TWI379161B - Radiation sensitive resin composition, method for forming projections and spacers, projections and spacers, and liquid crystal display element with them - Google Patents

Radiation sensitive resin composition, method for forming projections and spacers, projections and spacers, and liquid crystal display element with them Download PDF

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TWI379161B
TWI379161B TW095111367A TW95111367A TWI379161B TW I379161 B TWI379161 B TW I379161B TW 095111367 A TW095111367 A TW 095111367A TW 95111367 A TW95111367 A TW 95111367A TW I379161 B TWI379161 B TW I379161B
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ethyl
methyl
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carbon atoms
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TW095111367A
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TW200700909A (en
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Daigo Ichinohe
Hitoshi Hamaguchi
Toru Kajita
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Jsr Corp
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials For Photolithography (AREA)
  • Liquid Crystal (AREA)
  • Polymerisation Methods In General (AREA)

Description

1379161 九、發明說明： 【發明所屬之技術領域】 本發明涉及一種用於同時形成垂直型液晶顯示元件的 突起和間隔物（spacer)的感放射線性樹脂組成物、由該組成 物形成的突起和間隔物、包含該突起和間隔物的液晶顯示 元件。 【先前技術】 液晶顯示面板目前廣泛用於平板顯示器。特別是，隨著 φ例如個人電腦和文字處理器等0A設備以及液晶電視等的 推廣，對TFT(薄膜電晶體）方式的液晶顯示面板（TFT-LCD) 的顯示品質的要求變得越來越嚴格。 在TFT-LCD之中，現在TN(扭轉向列，Twisted Nematic) 型LCD是使用最多的。該LCD是通過下述方法製造的：在 2塊透明電極的外側配置配向方向相差90度的偏光膜，並 在兩塊透明電極內側配置配向膜；在兩配向膜之間配置向 列型液晶，將液晶的配向方向以90度的角度從一個電極側 #轉向另一個電極側。當非偏光在該狀態下入射時，已穿 過一個偏光片的直線偏光穿過液晶，它的偏振方向改變 了，因此它能穿過另一個偏光片，形成光亮狀態。然後， 當向兩個電極都施加電壓而使液晶分子直立時，到達液晶 的直線偏光就這樣穿過，不會穿過另一個偏光片，形成黑 暗狀態。此後，再次停止施加電壓時，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CRT相當或更優越。 1379161 是視角狹 :轉向列， 直配向， 型液晶顯 列型液晶 的配向軸 LCD是將 向的配向 使用雙折 接近配向 方向，因 晶配向的 專利文獻 域可以取 側的電極 入射側的 錯開，形 等）。 有可以微 但是，TN型LCD仍有一個大問題需要解決，那就 窄。 作爲解決這種問題的方法，開發出了 STN(超枉 Super Twisted Nematic)型 LCD 和 MVA(多域垂 Multi-domain Vertically Aligned)型 LCD(垂直配向 示面板）。其中，STN型LCD是在TN型LCD的向 中混入作爲光活性物質的手性試劑，將液晶分子 在2塊電極間扭轉180度或以上。另外，MVA型 •具有負的介電常數各向異性的負型液晶和垂直方 膜組合，並不使用ΤΝ型LCD的旋光模式，而是 射模式的LCD :即使在不施加電壓的狀態下，在 膜的位置上的液晶配向方向也可以大致保持垂直 此，對比度、視角等優異，而且可以不進行使液 硏磨處理等，在製造步驟方面也是優異的（參照非 1和專利文獻1)。 在MVA型LCD中，爲了使液晶在一個圖元區 f個配向方向，作爲區域限製方法可以是使顯示 爲在1個圖元區域內具有狹縫的電極，而且在光 電極上的同一圖元區域內，將電極的狹縫和位置 成具有斜面的突起（例如，三角錐形，半凸透鏡形 這種突起通常可以通過光刻法形成，光刻法具 細加工、容易控製形狀的優點。 另一方面，必須在液晶面板中設置規定的間隔物，從而 將2塊基板保持一定間隔。目前，作爲這種間隔物使用具 1379161 έ Ν 有規定粒徑的玻璃珠、塑膠珠等間隔物粒子。但是，這些 間隔物粒子在玻璃基板上隨機分佈，所以在有效圖元部記 憶體在上述間隔物時，會受到間隔物的反射，入射光被散 射，具有液晶面板的對比度降低的問題。爲了解決這些問 題，提出了使用感放射線性樹脂組成物，通過光刻法在有 效圖元部以外形成間隔物的方法。 在使用利用感放射線性樹脂的光刻法形成突起和形成 間隔物時，可以使用同樣的方法，但是下述各自要求的性 •能有所不同。 (1) 突起和間隔物所要求的膜厚不同。 (2) 所要求的形狀不同，分別是突起爲半凸透鏡狀，而間 隔物爲柱狀或順圓錐狀。 另外’由於必須在突起上形成配向膜，所以在後續步驟 中形成配向膜時’爲了不產生排斥，要求配向膜材料有足 夠的塗布性》 另一方面，爲了使液晶面板不會由於外部壓力變形，間 φ隔物還必須有很高的壓縮強度。 此外，突起、間隔物還必須對之後的面板組裝步驟中施 加的熱量有足夠的承受力。 在突起上形成配向膜時，如果突起相對基板的圓錐角過 大，例如爲3 0度或以上時，則在突起的上部，會產生配向 膜的印刷不良，面板形成後，發生顯示不佳的可能性變高。 因此，'突起相對基板的圓錐角較佳爲30度或以下。 如上所述，由於突起和間隔物要求不同的形狀、不同的 1379161 化學性質，至今爲止必須使用不同的感放射線性材料，使 用不同的步驟形成。另外，在專利文獻2中還公開了使用 負型感光材料，同時形成突起和間隔物的設想，但是在該 公報中並未公開可以在這種用途中使用的感放射線性組成 物的具體方案，還不知道用於同時形成突起和間隔物的感 放射線性組成物，所以強烈需要提供這種材料。 【非專利文獻1】武田有廣，液晶，日本液晶學會，1 999 年 4 月 25 日，Vol.3，No.2，1 17 • 【專利文獻1】特開平1 1 -258605號公報 【專利文獻2】特開2001-83517號公報 另外，近年來，從液晶顯示元件的大面積化和提高生產 性等觀點出發，玻璃母板的大型化（例如，1,500x 1,800mm 左右）快速發展。然而，現在的基板的尺寸（680x880mm左右） 比掩模的尺寸更小，所以可以與整體曝光方式相適應，但 是在爲大型基板時，幾乎無法製造與該基板的尺寸相同程 度的掩模，難以適應整體曝光方式。 φ 因此’作爲適應大型基板的曝光方式，提倡分步曝光方 式。但是，分步曝光方式是對一塊基板進行幾次曝光，在 每次曝光時，使位置對齊和分步移動需要花費時間，與整 體曝光方式相比，可以認爲是降低生產能力的問題。 另外，在整體曝光方式中，可以是3,000〗/m2左右的曝 光量，但是在分步曝光時，必須使各次的曝光量更低，至 今爲止在間隔物的形成中使用的現有的感放射線性樹脂組 成物難以在l,20OJ/m2或以下的曝光量下形成足夠的間隔物 1379161 形狀和膜厚》 【發明內容】 本發明是根據以上的問題而提出的，其目的在於提供一 種感放射線性樹脂組成物’由該組成物形成的突起和間隔 物，具有該突起和間隔物的液晶顯示元件；其中該感放射 線性樹脂組成物是高靈敏度，即使在l,200J/m2或以下的曝 光量下也可以得到足夠的形狀，適合用於同時形成垂直配 向型液晶顯示元件的突起和間隔物》 • 根據本發明，上述課題第一是通過一種用於同時形成垂 直配向型液晶顯示元件的突起和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（ai)、（a2)共聚而得到的共聚物，其中（al)是 不飽和羧酸和/或不飽和羧酸酐，（a2)是（a 1)成分以外的其他 不飽和化合物； [B ]聚合性不飽和化合物；和 • [C]由下式（1)或（2)所示的化合物形成的感放射線性聚合 引發劑，1379161 IX. The present invention relates to a radiation-sensitive resin composition for simultaneously forming protrusions and spacers of a vertical type liquid crystal display element, protrusions formed of the composition, and A spacer, a liquid crystal display element including the protrusion and the spacer. [Prior Art] A liquid crystal display panel is currently widely used for a flat panel display. In particular, with the promotion of φ, such as personal computers and word processors, and LCD TVs, the display quality of TFT (Thin Film Transistor) liquid crystal display panels (TFT-LCDs) is becoming more and more demanding. strict. Among TFT-LCDs, TN (Twisted Nematic) type LCDs are now the most used. The LCD is manufactured by disposing a polarizing film having a direction difference of 90 degrees in the outer direction of the two transparent electrodes, and arranging an alignment film inside the two transparent electrodes; and disposing the nematic liquid crystal between the two alignment films. The alignment direction of the liquid crystal is shifted 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 linearly polarized light that has passed through one polarizer passes through the liquid crystal, and its polarization direction is changed, so that it can pass through the other polarizer to form a bright state. Then, when a voltage is applied to both electrodes to make the liquid crystal molecules stand upright, the linearly polarized light reaching the liquid crystal passes through, and does not pass through the other polarizer to form a dark state. Thereafter, when the application of the voltage is stopped again, it returns to the bright state. Although, due to technological advances in recent years, such a TN type LCD has become comparable or superior to a CRT in terms of frontal contrast and color reproducibility. 1379161 is a narrow viewing angle: the steering column, the direct alignment, the alignment axis LCD of the liquid crystal display type liquid crystal uses the birefringence to approach the alignment direction, and the patent document domain of the crystal alignment can take the staggered side of the incident side of the electrode. Shape, etc.). There is a slight difference. However, the TN type LCD still has a big problem to be solved, and it is narrow. As a method for solving this problem, an STN (Super Twisted Nematic) type LCD and an MVA (Multi-domain Vertically Aligned) type LCD (Vertical Alignment Display Panel) have been developed. Among them, the STN type LCD is a chiral agent which is a photoactive material mixed in the TN type LCD, and the liquid crystal molecules are twisted by 180 degrees or more between the two electrodes. In addition, MVA type • Negative liquid crystal and vertical square film combination with negative dielectric anisotropy do not use the optical rotation mode of the ΤΝ-type LCD, but the radiation mode LCD: even in the state where no voltage is applied, The liquid crystal alignment direction at the position of the film can be kept substantially perpendicular, and the contrast, the viewing angle, and the like are excellent, and the liquid honing treatment or the like is not performed, and the manufacturing process is also excellent (see Non-Patent 1 and Patent Document 1). In the MVA type LCD, in order to make the liquid crystals have a direction of alignment in one primitive region, the region limiting method may be to display an electrode having a slit in one primitive region and the same primitive region on the photoelectrode. Inside, the slits and positions of the electrodes are formed into beveled protrusions (for example, triangular pyramids, semi-convex lens-shaped protrusions can usually be formed by photolithography, and photolithography has the advantage of fine processing and easy control of shape. In addition, it is necessary to provide a predetermined spacer in the liquid crystal panel, and to keep the two substrates at a constant interval. At present, spacer particles such as glass beads and plastic beads having a predetermined particle diameter are used as the spacer. Since these spacer particles are randomly distributed on the glass substrate, when the memory of the effective element portion is in the spacer, the spacer is reflected and the incident light is scattered, which causes a problem that the contrast of the liquid crystal panel is lowered. The problem is a method of forming a spacer outside the effective pixel portion by photolithography using a radiation sensitive resin composition. When the protrusions and the spacers are formed by photolithography using a radiation sensitive resin, the same method can be used, but the properties required for the following can be different. (1) The film thickness required for the protrusions and spacers is different. (2) The required shape is different, that is, the protrusion is a semi-convex lens shape, and the spacer is columnar or conical. In addition, since the alignment film must be formed on the protrusion, when the alignment film is formed in the subsequent step' In order not to cause repulsion, the alignment film material is required to have sufficient coating properties. On the other hand, in order to prevent the liquid crystal panel from being deformed by external pressure, the inter-φ spacer must also have a high compressive strength. In addition, the protrusions and spacers are also It is necessary to have sufficient resistance to the heat applied in the subsequent panel assembly step. When the alignment film is formed on the protrusion, if the taper angle of the protrusion with respect to the substrate is too large, for example, 30 degrees or more, then in the upper portion of the protrusion, Printing defects of the alignment film are generated, and the possibility of poor display after the formation of the panel becomes high. Therefore, the taper angle of the protrusion to the substrate is preferably 30. Or as follows. As described above, since the protrusions and the spacers require different shapes and different 1791161 chemical properties, it has heretofore been necessary to use different radiation-sensitive materials, which are formed using different steps. Further, Patent Document 2 discloses The use of a negative-type photosensitive material to simultaneously form protrusions and spacers, but a specific scheme of the radiation-sensitive composition that can be used in such use is not disclosed in this publication, and it is not known to simultaneously form protrusions and spaces. The radiation-linear composition of the object is strongly required to provide such a material. [Non-Patent Document 1] Takeda Yuki, Liquid Crystal, Japanese Society of Liquid Crystals, April 25, 999, Vol. 3, No. 2, 1 17 [Patent Document 1] Japanese Laid-Open Patent Publication No. 2001-83517 (Patent Document 2) The large-scale (for example, around 1,500 x 1,800 mm) has developed rapidly. However, the size of the current substrate (about 680 x 880 mm) is smaller than the size of the mask, so that it can be adapted to the overall exposure mode. However, when it is a large substrate, it is almost impossible to manufacture a mask having the same level as the size of the substrate. Adapt to the overall exposure. φ Therefore, as a method of exposure to a large substrate, a step-by-step exposure method is advocated. However, the stepwise exposure method is to expose a substrate several times. It takes time to align the position and step by step in each exposure, which is considered to be a problem of lowering the productivity than the whole exposure method. Further, in the overall exposure method, the exposure amount may be about 3,000 Å/m2, but in the case of stepwise exposure, it is necessary to make the exposure amount of each time lower, and the conventional sensible radiation used in the formation of the spacer so far. The resin composition is difficult to form a sufficient spacer 1791161 shape and film thickness at an exposure amount of 1,20 OJ/m 2 or less. [Invention] The present invention has been made in view of the above problems, and an object thereof is to provide a radiation sensitive Resin composition 'protrusions and spacers formed of the composition, liquid crystal display elements having the protrusions and spacers; wherein the radiation sensitive resin composition is highly sensitive, even at an exposure of 1,200 J/m 2 or less It is also possible to obtain a sufficient shape for the protrusions and spacers for simultaneously forming the vertical alignment type liquid crystal display element. According to the present invention, the above object is firstly to provide a protrusion for simultaneously forming a vertical alignment type liquid crystal display element. And a radiation sensitive linear resin composition of the spacer, characterized in that the radiation sensitive resin composition is included [A] a copolymer obtained by copolymerizing the following (ai) and (a2), wherein (al) is an unsaturated carboxylic acid and/or an unsaturated carboxylic anhydride, and (a2) is other than the component (a1). a saturated compound; [B] a polymerizable unsaturated compound; and • [C] a radiation-sensitive polymerization initiator formed of a compound represented by the following formula (1) or (2),

其中’R，是選自碳原子數爲1~20的烷基、碳原子數爲3 1379161 » 〜8的環院基或苯基的基團，R2、R;分別是選自氫原子、 碳原子數爲1〜20的烷基、碳原子數爲3〜8的環烷基、取 代或未取代的苯基、或碳原子數爲7〜20的脂環基（但，碳 原子數爲7 ~8的環烷基除外）的基團，上述取代苯基的取代 基爲碳原子數爲1〜6的烷基、碳原子數爲1〜6的烷氧基、 苯基或鹵原子，是選自碳原子數爲4〜20的含氧雜環基、 碳原子數爲4〜20的含氮雜環基或碳原子數爲4〜20的含 硫雜環基的基團，Rs是選自氫、碳原子數爲1〜12的烷基 隹或碳原子數爲1〜12的烷氧基的基團’ η是1〜5的整數， m是0〜5的整數，n+mS 5，Wherein 'R, is a group selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a ring-membered group having a carbon number of 3 1379161 » 8 or a phenyl group, R 2 and R; each selected from a hydrogen atom and a carbon. An alkyl group having 1 to 20 atoms, a cycloalkyl group having 3 to 8 carbon atoms, a substituted or unsubstituted phenyl group, or an alicyclic group having 7 to 20 carbon atoms (however, the number of carbon atoms is 7) a group of the above-mentioned substituted phenyl group, wherein the substituent of the substituted phenyl group is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a phenyl group or a halogen atom, It is selected from the group consisting of an oxygen-containing heterocyclic group having 4 to 20 carbon atoms, a nitrogen-containing heterocyclic group having 4 to 20 carbon atoms or a sulfur-containing heterocyclic group having 4 to 20 carbon atoms, and Rs is selected. The group 'n" from hydrogen, an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms is an integer of 1 to 5, m is an integer of 0 to 5, n + mS 5 ,

癱其中，R,、R2、R3、R”、Rs、m以及η的定義與上述相 同，1 爲 0-6 的整數 ’ Rl' R2、R3、R4、R5' m、η 以及1 是 相互獨立的。 本發明的上述課題’第二點是通過一種同時形成突起和 間隔物的形成方法實現的’該方法的特徵在於：至少含有 下述順序記載的下述步驟： (1)在基板上形成上述感放射'線性樹S旨組成物1薄膜的步 驟， -11 - 1379161 ’ 和 驟 ， 。 步驟驟 的步步 /^J^1. f ^7 曝影熱 部顯加 一 膜膜 少薄薄 至該該 S 勺 勺 膜後後 薄光影 該曝顯 將將將 \—/ \1/ \1/ 2 3 4 /V /IN /|\ 題 課 述 上 的 明 發 本 射 放 感 的. W ΤΙΡΓ 記 。 述的 上現 由實 過物 通隔 是間 點和 三起 第突 的 成 形 物 成 組 脂 樹 性 線 題 ml·/ 述 上 的 明 發 本Wherein, R, R2, R3, R", Rs, m, and η have the same definitions as above, and 1 is an integer of 0-6 'Rl' R2, R3, R4, R5' m, η, and 1 are independent of each other The second aspect of the present invention is achieved by a method of forming a protrusion and a spacer simultaneously. The method is characterized in that it comprises at least the following steps described in the following order: (1) formation on a substrate The above-mentioned sensible radiation 'linear tree S is the step of the composition 1 film, -11 - 1379161 ' and the step, the step of the step / ^ J ^ 1. f ^ 7 exposure of the hot part of the film is less thin After the S spoon scoop film, the thin light shadow will be exposed to the \-/ \1/ \1/ 2 3 4 /V /IN /|\ lesson. ΤΙΡΓ 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。

元 示 顯 晶 液 3 的式 物方 隔施 間實 和C 起 突 的 載 記 述 上 有 具 過 通。 是的 點現 四實 第件 明 說 細 詳物 行成 進組 明脂 發樹 本性 對線 I射 下放 以感 [A]共聚物： 本發明的感放射線性樹脂組成物中使用的[A]共聚物是 將（al)不飽和羧酸和/或不飽和羧酸酐，U2) (al)成分以外 的其他不飽和化合物共聚物得到的。 在構成[A]共聚物的各成分中，作爲（al)不飽和羧酸和/ 或不飽和羧酸酐（將它們總稱爲“（al)不飽和羧酸類化合 #")，可以列舉出例如丙烯酸、甲基丙烯酸、巴豆酸、2· 丙烯醯氧基乙基琥珀酸、2-甲基丙烯醯氧基乙基琥珀酸、 2-丙烯醯氧基乙基六氫鄰苯二甲酸、2-甲基丙烯醯氧基乙 基六氫鄰苯二甲酸等一元羧酸類；馬來酸、富馬酸、檸康 酸、中康酸、衣康酸等二元羧酸類；上述二元羧酸的酸酐 類等。 在這些（a 1)不飽和羧酸類化合物中，從共聚反應性、所 得的[A]共聚物對鹼性顯影液的溶解性和容易獲得方面出 -12- 1379161 發’較佳爲丙烯酸、甲基丙烯酸、2-丙烯醯氧基乙基琥珀 酸、2·甲基丙烯醯氧基乙基琥珀酸等。 在[A]共聚物中，（ai)不飽和羧酸類化合物可以單獨使 用’也可以將2種或更多種混合後使用。 在[A]共聚物中，來自（al)不飽和羧酸類化合物的重複單 元的含有率爲5〜60重量％，較佳爲10〜50重量％，更較佳 爲15〜40重量％(其中，（ai)+(a2)=100重量％，下同）。此 時’來自U1)不飽和羧酸類化合物的重複單元的含有率小於 重量％時，對鹼性顯影液的溶解性有降低的趨勢；另一方 面’如果超過60重量％，則該共聚物對鹼性顯影液的溶解 性有變得過大的危險。 作爲（a2)其他不飽和化合物，首先可以列舉出含有環氧 基的不飽和化合物。 作爲含有環氧基的不飽和化合物，可以列舉出例如丙烯 酸縮水甘油酯、丙烯酸2-甲基縮水甘油酯、丙烯酸4-羥丁 基酯縮水甘油醚、丙烯酸-3,4-環氧丁基酯、丙烯酸-6,7·環 #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 -13- 1379161 我 庚基酯、α-乙基丙烯酸3,4-環氧環己基酯等其他的^^ -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-乙烯基苄基縮水甘油醚等縮水甘油醚類等。 在這些含有環氧基的不飽和化合物中，從共聚反應性以 及間隔物和突起材料的強度方面出發，較佳甲基丙烯酸縮 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-羥基丁基酯縮水甘油醚、鄰-乙烯基 ®〒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。 在[Α]共聚物中，（a2)含環氧基的不飽和化合物可以單獨 使用，也可以將2種或更多種混合後使用。 另外，作爲U2)其他不飽和化合物，除了上述含環氧基 的不飽和化合物以外，還可以列舉出例如丙烯酸甲酯、丙 嫌酸正丙酯、丙烯酸異丙酯、丙烯酸正丁酯、丙烯酸仲丁 酯、丙烯酸叔丁酯等丙烯酸烷基酯類： • 甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丙 酯、甲基丙烯酸異丙酯、丙酸正丁酯、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； 丙烯酸環己基酯、丙烯酸2·甲基環己基酯、丙烯酸三環 [5.2.1·02·6]癸-8-基酯、丙烯酸 2-(三環[5.2.1.02·6]癸烷-8-基 氧基）乙基酯、丙烯酸異佛爾酮酯等丙烯酸脂環酯類； 甲基丙烯酸環己基酯、甲基丙烯酸2-甲基環己基酯、甲 基丙烯酸三環[5.2. 1.026]癸-8-基酯、甲基丙烯酸2-(三環 -14- Ι379·161 [5.2.1.02 δ]癸烷-8-基氧基）乙基酯、甲基丙烯酸異佛爾酮酯 等甲基丙烯酸脂環酯類： 馬來酸二乙酯、富馬酸二乙酯、衣康酸二乙酯等不飽和 二元羧酸二烷基酯類； 丙燒酸四氨映喃-2-基醋、丙嫌酸四氣卩比喃-2-基醋、丙 烯酸2-甲基四氫吡喃-2-基酯等具有含氧五元雜環或含氧 六元雜環的丙烯酸酯類； 甲基丙稀酸四氫肤喃-2-基醋、甲基丙稀酸四氫卩比喃- 2-酯、甲基丙烯酸2-甲基四氫吡喃-2-基酯等具有含氧五元 雜環或含氧六元雜環的甲基丙烯酸酯類； 苯乙烯、α-甲基苯乙烯、間-甲基苯乙烯、對-甲基苯乙 烯、對-甲氧基苯乙烯等乙烯基芳香族化合物： 1，3-丁二烯、異戊二烯、2,3-二甲基-1，3-丁二烯等共軛二 烯類化合物，以及丙烯腈、甲基丙烯腈、丙烯醯胺、甲基 丙烯醯胺、氯乙烯、偏二氯Ζ烯、醋酸乙烯酯等。 在上述含有環氧基的不飽和化合物以外的U2)其他不飽 化合物中，從共聚反應性和所得的[Α]共聚物對鹼水溶液 的溶解性方面出發，較佳爲丙烯酸2-甲基環己基酯、甲基 丙烯酸叔丁酯、甲基丙烯酸三環[ 5.2.1 .0 2 6]癸-8-基酯、苯 乙烯、對-甲氧基苯乙烯、甲基丙烯酸四氫呋喃-2-基酯、1,3-丁二烯等。 在[A]共聚物中，含有環氧基的不飽和化合物以外的（a2) 其他不飽和化合物可以單獨使用，也可以將2種或更多種 混合後使用。 -15- 1379161 在[A]共聚物中，（a 2)可以使用2種或以上，來自它們的 重複單元的總含量爲40~95重量％，較佳爲50~90重量％， 更較佳爲60〜85重量％。此時，來自（a2)的重複單元的總含 量小於40重量％時，在顯影時可能會產生膨脹以及出現溶 液黏度增加；另一方面如果超過95重量％，則對顯影液的 ' 溶解性可能會降低。可能會產生顯影時膨脹和溶液黏度增 加。 [A]共聚物，例如可以在適當地溶劑中、在自由基聚合 •引發劑的存在下，將（al)不飽和羧酸類化合物、U2)(al)以 外的不飽和化合物聚合而製造。 作爲上述聚合中使用的溶劑，可以列舉出例如甲醇、乙 醇、正丙醇、異丙醇等醇類：四氫呋喃、二噚烷等醚類： 乙二醇單甲基醚、乙二醇單乙基醚、乙二醇單正丙基醚、 乙二醇單正丁基醚等乙二醇單烷基醚類；乙二醇單甲基醚 乙酸酯、乙二醇單乙基酸乙酸酯、乙二醇單正丙基醚乙酸 酯、乙二醇單正丁基醚乙酸酯等乙二醇單烷基醚乙酸酯類； φ 乙二醇單甲基醚丙酸酯、乙二醇單乙基醚丙酸酯、乙二 醇單正丙基醚丙酸酯、乙二醇單正丁基醚丙酸酯等乙二醇 單烷基醚丙酸酯類；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、二甘醇甲基乙基醚等 • 二甘醇烷基醚類： _ 丙二醇單甲基醚、丙二醇單乙基醚、丙二醇單正丙基 醚、丙二醇單正丁基醚等丙二醇單烷基醚類；二丙二醇單 甲基醚、二丙二醇單乙基醚、二丙二醇二甲基醚、二丙二 -16- 1379161 醇二乙基醚、二丙二醇甲基乙基醚等二丙二醇單烷基醚類； 丙二醇單甲基醚乙酸酯、丙二醇單乙基醚乙酸酯、丙二 醇單正丙基醚乙酸酯、丙二醇單正丁基醚乙酸酯等丙二醇 單烷基醚乙酸酯類；丙二醇單甲基醚丙酸酯、丙二醇單乙 基醚丙酸酯、丙二醇單正丙基醚丙酸酯、丙二醇單正丁基 醚丙酸酯等丙二醇單烷基醚丙酸酯類： 甲苯、二甲苯等芳烴類；甲乙酮、2-戊酮、3-戊酮、環 己酮、4-羥基-4-甲基-2-戊酮等酮類； • 2-甲氧基丙酸甲酯、2-甲氧基丙酸乙酯、2-甲氧基丙酸 正丙酯、2-甲氧基丙酸正丁酯、2-乙氧基丙酸甲酯、2·乙氧 基丙酸乙酯、2-乙氧基丙酸正丙酯、2-乙氧基丙酸正丁酯、 2-正丙氧基丙酸甲酯、2-正丙氧基丙酸乙酯、2-正丙氧基丙 酸正丙酯、2-正丙氧基丙酸正丁酯、2-正丁氧基丙酸甲酯、 2- 正丁氧基丙酸乙酯、2_正丁氧基丙酸正丙酯、2-正丁氧基 丙酸正丁酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-甲氧基丙酸正丙酯、3 -甲氧基丙酸正丁酯、3 -乙氧基丙酸 •甲酯、3-乙氧基丙酸乙酯、3-乙氧基丙酸正丙酯、3-乙氧基 丙酸正丁酯、3-正丙氧基丙酸甲酯、3-正丙氧基丙酸乙酯、 3- 正丙氧基丙酸正丙酯、3-正丙氧基丙酸正丁酯、3-正丁氧 基丙酸甲酯、3-正丁氧基丙酸乙酯、3-正丁氧基丙酸正丙 酯、3-正丁氧基丙酸正丁酯等烷氧基丙酸烷基酯類； 以及醋酸甲酯、醋酸乙酯、醋酸正丙酯、醋酸正丁酯' 羥基醋酸甲酯、羥基醋酸乙酯、羥基醋酸正丙酯、羥基醋 酸正丁酯、乳酸甲酯、乳酸乙酯、乳酸正丙酯、乳酸正丁 -17- 1379161 1 酯、2-羥基-2_甲基丙酸甲酯、2-羥基-2-甲基丙酸乙酯、3-羥基丙酸甲酯、3-羥基丙酸乙酯、3-羥基丙酸正丙酯、3· 羥基丙酸正丁酯、2-羥基-3-甲基丁酸甲酯、甲氧基醋酸甲 酯 '甲氧基醋酸乙酯、甲氧基醋酸正丙酯、甲氧基醋酸正 丁酯、乙氧基醋酸甲酯、乙氧基醋酸乙酯、乙氧基醋酸正 丙酯、乙氧基醋酸正丁酯、正丙氧基醋酸甲酯、正丙氧基 醋酸乙酯、正丙氧基醋酸正丙酯、正丙氧基醋酸正丁酯、 正丁氧基醋酸甲酯、正丁氧基醋酸乙酯 '正丁氧基醋酸正 ®丙酯、正丁氧基醋酸正丁酯等其他酯類等。 在這些溶劑中，較佳爲二甘醇烷基醚類、丙二醇單烷基 醚乙酸酯類、烷氧基丙酸烷基酯類等。 上述溶劑可以單獨使用，也可以將2種或更多種混合後 使用。 相對於（al)、（a2)成分的總量100重量份，以上溶劑的用 量爲150〜450重量份、較佳爲200〜400重量份。 另外，作爲上述自由基聚合引發劑沒有特別的限定，可 •以列舉出例如2,2’-偶氮二異丁腈、2,2’·偶氮二（2,4-二甲基 戊腈）、2,2，-偶氮二（4-甲氧基-2,4-二甲基戊腈）、4,4，-偶氮 二（4-氰基戊酸）、二甲基-2,2’-偶氮二（2-甲基丙酸酯）、2,2’-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；過氧化氫 等》 另外，在使用過氧化物作爲自由基聚合引發劑時，可以 -18 - 1379161 將其與還原劑一起作爲氧化還原型引發劑使用。 這些自由基聚合引發劑可以單獨使用，也可以將2種或 更多種混合後使用。 相對於（a 1)、U2)成分的總量100重量份，自由基聚合引 發劑的用量爲1〜20重量份，較佳爲3〜15重量份。 在自由基聚合時，除此以外，還可以和表面活性劑、鏈 轉移劑等一起使用。 另外，自由基聚合條件是溫度爲50〜1 10°C、較佳爲60 I 100 °C，聚合時間爲180〜480分鐘，較佳爲240〜420分 鐘左右。 [A] 共聚物的凝膠滲透色譜法（GPC)的聚苯乙烯換算重均 分子量（下文，稱作“ Mw” ）爲 2,000~100,000，較佳爲 5,000~50,000。此時，在Mw小於2,000時，所得的塗膜的 鹼顯影性、殘膜率等降低，或者圖案形狀、耐熱性等受損 的危險；另一方面，如果超過1 00,000，則有清晰度降低或 者圖案形狀受損的危險。 • [A]共聚物的分子量可以通過溶劑相對於共聚物（a l)、（a2) 成分的總量的量、自由基聚合引發劑的量、聚合時間、聚 合溫度、使用的鏈轉移劑調節。 [B ]聚合性不飽和化合物： [B] 聚合性不飽和化合物由在感放射線性聚合引發劑的 存在下，通過放射線曝光聚合的不飽和化合物形成。 作爲這種[B ]聚合性不飽和化合物沒有特別的限製，例 如’較佳單官能、2官能、3官能或以上的（甲基）丙烯酸酯 -19- 1379161 類，這是由於其共聚性良好，可以提高所得的突起和間隔 物的強度。 作爲上述單官能（甲基）丙烯酸酯類，可以列舉出例如丙 烯酸2-羥乙基酯 '甲基丙烯酸2-羥乙基酯、二甘醇單乙基 醚丙烯酸酯、二甘醇單乙基醚甲基丙烯酸酯、丙烯酸異佛 爾酮酯、甲基丙烯酸異佛爾酮酯、丙烯酸3 -甲氧基丁基酯、 甲基丙烯酸3-甲氧基丁基酯、（2-丙烯醯氧基乙基）（2-羥基 丙基）鄰苯二甲酸酯、（2-甲基丙烯醯氧基乙基）（2·羥基丙基） •鄰苯二甲酸酯等·。另外，作爲市售品，可以列舉出例如 ARONIX M-101、ARONIX M-lll、ARONIX Μ·114(以上，東 亞合成（株）製）；KAYARAD TC-110S、KAYARAD TC-120S(以 上，曰本化藥（株）製）；VISCOAT 158、VISCOAT 2311(以上， 大阪有機化學工業（株）製）等商品。 另外，作爲上述2官能的（甲基）丙烯酸酯類，可以列舉 出例如乙二醇二丙烯酸酯、乙二醇二甲基丙烯酸酯、二甘 醇二丙烯酸酯、二甘醇二甲基丙烯酸酯、四甘醇二丙烯酸The indications of the metamorphic liquid crystal 3 and the C-cracking are described above. Yes, the first part of the article is said to be detailed, and the details are as follows: the group is made into the group, and the hair is made into the group. The line I is shot down. [A] Copolymer: [A] copolymer used in the radiation sensitive resin composition of the present invention. The material is obtained by copolymerizing an unsaturated compound other than the (al) unsaturated carboxylic acid and/or unsaturated carboxylic anhydride, U2) (al) component. Among the components constituting the [A] copolymer, as the (al) unsaturated carboxylic acid and/or the unsaturated carboxylic anhydride (togetherly referred to as "(al) unsaturated carboxylic acid compound #"), for example, Acrylic acid, methacrylic acid, crotonic acid, 2· propylene methoxyethyl succinic acid, 2-methyl propylene methoxyethyl succinic acid, 2-propenyl methoxyethyl hexahydrophthalic acid, 2- a monocarboxylic acid such as methacryloxyethyl hexahydrophthalic acid; a dicarboxylic acid such as maleic acid, fumaric acid, citraconic acid, mesaconic acid or itaconic acid; and the above dicarboxylic acid An acid anhydride or the like. Among these (a 1) unsaturated carboxylic acid compounds, from the copolymerization reactivity, the solubility of the obtained [A] copolymer to an alkaline developer, and the easy availability, it is preferable that -12-1379161 is produced. It is acrylic acid, methacrylic acid, 2-propenyloxyethyl succinic acid, 2-methacryloxyethyl succinic acid, etc. In the [A] copolymer, the (ai) unsaturated carboxylic acid compound can be used alone. It can also be used after mixing 2 or more. In [A] copolymer, from (al) unsaturated carboxylic acid The content of the repeating unit of the compound is 5 to 60% by weight, preferably 10 to 50% by weight, more preferably 15 to 40% by weight (wherein (ai) + (a2) = 100% by weight, the same When the content of the repeating unit of the unsaturated carboxylic acid compound from "U1" is less than the weight%, the solubility in the alkaline developing solution tends to decrease; on the other hand, if it exceeds 60% by weight, the copolymerization The solubility of the substance in the alkaline developing solution may be excessively increased. As the (a2) other unsaturated compound, an epoxy group-containing unsaturated compound may be mentioned first. Examples of the epoxy group-containing unsaturated compound include For example, glycidyl acrylate, 2-methylglycidyl acrylate, 4-hydroxybutyl acrylate glycidyl ether, 3,4-epoxybutyl acrylate, acetyl-6,7·cyclo#heptyl ester Acrylic epoxy (cyclo)alkyl esters such as 3,4_epoxycyclohexyl acrylate: glycidyl methacrylate, 2-methylglycidyl methacrylate, methacrylic acid-3,4-ring Oxybutyl acrylate, -6,7-epoxyheptyl methacrylate, methacryl Ethylene (epoxy) alkyl methacrylates such as acid 3,4-epoxycyclohexyl ester; glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, shrinkage of α-n-butyl acrylate Glyceryl ester, α-ethyl acrylate 6,7-epoxy-13- 1379161 Iheptyl ester, α-ethyl acrylate 3,4-epoxycyclohexyl ester and other ^^-alkyl acrylate epoxy (ring Alkyl esters; glycidyl ethers such as o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, etc. Among the saturated compounds, glycidyl methacrylate, 2-methylglycidyl methacrylate, and 6,7-epoxyglycol methacrylate are preferred from the viewpoints of copolymerization reactivity and strength of the spacer and the protrusion material. A base ester, 4-hydroxybutyl acrylate glycidyl ether, o-vinyl fluorenyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinyl vinyl glycidyl ether, and the like. In the [Α] copolymer, the (a2) epoxy group-containing unsaturated compound may be used singly or in combination of two or more. Further, as the other unsaturated compound of U2), in addition to the above epoxy group-containing unsaturated compound, for example, methyl acrylate, n-propyl propyl acrylate, isopropyl acrylate, n-butyl acrylate, and acrylic acid may be mentioned. Alkyl acrylates such as butyl ester and tert-butyl acrylate: • Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl propionate, methacrylic acid Alkyl methacrylates such as sec-butyl ester and tert-butyl methacrylate; cyclohexyl acrylate, 2·methylcyclohexyl acrylate, tricyclo[5.2.1·02·6]癸-8-yl Ester, acrylate alicyclic esters such as 2-(tricyclo[5.2.1.02·6]decane-8-yloxy)ethyl acrylate and isophorone acrylate; cyclohexyl methacrylate, methyl 2-methylcyclohexyl acrylate, tricyclo[5.2.1.026]non-8-yl methacrylate, 2-(tricyclo-14- Ι379.161 [5.2.1.02 δ]decane-8 Ethyl methacrylate alicyclic esters such as -ethyloxy)ethyl ester and isophorone methacrylate: diethyl maleate, rich Dialkyl esters of unsaturated dicarboxylic acid such as diethyl acid and diethyl itaconate; tetraammine-2-yl vinegar of propionate, tetrahydropyrene-2-ethyl vinegar An acrylate having an oxygen-containing five-membered heterocyclic ring or an oxygen-containing six-membered heterocyclic ring, such as 2-methyltetrahydropyran-2-yl acrylate; methacrylic acid tetrahydrofuran-2-yl vinegar, Methyl acrylate having an oxygen-containing five-membered heterocyclic ring or an oxygen-containing six-membered heterocyclic ring, such as tetrahydroindole methan-2-ethyl methacrylate or 2-methyltetrahydropyran-2-yl methacrylate Esters; vinyl aromatic compounds such as styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene: 1,3-butadiene, different a conjugated diene compound such as pentadiene or 2,3-dimethyl-1,3-butadiene, and acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl chloride, and partial Dichlorodecene, vinyl acetate, and the like. Among the other unsaturated compounds other than the above epoxy group-containing unsaturated compound, from the viewpoint of copolymerization reactivity and solubility of the obtained [Α] copolymer to an aqueous alkali solution, a 2-methyl ring of acrylic acid is preferred. Hexyl ester, tert-butyl methacrylate, tricyclo[5.2.1 .0 2 6]non-8-yl methacrylate, styrene, p-methoxystyrene, tetrahydrofuran-2-yl methacrylate Ester, 1,3-butadiene, and the like. In the [A] copolymer, the (a2) other unsaturated compound other than the epoxy group-containing unsaturated compound may be used singly or in combination of two or more. -15- 1379161 In the [A] copolymer, (a 2) may be used in two or more kinds, and the total content of the repeating units derived therefrom is 40 to 95% by weight, preferably 50 to 90% by weight, more preferably It is 60 to 85% by weight. At this time, when the total content of the repeating unit derived from (a2) is less than 40% by weight, expansion may occur during development and an increase in viscosity of the solution may occur; on the other hand, if it exceeds 95% by weight, the solubility to the developing solution may be Will decrease. Expansion during development and increased viscosity of the solution may occur. The [A] copolymer can be produced, for example, by polymerizing an unsaturated compound other than the (al) unsaturated carboxylic acid compound or U2) (al) in a suitable solvent in the presence of a radical polymerization initiator. Examples of the solvent used in the polymerization include alcohols such as methanol, ethanol, n-propanol, and isopropanol: ethers such as tetrahydrofuran and dioxane: ethylene glycol monomethyl ether, ethylene glycol monoethyl Ethylene glycol monoalkyl ethers such as ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl acetate Ethylene glycol monoalkyl ether acetate such as ethylene glycol mono-n-propyl ether acetate or ethylene glycol mono-n-butyl ether acetate; φ ethylene glycol monomethyl ether propionate, ethylene Alcohol monoethyl ether propionate, ethylene glycol mono-n-propyl ether propionate, ethylene glycol mono-n-butyl ether propionate, etc. ethylene glycol monoalkyl ether propionate; diethylene glycol monomethyl Ethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, etc. • Diethylene glycol alkyl ethers: _ Propylene glycol monomethyl Propylene glycol monoalkyl ethers such as ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether; dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether Dipropylene glycol monoalkyl ethers such as dipropylene dihydrochloride diethyl ether and dipropylene glycol methyl ethyl ether; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol Propylene glycol monoalkyl ether acetate such as n-propyl ether acetate, propylene glycol mono-n-butyl ether acetate; propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol mono-n-propyl Propylene glycol monoalkyl ether propionates such as ether propionate, propylene glycol mono-n-butyl ether propionate: aromatic hydrocarbons such as toluene and xylene; methyl ethyl ketone, 2-pentanone, 3-pentanone, cyclohexanone, 4 Ketones such as -hydroxy-4-methyl-2-pentanone; • methyl 2-methoxypropionate, ethyl 2-methoxypropionate, n-propyl 2-methoxypropionate, 2- N-butyl methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, n-propyl 2-ethoxypropionate, n-butyl 2-ethoxypropionate , 2-n-propoxypropionic acid methyl ester, 2-n-propoxy propionate ethyl ester, 2-n-propoxy propionate n-propyl ester, 2-n-propoxy propionate n-butyl ester, 2-positive Methyl butoxypropionate, ethyl 2-n-butoxypropionate, 2-n-butoxy N-propyl propionate, n-butyl 2-n-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, n-propyl 3-methoxypropionate, 3 - n-butyl methoxypropionate, methyl 3-ethoxypropionic acid, ethyl 3-ethoxypropionate, n-propyl 3-ethoxypropionate, 3-ethoxypropionic acid Butyl ester, methyl 3-n-propoxypropionate, ethyl 3-n-propoxypropionate, n-propyl 3-n-propoxypropionate, n-butyl 3-n-propoxypropionate, 3 - alkoxypropionic acid such as methyl n-butoxypropionate, ethyl 3-n-butoxypropionate, n-propyl 3-n-butoxypropionate, n-butyl 3-n-butoxypropionate Alkyl esters; and methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate 'methyl hydroxyacetate, ethyl hydroxyacetate, n-propyl hydroxyacetate, n-butyl hydroxyacetate, methyl lactate, Ethyl lactate, n-propyl lactate, n-butyl 17- 1379161 1 lactate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, 3-hydroxypropionic acid Methyl ester, ethyl 3-hydroxypropionate, n-propyl 3-hydroxypropionate, n-butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, Methyl oxyacetate 'methoxyethyl acetate, n-propyl methoxyacetate, n-butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, n-propyl ethoxyacetate , n-butyl ethoxyacetate, methyl n-propoxyacetate, ethyl n-propoxyacetate, n-propyl n-propoxyacetate, n-butyl n-propoxyacetate, methyl n-butoxyacetate Other esters such as n-butoxyacetate ethyl n-butoxyacetic acid n-propyl ester and n-butyl n-butoxyacetate. Among these solvents, diethylene glycol alkyl ethers, propylene glycol monoalkyl ether acetates, alkoxypropionic acid alkyl esters and the like are preferable. The above solvents may be used singly or in combination of two or more. The solvent is used in an amount of 150 to 450 parts by weight, preferably 200 to 400 parts by weight, based on 100 parts by weight of the total of the components (a1) and (a2). Further, the radical polymerization initiator is not particularly limited, and examples thereof include 2,2'-azobisisobutyronitrile and 2,2'-azobis(2,4-dimethylvaleronitrile). ), 2,2,-azobis(4-methoxy-2,4-dimethylvaleronitrile), 4,4,-azobis(4-cyanovaleric acid), dimethyl-2 , 2'-azobis(2-methylpropionate), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) and other azo compounds; benzamidine Organic peroxides such as base peroxide, lauryl peroxide, t-butyl peroxypivalate, 1,1-di(tert-butylperoxy)cyclohexane; hydrogen peroxide, etc. When a peroxide is used as the radical polymerization initiator, it can be used as a redox type initiator together with a reducing agent in the range of -18 - 1379161. These radical polymerization initiators may be used singly or in combination of two or more. The radical polymerization initiator is used in an amount of 1 to 20 parts by weight, preferably 3 to 15 parts by weight, based on 100 parts by weight of the total of the components (a1) and U2). In the case of radical polymerization, it may be used together with a surfactant, a chain transfer agent or the like. Further, the radical polymerization conditions are a temperature of 50 to 1 10 ° C, preferably 60 I 100 ° C, and a polymerization time of 180 to 480 minutes, preferably about 240 to 420 minutes. The polystyrene-equivalent weight average molecular weight (hereinafter, referred to as "Mw") of the gel permeation chromatography (GPC) of the copolymer is 2,000 to 100,000, preferably 5,000 to 50,000. In this case, when the Mw is less than 2,000, the alkali developability, the residual film ratio, and the like of the obtained coating film are lowered, or the shape, heat resistance, and the like are impaired. On the other hand, if it exceeds 100,000, the clarity is lowered. Or the danger of the shape of the pattern being damaged. • The molecular weight of the [A] copolymer can be adjusted by the amount of the solvent relative to the total amount of the copolymers (a1) and (a2), the amount of the radical polymerization initiator, the polymerization time, the polymerization temperature, and the chain transfer agent used. [B] Polymerizable unsaturated compound: [B] The polymerizable unsaturated compound is formed of an unsaturated compound which is polymerized by radiation exposure in the presence of a radiation-sensitive linear polymerization initiator. The [B] polymerizable unsaturated compound is not particularly limited, and is, for example, a preferred (monofunctional, bifunctional, trifunctional or higher (meth)acrylate-19-1379161 type because of good copolymerizability. The strength of the resulting protrusions and spacers can be increased. Examples of the monofunctional (meth) acrylates include 2-hydroxyethyl acrylate 2-hydroxyethyl methacrylate, diethylene glycol monoethyl acrylate, and diethylene glycol monoethyl. Ether methacrylate, isophorone acrylate, isophorone methacrylate, 3-methoxybutyl acrylate, 3-methoxybutyl methacrylate, (2-propene oxime) (ethyl) (2-hydroxypropyl) phthalate, (2-methacryloxyethyl) (2, hydroxypropyl), phthalate, etc. In addition, as a commercial item, for example, ARONIX M-101, ARONIX M-lll, ARONIX Μ·114 (above, manufactured by Toagosei Co., Ltd.); KAYARAD TC-110S, KAYARAD TC-120S (above, 曰本Chemicals Co., Ltd.); products such as VISCOAT 158 and VISCOAT 2311 (above, Osaka Organic Chemical Industry Co., Ltd.). Further, examples of the bifunctional (meth) acrylate include ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, and diethylene glycol dimethacrylate. Tetraethylene glycol diacrylate

、四甘醇二甲基丙烯酸酯、1，6·己二醇二丙烯酸酯、1，6-己二醇二甲基丙嫌酸酯、1，9-壬二醇二丙烯酸醋、ι，9-壬二 醇二甲基丙烯酸酯 '二苯氧基乙醇芴二丙烯酸酯、二苯氧 基乙醇芴二甲基丙烯酸酯、聚酯兩末端（甲基）丙烯基改 性、聚丙二醇兩末端（甲基）丙烯基改性、聚1，4-丁二醇兩末 端（甲基）丙烯基改性。另外，作爲市售品，可以列舉出例 如 ARONIX M-210、ARONIX M-240、ARONIX M-6200(以 上’東亞合成（株）製），KAYARAD HDDA、KAYARAD -20- 1379161 HX-220、KAYARAD R-604(以上，曰本化藥（株）製）， VISCOAT 260、VISCOAT 312' VISCOAT 335HP(以上，大 阪有機化學工業（株）製），U-108A、U-200AX' UA-4100、 UA-4400 ' UA3 4 0P、UA-22 3 5 PE、UA-160TM、UA-6100、 U-2PPA200A(以上，新中村化學工業（株）製）等， UN-9000PEP、 UN-9200A、 UN-7600' UN-5200、 UN-1003、 UN-1255、UN-6060PTM、UN-6060P、SH-500B(以上，根上 工業（株）製）等商品。 • 此外，作爲上述3官能或以上的（甲基）丙烯酸酯類，可 以列舉出例如三羥甲基丙烷三丙烯酸酯、三羥甲基丙烷三 甲基丙烯酸酯、季戊四醇三丙烯酸酯、季戊四醇三甲基丙 烯酸酯、季戊四醇四丙烯酸酯、季戊四醇四甲基丙烯酸酯、 二季戊四醇五丙烯酸酯、二季戊四醇五甲基丙烯酸酯、二 季戊四醇六丙烯酸酯、二季戊四醇六甲基丙烯酸酯、三（2-丙烯醯氧基乙基）磷酸酯、三（2-甲基丙烯醯氧基乙基）磷酸 酯；以及作爲9官能或以上的（甲基）丙烯酸酯類，可以列 •舉出具有直鏈亞烷基和脂環結構且具有2個或更多個異氰 酸酯的化合物，和在分子內具有1個或更多個羥基且具有 3個、4個或5個丙烯醯氧基和/或甲基丙烯醯氧基的化合 物反應得到的多官能聚氨酯丙烯酸酯類化合物等。. 作爲3官能或以上的（甲基）丙烯酸酯類的市售品，可以列 舉出例如 ARONIX Μ-3 09 ' ARONIX Μ-400 ' ARONIX Μ-405、ARONIX M-450、ARONIX M-7100、ARONIX M-8030、ARONIX M-8060、ARONIX TO-1450(以上，東亞 -21 - 1379161 合成（株）製），KAYARAD TMPTA、KAYARAD DPHA、 KAYARAD DPCA-20、KAYARAD DPCA-30、KAYARAD DPCA-60、KAYARAD DPCA-120(以上，日本化藥（株）製）， VISCOAT 295、VISCOAT 3 00、VISCOAT 3 60、VISCOAT GPT、VISCOAT 3PA、V IS C Ο A T 4 0 0 (以上，大阪有機化學 工業（株）製）的等》作爲含有多官能聚氨酯丙烯酸酯類的市 售品，可以列舉出New Frontier R-1150(以上，第一工業製 藥（株）製），KAYARAD DPHA-40H(以上，日本化藥（株）製）， Λ-4ΗΑ ' U-6HA、U-6LPA、U-15HA、UA-32P、U-324A、 U-4H、U-6H(以上，新中村化學工業（株）製），UN9000H、 UN -3 3 20HA 、 UN-3 320HB 、 UN-3 320HC 、 UN-901T 、 UN- 1 200TPK(以上，根上工業（株）製）等。 在這些單官能、2官能、3官能或以上的（甲基）丙烯酸酯 類中，更較佳爲2官能或以上的（甲基）丙烯酸酯類，特別 較佳爲聚酯兩末端丙烯基改性、三羥甲基丙烷三丙烯酸 酯、季戊四醇三丙烯酸酯、季戊四醇四丙烯酸酯' 二季戊 #3醇五丙烯酸酯、二季戊四醇六丙烯酸酯以及含有多官能 聚氨酯丙烯酸酯類化合物的市售商品等》 上述單官能、2官能、3官能或以上的（甲基）丙烯酸酯類 可以單獨使用’也可以將2種或更多種混合後使用。 在本發明的感放射線性樹脂組成物中，相對於1〇〇重量 份[Α]共聚物，[Β]聚合性不飽和化合物的用量較佳爲1〜 120重量份，更較佳爲3〜100重量份。此時，在[β]共聚物 不飽和化合物的用量小於〗重量份時，在顯影時可能會產 -22- 1379161 生顯影殘缺；另一方面，如果超過120重量份，則 突起和間隔物的密合性有降低的趨勢。 [C]感放射線性聚合引發劑： [C]感放射線性聚合引發劑較佳由〇-乙醯基肟型 劑形成的，特別是上述式（1)或（2)表示的化合物（以下 爲“光聚合引發劑[C]” ）。 本發明的光聚合引發劑指：通過可視光線、紫外線 紫外線、帶電粒子束、X射線等放射線曝光，引發聚 ®化合物[B]的聚合，產生活性種子的成分.。 前述式（1)或（2)所示的光聚合引發劑[C]中，R,是選 原子數爲1~20的烷基、碳原子數爲3〜8的環烷基或 的基團。和R3分別是選自氫原子、碳原子數爲1〜 烷基、碳原子數爲3〜8的環烷基、取代或未取代的薄 或碳原子數爲7〜20的脂環基（除去碳原子數爲7-8的 基以外）的基團。上述取代苯基的取代基爲碳原子數爲 的烷基、碳原子數爲1〜6的烷氧基、苯基和鹵原子。 ®取代基可爲1-5個。R4是選自碳原子數爲4〜20的含 環基、碳原子數爲4〜20的含氮雜環基、或碳原子數 〜20的含硫雜環基。1是選自氫、碳原子數爲i〜12 基、或碳原子數爲1〜12的烷氧基的基團。η是1〜5 數’ m是0〜5的整數，n+m< 5，1是0〜6的整數。 作爲式（1)或（2)中的R,的碳原子數爲1~20的烷基可 鏈或支鏈狀烷基，具體可以列舉出例如甲基、乙基、 基、異丙基、正丁基、仲丁基、叔丁基'正戊基、正己 得的 :引發 ，稱 …遠 合性 自碳 苯基 20的 E基、 環烷 1〜6 這些 氧雜 爲4 的院 的整 爲直 正丙 L基、 -23- 1379161 正庚基、正辛基、正壬基、正癸基、正十一烷基' 正十二 烷基。作爲碳原子數爲3~8的環烷基，可以例舉出例如環 戊基、環己基等。 另外，R2、R3的碳原子數爲1〜20的烷基可爲直鏈或支 鏈狀，具體可以列舉出例如甲基、乙基、正丙基、異丙基、 正丁基、仲丁基、叔丁基、正戊基、正己基、正庚基、正 辛基、正壬基、正癸基、正十一烷基、正十二烷基。作爲 碳原子數爲3~8的環院基’可以例舉出例如環戊基、環己 •基等。 作爲R2、R3的取代苯基的取代基的碳原子數爲的烷 基可爲直鏈、支鏈、環狀’具體可以列舉出甲基、乙基、 正丙基、異丙基、正丁基、仲丁基、叔丁基、正戊基、正 己基、環戊基、環己基等。 另外，作爲碳原子數爲1~6的烷氧基可爲直鏈、支鏈、 環狀，具體可以列舉出甲氧基' 乙氧基、正丙氧基、異丙 氧基、正丁氧基、叔丁氧基等。作爲鹵原子，可以列舉出 φ例如氟原子、氯原子等。 作爲碳原子數爲7~20的脂環基（除了碳原子數爲7~8的 環烷基以外），可以列舉出例如二環烷基、三環烷基、螺環 烷基、三環烷基、含萜骨架的基團、含金剛烷骨架的基團 等。 R4的碳原子數爲4~20的含氮雜環基、碳原子數爲4~20 的含氧雜環基、碳原子數爲4~20的含硫雜環基’可以列舉 出例如四氫噻吩基、吖庚因基、二氫吖庚因基、二喝院基、 -24- 1379161 三哄基、噚噻基、噻唑基、噚二畊基、二噚茚滿基、二吡 萘基、呋喃基、苯硫基、吡咯基、噚唑烷基、異噚唑烷基、 噻唑基、異噻唑基、吡唑基、呋咕基、吡喃基、吡啶基、 唔哄基、嘧啶基、吡阱基、吡咯烷基、嗎啉基、脈阱基、 奎寧基、吲哚基、異吲哚基、苯並呋喃基、苯並苯硫基、 二氫吲哚基、色烯基、喹啉基、異喹啉基、嘌呤基）、喹唑 啉基、噌啉基、酞畊基、蝶啶基、咔唑基、吖啶基、菲啶 基、噻噸基、吩阱基、酚噻阱基、酚噻噚基、酚噚哄基、 ®噻嗯基、四氫呋喃 '四氫吡喃基等。其中，特別較佳四氫 呋喃基、四氫卩比喃基等。 作爲R5的碳原子數爲1〜12的烷基可爲直鏈、支鏈或環 狀’具體可以列舉出例如甲基、乙基、正丙基、異丙基、 正丁基、仲丁基、叔丁基、正戊基、正己基、正庚基、正 辛基、正壬基、正癸基、正十一烷基、正十二烷基、環戊 基、環己基等。 另外’作爲碳原子數爲1〜12的烷氧基可爲直鏈、支鏈 •或環狀的，具體可以列舉出甲氧基、乙氧基、正丙氧基、 異丙氧基、正丁氧基、叔丁氧基、正戊氧基等。 作爲R5’其中特別較佳爲甲基、乙基、正丙基、異丙基 正丁基、甲氧基、乙氧基。 n較佳爲1。111較佳爲〇、1或2的任一個’特別較佳爲 另外’ 1較佳爲〇、1或2的任一個，特別較佳爲1。 作爲該化合物[C]的具體例子，可以列舉出： 乙酮，1-[9 -乙基-6-(2 -甲基-2 -四氫呋喃基氧基苯甲醯 -25- 1379161 基）-9·Η·-咔唑-3-基]-，l-(0-乙醯基肟） 乙酮，1-[9 -乙基-6-(2 -甲基-2-四氫吡喃基氧基苯甲醯 基）-9.H.-咔唑-3-基]-,1-(0-乙醯基肟） 乙酮，Μ9·乙基- 6-(2-甲基-2-四氫呋喃基甲氧基苯甲醯 基）-9·Η.-咔唑-3-基]-,M〇-乙醯基肟） 乙酮，Μ9_乙基- 6-(2-甲基-2-四氫吡喃基甲氧基苯甲醯 基）-9.H·-咔唑-3-基]-,1-(0-乙醯基肟） 乙酮，1-[9 -乙基-6-(2 -甲基-3-四氫呋喃基氧基苯甲醯 _基）-9.H·-咔唑-3-基]-，1-(0-乙醯基肟） 乙酮，1-[9 -乙基-6-(2 -甲基-3 -四氫吡喃基氧基苯甲醯 基）-9·Η· -咔唑-3 -基]-,1-(0 -乙醯基肟） 乙酮，1-[9-乙基- 6-(2-甲基-3-四氫呋喃基甲氧基苯甲醯 基）-9·Η·-咔唑-3-基]-,1-(0-乙醯基肟） 乙酮，1-[9-乙基- 6-(2-甲基-3-四氫吡喃基甲氧基苯甲醯 基）-9.H·-咔唑-3 -基]-,1-(0 -乙醯基肟） 乙酮，1-[9 -乙基-6-(2 -甲基-4-四氫呋喃基氧基苯甲醯 鲁基）-9·Η·-咔唑-3-基]-,1-(0-乙醯基肟） 乙酮，1-[9 -乙基-6-(2 -甲基-4-四氫吡喃基氧基苯甲醯 基）-9.H.-咔唑-3-基]-，1-(0-乙醯基肟） 乙酮，1-[9-乙基- 6-(2-甲基-4-四氫呋喃基甲氧基苯甲醯 基）-9·Η·-咔唑-3-基]-,1-(0-乙醯基肟） 乙酮，1-[9-乙基- 6-(2-甲基-4-四氫吡喃基甲氧基苯甲醯 基）-9.H·-咔唑-3-基]-,1-(0 -乙醯基肟） 乙酮，1-[9 -乙基-6-(2 -甲基-5-四氫呋喃基氧基苯甲醯 -26- 1379161 < 基）-9.Η.-咔唑-3-基]-，1-(0-乙醯基肟） 乙酮，1-[9 -乙基-6-(2 -甲基-5-四氫吡喃基氧基苯甲醯 基）-9·Η·-咔唑-3-基]-,1-(0-乙醯基肟） 乙酮，1-[9-乙基- 6-(2-甲基-5-四氫呋喃基甲氧基苯甲醯 基）-9·Η·-咔唑-3-基]-，l-(0-乙醯基肟） 乙酮，1-[9-乙基- 6-(2-甲基-5-四氫吡喃基甲氧基苯甲醯 基）-9.H.-咔唑-3-基]-，1-(0-乙醯基肟） 乙酮，1-[9 -乙基- 6-(2 -甲基-2-四氫呋喃基氧基苯甲醯 龜 )-9·Η·-咔唑-3·基]-,1-(0-苯甲醯基乙醯基肟） 乙酮，1-[9 -乙基- 6-(2 -甲基-2-四氫吡喃基氧基苯甲醯 基）-9.H.-咔唑-3-基]-,1-(0-苯甲醯基乙醯基肟） 乙嗣，1-[9-乙基- 6-(2-甲基-2-四氫呋喃基甲氧基苯甲醯 基）-9.H.-咔唑-3-基]-,1-(0-苯甲醯基乙醯基肟） 乙酮，1-[9-乙基- 6-(2-甲基-2-四氫吡喃基甲氧基苯甲醯 基）-9·Η·-咔唑-3-基]-,1-(0-苯甲醯基乙醯基肟） 乙酮，1-[9 -乙基- 6-(2-甲基-3-四氫呋喃基氧基苯甲醯 _ )-9.H··咔唑-3-基]-,1-(0-苯甲醯基乙醯基肟） 乙嗣，1-[9 -乙基- 6-(2 -甲基-3 -四氫吡喃基氧基苯甲醯 基）-9.H·-咔唑-3-基]-,1-(0-苯甲醯基乙醯基肟） 乙酮，1-[9-乙基-6-(2-甲基-3-四氫呋喃基甲氧基苯甲醯 基）-9.H.-咔唑-3-基]-,1-(0-苯甲醯基乙醯基肟） 乙酮，1-[9-乙基-6-(2-甲基-3-四氫吡喃基甲氧基苯甲醯 基）-9·Η·-咔唑-3-基]-，l-(0-苯甲醯基乙醯基肟） 乙酮，1-[9 -乙基- 6-(2 -甲基-4 -四氫呋喃基氧基苯甲醯 -27- 1379161 基）-9·Η·-咔唑-3-基]-,1-(0-苯甲醯基乙醯基肟） 乙酮，1-[9 -乙基-6-(2 -甲基-4 -四氫吡喃基氧基苯甲醯 基）-9·Η·-咔唑-3-基]-,1-(0-苯甲醯基乙醯基肟） 乙酮，1-[9-乙基-6-(2_甲基-4-四氫呋喃基甲氧基苯甲醯 基）·9·Η·-咔唑-3-基]-,1-(0-苯甲醯基乙醯基肟） 乙酮，1-[9-乙基- 6-(2-甲基-4-四氫吡喃基甲氧基苯甲醯 基）-9·Η·-咔唑-3-基]-,1-(0-苯甲醯基乙醯基肟） 乙酮，1-[9 -乙基-6-(2 -甲基-5-四氫呋喃基氧基苯甲醯 )-9·Η.-咔唑-3-基]-,1-(0-苯甲醯基乙醯基肟） 乙酮，M9 -乙基-6-(2 -甲基-5 -四氫吡喃基氧基苯甲醯 基）-9·Η·-咔唑-3-基]苯甲醯基乙醯基肟） 乙酮，1-[9 -乙基- 6- (2-甲基-5-四氫呋喃基甲氧基苯甲醯 基）-9.H.-咔唑-3-基]-,1-(0-苯甲醯基乙醯基肟） 乙酮，1-[9-乙基- 6-(2-甲基-5-四氫吡喃基甲氧基苯甲醯 基）-9·Η.-咔唑-3-基]-，l-(0-苯甲醯基乙醯基肟） 乙酮，1-[9-乙基- 6-[2-甲基-4-(2,2-二甲基-1,3-二腭烷基） 氧基苯甲醯基]-9·Η·-咔唑-3-基]-,1-(0-乙醯基肟）等。 其中，較佳爲乙酮，1-[9-乙基- 6-(2-甲基-4-四氫呋喃基甲 氧基苯甲醯基咔唑-3 -基]-,1-(0-乙醯基肟）；乙 酮，M9-乙基-6-(2-甲基-4-四氫吡喃基甲氧基苯甲醯 基）-9.H.-咔唑-3-基]-,1-(0-乙醯基肟）；乙酮，1-[9-乙基- 6-(2-甲基-5-四氫呋喃基甲氧基苯甲醯基）-9.H.-咔唑-3-基]-,1-(0-乙醯基肟）；乙酮，1-[9-乙基- 6-(2-甲基-5-四氫吡喃 基甲氧基苯甲醯基）-9.H.-咔唑-3-基]-,1-(0-乙醯基肟）和乙 -28- 1379161, tetraethylene glycol dimethacrylate, 1,6·hexanediol diacrylate, 1,6-hexanediol dimethylpropane acid ester, 1,9-nonanediol diacrylate vinegar, ι,9 - decanediol dimethacrylate 'diphenoxyethanol oxime diacrylate, diphenoxyethanol oxime dimethacrylate, polyester both terminal (meth) propylene group modification, polypropylene glycol both ends ( Methyl) propylene-modified, poly-1,4-butanediol modified at both ends (meth) propylene. In addition, as a commercial item, for example, ARONIX M-210, ARONIX M-240, ARONIX M-6200 (above 'manufactured by Toagosei Co., Ltd.), KAYARAD HDDA, KAYARAD -20-1379161 HX-220, KAYARAD R -604 (above, manufactured by Sakamoto Chemical Co., Ltd.), VISCOAT 260, VISCOAT 312' VISCOAT 335HP (above, Osaka Organic Chemical Industry Co., Ltd.), U-108A, U-200AX' UA-4100, UA- 4400 ' UA3 4 0P, UA-22 3 5 PE, UA-160TM, UA-6100, U-2PPA200A (above, manufactured by Shin-Nakamura Chemical Co., Ltd.), UN-9000PEP, UN-9200A, UN-7600' Products such as UN-5200, UN-1003, UN-1255, UN-6060PTM, UN-6060P, and SH-500B (above, manufactured by Kokusai Kogyo Co., Ltd.). In addition, examples of the above-mentioned trifunctional or higher (meth) acrylates include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, and pentaerythritol trimethyl. Acrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethyl acrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, tris(2-propene oxime) Oxyethyl) phosphate, tris(2-methylpropenyloxyethyl) phosphate; and as a 9-functional or higher (meth) acrylate, which may be listed as having a linear alkylene group And a compound having an alicyclic structure and having 2 or more isocyanates, and having 1 or more hydroxyl groups in the molecule and having 3, 4 or 5 propylene oxy groups and/or methacryloxy groups A polyfunctional urethane acrylate compound obtained by reacting a compound of a group. The commercially available product of a trifunctional or higher (meth) acrylate may, for example, be ARONIX Μ-3 09 ' ARONIX Μ-400 ' ARONIX Μ-405, ARONIX M-450, ARONIX M-7100, ARONIX. M-8030, ARONIX M-8060, ARONIX TO-1450 (above, East Asia-21 - 1379161 Synthetic Co., Ltd.), KAYARAD TMPTA, KAYARAD DPHA, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120 (above, manufactured by Nippon Kayaku Co., Ltd.), VISCOAT 295, VISCOAT 3 00, VISCOAT 3 60, VISCOAT GPT, VISCOAT 3PA, V IS C Ο AT 4 0 0 (above, Osaka Organic Chemical Industry Co., Ltd.) As a commercial product containing a polyfunctional urethane acrylate, New Frontier R-1150 (above, First Industrial Co., Ltd.), KAYARAD DPHA-40H (above, Nippon Chemical Co., Ltd.)株-4ΗΑ ' U-6HA, U-6LPA, U-15HA, UA-32P, U-324A, U-4H, U-6H (above, Shin-Nakamura Chemical Industry Co., Ltd.), UN9000H , UN -3 3 20HA, UN-3 320HB, UN-3 320HC, UN-901T, UN-1 200TPK (above, SG Tech) Wait. Among these monofunctional, bifunctional, trifunctional or higher (meth) acrylates, more preferably a bifunctional or higher (meth) acrylate, particularly preferably a propylene base of the polyester. , trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate 'dipenta #3 alcohol pentaacrylate, dipentaerythritol hexaacrylate, and commercially available products containing polyfunctional urethane acrylate compounds, etc." The above-mentioned monofunctional, bifunctional, trifunctional or higher (meth) acrylates may be used singly or in combination of two or more. In the radiation sensitive resin composition of the present invention, the amount of the [Β] polymerizable unsaturated compound is preferably from 1 to 120 parts by weight, more preferably from 3 parts by weight to 1 part by weight of the [Α] copolymer. 100 parts by weight. At this time, when the amount of the [β] copolymer unsaturated compound is less than the weight part, a development defect may occur in the development of -22 to 1379161; on the other hand, if it exceeds 120 parts by weight, the protrusion and the spacer are Adhesion has a tendency to decrease. [C] Radiation-Temperature Polymerization Initiator: [C] The radiation-sensitive polymerization initiator is preferably formed of a quinone-ethenyl hydrazine type agent, particularly a compound represented by the above formula (1) or (2) (hereinafter referred to as "Photopolymerization initiator [C]"). The photopolymerization initiator of the present invention refers to a component which generates an active seed by polymerization of visible light, ultraviolet ultraviolet rays, charged particle beam, X-ray or the like to cause polymerization of the poly(TM) compound [B]. In the photopolymerization initiator [C] represented by the above formula (1) or (2), R is an alkyl group having 1 to 20 atoms, a cycloalkyl group having 3 to 8 carbon atoms or a group. . And R3 are each a cycloalkyl group selected from a hydrogen atom, a carbon number of 1 to an alkyl group, a carbon number of 3 to 8, a substituted or unsubstituted thin or alicyclic group having 7 to 20 carbon atoms (removal A group other than a group having 7 to 8 carbon atoms. The substituent of the above substituted phenyl group is an alkyl group having a carbon number, an alkoxy group having 1 to 6 carbon atoms, a phenyl group and a halogen atom. The number of ® substituents can be from 1 to 5. R4 is a nitrogen-containing heterocyclic group having 4 to 20 carbon atoms, a nitrogen-containing heterocyclic group having 4 to 20 carbon atoms, or a sulfur-containing heterocyclic group having 20 to 20 carbon atoms. 1 is a group selected from the group consisting of hydrogen, an alkoxy group having a carbon number of i to 12 groups, or a carbon number of 1 to 12. η is 1 to 5 and 'm is an integer of 0 to 5, and n + m < 5, 1 is an integer of 0 to 6. The alkyl group or branched alkyl group having 1 to 20 carbon atoms as R in the formula (1) or (2), and specific examples thereof include a methyl group, an ethyl group, a group, and an isopropyl group. N-butyl, sec-butyl, tert-butyl 'n-pentyl, n-hexane: initiated, said ... far from the carbon base 20 E group, cycloalkane 1 ~ 6 these oxygen is 4 It is a straight propyl L group, -23-1379161 n-heptyl, n-octyl, n-decyl, n-decyl, n-undecyl 'n-dodecyl. The cycloalkyl group having 3 to 8 carbon atoms may, for example, be a cyclopentyl group or a cyclohexyl group. Further, the alkyl group having 1 to 20 carbon atoms of R2 and R3 may be linear or branched, and specific examples thereof include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, and a sec-butyl group. Base, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-decyl, n-undecyl, n-dodecyl. The ring-shaped base group having a carbon number of 3 to 8 may, for example, be a cyclopentyl group or a cyclohexyl group. The alkyl group having a substituent of the substituted phenyl group for R2 and R3 may be a straight chain, a branched chain or a cyclic group. Specific examples thereof include a methyl group, an ethyl group, a n-propyl group, an isopropyl group and a n-butyl group. Base, sec-butyl, tert-butyl, n-pentyl, n-hexyl, cyclopentyl, cyclohexyl and the like. Further, the alkoxy group having 1 to 6 carbon atoms may be a straight chain, a branched chain or a cyclic group, and specific examples thereof include a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, and a n-butoxy group. Base, tert-butoxy, and the like. Examples of the halogen atom include φ such as a fluorine atom and a chlorine atom. Examples of the alicyclic group having 7 to 20 carbon atoms (except for a cycloalkyl group having 7 to 8 carbon atoms) include a bicycloalkyl group, a tricycloalkyl group, a spirocycloalkyl group, and a tricycloalkane. a group, a group containing an anthracene skeleton, a group containing an adamantane skeleton, and the like. The nitrogen-containing heterocyclic group having 4 to 20 carbon atoms of R4, the oxygen-containing heterocyclic group having 4 to 20 carbon atoms, and the sulfur-containing heterocyclic group having 4 to 20 carbon atoms may, for example, be tetrahydrogen. Thienyl, azepine, dihydroazepine, dioxin, -24-1379161 tridecyl, thiol, thiazolyl, hydrazine, diterpene, dipyridyl , furyl, phenylthio, pyrrolyl, oxazolidinyl, isoxazolidinyl, thiazolyl, isothiazolyl, pyrazolyl, furazyl, pyranyl, pyridyl, fluorenyl, pyrimidinyl , pyridyl, pyrrolidinyl, morpholinyl, porphyrin, quinuclyl, fluorenyl, isodecyl, benzofuranyl, benzophenylthio, indanyl, chromenyl , quinolyl, isoquinolyl, fluorenyl), quinazolinyl, porphyrinyl, hydrazine, pteridinyl, oxazolyl, acridinyl, phenanthryl, thioxanyl, phenanthrenyl , phenolthiophene group, phenothiphenyl, phenolphthalein, ® thiol, tetrahydrofuran 'tetrahydropyranyl and the like. Among them, tetrahydrofuranyl, tetrahydroanthracenyl and the like are particularly preferable. The alkyl group having 1 to 12 carbon atoms as R5 may be linear, branched or cyclic, and specific examples thereof include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, and a sec-butyl group. , tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-decyl, n-undecyl, n-dodecyl, cyclopentyl, cyclohexyl and the like. Further, 'the alkoxy group having 1 to 12 carbon atoms may be linear, branched or cyclic, and specific examples thereof include a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, and a positive group. Butoxy, tert-butoxy, n-pentyloxy and the like. Among them, R5' is particularly preferably a methyl group, an ethyl group, a n-propyl group, an isopropyl-n-butyl group, a methoxy group or an ethoxy group. n is preferably 1. 111 is preferably any one of 〇, 1 or 2, and particularly preferably another ー is preferably any of 〇, 1 or 2, particularly preferably 1. Specific examples of the compound [C] include: ethyl ketone, 1-[9-ethyl-6-(2-methyl-2-tetrahydrofuranyloxybenzamide-25-1379161)-9 ·Η·-carbazol-3-yl]-,l-(0-acetamidino)ethanone, 1-[9-ethyl-6-(2-methyl-2-tetrahydropyranyloxy) Benzobenzhydryl)-9.H.-oxazol-3-yl]-,1-(0-acetamidofluorene) Ethyl ketone, hydrazine 9·ethyl-6-(2-methyl-2-tetrahydrofuran Methoxymethoxybenzylidene)-9·Η.-carbazol-3-yl]-, M〇-acetamido oxime) Ethyl ketone, Μ9_ethyl-6-(2-methyl-2- Tetrahydropyranylmethoxybenzylidene)-9.H--oxazol-3-yl]-,1-(0-ethylhydrazinyl)ethanone, 1-[9-ethyl-6 -(2-methyl-3-tetrahydrofuranyloxybenzhydryl-yl)-9.H--oxazol-3-yl]-,1-(0-ethylhydrazinyl)ethanone, 1-[ 9-Ethyl-6-(2-methyl-3-tetrahydropyranyloxybenzhydryl)-9·Η·-carbazole-3-yl]-, 1-(0-ethenyl肟) Ethylketone, 1-[9-ethyl-6-(2-methyl-3-tetrahydrofurylmethoxybenzylidene)-9·Η·-carbazol-3-yl]-, 1- (0-ethylhydrazine) Ethyl ketone, 1-[9-ethyl-6-(2-methyl-3-tetrahydropyranylmethoxybenzylidene)-9.H--carbazole -3 -yl]-,1-(0-ethenylhydrazine) ethyl ketone, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranyloxybenzoguanylidene)-9 ·Η·-carbazol-3-yl]-, 1-(0-acetamidofluorene) ethyl ketone, 1-[9-ethyl-6-(2-methyl-4-tetrahydropyranyloxy) Benzobenzhydryl)-9.H.-carbazol-3-yl]-, 1-(0-ethylhydrazinyl)ethanone, 1-[9-ethyl-6-(2-methyl- 4-tetrahydrofuranylmethoxybenzylidene)-9·Η·-carbazol-3-yl]-, 1-(0-ethylhydrazinyl)ethanone, 1-[9-ethyl-6- (2-methyl-4-tetrahydropyranylmethoxybenzylidene)-9.H--oxazol-3-yl]-,1-(0-ethylhydrazinyl)ethanone, 1 -[9-ethyl-6-(2-methyl-5-tetrahydrofuranylbenzophenone-26-1379161 <yl)-9.Η.-carbazol-3-yl]-, 1-( 0-Ethyl hydrazide) Ethyl ketone, 1-[9-ethyl-6-(2-methyl-5-tetrahydropyranyloxybenzylidene)-9·Η·-carbazole-3 -yl]-,1-(0-ethenylhydrazine) ethyl ketone, 1-[9-ethyl-6-(2-methyl-5-tetrahydrofurylmethoxybenzylidene)-9·Η ·-oxazol-3-yl]-,l-(0-acetamidino)ethanone, 1-[9-ethyl-6-(2-methyl-5-tetrahydropyranylmethoxy) Benzyl hydrazino)-9.H.-carbazol-3-yl]-, 1-(0-B Base ketone, 1-[9-ethyl-6-(2-methyl-2-tetrahydrofuranyloxybenzoquinone)-9·Η·-carbazole-3·yl]-, 1- (0-Benzylmercaptoacetoxime) Ethylketone, 1-[9-ethyl-6-(2-methyl-2-tetrahydropyranyloxybenzylidene)-9.H. -oxazol-3-yl]-, 1-(0-benzylidene ethylene hydrazide) acetamidine, 1-[9-ethyl-6-(2-methyl-2-tetrahydrofuranylmethoxy) Benzyl hydrazino)-9.H.-carbazol-3-yl]-, 1-(0-benzylidene acetyl hydrazide) ethyl ketone, 1-[9-ethyl-6-(2- Methyl-2-tetrahydropyranylmethoxybenzylidene)-9·Η·-carbazol-3-yl]-, 1-(0-benzylideneacetylhydrazinyl)ethanone, 1-[9-ethyl-6-(2-methyl-3-tetrahydrofuranyloxybenzhydrazide)-9-H-oxazol-3-yl]-, 1-(0-benzamide Ethyl hydrazide hydrazine, 1-[9-ethyl-6-(2-methyl-3-tetrahydropyranyloxybenzhydryl)-9.H--carbazole-3- Base]-,1-(0-benzylideneacetinyl)ethanone, 1-[9-ethyl-6-(2-methyl-3-tetrahydrofurylmethoxybenzylidene)- 9.H.-carbazol-3-yl]-, 1-(0-benzylideneacetinyl)ethanone, 1-[9-ethyl-6-(2-methyl-3-tetra Hydropyranylmethoxybenzylidene)-9 ·Η·-carbazol-3-yl]-,l-(0-benzylideneacetinyl)ethanone, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranyl) Oxylbenzhydryl -27- 1379161 yl)-9-indole-oxazol-3-yl]-, 1-(0-benzylidene acetyl hydrazide) ethyl ketone, 1-[9-ethyl -6-(2-methyl-4-tetrahydropyranyloxybenzhydryl)-9·Η·-oxazol-3-yl]-, 1-(0-benzylidene ethenyl)肟) Ethylketone, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofurylmethoxybenzylidene)·9·Η·-carbazol-3-yl]-, 1- (0-benzylideneacetinyl) ethyl ketone, 1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylmethoxybenzylidene)-9·Η ·-oxazol-3-yl]-, 1-(0-benzylideneacetinyl) ethyl ketone, 1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranyloxy) Benzamidine)-9·Η.-carbazol-3-yl]-,1-(0-benzylideneacetinyl)ethanone, M9-ethyl-6-(2-methyl-5 -tetrahydropyranyloxybenzimidyl)-9·Η·-carbazol-3-yl]benzhydrylacetinyl)ethanone, 1-[9-ethyl-6- (2 -methyl-5-tetrahydrofuranylmethoxybenzylidene)-9.H.-carbazol-3-yl]-, 1-(0-benzylideneacetylhydrazinyl)ethanone, 1- [9-B - 6-(2-Methyl-5-tetrahydropyranylmethoxybenzylidene)-9·Η.-carbazol-3-yl]-,l-(0-benzylidene acetyl Ethyl ketone, 1-[9-ethyl-6-[2-methyl-4-(2,2-dimethyl-1,3-dioxanyl)oxybenzylidene]- 9·Η·-carbazol-3-yl]-, 1-(0-ethylindenyl) and the like. Among them, preferred is ethyl ketone, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylmethoxybenzylidenecarbazole-3-yl)-, 1-(0-B Ethyl ketone, M9-ethyl-6-(2-methyl-4-tetrahydropyranylmethoxybenzylidene)-9.H.-carbazol-3-yl]- , 1-(0-ethenylhydrazine); ethyl ketone, 1-[9-ethyl-6-(2-methyl-5-tetrahydrofurylmethoxybenzylidene)-9.H.-咔Zyridin-3-yl]-, 1-(0-ethenylhydrazine); ethyl ketone, 1-[9-ethyl-6-(2-methyl-5-tetrahydropyranylmethoxybenzoate) Mercapto)-9.H.-carbazol-3-yl]-, 1-(0-ethenylhydrazine) and B-28- 1379161

I 酮，l-[9-乙基-6-[2-甲基-4-(2,2-二甲基-1，3-二嗶烷基）甲氧 基苯甲醯基]咔唑-3-基]·，ι·(0·乙醯基肟）。 這些光聚合引發劑[C]可以單獨或2種或更多種—同使 用。 作爲光聚合引發劑[C]，也可以同時使用上述式（1)以外 的〇·醯基肟型光聚合引發劑（以下，稱爲“光聚合引發劑 [C-2]，，）。 作爲這些光聚合引發劑[C-2]的具體實例，可以例舉出， ·，2-辛二酮- :144-(苯硫基）苯基]_2·(〇·苯甲醯基肟）；1，2-丁 二酮-1-[4-(苯硫基）苯基]-2-(0-苯甲醯基肟）；1，2-丁二酮 -卜[4-(苯硫基）苯基]-2-(0-乙醯基肟）；l，2-辛二酮·1-[4-(甲 硫基）本基]-2-(0 -本甲醒基fe) ; 1，2 -辛二嗣-1-[4-(苯硫基） 苯基]-2-(0-(4-甲基苯甲醯基肟））等。它們之中，特別較佳 1,2-辛二酮-l-[4-(苯硫基）苯基]-2-(0-苯甲醯基肟）。光聚合 引發劑[C-2]較佳使用光聚合引發劑[C]的30重量％或以下。 在本發明中，通過使用[C]感放射線性聚合引發劑，即使 φΕ l，200〗/m2或以下的曝光量下，也可以達到足夠的靈敏 度’且可以得到具有良好的黏合性的突起和間隔物。 在本發明的感放射線性樹脂組成物中，相對於1 00重量 份[B]聚合性不飽和化合物，[c]感放射線性聚合引發劑的用 量較佳爲5〜30重量份，更較佳爲5~ 20重量份。此時，[C] 感放射線性聚合引發劑的用量小於5重量份時，顯影時的 殘膜率有降低的傾向；另一方面，如果超過3 〇重量份，則 顯影時未曝光部對鹼性顯影液的溶解性有降低的傾向。 -29- 1379161 f 此外，在本發明的感放射線性樹脂組成物中’還可以將 一種或以上的其他感放射線性樹脂組成物和[c]感放射線 性聚合引發劑一起使用。 作爲上述其他的光聚合引發劑，可以例舉出比如’二咪 唑類化合物、安息香類化合物、苯乙酮類化合物、二苯酮 類化合物、α-二酮類化合物、多核醌類化合物、咕噸酮類 化合物、膦類化合物、三阱類化合物等。它們之中，較佳 苯乙酮類化合物（以下，有時稱爲“（D)成分”）、二咪唑類化 ®合物（以下，有時稱爲“（E)成分”）。作爲上述其他感放射線 性聚合引發劑，可以列舉出例如苯乙酮類化合物、二咪唑 類化合物、安息香類化合物、二苯酮類化合物、α -二酮類 化合物、多核醌類化合物、噻噸酮類化合物、膦類化合物、 三畊類化合物等，其中，較佳苯乙酮類化合物、二咪唑類 化合物等。 (D)成分：苯乙酮類化合物 另外，作爲上述苯乙酮類化合物，可以列舉出例如α -•徑基酮類化合物，α -胺基酮類化合物、這些以外的化合物 等。 作爲α -羥基酮類化合物的具體實例，可以列舉出例如 1-苯基-2-羥基-2 -甲基-丙-1-酮、1-(4 -異丙基苯基μ〗 -羥基 -2-甲基-丙-i_酮、4-(2-羥基乙氧基）苯基-(2-羥基-2-丙基） 酮、卜羥基環己基苯基酮等。作爲上述α-胺基酮類化合物 的具體實例，可以列舉出例如2-甲基-1-[4-(甲基硫基）苯 基]-2-嗎啉基-丙-1-酮、2-苄基-2-二甲基胺基-丨气^嗎啉基 -30- 1379161I ketone, l-[9-ethyl-6-[2-methyl-4-(2,2-dimethyl-1,3-dioxanyl)methoxybenzylidene] oxazole- 3-based]·, ι·(0· 醯 醯 肟). These photopolymerization initiators [C] may be used singly or in combination of two or more. As the photopolymerization initiator [C], a ruthenium-based ruthenium-based photopolymerization initiator other than the above formula (1) (hereinafter referred to as "photopolymerization initiator [C-2],) may be used at the same time. Specific examples of the photopolymerization initiator [C-2] include, for example, 2-octanedione-:144-(phenylthio)phenyl]_2.(〇·benzylidenehydrazine); 1,2-butanedione-1-[4-(phenylthio)phenyl]-2-(0-benzhydrylhydrazine); 1,2-butanedione-bu [4-(phenylthio) Phenyl]-2-(0-acetamidoxime); l,2-octanedione 1-[4-(methylthio)benzyl]-2-(0-benmethanyl fe); 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(0-(4-methylbenzhydrylhydrazine)), etc. Among them, particularly preferred is 1, 2-octanedione-l-[4-(phenylthio)phenyl]-2-(0-benzylidenehydrazine). Photopolymerization initiator [C-2] is preferably a photopolymerization initiator [C 30% by weight or less. In the present invention, by using the [C] radiation-sensitive polymerization initiator, sufficient sensitivity can be obtained even at an exposure amount of φ Ε l, 200 Å/m 2 or less. Protrusions and spacers with good adhesion. In the radiation sensitive resin composition of the present invention, the amount of the [c] radiation-sensitive polymerization initiator is preferably 5 to 30 parts by weight, more preferably 100 parts by weight of the [B] polymerizable unsaturated compound. When the amount of the [C] radiation-sensitive polymerization initiator is less than 5 parts by weight, the residual film ratio during development tends to decrease; on the other hand, if it exceeds 3 parts by weight, The solubility of the unexposed portion to the alkaline developing solution tends to decrease during development. -29- 1379161 f Further, in the radiation sensitive resin composition of the present invention, one or more other radiation sensitive resins may be further composed. The photopolymerization initiator is used together with the [c] radiation-sensitive polymerization initiator. Examples of the other photopolymerization initiator include a 'diimidazole compound, a benzoin compound, an acetophenone compound, and a benzophenone compound. An α-diketone compound, a polynuclear quinone compound, a xanthone compound, a phosphine compound, a triple well compound, etc. Among them, an acetophenone compound (hereinafter, sometimes referred to as "(D)) ingredient And a diimidazole compound (hereinafter sometimes referred to as "(E) component).) Examples of the other radiation-sensitive polymerization initiator include acetophenone compounds, diimidazole compounds, and benzoin. a compound, a benzophenone compound, an α-diketone compound, a polynuclear hydrazine compound, a thioxanthone compound, a phosphine compound, a tri-farming compound, etc., among which acetophenone compounds and diimidazoles are preferred. (D) component: acetophenone-based compound The acetophenone-based compound may, for example, be an α-• ketone ketone compound, an α-amino ketone compound or a compound other than these. Specific examples of the α-hydroxyketone compound include, for example, 1-phenyl-2-hydroxy-2-methyl-propan-1-one and 1-(4-isopropylphenyl)-hydroxy- 2-methyl-propyl-i-ketone, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl) ketone, hydroxycyclohexyl phenyl ketone, etc. as the above α-amine Specific examples of the ketone compound include, for example, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-propan-1-one, 2-benzyl-2. -Dimethylamino-helium^morpholinyl-30- 1379161

t I 苯基）-丁 -1-酮、2-(4-甲基苯甲醯基）-2-二甲基胺基-1-(4-嗎 啉基苯基）-丁 -1-酮等。作爲這些以外的化合物的具體實 例，例如可以列舉出2,2·二甲氧基苯乙酮、2,2 -二乙氧基苯 乙酮、2,2-二甲氧基-2-苯基苯乙酮等。 這些苯乙酮類化合物可以單獨使用，也可以將2種或更 ' 多種混合後使用。 通過使用這些苯乙酮類化合物，可以進一步改善靈敏 度、間隔物和突起的形狀和壓縮強度。 ® (E)成分：二咪唑類化合物 作爲二咪唑類化合物的具體實例可以列舉出例如2,2’_ 二（2-氯代苯基）_4,4，，5,5，-四（4-乙氧基羰基苯基）-1，2’_二咪 唑、2,2，-二（2-溴代苯基）-4,4’，5,5，-四（4-乙氧基羰基苯 基）-1，2’-二咪唑、2,2’-二（2-氯代苯基）-4,4’，5,5’-四苯基 -1,2，-二咪唑、2,2，_ 二（2,4-二氯代苯基）-4,4，，5,5，-四苯基 -1，2’-二咪唑、2,2，_二（2,4,6-三氯代苯基）-4,4’，5,5’-四苯基 -1，2’-二咪唑、2,2，·二（2-溴代苯基）-4,4’，5,5，-四苯基-I，2’· •二咪唑、2,2，-二（2,4-二溴代苯基）-4,4’，5,5’-四苯基二 咪唑、2,2，-二（2,4,6-三溴代苯基）_4,4，，5,5’-四苯基-丨，2’-二 咪唑等。 在這些二咪π坐類化合物中，較佳 2,2’·二（2-氯代本 • 基）-4,4，，5,5，-四苯基-1，2，-二咪唑、2,2，-二（2,4-二氯代苯 基）_4,4，，5,5，-四苯基-1,2，-二咪唑、2,2’-二（2,4,6-三氯代苯 基）-4,4，，5,5，-四苯基-1,2’-二咪唑等’特別較佳2,2’-二（2’4-二氯代苯基）-4,4，，5,5，-四苯基-1，2’-二咪唑。 -31 - 1379,161 t 上述二咪唑類化合物可以單獨使用，也可以將 多種混合後使用。 通過使用這些二咪唑類化合物，可以進一步 度、解析度和密合性。 另外，爲了增加二咪唑類化合物的靈敏度，可 有二烷基胺基的脂肪族類或芳香族類化合物（以 “增感劑[E-2]”）。 作爲上述增感劑[E - 2 ]的具體實例，可以列舉t 基二乙醇胺、4,4’-二（二甲基胺基）二苯酮、4,4 基胺基）二苯酮 '對-二甲基胺基苯甲酸乙酯、對_ 基苯甲酸異戊酯等。在這些增感劑中，較佳爲4, 乙基胺基）二苯酮。 上述增感劑[E-2]可以單獨使用，也可以將多種 用。 相對100重量份[A]，增感劑[E-2]的使用量 0.1-50重量份，更較佳含有1-20重量份。 # 增感劑[E-2]的用量小於0.1重量份時，具有發 間隔物和突起的薄膜減少或圖案形狀不良的傾向 如果超過50重量份的話，同樣具有產生圖案形狀 向。 在使用二咪唑類化合物時，可以添加硫醇類4 下’有時稱爲"硫醇類化合物[Ε-3Γ )作爲供氫化 咪唑類化合物通過具有二烷基胺基的二苯酮類化 而破裂’產生咪唑自由基。在此場合無法顯現出 2種或更 改善靈敏 以添加具 下，稱作 B例如N-二（二乙 二甲基胺 4，-二（二 混合後使 較佳含有 生所得的 ，另外， 不良的傾 匕合物（以 ，合物。二 合物增感 高的聚合 -32- 1379161 引發能，所得的間隔物大多爲倒圓錐形狀這樣不希望的形 狀。該問題可通過在二咪唑類化合物和具有二烷基胺基的 二苯酮類化合物共存的系統中，添加硫醇類化合物[E-3]而 緩解。通過對咪唑自由基提供來自硫醇類化合物的氫自由 基’而產生中性的咪唑和具有高聚合引發能的硫自由基的 化合物。由此，間隔物的形狀爲更較佳的順圓錐狀。 相對100重量份化合物[C]，上述硫醇類化合物[E-3]的 使用比例’較佳含有0.1-50重量份，更較佳含有1-20重量 分。硫醇類化合物[E-3]的用量小於〇.1重量份時，具有發 生所得的間隔物和突起的薄膜減少或圖案形狀不良的傾 向’另外’如果超過50重量份的話，同樣具有產生圖案形 狀不良的傾向。 作爲其具體實例，可以列舉出例如2 -锍基苯并噻唑、2 -锍基苯并噚唑、2 -锍基苯并咪唑、2 -毓基-5-甲氧基苯并噻 唑、2 -疏基-5·甲氧基苯并咪唑等芳香族硫醇；3 -锍基丙酸、 3 -毓基丙酸甲酯、3 -毓基丙酸乙酯、3 -锍基丙酸辛酯等脂肪 •疾單硫醇：作爲2官能或更多官能的脂肪族硫醇可以例舉 出3,6-二氧雜-1,8-辛-二硫醇、季戊四醇四（巯基乙酸酯）、 季戊四醇四（3 -锍基丙酸酯）等。 作爲上述噻噸酮類化合物’可以列舉出2 -異丙基噻噸 酮、2,4-二甲基噻噸酮、2,4 -二乙基噻噸酮、2,4 -二氯代噻 噸酮等。 作爲上述膦類化合物，可以列舉出氧化2,4,6 -三甲基苯 甲醯基二苯基膦、氧化2,4,6-三甲基苯甲醯基苯基乙基膦、 -33- I379J61 氧化二（2,4,6·三甲基苯甲醯基）苯基膦等。 其他光聚合引發劑的使用比例相對於全部的光聚合引 發劑100重量份，較佳爲1〇〇重量份或以下，更較佳爲8〇 重量份或以下，特別較佳爲60重量份或以下。此時，其他 光聚合引發劑的使用比例如果超過丨00重量份，則可能會 損害本發明所預期的效果。 添加劑： 在不損害本發明所預期的效果的範圍內，在本發明的感 t政射線性樹脂組成物中，根據需要，除了添加上述成分以 外，還可以添加表面活性劑、黏結助劑、保存穩定劑、耐 熱性提高劑等添加劑。 上述表面活性劑是具有改善塗布性的作用的成分，較佳 氟類表面活性劑和有機矽類表面活性劑》 作爲上述氟類表面活性劑較佳爲在末端、主鏈和側鏈的 至少一個部位上具有氟代烷基或氟代亞烷基的化合物，作 爲其具體的例子，可以列舉出1,1,2,2-四氟辛基（1,1，2,2-四 _代正丙基）醚、1,1，2,2-四氟代正辛基（正己基）醚' 八乙二 醇二（1，1，2,2-四氟正丁基）醚、六乙二醇（1，1,2,2,3,3-六氟正 戊基）醚、八丙二醇二（1，1,2,2-四氟正丁基）醚、六丙二醇二 (1，1，2,2,3,3-六氟正戊基）醚、1，1，2,2,3,3-六氟正癸烷、 1，1，2,2,8,8,9,9,10,10-十氟正十二烷、全氟正十二烷磺酸鈉 和、氟代烷基苯磺酸鈉類 '氟代烷基亞磷酸鈉類' 氟代烷 基羧酸鈉類、氟代烷基聚氧乙烯醚類 '二甘油四（氟代烷基 聚氧乙烯基醚）類、氟代烷基銨碘化合物類' 氟代院基甜萊 •34- 1379161 , 鹼類、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、氟類烷基酯類等。 作爲氟類表面活性劑的市售商品，可列舉出例如商品名 爲 BM-1 〇〇〇、BM-1 1 00(以上，BMCHEMIE(株）製），Megafac F142D、Megafac F172、Megafac F1 7 3、Megafac F1 8 3、 Megafac F178 ' Megafac F 1 9 1、Megafac F4 7 1、Megafac F476(以上，大日本油墨化學工業（株）製），Fluorad FC-170C、 Fluorad FC-171 、 Fluorad FC-430 、 Fluorad FC-431(以上， 籲住友只 U — 工厶（株）製），Surflon S-112、Surflon S-113、 Surflon S-131、Surflon S-141、Surflon S -14 5、Surflon S-3 82 ' Surflon SC- 1 01 ' S ur fl ο n S C -1 0 2 ' Surflon SC-103、 Surflon SC-104、Surflon SC-105、Surflon SC-106(以上， 旭硝子（株）製），Eftop EF301、Eftop EF303、Eftop EF352(以 上，新秋田化成（株）製）、Ftergent FT-100、Ftergent FT-110、 Ftergent FT-140A' Ftergent FT-150、 Ftergent 卜 FT-250、 Ftergent FT-251、Ftergent FTX-251、Ftergent FTX-218、 t e r g e n t FT-300 'Ftergent FT-3 10 'Ftergent FT-400S(以上， Rios (株）製）等。 作爲上述有機矽系表面活性劑，作爲市售商品可列舉出 例.如商品名爲 Toray Silicone DC3PA、Toray Silicone DC7PA、Toray Silicone SHI 1PA、Toray Silicone SH21PA、 Toray Silicone SH28PA、Toray Silicone SH29PA、Toray Silicone SH30PA ' Toray Silicone SH-190 ' Toray Silicone SH-193 、 Toray Silicone SZ-6032 、 Toray Silicone -35- 1379,161 SF-8428、Toray Silico.ne DC-57、Toray Silicone DC-190(以 上、Toray，Corning Silicne (株）製），TSF-4440、TSF-4300、 TSF-4445、TSF-4446、TSF-4460、TSF-4452(以上，GE 東 芝Silicone (株）製）等的商品。 另外，作爲上述以外的表面活性劑，可舉出聚氧乙烯月 桂基醚、聚氧乙烯硬脂醯基醚、聚氧乙烯油烯基醚等的聚 氧乙烯烷基醚類：聚氧乙烯正辛基苯基醚、聚氧乙烯正壬 基苯基醚等的聚氧乙烯芳基'醚類；聚氧乙烯二月桂酸酯、 %氧乙烯二硬脂酸酯等的聚氧乙烯二烷基酯等的非離子性 表面活性劑；以及作爲市售商品，可以列舉出例如 KP341(信越化學工業（株）製）、Polyflow No.57、P〇lyfi〇w No.95(以上，共榮社化學（株）製）等商品。 上述表面活性劑可以單獨使用，可以將2種或更多種混 合使用。 相對於1 00重量份[A]共聚物，表面活性劑的配合量較佳 的是5重量份或以下、進而較佳的是2重量份或以下。此 β，表面活性劑配合量超過5重量份時，有容易在塗布時 生成膜粗糙的傾向。 上述黏結助劑是具有改善突起和間隔物與基體的密、合· 性的作用的成份，較佳爲官能性矽烷偶聯劑。 作爲上述官能性矽烷偶聯劑，可以列舉出例如具有较 基、甲基丙烯醯基、乙烯基、異氰酸酯基、環氧基等的反 應性官能基化合物。更具體地，可列舉出三甲氧基甲 基苯甲酸、Τ -甲基丙烯醯氧丙基三甲氧基矽烷、乙锦基三 -36- 1379161 乙醯氧基矽烷、乙烯基三甲氧基矽烷、異氰酸 三乙氧基矽烷、r-環氧丙氧基丙基三甲氧基矽院 環氧環己基）乙基三甲氧基矽烷等。 這些黏結助劑可以單獨使用，也可以將2種或 合使用。 相對於[A]共聚物100重量份，黏結助劑的混合 是20重量份或以下、更較佳的是10重量份以下 黏結助劑的混合量如果超過20重量份，則有容易 •袭缺的傾向。 作爲上述保存穩定劑，可列舉出例如硫、醌類、 聚氧化合物、胺類、硝基亞硝基化合物等，更具 出4-甲氧基苯酚' N-亞硝基-N-苯基羥基胺鋁等。 這些保存穩定劑可以單獨使用，或混合2種或 用。 相對於100重量份[A]共聚物，保存穩定劑的配 的是3重量份或以下、更較佳的是〇.〇〇!〜〇.5重 ##，保存穩定劑的混合量超過3重量份時，可能 度損害圖形形狀。 作爲上述耐熱性提高劑，可列舉出例如N-(烷I 甘脲化合物、N-(烷氧基甲基）三聚氰胺化合物、| 或更多個環氧基的化合物等。t I phenyl)-butan-1-one, 2-(4-methylbenzimidyl)-2-dimethylamino-1-(4-morpholinylphenyl)-butan-1-one Wait. Specific examples of the compound other than these include, for example, 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, and 2,2-dimethoxy-2-phenyl. Acetophenone and the like. These acetophenone compounds may be used singly or in combination of two or more. By using these acetophenone compounds, the shape and compressive strength of the sensitivity, spacers and protrusions can be further improved. ® (E) component: diimidazole compound Specific examples of the diimidazole compound may, for example, be 2,2'-bis(2-chlorophenyl)_4,4,5,5,-tetra(4- Ethoxycarbonylphenyl)-1,2'-diimidazole, 2,2,-bis(2-bromophenyl)-4,4',5,5,-tetrakis(4-ethoxycarbonylbenzene 1,1,2'-diimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2,-diimidazole, 2, 2,_bis(2,4-dichlorophenyl)-4,4,5,5,-tetraphenyl-1,2'-diimidazole, 2,2,_di(2,4,6 -trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole, 2,2,bis(2-bromophenyl)-4,4', 5,5,-tetraphenyl-I,2'· •diimidazole, 2,2,-bis(2,4-dibromophenyl)-4,4',5,5'-tetraphenyl Imidazole, 2,2,-bis(2,4,6-tribromophenyl)-4,4,5,5'-tetraphenyl-indole, 2'-diimidazole and the like. Among these dimethine π sitting compounds, 2,2'·bis(2-chlorobenzyl)-4,4,5,5,-tetraphenyl-1,2,-diimidazole is preferred. 2,2,-bis(2,4-dichlorophenyl)_4,4,5,5,-tetraphenyl-1,2,-diimidazole, 2,2'-di(2,4, 6-trichlorophenyl)-4,4,5,5,-tetraphenyl-1,2'-diimidazole, etc. 'particularly preferred 2,2'-bis(2'4-dichlorobenzene) Base 4,4,5,5,-tetraphenyl-1,2'-diimidazole. -31 - 1379,161 t The above diimidazole compounds may be used singly or in combination of plural kinds. Further, resolution and adhesion can be obtained by using these diimidazole compounds. Further, in order to increase the sensitivity of the diimidazole compound, a dialkylamino group-based aliphatic or aromatic compound ("sensitizing agent [E-2]") may be mentioned. Specific examples of the above sensitizer [E - 2 ] include t-based diethanolamine, 4,4'-bis(dimethylamino)benzophenone, and 4,4-aminoamino)benzophenone - Ethyl dimethylaminobenzoate, isoamyl p-benzoate, and the like. Among these sensitizers, preferred is 4, ethylamino)benzophenone. The above sensitizer [E-2] may be used singly or in combination. The sensitizer [E-2] is used in an amount of 0.1 to 50 parts by weight, more preferably 1 to 20 parts by weight, per 100 parts by weight of [A]. When the amount of the sensitizer [E-2] is less than 0.1 part by weight, the film having the spacer and the projection is reduced or the pattern shape is unfavorable. If it exceeds 50 parts by weight, the pattern shape is similarly generated. When a diimidazole compound is used, a thiol group 4 may be added, which is sometimes referred to as a "thiol compound [Ε-3Γ], as a hydrogenated imidazole compound through a benzophenone having a dialkylamine group; And the rupture' produces imidazole free radicals. In this case, it is not possible to show two or more improved sensitivities, such as B, for example, N-di(diethylenedimethylamine 4,-di (two kinds of mixed, preferably containing raw, and, in addition, bad) The pour condensate (in the compound, the high sensitization of the polymer-32- 1379161), the resulting spacers are mostly undesired shapes of inverted cone shape. The problem can be solved by diimidazole compounds. In a system in which a benzophenone compound having a dialkylamine group is present, the thiol compound [E-3] is added to be alleviated. The hydrogen radical from the thiol compound is supplied to the imidazole radical. a compound of imidazole and a sulfur radical having a high polymerization initiating energy. Thus, the shape of the spacer is more preferably a conical shape. The above mercaptan compound [E-3] relative to 100 parts by weight of the compound [C] The use ratio 'is preferably from 0.1 to 50 parts by weight, more preferably from 1 to 20 parts by weight. When the amount of the thiol compound [E-3] is less than 0.1 part by weight, the resulting spacer and The tendency of the raised film to decrease or the shape of the pattern to be poor If it exceeds 50 parts by weight, the pattern shape tends to be poor. As a specific example thereof, for example, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-nonylbenzene may be mentioned. An aromatic thiol such as imidazole, 2-mercapto-5-methoxybenzothiazole, 2-carbyl-5-methoxybenzimidazole; 3-mercaptopropionic acid, 3-mercaptopropionic acid Fats such as esters, ethyl 3-mercaptopropionate, and octyl 3-mercaptopropionate. Monomers: As a bifunctional or more functional aliphatic thiol, 3,6-dioxa- 1,8-octane-dithiol, pentaerythritol tetrakis(mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), etc. As the above thioxanthones, '2-isopropylthioxene a ketone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, etc. Examples of the phosphine compound include oxidation 2, 4, 6-trimethylbenzimidyl diphenylphosphine, 2,4,6-trimethylbenzimidylphenylethylphosphine oxide, -33- I379J61 Oxidized di(2,4,6·trimethyl Benzopyridyl)phenylphosphine, etc. Other photopolymerization The use ratio is preferably 1 part by weight or less, more preferably 8 parts by weight or less, and particularly preferably 60 parts by weight or less, based on 100 parts by weight of the total photopolymerization initiator. If the ratio of use of other photopolymerization initiators exceeds 00 parts by weight, the effects expected by the present invention may be impaired. Additives: In the range which does not impair the effects expected by the present invention, the sensibility of the present invention In addition to the above-mentioned components, additives such as a surfactant, a binder, a storage stabilizer, and a heat resistance improver may be added to the resin composition as needed. The surfactant is a component having an effect of improving coatability. Preferred fluorine-based surfactants and organic terpene surfactants are preferred as the above-mentioned fluorine-based surfactants having a fluoroalkyl group or a fluoroalkylene group at at least one of a terminal group, a main chain and a side chain. The compound, as a specific example thereof, may be exemplified by 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetra-n-propyl)ether, 1,1,2,2-tetra. Fluorinated n-octyl (n-hexyl) 'Ethylene glycol di(1,1,2,2-tetrafluoro-n-butyl)ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoro-n-pentyl) ether, octapropylene glycol Bis(1,1,2,2-tetrafluoro-n-butyl)ether, hexapropanediol di(1,1,2,2,3,3-hexafluoro-n-pentyl)ether, 1,1,2,2, 3,3-hexafluoro-n-decane, 1,1,2,2,8,8,9,9,10,10-decafluoro-n-dodecane, sodium perfluoro-n-dodecanesulfonate, and fluorinated Sodium alkylbenzene sulfonates - sodium fluoroalkyl phosphites - sodium fluoroalkyl carboxylates, fluoroalkyl polyoxyethylene ethers - diglycerol tetra (fluoroalkyl polyoxyethylene ether) Class, fluoroalkylammonium iodine compounds 'Fluorine-based sweet • 34- 1379161, alkali, fluoroalkyl polyoxyethylene ethers, perfluoroalkyl polyoxyl alcohols, perfluoroalkyl alkane oxidation Materials, fluorine alkyl esters, and the like. For example, BM-1 〇〇〇, BM-1 00 (above, BMCHEMIE Co., Ltd.), Megafac F142D, Megafac F172, Megafac F1 7 3, which are commercially available as a fluorine-based surfactant, may be mentioned. , Megafac F1 8 3, Megafac F178 ' Megafac F 1 9 1 , Megafac F4 7 1 , Megafac F476 (above, manufactured by Dainippon Ink and Chemicals Co., Ltd.), Fluorad FC-170C, Fluorad FC-171, Fluorad FC-430 , Fluorad FC-431 (above, Sumitomo only U - Industrial Co., Ltd.), Surflon S-112, Surflon S-113, Surflon S-131, Surflon S-141, Surflon S -14 5, Surflon S- 3 82 ' Surflon SC- 1 01 ' S ur fl ο n SC -1 0 2 ' Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-106 (above, Asahi Glass Co., Ltd.), Eftop EF301, Eftop EF303, Eftop EF352 (above, New Akita Chemicals Co., Ltd.), Ftergent FT-100, Ftergent FT-110, Ftergent FT-140A' Ftergent FT-150, Ftergent FT-250, Ftergent FT-251, Ftergent FTX-251, Ftergent FTX-218, tergent FT-300 'Ftergent FT-3 10 'Ftergent FT-400S (above, Ri Os (produced by the company) and so on. Examples of the above-mentioned organic fluorene-based surfactants include commercially available products such as Toray Silicone DC3PA, Toray Silicone DC7PA, Toray Silicone SHI 1PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA. 'Toray Silicone SH-190 ' Toray Silicone SH-193, Toray Silicone SZ-6032, Toray Silicone -35- 1379,161 SF-8428, Toray Silico.ne DC-57, Toray Silicone DC-190 (above, Toray, Corning Silicne Co., Ltd., TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 (above, GE Toshiba Silicone Co., Ltd.). Further, examples of the surfactant other than the above include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether: polyoxyethylene Polyoxyethylene aryl 'ethers such as octyl phenyl ether and polyoxyethylene n-decyl phenyl ether; polyoxyethylene dialkyl groups such as polyoxyethylene dilaurate and % oxyethylene distearate A non-ionic surfactant such as an ester; and a commercially available product, for example, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 57, P〇lyfi〇w No. 95 (above, Kyoeisha) Products such as Chemical Co., Ltd.). The above surfactants may be used singly or in combination of two or more. The amount of the surfactant blended is preferably 5 parts by weight or less, more preferably 2 parts by weight or less, based on 100 parts by weight of the [A] copolymer. When the amount of the surfactant is more than 5 parts by weight, the β tends to be rough at the time of coating. The above-mentioned adhesion aid is a component having an effect of improving the adhesion and the adhesion between the protrusion and the spacer and the substrate, and is preferably a functional decane coupling agent. The functional decane coupling agent may, for example, be a reactive functional group compound having a comparative group, a methacryl group, a vinyl group, an isocyanate group or an epoxy group. More specifically, it may, for example, be trimethoxymethylbenzoic acid, fluorenyl-methylpropenyloxypropyltrimethoxydecane, ethylamine tris-36- 1379161 ethoxylated decane, vinyltrimethoxydecane, Isocyanic acid triethoxy decane, r-glycidoxypropyltrimethoxy fluorene epoxy cyclohexyl) ethyl trimethoxy decane, and the like. These bonding aids may be used singly or in combination of two or more. The mixing amount of the adhesion aid is 20 parts by weight or less, more preferably 10 parts by weight or less, based on 100 parts by weight of the copolymer of the [A] copolymer, and if the amount of the adhesion aid is more than 20 parts by weight, it is easy to be smashed. Propensity. Examples of the storage stabilizer include sulfur, an anthracene, a polyoxygen compound, an amine, a nitronitroso compound, and the like, and a 4-methoxyphenol 'N-nitroso-N-phenyl group. Hydroxylamine aluminum and the like. These storage stabilizers may be used singly or in combination of two or more. The storage stabilizer is formulated in an amount of 3 parts by weight or less based on 100 parts by weight of the [A] copolymer, more preferably 〇.〇〇!~〇.5重##, and the mixing amount of the storage stabilizer exceeds 3 When the parts are parts by weight, the shape of the figure may be damaged. The heat resistance improving agent may, for example, be an N-(alkyl I glycoluril compound, an N-(alkoxymethyl) melamine compound, a compound having more than one epoxy group, or the like.

作爲上述N·(烷氧基甲基）甘脲化合物，可列 Ν，Ν，Ν，Ν·四（甲氧基甲基）甘脲' N，N，N，N-四（乙氧義 脲、N，N，N，N -四（正丙氧基甲基）甘脲、n，N，N，N - E 酯基丙基 ' 2-(3,4- 更多種混 量較佳的 ^此時， 產生顯影 氫醌類、 體地可舉 更多種使 合量較佳 量份。此 降低靈敏 I基甲基） I：有2個 舉出例如 甲基）甘 (異丙氧 -37- 1379161 , 基甲基）甘脲、N，N，N，N-四（正丁氧基甲基）甘脲、N，N，n，N-四（叔丁氧基甲基）甘脲等。 這些N-(院氧基甲基）甘脲化合物中，特別較佳的是 N，N，N，N-四（甲氧基甲基）甘脲。 作爲上述N·(烷氧基甲基）三聚氰胺化合物，可列舉出例 如1^，比义1'<1，1^，^六（甲氧基甲基）三聚氰胺、^1^，1^，屮 六（乙氧基甲基）三聚氰胺、Ν,Ν,Ν,Ν,Ν,Ν-六（正丙氧基甲基） 三聚氰胺、Ν，Ν，Ν,Ν，Ν，Ν-六（異丙氧基甲基）三聚氰胺、 Α，Ν，Ν，Ν，Ν，Ν -六（正丁氧基甲基）三聚氰胺、ν,ν,νν,ν,ν-六 (叔丁氧基甲基）三聚氰胺等。 這些Ν-(烷氧基甲基）三聚氰胺化合物中，特別較佳的是 山川^义1^,1六（甲氧基甲基）三聚氰胺，作爲其市售品，可 舉出例如 Nikalac N-2702、Nikalac MW-30M(以上，三和化 學（株）製）的商品等。 另外’作爲具有上述2個或更多個環氧基的化合物，可 舉出例如乙二醇二縮水甘油醚、二甘醇二縮水甘油醚、聚 二醇二縮水甘油醚' 丙二醇二縮水甘油醚、三丙二醇二 縮水甘油醚、聚丙二醇二縮水甘油醚、新戊二醇二縮水甘 油醚、1，6-己二醇二縮水甘油醚、甘油二縮水甘油醚、甘油 三縮水甘油醚、三羥甲基丙烷三縮水甘油醚、氫化雙酚A 二縮水甘油醚、雙酚A二縮水甘油醚、鄰甲酚酚醛型環氧 樹脂。此外，作爲市售品，可舉出例如Epolid 40E、Epolid 100E、Epolid 2 00E、Epolid 70P、Epolid 200P、Epolid 400P、Epolid 15 00NP' Epolid 1 600 ' Epolid 80MF' Epolid -38- 1379161 100MF、Epolid 3002、Epolid 4000(以上，共榮社化學（株） 製），EOCN102、EOCN103S、EOCN104S、EOCN 1 020、 EOCN1025、EOCN1027(日本化藥（株）製），Epikote 1 80S(Japan · Epoxy · r e s i η 公司製）等商品。 這些耐熱性提高劑可以單獨使用，也可以將2種或更多 種混合使用。 相對於100重量份[A]共聚物，耐熱性提高劑的混合量較 佳的是30重量份或以下，更較佳的是20重量份或以下。 時，耐熱性提高劑的混合量如果超過3 0重量份，則感放 射線性樹脂組成物的保存穩定性有降低的趨勢。 本發明的感放射線性樹脂組成物，較佳的是使用溶解在 適當溶劑中的組成物溶液。 作爲上述溶劑可以使用可均一地溶解構成感放射線性 樹脂組成物的各成份，而且不與各成份反應、具有適當的 揮發性的溶劑，從各成分的溶解能、與各成分的反應性和 容易形成塗膜的觀點出發，較佳爲醇類、乙二醇單烷基醚 酸酯類、二甘醇單烷基醚乙酸酯、二甘醇烷基醚類、丙 二醇單烷基醚乙酸酯類、烷氧基丙酸烷基酯類等，特別較 佳的是苯甲醇、2-苯基乙醇、3-苯基-1-丙醇、乙二醇單正 丁基醚乙酸酯、二甘醇單乙基醚乙酸酯、二甘醇二甲基醚、 二甘醇二乙基醚、二甘醇乙基甲基醚、丙二醇單甲基醚乙 酸酯、丙二醇單乙基醚乙酸酯等。 上述溶劑可以單獨使用，也可以將2種或更多種混合後 使用。 -39- 1379,161 在本發明中’進一步的，還將高沸點溶劑和上述溶劑一 起使用。 作爲上述高沸點溶劑，可列舉出例如N_甲基甲醯胺、 N，N-二甲基甲醯胺、N_甲基甲醯苯胺、N_甲基乙醯胺、NN_ 二甲基乙醯胺、Ν·甲基吡咯烷酮、二甲基亞颯、苄基乙基 酸、二正己基醚、丙酮基丙酮、異佛爾酮、己酸、辛酸、 1-辛醇、1-壬醇、苯甲醇、醋酸苄酯、苯甲酸乙酯、草酸 二乙酯、馬來酸二乙酯、丁內酯、碳酸乙烯酯、碳酸丙 %酯、乙二醇單苯基醚乙酸酯等。 這些高沸點溶劑可以單獨使用，也可以將2種或更多種 混合使用。 在所有溶劑中，高沸點溶劑的用量較佳爲5 0重量％或以 下，更較佳爲30重量％或以下。 另外，以上溶劑的用量通常是使本發明的感放射線性樹 脂組成物的固態成分的濃度爲15~45重量％、較佳爲20~40 重量％左右的量》 # 另外，上述調製的組成物溶液也可用孔徑0.5/zm左右 的微孔過濾器等過濾後使用。 本發明的感放射線性樹脂組成物非常適合用於形成垂 直配向型液晶顯示元件的突起和間隔物。 突起和間隔物的形成方法 以下，對於使用本發明的感放射線性樹脂組成物形成本 發明的突起和間隔物的方法進行說明。 本發明的突起和間隔物的形成方法至少包括下述順序 -40 - 1379,161 記載的下述步驟。 (i) 在基板上形成本發明的感放射線性樹脂組成物 的步驟， (ii) 將該薄膜的至少一部分曝光的步驟， (iii) 顯影曝光後的該薄膜的步驟，以及 (iv) 加熱顯影後的該薄膜的步驟。 以下，對於這些步驟依次進行說明。 (i)步驟 ® 在透明基板的一面上形成透明導電膜，在該透明導 上塗覆感放射線性樹脂組成物、較佳爲組成物溶液後 熱塗覆面（預烘烤）形成薄膜。 作爲用於形成間隔物的透明基板，可列舉出例如玻 板、樹脂基板等。更具體地，可舉出鹼石灰玻璃、無 璃等的玻璃基板；聚對苯二甲酸乙二醇酯 '聚對苯二 丁二醇酯、聚醚颯、聚碳酸酯、聚醯亞胺等的塑膠形 樹脂基板。 • 作爲在透明基板的一面上設置的透明導電膜，可舉 氧化錫（SnO〇形成的NESA膜（美國PPG社的注冊商標 化銦-氧化錫（In2〇3-Sn〇2)形成的ITO膜等。 作爲形成本發明的感光性樹脂組成物塗膜的方法， 可以通過（1)塗布法、（2)乾燥薄膜法進行。 作爲組成物溶液的塗覆方法，例如可採用噴射法、 法、旋轉塗覆法（旋塗法）' 狹縫塗覆法 '刮條塗覆法 墨噴射塗覆法等適宜的方法，特別較佳旋塗法、狹縫 薄膜 電膜 ，加 璃基 驗玻 甲酸 成的 出由 )、氧 例如 輥塗 、油 塗覆 -41 - 1379161t 法。 另外，在採用（2)乾燥薄膜法形成本發明的感光性箱 成物的塗膜時，該乾燥薄膜是在基底薄膜、較佳爲赛 的基底薄膜上，層壓由本發明的感光性樹脂組成物开 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甲 光性樹脂組成物、較佳爲液狀組成物後，乾燥，層歷 性層形成。作爲感光性乾燥薄膜的基底薄膜，例如互 % 聚對苯二甲酸乙二醇酯（PET)、聚乙烯 '聚丙烯、赛 酯、聚氯乙烯等合成樹脂薄膜。基底薄膜的厚度合遲 15〜125/zm。所得的感光性層的厚度較佳爲1〜3〇ν 右。 另外，感光性乾燥薄膜在未使用時，可以在該感为 上進一步層壓保護膜進行保存。該保護膜在未使用時 剝離，在使用時可以容易地剝離，所以必須有適當的 性。作爲滿足這種條件的保護膜，可以列舉出例如在 _膜、聚丙烯薄膜、聚乙烯薄膜、聚氯乙烯薄膜等合 脂的表面上，塗覆或燒結有機矽類脫模劑形成的薄膜 護膜的厚度通常爲25#m左右。 另外，預烘烤的條件，根據各成份的種類、混合比 而異，通常在70〜120 °C下，爲1-15分鐘左右。 (ii)步驟 接著，將形成的薄膜的至少一部分曝光。此時， 的一部分上曝光時，通過具有規定圖形的光掩模曝 脂組 韌性 成的 的感 感光 以使 碳酸 的是 m左 性層 ，不 脫模 PET 成樹 。保 例等 薄膜 。此 -42- 1379.161 . 時’如果考慮生產性，較佳對形成突起的區域和作爲間隔 物的區域，以實質上相同的曝光量曝光。此時，在曝光間 隙一定時’掩模的開口寬度越小，曝光照明度越低，所以 交聯度越低’結果是，後烘烤時容易流動，產生高度差。 另外，還可以通過具有放射線透過率大的部分和放射線 透過率小的部分的圖案掩模進行曝光。 作爲曝光時使用的放射線，可以使用例如可視光線、紫 外線、遠紫外線、電子束、X射線等，較佳波長範圍是190 t 45 0nm的放射線，特別較佳含有365nm的紫外線的放射 線。 曝光量是通過光度計（OAI model 3 5 6，OAI Optical Associates Inc.製造）測定曝光的放射線波長爲365nm的強 度的値，通常是100〜3,000J/m2,較佳爲200〜l,200J/m2。 (iii)步驟 接著，通過將曝光後的薄膜顯影，除去不要的部分形成 規定的圖形。 # 作爲用於顯影的顯影液，較佳爲鹼性顯影液，作爲其例 子可以列舉出氫氧化鈉、氫氧化鉀、碳酸鈉、矽酸鈉、甲 基矽酸鈉、氨等無機鹼類；乙胺、正丙胺等脂肪族伯胺類： 二乙胺 '二正丙胺等脂肪族仲胺類；三甲胺、甲基二乙胺、 二甲基乙胺、三乙胺等的脂肪族叔胺類；吡咯、哌啶、N-甲基哌啶、N-甲基吡咯烷、1,8-二氮雜二環[5.4.01-7-十~ 碳烯' 1,5-二氮雜二環[4.3.0]-5-壬烯等的脂環族叔胺類； 吡啶、三甲基吡啶、二甲基吡啶、喹啉等的芳香族叔胺類； • 43· 1379,161. 二甲基乙醇胺，甲基二乙醇胺、三乙醇胺等鏈烷醇胺類： #氧化四甲基銨、氫氧化四乙基銨等季銨鹽等鹼性化合物 的水溶液。 另外，在上述鹼性化合物的水溶液中也可添加適當量的 甲醇、乙醇等水溶性有機溶劑和表面活性劑後使用。 作爲顯影方法，也可以盛液法、浸漬法、噴淋法等的任 意一種方法，顯影時間通常是10〜180秒左右。 顯影後，例如流水洗滌30〜90秒後，例如通過壓縮空 I或壓縮氮氣風乾形成所希望的圖形。 (iv)步驟 接著，將得到的圖形通過例如熱板、烘箱等加熱裝置加 熱（後烘烤）到規定溫度，例如150〜250°C，規定時間，例 如對於熱板上是5〜30分鐘、對於供箱中是30〜180分鐘， 可得到規定的突起和間隔物。 本發明的感放射線性樹脂組成物是高靈敏度的，可以同 時形成垂直配向型液晶顯示元件的突起和間隔物，可以得 #!J足夠的圖形形狀，可以形成間隔物強度、耐硏磨性、和 透明基板的密合性、耐熱性等都優異的垂直配向型液晶顯 示元件使用的突起和間隔物。 另外，本發明的垂直配向型液晶顯示元件具有圖形形 狀、間隔物強度、耐硏磨性、與透明基板的密合性、耐熱 性等各種性能都優異的突起和間隔物，經過很長時間也可 以顯示出高的可靠性。 實施例 -44- 1379.161. 以下’用實施例對本發明的實施方式進行更具體的說 明。這裏，份和％是重量基準。 合成例1 在具備冷卻管、攪拌機的燒瓶中，加入5份2,2，-偶氮二 異丁腈和250份二甘醇甲基乙基醚，接著，加入35份2_ 甲基丙烯醯氧基乙基琥珀酸、25份甲基丙烯酸正丁酯、35 份甲基丙烯酸苄酯，氮氣置換後，再加入5重量份1,3-丁 二烯，慢慢攪拌且將溶液的溫度上升到90°C，在該溫度下 %持5小時進行聚合，得到固態成分濃度爲28.0%的[A]共 聚物溶液。將其作爲[A-1]聚合物。 所得的[A-1]聚合物使用 GPC(凝膠滲透色譜 法）HLC-8020(商品名，TOSOH(株）製）測定 Mw，爲 1 2,000。 合成例2 在具備冷卻管、攪拌機的燒瓶中，加入5重量份2，2，· 偶氮二（2,4-二甲基戊腈）和200份二甘醇甲基乙基醚，接 著，力Q入18份甲基丙烯酸、40份甲基丙烯酸縮水甘油酯、 重量份苯乙烯、32份甲基丙烯酸三環[5.2.1.02.6]癸-8-基 酯、氮氣置換後，再加入5份1,3-丁二烯，慢慢攪拌且將 溶液的溫度上升到7CTC，保持該溫度5小時進行聚合，得 到共聚物[A - 2 ]的溶液。 該溶液的固態成分濃度爲33.0重量％，共聚物[A-2]的 Mw，爲 1 1 ,〇〇〇。 實施例1 組成物溶液的配製 -45- 1379161 將100份作爲[A]成份的由合成例1得到的[A】共聚物溶 液共聚物[A-1 ]’ 60份作爲[B]成份的二季戊四醇六丙烯酸 醋（商品名KAYARAD DPHA、日本化藥（株）製）、5份作爲[C] 成份的乙酮，1-[9-乙基- 6-(2-甲基-4-四氫呋喃甲氧基苯甲醯 基）·9·Η._咔唑-3-基]-，1·(〇-乙醯基肟）混合，溶解到丙二醇 單甲基醚乙酸酯中’使固態成分濃度成爲30%，然後用孔 徑0.5/zm的微孔過濾器過濾，配製組成物溶液。 突起和間隔物的形成 • 在無鹼玻璃基板上使用旋轉噴射器塗覆上述組成物溶 液後’在80 °C的熱板上預烘烤3分鐘形成膜厚4.0/zm的薄 膜。 接著，在得到的薄膜上通過殘留5/zm和15/zm圓的圖 形的光掩模’以曝光狹縫200 //m，365nm的強度爲250W/m2 的紫外線曝光4秒鐘。此時的實際曝光量相當於i 000〗/m2。 然後’用0.05重量％的氫氧化鉀水溶液在25 °C下顯影規定 時間後，用純水洗滌1分鐘，再在22CTC的烘箱中加熱60 β鐘，一次曝光同時形成突起和間隔物。通過殘留5//m的 圖形的光掩模形成突起，通過殘留15//m的圓的圖形的光 掩模形成間隔物》 接著，根據下述要領，進行各種評價。評價結果如表2 所示。 (1)靈敏度評價 在所得的圖形中，顯影後的殘膜率爲90%或以上的靈敏 度爲1200〗/m2或以下時，可以認爲靈敏度良好。 -46- 1379.161 ‘ (2) 剖面形狀的評價 用掃描型電子顯微鏡觀察所得的突起和間隔物的剖面 形狀，根據是否符合於第1圖所示的A〜E的任何一種進行 評價。對於突起的情況來說，剖面形狀爲第1圖（D)這樣的 半凸透鏡狀時，是良好的；在爲第1圖（E)這樣的正三角形 時，從配向膜的塗布性來說是不好的》 另一方面，對於間隔物的情況來說，在形成第1圖（A) 這樣的柱狀或者第1圖（B)這樣的順圓錐狀時，剖面形狀良 。相對於此·，在爲第1圖（C)所示的倒圓錐狀（剖面形狀是 薄膜表面的邊緣比基板側的邊緣更長的倒三角形）時，在後 期硏磨處理時由於圖形極有可能剝落，所以剖面形狀不好。 (3) 間隔物強度的評價 對所得的間隔物，用微小壓縮試驗機（商品名 MCTM-200、（株）島津製作所製造），用直徑50// m的平面壓 子’以2.6mN/s的負荷速度，測定加入lOmN的負荷時的變 形量（測定溫度爲2 3 °C )。該値在0.5 // m或以下時，可以認 β爲間隔物的強度良好。 (4) 耐硏磨性的評價 用液晶配向膜塗覆用印刷機將作爲液晶配向劑的 AL3046(商品名，：iSR(株）製）塗覆在形成有間隔物的基板上 後’在180°C下乾燥1小時，形成膜厚〇.〇5 m液晶配向劑 的塗膜。 而後’在該塗膜上，使用具有捲繞聚醯胺製布的輥的硏 磨機進行硏磨處理，輥的轉速是500rpm、載物台的移動速 -47- 1379161 * «! 度是lcm/s。此時評價圖形有無被切削或者剝離。 (5) 密合性的評價 除了不使用光掩模外，與上述間隔物的形成相同地實 施，形成固化膜。而後，根據〗IS K-5400(1900)8.5的黏著 性試驗中的8.5· 2的棋盤格膠帶法進行評價。此時100個的 棋盤格中殘留的棋盤格的數量如表2所示。 (6) 耐熱性的評價 除了不使用光掩模外，與上述間隔物的形成相同地實 A拖，形成固化膜，之後，在240°C的烘箱中加熱60分鐘， 測定加熱前後的膜厚，通過殘膜率（加熱後的膜厚X 1 00/初期 膜厚）評價。 實施例2 ~ 1 2、比較例1〜4 在實施例1中，將表1的各成分以及5份作爲黏接助劑 的r -環氧丙氧基丙基三甲氧基矽烷、0.5份作爲表面活性 劑的 FTX-21 8、0.5份作爲保存穩定劑的4-甲氧基苯酚混 合，溶解在丙二醇單甲基醚乙酸酯中，以使固態成分濃度 β爲30%後，用孔徑0.5 // m的微孔過濾器過濾，製備組成物 溶液。之後，與實施例1同樣地，形成突起和間隔物，與 實施例1同樣地評價。結果如表2所示。 在表1中，聚合物以外的各成分，如下所述。 B-1 :二季戊四醇六丙烯酸酯（商品名KAYARAD DPHA) B-2:含多官能聚氣酯_丙稀酸酯類化合物市售品（商品名 KAYARAD DPHA-40H) [C]成分 • 48 · 1379,161 t 〆 C-l:乙醇，l-[9-乙基- 6-(2-甲基-4-四氫呋喃甲氧基苯甲 醯基）-9·Η·-咔唑-3-基）-,1-(0-乙醯基肟） (：-2:乙酮，1-[9-乙基-6-[2-甲基-4-(2,2-二甲基-1,3.-二噚 烷基）甲氧基苯甲醯基]昨唑-3-基]-,1-(0-乙醯基肟） D-1 : 2 -甲基-1-(4-甲基硫代本基）-2-嗎琳基-丙-1-嗣（商 品名 Irgacure 907，Ciba Speciality Chemicals 社製） D-2: 2-(4-甲基苯甲酰基）-2-(二甲基胺基）-1-(4-嗎啉基 苯基）-丁 -1 -酮（商品名 Irgacure 37 9，Ciba Speciality hemicals 社製） E-l : 2,2’-二（2,4-二氯代苯基）-4,4’，5,5’-四苯基-1,2’-二 咪唑 E-2 : 2,2’-二（2-氯代苯基）-4,4’，5 ,5’-四苯基-1,2’ -二咪唑 E-3: 4,4’-二（二乙基胺基）二苯酮 E-4: 2 -毓基苯并噻唑 ?-1:2,4-二乙基噻噸酮 F-2:氧化2,4,6-三甲基苯甲醯基二苯基 • -49- 1379161,As the above N·(alkoxymethyl)glycolide compound, it can be listed as Ν, Ν, Ν, Ν·tetrakis(methoxymethyl)glycolide 'N,N,N,N-tetrakis (ethoxydicarbamide) , N, N, N, N - tetra (n-propoxymethyl) glycoluril, n, N, N, N - E ester propyl ' 2- (3, 4- more mixed amount ^ At this time, a developing hydroquinone is produced, and a plurality of kinds of the mixture are preferably added in a preferred amount. This lowers the sensitivity of the methyl group of the methyl group. I: There are two, for example, methyl) glycine (isopropyloxy- 37- 1379161 , dimethylmethyl) glycoluril, N, N, N, N-tetrakis (n-butoxymethyl) glycoluril, N, N, n, N-tetrakis (tert-butoxymethyl) glycoluril Wait. Among these N-(homoyloxymethyl)glycoluric compounds, N,N,N,N-tetrakis(methoxymethyl)glycolil is particularly preferred. Examples of the N-(alkoxymethyl)melamine compound include, for example, 1^, 1'<1,1^,^hexa(methoxymethyl)melamine, ^1^, 1^, Hexa(ethoxymethyl)melamine, ruthenium, osmium, iridium, osmium, iridium, osmium-hexa(n-propoxymethyl) melamine, hydrazine, hydrazine, hydrazine, hydrazine, hydrazine, hydrazine-hexa-isopropyl Oxymethyl) melamine, hydrazine, hydrazine, hydrazine, hydrazine, hydrazine, hydrazine - hexa(n-butoxymethyl) melamine, ν, ν, νν, ν, ν-hexa(tert-butoxymethyl) melamine Wait. Among these fluorene-(alkoxymethyl) melamine compounds, yam (1 methoxy) melamine is particularly preferable, and as a commercially available product, for example, Nikalac N-2702 is mentioned. And Nikalac MW-30M (above, manufactured by Sanwa Chemical Co., Ltd.). Further, 'as a compound having the above two or more epoxy groups, for example, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyglycol diglycidyl ether 'propylene glycol diglycidyl ether , tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, trihydroxyl Methylpropane triglycidyl ether, hydrogenated bisphenol A diglycidyl ether, bisphenol A diglycidyl ether, o-cresol novolac type epoxy resin. Further, as a commercial item, for example, Epolid 40E, Epolid 100E, Epolid 2 00E, Epolid 70P, Epolid 200P, Epolid 400P, Epolid 15 00NP' Epolid 1 600 ' Epolid 80MF' Epolid -38-1379161 100MF, Epolid 3002 Epolid 4000 (above, Kyoeisha Chemical Co., Ltd.), EOCN102, EOCN103S, EOCN104S, EOCN 1 020, EOCN1025, EOCN1027 (manufactured by Nippon Kayaku Co., Ltd.), Epikote 1 80S (Japan · Epoxy · resi η Products). These heat resistance improvers may be used singly or in combination of two or more. The amount of the heat resistance improving agent to be blended is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, based on 100 parts by weight of the [A] copolymer. In the case where the amount of the heat-resistant improver is more than 30 parts by weight, the storage stability of the radiation-sensitive resin composition tends to be lowered. In the radiation sensitive resin composition of the present invention, it is preferred to use a composition solution dissolved in a suitable solvent. As the solvent, a solvent which can uniformly dissolve the components constituting the radiation sensitive resin composition and which does not react with each component and has appropriate volatility can be used, and the solubility of each component and the reactivity with each component are easy. From the viewpoint of forming a coating film, preferred are alcohols, ethylene glycol monoalkyl ether esters, diethylene glycol monoalkyl ether acetate, diethylene glycol alkyl ethers, propylene glycol monoalkyl ether acetate. Particularly preferred are alkyl, alkoxypropionic acid esters and the like, and particularly preferred are benzyl alcohol, 2-phenylethanol, 3-phenyl-1-propanol, ethylene glycol mono-n-butyl ether acetate, and Glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Acid esters, etc. The above solvents may be used singly or in combination of two or more. -39-1379,161 In the present invention, further, a high boiling point solvent is used together with the above solvent. Examples of the high boiling point solvent include N-methylformamide, N,N-dimethylformamide, N-methylformamide, N-methylacetamide, NN_dimethyl B. Indamine, hydrazine, methyl pyrrolidone, dimethyl hydrazine, benzyl ethyl acid, di-n-hexyl ether, acetone acetone, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, Benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetate, and the like. These high boiling solvents may be used singly or in combination of two or more. The high boiling point solvent is preferably used in an amount of 50% by weight or less, more preferably 30% by weight or less, based on all the solvents. Further, the amount of the above solvent is usually such that the concentration of the solid content of the radiation sensitive resin composition of the present invention is from 15 to 45% by weight, preferably from about 20 to 40% by weight. The solution can also be used after being filtered by a micropore filter having a pore size of about 0.5/zm or the like. The radiation sensitive resin composition of the present invention is very suitable for forming protrusions and spacers of a vertical alignment type liquid crystal display element. Method of Forming Protrusions and Spacers Hereinafter, a method of forming the protrusions and spacers of the present invention using the radiation sensitive resin composition of the present invention will be described. The method for forming the protrusions and spacers of the present invention includes at least the following steps described in the following sequence -40 - 1379,161. (i) a step of forming the radiation sensitive resin composition of the present invention on a substrate, (ii) a step of exposing at least a portion of the film, (iii) a step of developing the film after exposure, and (iv) heating and developing The step of the film after. Hereinafter, these steps will be sequentially described. (i) Step ® A transparent conductive film is formed on one surface of the transparent substrate, and a radiation-sensitive resin composition, preferably a composition solution, is applied onto the transparent conductive layer, and then the surface is thermally coated (prebaked) to form a film. Examples of the transparent substrate for forming the spacer include a glass plate, a resin substrate, and the like. More specifically, a glass substrate such as soda lime glass or glass-free; polyethylene terephthalate 'polybutylene terephthalate, polyether oxime, polycarbonate, polyimine, etc. Plastic resin substrate. • As a transparent conductive film provided on one surface of a transparent substrate, tin oxide (NESO film formed of SnO〇 (registered trademark indium-tin oxide (In2〇3-Sn〇2) of PPG, USA) The method of forming the coating film of the photosensitive resin composition of the present invention can be carried out by (1) coating method and (2) dry film method. As the coating method of the composition solution, for example, a spraying method, a method, or the like can be employed. Rotary coating method (spin coating method) 'slit coating method' scraper coating method ink jet coating method and the like, particularly preferred spin coating method, slit film electric film, glass based test formic acid In the case of the coating film of the photosensitive container of the present invention by the (2) dry film method, the dried film is on the substrate. The photosensitive film composition of the present invention is formed by laminating a photosensitive layer of a photosensitive resin composition of the present invention (hereinafter referred to as "photosensitive dry film"). The photosensitive dried film is a base film. Applying the hair light tree The composition, preferably a liquid composition, is dried and formed into a layer of a layer. As a base film of the photosensitive dried film, for example, poly(ethylene terephthalate) (PET) or polyethylene 'polypropylene A synthetic resin film such as celery ester or polyvinyl chloride. The thickness of the base film is 15 to 125/zm later. The thickness of the photosensitive layer obtained is preferably 1 to 3 〇ν right. In addition, the photosensitive dried film is not used. In this case, the protective film can be further laminated and stored. The protective film is peeled off when it is not used, and can be easily peeled off during use. Therefore, it is necessary to have appropriate properties. As a protective film satisfying such conditions, For example, on the surface of the fat-bonding such as a film, a polypropylene film, a polyethylene film, or a polyvinyl chloride film, the thickness of the film film formed by coating or sintering the organic oxime release agent is usually about 25 #m. Further, the prebaking conditions vary depending on the type and mixing ratio of each component, and are usually about 1 to 15 minutes at 70 to 120 ° C. (ii) Step Next, at least a part of the formed film is exposed. At this time, one In the case of partial exposure, the sensitization of the toughness of the photo-adhesive group with a predetermined pattern is such that the carbonic acid is the m-left layer, and the mold-free PET is formed into a tree. The film is protected by a film such as -42- 1379.161. 'If productivity is considered, it is preferable to expose the region where the protrusion is formed and the region as the spacer with substantially the same exposure amount. At this time, when the exposure gap is constant, the smaller the opening width of the mask, the more the exposure illumination is. When it is low, the degree of cross-linking is lower. As a result, it is easy to flow during post-baking, and a height difference is generated. Further, it is also possible to perform exposure by a pattern mask having a portion having a large radiation transmittance and a portion having a small radiation transmittance. For the radiation to be used for the exposure, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like can be used, and a radiation having a wavelength of preferably 190 t 45 0 nm is preferable, and a radiation containing ultraviolet light of 365 nm is particularly preferable. The amount of exposure is measured by a photometer (OAI model 356, manufactured by OAI Optical Associates Inc.), and the intensity of the exposed radiation having a wavelength of 365 nm is usually 100 to 3,000 J/m2, preferably 200 to 1,200 J/ M2. (iii) Step Next, by developing the exposed film, unnecessary portions are removed to form a predetermined pattern. As the developer for development, an alkaline developer is preferred, and examples thereof include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium methyl citrate, and ammonia; Aliphatic primary amines such as ethylamine and n-propylamine: aliphatic secondary amines such as diethylamine 'di-n-propylamine; aliphatic tertiary amines such as trimethylamine, methyldiethylamine, dimethylethylamine and triethylamine Class; pyrrole, piperidine, N-methylpiperidine, N-methylpyrrolidine, 1,8-diazabicyclo[5.4.01-7-deca-carbene' 1,5-diaza An alicyclic tertiary amine such as a ring [4.3.0]-5-pinene; an aromatic tertiary amine such as pyridine, trimethylpyridine, lutidine or quinoline; • 43· 1379,161. An alkanolamine such as methylethanolamine or methyldiethanolamine or triethanolamine: an aqueous solution of a basic compound such as a quaternary ammonium salt such as tetramethylammonium or tetraethylammonium hydroxide. Further, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol and a surfactant may be added to the aqueous solution of the above basic compound. As the developing method, any one of a liquid-filling method, a dipping method, and a shower method may be used, and the development time is usually about 10 to 180 seconds. After development, for example, after running for 30 to 90 seconds in flowing water, the desired pattern is formed, for example, by air drying or compressed nitrogen. (iv) Step Next, the obtained pattern is heated (post-baked) to a predetermined temperature, for example, 150 to 250 ° C by a heating means such as a hot plate or an oven, for a predetermined time, for example, 5 to 30 minutes on a hot plate, For the case of 30 to 180 minutes in the case, predetermined protrusions and spacers can be obtained. The radiation sensitive resin composition of the present invention is highly sensitive, and can simultaneously form protrusions and spacers of the vertical alignment type liquid crystal display element, and can obtain a sufficient pattern shape of #!J, and can form spacer strength, honing resistance, A protrusion and a spacer used in a vertical alignment type liquid crystal display element excellent in adhesion to a transparent substrate, heat resistance, and the like. Further, the vertical alignment type liquid crystal display device of the present invention has protrusions and spacers excellent in various properties such as a pattern shape, a spacer strength, a honing resistance, an adhesion to a transparent substrate, and heat resistance, and it takes a long time. Can show high reliability. EXAMPLES - 44 - 1379.161. Hereinafter, embodiments of the present invention will be more specifically described by way of examples. Here, parts and % are weight basis. Synthesis Example 1 In a flask equipped with a cooling tube and a stirrer, 5 parts of 2,2,-azobisisobutyronitrile and 250 parts of diglycol methyl ethyl ether were added, followed by the addition of 35 parts of 2 -methacryloxyl Base ethyl succinic acid, 25 parts of n-butyl methacrylate, 35 parts of benzyl methacrylate, after nitrogen replacement, add 5 parts by weight of 1,3-butadiene, slowly stir and raise the temperature of the solution to The polymerization was carried out at 90 ° C for 5 hours at this temperature to obtain a [A] copolymer solution having a solid concentration of 28.0%. This was designated as [A-1] polymer. The obtained [A-1] polymer was measured for Mw by a GPC (gel permeation chromatography) HLC-8020 (trade name, manufactured by TOSOH Co., Ltd.) to be 12,000. Synthesis Example 2 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 of diethylene glycol methyl ethyl ether were added, followed by Force Q into 18 parts of methacrylic acid, 40 parts of glycidyl methacrylate, parts by weight of styrene, 32 parts of tricyclo [5.2.1.02.6] 癸-8-yl methacrylate, after nitrogen replacement, then add 5 parts of 1,3-butadiene was slowly stirred and the temperature of the solution was raised to 7 CTC, and the temperature was maintained for 5 hours to carry out polymerization to obtain a solution of the copolymer [A-2]. The solid concentration of the solution was 33.0% by weight, and the Mw of the copolymer [A-2] was 1 1 , 〇〇〇. Example 1 Preparation of Composition Solution - 45 - 1379161 100 parts of [A] copolymer solution copolymer [A-1 ]' obtained as the component [A] as the component [A] was used as the component [B] Pentaerythritol hexaacrylate (trade name: KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.), 5 parts of ethyl ketone as [C], 1-[9-ethyl-6-(2-methyl-4-tetrahydrofuran) Oxybenzhydryl)·9·Η._oxazol-3-yl]-,1·(〇-ethinylhydrazine) mixed, dissolved in propylene glycol monomethyl ether acetate The composition was made up to 30%, and then filtered with a micropore filter having a pore size of 0.5/zm to prepare a composition solution. Formation of protrusions and spacers • After coating the above composition solution on a non-alkali glass substrate using a rotary ejector, 'pre-bake on a hot plate at 80 °C for 3 minutes to form a film having a film thickness of 4.0/zm. Next, on the obtained film, a photomask of a pattern of 5/zm and 15/zm circles was left exposed to ultraviolet light having an exposure slit of 200 // m and a intensity of 365 nm of 250 W/m 2 for 4 seconds. The actual exposure at this time is equivalent to i 000 〗 / m2. Then, after developing for a predetermined period of time at 25 ° C with a 0.05% by weight aqueous potassium hydroxide solution, it was washed with pure water for 1 minute, and further heated in a 22 CTC oven for 60 β, and simultaneously exposed to form protrusions and spacers. A projection was formed by a photomask having a pattern of 5//m remaining, and a spacer was formed by a photomask having a pattern of a circle of 15//m. Next, various evaluations were made according to the following methods. The evaluation results are shown in Table 2. (1) Sensitivity evaluation In the obtained pattern, when the sensitivity of the residual film ratio after development of 90% or more is 1200 Å/m2 or less, the sensitivity is considered to be good. -46- 1379.161 ‘ (2) Evaluation of cross-sectional shape The cross-sectional shape of the protrusion and the spacer observed by a scanning electron microscope was evaluated according to whether or not it conformed to any of A to E shown in Fig. 1 . In the case of a projection, the cross-sectional shape is good in the case of a semi-convex lens shape as shown in Fig. 1(D), and in the case of an equilateral triangle such as Fig. 1(E), the coating property from the alignment film is On the other hand, in the case of the spacer, when the columnar shape as shown in Fig. 1(A) or the straight cone shape as shown in Fig. 1(B) is formed, the cross-sectional shape is good. On the other hand, in the case of the inverted conical shape shown in Fig. 1(C) (the cross-sectional shape is an inverted triangle whose edge of the film surface is longer than the edge on the substrate side), the pattern is extremely high in the later honing process. May peel off, so the profile is not good. (3) Evaluation of the spacer strength The obtained spacer was measured by a micro compression tester (trade name: MCTM-200, manufactured by Shimadzu Corporation) using a plane pressure of 50/m in diameter of 2.6 mN/s. The load speed was measured for the amount of deformation when the load of 10 mN was added (the measured temperature was 23 ° C). When the enthalpy is 0.5 // m or less, the strength of the spacer can be recognized as good. (4) Evaluation of honing resistance After coating a substrate on which a spacer is formed, AL3046 (product name: manufactured by iSR Corporation) as a liquid crystal alignment agent is applied to a liquid crystal alignment film coating printer. The film was dried at ° C for 1 hour to form a film having a film thickness of 〇. 5 m liquid crystal alignment agent. Then, on the coating film, honing was performed using a honing machine having a roll of a polyamide-made cloth, the rotation speed of the roller was 500 rpm, and the moving speed of the stage was -47 - 1379161 * «! Degree is lcm /s. At this time, the evaluation pattern was cut or peeled off. (5) Evaluation of adhesion A cured film was formed in the same manner as the formation of the above spacer except that the photomask was not used. Then, it was evaluated according to the 8.5·2 checkerboard tape method in the adhesion test of IS K-5400 (1900) 8.5. The number of checkerboards remaining in the 100 checkerboards is shown in Table 2. (6) Evaluation of heat resistance The cured film was formed in the same manner as the formation of the spacer except that the photomask was not used, and then heated in an oven at 240 ° C for 60 minutes to measure the film thickness before and after heating. The film was evaluated by the residual film ratio (film thickness after heating X 1 00 / initial film thickness). Examples 2 to 2, Comparative Examples 1 to 4 In Example 1, each component of Table 1 and 5 parts of r-glycidoxypropyltrimethoxydecane as an adhesion aid, and 0.5 parts were used. Surfactant FTX-21 8 and 0.5 parts of 4-methoxyphenol as a storage stabilizer are mixed and dissolved in propylene glycol monomethyl ether acetate so that the solid content concentration β is 30%, and the pore diameter is 0.5. The microporous filter of // m was filtered to prepare a composition solution. Thereafter, in the same manner as in Example 1, protrusions and spacers were formed, and they were evaluated in the same manner as in Example 1. The results are shown in Table 2. In Table 1, each component other than a polymer is as follows. B-1: dipentaerythritol hexaacrylate (trade name KAYARAD DPHA) B-2: polyfunctional polyglycol ester _ acrylate compound (commercial name KAYARAD DPHA-40H) [C] ingredient • 48 · 1379,161 t 〆Cl: ethanol, l-[9-ethyl-6-(2-methyl-4-tetrahydrofuranmethoxybenzylidene)-9·Η·-carbazol-3-yl)- , 1-(0-ethylhydrazine) (:-2: ethyl ketone, 1-[9-ethyl-6-[2-methyl-4-(2,2-dimethyl-1,3. -didecyl)methoxybenzylidene]-oxazolyl-3-yl]-,1-(0-ethylindenyl) D-1 : 2-methyl-1-(4-methylsulfide代本基)-2-Merynyl-propan-1-indole (trade name Irgacure 907, manufactured by Ciba Speciality Chemicals) D-2: 2-(4-methylbenzoyl)-2-(dimethyl Amino)-1-(4-morpholinylphenyl)-butan-1-one (trade name: Irgacure 37, manufactured by Ciba Speciality hemicals) El: 2,2'-di(2,4-dichloro Phenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole E-2 : 2,2'-bis(2-chlorophenyl)-4,4',5 , 5'-tetraphenyl-1,2'-diimidazole E-3: 4,4'-bis(diethylamino)benzophenone E-4: 2-mercaptobenzothiazole-1: 2,4-diethylthioxanthone F-2 : Oxidation of 2,4,6-trimethylbenzhydryldiphenyl • -49- 1379161,

φ 重置份 1 ur» 1 I I νη I ιη I m c>i 1 wn cs 1 1 I I uu 種類 1 Ξ 1 1 < Ξ 1 〇4 1 Ξ I 1 ci 1 1 < 1 E成分 重量份 1 1 t 10+10+5 I I 10+10+5 1 t • t 1 1 1 I 1 種類 1 1 1 Ε-2+Ε-3+Ε-4 1 1 Ε-2+Ε-3+Ε-4 1 1 1 I 1 1 1 1 1 D成分 重量份 1 Ο ο 1 1 ο 1 1 1 ο I o ο ο & limn 1 CS ά t 1 > < ά 1 t 1 ά I ώ ά CN ά ά 03 ά c成分 重量份 IT) _ ·Η « CN »—Η W) •拜< 1 1 1 1 ιίτττίΐ W 1 ύ ύ ύ ύ ι 1 ύ CS ύ CM ύ OJ ύ CN ΰ 1 1 1 1 B成分 重量份 s S S 40+20 S 40+20 40+20 S s s S ο > 1 S ο S m •MS «1mi1 w ώ ώ ώ Β-1+Β-2 PQ PQ Β-1+Β-2 Β-1+Β-2 ώ PQ ώ r^i PQ ώ PQ ώ ώ A成分 重量份 ο ο ο ο Ο 1 < Ο * · < ο ^ ο ο » < ο ο 〇 ο Ο ο ο »"< 種類 聚合物A-l 聚合物Α-1 聚合物Α-1 聚合物Α-1 聚合物Α-2 聚合物Α-2 聚合物Α-2 聚合物Α-2 聚合物Α-1 聚合物Α-1 聚合物Α-2 聚合物A-2 聚合物Α-1 聚合物Α-1 聚合物Α-2 聚合物Α-2 組成物 種類 (S-l) (S-2) (S-3) (S-4) (S-5) (S-6) (S-7) (S-8) (S-9) (S-10) (S-ll) (S-12) (s-l) § (s-4) 實施例1 實施例2 1實施例3 實施例4 實施例5 實施例6 實施例7 實施例8 實施例9 實施例10 實施例11 實施例12 比較例1 比較例2 1比較例3 比較例4 1379,161 表2 組成物 靈敏度 剖面形狀 分隔物強度 耐硏磨性實驗 密洽性 耐熱性 種類 (J/m2) 突起 分隔物 (⑽ 有無剝離 (/100) (%) 實施例1 (S-1) 700 D B 0.6 無 100 80 實施例2 (S-2) 800 D B 0.7 無 100 81 實施例3 (S-3) 1000 D A 0.6 Μ 100 83 實施例4 (S-4) 1000 D B 0.8 無 100 82 實施例5 (S-5) 600 D B 0.7 5Ε 100 93 實施例6 (S-6) 700 D B 0.7 無 100 93 實施例7 (S-7) 800 D A 0.9 無 100 92 實施例8 (S-8) 800 D B 0.8 Μ 100 90 實施例9 (S-9) 600 D B 0.6 Μ /1、、 100 80 實施例10 (S-10) 750 D B 0.7 4ττΤ. 無 100 80 實施例11 (S-11) 600 D B 0.7 Am. 無 100 92 實施例12 (S-12) 650 D B 0.7 無 100 92 比較例1 (s-1) 2000 E C 0.5 有 90 75 比較例2 (s-2) 2500 D A 0.7 Μ 100 78 比較例3 (s-3) 1800 D B 0.6 Μ /tw 100 89 比較例4 (s-4) 2200 D A 0.7 Ά n\\ 100 90 【圖式簡單說明】 第1圖是例示間隔物的剖面形狀的示意圖。 -51 -φ reset part 1 ur» 1 II νη I ιη I m c>i 1 wn cs 1 1 II uu type 1 Ξ 1 1 < Ξ 1 〇4 1 Ξ I 1 ci 1 1 < 1 E component parts by weight 1 1 t 10+10+5 II 10+10+5 1 t • t 1 1 1 I 1 Type 1 1 1 Ε-2+Ε-3+Ε-4 1 1 Ε-2+Ε-3+Ε-4 1 1 1 I 1 1 1 1 1 D component parts by weight 1 Ο ο 1 1 ο 1 1 1 ο I o ο ο & limn 1 CS ά t 1 >< ά 1 t 1 ά I ώ ά CN ά ά 03 ά c component parts by weight IT) _ ·Η « CN »—Η W) • By < 1 1 1 1 ιίτττίΐ W 1 ύ ύ ύ ι ι 1 ύ CS ύ CM ύ OJ ύ CN ΰ 1 1 1 1 B component Parts by weight s SS 40+20 S 40+20 40+20 S ss S ο > 1 S ο S m •MS «1mi1 w ώ ώ ώ Β-1+Β-2 PQ PQ Β-1+Β-2 Β -1+Β-2 ώ PQ ώ r^i PQ ώ PQ ώ ώ A component weight ο ο ο ο Ο 1 < Ο * · < ο ^ ο ο » < ο ο 〇ο Ο ο ο »&quot ; < type polymer Al polymer Α-1 polymer Α-1 polymer Α-1 polymer Α-2 polymer Α-2 polymer Α-2 polymer Α-2 polymer Α-1 polymer Α -1 polymer Α-2 polymer A-2 polymer Α-1 polymer Α-1 Polymer Α-2 Polymer Α-2 Composition Type (Sl) (S-2) (S-3) (S-4) (S-5) (S-6) (S-7) (S-8 (S-9) (S-10) (S-ll) (S-12) (sl) § (s-4) Embodiment 1 Embodiment 2 1 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6 Implementation Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Comparative Example 1 Comparative Example 2 1 Comparative Example 3 Comparative Example 4 1379, 161 Table 2 Composition sensitivity profile shape separator strength honing resistance test close Heat resistance type (J/m2) Protrusion partition ((10) With or without peeling (/100) (%) Example 1 (S-1) 700 DB 0.6 No 100 80 Example 2 (S-2) 800 DB 0.7 No 100 81 Example 3 (S-3) 1000 DA 0.6 Μ 100 83 Example 4 (S-4) 1000 DB 0.8 No 100 82 Example 5 (S-5) 600 DB 0.7 5Ε 100 93 Example 6 (S-6 700 DB 0.7 No 100 93 Example 7 (S-7) 800 DA 0.9 No 100 92 Example 8 (S-8) 800 DB 0.8 Μ 100 90 Example 9 (S-9) 600 DB 0.6 Μ /1 100 80 Example 10 (S-10) 750 DB 0.7 4ττΤ. No 100 80 Example 11 (S-11) 600 DB 0.7 Am. No 100 92 Example 12 (S-12) 650 DB 0.7 No 100 92 Comparative Example 1 (s-1) 2000 EC 0.5 with 90 75 Comparative Example 2 (s-2) 2500 DA 0.7 Μ 100 78 Comparative Example 3 (s-3) 1800 DB 0.6 Μ /tw 100 89 Comparative Example 4 (s -4) 2200 DA 0.7 Ά n\\ 100 90 [Simplified description of the drawings] Fig. 1 is a schematic view showing the cross-sectional shape of the spacer. -51 -

Claims (1)

1379161 公告本 修正本 第 095111367 號1379161 Announcement Amendment No. 095111367 物之形成方法、 件」專利案Method of forming a piece of material, patent case [A]將下述（al)〜（a2)共聚而得到的共聚物，其中（ai) • 是不飽和羧酸及/或不飽和羧酸酐，U2)是（a Π成分以外的 其他不飽和化合物； 隔物的感放射線性樹脂組成物，其特徵在於：包括， [Β ]聚合性不飽和化合物；和 [C]由下式（1)或（2)所示的化合物所形成的感放射線 性聚合引發劑，[A] a copolymer obtained by copolymerizing the following (al) to (a2), wherein (ai) is an unsaturated carboxylic acid and/or an unsaturated carboxylic anhydride, and U2) is an unsaturated other than the a component a radiation-sensitive resin composition of a spacer, comprising: [Β] a polymerizable unsaturated compound; and [C] a radiation-sensitive agent formed of a compound represented by the following formula (1) or (2) Polymerization initiator, 其中’Ri是碳原子數爲1~20的垸基、碳原子數爲3〜8 的環院基或苯基，R_2、R3分別是氫原子、碳原子數爲1〜20 的院基、碳原子數爲3〜8的環院基、取代或未取代的苯 基、或碳原子數爲7〜20的脂環基（其中，碳原子數爲7〜8 的環烷基除外），上述取代苯基的取代基爲碳原子數爲 1~6的烷基、碳原子數爲1〜6的烷氧基、苯基或齒原子， 1379161 I v- 修正本 BU是碳原子數爲4〜20的含氧雜環基，r5是氫、碳原子 數爲1〜12的烷基或碳原子數爲u2的烷氧基，η是1〜5 的整數，m是0~2的整數，n+m2 5,Wherein 'Ri is a fluorenyl group having 1 to 20 carbon atoms, a ring-shaped group having 3 to 8 carbon atoms or a phenyl group, and R 2 and R 3 are each a hydrogen atom, a carbon atom having a carbon number of 1 to 20, and carbon. a ring-based group having 3 to 8 atoms, a substituted or unsubstituted phenyl group, or an alicyclic group having 7 to 20 carbon atoms (excluding a cycloalkyl group having 7 to 8 carbon atoms), and the above substitution The substituent of the phenyl group is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a phenyl group or a tooth atom, and 1379161 I v- modified Ben BU is a carbon number of 4 to 20 The oxygen-containing heterocyclic group, r5 is hydrogen, an alkyl group having 1 to 12 carbon atoms or an alkoxy group having a carbon number of u2, η is an integer of 1 to 5, m is an integer of 0 to 2, n+ M2 5, 述相同，1爲0〜6的整數，R, 、 r2 、 r3 、 r4 、 r5 、 m 、 以及1是相互獨立的。 2 . —種同時形成垂直配向型液晶顯示元件的突起和間隔物 的形成方法，其特徵在於：含有下述順序記載的下述步 驟， (1 )在基板上形成如申請專利範圍第1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，和 (4) 加熱步驟。 3.—種垂直配向型液晶顯示元件的突起和間隔物，其由如 申請專利範圍第2項之方法所形成。 4 _ 一種液晶顯示元件，其具有如申請專利範圍第3項之垂 直配向型液晶顯示元件的突起和間隔物。 -2-In the same manner, 1 is an integer of 0 to 6, and R, , r2, r3, r4, r5, m, and 1 are independent of each other. 2. A method of forming a protrusion and a spacer for simultaneously forming a vertical alignment type liquid crystal display element, comprising the following steps described in the following order, (1) forming on the substrate as in the first item of the patent application scope a step of sensing a coating film of the radiation composition, (2) a step of irradiating at least a portion of the coating film with radiation, (3) a developing step, and (4) a heating step. A protrusion and a spacer of a vertical alignment type liquid crystal display element, which are formed by the method of the second aspect of the patent application. A liquid crystal display element having projections and spacers of a vertical alignment type liquid crystal display element of claim 3 of the patent application. -2-
TW095111367A 2005-04-01 2006-03-31 Radiation sensitive resin composition, method for forming projections and spacers, projections and spacers, and liquid crystal display element with them TWI379161B (en)

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