TW200907573A - Radiation- induced resin composition, spacer, protection film and forming method thereof - Google Patents

Radiation- induced resin composition, spacer, protection film and forming method thereof Download PDF

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TW200907573A
TW200907573A TW097118787A TW97118787A TW200907573A TW 200907573 A TW200907573 A TW 200907573A TW 097118787 A TW097118787 A TW 097118787A TW 97118787 A TW97118787 A TW 97118787A TW 200907573 A TW200907573 A TW 200907573A
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compound
radiation
film
group
resin composition
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TW097118787A
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TWI434137B (en
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Hitoshi Hamaguchi
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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
    • C08F20/00—Homopolymers and 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
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • 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
    • G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0755—Non-macromolecular compounds containing Si-O, Si-C or Si-N bonds

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Materials For Photolithography (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Liquid Crystal (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

The invention relates to an inductance irradiation linear resin combination, a spacer and a protecting film and a forming method thereof, characterized by comprising: (A) a copolymer including an unsaturated compound selected from at least one of unsaturated carboxylic acid and unsaturated carboxyl anhydride; (B) polymerized unsaturated compound; (C) inductance irradiation linear polymerization initiator; and (D) a compound with the structure in the formula (1).

Description

200907573 九、發明說明 【發明所屬之技術領域】 本發明係關於一種敏輻射線性樹脂組成物、液晶顯示 元件的間隔件及保護膜以及此等之形成方法。 【先前技術】 使用於液晶顯示元件之構件中，間隔件、保護膜等許 多係以光微影蝕刻所形成（例如有關間隔件，參照特開 200 1 -26 1 76 1 )。近年，液晶顯示元件面板的普及與大型化 迅速地進展，故從刪減成本及縮短步驟時間的觀點，在光 微影蝕刻步驟中，期盼輻射線之照射時間的縮短或顯像時 間之縮短。 然而，若使用自以往所知之敏輻射線性樹脂組成物而 縮短照射時間即藉低曝光量的輻射線照射步驟以形成間隔 件或保護膜，所得到之圖型狀薄膜的強度會不足，或圖型 尺寸小於所希望之値而無法得到所希望的圖型尺寸，而有 成爲面板不良的原因之問題。 另外，爲實施顯像時間之縮短，嘗試使用高濃度之顯 像液或提昇顯像性之敏輻射線性樹脂組成物。但，此等之 任一者的對策，亦於顯像時產生圖型狀薄膜的一部分剝離 之不佳情形，尤其，當形成間隔件時係圖型之截面形狀成 爲逆推拔狀（膜表面之邊長爲較基板側之邊長還長之逆梯 形形狀）而於其後進行之液晶配向膜的摩擦步驟時有時產 生圖型剝離之問題。尤其，採用上述所縮短之輻射線照射 -5- 200907573 步驟時易產生顯像時或摩擦步驟時之圖型剝離。 又，從刪減成本之觀點，液晶顯示元件面板製造之各 步驟產生不良之情形，使不良基板進行再生使用。尤其， 在形成間隔件或保護膜後之液晶配向膜形成步驟中產生不 良時，藉配向膜剝離液暫時剝離所形成之液晶配向膜，再 度形成液晶配向膜爲一般化。此處，從以往所知之敏輻射 線性樹脂組成物所形成之間隔件或保護膜係對於配向膜剝 離液之耐性不足，故產生在液晶配向膜再生步驟中之製品 良率降低的問題。 進一步，在使用以往所知之敏輻射線性樹脂組成物的 液晶顯示元件之間隔件或保護膜的形成中，加熱步驟之際 產生昇華物之問題仍存在，恐生產線步驟及液晶顯示元件 之污染。 進一步尙且，間隔件或保護膜係殘存於液晶顯示元件 內之「永久膜」，故要求雜質不會從此等溶出於元件內。 但，具備從以往所知之敏輻射線性樹脂組成物所形成之保 護膜、間隔件之液晶顯示元件係有時會產生被推斷爲起因 於所溶出之雜質的「預燒」，造成問題。 如此，用以形成近年之液晶顯示元件的間隔件或保護 膜之敏輻射線性樹脂組成物中，係具有高的輻射線感度， 即使以低曝光量亦可以所希望的圖型尺寸形成強度優之圖 型狀薄膜，所得到之圖型狀薄膜係於顯像步驟或摩擦步驟 中不會剝離，對於液晶配向膜剝離液之耐久性優，作爲液 晶顯示元件時不產生「預燒」，而且在形成圖型狀薄膜時 -6 - 200907573 之加熱步驟中而不產生昇華物已被要求。但，滿足上述全 部要求之敏輻射線性樹脂組成物係以往所未知。 【發明內容】 發明之揭示 本發明係依據上述之事情而成者，其目的係在於提供 一種具有高的輻射線感度，且即使以低曝光量亦具有所希 望的圖型尺寸且可得到強度優之圖型狀薄膜，於顯像步驟 或摩擦步驟中圖型不會剝離，對於液晶配向膜剝離液之耐 久性（耐藥品性）優，作爲液晶顯示元件時可形成不產生 「預燒」之間隔件或保護膜，而且在形成此等時之加熱步 驟中而不產生昇華物之敏輻射線性樹脂組成物。 本發明之另一目的係在於提供一種使用上述敏輻射線 性樹脂組成物之液晶顯示元件的間隔件或保護膜之形成方 法。本發明之再另一目的係在於提供一種從上述敏輻射線 性樹脂組成物所形成之液晶顯示元件的間隔件或保護膜， 進一步在於提供一種長期信賴性優之液晶顯示元件。 若依本發明，本發明之上述目的，第一係，藉由含有 如下之敏輻射線性樹脂組成物來達成： (A) 含有（a 1)選自由不飽和羧酸及不飽和羧酸酐所構 成之群的至少一種而成之不飽和化合物的共聚物（以下亦 稱爲「（A)共聚物」）、 (B) 聚合性不飽和化合物、 (C) 敏輻射線性聚合起始劑、以及 200907573 (D)具有以下述式（1) 本BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a radiation sensitive linear resin composition, a spacer for a liquid crystal display element, a protective film, and a method of forming the same. [Prior Art] Among the members used for the liquid crystal display element, many of the spacers, the protective film, and the like are formed by photolithography (for example, the spacer, see JP-A-200 1-26 1 76 1). In recent years, the popularity and large-scale development of liquid crystal display device panels have progressed rapidly. Therefore, in the photolithography etching step, the irradiation time of the radiation is shortened or the development time is shortened from the viewpoint of cost reduction and step time reduction. . However, if the irradiation time is shortened by using a radiation-sensitive linear resin composition known from the prior art, that is, by a low-exposure radiation irradiation step to form a spacer or a protective film, the resulting pattern-like film may be insufficient in strength, or The pattern size is smaller than the desired size and the desired pattern size cannot be obtained, and there is a problem that the panel is defective. Further, in order to shorten the development time, it is attempted to use a high-concentration imaging liquid or a sensitive radiation-sensitive linear resin composition for enhancing development. However, the countermeasure against any of these methods also causes a poor peeling of a part of the pattern-shaped film at the time of development, and in particular, when the spacer is formed, the cross-sectional shape of the pattern is reversed (film surface) When the side length is longer than the side of the substrate side and the reverse trapezoidal shape is long, and the rubbing step of the liquid crystal alignment film is performed later, the pattern peeling may occur. In particular, the use of the above-described shortened radiation irradiation -5-200907573 step is liable to cause pattern peeling during development or during the rubbing step. Further, from the viewpoint of cost reduction, the steps of manufacturing the liquid crystal display panel are defective, and the defective substrate is reused. In particular, when the liquid crystal alignment film forming step is not performed in the step of forming the liquid crystal alignment film after forming the spacer or the protective film, the liquid crystal alignment film formed by temporarily peeling off the film peeling liquid is formed, and the liquid crystal alignment film is formed again. Here, the spacer or the protective film formed from the conventionally known radiation-sensitive linear resin composition is insufficient in resistance to the alignment film peeling liquid, so that the yield of the product in the liquid crystal alignment film regeneration step is lowered. Further, in the formation of a spacer or a protective film of a liquid crystal display element using a conventionally known radiation-sensitive linear resin composition, there is still a problem that a sublimate is generated at the time of the heating step, which may cause contamination of the production line step and the liquid crystal display element. Further, since the spacer or the protective film remains in the "permanent film" in the liquid crystal display element, impurities are not required to be dissolved from the element. However, the liquid crystal display element having the protective film or the spacer formed of the linear radiation-sensitive resin composition known in the prior art may cause "pre-burning" which is estimated to be caused by the eluted impurities, which causes a problem. Thus, the sensitive radiation linear resin composition for forming the spacer or the protective film of the liquid crystal display element of recent years has high radiation sensitivity, and the desired pattern size can be formed with excellent strength even at a low exposure amount. In the pattern-shaped film, the obtained pattern-shaped film is not peeled off in the developing step or the rubbing step, and is excellent in durability against the liquid crystal alignment film peeling liquid, and does not cause "pre-burning" as a liquid crystal display element, and It has been required to produce a sublimate in the heating step of -6 - 200907573 when forming a patterned film. However, the sensitive radiation linear resin composition satisfying all of the above requirements has not been known in the past. Disclosure of the Invention The present invention has been made in view of the above, and an object thereof is to provide a radiation sensitivity which is high, and which has a desired pattern size and excellent strength even at a low exposure amount. The pattern-shaped film does not peel off in the developing step or the rubbing step, and has excellent durability (chemical resistance) for the liquid crystal alignment film peeling liquid, and can be formed as a liquid crystal display element without "burning". A spacer or a protective film, and in the heating step of forming such a time, does not produce a sensitive radiation linear resin composition of the sublimate. Another object of the present invention is to provide a method of forming a spacer or a protective film of a liquid crystal display element using the above-described radiation sensitive resin composition. Still another object of the present invention is to provide a spacer or a protective film for a liquid crystal display element formed of the above-mentioned radiation sensitive resin composition, and further to provide a liquid crystal display element excellent in long-term reliability. According to the present invention, the first object of the present invention is achieved by the following linear composition of a radiation sensitive resin: (A) containing (a1) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides. a copolymer of at least one unsaturated compound (hereinafter also referred to as "(A) copolymer"), (B) a polymerizable unsaturated compound, (C) a radiation polymerization linear polymerization initiator, and 200907573 (D) has the following formula (1)

(式（1)中，「*」表示鍵結鍵） 所示之構造的化合物（以下亦稱爲「（D)成分」）。 本發明之上述目的，第二係，藉由液晶顯示元件之間 隔件或保護膜的形成方法來達成，其特徵在於··以下述記 載之順序含有至少下述（1)〜（4)之步驟： (1 )使上述之敏輻射線性樹脂組成物的被膜形成於基 板上之步驟； (2) 對該被膜之至少一部分照射輻射線之步驟； (3) 使輻射線照射後之被膜進行顯像的步驟；及 (4) 加熱顯像後之被膜的步驟。 本發明之上述目的’第三係藉由上述方法所形成之液 晶顯示元件之間隔件或保護膜來達成，第四係藉由具備上 述間隔件或保護膜之液晶顯示元件來達成。 用以實施發明之最佳形態 〈敏輻射線性樹脂組成物〉 以下，詳述有關本發明之敏輻射線性樹脂組成物的各 -8- 200907573 成分。 (A)共聚物 於本發明之敏輻射線性樹脂組成物所含有的（A)共聚 物，係含有（a 1)選自由不飽和羧酸及不飽和羧酸酐所構成 之群的至少一種（以下稱爲「化合物（al)」）而成之不飽和 化合物的共聚物。如此之（A)共聚物係可使含有化合物（al) 而成之不飽和化合物較佳係在溶劑中、適當的自由基聚合 起始劑的存在下進行自由基聚合來製造。 化合物（al)係只要具有羥基或羧酸酐構造與聚合性不 飽和鍵者即可，並無特別限定，但可舉例如不飽和單羧酸 化合物、不飽和二羧酸化合物、不飽和二羧酸化合物的酸 酐' 多環式之不飽和羧酸化合物、多環式之不飽和二羧酸 化合物、多環式之不飽和二羧酸化合物的酸酐等。 上述不飽和單羧酸化合物係可舉例如（甲基）丙烯酸、 巴豆酸、2-(甲基）丙烯醯氧基乙基琥珀酸、2-(甲基）丙烯 醯氧基乙基六氫酞酸、酞酸單羥乙基（甲基）丙烯酸酯、 ω-羧基聚己內酯單丙烯酸酯（從東亞合成（股）市售爲商品 名「Aronix Μ-53 00」）等； 上述不飽和二羧酸化合物係可舉例如馬來酸、富馬 酸、檸康酸、中康酸、衣康酸等； 上述不飽和二羧酸化合物之酸酐可舉例如例示來作爲 上述不飽和二羧酸化合物之化合物的酸酐等； 上述多環式之不飽和羧酸化合物可舉例如5_羧基雙 環[2.2.1]庚-2-烯、5-羧基-5-甲基雙環[2_2.1]庚-2-烯、5_ 200907573 羧基-5-乙基雙環[^^庚-】-烯' 5-羧基-6-甲基雙環 [2.2.1]庚-2-烯、5-羧基-6-乙基雙環[2.2.1]庚-2-烯等。 上述多環式之不飽和二羧酸化合物可舉例如5,6-二錢 基雙環[2.2.1]庚·2 -稀等。 上述多環式之不飽和二羧酸化合物之酸酐係可分別舉 例如例示來作爲上述多環式之不飽和二羧酸化合物之化合 物的酸酐等。 此等化合物（a 1)之中，從共聚合反應性、對於所得到 之共聚物之鹼顯像液的溶解性及取得容易性而言，宜爲丙 烯酸、（甲基）丙烯酸、馬來酸酐或2-甲基丙烯醯氧乙基六 氫酞酸。 在（A)共聚物之合成中，化合物（al)係可單獨或混合2 種以上而使用。 又，化合物（a 1)具有羧基者之情形，係亦可保護羧基 後供給至聚合，然後藉由去保護使羧基再生。此處，保護 羧基之保護基係無特別限定，而可使用公知者作爲羧基之 保護基。可舉例如三烷基甲矽烷基、1-烷氧基烷基、環狀 1 -烷氧基烷基等。更具體地可舉例如三甲基甲砂院基、二 甲基丁基甲矽烷基、1-乙氧基乙基、1-丙氧基乙基、四氫 呋喃基、四氫吡喃基、三苯基甲基等。 (A)共聚物係亦可爲僅含有如上述之化合物（al)而成 之不飽和化合物的共聚物，或亦可爲化合物（al)之外尙含 有（a2)其他之不飽和化合物（以下「稱爲化合物（a2)」）而 成之不飽和化合物的共聚物。 -10- 200907573 上述化合物（a2)較佳係選自由具有環氧乙烷基之聚合 性不飽和化合物及具有氧雜環丁基之聚合性不飽和化合物 所構成之群的至少一種（以下稱爲「化合物（a2-l)」）以及 選自上述化合物（al)、（a2-l)以外之不飽和化合物（以下稱 爲「化合物（a2-2)」）的至少一種。 上述化合物U2-1)例如具有環氧乙烷基之聚合性不飽 和化合物可舉例如具有環氧乙烷基之（甲基）丙烯酸酯化合 物、具有環氧乙烷基之α -烷基（甲基）丙烯酸酯化合物、 縮水甘油基醚化合物等。 此等之具體例，具有環氧乙烷基之（甲基）丙烯酸酯、 縮水甘油基酯係可舉例如（甲基）丙烯酸縮水甘油基酯、 (甲基）丙烯酸2-甲基縮水甘油基酯、（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_環氧基環甲酯等； 具有環氧乙烷基之α -烷基（甲基）丙烯酸酯化合物可 舉例如α-乙基丙烯酸縮水甘油基酯、正丙基丙烯酸縮 水甘油基酯、α-正丁基丙烯酸縮水甘油基酯、乙基丙 烯酸6,7-環氧基庚酯等； 縮水甘油基醚化合物分別可舉例如鄰乙烯基苯甲基縮 水甘油基醚、間乙烯基苯甲基縮水甘油基醚、對乙烯基苯 甲基縮水甘油基醚等。 具有氧雜環丁基之聚合性不飽和化合物係例如具有氧 雜環丁基之（甲基）丙烯酸酯等，其具體例係可舉例如3-((甲基）丙烯醯氧基甲基）氧雜環丁烷、3-((甲基）丙烯醯氧 -11 - 200907573 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 -二氟甲基氧雜環丁 烷、3-((甲基）丙烯醯氧基甲基）-2,2,4-三氟甲基氧雜環丁 烷、3-((甲基）丙烯醯氧基甲基）-2,2,4，4-四氟甲基氧雜環 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）丙烯醯氧基乙基）-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、2-((甲基）丙烯醯氧基乙基）氧雜環丁烷、2-甲基-2-((甲基） 丙烯醯氧基甲基）氧雜環丁烷、3 -甲基-2-((甲基）丙烯醯氧 基甲基）氧雜環丁烷、4 -甲基-2-((甲基）丙烯醯氧基甲基） 氧雜環丁烷、2-((甲基）丙烯醯氧基甲基）_2_三氟甲基氧雜 環丁烷、2-((甲基）丙烯醯氧基甲基）-3_三氟甲基氧雜環丁 烷、2-((甲基）丙烯醯氧基甲基）-4-三氟甲基氧雜環丁烷、 2-((甲基）丙烯醯氧基甲基）-2 -五氟乙基氧雜環丁烷、2_ ((甲基）丙烯醯氧基甲基）-3 -五氟乙基氧雜環丁烷、2-((甲 基）丙烯醯氧基甲基）-4-五氟乙基氧雜環丁烷、2-((甲基）丙 -12- 200907573 烯醯氧基甲基）-2-苯基氧雜環丁烷、2-((甲基）丙烯醯氧基 甲基）-3-苯基氧雜環丁烷、2-((甲基）丙烯醯氧基甲基）_4_ 苯基氧雜環丁院、2,3-二氟-2-((甲基）丙儲醯氧基甲基）氧 雜環丁院、2,4 -二氟- 2- ((甲基）丙烯醯氧基甲基）氧雜環丁 烷、3,3-二氟-2-((甲基）丙烯醯氧基甲基）氧雜環丁烷、 3,4 -二氟- 2- ((甲基）丙烯醯氧基甲基）氧雜環丁烷、4,4_二 氟-2-((甲基）丙烯醯氧基甲基）氧雜環丁烷、2_((甲基）丙烯 醯氧基甲基）-3,3,4-三氟氧雜環丁院、2-((甲基）丙烧醯氧 基甲基）-3,4,4-三氟氧雜環丁烷、2-((甲基）丙烯醯氧基甲 基）-3,3,4,4 -四氟氧雜環丁烷、2-((甲基）丙烯醯氧基乙基） 氧雜環丁院、2-(2-(2·甲基氧雜環丁基））乙基（甲基）丙稀酸 酯、2-(2-(3 -甲基氧雜環丁基））乙基（甲基）丙烯酸酯、2_ ((甲基）丙嫌酿氧基乙基）-2 -甲基氧雜環丁院、2-((甲基）丙 烯醯氧基乙基）-4 -甲基氧雜環丁烷、2-((甲基）丙烯醯氧基 乙基）-2 -三氟甲基氧雜環丁烷、2-((甲基）丙烯醯氧基乙 基）-3 -三氟甲基氧雜環丁烷、2_((甲基）丙烯醯氧基乙基）_ 4 -三氟甲基氧雜環丁烷、2_((甲基）丙烯醯氧基乙基）_2_五 氟乙基氧雜環丁烷、2-((甲基）丙烯醯氧基乙基）_3_五氟乙 基氧雜環丁烷、2-((甲基）丙烯醯氧基乙基）_4_五氟乙基氧 雜環丁烷、2-((甲基）丙烯醯氧基乙基）_2 -苯基氧雜環丁 烷、2-((甲基）丙烯醯氧基乙基）-3-苯基氧雜環丁烷、2_ ((甲基）丙烯醯氧基乙基）-4-苯基氧雜環丁烷、2,3-二氟-2-((甲基）丙烯醯氧基乙基）氧雜環丁烷、2，4-二氟- 2-((甲基） 丙烯醯氧基乙基）氧雜環丁烷、3,3-二氟-2-((甲基）丙烧醯 -13- 200907573 氧基乙基）氧雜環丁烷、3，4_二氟-2-((甲基）丙烯醯氧基乙 基）氧雜環丁烷、4，4-二氟- 2-((甲基）丙烯醯氧基乙基）氧雜 環丁烷、2-((甲基）丙烯醯氧基乙基）-3,3,4-三氟氧雜環丁 烷、2-((甲基）丙烯醯氧基乙基）-3,4,4-三氟氧雜環丁烷、 2- ((甲基）丙烯醯氧基乙基）-3,3,4,4-四氟氧雜環丁烷等。 此等化合物（a2-l)之中’就敏輻射線性樹脂組成物之 保存安定性高、所得到之間隔件或保護膜的耐熱性、耐藥 品性可更提昇而言，較宜使用（甲基）丙烯酸縮水甘油基 酯、（甲基）丙烯酸2-甲基縮水甘油基酯、（甲基）丙烯酸 3,4-環氧基環己基甲酯、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）-2-三氟甲基氧雜環丁烷、 3- (甲基丙烯醯氧基甲基）-2-苯基氧雜環丁烷、2-(甲基丙 烯醯氧基甲基）氧雜環丁烷或2-(甲基丙烯醯氧基甲基）_4-三氟甲基氧雜環丁烷。 化合物（a2-l)係可單獨或組合2種以上而使用。 上述化合物（a2-2)可舉例如（甲基）丙烯酸烷基酯、（甲 基）丙烯酸之脂環族酯、（甲基）丙烯酸芳酯、不飽和二羧 酸之二酯、（甲基）丙烯酸羥基烷酯、聚醚之（甲基）丙烯酸 酯化合物、芳香族乙烯基化合物及其他之不飽和化合物。 此等之具體例就（甲基）丙烯酸烷酯而言，可舉例如甲 基（甲基）丙烯酸酯、乙基（甲基）丙烯酸酯、正丙基（甲基） 丙烯酸酯、異丙基（甲基）丙烯酸酯、正丁基（甲基）丙烯酸 酯、異丁基（甲基）丙烯酸酯、第二丁基（甲基）丙烯酸酯、 第三丁基（甲基）丙烯酸酯等； ~ 14 - 200907573 就（甲基）丙烯酸之脂環族酯而言，可舉例如環己基 (甲基）丙烯酸酯、2 -甲基環己基（甲基）丙烯酸酯、三環 [5.2.1.02’6]癸-8-基（甲基）丙烯酸酯（以下，亦使「三環 [5.2.1.02’6]癸-8-基」稱爲「二環戊基」）、2-二環戊基氧 乙基（甲基）丙烯酸酯、異冰片基（甲基）丙烯酸酯、四氫糠 基（甲基）丙烯酸酯等； 就（甲基）丙烯酸酯芳酯而言，可舉例如苯基（甲基）丙 烯酸酯、苯甲基（甲基）丙烯酸酯等之（甲基）丙烯酸酯芳 酯；苯基（甲基）丙烯酸酯、苯甲基（甲基）丙烯酸酯等； 就不飽和二殘酸之二酯而言，可舉例如馬來酸二乙 酯、富馬酸二乙酯、衣康酸二乙酯等； 就（甲基）丙烯酸羥基烷酯而言，可舉例如2-羧基乙 基（甲基）丙烯酸酯、2-羥基丙基（甲基）丙烯酸酯等： 就聚醚之（甲基）丙烯酸酯化合物而言，可舉例如聚乙 二醇單（甲基）丙烯酸酯、聚丙二醇單（甲基）丙烯酸酯等； 就芳香族乙燒基化合物而言，可舉例如苯乙嫌、α_ 甲基苯乙烯、間甲基苯乙烯、對甲基苯乙烯、對甲氧基苯 乙烯等； 就其他之不飽和化合物而言，可分別舉例如（甲基）丙 烯腈、氯化乙烯、偏氯乙烯、（甲基）丙嫌醯胺、醋酸乙烯 酯、1，3-丁二烯、異戊二烯、2,3-二甲基-1,3-丁二烯、四 氫糠基（甲基）丙烯酸酯、Ν-環己基馬來醯亞胺、Ν-苯基馬 來醯亞胺、Ν -苯甲基馬來醯亞胺、N-琥珀醯亞胺二基- 3-馬來醯亞胺苯甲酸酯、Ν -琥珀醯亞胺二基-4-馬來醢亞胺 -15- 200907573 丁酸酯、N-琥珀醯亞胺二基-6-馬來醯亞胺戊酸酯、N-琥 珀醯亞胺二基-3-馬來醯亞胺丙酸酯、N-(9 -丙烯二基）馬來 醯亞胺等。 此等化合物（a2-2)之中，苯甲基（甲基）丙烯酸酯、正 丁基（甲基）丙烯酸酯、二環戊基（甲基）丙烯酸酯、苯乙 烯、1，3 -丁二烯或四氫糠基（甲基）丙烯酸酯就共聚合反應 性而言，佳。 化合物（a2 _ 2 )係可單獨或混合2種以上而使用。 於本發明之敏輻射線性樹脂組成物所含有的（A)共聚 物較佳係如上述般爲化合物（a 1)及（a2 )之共聚物，但（A)共 聚物係依據衍生自化合物（al)及（a2)之重複單元的合計， 含有衍生自化合物（al)之構成單元5〜40重量％，更宜爲含 有1 0〜3 0重量％。 使用於（A)共聚物之製造的化合物（a2)係宜含有化合 物（a2-l)。此時化合物（a2-l)及化合物（a2-2)之合計佔有的 化合物U2-1)之比率宜爲10重量％以上，更宜爲15〜75重 量%。 (A)共聚物係尤宜爲化合物（al)、（a2-l)及（a2-2)之共 聚物，使衍生自化合物（al)之構成單元、衍生自化合物 (a2-l)之構成單元及衍生自化合物（a2-2)之構成單元’依 據衍生自化合物（al)、（a2-l)及（a2-2)之重複單元的合計’ 宜對於化合物（al)含有〜40重量。/。、對於化合物（a2-l)含 有10〜70重量。/。及對於化合物（a2-2)含有10〜7〇重量％， 更宜對於化合物（a 1)含有5〜3 0重量％、對於化合物（a2 -1) 200907573 含有15〜60重量％及^於化合物（a2-2)含有15〜60重量 %。 含有如此之共聚物比率的（A)共聚物之本發明的敏輻 射線性樹脂組成物係保存安定性及對於鹼顯像液之溶解性 優，所得到之間隔件或保護膜具有充分的強度，可更容易 地得到所希望的圖型尺寸而言，佳。 (A)共聚物以凝膠滲透色層分析（GPC)所得到之聚苯乙 烯換算重量平均分子量（以下，稱爲「Mw」）宜爲 2000〜100000，更宜爲 5000〜50000。此時，若 Mw不足 2000，所得到之被膜的顯像性、殘膜率等會不足，恐損及 耐熱性等，另外，若Mw超過1 00000，有時顯像性、解 析度等不充分。 可使用於（A)共聚物之製造的溶劑並無特別限定，但 可舉例如二乙二醇、丙二醇單甲基醚、苯甲基醇、2-苯基 乙基醇、3-苯基-1-丙醇、3-甲氧基丁醇等之醇化合物； 乙二醇單甲基醚乙酸酯、乙二醇單乙基醚乙酸酯、乙 二醇單丁基醚乙酸酯、二乙二醇單甲基醚乙酸酯、二乙二 醇單乙基醚乙酸酯、丙二醇單甲基醚乙酸酯、丙二醇單乙 基醚乙酸酯、二丙二醇單甲基醚乙酸酯、二丙二醇單乙基 醚乙酸酯、3-甲氧基丁基乙酸酯、環己醇乙酸酯等之（聚） 伸烷基甘醇單烷基醚乙酸酯化合物； 二乙二醇二甲基醚、二乙二醇乙基甲基醚、二乙二醇 二乙基醚、二丙二醇二甲基醚、二丙二醇甲基乙基醚、二 丙二醇二乙基醚等之（聚）伸烷基甘醇二醚化合物； -17- 200907573 四氫呋喃等之其他的醚化合物； 甲乙酮、環己酮、2-庚酮、3-庚酮等之酮化合物； 二丙酮醇（亦即，4-羥基-4-甲基戊烷-2-酮）、4-羥基-4 -甲基己烷-2-酮等之酮醇化合物； 乳酸甲酯 '乳酸乙酯等之乳酸烷酯化合物； 2-羥基-2-甲基丙酸乙酯、羥基醋酸乙酯、2-羥基- 3-甲基丁酸甲酯、3 -甲氧基丙酸甲酯、3 -甲氧基丙酸乙酯、 3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、乙氧基醋酸乙 酯、3_甲基-3-甲氧基丁基乙酸酯' 3_甲基_3_甲氧基丁基 丙酸酯、醋酸乙酯、醋酸正丙酯、醋酸異丙酯、醋酸正丁 酯、醋酸異丁酯、蟻酸正戊酯、醋酸異戊酯、丙酸正丁 酯、酪酸乙酯、酪酸正丙酯、酪酸異丙酯、酪酸正丁酯、 丙酮酸甲酯、丙酮酸乙酯、丙酮酸正丙酯、乙醯基醋酸甲 酯、乙醯基醋酸乙酯、2 -氧丁酸乙酯等之其他酯化合物； 甲苯、二甲苯等之芳香族烴化合物； N-甲基吡咯烷酮、N，N-二甲基甲醯胺、Ν,Ν-二甲基乙 醯胺等之醯胺化合物等。 此等之溶劑中，從聚合性、作爲敏輻射線性樹脂組成 物時之各成分的溶解性、被膜形成的容易性等觀點，宜爲 丙二醇單甲基醚、乙二醇單甲基醚乙酸酯、二乙二醇單甲 基醚乙酸酯、二乙二醇單乙基醚乙酸酯、丙二醇單甲基醚 乙酸酯、丙二醇單乙基醚乙酸酯、二丙二醇單甲基醚乙酸 酯、二乙二醇二甲基醚、二乙二醇甲基乙基醚、二丙二醇 二甲基醚、3-甲氧基丁基乙酸酯、環己酮、2-庚酮、3-庚 -18- 200907573 酮、3-甲氧基丙酸乙酯、3_乙氧基丙酸甲酯、3_乙氧基丙 酸乙酯、3 -甲基_3_甲氧基丁基丙酸酯、醋酸正丁酯、醋 酸異丁酯、犠酸正戊酯、醋酸異戊酯、丙酸正丁酯、酪酸 乙酯、酪酸異丙酯、酪酸正丁酯或丙酮酸乙酯。 此等之溶劑係可單獨或混合2種以上而使用。 可使用於（a)共聚物的製造之自由基聚合起始劑並無 特別限定’可舉例如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）、4,4’-偶氮雙（4-氰戊酸）、二甲基- 2,2，-偶氮雙（2-甲基 丙酸酯）、2,2’-偶氮雙（4-甲氧基-2,4-二甲基戊腈）等之偶 氮化合物·，過氧化苯甲醯基、過氧化月桂醯基、第三丁基 過氧化三甲基乙酸酯、1,1-雙（過氧化第三丁基）環己烷等 之有機過氧化物；過氧化氫等。使用過氧化物作爲自由基 聚合起始劑時，係亦可併用還原劑而作爲氧化還原起始 劑。 此等之自由基聚合起始劑係可單獨或混合2種以上而 使用。 自由基聚合起始劑的使用量係相對於全不飽和化合物 100重量份，宜爲0.1-30重量份，更宜爲0.1~15重量 份。 聚合溫度宜爲0〜150°C ’更宜爲50~12〇C '聚合時間 宜爲10分〜20小時，更宜爲1〜7小時。 如此做法所得到之（A)共聚物係亦可直接供給至含有 此之聚合物溶液的敏輻射線性樹脂組成物調製，或從聚合 -19- 200907573 物溶液分離之後供給至敏輻射線性樹脂組成物的調製。 (B)聚合性不飽和化合物 就於本發明之敏輻射線性樹脂組成物所含有的（B)聚 合性不飽和化合物而言，宜爲於一分子中具有聚合性不飽 和鍵4個以上之化合物（以下稱爲「聚合性不飽和化合物 (B1)」）或於一分子中具有聚合性不飽和鍵1~3個之化合 物（以下稱爲「聚合性不飽和化合物（B2)」）。 如此之聚合性不飽和化合物（B 1)係可舉例如季戊四醇 四（甲基）丙烯酸酯、二季戊四醇五（甲基）丙烯酸酯、二季 戊四醇六（甲基）丙烯酸酯、三（2-(甲基）丙烯醯氧基乙基） 磷酸酯等之外，尙可舉例如具有直鏈烷撐基及脂環式構造 且具有2個以上之異氰酸酯基的化合物、與於分子內具有 一個以上之羥基且具有3〜5個之（甲基）丙烯醯氧基的化合 物反應所得到之胺基甲酸酯（甲基）丙烯酸酯化合物等。 聚合性不飽和化合物（B1)之市售品可舉例如 Aronix M-400 、 Aronix M-402 、 Aronix M-405 、 Aronix M-450 、 Aronix M-1310、Aronix M- 1 600、Aronix M- 1 960、Aronix M-7100、Aronix M-80 3 0、Aronix M-8060、Aronix M-8100、Aronix M8 53 0、Aronix M- 85 60、Aronix M-9050、 Aronix TO- 1 45 0、Aronix TO- 1 3 82(以上東亞合成（股） 製）、KAYARAD DPHA、KAYARAD DPCA-20、KAYARAD DPCA-30、KAYARAD DPCA-60、KAYARAD DPCA-120、 KAYARAD MAX-35 1 0(以上，日本化藥（股）製）、VI S C O A T 295 、 VISCOAT 3 00、 VISCOAT 3 60、 VISCOAT GPT、 -20- 200907573 VISCOAT 3PA、VISCOAT 400(以上，大阪有機化學工業 (股）製）、或就胺基甲酸酯丙烯酸酯化合物而言，可舉例 如 New Frontier R-l 150(第一工業製藥（股）製）、 KAYARAD DPHA-40H、UX-5 000(以上，日本化藥（股） 製）、UN-9000H(根上工業（股）製）等。 上述聚合性不飽和化合物（B2)可舉例如ω -羧基聚己 內酯單（甲基）丙烯酸酯、乙二醇（甲基）丙烯酸酯、1，6-己 二醇二（甲基）丙烯酸酯' 1,9-壬二醇二（甲基）丙烯酸酯、 四乙二醇二（甲基）丙烯酸酯、聚乙二醇二（甲基）丙烯酸 酯 '聚丙二醇二（甲基）丙烯酸酯、雙苯氧基乙二醇芴二 (甲基）丙烯酸酯、雙苯氧基乙二醇芴二（甲基）丙烯酸酯、 二羥甲基三環癸烷二（甲基）丙烯酸酯、2-羥基-3-(甲基）丙 烯醯氧基丙基甲基丙烯酸酯、2-(2’-乙烯氧基乙氧基）乙基 (甲基）丙烯酸酯 '三羥甲基丙烷三（甲基）丙烯酸酯、季戊 四醇三（甲基）丙烯酸酯等。 聚合性不飽和化合物（B2)之市售品可舉例如 Aronix M-5 3 00、M-5 600、M-5 700、M-210、M-220、M-240、M-270、M-6200、M-305、M-309、M-310、M-315(以上，東 亞合成（股）製）、KAYARAD HDDA、KAYARAD HX-220、 KAYARAD HX-620、KAYARAD R-526、KAYARAD R-167、KAYARAD R-604、KAYARAD R-684、KAYARAD R-551、KAYARAD R - 7 1 2、U X - 2 2 0 1、U X - 2 3 0 1、UX - 3 2 0 4、 UX-3 3 0 1、UX-4101、UX-6101、UX-7101、UX-8101、 UX-0937、MU-2100、MU-4001 (以上，日本化藥（股）製）、 -21 - 200907573(In the formula (1), "*" indicates a compound having a structure shown by a bonding bond) (hereinafter also referred to as "(D) component"). According to the above object of the present invention, the second aspect is achieved by a method of forming a spacer or a protective film for a liquid crystal display device, characterized in that it comprises at least the following steps (1) to (4) in the order described below. (1) a step of forming a film of the above-mentioned sensitive radiation linear resin composition on a substrate; (2) a step of irradiating at least a part of the film with radiation; (3) developing a film after irradiation of the radiation And (4) the step of heating the film after development. The above object of the present invention is achieved by the spacer or the protective film of the liquid crystal display element formed by the above method, and the fourth system is achieved by a liquid crystal display element having the above spacer or protective film. BEST MODE FOR CARRYING OUT THE INVENTION <Sensitive Radiation Linear Resin Composition> Hereinafter, the components of each of the -8-200907573 relating to the sensitive radiation linear resin composition of the present invention will be described in detail. (A) Copolymer The (A) copolymer contained in the radiation sensitive linear resin composition of the present invention contains (a1) at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (hereinafter, A copolymer of an unsaturated compound called "compound (al)"). The (A) copolymer can be produced by subjecting an unsaturated compound containing the compound (al) to a radical polymerization in the presence of a suitable radical polymerization initiator in a solvent. The compound (al) is not particularly limited as long as it has a hydroxyl group or a carboxylic anhydride structure and a polymerizable unsaturated bond, and examples thereof include an unsaturated monocarboxylic acid compound, an unsaturated dicarboxylic acid compound, and an unsaturated dicarboxylic acid. An acid anhydride of a compound: a polycyclic unsaturated carboxylic acid compound, a polycyclic unsaturated dicarboxylic acid compound, an acid anhydride of a polycyclic unsaturated dicarboxylic acid compound, or the like. The unsaturated monocarboxylic acid compound may, for example, be (meth)acrylic acid, crotonic acid, 2-(meth)acryloxyethyl succinic acid or 2-(methyl)acryloxyethyl hexahydroquinone. Acid, monohydroxyethyl (meth) acrylate, ω-carboxy polycaprolactone monoacrylate (commercially available from East Asia Synthetic Co., Ltd. under the trade name "Aronix Μ-53 00"); The dicarboxylic acid compound may, for example, be maleic acid, fumaric acid, citraconic acid, mesaconic acid or itaconic acid; and the anhydride of the above unsaturated dicarboxylic acid compound may, for example, be exemplified as the above unsaturated dicarboxylic acid. An acid anhydride or the like of the compound of the compound; and the above polycyclic unsaturated carboxylic acid compound may, for example, be 5-carboxybicyclo[2.2.1]hept-2-ene or 5-carboxy-5-methylbicyclo[2_2.1]g -2-ene, 5_ 200907573 carboxy-5-ethylbicyclo[^^h-]-ene' 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-B Bicyclo[2.2.1]hept-2-ene and the like. The polycyclic unsaturated dicarboxylic acid compound may, for example, be 5,6-dicarbylbicyclo[2.2.1]heptane-2-diene. The acid anhydride of the polycyclic unsaturated dicarboxylic acid compound may, for example, be an acid anhydride or the like which is exemplified as a compound of the above polycyclic unsaturated dicarboxylic acid compound. Among these compounds (a1), acrylic acid, (meth)acrylic acid, and maleic anhydride are preferred from the viewpoints of copolymerization reactivity, solubility in the alkali developing solution of the obtained copolymer, and ease of availability. Or 2-methacryloyloxyethyl hexahydrophthalic acid. In the synthesis of the (A) copolymer, the compound (al) may be used singly or in combination of two or more. Further, in the case where the compound (a1) has a carboxyl group, the carboxyl group may be protected and supplied to the polymerization, and then the carboxyl group may be regenerated by deprotection. Here, the protecting group for protecting the carboxyl group is not particularly limited, and a known one may be used as a protecting group for a carboxyl group. For example, a trialkylcarbenyl group, a 1-alkoxyalkyl group, a cyclic 1-alkoxyalkyl group, or the like can be given. More specifically, for example, trimethyl methacrylate, dimethylbutylmethanyl, 1-ethoxyethyl, 1-propoxyethyl, tetrahydrofuranyl, tetrahydropyranyl, triphenyl Base. (A) the copolymer may be a copolymer containing only the unsaturated compound of the above compound (al), or may be a compound (al) and (a2) other unsaturated compound (hereinafter) A copolymer of an unsaturated compound "called compound (a2)"). -10-200907573 The compound (a2) is preferably at least one selected from the group consisting of a polymerizable unsaturated compound having an oxiranyl group and a polymerizable unsaturated compound having an oxetanyl group (hereinafter referred to as "Compound (a2-l)") and at least one selected from the group consisting of the above-mentioned compounds (al) and unsaturated compounds other than (a2-l) (hereinafter referred to as "compound (a2-2)"). The above compound U2-1), for example, a polymerizable unsaturated compound having an oxiranyl group may, for example, be a (meth) acrylate compound having an oxiranyl group or an α-alkyl group having an oxirane group (A) An acrylate compound, a glycidyl ether compound, or the like. Specific examples of such a (meth) acrylate or glycidyl ester having an oxiranyl group include, for example, glycidyl (meth)acrylate and 2-methylglycidyl (meth)acrylate. Ester, 3,4-epoxybutyl (meth)acrylate, 6,7-epoxyheptyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, (A) 3,4-epoxycyclomethyl acrylate, etc.; an α-alkyl (meth) acrylate compound having an oxiranyl group, for example, α-ethyl methacrylate, n-propyl acrylate a glycidyl ester, a glycidyl α-n-butyl acrylate, a 6,7-epoxyheptyl ethoxide or the like; and a glycidyl ether compound, for example, o-vinylbenzyl glycidyl ether, m-Vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and the like. The polymerizable unsaturated compound having an oxetanyl group is, for example, a (meth) acrylate having an oxetanyl group, and a specific example thereof is, for example, 3-((meth)acryloxymethyl) Oxetane, 3-((meth)acrylooxime-11 - 200907573 methyl)-3-ethyloxetane 3-((meth)propenyloxymethyl)- 2_methyloxetane, 3-((meth)acryloxymethyl)_2-trifluoromethyloxetane, 3-((meth)acryloxymethyl) _2_pentafluoroethyloxetane, 3-((meth)acryloxymethyl)-2-phenyloxetane, 3-((meth)propenyloxymethyl -2,2-difluoromethyloxetane, 3-((meth)acryloxymethyl)-2,2,4-trifluoromethyloxetane, 3-( (Meth)acryloxymethyl)-2,2,4,4-tetrafluoromethyloxetane, 3-((meth)acryloxyethyl)oxetane, 3-((Meth) propylene methoxyethyl)-3-ethyloxetane, 2-ethyl-3-((meth) propylene methoxyethyl) oxetane, 3 -((Meth)acryloxyethyl) _2_trifluoromethyloxetane, 3-((meth)acryloxyethyl)_2-pentafluoroethyloxetane, 3-((meth)propenyloxyethyl -2 -phenyloxetane, 2,2-difluoro-3-((meth)propenyloxyethyl)oxetane, 3-((meth)propenyloxy Ethyl)-2,2,4-trifluorooxetane, 3-((meth)acryloxyethyl)-2,2,4,4-tetrafluorooxetane, 2 -((Meth)acryloxyethyl)oxetane, 2-methyl-2-((meth)acryloxymethyl)oxetane, 3-methyl-2 -((Meth)acryloxymethyl)oxetane, 4-methyl-2-((meth)propenyloxymethyl)oxetane, 2-((methyl ) propylene methoxymethyl) 2 - trifluoromethyl oxetane, 2-((meth) propylene methoxymethyl) - 3 - trifluoromethyl oxetane, 2- ( (Meth) propylene methoxymethyl)-4-trifluoromethyl oxetane, 2-((meth) propylene methoxymethyl)-2 -pentafluoroethyl oxetane , 2_((Meth)acryloxymethyl)-3-pentafluoroethyloxetane, 2-((methyl) Propylene methoxymethyl)-4-pentafluoroethyl oxetane, 2-((methyl)propan-12-200907573 olefinoxymethyl)-2-phenyl oxetane, 2-((Meth)acryloxymethyl)-3-phenyloxetane, 2-((meth)propenyloxymethyl)_4_phenyloxetane, 2, 3-difluoro-2-((methyl)propanyloxymethyl)oxetine, 2,4-difluoro-2-((methyl)propenyloxymethyl)oxyheterocycle Butane, 3,3-difluoro-2-((meth)acryloxymethyl)oxetane, 3,4-difluoro-2-((methyl)propenyloxymethyl) Oxetane, 4,4-difluoro-2-((meth)acryloxymethyl)oxetane, 2-((meth)acryloxymethyl)-3, 3,4-trifluorooxetine, 2-((methyl)propanoxycarbonylmethyl)-3,4,4-trifluorooxetane, 2-((meth)propene醯oxymethyl)-3,3,4,4-tetrafluorooxetane, 2-((meth)acryloxyethyl) oxetane, 2-(2-(2) · Methyloxetanyl))ethyl (meth) acrylate, 2-(2-(3-methyloxetanyl))ethyl (methyl) propyl Ethyl ester, 2-((methyl)propanoloxyethyl)-2-methyloxetine, 2-((meth)acryloxyethyl)-4-methyloxa Cyclobutane, 2-((meth)acryloxyethyl)-2-trifluoromethyloxetane, 2-((meth)propenyloxyethyl)-3-trifluoro Methyl oxetane, 2-((meth) propylene methoxyethyl) 4 - trifluoromethyl oxetane, 2 - ((meth) propylene oxiranyl ethyl) 2 - 5 Fluoroethyl oxetane, 2-((meth) propylene oxiranyl) _3_pentafluoroethyl oxetane, 2-((meth) propylene methoxyethyl) _4 _ pentafluoroethyl oxetane, 2-((meth) propylene oxyethyl) 2 -phenyl oxetane, 2-((meth) propylene oxiranyl)- 3-phenyloxetane, 2-((meth)acryloxyethyl)-4-phenyloxetane, 2,3-difluoro-2-((meth)propene oxime Oxyethyl)oxetane, 2,4-difluoro-2-((meth)propenyloxyethyl)oxetane, 3,3-difluoro-2-((A) Ke) 醯 醯-13- 200907573 oxyethyl) oxetane, 3,4-difluoro-2 -((Meth)acryloxyethyl)oxetane, 4,4-difluoro-2-((meth)propenyloxyethyl)oxetane, 2-(( Methyl)propenyloxyethyl)-3,3,4-trifluorooxetane, 2-((meth)acryloxyethyl)-3,4,4-trifluoroox Cyclobutane, 2-((meth)acryloxyethyl)-3,3,4,4-tetrafluorooxetane, and the like. Among these compounds (a2-l), it is preferred to use a sensitive linear resin composition with high stability and stability, and the heat resistance and chemical resistance of the obtained separator or protective film can be improved. Glycidyl acrylate, 2-methyl glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, 3-(methacryloxymethyl) Oxetane, 3-(methacryloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloxymethyl)-2-phenyloxy Heterocyclobutane, 2-(methacryloxymethyl)oxetane or 2-(methacryloxymethyl)_4-trifluoromethyloxetane. The compound (a2-l) can be used singly or in combination of two or more. The compound (a2-2) may, for example, be an alkyl (meth)acrylate, an alicyclic ester of (meth)acrylic acid, an aryl (meth)acrylate, a diester of an unsaturated dicarboxylic acid, or (methyl). A hydroxyalkyl acrylate, a polyether (meth) acrylate compound, an aromatic vinyl compound, and other unsaturated compounds. Specific examples of such (meth)acrylic acid alkyl esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and isopropyl. (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, second butyl (meth) acrylate, tert-butyl (meth) acrylate, etc.; ~ 14 - 200907573 The cycloaliphatic ester of (meth)acrylic acid may, for example, be cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate or tricyclo [5.2.1.02' 6] 癸-8-yl (meth) acrylate (hereinafter, "tricyclic [5.2.1.0''6] 癸-8-yl" is called "dicyclopentyl"), 2-dicyclopentyl Oxyethyl (meth) acrylate, isobornyl (meth) acrylate, tetrahydroindenyl (meth) acrylate, etc.; as the (meth) acrylate aryl ester, for example, phenyl ( (meth) acrylate aryl ester such as methyl acrylate or benzyl (meth) acrylate; phenyl (meth) acrylate, benzyl ( Methyl) acrylate or the like; as the diester of the unsaturated dihydric acid, for example, diethyl maleate, diethyl fumarate, diethyl itaconate, etc.; The hydroxyalkyl ester may, for example, be 2-carboxyethyl (meth) acrylate or 2-hydroxypropyl (meth) acrylate. For the polyether (meth) acrylate compound, for example, For example, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, etc.; as the aromatic ethylenic compound, for example, phenethyl phenate, α-methyl styrene, m-methyl Styrene, p-methylstyrene, p-methoxystyrene, etc.; for other unsaturated compounds, for example, (meth)acrylonitrile, vinyl chloride, vinylidene chloride, (methyl)propyl Defensin, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, tetrahydrofurfuryl (meth) acrylate, hydrazine- Cyclohexylmaleimide, fluorenyl-phenylmaleimide, fluorenyl-benzylmaleimide, N-succinimide diyl-3-meremapine benzophenone Acid ester, hydrazine-succinimide diamine-4-maleimide-15- 200907573 butyrate, N-succinimide diyl-6-maleimide valerate, N-amber Yttrium diamine-3-maleimide propionate, N-(9-propylenediyl)maleimide, and the like. Among these compounds (a2-2), benzyl (meth) acrylate, n-butyl (meth) acrylate, dicyclopentyl (meth) acrylate, styrene, 1, 3-but The diene or tetrahydroindenyl (meth) acrylate is preferred in terms of copolymerization reactivity. The compound (a2 _ 2 ) may be used singly or in combination of two or more. The (A) copolymer contained in the sensitive radiation linear resin composition of the present invention is preferably a copolymer of the compounds (a1) and (a2) as described above, but the (A) copolymer is derived from a compound ( The total of the repeating units of a) and (a2) contains 5 to 40% by weight of the constituent unit derived from the compound (al), and more preferably 10 to 30% by weight. The compound (a2) used in the production of the (A) copolymer preferably contains the compound (a2-l). In this case, the ratio of the compound U2-1) which is a total of the compound (a2-l) and the compound (a2-2) is preferably 10% by weight or more, more preferably 15 to 75% by weight. (A) The copolymer is particularly preferably a copolymer of the compounds (al), (a2-l) and (a2-2), which is derived from the constituent unit of the compound (al) and derived from the compound (a2-l). The unit and the constituent unit derived from the compound (a2-2) are preferably contained in an amount of ～40 by weight based on the total of the repeating units derived from the compounds (al), (a2-l) and (a2-2). /. The compound (a2-l) contains 10 to 70% by weight. /. And the compound (a2-2) contains 10 to 7% by weight, more preferably 5 to 30% by weight for the compound (a1), and 15 to 60% by weight of the compound (a2 -1) 200907573. (a2-2) contains 15 to 60% by weight. The radiation sensitive linear resin composition of the present invention containing the (A) copolymer having such a copolymer ratio has excellent stability in storage stability and solubility in an alkali developing solution, and the obtained spacer or protective film has sufficient strength. It is better to obtain the desired pattern size more easily. The polystyrene-equivalent weight average molecular weight (hereinafter referred to as "Mw") of the (A) copolymer obtained by gel permeation chromatography (GPC) is preferably from 2,000 to 100,000, more preferably from 5,000 to 50,000. In this case, when the Mw is less than 2,000, the development properties, the residual film ratio, and the like of the obtained film may be insufficient, and the Mw may exceed 100,000, and the development, resolution, and the like may be insufficient. . The solvent which can be used for the production of the (A) copolymer is not particularly limited, and examples thereof include diethylene glycol, propylene glycol monomethyl ether, benzyl alcohol, 2-phenylethyl alcohol, and 3-phenyl- An alcohol compound such as 1-propanol or 3-methoxybutanol; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, Diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate (poly)alkylglycol monoalkyl ether acetate compound such as ester, dipropylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, cyclohexanol acetate; Glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl ethyl ether, dipropylene glycol diethyl ether, etc. Poly)alkylglycol diether compound; -17- 200907573 other ether compounds such as tetrahydrofuran; ketone compounds such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; diacetone alcohol (ie a keto alcohol compound such as 4-hydroxy-4-methylpentan-2-one) or 4-hydroxy-4-methylhexane-2-one; a lactate compound such as methyl lactate, ethyl lactate or the like ; 2-hydroxy-2-methylpropionic acid ethyl ester, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, 3-methoxypropionic acid Ester, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methyl-3-methoxybutyl acetate '3_methyl_ 3_methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate , ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoxyacetate, ethyl acetoxyacetate, Other ester compounds such as 2-oxobutyrate; aromatic hydrocarbon compounds such as toluene and xylene; N-methylpyrrolidone, N,N-dimethylformamide, hydrazine, hydrazine-dimethylacetamide A guanamine compound such as an amine. Among these solvents, propylene glycol monomethyl ether and ethylene glycol monomethyl ether acetate are preferred from the viewpoints of polymerizability, solubility of each component as a radiation sensitive linear resin composition, and ease of film formation. Ester, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether Acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol dimethyl ether, 3-methoxybutyl acetate, cyclohexanone, 2-heptanone, 3-hept-18- 200907573 Ketone, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxylated Propionate, n-butyl acetate, isobutyl acetate, n-amyl citrate, isoamyl acetate, n-butyl propionate, ethyl butyrate, isopropyl butyrate, n-butyl butyrate or ethyl pyruvate . These solvents may be used singly or in combination of two or more. The radical polymerization initiator which can be used for the production of the (a) copolymer is not particularly limited, and may, for example, be 2,2'-azobisisobutyronitrile, 2,2,-azobis-(2,4) - dimethyl valeronitrile), 2,2'-azobis-(4-methoxy-2,4-dimethylvaleronitrile), 4,4'-azobis(4-cyanovaleric acid) , dimethyl-2,2,-azobis(2-methylpropionate), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), etc. An organic compound such as azo compound, benzoyl peroxide, barium lauryl peroxide, tributyl peroxy trimethyl acetate, 1,1-bis(t-butylperoxy)cyclohexane, etc. Peroxide; hydrogen peroxide and the like. When a peroxide is used as the radical polymerization initiator, a reducing agent may be used in combination as a redox initiator. These radical polymerization initiators can be used singly or in combination of two or more. The radical polymerization initiator is used in an amount of preferably 0.1 to 30 parts by weight, more preferably 0.1 to 15 parts by weight, per 100 parts by weight of the total unsaturated compound. The polymerization temperature is preferably from 0 to 150 ° C. More preferably from 50 to 12 ° C. The polymerization time is preferably from 10 minutes to 20 hours, more preferably from 1 to 7 hours. The (A) copolymer obtained in this manner can also be directly supplied to the radiation sensitive linear resin composition containing the polymer solution, or can be supplied to the sensitive radiation linear resin composition after being separated from the polymerization solution of the polymerization solution of the period of the use of the polymerization. Modulation. (B) Polymerizable unsaturated compound The (B) polymerizable unsaturated compound contained in the radiation sensitive linear resin composition of the present invention is preferably a compound having four or more polymerizable unsaturated bonds in one molecule. (hereinafter referred to as "polymerizable unsaturated compound (B1)") or a compound having 1 to 3 polymerizable unsaturated bonds in one molecule (hereinafter referred to as "polymerizable unsaturated compound (B2)"). Examples of the polymerizable unsaturated compound (B 1) include pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and tris(2-(A). In addition to the acryloyloxyethyl) phosphate, etc., the compound may have, for example, a compound having a linear alkylene group and an alicyclic structure and having two or more isocyanate groups, and one or more hydroxyl groups in the molecule. Further, a urethane (meth) acrylate compound obtained by reacting a compound having 3 to 5 (meth) acryloxy groups is used. Commercial products of the polymerizable unsaturated compound (B1) include, for example, Aronix M-400, Aronix M-402, Aronix M-405, Aronix M-450, Aronix M-1310, Aronix M-1600, Aronix M-1. 960, Aronix M-7100, Aronix M-80 3 0, Aronix M-8060, Aronix M-8100, Aronix M8 53 0, Aronix M-85 60, Aronix M-9050, Aronix TO- 1 45 0, Aronix TO- 1 3 82 (above East Asia Synthetic Co., Ltd.), KAYARAD DPHA, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120, KAYARAD MAX-35 1 0 (above, Nippon Kayaku Co., Ltd. )), VI SCOAT 295, VISCOAT 3 00, VISCOAT 3 60, VISCOAT GPT, -20- 200907573 VISCOAT 3PA, VISCOAT 400 (above, Osaka Organic Chemical Industry Co., Ltd.), or urethane acrylate The compound may, for example, be New Frontier Rl 150 (manufactured by Daiichi Kogyo Co., Ltd.), KAYARAD DPHA-40H, UX-5 000 (above, Nippon Kayaku Co., Ltd.), and UN-9000H (Kaisho Industrial Co., Ltd.) Stock system) and so on. The polymerizable unsaturated compound (B2) may, for example, be ω-carboxypolycaprolactone mono(meth)acrylate, ethylene glycol (meth)acrylate or 1,6-hexanediol di(meth)acrylic acid. Ester ' 1,9-nonanediol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate 'polypropylene glycol di(meth)acrylate , bisphenoxyethylene glycol bis(meth) acrylate, bisphenoxyethylene glycol bis(meth) acrylate, dimethylol tricyclodecane di(meth) acrylate, 2 -hydroxy-3-(methyl)propenyloxypropyl methacrylate, 2-(2'-vinyloxyethoxy)ethyl (meth) acrylate 'trimethylolpropane tris(III) Acrylate, pentaerythritol tri(meth)acrylate, and the like. Commercial products of the polymerizable unsaturated compound (B2) include, for example, Aronix M-5 00, M-5 600, M-5 700, M-210, M-220, M-240, M-270, M-. 6200, M-305, M-309, M-310, M-315 (above, East Asia Synthetic Co., Ltd.), KAYARAD HDDA, KAYARAD HX-220, KAYARAD HX-620, KAYARAD R-526, KAYARAD R-167 , KAYARAD R-604, KAYARAD R-684, KAYARAD R-551, KAYARAD R - 7 1 2, UX - 2 2 0 1 , UX - 2 3 0 1 , UX - 3 2 0 4, UX-3 3 0 1 , UX-4101, UX-6101, UX-7101, UX-8101, UX-0937, MU-2100, MU-4001 (above, Nippon Chemical Co., Ltd.), -21 - 200907573

Art Resin UN-9000PEP、UN-9200A、UN-7600、UN- 3 3 3、 UN- 1 003、UN- 1 25 5、UN-6060PTM、UN-6060P(以上’根 上工業（股）製）、SH-500B VISCOAT 260、VISCOAT 312、 VI SCO AT 3 3 5 HP(以上，大阪有機化學工業（股）製）等。 在本發明中，（B)聚合性不飽和化合物係可單獨或混 合2種以上而使用。 在本發明之敏輻射線性樹脂組成物中的（B)聚合性不 飽和化合物之使用比率係相對於（A)鹼可溶性共聚物1 00 重量份宜爲40〜25 0重量份，更宜爲60- 1 80重量份。 (B) 聚合性不飽和化合物係宜分別含有聚合性不飽和 化合物（B1)與（B2)至少一種類。此時，聚合性不飽和化合 物（B1)及（B2)之合計佔有的聚合性不飽和化合物（B1)之比 率宜爲40~99重量％，更宜爲60〜95重量％。 以如此之比率含有（B)聚合性不飽和化合物，俾本發 明之敏輻射線性樹脂組成物係即使在低曝光量中亦可更容 易地形成具有所希望的圖型尺寸之圖型狀薄膜，佳。 (C) 敏輻射線性聚合起始劑 於本發明之敏輻射線性樹脂組成物所含有的（C)敏輻 射線性聚合起始劑係對輻射線感應而產生可起始（B)聚合 性不飽和化合物之聚合的活性種之成分。 如此之（C)敏輻射線性聚合起始劑係可舉例如0-醯基 肟化合物、乙醯苯化合物、雙咪唑化合物、敏輻射線性陽 離子聚合起始劑、苯偶因化合物、二苯甲酮化合物、α -二酮化合物、多核醌化合物、氧雜蔥酮化合物、磷化合 -22- 200907573 物、三嗪化合物等。 上述〇-醯基肟化合物的具體例可舉例如 1-[9 -乙基-6-苯甲醯基-9.H. -咔唑-3 -基]-1,2 -壬烷-2-肟-0-苯甲酸酯、1-[9-乙基-6-苯甲醯基-9.H.-咔唑-3-基]-1，2-壬烷-2-肟-0-乙酸酯、1-[9-乙基-6-苯甲醯基-9.H.-咔 唑-3-基]-1,2-戊烷-2-肟-〇-乙酸酯、1-[9-乙基-6-苯甲醯 基-9.H.-咔唑-3-基]-辛烷-1-酮肟-0-乙酸酯、1-[9-乙基-6-(2-甲基苯甲醯基）-9.H.-咔唑-3-基]-乙烷-1-酮肟-〇-苯甲 酸酯、1-[9-乙基-6-(2-甲基苯甲醯基）-9.H.-咔唑-3-基]-乙 烷-1-酮肟-0-乙酸酯、1-[9-正丁基-6-(2-乙基苯甲醯基）-9.H.-咔唑-3-基]-乙烷-1-酮肟-0-苯甲酸酯、乙酮-l-[9-乙 基- 6-(2 -甲基-4-四氫呋喃基苯甲醯基）-9.H.-咔唑-3-基]-1-(◦-乙醯基肟）、乙酮- l-[9-乙基-6-(2-甲基-4-四氫吡喃基 苯甲醯基）-9.Η·-咔唑-3-基]-1-(0-乙醯基肟）、乙酮- l-[9-乙基- 6- (2 -甲基-5-四氫呋喃基苯甲醯基咔唑-3-基]-卜（0-乙醯基肟）、乙酮- l-[9-乙基- 6-(2-乙基-5-四氫吡喃 基苯甲醯基）-9.H·-咔唑-3-基]-1-(◦-乙醯基肟）、乙酮-1-[9-乙基-6-(2-甲基-4-(2,2-二甲基-1，3-二氧雜環戊基）苯甲 醯基）-9·Η·-咔唑-3-基]-1-(0-乙醯基肟）、乙酮-l-[9-乙基-6-(2 -甲基-4-四氫呋喃基甲氧基苯甲醯基）-9.H.-咔唑- 3-基]-1-(◦-乙醯基肟）、乙酮- l-[9-乙基-6-(2-甲基-4-四氫 吡喃基甲氧基苯甲醯基）-9.H. -咔唑-3 -基]-1-(0 -乙醯基 肟）、乙酮-l-[9-乙基-6-(2-甲基-5-四氫呋喃基甲氧基苯甲 醯基）-9·Η·-咔唑-3-基]-1-(0-乙醯基肟）、乙酮- l-[9-乙基- -23- 200907573 6-(2-甲基-5-四氫吡喃基甲氧基苯甲醯基）-9·Η.-咔唑-3-基]-1-(◦-乙醯基肟）、乙酮-1-[9-乙基-6-(2-甲基- 4-(2,2-二甲基-1，3-二氧雜環戊基）甲氧基苯甲醯基）-9.H·-昨唑-3-基]-1-(〇-乙醯基肟）等。 此等之〇-醯基肟化合物之中，可舉例如1-[9-乙基-6-(2-甲基苯甲醯基）-9.H.-咔唑-3-基]-乙烷-1-酮肟-〇-乙酸 醋、乙嗣- l- [9 -乙基-6- (2·甲基-4-四氮咲喃基甲氧基苯甲 醯基）-9·Η_-咔唑-3-基]-1-(〇 -乙醯基肟）或乙酮- 乙基- 6-(2-甲基- 4-(2,2-二甲基-1，3-二氧雜環戊基）甲氧基苯甲醯 基）-9.Η·-咔唑-3-基]-l-(〇-乙醯基肟）等作爲較佳者。 此等0 -醯基肟化合物係可單獨或混合2種以上而使 用。 上述乙醯苯化合物係可舉例如α -胺基酮化合物、α -羥基酮化合物及其他之乙醯苯化合物。 此等之具體例’就α -胺基酮化合物而言，可舉例如 2_苯甲基-2-二甲基胺基-1-(4 -嗎啉基苯基）-丁烷-1-酮、2-二甲基胺基-2_(4 -甲基苯甲基）-1-(4 -嗎啉-4 -基-苯基）-丁 烷-1-酮、2-甲基-1-(4-甲基硫苯基）-2 -嗎啉基丙烷-1-酮 等； 就α-羥基酮化合物而言，可舉例如丨_苯基-2-羥基- 2-甲基丙烷-卜酮' 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-羥基-2-丙基）酮、1-羥基環 己基苯基酮等； 就其他之乙醯苯化合物而言，可分別舉例如2，2 _二甲 -24- 200907573 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。 此等乙醯苯化合物之中，宜爲α -胺基酮化合物，尤 宜爲2-苯甲基-2-二甲基胺基-1_ (4-嗎啉基苯基）-丁烷-1-酮 或2-二甲基胺基-2-(4-甲基苯甲基）-1-(4-嗎啉-4-基-苯基）-丁烷-1-酮。 就上述聯咪唑化合物之具體例而言，可舉例如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。 此等聯咪唑化合物之中，宜爲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’-聯咪唑或2,2’-雙（2,4,6-三氯苯基）-4,4，，5,5’-四苯基-1,2’-聯咪唑，尤宜爲2,2’-雙（2,4-二氯苯 基）_4,4’，5,5’-四苯基-1,2’-聯咪唑。 在本發明之敏輻射線性樹脂組成物中，使用聯咪唑化 合物作爲（C)敏輪射線性聚合起始劑時’可添加is自具有 二烷基胺基之脂肪族或芳香族化合物（以下’稱爲^安^ -25- 200907573 系增感劑」）及硫醇化合物之至少一種。 上述胺基系增感劑係具有使聯咪唑化合物之輻射線感 度進行增感，且提高咪唑自由基的產生效率之功能的化合 物，就提高敏輻射線性樹脂組成物之感度及解析度，更提 昇對於所形成之間隔件或保護膜的基板之密著性的目的而 言可添加。如此之胺基系增感劑可舉例如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-二甲基胺基安息香酸乙酯、對-二甲基胺基 安息香酸異戊酯等。此等之胺基系增感劑之中，尤宜爲 4,4’-雙（二乙基胺基）二苯甲酮。此等之胺基系增感劑係可 單獨或混合2種以上而使用。 胺基系增感劑之添加量係相對於聯咪唑化合物1 〇〇重 量份，宜爲0.1~50重量份，更宜爲1〜20重量份。胺基系 增感劑之添加量不足0.1重量份時，有時感度、解析度或 密著性之改善效果變成不充分，另外，若超過5 0重量 份，有時損及所得到之間隔件的形狀。 上述硫醇化合物係對咪唑自由基供給氫自由基，其結 果具有產生具硫自由基之成分的功能之化合物。聯咪唑化 合物受到輻射線之照射而裂解所產生的咪唑自由基之聚合 起始能爲中程度，非爲極高者，故若直接使用此於液晶顯 示元件之間隔件的形成，間隔件之截面形狀成爲逆推拔狀 之不佳的形狀。但，藉由於其中添加硫醇化合物，對咪唑 自由基從硫醇化合物供予氫自由基，結果，咪唑自由基改 變成中性之咪唑，同時產生具有聚合起始能更高之硫自由 -26- 200907573 基的成分，藉其’可使間隔件之形狀確實地形成更佳之順 推拔狀。如此之硫醇化合物係可舉例如2-氫硫基苯並噻 唑、2 -氫硫基苯並噁唑、2 -氫硫基苯並咪唑、2 -氫硫基- 5-甲氧基苯並噻唑、2 -氫硫基-5-甲氧基苯並咪唑等之芳香 族硫醇化合物；3 -氫硫基丙酸、3 -氫硫基丙酸甲酯、3 -氫 硫基丙酸乙酯、3-氫硫基丙酸辛酯等之脂肪族單硫醇化合 物；3,6 -二噁-1，8 -辛二硫醇、季戊四醇四（氫硫基乙酸 酯）、季戊四醇四（3-氫硫基丙酸酯）等之2官能以上的脂肪 族硫醇化合物等。此等之硫醇化合物中，尤宜爲2-氫硫 基苯並噻唑。 硫醇化合物之添加量係相對於聯咪唑化合物1 〇〇重量 份，宜爲0.1〜50重量份，更宜爲1〜20重量份。硫醇化合 物之添加量不足0.1重量份時，有時間隔件的形狀之改善 效果不充分，另外，若超過50重量份，有時反而損及所 得到之間隔件的形狀。 本發明之敏輻射線性樹脂組成物中，使用聯咪唑化合 物作爲（C)敏輻射線性聚合起始劑時，宜添加上述胺基系 增感劑及硫醇化合物之兩者。 進一步，上述敏輻射線陽離子聚合起始劑係可舉例如 鑰鹽、—茂金屬（metallocene)化合物等。鐵鹽可舉例如苯 基二偶氮鑰四氟硼酸鹽、苯基二偶氮鎗六氟磷酸鹽、苯基 二偶氮鐵六氟砷酸鹽、苯基二偶氮鑰三氟甲烷磺酸鹽、苯 基二偶氮鑷三氟乙酸鹽、苯基二偶氮鎗對-甲苯磺酸鹽、 4-甲氧基苯基二偶氮鐵四氟硼酸鹽、4-甲氧基苯基二偶氮 -27- 200907573 鑰六氟磷酸鹽、4-甲氧基苯基二偶氮鑰六氟砷酸鹽、4-甲 氧基苯基二偶氮鑰三氟甲烷磺酸鹽、4-甲氧基苯基二偶氮 鑰三氟乙酸鹽、4 -甲氧基苯基二偶氮鎗對-甲苯磺酸鹽、 4-第三丁基苯基二偶氮鑰四氟硼酸鹽、4-第三丁基苯基二 偶氮鑰六氟磷酸鹽、4-第三丁基苯基二偶氮鑰六氟砷酸 鹽、4-第三丁基苯基二偶氮鑰三氟甲烷磺酸鹽、4-第三丁 基苯基二偶氮鑰三氟乙酸鹽、4-第三丁基苯基二偶氮鑰 對-甲苯磺酸鹽等之二偶氮鑰鹽； 三苯基硫鎗四氟硼酸鹽、三苯基硫鎗六氟磷酸鹽、三 苯基硫鑰六氟砷酸鹽、三苯基硫鑰三氟甲烷磺酸鹽、三苯 基硫鑰三氟乙酸鹽、三苯基硫鑰對-甲苯磺酸鹽、4-甲氧 基苯基二苯基硫鏺四氟硼酸鹽、4 -甲氧基苯基二苯基硫鑰 六氟磷酸鹽、4-甲氧基苯基二苯基硫鑰六氟砷酸鹽、4-甲 氧基苯基二苯基硫鑰三氟甲烷磺酸鹽、4 -甲氧基苯基二苯 基硫鏺三氟乙酸鹽、4-甲氧基苯基二苯基硫鏺對-甲苯磺 酸鹽、4 -苯基硫苯基二苯基四氟硼酸鹽、4 -苯基硫苯基二 苯基六氟磷酸鹽、4-苯基硫苯基二苯基六氟砷酸鹽、4-苯 基硫苯基二苯基三氟甲烷磺酸鹽、4-苯基硫苯基二苯基三 氟乙酸鹽、4-苯基硫苯基二苯基對-甲苯磺酸鹽等之硫鑰 鹽；雙（對二甲苯基）碘鑰四（五氟苯基）硼酸鹽、（對二甲苯 基）（對異丙基苯基）碘鎗四（五氟苯基）硼酸鹽等之碘鎗鹽 等。 又，二茂金屬可舉例如（1-6- 7/ -枯基）（7?-環戊二基）鐵 (1+)六氟化磷酸（1-)等。 -28- 200907573 此等敏輻射線陽離子聚合起始劑之市售品可舉例如二 偶氮鍚鹽之 Adeca Ultra set PP-33((股）ADEKA 製）、硫鑰 鹽之 OPTOMER SP-150 &gt; 170(以上，ADEKA 製）、及二茂 金屬之 Irgacure 261(Ciba Specialty Chemicals 公司製） 等。 上述之（C)敏輻射線性聚合起始劑係可單獨或混合2 種以上而使用。 在本發明之敏輻射線性樹脂組成物中，（C)敏輻射線 性聚合起始劑之使用比率係相對於（A)共聚物1 00重量 份，宜爲1~50重量份，更宜爲3〜40重量份。 本發明之敏輻射線性樹脂組成物所含有的（C)敏輻射 線性聚合起始劑係宜含有選自由0-醯基肟化合物及乙醯 苯化合物所構成之群的至少一種，更宜含有選自由0-醯 基肟化合物及乙醯苯化合物所構成之群的至少一種以及聯 咪唑化合物。此時，宜倂用聯咪唑化合物以及上述胺基系 增感劑及硫醇化合物之中的至少一種。 (C )敏輻射線性聚合起始劑中之0 -醯基肟化合物及乙 醯苯化合物的比率係其合計量相對於（C)敏輻射線性聚合 起始劑之全量宜爲40重量％以上，更宜爲45重量％以 上，最宜爲50重量％以上。 藉由以如此之比率使用（C)敏輻射線性聚合起始劑， 本發明之敏輻射線性樹脂組成物係即使爲低曝光量之情 形 &gt; 亦可以局感度形成具有更商的強度及密著性的間隔件 或保護膜。 -29- 200907573 (D)成分 在本發明之敏輻射線性樹脂組成物中添加（D)成分， 俾可極高地提昇敏輻射線性樹脂組成物之輻射線感度’可 提高對於所得到之間隔件或保護膜的基板之密著性。 (D)成分係具有以上述式（1)所示之構造的化合物， 宜爲具有以下述式Art Resin UN-9000PEP, UN-9200A, UN-7600, UN-3 3 3, UN-1 003, UN-1 25 5, UN-6060PTM, UN-6060P (above 'Gongshang Industrial Co., Ltd.), SH -500B VISCOAT 260, VISCOAT 312, VI SCO AT 3 3 5 HP (above, Osaka Organic Chemical Industry Co., Ltd.). In the present invention, the (B) polymerizable unsaturated compound may be used singly or in combination of two or more. The use ratio of the (B) polymerizable unsaturated compound in the radiation sensitive linear resin composition of the present invention is preferably 40 to 25 parts by weight, more preferably 60 parts by weight based on 100 parts by weight of the (A) alkali-soluble copolymer. - 1 80 parts by weight. (B) The polymerizable unsaturated compound preferably contains at least one of the polymerizable unsaturated compounds (B1) and (B2), respectively. In this case, the ratio of the polymerizable unsaturated compound (B1) which is a total of the polymerizable unsaturated compound (B1) and (B2) is preferably 40 to 99% by weight, more preferably 60 to 95% by weight. The (B) polymerizable unsaturated compound is contained in such a ratio that the sensitive radiation linear resin composition of the present invention can more easily form a pattern-like film having a desired pattern size even at a low exposure amount. good. (C) sensitizing radiation linear polymerization initiator (C) radiation radiation linear polymerization initiator contained in the sensitive radiation linear resin composition of the present invention is radiation-induced to initiate (B) polymerizable unsaturated A component of the active species of the polymerization of the compound. The (C) radiation-sensitive linear polymerization initiator may, for example, be a 0-fluorenyl hydrazine compound, an acetophenone compound, a diimidazole compound, a radiation-sensitive linear cationic polymerization initiator, a benzoin compound, and a benzophenone. A compound, an α-diketone compound, a polynuclear hydrazine compound, an oxalyl ketone compound, a phosphine-22-200907573 compound, a triazine compound, or the like. Specific examples of the above fluorenyl-fluorenyl hydrazine compound include, for example, 1-[9-ethyl-6-benzoguanidino-9.H.-carbazol-3-yl]-1,2-decane-2-肟-0-benzoate, 1-[9-ethyl-6-benzylidene-9.H.-carbazol-3-yl]-1,2-decane-2-indole-0- Acetate, 1-[9-ethyl-6-benzylidenyl-9.H.-carbazol-3-yl]-1,2-pentane-2-indole-indole-acetate, 1 -[9-ethyl-6-benzhydryl-9.H.-oxazol-3-yl]-octane-1-one oxime-0-acetate, 1-[9-ethyl-6 -(2-methylbenzhydryl)-9.H.-oxazol-3-yl]-ethane-1-one oxime-indole-benzoate, 1-[9-ethyl-6- (2-methylbenzhydryl)-9.H.-oxazol-3-yl]-ethane-1-one oxime-0-acetate, 1-[9-n-butyl-6-( 2-ethylbenzhydryl)-9.H.-oxazol-3-yl]-ethane-1-one oxime-0-benzoate, ethyl ketone-l-[9-ethyl-6 -(2-methyl-4-tetrahydrofuranylbenzimidyl)-9.H.-carbazol-3-yl]-1-(anthracene-ethenylhydrazine), ethyl ketone-l-[9-B -6-(2-methyl-4-tetrahydropyranylbenzylidene)-9.Η--oxazol-3-yl]-1-(0-ethylindenyl), ethyl ketone- 1-[9-Ethyl-6-(2-methyl-5-tetrahydrofuranylbenzylidenecarbazol-3-yl]-b (0-acetamidoxime), ethyl ketone-l-[9- Ethyl-6-(2 -ethyl-5-tetrahydropyranylbenzylidene)-9.H--oxazol-3-yl]-1-(anthracene-ethenyl), ethyl ketone-1-[9-B -6-(2-methyl-4-(2,2-dimethyl-1,3-dioxo)benzoyl)-9·Η·-carbazol-3-yl] 1-(0-acetamidoxime), ethyl ketone-l-[9-ethyl-6-(2-methyl-4-tetrahydrofurylmethoxybenzylidene)-9.H.-咔Oxazol-3-yl]-1-(indolyl hydrazide), ethyl ketone-l-[9-ethyl-6-(2-methyl-4-tetrahydropyranylmethoxybenzhydrazide -9.H.-carbazole-3-yl]-1-(0-acetamidoxime), ethyl ketone-l-[9-ethyl-6-(2-methyl-5-tetrahydrofuranyl) Methoxybenzylidene)-9·Η·-carbazol-3-yl]-1-(0-ethylindenyl), ethyl ketone-l-[9-ethyl- -23- 200907573 6- (2-Methyl-5-tetrahydropyranylmethoxybenzylidene)-9·Η.-carbazol-3-yl]-1-(anthracene-ethenyl), ethyl ketone-1 -[9-ethyl-6-(2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzylidene)-9.H· - oxazol-3-yl]-1-(indolyl hydrazide), etc. Among these oxime-indenyl hydrazine compounds, for example, 1-[9-ethyl-6-(2-A Benzomethane)-9.H.-carbazol-3-yl]-ethane-1-one oxime-〇- Sour vinegar, acetamidine- l-[9-ethyl-6-(2.methyl-4-tetrazinoindenylmethoxybenzylidene)-9·Η_-carbazol-3-yl]- 1-(〇-acetamido) or ethyl ketone-ethyl-6-(2-methyl-4-(2,2-dimethyl-1,3-dioxolyl)methoxy Benzomidine)-9.Η·-carbazol-3-yl]-l-(〇-ethenylhydrazine) and the like are preferred. These 0-mercaptopurine compounds can be used singly or in combination of two or more. The above-mentioned acetophenone compound may, for example, be an α-amino ketone compound, an α-hydroxyketone compound or another acetophenone compound. Specific examples of such 'in terms of the α-aminoketone compound, for example, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butane-1- Ketone, 2-dimethylamino-2_(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, 2-methyl-1 -(4-methylthiophenyl)-2- morpholinylpropan-1-one or the like; as the α-hydroxyketone compound, for example, 丨-phenyl-2-hydroxy-2-methylpropane- Butyl ' 1-(4-isopropylphenyl) 2 -hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-hydroxy-2-propyl)one, 1-hydroxycyclohexyl phenyl ketone, etc.; for other acetophenone compounds, for example, 2,2 _ dimethyl-24- 200907573 oxy acetophenone, 2,2-diethoxy acetamidine, respectively Benzene, 2,2-dimethoxy-2-phenylethyl benzene, and the like. Among these acetophenone compounds, an α-amino ketone compound is preferred, and 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butane-1 is particularly preferred. a ketone or 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one. Specific examples of the above biimidazole compound include, 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'-linked Imidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-di Chlorophenyl)-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-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2,-bis ( 2,4,6-Trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole. Among these biimidazole compounds, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2' is preferred. - bis(2,4-dichlorophenyl)-4,4,5,5'-tetraphenyl-1,2'-biimidazole or 2,2'-bis(2,4,6-trichloro Phenyl)-4,4,5,5'-tetraphenyl-1,2'-biimidazole, especially 2,2'-bis(2,4-dichlorophenyl)-4,4', 5,5'-tetraphenyl-1,2'-biimidazole. In the sensitive radiation linear resin composition of the present invention, when a biimidazole compound is used as the (C) photosensitive radiation polymerization initiator, an aliphatic or aromatic compound having a dialkylamine group can be added (hereinafter ' It is called at least one of ^^25-200907573 is a sensitizer") and a thiol compound. The amine-based sensitizer has a function of sensitizing the radiation sensitivity of the biimidazole compound and improving the production efficiency of the imidazole radical, thereby improving the sensitivity and resolution of the radiation-sensitive linear resin composition. It can be added for the purpose of the adhesion of the formed spacer or the substrate of the protective film. Such an amine-based sensitizer may, for example, be N-methyldiethanolamine, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)di Benzophenone, p-dimethylamino benzoic acid ethyl ester, p-dimethylamino benzoic acid isoamyl ester, and the like. Among these amine-based sensitizers, 4,4'-bis(diethylamino)benzophenone is particularly preferred. These amine-based sensitizers can be used singly or in combination of two or more. The amount of the amine-based sensitizer added is preferably from 0.1 to 50 parts by weight, more preferably from 1 to 20 parts by weight, per part by weight of the biimidazole compound. When the amount of the amine-based sensitizer added is less than 0.1 part by weight, the effect of improving the sensitivity, the resolution, or the adhesion may be insufficient, and if it exceeds 50 parts by weight, the obtained spacer may be damaged. shape. The above thiol compound is a compound which supplies a hydrogen radical to an imidazole radical, and as a result, has a function of generating a component having a sulfur radical. The polymerization initiation energy of the imidazole radical generated by the cleavage of the biimidazole compound by irradiation with radiation is moderate to high, so if the spacer of the liquid crystal display element is directly used, the cross section of the spacer The shape becomes a poor shape that is reversed. However, by adding a thiol compound thereto, the imidazole radical is supplied with a hydrogen radical from the thiol compound, and as a result, the imidazole radical is changed to a neutral imidazole, and at the same time, a sulfur free radical having a higher polymerization initiation energy is produced-26 - 200907573 The composition of the base, by which it can make the shape of the spacers form a better shape. Such a thiol compound may, for example, be 2-hydrothiobenzothiazole, 2-hydrothiobenzoxazole, 2-hydrothiobenzimidazole, 2-hydrothio- 5-methoxybenzo An aromatic thiol compound such as thiazole or 2-hydrothio-5-methoxybenzimidazole; 3-hydrothiopropylpropionic acid, methyl 3-hydrothiopropylpropionate, and 3-hydroxythiopropionic acid An aliphatic monothiol compound such as ester, octyl 3-hydrothiopropionate; 3,6-dioxin-1,8-octanedithiol, pentaerythritol tetrakis(hydrothioacetate), pentaerythritol tetra(3) An aliphatic thiol compound having two or more functional groups such as a hydrogenthiopropyl propionate. Among these thiol compounds, 2-hydrothiobenzothiazole is particularly preferred. The amount of the thiol compound added is preferably from 0.1 to 50 parts by weight, more preferably from 1 to 20 parts by weight, per part by weight of the biimidazole compound. When the amount of the thiol compound added is less than 0.1 part by weight, the effect of improving the shape of the separator may be insufficient, and if it exceeds 50 parts by weight, the shape of the obtained spacer may be adversely affected. In the sensitive radiation linear resin composition of the present invention, when the biimidazole compound is used as the (C) radiation-sensitive linear polymerization initiator, it is preferred to add both of the above-mentioned amine-based sensitizer and thiol compound. Further, the above-mentioned radiation radiation cationic polymerization initiator may, for example, be a key salt, a metallocene compound or the like. The iron salt may, for example, be phenyldiazolium tetrafluoroborate, phenyldiazo gun hexafluorophosphate, phenyldiazo hexafluoroarsenate or phenyldiazotrifluoromethanesulfonic acid. Salt, phenyldiazo fluorene trifluoroacetate, phenyl diazo gun p-toluene sulfonate, 4-methoxyphenyl diazo iron tetrafluoroborate, 4-methoxyphenyl di Azo-27- 200907573 key hexafluorophosphate, 4-methoxyphenyl diazo hexafluoroarsenate, 4-methoxyphenyl diazotrifluoromethanesulfonate, 4-methyl Oxyphenyldiazo-trifluoroacetate, 4-methoxyphenyldiazo gun p-toluenesulfonate, 4-tert-butylphenyldiazo-tetrafluoroborate, 4- Tert-butylphenyl diazo hexafluorophosphate, 4-tert-butylphenyldiazo hexafluoroarsenate, 4-tert-butylphenyldiazotrifluoromethanesulfonic acid Salt, 4-tert-butylphenyldiazo-trifluoroacetate, di-azo salt of 4-tert-butylphenyldiazo-p-toluenesulfonate; triphenylsulfide gun Tetrafluoroborate, triphenylsulfide hexafluorophosphate, triphenylsulfide hexafluoroarsenate, three Thiofluorotrifluoromethanesulfonate, triphenylsulfonyl trifluoroacetate, triphenylsulfonyl p-toluenesulfonate, 4-methoxyphenyldiphenylsulfonium tetrafluoroborate, 4 -Methoxyphenyldiphenylsulfonium hexafluorophosphate, 4-methoxyphenyldiphenylsulfonium hexafluoroarsenate, 4-methoxyphenyldiphenylthiotrifluoromethanesulfonate Acid salt, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium p-toluenesulfonate, 4-phenylthiophenyldiphenyltetra Fluoroborate, 4-phenylthiophenyldiphenylhexafluorophosphate, 4-phenylthiophenyldiphenylhexafluoroarsenate, 4-phenylthiophenyldiphenyltrifluoromethanesulfonic acid Salt, 4-phenylthiophenyldiphenyltrifluoroacetate, 4-phenylthiophenyldiphenyl-p-toluenesulfonate, etc.; bis(p-xylylene) iodide IV Iodine salt of pentafluorophenyl)borate, (p-xylylene) (p-isopropylphenyl) iodine gun tetrakis(pentafluorophenyl)borate, and the like. Further, the metallocene may, for example, be (1-6-7/-cumyl)(7?-cyclopentadienyl)iron (1+)hexafluorophosphoric acid (1-) or the like. -28- 200907573 Commercial products of such a sensitizing radiation cationic polymerization initiator include, for example, Adeca Ultra set PP-33 (manufactured by ADEKA) of diazo bismuth salt, and OPTOMER SP-150 &gt of sulphur salt. 170 (above, manufactured by ADEKA), and Irgacure 261 (manufactured by Ciba Specialty Chemicals Co., Ltd.) of a metallocene. The above-mentioned (C) radiation-sensitive linear polymerization initiator may be used singly or in combination of two or more. In the sensitive radiation linear resin composition of the present invention, the use ratio of the (C) radiation-sensitive linear polymerization initiator is preferably 1 to 50 parts by weight, more preferably 3 parts by weight based on 100 parts by weight of the (A) copolymer. ~40 parts by weight. The (C) radiation sensitive linear polymerization initiator contained in the sensitive radiation linear resin composition of the present invention preferably contains at least one selected from the group consisting of a 0-fluorenyl hydrazine compound and an acetophenone compound, and more preferably contains At least one of a group consisting of a free 0-fluorenyl compound and an acetophenone compound, and a biimidazole compound. In this case, it is preferred to use at least one of a biimidazole compound and the above amine-based sensitizer and thiol compound. (C) The ratio of the 0-mercaptopurine compound and the acetophenone compound in the linear polymerization initiator of the radiation radiation is preferably 40% by weight or more based on the total amount of the (C) radiation-sensitive linear polymerization initiator. More preferably, it is 45% by weight or more, and most preferably 50% by weight or more. By using (C) a radiation-sensitive linear polymerization initiator in such a ratio, the sensitive radiation linear resin composition of the present invention can form a more favorable strength and adhesion even if it is a low exposure amount. Sexual spacer or protective film. -29- 200907573 (D) component Adding component (D) to the sensitive radiation linear resin composition of the present invention, 俾 can greatly enhance the radiation sensitivity of the radiation sensitive linear resin composition' can improve the obtained spacer or The adhesion of the substrate of the protective film. The component (D) has a compound having a structure represented by the above formula (1), and preferably has the following formula

-30- 200907573-30- 200907573

(式（2)〜（10)中，「*」表示鍵結鍵’式（1〇)中之R係分別 獨立地表示氫原子、碳數3〜3〇之二級或三級之烷基、碳 數5〜12之環狀烷基、烯丙基、碳數7〜3〇之芳烷基或碳數 2〜30之醯基） 之任一者所示之構造的化合物。 如此之化合物係可分別舉例如具有以上述式（2)所示 之構造的化合物可舉例如以下述式（2 — 1)〜（2 - 1 0)所示之 化合物等，以上述式（3 )所示之構造的化合物可舉例如以 下述式（3 — 1)〜（3 - 3)所示之化合物等，以上述式（4)所示 之構造的化合物可舉例如以下述式（4 - 1)〜（4- 7)所示之化 合物等，以上述式（5)所示之構造的化合物可舉例如以下 述式（5 — 1)及（5 — 2)所示之化合物等，分別以上述式 (6)〜（10)所示之構造的化合物可舉例如以下述式（6 — 1)、 (7 — 1)、（8 — 1)、（9一1)、及（10— 所示之化合物等。 -31 - 200907573(In the formulas (2) to (10), "*" indicates that the R bond in the bond bond formula (1〇) independently represents a hydrogen atom, a secondary or tertiary alkyl group having a carbon number of 3 to 3 Å. A compound having a structure represented by any one of a cyclic alkyl group having 5 to 12 carbon atoms, an allyl group, an aralkyl group having 7 to 3 carbon atoms, or a fluorenyl group having 2 to 30 carbon atoms. The compound having a structure represented by the above formula (2), for example, may be, for example, a compound represented by the following formula (2 - 1) to (2 - 1 0), and the above formula (3) The compound of the structure shown by the following formula (3 - 1) - (3 - 3), etc., and the compound of the structure represented by the above formula (4) is, for example, the following formula (4) -1) The compound represented by the formula (5), and the compound represented by the above formula (5), for example, a compound represented by the following formulas (5-1) and (5-2), Examples of the compound having a structure represented by the above formulas (6) to (10) include, for example, the following formulas (6-1), (7-1), (8-1), (9-1), and (10). — compounds shown, etc. -31 - 200907573

-32- 200907573-32- 200907573

(3-2)(3-2)

-33- 200907573-33- 200907573

34- 200907573 ο 〇34- 200907573 ο 〇

(5-1 )(5-1)

(7-1) -35- 200907573(7-1) -35- 200907573

(上述式中，R係分別獨立地表示氫原子、碳數3〜3 〇之二 級或三級之院基、碳數5〜12之環狀烷基、烯丙基、碳數 7〜30之芳烷基或碳數2〜30之醯基） 以上述式中之R所示的碳數3〜30的二級或三級的院 基宜爲例如異丙基、2 - 丁基、第三丁基、2 -戊基、第三 戊基等； 碳數5~12之環狀院基係可舉例如環戊基、環己基、 環十二碳基； 碳數7~30之芳烷基係可舉例如苯甲基、α -甲基苯 甲基、肉桂基等； 碳數2〜30之醯基係分別可舉例如乙醯基、丙醯基、 丁驢基、苯甲酿基、乙酿基乙酿基（丙嗣基簾基）、環己基 親基、丙烧酿基、甲氧基鑛基、本甲基氧裁基寺。在上述 -36 - 200907573 式中之R係宜爲氫原子、乙醯基、苯甲醯基、烯丙基、苯 甲基或第三丁基。 本發明之敏輻射線性樹脂組成物所含有的（D)成分宜 使用以上述式（2 — 1)、（2-5)、（2 - 8)、（4 — 1)、（6-1)或 (10 — 1)所示之化合物，更宜使用N-羥基琥珀醯亞胺、N _羥基一 5 -降冰片烯基一2,3 —二羧基醯亞胺、N -羥基 酞醯亞胺、N-乙醯氧基酞醯亞胺、N—苯甲氧基酞醯亞 胺、N—羥基一 1，8 -萘醯亞胺或三羥基醯亞胺三聚氰胺 酸，尤宜爲N -羥基琥珀醯亞胺、N—羥基酞醯亞胺、N -乙醯氧基酞醯亞胺、N-羥基- 1，8 -萘醯亞胺或三羥基 醯亞胺三聚氰胺酸。 在本發明之敏輻射線性樹脂組成物中，（D)成分係可 1種單獨或混合2種以上而使用。 在本發明之敏輻射線性樹脂組成物中的（D)成分之使 用比率係相對於（A)共聚物 100重量份，宜爲0.05〜20 重量份，更宜爲0.2〜10重量份。以如此之比率使用（D) 成分，俾可更提昇敏輻射線性樹脂組成物之輻射線感度及 所得到之間隔件或保護膜的基板之密著性，而且可使敏輻 射線性樹脂組成物之溶劑的溶解性保持於適當範圍，佳。 其他之成分 本發明之敏輻射線性樹脂組成物係含有上述之（A)共 聚物、（B)聚合性不飽和化合物、（C)敏輻射線性聚合起始 劑及（D)成分作爲必要成分，但只要在無損本發明之效 -37- 200907573 果，可含有其他之成分，如此之其他的成分，可舉例如（E) 於一分子中具有2個以上之環氧乙烷基的化合物、（F)黏 著助劑、（G)界面活性劑、（H)保存安定劑、（I)耐熱性提昇 劑等。 上述（E)於一分子中具有2個以上之環氧乙烷基的化 合物（以下，亦稱爲「（E)成分」）係可添加用以進一步提昇 所得到之間隔件或保護膜的硬度。如此之（E)成分可舉例 如於一分子內具有2個以上之3，4-環氧基環己基的化合 物及其他之（E)成分。 上述於一分子內具有2個以上之3,4 -環氧基環己基 的化合物係可舉例如3,4-環氧基環己基甲基—3’，4’-環 氧基環己烷羧酸酯、2—（3，4 一環氧基環己基一 5，5-螺— 3,4_環氧基）環己烷一間一二噁烷、雙（3,4 —環氧基環己 基甲基）己二酸酯、雙（3,4 -環氧基一6-甲基環己基甲基） 己二酸、3,4_環氧基一6 —甲基環己基-3’，4’一環氧基- 6，-甲基環己烷羧酸酯、亞甲基雙（3,4_環氧基環己烷）、二環 戊二烯二環氧化物、乙二醇之二（3,4—環氧基環己基甲基） 醚、亞乙烯基雙（3，4 一環氧基環己烷羧酸酯）、內酯改性 3,4—環氧基環己基甲基-3’，4’-環氧基環己烷羧酸酯等。 上述其他之（E)成分可舉例如雙酚 A二縮水甘油基 醚、雙酚F二縮水甘油基醚、雙酚S二縮水甘油基醚、添 加氫之雙酚A二縮水甘油基醚、添加氫之雙酚F二縮水 甘油基醚、添加氫之雙酚AD二縮水甘油基醚、溴化雙酚 A二縮水甘油基醚、溴化雙酚F二縮水甘油基醚、溴化雙 -38- 200907573 酚S二縮水甘油基醚等之雙酚化合物的二縮水甘油基醚； 1，4 一丁二醇二縮水甘油基醚、1，6—己二醇二縮水甘 油基醚、甘油三縮水甘油基醚、三羥甲基丙烷三縮水甘油 基醚、聚乙二醇二縮水甘油基醚、聚丙二醇二縮水甘油基 醚等之多元醇的聚縮水甘油基醚； 乙二醇、丙二醇、甘油等之脂肪族多元醇加成1種或 2種以上之環氧烷所得到之聚醚多元醇的聚縮水甘油基 醚； 酚酚醛清漆型環氧樹脂； 甲酚酹醛清漆型環氧樹脂； 聚酚型環氧樹脂； 脂肪族長鏈二鹼酸的二縮水甘油基酯； 高級脂肪酸之縮水甘油基酯； 環氧化大豆油、環氧化蓖麻油等。 此等之市售品例如雙酚 A型環氧樹脂，可舉例如 Epicote 1001 、 Epicote 1002 、 Epicote 1003 、 Epicote 1004 、 Epicote 1007 、 Epicote 1009 、 Epicote 1010 、 Epicote 828(以上，Japan Epoxy Resin(股）製）等；雙酸 F 型環氧樹脂，可舉例如Epicote 807(Japan Epoxy Resin(股） 製）等； 酚酚醛清漆型環氧樹脂可舉例如 Epicote 152、 Epicote 154 、 Epicote 15 7 S 6 5 (以上，Japan Epoxy Resin(股）製）、EPPN 201、EPPN 202(以上，日本化藥（股） 製）等； -39- 200907573 甲酚酚醛清漆型環氧樹脂可舉例如E0CN 102、 103S、104S、1020、1025、1027(以上’日本化藥（股） 製）、Epicote 180S75(以上，Japan Epoxy Resin(股）製） 等； 聚酚型環氧樹脂可舉例如Epicote 1 032H60、XY — 4000(以上，Japan Epoxy Resin(股）製）等； 環狀脂肪族環氧樹脂可舉例如CY— 175、177、179、(In the above formula, R each independently represents a hydrogen atom, a secondary or tertiary group having a carbon number of 3 to 3 Å, a cyclic alkyl group having a carbon number of 5 to 12, an allyl group, and a carbon number of 7 to 30. The aralkyl group or the fluorenyl group having a carbon number of 2 to 30. The secondary or tertiary group having a carbon number of 3 to 30 represented by R in the above formula is preferably, for example, isopropyl or 2-butyl. a tributyl group, a 2-pentyl group, a third pentyl group or the like; and a ring-based group having a carbon number of 5 to 12, for example, a cyclopentyl group, a cyclohexyl group, a cyclododecacarbyl group; an aralkyl group having a carbon number of 7 to 30 The base system may, for example, be a benzyl group, an α-methylbenzyl group or a cinnamyl group; and the fluorenyl group having a carbon number of 2 to 30 may, for example, be an ethyl fluorenyl group, a propyl fluorenyl group, a butyl fluorenyl group or a benzoyl group. , E-branched ethyl ketone (propyl fluorenyl base), cyclohexyl parent group, propylene burning base, methoxy mineral base, the present methyl oxygen cutting base temple. R in the above formula -36 - 200907573 is preferably a hydrogen atom, an ethenyl group, a benzamidine group, an allyl group, a benzyl group or a tert-butyl group. The component (D) contained in the sensitive radiation linear resin composition of the present invention is preferably used in the above formulas (2 - 1), (2-5), (2 - 8), (4 - 1), (6-1). Or a compound represented by (10-1), more preferably N-hydroxysuccinimide, N-hydroxy-5-norbornene- 2,3-dicarboxy quinone imine, N-hydroxy quinone imine , N-ethoxy quinone imine, N-benzyloxy quinone imine, N-hydroxy-1,8-naphthoquinone imine or trihydroxy quinone imine melamine, especially N-hydroxyl Amber quinone imine, N-hydroxy quinone imine, N-ethoxy quinone imine, N-hydroxy- 1,8-naphthyl imine or trihydroxy quinone imine melamine. In the sensitive radiation linear resin composition of the present invention, the component (D) may be used singly or in combination of two or more. The use ratio of the component (D) in the radiation sensitive linear resin composition of the present invention is preferably 0.05 to 20 parts by weight, more preferably 0.2 to 10 parts by weight, per 100 parts by weight of the (A) copolymer. By using the component (D) in such a ratio, the radiation sensitivity of the linear radiation-sensitive resin composition and the adhesion of the substrate of the obtained spacer or the protective film can be further enhanced, and the radiation-sensitive linear resin composition can be made. The solubility of the solvent is maintained in an appropriate range, preferably. Other components The sensitive radiation linear resin composition of the present invention contains the above (A) copolymer, (B) a polymerizable unsaturated compound, (C) a radiation radiation linear polymerization initiator, and (D) a component as essential components. However, as long as it does not impair the effect of the present invention -37-200907573, it may contain other components, and such other components may, for example, be (E) a compound having two or more oxirane groups in one molecule, ( F) an adhesion aid, (G) a surfactant, (H) a storage stabilizer, and (I) a heat resistance enhancer. The above (E) compound having two or more oxirane groups in one molecule (hereinafter also referred to as "(E) component)" may be added to further increase the hardness of the obtained spacer or protective film. . The component (E) may, for example, be a compound having two or more 3,4-epoxycyclohexyl groups in one molecule and the other component (E). The compound having two or more 3,4-epoxycyclohexyl groups in one molecule may, for example, be 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate. Acid ester, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-di-dioxane, bis(3,4-epoxy ring Hexylmethyl) adipate, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexyl-3', 4'-epoxy-6,-methylcyclohexanecarboxylate, methylenebis(3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol Bis(3,4-epoxycyclohexylmethyl)ether, vinylidene bis(3,4-epoxycyclohexanecarboxylate), lactone modified 3,4-epoxycyclohexyl Alkyl-3',4'-epoxycyclohexanecarboxylate or the like. Examples of the other (E) component include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogen-added bisphenol A diglycidyl ether, and addition. Hydrogen bisphenol F diglycidyl ether, hydrogen added bisphenol AD diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bis-38 - 200907573 diglycidyl ether of bisphenol compound such as phenol S diglycidyl ether; 1,4-butylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol tri-condensate a polyglycidyl ether of a polyhydric alcohol such as glyceryl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether or polypropylene glycol diglycidyl ether; ethylene glycol, propylene glycol, glycerin a polyglycidyl ether of a polyether polyol obtained by adding one or more kinds of alkylene oxides to an aliphatic polyol; a phenol novolac type epoxy resin; a cresol novolac type epoxy resin; Polyphenol type epoxy resin; diglycidyl ester of aliphatic long-chain dibasic acid Glyceryl esters of higher fatty acid glycidyl; epoxidized soybean oil, epoxidized castor oil. Commercial products such as bisphenol A type epoxy resins include, for example, Epicote 1001, Epicote 1002, Epicote 1003, Epicote 1004, Epicote 1007, Epicote 1009, Epicote 1010, Epicote 828 (above, Japan Epoxy Resin). The bisphenol F-type epoxy resin may, for example, be Epicote 807 (manufactured by Japan Epoxy Resin Co., Ltd.) or the like; and the phenol novolac type epoxy resin may, for example, Epicote 152, Epicote 154, Epicote 15 7 S 6 5 (above, Japan Epoxy Resin Co., Ltd.), EPPN 201, EPPN 202 (above, Nippon Kayaku Co., Ltd.), etc.; -39- 200907573 cresol novolac type epoxy resin, for example, E0CN 102, 103S, 104S, 1020, 1025, 1027 (above 'Nippon Chemical Co., Ltd.'), Epicote 180S75 (above, manufactured by Japan Epoxy Resin Co., Ltd.), etc.; polyphenol type epoxy resin, for example, Epicote 1 032H60, XY-4000 (above, Japan Epoxy Resin Co., Ltd.), etc.; the cyclic aliphatic epoxy resin may, for example, be CY-175, 177, 179,

Araldite CY — 182、192、184(以上，Ciba SpecialtyAraldite CY — 182, 192, 184 (above, Ciba Specialty

Chemicals 公司製）、ERL_ 4234、4299、4221、4206(以 上，U.C.C公司製）、Showdyne 509(昭和電工（股）製）、 Epichlon 200、400(以上，大日本油墨（股）製）、EPicote 8 71、872(以上，Japan Epoxy Resin(股）製）、ED — 5661、 5662(以上，Celanese Coating 公司製）等； 就脂肪族聚縮水甘油基醚而言’可舉例如EPolite 100 MF(共榮社化學（股）製）、Epiol TMP(日本油脂（股）製） 等。 如此之環氧化合物（E)中，宜爲酚酚醛清漆型環氧樹 脂及聚酚型環氧樹脂。 上述（E)成分之使用比率係相對於（A)共聚物100重 量份，宜爲50重量份以下，更宜爲2~50重量份’最宜 爲5〜30重量份。藉由以如此之比率使用（E)成分，可實 現無損顯像性而所得到之間隔件或保護膜的硬度之更進一 步提昇。 又，（E)成分就不具有對於鹼顯像液的溶解性而言， -40 - 200907573 與（A)共聚物相異。 上述（F)黏著助劑係可使用來用以進—步提昇所得到 之間隔件或保護膜與基板之黏著性。 如此之（F)黏著助劑宜爲具有羧基、甲基丙烯醯基、 乙烯基 '異氰酸酯基、氧雜環丁基等之反應性官能基的官 能性矽烷偶合劑’其例可舉例如三甲氧基甲矽烷基安息香 酸、r —甲基丙烯氧丙基三甲氧基矽烷、乙烯基三乙醯氧 基矽烷、乙烯基三甲氧基矽烷、τ 一異氰酸酯基丙基三乙 氧基矽烷、r 一環氧丙氧基丙基三甲氧基矽烷、卢一（3,4 一環氧基環己基）乙基三甲氧基矽烷等。 此等之（F)黏著助劑係可單獨或混合2種以上而使 用。 (F)黏著助劑之使用量係相對於（A)共聚物1〇〇重量 份，宜爲20重量份以下，更宜爲15重量份以下。若（F) 黏著助劑之使用量超過20重量份，有易產生顯像殘留的 傾向。 上述（G)界面活性劑係可使用來用以提昇敏輻射線性 樹脂組成物之被膜形成性。 如此之（G)界面活性劑係可舉例如氟系界面活性劑、 聚矽氧界面活性劑及其他之界面活性劑。 上述氟系界面活性劑係宜爲於末端、主鏈、及側鏈的 至少一者之部位具有氟烷基及/或氟烷撐基之化合物，其 係可舉例如1，1，2,2-四氟-正辛基（1,1,2,2-四氟-正-丙基） 醚、1,1,2,2 -四氟-正·辛基（正己基）醚、六乙二醇二 -41 - 200907573 (1，1,2,2,3,3 -六氟正戊基）醚、八乙二醇二（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、 八丙二醇二（1，1，2,2 -四氟正丁基）醚、全氟正十二碳基磺 酸鈉、1，1，2,2,3,3-六氟正癸烷、l，1，2,2,3,3,9,9,10，10-十氟正十二碳烷 ’或氟 烷基苯磺酸鈉 、氟烷基磷酸鈉 、氟 烷基碳酸鈉、二甘油四（氟烷基聚氧乙烯基醚）、碘化氟烷 基銨、氟烷基甜菜鹼、其他之氟烷基聚氧乙烯基醚、全氟 烷基聚氧乙醇、全氟烷基烷氧基酯、碳酸氟烷基酯等。 氟系界面活性劑之市售品可舉例如BM - 1000、BM-1100(以上，BM CHEMIE 公司製）、Megafack F142D、 F172 ' F173、 F183、 F178、 F191、 F471、 F476 (以上，大 日本油墨化學工業（股）製）、FluoradFC-170C、FC-171、FC - 430、FC - 431(以上，住友 3M(股）製）、Sarflon S - 112、S - 113、S - 131、S - 141、S - 145、S - 382、 Sarflon SC - 101、SC - 102、SC - 103、SC - 104、SC -105、SC - 106(以上，旭硝子（股）製）、Eftop EF301、 3 03、3 5 2(以上，新秋田化成（股）製）等。Ftergent FT — 100、FT - 110、FT - 140A ' FT — 150、FT - 2 5 0 ' FT — 251、FT— 3 00、FT— 310、FT- 400S、Ftergent FTX-218、FTX— 251(以上，（股）Neos 製）等。 上述聚砍氧系界面活性劑係可舉例如Toray Silicone DC3PA 、 DC7PA 、 SH11PA 、 SH21PA 、 SH28PA 、 SH29PA ' SH30PA、SH - 190、SH - 193、SZ - 6032、SF-8428、DC-57、DC-190(以上，Toray Dow Corning -42- 200907573Chemicals company, ERL_ 4234, 4299, 4221, 4206 (above, UCC), Showdyne 509 (Showa EMI), Epichlon 200, 400 (above, Dainippon Ink), EPicote 8 71, 872 (above, Japan Epoxy Resin Co., Ltd.), ED-5661, 5662 (above, manufactured by Celanese Coating Co., Ltd.), etc.; as far as the aliphatic polyglycidyl ether is concerned, for example, EPolite 100 MF (co-prosperity) Seiko Chemical Co., Ltd., Epiol TMP (Nippon Oil & Fat Co., Ltd.), etc. Among such epoxy compounds (E), a phenol novolak type epoxy resin and a polyphenol type epoxy resin are preferable. The use ratio of the component (E) is preferably 50 parts by weight or less, more preferably 2 to 50 parts by weight, most preferably 5 to 30 parts by weight, per 100 parts by weight of the (A) copolymer. By using the component (E) in such a ratio, the hardness of the spacer or the protective film obtained can be further improved without loss of development. Further, the component (E) does not have solubility in the alkali developing solution, and -40 - 200907573 is different from the (A) copolymer. The above (F) adhesion aid can be used to further enhance the adhesion of the resulting spacer or protective film to the substrate. The (F) adhesion aid is preferably a functional decane coupling agent having a reactive functional group such as a carboxyl group, a methacryl fluorenyl group, a vinyl 'isocyanate group or an oxetanyl group, and examples thereof include trimethoxy Mercaptoalkyl benzoic acid, r-methacryloxypropyl trimethoxy decane, vinyl triethoxy decane, vinyl trimethoxy decane, τ-isocyanate propyl triethoxy decane, r Glycidoxypropyltrimethoxydecane, Lu (3,4-epoxycyclohexyl)ethyltrimethoxydecane, and the like. These (F) adhesion aids can be used singly or in combination of two or more. The amount of the (F) adhesion aid to be used is preferably 20 parts by weight or less, more preferably 15 parts by weight or less based on 1 part by weight of the (A) copolymer. If the amount of the (F) adhesion aid used exceeds 20 parts by weight, there is a tendency that development remains liable. The above (G) surfactant can be used to enhance the film formability of the radiation sensitive linear resin composition. Examples of such (G) surfactants include fluorine-based surfactants, polyoxyn surfactants, and other surfactants. The fluorine-based surfactant is preferably a compound having a fluoroalkyl group and/or a fluoroalkyl group in at least one of a terminal group, a main chain, and a side chain, and examples thereof include 1, 1, 2, and 2 -tetrafluoro-n-octyl (1,1,2,2-tetrafluoro-n-propyl)ether, 1,1,2,2-tetrafluoro-n-octyl (n-hexyl)ether, hexaethylene Alcohol two-41 - 200907573 (1,1,2,2,3,3-hexafluoro-n-pentyl) ether, octaethylene glycol di(1,1,2,2-tetrafluoro-n-butyl) ether, six Propylene glycol di(1,1,2,2,3,3-hexafluoro-n-pentyl)ether, octapropylene glycol bis(1,1,2,2-tetrafluoro-n-butyl)ether, perfluoro-n-dodecyl Sodium sulfonate, 1,1,2,2,3,3-hexafluoro-n-decane, 1,1,2,2,3,3,9,9,10,10-decafluoro-n-dodecane Or sodium fluoroalkylbenzenesulfonate, sodium fluoroalkylphosphate, sodium fluoroalkyl carbonate, diglycerol tetrakis(fluoroalkylpolyoxyvinyl ether), fluoroalkylammonium iodide, fluoroalkyl betaine, others Fluoroalkyl polyoxyethylene ether, perfluoroalkyl polyoxyethylene, perfluoroalkyl alkoxy ester, fluoroalkyl carbonate, and the like. Commercial products of a fluorine-based surfactant include, for example, BM-1000, BM-1100 (above, BM CHEMIE), Megafack F142D, F172 'F173, F183, F178, F191, F471, F476 (above, Dainippon ink) Chemical Industry Co., Ltd., Fluorad FC-170C, FC-171, FC-430, FC-431 (above, Sumitomo 3M Co., Ltd.), Sarflon S-112, S-113, S-131, S-141 , S-145, S-382, Sarflon SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (above, Asahi Glass Co., Ltd.), Eftop EF301, 3 03, 3 5 2 (above, the new Akita Chemicals Co., Ltd.) and so on. Ftergent FT — 100, FT - 110, FT - 140A 'FT — 150, FT - 2 5 0 'FT — 251, FT-3 00, FT-310, FT-400S, Ftergent FTX-218, FTX—251 (above , (shares) Neos system) and so on. The above-mentioned polyoxo-based surfactants may, for example, be Toray Silicone DC3PA, DC7PA, SH11PA, SH21PA, SH28PA, SH29PA 'SH30PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC- 190 (above, Toray Dow Corning -42- 200907573

Silicon(股）製）、TSF - 4440、TSF - 4300、TSF - 4445、 TSF - 4446 ' TSF - 4460、TSF - 4452(以上，GE 東芝 Silicone(股）製）、〇rgano Siloxane Poly KP341(信越化學 工業（股）製）等之商品名所市售者。 上述其他之界面活性劑係可舉例如聚氧乙烯月桂基 醚、聚氧乙烯硬脂基醚、聚氧乙烯油基醚等之聚氧乙烯烷 基醚；聚氧乙烯正辛基苯基醚、聚氧乙烯正壬基苯基醚等 之聚氧乙烯芳基醚；聚氧乙烯二月桂酸酯、聚氧乙烯二硬 脂酸酯等之聚氧乙烯二烷基酯等之非離子系界面活性劑、 (甲基）丙烯酸酯系共聚物Polyflow No.5 7、95(以上，共榮 公司化學（股）製）等。 此等之（G)界面活性劑係可單獨或混合2種以上而使 用。 (G)界面活性劑之使用量係相對於（A)共聚物 1〇〇重 量份，宜爲1.0重量份以下，更宜爲〇·5重量份以下。此 時若（G)界面活性劑之使用量超過1 .0重量份，有時易產 生膜不均。 上述（H)保存安定劑可舉例如硫、醌化合物、氫醌化 合物、聚氧化合物、胺、硝基亞硝基化合物等，更具體地 可舉例如4 -甲氧基酚、N -亞硝基-N-苯基羥基胺鋁 等。 此等之（H)保存安定劑係可單獨或混合2種以上而使 用。 (Η)保存安定劑之使用量係相對於（A)共聚物1 〇 〇重 -43- 200907573 量份，宜爲3.0重量份以下’更宜爲〇·5重量份以下。此 時若（Η)保存安定劑之調配量超過3·0重量份’有時感度 會降低而圖型形狀會劣化。 上述（I)耐熱性提昇劑可舉例如Ν —(焼氧基甲基）甘腺 化合物、Ν—（焼氧基甲基）三聚氰胺化合物等。 上述Ν -（烷氧基甲基）甘脲化合物可舉例如 Ν，Ν,：Ν，，Ν，一四（甲氧基甲基）甘脲、^，化一四丨乙氧基 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’-Η(ΕΤ 氧基甲基）甘脲、&gt;^，:^3，，『一四（第三丁氧基甲基）甘脲 等。此等之 Ν -（院氧基甲基）甘服化合物中宜爲 ]^3少，，&gt;^一四（甲氧基甲基）甘脲° 上述Ν —（烷氧基甲基）三聚氰胺化合物可舉例如 ν，ν，ν，，ν，，ν，，，ν，，一六（甲氧基甲基）三聚氰胺、 Ν,Ν,Ν，，Ν，，Ν，，，Ν” 一六（乙氧基甲基）三聚氰胺、 Ν，Ν，Ν，，Ν，，Ν”，Ν” 一六（正丙氧基甲基）三聚氰胺、 Ν，Ν,Ν’，Ν，，Ν”，Ν” 一六（異丙氧基甲基）三聚氰胺、 Ν,Ν,Ν，，Ν，，Ν”，Ν” 一六（正丁氧基甲基）三聚氰胺、 Ν，Ν,Ν，，Ν，，Ν”，Ν”—六（第三丁氧基甲基）三聚氰胺等。此等 之Ν —（烷氧基甲基）三聚氰胺中宜爲Ν，Ν，Ν’，Ν’，Ν”，Ν” — 六（甲氧基甲基）三聚氰胺。其市售品可舉例如Nicalac Ν 一 2702、MW — 30M(以上，（股）三和 Chemical 製）等。 &lt;敏輻射線性樹脂組成物之調製&gt; -44 - 200907573 本發明之敏輻射線性樹脂組成物係可藉由 上述之（A)共聚物、（B)聚合性不飽和化合物 線性聚合起始劑及（D)成分以及如上述任意添 分而調製。本發明之敏輻射線性樹脂組成物係 當的溶劑而以溶液狀態使用。例如藉由以特定 (A)共聚物、（B)聚合性不飽和化合物、（C)敏 合起始劑及（D)成分以及如上述任意添加之其 調製溶液狀態之敏輻射線性樹脂組成物。 於本發明之敏輻射線性樹脂組成物的調製 劑，係可使用將（A)共聚物、（B)聚合性不飽和 敏輻射線性聚合起始劑及（D)成分以及如上述 其他成分的各成分均一地溶解，且不與各成分 如此之溶劑係可舉例如與例示來作爲可使 造上述之（A)共聚物的溶劑者同樣者。 如此之溶劑中，從各成分之溶解性、與各 性、被膜形成之容易性等，尤宜使用例如二乙 二醇單乙基醚乙酸酯、二乙二醇二乙基醚、二 甲基醚、二乙二醇二甲基醚、丙二醇甲基醚、 基醚乙酸酯、丙二醇單甲基醚乙酸酯、二丙二 乙酸酯、3-甲氧基丁基乙酸酯、環己醇乙酸 醇、2—苯基乙基醇、3 —苯基一 1一丙醇或3 醇。此等之溶劑係可只單獨使用一種’亦可混 而使用。 進一步，爲提局目(J述溶劑以及膜厚之面內 均一地混合 、（C)敏輻射 加之其他成 宜溶解於適 之比率混合 輻射線性聚 他成分，可 所使用的溶 化合物、（C) 任意添加之 反應者。 用來用以製 成分之反應 二醇、二乙 乙二醇乙基 乙二醇單丁 醇單甲基醚 酯、苯甲基 一甲氧基丁 合2種以上 均一性，亦 -45 - 200907573 可倂用高沸點溶劑。可倂用之高沸點溶劑，係可舉例如 N-甲基甲醯胺、n，N-二甲基甲醯胺、N -甲基甲醯苯 胺、N -甲基乙醯胺、N，N -二甲基乙醯胺、N -甲基吡咯 烷酮、二甲基亞楓、苯甲基乙醚 '二己基醚、丙酮基丙 酮、異佛爾酮、己酸、辛酸、1-辛醇、1-壬醇、醋酸苯 甲酯、安息香酸乙酯、草酸二乙酯、馬來酸二乙酯、7 -丁內酯、碳酸乙烯酯、碳酸丙烯酯、苯基溶纖劑乙酸酯 等。此等之中’宜爲N -甲基吡咯烷酮、r -丁內酯或 N，N -二甲基乙醯胺。 就本發明之敏輻射線性樹脂組成物的溶劑而言，倂用 高沸點溶劑時，其使用量係相對於溶劑全量宜爲5 0重量 %以下，宜爲40重量％以下，更宜爲30重量％以下。高 沸點之使用量若超過此使用量，有時塗膜之膜厚均一性、 感度及殘膜率會不充分。 調製本發明之敏輻射線性樹脂組成物作爲溶液狀態 時，固形分濃度（組成物溶液中佔有之溶劑以外的成分亦 即（A)鹼可溶性共聚物、（B)成分、（C)成分、及（D)成分以 及任意添加之其他成分的合計量之比率）係可依使用之目 的或所希望之膜厚的値等任意地設定，例如爲5〜50重量 %。進一步較佳的固形分濃度係依於基板上之被膜的形成 方法而異，但有關此係後述。 如此做法所調製之組成物溶液係使用孔徑〇 . 5 μιη左右 的微孔過濾器（Milipore Filter)等而過濾後可供給使用。 -46- 200907573 &lt;間隔件或保護膜之形成方法&gt; 然後’說明有關使用本發明之敏輻射線性樹脂組成物 而形成間隔件或保護膜的方法。 本發明之間隔件或保護膜之形成方法，其特徵在於： 以下述記載之順序含有至少下述之步驟（1)~(4): (υ使本發明之敏輻射線性樹脂組成物的被膜形成於 基板上之步驟； (2) 對該被膜之至少一部分照射輻射線之步驟； (3) 使輻射線照射後之被膜進行顯像的步驟；及 (4) 加熱顯像後之被膜的步驟。 以下，依序說明有關此等之各步驟。 (1)於基板上形成本發明之敏輻射線性樹脂組成物的 被膜之步驟 於透明基板之單面形成透明導電膜，於該透明導電膜 之上形成本發明之敏輻射線性樹脂組成物的被膜。 於此處所使用之透明基板可舉例如玻璃基板、樹脂基 板等’更具體地可舉例如鈉玻璃、無鹼玻璃等之玻璃基 板；聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚醚 颯、聚碳酸酯、聚醯亞胺、聚（脂環式烯烴）、聚（脂環式 烯烴）之氫添加物等的塑膠所構成的樹脂基板。 設於透明基板之一面的透明導電膜係可舉例如由氧化 錫（Sn〇2)所構成之NESA膜（美國PPG公司之註冊商標）、 氧化銦一氧化錫（I η 2 Ο 3 - S η 0 2)所構成IΤ Ο膜等。 被膜之形成方法係可依塗佈法或乾膜法來實施。 -47- 200907573 以塗佈法形成被膜時，於上述透明導電膜之上塗佈本 發明之敏輻射線性樹脂組成物的溶液後，較佳係藉由加熱 塗佈面（預烘烤），俾可形成被膜。使用於塗佈法之組成物 溶液的固形分濃度宜爲5〜50重量％，更宜爲10〜40重量 % ’尤宜爲1 5〜3 5重量％。組成物溶液的塗佈方法並無特 別限定，可採用例如噴塗法、輥塗法、旋轉塗佈法（旋塗 法）、模縫式塗佈法、桿塗佈法、噴墨塗佈法等之適當方 法，尤宜爲旋轉塗佈法或模縫式塗佈法。 另外’藉乾薄膜法形成被膜時所使用的乾薄膜係底 膜、較佳係於可塗性之底膜上，層合由本發明之敏輻射線 性樹脂組成物所構成之敏輻射線性層而成者（以下稱爲 「敏輻射線性乾薄膜」）。 上述敏輻射線性乾薄膜係藉由塗佈本發明之敏輻射線 性樹脂組成物較佳係作爲組成物溶液後除去溶劑，俾層合 敏輻射線性層而形成。使用來用以層合敏輻射線性乾薄膜 之敏輻射線性層之組成物溶液的固形分濃度宜爲5〜50重 量％’更宜爲10〜50重量％，最宜爲20〜50重量。/〇，尤宜 爲3 0〜5 0重量％。敏輻射線性乾薄膜之底膜係可使用聚 對苯二甲酸乙二酯（PET)、聚乙烯、聚丙烯、聚碳酸酯、 聚氯化乙醯等之合成樹脂的薄膜。底膜之厚度係 15~125μπι之範圍爲適者。敏輻射線性層之厚度宜爲 1 ~3 0 μπι 左右。 敏輻射線性乾薄膜係未使用時亦可於其敏輻射線性層 上層合覆蓋膜而保存。此覆蓋膜係未使用時未被剝離，而 -48- 200907573 使用時可容易地剝離，宜爲具有適度的離型性者^滿足如 此之條件之覆蓋膜係例如可於PET薄膜、聚丙烯薄膜、 聚乙烯薄膜、聚氯化乙烯薄膜、聚胺基甲酸酯薄膜等之合 成樹脂薄膜的表面塗佈或預燒聚矽氧系離型劑之薄膜。覆 蓋膜之厚度宜爲5〜30μϊη左右。此等覆蓋膜係亦可形成層 合有2層或3層之層合型覆蓋膜。 使如此之乾薄膜於透明基板之透明導電膜上以熱壓接 法等之適當的方法進行積層，俾可形成被膜。 如上述般’較佳係藉塗佈法或乾薄膜法所形成之被 膜’較佳係然後預烘烤。預烘烤之條件係亦依各成分之種 類、調配比率等而異，但較佳係70〜12〇t，1~15分鐘左 右。 被膜之預烘烤後之膜厚宜爲0.5~10μιη，更宜爲 1·〇〜7_0μιη 左右。 (2)對該被膜之至少一部分照射輻射線之步驟 然後，對所形成之被膜之至少一部分照射輻射線。此 時’只照射被膜之一部分時，係可介由例如具有特定之圖 型的光罩進行照射之方法。 於照射所使用之輻射線可舉例如可見光、紫外線、遠 紫外線等。其中，宜爲波長在於250〜550 nm之範圍的輻 射線’尤宜爲含有3 65 nm之紫外線的輻射線。 輻射線照射量（曝光量）係藉照度計（〇AI model 3 5 6; Optical Associates Inc製）測定所照射之輻射線的波長3 65 nm的強度之値，較佳爲1 00〜5000J/m2，更佳係2〇〇〜3〇〇〇 -49- 200907573 J/m2 物比 J/m2 膜厚 保護 不需 鉀、 正丙 族2 胺等 Π定、 烯、 胺； 級胺 胺； 鹼性 添加 性劑 任何 本發明之敏輻射線性樹脂組成物係與以往所知之組成 較而爲輻射線感度極高，上述輻射線照射量爲6 0 0 以下，具有即使在400 J/m2以下亦可得到所希望之 、良好的形狀、優異之密著性及高的硬度之間隔件或 膜之優點。 (3 )使輻射線照射後之被膜進行顯像之步驟 然後’藉由使輻射線照射後之被膜進行顯像，以除去 要的部分，形成特定的圖型。 使用於顯像之顯像液係可使用例如氫氧化鈉、氫氧化 碳酸鈉、矽酸鈉、準矽酸鈉、氨等之無機鹼；乙胺、 胺等之脂肪族1級胺；二乙胺、二正丙基胺等之脂肪 級胺；三乙胺、甲基二乙基胺、二甲基乙醇胺、三乙 之脂肪族3級胺；吡咯、六氫吡啶、N-甲基六氫吡 N-甲基吡咯烷、ι，8 -二偶氮雙環[54〇]_ 7_十—碳 1’5 -二偶氮雙環[4 3 〇] _ 5 -壬烷等之脂環族3級 眼；D定、三甲基吡啶、二甲基吡啶、喹啉等之芳香族3 ;二甲基乙醇胺、甲基二乙醇胺、三乙醇胺等之烷醇 S氧化四甲基銨、氫氧化四乙基銨等之四級胺鹽等之 化合物的水溶液。於上述鹼性化合物的水溶液中亦可 適當量甲醇、乙醇等之水溶性有機溶劑及/或界面活 而使用。 顯像方法係可使用例如盛液法、浸漬法、噴灑法等之 一者’顯像時間係宜在常溫下爲1〇〜丨8 〇秒左右。 -50- 200907573 顯像後例如進行流水洗淨3 0〜9 0秒之後例如以壓縮空 氣或壓縮氮氣進行風乾而得到所希望之圖型。 (4)加熱顯影後之被膜的步驟 然後，使所得到之圖型狀被膜藉由例如加熱板、烘箱 等之適當的加熱裝置，以特定溫度例如100~250°C、特定 時間例如在加熱板上進行加熱（後烘烤）5〜3 0分鐘、在烘箱 中進行加熱（後烘烤）3 0〜1 80分鐘，可得到所希望之間隔件 或保護膜。 如以上做法般，可以所希望的圖型尺寸得到壓縮強 度、對液晶配向膜的摩擦步驟之耐性、與基板之密著性等 的各性能優之間隔件或保護膜。 &lt;液晶顯示元件&gt; 本發明之液晶顯示元件係例如可藉由以下之方法（a) 或（b)來製作。 (a)首先準備一對（2片）於單面具有透明導電膜（電極） 之透明基板，於其中之一片的基板之透明導電膜上，使用 本發明之敏輻射線性樹脂組成物而依據上述之方法以形成 間隔件或保護膜或其二者。繼而，於此等之基板的透明導 電膜及間隔件或保護膜上形成具有液晶配向能之配向膜。 使此等基板，使形成其配向膜之側的面作爲內側，而以各 別之配向膜的液晶配向方向成爲正交或逆平行之方式介由 一定之間隙（晶胞間隙）而對向配置，於被基板之表面（配 向膜）及間隔件所區隔之晶胞間隙內塡充液晶，密封塡充 -51 - 200907573 孔而構成液晶晶胞。繼而，於液晶晶胞之兩外表面，使偏 光板以其偏光方向與形成於該基板之一面的配向膜之液晶 配向方向一致或正交之方式貼合，俾可得到本發明之液晶 顯示元件。 (b)首先，與上述方法（a)同樣做法而準備形成透明導 電膜、間隔件或保護膜或其兩者、與配向膜之一對的透明 基板。其後，沿著一者之基板的端部，而使用點膠機以塗 佈紫外線硬化型密封劑，然後，使用液晶點膠機而呈微小 液滴狀滴下液晶，於真空下貼合兩基板。繼而，於前述之 密封劑部使用高壓水銀泵而照射紫外線以密封兩基板。最 後藉由於液晶晶胞之兩外表面貼合偏光板，俾得到本發明 之液晶顯示元件。 在上述之各方法中所使用之液晶可舉例如向列型液 晶、層列型液晶。其中，宜爲向列型液晶，可使用例如席 夫鹼（Schiff base)系液晶、氧化偶氮系液晶、聯苯基系液 晶、苯基環己烷系液晶、酯系液晶、聯三苯基系液晶、聯 苯基環己烷系液晶、嘧啶系液晶、二噁烷系液晶、聯環辛 烷系液晶、立方烷系液晶等。又，於此等之液晶中，亦可 添加例如氯化膽固醇、膽固醇壬酸酯、膽固醇碳酸酯等之 膽固醇液晶；商品名「C —〗5」、「CB — 1 5」（以上， MercK公司製）所販售之掌對異構物劑；對去氧苄叉基-對-胺基-2 -甲基丁基肉桂酸酯等之強介電性液晶等而使 用。 又’使用於液晶晶胞的外側之偏光板，係可舉例如一 -52- 200907573 邊使聚乙烯醇延伸配向，一邊使被稱爲吸收碘之「Η膜」 的偏光膜以醋酸纖維素保護膜所挾住的偏光板或Η膜本 身所構成之偏光板等。 【實施方式】 實施例 以下表示合成例、實施例，而更具體地說明本發明， 但本發明係不限定於以下之記載。 在以下之合成例中，共聚物之重量平均分子量Mw的 測定係依據下述之裝置及條件，以凝膠滲透色層分析 (G P C)來測定。 裝置：GPC— 101 (昭和電工（股）製） 管柱：使 GPC— KF — 801、GPC—KF — 802、GPC — KF — 803 及 GPC— KF — 804 連結。 移動相：含有磷酸0.5重量％之四氫呋喃。 &lt; (A)共聚物之合成例〉 合成例1 於具備冷卻管、攪拌機之燒瓶中，饋入2,2’ -偶氮 雙（異丁腈）5重量份及丙二醇單甲基醚乙酸酯220重量 份。繼而，饋入苯乙烯5重量份、甲基丙烯酸1〇重量 份、丙烯酸酯5重量份、甲基丙烯酸正丁酯35重量份及 甲基丙烯酸苯甲基酯40重量份，進行氮取代後，進一步 饋入1，3- 丁二烯5重量份，一邊徐緩地攪拌一邊使溶液 -53- 200907573 之溫度上昇至8 0 °C，保持此溫度5小時而聚合，俾得到 含有共聚物（A - 1)之溶液。所得到之聚合物溶液之固形分 濃度（於聚合物溶液的全重量所佔有之聚合物重量的比例） 爲31.0重量％,聚合物（A-1)之重量平均分子量Mw爲 9800 ° 合成例2 於具備冷卻管、攪拌機之燒瓶中’饋入2,2’ -偶氮 雙（2,4-二甲基戊腈）4重量份及二乙二醇乙基甲基醚250 重量份。繼而，饋入苯乙烯5重量份、甲基丙烯酸20重 量份、甲基丙烯酸三環[5·2.1.02,6]癸烷-8 -基酯30重量 份及甲基丙烯酸縮水甘油基酯40重量份，進行氮取代 後，進一步饋入1,3 -丁二嫌5重量份，一邊徐緩地攪拌一 邊使溶液之溫度上昇至7〇 °C，保持此溫度5小時而聚 合，俾得到含有共聚物（A - 2)之溶液。所得到之聚合物溶 液之固形分濃度爲28.0重量％，聚合物（A-2)之重量平均 分子量Mw爲1 2000。 合成例3 於具備冷卻管、攪拌機之燒瓶中，饋入2，2’ -偶氮 雙（異丁腈）5重量份及3-甲氧基丁基乙酸酯220重量份。 繼而，饋入苯乙烯5重量份、丙烯酸15重量份、甲基丙 烯酸正丁酯20重量份、甲基丙烯酸苯甲基酯15重量份及 3-(甲基丙烯醯氧甲基）-3 -乙基氧雜環丁烷40重量份，進 -54- 200907573 行氮取代後，進一步饋入1,3- 丁二烯5重量份，一邊徐 緩地攪拌一邊使溶液之溫度上昇至80 °C，保持此溫度5 小時而聚合，俾得到含有共聚物（A - 3)之溶液。所得到之 聚合物溶液之固形分濃度爲30.0重量％，聚合物（A-3)之 重量平均分子量Mw爲10500。 合成例4 於具備冷卻管、攪拌機之燒瓶中，饋入2,2’ -偶氮 雙（2,4 -二甲基戊腈）4重量份及二乙二醇甲基乙基醚250 重量份。繼而，饋入苯乙烯5重量份、甲基丙烯酸20重 量份、甲基丙烯酸四氫糠基酯20重量份、甲基丙烯酸縮 水甘油基酯30重量份及3-(甲基丙烯醯氧甲基）-3-乙基氧 雜環丁烷25重量份，進行氮取代後，進一步饋入i，3- 丁 二烯5重量份，一邊徐緩地攪拌一邊使溶液之溫度上昇至 70°C，保持此溫度5小時而聚合，俾得到含有共聚物（A -4)之溶液。所得到之聚合物溶液之固形分濃度爲28.3重 量％，聚合物（A-4)之重量平均分子量Mw爲1 1〇〇〇。 實施例1〜1 3、比較例1〜3 &lt;敏輻射線性樹脂組成物溶液之調製&gt; 使表1記載之種類及量的（A)共聚物、（B)聚合性不飽 和化合物、（C )敏輻射線性聚合起始劑（視情況，倂用胺基 系增感劑及硫醇化合物之中的一者或兩者）、（D)成分及（E) 成分進行混合，進一步，混合r -環氧丙氧基丙基三甲氧 -55- 200907573 基矽烷5重量份作爲（F)黏著助劑、FTX — 21 8(商品名、 (股）Neos製）0.5重量份作爲（G)界面活性劑及4—甲氧基 酚0.5重量份作爲（H)保存安定劑，以固形分濃度成爲30 重量％之方式，分別添加丙二醇單甲基醚乙酸酯後，藉由 以孔徑〇 · 5 μιη之微孔過濾器進行過濾，分別調製敏輻射線 性樹脂組成物之溶液。 又，（Α)共聚物係添加成爲含有表1記載之共聚物的 聚合物溶液（上述合成例1〜4之任一者所得到者），其含有 之共聚物的量成爲表1記載的量。 &lt;敏輻射線性樹脂組成物溶液的評估&gt; 如以下般實施如上述做法所調製之敏輻射線性樹脂組 成物的評估。評估結果表示於表2中。 (I)顯像性之評估 於無鹼玻璃基板上，分別藉旋塗器塗佈上述所調製之 敏輻射線性樹脂組成物的溶液後，於8 0 °C之加熱板預烘 烤3分鐘，以形成敏輻射線性樹脂組成物之被膜（膜厚 4.0 μιη)。 於所得到之被膜上，設置分別具有複數直徑8〜15μιη 範圍不同大小的圓狀殘留圖型之光罩。此時，於被膜表面 與光罩之間設有特定之間隙（曝光間隙）。然後，於被膜上 介由上述光罩而使用高壓水銀燈以1000 J/m2之曝光量照 射輻射線。其後，使用0.05重量％氫氧化鉀水溶液而以 2 5 °C 40秒之顯像時間藉噴灑法進行顯像後，進行純水洗 -56- 200907573 淨1分鐘’進一步’於烘箱中以23 〇t後烘烤20分鐘， 俾形成圖型狀薄膜。 此時’以使所形成之圓狀圖型以外的部分顯像殘渣不 殘留時作爲顯像性「良」。 (II) 顯影時密著性之評估 使輕射線照射之曝光量爲4 0 0 J / m2，顯像之條件係使 用0.1 5重量％氫氧化鉀水溶液而以2 5 〇c、丨8 〇秒鐘以 外，其餘係與上述「（I)顯像性之評估」同樣做法而於基 板上形成圖型狀薄膜。 此時，藉雷射顯微鏡（VK — 8500)、（股）Keyence製）硏 究藉8 μιη之圓狀殘留圖型的1〇〇個應形成之圖型1〇〇個 之中殘留於基板上之圖型的數目，以此作爲顯像時密著性 之値。 (III) 硬化度之評估 不使用光罩而使輻射線照射之曝光量爲100 j/m2，不 進行輻射線照射後之顯像步驟以外，其餘係與上述「（I) 顯像性之評估」同樣做法而於基板上形成薄膜。 有關此薄膜，使用微小壓縮試驗機（DUH- 201、島津 製作所製），藉由直徑5〇μιη之平面壓子，施加100 mN之 荷重時，硏究於膜上是否殘留平面壓子之痕跡。平面壓子 之痕跡未殘留時評估爲硬化度「良」’痕跡殘留時評估爲 硬化度「不良」。 (IV) 圖型尺寸之評估 使輻射線照射之曝光量爲200 J/m2 ’顯像之時間爲 -57- 200907573 60秒鐘以外，其餘係與上述「（I)顯像性之評估」同樣做 法而於基板上形成圖型狀薄膜。 此時，藉雷射顯微鏡（VK— 8 5 00)、（股）Keyence製）硏 究藉15μχη之圓狀殘留圖型所形成之圖型的平均直徑。 此値爲30μηι以上時，圖型尺寸係良好，因此，可謂感度 良好。 (V) 耐熱性評估 不使用光罩而使輻射線照射之曝光量爲200 J/m2，不 進行輻射線照射後之顯像步驟以外，其餘係與上述「（I) 顯像性之評估」同樣做法而於基板上形成薄膜。 藉觸針式膜厚測定機U步驟IQ、KLA Tencol公司製） 測定此薄膜之膜厚（加熱前膜厚），進一步於烘箱中以23 0 °C加熱20分鐘後的膜厚（加熱後膜厚）而比較兩者。藉下 述式所算出之膜厚變化率作爲耐熱性之値。 膜厚變化率（％)=(加熱後膜厚+加熱前膜厚）xl〇〇 (VI) 耐藥品性之評估 與上述「（V)耐熱性之評估」同樣做法而於基板上形 成薄膜。 藉觸針式膜厚測定機U步驟IQ、KLA Tencol公司製） 測定此薄膜之膜厚（浸漬前膜厚），然後，使附有此薄膜之 基板浸漬於加溫至60°C之配向膜剝離液（Chemi-Clean TS —204、三洋化成工業（股）製）中15分鐘，水洗後，於烘 -58- 200907573 箱中以120°C乾燥15分鐘後的膜厚（浸漬後膜厚）而比較兩 者。藉下述式所算出之膜厚變化率作爲耐藥品性之値。 膜厚變化率（％)=(浸漬後膜厚+浸漬前膜厚）χ 100 (VII)昇華物量之評估 與上述「（V)耐熱性之評估」同樣做法而於基板上形 成薄膜。 有關將附有此薄膜之基板切割成1 cmx 1 cm者，使用 Head space Sampra JHS — 100A(日本分析工業（股）製）及氣 體色層分析/質量分析裝置JEOL JMS— AX 5 05W(日本電 子（股）製）而硏究以分析溫度範圍25〜230 °C、昇溫速度 100 °C /10分的條件下以Head space氣體色層分析/質量分 析法所產生之昇華物的量。於昇華物量之定量係使用辛烷 (比重：0.701、注入量：〇.〇2μί)作爲標準物質，以其譜峰 面積作爲基準而依下述式求出每單位面積之昇華物量作爲 辛烷換算之値。 昇華物量（pg/cm2)=(每lcm2之昇華物的譜峰面積+ 辛烷之譜峰面積）x〇.02x0.701 此昇華物量爲2Mg/cm2以下之時，評估爲昇華物量 「少」。 (VIII)耐摩擦性之評估 -59- 200907573 使輻射線照射之曝光量爲400 J/m2，顯像時間爲60 秒鐘以外’其餘係與上述「（I)顯像性之評估」同樣做法 而於基板上形成圖型狀薄膜。於此薄膜上利用液晶配向膜 塗佈用印刷機使AL 3 046(商品名，JSR(股）製）塗佈作爲液 晶配向劑後，以18(TC加熱1小時，形成膜厚0.05μιη之 液晶配向劑的被膜。然後，對於此液晶配向劑的被膜，使 用具有捲繞聚醯胺製之布的輥之摩擦機器，使輥之旋轉數 爲500 rpm、平台之移動速度爲1 cm/sec，進行摩擦處 理。 此時，對於由1 5 μηι之圓狀殘留圖型所形成之圖型， 硏究有無圖型之剝離或切削。 (IX)電壓保持率之評估 於表面形成防止鈉離子溶出之Si 02膜，進一步，於 蒸鍍ITO(銦-氧化錫合金）電極成特定形狀的鈉玻璃基板 上，使上述所調製之敏輻射線性樹脂組成物的溶液分別藉 旋塗器塗佈後，於90°c之潔淨烘箱內預烘烤1 0分鐘，俾 形成敏輻射線性樹脂組成物之被膜（膜厚2.0 μ m)。 對於此被膜不介由光罩而以曝光量500 J/m2照射輻射 線。其後，使用〇·〇4重量％氫氧化鉀水溶液而以23°C 1 分鐘之顯像時間藉浸漬法進行顯像後，進行純水洗淨1分 鐘，進一步，於烘箱中以23 0 °C後烘烤30分鐘，俾形成 硬化膜。 使具有此硬化膜之基板、與只形成Si〇2膜及IT0電 極之基板，使用混合有〇_8mm之玻璃珠的密封劑而使硬 -60- 200907573 化膜與ITO電極對向而貼合後’於其間隙注入Merck公 司製液晶MLC 6608(商品名），以製作液晶晶胞。 將此液晶晶胞注入於6 0 °C之恆溫層，藉（股）東陽 Technic製液晶電壓保持率測定系統「VHR — 1A型」（商 品名）測定液晶晶胞之電壓保持率。此時之施加電壓係5.5 V之方形波，測定頻率爲6 0 Η z。此處，電壓保持率係依 下述式所計算之値而進行測定。 電壓保持率（％ )=( 1 6 · 7毫秒後之液晶晶胞電位差/以〇 毫秒施加之電壓）xl〇〇 若液晶晶胞之電壓保持率爲90%以下，液晶晶胞係無 法使16.7毫秒之時間、施加電壓保持於特定程度，而無 法使液晶充分地配向，產生殘像等之”預燒”之虞很高。 實施例1 4及1 5 &lt;敏輻射線性樹脂組成物溶液之調製&gt; 使表1記載之種類及量的（A)共聚物、（B)聚合性不飽 和化合物、（C)敏輻射線性聚合起始劑及（D)成分以及實施 例 15之情形係（E)成分進行混合，進一步尙且，混合r -環氧丙氧基丙基三甲氧基矽烷5重量份作爲（F)黏著助 劑、FTX—218(商品名、（股）Neos製）〇.5重量份作爲（G) 界面活性劑及4-甲氧基酧0.5重量份作爲（H)保存安定 劑，以固形分濃度成爲5 0重量％之方式’分別添加丙二 -61 - 200907573 醇單甲基醚乙酸酯後，藉由以孔徑0·5μιη之微孔過濾器進 行過濾，分別調製敏輻射線性樹脂組成物之溶液。 又，（Α)共聚物係添加成爲含有表1記載之共聚物的 聚合物溶液（上述合成例1或2所得到者），其含有之共聚 物的量成爲表1記載的量。 &lt;敏輻射線性樹脂組成物溶液的評估&gt; 分別使用如上述般做法所調製之敏輻射線性樹脂組成 物，藉如下述之轉印法進行於基板上形成敏輻射線性樹脂 組成物之被膜，又，曝光時使用光罩之際，使用具有複數 直徑30μηι之圓狀殘留圖型的光罩作爲光罩，再接觸於被 膜而設置以外，其餘係與實施例1 ~ 1 3及比較例1〜3同樣 做法而形成薄膜以進行評估。 但’在「（II)顯像時密著性的評估」中係評估有關爲 以 30μηι之圓狀殘留圖型的1〇〇個應形成之圖型 ι〇0 個’在「（IV)圖型尺寸之評估」及「（VIII)耐摩擦性之評 估」中評估有關爲從30μιη之圓狀殘留圖型所形成之圖 型 。 評估之結果表示於表2中。 &lt;以轉印法形成敏輻射線性樹脂組成物之被膜&gt; 於厚3 8 μηι之聚對苯二甲酸乙二酯（pet)薄膜上，使 用薄塗器而塗佈上述所調製之敏輻射線性樹脂組成物的溶 液，以1 〇 〇 °C加熱5分鐘，製作具有厚4 · 0 μ m之敏輻射線 -62- 200907573 性轉印層之乾薄膜。此乾薄膜，在無鹼玻璃基板的表面 (「（IX)電壓保持率的評估」中係於表面形成Si02膜及 ITO電極之鈉玻璃基板上）貼合成敏輻射線性轉印層的表 面密著，借熱壓接法於玻璃基板上轉印敏輻射線性層。 -63- 200907573 £ 1 (E)成分 重量份1 〇 1 〇 1 〇 〇 〇 〇 〇 〇 〇 〇 〇 1 〇 o I o |種類| 丁 UJ 1 1 1 1 1 1 E-2 1 1 1 1 CM 山 * UJ l I l ⑼成分 重量份 一 \n - ιό 〇· - 1 I 1 m P D-1 D-1 D-2 D-3 〇 D-1 0-4 D-5 1 〇 D-2 D-5 D-1 a 〇 D-1 i 1 i \ 靭勸 mm 璨飽 騵恢 重量份 5/10 | 5/t0 5/10 5/10 5/10 5/5/2 5/10 1 5/10 L5/10/5/1 5/10/2/2/1 5/10/5/1 5/10 5/10/5/1 in in 5/10 5/10 5/10/5/1 種類 C-1/C-2 C-1/C-2 C-1/G-Z C-1/C-2 C-1/C-2 C-3/C-4/C-5 C-1/C-2 C-1/C-2 C-1/C-2/C-3/C-5 C-1 /C-2/C-3/C-4/C-5 C-1/C-2/C-3/C-5 C-1/C-2 C-1/C-2/C-3/C-5 C-1/C-2 C-1/C-2 C-1/C-2 C-1/C-2 C-1/C-2/C-3/C-5 ⑻聚雜不飽和化合物 重量份 100/10/5 100/10 100/10/5 100/5 S 100/10/5 100/10/5 100/10/5 100/20/10/5 1' 100/20/10/5 100/20/10/5 150/10/5 150/10/5 100/10 100/20/10/5 100/10/5 100/10 100/20/10/5 種類 B-1/B-3/B-4 B-1/B-3 B-1/B-3/B-4 B-1/B-4 1 B-1/B-3/B-4 B-1/B-3/B-4 B-1/B-3/B-4 Β-1/Β-2/Β-3/Β-4 Β-1/Β-2/Β-3/Β-4 Β-1/Β-2/Β-3/Β-4 Β-1/Β-3/Β-4 B-1/B-3/B-4 B-1/B-3 B-1/B-2/B-3/B-4 B-1/B-3/B-4 B-1/B-3 B-1/B-2/B-3/B-4 (A)共聚物 S S 8 r* 100 50/50 50/50 50/50 50/50 50/50 50/50 50/50 50/50 J 50/50 8 I 50/50 1 100 100 50/50 W 郷 A-1 A-2 A-3 A-4 A-1/A-2 A-1/A-2 A-1/A-2 A-1/A-3 Α-1/Α-2 Α-1/Α-2 A-VA-2 Α-1/Α-2 A-1/A-3 A-2 A-1/A-2 A-1 A-2 A-1/A-2 I實施例1 |實施例2 |實施例3 | |實施例4 |實施例5 f實施例6 |實施例7 I實施例β |實施例9 | 「實施例 「實施例” |實施例12 |實施例13 |實施例14 1 |實施例15 |比較例1 |比較例2 |比較例3 -64- 200907573 表1中，各成分之簡稱分別爲如下之意義。 (B) 聚合性不飽和化合物 B— 1:二季戊四醇六丙烯酸酯 B - 2 : KAYARAD DPHA - 40 Η(日本化藥（股）製） Β— 3: 1,9-壬二醇二丙烯酸酯 Β - 4 : Aronix Μ - 5300 :(東亞合成（股）製） (C) 敏福射線性聚合起始劑、胺基系增感劑及硫醇化 合物 C— 1:乙酮一 1— [9 —乙基一6— (2 —甲基苯甲醯基） 一 9 Η —咔哩—3 —基]一 1_(0 —乙醯基肪）（商品名 「Irgacure 0ΧΕ 02」、Ciba Specialty Chemicals 公司製） C— 2: 2—二甲基胺基一2 —（4 —甲基苯甲基）一i— (4 一嗎琳—4 一基—苯基）一丁院一 1—嗣（商品名「irgacure 379」、Ciba Specialty Chemicals 公司製） C 一 3 : 2,2’_ 雙（2 —氯苯基）—4,4’，5,5’ 一四苯基一 1,2’ 一聯咪唑 C 一 4: 4,4’_雙（二乙基胺基）二苯甲酮（胺基系增感劑） C 一 5 : 2 —氫硫基苯並噻唑（硫醇化合物） (D) 成分 D — 1 : N —羥基酞醯亞胺 D- 2: N—羥基琥珀酸醯亞胺 D — 3: N —羥基—1，8 —萘醯亞胺、 D— 4: N —乙醯氧基酞醯亞胺、 D — 5:三羥基亞胺基三聚氰酸、 -65- 200907573 (E)成分 E— 1:酚醛清漆型環氧樹脂（商品名「Epicote 152」、Japan Epoxy resin(股）製） E_2:酚醛清漆型環氧樹脂（商品名「Epicote 157S65」、Japan Epoxy resin(股）製） 又，欄中之「-」係表示不使用該成分。 -66 - 200907573 電壓保持率 (%) in σ» 卜 cn 卜 σ\ 卜 σ&gt; σ\ σ\ 卜 σ\ r* σ\ 卜 σι σ\ 卜 σ\ Γ0 &lt;J\ s; 耐摩擦性 (有無剝離·切削） 進 摧 墚 涯 摧 m 堞 壊 壊 璀 壊 堞 * 壊 摧 揉 捶 昇華物量 七、 七、 七、 七、 耐藥品性 (%) V£) σ\ &gt;99 &gt;99 &gt;99 &gt;99 &gt;99 &gt;99 &gt;99 &gt;99 &gt;99 &gt;99 &gt;99 &gt;99 &gt;99 &gt;99 Ch 00 σ\ 00 σ\ 耐熱性 (%) &gt;99 &gt;99 &gt;99 &gt;99 &gt;99 &gt;99 &gt;99 &gt;99 &gt;99 &gt;99 &gt;99 &gt;99 &gt;99 &gt;99 in σ\ 03 CTi 00 (Τ\ 圖型尺寸法 (um) ο CN3 ΓΟ Ln ιΗ Γ〇 Η Γ0 CM rH Γ〇 m 〇 ΓΟ LO σ&gt; tN 00 rH Γ0 〇&gt; rH Γ0 τΗ CV3 ΓΟ CN rH ro U1 CNJ Γ0 Η m ΓΟ m η 1—1 m Γ0 σι m m ΓΟ 00 CM ι—Ι CO OJ i—( σ\ CN 硬化度 扯ί ί3$( 從( 不良 不良 顯像時密著性 86/100 100/100 100/100 100/100 95/100 I 69/100 100/100 100/100 100/100 100/100 100/100 100/100 100/100 I 100/100 j 100/100 0/100 34/100 51/100 顯像性 ·〇£( -¾ -0¾ 1實施例1 實施例2 實施例3 1實施例4 實施例5 實施例6 1實施例7 實施例8 |實施例9 1實施例10 實施例11 「實施例12 實施例13 |實施例14 實施例15 1比較例1 1比較例2 比較例3 -67- 200907573 在表2中，所謂「（V)耐熱性之評估」及「（VI)耐藥 品性之評估」中的「&gt; 99」係表示膜厚變化率之計算値超 過99%而爲100%以下。 又，在比較例1中之「（VIII)耐摩擦性的評估」中係 於摩擦後之圖型可看到剝離及切削之兩者。 發明之效果 本發明之敏輻射線性樹脂組成物係具有高的輻射線感 度，即使爲低曝光量，亦於顯像步驟中無圖型剝離，可以 所希望之圖型尺寸容易地形成強度優之圖型狀薄膜。又， 在圖型狀薄膜形成時之加熱步驟中未產生昇華物。本發明 之敏輻射線性樹脂組成物係特別宜使用來用以形成液晶顯 示元件之間隔件或保護膜。 從本發明之敏輻射線性樹脂組成物所形成的本發明之 間隔件或保護膜係尺寸精度、強度、耐熱性等之各性能 優，可適宜地使用於液晶顯示元件。又，因對於液晶配向 膜剝離液之耐久性（耐藥品性）亦優，故可提昇基板再生步 驟中之製品良率。進一步，本發明之間隔件係在液晶配向 膜之摩擦步驟中無圖型剝離。 具備上述間隔件或保護膜之本發明的液晶顯示元件係 可抑制「預燒」之產生者，且長期信賴性優。 -68-Silicon Co., TSF-4440, TSF-4300, TSF-4445, TSF-4446' TSF-4460, TSF-4452 (above, GE Toshiba Silicone), 〇rgano Siloxane Poly KP341 (Shin-Etsu Chemical) The market name of the trade name such as the industrial (share) system. Examples of the other surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene n-octyl phenyl ether; Non-ionic interfacial activity of polyoxyethylene aryl ether such as polyoxyethylene n-nonylphenyl ether; polyoxyethylene dialkyl ester such as polyoxyethylene dilaurate or polyoxyethylene distearate (meth)acrylate copolymer Polyflow No. 5 7, 95 (above, Co., Ltd.). These (G) surfactants can be used singly or in combination of two or more. The amount of the (G) surfactant to be used is preferably 1.0 part by weight or less, more preferably 5% by weight or less, based on 1 part by weight of the (A) copolymer. At this time, if the amount of the (G) surfactant used exceeds 1.0 part by weight, film unevenness may occur easily. The above (H) storage stabilizer may, for example, be sulfur, a hydrazine compound, a hydroquinone compound, a polyoxygen compound, an amine, a nitronitroso compound or the like, and more specifically, for example, 4-methoxyphenol or N-nitrous oxide Base-N-phenylhydroxylamine aluminum and the like. These (H) storage stabilizers can be used singly or in combination of two or more. (Η) The amount of the stabilizer to be used is 1 part by weight to the amount of the (A) copolymer, and is preferably 3.0 parts by weight or less, more preferably 5% by weight or less. At this time, if the amount of the stabilizer to be stored exceeds 3.0 parts by weight, the sensitivity may be lowered and the shape of the pattern may be deteriorated. The above (I) heat resistance improving agent may, for example, be a fluorenyl-(decyloxymethyl)glycine compound or a fluorenyl-(decyloxymethyl)melamine compound. The above hydrazone-(alkoxymethyl)glycolide compound may, for example, be hydrazine, hydrazine, hydrazine, hydrazine, tetrakis(methoxymethyl)glycoluril, or fluorene-tetraethoxymethyl) Glycoluril, hydrazine, hydrazine, hydrazine, Ν'-tetra(n-propoxymethyl) glycoluril, hydrazine, hydrazine, hydrazine, hydrazine, tetrakis(isopropoxymethyl) glycoluril, hydrazine, hydrazine , Ν', Ν'-Η (ΕΤ oxymethyl) glycoluril, &gt;^, :^3,, "four tetra(th-butoxymethyl) glycoluril and the like. Such a Ν-(Oxyloxymethyl) melamine is preferably selected from the above-mentioned ^-(3, methoxymethyl) glycoluril. The compound may, for example, be ν, ν, ν, ν, ν,,, ν, hexa(methoxymethyl)melamine, ruthenium, osmium, iridium, osmium, iridium, osmium, yttrium (Ethoxymethyl) melamine, hydrazine, hydrazine, hydrazine, hydrazine, hydrazine, hydrazine, hexa(n-propoxymethyl)melamine, hydrazine, hydrazine, hydrazine, hydrazine, hydrazine, hydrazine " hexa(isopropoxymethyl) melamine, hydrazine, hydrazine, hydrazine, hydrazine, hydrazine, hydrazine" hexa(n-butoxymethyl) melamine, hydrazine, hydrazine, hydrazine, hydrazine, Ν", Ν" - hexa(t-butoxymethyl) melamine, etc. These Ν - (alkoxymethyl) melamine should be Ν, Ν, Ν ', Ν ', Ν Ν, Ν Ν — hexa(methoxymethyl)melamine. Commercially available products include, for example, Nicalac® 2702, MW-30M (above, (3) and Chemical). &lt;Preparation of Sensitive Radiation Linear Resin Composition&gt; -44 - 200907573 The radiation sensitive linear resin composition of the present invention can be obtained by the above (A) copolymer, (B) polymerizable unsaturated compound linear polymerization initiator And (D) component and arbitrarily added as described above. The sensitive radiation linear resin composition of the present invention is used as a solvent in a solution state. For example, a sensitive radiation linear resin composition in a state in which a specific (A) copolymer, (B) a polymerizable unsaturated compound, (C) a sensitizing initiator, and (D) component, and any of the above-mentioned modulating solutions are added as described above . In the preparation of the sensitive radiation linear resin composition of the present invention, each of the (A) copolymer, (B) polymerizable unsaturated radiation radiation linear polymerization initiator, and (D) component and the other components as described above may be used. The solvent is uniformly dissolved, and the solvent is not the same as the solvent. For example, it can be exemplified as the solvent which can make the above-mentioned (A) copolymer. In such a solvent, it is preferable to use, for example, diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, or dimethyl, from the solubility of each component, the properties, and the ease of formation of a film. Ether, diethylene glycol dimethyl ether, propylene glycol methyl ether, ether ether acetate, propylene glycol monomethyl ether acetate, dipropylene diacetate, 3-methoxybutyl acetate, Cyclohexanol acetate, 2-phenylethyl alcohol, 3-phenyl-1-propanol or 3-alcohol. These solvents may be used singly or in combination. Further, in order to improve the content of the solvent and the film thickness, (C) sensitive radiation plus other suitable to dissolve in a suitable ratio of mixed radiation linear polymerization component, the dissolved compound can be used, (C Any one of the reactants used for the preparation of the reaction diol, ethylene glycol ethyl ethane glycol monobutyl ether monomethyl ether ester, benzyl methoxy butyl ketone , -45 - 200907573 can use high boiling point solvent. High boiling point solvent which can be used, for example, N-methylformamide, n,N-dimethylformamide, N-methyl Aniline, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzyl ether 'dihexyl ether, acetone acetone, isophor Ketone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, 7-butyrolactone, ethylene carbonate, carbonic acid Propylene ester, phenyl cellosolve acetate, etc. Among these, 'preferably N-methylpyrrolidone, r-butyrolactone or N,N-dimethylacetamide The solvent of the sensitive radiation linear resin composition of the present invention is preferably used in an amount of 50% by weight or less, preferably 40% by weight or less, more preferably 30% by weight based on the total amount of the solvent. When the amount of use of the high boiling point exceeds the amount used, the film thickness uniformity, sensitivity, and residual film ratio of the coating film may be insufficient. When the sensitive radiation linear resin composition of the present invention is prepared as a solution state, the solid content is determined. The concentration (the ratio of the components other than the solvent occupied in the composition solution, that is, the ratio of the (A) alkali-soluble copolymer, the component (B), the component (C), and the component (D) and the arbitrarily added component) is It may be arbitrarily set depending on the purpose of use or the desired thickness of the film, for example, 5 to 50% by weight. Further preferably, the solid content concentration varies depending on the method of forming the film on the substrate, but The composition solution prepared by the above method can be supplied by using a micropore filter having a pore diameter of about 5 μm or the like, and can be supplied for use. -46- 200907573 &lt;Method of Forming Spacer or Protective Film&gt; Next, a method of forming a spacer or a protective film using the radiation sensitive linear resin composition of the present invention will be described. The method for forming a spacer or a protective film according to the present invention is characterized by comprising at least the following steps (1) to (4) in the order described below: (υ forming a film of the sensitive radiation linear resin composition of the present invention a step on the substrate; (2) a step of irradiating at least a portion of the film with radiation; (3) a step of developing a film after the irradiation of the radiation; and (4) a step of heating the film after development. Hereinafter, the steps relating to the above are sequentially described. (1) The step of forming a film of the radiation sensitive linear resin composition of the present invention on a substrate, forming a transparent conductive film on one side of the transparent substrate, above the transparent conductive film The film of the radiation sensitive linear resin composition of the present invention is used. The transparent substrate used herein may, for example, be a glass substrate or a resin substrate. More specifically, a glass substrate such as soda glass or alkali-free glass may be mentioned; polyparaphenylene; Plastics such as ethylene diformate, polybutylene terephthalate, polyether oxime, polycarbonate, polyimine, poly(alicyclic olefin), poly(alicyclic olefin) hydrogen additive Composed The transparent conductive film provided on one surface of the transparent substrate is, for example, a NESA film composed of tin oxide (Sn〇2) (registered trademark of PPG Corporation, USA), and indium tin oxide (I η 2 Ο 3). - S η 0 2) I Τ film, etc. The film formation method can be carried out by a coating method or a dry film method. -47- 200907573 When a film is formed by a coating method, it is coated on the above transparent conductive film. After the solution of the sensitive radiation linear resin composition of the present invention is preferably formed by heating the coated surface (prebaking), the film can be formed into a film. The solid content concentration of the composition solution used in the coating method is preferably 5 ～50% by weight, more preferably 10 to 40% by weight, and particularly preferably 1 to 55% by weight. The coating method of the composition solution is not particularly limited, and for example, a spray coating method, a roll coating method, or a spin coating method can be employed. A suitable method such as a spin coating method, a die coating method, a rod coating method, or an inkjet coating method is preferably a spin coating method or a die slit coating method. The dry film base film used for forming the film, preferably on the coatable base film, laminated The linear layer of sensitive radiation composed of the sensitive radiation linear resin composition of the present invention (hereinafter referred to as "sensitive radiation linear dry film"). The above-mentioned radiation-sensitive linear dry film is coated with the sensitive radiation linear resin of the present invention. Preferably, the composition is formed as a composition solution, the solvent is removed, and the ruthenium layer is formed by sensitizing the linear layer of radiation. The solid concentration of the composition solution used to laminate the sensitive radiation linear layer of the sensitive radiation linear dry film is preferably 5 〜50重量%' is more preferably 10 to 50% by weight, most preferably 20 to 50% by weight. / 〇, particularly preferably 30 to 50% by weight. The base film of the sensitive radiation linear dry film can be used with polyparaphenylene. A film of a synthetic resin such as ethylene dicarboxylate (PET), polyethylene, polypropylene, polycarbonate, or polyethyl acetonitrile. The thickness of the base film is in the range of 15 to 125 μm. The thickness of the sensitive radiation linear layer should be about 1 ~ 30 μπι. The sensitive radiation linear dry film can also be deposited on the linear layer of the sensitive radiation when it is not used. The cover film is not peeled off when not in use, and -48-200907573 can be easily peeled off when used, preferably having a moderate release property. The cover film satisfying such conditions can be, for example, a PET film or a polypropylene film. A surface of a synthetic resin film such as a polyethylene film, a polyvinyl chloride film or a polyurethane film, or a film of a pre-fired polyoxo-type release agent. The thickness of the cover film is preferably about 5 to 30 μϊη. These cover films may also form a laminate type cover film in which two or three layers are laminated. Such a dry film is laminated on a transparent conductive film of a transparent substrate by a suitable method such as thermocompression bonding, and a film can be formed. Preferably, the film formed by the coating method or the dry film method is preferably pre-baked as described above. The pre-baking conditions vary depending on the type of each component, the blending ratio, etc., but are preferably 70 to 12 Torr, about 1 to 15 minutes. The film thickness after pre-baking of the film is preferably 0.5 to 10 μm, more preferably about 1·〇~7_0μιη. (2) a step of irradiating at least a part of the film with radiation. Then, at least a part of the formed film is irradiated with radiation. At this time, when only one portion of the film is irradiated, it is possible to irradiate the film by, for example, a mask having a specific pattern. Examples of the radiation used for the irradiation include visible light, ultraviolet light, and far ultraviolet light. Among them, it is preferable that the radiation having a wavelength in the range of 250 to 550 nm is particularly a radiation containing ultraviolet rays of 3 to 65 nm. The radiation exposure amount (exposure amount) is measured by the illuminance meter (〇AI model 3 5 6; manufactured by Optical Associates Inc.), and the intensity of the irradiated radiation is 3 65 nm, preferably 1 00 to 5000 J/m 2 . , better system 2〇〇~3〇〇〇-49- 200907573 J/m2 material ratio J/m2 film thickness protection does not require potassium, n-propyl 2 amine, etc., alkene, amine; aminamine; alkaline Additive agent Any of the sensitive radiation linear resin compositions of the present invention has a radiation sensitivity which is extremely high compared to the conventionally known composition, and the radiation dose is 60 or less, and may be at least 400 J/m2 or less. The advantages of a spacer or film of desired shape, good shape, excellent adhesion and high hardness are obtained. (3) A step of developing the film after the irradiation of the radiation. Then, by developing the film after the irradiation of the radiation, the desired portion is removed to form a specific pattern. For the imaging liquid used for development, for example, an inorganic base such as sodium hydroxide, sodium carbonate, sodium citrate, sodium citrate, ammonia or the like; an aliphatic primary amine such as ethylamine or an amine; Fatty amines such as amines, di-n-propylamines; triethylamine, methyldiethylamine, dimethylethanolamine, triethylaliphatic tertiary amines; pyrrole, hexahydropyridine, N-methylhexahydro Alicyclic group 3 such as pyridinium N-methylpyrrolidine, iota, 8-diazobicyclo[54〇]_ 7_deca-carbon 1'5-diazobicyclo[4 3 〇] _ 5 -decane Grade 3; aromatic D of D-, trimethylpyridine, lutidine, quinoline, etc.; alkanol S-oxidized tetramethylammonium, such as dimethylethanolamine, methyldiethanolamine, triethanolamine, etc. An aqueous solution of a compound such as a quaternary ammonium salt such as ethylammonium. An aqueous solution of the above basic compound may be used in an appropriate amount of a water-soluble organic solvent such as methanol or ethanol and/or an interface. For the development method, for example, one of the liquid-filling method, the dipping method, the spraying method, and the like can be used. The development time is preferably about 1 〇 to 8 〇 seconds at normal temperature. -50- 200907573 After the development, for example, after washing with running water for 30 to 90 seconds, for example, it is air-dried by compressed air or compressed nitrogen to obtain a desired pattern. (4) Step of heating the film after development, and then obtaining the pattern-shaped film obtained by a suitable heating means such as a hot plate, an oven, or the like at a specific temperature, for example, 100 to 250 ° C, for a specific time, for example, on a heating plate Heating (post-baking) is carried out for 5 to 30 minutes, and heating (post-baking) in an oven for 30 to 180 minutes to obtain a desired spacer or protective film. As described above, a spacer or a protective film having excellent properties such as compression strength, resistance to a rubbing step of a liquid crystal alignment film, and adhesion to a substrate can be obtained in a desired pattern size. &lt;Liquid Crystal Display Element&gt; The liquid crystal display element of the present invention can be produced, for example, by the following method (a) or (b). (a) first preparing a pair (two pieces) of a transparent substrate having a transparent conductive film (electrode) on one side, and using the sensitive radiation linear resin composition of the present invention on the transparent conductive film of one of the substrates, according to the above The method to form a spacer or a protective film or both. Then, an alignment film having a liquid crystal alignment energy is formed on the transparent conductive film of the substrate and the spacer or the protective film. These substrates are placed on the side on which the alignment film is formed, and the liquid crystal alignment directions of the respective alignment films are aligned orthogonally or antiparallel through a certain gap (cell gap). The liquid crystal is filled in the cell gap separated by the surface of the substrate (alignment film) and the spacer, and the liquid crystal cell is formed by sealing the hole of -51 - 200907573. Then, on the outer surfaces of the liquid crystal cell, the polarizing plate is bonded in such a manner that the polarizing direction thereof is aligned or orthogonal to the alignment direction of the liquid crystal of the alignment film formed on one surface of the substrate, and the liquid crystal display element of the present invention can be obtained. . (b) First, a transparent substrate in which a transparent conductive film, a spacer or a protective film or both, and a pair of alignment films are formed is prepared in the same manner as in the above method (a). Thereafter, the ultraviolet curable sealant is applied by using a dispenser along the end of one of the substrates, and then the liquid crystal is dripped in a droplet form using a liquid crystal dispenser, and the two substrates are bonded under vacuum. . Then, a high-pressure mercury pump was used in the above-mentioned sealant portion to irradiate ultraviolet rays to seal the two substrates. Finally, the liquid crystal display element of the present invention is obtained by bonding the polarizing plates to the outer surfaces of the liquid crystal cells. The liquid crystal used in each of the above methods may, for example, be a nematic liquid crystal or a smectic liquid crystal. Among them, a nematic liquid crystal is preferable, and for example, a Schiff base liquid crystal, an oxidized azo liquid crystal, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal, an ester liquid crystal, or a triphenyl group can be used. Liquid crystal, biphenylcyclohexane liquid crystal, pyrimidine liquid crystal, dioxane liquid crystal, bicyclooctane liquid crystal, cetane liquid crystal, or the like. Further, in such liquid crystals, for example, cholesteric liquid crystals such as chlorinated cholesterol, cholesterol phthalate, and cholesterol carbonate may be added; trade names "C-〗 5" and "CB-1 5" (above, MercK Corporation) A commercially available palmitic isomer; a strong dielectric liquid crystal such as deoxybenzylidene-p-amino-2-methylbutylcinnamate or the like. Further, the polarizing plate used for the outer side of the liquid crystal cell is a cellulose acetate protective film which is a polarizing film called a ruthenium film which absorbs iodine while extending the alignment of polyvinyl alcohol, for example, from -52 to 200907573. A polarizing plate or a polarizing plate composed of the ruthenium film itself. [Embodiment] Hereinafter, the present invention will be described more specifically with reference to Synthesis Examples and Examples, but the present invention is not limited to the following description. In the following synthesis examples, the measurement of the weight average molecular weight Mw of the copolymer was carried out by gel permeation chromatography (G P C) in accordance with the apparatus and conditions described below. Device: GPC-101 (Showa Denko Co., Ltd.) Pipe column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 are connected. Mobile phase: tetrahydrofuran containing 0.5% by weight of phosphoric acid. &lt;(A) Synthesis Example of Copolymer> Synthesis Example 1 In a flask equipped with a cooling tube and a stirrer, 5 parts by weight of 2,2'-azobis(isobutyronitrile) and propylene glycol monomethyl ether acetate were fed. The ester was 220 parts by weight. Then, 5 parts by weight of styrene, 1 part by weight of methacrylic acid, 5 parts by weight of acrylate, 35 parts by weight of n-butyl methacrylate, and 40 parts by weight of benzyl methacrylate were fed, and after nitrogen substitution, Further, 5 parts by weight of 1,3-butadiene was fed, and the temperature of the solution -53-200907573 was raised to 80 ° C while stirring slowly, and the temperature was maintained for 5 hours to be polymerized, and the copolymer was obtained (A - 1) The solution. The solid content concentration of the obtained polymer solution (the ratio of the weight of the polymer in the total weight of the polymer solution) was 31.0% by weight, and the weight average molecular weight Mw of the polymer (A-1) was 9800 °. Synthesis Example 2 In a flask equipped with a cooling tube and a stirrer, 4 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) and 250 parts by weight of diethylene glycol ethyl methyl ether were fed. Then, 5 parts by weight of styrene, 20 parts by weight of methacrylic acid, 30 parts by weight of tricyclo[5·2.1.02,6]decane-8-yl methacrylate, and glycidyl methacrylate 40 were fed. After the nitrogen substitution, the mixture was further fed with 5 parts by weight of 1,3 -butane, and the temperature of the solution was raised to 7 ° C while stirring slowly, and the temperature was maintained for 5 hours to be polymerized, and the mixture was copolymerized. A solution of the substance (A-2). The solid solution concentration of the obtained polymer solution was 28.0% by weight, and the weight average molecular weight Mw of the polymer (A-2) was 12,000. Synthesis Example 3 In a flask equipped with a cooling tube and a stirrer, 5 parts by weight of 2,2'-azobis(isobutyronitrile) and 220 parts by weight of 3-methoxybutyl acetate were fed. Then, 5 parts by weight of styrene, 15 parts by weight of acrylic acid, 20 parts by weight of n-butyl methacrylate, 15 parts by weight of benzyl methacrylate, and 3-(methacryloxymethyl)-3 - 40 parts by weight of ethyloxetane, and after nitrogen substitution in -54-200907573, 5 parts by weight of 1,3-butadiene was further fed, and the temperature of the solution was raised to 80 ° C while stirring slowly. This temperature was maintained for 5 hours to be polymerized, and a solution containing the copolymer (A-3) was obtained. The solid solution concentration of the obtained polymer solution was 30.0% by weight, and the weight average molecular weight Mw of the polymer (A-3) was 10,500. Synthesis Example 4 In a flask equipped with a cooling tube and a stirrer, 4 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) and 250 parts by weight of diethylene glycol methyl ethyl ether were fed. . Then, 5 parts by weight of styrene, 20 parts by weight of methacrylic acid, 20 parts by weight of tetrahydrofurfuryl methacrylate, 30 parts by weight of glycidyl methacrylate, and 3-(methacryloxymethyl group) were fed. 25 parts by weight of 3-ethyloxetane, after nitrogen substitution, 5 parts by weight of i,3-butadiene was further fed, and the temperature of the solution was raised to 70 ° C while stirring slowly, keeping This temperature was polymerized for 5 hours, and a solution containing the copolymer (A-4) was obtained. The solid solution concentration of the obtained polymer solution was 28.3% by weight, and the weight average molecular weight Mw of the polymer (A-4) was 11 Å. Examples 1 to 1 3, Comparative Examples 1 to 3 &lt;Preparation of Sensitive Radiation Linear Resin Composition Solution&gt; The (A) copolymer, (B) polymerizable unsaturated compound, and (C) radiation radiation linear polymerization initiator of the type and amount described in Table 1 (as appropriate) And mixing one or both of an amine sensitizer and a thiol compound, (D) component and (E) component, and further mixing r-glycidoxypropyltrimethoxy- 55- 200907573 5 parts by weight of decane as 0.5% by weight of (F) adhesion aid, FTX-21 2 (trade name, manufactured by Neos) as (G) surfactant and 0.5 parts by weight of 4-methoxyphenol As a (H) storage stabilizer, propylene glycol monomethyl ether acetate was added so that the solid content concentration was 30% by weight, and then filtered by a micropore filter having a pore diameter of 5 μm. A solution of a linear resin composition. In addition, the (Α) copolymer was added as a polymer solution containing the copolymer described in Table 1 (obtained in any of the above Synthesis Examples 1 to 4), and the amount of the copolymer contained therein was the amount shown in Table 1. . &lt;Evaluation of Sensitive Radiation Linear Resin Composition Solution&gt; Evaluation of the sensitive radiation linear resin composition prepared as described above was carried out as follows. The results of the evaluation are shown in Table 2. (I) Evaluation of development on an alkali-free glass substrate, respectively, coating a solution of the above-mentioned prepared radiation-sensitive linear resin composition by a spinner, and pre-baking at 80 ° C for 3 minutes. To form a film of a radiation sensitive linear resin composition (film thickness: 4.0 μm). On the obtained film, a mask having a circular residual pattern having a plurality of different diameters in the range of 8 to 15 μm was provided. At this time, a specific gap (exposure gap) is provided between the surface of the film and the mask. Then, the radiation was irradiated on the film through the above-mentioned photomask using a high pressure mercury lamp at an exposure amount of 1000 J/m2. Thereafter, after developing with a 0.05 wt% potassium hydroxide aqueous solution at a developing time of 25 ° C for 40 seconds, a pure water washing-56-200907573 was performed for 1 minute 'further' in an oven at 23 〇. After t baking for 20 minutes, the crucible formed a pattern-like film. In this case, the development property is "good" when the portion of the development residue other than the formed circular pattern does not remain. (II) The evaluation of the adhesion during development is such that the exposure amount of the light ray irradiation is 400 μm / m 2 , and the condition for development is to use 0.1 5 wt% aqueous potassium hydroxide solution to be 2 5 〇c, 丨 8 〇 second Other than the clock, the rest of the film was formed into a pattern-like film on the substrate in the same manner as in the above "(I) Evaluation of development). At this time, one of the ones to be formed by the laser microscope (VK-8500) and the Keyence system) is left on the substrate by one of the patterns of the circular pattern of 8 μm. The number of patterns is used as the seal of the image. (III) Evaluation of the degree of hardening: The exposure amount of the radiation is 100 j/m2 without using a mask, and the imaging procedure after the irradiation without radiation is performed, and the evaluation of the above (I) development is performed. In the same manner, a film is formed on the substrate. In the film, a micro-compression tester (DUH-201, manufactured by Shimadzu Corporation) was used, and when a load of 100 mN was applied by a plane pressure of 5 〇 μηη, it was investigated whether or not a trace of a plane pressure remained on the film. When the trace of the plane pressure was not left, the degree of hardening was evaluated as "good". When the trace residue remained, the degree of hardening was evaluated as "poor". (IV) The evaluation of the pattern size is such that the exposure amount of the radiation irradiation is 200 J/m2 'the time of development is -57-200907573 60 seconds, and the rest is the same as the above "(I) evaluation of imaging performance" A pattern-like film is formed on the substrate. At this time, the average diameter of the pattern formed by the circular residual pattern of 15 μχη was examined by a laser microscope (VK-8500) and Keyence. When the 値 is 30 μηι or more, the pattern size is good, and therefore, the sensitivity is good. (V) Heat resistance evaluation: The exposure amount of the radiation is 200 J/m2 without using a mask, and the development procedure after the radiation irradiation is not performed, and the above evaluation of "(I) development" The film is formed on the substrate in the same manner. The film thickness of the film (manufactured by KLA Tencol Co., Ltd.) was measured by a needle-type film thickness measuring machine (manufactured by KLA Tencol Co., Ltd.), and the film thickness after heating at 230 ° C for 20 minutes in an oven (film after heating) Thick) and compare the two. The film thickness change rate calculated by the following formula is used as the heat resistance. Film thickness change rate (%) = (film thickness after heating + film thickness before heating) xl (VI) Evaluation of chemical resistance A film was formed on a substrate in the same manner as in the above "(V) evaluation of heat resistance". The film thickness of the film (manufactured by KLA Tencol Co., Ltd.) was measured by a needle-type film thickness measuring machine (manufactured by KLA Tencol Co., Ltd.), and then the substrate with the film was immersed in an alignment film heated to 60 ° C. Film thickness (after immersion film thickness) after peeling (Chemi-Clean TS-204, manufactured by Sanyo Chemical Industries Co., Ltd.) for 15 minutes, washing with water, and drying at 120 ° C for 15 minutes in a baking-58-200907573 box And compare the two. The film thickness change rate calculated by the following formula is used as the chemical resistance. Film thickness change rate (%) = (film thickness after immersion + film thickness before immersion) χ 100 (VII) Evaluation of sublimation amount The film was formed on the substrate in the same manner as in the above "(V) evaluation of heat resistance". For cutting the substrate with this film into 1 cm x 1 cm, use Head space Sampra JHS — 100A (manufactured by Nippon Analytical Industries Co., Ltd.) and gas chromatography/mass spectrometer JEOL JMS — AX 5 05W (Japan Electronics (Stock) system) The amount of sublimate produced by Head space gas chromatography/mass spectrometry under the conditions of an analysis temperature range of 25 to 230 ° C and a temperature increase rate of 100 ° C / 10 minutes. The amount of sublimation (the specific gravity: 0.701, injection amount: 〇.〇2μί) was used as the standard substance, and the amount of sublimation per unit area was determined by the following formula using the peak area as the reference. After that. Sublimation amount (pg/cm2) = (peak area per liter of sublimate + peak area of octane) x〇.02x0.701 When the amount of sublimation is 2Mg/cm2 or less, the amount of sublimation is evaluated as "less" . (VIII) Evaluation of rub resistance -59- 200907573 The exposure amount of radiation exposure was 400 J/m2, and the development time was 60 seconds. 'The rest of the system is the same as the above evaluation of "(I) imaging performance" A pattern-like film is formed on the substrate. On the film, AL 3 046 (trade name, manufactured by JSR) was applied as a liquid crystal alignment agent by a printer for coating a liquid crystal alignment film, and then heated at 18 (TC for 1 hour to form a liquid crystal having a film thickness of 0.05 μm). A film of the alignment agent. Then, for the film of the liquid crystal alignment agent, a rubbing machine having a roll of a cloth made of polyamide was used, and the number of rotations of the roll was 500 rpm, and the moving speed of the stage was 1 cm/sec. At this time, for the pattern formed by the circular residual pattern of 15 μm, the pattern is peeled off or cut. (IX) Evaluation of voltage retention is performed on the surface to prevent sodium ion elution. The Si 02 film is further coated on a soda glass substrate having a specific shape by vapor deposition of an ITO (indium-tin oxide alloy) electrode, and the solution of the above-mentioned prepared radiation-sensitive linear resin composition is coated by a spin coater, respectively. Pre-baked in a clean oven at 90 ° C for 10 minutes, forming a film of a sensitive linear resin composition (film thickness 2.0 μm). The film is irradiated with an exposure amount of 500 J/m2 without passing through the mask. Line. After that, use 〇·〇 4% by weight The potassium hydroxide aqueous solution was developed by a dipping method at a development time of 23 ° C for 1 minute, and then washed with pure water for 1 minute, and further baked in an oven at 23 ° C for 30 minutes to form a hardening. The substrate having the cured film and the substrate on which only the Si〇2 film and the IT0 electrode are formed are made of a sealing agent mixed with glass beads of 〇8 mm, and the hard-60-200907573 film is opposed to the ITO electrode. After laminating, a liquid crystal cell MLC 6608 (trade name) manufactured by Merck Co., Ltd. was injected into the gap to prepare a liquid crystal cell. This liquid crystal cell was injected into a constant temperature layer at 60 ° C, and the liquid crystal voltage was maintained by Dongyang Technic. The rate measurement system "VHR-1A type" (trade name) measures the voltage holding ratio of the liquid crystal cell. At this time, the applied voltage is a square wave of 5.5 V, and the measurement frequency is 60 Η z. Here, the voltage holding ratio is The measurement was carried out by the following equation: Voltage holding ratio (%) = (liquid crystal cell potential difference after 1 6 · 7 msec / voltage applied in 〇 msec) xl 〇〇 if the liquid crystal cell voltage retention rate Below 90%, the liquid crystal cell system cannot make 16.7 milliseconds Applied voltage is held at a certain level, the liquid crystal method without sufficient alignment, an afterimage, etc. "burn" high danger of Example 14 and 15 &lt;Preparation of Sensitive Radiation Linear Resin Composition Solution&gt; (A) copolymer, (B) polymerizable unsaturated compound, (C) radiation radiation linear polymerization initiator and (D) of the types and amounts described in Table 1 In the case of the component 15 and the component (E), the component (E) was mixed, and further, 5 parts by weight of r-glycidoxypropyltrimethoxydecane was mixed as (F) adhesion aid, FTX-218 (product) 5 parts by weight of (G) surfactant and 0.5 parts by weight of 4-methoxy oxime as (H) storage stabilizer, in a manner that the solid content concentration is 50% by weight' After separately adding the propylene-61 - 200907573 alcohol monomethyl ether acetate, the solution of the radiation-sensitive linear resin composition was separately prepared by filtration through a micropore filter having a pore diameter of 0.5 μm. Further, the (Α) copolymer was added as a polymer solution containing the copolymer described in Table 1 (obtained in the above Synthesis Example 1 or 2), and the amount of the copolymer contained therein was the amount shown in Table 1. &lt;Evaluation of Sensitive Radiation-Linear Resin Composition Solution&gt; Using a sensitive radiation linear resin composition prepared as described above, a film of a radiation-sensitive linear resin composition is formed on a substrate by a transfer method as described below, Further, when a photomask was used for the exposure, a photomask having a circular residual pattern of a plurality of diameters of 30 μm was used as a mask, and the film was placed in contact with the film, and the other examples were compared with Examples 1 to 13 and Comparative Example 1 to 3 A film was formed in the same manner for evaluation. However, in the "Evaluation of Adhesion in (II) Imaging", it is evaluated that one of the patterns that should be formed in a circular pattern of 30μηι should be formed by ι〇0 'in '(IV) The pattern of the round-shaped residual pattern from 30 μm is evaluated in the "Evaluation of the size" and "(VIII) Evaluation of the abrasion resistance". The results of the evaluation are shown in Table 2. &lt;Formation of a radiation-sensitive linear resin composition by a transfer method&gt; On a polyethylene terephthalate (pet) film having a thickness of 38 μm, a thin applicator is used to apply the above-mentioned modulated radiation. A solution of the linear resin composition was heated at 1 ° C for 5 minutes to prepare a dry film having a thickness of 4 · 0 μm of the sensitive radiation - 62 - 200907573 transfer layer. This dry film is adhered to the surface of the synthetic radiation linear transfer layer on the surface of the alkali-free glass substrate ("(IX) Evaluation of Voltage Retention Rate" on the surface of the soda glass substrate on which the SiO 2 film and the ITO electrode are formed). The linear layer of sensitive radiation is transferred onto the glass substrate by thermocompression bonding. -63- 200907573 £ 1 (E) Ingredient parts by weight 1 〇1 〇1 〇〇〇〇〇〇〇〇〇1 〇o I o |Type | D UJ 1 1 1 1 1 1 E-2 1 1 1 1 CM Mountain* UJ l I l (9) Component parts by weight \n - ιό 〇· - 1 I 1 m P D-1 D-1 D-2 D-3 〇D-1 0-4 D-5 1 〇D-2 D-5 D-1 a 〇D-1 i 1 i \ 劝 mm mm 璨 璨 騵 5 5 5 5/10 | 5/t0 5/10 5/10 5/10 5/5/2 5/10 1 5 /10 L5/10/5/1 5/10/2/2/1 5/10/5/1 5/10 5/10/5/1 in in 5/10 5/10 5/10/5/1 Category C-1/C-2 C-1/C-2 C-1/GZ C-1/C-2 C-1/C-2 C-3/C-4/C-5 C-1/C -2 C-1/C-2 C-1/C-2/C-3/C-5 C-1 /C-2/C-3/C-4/C-5 C-1/C-2 /C-3/C-5 C-1/C-2 C-1/C-2/C-3/C-5 C-1/C-2 C-1/C-2 C-1/C- 2 C-1/C-2 C-1/C-2/C-3/C-5 (8) Polyunsaturated compound parts by weight 100/10/5 100/10 100/10/5 100/5 S 100/ 10/5 100/10/5 100/10/5 100/20/10/5 1' 100/20/10/5 100/20/10/5 150/10/5 150/10/5 100/10 100 /20/10/5 100/10/5 100/10 100/20/10/5 Category B-1/B-3/B-4 B-1/B-3 B-1/B-3/B- 4 B-1/B-4 1 B-1/B-3/B-4 B-1/B-3/B-4 B-1/B-3/B-4 Β-1/Β-2/ Β-3/Β-4 Β-1/Β-2/Β-3/Β-4 Β-1/Β-2/Β-3/Β-4 Β-1/Β- 3/Β-4 B-1/B-3/B-4 B-1/B-3 B-1/B-2/B-3/B-4 B-1/B-3/B-4 B -1/B-3 B-1/B-2/B-3/B-4 (A) Copolymer SS 8 r* 100 50/50 50/50 50/50 50/50 50/50 50/50 50 /50 50/50 J 50/50 8 I 50/50 1 100 100 50/50 W 郷A-1 A-2 A-3 A-4 A-1/A-2 A-1/A-2 A- 1/A-2 A-1/A-3 Α-1/Α-2 Α-1/Α-2 A-VA-2 Α-1/Α-2 A-1/A-3 A-2 A- 1/A-2 A-1 A-2 A-1/A-2 I Example 1 | Example 2 | Example 3 | | Example 4 | Example 5 f Example 6 | Example 7 I Example β | Example 9 | "Example "Example" | Example 12 | Example 13 | Example 14 1 | Example 15 | Comparative Example 1 | Comparative Example 2 | Comparative Example 3 - 64 - 200907573 In Table 1, The abbreviations of the components are as follows. (B) Polymerizable unsaturated compound B-1: dipentaerythritol hexaacrylate B - 2 : KAYARAD DPHA - 40 Η (made by Nippon Kayaku Co., Ltd.) Β - 3: 1,9-nonanediol diacrylate Β - 4 : Aronix Μ - 5300 : (East Asia Synthetic (Share)) (C) Minfu Radiation Polymerization Starter, Amine Sensitizer and Thiol Compound C-1: Ethyl Ketone-1 - [9 — Ethyl-6-(2-methylbenzhydryl)-9-indole-3-indenyl-1-(0-ethylhydrazine) (trade name "Irgacure 0ΧΕ 02", manufactured by Ciba Specialty Chemicals C-2: 2-dimethylamino 2-(4-methylbenzyl)-i-(4------- 4-yl-phenyl)-Dingyuan-1-嗣 (trade name) "irgacure 379", manufactured by Ciba Specialty Chemicals Co., Ltd.) C-3: 2,2'_bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole C-4: 4,4'-bis(diethylamino)benzophenone (amine-based sensitizer) C-5: 2-Hydroxythiobenzothiazole (thiol compound) (D) D - 1 : N - hydroxy quinone imine D-2 : N-hydroxy succinate Amine D - 3: N - hydroxy - 1,8 - naphthyl imine, D-4: N - ethoxy quinone imine, D - 5: trihydroxyimido cyanuric acid, -65- 200907573 (E) Component E-1: Novolac type epoxy resin (product name "Epicote 152", made by Japan Epoxy resin) E_2: Novolac type epoxy resin (trade name "Epicote 157S65", Japan Epoxy resin (share) system) Further, the "-" in the column indicates that the component is not used. -66 - 200907573 Voltage holding ratio (%) in σ» Bu cn 卜 σ\ 卜 σ&gt; σ\ σ\ 卜 σ\ r* σ\ 卜 σι σ\ 卜 σ\ Γ0 &lt;J\ s; Rubbing resistance (with or without peeling and cutting) Invading the end of the world to destroy m 堞壊壊璀壊堞* 壊 揉捶 揉捶 揉捶 揉捶 揉捶 七 VII, seven, seven, seven, chemical resistance (%) V £ σ\ &gt;99 &gt;99 &gt;99 &gt;99 &gt;99 &gt;99 &gt;99 &gt;99 &gt;99 &gt;99 &gt;99 &gt;99 &gt;99 &gt;99 Ch 00 σ\ 00 σ\ heat resistance (%) &gt;99 &gt;99 &gt;99 &gt;99 &gt;99 &gt;99 &gt;99 &gt;99 &gt;99 &gt;99 &gt;99 &gt;99 &gt;99 &gt;99 in σ\ 03 CTi 00 (Τ\ graphic size method (um) ο CN3 ΓΟ Ln ιΗ Γ 0 CM rH Γ〇m 〇ΓΟ LO σ&gt; tN 00 rH Γ0 〇&gt; rH Γ0 τΗ CV3 ΓΟ CN rH ro U1 CNJ Γ0 Η m ΓΟ m η 1—1 m Γ0 σι mm ΓΟ 00 CM ι—Ι CO OJ i—( σ\ CN hardening degree ί ί3$ (from (bad bad imaging when adhesion 86/100 100/ 100 100/100 100/100 95/100 I 69/100 100/100 100/100 100/100 100/100 100/100 100/100 100/100 I 100/100 j 100/100 0/100 34/100 51 /100 Developmentality (〇3) - Example 1 Example 2 Example 3 1 Example 4 Example 5 Example 6 1 Example 7 Example 8 | Example 9 1 Example 10 Example 11 "Example 12 Example 13 | Example 14 Example 15 1 Comparative Example 1 1 Comparative Example 2 Comparative Example 3 -67- 200907573 In Table 2, "&gt; 99" in "Evaluation of (V) heat resistance" and "(VI) Evaluation of chemical resistance" means that the calculation of the film thickness change rate exceeds 99% and is 100% or less. Further, in the "Evaluation of the abrasion resistance of (VIII) in Comparative Example 1, both the peeling and the cutting can be seen in the pattern after the rubbing. Effect of the Invention The sensitive radiation linear resin composition of the present invention has The high radiation sensitivity, even for a low exposure amount, is not peeled off in the developing step, and a pattern-like film having an excellent strength can be easily formed with a desired pattern size. Further, no sublimate was generated in the heating step at the time of formation of the pattern-shaped film. The radiation sensitive linear resin composition of the present invention is particularly preferably used to form a spacer or a protective film of a liquid crystal display element. The spacer or the protective film of the present invention formed from the sensitive radiation linear resin composition of the present invention is excellent in dimensional accuracy, strength, heat resistance and the like, and can be suitably used for a liquid crystal display element. Further, since the durability (chemical resistance) of the liquid crystal alignment film peeling liquid is also excellent, the product yield in the substrate regeneration step can be improved. Further, the spacer of the present invention is free from pattern peeling in the rubbing step of the liquid crystal alignment film. The liquid crystal display element of the present invention having the above-mentioned spacer or protective film can suppress the occurrence of "pre-burning" and has excellent long-term reliability. -68-

Claims (1)

200907573 十、申請專利範圍 1 · 一種敏輻射線性樹脂組成物，其特徵在於含有： (A) 含有（al)選自由不飽和羧酸及不飽和羧酸酐所構 成之群的至少一種而成之不飽和化合物的共聚物、 (B) 聚合性不飽和化合物、 (C) 敏輻射線性聚合起始劑、以及 (D) 具有以下述式（1)200907573 X. Patent Application No. 1: A sensitive radiation linear resin composition comprising: (A) containing (al) a non-saturated carboxylic acid and an unsaturated carboxylic anhydride, at least one selected from the group consisting of a copolymer of a saturated compound, (B) a polymerizable unsaturated compound, (C) a radiation-sensitive linear polymerization initiator, and (D) having the following formula (1) N—Ο-* ( 1 ) 〇 (式（1)中，「*」表示鍵結鍵） 所示之構造的化合物。 2 .如申請專利範圍第1項之敏輻射線性樹脂組成物， 其中（D)成分爲以下述式N—Ο-* ( 1 ) 〇 (In the formula (1), "*" indicates a bond) The compound of the structure shown. 2. The sensitive radiation linear resin composition of claim 1, wherein the component (D) is of the following formula -69- 200907573-69- 200907573 (上述式中，R係分別獨立地表示氫原子、碳數： 級或三級之院基、碳數5〜12之環狀院基、嫌丙 7〜30之芳烷基或碳數2〜30之醯基） 之任一者所示之化合物。 3.如申請專利範圍第2項之敏輻射線性 物，其中（D)成分爲N-羥基琥珀酸醯亞胺、N-羥 片烯-2,3-二羧基醯亞胺、N-羥基酞醯亞胺、N-酞醯亞胺、N-苯醯氧基酞醯亞胺、N-羥基-1，8-亞胺或三羥基醯亞胺三聚氰酸。 4 .如申請專利範圍第1項之敏輻射線性樹脂 其中（A)共聚物爲含有（al)選自由不飽和羧酸及 酸酐所構成之群的至少一種、以及（a2-l)選自由 乙烷基之聚合性不飽和化合物及具有氧雜環丁基 不飽和化合物所構成之群的至少一種而成之不飽 3〜30之二 基、碳數 樹脂組成 基-5 -降冰 乙醯氧基 萘二甲醯 組成物， 不飽和羧 具有環氧 之聚合性 和化合物 -70 - 200907573 之共聚物。 5 ·如申請專利範圍第2項之敏輻射線性樹脂組成物， 其中（A)共聚物爲含有（al)選自由不飽和羧酸及不飽和羧 酸酐所構成之群的至少一種、以及（a2-l)選自由具有環氧 乙烷基之聚合性不飽和化合物及具有氧雜環丁基之聚合性 不飽和化合物所構成之群的至少一種而成之不飽和化合物 的共聚物。 6.如申請專利範圍第3項之敏輻射線性樹脂組成物， 其中（A)共聚物爲含有（a 1)選自由不飽和羧酸及不飽和羧 酸酐所構成之群的至少一種 '以及（a2-l)選自由具有環氧 乙烷基之聚合性不飽和化合物及具有氧雜環丁基之聚合性 不飽和化合物所構成之群的至少一種而成之不飽和化合物 之共聚物。 7 ·如申請專利範圍第1 ~6項中任一項之敏輻射線性樹 脂組成物，其中（B)聚合性不飽和化合物含有於一分子中 具有聚合性不飽和鍵1〜3個之聚合性不飽和化合物、與於 一分子中具有聚合性不飽和鍵4個以上之聚合性不飽和化 合物各至少一種。 8 .如申請專利範圍第1〜6項中任一項之敏輻射線性樹 脂組成物，其中（C)敏輻射線性聚合起始劑含有選自由 〇-醯基肟化合物及乙醯苯化合物所構成之群的至少一種。 9.如申請專利範圍第1 ~6項中任一項之敏輻射線性樹 脂組成物，其中進一步含有（E)於一分子中具有2個以上 之環氧乙院基之化合物。 -71 - 200907573 1 〇.如申請專利範圍第1〜6項中任一項之敏輻射線性 樹脂組成物’其係可使用於用以形成液晶顯示元件之間隔 件或保護膜。 11. 一種液晶顯示元件之間隔件的形成方法，其特徵 在於：以下述記載之順序含有至少下述（1)〜（4)之步驟： (1) 使如申請專利範圍第1〜6項中任一項之敏輻射線 性樹脂組成物的被膜形成於基板上之步驟； (2) 對該被膜之至少一部分照射輻射線之步驟； (3 )使輻射線照射後之被膜進行顯像的步驟；及 (4)加熱顯像後之被膜的步驟。 1 2 · —種液晶顯示元件之間隔件，其係藉由如申請專 利範圍第1 1項之方法來形成。 13. —種液晶顯示元件’其特徵在於具備如申請專利 範圍第1 2項之間隔件。 14. 一種液晶顯示元件之保護膜的形成方法，其特徵 在於··以下述記載之順序含有至少下述（1)〜（4)之步驟： (1) 使如申請專利範圍第1〜6項中任一項之敏輻射線 性樹脂組成物的被膜形成於基板上之步驟； (2) 對該被膜之至少一部分照射輻射線之步驟； (3) 使輻射線照射後之被膜進行顯像的步驟；及 (4) 加熱顯像後之被膜的步驟。 1 5 · —種液晶顯示元件之保護膜，其係藉由如申請專 利範圍第1 4項之方法來形成。 16.—種液晶顯示元件，其特徵在於：具備如申請專利 -72- 200907573 範圍第1 5項之保護膜 200907573 七、指定代表圖： (一） 、本案指定代表圖為：無 (二） 、本代表圖之元件代表符號簡單說明：無 八、本案若有化學式時，請揭示最能顯示發明特徵的化學 式：無(In the above formula, R each independently represents a hydrogen atom, a carbon number: a tertiary or tertiary source, a cyclical group having a carbon number of 5 to 12, an aralkyl group having a carbon number of 7 to 30, or a carbon number of 2~ A compound represented by any one of 30). 3. The sensitive radiation linear substance of claim 2, wherein the component (D) is N-hydroxysuccinic acid imine, N-hydroxylene-2,3-dicarboxy quinone imine, N-hydroxy hydrazine Yttrium imine, N-quinone imine, N-benzoquinone imine, N-hydroxy-1,8-imine or trihydroxyquinone imine cyanuric acid. 4. The radiation sensitive linear resin according to claim 1, wherein the (A) copolymer is at least one selected from the group consisting of (al) selected from the group consisting of unsaturated carboxylic acids and acid anhydrides, and (a2-l) selected from the group consisting of a polymerizable unsaturated compound of an alkyl group and at least one of the group consisting of an oxetanyl unsaturated compound, which is a non-saturated 3 to 30 bis group, a carbon number resin group-5 - an ice acetonitrile The quinone dioxime composition, the unsaturated carboxy group has a copolymer of epoxy and a copolymer of the compound -70 - 200907573. 5. The radiation sensitive linear resin composition according to item 2 of the patent application, wherein the (A) copolymer is at least one selected from the group consisting of (al) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and (a2) And a copolymer of an unsaturated compound selected from the group consisting of a polymerizable unsaturated compound having an oxiranyl group and a polymerizable unsaturated compound having an oxetanyl group. 6. The sensitive radiation linear resin composition of claim 3, wherein the (A) copolymer is at least one selected from the group consisting of (a1) an unsaturated carboxylic acid and an unsaturated carboxylic anhydride; A2-l) a copolymer of an unsaturated compound selected from the group consisting of a polymerizable unsaturated compound having an oxirane group and a polymerizable unsaturated compound having an oxetanyl group. The sensitive radiation linear resin composition according to any one of claims 1 to 6, wherein (B) the polymerizable unsaturated compound contains one to three polymerizable unsaturated bonds in one molecule. The unsaturated compound and at least one of four or more polymerizable unsaturated compounds having a polymerizable unsaturated bond in one molecule. The sensitive radiation linear resin composition according to any one of claims 1 to 6, wherein the (C) radiation sensitive linear polymerization initiator comprises a compound selected from the group consisting of a ruthenium-indenyl ruthenium compound and an acetophenone compound. At least one of the groups. 9. The radiation sensitive linear resin composition according to any one of claims 1 to 6, which further comprises (E) a compound having two or more epoxy groups in one molecule. The radiation sensitive linear resin composition of any one of claims 1 to 6 can be used for a spacer or a protective film for forming a liquid crystal display element. A method of forming a spacer for a liquid crystal display device, comprising the steps of at least the following (1) to (4) in the order described below: (1) as in the first to sixth aspects of the patent application; a step of forming a film of the sensitive radiation linear resin composition on the substrate; (2) a step of irradiating at least a part of the film with the radiation; (3) a step of developing the film after the irradiation of the radiation; And (4) a step of heating the film after development. 1 2 - A spacer for a liquid crystal display element, which is formed by the method of claim 11 of the patent application. A liquid crystal display element' is characterized in that it has a spacer as disclosed in claim 12 of the patent application. 14. A method of forming a protective film for a liquid crystal display device, comprising: at least the following steps (1) to (4) in the order described below: (1) making items 1 to 6 as claimed in the patent application. a step of forming a film of the sensitive radiation linear resin composition on the substrate; (2) a step of irradiating at least a part of the film with the radiation; (3) a step of developing the film after the irradiation of the radiation And (4) the step of heating the film after development. A protective film for a liquid crystal display element is formed by the method of claim 14 of the patent application. 16. A liquid crystal display element, comprising: a protective film of the item 15 of the scope of the patent application-72-200907573, and a designated representative figure: (1), the designated representative figure of the case is: no (2), The representative symbol of the representative figure is a simple description: No. 8. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: None
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