of coating. The above-mentioned adhesion aid is a component having an effect of further improving the adhesion between the spacer and the substrate, and is preferably a functional decane coupling agent. The functional sand chamber coupling agent' is, for example, a compound having a reactive functional group such as a residue, a methacrylic acid group, a vinyl group, an isocyanate group or an epoxy group. Specifically, there are, for example, trimethoxylethane-based benzoic acid, γ-methacryloxypropyltrimethoxydecane 'vinyltriethoxydecane, vinyltrimethoxydecane, γ-isocyanate Propyltriethoxydecane, γ-glycidoxypropyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, and the like. These adjunct agents may be used alone or in combination of two or more. The amount of the auxiliary agent added is preferably 10 parts by weight or less, more preferably 1 part by weight or less, per 100 parts by weight of the [A] polymer. When the amount of the auxiliary agent added exceeds 20 parts by weight, the tendency to cause development residual is likely to occur. -33- 200903150 The above-mentioned preservation stabilizers are, for example, sulfur, hydrazines, hydroquinones, polyhydroxy compounds, amines, nitronitroso compounds, and the like, more specifically, for example, 4-methoxyphenol, N-nitroso- N-phenylhydroxylamine aluminum and the like. These preservation stabilizers may be used alone or in combination of two or more. The amount of the stabilizer to be added is preferably 3 parts by weight or less, more preferably 0 parts by weight, based on 100 parts by weight of the [A] polymer. Ooi ~ 〇, 5 parts by weight. When the amount of the stabilizer to be added exceeds 3 parts by weight, the sensitivity is lowered and the shape of the pattern may be impaired. The heat resistance improving agent is, for example, an N-(alkoxymethyl)glycolide compound or an N-(alkoxymethyl)melamine compound. The aforementioned N-(alkoxymethyl) glycoluril compound is, for example, N,N,N,,N'-tetrakis(methoxymethyl)glycoluril, ruthenium, osmium, iridium, osmium, tetrakis Methyl)glycolour, hydrazine, hydrazine, hydrazine, Ν'-tetrakis (n-propoxymethyl) glycoluril, hydrazine, hydrazine, hydrazine, Ν'-tetrakis(isopropoxymethyl) glycoluril , Ν, Ν, Ν ', Ν, - tetra (n-butoxymethyl) glycoluril, hydrazine, hydrazine, hydrazine, Ν'-tetrakis(t-butoxymethyl) glycoluril, and the like. Among these Ν-(alkoxymethyl)glycoluric compounds, particularly preferred are ν, ν, ν', ν'-tetrakis(methoxymethyl) glycoluril. The above fluorenyl-(alkoxymethyl)melamine compound has, for example, ν, ν, ν, ν', ν'', ν''-hexa(methoxymethyl)melamine, ν, ν, ν, ν ,,ν'',ν''-hexa(ethoxymethyl)melamine, ν,ν,ν,,ν,,ν,,,ν''-hexa(n-propoxymethyl)melamine' ν ,ν,ν,,ν,,ν,,,ν,'-hexa(isopropoxymethyl)trimeric amine 'Ν,Ν,Ν,Ν,Ν,Ν,Ν''-six (n-butoxymethyl) melamine, -34- 200903150 N, N, N', N', N'', N''-hexa(t-butoxymethyl) melamine, and the like. Among these N-(alkoxymethyl)melamine compounds, it is particularly preferred to be MU4^,>^,>^', 1^'-hexa(methoxymethyl)melamine, which is commercially available. The trade names include, for example, Nikalac N-2 702 and the same MW-30M (above, Sanwa Chemical Co., Ltd.). The heat resistance improving agent may be used singly or in combination of two or more. The amount of the heat-resistant enhancer added is 100 parts by weight, preferably 30 parts by weight or less, more preferably 20 parts by weight or less based on the [A] polymer. When the amount of the heat-resistant enhancer added exceeds 30 parts by weight, the storage stability of the radiation-sensitive linear resin composition tends to decrease. The sensitive radiation linear resin composition of the present invention is preferably used in the form of a solution of a composition dissolved in a suitable solvent. The solvent is used to uniformly dissolve the components constituting the linear radiation-sensitive resin composition, and does not react with each component, and has moderate volatility, but the solubility of each component, the reactivity with each component, and the formation of a coating film are easy. Preferred from the viewpoint of alcohol, ethylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, diethylene glycol alkyl ether, propylene glycol monoalkyl ether acetate, dipropylene glycol alkyl ether, Alkoxy alkanoate, acetate, etc., particularly preferably benzyl alcohol, 2-phenylethanol, 3-phenyl-propanol, ethylene glycol mono-n-butyl ether acetate, diethylene glycol single Ethyl acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol dimethyl ether, 3-methoxybutyl acetate, 2-methoxyethyl acetate, and the like. These solvents may be used alone or in combination of two or more. -35- 200903150 In the present invention, the above solvent and a high boiling point solvent can be used. The above high boiling point solvent is, for example, N-methylformamide, ν, ν·dimethylformamide, Ν-methylformanilide, Ν_methylacetamide, hydrazine, hydrazine _: methyl acetamide , Ν-methylpyrrolidone, dimethyl benzylidene, benzyl ether, di-η-hexyl ether, acetone acetone, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl alcohol, Benzyl acetate, ethyl benzoate, diethyl oxalate, maleic acid monoethyl acetate, γ·butyrolactone, ethylene carbonate, propyl carbonate, ethylene glycol monophenyl ether acetate, and the like. These high boiling point solvents can be used individually or in mixture of 2 or more types. Further, the composition solution prepared as described above is a pore size of 0. The 5 μιη micropore filter is filtered and used. The sensitive radiation linear resin composition of the present invention is particularly suitable for forming spacers for liquid crystal display elements. Method of Forming Spacer The method of forming the spacer for a liquid crystal display element of the present invention will be described below using the radiation sensitive linear resin composition of the present invention. The method for forming a spacer for a liquid crystal display device of the present invention contains at least the following steps in the following order. (a) a step of forming a film of the radiation sensitive linear resin composition of the present invention on a substrate, (b) a step of exposing at least a portion of the film, and (c) a step of developing the film after exposure and (D) A step of heating the film after development. -36- 200903150 These steps are described in order below. - (a) step - forming a transparent conductive film on one surface of the transparent substrate, and preferably applying a solution of the radiation sensitive linear resin composition to the transparent conductive film, the coated surface is heated, that is, pre- Baking forms a film. A transparent substrate for forming a spacer, for example, a glass substrate, a resin substrate, or the like. More specifically, a glass substrate such as soda lime glass or alkali-free glass; polyethylene terephthalate or polybutylene terephthalate; A resin substrate composed of a plastic such as polyether, polycarbonate or polyimine. As the transparent conductive film provided on one surface of the transparent substrate, a NESA film (registered trademark of PPG, USA) composed of tin oxide (SnO 2 ), an ITO film composed of indium oxide-tin oxide (In203-SnO 2 ), or the like can be used. The coating method of the composition solution is a method of forming the film of the radiation sensitive linear resin of the present invention, and for example, (1) coating method and (2) dry film method can be used. The coating method of the composition solution may be a suitable method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, or an inkjet coating method. Spin coating method, slit die coating method. When the film of the sensitive radiation linear resin composition of the present invention is formed, when the (2) dry film method is used, the dry film is preferably laminated with the sensitive radiation linear layer composed of the sensitive radiation linear resin composition of the present invention to the base film. Preferably, it is composed of a flexible base film (hereinafter referred to as "sensitive radiation linear dry film"). -37- 200903150 ±Sensitivity Radiation Linear Dry Film is formed by applying the sensitive radiation linear resin composition or liquid composition of the present invention onto a base film, and then drying the linear layer by absorbing the radiation. As the base film of the radiation-sensitive linear dry film, for example, a synthetic resin film of polyethylene terephthalate (PET), polyethylene, polypropylene, polycarbonate, polyvinyl chloride or the like can be used. The thickness of the base film is desirably 1 5 to 1 25 μπα. The thickness of the obtained linear layer of the sensitive radiation is preferably 1 to 3 0 μηι 〇 The radiation-sensitive linear dry film can be deposited by laminating the protective film on the sensitive radiation linear layer when not in use. This protective film does not peel off when not in use, and is easily peeled off during use. The protective film which satisfies such a condition can be coated with a surface of a synthetic resin film such as a PET film, a polypropylene film, a polyethylene film, or a polyvinyl chloride, or a film of a baked polyoxyl type release agent. The thickness of the protective film is usually 25 μm. The prebaking conditions vary depending on the type of each component, the ratio of use, etc., and are usually 70 to 120 ° C for 1 to 15 minutes. - (B) Step - Next, at least a portion of the formed film is exposed. At this time, when a part of the film is exposed, the radiation beam for exposure and exposure by a mask having a predetermined pattern is usually used, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray, etc., but at a wavelength of 19 The radiation of 0 to 4 50 nm is preferred, and the radiation of ultraviolet rays containing 365 nm is particularly preferred. Exposure is based on illuminance meter (OAI model 356, OAI Optical -38- 200903150)

Associates Inc.製）測定曝光之Ι§射線波長365nm之強度 値，通常爲 1〇〇〜1 0,00 0J/m2’ 更佳爲 5 00 〜l,500J/m2。 -(丙）步驟- 其次，曝光後之被膜經顯像’除去不要部份，形成所 定之圖型。 顯像用之顯像液較佳爲鹼顯像液，例如氫氧化鈉、氫 氧化鉀、碳酸鈉、矽酸鈉、偏矽酸鈉、氨等無機鹼；乙胺 、正丙胺等脂肪族1級胺；二乙胺、二正丙基胺等脂肪族 2級胺；三甲胺、甲基二乙胺、二甲基乙胺、三乙胺等脂 肪族3級胺；吡咯、哌啶、N-甲基哌啶、N-甲基吡咯烷、 1，8-二氮雜二環〔5.4.0〕-7-十一烯、1，5-二氮雜二環〔 4 · 3.0〕- 5 -壬烯等脂環族3級胺；吡啶、三甲基吡啶、二 甲基吡啶、喹啉等芳香族3級胺；乙醇二甲胺、甲基二乙 醇胺、三乙醇胺等烷醇胺；四甲基氫氧化銨、四乙基氫氧 化銨等4級銨鹽等鹼性化合物之水溶液。 又，該鹼性化合物之水溶液中可添加使用適當之甲醇 、乙醇等水溶性有機溶劑或界表面活性劑。 顯像方法可爲盛液法、浸漬法、淋浴法等’顯像時間 通常爲約1 0〜1 8 0秒。 顯像後例如以流水洗淨3 0〜9 0秒，再以例如壓縮空 氣或壓縮氮風乾，而形成所希望之圖型。 -(丁）步驟- -39- 200903150 接著，製得之圖型例如以加熱板、烤箱等加熱裝置， 在所定溫度，例如100〜23 0 °C，所定時間，例如加熱板上 爲5〜30分鐘’烤箱中爲30〜180分鐘加熱，即後供烤可 得到所定之間隔物。 間隔物形成用之以往之敏輻射線性樹脂組成物，未以 1 80〜23 0°C以上之溫度進行加熱處理時，無法發揮所得之 間隔物的充分性能，但是本發明之敏輻射線性樹脂組成物 ’其加熱溫度可爲低於以往之低溫，結果樹脂基板不會變 黃或變形，可形成壓縮強度、液晶配向時之耐摩擦性、與 基板之密著性等各種特性優異的間隔物。 液晶顯示元件 本發明之液晶顯示元件係具備上述所形成之本發明的 間隔物。 本發明之液晶顯示元件的構造無特別限制，例如第1 Η所示，具有在基板上形成彩色濾光片層與間隔物，經由 液晶層配置之2片配向膜、對向之透明電極、對向之基板 等的構造。又如第1圖所示，必要時可在偏光板或彩色濾 光片層上形成保護膜。 另外，如第2圖所示，在基板上形成彩色濾光片層與 間隔物，經由配向膜及液晶層，使與薄膜晶體（TFT )陣 列對向可形成TN-TFT型之液晶顯示元件。必要時，在偏 光板或形成於濾色濾光片層上形成保護膜。 如上述，本發明之敏輻射線性樹脂組成物可得到高感 -40- 200903150 度且高解像度，即使在100 (Η/m2以下之曝光量也可得到 充分之圖型形狀，可形成顯像性優異，彈性回復性、耐摩 擦性、與基板之密著性、耐熱性等優異，且製得之圖型表 面無凹凸狀之表面粗糙之液晶顯示元件用間隔物，又，樹 脂基板不會產生變黃或變形。 本發明之液晶顯示元件係具備感度、顯像性、彈性回 復性、耐摩擦性、與基板之密著性、耐熱性等各種性能之 優異，且圖型表面無凹凸狀之表面粗糙之間隔物者，具有 長期高信賴性。 【實施方式】 實施例 以下舉實施例具體說明本發明之實施形態。此處份及 %係重量基準。 合成例1 將2,2'-偶氮雙異丁腈5重量份及乙酸3-甲氧基丁酯 25 0重量份投入具備冷卻管及攪拌機之燒瓶內，接著添加 甲基丙烯酸18重量份、甲基丙烯酸三環〔5.2.1.02’6〕癸 烷-8-酯25重量份、甲基丙烯酸2 -羥乙酯30重量份及甲 基丙烯酸苄酯22重量份’然後進行氮取代後，緩緩攪拌 下，使溶液溫度上升至8 0 °C ’此溫度下保持5小時進行聚 合，得到固形份濃度28.8%之共聚物〔α-l〕溶液。 製得之共聚物〔α-l〕使用GPC (凝膠滲透色譜法） -41 - 200903150 GPC-101 (昭和電工（股）製）測得Mw爲1 3,0〇〇。 接著，將2-甲基丙烯醯氧基乙基異氰酸酯（商品^ karenzMOI、昭和電工（股）製）14重量份與4 -甲氧基苯 酚〇_1重量份添加於前述共聚物〔α-l〕溶液後，以4(Γ(： 、攪拌1小時，再以60t、攪拌2小時產生反應。來自2_ 甲基丙烯醯氧基乙基異氰酸酯之異氰酸酯基與共聚物[α_ 1〕之羥基之反應進行係藉由IR (紅外線吸收）光譜認、 。聚合物溶液〔α -1〕、1小時反應後之溶液及4 0 °C、1小 時，再以6 0 °C、2時間反應後之溶液各以IR光譜確認來 自2-甲基丙烯醯氧基乙基異氰酸酯之異氰酸酯基在 2,2 7 0(:1^1附近之波峰減少。得到固形份濃度30.0%之〔a 〕聚合物溶液。此〔A〕聚合物爲聚合物（A-1)。 合成例2 與合成例1相同’將2-丙烯醯氧基乙基異氰酸酯（商 品名karenz AOI、昭和電工（股）製）14重量份與4 -甲 氧基苯酣0 · 1重量份添加於前述共聚物〔a -1〕溶液後，以 4 0 °C、攪拌1小時’再以6 0 °C、攪拌2小時產生反應。得 到固形份濃度3 0 · 5 %之〔A〕聚合物溶液。此〔A〕聚合物 爲聚合物（A-2 )。 合成例3 與合成例1相同，將甲基丙烯醯氧基丁基異氰酸酯 (商品名karenz MOI-C4、昭和電工（股）製）17重量份 -42- 200903150 與4-甲氧基苯酚o.l重量份添加於前述共聚物〔α-1〕溶 液後，以4 0。(：、攪拌1小時，再以6 0。(：、攪拌2小時產生 反應。得到固形份濃度3 1 . 0 %之〔A〕聚合物溶液。此〔Α 〕聚合物爲聚合物（Α-3)。 合成例4 將2，2’-偶氮雙異丁腈5重量份、乙酸3-甲氧基丁酯 重量份及丙二醇單甲醚乙酸酯125重量份投入具備冷 卻管及攪拌機之燒瓶內，接著添加甲基丙烯酸18重量份 、甲基丙烯酸三環〔5.2.1.〇2,6〕癸烷-8-酯25重量份及苯 乙稀5重量份、丁二烯5重量份、甲基丙烯酸2_( 6_羥基 己醯氧基）乙基酯（商品名PLACCEL FMlD(Dicel化學 工業（股）製）25重量份及甲基丙烯酸四氫呋喃-2_酯22 重里份’然後進行氮取代後，緩緩攪拌下，使溶液溫度上 •_ 2〕溶液。 α_2〕使用GPC (凝膠滲透色譜法 升至80 C ’此溫度下保持5小時進行聚合，得到固形份濃 度29.1%之共聚物 製得之共聚物 GW (昭誠Χ (股）製）測得心爲18,〇〇〇。 接著’將2·甲基丙烯醯氧基乙基異氰酸酯（商品名 karenz MOI日口和電工（股）製）14重量份與甲氧基 本酌〇· 1重量份添加於前述共聚物〔α-2〕溶液後，以 4〇 C攪拌1 時’再以6代、攪拌2小時產生反應。得 到固形份濃度3 1 .〇%之〔A〕聚合物溶液。此〔a〕聚合物 爲聚合物（A - 4 )。 -43- 200903150 合成例5 將2，2'-偶氮雙（2，4 -二甲基戊腈）7重量份與二乙二 醇甲基乙醚250重量份投入具備冷卻管及攪拌機之燒瓶內 ’接著添加甲基丙烯酸18重量份、甲基丙烯酸三環〔 5.2.1.02’6〕癸烷-8-酯34重量份、苯乙烯5重量份、丁二 烯5重量份及甲基丙烯酸縮水甘油酯40重量份，然後進 行氮取代後’緩緩攪拌下’使溶液溫度上升至7 0。(：，此溫 度下保持5小時進行聚合，得到固形份濃度3丨.0 %之共聚 物〔β -1〕溶液。製得之共聚物〔β -1〕溶液使用G P C (凝 膠滲透色譜法）GP C -1 0 1 (昭和電工（股）製）測得μ w 爲 1 1,000。 合成例6 將2,2'-偶氮雙（2,4-二甲基戊腈）7重量份與丙二醇 單乙醚乙酸酯200重量份投入具備冷卻管及攪拌機之燒瓶 內，接著添加苯乙烯19重量份、甲基丙烯酸三環〔 5.2.1.02,6〕癸烷-8-酯38重量份、甲基丙烯酸13重量份 及甲基丙烯酸甲基縮水甘油酯3 0重量份，然後進行氮取 代後，緩緩攪拌下’使溶液溫度上升至70°C ’此溫度下保 持7小時進行聚合，得到含有共聚物〔β-2〕之聚合物溶 液。此聚合物溶液之固形份濃度爲3 2 · 9 %。 製得之共聚物〔β-2〕溶液使用GPC (凝膠滲透色譜 法）G P C -1 0 1 (昭和電工（股）製）測得M w爲1 2，0 0 〇。 -44- 200903150 合成例7 將2,2'-偶氮雙（2,4-二甲基戊腈）7重量份與二乙二 醇甲基乙醚250重量份投入具備冷卻管及攪拌機之燒瓶內 ，接著添加甲基丙烯酸18重量份、甲基丙烯酸三環〔 5_2. 1 ·〇2’6〕癸烷-8-酯34重量份、苯乙烯5重量份、丁二 烯5重量份、甲基丙烯酸3，4-環氧基環己基甲酯20重量 份及甲基丙烯酸四氫呋喃-2-酯20重量份，然後進行氮取 代後，緩緩攪拌下，使溶液溫度上升至70°C，此溫度下保 持5小時進行聚合，得到固形份濃度30.0%之共聚物〔β-3 〕溶液。製得之共聚物〔β-3〕溶液使用GPC (凝膠滲透 色譜法）GPC-101 (昭和電工（股）製）測得 Mw爲 1 1，000 ° 合成例8 將2,2’-偶氮雙（2,4-二甲基戊腈）7重量份與丙二醇 單甲醚乙酸酯250重量份投入具備冷卻管及攪拌機之燒瓶 內，接著添加苯乙烯5重量份、甲基丙烯酸18重量份、 甲基丙烯酸三環〔5.2.1.02’6〕癸烷-8-酯17重量份、3-( 甲基丙烯醯氧基甲基）-3-乙基氧雜環丁烷40重量份、甲 基丙烯酸四氫呋喃-2-酯20重量份，然後進行氮取代後， 緩緩攪拌下，使溶液溫度上升至70 °C，此溫度下保持5小 時進行聚合，得到含有共聚物〔β_4〕之聚合物溶液。此 聚合物溶液之固形份濃度爲29.0%，使用GPC (凝膠滲透 -45- 200903150 色譜法）GPC-101 (昭和電工（股）製）測得Mw爲 14,000 〇 實施例1 組成物溶液之調製 混合[A]成份爲合成例1製得之[A]聚合物溶液作爲聚 合物（A-1 ) 100重量份、合成例5製得之共聚物〔β_ι〕 10重量份，[Β]成份爲二季戊四醇六丙烯酸酯（商品名 KAYARAD DPHA，曰本化藥公司製）1〇〇重量份，[C]成 份爲1-[9-乙基-6- ( 2-甲基苯醯基）-9.Η.-咔唑_3_基]•乙 烷-1-酮肟-〇·乙酸酯）（商品名「IRGACURE 0X02，Ciba Specialty Chemicals Inc 公司製」）5 重量份、2,2' -雙（2-氯苯基）-4，4’，5,5、四苯基-1，2'-聯咪唑5重量份、4,4’-雙 (二乙基胺基）二苯甲酮5重量份、2 -氫硫基苯并噻唑 2.5重量份、接著助劑之γ-環氧丙氧基丙基三甲氧基矽烷 5重量份、界面活性劑之FTX-218 (商品名、（股）Neos 製）0.5重量份及保存安定劑之4-甲氧基苯酹0.5重量份 ，溶解於丙二醇單甲醚乙酸酯中，使固形份濃度成30%後 ，以孔徑〇 . 5 μιη之微孔過濾器過濾，調製出組成物溶液。 表1中，聚合物以外之各成份如下述。 〔Β〕成份 (Β-1 ):二季戊四醇六丙烯酸酯（日本化藥公司 製，商品名「KAYARAD DPHA」） -46 - 200903150 (B_2):含有多官能胺基甲酸乙酯丙体^醋系化 合物的市售品（商品名KAYARADDPHA-40H) (B-3 ):季戊四醇四丙烯酸酯（商品名「aronix M-450」’東亞合成（股）製） (B-4 ) : ω-羧基聚己內酯單丙烯酸酯（（商品名 「aTDiiix M-5300」，東亞合成公司製） (B-5) : 1,9-壬烷二丙烯酸酯（商品名「light丙 烯酸酯1，9-NDA」共榮社（股）製） 〔C〕成份 (C-1) :1-[9-乙基-6-(2-甲基苯醯基）-9.1-咔 唑-3-基]-乙烷-丨·酮肟-〇_乙酸酯）（商品名「irgacuRE 0X02 ’ Ciba Speciaity Chemicals Inc 公司製」） (C-2):乙酮-1-[9-乙基-6-[2-甲基-4-(2,2-二甲 基-1,3-二氧雜環戊基）甲氧基苯醯基咔唑-3-基]-1-(0 -乙醯基肟）（ADEKA公司製，N-1919) (C-3) : 2 -甲基-1-( 4 -甲基苯硫基）-2 -嗎啉基丙 垸-1-嗣（商品名 Irgacure907 ， Ciba. Speciality. Chemicals 公司製） (C-4 ) :2-(4-甲基苄基）-2-(二甲胺基）-l_( 4-嗎啉基苯基）-丁院-1-嗣（茼品名Irgacure 379、 Ciba · Speciality . Chemicals 公司製） (C-5) : 2,2'-雙（2-氯苯基）-4,4',5,5' -四苯基- 1,2’-聯咪唑 -47- 200903150 (C-6 ) : 4,4’-雙（二乙基胺基）二苯甲酮 (C-7) :2 -氫硫基苯并噻唑 〔D〕成份 (D-1):多官能酚醛型環氧樹脂（商品名，曰本 環氧基樹脂（股）製，epitokel52) 實施例2〜1 6、比較例1〜5係與實施例1同樣調製組 成物溶液。結果如表1所示。 又，實施例1 7、比較例6係以乾薄膜法實施。 間隔物之形成 實施例2〜1 6、比較例1〜5係使用旋轉塗佈器塗佈於 基板，形成間隔物。詳述如下。 使用旋轉塗佈器將前述組成物溶液塗佈於無鹼玻璃基 板上’在100°C之加熱板預熱3分鐘，形成膜厚3.5μηι之 被膜。 其次’經由ΙΟμπι正方之殘餘圖型光罩，對所得之被 膜曝光。然後’以氫氧化鋰0.05重量％水溶液在25 °C下顯 像後’使用純水洗淨1分鐘，再以2 3 0 t之烘箱中加熱3 0 分鐘，形成間隔物。 實施例1 5係以乾薄膜法形成間隔物。詳述如下。 實施例1 7 將敏幅射線性樹脂組成物之液狀組成物（S -1 7 )以乾 -48- 200903150 薄膜法製作塗膜外’其餘與實施例1〜14相同形 薄膜進行評價。各成份如表1所示。曝光步驟前 基礎薄膜。評價結果如表2所示。下述之轉印性 果也如表2所示。 如下述製作乾薄膜及轉印。 使用塗佈器將敏輻射線性樹脂組成物之液狀 S-17)塗佈於厚度38μιη之聚對苯甲酸乙二酯（ 膜上，塗膜以1〇〇 °C加熱5分鐘，製作厚度4μιη 線性乾薄膜（J-1 )。其次，將敏輻射線性轉印 疊於玻璃基板表面’使敏輻射線性轉印層之表面 接’再以熱壓黏法將敏輻射線性乾薄膜（J-1 ) 璃基板。 -乾薄膜轉印至玻璃基板之轉印性的評價-以熱壓黏法將敏輻射線性乾薄膜轉印至玻璃 ’乾薄膜可均勻轉印至玻璃基板上時，評價爲「 薄膜一部份殘留於基礎薄膜上，或乾薄膜無法密 基板等，乾薄膜無法均勻轉印至玻璃基板上時， X ( 〇 比較例6 使用敏輻射線性樹脂組成物之液狀組成物 代實施例1 7之敏輻射線性樹脂組成物之液狀組 1 7 )外，與實施例1 7同樣製作敏輻射線性乾薄| 成圖型狀 剝離除去 之評價結 組成物（ PET )薄 之敏輻射 乾薄膜重 被接觸連 轉印至玻 基板上時 〇」，乾 著於玻璃 評價爲「 :s_6)取 成物（S-莫（J-2 ) -49- 200903150 後，形成圖型狀薄膜進行評價。各成份如表1所示。 結果如表2所示。轉印性之評價結果也如表2所示。 接著，以下述要領進行各種評價。評價結果如表 不 ° (1 )顯像時間之評價 顯像時間設定爲30、 40、 50、 60、 70、 80、 90】 秒，在各顯像時間以光學顯微鏡觀察未曝光部之殘德 顯像時間，確認未曝光部無殘渣時之最短顯像時間如 所示。顯像時間越短，判斷爲顯像性越佳。 (2 )感度之評價 與間隔物之形成相同，形成間隔物時，曝光烘烤 殘膜率（曝光烘烤後之膜厚XI 00/曝光後膜厚）成爲 以上之曝光量當作感度。此曝光量爲l,00(U/m2以下 表示感度良好。 (3 )彈性回復率之評價 對於製得之間隔物使用微小壓縮試驗機（商 DUH-201，島津製作所（股）製），以直徑50μπι之 壓子其負荷速度及除荷速度均爲2.6mN/秒，負荷至 5 0mN，保持5秒後除去負荷，製作負荷時之荷重-變 曲線及除荷時之荷重-變形量曲線。此時，如第3圖 ，負荷時之荷重 5〇mN之變形量爲 L1，除荷時之 評價 2所 100 。各 表2 後之 90% 時， 品名 平面 荷重 形量 所示 荷重 -50- 200903150 50mN之變形量爲L2’由下式算出彈性回復率。 彈性回復率（％ ) = L 2 X 1 0 〇 /L 1 彈性回復率（％ )與變形量爲L1 ( μ m )如表2所示。 (4 )耐摩擦性之評價 使用液晶配向膜塗佈用印刷機將液晶配向劑AL3 046 (商品名’ JSR (股）製）塗佈於形成間隔物之基板上， 然後以1 8 0 °C乾燥1小時，形成膜厚〇 · 〇 5 μηι之液晶配向劑 的塗膜。 然後’以具有捲繞聚醯胺製之布料之滾筒的摩擦機， 以滾筒轉數5 00rpm、控制台移動速度1 cm/秒的條件，對 此塗膜進行摩擦處理。此時評價圖型有無切削或剝離。 (5 )密著性之評價 除未使用光罩外，其他與上述間隔物之形成相同，形 成硬化膜後’以JIS K-5400 ( 1 900 ) 8.5之附著性試驟中 之8.5 · 2之棋盤格膠帶法評價。此時，丨〇 〇個棋盤格中殘 留之棋盤格的數目如表2所示。 (6 )耐熱性之評價 除了未使用光罩外，其他與上述間隔物之形成相同， 形成硬化膜後’在24(TC烘箱中加熱60分鐘，測定加熱前 -51 - 200903150 後之膜厚，以殘膜率（加熱後之膜厚x 1 00/加熱前之膜厚 )進行評價。 (7 )間隔物圖型面之評價 以掃描型電子顯微鏡觀察所得之間隔物表面。觀察到 凹凸狀之表面粗糙時，評價爲X，未觀察到凹凸狀之表面 粗糙時，評價爲〇。結果如表2所示。 -52- 200903150 B成份 重量份 100 〇 100 100 80+60+5 〇 o 100 100 〇 50+50 85+15 80+60+7.5 80+60+7.5 80+60+7.5 80+60+7.5 〇 100 100 o o 100 o o 100 騷 “mil w 1 1 Β-1 丨 Β-1 B-1+B-2+B-4 ί____ΒΓ1 l CD l B-1 B-1+B-3 B-1+B-5 B-1+B-2+B-4 B-1+B-2+B-4 B-1+B-2+B-4 B-1+B-2+B-4 l B-1 B-1 m B-1 ! CD B-1 CA2] 重量份 〇 〇 〇 〇 Ο o O o o o o o o o LO CO 1 1 1 1 1 1 種類 QQ. ί CM β-3 ί CVJ CO CM CM CM c〇 对 CNJ 4 1 1 1 1 1 1 〔A1〕 重景份 〇 100 〇 ! 1〇〇 〇 τ— 〇 o 100 100 o o 〇 o o O T— o o o o o 100 o o o 100 I 100 100 種類 Α-1 Α-2 Α-3 A-1 Α-1 A-1 1__ A-1 1 A-4 ! A-4 1A-4I IA-4I IA-4I 1A-41 lA-4_I 1__A-4__I A-4 1A-4__I τ- Ι a a —2 < A-1 Ί A-1 j 組成物種 (S-1) (S-2) (S-3) (S-4) (S-5) (S-6) (S-7) (S-8) (S-9) 1 (S-10) I (S-11) ! (S-12) | (S-13) (S-14) [(S-15) I (S-16) I (S-17) I I (s-1) i (s-2) (s-3) (s-4) (s-5) j (s-6) 實施例1 CN 舾 I實施例3 I 實施例4 丨實施例5 I 丨實施例6 1 實施例7j 1實施例8 | 丨實施例9」 實施例10 I實施例11 I 實施例12 實施例13 實施例14 I實施例15 I 實施例16 |實施例17 1 1—H AJ -1Λ 丨比較例2 | Λ3 JA 1比較例4 UJ 比較例6 -53- 200903150 i Im ¢1 Hffl 1 1 1 1 \ 1 1 寸 o 〇 Q 種類 1 1 1 1 1 1 Q 1 D-1 1 D-1 ig u 1 重量份 5+5+5+2.5 5+5+5+2.5 5+5+5+2.5 5+5+5+2.5 5+5+5+2.5 5+5+5+2.5 5+5+5+2.5 ! 5+5+5+2.5 5+5+5+2.5 5+5+5+2.5 5+15 5+15 ! 5+5+5+2+2+1 5+5+5+2+2+1 5+5+5+2+2+1 5+5+5+2+2+1 5+5+2+2+1 5+5+5+2.5 5+5+5+2.5 5+5+5+2.5 寸 駿 w C-1 + C-5 + C-6 + C-7 I______ C-1 + C-5 + C-6 + C-7 ! C-1 + C-5 + C-6 + C-7 C-1 + C-5 + C~6 + C~7 1 C_2 + C~5 + C~6 + C_7 c-t + G-5 + G-6 + G-7 C~1 + C-5 + C~6 + C~7 ! C-1 + C-5 + C-6 + C-7 C~1 + C~5 + C—6 + C~7 C—1 + C~~5 + C~6 + C—7 C-1+C-4 C-1+C-4 C-1+C-3+C-4+C-5+C-6+C-7 | C-1+C-3+C-4+C-5+C-6+C-7 C-1 +C-3+C-4+C-5+C-6+07 C-1 +C-3+C-4+C-5+C-6+C-7 C-1 +C-3+C-5+C-6+C-7 C-1 + C-5 + C-6 + C-7 C~1 + C-5 + C~6 + C_7 C-3 C-3 C~1 + C_5 + C~6 + C~7 C-3 組成物種 (S-1) (S-2) (S-3) (S-4) (S-5) (S-6) (S-7) 1 (S-8) (S-9) ί (s-io) | (s—11) | (S-12) I I (S-13) I | (S-14) | | (s-15) 1 | (s-16) I | (s-17) 1 | (s-1) | (s-2) | (s-3) (s-4) (s-5) 1 (s-6) 實施例1 CN 闺 H 實施例3 寸 § 闺 實施例5 1 丨實施例6 1 闺 丨實施例8 I 丨實施例9 實施例10 實施例11 實施例12 實施例13 實施例14 實施例11j 實施例16 實施例17 鎰 JJ) JA 比較例2 cn 比較例4 XT) m 鎰 ΟΛ 比較例6 -54 - 200903150 z^ 條 回 m amL 變位量(um) 0.51 0.53 0.61 0.45 0.51 0.65 0.55 0.54 0.53 0.61 0.71 0.68 0.71 0.64 0.71 0.77 0.52 0.65 0.66 0.55 0.51 0.63 0.44 |彈性回復率(％) § 〇〇 CO CO in co S 00 in CO s s s s s o s in CO CO to o s s 感度 ! (J/mz) ! 1000 〇 g 900 1000 800 800 I 900 I 900 700 800 1000 900 700 700 700 700 j 400 ! 3000 j 2000 | 2000 1 2000 2000 | 700 顯像時間 (秒） 〇 〇 s 〇 〇 g o o s o o o in s o o o 〇 g o 敏輻射線 性乾薄膜 I 1 I 1 I I I I I 1 I 1 I 1 1 1 1 1 1 I I J-2 組成物種 (S-1) (S-2) I (S-3) (S-4) | (S-5) I (S-6) | I (S-7) I | (S-8) I I_(S-9)_I I (s-io) | I (S-1D | | (S-12) 1 | (S-13) I | (S-14) I (S-15) I | (S-16) I (S-17) I | (s-1) | (s-2) (s-3) (s-4) | (s-5) | (s-6) L實施例1 1 1實施例2 I I實施例3 | 寸 叙 in 辑 Μ m m § 丨實施例8 I L實施例9 I 實施例10 實施例11 |實施例12 | 實施例13 實施例14 實施例15 實施例16 ! 實施例17 比較例1 比較例2 比較例3 比較例4 比較例5 比較例6 -55- 200903150 N& mm 齪s 1 I 1 〇 1 1 X mm w賴 細 mm 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 X 〇 X 耐熱性 L (%) g 00 σ> CO σ> σ> α> 00 σ> CO σ> 00 Oi § 00 〇i 00 σ> 00 σ> 00 σ> 00 σ> CO σ> s 00 σ> S s s σ> 00 σ> 00 σ> s 铝a ws 铂s Ο ο ο ο 〇 Τ-» ο o o o ο ο ο τ—· ο ο ο ο τ— Ο § LT5 σ> ο ο ο S mm 钽诹 fi-N 戰龌 *冢 _ m 廉 廉 堆 Ι-: 廉 m m m m m m m 嫉 鹿 m 藤 体 体 m 廉 廉 m 組成物種 (S-1) (S-2) 1 (S-3) 1 1 (S-4) 1 | (S-5) I ί JS-6) J [(S-7)」 1 (S-8) I 1 (S-9) J (S-10) (S-11) (S-12) (S-13) (S-14) L (S-15) I (s-16) 1 (S-17) J s l ΐ5 ίο ί ίο <p 實施例1 實施例2」 1實施例3 寸 U |B： vr> m w r-» § 1實施例81 1實施例9 ] 實施例10 實施例11 實施例12 實施例13 1 實施例14 實施例15 實施例16 卜 i 闺 in 比較例1 比較例2 比較例3 比較例4 比較例5 比較例6 -56- 200903150 【圖式簡單說明】 圖1係說明液晶顯示元件之構造之一例的模式圖。 圖2係說明液晶顯示元件之構造之其他例的模式圖。 圖3係例示彈性回復率評價之負荷時及去除負荷時之 荷重-變形量曲線圖。 -57-Measured by the Associates Inc.) The intensity of the Ι ray wavelength of 365 nm is usually 1 〇〇 to 1 0,00 0 J/m 2 ', more preferably 5 00 〜1,500 J/m 2 . - (C) Step - Next, the film after exposure is subjected to development to remove unnecessary portions to form a predetermined pattern. The developing solution for imaging is preferably an alkali developing solution such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, ammonia or the like; an aliphatic group such as ethylamine or n-propylamine; An amine; an aliphatic secondary amine such as diethylamine or di-n-propylamine; an aliphatic tertiary amine such as trimethylamine, methyldiethylamine, dimethylethylamine or triethylamine; pyrrole, piperidine, N -methylpiperidine, N-methylpyrrolidine, 1,8-diazabicyclo[5.4.0]-7-undecene, 1,5-diazabicyclo[4.3.0]-5 - an alicyclic tertiary amine such as decene; an aromatic tertiary amine such as pyridine, trimethylpyridine, lutidine or quinoline; an alkanolamine such as ethanol dimethylamine, methyldiethanolamine or triethanolamine; An aqueous solution of a basic compound such as a methyl ammonium salt such as methyl ammonium hydroxide or tetraethylammonium hydroxide. Further, a water-soluble organic solvent such as methanol or ethanol or an interfacial surfactant may be added to the aqueous solution of the basic compound. The development method may be a liquid filling method, a dipping method, a shower method, etc. The development time is usually about 10 to 180 seconds. After the development, for example, it is washed with running water for 30 to 90 seconds, and then dried by, for example, compressed air or compressed nitrogen to form a desired pattern. - (丁)Step - -39- 200903150 Next, the pattern obtained is, for example, a heating device such as a hot plate or an oven, at a predetermined temperature, for example, 100 to 23 ° C, for a predetermined time, for example, 5 to 30 on a hot plate. In minutes, the oven is heated for 30 to 180 minutes, that is, it can be baked to obtain the predetermined spacer. In the case of the conventional sensitive radiation linear resin composition for forming a spacer, when the heat treatment is not performed at a temperature of 180 ° to 30 ° C or higher, sufficient performance of the obtained spacer cannot be exhibited, but the sensitive radiation linear resin of the present invention is composed. In the case where the heating temperature is lower than the conventional low temperature, the resin substrate does not become yellow or deformed, and a spacer excellent in various properties such as compressive strength, abrasion resistance at the time of liquid crystal alignment, and adhesion to a substrate can be formed. Liquid crystal display element The liquid crystal display element of the present invention comprises the spacer of the present invention formed as described above. The structure of the liquid crystal display device of the present invention is not particularly limited. For example, as shown in FIG. 1 , a color filter layer and a spacer are formed on a substrate, and two alignment films and opposite transparent electrodes are disposed via a liquid crystal layer. The structure to the substrate or the like. Further, as shown in Fig. 1, a protective film can be formed on the polarizing plate or the color filter layer as necessary. Further, as shown in Fig. 2, a color filter layer and a spacer are formed on the substrate, and a TN-TFT type liquid crystal display element can be formed by facing the thin film crystal (TFT) array via the alignment film and the liquid crystal layer. If necessary, a protective film is formed on the polarizing plate or on the color filter layer. As described above, the sensitive radiation linear resin composition of the present invention can obtain a high-sensitivity of -40 to 200903150 degrees and a high resolution, and a sufficient pattern shape can be obtained even at an exposure amount of 100 (Η/m2 or less), and development can be formed. Excellent, elastic recovery, abrasion resistance, adhesion to a substrate, heat resistance, etc., and a spacer for a liquid crystal display element having a rough surface having no uneven surface, and a resin substrate is not produced. Yellowing or deformation. The liquid crystal display device of the present invention is excellent in various properties such as sensitivity, developability, elastic recovery, abrasion resistance, adhesion to a substrate, heat resistance, and the like, and the surface of the pattern has no irregularities. The separator having a rough surface has long-term high reliability. EXAMPLES Hereinafter, examples of the present invention will be specifically described by way of examples. Here, % and % are based on weight. Synthesis Example 1 2, 2'-even 5 parts by weight of nitrogen bisisobutyronitrile and 25 parts by weight of 3-methoxybutyl acetate were placed in a flask equipped with a cooling tube and a stirrer, followed by adding 18 parts by weight of methacrylic acid and tricyclomethacrylate [5.2.1.02' 6 ] 25 parts by weight of decane-8-ester, 30 parts by weight of 2-hydroxyethyl methacrylate and 22 parts by weight of benzyl methacrylate', and then nitrogen substitution, the temperature of the solution is raised to 80 by stirring slowly. °C 'The polymerization was carried out for 5 hours at this temperature to obtain a copolymer [α-l] solution having a solid concentration of 28.8%. The obtained copolymer [α-l] was subjected to GPC (gel permeation chromatography) -41 - 200903150 GPC-101 (manufactured by Showa Denko Electric Co., Ltd.) has a Mw of 1,3,0. Next, 2-methylpropenyloxyethyl isocyanate (commercial product: karenz MOI, Showa Denko) After adding a part by weight of 4-methoxyphenol oxime to the copolymer [α-l] solution, the reaction was carried out at 4 (Γ, stirring for 1 hour, and then stirring at 60 t for 2 hours. From 2_ The reaction of the isocyanate group of methacryloxyethyl isocyanate with the hydroxyl group of the copolymer [α-1] is carried out by IR (infrared absorption) spectroscopy, the polymer solution [α -1], after 1 hour of reaction The solution and the solution after reacting at 40 ° C for 1 hour and then at 60 ° C for 2 hours were confirmed by IR spectroscopy. The isocyanate group of 2-methacryloxyethyl isocyanate is reduced in the vicinity of 2,270 (1:1) to obtain a [a] polymer solution having a solid content of 30.0%. This [A] polymer The polymer (A-1). Synthesis Example 2 The same as in Synthesis Example 1 '14 parts by weight of 2-propenyloxyethyl isocyanate (trade name: karenz AOI, manufactured by Showa Denko Co., Ltd.) and 4-methoxy group After adding 0.1 part by weight of benzoquinone to the copolymer [a-1] solution, the mixture was stirred at 40 ° C for 1 hour and stirred at 60 ° C for 2 hours to cause a reaction. A [A] polymer solution having a solid concentration of 30% to 5% was obtained. This [A] polymer is a polymer (A-2). Synthesis Example 3 In the same manner as in Synthesis Example 1, methacryloxybutyl butyl isocyanate (trade name: karenz MOI-C4, manufactured by Showa Denko Co., Ltd.), 17 parts by weight, -42 to 200903150, and 4-methoxyphenol ol weight were used. After adding the above-mentioned copolymer [α-1] solution, it was 40. (:, stirring for 1 hour, and then taking 60. (:, stirring for 2 hours to produce a reaction. Obtaining a solid solution concentration of 31.0% [A] polymer solution. This [Α] polymer is a polymer (Α- 3) Synthesis Example 4 5 parts by weight of 2,2'-azobisisobutyronitrile, 0 parts by weight of 3-methoxybutyl acetate, and 125 parts by weight of propylene glycol monomethyl ether acetate were placed in a cooling tube and a mixer. In the flask, 18 parts by weight of methacrylic acid, 25 parts by weight of tricyclo [5.2.1.〇2,6]nonane-8-ester, and 5 parts by weight of styrene and 5 parts by weight of butadiene were added. 2,(6-hydroxyhexyloxy)ethyl methacrylate (trade name: PLACCEL FM1D (manufactured by Dicel Chemical Industry Co., Ltd.) 25 parts by weight and tetrahydrofuran-2-ester methacrylate 22 aliquots' followed by nitrogen After the substitution, slowly stir the solution to make the solution temperature _ 2] solution. α 2 ] Polymerization was carried out by GPC (gel permeation chromatography to 80 C ' at this temperature for 5 hours to obtain a copolymerization of solid concentration of 29.1%. The copolymer GW (made by Zhaocheng Co., Ltd.) was measured to have a heart of 18, 〇〇〇. Then '2 methacrylofluorene 14 parts by weight of ethyl isocyanate (trade name: karenz MOI, manufactured by Otsuka Electric Co., Ltd.) and methoxy group, 1 part by weight, added to the copolymer [α-2] solution, and stirred at 4 ° C for 1 hour. 'The reaction was further carried out by stirring for 2 hours in 6 passages to obtain a polymer solution having a solid concentration of 31% by weight. [a] The polymer was a polymer (A-4). -43- 200903150 Synthesis Example 5 Put 7 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) and 250 parts by weight of diethylene glycol methyl ether into a flask equipped with a cooling tube and a stirrer. Then add methacrylic acid. 18 parts by weight, 34 parts by weight of tricyclo [5.2.1.02'6] decane-8-ester, 5 parts by weight of styrene, 5 parts by weight of butadiene, and 40 parts by weight of glycidyl methacrylate, and then After nitrogen substitution, 'slow stirring' was carried out to raise the temperature of the solution to 70. (:, the polymerization was carried out for 5 hours at this temperature to obtain a copolymer [β-1] solution having a solid concentration of 3丨.0%. The copolymer [β -1] solution was obtained by GPC (gel permeation chromatography) GP C -1 0 1 (Showa Denko Co., Ltd.) The μ w was measured to be 1 1,000. Synthesis Example 6 7 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts by weight of propylene glycol monoethyl ether acetate were placed in a cooling tube and a mixer. In the flask, 19 parts by weight of styrene, 38 parts by weight of tricyclo [5.2.1.02,6]decane-8-ester, 13 parts by weight of methacrylic acid and methyl glycidyl methacrylate 3 were added. After 0 parts by weight, nitrogen substitution was carried out, and the temperature was raised to 70 ° C under stirring for 7 hours at this temperature to carry out polymerization to obtain a polymer solution containing the copolymer [β-2]. The solids concentration of this polymer solution was 3 2 · 9 %. The obtained copolymer [β-2] solution was measured by GPC (gel permeation chromatography) G P C -1 0 1 (manufactured by Showa Denko Co., Ltd.) to have a M w of 1,200 Å. -44- 200903150 Synthesis Example 7 7 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) and 250 parts by weight of diethylene glycol methyl ether were placed in a flask equipped with a cooling tube and a stirrer. Then, 18 parts by weight of methacrylic acid, 34 parts by weight of tricyclo [5-2. 1 〇 2'6] decane-8-ester methacrylate, 5 parts by weight of styrene, 5 parts by weight of butadiene, and methyl group were added. 20 parts by weight of 3,4-epoxycyclohexylmethyl acrylate and 20 parts by weight of tetrahydrofuran-2-methacrylate, and then nitrogen substitution, the temperature of the solution is raised to 70 ° C under gentle stirring, this temperature The polymerization was carried out for 5 hours while maintaining a copolymer [β-3] solution having a solid concentration of 30.0%. The obtained copolymer [β-3] solution was measured by GPC (gel permeation chromatography) GPC-101 (manufactured by Showa Denko Co., Ltd.) to have a Mw of 11,000 °. Synthesis Example 8 2, 2'-even 7 parts by weight of nitrogen bis(2,4-dimethylvaleronitrile) and 250 parts by weight of propylene glycol monomethyl ether acetate were placed in a flask equipped with a cooling tube and a stirrer, followed by adding 5 parts by weight of styrene and 18 parts by weight of methacrylic acid. a portion, 17 parts by weight of tricyclo [5.2.1.02'6]nonane-8-ester, 40 parts by weight of 3-(methacryloxymethyl)-3-ethyloxetane, 20 parts by weight of tetrahydrofuran-2-methacrylate, and then subjected to nitrogen substitution, the temperature of the solution was raised to 70 ° C with stirring, and the polymerization was carried out for 5 hours at this temperature to obtain a polymerization containing the copolymer [β_4]. Solution. The solid solution concentration of the polymer solution was 29.0%, and the composition of the composition solution of Example 1 was measured using GPC (gel permeation-45-200903150 chromatography) GPC-101 (manufactured by Showa Denko Co., Ltd.). The [A] component was prepared as the [A] polymer solution obtained in Synthesis Example 1 as 100 parts by weight of the polymer (A-1), and the copolymer [β_ι] obtained in Synthesis Example 5 was 10 parts by weight, and the [Β] component was Dipentaerythritol hexaacrylate (trade name: KAYARAD DPHA, manufactured by Sakamoto Chemical Co., Ltd.) 1 part by weight, [C] is 1-[9-ethyl-6-(2-methylbenzoinyl)-9 .Η.-carbazole_3_yl]-ethane-1-ketooxime-oxime acetate (trade name "IRGACURE 0X02, manufactured by Ciba Specialty Chemicals Inc") 5 parts by weight, 2, 2' - Bis(2-chlorophenyl)-4,4',5,5, tetraphenyl-1,2'-biimidazole 5 parts by weight, 4,4'-bis(diethylamino)benzophenone 5 parts by weight, 2.5 parts by weight of 2-hydrothiobenzothiazole, 5 parts by weight of γ-glycidoxypropyltrimethoxydecane followed by an auxiliary agent, FTX-218 of a surfactant (trade name, ) Neos system) 0.5 parts by weight and 4 to maintain the stabilizer Sprinkle benzene 0.5 parts by weight, dissolved in propylene glycol monomethyl ether acetate, so that the solid content concentration of 30% with an aperture diameter square. Microfilter 5 μιη by filtration, to prepare a composition solution. In Table 1, the components other than the polymer are as follows. [Β] Ingredients (Β-1): Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name "KAYARAD DPHA") -46 - 200903150 (B_2): Contains polyfunctional urethane acrylate vinegar Commercial product of the compound (trade name KAYARADDPHA-40H) (B-3): pentaerythritol tetraacrylate (trade name "aronix M-450" 'made by East Asia Synthetic Co., Ltd.) (B-4) : ω-carboxy poly Lactone monoacrylate (trade name "aTDiiix M-5300", manufactured by Toagosei Co., Ltd.) (B-5) : 1,9-decane diacrylate (trade name "light acrylate 1,9-NDA" Rongshe Co., Ltd.) [C] Ingredient (C-1): 1-[9-Ethyl-6-(2-methylphenylindenyl)-9.1-oxazol-3-yl]-ethane-丨·ketooxime-〇-acetate) (trade name “irgacuRE 0X02 'Ciba Speciaity Chemicals Inc.) (C-2): Ethyl-1-[9-ethyl-6-[2-methyl -4-(2,2-Dimethyl-1,3-dioxolanyl)methoxybenzoinoxazol-3-yl]-1-(0-ethylindenyl) (ADEKA Corporation , N-1919) (C-3) : 2 -Methyl-1-(4-methylphenylthio)-2-morpholinylpropan-1-yl (trade name Irgacure907, Ciba. Speciali Ty. Chemicals Co., Ltd.) (C-4): 2-(4-methylbenzyl)-2-(dimethylamino)-l-(4-morpholinylphenyl)-butylamine-1-anthracene茼 Product name Irgacure 379, Ciba · Speciality . Chemicals company (C-5) : 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl- 1,2 '-Biimidazole-47- 200903150 (C-6) : 4,4'-bis(diethylamino)benzophenone (C-7): 2-Hydroxythiobenzothiazole [D] D-1): a polyfunctional novolac type epoxy resin (trade name, epitokel 52, epitokel 52) Examples 2 to 16 and Comparative Examples 1 to 5 were prepared in the same manner as in Example 1. Solution. The results are shown in Table 1. Further, Example 17 and Comparative Example 6 were carried out by a dry film method. Formation of spacers Examples 2 to 16 and Comparative Examples 1 to 5 were applied to a substrate by using a spin coater to form a spacer. Details are as follows. The composition solution was applied onto an alkali-free glass substrate using a spin coater and preheated on a hot plate at 100 ° C for 3 minutes to form a film having a film thickness of 3.5 μm. Next, the resulting film was exposed through a residual pattern mask of ΙΟμπι square. Then, it was washed with pure water of 0.05% by weight in a lithium hydroxide solution at 25 ° C for 1 minute, and then heated in an oven at 230 ° for 30 minutes to form a spacer. Example 1 5 A spacer was formed by a dry film method. Details are as follows. Example 1 7 The liquid composition (S -1 7 ) of the radiation-sensitive resin composition was prepared by the film method of the dry-48-200903150 film method, and the film was evaluated in the same manner as in Examples 1 to 14. The components are shown in Table 1. The base film before the exposure step. The evaluation results are shown in Table 2. The transfer properties described below are also shown in Table 2. Dry film and transfer were made as follows. The liquid S-17) of the sensitive radiation linear resin composition was applied to a polyethylene terephthalate having a thickness of 38 μm using an applicator (the film was heated at 1 ° C for 5 minutes to prepare a thickness of 4 μm). Linear dry film (J-1). Secondly, the linear transfer of the sensitive radiation is superimposed on the surface of the glass substrate to make the surface of the linear transfer layer of the sensitive radiation connect to the linear dry film of the sensitive radiation by thermal compression bonding (J-1). ) Glass substrate - Evaluation of transferability of dry film transfer to glass substrate - Transfer of sensitive radiation linear dry film to glass 'dry film by thermal compression bonding method can be uniformly transferred onto a glass substrate, and evaluated as " When a part of the film remains on the base film, or the dry film cannot be densely bonded to the substrate, etc., and the dry film cannot be uniformly transferred onto the glass substrate, X (〇Comparative Example 6 uses a liquid composition of the sensitive radiation linear resin composition) Example 1 7: The liquid group of the sensitive radiation linear resin composition 1 7 ), the same as in Example 1 7 was used to prepare the radiation-sensitive linear dry thin film; the pattern-like peeling removal evaluation of the knot composition (PET) thin sensitive radiation dry film Heavy transfer onto the glass substrate At the time of the evaluation, the film was evaluated as ":s_6" (S-Mo (J-2) -49-200903150, and a pattern-shaped film was formed for evaluation. The components are shown in Table 1. Table 2 shows the evaluation results of the transferability as shown in Table 2. Next, various evaluations were carried out in the following manner. The evaluation results were as shown in Table 1. (1) The development time of the development time was set to 30, 40, 50, 60, 70, 80, 90] seconds, the residual image development time of the unexposed portion was observed with an optical microscope at each development time, and the shortest development time when no residue was observed in the unexposed portion was as shown. The shorter the film, the better the imageability is. (2) The evaluation of the sensitivity is the same as the formation of the spacer. When the spacer is formed, the residual film ratio of the exposure is exposed (film thickness after exposure baking XI 00 / film thickness after exposure) The above exposure amount is taken as the sensitivity. The exposure amount is 1,00 (U/m2 or less indicates good sensitivity. (3) Evaluation of elastic recovery rate For the spacer obtained, a micro compression tester (DUH-201) is used. , Shimadzu Manufacturing Co., Ltd.), with a load of 50 μm in diameter, its load speed and de-loading The speed is 2.6mN/sec, the load is up to 50mN, the load is removed after 5 seconds, and the load-variation curve and the load-deformation curve at the time of load are produced. At this time, as shown in Fig. 3, the load is The deformation of the load of 5〇mN is L1, and the evaluation of the load is 2100. When 90% of the weight of each table 2, the load of the product name plane load is -50-200903150 50mN, the deformation is L2' Calculate the elastic recovery rate. Elastic recovery rate (%) = L 2 X 1 0 〇/L 1 Elastic recovery rate (%) and deformation amount L1 (μ m ) are shown in Table 2. (4) Evaluation of the abrasion resistance The liquid crystal alignment agent AL3 046 (trade name 'JSR (manufactured)) was applied onto a substrate on which spacers were formed, using a liquid crystal alignment film coating printer, and then at 180 ° C. After drying for 1 hour, a coating film of a liquid crystal alignment agent having a film thickness of 〇·〇5 μηι was formed. Then, the coating film was subjected to a rubbing treatment under the conditions of a drum rotation number of 500 rpm and a table moving speed of 1 cm/sec by a friction machine having a roll of a cloth made of polyamide. At this time, the pattern is evaluated for cutting or peeling. (5) Evaluation of adhesion is the same as the formation of the above-mentioned spacer except that the mask is not used, and after forming the cured film, 8.5 of the adhesion test of JIS K-5400 (1900) 8.5 Checkerboard tape method evaluation. At this time, the number of the remaining checkers in the checkerboard is as shown in Table 2. (6) The evaluation of the heat resistance was the same as the formation of the spacer except that the mask was not formed, and after the cured film was formed, it was heated at 24 (TC oven for 60 minutes, and the film thickness after -51 - 200903150 before heating was measured, The residual film ratio (film thickness after heating x 1 00 / film thickness before heating) was evaluated. (7) Evaluation of spacer pattern surface The surface of the obtained spacer was observed by a scanning electron microscope. When the surface was rough, it was evaluated as X, and when the surface roughness of the unevenness was not observed, it was evaluated as 〇. The results are shown in Table 2. -52 - 200903150 B component parts by weight 100 〇 100 100 80+60+5 〇o 100 100 〇50+50 85+15 80+60+7.5 80+60+7.5 80+60+7.5 80+60+7.5 〇100 100 oo 100 oo 100 Sao “mil w 1 1 Β-1 丨Β-1 B-1 +B-2+B-4 ί____ΒΓ1 l CD l B-1 B-1+B-3 B-1+B-5 B-1+B-2+B-4 B-1+B-2+B- 4 B-1+B-2+B-4 B-1+B-2+B-4 l B-1 B-1 m B-1 ! CD B-1 CA2] Parts by weight 〇〇〇〇Ο o O Ooooooo LO CO 1 1 1 1 1 1 Type QQ. ί CM β-3 ί CVJ CO CM CM CM c〇 to CNJ 4 1 1 1 1 1 1 [A1] Re-scene 〇100 〇! 1〇〇 Τ— 〇o 100 100 oo 〇oo OT— ooooo 100 ooo 100 I 100 100 Category Α-1 Α-2 Α-3 A-1 Α-1 A-1 1__ A-1 1 A-4 ! A-4 1A -4I IA-4I IA-4I 1A-41 lA-4_I 1__A-4__I A-4 1A-4__I τ- Ι aa —2 < A-1 Ί A-1 j Composition species (S-1) (S-2 ) (S-3) (S-4) (S-5) (S-6) (S-7) (S-8) (S-9) 1 (S-10) I (S-11) ! ( S-12) | (S-13) (S-14) [(S-15) I (S-16) I (S-17) II (s-1) i (s-2) (s-3) (s-4) (s-5) j (s-6) Example 1 CN 舾I Example 3 I Example 4 丨 Example 5 I 丨 Example 6 1 Example 7j 1 Example 8 | 丨 Example 9] Example 10 I Example 11 I Example 12 Example 13 Example 14 I Example 15 I Example 16 | Example 17 1 1 -H AJ -1Λ 丨Comparative Example 2 | Λ3 JA 1 Comparative Example 4 UJ Comparative Example 6 -53- 200903150 i Im ¢1 Hffl 1 1 1 1 \ 1 1 inch o 〇Q Type 1 1 1 1 1 1 Q 1 D-1 1 D-1 ig u 1 Parts by weight 5+5+5+ 2.5 5+5+5+2.5 5+5+5+2.5 5+5+5+2.5 5+5+5+2.5 5+5+5+2.5 5+5+5+2.5 ! 5+5+5+ 2.5 5+5+5+2.5 5+5+5+2.5 5+15 5+15 ! 5+5+5+2+2+1 5+5+5+2+2+1 5+5+5+ 2+2+1 5+5+5+2+2+1 5+5+2+2+ 1 5+5+5+2.5 5+5+5+2.5 5+5+5+2.5 inch Chun w C-1 + C-5 + C-6 + C-7 I______ C-1 + C-5 + C -6 + C-7 ! C-1 + C-5 + C-6 + C-7 C-1 + C-5 + C~6 + C~7 1 C_2 + C~5 + C~6 + C_7 ct + G-5 + G-6 + G-7 C~1 + C-5 + C~6 + C~7 ! C-1 + C-5 + C-6 + C-7 C~1 + C~5 + C—6 + C~7 C—1 + C~~5 + C~6 + C—7 C-1+C-4 C-1+C-4 C-1+C-3+C-4+ C-5+C-6+C-7 | C-1+C-3+C-4+C-5+C-6+C-7 C-1 +C-3+C-4+C-5 +C-6+07 C-1 +C-3+C-4+C-5+C-6+C-7 C-1 +C-3+C-5+C-6+C-7 C- 1 + C-5 + C-6 + C-7 C~1 + C-5 + C~6 + C_7 C-3 C-3 C~1 + C_5 + C~6 + C~7 C-3 (S-1) (S-2) (S-3) (S-4) (S-5) (S-6) (S-7) 1 (S-8) (S-9) ί (s- Io) | (s-11) | (S-12) II (S-13) I | (S-14) | | (s-15) 1 | (s-16) I | (s-17) 1 | (s-1) | (s-2) | (s-3) (s-4) (s-5) 1 (s-6) Example 1 CN 闺H Example 3 Inch § Example 5 1 丨Example 6 1 闺丨 Example 8 I 丨 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Example 11j Example 16 Example 17 镒JJ) JA Comparative Example 2 cn Comparative Example 4 XT m 镒ΟΛ Comparative Example 6 -54 - 200903150 z^ Back to m amL Modification amount (um) 0.51 0.53 0.61 0.45 0.51 0.65 0.55 0.54 0.53 0.61 0.71 0.68 0.71 0.64 0.71 0.77 0.52 0.65 0.66 0.55 0.51 0.63 0.44 | Elastic recovery rate (%) § COCO CO in co S 00 in CO sssssos in CO CO to oss Sensitivity! (J/mz) ! 1000 〇g 900 1000 800 800 I 900 I 900 700 800 1000 900 700 700 700 700 j 400 ! 3000 j 2000 | 2000 1 2000 2000 | 700 Development time (seconds) 〇〇s 〇〇goosooo in sooo 〇go sensitive radiation linear dry film I 1 I 1 IIIII 1 I 1 I 1 1 1 1 1 1 II J-2 Composition species (S-1) (S-2) I (S- 3) (S-4) | (S-5) I (S-6) | I (S-7) I | (S-8) I I_(S-9)_I I (s-io) | I ( S-1D | | (S-12) 1 | (S-13) I | (S-14) I (S-15) I | (S-16) I (S-17) I | (s-1) (s-2) (s-3) (s-4) | (s-5) | (s-6) L Embodiment 1 1 1 Embodiment 2 II Example 3 | Inch in Μ mm § 丨Example 8 IL Example 9 I Example 10 Example 11 | Example 12 | Example 13 Example 14 Example 15 Example 16 ! Example 17 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 -55- 200903150 N& mm 龊s 1 I 1 〇1 1 X mm w rying mm 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇X 〇X Heat resistance L (%) g 00 σ > CO σ > σ > α > 00 σ > CO σ > 00 Oi § 00 〇i 00 σ > 00 σ > 00 σ > 00 σ > CO σ > s 00 σ > S ss σ > 00 σ > 00 σ> s aluminum a ws platinum s Ο ο ο ο 〇Τ-» ο ooo ο ο ο τ—· ο ο ο ο τ Ο § § LT5 σ> ο ο ο S mm 钽诹fi-N 龌 龌 冢 冢m cheap stacking -: cheap mmmmmmmm elk m vine body m cheap m constituent species (S-1) (S-2) 1 (S-3) 1 1 (S-4) 1 | (S-5 ) I ί JS-6) J [(S-7)" 1 (S-8) I 1 (S-9) J (S-10) (S-11) (S-12) (S-13) ( S-14) L (S-15) I (s-16) 1 (S-17) J sl ΐ5 ίο ί ίο <p Embodiment 1 Embodiment 2" 1 Embodiment 3 Inch U | B: vr> mw R-» § 1 Example 81 1 Example 9] Example 10 Example 11 Example 12 Example 13 1 Example 14 Example 15 Example 16 Bu I 闺in Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 ratio Comparative Example 6 Comparative Example 6 - 56 - 200903150 [Brief Description of the Drawings] Fig. 1 is a schematic view showing an example of the structure of a liquid crystal display element. Fig. 2 is a schematic view showing another example of the structure of a liquid crystal display element. Fig. 3 is a graph showing the load-deformation amount at the time of load evaluation of the elastic recovery rate and the load removal. -57-

Claims (1)

200903150 十、申請專利範圍 1.—種敏輻射線性樹脂組成物，其特徵係含有：[A1 ] 使下述式（1)表示之含異氰酸酯基之不飽和化合物與（ al)選自由不飽和羧酸及不飽和羧酸酐所成群之至少一種 與（a2) 1分子中含有至少1個羥基之不飽和化合物之共 聚物反應所得之聚合物，及200903150 X. Patent application scope 1. A sensitive radiation linear resin composition characterized by: [A1] an isocyanate group-containing unsaturated compound represented by the following formula (1) and (al) selected from unsaturated carboxylic acid a polymer obtained by reacting at least one of a group of an acid and an unsaturated carboxylic anhydride with a copolymer of an unsaturated compound containing at least one hydroxyl group in (a2) 1 molecule, and H2C=C—C—〇 -N=C=0 (式中’ R1係氫原子或甲基，η係1〜12之整數） [Α2] (ai)選自不飽和羧酸及不飽和羧酸酐所成群之 至少一種與（a3)具有氧環乙基或氧環丁基之不飽和化合 物的共聚物。 2 ·如申請專利範圍第1項之敏輻射線性樹脂組成物， 其中該（a2)成份爲下述式（2)表示的不飽和化合物，H2C=C—C—〇-N=C=0 (wherein R1 is a hydrogen atom or a methyl group, and η is an integer of 1 to 12) [Α2] (ai) is selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides. At least one of the groups is copolymerized with (a3) an unsaturated compound having an oxocycloethyl group or an oxocyclobutyl group. 2. The sensitive radiation linear resin composition of claim 1, wherein the component (a2) is an unsaturated compound represented by the following formula (2), (式中，R2係氫原子或甲基，1係1〜12的整數，m係1 〜6之整數）。 3 ·如申請專利範圍第1或2項之敏輻射線性樹脂組成 物’其係尙含有[B]聚合性不飽和化合物與[C]敏輻射線性 200903150 聚合引發劑。 4. 如申請專利範圍第1〜3項中任一項之敏輻射線性 樹脂組成物’其係用於形成液晶顯示元件用間隔物。 5. —種液晶顯示元件用間隔物，其特徵係由申請專利 範圍第1〜3項中任一項之敏輻射線性樹脂組成物形成所 成。 6. —種液晶顯示元件用間隔物之形成方法，其特徵係 至少含有以下記載順序之以下的步驟， (甲）在基板上形成申請專利範圍第1項之敏輻射線 性樹脂組成物之被膜的步驟， (乙）對該被膜之至少一部份進行曝光的步驟， (丙）使曝光後之該被膜進行顯像的步驟，及 (丁）使顯像後之該被膜進行加熱的步驟。 7 · —種液晶顯示元件，其特徵係具備申請專利範圍第 5項之間隔物。 -59-(wherein R2 is a hydrogen atom or a methyl group, and 1 is an integer of 1 to 12, and m is an integer of 1 to 6). 3. The sensitive radiation linear resin composition as claimed in claim 1 or 2, which contains [B] a polymerizable unsaturated compound and [C] a radiation radiation linearity 200903150 polymerization initiator. 4. The radiation sensitive linear resin composition of any one of claims 1 to 3 is used for forming a spacer for a liquid crystal display element. A spacer for a liquid crystal display element, which is characterized in that it is formed by forming a radiation sensitive linear resin composition according to any one of claims 1 to 3. 6. A method of forming a spacer for a liquid crystal display element, characterized in that it comprises at least the following steps in the order described below, (a) forming a film of the radiation-sensitive linear resin composition of claim 1 on the substrate. And (b) a step of exposing at least a portion of the film, (c) a step of developing the film after exposure, and a step of heating the film after development. 7 - A liquid crystal display element characterized by having a spacer of the fifth item of the patent application. -59-
TW097109643A 2007-03-20 2008-03-19 Sensitive linear resin composition and spacer for liquid crystal display device and method for manufacturing the same TWI427409B (en)

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