200424776 玖、發明說明： 【發明所屬之技術領域】 本發明係關於一種用於感光性樹脂組成物’更詳細地 係半導體裝置、平面顯示器（FPD)等的製造，特別是使用於 半導體裝置及FPD等的層間絶緣膜或平坦化膜等的形成爲 適當地感光性樹脂組成物及該感光性樹脂組成物之FPD、 或使用於半導體裝置以及前記感光性樹脂組成物的耐熱性 薄膜之形成方法。 【先前技術】 LSI等的半導體積體電路、或FPD的顯示面之製造、熱 焙等的電路基板之製造等係開始使用於廣泛的領域，爲了 進行微細元件之形成或微細加工，係利用以往的微影術技 術。在微影術技術中，爲了形成光阻圖案係使用正型或負 型感光性樹脂組成物。近年來，此等感光性樹脂組成物的 新用途，如半導體積體電路或FPD等的層間絶緣膜或平坦 化膜之形成技術係受到注目。特別是對於FPD顯示面的高 精細化市場的期望強者，爲了達成該高精細化係需要透明 性高、絶緣性優異的平坦化膜係爲必須材料。關於使用於 此等用途的感光性樹脂組成物係有多數的硏究、專利出願 公開（參照例如：專利文獻1及2)。但是，其中記載的組成 物爲了使耐熱性變高交聯劑係爲必要，所以經時安定性惡 化、與使用於微細加工一般的正型光阻相比，組成物的保 存環境係需要特別注意。另外，FPD顯示面製作步驟中的 微影術’係利用重覆使用顯像液之再生顯像液。在該再生 顯像液中’薄膜電晶體（TFT)製作用正型光阻與含有上述交 200424776 聯劑之感光性樹脂組成物混合時，由於正型光阻與該組成 物中所含有的交聯劑進行反應，顯像液會有不溶的析出物 大量地發生的問題。發明者人等係針對具有鹼可溶性樹脂 及苯醌二疊氮基之感光劑、含有下述通式（I)所示之酚性化 合物及具有環氧基之硬化劑之感光性樹脂組成物進行檢討 (特願 200 1 -38960 1 號、特願 2002-5 1487號）。 [化4]200424776 发明 Description of the invention: [Technical field to which the invention belongs] The present invention relates to a method for manufacturing a photosensitive resin composition in more detail, such as the manufacture of semiconductor devices, flat panel displays (FPDs), and the like, and is particularly used in semiconductor devices and FPDs. The formation of an interlayer insulating film, a flattening film, or the like is an appropriate method for forming a photosensitive resin composition and the FPD of the photosensitive resin composition, or a heat-resistant film used in semiconductor devices and the photosensitive resin composition described above. [Prior art] Semiconductor integrated circuits such as LSIs, or the production of display substrates for FPDs, and the manufacture of circuit boards such as hot-baking, are beginning to be used in a wide range of fields. Lithography technique. In the lithography technique, a positive or negative photosensitive resin composition is used to form a photoresist pattern. In recent years, new applications of these photosensitive resin compositions, such as the formation of interlayer insulating films or planarizing films of semiconductor integrated circuits or FPDs, have attracted attention. In particular, in the high-definition market for FPD display surfaces, high-definition systems are required to achieve this high-definition system. A flattening film system having high transparency and excellent insulation is an essential material. There are many researches and patent publications concerning photosensitive resin compositions used for these applications (see, for example, Patent Documents 1 and 2). However, the composition described therein is necessary to increase the heat resistance of the cross-linking agent system. Therefore, the stability of the composition deteriorates with time. Compared with the positive photoresist used in microfabrication, special attention must be paid to the storage environment of the composition. . In addition, the lithography in the FPD display surface preparation step is a regenerating developing solution using a developing solution repeatedly. When the positive photoresist for the production of a thin film transistor (TFT) in the regenerating developing solution is mixed with the photosensitive resin composition containing the above-mentioned crosslink 200424776, the positive photoresist is mixed with the crosslink contained in the composition. When the reagent is reacted, a large amount of insoluble precipitates are generated in the developing solution. The inventors have performed a photosensitive resin composition containing an alkali-soluble resin and a benzoquinonediazide group, a photosensitive resin composition containing a phenolic compound represented by the following general formula (I), and a hardener having an epoxy group. Review (Japanese Patent No. 200 1 -38960, Japanese Patent No. 2002-5 1487). [Chemical 4]
(式中’ R〗、R2、R3、R4、R5、尺6及尺7係各自獨立地表示 H ' Cl-C4之烷基或下式所示之基， [化5](Wherein “R”, R2, R3, R4, R5, ruler 6 and ruler 7 each independently represent an alkyl group of H′Cl-C4 or a group represented by the following formula, [Chem. 5]
瓜及11係各自獨立地表示〇〜2之整數，a、b、c、d: 、g 及 h係滿足 a + b$5、c 十 d$5、e + f$5、g十 h$5之 〇〜5 的整數、i爲0〜2之整數）。 但是，關於層間絶緣膜、平坦化膜等中透明性、耐溶 齊!！ 1生等的要求，又感光性樹脂組成物的經時安定性的要 求’進一步提高時，係要求進一步改善現狀。 200424776 [專利文獻1 ] 特開平7-248629號公報 [專利文獻2] 特開平8-262709號公報 【發明內容】 [解決發明之課題] 有鑑於上述的狀況，本發明的目的係提供一種鹼可溶 性樹脂、感光劑、含有上述通式（I)所示之酚性化合物及具 有環氧基之硬化劑的感光性樹脂組成物、在高温烘乾後亦 可保持膜表面的平坦性、可形成具有低介電率且良好光透 過率的薄膜之感光性樹脂組成物。 又，本發明的目的係在上述感光性樹脂組成物中，提 供一種經時安定性改善的感光性樹脂組成物。. 另外，本發明的目的係在上述感光性樹脂組成物中， 提供一種耐溶劑性優異、可形成具有低介電率且良好光透 過率之薄膜的感光性樹脂組成物。 再者，本發明係提供一種具有由上述感光性樹脂組成 物所形成的層間絶緣膜或平坦化膜等之FPD或半導體元 件。 此外，本發明係提供一種使用上述感光性樹脂組成物 圖案化後，進行全面曝光、接者藉由後焙形成耐熱性薄膜 之方法。 [解決課題之手段] 本發明人們由進行專心一意的硏究、檢討的結果，在 含有具鹼可溶性樹脂及苯醌二疊氮基之感光劑的感光性樹 -10- 200424776 脂組成物中，鹼可溶性樹脂係使用不含有氰基之偶氮系聚 合起始劑或不含有氰基之偶氮系聚合起始劑與含有氰基之 偶氮系聚合起始劑所合成的樹脂，且由於進一步含有特定 的酚性化合物及具有環氧基之硬化劑，而可達成上述目 的，即經時安定性佳，又即使在例如220 °C、 1小時高温的 加熱處理後亦可保持膜表面的平坦性、而發現可得到顯示 良好光透過率、高耐溶劑性之感光性樹脂組成物，而達成 本發明者。 換言之，本發明係關於下述[1]〜[9]之感光性樹脂組成 物。 [1 ]一種感光性樹脂組成物，其係含有具鹼可溶性樹脂 及苯醌二疊氮基之感光劑之感光性樹脂組成物，其中鹼可 溶性樹脂係爲使用不含有氰基之偶氮系聚合起始劑所合成 1 · 的丙烯酸系樹脂，且含有上述通式（I)所示之酚性化合物及 具有環氧基之硬化劑。 [2] 如上述[1]之感光性樹脂組成物，其中該丙烯酸系樹 脂係使用含有氰基之偶氮系聚合起始劑、與含有氰基之偶 氮系聚合起始劑所合成的两烯酸系樹脂。 [3] 如上述[2]之感光性樹脂組成物，其中不含有氰墓之 偶氮系聚合起始劑與含有氰基之偶氮系聚合起始劑之莫耳 比爲 20:80 〜80:20。 [4] 如上述[1]〜[3]中任一項之感光性樹脂組成物，其 中丙烯酸系_脂係含有烷基（甲基）丙烯酸酯由來的構成單 位與（甲基）丙烯酸酸由來的構成單位。 [5] 如上述[1]〜[4]中任一項之感光性樹脂組成物，其 200424776 中丙烯酸系樹脂係含有5〜30莫耳％ (甲基）丙烯酸酸由來 的構成單位。 [6] 如上述[1]〜（5)中任一項之感光性樹脂組成物，其 中具有苯醌二疊氮基之感光劑係申請專利範圍第i項之通 式（I)所示之化合物與萘醌二疊氮化合物的反應生成物。 [7] 如上述[1]〜[6]中任一項之感光性樹脂組成物，其 中通式（I)所示之酚性化合物係爲下述式（II)所表示之化合 物。Gua and 11 are each independently an integer of 0 ~ 2, a, b, c, d :, g, and h are a + b $ 5, c ten d $ 5, e + f $ 5, and g ten h $ 5. An integer of 5 and i is an integer of 0 to 2). However, regarding the interlayer insulation film, the flattening film, etc., they are transparent and solvent-resistant! When the requirements of the raw materials, etc., and the requirements for the stability of the photosensitive resin composition over time are further increased, it is required to further improve the status quo. 200424776 [Patent Document 1] Japanese Patent Application Laid-Open No. 7-248629 [Patent Literature 2] Japanese Patent Application Laid-Open No. 8-262709 [Summary of the Invention] [Solving the Problems of the Invention] In view of the above-mentioned circumstances, an object of the present invention is to provide an alkali-soluble A resin, a photosensitizer, and a photosensitive resin composition containing a phenolic compound represented by the general formula (I) and a hardener having an epoxy group, which can maintain the flatness of the film surface even after high-temperature drying, and can form A photosensitive resin composition of a film having a low dielectric constant and a good light transmittance. An object of the present invention is to provide a photosensitive resin composition having improved stability over time in the photosensitive resin composition. In addition, an object of the present invention is to provide a photosensitive resin composition having excellent solvent resistance and capable of forming a thin film having a low dielectric constant and a good light transmittance in the photosensitive resin composition. The present invention also provides an FPD or a semiconductor device having an interlayer insulating film, a planarizing film, or the like formed of the photosensitive resin composition. In addition, the present invention provides a method for patterning using the above-mentioned photosensitive resin composition, performing full exposure, and then forming a heat-resistant film by post-baking. [Means for Solving the Problem] As a result of intensive research and review by the present inventors, in the photosensitive tree-10-200424776 lipid composition containing an alkali-soluble resin and a benzoquinonediazide-based photosensitizer, The alkali-soluble resin is a resin synthesized by using an azo-based polymerization initiator containing no cyano group or an azo-based polymerization initiator containing no cyano group and an azo-based polymerization initiator containing a cyano group. Contains specific phenolic compounds and hardeners with epoxy groups, which can achieve the above purpose, that is, it has good stability over time, and can maintain the flatness of the film surface even after heat treatment at 220 ° C for 1 hour The inventors have found that a photosensitive resin composition exhibiting good light transmittance and high solvent resistance can be obtained. In other words, the present invention relates to the photosensitive resin composition of the following [1] to [9]. [1] A photosensitive resin composition, which is a photosensitive resin composition containing a photosensitive agent having an alkali-soluble resin and a benzoquinonediazide group, wherein the alkali-soluble resin is an azo-based polymerization using no cyano group The acrylic resin synthesized by the initiator as 1 · contains a phenolic compound represented by the general formula (I) and a curing agent having an epoxy group. [2] The photosensitive resin composition according to the above [1], wherein the acrylic resin is a two-synthesizer synthesized using a cyano-containing azo-based polymerization initiator and a cyano-containing azo-based polymerization initiator. Enoic resin. [3] The photosensitive resin composition as described in the above [2], in which the molar ratio of the azo-based polymerization initiator containing no cyano gravy and the azo-based polymerization initiator containing cyano is 20:80 to 80 : 20. [4] The photosensitive resin composition according to any one of the above [1] to [3], wherein the acrylic-lipid system contains a constituent unit derived from an alkyl (meth) acrylate and a derived unit from (meth) acrylic acid Constituent units. [5] The photosensitive resin composition according to any one of [1] to [4] above, in 200424776, the acrylic resin contains 5 to 30 mole% (meth) acrylic acid as a constituent unit. [6] The photosensitive resin composition according to any one of the above [1] to (5), wherein the photosensitizer having a benzoquinonediazide group is the one represented by the general formula (I) in item i of the patent application scope. The reaction product of a compound and a naphthoquinonediazide compound. [7] The photosensitive resin composition according to any one of the above [1] to [6], wherein the phenolic compound represented by the general formula (I) is a compound represented by the following formula (II).
OHOH
[8]如上述[1]〜[7]中任一項之感光性樹脂組成物，其 中丙烯酸系樹脂的聚苯乙烯換算平均分子量爲5,000〜 30,000 ° [9 ]如上述[1 ]〜[8 ]中任一項之感光性樹脂組成物，其 中係更含有硬化促進劑。 又，本發明係亦關於以下的[10]記載之平面顯示器、[11] 記載之半導體裝置、[12]記載之耐熱性薄膜之形成方法。 [10] —種平面顯示器，其係含有由上述[1]〜[9]項中任 一項之感光性樹脂組成物形成的平坦化膜或層間絶緣膜。 [H] —種半導體裝置，其係含有由上述[1]〜[9]項中任 -12- 200424776 一項之感光性樹脂組成物形成的平坦化膜或層間絶緣 [12]—種耐熱性薄膜之形成方法，其係使用上述 [9]項中任一項之感光性樹脂組成物圖案化後、進行全 光、接者進行後焙。 以下，係進一步詳細地說明本發明。 本發明的感光性樹脂組成物含有具鹼可溶性樹月旨 醌二疊氮基之感光劑、鹼可溶性樹脂係使用不含有氰 偶氮系聚合起始劑或不含有氰基之偶氮系聚合起始劑 有氰基之偶氮系聚合起始劑所合成的丙烯酸系樹脂， 有上述通式（I)所示之酚性化合物及具有環氧基之硬化 爲必要。 在本發明的感光性樹脂組成物中所使用的鹼可溶 丙烯酸系樹脂，係於合成時使用，不含有氰基之偶氮 合起始劑可舉例如：1，1 ’ -偶氮雙（1 -乙醯氧基-1 -苯 烷）、1，1’-偶氮雙（1-丙醯氧基-1-苯基乙烷）、1，1’-偶氮 異丁醯氧基-1-苯基乙烷）、1，1’-偶氮雙（卜三甲基乙醯 •1-苯基乙烷）、1，1’-偶氮雙（1-乙醯氧基-1-苯基丙烷、 偶氮雙[1-乙醯氧基-1-(對甲基苯基）乙烷]、1，1’-偶氮 乙醯氧基-1·(對氯苯基）乙烷]、1，1，-偶氮雙（1-乙醯氧 苯基丁烷）、二甲基2,2’-偶氮雙（2-甲基丙酸酯）、1，1’· 雙（1-氯-卜苯基乙烷）、1，1’-偶氮雙（1-氯-1-丙烷）、1， 氮雙[1-氯-1-(對甲基苯基）乙烷]、1，1’-偶氮雙[1-氯-氯苯基）乙烷]、1，1、偶氮雙（卜氯-1-苯基丁烷）、2,2’· 雙（2-乙醯氧基- 3,3-二甲基丁烷）、2,2’-偶氮雙（2-乙醯 -4_甲基戊烷）、2,2’-偶氮雙（2-丙醯氧基-3,3-二甲基丁 膜。 [1]〜 面曝 與苯 基之 與含 又含 劑係 性之 系聚 基乙 雙（1-氧基 1，1，-雙[1-基-1 _ -偶氮 1，-偶 卜（對 •偶氮 氧基 院）、 -13- 200424776 2，2’-偶氮雙（2_丙醯氧基-4-甲基戊烷）、2,2’-偶氮雙（2_異丁 氧基-3,3-二甲基丁烷）、2,2’-偶氮雙（2-異丁氧基-4-甲基戊 烷）、2,2’-偶氮雙（2-三甲基乙醯氧基-3,3-二甲基丁烷）、 2,2’-偶氮雙（2-三甲基乙醯氧基-4-甲基戊烷）、2,2，-偶氮雙 (2-苯醯氧基-3,3-二甲基丁烷）、2,2’-偶氮雙（2-苯醯氧基-4-甲基戊烷）、2,2’-偶氮雙（2-乙醯氧基丙烷）、2,2’·偶氮雙（2-乙醯氧基丁烷）、2,2’·偶氮雙（2-乙醯氧基-3-甲基丁烷）、 2,2’-偶氮雙（2-丙醯氧基丙烷、2,2’-偶氮雙（2-丙醯氧基丁 烷）、2,2’·偶氮雙（2-丙醯氧基-3-甲基丙烷、2,2’-偶氮雙（2-異丁醯氧基丙烷、2,2’-偶氮雙（2-異丁醯氧基丁烷）、2,2，-偶氮雙（2 -異丁醯氧基-3-甲基丁烷）、2,2’-偶氮雙（2 -三甲基 乙醯氧基丙烷、2,2，-偶氮雙（2-三甲基乙醯氧基丁烷）、2,2，_ 偶氮雙（2-丙醯氧基-3-甲基丁烷）、2,2，·偶氮雙（2,4,4-三甲 基戊烷）、2,2’-偶氮雙（2-甲基丙烷、l，r-偶氮雙（1-甲氧基 環己烷）、2,2’-偶氮雙（2-甲基苯基丙醯脒基）二羥基氯、 2，2’-偶氮雙[Ν·(4-羥基苯基）-2-甲基丙醯脒基]二羥基氯、 2，2’-偶氮雙[2-甲基-N-(2-丙烯基）丙醯脒基]二羥基氯、 2,2’-偶氮雙[N-(2-羥基乙基甲基丙醯脒基]二羥基氯、 2，2’-偶氮雙[2-(5-甲基-2-咪唑啉-2-基）丙烷]二羥基氯、 2,2’-偶氮雙[2-(4,5,6,7-四氫-111-1，3-二吖庚因-2-基）丙烷] 二羥基氯、2,2’-偶氮雙[2-(5-羥基-3,4,5,6-四氫嘧啶-2-基） 丙烷]二羥基氯、2,2，-偶氮雙[N-(2-丙基）-2-甲基丙醯醯 胺、2,2、偶氮雙[2-(2-咪唑啉-0-基）丙烷]、2,2’-偶氮雙{2-甲基雙（羥基甲基）-2-羥基乙基}丙醯醯胺卜2，2，-偶氮雙 {2-甲基-N-[l，l-雙（羥基甲基）乙基]丙醯胺基卜2，2，-偶氮雙 -14- 200424776 [2-甲基-N-(2-羥基甲基）丙醯胺基]、2,2’-偶氮雙{2-甲基丙 醯胺基}二水合物等，較佳的聚合起始劑爲1，1’-偶氮雙（1-乙醯氧基-1-苯基乙烷）、1，1’-偶氮雙（1-丙醯氧基-1-苯基乙 烷）、1，1’-偶氮雙（1-異丁醯氧基-1-苯基乙烷）、1，1’-偶氮雙 (1-三甲基乙醯氧基-1-苯基乙烷）、1，1、偶氮雙（1-乙醯氧基 -1-苯基丙烷、1，1’-偶氮雙[1-乙醯氧基-1-(對甲基苯基）乙 烷]、1，1’-偶氮雙[1-乙醯氧基-1-(對氯苯基）乙烷]、1，1’-偶 氮雙（1-乙醯氧基-1-苯基丁烷）、二甲基2，2’-偶氮雙（2-甲基 丙酸酯）。 · 又，含有氰基之偶氮系聚合起始劑可舉例如1，1’-偶氮 雙（環己烷-1-腈）、2、2，-偶氮雙（2-甲基丁腈）、2、2，-偶氮 雙異丁腈、2、2，-偶氮雙（2,4-二甲基戊腈）、2、2，-偶氮雙 (2,4-二甲基-4-甲氧基戊腈）、二甲基2,2、偶氮雙（2-甲基丙 酸酯），較佳的聚合起始劑係有2、2，-偶氮雙異丁腈、二甲 基2，2’-偶氮雙（2-甲基丙酸酯）。又不含有氰基之偶氮系聚 合起始劑與含有氰基之偶氮系聚合起始劑之莫耳比係爲 100:0〜20:80。含有氰基之偶氮系聚合起始劑之莫耳比爲 φ 超過80莫耳％時，得到膜的光透過率係無法呈現出所期望 的透過率，且經時安定性亦有問題。聚合起始劑係倂用不 含有氰基之偶氮系聚合起始劑與含有氰基之偶氮系聚合起 始劑時’不含有氰基之偶氮系聚合起始劑與含有氰基之偶 氮系聚合起始劑之莫耳比係較佳爲20:80〜80:20、更佳爲 30:70 〜70:30 ° 製造本發明的感光性樹脂組成物中使用的驗可溶性丙 嫌酸系樹脂時，除了聚合起始劑以外的條件，從來習知的 -15- 200424776 條件均亦可使用。又，聚合法若爲從來習知的方法，係以 溶液聚合法爲佳方法。溶液聚合時所使用的聚合溶劑可舉 例如甲醇、乙醇等的醇類；四氫呋喃等的醚類；乙二醇單甲 基_、乙二醇二甲基醚、乙二醇單甲基乙基醚、乙二醇單 乙基醚等的醇醚類；乙二醇單甲基醚乙酸酯、乙二醇車乙基 醚乙酸酯等的乙二醇烷基醚乙酸酯類；二乙二醇單甲基 醚、二乙二醇二乙基醚、二乙二醇二甲基醚、二乙二醇乙 基甲基醚、二乙二醇單乙基醚、二乙二醇單丁基醚等的二 乙二醇類；丙二醇單甲基醚乙酸酯、丙二醇單乙基醚乙酸酯馨 等的丙二醇單烷基醚乙酸酯類；甲苯、二甲苯等的芳香族烴 類；甲基乙基酮、環己酮、4 -羥基_4_甲基-2-戊酮等的酮類；2-經基丙酸乙酯、2-羥基-2-甲基丙酸甲酯、2-羥基-2-甲基丙 酸乙酯、乙氧基乙酸乙酯、羥基乙酸乙酯、2_羥基甲基 丁烷酸甲酯、3 -甲氧基丙酸甲酯、3 -甲氧基丙酸乙酯、％ 乙氧基丙酸甲酯、3·乙氧基丙酸乙酯、乙酸乙酯、乙酸丁 酯等的酯類。此等之中、乙二醇二甲基醚等的醇醚類；乙二 醇單乙基醚乙酸酯等的乙二醇單烷基醚乙酸酯類；丙二醇 鲁 單甲基醚乙酸酯等的丙二醇單烷基醚乙酸酯類；2 -羥基丙 酸乙酯、3-甲氧基丙酸甲酯、3-乙氧基丙酸乙酯等的酯類； 一乙一醇二甲基醱等的二乙二醇類，從各單體的溶解性及 聚合反應時不會發生凝膠發生的觀點而言，以作爲溶劑爲 適當。在溶液聚合中，丙烯酸酸酯、甲基丙烯酸酯、其他 的聚合性單體係以適宜的濃度溶解於溶劑中，在該溶液中 添加聚合起始劑，以合適的温度進行聚合。 本發明的感光性樹脂組成物中所使用的鹼可溶性丙烯 -16- 200424776 酸系樹脂，可舉例如（a)鹼可溶性的聚丙烯酸酸酯、（b)鹼可 溶性的聚甲基丙烯酸酯、及（〇含有至少一種丙烯酸酸酯與 至少一種甲基丙烯酸酯爲構成單位的鹼可溶性之聚（丙烯 酸酸酯•甲基丙烯酸酯）。此等丙烯酸系樹脂係可單獨或二 種以上倂用。又，此等丙烯酸系樹脂由於樹脂爲鹼可溶性， 雖然其含有有機酸單體爲共聚合成分者爲佳，但是並不限 於賦予樹脂鹼可溶性之共聚合成分爲有機酸單體。 構成此等鹼可溶性的聚丙烯酸酸酯、聚甲基丙烯酸酯、 聚（丙烯酸酸酯·甲基丙烯酸酯）之單體成分，可舉例如丙 烯酸酸酯、甲基丙烯酸酯、有機酸單體及其他的共聚合性 單體。構成此等聚合物的單體成分係以下述例示的丙烯酸 酸酯、甲基丙烯酸酯、有機酸單體爲佳。 丙烯酸酸酯： 甲基丙烯酸酯、乙基丙烯酸酯、正丙基丙烯酸酯、正 丁基丙烯酸酯、正己基丙烯酸酯、異丙基丙烯酸酯、異丁 基丙烯酸酯、第三丁基丙烯酸酯、環己基丙烯酸酯、苯甲 基丙烯酸酯、2-氯乙基丙烯酸酯、甲基-氯丙烯酸酯、苯基 -α -溴丙烯酸酯等 甲基丙烯酸酯： 甲基甲基丙烯酸酯、乙基甲基丙烯酸酯、正丙基甲基 丙烯酸酯、正丁基甲基丙烯酸酯 '正己基甲基丙烯酸酯、 異丙基甲基丙烯酸酯、異丁基甲基丙烯酸酯、第三丁基甲 基丙烯酸酯、環己基甲基丙烯酸酯、苯甲基甲基丙烯酸酯、 苯基甲基丙烯酸酯、1-苯基乙基甲基丙烯酸酯、2-苯基乙 基甲基丙烯酸酯、糠基甲基丙烯酸酯、二苯基甲基甲基丙 -17- 200424776 烯酸酯、五氯苯基甲基丙烯酸酯、萘基甲基丙烯酸酯、異 佛爾酮基甲基丙烯酸酯、羥基乙基甲基丙烯酸酯、羥基丙 基甲基丙烯酸酯等 有機酸單體： 丙烯酸酸、申基丙烯酸、丁烯酸等的單羧酸、依康酸、 馬來酸、富馬酸、順式甲基丁烯二酸、中康酸等的二羧酸 及此等二羧酸的酐、2-丙烯醯基氫二烯鄰苯二甲酸酯、2-丙烯醯基羥基丙基氫二烯鄰苯二甲酸酯等 再者，其以外的共聚合性單體可舉例如馬來酸二酯、 鲁 富馬酸二酯、苯乙烯及苯乙烯衍生物、丙烯腈、（甲基）丙 烯酸醯胺基、乙酸乙烯酯、氯化乙烯、氯化亞乙烯酯等。 除了此等以外的共聚合性單體可視需要使用，其量即丙烯 酸系樹脂係使用達成本發明的目的範圍内的量。 本發明中作爲丙烯酸系樹脂，係較佳爲含有烷基（甲基） 丙烯酸酯由來的構成單位與（甲基）丙烯酸酸由來的構成單 位之共聚合物，更佳係含有5〜3 0莫耳％ (甲基）丙烯酸酸。 又，使用於本發明的感光性樹脂組成物、含有苯醌二 φ 疊氮基之感光劑，係含有苯醌二疊氮基之感光劑均可，但 是爲如萘醌二疊氮磺酸氯化物或苯并苯醌二疊氮磺酸氯化 物的苯醌二疊氮磺酸鹵化物時，藉由含有該酸鹵化物與可 縮合反應之官能基的低分子化合物或高分子化合物反應而 得到者爲佳。因此，酸鹵化物與可縮合的官能基係舉例如 羥基、胺基等，以羥基爲特別適當。含有羥基之低分子化 合物可舉例如上述通式（I)所不之酣性化合物。含有此等苯 醌二疊氮基之感光劑在本發明中，相對於感光性樹脂組成 -18- 200424776 物中樹脂成分100重量份，一般係以i〜30重量份的量使用。 又’本發明的感光性樹脂組成物係含有上述通式（I)所 示之酚性化合物。上述通式（.1)所示之具有酚性羥基之低分 子化合物，在調整本發明的感光性樹脂組成物中係爲了調 整一般溶解抑制劑之溶解速度、或爲了提昇感光性樹脂組 成物的殘膜率或感度的調整而適當的使用。 上述通式（I)所示之具有酚性羥基之低分子化合物可舉 例如0-甲酚、m-甲酣、P-甲酌、2,4-二甲苯酣、2,5_二甲苯 酚、2,6-二甲苯酚、雙酚A、B' C、E' F及G、4,4·，4，|-次籲 甲基三酚、2,6-雙[(2-經基甲基苯基）甲基]-4_甲基酣、 4.4, -[1_[4_[1-(4-羥基苯基）-1-甲基乙基]苯基]亞乙基]雙 酚、4,41^4-^-(4-羥基苯基）_2·丙基]苯基]亞乙基]雙 酚、4,4，，4"_次乙基三酚、4_[雙（4_經基苯基）甲基]_2·甲氧 基酚、4,4，-[(2·羥基苯基）伸甲基]雙[2,3·二甲基酌]、 4,4，-[(3-羥基苯基）伸甲基]雙[2,6_二甲基酌]、4,4M(4_經基 苯基）伸甲基]雙[2,6·二甲基酚]' 2,2 羥基本基）伸甲基] 雙[3,5-二甲基酚]、2,2，·[(4_經基苯基）伸甲基]雙[3,5_二甲鲁 基酚]' 4,4，-[(3,4-二羥基苯基）伸甲基]雙[2,3,6-三甲基 酚]、4-[雙（3-環己基-4·羥基-6_甲基苯基）甲基]-1，2-苯二 酚、4,6-雙[(3,5-二甲基-4-羥基苯基）甲基]-1，2,3·苯三酚、 4.4, -[(2-經基笨基）伸甲基]雙[3·甲基酣]、4,4，，4"·(3-甲基 小丙基_3_啶）三酚、4,4|，4，，，4，，|’-(1，4-亞苯二次甲基）四 酚、2,4,6-三[(3,5_二甲基_4-羥基苯基）甲基]-1，3·苯二酚、 2,4>三[(L-二甲基I經基苯基）甲基]-1，3-苯二酌' 4,4，-[卜羥基雙[(羥基_3-甲基苯基）甲基]苯 -19- 200424776 基]-1-甲基乙基]苯基]亞乙基]雙[2,6-雙（羥基-3-甲基苯基） 甲基]酚等。又較佳的化合物可舉例如4,4’，4"-次甲基三 酚、2,6 -雙[(2 -羥基-5-甲基苯基）甲基]-4-甲基酚、 4,4·-[1-[4-[1-(4-羥基苯基.）-1-甲基乙基]苯基]亞乙基]雙 酣、4,4’-[1-[4-[2-(4 -經基苯基）-2 -丙基]本基]亞乙墓]雙 酚、4,4’，4"-次乙基三酚等。 此等具有酚性羥基之低分子化合物之中’特別是以上 述式（II)所示之化合物或下述式（ΙΠ)所示之化合物爲佳。 [化 7] φ[8] The photosensitive resin composition according to any one of the above [1] to [7], wherein the polystyrene-equivalent average molecular weight of the acrylic resin is 5,000 to 30,000 ° [9] as described in [1] to [8] ] The photosensitive resin composition according to any one of the above, further comprising a hardening accelerator. The present invention also relates to a method for forming the flat display described in the following [10], the semiconductor device described in [11], and the heat-resistant film described in [12]. [10] A flat panel display comprising a flattening film or an interlayer insulating film formed from the photosensitive resin composition according to any one of the above [1] to [9]. [H] A semiconductor device containing a flattened film or interlayer insulation formed from the photosensitive resin composition of any one of the items [1] to [9] described above in [12] to 200424776 [12]-a type of heat resistance The method for forming a thin film is patterned using the photosensitive resin composition according to any one of the above [9], followed by full light, followed by post-baking. Hereinafter, the present invention will be described in more detail. The photosensitive resin composition of the present invention contains a photosensitizer having an alkali-soluble tree quinone diazide group, and the alkali-soluble resin is polymerized by using an cyano-azo-free polymerization initiator or an cyano-containing azo-based polymer. The initiator is an acrylic resin synthesized by a cyano-azo polymerization initiator, and it is necessary to have a phenolic compound represented by the general formula (I) and an epoxy group to harden. The alkali-soluble acrylic resin used in the photosensitive resin composition of the present invention is used at the time of synthesis, and examples of the azo-containing azo initiator without cyano group include, for example, 1,1′-azobis ( 1 -Ethyloxy-1 -phenane), 1,1'-azobis (1-propioxyl-1-phenylethane), 1,1'-azoisobutyryloxy- 1-phenylethane), 1,1'-azobis (butrimethylacetamidine1-1-phenylethane), 1,1'-azobis (1-ethylfluorenyloxy-1- Phenylpropane, azobis [1-ethylfluorenoxy-1- (p-methylphenyl) ethane], 1,1'-azoethylfluorenyloxy-1 · (p-chlorophenyl) ethane ], 1,1, -Azobis (1-acetamidophenylbutane), dimethyl2,2'-azobis (2-methylpropionate), 1,1 '· bis ( 1-chloro-phenylphenylethane), 1,1'-azobis (1-chloro-1-propane), 1, azabis [1-chloro-1- (p-methylphenyl) ethane] , 1,1'-azobis [1-chloro-chlorophenyl) ethane], 1,1, azobis (1-chloro-1-phenylbutane), 2,2 '· bis (2- Acetyloxy-3,3-dimethylbutane), 2,2'-azobis (2-acetamidine-4_methylpentane), 2,2'-even Nitrobis (2-propoxyl-3,3-dimethylbutyl film. [1] ~ Polyethylenebis (1-oxyl, 1, -bis [1-yl-1 _ -azo1, -azo (p-Azooxy), -13- 200424776 2,2'-azobis (2-propoxyl-4 -Methylpentane), 2,2'-azobis (2-isobutoxy-3,3-dimethylbutane), 2,2'-azobis (2-isobutoxy- 4-methylpentane), 2,2'-azobis (2-trimethylacetoxy-3,3-dimethylbutane), 2,2'-azobis (2-tri Methyl ethoxy-4-methylpentane), 2,2, -azobis (2-phenylfluorenoxy-3,3-dimethylbutane), 2,2'-azobis (2-Phenyloxy-4-methylpentane), 2,2'-Azobis (2-Ethyloxypropane), 2,2 '· Azobis (2-Ethyloxybutane) Alkane), 2,2 '· azobis (2-ethoxymethyl-3-methylbutane), 2,2'-azobis (2-propioxyloxypropane, 2,2'-couple Azobis (2-Propanyloxybutane), 2,2 '· Azobis (2-propioxyl-3-methylpropane, 2,2'-Azobis (2-isobutyrazine) Propane, 2,2'-azobis (2-isobutyl Oxybutane), 2,2, -azobis (2-isobutyryloxy-3-methylbutane), 2,2'-azobis (2-trimethylacetoxypropane) , 2,2, -Azobis (2-trimethylacetoxybutane), 2,2, _Azobis (2-propanyloxy-3-methylbutane), 2,2 ·· Azobis (2,4,4-trimethylpentane), 2,2'-azobis (2-methylpropane, 1, r-azobis (1-methoxycyclohexane ), 2,2'-azobis (2-methylphenylpropionyl) dihydroxy chloride, 2,2'-azobis [N · (4-hydroxyphenyl) -2-methylpropane Fluorenyl] dihydroxychloride, 2,2'-azobis [2-methyl-N- (2-propenyl) propanyl] dihydroxychloride, 2,2'-azobis [N- (2-hydroxyethylmethylpropanyl) dihydroxychloride, 2,2'-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydroxychloride, 2 , 2'-azobis [2- (4,5,6,7-tetrahydro-111-1,3-diazepine-2-yl) propane] dihydroxy chloride, 2,2'-azo Bis [2- (5-hydroxy-3,4,5,6-tetrahydropyrimidin-2-yl) propane] dihydroxy chloride, 2,2, -azobis [N- (2-propyl) -2 -Methylpropionamine, 2,2, azobis [2- (2-imidazolin-0-yl) propane ], 2,2'-azobis {2-methylbis (hydroxymethyl) -2-hydroxyethyl} propanilamine 2,2, -azobis {2-methyl-N- [ l, l-bis (hydroxymethyl) ethyl] propanamido 2,2, -azobis-14- 200424776 [2-methyl-N- (2-hydroxymethyl) propanamido] , 2,2'-azobis {2-methylpropanamido} dihydrate, and the like, and the preferred polymerization initiator is 1,1'-azobis (1-acetamidooxy-1- Phenyl ethane), 1,1'-azobis (1-propanyloxy-1-phenylethane), 1,1'-azobis (1-isobutylfluorenyloxy-1-benzene Ethane), 1,1'-azobis (1-trimethylethylfluorenoxy-1-phenylethane), 1,1, azobis (1-ethylfluorenoxy-1-benzene Propane, 1,1'-azobis [1-ethylfluorenyl-1- (p-methylphenyl) ethane], 1,1'-azobis [1-acetamyloxy-1- ((P-chlorophenyl) ethane), 1,1'-azobis (1-acetamido-1-phenylbutane), dimethyl 2,2'-azobis (2-methyl Propionate). · Examples of the azo-based polymerization initiator containing a cyano group include 1,1'-azobis (cyclohexane-1-nitrile), 2,2, -azobis (2-methylbutyronitrile) ), 2,2, -azobisisobutyronitrile, 2,2, -azobis (2,4-dimethylvaleronitrile), 2,2, -azobis (2,4-dimethyl -4-methoxyvaleronitrile), dimethyl 2,2, azobis (2-methylpropionate), and the preferred polymerization initiator is 2, 2, -azobisisobutyronitrile Dimethyl 2,2'-azobis (2-methylpropionate). The molar ratio of the azo-based polymerization initiator containing no cyano group and the azo-based polymerization initiator containing cyano group is 100: 0 to 20:80. When the molar ratio of the cyano-containing azo-based polymerization initiator is more than 80 mol%, the light transmittance of the obtained film cannot exhibit the desired transmittance, and stability over time is also problematic. When the polymerization initiator is used, an azo-based polymerization initiator containing no cyano group and an azo-based polymerization initiator containing cyano group are used. The molar ratio of the azo-based polymerization initiator is preferably 20:80 to 80:20, and more preferably 30:70 to 70: 30 °. The soluble acrylic resin used in the production of the photosensitive resin composition of the present invention In the case of acid resins, conditions other than the polymerization initiator may be used under conditions of -15-200424776, which are conventionally known. If the polymerization method is a conventional method, a solution polymerization method is preferred. Examples of the polymerization solvent used in the solution polymerization include alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, and ethylene glycol monomethyl ethyl ether And alcohol ethers such as ethylene glycol monoethyl ether; ethylene glycol monoether ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol ethyl ether acetate; diethylene glycol Alcohol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl Diethylene glycols such as ethers; propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; aromatic hydrocarbons such as toluene and xylene; Ketones such as ethyl ethyl ketone, cyclohexanone, 4-hydroxy_4-methyl-2-pentanone; ethyl 2-methylpropionate, methyl 2-hydroxy-2-methylpropionate, 2 -Ethyl hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxymethylbutanoate, methyl 3-methoxypropionate, 3-methoxy Ethyl propionate,% ethoxy propionate, 3 · ethoxy Esters propionate, ethyl acetate, butyl acetate and the like. Among these, alcohol ethers such as ethylene glycol dimethyl ether; ethylene glycol monoalkyl ether acetates such as ethylene glycol monoethyl ether acetate; propylene glycol monomethyl ether acetate Propylene glycol monoalkyl ether acetates, etc .; esters of ethyl 2-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate; etc. Diethylene glycol and the like are suitable as a solvent from the viewpoint of the solubility of each monomer and the occurrence of gelation during the polymerization reaction. In solution polymerization, acrylic acid ester, methacrylic acid ester, and other polymerizable single systems are dissolved in a solvent at an appropriate concentration, a polymerization initiator is added to the solution, and polymerization is performed at an appropriate temperature. Examples of the alkali-soluble propylene-16-200424776 acid-based resin used in the photosensitive resin composition of the present invention include (a) alkali-soluble polyacrylate, (b) alkali-soluble polymethacrylate, and (〇 Alkali-soluble poly (acrylate / methacrylate) containing at least one acrylate and at least one methacrylate as constituent units. These acrylic resins can be used alone or in combination of two or more. Since these acrylic resins are alkali soluble, although the organic acid monomers containing the copolymers are preferably copolymerized components, they are not limited to the copolymerizable components that impart alkali solubility to the resins as organic acid monomers. The monomer components of polyacrylate, polymethacrylate, poly (acrylate, methacrylate) include, for example, acrylate, methacrylate, organic acid monomer, and other copolymerizability Monomers. The monomer components constituting these polymers are preferably acrylate, methacrylate, or organic acid monomers as exemplified below. Acrylates: Acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, n-hexyl acrylate, isopropyl acrylate, isobutyl acrylate, third butyl acrylate, cyclohexyl acrylate, Methacrylates such as benzyl acrylate, 2-chloroethyl acrylate, meth-chloro acrylate, and phenyl-α-bromo acrylate: methyl methacrylate, ethyl methacrylate, n- Propyl methacrylate, n-butyl methacrylate 'n-hexyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, third butyl methacrylate, cyclohexyl methacrylate, benzyl Methyl methacrylate, phenyl methacrylate, 1-phenylethyl methacrylate, 2-phenylethyl methacrylate, furfuryl methacrylate, diphenylmethyl methacrylate -17- 200424776 enoate, pentachlorophenyl methacrylate, naphthyl methacrylate, isophorone methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, etc. Organic acid monomer Monocarboxylic acids such as acrylic acid, succinic acid, butenoic acid, dicarboxylic acids such as econic acid, maleic acid, fumaric acid, cis methylbutenedioic acid, mesaconic acid, and these dicarboxylic acids Acid anhydrides, 2-propenylhydrodiene phthalate, 2-propenylhydroxypropylhydrodiene phthalate and the like. Examples of other copolymerizable monomers include Such as maleic acid diester, roufumaric acid diester, styrene and styrene derivatives, acrylonitrile, amido (meth) acrylate, vinyl acetate, vinyl chloride, vinyl chloride, etc. Copolymerizable monomers other than these may be used as needed, and the amount thereof is an amount within the range of the purpose of the acrylic resin used in the present invention. As the acrylic resin in the present invention, it is preferable to contain an alkyl group (methyl). The copolymer of the constituent unit derived from acrylate and the constituent unit derived from (meth) acrylic acid preferably contains 5 to 30 mole% (meth) acrylic acid. In addition, the photosensitive resin composition used in the present invention and the sensitizer containing a benzoquinone diφazide group may be a sensitizer containing a benzoquinonediazide group, but it is, for example, naphthoquinonediazidesulfonic acid chloride. Compounds or benzoquinonediazidesulfonate halides are obtained by reacting low-molecular or high-molecular compounds containing the acid halide with a functional group capable of condensation reaction. Those are better. Therefore, examples of the acid halide and the condensable functional group include a hydroxyl group and an amino group, and a hydroxyl group is particularly suitable. Examples of the low-molecular-weight compound containing a hydroxyl group are exemplified by the above-mentioned general compounds (I). Photosensitizers containing these benzoquinonediazide groups are generally used in an amount of i to 30 parts by weight based on 100 parts by weight of the resin component in the photosensitive resin composition -18-200424776. Furthermore, the photosensitive resin composition of the present invention contains a phenolic compound represented by the general formula (I). The low-molecular-weight compound having a phenolic hydroxyl group represented by the general formula (.1) is used to adjust the dissolution rate of a general dissolution inhibitor in the adjustment of the photosensitive resin composition of the present invention, or to improve the solubility of the photosensitive resin composition. Adjust the residual film rate or sensitivity to use appropriately. Examples of the low-molecular-weight compound having a phenolic hydroxyl group represented by the general formula (I) include 0-cresol, m-formamidine, P-formaldehyde, 2,4-xylylenesulfonate, and 2,5-xylenol. , 2,6-xylenol, bisphenol A, B 'C, E' F and G, 4,4 ·, 4, | -hypomethyltriphenol, 2,6-bis [(2- mesogen Methylphenyl) methyl] -4-methylfluorene, 4.4,-[1_ [4_ [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylene] bisphenol, 4,41 ^ 4-^-(4-hydroxyphenyl) _2 · propyl] phenyl] ethylene] bisphenol, 4,4,, 4 " _ hypoethyltriphenol, 4_ [bis (4_ Transylphenyl) methyl] _2 · methoxyphenol, 4,4,-[(2 · hydroxyphenyl) methyl] bis [2,3 · dimethyl], 4,4,-[ (3-hydroxyphenyl) methyl] bis [2,6-dimethyl], 4,4M (4-methylphenyl) methyl] bis [2,6 · dimethylphenol] ' 2,2 hydroxybenzyl) methylene] bis [3,5-dimethylphenol], 2,2, [(4-methylphenyl) methylene] bis [3,5_dimethylol Phenol] '4,4,-[(3,4-dihydroxyphenyl) methyl] bis [2,3,6-trimethylphenol], 4- [bis (3-cyclohexyl-4 · Hydroxy-6-methylphenyl) methyl] -1,2-benzenediol, 4,6-bis [(3,5-dimethyl-4-hydroxyphenyl) Radical] -1,2,3 · pyroglycerol, 4.4,-[(2-terbenylbenzyl) methyl] bis [3 · methylfluorene], 4,4,, 4 " · (3-methyl Propyl small propyl_3_pyridine) triphenol, 4,4 |, 4 ,,, 4 ,, | '-(1,4-phenylene dimethylene) tetraphenol, 2,4,6-tris [ (3,5-Dimethyl_4-hydroxyphenyl) methyl] -1,3 · benzenediol, 2,4 > tris [(L-dimethylI-ylphenyl) methyl] -1 , 3-Benzodiazepine '4,4,-[[Hydroxybis [(hydroxy_3-methylphenyl) methyl] benzene-19-200424776yl] -1-methylethyl] phenyl] ethylene Group] bis [2,6-bis (hydroxy-3-methylphenyl) methyl] phenol and the like. Further preferred compounds include, for example, 4,4 ', 4 " -methinetriol, 2,6-bis [(2-hydroxy-5-methylphenyl) methyl] -4-methylphenol, 4,4 ·-[1- [4- [1- (4-hydroxyphenyl.)-1-methylethyl] phenyl] ethylene] bisfluorene, 4,4 '-[1- [4 -[2- (4- (Ethyl) phenyl) -2-propyl] benzyl] ethylene glycol] bisphenol, 4,4 ', 4 " -ethylidene triphenol and the like. Among these low-molecular compounds having a phenolic hydroxyl group, a compound represented by the above formula (II) or a compound represented by the following formula (II) is particularly preferred. [Chem 7] φ
OH OHOH OH
此等具有酚性羥基之低分子化合物，相對於鹼可溶性 樹脂1〇〇重量份，係以1〜20重量份之量使用。 本發明的感光性樹脂組成物係含有具環氧基之硬化 φ 劑。具有該環氧基之硬化劑可舉例如雙酚型環氧樹脂、甲 酚酚醛清漆型環氧樹脂、環狀脂肪族系環氧樹脂、縮水甘 油基醚系環氧樹脂、縮水甘油基胺系環氧樹脂、雜環式環 氧樹脂等。又若不使用上述高分子系環氧樹脂的話，本發 明所使用的硬化劑係亦可使用低分子系環氧化合物之雙酚 A或雙酚F之縮水甘油基醚等。具有環氧基之硬化劑，相對 於鹼可溶性樹脂100重量份，係以2〜60重量份爲佳、10〜 40重量份爲更佳。 -20- 200424776 又，本發明的感光性樹脂組成物進一步含有促進環氧 基與（甲基）丙烯酸酸的交聯反應之硬化促進劑爲佳。該硬 化促進劑可舉例如:SI-60L、SI-80L、SI-IOOL、SI-1 10L(以 上、三新化學工業股份有限公司製）等的芳香族鎏鹽、 U-CATSA102、U-CATSAI06、U-CATSA506、U-CATSA603、 U-CAT5002(以上係由三洋化成股份有限公司製）等的二氮 雜二環十一烯鹽、U-CAT5 00 3、U-CATI8X(以上係由三洋化 成股份有限公司製）。另外，咪唑系可舉例如挫阿做如 1B2PZ(四國化成工業股份有限公司製）。藉由將此等硬化促 0 進劑含有於本發明的感光性樹脂組成物中，可形成更耐溶 劑性優異的硬化膜，且同時可得到經時安定性亦優異的感 光性樹脂組成物。該硬化膜的耐溶劑性之改善於使用硬化 促進劑時，硬化劑的量亦可減少。又，硬化膜的耐溶劑性 之改善，鹼可溶性樹脂係比照單獨使用作爲聚合起始劑的 不含有氰基之偶氮系聚合起始劑時，可得到比倂用不含有 氰基之偶氮系聚合起始劑與含有氰基之偶氮系聚合起始劑 所合成的丙烯酸系樹脂的情形更好的結果。硬化促進劑相 對於具有環氧基之硬化劑1〇〇重量份，係以〇」〜“重量份 鲁 爲佳、1〜10重量份爲更佳。 溶解本發明的鹼可溶性樹脂、感光劑、具有酚性羥基 之化合物、具有環氧基之硬化劑之溶劑可舉例如乙二醇單 甲基醚、乙二醇單乙基醚等的乙二醇單烷基醚類、乙二醇 單甲基醚乙酸酯、乙二醇單乙基醚乙酸酯等的乙二醇單烷 基醚乙酸酯類、丙二醇單甲基醚、丙二醇單乙基醚等的丙 二醇單烷基醚類、丙二醇單甲基醚乙酸酯、丙二醇單乙基 醚乙酸酯等的丙二醇單烷基醚乙酸酯類、乳酸甲酯、乳酸 •21· 200424776 乙酯等的乳酸酯類，甲苯、二甲苯等的芳香族烴類、甲基 乙基酮、2 -庚酮、環己酮等的酮類，N，N -二甲基乙醯胺基、 正甲基吡咯啶酮等的醯胺基類、7-丁內酯等的內酯類等。 此等溶劑可單獨或2種以上混合使用。 本發明的感光性樹脂組成物可視薷要配合黏著助劑及 界面活性劑等。黏著助劑之例可舉例如烷基咪唑啉、酪酸、 烷基酸、聚羥基苯乙烯、聚乙烯甲基醚、第三丁基酚醛清 漆、乙氧基矽烷、乙氧基聚合物、矽烷等，界面活性劑之 例可舉例如非離子系界面活性劑、例如多元醇類及其衍生 0 物、換言之聚丙二醇或聚環氧乙烷月桂基醚、含氟界面活 性齊!ί、例如普羅拉多（商品名，住友3M社製）、梅卡法古（商 品名’大日本油墨化學工業股份有限公司製）、斯奴芙若（商 品名，旭硝子股份有限公司製）、或有機矽氧烷界面活性 劑、例如ΚΡ3 4 1 (商品名，信越化學工業股份有限公司製）。 本發明的感光性樹脂組成物，各成分係溶解於所定量 溶劑加以調製。此時，將各成分分別預先個別地溶劑溶解， 亦可使用之前各成分係以所定比例混合調製。通常感光性 樹脂組成物的溶液係使用〇·2// m的過濾器等濾過之後，供 翁 作使用。 本發明的感光性樹脂組成物係藉由如下列之方法，而 變成高絶緣性、高透明性、高耐熱性薄膜。因此，該薄膜 可作爲平坦膜或層間絶緣膜等而適當地利用。換言之、首 先本發明的感光性樹脂組成物之溶液，可視需要電路圖案 或半導體元件等係塗布至形成的基板上、進行預烘乾，以 形成感光性樹脂組成物之塗膜。接者，透過所定的裝照進 行圖案曝光後，使用鹼顯像液進行顯像處理，可視需要進 -22- 200424776 行清洗處理，以形成感光性樹脂組成物之薄膜正型圖案。 如此形成的薄膜正型圖案係於全面曝光後後焙，作爲半導 體元件或液晶表示裝置、電漿顯示器等的FPD的平坦化膜 或層間絶緣膜等利用。由此，可形成耐熱温度高的薄膜。 此時藉由全面曝光係認爲可使感光劑分解、形成酸、’促進 具有乙氧基之硬化劑的硬化，形成高耐熱性的被膜。 在上述薄膜之形成中，感光性樹脂組成物溶液之塗布 方法可使用旋塗法、輥塗法、接合塗布法、噴塗法、流延 塗布法、浸漬塗布法等任意之方法。又，曝光所使用的放 φ 射線可舉例如例如g線、i線等的紫外線、KrF準分子雷射光 或ArF準分子雷射光等的遠紫外線、X線、電子線等。另外， 顯像法係亦可依照攪拌顯像法、浸漬顯像法、揺動浸漬顯 像法等從來光阻的顯像法而使用的方法。又顯像劑可舉例 如氫氧化鈉、氫氧化鉀、碳酸鈉、矽酸鈉等的無機鹼、氨、 乙基胺、丙基胺、二乙基胺、二乙基胺乙醇、三乙基胺等 的有機胺、四甲基銨羥基酯等的第四級胺等。 【實施方式】 以下本發明係藉由實施例進一步説明，但是本發明的 鲁 態樣係不限定於此等實施例。 合成例1 在具備攪拌機、冷却管、温度計、氮氣導入管之2000ml 的4口燒瓶中，將丙二醇單甲基醚乙酸酯700克、甲基丙烯 酸甲基171克、甲基丙烯酸2 -羥基丙基90克、甲基丙烯酸39 克、二甲基2,2’-偶氮雙（2-甲基丙酸酯）[分子量：230.26]6·3 克、2,2’-偶氮雙異丁腈[分子量·· i 64.21 ]4·5克投入攪拌，邊 吹入氮氣邊昇温、於85 t下聚合8小時，可得到重量平均分 -23- 200424776 子量爲11，〇〇〇的丙嫌酸共聚物1。 合成例2 在具備攪拌機、冷却管、温度計、氮氣導入管之2000ml 的4口燒瓶中，將丙二醇單甲基醚乙酸酯7 00克、甲基丙烯 酸甲基171克、甲基丙烯酸2-羥基丙基9 0克、甲基丙烯酸39 克、二甲基2，2’-偶氮雙（2-甲基丙酸酯）12.6克投入攪拌，邊 吹入氮氣邊昇温、於85 °C下聚合8小時，可得到重量平均分 子量爲11，000的丙烯酸共聚物2。 合成例3 在具備攪拌機、冷却管、温度計、氮氣導入管之2000ml 的4口燒瓶中，將丙二醇單甲基醚乙酸酯7 00克、甲基丙烯 酸甲基171克、甲基丙烯酸2-羥基丙基9 0克、甲基丙烯酸39 克、2,2’-偶氮雙異丁腈9克投入攪拌，邊吹入氮氣邊昇温、 於85°C下聚合8小時，可得到重量平均分子量爲11，000的丙 烯酸共聚物3。 實施例1 將1〇〇重量份合成例1所得之丙烯酸共聚物1與上述式 (II)所示之化合物與1，2-萘醌二疊氮-5-磺醯氯之酯化物25 重量份、式（Π)所示之酚性化合物5重量份、德谷摸 VG3101L(三井化學股份有限公司製）20重量份、 U-C AT SA1 02 (三洋化成股份有限公司製）0.4重量份，溶解於 丙二醇單甲基醚乙酸酯/乳酸乙基（75/2 5)中，回轉塗布時光 阻膜上產生放射線狀的摺鈹、即爲了防止所謂的條痕 (striation)，又添加氟系界面活性劑、梅卡法古R-〇8(大日 本油墨化學工業股份有限公司製）3〇〇ppm，攪拌之後，以0·2 μ m的過濾器過濾，以調製本發明的感光性樹脂組成物1。 -24- 200424776 <薄膜圖案之形成> 將該組成物於4英吋矽晶片上回轉塗布，以100 °C、90 秒熱板烘乾後，得到3.0 // m厚的光阻膜。該光阻膜係以佳 能股份有限公司製g + h + i線光罩調整器（PLA-501F)調整線 與空白寬爲1 : 1所成的各種線寬及接觸孔的測試圖案以最 適曝光量曝光，以0.4重量％氫氧化四甲基銨水溶液在230 °C、經60秒間顯像，形成線與空白寬爲1:1的圖案及接觸 孔。又，所形成的圖案4英吋矽晶片以PLA-5 01F全面曝光 後，於烘箱中經220°C、60分鐘加熱以進行後焙處理。 | <透過率之評價> 除了使用7〇mmx70mm的石英玻璃基板以外，進行與上 述同樣的操作，得到具有薄膜圖案之玻璃基板。使用紫外-可視光分光光度計CARY4E(Barrian社製），測試具有該薄膜 圖案之玻璃基板的400η m透過率。結果如表1所示。 <耐溶劑性之評價> 進行與透過率之評價同樣的操作所得的玻璃基板，於 RemoverlOO(Client社製）中經800°C、1分鐘浸漬之後，進行 純粹清洗，進行200°C、15分鐘的再烘乾處理。溶劑浸漬前 · 的透過率與再烘乾處理後的透過率差低於3%者係評價爲 ◎、透過率差低於5%者評價爲〇、透過率差爲5 %以上者評 價爲X。結果如表1所示。 <經時安定性之評價> 組成物1於5°c、10天静置的光阻爲樣本A，於23°c、10 天静置的光阻爲樣本B。樣本A及樣本B係分別於4英吋矽晶 片上回轉塗布，lOOt、90秒間熱壓合且烘乾後，得到3.0 // m厚的光阻膜。該光阻膜係以佳能股份有限公司製g + h + i -25- 200424776 線光罩調整器（PL A-5 OIF)調整線與空白寬爲1:1的各種線 寬及接觸孔的測試圖案，係以最適曝光量進行曝光、以0.4 重量％氫氧化四甲基銨水溶液經23 °C、60秒間顯像，形成 線與空白寬爲1:1的圖案及接觸孔。顯像後的光阻膜厚除塗 布後的光阻膜厚之値，以百分率表示之値係定義爲殘膜 率，且用該殘膜率之値評價經時安定性。評價係樣本A與樣 本B的殘膜率之差低於3%者爲◎、低於3〜5%者爲〇、5以 上者爲X而進行。結果如表1所示。. 〈熱收縮性之評價〉 | 以22 0 °C、6 0分鐘後焙處理前後之膜厚進行測定，後焙 處理前的膜厚與處理後的膜厚差低於4000人者爲〇、膜厚差 爲4000A以上者爲X。結果如表1所示。 實施例2 除了丙烯酸共聚物1取代爲使用合成例2所得之丙烯酸 共聚物2以外，與實施例1同樣地進行，得到表1的結果。 實施例3 除了丙烯酸共聚物1取代爲使用合成例2所得之丙烯酸 共聚物2、德谷摸VG310I L(三井化學股份有限公司製）爲1〇 φ 重量份、不使用U-CATSA102(SAN-APR〇股份有限公司製） 以外，與實施例1同樣地進行，得到表1的結果。 比較例1 除了合成例1所得之丙烯酸共聚物1取代爲使用合成例 3所得之丙烯酸共聚物3以外，與實施例1同樣地進行、得到 _ 1的結果。 -26- 200424776 表1 透過率(％) 耐溶劑性 經時安定性 熱收縮性 實施例1 94.5 ◎ ◎ 〇 實施例2 96.7 ◎ ◎ 〇 實施例3 96.8 〇 ◎ 〇 比較例1 83.5 ◎ X 〇 根據以上之結果，已知在丙烯酸系樹脂的合成中，由 於聚合起始劑係使用不含有氰基之偶氮系聚合起始劑，可 形成透過率極佳的膜而得到感光性樹脂組成物。又，可知 聚合起始劑由於倂用不含有氰基之偶氮系聚合起始劑與含 有氰基之偶氮系聚合起始劑，可得到透過率、耐溶劑性、 經時安定性、耐熱性等的各種特性平衡佳且優異的感光性 樹脂組成物。 另外，藉由使用硬化促進劑可維持感光性樹脂組成物 的經時安定性，且可改善耐溶劑性。 又，由本發明的感光性樹脂組成物所形成的膜，在高 温烘乾後膜的平坦性及保持性係均爲良好，顯示低介電 率、可滿足TFT等的層間絶緣膜、平坦化膜等要求的絶緣性 之條件。 根據以上所述，本發明的感光性樹脂組成物係不僅透 明性良好、且各種特性亦爲優異，除了作爲光阻材料使用 之外，作爲特別是FPP、半導體元件等的層間絶緣膜、平 坦化膜等的元件係爲適當。 [發明的効果] -27- 200424776 由以上述，本發明的感光性樹脂組成物係具有後培後 的良好透明性，同時經時安定性優異、形成的膜之耐熱性、 耐溶劑性、絶緣性，且由於高温烘乾後膜表面的平坦性之 保持性亦爲優異，特別是作爲FPD、半導體元件等的平坦 化膜、層間絶緣膜等可適當地使用D ♦ 【圖式簡單說明】：無These low molecular compounds having a phenolic hydroxyl group are used in an amount of 1 to 20 parts by weight based on 100 parts by weight of the alkali-soluble resin. The photosensitive resin composition of the present invention contains an epoxy-based hardening φ agent. Examples of the curing agent having the epoxy group include bisphenol epoxy resin, cresol novolac epoxy resin, cyclic aliphatic epoxy resin, glycidyl ether epoxy resin, and glycidylamine epoxy resin. Epoxy resin, heterocyclic epoxy resin, etc. If the polymer-based epoxy resin is not used, the hardener used in the present invention may be bisphenol A or glycidyl ether of bisphenol F, which is a low-molecular epoxy compound. The hardening agent having an epoxy group is preferably 2 to 60 parts by weight, and more preferably 10 to 40 parts by weight based on 100 parts by weight of the alkali-soluble resin. -20-200424776 It is preferable that the photosensitive resin composition of the present invention further contains a hardening accelerator that accelerates the crosslinking reaction between the epoxy group and the (meth) acrylic acid. Examples of the hardening accelerator include: SI-60L, SI-80L, SI-IOOL, SI-1 10L (above, manufactured by Sanxin Chemical Industry Co., Ltd.), aromatic sulfonium salts, U-CATSA102, U-CATSAI06 , U-CATSA506, U-CATSA603, U-CAT5002 (the above are manufactured by Sanyo Chemical Co., Ltd.) and other diazabicycloundecene salts, U-CAT5 00 3, U-CATI8X (the above are manufactured by Sanyo Chemical Co., Ltd.). In addition, the imidazole system can be exemplified by 1A2PZ (made by Shikoku Chemical Industry Co., Ltd.). By containing such a hardening accelerator in the photosensitive resin composition of the present invention, a cured film having more excellent solvent resistance can be formed, and at the same time, a photosensitive resin composition having excellent stability over time can be obtained. The solvent resistance of this cured film is improved. When a hardening accelerator is used, the amount of the curing agent can be reduced. In addition, the solvent resistance of the cured film is improved. When an alkali-soluble resin is used alone as a polymerization initiator without an cyano-containing azo polymerization initiator, a cyano-containing azo-free resin can be obtained. A better result is obtained in the case of an acrylic resin synthesized with a cyano-based azo-based polymerization initiator and a polymerization initiator. The hardening accelerator is preferably 100% by weight relative to 100 parts by weight of the epoxy-based hardener, and more preferably 1 to 10 parts by weight. The alkali-soluble resin, photosensitizer, Examples of the solvent of the compound having a phenolic hydroxyl group and the hardener having an epoxy group include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, and ethylene glycol monomethyl ether. Ethyl glycol monoalkyl ether acetates such as ethylene ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol monoalkyl ethers, propylene glycol Propylene glycol monoalkyl ether acetates such as monomethyl ether acetate, propylene glycol monoethyl ether acetate, lactate esters such as methyl lactate, lactic acid • 21 · 200424776 ethyl esters, toluene, xylene, etc. Aromatic hydrocarbons, ketones such as methyl ethyl ketone, 2-heptanone, and cyclohexanone; amides such as N, N-dimethylacetamido, and n-methylpyrrolidone; 7 -Lactones such as butyrolactone, etc. These solvents may be used alone or as a mixture of two or more. The photosensitive resin composition of the present invention It may be necessary to add an adhesion aid and a surfactant. Examples of the adhesion aid include alkylimidazoline, butyric acid, alkyl acid, polyhydroxystyrene, polyvinyl methyl ether, third butyl novolac, Examples of the surfactant include ethoxysilane, ethoxy polymer, and silane. Examples of the surfactant include nonionic surfactants, such as polyols and derivatives thereof, in other words, polypropylene glycol or polyethylene lauryl. Ether, fluorine-containing interfacial activity! 例如, such as Prolado (trade name, manufactured by Sumitomo 3M), Mekafagu (trade name: Dainippon Ink Chemical Industry Co., Ltd.), Snuffro (trade name , Manufactured by Asahi Glass Co., Ltd.), or an organosiloxane surfactant such as PK3 4 1 (trade name, manufactured by Shin-Etsu Chemical Industry Co., Ltd.). In the photosensitive resin composition of the present invention, each component is dissolved in a predetermined amount. The solvent is prepared. In this case, each component is individually dissolved in advance in a solvent, and the components may be mixed and prepared at a predetermined ratio before use. Generally, a solution of the photosensitive resin composition is used. 〇 2 // m filter, etc., after filtration, for the use of Weng. The photosensitive resin composition of the present invention is made into a film with high insulation, high transparency and high heat resistance by the following method. This film can be suitably used as a flat film or an interlayer insulating film, etc. In other words, first, the solution of the photosensitive resin composition of the present invention may be coated on a formed substrate with a circuit pattern or a semiconductor element, if necessary, and pre-baked It is dried to form a coating film of the photosensitive resin composition. Then, after pattern exposure is performed through a predetermined photo, an alkali developing solution is used for development processing. If necessary, -22- 200424776 cleaning treatment is performed to form a photosensitive material. The positive pattern of the thin film of the resin composition. The positive pattern of the thin film formed in this manner is post-baked after full exposure, and is used as a flattening film or an interlayer insulating film for FPDs such as semiconductor elements, liquid crystal display devices, and plasma displays. Thereby, a thin film having a high heat-resistant temperature can be formed. At this time, it is thought that the photosensitizer can decompose, form an acid, and promote the hardening of the hardening agent having an ethoxy group by the full exposure system to form a film having high heat resistance. In the above-mentioned film formation, the photosensitive resin composition solution can be applied by any method such as a spin coating method, a roll coating method, a joint coating method, a spray coating method, a cast coating method, or a dip coating method. Examples of the radiation φ used for the exposure include ultraviolet rays such as g-line and i-line, far-ultraviolet rays such as KrF excimer laser light and ArF excimer laser light, X-rays, and electron rays. In addition, the development method may be a method using a non-photoresist development method such as a stirring development method, an immersion development method, or a immersion immersion development method. Examples of the developer include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, and sodium silicate, ammonia, ethylamine, propylamine, diethylamine, diethylamine ethanol, and triethyl. Organic amines such as amines, and tertiary amines such as tetramethylammonium hydroxyester. [Embodiment] The present invention is further described below by way of examples, but the system of the present invention is not limited to these examples. Synthesis Example 1 In a 2000 ml 4-necked flask equipped with a stirrer, a cooling tube, a thermometer, and a nitrogen introduction tube, 700 g of propylene glycol monomethyl ether acetate, 171 g of methacrylic acid, and 2-hydroxy methacrylic acid 90 grams of propyl, 39 grams of methacrylic acid, dimethyl 2,2'-azobis (2-methylpropionate) [Molecular weight: 230.26] 6.3 grams, 2,2'-azobisiso Nitrile [molecular weight · 64.21] 4.5 grams was put into stirring, and the temperature was raised while blowing nitrogen, and polymerization was performed at 85 t for 8 hours, and a weight average score of 23-200424776 was obtained. Propionic acid copolymer 1. Synthesis Example 2 In a 2000 ml 4-necked flask equipped with a stirrer, a cooling tube, a thermometer, and a nitrogen introduction tube, 7000 g of propylene glycol monomethyl ether acetate, 171 g of methacrylic acid, and 2-methacrylic acid 2- 90 grams of hydroxypropyl, 39 grams of methacrylic acid, and 12.6 grams of dimethyl 2,2'-azobis (2-methylpropionate) were stirred and heated at 85 ° C while blowing nitrogen gas. The polymerization was carried out for 8 hours to obtain an acrylic copolymer 2 having a weight average molecular weight of 11,000. Synthesis Example 3 In a 2000 ml 4-necked flask equipped with a stirrer, a cooling tube, a thermometer, and a nitrogen introduction tube, 700 g of propylene glycol monomethyl ether acetate, 171 g of methacrylic acid, and 2-methacrylic acid 2- 90 grams of hydroxypropyl, 39 grams of methacrylic acid, and 9 grams of 2,2'-azobisisobutyronitrile were put into agitation, heated while blowing nitrogen, and polymerized at 85 ° C for 8 hours to obtain a weight average. Acrylic copolymer 3 with a molecular weight of 11,000. Example 1 25 parts by weight of 100 parts by weight of an esterified product of the acrylic copolymer 1 obtained in Synthesis Example 1 with the compound represented by the above formula (II) and 1,2-naphthoquinonediazide-5-sulfonyl chloride 5 parts by weight of a phenolic compound represented by formula (Π), 20 parts by weight of Tokumo VG3101L (manufactured by Mitsui Chemicals Co., Ltd.), 0.4 parts by weight of UC AT SA1 02 (manufactured by Sanyo Chemical Co., Ltd.), and dissolved in propylene glycol In monomethyl ether acetate / ethyl lactate (75/2 5), a radial beryllium is generated on the photoresist film during spin coating, that is, a fluorine-based surfactant is added to prevent so-called striation. 2. Mercafagus R-〇8 (manufactured by Dainippon Ink Chemical Industry Co., Ltd.) at 300 ppm, and after stirring, it is filtered through a filter of 0.2 μm to prepare the photosensitive resin composition 1 of the present invention. . -24- 200424776 < Formation of thin film pattern > The composition was spin-coated on a 4-inch silicon wafer and dried at 100 ° C for 90 seconds on a hot plate to obtain a 3.0 // m thick photoresist film. The photoresist film is tested with various line widths and contact hole test patterns made by Canon's g + h + i-line photomask adjuster (PLA-501F) to adjust the line and blank width to 1: 1. After exposure to light, a 0.4 wt% tetramethylammonium hydroxide aqueous solution was developed at 230 ° C for 60 seconds to form a pattern with a line and space width of 1: 1 and contact holes. In addition, the patterned 4-inch silicon wafer was fully exposed with PLA-5 01F, and then heated in an oven at 220 ° C for 60 minutes for post-baking treatment. < Evaluation of transmittance > A glass substrate having a thin film pattern was obtained by performing the same operation as above except that a quartz glass substrate of 70 mm × 70 mm was used. A UV-visible spectrophotometer CARY4E (manufactured by Barrian) was used to measure the transmittance of 400 ηm of the glass substrate having the thin film pattern. The results are shown in Table 1. < Evaluation of solvent resistance > The glass substrate obtained by performing the same operation as the evaluation of the transmittance was immersed in Remover100 (manufactured by Client) for 1 minute at 800 ° C, followed by pure cleaning. 15 minutes of re-drying. The difference between the transmittance before solvent immersion and the transmittance after rebaking treatment is less than 3% is evaluated as ◎, the difference between transmittance is less than 5% is evaluated as 0, and the difference between transmittance is more than 5% is evaluated as X . The results are shown in Table 1. < Evaluation of stability over time > The photoresist of composition 1 standing at 5 ° C for 10 days is Sample A, and the photoresist standing at 23 ° C for 10 days is Sample B. Sample A and sample B were spin-coated on 4 inch silicon wafers respectively, and after heat pressing and drying at 100 t and 90 seconds, a 3.0 // m thick photoresist film was obtained. The photoresist film is tested with various line widths and contact holes of 1: 1 adjustment line and blank width of the line mask adjuster (PL A-5 OIF) made by Canon Co., Ltd. g + h + i -25- 200424776 The pattern was exposed at an optimum exposure amount and developed with a 0.4 wt% tetramethylammonium hydroxide aqueous solution at 23 ° C for 60 seconds to form a pattern with a line and space width of 1: 1 and contact holes. The thickness of the photoresist film after development is divided by the thickness of the photoresist film after coating, and the system expressed as a percentage is defined as the residual film rate, and the stability over time is evaluated using the residual film rate. The evaluation was performed when the difference between the residual film rate of sample A and sample B was less than 3%, ◎ was less than 3 to 5%, and 0 or more was X. The results are shown in Table 1. "Evaluation of heat shrinkability" | Measured at 22 ° C and 60 minutes after post-baking treatment. The difference between the film thickness before and after the post-baking treatment is less than 4,000. The film thickness difference is 4000A or more is X. The results are shown in Table 1. Example 2 The same procedure as in Example 1 was performed except that the acrylic copolymer 1 was replaced with the acrylic copolymer 2 obtained in Synthesis Example 2. The results in Table 1 were obtained. Example 3 Except that the acrylic copolymer 1 was replaced with the acrylic copolymer 2 obtained in Synthesis Example 2, Tokumo VG310I L (manufactured by Mitsui Chemicals Co., Ltd.) was 10 φ parts by weight, and U-CATSA102 (SAN-APR) was not used. 〇 Except for Co., Ltd.), the same procedure as in Example 1 was performed, and the results in Table 1 were obtained. Comparative Example 1 The same procedure as in Example 1 was performed except that the acrylic copolymer 1 obtained in Synthesis Example 1 was replaced with the acrylic copolymer 3 obtained in Synthesis Example 3, and a result of -1 was obtained. -26- 200424776 Table 1 Transmission rate (%) Solvent resistance Over time Stability Heat shrinkability Example 1 94.5 ◎ ◎ Example 2 96.7 ◎ ◎ Example 3 96.8 ○ ◎ 〇 Comparative Example 1 83.5 ◎ X 〇 According to From the above results, it is known that in the synthesis of an acrylic resin, a azo-based polymerization initiator not containing a cyano group is used as a polymerization initiator, and a film having excellent transmittance can be formed to obtain a photosensitive resin composition. In addition, it was found that since the polymerization initiator uses an azo-based polymerization initiator that does not contain a cyano group and an azo-based polymerization initiator that contains a cyano group, it can obtain transmittance, solvent resistance, stability over time, and heat resistance. Various photosensitive resin compositions having excellent balance of various properties such as properties. In addition, by using a hardening accelerator, the stability of the photosensitive resin composition over time can be maintained, and the solvent resistance can be improved. In addition, the film formed from the photosensitive resin composition of the present invention has good flatness and retention properties of the film after high-temperature drying, and exhibits a low dielectric constant, and can be an interlayer insulating film and a flattening film that can satisfy TFT and the like. And other required insulation conditions. As described above, the photosensitive resin composition system of the present invention is not only good in transparency but also excellent in various characteristics. In addition to being used as a photoresist material, it is particularly useful as an interlayer insulating film for FPP, semiconductor devices, and planarization. Elements such as a film are suitable. [Effects of the Invention] -27- 200424776 From the above, the photosensitive resin composition of the present invention has good transparency after post-cultivation, excellent stability over time, heat resistance of the formed film, solvent resistance, and insulation And because the flatness of the surface of the film after high temperature drying is also excellent, especially as flattening films for FPDs, semiconductor elements, interlayer insulation films, etc. D can be used appropriately ♦ [Schematic description]: no
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