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Publication number
TWI321702B
TWI321702B TW093111495A TW93111495A TWI321702B TW I321702 B TWI321702 B TW I321702B TW 093111495 A TW093111495 A TW 093111495A TW 93111495 A TW93111495 A TW 93111495A TW I321702 B TWI321702 B TW I321702B
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TW
Taiwan
Prior art keywords
liquid crystal
spacer
weight
alkali
crystal display
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TW093111495A
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Chinese (zh)
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TW200500802A (en
Inventor
Kimiyasu Sano
Takaki Minowa
Chie Saito
Michinori Nishikawa
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Jsr Corp
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Publication of TWI321702B publication Critical patent/TWI321702B/zh

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G9/00—Cultivation in receptacles, forcing-frames or greenhouses; Edging for beds, lawn or the like
    • A01G9/02—Receptacles, e.g. flower-pots or boxes; Glasses for cultivating flowers
    • A01G9/029—Receptacles for seedlings
    • A01G9/0295—Units comprising two or more connected receptacles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G9/00—Cultivation in receptacles, forcing-frames or greenhouses; Edging for beds, lawn or the like
    • A01G9/02—Receptacles, e.g. flower-pots or boxes; Glasses for cultivating flowers
    • A01G9/029—Receptacles for seedlings
    • A01G9/0293—Seed or shoot receptacles

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  • Life Sciences & Earth Sciences (AREA)
  • Environmental Sciences (AREA)
  • Materials For Photolithography (AREA)
  • Liquid Crystal (AREA)

Description

1321702 (1) 玖、發明說明 【發明所屬之技術領域】 本發明係有關形成垂直配向型液晶顯示元件用之突起 及/或間隔件之輻射敏感性樹脂組成物’由該組成物所形 成之垂直配向型液晶顯示元件用之突起及/或間隔件，具 備突起及/或間隔件之垂直配向型液晶顯不兀件及形成突 起及/或間隔件的方法。 【先前技術】 液晶顯示元件係平面面板顯示器中最被廣泛使用，隨 著近年個人電腦、文字處理機之OA設備或液晶電視等之 普及，對於TFT(薄膜電晶體）方式之液晶顯示器（TFT — LCD)之顯示品質之性能要求日趨嚴苛。 TFT — LCD中目前最被使用之方式係TN (扭轉向列）型 LCD，此方式係於具有二片透明電極之基板（以下稱爲透 明電極基板）之兩外側分別配置配向方向爲相差90度之的 偏光膜，而二片透明電極基板內側配置配向膜，並於兩配 向膜間配置向列型液晶，液晶之配向方向爲從一方之電極 側至另一方電極側扭轉90度。此狀態下，以無偏光之光 入射時，穿透其中之一偏光板之直線偏光因偏光方向偏移 的狀態下穿透液晶中，因此可穿透另一偏光板，成爲亮狀 態。其次，電壓施加兩電極，使液晶分子直立時，因抵達 液晶之直線偏光可直接穿透’因此無法穿透另一偏光板’ 成爲暗狀態。然後’形成不施加電壓狀態時’又回到亮狀 -5- (2) (2)1321702 難〇1321702 (1) Field of the Invention The present invention relates to a radiation-sensitive resin composition for forming a protrusion and/or a spacer for a vertical alignment type liquid crystal display element, which is formed vertically by the composition. A protrusion and/or a spacer for an alignment type liquid crystal display element, a vertical alignment type liquid crystal display element having a protrusion and/or a spacer, and a method of forming a protrusion and/or a spacer. [Prior Art] Liquid crystal display elements are the most widely used in flat panel displays. With the popularization of OA equipment or LCD TVs for personal computers and word processors in recent years, TFT (Thin Film Transistor) liquid crystal displays (TFT — The performance requirements for display quality of LCDs are becoming more stringent. TFT—The most commonly used method in LCD is the TN (Twisted Nematic) LCD. This method is to arrange the alignment direction at 90 degrees on both sides of the substrate with two transparent electrodes (hereinafter referred to as the transparent electrode substrate). In the polarizing film, an alignment film is disposed inside the two transparent electrode substrates, and a nematic liquid crystal is disposed between the two alignment films, and the alignment direction of the liquid crystal is twisted by 90 degrees from one electrode side to the other electrode side. In this state, when the light is incident on the unpolarized light, the linearly polarized light penetrating one of the polarizing plates penetrates the liquid crystal in a state where the polarization direction is shifted, so that it can penetrate the other polarizing plate and become a bright state. Next, when the voltage is applied to the two electrodes so that the liquid crystal molecules stand upright, the linearly polarized light reaching the liquid crystal can directly penetrate "and thus cannot penetrate the other polarizing plate" to become a dark state. Then 'when the voltage is not applied,' returns to bright. -5- (2) (2) 1321702

這種ΤΝ型LCD因近年技術改良，正面之對比或顏色 再現性等已相等或優於映像管（CRT)。然而，TN型LCD 視角狹窄爲一大問題。 爲解決此問題，而開發 MVA(Multi — domain Vertically Aligned)型 L C D (垂直配向型彩色液晶顯示 器）。 此 MVA 型 LCD 如「液晶」Vol.3，Νο·2，117(1999) 及曰本專利特開平丨1 — 25 8605號公報所記載，係利用組 合具有負介電率各向異性之負型液晶與垂直方向之配向膜 的雙折射模式，而非ΤΝ型LCD之旋光模式，即使在不施 加電壓狀態下，接近配向膜之液晶的配向方向大約維持垂 直’因此對比 '視角等優異，且也可不進行使液晶產生配 向之硏磨處理等，在製程上也具有優勢。 MVA型LCD中，在一像素區域內使液晶有多數配向 方向之區域規範手段：顯示側之電極於一像素區域內具有 狹縫者’同時於光入射側電極上同一像素區域內，與電極 之狹縫不同位置形成具有斜面之突起，例如三角錐狀、半 凸透鏡狀等。 一般而言，以往之液晶顯示器爲了將兩片透明電極基 板間之晶胞間隙維持一定，因此使用樹脂或陶瓷等之球形 或棒狀之間隔件。此間隔件貼於兩片透明電極基板時，散 佈於其中之一的基板上，間隔件係以間隔件之直徑來限 定。 -6- (3) (3)1321702 爲了避免因間隔件之直徑偏差造成晶胞間隙之不均勻 等的現象發生’因此日本特開2001-201750號公報提案 使用光阻形成突起及間隔件的方法。此方法具有可微細加 工’容易控制形狀之優點。但是日本特開2 00 1 — 20 1 750 號公報中未具體記載光阻之組成，形成之突起及間隔件之 性能也不明確。 形成垂直配向型液晶顯示元件用之突起及/或間隔件 之光阻所要求的性能：斷面形狀適當，·對於其後之配向膜 形成步驟所用之溶劑之耐性；對於配向膜形成步驟所施加 之熱的耐熱性、透明性、解像度、殘膜率等優異性能。製 得之垂直配向型液晶顯示元件需要優異的配向性、電壓保 持率等。 本案申請人已提案含有〔A〕（al)不飽和羧酸及/或不 飽和羧酸酐’（a2)含有環氧基之不飽和化合物及（a3)這些 以外之不飽和化合物’ [B ]不飽和聚合性化合物及[C ]輻射 敏感性聚合引發劑之同時形成突起及間隔件之輻射敏感性 樹脂組成物，由該組成物所形成之突起及間隔件，及具備 該突起及間隔件之液晶顯示元件（日本特開2 0 0 3 - 2 9 4 0 5 號公報）。 但是可用於形成垂直配向型液晶顯示元件之突起及/ 或間隔件之輻射敏感性樹脂組成物之開發僅剛開始，對於 TFT- LCD之急速普及及性能要求越來越嚴格，因此開發 具有優異性能之突起及間隔件之新的輻射敏感性樹脂組成 物成爲重要的技術。 1321702This type of LCD has been improved in recent years, and the front contrast or color reproducibility has been equal or better than the image tube (CRT). However, the narrow viewing angle of the TN type LCD is a big problem. To solve this problem, an MVA (Multi-domain Vertically Aligned) type L C D (vertical alignment type color liquid crystal display) was developed. The MVA type LCD is described in the "Liquid Crystal" Vol. 3, Ν · 2, 117 (1999), and the Japanese Patent Application Laid-Open No. Hei No. Hei. The birefringence mode of the alignment film of the liquid crystal and the vertical direction, and the optical rotation mode of the non-ΤΝ type LCD, even in the state where no voltage is applied, the alignment direction of the liquid crystal close to the alignment film is maintained to be approximately 'therefore, 'the contrast angle' is excellent, and also It is not necessary to perform honing treatment for aligning the liquid crystal, and it is also advantageous in the process. In an MVA type LCD, a region in which a liquid crystal has a plurality of alignment directions in a pixel region means that the electrode on the display side has a slit in a pixel region while being in the same pixel region on the light incident side electrode, and the electrode Protrusions having a slope, such as a triangular pyramid shape, a semi-convex lens shape, or the like, are formed at different positions of the slit. In general, in the conventional liquid crystal display, a spherical or rod-shaped spacer such as resin or ceramic is used in order to maintain a constant cell gap between the two transparent electrode substrates. When the spacer is attached to the two transparent electrode substrates, it is spread on one of the substrates, and the spacer is defined by the diameter of the spacer. -6- (3) (3) 1321702 In order to avoid the occurrence of unevenness of the cell gap due to the diameter deviation of the spacers, JP-A-2001-201750 proposes a method of forming a protrusion and a spacer using a photoresist. . This method has the advantage of being able to be finely processed to easily control the shape. However, the composition of the photoresist is not specifically described in Japanese Laid-Open Patent Publication No. 2000-201, and the performance of the formed projections and spacers is not clear. The properties required for forming the photoresist for the protrusions and/or spacers of the vertical alignment type liquid crystal display element: the cross-sectional shape is appropriate, the resistance to the solvent used in the subsequent alignment film formation step, and the application for the alignment film formation step The heat has excellent properties such as heat resistance, transparency, resolution, and residual film ratio. The vertically aligned liquid crystal display element produced requires excellent alignment, voltage retention, and the like. The applicant of the present application has proposed that [A] (al) unsaturated carboxylic acid and / or unsaturated carboxylic anhydride ' (a2) contains an epoxy group-containing unsaturated compound and (a3) other unsaturated compounds '[B] not a radiation-sensitive resin composition in which a protrusion and a spacer are simultaneously formed by a saturated polymerizable compound and a [C] radiation-sensitive polymerization initiator, protrusions and spacers formed of the composition, and liquid crystals having the protrusions and spacers Display element (Japanese Patent Publication No. 2 0 0 3 - 2 9 4 0 5). However, the development of a radiation-sensitive resin composition which can be used to form protrusions and/or spacers of a vertical alignment type liquid crystal display element has only just begun, and the rapid development and performance requirements of TFT-LCD have become stricter, so that development has excellent performance. The new radiation-sensitive resin composition of the protrusions and spacers has become an important technology. 1321702

【發明內容】 本發明之目的係提供形成垂直配向型液晶顯示元件用 之突起及/或間隔件之輻射敏感性樹脂組成物。 本發明之其他目的係提供光阻之解像度及殘膜率優 異’且可形成圖案形狀、耐熱性、耐溶劑性、透明性優異 之突起及間隔件，且可得到配向性、電壓保持率等優異之 垂直配向型液晶顯示元件的輻射敏感性樹脂組成物。 本發明之其他目的係提供使用本發明之上述輻射敏感 性樹脂組成物之垂直配向型液晶顯示元件用之突起及/或 間隔件的形成方法。 本發明之其他目的及優點如下述。 依據本發明時’本發明之上述目的及優點第〗可藉由 含有U)鹼可溶性樹脂及（b) 1，2 -苯醌二疊氮化合物，且 爲垂直配向型液晶顯示元件用之突起及/或間隔件之形成 用之輻射敏感性樹脂組成物來達成。 依據本發明時’本發明之上述目的及優點第2可藉由 本發明之輻射敏感性樹脂組成物所形成之垂直配向型液晶 顯示元件用突起來達成。 依據本發明時’本發明之上述目的及優點第3可藉由 本發明之輻射敏感性樹脂組成物所形成之垂直配向型液晶 顯示元件用間隔件來達成。 依據本發明時，本發明之上述目的及優點第4可藉由 本發明之具備上述突起及/或間隔件之垂直配向型液晶顯 (5) (5)1321702 示元件來達成。 依據本發明時’本發明之上述目的及優點第5可藉由 在基板上形成本發明之輻射敏感性樹脂組成物之被膜的步 驟；經由光罩對該被膜進行輻射曝光的步驟：將曝光後之 被膜以鹼顯像液顯像形成圖案之步驟；及對該圖案進行輻 射曝光之步驟所構成爲特徵之垂直配向型液晶顯示元件用 突起及/或間隔件之形成方法來達成。 發明之較佳的實施形態 以下詳細說明本發明之輻射敏感性樹脂組成物之各成 分。 (a)鹼可溶性樹脂 本發明用之鹼可溶性樹脂之「鹼可溶性」係指藉由下 述之突起及/或間隔件之形成方法，在基板上形成本發明 之輻射敏感性樹脂組成物之被膜，經曝光後，曝光後之該 被膜以鹼顯像顯像時，曝光後之該被膜之曝光部實質上全 部溶解除去的特性。 本發明用之鹸可溶性樹脂只要具有前述特性即無特別 限定。例如有具有苯酚性羥基及/或羧基之自由基聚合性 單體（以下稱爲「酸性自由基聚合性單體」）之單獨聚合 物、酸性自由基聚合性單體彼此之共聚物或酸性自由基聚 合性單體與其他之自由基聚合性單體（以下稱爲「其他自 由基聚合性單體」）之共聚物（以下這些單獨聚合物及共聚 (6) (6)1321702 物統稱爲「（a 1)鹼可溶性樹脂」）。 酸性自由基聚合性單體例如有鄰羥基苯乙烯、間羥基 苯乙烯、對羥基苯乙烯、鄰羥基- α —甲基苯乙烯、間羥 基一 α -甲基苯乙烯 '對羥基- α—甲基苯乙烯及這些化合 物中之苯環被選自羧基、碳數1〜4之直鏈或支鏈之烷 基、碳數1〜4之直鏈或支鏈之烷氧基、碳數1〜4之直鏈 或支鏈之鹵化烷基' 鹵原子、硝基、氰基、碳數1〜4之 直鏈或支鏈之醯胺基及碳數2〜8之直鏈或支鏈之酯基所 成群中至少一個基取代之取代羥基苯乙烯： 乙烯基對苯二酚、5—乙烯基焦掊酚、6-乙烯基焦掊 酚、1 -乙烯基氟乙醇胺等之聚羥基乙烯基多酚； 鄰乙烯基苯甲酸、間乙烯基苯甲酸、對乙烯基苯甲酸 及這些之苯環被選自碳數1〜4之直鏈或支鏈之烷基、碳 數1〜4之直鏈或支鏈之烷氧基、碳數1〜4之直鏈或支鏈 之鹵化烷基、鹵原子、硝基、氰基、碳數1〜4之直鏈或 支鏈之醯胺基及碳數2〜8之直鏈或支鏈之酯基所成群中 至少一個基取代之取代乙烯基苯甲酸； 丙烯酸、甲基丙烯酸及丙烯酸之α-位置被選自碳數 1〜4之直鏈或支鏈之烷氧基、碳數1〜4之直鏈或支鏈之 鹵化烷基、鹵原子、硝基及氰基所成群之基取代之α -取 代不飽和羧酸； 馬來酸、馬來酸酐、富馬酸、富馬酸酐' 檸康酸、中 康酸、衣康酸、1，4_環己烯二羧酸之不飽和羧酸及這些 不飽和羧酸中之羧基以甲基、乙基、正丙基、異丙基、正 -10- (7) (7)1321702 丁基、異丁基、第二丁基、第三丁基、苯基、鄰甲苯基、 間甲苯基或對甲苯基酯化之半酯、這些不飽和羧酸中之羧 基轉變成碳數1〜4之直鏈或支鏈之醯胺基之半醯胺之不 飽和羧酸眼生物等。 這些酸性自由基聚合性單體中較佳者爲間羥基苯乙 烯、對羥基苯乙烯、丙烯酸、甲基丙烯酸、馬來酸、馬來 酸酐、衣康酸等。 前述酸性自由基聚合性單體可單獨使用或混合兩種以 上使用。 其他自由基聚合性單體例如有苯乙烯、α-甲基苯乙 烯及這些化合物中之苯環被選自羧基、碳數1〜4之直鏈 或支鏈之烷基、碳數1〜4之直鏈或支鏈之烷氧基、碳數 1〜4之直鏈或支鏈之鹵化烷基' 鹵原子、硝基、氰基、 碳數1〜4之直鏈或支鏈之醯胺基及碳數2〜8之直鏈或支 鏈之酯基所成群中至少一個基取代之取代苯乙烯； 1 ’ 3— 丁二烯、異戊二烯、氯戊二烯之共軛二烯烴； 甲基（甲基）丙烯酸酯、乙基（甲基）丙烯酸酯、正丙基 (甲基）丙烯酸酯、異丙基（甲基）丙烯酸酯、正丁基（甲基） 丙烯酸酯、異丁基（甲基）丙烯酸酯、第二丁基（甲基）丙烯 酸酯、第三丁基（甲基）丙烯酸酯.正戊基（甲基）丙烯酸 酯' 新戊基（甲基）丙烯酸酯、異戊基（甲基）丙烯酸酯、月 桂基（甲基）丙烯酸酯、環己基（甲基）丙烯酸酯、烯丙基（甲 基）丙烯酸酯、丙炔基（甲基）丙烯酸酯、苯基（甲基）丙烯酸 酯、萘基（甲基）丙烯酸酯、蒽基（甲基）丙烯酸酯、蒽醌基 -11 - (8) (8)1321702 (甲基）丙烧酸醋' 胡椒基（甲基）丙嫌酸醋、水楊基（甲基） 丙烯酸酯、苯甲基（甲基）丙烯酸酯、苯乙基（甲基）丙烯酸 酯、甲苯基（甲基）丙烯酸酯 '三苯基甲基（甲基）丙烯酸 酯' 枯烯基（甲基）丙烯酸酯、金剛烷基（甲基）丙烯酸酯' 三環〔5.2.1.02 6〕癸烷—8 —基（甲基）丙烯酸酯、2_羥 乙基（甲基）丙烯酸酯、2-羥丙基（甲基）丙烯酸酯、 3 —羥丙基（甲基）丙烯酸酯、2，2，2 —三氟乙基（甲 基）丙烯酸酯、五氟乙基（甲基）丙烯酸酯、七氟正丙基（甲 基）丙烯酸酯、七氟異丙基（甲基）丙烯酸酯、縮水甘油基 (甲基）丙烯酸酯、2—（N，N—二甲胺基）乙基（甲基）丙烯酸 酯、3 -（Ν’ N-二甲胺基）丙基（甲基）丙烯酸酯、呋喃基 (甲基）丙烯酸酯、糠基（甲基）丙烯酸酯之（甲基）丙烯酸 酯； (甲基）丙烯腈、α—氯丙烯腈' 偏二氰乙烯之不飽和 腈化合物； 丙烯醛 '氯乙烯、偏氯乙烯、氟乙烯、偏氟乙烯、Ν 一乙烯基吡咯烷酮 '乙烯基吡啶、醋酸乙烯、Ν -苯基馬 來醯亞胺、Ν —（對羥基苯基）馬來醯亞胺、Ν —環己基馬來 醯亞胺、Ν -（甲基）丙烯醯基 基醯亞胺' Ν—丙烯醯基 基醯亞胺、對乙烯基苯甲基縮水甘油醚等。 這些其他自由基聚合性單體中，較佳者爲苯乙烯、 1，3- 丁二烯、苯基（甲基）丙烯酸酯、月桂基（甲基）丙烯 酸酯、三環〔5.2.1.02’6〕癸烷—8 —基（甲基）丙烯酸酯、 2 -羥乙基（甲基）丙烯酸酯、縮水甘油基（甲基）丙烯酸酯、 -12- (9) (9)1321702 N_環己基馬來醯亞胺、對乙烯基苯甲基縮水甘油醚等。 自由基聚合性單體可單獨使用或混合兩種以上使用。 U1)鹼可溶性樹脂中，其他自由基聚合性單體之共聚 比例係對於全單體100重量份時’爲60〜95重量份，更 理想爲65〜90重量份。此時其他自由基聚合性單體之共 聚比例低於60重量份時，有時製得之樹脂對於鹼顯像液 之溶解性太高，不易無法保持鹼顯像後之被膜之適當厚 度，超過95重量份時，有時製得之樹脂對於鹼顯像液之 溶解性不足。 本發明之（a 1 )鹼可溶性樹脂例如有聚（對羥基苯乙 烯）、對羥基苯乙烯/對羥基- α -甲基苯乙烯共聚物、對 羥基苯乙烯/苯乙烯共聚物、（甲基）丙烯酸/苯乙烯/縮水甘 油基（甲基）丙烯酸酯共聚物、（甲基）丙烯酸/苯乙烯/三環 〔5.2.1_02’6〕癸烷_8_基（甲基）丙烯酸酯共聚物、（甲基） 丙烯酸/苯乙烯/縮水甘油基（甲基）丙烯酸酯/Ν —環己基馬 來醯亞胺共聚物 '(甲基）丙烯酸/苯乙烯/縮水甘油基（甲基） 丙烯酸酯/Ν -環己基馬來醯亞胺/對乙烯基苯甲基縮水甘 油醚共聚物、（甲基）丙烯酸/苯乙烯/三環〔5.2.1.02’6〕癸 烷一 8 —基（甲基）丙烯酸酯/縮水甘油基（甲基）丙烯酸酯 /1，3 - 丁二烯共聚物、（甲基）丙烯酸/苯乙烯/三環 〔5.2.1.02’6〕癸烷—8_基（甲基）丙烯酸酯/縮水甘油基 (甲基）丙烧酸醋/對乙燒基苯甲基縮水甘油酸共聚物、（甲 基）丙烯酸/2 -羥乙基（甲基）丙烯酸酯/三環〔5_2·1·02·6〕 癸烷-8-基（甲基）丙烯酸酯/縮水甘油基（甲基）丙烯酸酯/ -13· (10) (10)1321702 對乙烯基苯甲基縮水甘油醚共聚物、（甲基）丙烯酸/月桂基 (甲基）丙烯酸酯/三環〔5.2.1.02’6〕癸烷一8—基（甲基）丙 烯酸酯/縮水甘油基（甲基）丙烯酸酯/對乙烯基苯甲基縮水 甘油醚共聚物、（甲基）丙烯酸/苯乙烯/三環〔 5.2.1.02 6〕 癸烷一8-基（甲基）丙烯酸酯/N-環己基馬來醯亞胺/1，3 —丁二烯共聚物等。 (a 1)鹼可溶性樹脂例如將酸性自由基聚合性單體視情 況與其他自由基聚合性單體在適當之溶劑中，使用自由基 聚合引發劑進行聚合來製造。 聚合用之溶劑例如有甲醇、乙醇、二丙酮醇等醇類； 四氫化呋喃、四氫化吡喃、二噁烷等之醚類；乙二醇單甲 醚、乙二醇單乙醚、乙二醇二甲醚、乙二醇二乙醚乙二醇 醚類；乙二醇甲醚乙酸酯、乙二醇單乙醚乙酸酯之乙二醇 烷醚乙酸酯類；二乙二醇單甲醚、二乙二醇單乙醚、二乙 二醇二甲醚、二乙二醇二乙醚、二乙二醇二乙基甲醚之二 乙二醇醚類；丙二醇甲醚、丙二醇乙醚、丙二醇單正丙 醚、丙二醇單正丁醚之丙二醇醚類；丙二醇甲醚乙酸酯、 丙二醇乙醚乙酸酯 '丙二醇正丙醚乙酸酯、丙二醇正丁醚 乙酸酯之丙二醇醒乙酸醋類；丙二醇甲醚丙酸酯、丙二醇 乙醚丙酸酯、丙二醇正丙醚丙酸酯、丙二醇正丁醚丙酸酯 等之丙二醇烷醚丙酸酯類；甲苯、二甲苯等之芳香族烴 類；甲基乙基酮、環己酮' 4一羥基—4 一甲基—2—戊酮 等之酮類； 醋酸甲酯、醋酸乙酯、醋酸正丙酯、醋酸正丁酯、羥 -14 - (11) (11)1321702 基醋酸甲酯、羥基醋酸乙酯、羥基醋酸正丁酯、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、乳酸甲酯、乳酸乙酯、 乳酸正丙酯、乳酸正丁酯、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-羥基一 2 —甲基丙酸甲酯' 2 —羥基_2 -甲基丙酸乙酯、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 一甲氧基丙酸正丁酯、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' 2—羥基一3_甲基丁酸甲 -15- (12) (12)1321702 紙等其他酯類。 這些溶媒之使用量係對於全自由基聚合性單體】〇〇重 量份時’理想爲使用20〜1，〇〇〇重量份。 聚合所使用之自由基聚合引發劑，例如有2，2，一偶 氮一異丁腈、2’ 2’一偶氮二—（2，4 —二甲基戊腈）、2， 2’一偶氮二—（4 —甲氧基一2，4 —二甲基戊腈）等之偶氮 化合物；過氧化苯酿' 過氧化月桂醯、第三丁基過三甲基 乙烯酯、1，1’ 一雙一（第三丁基過氧）環己烷等之有機過 氧化物；及過氧化氫。過氧化物與還原劑所構成之氧化還 原系引發劑等。 (al)鹼可溶性樹脂之另外的製造方法例如將前述自由 基聚合性單體之苯酚性羥基及/或羧基以烷基、乙醯基、 苯酿甲基等保護基保護之單體進行（共）聚合後，以水解 等除該保護基的方法。 本發明中，鹼可溶性樹脂含有碳一碳不飽和鍵時，可 經氫化後來使用，可調整透明性或軟化點。 鹼可溶性樹脂之聚苯乙烯換算重量平均分子量（以下 稱爲「Mw」）爲2,000〜100,000的範圍，理想爲3,000〜 50,000的範圍，特別理想爲5,000〜3〇,〇〇〇的範圍。具有 此範圍之Mw之鹸可溶性樹脂，可提到解像度、顯像性及 感度優異之輻射敏感性樹脂組成物，且可形狀及耐熱性優 異之突起及間隔件。 本發明之鹼可溶性樹脂之市售品例如有marukarinker 一 Μ、PH Μ — C(以上爲九善石油化學（股）製）、VP - -16- (13) (13)1321702 1500(日本曹達（股）製）等之羥基苯乙烯（共）聚合物或其部 分氫化物等。 本發明之鹼可溶性樹脂可單獨或混合兩種以上使用。 (b)l，2-醌二疊氮化合物 本發明使用之（b) 1，2 -醌二疊氮化合物係藉由輻射 線曝光產生羧酸之化合物，例如有1，2 -苯醌二疊氮- 4 —磺酸酯、〗，2_苯醌二疊氮_5-磺酸酯、1，2 —萘醌 二疊氮—4 一磺酸酯、1，2 —萘醌二疊氮一 5 —磺酸酯、 1，2 -苯醌二疊氮—4_磺酸醯胺、1，2 -苯醌二疊氮—5 一磺酸醯胺、1，2~萘醌二疊氮—4_磺酸醯胺、1，2_ 萘醌二疊氮一 5 —磺酸醯胺等，其中較佳者爲1，2-萘醌 二疊氮_4_磺酸酯、1，2 —萘醌二疊氮一 5 —磺酸酯。 I，2-萘醒二疊氮—4_擴酸醋、1，2 —萘醌二疊氮 _5 —磺酸酯之具體例有2，3，4一三羥基二苯甲酮_1， 2 -萘醌二疊氮—4—磺酸酯、2，3，4 -三羥基二苯甲酮 一 1，2 —萘醌二疊氮_5_磺酸酯、2，4，6 —三羥基二苯 甲酮_1，2—萘醌二疊氮—4一磺酸酯、2，4，6 —三羥基 二苯甲酮—1，2 —萘醌二疊氮—5 —磺酸酯等三羥基二苯. 甲酮之1，2_萘醌二疊氮一4一磺酸酯； 2，2，，4，4’ 一四羥基二苯甲酮—1，2_萘醌二疊氮 —4—磺酸酯、2，2，，4，4，一四羥基二苯甲酮一1，2 — 萘醌二疊氮一5 —磺酸酯' 2，3，4，3^四羥基二苯甲酮 _1，2_萘醌二疊氮—4一磺酸酯、2，3，4，3’一四羥基 二苯甲酮—1，2 —萘醌二疊氮一5 —磺酸酯、2，3，4，4’ -17- (14) (14)1321702 —四羥基二苯甲酮一 1，2 -萘醌二疊氮一 4 —磺酸酯、2, 3，4，4’ -四羥基二苯甲酮一1，2—萘醌二疊氮—5 —磺 酸酯、2，3，4，2’一四羥基_4，_甲基二苯甲嗣一 1，2 一萘醌二疊氮_4_磺酸酯、2’ 3’ 4，2’一四羥基—4’_ 甲基二苯甲酮一 1，2_萘醌二疊氮一 5_磺酸酯' 2，3, 4，4’_四羥基_3’ 一甲氧基二苯甲酮_1，2_萘醌二疊 氮一4 -磺酸酯、2，3，4，4’ 一四羥基_3’_甲氧基二苯 甲酮_1，2_萘醌二疊氮_5 -磺酸酯等之四羥基二苯甲 酮之1，2-萘醒二疊氮碯酸醋； 2，3，4，2，，6’_五羥基二苯甲酮_1，2 —萘醌二 疊氮_4_磺酸酯、2，3，4，2’’ 6’一五羥基二苯甲酮— 1，2 -萘醌二疊氮一 5 —磺酸酯等之五羥基二苯甲酮之 1，2-萘醌二疊氮磺酸酯； 2，4，6，3’，4’ ，5 —六控基一苯甲嗣_1’2 —蔡 醌二疊氮—4 —磺酸酯' 2，4，6，3，，4’，5’_六羥基二 苯甲酮一1，2_萘醌二疊氮一5_磺酸酯、3，4，5，3，， 4’ ，5’ —六羥基二苯甲酮_1，2_萘醌二疊氮_4一磺酸 酯、3，4，5，3，，4’ ，5’ 一六羥基二苯甲酮_1，2_萘 醌二疊氮一 5_磺酸酯等之六羥基二苯甲酮之1，2-萘醌 二疊氮磺酸酯： 雙（2，4_二控苯基）甲院一1，2—萘醌二疊氮—4 — 磺酸酯 '雙（2，4 —二羥苯基）甲烷一1，2_萘醌二疊氮一 5 —磺酸酯、雙（對羥苯基）甲烷_1，2_萘醌二疊氮—4 — 磺酸酯、雙（對羥苯基）甲烷一 1，2_萘醌二疊氮_5—磺 -18- (15) (15)1321702 酸酯、三（對羥苯基）甲烷一 1，2 -萘醌二疊氮一 4 一磺酸 酯、三（對羥苯基）甲烷一 1，2 -萘醌二疊氮—5_磺酸 酯、2，2，2 —三（對羥苯基）乙烷_1，2-萘醌二疊氮_4 _磺酸酯，2，2，2—三（對羥苯基）乙烷—1 ’ 2 —萘醌二 疊氮—5_磺酸酯、雙（2，3，4 —三羥苯基）甲烷一1，2-萘醌二疊氮—4 -磺酸酯、雙（2，3，4 —三羥苯基）甲烷— 1，2 —萘醌二疊氮-5—磺酸酯、2，2 -雙（2，3，4-三 羥苯基）丙烷_1，2-萘醌二疊氮_4_磺酸酯、2，2_雙 (2，3，4 -三羥苯基）丙烷_1，2-萘醌二疊氮_5_磺酸 酯、1，1，3 —三（2，5_二甲基_4一羥苯基）_3 —苯基 丙烷—1，2 —萘醌二疊氮—4一磺酸酯、1，1，1 一三（2, 5 —二甲基—4一羥苯基）一3_苯基丙烷_1，2 —萘醌二疊 氮—5 —礦酸醋、4，4’—〔1一〔4—〔1—〔4一控苯基〕 _1一甲基乙基〕苯基〕亞乙基〕雙酚一1，2_萘醌二疊 氮—4 一 磺酸酯、4，4’— 〔] — 〔4—〔1—〔4一羥苯基〕 —1—甲基乙基〕苯基〕亞乙基〕雙酚一1，2_萘醌二疊 氮一 5 —磺酸酯、雙（2，5 —二甲基一4_羥苯基）（2 —羥苯 基）甲烷一1，2 —萘醌二疊氮—4 -磺酸酯 '雙（2，5 -二 甲基一 4_羥苯基）（2_羥苯基）甲烷—1，2_萘醌二疊氮 —5 —磺酸酯、3，3，3，’ 3’一四甲基—1’ 1’一螺二 — 5，6，7，5，，6，，7’ 一 己醇一 1，2 -萘醌二疊氮-4—磺 酸酯 ' 3，3，3，，3, _ 四甲基一1，1，一螺二 _5，6， 7，5，，6’，7’ 一己醇_1，2 —萘醌二疊氮—5_磺酸酯、 2，2，4 —三甲基_7，2，，4’一三羥基黃烷一1，2_萘醌 -19- (16) (16)1321702 二疊氮_4_磺酸酯、2，2’ 4一三甲基_7’ 2’，4，_三 羥基黃烷_1，2_萘醌二疊氮一 5_磺酸酯、2 —甲基—2 一（2，4 —二羥苯基）_4_(4 一羥苯基）-7 -羥基色滿— 1，2_萘醌二疊氮—4一磺酸酯、2-甲基—2_(2，4_二 羥苯基）—4一（4 一羥苯基）—7_羥基色滿一 1，2—萘醌二 疊氮_5_磺酸酯、2 - [雙（5 —異丙基_4_羥基一 2 —甲 基苯基）甲基]苯酚一 1，2 —萘醌二疊氮_4_磺酸酯、2 — [雙（5_異丙基一4 —羥基_2 —甲基苯基）甲基]苯酚—1，2 —蔡醒二疊氮—5 —擴酸醋'1—〔1_ 〔3 -〔1_〔4_經 苯基〕_1_甲基乙基〕_4，6—二羥苯基〕_1_甲基乙 基〕—3_ 〔1— 〔3_ 〔1— 〔4_羥苯基〕—1-甲基乙 基〕一4，6_二經苯基〕—1_甲基乙基〕苯_1，2 —蔡 酿二疊氮一 4_磺酸醋、1_ 〔1— 〔3— 〔1_ 〔4 —經苯 基〕一1_甲基乙基〕_4，6_二羥苯基〕_1_甲基乙 基〕—3— 〔1一 〔3— 〔1— 〔4 —羥苯基〕—1-甲基乙 基〕—4，6 ——經苯基〕一 1 一甲基乙基〕苯_1，2_蔡 酸二疊氮—5 —擴酸醋、4，6 —雙〔1— (4 一經苯基）一1 — 甲基乙基〕一1，3 —二淫基苯一1，2 —蔡酸—疊氮一 4 — 磺酸酯、4，6_雙〔1-(4 —羥苯基）一1 一甲基乙基〕一 1，3_二羥基苯一 1，2 —萘醌二疊氮一 5_磺酸酯之聚（羥 苯基）烷之1，2-萘醌二疊氮磺酸酯等。 這些化合物外，可使用J. Kosar著” Light — Sensitive Systems” 339 — 352(1965)， John Wiley & Sons 公司或 W. S. De Forest 著 “Photoresist” 50(1975)， Me Graw — -20- (17) (17)1321702SUMMARY OF THE INVENTION An object of the present invention is to provide a radiation-sensitive resin composition for forming protrusions and/or spacers for a vertical alignment type liquid crystal display element. Another object of the present invention is to provide protrusions and spacers which are excellent in resolution and residual film ratio of photoresist, and which are excellent in pattern shape, heat resistance, solvent resistance, and transparency, and are excellent in alignment property and voltage holding ratio. A radiation-sensitive resin composition of a vertical alignment type liquid crystal display element. Another object of the present invention is to provide a method for forming a protrusion and/or a spacer for a vertical alignment type liquid crystal display element using the above radiation-sensitive resin composition of the present invention. Other objects and advantages of the present invention are as follows. According to the present invention, the above objects and advantages of the present invention can be achieved by containing U) an alkali-soluble resin and (b) 1,2-benzoquinonediazide compound, and are protrusions for a vertical alignment type liquid crystal display element. / or the formation of the spacer is achieved with a radiation-sensitive resin composition. According to the present invention, the above objects and advantages of the present invention can be attained by the protrusions for the vertical alignment type liquid crystal display element formed by the radiation-sensitive resin composition of the present invention. According to the present invention, the above objects and advantages of the present invention can be attained by a spacer for a vertical alignment type liquid crystal display device formed by the radiation-sensitive resin composition of the present invention. According to the present invention, the above objects and advantages of the present invention can be attained by the elements of the vertical alignment type liquid crystal display (5) (5) 1321702 of the present invention having the above-mentioned protrusions and/or spacers. According to the present invention, the above objects and advantages of the present invention can be achieved by the step of forming a film of the radiation-sensitive resin composition of the present invention on a substrate; the step of irradiating the film through a photomask: after exposure The film is formed by patterning with an alkali developing solution, and a method of forming a protrusion for a vertical alignment type liquid crystal display element and/or a spacer for forming the pattern by radiation exposure. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the components of the radiation-sensitive resin composition of the present invention will be described in detail. (a) Alkali-soluble resin The "alkali-soluble" of the alkali-soluble resin used in the present invention means that the film of the radiation-sensitive resin composition of the present invention is formed on a substrate by the following method for forming protrusions and/or spacers. After the exposure, after the exposure, the film is developed by alkali development, and the exposed portion of the film after exposure is substantially completely dissolved and removed. The bismuth soluble resin used in the present invention is not particularly limited as long as it has the aforementioned characteristics. For example, a single polymer of a radical polymerizable monomer having a phenolic hydroxyl group and/or a carboxyl group (hereinafter referred to as "acid radical polymerizable monomer"), a copolymer of acidic radical polymerizable monomers, or an acid free Copolymer of a base polymerizable monomer and another radical polymerizable monomer (hereinafter referred to as "other radical polymerizable monomer") (hereinafter, these individual polymers and copolymerization (6) (6) 1321702 are collectively referred to as " (a 1) Alkali soluble resin"). The acid radical polymerizable monomer is, for example, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o-hydroxy-α-methylstyrene, m-hydroxy-α-methylstyrene-p-hydroxy-α- The styrene and the benzene ring in these compounds are selected from a carboxyl group, a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched alkoxy group having 1 to 4 carbon atoms, and a carbon number of 1 to 4. a linear or branched halogenated alkyl group of 4, a halogen atom, a nitro group, a cyano group, a linear or branched decylamino group having 1 to 4 carbon atoms, and a linear or branched ester having 2 to 8 carbon atoms; Substituted hydroxystyrene substituted with at least one group in the group: polyhydroxyvinyl group such as vinyl hydroquinone, 5-vinyl pyrogallol, 6-vinyl pyrogallol, 1-vinylfluoroethanolamine Polyphenol; o-vinylbenzoic acid, m-vinylbenzoic acid, p-vinylbenzoic acid and benzene rings thereof are selected from a straight or branched alkyl group having a carbon number of 1 to 4, and a carbon number of 1 to 4 a chain or branched alkoxy group, a linear or branched halogenated alkyl group having 1 to 4 carbon atoms, a halogen atom, a nitro group, a cyano group, a linear or branched amidino group having 1 to 4 carbon atoms; a substituted vinyl benzoic acid substituted with at least one group of a linear or branched ester group of 2 to 8; the α-position of acrylic acid, methacrylic acid and acrylic acid is selected from a linear chain having a carbon number of 1 to 4 Or a branched alkoxy group, a linear or branched halogenated alkyl group having 1 to 4 carbon atoms, a halogen atom, a nitro group and a cyano group group-substituted α-substituted unsaturated carboxylic acid; maleic acid , maleic anhydride, fumaric acid, fumaric anhydride' citraconic acid, mesaconic acid, itaconic acid, 1,4-cyclohexene dicarboxylic acid unsaturated carboxylic acid and carboxyl groups in these unsaturated carboxylic acids Methyl, ethyl, n-propyl, isopropyl, n--10-(7) (7) 1321702 butyl, isobutyl, t-butyl, tert-butyl, phenyl, o-tolyl, inter A tolyl or p-tolyl esterified half ester, a carboxyl group in these unsaturated carboxylic acids, which is converted into a linear or branched guanamine group of a decylamine having a carbon number of 1 to 4, and an unsaturated carboxylic acid. Preferred among these acidic radical polymerizable monomers are m-hydroxystyrene, p-hydroxystyrene, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid and the like. The above acid radical polymerizable monomers may be used singly or in combination of two or more. Other radical polymerizable monomers such as styrene, α-methylstyrene, and a benzene ring of these compounds are selected from a carboxyl group, a linear or branched alkyl group having 1 to 4 carbon atoms, and a carbon number of 1 to 4. a linear or branched alkoxy group, a linear or branched halogenated alkyl group having 1 to 4 carbon atoms, a halogen atom, a nitro group, a cyano group, a linear or branched decylamine having 1 to 4 carbon atoms. a substituted styrene substituted with at least one group of a straight or branched chain ester group having 2 to 8 carbon atoms; 1 '3-butadiene, isoprene, chloroprene conjugated Olefins; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, Isobutyl (meth) acrylate, second butyl (meth) acrylate, tert-butyl (meth) acrylate. n-pentyl (meth) acrylate 'neopentyl (meth) acrylate Ester, isoamyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, allyl (meth) acrylate, c Alkynyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, decyl (meth) acrylate, decyl-11 - (8) (8) 1321702 ( Methyl)propanol vinegar ' pepper base (methyl) propylene vinegar, salicyl (meth) acrylate, benzyl (meth) acrylate, phenethyl (meth) acrylate, toluene (meth) acrylate 'triphenylmethyl (meth) acrylate ' cumenyl (meth) acrylate, adamantyl (meth) acrylate 'tricyclo [5.2.1.02 6] decane —8 —yl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2, 2 , 2-trifluoroethyl (meth) acrylate, pentafluoroethyl (meth) acrylate, heptafluoro-n-propyl (meth) acrylate, heptafluoroisopropyl (meth) acrylate, shrinkage Glyceryl (meth) acrylate, 2-(N,N-dimethylamino)ethyl (meth) acrylate, 3-(Ν' N-dimethylamino) propyl (methyl) Ethylenate, furyl (meth) acrylate, mercapto (meth) acrylate (meth) acrylate; (methyl) acrylonitrile, α-chloroacrylonitrile 'divinyl cyanohydrin unsaturated nitrile Acrolein 'vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, fluorene monovinylpyrrolidone 'vinyl pyridine, vinyl acetate, fluorenyl-phenylmaleimide, fluorene-(p-hydroxyphenyl) Maleic imine, Ν-cyclohexylmaleimide, Ν-(meth) propylene fluorenyl imine Ν 醯 醯 醯 醯 醯 醯 imine, p-vinyl benzyl glycidyl ether, etc. . Among these other radical polymerizable monomers, preferred are styrene, 1,3-butadiene, phenyl (meth) acrylate, lauryl (meth) acrylate, and tricyclo [5.2.1.02' 6] decane-8-yl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, -12- (9) (9) 1321702 N_ ring Hexamadrene, p-vinylbenzyl glycidyl ether, and the like. The radically polymerizable monomers may be used singly or in combination of two or more. In the alkali-soluble resin, the copolymerization ratio of the other radical polymerizable monomer is 60 to 95 parts by weight, more preferably 65 to 90 parts by weight, per 100 parts by weight of the total monomer. When the copolymerization ratio of the other radical polymerizable monomer is less than 60 parts by weight at this time, the solubility of the obtained resin to the alkali developing solution is too high, and it is difficult to maintain the proper thickness of the film after alkali development, and it is more than When the amount is 95 parts by weight, the solubility of the obtained resin may be insufficient for the alkali developing solution. The (a 1 ) alkali-soluble resin of the present invention is, for example, poly(p-hydroxystyrene), p-hydroxystyrene/p-hydroxy-α-methylstyrene copolymer, p-hydroxystyrene/styrene copolymer, (methyl) Acrylic/styrene/glycidyl (meth) acrylate copolymer, (meth)acrylic acid/styrene/tricyclo[5.2.1_02'6]decane-8-yl (meth) acrylate copolymer , (meth)acrylic acid/styrene/glycidyl (meth)acrylate/Ν-cyclohexylmaleimide copolymer '(meth)acrylic acid/styrene/glycidyl (meth) acrylate /Ν-cyclohexylmaleimide/p-vinylbenzyl glycidyl ether copolymer, (meth)acrylic acid/styrene/tricyclo[5.2.1.0''6]decane-8-yl (methyl Acrylate/glycidyl (meth) acrylate/1,3-butadiene copolymer, (meth)acrylic acid/styrene/tricyclo[5.2.1.0''6]decane-8-yl (A) Acrylate/glycidyl (meth) propyl sulphuric acid vinegar / p-ethyl benzyl methalic acid copolymer, (methyl) Acrylic acid / 2-hydroxyethyl (meth) acrylate / tricyclo [5_2 · 1 · 02 · 6] decane-8-yl (meth) acrylate / glycidyl (meth) acrylate / - 13· (10) (10)1321702 p-vinylbenzyl glycidyl ether copolymer, (meth)acrylic acid / lauryl (meth) acrylate / tricyclo [5.2.1.0''6] decane - 8 - (meth) acrylate / glycidyl (meth) acrylate / p-vinyl benzyl glycidyl ether copolymer, (meth) acrylate / styrene / tricyclo [5.2.1.02 6] decane 8-based (meth) acrylate / N-cyclohexyl maleimide / 1,3 - butadiene copolymer. (a1) The alkali-soluble resin is produced by, for example, polymerizing an acid radical polymerizable monomer with another radical polymerizable monomer in a suitable solvent using a radical polymerization initiator. Examples of the solvent for polymerization include alcohols such as methanol, ethanol, and diacetone; ethers such as tetrahydrofuran, tetrahydropyran, and dioxane; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol. Dimethyl ether, ethylene glycol diethyl ether glycol ether; ethylene glycol methyl ether acetate, ethylene glycol alkyl ether acetate of ethylene glycol monoethyl ether acetate; diethylene glycol monomethyl ether, Diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol diethyl ether diethylene glycol ether; propylene glycol methyl ether, propylene glycol ether, propylene glycol single positive Ether, propylene glycol mono-n-butyl ether propylene glycol ether; propylene glycol methyl ether acetate, propylene glycol diethyl ether acetate 'propylene glycol n-propyl ether acetate, propylene glycol n-butyl ether acetate propylene glycol acetate acetic acid; propylene glycol methyl ether Propylene glycol alkane propionate such as propionate, propylene glycol diethyl ether propionate, propylene glycol n-propyl ether propionate, propylene glycol n-butyl ether propionate; aromatic hydrocarbons such as toluene and xylene; methyl ethyl Ketones such as ketone and cyclohexanone ' 4-hydroxy-4-methyl-2-pentanone; methyl acetate , ethyl acetate, n-propyl acetate, n-butyl acetate, hydroxy-14 - (11) (11) 1321702 methyl acetate, ethyl hydroxyacetate, n-butyl hydroxyacetate, methyl methoxyacetate, Ethyl oxyacetate, n-propyl methoxyacetate, n-butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, n-propyl ethoxyacetate, n-butyl ethoxyacetate Ester, methyl n-propoxyacetate, ethyl n-propoxyacetate, n-propyl n-propoxyacetate, n-butyl n-propoxyacetate, methyl n-butoxyacetate, n-butoxyacetate Ester, n-propyl n-butoxyacetate, n-butyl n-butoxyacetate, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, methyl 3-hydroxypropionate, 3-hydroxypropyl Ethyl ethyl ester 'n-propyl propyl propionate, n-butyl 3-hydroxypropionate, methyl 2-hydroxy-2-methylpropanoate '2-hydroxy-2-methyl propionate, 2 — Methyl methoxypropionate, ethyl 2-methoxypropionate, n-propyl 2-methoxypropionate, n-butyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2 — Ethyl ethoxy propionate, 2 —n-propyl ethoxypropionate, n-butyl 2-ethoxypropionate, methyl 2-n-propoxypropionate, ethyl 2-n-propoxypropionate 2-n-propoxypropane N-propyl acrylate, n-butyl 2-n-propoxypropionate, methyl 2-n-butoxypropionate, ethyl 2-n-butoxypropionate, n-propyl 2-n-butoxypropionate , n-butyl 2-n-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-n-methoxypropionate, 3-methoxypropane N-butyl acrylate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, n-propyl 3-ethoxypropionate, n-butyl 3-ethoxypropionate, 3-positive Methyl propoxypropionate, ethyl 3-n-propoxypropionate, n-propyl 3-n-propoxypropionate, n-butyl 3-n-propoxypropionate, 3-n-butoxypropane Methyl ester, ethyl 3-n-butoxypropionate, n-propyl 3-n-butoxypropionate, n-butyl 3-n-butoxypropionate 2-hydroxy-3-methylbutyric acid -15- (12) (12) 1321702 Other esters such as paper. When the amount of these solvents is used for the total radical polymerizable monomer, the amount of the solvent is desirably 20 to 1, and the weight is used. The radical polymerization initiator used for the polymerization, for example, 2, 2, azo-isobutyronitrile, 2' 2'-azobis-(2,4-dimethylvaleronitrile), 2, 2'- An azo compound such as azobis(4-methoxy-2,4-dimethylvaleronitrile); benzene peroxide-peroxidized laurel, tributylperoxytrimethyl vinyl ester, 1, 1' an organic peroxide such as a double (t-butyl peroxy) cyclohexane; and hydrogen peroxide. An oxidation-reducing initiator composed of a peroxide and a reducing agent. (al) another method for producing an alkali-soluble resin, for example, a monomer in which a phenolic hydroxyl group and/or a carboxyl group of the radical polymerizable monomer is protected with a protecting group such as an alkyl group, an ethyl sulfonyl group or a phenylmethyl group; After the polymerization, the protecting group is removed by hydrolysis or the like. In the present invention, when the alkali-soluble resin contains a carbon-carbon unsaturated bond, it can be used after hydrogenation to adjust the transparency or softening point. The polystyrene-equivalent weight average molecular weight (hereinafter referred to as "Mw") of the alkali-soluble resin is in the range of 2,000 to 100,000, preferably in the range of 3,000 to 50,000, particularly preferably in the range of 5,000 to 3 Torr. As the soluble resin of Mw having such a range, a radiation-sensitive resin composition excellent in resolution, developability, and sensitivity can be mentioned, and protrusions and spacers excellent in shape and heat resistance can be mentioned. Commercially available products of the alkali-soluble resin of the present invention include, for example, marukarinker, PH Μ - C (above, Jiushan Petrochemical Co., Ltd.), VP - -16- (13) (13) 1321702 1500 (Japan Soda ( a hydroxystyrene (co)polymer or a partial hydride thereof, or the like. The alkali-soluble resin of the present invention can be used singly or in combination of two or more. (b) 1,2-quinonediazide compound (b) 1,2-quinonediazide compound used in the present invention is a compound which produces a carboxylic acid by radiation exposure, for example, 1,2-benzoquinone Nitrogen 4-sulfonate, 〗 2, benzoquinonediazide-5-sulfonate, 1,2-naphthoquinonediazide-4 sulfonate, 1,2-naphthoquinonediazide 5-sulfonate, 1,2-benzoquinonediazide-4-sulfonic acid decylamine, 1,2-benzoquinonediazide-5-sulfonic acid decylamine, 1,2-naphthoquinonediazide- 4_sulfonic acid decylamine, 1,2-naphthoquinonediazide-5-sulfonic acid decylamine, etc., of which 1,2-naphthoquinonediazide_4_sulfonate, 1,2-naphthyl is preferred. Bismuth azide-5-sulfonate. A specific example of I, 2-naphthalene diazide-4_expanded vinegar and 1,2-naphthoquinonediazide-5-sulfonate is 2,3,4-trihydroxybenzophenone-1. 2-naphthoquinonediazide-4-sulfonate, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide_5_sulfonate, 2,4,6-three Hydroxybenzophenone_1,2-naphthoquinonediazide-4-sulfonate, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate 1,3,2-naphthoquinonediazide-4 sulfonate; 2,2,,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinone Nitrogen 4-sulfonate, 2,2,4,4,tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate' 2,3,4,3^4 Hydroxybenzophenone_1,2-naphthoquinonediazide-4-sulfonate, 2,3,4,3'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5 Sulfonate, 2,3,4,4' -17- (14) (14)1321702 - tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-oxalate, 2, 3, 4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate Acid ester, 2,3,4,2'-tetrahydroxy-4,-methylbenzhydryl- 1,2-naphthoquinonediazide_4_sulfonate, 2' 3' 4,2' Tetrahydroxy-4'-methylbenzophenone-1,2-naphthoquinonediazide-5-sulfonate '2,3,4,4'-tetrahydroxy-3'-methoxybiphenyl Keto-1,2_naphthoquinonediazide 4- 4 sulfonate, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone-1,2-naphthoquinonediazide _5-sulfonic acid ester such as tetrahydroxybenzophenone 1,2-naphthalene diazide citrate; 2,3,4,2,6'-pentahydroxybenzophenone_1,2 - naphthoquinone diazide _4_ sulfonate, 2,3,4,2'' 6'-pentahydroxybenzophenone - 1,2-naphthoquinonediazide-5-sulfonate 1,2-naphthoquinonediazide sulfonate of hydroxybenzophenone; 2,4,6,3',4',5-hexa-controlled benzoquinone_1'2 - Cai 醌 叠 azide —4 —sulfonate ' 2,4,6,3,,4',5'-hexahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate, 3,4,5 ,3,,4' ,5'-hexahydroxybenzophenone_1,2-naphthoquinonediazide_4 monosulfonate, 3,4,5 1,2-naphthoquinonediazide sulfonic acid of hexahydroxybenzophenone such as 3,,4',5' hexahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate Acid ester: bis(2,4_diphenyl)aphthalene-1,2-naphthoquinonediazide-4 sulfonate 'bis(2,4-dihydroxyphenyl)methane-1,2_ Naphthoquinonediazide-5-sulfonate, bis(p-hydroxyphenyl)methane-1,2-naphthoquinonediazide-4-sulfonate, bis(p-hydroxyphenyl)methane-1,2_ Naphthoquinonediazide_5-sulfon-18-(15) (15)1321702 acid ester, tris(p-hydroxyphenyl)methane-1,2-naphthoquinonediazide-4 sulfonate, three (pair Hydroxyphenyl)methane-1,2-naphthoquinonediazide-5-sulfonate, 2,2,2-tris(p-hydroxyphenyl)ethane_1,2-naphthoquinonediazide_4 _ Sulfonate, 2,2,2-tris(p-hydroxyphenyl)ethane-1'2-naphthoquinonediazide-5-sulfonate, bis(2,3,4-trihydroxyphenyl)methane 1,2-naphthoquinonediazide-4-sulfonate, bis(2,3,4-trihydroxyphenyl)methane-1,2-naphthoquinonediazide-5-sulfonate, 2, 2-bis(2,3,4-trihydroxyphenyl)propane_1,2- Bismuth azide_4_sulfonate, 2,2_bis(2,3,4-trihydroxyphenyl)propane 1,2-naphthoquinonediazide_5_sulfonate, 1,1, 3-tris(2,5-dimethyl-4-ylhydroxyphenyl)_3-phenylpropane-1,2-naphthoquinonediazide-4-sulfonate, 1,1,1-three (2, 5-dimethyl-4-hydroxyphenyl)-3-phenylpropane_1,2-naphthoquinonediazide-5-mineral acid vinegar, 4,4'-[1 -[4-[1-[ 4-monophenyl] _1 monomethylethyl]phenyl]ethylidene bisphenol-1,2-naphthoquinonediazide-4 tetrasulfonate, 4,4'-[] - [4— [1-[4-Hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol-1,2-naphthoquinonediazide-5-sulfonate, double (2,5- Dimethyl-4-hydroxyphenyl)(2-hydroxyphenyl)methane-1,2-naphthoquinonediazide-4-sulfonate 'bis(2,5-dimethyl-4-hydroxyphenyl) (2_hydroxyphenyl)methane-1,2-naphthoquinonediazide-5-sulfonate, 3,3,3,' 3'-tetramethyl-1' 1'-snail II-5 6,7,5,,6,7'-hexanol-1,2-naphthoquinonediazide-4-sulfonate ' 3,3,3,,3, _ tetramethyl-1,1,-snail two_5,6, 7,5,,6',7'-hexanol-1,2-naphthoquinonediazide- 5_sulfonate, 2,2,4-trimethyl-7,2,4'-trihydroxyflavan-1,2-naphthoquinone-19- (16) (16)1321702 diazide_4 _ sulfonate, 2,2' 4 -trimethyl -7' 2', 4, _ trihydroxy flavan 1, 1 - naphthoquinone diazide-5 sulfonate, 2-methyl-2 Mono(2,4-dihydroxyphenyl)_4_(4-hydroxyphenyl)-7-hydroxychroman-1,2-naphthoquinonediazide-4-sulfonate, 2-methyl-2_(2 , 4_dihydroxyphenyl)-4-iso(4-hydroxyphenyl)-7-hydroxychroman, 1,2-naphthoquinonediazide_5_sulfonate, 2 - [double (5-isopropyl) _4_hydroxy-2-methylphenyl)methyl]phenol-1,2-naphthoquinonediazide_4_sulfonate, 2 — [bis(5-isopropyl-4-hydroxy-_2) —Methylphenyl)methyl]phenol—1,2—Cai Xing Diazide—5—Expanded vinegar '1—[1_[3 -[1_[4_Phenyl]_1_methylethyl] _4,6-Dihydroxyphenyl]_1_methylethyl]-3_[1-[3_[1-[4-hydroxyphenyl]-1-methylethyl] a 4,6-di-phenyl]-l-methylethyl]benzene_1,2 - Cai brewed diazide-4_sulfonic acid vinegar, 1_[1—[3—[1_[4--benzene —1—Methylethyl]_4,6-dihydroxyphenyl]_1_methylethyl]-3—[1—[3-[1-[4-hydroxyphenyl]-1-methyl Ethyl]-4,6-Phenyl]-l-methylethyl]benzene_1,2_carotic acid diazide-5-acid vinegar, 4,6-bis[1—(4 Phenyl)-1 -methylethyl]-1,3-dipronylbenzene-1,2-cacoic acid-azido-4-sulfonate, 4,6-bis[1-(4-hydroxybenzene) 1,2-naphthoquinone di(1,3-naphthoquinone) of 1,1-methyl-hydroxyethyl-1,2-dihydroxybenzene-1,2-naphthoquinonediazide-5-sulfonate Azide sulfonate and the like. In addition to these compounds, J. Kosar can be used with "Light — Sensitive Systems" 339 — 352 (1965), John Wiley & Sons or WS De Forest with “Photoresist” 50 (1975), Me Graw — -20- (17 ) (17)1321702

Hill > Inc.所記載之1’ 2 -萘醌二疊氮-4—磺酸酯或 1，2—萘醌二疊氮一 5-磺酸酯。 這些1,2 —萘醌二疊氮一 4~磺酸酯及1’ 2—萘醌二 疊氮一5 —磺酸酯中，較佳者爲】，2 -萘醌二疊氮一5 -磺酸酯’特別理想爲2’3’4 —三羥基二苯甲酮—]’2一 萘醌二疊氮一 5-磺酸酯、2’ 3’ 4’ 3’一四羥基二苯甲酮 _1，2 —萘醌二疊氮—5—磺酸酯、1 ’】’ 3—三（2’ 5 — 二甲基—4 —羥苯基）—3 —苯基丙烷—1，2—萘醌二疊氮 —5 —磺酸酯、4，4, - 4，4’ 一 [ 1 - ( 4 - 〔1- 〔4 一羥 苯基〕一 1-甲基乙基〕苯基〕亞乙基〕雙酚一1，2-萘 醌二疊氮—5—磺酸酯、2，2，4一三甲基一 7，2’，4’ 一 三羥基黃烷一1，2—萘醌二疊氮一 5—磺酸酯、2 —甲基一 2 -（2，4 一二羥苯基）一 4 — (4 —羥苯基）—7—羥基色滿一 1，2 —萘醌二疊氮—5 —磺酸酯等可用於抑制（a)鹼可溶性 樹脂溶解於鹼顯像液的效果。 前述1，2 -醌二疊氮化合物可單獨或混合兩種以上 使用。 1，2-醌二疊氮化合物之添加量係對於（a)鹼可溶性 樹脂100重量份時，添加5〜50重量份，更理想爲]0〜 40重量份。此1，2-醌二疊氮化合物之添加量低於5重 量份時，曝光產生之羧酸量降低’圖案不易形成，又超過 50重量份時，以短時間曝光有時無法完全分解所添加之 1，2 —醌二疊氮化合物，利用鹼顯像液之顯像困難。 1321702 8) 加 添 可 中 物 成 組 脂 樹 性 感 敏 射 輻 之 y 月 齊 Φ 加發 添本 述 下 以 式1'2-naphthoquinonediazide-4-sulfonate or 1,2-naphthoquinonediazide-5-sulfonate described by Hill > Inc. Among these 1,2-naphthoquinonediazide-4-sulfonate and 1'2-naphthoquinonediazide-5-sulfonate, preferably, 2-naphthoquinonediazide-5- The sulfonate 'is particularly ideally 2'3'4-trihydroxybenzophenone-]'2-naphthoquinonediazide-5-sulfonate, 2' 3' 4' 3'-tetrahydroxydiphenyl Keto-1,2-naphthoquinonediazide-5-sulfonate, 1 ']' 3-tris(2' 5-dimethyl-4-hydroxyphenyl)-3-phenylpropane-1,2 -naphthoquinonediazide-5-sulfonate, 4,4,-4,4'-[1 -(4-[1-[4-hydroxyphenyl]-l-methylethyl]phenyl] Ethylene]bisphenol-1,2-naphthoquinonediazide-5-sulfonate, 2,2,4-trimethyl-7,2',4'-trihydroxyflavan-1,2- Naphthoquinonediazide-5-sulfonate, 2-methyl-2-(2,4-dihydroxyphenyl)-4-(4-hydroxyphenyl)-7-hydroxychroman-1,2 — Naphthoquinone diazide-5-sulfonate or the like can be used for suppressing the effect of (a) the alkali-soluble resin being dissolved in the alkali developing solution. The above-mentioned 1,2-quinonediazide compound may be used alone or in combination of two or more. The amount of the 1,2-quinonediazide compound to be added is 5 to 50 parts by weight, more preferably 0 to 40 parts by weight, based on 100 parts by weight of the (a) alkali-soluble resin. When the amount of the azide compound added is less than 5 parts by weight, the amount of the carboxylic acid produced by the exposure is lowered, 'the pattern is not easily formed, and when it exceeds 50 parts by weight, the exposure may not be completely decomposed in a short time, and the added 1,2 - 2 Azide compound, difficult to develop with alkali imaging solution. 1321702 8) Adding a smear of a group of lipid trees to the sensitive sensitivity of the y.

(式中’ R〜R6係互相獨立之氫原子或_CH2OR基 -’ R爲氫原子或碳數1〜6之直鏈或支鏈狀之烷基）表示 之化合物（以下稱爲「化合物（c)」）及/或（d)分子內具有2 個以上之環氧基之鹼不溶性或鹼難溶性之化合物（以下稱 爲「化合物（d)」）。 一化合物（c) — 化合物（〇例如有六羥甲基三聚氰胺、六羥丁基三聚 氰胺 '部分羥甲基化三聚氰胺及這些化合物中之至少一個 徑基之氫原子被碳數1〜6之直鏈或支鏈之烷基取代之化 合物等。 化合物（c)之市售品例如有S i m e 1 2 0 2、2 3 8、2 6 6、 267 ' 272 、 300 、 301 、 303 、 325 、 327 、 370 、 701 、 1141、1156' 1158(以上爲三井 Sianzmid(股）製）、Nikalac Mx- 31、40、45、03 2、706、708、750、Nikalac Ms -]1、00]、Nikalac Mw — 22、30(以上爲三和 Chemical 公 -22- (19) (19)1321702 司製）等。 化合物（c)可單獨或混合兩種以上使用。 使用化合物（c)時之添加量對於（a)鹼可溶性樹脂1〇〇 重量份時，添加1〜50重量份，更理想爲5〜40重量份。 添加此範圍之化合物（c)可形成良好形狀之突起及間隔 件，且可得到對於鹼顯像液具有適當溶解性之輻射敏感性 樹脂組成物。 一化合物（d) — 化合物（d)例如有雙酚A型環氧樹脂、雙酚F型環氧 樹脂、酚醛淸漆型環氧樹脂、酚醛淸漆型環氧樹脂、環脂 肪族聚縮水甘油醚、脂肪族聚縮水甘油醚、雙酚A之縮 水甘油醚、雙酚F型之縮水甘油醚等。 這些化合物（d)中，從輻射敏感性樹脂組成物之鹼顯 像性與製得之突起及間隔件之形狀控制的觀點，較佳者爲 雙酚A型環氧樹脂、雙酚F型環氧樹脂、酚醛淸漆型環 氧樹脂、酚醛淸漆型環氧樹脂、脂肪族聚縮水甘油醚。 化合物（d)之市售品例如有 Epycoat 82 8、1001、 1002、 1003、 1004' 1007、 1009、 1010(油化 Shell(wherein R to R6 are mutually independent hydrogen atoms or _CH2OR group - 'R is a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms) (hereinafter referred to as "compound ( c)") and/or (d) a compound having two or more epoxy groups in an alkali-insoluble or alkali-insoluble (hereinafter referred to as "compound (d)"). a compound (c) - a compound (for example, hexamethylol melamine, hexahydroxybutyl melamine), partially methylolated melamine, and at least one of these compounds, a hydrogen atom of a carbon number of 1 to 6 Or a branched alkyl substituted compound, etc. Commercial products of the compound (c) are, for example, Sime 1 2 0 2, 2 3 8 , 2 6 6 , 267 ' 272 , 300 , 301 , 303 , 325 , 327 , 370, 701, 1141, 1156' 1158 (above is Mitsui Sianzmid (share)), Nikalac Mx- 31, 40, 45, 03 2, 706, 708, 750, Nikalac Ms -] 1, 00], Nikalac Mw — 22, 30 (The above is the three and Chemical Gong-22- (19) (19) 1321702 system), etc. The compound (c) may be used alone or in combination of two or more. The amount of addition when using the compound (c) is (a) When the alkali-soluble resin is used in an amount of 1 part by weight, it is added in an amount of 1 to 50 parts by weight, more preferably 5 to 40 parts by weight. The compound (c) in this range is added to form a protrusion and a spacer of a good shape, and a base can be obtained. The developing solution has a radiation-sensitive resin composition having a suitable solubility. A compound (d) - The compound (d) is, for example, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenolic lacquer type epoxy resin, a phenolic lacquer type epoxy resin, a cycloaliphatic polyglycidyl ether, an aliphatic polycondensation water. Glycidyl ether, glycidyl ether of bisphenol A, glycidyl ether of bisphenol F type, etc. Among these compounds (d), the alkali developability of the radiation-sensitive resin composition and the shape of the resulting protrusions and spacers The control point of view is preferably bisphenol A epoxy resin, bisphenol F epoxy resin, phenolic lacquer epoxy resin, phenolic lacquer epoxy resin, aliphatic polyglycidyl ether. Commercial products such as Epycoat 82 8, 1001, 1002, 1003, 1004' 1007, 1009, 1010 (oiled shell)

Epox(股）製）等雙酚 A型環氧樹脂；Epycoat 807(油化 Shell Epox(股）製）等之雙酚F型環氧樹脂；Epycoat 152、 154(油化 Shell Epox(股）製）、EPPN 201' 202(日本化藥 (股）製）等之苯酚酚醛型環氧樹脂：EOCN-102、103S、 1 04S、1 020、1 02 5 ' 1 02 7(日本化藥（股）製）、Epycoat -23- (20) (20)1321702 180S75(油化 She丨1 Epox(股）製）等之甲階酚醛型環氧樹 脂；CY-175、177、179(Ciba gaigy 公司製）、ERL — 4206 ' 4221、4234、4299(U.C.C(股）製）、Shodine 509( B召 和電工（股）製）、Aldalite CY - 182、184、i92(Ciba gaigy(公司）製）、Epyclone 200、400(大日本油墨（股） 製）、Epycoat 871、872(油化 Shell Epox(股）製）、ED -5 66 1、5662(Ceraneedscoating(股）製）等之環脂肪族環氧樹 脂；Epolite 100MF(共榮社油脂化學工業（股）製）、Epyol TMP(日本油脂（股）製）等之脂肪族聚縮水甘油醚。 前述化合物（d)可單獨或混合兩種以上使用。 使用化合物（d)時之添加量對於（a)鹼可溶性樹脂100 重量份時，添加1〜50重量份，更理想爲5〜30重量份。 添加此範圍之化合物（d)可形成耐熱性及耐摩擦性優異之 突起及間隔件。化合物（d)之添加量低於1重量份時， (b)l，2-醌二疊氮化合物與曝光所生成之羧酸之反應不 易充分進行，且形成之突起及間隔件之耐熱性或耐溶劑性 可能不良，又超過50重量份時，形成之突起及間隔件之 軟化點降低，這些之形成步驟之加熱處理中，有時很難維 持形狀。 其他之添加劑 本發明之輻射敏感性樹脂組成物中必要時可添加下述 之其他之添加劑。 -24 - (21) 1321702 一增感劑一 增感劑係具有可提高輻射敏感性樹脂組成物之感度的 作用。 這種增感劑例如有2 Η -吡啶—（3 ’ 2 - b) — ] ’ 4 一噁 嗪- 3(4H)—酮類、10H -吡啶一（3’ 2 - b)-(l，4)-苯並 噻嗪類、尿唑類、乙內醯尿類、丙二醯尿類、甘氨酸酐 類、I -羥基苯並三唑類、阿尿類、順丁醯二胺類、黃酮 類、二苄叉丙酮類、二苄叉環己酮類、芳基丙烯醯芳烴 類、咕_類 '硫咕噸類、叶琳、社菁類、D丫 U定類、葱類、 二苯甲酮類、苯乙酮類、在第3位置及/或第7位置上具 ~取代基之香豆素類等。 道些增感劑可單獨或混合兩種以上使用。 增感劑之添加量係（a)鹼可溶性樹脂1〇〇重量份時， 添加30重量份以下，理想爲〇〜2〇重量份。 〜含三鹵甲基一S —三嗪〜 含三鹵甲基一S —Epoxy A type epoxy resin such as Epox (manufactured by Epox); bisphenol F type epoxy resin such as Epycoat 807 (oiled by Shell Epox); Epycoat 152, 154 (oiled Shell Epox) ), phenol novolac type epoxy resin such as EPPN 201' 202 (manufactured by Nippon Kayaku Co., Ltd.): EOCN-102, 103S, 1 04S, 1 020, 1 02 5 ' 1 02 7 (Nippon Chemical Co., Ltd.) , Epycoat -23- (20) (20) 1321702 180S75 (oiled She丨1 Epox (manufactured)), etc., a resol type epoxy resin; CY-175, 177, 179 (Ciba gaigy company) , ERL — 4206 ' 4221, 4234, 4299 (UCC), Shodine 509 (B Call and Electrician), Aldalite CY - 182, 184, i92 (Ciba gaigy (company)), Epyclone 200 , a cycloaliphatic epoxy resin such as 400 (manufactured by Dainippon Ink Co., Ltd.), Epycoat 871, 872 (manufactured by Oiled Shell Epox Co., Ltd.), ED-566 1, and 5662 (Ceraneedscoating Co., Ltd.); An aliphatic polyglycidyl ether such as Epolite 100MF (manufactured by Kyoei Oil & Fat Chemicals Co., Ltd.) or Epyol TMP (manufactured by Nippon Oil & Fats Co., Ltd.). The above compound (d) may be used singly or in combination of two or more. The amount of the compound (d) to be added is 1 to 50 parts by weight, more preferably 5 to 30 parts by weight, per 100 parts by weight of the (a) alkali-soluble resin. The addition of the compound (d) in this range forms a projection and a spacer excellent in heat resistance and abrasion resistance. When the amount of the compound (d) added is less than 1 part by weight, the reaction of the (b) 1,2-quinonediazide compound with the carboxylic acid formed by the exposure is not sufficiently performed, and the heat resistance of the formed protrusion and the spacer or The solvent resistance may be poor. When the amount is more than 50 parts by weight, the softening point of the formed protrusions and the spacers is lowered, and in the heat treatment of the forming step, it may be difficult to maintain the shape. Other Additives The radiation-sensitive resin composition of the present invention may be added with other additives as described below as necessary. -24 - (21) 1321702 A sensitizer-sensitizer has the effect of increasing the sensitivity of the radiation-sensitive resin composition. Such sensitizers are, for example, 2 Η-pyridine-(3 ' 2 - b) — ] 4 tetraoxazin-3(4H)-ketones, 10H-pyridine-(3' 2 - b)-(l, 4)-benzothiazide, urinazole, intrathyroid, urethane, glycine anhydride, I-hydroxybenzotriazole, anuria, cis-butane diamine, flavonoids Class, dibenzylidene acetonide, dibenzylidenecyclohexanone, aryl propylene fluorene aromatic hydrocarbons, 咕_class thiophene quinone, YE Lin, 社菁, D丫U categorized, onion, diphenyl A ketone or an acetophenone, a coumarin having a substituent at the third position and/or the seventh position. These sensitizers may be used singly or in combination of two or more. When the amount of the sensitizer added is (a) 1 part by weight of the alkali-soluble resin, 30 parts by weight or less is added, and preferably 〇 2 2 parts by weight. ~ contains trihalomethyl-S-triazine~ contains trihalomethyl-S-

化合物所Compound institute

〔式中X係表示鹵原子 A係一 CX3或以下述式⑴ '25- 1321702Wherein X represents a halogen atom, A is a CX3 or is represented by the following formula (1) '25- 1321702

表示之基，B、D及E係分別爲氫原子、鹵原子、氰 基、硝基、羧基、碳數1〜10之直鏈或支鏈狀之烷基、碳 數6〜12之芳基、碳數1〜10之直鏈或支鏈狀之烷氧基' 碳數1〜10之直鏈或支鏈狀之烷硫基、碳數6〜12之芳氧 基、碳數6〜12之芳硫基、具有碳數1〜1〇之直鏈或支鏈 狀之烷基之二級胺基、碳數1〜10之直鏈或支鏈狀之酮烷 基、碳數6〜12之酮芳基、碳數2〜20之直鏈或支鏈狀之 烷氧基羰基或碳數2〜20之直鏈或支鏈狀之烷基羰氧基， m爲1〜5之整數。 含三鹵甲基一S-三嗪例如有2，4，6_三（三氯甲基） _S —二曝、2—苯基—4，6-雙（三氯甲基）一 S—三嗪、2 -(4-氯苯基）一 4，6 —雙（三氯甲基）一S —三嗪、2-(3-氯苯基）—4，6 —雙（三氯甲基）一S —三嗪、2—（2-氯苯基） • 26 - (23) (23)1321702 —4，6_雙（三氯甲基）_S —三嗪、2—（4 —甲氧基苯基）— 4，6 -雙（三氯甲基）一S —三嗪、2-(3 -甲氧基苯基）一 4，6 -雙（三氯甲基）一S —三嗪、2 - (2 —甲氧基苯基）一 4，6 —雙（三氯甲基）-S -三嗪、2 -（4-甲基苯硫基）一 4，6 -雙（三氯甲基）一S_三嗪、2 - (3 —甲基苯硫基）-4，6 —雙（三氯甲基）一S—三嗪' 2-(2 -甲基苯硫基）一 4，6——雙（三氯甲基）_S —三嗪、2_(4_甲氧基一β — 苯乙烯基）一4，6 —雙（三氯甲基）—S_三嗪' 2— (3_甲氧 基_β_苯乙烯基）—4，6—雙（三氯甲基）_S —三嗪、2-(2 —甲氧基_β —苯乙烯基）_4，6_雙（三氯甲基）一S -三 嗪、2_(3，4，5 —三甲氧基一β_苯乙烯基）_4，6 —雙 (三氯甲基）一S —三嗪、2— (4_甲硫基一β -苯乙烯基）一 4，6—雙（三氯甲基）一S —三嗪、2 — (3_甲硫基一β_苯 乙烯基）一4，6 —雙（三氯甲基）一S—三嗪' 2_(2 —甲硫基 _β —苯乙烯基）一4，6 —雙（三氯甲基）一S -三嗪、2— (4 —甲氧基萘基）一4，6 —雙（三氯甲基）一S —三嗪、2— (3 — 甲氧基萘基）_4，6 —雙（三氯甲基）一 S —三嗪' 2_(2—甲 氧基萘基）_4，6_雙（三氯甲基）_S —三嗪等。 這些化合物中較佳者爲2 — (3 _氯苯基）_4，6-雙 (三氯甲基）_S —三嗪' 2_(4_甲氧基苯基）一4，6_雙 (三氯甲基）_S_三嗪、2_(4 —甲基苯硫基）_4，6 —雙 (二氯甲基）一S_二曉、2— (4 —甲氧基一β_苯乙燒基）~ 4，6_雙（三氯甲基）一S —三嗪、2 -（4_甲氧基萘基）一 4，6 -雙（三氯甲基）_S —三嗪等。 -27- (24) (24)1321702 則述.含二®甲基一 S —二曉可單獨使用或混合兩種以 上使用。 含二齒甲基_ S -三曉之添加量係對於（a)驗可溶性樹 脂1 0 0重量份時，添加1 〇重量份以下，理想爲1 〇重量份 以下，更理想爲5重量份以下。 -其他含苯酚性羥基之低分子化合物- 其他含苯酚性羥基之低分子化合物例如有1，1 一雙 (2’ 5 ——甲基一4 —經苯基）丙嗣、1’ 1—雙（2，4 —二經 苯基）丙酮、1，1—雙（2，6_二甲基一 4 一羥苯基）丙酮、 4’ 6 -雙〔1— (4 —羥苯基）—1-甲基乙基〕—丨，3 —二 經基苯、4’ 6 —雙〔i-(4 —羥苯基）一1—甲基乙基〕— 1，3—二羥基一2一甲基苯等。 這些其他含苯酚性羥基之低分子化合物可單獨使用或 混合兩種以上使用。 g t '丨生羥基之低分子化合物之添加量係對於（a) 驗可溶性樹脂1 00重量份時，添加50重量份以下，理想 爲45重量份以下。 -鎗鹽化合物〜 鐺鹽化合物係以下述式（3) (A ) n Z Υ -28- (25) (25)1321702 〔式中A之定義係與上述一般式（2)相同，η爲2或 3; Ζ+表示 S+或 I+ ； Y一 係表示 BF4_、PF6 、SbF6 -、 AsFT、對甲苯磺酸陰離子、三氟甲烷磺酸陰離子或三氟 乙酸陰離子〕表示之化合物所構成。 鎰鹽化合物例如有二苯基碘錙四氟硼酸酯、二苯基碘 鑰六氟磷酸酯、二苯基碘鎰六氟砷酸酯、二苯基碘鎰三氟 甲烷磺酸酯、二苯基碘鎗三氟乙酸酯、二苯基碘鐵對甲苯 磺酸酯、4一甲氧基苯基苯基碘鑰四氟硼酸酯、4-甲氧基 苯基苯基碘鎰六氟磷酸酯、4一甲氧基苯基苯基碘鎰三氟 甲烷磺酸酯、4 -甲氧基苯基苯基碘鍚三氟乙酸酯、4一甲 氧基苯基苯基碘鎰-對甲苯磺酸酯、雙（4-第三丁基苯基） 碘鎗四氟硼酸酯、雙（4 一第三丁基苯基）碘鐵六氟磷酸 酯、雙（4-第三丁基苯基）碘鎗六氟胂酸酯、雙（4-第三 丁基苯基）碘鎗三氟甲烷磺酸酯、雙（4 -第三丁基苯基）碘 鐵三氟乙酸酯、雙（4 —第三丁基苯基）碘鎗對甲苯磺酸酯 等之二芳基碘鎗鹽； 三苯基锍四氟硼酸酯、三苯基锍六氟磷酸酯、三苯基 锍六氟胂酸酯、三苯基銃三氟甲烷磺酸酯、三苯基锍三氟 乙酸酯、三苯基銃一對甲苯磺酸酯、4 一甲氧基苯基二苯 基銃四氟硼酸酯、4 -甲氧基苯基二苯基锍六氟磷酸酯、4 -甲氧基苯基二苯基銃六氟砷酸酯、4 -甲氧基苯基二苯 基锍三氟甲烷磺酸酯、4_甲氧基苯基二苯基銃三氟乙酸 酯、4一甲氧基苯基二苯基锍一對甲苯磺酸酯、4 —苯基硫 代苯基二苯基銃四氟硼酸酯、4-甲基硫代苯基二苯基銃 -29- (26) (26)1321702 六氟磷酸醋、4-苯基硫代苯基二苯基锍六氟胂酸酯、4一 苯基硫代苯基二苯基锍三氟甲烷磺酸酯、4-苯基硫代苯 基二苯基锍三氟乙酸酯、4_苯基硫代苯基二苯基銃-對 甲苯磺酸酯等之三芳基銃鹽等。 這些化合物中’較佳者爲二苯基碘鑰三氟甲烷磺酸 酯、二苯基碘鎗三氟乙酸酯、4-甲氧基苯基苯基碘鎗三 氟甲苯磺酸酯' 4-甲氧基苯基苯基碘錙三氟乙酸酯、三 苯基锍三氟甲烷磺酸酯、三苯基锍三氟乙酸酯、4 -甲氧 基苯基二苯基銃三氟甲烷磺酸酯、4_甲氧基苯基二苯基 銃三氟乙酸酿、4 -苯基硫代苯基二苯基锍三氟甲烷磺酸 酯、4 -苯基硫代苯基二苯基锍三氟乙酸酯等。 前述銷鹽化合物可單獨使用或混合兩種以上使用。 鑰鹽化合物之添加量係對於（a)鹼可溶性樹脂1 〇〇重 量份時’添加1 〇重量份以下，理想爲5重量份以下。 -界面活性劑- 界面活性劑係具有改善塗佈性例如防止條紋或改良被 膜形成後之曝光部之鹼顯像性之作用的成分。 這種界面活性劑例如聚氧乙烯月桂基醚、聚氧乙烯硬 脂基醚、聚氧乙烯油基醚等聚氧乙烯烷基醚；聚氧乙烯正 辛基苯基醚、聚氧乙烯正壬基苯基醚等聚氧乙烯芳基醚； 聚乙二醇二月桂酸酯、聚乙二醇二硬脂酸酯等之聚乙二醇 二烷脂等之非離子系界面活性劑；及EFTOP EF301、 EF303，EF352(新秋田化成（股）製造）' MegafacF171、 -30- (27) (27)1321702 172、173(大日本油墨工業（股）製造）’ Fl〇lard FC430 'The group represented by B, D and E are respectively a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carboxyl group, a linear or branched alkyl group having a carbon number of 1 to 10, and an aryl group having a carbon number of 6 to 12. a linear or branched alkoxy group having a carbon number of 1 to 10, a linear or branched alkylthio group having 1 to 10 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, and a carbon number of 6 to 12 An arylthio group, a secondary amine group having a linear or branched alkyl group having 1 to 1 carbon atom, a linear or branched ketoalkyl group having 1 to 10 carbon atoms, and a carbon number of 6 to 12 a ketone aryl group, a linear or branched alkoxycarbonyl group having 2 to 20 carbon atoms or a linear or branched alkylcarbonyloxy group having 2 to 20 carbon atoms, and m is an integer of 1 to 5. The trihalomethyl-S-triazine contains, for example, 2,4,6-tris(trichloromethyl) _S-di-exposed, 2-phenyl- 4,6-bis(trichloromethyl)-S-three Oxazine, 2-(4-chlorophenyl)- 4,6-bis(trichloromethyl)-S-triazine, 2-(3-chlorophenyl)-4,6-bis(trichloromethyl) S-triazine, 2-(2-chlorophenyl) • 26 - (23) (23) 1321702 — 4,6-bis(trichloromethyl)_S-triazine, 2-(4-methoxyl) Phenyl)-4,6-bis(trichloromethyl)-S-triazine, 2-(3-methoxyphenyl)- 4,6-bis(trichloromethyl)-S-triazine, 2-(2-methoxyphenyl)- 4,6-bis(trichloromethyl)-S-triazine, 2-(4-methylphenylthio)- 4,6-bis(trichloromethane) A) S-triazine, 2-(3-methylphenylthio)-4,6-bis(trichloromethyl)-S-triazine' 2-(2-methylphenylthio)-4 , 6 - bis(trichloromethyl)_S-triazine, 2_(4-methoxy-β-styryl)-4,6-bis(trichloromethyl)-S_triazine' 2- (3_methoxy_β_styryl)-4,6-bis(trichloromethyl)_S-triazine, 2-(2-methoxy _β-styryl)_4,6_bis(trichloromethyl)-S-triazine, 2_(3,4,5-trimethoxy-β-styryl)_4,6-bis(trichloromethane) A) S-triazine, 2-(4-methylthio-β-styryl)-4,6-bis(trichloromethyl)-S-triazine, 2-(3-methylthio-one) Β_styryl)-4,6-bis(trichloromethyl)-S-triazine' 2_(2-methylthio-β-styryl)-4,6-bis(trichloromethyl) An S-triazine, 2-(4-methoxynaphthyl)- 4,6-bis(trichloromethyl)-S-triazine, 2-(3-methoxynaphthyl)_4,6- Bis(trichloromethyl)-S-triazine' 2_(2-methoxynaphthyl)_4,6-bis(trichloromethyl)_S-triazine. Preferred among these compounds is 2-(3-cyanophenyl)_4,6-bis(trichloromethyl)_S-triazine' 2_(4-methoxyphenyl)- 4,6-bis (three Chloromethyl)_S_triazine, 2_(4-methylphenylthio)_4,6-bis(dichloromethyl)-S_dixiao, 2-(4-methoxy-β-phenylene bromide Base) ~ 4,6_bis(trichloromethyl)-S-triazine, 2-(4-methoxynaphthyl)- 4,6-bis(trichloromethyl)_S-triazine, and the like. -27- (24) (24) 1321702. The product containing di-methyl-S-di-di- can be used alone or in combination. When the amount of the di-dentate methyl group-S-Sanxiao is (a) when the amount of the soluble resin is 100 parts by weight, 1 part by weight or less is added, preferably 1 part by weight or less, more preferably 5 parts by weight or less. . - other low molecular compounds containing phenolic hydroxyl groups - other low molecular compounds containing phenolic hydroxyl groups, for example, 1,1 double (2' 5 -methyl-4-isophenyl) propionium, 1' 1 - double (2,4-diphenyl)acetone, 1,1-bis(2,6-dimethyl-1,4-hydroxyphenyl)acetone, 4' 6-bis[1-(4-hydroxyphenyl)- 1-methylethyl]-indole, 3-di-diphenyl, 4'-6-bis[i-(4-hydroxyphenyl)-1-methylethyl]-1,3-dihydroxy-2 Methylbenzene and the like. These other low molecular compounds containing a phenolic hydroxyl group may be used singly or in combination of two or more. The amount of the low-molecular compound added to the hydroxy group is 50 parts by weight or less, preferably 45 parts by weight or less, based on (a) 100 parts by weight of the soluble resin. - gun salt compound ~ sulfonium salt compound is represented by the following formula (3) (A ) n Z Υ -28- (25) (25) 1321702 [wherein A is defined as the above general formula (2), and η is 2 Or 3; Ζ+ represents S+ or I+; Y-series represents a compound represented by BF4_, PF6, SbF6-, AsFT, p-toluenesulfonic acid anion, trifluoromethanesulfonate anion or trifluoroacetic acid anion]. The onium salt compound is, for example, diphenyliodonium tetrafluoroborate, diphenyliodide hexafluorophosphate, diphenyliodonium hexafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, Phenyl iodide trifluoroacetate, diphenyl iodonate p-toluene sulfonate, 4-methoxyphenyl phenyl iodide tetrafluoroborate, 4-methoxyphenyl phenyl iodonium Fluorophosphate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoroacetate, 4-methoxyphenylphenyliodonium - p-toluenesulfonate, bis(4-tert-butylphenyl) iodine gun tetrafluoroborate, bis(4-butylphenyl) iron iodide hexafluorophosphate, double (4-third Butyl phenyl) iodine gun hexafluoroantimonate, bis(4-tert-butylphenyl) iodine trifluoromethane sulfonate, bis(4-butylbutylphenyl) iodine trifluoroacetic acid Diaryl iodine salt of ester, bis(4-t-butylphenyl) iodine gun p-toluenesulfonate; triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphate, triphenyl Hexafluorodecanoate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoride Acid ester, triphenylsulfonium toluenesulfonate, 4-methoxyphenyldiphenylphosphonium tetrafluoroborate, 4-methoxyphenyldiphenylphosphonium hexafluorophosphate, 4-methyl Oxyphenyl diphenyl sulfonium hexafluoroarsenate, 4-methoxyphenyl diphenyl fluorene trifluoromethane sulfonate, 4-methoxyphenyl diphenyl fluorene trifluoroacetate, 4 1-methoxyphenyldiphenylphosphonium tosylate, 4-phenylthiophenyldiphenylphosphonium tetrafluoroborate, 4-methylthiophenyldiphenylphosphonium-29- (26) (26)1321702 Hexafluorophosphoric acid vinegar, 4-phenylthiophenyldiphenylphosphonium hexafluoroantimonate, 4-phenylthiophenyldiphenylfluorene trifluoromethanesulfonate, 4 a triarylsulfonium salt such as phenylthiophenyldiphenylphosphonium trifluoroacetate or 4-phenylthiophenyldiphenylphosphonium-p-toluenesulfonate. Among these compounds, 'preferably diphenyl iodine trifluoromethanesulfonate, diphenyl iodine trifluoroacetate, 4-methoxyphenyl phenyl iodide trifluorotoluene sulfonate' 4 -Methoxyphenylphenyliodonium trifluoroacetate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylphosphonium trifluoride Methanesulfonate, 4-methoxyphenyldiphenylfluorene trifluoroacetic acid, 4-phenylthiophenyldiphenylfluorene trifluoromethanesulfonate, 4-phenylthiophenyldiphenyl Based on trifluoroacetate and the like. The above-mentioned pin salt compounds may be used singly or in combination of two or more. The amount of the key salt compound to be added is 1 part by weight or less, and preferably 5 parts by weight or less, based on 1 part by weight of the (a) alkali-soluble resin. - Surfactant - The surfactant has a function of improving the coating property, for example, preventing streaking or improving the alkali developability of the exposed portion after the formation of the film. Such a surfactant such as polyoxyethylene alkyl ether such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene n-octyl phenyl ether, polyoxyethylene hydrazine a polyoxyethylene aryl ether such as a phenyl ether; a nonionic surfactant such as a polyethylene glycol dialkyl ester such as polyethylene glycol dilaurate or polyethylene glycol distearate; and EFTOP EF301, EF303, EF352 (manufactured by New Akita Chemicals Co., Ltd.) ' MegafacF171, -30- (27) (27) 1321702 172, 173 (Manufactured by Dainippon Ink Industry Co., Ltd.) 'Fl〇lard FC430 '

FC431(住友 3M(股）製造），Asahi guard AG710' SurflonS -382、SC - 10 1 ' SC - 102、SC — 107、SC — 104、SC - 1 0 5、S C - 1 0 6 (旭玻璃（股）製造）等之氟系界面活性劑； kp 34i(信越化學工業（股）製造）；P〇iyfi〇w Ν〇· 57、 95(共榮社化學（股）製造）等。 前述界面活性劑可單獨使用或混合兩種以上使用。 界面活性劑之添加量係對於輻射敏感性樹脂組成物之 全固形份時，通常添加0.5重量份以下，更理想爲〇.2重 量份以下。 組成物溶液 本發明之輻射敏感性樹脂組成物較佳係以溶解於適當 之溶劑的溶液（以下稱爲「組成物溶液」）來使用。 組成物溶液所使用之溶劑例如可使用溶解輻射敏感性 樹脂組成物之各成分，且與各成分不反應，具有適當蒸氣 壓者較佳。 這種溶劑例如有乙二醇單甲醚、乙二醇單乙醚等之乙 二醇醚；乙二醇甲醚乙酸酯、乙二醇乙醚乙酸酯等之乙二 醇烷醚乙酸酯：二乙二醇二甲醚、二乙二醇二乙醚、二乙 二醇甲基乙醚等之二乙二醇二烷醚；丙二醇甲醚乙酸酯 丙二醇乙醚乙酸酯、丙二醇正丙醚乙酸酯等之丙二醇烷醚 乙酸酯；甲乙基酮、2 -庚酮、甲基異丁酮、環己酮等之 酮；乙酸乙酯、乙酸正丁酯、3 —甲基一3 —甲氧基丁基乙 -31 - (28) (28)1321702 酸酯、羥基乙酸乙酯、乙氧基乙酸乙酯、3—甲基—3 —甲 氧基丁基丙酸酯、乳酸甲酯、乳酸乙酯、2_淫基—2_甲 基丙酸乙酯、3—甲氧基丙酸甲酯、3—甲氧基丙酸乙醋、 3 -甲氧基丙酸正丁酯、2 —羥基一 3~甲基丁酸甲醋、3 — 甲基一 3 -甲氧基丁基丁酸酯之酯類等。 這些溶劑可單獨或混合兩種以上使用。 必要時’則述溶劑也可倂用商沸點溶劑，例如有苯甲 基乙基醚、二己基醚、二乙二醇單甲醚、二乙二醇單乙 醚、二乙二醇單正丁醚 '乙醯丙酮、異佛爾酮、己酸、辛 酸、1—辛醇、1_壬醇、苯甲醇、醋酸苯甲酯、苯甲酸乙 酯 '草酸二乙酯、順丁烯二酸二乙酯、γ_ 丁內酯、碳酸 乙烯酯、碳酸丙烯酯 '苯基二乙二醇乙酸酯 '乙酸卡必醇 酯等。 本發明之組成物溶液之固形份濃度調整成爲20〜40 重量％ ，必要時可使用孔徑〇·2μηι之過濾器過濾後再使 用0 突起及或間隔件之形成方法 其次說明使用本發明之輻射敏感性樹脂組成物，在基 板上形成垂直配向型液晶顯示元件用突起及/或垂直配向 型液晶顯示元件用間隔件，理想爲僅形成垂直配向型液晶 顯示元件用突起或該突起及垂直配向型液晶顯示元件用間 隔件的方法。 首先，在基板上塗佈組成物溶液後，藉由預烘烤除去 -32- (29) (29)1321702 溶劑形成被膜。 前述基板可使用例如玻璃、石英、矽、聚碳酸酯等所 構成者。 組成物溶液之塗佈方法例如可使用噴塗、輥塗、旋轉 塗佈法等各種方法。 預烘烤之條件係依各成分之種類、使用比例等而異’ 預烘烤之較佳條件爲7 0〜9 0 °C、1〜1 5分鐘的條件。 其次，以紫外線等之輻射線照射被膜後，藉由鹼顯像 液顯像去除不需要部分，形成所定圖案。 曝光時所用之圖案光罩及曝光操作例如有（甲）使用具 有突起部份及間隔件部份之兩圖案之一種光罩，進行一次 曝光的方法’（乙）使用僅有突起部份光罩及僅有間隔件部 份之光罩之兩種，進行二次曝光的方法。 (甲）方法所用之圖案光罩例如也可使用突起部份與間 隔件部份之穿透率不同者。 欲在基板上僅形成突起或間隔件其中之一時，可採用 (丙）使用僅有突起部份光罩或僅有間隔件部份之光罩其中 之一種’進行一次曝光的方法。此時，垂直配向型液晶顯 示兀件所需之剩餘之突起或間隔件，可藉由以往公知的方 法來形成。 曝光所用之輻射線可使用可見光、紫外線、遠紫外 線、電子射線、X線等，其中以紫外線較佳。 前述驗顯像液例如可使用氫氧化鈉、氫氧化狎、碳酸 鈉、砂酸鈉、偏政酸鈉、氣水等無機驗；乙胺、正丙|安等 -33- (30) (30)1321702 一級胺類；二乙胺、二正丙胺等二級胺類；三乙胺、甲基 二乙胺等三級胺類；二甲基乙醇胺 '甲基二乙醇胺、三乙 醇胺等醇胺類；吡咯、哌啶、N -甲基哌啶、N -甲基吡 咯、1，8-二氧雜二環 _[5.40]一7_ 十一烯 ' 1，5 —二 氧雜二環-[4.3.0] - 5 -壬烷等環狀三級胺；吡啶、三甲 基吼啶、二甲基吡啶、哇啉之芳香族三級胺：四甲基氫氧 化敍、四乙基氫氧化銨等之四級銨鹽等之水溶液。 前述顯像液中可添加適量之甲醇、乙醇等之水溶性有 機溶媒及/或或界面活性劑。 顯像方法可利用搖動浸漬法 '浸漬法、噴灑法等，顯 像時間通常爲3 0〜1 8 0秒。 鹼顯像後，例如以流水洗淨3 0〜90秒，使用壓縮空 氣或壓縮氮乾燥，形成圖案。 接著對於鹼顯像後之圖案再度進行輻射曝光後，例如 以加熱板、烤箱等加熱裝置使用所定之溫度，例如1 5 0〜 2 5 〇 °C，所定時間例如在加熱板上爲5〜3 0分鐘，在烤箱 中爲30〜90分鐘進行後烘烤，可形成所定之突起及/或間 隔件。此步驟之曝光可使用或不使用光罩。 如上述所形成之突起之高度爲〇.1〜3.0μιη，理想舄 0.5〜2.0μηι，更理想爲1·〇〜1.5μιη。又間隔件之高度爲1 〜】Ομηι，理想爲2〜8μηι’更理想爲3〜5μιη。 依據如上述本發明之垂直配向型液晶顯示元件用之突 起及/或間隔件之形成方法時’可進行微細加工，且可容 易控制形狀及尺寸例如高度或底部尺寸，可以高效率、穩 -34- (31) (31)1321702 定形成圖案形狀、耐熱性、耐溶劑性、透明性等優異之突 起及間隔件’且可得到配向性、電壓保持率等優異之垂直 配向型液晶顯示元件。 【實施方式】 實施例 以下藉由實施例更具體說明本發明之實施形態，但是 本發明不受此限。 合成例1 將2’ 2’一偶氮雙（2，4 —二甲基戊腈）10重量份及二 乙二醇乙基甲醚250重量份投入具備冷卻管及攪拌機之燒 瓶內’接著添加甲基丙烯酸22重量份、苯乙烯5重量 份、三環[5.2.1.02’6]癸烷一 8—基甲基丙烯酸酯28重量 份、甲基丙烯酸縮水甘油酯45重量份及α—甲基苯乙烯 二聚物5重量份，經氮取代後，開始緩慢攪拌。使溶液溫 度上升至7 0 °C，保持此溫度進行聚合4小時，得到鹼可 溶性樹脂之溶液（固形份濃度爲29.8重量％ )。 製得之鹼可溶性樹脂之M w爲8,0 0 0。此鹼可溶性樹 月曰爲「樹脂（a — ])」。 合成例2 將2’ 2’—偶氮雙（2，4_二甲基戊腈）】〇重量份及二 乙二醇乙基甲醚250重量份投入具備冷卻管及攪拌機之燒 -35- (32) (32)1321702 瓶內，接著添加甲基丙烯酸15重量份、苯乙烯12重量 份、三環[5.2.1.02’6]癸烷一 8—基甲基丙烯酸酯28重量 份、甲基丙烯酸縮水甘油酯45重量份及α—甲基苯乙烯 二聚物5重量份，經氮取代後，開始緩慢攪拌。使溶液溫 度上升至70°C，保持此溫度進行聚合4小時，得到鹼可 溶性樹脂之溶液（固形份濃度爲29.0重量％ )。 製得之鹼可溶性樹脂之Mw爲7，800。此鹸可溶性 樹脂爲「樹脂（a - 2)」。 合成例3 將2，2’ 一偶氮雙（2，4 —二甲基戊腈）7重量份及二 乙二醇乙基甲醚2 00重量份投入具備冷卻管及攪拌機之燒 瓶內，接著添加甲基丙烯酸18重量份、苯乙烯6重量 份 '三環[5.2.1.02·6]癸烷_8—基甲基丙烯酸酯1〇重量 份、對乙烯基苯甲基縮水甘油醚33重量份及α -甲基苯 乙烯二聚物3重量份，經氮取代後，開始緩慢攪拌。使溶 液溫度上升至70°C，保持此溫度進行聚合5小時，得到 鹼可溶性樹脂之溶液（固形份濃度爲3 1 .5重量％ )。 製得之鹼可溶性樹脂之Mw爲1 1,〇〇〇。此鹼可溶性樹 脂爲「樹脂（a — 3)」。 合成例3 將2，2’一偶氮雙（2 ’4 一二甲基戊腈）7重量份及二 乙二醇乙基甲醚200重量份投入具備冷卻管及攪拌機之燒 -36 · (33) (33)1321702 瓶內，接著添加甲基丙烯酸18重量份、苯乙烯6重量 份、三環[5.2.1.02’6]癸烷一8 —基甲基丙烯酸酯1〇重量 份、對乙烯基苯甲基縮水甘油醚33重量份及α-甲基苯 乙烯二聚物3重量份，經氮取代後，開始緩慢攪拌。使溶 液溫度上升至7〇°C，保持此溫度進行聚合5小時，得到 鹼可溶性樹脂之溶液（固形份濃度爲3 1 . 5重量％ )。 製得之鹼可溶性樹脂之Mw爲1 1,000。此鹼可溶性樹 脂爲「樹脂（a — 3)」。 合成例4 將2，2’ 一偶氮雙（2，4_二甲基戊腈）6重量份及二 乙二醇乙基甲醚200重量份投入具備冷卻管及攪拌機之燒 瓶內，接著添加甲基丙烯酸12重量份、2_羥乙基甲基丙 烯酸酯25重量份、三環[5.2.1.02’6]癸烷一 8_基甲基丙 烯酸酯6重量份、縮水甘油基甲基丙烯酸酯27重量份、 對乙烯基苯甲基縮水甘油醚30重量份及α-甲基苯乙烯 二聚物3重量份’經氮取代後，開始緩慢攪拌。使溶液溫 度上升至7 01，保持此溫度進行聚合4.5小時，得到鹼可 溶性樹脂之溶液（固形份濃度爲3 2 · 7重量％ )。 製得之鹼可溶性樹脂之Mw爲13,000。此鹼可溶性樹 脂爲「樹脂（a — 4)」。 合成例5 將2’ 2’一偶氮雙（2，4 —二甲基戊腈）8·5重量份及二 -37- (34) (34)1321702 乙二醇乙基甲醚22 0重量份投入具備冷卻管及攪拌機之燒 瓶內，接著添加甲基丙烯酸15重量份、月桂基甲基丙烯 酸酯10重量份、三環[5.2.1.02’6]癸烷一 8_基甲基丙烯 酸酯30重量份、縮水甘油基甲基丙烯酸酯35重量份、對 乙烯基苯甲基縮水甘油醚10重量份及α —甲基苯乙烯二 聚物3重量份，經氮取代後，開始緩慢攪拌。使溶液溫度 上升至7 0 °C，保持此溫度進行聚合4.5小時，得到鹼可溶 性樹脂之溶液（固形份濃度爲3 1 .5重量％ )。 製得之鹼可溶性樹脂之Mw爲8,000。此鹼可溶性樹 脂爲「樹脂（a _ 5 )」。 實施例1 混合（a)成分之樹脂（a — 1)100重量份、（b)成分：4， 4’ _ 〔1— 〔4— 〔1— 〔4 —羥苯基〕一1—甲基乙基〕苯 基〕亞乙基〕雙酚1.0莫耳與1，2 —萘醌二疊氮_5—磺 酸氯2.0莫耳之縮合物所構成之4，4, 一〔1_〔4_〔1 — 〔4 -羥苯基〕—i_甲基乙基〕苯基〕亞乙基〕雙酚— 1’ 2—萘醌二疊氮一5—磺酸酯30重量份及界面活性劑： Megafac F172 0.01 重量份，（c)成分：Epycoat 828(油化 Shell EP〇x(股）製）20.0重量份’以二乙二醇乙基甲醚稀 釋、溶解，使整體之固形份濃度成爲25重量％後，以孔 徑〇·2μπι之薄膜過濾器過濾調製組成物溶液（S_ 1}。 接著依下述步驟形成突起及間隔件’進行各種評價。 評價結果如表2及表3。 -38- (35) (35)1321702 (1 - υ突起及間隔件之形成 使用旋轉塗佈器將組成物溶液（S - 1 )塗佈於在玻璃基 板上’然後，藉由9 0 °C之加熱板上預烘烤2分鐘，形成 膜厚4·0μΐΏ之被膜。然後留下相當於突起部份之5μΠ1寬 度’及留下相當於圖案與間隔件部份之30μπι點（dot)，經 由具有圖案之光罩，以波長365nm之強度爲l〇〇W/cm2之 紫外線曝光10秒。然後，使用0.4重量％四甲基氫氧化 銨水溶液以25 °C顯像60秒鐘，以純水淸洗。再以波長 365nm之強度爲l〇〇W/Cm2之紫外線曝光30秒後，在烤箱 中，以220°C進行後烘烤（post bake)60分鐘，形成突起及 間隔件。 (1 — 2)突起及間隔件之形成 使用旋轉塗佈器將組成物溶液（S - 1 )塗佈於在玻璃基 板上，然後，藉由90°C之加熱板上預烘烤2分鐘，形成 膜厚4·0μΐΏ之被膜。然後留下相當於突起部份之5μπι寬 度，經由具有圖案之光罩，以波長3 6 5 nm之強度爲 1 0 0 W / c m2之紫外線曝光1 〇秒。然後留下相當於間隔件部 份之30μηι點（dot) ’經由具有圖案之光罩，以波長3 65nm 之強度爲l〇〇W/cm2之紫外線曝光1〇秒。使用〇 4重量％ 四甲基氫氧化銨水溶液以25 °C顯像60秒鐘，使用純水淸 洗。再以波長365nm之強度爲i〇〇w/cm2之紫外線曝光30 秒後’在烤箱中’以22(TC進行後烘烤60分鐘，形成突 -39- (36) (36)1321702 起及間隔件。 (2)解像度之評價 以上述（1_1)及（1 一 2)之步驟形成圖案時，圖案可解 像時，評價爲「良好」，無法解像時，評價爲「不 良」。 (3)殘膜率之評價 使用輻射敏感性樹脂組成物形成突起及間隔件時，如 日本特開200 1 - 20 1 7750號公報所揭示，改變曝光能量 (曝光時間）時，鹼顯像時之膜減少量之變化爲溫和的，且 具有高殘膜率者較佳。分別測定以波長3 6 5nm之強度爲 1 00W/cm2之紫外線曝光4秒、5秒及6秒時之殘膜率， 曝光4秒及6秒時之殘膜率對曝光5秒之殘膜率爲90〜 1 1 0%之範圍內時評價爲「良好」。 (4 _ 1)突起之斷面形狀之評價 突起之斷面形狀A、B或C之定義如下時，使用掃瞄 型電子顯微鏡觀察形成之突起之斷面形狀，A或B評價 爲「良好」，C評價爲「不良」。突起之斷面形狀a、b 或C之模式圖如圖1所示。 A.底部之尺寸爲5μηι以上，7μιη以下時， Β :底部之尺寸爲7μπι以上時， C:不論底部之尺寸，爲台形形狀時。 -40- (37) (37)1321702 (4 一 1)間隔件之斷面形狀之評價 間隔件之斷面形狀A、B或C之定義如下時，使用掃 目苗型電子顯微鏡觀察形成之間隔件之斷面形狀，A或C評 價爲「良好」’B評價爲「不良」。間隔件之斷面形狀 A、B或C之模式圖如圖1所示。 八：底部之尺寸爲30μηι以上，36μηι以下時， Β:底部之尺寸爲36μηι以上時， C:不論底部之尺寸，爲台形形狀時。 〔耐熱性之評估〕 使用旋轉塗佈器將組成物溶液（S — 1 )塗佈於在玻璃基 板上’然後，藉由9(TC之加熱板上預烘烤2分鐘，形成 膜厚4.Ομιη之被膜後，對於製得之被膜使用 canon PLA50IF(Canon(股）製）曝光機，以波長3 65nm之強度爲 1 00W/cm2之紫外線曝光1 〇秒。然後將此基板置於無塵烘 箱內，以22 0°C進行後烘烤1小時，形成硬化膜，測定該 硬化膜之膜厚（T〗）。另外，將形成此硬化膜之基板置於無 塵烘箱內，以240°C再進行後烘烤1小時後，測定該硬化 膜之膜厚（T2) ’算出追加烘烤所產生之膜厚變化率（丨T2 -T1丨/ T1)M00(% )進行評價。此値爲5%以下時，表示 耐熱性良好。 (6)耐溶劑性之評價 -41 - 20 (38) 1321702 與前述（5)之步驟相同測定硬化膜之膜厚（T2)。然後 將形成此硬化膜之基板浸漬於保持7〇°C之二甲亞碩中 分鐘，然後測定硬化膜之膜厚（t2 )，算出浸漬所產生之 厚變化率（| t2 — T2丨/ Τ2)χ〗00(% )進行評價。此値爲5 以下時，表示耐溶劑性良好。 (7)透明性之評價 除使用玻璃基板「Corning 7059(Corning公司）製」 代矽基板外，其餘與前述（5)之步驟相同，在玻璃基板 形成硬化膜。對於此基板使用分光光度計^ 150- 20 double beam((股）日立製作所製）」測定在400〜800nm 波長範圍之光線穿透率，進行評價。其數値在95%以 時，表示透明性良好。 (8)配向性及電壓保持率 使用組成物溶液（S-1)在具有電極之ITO(摻雜錫之 化銦）膜之玻璃基板之電極面，與前述（1 - 1)之步驟相 形成突起及間隔件。然後藉由液晶配向膜塗佈用印刷機 液晶配向劑AL1H659(商品名、JSR(股）製）塗佈於形成 起及間隔件之玻璃基板後，以1 8 (TC乾燥1小時，形成 厚0.05μηι之被膜。 另外，藉由液晶配向膜塗佈用印刷機將液晶配向 AL1H659塗佈於具有ΙΤΟ膜之其他玻璃基板之電極面 以1 8 Ot：乾燥1小時，形成膜厚〇 · 〇 5 μιη之被膜。 膜 % 取 上 型 之 上 氧 同 將 突 膜 劑 -42- (39) (39)1321702 接著將製得之兩基板之各液晶配向膜之外面放置直徑 5 μηι之玻璃纖維，藉由網版引刷塗佈環氧樹脂黏著劑，將 兩基板之液晶配向膜面相對，予以重疊壓黏後，使黏著劑 硬化。然後將Merk公司製MLC — 660 8 (商品名）由液晶注 入口塡充於兩基板間，再以環氧系黏著劑封住液晶注入 口，將偏光板之偏光方向呈直交，貼於兩基板之外面，製 作垂直配向型液晶顯示元件。製得之垂直配向型液晶顯示 元件之縱斷面圖之模式圖如圖2所示。圖2中，1爲間隔 件，2爲突起，3爲液晶，4爲液晶配向膜，5爲彩色濾光 片，6爲玻璃基板。 對於製得之垂直配向型液晶顯示元件之配向性及電壓 保持率如下述評價。 配向性之評價時，以偏光顯微鏡觀察當電壓ON/OFF 時，液晶晶胞中是否產生異常區域，若無異常區域時表示 「良好」。 電壓保持率之評價時，對液晶顯示元件施加5V之電 壓後，在開路下，測定其1 6.7毫秒後之保持電壓，計算 對於該施加電壓（5V)之比例，其値爲98%以上時，表示 「良好」，未達98%時，表示「不良」。 實施例2〜1 4 除了使用表1所示之各成分，顯像液之四甲基氫氧化 銨水溶液之濃度如表1所示外，其餘同實施例1調製組成 物溶液，形成突起及間隔件，然後進行各種評價。評價結 -43- (40) (40)1321702 果如表2及表3所示。 表1 \ (a)成份 (重量部） (b )成份 (重量部） (c)成份 (重量部） (d )成份 (重量部） 顯像液之 濃度 (重量％) 實施例1 a-1(100) b-1(30) _ _ 0.4 實施例2 a-1(100) b-1(3 0) c-1(20) 一 1.5 實施例3 a-2(100) b-1(30) c-1(20) _ 2.38 實施例4 a-3(100) b-1(30) c-1(20) _ 0.4 實施例5 a-4(100) b-1(30) c-1(20) 一 0.4 實施例6 a-5(100) b-1(30) c-1(20) 一 2.38 實施例7 a-1(100) b-2(3 0) c-1(20) 一 0.4 實施例8 a-1(100) b-3(30) c-1(20) _ 0.4 實施例9 a-1(100) b-4(30) c-1(20) 一 0.4 實施例10 a-1(100) b-5(30) c-1(20) 一 0.4 實施例11 a-1(100) b-l(30) c-2(20) 一 0.4 實施例12 a-1(100) b-1(30) c-3(20) 一 0.4 實施例13 a-1(100) b-1(30) 一 d-1(20) 0.4 實施例14 a-1(1 00) b-1(30) _ d-2(20) 0.4 表1之（b)〜（d)成分如下述。 b — ]:4，4' 一〔1 —〔4 —〔1 —〔4 —經苯基〕一 1 — 甲基乙基〕苯基〕亞乙基〕雙酚1.0莫耳與1，2 —萘醌二 -44- (41) (41)1321702 疊氮一 5 -擴酸氯2.0旲耳之縮合物 b_2: 2，3，4 —三羥基二苯甲酮1_0莫耳與1，2 — 萘醌二疊氮- 5 -磺酸氯2.6莫耳之縮合物 b— 3: 2，3，4，4，一四羥基二苯甲酮1.0莫耳與1， 2-萘醌二疊氮—5—磺酸氯2.5莫耳之縮合物 b-4: 1，1，1-三（2，5 —二甲基一4 —羥苯基）—3 一苯基丙烷1.0莫耳與1，2—萘醌二疊氮~5 —磺酸氯 1 . 9莫耳之縮合物FC431 (manufactured by Sumitomo 3M), Asahi guard AG710' SurflonS -382, SC - 10 1 'SC - 102, SC - 107, SC - 104, SC - 1 0 5, SC - 1 0 6 (Asahi Glass ( a fluorine-based surfactant such as Manufacture); kp 34i (manufactured by Shin-Etsu Chemical Co., Ltd.); P〇iyfi〇w 57 57, 95 (manufactured by Kyoeisha Chemical Co., Ltd.). The aforementioned surfactants may be used singly or in combination of two or more. The amount of the surfactant added is usually 0.5 parts by weight or less, more preferably 〇.2 parts by weight or less, based on the total solid content of the radiation-sensitive resin composition. Composition Solution The radiation-sensitive resin composition of the present invention is preferably used in a solution (hereinafter referred to as "composition solution") dissolved in a suitable solvent. The solvent used for the composition solution can be, for example, a component which dissolves the composition of the radiation-sensitive resin, and does not react with each component, and it is preferred to have a suitable vapor pressure. Such a solvent is, for example, a glycol ether such as ethylene glycol monomethyl ether or ethylene glycol monoethyl ether; ethylene glycol alkyl ether acetate such as ethylene glycol methyl ether acetate or ethylene glycol ethyl ether acetate. : diethylene glycol dialkyl ether such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ether; propylene glycol methyl ether acetate propylene glycol diethyl ether acetate, propylene glycol n-propyl ether a propylene glycol alkyl ether acetate such as an acid ester; a ketone such as methyl ethyl ketone, 2-heptanone, methyl isobutyl ketone or cyclohexanone; ethyl acetate, n-butyl acetate, 3-methyl-3-methyl Oxybutyl butyl-31 - (28) (28) 1321702 acid ester, ethyl hydroxyacetate, ethyl ethoxyacetate, 3-methyl-3-methoxybutyl propionate, methyl lactate, Ethyl lactate, 2- keto-2-ethyl propionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, n-butyl 3-methoxypropionate, 2 - an ester of hydroxy-3~methylbutyrate methyl acetonate, 3-methyl-3-methoxy butyl butyrate, and the like. These solvents may be used singly or in combination of two or more. If necessary, the solvent may also be used as a solvent, such as benzyl ethyl ether, dihexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether. 'Acetylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate Ester, γ-butyrolactone, ethylene carbonate, propylene carbonate 'phenyl diethylene glycol acetate' acetic acid carbitol ester and the like. The solid content concentration of the composition solution of the present invention is adjusted to 20 to 40% by weight, and if necessary, it can be filtered using a filter having a pore size of 〇·2μηι, and then a method of forming a protrusion or a spacer is used. Next, the radiation sensitivity using the present invention will be described. The resin composition is a vertical alignment type liquid crystal display element protrusion and/or a vertical alignment type liquid crystal display element spacer, and it is preferable to form only a vertical alignment type liquid crystal display element protrusion or the protrusion and the vertical alignment type liquid crystal. A method of displaying a spacer for an element. First, after coating a composition solution on a substrate, a solvent is formed by prebaking to remove -32-(29)(29)1321702 solvent. As the substrate, for example, glass, quartz, rhodium, polycarbonate or the like can be used. The coating method of the composition solution can be, for example, various methods such as spray coating, roll coating, and spin coating. The prebaking conditions vary depending on the type of the components, the ratio of use, etc. The conditions for prebaking are 70 to 90 ° C for 1 to 15 minutes. Next, after the film is irradiated with radiation such as ultraviolet rays, the unnecessary portion is removed by alkali imaging to form a predetermined pattern. The pattern mask used for exposure and the exposure operation include, for example, a method of performing one exposure using a mask having two patterns of a protruding portion and a spacer portion. (B) using only a protruding portion mask And two methods of masking only the spacer part, and performing the double exposure method. (a) The pattern mask used in the method may, for example, also use a difference in the transmittance of the protruding portion and the spacer portion. In order to form only one of the protrusions or spacers on the substrate, a method of performing one exposure using one of the photomasks having only the protruding portion mask or only the spacer portion may be employed. At this time, the remaining protrusions or spacers required for the vertical alignment type liquid crystal display element can be formed by a conventionally known method. The radiation used for the exposure may be visible light, ultraviolet light, far ultraviolet light, electron ray, X-ray or the like, of which ultraviolet light is preferred. For the above-mentioned test imaging liquid, for example, an inorganic test such as sodium hydroxide, barium hydroxide, sodium carbonate, sodium silicate, sodium metabasic acid or gas water can be used; ethylamine, n-propyl | anthene, etc. -33- (30) (30 1321702 primary amines; secondary amines such as diethylamine and di-n-propylamine; tertiary amines such as triethylamine and methyldiethylamine; and alcoholic amines such as dimethylethanolamine, methyldiethanolamine and triethanolamine ; pyrrole, piperidine, N-methylpiperidine, N-methylpyrrole, 1,8-dioxabicyclo-[5.40]-7-undecene' 1,5-dioxabicyclo-[4.3 a cyclic tertiary amine such as -5-decane; an aromatic tertiary amine of pyridine, trimethyl acridine, lutidine or morpholine: tetramethylammonium hydroxide, tetraethylammonium hydroxide An aqueous solution of a quaternary ammonium salt or the like. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol and/or a surfactant may be added to the developing solution. The development method can be carried out by a shaking impregnation method, a dipping method, a spraying method, etc., and the development time is usually from 30 to 180 seconds. After alkali development, for example, it is washed with running water for 30 to 90 seconds, and dried using compressed air or compressed nitrogen to form a pattern. Then, after the alkali-developed pattern is irradiated again, for example, a heating device such as a hot plate or an oven is used, for example, a temperature of, for example, 1 5 0 to 2 5 〇 ° C, for a predetermined time, for example, 5 to 3 on a hot plate. After 0 minutes, post-baking is carried out in an oven for 30 to 90 minutes to form predetermined protrusions and/or spacers. Exposure to this step may or may not use a reticle. The height of the protrusion formed as described above is 〇1 to 3.0 μm, and ideally 舄 0.5 to 2.0 μm, more preferably 1·〇 to 1.5 μm. Further, the height of the spacer is 1 to Ομηι, and ideally 2 to 8 μηι' is more preferably 3 to 5 μm. According to the above-described method for forming a protrusion and/or a spacer for a vertical alignment type liquid crystal display device of the present invention, 'fine processing can be performed, and the shape and size such as height or bottom size can be easily controlled, and high efficiency and stability can be achieved. (31) (31) 1321702 A vertical alignment type liquid crystal display element having excellent patterning, heat resistance, solvent resistance, transparency, and the like, and a spacer, and excellent in alignment property, voltage holding ratio, and the like. [Embodiment] Hereinafter, embodiments of the present invention will be described more specifically by way of examples, but the invention is not limited thereto. Synthesis Example 1 10 parts by weight of 2' 2'-azobis(2,4-dimethylvaleronitrile) and 250 parts by weight of diethylene glycol ethyl methyl ether were placed in a flask equipped with a cooling tube and a stirrer. 22 parts by weight of methacrylic acid, 5 parts by weight of styrene, 28 parts by weight of tricyclo[5.2.1.0'6]decane-8-methacrylic acid ester, 45 parts by weight of glycidyl methacrylate, and α-methyl group 5 parts by weight of the styrene dimer was slowly stirred after being replaced by nitrogen. The temperature of the solution was raised to 70 ° C, and the temperature was maintained at this temperature for 4 hours to obtain a solution of an alkali-soluble resin (solid content concentration: 29.8% by weight). The M w of the alkali-soluble resin obtained was 8,0 0. The alkali-soluble tree sorghum is "resin (a - ])". Synthesis Example 2 2' 2'-azobis(2,4-dimethylvaleronitrile) ruthenium by weight and 250 parts by weight of diethylene glycol ethyl methyl ether were charged into a cooling tube and a mixer-35- (32) (32) 1321702 bottle, followed by adding 15 parts by weight of methacrylic acid, 12 parts by weight of styrene, 28 parts by weight of tricyclo [5.2.1.0''6] decane 8-octyl methacrylate, methyl 45 parts by weight of glycidyl acrylate and 5 parts by weight of α-methylstyrene dimer were slowly stirred after being substituted by nitrogen. The temperature of the solution was raised to 70 ° C, and the temperature was maintained at this temperature for 4 hours to obtain a solution of an alkali-soluble resin (solid content concentration: 29.0% by weight). The Mw of the obtained alkali-soluble resin was 7,800. The bismuth soluble resin is "resin (a - 2)". Synthesis Example 3 7 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol ethyl methyl ether were placed in a flask equipped with a cooling tube and a stirrer, followed by 18 parts by weight of methacrylic acid, 6 parts by weight of styrene, 1 part by weight of 'tricyclo[5.2.1.02·6]decane-8-methacrylic acid ester, and 33 parts by weight of p-vinylbenzyl glycidyl ether And 3 parts by weight of the α-methylstyrene dimer, after being substituted by nitrogen, started to stir slowly. The temperature of the solution was raised to 70 ° C, and the temperature was maintained at this temperature for 5 hours to obtain a solution of an alkali-soluble resin (solid content concentration of 31.5 % by weight). The Mw of the obtained alkali-soluble resin was 1,1 Torr. This alkali-soluble resin is "resin (a - 3)". Synthesis Example 3 7 parts by weight of 2,2'-azobis(2'4-dimethylpentanenitrile) and 200 parts by weight of diethylene glycol ethyl methyl ether were charged into a cooling tube and a stirrer-36. 33) (33) 1321702 bottle, followed by adding 18 parts by weight of methacrylic acid, 6 parts by weight of styrene, tricyclo [5.2.1.02'6] decane-8 methacrylate 1 part by weight, for ethylene 33 parts by weight of benzyl methacrylate and 3 parts by weight of α-methylstyrene dimer were slowly stirred after being substituted by nitrogen. The temperature of the solution was raised to 7 ° C, and the temperature was maintained for 5 hours to obtain a solution of an alkali-soluble resin (solid content of 31.5 wt%). The Mw of the obtained alkali-soluble resin was 11,000. This alkali-soluble resin is "resin (a - 3)". Synthesis Example 4 6 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol ethyl methyl ether were placed in a flask equipped with a cooling tube and a stirrer, followed by addition. 12 parts by weight of methacrylic acid, 25 parts by weight of 2-hydroxyethyl methacrylate, 6 parts by weight of tricyclo [5.2.1.0''6] decane-8 methacrylate, glycidyl methacrylate 27 parts by weight, 30 parts by weight of p-vinylbenzyl glycidyl ether and 3 parts by weight of α-methylstyrene dimer, were replaced by nitrogen, and stirring was started slowly. The temperature of the solution was raised to 701, and the temperature was maintained at this temperature for 4.5 hours to obtain a solution of an alkali-soluble resin (solid content concentration of 3 2 · 7 wt%). The Mw of the obtained alkali-soluble resin was 13,000. This alkali-soluble resin is "resin (a - 4)". Synthesis Example 5 8'5 parts by weight of 2' 2'-azobis(2,4-dimethylvaleronitrile) and 2,37-(34) (34)1321702 ethylene glycol ethyl methyl ether 22 0 weight The mixture was placed in a flask equipped with a cooling tube and a stirrer, followed by adding 15 parts by weight of methacrylic acid, 10 parts by weight of lauryl methacrylate, and tricyclo [5.2.1.0''6] decane-8 methacrylate 30. Parts by weight, 35 parts by weight of glycidyl methacrylate, 10 parts by weight of p-vinylbenzyl glycidyl ether and 3 parts by weight of α-methylstyrene dimer were slowly stirred after being substituted by nitrogen. The temperature of the solution was raised to 70 ° C, and the temperature was maintained for 4.5 hours to obtain a solution of an alkali-soluble resin (solid content concentration of 31.5 % by weight). The Mw of the obtained alkali-soluble resin was 8,000. This alkali-soluble resin is "resin (a _ 5 )". Example 1 100 parts by weight of the resin of (a) component (a-1), (b) component: 4, 4' _ [1 - [4-[4-[4-hydroxyphenyl]-1-methyl Ethyl]phenyl]ethylidene]bisphenol 1.0 molar and 1,2-naphthoquinonediazide-5-sulfonic acid chloride 2.0 molar condensate 4,4, one [1_[4_[ 1 —[4-Hydroxyphenyl]-i-methylethyl]phenyl]ethylidene]bisphenol-1'2-naphthoquinonediazide-5-sulfonate 30 parts by weight and surfactant: Megafac F172 0.01 parts by weight, component (c): Epycoat 828 (manufactured by Oiled Shell EP®x) 20.0 parts by weight 'diluted with diethylene glycol ethyl methyl ether, dissolved, so that the overall solid concentration is 25 After the weight %, the composition solution (S_1} was filtered by a membrane filter having a pore size of μ·2 μm. Then, the protrusions and the spacers were formed in the following steps to carry out various evaluations. The evaluation results are shown in Table 2 and Table 3. -38- (35) (35) 1321702 (1 - Formation of υ protrusions and spacers Using a spin coater to apply the composition solution (S - 1 ) on a glass substrate ' Then, with a heating plate of 90 ° C Pre-baking 2 minutes, a film having a film thickness of 4·0 μΐΏ was formed, and then a width of 5 μΠ1 corresponding to the protruding portion was left and a dot of 30 μπι corresponding to the pattern and the spacer portion was left, via a patterned mask. An ultraviolet light having a wavelength of 365 nm and an intensity of 10 W/cm 2 was exposed for 10 seconds, and then developed with a 0.4 wt% aqueous solution of tetramethylammonium hydroxide at 25 ° C for 60 seconds, rinsed with pure water, and then wavelength 365 nm. After exposure to ultraviolet light of intensity l〇〇W/Cm2 for 30 seconds, post bake was performed in an oven at 220 ° C for 60 minutes to form protrusions and spacers. (1 - 2) protrusions and spacers Formation The composition solution (S-1) was applied onto a glass substrate using a spin coater, and then prebaked on a hot plate at 90 ° C for 2 minutes to form a film having a film thickness of 4.0 μm. Then, a width of 5 μm corresponding to the protruding portion is left, and the ultraviolet ray having a wavelength of 3 6 5 nm and an intensity of 100 W / c m 2 is exposed for 1 〇 second through a mask having a pattern, and then left equivalent to the spacer portion. 30μηι dot (via dot) through a patterned mask at a wavelength of 3 65nm UV exposure of l〇〇W/cm2 for 1 sec., using 〇4 wt% aqueous solution of tetramethylammonium hydroxide for 25 seconds at 25 °C, rinsed with pure water, and then with a wavelength of 365 nm. The UV exposure of i〇〇w/cm2 was exposed for 30 seconds and then 'baked in the oven' at 22 (TC for 60 minutes to form the protrusion -39-(36) (36) 1321702 and the spacer. (2) Evaluation of resolution When the pattern was formed by the above steps (1_1) and (1), the pattern was evaluated as "good" when the pattern was resolved, and "not good" when the pattern could not be resolved. (3) Evaluation of Residual Film Rate When a protrusion and a spacer are formed using a radiation-sensitive resin composition, as disclosed in Japanese Laid-Open Patent Publication No. 2001-201-7750, when the exposure energy (exposure time) is changed, alkali imaging is performed. The change in the amount of film reduction is mild, and it is preferable to have a high residual film rate. The residual film rate at 4 seconds, 5 seconds, and 6 seconds after exposure to ultraviolet rays having a wavelength of 3 6 5 nm at a frequency of 1 00 W/cm 2 was measured, and the residual film ratio at exposure time of 4 seconds and 6 seconds to the residual film rate at 5 seconds of exposure was measured. When it is in the range of 90 to 110%, it is evaluated as "good". (4 _ 1) Evaluation of the cross-sectional shape of the protrusions When the cross-sectional shape A, B or C of the protrusion is defined as follows, the cross-sectional shape of the formed protrusion is observed using a scanning electron microscope, and A or B is evaluated as "good". C is rated as "bad". A schematic diagram of the cross-sectional shape a, b or C of the protrusion is shown in Fig. 1. A. When the size of the bottom portion is 5 μηι or more and 7 μηη or less, Β : When the size of the bottom portion is 7 μπι or more, C: When the size of the bottom portion is a trapezoidal shape. -40- (37) (37)1321702 (4-1) Evaluation of the cross-sectional shape of the spacers When the cross-sectional shape A, B or C of the spacer is defined as follows, the interval formed by the scanning electron microscope is observed. The cross-sectional shape of the piece was evaluated as "good" by A or C and "bad" by B. The cross-sectional shape of the spacer A, B or C is shown in Figure 1. Eight: When the size of the bottom is 30 μηι or more, 36 μηι or less, Β: When the size of the bottom is 36 μηι or more, C: When the size of the bottom is a trapezoidal shape. [Evaluation of heat resistance] A composition solution (S-1) was applied onto a glass substrate using a spin coater', and then a film thickness was formed by prebaking for 2 minutes on a hot plate of 9 (TC). After the film of Ομιη, the obtained film was exposed to ultraviolet light having a wavelength of 3 65 nm and an intensity of 100 W/cm 2 for 1 sec. using a canon PLA50IF (manufactured by Canon). The substrate was then placed in a dust-free oven. Thereafter, post-baking was performed at 22 ° C for 1 hour to form a cured film, and the film thickness (T) of the cured film was measured. Further, the substrate on which the cured film was formed was placed in a dust-free oven at 240 ° C. After the post-baking was performed for 1 hour, the film thickness (T2) of the cured film was measured and the film thickness change rate (丨T2 - T1 丨 / T1) M00 (%) due to the additional baking was calculated and evaluated. When the amount is 5% or less, the heat resistance is good. (6) Evaluation of solvent resistance - 41 - 20 (38) 1321702 The film thickness (T2) of the cured film is measured in the same manner as in the above step (5). The substrate was immersed in a dimethyl sulfoxide maintained at 7 ° C for a minute, and then the film thickness (t2 ) of the cured film was measured to calculate the impregnation. The thickness change rate (| t2 - T2 丨 / Τ 2) χ 00 (%) was evaluated. When the 値 was 5 or less, the solvent resistance was good. (7) Evaluation of transparency except glass substrate "Corning 7059" In the same manner as in the above (5), a cured film is formed on the glass substrate, and the spectrophotometer is used as a substrate (150- 20 double beam (manufactured by Hitachi, Ltd.). The light transmittance in the wavelength range of 400 to 800 nm was measured and evaluated. When the number was 95%, the transparency was good. (8) The alignment property and the voltage retention ratio were as follows using the composition solution (S-1). The electrode surface of the glass substrate of the ITO (tin-doped indium oxide) film of the electrode forms a protrusion and a spacer with the above step (1 - 1), and then the liquid crystal alignment agent AL1H659 is applied by the liquid crystal alignment film coating. (product name, manufactured by JSR) was applied to a glass substrate on which a spacer and a spacer were formed, and then dried at 18 (TC for 1 hour to form a film having a thickness of 0.05 μm. Further, printing by liquid crystal alignment film coating was carried out. The machine will apply liquid crystal alignment to AL1H659 with ΙΤΟ The electrode surface of the other glass substrate was dried at 1 8 Ot: for 1 hour to form a film having a film thickness of 〇·〇5 μm. The film % was taken on top of the oxygen-based film-42-(39) (39) 1321702 Then, a glass fiber having a diameter of 5 μm is placed on the outer surface of each of the liquid crystal alignment films of the two substrates, and the epoxy resin adhesive is applied by the screen printing, and the liquid crystal alignment films of the two substrates are opposed to each other to be overlapped and pressed. After that, the adhesive is hardened. Then, MLC-660 8 (trade name) manufactured by Merk Co., Ltd. is filled between the two substrates by a liquid crystal injection port, and the liquid crystal injection port is sealed with an epoxy adhesive, and the polarizing direction of the polarizing plate is orthogonal, and is attached to the two substrates. On the outside, a vertical alignment type liquid crystal display element is fabricated. A schematic diagram of a longitudinal section of the vertically aligned liquid crystal display device is shown in Fig. 2. In Fig. 2, 1 is a spacer, 2 is a protrusion, 3 is a liquid crystal, 4 is a liquid crystal alignment film, 5 is a color filter, and 6 is a glass substrate. The alignment and voltage holding ratio of the obtained vertical alignment type liquid crystal display element were evaluated as follows. In the evaluation of the alignment, it was observed by a polarizing microscope whether or not an abnormal region occurred in the liquid crystal cell when the voltage was turned ON/OFF, and "good" if there was no abnormal region. In the evaluation of the voltage holding ratio, after a voltage of 5 V was applied to the liquid crystal display element, the holding voltage after 1 6.7 milliseconds was measured under an open circuit, and when the ratio of the applied voltage (5 V) was calculated to be 98% or more, It means "good". If it is less than 98%, it means "bad". Examples 2 to 1 4 Except that the components shown in Table 1 were used, the concentration of the tetramethylammonium hydroxide aqueous solution of the developing solution was as shown in Table 1, and the composition solution was prepared in the same manner as in Example 1 to form protrusions and spaces. Pieces, and then carry out various evaluations. Evaluation Results -43- (40) (40) 1321702 The results are shown in Tables 2 and 3. Table 1 \ (a) Ingredient (weight) (b) Ingredient (weight) (c) Ingredient (weight) (d) Ingredient (weight) Concentration (% by weight) of developing solution Example 1 a-1 (100) b-1(30) _ _ 0.4 Example 2 a-1(100) b-1(3 0) c-1(20) a 1.5 Example 3 a-2(100) b-1(30 C-1(20) _ 2.38 Example 4 a-3(100) b-1(30) c-1(20) _ 0.4 Example 5 a-4(100) b-1(30) c-1 (20) a 0.4 Example 6 a-5(100) b-1(30) c-1(20) A 2.38 Example 7 a-1(100) b-2(3 0) c-1(20) a 0.4 Example 8 a-1 (100) b-3 (30) c-1 (20) _ 0.4 Example 9 a-1 (100) b-4 (30) c-1 (20) - 0.4 Example 10 a-1 (100) b-5 (30) c-1 (20) - 0.4 Example 11 a-1 (100) bl (30) c-2 (20) - 0.4 Example 12 a-1 (100 B-1(30) c-3(20)-0.4 Example 13 a-1(100) b-1(30)-d-1(20) 0.4 Example 14 a-1(1 00) b- 1(30) _ d-2(20) 0.4 The components (b) to (d) of Table 1 are as follows. b — ]: 4,4′-[1—[4—[1—[4—Phenyl]-l-methylethyl]phenyl]ethylidene]bisphenol 1.0 Moule and 1,2 — Naphthoquinone di-44-(41) (41)1321702 azide-5-propionic acid chloride 2.0 condensate b_2: 2,3,4-trihydroxybenzophenone 1_0 molar and 1,2-naphthalene醌Diazide-5-sulfonic acid chloride 2.6 molar condensate b-3: 2,3,4,4,tetrahydroxybenzophenone 1.0 molar and 1,2-naphthoquinonediazide-5 - sulfonic acid chloride 2.5 mole condensate b-4: 1,1,1-tris(2,5-dimethyl-4-hydroxyphenyl)-3 monophenylpropane 1.0 molar and 1,2- Naphthoquinone diazide ~5-sulfonic acid chloride 1. 9 molar condensate

b-5: 2—甲基 一2-(2，4 -二羥苯基）一4-(4 -羥 苯基）_7 —羥基色滿1.0莫耳與1，2 —萘醌二疊氮一 5_ 磺酸氯3.0莫耳之縮合物 c — 1 : S i m e 1 3 0 0 c — 1 : Simel 2 7 2 c— 1 ： Nikalac Ms— 11 d — 1 : Epycoat 8 2 8 d — 2 : Epolite 1 00MF -45 - (42)1321702 表2 \ 解像度 殘膜率 斷面形狀 突起 間隔件 形狀 判定 形狀 判定 實施例1 良好 良好 A 良好 C 良好 實施例2 良好 良好 B 良好 C 良好 實施例3 良好 良好 B 良好 A 良好 實施例4 良好 良好 B 良好 A 良好 實施例5 良好 良好 B 良好 A 良好 實施例6 良好 良好 B 良好 A 良好 實施例7 良好 良好 B 良好 A 良好 實施例8 良好 良好 B 良好 C 良好 實施例9 良好 良好 B 良好 C 良好 實施例10 良好 良好 B 良好 c 良好 實施例11 良好 良好 B 良好 A 良好 實施例12 良好 良好 B 良好 A 良好 實施例13 良好 良好 B 良好 A 良好 實施例14 良好 良好 B 良好 A 良好 -46 - (43) (43)1321702 表3 耐熱性 (%) 耐溶劑性 (%) 透明性 (%) 配向性 電壓保持率 實施例1 3 3 9 7 良好 良好 實施例2 2 2 9 6 良好 良好 實施例3 3 3 9 8 良好 良好 實施例4 3 3 9 5 良好 良好 實施例5 3 3 9 6 良好 良好 實施例6 2 2 9 6 良好 良好 實施例7 3 3 9 6 良好 良好 實施例8 3 3 9 5 良好 良好 實施例9 3 3 9 6 良好 良好 實施例10 2 3 9 7 良好 良好 實施例11 4 4 9 6 良好 良好 實施例12 3 3 9 5 良好 良好 實施例13 3 3 9 7 良好 良好 實施例14 3 3 9 5 良好 良好 實施例1 5 使用實施例1調製之組成物溶液（S -])，藉由旋轉塗 佈器將組成物溶液（S - 1 )塗佈於在玻璃基板上，然後，藉 由90°C之加熱板上預烘烤2分鐘，形成膜厚4.0μπι之被 膜。然後留下相當於突起部份之5 μπι寬度，經由具有圖 案之光罩，以波長365nm之強度爲】OOW/cm2之紫外線曝 -47- (44) (44)1321702 光1 〇秒。然後使用〇·4重量％四甲基氫氧化銨水溶液以 25°C顯像60秒鐘，再使用純水淸洗。以波長365nm之強 度爲100W/cm2之紫外線曝光3〇秒後，在烤箱中，以22〇 C進仃後供烤6 0分鐘，形成突起。 對於製得之突起’使用與前述（4-1)之步驟相同，使 用掃瞄型電子顯微鏡觀察斷面形狀，評價結果爲A。 如上述’本發明之形成垂直配向型液晶顯示元件用突 起及/或間隔件之輻射敏感性樹脂組成物係解像度及殘膜 率優異’且可形成圖案形狀、耐熱性、耐溶劑性、透明性 等優異之突起及/或間隔件，且可得到配向性、電壓保持 率等優異之垂直配向型液晶顯示元件。 本發明之垂直配向型液晶顯示元件用突起及/或間隔 件之形成方法可微細加工，且可容易控制形狀及尺寸例如 高度或底部尺寸，可以高效率、穩定形成圖案形狀、耐熱 性、耐溶劑性、透明性等優異之突起及間隔件，且可得到 配向性、電壓保持率等優異之垂直配向型液晶顯示元件。 【圖式簡單說明】 圖1係突起及間隔件之斷面形狀的模式圖之一例。 圖2係具有突起及間隔件之垂直配向型液晶顯示元件 之斷面形狀的模式圖之一例。 -48-B-5: 2-methyl-2-(2,4-dihydroxyphenyl)-4-(4-hydroxyphenyl)-7-hydroxyl-filled 1.0-mole with 1,2-naphthoquinonediazide 5_ sulfonic acid chloride 3.0 mole condensate c — 1 : S ime 1 3 0 0 c — 1 : Simel 2 7 2 c— 1 : Nikalac Ms— 11 d — 1 : Epycoat 8 2 8 d — 2 : Epolite 1 00MF -45 - (42)1321702 Table 2 \ Resolved residual film rate cross-sectional shape protrusion spacer shape determination shape determination Example 1 Good good A Good C Good example 2 Good good B Good C Good example 3 Good good B Good A Good Example 4 Good Good B Good A Good Example 5 Good Good B Good A Good Example 6 Good Good B Good A Good Example 7 Good Good B Good A Good Example 8 Good Good B Good C Good Example 9 Good Good B Good C Good Example 10 Good Good B Good c Good Example 11 Good Good B Good A Good Example 12 Good Good B Good A Good Example 13 Good Good B Good A Good Example 14 Good Good B Good A Good-46 - (43) (43) 1321702 Table 3 Heat resistance (%) Solvent resistance (%) Transparency (%) Oscillation voltage retention rate Example 1 3 3 9 7 Good good example 2 2 2 9 6 good good example 3 3 3 9 8 good good example 4 3 3 9 5 good good example 5 3 3 9 6 good good example 6 2 2 9 6 good good example 7 3 3 9 6 good good example 8 3 3 9 5 good good example 9 3 3 9 6 good good example 10 2 3 9 7 good good example 11 4 4 9 6 good good example 12 3 3 9 5 good good example 13 3 3 9 7 Good Good Example 14 3 3 9 5 Good Good Example 1 5 Using the composition solution (S -) prepared in Example 1, the composition solution (S - 1 ) was applied to the glass by a spin coater. The substrate was then prebaked on a hot plate at 90 ° C for 2 minutes to form a film having a film thickness of 4.0 μm. Then, a width of 5 μm corresponding to the protruding portion is left, and the intensity of the wavelength of 365 nm is -70-(44) (44)1321702 light 1 〇 second through the mask having the pattern. Then, it was developed at 25 ° C for 60 seconds using a 4 wt% aqueous solution of tetramethylammonium hydroxide, and then washed with pure water. After exposure to ultraviolet light having a wavelength of 365 nm and a intensity of 100 W/cm 2 for 3 seconds, it was baked in an oven at 22 〇 C for baking for 60 minutes to form a protrusion. With respect to the obtained projections, the cross-sectional shape was observed using a scanning electron microscope in the same manner as in the above (4-1), and the evaluation result was A. As described above, the radiation-sensitive resin composition for forming the protrusions and/or spacers for the vertical alignment type liquid crystal display device of the present invention is excellent in resolution and residual film ratio, and can form a pattern shape, heat resistance, solvent resistance, and transparency. A fine alignment type liquid crystal display element excellent in alignment property, voltage holding ratio, and the like can be obtained by using an excellent protrusion and/or a spacer. The method for forming protrusions and/or spacers for a vertical alignment type liquid crystal display device of the present invention can be finely processed, and can easily control the shape and size such as height or bottom size, and can form pattern shape, heat resistance, and solvent resistance with high efficiency and stability. A vertical alignment type liquid crystal display element excellent in alignment properties, voltage holding ratio, and the like can be obtained by using protrusions and spacers excellent in properties and transparency. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an example of a schematic view of a cross-sectional shape of a projection and a spacer. Fig. 2 is a view showing an example of a sectional view of a cross-sectional shape of a vertical alignment type liquid crystal display element having projections and spacers. -48-

Claims (1)

1321702 41321702 4 拾、申請專利範圍 -一 第93 1 1 1 495號專利申請案 中文申請專利範圍修正本 民國98年2月25日修正 !·—種垂直配向型液晶顯示元件用突起及間隔件之 形成方法，其特徵爲含有（a)鹼可溶性樹脂，（b)l，2 —醌 二疊氮化合物，（c)下述式（1 )表示之化合物及/或（d ) 分子內具有2個以上之環氧基之鹼不溶性或難溶性的化合 物，Picking up, applying for a patent scope - a patent application No. 93 1 1 1 495, a Chinese patent application scope revision, revised on February 25, 1998, a method for forming a protrusion and a spacer for a vertical alignment type liquid crystal display element, It is characterized in that it contains (a) an alkali-soluble resin, (b) a 1,2-quinonediazide compound, (c) a compound represented by the following formula (1) and/or (d) having two or more rings in the molecule. a compound in which an alkali base is insoluble or poorly soluble, (式中，R1〜R6係互相獨立表示氫原子或—CH2OR基，R 爲氫原子或碳數1〜6之直鏈或支鏈狀之烷基），且爲垂直 配向型液晶顯示元件用之突起及間隔件之形成用之輻射敏 感性樹脂組成物之被膜在基板上形成的步驟；介由突起及 間隔件形成用之光罩，對該被膜進行輻射曝光的步驟；將 曝光後之被膜以鹼顯像液顯像形成突起及間隔件之圖案的 步驟；及對該圖案進行輻射曝光的步驟所構成。 2 .如申請專利範圍第1項之垂直配向型液晶顯示元 件用突起及間隔件之形成方法，其中（a)鹼可溶性樹脂含 有具有酚性羥基及/或羧基之自由基聚合性單體之單獨聚 1321702 合物或共聚物。 3 . —種垂直配向型液晶顯示元件用突起及間隔件， 其特徵係藉由申請專利範圍第1或2項之垂直配向型液晶 顯示元件用突起及間隔件之形成方法所形成。 4. 一種垂直配向型液晶顯示元件，其特徵爲具備申 請專利範圍第3項之突起及間隔件。(wherein R1 to R6 each independently represent a hydrogen atom or a -CH2OR group, and R is a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms), and is used for a vertical alignment type liquid crystal display device. a step of forming a film of a radiation-sensitive resin composition for forming a protrusion and a spacer on a substrate; a step of irradiating the film through a mask for forming a protrusion and a spacer; and exposing the film after exposure The alkali developing solution develops a pattern of protrusions and spacers; and a step of irradiating the pattern with radiation exposure. 2. The method for forming a protrusion for a vertical alignment type liquid crystal display element and a spacer according to the first aspect of the invention, wherein (a) the alkali-soluble resin contains a radical polymerizable monomer having a phenolic hydroxyl group and/or a carboxyl group. Poly 1321702 compound or copolymer. A protrusion and a spacer for a vertical alignment type liquid crystal display element, which are characterized by the method for forming a protrusion for a vertical alignment type liquid crystal display element and a method for forming a spacer according to the first or second aspect of the invention. A vertical alignment type liquid crystal display device characterized by having a projection and a spacer of the third item of the patent application.
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US8389593B2 (en) * 2008-12-24 2013-03-05 Lg Chem, Ltd. Composition for simultaneously forming two isolated column spacer patterns
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