200937118 六、發明說明： 【發明所屬之技娜^領域】 發明領域 本發明係關於一種具有優異抗剝性之光敏性樹脂組成 5物及一種使用該組成物之濾色器。特定言之，本發明係關 於當濾色器开> 成於TFT陣列基板上時具有優異抗剝性來確 保高縱橫比之一種鹼性水溶液可顯影之光敏性樹脂組成物 及包括該組成物之一種遽色器。 t Λ* ^tT ^ 10 發明背景 大致上，濾色器用於液晶顯示器（LCD)、照相機之光學 濾鏡等。濾色器可經由於電荷耦合裝置或透明基板上以三 色或更多色著色塗覆一精細區而製造。染色、印刷、電泳 沈積(EPD)、顏料分散等屬於彩色薄膜製造之技術實例。 15 經由於基板上以染色劑染色影像然後使用直接染料染 料該影像可藉染色形成彩色薄膜。可用於製造彩色薄膜之 染色劑之實例包括天然光敏性樹脂諸如明膠等、胺改性之 聚乙烯醇、胺改性之丙烯酸系樹脂等。但染色過程複雜冗 長，原因在於需改變色彩來於同一片基板上形成多彩薄膜 2〇 時須包括防染印刷。此外，多種常用之染料及樹脂具有良 好色彩清晰度及分散性，但也具有不良的光堅牢度、防水 性及耐熱性，此乃極為重要特性。舉例言之’韓國專利公 開案第1991-4717號及第1994-7778號包括偶氮化合物料及 疊氮化合物作為染料，其比較顏料之财熱性及财用性低劣。 200937118 5 Ο 10 15 ❹ 20 經由將顏料分散於可熱固化樹脂或可光固化樹脂内且 以熱或以錢化之’所製備之墨水藉印刷可形成彩色薄 膜。此種方法比較其它方法之#料成本增高，但難以形成 精細與精準的影像，且要求使用印刷技術來獲得均勾薄膜 層。韓國專利公開案第1995-7003746號揭示一種使用喷墨 法製造濾色器之方法。但，所得濾色器有使用染色技術製 造濾色器之類似問題，諸如耐用性及耐熱性低劣問題，原 因在於喷墨印刷法也使用由噴嘴分散之染料型彩色防染組 成物來完成精細且精確的彩色印刷。 韓國專利公開案第1993-7〇0〇858及1996-29904號揭示 使用電沈澱法之電泳沈積(EPD)。電泳沈積(EPD)由於包括 顏料故可形成具有優異耐熱性及光堅牢度之精準彩色薄 膜。但當未來更複雜的像素需要更精細的電極圖案時，可 能難以使用此種方法來製造需要高度複雜度的濾色器，原 因在於由於電阻緣故彩色薄膜於兩端可能被污染或增厚。 經由重複一系列處理程序，諸如於包括黑矩陣之一透 明基板上，塗覆、曝光、顯影及固化光聚合物組成物，顏 料分散液可形成彩色薄膜。顏料分散液可改良耐熱性及耐 用性，此乃濾色器之極為重要的特性，而可提供均勻薄膜 厚度。舉例言之，韓國專利公開案第1992-7002502及 1995-7000359號及韓國專利公告案第1994-5617及 1995-11163號揭示使用顏料分散法製造防染層之方法。 當用於濾色器之光敏性樹脂組成物係使用顏料分散法 製備時’組成物通常包括一連結劑樹脂、一光聚合單體、 5 200937118 一光聚合起始劑、一環氧樹脂、一溶劑、及其它添加劑。 例如黏結劑樹脂包括含幾基之丙烯酸系共聚物諸如日本專 利公開案第 Pyung 7-140654及 10-254133號。 濾色器於製造過程接受多項化學處理。如此，要求彩 色光敏性樹脂具有顯影邊際及化學耐性，因而可達成濾色 器之良率改善俾便維持於前述條件下所形成之圖案。 舉例言之’於分開步驟製造用於習知彩色液晶顯示器 (LCD)顯示彩色影像之濾色器基板及其上設置薄膜電晶體 (TFT)之工作基板’以及然後將濾色器基板與其上設置TFT之 10工作基板共同結合。但結合濾色器基板及工作基板之方法於結 合過程卡之排列準確度低，如此此等方法可能要求有大寬度之 陰影層。如此難以提高孔徑比(活性發光面積對總像素面積之 比）。此外，隨著玻璃基板及液晶顯示器(LCD)之LCD螢幕尺寸 的加大’基板需要較大面積來於結合後進行液晶的真空植入。 Μ液晶組成物也需耗時長時間來均勻展開於基板上方。曾經提示 -種方法來職縮短印卿封材料且贿晶滴落驗頂塗覆 所需時間’但有排列問題造成排列準確度之驟然劣化。 至於替代之道，曾經提示於TFT彩色液晶顯示器（咖） 之工作啊陣列基板上形成濾色器之方法。由於無需遽色器 基板，故此種方法經由通過濺鑛製造透明基板後將兩片 基板結合而具有排列簡單與縱橫比增加之優點。 守’於微影術方法中使 像素電極。如此，於 不电顿。如此，於 經由於濾色器之彩 當於TFT陣列基板上形成濾色器時， 用常用正型光阻而於濾色器上形成一像 電極形成後需要移除光阻層。換言之， 200937118 色像素上形成透明電極層，將正型光阻塗覆於其上，以及 圖案化、曝光、及顯影而製成一像素電極。然後像素電極 上殘留之光阻層經剝除及使用光阻剝除劑移除。如此，濾 色器需要對抗正型光阻剝除劑之抗性。但習知可光固化彩 5 色組成物典型具有微弱抗剝性。 經由於渡色器上形成具有抗剝性之像素保護層，可製 造像素電極。此外，經由於較溫和條件下使用剝除劑及於 低溫長時間剝除正型光阻而未塗覆像素保護層，可製造像 〇 素電極。但此等技術有其問題’諸如良率及製造效率低劣 10 問題，原因在於其需要較多製程步驟及較長的製造時間。 為了解決此等問題’可使用對剝除劑溶液具有膨脹率 低於5%之輻射敏感組成物來製造於陣列上濾色器（c〇A)方 法中製造形成彩色層之固化層。此外，經由使用多官能基 環脂族環氧化合物於熱聚合交聯劑，及使用二苯甲酮系過 15 氧化物作為光熱聚合起始劑，可改良濾色器之熱聚合交聯 性質。於本方法中，濾色器可於低溫短時間固化，因而具 ® 有優異耐用性及緊密接觸(黏著)性質。但隨著比較使用習知 技術所製造者要求有更高影像品質之更大型螢幕需求的增 加’需要有更高縱橫比及更高效能的濾色器。 20 【明内】 發明概要 本發明之具體實施例提供一種可用於濾色器之製造之 光敏性樹脂組成物。本發明之光敏性樹脂組成物為鹼性水 溶液可顯影。該光敏性樹脂組成物特別可用於TFτ陣列基板 7 200937118 上之滤色器的製造，原因在於該組成物具有與下層之優異 的接觸（黏著）性質及對抗光阻剝除劑諸如像素電極製造中 所使用之光阻剝除劑之優異抗性。如此該光敏性樹脂組成 物也對所得裝置提供高孔徑比。 5 树明之另—個實施例提供-種經由使用光敏性樹脂 組成物所製備之高品質濾色器，可包括形成於TFT陣列基板 上之濾色器。本發明之又另一個實施例提供一種包括使用 光敏性樹脂組成物所製備之濾色器之裝置，包括其中涑色 器係形成於TFT陣列基板上之裝置。 10 本發明之實施例並未囿限於前述技術目的，熟諳技藝 人士可了解其它技術目的。 根據本發明之一個實施例，提供一種用於濾色器之光敏性 樹脂組成物，包括：（A)—含羧基之丙烯酸系連結劑樹脂；（B) 下式1表示之一含雙鍵之丙烯酸系羧酸酯樹脂；（c)一丙烯酸系 15 光聚合單體；（D)一光聚合起始劑；（E)—顏料；及(F) —溶劑。 [化學式1]BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition having excellent peeling resistance and a color filter using the same. In particular, the present invention relates to a photosensitive resin composition which is excellent in peeling resistance when the color filter is formed on a TFT array substrate to ensure high aspect ratio, and which comprises an alkaline aqueous solution developable photosensitive resin composition. A color cleaner. t Λ* ^tT ^ 10 BACKGROUND OF THE INVENTION Generally, color filters are used for liquid crystal displays (LCDs), optical filters for cameras, and the like. The color filter can be fabricated by color-coating a fine region in three or more colors on a charge coupled device or a transparent substrate. Dyeing, printing, electrophoretic deposition (EPD), pigment dispersion, etc. are examples of techniques for color film fabrication. 15 The image can be dyed to form a colored film by dyeing the image with a dye on the substrate and then dyeing it with a direct dye. Examples of the coloring agent which can be used for the production of a color film include a natural photosensitive resin such as gelatin, an amine-modified polyvinyl alcohol, an amine-modified acrylic resin, and the like. However, the dyeing process is complicated and cumbersome because it is necessary to change the color to form a colorful film on the same substrate. In addition, many commonly used dyes and resins have good color definition and dispersibility, but also have poor light fastness, water repellency and heat resistance, which are extremely important characteristics. For example, Korean Patent Publication Nos. 1991-4717 and 1994-7778 include azo compound materials and azide compounds as dyes, which are comparatively inferior in the heat and financial properties of the pigments. 200937118 5 Ο 10 15 ❹ 20 A color film can be formed by dispersing a pigment in a heat curable resin or a photocurable resin and printing it by heat or by using a prepared ink. This method is more costly than other methods, but it is difficult to form fine and precise images, and printing technology is required to obtain a uniform film layer. Korean Patent Publication No. 1995-7003746 discloses a method of manufacturing a color filter using an ink jet method. However, the resulting color filter has similar problems in that a color filter is manufactured using a dyeing technique, such as durability and heat resistance, because the inkjet printing method also uses a dye-type color anti-dyeing composition dispersed by a nozzle to perform fineness and Precise color printing. Korean Patent Publication Nos. 1993-7〇0〇858 and 1996-29904 disclose electrophoretic deposition (EPD) using electroprecipitation. Electrophoretic deposition (EPD), due to the inclusion of pigments, results in a precise color film with excellent heat resistance and light fastness. However, when more complex pixels in the future require finer electrode patterns, it may be difficult to use such a method to fabricate color filters that require a high degree of complexity because the color film may be contaminated or thickened at both ends due to resistance. The pigment dispersion can form a colored film by repeating a series of processing procedures, such as coating, exposing, developing, and curing the photopolymer composition on a transparent substrate comprising one of the black matrices. The pigment dispersion improves heat resistance and durability, which is an extremely important property of a color filter, and provides a uniform film thickness. For example, Korean Patent Publication Nos. 1992-7002502 and 1995-7000359, and Korean Patent Publication Nos. 1994-5617 and 1995-11163 disclose a method of producing an anti-staining layer by a pigment dispersion method. When the photosensitive resin composition for a color filter is prepared by a pigment dispersion method, the composition usually includes a binder resin, a photopolymerizable monomer, 5 200937118, a photopolymerization initiator, an epoxy resin, and a Solvents, and other additives. For example, the binder resin includes an acrylic copolymer containing a plurality of groups such as Japanese Patent Publications Pyung 7-140654 and 10-254133. The color filter accepts multiple chemical treatments during the manufacturing process. Thus, the color photosensitive resin is required to have a development margin and chemical resistance, so that the color filter can be improved in yield and the pattern formed under the above conditions can be maintained. For example, in the separate step, a color filter substrate for displaying a color image on a conventional color liquid crystal display (LCD) and a working substrate on which a thin film transistor (TFT) is disposed are fabricated, and then the color filter substrate is disposed thereon The 10 working substrates of the TFT are combined. However, the method of combining the color filter substrate and the working substrate has a low alignment accuracy in the bonding process card, and thus such methods may require a shadow layer having a large width. It is thus difficult to increase the aperture ratio (ratio of the active light-emitting area to the total pixel area). In addition, as the size of the LCD screen of the glass substrate and the liquid crystal display (LCD) increases, the substrate requires a large area to perform vacuum implantation of the liquid crystal after bonding. The liquid crystal composition also takes a long time to spread evenly over the substrate. It has been suggested that the method will shorten the time required for the printing of the seal material and the brittle crystal dripping test. However, the alignment problem causes the alignment accuracy to suddenly deteriorate. As for the alternative, a method of forming a color filter on an array substrate has been suggested for the operation of a TFT color liquid crystal display (coffee). Since the color filter substrate is not required, this method has the advantages of simple arrangement and increased aspect ratio by bonding two substrates after manufacturing a transparent substrate by sputtering. Shou's the pixel electrode in the lithography method. So, don't get it. Thus, when a color filter is formed on the TFT array substrate due to the color filter, the photoresist layer needs to be removed after forming an image electrode on the color filter by using a conventional positive photoresist. In other words, a transparent electrode layer is formed on the 200937118 color pixel, a positive photoresist is applied thereon, and patterned, exposed, and developed to form a pixel electrode. The photoresist layer remaining on the pixel electrode is then stripped and removed using a photoresist stripper. As such, the color filter needs to resist the resistance of the positive photoresist stripper. However, the conventional photocurable color composition typically has a weak peel resistance. The pixel electrode can be fabricated by forming a pixel protective layer having peeling resistance on the color filter. Further, an elemental electrode can be produced by using a stripping agent under mild conditions and stripping the positive type resist at a low temperature for a long time without coating the pixel protective layer. However, these technologies have problems such as yield and manufacturing inefficiency 10 because they require more process steps and longer manufacturing time. In order to solve such problems, a cured layer forming a color layer can be produced by using a radiation-sensitive composition having a swelling ratio of less than 5% for a stripper solution to be manufactured in a color filter (c〇A) method on an array. Further, the thermal polymerization crosslinking property of the color filter can be improved by using a polyfunctional cycloaliphatic epoxy compound in a thermally polymerizable crosslinking agent and using a benzophenone-based 15 oxide as a photothermal polymerization initiator. In this method, the color filter can be cured at a low temperature for a short period of time, so that it has excellent durability and close contact (adhesion) properties. However, as the use of conventional techniques requires manufacturers to increase the demand for larger screens with higher image quality, a color filter with a higher aspect ratio and higher performance is required. [Explanation] Summary of the Invention A specific embodiment of the present invention provides a photosensitive resin composition which can be used for the manufacture of a color filter. The photosensitive resin composition of the present invention can be developed as an alkaline aqueous solution. The photosensitive resin composition is particularly useful for the manufacture of a color filter on a TFτ array substrate 7 200937118 because the composition has excellent contact (adhesion) properties with the underlying layer and is resistant to photoresist stripping agents such as pixel electrode fabrication. Excellent resistance to the photoresist stripping agent used. Thus, the photosensitive resin composition also provides a high aperture ratio to the resulting device. Another embodiment of the present invention provides a high-quality color filter prepared by using a photosensitive resin composition, which may include a color filter formed on a TFT array substrate. Still another embodiment of the present invention provides an apparatus comprising a color filter prepared using a photosensitive resin composition, comprising a device in which a color former is formed on a TFT array substrate. The embodiments of the present invention are not limited to the foregoing technical purposes, and those skilled in the art will be able to understand other technical purposes. According to an embodiment of the present invention, there is provided a photosensitive resin composition for a color filter comprising: (A) a carboxyl group-containing acrylic binder resin; (B) Formula 1 below represents a double bond Acrylic carboxylic acid ester resin; (c) an acrylic 15-polymerizable monomer; (D) a photopolymerization initiator; (E)-pigment; and (F)-solvent. [Chemical Formula 1]
〇=/° 8 200937118 上式中，各Ri獨立地為氫或甲基；R2為氫、經基、C! 至C10院基、或-CO-R5-COOH，其中R5為衍生自酸針之一部 分；R3為R6COO-其中R6為芳基；R4為R7COO-其中R7為烷 基；5Sm《50 ; l<nS20 ;及 1(K〇S100。 5 根據本發明之另一個實施例’提供一種經由使用該光 敏性樹脂組成物形成圖案所製造之濾色器。 後文將說明本發明之實施例之細節。 由於該光敏性樹脂組成物具有優異的抗剝性，特別對 負型光阻樹脂剝除劑之抗剝性，故可用於製造TFT陣列基板 10 上之濾色器來確保獲得高孔徑比。 C實施方式;3 較佳實施例之詳細說明 現在將於後文發明之詳細說明部分更完整說明本發明 之進一步細節如後’其中說明若干但非全部本發明之實施 15 例。確實，本發明可以多種不同形式實施，但不應解譯為 限制於此處列舉之該等實施例；反而提供此等實施例讓本 揭示可滿足適用之法定要求。 如此處使用，當未提供特定定義時，「烷基」一詞係指 C1-C30烷基，「芳基」一詞係指C6-C30芳基，及酸酐一詞 20 係衍生自C1-C30羧酸。 根據本發明之一個實施例之光敏性樹脂組成物包括： (A)—含羧基之丙烯酸系連結劑樹脂；（B)下式1表示之—含 雙鍵之丙稀酸系叛酸醋樹脂，（C)一丙稀酸系光聚合單體· (D)—光聚合起始劑；（E) —顏料；及(f)一溶劑。 9 200937118 後文，將說明根據本發明之一個實施例用於濾色器之 該光敏性樹脂組成物之各個組分之細節。 (_A)含羧基之丙烯酸系遠钴劑接^ afe 含叛基之丙烯酸系連結劑樹脂為包括至少一個叛基之 5 第一烯屬不飽和單體與與該第一烯屬不飽和單體可共聚合 之一第二烯屬不飽和單體之共聚物。該含羧基之丙烯酸系 連結劑樹脂包括以丙烯酸系連結劑樹脂中之單體總重為基 準’ 5 wt%至50 wt%含量之第一含羧基烯屬不飽和單體。於 一個實施例中，該含羧基之丙烯酸系連結劑樹脂包括含量 10 為川wt%至40 wt%之第一含羧基之烯屬不飽和單體；及於 另一個實施例中，含量為20 wt%至30 wt%。 含羧基之丙烯酸系連結劑樹脂具有1〇,〇〇〇至7〇,〇〇〇之 分子量(Mw)。於一個實施例中，該含羧基之丙烯酸系連結 劑樹脂具有20,000至5〇,〇〇〇之分子量。 15 該含羧基之丙烯酸系連結劑樹脂也具有25毫克KOH/ 克至160毫克KOH/克之酸價。於一個實施例中，該含羧基 之丙烯酸系連結劑樹脂也具有3〇毫克KOH/克至150毫克 KOH/克之酸價。當該含羧基之丙烯酸系連結劑樹脂具有於 前述範圍之分子量及酸價時，該連結劑樹脂可提供具有優 20 異顯影性之光阻。 適合用於本發明之第一含羧基之烯屬不飽和單體之實 例包括但非限於丙烯酸、甲基丙烯酸、順丁烯二酸、衣康 酸、反丁烯二酸等及其組合。含羧基之丙烯酸系連結劑樹 脂包括前述化合物作為第一單體。 200937118 5 脅 10 15 ❹ 20 適合用於本發明之與含羧基之烯屬不飽和單體可共聚 合之第一浠屬不飽和單體之實例包括但非限於：稀基芳香 族單體諸如苯乙烯、OC-曱基笨乙烯、乙烯基甲笨、乙烯基 卞基甲基喊，不飽和碳酸醋類諸如丙稀酸甲I旨、曱基丙烯 酸甲酯、丙稀酸乙酯、曱基丙稀酸乙酯、丙稀酸丁醋、甲 基丙烯酸丁酯、丙烯酸2-羥基乙酯、曱基丙烯酸2-羥基乙 酯、丙烯酸2-羥基丁酯、甲基丙烯酸2-羥基丁酯、丙烯酸苄 酯、甲基丙烯酸苄酯、丙烯酸環己酯、甲基丙烯酸環己酯、 丙烯酸苯酯、甲基丙烯酸苯酯等；不飽和碳酸胺基烷酯諸 如丙稀酸2-胺基乙醋、甲基丙稀酸2_胺基乙g旨、丙稀酸2-二甲基胺基乙酯、甲基丙烯酸2-二甲基胺基乙酯等；碳酸 乙烯酯諸如乙酸乙烯酯、苯甲酸乙烯酯等；不飽和碳酸縮 水甘油酯諸如丙烯酸縮水甘油酯、曱基丙烯酸縮水甘油酿 等；乙稀基氰化化合物諸如丙浠腈、甲基丙稀腈等’及不 飽和醯胺類諸如丙稀醯胺、甲基丙稀醯胺等，及其組合。 含羧基之丙烯酸系連結劑樹脂包括前述化合物中之炱少/ 者作為第二單體。 由前述單體所製備之含缓基之丙烯酸系連結劑樹脂之 特例包括但非限於曱基丙烯酸/甲基丙烯酸甲酯共聚物、甲 基丙烯酸/甲基丙烯酸节酯共聚物、甲基丙烯酸/甲基丙歸酸 苄酯共聚物/苯乙烯共聚物、甲基丙烯酸/甲基丙烯酸苄酯共 聚物/甲基丙烯酸2-羥基乙酯共聚物、及甲基丙烯酸/甲基丙 烯酸苄酯共聚物/苯乙烯/曱基丙烯酸2_羥基乙酯共聚物。 甲基丙烯酸/甲基丙烯酸苄酯共聚物屬於含羥基之丙 11 200937118 烯酸系連結劑樹脂中之一者依據酸價及分子量而定可對光 阻提供顯著顯影結果。具有期望之顯影性質之含羧基之丙 稀酸系連結劑樹脂實例為呈重量比25/75 w/w (%)，具有酸 價於80至120毫克ΚΌΗ/克之範圍，及分子量於20,000至 5 40,000之範圍之甲基丙烯酸/甲基丙烯酸苄酯。 以光敏性樹脂組成物總重為基準，該光敏性樹脂組成 物包括0.5 wt%至20 wt%含量之含羧基之丙烯酸系連結劑 樹脂。當該光敏性樹脂組成物包括連結劑樹脂之含量低於 0.5 wt%時，該光阻可能無法於鹼性顯影溶液中顯影。當該 参 1〇光敏性樹脂組成物包括連結劑樹脂之含量超過20 wt%時， 該光阻可能缺乏交聯因而具有較高表面粗度。 ii)含雙鍵之丙烯酸_系羧酴酷樹啤 含雙鍵之丙稀酸系㈣_脂為下式1表示之共聚物。 [化學式1]〇=/° 8 200937118 In the above formula, each Ri is independently hydrogen or methyl; R2 is hydrogen, thiol, C! to C10, or -CO-R5-COOH, wherein R5 is derived from acid needle a portion; R3 is R6COO- wherein R6 is aryl; R4 is R7COO- wherein R7 is alkyl; 5Sm "50; l<nS20; and 1 (K〇S100. 5 according to another embodiment of the present invention) provides a via A color filter manufactured by patterning using the photosensitive resin composition. Details of the embodiment of the present invention will be described later. Since the photosensitive resin composition has excellent peeling resistance, especially for negative resist resin peeling The stripping resistance of the removing agent can be used to manufacture a color filter on the TFT array substrate 10 to ensure a high aperture ratio. C Embodiments 3 Detailed description of the preferred embodiment will now be further described in the detailed description of the following invention. Further details of the invention are set forth in the following <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; Rather, providing such embodiments allows the disclosure to be full Applicable statutory requirements. As used herein, when a specific definition is not provided, the term "alkyl" refers to C1-C30 alkyl, the term "aryl" refers to C6-C30 aryl, and the anhydride number 20 Derived from a C1-C30 carboxylic acid. The photosensitive resin composition according to one embodiment of the present invention comprises: (A) a carboxyl group-containing acrylic binder resin; (B) the following formula 1 - a double bond-containing C Dilute acid vinegar resin, (C) monoacrylic photopolymerizable monomer · (D) - photopolymerization initiator; (E) - pigment; and (f) a solvent. 9 200937118 The details of the respective components of the photosensitive resin composition for a color filter according to an embodiment of the present invention are explained. (_A) A carboxyl group-containing acrylic far-cobalt agent is attached to afe-containing acrylic-based linker resin. And a copolymer of a second ethylenically unsaturated monomer copolymerizable with the first ethylenically unsaturated monomer and at least one of the second ethylenically unsaturated monomers. The binder resin includes a content of '5 wt% to 50 wt% based on the total weight of the monomers in the acrylic binder resin. a first carboxyl group-containing ethylenically unsaturated monomer. In one embodiment, the carboxyl group-containing acrylic binder resin comprises a first carboxyl group-containing ethylenically unsaturated monomer in an amount of 10% by weight to 40% by weight; And in another embodiment, the content is from 20 wt% to 30 wt%. The carboxyl group-containing acrylic binder resin has a molecular weight (Mw) of 1 Å, 〇〇〇 to 7 〇, 〇〇〇. In one embodiment The carboxyl group-containing acrylic binder resin has a molecular weight of 20,000 to 5 Å, and the carboxyl group-containing acrylic binder resin also has an acid value of 25 mgKOH/g to 160 mgKOH/g. In one embodiment, the carboxyl group-containing acrylic binder resin also has an acid value of from 3 mg KOH/g to 150 mg KOH/g. When the carboxyl group-containing acrylic binder resin has a molecular weight and an acid value in the above range, the binder resin can provide a photoresist having excellent development properties. Examples of the first carboxyl group-containing ethylenically unsaturated monomer suitable for use in the present invention include, but are not limited to, acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, and the like, and combinations thereof. The carboxyl group-containing acrylic binder resin includes the aforementioned compound as the first monomer. 200937118 5 Threat 10 15 ❹ 20 Examples of the first fluorene-unsaturated monomer copolymerizable with the carboxyl group-containing ethylenically unsaturated monomer suitable for use in the present invention include, but are not limited to, a dilute aromatic monomer such as benzene Ethylene, OC-fluorenyl stupid ethylene, vinyl methyl stupid, vinyl mercaptomethyl shunt, unsaturated carbonated vinegar such as acrylic acid methyl ester, methyl methacrylate, ethyl acrylate, mercapto acrylate Ethyl ester, butyl acrylate, butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, benzyl acrylate , benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, etc.; unsaturated alkyl alkanoate such as 2-aminoethyl acrylate, methyl Acrylic acid 2_Aminoethylene g, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, etc.; ethylene carbonate such as vinyl acetate, vinyl benzoate Etc.; unsaturated glycidyl carbonate such as glycidyl acrylate, methacrylic acid shrinkage Glycerol is brewed, etc.; ethylene cyanide compounds such as acrylonitrile, methyl acrylonitrile, and the like, and unsaturated guanamines such as acrylamide, methyl acrylamide, and the like, and combinations thereof. The carboxyl group-containing acrylic binder resin includes less of the above compounds as the second monomer. Specific examples of the buffer-containing acrylic binder resin prepared from the foregoing monomers include, but are not limited to, mercaptoacrylic acid/methyl methacrylate copolymer, methacrylic acid/methacrylic acid ester copolymer, methacrylic acid/ Benzyl methacrylate copolymer/styrene copolymer, methacrylic acid/benzyl methacrylate copolymer/2-hydroxyethyl methacrylate copolymer, and methacrylic acid/benzyl methacrylate copolymer / Styrene / methacrylic acid 2-hydroxyethyl ester copolymer. The methacrylic acid/benzyl methacrylate copolymer belongs to the hydroxyl group-containing C. 11 200937118 One of the olefinic linker resins provides significant development results for the photoresist depending on the acid value and molecular weight. Examples of the carboxyl group-containing acrylic acid binder resin having a desired developing property are a weight ratio of 25/75 w/w (%), an acid value of 80 to 120 mg ΚΌΗ/g, and a molecular weight of 20,000 to 5 Methyl acrylate/benzyl methacrylate in the range of 40,000. The photosensitive resin composition includes a carboxyl group-containing acrylic binder resin in an amount of from 0.5% by weight to 20% by weight based on the total mass of the photosensitive resin composition. When the photosensitive resin composition includes the binder resin in an amount of less than 0.5% by weight, the photoresist may not be developable in the alkaline developing solution. When the content of the photosensitive resin composition including the binder resin exceeds 20% by weight, the photoresist may lack crosslinking and thus have a high surface roughness. Ii) Acrylic acid containing a double bond _ carboxy carbaryl tree beer The acrylic acid system containing a double bond (IV) _ lipid is a copolymer represented by the following formula 1. [Chemical Formula 1]
上式中，〜為氫或甲基；R2為氣、經基、dCi戒基、 12 200937118 或-CO-R5-COOH其中R5為衍生自酸酐之一部分；R3為 R6COO-其中R6為芳基；R4為R7COO-其中R7為烧基； 5Sm<50 ; 1<η<2〇 ;及HKoSlOO。 5 Ο 10 15 20 上式1中，於支鏈（分支鏈)之雙鍵具有類似於光聚合單 體中之光反應性官能基之結構。由於雙鍵可形成藉光聚合 起始劑所衍生之基團，如此由於樹脂内部之光聚合反應可 促成樹脂之交聯。 含雙鍵之丙烯酸系羧酸酯樹脂具有3000至150,000之分 子量，於一個實施例中其具有5000至50,000之分子量。含雙 鍵之丙烯酸系羧酸酯樹脂具有由20至70毫克KOH/克之範圍 之酸價。當含雙鍵之丙烯酸系羧酸酯樹脂具有於此範圍内之 分子量及酸價時，可製備具有優異顯影性質之光阻。 含雙鍵之丙烯酸系羧酸酯樹脂之光起始的交聯程度或 交聯量可由該樹脂組成物中之光聚合單體與光聚合起始劑 之比確定’如此可藉改變其個別比例控制。 以光敏性樹脂組成物之總重為基準，該光敏性樹脂組 成物包括5 wt%至30 wt%數量之含雙鍵之丙烯酸系羧酸酯 樹脂。當該光敏性樹脂組成物包括含雙鍵之丙烯酸系羧酸 酯樹脂之含量低於5 wt%時，對化學耐性之改良之效果低。 當該光敏性樹脂組成物包括含雙鍵之丙烯酸系羧酸酯樹脂 之含量大於30 wt%時’對圖案安定性有影響且造成透光特 性的劣化。 (C)丙烯酸糸光聚厶n 適合用於本發明之丙烯酸系光聚合單體之實例包括但 13 200937118 非限於乙二醇二丙稀酸酯、三乙二酵二丙稀酸酯、1,4-丁一 醇二丙烯酸酯、1,6-己二醇二丙烯酸酯、新戊二·醇二丙烯酸 醋、季戊四醇二丙稀酸酯、季戊四醇三丙烯酸酯、二季戊 四醇二丙烯酸酯、二季戊四醇三丙烯酸酯、二·季戊四醇五 5 丙稀酸自曰、季戊四醇六丙稀酸醋、雙盼A二丙稀酸®曰、二經 曱基丙烷三丙烯酸酯、酚醛清漆環氧樹脂丙烯酸酯、乙二 醇二甲基丙烯酸酯、二乙二醇二甲基丙烯酸酯、三乙二醇 二曱基丙烯酸酯、丙二醇二甲基丙烯酸酯、1，4-丁二醇二曱 基丙烯酸酯、1，6-己二醇二甲基丙烯酸酯等及其組合。 10 以光敏性樹脂組成物總重為基準，該光敏性樹脂組成 物可包括含量為〇 5 wt%至20 wt%之丙稀酸系光聚合單 體。當光敏性樹脂組成物包括丙烯酸系光聚合單體之含量 低於0.5 wt%時，該丙烯酸系光聚合單體無法促成清晰圖案 邊緣的形成。當該光敏性樹脂組成物包括丙烯酸系光聚合 15單體之含量大於20糾％時，光阻可能無法於鹼性顯影溶液 中顯影。 m)光聚合起始彳丨 適σ用於本發明之光聚合起始劑之實例包括但非限於 三啫系化合物、苯乙酮系化合物、二苯甲酮系化合物、嘍 2〇 山酮系化合物、安息香系化合物、肟系化合物等及其組合。 三畊系化合物之實例包括但非限於2,4,6-三氣-均-三 讲、2-苯基-4,6-貳(三氯甲基)_均三呌、2_(3，，4’_二甲氧基笨 乙稀基)·4,6-武(三氣曱基)_均_三畊、2 (4，甲氧基萘基)4,6_ 貳（三氣甲基)-均-三。井、2_(對甲氧基笨基)·46武（三氯甲 200937118 基)-均-三讲、2-(對-甲苯基)-4,6-貳（三氯甲基)-均-三讲、2-聯苯基-4,6-貳（三氣曱基)-均-三讲、貳（三氯曱基)-6-苯乙烯 基-均-三畊、2-(萘-1-基)-4,6-貳（三氯甲基)-均-三畊、2-(4-甲氧基萘-1-基)-4,6-貳（三氣曱基)-均-三畊、2,4-三氣曱基 5 (胡椒醯基)-6-三啡、2,4-三氣甲基(4，-曱氧基苯乙烯基)-6-三畊等及其組合。 苯乙酮系化合物之實例包括但非限於2,2’-二乙氧基苯 乙酮、2,2’-二丁氧基苯乙銅、2-羥基-2-曱基苯丙酮、對-第 0 三-丁基三氯苯乙酮、對-第三-丁基二氯苯乙酮、4-氯苯乙 10 酮、2,2’-二氯-4-苯氧基苯乙酮、2-曱基-1-(4-(甲硫基）苯 基)-2-咮啉基丙-1-酮、2-苄基-2-二甲基胺基-1-(4-咮啉基苯 — 基)-丁-1-酮等及其組合。 ' 二苯甲酮系化合物之實例包括但非限於二苯甲酮、苯 甲酸苯甲醯、甲基苯甲酸苯甲醯、4-苯基二苯甲酮、羥基 15 二苯甲酮、丙烯酸化二苯甲酮、4,4’-貳（二甲基胺基)二苯曱 酮、4,4’-貳（二乙基胺基)二苯甲酮、4,4’-二甲基胺基二苯甲 ® 酮、4,4’-二氯二苯甲酮、3,3’-二曱基-2-甲氧基二苯甲酮等 及其組合。 噻°山酮系化合物之實例包括但非限於嘍°山酮、2-曱基 20 噻α山酮、異丙基噻咄酮、2,4-二乙基嘍α山酮、2,4-二異丙基 嘆》山酮、2-氣嗔'1山酮等及其組合。 安息香系化合物之實例包括但非限於安息香、安息香 甲醚、安息香乙醚、安息香異丙醚、安息香異丁醚、安息 香二甲基縮醛等及其組合。 15 200937118 防系化合物之實例包括但非限於2-(鄰-节醯基 將)小[4-(苯硫基）苯基辛二酮]、i•(鄰_乙醯基·Η_[9_ 乙基-6-(2-甲基苄醯基)_9H-咔唑-3-基]乙酮等及其組合。 光聚合起始劑進一步包括叶"坐系化合物、二酮系化合 5 物、硼酸鎳系化合物、重氮系化合物、貳咪》坐系化合物等 及其組合。 以光敏性樹脂組成物之總重為基準，該光敏性樹脂組 成物可包括0.1 Wt%至10 wt%含量之光聚合起始劑。當該光 敏性樹脂組成物包括光聚合起始劑之數量低於0.1 wt% 0 10 時’於圖案形成過程於曝光期間之光聚合反應不足。當該 光敏性樹脂組成物包括光聚合起始劑之數量大於1〇 wt% 時，光聚合後可能殘留過量未反應的起始劑可能造成透射 比的劣化。 (E)^j£ 15 顏料包括紅色、綠色、藍色、黃色及紫色。適合用於 本發明之顏料之實例包括但非限於蔥醌系顏料、縮合多環 顏料諸如花系顏料等、酞花青顏料、偶氮系顏料等。顏料 0 可單獨使用或兩種或多種組合使用。兩種或多種顏料的組 合允許調整最大吸收波長、交又點、串擾等。 2〇 顏料可製備成分散液且含括於光敏性樹脂組成物。顏 料分散液可包括乙二醇乙酸_、乙基溶纖素、丙二醇甲喊 乙酸醋、乳酸乙醋、聚乙二醇、環己酮、丙二酵甲醚等及 其組合。 此外，顏料可包括分散劑來實質上均勻分散顏料。適 16 200937118 合用於本發明之分散劑之實例包括全部非離子性、陰離子 性或陽離子性分散劑例如聚烷二醇及其酯類、聚氧烯、多羥 基醇酯環氧烷加合物、醇環氧烷加合物、磺酸酯類、磺酸鹽 類、羧酸酯類、綾酸鹽類、烷基醯胺環氧烷加合物、烷基胺 類等。此等分散劑可單獨使用或兩種或多種組合使用。 此外，含羧基之丙烯酸系連結劑樹脂及分散劑可添加 至顏料來改良顏料分散液之安定性及像素圖案。 Ο 10 15 20 顏料可具有由10奈米至80奈米之一次粒子直徑。於另 「個實施射，顏料可具有1G奈米至7()奈米之—次粒子直 後。當顏料具有於前述範圍内之_次粒子直徑時，顏料於 分散液中具有優異安定性以會造成像素解析度的降級。 此外’分散於分散液之顏料對二次粒子直徑而言並無 私殊限制’依據像素解析度而定可具有少於細奈米之二次 2餘。於另-個實施例中，顏料可具有由财求至觸 蛋米之範圍之二次粒子直徑。In the above formula, ~ is hydrogen or methyl; R2 is a gas, a trans group, a dCi group, 12 200937118 or -CO-R5-COOH wherein R5 is a moiety derived from an acid anhydride; R3 is R6COO- wherein R6 is an aryl group; R4 is R7COO-wherein R7 is a burnt group; 5Sm<50;1<η<2〇; and HKoS100. 5 Ο 10 15 20 In the above formula 1, the double bond in the branched chain (branched chain) has a structure similar to the photoreactive functional group in the photopolymerizable monomer. Since the double bond can form a group derived from the photopolymerization initiator, the crosslinking of the resin can be promoted by photopolymerization inside the resin. The acrylic carboxylate resin containing a double bond has a molecular weight of from 3,000 to 150,000, and in one embodiment it has a molecular weight of from 5,000 to 50,000. The acrylic resin containing a double bond has an acid value in the range of 20 to 70 mgKOH/g. When the double-bonded acrylic carboxylic acid resin has a molecular weight and an acid value within this range, a photoresist having excellent developing properties can be prepared. The photo-initiated crosslinking degree or crosslinking amount of the double-bonded acrylic carboxylate resin can be determined by the ratio of the photopolymerizable monomer to the photopolymerization initiator in the resin composition, so that the individual ratio can be changed by control. The photosensitive resin composition includes, in terms of the total weight of the photosensitive resin composition, an acrylic carboxylic acid resin containing a double bond in an amount of from 5 wt% to 30 wt%. When the photosensitive resin composition contains a double bond-containing acrylic carboxylic acid resin in an amount of less than 5 % by weight, the effect of improving chemical resistance is low. When the photosensitive resin composition contains a double bond-containing acrylic carboxylic acid resin in an amount of more than 30% by weight, it has an influence on pattern stability and causes deterioration of light transmission characteristics. (C) Acrylic acid polyfluorene n Examples of acrylic photopolymerizable monomers suitable for use in the present invention include but 13 200937118 are not limited to ethylene glycol diacrylate, triethylene glycol diacrylate, 1, 4-butanol diacrylate, 1,6-hexanediol diacrylate, neopentyl alcohol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, dipentaerythritol diacrylate, dipentaerythritol Acrylate, dipentaerythritol penta-5 acrylic acid fluorene, pentaerythritol hexaacetic acid vinegar, bispan A dipropylene acid hydrazine, dipyridyl propane triacrylate, novolac epoxy resin acrylate, ethylene Alcohol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimercapto acrylate, propylene glycol dimethacrylate, 1,4-butanediol dimercapto acrylate, 1,6 - hexanediol dimethacrylate, and the like, and combinations thereof. The photosensitive resin composition may include an acrylic photopolymerizable monomer in an amount of from 〇 5 wt% to 20 wt%, based on the total mass of the photosensitive resin composition. When the content of the photosensitive resin composition including the acrylic photopolymerizable monomer is less than 0.5% by weight, the acrylic photopolymerizable monomer cannot contribute to the formation of sharp pattern edges. When the content of the photosensitive resin composition including the acrylic photopolymerizable monomer is more than 20%, the photoresist may not be developed in the alkaline developing solution. m) Photopolymerization initiation σ σ Examples of photopolymerization initiators used in the present invention include, but are not limited to, triterpenoid compounds, acetophenone compounds, benzophenone compounds, and oxime 2 ketone systems. Compounds, benzoin compounds, lanthanide compounds, and the like, and combinations thereof. Examples of three-tillage compounds include, but are not limited to, 2,4,6-tri-gas-homo-tris, 2-phenyl-4,6-indole (trichloromethyl)------, (3,, 4'_Dimethoxyethylidene)·4,6-武(三气曱基)_均_三耕, 2 (4,methoxynaphthyl) 4,6_ 贰 (trimethyl) - Both - three. Well, 2_(p-methoxyphenyl)·46wu (trichloromethyl 200937118 base)-all-three-speaker, 2-(p-tolyl)-4,6-indole (trichloromethyl)-all- Three lectures, 2-biphenyl-4,6-anthracene (three gas fluorenyl)---three-speaking, hydrazine (trichloroindenyl)-6-styryl-average-three tillage, 2-(naphthalene- 1-yl)-4,6-indole (trichloromethyl)-average-three-pill, 2-(4-methoxynaphthalen-1-yl)-4,6-indole (trioxanyl)-all - three tillage, 2,4-trimethyl sulfhydryl 5 (pepperyl)-6-trimorphine, 2,4-trimethylmethyl (4,-decyloxystyryl)-6-three tillage, etc. Its combination. Examples of the acetophenone-based compound include, but are not limited to, 2,2'-diethoxyacetophenone, 2,2'-dibutoxyphenethyl copper, 2-hydroxy-2-mercaptopropiophenone, p- 0th tri-butyltrichloroacetophenone, p-t-butyldichloroacetophenone, 4-chlorophenylethyl ketone, 2,2'-dichloro-4-phenoxyacetophenone, 2-mercapto-1-(4-(methylthio)phenyl)-2-indolyl propan-1-one, 2-benzyl-2-dimethylamino-1-(4-porphyrin Benzo-yl)-butan-1-one and the like, and combinations thereof. Examples of benzophenone-based compounds include, but are not limited to, benzophenone, benzamidine benzoate, benzamidine methylbenzoate, 4-phenylbenzophenone, hydroxy15 benzophenone, acrylated Benzophenone, 4,4'-fluorene (dimethylamino)benzophenone, 4,4'-fluorene (diethylamino)benzophenone, 4,4'-dimethylamine Bis-benzophenone® ketone, 4,4'-dichlorobenzophenone, 3,3'-dimercapto-2-methoxybenzophenone, and the like, and combinations thereof. Examples of the thioxanthone-based compound include, but are not limited to, oxime ketone, 2-mercapto 20 thia-alpha ketone, isopropyl thiazinone, 2,4-diethyl fluorene ketone, 2,4- Diisopropyl sulphate, ketone, 2-ketone, ketone, and the like, and combinations thereof. Examples of benzoin-based compounds include, but are not limited to, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin dimethyl acetal, and the like, and combinations thereof. 15 200937118 Examples of defense compounds include, but are not limited to, 2-(o-thyl-fluorenyl) small [4-(phenylthio)phenyloctanedione], i•(o-_ethylidene·Η_[9_ B a group of 6-(2-methylbenzylidene)- 9H-indazol-3-yl]ethanone and the like, and combinations thereof. The photopolymerization initiator further includes a leaf "salt compound, a diketone compound 5, a nickel borate compound, a diazo compound, a ruthenium compound, or the like, and a combination thereof. The photosensitive resin composition may include a content of 0.1 Wt% to 10% by weight based on the total weight of the photosensitive resin composition. Photopolymerization initiator. When the amount of the photosensitive resin composition including the photopolymerization initiator is less than 0.1 wt% 0 10, the photopolymerization reaction during the pattern formation process is insufficient during the exposure. When the photosensitive resin composition When the amount of the photopolymerization initiator is more than 1% by weight, an excessive amount of unreacted initiator may remain after photopolymerization, which may cause deterioration of transmittance. (E)^j£ 15 Pigments include red, green, blue, Yellow and purple. Examples of pigments suitable for use in the present invention include, but are not limited to, onion pigments, condensed polycyclic pigments Such as flower pigments, phthalocyanine pigments, azo pigments, etc. Pigment 0 may be used singly or in combination of two or more kinds. The combination of two or more pigments allows adjustment of the maximum absorption wavelength, cross point, crosstalk, and the like. The pigment may be prepared as a dispersion and included in the photosensitive resin composition. The pigment dispersion may include ethylene glycol acetate _, ethyl cellosolve, propylene glycol methyl acetate vinegar, lactic acid ethyl acetate, polyethylene glycol, Further, the pigment may include a dispersing agent to substantially uniformly disperse the pigment. Suitable examples of the dispersing agent to be used in the present invention include all nonionic, anionic or cationic Dispersing agents such as polyalkylene glycols and their esters, polyoxyalkylenes, polyhydric alcohol esters, alkylene oxide adducts, alcohol alkylene oxide adducts, sulfonates, sulfonates, carboxylates , phthalic acid esters, alkyl decylamine alkylene oxide adducts, alkyl amines, etc. These dispersing agents may be used singly or in combination of two or more. Further, carboxyl group-containing acrylic binder resin and dispersion Can be added to the pigment The stability of the pigment dispersion and the pixel pattern. Ο 10 15 20 The pigment can have a primary particle diameter of from 10 nm to 80 nm. In another implementation, the pigment can have a nanometer to 7 () nanometer. When the pigment has a _ secondary particle diameter within the above range, the pigment has excellent stability in the dispersion to cause degradation of the pixel resolution. Further, the pigment dispersed to the dispersion is a secondary particle. There is no special restriction on the diameter. 'Depending on the resolution of the pixel, it may have less than 2 times of the fine nanometer. In another embodiment, the pigment may have a second range from the financial demand to the touched rice. Particle diameter.
以光敏性樹脂組成物之總重A Λ 马基準，光敏性樹脂組成 物可包括0.1 wt%至40 wt%含量之嚭 、^ t 顯枓。當該光敏性樹脂組 成物包括顏料之含量低於0.1 wt%昧 .^ 寺’該顏料具有極少著色 效果。當該光敏性樹脂組成物包 匕括顏料數量大於40 wt% 時，該顏料可能造成顯影效能的急遽降級 適合用於本發明之溶劑之實 ]包括但非限於乙二醇乙 酸酯、乙基溶纖素、丙二醇甲醚乙 t 酸酯、乙氧基丙酸乙酯、 乳酸乙酯、聚乙二醇、環己酮、而_ ~一醇甲醚等。此等溶劑 17 200937118 可單獨使用或兩種或多種組合使用。 溶劑之實例包括但非限於：乙二醇類諸如乙二醇、二 乙-醇等；二醇贿諸如乙二醇一甲謎、二乙二醇一甲鍵、 乙-醇二乙謎、二乙二醇二甲喊等；二醇鍵乙酸醋類諸如 5乙二醇一乙醚乙酸酯、二乙二醇一乙醚乙酸酯、乙二醇一 丁喊乙酸醋等；丙二醇類諸如丙二酵；丙二醇_諸如丙 一醇一甲醚、丙二醇一乙醚、丙二醇一丙醚、丙二醇一丁 醚、丙二醇二甲醚、二丙二醇二曱醚、丙二醇二乙醚、二 丙一醇二乙醚等；丙二醇醚乙酸酯類諸如丙二醇一甲醚乙 ◎ 10 酸酯、二丙二醇一乙醚乙酸酯等；醯胺類諸如队甲基吡咯 啶酮、二甲基甲醯胺、二甲基乙醯胺等；_類諸如異丁酮 (MEK)、曱基異丁基曱酮(MIBK)、環己酮等；石油類諸如 甲本一甲苯、溶劑石腦油等；及醋類諸如乙酸乙酯、乙 酸丁酯、乳酸乙酯等。此等溶劑可單獨使用或組合二者或 15 多者使用。The photosensitive resin composition may include a ruthenium of 0.1% by weight to 40% by weight based on the total weight of the photosensitive resin composition. When the photosensitive resin composition includes a pigment content of less than 0.1 wt%, the pigment has little coloring effect. When the photosensitive resin composition includes a pigment amount of more than 40% by weight, the pigment may cause a drastic deterioration in development performance, which is suitable for use in the solvent of the present invention, including but not limited to ethylene glycol acetate, ethyl Cellulose, propylene glycol methyl ether ethyl t-ate, ethyl ethoxy propionate, ethyl lactate, polyethylene glycol, cyclohexanone, and monomethyl ether. These solvents 17 200937118 may be used singly or in combination of two or more. Examples of the solvent include, but are not limited to, ethylene glycols such as ethylene glycol, diethyl alcohol, and the like; glycol brittles such as ethylene glycol-a-mystery, diethylene glycol-monomethyl bond, and ethyl alcohol-II puzzle, two Ethylene glycol dimethyl sulfonate; glycol linkage acetic acid vinegar such as 5 ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, ethylene glycol monobutyl acetate vinegar, etc.; propylene glycol such as C Propylene glycol propylene glycol such as propanol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, dipropylene glycol dioxime ether, propylene glycol diethyl ether, dipropanol diethyl ether, etc.; Ether acetates such as propylene glycol monomethyl ether ethyl benzoate, dipropylene glycol monoethyl ether acetate, etc.; guanamines such as methylpyrrolidone, dimethylformamide, dimethylacetamide, etc.; _ such as isobutyl ketone (MEK), mercaptoisobutyl fluorenone (MIBK), cyclohexanone, etc.; petroleum such as methylprednisolone, solvent naphtha, etc.; and vinegar such as ethyl acetate, acetic acid Ester, ethyl lactate, and the like. These solvents may be used singly or in combination of two or more.
溶劑可以餘量使用，但於另一個實施例中，以光敏性 樹脂組成物之總重為基準，光敏性樹脂組成物可包括由2〇 Q wt%至90 wt%含量之溶劑。當光敏性樹脂組成物包括於此 範圍之含量之溶劑時，光敏性樹脂組成物具有優異的塗覆 ί1 生質且於1微米層或更厚層維持平坦。 它添·知, —除了組分⑷至(F)外’用於據色器之光敏性樹脂組成物進 —步可包括前述分㈣俾均勻分散(聰·分於(F)溶劑。 用於應色器之光敏性樹脂組成物也進—步包括其它添 18 200937118 加劑，諸如但非限於丙二酸、3_胺基q，2_丙二酵、含乙烯 基或含（甲基）丙烯醯氧基之矽烷系偶合劑、及氟系界面活性 劑俾防止塗覆期間之玷染或斑點，俾調整均平或防止由於 未顯影所造成的圖案殘值。依據期望性質而定，此等添加 5 劑可以經調整之數量含括。 此外，若有所需，本發明之光敏性樹脂組成物額外包 括環氧化合物來改良黏附性及其它特性。適合用於本發明 之環氧化合物之實例包括但非限於環氧酚醛清漆丙烯酸系 羧酸酯樹脂、鄰甲酚酚醛清漆環氧樹脂、酚酚醛清漆環氧 1〇 樹脂、四曱基聯苯環氧樹脂、雙酚A型環氧樹脂、環脂族環 氧樹脂等及其組合。以光敏性樹脂組成物之總重為基準， 光敏性樹脂組成物包括〇〇1份重量比至5份重量比含量之 環氧化合物。當光敏性樹脂組成物包括0.01份重量比至5份 重量比範圍含量之環氧化合物時，環氧化合物可改良儲存 15 特性、黏附特性、及其它特性。 當含括環氧化合物時，可額外含括過氧化物起始劑或 自由基聚合起始劑諸如偶氮貳系起始劑。 本發明之另一個實施例提供一種使用光敏性樹脂組成 物形成濾色器之方法，包括於TFT陣列基板上形成濾色器之 2〇 方法，及形成包括使用光敏性樹脂組成物之濾色器之裝置 之方法，包括其中濾色器係形成於TFT陣列基板上之裝置。 根據本發明之一個實施例，藉例如旋塗法、隙塗法等 方法，光敏性樹脂組成物塗覆於其上有厚5〇〇埃至15〇〇埃 SiNx (保護層）之玻璃基板上至31微米至3·4微米厚度。塗覆 200937118 後，光敏性樹脂組成物藉照光而形成渡色器所需圖案。其 次，當塗覆層以驗性顯影溶液處理來溶解未照光部分時形 成滅色器圖案。依據R、G、及b色彩數目而定，此項程序 可重複多次來提供具有期望之圖案之渡色器。於本方法 5中，已顯影之影像圖案可藉光化射線加熱或固化來改良耐 裂性、溶劑耐性等。 大致上，由於負型光敏樹脂不易藉有機溶劑剝除，其 殘值可能污染下層。此外，負型光敏樹脂比正型光敏樹脂 具有對下層更微弱的緊密接觸性質(黏著性），因而增加凹㈣ ^ 10的可能。本發明之用於濾色器之光敏性樹脂組成物具有改 良抗剝性’如此比較負型光敏樹脂減少污染風險且改良與 下層之黏著性（緊密接觸性質）。 下列實例舉例說明本發明之進一步細節。但須了解本 - 發明並未受此等實例所限。 15 合成例1:含雙鍵之丙烯酸系羧酸酯樹脂之合成 10份重量比2,2’-偶氮貳(2,4·二甲基戊腈，200份重量比 丙二醇一甲醚乙酸酯、15份重量比甲基丙烯酸、25份重量 〇 比苯乙烯、及60份重量比羥基丙烯醯基乙氧基甲基丙烯酸 酯置於裝配有冷卻器及攪動器之燒瓶内，置於氮氣氣氛下 20 然後徐緩攪動。反應溶液加熱至8(TC然後維持8小時，製備 含雙鍵之丙烯酸系羧酸酯聚合物。聚合物溶液具有35 wt% 之固型物濃度，及聚合物具有17,000之重量平均分子量。 如此處使用’重量平均分子量指示以GPC測定平均分子量 降至聚苯乙烯之分子量。 20 200937118 ^ 實例1 經由使用下列組分製備光敏性樹脂組成物。首先，光 聚合起始騎解於㈣I及於室溫攪動2小時。其次，含敌基 之丙烯酸系連結劑樹脂、含雙鍵之丙烯酸系羧酸酯樹脂及 5光聚合單體添加至其中。所得混合物於室溫攪拌2小時。然 後，顏料分散液添加至其中及於室溫攪拌丨小時。隨後氟系 界面活性劑添加至其中且於室溫攪拌1小時。所得溶液過濾 三次去除雜質。 φ (A)含羧基之丙烯酸系連結劑樹脂6.0克 10 (al)/(a2)=25/75(w/w)，分子量(Mw)=25,000 (a!):甲基丙烯酸 . (a2).曱基丙浠酸节g旨 • (B)含雙鍵之丙烯酸系羧酸酯樹脂 (合成例1製備之聚合物）3·9克 15 分子量(Mw)=17,000，酸價=65毫克ΚΟΗ/克 (C) 丙烯酸系光聚合單體 參 二季戊四醇六丙烯酸酯(DPHA) 4.1克 (D) 光聚合起始劑 TPP (汽巴特用化學品公司）0.2克 20 (E)顏料分散液46.8克 紅（汽巴特用化學品公司BT-CF) (6 · 2克） 黃（汽巴特用化學品公司2RP-CF) (2· 8克） 丙烯酸系分散劑(2.4克） 前述(A)含羧基之丙烯酸系連結劑樹脂(5·4克） 21 200937118 - * 溶劑(PGMEA) (30.0克） (F)溶劑 丙二醇一甲醚乙酸酯26.0克 乙氧基丙酸乙酯12.9克 5 (G)添加劑 F-475 (氟系界面活性劑）〇. 1克 比較例1The solvent may be used in the balance, but in another embodiment, the photosensitive resin composition may include a solvent having a content of from 2 〇 Q wt% to 90 wt% based on the total weight of the photosensitive resin composition. When the photosensitive resin composition includes a solvent in a range of this range, the photosensitive resin composition has excellent coating quality and is maintained flat in a 1 micron layer or a thick layer. It is known that - in addition to the components (4) to (F), the photosensitive resin composition for the color filter may further comprise the above-mentioned sub-(4) 俾 uniformly dispersed (Cong·(F) solvent. The photosensitive resin composition of the color filter also includes other additions 18 200937118 additives such as, but not limited to, malonic acid, 3-amino group q, 2 - propylene glycol, vinyl or (meth) An acryloxy-based decane-based coupling agent and a fluorine-based surfactant 俾 prevent contamination or speckle during coating, adjust the level or prevent pattern residual values due to undeveloped, depending on the desired properties, The addition of 5 agents may be included in the adjusted amount. Further, if necessary, the photosensitive resin composition of the present invention additionally includes an epoxy compound to improve adhesion and other characteristics. It is suitable for use in the epoxy compound of the present invention. Examples include, but are not limited to, epoxy novolac acrylate carboxylic acid resin, o-cresol novolac epoxy resin, phenol novolac epoxy 1 〇 resin, tetradecyl biphenyl epoxy resin, bisphenol A epoxy resin , cycloaliphatic epoxy resin, etc. and combinations thereof. The photosensitive resin composition includes an epoxy compound in an amount of from 1 part by weight to 5 parts by weight based on the total weight of the photosensitive resin composition. When the photosensitive resin composition comprises 0.01 parts by weight to 5 parts by weight In the case of a range of epoxy compounds, the epoxy compound can improve the storage properties, adhesion characteristics, and other characteristics. When an epoxy compound is included, it may additionally include a peroxide initiator or a radical polymerization initiator such as An arsenazo-based initiator. Another embodiment of the present invention provides a method of forming a color filter using a photosensitive resin composition, comprising a method of forming a color filter on a TFT array substrate, and forming including using photosensitive A method of a device for a color filter of a resin composition, comprising a device in which a color filter is formed on a TFT array substrate. According to an embodiment of the present invention, photosensitivity is performed by, for example, a spin coating method, a gap coating method, or the like. The resin composition is applied to a glass substrate having a thickness of 5 Å to 15 Å of SiNx (protective layer) to a thickness of 31 μm to 3.5 μm. After coating 200937118, the photosensitive resin The object forms a pattern required by the color filter by light. Secondly, a color caster pattern is formed when the coating layer is treated with an inert developing solution to dissolve the unilluminated portion. Depending on the number of colors of R, G, and b, this The program can be repeated a plurality of times to provide a color filter having a desired pattern. In the method 5, the developed image pattern can be heated or cured by actinic rays to improve crack resistance, solvent resistance, etc. Generally, due to negative The photosensitive resin is not easily stripped by an organic solvent, and its residual value may contaminate the lower layer. In addition, the negative photosensitive resin has a weaker contact property (adhesion) to the lower layer than the positive photosensitive resin, thereby increasing the possibility of concave (four) ^ 10 The photosensitive resin composition for a color filter of the present invention has improved peeling resistance. Thus, the comparative negative photosensitive resin reduces the risk of contamination and improves the adhesion to the underlying layer (close contact property). The following examples illustrate further details of the invention. However, it must be understood that this invention is not limited by these examples. 15 Synthesis Example 1: Synthesis of acrylic acid carboxylate resin containing double bond 10 parts by weight of 2,2'-arsenazo (2,4·dimethylvaleronitrile, 200 parts by weight of propylene glycol monomethyl ether acetate) Ester, 15 parts by weight of methacrylic acid, 25 parts by weight of styrene, and 60 parts by weight of hydroxypropenyl ethoxy methacrylate were placed in a flask equipped with a cooler and an agitator, and placed in a nitrogen gas Under the atmosphere 20, the agitation was slowly stirred. The reaction solution was heated to 8 (TC and then maintained for 8 hours to prepare a double bond-containing acrylic carboxylate polymer. The polymer solution had a solid concentration of 35 wt%, and the polymer had 17,000. Weight average molecular weight. As used herein, 'weight average molecular weight indicates that the average molecular weight is determined by GPC to decrease the molecular weight of polystyrene. 20 200937118 ^ Example 1 A photosensitive resin composition was prepared by using the following components. First, photopolymerization started riding The solution was stirred at room temperature for 2 hours. Next, an acrylic-based linker resin containing an anchor group, an acrylic carboxylate resin containing a double bond, and a 5-photopolymerizable monomer were added thereto. The resulting mixture was stirred at room temperature 2 Then, the pigment dispersion was added thereto and stirred at room temperature for several hours, and then a fluorine-based surfactant was added thereto and stirred at room temperature for 1 hour. The resulting solution was filtered three times to remove impurities. φ (A) carboxyl group-containing acrylic acid Linking agent resin 6.0 g 10 (al) / (a2) = 25 / 75 (w / w), molecular weight (Mw) = 25,000 (a!): methacrylic acid. (a2). mercaptopropionate section g (B) Acrylic carboxylic acid ester resin containing double bond (polymer prepared in Synthesis Example 1) 3·9 g 15 Molecular weight (Mw) = 17,000, acid value = 65 mg ΚΟΗ / 克 (C) Acrylic light Polymerized monomer dipentaerythritol hexaacrylate (DPHA) 4.1 g (D) Photopolymerization initiator TPP (Cadbat Chemicals) 0.2 g 20 (E) pigment dispersion 46.8 g red (Steam Bart Chemicals) BT-CF) (6 · 2g) Yellow (2RP-CF from Steam Batt Chemical Company) (2.8g) Acrylic dispersant (2.4g) The above (A) carboxyl group-containing acrylic binder resin (5 · 4g) 21 200937118 - * Solvent (PGMEA) (30.0g) (F) Solvent propylene glycol monomethyl ether acetate 26.0g Ethyl ethoxypropionate 12.9g 5 (G) Additive F-475 (Fluorine Surfactant) square. Comparative Example 1 1 g
根據實例1之相同方法製備光敏性樹脂組成物，但使用 環氧基丙烯酸系叛酸酯樹脂(EOCN，日本化藥公司（Nippon Q 10 Kayaku))用來替代含雙鍵之丙烯酸系羧酸酯樹脂。 比較例2 根據實例1之相同方法製備光敏性樹脂組成物，但未使 用含雙鍵之丙烯酸系羧酸酯樹脂。 · 根據實例1及比較例1至2之樹脂組成物評估抗剝性。 15 實例1及比較例1至2之光敏性樹脂組成物使用旋塗機 於具有500埃SiNx層之玻璃板上塗覆形成厚3·!微米至3 4微 米層。其次’使用熱板將該層於80。(：軟烤乾150秒。然後該 〇 層使用曝光裝置曝光於60毫焦耳光，且使用顯影劑顯影6〇 秒，洗滌60秒，及離心乾燥25秒。然後於25。(：於1%氫氧化 20 鉀溶液進行顯影。然後該層於230°C烤爐内硬烤乾30分鐘。 有關色彩變化於硬烤乾後使用比色計測量如下。 硬烤乾試驗件浸潰於70°C剝除劑溶液（傑提貝克(J T Baker) PRS-2000) 10分鐘及使用DIW乾燥，然後使用比色計 及顯微鏡檢查其上彩色光敏樹脂之色彩變化及剝落現象。 22 200937118 結果歸類如下。 色彩變4匕 剝除劑處理後微弱色彩變化：優異 剝除劑處理後強烈色彩變化：不佳 5 剝離 彩色光敏樹脂無剝離：優異 彩色光敏樹脂部分剝離：不佳 結果提供於下表1。 〇 [表 1] 色彩變化 光敏性樹脂組成物之剝離 裸玻璃 SiNx 裸玻璃 SiNx 實例1 優異 優異 優異 優異 比較例1 優異 優異 不足 不足 比較例2 優異 優異 不佳 不佳 10 如表1所示，本發明之光敏性樹脂組成物對剝除劑具有 優異抗性。 熟諳技藝人士由前文說明提供之教示獲益將可了解多 項本發明之修改及其它實施例。因此須了解本發明並未囿 限於所揭示之特定實施例，修改及其它實施例意圖含括於 15 隨附之申請專利範圍。雖然於此處使用特定術語，但係以 通俗描述性定義使用而非意圖為限制性，本發明之範圍係 界定於申請專利範圍。 C圖式簡單說明I (無） 20 【主要元件符號說明】 (無） 23A photosensitive resin composition was prepared in the same manner as in Example 1, except that an epoxy acrylate-based oleic acid ester resin (EOCN, Nippon Q 10 Kayaku) was used instead of the acrylic acid carboxylate containing a double bond. Resin. Comparative Example 2 A photosensitive resin composition was prepared in the same manner as in Example 1 except that an acrylic carboxylic acid resin containing a double bond was not used. The peeling resistance was evaluated according to the resin compositions of Example 1 and Comparative Examples 1 to 2. The photosensitive resin composition of Example 1 and Comparative Examples 1 to 2 was coated on a glass plate having a 500 Å SiNx layer using a spin coater to form a layer having a thickness of from 0.3 μm to 34 μm. Next, the layer was placed at 80 using a hot plate. (: Soft bake for 150 seconds. The layer was then exposed to 60 mJ light using an exposure apparatus and developed with a developer for 6 sec, washed for 60 sec, and centrifuged for 25 sec. then at 25. (: at 1%) The potassium hydroxide solution was used for development. The layer was then baked in a 230 ° C oven for 30 minutes. The color change was measured by a colorimeter after hard baking. The hard baked test piece was dipped at 70 ° C. The stripping agent solution (JT Baker PRS-2000) was dried for 10 minutes and dried using DIW, and then the color change and peeling of the colored photosensitive resin thereon were examined using a colorimeter and a microscope. 22 200937118 The results are classified as follows. Color change 4 匕 peeling agent after weak color change: strong color change after excellent stripping agent treatment: poor 5 peeling color photosensitive resin without peeling: excellent color photosensitive resin partial peeling: poor results are provided in Table 1 below. [Table 1] Color change photosensitive resin composition exfoliated bare glass SiNx bare glass SiNx Example 1 Excellent, excellent, excellent, excellent, Comparative Example 1 Excellent, excellent, insufficient, insufficient, Comparative Example 2 Excellent, excellent, poor, poor As shown in Table 1, the photosensitive resin composition of the present invention has excellent resistance to the stripping agent. A person skilled in the art will appreciate many modifications and other embodiments of the present invention from the teachings provided in the foregoing description. The invention is not limited to the specific embodiments disclosed, and the modifications and other embodiments are intended to be included in the scope of the accompanying claims. For the sake of limitation, the scope of the present invention is defined in the scope of the patent application. C is a simple description of I (none) 20 [Description of main component symbols] (none) 23