201042384 六、發明說明： 【發明所屬之技術領域】 本發明是有關感光性鹼性水溶液顯像型的樹脂組成 物、以及使用該樹脂組成物而形成之硬化膜以及隔板，尤 其是關於在基板上形成微細之隔板時所適用的黑色阻劑 (Black Resist)用的感光性樹脂組成物、以及藉由該感光 性樹脂組成物所形成之隔板。 【先前技術】 彩色濾光片通常是在玻璃、塑膠薄片等透明基板的表 〇 面上形成黑色之矩陣（黑色矩陣；Black Matrix)，接著， 依序將紅、綠、藍等3種以上的不同色相，形成條紋（stripe) 狀或馬赛克（mosaic)狀等之彩色圖案。圖案大小是隨彩色 慮光片的用途以及各自的顏色而異，一般是5至了⑽以瓜左 右。又，重疊之位置精準度是數至數十，藉由尺寸 精度南的微細加工技術來製造。 彩色瀘、光片的代表性製造方法，有染色法、印刷法、 顏料分散法、電沉積（electrodeposition)法等。其中，尤 其是將含有色材料之光聚合性組成物塗布在透明基板上， 藉由重複進行圖像曝光、顯像、視需要之硬化而形成彩色 慮光片圖像之顏料分散法，係由於可得到彩色濾光片像素 (p i xe 1)之位置、膜厚等之精度高、耐光性/耐熱性等耐^ 性優良，且針孔等缺陷少之濾光片，故而廣泛被採用。 其中，黑色矩陣在紅、綠、藍之彩色圖案間，一般是 配置成格子狀、條紋狀或是馬赛克狀，藉由抑制各色間之 321906 4 201042384 Ο ο 混色而發揮提高對比度或是防止由於漏光所造成的TFT錯 誤動作之功效。因此，對黑色矩陣要求有高的遮光性。以 往，黑色矩陣一般是依據以鉻等金屬膜來形成的方法而 成。此手法因為是在透明基板上蒸鍍鉻等金屬後，歷經光 微影（Photol i thography )步驟將鉻層進行蝕刻處理而成 者’故在薄的膜厚之下可以高精度得到高遮光性。相反的， 其係製造步驟長且生產性低的手法，而會有高成本、因# 刻處理之廢液等而造成環境問題等之問題。 在此，作為解決此等問題者，專利文獻i提案使用感 光性樹脂之光«彡法。錢，以財法所得讀脂遮光膜， 為了表現與由料金屬膜所成之黑色矩陣同等的遮光性 (光學漢度），遮光性之顏料等之含量必需為大量，但㈣ 脂黑色矩陣般在光全波長區域中要求遮光能力時，在照射 紫外線而光硬化之過程中，由於遮光性之顏料會吸收紫外 線’導致U)即使在曝光部分中’亦會產生相對於膜厚方 向之交聯密度之差，並且在塗膜表面即使充分光硬化，在 基底面也很難光硬化；2)«使曝光部分與未曝 的交聯密度之差變顯著；3)由於摻配有大量不溶於顯ς 之遮光性顏料，以致顯像性顯著下降等；因此， / 阻劑的光感度、解像性、密著性、顯像性、而有黑色 狀之明晰（sharp)性等方面之課題。 、’（时ge)形 隹寻利又馱2揭不含有將特定之芳香族严 _ 物與（甲基）丙烯酸之反應物進一步與多元竣酸嘎其& _匕& 應而得之含有不飽和基之化合物作為樹脂 /、S文酐反 战分的黑色阻 321906 5 201042384 劑’係具有高遮光率’容㈣由光微影法而形成精細圖案， 並且成為絕緣性、耐熱性、密著性、及室溫保存安定性也 優異之遮光性薄膜形成用組成物。然而，此專利文獻2是 適於黑色矩陣的標準膜厚為右之薄膜用黑色阻劑 者，有關膜厚超過1.5//m者之光硬化性、顯像特性等則完 全未探討。 為了達成1%明免色彩化/高精細化’彩色濾光片相關 材料之一的樹脂黑色矩陣，係以膜厚i # m左右的薄膜的使 用範圍為主流，但近年來，要求比目前為止更高之高遮光fJ 化，超過膜厚1. 5 // m之樹脂黑色矩陣也新登場。又，最近， 導入在陣列上之彩色濾光片（c〇1〇r Filter 〇n Array)之技 術的面板正受到矚目。此技術是將彩色濾光片基板與TFT 陣列基板-體化者，不需要2種基板之精密之位置相合， 使彩色遽光片之紅、藍、綠各像素可微細化至極限，因而 使面板達成南精細化。然而，如此之在陣列上之彩色渡光 片所用的樹脂黑色輯，由於f要高遮光性 ，所以通常膜 厚必需為2/zm以上。 y &而’隨著樹脂黑色矩陣之膜厚增大，曝光部分之相 =於膜厚方向的交聯密度之差擴大，故更難得到達成高感 1且形狀良好的黑色圖案。又，在之後的減成過程中， =曝光部分之相對於膜厚方向的交聯密度有差異，所以 a膜表面與基板附近之熱硬化收縮會產生差異，塗膜表 面粗輪度增大’表面平滑性惡化，可能在表面起敏紋，或 對之後的紅、藍、綠的各像素形成會有不好之影響。 6 321906 201042384 -於專=獻之:色濾、光片相關材料的例子，可見 法重覆進行薄膜印刷而成膜到15至18_/由= 0 ，故其為製膜需要長時間的方法，並且，由於並非關於樹脂 黑⑽’而是關於紅、藍、綠等彩色矩陣之形 内合’故作為遮光犋利用時，遮光能力不足夠。又利 文獻4係藉由背面光而形成厚膜之方法，但此等 色，而是將藍色物作為遮光膜利用，在遮光性方面並不^充 足，再者’由於是進行與通常製程不同之背面曝光，所以 在生產性或收率方面有問題。再者，專利文獻5係有關換 配無機氧化物凝膠之平坦化性能優異之彩色濾光片用保護 膜的内容’使用該文獻記載之組成物形成遮光膜時， 能力係大巾i不足。 ^ 又’在專利文獻6中，係例示含有粒狀氧化矽（silica) 之樹脂黑色矩陣用感光性樹脂組成物。使塗布在透明基板 ❹上之感光性樹脂組成物（塗膜）硬化而形成隔板（塑膠矩陣） 時’通常，係以使塗膜光硬化而形成預定圖案之隔板的方 式顯像後，進行熱處理（後烘烤（post-bake))。如上所述， 若只進行光硬化，則塗膜之厚度方向之基底面側之硬化恐 怕會不充分，最後係藉由後烘烤而形成隔板。然而，如第 2圖所示，將顯像後之塗膜2(第2圖（a)所示之狀態，2a 是光硬化之部分）進行後烘烤時，變成在基板侧具有緣邊 (hem)之隔板（第2圖（b)所示之狀態）。此係因藉由熱會使 部分樹脂軟化之故，亦即所謂的坍塌現象。於是，專利文 7 321906 201042384 而破保後叫^ 餘$含絲狀氧化石夕， 3所干，以m 定性，最終是如第2圖⑹之符號 ^ 1保住顯像後之塗膜形狀的隔板為目標。 二而’㈣氧切由於凝聚力高’在分散安 尚有改善之餘地。又，將含有今 細m ^ #含㈣錄乳切之感光性樹脂 、、、成㈣在純上之後，當崎乾燥錢輯時，氧化 I粒子因為有高凝聚力所以粒子相互間會凝聚，故作為遮 先性成分使狀碳聽子_距離會接近，恐料致體積 電阻率下降。再者，粒狀氧㈣由於對有機溶劑之親和性 低，故為了破保後供烤後的形狀安定性而必需推配一定量 以上’但粒狀氧㈣之含量增加時，對圖案直線性等顯像 特性可能會有不良影響。 而且’雖也曾試著使用大量遮光性成分作為高遮光化 之手段，但在使用碳等導電性材料作為顏料時，黑色矩陣 之體積電阻會下降，則顯示裝置等之可靠度恐怕會降低。 [先前技術文獻] (專利文獻）[Technical Field] The present invention relates to a resin composition for a photosensitive alkaline aqueous solution development type, and a cured film and separator formed using the resin composition, and more particularly to a substrate. A photosensitive resin composition for a black resist (Black Resist) to be used for forming a fine separator, and a separator formed of the photosensitive resin composition. [Prior Art] A color filter usually forms a black matrix (Black Matrix) on the surface of a transparent substrate such as glass or plastic sheet, and then three or more kinds of red, green, and blue are sequentially arranged. Different hue forms a color pattern such as a stripe or a mosaic. The size of the pattern varies with the purpose of the color filter and the color of each color, and is generally 5 to (10) to the left of the melon. Moreover, the positional accuracy of the overlap is several to several tens, and it is manufactured by the micro-machining technique of the size accuracy south. Representative methods for producing colored enamels and light sheets include dyeing methods, printing methods, pigment dispersion methods, and electrodeposition methods. Among them, in particular, a pigment dispersion method in which a photopolymerizable composition containing a color material is coated on a transparent substrate and a color light-receiving sheet image is formed by repeating image exposure, development, and, if necessary, hardening, is A color filter pixel (pi xe 1) has a high precision such as a film thickness and a film thickness, and is excellent in light resistance and heat resistance, and a filter having few defects such as pinholes is widely used. Among them, the black matrix is generally arranged in a lattice shape, a stripe shape or a mosaic shape between the red, green and blue color patterns, and the contrast is prevented by the color mixing between the colors of the colors, and the light is prevented from leaking due to the color difference between the colors 321906 4 201042384 Ο ο The effect of the TFT error action caused. Therefore, a high opacity is required for the black matrix. In the past, the black matrix was generally formed by a method of forming a metal film such as chromium. In this method, since a metal such as chromium is vapor-deposited on a transparent substrate, the chromium layer is etched by a photolithography step, so that a high light-shielding property can be obtained with high precision under a thin film thickness. On the contrary, it is a technique in which the manufacturing steps are long and the productivity is low, and there are problems such as high cost, environmental problems caused by the waste liquid treated by the engraving, and the like. Here, as a person who solves such problems, Patent Document i proposes to use a light-sensitive resin method. Money, the fat-shielding film obtained by the financial method, in order to express the same light-shielding property (optical hardness) as the black matrix made of the metal film, the content of the light-shielding pigment must be large, but (4) the fat black matrix When the light-shielding ability is required in the full-wavelength region of the light, the light-blocking pigment absorbs the ultraviolet rays during the photo-curing process, causing the cross-linking with respect to the film thickness direction even in the exposed portion. The difference in density, and even sufficient photohardening on the surface of the coating film, it is difficult to photoharden on the base surface; 2) «the difference between the exposed portion and the unexposed crosslink density becomes significant; 3) due to the incorporation of a large amount of insoluble Obviously, the light-shielding pigment is so marked that the development property is remarkably lowered. Therefore, the light sensitivity, the resolving property, the adhesion property, the developing property, and the blackness of the resist are sharp. . , '(时 ge) shape 隹 驮 驮 驮 揭 揭 揭 揭 揭 揭 揭 揭 揭 揭 揭 揭 揭 揭 揭 揭 揭 揭 揭 揭 揭 特定 特定 特定 特定 特定 特定 特定 特定 特定 特定 特定 特定 特定 特定 特定 特定 特定 特定 特定 特定 特定 特定 特定 特定A compound containing an unsaturated group as a resin/, S-anhydride anti-war fraction black resist 321906 5 201042384 agent 'has a high light-shield ratio' (4) formed by a fine pattern of photolithography, and becomes insulating, heat-resistant, A composition for forming a light-shielding film which is excellent in adhesion and room temperature stability. However, this Patent Document 2 is a black resist for a film having a standard film thickness of a black matrix, and the photocurability and development characteristics of a film having a film thickness of more than 1.5/m are not discussed at all. In order to achieve a resin black matrix of one of the 1% color-removing/high-definition color filter-related materials, the use range of the film having a film thickness of i #m is the mainstream, but in recent years, the demand is higher than The higher the black shading, the resin black matrix that exceeds the film thickness of 1. 5 // m is also new. Further, recently, panels for introducing color filters (c〇1〇r Filter 〇n Array) on an array are attracting attention. In this technique, the color filter substrate and the TFT array substrate-body are combined, and the precise positions of the two types of substrates are not required, so that the red, blue, and green pixels of the color light-emitting sheet can be miniaturized to the limit, thereby The panel reached a southern refinement. However, in the resin black series used for the color light-emitting sheet on the array, since f is required to have high light-shielding property, the film thickness is usually required to be 2/zm or more. y & and as the film thickness of the resin black matrix increases, the difference in the cross-link density of the phase of the exposed portion in the film thickness direction is increased, so that it is more difficult to obtain a black pattern having a high-sensitivity 1 and a good shape. Further, in the subsequent subtraction process, the crosslink density of the exposed portion with respect to the film thickness direction is different, so that the thermal hardening shrinkage of the surface of the a film and the vicinity of the substrate is different, and the rough rotation of the surface of the coating film is increased' The surface smoothness is deteriorated, and it may be sensitive to the surface, or may have a bad influence on the formation of each of red, blue, and green pixels. 6 321906 201042384 - In the special = contribution: color filter, light film related materials, can be seen repeated film printing film to 15 to 18_ / by = 0, so it takes a long time to film, Further, since it is not related to the resin black (10)' but in the form of a color matrix such as red, blue or green, the light-shielding ability is not sufficient when it is used as a light-shielding device. Further, the document 4 is a method of forming a thick film by back light, but the blue color is used as a light-shielding film, and the light-shielding property is not sufficient, and the process is performed as usual. Different back exposures are problematic in terms of productivity or yield. In addition, Patent Document 5 relates to a protective film for a color filter excellent in flattening performance of an inorganic oxide gel. When a light-shielding film is formed using the composition described in the document, the capacity is insufficient. Further, in Patent Document 6, a photosensitive resin composition for a resin black matrix containing granular cerium oxide is exemplified. When the photosensitive resin composition (coating film) coated on the transparent substrate is cured to form a separator (plastic matrix), it is usually "imaged" in such a manner that the coating film is photocured to form a separator having a predetermined pattern. A heat treatment (post-bake) is performed. As described above, if only photocuring is performed, the hardening of the base surface side in the thickness direction of the coating film may be insufficient, and finally, the separator is formed by post-baking. However, as shown in Fig. 2, when the coated film 2 (the state shown in Fig. 2(a) and the portion where 2a is photohardened) is post-baked, it has a rim on the substrate side ( The hem) partition (state shown in Figure 2 (b)). This is due to the fact that some of the resin is softened by heat, which is called a collapse phenomenon. Therefore, the patent text 7 321906 201042384 and after the breach of insurance called ^ surplus $ containing filamentous oxidized stone evening, 3 dry, m qualitative, and finally the symbol ^ 2 as shown in Figure 2 (6) to retain the shape of the film after development The partition is the target. Second, the '(four) oxygen cuts have room for improvement due to high cohesion. In addition, when the photosensitive resin is contained in the fine m ^ # containing (4) milk, and after (4) is pure, the particles of the oxidized I particles will condense because of the high cohesive force. As a precautionary component, the carbon listener _ distance will be close, and the volume resistivity will decrease. Further, since the granular oxygen (IV) has a low affinity for the organic solvent, it is necessary to push a certain amount or more in order to ensure the shape stability after baking, but when the content of the granular oxygen (four) is increased, the pattern is linear. Imaging characteristics may have adverse effects. Further, although a large amount of light-shielding components have been tried as a means for high light-shielding, when a conductive material such as carbon is used as a pigment, the volume resistance of the black matrix is lowered, and the reliability of a display device or the like may be lowered. [Previous Technical Literature] (Patent Literature)
專利文獻1:日本特開平4-177202號公報 專利文獻2 :日本特開平8_278629號公報 專利文獻3·日本特開平5-〇45513號公報 專利文獻4·日本特開平5-181009號公報 專利文獻5.日本特開平5-288926號公報 專利文獻6 :日本特開2008-304583號公報 【發明内容J 321906 8 201042384 — (發明欲解決之課題） - 在此，本發明人等針對在使塗布感光性樹脂組成物而 成之塗膜硬化時之形狀安定性為優異，尤其在含有遮光性 成分而作成厚膜時也可得到顯像特性優良之硬化膜，並且 刀散女疋性為優良的感光性樹脂組成物加以專心檢討之結 果，發現藉由摻配預定之丙烯酸系樹脂粒子，即可完全解 決以往之問題點，因而完成本發明。 因此’本發明之目的係提供一種感光性樹脂組成物， 〇 其可解決上述課題，例如，即使在得到超過1.5# m之厚膜 之硬化膜時，圖案尺寸安定性也優異，同時，可得到顯像 邊際（margin)、圖案之邊緣形狀的明晰性等為良好的圖 案’並且，使用碳等導電性材料作為遮光性成分時，體積 電阻也不會下降。 又’本發明之另外目的係提供使用該感光性樹脂組成 物而形成之硬化膜及隔板。 Q (解決課題之手段） 亦即，本發明係提供一種感光性樹脂組成物，係以（1) 光硬化性樹脂及/或光硬化性單體、以及（2)丙浠酸系樹脂 粒子作為必需成分’其特徵為：（2)成分之丙烯酸系樹脂粒 子的一次粒徑之平均值為5〇至2〇〇 nm，前述組成物中的 丙稀酸系樹脂粒子（2)與光硬化性樹脂及/或光硬化性單 體（1)之重量比（（2)/(0)為〇.丨至2.0之範圍。 又，本發明係提供一種感光性樹脂組成物，係以（1) 光硬化性樹脂及/或光硬化性單體、以及（2)丙烯酸系樹脂 9 321906 201042384 粒子作為必需成分，且復含有（3)至少1種選自黑色有機顏 料、混色有機顏料及遮光材中之遮光性成分而成，其特徵 為：（2)成分之丙烯酸系樹脂粒子的一次粒徑之平均值為 50至200 nm，前述組成物中的丙烯酸系樹脂粒子（2)及遮 光性成分（3)的總重量、與光硬化性樹脂及/或光硬化性單 體（1)之重量比（（2) + (3)/(1))為0. 1至2.0之範圍。 進一步’本發明係提供一種硬化膜，係將上述感光性 樹脂組成物塗布在基板上並乾燥後，必需歷經（a)藉由紫外 線曝光裝置進行曝光、（b)藉由鹼性水溶液進行顯像、及（c) 熱處理之各步驟而得。 再者，本發明係提供一種隔板，係將上述感光性樹脂 組成物塗布在基板上並乾燥後，必需歷經（a)藉由紫外線曝 光裝置進行曝光、（b)藉由驗性水溶液進行顯像、及（c)熱 處理之各步驟而得，且纟基板上區劃出複數個像素區域的 隔板’高度為1.5至4/zm’並且，錐形角（1：叩打 在60°以上。 (發明效果） 本發明之感光性樹脂組成物係由於分散安定 並且，硬化時之形狀技性優異，同時，顯像特性也優卜 故可用於作為以彩色遽光片為首之EL - # 乂 料。尤其是在含有遮光性成分而得到厚祺之= 宜，例如，即使在得砂1.、左右切過其之厚膜的^ 色矩陣時，也可得到圖案尺寸安定性倍 、的'，·、 、I工霞共，日晏貝傻、多 圖案的邊緣形狀的明晰性等良好的圖宏 ^ ”、、豕透I示、 固系。再者，本發明之 321906 10 201042384 ' 感光性樹脂組成物在使用碳等導電性材料作為遮光性成分 - 時，也可盡量減少其體積電阻之下降。 【實施方式】 ，以下，對本發明詳細說明。 本發明之組成物係含有（1)及（2)成分作為必需成分， 在得到遮光性之硬化膜時，復含有（3)成分作為必需成分。 在此’（1)成分的光硬化性樹脂，例如，以如下述之含有不 飽和基之化合物為佳。亦即，使具有由雙紛類所衍生之2 〇 個縮水甘油醚（glycidyl ether)基的環氧化合物、與（甲基） 丙烯酸（在此，是指「丙烯酸及/或甲基丙烯酸」之意）反 應而得到具有羥基之化合物，再使該具有羥基之化合物與 多元羧酸或其酸酐反應而得到的環氧（曱基）丙烯酸酯酸加 成物。在此，由雙酚類所衍生之環氧化合物係指藉由使雙 酚類與表鹵醇（epihalohydrin)反應而得的環氧化合物之 意。該環氧化合物及由該環氧化合物所衍生之含有不飽和 Q基之化合物（環氧（曱基）丙烯酸酯酸加成物），係由前述專 利文獻2等而為公知，可廣泛使用相關之化合物。 上述之情形，（1)成分之光硬化性樹脂，因為同時具有 乙烯性不飽和雙鍵與敌基，故職予感光性樹脂組成物優良 之光硬化性、良好的顯像性、圖案特性，而提升硬化膜之 物性。 亦即，（1)成分之光硬化性樹脂，係以由下述通式G) 所示的環氧化合物所衍生者為佳。此環氧化合物是由雙盼 類所衍生者。因此，藉由說明雙盼類，即可瞭解含有不飽 321906 11 201042384 和基之化合物，所以較佳之具體例係藉由雙賴來說明 ch2-ch-ch2〇Patent Document 1: Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. When the coating film is cured by a resin composition, the shape stability is excellent, and in particular, when a light-shielding component is contained and a thick film is formed, a cured film having excellent development characteristics can be obtained, and the glazing property is excellent in photosensitivity. As a result of intensive review of the resin composition, it has been found that the conventional problems can be completely solved by blending predetermined acrylic resin particles, and thus the present invention has been completed. Therefore, the object of the present invention is to provide a photosensitive resin composition which can solve the above problems. For example, even when a cured film of a thick film exceeding 1.5 mm is obtained, the pattern size stability is excellent, and at the same time, When the development margin and the sharpness of the edge shape of the pattern are good patterns, and the conductive material such as carbon is used as the light-shielding component, the volume resistance does not decrease. Further, another object of the present invention is to provide a cured film and a separator formed using the photosensitive resin composition. Q (Means for Solving the Problem) In other words, the present invention provides a photosensitive resin composition comprising (1) a photocurable resin and/or a photocurable monomer, and (2) a propionic acid resin particle. The essential component is characterized in that the average particle diameter of the acrylic resin particles of the component (2) is 5 Å to 2 〇〇 nm, and the acrylic resin particles (2) and the photocurability in the above composition are. The weight ratio of the resin and/or photocurable monomer (1) ((2)/(0) is in the range of 〇.丨 to 2.0. Further, the present invention provides a photosensitive resin composition, which is (1) Photocurable resin and/or photocurable monomer, and (2) acrylic resin 9 321906 201042384 particles as an essential component, and (3) at least one selected from the group consisting of a black organic pigment, a mixed color organic pigment, and a light shielding material The light-shielding component is characterized in that the average particle diameter of the acrylic resin particles of the component (2) is 50 to 200 nm, and the acrylic resin particles (2) and the light-shielding component in the composition ( 3) total weight, photocurable resin and/or photocurable single The weight ratio of the body (1) ((2) + (3) / (1)) is in the range of 0.1 to 2.0. Further, the present invention provides a cured film by coating the above photosensitive resin composition on a substrate. After drying and drying, it is necessary to obtain (a) exposure by an ultraviolet exposure apparatus, (b) development by an aqueous alkaline solution, and (c) heat treatment. Further, the present invention provides a spacer. In the plate, after the photosensitive resin composition is applied onto a substrate and dried, it is necessary to perform (a) exposure by an ultraviolet exposure device, (b) development by an aqueous solution by an aqueous solution, and (c) heat treatment. And a separator having a height of 1.5 to 4/zm in a plurality of pixel regions on the substrate, and a taper angle (1: beaten at 60° or more. (Effect of the invention) The photosensitive resin of the present invention Since the composition is excellent in dispersion and stability, it is excellent in shape and skill at the time of hardening, and at the same time, it is excellent in development characteristics, and can be used as an EL-# pigment which is mainly composed of a color light-receiving sheet, especially in the case of containing a light-shielding component. Thick 祺 = 宜, for example, even in the sand 1 . When the color matrix of the thick film is cut, the pattern size stability is doubled, and the ', ·, I, I, Xia, and the shape of the edge of the multi-pattern are good. In the case of the photosensitive resin composition, when a conductive material such as carbon is used as a light-shielding component, the volume can be minimized as much as possible. [Embodiment] The present invention will be described in detail below. The composition of the present invention contains the components (1) and (2) as essential components, and when a cured film having a light-shielding property is obtained, the component (3) is further contained. As an essential ingredient. The photocurable resin of the component (1) is preferably, for example, a compound containing an unsaturated group as described below. That is, an epoxy compound having 2 glycidyl ether groups derived from a double genus, and (meth)acrylic acid (herein, "acrylic acid and/or methacrylic acid") An epoxy(fluorenyl) acrylate acid addition product obtained by reacting a compound having a hydroxyl group with a compound having a hydroxyl group and a polyvalent carboxylic acid or an anhydride thereof. Here, the epoxy compound derived from a bisphenol is an epoxy compound obtained by reacting a bisphenol with an epihalohydrin. The epoxy compound and the unsaturated Q group-containing compound (epoxy thiol acrylate acid adduct) derived from the epoxy compound are known from the above-mentioned Patent Document 2 and the like, and can be widely used. Compound. In the case of the photocurable resin of the component (1), since the ethylenically unsaturated double bond and the host group are simultaneously provided, the photosensitive resin composition has excellent photocurability, good developability, and pattern characteristics. And improve the physical properties of the cured film. In other words, the photocurable resin of the component (1) is preferably derived from an epoxy compound represented by the following formula G). This epoxy compound is derived from the double expectant class. Therefore, by explaining the double-seeking class, it is possible to understand the compound containing the unsaturated 321906 11 201042384 and the base, so the preferred specific example is explained by the double lyrics ch2-ch-ch2〇
LR2 γLR2 γ
OCH2-CH-CH20. R2 OHOCH2-CH-CH20. R2 OH
(惟，式中UR2獨立地表示氫原子、碳數丨至5之烧基、 苯基、或#原子之任一者，X獨立地表示單鍵、_C0_、〜s〇2_、 -C(CF3)2-、-Si(CH3)2- m(CH3)2-、-〇-或下述式⑵ 所示之9, 9-苐基，η是0至ι〇之數；）。 0¾⑵ 較佳的賦予含有不飽和基之化合物的雙酚類，可列舉 如：含有雙（4—羥基苯基）酮、雙（4-羥基-3, 5-二甲基苯基） 酮、雙（4-羥基-3, 5-二氯苯基）酮、雙（4_羥基苯基）礙、雙 (4-羥基-3, 5-二曱基苯基）颯、雙（4_羥基_3, 5_二氣苯基） 砜、雙（4-羥基苯基）六氟丙烷、雙（4_羥基_3, 5_二甲基苯 基）六氟丙烷、雙（4-羥基-3, 5-二氯苯基）六氟丙烷、雙（4_ 羥基苯基）二曱基矽烷、雙（4—羥基一3, 5_二甲基苯基）二曱 基矽烷、雙（4-羥基-3, 5-二氣苯基）二甲基矽烷、雙（4_羥 基苯基）甲烷、雙（4-羥基-3, 5-二氣笨基）曱烷、雙（4-羥基 -3, 5-二溴苯基）甲烷、2, 2-雙（4-羥基苯基）丙烷、2, 2-雙 (4-羥基-3, 5-二曱基笨基）丙烷、2, 2-雙（4-羥基-3, 5-二氣 苯基）丙烧、2, 2-雙（4-羥基-3-甲基苯基）丙烷、2, 2-雙（4- 321906 12 201042384 - 羥基-3-氯苯基）丙烷、雙（4-羥基苯基）醚、雙（4-羥基-3, 5- ' 二甲基苯基）鍵、雙（4-經基-3, 5-二氯苯基）鍵等之化合 物，或X為前述9, 9-第基之9, 9-雙（4-羥基苯基）苐、9, 9- . 雙（4-羥基-3-曱基苯基）1、9, 9-雙（4-羥基-3-氣苯基） 苐、9, 9-雙（4-羥基-3-溴苯基）苐、9, 9-雙（4-羥基-3-氟苯 基）苐、9, 9-雙（4-羥基-3-甲氧基苯基）苐、9, 9-雙（4-羥基 -3, 5-二甲基苯基）苐、9, 9-雙（4-羥基-3, 5-二氣苯基）苐、 9, 9-雙（4-羥基-3, 5-二溴苯基）苐等，或是4, 4’-聯酚 Ο (4, 4’ -biphenol)、3, 3’ -聯紛等化合物。 由於（1)成分之光硬化性樹脂係由上述雙酚類所衍生 之環氧化合物而得，故從透明性、耐熱性、顯像特性等優 異之觀點而言，為較佳者。除了該環氧化合物以外，如酚 紛酸清漆（phenol novolac)型環氧化合物、或曱酌·紛酸清 漆型環氧化合物等，只要為有意義地含有2個縮水甘油醚 基之化合物者，則亦可使用。又，使雙酚類進行縮水甘油 醚化時，雖會混入寡聚物單元，但若在式（1)中之η之平均(In the formula, UR2 independently represents a hydrogen atom, a carbon number of 烧 to 5, a phenyl group, or a # atom, and X independently represents a single bond, _C0_, ~s〇2_, -C (CF3) 2, -Si(CH3)2- m(CH3)2-, -〇- or 9,9-fluorenyl group represented by the following formula (2), η is the number of 0 to ι〇;). 03⁄4 (2) Preferred are bisphenols which impart a compound containing an unsaturated group, and examples thereof include bis(4-hydroxyphenyl) ketone, bis(4-hydroxy-3, 5-dimethylphenyl) ketone, and bis (4-hydroxy-3,5-dichlorophenyl)one, bis(4-hydroxyphenyl), bis(4-hydroxy-3,5-didecylphenyl)anthracene, bis(4-hydroxyl) 3, 5_di-phenyl) sulfone, bis(4-hydroxyphenyl)hexafluoropropane, bis(4-hydroxy-3,5-dimethylphenyl)hexafluoropropane, bis(4-hydroxy-3) , 5-dichlorophenyl) hexafluoropropane, bis(4-hydroxyphenyl)dioxandecane, bis(4-hydroxy-3,5-dimethylphenyl)didecyldecane, bis(4-hydroxyl -3, 5-diphenyl) dimethyl decane, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-3, 5-dioxaphenyl) decane, bis(4-hydroxy-3) , 5-dibromophenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3, 5-dimercapto)propane, 2, 2- Bis(4-hydroxy-3,5-diphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-321906 12 201042384 - hydroxyl 3-chlorophenyl)propane, double (4- a compound such as a phenyl)ether, a bis(4-hydroxy-3,5'-dimethylphenyl) bond, a bis(4-amino-3,5-dichlorophenyl) bond, or X is the aforementioned 9, 9-diyl 9, 9-bis(4-hydroxyphenyl)anthracene, 9, 9-. bis(4-hydroxy-3-indolylphenyl) 1,9,9-bis(4-hydroxyl 3-oxophenyl) ruthenium, 9,9-bis(4-hydroxy-3-bromophenyl)anthracene, 9,9-bis(4-hydroxy-3-fluorophenyl)anthracene, 9,9-double (4-hydroxy-3-methoxyphenyl)indole, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)anthracene, 9,9-bis(4-hydroxy-3, 5 -diphenyl)anthracene, 9,9-bis(4-hydroxy-3,5-dibromophenyl)anthracene, or 4,4'-biphenolol (4,4'-biphenol), 3 , 3' - combined with other compounds. Since the photocurable resin of the component (1) is obtained from the epoxy compound derived from the above bisphenol, it is preferable from the viewpoint of excellent transparency, heat resistance, development characteristics and the like. In addition to the epoxy compound, such as a phenol novolac type epoxy compound or a phthalic acid type epoxide type compound, if it is a compound which contains two glycidyl ether groups meaningfully, Can also be used. Further, when the bisphenol is glycidated, the oligomer unit is mixed, but the average of η in the formula (1)
Q 值為0至10，較佳是0至2之範圍的話，本樹脂組成物之 性能就沒有問題。 又，使如此之環氧化合物與（甲基）丙烯酸反應而得到 環氧（曱基）丙烯酸酯，而可與該環氧（曱基）丙烯酸酯分子 中之羥基反應的多元羧酸或其酸酐係可列舉如：馬來酸、 號珀酸、衣康酸、苯二甲酸（phthalic acid)、四氫苯二甲 酸、六氫苯二甲酸、甲基内亞曱基四氫苯二曱酸（methyl endomethylenetetrahydrophthaic acid)、氣橋酸 13 321906 201042384 (Chlorendic Acid)、甲基四氫苯二甲酸、偏苯三甲酸 acid)、均苯四？酸（叩1^〇贴111以(：acid) 等或其酸if、或是二苯f _四_、聯苯四㈣、聯苯趟 四竣酸等芳香族多元幾酸或此等之酸二酐等。因此，關於 酸酐與酸二酐之使用比率，可依藉由曝光、驗性顯像操作 而形成微細圖案之方式來選擇適當之比率。 有關（1)成分之光硬化性樹脂，可只使用其中之丨種， 也可使用2種以上之混合物。又，環氧化合物與（甲基）丙 烯酸的反應、由該反應所得之環氧（甲基）丙稀酸醋與多元 酸或其酸酐的反應，係可採用上述專利文獻2等所揭示之 公知的方法，但無特別之限制。 又，在本發明中，（1)成分只要是會因光而硬化（聚合） 者即可，故感光性樹脂組成物在未硬化之狀態下係包括只 含有未樹脂化的成分（單體）之情形。亦即，作為（1)成分而 使用之光硬化性單體，係具有至少i個以上之乙稀性不飽 和鍵的光聚合性單體，例如，可列舉如：（甲基）丙稀酸 翹基乙醋、（甲基）丙稀酸2_經基丙醋、（甲基）丙婦酸2-^基，酯等具有羥基之單體，或乙二醇二(甲基)丙烯酸 s曰、—乙二醇二（曱基）丙烯酸酯、三乙二醇二（甲美）而说 酸酯、四乙二醇二（甲基）丙烯酸醋、四亞甲基二醇二曱基） 丙烯酸酯、三羥曱基丙烷三（曱基）丙烯酸酯、三羥曱基乙 烷二(一甲基）丙烯酸酯、季戊四醇二（甲基）丙烯酸酯、季戊 四醇三（甲基）丙烯酸酯、季戊四醇四（甲基）丙烯酸酯、二 季戊四醇四（甲基）丙烯酸醋、二季戊_六（甲基）丙稀酸 321906 14 201042384 - 醋、甘油（甲基）丙烯酸酯等（甲基）丙烯酸酯類，此等化合 . 物可單獨只使用其中之1種，此外也可併用2種以上來使 用。 , 本發明之感光性樹脂組成物雖含有（1)成分之光聚合 性化合物’但為了使其光硬化’以含有光聚合起始劑為佳。 光聚合起始劑係因照射紫外線光而產生自由基種，加成在 光聚合性化合物而開始自由基聚合，使樹脂組成物硬化。 光聚合起始劑可列舉如：二苯甲酮、米希勒_ 〇 (*^比161'’5 1^1：0116)、^『一四甲基-4,4’-二胺基二苯甲 酮、4-甲氧基-4’-二曱基胺基二苯曱酮、4, 4，-二乙基胺基 二苯甲酮、2-乙基蒽醌、菲等芳香族酮；苯偶因甲基醚、 本偶因乙基鱗、苯偶因苯基醚等苯偶因謎類；甲基苯偶因、· 乙基本偶因荨苯偶因，2-(鄰-氯苯基）-4，5_苯基味坐二聚 物、2-(鄰-氯苯基）-4, 5-二（間-甲氧基苯基）咪唑二聚 物、2-(鄰-氟苯基）-4,5-二苯基咪唑二聚物、2-(鄰-曱氧 ^ 基苯基）~4, 5 -二苯基咪唑二聚物、2, 4, 5-三芳基咪唑二聚 物、2-苄基-2-二甲基胺基-1-(4-嗎琳基苯基）丁酮、2-三 氯甲基-5-苯乙烯基-1，3, 4-噚二唑、2-三氯甲基-5-(對一 亂基本乙晞基）-1，3, 4_曙二〇坐、2-三氣甲基-5~(對-甲氧基 苯乙烯基）~ 1,3,4-〇¥二哇等函曱基嘆唆化合物；2,4,6~ 參（二氯曱基）-1，3, 5-三哄、2-曱基-4, 6-雙（三氣甲基） -1，3, 5-二卩井、2-苯基-4, 6-雙（三氯甲基）-1，3, 5-三明：、 2-(4-氯苯基）-4, 6-雙（三氯R甲基）-1，3, 5-三啡、2-(4-曱氧基苯基）-4,6-雙（三氯曱基）-1，3, 5-三啡、2-(4-甲氧 321906 15 201042384 基^基）4, 6 -雙（二氯r曱基）_j，3, 5_三哄、2_(4-甲氧基 苯乙稀基）' 4,6-雙（三氯甲基M，3,5-三畊、2-(3,4,5_ 三甲氧基苯乙烯基)-4,6—雙(三氯甲基)]，3,5一三畊、 2-(4-曱硫基苯乙烯基）_4, 6_雙（三氯甲基Μ，〗』—三啡等 鹵甲基S — [I井系化合物；2, 2_二曱氧基乂 2—二苯基乙院 :卜酮、2-甲基小[4_(甲硫基）苯基]嗎琳基丙綱、2_ 苄基2 一甲基胺基_1_[4_嗎琳基苯基卜丁酮— I，〗 —經基一 。裒己基苯基_等光聚合^始劑；如日本特表 號a報所6己載之肟酯（〇xime ester)系起始劑。 此等光聚合起始劑可單獨或混合2種以上而使用。 亦可添加其本身雖並沒有作為光聚合起始劑或增感劑 之作用，但藉由與上述化合物組合使用而可增大光聚合起 始劑或增感劑之能力的化合物。如此之化合物可列舉如： 當與二苯甲馳合使用時有效果之三乙醇胺等三級胺。 以（1)成分之合計100重量份為基準，光聚合起始劑之 使用！係以7至5G重量份為適宜。光聚合起始劑之推配比 率未達7重量份m合之速度變緩慢，感度會下降， 方面超過50重量份時，感度會過強，圖案線寬相對 =圖案遮罩變成太粗之狀態，恐怕會發生對於遮罩不能忠 、也重現線寬4圖案邊緣成為鑛齒狀而不明晰等的問題。 (2)成力之丙烯酸系樹脂粒子，雖不受限於製造法或形 狀（球狀、非球狀、單核結構、芯殼結構等），但為了使凝 给良’並且為了在將該感光性樹脂組成物 主布在基板上並乾燥後，使歷經藉由紫外線曝光裝置曝 32J906 16 201042384 光、藉由驗性水溶液顯像、熱處理的各步驟而得到 膜的錐利成為6()、上，贿狀、單核結構為佳。在此， 硬倾之錐形角是指Μ 1圖之剖面說則騎，顯像成 預疋之形狀’在經熱處理而得之硬化膜（#為彩色渡光 時則是隔板）的基板侧所成的Θ角度。錐形角為60。以上係 表示所得之硬化膜的形狀i安定性優良之意。同時，錐形角 之上限係排除成為逆錐形狀之情形，理論上是9〇。。When the Q value is from 0 to 10, preferably from 0 to 2, the performance of the resin composition is not problematic. Further, a polycarboxylic acid or an anhydride thereof which reacts such an epoxy compound with (meth)acrylic acid to obtain an epoxy (mercapto) acrylate and reacts with a hydroxyl group in the epoxy (fluorenyl) acrylate molecule Examples thereof include maleic acid, crotonic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, and methyl endonyltetrahydrophthalic acid ( Methyl endomethylenetetrahydrophthaic acid), gas bridge acid 13 321906 201042384 (Chlorendic Acid), methyl tetrahydrophthalic acid, trimellitic acid acid), benzene tetra? Acid (叩1^〇贴111 to (:acid) or its acid if, or diphenyl f _ tetra _, biphenyl tetra (tetra), biphenyl fluorene tetradecanoic acid, etc. or such acid A dianhydride or the like. Therefore, the ratio of the use ratio of the acid anhydride to the acid dianhydride can be selected in accordance with the method of forming a fine pattern by an exposure and an image forming operation. The photocurable resin of the component (1), It is possible to use only one of them, or a mixture of two or more kinds thereof. Further, the reaction of the epoxy compound with (meth)acrylic acid, the epoxy (meth)acrylic acid vinegar obtained from the reaction, and the polybasic acid or In the reaction of the acid anhydride, a known method disclosed in Patent Document 2 or the like can be used, but it is not particularly limited. In the present invention, the component (1) may be cured (polymerized) by light. Therefore, in the uncured state, the photosensitive resin composition includes a component (monomer) which contains only unresinized. That is, the photocurable monomer used as the component (1) has at least i. a photopolymerizable monomer having more than one ethylidene unsaturated bond, for example, For example, (meth)acrylic acid ethyl acetoacetate, (meth) acrylic acid 2 _ propyl propyl vinegar, (methyl) propyl benzoic acid 2- yl group, ester and other monomers having a hydroxyl group, or Ethylene glycol di(meth)acrylic acid s 曰, ethylene glycol bis(indenyl) acrylate, triethylene glycol bis(methylamide), acid ester, tetraethylene glycol di(meth)acrylic acid vinegar, Tetramethylene glycol dimercapto) acrylate, trishydroxypropyl propane tris(mercapto) acrylate, trishydroxy ethane di(monomethyl) acrylate, pentaerythritol di(meth) acrylate, Pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate vinegar, dipenta-hexa(methyl)acrylic acid 321906 14 201042384 - vinegar, glycerol (methyl) (meth) acrylates such as acrylates, and the like may be used alone or in combination of two or more. The photosensitive resin composition of the present invention contains the photopolymerizable compound 'of the component (1), but it is preferred to contain a photopolymerization initiator for photohardening. The photopolymerization initiator generates radical species by irradiation with ultraviolet light, and is added to a photopolymerizable compound to initiate radical polymerization to cure the resin composition. The photopolymerization initiator may, for example, be benzophenone, Michelle _ 〇 (*^ ratio 161''5 1^1:0116), ^"tetramethyl-4,4'-diamino group II Benzophenone, 4-methoxy-4'-didecylaminodibenzophenone, 4, 4,-diethylaminobenzophenone, 2-ethyl anthracene, phenanthrene and other aromatic ketones Benzoin methyl ether, bis-ethyl scale, benzoin phenyl ether and other benzoin mysteries; methyl benzene, ethyl acetoin, 2-(o-chloro Phenyl)-4,5-phenyl-sodium dimer, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)imidazole dimer, 2-(o- Fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-indolyloxyphenyl)~4,5-diphenylimidazole dimer, 2, 4, 5-triaryl Imidazole dimer, 2-benzyl-2-dimethylamino-1-(4-morphinylphenyl)butanone, 2-trichloromethyl-5-styryl-1,3, 4 -oxadiazole, 2-trichloromethyl-5-(for a chaotic basic acetyl group)-1,3,4_曙二〇, 2-trismethyl-5~(p-methoxy Styryl)~ 1,3,4-〇¥二哇, etc. 曱 唆 唆 compound; 2,4,6~ ginseng(dichloroindenyl)-1,3, 5-trimium, 2-曱Base-4,6-bis(trismethyl)-1,3,5-dioxin, 2-phenyl-4,6-bis(trichloromethyl)-1,3, 5-trim: 2-(4-chlorophenyl)-4,6-bis(trichloro-R-methyl)-1,3,5-trimorphine, 2-(4-decyloxyphenyl)-4,6-bis ( Trichloroindolyl-1,3,5-trimorphine, 2-(4-methoxy 3,210,906, 15,2010, 384, yl) 4,6-bis(dichloror-yl)_j, 3, 5_trimium, 2_(4-methoxystyrene)' 4,6-bis(trichloromethyl M,3,5-three tillage, 2-(3,4,5-trimethoxystyryl)-4, 6-bis(trichloromethyl)], 3,5-three tillage, 2-(4-sulfonylstyryl)_4,6_bis(trichloromethylhydrazine, 〗 〖-trihalide Base S — [I well compound; 2, 2_didecyloxy 乂 2 - diphenyl ethoxylate: ketone, 2-methyl small [4_(methylthio)phenyl] phenanthyl propyl, 2_benzyl 2 monomethylaminol_1_[4_morphinyl phenylbutanone - I, 〗 - via the group of 1. hexyl phenyl _ _ photopolymerization initiator; such as the Japanese special table number a The above-mentioned oxime ester (〇xime ester) is an initiator. These photopolymerization initiators may be used singly or in combination of two or more kinds. a compound which functions as a polymerization initiator or a sensitizer, but which can increase the ability of a photopolymerization initiator or a sensitizer by use in combination with the above compound. Such a compound can be exemplified by: A tertiary amine such as triethanolamine which is effective when used. The use of a photopolymerization initiator based on 100 parts by weight of the total of the components (1)! It is suitably 7 to 5 G parts by weight. When the ratio of the photopolymerization initiator is less than 7 parts by weight, the speed of the combination becomes slow, and the sensitivity is lowered. When the amount exceeds 50 parts by weight, the sensitivity is too strong, and the pattern line width is relatively = the pattern mask becomes too thick. I am afraid that there is a problem that the mask is not loyal, and the line width 4 pattern edge becomes a mineral tooth shape and is not clear. (2) The acrylic resin particles to be formed are not limited to the production method or shape (spherical, non-spherical, mononuclear structure, core-shell structure, etc.), but in order to After the photosensitive resin composition is mainly laid on the substrate and dried, the film is obtained by exposing 32J906 16 201042384 light by an ultraviolet exposure device, and the film is obtained by an aqueous solution of an aqueous solution and heat treatment to obtain a film having a taper of 6 (). On the other hand, a bribe-like, single-core structure is preferred. Here, the taper angle of the hard tilt refers to the substrate of the Μ 1 map, which is said to ride, and is developed into a shape of a pre-formed 'hardened film obtained by heat treatment (# is a separator when color is light) The angle of the side formed by the side. The taper angle is 60. The above shows that the shape of the obtained cured film is excellent in stability. At the same time, the upper limit of the taper angle is excluded from the shape of the inverse cone, which is theoretically 9 〇. .
又’丙烯酸系樹脂粒子之—次粒徑平均值必須在至 200 mn之範圍内，而以在7〇至15〇⑽之範圍内為佳。在 Ο 此，粒子之一次粒徑之平均值係藉由穿透型電子顯微鏡進 行粒徑觀察，不特定地選出丨⑽個粒子，測定粒子之長軸 長度與短軸長度，藉由將該等相加平均而求得。此時，在 構成凝聚塊絲錢（aggregate)時，—絲子是指構成此 等之粒子。丙烯酸系樹脂粒子之一次粒徑之平均值未達如 nm時，分散性方面並不佳。相反的，超過2〇〇時，表 面粗糙度惡化，在維持體積電阻值之方面並不佳。又，在 提高形狀安定性上，粒徑變得過大時，相對於粒子重量， 粒子體積比會下降而有必要添加大量之丙烯酸系樹脂粒 子，對於鹼性水溶液很難維持良好之顯像性。將在可維持 良好之顯像性範圍内添加粒徑超過· nm之丙烯酸系樹脂 粒子的該感光性樹脂組成物塗布在基板上並乾燥後，歷經 藉由紫外線曝光裝置曝光 '藉由鹼性水溶液顯像、熱處理 的各步驟而得到的硬化膜，會如所謂的坍塌現象而變成潰 散之形狀’其側面會變成圓弧狀。同時，丙烯酸系樹脂粒 321906 201042384 子之粒度分布雖沒有特別限制，但為了保持粒子分散性， 相對於以上述方料得之—:錄社平均值，以在+3σ範 圍内有80%以上為佳。 關於丙烯酸系樹脂粒子之摻配比率，組成物中之丙烯 酸系樹絲子⑵與光硬化性《及/或光硬化性單體⑴ 之重量比（⑵/(1))為G.1纟2.0之範圍，而以成為〇 5 至1· 5之範圍為佳。重量比未達〇1時，則變得缺乏提高 硬化膜之形狀安定性的效果，相反的，超過2. 0時’顯像 性能會下降’或是體積電阻值恐怕會下降。又，在本發明 中，樹脂組成物雖可含有（3)之遮光性成分，但此時可認為 疋將。卩分丙烯酸系微粒子以遮光性成分取代，故丙烯酸 系樹脂粒子（2)及遮光性成分（3)之總重量、與光硬化性樹 脂及/或光硬化性單體（丨）的重量比（（2) + (3)/(1))為〇. i 至2.0之範圍，而以成為〇· 5至15之範圍為佳。此時之 重量比的下限與上限之各別定義係與先前所述者同樣。 關於丙婦酸系樹脂粒子（2 )’其表面以經酸處理為佳。 藉由實施表面酸處理而使粒子分散性提高，並且，在將咸 光性樹脂組成物塗布在基板上並乾燥後，且在藉由紫外線 曝光裝置曝光後，若進行表面酸處理，則可使驗性水溶液 之顯像性更加提高’而可得到直線性良好的圖案。 又，本發明之感光性樹腊組成物也可摻配遮光性成分 (3)而製成得到遮光性硬化膜之態樣。遮光性成分（3)係^ 自黑色有機顏料、混色有機顏料、及遮光材中之至少丨種| (3)成分之遮光性成分以耐熱性、耐光性及耐溶劑性優異者 3219〇6 18 201042384 為佳< 在此 Ο Ο 黑色有機顏料可列舉如花黑（perylene blaCk)花月黑（Cyanine black)等。混色有機顏料可列舉 如將&自紅、藍、綠、紫、黃色、花青(Cyanine)、洋紅 (magenta)等中之至彡2種之顏料混合並經擬似黑色化 :。材可列舉如碳黑、氧化鉻、氧化鐵、鈦黑、苯胺 黑化月黑’也可適當地選擇2種以上而使用，尤其從遮 '表面平滑性 '分散安定性、與樹脂之相溶性為良好 之觀點而言’以碳黑為較佳者。 相對於上述（1)成分之合計100重量份（在含有光聚合 成分時’是包含其之合計100重量份），（3)成分之 摻配比例以u J 乂川至150重量份為佳。比5〇重量份少時，則 遜光性變;^并 .于並不足夠’超過150重量份時，則由於本來作 馬黏結劑 R lnder)的感光性樹脂的含量減少，故會發生在 f生之同時亦損及膜形成能力而不佳之問題。 之外發明之感光性樹脂組成物中，在上述（1)至(3)成分 、使用^谷劑為佳。溶劑可列舉如：甲醇、乙醇、正 、 ϊρ (Terp.、丙醇、乙二醇、丙二醇等醇類；α-或松油醇 ne〇i)等萜烯（七打卯此）類 等；丙酮、甲基乙基酮、 某苯等从〜甲基一2-吡咯啶酮等酮類；曱笨、二曱苯、四曱 乙美、、办芳香族煙類；溶纖劑（cellosolve)、甲基溶纖劑、 醇、丁$劑、卡必醇（carbitol)、曱基卡必醇、乙基卡必 丙醇 丙 必醇 乙 丙二醇單甲基醚、丙二醇單乙基醚、二 單甲基醚、二丙二醇單乙基醚、三乙二醇單甲基醚、 醇單乙基趟等甘醇趟（glycol ether)類；乙酸乙 321906 19 201042384 酉旨、乙酸丁醋、溶纖劑乙酸醋、乙基溶纖劑乙酸g旨、丁基 溶纖劑乙酸醋、卡必醇乙酸醋、乙基卡必醇乙酸I旨、丁基 卡必醇乙酸酯、丙二醇單甲基醚乙酸酯、丙二醇單乙基醚 乙酸酯等乙酸酯類等；藉由使用此等並溶解、混合，即玎 作成均勻之溶液狀組成物。 又’在本發明之感光性樹脂組成物中，因應需求也< 摻配硬化促進劑、熱聚合抑制劑、可塑劑、充填材、溶劑、 塗平劑、消泡劑等添加劑。熱聚合抑制劑可列舉如：氮酿、 氫醌單甲基醚、焦掊酚（pyrogallol)、三級丁基兒茶齡、 吩噻畊（phenothiazine)等，可塑劑可列舉如：苯二甲酸二 丁酯、苯二甲酸二辛酯、三曱苯基等，又，消泡劑或塗平 劑可列舉如：矽系、氟系、丙烯酸系之化合物。 本發明之感光性樹脂組成物，在除去溶劑之固形份（固 形份中包含硬化後變成固形份之單體）中，（1)至（3)成分合 計是在70 wt%以上，而以在80 wt%為佳，更佳是含有⑽wt〇/〇 以上。在樹脂組成物中，溶劑之含有比例係隨著塗布所使 用之塗布機而使最適黏度範圍變化，一般以在5 ^ m # υ 主 90 wt% 的对圍為佳。 又，本發明之硬化膜，可使用上述本發明之 脂組成物並藉由光微影法而形成。可列舉如下述、、f 就其製造步驟而言，首先，將感光性樹脂組成.方去 X-x yih -h J-c: -T- 乍成〉谷液 而盒不在基板表面上，其次，使溶劑乾燥（預烘 bake))後，在如此而得之被膜上蓋上光罩，照射紫（pre~ 使曝光部分硬化，再使用鹼性水溶液，進行本”外線而 炎未曝光部分 321906 20 201042384 溶出之顯像而形成圖案，再進行作為後乾燥之後烘烤的方 法0 塗布感光性樹脂組成物溶液之基板，可使用在破璃、 透明薄膜（例如聚碳酸酯、聚對苯二曱酸乙二酯、聚醚颯等） 上条鍵IT0、金專透明電極或經圖案化者等。 將該感光性樹脂組成物溶液塗布在基板上之方法，可 適用習知之手段，例如除了溶液浸潰法、噴霧法之外，也 可採取使用輥塗機、溢面塗布機（land c〇at〇r)或旋轉機 ° (sPinner)之方法等任何方法。以此等方法塗布到所期望之 厚度後，藉由除去溶劑（預烘烤）而形成被膜。預烘烤係藉 由烘箱、熱盤等加熱而進行。預烘烤中之加熱溫度及加熱 時間是對應使用之溶劑而適當選擇，例如在80至120它‘”' 溫度下進行1至10分鐘。 預烘烤後進行之曝光係可藉由曝光機來進行，藉由隔 著光罩曝光，而只使對應圖案部分之阻劑進行感光。經適 ❹當選擇曝光機及其曝光照射條件，並使用超高壓水銀燈、 南壓水銀燈、金屬幽素燈、遠紫外線燈等光源來進行曝光， 而使塗膜中之樹脂組成物光硬化。 曝光後之鹼性顯像是以除去未曝光部分之阻劑為目的 而進行，藉由此顯像而形成所期望之圖案。作為適於此鹼 性顯像之顯像液者，雖可舉例如鹼金屬或鹼土金屬之碳酸 鹽水溶液、鹼金屬之氫氧化物之水溶液等，但尤其以使用 含有0. 05至3重量％之碳酸鈉、碳酸鉀、碳酸鋰等碳酸睡 的弱鹼性水溶液在20至30t溫度下來顯像為佳，可使^ 321906 21 201042384 市售之顯像機或超音波洗淨機等而精密地形成微細之 像。 經如此顯像後’例如在180至250t之溫度、及20至 1〇〇分鐘之條件下進行熱處理（後烘烤）。該後烘烤是為了 提高經圖案化之遮光膜與基板的密著性等目的而進行。其 疋與預烘烤相同地，藉由烘箱、熱盤等加熱來進行。本發 明之經圖案化之硬化膜，係藉由以上之光微影法並歷經各 步驟而形成。於是，由本發明之樹脂組成物而得之硬化膜， 係體積電阻值為1〇1°—以上，而以在l〇%cm以上為佳。 尤其在形成隔板時，可得到高度幻5至4_，並且錐形 角為60°以上者。又，因為0D值（光學濃度）也可達到2.0 至4. 5///m，故可適合作為具有高遮光性、高電阻值之彩 色濾光片所適用的彩色濾光片用黑色矩陣。又，亦可適合 作為對應喷墨製程之彩色濾光片用黑色矩陣來使用。 本發明之感光性樹脂組成物，雖如前述係適合經由曝 光、驗性顯像等操作而形成微細之圖案，但即使是經由以 往之網版印刷而形成圖案，亦可得到同樣之硬化膜。 本發明之感光性樹脂組成物可適合作為如形成硬化膜 之塗布材來使用，尤其除了在液晶顯示裝置或攝影元件中 所使用之R、G、B等各顏色彩色渡光片用之印墨或如黑色 矩陣（隔S)之遮光膜㈣成之#，在作4液4投影機用的 黑色矩陣等方面也有用。再者，本發明之感光性樹脂組成 物’除了可適用於如上述彩色液晶顯示器之彩色濾光片印 墨之外K適用於彩色液晶顯示器裝置、彩色傳真機、 321906 22 201042384 一 圖像感應器（i贴狀sensor)等各種之多色顯示體印墨讨 • 料，或在EL元件等中的顯示元件材料。 實施例 <含有丙烯酸系樹脂粒子之分散液之製造例至了、 及 a-Ι 至 a-2 > 將丙烯酸系樹脂粒子（日本paint公司製Fine sphere)、高分子分散劑及丙二醇單甲基醚乙酸酯以表上所 示之比率混合，在珠磨機（Beads Mill)中進行分散，製造 〇 含有丙稀酸系樹脂粒子之分散液A-1至A-4及a-Ι。又， 將丙烯酸系樹脂粒子（日本paint公司製Fine sphere)、 作為遮光性顏料（遮光性成分）之經樹脂被覆之碳黑（三菱 化學公司製MS18E ’粒徑25nm)、高分子分散劑及丙二醇單 曱基謎乙酸醋以表1所示之比率混合，在珠磨機中進行分 散，作成同時含有丙烯酸系樹脂粒子/遮光性顏料兩者之 分散液A - 5。同樣地’將作為遮光性顏料之碳黑改用鈦黑（三 ❹菱材料製，粒徑30 nm)或混色有機顏料黑（御國色素製， 粒徑30 nm)，調製同時含有丙烯酸系樹脂粒子/遮光性顏 料兩者之分散液A-6至A-7。製造編號9之分散液a_2是 未掺配丙烯酸系樹脂粒子，只含有作為遮光性顏料之經樹 月曰被覆之碳黑（二菱材料製MS18E，粒徑25 run)的分散液。 又，製造編號1至8所使用之丙烯酸系樹脂粒子係任—者 皆為將單一組成之丙烯酸系樹脂（單核組成）控制成如球狀 而製造者’一次粒徑之平均值係如表1所示。又，製造編 號1、4至8者是經由以在粒子表面使酸性官能基存在之方 321906 23 201042384 式處理表面而成者，製造 驗性官能基存^ U以録子表面使 表面盎處4在::式f理表面而成者’製造編號2者是 透型雷。 之—讀鼓平均值是藉由穿 顯微鏡進行粒徑觀察’不料地選出_個粒子 子之長轴長度與短軸長度，藉由將該等相加平均 此時，在構成凝聚塊或聚集體時，—次粒子是指 構成此等之粒子。 [表1 ] 製造 分散ί 兩烯酸系 樹脂粒子 顏料 編號 夜編號 表面處理 形狀 1 A-1 酸處理 过你霣4禽 2 A-2 無處理 3 A-3 鹼處理 4 A-4 酸處理 5 A-5 ——— 酸處理 6 A-6 酸處理 7 A-7 酸處理 8 a-1 酸處理 9 a-2 粒徑（η«〇 — 種類 100 狀· 玄 70 球狀單核 70 球狀單核 150 · I -- 球狀單核 100 1-----——. 碳黑 球狀單核 100 -1 —--- 鈦黑 球狀單核 100 """ _ 混色 右德ifi姓 球狀單核 500 • . 1 碳黑 組成 (重董份） 丙烯酸系 樹脂粒子 20 20 20 20 6.4 10 6.4 20 遮光性 顏料 — 一 — — 13.6 50 13.6 20 分散劑 溶劑 5 75 5 75 5 75 5 75 5 75 7 5 5 5 黏度（ffi 黏度 安定性 Pa-s) 室溫 25 〇 30 〇 40 X 22 一- ~ 〇 11 ·—' 16 75 11 75 14 75 7 〇 〇 〇 π 40°C 〇 X X 〇 〇 〇 __〇 〇 〇 〇 關於上述所調製之分散液的黏度，係使用E型黏度 計，在20 rpm、25.0±0.5°C進行測定。並且，測定在室^ 下放置1個月後及在40°C下保管1週後之黏度，以其黏度 、菱化率來评估黏度女疋性。結果’關於含有酸處理及單核 結構之丙烯酸系樹脂粒子的分散液Α4、Α_4至A_7及a—卜 以及不含丙；)#酸糸樹月曰粒子的分散液a-1，測定在室溫下 321906 24 201042384 月*後及。在，C下保管1週後之黏度時，其黏度變 樹r粒子八1G/(在表1巾以0標示）。無處理之丙埽酸系 曰9刀散液A-2、及驗處理之丙職系樹脂粒子分散 「眘⑽] 疋在10%以上（在表1中以x標示）。 [實施例Uu、啸们至4] 〈隔板用感光性樹脂組成物之調製〉Further, the average particle size of the acrylic resin particles must be in the range of up to 200 mn, and preferably in the range of from 7 Å to 15 Å (10). In this case, the average value of the primary particle diameter of the particles is observed by a transmission electron microscope, and 丨(10) particles are not specifically selected, and the major axis length and the minor axis length of the particles are measured. Calculated by adding the average. At this time, when forming agglomerate aggregates, the term "silk" refers to particles constituting such a mass. When the average value of the primary particle diameter of the acrylic resin particles is less than, for example, nm, the dispersibility is not good. On the contrary, when the thickness exceeds 2 Å, the surface roughness deteriorates, and it is not preferable in terms of maintaining the volume resistance value. Further, when the particle size is too large in terms of improving the shape stability, the particle volume ratio is lowered with respect to the weight of the particles, and it is necessary to add a large amount of acrylic resin particles, and it is difficult to maintain good developability with respect to the alkaline aqueous solution. The photosensitive resin composition in which acrylic resin particles having a particle diameter exceeding Mn is added to a substrate in a range capable of maintaining good developability is applied onto a substrate and dried, and then exposed by an ultraviolet exposure device. The cured film obtained by each step of development and heat treatment becomes a collapsed shape as a so-called collapse phenomenon, and its side surface becomes an arc shape. Meanwhile, although the particle size distribution of the acrylic resin particles 321906 201042384 is not particularly limited, in order to maintain the particle dispersibility, it is 80% or more in the range of +3σ with respect to the average value of the above-mentioned materials. good. The blending ratio of the acrylic resin particles in the composition, the weight ratio of the acrylic resin (2) to the photocurability "and/or the photocurable monomer (1) ((2) / (1)) is G.1 纟 2.0" The range is preferably in the range of 〇5 to 1.5. When the weight ratio is less than 〇1, the effect of improving the shape stability of the cured film is lacking. Conversely, when the temperature exceeds 2.0, the development performance is lowered, or the volume resistance value may be lowered. Further, in the present invention, the resin composition may contain the light-shielding component (3), but in this case, it is considered to be a ruthenium. Since the acryl-based fine particles are replaced by a light-shielding component, the total weight of the acrylic resin particles (2) and the light-shielding component (3) and the weight ratio of the photocurable resin and/or the photocurable monomer (丨) ( (2) + (3)/(1)) is in the range of 〇. i to 2.0, and is preferably in the range of 〇·5 to 15. The respective definitions of the lower limit and the upper limit of the weight ratio at this time are the same as those previously described. The surface of the propylene glycol-based resin particles (2)' is preferably treated with an acid. By performing surface acid treatment, the particle dispersibility is improved, and after the salty resin composition is applied onto a substrate and dried, and after being exposed by an ultraviolet exposure device, if surface acid treatment is performed, The developability of the aqueous solution is further improved, and a pattern having good linearity can be obtained. Further, the photosensitive wax composition of the present invention may be blended with the light-shielding component (3) to obtain a light-shielding cured film. The light-shielding component (3) is at least one of the black organic pigment, the mixed color organic pigment, and the light-shielding material. (3) The light-shielding component of the component is excellent in heat resistance, light resistance, and solvent resistance. 3219〇6 18 201042384 is preferable. Here, black organic pigments include, for example, perylene blaCk, Cyanine black, and the like. The color mixed organic pigment may be, for example, a mixture of red, blue, green, purple, yellow, Cyanine, magenta, and the like, and is intended to be blackened: The material may be, for example, carbon black, chromium oxide, iron oxide, titanium black or aniline blackened black. It may be appropriately selected from two or more types, and in particular, from the 'surface smoothness' dispersion stability and compatibility with a resin. For a good point of view, 'carbon black is preferred. The total content of the component (1) is 100 parts by weight (when the photopolymerizable component is contained, and is 100 parts by weight in total), and the blending ratio of the component (3) is preferably from 5% to 150 parts by weight. When it is less than 5 parts by weight, it is inferior to light; when it is not enough, when it is not more than 150 parts by weight, the content of the photosensitive resin which is originally used as a horse binder R lnder is reduced, so it occurs in f is also a problem of poor film formation ability. In the photosensitive resin composition of the invention, it is preferred to use the components (1) to (3) and the gluten. Examples of the solvent include decenes such as methanol, ethanol, n-, ϊρ (alrt., propanol, ethylene glycol, propylene glycol, etc.; α- or terpineol ne〇i); Acetone, methyl ethyl ketone, a certain benzene, etc. from ketones such as methicone-2-pyrrolidone; 曱 、, 曱 曱 benzene, 曱 曱 、 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , methyl cellosolve, alcohol, butyl agent, carbitol, decyl carbitol, ethyl carbitol propanol ethylene glycol monomethyl ether, propylene glycol monoethyl ether, two Glycol ether such as methyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, alcohol monoethyl hydrazine; acetic acid B 321906 19 201042384 酉 、, acetic acid butyl vinegar, cellosolve Acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate An acetate or the like such as propylene glycol monoethyl ether acetate; and by using such a solution, it is dissolved and mixed, that is, it is formed into a homogeneous solution-like composition. Further, in the photosensitive resin composition of the present invention, additives such as a hardening accelerator, a thermal polymerization inhibitor, a plasticizer, a filler, a solvent, a coating agent, and an antifoaming agent are blended in accordance with the demand. Examples of the thermal polymerization inhibitor include nitrogen brewing, hydroquinone monomethyl ether, pyrogallol, tertiary butyl tea age, phenothiazine, and the like, and plasticizers include, for example, phthalic acid. Examples of the dibutyl ester, dioctyl phthalate, triterpene phenyl, and the like, and the antifoaming agent or the coating agent may, for example, be a fluorene-based, fluorine-based or acrylic-based compound. In the photosensitive resin composition of the present invention, in the solid content of the solvent (the monomer which becomes a solid component after hardening is contained in the solid portion), the total of the components (1) to (3) is 70 wt% or more, and 80 wt% is preferred, and more preferably (10) wt 〇 / 〇 or more. In the resin composition, the content ratio of the solvent varies depending on the coater used for coating, and it is generally preferable to have a 90% by weight of 5 ^ m # υ main. Further, the cured film of the present invention can be formed by the photolithography method using the above-described fat composition of the present invention. For example, in the following, f, in terms of the manufacturing steps, first, the photosensitive resin is composed of Xx yih -h Jc: -T- 〉 〉 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷(pre-bake), the mask is covered with the mask, and the violet is irradiated (pre~ the exposed portion is hardened, and then the alkaline aqueous solution is used to perform the "outer line" and the unexposed portion is 321906 20 201042384. Forming a pattern, and performing the method of post-drying and baking. 0. Coating a substrate of a photosensitive resin composition solution, and using a glass or transparent film (for example, polycarbonate or polyethylene terephthalate, Polyether oxime, etc.) Upper bar key IT0, gold-specific transparent electrode or patterned person, etc. The method of applying the photosensitive resin composition solution onto a substrate can be applied by conventional means such as solution dipping method, spraying In addition to the method, any method such as a roll coater, a surface coater (land c〇at〇r) or a rotary machine (sPinner) may be employed, and after being applied to a desired thickness by such methods, Removed solvent The film is formed by baking. The prebaking is performed by heating in an oven, a hot plate, etc. The heating temperature and the heating time in the prebaking are appropriately selected depending on the solvent to be used, for example, at 80 to 120. The temperature is carried out for 1 to 10 minutes. The exposure after prebaking can be performed by an exposure machine, and the resist of the corresponding pattern portion is exposed to light by exposure through the photomask. The machine and its exposure conditions are irradiated with a light source such as an ultrahigh pressure mercury lamp, a south pressure mercury lamp, a metal nucleus lamp, or a far ultraviolet lamp, and the resin composition in the coating film is photohardened. It is carried out for the purpose of removing the resist of the unexposed portion, and the desired pattern is formed by the development. As the developer suitable for the alkaline development, for example, an alkali metal or an alkaline earth metal may be used. An aqueous solution of a carbonate solution, an alkali metal hydroxide, or the like, but in particular, a weakly alkaline aqueous solution containing 0.05 to 3% by weight of sodium carbonate, potassium carbonate, lithium carbonate or the like is used at a temperature of 20 to 30 t. Like It is possible to precisely form a fine image by a commercially available video camera or ultrasonic cleaner, etc. After such development, for example, at a temperature of 180 to 250 tons, and 20 to 1 minute. The heat treatment (post-baking) is carried out under the condition that the post-baking is performed for the purpose of improving the adhesion between the patterned light-shielding film and the substrate, etc., and the same as the pre-baking, by the oven and the hot plate The patterned cured film of the present invention is formed by the above photolithography method and subjected to each step. Thus, the cured film obtained from the resin composition of the present invention has a volume resistivity value. It is preferably 1 〇 1 ° or more, and more preferably 10 〇 % cm or more. Especially in the case of forming a separator, a height of 5 to 4 Å and a taper angle of 60 or more can be obtained. Further, since the 0D value (optical density) can also be 2.0 to 4.5///m, it can be suitably used as a black matrix for a color filter to which a color filter having high light-shielding property and high resistance value is applied. Further, it can also be suitably used as a black matrix for a color filter corresponding to an ink jet process. The photosensitive resin composition of the present invention is suitable for forming a fine pattern by exposure or the like, as described above. However, even if the pattern is formed by conventional screen printing, the same cured film can be obtained. The photosensitive resin composition of the present invention can be suitably used as a coating material for forming a cured film, in particular, an ink for color light-passing sheets of various colors such as R, G, and B used in a liquid crystal display device or a photographic element. Or, as a black matrix (separating S), the light-shielding film (four) into the # is also useful as a black matrix for a four-liquid 4 projector. Furthermore, the photosensitive resin composition of the present invention is applicable to a color liquid crystal display device, a color facsimile machine, and a 321906 22 201042384 image sensor, in addition to being applicable to a color filter ink such as the above-described color liquid crystal display. (i-stick sensor) and other multi-color display body printing inks, or display element materials in EL elements and the like. Example <Production Example of Dispersion Liquid Containing Acrylic Resin Particles, and a-Ι to a-2> Acrylic Resin Particles (Fine sphere, manufactured by Nippon Paint Co., Ltd.), polymer dispersant, and propylene glycol monomethyl The ether ether acetate was mixed at a ratio shown in the table, and dispersed in a bead mill (Beads Mill) to prepare dispersions A-1 to A-4 and a-fluorene containing acrylic resin particles. Further, acrylic resin particles (Fine sphere manufactured by Nippon Paint Co., Ltd.) and resin-coated carbon black (MS18E's particle size 25 nm manufactured by Mitsubishi Chemical Corporation), a polymer dispersant, and propylene glycol were used as a light-shielding pigment (light-shielding component). The monothiol vinegar was mixed at a ratio shown in Table 1, and dispersed in a bead mill to prepare a dispersion A-5 containing both acrylic resin particles and light-shielding pigment. Similarly, the carbon black as a light-shielding pigment is changed to titanium black (made by Sankening Material, particle size: 30 nm) or mixed color organic pigment black (made by Yukisei pigment, particle size: 30 nm), and contains acrylic resin. A dispersion of both particles/light-blocking pigments A-6 to A-7. The dispersion a_2 of the manufacturing number 9 is a dispersion liquid which is not blended with acrylic resin particles and contains only carbon black (MS18E manufactured by Mitsubishi Materials, particle size 25 run) which is coated as a light-shielding pigment. Further, all of the acrylic resin particles used in the production of Nos. 1 to 8 are controlled such that the acrylic resin (single core composition) of a single composition is controlled to have a spherical shape, and the average of the primary particle diameters is as follows. 1 is shown. Further, in the case of manufacturing Nos. 1, 4 to 8, the surface is treated by the method of treating the surface with the acidic functional group on the surface of the particle 321906 23 201042384, and the surface of the recording surface is made to make the surface angstrom 4 In the :: formula f surface of the original 'manufacturing number 2 is a transparent mine. The average value of the reading drum is obtained by observing the particle diameter by wearing a microscope. 'Unexpectedly, the length of the major axis and the length of the short axis of the particle are selected, and by averaging the phases, the agglomerates or aggregates are formed at this time. At the time, the secondary particles refer to the particles constituting these. [Table 1] Manufacturing Dispersion 两 Dienoic Acid Resin Particle Pigment No. Night No. Surface Treatment Shape 1 A-1 Acid Treated You 霣 4 Poultry 2 A-2 No Treatment 3 A-3 Alkali Treatment 4 A-4 Acid Treatment 5 A-5 ——— Acid treatment 6 A-6 Acid treatment 7 A-7 Acid treatment 8 a-1 Acid treatment 9 a-2 Particle size (η«〇- species 100 shape · Xuan 70 spherical mononuclear 70 sphere Single Core 150 · I -- Spherical Single Core 100 1------. Carbon Black Spherical Single Core 100 -1 —--- Titanium Black Spherical Single Core 100 """ _ Mixed Color Right Deifi surname spheroidal single core 500 • . 1 carbon black composition (heavy Dong) acrylic resin particles 20 20 20 20 6.4 10 6.4 20 light-blocking pigment - one - 13.6 50 13.6 20 dispersant solvent 5 75 5 75 5 75 5 75 5 75 7 5 5 5 Viscosity (ffi viscosity stability Pa-s) Room temperature 25 〇30 〇40 X 22 One - ~ 〇11 ·—' 16 75 11 75 14 75 7 〇〇〇π 40°C 〇 XX 〇〇〇 __ 〇〇〇〇 The viscosity of the dispersion prepared above was measured at 20 rpm and 25.0 ± 0.5 ° C using an E-type viscometer. month And the viscosity after storage for 1 week at 40 ° C, the viscosity and the scent rate were used to evaluate the viscosity of the female genital. Results 'About the dispersion of acrylic resin particles containing acid-treated and mononuclear structure Α 4, Α_4 to A_7 And a-b and no C;; ## 糸 曰 曰 的 的 的 的 a 。 。 321 321 321 321 321 321 321 321 321 321 321 321 321 321 321 321 321 321 321 321 321 When the viscosity after 1 week was stored under C, the viscosity of the tree was changed to 8 G / (indicated by 0 in Table 1). Untreated propionic acid 曰 9 knife powder A-2, and the processing of the propylene resin particle dispersion "Chen (10)] 疋 at 10% or more (indicated by x in Table 1). [Example Uu, Xiao Min to 4] <Modulation of photosensitive resin composition for separators>
一將^述所得之分散液與表2記載之各成分分別以表中 7、率恳5，然後加入石夕院偶合劑S-510(信越化學製） (U3伤與兩二醇單甲基趟乙酸醋，使全量成為彻重量 伤，固形份濃度成為2〇重量％。然後，加入矽系界面活性 齊'J SH3775M (Toray · D〇wnCOrning 製）0.005 重量份，使用 2/ζιη之聚丙烯製薄膜過濾器且在加壓〇 2吆/⑽2下過 遽，δ周製感光性樹腾組成物。又，表2中記載之各成分的 付號分別表示如下述之物質。The dispersion obtained by the above description and the components described in Table 2 are respectively listed in Table 7, at a rate of 5, and then added to Shi Xiyuan coupling agent S-510 (manufactured by Shin-Etsu Chemical Co., Ltd.) (U3 wound and di-diol monomethyl group)趟acetic acid vinegar, the total amount is completely weight-damaged, and the solid content concentration is 2% by weight. Then, 0.005 parts by weight of the lanthanide interface activity 'J SH3775M (manufactured by Toray · D〇wn Corning) is added, and 2/ζιη polypropylene is used. The membrane filter was passed through a 〇2吆/(10)2 under pressure, and a photosensitive dendritic composition of δ was produced. Further, the symbols of the respective components described in Table 2 indicate the following.
a、3:奈米級氧化矽分散液，MN〇 byk-3650(BYK Japan 製，粒徑20至25 nm) 1 :具有苐骨架之環氧丙烯酸酯的酸酐聚縮合物的丙二 醇單甲基醚乙酸酯溶液（樹脂固形份濃度= 56.1重 量％，新曰鐵化學公司製商品名V259ME) C、1 :二季戊四醇六丙烯酸酯與二季戊四醇五丙烯酸酯之 混合物（曰本化藥公司製商品名DPHA) C〜2 :三羥曱基丙烷三丙烯酸酯（巴工業製商品名 SARTOMER SR-351S) 乃、1 :光聚合起始劑’ IRGACURE OXE01 (汽巴日本製） 25 321906 201042384 D-2:光聚合起始劑，IRGACURE 〇χΕ〇2(汽巴日本製） 實* £例 1 2 3 4 5 6 7 8 9 10 11 比較例1 比較例2 比較例3 tb較例4 銥威 (重*») 分散液 A-1 45. 00 A-1 15. 00 A-2 45.00 Α-3 45.00 A-4 45. 00 A-5 45.00 A-5 50.00 A-5/a-2 22. 5/22. 5 A-5 45.00 A-6 15,00 A-7 45.00 a-1 45.00 a-2 45.00 a-3 36.00 A-1 60.00 (2) 重量 (3) 重量 9.00 0.00 3.00 0. 00 9,00 Q. 00 9.00 0.00 9.00 0.00 2.88 6.12 3.20 6. 80 1.44 7.46 2.88 6.12 1.50 7.50 2.88 6.12 9.00 0.00 0.00 9.00 0.00 9.00 3.84 8. 04 mm B-1 10.81 B-1 20.41 B-1 10.81 B-1 10.81 B-1 10.81 ΒΊ 9.46 B-1 S. 06 B-1 9.46 B-1 9.84 B-1 10.80 B-1 9.46 B-1 10.81 B-1 9.44 B-1 10.93 B-1 6.01 箪tt C-1 2.01 C-1 3.80 C-! 2.01 C-1 2.01 C-1 2.01 C-1 t.76 C-1 1.50 C-1 1.76 C-1 1.55 C-1 2. 01 C-1 1.76 C-1 2. ¢1 C-1 149 C-1 2. 03 C-1 U2 ⑴總重量 8.07 15. 25 8.07 8.07 8.07 7. 07 6.01 7. 07 7. 07 8.07 7. 07 8. 07 6.79 δ. 16 4.48 D-1 0.40 D-1 0. 76 D-1 0.40 D-Ι 0.40 D-1 0.40 D-2 1.41 D-2 i.20 D-2 i.41 t>-2 i.41 D-2 t.61 D-2 1.41 D-1 0.40 D-2 1.69 D-i 0.41 D-l 0.22 級成 重ttt (2)+(3) /(1) 1.12 0.20 1.12 1.12 1.12 1.27 1.66 1.26 1.27 1.12 1.27 1.12 1.33 1.10 2.65 重布異物 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 Q 感度 10 10 10 10 10 25 30 35 30 30 35 10 35 10 10 飆像密著仕 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 X 圖案直線性 〇 〇 X X 〇 〇 Δ 0 〇 〇 〇 〇 〇 X Ra 〇 〇 〇 〇 o 〇 〇 〇 〇 〇 〇 X 〇 〇 雖形狀 〇 Δ Ο 〇 Δ 〇 〇 〇 0 〇 〇 / tt積電扭 £14 E14 El 4 £14 E14 E14 E14 E13 E13 E14 £14 £14 E10 £14 Ell ---1 2. i 2,4 2.7 2.3 2,3 2.3 3.8 - ~ [表 2] __ 使用旋轉塗布機，在125 mmxl25 mm之玻璃基板上， 以使後烘烤後之膜厚成為2. lyjn之方式塗布上述所得之 各感光性樹脂組成物，纟啊預供烤]分鐘。之後，將曝 光間隙調整成8G_，在乾燥塗膜上覆蓋線/間距（line/ sp^ce) 之負型光罩’以j線照度3〇祝/ ⑽2之超高壓核燈騎⑽mj八m2之料線，使感光部 分進行光硬化反應。 其次。’將此完成曝光之塗板在〇 〇5%氫氧化卸水溶液 ^ 23C進行1 kgf/cm壓力之沖洗顯像，將觀察到圖 案之時間作為顯像間斷時間（BT(break time)，秒），再進 321906 26 201042384 行20秒之顯像後，進行5壓力之 塗膜之未料料，而纽縣板上料^務=，除去 使用熱風乾燥機在23(rc進行3〇分鐘之^ 之^ 例及比較例所得到之硬化膜的評 *方、>。各實施 述。 興方法係如下所 [塗布異物] Ο <不=轉Γ後之㈣上觀察耻射狀條料表示為X 不良>，未觀察到時則表示為〇< 良好:>。 [感度] 進遮罩（stepmusk)，測定在BT+2G秒觀測到殘 旗之曝光量（mj/cm2)。 [顯像密著性] 、將在BT+40秒時殘留有2〇//m圖案之情形以〇表示， 立將剝離者以X表示。 [圖案直線性] ο 簡微鏡觀察後烘烤後之2G/Zm線，觀察到有鑛齒狀 日·以X表示，無鑛齒狀時以〇表示。又，在局部觀察到有鑛 #狀時以△表示。 [膜厚及表面粗糙度（表面粗糙度Ra : JIS B0601_1994)] 0使用觸針式膜厚計（Tencor(股）製）測定。表面粗糙度 疋在黑色矩陣表面上隔2 mm寬處之Ra，當未達i5〇時為 〇，超過150 A時為x。 [錐形狀] 在顯像時間為間斷時間+10至3〇秒時，以操作型電子 27 321906 201042384 顯微鏡觀察後烘烤後之20/zm線剖面，基板與結構物（硬化 膜）錐形部所成之角度皆在60°以上者為〇，未達60°則為 △，圓弧形狀（第2圖之（b))時則以X表示。 [體積電阻值] 在全面經鉻蒸鍍之玻璃基板上進行與前述相同之操 作，形成後烘烤後有2. 1/zm膜厚之塗膜。在塗膜上形成 10 _ Φ之铭蒸鑛膜，在Cr-A 1間外加1至10 V之電壓， 測定電流值，求得電阻。 [0D測定] 使用後烘烤後為2. 1 μ m膜厚之塗膜，使用大塚電子製 0D計測定，記載為每1 // m之OD值。 在實施例1、3、4、6至11中任一者之錐形角都是 60°以上，體積電阻值也顯示良好之值。然而，在使用粒徑 大之丙烯酸系樹脂粒子的比較例1、以及沒有丙烯酸系樹 脂粒子的比較例2中，則錐形角形狀皆為圓弧狀，尤其在 比較例2可看出體積電阻值也下降。又，含有氧化矽粒子 的比較例3、以及丙烯酸系樹脂粒子的添加量多的比較例4 則顯像特性並不佳。 [實施例12] 使用實施例6至11所用之感光性樹脂組成物，形成開 口部（像素區域）為300 //mxl00/im且具有線寬為30y m、 膜厚（高度）為2. 1 /im之遮光性隔板的矩陣。之後’在氧大 氣壓電漿處理3秒後，在CF4大氣壓電漿進行處理3秒。在 該遮光性隔板（遮光膜）上使用水或丁基卡必醇乙酸酯 28 321906 201042384 r (BCA) ’測定靜態接觸角時，分別顯示100°、50°。對此黑 * 色矩陣中，使用東芝科技製之喷墨頭，打入黏度9 mPa · sec且固形分濃度20%之紅、藍、綠色印墨，在230°C進行 後烘烤，形成彩色濾光片。結果，可得到良好之彩色濾光 片。 【圖式簡單說明】 第1圖表示在基板上所形成之硬化膜（隔板）之態樣的 剖面說明圖。 〇 第2圖（a)及（b)表示以往例中之感光性樹脂組成物 (塗膜）之硬化之態樣的剖面說明圖。 【主要元件符號說明】 1 基板 2 塗膜 2a 塗膜之硬化部分 3 塗膜後之塗膜之理想形狀 Θ 角度 29 321906a, 3: nano-sized cerium oxide dispersion, MN 〇byk-3650 (made by BYK Japan, particle size 20 to 25 nm) 1 : propylene glycol monomethyl ether of an acid anhydride polycondensate of an epoxy acrylate having an anthracene skeleton Acetate solution (resin solid concentration = 56.1% by weight, trade name V259ME, manufactured by Niigato Iron Chemical Co., Ltd.) C, 1: Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (trade name of Sakamoto Chemical Co., Ltd.) DPHA) C~2: Trihydroxydecylpropane triacrylate (trade name SARTOMER SR-351S), 1: Photopolymerization initiator ' IRGACURE OXE01 (Ciba made in Japan) 25 321906 201042384 D-2: Photopolymerization initiator, IRGACURE 〇χΕ〇2 (Ciba made in Japan) Real* £1 1 3 3 4 5 6 7 8 9 10 11 Comparative Example 1 Comparative Example 2 Comparative Example 3 tb Comparative Example 4 Converse (Heavy* ») Dispersion A-1 45. 00 A-1 15. 00 A-2 45.00 Α-3 45.00 A-4 45. 00 A-5 45.00 A-5 50.00 A-5/a-2 22. 5/22 5 A-5 45.00 A-6 15,00 A-7 45.00 a-1 45.00 a-2 45.00 a-3 36.00 A-1 60.00 (2) Weight (3) Weight 9.00 0.00 3.00 0. 00 9,00 Q 00 9.00 0.00 9.00 0.00 2.88 6.12 3.20 6. 80 1.44 7.46 2.88 6.12 1.50 7.50 2.88 6.12 9.00 0.00 0.00 9.00 0.00 9.00 3.84 8. 04 mm B-1 10.81 B-1 20.41 B-1 10.81 B-1 10.81 B-1 10.81 ΒΊ 9.46 B-1 S. 06 B-1 9.46 B -1 9.84 B-1 10.80 B-1 9.46 B-1 10.81 B-1 9.44 B-1 10.93 B-1 6.01 箪tt C-1 2.01 C-1 3.80 C-! 2.01 C-1 2.01 C-1 2.01 C -1 t.76 C-1 1.50 C-1 1.76 C-1 1.55 C-1 2. 01 C-1 1.76 C-1 2. ¢1 C-1 149 C-1 2. 03 C-1 U2 (1) Weight 8.07 15. 25 8.07 8.07 8.07 7. 07 6.01 7. 07 7. 07 8.07 7. 07 8. 07 6.79 δ. 16 4.48 D-1 0.40 D-1 0. 76 D-1 0.40 D-Ι 0.40 D- 1 0.40 D-2 1.41 D-2 i.20 D-2 i.41 t>-2 i.41 D-2 t.61 D-2 1.41 D-1 0.40 D-2 1.69 Di 0.41 Dl 0.22 grade weight Ttt (2)+(3) /(1) 1.12 0.20 1.12 1.12 1.12 1.27 1.66 1.26 1.27 1.12 1.27 1.12 1.33 1.10 2.65 Heavy cloth foreign matter 〇〇〇〇〇〇〇〇〇〇〇〇〇〇Q Sensitivity 10 10 10 10 10 25 30 35 30 30 35 10 35 10 10 飙 密 〇〇〇〇〇〇〇〇〇〇〇〇〇 X Pattern linearity 〇〇 〇〇 0 0 〇〇〇〇〇X Ra 〇〇〇 〇o 〇〇 〇〇〇X 〇〇 Although the shape 〇Δ Ο 〇Δ 〇〇〇0 〇〇/ tt accumulated electric torque £14 E14 El 4 £14 E14 E14 E14 E13 E13 E14 £14 £14 E10 £14 Ell ---1 2 i 2,4 2.7 2.3 2,3 2.3 3.8 - ~ [Table 2] __ Using a spin coater, apply the above film on a 125 mm x 125 mm glass substrate so that the film thickness after post-baking becomes 2. lyjn Each of the obtained photosensitive resin compositions was pre-baked for a minute. After that, the exposure gap is adjusted to 8G_, and the negative mask of line/sp^ce is covered on the dry coating film. The j-line illumination is 3 〇 / / (10) 2 ultra-high pressure nuclear lamp ride (10) mj eight m2 The material line is subjected to a photohardening reaction of the photosensitive portion. Second. 'This finished coated plate was subjected to a 1 kgf/cm pressure rinsing in a 5% NaOH aqueous solution of the aqueous solution ^ 23 C, and the time of the pattern was observed as the BT (break time), sec. After entering the 321906 26 201042384 line for 20 seconds, the unpressurized film of the 5 pressure film was applied, and the material of the New County board was replaced by the hot air dryer at 23 (rc for 3 minutes). ^ Evaluation of the cured film obtained in the examples and the comparative examples, > each embodiment. The method is as follows: [coating foreign matter] Ο <not = after turning (4), the shame-like strip is expressed as X is bad>, when not observed, it is expressed as 〇 < good: > [sensitivity] In the mask (stepmusk), the exposure amount (mj/cm2) of the residual flag observed in BT+2G seconds is measured. Development adhesion], the case where 2〇//m pattern remains at BT+40 seconds is indicated by ,, and the peeler is represented by X. [Pattern linearity] ο After microscopic observation and post-baking On the 2G/Zm line, it is observed that there is a mineral toothed day, which is represented by X, and when there is no orthodontic tooth, it is represented by 〇. In addition, when it is observed locally, it is represented by △. Surface roughness (surface roughness Ra: JIS B0601_1994)] 0 was measured using a stylus type film thickness meter (manufactured by Tencor Co., Ltd.). The surface roughness Ra was 2 mm wide on the black matrix surface, and was not reached. When i5〇 is 〇, when it exceeds 150 A, it is x. [Cone shape] When the development time is intermittent time +10 to 3 〇 seconds, the 20/zm line after post-baking is observed by the operating electron 27 321906 201042384 microscope. In the cross section, the angle formed by the tapered portion of the substrate and the structure (hardened film) is 60° or more, and is Δ when it is less than 60°, and is X when it is less than 60° (Fig. 2(b)). [Volume resistance value] The same operation as described above was carried out on a fully chrome-plated glass substrate to form a coating film having a film thickness of 2. 1 / zm after post-baking. 10 _ Φ was formed on the coating film. Ming steamed film, add 1 to 10 V voltage between Cr-A 1, measure the current value, and obtain the resistance. [0D measurement] After baking, use a film thickness of 2. 1 μ m film, use large 冢The measurement by the electronic OD meter is described as an OD value of 1 / m. The taper angle of any of the examples 1, 3, 4, 6 to 11 is 60 or more, and the volume resistance value is However, in Comparative Example 1 in which acrylic resin particles having a large particle diameter were used, and Comparative Example 2 in which the acrylic resin particles were not used, the tapered angular shape was all in an arc shape, especially in Comparative Example 2. In addition, in Comparative Example 3 containing cerium oxide particles and Comparative Example 4 in which the amount of acrylic resin particles added was large, the development characteristics were not good. [Example 12] The photosensitive resin composition used in Examples 6 to 11 was used to form an opening (pixel region) of 300 // mxl00/im and a line width of 30 μm and a film thickness (height) of 2.1. /im's matrix of opaque spacers. Thereafter, after treatment with oxygen gas slurry for 3 seconds, the CF4 atmospheric piezoelectric slurry was treated for 3 seconds. When the static contact angle was measured using water or butyl carbitol acetate 28 321906 201042384 r (BCA) ' on the light-shielding separator (light-shielding film), 100 ° and 50 °, respectively. In this black color matrix, a Toshiba technology inkjet head was used, and red, blue, and green inks having a viscosity of 9 mPa·sec and a solid concentration of 20% were printed, and post-baked at 230 ° C to form a color. Filter. As a result, a good color filter can be obtained. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional explanatory view showing a state of a cured film (separator) formed on a substrate. 〇 Fig. 2(a) and (b) are cross-sectional explanatory views showing a state in which the photosensitive resin composition (coating film) in the conventional example is cured. [Description of main components] 1 Substrate 2 Coating 2a Hardened part of coating film 3 Ideal shape of coating after coating Θ Angle 29 321906