TWI379130B - Radiation sensitive resin composition, projections and spacers, vertically aligned type liquid crystal display element, and the method for forming projections, and spacers - Google Patents

Radiation sensitive resin composition, projections and spacers, vertically aligned type liquid crystal display element, and the method for forming projections, and spacers Download PDF

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TWI379130B
TWI379130B TW095111365A TW95111365A TWI379130B TW I379130 B TWI379130 B TW I379130B TW 095111365 A TW095111365 A TW 095111365A TW 95111365 A TW95111365 A TW 95111365A TW I379130 B TWI379130 B TW I379130B
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liquid crystal
crystal display
weight
spacers
dimethyl
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TW200641489A (en
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Hiroshi Shiho
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Jsr Corp
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C09D201/06—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
    • C09D201/08—Carboxyl groups
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0755—Non-macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • 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)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Liquid Crystal (AREA)
  • Materials For Photolithography (AREA)
  • Polyethers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Description

1379130 c j 九、發明說明： 【發明所屬之技術領域】 所 成 突 顯 人 對 質 在 CJR 週 作 90 在 度 在 光 兩 線 本發明涉及一種用於形成垂直配向型液晶顯示元件 • 使用的突起和/或間隔物（spacer)的感放射線性樹脂組 . 物、由該組成物形成的垂直配向型液晶顯示元件使用的 起和間隔物、包含該突起和/或間隔物的垂直配向型液晶 示元件以及形成該突起和/或該間隔物的方法。 【先前技術】 φ 液晶顯示元件廣泛用於平板顯示器。近年來，隨著個 電腦和文字處理器等OA設備以及液晶電視等的推廣， TFT(薄膜電晶體）方式的液晶顯示器（TFT-LCD)的顯示品 的要求正變得越來越嚴格。在 TFT-LCD之中，現 TN(Twisted Nematic)型LCD是最受歡迎的。該LCD是通 下述方法製造的：在2塊具有透明電極的基板（以下，稱 “透明電極基板”。）的兩外側分別配置配向方向相差 . 度的偏光膜，並在兩個透明電極基板內側配置配向膜； φ 兩配向膜之間配置向列型液晶，將液晶的配向方向以90 的角度從一個電極側扭轉向另一個電極側。當非偏振光 該狀態下入射時，因透過一面偏光板的直線偏光偏離偏 方向而透過另一面偏光板，形成光亮狀態。然後，當向 個電極都施加電壓而使液晶分子直立時，到達液晶的直 偏振光直接穿過，不會穿過另一個偏光片，形成黑暗狀樓 λ 此後，當停止施加電壓時，就恢復成光亮狀態。 雖然，由於近年來的技術進步，在正面的對比度和色彩 再現性等方面，這種TN型LCD變得與陰極射線管（CRT) 1379130 c. » 相當或更優越。但是，TN型LCD仍有一個大問題需要解 決，那就是視角狹窄。作爲解決這種問題的方法，開發出 了 MVA(Multi-domain Vertically Aligned)型 LCD(垂直配向 • 型液晶顯示器）。如非專利文獻1和專利文獻1所記載，該 . MVA型LCD並不是TN型LCD的旋光模式，而是將具有負 的介電常數各向異性的負型液晶和垂直方向的配向膜組合 的雙折射模式的LCD，使用這種雙折射模式的LCD ;即使 在沒有施加電壓的狀態下，在接近配向膜的位置上的液晶 # 配向方向也可以大致保持垂直方向，因此，對比度、視角 等優異’而且可以不進行使液晶配向的硏磨處理等，在製 造步驟方面也是優異的。 在MVA型LCD中，爲了使液晶在一個圖元區域可以取 多個配向方向，作爲區域限製方法可以是使顯示側的電極 爲在1個圖元區域內具有狹縫的電極，而且在光入射側的 電極基板上的同一圖元區域內，在和電極的狹縫不同的位 • 置上形成具有斜面的突起（例如，三角錐形，半凸透鏡形狀 φ 等）。另外，在目前的液晶顯示器中，一般是使用樹脂和陶 瓷等球形或棒狀的間隔物，將2塊透明電極基板的間.隙（單 元間隙）（cell gap)保持一定。在貼合2塊透明電極基板時， 間隔物可以散佈在任何一個基板上，根據間隔物的直徑決 定單元間隙。 • 另外，爲了避免間隔物直徑差異引起的單元間隙不均勻 等問題’在專利文獻2中’還公開了使用光阻材料形成突 » 起和間隔物的方法，該方法具有如下優點：可以微細加工， 容易控製形狀。但是在專利文獻2中並未具體記載光阻材 13乃13()…- 料的組成’也沒有表明形成的突起和間隔物的性能。 【非專利文獻1】武田有廣，液晶，日本液晶學會， 年 4 月 25 日，Vol.3，No.2，117 【專利文獻1】特開平1 1 -25 8605號公報 • 【專利文獻2】特開2001-201750號公報 作爲垂直配向型液晶顯示元件使用的突起和間隔 形成中使用的光阻材料所要求的性能，可以列舉出-如 點。也就是，突起和間隔物除了剖面形狀要適當外， ® 求對之後的配向膜形成步驟中使用的溶劑的承受性、 向膜形成步驟施加的熱的承受性、透明性、解析度Λ 率等性能較高。另外，還要求所得的垂直配向型液晶 兀件的配向性、電壓保持率等優異。本申請人已經提 用於同時形成突起和間隔物的感放射線性樹脂組成物 樹脂組成物包括[A ]由（a 1)不飽和殘酸和/或不飽和 歡；、（a 2)含有的不飽和化合物以及（a3)這、些之外 - 飽和化合物形成的共聚物，[B ]不飽和聚合性化合物以. • 感放射線性聚合引發劑；還提出了由該樹脂組成物形 突起和間隔物’以及包含該突起和間隔物的液晶顯示 (參照專利文獻3)。但是，只是開發了對垂直配向型液 示元件的突起和間隔物的形成有用的感放射線性樹脂 物’開發出與TFT-LCD的快速普及和越來越嚴格的性 , 求相適應的，可以形成具有優異的性能的突起和間隔 新型的感放射線性樹脂組成物正成爲重要的技術課題 * 【專利文獻3】特開2003-29405號公報 【發明內容】 1999 物的 下幾 還要 對配 殘膜 顯示 出了 ，該 羧酸 的不 泛[C] 成的 元件 晶顯 組成 能要· 物的 1379130t , 本發明是根據以上的問題而提出的，該課題在於提供用 於形成垂直配向型液晶顯示元件所使用的突起和/或間隔 物的感放射線性樹脂組成物，更具體地，提供作爲光阻材 料，解析度和殘膜率優異且能形成圖案形狀 '耐熱性、耐 溶劑性、透明性等優異的突起和間隔物，而且可以得到配 向性、電壓保持率等優異的垂直配向型液晶顯示元件的感 放射轉性樹脂組成物，以及使用該放射線樹脂組成物形成 垂直配向型液晶顯示元件使用的突起和/或間隔物的方法。 根據本發明’本發明的上述目的和優點，第1是通過一 種用於形成垂直配向型液晶顯示元件所使用的突起和/或 間隔物的感放射線性樹脂組成物實現的，該感放射線性樹 脂組成物的特徵在於：包括， [A] 將下述U1)〜（a3)共聚而得到的共衆物（以下，稱作 “共聚物[AD ’其中（al)是不飽和殘酸和/或不飽和羧酸酐 (以下，稱作“化合物（a 1)”）， U2)是具有環氧基或氧雜環丁院基的不飽和化合物（以 下，稱作“化合物（a2)”）， U3)是上述UU和（a2)成分以外的懷 (以下’稱作“化合物（a3)”）；和 [B] 光陽離子聚合引發劑。 本發明的目的和優點，第2是通過由上述感放射線性樹 脂組成物形成的垂直配向型液晶顯示元件使用的突起實現 的。 本發明的目的和優點’第3是通過由上述感放射線性樹 脂組成物形成的«配向型液晶顯示元{牛{吏用的間隔物實1379130 cj IX. Description of the invention: [Technical field to which the invention pertains] The present invention relates to the use of protrusions and/or protrusions for forming vertical alignment type liquid crystal display elements in a CJR cycle. a radiation-sensitive resin group of a spacer, a spacer and a spacer used for a vertical alignment type liquid crystal display element formed of the composition, a vertical alignment type liquid crystal display element including the protrusion and/or the spacer, and formation The method of the protrusion and/or the spacer. [Prior Art] φ liquid crystal display elements are widely used in flat panel displays. In recent years, with the promotion of OA equipment such as computers and word processors, and LCD TVs, the demand for display products of TFT (Thin Film Transistor) liquid crystal displays (TFT-LCDs) has become stricter. Among the TFT-LCDs, the TN (Twisted Nematic) type LCD is currently the most popular. The LCD is manufactured by disposing a polarizing film having a phase difference of a degree of alignment in two outer sides of two substrates having transparent electrodes (hereinafter referred to as "transparent electrode substrates"), and on two transparent electrode substrates. The alignment film is disposed on the inner side; φ the nematic liquid crystal is disposed between the two alignment films, and the alignment direction of the liquid crystal is twisted from one electrode side to the other electrode side at an angle of 90 degrees. When the non-polarized light is incident in this state, the linear polarized light that has passed through the polarizing plate is deflected by the polarizing plate and passes through the other polarizing plate to form a bright state. Then, when a voltage is applied to each of the electrodes to make the liquid crystal molecules stand upright, the linearly polarized light reaching the liquid crystal passes straight through, does not pass through the other polarizer, and forms a dark floor λ. Thereafter, when the application of the voltage is stopped, the recovery is resumed. In a bright state. Although, due to technological advances in recent years, such a TN type LCD has become comparable or superior to a cathode ray tube (CRT) 1379130 c. » in terms of front contrast and color reproducibility. However, there is still a big problem with the TN LCD that needs to be solved, that is, the viewing angle is narrow. As a method for solving such a problem, an MVA (Multi-domain Vertically Aligned) type LCD (vertical alignment type liquid crystal display) was developed. As described in Non-Patent Document 1 and Patent Document 1, the MVA type LCD is not an optical rotation mode of a TN type LCD, but a combination of a negative type liquid crystal having a negative dielectric anisotropy and a vertical alignment film. In the birefringence mode LCD, the LCD of this birefringence mode is used; even in the state where no voltage is applied, the alignment direction of the liquid crystal # at the position close to the alignment film can be substantially maintained in the vertical direction, and therefore, the contrast, the viewing angle, and the like are excellent. Further, it is also possible to perform honing treatment or the like for aligning the liquid crystal, and is also excellent in terms of the production steps. In the MVA type LCD, in order to allow the liquid crystal to take a plurality of alignment directions in one primitive region, the region limiting method may be to make the electrode on the display side be an electrode having a slit in one primitive region, and to be incident on the light. In the same element region on the side electrode substrate, a protrusion having a slope (for example, a triangular pyramid shape, a semiconvex lens shape φ, or the like) is formed at a position different from the slit of the electrode. Further, in the conventional liquid crystal display, a spherical or rod-shaped spacer such as a resin or a ceramic is generally used, and the gap between the two transparent electrode substrates is kept constant. When the two transparent electrode substrates are bonded, the spacers may be spread on any one of the substrates, and the cell gap is determined according to the diameter of the spacer. In addition, in order to avoid the problem of unevenness of the cell gap caused by the difference in the diameter of the spacers, 'Patent Document 2' also discloses a method of forming a protrusion and a spacer using a photoresist material, which has the following advantages: fine processing , easy to control the shape. However, Patent Document 2 does not specifically describe that the photoresist member 13 is a composition of the material and does not indicate the properties of the formed protrusions and spacers. [Non-Patent Document 1] Takeda Yusuke, Liquid Crystal, Japanese Society of Liquid Crystal, April 25, Vol. 3, No. 2, 117 [Patent Document 1] Japanese Patent Laid-Open No. Hei 1 1 - 25 8605 (Patent Document 2) JP-A-2001-201750 discloses the performance required for the protrusions used in the vertical alignment type liquid crystal display element and the photoresist used in the formation of the spacers, and examples thereof include dots. In other words, in addition to the cross-sectional shape of the projections and the spacers, the tolerance of the solvent used in the subsequent alignment film formation step, the heat tolerance imparted to the film formation step, the transparency, the resolution, and the like are determined. High performance. Further, the obtained vertical alignment type liquid crystal element is required to have excellent alignment properties, voltage holding ratio, and the like. The radiation-sensitive resin composition resin composition which has been proposed by the applicant to simultaneously form protrusions and spacers includes [A] from (a1) unsaturated residual acid and/or unsaturated acid; (a2) An unsaturated compound and (a3) a copolymer of these and other unsaturated compounds, a [B] unsaturated polymerizable compound, a radiation sensitive linear polymerization initiator, and a protrusion and space formed by the resin. The object 'and the liquid crystal display including the protrusion and the spacer (refer to Patent Document 3). However, it has only been developed that the radiation-sensitive resin that is useful for the formation of protrusions and spacers of the vertical alignment type liquid display element has been developed to be compatible with the rapid spread of the TFT-LCD and the increasingly strict nature. It is an important technical issue to form a new type of radiation-sensitive resin composition having excellent performance and a new type of radiation. [Patent Document 3] JP-A-2003-29405 [Summary of the Invention] 1999 The present invention has been proposed to provide a vertical alignment type liquid crystal display according to the above problems, in which the element of the carboxylic acid is not substantially [C] crystallized to form a constituent material of 1379130t. The radiation-sensitive resin composition of the protrusions and/or spacers used for the element, more specifically, is provided as a photoresist material, and has excellent resolution and residual film ratio, and can form a pattern shape 'heat resistance, solvent resistance, transparency Excellent protrusions and spacers, and a radiation-sensitive resin composition of a vertical alignment type liquid crystal display element excellent in alignment property, voltage holding ratio, and the like And a method of forming protrusions and/or spacers used in the vertical alignment type liquid crystal display element using the radiation resin composition. According to the present invention, the above objects and advantages of the present invention are attained by a radiation sensitive resin composition for forming protrusions and/or spacers used for a vertical alignment type liquid crystal display element, which is a radiation sensitive resin. The composition is characterized by comprising: [A] a confocal product obtained by copolymerizing the following U1) to (a3) (hereinafter, referred to as "copolymer [AD' wherein (al) is an unsaturated residual acid and/or The unsaturated carboxylic anhydride (hereinafter referred to as "compound (a 1)"), U2) is an unsaturated compound having an epoxy group or an oxetane group (hereinafter, referred to as "compound (a2)"), U3 It is the above-mentioned UU and (a2) component (hereinafter referred to as "compound (a3)"); and [B] photocationic polymerization initiator. The object and advantage of the present invention, the second is by the above-mentioned radiation The object of the present invention is achieved by the protrusions used in the vertical alignment type liquid crystal display element formed by the resin composition. The third object is the "alignment type liquid crystal display element" formed by the above-mentioned radiation sensitive resin composition. Spacer

1379130 I I 現的。 本發明目的和優點，第4是通過包含上述突起和/或上述 間隔物的垂直配向型液晶顯示元件實現的。 本發明的目的和優點，第5是通過形成突起和/或間隔物 的方法實現的’該方法的特徵在於至少包含如下步驟： U)在基板上形成申請專利範圍第1項感放射線性組成 物塗膜的步驟： (2) 對該塗膜的至少—部分照射放射線的步驟； (3) 顯影步驟； (4) 加熱步驟。 用於形成本發明的垂直配向型液晶顯示元件使用的突 起和/或間隔物的感放射線性樹脂組成物，可以形成解析度 和殘膜率優異，且圖案形狀、耐熱性、耐溶劑性、透明性 等優異的突起和/或間隔物，而且還可以提供配向性、電壓 保持率等優異的垂直配向型液晶顯示元件。另外，本發明 的垂直配向型液晶顯示元件使用的突起和/或間隔物的形 成方法，可以微細加工，而且容易控製形狀和尺寸（高度和 底部尺寸），可以穩定且生產性高地形成圖案形狀、耐熱 性、耐溶劑性、透明性等優異的微細的突起和間隔物，而 且還可以提供配向性、電壓保持率等優異的垂直配向型液 晶顯示元件》 【實施方式】 以下，對本發明的感放射線性樹脂組成物的各成分進行 詳細說明。 1379130 t » 共聚物[A]通過在溶劑中，在聚合引發劑的存在下，使 化合物（a 1 )、化合物（a2)和化合物（a 3)進行自由基聚合而合 成。 本發明中使用的共聚物[A]較佳含有5〜40重量％來自化 合物（al)的構成單元，特別較佳含有1〇〜35重量％。該構 成單元小於5重量％的共聚物難以溶解到鹼性水溶液中，另 外’超過4 0重量％的共聚物對鹼性水溶液的溶解性有變得 過大的趨勢。 作爲化合物（a 1 )，可以列舉出例如丙烯酸、甲基丙烯酸、 巴豆酸等一元羧酸類，馬來酸、富馬酸、檸康酸、中康酸、 衣康酸等二元羧酸類和它們的酸酐，琥珀酸單[2-(甲基）丙 烯醯氧基乙基]酯、苯二甲酸單[2-(甲基）丙烯醯氧基乙基] 酯等2元或以上的多元羧酸的單[(甲基）丙烯醯氧基烷基] 酯類’ ω-羧基聚己內酯單（甲基）丙烯酸酯等兩末端具有羧 基和羥基的聚合物的單（甲基）丙烯酸酯類等。其中，從共 聚反應性、對鹼性水溶液的溶解性和容易獲得方面出發， 較佳使用丙&酸 '甲基丙烯酸、馬來酸酐等。它們可以單 獨使用，也可以結合使用。 本發明中使用的共聚物[Α]較佳含有5〜60重量％來自化 合物（a2)的構成單元，特別較佳含有1〇〜50重量％。該構 成單元小於5重量％時，所得的塗膜的耐熱性有降低的趨 勢’另一方面’如果超過60重量％，則共聚物的保存穩定 性有降低的趨勢。 作爲化合物（a2)可以列舉出含有環氧基的不飽和化合物 或含有氧雜環丁基的不飽和化合物。 -10- 1379130 * · 不飽和化合物，可以列舉出例如丙烯1379130 I I Presented. SUMMARY OF THE INVENTION A fourth object of the present invention is achieved by a vertical alignment type liquid crystal display element comprising the above-mentioned protrusions and/or the above spacers. The object and advantage of the present invention, the fifth is achieved by a method of forming protrusions and/or spacers. The method is characterized in that it comprises at least the following steps: U) forming a radiation sensitive composition of claim 1 on the substrate. The step of coating the film: (2) a step of irradiating at least a portion of the film with radiation; (3) a developing step; and (4) a heating step. The radiation-sensitive resin composition for forming the protrusions and/or spacers used in the vertical alignment type liquid crystal display element of the present invention can be excellent in resolution and residual film ratio, and has a pattern shape, heat resistance, solvent resistance, and transparency. A protrusion and/or a spacer excellent in properties and the like, and a vertical alignment type liquid crystal display element excellent in an alignment property, a voltage holding ratio, and the like can be provided. Further, the method of forming the protrusions and/or spacers used in the vertical alignment type liquid crystal display element of the present invention can be finely processed, and the shape and size (height and bottom size) can be easily controlled, and the pattern shape can be stably and productively formed. A fine alignment protrusion and a spacer which are excellent in heat resistance, solvent resistance, transparency, and the like, and a vertical alignment type liquid crystal display element excellent in an alignment property and a voltage holding ratio, etc. [Embodiment] Hereinafter, the radiation of the present invention is obtained. Each component of the resin composition will be described in detail. 1379130 t » The copolymer [A] is synthesized by radical polymerization of the compound (a 1 ), the compound (a2) and the compound (a 3) in the presence of a polymerization initiator in a solvent. The copolymer [A] used in the present invention preferably contains 5 to 40% by weight of the constituent unit derived from the compound (al), and particularly preferably 1 to 35% by weight. The copolymer having less than 5% by weight of the constituent unit is difficult to dissolve in the alkaline aqueous solution, and the solubility of the copolymer exceeding 70% by weight in the alkaline aqueous solution tends to become excessive. Examples of the compound (a 1 ) include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid, and dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid, and the like. An acid anhydride, succinic acid mono [2-(methyl) propylene methoxyethyl] ester, phthalic acid mono [2-(methyl) propylene methoxyethyl] ester or the like 2 or more polycarboxylic acids Single [(meth) propylene oxiranyl] ester ' ω-carboxy polycaprolactone mono (meth) acrylate, such as a mono(meth) acrylate of a polymer having a carboxyl group and a hydroxyl group at both ends Wait. Among them, C&acid 'methacrylic acid, maleic anhydride, and the like are preferably used from the viewpoints of copolymerization reactivity, solubility in an aqueous alkaline solution, and easy availability. They can be used alone or in combination. The copolymer [Α] used in the present invention preferably contains 5 to 60% by weight of the constituent unit derived from the compound (a2), and particularly preferably contains 1 to 50% by weight. When the amount of the constituent unit is less than 5% by weight, the heat resistance of the obtained coating film tends to decrease. On the other hand, if it exceeds 60% by weight, the storage stability of the copolymer tends to be lowered. The compound (a2) may, for example, be an epoxy group-containing unsaturated compound or an oxetanyl group-containing unsaturated compound. -10- 1379130 * · An unsaturated compound, for example, propylene

作爲含As containing

酸縮水甘油酯、丙綠酸2-甲基縮水甘油酯、丙烯酸4-羥基 丁基酯縮水甘油醆、丙烯酸3，4-環氧丁基酯、丙烯酸6,7_ 環氧庚基酯、丙烯酸3，·4-環氧環己基酯等丙烯酸環氧（環） 烷基酯類，甲基丙烯酸縮水甘油酯、甲基丙烯酸2-甲基縮 水甘油酯、甲基丙烯酸3,4-環氧丁基酯、甲基丙烯酸6,7-環氧庚基酯、甲基丙烯酸3,4-環氧環己基酯等甲基丙烯酸 環氧（環）烷基酯類，α-乙基丙烯酸縮水甘油酯、α-正丙基 丙烯酸縮水甘油酯、α-正丁基丙烯酸縮水甘油酯、α -乙 基丙烯酸6,7-環氧庚基酯、α-乙基丙烯酸3,4-環氧環己基 酯等其他的α-烷基丙烯酸環氧（環）烷基酯類；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 基縮氷甘油醚等縮水甘油醚類等。 作爲含有氧雜環丁基的不飽和化合物，可以列舉出例如 3-(甲基丙烯醯氧基甲基）氧雜環丁烷' 3-(甲基丙烯醯氧基 甲基）-3 -乙基氧雜環丁烷、3-(甲基丙烯醯氧基甲基）-3 -甲基 氧雜環丁烷、3-(甲基丙烯醯氧基甲基）-2 -甲基氧雜環丁 烷、3-(甲基丙烯醯氧基甲基）-2 -三氟甲基氧雜環丁烷、3-(甲 基丙烯醯氧基甲基）-2-五氟乙基氧雜環丁烷、3-(甲基丙烯 醯氧基甲基）-2-苯基氧雜環丁烷、3-(甲基丙烯醯氧基甲 基）·2,2-二氟代氧雜環丁烷、3-(甲基丙烯醯氧基甲 基）-2,2，4 -三氟代氧雜環丁烷、3“甲基丙烯醯氧基甲 基）-2,2,4.，4-四氟代氧雜環丁烷、3-(甲基丙烯醯氧基乙基） 氧雜環丁烷、3-(甲基丙烯醯氧基乙基）-3 -乙基氧雜環丁 烷、2-乙基- 3-(甲基丙烯醯氧基乙基）氧雜環丁烷、3-(甲基 1379130 r · 丙烯醯氧基乙基）-2-三氟甲基氧雜環丁烷、3-(甲基丙烯醯 氧基乙基）-2-五氟乙基氧雜環丁烷、3-(甲基丙烯醯氧基乙 基）-2-苯基-氧雜環丁烷、2,2-二氟代- 3-(甲基丙烯醯氧基乙 • 基）氧雜環丁烷、3-(甲基丙烯醯氧基乙基）-2,2,4-三氟代氧 . 雜環丁烷、3-(甲基丙烯醯氧基乙基）-2,2,4,4-四氟代氧雜環 丁烷， 2-(甲基丙烯醯氧基甲基）氧雜環丁烷' 2-甲基-2-(甲基丙 烯醯氧基甲基）氧雜環丁烷、3·甲基- 2-(甲基丙烯醯氧基甲 • 基）氧雜環丁烷、4-甲基-2-(甲基丙烯醯氧基甲基）氧雜環丁 烷、2-(甲基丙烯醯氧基甲基）-2-三氟甲基氧雜環丁烷、2-(甲 基丙烯醯氧基甲基）-3 -三氟甲基氧雜環丁烷、2-(甲基丙烯 醯氧基甲基）-4 _三氟甲基氧雜環丁烷、2-(甲基丙烯醯氧基 甲基）-2-五氟乙基氧雜環丁烷、2-(甲基丙烯醯氧基甲基）-3-五氟乙基氧雜環丁烷、2-(甲基丙烯醯氧基甲基）-4-五氟乙 基氧雜環丁烷、2-(甲基丙烯醯氧基甲基）-2-苯基氧雜環丁 烷、2-(甲基丙烯醯氧基甲基）-3-苯基氧雜環丁烷、2-(甲基 φ 丙烯醯氧基甲基）-4-苯基氧雜環丁烷、2,3-二氟代- 2-(甲基 丙烯醯氧基甲基）氧雜環丁烷、2,4-二氟代- 2-(甲基丙烯醯氧 基甲基）氧雜環丁烷、3,3-二氟代·2·(甲基丙烯醯氧基甲基） 氧雜環丁烷、3,4-二氟代- 2-(甲基丙烯醯氧基甲基）氧雜環丁 烷、4,4-二氟代-2·(甲基丙烯醯氧基甲基）氧雜環丁烷、2-(甲 ; 基丙烯醯氧基甲基）-3,3,4-三氟代氧雜環丁烷、2-(甲基丙烯 醯氧基甲基）-3,4,4-三氟代氧雜環丁烷、2-(甲基丙烯醯氧基 甲基）-3,3,4,4-四氟代氧雜環丁烷， .2-(甲基丙烯醯氧基乙基）氧雜環丁烷、甲基丙烯酸 -12- 1379130 9 · 2-(2-(2 ·甲基氧雜環丁基））乙基酯、甲基丙烯酸2-(2-(3-甲基 氧雜環丁基））乙基酯、2-(甲基丙烯醯氧基乙基）-2-甲基氧雜 環丁烷、2-(甲基丙烯醯氧基乙基）-4-甲基氧雜環丁烷、2-(甲 * 基丙烯醯氧基乙基）·2-三氟甲基氧雜環丁烷、2-(甲基丙烯 . 醯氧基乙基）-3-三氟甲基氧雜環丁烷、2-(甲基丙烯醯氧基 乙基）-4·三氟甲基氧雜環丁烷、2-(甲基丙烯醯氧基乙基）-2-五氟乙基氧雜環丁烷、2-(甲基丙烯醯氧基乙基）-3-五氟乙 基氧雜環丁烷、2-(甲基丙烯醯氧基乙基）-4-五氟乙基氧雜 # 環丁烷、2-(甲基丙烯醯氧基乙基）-2-苯基氧雜環丁烷、2-(甲 基丙烯醯氧基乙基）-3-苯基氧雜環丁烷、2-(甲基丙烯醯氧 基乙基）-4-苯基氧雜環丁烷、2,3-二氟代- 2-(甲基丙烯醯氧 基乙基）氧雜環丁烷、2,4-二氟代-2-(甲基丙烯醯氧基乙基） 氧雜環丁烷、3,3-二氟代- 2-(甲基丙烯醯氧基乙基）氧雜環丁 烷、3,4-二氟代-2-(甲基丙烯醯氧基乙基）氧雜環丁烷、4,4-二氟代-2-(甲基丙烯醯氧基乙基）氧雜環丁烷、2-(甲基丙烯 醯氧基乙基）-3,3,4-三氟代氧雜環丁烷' 2-(甲基丙烯醯氧基 ^ 乙基）-3,4,4-三氟代氧雜環丁烷' 2·(甲基丙烯醯氧基乙 基）-3,3,4,4-四氟代氧雜環丁烷等甲基丙烯酸酯類； 3-(丙烯醯氧基甲基）氧雜環丁烷、3-(丙烯醯氧基甲 基）-3-乙基氧雜環丁烷、3-(丙烯醯氧基甲基）-3-甲基氧雜環 丁烷' 3-.(丙烯醯氧基甲基）-2-甲基氧雜環丁烷' 3-(丙烯醯 ； 氧基甲基）-2-三氟甲基氧雜環丁烷、3-(丙烯醯氧基甲基）-2- 五氟乙基氧雜環丁烷、3-(丙烯醯氧基甲基）-2-苯基氧雜環 f 丁烷、3-(丙烯醯氧基甲基）-2,2-二氟代氧雜環丁烷、3-(丙 烯醯氧基甲基）-2,2，4-三氟代氧雜環丁烷、3-(丙烯醯氧基甲 1379130 基）-2,2，4,4-四氟代氧雜環丁烷、3-(丙烯醯氧基乙基）氧雜環 丁烷、3-(丙烯醯氧基乙基）-3 -乙基·氧雜環丁烷' 2 -乙基 •3-(丙烯醯氧基乙基）氧雜環丁烷、3-(丙烯醯氧基乙基）·2-二氟甲基氧雜環丁院、3.(丙燃醯氧基乙基）-2 -五氟乙基氧 ' 雜環丁烷、3-(丙烯醯氧基乙基）-2 -苯基氧雜環丁烷、2,2-二氟代- 3- (丙烯醯氧基乙基）氧雜環丁院、3-(丙稀醯氧基乙 基）-2,2,4-三氟代氧雜環丁烷、3-(丙烯醯氧基乙基）-2,2,4，4-四氟代氧雜環丁烷， ® 2-(丙烯醯氧基甲基）氧雜環丁烷、2-甲基- 2-(丙烯醯氧基 甲基）氧雜環丁烷、3-甲基-2-(丙烯醯氧基甲基）氧雜環丁 烷、4-甲基- 2-(丙烯醯氧基甲基）氧雜環丁烷、2-(丙烯醯氧 基甲基）-2-三氟甲基氧雜環丁烷、2-(丙烯醯氧基甲基）·3-三氟甲基氧雜環丁烷、2-(丙烯醯氧基甲基）-4-三氟甲基氧 雜環丁烷、2-(丙烯醯氧基甲基）-2-五氟乙基氧雜環丁烷、 2-(丙烯醯氧基甲基）-3-五氟乙基氧雜環丁烷、2-(丙.烯醯氧 基甲基）-4-五氟乙基氧雜環丁烷、2-(丙烯醯氧基甲基）·2-Φ 苯基氧雜環丁烷、2-(丙烯醯氧基甲基）-3·苯基氧雜環丁 烷、2-(丙烯醯氧基甲基）-4-苯基氧雜環丁烷、2,3-二氟代 -2-(丙烯醯氧基甲基）氧雜環丁烷、2,4-二氟代-2·(丙烯醯氧 基甲基）氧雜環丁烷、3,3-二氟代- 2-(丙烯醯氧基甲基）氧雜 環丁烷、3,4 -二氟代- 2- (丙烯醯氧基甲基）氧雜環丁烷、4,4-： 二氟代- 2-(丙烯醯氧基甲基）氧雜環丁烷、2-(丙烯醯氧基甲 基）-3,3,4-三氟代氧雜環丁烷、2-(丙烯醯氧基甲基）-3,4,4- « 三氟代氧雜環丁烷、2-(丙烯醯氧基甲基）-3, 3,4,4-四氟代氧 雜環丁烷， -14- 1379130 2-(丙烯醯氧基乙基）氧雜環丁烷、甲基丙烯酸2-(2-(2-甲基氧雜環丁基））乙基酯、甲基丙烯酸2-(2-(3-甲基氧雜環 丁基））乙基酯、2-(丙烯醯氧基乙基）-2-.甲基氧雜環丁烷、 2-(丙烯醯氧基乙基）-4-甲基氧雜環丁烷、2·(丙烯醯氧基乙 • 基）-2-三氟甲基氧雜環丁烷、2-(丙烯醯氧基乙基）-3-三氟甲 基氧雜環丁烷、2-(丙烯醯氧基乙基）-4-三氟甲基氧雜環丁 烷、2·(丙烯醯氧基乙基）-2-五氟乙基氧雜環丁烷、2-(丙烯 醯氧基乙基）-3-五氟乙基氧雜環丁烷、2-(丙烯醯氧基乙 ® 基）-4-五氟乙基氧雜環丁烷、2·(丙烯醯氧基乙基）-2-苯基氧 雜環丁烷、2-(丙烯醯氧基乙基）-3-苯基氧雜環丁烷、2-(丙 烯醯氧基乙基卜4-苯基氧雜環丁烷、2,3-二氟代·2-(丙烯醯 氧基乙基）氧雜環丁烷、2,4-二氟代- 2-(丙烯醯氧基乙基）氧 雜環丁烷' 3,3-二氟代-2-(丙烯醯氧基乙基）氧雜環丁烷、 3,4-二氟代-2·(丙烯醯氧基乙基）氧雜環丁烷、4,4-二氟代 _2-(丙烯醯氧基乙基）氧雜環丁烷、2-(丙烯醯氧基乙 基）-3,3,4-三氟代氧雜環丁烷、2-(丙烯醯氧基乙基）-3,4,4-• 三氟代氧雜環丁烷、2-(丙烯醯氧基乙基）-3,3,4,4·四氟代氧 雜環丁烷等丙烯酸酯類。 其中，從所得的感光性樹脂組成物的製程範圍寬、且可 以提高所得的突起和間隔物的耐化學腐蝕性方面出發，作 爲含有環氧基的不飽和化合物，較佳使用甲基丙烯酸縮水 : 甘油酯、甲基丙烯酸2-甲基縮水甘油酯、甲基丙烯酸6,7- 環氧庚基酯、丙烯酸4-羥丁基酯縮水甘油醚、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；作爲含有氧雜環丁基的不飽和化合物，較 -15- 1379130 ♦ « 佳使用3-(甲基丙烯醯氧基甲基）氧雜環丁烷、3-(甲基丙烯 醯氧基甲基）-2-三氟甲基氧雜環丁烷、3-(甲基丙烯醯氧基 甲基）-2-苯基氧雜環丁烷、2-(甲基丙烯醯氧基甲基）氧雜環 丁烷、2·(甲基丙烯醯氧基甲基）-4-三氟甲基氧雜環丁烷、 3-(甲基丙烯醯氧基甲基）-3-乙基氧雜環丁烷、3-(甲基丙烯 醯氧基甲基）-3-甲基氧雜環丁烷、3-(丙烯醯氧基甲基）-3-乙基氧雜環丁烷、3-(丙烯醯氧基甲基）-3·甲基氧雜環丁烷 等。它們可以單獨使用，也可以組合後使用。 本發明中使用的共聚物[A]較佳含有10〜80重量％來自 化合物U3)的構成單元，特別較佳含有20〜70重量％。該 構成單元小於10重量％時，共聚物[A]的保存穩定性有降低 的趨勢，另一方面，如果超過80重量％，則共聚物[A]難溶 於鹼性水溶液。 作爲化合物（a3)可以列舉出甲基丙烯酸甲酯、甲基丙烯酸 乙酯、甲基丙烯酸正丁酯、甲基丙烯酸仲丁酯、甲基丙烯 酸叔丁酯等甲基丙烯酸烷基酯類，丙烯酸甲酯、丙烯酸異 丙酯等丙烯酸烷基酯類；甲基丙烯酸環己酯、甲基丙烯酸 2 -甲基環己酯 '甲基丙烯酸三環[5.2.1.〇2.6]癸-8-基酯（作爲 該領域中常用的名稱’也稱作甲基丙烯酸二環戊烷基酯）、 甲基丙烯酸二環戊烷氧基乙酯、甲基丙烯酸異佛爾酮酯等 甲基丙烯酸環狀烷基酯類，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·8_基酯（作爲該領域中常 用的名稱，也稱作丙烯酸二環戊烷基酯）、丙烯酸二環戊烷 氧基乙酯' 丙烯酸異佛爾酮酯等丙烯酸環狀烷基酯類，甲 基丙烯酸苯酯、甲基丙烯酸苄酯等甲基丙烯酸芳基酯 -16- 1379130 ♦ · 類，丙烯酸苯酯、丙烯酸苄酯等丙烯酸芳基酯類，馬來酸 二乙酯、富馬酸二乙酯、衣康酸二乙酯等二元羧酸二酯， 甲基丙烯酸2-羥乙基酯、甲基丙烯酸2-羥丙基酯等羥烷基 酯類； 二環[2.2. 1]庚-2-烯、 5-甲基二環[2.2.1]庚-2-烯' 5-乙基二環[2.2.1]庚-2-烯、 5-羥基二環[2.2.1]庚-2-烯、 5-羧基二環[2.2.1]庚-2-烯、 5 -羥甲基二環[2.2.1]庚-2-烯、 5-(2’-羥乙基）二環[2.2.1]庚-2-烯、 5-甲氧基二環[2.2.1]庚-2-烯、 5-乙氧基二環[2.2.1]庚-2-烯、 5.6- 二羥基二環[2.2.1]庚-2-烯、 5.6- 二羧基二環[2.2.1]庚-2-烯、 5.6- 二（羥甲基）二環[2.2.1]庚-2-烯、 5.6- 二（2’-羥乙基）二環[2.2.1]庚-2-烯、 5.6- 二甲氧基二環[2.2.1]庚-2-烯、 5.6- 二乙氧基二環[2.2.1]庚-2-烯、 5 -羥基-5-甲基二環[2.2.1]庚-2-烯、 5-羥基-5-乙基二環[2.2.1]庚-2-烯、 5-羧基-5-甲基二環[2.2.1]庚-2-烯、 5-羧基-5-乙基二環[2.2.1]庚-2-烯、 5-羥甲基-5-甲基二環[2.2.1]庚-2-烯、 5-羧基-6-甲基二環[2.2.1]庚-2-烯、 -17- 1379130 》 5-羧基-6-乙基二環[2.2.1]庚-2-烯、 5.6 - 一殘基—環[2.2.1]庚·2·烧酸野（降冰片燒二酸酐）、 5-叔丁氧基羰基二環[2.2.1]庚-2-烯、 5-環己氧基羰基二環[2.2.1]庚-2-烯、 5-苯氧基羰基二環[2.2.1]庚-2-烯、 5，6-—(叙丁氧基锻基）二環[2.2.1]庚-2-嫌、 5.6 -二（環己氧基羰基）二環[2.2.1]庚-2-烯等二環不飽和 化合物類； 苯基馬來醯亞胺、環己基馬來醯亞胺、苄基馬來醯亞 胺、Ν -琥珀醯亞胺基-3-馬來醯亞胺苯甲酸酯、n-琥拍醯亞 胺基-4-馬來酸醯亞胺丁酸酯、Ν-琥珀醯亞胺基·6-馬來醯亞 胺己酸酯、Ν -琥珀醯亞胺基-3-馬來醯亞胺丙酸酯、ν-(9-吖啶基）馬來醯亞胺等二羰基醯亞胺衍生物類； 苯乙烯、α -甲基苯乙烯 '間-甲基苯乙烯、對-甲基苯乙 烯、乙烯基甲苯、對-甲氧基苯乙烯、丙烯腈、甲基丙烯腈、 氯乙烯 '偏二氯乙烯、丙烯醯胺、甲基丙烯醯胺、醋酸乙 烯酯、1,3-丁二烯、異戊二烯、2,3-二甲基-1,3-丁二烯、丙 烯酸縮水甘油酯、甲基丙烯酸縮水甘油酯、乙基丙烯酸 縮水甘油酯、α-正丙基丙烯酸縮水甘油酯、正丁基丙 烯酸縮水甘油酯、丙烯酸-3，4·環氧丁基酯 '甲基丙烯酸- 3,4-環氧丁基酯、丙烯酸-6,7.環氧庚基酯、甲基丙烯酸-6,7-環 氧庚基酯、乙基丙烯酸6,7-環氧庚基酯、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。 其中，從共聚反應性和對鹼性水溶液的溶解性方面出 -18- 1379130 發’較佳爲苯乙烯、甲基丙烯酸叔丁酯、甲基丙烯酸二環 戊烷基酯、對·甲氧基苯乙烯、丙烯酸2-甲基環己酯、1,3-丁二烯 '甲基丙烯酸縮水甘油酯、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、苯基馬來醯亞胺、環己基馬來醯亞胺、二環[2.2.1]庚 -2-烯等。它們可以單獨或組合後使用。 如上所述，本發明中使用的共聚物[A]具有羧基和/或羧 酸酐基以及氧雜環丁基，對鹼性水溶液有適當的溶解性， • 而且不和特定的固化劑一起使用也可以通過加熱容易地固 化。 含有上述的共聚物[A ]的感放射線性樹脂組成物在顯影 時’不會產生顯影殘留，也不會出現膜減少，容易形成規 定圖案的塗膜。 作爲.在合成共聚物[A]時使用的溶劑，具體地，可以列 舉出例如甲醇、乙醇等醇類；四氫呋喃等醚類；乙二醇單 甲基醚、乙二醇單乙基醚等二醇醚類；甲基溶纖劑乙酸酯' • 乙基溶纖劑乙酸酯等乙二醇烷基醚乙酸酯類；二甘醇單甲 基醚、二甘醇單乙基醚 '二甘醇二甲基醚、二甘醇二乙基 醚 '二甘醇乙基甲基醚等二甘醇類；丙二醇甲基醚、丙二 醇乙基醚、丙二醇丙基醚、丙二醇丁基醚等丙二醇單烷基 醚類；丙二醇甲基醚乙酸酯、丙二醇乙基醚乙酸酯、丙二 ： 醇丙基醚乙酸酯、丙二醇丁基醚乙酸酯等丙二醇烷基醚乙 酸酯類；丙二醇甲基醚丙酸酯、丙二醇乙基醚丙酸酯 '丙 ’二醇丙基醚丙酸酯、丙二醇丁基醚丙酸酯等丙二醇烷基醚 丙酸酯類；甲苯 '二甲苯等芳香族烴類； -19- 1379130 ♦ m 甲乙酮、環己酮' 4·羥基-4·甲基-2·戊酮等 醋、乙酸乙酯、乙酸丙酯、乙酸丁酯、2·經 2-羥基-2-甲基丙酸甲酯、2-羥基-2·甲基丙酸 * 酸甲酯、羥基乙酸乙酯、羥基乙酸丁酯、乳 • 乙酯 '乳酸丙酯 '乳酸丁酯、3-羥基丙酸甲 酸乙酯、3 -羥基丙酸丙酯、3 -羥基丙酸丁酯 基丁酸甲酯、甲氧基乙酸甲酯、甲氧基乙酸 乙酸丙酯、甲氧基乙酸丁酯、乙氧基乙酸甲 Φ 酸乙酯、乙氧基乙酸丙酯、乙氧基乙酸丁酯 甲酯、丙氧基乙酸乙酯、丙氧基乙酸丙酯、 酯、丁氧基乙酸甲酯、丁氧基乙酸乙酯、丁氧 丁氧基乙酸丁醋、2 -甲氧基丙酸甲醋、2·甲氧 2 -甲氧基丙酸丙酯、2 -甲氧基丙酸丁酯、2-酯、2-乙氧基丙酸乙酯、2-乙氧基丙酸丙酯、 丁酯、2 -丁氧基丙酸甲酯、2 -丁氧基丙酸乙酿 酸丙酯、2 -丁氧基丙酸丁酯、3 -甲氧基丙酸甲 鲁丙酸乙酯、3·甲氧基丙酸丙酯、3-甲氧基丙酸 基丙酸甲酯、3 -乙氧基丙酸乙酯、3 -乙氧基 乙氧基丙酸丁酯、3 -丙氧基丙酸甲酯、3 -丙氧 3_丙氧基丙酸丙酯、3-丙氧基丙酸丁酯、3-酯、3-丁氧基丙酸乙酯、3-丁氧基丙酸丙酯、 ： 丁酯等酯類。 另外’作爲共聚物[Α]的製造中使用的聚 以使用已知的自由基聚合引發劑，可以列舉 偶氮二異丁腈、2，2’-偶氮二-(2，4-二甲基 酮類；乙酸甲 基丙酸乙酯、 乙酯、羥基乙 酸甲酯、乳酸 酯、3-羥基丙 、2-羥基-3-甲 乙酯、甲氧基 酯、乙氧基乙 、丙氧基乙酸 丙氧基乙酸丁 ,基乙酸丙酯、 ,基丙酸乙酯、 乙氧基丙酸甲 2- 乙氧基丙酸 3、2-丁氧基丙 1酯、3-甲氧基 ^ 丁酯、3·乙氧 丙酸丙酯、3-,基丙酸乙酯、 丁氧基丙酸甲 3- 丁氧基丙酸 合引發劑，可 出例如2，2 ’ -戊腈）、2，2’- -20- 9 1379130 _ 偶氮二-(4-甲氧基-2，4-二甲基戊腈）等偶氮化合物，苯甲醯 基過氧化物、月桂醯基過氧化物、叔丁基過氧化新戊酸酯、 1，1 二-(叔丁基過氧化）環己烷等有機過氧化物以及過氧化 氫。在使用過氧化物作爲自由基聚合引發劑時，還可以將 ' 過氧化物和還原劑一起使用，作爲氧化-還原型引發劑β 在共聚物[Α]的製造中，可以使用調節分子量的分子量 調節劑。作爲其具體的例子，可以列舉出氯仿、四溴化碳 等鹵代烴類，正己基硫醇、正辛基硫醇、正十二烷基硫醇、 ® 叔十二烷基硫醇、锍基乙醇酸等硫醇類，硫化二甲基黃原、 一硫化二異丙基黃原等黃原類，礙品油烧、α -甲基苯乙燃 二聚物等。 本發明中使用的共聚物[Α]的聚苯乙烯換算的重量平均 分子量（以下，稱作"Mw”），通常爲2χ103〜5χ105、較佳 爲5xl〇3〜ιχ1〇5。如果Mw小於2χ103，則顯影後的殘膜率 有降低的傾向，如果超過5χ 1 05，則產生顯影殘留。 離子聚合引發劑丨τη Φ 作爲光陽離子聚合引發劑[Β ]，可以列舉出鑰鹽。鑰鹽由 鎰陽離子和來自路易士酸的陰離子構成。 作爲前述陽離子具體地，可以列舉出二苯基碘鑰、二（對 甲苯基）碘鑰、二（對-叔丁基苯基）碘鑰 '二（對-辛基苯基） 姚鐵、二（對-十八烷基苯基）碘鐡、二（對-辛氧基苯基）碘 : 鐡、二（對-十八烷氧基苯基）碘鑰、苯基（對-十八烷氧基苯 t 基）姚鏺、（對-甲苯基）（對-異丙基苯基）碘鑰、甲基萘基碘 鑰、乙基萘基碘鑰、三苯基鏑 '三（對-甲苯基）鏑、三（對_ 異丙基苯基）毓、三（2,6_二甲基苯基）鏑、三（對-叔丁基苯基） -21 - 1379130 ^ > 鏑、三（對-氰基苯基.）毓、三（對-氯代苯基）銃、二甲基萘基 锍、二乙基萘基鏑' 二甲基（甲氧基）鏑、二甲基（乙氧基） 蔬、一甲基（丙氧基）蔬、二甲基（丁氧基）蔬、二甲基（辛氧 ' 基）鏑、二甲基（十八烷氧基）鏑、二甲基（異丙氧基）鏑、二 - 甲基（叔丁氧基）毓、二甲基（環戊氧基）銃、二甲基（環己氧 基）鏑、二甲基（氟代甲氧基）毓、二甲基（2-氯代乙氧基）銃、 二甲基（3-溴代丙氧基）鏑、二甲基（4-氰基丁氧基）銃、二甲 基（8-硝基辛氧基）毓、二甲基（18-三氟甲基十八烷氧基）銃、 • 二甲.基（2-羥基異丙氧基）锍、二甲基（三（三氯甲基）甲基）鏑 等。較佳爲二（對-甲苯基）碘鎗、（對-甲苯基）（對-異丙基苯 基）碘鐺、二（對·叔丁基苯基）碘鑰、三苯基鏑 '三（對-叔丁 基苯基）鏑等。 作爲前述來自路易士酸的陰離子，具體地可以列舉出六 氟磷酸鹽、六氟鋁酸鹽、六氟銻酸鹽、四（五氟苯基）硼酸 鹽等’較佳爲六氟銻酸鹽、四（五氟苯基）硼酸鹽。 可以將前述錄陽離子和來自路易士酸的陰離子任意組 • 合。 具體地’作爲[B ]光陽離子聚合引發劑，可以列舉出二苯 基碘錄六氟磷酸鹽、二（對甲苯基）碘_六氟磷酸鹽、二（對· 叔丁基苯基）碘鑰六氟磷酸鹽、二（對-辛基苯基）碘鎰六氟磷 酸鹽、二（對-十八烷基苯基）碘鑰六氟磷酸鹽、二（對-辛氧 : 基苯基）碘鑰六氟磷酸鹽、二（對-十八烷氧基苯基）碘鑰六氟 磷酸鹽、苯基（對-十八烷氧基苯基）碘鏺六氟磷酸鹽 '(對- r 甲苯基）（對-異丙基苯基）碘鑰六氟磷酸鹽、甲基萘基碘鐵六 氟磷酸鹽、乙基萘基碘鑰六氟磷酸鹽、三苯基鏑六氟磷酸 -22- 1379130 » *· 鹽、三（對-甲苯基）锍六氟磷酸鹽、三（對-異丙基苯基）锍六 •氟磷酸鹽、三（2,6·二甲基苯基）锍六氟磷酸鹽、三（對-叔丁 基苯基）毓六氟磷酸鹽、三（對-氰基苯基）銃六氟磷酸鹽、三 ' (對-氯代苯基）銃六氟磷酸鹽、二甲基萘基锍六氟磷酸鹽、 • 二乙基萘基錡六氟磷酸鹽、二甲基（甲氧基）鏑六氟磷酸 鹽、二甲基（乙氧基）鏑六氟磷酸鹽、二甲基（丙氧基）鏡六氟 磷酸鹽、二甲基（丁氧基）锍六氟磷酸鹽、二甲基（辛氧基） 锍六氟磷酸鹽、二甲基（十八烷氧基）锍六氟磷酸鹽、二甲 • 基（異丙氧基）锍六氟磷酸鹽、二甲基（叔丁氧基)銃六氟磷酸 鹽、二甲基（環戊氧基）毓六氟磷酸鹽、二甲基（環己氧基） 鏑六氟磷酸鹽、二甲基（氟代甲氧基）鏑六氟磷酸鹽、二甲 基（2-氯代乙氧基）鏑六氟磷酸鹽、二甲基（3_溴代丙氧基）毓 .六氟磷酸鹽、二甲基（4-氰基丁氧基）鏑六氟磷酸鹽、二甲基 (8-硝基辛氧基）銃六氟磷酸鹽、二甲基（18_三氟甲基十八烷 氧基）鏑六氟磷酸鹽、二甲基（2-羥基異丙氧基）锍六氟磷酸 鹽、二甲基（三（三氯甲基）甲基）鏑六氟磷酸鹽； • 二苯基碘鑰六氟鋁酸鹽、二（對甲苯基）碘鑰六氟鋁酸 鹽、二（對-叔丁基苯基）碘鑰六氟鋁酸鹽、二（對-辛基苯基） 碘鑰六氟鋁酸鹽、二（對-十八烷基苯基）碘鑰六氟鋁酸鹽、 二（對-辛氧基苯基）碘鑰六氟鋁酸鹽、二（對-十八烷氧基苯 基）碘鑰六氟鋁酸鹽、苯基（對-十八烷氧基苯基）碘鑰六氟鋁 : 酸鹽、（對-甲苯基）（對-異丙基苯基）碘鑰六氟鋁酸鹽、甲基 萘基碘鑰六氟鋁酸鹽、乙基萘基碘鐡六氟鋁酸鹽、三苯基 f 锍六氟鋁酸鹽、三（對-甲苯基）鏑六氟鋁酸鹽、三（對-異丙 基苯基）锍六氟鋁酸鹽、三（2,6-二甲基苯基）鏑六氟鋁酸 -23- 1379130 ， y 鹽、三（對-叔丁基苯基）锍六氟鋁酸鹽、.三（對-氰基苯基）锍 六氟鋁酸鹽、三（對-氯代苯基）ίί六氟鋁酸鹽、二甲基萘基 锍六氟鋁酸鹽、二乙基萘釋锍六氟鋁酸鹽、二甲基（甲氧基） ' 鏑六氟鋁酸鹽、二甲基（乙氧基）鏑六氟鋁酸鹽、二甲基（丙 - 氧基）锍六氟鋁酸鹽、二甲基（丁氧基）锍六氟鋁酸鹽、二甲 基（辛氧基）鏡六氟鋁酸鹽 '二甲基（十八烷氧基）毓六氟鋁酸 鹽、二甲基（異丙氧基）锍六氟鋁酸鹽、二甲基（叔丁氧基） 锍六氟鋁酸鹽、二甲基（環戊氧基）鏑六氟鋁酸鹽、二甲基（環 # 己氧基）鏑六氟鋁酸鹽、二甲基（氟代甲氧基）锍六氟鋁酸 鹽、二甲基（2-氯代乙氧基）鏑六氟鋁酸鹽、二甲基（3-溴代 丙氧基）毓六氟鋁酸鹽、二甲基（4-氰基丁氧基）毓六氟鋁酸 鹽、二甲基（8-硝基辛氧基）锍六氟鋁酸鹽、二甲基（18-三氟 甲基十八烷氧基）鏑六氟鋁酸鹽、二甲基（2-羥基異丙氧基） 锍六氟鋁酸鹽、二甲基（三（三氯甲基）甲基）鏑六氟鋁酸鹽； 二苯基碘鑰六氟銻酸鹽、二（對甲苯基）碘鎰六氟銻酸 鹽、二（對-叔丁基苯基）碘鎰六氟銻酸鹽、二（對-辛基苯基） φ 碘鍤六氟銻酸鹽、二（對-十八烷基苯基）碘鑰六氟銻酸鹽、 二（對·辛氧基苯基）碘鎰六氟銻酸鹽、二（對-十八烷氧基苯 基）碘鑰六氟銻酸鹽、苯基（對-十八烷氧基苯基）碘鏺六氟銻 酸鹽、（對-甲苯基）（對-異丙基苯基）碘鎰六氟銻酸鹽、甲基 萘基碘鐵六氟銻酸鹽、乙基萘基碘鐺六氟銻酸鹽、三苯基Glycidyl acrylate, 2-methylglycidyl chloroformate, 4-hydroxybutyl acrylate glycidyl acrylate, 3,4-epoxybutyl acrylate, 6,7-epoxyheptyl acrylate, acrylic acid 3 Acrylic (cyclo)alkyl acrylates such as 4-epoxycyclohexyl ester, glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxybutyl methacrylate Epoxy (cyclo)alkyl methacrylates such as esters, 6,7-epoxyheptyl methacrylate, 3,4-epoxycyclohexyl methacrylate, α-ethyl glycidyl acrylate, Glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, 6,7-epoxyheptyl α-ethyl acrylate, 3,4-epoxycyclohexyl α-ethyl acrylate, etc. Other α-alkyl acrylate epoxy (cyclo)alkyl esters; o-vinyl benzyl glycidyl ether 'm-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether and other glycidol Ethers, etc. Examples of the oxetanyl group-containing unsaturated compound include 3-(methacryloxymethyl)oxetane' 3-(methacryloxymethyl)-3-B. Oxycyclobutane, 3-(methacryloxymethyl)-3-methyloxetane, 3-(methacryloxymethyl)-2-methyloxene Butane, 3-(methacryloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloxymethyl)-2-pentafluoroethyloxycyclohexane Butane, 3-(methacryloxymethyl)-2-phenyloxetane, 3-(methacryloxymethyl)-2,2-difluorooxetane Alkane, 3-(methacryloxymethyl)-2,2,4-trifluorooxetane, 3"methacryloxymethyl"-2,2,4.,4 -tetrafluorooxetane, 3-(methacryloxyethyl)oxetane, 3-(methacryloxyethyl)-3-ethyloxetane 2-ethyl-3-(methacryloxyethyl)oxetane, 3-(methyl 1379130 r · propylene methoxyethyl)-2-trifluoromethyl oxetane Alkane, 3-(methacryloxy) -2-pentafluoroethyl oxetane, 3-(methacryloxyethyl)-2-phenyl-oxetane, 2,2-difluoro-3-(A Acryloxyethyl oxetane, 3-(methacryloxyethyl)-2,2,4-trifluoroox. Heterocyclobutane, 3-(methacryl醯oxyethyl)-2,2,4,4-tetrafluorooxetane, 2-(methacryloxymethyl)oxetane' 2-methyl-2-( Methyl propylene methoxymethyl) oxetane, 3·methyl-2-(methacryloxymethyl) oxetane, 4-methyl-2-(methacryl)醯oxymethyl)oxetane, 2-(methacryloxymethyl)-2-trifluoromethyloxetane, 2-(methacryloxymethyl)- 3-trifluoromethyloxetane, 2-(methacryloxymethyl)-4-trifluoromethyloxetane, 2-(methacryloxymethyl)- 2-pentafluoroethyloxetane, 2-(methacryloxymethyl)-3-pentafluoroethyloxetane, 2-(methacryloxymethyl)- 4-pentafluoroethyl oxetane, 2-(methacryloxymethyl)-2-phenyloxy Cyclobutane, 2-(methacryloxymethyl)-3-phenyloxetane, 2-(methylφ propylene methoxymethyl)-4-phenyl oxetane , 2,3-difluoro-2-(methacryloxymethyl)oxetane, 2,4-difluoro-2-(methacryloxymethyl)oxyheterocycle Butane, 3,3-difluoro.2(methacryloxymethyl)oxetane, 3,4-difluoro-2-(methacryloxymethyl)oxy Heterocyclobutane, 4,4-difluoro-2·(methacryloxymethyl)oxetane, 2-(methyl; propylene methoxymethyl)-3,3,4 -Trifluorooxetane, 2-(methacryloxymethyl)-3,4,4-trifluorooxetane, 2-(methacryloxymethyl) -3,3,4,4-tetrafluorooxetane, .2-(methacryloxyethyl)oxetane, methacrylic acid-12-1379130 9 · 2-(2 -(2 ·methyloxetanyl))ethyl ester, 2-(2-(3-methyloxetanyl))ethyl methacrylate, 2-(methacryloxyloxy) Ethyl)-2-methyloxetane, 2-(methacryloxyethyl)-4-methyloxetane 2-(Methyl propylene oxiranyloxy) 2-trifluoromethyl oxetane, 2-(methyl propylene. methoxyethyl)-3-trifluoromethyl oxetane Alkane, 2-(methacryloxyethyl)-4.trifluoromethyloxetane, 2-(methacryloxyethyl)-2-pentafluoroethyloxetane Alkane, 2-(methacryloxyethyl)-3-pentafluoroethyloxetane, 2-(methacryloxyethyl)-4-pentafluoroethyloxa# ring Butane, 2-(methacryloxyethyl)-2-phenyloxetane, 2-(methacryloxyethyl)-3-phenyloxetane, 2 -(methacryloxyethyl)-4-phenyloxetane, 2,3-difluoro-2-(methacryloxyethyl)oxetane, 2, 4-difluoro-2-(methacryloxyethyl)oxetane, 3,3-difluoro-2-(methacryloxyethyl)oxetane, 3,4-difluoro-2-(methacryloxyethyl)oxetane, 4,4-difluoro-2-(methacryloxyethyl)oxetane Alkane, 2-(methacryloxyethyl)-3,3,4-trifluorooxetane' 2-(methyl Alkyloxy^ethyl)-3,4,4-trifluorooxetane' 2·(methacryloxyethyl)-3,3,4,4-tetrafluorooxa Methyl acrylate such as cyclobutane; 3-(acryloxymethyl)oxetane, 3-(acryloxymethyl)-3-ethyloxetane, 3-( Propylene methoxymethyl)-3-methyloxetane' 3-.(Acryloxymethyl)-2-methyloxetane' 3-(acrylofluorene; oxymethyl )-2-trifluoromethyloxetane, 3-(acryloxymethyl)-2-pentafluoroethyloxetane, 3-(acryloxymethyl)-2- Phenyloxyheterocycle, butane, 3-(propenyloxymethyl)-2,2-difluorooxetane, 3-(acryloxymethyl)-2,2,4- Trifluorooxetane, 3-(acryloxymethyl 1379130)-2,2,4,4-tetrafluorooxetane, 3-(acryloxyethyl)oxalate Cyclobutane, 3-(acryloxyethyl)-3-ethyl.oxetane'2-ethyl•3-(acryloxyethyl)oxetane, 3-( Propylene oxiranyl ethyl) 2-difluoromethyl oxetane, 3. (propionyloxyethyl)-2 -pentafluoro Ethyloxy 'heterocyclobutane, 3-(acryloxyethyl)-2-phenyloxetane, 2,2-difluoro-3-(propyleneoxyethyl) oxalate环丁院, 3-(acrylamidoethyl)-2,2,4-trifluorooxetane, 3-(acryloxyethyl)-2,2,4,4- Tetrafluorooxetane, ® 2-(propylene methoxymethyl) oxetane, 2-methyl-2-(propylene methoxymethyl) oxetane, 3-methyl 2-(acryloxymethyl)oxetane, 4-methyl-2-(propylene methoxymethyl)oxetane, 2-(acryloxymethyl)- 2-trifluoromethyloxetane, 2-(acryloxymethyl)-trifluoromethyloxetane, 2-(acryloxymethyl)-4-trifluoro Methyl oxetane, 2-(acryloxymethyl)-2-pentafluoroethyl oxetane, 2-(propylene methoxymethyl)-3-pentafluoroethyl oxalate Cyclobutane, 2-(propenyl methoxymethyl)-4-pentafluoroethyl oxetane, 2-(propylene methoxymethyl)·2-Φ phenyl oxetane , 2-(acryloxymethyl)-3 phenyl oxetane, 2-(acryloxymethyl)-4-benzene Oxetane, 2,3-difluoro-2-(acryloxymethyl)oxetane, 2,4-difluoro-2·(acryloxymethyl)oxalate Cyclobutane, 3,3-difluoro-2-(propenyloxymethyl)oxetane, 3,4-difluoro-2-(propenyloxymethyl)oxetane Alkane, 4,4-: difluoro-2-(propenyloxymethyl)oxetane, 2-(acryloxymethyl)-3,3,4-trifluorooxocycle Butane, 2-(acryloxymethyl)-3,4,4- «trifluorooxetane, 2-(acryloxymethyl)-3, 3,4,4-tetra Fluorooxetane, -14-1379130 2-(acryloxyethyl)oxetane, 2-(2-(2-methyloxetanyl)ethyl methacrylate Ester, 2-(2-(3-methyloxetanyl))ethyl methacrylate, 2-(acryloxyethyl)-2-.methyloxetane, 2- (Allyloxyethyl)-4-methyloxetane, 2·(acryloxyethoxy)-2-trifluoromethyloxetane, 2-(acryloxyloxy) Ethyl)-3-trifluoromethyloxetane, 2-(acryloxyethyl)-4-trifluoromethyloxetane 2·(Propyloxyethyl)-2-pentafluoroethyloxetane, 2-(acryloxyethyl)-3-pentafluoroethyloxetane, 2-(propylene醯ethoxyethyl)-4-pentafluoroethyl oxetane, 2·(propylene methoxyethyl)-2-phenyl oxetane, 2-(acryloxyethyl) -3-phenyloxetane, 2-(acryloxyethyl bromide 4-phenyloxetane, 2,3-difluoro-(2-propenyloxyethyl) Oxetane, 2,4-difluoro-2-(propenyloxyethyl)oxetane 3,3-difluoro-2-(acryloxyethyl)oxalate Cyclobutane, 3,4-difluoro-2·(acryloxyethyl)oxetane, 4,4-difluoro-2-(propenyloxyethyl)oxetane Alkane, 2-(acryloxyethyl)-3,3,4-trifluorooxetane, 2-(acryloxyethyl)-3,4,4-•trifluoroox Acrylates such as heterocyclobutane and 2-(acryloxyethyl)-3,3,4,4.tetrafluorooxetane. Among them, from the viewpoint that the obtained photosensitive resin composition has a wide process range and the chemical resistance of the obtained protrusions and spacers can be improved, it is preferable to use methacrylic acid to shrink as an epoxy group-containing unsaturated compound: Glyceride, 2-methylglycidyl methacrylate, 6,7-epoxyheptyl methacrylate, 4-hydroxybutyl acrylate glycidyl ether, o-vinylbenzyl glycidyl ether, inter Vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether; as an oxetanyl-containing unsaturated compound, -15-1379130 ♦ « Good use of 3-(methacryloxymethyl) Oxetane, 3-(methacryloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloxymethyl)-2-phenyloxy Heterocyclobutane, 2-(methacryloxymethyl)oxetane, 2·(methacryloxymethyl)-4-trifluoromethyloxetane, 3- (methacryloxymethyl)-3-ethyloxetane, 3-(methacryloxymethyl)-3-methyloxetane, 3-(propylene oxide) Base armor ) -3-ethyl oxetane, 3- (Bing Xixi yloxy) -3-methyl oxetane. They can be used alone or in combination. The copolymer [A] used in the present invention preferably contains 10 to 80% by weight of the constituent unit derived from the compound U3), and particularly preferably contains 20 to 70% by weight. When the constituent unit is less than 10% by weight, the storage stability of the copolymer [A] tends to be lowered. On the other hand, when it exceeds 80% by weight, the copolymer [A] is hardly soluble in the alkaline aqueous solution. Examples of the compound (a3) include alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate and t-butyl methacrylate, and acrylic acid. Alkyl acrylates such as methyl ester and isopropyl acrylate; cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate-trimethyl methacrylate [5.2.1.〇2.6]癸-8-yl Ester (as a commonly used name in the field 'also known as dicyclopentanyl methacrylate), dimethyl pentaneoxyethyl methacrylate, isophorone methacrylate, etc. Alkyl esters, cyclohexyl acrylate, 2-methylcyclohexyl acrylate 'tricyclo[5.2.1 · 02·6] 癸·8-yl ester (also known as acrylic acid in the field) A cycloalkyl acrylate such as dicyclopentanyl acrylate, dicyclopentanyloxyethyl acrylate, isophorone acrylate, aryl methacrylate such as phenyl methacrylate or benzyl methacrylate Ester-16-1379130 ♦ · Classes, aryl acrylates such as phenyl acrylate and benzyl acrylate, Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, etc. Base esters; bicyclo [2.2. 1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene' 5-ethylbicyclo[2.2.1]hept-2-ene , 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-carboxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene , 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[ 2.2.1]hept-2-ene, 5.6-dihydroxybicyclo[2.2.1]hept-2-ene, 5.6-dicarboxybicyclo[2.2.1]hept-2-ene, 5.6-di(hydroxyl) Bi)[2.2.1]hept-2-ene, 5.6-bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5.6-dimethoxybicyclo[2.2. 1]hept-2-ene, 5.6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5- Hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] Hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1]Hept-2-ene, -17-1379130 》 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene, 5.6 - one residue-ring [2.2.1]g ·2·Sodium sulphate (norbornic acid dianhydride), 5-tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]heptane- 2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-((su-butoxy)-bicyclo[2.2.1]hept-2-, 5.6 a bicyclic unsaturated compound such as bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene; phenylmaleimide, cyclohexylmaleimide, benzylamidine Imine, hydrazine-amber succinimide-3-maleimide benzoate, n-succinimide-4-amine sulphonate, samarium-succinimide ·6-maleimide caproate, Ν-amber quinone imine-3-maleimide propionate, ν-(9-acridinyl)maleimide, etc. Imine derivatives; styrene, α-methylstyrene 'm-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, Vinyl chloride 'vinylidene chloride, acrylamide, methyl Enamine, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, glycidyl acrylate, glycidyl methacrylate, B Glycidyl acrylate, glycidyl α-n-propyl acrylate, glycidyl n-butyl acrylate, 3,4·butyl butyl acrylate methacrylate - 3,4-epoxybutyl ester, Acrylic acid-6,7. epoxyheptyl ester, -6,7-epoxyheptyl methacrylate, 6,7-epoxyheptyl ethacrylate, o-vinylbenzyl glycidyl ether, between Vinylbenzyl glycidyl ether, p-vinylbenzyl condensation, glyceryl ether, and the like. Among them, from the copolymerization reactivity and the solubility in an aqueous alkaline solution, -18-1379130 is produced, preferably styrene, tert-butyl methacrylate, dicyclopentanyl methacrylate, p-methoxy Styrene, 2-methylcyclohexyl acrylate, 1,3-butadiene 'glycidyl methacrylate, o-vinylbenzyl glycidyl* ether, m-vinylbenzyl glycidyl ether, p- Vinylbenzyl glycidyl ether, ether, phenylmaleimide, cyclohexylmaleimide, bicyclo[2.2.1]hept-2-ene, and the like. They can be used singly or in combination. As described above, the copolymer [A] used in the present invention has a carboxyl group and/or a carboxylic anhydride group and an oxetanyl group, and has an appropriate solubility to an alkaline aqueous solution, and is not used together with a specific curing agent. It can be easily cured by heating. The radiation-sensitive resin composition containing the above copolymer [A] does not cause development residue during development, and film formation does not occur, and a coating film of a predetermined pattern is easily formed. The solvent to be used in the synthesis of the copolymer [A] may, for example, be an alcohol such as methanol or ethanol; an ether such as tetrahydrofuran; ethylene glycol monomethyl ether or ethylene glycol monoethyl ether; Alcohol ethers; methyl cellosolve acetate' • Ethyl cellosolve acetate and other glycol alkyl ether acetates; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether 'two Diethylene glycol such as glycol dimethyl ether, diethylene glycol diethyl ether 'diethylene glycol ethyl methyl ether; propylene glycol such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether Monoalkyl ethers; propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene: alcohol propyl ether acetate, propylene glycol butyl ether acetate, etc.; propylene glycol alkyl ether acetate; propylene glycol Propylene glycol alkyl ether propionate such as methyl ether propionate, propylene glycol ethyl ether propionate 'propylene' glycol propyl ether propionate, propylene glycol butyl ether propionate; aromatics such as toluene' xylene Hydrocarbons; -19- 1379130 ♦ m methyl ethyl ketone, cyclohexanone ' 4 · hydroxy - 4 · methyl - 2 · pentanone and other vinegar, ethyl acetate, acetic acid , butyl acetate, 2·methyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2·methylpropionic acid* methyl ester, ethyl hydroxyacetate, butyl glycolate, milk • ethyl ester 'Lactate propyl ester' butyl lactate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, methyl 3-butoxybutyrate, methyl methoxyacetate, methoxyacetic acid Propyl acetate, butyl methoxyacetate, ethyl methoxyacetate, propyl ethoxyacetate, methyl butyl ethoxide, ethyl propoxyacetate, propyl propoxy propyl acetate , ester, methyl butoxyacetate, ethyl butoxide, butyl acetobutoxyacetate, methyl 2-methoxypropionate, propyl 2-methoxy 2-propoxypropionate, Butyl 2-methoxypropionate, 2-ester, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl ester, methyl 2-butoxypropionate, 2-but Propyl propyl propionate, butyl 2-butoxypropionate, ethyl 3-methylmethoxypropionate, propyl 3-methoxypropionate, 3-methoxypropane Methyl acid propionate, ethyl 3-ethoxypropionate, butyl 3-ethoxyethoxypropionate, Methyl 3-propoxypropionate, propyl 3-propoxy 3-propoxypropanoate, butyl 3-propoxypropionate, 3-ester, ethyl 3-butoxypropionate, 3- Esters such as propyl butoxypropionate and : butyl ester. Further, 'the polymerization used in the production of the copolymer [Α] is a known radical polymerization initiator, and examples thereof include azobisisobutyronitrile and 2,2'-azobis-(2,4-dimethyl). Ketones; ethyl acetate methyl propionate, ethyl ester, methyl hydroxyacetate, lactate, 3-hydroxypropane, 2-hydroxy-3-methylethyl ester, methoxy ester, ethoxylate B, C Oxyacetic acid propoxyacetic acid butyl, propyl acetate, ethyl propyl propionate, methoxy propionic acid methyl 2-ethoxypropionic acid 3, 2-butoxy propane 1, 3-methoxy ^ Butyl ester, propyl ethoxypropionate, 3-, ethyl propionate, methyl 3-butoxypropionic acid initiator, such as 2,2 '-pentanenitrile) , 2,2'- -20- 9 1379130 _ azo-(4-methoxy-2,4-dimethylvaleronitrile) and other azo compounds, benzhydryl peroxide, lauryl Organic peroxides such as oxides, t-butyl peroxypivalate, 1,1 di-(tert-butylperoxy)cyclohexane, and hydrogen peroxide. When a peroxide is used as the radical polymerization initiator, a peroxide can be used together with a reducing agent as an oxidation-reduction initiator β. In the production of a copolymer [Α], a molecular weight adjusting molecular weight can be used. Conditioner. Specific examples thereof include halogenated hydrocarbons such as chloroform and carbon tetrabromide, n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, and ethyl t-dodecyl mercaptan. Mercaptans such as glycolic acid, xylogens such as dimethyl sulphate and diisopropyl xanthogen, which are obstructed by oil burning, α-methyl benzene ethane dimer, and the like. The polystyrene-equivalent weight average molecular weight (hereinafter referred to as "Mw") of the copolymer [Α] used in the present invention is usually 2χ103 to 5χ105, preferably 5xl〇3 to ιχ1〇5. If Mw is smaller than 2χ103, the residual film ratio after development tends to decrease, and if it exceeds 5 χ 105, development residue occurs. Ionic polymerization initiator 丨τη Φ As a photocationic polymerization initiator [Β], a key salt can be mentioned. It is composed of a ruthenium cation and an anion derived from Lewis acid. Specific examples of the cation include diphenyl iodine, bis(p-tolyl) iodine, and di(p-tert-butylphenyl) iodine (p-octylphenyl) Yao iron, bis(p-octadecylphenyl)iodonium, bis(p-octyloxyphenyl)iodine: ruthenium, di(p-octadecyloxyphenyl) Iodine, phenyl (p-octadecyloxybenzene t-based) Yao, (p-tolyl) (p-isopropylphenyl) iodine, methyl naphthyl iodide, ethyl naphthyl Iodine, triphenylsulfonium tris(p-tolyl)pyrene, tris(p-isopropylphenyl)anthracene, tris(2,6-dimethylphenyl)anthracene, Tris(p-tert-butylphenyl) -21 - 1379130 ^ > ruthenium, tris(p-cyanophenyl) oxime, tris(p-chlorophenyl)anthracene, dimethylnaphthyl fluorene, two Ethylnaphthyl anthracene dimethyl (methoxy) hydrazine, dimethyl (ethoxy) vegetable, monomethyl (propoxy) vegetable, dimethyl (butoxy) vegetable, dimethyl ( Octyloxy, dimethyl(octadecyloxy)phosphonium, dimethyl(isopropoxy)phosphonium, di-methyl(tert-butoxy)phosphonium, dimethyl(cyclopentyloxy)铳, dimethyl (cyclohexyloxy) hydrazine, dimethyl (fluoromethoxy) hydrazine, dimethyl (2-chloroethoxy) hydrazine, dimethyl (3-bromopropoxy oxy)镝, dimethyl (4-cyanobutoxy) hydrazine, dimethyl (8-nitrooctyloxy) hydrazine, dimethyl (18-trifluoromethyloctadecyloxy) hydrazine, • Dimethyl (2-hydroxyisopropoxy) hydrazine, dimethyl (tris(trichloromethyl)methyl) hydrazine, etc., preferably di(p-tolyl) iodine gun, (p-toluene) (p-isopropylphenyl) iodonium, di(p-tert-butylphenyl) iodine, triphenylsulfonium tris(p-tert-butylphenyl) The anion derived from the Lewis acid may specifically be hexafluorophosphate, hexafluoroaluminate, hexafluoroantimonate or tetrakis(pentafluorophenyl)borate, preferably hexafluoro. Citrate, tetrakis(pentafluorophenyl)borate. The above-mentioned cation can be arbitrarily combined with an anion derived from Lewis acid. Specifically, as the [B] photocationic polymerization initiator, diphenyl can be exemplified. Iodine hexafluorophosphate, bis(p-tolyl)iodine-hexafluorophosphate, bis(p-t-butylphenyl) iodine hexafluorophosphate, bis(p-octylphenyl)iodonium hexafluorophosphate Phosphate, di(p-octadecylphenyl) iodine hexafluorophosphate, bis(p-octyloxy: phenyl) iodine hexafluorophosphate, di(p-octadecyloxyphenyl) Iodine hexafluorophosphate, phenyl (p-octadecyloxyphenyl) iodonium hexafluorophosphate '(p-r-tolyl) (p-isopropylphenyl) iodine hexafluorophosphate , methyl naphthyl iron iodide hexafluorophosphate, ethyl naphthyl iodine hexafluorophosphate, triphenyl sulfonium hexafluorophosphate-22- 1379130 » *· salt, three (p--a Hexafluorophosphate, tris(p-isopropylphenyl)phosphonium hexafluorophosphate, tris(2,6-dimethylphenyl)phosphonium hexafluorophosphate, tris(p-tert-butyl) Phenyl)phosphonium hexafluorophosphate, tris(p-cyanophenyl)phosphonium hexafluorophosphate, tris(p-chlorophenyl)phosphonium hexafluorophosphate, dimethylnaphthylphosphonium hexafluorophosphate , • diethylnaphthylphosphonium hexafluorophosphate, dimethyl(methoxy)phosphonium hexafluorophosphate, dimethyl(ethoxy)phosphonium hexafluorophosphate, dimethyl (propoxy) mirror Hexafluorophosphate, dimethyl(butoxy)phosphonium hexafluorophosphate, dimethyl(octyloxy)phosphonium hexafluorophosphate, dimethyl(octadecyloxy)phosphonium hexafluorophosphate, two Methyl(isopropoxy)phosphonium hexafluorophosphate, dimethyl(tert-butoxy)phosphonium hexafluorophosphate, dimethyl(cyclopentyloxy)phosphonium hexafluorophosphate, dimethyl (ring Hexyloxy) hexafluorophosphate, dimethyl(fluoromethoxy)phosphonium hexafluorophosphate, dimethyl(2-chloroethoxy)phosphonium hexafluorophosphate, dimethyl (3_ Bromopropoxy) quinone hexafluorophosphate, dimethyl (4 -Cyanobutoxy)phosphonium hexafluorophosphate, dimethyl(8-nitrooctyloxy)phosphonium hexafluorophosphate, dimethyl (18-trifluoromethyloctadecyloxy)phosphonium hexafluorophosphate Phosphate, dimethyl(2-hydroxyisopropoxy)phosphonium hexafluorophosphate, dimethyl(tris(trichloromethyl)methyl)phosphonium hexafluorophosphate; • diphenyl iodine hexafluoroaluminum Acid salt, di(p-tolyl) iodine hexafluoroaluminate, di(p-tert-butylphenyl) iodine hexafluoroaluminate, di(p-octylphenyl) iodine hexafluoroaluminate Salt, di(p-octadecylphenyl) iodine hexafluoroaluminate, bis(p-octyloxyphenyl) iodine hexafluoroaluminate, di(p-octadecyloxyphenyl) Iodine hexafluoroaluminate, phenyl (p-octadecyloxyphenyl) iodine hexafluoroaluminum: acid salt, (p-tolyl) (p-isopropylphenyl) iodine hexafluoro Aluminate, methylnaphthyl iodine hexafluoroaluminate, ethylnaphthyl iodonium hexafluoroaluminate, triphenyl f hexafluoroaluminate, tris(p-tolyl) hexafluoroaluminum Acid salt, tris(p-isopropylphenyl)phosphonium hexafluoroaluminate, tris(2,6-dimethylphenyl)phosphonium hexafluoride Aluminate-23- 1379130, y salt, tris(p-tert-butylphenyl)phosphonium hexafluoroaluminate, tris(p-cyanophenyl)phosphonium hexafluoroaluminate, tris(p-chloro Phenyl), hexafluoroaluminate, dimethylnaphthylphosphonium hexafluoroaluminate, diethyl naphthoquinone hexafluoroaluminate, dimethyl(methoxy)' hexafluoroaluminate, Dimethyl(ethoxy)phosphonium hexafluoroaluminate, dimethyl(propyl-oxy)phosphonium hexafluoroaluminate, dimethyl(butoxy)phosphonium hexafluoroaluminate, dimethyl ( Octyloxy) hexafluoroaluminate 'dimethyl(octadecyloxy)phosphonium hexafluoroaluminate, dimethyl(isopropoxy)phosphonium hexafluoroaluminate, dimethyl (tert-butyl) Oxyl) hexafluoroaluminate, dimethyl (cyclopentyloxy) ruthenium hexafluoroaluminate, dimethyl (cyclohexyloxy) hexafluoroaluminate, dimethyl (fluoromethyl) Oxy) hexafluoroaluminate, dimethyl(2-chloroethoxy)phosphonium hexafluoroaluminate, dimethyl(3-bromopropoxy)phosphonium hexafluoroaluminate, dimethyl (4-cyanobutoxy)phosphonium hexafluoroaluminate, dimethyl(8-nitrooctyloxy)phosphonium hexafluoroaluminate, dimethyl (18-trifluoromethyloctadecyloxy)phosphonium hexafluoroaluminate, dimethyl(2-hydroxyisopropoxy)phosphonium hexafluoroaluminate, dimethyl (tris(trichloromethyl) )methyl)phosphonium hexafluoroaluminate; diphenyl iodine hexafluoroantimonate, bis(p-tolyl)iodonium hexafluoroantimonate, di(p-tert-butylphenyl)iodonium hexafluorophosphate Citrate, bis(p-octylphenyl) φ iodonium hexafluoroantimonate, bis(p-octadecylphenyl) iodine hexafluoroantimonate, di(p-octyloxyphenyl) Iodine hexafluoroantimonate, di(p-octadecyloxyphenyl) iodine hexafluoroantimonate, phenyl (p-octadecyloxyphenyl) iodonium hexafluoroantimonate, (p-tolyl)(p-isopropylphenyl)iodonium hexafluoroantimonate, methylnaphthyl iodide hexafluoroantimonate, ethylnaphthyliodonium hexafluoroantimonate, triphenyl

V ! 鏑六氟銻酸鹽、三（對·甲苯基）毓六氟銻酸鹽、三（對-異丙 基苯基）鏑六氟銻酸鹽、三（2,6-二甲基苯基）鏑六氟銻酸 t 鹽、三（對-叔丁基苯基）锍六氟銻酸鹽、三（對-氰基苯基）鏑 六氟銻酸鹽、三（對-氯代苯基）毓六氟銻酸鹽、二甲基萘基 -24- 1379130 * » 鏑六氟銻酸鹽、二乙基萘基锍六氟銻酸鹽、二甲基（甲氧基） 鏑六氟銻酸鹽、二甲基（乙氧基）鏑六氟銻酸鹽、二甲基（丙 氧基）鏑六氟銻酸鹽 '二甲基（丁氧基）鏑六氟銻酸鹽、二甲 ' 基（辛氧基）鏑六氟銻酸鹽、二甲基（十八烷氧基）锍六氟銻酸 鹽、二甲基（異丙氧基）毓六氟銻酸鹽、二甲基（叔丁氧基） 毓六氟銻酸鹽、二甲基（環戊氧基）鏑六氟銻酸鹽、二甲基（環 己氧基）鏑六氟銻酸鹽、二甲基（氟代甲氧基）锍六氟銻酸 鹽、二甲基（2-氯代乙氧基）鏑六氟銻酸鹽、二甲基（3_溴代 Φ 丙氧基）鏡六氟錄酸鹽、二甲基（4-氰基丁氧基）锍六氟銻酸 鹽、二甲基（8 -硝基辛氧基）毓六氟銻酸鹽、二甲基（18_三氟 甲基十八烷氧基）毓六氟銻酸鹽、二甲基（2_羥基異丙氧基） 锍六氟銻酸鹽 '二甲基（三（三氯甲基）甲基）鏑六氟銻酸鹽； 二苯基碘鑰四（五氟苯基）硼酸鹽、二（對甲苯基）碘鏺四 (五氟苯基）硼酸鹽 '二（對-叔丁基苯基）碘鎰四（五氟苯基） 硼酸鹽、二（對-辛基苯基）碘鎗四（五氟苯基）硼酸鹽、二（對 -十八烷基苯基）碘鎰四（五氟苯基）硼酸鹽、二（對-辛氧基苯 • 基）碘鎰四（五氟苯基）硼酸鹽、二（對-十八烷氧基苯基）碘鑰 四（五氟苯基）硼酸鹽、苯基（對-十八烷氧基苯基）碘鑰四（五 氟苯基）硼酸鹽、（對-甲苯基）（對-異丙基苯基）碘鎰四（五氟 苯基）硼酸鹽、甲基萘基碘鑰四（五氟苯基）硼酸鹽、乙基萘 基碘鑰四（五氟苯基）硼酸鹽 '三苯基毓四（五氟苯基）硼酸 | 鹽、三（對·甲苯基）锍四（五氟苯基）硼酸鹽、三（對-異丙基苯 基）鏑四（五氟苯基）硼酸鹽、三（2,6-二甲基苯基）锍四（五氟 苯基）硼酸鹽、三（對-叔丁基苯基）鏑四（五氟苯基）硼酸鹽、 三（對-氰基苯基）锍四（五氟苯基）硼酸鹽、三（對-氯代苯基） -25- 1379130 锍四（五氟苯基）硼酸鹽、二甲基萘基锍四（五氟苯基）硼酸 鹽、二乙基萘基鏑四（五氟苯基）硼酸鹽、二甲基（甲氧基） 鏑四（五氟苯基）硼酸鹽、二甲基（乙氧基）鏑四（五氟苯基）砸 ' 酸鹽、二甲基（丙氧基）毓四（五氟苯基）硼酸鹽、二甲基（丁 • 氧基）鏑四（五氟苯基）硼酸鹽、二甲基（辛氧基）鏑四（五氟苯 基）硼酸鹽、二甲基（十八烷氧基）锍四（五氟苯基）硼酸鹽、 二甲基（異丙氧基）銃四（五氟苯基）硼酸鹽、二甲基（叔丁氧 基）锍四（五氟苯基）硼酸鹽、二甲基（環戊氧基）锍四（五氟苯 • 基）硼酸鹽、二甲基（環己氧基）鏑四（五氟苯基）硼酸鹽、二 甲基（氟代甲氧基）銃四（五氟苯基）硼酸鹽、二甲基（2-氯代 乙氧基）銃四（五氟苯基）硼酸鹽、二甲基（3-溴代丙氧基）銃 四（五氟苯基）硼酸鹽、二甲基（4-氰基丁氧基）銃四（五氟苯 基）硼酸鹽、二甲基（8 -硝基辛氧基）鏑四（五氟苯基）硼酸 鹽、二甲基（18 -三氟甲基十八烷氧基）銃四（五氟苯基）硼酸 鹽、二甲基（2-羥基異丙氧基）锍四（五氟苯基）硼酸鹽、二甲 基（三（三氯甲基）甲基）鏑四（五氟苯基）硼酸鹽等。 φ 較佳爲二（對-甲苯基）碘鐵六氟磷酸鹽、（對-甲苯基）（對 -異丙基苯基）碘銷六氟磷酸鹽、二（對-叔丁基苯基）碘鐵六 氟磷酸鹽、三苯基毓六氟磷酸鹽、三（對-叔丁基苯基）锍六 氟磷酸鹽、二（對-甲苯基）碘鑰六氟鋁酸鹽、（對-甲苯基）（對 異丙基苯基）碘鑰六氟鋁酸鹽、二（對-叔丁基苯基）碘鎰六 . 氟鋁酸鹽、三苯基毓六氟鋁酸鹽、三（對-叔丁基苯基）鏑六 氟鋁酸鹽、二（對-甲苯基）碘錄六氟銻酸鹽、（對-甲苯基）（對 ' -異丙基苯基）碘鎰六氟銻酸鹽 '二（對-叔丁基苯基）碘鎰六 氟銻酸鹽、三苯基鏑六氟銻酸鹽、三（對-叔丁基苯基）鏑六 -26- 1379130 f , * 氟鍊酸鹽、二（對-甲苯基）碘鐵四（五氟苯基）硼酸鹽、（對-甲苯基）（對-異丙基苯基）碘鐽四（五氟苯基）硼酸鹽、二（對-叔丁基苯基）碘鎗四（五氟苯基）硼酸鹽、三苯基锍四（五氟 ' 苯基）硼酸鹽、三（對-叔丁基苯基）鏑四（五氟苯基）硼酸鹽 . 等。 更佳爲二（對-甲苯基）碘鑰六氟銻酸鹽、（對·甲苯基）（對 -異丙基苯基）碘鎗六氟銻酸鹽、二（對-叔丁基苯基）碘鑰六 氟銻酸鹽、三苯基锍六氟銻酸鹽、三（對-叔丁基苯基）锍六 • 氟銻酸鹽 '二（對-甲苯基）碘鑰四（五氟苯基）硼酸鹽、（對- 甲苯基）（對-異丙基苯基）碘鑰四（五氟苯基）硼酸鹽、二（對-叔丁基苯基）碘鑰四（五氟苯基）硼酸鹽、三苯基锍四（五氟 苯基）硼酸鹽、三（對-叔丁基苯基）锍四（五氟苯基）硼酸鹽 等。 相對於100重量份共聚物[A]，[B]成分的使用比例爲0.01 〜15重量份，較佳爲0.1〜10重量份。以前述基準計，該 用量如果爲0.0 1〜1 5重量份，就可以提高曝光部分的固化 φ 速度，抑製顯影時圖案的膜減少，提高殘膜率，所以是較 佳的。 噻噸酮類化合物丨C1 作爲[C ]噻噸酮類化合物，可以列舉出例如噻噸酮、2 -異丙基噻噸酮、4 -異丙基噻噸酮、2,3-二乙基噻噸酮、2,4-. 二乙基噻噸酮、2,4 -二氯代噻噸酮、卜氯-4-丙氧基噻噸酮、 2-環己基噻噸酮、4-環己基噻噸酮等。 7 相對於100重量份共聚物[A]，[C]成分的使用比例通 常是1 5重量份或以下，較佳爲0.0 1〜1 5重量份’更佳爲 -27- 1379130 Ό.1〜10重量份。[C]成分的含量爲〇 〇1〜丨纟重量份時，可 以對光陽離子聚合引發劑增敏，提高固化時的固化速度， 抑製固化時的解析度降低’進而提高固化膜的耐溶劑性， 所以是較佳的。 其他成分 本發明的感放射線性樹脂組成物含有上述共聚物[Α]和 [Β]成分，或者[C]成分爲必要成分，根據需要還可以含有[1>] 交聯劑、[Ε]聚合性單體‘、[F]表面活性劑或者[G7]黏合助劑。 上述[D]交聯劑是在作爲[Α]成分的特定的可溶於鹼的樹 脂分子間形成交聯結構的成分。作爲這種交聯劑可以使用 尿素和甲醛的縮合產物（以下，稱作“尿素-甲醛縮合產 物”）、三聚氰胺和甲醒的縮合產物（以下，稱作"三聚氰 胺-甲醛的縮合產物”）、由這些縮合產物和醇類得到的羥 甲基尿素烷基醚類以及羥甲基三聚氰胺烷基酸類等。 作爲前述尿素-甲醛縮合產物的具體例子，可以列舉出 單羥甲基尿素、二羥甲基尿素等。 作爲前述三聚氰胺-甲醛縮合產物的具體例子，可以列 舉出六羥甲基三聚氰胺，此外還可以使用三聚氰胺和甲醛 部分縮合的產物。 前述羥甲基尿素烷基醚類是尿素·甲酸縮合產物中的羥 甲基的一部分或全部和醇反應而得到的’其具體的例子可 以列舉出單羥甲基尿素甲基醚、二羥甲基尿素甲基醚等。 前述羥甲基三聚氰胺烷基醚類是三聚氰胺·甲醛縮合產 物的羥甲基的一部分或全部與甲醇' 正丁醇等醇類反應而 得到的，其具體的例子可以列舉出六經甲基三聚氰胺六甲 -28- 1379130 裊 « 基醚、六羥甲基三聚氰胺六正丁基醚、具有三聚 基的氫原子用羥甲基和甲氧基甲基取代的結構的 具有三聚氰胺的氨基的氫原子用丁氧基甲基和甲 ’ 取代的結構的化合物等。 • 其中，較佳使用羥甲基三聚氰胺烷基醚類，作 甲基三聚氰胺烷基醚類的市售品可以列舉出三井 式會社製造的 “CYMEL 300” 、“CYMEL370” 、 2 3 2 ” 、 “ Μ Y C 0 D 5 0 5 ” 等。 ® 相對於10G重量份[Α]成分，[〇]交聯劑的使用 爲50重量份或以下，更佳爲3〇重量份或以下。 該比例超過50重量份時，在顯影處理中，塗 放射線部分的厚度顯著減少，而且所得的塗膜的 低。 作爲[E ]聚合性單體，例如可以使用受熱能自由 聚合性單體’能陽離子聚合的聚合性單體等。 作爲能自由基聚合的聚合性單體，可以列舉出 φ 聚合性碳-碳不飽和鍵的化合物，可以是單官能 體’也可以是2官能的聚合性單體、3官能或更 聚合性單體等多官能的聚合性單體。 作爲單官能的聚合性單體，可以列舉出例如壬 必醇丙稀酸醋、壬基苯基卡必醇甲基丙烯酸酯、 - 链基·3 -苯氧基丙基酯、甲基丙烯酸2 -羥基·3 -苯 , 醒、2·乙基己基卡必醇丙烯酸酯、2 -乙基己基卡 丙嫌酸醋、丙烯酸2 -羥乙基酯、甲基丙烯酸2 -羥 Ν -乙燃基卩比略院嗣等。 氰胺的氨 化合物， 氧基甲基 爲這種羥 Cytec 株 “ CYMEL 比例較佳 膜未照射 透明性降 基聚合的 例如具有 聚合性單 多官能的 基苯基卡 S烯酸2-氧基丙基 必醇甲基 乙基酯' -29- 1379130 .作爲2官能的聚合性單體，可以列舉出例如 二丙烯酸酯、1,6-己二醇二甲基丙烯酸酯、乙二 醋、乙二醇二甲基丙烯酸酯、新戊二醇二丙烯 二醇二甲基丙燒酸醋、三甘醇二丙焼酸醋、三 丙烯酸酯、雙酚A的二（丙烯醯氧基乙基）醚、 .醇二丙烯酸酯、3·甲基戊二醇二甲基丙烯酸酯〗 作爲上述3官能或以上的聚合性單體，可以 羥甲基丙烷三丙烯酸酯、三羥甲基丙烷三甲基 季戊四醇三丙烯酸酯'季戊四醇三甲基丙烯酸 醇四丙烯酸酯、季戊四醇四甲基丙烯酸酯、季 烯酸酯、季戊四醇五甲基丙烯酸酯、二季戊四 酯、二季戊四醇六甲基丙烯酸酯等。在前述聚爸 較佳使用2官能或3官能或以上的聚合性單體 較佳爲季戊四醇四两烯酸酯、二季戊四醇六丙 更較佳爲二季戊四醇六丙烯酸酯。另外，也可 或3官能或以上的聚合性單體和單官能的聚合 使用。 作爲能陽離子聚合的聚合性單體，可以列舉 乙烯基醚基、丙烯基醚基、環氧基、氧雜環丁 聚合性官能團的聚合性單體。具體地，作爲含 的化合物’可以列舉出例如三甘醇二乙烯基醚 甲醇二乙烯基醚、4 -羥丁基乙烯基醚、十二烷 等；作爲含丙烯基醚基的化合物，可以列舉出 基甲基）-1，3 -二氧戊環-2-酮等；作爲含有環氧基 可以列舉出雙酚A型環氧樹脂、酚醛清漆型環 1,6-己二醇 醇二丙烯酸 酸酯、新戊 甘醇二甲基 3- 甲基戊二 等。 列舉例如三 丙烯酸酯、 酯、季戊四 戊四醇五丙 醇六丙烯酸 Γ性單體中， 。臭體地， 烯酸酯等， 以將2官能 性單體一起 出例如具有 基等陽離子 乙烯基醚基 、1，4 -環己二 基乙烯基醚 4- (1 -丙稀氧 :的化合物， 氧樹脂、甲 -30- 1379130 • 酚酚醛清漆型環氧樹脂、環狀脂肪族環氧樹脂、縮水甘油 酯型環氧樹脂、縮水甘油基胺型環氧樹脂、雜環型環氧樹 脂；作爲含有氧雜環丁基的化合物，可以列舉出二{3-(3-' 乙基氧雜環丁基）甲基}醚、1，4-二{3 “3-乙基氧雜環丁基） . 甲氧基}苯、1，4-二{3-(3·乙基氧雜環丁基）甲氧基}甲苯、1，4-二{3-(3-乙基氧雜環丁基）甲氧基丨環己烷、1,4-二{3-(3-乙基 氧雜環丁基）甲氧基丨甲基環己烷、3-(3-乙基氧雜環丁基）甲 基化酚醛清漆樹脂等。 • 使用前述聚合性單體時，可以分別單獨使用，也可以將 多種一起使用。相對於100重量份共聚物[A]，本發明的感 放射線性樹脂組成物中的[E]聚合性單體的添加量較佳爲 30重量份或以下。 本發明的感放射線性樹脂組成物中可以使用上述[F]表 面活性劑以進一步提高塗布性。這裏使用的[F]表面活性 劑，可以使用氟表面活性劑、有機矽類表面活性劑和非離 子性表面活性劑。 B 作爲氟系表面活性劑的具體例子，可以列舉1，1，2,2·四氟 辛基（1,1,2,2 -四氟丙基）醚、1,1,2,2-四氟辛基己醚、八乙二 醇二（1，1，2,2-四氟丁基）醚、六乙二醇（1，1,2,2,3,3-六氟戊基） 醚、八丙二醇二（1,1，2,2-四氟丁基）醚、六丙二醇二 U,1，2,2,3,3-六氟戊基）醚、全氟十二烷基磺酸鈉、 . 1，1，2,2,8,8,9,9，10，10-十氟十二烷、1，1,2,2,3,3-六氟癸烷， 以及氟代烷基苯磺酸鈉類，氟代烷基氧乙烯醚類，碘化氟 r 代烷基銨類，氟代烷基聚氧乙烯醚類，全氟烷基聚氧乙醇 類，全氟烷基烷氧化物類，氟烷基酯類等。另外，作爲它 -31 - 1379130 • .V ! hexafluoroantimonate, tris(p-tolyl)phosphonium hexafluoroantimonate, tris(p-isopropylphenyl)phosphonium hexafluoroantimonate, tris(2,6-dimethylbenzene Bismuth hexafluoroantimonate t salt, tris(p-tert-butylphenyl)phosphonium hexafluoroantimonate, tris(p-cyanophenyl)phosphonium hexafluoroantimonate, tris(p-chlorobenzene) Hexafluoroantimonate, dimethylnaphthyl-24- 1379130 * » hexafluoroantimonate, diethylnaphthylphosphonium hexafluoroantimonate, dimethyl(methoxy)phosphonium hexafluorophosphate Phthalate, dimethyl(ethoxy)phosphonium hexafluoroantimonate, dimethyl(propoxy)phosphonium hexafluoroantimonate 'dimethyl(butoxy)phosphonium hexafluoroantimonate, two Methyl(octyloxy)phosphonium hexafluoroantimonate, dimethyl(octadecyloxy)phosphonium hexafluoroantimonate, dimethyl(isopropoxy)phosphonium hexafluoroantimonate, dimethyl (tert-butoxy) hexafluoroantimonate, dimethyl(cyclopentyloxy)phosphonium hexafluoroantimonate, dimethyl(cyclohexyloxy)phosphonium hexafluoroantimonate, dimethyl ( Fluoromethoxy)phosphonium hexafluoroantimonate, dimethyl(2-chloroethoxy)phosphonium hexafluoroantimonate, dimethyl (3_ Φ propyl propyl) hexafluoroantimonate, dimethyl (4-cyanobutoxy) hexafluoroantimonate, dimethyl (8-nitrooctyloxy) hexafluoroantimonate , dimethyl (18-trifluoromethyloctadecyloxy) hexafluoroantimonate, dimethyl (2-hydroxyisopropoxy) hexafluoroantimonate 'dimethyl (three (three) Chloromethyl)methyl)phosphonium hexafluoroantimonate; diphenyl iodine tetrakis(pentafluorophenyl)borate, bis(p-tolyl)iodonium tetrakis(pentafluorophenyl)borate 'two (pair -tert-butylphenyl)iodonium tetrakis(pentafluorophenyl)borate, bis(p-octylphenyl) iodine gun tetrakis(pentafluorophenyl)borate, di(p-octadecylphenyl) Iodine tetrakis(pentafluorophenyl)borate, bis(p-octyloxyphenyl) iodonium tetrakis(pentafluorophenyl)borate, di(p-octadecyloxyphenyl) iodine Tetrakis(pentafluorophenyl)borate, phenyl(p-octadecyloxyphenyl)iodyltetrakis(pentafluorophenyl)borate, (p-tolyl)(p-isopropylphenyl) Iodine tetrakis(pentafluorophenyl)borate, methylnaphthyl iodide tetrakis(pentafluorophenyl)borate Ethylnaphthyl iodide tetrakis(pentafluorophenyl)borate 'triphenylphosphonium tetrakis(pentafluorophenyl)borate|salt, tris(p-tolyl)phosphonium tetrakis(pentafluorophenyl)borate, Tris(p-isopropylphenyl)phosphonium tetrakis(pentafluorophenyl)borate, tris(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate, tris(p-tert-butyl) Phenyl) ruthenium tetrakis(pentafluorophenyl)borate, tris(p-cyanophenyl)phosphonium tetrakis(pentafluorophenyl)borate, tris(p-chlorophenyl)-25- 1379130 (pentafluorophenyl)borate, dimethylnaphthylphosphonium tetrakis(pentafluorophenyl)borate, diethylnaphthylphosphonium tetrakis(pentafluorophenyl)borate, dimethyl(methoxy)anthracene Tetrakis(pentafluorophenyl)borate, dimethyl(ethoxy)phosphonium tetrakis(pentafluorophenyl)phosphonate, dimethyl(propoxy)phosphonium tetrakis(pentafluorophenyl)borate, Dimethyl(butyloxy)phosphonium tetrakis(pentafluorophenyl)borate, dimethyl(octyloxy)phosphonium tetrakis(pentafluorophenyl)borate, dimethyl(octadecyloxy)phosphonium Tetrakis(pentafluorophenyl)borate, dimethyl (isopropoxy) Tetrakis(pentafluorophenyl)borate, dimethyl(tert-butoxy)phosphonium tetrakis(pentafluorophenyl)borate, dimethyl(cyclopentyloxy)phosphonium tetrakis(pentafluorophenyl) bromide Salt, dimethyl(cyclohexyloxy)phosphonium tetrakis(pentafluorophenyl)borate, dimethyl(fluoromethoxy)phosphonium tetrakis(pentafluorophenyl)borate, dimethyl (2-chloro) Ethoxylated) ruthenium tetrakis(pentafluorophenyl)borate, dimethyl(3-bromopropoxy)phosphonium tetrakis(pentafluorophenyl)borate, dimethyl(4-cyanobutoxy)铳tetrakis(pentafluorophenyl)borate, dimethyl(8-nitrooctyloxy)phosphonium tetrakis(pentafluorophenyl)borate, dimethyl (18-trifluoromethyloctadecyloxy)铳tetrakis(pentafluorophenyl)borate, dimethyl(2-hydroxyisopropoxy)phosphonium tetrakis(pentafluorophenyl)borate, dimethyl(tris(trichloromethyl)methyl)anthracene Tetrakis(pentafluorophenyl)borate. φ is preferably bis(p-tolyl)iodoferric hexafluorophosphate, (p-tolyl) (p-isopropylphenyl) iodine pin hexafluorophosphate, di(p-tert-butylphenyl) Iodine iron hexafluorophosphate, triphenylsulfonium hexafluorophosphate, tris(p-tert-butylphenyl)phosphonium hexafluorophosphate, di(p-tolyl) iodine hexafluoroaluminate, (p- Tolyl)(p-isopropylphenyl)iodonium hexafluoroaluminate, di(p-tert-butylphenyl)iodonium hexafluoroaluminate, triphenylsulfonium hexafluoroaluminate, tri p-tert-Butylphenyl)phosphonium hexafluoroaluminate, bis(p-tolyl)iodonium hexafluoroantimonate, (p-tolyl) (p-'-isopropylphenyl)iodonium hexafluoro 'Citrate' bis(p-tert-butylphenyl) iodonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate, tris(p-tert-butylphenyl)phosphonium-6-26- 1379130 f , * fluoroalginate, di(p-tolyl)iron iodide tetrakis(pentafluorophenyl)borate, (p-tolyl)(p-isopropylphenyl)iodonium tetrakis(pentafluorophenyl)borate Salt, di(p-tert-butylphenyl) iodine gun tetrakis(pentafluorophenyl)borate, triphenylsulfonium Tetrakis(pentafluoro 'phenyl)borate, tris(p-tert-butylphenyl)phosphonium tetrakis(pentafluorophenyl)borate. More preferably bis(p-tolyl) iodine hexafluoroantimonate, (p-tolyl) (p-isopropylphenyl) iodine hexafluoroantimonate, di(p-tert-butylphenyl) Iodine hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate, tris(p-tert-butylphenyl)phosphonium hexafluoroantimonate bis(p-tolyl) iodine tetras(pentafluoro) Phenyl) borate, (p-tolyl) (p-isopropylphenyl) iodine tetrakis(pentafluorophenyl)borate, di(p-tert-butylphenyl) iodine tetrakis(pentafluorobenzene) a borate, triphenylsulfonium tetrakis(pentafluorophenyl)borate, tris(p-tert-butylphenyl)phosphonium tetrakis(pentafluorophenyl)borate, and the like. The component [B] is used in a proportion of 0.01 to 15 parts by weight, preferably 0.1 to 10 parts by weight, per 100 parts by weight of the copolymer [A]. In the above-mentioned range, if the amount is from 0.01 to 15 parts by weight, the curing φ speed of the exposed portion can be increased, the film of the pattern at the time of development can be reduced, and the residual film ratio can be improved, which is preferable. The thioxanthone compound 丨C1 is a [C] thioxanthone compound, and examples thereof include thioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, and 2,3-diethyl. Thioxanthone, 2,4-. diethylthioxanthone, 2,4-dichlorothioxanthone, chloro-4-propoxythioxanthone, 2-cyclohexylthioxanthone, 4-ring Hexyl thioxanthone and the like. 7 The ratio of the component [C] is usually 15 parts by weight or less, preferably 0.01 to 15 parts by weight, more preferably -27 to 1379130 Ό.1 to 100 parts by weight of the copolymer [A]. 10 parts by weight. When the content of the component [C] is 〇〇1 to 丨纟 by weight, the photocationic polymerization initiator can be sensitized, the curing speed at the time of curing can be increased, and the resolution at the time of curing can be suppressed from decreasing, thereby improving the solvent resistance of the cured film. , so it is better. Other components The radiation sensitive resin composition of the present invention contains the above-mentioned copolymer [Α] and [Β] components, or the [C] component is an essential component, and may further contain [1> a crosslinking agent, [Ε] polymerization if necessary. Sex monomer', [F] surfactant or [G7] adhesion aid. The above [D] crosslinking agent is a component which forms a crosslinked structure between specific alkali-soluble resin molecules as a [Α] component. As such a crosslinking agent, a condensation product of urea and formaldehyde (hereinafter referred to as "urea-formaldehyde condensation product"), a condensation product of melamine and awakening (hereinafter, referred to as "condensation product of melamine-formaldehyde") can be used. And hydroxymethyl urea alkyl ethers obtained from these condensation products and alcohols, and methylol melamine alkyl acids, etc. Specific examples of the urea-formaldehyde condensation product include monomethylol urea and dihydroxyl. Methyl urea, etc. As a specific example of the melamine-formaldehyde condensation product, hexamethylol melamine may be mentioned, and a product in which melamine and formaldehyde are partially condensed may be used. The aforementioned hydroxymethyl urea alkyl ether is urea·formic acid. Specific examples of the reaction of a part or all of the methylol group in the condensation product with an alcohol include monomethylol urea methyl ether, dimethylol urea methyl ether, etc. The aforementioned methylol melamine The ether is a part or all of the methylol of the melamine-formaldehyde condensation product and is reacted with an alcohol such as methanol 'n-butanol. The specific examples thereof include hexamethylene methyl melamine hexa-28- 1379130 袅 yl ether, hexamethylol melamine hexa-butyl ether, hydrogen atom having a trimer group, hydroxymethyl group and methoxy group. a compound having a structure in which a hydrogen atom of an amino group having a melamine is substituted with a butoxymethyl group and a methyl group, etc.. Among them, a methylol melamine alkyl ether is preferably used as a methyl melamine alkane. Commercial products such as "CYMEL 300", "CYMEL370", 2 3 2", "Μ YC 0 D 5 0 5" manufactured by Mitsui Club Co., Ltd., and the like can be cited. The use of the [〇] crosslinking agent is 50 parts by weight or less, more preferably 3 parts by weight or less, relative to 10 parts by weight of the [Α] component. When the ratio exceeds 50 parts by weight, the thickness of the coating ray portion is remarkably reduced in the development treatment, and the obtained coating film is low. As the [E] polymerizable monomer, for example, a polymerizable monomer capable of cationically polymerizing a heat-recyclable monomer can be used. Examples of the radically polymerizable polymerizable monomer include a compound having a φ polymerizable carbon-carbon unsaturated bond, and may be a monofunctional 'or a bifunctional polymerizable monomer, a trifunctional or a polymerizable single. A polyfunctional polymerizable monomer. Examples of the monofunctional polymerizable monomer include stilbene acryl vinegar, decyl phenyl carbitol methacrylate, - chain -3- methoxy propyl ester, and methacrylic acid 2 -hydroxy-3-benzene, awake, 2·ethylhexyl carbitol acrylate, 2-ethylhexyl carbaryl vinegar, 2-hydroxyethyl acrylate, 2-hydroxyindole methacrylate卩比略院嗣 etc. Amino compound of cyanamide, oxymethyl group is a hydroxy-Cytec strain. CYMEL ratio is preferred. The film is not irradiated with a transparent group of underlying radical polymerization, for example, a polymerizable monofunctional phenyl phenylene senoate 2-oxypropane. Benzyl alcohol methyl ethyl ester ' -29- 1379130. Examples of the bifunctional polymerizable monomer include diacrylate, 1,6-hexanediol dimethacrylate, ethylene diacetate, and ethylene. Alcohol dimethacrylate, neopentyl glycol dipropylene glycol dimethyl propionate vinegar, triethylene glycol dipropionate vinegar, triacrylate, bisphenol A bis(propylene oxiranyl ethyl ether) Alcohol diacrylate, 3·methyl pentanediol dimethacrylate As the above-mentioned trifunctional or higher polymerizable monomer, it may be methylolpropane triacrylate or trimethylolpropane trimethylpentaerythritol. Triacrylate 'pentaerythritol trimethacrylate tetraacrylate, pentaerythritol tetramethacrylate, quaternary acid ester, pentaerythritol pentamethyl acrylate, dipentaerythritol, dipentaerythritol hexamethacrylate, etc. Dad prefers to use 2- or 3-functional or The polymerizable monomer is preferably pentaerythritol tetraenoate, dipentaerythritol hexapropylene or more preferably dipentaerythritol hexaacrylate. Alternatively, it may be used as a trifunctional or higher polymerizable monomer and a monofunctional polymerization. Examples of the polymerizable monomer capable of cationic polymerization include a polymerizable monomer having a vinyl ether group, a propenyl ether group, an epoxy group, and an oxetan polymerizable functional group. For example, triethylene glycol divinyl ether methanol divinyl ether, 4-hydroxybutyl vinyl ether, dodecane, etc.; as the propylene group-containing compound, a methyl group-1,3 - Dioxolane-2-one or the like; as the epoxy group-containing epoxy resin, a bisphenol A type epoxy resin, a novolac type ring 1,6-hexanediol alcohol diacrylate, and neopentyl glycol dimethyl group 3-methylpentane, etc., for example, a triacrylate, an ester, a pentaerythritol pentapropanol hexaacrylate hexamethylene acrylate monomer, a odorant, an enoate, etc., to a bifunctional monomer Together, for example, a cationic vinyl ether group having a base, etc. 4-cyclohexanediyl vinyl ether 4-(1-propoxy oxygen: compound, oxy resin, A-30-1379130 • Phenolic novolak type epoxy resin, cyclic aliphatic epoxy resin, glycidyl ester type Epoxy resin, glycidylamine type epoxy resin, heterocyclic epoxy resin; as a compound containing an oxetanyl group, bis{3-(3-'ethyl oxetanyl) A Ether, 1,4-di{3"3-ethyloxetanyl). methoxy}benzene, 1,4-di{3-(3·ethyloxetanyl)methoxy Toluene, 1,4-bis{3-(3-ethyloxetanyl)methoxyindole, 1,4-di{3-(3-ethyloxetanyl) Methoxyquinonemethylcyclohexane, 3-(3-ethyloxetanyl)methylated novolac resin, and the like. • When the above polymerizable monomers are used, they may be used singly or in combination of two or more. The amount of the [E] polymerizable monomer to be added to the radiation-sensitive resin composition of the present invention is preferably 30 parts by weight or less based on 100 parts by weight of the copolymer [A]. The above [F] surfactant can be used in the radiation sensitive resin composition of the present invention to further improve coatability. As the [F] surfactant to be used herein, a fluorosurfactant, an organic terpene surfactant, and a nonionic surfactant can be used. B. Specific examples of the fluorine-based surfactant include 1,1,2,2·tetrafluorooctyl (1,1,2,2-tetrafluoropropyl)ether, 1,1,2,2-tetra. Fluoxenyl hexyl ether, octaethylene glycol bis(1,1,2,2-tetrafluorobutyl)ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether , propylene glycol bis(1,1,2,2-tetrafluorobutyl)ether, hexapropylene glycol di-U,1,2,2,3,3-hexafluoropentyl)ether, perfluorododecyl sulfonic acid Sodium, .1,2,2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, and fluoroalkane Sodium benzene sulfonate, fluoroalkyl oxyethylene ether, fluoroalkyl halide, fluoroalkyl polyoxyethylene ether, perfluoroalkyl polyoxyl, perfluoroalkyl Oxides, fluoroalkyl esters, and the like. Also, as it -31 - 1379130 • .

們的市售品，可以列舉出 BM-1000、BM-1100(以上 BM Chemie 社製），MEGAFAC F142D、MEG AF AC F172' MEGAFAC F17 3、MEGAFAC F183、MEGAFAC F178、 MEGAFAC F191、MEGAFAC F471(以上，大日本油墨化學 工業（株）製），FLUORAD FC-170C、FC-171 ' FC-430、 FC-431(以上，住友 3M(株）製），SURFLOW S-112、SURFLOW S-113、SURFLOW S-1 3 1 ' SURFLOW S-141、SURFLOW S-145、SURFLOW S-3 82、SURFLOW SC-101' SURFLOW SC-102、SURFLOW SC-103、SURFLOW SC-104、SURFLOW SC-105、SURFLOW SC-106(以上，旭硝子（株）製），EFTOP EF301 ' EFTOP EF 303 ' EFTOP EF 352(以上，新秋田化成 (株）製），SH-28PA、SH-190、SH-193' SZ-6032、SF-8428、 DC-57、DC-1 90(Toray Silicone(株）製）等。 另外，作爲矽酮類表面活性劑，可以列舉例如以To ray silicone DC3PA、Toray silicone DC7PA、Toray silicone SH11PA、Toray silicone SH21PA、Toray silicone SH28PA、 Toray silicone SH29PA ' Toray silicone SH30PA、Toray silicone FS-1265-300(以上 Toray Dow Corning(株）製）， TSF-4440 、 TSF-4300 、 TSF-4445 、 TSF-4446 、 TSF-4460 、 TSF-44 5 2(以上，GE東芝Silicone(株）製）等商品名銷售的 產品。 作爲上述非離子性表面活性劑’可以使用例如聚氧乙烯 月桂基醚' 聚氧乙烯硬脂醯基醚、聚氧乙烯油烯基醚等聚 氧乙烯烷基醚類；聚氧乙烯辛基苯基醚、聚氧乙烯壬基苯 基醚等聚氧乙烯芳基醚類；聚氧乙烯二月桂酸酯、聚氧乙 -32- 1379130 烯二硬脂酸酯等聚氧乙烯二烷基酯類等，以及（甲基）丙烯 酸類共聚物POLYFLOW No.57 ' 95(共榮社化學（株）製）等。 這些表面活性劑，可以單獨或混合2種或以上使用。 ’ 相對於1〇〇重量份共聚物[A]，表面活性劑[F]較佳使用5 • 重量份或以下’進一步較佳爲2重量份或以下。此時，表 面活性劑[F]的用量如果超過5重量份，在基板上形成塗膜 時，塗膜容易發生膜粗糙。 另外，爲了進一步提高與基板的黏合性，可以在本發明 # 的感放射線性樹脂組成物中混合黏合助劑[G] » 作爲這種黏合助劑[G]，較佳使用官能性矽烷偶聯劑， 例如可以列舉出具有羧基、甲基丙烯醯基、異氰酸酯基、 環氧基等反應性取代基的矽烷偶聯劑。具體地，可以列舉 出三甲氧基矽烷基苯甲酸、7-甲基丙烯醯氧基丙基三甲氧 基矽烷、乙烯基三乙醯氧基矽烷、乙烯基三甲氧基矽烷、 7-異氰酸醋基丙基三乙氧基政院、7-環氧丙氧基丙基三 甲氧基矽烷、/3 -(3,4·環氧環己基）乙基三甲氧基矽烷等。 • 相對於100重量份共聚物[A]’這種黏合助劑[G]的混合量較 佳爲20重量份或以下，更較佳1〇重量份或以下。黏合助 劑的量超過20重量份時，在顯影步驟中，容易產生顯影殘 像。 感放射線性樹脂細成物 . 本發明的感放射線性樹脂組成物，可以通過將上述共聚 物[A]、[B]成分以及如上任意添加的其他成分均勻混合而 « 製備。通常’本發明的放射線樹脂組成物是溶解在適當的 溶劑中’以溶液的狀態使用。例如，將共聚物[A ]、[ B ]成 -33- 1379130 分以及任意添加的其他成分以所定比例混合’製備溶液狀 態的感放射線性樹脂組成物。 作爲本發明的感放射線性樹脂組成物製備中使用的溶 ' 劑，可以使用能均勻地溶解共聚物[A]、[B]成分以及任意 添加的其他成分的各種成分，且不與各成分反應的溶劑。 作爲這種溶劑可以列舉與製造上述共聚物[A]時所例示 的溶劑相同的溶劑。 這些溶劑中，從各成分的溶解能、與各成分的反應性和 • 塗膜形成的容易性的觀點出發，較佳使用二醇醚、乙二醇 烷基醚乙酸酯類、酯類和二甘醇類。其中，特別較佳使用 二甘醇乙基甲基醚、二甘醇二甲基醚、丙二醇單甲基醚、 丙二醇單甲基醚乙酸酯、甲氧基丙酸甲酯、乙氧基丙酸乙 酯。 在製備溶液狀態的本發明感放射線性樹脂組成物時，溶 液中的溶劑以外的成分（也就是，共聚物[A]、[B]成分和任 意添加的其他成分的總量）的比例，可以根據使用目的和所 • 希望的膜厚値等任意設定，通常爲5〜50重量％、較佳爲 10〜40重量％、更較佳爲15〜35重量％ ^ 這樣製備的組成物溶液，用孔徑〇. 2 // m左右的微孔過 濾器等過濾後使用。 突起和/或間隔物的形 . 接著’對用本發明感放射線性樹脂組成物形成本發明突 起和或間隔物的方法進行說明。本發明的突起和/或間隔物 » 的形成方法，至少包含以下步驟。 (1)在基板上形成本發明感放射線性樹脂組成物塗膜的 -34- 13,79130 步驟。 (2) 在該塗膜的至少一部分上照射放射線的步驟。 (3) 顯影步驟》 • (4)加熱步驟。 • 板上形成本發明感放射線件樹脂組成物塗膜的 步驟 在上述（1)步驟中，將本發明的組成物溶液塗布到基板表 ® ’預烘烤除去溶劑，形成感放射線性樹脂組成物塗膜。 ® 作爲本發明中使用的基板的種類，可以列舉出玻璃基 木反' 矽圓晶片以及在它們表面形成各種金屬的基板。 作爲形成本發明的感光性樹脂組成物塗膜的方法，例如 可以採用（1)塗布法、（2)乾燥薄膜法。 作爲組成物溶液的塗布方法，例如可以採用噴霧法、滾 塗法、旋轉塗布法（旋塗法）、狹縫塗布法、刮棒塗布法、 噴墨塗布法等適宜的方法，特別較佳旋轉塗布法、狹縫塗 布法。 • 另外’在採用（2)乾燥薄膜法形成本發明的感光性樹脂組 成物的塗膜時’該乾燥.薄膜是在基底薄膜、較佳爲可撓性 @ S底薄膜上’層壓由本發明的感光性樹脂組成物形成的 感光性層形成的（以下，稱作“感光性乾燥薄膜”）。 上述感光性乾燥薄膜是在基底薄膜上塗布本發明的感. • 光性樹脂組成物、較佳爲液狀組成物後，乾燥，層壓感光 性層形成《作爲感光性乾燥薄膜的基底薄膜，例如可以使 ζ 用聚對苯二甲酸乙二醇酯（ρΕΤ)、聚乙烯、聚丙烯、聚碳酸 II '聚氯乙烧等合成樹脂薄膜。基底薄膜的厚度合適的是 -35- 1379130 15〜125 #m。所得的感光性層的厚度較佳爲1〜30/zm左 右。 另外，感光性乾燥薄膜在未使用時，.可以在該感光性層 * 上進一步層壓保護膜進行保存。該保護膜在未使用時不剝 . 離，在使用時可以容易地剝離，所以必須有適當的脫模性》 作爲滿足這種條件的保護膜，可以列舉出例如在PET薄 膜、聚丙烯薄膜、聚乙烯薄膜、聚氯乙烯薄膜等合成樹脂 的表面上，塗覆或燒結有機矽類脫膜劑形成的薄膜。保護 • 膜的厚度通常爲25/zm左右即可。預烘烤的條件根據各成 分的種類、使用比例等而異。例如，可以是在60〜1 1 0°C下 進行3 0秒鐘〜1 5分鐘左右。 (2)對該塗膜的至少一部分照射放射線的步驟 在上述（2)步驟中，通過具有規定圖案的掩模，照射放射 線後’使用顯影液進行顯影處理除去放射線照射部分，在 形成的塗膜上布圖。作爲此時使用的放射線，可、以列舉出 例如紫外線、遠紫外線' X射線 '帶電粒子束等。 φ 作爲上述紫外線，可以列舉出例如g線（波長4；36nm)、i 線（波長3 65 nm)等。作爲遠紫外線，可以列舉出例如KrF 准分子鐳射等。作爲X射線，可以列舉出例如同步加速器 放射線等。作爲帶電粒子束，可以列舉出例如電子束等。 其中’較佳紫外線，特別佳爲含有g線和/或i線的放射 . 線。 ； ί乍胃曝光時使用的圖案掩模和曝光操作可以是：（1)使用 具有突起部分和間隔物部分的兩個圖案的1種光掩模，一 次曝光的方法（掩模的部分越小的位置，越不能忽視透過的 -36- 1379130 t * 光的影響，和烘烤時的熔體流動相應，形虑 使用只有突起部分的光掩模和只有間隔物的 進行2次曝光的方法。另外，作爲（1)的方法 掩模’也可以使用突起部分和間隔物部分具 的掩模。但是’在本發明中，根據情況，也 只形成突起和間隔物中的一種，在這種情況 (3)只有突起部分的光掩模和只有間隔物部 任何一種’進行一次曝光的方法。另外，在 在垂直配向型液晶顯示元件中必須殘留的突 過現有公知的方法形成。 (3)顯影步驟 作爲顯影處理中使用的顯影液，可以使用 氧化鉀、碳酸鈉、矽酸鈉、甲基矽酸鈉、氨 胺、二乙胺、二乙基氨基乙醇、二正丙基胺 基二乙基胺、二甲基乙醇胺、三.乙醇胺、氫氧 氫氧化四乙基銨、吡咯、哌啶、1，8 -二氮雜 十一碳烯、1,5-二氮雜雙環[4,3,0]-5-壬烷； 液。另外’在上述鹼性水溶液中，可以適當 醇等水溶性有機溶劑和表面活性劑形成水溶 溶液，或者溶解本發明的組成物的各種有機 液使用。此外，作爲顯影方法，可以是盛液 搖動浸漬法、沖淋法等適當的方法。此時的 組成物的組成而異，通常爲3 0〜1 8 0秒左右For the commercial products, BM-1000, BM-1100 (manufactured by BM Chemie Co., Ltd.), MEGAFAC F142D, MEG AF AC F172' MEGAFAC F17 3, MEGAFAC F183, MEGAFAC F178, MEGAFAC F191, MEGAFAC F471 (above, Dainippon Ink Chemical Industry Co., Ltd., FLUORAD FC-170C, FC-171 'FC-430, FC-431 (above, Sumitomo 3M Co., Ltd.), SURFLOW S-112, SURFLOW S-113, SURFLOW S -1 3 1 'SURFLOW S-141, SURFLOW S-145, SURFLOW S-3 82, SURFLOW SC-101' SURFLOW SC-102, SURFLOW SC-103, SURFLOW SC-104, SURFLOW SC-105, SURFLOW SC-106 (above, Asahi Glass Co., Ltd.), EFTOP EF301 ' EFTOP EF 303 ' EFTOP EF 352 (above, New Akita Chemicals Co., Ltd.), SH-28PA, SH-190, SH-193' SZ-6032, SF- 8428, DC-57, DC-1 90 (manufactured by Toray Silicone Co., Ltd.). In addition, examples of the anthrone-based surfactant include Toray silicone DC3PA, Toray silicone DC7PA, Toray silicone SH11PA, Toray silicone SH21PA, Toray silicone SH28PA, Toray silicone SH29PA 'Toray silicone SH30PA, Toray silicone FS-1265-300. (Toray Dow Corning Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-44 5 2 (above, GE Toshiba Silicone Co., Ltd.) Products on sale. As the nonionic surfactant, for example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and the like can be used; polyoxyethylene octylbenzene; Polyoxyethylene aryl ethers such as ethers and polyoxyethylene nonylphenyl ethers; polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene-32-1379130 ened distearate And (meth)acrylic copolymer POLYFLOW No. 57 '95 (manufactured by Kyoeisha Chemical Co., Ltd.). These surfactants can be used singly or in combination of two or more. The surfactant [F] is preferably used in an amount of 5 parts by weight or less based on 1 part by weight of the copolymer [A], and further preferably 2 parts by weight or less. At this time, when the amount of the surfactant [F] is more than 5 parts by weight, when the coating film is formed on the substrate, the coating film is likely to be rough. Further, in order to further improve the adhesion to the substrate, the adhesion aid [G] can be mixed in the radiation sensitive resin composition of the invention # as the adhesion aid [G], preferably using a functional decane coupling. The agent may, for example, be a decane coupling agent having a reactive substituent such as a carboxyl group, a methacryl group, an isocyanate group or an epoxy group. Specific examples thereof include trimethoxydecyl benzoic acid, 7-methacryloxypropyltrimethoxydecane, vinyltriethoxydecane, vinyltrimethoxydecane, and 7-isocyanate. Acetylpropyltriethoxyol, 7-glycidoxypropyltrimethoxydecane, /3-(3,4.epoxycyclohexyl)ethyltrimethoxydecane, and the like. • The amount of the adhesion aid [G] is preferably 20 parts by weight or less, more preferably 1 part by weight or less, per 100 parts by weight of the copolymer [A]'. When the amount of the adhesion aid exceeds 20 parts by weight, development of the image is liable to occur in the development step. Radiation-sensitive resin composition. The radiation-sensitive resin composition of the present invention can be prepared by uniformly mixing the above-mentioned copolymer [A], [B] components and other components added as described above. Usually, the radiation resin composition of the present invention is dissolved in a suitable solvent and used in the form of a solution. For example, the copolymer [A ], [B] is added in a ratio of -33 to 1379130, and other components added arbitrarily in a predetermined ratio to prepare a radiation-sensitive resin composition in a solution state. As the solvent used in the preparation of the radiation sensitive resin composition of the present invention, various components which can uniformly dissolve the copolymer [A], [B] component and any other components added can be used, and do not react with each component. Solvent. As such a solvent, the same solvent as that exemplified in the case of producing the above copolymer [A] can be mentioned. Among these solvents, glycol ether, ethylene glycol alkyl ether acetate, ester and two are preferably used from the viewpoints of the solubility of each component, the reactivity with each component, and the ease of formation of a coating film. Glycols. Among them, it is particularly preferable to use diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl methoxypropionate, ethoxy propyl Ethyl acetate. When preparing the radiation sensitive linear resin composition of the present invention in a solution state, the ratio of components other than the solvent in the solution (that is, the total amount of the copolymer [A], [B] component, and any other components added arbitrarily) may be The composition solution prepared in accordance with the purpose of use and the desired film thickness, etc., is usually 5 to 50% by weight, preferably 10 to 40% by weight, more preferably 15 to 35% by weight. Aperture 〇. 2 / m or so microporous filter is filtered and used. Shape of protrusions and/or spacers Next, a method of forming the protrusions or spacers of the present invention using the radiation sensitive resin composition of the present invention will be described. The method of forming the protrusions and/or spacers of the present invention comprises at least the following steps. (1) A step of forming -34 - 13,79130 of the coating film of the radiation sensitive resin composition of the present invention on a substrate. (2) a step of irradiating radiation on at least a part of the coating film. (3) Development step • (4) Heating step. • The step of forming the coating film of the radiation-sensitive adhesive resin composition of the present invention on the board. In the above step (1), the composition solution of the present invention is applied to the substrate table® to pre-baking the solvent to form a radiation-sensitive resin composition. Coating film. ® As the type of the substrate used in the present invention, a glass-based inverted circular wafer and a substrate on which various metals are formed on the surface thereof can be cited. As a method of forming the coating film of the photosensitive resin composition of the present invention, for example, (1) coating method and (2) dry film method can be employed. As a coating method of the composition solution, for example, a suitable method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit coating method, a bar coating method, or an inkjet coating method can be employed, and it is particularly preferable to rotate. Coating method, slit coating method. • In addition, when the coating film of the photosensitive resin composition of the present invention is formed by the (2) dry film method, the film is dried on the base film, preferably a flexible @S base film. The photosensitive layer formed of the photosensitive resin composition is formed (hereinafter referred to as "photosensitive dry film"). The photosensitive dried film is coated on the base film with the feeling of the present invention. • The photosensitive resin composition, preferably a liquid composition, is dried, and the photosensitive layer is laminated to form a base film as a photosensitive dried film. For example, a synthetic resin film such as polyethylene terephthalate (ρΕΤ), polyethylene, polypropylene, or polycarbonate II 'polychloroethane can be used. The thickness of the base film is suitably -35 - 1379130 15~125 #m. The thickness of the resulting photosensitive layer is preferably about 1 to 30/zm. Further, when the photosensitive dried film is not used, a protective film may be further laminated on the photosensitive layer * for storage. The protective film is not peeled off when it is not used, and can be easily peeled off during use. Therefore, it is necessary to have appropriate mold release property. As a protective film satisfying such conditions, for example, a PET film or a polypropylene film can be cited. A film formed by coating or sintering an organic bismuth release agent on the surface of a synthetic resin such as a polyethylene film or a polyvinyl chloride film. Protection • The thickness of the film is usually around 25/zm. The conditions for prebaking vary depending on the type of each component, the ratio of use, and the like. For example, it may be carried out at 60 to 1 10 ° C for about 30 seconds to about 15 minutes. (2) a step of irradiating at least a part of the coating film with radiation in the step (2), irradiating the radiation with a mask having a predetermined pattern, and performing a development treatment using a developing solution to remove the radiation-irradiating portion, and the formed coating film On the map. Examples of the radiation to be used at this time include ultraviolet rays, far ultraviolet rays 'X-rays', charged particle beams, and the like. φ As the ultraviolet rays, for example, a g line (wavelength 4; 36 nm), an i line (wavelength 3 65 nm), or the like can be given. Examples of the far ultraviolet rays include KrF excimer lasers and the like. Examples of the X-ray include a synchrotron radiation and the like. Examples of the charged particle beam include an electron beam and the like. Among them, a preferred ultraviolet ray is particularly preferred as a radiation containing a g-line and/or an i-line. The pattern mask and exposure operation used in the gastric exposure may be: (1) a photomask using two patterns having a protruding portion and a spacer portion, and a method of one exposure (the smaller the portion of the mask) The position, the less the influence of the transmitted light of -36-1379130 t*, the corresponding to the melt flow during baking, the use of a photomask having only a protruding portion and a method of performing only two exposures of the spacer. Further, as the method mask of (1), a mask having a protruding portion and a spacer portion may be used. However, in the present invention, only one of a protrusion and a spacer is formed depending on the case, in which case (3) A photomask having only a protruding portion and a method of performing only one exposure of the spacer portion. Further, it is formed by a conventionally known method which must remain in the vertical alignment type liquid crystal display element. (3) Development Steps As the developer used in the development treatment, potassium oxide, sodium carbonate, sodium citrate, sodium methyl citrate, aminoamine, diethylamine, diethylaminoethanol, di-n-propylaminodiamine can be used. Amine, dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazaundecene, 1,5-diazabicyclo[4,3 Further, in the above alkaline aqueous solution, a water-soluble solution such as a suitable water-soluble organic solvent such as an alcohol or a surfactant may be used, or various organic liquids in which the composition of the present invention is dissolved may be used. As the developing method, an appropriate method such as a liquid shaking method or a shower method may be used. The composition of the composition at this time varies, and is usually about 30 to 180 seconds.

Li)加熱步驟 在如上進行的（3)顯影步驟後，較佳對布圖 ，高度差）：（2) 2種光掩模， 中使用的圖案 有不同透過率 可以在基板上 下，可以採用 分的光掩模的 這種情況下， 起或間隔物通 氫氧化鈉、氫 、乙胺、正丙 、三乙胺、甲 化四甲基銨、 雙環[5,4,0]·7-亭鹼類的水溶 添加甲醇、乙 液，將形成水 溶劑作爲顯影 法、浸漬法、 顯影時間根據 〇 的薄膜進行基 -37- 1379130 於流水洗滌的沖淋處理’再較佳通過高壓水銀燈等全面照 射放射線（後曝光），對該薄膜中殘留的1，2 -醌二疊氮化合物 進行分解處理後，通過熱板、烘箱等加熱裝置對該薄膜進 行加熱處理（後烘烤處理），對該薄膜進行固化處理。上述 • 後曝光步驟中的曝光量較佳爲2,0〇〇〜5,000〗/π^左右。另 外，該固化處理的燒製溫度’例如爲1 2 〇〜2 5 01，加熱時 間根據加熱器的種類而異，例如在熱板上進行加熱處理 時’是5〜30分鐘，在烘箱中進行加熱處理時，是30-90 ® 分鐘。此時’也可以使用進行2次或以上的加熱步驟的分 步烘烤法等。 如此，可以在基板表面形成與目標的突起和/或間隔物相 對應的圖案狀的薄膜。 如此形成的突起的高度通常是〇.1〜3.0；^111，較佳爲 ◦ . 5〜2 · 0 // m，特別較佳爲1 _ 0〜1. 5 // m ;而且間隔物的高度 通常是1〜10//m’較佳爲2〜8//m，特別較佳爲3〜5/zme 根據這樣的本發明的垂直配向型液晶顯示元件使用的 • 突起和/或間隔物的形成方法，可以微細加工，而且容易控 製形狀和尺寸（高度和底部尺寸）’可以穩定且生產性高地 形成圖案形狀、耐熱性、耐溶劑性、透明性等優異的微細 的突起和間隔物，而且還可以提供配向性、電壓保持率等 優異的垂直配向型液晶顯示元件。 . 形成本發明之垂直配向型液晶顯示元件使用的突起和/ 或分隔物的感放射線性樹脂組成物，解析度及殘膜率優 異，且可形成圖案形狀、耐熱性、耐溶劑性、透明性等優 異的微細的突起和間隔物，而且還可以提供配向性、電壓 -38- 1379130 » *« 保持率等優異的垂直配向型液晶顯示元件。又，本發明之 垂直配向型液晶顯示元件使用的突起和/或分隔物的形成 方法’可以微細加工，而且容易控制形狀和尺寸（高度和底 ' 部尺寸），可以穩定且生產性高地形成圖案形狀、耐熱性、 • 耐溶劑性' 透明性等優異的微細突起和間隔物，而且還可 提供配向性、外’還要求所得的垂直配向型液晶顯示元件 的配向性、電壓保持率等優異之垂直配向型液晶顯示元件。 [實施例] • 下面，顯示合成例和實施例，更具體地說明本發明，但 本發明並不限於這些實施例。 共聚物f A1的合成例 合成例1 在具備冷卻管、攪拌器的燒瓶中，加入5重量份2,2，-偶氮二（2,4-二甲基戊腈）、200重量份二甘醇甲基乙基醚， 再加入18重量份甲基丙烯酸、40重量份甲基丙烯酸縮水甘 油酯、5重量份苯乙烯、32重量份甲基丙烯酸三環[5.2.1.〇2.6] 鲁 癸院-8-基，氮置換後’加入5重量份1,3 -丁二烧，一邊緩 緩攪拌一邊使溶液溫度上升到7(TC，保持在該溫度5小時 聚合，得到共聚物[A -1 ]的溶液。 該溶液的固體成分濃度爲33.0重量％，共聚物[A-1]的 Mv/爲11,000’分子量分佈（重量平均分子量/數均分子量的 . 比）爲1.8。另外，重量平均分子量和數均分子量是使用 , GpC(凝膠滲透色譜法（TOSOH(株）製HLC-8020)測定的聚苯 乙烯換算的平均分子量。 合成例2 -39- 1379130 在具備冷卻管、攪拌器的燒瓶中，加入7重量份2,2’-偶氮二（2,4-二甲基戊腈）、220重量份丙二醇單甲基醚乙酸 酯。再加入20重量份苯乙烯、25重量份甲基丙烯酸、20 ’ 重量份苯基馬來醯亞胺、35重量份3-(甲基丙烯醯氧基甲 • 基）-3-乙基氧雜環丁烷、1.5份α·甲基苯乙烯二聚物，一邊 氮置換，一邊開始緩慢攪拌。使溶液溫度上升至70°C，在 該溫度加熱5小時，得到含共聚物[A-2]的聚合物溶液。所 得的聚合物溶液的固體成分濃度爲31.0%，聚合物的重量 • 平均分子量爲21，000，分子量分佈爲2.1。 合成例3 在具備冷卻管、攪拌器的燒瓶中，加入7重量份2,2’-偶氮二（2,4 -二甲基戊腈）、220重量份丙二醇單甲基醚乙酸 酯。再加入28重量份苯乙烯、18重量份甲基丙烯酸、54 份3-(甲基丙烯醯氧基甲基）-3 -乙基氧雜環丁烷，一邊氮置 換’一邊開始緩慢攪拌。使溶液溫度上升至7〇 t ,在該溫 度加熱5小時，得到含共聚物[a - 3 ]的聚合物溶液。所得的 • 聚合物溶液的固體成分濃度爲31.2%，聚合物的重量平均 分子量爲23,000，分子量分佈爲2.6。 實施例1 [感放射線性樹脂組成物的製備] 將相當於100重量份聚合物[A-I](固體成分）的量的作爲 .上述合成例1合成的[Α]成分的含有聚合物[Α-1]的溶液，和 3重量份作爲成分[Β]的二（對·甲苯基）碘鎗六氟銻酸鹽（Β1) 混合’溶解到二甘醇乙基甲基醚中，使固體成分濃度爲3〇 重量％後’用口徑爲〇.2vm的薄膜過濾器過濾，製備感放 * 40 - 1379130 射線性樹脂組成物溶液（s-i)。 實施例2〜4 除了在實施例1中，使用表1所記載的種類 '量的[A] ' 成分' [B]成分和[C]成分以外，進行與實施例1同樣的處 . 理，製備感放射線性樹脂組成物的溶液（S-2)~(S-4) ° 另外，表1中的成分的簡稱表示如下化合物。 (B-1):二（對-甲苯基）碘鎰六氟銻酸鹽 (B-2):(對-甲苯基）（對-異丙基苯基）姚鑰四（五氟苯基） 9 硼酸鹽[Rhodorsil Phot〇initiator 2〇74(Rhodia 社製）] (C-l) : 2,4-二甲基噻噸酮Li) heating step after the (3) development step as described above, preferably for layout, height difference): (2) 2 kinds of photomasks, the patterns used in the patterns have different transmittances on the substrate, and can be used In this case of photomask, the spacer or the spacer is passed through sodium hydroxide, hydrogen, ethylamine, n-propyl, triethylamine, tetramethylammonium tetrachloride, bicyclo[5,4,0]·7-kid Alkali water-soluble methanol and ethyl alcohol are added, and a water solvent is formed as a developing method, a dipping method, and a developing time is carried out according to a film of ruthenium---37-130130 in a water-washing process of water-flowing, and further preferably by a high-pressure mercury lamp or the like. After the radiation (post-exposure), the 1,2-quinonediazide compound remaining in the film is subjected to decomposition treatment, and then the film is subjected to heat treatment (post-baking treatment) by a heating device such as a hot plate or an oven, and the film is subjected to heat treatment (post-baking treatment). Curing treatment is carried out. The exposure amount in the above-mentioned post-exposure step is preferably about 2,0〇〇~5,000〗/π^. Further, the firing temperature of the curing treatment is, for example, 1 2 〇 to 2 5 01, and the heating time varies depending on the type of the heater. For example, when heat treatment is performed on a hot plate, it is 5 to 30 minutes, and is carried out in an oven. When heat treated, it is 30-90 ® minutes. At this time, a step-by-step baking method or the like which performs a heating step of 2 times or more may be used. Thus, a pattern-like film corresponding to the target projections and/or spacers can be formed on the surface of the substrate. The height of the protrusion thus formed is usually 〇1 to 3.0; ^111, preferably ◦ 5 to 2 · 0 // m, particularly preferably 1 _ 0 to 1. 5 // m ; The height is usually 1 to 10//m', preferably 2 to 8/m, and particularly preferably 3 to 5/zme. • Protrusions and/or spacers used in the vertical alignment type liquid crystal display element of the present invention. The method of forming the film can be finely processed, and the shape and size (height and bottom size) can be easily controlled. The fine protrusions and spacers excellent in pattern shape, heat resistance, solvent resistance, transparency, and the like can be formed stably and productively. Further, it is possible to provide a vertical alignment type liquid crystal display element excellent in alignment property, voltage holding ratio, and the like. The radiation-sensitive resin composition for forming the protrusions and/or separators used in the vertical alignment type liquid crystal display device of the present invention is excellent in resolution and residual film ratio, and can form a pattern shape, heat resistance, solvent resistance, and transparency. Excellent fine protrusions and spacers, and excellent vertical alignment type liquid crystal display elements with excellent alignment, voltage -38-1379130 » *« retention. Further, the method of forming the protrusions and/or the spacers used in the vertical alignment type liquid crystal display element of the present invention can be finely processed, and the shape and size (height and bottom portion size) can be easily controlled, and the pattern can be stably and productively formed. Excellent fine protrusions and spacers such as shape, heat resistance, solvent resistance, transparency, etc., and also excellent in alignment properties and voltage retention ratios of the vertical alignment type liquid crystal display element which is required to provide an alignment property. Vertical alignment type liquid crystal display element. [Examples] Hereinafter, the present invention will be more specifically described by showing Synthesis Examples and Examples, but the present invention is not limited to these Examples. Synthesis Example of Copolymer f A1 Synthesis Example 1 In a flask equipped with a cooling tube and a stirrer, 5 parts by weight of 2,2,-azobis(2,4-dimethylvaleronitrile) and 200 parts by weight of digan were added. Alcohol methyl ethyl ether, further added 18 parts by weight of methacrylic acid, 40 parts by weight of glycidyl methacrylate, 5 parts by weight of styrene, 32 parts by weight of trimethyl methacrylate [5.2.1. 〇 2.6] After the -8-base, after the nitrogen substitution, 'add 5 parts by weight of 1,3 - butyl bromide, and slowly increase the temperature of the solution to 7 (TC, while maintaining the temperature at this temperature for 5 hours to obtain a copolymer [A - The solution has a solid content concentration of 33.0% by weight, and the copolymer [A-1] has a Mv/11,000' molecular weight distribution (weight average molecular weight/number average molecular weight ratio) of 1.8. The molecular weight and the number average molecular weight are the average molecular weights in terms of polystyrene measured by GpC (gel permeation chromatography (HLC-8020, manufactured by TOSOH Co., Ltd.). Synthesis Example 2 - 39 - 1379130 With a cooling tube and a stirrer In the flask, 7 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) and 220 parts by weight of propylene glycol were added. Methyl ether acetate. Further adding 20 parts by weight of styrene, 25 parts by weight of methacrylic acid, 20 parts by weight of phenyl maleimide, and 35 parts by weight of 3-(methacryloxymethyl group) 3-ethyloxetane and 1.5 parts of α-methylstyrene dimer were slowly stirred while being replaced with nitrogen. The temperature of the solution was raised to 70 ° C, and the temperature was heated at this temperature for 5 hours to obtain a polymer solution of the copolymer [A-2]. The obtained polymer solution had a solid content concentration of 31.0%, a weight of the polymer, an average molecular weight of 21,000, and a molecular weight distribution of 2.1. Synthesis Example 3 In a flask of the agitator, 7 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile), 220 parts by weight of propylene glycol monomethyl ether acetate, and 28 parts by weight of styrene were added. 18 parts by weight of methacrylic acid and 54 parts of 3-(methacryloxymethyl)-3-ethyloxetane were slowly stirred while nitrogen was being replaced. The temperature of the solution was raised to 7 〇t. Heating at this temperature for 5 hours gave a polymer solution containing the copolymer [a - 3 ]. The obtained polymer solution The body component concentration was 31.2%, the weight average molecular weight of the polymer was 23,000, and the molecular weight distribution was 2.6. Example 1 [Preparation of Radiation-sensitive Resin Composition] 100 parts by weight of polymer [AI] (solid content) A solution containing the polymer [Α-1] of the [Α] component synthesized in the above Synthesis Example 1, and 3 parts by weight of a di(p-tolyl) iodine hexafluoroantimonate as a component [Β] (Β1) The mixture was dissolved in diethylene glycol ethyl methyl ether to have a solid concentration of 3 〇% by weight, and then filtered through a membrane filter having a diameter of 〇.2 vm to prepare a sensitizing * 40 - 1379130 ray resin. Composition solution (si). Examples 2 to 4 In the same manner as in Example 1, except that the [A] component [B] component and the component [C] of the type 'amount of the amount described in Table 1 were used, the same procedure as in Example 1 was carried out. Solution (S-2) to (S-4) ° of the radiation sensitive resin composition was prepared. Further, the abbreviations of the components in Table 1 indicate the following compounds. (B-1): bis(p-tolyl)iodonium hexafluoroantimonate (B-2): (p-tolyl) (p-isopropylphenyl) Yaosin tetra(pentafluorophenyl) 9 borate [Rhodorsil Phot〇initiator 2〇74 (manufactured by Rhodia)] (Cl) : 2,4-dimethylthioxanthone

-41 - 1379130 S 9 【表1】 組成物名 共聚ί _ [Β诚分 [C诚分 種類 量 (重量份) 種類 量 (重·量份) 種類 量 (重量份) 實施例1 (S-1) [Α-1] 100 [Β-1] 3 實施例2 (S-2) [Α-2] 100 [Β-2] 3 實施例3 (S-3) [Α-3] 100 [Β-1] 2.5 實施例4 (S-4) [Α-1] 100 [Β-1] 3 [C-1] 2 使用如上製備的感放射線性樹脂組成物，如下形成突起 和間隔物，評價各種性質。 [突起和間隔物的形成] 用旋轉器將上述組成物塗布在矽基板上後，在90°C下在 熱板上預烘烤2分鐘形成膜厚4.0 /z m的塗膜。之後，通過 具有相當於突起部分的剩餘5 /z m寬的圖案和相當於間隔 物部分的剩餘30 μ m的點的圖案的光掩模，通過Canon (株） 製的PLA-501F曝光機（超高壓水銀燈），改變曝光時間，進 行曝光。之後，通過表中記載的2 5 °C的顯影液種類、顯影 液濃度、顯影方法，進行100秒顯影後，用純水洗滌1分 鐘，乾燥，在圓晶片上形成圖案。測定用於形成相當於突 起部分的剩餘5 μ m寬的圖案和相當於間隔物部分的剩餘 30ym的點的圖案所需要的曝光量。將該値作爲靈敏度， 在表中表示。該値在3500J/m2或以下時，可以稱之爲靈敏 度良好。 [突起的剖面形狀的評價] 在突起的剖面形狀A、B或C如下定義時，通過掃描型 電子顯微鏡觀察形成的突起的剖面形狀，以A或B的情況 -42- 1379130-41 - 1379130 S 9 [Table 1] Composition name copolymerization ί _ [Β诚分 [C Cheng categorical amount (parts by weight) Type (weight/volume) Type (parts by weight) Example 1 (S- 1) [Α-1] 100 [Β-1] 3 Example 2 (S-2) [Α-2] 100 [Β-2] 3 Example 3 (S-3) [Α-3] 100 [Β -1] 2.5 Example 4 (S-4) [Α-1] 100 [Β-1] 3 [C-1] 2 Using the radiation sensitive resin composition prepared as above, protrusions and spacers were formed as follows, and various evaluations were evaluated. nature. [Formation of protrusions and spacers] After the above composition was coated on a ruthenium substrate with a spinner, it was prebaked on a hot plate at 90 ° C for 2 minutes to form a coating film having a film thickness of 4.0 / z m. Thereafter, the PLA-501F exposure machine (super) manufactured by Canon Co., Ltd. was passed through a photomask having a pattern corresponding to the remaining 5/zm width of the protruding portion and a pattern of dots corresponding to the remaining 30 μm of the spacer portion. High-pressure mercury lamp), change the exposure time, and perform exposure. Thereafter, the film was developed for 100 seconds by the type of developing solution at 25 °C, the developer concentration, and the developing method described in the table, and then washed with pure water for 1 minute, dried, and patterned on a wafer. The amount of exposure required for forming a pattern of the remaining 5 μm width corresponding to the protruding portion and a pattern corresponding to the remaining 30 μm dots of the spacer portion was measured. This enthalpy is shown as sensitivity in the table. When the crucible is 3500 J/m2 or less, it can be said that the sensitivity is good. [Evaluation of the cross-sectional shape of the protrusion] When the cross-sectional shape A, B or C of the protrusion is defined as follows, the cross-sectional shape of the formed protrusion is observed by a scanning electron microscope, in the case of A or B - 42 - 1379130

* I 爲“良好”，以c的情況爲“不好”。突起的剖面形狀的 A、B和C圖示地在第1圖中例示。 A:底部尺寸大於小於等於7/zm的情形， ' B:底部尺寸大於7;/ m的情形， • C:與底部尺寸無關，爲台形形狀的情形。 [間隔物的剖面形狀的評價] 在間隔物的剖面形狀A、B或C如下定義時，通過掃描 型電子顯微鏡觀察形成的間隔物的剖面形狀，以A或C的 Φ 情況爲“良好”，以C的情況爲“不好”。間隔物的剖面 形狀的A、B和C圖示地在第1圖中例示。 A :底部尺寸大於30 M m小於等於36 // m的情形， B:底部尺寸大於36em的情形， C :與底部尺寸無關，爲台形形狀的情形。 [耐溶劑性評價] 用旋轉器將組成物塗布在矽基板上後，在90t下在熱板 上預烘烤2分鐘形成膜厚3_0μιη的塗膜。之後，通過Canon φ (株）製的’ PLA-501F曝光機（超高壓水銀燈）以累積照射量* I is "good" and c is "not good". A, B, and C of the cross-sectional shape of the protrusion are illustrated in Fig. 1 as shown. A: The case where the bottom size is larger than or equal to 7/zm, 'B: the case where the bottom size is larger than 7; / m, • C: The case where the bottom size is a mesa shape. [Evaluation of Cross-Sectional Shape of Spacer] When the cross-sectional shape A, B, or C of the spacer is defined as follows, the cross-sectional shape of the formed spacer is observed by a scanning electron microscope, and the Φ of A or C is "good". In the case of C, it is "not good." The cross-sectional shape of the spacers A, B and C are illustrated diagrammatically in Fig. 1. A: The case where the bottom size is larger than 30 M m and less than or equal to 36 // m, B: the case where the bottom size is larger than 36 em, and C: the case where the bottom size is a table shape. [Evaluation of Solvent Resistance] After the composition was applied onto a ruthenium substrate by a spinner, it was prebaked on a hot plate at 90 Torr for 2 minutes to form a coating film having a film thickness of 3 _0 μm. After that, the ' PLA-501F exposure machine (ultra-high pressure mercury lamp) manufactured by Canon φ Co., Ltd. was used to accumulate the amount of exposure.

3,000〗/m2對所得的塗膜進行曝光。將該矽基板在清潔烘箱 內，在22CTC下，加熱1小時，得到固化膜。測定所得的固 化膜的膜厚（T1)。然後，將該形成固化膜的矽基板在溫度 控製爲70°C的二甲基亞諷中浸漬20分鐘後，測定該固化膜 . 的膜厚（tl)，算出浸漬引起的膜厚變化率{Itl-Tll/Tl } X 100(%)。結果如表2所示。在該値爲5%或以下時，認爲耐 溶劑性良好。 另外，在耐溶劑性的評價中，由於不需要對形成的薄膜 -43- 1379130 4 > 布圖，所以可以省略放射線的照射步驟和顯影步驟，用於 只進行塗膜形成步驟、後烘烤步驟和加熱步驟的評價。 [耐熱性評價] ' 與上述耐溶劑性評價同樣地形成固化膜，測定所得的固 . 化膜的膜厚（T2)。然後，將該固化膜基板在清潔烘箱內， 在240°C下追加烘烤1小時後，測定該固化膜的膜厚（t2), 算出追加烘烤引起的膜厚變化率{It2-T2l/T2}xl00(%)。結果 如表2所示。在該値爲5 %或以下時，認爲耐熱性良好。 • [透明性評價] 在上述耐溶劑性評價中，除了使用玻璃基板“Corning 7 059” （Corning社製）代替矽基板以外，同樣地在玻璃基板 上形成固化膜。使用分光光度計“ 150-20型Donlole beam((株）日立製作所製），在400〜800nm的波長下，測定 具有該固化膜的玻璃基板的光透過率。此時，最低光線透 過率如表2所示。該値爲9 0 °/。或以上時，認爲透明性良好。 [配向性和電壓保持率的評價] φ 使用組成物溶液，在具有作爲電極的ITO(塗布錫的氧化 銦）膜的玻璃基板的電極面上，與前述方法同樣地形成突起 和間隔物。之後，通過液晶配向膜塗布用印刷機，在形成 突起和間隔物的玻璃基板上塗布作爲液晶配向劑的 AL1H65 9(商品名，JSR(株）製）後，在180°C下乾燥1小時， 形成膜厚0.05；am的塗膜。另外，通過液晶配向膜塗布用 印刷機，在具有IT0膜的另一塊玻璃基板的電極面上塗布 * 作爲液晶配向劑的AL1H659，在18(TC下乾燥1小時，形成 膜厚0.05；ani的塗膜。接著，在所得的兩基板的各液晶配 -44- 1379130 • % 向膜的外表面上，絲網印刷塗.布加入直徑5 // m的玻璃織維 的環氧樹脂黏合劑，將兩基板壓合以使液晶配向膜表面相 對地重合，之後使黏合劑固化。之後，從液晶注入口在兩 基板間塡充Merck社製造的液晶MLC-6608(商品名），通過 環氧類黏合劑將液晶注入口密封後，在兩基板外表面貼合 偏光片，使其偏振方向正交，製造垂直配向型液晶顯示元 件。在第2圖中圖示表示所得的垂直配向型液晶顯示元件 的縱剖視圖，其中標號1表示間隔物、標號2表示突起、 標號3表示液晶、標號4表示液晶配向膜、標號5表示彩 色據光片、標號6表示玻璃基板。 接著，如下評價所得的垂直配向型液晶顯示元件的配向 性和電壓保持率。 配向性的評價是，在開、關電壓時，通過偏光顯微鏡觀 察在液晶盒中是否會產生異常區域，以確認沒有異常區域 的情況爲“良好”。另外，在評價電壓保持率時，是在液 晶顯示元件上施加5 V電壓後，斷開電路，測定1 6.7毫秒 後的保持電壓，計算出保持電壓相對於施加電壓（5V)的比 例。該値爲98 %或以上時，認爲是良好的。 -45· 1379130The obtained coating film was exposed at 3,000 Å/m2. The crucible substrate was heated in a cleaning oven at 22 CTC for 1 hour to obtain a cured film. The film thickness (T1) of the obtained cured film was measured. Then, the ruthenium substrate on which the cured film was formed was immersed in dimethyl enamel at a temperature of 70 ° C for 20 minutes, and then the film thickness (t1) of the cured film was measured, and the film thickness change rate due to immersion was calculated. Itl-Tll/Tl } X 100 (%). The results are shown in Table 2. When the enthalpy is 5% or less, the solvent resistance is considered to be good. Further, in the evaluation of the solvent resistance, since the formed film-43- 1379130 4 > layout is not required, the irradiation step and the development step of the radiation can be omitted for performing only the coating film forming step and the post-baking. Evaluation of the steps and heating steps. [Evaluation of heat resistance] A cured film was formed in the same manner as the evaluation of the solvent resistance described above, and the film thickness (T2) of the obtained solid film was measured. Then, the cured film substrate was additionally baked at 240 ° C for 1 hour in a cleaning oven, and then the film thickness (t2) of the cured film was measured, and the film thickness change rate due to additional baking was calculated {It2-T2l/ T2}xl00 (%). The results are shown in Table 2. When the enthalpy is 5% or less, the heat resistance is considered to be good. [Evaluation of the transparency] The cured film was formed on the glass substrate in the same manner as in the case of using the glass substrate "Corning 7 059" (manufactured by Corning Co., Ltd.) instead of the ruthenium substrate. The light transmittance of the glass substrate having the cured film was measured at a wavelength of 400 to 800 nm using a spectrophotometer "150-20 type Donlole beam (manufactured by Hitachi, Ltd.). At this time, the lowest light transmittance is shown in the table. (2) When the enthalpy is 90 ° / or more, the transparency is considered to be good. [Evaluation of the alignment property and the voltage retention ratio] φ Using the composition solution, having ITO as an electrode (tin oxide coated with tin) On the electrode surface of the glass substrate of the film, protrusions and spacers were formed in the same manner as in the above-described method. Thereafter, the liquid crystal alignment film coating printer was used to apply AL1H65 9 as a liquid crystal alignment agent on the glass substrate on which the protrusions and the spacers were formed. (product name, manufactured by JSR Co., Ltd.), and dried at 180 ° C for 1 hour to form a coating film having a film thickness of 0.05; am, and another glass having an IT0 film by a printer for coating a liquid crystal alignment film. On the electrode surface of the substrate, AL1H659, which is a liquid crystal alignment agent, was applied, and dried at 18 (TC for 1 hour to form a film thickness of 0.05; ani. Then, the liquid crystals of the obtained two substrates were matched - 44 - 1379130 • % Out of the membrane On the surface, the screen printing coating cloth is added with a glass woven epoxy resin adhesive having a diameter of 5 // m, and the two substrates are pressed together to make the liquid crystal alignment film surface relatively overlap, and then the adhesive is cured. The liquid crystal injection port is filled with liquid crystal MLC-6608 (trade name) manufactured by Merck Co., Ltd. between the two substrates, and the liquid crystal injection port is sealed by an epoxy adhesive, and the polarizing plate is bonded to the outer surfaces of the two substrates to make the polarization direction positive. A vertical alignment type liquid crystal display element is produced, and a vertical cross-sectional view of the obtained vertical alignment type liquid crystal display element is shown in Fig. 2, wherein reference numeral 1 denotes a spacer, reference numeral 2 denotes a protrusion, reference numeral 3 denotes a liquid crystal, and reference numeral 4 denotes The liquid crystal alignment film, reference numeral 5 denotes a color light-receiving sheet, and reference numeral 6 denotes a glass substrate. Next, the alignment property and voltage holding ratio of the obtained vertical alignment type liquid crystal display element were evaluated as follows. The alignment property was evaluated when the voltage was turned on and off. Whether an abnormal region is generated in the liquid crystal cell by a polarizing microscope to confirm that there is no abnormal region is "good". At the time of the application, after applying a voltage of 5 V to the liquid crystal display element, the circuit was turned off, and the holding voltage after 1 6.7 msec was measured, and the ratio of the holding voltage to the applied voltage (5 V) was calculated. When the 値 was 98% or more , think it is good. -45· 1379130

電壓 保持率 (%) 99.7 1 99.7 99.7 99.7 取向性 良好 良好 良好 良好 透明性 (%) 耐熱性 膜厚 變化率 (%) m cn ^Η 固化後 膜厚 (/zm) 寸 (N 寸 (N cnS 寸 耐溶劑性 膜厚 變化率 (%) ΓΝΪ (N ψ < 固化後 膜厚 丨 寸 oi 寸 <N 寸 <Ν 剖面形狀 分隔物 〇 U υ U 突起 < < < < 靈敏度評價 1靈敏度 J/m2 2800 1 2500 2200 2800 顯影液 濃度 (重量％) 寸 寸 Ο 寸 Ο 顯影液 TMAH K0H ΤΜΗΑ ΤΜΑΗ 顯影 方法 盛液法 盛液法 沖淋法 沖淋法 組合物 種類 (S-1) (S-2) (S-3) -1 (S-4) 實施例1 實施例2 實施例3 實施例4 1379130 【圖式簡單說明】 第1圖分別表示突起和間隔物的剖面形狀的示意圖〃 第2圖係表示具有突起和間隔物的垂直配向型液晶顯示 兀件的剖面形狀的示意圖。 【主要元件符號說明】 1 間隔物 2 突起Voltage holding ratio (%) 99.7 1 99.7 99.7 99.7 Good orientation Good good good transparency (%) Heat resistance film thickness change rate (%) m cn ^Η Film thickness after curing (/zm) inch (N inch (N cnS Inch solvent resistance film thickness change rate (%) ΓΝΪ (N ψ < film thickness after curing oi inch &< N inch < Ν section shape separator 〇 U υ U protrusion <<<< Evaluation 1 Sensitivity J/m2 2800 1 2500 2200 2800 Developer concentration (% by weight) inch inch Ο inch 显影 developer TMAH K0H ΤΜΗΑ 显影 development method liquid method liquid method shower method shower composition type (S-1) (S-2) (S-3) -1 (S-4) Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 1379130 [Simplified description of the drawings] Fig. 1 is a schematic view showing the cross-sectional shapes of protrusions and spacers, respectively. 〃 Fig. 2 is a schematic view showing the cross-sectional shape of a vertical alignment type liquid crystal display element having protrusions and spacers. [Main element symbol description] 1 spacer 2 protrusion

3 液晶 4 液晶配向膜 5 彩色濾光片 6 玻璃基板3 Liquid crystal 4 Liquid crystal alignment film 5 Color filter 6 Glass substrate

-47--47-

Claims (1)

I379J30 修正本 第095 1 1 1365號「感放射線性樹脂組合物、突起、間隔 物、垂直配向型液晶顯示元件、與突起及/或間隔物之形 成方法」專利案 (2012年7月25日修正） 十、申請專利範圍： 1. 一種感放射線性樹脂組成物’其係用以形成垂直配向型 液晶顯示元件用的突起及/或間隔物’其特徵在於：包括 [A] 共聚物，其係將下述（al)〜（a3)共聚而得到的共 聚物，其中 (al)是不飽和羧酸及/或不飽和羧酸酐， (a2)是具有環氧基或氧雜環丁烷基的不飽和化合物， (a3)是上述（al)及（a2)以外的烯烴類不飽和化合物； 共聚物[A]係包含： 5〜40重量％自化合物（al)所衍生的構成單元、 5〜60重量％自化合物（a2)所衍生的構成單元、及 10〜80重量％自化合物U3)所衍生的構成單元 (a 1、a2及a3之合計爲100重量％)之共聚物；與 [B] 光陽離子聚合引發劑，相對於100重量份共聚物 [A]，光陽離子聚合引發劑爲0.01〜15重量份。 2 .如申請專利範圍第1項之感放射線性樹脂組成物’其用 以形成垂直配向型液晶顯示元件用的突起及/或間隔物’ 且其進一步含有[C]噻噸酮類化合物。 3 .—種垂直配向型液晶顯示元件用之突起’該突起係由如 I37S130 r H年叫月^修正替攘蔓本 申請專利範圍第1或2項之感放射線性樹脂組成物所形 成0 4 . 一種垂直配向型液晶顯示元件用之間隔物，該間隔物係 由如申請專利範圍第1或2項之感放射線性樹脂組成物 所形成。 5.—種薄膜電晶體方式的液晶顯示器用垂直配向型液晶顯 示元件，該垂直配向型液晶顯示元件係具備如申請專利 範圍第3項之突起及/或如申請專利範圍第4項之間隔物 6.—種突起及/或間隔物之形成方法，其特徵在於：至少包 含如下步驟， (1 )在基板上形成如申請專利範圍第丨項之感放射線 性組成物的塗膜的步驟； (2) 對該塗膜的至少一部分照射放射線的步驟； (3) 顯影步驟； (4) 加熱步驟。I379J30 Revised the patent No. 095 1 1 1365 "Methods for the formation of radiation sensitive resin compositions, protrusions, spacers, vertical alignment type liquid crystal display elements, and protrusions and/or spacers" (Revised on July 25, 2012) X. Patent application scope: 1. A radiation sensitive resin composition which is used to form protrusions and/or spacers for a vertical alignment type liquid crystal display element, characterized in that it includes [A] copolymer, which is a copolymer obtained by copolymerizing the following (al) to (a3), wherein (al) is an unsaturated carboxylic acid and/or an unsaturated carboxylic anhydride, and (a2) is an epoxy group or an oxetane group; The unsaturated compound, (a3) is an olefinic unsaturated compound other than the above (al) and (a2); the copolymer [A] contains: 5 to 40% by weight of a constituent unit derived from the compound (al), 5~ 60% by weight of a constituent unit derived from the compound (a2), and 10 to 80% by weight of a copolymer derived from the compound U3) (a total of a1, a2 and a3 is 100% by weight); and [B Photocationic polymerization initiator relative to 100 parts by weight of copolymer [A], the photocationic polymerization initiator is 0.01 to 15 parts by weight. 2. The radiation sensitive resin composition of claim 1 which is used to form protrusions and/or spacers for a vertical alignment type liquid crystal display element and further contains a [C] thioxanthone compound. 3. A type of protrusion for a vertical alignment type liquid crystal display element. The protrusion is formed by a radiation-sensitive resin composition such as I37S130RH, which is called a moon, and is modified by the radiation-sensitive resin composition of the first or second aspect of the patent application. A spacer for a vertical alignment type liquid crystal display element formed of a radiation sensitive resin composition as disclosed in claim 1 or 2. 5. A vertical alignment type liquid crystal display element for a liquid crystal display of a thin film transistor type, the vertical alignment type liquid crystal display element having a protrusion as in the third aspect of the patent application and/or a spacer as in the fourth aspect of the patent application 6. A method for forming a protrusion and/or a spacer, comprising: at least the following step, (1) a step of forming a coating film of a radiation sensitive composition according to the scope of the patent application of the patent application; 2) a step of irradiating at least a portion of the coating film with radiation; (3) a developing step; and (4) a heating step.
TW095111365A 2005-04-01 2006-03-31 Radiation sensitive resin composition, projections and spacers, vertically aligned type liquid crystal display element, and the method for forming projections, and spacers TWI379130B (en)

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KR20060105630A (en) 2006-10-11
JP2006284975A (en) 2006-10-19
CN1841195A (en) 2006-10-04

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