200914896 jjau/ujuz z^^85twf.doc/n 九、發明說明： 【發明所屬之技術領域】 本發明是有關於一種感光性樹脂組成物，且特別是有 關於一種彩色濾光片的保護膜用感光性樹脂組成物。 【先前技術】 習知，液晶顯示器面板之彩色濾光片的製作方法為， 先在玻璃基板上形成多個黑色矩陣(black matrixes)，然後 〇 在相鄰的黑色矩陣之間依序形成紅(red，R)、綠(green，G)、 藍(blue，B)的顏色層，以作為晝素(pixel)，而當光線通過晝 素時即會顯現出顏色。另外，在彩色濾光片製作完成後， 接著會形成透明電極膜，覆蓋黑色矩陣與顏色層。通常， 在彩色濾光片和透明電極之間還會形成一層保護膜 (overcoating layer) ’使彩色濾光片的表面較為平坦化，有 助於透明電極的製造，且亦可保護彩色濾光片不受後續製 程的影響。一般而言，上述之保護膜必須具備有高透光度 I (transmittance) ’ 南附著度（close adhesivity) ’ 高耐熱性 (thermal resistance)，高而:丨·酸性(acid resistance)及高而子驗性 (base resistance)等特性，始可應用於此領域中。 在一些文獻中，例如 US 6582862、US 7097959、WO 2006/129924等專利，皆提出了有關彩色濾光片的保護膜 的相關技術。在上述文獻中，揭露彩色濾光片的保護膜為 負型光阻組成物(negative resist composition)，其包括驗可 /谷性樹脂膠合劑(alkaH dissolvable resin binder)、光聚合型 化合物（photopolymerization compound)、光起始劑 200914896 jjau/uju^ z^^85twf.doc/n 這些文獻中 、耐熱@ & (photopolymerization initiator)及溶劑。然而， 所提出之組成物的特性，例如耐鹼性、耐酸性 性及透光度，皆較差。 之組成物的研發及其特 題之一〇 因此’彩色濾光片的保護膜用 性提昇’已成為業界發展的重要課 【發明内容】 本务明的目的就S在提供—種彩色濾光片的保護膜 Γ、 肖感光性樹脂組成物，能夠避Μ知的問題發生，且此感 光性樹脂組成物具有高光穿透度等特性。χ ^ 本發明提出-種顯示面板的高彈性間隔物用感光性 樹脂組成物，其包括：（Α)光反應型驗可溶性樹脂膠合劑、 ⑻光聚合型含⑽性純和基的化合物、（c)光起始劑、 (D)有機酸gf、⑻分子中至少含有2個環氧基的化合物， S及(F)有機溶劑。其中，⑷光反應型鹼可溶性樹脂膠合 包括(a-l)含酸基的乙稀性不飽和單體、（a_2)可與(心丄) 〇 共聚合，且在側接有軟鏈的乙烯性不飽和單體，其中軟鏈 為C6〜C12的環狀烷基，以及(a_3)含環氧基的乙烯性不飽 和單體。 ^本發明之感光性樹脂組成物，適用於彩色濾光片的保 護膜，其可具有更高的光穿透度、附著度、表面平坦性， 且具有更較佳的耐熱性、财酸驗性及耐熱變色性，以提高 元件效能。 ’ ▲為讓本發明之上述和其他目的、特徵和優點能更明顯 易懂，下文特舉較佳實施例，並配合所附圖式，作詳細說 200914896 uau/u^uz z^fj35twf.doc/n 明如下。 【實施方式】 本發明提出一種彩色濾光片的保護膜用感光性樹脂 組成物，不僅具有更高的光穿透度、附著度、表面平坦性， 且具有更較佳的对熱性、耐酸鹼性及耐熱變色性。 本發明之彩色濾光片的保護膜用感光性樹脂組成 物，其組成包括：（A)光反應型鹼可溶性樹脂膠合劑、（B) 光聚合型含乙烯性不飽和基的化合物、（C)光起始劑、（D) 有機酸酐、(E)分子中至少含有2個環氧基的化合物以及(巧 有機溶劑。 本發明之樹脂組成物的(B)光聚合型含乙烯性不飽和 基的化合物，為具有至少一個乙烯性不飽和基的乙烯性不 飽和化合物。（B)光聚合型含乙烯性不飽和基的化合物，例 如是乙二醇二曱基丙烯酸醋（ethylene glycol di(meth)acrylate)、具有 2-14 個環氧乙炫基(ethyleneoxide group)的聚乙二醇二曱基丙烯酸酯（polyethylene glycol di(meth)acrylate)、三曱醇丙燒二曱基丙稀酸酯(trimethylol propane di(meth)acrylate)、三曱醇丙悅三曱基丙稀酸酯 (trimethylol propane tri(meth)acrylate)、異戊四醇三曱基丙 稀酸 S旨(pentaerythritol tri(meth)acrylate)、異戊四醇四曱基 丙烯酸S旨(pentaerythritol tetra(meth)acrylate)、具有 2-14 個 環氧丙烧基(propyleneoxide group)的丙烯甘醇二甲基丙烯 酸醋(propyleneglycol di(meth)acrylate)、二季戊四醇五曱基 丙稀酸S旨（dipentaerythritol penta(meth)acrylate)、二季戊四 200914896 uy^\j ikjdkja 85twf.doc/n 醇六甲基丙烯酸酯（dipentaerythritol hexa(meth)acrylate， DPHA)、三羥曱基丙烧三縮水甘油醚丙烯酸添加劑 (trimethylolpropanetriglycidylether acrylic acid additives) ' 雙紛A二縮水甘油醚丙稀酸添加劑（bisphenol A diglycidylether acrylic acid additives)、鄰苯二曱酸二S旨類的 (曱基）丙稀酸-β-經乙酉旨（phthalate diesters of β -hydroxyethyl(meth)acrylate)、曱苯二異氫酸g旨添加劑的（甲 基）丙烯酸-/3 -經乙醋（toluene diisocyanate additives of 冷 -hydroxyethyl(meth)acrylate)，以及具有乙烯性不飽和鍵 (ethylenically unsaturated bond)的聚合性化合物(polymeric compound)，其中乙稀性不飽和鍵是選自由二三經基甲基 丙烧四丙烯酸醋（ditrimethylol propanetetraacrylate)、乙氧 基化三聚異氫酸三丙烯酸酯 (tris(2-acryloxyethyl)isocyanurate)、含乙氧基季戊五醇四丙 稀酸醋（ethoxylated pentaerylthritoltetraacrylate) (EO 4 mol)、季戊五醇四丙稀酸 S旨（pentaerythritoltetraacrylate) (EO 35 mol)、含乙氧基三羥甲基丙烷三丙烯酸酯 (ethoxylated trimethylolpropanetriacrylate) (EO 9 mol)、含乙 氧基三羥曱基丙烷三丙烯酸酯（EO 3 mol)、含丙氧基三羥 曱基丙 烧三丙 浠酸醋 (propxylated pentaerythritoltetraacrylate) (PO 4 mol)、九乙二醇二丙稀酸 酯(nonaethylene glycol diacrylate)、以己内酯改質的雙季戊 四醇六丙烯酸醋（dipentaerythritolhexaacrylate-modifled caprolactone)、三經甲基丙烧丙氧基三丙稀酸g旨 200914896 jjau/ujuz /4^85twf.doc/n (trimethyl〇lpr〇panepr〇poxylate 出⑽咖⑹所組成之群組。 上述之光聚合型含乙烯性不飽和基的化合物可單獨或混合 數種使用。而且，基於(A)光反應型鹼可溶性樹脂膠合劑為 100重量份，（B)光聚合型含乙烯性不飽和基的化合物之含 量為1〜250重量份。 (c)光起始劑，例如為氧化膦(phosphine oxide)系化合 物、羰基(carbonyl)系化合物、胺羰(amin〇carb〇nyl)系化合 物、三嗪(triazine)系化合物、肟(oxime)系化合物、胺(amine) 糸化合物、烧氧基駢葱（alkoxyantharcene)系化合物與嗟嘴 (thioxanthone)系化合物所組合之族群的其中之一。其中， 氧化膦（phosphine oxide)系化合物例如是芳膦氧化物 (arylphosphine oxide)、醯膦(aCylph〇Sphine oxide)、雙醯膦 (bisacylphosphine oxide)、2,4,6-三曱基苯甲醯基-二苯基氧膦 (2,4,6-trimethylbenzoyldiphenylphosphine oxide (TPO))、2,6-二 乙基苯甲醯基-二苯基氧膦 (2,6-(^111}^6112；〇}4(%]1611>^11〇3卩1111^(^(!6)、2,6-二曱基苯曱醯 基-二苯基氧膦（2,6-dimethoxybenzoyldiphenylphosphine oxide) 、2,6-二氣苯曱醯基-二苯基氧膦 (2,6-dichlorobenzoyldiphenylphosphine oxide)、2,3,5,6-四曱基苯 曱 醯基 -二苯 基氧膦 (2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide)、笨曱酿二 (2,6- 二曱 苯基） 膦酸 (benzoyldi(2,6-dimethylphenyl)phosphonate)、2,4,6-三曱基苯曱 醯基 苯基膦 酸乙酯 200914896 υΑυ/υ^υ/ Z4j85twf.doc/n (2,4,6-trimethylbenzoylethoxyphenylphosphine oxide)、雙(2,4,6-三甲 基苯甲 醯基）苯基氧化 膦)(1^(2,4,6-1；]^11161;11丫出6112〇>^)卩1^11}^11〇8卩1±16(1-819))、雙(2,6-甲氧苯甲醯基）-2,4,4-三甲基苯基氧膦 (bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide))。幾基(carbonyl)系化合物、胺幾(aminocarbonyl)系化 合物、三^(triazine)系化合物、將(oxime)系化合物等系列 化合物例如是乙酿苯（acetophenone)、二苯曱酮 (benzophenone)、二苯基酮(biphenylketone)、1-經基-1-環己基 苯基曱酮(1 -hydroxy-1 -benzoylcyclohexane (I-184))、苄基丙酮 2.2- 二曱氧基-1,2-二苯乙烧-1-酮（benzyldimethylketal 2.2- dimethoxy-l，2-diphenylethane-l-one (1-651))、1-苄基-1-二曱 基叔胺 -1-(4- 嗎琳-苯甲酿）丙炫 (1 -benzyl-1 -dimethylamino-1 -(4-morpholino-benzoyl)propane (1-369)) 、2-嗎啉-2-(4-曱硫基）苯曱醯丙烷 (2-morpholyl-2-(4-methylmercapto)benzoylpropane (1-907))、 ethylantraquinone、4-苯曱驢基-4-曱基二苯硫醚 (4-benzoyl-4-methyldiphenylsulfide)、苯曱酿苯曱醇丁醚 (benzoinbutylether) 、 2-經基-2-苯曱醯丙燒 (2-hydroxy-2-benzoylpropane)、2-羥基-2-(4-異丙基)苯曱隨丙炫 (2-hydroxy-2-(4-isopropyl)benzoylpropane)、4-丁基苯曱酿三氣 曱烧(4-131117^^1^〇>^1^]11〇1'〇11161;1见1^)、4-苯氧基笨曱酿二氯曱 烧（4-phenoxybenzoyldichloromethane)、苯曱醯曱酸曱酉旨 (benzoylmethylformate) 、1，7-雙（9- °丫 淀基）庚烧 200914896 t z.*+i 8 5 twf. doc/n (l，7-bis(9-acridinyl)heptane)、9-n- 丁基-3,6-雙（2-嗎琳 -isobutyloyl) 〇卡 〇坐 (9-n-butyl-3,6-bis(2-morpholino-isobutyloyl)carbazole)、10-丁基 -2-chloroacrydone(10-butyl-2-chloroacrydone)、2-[2-(4-曱氧基-苯基）-乙烯基]-4,6-雙-三氣甲基-[1,3,5]三嗪 (2-[2-(4-methoxy-phenyl)-vinyl]-4,6-bis-trichloromethyl-[l,3,5]tr iazine)、2-(4-曱氧基•萘-1-基)-4,6-雙-三氯曱基-[1，3,5]三嗪 ζ\ (2-(4-methoxy-naphthalen-1 -y 1)-4,6-bis-trichloromethyl- [ 1,3,5]tri azine)、2-曱苯[1,3]二氧雜環戊烯-5-基-4,6-雙-三氯曱基-[1,3,5] 三 °秦 (2-benzo[l，3]dioxol-5-yl-4,6-bis-trichloromethyl-[l，3,5]triazine) 、2-甲基-4,6-雙（三氯甲基）-s-三嗪 (2-methyl-4,6-bis(trichloromethyl)-s-triazine)、2-苯基-4,6-雙(三 氯曱基)令三嗪(2-卩1^11>4-4,6-1^(111(土1〇1*〇11161;]154)-3-1；1^71116)、2-萘酯 -4,6- 雙（三氯曱基 ）-S- 三嗪 (2-naphthyl-4,6-bis(trichloromethyl)-s-triazine)、1-[9-乙基-6-(2-U 甲基苯曱醯基)-9.H-咔唑-3-基]-二環庚基甲烷-1-酮肟-〇-乙酸 酯、1-[9-乙基-6-(2-甲基苯曱醯基)-9.H_咔唑-3-基]••二環庚基-1-酮肟-0-乙酸酯、1-[9-乙基-6-(2-甲基苯曱醯基)-9.H-咔唑-3-基]-金剛烷基曱烷-1-酮肟-〇-苯曱酸酯、1-[9-乙基-6-(2-曱基苯曱醯 基)-9.H-咔唑-3-基]-金剛烷基曱烷-1-酮肟-〇-乙酸酯、1-[9-乙基 -6-(2-曱基苯曱醢基)-9.H-咔唑-3-基]-四氢呋喃基曱烷小酮肟 -0-苯曱酸酯、1-[9-乙基-6-(2-曱基苯曱醯基)-9.H-咔唑-3-基]-四氢呋喃基曱烷-1-酮肟-〇_乙酸酯、1-[9-乙基-6-(2-甲基苯曱醯 11 200914896 ^Hj85twf.doc/n 基)-9.H-咔唑-3-基]-塞吩基曱烷小酮肟_〇_苯曱酸醋、μ卜乙基 -6-(2-甲基苯曱醯基)_9.Η-咔唑-3-基]-塞吩基曱烷小酮肟_〇_乙 酸酯、1-[9-乙基-6-(2-甲基苯甲醯基)-9.Η-咔唑-3-基]-碼吩基甲 烷-1，肟-0-苯甲酸酯、Η9-乙基_6_(2_甲基苯曱醯基)_9凡咔 唑-3-基]-碼吩基曱烷-μ酮肟_〇_乙酸酯、^[9_乙基_6_(2_曱基苯 曱醒基)-9.Η-咔嗤-3-基]-乙烧-1-酮將-〇-二環丁烧酸酯、丨_[9_ 乙基-6-(2-甲基苯甲醯基)_9.Η-咔嗤-3-基]-乙燒小酮肟_〇_三環 (') 撥烧酸醋、1-[9_乙基-6-(2-甲基苯甲酸基)-9.1^卡唾-3-基]-乙烧 -1-酮肟-0-金剛烷酸酯、1,2-辛二酮小[4-(苯硫基)苯基]_2_(〇_ 苯曱醯基肟）、1,2-丁二酮-1-[4-(苯硫基)苯基]-2-(〇苯曱醯基 肟）、I,2-丁二酮小[4-(苯硫基)苯基]_2_(〇_乙醯基蔣）、L2-辛二 酮-1-[4-(曱硫基)苯基]-2_(〇-苯甲醯基將）、辛二酮小[4_(苯 硫基)苯基]-2-(0-曱基苯甲酸基肪）。胺系化合物例如是三乙醇 胺(triethanolamine)、曱基二乙醇胺(methyldiethanolamine)、三 異丙醇胺(triisopropylamine)、4-二曱基胺基甲基苯甲酸乙酯 (4-dimethylaminomethyl benzoate)、4-二曱基胺基乙基苯曱酸乙 () , 醋(4-dimethylaminoethy 1 benzoate)、4-二曱基胺基異戊基苯甲 酸乙酉旨(4-methylaminoisoamyl benzoate)、2-曱基胺基乙基苯甲 酸乙醋(2-methylaminoethyl benzoate)、4-二曱基胺基-2-乙基已 基苯曱酸乙醋(4-dimethylamino-2-ethylhexyl benzoate)、Ν,Ν-曱基對曱苯胺(>^,]^-11^1;]1}^&瓜的11^出1^)、4,4’-雙(二曱基胺基) 二苯曱酮(4,4’-bis(dimethylammo)benzophenone)、4,4’-雙(二乙 基胺基)二苯曱酮(4,4’-1^((^也}^111^1〇片61^〇卩11611〇1^)、4,4’-雙 (乙 基曱基胺基）二笨曱酮 12 200914896 u^wj zHJ85twf-doc/n (4,4’-bis(ethylmethylamino)benzophenone)。烧氧基骄蒽系化合 物例如是9，10-二曱氧基蒽(9,10-(1丨11^1;11〇父3^111;]1^〇61^)、9，10-二乙氧基蒽(9，10-diethoxyanthracene)、2-乙基 9，10-二曱氧基 蒽(2-ethyl-9,10-dimethoxyanthracene)、2-乙基 9,10-二乙氧基蒽 (2-ethyl-9，10-diethoxyanthracene)。0塞嘲系化合物例如是 2-異 丙基°塞°頓酮（2-isopropylthioxanthone)、4-異丙基嘆β镇酮 (4-isopropylthioxanthone (ΙΡΤΧ))、2,4-二乙基。塞啼嗣 (1 (2,4-diethylthioxanthone (DETX))、2,4-三氯基嗟嘲酮 (2,4-trichlorothioxanthone) 、 1-氯-4-丙基嗟嘲酮] (1 -chloro-4-propoxythioxanthone)。上述之光起始劑可單獨或 混合數種使用。而且’基於(A)光反應型鹼可溶性樹脂膠合 劑為100重量份，（C)光起始劑之含量為0.1〜100重量份。 (D) 有機酸酐，例如為順丁烯二酸酐（maleic anhydride，ΜΑ)、伊康酸酐(itaconic anhydride)、四氫酞酐 (tetrahydrophthalic anhydride)、檸康酸酐（citrac〇nic anhydride)或中康酸gf(mesaconic anhydride)。上述之有機 ^ 酸酐可單獨或混合數種使用。而且，基於(A)光反應型驗可 溶性樹脂膠合劑為1〇〇重量份，（D)有機酸酐之含量為〇 1 〜100重量份。 (E) 分子中至少含有2個環氧基的化合物，例如是雙紛 A環氧樹脂(bisphenol Atype epoxy)化合物、雙酚s環氧樹脂 (bisphenol S type epoxy)化合物、芴冬雙酚二環氧甘油鍵 (Fluorene-9-bisphenol diglycidyl Ether (FBDE))、雙酚 a 型環氧 樹脂(bisphenol A type epoxy resin，例如：油化 Shell Ep〇xy 公 13 200914896 u^v/v3vz zHJ85twf.doc/n 司製’商品名為 Epikote828、1001、1002、1004 等）、雙紛 A 型環氧樹脂之醇型經基(alcoholic hydroxyl)與環氧氣丙烧 (epichlorohydrin)反應而得之環氧樹脂(例如：曰本化藥公司 製’商品名為NER-1302 ’環氧當量323，軟化點76。〇、雙紛 F 型環氧樹脂(bisphenol F type epoxy resin，例如：油化 Shell200914896 jjau/ujuz z^^85twf.doc/n IX. Description of the Invention: [Technical Field] The present invention relates to a photosensitive resin composition, and particularly to a protective film for a color filter A photosensitive resin composition. [Prior Art] Conventionally, a color filter of a liquid crystal display panel is formed by first forming a plurality of black matrixes on a glass substrate, and then sequentially forming red between adjacent black matrices ( The color layers of red, R), green (green), and blue (blue, B) are used as pixels, and the color appears when the light passes through the element. Further, after the color filter is completed, a transparent electrode film is formed to cover the black matrix and the color layer. Usually, an overcoating layer is formed between the color filter and the transparent electrode. The surface of the color filter is flattened to facilitate the manufacture of the transparent electrode, and the color filter can also be protected. Not affected by subsequent processes. In general, the above protective film must have a high transmittance I (close adhesivity) 'high thermal resistance, high: acid resistance and high Characteristics such as base resistance can be applied to this field. In some documents, for example, the patents of US Pat. No. 6,582,862, US Pat. In the above documents, the protective film of the color filter is disclosed as a negative resist composition, which includes an alkaH dissolvable resin binder and a photopolymerization compound. ), photoinitiator 200914896 jjau/uju^ z^^85twf.doc/n Among these documents, heat resistance @ & (photopolymerization initiator) and solvent. However, the properties of the proposed composition, such as alkali resistance, acid resistance and light transmittance, are inferior. The development of the composition and one of its special problems, therefore, the 'enhancement of the protective film for color filters' has become an important part of the development of the industry. [Inventive content] The purpose of this service is to provide color filtering. The protective film 肖 and the opaque photosensitive resin composition of the sheet can avoid the problem of knowing, and the photosensitive resin composition has characteristics such as high light transmittance. χ ^ The present invention provides a photosensitive resin composition for a high elastic spacer of a display panel, which comprises: (Α) a photoreactive type soluble resin binder, (8) a photopolymerizable type (10) pure sulfhydryl compound, ( c) a photoinitiator, (D) an organic acid gf, (8) a compound having at least two epoxy groups in the molecule, S and (F) an organic solvent. Wherein, (4) the photoreactive alkali-soluble resin is cemented to include (al) an ethylenically unsaturated monomer having an acid group, (a_2) may be copolymerized with (heart-rhodium) ruthenium, and the ethylenic group having a soft chain attached thereto is not A saturated monomer wherein the soft chain is a C6-C12 cyclic alkyl group, and (a-3) an epoxy group-containing ethylenically unsaturated monomer. The photosensitive resin composition of the present invention is suitable for a protective film of a color filter, which can have higher light transmittance, adhesion, surface flatness, and has better heat resistance and acidity test. Sex and heat discoloration to improve component performance. The above and other objects, features, and advantages of the present invention will become more apparent and understood. /n is as follows. [Embodiment] The present invention provides a photosensitive resin composition for a protective film of a color filter, which has not only higher light transmittance, adhesion, surface flatness, but also better heat resistance and acid resistance. Alkaline and heat resistant discoloration. The photosensitive resin composition for a protective film of a color filter of the present invention, comprising: (A) a photoreactive alkali-soluble resin binder, (B) a photopolymerizable ethylenically unsaturated group-containing compound, (C) a photoinitiator, (D) an organic acid anhydride, a compound containing at least two epoxy groups in (E) a molecule, and (a) an organic solvent. (B) Photopolymerizable type of ethylenically unsaturated compound of the resin composition of the present invention The compound of the group is an ethylenically unsaturated compound having at least one ethylenically unsaturated group. (B) a photopolymerizable ethylenically unsaturated group-containing compound such as ethylene glycol dimethacrylate (ethylene glycol di (ethylene glycol di) Meth)acrylate, polyethylene glycol di(meth)acrylate with 2-14 ethylene oxide groups, trimethyl alcohol-propyl dimethacrylate Trimethylol propane di (meth)acrylate, trimethylol propane tri(meth)acrylate, pentaerythritol tridecyl acrylate S (pentaerythritol tri(meth) )acrylate), isopentitol tetradecyl acrylate (pentaerythritol tetra(meth)acrylate), propyleneglycol di(meth)acrylate with 2-14 propylene oxide groups, dipentaerythritol pentadecyl acrylate S Dipentaerythritol penta(meth)acrylate, dipentaerythritol 200914896 uy^\j ikjdkja 85twf.doc/n dipentaerythritol hexa(meth)acrylate, DPHA, trishydroxypropylpropane triglycidyl Trimethylolpropanetriglycidylether acrylic acid additive (bisphenol A diglycidylether acrylic acid additive), phthalic acid bis(A) thiol acid-β- (meth)acrylic acid-/3-acetic acid (toluene diisocyanate) And a polymeric compound having an ethylenically unsaturated bond, wherein the ethylenically unsaturated bond is selected Ditrimethylol propanetetraacrylate, tris(2-acryloxyethyl)isocyanurate, ethoxylated pentaerythritol tetrapropyl acrylate Ethoxylated pentaerylthritoltetraacrylate (EO 4 mol), pentaerythritoltetraacrylate (EO 35 mol), ethoxylated trimethylolpropanetriacrylate (EO 9) Mol), ethoxylated trihydrocarbyl propane triacrylate (EO 3 mol), propoxylated triphenyl sulfonyl propylene triacetate (prop 4 ) Nonaethylene glycol diacrylate, dipentaerythritol hexaacrylate-modifled caprolactone modified with caprolactone, trimethyl methacrylate propylene triacetate g 200914896 jjau/ujuz / 4^85twf.doc/n (trimethyl〇lpr〇panepr〇poxylate out (10) coffee (6) group. The above photopolymerizable ethylenically unsaturated group-containing compound may be used singly or in combination of several kinds. Further, the content of the (B) photopolymerizable ethylenically unsaturated group-containing compound is from 1 to 250 parts by weight based on 100 parts by weight of the (A) photoreactive alkali-soluble resin binder. (c) a photoinitiator, for example, a phosphine oxide compound, a carbonyl compound, an amin〇carb〇nyl compound, a triazine compound, or oxime. One of a group of a compound, an amine ruthenium compound, an alkoxyantharcene-based compound, and a thioxanthone-based compound. Wherein, the phosphine oxide compound is, for example, an arylphosphine oxide, aCylph〇Sphine oxide, bisacylphosphine oxide, 2,4,6-trimercaptobenzamide 2,4,6-trimethylbenzoyldiphenylphosphine oxide (TPO), 2,6-diethylbenzylidene-diphenylphosphine oxide (2,6-(^111}^6112; 〇}4(%]1611>^11〇3卩1111^(^(!6), 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,3,5,6-tetradecylbenzoyl-diphenylphosphine oxide (2,3,5 ,6-tetramethylbenzoyldiphenylphosphine oxide), benzoyldi(2,6-dimethylphenyl)phosphonate, 2,4,6-trimercaptophenylphenyl Ethylphosphonate 200914896 υΑυ/υ^υ/ Z4j85twf.doc/n (2,4,6-trimethylbenzoylethoxyphenylphosphine oxide), bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide) ^(2,4,6-1;]^11161;11丫6112〇>^)卩1^11}^11〇8卩1± 16(1-819)), bis(2,6-methoxybenzhydryl)-2,4,4-trimethylphenylphosphine oxide (bis(2,6-dimethoxybenzoyl)-2,4,4 -trimethylpentylphosphine oxide)) A series of compounds such as a carbonyl compound, an aminocarbonyl compound, a triazine compound, and an oxime compound, such as acetophenone and diphenyl Benzophenone, biphenylketone, 1-hydroxy-1-benzoylcyclohexane (I-184), benzylacetone 2.2-dioxane Benzyldimethylketal 2.2- dimethoxy-l, 2-diphenylethane-l-one (1-651), 1-benzyl-1-didecyl tertiary amine-1 -(4-Merlin-Benzyl) propyl (1-benzyl-1 -dimethylamino-1 -(4-morpholino-benzoyl)propane (1-369)), 2-morpholin-2-(4-曱2-morpholyl-2-(4-methylmercapto)benzoylpropane (1-907), ethylantraquinone, 4-phenylmercapto-4-mercaptodiphenyl sulfide (4-benzoyl-4) -methyldiphenylsulfide), benzoinbutylether, 2-hydroxy-2-benzopyrene (2-hydroxy-2) -benzoylpropane), 2-hydroxy-2-(4-isopropyl)benzoquinone with 2-hydroxy-2-(4-isopropyl)benzoylpropane, 4-butylbenzoquinone -131117^^1^〇>^1^]11〇1'〇11161;1 see 1^), 4-phenoxybenzoyldichloromethane, bismuth benzoate Benzylmethylformate, 1,7-bis(9- °丫 基)g. 200914896 t z.*+i 8 5 twf. doc/n (l,7-bis(9-acridinyl)heptane),9 -n-butyl-3,6-bis(2-morphine-isobutyloyl) 9-n-butyl-3,6-bis(2-morpholino-isobutyloyl)carbazole, 10-butyl- 2-chloroacrydone (10-butyl-2-chloroacrydone), 2-[2-(4-decyloxy-phenyl)-vinyl]-4,6-bis-tris-methyl-[1,3,5 Triazine (2-[2-(4-methoxy-phenyl)-vinyl]-4,6-bis-trichloromethyl-[l,3,5]tr iazine), 2-(4-decyloxy•naphthalene- 1-yl)-4,6-bis-trichloroindenyl-[1,3,5]triazinium\(2-(4-methoxy-naphthalen-1 -y 1)-4,6-bis-trichloromethyl - [ 1,3,5]tri azine), 2-indolyl [1,3]dioxol-5-yl-4,6-bis-trichloroindolyl-[1,3,5] 3-benzo[2-,[l,3]dioxol-5-yl-4,6-bis-trichlor Omethyl-[l,3,5]triazine), 2-methyl-4,6-bis(trichloromethyl)-s-triazine (2-methyl-4,6-bis(trichloromethyl)-s-triazine ), 2-phenyl-4,6-bis(trichloroindenyl)-triazine (2-卩1^11>4-4,6-1^(111(土1〇1*〇11161;]154) )-3-1;1^71116), 2-naphthyl-4,6-bis(trichloromethyl)-s-triazine ,1-[9-ethyl-6-(2-U-methylphenylindenyl)-9.H-indazol-3-yl]-bicycloheptylmethane-1-one oxime-indole-acetic acid Ester, 1-[9-ethyl-6-(2-methylphenylhydrazino)-9.H-indazol-3-yl]••bicycloheptyl-1-oneindole-0-acetic acid Ester, 1-[9-ethyl-6-(2-methylphenylhydrazino)-9.H-carbazol-3-yl]-adamantyl decane-1-one oxime-indole-benzoquinone Acid ester, 1-[9-ethyl-6-(2-mercaptophenyl)-9-H-indazol-3-yl]-adamantyl decane-1-one oxime-〇-B Acid ester, 1-[9-ethyl-6-(2-mercaptophenyl)-9-H-indazol-3-yl]-tetrahydrofuranyl decane ketone oxime-0-benzoate , 1-[9-ethyl-6-(2-mercaptophenylhydrazino)-9.H-carbazol-3-yl]-tetrahydrofuranyl decane-1-one oxime-indole-acetate, 1-[9-ethyl-6-(2-methylphenylhydrazine 11 200914896 ^Hj85twf.doc/n -9.H-carbazol-3-yl]-cefenyl decane ketone oxime 〇 〇 曱 benzoic acid vinegar, μ 乙基 ethyl-6-(2-methylphenyl fluorenyl) _9. Η-咔Zyridin-3-yl]-cefenyl nonane ketone oxime oxime acetate, 1-[9-ethyl-6-(2-methylbenzylidene)-9.indole-carbazole- 3-yl]-code phenethyl methane-1, 肟-0-benzoate, Η9-ethyl_6_(2-methylphenyl fluorenyl)_9 valazol-3-yl]-code phenyl曱--- ketone 肟 〇 乙酸 乙酸 acetate, ^ [9_ethyl _6_(2_mercaptophenyl fluorenyl)-9. Η-咔嗤-3-yl] 〇-〇-bicyclobutyrate, 丨_[9_ethyl-6-(2-methylbenzhydryl)_9.Η-咔嗤-3-yl]-acetone ketone 肟_〇_ Tricyclic (') sauerkraut, 1-[9-ethyl-6-(2-methylbenzoate)-9.1^carbin-3-yl]-ethid-1-one oxime-0- Adamantane ester, 1,2-octanedione small [4-(phenylthio)phenyl]_2_(〇_phenylhydrazinyl), 1,2-butanedione-1-[4-(benzene Thio)phenyl]-2-(indolyl hydrazide), I,2-butanedione [4-(phenylthio)phenyl]_2_(〇_乙醯基蒋), L2-xin Diketo-1-[4-(indolyl)phenyl]-2_(indole-benzylidene), octanedione [4_(phenylthio)phenyl]-2-(0-fluorenyl) Benzoic acid based). The amine compound is, for example, triethanolamine, methyldiethanolamine, triisopropylamine, 4-dimethylaminomethyl benzoate, 4- 4-dimethylaminoethy benzoate, 4-methylaminoisoamyl benzoate, 2-mercaptoamine 2-methylaminoethyl benzoate, 4-dimethylamino-2-ethylhexyl benzoate, hydrazine, fluorenyl-fluorenyl Aniline (>^,]^-11^1;]1}^& melon 11^1^), 4,4'-bis(didecylamino)benzophenone (4,4 '-bis(dimethylammo)benzophenone), 4,4'-bis(diethylamino)benzophenone (4,4'-1^((^also}^111^1〇片61^〇卩11611 〇1^), 4,4'-bis(ethyl decylamino) dioxin 12 200914896 u^wj zHJ85twf-doc/n (4,4'-bis(ethylmethylamino)benzophenone). The lanthanoid compound is, for example, 9,10-dimethoxy oxime (9,10-(1丨11^1; 11〇父3^111;]1^〇61^), 9,10 -1,10-diethoxyanthracene, 2-ethyl 9,10-dimethoxyanthracene, 2-ethyl 9,10-diethoxy 2-ethyl-9,10-diethoxyanthracene. 0 塞 mocking compound is, for example, 2-isopropylthioxanthone, 4-isopropylthioxanthone (ΙΡΤΧ)), 2,4-diethyl, 1 (2,4-diethylthioxanthone (DETX)), 2,4-trichlorothioxanthone, 1-chloro 4-propyl-4-methyloxypropanthione (1 -chloro-4-propoxythioxanthone). The above photoinitiators can be used singly or in combination of several kinds. Further, the content of the (C) photoinitiator is 0.1 to 100 parts by weight based on 100 parts by weight of the (A) photoreactive alkali-soluble resin binder. (D) an organic acid anhydride such as maleic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, citrac〇nic anhydride or mesaconic acid Gf (mesaconic anhydride). The above organic acid anhydrides may be used singly or in combination of several kinds. Further, the content of the (D) organic acid anhydride is 〇 1 to 100 parts by weight based on the (A) photoreaction type testable soluble resin binder. (E) a compound having at least two epoxy groups in the molecule, for example, a bisphenol Atype epoxy compound, a bisphenol S type epoxy compound, and an anthraquinone bisphenol bicyclic ring Fluorene-9-bisphenol diglycidyl Ether (FBDE), bisphenol A type epoxy resin (eg: oiled Shell Ep〇xy public 13 200914896 u^v/v3vz zHJ85twf.doc/ n Manufactured under the trade name 'Epikote 828, 1001, 1002, 1004, etc.), an epoxy resin obtained by reacting an alcoholic hydroxyl group with an epichlorohydrin (for example) : 曰本化药公司's 'commercial name NER-1302' epoxy equivalent 323, softening point 76. bis, bisphenol F type epoxy resin (for example: oiled shell
Epoxy 公司製，商品名為 Epikote807、4001、4002、4004 等）、 雙紛F型環氧樹脂之醇型經基(alc〇h〇lic hydroxyl)與環氧氯丙 Π 览(ePichlorohydrin)反應而得之環氧樹脂(例如：日本化藥公司 製’商品名為NER-7406 ’環氧當量35〇，軟化點66°C)、二苯 基縮水甘油醚(biphenyl glycidyl ether，例如：油化 Shell Epoxy a司衣，商名為Epikote YX4000)、（笨)驗搭型環氧樹脂 (phenol novolac type epoxy resin，例如：日本化藥公司製，商 品名為EPPN-201，油化Shell Epoxy公司製，商品名為 Epikotel52、154、157S65、157S70，陶氏化學公司製，商品 名為DEN-438)、曱（苯)驗藤型環氧樹脂(cres〇i n〇v〇iac ^ epoxy resin ’例如：日本化藥公司製，商品名為E〇CN]〇2S、 U 1020、104S)、三縮水甘油異氰尿酸酯(吨如办丨is〇cyanumte， 例如：日產化學公司製，商品名為TEPIC)、三酚曱烷型環氧 樹脂(trisphenol methane type epoxy resin，例如：日本化藥公司 製，商品名為 EPPN-501、-502、-5〇3)、fluorene type epoxy resin(例如：新曰鐵化學公司製，商品名為ESF_3〇〇)、脂環式 環氧樹脂（例如：Daicel化學工業公司製，商品名為 Cell〇Xide2021P、EHPE)、及環氧化聚丁二烯樹脂(ep〇xidized polybutadiene，例如：Daicel化學工業公司製，商品名為Ep〇lead 14 200914896 u^v/ν^υΔ /.Hj85twf.doc/n PB3600)等。而且，基於(a)光反應型鹼可溶性樹脂膠合劑 為100重量份，（E)分子中至少含有2個環氧基的化合物之 含量為0.1〜100重量份。 (F)有機溶劑’例如是笨(benzene)、甲苯(toluene)、二甲 苯(xylene)、甲醇(methanol)、乙醇(ethanol)、乙醇單丙醚 (ethylene glycol monopropyl ether)、二乙二醇二曱 i|(diethylene glycol dimethyl ether)、二乙二醇曱醚(diethylene glycol methyl f) ether)、曱氧基丙酸甲酯 methyl methoxypropionate)、乙氧基丙 酸乙酉旨(ethyl ethoxypropionate (EEP))、乳酸乙g旨(ethyllactate)、 四氫呋喃(tetrahydrofUran (THF))、乙醇單曱醚(ethylene glycol monomethyl ether)、乙醇單乙躂(ethylene glycol monoethyl ether)、曱基溶纖劑乙酸酯(methyl cellosolve acetate)、乙基溶 纖劑乙酸酯(ethyl cellosolve acetate)、二乙醇單曱醚(diethylene glycol monomethyl ether)、二乙醇單乙醚(diethylene glycol monoethyl ether)、二乙醇單丁醚(diethylene glycol monobutyl ether)、丙二醇曱醚醋酸g旨(propylene glycol methyl ether acetate [) ’ (PGMEA))、丙二醇乙醚醋酸醋(propylene glycol ethyl ether acetate)、丙二醇丙鍵醋酸 g旨(propylene glycol propyl ether acetate)、甲基異丁酮(methyl isobutyl ketone)、曱醚酮(methyl ether ketone)、丙酮(acetone)、環己酮(cyclohexanone)、二曱基 曱醯胺（dimethylformamide (DMF))、N，N-二曱基乙醯胺 (Ν,Ν-dimethylacetamide (DMAc)) 、1ST-曱基0比 17各酮 (N-methyl-2-pyrrolidone (NMP))、γ-丁内醋(γ-butyrolactone)。 上述之有機溶劑可單獨或混合數種使用。而且，基於(A) 15 200914896 υ^κ) "+j85twf.doc/n 1〇〇重量份，（F)有機溶劑 光反應型鹼可溶性樹脂膠合劑為 之含量為1〜250重量份。 另外，⑷光反應型驗可溶性樹脂膠合劑還包括 含酸基的乙躲不飽和單體、（a_2)可與㈣共聚合的( 性不飽和單m(a_3)含環氧基紅雜不飽和單體。 (A)光反應型鹼可溶性樹脂膠合劑的重量平均分 2,000〜500,000，其酸價為 1〇〜4〇〇 mgK〇H/g。里苟 其中’（a-Ι)含酸基的乙稀性不飽和單體，例如是（甲基) 丙烯酸、丁烯酸(crotonic acid)、α _氯（甲基）丙烯酸、（乙^ 丙烯酸以及桂皮酸(cinnamic acid)等不飽和一元酸類；馬1 酸、順丁烯二酸酐(maleic anhydride)、反丁烯二酸(fumaric acid)、伊康酸（uaconic acid)、伊康酸酐（itac〇nic anhydride)、擰康酸(citmconic acid) ' 檸康酸軒㈣咖。— anhydride)、中康酸(mesaconic acid)、中康酸酐(mesac〇nic anhydride)等不飽和二元酸(anhydride)類；三價以上的不飽 和多價酸(anhydride)類等。這些含酸基的乙烯性不飽和單 體可單獨或混合數種使用。基於(a-1)、（a_2)與(a_3)的總和 為100重量份，（a-1)含酸基的乙稀性不飽和單體之含量為 10〜90重量份。 本發明之感光性樹脂組成物中’（a-2)可與(a_i)共聚合 的乙稀性不飽和單體為在側接有軟鏈的乙烯性不飽和單 體’其中軟鍵為C6·〜'C12的壞狀烧基。因此，可得到透光 度為大於等於97%之感光性樹脂組成物，而可更適合應用 於製程中，以更加提南元件效能。（a-2)可與(a_i)共聚合的 乙烯性飽和單體’例如是甲基丙烯酸烯丙酯（allyl 16 200914896 ww 二 z.^85twf.doc/n (meth)acrylate)等含丙烯基(allyl group)的乙稀基化合物；乙 二醇二曱基丙烯酸醋（ethylene glycol di(meth)acrylate)、二 環戊烯二曱基丙烯酸酯（dicyclopentenyl di(meth)acrylate)、丙二醇二甲基丙稀酸醋(propylene glycol 出(11161:11)3(^加6)、2,2-二曱基-1,3-丙二醇二曱基丙烯酸醋 (2,2-dimethyl-l,3-propylene glycol di(meth)acrylate)、三乙 二醇二曱基丙烯酸g旨(triethylene glycol di(meth)acrylate)、 四甘醇二甲基丙烯酸酯（tetraethylene glycol di(meth)acrylate)、三（2-經乙基）異氰酸曱基丙稀酸酯 (tri(2-hydroxyethyl)isocyanate di(meth)acrylate)等含有兩個 丙烯酸基的乙烯基化合物；（曱基）丙烯腈 ((meth)acrylonitrile) 、 α-氯（曱基）丙烯腈 (a-chloro(meth)acrylonitrile)等之腈化乙烯基化合物；苯乙 烯、曱基笨乙烯、甲氧基苯乙烯等之芳香族乙烯基化合物； C6-C12之環狀烷基（曱基)丙烯酸等乙烯基化合物。較佳的 是，曱基丙烯酸雙環戊酯(dicyclopentanylmethacrylate)、苯 乙烯(styrene)、丙稀酸異辛g旨(iso-octylacrylate)、丙烯基（曱 基壓克力）（allylmethacrylate)、曱基丙稀腈 (methacrylonitrile)、2,2-二甲基-1，3_ 丙二醇雙壓克力 (2,2-dimethyl-l，3-propylene glycoldiacrylate)。這些與（a-1) 共聚合的乙稀性不飽和單體可單獨或混合數種使用。基於 (a-1)、（a-2)與(a-3)的總和為100重量份，（a_2)可與(a-Ι)共 聚合的乙烯性不飽和單體之含量為1〇〜9〇重量份。 承上述，本發明之感光性樹脂組成物可選擇性地加入 苯乙烯’以更加提高樹脂組成物的耐熱性及耐化性。 17 200914896 jl/^w / ^.-r-»85twf.doc/n (a-3)含環氧基的乙烯性不飽和單體，例如是（曱美）丙 烯酸縮水甘油酯(glycidyl (meth)acrylate)、（乙基）丙稀酸縮 水甘油酯(glycidyl (ethyl)aCrylate)、3,4-(曱基)丙烯酸環氧^ 酯(3,4-eP〇Xybutyl (methacrylate)、6,7-(甲基)丙烯酸環氧庚 酯(6,7-epoxyheptyl (meth)acrylate)、6,7-(乙基）丙烯酸環氧 庚酯(6,7-epoxyheptyl (ethyl)acrylate)、鄰乙烯基笨基縮水甘 油醚(o-vinylbenzylglycidylether)、間乙烯基苯基縮水甘油 n _(m-vinylbenzylglyCidylether)、對乙烯基苯基縮水甘油醚 (p-vinylbenzylglyddylether)。這些含環氧基的乙烯性不飽 和單體可單獨或混合數種使用。基於(a-1)、（a-2)與(a_3)的 總和為100重量份’而（a_3)含環氧基的乙烯性不飽 之含量為10〜90重量份。 — 在一實施例中’於本發明之感光性樹脂組成物中，可 進一步加入密著助劑(coupling agent)，以增進感光性樹脂組 成物的附著度。基於感光性樹脂組成物為10〇重量份，密著 助劑使用量可例如為0.01〜30重量份，較佳為〇.5〜3重量份。 ^ 密著助劑例如是含環氧基或含氨基之矽化合物，其例如為冷 -(3,4-環氧環己烷）乙基三甲氧基矽炫 出-(3,4-6卩〇父>^>^1〇116父；71)6也；71仿11^11〇乂>^1&1^)、冷-(3,4-環氧環 己烧）乙基二乙氧基石夕烧（p_(3,4-epoxycyclohexyl)ethyl triethoxysilane)、γ-環氧丙烷三曱氧基矽烷fr_glycid〇xypn)pyl Mmethoxysilane(GMS))、γ-環氧丙烷甲基二甲氧基矽烷 (γ-glycidoxypropyl methyldimethoxysilane)、γ-環氧丙烧甲基二 乙氧基石夕院(γ-glycidoxypropyl methyldiethoxysilane)、γ-環氧丙 18 200914896 …….J85twf.doc/n 烧二曱氧基乙氧基石夕烧（γ-glycidoxypropyl dimethoxy(ethoxy)silane)、γ-環氧丙烷二甲基曱氧基矽烷 (γ-glycidoxypropyl dimethyl(methoxy)silane)、γ-環氧丙烧二甲 基乙軋基石夕烧(丫-邑1}^<1€«;^1*〇|)71(1^1161:11)4(^111〇乂丫知1〇1^)、3,4-環氧丁基三曱氧基石夕烧(3,4-epoxybutyltrimethoxysilane)、3,4-環氧丁基三乙氧基石夕烧(3,4-epoxybutyltriethoxysilane)、N-(2-胺乙基）-3-胺丙基二曱氧基二曱基石夕烧 (、 (N-(2-aminoethyl)-3-aminopropyldimethoxymethylsilane ) > (3- 胺丙基)三曱氧基石夕烧((3-aminopropyl)trimethoxysilane)、（3-胺 丙基二乙氧基石夕烧((3-aminopropyl)triethoxysilane)、（N，N-二乙 基 -3- 胺丙基）三曱氧基石夕烧 ((N，N-diethyl-3-aminopropyl)trimethoxysilane)、Ν-β(胺乙基)γ-胺丙基三曱氧基石夕院）(N-p(aminoethyl)Y-aminopropyl trimethoxysilane)等，上述之密著助劑可單獨使用，亦可2種或 2種以上混合使用。 在另一實施例中，本發明的感光性樹脂組成物亦可進一 G 步加入界面活性劑(surfactant)。基於感光性樹脂組成物為ι〇〇 重量份，界面活性劑的使用量為0.01〜30重量份，較佳為0.5 〜3重量份。界面活性劑，例如是聚氧乙稀院醚 (polyoxyethylene alkyl ethers)(例如：聚氧乙烯月桂醚 (polyoxyethylene lauryl ether)、聚氧乙烯硬脂醚 (polyoxyethylene stearyl ether)、聚氧乙烯油基醚 (polyoxyethylene oleyl ether)等）、聚氧乙烯芳醚 (polyoxyethylene aryl ethers)(例如：聚氧乙烯辛基笨基醚 (polyoxyethylene octyl phenyl ether)、壬基酚聚氧乙烯醚 19 200914896 l^^wj / j85twfldoc/n (polyoxyethylene nonyl phenyl ether)等）、聚乙稀乙二醇二燒基 酉旨(polyethylene glycol dialkyl esters)(例如：聚乙稀乙二醇二月 桂酸(polyethylene glycol dilaurate)、聚乙烯乙二醇二硬脂酸 (polyethylene glycol distearate)等）、有機石夕氧烧聚合物 (organosiloxane polymer)(例如：KP341(由 Shin-Etsu Chemical Industry Co_, Ltd.製造）；（甲基)丙浠酸聚合物((metii)acrylic acid polymer)，例如：Polyflow No. 75、90、95(由 Kyoei-ShaYushi Kagaku Kogyo Co.，Ltd·製造）、Megafac F171、F172、F173、 F475(由 Dainippon Chemicals ana Ink Co.，Ltd·製造）、Florard FC430、FC431(由 Sumitomo 3M Co.，Ltd.製造）、Asahi Gard G710、Serflon S382、SC-101、SC-102、SC-103、Sc-104、SC-105、 SC-1068(由Asahi Glass Co.，Ltd.製造)等）’上述之界面活性劑 可單獨使用，亦可2種或2種以上混合使用。 在其他實施例中，本發明的感光性樹脂組成物還可進一 步加入其匕添加劑，其例如是消泡劑(def〇rmer)、調平劑 (leveling agent)、熱聚合抑制劑(thermal p〇lymerizaticm 恤化― agent)等。 以下，說明本發明之感光性樹脂組成物及(A)光反應型 驗可溶性樹脂膠合劑的製備方法。 [(A)光反應型驗可溶性樹脂膠合劑的製備方法] (A)^反應型鹼可溶性樹脂膠合劑例如是，由(a_丨)含酸 基的乙烯性不飽和單體與(a_2)可與(a-1)共聚合，且在側接 有軟鏈的&驗不飽和賴騎絲合反應，之後經酿化 反應盆將㈣含環氧基的乙不飽和單體接枝而形成。 /、中在‘造(A)光反應型驗可溶性樹脂膠合劑時， 20Epoxy company, trade name Epikote 807, 4001, 4002, 4004, etc.), double-type F-type epoxy resin alcoholic base (alc〇h〇lic hydroxyl) and epoxy chloroprene (ePichlorohydrin) reaction Epoxy resin (for example: Nippon Chemical Co., Ltd.'s trade name NER-7406 'epoxy equivalent 35 〇, softening point 66 ° C), diphenyl glycidyl ether (for example: oiled Shell Epoxy a clothing, trade name Epikote YX4000), phenol novolac type epoxy resin (for example: manufactured by Nippon Kayaku Co., Ltd., trade name EPPN-201, manufactured by Oily Shell Epoxy Co., Ltd., Named as Epikotel 52, 154, 157S65, 157S70, manufactured by The Dow Chemical Company, trade name DEN-438), 曱 (Benzene) vine-type epoxy resin (cres〇in〇v〇iac ^ epoxy resin 'example: Japan Manufactured by a pharmaceutical company, trade name is E〇CN]〇2S, U 1020, 104S), triglycidyl isocyanurate (for example, 丨is〇cyanumte, for example: manufactured by Nissan Chemical Co., Ltd., trade name TEPIC), Trisphenol methane type epoxy resin (for example: Made by Nippon Kayaku Co., Ltd., trade name is EPPN-501, -502, -5〇3), fluorene type epoxy resin (for example, manufactured by Shinkai Iron Chemical Co., Ltd., trade name is ESF_3〇〇), alicyclic epoxy resin (Example: manufactured by Daicel Chemical Industry Co., Ltd., trade name: Cell 〇 Xide 2021P, EHPE), and ep〇xidized polybutadiene (for example, manufactured by Daicel Chemical Industry Co., Ltd., trade name Ep〇lead 14 200914896 u ^v/ν^υΔ /.Hj85twf.doc/n PB3600) and so on. Further, the content of the compound having at least two epoxy groups in the (E) molecule is 0.1 to 100 parts by weight based on 100 parts by weight of the (a) photoreactive alkali-soluble resin binder. (F) organic solvent 'for example, benzene, toluene, xylene, methanol, ethanol, ethylene glycol monopropyl ether, diethylene glycol II曱i|(diethylene glycol dimethyl ether), diethylene glycol methyl f ether, methyl methoxypropionate, ethyl ethoxypropionate (EEP) , ethyl lactate, tetrahydrofUran (THF), ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve Acetate), ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether ), propylene glycol methyl ether acetate [) ' (PGMEA), propylene glycol ethyl ether acetate, propylene glycol Propylene glycol propyl ether acetate, methyl isobutyl ketone, methyl ether ketone, acetone, cyclohexanone, dimethyl decyl amide (dimethylformamide (DMF)), N,N-dimethylacetamide (DMA), 1ST-mercapto 0- 17 ketone (N-methyl-2-pyrrolidone (NMP)), Γ-butyrolactone. The above organic solvents may be used singly or in combination of several kinds. Further, based on (A) 15 200914896 υ^κ) "+j85twf.doc/n 1 part by weight, (F) organic solvent photoreactive alkali-soluble resin binder is contained in an amount of 1 to 250 parts by weight. In addition, (4) photoreactive type soluble resin binder further includes an acid-containing ethylidene-unsaturated monomer, (a_2) can be copolymerized with (iv) (sexually unsaturated single m(a_3) epoxy-containing red hetero-saturated (A) The photoreactive alkali-soluble resin binder has an average weight of 2,000 to 500,000, and its acid value is 1 〇 to 4 〇〇 mgK 〇 H / g. The sputum contains '(a- Ι) acid group The ethylenically unsaturated monomer is, for example, (meth)acrylic acid, crotonic acid, α-chloro(meth)acrylic acid, (ethyl acrylate, cinnamic acid, etc.) ; horse 1 acid, maleic anhydride, fumaric acid, uaconic acid, itaconic acid, citmconic acid 'Citronic acid Xuan (four) coffee. - anhydride), mesaconic acid (mesaconic acid), mesaconic acid (mesac〇nic anhydride) and other unsaturated dibasic acid (anhydride); trivalent or higher unsaturated polyvalent acid ( Anhydride, etc. These acid-containing ethylenically unsaturated monomers can be used singly or in combination of several types. Based on (a-1), (a_2) The sum of (a_3) is 100 parts by weight, and the content of the (a-1) acid group-containing ethylenically unsaturated monomer is 10 to 90 parts by weight. In the photosensitive resin composition of the present invention '(a-2) The ethylenically unsaturated monomer copolymerizable with (a-i) is a poorly burnt group in which an ethylenically unsaturated monomer flanked by a soft chain, wherein the soft bond is C6·~'C12. A photosensitive resin composition having a luminosity of 97% or more, which is more suitable for use in a process to further improve the performance of the device. (a-2) An ethylenic saturated monomer copolymerizable with (a-i) Is an allyl group-containing ethylene compound such as allyl methacrylate (allyl 16 200914896 ww two z.^85twf.doc/n (meth)acrylate); ethylene glycol dimercapto acrylate vinegar (ethylene) Glycol di(meth)acrylate), dicyclopentenyl di(meth)acrylate, propylene glycol dimethyl acrylate (propylene glycol (11161:11) 3 (^ plus 6), 2,2-Dimethyl-1,3-propanediol di(meth)acrylate, triethylene glycol dimercaptoacrylic acid g Triethylene glycol di(meth)acrylate), tetraethylene glycol di(meth)acrylate, tris(2-ethyl)isocyanurate (tri(2-hydroxyethyl) Isocyanate di(meth)acrylate), etc.; vinyl compound containing two acrylic groups; (meth)acrylonitrile (meth) acrylonitrile, alpha-chloro(meth)acrylonitrile A nitrile vinyl compound; an aromatic vinyl compound such as styrene, fluorenyl styrene or methoxy styrene; or a vinyl compound such as a cyclic alkyl (indenyl) acrylate of C6-C12. Preferably, dicyclopentanylmethacrylate, styrene, iso-octylacrylate, allylmethacrylate, thiol-propyl Methacrylonitrile, 2,2-dimethyl-l, 3-propylene glycoldiacrylate. These ethylenically unsaturated monomers copolymerized with (a-1) may be used singly or in combination of several kinds. The content of the (a-2) ethylenically unsaturated monomer copolymerizable with (a-Ι) is 1 〇 based on the total of (a-1), (a-2) and (a-3) being 100 parts by weight. 9 parts by weight. As described above, the photosensitive resin composition of the present invention can be selectively added with styrene' to further improve the heat resistance and chemical resistance of the resin composition. 17 200914896 jl/^w / ^.-r-»85twf.doc/n (a-3) Epoxy-containing ethylenically unsaturated monomer, for example, glycidyl (meth) Acrylate, (glycidyl (ethyl) a Crylate), 3,4-(indenyl)acrylic acid epoxy (3,4-eP〇Xybutyl (methacrylate), 6,7- 6,7-epoxyheptyl (meth)acrylate, 6,7-epoxyheptyl (ethyl)acrylate, o-vinyl stupid O-vinylbenzylglycidylether, m-vinylbenzylgly Cidylether, p-vinylbenzylglyddetherether. These epoxy-containing ethylenically unsaturated monomers The body may be used singly or in combination of several. The sum of (a-1), (a-2) and (a_3) is 100 parts by weight 'the (a_3) epoxy group-containing ethylenic unsaturated content is 10~ 90 parts by weight - In an embodiment of the photosensitive resin composition of the present invention, a adhesion agent may be further added to enhance the attachment of the photosensitive resin composition. The amount of the adhesion aid may be, for example, 0.01 to 30 parts by weight, preferably 0.5 to 3 parts by weight, based on the photosensitive resin composition. The adhesion aid is, for example, an epoxy resin. Or an amino group-containing hydrazine compound, which is, for example, cold-(3,4-epoxycyclohexane)ethyltrimethoxy hydrazone-(3,4-6卩〇父>^>^1〇 116 father; 71) 6 also; 71 imitation 11^11〇乂>^1&1^), cold-(3,4-epoxycyclohexane)ethyldiethoxylate (p_(3, Ep-glycidoxypropyl methyldimethoxysilane Gamma-glycidoxypropyl methyldiethoxysilane, γ-epoxypropyl 18 200914896 .......J85twf.doc/n γ-glycidoxypropyl dimethoxy(γ-glycidoxypropyl dimethoxy( Ethoxy) silane, γ-glycidoxypropyl dimethyl (methoxy) silane, γ-glycidyl dimethyl dimethyl kiln kiln (丫-邑1}^< ;1€«;^1*〇| 71(1^1161:11)4(^111〇乂丫知1〇1^), 3,4-epoxybutyltrimethoxysilane, 3,4-ring Oxybutyl butyl triethoxysilane (3,4-epoxybutyltriethoxysilane), N-(2-aminoethyl)-3-aminopropyldimethoxy fluorenyl ruthenium ( (N-(2-aminoethyl) )-3-aminopropyldimethoxymethylsilane ) > (3-aminopropyl) trimethoxysilane, (3-aminopropyl) triethoxysilane , (N,N-diethyl-3-aminopropyl)trimethoxysilane, Ν-β(aminoethyl)γ-aminopropyl (Np (aminoethyl) Y-aminopropyl trimethoxysilane), etc., the above-mentioned adhesion aids may be used singly or in combination of two or more kinds. In another embodiment, the photosensitive resin composition of the present invention may be further added to a surfactant. The surfactant is used in an amount of from 0.01 to 30 parts by weight, preferably from 0.5 to 3 parts by weight, based on the mass of the photosensitive resin composition. The surfactant, for example, polyoxyethylene alkyl ethers (for example: polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether) Polyoxyethylene oleyl ether), polyoxyethylene aryl ethers (eg polyoxyethylene octyl phenyl ether, nonylphenol ethoxylate 19 200914896 l^^wj / j85twfldoc /n (polyoxyethylene nonyl phenyl ether), etc., polyethylene glycol dialkyl esters (for example: polyethylene glycol dilaurate (polyethylene glycol dilaurate), polyethylene ethylene Polyethylene glycol distearate or the like, an organosiloxane polymer (for example, KP341 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.); (meth)propionic acid polymerization (metii)acrylic acid polymer, for example: Polyflow No. 75, 90, 95 (manufactured by Kyoei-ShaYushi Kagaku Kogyo Co., Ltd.), Megafac F171, F172, F173 , F475 (manufactured by Dainippon Chemicals ana Ink Co., Ltd.), Florard FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), Asahi Gard G710, Serflon S382, SC-101, SC-102, SC-103 , Sc-104, SC-105, SC-1068 (manufactured by Asahi Glass Co., Ltd.), etc.) The above-mentioned surfactants may be used singly or in combination of two or more kinds. In other embodiments, the photosensitive resin composition of the present invention may further be further added with an antimony additive such as a defoamer, a leveling agent, or a thermal polymerization inhibitor. Lymerizaticm shirt - agent) and so on. Hereinafter, a method for producing the photosensitive resin composition of the present invention and (A) a photoreactive type soluble resin binder will be described. [(A) Method for preparing photoreactive type soluble resin binder] (A) Reactive type alkali-soluble resin binder is, for example, (a_丨) acid group-containing ethylenically unsaturated monomer and (a_2) It can be copolymerized with (a-1), and the unsaturated chain is reacted with a soft chain, and then the (iv) epoxy group-containing ethylenically unsaturated monomer is grafted through the brewing reaction pot. form. /, in the "making (A) photoreactive type of soluble resin binder, 20
V V200914896 “……似 ^J85twf.doc/n 所用的溶劑可例如是使用與(F)有機溶劑相同或不同之溶 劑，其例如是苯(benzene)、曱苯(toluene)、二曱苯(xylene)、 甲醇(methanol)、乙醇(ethanol)、乙醇單丙 i|(ethylene glycol monopropyl ether)、二乙二醇二甲醚(diethylene glycol dimethyl ether)、二乙二醇甲醚(diethylene glycol methyl ether)、曱氧基 丙酸甲酯methyl methoxypropionate)、乙氧基丙酸乙酯(ethyl ethoxypropionate (EEP))、乳酸乙酯(ethyllactate)、四氫吱喃 (tetrahydroforan (THF))、乙醇單曱趟（ethylene glycol monomethyl ether)、乙醇單乙謎（ethylene glycol monoethyl ether)、曱基溶纖劑乙酸酯(methyl cellosolve acetate)、乙基溶 纖劑乙酸酯(ethyl cellosolve acetate)、二乙醇單曱醚(diethylene glycol monomethyl ether)、二乙醇單乙醚(diethylene glycol monoethyl ether)、二乙醇單丁鱗(diethylene glycol monobutyl ether)、丙二醇曱醚醋酸酯(propylene glycol methyl ether acetate (PGMEA))、丙二醇乙醚醋酸醋(propylene glycol ethyl ether acetate)、丙二醇丙醚醋酸 g旨(propylene glycol propyl ether acetate)、曱基異丁嗣(methyl isobutyl ketone)、甲 _酮(methyl ether ketone)、丙酮(acetone)、環己酮(cyclohexanone)、二曱基 曱酸胺（dimethylformamide (DMF))、N,N-二甲基乙醯胺 (Ν,Ν-dimethylacetamide (DMAc)) 、N-甲基 n比洛酮 (N-methyl-2-pyrrolidone (NMP))、r -butylolactone 等，這些 溶劑可單獨或混合數種使用。 另外，在製造(A)光反應型鹼可溶性樹脂膠合劑時， 所用的起始劑可例如是使用一般的聚合起始劑，其例如是 偶氮二異丁腈（AIBN)、偶氮二異庚腈 21 200914896V V200914896 "...the solvent used by ^J85twf.doc/n can be, for example, the same or different solvent as the (F) organic solvent, which is, for example, benzene, toluene, xylene. ), methanol, ethanol, ethylene glycol monopropyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ether , methyl methoxypropionate), ethyl ethoxypropionate (EEP), ethyl lactate, tetrahydroforan (THF), ethanol monoterpene ( Ethylene glycol monomethyl ether), ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethanol monoterpene ether (diethylene glycol monomethyl ether), diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acet Ace (PGMEA)), propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, methyl isobutyl ketone, methyl ether ketone ), acetone (acetone), cyclohexanone, dimethylformamide (DMF), N,N-dimethylacetamide (DMA), N- N-methyl-2-pyrrolidone (NMP), r-butylolactone, etc., these solvents may be used singly or in combination. Further, in the production of the (A) photoreactive type alkali-soluble resin binder, the initiator used may, for example, use a general polymerization initiator such as azobisisobutyronitrile (AIBN) or azobis. Heptonitrile 21 200914896
Uj\v /vjvj. zh j 8 5twf. doc/n (2,2 ’ -azobis-(2,4-dimethylvaleronitrile))、2,2'-偶氮雙(4-甲氧 _2,4- 二 甲基戊 腈)(2,2’-azobis-(4-methoxy-2,4-dimethylvaleronitrile))、偶氮 二異戊腈(2,2’-azobis-2-methyl butyronitrile)等偶氮(azo)化 合物’以及過氧化苯甲酸(benzoylperoxide)等過氧化物。 本發明之感光樹脂組成物的製備方法，是將上述之化 合物(A)〜(F)，於攪拌器或混合器中均勻混合成一混合溶 ^ 液。然後’例如是利用孔徑Ο.ίμηι的微孔過濾器或其他過 渡器，將混合溶液進行過濾即可製成組成物溶液。當然， 可視需要添加密著助劑、界面活性劑、消泡劑、調平劑、熱 聚合抑制劑或其他添加劑。本發明之感光性樹脂組成物，於 25 C下所測得的黏度介於1〜200 cps之間。 本發明之感光性樹脂組成物，適用於彩色濾光片的保 護膜，其可具有更高的光穿透度、附著度、表面平坦性， 且具有更較佳的耐熱性、耐酸鹼性及耐熱變色性，以提高 元件效能。 ° J 一雖然本發明已以較佳實施例揭露如上，然其並非用以 限=本發明，任何熟習此技藝者，在不脫離本發明之精神 =範圍内，當可作些許之更動與潤飾，因此本發明之保護 圍當視後附之申請專利範圍所界定者為準。 【圖式簡單；明】 益 【主要元件符號說明】 無 22Uj\v /vjvj. zh j 8 5twf. doc/n (2,2 '-azobis-(2,4-dimethylvaleronitrile)), 2,2'-azobis(4-methoxy-2,4-di Azo (2,2'-azobis-(4-methoxy-2,4-dimethylvaleronitrile), azobisisovaleronitrile (2,2'-azobis-2-methyl butyronitrile) Compounds and peroxides such as benzoylperoxide. The photosensitive resin composition of the present invention is prepared by uniformly mixing the above compounds (A) to (F) into a mixed solution in a stirrer or a mixer. Then, for example, a composition solution is prepared by filtering a mixed solution using a pore filter of a pore size of Ο.ίμηι or another separator. Of course, adhesion aids, surfactants, defoamers, leveling agents, thermal polymerization inhibitors or other additives may be added as needed. The photosensitive resin composition of the present invention has a viscosity measured at 25 C of between 1 and 200 cps. The photosensitive resin composition of the present invention is suitable for a protective film of a color filter, which can have higher light transmittance, adhesion, surface flatness, and has better heat resistance and acid and alkali resistance. And heat-resistant discoloration to improve component performance. Although the present invention has been disclosed in the above preferred embodiments, it is not intended to limit the invention, and those skilled in the art can make some modifications and refinements without departing from the spirit of the invention. Therefore, the protection of the present invention is defined by the scope of the patent application. [Simple diagram; Ming] Benefits [Main component symbol description] None 22