200909536 九、發明說明： 【發明所屬技術領域】 本發明係有關於一種有機保護膜組成物，更詳細地 說，係有關於一種有機保護膜組成物，對l2〇t以下之低^ 5固化步驟，接著力、絕緣性、平坦性等之性能優異，適於 液晶顯示元件之影像形成用材料之用，特別可提升在後_ 製程中顯示元件之耐熱性及相對於溶劑、酸或驗等之耐化 學性。200909536 IX. DESCRIPTION OF THE INVENTION: 1. Field of the Invention The present invention relates to an organic protective film composition, and more particularly to an organic protective film composition, which has a low curing step of less than 1 〇t. Further, it is excellent in properties such as force, insulation, and flatness, and is suitable for use in an image forming material for a liquid crystal display element, and particularly improves heat resistance of a display element in a post-process and relative to a solvent, an acid, or the like. Chemical resistance.
t先前技術:J 10 纟製造LCD等之光裝置之製程中，為了防止顯示元件 接受溶劑、酸或鹼等之化學處理，或在藉濺射形成佈線電 極層時元件表面局部裸露在高溫，致使劣化或受到損傷之 情況，而使用對如此處理具有耐性之保護膜。 對於如此保護膜，要求相對於不得不形成該保護膜之 15基板或形成在保護膜上之層之密著性。又，要求保護膜之 平滑性優異且強勃、透明，耐熱性及耐光性高，長期使用 後亦不能引起著色、黃變、白化等變質，财水性、耐溶劑 性、耐酸性及耐鹼性優異。 最近為了在金或有機/無機層等之減膜上形成佈 2〇線電極(IT〇 :銦錫氧化物、IZ〇 :銦辞氧化物）之圖案，而 藉錢射形成薄膜，且有使用強酸或強驗等化學處理方式之 情況。為此，保護膜是為了保護在濺射時有表面局部裸露 在高溫，或受到一些藥品處理而使用。因此，不用說須要 求具有對其等處理之耐性，並且在藥品處理上亦要求叮〇 200909536 與保護膜間之密著性。作為用以形成具有如此多種不同性 能之保護膜之材料，已知包含有縮水甘油基之聚合物之熱 固化性組成物。 又，經由最近的面板基板的大型化，在保護膜形成上 5 使用熱固化性組成物時，因殘留極微量之未反應單體昇華 而堆積在烤爐内部，而污染烘烤爐，使烘烤條件之控制變 得困難，或是所堆積之未反應單體及/或熱變物附著在面板 基板上而受污染，發生顯示不良，而成問題所在。 此外，在既有的LCD製程中，保護膜形成條件為高溫， 10 因此固化度很高，使用包含有縮水甘油基之聚合物之熱固 化性組成物時，亦對於後續製程上保護膜本身之耐化學 性、耐熱性等之保護膜之一般要求性能上問題不大，但如 有機TFT製程、、可撓性顯示器、OLED製程般使用對熱不 強之基板時，則有問題發生。尤其是在可撓性顯示器製程 15 上所使用的基板本身不耐高溫，因此所使用之保護膜形成 條件亦須為低溫，在接下來的後續製程中，要受到更嚴苛 的藥品處理，因此必須提升耐化學性。又，在OLED製程上， 有機發光元件因高溫而容易劣化，在有機TFT製程之物質亦 因高溫而顯示出脆弱的特性。 20 惟，在既有的製程中所使用之具有縮水甘油基之固化 性樹脂組成物一般是經過220°C以上之高溫製程，才能具備 作為保護膜之用的一般所需性能，另外，以習知之保護膜 形成材料而言，以如此之低溫固化條件時，不能獲得充分 的耐化學性、耐熱性等作為保護膜之用的一般所需性能。 200909536 C 明内容3 為解決如此技術背景下之問題點，本發明之目的係於 提供一種有機保護膜組成物及含有前述有機保護膜組成物 之固化體之光顯示元件，在12(TC以下之低溫固化步驟，接 5 著力、絕緣性、平坦性等之性能亦優異，適於液晶顯示元 件之影像形成用材料之用，尤其可提升對後續製程之顯示 元件之耐熱性、及對溶劑、酸或鹼等之耐化學性。 為達成前述目的，本發明乃提供一種有機保護膜組成 物’叇有機保護膜組成物包含有：（a)丙烯酸系共聚物100 10重量份，係使⑴以下列化學式1所示之化合物5至95重量 /〇’及(η)可與前述化學式丨之化合物共聚合之烯烴系不飽和 化合物5至95重量％共聚合製造者；（b)⑴熱引發劑0.001至5 重量份;或ii)光引發劑0.001至30重量份；（c)酸酐化合物1至 8〇重量份；（d)咪唑系三級胺化合物〇㈨至1重量份；及， 15 (e)有機溶劑，係使前述(a)至⑷的成分成為有機保護膜組成 物之10至50重量％者， 〔化學式1〕t Prior art: J 10 纟In the manufacturing process of an optical device such as an LCD, in order to prevent the display element from being subjected to chemical treatment such as solvent, acid or alkali, or when the wiring electrode layer is formed by sputtering, the surface of the element is locally exposed to a high temperature, resulting in a high temperature. In the case of deterioration or damage, a protective film resistant to such treatment is used. With such a protective film, adhesion to a substrate which has to be formed with the protective film or a layer formed on the protective film is required. Further, the protective film is required to have excellent smoothness, strong elasticity, transparency, high heat resistance and light resistance, and can not cause deterioration such as coloring, yellowing, whitening, etc. after long-term use, and is rich in water, solvent, acid and alkali. Excellent. Recently, in order to form a pattern of a 2-wire electrode (IT〇: indium tin oxide, IZ〇: indium oxide) on a film such as gold or an organic/inorganic layer, a film is formed by borrowing a film, and it is used. The case of chemical treatment such as strong acid or strong test. For this reason, the protective film is used to protect the surface from being exposed to high temperatures during sputtering or to be treated by some chemicals. Therefore, it is needless to say that it is required to have resistance to the treatment, and the adhesion between the 叮〇200909536 and the protective film is also required in the treatment of the drug. As a material for forming a protective film having such a plurality of different properties, a heat curable composition containing a glycidyl group-containing polymer is known. In addition, when a thermosetting composition is used in the formation of the protective film 5 by the recent enlargement of the panel substrate, a very small amount of unreacted monomer remains sublimated and accumulates in the inside of the oven to contaminate the baking furnace and bake. It is difficult to control the baking conditions, or the unreacted monomers and/or thermal alterations deposited on the panel substrate are contaminated, and display defects occur, which is a problem. In addition, in the existing LCD process, the protective film is formed at a high temperature, 10 and thus the degree of curing is high, and when the thermosetting composition containing the glycidyl group-containing polymer is used, the protective film itself is also used for the subsequent process. The general requirements for the chemical resistance, heat resistance, and the like are not critical, but problems such as an organic TFT process, a flexible display, or an OLED process using a substrate that is not hot are problematic. In particular, the substrate used in the flexible display process 15 itself is not resistant to high temperatures, so the protective film formation conditions used must also be low temperature, and in the subsequent subsequent processes, it is subject to more severe drug treatment, so Chemical resistance must be improved. Further, in the OLED process, the organic light-emitting device is easily deteriorated due to high temperature, and the material in the organic TFT process exhibits fragile characteristics due to high temperature. 20 However, the curable resin composition having a glycidyl group used in the existing process is generally subjected to a high-temperature process of 220 ° C or more in order to have the general required performance as a protective film, and In the case of the protective film forming material, when it is subjected to such low-temperature curing conditions, sufficient chemical resistance, heat resistance, and the like as a general performance required for the protective film cannot be obtained. 200909536 C. In order to solve the problems in the technical background, the object of the present invention is to provide an organic protective film composition and a light-display element comprising the cured body of the organic protective film composition, which is 12 or less The low-temperature curing step is excellent in performance such as adhesion, insulation, and flatness, and is suitable for use in image forming materials for liquid crystal display elements, and particularly improves heat resistance of display elements for subsequent processes, and solvent and acid. The chemical resistance of the base or the like. In order to achieve the above object, the present invention provides an organic protective film composition 'the organic protective film composition comprising: (a) 10 parts by weight of the acrylic copolymer 100, wherein (1) is as follows a compound represented by Chemical Formula 1 wherein 5 to 95 parts by weight/〇' and (η) may be copolymerized with 5 to 95% by weight of an olefin-based unsaturated compound copolymerized with a compound of the above formula; (b) (1) Thermal initiator 0.001 To 5 parts by weight; or ii) 0.001 to 30 parts by weight of the photoinitiator; (c) 1 to 8 parts by weight of the acid anhydride compound; (d) 9% (9) to 1 part by weight of the imidazole-based tertiary amine compound; )Have The solvent of the above-mentioned (a) to (4) is 10 to 50% by weight of the composition of the organic protective film, [Chemical Formula 1]
且，在前述化學式1中，x為氫或曱基。 又，本發明提供一種光顯示元件，其包含有前述有機 4呆護膜組成物之固化體。 [發明之效果] 200909536 依本發明之有機保護膜組成物係對於12〇t以下之低 溫固化步驟，接著力、絕緣性、平坦性等之性能亦優異， 適於液晶顯示元件之影像形成用材料之用，尤其對於後續 製程，可提昇顯示元件之耐熱性及對溶劑'酸或驗等之财 5化學性，在作為TFT型液晶顯示元件、有機TFT型液晶顯示 凡件、OLED型液晶顯不元件、可撓性顯示器用之液晶顯示 元件等之有機絕緣膜樹脂、保護膜（〇verc〇at)用抗蝕劑樹 月曰、黑矩陣用抗蚀劑樹脂、柱間隔件用抗姓劑樹脂、滤色 Θ用抗钱職脂等使㈣，有助於耐熱性制化學性的提 10 昇。 [圖式簡單說明] 無Further, in the above Chemical Formula 1, x is hydrogen or a fluorenyl group. Further, the present invention provides an optical display element comprising the cured body of the above-mentioned organic film composition. [Effects of the Invention] 200909536 The organic protective film composition according to the present invention is excellent in properties such as force, insulation, flatness, and the like for a low-temperature curing step of 12 〇t or less, and is suitable for an image forming material of a liquid crystal display element. For the subsequent process, it can improve the heat resistance of the display element and the chemical property of the solvent, such as the acidity or the test. In the case of the TFT type liquid crystal display element, the organic TFT type liquid crystal display, the OLED type liquid crystal is not used. Organic insulating film resin such as a liquid crystal display element for a flexible display, a resist resin for a protective film, a resist resin for a black matrix, and an anti-surname resin for a column spacer (4), which is used to improve the chemical properties of heat resistance. [Simple diagram] No
C實施方式]I 以下詳細說明本發明。 15 本發明之烯丙基丙稀酸系有機保護膜組成物 包含有： (a)丙烯酸系共聚物⑽重量份，係使⑴下列化學式1所示之 化^物5至95重量％及(ii)可與前述化學式1之化合物共聚合 之烯烴系不飽和化合物5至95重量％共聚合製造者· 熱引發劑請1至5重量份；或ii)光引發劑G.001至30重量 20 份；（c)酸酐化合物1至如去θ 80重ϊ份；（d)咪唑系三級胺化合物 0.0001至1重量份.另 . ’久’（e)有機溶劑，係使前述⑻至⑷的 成分成為有機保護膜組成物之1〇至5〇重量％者。 本毛明所使用之前述(a)丙稀酸系共聚物係具有如下作 用即在成膜中進行2次交聯，提高膜之交聯度’使而才化 200909536 學性及耐熱性優異者。 前述(a)之丙烯酸系共聚物可使⑴以前述化學式1所示 之稀丙基丙烯酸系化合物、（ii)可與前述化學式1之化合物 共聚合之烯烴系不飽和化合物為單體，在溶劑及聚合引發 5劑之存在下進行游離基反應而製造者。 月述化學式1所示之化合物，具體上可使用諸如丙稀酸 烯丙酯或甲基丙烯酸烯丙酯等。 月il述歸丙基丙婦酸系化合物，宜於整體總單體中含有5 至95重s°/° ’更含有20至70重量％為佳。其含量不足5重量 10 %時’有不能完成追加交聯之作用，不能提昇耐化學性及 耐熱性之問題’而超過95重量％時，則在成膜時，有因為 不能完成追加交聯之作用的殘留化合物，易於造成剝離劑 (stripper)或蝕刻液之滲透，而降低耐化學性之問題存在。 本發明之丙烯酸系共聚物製造時所使用之單體之前述 15 (幻…)之烯烴系不飽和化合物係可使用諸如：甲基丙婦酸甲 酯、甲基丙烯酸乙酯、甲基丙烯酸正丁酯、甲基丙稀酸第 二丁酯、甲基丙烯酸第三丁酯、丙烯酸曱酯、丙烤酸異丙 酯、曱基丙烯酸環己酯、甲基丙烯酸2—甲基環己能、兩歸 酸二環戊稀酯、丙浠酸二環戊酯、甲基丙烯酸二環戊歸面t 2〇曱基丙烯酸二環戊酯、丙烯酸金剛烷酯、甲基丙烯醆j —金剛烷酯、曱基丙烯酸二環戊基氧基乙酯、甲基内稀酸 異冰片酯、丙烯酸環己酯、丙烯酸2—甲基環己酯、兩歸酸 二環戊基氧基乙酯、丙烯酸異冰片酯、笨基甲基丙烯酸酯、 苯基丙烯酸酯、丙烯酸苯甲酯、甲基丙稀酸2—羥基乙酉b 200909536 苯乙烯、σ—甲基苯乙烯、間甲基苯乙烯、對曱基苯乙烯、 乙烯基甲苯、對曱氧基苯乙烯、1，3 — 丁二稀、異戊二烯、 2,3_二甲基1,3 — 丁二烯、丙烯酸縮水甘油酯、甲基丙烯酸 縮水甘油i旨、α —乙基丙稀酸縮水甘油醋、α —正丙基丙 5 烯酸縮水甘油S旨、α —正丁基丙烯酸縮水甘油S旨、丙稀酸 一 —曱基縮水甘油醋、甲基丙烯酸_ —甲基縮水甘油 酉旨、丙稀酸一β —乙基縮水甘油醋、甲基丙稀酸一β —乙 基縮水甘油酯、丙烯酸一3,4—環氧丁酯、甲基丙烯酸一3,4 —環氧丁酯、丙烯酸一 6,7—環氧庚酯、甲基丙烯酸一6,7 10 一環氧庚酯、α _乙基丙烯酸一 6,7—環氧庚酯、鄰乙烯基 苯曱基縮水甘油醚、間乙烯基苯甲基縮水甘油醚、及、對 乙烯基苯甲基縮水甘油醚等，並可單獨使用前述化合物1種 或混合2種以上使用。 甚者，前述烯烴系不飽和化合物係使用苯乙烯、甲基 15 丙烯酸二環戊基曱酯、曱基丙烯酸縮水甘油酯、甲基丙烯 酸一 yS —甲基縮水甘油S旨、曱基丙烯酸_ 6,7 —環氧庚g旨、 鄰乙烯基苯甲基縮水甘油醚、間乙烯基苯曱基縮水甘油 醚、或對乙稀基苯甲基縮水甘油醚、對甲氧基苯乙烯時， 對於提昇共聚反應性及耐熱性之面來說，更佳。 20 前述烯烴系不飽和化合物係對整體總單體，以含有5至 95重量％為佳，更以含有30至80重量％為佳。其含量超出前 述範圍之外時，會有如下問題衍生，即丙烯酸系共聚物之 保存穩定性降低，丙稀酸系共聚物之極性極端地變高或變 低，容易溶解於特定剝離劑或強酸、鹼性溶液者。 10 200909536 使前述單體與丙晞酸系共聚物聚合時所使用之溶劑係 可使用諸如：甲醇、四氫呋喃、乙二醇單乙醚、乙二醇單 乙鍵、甲基溶纖素乙酸酯、乙基溶纖素乙酸酯、二乙二醇 單甲峻、二乙二醇單乙醚、乙二醇二曱醚、乙二醇二乙醚、 5乙二醇甲基乙醚、丙二醇單曱醚、丙二醇單乙醚、丙二醇 丙醚、丙二醇丁醚、丙二醇甲醚乙酸酯、丙二醇乙醚乙酸 酿、丙二醇丙醚乙酸酯、丙二醇丁醚乙酸酯、丙二醇甲基 乙基丙酸酯、丙二醇乙醚丙酸酯、丙二醇丙醚丙酸酯、丙 二醇丁醚丙酸酯、甲苯、二甲苯、甲基乙酮、環己酮、4一 10羥基4—甲基2—戊酮、乙酸甲酯、乙酸乙酯、乙酸丙酯、 乙酸丁自旨、2—經基丙酸乙醋、2 —經基2 —甲基丙酸甲g旨、 2—經基2—曱基丙酸乙酯、羥基乙酸甲酯、羥基乙酸乙酯、 經基乙酸丁酯、乳酸甲酯、乳酸乙酯、乳酸丙酯、乳酸丁 醋、3 —經基丙酸曱酯、3 —經基丙酸乙酯、3 —經基丙酸丙 15 酯、3—經基丙酸丁酯、2 —經基3—曱基丁酸甲酯、甲氧基 乙酸曱酯、曱氧基乙酸乙酯、曱氧基乙酸丙酯、曱氧基乙 酸丁酯、乙氧基乙酸甲酯、乙氧基乙酸乙酯、乙氧基乙酸 丙酯、乙氧基乙酸丁酯、丙氧基乙酸甲酯、丙氧基乙酸乙 酯、丙氧基乙酸丙酯、丙氧基乙酸丁酯、丁氧基乙酸甲酯、 2〇 丁氧基乙酸乙酯、丁氧基乙酸丙酯、丁氧基乙酸丁酯、2 — 甲氧基丙酸甲酯、2_甲氧基丙酸乙酯、2 —甲氧基丙酸丙 酯、2—曱氧基丙酸丁酯、2—乙氧基丙酸甲酯、2—乙氧基 丙酸乙酯、2 —乙氧基丙酸丙酯、2—乙氧基丙酸丁酯、2 — 丁氧基丙酸甲酯、2 — 丁氧基丙酸乙酯、2 — 丁氧基丙酸丙 11 200909536C Embodiment] I Hereinafter, the present invention will be described in detail. The allyl acrylic acid-based organic protective film composition of the present invention comprises: (a) an acrylic copolymer (10) by weight, based on (1) a chemical compound represented by the following Chemical Formula 1 of 5 to 95% by weight and (ii) 5 to 95% by weight of the olefin-based unsaturated compound copolymerizable with the compound of the above Chemical Formula 1; 1 to 5 parts by weight of the thermal initiator; or ii) Photoinitiator G.001 to 30 by weight 20 parts (c) an acid anhydride compound 1 to, for example, a θ 80 weight portion; (d) an imidazole-based tertiary amine compound: 0.0001 to 1 part by weight. Further, a 'long' (e) organic solvent is a component of the above (8) to (4) It is 1 to 5 % by weight of the composition of the organic protective film. The (a) acrylic acid-based copolymer used in the present invention has the following effects: that is, crosslinking twice in the film formation, and improving the degree of crosslinking of the film, and then the 200909536 is excellent in the academic and heat resistance. . The acrylic copolymer of the above (a) may be (1) a propyl acrylate-based compound represented by the above Chemical Formula 1, and (ii) an olefin-based unsaturated compound copolymerizable with the compound of the above Chemical Formula 1 as a monomer in a solvent. It is produced by performing a radical reaction in the presence of 5 polymerization initiators. The compound represented by Chemical Formula 1 is specifically described, and specifically, allyl acrylate or allyl methacrylate can be used. The propyl propyl acrylate compound is preferably contained in an amount of from 5 to 95 s ° / ° Å and more preferably from 20 to 70 % by weight in the total monomer. When the content is less than 5 wt%, the effect of the additional cross-linking cannot be completed, and the problem of chemical resistance and heat resistance cannot be improved. When the content exceeds 95% by weight, the additional cross-linking cannot be completed at the time of film formation. The residual compound that acts is liable to cause penetration of a stripper or an etchant, and the problem of reducing chemical resistance exists. The above-mentioned 15 (phantom) olefin-based unsaturated compound of the monomer used in the production of the acrylic copolymer of the present invention may be, for example, methyl methyl acetoacetate, ethyl methacrylate or methacrylic acid. Butyl ester, second butyl methacrylate, tert-butyl methacrylate, decyl acrylate, isopropyl propionate, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, Bicyclopentyl diester, dicyclopentyl propionate, dicyclopentanyl methacrylate, dicyclopentanyl t 2 decyl acrylate, adamantyl acrylate, methacryl 醆j - adamantyl ester , dicyclopentyloxyethyl methacrylate, isobornyl methyl dimethacrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, dicyclopentyloxyethyl diacetate, acrylic acid Borneol ester, stupid methacrylate, phenyl acrylate, benzyl acrylate, methyl acrylate 2-hydroxy ethane b 200909536 styrene, σ-methyl styrene, m-methyl styrene, fluorenyl Styrene, vinyl toluene, p-nonyloxystyrene, 1,3-butadiene, isoprene Alkene, 2,3-dimethyl 1,3-butadiene, glycidyl acrylate, glycidyl methacrylate, α-ethyl propylene glycol vinegar, α-n-propyl propylene 5-enoic acid Glycidyl S, α-n-butyl acrylate glycidol S, acrylic acid mono- fluorenyl glycerol vinegar, methacrylic acid _ methyl glycidol hydrazine, acrylic acid - β-ethyl glycidol vinegar , methacrylic acid-β-ethyl glycidyl ester, acrylic acid 3,4-epoxybutyl ester, methacrylic acid-3,4-epoxybutyl ester, acrylic acid 6,7-epoxyheptyl ester, Methacrylic acid-6,7 10-epoxyheptyl ester, α-ethyl acrylate-6,7-epoxyheptyl ester, o-vinylbenzoglycidyl ether, m-vinylbenzyl glycidyl ether, and The p-vinyl benzyl glycidyl ether or the like may be used singly or in combination of two or more kinds thereof. Further, the olefin-based unsaturated compound is styrene, methyl 15-cyclopentyl decyl decyl acrylate, glycidyl methacrylate, methacrylic acid mono-y-methyl glycidol S, methacrylic acid _ 6 , 7 - epoxide g, o-vinyl benzyl glycidyl ether, m-vinyl benzoyl glycidyl ether, or p-vinyl benzyl glycidyl ether, p-methoxy styrene, It is more preferable in terms of improving the copolymerization reactivity and heat resistance. The above olefin-based unsaturated compound is preferably from 5 to 95% by weight, more preferably from 30 to 80% by weight, based on the total monomer. When the content is outside the above range, there is a problem that the storage stability of the acrylic copolymer is lowered, the polarity of the acrylic copolymer is extremely high or low, and it is easily dissolved in a specific release agent or strong acid. , alkaline solution. 10 200909536 The solvent used in the polymerization of the above monomer and the propionic acid copolymer may be, for example, methanol, tetrahydrofuran, ethylene glycol monoethyl ether, ethylene glycol monoethyl bond, methyl cellosolve acetate, Ethyl cellosolve acetate, diethylene glycol monomethyl sulphate, diethylene glycol monoethyl ether, ethylene glycol dioxime ether, ethylene glycol diethyl ether, 5 ethylene glycol methyl ether, propylene glycol monoterpene ether, Propylene glycol monoethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, propylene glycol methyl ether acetate, propylene glycol diethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, propylene glycol methyl ethyl propionate, propylene glycol diethyl ether Acid ester, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate, toluene, xylene, methyl ethyl ketone, cyclohexanone, 4-10 hydroxyl 4-methyl-2-pentanone, methyl acetate, acetic acid Ester, propyl acetate, butyl acetate, 2-ethyl propyl acetonate, 2-methyl 2-methylpropionic acid, 2-ethyl 2-methyl propyl propionate, glycolic acid Ester, ethyl hydroxyacetate, butyl acetate, methyl lactate, ethyl lactate, propyl lactate, Butic acid vinegar, 3-propenyl decanoate, 3-ethyl propyl propionate, 3-propyl propionate, butyl 3-propionate, 2-methoxy-3-butyrate Methyl ester, methoxy methoxyacetate, ethyl decyloxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, ethoxyacetic acid Propyl ester, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, 2-butoxy Ethyl acetate, propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2- Butyl methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, 2 — Methyl butoxypropionate, ethyl 2-butoxypropionate, propionic acid 2-butoxypropionic acid 11 200909536
Sg、2 — 丁氧基丙酸丁 g旨、3—甲氧基丙酸曱醋、3 —曱氧基 丙酸乙酯、3—甲氧基丙酸丙酯、3~甲氧基丙酸丁酯、3一 乙氧基丙酸曱酯、3—乙氧基丙酸乙酯、3—乙氧基丙酸丙 面曰、3 —乙氧基丙酸丁酯、3 —丙氧基丙酸曱酯、3—丙氧基 丙酸乙酯、3—丙氧基丙酸丙酯、3—丙氧基丙酸丁酯、3一 丁氧基丙酸甲酯、3 — 丁氧基丙酸乙酯、3 — 丁氧基丙酸丙 醋、或3_丁氧基丙酸丁酯等之化合物等等，前述化合物可 單獨使用或混合2種以上使用。 使前述單體與丙稀酸系共聚物聚合而所使用之聚合引 10發劑係可使用游離基聚合引發劑，具體而言，可使用諸如 2,2〜偶氮二異丁腈、2,2 —偶氮雙(2,4 —二曱基戊腈）、2,2 —偶氮雙(4_甲氧基2,4一二甲基戊腈）、丨丨一偶氮雙(環己 烧1 一猜）、或一甲基2,2 —偶氬—異丁酸醋；過氧化苯甲 醯、過氧化月桂醯、過氧化第三丁基三甲基乙酸酯、丨i — 15雙〜（第三丁基過氧)環己烷或者含過氧化氫或過氧化物之 氧化還原型引發劑之1種以上。 使前述單體在溶劑與聚合引發劑的存在下進行游離其 反應而製造之(a)丙烯酸共聚物之聚苯乙烯換算重量％ : 子量（Mw)係以3，_至50，_為佳，更以15 1 20 乂土 “ ’ 王 25,〇〇〇 為 佳。對於前述聚苯乙稀換算重量平騎子量科3，嶋 機保護膜組成物，有耐化學性降低，或耐熱性不佳 存在，超過5〇,〇〇〇時，雖有提高耐熱性或耐化題 但是卻有保賴之基本要件所在之平坦度劣化之問題點’ 本發明所使用之前述⑻⑴之熱引發劑係可達成誘導妓 12 200909536 聚物中烯丙基作用基之鏈反應之作用，具體而言，可使用 2,2—偶氮二異丁腈、2,2—偶氮雙(2,4一二甲基戊腈）、2,2 一偶氮雙(4一曱氧基2,4—二曱基戊腈）、1,1 一偶氮雙(環己 烷一 1 一腈）、或二甲基2,2—偶氮二異丁酸酯；過氧化苯甲 5 醯、過氧化月桂醯、過氧化第三丁基三甲基乙酸酯、1，1一 雙一（第三丁基過氧）環己烷或者含過氧化氫或過氧化物之 氧化還原型引發劑等等。 前述熱引發劑係相對於前述丙浠酸系共聚物100重量 份，以含有0.001至5重量份者為佳。前述含量不足0.001重 10 量份時，鏈反應誘導微弱，交聯度不足，耐熱性降低，超 過5重量份時，則作為雜質而殘留在膜内部，造成耐化學性 降低，或保存穩定性降低。 又，本發明所使用之前述（ii)之光引發劑係可使用 Irgacure 369、Irgacure 651、Irgacure 907、Darocur TPO、 15 Irgacure 819、三嗓系、苯偶因、苯乙綱系、味。坐系或咭4頁 酮系等之化合物。具體而言，前述光引發劑可單獨使用或 混合2種以上之2,4一雙三氣甲基一6—對甲氧基苯乙烯基 一均三嗪、2—對甲氧基苯乙烯基一 4,6—雙三氯甲基一均 三嗪、2,4—三氯曱基一 6—三嗪、2,4 —三氯甲基一4一甲基 20 萘基一 6—三嗪、二苯曱酮、對（二乙基胺基)二苯甲酮、2,2 一二氯一4 —苯氧基苯乙酮、2,2—二乙氧基苯乙酮、2 — 二烧基咕嘲酮、2,4 —二曱基咕°頓_、2,4 _二乙基咕°頓酿I、 及2,2 —雙一2 —氣苯基一4,5,4,5 —四苯基一2 — 1,2 —聯二 咪唑等之化合物。 13 200909536 月J述光引發劑係相對於前述丙烯酸系共聚物1⑻重量 =，以含有0.001至30重量份者為佳，且含有〇〇1至2〇重量 份者更佳。前述光引發劑的含量不足〇〇〇1重量份時，鍵反 應誘導微弱，交聯度;熱性降低，超過3()重量份時， 5則作為雜質而殘留在臈内部，造成财化學性降低，或保存 穩定性降低。 又本發明所使用之前述(c)酸酐化合物係可選擇使用 偏苯—酸酐、馬來酸酐、衣康酸酐、檸康酸酐、順式_ 1，2, 〜四氫鄰苯二甲酸酐、鄰苯二甲酸酐等等。 1〇 珂述(c)酸酐化合物係相對於前述丙烯酸共聚物1〇〇重 量份，含有1至80重量份，且以含有丙烯酸系共聚物中所含 之環氧作用基之莫耳對比〇_8倍至丨.2倍之莫耳者為佳。在前 述範圍内時，即使在低溫固化步驟中，亦能具備優異的接 著力、絕緣性、平坦性等性能。 5 又，本發明所使用之前述(d)咪唑系三級胺化合物係作 為觸媒而作用在丙烯酸系共聚物中之環氧作用基與酸酐之 缩合反應，具體而言，宜選自於由：咪唑、丨一甲基咪唑、 曱基咪唑、4(5)—甲基咪唑、1_乙烯基咪唑、丨,—二 甲基咪唑、2—乙基咪唑、1 —烯丙基咪唑、2一甲基—i — 己稀基味°坐、2—丙基咪β坐、2 —乙基一4 —甲基咪唾、2一 異丙基咪唑、4一咪唑羧酸、咪唑一2—羧酸、咪唑[ny °比唆、苯並咪唑、4_氮雜苯並咪唑、1 — 丁基咪唾、5—甲 基苯並咪°坐、2—甲基苯並咪嗤、2—苯基°米η坐、1 —笨基咪 唑、4一苯基咪唑、2—乙基苯並咪唑、及5,6—二甲基苯並 14 200909536 咪唑構成之群之1種以上使用。 本發明所使用之前述⑷咪唾系三級胺化合物係相對於 前述丙婦酸系共聚物100重量份，以含有㈣謝幻重心 為佳。前述含量不足0.0001重量份時，不能對反應有= 5的助益，超過1重量份時，則有作為雜質而殘留在膜内部， 造成耐化學性降低之問題衍生。 又，本發明所使用之(e)溶劑係作為不發生有機保護膜 之平坦性及塗層不均之情況，且以形成均勻的保護膜之 用。前述溶劑係可使用：甲醇、乙醇等之醇類；四氯咬喃 等之醚類；乙二醇單甲醚、乙二醇單乙醚等之二醇嶋； 甲基溶纖素乙酸酯、乙基溶纖素乙酸酯等之乙二醇烷基醚 乙酸酯類；二乙二醇單甲醚、二乙二醇單乙醚、二乙二醇 二甲醚等之二乙二醇類；丙二醇甲醚、丙二醇乙醚、丙二 醇丙醚、丙二醇丁醚等之丙二醇單烷基醚類；丙二醇甲醚 15乙酸酯、丙二醇乙醚乙酸酯、丙二醇丙醚乙酸酯、丙二醇 丁醚乙酸酯等之丙二醇烷基醚乙酸酯類；丙二醇甲醚丙酸 S曰、丙二醇乙醚丙酸酯、丙二醇丙醚丙酸酯、丙二醇丁趟 丙酸S旨等之丙二醇院基謎丙酸g旨類；甲苯、二甲苯等之芳 香族碳化氫類；甲基乙酮、環己酮、4一羥基4—曱基2—戊 20酮等之酮類；或，乙酸甲酯、乙酸乙酯、乙酸丙酯、乙酸 丁酯、2—經基丙酸乙酯、2 —經基2 —甲基丙酸甲酯、2 — 經基2—甲基丙酸乙酯、羥基乙酸甲酯、羥基乙酸乙酯、羥 基乙酸丁酯、乳酸甲酯、乳酸乙酯、乳酸丙酯、乳酸丁酯、 3 —羥基丙酸甲酯、3 —羥基丙酸乙酯、3—羥基丙酸丙酯、 15 200909536 3—羥基丙酸丁酯、2 —羥基3 —甲基丁酸甲酯、甲氧基乙酸 甲酯、甲氧基乙酸乙酯、甲氧基乙酸丙酯、甲氧基乙酸丁 醋、乙氧基乙酸曱S旨、乙氧基乙酸乙醋、乙氧基乙酸丙醋、 乙氧基乙酸丁酯、丙氧基乙酸甲酯、丙氧基乙酸乙酯、丙 5 氧基乙酸丙酯、丙氧基乙酸丁酯、丁氧基乙酸甲酯、丁氧 基乙酸乙酯、丁氧基乙酸丙酯、丁氧基乙酸丁酯、2 —甲氧 基丙酸甲酯、2—甲氧基丙酸乙酯、2—甲氧基丙酸丙酯、2 一甲氧基丙酸丁醋、2—乙氧基丙酸甲g旨、2 —乙氧基丙酸 乙S曰、2—乙氧基丙酸丙g旨、2 —乙氧基丙酸丁 g旨、2—丁氧 10基丙酸甲酯、2—丁氧基丙酸乙酯、2—丁氧基丙酸丙酯、2 丁氧基丙酸丁 S旨、3—甲氧基丙酸甲醋、3 —甲氧基丙酸 乙醋、3—甲氧基丙酸丙酯、3 —甲氧基丙酸丁酯、3 —乙氧 基丙酸甲酯、3—乙氧基丙酸乙酯、3_乙氧基丙酸丙酯、3 一乙氧基丙酸丁酯、3—丙氧基丙酸曱酯、3—丙氧基丙酸 5 乙Sb 3丙氧基丙酸丙g旨、3 —丙氧基丙酸丁自旨、3 — 丁氧 基丙酸甲酯、3 — 丁氧基丙酸乙酯、3 — 丁氧基丙酸丙酯、 或3—丁氧基丙酸丁酯等酯類單獨丨種或混合2種以上使用。 尤其則述溶劑宜選自於由溶解性、與各成分之反應性 及塗佈膜形成容易之二醇謎類、乙撐基院基_乙酸酯類及 20二乙二醇類構成之群中之1種以上使用。 雨述溶劑之含量係使整體有機保護膜組成物之固態部 分含量成為10至50重量％時為佳，具有前述範圍之固態部 分之組成物係以經過〇. 1至〇. 2 // m之米利波亞過濾器過濾 後使用者為佳。更以含有成為15至40重量％者為佳。前述 16 200909536 整體組成物之固態部分含量不足10重量％時，塗膜厚度過 薄，有塗膜平坦性降低之問題，超過5〇重量％時，塗膜厚 度過厚，則有所謂對於塗佈時對塗佈裝置造成負擔之問題 衍生。 5 由前述成分形成之本發明之有機保護膜組成物，因應 必要，可更進一步含有（f)光增感劑及(g)界面活性劑。 前述(f)光增感劑係對所使用之紫外線具有適當的靈敏 度，透過比光引發劑還快速之光引發反應，使能量轉移到 光引發劑’助益於光引發劑之光引發反應速度。前述光增 10感劑係可使DETX、ITX、正丁基吖啶酮或2 —乙基己基一二 甲基胺基苯甲酸酯單獨使用或混合2種以上使用。 前述(f)光增感劑係相對於前述(ii)光引發劑100重量 份’以含有0.001至40重量份為佳，其含量在前述範圍内 時，在提昇負型感光性樹脂組成物之光固化速度來說，更 15 佳。 前述(g)界面活性劑係具有提昇有機保護膜組成物之塗 佈性及平坦性之作用。前述界面活性劑可使用聚氧乙撐基 辛基苯基醚、聚氧基乙撐基壬基苯基醚、F171、F172、 F173(商品名稱：曰商大曰本ink公司）、FC430、FC431(商 20 品名稱：日商住友3M公司）、或KP341(商品名稱：日商信 越化學工業公司）等等。 前述界面活性劑係相對於前述(a)丙烯酸系共聚物100 重量份’以含有0.0001至2重量份者為佳，其含量在前述範 圍内時，在提昇有機保護膜組成物之塗佈性及平坦性來 17 200909536 說，更佳。 又，本發明之有機保護膜組成物， 因應需要，可在前 Γ 二加熱聚合禁止劑、消泡削等具相溶性之添加 件之=同，亦可添加鱗。例如TFT龍晶顯示元 蝕劍你、^成用材料之一的黑矩陣用抗银劑及遽色器用抗 、於前述組成物調配有顏料者，此時，顏料俜按里矩 ::抗_及遽色__用途，而可=用 …、機顏料及有機顏料都可使用。 10 15 固4本發明係提供一種含有前述有機保護膜組成物之 _匕體之光顯示元件，前述光顯示元件可ATF丁型 •jrr 7/1 有機TFT型液晶顯示元件、〇LED型光顯示元件、或 了繞性顯示器之光顯示元件。 曰較佳的是’前述有機保護膜組成物之固化體係TFT型液 貝示元件之有機絕緣膜、保護膜用之抗蚀劑、黑矩陣用 抗蝕劑、柱間隔件用抗蝕劑、或濾色器用抗蝕劑。 具體而言，如下舉一例，說明使用前述有機保護膜組 成物，形成TFT型液晶顯示元件之圖案，製造光顯示元件之 方法。 首先使本發明之有機保護膜組成物以噴霧法、觀塗 2〇 &、轉塗法等，塗佈在基板表面，藉前烘烤除去溶劑，形 成塗佈膜。此時，前述前烘烤藉以70至110。(：之溫度實施i 至15分鐘者為佳。 由前述有機保護膜組成物所形成之保護膜係可藉烤箱 等加熱裝置，以120至25〇t之溫度加熱30到90分鐘，得到 18 200909536 最後的保護膜。 使用有（b)(ii)之光引發劑之有機保護膜組成物時，在前 烘烤後，使可見光線、紫外線、遠紫外線、幅射線、X射線 等照射在前述所形成之塗佈膜，進行後製程，即可得到目 5 標所在之保護膜。 藉如此本發明之有機保護膜組成物，在120°C以下之低 溫固化步驟中，接著力、耐熱性、平坦性、耐化學性等之 性能亦優異，適於液晶顯示元件之影像形成用材料之用， 在形成液晶顯示元件之有機絕緣膜時，由於UV透射率佳， 10 因此可適合作為層間有機絕緣膜使用，可使用在保護膜用 抗蝕劑樹脂、黑矩陣用抗蝕劑樹脂、柱間隔件用抗蝕劑樹 脂、或濾色器用抗蝕劑樹脂，尤其可提昇耐熱性及耐化學 性。 以下，為理解本發明乃提示較佳實施例，但下述實施 15 例只不過是舉例說明本發明而已，本發明範圍並不受限於 下述實施例者。 [實施例] 實施例1 (製造烯丙基丙烯酸系共聚物） 20 在具備冷卻管及攪拌器之燒瓶，放入2,2 —偶氮雙(2,4 —二甲基戊腈）1〇重量份、丙二醇甲醚乙酸酯400重量份、 下述化學式la之甲基丙烯酸烯丙酯30重量份、甲基丙烯酸 縮水甘油酯60重量份、及苯乙浠10重量份，做過氮置換之 後，再緩慢地攪拌。將前述反應溶液昇溫到55°C，一邊維 19 200909536 持這個溫度20小時，一邊製造含有丙烯酸系共聚物之聚合 物溶液。 如前述製造之丙烯酸系共聚物之固態部分濃度為30重 量％，聚合物之重量平均分子量為15,000之聚合物溶液。此 5 時，重量平均分子量為使用GPC所測定之聚苯乙烯換算平 均分子量。 (製造烯丙基丙烯酸系有機保護膜組成物） 本發明之有機保護膜組成物製造成二液型形態。以含 有前述所製造之丙烯酸系共聚物之丙二醇甲醚乙酸酯聚合 10 物溶液100重量份、矽系界面活性劑混合了 0.005重量份。 在前述混合物加入丙二醇甲醚乙酸酯溶解，使固態部分濃 度成為25重量％，製造溶液A。 溶液B是作為熱引發劑，混合了 2,2 —偶氮雙(2,4一二甲 基戊腈）1.5重量份、偏苯三酸酐10重量份、三級胺系甲基苯 15 並咪唑0.002重量份。在前述混合物加入二乙二醇乙基甲醚 溶解之，使固態部分濃度成為1〇重量％，製造溶液B。 以4 : 1重量比率混合溶液A及溶液B之後，以0.2/zm之 米利波亞過濾器過濾，製造了有機保護膜組成物。 [化學式la]Sg, 2 - butoxypropionic acid, glycerol 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionic acid Butyl ester, decyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methoxypropyl propionate, butyl 3-ethoxypropionate, 3-propoxypropane Oxalate ester, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, 3-butoxypropane A compound such as ethyl acetate, 3-butoxypropionic acid propyl vinegar, or butyl 3-butoxypropionate, or the like may be used alone or in combination of two or more. The polymerization initiator used for polymerizing the above monomer and the acrylic acid copolymer may be a radical polymerization initiator, and specifically, for example, 2,2 to azobisisobutyronitrile, 2, may be used. 2 —Azobis(2,4-dimercaptophthalonitrile), 2,2-Azobis(4-methoxy 2,4-dimethylpentanenitrile), 丨丨-azobis (cyclohexane) Burn 1 guess, or monomethyl 2,2- argon-isobutyrate; benzammonium peroxide, laurel peroxide, tributyltrimethyl acetate, 丨i-15 One or more of bis(t-butylperoxy)cyclohexane or a redox type initiator containing hydrogen peroxide or a peroxide. The polystyrene equivalent weight % of the (a) acrylic copolymer is produced by reacting the above monomer in the presence of a solvent and a polymerization initiator: the amount of the sub-component (Mw) is preferably 3, _ to 50, _ , 15 15 20 乂 " " Wang 25, 〇〇〇 is better. For the aforementioned polystyrene conversion weight flat rider volume 3, the protective film composition, chemical resistance, or heat resistance Poorly present, more than 5 〇, 〇〇〇, although there is a problem of improving the heat resistance or resistance, but there is a problem that the flatness of the basic elements of the protection is degraded. The thermal initiator of the above (8) (1) used in the present invention The effect of inducing the chain reaction of the allyl group in the 09512 200909536 polymer can be achieved. Specifically, 2,2-azobisisobutyronitrile and 2,2-azobis (2,4) can be used. Dimethylvaleronitrile), 2,2-azobis(4-monooxy 2,4-dimercaptophthalonitrile), 1,1-azobis(cyclohexane-l-carbonitrile), or two Methyl 2,2-azobisisobutyrate; benzoyl peroxide 5 醯, laurel, butyl trimethyl acetate, 1,1 bis(tributyl) Over Oxygen) cyclohexane or a redox type initiator containing hydrogen peroxide or a peroxide, etc. The above thermal initiator is contained in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of the above-mentioned propionic acid copolymer. When the content is less than 0.001 by weight and 10 parts by weight, the chain reaction is weakly induced, the degree of crosslinking is insufficient, and the heat resistance is lowered. When it exceeds 5 parts by weight, it remains as an impurity in the inside of the film, resulting in a decrease in chemical resistance or storage stability. Further, the photoinitiator of the above (ii) used in the present invention may be Irgacure 369, Irgacure 651, Irgacure 907, Darocur TPO, 15 Irgacure 819, triterpenoid, benzoin, phenylethylamine, A compound such as a ketone system or a ketone system. Specifically, the photoinitiator may be used alone or in combination of two or more kinds of 2,4-bistrimethylmethyl-6-p-methoxystyryl. Monos-triazine, 2-p-methoxystyryl-4,6-bistrichloromethyl-mono-s-triazine, 2,4-trichloroindolyl-6-triazine, 2,4-trichloromethyl 4-Methyl 20 Naphthyl- 6-triazine, benzophenone, p-(diethylamino)benzol Ketone, 2,2-dichloro-4-phenoxyacetophenone, 2,2-diethoxyacetophenone, 2-dialkylpyridinone, 2,4-dimercaptopurine _ , 2,4 _diethyl 咕 ° 酿 I, and 2, 2 - bis 2 - phenyl phenyl - 4,5,4,5 - tetraphenyl 1-2, 1, 2-diimidazole, etc. The compound of the present invention is preferably more preferably 0.001 to 30 parts by weight, and more preferably 1 to 2 parts by weight, based on the weight of the acrylic copolymer 1 (8). When the content of the photoinitiator is less than 1 part by weight, the bond reaction is weakly induced, and the degree of crosslinking is lowered; the heat is lowered, and when it exceeds 3 parts by weight, 5 remains as an impurity in the interior of the crucible, resulting in a decrease in chemical properties. , or the storage stability is reduced. Further, in the above (c) acid anhydride compound used in the present invention, a benzene-anhydride, maleic anhydride, itaconic anhydride, citraconic anhydride, cis-1, 2, tetrahydrophthalic anhydride, or the like may be optionally used. Phthalic anhydride and the like. (1) The (c) acid anhydride compound is contained in an amount of 1 to 80 parts by weight based on 1 part by weight of the acrylic copolymer, and is contained in a molar ratio of the epoxy group contained in the acrylic copolymer. 8 times to 丨. 2 times the molar is better. When it is in the above range, it can have excellent properties such as adhesion, insulation, and flatness even in the low-temperature curing step. Further, the (d) imidazole-based tertiary amine compound used in the present invention is a condensation reaction of an epoxy group and an acid anhydride which act on the acrylic copolymer as a catalyst, and specifically, is preferably selected from : imidazole, fluorenylmethylimidazole, mercapto imidazole, 4(5)-methylimidazole, 1-vinylimidazole, hydrazine, dimethylimidazole, 2-ethylimidazole, 1-allyl imidazole, 2 Monomethyl-i - dilute base, sitting, 2-propylimidinol, 2-ethyl-4-methylammonium, 2-isopropylimidazole, 4-imidazolecarboxylic acid, imidazole-2 Carboxylic acid, imidazole [ny ° 唆, benzimidazole, 4-azabenzimidazole, 1-butylimidazole, 5-methylbenzopyrene, 2-methylbenzimidazole, 2- One or more of the group consisting of phenyl group η sit, 1 - strepyrazole, 4-phenylimidazole, 2-ethylbenzimidazole, and 5,6-dimethylbenzo-14 200909536 imidazole. The above (4) imazoid tertiary amine compound used in the present invention is preferably contained in an amount of (4) a critical center of gravity relative to 100 parts by weight of the above-mentioned glycerol-based copolymer. When the content is less than 0.0001 part by weight, the reaction does not have a benefit of 5%. When the amount exceeds 1 part by weight, the film may remain as an impurity and may cause a decrease in chemical resistance. Further, the solvent (e) used in the present invention is used to form a uniform protective film without causing flatness of the organic protective film and uneven coating. As the solvent, an alcohol such as methanol or ethanol; an ether such as tetrachloropyran; a glycol oxime such as ethylene glycol monomethyl ether or ethylene glycol monoethyl ether; methyl fibrin acetate; Ethylene glycol alkyl ether acetate such as ethyl cellosolve acetate; diethylene glycol such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether or diethylene glycol dimethyl ether; Propylene glycol monoalkyl ethers such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether; propylene glycol methyl ether 15 acetate, propylene glycol diethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate Propylene glycol alkyl ether acetates; propylene glycol methyl ether propionic acid S 曰, propylene glycol diethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl phthalic acid S, etc. An aromatic hydrocarbon such as toluene or xylene; a ketone such as methyl ethyl ketone, cyclohexanone or 4-hydroxy-4-indenyl-2-pentanone; or methyl acetate, ethyl acetate or ethyl acetate Ester, butyl acetate, ethyl 2-propionic acid propionate, 2-methyl 2-methylpropionate, 2-yl group 2-A Ethyl propyl propionate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl glycolate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, 3-hydroxypropionic acid Ethyl ester, propyl 3-hydroxypropionate, 15 200909536 butyl 3-hydroxypropionate, methyl 2-hydroxy 3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, methoxy Propyl acetate, methoxyacetic acid butyl vinegar, ethoxyacetic acid 曱S, ethoxyacetic acid vinegar, ethoxyacetic acid propylene vinegar, butyl ethoxyacetate, methyl propoxyacetate, propoxy Ethyl acetate, propyl propoxy propyl acetate, butyl oxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butyl butoxyacetate, 2-methyl Methyl oxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2 methoxypropionic acid butyl vinegar, 2-ethoxypropionic acid 甲g, 2 — Ethyl ethoxypropionate, 2-ethoxypropyl propionate, 2-ethoxypropanoic acid, 2-butoxymethyl 10-methyl propionate, 2-butoxypropionic acid Ester, 2-butoxypropane Propyl ester, 2-butoxypropionic acid butyl S, 3-methoxypropionic acid methyl vinegar, 3-methoxypropionic acid ethyl vinegar, 3-methoxypropionic acid propyl ester, 3-methoxypropionic acid Butyl ester, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, 3-propoxypropionic acid Oxime ester, 3-propoxypropionic acid 5 Ethyl Sb 3 propoxypropionic acid propyl g, 3-propoxypropionic acid butyl, methyl 3-butoxypropionate, 3-butoxy propyl An ester such as ethyl acetate, propyl 3-butoxypropionate or butyl 3-butoxypropionate may be used alone or in combination of two or more. In particular, the solvent is preferably selected from the group consisting of a diol mystery, an ethylene-based compound, an acetate, and a 20-diethylene glycol, which are soluble, and have reactivity with each component and a coating film. One or more of them are used. The content of the solvent is preferably such that the solid portion of the organic protective film composition is 10 to 50% by weight, and the composition of the solid portion having the above range is 〇. 1 to 〇. 2 // m It is preferred that the user is filtered after the Miriboi filter. It is preferable to contain 15 to 40% by weight. 16 200909536 When the content of the solid portion of the overall composition is less than 10% by weight, the thickness of the coating film is too thin, and the flatness of the coating film is lowered. When the thickness of the coating film is too thick, the thickness of the coating film is too thick, so that coating is applied. The problem of burdening the coating device is derived. The organic protective film composition of the present invention formed from the above components may further contain (f) a photosensitizer and (g) a surfactant, if necessary. The above (f) photosensitizer has appropriate sensitivity to the ultraviolet light used, and the light is induced by a rapid photo-initiator to transfer the energy to the photoinitiator to help the photoinitiator to initiate the reaction. . The photo-enhanced sensitizer may be used alone or in combination of two or more kinds of DETX, ITX, n-butylacridone or 2-ethylhexyl monodimethylamino benzoate. The above (f) photosensitizer is preferably contained in an amount of 0.001 to 40 parts by weight based on 100 parts by weight of the above (ii) photoinitiator, and when the content is within the above range, the negative photosensitive resin composition is raised. In terms of light curing speed, it is even better. The above (g) surfactant has an effect of improving the coatability and flatness of the composition of the organic protective film. As the surfactant, polyoxyethylene octyl phenyl ether, polyoxyethylene decyl phenyl ether, F171, F172, F173 (trade name: 曰商大曰本ink company), FC430, FC431 can be used. (Shang 20 product name: Japanese business Sumitomo 3M company), or KP341 (commodity name: Nissho Shin-Etsu Chemical Industry Co., Ltd.) and so on. The surfactant is preferably contained in an amount of 0.0001 to 2 parts by weight based on 100 parts by weight of the (a) acrylic copolymer, and when the content is within the above range, the coating property of the organic protective film composition is improved. Flatness comes 17 200909536 says better. Further, the organic protective film composition of the present invention may be added in the same manner as in the case of the additive having the compatibility of the prepolymerization, the defoaming, and the like. For example, TFT Longjing shows that the black matrix of one of the materials used in the material is used as an anti-silver agent and a color resist for the black matrix, and the pigment is blended with the above composition. At this time, the pigment is pressed in the moment:: And 遽__ use, but can be used with..., machine pigments and organic pigments. 10 15 solid 4 The present invention provides an optical display element comprising the above-mentioned organic protective film composition, the optical display element can be ATF-type, jrr 7/1 organic TFT type liquid crystal display element, 〇LED type light display An element, or a light display element of a revolving display. Preferably, the curing system of the organic protective film composition is an organic insulating film of a TFT type liquid-imaging element, a resist for a protective film, a resist for a black matrix, a resist for a pillar spacer, or A color filter is used for the resist. Specifically, a method of producing a light-display element by forming a pattern of a TFT-type liquid crystal display element using the organic protective film composition will be described below. First, the organic protective film composition of the present invention is applied onto the surface of a substrate by a spray method, a coating method, a transfer coating method, or the like, and the solvent is removed by baking to form a coating film. At this time, the aforementioned prebaking is performed by 70 to 110. (The temperature is preferably from i to 15 minutes. The protective film formed by the above organic protective film composition can be heated by a heating device such as an oven at a temperature of 120 to 25 Torr for 30 to 90 minutes to obtain 18 200909536 Final protective film. When using the organic protective film composition of the photoinitiator of (b) (ii), after the prebaking, visible light, ultraviolet light, far ultraviolet light, radiation, X-ray, etc. are irradiated on the foregoing. The formed coating film is subjected to a post-process to obtain a protective film of the target. The organic protective film composition of the present invention, in the low-temperature curing step at 120 ° C or less, is followed by force, heat resistance, It is also excellent in properties such as flatness and chemical resistance, and is suitable for use as an image forming material for liquid crystal display elements. When an organic insulating film of a liquid crystal display element is formed, since it has a good UV transmittance, 10 can be suitably used as an interlayer organic insulating layer. For the film, a resist resin for a protective film, a resist resin for a black matrix, a resist resin for a pillar spacer, or a resist resin for a color filter can be used, and in particular, heat resistance and chemical resistance can be improved. The following is a description of the preferred embodiments, but the following examples are merely illustrative of the invention, and the scope of the invention is not limited by the following examples. 1 (Production of allylacrylic copolymer) 20 In a flask equipped with a cooling tube and a stirrer, 2,2-azobis(2,4-dimethylvaleronitrile) 1 part by weight, propylene glycol methyl ether 400 parts by weight of the acetate, 30 parts by weight of allyl methacrylate of the following formula la, 60 parts by weight of glycidyl methacrylate, and 10 parts by weight of phenethyl hydrazine, after being replaced by nitrogen, stirring slowly The temperature of the reaction solution was raised to 55 ° C, and the polymer solution containing the acrylic copolymer was produced while maintaining the temperature for 20 hours. The solid portion concentration of the acrylic copolymer produced as described above was 30% by weight. A polymer solution having a weight average molecular weight of the polymer of 15,000. At this time, the weight average molecular weight is a polystyrene-converted average molecular weight measured by GPC. (Production of an allyl acrylic organic protective film group) The organic protective film composition of the present invention is produced in a two-liquid form, and 100 parts by weight of a propylene glycol methyl ether acetate polymerization 10 solution containing the acrylic copolymer produced as described above, and a lanthanoid surfactant mixed with 0.005 In the above mixture, propylene glycol methyl ether acetate was added to dissolve, and the solid portion concentration was 25% by weight to prepare solution A. Solution B was used as a thermal initiator, and 2,2-azo double (2,4 was mixed). 1.5 parts by weight of dimethylvaleronitrile, 10 parts by weight of trimellitic anhydride, and 0.002 parts by weight of tertiary amine methylbenzene 15 and imidazole. The mixture is dissolved in diethylene glycol ethyl methyl ether to make the solid portion concentration 1 〇% by weight, solution B was produced. After the solution A and the solution B were mixed at a weight ratio of 4:1, they were filtered through a 0.2/zm Millipore filter to prepare an organic protective film composition. [chemical formula la]
X 20 0 在上述式中，X為CH3。 實施例2 在前述實施例1之丙烯酸系共聚物製造上，除了以化學 20 200909536 式la之甲基丙烯酸烯丙酯20重量份、甲基丙烯酸縮水甘油 酯60重量份、及苯乙烯20重量份，製造固態部分的濃度為 30重量％，重量平均分子量為15,000之丙烯酸系共聚物之 外，其餘以與前述實施例1同一之方法實施，製造了有機保 5 護膜組成物。 實施例3 在前述實施例1之丙烯酸系共聚物製造上，除了以化學 式la之甲基丙烯酸烯丙酯10重量份、甲基丙烯酸縮水甘油 酯60重量份、及苯乙烯30重量份，製造固態部分的濃度為 10 30重量％，重量平均分子量為15,000之丙浠酸系共聚物之 外，其餘以與前述實施例1同一之方法實施，製造了有機保 護膜組成物。 實施例4 在前述實施例1之丙稀酸系共聚物製造上，除了使用化 15 學式la之甲基丙稀酸烯丙S旨60重量份及苯乙稀40重量份， 製造固態部分的濃度為30重量％，且重量平均分子量為 15,000之丙烯酸系共聚物之外，其餘以與前述實施例1同一 之方法實施，製造了有機保護膜組成物。 實施例5 20 在前述實施例1之丙烯酸系共聚物製造上，除了以2,2 —偶氮雙(2,4一二甲基戊腈）10重量份、丙二醇甲醚乙酸酯 400重量份、下述化學式lb之丙烯酸烯丙酯30重量份、甲基 丙烯酸縮水甘油酯60重量份、及苯乙烯10重量份，製造聚 合物溶液，得到固態部分的濃度為30重量％，重量平均分 21 200909536 子量為15,000之丙烯酸系共聚物之外，其餘以與前述實施 例1同一之方法實施，製造了有機保護膜組成物。 [化學式lb]X 20 0 In the above formula, X is CH3. Example 2 In the production of the acrylic copolymer of the above-mentioned Example 1, except 20 parts by weight of allyl methacrylate of the formula 20 200909536, 60 parts by weight of glycidyl methacrylate, and 20 parts by weight of styrene. An organic protective film composition was produced in the same manner as in the above Example 1 except that an acrylic copolymer having a solid content of 30% by weight and a weight average molecular weight of 15,000 was produced. Example 3 In the production of the acrylic copolymer of the above-mentioned Example 1, except that 10 parts by weight of allyl methacrylate, 60 parts by weight of glycidyl methacrylate, and 30 parts by weight of styrene, The organic protective film composition was produced in the same manner as in the above Example 1 except that the concentration was 10 30% by weight and the acrylic acid-based copolymer having a weight average molecular weight of 15,000 was used. Example 4 In the production of the acrylic acid copolymer of the above-mentioned Example 1, except for using 60 parts by weight of methyl acrylic acid allyl S and 40 parts by weight of styrene, a solid portion was produced. An organic protective film composition was produced in the same manner as in the above Example 1 except that the acrylic copolymer having a concentration of 30% by weight and a weight average molecular weight of 15,000 was used. Example 5 20 In the production of the acrylic copolymer of the foregoing Example 1, except that 10 parts by weight of 2,2-azobis(2,4-dimethylpentanenitrile) and 400 parts by weight of propylene glycol methyl ether acetate were used. 30 parts by weight of acryl allyl ester of the following chemical formula lb, 60 parts by weight of glycidyl methacrylate, and 10 parts by weight of styrene, and a polymer solution was obtained, and the concentration of the solid portion was 30% by weight, and the weight average score was 21 An organic protective film composition was produced in the same manner as in the above Example 1 except that the amount of the acrylic copolymer was 15,000. [Chemical Formula lb]
5 在上述式中，X為Η。 比較例1 在前述實施例1之丙烯酸系共聚物製造上，除了不使用 化學式la之甲基丙烯酸烯丙酯，而是以2,2 —偶氮雙(2,4 — 二甲基戊腈）1〇重量份、丙二醇甲醚乙酸酯400重量份、甲 10 基丙烯酸縮水甘油S旨60重量份、甲基丙浠酸甲S旨20重量 份、及苯乙烯20重量份，製造聚合物溶液，得到固態部分 的濃度為30重量％，且重量平均分子量為15,000之丙烯酸系 共聚物之外，其餘以與前述實施例1同一之方法實施，製造 了有機保護膜組成物。 15 比較例2 在前述實施例1之丙烯酸系共聚物製造上，除了不使用 化學式la之曱基丙烯酸烯丙酯，而是以2,2 —偶氮雙(2,4_ 二甲基戊腈）1〇重量份、丙二醇甲醚乙酸酯400重量份、曱 基丙烯酸縮水甘油ί旨60重量份、及苯乙稀40重量份，製造 20 聚合物溶液，得到固態部分的濃度為30重量％，且重量平 均分子量為15,000之丙烯酸系共聚物之外，其餘以與前述 實施例1同一之方法實施，製造了有機保護膜組成物。 22 200909536 利用前述實施例1至5及比較例1或2製造之有機保護模 組成物，以下述方法評價物性之後，將結果示於下述表丄。 (A) 耐熱性一對形成有保護膜之基板，在烤箱中以 。(：加熱2小時’進行TGA分析。TGA分析條件係一邊從常溫 5至9〇〇°C之間每分鐘昇溫2(TC，一邊測定Td值，進行評價。 (B) 耐化學性—使形成有保護膜之基板浸泡在丨％氟酸 (30°C、120秒）、剥離劑（7(rc、6〇〇秒）、顯影劑（4〇〇c、8〇 秒)之後，以超純水洗淨90秒至150秒，且使其乾燥。此時， 厚度的變化率是以前烘烤所得到之膜的厚度為基準， 10 〇〜10%時為優秀、10〜40%時為良好、超過40%時為不良。 再一追加評價是比較業經化學物質處理之基板與業經 前烘烤所得到之基板之昇華物發生程度。令前烘烤所得到 之基板之昇華物為1〇0%，換算業經各化學物質處理之基板 之昇華物量，進行評價。 15 透過前述表1，使用藉本發明含有稀丙基丙稀酸系化合 物製造之丙烯酸系共聚物之實施例⑴之Td值與比較例i 及2相較之下，得龍高之測定值，這顯示依烯两基作用基 20 =作狀附加性的交聯可大大促成賴性的提昇者。特別 是，實施例1至4和實施例5相比可知更具較高之⑽，料 具有更優異之耐熱性者。 23 200909536 [表2] (he ^ 實施例 比較例 1 2 3 4 5 1 2 耐 化 學 性 氟酸 優秀 優秀 優秀 良好 良好 不良 不良 剝離劑 優秀 優秀 良好 良好 優秀 不良 良好 顯影劑 優秀 優秀 優秀 優秀 優秀 良好 不良 透過前述表2,比較使用藉本發明含有烯丙基丙烯酸系 化合物製造之丙烯酸系共聚物之實施例1至5之厚度變化 5 時，與比較例1及2相較之下，顯示明顯優異之效果。 [表3] 實施例 比較例 1 2 3 4 5 1 2 财 化 學 性 氟酸 100% 99% 100% 99% 99% 93% 95% 剝離劑 100% 99% 99% 99% 99% 92% 99% 顯影劑 100% 100% 100% 99% 99% 98% 96% 透過前述表3，比較使用藉本發明含有烯丙基丙烯酸系 10 化合物製造之丙烯酸系共聚物之實施例1至5之昇華物含量 變化時，與比較例1及2相較之下，顯示明顯優異之效果。 【圖式簡單說明3 無 【主要元件符號說明】 無 245 In the above formula, X is Η. Comparative Example 1 In the production of the acrylic copolymer of the above Example 1, except that the allyl methacrylate was not used, but 2,2-azobis(2,4-dimethylvaleronitrile) was used. 1 part by weight, 400 parts by weight of propylene glycol methyl ether acetate, 60 parts by weight of methyl methacrylate glycosyl S, 20 parts by weight of methyl propyl phthalate, and 20 parts by weight of styrene to prepare a polymer solution An organic protective film composition was produced in the same manner as in the above Example 1 except that an acrylic copolymer having a solid content of 30% by weight and a weight average molecular weight of 15,000 was obtained. 15 Comparative Example 2 In the production of the acrylic copolymer of the above Example 1, except that the allyl mercapto acrylate was not used, but 2,2-azobis(2,4-dimethylvaleronitrile) was used. 1 part by weight, 400 parts by weight of propylene glycol methyl ether acetate, 60 parts by weight of glycidyl methacrylate, and 40 parts by weight of styrene, a 20 polymer solution was obtained, and the concentration of the solid portion was 30% by weight. An organic protective film composition was produced in the same manner as in the above Example 1 except that the acrylic copolymer having a weight average molecular weight of 15,000 was used. 22 200909536 Using the organic protective mold compositions manufactured in the above Examples 1 to 5 and Comparative Example 1 or 2, the physical properties were evaluated by the following methods, and the results are shown in the following Tables. (A) Heat resistant pair of substrates on which a protective film is formed, in an oven. TMA analysis was carried out by heating for 2 hours. The TGA analysis conditions were evaluated by measuring the Td value by heating 2 (TC) per minute from room temperature 5 to 9 ° C. (B) Chemical resistance - formation The substrate with the protective film is immersed in 丨% fluoric acid (30 ° C, 120 sec), stripper (7 (rc, 6 〇〇 seconds), developer (4 〇〇 c, 8 〇 seconds), super pure Washing with water for 90 seconds to 150 seconds, and drying it. At this time, the rate of change in thickness is based on the thickness of the film obtained by baking in the past, and is excellent when 10 〇 10 10%, and 10 10% is good. More than 40% is bad. Another additional evaluation is to compare the degree of sublimation of the substrate treated with the chemical substance and the substrate obtained by pre-baking. The sublimation of the substrate obtained by the prebaking is 1〇0. %, the amount of sublimation of the substrate treated with each chemical substance was converted and evaluated. 15 Through the above Table 1, the Td value of the example (1) of the acrylic copolymer produced by the present invention containing a propyl acrylate-based compound was used. Comparing the results of the comparison of the examples i and 2, the measured value of the sorghum, which shows the olefinic group 20 = the additional cross-linking can greatly contribute to the enhancer of the dependence. In particular, the examples 1 to 4 and the example 5 are known to have a higher (10) ratio, and are more excellent in heat resistance. 200909536 [Table 2] (he ^ Example Comparative Example 1 2 3 4 5 1 2 Chemical-resistant fluoric acid Excellent Excellent Excellent Good Good bad bad release agent Excellent Excellent Good Good Excellent Good Good Developer Excellent Excellent Excellent Excellent Excellent Good Bad In the above Table 2, when the thickness variation 5 of Examples 1 to 5 using the acrylic copolymer produced by the present invention containing the allyl acrylic compound was compared, the results were remarkably excellent as compared with Comparative Examples 1 and 2. [Table 3] Example Comparative Example 1 2 3 4 5 1 2 Chemically chemical hydrofluoric acid 100% 99% 100% 99% 99% 93% 95% Release agent 100% 99% 99% 99% 99% 92% 99 % Developer 100% 100% 100% 99% 99% 98% 96% By comparing the above-mentioned Table 3, the sublimates of Examples 1 to 5 using the acrylic copolymer produced by the present invention containing the allylacrylic 10 compound were compared. When the content changes, compared with Comparative Examples 1 and 2 Under more, show a significant effect of excellent. [Brief Description of the drawings The main element 3 None None REFERENCE SIGNS 24