200914956 DX070301 24384twf.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 關於一種顯示面板的間隔物用感光性樹脂組成物。 【先前技術】 由於，在液晶顯示面板之大型基板的製程中，並無法 ) 製備與基板尺寸相同的光罩(mask)，因此難以應用一次性 曝光的方式來進行曝光。於是’業界提出了 一種非一次性 曝光方式’即分步曝光的方式’以解決此問題。但是，採 用一次性曝光方式時，感光性可交聯樹脂組成物對感光靈 敏度的要求不高，其僅要能允許約300 mJ/cm2的曝光量即 可。採用分步曝光方式時，感光性可交聯樹脂組成物則必 須要在120 mJ/cm2以下的曝光量下，仍足以形成所需的間 隔板的形狀和膜厚。 在一些專利文獻中，例如US 6,582,862、[Technical Field] The present invention relates to a photosensitive resin composition, and more particularly to a photosensitive resin composition for a spacer of a display panel. [Prior Art] Since a mask having the same size as a substrate cannot be prepared in the process of a large substrate of a liquid crystal display panel, it is difficult to perform exposure by applying one-time exposure. Thus, the industry has proposed a non-disposable exposure method, that is, a step-by-step exposure method to solve this problem. However, in the case of the one-time exposure method, the photosensitive crosslinkable resin composition is not required to have a photosensitive sensitivity, and it is only required to allow an exposure amount of about 300 mJ/cm2. In the case of the stepwise exposure method, the photosensitive crosslinkable resin composition must be sufficient to form the desired shape and film thickness of the spacer at an exposure of 120 mJ/cm2 or less. In some patent documents, such as US 6,582,862,
2006/0229376、JP 2001/261761、JP 2003/173025、JP 2005/234362'JP 2006/030809'CN 1,655,060-CN 1,765,948 等專利’皆提出了有關感光性可交聯樹脂組成物的相關技 術，然這些專利文獻仍存在有一些問題。 因此，如何發展出適合目前製程所需之顯示面板的間 隔物用感光性樹脂組成物’已成為業界一致努力的目標之 5 Ο2006/0229376, JP 2001/261761, JP 2003/173025, JP 2005/234362 'JP 2006/030809'CN 1,655,060-CN 1,765,948, etc., all of which are related to the photosensitive crosslinkable resin composition, and these There are still some problems in the patent literature. Therefore, how to develop a photosensitive resin composition for a spacer suitable for a display panel required for the current process has become a goal of the industry's concerted efforts.
200914956 DX070301 24384twf.doc/n 【發明内容】 本發明的目的就是在提供—_示面板的間隔物用 感光性樹脂組成物，能夠避免習知的問題發生，且 光I的條件下，此感光性樹脂組成物亦可形成所的門 隔物之形狀與膜厚。 而〆 曰 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)歧應魏可溶性樹脂膠合劑、 (Β)光聚合型含乙烯性不飽和基的化合物、（c)光起始劑、 ⑼有機麟、⑹分子巾至少含有2個環氧絲化合物， 以及(F)錢溶劑。其巾’⑷紐應型鹼可紐樹脂膠合 劑，包括(a-Ι)含酸基的乙烯性不飽和單體、（a 2)可與 共聚合的乙雜不飽和單體，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，適用於顯示面板的間隔 物，且為剛性之感光性樹脂組成物，且在曝光量小於等於 120 mJ/cm2時，也可以得到所需求的間隔板之形狀與膜厚。 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 明如下。 【實施方式】 本發明提出一種顯示面板的間隔物用感光性樹脂組 成物’其在曝光量小於等於12〇mJ/cm2時，也可以得到所 需求的間隔板之形狀與膜厚。 200914956 υχυ/υ3υι ^84twf.d〇c/n 本發明之顯示面板的間隔物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(f)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 如是乙二醇二甲基丙烯酸酯（ethylene glyc〇1 di(meth)acrylate)、具有 2-14 個環氧乙烷基(ethyieneoxide group)的聚乙二醇二曱基丙烯酸酯（p〇iyethyiene giycol di(meth)acrylate)、三曱醇丙烷二曱基丙烯酸酯(trimethyl〇1 propane di(meth)acrylate)、三甲醇丙烷三曱基丙烯酸酯 (trimethylol propane tri(meth)acrylate)、異戍四醇三曱基丙 炼酸酯(pentaerythritol tri(meth)acrylate)、異戊四醇四曱基 丙烯酸酯(卩611^615^111^1：〇116打&(11161；11)&〇71&{6)、具有2-14個 環氧丙烧基(propyleneoxide group)的丙嫦甘醇二曱基丙烯 酸酉旨(propyleneglycol di(meth)acrylate)、二季戊四醇五曱基 丙稀酸醋（dipentaerythritol penta(meth)acrylate)、二季戊四 醇六甲基丙烤酸醋（dipentaerythritol hexa(meth)acrylate ’ DPHA)、三經曱基丙烧三縮水甘油醚丙烯酸添力口劑 (trimethylolpropanetriglycidylether acrylic acid additives) ' 雙驗A二縮水甘油醚丙烯酸添加劑（bisphenol A diglycidylether acrylic acid additives)、鄰苯二曱酸二西旨類的 200914956 DAUVU^ui Z4384twf.doc/n (曱基）丙烯酸- /5-經乙酯（phthalate diesters of石 -hydroxyethyl(meth)acrylate)、曱苯二異氫酸酉旨添加劑的（曱 基）丙烯酸-冷-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)，其中乙烯性不飽和鍵是選自由二三羥基曱基 丙烧四丙烯酸醋（ditrimethylol propanetetraacrylate)、乙氧 基化三聚異氳酸三丙烯酸酯 (tris(2-acryloxyethyl)isocyanurate)、含乙氧基季戊五醇四丙 烯酸 S旨（ethoxylated pentaerylthritoltetraacrylate) (EO 4 mol)、季戊五醇四丙稀酸醋（pentaerythritoltetraacrylate) (EO 35 mol)、含乙氧基三羥曱基丙烷三丙烯酸酯 (ethoxylated trimethylolpropanetriacrylate) (EO 9 mol)、含乙 氧基三經曱基丙烧三丙烯酸S旨（EO 3 mol)、含丙氧基三經 曱基丙烧三丙稀酸醋(propxylated pentaerythritoltetraacrylate) (PO 4 mol)、九乙二醇二丙烯酸 酉旨(nonaethylene glycol diacrylate)、以己内酯改質的雙季戊 四醇六丙稀酸酯（dipentaerythritolhexaacrylate-modified caprolactone)、三羥曱基丙烷丙氧基三丙烯酸酯 (trimethylolpropanepropoxylate triacrylate)所組成之群組。 上述之光聚合型含乙稀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。 200914956 i;au/ujk;j /4j>84twf.doc/n (C)光起始劑’例如為氧化膦(ph〇Sphine 〇xide)系化合 物、羰基(carbonyl)系化合物、胺羰(amin〇carb〇nyl)系化合 物、二嗓(triazine)糸化合物、將(oxime)系化合物、胺(amine) 糸化合物、烧氧基耕蒽（alkoxyantharcene)系化合物與β塞〇镇 (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 ❹ （bisacylphosphine oxide)、2,4,6-三曱基苯曱酿基-二笨基氧膦 (2,4,6-trimethylbenzoyldiphenylphosphine oxide (TPO))、2,6-二 乙基苯曱醯基-二苯基氧膦 (2,6-diethylbenzoyldiphenylphosphine oxide)、2,6-二曱基苯曱醯 基-二苯基氧膦（2,6-dimethoxybenzoyldiphenylphosphine oxide) 、2,6-二氯苯甲醯基-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)、苯曱酿二 〇 (2,6- 二曱 苯基） 膦酸 0^似〇丫1出(2,6-出11161;11>^)11^11>4)卩]1〇5卩]1〇1^6)、2,4,6-三甲基苯甲 醯基 苯基膦 酸乙酯 (2,4,6-trimethylbenzoylethoxyphenylphosphine oxide)、雙(2,4,6- 三曱基苯曱 醯基）苯基氧化 膦)(恤(2,4,641±〇^11^心1^〇>4)卩1^11}^]1(^1^1^(1-819))、雙(2,6-曱氧苯曱醯基）-2,4,4-三曱基苯基氧膦 (bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine 200914956 DX070301 24384twf.doc/n oxide))。獄基(carbonyl)系化合物、胺幾(aminocarbonyl)系化 合物、三唤(triazine)系化合物、將(oxime)系化合物等系列 化合物例如是乙醯苯（acetophenone)、二苯曱酮 (benzophenone)、二苯基 _(biphenylketone)、 1-羥基-1-環己基 苯基甲酮(1 -hydroxy-1 -benzoylcyclohexane (I-18句）、苄基丙酮 2.2- 二曱氧基-1,2-二苯乙炫-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）丙烧 (1 -benzyl-1 -dimethy lamino-1 -(4-morpholino-benzoy l)pr〇pane (1-369)) 、2-嗎淋-2-(4-曱硫基）苯曱酿丙娱J (2-morpholyl-2-(4-methylmercapto)benzoylpropane (1-907))、 ethylantraquinone、4-苯甲酿基-4-甲基二苯硫醚 (4-benzoyl-4-methyldiphenylsulfide)、 苯甲醯苯曱醇丁醚 (benzoinbutylether) 、 2-經基-2-苯曱醯丙烧 (2-hydroxy-2-benzoylpropane)、2-羥基-2-(4-異丙基)苯甲醯丙烷 (2-hydroxy-2-(4-isopropyl)benzoylpropane)、4-丁基苯甲醯三氣 曱烧(4-butylbenzoyltrichloromethane)、4-苯氧基苯曱醢二氣曱 烧（4-phenoxybenzoyldichloromethane)、苯曱酿曱酸曱酉旨 (benzoylmethylformate) 、1，7-雙（9_ 〇丫 唆基）庚院 (l，7-bis(9-acridinyl)heptane)、9-n- 丁基-3,6-雙（2-嗎淋 -isobutyloyl) °卡 〇全 (9-n-butyl-3,6-bis(2-morpholino-isobutyloyl)carbazole)、10-丁基 -2-chloroacrydone(10-butyl-2-chloroacrydone)、2-[2-(4_ 甲氧基- 苯基）-乙細基]-4,6-雙-二氯甲基-[1,3,5]三°秦 200914956 νχΌΐνόυι Mj^4twf.doc/n (2-[2-(4-methoxy-phenyl)-vinyl]-4,6-bis-trichloromethyl-[l,3,5]tr iazine)、2-(4-曱氧基-萘小基)-4,6-雙-三氯曱基-[1,3,5]三嗪 (2-(4-methoxy-naphthalen-l-yl)-4,6-bis-trichloromethyl-[l,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 嗪 (2-benzo[l,3]dioxol-5-yl-4,6-bis-trichloromethyl-[l,3,5]triazine) 、2-甲基-4,6-雙（三氣甲基）-s-三噪 (2-11161;11丫1-4,6-1^(柄〇]11〇1：〇111过11>4)-541^2丨1^)、2-苯基-4,6-雙(三 氯甲基)-s-三嗪(2-phenyl-4,6-bis(trichloromethyl)-s-triazine)、2- 萘酯-4,6-雙（三氯曱基）-s-三嗓 (2-naphthyl-4,6-bis(trichloromethyl)-s-triazine)、1-[9-乙基-6-(2- 曱基苯曱醯基)-9_H-咔唑-3-基]-二環庚基甲烷-1-酮肟-α乙酸 酯、1-[9-乙基-6-(2-曱基苯曱醯基)-9.Η-咔唑-3-基]-二環庚基4_ 酉同將-0-乙酸酉旨、1-[9-乙基-6-(2-甲基苯甲酿基)-9丑-0卡。坐_3-基]_ 金剛烷基曱烷-1 -酮肟-0-苯甲酸酯、1-[9-乙基-6-(2-甲基笨甲酿 基)-9·Η-咔唑-3-基]-金剛烷基甲烷-1-酮肟-0-乙酸酯、1_[9_乙基 〇 -6-(2-甲基苯曱醯基)-9·Η-咔唑-3-基]-四氢呋喃基甲烷小酮蹄 -0-苯曱酸酯、1-[9-乙基-6-(2-曱基苯曱醯基)-9·Η-咔唑基]一 四氢呋喃基曱烷-1-酮肟-〇-乙酸酯、1-[9-乙基-6_(2-曱基笨甲酸 基)-9.Η-咔唑-3-基]-塞吩基曱烷-1-酮肟-0-笨曱酸酯、；乙笑 -6-(2-曱基苯曱酿基)-9.H-叶π坐-3-基]-塞吩基曱炫特乙 酸酯、1-[9-乙基-6-(2-甲基苯甲醯基)-9.Η-咔唑-3-基；μ馬吩基甲 烷-1-酮肟-0-苯甲酸酯、1-[9-乙基-6-(2-甲基苯甲醯基 嗤-3-基]碼吩基曱烧-1-嗣將-0_乙酸S旨、1-[9-乙基-6-(2-甲夷笨 11 200914956 JL/Λυ /υ^υι 34twf. doc/n 甲醯基)-9.H-咔唑-3-基]-乙烷-1-酮肟-〇-二環丁烷酸酯、l_[9_ 乙基-6-(2-甲基笨曱醯基)-9.H-咔唑-3-基]-乙烷-1-酮肟-〇-三環 揆烷酸酯、1-[9-乙基-6-(2-曱基苯曱醯基)-9.H-咔唑-3-基]-乙烷 -1-酮肟-0-金剛烷酸酯、1，2-辛二酮-1-[4-(苯硫基)苯基]-2-(〇-苯曱醯基肟）、1,2-丁二酮-l-[4-(苯硫基)苯基]-2-(0-苯甲醯基 肟）、I,2-丁二終1-[4-(苯硫基)苯基]-2_(〇-乙醯基肟）、L2-辛二 酮曱硫基)苯基]-2-(0-苯f醯基肟）、1，2-辛二酮小[4-(苯 f、 硫基)笨基]-2-(0-甲基苯曱醯基肟）。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曱酸乙酯 (4-dimethylaminomethyl benzoate)、4-二曱基胺基乙基苯曱酸乙 醋(4-dimethylaminoethyl benzoate)、4-二曱基胺基異戊基苯甲 酸乙醋(4-methylaminoisoamyl benzoate)、2-曱基胺基乙基苯甲 酸乙 S旨(2-methylaminoethyl benzoate)、4-二甲基胺基-2-乙基已 基苯曱酸乙酯(4-dimethylamino-2-ethylhexyl benzoate)、Ν,Ν-曱基對曱苯胺0^,1^-11^1;]1>^&瓜1;〇11^(111^)、4,4’-雙(二曱基胺基) Ο 二苯甲酮(4,4’-bis(dimethylamino)benzophenone)、4,4’-雙(二乙 基胺基)二苯曱酮(4,4’-bis(diethylamino)benzophenone)、4,4’-雙 ( 乙基曱 基胺基）二笨曱 嗣 (4,4’-bis(ethylmethylamino)benzophenone)。烧氧基耕蒽系化合 物例如是 9,10-二曱氧基蒽(9,10-dimethoxyanthracene)、9,10-二乙氧基蒽(9，10-diethoxyanthracene)、2-乙基 9,10-二曱氧基 蒽(2-ethy 1-9,10-dimethoxyanthracene)、2-乙基 9,10,二乙氧基慧 (2-ethyl-9,10-diethoxyanthracene) 13 嗟 °镇系化合物例如是 2-異 12 200914956 jl>au/ujui z^84twf.doc/n 丙基隹"頓酮（2-isopropylthioxanthone)、4_異丙基π塞嘲酮 (4-isopropylthioxanthone (IPTX))、2,4-二乙基噻噸酮 (2,4-diethylthioxanthone (DETX))、2,4-三氯基噻嘲嗣 (2,4-trichlorothioxanthone) 、1-氣-4_ 丙基噻噸酮 (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（umoo重量份。 (D) 有機酸酐，例如為順丁烯二酸酐加也比 anhydride，ΜΑ)、伊康酸酐(itaconic anhydride)、四氫g太酐 (tetrahydrophthalic anhydride)、擰康酸酐（citrac〇nic anhydride)或中康酸酐(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100重量份，（P)有機酸酐之含量為〇工 〜100重量份。 (E) 分子中至少含有2個環氧基的化合物，例如是雙酚 A環氧樹脂(bisphenol A type ep0Xy)化合物、雙酚s環氧樹脂 (bisphenol S type epoxy)化合物、芴_9_雙酚二環氧甘油醚 (Fluorene-9-bisphenol diglycidyl Ether (FBDE))、雙酚 A 型環氧 樹脂(bisphenol A type epoxy resin，例如：油化 shell Epoxy 公 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)與環氧氯丙烧 (epichlorohydrin)反應而得之環氧樹脂(例如：日本化藥公司 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 Shell 13 200914956 υΛυ /ujui η j 84twf.doc/nSUMMARY OF THE INVENTION The object of the present invention is to provide a photosensitive resin composition for a spacer of a panel, which can avoid the occurrence of conventional problems, and the photosensitivity under the condition of light I The resin composition can also form the shape and film thickness of the door spacer. According to the present invention, there is provided a photosensitive resin composition for a high elastic spacer of a display panel, which comprises: (Α) a Wei-soluble resin binder, and a (photo) polymerizable ethylenically unsaturated group-containing compound. And (c) a photoinitiator, (9) an organic lining, (6) a molecular towel containing at least two epoxy resin compounds, and (F) a money solvent. Its towel '(4) New type alkali-based resin adhesive, including (a-Ι) acid-containing ethylenically unsaturated monomer, (a 2) copolymerizable ethylenically unsaturated monomer, and (a_3) An epoxy group-containing ethylenically unsaturated monomer. The photosensitive resin composition of the present invention is suitable for a spacer of a display panel and is a rigid photosensitive resin composition, and when the exposure amount is 120 mJ/cm 2 or less, the desired shape of the spacer can be obtained. Film thickness. The above and other objects, features and advantages of the present invention will become more <RTIgt; [Embodiment] The present invention provides a photosensitive resin composition for a spacer of a display panel. When the exposure amount is 12 〇mJ/cm 2 or less, the shape and film thickness of the desired spacer can be obtained. 200914956 υχυ/υ3υι ^84twf.d〇c/n The photosensitive resin composition for the spacer of the display panel of the present invention comprises: (A) a photoreactive alkali-soluble resin binder, and (B) a photopolymerizable type. a compound having an ethylenically unsaturated group, (C) a photoinitiator, (D) an organic acid anhydride, a compound having at least two epoxy groups in (E) a molecule, and (f) an organic solvent. The (B) photopolymerizable ethylenically unsaturated group-containing compound of the resin composition of the present invention is an ethylenically unsaturated compound having at least one ethylenically unsaturated group. (B) a photopolymerizable ethylenically unsaturated group-containing compound, for example, ethylene glyc〇1 di(meth)acrylate, having 2-14 ethylene oxide groups (ethyieneoxide group) Polyethylene glycol dimercaptoacrylate (p〇iyethyiene giycol di(meth)acrylate), trimethyl〇1 propane di(meth)acrylate, trimethylolpropane tridecyl Trimethylol propane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetradecyl acrylate (卩611^615^111^1) : 〇 116 打 &(11161; 11) & 〇 71 & {6), propylene glycol dimercapto acrylate with 2-14 propylene oxide groups (propyleneglycol di (meth) Acetate), dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate 'DPHA), triterpenoid propyl propylene triacetate Glycerol ether acrylic acid (trimethylolpropanetriglycidylether acrylic) Acid alternatives 'bisphenol A diglycidylether acrylic acid additives', 200914956 DAUVU^ui Z4384twf.doc/n (fluorenyl) acrylic acid - /5- Toluene diisocyanate (toluene diisocyanate) of cold-hydroxyethyl (meth)acrylate by phthalate diesters of stone-hydroxyethyl (meth) acrylate, toluene diisocyanate And a polymeric compound having an ethylenically unsaturated bond, wherein the ethylenically unsaturated bond is selected from the group consisting of ditrimethylol propanetetraacrylate, ethoxylated Tris(2-acryloxyethyl)isocyanurate, ethoxylated pentaerylthritoltetraacrylate (EO 4 mol), pentaerythritol tetraacetic acid vinegar (ethoxylated pentaerylthritoltetraacrylate) Pentaerythritoltetraacrylate) (EO 35 mol), ethoxylated trimethylolpropanetriacrylate (EO 9 mol), ethoxylated trisyl mercaptopropane triacrylate S (EO 3 mol), propoxylated triphenyl thioacetate (PO 4 mol), nine Nonaethylene glycol diacrylate, dipentaerythritol hexaacrylate-modified caprolactone, trimethylolpropane propoxylate triacrylate The group that makes up. The above photopolymerizable ethylenically unsaturated group-containing compound may be used singly or in combination of several kinds. Further, the content of the (A) photoreactive alkali-soluble resin binder is 100 parts by weight of the (B) photopolymerizable ethylenically unsaturated group-containing compound in an amount of from 1 to 250 parts by weight. 200914956 i;au/ujk;j /4j>84twf.doc/n (C) Photoinitiator 'for example, phosphine oxide (ph〇Sphine 〇xide) compound, carbonyl compound, amine carbonyl (amin〇 Carb〇nyl) compound, triazine ruthenium compound, oxime compound, amine ruthenium compound, alkoxyantharcene compound and β thioxanthone compound One of the combined ethnic groups. Wherein, the phosphine oxide compound is, for example, an arylphosphine oxide, aCylph〇sphine oxide, bisacylphosphine oxide, 2,4,6-trimercaptobenzoquinone 2,6-6-trimethylbenzoyldiphenylphosphine oxide (TPO), 2,6-diethylbenzoyldiphenylphosphine oxide, 2, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2 ,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, 2,6-diphenylphenylphosphonic acid 0^like 〇丫1 out (2,6-out 11161;11>^)11^11>4)卩]1〇5卩]1〇1^6), 2,4,6-trimethylbenzene 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, bis(2,4,6-trimercaptophenyl)phenylphosphine oxide) (2,4,641±〇^11 ^心1^〇>4)卩1^11}^]1(^1^1^(1-819)), double (2,6-曱 oxygen Benzoyl)-2,4,4-trimethoxybenzophosphine-2,4,4-trimethylpentylphosphine 200914956 DX070301 24384twf.doc/n oxide)). A series of compounds such as a carbonyl compound, an aminocarbonyl compound, a triazine compound, and an oxime compound are, for example, acetophenone or benzophenone. Biphenylketone, 1-hydroxy-1-cyclohexyl phenyl ketone (1 -hydroxy-1 -benzoylcyclohexane (I-18 sentence), benzyl acetone 2.2-dimethoxy-1,2-di Benzyldimethylketal 2.2- dimethoxy-l, 2-diphenylethane-l-one (1-651), 1-benzyl-1-didecyl tertiary amine-1-(4-Merlin- 1-benzyl-1 -dimethy lamino-1 -(4-morpholino-benzoy l)pr〇pane (1-369)), 2-oxalin-2-(4-sulfonylthio) Benzoquinone-2-(4-methylmercapto)benzoylpropane (1-907), ethylantraquinone, 4-benzylidene-4-methyldiphenyl sulfide (4-benzoyl-4- Methyldiphenylsulfide), benzoinbutylether, 2-hydroxy-2-benzoylpropane, 2-hydroxy-2-(4-isopropyl) 2-hydroxy-2-(4-isopropyl)benzoylpropane, 4-butylbenzhydrazide 4-butylbenzoyltrichloromethane, 4-phenoxybenzoyldichloromethane, benzoylmethylformate, 1,7-bis(9-fluorenyl)g (1,7-bis(9-acridinyl)heptane), 9-n-butyl-3,6-bis(2-morphine-isobutyloyl) ° cardinal (9-n-butyl-3,6- Bis(2-morpholino-isobutyloyl)carbazole), 10-butyl-2-chloroacrydone (10-butyl-2-chloroacrydone), 2-[2-(4-methoxy-phenyl)-ethyl]-4 ,6-bis-dichloromethyl-[1,3,5]三°秦200914956 νχΌΐνόυι Mj^4twf.doc/n (2-[2-(4-methoxy-phenyl)-vinyl]-4,6- Bis-trichloromethyl-[l,3,5]tr iazine), 2-(4-decyloxy-naphthalene)-4,6-bis-trichloroindolyl-[1,3,5]triazine 2-(4-methoxy-naphthalen-l-yl)-4,6-bis-trichloromethyl-[l,3,5]tri azine), 2-indolyl[1,3]dioxole-5 -yl-4,6-bis-trichloroindolyl-[1,3,5]triazine (2-benzo[l,3]dioxol-5-yl-4,6-bis-trichloromethyl-[l,3 ,5]triazine), 2-methyl-4,6-bis(trimethyl)-s-three noise (2-11161; 11丫1-4,6-1^(handle)11〇1: 〇111过11>4)-541^2丨1^), 2- 4-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-naphthyl ester-4,6-bis(trichloro) 2-naphthyl-4,6-bis(trichloromethyl)-s-triazine, 1-[9-ethyl-6-(2-mercaptophenyl)--9-H- Oxazol-3-yl]-bicycloheptylmethane-1-one oxime-α acetate, 1-[9-ethyl-6-(2-mercaptophenylhydrazino)-9.Η-咔Zyridin-3-yl]-bicycloheptyl 4_ oxime is a combination of -0-acetic acid, 1-[9-ethyl-6-(2-methylbenzoyl)-9 ugly-0 card. Sit 3-3-yl]_adamantyl decane-1 -ketooxime-0-benzoate, 1-[9-ethyl-6-(2-methylbenzamide)-9·Η- Oxazol-3-yl]-adamantyl methane-1-one oxime-0-acetate, 1-[9-ethyl hydrazine-6-(2-methylphenylhydrazino)-9·Η-咔Zyrid-3-yl]-tetrahydrofuranyl methane ketone hoof 0-phenyl phthalate, 1-[9-ethyl-6-(2-mercaptophenyl)-9-indole-carbazolyl] Tetrahydrofuranyl decane-1-one oxime-indole-acetate, 1-[9-ethyl-6-(2-mercaptobenzoic acid)-9.indole-indazole-3-yl]-cetin曱 -1- 肟 肟 肟 肟 - - - - - ; ; ; ; ; ; ; ; ; ; ; - - - - - - - - - - - - - - - - - - - Hyun acetate, 1-[9-ethyl-6-(2-methylbenzhydryl)-9.indole-carbazol-3-yl; μ-hortyl-methane-1-one oxime-0 -benzoate, 1-[9-ethyl-6-(2-methylbenzylidinyl-3-yl)-phenanthryl-pyrene-1-yl---acetic acid-S, 1- [9-ethyl-6-(2-甲夷笨11 200914956 JL/Λυ /υ^υι 34twf. doc/n carbaryl)-9.H-carbazol-3-yl]-ethane-1- Ketooxime-indole-bicyclobutanoate, l_[9_ethyl-6-(2-methylcumenyl)-9.H-carbazol-3-yl]-ethane-1-one oxime -〇-tricyclic decanoate, 1-[9-ethyl-6-( 2-mercaptobenzoyl)-9.H-carbazol-3-yl]-ethane-1-one oxime-0-adamantanate, 1,2-octanedione-1-[4- (phenylthio)phenyl]-2-(anthracene-phenylhydrazinium), 1,2-butanedione-l-[4-(phenylthio)phenyl]-2-(0-benzene醯基肟), I, 2-butadiene 1-[4-(phenylthio)phenyl]-2_(anthracene-ethenyl), L2-octanedione sulfonyl)phenyl]-2 -(0-Benzenefluorenyl), 1,2-octanedione [4-(phenylf, thio)phenyl]-2-(0-methylphenylhydrazinyl). The amine compound is, for example, triethanolamine, methyldiethanolamine, triisopropylamine, 4-dimethylaminomethyl benzoate, 4 -4-dimethylaminoethyl benzoate, 4-methylaminoisoamyl benzoate, 2-mercaptoaminoethyl benzene 2-methylaminoethyl benzoate, 4-dimethylamino-2-ethylhexyl benzoate, hydrazine, hydrazino-p-anilide 0^,1^-11^1;]1>^& melon 1; 〇11^(111^), 4,4'-bis(didecylamino) benzophenone (4,4' -bis(dimethylamino)benzophenone), 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethyldecylamine) Base) 4,4'-bis(ethylmethylamino)benzophenone. The oxyalkylene compound is, for example, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl 9,10 2-ethy 1-9,10-dimethoxyanthracene, 2-ethyl 9,10,diethoxyanthracene 13 嗟° 镇 compounds Is 2-iso 12 200914956 jl>au/ujui z^84twf.doc/n propyl quot " 2-isopropylthioxanthone, 4-isopropylthioxanthone (IPTX), 2 , 2,4-diethylthioxanthone (DETX), 2,4-trichlorothioxanthone, 1-gas-4-propylthioxanthone (1 -chloro-4-propoxythioxanthone). The above photoinitiators can be used singly or in combination of several kinds. Further, the content of the (A) photoreactive alkali-soluble resin binder based on 100 parts by weight of '(C) photoinitiator is (umoo parts by weight. (D) Organic acid anhydride, for example, maleic anhydride plus Anhydride, itaconic anhydride, tetrahydrophthalic anhydride, citrac〇nic anhydride or mesaconic anhydride. The above organic acid anhydrides may be used singly or in combination of several kinds. Further, the content of the (P) organic acid anhydride is from 100 to 100 parts by weight based on 100 parts by weight of the (A) photoreactive type testable soluble resin binder. (E) a compound having at least two epoxy groups in the molecule, for example, a bisphenol A type ep0Xy compound, a bisphenol S type epoxy compound, and a 芴_9_ double Fluorene-9-bisphenol diglycidyl Ether (FBDE), bisphenol A type epoxy resin (for example: oily shell Epoxy company, trade name Epikote 828, 1001, 1002 , 1004, etc.), an epoxy resin obtained by reacting an alcoholic hydroxyl group with an epichlorohydrin (for example, manufactured by Nippon Kayaku Co., Ltd., trade name NER) -1302, epoxy equivalent 323, softening point 76. bisphenol F type epoxy resin (for example: oily Shell 13 200914956 υΛυ /ujui η j 84twf.doc/n
Epoxy 公司製，商品名為 Epikote807、4001、4002、4004 等）、 雙盼F型ί哀乳樹脂之If·型輕基(alcoholic hydroxyl)與環氧氣丙 烷(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350 ’軟化點66。〇、二苯 基縮水甘油醚(biphenyl glycidyl ether，例如：油化 Shell Epc^y 公司製，商品名為Epikote YX4000)、（苯)酚醛型環氧樹脂 (phenol novolac type epoxy resin，例如：曰本化藥公司製，商 1 品名為EPPN-201，油化Shell Epoxy公司製，商品名為 EpikotelU、1M、U7S65、l57S7〇，陶氏化學公司製，商品 名為DEN-438)、甲（苯)盼醛型環氧樹脂(cres〇1 n〇v〇iac epoxy resin ’例如：日本化藥公司製，商品名為E〇CN_1〇2S、 1020、104S)、三縮水甘油異氣尿酸醋(triglycidyl is〇cyanm>ate， 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 从’商品名為 EPPN-501、-502、-503)、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Epoxy Co., Ltd., trade name: Epikote 807, 4001, 4002, 4004, etc.), Epoxy resin obtained by reacting an alcoholic hydroxyl with an epichlorohydrin For example, Nippon Chemical Co., Ltd.'s trade name is NER-7406, epoxy equivalent 350' softening point 66. Biphenyl glycidyl ether (for example, oiled Shell Epc^y company, trade name It is Epikote YX4000), phenol novolac type epoxy resin (for example, manufactured by Sakamoto Chemical Co., Ltd., trade name EPPN-201, manufactured by Oiled Shell Epoxy Co., Ltd., trade name EpikotelU, 1M , U7S65, l57S7〇, manufactured by The Dow Chemical Company, trade name DEN-438), and acetaldehyde-type epoxy resin (cres〇1 n〇v〇iac epoxy resin ', for example, manufactured by Nippon Kayaku Co., Ltd. The trade name is E〇CN_1〇2S, 1020, 104S), triglycidyl is〇cyanm>ate, for example, manufactured by Nissan Chemical Co., Ltd. under the trade name TEPIC, and trisphenol decane type epoxy resin. (trisphenol methane type epoxy resin, for example : Nippon Kayaku Co., Ltd. from 'commercial name EPPN-501, -502, -503), fluorene type epoxy resin (for example: 'Shop name ESF_3〇〇 made by Niigata Iron Chemical Co., Ltd.), alicyclic type epoxy resin (Example: Daicel Chemical Industry Co., Ltd., trade name
Cell〇Xide2021P、EHPE)、及環氧化聚丁二烯樹脂(印〇说_ P〇lybutadiene，例如：Daicel化學工業公司製，商品名為Ep〇lead 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，分子中至少含有2個環氧基的化合物之 含量為0.1〜1〇〇重量份。 (F)有機溶劑，例如是苯(benzene)、甲苯(t〇iuene)、二甲 苯(xylene)、甲醇(methanol)、乙醇(ethanol)、乙醇單丙醚 14 200914956 l_yyvu / i 34 twf! doc/Π (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)、曱氧基丙酸曱酯(methyl methoxypropionate)、乙氧基丙 酸乙酉旨(6111>4 61；]10父}^0卩1〇1^6(£丑？)）、乳酸乙3旨(6111)41&以&{6)、 四氫π夫喃(tetrahydrofiiran (THF))、乙醇單甲醚(ethylene glycol monomethyl ether)、乙醇單乙醚(ethylene glycol monoethyl ether)、曱基溶纖劑乙酸醋(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 etiier)、丙二醇甲醚醋酸酯(propylene glycol methyl etiier acetate (PGMEA))、丙二醇乙醚醋酸醋(pr0pyiene glyC〇i ethyl ether acetate)、丙二醇丙醚醋酸 g旨（pr〇pyiene giyC〇i pr〇pyi ether acetate)、曱基異丁酮(methyl isobutyl ketone)、甲醚酮(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)) 、N-曱基《比洛酮 (N-methyl-2-pyrrolidone (NMP))、γ- 丁内 g旨(γ-butyrolactone)。 上述之有機溶劑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100重量份，（F)有機溶劑 之含量為1〜250重量份。 另外，（A)光反應型鹼可溶性樹脂膠合劑還包括：（aq) 含酸基的乙烯性不飽和單體、（a_2)可與共聚合的乙烯 性不飽和單體，以及(a_3)含環氧基的乙烯性不飽和單體。 15 200914956 ^H^>〇4twf.doc/n (A)光反應型驗可溶性樹脂膠合劑的重量平均分子量為 2,000〜500,000，其酸價為 10〜4〇〇mgK〇H/g。 其中，（a-Ι)含酸基的乙烯性不飽和單體，例如是（甲基） 丙烯酸、丁烯酸(crotonicacid)、〇：-氣（甲基）丙烯酸、（乙基） 丙烯酸以及桂皮酸(cinnamic acid)等不飽和一元酸類；馬來 酸、順丁烯二酸酐(maleic anhydride)、反丁烯二酸(fumaric acid)、伊康酸（itaconic acid)、伊康酸酐（itac〇nic 0 anhydride)、檸康酸(citrac〇nic acid)、檸康酸酐(citrac〇nic 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。 (a-2)可與(a-Ι)共聚合的乙烯性飽和單體，例如是曱基 丙烯酸烯丙酯(allyl (metli)acrylate)等含丙烯基(auyi group) ϋ 的乙烯基化合物；乙二醇二甲基丙浠酸酯(ethylene glycol di(meth)acrylate)、二環戊烯二曱基丙烯酸酯 (dicyclopentenyl di(meth)acrylate)、丙二醇二曱基丙稀酸酉旨 (propylene glycol di(meth)acrylate)、2,2-二曱基-1,3-丙二醇 二甲基丙烯酸酉旨（2,2-dimethyl-1,3-propylene glycol di(meth)acrylate)、三乙二醇二曱基丙嫦酸醋（triethylene glycol di(meth)acrylate)、四甘醇二曱基丙稀酸酉旨 (tetraethylene glycol di(meth)acrylate)、三(2-經乙基)異氰酸 16 200914956 j^\j I \j i ^-T-*34twf,doc/n 曱基丙焊酉义酉曰（tri(2-hydroxyethyl)isocyanate di(meth)acrylate)等含有兩個丙烯酸基的乙烯基化合物；（甲 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、甲基苯乙烯、曱氧基苯乙烯等之芳香族乙烯基化合物 等。這些與(a-Ι)共聚合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1〇〇重量份， 、 （a-2)可與(a-Ι)共聚合的乙烯性不飽和單體之含量為1〇〜 90重量份。 (a-3)含環氧基的乙稀性不飽和單體，例如是（曱基)丙 烯酸縮水甘油自旨(glycidyl (meth)acrylate)、（乙基)丙稀酸縮 水甘油酯(glycidyl (ethyl)acrylate)、3,4-(甲基）丙烯酸環氧丁 酯(3,4-epoxybutyl (meth)acrylate)、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)、鄰乙烯基苯基縮水甘 油醚(0-¥丨1^如!1矽1§汐(^办1以1^]：)、間乙烯基苯基縮水甘油 ’醚(m-vinylbenzylglyddylether)、對乙烯基苯基縮水甘油醚 (p-vinylbenzylglycidylether)。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_l)、（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和單體 之含置為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1〇〇重量份，密著 17 200914956 uys.KJ 84twf.doc/n 助劑使用量可例如為0.01〜30重量份，較佳為0.5〜3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-環氧環己烧）乙基三曱氧基石夕炫 (戸-(3,4-6卩〇父7〇;/(：1〇1^父71)61;11>41:011161;11〇乂75似1^)、/3-(3,4-環氧環 己烧）乙基三乙氧基石夕烧（β-(3,4-epoxy cyclohexyl)ethyl triethoxysilane)、γ-環氧丙烧三曱氧基石夕烧(γ-glycidoxypropyl trimethoxysUane(GMS))、γ-環氧丙烷曱基二曱氧基矽烷 (γ-glycidoxypropyl methyldimethoxysilane)、γ-環氧丙烧甲基二 乙氧基發院(γ-glycidoxypropyl methyldiethoxysilane) 、γ-環氧丙 烧二曱氧基乙氧基石夕燒（γ-glycidoxypropyl dimethoxy(ethoxy)silane)、γ-環氧丙烷二曱基甲氧基矽烷 (γ-glycidoxypropyl dimethyl(methoxy)silane)、γ-環氧丙烧二曱 基乙氧基石夕烧(γ-glycidoxypropyl dimethyl(ethoxy)silane)、3,4- 環氧丁基三曱氧基石夕烧(3,4-6卩〇义}^1^111111161;11〇乂)^如1^)、3,4-環氧丁基二乙氧基石夕烧(3,4-6卩〇乂}^3111^1沾6111〇乂5^1&1^)、乂(2-胺乙基）-3-胺丙基二曱氧基二曱基矽烷 (N-(2-aminoethyl)-3-aminopropyldimethoxymethylsilane ) ' (3-胺丙基)二甲氧基石夕烧((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）三曱氧基石夕炫 ((N，N-diethyl-3-aminopropyl)trimethoxysilane)、Ν-β(胺乙基)γ-胺丙基三甲氧基石夕院）(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。 18 200914956 j^a.u/ujui ‘"+_> 34twf.doc/n 在另一實施例中，本發明的感光性樹脂組成物亦可進— 步加入界面活性劑(surfactant)。基於感光性樹脂組成物為i〇〇 重量份，界面活性劑的使用量為〇.〇1〜30重量份，較佳為〇 5 〜3重量份。界面活性劑，例如是聚氧乙婦烧鍵 (polyoxyethylene alkyl ethers)(例如：聚氧乙烯月桂謎 (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)、壬基酚聚氧乙稀醚 (polyoxyethylene nonyl phenyl ether)等）、聚乙烯乙二醇二烧基 酯(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）、有機矽氧烷聚合物 (organosiloxane polymer)(例如：KP341(由 Shin-Etsu Chemical Industry Co.，Ltd.製造）；（曱基)丙烯酸聚合物((meth)acrylic acid O polymer) ’ 例如：Polyflow No. 75、90、95(由 Kyoei-ShaYushi Kagaku Kogyo Co., Ltd.製造）、Megafac F17卜 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-10卜 SC-102、SC-103、Sc-104、SC-1 〇5、 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 19 200914956 步加入其它添加劑，其例如是消泡劑(def〇rmer)、調平劑 (leveling agent)' (thermal polymerization inhibitor agent)等。 以下，說明本發明之感光性樹脂組成物及(A)光反應型 鹼可溶性樹脂膠合劑的製備方法。 [(A)光反應型鹼可溶性樹脂膠合劑的製備方法] (A)光反應型驗可洛性樹脂膠合劑例如是，由(a_ 1)含酸 q 基的乙烯性不飽和單體與(a-2)可與〇1)共聚合的乙烯性不 飽和單體進行共聚合反應，之後經酯化反應，將(a_3)含環 氧基的乙烯性不飽和單體接枝而形成。 其中，在製造(A)光反應型鹼可溶性樹脂膠合劑時， 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)、乙醇單丙鍵(et；hylene glycol monopropyl ether)、二乙二醇二甲醚(diethylene glycol dimethyl ether)、二乙二醇曱謎(diethylene glycol methyl ether)、甲氧基 〇 丙酸曱酯methyl methoxypropionate)、乙氧基丙酸乙酯(ethyl ethoxypropionate (EEP；))、乳酸乙酯(ethyllactate)、四氫呋喃 (tetrahydrofiiran (THF))、乙醇單曱醚（ethylene glycol monomethyl ether)、乙醇單乙醚(ethylene glycol monoethyl ether)、曱基溶纖劑乙酸酯(methyl cellosolve acetate)、乙基溶 纖劑乙酸酉旨(ethyl cellosolve acetate)、二乙醇單曱醚(diethylene glycol monomethyl ether)、二乙醇單乙 _(diethylene glycol monoethyl ether)、二乙醇單丁喊(diethylene glycol monobutyl 20 200914956 _________ _ .. 84twf.doc/n ether)、丙二醇曱 _醋酸g旨(propylene glycol methyl ether acetate (PGMEA))、丙二醇乙醋酸醋(propylene glycol ethyl ether acetate)、丙二醇丙醚醋酸醋（propylene glycol propyl ether acetate)、曱基異丁酮(methyl isobutyl ketone)、甲醚酮(methyl ether ketone)、丙酮(acetone)、環己酮(cyclohexanone)、二曱基 曱酸胺（dimethylformamide (DMF))、N,N-二曱基乙醯胺 (Ν,Ν-dimethylacetamide (DMAc)) 、N-曱基0比咯酮 (N-methyl-2-pyrrolidone (NMP》、γ-丁内醋（τ -butyrolactone)Cell〇Xide 2021P, EHPE), and epoxidized polybutadiene resin (Indigo _P〇lybutadiene, for example, manufactured by Daicel Chemical Industries, Inc., trade name Ep〇lead PB3600). Further, the content of the compound containing at least two epoxy groups in the molecule is 0.1 to 1 part by weight based on 100 parts by weight of the (A) photoreactive alkali-soluble resin binder. (F) an organic solvent such as benzene, toluene, xylene, methanol, ethanol, ethanol monopropyl ether 14 200914956 l_yyvu / i 34 twf! doc/ Glycol (ethylene glycol monopropyl ether), diethylene glycol dimethyl ether, diethylene glycol methyl ether, methyl methoxypropionate, ethoxylate Propionate (6111>4 61;]10 parent}^0卩1〇1^6 (£ ug?)), lactic acid B3 (6111)41&&{6), tetrahydropyrr (tetrahydrofiiran (THF)), ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate Ethyl cellosolve acetate), diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl etiier, propylene glycol methyl etiier Acetate (PGMEA)), propylene glycol B Pr0pyiene glyC〇i ethyl ether acetate, pr〇pyiene giyC〇i pr〇pyi ether acetate, methyl isobutyl ketone, methyl ether ketone ), acetone (acetone), cyclohexanone, dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N- N-methyl-2-pyrrolidone (NMP), γ-butyrolactone. The above organic solvents may be used singly or in combination of several kinds. Further, the content of the (F) organic solvent is from 1 to 250 parts by weight based on 100 parts by weight of the (A) photoreactive type soluble resin binder. Further, the (A) photoreactive alkali-soluble resin binder further comprises: (aq) an ethylenically unsaturated monomer having an acid group, (a_2) a copolymerizable ethylenically unsaturated monomer, and (a-3) Epoxy group of ethylenically unsaturated monomers. 15 200914956 ^H^>〇4twf.doc/n (A) Photoreactive type test The soluble resin binder has a weight average molecular weight of 2,000 to 500,000 and an acid value of 10 to 4 〇〇 mg K 〇 H / g. Wherein (a-Ι) an ethylenically unsaturated monomer having an acid group, such as (meth)acrylic acid, crotonic acid, fluorene:-gas (meth)acrylic acid, (ethyl)acrylic acid, and cassia An unsaturated monobasic acid such as cinnamic acid; maleic acid, maleic anhydride, fumaric acid, itaconic acid, and itaconic acid (itac〇nic) 0 anhydride), citrac〇nic acid, citrac〇nic anhydride, mesaconic acid, mesac〇nic anhydride, etc. Class; unsaturated trivalent or higher polyvalent acid or the like. These acid group-containing ethylenically unsaturated monomers may be used singly or in combination of several kinds. The content of the (a-1) acid group-containing ethylenically unsaturated monomer is 10 to 90 parts by weight based on 100 parts by weight based on the total of (a-1), (a-2) and (a-3). (a-2) an ethylenic saturated monomer copolymerizable with (a-fluorene), for example, a vinyl compound containing an auyi group such as allyl (meth) acrylate; Ethylene glycol di(meth)acrylate, dicyclopentenyl di(meth)acrylate, propylene glycol dimercapto acrylate Di(meth)acrylate), 2,2-dimethyl-1,3-propanediol di(meth)acrylate, triethylene glycol Triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tris(2-ethyl)isocyanate 16 200914956 j^\j I \ji ^-T-*34twf, doc/n Tri(2-hydroxyethyl)isocyanate di(meth)acrylate) ; (meth)acrylonitrile (meth) acrylonitrile, a-chloro (meth) acrylonitrile and other nitrile vinyl compounds; styrene, methyl styrene, hydrazine An aromatic vinyl compound such as oxystyrene or the like. These ethylenically unsaturated monomers copolymerized with (a-fluorene) may be used singly or in combination of several kinds. The content of the ethylenically unsaturated monomer copolymerizable with (a-Ι) is (a-2) based on the sum of (a-1), (a_2) and (a-3) being 1 part by weight. 1〇~ 90 parts by weight. (a-3) Epoxy-containing ethylenically unsaturated monomer, for example, glycidyl (meth)acrylate, (ethyl)glycidyl (glycidyl (glycidyl) Ethyl)acrylate), 3,4-epoxybutyl (meth)acrylate, 6,7-epoxyheptyl (6,7-epoxyheptyl (6,7-epoxyheptyl) Meth)acrylate), 6,7-epoxyheptyl (ethyl)acrylate, o-vinylphenyl glycidyl ether (0-¥丨1^如!1矽1 §汐(1)1):), m-vinylbenzylglyddylether, p-vinylbenzylglycidylether. These epoxy-containing ethylenic groups The unsaturated monomers may be used singly or in combination of several. The total of (a-1), (a_2) and (a-3) is 100 parts by weight ', and the content of (a_3) epoxy group-containing ethylenically unsaturated monomer is set to 10 to 90 parts by weight. In one embodiment, a bonding agent may be further added to the photosensitive resin composition of the present invention to enhance the adhesion of the photosensitive resin composition. The resin composition is 1 part by weight, and the adhesion amount can be, for example, 0.01 to 30 parts by weight, preferably 0.5 to 3 parts by weight, based on the amount of the auxiliary agent. It is an epoxy group-containing or amino group-containing ruthenium compound, which is, for example, cold-(3,4-epoxycyclohexane)ethyltrimethoxyxanthine (炫-(3,4-6卩〇父7〇) ;/(:1〇1^父71)61;11>41:011161;11〇乂75like 1^), /3-(3,4-epoxycyclohexane)ethyltriethoxylate (β-(3,4-epoxy cyclohexyl)ethyl triethoxysilane), γ-glycidoxypropyl trimethoxys Uane (GMS), γ-epoxypropane decyl dimethoxy decane ( Γ-glycidoxypropyl methyldimethoxysilane, γ-glycidoxypropyl methyldiethoxysilane, γ-glycidoxypropyl dimethoxy(ethoxy) Silane), γ-glycidoxypropyl dimethyl (methoxy) silane, γ-glycidoxypropyl dimethyl (ethoxy) silane , 3,4- Epoxybutyl trimethoxy sulphide (3,4-6 卩〇}}^1^111111161; 11 〇乂) ^ such as 1 ^), 3,4-epoxybutyl diethoxy zebra ( 3,4-6卩〇乂}^3111^1 dip 6111〇乂5^1&1^), 乂(2-aminoethyl)-3-aminopropyldimethoxy decyl decane (N- (2-aminoethyl)-3-aminopropyldimethoxymethylsilane ) '(3-aminopropyl)trimethoxysilane, (3-aminopropyldiethoxylate) Triethoxysilane), (N,N-diethyl-3-aminopropyl)trimethoxysilane, Ν-β(aminoethyl)γ- (N-P (aminoethyl) y-aminopropyl trimethoxysilane), the above-mentioned adhesion aids may be used singly or in combination of two or more kinds. 18 200914956 j^a.u/ujui ‘"+_> 34twf.doc/n In another embodiment, the photosensitive resin composition of the present invention may further be added to a surfactant. The amount of the surfactant to be used is 1 to 30 parts by weight, preferably 5 to 3 parts by weight, based on the weight 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), etc., polyoxyethylene aryl ethers (for example: polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether) Etc.), polyethylene glycol dialkyl esters (for example: polyethylene glycol dilaurate, polyethylene glycol distearate) And the like, an organosiloxane polymer (for example, KP341 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.); (meth)acrylic acid O polymer) : Polyflow No. 75, 90, 95 (manufactured by Kyoei-ShaYushi Kagaku Kogyo Co., Ltd.), Megafac F17 Bu F172, F173, F475 (by Dainippon Chemicals ana Ink Co., Ltd.), Florard FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), Asahi Gard G710, Serflon S382, SC-10, SC-102, SC-103, Sc-104, SC- 1 〇5, 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 incorporate other additives, such as a def〇rmer, a leveling agent (thermal polymerization inhibitor agent), in a step of 2009. Wait. Hereinafter, a method for producing the photosensitive resin composition of the present invention and (A) a photoreactive alkali-soluble resin binder will be described. [(A) Method for Producing Photoreactive Alkali-Soluble Resin Glue] (A) Photoreactive Type Kellow Resin Glue, for example, is an (a-1) ethylenically unsaturated monomer having an acid q group and A-2) The ethylenically unsaturated monomer copolymerizable with 〇1) is subjected to a copolymerization reaction, and then an (a-3) epoxy group-containing ethylenically unsaturated monomer is grafted to form an (a-3) epoxy group-containing ethylenically unsaturated monomer. In the case of producing the (A) photoreactive alkali-soluble resin binder, the solvent to be used may, for example, be the same or different solvent as the (F) organic solvent, and is, for example, benzene, toluene, Xylene (Xylene), methanol, ethanol, ethanol, monoethylene ether, diethylene glycol dimethyl ether, diethylene glycol dimethyl ether (diethylene glycol methyl ether), methyl methoxypropionate, ethyl ethoxypropionate (EEP;), ethyl lactate, tetrahydrofiiran (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 20 200914956 _________ _ .. 84 Twf.doc/n ether), propylene glycol methyl ether acetate (PGMEA), propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, Methyl isobutyl ketone, methyl ether ketone, acetone, cyclohexanone, dimethylformamide (DMF), N, N-di N-methylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), γ-butyrolactone (τ-butyrolactone)
m I 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 (2,2’-azobis-(2,4-dimethylvaleronitrile))、2,2’_偶氮雙(4-甲氧 二 曱基戊 腈)(2,2’-azobis-(4-methoxy-2,4-dimethylvaleronitrile))、偶氣 二異戊腈(2,2’42〇1^-2-11^1^11)1^1'〇1^1'以)等偶氮(&2〇)化 合物，以及過氧化苯曱酸(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) ’於授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.ΐμπι的微孔過濾器或其他過 濾器’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。 21 200914956 _________ —S4twf.doc/n 綜上所述，本發明之感光性樹脂組成物，適用於顯示 面板的間隔物，且為剛性之感光性樹脂組成物，且在曝光 量小於等於120 mJ/cm2時，也可以得到所需求的間隔板之 形狀與膜厚。 雖然本發明已以較佳實施例揭露如上，然其並非用以 任何熟習此技藝者，在不脫離本發明之精神m I and the like, these solvents may be used singly or in combination of several kinds. Further, in the case of producing 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. 2,2'-azobis-(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxybisinvaleronitrile) (2,2'-azobis-(4-methoxy -2,4-dimethylvaleronitrile)), Ozon Diisovaleronitrile (2,2'42〇1^-2-11^1^11)1^1'〇1^1'), etc. Azo (& 2)) a compound, and a peroxide such as benzoylperoxide. The photosensitive resin composition of the present invention is prepared by uniformly mixing the above compounds (A) to (F)' into a mixer or a mixer to form a mixed solution. Then, the composition solution is prepared by, for example, filtering the mixed solution with a pore filter of a pore size of Ο.ΐμπι or other filters. 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. 21 200914956 _________ —S4twf.doc/n As described above, the photosensitive resin composition of the present invention is suitable for a spacer of a display panel and is a rigid photosensitive resin composition, and has an exposure amount of 120 mJ or less. At the time of cm2, the shape and film thickness of the desired spacer can also be obtained. Although the present invention has been disclosed above in the preferred embodiments, it is not intended to be used by anyone skilled in the art without departing from the spirit of the invention.
範圍當視後附之申請專利範圍所界匕本發明之保護 【圖式簡單說明】 無 【主要元件符號說明】 無The scope is defined by the scope of the patent application attached to the patent protection [Simplified description of the drawing] None [Main component symbol description] None
22twenty two