TWI380065B - Radiation sensitive resin composition for forming spacer, spacer and the forming method thereof, and liquid crystal display element - Google Patents

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

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TWI380065B
TWI380065B TW094104389A TW94104389A TWI380065B TW I380065 B TWI380065 B TW I380065B TW 094104389 A TW094104389 A TW 094104389A TW 94104389 A TW94104389 A TW 94104389A TW I380065 B TWI380065 B TW I380065B
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spacer
weight
compound
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radiation
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TW094104389A
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TW200537168A (en
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Daigo Ichinohe
Tomoko Iwabuchi
Toshihiro Nishio
Toru Kajita
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Jsr Corp
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0755—Non-macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds

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

Description

修正本 九、發明說明： 【發明所屬之技術領域】 本發明係關於間隔物形成用放射線敏感性樹脂組合 物間隔物及其形成方法和液晶顯示元件，更具體而言 本發明係關於適合用來作為形成液晶顯示面板或觸摸 式面板等顯示面板中使用的間隔物用的放射線敏感性樹 月曰組合物、由該組合物形成的間隔物及其形成方法 '以 /、有該間隔物的液晶顯示元件。 【先前技術】 以往，為了使兩片透明基板之間的間隔（胞間隙）保 持一定，在液晶顯示元件中使用具有規定粒徑的玻璃微 珠或塑膠微珠等間隔物粒子，但是，由於這些間隔物粒 子疋隨機地散佈在玻璃基板等透明基板上’因而當像素 形成區域中存在間隔物粒子時，就會發生間隔物粒子被 寫入的現象，或者入射光發生散射，使液晶顯示元件的 對比度降低等問題。 為了解決這些問題，人們採用光刻形成間隔物的方 法。這種方法是，在基板上形成放射線敏感性樹脂組合 物的被膜，通過規定的光罩進行紫外線曝光，然後顯影 ，形成點狀或條紋狀的間隔物，由於可以只在像素形成 區域以外的規定部位形成間隔物，因而基本上解決了上 述的問題。 可是’在實際形成間隔物的過程中，例如採用光刻 在濾色片等中所使用的透明基板上形成間隔物的場合， 往往使用接近式曝光機。在進行這種接近式曝光時，比 修正本 ^380065 較理想的方法是’在曝光所用光罩與形成了放射線敏感 性樹脂組合物被膜的基板之間設置—定的間隔後進行曝 光’這樣就可以按照光罩的圖案進行曝光。然而，由於 在5亥間隔中充滿了空氣或氮氣’使得透過光罩的開口部（ •透明部）的光線在該間隙中擴散而變寬，因而出現所謂曝 • 光比光罩圖案的設計尺寸要寬等的問題。 為了解決這一問題，本申請人發現並在專利文獻1 中指出，通過使用1，2 -辛二酮-1-[4-(苯硫基）苯基]-2-(0-籲苯曱酿基肟）作為放射線敏感性樹脂組合物的放射線敏 感性聚合引發劑，即使是進行接近式曝光，也可以忠實 地再現光罩圖案的設計尺寸’此外，可以形成強度和耐 熱性等均優異的顯示面板用間隔物。 專利文獻1 :特開200 1-261761號公報 ： 另外’近年來，隨著液晶顯示元件的大面積化和生 產率的提咼’母體玻璃基板的尺寸已從過去的680x880 mm左右增大至1,500x1，800 mm左右。在間隔物的形成步 Φ驟中’通常是將間隔物形成用放射線敏感性樹脂組合物 塗布在透明基板上’在熱板上通過燒成來除去溶劑，然 後進行曝光和顯影，從而形成間隔物。然而，伴隨這基 板的.大型化’在間隔物的形成過程中，由於放射線敏感 性樹脂組合物中的放射線敏感性聚合引發劑成分發生昇 華’導致燒成爐或光罩受污染的問題，並引起生產節拍 的降低和生產成本的上升，因此令人擔心。 進而’本申請人在專利文獻2中指出，通過使用l_(2_ 溴-4-味淋并笨基）-2 -苄基-2-二甲胺基丁烧-i__或ι_(3_ 1380065 修正本 溴-4-咮啉并笨基）-2-苄基_2_二甲胺基丁烷丨酮等的溴 取代苯乙酮系化合物作為放射線敏感性樹脂組合物的玫 射線敏感性聚合引發劑，可以減輕由於放射線敏感性聚 合引發劑成分的昇華所造成的燒成爐或排氣管道的污染 ，並忐減輕在反覆使用顯影液時所造成的設置在顯影生 • 產線_的過濾器的堵塞等。 專利文獻2 :特開2001 -2356 17號公報 可用於形成間隔物的放射線敏感性樹脂組合物通常 含有（曱基）丙稀酸酯等的聚合性不飽和化合物或具有環 氧基等熱交聯性基團的化合物，因此，為了防止在保存 時發生的聚合或交聯反應，在多數情況下都是將其作為 組合物溶液在低於室溫的溫度下保存。然而，在專利文 獻2中記載的溴取代苯乙酮系化合物在較低溫度下保存 時往往會由於再結晶而析出，又’溴取代的苯乙酮系化 合物再結晶化之組合物溶液之溫度即使升高到室溫以上 ’也難以使再結晶化之成分再溶解，它在間隔物的形成 #步驟中就作為液體中的異物而殘存下來，因此使得在塗 布到基板上時引起條紋不均勻或靈敏度降低等現象的可 能性非常高。 然而’專利文獻1和專利文獻2中記載的化合物包括 在内’以往在形成間隔物時使用的放射線敏感性樹脂組 合物’在防止由於放射線敏感性聚合引發劑成分的昇華 所造成的燒成爐或光罩等的污染和液體中異物的發生等 方面不夠好，因此人們強烈希望開發同時具有這些特性 的放射線敏感性樹脂組合物。 丄 JOUUO!) 修正本The present invention relates to a radiation sensitive resin composition spacer for forming a spacer, a method of forming the same, and a liquid crystal display element, and more particularly, the present invention relates to a suitable A radiation-sensitive sapphire composition for forming a spacer used in a display panel such as a liquid crystal display panel or a touch panel, a spacer formed of the composition, and a method for forming the same, and a liquid crystal having the spacer Display component. [Prior Art] Conventionally, in order to keep the interval (cell gap) between two transparent substrates constant, spacer particles such as glass beads or plastic beads having a predetermined particle diameter are used for the liquid crystal display device. The spacer particles are randomly dispersed on a transparent substrate such as a glass substrate. Thus, when spacer particles are present in the pixel formation region, spacer particles are written, or incident light is scattered to cause liquid crystal display elements. Problems such as reduced contrast. In order to solve these problems, a method of forming spacers by photolithography has been employed. In this method, a film of a radiation-sensitive resin composition is formed on a substrate, exposed to ultraviolet light by a predetermined mask, and then developed to form a dot-like or stripe-shaped spacer, which can be specified only in the pixel formation region. The portion forms a spacer, thus substantially solving the above problems. However, in the case where a spacer is actually formed, for example, a spacer is formed on a transparent substrate used for a color filter or the like by photolithography, a proximity exposure machine is often used. In the case of such proximity exposure, it is preferable to perform the exposure after the interval between the photomask used for the exposure and the substrate on which the radiation-sensitive resin composition is formed, as in the case of the correction of the "380065". The exposure can be performed in accordance with the pattern of the reticle. However, since the light passing through the opening (or the transparent portion) of the reticle is diffused and widened in the interval of 5 hai, the design size of the so-called exposure light reticle pattern appears. To be wide and so on. In order to solve this problem, the Applicant has found and pointed out in Patent Document 1 that by using 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(0-phenylindole) The radiation-sensitive polymerization initiator which is a radiation-sensitive resin composition can faithfully reproduce the design size of the mask pattern even when the proximity exposure is performed. In addition, it is excellent in strength and heat resistance. A spacer for the display panel. Patent Document 1: JP-A-200 1-261761: In addition, in recent years, with the increase in the area of liquid crystal display elements and the improvement in productivity, the size of the mother glass substrate has increased from 680x880 mm to 1,500x1 in the past. , about 800 mm. In the formation step of the spacers, 'the radiation-sensitive resin composition for spacer formation is usually coated on a transparent substrate'. The solvent is removed by firing on a hot plate, and then exposed and developed to form a spacer. . However, with the enlargement of the substrate, 'the sublimation of the radiation-sensitive polymerization initiator component in the radiation-sensitive resin composition during the formation of the spacer causes the contamination of the firing furnace or the reticle, and This is a cause of concern for the reduction in production tact and the increase in production costs. Further, the applicant has pointed out in Patent Document 2 that by using l_(2_bromo-4-mylin and stupid)-2-benzyl-2-dimethylaminobutyrate-i__ or ι_(3_ 1380065 A bromine-substituted acetophenone-based compound such as the present bromo-4-porphyrin-p-phenyl)-2-benzyl-2-dimethylaminobutanone as a radiation sensitive resin composition The agent can reduce the contamination of the firing furnace or the exhaust pipe caused by the sublimation of the radiation-sensitive polymerization initiator component, and reduce the filter disposed on the development line when the developer is repeatedly used. The blockage and so on. The radiation sensitive resin composition which can be used for forming a spacer usually contains a polymerizable unsaturated compound such as (mercapto) acrylate or a thermal crosslinking such as an epoxy group. The compound of the group, therefore, in order to prevent the polymerization or crosslinking reaction which occurs during storage, it is usually stored as a composition solution at a temperature lower than room temperature. However, when the bromine-substituted acetophenone-based compound described in Patent Document 2 is stored at a relatively low temperature, it tends to be precipitated by recrystallization, and the temperature of the composition solution of the bromine-substituted acetophenone-based compound is recrystallized. Even if it rises above room temperature, it is difficult to redissolve the recrystallized component, which remains as a foreign matter in the liquid in the formation of the spacer #, thus causing uneven streaks when applied to the substrate. Or the possibility of a decrease in sensitivity or the like is very high. However, the compounds described in Patent Document 1 and Patent Document 2 include a radiation-sensitive resin composition used in the conventional formation of a spacer to prevent the sublimation of the polymerization initiator component due to radiation sensitivity. The contamination of the reticle or the like and the occurrence of foreign matter in the liquid are not good enough, and therefore it is strongly desired to develop a radiation-sensitive resin composition having these characteristics at the same time.丄 JOUUO!) Revision

種間隔物用 制由於放射 引發劑成分的昇華所 3丨& Μ β 带所引起的燒成爐或光I 會產生液體中的異物，而B-r 一初而且可以容易地开 【發明内容】 本發明的任務在於提供一 樹脂組合物，該組合物能夠抑 靈敏度和高㈣像解析度、同時在斷面形 对摩擦性、與透明基板的黏附性等各種 間隔物；本發明的任務還在於提供一種由 合物形成的間隔物及其形成方法、以及具 液晶顯示元件。 本發明的第一方面是一種間隔物形成 性樹脂組合物，其特徵在於，該組合物含 [A ] (a 1)不飽和羧酸和/或不飽和羧酸画 氧基的不飽和化合物與（a3)其他不飽和化 放射線敏感性 線敏感性聚合 等的污染、不 成一種具有高 狀、抗壓強度 性能均優良的 上述的樹脂組 有該間隔物的 用放射線敏感 有： 卜、（a2)含有環 合物的共聚物 為必要成分的 [B ]聚合性不飽和化合物；以及 [C ]以由下列通式（1)表示的化合物作 放射線敏感性聚合引發劑；In the case of a spacer, the firing furnace or the light I caused by the sublimation of the radiation initiator component can generate foreign matter in the liquid, and Br can be easily opened at the beginning of the invention. SUMMARY OF THE INVENTION It is an object of the invention to provide a resin composition which is capable of suppressing sensitivity and high (four) image resolution, and at the same time, various types of spacers such as cross-sectional shape frictional property and adhesion to a transparent substrate; A spacer formed of a composition, a method of forming the same, and a liquid crystal display element. A first aspect of the invention is a spacer-forming resin composition characterized by comprising an unsaturated compound of [A] (a 1) unsaturated carboxylic acid and/or unsaturated carboxylic acid oxirane and (a3) Other unsaturated semiconductor radiation-sensitive line-sensitive polymerization, etc., and the above-mentioned resin group which is excellent in both high-strength and compressive strength properties, the radiation sensitive of the spacer is: (a2) a BD composition-containing copolymer is an essential component of the [B] polymerizable unsaturated compound; and [C] is a compound represented by the following formula (1) as a radiation-sensitive polymerization initiator;

在（1)式中，R1表示碳原子數1-12的直 狀的烷基；R2和R3彼此獨立地表示氫原子， 鏈、支鏈或環 碳原子數1 -1 2 1380065 修正本 的直鏈、支鏈或環狀的烷基或爷基；R4、R5、R7和R8彼 此獨立地表示氫原子；鹵素原子，碳原子數1-12的直鏈 、支鏈或環狀的烷基或者碳原子數1-4的直鏈或支鏈狀的 燒氧基；R6表示鹵素原子，碳原子數1-12的直鏈、支鏈 或故狀的烧基，經選自羥基和碳原子數1_4的直鏈或支鏈 狀的烧氧基組成之群的取代基所取代的碳原子數卜12的 直鍵、支鏈或環狀的烷基，碳原子數丨_4的直鏈或支鏈狀 鳙的燒氧基’或者經選自羥基和碳原子數1-4的直鏈或支鏈 狀的烧氧基組成之群的取代基所取代的碳原子數2_4的 直鏈或支鏈狀的烷氧基。 本發明中所謂之“放射線”是指包括紫外線、遠紫 卜線、X射線、電子射線 '分子射線、γ射線、同步加速 器輻射線、質子束射線等在内的各種射線。 本發明的第二方面是由上述的間隔物形成用放射線 敏感性樹脂組合物形成的間隔物構成。 本發明的第三方面是由間隔物的形成方法構成，其 特徵在於，該方法至少包含下述（1)〜（句的步驟： /1)在基板上形成申請專利範圍第i項中記載的間隔 /成用放射線敏感性樹脂組合物的被膜的步驟； (2) 對忒被膜的至少一部分用放射線進行曝光 騍； (3) 將曝光後的上述被膜顯影的步驟； (4) 將顯影後的上述被膜加熱的步驟。 _本發明的第四方面是由具有上述間隔物的液晶顯示 %件構成。 -10- 1380065 修正本 【實施方式】 〈間隔物用放射線敏感性樹脂組合物&gt; 下面對本發明的間隔物用放射線敏感性樹脂組合物 (以下簡稱“放射線敏感性樹脂組合物”）進行詳細描述。 ' 共聚物[A] ， 在本發明的放射線敏感性樹脂組合物中的[A]成分 ，是由（a 1)不飽和羧酸和/或不飽和羧酸酐（以下簡稱“化 合物（al)”）、（a2)含有環氧基的不飽和化合物（以下簡稱 鲁“不飽和化合物（a2)” ）和（a3)其他的不飽和化合物（以 下簡稱“化合物（a3)” ）形成的共聚物（以下簡稱“共聚 物[A]”）所組成。 作為化合物（a 1)’例如可以舉出：丙烯酸、甲基丙 烯酸、巴豆酸、琥珀酸一（2-丙烯醯氧基乙酯）、琥珀酸一 (2-甲基丙烯醯氧基乙酯）、六氫鄰苯二甲酸一（2_丙烯醯 氧基乙酯）、六氫鄰苯二甲酸一（2_曱基丙烯醯氧基乙酯） 等一几缓酸類；馬來酸、富馬酸、檸康酸、中康酸、衣 籲康酸等二元羧酸類；上述二元缓酸的酐類等。 在這些化合物（al)中，從共聚合反應性和容易得到 的角度考慮，較佳為丙烯酸、甲基丙烯酸、馬來酸酐等 〇 上述的化合物（a 1)可以單獨使用或者2種以上混合 使用。 在共聚物[A]中’來自化合物（al)之構成單元的含有 率較佳為5·50重量％，更佳為10-40重量％。當該構成單 凡的含有率低於5重量％時所獲間隔物的抗壓強度、耐 -11- 1380065 修正本 熱性或耐藥品性有降低的傾向’反之，超過5〇重量％時 ’放射線敏感性樹脂組合物的保存穩定性有可能降低。 另外’作為化合物（a2) ’例如可以舉出：丙稀酸縮 水甘油醋、曱基丙烯酸縮水甘油酯、α -乙基丙烯酸縮水 甘油醋、α -正丙基丙烯酸縮水甘油酯、α -正丁基丙烯 -酸縮水甘油酯、丙烯酸3，4 -環氧基丁酯、甲基丙烯酸3，4 _ 環氧基丁醋、α -乙基丙烯酸3,4-環氧基丁酯、丙烯酸6,7_ 環氧基庚酯、曱基丙烯酸6,7-環氧基庚酯、α -乙基丙婦 ® 酸6,7-環氧基庚酯、丙烯酸β_曱基縮水甘油酯、甲基丙稀 酸β-甲基縮水甘油酯、丙烯酸β·乙基縮水甘油酯、甲基 丙烯酸β-乙基縮水甘油酯、丙烯醆β_正丙基縮水甘油醋 、曱基丙烯酸β-正丙基縮水甘油酯、丙稀酸3,4-環氧基環 己醋 '甲基丙烯酸3，4-環氧基環己酯等羧酸酯類；鄰乙 烯基苄基縮水甘油醚、間乙烯基苄基縮水甘油醚、對乙 烯基苄基縮水甘油醚等的醚類等。 在這些化合物（a2)中’從提高共聚合反應性和所獲 •間隔物強度的角度考慮’較佳為甲基丙烯酸縮水甘油醋 、甲基丙烯酸6,7-環氧基庚酯、甲基丙烯酸β·曱基縮水甘 油醋、曱基丙烯酸3，4-環氧基環己酯、鄰乙烯基苄基縮 水甘油喊、間乙稀基卞基lis水甘油驗、對乙烯基节其縮 水甘油醚等。 上述化合物（a2)可以單獨使用或者2種以上混合使 用。 在共聚物[A]中，來自化合物（a2)的構成單元的含有 率較佳為10-70重量°/〇’更佳為20-60重量％。在此情況下 -12- 1380065 修正本 ’當該構成單元的含有率低於丨0重量％時所得到的間 隔物的抗壓強度、耐熱性或耐藥品性有降低的傾向，反 之，超過70重量。/。時，放射線敏感性樹脂組合物的保存 穩定性有降低的傾向^ 此外，作為化合物（a3)，例如可以舉出丙烯酸甲酯 、丙烯酸乙酯、丙烯酸正丙酯、丙烯酸異丙酯、丙烯酸 正丁酯、丙稀酸異丁酯、丙浠酸二級丁酯、丙稀酸三級 丁酯等的丙烯酸烷基酯類；曱基丙烯酸甲酯、曱基丙烯 •酸乙酯、甲基丙烯酸正丙酯、曱基丙烯酸異丙酯、曱基 丙烯酸正丁酯、曱基丙烯酸異丁酯、曱基丙烯酸二級丁 酯、曱基丙烯酸三級丁酯等的曱基丙烯酸烷基酯類；丙 烯酸環己酯、丙烯酸2-甲基環己酯、丙烯酸三環 [5.2.1.02’6]癸烷-8-基酯（以下將“三環[5.2.1.02,6]癸烷 -8-基”稱為“二環戊基”）、丙烯酸2-二環戊氧基乙基酯 、丙稀酸異冰片基S旨、丙稀酸四氫υ夫喃基g旨等丙稀酸的 脂環族酯類；曱基丙烯酸環己酯、甲基丙烯酸2 -甲基環 φ 己酯、曱基丙烯酸二環戊酯、甲基丙稀酸2 -二環戊氧基 乙酯、甲基丙稀酸異冰片基酯、甲基丙烯酸四氫°夫鳴基 酯等甲基丙烯酸的脂環族酯類；丙烯酸苯酯、丙烯酸苄 酯等的丙烯酸芳基酯頬；甲基丙烯酸苯酯、曱基丙烯酸 苄酯等的曱基丙稀酸芳基酯類； 馬來酸二乙酯、富馬酸二乙酯、衣康酸二乙酯等的 二羧酸二酯類；丙烯釀2-羥乙酯、丙烯酸2-羥丙酯等的 丙烯酸羥烷基酯類；甲基丙稀酸2-羥乙酯、甲基丙烯酸 2-羥丙酯等的甲基丙烯酸羥烷基酯類；苯乙烯、α -甲基 -13- 1380065 修正本 笨乙烯、間甲基苯乙烯、對曱基苯乙烯、對甲氧基苯乙 細等芳香族乙細基化合物；或者丙稀腈、甲基丙烯猜、 氯乙烯、偏氯乙烯、丙烯醯胺、曱基丙烯醯胺、醋酸乙 烯、1，3-丁二烯、異戊二烯、2,3-二甲基-1,3-丁 二烯、N-環己基馬來醯亞胺、N-苯基馬來醯亞胺、N-爷基馬來醯 -亞胺、N -琥拍酿亞胺基-3-馬來醯亞胺基苯甲酸酷、N -琥 轴醯亞胺基-4-馬來醯亞胺基丁酸酯、N_琥珀醯亞胺基-6-馬來醯亞胺基己酸酯、N-琥珀醯亞胺基_3_馬來醯亞胺基 丙酸酯、N-(9-吖啶基）馬來醯亞胺等。 在這些化合物（a3)中，從共聚合反應性方面考慮， 較佳為丙烯酸2-甲基環己酯、甲基丙烯酸三級丁酯、曱 基丙烯酸二環戊酯、甲基丙稀酸四氫呋喃基酯、苯乙烯 、對曱氧基苯乙烯、1,3-丁二烯等。 上述化合物（a3)可以單獨使用或者2種以上混合使 用。 在共聚物[A]中，來自化合物（a3)的構成單元的含有 鲁率較佳為10_80重量％，更佳為2〇 6〇重量。在此情況下 ，^述構成單元的含有率低於10重量％時，放射線敏感 性f脂組合物的保存穩定性有可能降低，反之，超過 重1%時，顯影性有可能降低。 採用，凝膠滲透色譜法（GPC)測得的共聚物[A]的聚苯 二广換算重均分子量(以下簡稱“Mw”）通常為2x103-5x ’較佳為5xl〇3-lxl〇5。在此情況下，共聚物 小方^ 2 y 1 Π 3 士 傾向，時，所獲間隔物的抗壓強度或耐熱性有降低的 ° ，反之，在超過5xl〇5時，顯影性有降低的傾向。 -14- 1380065 修正本 在本發明中，共聚物[A]可以單獨使用或者2種以上 混合使用。 共聚物[A]例如可以通過將化合物（al)、化合物（a2) 和化合物（a3)在溶劑中和在聚合引發劑的存在下進行自 由基聚合來製造。 - 作為在製造共聚物[A]時使用的溶劑，例如可以舉出 甲醇、乙醇、正丙醇、異丙醇、苄醇、2-苯基乙醇 ® 、3 -苯基-1-丙醇等醇類； 四氫吱喃、二0f烧等醚類； 二乙二醇一甲醚、二乙二醇一乙醚、二乙二醇一正 丙基醚、二乙二醇一正丁基醚等二乙二醇一烷基醚類； 二乙二醇一曱醚乙酸酯、二乙二醇一乙醚乙酸酯、 二乙二醇一正丙基醚乙酸酯、二乙二醇一正丁基醚乙酸 酯等二乙二醇一烷基醚乙酸酯類； 二乙二醇一甲醚乙酸酯、二乙二醇一乙醚乙酸酯等 φ 二乙二醇一烷基醚乙酸酯類； 二乙二醇一甲醚丙酸酯、二乙二醇一乙醚丙酸酯、 二乙二醇一正丙基醚丙酸酯、二乙二醇一正丁基醚丙酸 酯等二乙二醇一烷基醚丙酸酯類； 二乙二醇一甲醚、二乙二醇一乙醚、二乙二醇二曱 醚、二乙二醇二乙醚、二乙二醇乙基曱基醚等二乙二醇 烷基醚類； 丙二醇一曱鍵、丙二醇一乙喊、丙二醇一正丙基 、丙二醇一正丁基醚等丙二醇一烷基醚類； -15- 1380065 修正本 丙二醇一曱醚乙酸酯、丙二醇一乙醚乙酸酯、丙二 醇一正丙基醚乙酸酯、丙二醇一正丁基醚乙酸酯等丙二 醇一烷基醚乙酸酯類； 丙二醇一曱醚丙酸酯、丙二醇一乙醚丙酸酯、丙二 ‘ 醇一正丙基醚丙酸酯、丙二醇一正丁基醚丙酸酯等丙二 - 醇一烷基醚丙酸酯類； 曱苯、二曱苯等芳香族烴類； 丁酮、2-戊酮、3-戊酮、環己酮、4-羥基-4-甲基-2- 籲戊嗣等酮類； 2-曱氧基丙酸曱酯、2-甲氧基丙酸乙酯、2-甲氧基丙 酸正丙基酯、2-甲氧基丙酸正丁基酯、2-乙氧基丙酸甲 醋、2-乙氧基丙酸乙酯' 2-乙氧基丙酸正丙基酯、2-乙氧 基丙酸正丁基酯、2 -正丙氧基丙酸甲酯、2 -正丙氧基丙 酸乙酯、2 -正丙氧基丙酸正丙基酯、2 -正丙氧基丙酸正 丁基酯、2-正丁氧基丙酸甲酯、2-正丁氧基丙酸乙酯、 2- 正丁氧基丙酸正丙基酯、2-正丁氧基丙酸正丁基酯、 φ 3 -曱氧基丙酸甲酯、3 -曱氧基丙酸乙酯、3 -甲氧基丙酸正 丙基酯、3 -甲氧基丙酸正丁基酯、3 -乙氧基丙酸曱酯、 3- 乙氧基丙酸乙酯、3 -乙氧基丙酸正丙基酯、3 -乙氧基丙 酸正丁基酯、3 -正丙氧基丙酸曱酯、3 -正丙氧基丙酸乙 酯、3 -正丙氧基丙酸正丙基酯、3 -正丙氧基丙酸正丁基 酯、3 -正丁氧基丙酸曱酯、3 -正丁氧基丙酸乙酯、3 -正丁 氧基丙酸正丙基酯、3 -正丁氧基丙酸正丁基酯等烷氧基 丙酸烷基酯類； 乙酸甲酯、乙酸乙酯、乙酸正丙酯、乙酸正丁酯、 -16- 修正本 羥基乙酸甲酯 乙酸正丁酯、二工丞酸乙酯、羥基乙酸正丙酯、羥基 正丁酯、2-羥^酸甲酯 '乳酸乙酯、乳酸正丙酯、乳酸 酯、3-麵其·2~甲基丙酸甲酯、2_羥基-2·曱基丙酸乙 搜基丙酸甲 m &gt; 3 e、3·羥基丙酸乙酯、3-羥基丙酸正丙 經暴丙暖正 基乙酸甲酯、甲t 8曰' 2-羥基-3-甲基丁酸甲酯、曱氧 氧基乙酸正丁酯乳基乙酸乙酯、甲氧基乙酸正丙酯、甲 乙匐I 曰 乙氧基乙酸甲酯、乙氧基乙酸乙酯、 〇乳基乙酸正丙萨 — 敗曰、 甲酯、正丙氧美曰、乙氧基乙酸正丁酯、正丙氧基乙酸 氧基乙酸正二二己酸乙顆、正丙氧基乙酸正丙酯、正丙 酉旨、正 日、正丁氧基乙酸甲酯、正丁氧基乙酸乙 J乳i乙酸τ Έ 的酯類。 丙醋、正丁氧基乙酸正丁酯等其他 在這些溶劑中 一-^ 較佳為二乙·一和娱*基鍵類、雨-龄 烷基醚乙酸酯_ 呢頰丙—醇 賴、烷氧基丙酸烷基酯類等。In the formula (1), R1 represents a straight alkyl group having 1 to 12 carbon atoms; R2 and R3 each independently represent a hydrogen atom, and the number of chains, branches or ring carbon atoms is 1 - 1 2 1380065 a chain, a branched or a cyclic alkyl group or a aryl group; R 4 , R 5 , R 7 and R 8 each independently represent a hydrogen atom; a halogen atom, a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms or a linear or branched alkoxy group having 1 to 4 carbon atoms; R6 represents a halogen atom, a linear, branched or a burnt group having 1 to 12 carbon atoms selected from a hydroxyl group and a carbon atom a straight or branched alkyl group having 12 carbon atoms substituted by a substituent of a linear or branched alkoxy group of 1 to 4, a straight chain or a branch having a carbon number of 丨4 a linear or branched carbon group having 2 to 4 carbon atoms substituted by a group of substituents selected from the group consisting of a hydroxyl group and a linear or branched alkoxy group having a carbon number of 1 to 4; Alkoxy group. The term "radiation" as used in the present invention means various rays including ultraviolet rays, far purple rays, X-rays, electron rays 'molecular rays, gamma rays, synchrotron radiation rays, proton beam rays, and the like. According to a second aspect of the invention, the spacer is formed of the above-described spacer-forming radiation-sensitive resin composition. According to a third aspect of the present invention, there is provided a method of forming a spacer, characterized in that the method comprises at least the following (1) to (the step of the sentence: /1) forming a substrate according to the item i of the patent application scope. a step of separating/forming a film of the radiation sensitive resin composition; (2) exposing at least a part of the film to radiation; (3) developing the film after exposure; (4) developing the film The above step of heating the film. The fourth aspect of the invention is constituted by a liquid crystal display % member having the above spacer. -10- 1380065 MODIFICATION [Embodiment] <The radiation-sensitive resin composition for a spacer> The radiation-sensitive resin composition for a spacer of the present invention (hereinafter referred to as "radiation-sensitive resin composition") will be described in detail below. . 'Copolymer [A], the component [A] in the radiation sensitive resin composition of the present invention is composed of (a 1) unsaturated carboxylic acid and/or unsaturated carboxylic anhydride (hereinafter referred to as "compound (al)" And (a2) a copolymer of an epoxy group-containing unsaturated compound (hereinafter referred to as "unsaturated compound (a2)") and (a3) another unsaturated compound (hereinafter referred to as "compound (a3)") ( Hereinafter, it is composed of "copolymer [A]"). Examples of the compound (a 1)' include acrylic acid, methacrylic acid, crotonic acid, mono(2-propenyloxyethyl) succinate, and mono(2-methylpropenyloxyethyl) succinate. , hexahydrophthalic acid mono (2-propenyloxyethyl ester), hexahydrophthalic acid mono(2- mercaptopropoxyethyl ester), etc.; maleic acid, fumar Dicarboxylic acids such as acid, citraconic acid, mesaconic acid, and ketoconic acid; and the above-mentioned binary acid-reducing anhydrides. In the above-mentioned compound (al), from the viewpoint of copolymerization reactivity and easy availability, it is preferred that the above compound (a1) such as acrylic acid, methacrylic acid or maleic anhydride may be used singly or in combination of two or more kinds. . The content of the constituent unit derived from the compound (al) in the copolymer [A] is preferably from 5 to 50% by weight, more preferably from 10 to 40% by weight. When the content of the constituent is less than 5% by weight, the compressive strength of the obtained spacer, and the resistance to -11 to 1380065 are corrected, and the heat or chemical resistance is lowered. On the contrary, when it exceeds 5% by weight, the radiation is emitted. The storage stability of the sensitive resin composition may be lowered. Further, 'as compound (a2)' may, for example, be glycerol acrylate, glycidyl methacrylate, α-ethyl acrylate glycerin, α-n-propyl acrylate, or α-n-butyl Propylene glycidyl ester, 3,4-epoxybutyl acrylate, 3,4 _ epoxy butyl acrylate, 3,4-epoxy butyl α-ethyl acrylate, acrylic acid 6, 7_ epoxide heptyl ester, 6,7-epoxyheptyl methacrylate, α-ethyl propyl benzoate 6,7-epoxyheptyl ester, β-mercapto glycidyl acrylate, methyl propyl Dilute acid β-methyl glycidyl ester, β-ethyl glycidyl acrylate, β-ethyl glycidyl methacrylate, propylene 醆β-n-propyl glycidol vinegar, β-n-propyl methacrylate Carboxylic esters such as glyceride, 3,4-epoxycyclohexanoic acid acrylate, 3,4-epoxycyclohexyl methacrylate; o-vinylbenzyl glycidyl ether, m-vinyl benzyl An ether such as glycidyl ether or p-vinylbenzyl glycidyl ether. In these compounds (a2), 'from the viewpoint of improving the copolymerization reactivity and the strength of the obtained spacers, 'preferably glycidyl methacrylate, 6,7-epoxyheptyl methacrylate, methyl group Acetic acid β·decyl glycidol vinegar, 3,4-epoxycyclohexyl methacrylate, o-vinyl benzyl glycidyl sulphate, m-diethyl hydrazine hydrhydrin, and glycidol Ether, etc. The above compound (a2) may be used singly or in combination of two or more kinds. In the copolymer [A], the content of the constituent unit derived from the compound (a2) is preferably from 10 to 70% by weight, more preferably from 20 to 60% by weight. In this case, -12-1380065 is corrected. When the content of the constituent unit is less than 丨0% by weight, the compressive strength, heat resistance, or chemical resistance of the spacer obtained tends to decrease. weight. /. In the case of the compound (a3), for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate or butyl acrylate may be mentioned. Alkyl acrylates such as esters, isobutyl acrylate, butyl acrylate, and butyl acrylate; methyl methacrylate, decyl propylene, ethyl acrylate, methacrylic acid Alkyl methacrylates such as propyl ester, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, butyl methacrylate, and butyl methacrylate; Cyclohexyl ester, 2-methylcyclohexyl acrylate, tricyclo[5.2.1.02'6]nonane-8-yl acrylate (hereinafter "Tricyclo[5.2.1.02,6]decane-8-yl" An alicyclic group called "dicyclopentyl"), 2-dicyclopentyloxyethyl acrylate, isobornyl acrylate, and tetrahydrofurfuryl propyl acrylate Esters; cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, dicyclopentyl methacrylate, methyl acrylate An alicyclic ester of methacrylic acid such as 2-dicyclopentyloxyethyl ester, isobornyl methacrylate, tetrahydroc-butyl methacrylate, phenyl acrylate or benzyl acrylate Aryl acrylate phthalate; aryl acrylate aryl esters such as phenyl methacrylate or benzyl methacrylate; diethyl maleate, diethyl fumarate, diethyl itaconate, etc. Dicarboxylic acid diesters; hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate Hydroxyalkyl methacrylates; styrene, α-methyl-13- 1380065 modified aromatic ethylene, m-methyl styrene, p-nonyl styrene, p-methoxy styrene, etc. Fine base compound; or acrylonitrile, methacrylic, vinyl chloride, vinylidene chloride, acrylamide, mercapto acrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3 - dimethyl-1,3-butadiene, N-cyclohexylmaleimide, N-phenylmaleimide, N-gummaine-imine, N-sodium Amino-3-maleimide Benzoic acid, N-succinimide, imino-4-maleimido butyrate, N-succinimide-6-maleimidohexanoate, N-amber Imino-3_maleimide propionate, N-(9-acridinyl)maleimide, and the like. Among these compounds (a3), 2-methylcyclohexyl acrylate, butyl methacrylate, dicyclopentanyl methacrylate, and tetrahydrofuran methacrylate are preferable from the viewpoint of copolymerization reactivity. Base ester, styrene, p-nonyloxystyrene, 1,3-butadiene, and the like. The above compound (a3) may be used singly or in combination of two or more kinds. In the copolymer [A], the content of the constituent unit derived from the compound (a3) is preferably from 10 to 80% by weight, more preferably from 2 to 6 % by weight. In this case, when the content of the constituent unit is less than 10% by weight, the storage stability of the radiation-sensitive f-fat composition may be lowered. On the other hand, when the content exceeds 1%, the developability may be lowered. The polystyrene-converted weight average molecular weight (hereinafter referred to as "Mw") of the copolymer [A] measured by gel permeation chromatography (GPC) is usually 2 x 10 3-5 x ' preferably 5 x l 〇 3-l x l 〇 5 . In this case, when the copolymer is in a small square of 2 y 1 Π 3 士, the compressive strength or heat resistance of the obtained spacer is lowered by °, and conversely, when it exceeds 5 x 1 〇 5, the developability is lowered. tendency. -14- 1380065 In the present invention, the copolymer [A] may be used singly or in combination of two or more. The copolymer [A] can be produced, for example, by subjecting the compound (al), the compound (a2) and the compound (a3) to a radical polymerization in the presence of a polymerization initiator in the presence of a polymerization initiator. - Examples of the solvent used in the production of the copolymer [A] include methanol, ethanol, n-propanol, isopropanol, benzyl alcohol, 2-phenylethanol®, 3-phenyl-1-propanol, and the like. Alcohols; ethers such as tetrahydrofuran and dioxin; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, etc. Diethylene glycol monoalkyl ether; diethylene glycol monoterpene ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-propyl ether acetate, diethylene glycol Diethylene glycol monoalkyl ether acetate such as butyl ether acetate; φ diethylene glycol monoalkyl ether acetate such as diethylene glycol monomethyl ether acetate or diethylene glycol monoethyl ether acetate Ester; diethylene glycol monomethyl propionate, diethylene glycol monoethyl ether propionate, diethylene glycol mono-n-propyl ether propionate, diethylene glycol mono-n-butyl ether propionate, etc. Diethylene glycol monoalkyl ether propionate; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dioxime ether, diethylene glycol diethyl ether, diethylene glycol ethyl hydrazine Diethylene glycol alkyl ethers such as ethers; propylene glycol a propylene glycol monoalkyl ether such as a bond, propylene glycol-ethyl propylene, propylene glycol mono-n-propyl or propylene glycol mono-n-butyl ether; -15- 1380065 modified propylene glycol monoterpene ether acetate, propylene glycol monoethyl ether acetate, propylene glycol Propylene glycol monoalkyl ether acetates such as n-propyl ether acetate, propylene glycol mono-n-butyl ether acetate; propylene glycol monoterpene ether propionate, propylene glycol monoethyl ether propionate, propylene glycol propylene glycol Propylene dipropionate such as ether propionate, propylene glycol mono-n-butyl ether propionate; aromatic hydrocarbons such as toluene and diphenyl; butanone, 2-pentanone, 3- Ketones such as pentanone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanthene; 2-nonyloxypropionate, 2-methoxypropionate, 2-methoxy N-propyl propionate, n-butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, n-propyl 2-ethoxypropionate , n-butyl 2-ethoxypropionate, methyl 2-n-propoxypropionate, ethyl 2-n-propoxypropionate, n-propyl 2-n-propoxypropionate, 2- N-butyl n-propoxypropionate, methyl 2-n-butoxypropionate Ethyl 2-n-butoxypropionate, n-propyl 2-n-butoxypropionate, n-butyl 2-n-butoxypropionate, methyl φ 3 -decyloxypropionate, 3- Ethyl methoxypropionate, n-propyl 3-methoxypropionate, n-butyl 3-methoxypropionate, decyl 3-ethoxypropionate, ethyl 3-ethoxypropionate Ester, n-propyl 3-ethoxypropionate, n-butyl 3-ethoxypropionate, decyl 3-n-propoxypropionate, ethyl 3-n-propoxypropionate, 3- N-propyl n-propoxypropionate, n-butyl 3-n-propoxypropionate, decyl 3-n-butoxypropionate, ethyl 3-n-butoxypropionate, 3-n-butyl Alkoxypropionic acid alkyl esters such as n-propyl oxypropionate and n-butyl 3-n-butoxypropionate; methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, -16- Correction of methyl hydroxyacetate n-butyl acetate, di-ethyl decanoate, n-propyl glycolate, hydroxy-n-butyl ester, 2-hydroxyl-methyl ester 'ethyl lactate, n-propyl lactate, milk Acid ester, 3-faced 2-methyl propyl propionate, 2-hydroxy-2-mercaptopropionic acid ethyl methionine m &gt; 3 e, 3 · hydroxypropionic acid Ethyl ester, 3-hydroxypropionic acid, n-propyl, methyl thioglycolate, methyl t 8 曰 '2-hydroxy-3-methylbutyric acid methyl ester, n-butyl decyloxyacetate , n-propyl methoxyacetate, methyl ethyl hydrazine I ethoxylate methyl acetate, ethyl ethoxyacetate, 丙 〇 正 — — — — 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰N-butyl acetate, n-propoxyacetoxyacetic acid n-dihexanoic acid ethyl, n-propoxyacetic acid n-propyl ester, n-propyl acetate, n-day, n-butoxyacetic acid methyl ester, n-butoxy Esters of ethyl acetate J milk i τ Έ. Propylene vinegar, n-butyl n-butoxyacetate, etc., among other solvents, preferably -diethyl-anthracene-based linkages, rain-age alkyl ether acetates , alkoxypropionic acid alkyl esters and the like.

上述溶劑可以„D 另 J M早獨使用或者2種以上混合使用。 外，作為在製造共聚物[A]時使用的聚合引發 引芯用::些通常已知可作為自由基聚合,丨發劑使用的 (2 4二例如可以舉出2,2，-偶氮二異丁腈、2,2，_偶氮二 猜):〜甲基戊腈）、2,2、偶氮二(4·曱氧基乂心二甲基戊 :、M’-偶氮二⑷氰基戊酸）、二甲基_2,2，_偶氮二 偶=酸醋）'2,2，-偶氮二（4·曱氧基_2,4_二甲基戊猜）等 化3物；過氧化苯甲醯、過氧化月桂 __ 過S儿 一趿丁基 乳化新戊酸酯、1，1-二（三級丁基過氧化）環 /L 7衣匕烷4有機 過氧化物；以及過氧化氫等。在使用過氧化 乍為自由 基聚合引發劑的場合，也可以併用還原劑竹&amp; ^ 叫邛為軋化還原 -17- 1380065 修正本 型引發劑。 這些自由基聚合引發劑可以單獨使用或者2種以上 &gt;見合使用。 聚合性不飽和化合物[B] 在本發明的放射線敏感性樹脂組合物中，作為聚合 ' 性不飽和化合物’較佳為雙官能以上的丙烯酸酯類和甲 基丙烯酸酯類（以下將它們統稱為“（甲基）丙烯酸酯類” )0 ® 作為雙官能的（甲基）丙烯酸酯類，例如可以舉出： 丙烯酸二乙二醇酯、曱基丙烯酸二乙二醇酯、1,6-己二 醇二丙烯酸酯、1，6 -己二醇二曱基丙烯酸酯、1,9 -壬二醇 —丙稀酸自旨、1，9 -壬二醇二甲基丙稀酸g旨、四乙二醇二 丙烯酸酯、四乙二醇二曱基丙烯酸酯、聚丙二醇二丙烯 酸酯、聚丙二醇二曱基丙烯酸酯、雙（苯氧基乙醇）芴二 丙烯酸酯、雙（苯氧基乙醇）芴二甲基丙烯酸酯等。 作為雙官能（曱基）丙烯酸酯類的市售商品，例如可 •以舉出：ARONIX M-201、ARONIX M-240、ARONIX M-6200(以上產品為東亞合成（股）製造）；KAYARAD HDDA、KAYARAD HX-220、KAYARAD R-604、 KAYARAD UX-2201、KAYARAD UX-2301、KAYARAD UX-3204、KAYARAD UX-330 1、KAYARAD UX-4101、 KAYARAD UX-6101、KAYARAD UX-7101、KAYARAD UX-8101、KAYARAD MU-2100、KAYARAD MU-4001 ( 以上產品為曰本化藥（股）製造）；VISCOAT260、 VISCOAT3 12、VISCOAT335HP(以上產品為大阪有機化 -18- 1380065 修正本 學工業（股）製造）等。 作為三官能以上的（曱基）丙烯酸酯類，例如可以舉 出：三羥甲基丙烷三丙烯酸酯、三羥曱基丙烷三曱基丙 烯酸酯、四級戊四醇三丙稀酸酯、四級戊四醇三甲基丙 • 稀酸酯、四級戊四醇四丙烯酸酯、四級戊四醇四甲基丙 烯酸酯、二四級戊四醇五丙稀酸酯、二四級戊四醇五甲 基丙稀酸酯、二四級戊四醇六丙烯酸酯、二四級戊四醇 六曱基丙烯酸酯、三（2-丙烯醯氧基乙基）磷酸酯、三（2-® 曱基丙烯醯氧基乙基）磷酸酯。作為9官能以上的（甲基） 丙烯酸酯類，可以舉出使具有直鏈亞烷基和脂環式結構 且含有2個以上異氰酸酯基的化合物與分子内具有1個以 上經基且含有3個、4個或5個丙烯醯氧基和/或甲基丙稀 醯氧基的化合物反應而得到的尿烷丙烯酸醋類化合物等 另外，作為3官能以上的（甲基）丙烯酸酯類的市售商 品，例如可以列舉：ARONIX M-309、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-8030、ARONIX M-8060、 ARONIX M-8100、ARONIX M-8530、ARONIX M-8560、 ARONIX M-905 0、ARONIX TO- 1450(以上產品為東亞合The above solvent may be used alone or in combination of two or more. In addition, as a polymerization initiating core used in the production of the copolymer [A]:: generally known as a radical polymerization, a hair styling agent (2, 2, for example, 2,2,-azobisisobutyronitrile, 2,2,_azobis): ~methylvaleronitrile), 2,2, azobis (4·曱 乂 乂 二 dimethyl pentane: M'-azobis(4) cyanovalerate), dimethyl 2, 2, azobis couple = vinegar) '2,2,-azo two (4·曱oxy-2,4_dimethylpentan) equating 3; benzammonium peroxide, laurel peroxide __ S 儿 趿 butyl emulsified pivalate, 1,1- a bis(tertiary butyl peroxy) ring/L 7 decane 4 organic peroxide; and hydrogen peroxide, etc. When ruthenium peroxide is used as a radical polymerization initiator, a reducing agent bamboo & ^ 邛 邛 is rolling reduction -17- 1380065 Correction type initiator. These radical polymerization initiators may be used alone or in combination of two or more. Polymeric unsaturated compounds [B] Radiation sensitivity in the present invention Resin composition As the polymerized 'unsaturated compound', difunctional or higher acrylates and methacrylates (hereinafter collectively referred to as "(meth)acrylates") 0 ® are used as difunctional (methyl) The acrylates include, for example, diethylene glycol acrylate, diethylene glycol methacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimercapto acrylate, 1,9-nonanediol-acrylic acid, 1,9-nonanediol dimethyl acrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimercapto acrylate, polypropylene glycol Diacrylate, polypropylene glycol dimercapto acrylate, bis(phenoxyethanol) fluorene diacrylate, bis(phenoxyethanol) fluorene dimethacrylate, etc. as difunctional (fluorenyl) acrylate Commercially available products, for example, can be cited as: ARONIX M-201, ARONIX M-240, ARONIX M-6200 (the above products are manufactured by East Asia Synthetic Co., Ltd.); KAYARAD HDDA, KAYARAD HX-220, KAYARAD R-604, KAYARAD UX-2201, KAYARAD UX-2301, KAYARAD UX-3204, KAYARAD UX-330 1, KAYARAD UX- 4101, KAYARAD UX-6101, KAYARAD UX-7101, KAYARAD UX-8101, KAYARAD MU-2100, KAYARAD MU-4001 (The above products are manufactured by Sakamoto Chemical Co., Ltd.); VISCOAT260, VISCOAT3 12, VISCOAT335HP (the above products are Osaka Organicization -18- 1380065 Revision of the industry (stock) manufacturing). Examples of the trifunctional or higher (fluorenyl) acrylates include trimethylolpropane triacrylate, trihydroxymercaptopropane tridecyl acrylate, tetrapentaerythritol triacrylate, and four. Pentaerythritol trimethyl propyl sulphate, quaternary pentaerythritol tetra acrylate, quaternary pentaerythritol tetramethacrylate, diquaternary pentaerythritol penta acrylate, quaternary tetrapenta Alcohol pentamethyl acrylate, diquaternary pentaerythritol hexaacrylate, diquaternary pentaerythritol hexamethylene acrylate, tris(2-propenyloxyethyl) phosphate, tris(2-® Mercapto propylene oxyethyl) phosphate. Examples of the hexa-functional or higher (meth) acrylate include a compound having a linear alkylene group and an alicyclic structure and having two or more isocyanate groups, and one or more molecules in the molecule and three. A urethane acryl vine compound obtained by reacting four or five acryloxy groups and/or methyl propyl fluorenyl compounds, and commercially available as a trifunctional or higher (meth) acrylate. Commercial products include, for example, ARONIX M-309, 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-8030, ARONIX M-8060, ARONIX M-8100, ARONIX M-8530, ARONIX M-8560, ARONIX M-905 0, ARONIX TO- 1450 (The above products are East Asian

成（股）製造）；KAYARAD TMPTA、KAYARAD DPHA、 KAYARAD DPCA-20、KAYARAD DPCA-30、KAYARAD DPCA-60、KAYARAD DPCA-1 20、KAYARAD MAX-3510(以上產品為曰本化藥（股）製造）；VISCOAT295、 -19- 1380065 修正本 VISCOAT300 、 VISCOAT360 、 VISCOATGPT 、 VISCOAT3PA、VISCOAT400(以上產品為大阪有機化學 工業（股）製造）；作為含有尿烷丙烯酸酯類化合物的市售 商品，可以列舉New Frontier R-1150(第一工業製藥（股） 製造）、KAYARAD DPHA-40H(日本化藥（股）製造）等。 在本發明中，聚合性不飽和化合物可以單獨使用或 者2種以上混合使用。(manufactured by Cheng); KAYARAD TMPTA, KAYARAD DPHA, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-1 20, KAYARAD MAX-3510 (The above products are manufactured by Sakamoto Chemical Co., Ltd.) );VISCOAT295, -19- 1380065 Revised this VISCOAT300, VISCOAT360, VISCOATGPT, VISCOAT3PA, VISCOAT400 (the above products are manufactured by Osaka Organic Chemical Industry Co., Ltd.); as a commercial product containing urethane acrylate compounds, New Frontier R-1150 (manufactured by Daiichi Kogyo Co., Ltd.), KAYARAD DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), etc. In the present invention, the polymerizable unsaturated compound may be used singly or in combination of two or more kinds.

在本發明的放射線敏感性樹脂組合物中’相對於1 00 重量份的共聚物[A]，聚合性不飽和化合物的用量較佳為 30-200重量份，更佳為5〇_14〇重量份。在此情況下，聚 合性不飽和化合物的用量不到3 〇重量份時，所獲間隔物 容易發生膜減少或強度的降低，反之，其用量超過200 重量份時’所得間隔物的黏附性往往不夠好。 放射線敏感性聚合引發劑[c] 本發明的放射線敏感性樹脂組合物中的放射線敏感 |·生聚&amp;引發劑是以上述通式（丨）表示的化合物（以下稱為 “化合物（1)”）作為必要成分的引發劑。In the radiation sensitive resin composition of the present invention, the amount of the polymerizable unsaturated compound is preferably from 30 to 200 parts by weight, more preferably from 5 to 14% by weight, based on 100 parts by weight of the copolymer [A]. Share. In this case, when the amount of the polymerizable unsaturated compound is less than 3 parts by weight, the obtained spacer is liable to cause a decrease in film or a decrease in strength. On the other hand, when the amount exceeds 200 parts by weight, the adhesion of the resulting spacer tends to be often not good enough. Radiation-sensitive polymerization initiator [c] Radiation-sensitive in the radiation-sensitive resin composition of the present invention|Biopolymerization &amp; initiator is a compound represented by the above formula (丨) (hereinafter referred to as "compound (1) ") An initiator as an essential component.

R 在通式（1)中’作為Rl、r2、r3、y 、 R的石反原子數Μ2的直鏈、支鏈或環狀的烷基’例如可 以舉出甲基、乙基、正丙基、異丙基、正丁基、異丁基 級丁基、二級丁基、正戊基、正己基、正庚基、正 辛基、正壬基、正癸基、正十一烷基、正十二烷基、環 戊基、環己基等。 另外 可以舉出 ，作為R4、R5、R6、R7和118的_素原子，例如 氟原子、氣原子、溴原子等。 -20- 修正本 鰱、卜作為R4、r5、r6、r7和R8的碳原子數u 支鏈或環狀的烷氧基，例如可以舉出 、直 暴、正丙惫糞 軋基、乙氧 氣基、三級丁氧基等》 基、二級 鍵狀二在/之經選自經基和碳原子數Η的直鏈或支 凡氣基中的取代基所取代的碳原子數 支鏈或瑗壯以 i2的直鏈 —衣狀的烷基中’作為碳原子數1 -4的直絲+ 狀的烷負其， 息鍵或支鏈 乳暴’例如可以舉出那些與上述R4、 和 R8 的;ε山 E ^ ' R ' R7 、反原子數1-4的直鏈或支鏈狀的烷氧基 的同樣的基團。 土中所例示 _相對於R6之經取代的碳原子數1-12的直鏈、 環狀的烷基，作為取代基，例如較佳為羥基鏈或 。 T氧基等 在R6之經取代的碳原子數1-12的直鏈、支鍵 的烷基，例如可以舉出那些與上述Ri、R2、R3 ％狀 &gt; Ώ 6 p 7 &lt; 〇 g 、R、R5 R、R和R的碳原子數！_12的直鏈、支鏈或環狀㈣ 基中所例示的同樣的基團。 在R6之經取代的碳原子數卜12的直鏈、支鏈或環狀 的烧基中’可以存在1種以上或1個以上的取代基。R, in the general formula (1), as a linear, branched or cyclic alkyl group of the anti-atomic number Μ2 of R1, r2, r3, y, R, for example, methyl, ethyl or n-propyl Base, isopropyl, n-butyl, isobutyl butyl, secondary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-decyl, n-undecyl , n-dodecyl, cyclopentyl, cyclohexyl and the like. Further, examples of the atom of R4, R5, R6, R7 and 118 include a fluorine atom, a gas atom, a bromine atom and the like. -20- Amendment 鲢, 卜 as R4, r5, r6, r7 and R8, the number of carbon atoms, a branched or cyclic alkoxy group, for example, direct turbidity, n-propyl hydrazine, ethylene oxide a group of carbon atoms or a substituent of a secondary bond, which is substituted with a substituent selected from a straight chain or a branched gas group having a fluorene group and a carbon atom; In the linear-cloth-like alkyl group of i2, 'as a straight-line + alkane having a carbon number of 1-4, a poly- or a branched-chain emulsion" can be exemplified by those described above with R4, and The same group of R8; εMoule E ^ ' R ' R7 , a straight or branched alkoxy group having an inverse number of 1-4. The linear or cyclic alkyl group having 1 to 12 carbon atoms substituted with respect to R6 is exemplified in the soil, and as the substituent, for example, a hydroxyl chain or a group is preferable. Examples of the straight-chain or branched alkyl group having 1 to 12 carbon atoms which are substituted with a T-oxy group or the like at R6 include, for example, those of Ri, R2 and R3 as described above. Ώ 6 p 7 &lt; 〇g , R, R5 R, R and R carbon number! The same group as exemplified in the linear, branched or cyclic (tetra) group of -12. One or more or one or more substituents may be present in the linear, branched or cyclic alkyl group in which the number of carbon atoms substituted by R6 is 12.

另外，在R6之經選自羥基和碳原子數1 _4的直鏈或支 鏈狀的烷氧基之取代基所取代的碳原子數24的直鏈或 支鏈狀的院氧基中，作為碳原子數丨_4的直鏈或支鏈狀的 烷氧基，例如可以舉出那些與上述R4、R5、r6、rS 的碳原子數1-4的直鏈或支鏈狀的烷氧基中所例示的同 樣的基團。 -21 - 1380065 修正本 對於R6之經取代的碳原子數2-4的直鏈或支鏈狀的 烷氧基，作為取代基，例如較佳為羥基、甲氧基等。 在R6之經取代的碳原子數2-4的直鏈或支鏈狀的烷 氧基，例如可以舉出乙氧基、正丙氧基、異丙氧基、正 '丁氧基、異丁氧基、二級丁氧基、三級丁氧基等。 - 在R6之經取代的碳原子數2-4的直鏈或支鏈狀的烷 氧基中，可以存在1種以上或1個以上的取代基。 在通式（1)中，作為R1，較佳為曱基、乙基、正丙基 ® 、異丙基 '正丁基、異丁基、二級丁基、三級丁基、正 戊基、正己基等。 另外，作為R2和R3，較佳為甲基、乙基、正丙基、 異丙基、正丁基、異丁基、二級丁基、三級丁基、正戊 基、正己基、正庚基、正辛基等。 另外，作為R4、R5、R7和R8，較佳為氫原子、曱基 、乙基等。 進而，作為R6，較佳為曱基、乙基、正丙基、異丙 φ 基、正丁基、異丁基、二級丁基、三級丁基、正戊基、 正己基、正庚基、正辛基、正癸基、正十二烷基、羥曱 基、2-羥乙基、甲氧甲基、2-曱氧乙基、甲氧基、乙氧 基、正丙氧基、異丙氧基、正丁氧基、羥基曱氧基、2-羥基乙氧基、甲氧曱氧基、2-甲氧乙氧基等。 在本發明十較佳化合物（1)之具體例，可以舉出： 2-(4-曱基苄基）-2-(二甲胺基）-1-(4-味啉并苯基）丁 烷-1-酮、 2-(4-乙基苄基）-2-(二曱胺基）-1-(4-咮啉并苯基）丁 -22- 1380065 修正本 烧-1 -酮、 2-(4-異丙基苄基）-2-(二曱胺基）-1-(4-味啉并苯基） 丁烷-1-酮、 2-(4-正丁基卞基）-2-(二曱胺基）-1-(4-味淋弁苯基） • 丁烷-1-酮、 • 2-(4-異丁基卞基）-2-(二甲胺基）-1-(4 -味嚇弁苯基） 丁烷-1-酮、 2-(4-正十二烷基苄基）-2-(二曱胺基）-1-(4-咮啉并苯 鲁基）丁烧-1-酮、 2-(3,4-二甲基苄基）-2-(二甲胺基）-1-(4-咮啉并苯基 )丁烷-1-酮、 2-(4-曱氧基苄基）-2-(二甲胺基）-1-(4-味啉并苯基） 丁烷-1-酮、 2-(4-乙氧基苄基）-2-(二曱胺基）-1-(4-味啉并苯基） 丁烷-1-酮、 2-(4-羥曱基苄基）-2-(二甲胺基）-1-(4-咮啉并苯基） ^ 丁烧-1 -酮、 2-[4-(2-羥基乙氧基）苄基]-2-(二甲胺基）-1-(4-味啉 并苯基）丁烷-1-酮、 2-[4-(2-甲氧基乙氧基）苄基]-2-(二曱胺基）-1-(4-咮 啉并苯基）丁烷-1-酮、 2-(4-異丙基苄基）-2-[(正丁基）（甲基）胺基]-1-(4-咮 琳并苯基）丁院-1-S同、 2-(4-正丁基苄基）-2-[(正丁基）（曱基）胺基]-1-(4-味 啉并苯基）丁烷-1-酮、 -23- 1380065 修正本 2-(4-異丙基苄基） 戊炫-1 -酮、 曱胺基）-1-(4-味淋并苯基） (4_異丁基苄基)·2·[(正丁基)(甲基)胺 琳并笨基）戊烷-1·嗣 攻也I H i T氧基卡基）·2·[(正丁基）（甲基）胺基]-1]4. 咪啉开苯基）戊烷-1·_、 1 2-(4 -曱基节基立甘、 I 一（正辛基）胺基]-1-(4-味啉并苯 基）己烧-1-嗣、 2-(4-正十二院基苄其、 卞基）-2-(二甲胺基）-1-(4-味啉并苯 基）辛烧-1 -酮等。 __在匕二化口物⑴中，特別較佳為2-(4-甲基节基卜2_( 二甲胺基）]-(4·味琳并苯基）丁烧]-酮、2-(4-乙基节基 )」2_(二甲胺基）小（4_味啉并苯基）丁烧小酮、2-(4_異丙^ 卞基）-2-(二曱胺基卜丨·。-味啉并苯基）丁烷_丨酮等。 化合物（1)是一種能夠形成優良間隔物的成分，它在 溶劑中的溶解性優良’不會產生未溶解物、析出物等的 異物，同時不會由於昇華而導致燒成爐或光罩等的污染 ’而且不會造成圖案的遺漏和缺損。 在本發明中，化合物（1)可以單獨使用或者2種以上 混合使用。 在本發明的放射線敏感性樹脂組合物中，相對於l〇〇 重量份的共聚物[A] ’化合物（1)的使用量較佳為5〜5〇重 莖份，更佳為5〜30重量份。在此情況下，當化合物（i) 的使用量小於5重量份時，殘膜率有降低的傾向，反之， 當超過50重量份時，未曝光部分在鹼性顯影液中的溶解 •24- 1380065 修正本 性有降低的傾向。 另外，在本發明的放射線敏感性樹脂組合物中，化 合物（1)可以與至少1種其他的放射線敏感性聚合引發劑 合併使用。 作為上述其他的放射線敏感性聚合引發劑，例如可 ' 以舉出：〇-醯基肟型化合物、苯乙酮類化合物、雙咪唑 類化合物、苯偶姻類化合物、二苯曱酮類化合物、α -二酮類化合物、多核酿類化合物、咕°頓_類化合物、膦 •類化合物、三啩類化合物等。 在這些其他的放射線敏感性聚合引發劑中’較佳為 〇-醯基肟型化合物、苯乙酮類化合物、雙咪唑類化合物 〇 上述的0-驢基聘型化合物是一類具有進一步提高靈 敏度作用的成分。 作為0-醯基肟型化合物的具體例，可以舉出1-(9-乙 基-6-苯甲醯基咔唑-3-基）壬烷-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）壬烷 -1,2 -壬院-2-月亏-0 -乙酸醋、1-(9 -己基-6-苯甲酿基-咔唑-3-基）戊烷-1,2-戊烷-2-肟-〇-乙酸酯、1-(9-乙基-6-苯曱醯基-9.H·-咔唑-3-基）辛烷-1-酮肟-〇-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 •0-苯曱酸酯、1-[9-乙基-6-(2-甲基苯曱醯基）-9·Η·-咔唑 •3-基]乙烷-1-酮肟-〇-乙酸酯、1-[9-乙基-6-(1,3,5-三曱基 苯甲醯基）-9.H.-咔唑-3-基]乙烷-卜酮肟-〇-苯曱酸酯、 1-[9-正丁基-6-(2-乙基苯甲醯基）·9·Η·-咔唑-3-基]乙烷 -25- 1380065 修正本 -1-酮肪苯甲酸酿、丨，2_辛二酮_WM苯硫基）苯基 ]-2,笨甲酿基聘）、以·丁二酮小[4_(苯硫基）苯基 ]-2-(〇-笨甲酿基肪）、j，2 丁二酮_1[4 (苯硫基）苯基 ]# (〇乙醯基肟）、12_辛二酮^[4(甲硫基）笨基]-2_(〇_ 苯甲醯基肟）、1，2_辛二酮小[4_(苯硫基）苯基]_2_[〇_(4· •甲基苯甲醯基肟）]等。 在這些〇-酸基肟型化合物中，較佳為1-[9-乙基 \6-f-甲基苯甲醯基）_9 Η._咔唑_3•基]乙烷酮肟乙 酸酉旨、1，2-辛二酮小[4_(苯硫基）苯基]_2_(〇·苯甲酿基將） 等。 上述的0-醯基肟型化合物可以單獨使 上混合使用 相對於共聚物[A] 1〇〇重量份，〇_醯基肟型化合物 使用量較佳為30重量份以下更佳為2〇重量份以下。在 此情況下，當Ο-酿基肪型化合物的使用量超過3〇 時，未曝光部分在驗性顯影液中的溶解性有降低的傾: 二且由於0-醯基肟型化合物的昇華所導致 ： :罩等的污染有增高的傾向。另外，當㈣基將型^ 的使用量小於5重量份時，殘膜率有可能降低。。 上述的|乙酮類化合物是對形成的間隔物的 有s周節作用的成分。 具 作為苯乙酮類化合物’例如可以舉出… 0物、α -胺基酮類化合物等。 匕 作為上〇_錄_化合㈣具體例，彳以 本基I經基_2-甲基丙燒小_、W心異丙基苯基）.2,基 -26- 1380065 修正本 -2·曱基丙烷_丨_酮、4_(2_羥基乙氧基）苯基_(2羥基丙 基）酮' 1-羥基環己基苯基酮等；作為上述^^_胺基酮類化 合物的具體例，可以舉出2-甲基·丨·^、甲硫基）苯基]·2_ 味啉并丙烷-1-酮、2-苄基-2-(二甲胺基）味啉并苯基 )丁烷-1-酮、1_(2_溴_4_咮嗒并笨基）·2_苄基_2_二甲胺基 丁烷-1-酮、2·(2_溴苄基）·2_(二曱胺基μι_(4•味啉并苯基 )丁烷-1_酮、2·(4·溴苄基）-2_(二曱胺基）-1-(4•味啉并苯基 )丁烷-1-酮等。作為這些化合物以外的苯乙酮類化合物的 具體例’可以舉出2,2_二甲氧基笨乙酮、2,2_二乙氧基笨 乙酮、2,2-二甲氧基_2_苯基苯乙酮等。 在這些苯乙酮類化合物中，較佳為2_甲基_1[4 (曱 硫基）苯基]-2-咮啉并丙烷-1-酮、2_苄基_2_(二甲胺基 )γ1-(4-咮啉并笨基）丁烷_丨_酮、丨_(2_溴4咮啉并苯基 苄基-2-二甲胺基丁烷酮、2_(4·溴苄基）2_(二曱胺基 )-1-(4-味啉并笨基）丁烷-丨_酮等。 上述的苯乙酮類化合物可以單獨使用或者2種以上 _ 混合使用。 相對於共聚物[A] 100重量份，苯乙酮類化合物的使 用量較佳為30重量份以下，更佳為20重量份以下。在此 情況下，當苯乙酮類化合物的使用量超過3〇重量份時， 由於苯乙酮類化合物的昇華所導致的燒成爐或光罩等的 污染和液體中異物的產生有增高的傾向。另外，當苯乙 酮類化合物的使用量小於丨重量份時，顯影時的殘膜率有 可能降低。 、 上述的雙咪唑類化合物是一種對形成的間隔物的形 -27- 1380065 修正本 狀具有調節作用’而且能夠起刭冷 你 巧^進―步提高靈敏度、圖 像解析度或與基板的黏附性的作用 J β用的成分。 作為雙咪唑類化合物的1赞&amp; ^ J八體例，可以舉出：2,2，_二 (2 -氣苯基）_4,4’，5,5’-四（4 -乙氧耧其― 殘基本基）·1，2’-雙味峻、 ’2_ —（2-&gt;臭笨基）-4,4’，5,5’ -四（4 7 - ^ L 四（4-乙氧羰基苯基）-1，2，- 雙咪唑、2,2，_二（2_氯苯基）_ ，3,5 -四苯基-1，2，-雙咪唑 2,2 _ —（2,4-二氣苯基）_4,4，5 5， ^ 0 ; ’ 4,5 _四苯基-1,2，-雙咪唑、 2,2 -二（2,4,6-三氯苯基）·4,4, 5 5, _ w ，，5 -四苯基-1,2，-雙咪唑 、2’2 _二（2·溴苯基）-4,4，，5,5、四笑 | , n Λ ，四本基-1，2’-雙咪唑、2,2，- —(2,4-二溴苯基）_4 4, 5 5、 - 0 , ，，四本基-1，2，-雙咪唑、2,2，- —(:，6_三漠苯基…’从-四苯基-…-雙^坐等。 在這些雙㈣類化合物中’較佳為2,2， 基 W，4，5,5’_四苯基ip·雙喃唾、 )-4 4 &gt; &lt; c , 一（2,4 -— 氯本基 ，，5,5_四苯基-1,2，-雙咪11坐、9。， Μ 4, 又木坐、2,2，·二（2,4,6-三氯苯基 (2 4 __，四苯基_1，2 _雙味唾等，特別較佳為2,2，-二 ，4·二氯笨基）-4,4，，5,5，-四苯基·12，雙。米唾。 =述的雙味錢化合物，可以單獨使 以上 叱合使用。 用旦子於”聚物[Α] 1 00重量I，雙σ米唾類化合物的使 情況乂佳為5〇重$份以下，更佳為35重量份以下。在此 向曰田雙咪唑類化合物的使用量超過5 〇重量份時， 時:曰曰中的溶出物增加’使得電壓保持率容易降低同 的、、-2又咪唑類化合物的昇華所導致的燒成爐或光罩等 量^木有增高的傾向。反之，當雙咪唑類化合物的使用 ;〇 ·1重1份時，殘膜率有可能降低。 -28- 1380065 修正本 在本發明的放射線敏感性樹脂組合物中，當 咪唾類化合物作為放射線敏感性聚合引發劑成分 ’較佳為合併使用那些對雙咪唑類化合物具有增 用的含有二烷基胺基的化合物。 作為這類含有二烷基胺基的化合物，較佳為 •有一炫基胺基的二苯甲酮衍生物和含有二烧基胺 曱酸醋類，更具體地可以舉出，例如，4,4，-雙（二 )二苯〒酮、4,4’-雙（二乙胺基）二苯甲酮、對二曱 ^曱酸乙酯、對二乙胺基苯甲酸乙酯、對二曱胺基 異戊酯、對二乙胺基苯甲酸異戊酯等。 在這些含有二烷基胺基的化合物中，特佳為4 二乙胺基）二苯曱酮。 上述含有二烷基胺基的化合物可以單獨使用 種以上混合使用。 在並用雙咪唑類化合物和含有二烷基胺基的 的場合，相對於共聚物[A] 100重量份，含有二烧 ^ 的化合物的使用量較佳為0.1-50重量份，更佳為ι_ 份。在此情況下，當含有二烷基胺基的化合物的 小於0 · 1重量份時，所獲間隔物容易發生膜減少或 物的形狀不良，反之，在超過50重量份時，間隔 狀受損，同時，由於含有二烷基胺基的化合物的 導致的燒成爐或光罩等的污染有增高的傾向。 進而’在本發明的放射線敏感性樹脂組合物 並用雙咪唑類化合物與含有二烷基胺基的化合物 射線敏感性聚合引發劑成分的場合，較佳為添加 使用雙 的場合 敏感作 例如含 基的苯 曱胺基 胺基苯 苯甲酸 ，4，-雙（ I或者2 化合物 基胺基 20重量 使用量 者間隔 物的形 昇華所 中，當 作為放 一種對 -29- 修正本 雙咪唾類化合物 化合物。雙咪/、能夠供給氫自由基的作用的硫醇類 合物增敏：而化合物會由於被含有二烷基胺基的化 在硫醇類化人物x，產生咪唑自由基，但此時如果不存 ，所獲間隔則不能產生高的自由基聚合引發能力 然而，通=形成如倒雜形那樣的不理想的形狀。 物共存的體：：咪坐類化合物與含有二烷基胺基的化合 供給氫自由A :加硫醇類化合物’就能向咪唑自由基 ’同時產果使得咪°坐自由基轉變成中性的^坐 間P物的/有聚合引發能力高的硫自由基，從而使 m的形狀成為比較理想的正錐形。 :為上述的硫醇化合物’例如可以舉出：2_疏基笨 :° 、2-疏基苯并十坐、2·疏基苯并味。坐、2_疏基_5_ 甲氧基求并。塞唾、2-疏基_5•甲氧基笨并味。坐等芳香族化 合物，3·魏基丙酸、3_疏基丙酸甲§旨、3_疏基丙酸乙醋、 3-巯基丙酸辛酯等的脂肪族類一硫醇；3,6-二噚_1,8_辛烷 二硫醇 '四級戊四醇四（巯基乙酸酯）、四級戊四醇四 魏基丙酸酯）等的脂肪族多硫醇類化合物等。 這些硫醇化合物可以單獨使用或者2種以上混合使 用。 在將雙咪唑類化合物、含有二烷基胺基的化合物和 硫醇類化合物組合使用的場合，相對於共聚物[α] ι〇〇重 量份，硫醇類化合物的使用量較佳為〇丨_5〇重量份更 佳為1-20重量份。在此情況下，當硫醇類化合物的使用 量小於0.1重量份時’所獲間隔物存在容易發生膜減少或 形狀不良的傾向，反之’當超過50重量份時，間隔物的 -30- I38〇〇65 修正本 形狀可能受損，同時，由於硫醇類化合物的昇華，使得 燒成爐或光罩等受污染的可能性有增高的傾向。 在本發明的放射線敏感性樹脂組合物中，相對於全 部放射線敏感性聚合引發劑100重量份，其他放射線敏感 .性聚合引發劑的使用比例較佳為100重量份以下，更佳為 80重量份以下，特別較佳為60重量份以下。在此情況下 ，备其他的放射線敏感性聚合引發劑的使用比例超過丄〇 〇 重量份時，有可能損害本發明所期望的效果。 _ 一任意添加劑一 在本發明的放射線敏感性樹脂組合物中，可以根據 ^要在不損害本發明效果的範圍内混合上述成分以外 的任意添加劑，例如界面活性劑、黏結助劑保存穩定 劑、耐熱性提高劑等。 上述界面活性劑是用來提高塗布性能的混合成分， 較佳為氟類界面活性劑以及矽氧烷類界面活性劑。 作為上述的氟類界面活性劑，較佳為在末端、主鏈 φ和側鏈中的至少一個部位上具有氟烷基和/或伸氟烷基 的化合物，作為其例子，可以舉出：Μ，2,2四氟_正辛 基（Μ，2,2-四氤-正丙基）醚、Μ，2,2_四氟-正辛基（正己基 )鍵八乙二醇二（1，1，2,2 -四氟正丁基）醚、六甘醇 (1，1，2,2,3,3-六氟_正戊基）醚、八丙二醇二（1,1，2,2_四氟_ 正丁基）醚、六丙二醇二六氟_正戊基）醚、 1，1’2,2,3,3-六氟正癸烷、^^^^ ^十氟正十 二烷、全氟正十二烷磺酸鈉，以及氟烷基苯磺酸鈉類、 氟烷基膦酸鈉類、氟烷基羧酸鈉類、氟烷基聚氧乙烯醚 -31 - 1380065 修正本 類、二丙三醇四（氟烷基聚氧乙烯醚）類、氟烷基碘化銨 類、氟烷基甜菜鹼類、氟烷基聚氧乙烯醚類、全氟烷基 聚氧乙醇類、全氟烷基烷氧基酯類、氟系烷基酯類等。Further, in the linear or branched tertiary oxy group having 24 carbon atoms which is substituted with a substituent selected from a hydroxyl group and a linear or branched alkoxy group having 1 to 4 carbon atoms; The linear or branched alkoxy group having a carbon number of 丨4 may, for example, be a linear or branched alkoxy group having 1 to 4 carbon atoms with respect to the above R4, R5, r6 and rS. The same groups as exemplified in the above. -21 - 1380065 The linear or branched alkoxy group having 2 to 4 carbon atoms which is substituted with R6 is preferably a hydroxyl group or a methoxy group. Examples of the linear or branched alkoxy group having 2 to 4 carbon atoms which are substituted by R6 include an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, and an isobutyl group. Oxyl, secondary butoxy, tertiary butoxy, and the like. - One or more or one or more substituents may be present in the linear or branched alkoxy group having 2 to 4 carbon atoms which is substituted by R6. In the formula (1), as R1, a decyl group, an ethyl group, a n-propyl group, an isopropyl 'n-butyl group, an isobutyl group, a secondary butyl group, a tertiary butyl group, and a n-pentyl group are preferred. , Zhengjiji and so on. Further, as R2 and R3, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a secondary butyl group, a tertiary butyl group, a n-pentyl group, a n-hexyl group, and a positive group are preferable. Heptyl, n-octyl and the like. Further, as R4, R5, R7 and R8, a hydrogen atom, a fluorenyl group, an ethyl group or the like is preferable. Further, as R6, a decyl group, an ethyl group, a n-propyl group, an isopropyl φ group, a n-butyl group, an isobutyl group, a secondary butyl group, a tertiary butyl group, a n-pentyl group, a n-hexyl group, and a n-heptane are preferred. Base, n-octyl, n-decyl, n-dodecyl, hydroxydecyl, 2-hydroxyethyl, methoxymethyl, 2-decyloxyethyl, methoxy, ethoxy, n-propoxy , isopropoxy, n-butoxy, hydroxymethoxy, 2-hydroxyethoxy, methoxycarbonyl, 2-methoxyethoxy, and the like. Specific examples of the ten preferred compounds (1) of the present invention include: 2-(4-mercaptobenzyl)-2-(dimethylamino)-1-(4-carbophenyl)phenyl Alkan-1-one, 2-(4-ethylbenzyl)-2-(didecylamino)-1-(4- porphyrin phenyl) butyl-22- 1380065 2-(4-Isopropylbenzyl)-2-(didecylamino)-1-(4-morpholinophenyl)butan-1-one, 2-(4-n-butyldecyl) -2-(didecylamino)-1-(4-isolinylphenyl) • Butan-1-one, • 2-(4-isobutylfluorenyl)-2-(dimethylamino) -1-(4-flavored phenyl) butan-1-one, 2-(4-n-dodecylbenzyl)-2-(didecylamino)-1-(4-carboline Benzene)butan-1-one, 2-(3,4-dimethylbenzyl)-2-(dimethylamino)-1-(4-porphyrin-phenyl)butane-1- Ketone, 2-(4-decyloxybenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, 2-(4-ethoxybenzyl 2-(2-decylamino)-1-(4-morpholinophenyl)butan-1-one, 2-(4-hydroxydecylbenzyl)-2-(dimethylamino) -1-(4-porphyrin-phenyl) ^ butyl-1 - ketone, 2-[4-(2-hydroxyethoxy)benzyl]-2-(dimethylamino)-1-(4) -porphyrin Phenyl)butan-1-one, 2-[4-(2-methoxyethoxy)benzyl]-2-(didecylamino)-1-(4-porphyrin-phenyl) Butan-1-one, 2-(4-isopropylbenzyl)-2-[(n-butyl)(methyl)amino]-1-(4-indene-phenyl) dingyuan-1 -S, 2-(4-n-butylbenzyl)-2-[(n-butyl)(indolyl)amino]-1-(4-morpholinophenyl)butan-1-one, -23- 1380065 Amendment to 2-(4-isopropylbenzyl)pentan-1 -one, decylamino)-1-(4-flavorylphenyl) (4-I-butylbenzyl)· 2·[(n-butyl)(methyl)amine-lin and stupid)pentane-1·嗣 attack also IH i T-oxykaki)·2·[(n-butyl)(methyl)amino group] -1]4. morpholine-opened phenyl)pentane-1·_, 1 2-(4-mercaptobenzylidene, I-(n-octyl)amino]-1-(4-s Phenyl)hexan-1-yl, 2-(4-n-tetradecylbenzylidene, fluorenyl)-2-(dimethylamino)-1-(4-sodium phenyl) phenyl- 1 - ketone, etc. __ In the oxime (1), particularly preferably 2-(4-methylbenzylidene 2_(dimethylamino)]-(4·味琳和phenyl) butadiene ]-ketone, 2-(4-ethylhexyl)"2-(dimethylamino) small (4_morpholininophenyl) Small-one, 2- (4 _ ^ isopropyl Bian yl) -2- (Ji Boshu two Yue-amine. - morpholine phenyl) butane _ fluorenone and the like. The compound (1) is a component capable of forming an excellent spacer, and has excellent solubility in a solvent, and does not generate foreign matter such as undissolved matter or precipitates, and does not cause a firing furnace or a mask due to sublimation. The pollution 'does not cause omissions and defects in the pattern. In the present invention, the compound (1) may be used singly or in combination of two or more kinds. In the radiation sensitive resin composition of the present invention, the amount of the compound [1] used in the copolymer [A] 'pound (1) is preferably 5 to 5 ounces, more preferably 5 to 30 parts by weight. Parts by weight. In this case, when the amount of the compound (i) used is less than 5 parts by weight, the residual film ratio tends to decrease, and conversely, when it exceeds 50 parts by weight, the unexposed portion is dissolved in the alkaline developing solution. 1380065 Fixed a tendency to reduce the nature. Further, in the radiation sensitive resin composition of the present invention, the compound (1) can be used in combination with at least one other radiation sensitive polymerization initiator. Examples of the other radiation-sensitive polymerization initiator include, for example, a fluorene-fluorenyl compound, an acetophenone compound, a biimidazole compound, a benzoin compound, a benzophenone compound, and the like. An α-diketone compound, a polynuclear brewing compound, a sulfonium compound, a phosphine compound, a triterpenoid compound, and the like. Among these other radiation-sensitive polymerization initiators, 'preferably an anthracene-quinone-based compound, an acetophenone compound, a biimidazole compound, and the above-mentioned 0-fluorene-based compound are one type of further improving sensitivity. Ingredients. Specific examples of the 0-fluorenyl quinoid compound include 1-(9-ethyl-6-benzylidenecarbazol-3-yl)decane-1,2-decane-2-indole- 0-_ Benzoate, 1-(9-ethyl-6-benzylidenyl-9.H.-carbazol-3-yl)nonane-1,2 - brothel-2-month loss- 0 -acetic acid vinegar, 1-(9-hexyl-6-benzolic-oxazol-3-yl)pentane-1,2-pentane-2-indole-indole-acetate, 1-(9 -ethyl-6-phenylhydrazino-9.H--oxazol-3-yl)octane-1-one oxime-indole-acetate, 1-[9-ethyl-6-(2- Methylbenzylidene)-9.H--oxazol-3-yl]ethane-1-one oxime•0-benzoate, 1-[9-ethyl-6-(2-methyl Benzoyl)-9·Η·-carbazole•3-yl]ethane-1-one oxime-indole-acetate, 1-[9-ethyl-6-(1,3,5-three Mercaptobenzylidene)-9.H.-oxazol-3-yl]ethane-buxanthene-indole-benzoate, 1-[9-n-butyl-6-(2-ethyl Benzyl hydrazino)·9·Η·-oxazol-3-yl]ethane-25- 1380065 Amendment to this 1-keto fatty benzoic acid, hydrazine, 2 octanedione _WM phenylthio) phenyl ]-2, stupid brewing base), d-butyl diketone small [4_(phenylthio)phenyl]-2-(〇-笨甲甲脂), j,2丁二酮_1[4 (phenylthio)phenyl]# (〇乙醯基肟, 12_octanedione^[4(methylthio)phenyl]-2_(〇_benzhydrylhydrazine), 1,2-octanedione small [4_(phenylthio)phenyl]_2_[〇 _(4· •methylbenzhydryl hydrazine)] and the like. Among these oxime-acid oxime type compounds, 1-[9-ethyl\6-f-methylbenzhydryl)_9 Η._carbazole _3•yl]ethane ketone oxime acetate is preferred. It is intended to be 1,2-octanedione small [4_(phenylthio)phenyl]_2_(〇·benzoyl) and the like. The above-mentioned 0-fluorenyl hydrazine type compound may be used alone or in combination with respect to the copolymer [A] in an amount of 1 part by weight, and the hydrazine-based hydrazine type compound is preferably used in an amount of preferably 30 parts by weight or less, more preferably 2 parts by weight. The following. In this case, when the amount of the ruthenium-based fatty compound used exceeds 3 Å, the solubility of the unexposed portion in the test developer is lowered: and the sublimation of the compound is 0-fluorenyl Caused by: : The pollution of the cover and the like tends to increase. Further, when the amount of the (4) group is less than 5 parts by weight, the residual film ratio may be lowered. . The above-mentioned |ethylketone compound is a component having an s-circumferential action on the formed spacer. Examples of the acetophenone-based compound' include, for example, a substance, an α-amino ketone compound, and the like.匕 〇 〇 录 录 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Mercaptopropane_丨-ketone, 4_(2-hydroxyethoxy)phenyl-(2-hydroxypropyl)ketone' 1-hydroxycyclohexyl phenyl ketone, etc.; as specific of the above-mentioned amine ketone compound For example, 2-methyl·丨·^, methylthio)phenyl]·2_ morpholine propan-1-one, 2-benzyl-2-(dimethylamino) porphyrin and phenyl Butane-1-one, 1_(2_bromo_4_indolyl)·2_benzyl-2-dimethylaminobutan-1-one, 2·(2-bromobenzyl) · 2_(diamine-based μι_(4• benzophenothiphenyl)butane-1 ketone, 2·(4·bromobenzyl)-2_(diguanylamino)-1-(4• sulphonoline Phenyl) butan-1-one, etc. Specific examples of the acetophenone compound other than these compounds include 2,2-dimethoxyacetophenone and 2,2-diethoxy stupin Ketone, 2,2-dimethoxy-2-phenylacetophenone, etc. Among these acetophenones, 2-methyl-1[4(indolyl)phenyl]-2 is preferred. - porphyrin propane-1-one, 2-benzyl-2-(dimethylamino) gamma 1-(4- porphyrin and stupid) Butane_丨-ketone, 丨_(2_bromotetrazolinophenylbenzyl-2-dimethylaminobutanone, 2_(4·bromobenzyl)2_(didecylamino)-1- (4-norphline and stupid) butane-indole-ketone, etc. The above-mentioned acetophenone-based compounds may be used singly or in combination of two or more kinds. The acetophenones are used in an amount of 100 parts by weight based on the copolymer [A]. The amount of the compound to be used is preferably 30 parts by weight or less, more preferably 20 parts by weight or less. In this case, when the amount of the acetophenone compound is more than 3 parts by weight, the sublimation of the acetophenone compound The contamination of the firing furnace, the reticle, and the like, and the generation of foreign matter in the liquid tend to increase. When the amount of the acetophenone compound used is less than 丨 by weight, the residual film ratio during development may be lowered. The above-mentioned biimidazole compound is a kind of regulating effect on the shape of the formed spacer -27- 1380065, and can be used to improve the sensitivity, image resolution or adhesion to the substrate. The role of the component of J β. As a double imidazole compound, 1 like & ^ J eight body examples, can be cited :2,2,_2 (2-air phenyl)_4,4',5,5'-tetra (4-ethoxy oxime-residual basic group)·1,2'-Shuangweijun, '2_ (2-&gt; stinky base)-4,4',5,5'-tetra(4 7 - ^ L tetrakis(4-ethoxycarbonylphenyl)-1,2,-bisimidazole, 2,2, _Bis(2-chlorophenyl)_,3,5-tetraphenyl-1,2,-bisimidazole 2,2 _-(2,4-diphenyl)_4,4,5 5, ^ 0 ; '4,5 _tetraphenyl-1,2,-bisimidazole, 2,2-di(2,4,6-trichlorophenyl)·4,4, 5 5, _ w ,,5 - four Phenyl-1,2,-bisimidazole, 2'2 _bis(2.bromophenyl)-4,4,5,5,tetramide| , n Λ , tetrabenyl-1,2'-double Imidazole, 2,2,-(2,4-dibromophenyl)_4 4, 5 5, - 0 , ,, tetrakis-1,2,-bisimidazole, 2,2,- (:, 6_Three desert phenyl... 'from - tetraphenyl-...- double ^ sit and so on. Among these bis(four) compounds, 'preferably 2,2, yl W, 4,5,5'-tetraphenyl ip. bis-salt, -4 4 &gt;&lt; c , one (2, 4 - — chlorobenyl, 5,5_tetraphenyl-1,2,-shuangmi 11 sitting, 9., Μ 4, wooden sitting, 2,2,·2 (2,4,6-trichlorobenzene Base (2 4 __, tetraphenyl-1,2 _ double-flavored saliva, etc., particularly preferably 2,2,-di, 4·dichlorophenyl)-4,4,,5,5,-tetraphenyl Base 12, double. Rice saliva. = The double-flavor compound described above can be used alone. It is better to use the scorpion in the "polymer [Α] 1 00 weight I, double σ meter salic compound. It is 5 parts by weight or less, more preferably 35 parts by weight or less. When the amount of the bi-imidazole compound used in the field is more than 5 parts by weight, the increase in the elution in the crucible makes the voltage retention rate easy. Reducing the amount of calcination furnace or reticle of the same, and -2, and imidazole compounds, the amount of wood is increased. Conversely, when the use of biimidazoles is used; The film rate may be lowered. -28- 1380065 The present invention is in the radiation sensitive resin composition of the present invention, when As the radiation-sensitive polymerization initiator component, it is preferred to use a dialkylamine group-containing compound which is added to the biimidazole compound in combination with such a compound containing a dialkylamine group.佳••••••••••••••••••••••••••••••••••••••••••••••••••••••••••• , 4'-bis(diethylamino)benzophenone, p-dioxanoic acid ethyl ester, p-diethylaminobenzoic acid ethyl ester, p-diammonium isoamyl ester, p-diethylaminobenzene Isoamyl formate or the like. Among these compounds containing a dialkylamine group, particularly preferred is 4 diethylamino)diphenyl fluorenone. The above dialkylamino group-containing compound may be used singly or in combination of two or more kinds. In the case of using a bisimidazole compound and a dialkylamine group, the amount of the compound containing the dioctogen is preferably 0.1 to 50 parts by weight, more preferably 1 to 10 parts by weight based on 100 parts by weight of the copolymer [A]. In this case, when less than 0.1 part by weight of the compound containing a dialkylamine group The obtained spacer is likely to have a film reduction or a shape defect of the object. On the other hand, when it exceeds 50 parts by weight, the spacer is damaged, and at the same time, a baking furnace, a mask, or the like due to a compound containing a dialkylamine group is used. In the case where the radiation sensitive resin composition of the present invention is used in combination with a diimidazole compound and a dialkylamine group-containing compound radiation-sensitive polymerization initiator component, it is preferred to use a double. Occasionally sensitive to, for example, a phenylguanidinoaminobenzoic acid containing a group, 4,-bis (I or 2 compound amine group 20 weight usage amount of the spacer sublimation, when used as a pair of -29- Amend the compound of this dimethine salivary compound. The thiol compound that is capable of supplying hydrogen radicals is sensitized: while the compound is produced by the inclusion of a dialkylamine group in the thiolated group x, an imidazole radical is generated, but if If it does not exist, the obtained interval does not produce a high radical polymerization initiating ability. However, the pass = forms an undesired shape such as an inverted shape. The coexisting body: the compound of the amino compound and the compound containing a dialkylamine group supply hydrogen free A: the thiol compound can 'produce the fruit simultaneously to the imidazole radical', so that the free radical is converted into neutral The ^ sitting material P / has a high degree of polymerization initiation of sulfur radicals, so that the shape of m becomes a more ideal forward cone. The above-mentioned thiol compound 'is, for example, 2 - succinyl: °, 2- benzyl benzoxanthene, and 2 thiol benzoate. Sit, 2_ sparse _5_ methoxy sum. The sputum, 2- sparyl _5• methoxy is stupid. An aromatic monothiol such as an aromatic compound, 3·weikipropionic acid, 3-pyridylpropionic acid, xylopropionate, and octyl 3-mercaptopropionate; 3,6- An aliphatic polythiol compound such as diterpene-1,8-octanedithiol 'fourth-grade pentaerythritol tetrakis(mercaptoacetate), fourth-grade pentaerythritol tetraweipropionate). These thiol compounds may be used singly or in combination of two or more. When a biimidazole compound, a dialkylamine group-containing compound, and a thiol compound are used in combination, the amount of the thiol compound used is preferably 〇丨 based on the weight of the copolymer [α] oxime. More preferably, the amount of _5 parts by weight is from 1 to 20 parts by weight. In this case, when the amount of the thiol compound used is less than 0.1 parts by weight, the spacer obtained tends to be prone to film reduction or poor shape, whereas when it exceeds 50 parts by weight, the spacer -30-I38 〇〇65 Correction of this shape may be impaired, and at the same time, the possibility of contamination of the firing furnace or the reticle tends to increase due to the sublimation of the thiol compound. In the radiation-sensitive resin composition of the present invention, the use ratio of the other radiation-sensitive polymerization initiator is preferably 100 parts by weight or less, more preferably 80 parts by weight, based on 100 parts by weight of all the radiation-sensitive polymerization initiators. Hereinafter, it is particularly preferably 60 parts by weight or less. In this case, when the ratio of use of other radiation-sensitive polymerization initiators exceeds 丄〇 重量 by weight, the desired effects of the present invention may be impaired. _ an optional additive - in the radiation-sensitive resin composition of the present invention, any additive other than the above components may be mixed in a range not impairing the effects of the present invention, for example, a surfactant, a binder auxiliary storage stabilizer, Heat resistance improver, etc. The above surfactant is a mixed component for improving coating properties, and is preferably a fluorine-based surfactant and a siloxane-based surfactant. The fluorine-based surfactant is preferably a compound having a fluoroalkyl group and/or a fluoroalkyl group at at least one of a terminal group, a main chain φ and a side chain, and examples thereof include hydrazine. , 2, 2 tetrafluoro-n-octyl (Μ, 2,2-tetra-n-propyl) ether, hydrazine, 2,2_tetrafluoro-n-octyl (n-hexyl) bond octaethylene glycol di(1) , 1,2,2-tetrafluoro-n-butyl)ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoro-n-pentyl)ether, octapropylene glycol di(1,1,2, 2_tetrafluoro-n-butyl)ether, hexa-propylene glycol dihexafluoro-n-pentyl)ether, 1,1'2,2,3,3-hexafluoro-n-decane, ^^^^ ^ decafluoro-nine Dioxane, sodium perfluoro-n-dodecanesulfonate, sodium fluoroalkylbenzenesulfonate, sodium fluoroalkylphosphonate, sodium fluoroalkylcarboxylate, fluoroalkyl polyoxyethylene ether-31 - 1380065 Amendment to this class, diglycerol tetrakis(fluoroalkyl polyoxyethylene ether), fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl polyoxyethylene ether, perfluoroalkyl polyoxygen Ethanol, perfluoroalkyl alkoxy esters, fluoroalkyl esters, and the like.

另外，作為氟類界面活性劑的市售商品，例如可以 . 列舉：BM-1000、BM-1100(以上產品為BM CHEMIE公司 . 製造），MEGAFACE F142D、MEGAFACE F172、 MEGAFACE F173、MEGAFACE F178、MEGAFACE F183 、MEGAFACE F191、MEGAFACE F471、MEGAFACE • F476(以上產品為大曰本油墨化學工業（股）製造）， FLUORAD FC-170C、FLUORAD FC-171、FLUORAD FC-43 0、FLUORAD FC-43 1(以上產品為住友3M(股）製造 )，SURFLONS-112、SURFLON S-1 13、SURFLON S-131 、SURFLON S-141、SURFLON S-145、SURFLON S-382 、SURFLON SC-101、SURFLON SC-102、SURFLON SC-103' SURFLON S C-1 04' SURFLON S C -1 0 5 &gt; S URFLON SC-106(以上產品為旭硝子（股）製造），EFTOPEF301、 • EFTOP EF303、EFTOP EF3 52(以上產品為新秋田化成（ 股）製造），FTERGENT FT-100、FTERGENT FT-1 10、 FTERGENT FT-140A、FTERGENT FT-150、FTERGENT FT-250、FTERGENT FT-251、FTERGENT FT-300、 FTERGENT FT-310、FTERGENT FT-400S、FTERGENT FTX-21 8、FTERGENT FTX-251(以上產品為耐歐斯（股） 製造）等。 作為上述的矽氧烷類界面活性劑，例如可以列舉以 下列商品名銷售的產品：Toray Silicone DC3PA、Toray -32- 修正本 1380065Further, as a commercially available product of a fluorine-based surfactant, for example, BM-1000, BM-1100 (the above products are manufactured by BM CHEMIE Co., Ltd.), MEGAFACE F142D, MEGAFACE F172, MEGAFACE F173, MEGAFACE F178, MEGAFACE F183 , MEGAFACE F191, MEGAFACE F471, MEGAFACE • F476 (The above products are manufactured by Otsuka Ink Chemical Industry Co., Ltd.), FLUORAD FC-170C, FLUORAD FC-171, FLUORAD FC-43 0, FLUORAD FC-43 1 (above products) Manufactured for Sumitomo 3M Co., SURFLONS-112, SURFLON S-1 13, SURFLON S-131, SURFLON S-141, SURFLON S-145, SURFLON S-382, SURFLON SC-101, SURFLON SC-102, SURFLON SC-103' SURFLON S C-1 04' SURFLON SC -1 0 5 &gt; S URFLON SC-106 (The above products are manufactured by Asahi Glass Co., Ltd.), EFTOPEF301, EFTOP EF303, EFTOP EF3 52 (The above products are New Akita Chemical (manufacturing), FTERGENT FT-100, FTERGENT FT-1 10, FTERGENT FT-140A, FTERGENT FT-150, FTERGENT FT-250, FTERGENT FT-251, FTERGENT FT-300, FTERGENT FT-310, FTERGENT FT -400S, FTERGENT FTX-21 8, FTERGENT FTX-251 ( The above products are manufactured by Naos (shares) and so on. As the above-mentioned siloxane-based surfactant, for example, products sold under the following trade names: Toray Silicone DC3PA, Toray-32- Amendment 1380065

Silicone DC7PA、Toray Silicone SHllPA、Toray Silicone SH21PA、Toray Silicone SH28PA、Toray Silicone SH29PA、Toray Silicone SH30PA、Toray Silicone SH-190 、Toray Silicone SH-193、Toray Silicone SZ-6032、Toray Silicone SF-8428 ' Toray Silicone DC-57、Toray Silicone • DC-190(以上產品為 Toray Dow Corning Silicon (股）製造 )，TSF-4440、TSF-4300、TSF-4445、TSF-4446、TSF-4460 、TSF-4452(以上產品為GE東芝Silicon(股）製造）。 &gt; 此外，作為上述以外的界面活性劑，例如可以列舉 :聚氧乙烯十二烷基醚、聚氧乙烯十八烷基醚、聚氧乙 烯油基醚等聚氧乙烯烷基醚類；聚氧乙烯正辛基苯基醚 '聚氧乙稀正壬基笨基縫等聚氧乙烯芳基醚類；聚氧乙 烯二月桂酸酯、聚氧乙烯二硬脂酸酯等聚氧乙烯二烷基 酯類等非離子型界面活性劑；作為市售的商品可以列舉 KP341(信越化學工業（股）製造）、p〇lYFL〇w n〇 57、 P〇LYFLOW-No.95(以上產品為共榮社化學（股）製造）等。 | 這些界面活性劑可以單獨使用或者2種以上混合使 用。 相對於1 00重量份的平私r Λ Ί β J /、♦物[A]，界面活性劑的混合 量較佳為5重量份以下，更佳盔 θ 又住為2重量份以下。在此情況 下，界面活性劑的混合量超過$舌曰 、m 3重I份時，塗布時往往容 易產生塗膜粗糙。 上述的黏結助劑是用來進— 步知问與基板的黏附性 的混合成分。 作為如此的黏結助劑，動 权佳為官能性矽烷偶聯劑， -33- l38〇〇65 修正本 作為其例子’可以舉出：具有羧基、甲基兩歸 .烯基、異氰酸酯基、環氧基等反應性官能基的 劑，更具體而言，可以舉出三曱氧基甲矽烷基 τ -甲基丙烯醯氧基丙基三甲氧基矽烷、乙歸基 基石夕烧、乙稀基二甲氧基石夕烧、7 -異氰酸顆茂 氧基矽烷' r_環氧丙氧基丙基三甲氧基矽烷、 氧基環己基）乙基三甲氧基矽烷等。Silicone DC7PA, Toray Silicone SHllPA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH-190, Toray Silicone SH-193, Toray Silicone SZ-6032, Toray Silicone SF-8428 ' Toray Silicone DC -57, Toray Silicone • DC-190 (The above products are manufactured by Toray Dow Corning Silicon), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 (the above products are GE Toshiba Silicon Co., Ltd.). In addition, examples of the surfactant other than the above include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; Polyoxyethylene aryl ethers such as oxyethylene n-octyl phenyl ether 'polyoxyethylene divalent fluorenyl sulfhydryl base; polyoxyethylene dialkyl such as polyoxyethylene dilaurate or polyoxyethylene distearate Non-ionic surfactants such as esters; as commercially available products, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), p〇l YFL〇wn〇57, P〇LYFLOW-No. 95 (the above products are co-prosperous) Social chemical (share) manufacturing) and so on. These surfactants may be used singly or in combination of two or more. The blending amount of the surfactant is preferably 5 parts by weight or less based on 100 parts by weight of the flat ruthenium Ί J β J /, ♦ [A], and the helmet θ is more preferably 2 parts by weight or less. In this case, when the amount of the surfactant blended exceeds $ton, and m3 weighs one part, the coating film is likely to be rough at the time of coating. The above-mentioned bonding aid is a mixed component for further inspecting the adhesion to the substrate. As such a bonding aid, the activator is a functional decane coupling agent, -33-l38〇〇65, as an example thereof, which has a carboxyl group, a methyl group, an alkenyl group, an isocyanate group, and a ring. Examples of the reactive functional group such as an oxy group, more specifically, a trimethoxymethoxymethyl hydrazide τ-methyl propylene methoxy propyl trimethoxy decane, a condensed base sulphur, and a vinyl group. Dimethoxy zeoxime, 7-isocyanate methoxymethoxy decane 'r_glycidoxypropyltrimethoxydecane, oxycyclohexyl)ethyltrimethoxydecane, and the like.

酸基、乙 矽烷偶聯 笨甲酸、 三乙醯氧 丙基三乙 2_(3,4·環 這些黏結助劑可以單獨使用或者2種以上 此公使用 量 劑 餘 相對於1 〇〇重量份的共聚物[A]，黏結助劑的混合 較佳為20重量份以下，更佳為丨〇重量份以下。黏結助 的混合量如果超過20重量份，則往往容易產生顯影殘 作為上述的保存穩定劑，例如可以舉出：硫、醌類 、氫醌類、聚氧化合物、胺類、硝基亞硝基化合物等， 作為其例子，可以舉出4-甲氧基苯酚、N_亞硝基I苯基 羥基胺鋁等。 土 相對於100重量份的共聚物[A]，保存穩定劑的使用 量較佳為3.0重量份以下，更佳為〇 5重量份以下。在此情 況下，保存穩定劑的使用量超過3 〇重量份時，靈敏度降 低’所得間隔物的形狀可能受到損害。 作為上述的耐熱性提高劑，例如可以舉出n_(烷氧基 甲基）乙炔脲化合物、N_(烷氧基甲基）三聚氰胺化合物、 具有2個以上環氧基的化合物等。 作為上述的N-(.烷氧基甲基）乙炔脲化合物，例如可 以舉出：N，N，N，N-四（甲氧基甲基）乙炔脲、n，n，n,n_四（ -34 - 丄 JOl/UCO 修正本 丙氧基曱基）乙炔脲 、N，N，N，N-四（正丁 丁氧基曱基）乙炔脲 乙氧基曱基）乙炔脲、N，N，N，N•四（正 、n，n，n，n-四（異丙氧基甲基）乙块腺 氧基甲基）乙炔脲、N，N，N，N-四（三級 等。 〜、及 在运些N-(烷氧基曱基）乙 M M χτ χτ , 块腺化合物中’較佳為 Ν，Ν，Ν，Ν-四（甲氧基曱基）乙炔脲。 &amp; 作為上述的N-(烷氧基曱基）= )—t氰胺化合物，例如 可以舉出：N，N，N，N,N,N-六（曱4 f w Μ Μ Μ XT XT xr 1 Y氧基曱基）三聚氰胺、 N，N，N，N，N，N-六（乙氧基甲基）二取&amp; &gt; )—來虱胺、n，n，n，n，n，n- ✓、（正丙氧基曱基）三聚氰胺、 » , , , ^ N，N，N，N，N，N-六（異丙氧基 甲基）一 I 鼠胺、N，N，N，N，N N -丄'/w _ χτx ，，w 〇(正丁氧基甲基）三聚氰 胺、Ν，Ν，Ν，Ν，Ν，Ν-六（三級丁氡美 j礼基甲基）三聚氰胺等。 於此等N-(烷氧基曱基广臂 土）一眾亂胺化合物中，優先用 Ν,Ν,Ν,Ν，N，N-六（甲氧基甲其 &amp;甲基）二聚氰胺，作為其市售商 品，例如可以列舉nikalac ν_2702、腿alac MW-30M(以上產品為三和化學⑷製造）等。 作為上述具有2個以上環氧其 ^ 乳I的化合物，例如可以舉 出·乙二醇二縮水甘油_、二 _ —乙一醇二縮水甘油轉、聚 乙二醇二縮水甘油喊'丙-醇-始 π — ％ —縮水甘油醚、三丙二醇 二縮水甘油醚、聚丙-醢-始 祆丙一転一縮水甘油醚、新戊二醇二縮 水甘油醚、1，6 -己-醢-始士 | · 知一縮水甘油醚、丙三醇二.縮水甘 油鍵、三經甲基丙烷三縮水 H /田越、加虱雙紛A二縮水甘 油醚、雙酚A二縮水甘油醚等❶ 另外作為具有2個以上環氧基的化合物的市售商品 ，例如可以列舉伊波拉托40E、伊波拉托麵、伊波拉托 -35· U80065 修正本 2〇〇E、伊波拉托7〇P、伊波拉托2〇〇p、伊波拉托4〇〇p、 伊波拉托1 500NP、伊波拉托16〇〇、伊波拉托8〇]^1?、伊波 拉托100MF、伊波拉托3002、伊波拉托4〇〇〇(以上產品為 共榮社化學（股）製造）等。 這些耐熱性提高劑可以單獨使用或者2種以上混合 * 使用。 。Acid group, acetylene coupled with benzoic acid, triethyl methoxypropyl triethyl 2 _ (3, 4 · ring these adhesion auxiliaries can be used alone or two or more of this public use agent relative to 1 〇〇 by weight The copolymer [A], the mixing aid is preferably blended in an amount of 20 parts by weight or less, more preferably 5% by weight or less. If the amount of the binder is more than 20 parts by weight, the development residue tends to be stable as described above. Examples of the agent include sulfur, hydrazines, hydroquinones, polyoxygen compounds, amines, and nitronitroso compounds. Examples thereof include 4-methoxyphenol and N-nitroso I phenylhydroxylamine aluminum or the like. The amount of the storage stabilizer used is preferably 3.0 parts by weight or less, more preferably 5% by weight or less based on 100 parts by weight of the copolymer [A]. In this case, preservation is carried out. When the amount of the stabilizer is more than 3 parts by weight, the sensitivity is lowered. The shape of the obtained spacer may be impaired. Examples of the heat resistance improving agent include n-(alkoxymethyl)acetylene urea compound and N_( Alkoxymethyl)melamine compound A compound having two or more epoxy groups, etc. Examples of the N-(.alkoxymethyl)acetylene urea compound described above include N,N,N,N-tetrakis(methoxymethyl)acetylene. Urea, n, n, n, n_tetra (-34 - 丄JOl/UCO modified propoxy fluorenyl) acetylene urea, N, N, N, N-tetrakis (n-butylbutoxycarbonyl) acetylene urea Oxydecyl)acetylene urea, N,N,N,N•tetra(n-, n, n, n, n-tetrakis(isopropoxymethyl)ethylglyoxymethyl)acetylene urea, N, N, N, N-four (third grade, etc. ~, and in the transport of some N-(alkoxycarbonyl)-ethyl MM χτ χτ, in the block gland compound 'preferably Ν, Ν, Ν, Ν-four ( Methoxy methoxy) acetylene urea. &amp; As the above N-(alkoxymethyl)=)-c cyanamide compound, for example, N, N, N, N, N, N-hexa曱4 fw Μ Μ Μ XT XT xr 1 Y-oxyindenyl) melamine, N, N, N, N, N, N-hexa(ethoxymethyl) di- &&gt;) - decylamine, n,n,n,n,n,n- ✓, (n-propoxy fluorenyl) melamine, », , , ^ N,N,N,N,N,N-hexa(isopropoxy Methyl)-I murine amine, N,N,N,N,NN-丄'/w _ χτx ,,w 〇(n-butoxymethyl)melamine, hydrazine, hydrazine, hydrazine, hydrazine, hydrazine, hydrazine- Six (three-stage Ding Yimei j ritual methyl) melamine and the like. Among these N-(alkoxy fluorenyl-based broad-armed soil) agglomerated amine compounds, preference is given to the dimerization of ruthenium, osmium, iridium, osmium, N,N-hexa(methoxymethyl- &amp; methyl). Cyanamide, as a commercially available product, may, for example, be nicarac ν_2702 or leg alac MW-30M (the above products are manufactured by Sanwa Chemical (4)). Examples of the compound having two or more epoxy groups I include ethylene glycol diglycidyl glycerol, bis-ethylene glycol diglycidyl propylene glycol, and polyethylene glycol diglycidyl propylene glycol. -start π - % - glycidyl ether, tripropylene glycol diglycidyl ether, polypropylene - hydrazine - hydrazine, monoglycidyl glycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hex-fluorene-starter | · Know a glycidyl ether, glycerol II, glycidyl bond, trimethyl propylene trihydrate H / Tian Yue, Jiayu Shuanglian A diglycidyl ether, bisphenol A diglycidyl ether, etc. Commercially available products of two or more epoxy-based compounds include, for example, Iporato 40E, Ibolato, Ibolato-35·U80065, and the second 〇〇E, Ibolato 7〇P, Ipoto 2〇〇p, Ibolato 4〇〇p, Ibolato 1 500NP, Ibolato 16〇〇, Iporato 8〇]^1?, Ibolato 100MF, Ibolato 3002, Ebolato 4 〇〇〇 (The above products are manufactured by Gongrongshe Chemical Co., Ltd.). These heat resistance improvers may be used singly or in combination of two or more. .

本發月的放射線敏感性樹脂組合物，較佳為將其溶 解於適當的溶劑令，製成組合物溶液後使用。The radiation sensitive resin composition of the present month is preferably prepared by dissolving it in an appropriate solvent to prepare a composition solution.

作為上述的溶劑，可以使用那些能均勻溶解構成放 射線敏感性樹脂組合物的各成分、不與各成分反應並且 具有適度揮發性的溶劑。 作為廷樣的溶劑的例可以舉出與關於製造共 物[A]的聚合技術中所例示的同樣的溶劑。 A 在這些溶劑中，從各成分的溶解能力As the above solvent, those which can uniformly dissolve the components constituting the radiation sensitive resin composition, do not react with the respective components, and have moderate volatility can be used. Examples of the solvent of the sample are the same solvents as those exemplified for the polymerization technique for producing the compound [A]. A. The solubility of each component in these solvents

反隸和易於形成被瞑等角度考慮，較佳為醇類、二 …，基峻乙酸δ旨類、二乙二醇一院基喊乙酸酿類 一乙-醇烷基醚類、丙二醇一烷基醚乙酸 …基醋類等，更佳為笨甲醇、2_苯乙醇、3_;基氧 丙醇、乙二醇一 π1 丁： 丁基醚乙酸酯、二乙二醇一乙基喊 i曰、-乙二醇二甲醚、二乙 基甲基醚、丙二醇—田I 一&amp;一_ 酸酯等。 甲基醚乙酸酯、丙二醇-乙基啊 此 劑一起並用 41以早獨使用或者2種以上混合使用 卜在本發明中，還可以將上述溶劑 並用。 〃 -36- 1380065 修；本 作為上述的高沸點溶劑，例如可以舉出：N-肀 &gt; 乙 醯胺、Ν，Ν·二甲基甲醯胺、N-甲基甲醯苯胺、N-f基 ^ λ ίβ. 醯胺、Ν，Ν·二甲基乙醯胺、Ν-甲基吡咯烷酮、；τ 己 、苄基乙基醚、二己基醚、丙酮基丙酮、異佛爾綱’ Α*5 、 酸、辛酸、1-辛醇、1·壬醇、乙酸苄酯、苯甲酸乙 • 草酸一乙S旨、馬來酸二乙醋、7* -丁内自旨、碳酸变 碳酸亞丙酯、笨基溶纖劑乙酸酯等。 * 合^(氣 這些高沸點溶劑可以單獨使用或者2種以上妙 鲁用。 在右 這樣製備的組合物溶液，還可以用孔徑〇 · 5 &quot; 的微孔過濾器過濾後使用。 隔物的形成方法 &gt;身勿來 下面說明使用本發明的放射線敏感性樹脂·组β 形成本發明的間隔物的方法。 /4) 形成本發明的間隔物的方法至少包含下述（1)〜 的步驟。 φ (1)在基板上形成本發明的放射線敏感性樹脂組合 物的被膜的步驟； - (2)對該被膜的至少一部分用放射線進行曝光的步 驟， (3) 將曝光後的上述被膜顯影的步驟； (4) 將顯影後的上述被膜加熱的步驟。 下面依次而言明上述的各步驟。 —步驟（1)一 在透明基板的一個側面上形成透明導電膜，在該透 -37- 1380065 修正本 明導電膜上塗布本發明的放射線敏感性樹脂組合物的組 合物溶液’然後通過將該塗布面加熱（預烘烤）來形成被 膜。 作為在形成間隔物時使用的透明基板，例如可以舉 •出玻璃基板、樹脂基板等’更具體地可以舉出鹼石灰玻 -璃、無鹼玻璃等的玻璃基板；由聚對笨二甲酸二乙二醇 西a、水對苯_曱酸丁二醇醋、聚醚礙、聚碳酸酯、聚酿 亞胺等的塑膠製成的樹脂基板。Relief and easy to form bedding, etc., preferably alcohol, two..., base acid acetic acid δ, diethylene glycol, one hospital, acetic acid brewing, one ethyl alcohol alkyl ether, propylene glycol mono Ethyl ether acetic acid, vinegar, etc., more preferably stupid methanol, 2-phenylethyl alcohol, 3_; oxypropanol, ethylene glycol-π1 butane: butyl ether acetate, diethylene glycol monoethyl曰, - ethylene glycol dimethyl ether, diethyl methyl ether, propylene glycol - Tian I &amp; mono-acid ester, and the like. The methyl ether acetate and the propylene glycol-ethyl group may be used in combination with each other or in combination of two or more. In the present invention, the above solvents may be used in combination. 〃 -36- 1380065 修; The above-mentioned high-boiling point solvent, for example, N-肀&gt; acetamamine, hydrazine, hydrazine dimethylformamide, N-methylformanilide, Nf-based ^ λ ίβ. decylamine, hydrazine, hydrazine dimethyl acetamide, hydrazine-methylpyrrolidone, τ hexyl, benzyl ethyl ether, dihexyl ether, acetone acetone, isophora Α *5 , acid, caprylic acid, 1-octanol, 1-decyl alcohol, benzyl acetate, ethyl benzoic acid, oxalic acid, ethyl sulphate, maleic acid, diethyl sulphate, 7*-butylene, carbonic acid propylene carbonate , Stupid cellosolve acetate and the like. * Combine (the gas can be used alone or in combination of two or more kinds. The composition solution prepared on the right side can also be filtered by a microporous filter with a pore size of 〇·5 &quot; Forming Method&gt; The method of forming the spacer of the present invention using the radiation sensitive resin group β of the present invention will be described below. /4) The method of forming the spacer of the present invention includes at least the following steps (1) to . Φ (1) a step of forming a film of the radiation sensitive resin composition of the present invention on a substrate; - (2) a step of exposing at least a part of the film to radiation, and (3) developing the film after exposure. Step; (4) a step of heating the developed film after development. The above steps will be described in order below. a step (1) of forming a transparent conductive film on one side of the transparent substrate, and applying a composition solution of the radiation-sensitive resin composition of the present invention on the conductive film of the modified -37- 1380065 The coated surface is heated (prebaked) to form a film. Examples of the transparent substrate to be used for forming the spacer include a glass substrate, a resin substrate, and the like. More specifically, a glass substrate such as soda lime glass or alkali-free glass may be mentioned; A resin substrate made of a plastic such as ethylene glycol a, water-to-benzoic acid butanediol vinegar, polyether barrier, polycarbonate, or polyacrylonitrile.

•作為s又置在透明基板的一個侧面上的透明導電膜， 例如可以舉出由氧化錫（Sn〇2)形成的NESA膜（美國ppG 公司注冊商標）、由氧化銦-氧化錫（In2〇3_Sn〇2)形成的 ITO膜等。 作為組合物溶液的塗布方法，例如可以採用喷塗法 、輥塗法、旋轉塗法、狹縫模塗法、刮條塗法、喷墨塗 法專適宜的方法，較佳為旋轉塗法、狹縫模塗法。 另外’預烘烤的條件隨各成分的種類、混合比例等 籲的不同而異，但通常是在70〜12(rc的溫度下進行1〜15 分鐘左右。 一步驟（2) — 進而，對已形成的被膜的至少一部分用放射線進行 曝光。在此情況下，在對被膜的一部分進行曝光時，一 身又疋通過一種具有規疋的圖案的光罩進行曝光。 作為適用的放射、線’可以使用可見光線、紫外線、 遠紫外線、電子射線、X射線等，但較佳為波長在1 9〇〜 450nm範圍内的放射線，特別是含有波長為365nm的紫外 -38- 1380065 修正本 線的放射線為宜。 以使用照度計（0AI model 365，oaI Optical Associates公司製）測定的曝光放射線的波長為365nm的 光強度作為曝光量的值，該曝光量通常為ι〇〇〜 10,000J/m2，较佳為 5〇0 〜3 00〇j/m2。 一步驟（3 ) — ’從而形成預定的圖案• A transparent conductive film which is placed on one side of a transparent substrate as s, for example, a NESA film formed of tin oxide (Sn〇2) (registered trademark of ppG, USA), and indium oxide-tin oxide (In2〇) 3_Sn〇2) formed ITO film or the like. As a coating method of the composition solution, for example, a spray coating method, a roll coating method, a spin coating method, a slit die coating method, a bar coating method, or an inkjet coating method may be employed, and a spin coating method is preferred. Slot die coating method. In addition, the conditions for pre-baking vary depending on the type of each component, the mixing ratio, etc., but usually at 70 to 12 (about 1 to 15 minutes at rc temperature). One step (2) - further, At least a part of the formed film is exposed by radiation. In this case, when a part of the film is exposed, it is exposed through a mask having a regular pattern. As a suitable radiation, the line can be Use visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray, etc., but preferably radiation having a wavelength in the range of 19 〇 to 450 nm, especially ultraviolet ray having a wavelength of 365 nm to correct the radiation of the line. The light intensity of the exposure radiation having a wavelength of 365 nm measured by using an illuminometer (0AI model 365, manufactured by OaI Optical Associates Co., Ltd.) is used as the value of the exposure amount, and the exposure amount is usually ι 〇〇 10,000 J/m 2 , preferably 5〇0 ～3 00〇j/m2. One step (3) — ' thereby forming a predetermined pattern

作為適用於顯影的顯影液，例如可以使用氫氧化鈉 、氫氧化鉀、碳酸鈉、矽酸鈉、偏矽酸鈉、氨等的無機 驗類乙胺正丙胺等的脂肪族一級胺類；二乙胺、二 正丙胺等的脂肪族二級胺類；三甲胺、甲基二乙基胺、 一曱基乙基胺、三乙胺等的脂肪族三級胺類；吡咯、呱 口秦、N-曱基吸唪、·^ 条N-曱基°比咯烷、1,8-二氮雜雙環 [5.4.0]-7-十一碳烯、1 一虱雜雙裱[4·3.〇]-5-壬烯等的 脂ί哀族三級胺類；吡 二 _ 姑 疋一〒暴比01、一甲基。比啶、喹As the developer suitable for development, for example, an aliphatic primary amine such as inorganic test such as ethylamine n-propylamine such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate or ammonia can be used; Aliphatic secondary amines such as ethylamine and di-n-propylamine; aliphatic tertiary amines such as trimethylamine, methyldiethylamine, monodecylethylamine and triethylamine; pyrrole, gargle, N-fluorenyl hydrazine, ·^ N-mercapto-pyrrolidine, 1,8-diazabicyclo[5.4.0]-7-undecene, 1 azaindole [4·3 .〇]-5-decene and other lipids 哀 族 tri-amines; pyridinium 疋 〒 〒 〒 〒 01 01 01 01 01 01 01 01 01 01 01 01 Bisidine

進而逋過將曝光後的 啉等的芳香族三級胺錮 ，一曱基乙醇胺、曱基二乙醇胺 、三乙醇胺等的烷醇脸翻0酥妝Further, an aromatic tertiary amine such as a porphyrin after exposure, an alkanol face such as monodecylethanolamine, decyldiethanolamine or triethanolamine is turned over.

知胺類，虱氧化四甲銨、氫氧化四乙 銨等四級銨鹽等的於w 人L ^孔化四G 哥的鹼性化合物的水溶液。 另外也可以向上述的驗 適當量的甲醇、乙醇耸w 。物的水办液中添加 劑後使用。 ㈣機溶或界面活性 顯影的方法可以是流液法、 任 種，顯影的時門s —又/貝法、喷淋法等中的 g§ „ 衧間通常是在常溫下1〇〜180秒。 顯影後，例如；隹am 。 ^ 〜0秒鐘的流水沖洗，然後例 -39- 1380065 修正本 如用壓縮空氣或壓縮氮氣進行風乾 案0 從而形成所需的圖 一步驟（4)一An aqueous solution of a basic compound such as a tetra-ammonium salt such as tetramethylammonium oxide or tetraethylammonium hydroxide or the like. Alternatively, an appropriate amount of methanol or ethanol may be used as described above. It is used after adding the agent to the water solution of the object. (4) The method of machine-soluble or interfacial activity development may be a fluid-flow method, any kind, and the development time of the gate s--/bebe method, spray method, etc. g § 衧 usually at room temperature for 1 〇 to 180 seconds After development, for example; 隹am. ^~0 seconds of running water rinse, then example -39- 1380065 amendments such as using compressed air or compressed nitrogen to air dry the case 0 to form the desired figure one step (4) one

進 案在規 如在電 鐘，如 以 物如果 所獲的 射線敏 結果不 度、液 而，使用 疋的溫度 熱板上加 此進行加 往在形成 不在1 8 0 〃 間隔物就 感性樹脂 會導致樹 晶配向時 電熱板或烘箱等加熱裝I，將所獲的圖 例如100〜16(TC下加熱規定的時間例 熱5〜30分鐘，在烘箱中加熱3〇〜18〇分 熱（後烘烤），從而獲得所需的間隔物。 間隔物時使用的放射線敏感性樹脂組合 ^ 200°C左右以上的溫度進行加熱處理， 不能獲得充分的性能’但是本發明的放 組合物可使用比以往低的加熱溫度，且 脂基板的變黃或變形’並能獲得抗壓強 的耐摩擦性、與透明基板的黏附性等的 各種性能均優良的間隔物。 液晶顯示元# 本發明的液晶顯示元件具有如上述那樣形成的本發 鲁明的間隔物。 作為液晶顯示元件的結構沒有特殊限定，但是可以 舉出如第1圖所示那樣的結構，該結構是在透明基板上形 成彩色濾光片和本發明的間隔物，並具有通過液晶層配 置的兩片配向膜、相互對向的透明電極、相互對向的透 明基板等而形成的結構。另外，如第1圖所示，也可以根 據需要’在偏光板或彩色濾光片上設置保護膜。 如第2圖所示，在透明基板上形成彩色濾光片和本發 明的間隔物，並通過配向膜和液晶層而與薄膜電晶體 -40- i3_65 修正本 (TFT)陣列對向’這樣也可以構成TN-TFT型的液晶顯示 元件。在此情況下，也可以根據需要’在偏光板或在彩 色濾光片上設置保護膜。 本發明的間隔物形成用放射線敏感性樹脂組合物可 以抑制由於放射線敏感性聚合引發劑成分的昇華所造成 的繞成爐或光罩等的污染，不會產生液體中的異物，而 且具有高的靈敏度和高的圖像解析度，同時能夠容易地 0形成一種斷面形狀、抗壓強度、耐摩擦性、與透明基板 的點附性等各種性能均優良的間隔物，並且在形成間隔 物時可以降低後烘烤的溫度，不會導致樹脂基板的變黃 或變形。 本發明的液晶顯示元件由於具有一種斷面形狀、抗 壓強度、耐摩擦性、與透明基板的黏附性等各種性能均 優良的間隔物’因此可以長期地確保高的可靠性。 【實施方式】 下面舉出實施例來更具體而言明本發明的實施方式。 鲁合成例1 在帶有冷卻管和攪拌器的燒瓶中裝入2,2，_偶氮二 (2,4-二甲基戊腈）5重量份和二乙二醇乙基甲基醚25〇重 里份，接著裝入甲基丙烯酸17重量份、甲基丙烯酸縮水 甘油酯45重量份、苯乙烯20重量份和甲基丙烯酸二環戊 Sa 1 8重里伤’用氮氣置換後，—面緩慢地攪拌，一面使 =液的溫度上升至70乞，保持這—溫度4小時使之聚合， 件到含共聚物[A]的樹脂溶液（固體成分濃度=28 4重量 °/〇) °該共聚物[A]的Mw為1 6,000。 -41 - 1380065 修正本 將該共聚物[A ]稱為“共聚物（a _ 1)，，。 使用GPC(凝膠滲透色譜）HLC8〇2〇(東梭（股）製 (TOSOH))測定共聚物（A-1)和下述聚合物（α·2)的Mw。 合成例2 ’ 在帶有冷卻管和攪拌器的燒瓶中裝入2,2，·偶氮二 .(2,4 -二甲基戊腈）7重量份和二乙二醇乙基甲基醚250重 量份’接著裝入曱基丙烯酸18重量份、曱基丙烯酸縮水 甘油酯20重量份、苯乙烯5重量份、甲基丙烯酸二環戊酯 ’ 32重量份和曱基丙烯酸四氫糠酯25重量份，用氮氣置換 後一面缓慢地授拌’一面使溶液的溫度上升至7 〇 °c，保 持這一溫度4小時使之聚合，得到含有共聚物[A]的樹脂 /谷液（固體成分濃度=28.8重量％)。該共聚物[A]的Mw是 1 1,000 ° 將該共聚物[A]稱為“共聚物（A-2)，，。 實施例1 —組合物溶液之製備— • 將作為[A]成分而在合成例1中獲得的樹脂溶液作為 共聚物（A—1 )，以其加入量作為1 〇〇重量份（固體成分）、作 為[B]成分的二四級戊四醇六丙烯酸酯（商品名 KAYARAD DPHA、日本化藥（股）製造）80重量份以及作為 [C]成分的2-(4-曱基苄基）_2_(二甲胺基）-丨气心咮啉并苯 基）丁烧-1-酮（商品名IRGACURE 3 79,汽巴精業化學公司 製M0重量份、作為黏結助劑的r -環氧丙氧基丙基三甲 氧基石夕烧5重量份、作為界面活性劑的丁二烯ρτχ·2ΐ8產 品0.5重量份、作為保存劑的4甲氧基笨酚〇 5重量份混合 -42- 1380065 修正本 ’按固體成分濃度成為3〇重量％的比例溶解於丙二醇甲 基醚乙酸醋中，然後用孔徑0.5/Zm的微孔過慮器過遽， 製成組合物溶液。 一形成間隔物一 . 使用離心塗布機在無鹼玻璃基板上塗布上述組合物 •溶液，然後在電熱板上於8(TC下預烘烤3分鐘，形成膜厚 6 · 〇 // m的被膜。 接著，通過具有10//m正方形殘留圖案的光罩使 馨用波長為365nm、曝光強度為250W/m2的紫外線對所得被 膜進行10秒鐘的曝光。然後用〇〇5重量％的氫氧化鉀水溶 液在25 C下顯影60秒，用純水洗滌【分鐘。然後將其放入 烘箱中，在15CTC下進行120分鐘的後烘烤，形成規定圖 案的間隔物。 然後按下述（I)〜（VIII)的順序進行評價，評價結果 示於表2-1中β (I) 靈敏度的評價 φ 在形成間隔物時，以顯影後的殘膜率（顯影後的膜厚 X 100/初始膜厚，以下相同）達到9〇%的曝光量作為靈敏度 。以該曝光量為L500 j/m2以下時的靈敏度為良好。 (II) 圖像解析度的評價 在形成間隔物時，根據顯影後殘膜率為90%以上的 曝光量按照最小圖案尺寸法進行評價。 (III) 間隔物斷面形狀的評價 使用掃描電子顯微鏡觀察所得間隔物的斷面形狀， 根據其形狀相當於第3圖中所示的a-D中的某一種進行 -43- 1380065 修正本In the case of the electric clock, if the result of the ray sensitivity obtained by the object is not enough, the liquid is added to the hot plate using 疋, and the addition is made to the spacer which is not formed in the 180 〃 spacer. When the crystal is aligned, a heating plate such as a hot plate or an oven is used, and the obtained image is, for example, 100 to 16 (heated under TC for a predetermined period of time for 5 to 30 minutes, and heated in an oven for 3 to 18 minutes. Baking) to obtain a desired spacer. The radiation-sensitive resin combination used in the spacer is heat-treated at a temperature of about 200 ° C or higher, and sufficient performance cannot be obtained'. However, the composition of the present invention can be used. In the conventionally, a low heating temperature and a yellowing or deformation of a fat substrate are obtained, and a spacer excellent in various properties such as abrasion resistance against abrasion and adhesion to a transparent substrate can be obtained. Liquid crystal display element # Liquid crystal of the present invention The display element has the spacer of the present invention formed as described above. The configuration of the liquid crystal display element is not particularly limited, but a structure as shown in Fig. 1 may be mentioned. A color filter and a spacer of the present invention are formed on the substrate, and have a structure in which two alignment films are disposed through the liquid crystal layer, transparent electrodes facing each other, transparent substrates facing each other, and the like. As shown in Fig. 1, a protective film may be provided on a polarizing plate or a color filter as needed. As shown in Fig. 2, a color filter and a spacer of the present invention are formed on a transparent substrate, and passed through an alignment film. And the liquid crystal layer and the thin film transistor -40-i3_65 correction (TFT) array alignment "this can also constitute a TN-TFT type liquid crystal display element. In this case, it can also be used in a polarizing plate or in color as needed. A protective film is provided on the filter. The radiation-sensitive resin composition for spacer formation of the present invention can suppress contamination of a furnace or a mask due to sublimation of a radiation-sensitive polymerization initiator component, and does not generate a liquid. The foreign matter in the middle, and has high sensitivity and high image resolution, and can easily form a cross-sectional shape, compressive strength, abrasion resistance, and a point with a transparent substrate. A spacer having excellent properties such as an adhesive property, and the temperature of the post-baking can be lowered when the spacer is formed, and does not cause yellowing or deformation of the resin substrate. The liquid crystal display element of the present invention has a sectional shape and is resistant. The spacers excellent in various properties such as compressive strength, abrasion resistance, and adhesion to a transparent substrate can ensure high reliability for a long period of time. [Embodiment] Hereinafter, an embodiment will be described to more specifically describe the implementation of the present invention. The synthesis method 1 In a flask equipped with a cooling tube and a stirrer, 5 parts by weight of 2,2,-azobis(2,4-dimethylvaleronitrile) and diethylene glycol ethylmethyl group were charged. 25 parts by weight of ether, followed by 17 parts by weight of methacrylic acid, 45 parts by weight of glycidyl methacrylate, 20 parts by weight of styrene and dicyclopentane methacrylate methacrylate. After being replaced with nitrogen, The surface was slowly stirred, and the temperature of the liquid was raised to 70 Torr. The temperature was maintained for 4 hours to polymerize the mixture into a resin solution containing the copolymer [A] (solid content concentration = 28 4 weight ° / 〇) ° The copolymer [A] had a Mw of 16,000. -41 - 1380065 The copolymer [A] is referred to as "copolymer (a _ 1), and is determined by GPC (gel permeation chromatography) HLC8 〇 2 〇 (manufactured by Tosoh Corporation) Mw of the copolymer (A-1) and the following polymer (α·2). Synthesis Example 2 'In a flask equipped with a cooling tube and a stirrer, 2,2,·Azo2. (2,4) was charged. - dimethyl valeronitrile) 7 parts by weight and diethylene glycol ethyl methyl ether 250 parts by weight 'subject 18 parts by weight of methacrylic acid, 20 parts by weight of glycidyl methacrylate, 5 parts by weight of styrene, 32 parts by weight of dicyclopentanyl methacrylate and 25 parts by weight of tetrahydrofurfuryl methacrylate, slowly mixed with nitrogen, and the temperature of the solution was raised to 7 〇 ° C, maintaining this temperature 4 The polymer/valley solution (solid content concentration = 28.8% by weight) containing the copolymer [A] was obtained in an hour. The Mw of the copolymer [A] was 1 1,000 °. The copolymer [A] was referred to as "copolymerization". (A-2),,. Example 1 - Preparation of Composition Solution - The resin solution obtained in Synthesis Example 1 as the component [A] was used as the copolymer (A-1) in an amount of 1 part by weight (solid content). 80 parts by weight of quaternary pentaerythritol hexaacrylate (trade name: KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) as component [B] and 2-(4-mercaptobenzyl group) as component [C] _2_(Dimethylamino)-helium porphyrin phenyl)butan-1-one (trade name: IRGACURE 3 79, M0 parts by Ciba Specialty Chemicals Co., Ltd., r-epoxy as adhesion aid) 5 parts by weight of propoxypropyltrimethoxycarbazide, 0.5 parts by weight of butadiene ρτχ·2ΐ8 product as a surfactant, and 5 parts by weight of 4 methoxy phenolphthalein as a preservative - 42- 1380065 The present solution was dissolved in propylene glycol methyl ether acetate vinegar at a ratio of solid content concentration of 3% by weight, and then passed through a microporous separator having a pore size of 0.5/Zm to prepare a composition solution. The above-mentioned composition solution is applied to the alkali-free glass substrate by a centrifugal coater, and then heated The film was pre-baked at 8 (TC for 3 minutes to form a film having a film thickness of 6 · 〇 / / m. Next, a mask having a square residual pattern of 10 / / m was used to make the wavelength of the application 365 nm and the exposure intensity 250 W / The resulting film was exposed to ultraviolet light for 10 seconds, and then developed with a 5% by weight aqueous potassium hydroxide solution at 25 C for 60 seconds, washed with pure water for [minutes, and then placed in an oven at 15 CTC. The post-baking was carried out for 120 minutes to form a spacer having a predetermined pattern. Then, the evaluation was carried out in the order of (I) to (VIII) below, and the evaluation results are shown in Table 2-1 for the evaluation of β (I) sensitivity. When the spacer is formed, the exposure amount after development (the film thickness X 100 after development, the initial film thickness, the same applies hereinafter) reaches an exposure amount of 9% by weight as the sensitivity. When the exposure amount is L500 j/m 2 or less (II) Evaluation of image resolution When a spacer is formed, the exposure amount based on the residual film ratio after development is 90% or more is evaluated by the minimum pattern size method. (III) Evaluation of the cross-sectional shape of the spacer Observing the section of the resulting spacer using a scanning electron microscope The shape is corrected according to the shape of one of the a-Ds shown in Fig. 3 -43- 1380065

評價。此時’如A或B所示，RA 圖案邊緣為正錐形或垂直狀 這兩種情况均表示斷面形狀p^ , 即小狀良好。與此相反，如C所示 ，靈敏度不約好、殘膜查/pf 赵 # %膜革低 '斷面尺寸比Af〇B小、其形 狀為底面呈平面的半凸透鎊 Ό ± 达鏡狀廷一饧況表示斷面形狀 不良。另外’如D所示，圖査遠这&amp; 固案邊緣為倒錐形（在斷面形狀 中，膜表面的邊比基板一側的邊還長的倒三角 這一 情況在後續㈣擦處理時_案被㈣料能性 高， 因而斷面形狀不良。 (IV)抗壓強度的評價 使用微型抗壓試驗機（商品gMCTM 200、島津製作 所（股）製造）測定所得間隔物的抗壓強度，具體而言，在 =°c的溫度下使用直徑50 V m的平面壓頭施加i〇m°N的載 何，測定此時的變形量，當該值在〇 5 # m以下時，表明 抗壓強度良好。， &quot; (V)耐摩擦性的評價 使用液晶配向膜塗布用印刷機在形成了間隔物的基 鲁板上塗布AL3046(商品名、JSR(股）製造）作為液晶取向劑 ，然後在18〇t下乾燥1小時，形成膜厚0_05以m的液晶取 向劑的塗膜。 然後’使用具有纏繞聚醯胺製的布的輥的摩擦機 在輥轉速500 rpm、載物台移動速度lcm/秒的條件下， 該塗膜進行摩擦處理。這時，根據圖案是否被削去或： 離進行評價。 5旬 (VI)黏附性的評價 除了不使用光罩之外，與上述形成間隔物的場入同 -44- 1380065 修正本 樣操作，形成硬化膜。鈇诒 .TTr, m …、後在 JIS Κ-5400(1 900)8.5 的 附著性試驗中，按8 5 · 2的查丨I坆8® ««=丄 • 2的格膠▼法進行評價。這時， 在表2中示出了每ι〇〇個格子中殘留的格子數。 (VII)昇華性的評價 將上述组合物溶液塗布在基板上，然後將其乾燥， 形成了膜厚6.〇Am的被膜。使用正辛烷(比重=〇 7〇1， 注入量：0.02m)作為標準物f，以1〇代/1()分鐘作為清 潔（purge)條件，對上述被膜進行頂空氣相色譜法/品質分 析（頂空取樣器為日本分析工業（股）製的jhsi〇〇a ;氣相 色譜/品質分析裝置為曰本分析工業（股）製的je〇l JMS-AX5G5W型品質分析計），求出來自放射線敏感性聚 合引發劑的峰的面積A，按下述計算式算出按正辛烷換算 的揮發量。該揮發量越大，表明其昇華性越大。 瘦算的揮發晋的計笪式i 揮發量bg) = Αχ(正辛烷的量）（v g)/(正辛烷的峰面積） (VIII)液體中異物的評價 將上述組合物溶液在_丨5 〇C的溫度下保存7天，然後 用目視法觀察其中是否出現放射線敏感性聚合引發劑成 分的再結晶產物。進而，將保存過的上述組合物溶液的 液溫由-1 5°C升高至23°C時，用光散射式液中粒子檢測器 (商品名KS-28B，RION(股）製造）測定在每1#ι中的組合 物溶液中沒有再溶解而殘存下來的0.5 // m以上大小的固 體物（殘存異物）的數目。 實施例2 - 2 3 除了使用表1-1中所示各成分作為[A]成分、[B]成分 -45- 1380065 修正本 和[c]成刀之外，其餘與實施例i同樣操作，配製各組合 物溶液’形成間隔物，進行各種評價。評價結果示於表 2-1 中。 實施例24 • 將與實施例1同樣的各成分溶解在二乙二醇乙基甲 *基醚中，使固體成分濃度成為17.5重量％，然後用孔徑〇.5 // m的微孔過濾器過渡，製成組合物溶液。除此之外， 與實施例1同樣操作，形成間隔物，進行各種評價，評價 籲結果示於表2-1中。 比較例1〜8 除了使用表1-2中所示各成分作為[A]成分、[B]成分 和放射線敏感性聚合引發劑之外，其餘與實施例1同樣操 作，配製各組合物溶液，形成間隔物，進行各種評價。 評價結果示於表2 - 2中。 在表1-1和表1-2中，[A]成分以外的各種成分如下面 所述9 ^ B -1 :二四級戊四醇六丙晞酸酯； B-2 :商品名KAYARAD DPHA-40H(曰本化藥（股）製 造）； C-l :2-(4-甲基苄基）-2-(二甲胺基）-1-(4-味啉并笨基 )丁烷-1-酮； D-l: 1-[9 -乙基-6-(2 -甲基苯甲醯基）-9.Η·-咔唑_3_ 基]-乙烷-1-酮肟乙酸酯（商品名CGI-242，汽巴精業化 學公司製造） Ε-1 : 2-甲基-1-[4-(甲硫基）苯基]-2-咪啉并丙烷- -46 - 1380065 修正本 酮（商品名IRGACURE 907，汽巴精業化學公司製造）； E-2 . 2-卞基- 2- (二甲胺基）-1-(4 -味琳弁苯基）丁烧-1 · 酮（商品名IRGACURE 369，汽巴精業化學公司製造）； E-3 : 1-(2-溴-4-咪啉并苯基）-2-苄基-2-曱胺基-丁烷 -1-酮； F-1 : 2,2’-雙（2,4-二氯苯基）-4,4’，5,5’-四苯基-1，2’-雙咪唑； F-2: 4,4’-雙（二乙胺基）二苯甲酮； F-3 : 2-酼基苯并噻唑。Evaluation. At this time, as shown by A or B, the edge of the RA pattern is a forward taper or a vertical shape, and both of them represent the cross-sectional shape p^, that is, the shape is good. On the contrary, as shown by C, the sensitivity is not good, the residual film inspection / pf Zhao #% film leather low 'section size smaller than Af 〇 B, its shape is a flat surface of the semi-convex Ό Ό ± mirror The situation of the court shows that the shape of the section is poor. In addition, as shown in D, the image of this is the inverted cone (in the cross-sectional shape, the edge of the film surface is longer than the side of the substrate side of the inverted triangle in the subsequent (four) rubbing treatment (4) The material of the case was high (4), and the shape of the cross section was poor. (IV) Evaluation of compressive strength The compressive strength of the obtained spacer was measured using a micro-compression tester (product gMCTM 200, manufactured by Shimadzu Corporation). Specifically, at a temperature of = °c, a plane indenter having a diameter of 50 V m is used to apply the load of i〇m°N, and the amount of deformation at this time is measured. When the value is below 〇5 #m, it indicates (V) Evaluation of the abrasion resistance The AL3046 (trade name, manufactured by JSR) was applied as a liquid crystal aligning agent on a base plate on which a spacer was formed by using a printer for coating a liquid crystal alignment film. Then, it was dried at 18 Torr for 1 hour to form a coating film of a liquid crystal aligning agent having a film thickness of 0 to 05 m. Then, using a friction machine having a roll of a cloth made of polyamidamide at a roller rotation speed of 500 rpm, a stage The coating film is subjected to rubbing treatment under the condition of a moving speed of 1 cm/sec. According to whether the pattern is cut off or: Evaluation is performed. The evaluation of adhesion of the 5th (VI) is the same as the above-mentioned formation of the spacer, except that the mask is not used. -44- 1380065 Correct the operation to form a cured film.鈇诒.TTr, m ..., and then in the adhesion test of JIS Κ-5400 (1 900) 8.5, according to the 8 5 · 2 check I丨8® ««=丄• 2 In this case, the number of lattices remaining per 〇〇 grid is shown in Table 2. (VII) Evaluation of sublimation property The above composition solution was coated on a substrate, and then dried to form a film thickness of 6 . The film of 〇Am. Using n-octane (specific gravity = 〇7〇1, injection amount: 0.02m) as the standard f, the above film was topped with 1〇/1() minutes as a purge condition. Air phase chromatography/quality analysis (headspace sampler is jhsi〇〇a manufactured by Nippon Analytical Industries Co., Ltd.; gas chromatograph/quality analyzer is je〇l JMS-AX5G5W type manufactured by 曰本分析工业有限公司Quality analyzer), the area A of the peak derived from the radiation-sensitive polymerization initiator was determined, and the calculation was performed according to the following calculation formula. The amount of volatilization in terms of octane. The larger the amount of volatilization, the greater the sublimation property. The calculation of the volatilization of volatilization i volatilization amount bg) = Αχ (the amount of n-octane) (vg) / (positive symplectic (VIII) Peak area of the alkene) (VIII) Evaluation of foreign matter in the liquid The above composition solution was stored at a temperature of _丨5 〇C for 7 days, and then visually observed whether or not a recrystallized product of the radiation-sensitive polymerization initiator component appeared therein. . Further, when the liquid temperature of the stored composition solution is raised from -1 to 5 ° C to 23 ° C, it is measured by a light scattering liquid particle detector (trade name: KS-28B, manufactured by RION Co., Ltd.). The number of solids (residual foreign matter) having a size of 0.5 // m or more remaining without re-dissolving in the composition solution per 1#1. Example 2 - 2 3 The same procedure as in Example i was carried out except that each component shown in Table 1-1 was used as the [A] component, [B] component -45-1380065, and [c]. Each of the composition solutions was prepared to form a spacer, and various evaluations were performed. The evaluation results are shown in Table 2-1. Example 24: The same components as in Example 1 were dissolved in diethylene glycol ethyl methyl ether to have a solid content concentration of 17.5% by weight, and then a pore filter having a pore diameter of 5.5 // m was used. The transition is made into a composition solution. Otherwise, a spacer was formed in the same manner as in Example 1, and various evaluations were carried out, and the evaluation results are shown in Table 2-1. Comparative Examples 1 to 8 Each of the composition solutions was prepared in the same manner as in Example 1 except that each component shown in Table 1-2 was used as the component [A], the component [B], and the radiation-sensitive polymerization initiator. A spacer was formed and various evaluations were performed. The evaluation results are shown in Table 2-2. In Table 1-1 and Table 1-2, various components other than the component [A] are as follows: 9 ^ B -1 : quaternary pentaerythritol hexapropionate; B-2 : trade name KAYARAD DPHA -40H (manufactured by Sakamoto Chemical Co., Ltd.); Cl: 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholine-phenyl)butane-1 -ketone; Dl: 1-[9-ethyl-6-(2-methylbenzhydryl)-9.Η·-carbazole_3_yl]-ethane-1-one oxime acetate (product CGI-242, manufactured by Ciba Specialty Chemicals Co., Ltd.) Ε-1 : 2-methyl-1-[4-(methylthio)phenyl]-2-morphopropane--46 - 1380065 (trade name: IRGACURE 907, manufactured by Ciba Specialty Chemicals Co., Ltd.); E-2. 2-Mercapto-2-(dimethylamino)-1-(4-isolinylphenyl)butane-1·ketone (trade name: IRGACURE 369, manufactured by Ciba Specialty Chemicals Co., Ltd.); E-3: 1-(2-bromo-4-morpholinophenyl)-2-benzyl-2-indenyl-butane-1 -ketone; F-1 : 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-bisimidazole; F-2: 4,4'-bis(diethylamino)benzophenone; F-3: 2-mercaptobenzothiazole.

-47- 1380065 修正本 表ι_ι-47- 1380065 Amend this table ι_ι

[A]成分 (重量份） 同成分 (重量份） [C]成分 (重量份） 實施例1 A-1 (100) B-l (80) C-l (30) — 實施例2 A-1 (100) B-l (80) C-l (15) D-l (10) 實施例3 A-1 (100) B-l (80) C-l (25) E-l (10) 實施例4 A-1 (100) B-l (80) C-l (25) F-1/F-2/F-3 (10/10/5) 實施例5 A-1 (100) B-l (80) C-l (15) E-l (10) F-1/F-2/F-3 (10/10/5) 實施例6 A-1 (100) B-l (80) C-l (20) D-l (10) E-l (10) 實施例7 A-1 (100) B-l (80) C-l (10) D-l (10) E-l (10) F-1/F-2/F-3 (10/10/5) 實施例8 A-1 (100) B-l/B-2 (90/10) C-l (30) — 實施例9 A-1 (100) B-l/B-2 (90/10) C-l (15) D-l (10) 實施例10 A-1 (100) B-l/B-2 (90/10) C-l (25) E-l (10) 實施例11 A-1 (100) B-l/B-2 (90/10) C-l(25) F-1/F-2/F-3 (10/10/5) 實施例12 A-1 (100) B-l/B-2 (90/10) C-l (15) E-l (10) F-1/F-2/F-3 (10/10/5) 實施例13 A-1 (100) B-l/B-2 (90/10) C-l(20) D-l (10) E-l (10) 實施例14 A-1 (100) B-l/B-2 (90/10) C-l (10) D-l (10) E-l (10) F-1/F-2/F-3 (10/10/5) 實施例15 A-2(100) B-l/B-2 (80/20) C-l (30) — 實施例16 A-2(100) B-l/B-2 (80/20) C-l (15) D-l (10) 實施例17 A-2(100) B-l/B-2 (80/20) C-l (25) E-l (10) 實施例18 A-2(100) B-l/B-2 (80/20) C-l (25) F-1/F-2/F-3 (10/10/5) 實施例19 A-2(100) B-l/B-2 (80/20) C-l (15) E-l (10) F-1/F-2/F-3 (10/10/5) 實施例20 A-2(100) B-l/B-2 (80/20) C-l (20) D-l (10) E-l (10) 實施例21 A-2(100) B-l/B-2 (80/20) C-l(10) D-l (10) E-l (10) F-1/F-2/F-3 (10/10/5) 實施例22 A-1 (100) B-l (80) C-l (10) E-l/E-2 (10/10) F-1/F-2/F-3 (10/10/5) 實施例23 A-1 (100) B-l (80) C-l(15) D-l (10) E-l/E-2 (10/10) 實施例24 A-1 (100) B-l (80) C-l (30) — -48- 1380065 修正本[A] component (parts by weight) the same component (parts by weight) [C] component (parts by weight) Example 1 A-1 (100) Bl (80) Cl (30) - Example 2 A-1 (100) Bl (80) Cl (15) Dl (10) Example 3 A-1 (100) Bl (80) Cl (25) El (10) Example 4 A-1 (100) Bl (80) Cl (25) F -1/F-2/F-3 (10/10/5) Example 5 A-1 (100) Bl (80) Cl (15) El (10) F-1/F-2/F-3 ( 10/10/5) Example 6 A-1 (100) Bl (80) Cl (20) Dl (10) El (10) Example 7 A-1 (100) Bl (80) Cl (10) Dl ( 10) El (10) F-1/F-2/F-3 (10/10/5) Example 8 A-1 (100) Bl/B-2 (90/10) Cl (30) - Example 9 A-1 (100) Bl/B-2 (90/10) Cl (15) Dl (10) Example 10 A-1 (100) Bl/B-2 (90/10) Cl (25) El ( 10) Example 11 A-1 (100) Bl/B-2 (90/10) Cl(25) F-1/F-2/F-3 (10/10/5) Example 12 A-1 ( 100) Bl/B-2 (90/10) Cl (15) El (10) F-1/F-2/F-3 (10/10/5) Example 13 A-1 (100) Bl/B -2 (90/10) Cl(20) Dl (10) El (10) Example 14 A-1 (100) Bl/B-2 (90/10) Cl (10) Dl (10) El (10) F-1/F-2/F-3 (10/10/5) Example 15 A-2(100) Bl/B-2 (80/20) Cl (30) — Example 16 A-2(100) Bl/B-2 (80/20) Cl (15) Dl (10) Example 17 A-2(100) Bl/B-2 (80/20) Cl (25) El (10) Example 18 A-2 (100) Bl/B-2 (80/20) Cl (25) F-1/F-2/F-3 (10/10/5) Example 19 A- 2(100) Bl/B-2 (80/20) Cl (15) El (10) F-1/F-2/F-3 (10/10/5) Example 20 A-2(100) Bl /B-2 (80/20) Cl (20) Dl (10) El (10) Example 21 A-2(100) Bl/B-2 (80/20) Cl(10) Dl (10) El ( 10) F-1/F-2/F-3 (10/10/5) Example 22 A-1 (100) Bl (80) Cl (10) El/E-2 (10/10) F-1 /F-2/F-3 (10/10/5) Example 23 A-1 (100) Bl (80) Cl(15) Dl (10) El/E-2 (10/10) Example 24 A -1 (100) Bl (80) Cl (30) — -48- 1380065 Revision

表1-2 [A]成分 (重量份） [B]成分 (重量份） 放射線敏感性聚合引發劑 (重量份） 比較例1 A-1 (100) B-1 (80) — E-1 (30) 比較例2 A-1 (100) B-1 (80) — E-1 (10) 比較例3 A-1 (100) B-1 (80) — E-1 (30) F-1/F-2/F-3 (5/5/2.5) 比較例4 A-1 (100) B-1 (100) — D-1 (5) E-1 (30) 比較例5 A-1 (100) B-1 (80) — D-1 (5) E-1 (30) F-1/F-2/F-3 (5/5/2.5) 比較例6 A-1 (100) B-1/B-2 (90/10) — D-1 (5) E-1 (30) F-1/F-2/F-3 (5/5/2.5) 比較例7 A-1 (100) B-1 (80) 一 E-2 (30) 比較例8 A-1 (100) B-1 (80) — E-3 (30) -49- 1380065 修正本Table 1-2 [A] component (parts by weight) [B] component (parts by weight) Radiation-sensitive polymerization initiator (parts by weight) Comparative Example 1 A-1 (100) B-1 (80) - E-1 ( 30) Comparative Example 2 A-1 (100) B-1 (80) - E-1 (10) Comparative Example 3 A-1 (100) B-1 (80) - E-1 (30) F-1/ F-2/F-3 (5/5/2.5) Comparative Example 4 A-1 (100) B-1 (100) — D-1 (5) E-1 (30) Comparative Example 5 A-1 (100 B-1 (80) — D-1 (5) E-1 (30) F-1/F-2/F-3 (5/5/2.5) Comparative Example 6 A-1 (100) B-1 /B-2 (90/10) — D-1 (5) E-1 (30) F-1/F-2/F-3 (5/5/2.5) Comparative Example 7 A-1 (100) B -1 (80) E-2 (30) Comparative Example 8 A-1 (100) B-1 (80) — E-3 (30) -49- 1380065 Revision

表2-1 靈敏度 (J/m2) 圖像 解析度 (μηι) 斷面 形狀 抗壓 強度 耐摩 擦性 黏附性 昇華性 ㈣） 液中異物 再結晶化物 殘存異物 的數目 實施例1 3,000 12 A 0.29 無 100 0 無 0 實施例2 1,300 8 A 0.30 無 100 0 無 0 實施例3 2,800 10 B 0.47 無 100 0 無 0 實施例4 2,000 8 B 0.45 無 100 0 無 0 實施例5 1,500 10 B 0.52 無 100 0 無 0 實施例6 1,100 8 A 0.32 無 100 0 無 0 實施例7 1,000 8 A 0.25 無 100 0 無 0 實施例8 2,700 12 A 0.27 無 100 0 無 0 實施例9 1,100 8 A 0.28 無 100 0 無 0 實施例10 2,500 12 B 0.48 無 100 0 無 0 實施例11 1,800 10 B 0.47 無 100 0 無 0 實施例12 1,400 10 B 0.45 無 100 0 無 0 實施例13 1,000 8 A 0.26 無 100 0 無 0 實施例14 800 8 A 0.28 無 100 0 無 0 實施例15 2,500 10 A 0.27 無 100 0 無 0 實施例16 1,000 8 A 0.25 無 100 0 無 0 實施例17 2,200 8 A 0.26 無 100 0 無 0 實施例18 1,600 8 A 0.26 無 100 0 無 0 實施例19 1,000 8 A 0.25 無 100 0 無 0 實施例20 700 8 A 0.28 無 100 0 無 0 實施例21 600 8 A 0.25 無 100 0 無 0 實施例22 1,3〇〇 10 A 0.32 無 100 0 無 0 實施例23 900 8 A 0.26 無 100 0 無 0 實施例24 3,000 11 A 0.30 無 100 0 無 0 -50- 1380065 修正本 表2-2 靈敏度 (J/m2) 圖像 解析度 ㈣ 斷面 形狀 抗壓 強度 耐摩 擦性 黏附性 昇華性 (Rg) 液中異物 再結晶化物 殘存異物 的數目 比較例1 3,000 12 C 0.77 有 80 1.2 無 0 比較例2 4,000 12 C 0.91 有 60 0 無 0 比較例3 2,700 10 A 0.36 無 100 1.2 無 0 比較例4 2,500 8 D 0.32 有 80 1.1 無 0 比較例5 800 8 B 0.51 無 100 1.1 無 0 比較例6 800 8 B 0.56 100 1.1 無 0 比較例7 2,900 12 A 0.31 無 100 0 有 300 比較例8 5,200 12 A 0.34 無 100 0 有 450Table 2-1 Sensitivity (J/m2) Image resolution (μηι) Cross-sectional shape Compressive strength Friction-resistant Adhesive sublimation (4) Number of foreign matter remaining in liquid recrystallized recrystallized Example 1 3,000 12 A 0.29 None 100 0 No 0 Example 2 1,300 8 A 0.30 No 100 0 No 0 Example 3 2,800 10 B 0.47 No 100 0 No 0 Example 4 2,000 8 B 0.45 No 100 0 No 0 Example 5 1,500 10 B 0.52 No 100 0 None 0 Example 6 1,100 8 A 0.32 No 100 0 No 0 Example 7 1,000 8 A 0.25 No 100 0 No 0 Example 8 2,700 12 A 0.27 No 100 0 No 0 Example 9 1,100 8 A 0.28 No 100 0 No 0 Example 10 2,500 12 B 0.48 No 100 0 No 0 Example 11 1,800 10 B 0.47 No 100 0 No 0 Example 12 1,400 10 B 0.45 No 100 0 No 0 Example 13 1,000 8 A 0.26 No 100 0 No 0 Example 14 800 8 A 0.28 None 100 0 No 0 Example 15 2,500 10 A 0.27 No 100 0 No 0 Example 16 1,000 8 A 0.25 No 100 0 No 0 Example 17 2,200 8 A 0.26 No 100 0 No 0 Example 18 1,600 8 A 0.26 None 100 0 No 0 Example 19 1,000 8 A 0.25 No 100 0 none 0 embodiment 20 700 8 A 0.28 no 100 0 no 0 Example 21 600 8 A 0.25 no 100 0 no 0 Example 22 1,3〇〇10 A 0.32 No 100 0 No 0 Example 23 900 8 A 0.26 None 100 0 No 0 Example 24 3,000 11 A 0.30 No 100 0 No 0 -50- 1380065 Correction Table 2-2 Sensitivity (J/m2) Image Resolution (4) Section Shape Compressive Strength Friction Resistance Adhesion Sublimation The number of foreign matter remnants remaining in the (Rg) liquid. Comparative Example 1 3,000 12 C 0.77 80 1.2 No 0 Comparative Example 2 4,000 12 C 0.91 Yes 60 0 No 0 Comparative Example 3 2,700 10 A 0.36 No 100 1.2 No 0 Comparative Example 4 2,500 8 D 0.32 Yes 80 1.1 No 0 Comparative Example 5 800 8 B 0.51 No 100 1.1 No 0 Comparative Example 6 800 8 B 0.56 100 1.1 No 0 Comparative Example 7 2,900 12 A 0.31 No 100 0 There are 300 Comparative Example 8 5,200 12 A 0.34 without 100 0 with 450

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

-51 --51 -

Claims (1)

1380065 --- 修正本 公告本 第094 104389號「間隔物形成用放射線敏感性樹脂組合物 、間隔物和其形成方法、及液晶顯示元件」專利申請案 • (2〇12年2月21日修正） 十、申請專利範圍： 1 · 一種間隔物形成用放射線敏感性樹脂組合物，其特徵 在於，該組合物含有： [A](al)不飽和缓酸和/或不飽和缓酸酐、（a2)含有 環氧基的不飽和化合物與（a3)其他不飽和化合物的共 聚物； 在共聚物[A]中，來自化合物（al)之構成單元的含 有率為5-50重量％，來自化合物（a2)的構成單元的含有 率為10-70重量％，來自化合物（a3)的構成單元的含有 率為1 0 - 8 0重量％ ; ^ 里兩z入ιυ 〜 5Μ05’且為100重量份的共聚物；1380065 --- Revised 094 104389 "Radiation-sensitive resin composition for spacer formation, spacer, method of forming the same, and liquid crystal display element" Patent Application (Amended on February 21, 2002) X. Patent Application Range: 1 . A radiation sensitive resin composition for forming a spacer, characterized in that the composition contains: [A] (al) unsaturated acid and/or unsaturated acid anhydride, (a2) a copolymer of an epoxy group-containing unsaturated compound and (a3) another unsaturated compound; in the copolymer [A], the content of the constituent unit derived from the compound (al) is 5 to 50% by weight, derived from the compound ( The content of the constituent unit of a2) is from 10 to 70% by weight, and the content of the constituent unit derived from the compound (a3) is from 10 to 80% by weight; ^ two of the two are in the range of ιυ to 5Μ05' and are 100 parts by weight. Copolymer [Β]相對於1 〇〇重量份的共聚物[Α]為30〜200重量 份之雙官能以上的甲基丙烯酸酯；以及 [c]相對於1〇〇重量份的共聚物[Α]為5〜5〇重量份 之以由下列通式⑴表示的化合物作為必要成分的放射 線敏感性聚合引發劑；[Β] is a difunctional or higher methacrylate in an amount of 30 to 200 parts by weight based on 1 part by weight of the copolymer [Α]; and [c] is a copolymer [Α] with respect to 1 part by weight. 5 to 5 parts by weight of a radiation-sensitive polymerization initiator having a compound represented by the following formula (1) as an essential component; ⑴ -1 1380065 修正本 在通式（1)中，Ri表示碳原子數li2的直鏈、支鏈 或環狀的烷基；…和尺3彼此獨立地表 的直鏈、支鍵或環狀的烧基；〜、二8均表示 氫原子；R6表示碳原子數H2的直鏈、支鏈或環狀的 炫基。 2.-種間隔物’纟由如申請專利範圍第4之間隔物形成 用放射線敏感性樹脂組合物所形成。 3 · —種間隔物之形成方法，其特徵在於， 邊万法至少包 含下述（1)〜（4)之步驟： ⑴在基板上形成如申請專利範圍第i項之間隔物 形成用放射線敏感性樹脂組合物的被膜之I (2)對該被膜之至少一部分用放射線進光 驟； (3) 將曝光後之上述被膜顯影的步驟； (4) 將顯影後之上述被膜加熱的步驟。 4. 一種液晶顯示元件’其具備如申請專利範圍第2項(1) -1 1380065 In the general formula (1), Ri represents a linear, branched or cyclic alkyl group having a carbon number of li2; and the ruler 3 is linear, branched or cyclic independently of each other. The base is a hydrogen atom; and R6 represents a linear, branched or cyclic thio group having a carbon number H2. 2. The spacer 纟 is formed of a radiation sensitive resin composition as formed in the spacer of the fourth application. 3. A method of forming a spacer, characterized in that the edge method comprises at least the following steps (1) to (4): (1) forming a radiation sensitive layer for forming a spacer on the substrate as in the scope of the patent application. The film of the resin composition I (2) irradiates at least a part of the film with radiation; (3) a step of developing the film after exposure; and (4) a step of heating the film after development. 4. A liquid crystal display element' having the second item as claimed in the patent application 之間 隔物。 1380065 修正本 七、指定代表圖： (一） 本案指定代表圖為：無。 (二) 本代表圖之元件符號簡單說明: 無Between the partitions. 1380065 Amendment VII. Designation of Representative Representatives: (1) The representative representative of the case is: None. (2) A brief description of the component symbols of this representative figure: None 八、本案若有化學式時，請揭示最能顯示發明特徵的化學式： R2 O R18. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: R2 O R1
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