用以實施發明之形態 本發明係有關一種負型光敏樹脂組成物，其包含鹼可溶性樹脂(A)、聚合性化合物(B)、3官能以上之多官能硫醇化合物(C)、光聚合起始劑(D)及溶劑(E)，而前述鹼可溶性樹脂(A)包含：包含化學式1所示之重複單位之第一樹脂，及包含化學式2所示之重複單位之第二樹脂；且前述第一樹脂與前述第二樹脂之混合重量比為50：50～90：10；於低溫硬化條件下，仍可形成反應性優良及耐久性優良的圖型。 ＜光敏樹脂組成物＞ 本發明係有關一種負型光敏樹脂組成物，其包含鹼可溶性樹脂(A)、聚合性化合物(B)、3官能以上之多官能硫醇化合物(C)、光聚合起始劑(D)及溶劑(E)。 鹼可溶性樹脂(A) 本發明所用之鹼可溶性樹脂(A)係對於形成圖型時之顯影處理步驟所用之鹼顯影液，賦予可溶性的成分，其包含：包含下述化學式1所示之重複單位之第一樹脂，及包含下述化學式2所示之重複單位之第二樹脂。 [化6] [化學式1][式中，R1
、R2
及R3
分別獨自為氫或甲基； R4
係來自從包括甲基丙烯酸、丙烯酸、2‒丙烯醯氧基丁二酸乙酯、2‒丙烯醯氧基乙基六氫化鄰苯二甲酸酯、2‒丙烯醯氧基乙基鄰苯二甲酸酯、及2‒甲基丙烯醯氧基丁二酸乙酯的群組中選擇之單體之構造； R5
係來自從包括下述式(1)～(9)的群組中選擇之單體之構造； [化7]R6
係來自從包括下述式(10)～(12)的群組中選擇之單體之構造； [化8]a=10～30mol%，b=30～60mol%，c=20～50mol%。] [化9] [化學式2][式中，R7
、R8
、R9
及R10
分別獨自為氫或甲基； R11
係來自從包括甲基丙烯酸、丙烯酸、2‒丙烯醯氧基丁二酸乙酯、2‒丙烯醯氧基乙基六氫化鄰苯二甲酸酯、2‒丙烯醯氧基乙基鄰苯二甲酸酯、及2‒甲基丙烯醯氧基丁二酸乙酯的群組中選擇之單體之構造； R12
係來自從包括甲基丙烯酸苄酯、苯氧基乙二醇丙烯酸酯、苯氧基二乙二醇丙烯酸酯、(2‒苯基)苯氧基乙氧基丙烯酸酯、2‒羥基‒(2‒苯基)苯酚丙烯酸丙酯、2‒羥基‒(3‒苯基)苯氧基丙烯酸丙酯、丙烯酸四氫呋喃酯、苯乙烯、乙烯基甲苯、乙烯基萘、N‒苄基順丁烯二醯亞胺、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲氧基乙二醇甲基丙烯酸酯、甲氧基二乙二醇甲基丙烯酸酯、甲氧基三乙二醇甲基丙烯酸酯、甲氧基四乙二醇甲基丙烯酸酯、苯氧基乙二醇甲基丙烯酸酯、苯氧基二乙二醇甲基丙烯酸酯、及甲基丙烯酸四氫呋喃酯的群組中選擇之單體之構造； R13
係來自從包括前述式(1)～(9)的群組中選擇之單體之構造； R14
係來自從包括下述式(13)～(19)的群組中選擇之單體之構造； [化10]d=10～30mol%，e=10～20mol%，f=30～60mol%，g=10～30mol%。] 於本發明，化學式1及2所示之各重複單位不得限定解釋如化學式1及2，括弧內之子重複單位可於決定之莫耳%範圍內，位於鏈中任何位置。亦即，化學式1及2之各括弧係為了表現莫耳%而以1個嵌段表示，但各子重複單位若是在符合的樹脂內，可不受限制而呈嵌段或其所在各自分離。 本發明之化學式1之化合物的較佳例可舉出下述化學式1‒1之化合物。 [化11] [化學式1‒1][式中，R1
、R2
、及R3
分別獨自為氫或甲基；a=10～30mol%，b=30～60mol%，c=20～50mol%。] 又，本發明之化學式2之化合物的較佳例可舉出下述化學式2‒1之化合物。 [化12] [化學式2‒1][式中，R7
、R8
、R9
及R10
分別獨自為氫或甲基；d=10～30mol%，e=10～20mol%，f=30～60mol%，g=10～30mol%。] 本發明之第一樹脂發揮改善光敏樹脂組成物之耐化學性及反應性的功能，就該方面而言，第一樹脂之重量平均分子量宜為6,000～12,000。於前述分子量範圍，可顯示最優良的反應性及耐化學性。 本發明之第二樹脂發揮改善光敏樹脂組成物之圖型形成性及耐熱性等耐久性的功能，就該方面而言，第二樹脂之重量平均分子量宜為20,000～30,000。於前述分子量範圍，可顯示最優良的圖型形成性及耐熱性等。 本發明之第一樹脂與前述第二樹脂之混合重量比為50：50～90：10，更宜為70：30～80：20。第一樹脂含量若少於第二樹脂含量，低溫硬化性降低，產生顯影後殘渣。第一樹脂含量若超過第二樹脂重量之9倍，則圖型形成性降低。 本發明之第一樹脂與第二樹脂除了分別獨自為化學式1及2之重複單位以外，可進一步包含由習知的其他單體形成之重複單位，可僅由化學式1之重複單位形成。 作為形成可進一步添加於化學式1及2之重複單位之單體並未特別限定，可舉出例如：巴豆酸等單羧酸類；反丁烯二酸、中康酸、衣康酸等二羧酸類及該等二羧酸之酐；ω羧酸聚己內酯單(甲基)丙烯酸酯等兩末端具有羧基及羥基之聚合物之單(甲基)丙烯酸酯類；乙烯基甲苯、對氯苯乙烯、鄰甲氧苯乙烯、間甲氧苯乙烯、對甲氧苯乙烯、鄰乙烯基苯甲醚、間乙烯基苯甲醚、對乙烯基苯甲醚、鄰乙烯基苯環氧丙基醚、間乙烯基苯環氧丙基醚、對乙烯基苯環氧丙基醚等芳族乙烯基化合物；N-環己基順丁烯二醯亞胺、N-苄基順丁烯二醯亞胺、N-苯基順丁烯二醯亞胺、N-鄰羥基苯基順丁烯二醯亞胺、N-間羥基苯基順丁烯二醯亞胺、N-對羥基苯基順丁烯二醯亞胺、N-鄰甲基苯基順丁烯二醯亞胺、N-間甲基苯基順丁烯二醯亞胺、N-對甲基苯基順丁烯二醯亞胺、N-鄰甲氧基苯基順丁烯二醯亞胺、N-間甲氧基苯基順丁烯二醯亞胺、N-對甲氧基苯基順丁烯二醯亞胺等N-取代順丁烯二醯亞胺系化合物；(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、正(甲基)丙烯酸丙酯、異(甲基)丙烯酸丙酯、正(甲基)丙烯酸丁酯、異(甲基)丙烯酸丁酯、二級(甲基)丙烯酸丁酯或三級(甲基)丙烯酸丁酯等(甲基)丙烯酸烷酯類；環(甲基)丙烯酸苄酯、2-甲基環(甲基)丙烯酸己酯、2-二環吩坦尼氧(甲基)丙烯酸乙酯等脂環族(甲基)丙烯酸酯類；(甲基)丙烯酸苯酯等(甲基)丙烯酸芳酯類；3-(甲基丙烯醯氧甲基)氧雜環丁烷、3-(甲基丙烯醯氧乙基)-3-乙基氧雜環丁烷、3-(甲基丙烯醯氧甲基)-2-三氟甲基氧雜環丁烷、3-(甲基丙烯醯氧甲基)-2-苯基氧雜環丁烷、2-(甲基丙烯醯氧甲基)氧雜環丁烷、2-(甲基丙烯醯氧乙基)-4-三氟甲基氧雜環丁烷等不飽和氧雜環丁烷化合物等；甲基(甲基)丙烯酸縮水甘油酯等不飽和環氧乙烷化合物；及被碳數4～16之環烷或二環烷取代的(甲基)丙烯酸酯等。該等可單獨使用或混合兩種以上使用。 鹼可溶性樹脂(A)之酸價宜在20～200(KOHmg/g)之範圍。酸價若在前述範圍內，可具有優良的顯影性及經時安定性。 鹼可溶性樹脂(A)之含量並未特別限定，例如以固體粉為基準，相對於光敏樹脂組成物全100質量部，亦可含10～90質量部，更宜含25～70質量部。若含前述數值範圍內時，由於對顯影液之溶解性充分，因此顯影性良好，可形成具有優良機械物性之光硬化圖型。 聚合性化合物(B) 本發明之光敏樹脂組成物所用之聚合性化合物(B)可使製造步驟中之架橋密度增加，強化光硬化圖型之機械特性。 聚合性化合物(B)可無特別限制地使用該領域所用之物，例如單官能單體、2官能單體及其他多官能單體，其種類並未特別限定，可舉出下述化合物作為其例。 單官能單體之具體例可舉出壬基苯基丙烯酸卡必酯、2-羥基-3-苯氧丙烯酸丙酯、2-乙基己基丙烯酸卡必酯、2-羥基丙烯酸乙酯、N-乙烯基砒喀烷酮等。2官能單體之具體例可舉出1,6–己二醯二(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、雙酚A之雙(丙烯醯氧乙基)醚、3-甲基戊烷二醇(甲基)丙烯酸酯等。其他多官能單體之具體例可舉出三羥甲基丙烷三(甲基)丙烯酸酯、乙氧基化(乙氧化)三羥甲基丙烷三(甲基)丙烯酸酯、丙氧基化(丙氧化)三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、乙氧基化(乙氧化)二季戊四醇六(甲基)丙烯酸酯、丙氧基化(丙氧化)二季戊四醇六(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯等。該等單體中，宜使用2官能以上之多官能單體。 前述聚合性化合物(B)之含量並未特別限定，例如以光敏樹脂組成物中之固形粉為基準，相對於鹼可溶性樹脂100重量部，以10～90質量部，更宜以30～80質量部的範圍來使用。聚合性化合物(B)包含前述含量的範圍時，可具有優良的耐久性，可提升組成物之顯影性。 多官能硫醇化合物(C) 本發明之3官能以上之多官能硫醇化合物為3官能以上之硫醇化合物，發揮使架橋密度提升，使光硬化圖型之耐久性及其與基材之密著性提升，防止高溫下之黃變現象的功能。 本發明之3官能以上之多官能硫醇化合物，若是3官能以上之硫醇化合物，且可用於光敏樹脂組成物之化合物均可，並未特別限定，宜為4官能以上硫醇化合物。本發明之硫醇化合物可表示於例如下述化學式3。 [化13] [化學式3][式中，Z1
為亞甲基或碳數2～10之直鏈或分支鏈之亞烷基或烷基亞甲基，Y為單結合、‒CO‒、‒O‒CO‒或‒NHCO‒，n為3～10之整數，X係可具有1個或複數個醚結合之碳數2～70之n價碳氫基，或者n為3，X為下述化學式4所示之3價基。] [化14] [化學式4][式中，Z2
、Z3
及Z4
分別獨自為亞甲基或碳數2～6之亞烷基，「*」表示共價鍵。] n宜為4以上，又較宜為4～10之整數，更宜為4、6或8。 n為3時之X可舉出例如下述化學式5所示之3價基，n為4、6或8時之X可分別舉出例如下述化學式6所示之4、6或8價基等較適宜。 [化15] [化學式5][式中，「*」表示共價鍵。] [化16] [化學式6][式中，m為0～2之整數，「*」表示共價鍵。] 本發明之多官能硫醇化合物(C)之含量並未特別限定，例如以光敏樹脂組成物中之固形粉為基準，相對於鹼可溶性樹脂100重量部，以0.1～15質量部，更宜以1～10質量部的範圍來使用。多官能硫醇化合物(C)包含前述含量的範圍時，可發揮優良的低溫硬化性能。 光聚合起始劑(D) 本發明之光聚合起始劑(D)若是可使前述聚合性化合物(B)聚合之物，可無特別限定其種類而使用，例如從包括苯乙酮系化合物、二苯甲酮系化合物、三嗪系化合物、聯咪唑系化合物、噻吨酮系化合物、及肟酯系化合物的群組中選擇之1種化合物，宜使用肟酯系化合物。 前述苯乙酮系化合物之具體例可舉出二乙氧基苯乙酮、2-羥基-2-甲基-1–苯基丙烷-1-酮、苄基二甲基縮酮、2-羥基-1-[4-(2-羥基乙氧)苯基]-2-甲基丙烷-1-酮、1–羥基環己基苯酮、2–甲基-1-(4-甲基硫苯基)-2-嗎啉丙烷–1–酮、2-苄基-2-二甲胺-1-(4–嗎啉苯基)丁烷–1–酮、2-羥基-2-甲基-1-[4-(1-甲基乙烯基)苯基]丙烷-1-酮、2-(4‒甲基苄基)-2-(二甲胺)-1-(4–嗎啉苯基)丁烷–1–酮等。 前述二苯甲酮系化合物之具體例可舉出二苯甲酮、鄰苯甲醯基苯酸甲基、4–苯基二苯甲酮、4–苯醯–4'–甲基二苯基硫化物、3,3',4,4'–四(三級丁基過氧羧基)二苯甲酮、2,4,6–三甲基二苯甲酮等。 前述三嗪系化合物之具體例可舉出2,4–雙(三氯甲基)–6–(4-甲氧苯基)‒1,3,5‒三嗪、2,4–雙(三氯甲基)–6–(4‒甲氧萘基)‒1,3,5‒三嗪、2,4–雙(三氯甲基)–6–胡椒基‒1,3,5‒三嗪、2,4–雙(三氯甲基)–6–(4‒甲氧苯乙烯基)‒1,3,5‒三嗪、2,4–雙(三氯甲基)–6–[2‒(5‒甲基呋喃‒2‒基)乙烯基]‒1,3,5‒三嗪、2,4–雙(三氯甲基)–6–[2‒呋喃‒2‒基)乙烯基]‒1,3,5‒三嗪、2,4–雙(三氯甲基)–6–[2‒(4‒二乙胺‒2‒甲基苯基)乙烯基]‒1,3,5‒三嗪、2,4–雙(三氯甲基)–6–[2‒(3,4‒二甲氧苯基)乙烯基]‒1,3,5‒三嗪等。 前述聯咪唑系化合物之具體例可舉出2,2'-雙(2-氯苯)-4,4',5,5'-四苯聯咪唑、2,2'-雙(2,3-二氯苯)-4,4',5,5'-四苯聯咪唑、2,2'-雙(2-氯苯)-4,4',5,5'-四(烷氧苯)聯咪唑、2,2'-雙(2-氯苯)-4,4',5,5'-四(三烷氧苯)聯咪唑、2,2'-雙(2,6-二氯苯)-4,4',5,5'-四苯‒1,2'‒聯咪唑或4,4',5,5'位置之苯基被羧烷氧基取代的聯咪唑化合物等，較適宜者可舉出2,2'-雙(2-氯苯)-4,4',5,5'-四苯聯咪唑、2,2'-雙(2,3-二氯苯)-4,4',5,5'-四苯聯咪唑、2,2'-雙(2,6-二氯苯)-4,4',5,5'-四苯‒1,2'‒聯咪唑等。 前述噻吨酮系化合物之具體例可舉出2-異丙基噻噸酮、2,4–二乙基噻噸酮、2,4-二氯噻噸酮、1-氯-4-丙氧噻噸酮等。 前述肟酯系化合物之具體例可舉出鄰乙氧羧基-a-肟基-1-苯丙烷-1-酮、1,2‒辛二烯‒1‒(4‒苯硫)苯基‒2‒(鄰苯甲醯基)肟、乙酮‒1‒(9‒乙基)‒6‒(2‒甲基苯甲醯基‒3‒基)‒1‒(鄰乙醯肟)等；市售品包括CGI-124(Ciba‒Geigy)、CGI-224(Ciba‒Geigy)、Irgacure OXE-01(BASF)、Irgacure OXE-02(BASF)、N-1919(ADEKA)、NCI-831(ADEKA)等。 又，前述光聚合起始劑(D)為了使本發明之光敏樹脂組成物的感度提升，亦可進一步包含光聚合起始助劑。本發明之光敏樹脂組成物藉由包含光聚合起始助劑，感度進一步升高，可提升生產性。 前述光聚合起始助劑可舉出從包括胺化合物、羧酸化合物、及具有硫醇基之有機硫化合物的群組中選擇之1種以上的化合物。 前述胺化合物之具體例可舉出三乙基醇胺、甲基二乙醇胺、三異丙醇胺等脂肪族胺化合物、4-二甲基胺基苯甲酸甲基、4-二甲基胺基苯甲酸乙基、4-二甲基胺基苯甲酸異戊基、4-二甲基胺基苯甲酸‒2-乙基己基、苯甲酸(2-二甲基胺基)乙基、N,N-二甲基對甲苯胺、4,4'-雙(二甲基胺基)二苯甲酮(通稱：米其勒酮)、4,4'-雙(二乙基胺基)二苯甲酮等，宜使用芳族胺化合物。 前述羧酸化合物之具體例宜為芳族雜醋酸類，可舉出例如苯硫醋酸、甲基苯硫醋酸、乙基苯硫醋酸、甲基乙基苯硫醋酸、二甲基苯硫醋酸、甲氧苯硫醋酸、二甲氧苯硫醋酸、氯苯硫醋酸、二氯苯硫醋酸、N-苯甘胺酸、苯氧醋酸、萘硫醋酸、N-萘甘胺酸、萘氧醋酸等。 前述具有硫醇基之有機硫化合物之具體例可舉出2-巰基苯并噻唑、1,4-雙(3-巰基丁酸乙酯)丁烷、1,3,5-三(3-巰基丁酸乙酯)-1,3,5-三嗪-2,4,6(1H,3H,5H)-三酮、三羥甲基丙烷三(3–巰基丙酯)、新戊四醇肆(3–巰基丁酯)、新戊四醇肆(3–巰基丙酯)、二新戊四醇肆(3–巰基丙酯)、四乙二醇雙(3–巰基丙酯)等。 前述光聚合起始劑(D)之含量並未特別限定，例如以固體粉為基準，相對於光敏樹脂組成物全體100質量部，亦可含0.1～10質量部，更宜含0.1～5質量部的量。符合前述數值範圍時，由於光敏樹脂組成物之高感度化，曝光時間縮短，因此生產性提升，可維持高解像度，所形成的像素部之強度及像素度表面之平滑性良好，故較適宜。 溶劑(E) 溶劑(E)若是該領域一般所用之物，可無限制地使用任何溶劑。 前述溶劑之具體例可舉出：如乙二醇單甲醚、乙二醇單乙醚、乙二醇單丙醚及乙二醇單丁醚之乙二醇單烷醚類；二乙二醇二甲醚、二乙二醇二乙醚、二乙二醇二丙醚、二乙二醇二丁醚等二乙二醇二烷醚類；甲基賽路蘇乙酸酯、乙基賽路蘇乙酸酯、乙二醇單丁醚乙酸酯等乙二醇烷醚乙酸酯類；丙二醇單甲醚乙酸酯、丙二醇單乙醚乙酸酯、丙二醇單丙醚乙酸酯、甲氧丁基乙酸酯、甲氧苄基乙酸酯等亞烷基二醇烷醚乙酸酯類；丙二醇單甲醚、丙二醇單乙醚、丙二醇單丙醚、丙二醇單丁醚等丙二醇單烷醚類；丙二醇二甲醚、丙二醇二乙醚、丙二醇二丙醚、丙二醇丙基甲醚、丙二醇乙基丙醚等丙二醇二烷醚類；丙二醇甲醚丙酸酯、丙二醇乙醚丙酸酯、丙二醇丙醚丙酸酯、丙二醇丁醚丙酸酯等丙二醇烷醚丙酸酯類；甲氧丁醇、乙氧丁醇、丙氧丁醇、丁氧丁醇等丁二醇單烷醚類；甲氧丁基乙酸酯、乙氧丁基乙酸酯、丙氧丁基乙酸酯、丁氧丁基乙酸酯等丁二醇單烷醚乙酸酯類；甲氧丁基丙酸酯、乙氧丁基丙酸酯、丙氧丁基丙酸酯、丁氧丁基丙酸酯等丁二醇單烷醚丙酸酯類；二丙二醇二甲醚、二丙二醇二乙醚、二丙二醇甲基乙醚等二丙二醇二烷醚類；苯、甲苯、二甲苯、三甲苯等芳族碳化氫類；甲基乙酮、丙酮、甲基胺酮、甲基異丁酮、環己酮等酮類；乙醇、丙醇、丁醇、己醇、環己醇、乙二醇、甘油等醇類；醋酸甲基、醋酸乙基、醋酸丙基、醋酸丁基、2-羥基丙酸乙基、2-羥基-2-甲基丙酸甲基、2-羥基-2-甲基丙酸乙基、羥基醋酸乙基、羥基醋酸乙基、羥基醋酸丁基、乳酸乙基、乳酸丙基、乳酸丁基、3-羥基丙酸甲基、3-羥基丙酸乙基、3-羥基丙酸丙基、3-羥基丙酸丁基、2-羥基-3-甲基丙酸甲基、甲氧醋酸乙基、甲氧醋酸丙基、甲氧醋酸丁基、乙氧醋酸甲基、乙氧醋酸乙基、乙氧醋酸丙基、乙氧醋酸丁基、丙氧醋酸甲基、丙氧醋酸乙基、丙氧醋酸丙基、丙氧醋酸丁基、丁氧醋酸甲基、丁氧醋酸乙基、丁氧醋酸丙基、丁氧醋酸丁基、2-甲氧丙酸甲基、2-甲氧丙酸乙基、2-甲氧丙酸丙基、2-甲氧丙酸丁基、2-乙氧丙酸甲基、2-乙氧丙酸乙基、2-乙氧丙酸丙基、2-乙氧丙酸丁基、2-丁氧丙酸甲基、2-丁氧丙酸乙基、2-丁氧丙酸丙基、2-丁氧丙酸丁基、3-甲氧丙酸甲基、3-甲氧丙酸乙基、3-甲氧丙酸丙基、3-甲氧丙酸丁基、3-乙氧丙酸甲基、3-乙氧丙酸乙基、3-乙氧丙酸丙基、3-乙氧丙酸丁基、3-丙氧丙酸甲基、3-丙氧丙酸乙基、3-丙氧丙酸丙基、3-丙氧丙酸丁基、3-丁氧丙酸甲基、3-丁氧丙酸乙基、3-丁氧丙酸丙基、3-丁氧丙酸丁基等酯類；四氫呋喃、哌喃等環狀醚類；g-丁內酯等環狀酯類等。在此列舉之溶劑可分別單獨使用，或混合兩種以上使用。 前述溶劑在考慮到塗佈性及乾燥性時，宜使用亞烷基二醇烷醚乙酸酯類、酮類、丁二醇烷醚乙酸酯類、丁二醇單烷醚類、3-乙氧丙酸乙基、3-甲氧丙酸乙基等酯類，進而宜使用丙二醇單甲醚乙酸酯、丙二醇單乙醚乙酸酯、環己酮、甲氧丁基乙酸酯、甲氧丁醇、3-乙氧丙酸乙基、3-甲氧丙酸甲基等。 前述溶劑(E)之含量係相對於光敏樹脂組成物全體100質量部，亦可含40～95質量部，更宜含45～85質量部的量。符合前述範圍時，以旋轉塗佈機、狹縫與旋轉塗佈機、狹縫塗佈機(有時亦稱為「模塗佈機」、「淋幕式塗佈機」)、噴墨等塗佈裝置塗佈時，塗佈性變佳，故較適宜。 添加劑(F) 本發明之光敏樹脂組成物亦可因應需要，進一步包含填充劑、其他高分子化合物、硬化劑、均染劑、密著促進劑、抗氧化劑、紫外線吸收劑、凝集防止劑、鏈轉移劑等添加劑。 前述填充劑之具體例可舉出玻璃、氧化矽、氧化鋁等。 前述其他高分子化合物之具體例可舉出：環氧樹脂、順丁烯二醯亞胺樹脂等硬化性樹脂；及聚乙烯醇、聚丙烯酸、聚乙二醇單烷醚、聚氟丙烯酸烷酯、聚酯、聚氨酯等熱塑性樹脂等。 前述硬化劑是為了提高深部硬化及機械性強度而使用，硬化劑之具體例可舉出環氧化合物、多官能異氰酸酯化合物、三聚氰胺化合物、氧雜環丁烷化合物等。 前述硬化劑之環氧化合物之具體例可舉出雙酚A系環氧樹脂、溴化雙酚A系環氧樹脂、雙酚F系環氧樹脂、溴化雙酚F系環氧樹脂、酚醛型環氧樹脂、其他芳族系環氧樹脂、脂環族系環氧樹脂、縮水甘油酯系樹脂、縮水甘油胺系樹脂，又可舉出該類環氧樹脂之溴化衍生物、環氧樹脂及其溴化衍生物以外之脂肪族、脂環族或芳族環氧化合物、丁二烯(共)聚合物環氧化合物、異戊二烯(共)聚合物環氧化合物、縮水甘油基(甲基)丙烯酸酯(共)聚合物、三縮水甘油基異氰脲酸酯等。 前述硬化劑之氧雜環丁烷化合物之具體例可舉出碳酸酯雙氧雜環丁烷、二甲苯雙氧雜環丁烷、己二酸雙氧雜環丁烷、對苯二甲酸酯雙氧雜環丁烷、環己烷二羧酸雙氧雜環丁烷等。 前述硬化劑可將可使環氧化合物之環氧基、氧雜環丁烷化合物之氧雜環丁烷骨架進行開環聚合之硬化輔助化合物，與該硬化劑併用。前述硬化輔助化合物可舉出例如多價羧酸類、多價羧酸酐類、酸產生劑等。 前述羧酸酐類可利用作為環氧樹脂硬化劑市售之物。前述環氧樹脂硬化劑可舉出例如商品名ADEKA HARDENER EH-700(ADEKA工業股份有限公司製)、商品名RIKACID HH(新日本理化股份有限公司製)、商品名MH-700(新日本理化股份有限公司製)等。前述例示之硬化劑可單獨使用，或混合兩種以上使用。 前述均染劑可使用市售之界面活性劑，可舉出例如矽基系、氟素系、酯系、陽離子系、陰離子系、非離子系、雙性等之界面活性劑等；該等界面活性劑可分別單獨使用，或組合兩種以上使用。 前述界面活性劑除了例如聚氧乙烯烷醚類、聚氧乙烯烷基苯醚類、聚乙二醇二酯類、山梨糖醇酐脂肪酸酯類、脂肪酸改質聚酯類、三級胺改質聚氨酯類、聚乙烯亞胺類等以外，以商品名還可舉出KP(信越化學工業股份有限公司製)、POLYFLOW(共榮化學股份有限公司製)、EFTOP (Tohkem Products製)、MEGAFAC (DAINIPPON INK AND CHEMICALS製)、Flourad (Sumitomo 3M製)、Asahi guard、Surflon(以上為旭硝子製)、SOLSPERSE (Zeneca製)、EFKA(EFKA CHEMICALS製)、PB821(Ajinomoto股份有限公司製)等。 前述密著促進劑宜為矽烷系化合物，具體而言可舉出乙烯三甲氧基矽烷、乙烯三乙氧基矽烷、乙烯三(2–甲氧基乙氧基)矽烷、N–(2–胺乙基)–3–胺丙基甲基二甲氧基矽烷、N–(2–胺乙基)–3–胺丙基三甲氧基矽烷、3–胺丙基三乙氧基矽烷、3–環氧丙氧基丙基三甲氧基矽烷、3–環氧丙氧基丙基甲基二甲氧基矽烷、2–(3,4–環氧環己基)乙基三甲氧基矽烷、3–氯丙基甲基三甲氧基矽烷、3–氯丙基三甲氧基矽烷、3–甲基丙烯酸酯丙基三甲氧基矽烷、3–巰基丙基三甲氧基矽烷等。 前述抗氧化劑具體而言可舉出2-三級丁基-6- (3-三級丁基-2-羥基-5-甲基苄基)-4-甲基丙烯酸苯酯、2- [-1- (2-羥基-3,5-二-三級戊基苯基)乙基] -4,6-二-三級戊基丙烯酸苯酯、6- [3- (3-三級丁基-4-羥基-5-甲基苯基)丙氧基] -2,4,8,10-四-三級丁基二苯[d,f][1,3,2]二噁磷雜更環、3,9-雙[2-{3- (3-三級丁基-4-羥基-5-甲基苯基)丙醯氧}-1,1-二甲基乙基] -2,4,8,10-四氧雜螺[5,5]十一烷、2,2'-亞甲雙(6-三級丁基-4-甲基苯酚基)、4,4'-亞丁基雙(6-三級丁基-3-甲基苯酚基)、4,4'-硫雙(2-三級丁基-5-甲基苯酚基)、2,2'-硫雙(6-三級丁基-4-甲基苯酚基)、二月桂基‒3,3'-硫二丙酸酯、二十四基‒3,3'-硫二丙酸酯、二硬脂基‒3,3'-硫二丙酸酯、新戊四醇肆(3-月桂基硫丙酸酯)、1,3,5-三(3,5-二-三級丁基-4-羥基苄基)-1,3,5-三嗪-2,4,6(1H,3H,5H)-三酮、3,3',3'',5,5',5''-六-三級丁基-a,a',a''- (三甲苯-2,4,6-三基)三-對甲酚、新戊四醇肆[3- (3,5-二-三級丁基-4-羥基苯基)丙酸酯]、2,6-二-三級丁基-4-甲基苯酚等。 前述紫外線吸收劑具體而言可舉出2–(3–三級丁基–2–羥基-5-甲基苯基)–5–氯苯并三唑、烷氧苯并苯酚等。 前述凝集防止劑具體而言可舉出聚丙烯酸鈉等。 前述鏈轉移劑具體而言可舉出十二硫醇、2,4‒二苯基‒4‒甲基‒1‒戊烯等。 ＜光硬化圖型及圖像顯示裝置＞ 本發明之目的在於提供以前述光敏樹脂組成物製造之光硬化圖型，及包含前述光硬化圖型之圖像顯示裝置。 以前述光敏樹脂組成物製造之光硬化圖型係低溫硬化性優良，耐化學性、耐熱性等優良。因此，於圖像顯示裝置中，可利用於各種圖型，例如接著劑層、陣列平坦化膜、保護膜、絕緣膜圖型等，可利用於光阻劑、黑矩陣、柱狀間隔物(column spacer)圖型、黑色柱狀間隔物等，但不限定於此，尤其非常適宜作為光阻圖型。 備有該類光硬化圖型或於製造過程中使用前述圖型之圖像顯示裝置，可舉出液晶顯示裝置、OLED、可撓顯示器等，但不限於此，可舉出可適用之該領域中為人所知的所有圖像顯示裝置。 光硬化圖型可藉由於基材上，塗佈前述本發明之光敏樹脂組成物(依需要歷經顯影步驟後)，形成光硬化圖型來製造。 首先，於基板塗佈光敏樹脂組成物後，予以加熱乾燥，去出溶劑等揮發成分而獲得平滑的塗膜。 塗佈方法可藉由例如旋轉塗佈、柔軟塗佈法、輥塗佈法、狹縫與旋轉塗佈或狹縫塗佈法等來實施。塗佈後加熱乾燥(預烤)，或於減壓乾燥後加熱，使溶劑等揮發成分揮發。在此，加熱溫度為相對低溫之70～100℃。加熱乾燥後之塗膜厚度一般為1～8mm。於如此所獲得的塗膜，透過用以形成所需圖型之圖罩照射紫外線。此時，於曝光部全體均勻照射平行光線，又，宜使用圖罩對準器或步進機等裝置，以便進行圖罩與基板正確的位置對齊。若照射紫外線，則於照射到紫外線的部分會進行硬化。 前述紫外線可採用g線(波長：436nm)、h線、i線(波長：365nm)等。紫外線照射量可因應需要適當地選擇，於本發明不予以限定。若因應需要使硬化結束後之塗膜與顯影液接觸，令非曝光部溶解而顯影，則可形成所需圖型形狀。 前述顯影方法採用液添加法、滴下法、噴霧法等任一方法均無妨。又，顯影時，以任意角度傾斜基板均可。前述顯影液一般是含有鹼性化合物及界面活性劑之水溶液。前述鹼性化合物為無機及有機鹼性化合物之任一者均可。作為無機鹼性化合物之具體例可舉出氫氧化鈉、氫氧化鉀、磷酸氫二鈉、磷酸二氫鈉、磷酸氫二銨、磷酸二氫銨、磷酸二氫鉀、矽酸鈉、矽酸鉀、碳酸鈉、碳酸鉀、碳酸氫鈉、碳酸氫鉀、硼酸鈉、硼酸鉀、氨等。又，有機鹼性化合物之具體例可舉出四甲銨氫氧化物、2-羥基乙基三甲銨氫氧化物、單甲胺、二甲胺、三甲胺、單乙胺、二乙胺、三乙胺、單異丙胺、二異丙胺、乙醇胺等。 該等無機及有機鹼性化合物可分別單獨使用，或組合兩種以上使用。鹼顯影液中之鹼性化合物的濃度宜為0.01～10質量%，更宜為0.03～5質量%。 前述鹼顯影液中之界面活性劑可使用從非離子系界面活性劑、陰離子系界面活性劑或陽離子界面活性劑所組成的群組中選擇之至少一種。 前述非離子系界面活性劑之具體例可舉出聚氧乙烯烷醚、聚氧乙烯芳醚、聚氧乙烯烷基芳醚、其他聚氧乙烯衍生物、氧乙烯/氧丙烯嵌段共聚物、山梨糖醇酐脂肪酸酯、聚氧乙烯山梨糖醇酐脂肪酸酯、聚氧乙烯山梨醇脂肪酸酯、甘油脂肪酸酯、聚氧乙烯脂肪酸酯、聚氧乙烯烷胺等。 前述陰離子系界面活性劑之具體例可舉出月桂醇硫酸酯鈉或油醇硫酸酯鈉等高級醇硫酸酯類、月桂醇硫酸鈉或月桂醇硫酸銨等烷基硫酸鹽類、十二苯磺酸鈉或十二萘磺酸鈉等烷基烯丙硫酸鹽類等。 前述陽離子界面活性劑之具體例可舉出硬脂胺鹽酸鹽或月桂三甲基氯化銨等胺鹽或四級銨鹽等。該等界面活性劑可分別單獨使用，或組合兩種以上使用。 前述顯影液中之界面活性劑的濃度一般為0.01～10wt%，較宜為0.05～8wt%，更宜為0.1～5wt%。顯影後水洗，以相對低溫之70～100℃實施10～60分之後烤。 以下，為了有助於理解本發明而提示較佳實施例，但該等實施例僅止於例示本發明，不限制附加的申請專利範圍，對同業者而言，顯然可於本發明之範疇及技術思想範圍內，對於實施例施以各種變更及修正，該類變更及修正當然隸屬於附加的申請專利範圍。 調製例1：鹼可溶性樹脂(第一樹脂(A‒1))之合成 將備有回流冷卻器、滴下漏斗及攪拌機之1L燒瓶內置於氮氣氛下，放入甲基乙基二乙二醇300質量部，一面攪拌一面加熱至70℃。接著，將下述化學式5及6之混合物(莫耳比50：50)300質量部、縮水甘油基甲基丙烯酸酯150質量部、及甲基丙烯酸50質量部，溶解於甲基乙基二乙二醇140質量部，調製成溶液。 [化17] [化學式5][化18] [化學式6]使用滴下漏斗，歷經4小時，將調製的溶液滴下於保溫在70℃之燒瓶內。另一方面，使用別的滴下漏斗，將使聚合起始劑2,2'‒偶氮雙‒(2,4‒二甲基戊腈)30質量部溶解於甲基乙基二乙二醇225質量部而調製成的溶液，歷經4小時滴下於燒瓶內。聚合起始劑溶液的滴下結束後，維持在70℃達4小時，其後冷卻至室溫，獲得固體粉36.7mass%、酸價59mg‒KOH/g(固體粉換算)之共聚物(第一樹脂(A‒1))溶液。 所獲得的樹脂A‒1之重量平均分子量(Mw)為8,200，分子量分布為1.85。 此時，前述分散樹脂之重量平均分子量(Mw)及數量平均分子量(Mn)的測定係使用HLC‒8120GPC(TOSOH股份有限公司製)裝置，管柱係將TSK‒GELG4000HXL及TSK‒GELG2000HXL予以串聯連接使用，管柱溫度為40℃，轉移相溶劑為四氫呋喃，流速為1.0mL/分，注入量為50mL，檢測器係使用RI，測定試料濃度為0.6mass%(溶劑=四氫呋喃)，校正用標準物質採用TSK STANDARD POLYSTYRENE F‒40、F‒4、F‒1、A‒2500、A‒500(TOSOH股份有限公司製)。 前述所獲得的重量平均分子量及數量平均分子量的比設為分子量分布(Mw/Mn)。 調製例2：鹼可溶性樹脂(第二樹脂(A‒2))之合成 於備有回流冷卻器、滴下漏斗及攪拌機之1L燒瓶內，以0.02L/分流入氮而成為氮氣氛下，投入甲基乙基二乙二醇300質量部，一面攪拌一面加熱至70℃。接著，將苯乙烯30質量部、甲基丙烯酸45質量部、(甲基)丙烯酸縮水甘油酯135質量部、2‒(八氫‒4,7‒甲橋‒1H‒茚‒5‒基)甲基‒2‒丙烯酸乙酯65質量部，溶解於甲基乙基二乙二醇140質量部，調製成溶液。 使用滴下漏斗，歷經4小時，將調製的溶解液滴下於保溫在70℃之燒瓶內。另一方面，使用別的滴下漏斗，將使聚合起始劑2,2'‒偶氮雙‒(2,4‒二甲基戊腈)30質量部溶解於甲基乙基二乙二醇225質量部而調製成的溶液，歷經4小時滴下於燒瓶內。聚合起始劑溶液的滴下結束後，維持在70℃達4小時，其後冷卻至室溫，獲得固體粉32.4mass%、酸價31mg‒KOH/g(固體粉換算)之共聚物(第二樹脂(A‒2))溶液。 所獲得的樹脂A‒2之重量平均分子量(Mw)為28,000，分子量分布為3.20。 此時，前述分散樹脂之重量平均分子量(Mw)及數量平均分子量(Mn)的測定係使用HLC‒8120GPC(TOSOH股份有限公司製)裝置，管柱係將TSK‒GELG4000HXL及TSK‒GELG2000HXL予以串聯連接使用，管柱溫度為40℃，轉移相溶劑為四氫呋喃，流速為1.0mL/分，注入量為50mL，檢測器係使用RI，測定試料濃度為0.6mass%(溶劑=四氫呋喃)，校正用標準物質為TSK STANDARD POLYSTYRENE F‒40、F‒4、F‒1、A‒2500、A‒500(TOSOH股份有限公司製)。 前述所獲得的重量平均分子量及數量平均分子量的比設為分子量分布(Mw/Mn)。調製例 3 ：鹼可溶性樹脂 (A ‒ 3) 之合成
於備有攪拌機、溫度計回流冷卻管、滴下漏斗及氮導入管之燒瓶，裝入丙二醇單甲醚乙酸酯182g，以0.02L/分流入氮，使燒瓶內氣氛從空氣成為氮之後，升溫至100℃後，使用滴下漏斗，歷經2小時，於燒瓶滴下在包含甲基丙烯酸60質量部、甲基丙烯酸甲酯40質量部、2‒(八氫‒4,7‒甲橋‒1H‒茚‒5‒基)甲基‒2‒丙烯酸乙酯20質量部，及丙二醇單甲醚乙酸酯136g之混合物添加偶氮異丁腈3.6g而調製成的溶液，以100℃進一步繼續攪拌5小時。接著，於燒瓶內投入甲基丙烯酸縮水甘油酯30質量部、三二甲胺甲基苯酚0.9g及對苯二酚0.145g，以110℃進行6小時反應，獲得固體粉酸價110mgKOH/g之共聚物(第三樹脂(A‒3))。藉由GPC測定之聚苯乙烯換算之重量平均分子量為33,000，分子量分布(Mw/Mn)為4.0。 此時，前述分散樹脂之重量平均分子量(Mw)及數量平均分子量(Mn)的測定係使用HLC‒8120GPC(TOSOH股份有限公司製)裝置，管柱係將TSK‒GELG4000HXL及TSK‒GELG2000HXL予以串聯連接使用，管柱溫度為40℃，轉移相溶劑為四氫呋喃，流速為1.0mL/分，注入量為50mL，檢測器係使用RI，測定試料濃度為0.6mass%(溶劑=四氫呋喃)，校正用標準物質為TSK STANDARD POLYSTYRENE F‒40、F‒4、F‒1、A‒2500、A‒500(TOSOH股份有限公司製)。 前述所獲得的重量平均分子量及數量平均分子量的比設為分子量分布(Mw/Mn)。實施例及比較例
以下述表1所記載的組成來調製負型光敏樹脂組成物。 試驗方法
以中性洗劑、水及乙醇，依次洗淨2英吋見方之玻璃基板(EAGLE 2000，Corning製)後使其乾燥。於該玻璃基板上，分別旋轉塗佈前述實施例及比較例調製的光敏樹脂組成物後，利用加熱板，以90℃進行預烤125秒鐘。以常溫冷卻經進行前述預烤之基板後，將與石英玻璃製光罩之間隔設為150mm，使用曝光機(UX-1100SM；Ushio股份有限公司製)，以60mJ/cm2
之曝光量(365nm基準)照射光。此時，光罩是採用下一圖型形成於同一平面上之光罩。 具有30mm方形圖型之正四角形開口部(孔圖型)，相互間隔為100mm，於包含光照射後之非離子系界面活性劑0.12%及氫氧化鉀0.04%之水系顯影劑，將前述塗膜以25℃浸漬60秒鐘後顯影，水洗後於烤箱中，以90℃實施1小時後烤。如下將如此獲得之圖型實施物性評估，於下述表2表示其結果。 (1)孔線寬：孔圖型形成時測定之底面X方向及Y方向之平均值。於前述實施中，利用30mm方形圖型進行圖型形成。 (2)CD‒Bias(關鍵尺寸偏差值)：從製造之實際圖型尺寸，減去適用之圖罩尺寸後之值，實際圖型尺寸越接近適用之圖罩尺寸，可判斷圖型形成性能越優良。 此時，判斷具有接近0之組成為更優良之組成。 (3)顯影後殘渣：於孔圖型形成時，以顯微鏡確認於顯影階段後，是否殘留於未曝光部表面(未產生者較佳)。 (4)耐熱殘膜率：以90℃進一步將圖型形成結束之顯影後硬化物加熱1小時，進一步以230℃加熱30分，觀察因追加加熱所造成的膜收縮程度。於低溫硬化條件下硬化性能優良的材料，視為追加加熱中之膜收縮小，追加加熱後之耐熱殘膜率高者，可判斷低溫硬化性能更加優良。 (5)耐化學性評估：將以90℃加熱1小時，經硬化階段之塗膜，浸漬於HNO3
及HCl水溶液，進行45分/6分鐘處理。 其後，根據ASTM D‒3359‒08標準試驗條件，採用在以切斷器切斷的表面，黏貼膠帶後再剝離的方法來確認密著性。 進行藥液處理後，於Cutting/Tape試驗中，根據標準試驗法，將塗膜產生剝離的程度規定為0B～5B，判斷5B為具有最優良性能者(5B：剝離0%，4B：剝離小於5%，3B：剝離5以上～小於15%，2B：剝離15以上～小於35%，1B：剝離35以上～小於65%，0B：65%以上)。 (6)穿透率：以90℃加熱圖型形成結束後之顯影後硬化物1小時，進行最終硬化後，測定塗膜部分之穿透率。
參考前述表2，本發明之光敏樹脂組成物可確認於低溫硬化條件下製造之圖型之圖型形成特性及耐化學性、耐熱性等優良。 具體而言，僅使用第一樹脂之比較例1及未使用本發明之第二樹脂之比較例4，係孔圖型之具現特性明顯較低，僅使用第二樹脂之比較例2產生顯影殘渣，耐熱殘膜率小於70%，故可知低溫硬化性能差。 又，未使用硫醇化合物之比較例3及使用2官能硫醇之比較例5，可知可靠性明顯降低。The present invention relates to a negative photosensitive resin composition comprising an alkali-soluble resin (A), a polymerizable compound (B), a trifunctional or higher polyfunctional thiol compound (C), and photopolymerization. a starter (D) and a solvent (E), wherein the alkali-soluble resin (A) comprises: a first resin comprising a repeating unit represented by Chemical Formula 1, and a second resin comprising a repeating unit represented by Chemical Formula 2; The mixing ratio of the first resin to the second resin is 50:50 to 90:10; under low-temperature curing conditions, a pattern excellent in reactivity and excellent in durability can be formed. <Photosensitive Resin Composition> The present invention relates to a negative photosensitive resin composition comprising an alkali-soluble resin (A), a polymerizable compound (B), a trifunctional or higher polyfunctional thiol compound (C), and photopolymerization. Starter (D) and solvent (E). Alkali-soluble resin (A) The alkali-soluble resin (A) used in the present invention is a soluble component to the alkali developer for use in the development treatment step in forming a pattern, and comprises: a repeating unit represented by the following chemical formula 1 The first resin and the second resin including the repeating unit represented by the following Chemical Formula 2. [Chemical Formula 1] [Chemical Formula 1][where, R1
, R2
And R3
Individually hydrogen or methyl; R4
From the group consisting of methacrylic acid, acrylic acid, 2 ‒ propylene methoxy succinate, 2 propylene propylene oxyethyl hexahydrophthalate, 2 propylene propylene oxyethyl phthalate The structure of the monomer selected from the group of formate and 2-mercaptoethyl methacrylate succinate; R5
a structure derived from a monomer selected from the group consisting of the following formulas (1) to (9); [Chem. 7]R6
a structure derived from a monomer selected from the group consisting of the following formulas (10) to (12); [Chemical 8]a = 10 to 30 mol%, b = 30 to 60 mol%, and c = 20 to 50 mol%. ] [Chemical Formula 9] [Chemical Formula 2][where, R7
, R8
, R9
And R10
Individually hydrogen or methyl; R11
From the group consisting of methacrylic acid, acrylic acid, 2 ‒ propylene methoxy succinate, 2 propylene propylene oxyethyl hexahydrophthalate, 2 propylene propylene oxyethyl phthalate The structure of the monomer selected from the group of formate and 2-mercaptoethyl methacrylate succinate; R12
From the benzyl methacrylate, phenoxyethylene glycol acrylate, phenoxy diethylene glycol acrylate, (2 phenyl) phenoxy ethoxy acrylate, 2 ‒ hydroxy hydrazine (2 Phenyl phenyl) phenol propyl acrylate, 2 hydrazine hydroxy hydrazone (3 phenyl) phenoxy propyl acrylate, tetrahydrofurfuryl acrylate, styrene, vinyl toluene, vinyl naphthalene, N benzyl benzyl maleic acid Imine, methyl methacrylate, ethyl methacrylate, methoxyethylene glycol methacrylate, methoxy diethylene glycol methacrylate, methoxy triethylene glycol methacrylate, Monomer selected from the group consisting of methoxytetraethylene glycol methacrylate, phenoxyethylene glycol methacrylate, phenoxy diethylene glycol methacrylate, and tetrahydrofurfuryl methacrylate Construction; R13
a structure derived from a monomer selected from the group consisting of the above formulas (1) to (9);14
a structure derived from a monomer selected from the group consisting of the following formulas (13) to (19);d = 10 to 30 mol%, e = 10 to 20 mol%, f = 30 to 60 mol%, and g = 10 to 30 mol%. In the present invention, the respective repeating units shown in Chemical Formulas 1 and 2 are not limited to the explanations such as Chemical Formulas 1 and 2, and the sub-repeat unit in the parentheses may be located anywhere in the chain within the range of the determined molar %. That is, each of the parentheses of Chemical Formulas 1 and 2 is represented by one block in order to express the molar %, but each of the sub-repeat units can be separated into blocks or their respective ones without being restricted in the corresponding resin. A preferred example of the compound of Chemical Formula 1 of the present invention is a compound of the following Chemical Formula 1-1. [Chemical Formula 1] [Chemical Formula 1‒1][where, R1
, R2
And R3
Each is hydrogen or a methyl group; a = 10 to 30 mol%, b = 30 to 60 mol%, and c = 20 to 50 mol%. Further, preferred examples of the compound of Chemical Formula 2 of the present invention include the compounds of the following Chemical Formula 2‒1. [Chemical Formula 2] [Chemical Formula 2‒1][where, R7
, R8
, R9
And R10
Each is hydrogen or a methyl group; d = 10 to 30 mol%, e = 10 to 20 mol%, f = 30 to 60 mol%, and g = 10 to 30 mol%. The first resin of the present invention functions to improve the chemical resistance and reactivity of the photosensitive resin composition. In this respect, the weight average molecular weight of the first resin is preferably 6,000 to 12,000. In the above molecular weight range, the most excellent reactivity and chemical resistance can be exhibited. The second resin of the present invention functions to improve durability such as pattern formation property and heat resistance of the photosensitive resin composition. In this respect, the weight average molecular weight of the second resin is preferably 20,000 to 30,000. In the above molecular weight range, the most excellent pattern formability, heat resistance and the like can be exhibited. The mixing ratio by weight of the first resin of the present invention to the second resin is from 50:50 to 90:10, more preferably from 70:30 to 80:20. If the first resin content is less than the second resin content, the low-temperature hardenability is lowered to cause a residue after development. When the first resin content exceeds 9 times the weight of the second resin, the pattern formation property is lowered. The first resin and the second resin of the present invention may further comprise a repeating unit formed of a conventional other monomer, and may be formed only by a repeating unit of Chemical Formula 1, in addition to the repeating unit of Chemical Formulas 1 and 2, respectively. The monomer which can be further added to the repeating unit of Chemical Formulas 1 and 2 is not particularly limited, and examples thereof include monocarboxylic acids such as crotonic acid and dicarboxylic acids such as fumaric acid, mesaconic acid and itaconic acid. And the anhydride of the dicarboxylic acid; mono(meth)acrylate of a polymer having a carboxyl group and a hydroxyl group at both terminals, such as an omega carboxylic acid polycaprolactone mono(meth)acrylate; vinyl toluene, p-chlorobenzene Ethylene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinyl anisole, m-vinyl anisole, p-vinyl anisole, o-vinyl phenyl epoxy propyl ether , an aromatic vinyl compound such as vinyl phenyl epoxy propyl ether or p-vinyl phenyl epoxy propyl ether; N-cyclohexyl maleimide, N-benzyl maleimide , N-phenyl maleimide, N-o-hydroxyphenyl maleimide, N-m-hydroxyphenyl maleimide, N-p-hydroxyphenyl-butene Diquinone imine, N-o-methylphenyl maleimide, N-m-methylphenyl maleimide, N-p-methylphenyl maleimide, N-o-methoxyphenyl N-substituted maleimide, such as maleimide, N-m-methoxyphenyl maleimide, N-p-methoxyphenyl maleimide a compound; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, propyl iso (meth) acrylate, butyl (meth) acrylate, iso (methyl) a (meth)acrylic acid alkyl ester such as butyl acrylate, butyl (meth) acrylate or butyl (meth) acrylate; benzyl (meth) acrylate, 2-methyl ring (A) An alicyclic (meth) acrylate such as hexyl acrylate or ethyl 2-bicyclophenetan (meth) acrylate; or an aryl (meth) acrylate such as phenyl (meth) acrylate; 3-(methacrylomethoxymethyl)oxetane, 3-(methacrylomethoxyethyl)-3-ethyloxetane, 3-(methacryloxymethyl) -2-trifluoromethyloxetane, 3-(methacryloxymethyl)-2-phenyloxetane, 2-(methacrylofluorenyloxy) oxetane An unsaturated oxetane compound such as an alkane or a 2-(methacrylomethoxyethyl)-4-trifluoromethyloxetane; etc.; methyl (meth) propyl Unsaturated acids such as glycidyl compounds of ethylene oxide; and (meth) acrylate carbon atoms substituted cycloalkyl or bicyclic alkyl of 4 to 16 in. These may be used alone or in combination of two or more. The acid value of the alkali-soluble resin (A) is preferably in the range of 20 to 200 (KOH mg/g). If the acid value is within the above range, it can have excellent developability and stability over time. The content of the alkali-soluble resin (A) is not particularly limited, and may be, for example, 10 to 90 parts by mass, more preferably 25 to 70 parts by mass, based on 100 parts by mass of the photosensitive resin composition, based on the solid powder. When it is contained in the above numerical range, since the solubility in the developer is sufficient, the developability is good, and a photo-curing pattern having excellent mechanical properties can be formed. Polymerizable Compound (B) The polymerizable compound (B) used in the photosensitive resin composition of the present invention can increase the bridging density in the production step and enhance the mechanical properties of the photohardening pattern. The polymerizable compound (B) can be used without any particular limitation, for example, a monofunctional monomer, a bifunctional monomer, and other polyfunctional monomers, and the kind thereof is not particularly limited, and the following compounds are exemplified as example. Specific examples of the monofunctional monomer include mercaptophenyl carbitol, 2-hydroxy-3-phenoxy propyl acrylate, 2-ethylhexyl acrylic acid carbamide, 2-hydroxyethyl acrylate, N- Vinyl quinone and the like. Specific examples of the bifunctional monomer include hexamethylenedi(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and triethyl ethane. Diol (meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentane diol (meth) acrylate, and the like. Specific examples of the other polyfunctional monomer include trimethylolpropane tri(meth)acrylate, ethoxylated (ethoxylated) trimethylolpropane tri(meth)acrylate, and propoxylation ( Propoxylated) Trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ethoxylated (B) Oxidation) dipentaerythritol hexa(meth) acrylate, propoxylated (propoxylated) dipentaerythritol hexa(meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like. Among these monomers, a bifunctional or higher polyfunctional monomer is preferably used. The content of the polymerizable compound (B) is not particularly limited, and is, for example, 10 to 90 parts by mass, more preferably 30 to 80 parts by mass based on 100 parts by weight of the alkali-soluble resin, based on the solid powder in the photosensitive resin composition. The scope of the department is used. When the polymerizable compound (B) is in the range of the above content, it can have excellent durability and can improve the developability of the composition. Polyfunctional thiol compound (C) The trifunctional or higher polyfunctional thiol compound of the present invention is a trifunctional or higher thiol compound, which exhibits an increase in bridging density and makes the photohardenable pattern durable and dense with a substrate. Improve the function of the yellowing phenomenon under high temperature. The trifunctional or higher polyfunctional thiol compound of the present invention is not particularly limited as long as it is a compound having a trifunctional or higher thiol compound and can be used for the photosensitive resin composition, and is preferably a tetrafunctional or higher thiol compound. The thiol compound of the present invention can be represented, for example, by the following Chemical Formula 3. [Chemical Formula 3] [Chemical Formula 3][in the formula, Z1
Is a methylene group or an alkylene or alkylmethylene group having a linear or branched chain of 2 to 10 carbon atoms, and Y is a single bond, ‒CO‒, ‒O‒CO‒ or ‒NHCO‒, n is 3～ An integer of 10, X may have one or a plurality of ether-bonded n-valent hydrocarbon groups having 2 to 70 carbon atoms, or n is 3, and X is a trivalent group represented by the following Chemical Formula 4. ] [Chem. 14] [Chemical Formula 4][in the formula, Z2
,Z3
And Z4
Each is a methylene group or an alkylene group having 2 to 6 carbon atoms, and "*" represents a covalent bond. n is preferably 4 or more, and more preferably 4 to 10, more preferably 4, 6 or 8. When X is 3, for example, a trivalent group represented by the following Chemical Formula 5 may be mentioned, and when X is 4, 6 or 8, X may be, for example, a 4, 6 or 8 valent group represented by the following Chemical Formula 6 It is more suitable. [Chemical Formula 5] [Chemical Formula 5][wherein, "*" indicates a covalent bond. ] [Chem. 16] [Chemical Formula 6][wherein m is an integer of 0 to 2, and "*" represents a covalent bond. The content of the polyfunctional thiol compound (C) of the present invention is not particularly limited. For example, based on the solid powder in the photosensitive resin composition, it is preferably 0.1 to 15 parts by mass based on 100 parts by weight of the alkali-soluble resin. It is used in the range of 1 to 10 parts by mass. When the polyfunctional thiol compound (C) contains the above content, it exhibits excellent low-temperature curing properties. Photopolymerization initiator (D) The photopolymerization initiator (D) of the present invention can be used without any particular limitation, as long as it can polymerize the polymerizable compound (B), for example, from an acetophenone-based compound. An oxime ester compound is preferably used as the compound selected from the group consisting of a benzophenone compound, a triazine compound, a biimidazole compound, a thioxanthone compound, and an oxime ester compound. Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, and 2-hydroxyl group. 1-[4-(2-hydroxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexyl benzophenone, 2-methyl-1-(4-methylthiophenyl) )-2-morpholinepropane-1-ketone, 2-benzyl-2-dimethylamine-1-(4-morpholinylphenyl)butane-1-one, 2-hydroxy-2-methyl-1 -[4-(1-methylvinyl)phenyl]propan-1-one, 2-(4‒methylbenzyl)-2-(dimethylamine)-1-(4-morpholinylphenyl) Butane-1 1-ketone, etc. Specific examples of the benzophenone-based compound include benzophenone, o-benzylidene benzoic acid methyl, 4-phenylbenzophenone, and 4-benzoquinone-4'-methyldiphenyl. Sulfide, 3,3',4,4'-tetrakis(tert-butylperoxycarboxy)benzophenone, 2,4,6-trimethylbenzophenone, and the like. Specific examples of the aforementioned triazine-based compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)phosphonium 1,3,5-triazine, 2,4-bis (three) Chloromethyl)–6–(4‒methoxynaphthyl)‒1,3,5‒triazine, 2,4–bis(trichloromethyl)–6–piperonyl 1,3,5-triazine , 2,4–bis(trichloromethyl)-6–(4‒methoxyphenyl)‒1,3,5‒triazine, 2,4–bis(trichloromethyl)–6–[2 ‒(5‒methylfuran-2-yl)vinyl]‒1,3,5‒triazine, 2,4-bis(trichloromethyl)-6–[2‒furan-2-yl)vinyl ‒1,3,5‒Triazine, 2,4-bis(trichloromethyl)-6–[2‒(4‒diethylamine‒2‒methylphenyl)vinyl]‒1,3, 5 ‒ triazine, 2,4 - bis (trichloromethyl) - 6 - [2 ‒ (3, 4 ‒ dimethoxyphenyl) vinyl] ‒ 1,3, 5 ‒ triazine and the like. Specific examples of the biimidazole-based compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrabenzimidazole, 2,2'-bis (2,3- Dichlorobenzene)-4,4',5,5'-tetrabenzimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxybenzene) Imidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole, 2,2'-bis(2,6-dichlorobenzene) -4,4',5,5'-tetraphenylphosphonium 1,2'-linked imidazole or a biimidazole compound substituted with a carboxyalkoxy group at a 4,4',5,5' position, etc., preferably 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrabenzimidazole, 2,2'-bis(2,3-dichlorobenzene)-4,4 ',5,5'-tetrabenzimidazole, 2,2'-bis(2,6-dichlorobenzene)-4,4',5,5'-tetraphenylphosphonium 1,2'-linked imidazole. Specific examples of the thioxanthone-based compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxyl. Thioxanthone and the like. Specific examples of the above oxime ester-based compound include o-ethoxycarboxy-a-mercapto-1-phenylpropan-1-one and 1,2 octadiene oxime (‒4 phenylsulfonyl)phenylhydrazine 2 ‒(o-benzylidene) oxime, ethyl ketone oxime 1 ‒ (9 ‒ ethyl) ‒ 6 ‒ (2 ‒ 苯 ‒ ‒ ‒ ‒ ‒ ‒ ‒ ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; Products sold include CGI-124 (Ciba‒Geigy), CGI-224 (Ciba‒Geigy), Irgacure OXE-01 (BASF), Irgacure OXE-02 (BASF), N-1919 (ADEKA), NCI-831 (ADEKA) Wait. Further, the photopolymerization initiator (D) may further contain a photopolymerization initiation aid in order to improve the sensitivity of the photosensitive resin composition of the present invention. The photosensitive resin composition of the present invention further increases the sensitivity by including a photopolymerization initiation aid, and can improve productivity. The photopolymerization initiation aid may be one or more compounds selected from the group consisting of an amine compound, a carboxylic acid compound, and an organic sulfur compound having a thiol group. Specific examples of the amine compound include an aliphatic amine compound such as triethylolamine, methyldiethanolamine or triisopropanolamine, 4-dimethylaminobenzoic acid methyl group, and 4-dimethylamino group. Ethyl benzoate, isoamyl 4-dimethylaminobenzoate, hydrazine 2-ethylhexyl 4-dimethylaminobenzoate, (2-dimethylamino)ethyl benzoate, N, N-Dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone (general name: Michlerone), 4,4'-bis(diethylamino)diphenyl For ketone or the like, an aromatic amine compound is preferably used. Specific examples of the carboxylic acid compound are preferably aromatic heteroacetic acids, and examples thereof include phenylthioacetic acid, methylbenzenesulfuric acid, ethylbenzenesulfuric acid, methylethylbenzenesulfuric acid, and dimethylphenylsulfuric acid. Methoxybenzene sulfuric acid, dimethoxybenzene sulfuric acid, chlorophenyl sulfuric acid, dichlorobenzene sulfuric acid, N-phenylglycine, phenoxyacetic acid, naphthalene sulfuric acid, N-naphthylglycine, naphthyloxyacetic acid, etc. . Specific examples of the above-mentioned organic sulfur compound having a thiol group include 2-mercaptobenzothiazole, 1,4-bis(3-mercaptobutyrate)butane, and 1,3,5-tris(3-indenyl). Ethyl butyrate)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolpropane tris(3-nonylpropyl), neopentyl pentoxide (3 - mercaptobutyl ester), neopentyl alcohol oxime (3 - mercaptopropyl ester), dipentaerythritol bismuth (3 - mercaptopropyl ester), tetraethylene glycol bis (3- propyl propyl ester) and the like. The content of the photopolymerization initiator (D) is not particularly limited. For example, the solid powder may be contained in an amount of 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass based on 100 parts by mass of the photosensitive resin composition. The amount of the department. When the above-mentioned numerical range is satisfied, since the photosensitive resin composition is highly sensitive and the exposure time is shortened, productivity is improved, high resolution can be maintained, and the strength of the formed pixel portion and the smoothness of the pixel surface are good, which is preferable. Solvent (E) Solvent (E) If it is generally used in the art, any solvent can be used without limitation. Specific examples of the solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monoalkyl ether of ethylene glycol monobutyl ether; Diethylene glycol dialkyl ethers such as methyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether; methyl sarbuta acetate, ethyl 赛苏苏乙Ethylene glycol alkyl ether acetate such as acid ester or ethylene glycol monobutyl ether acetate; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl B An alkylene glycol alkyl ether acetate such as an acid ester or a methoxybenzyl acetate; a propylene glycol monoalkyl ether such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether or propylene glycol monobutyl ether; Propylene glycol dialkyl ethers such as ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol propyl methyl ether, propylene glycol ethyl propyl ether; propylene glycol methyl ether propionate, propylene glycol diethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol Propylene glycol alkane ether propionate such as butyl ether propionate; methoxybutanol, ethoxybutanol, propoxybutanol, butoxybutanol, etc. Glycol monoalkyl ethers; butanediol monoalkyl ether acetates such as methoxybutyl acetate, ethoxybutyl acetate, propoxybutyl acetate, butoxybutyl acetate; Butanediol monoalkyl ether propionate such as oxybutyl propionate, ethoxybutyl propionate, propoxybutyl propionate, butoxybutyl propionate; dipropylene glycol dimethyl ether, dipropylene glycol Dipropylene glycol dialkyl ethers such as diethyl ether, dipropylene glycol methyl ether; aromatic hydrocarbons such as benzene, toluene, xylene, and trimethylbenzene; methyl ethyl ketone, acetone, methyl ketone, methyl isobutyl ketone, Ketones such as cyclohexanone; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerol; methyl acetate, ethyl acetate, propyl acetate, butyl acetate, 2-hydroxyl Ethyl propionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropanoate, ethyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, ethyl lactate, Lactic acid propyl, butyl lactate, 3-hydroxypropionic acid methyl, 3-hydroxypropionic acid ethyl, 3-hydroxypropionic acid propyl, 3-hydroxypropionic acid butyl, 2-hydroxy-3-methylpropionic acid Methyl, ethyl methoxyacetate, Propyl oxypropylate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, methyl propyl oxyacetate, ethyl propyl oxyacetate, propoxyacetic acid Propyl, butyl acetoacetate, methyl butoxyacetate, ethyl butoxyacetate, butyl acetoacetate, butyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate , 2-methoxypropionic acid propyl, 2-methoxypropionic acid butyl, 2-ethoxypropionic acid methyl, 2-ethoxypropionic acid ethyl, 2-ethoxypropionic acid propyl, 2-ethoxy Butyl propionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, 2-butoxypropionic acid propyl, 2-butoxypropionic acid butyl, 3-methoxypropionic acid methyl, 3-methoxypropionic acid ethyl, 3-methoxypropionic acid propyl, 3-methoxypropionic acid butyl, 3-ethoxypropionic acid methyl, 3-ethoxypropionic acid ethyl, 3-ethoxypropane Acid propyl, 3-ethoxypropionic acid butyl, 3-propoxypropionic acid methyl, 3-propoxypropionic acid ethyl, 3-propoxypropionic acid propyl, 3-propoxypropionic acid butyl, 3 - esters such as methyl butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, butyl 3-butoxypropionate; cyclic ethers such as tetrahydrofuran and piper; g- Butyrolactone Esters like. The solvents listed herein may be used alone or in combination of two or more. When considering the coatability and drying property, the above solvent is preferably an alkylene glycol alkyl ether acetate, a ketone, a butanediol alkyl ether acetate, a butanediol monoalkyl ether, or a 3-ethoxy group. Ethyl propionate, ethyl 3-methoxypropionate, etc., and further preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, methoxybutyl acetate, methoxybutyl Alcohol, 3-ethoxypropionic acid ethyl, 3-methoxypropionic acid methyl, and the like. The content of the solvent (E) may be 40 to 95 parts by mass, and more preferably 45 to 85 parts by mass, based on 100 parts by mass of the entire photosensitive resin composition. When the above range is satisfied, a spin coater, a slit and a spin coater, a slit coater (also sometimes referred to as a "die coater" or a "spray coater"), an inkjet, etc. When the coating device is applied, the coating property is improved, which is preferable. Additive (F) The photosensitive resin composition of the present invention may further contain a filler, other polymer compound, a hardener, a leveling agent, a adhesion promoter, an antioxidant, an ultraviolet absorber, an aggregation inhibitor, and a chain, as needed. Additives such as transfer agents. Specific examples of the filler include glass, cerium oxide, aluminum oxide, and the like. Specific examples of the other polymer compound include a curable resin such as an epoxy resin or a maleimide resin; and polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate. , thermoplastic resins such as polyester and polyurethane. The curing agent is used to improve deep curing and mechanical strength. Specific examples of the curing agent include an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, and an oxetane compound. Specific examples of the epoxy compound of the curing agent include bisphenol A epoxy resin, brominated bisphenol A epoxy resin, bisphenol F epoxy resin, brominated bisphenol F epoxy resin, and phenol formaldehyde. Type epoxy resin, other aromatic epoxy resin, alicyclic epoxy resin, glycidyl ester resin, glycidylamine resin, and brominated derivatives of such epoxy resins, epoxy Aliphatic, alicyclic or aromatic epoxy compounds other than resins and their brominated derivatives, butadiene (co)polymer epoxy compounds, isoprene (co)polymer epoxy compounds, glycidyl groups (Meth) acrylate (co)polymer, triglycidyl isocyanurate, and the like. Specific examples of the oxetane compound of the above curing agent include carbonate dioxetane, xylene dioxetane, dioxetane adipate, and terephthalate. Dioxetane, cyclohexanedicarboxylic acid dioxetane, and the like. The hardening agent may be a hardening auxiliary compound which can ring-open and polymerize an epoxy group of an epoxy compound or an oxetane skeleton of an oxetane compound, and may be used in combination with the curing agent. The hardening auxiliary compound may, for example, be a polyvalent carboxylic acid, a polyvalent carboxylic acid anhydride or an acid generator. The carboxylic anhydrides are commercially available as an epoxy resin hardener. For example, the EIKA HARDENER EH-700 (made by ADEKA Industries Co., Ltd.), the trade name RIKACID HH (manufactured by Nippon Chemical and Chemical Co., Ltd.), and the trade name MH-700 (New Japan R&D Co., Ltd.) Ltd.) and so on. The hardeners exemplified above may be used singly or in combination of two or more. A commercially available surfactant can be used as the leveling agent, and examples thereof include a surfactant such as an anthracene-based, a fluorine-based, an ester-based, a cationic, an anionic, a nonionic or an amphoteric; and the like. The active agents may be used singly or in combination of two or more. In addition to the above surfactants, for example, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine upgrading In addition to polyurethanes and polyethyleneimine, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoei Chemical Co., Ltd.), EFTOP (manufactured by Tohkem Products), and MEGAFAC (DAINIPPON) are also available. Manufactured by INK AND CHEMICALS, Flourad (manufactured by Sumitomo 3M), Asahi guard, Surflon (above, manufactured by Asahi Glass), SOLSPERSE (manufactured by Zeneca), EFKA (manufactured by EFKA CHEMICALS), PB821 (manufactured by Ajinomoto Co., Ltd.), and the like. The adhesion promoter is preferably a decane compound, and specific examples thereof include ethylene trimethoxy decane, ethylene triethoxy decane, ethylene tris(2-methoxyethoxy) decane, and N-(2-amine). Ethyl)-3-aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3– Glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 2–(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3– Chloropropylmethyltrimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methacrylate propyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane, and the like. Specific examples of the antioxidant include 2-tributylbutyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methyl acrylate, 2-[- 1-(2-hydroxy-3,5-di-tri-pentylphenyl)ethyl]- 4,6-di-trisylpentyl phenyl acrylate, 6-[3-(3-tertiary butyl) 4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldiphenyl[d,f][1,3,2]dioxin Ring, 3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoxime-1,1-dimethylethyl]-2, 4,8,10-tetraoxaspiro[5,5]undecane, 2,2'-methylenebis(6-tributyl-4-methylphenol), 4,4'-butylene Bis(6-tris-butyl-3-methylphenol), 4,4'-thiobis(2-tert-butyl-5-methylphenol), 2,2'-thiobis(6- Tert-butyl-4-methylphenol), dilauryl ruthenium 3,3'-thiodipropionate, tetrakis(3,3,3'-thiodipropionate, distearyl ruthenium 3 , 3'-thiodipropionate, neopentyl pentoxide (3-lauryl thiopropionate), 1,3,5-tris(3,5-di-tertiary butyl-4-hydroxybenzyl )-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 3,3',3'',5,5',5''-hexa-tertiary Base-a, a', a''- (trimethyl-2,4,6-triyl)tri-p-cresol, neopentyl Alcohols store [3- (3,5-di - tert.butyl-4-hydroxyphenyl) propionate], 2,6-di - tert.butyl-4-methylphenol and the like. Specific examples of the ultraviolet absorber include 2 - (3 - tris-butyl - 2 - hydroxy-5-methylphenyl) - 5 - chlorobenzotriazole, alkoxybenzophenol, and the like. Specific examples of the aggregation inhibitor include sodium polyacrylate and the like. Specific examples of the chain transfer agent include dodecyl mercaptan and 2,4‒diphenylfluorene 4‒methyl‒1‒pentene. <Photo-curing pattern and image display device> An object of the present invention is to provide a photo-curing pattern produced by the above-mentioned photosensitive resin composition, and an image display device comprising the above-described photo-curing pattern. The photo-curing pattern produced by the photosensitive resin composition is excellent in low-temperature curability, and is excellent in chemical resistance, heat resistance, and the like. Therefore, in the image display device, it can be utilized in various patterns such as an adhesive layer, an array planarization film, a protective film, an insulating film pattern, etc., and can be utilized for a photoresist, a black matrix, and a column spacer ( Column spacer), but not limited to, a pattern, a black column spacer, etc., and is particularly suitable as a photoresist pattern. An image display device having such a photo-curing pattern or using the above-described pattern in the manufacturing process may be a liquid crystal display device, an OLED, a flexible display or the like, but is not limited thereto, and is applicable to the field. All image display devices known in the art. The photo-curing pattern can be produced by coating the photosensitive resin composition of the present invention (after a development step as needed) on the substrate to form a photo-curing pattern. First, the photosensitive resin composition is applied onto a substrate, and then dried by heating to remove a volatile component such as a solvent to obtain a smooth coating film. The coating method can be carried out, for example, by spin coating, soft coating, roll coating, slit and spin coating, slit coating, or the like. After coating, it is heated and dried (pre-baked), or dried under reduced pressure, and heated to volatilize volatile components such as a solvent. Here, the heating temperature is 70 to 100 ° C at a relatively low temperature. The thickness of the coating film after heat drying is generally 1 to 8 mm. The coating film thus obtained is irradiated with ultraviolet rays through a mask for forming a desired pattern. At this time, the entire portion of the exposure portion is uniformly irradiated with the parallel light, and it is preferable to use a device such as a mask aligner or a stepper to align the mask and the substrate in the correct position. When ultraviolet rays are irradiated, they are hardened in the portion where the ultraviolet rays are irradiated. The ultraviolet rays may be g lines (wavelength: 436 nm), h lines, i lines (wavelength: 365 nm), or the like. The amount of ultraviolet irradiation can be appropriately selected as needed, and is not limited in the present invention. If the coating film after the completion of the curing is brought into contact with the developing solution as needed, and the non-exposed portion is dissolved and developed, a desired pattern shape can be formed. The development method may be any of a liquid addition method, a dropping method, a spray method, and the like. Further, at the time of development, the substrate may be inclined at an arbitrary angle. The developer is generally an aqueous solution containing a basic compound and a surfactant. The basic compound may be any of an inorganic and an organic basic compound. Specific examples of the inorganic basic compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium citrate, and citric acid. Potassium, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium borate, potassium borate, ammonia, and the like. Further, specific examples of the organic basic compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, and trisole. Ethylamine, monoisopropylamine, diisopropylamine, ethanolamine, and the like. These inorganic and organic basic compounds may be used alone or in combination of two or more. The concentration of the basic compound in the alkali developing solution is preferably from 0.01 to 10% by mass, more preferably from 0.03 to 5% by mass. The surfactant in the alkali developer may be at least one selected from the group consisting of a nonionic surfactant, an anionic surfactant, and a cationic surfactant. Specific examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, and oxyethylene/oxypropylene block copolymers. A sorbitan fatty acid ester, a polyoxyethylene sorbitan fatty acid ester, a polyoxyethylene sorbitan fatty acid ester, a glycerin fatty acid ester, a polyoxyethylene fatty acid ester, a polyoxyethylene alkylamine, or the like. Specific examples of the anionic surfactant include higher alcohol sulfates such as sodium lauryl sulfate or sodium oleyl sulfate, alkyl sulfates such as sodium lauryl sulfate or ammonium lauryl sulfate, and dodecylsulfonate. An alkyl allylate such as sodium or sodium dodecyl sulfonate. Specific examples of the cationic surfactant include an amine salt such as stearylamine hydrochloride or lauryltrimethylammonium chloride or a quaternary ammonium salt. These surfactants may be used alone or in combination of two or more. The concentration of the surfactant in the developer is generally from 0.01 to 10% by weight, more preferably from 0.05 to 8% by weight, still more preferably from 0.1 to 5% by weight. After development, it is washed with water, and baked at a relatively low temperature of 70 to 100 ° C for 10 to 60 minutes. In the following, the preferred embodiments are presented to facilitate the understanding of the present invention, but the embodiments are merely illustrative of the present invention and are not intended to limit the scope of the appended claims. Within the scope of the technical idea, various changes and modifications are made to the embodiments, and such changes and modifications are of course subject to the scope of additional patent applications. Preparation Example 1: Synthesis of alkali-soluble resin (first resin (A‒1)) A 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer was placed under a nitrogen atmosphere, and methyl ethyl diethylene glycol 300 was placed. The mass portion was heated to 70 ° C while stirring. Next, 300 parts by mass of a mixture of the following chemical formulas 5 and 6 (mol ratio 50:50), 150 parts by mass of glycidyl methacrylate, and 50 parts by mass of methacrylic acid were dissolved in methylethyldiethyl 140 parts by mass of diol was prepared into a solution. [Chemical Formula 5] [Chemical Formula 5][Chemical Formula 6] [Chemical Formula 6]The prepared solution was dropped into a flask kept at 70 ° C over 4 hours using a dropping funnel. On the other hand, 30 parts by mass of the polymerization initiator 2,2'‒ azobisindole (2,4‒ dimethyl valeronitrile) was dissolved in methyl ethyl diethylene glycol 225 using another dropping funnel. The solution prepared by the mass portion was dropped into the flask over 4 hours. After the completion of the dropwise addition of the polymerization initiator solution, the temperature was maintained at 70 ° C for 4 hours, and then cooled to room temperature to obtain a copolymer of 36.7 mass% of solid powder and 59 mg ‒ KOH / g (in terms of solid powder). Resin (A‒1)) solution. The obtained resin A‒1 had a weight average molecular weight (Mw) of 8,200 and a molecular weight distribution of 1.85. In this case, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the dispersion resin were measured by using HLC(R) 8120GPC (manufactured by TOSOH Co., Ltd.), and the column was connected in series with TSK‒GELG4000HXL and TSK‒GELG2000HXL. The temperature of the column is 40 ° C, the solvent of the transfer phase is tetrahydrofuran, the flow rate is 1.0 mL / min, the injection amount is 50 mL, the detector is RI, the sample concentration is 0.6 mass% (solvent = tetrahydrofuran), and the calibration standard substance is used. TSK STANDARD POLYSTYRENE F‒40, F‒4, F‒1, A‒2500, and A‒500 (manufactured by TOSOH Co., Ltd.) were used. The ratio of the weight average molecular weight and the number average molecular weight obtained as described above is defined as a molecular weight distribution (Mw/Mn). Preparation Example 2: Synthesis of an alkali-soluble resin (second resin (A‒2)) in a 1 L flask equipped with a reflux condenser, a dropping funnel, and a stirrer, and flowing nitrogen into a nitrogen atmosphere at 0.02 L/min. 300 parts by weight of ethyl ethyl diethylene glycol was heated to 70 ° C while stirring. Next, 30 parts by mass of styrene, 45 parts by mass of methacrylic acid, 135 parts by weight of glycidyl (meth)acrylate, and 2 parts of octahydroquinone 4,7‒甲桥‒1H‒茚‒5‒ base The solution was prepared by dissolving in a mass portion of 2 parts of ethyl acrylate at a mass of 65 parts by mass. The prepared dissolution solution was dropped into a flask kept at 70 ° C over 4 hours using a dropping funnel. On the other hand, 30 parts by mass of the polymerization initiator 2,2'‒ azobisindole (2,4‒ dimethyl valeronitrile) was dissolved in methyl ethyl diethylene glycol 225 using another dropping funnel. The solution prepared by the mass portion was dropped into the flask over 4 hours. After the completion of the dropwise addition of the polymerization initiator solution, the temperature was maintained at 70 ° C for 4 hours, and then cooled to room temperature to obtain a copolymer of solid powder 32.4 mass% and acid value 31 mg ‒ KOH / g (in terms of solid powder) (second Resin (A‒2)) solution. The obtained resin A‒2 had a weight average molecular weight (Mw) of 28,000 and a molecular weight distribution of 3.20. In this case, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the dispersion resin were measured by using HLC(R) 8120GPC (manufactured by TOSOH Co., Ltd.), and the column was connected in series with TSK‒GELG4000HXL and TSK‒GELG2000HXL. The temperature of the column is 40 ° C, the solvent of the transfer phase is tetrahydrofuran, the flow rate is 1.0 mL / min, the injection amount is 50 mL, the detector is RI, the sample concentration is 0.6 mass% (solvent = tetrahydrofuran), and the calibration standard substance is used. TSK STANDARD POLYSTYRENE F‒40, F‒4, F‒1, A‒2500, A‒500 (manufactured by TOSOH Co., Ltd.). The ratio of the weight average molecular weight and the number average molecular weight obtained as described above is defined as a molecular weight distribution (Mw/Mn).Modulation example 3 : Alkali soluble resin (A ‒ 3) Synthesis
In a flask equipped with a stirrer, a thermometer reflux cooling tube, a dropping funnel, and a nitrogen introduction tube, 182 g of propylene glycol monomethyl ether acetate was charged, and nitrogen was introduced at 0.02 L/min, and the atmosphere in the flask was changed from air to nitrogen, and then the temperature was raised to After 100 ° C, the dropping funnel was used for 2 hours, and the flask was dropped to contain 60 parts by mass of methacrylic acid, 40 parts by mass of methyl methacrylate, and 2 ‒ (octahydroquinone 4,7‒甲桥‒1H‒茚‒). A solution prepared by adding 3.6 g of azoisobutyronitrile to a mixture of 20 parts by mass of methyl hydrazine 2 oxime ethyl acrylate and 136 g of propylene glycol monomethyl ether acetate was further stirred at 100 ° C for 5 hours. Next, 30 parts by weight of glycidyl methacrylate, 0.9 g of tridimethylaminomethylphenol, and 0.145 g of hydroquinone were placed in a flask, and the mixture was reacted at 110 ° C for 6 hours to obtain a solid powder acid value of 110 mgKOH/g. Copolymer (third resin (A‒3)). The weight average molecular weight in terms of polystyrene measured by GPC was 33,000, and the molecular weight distribution (Mw/Mn) was 4.0. In this case, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the dispersion resin were measured by using HLC(R) 8120GPC (manufactured by TOSOH Co., Ltd.), and the column was connected in series with TSK‒GELG4000HXL and TSK‒GELG2000HXL. The temperature of the column is 40 ° C, the solvent of the transfer phase is tetrahydrofuran, the flow rate is 1.0 mL / min, the injection amount is 50 mL, the detector is RI, the sample concentration is 0.6 mass% (solvent = tetrahydrofuran), and the calibration standard substance is used. TSK STANDARD POLYSTYRENE F‒40, F‒4, F‒1, A‒2500, A‒500 (manufactured by TOSOH Co., Ltd.). The ratio of the weight average molecular weight and the number average molecular weight obtained as described above is defined as a molecular weight distribution (Mw/Mn).Examples and comparative examples
The negative photosensitive resin composition was prepared by the composition described in the following Table 1. experiment method
A 2-inch square glass substrate (EAGLE 2000, manufactured by Corning) was washed successively with a neutral detergent, water, and ethanol, and then dried. The photosensitive resin composition prepared in the above Examples and Comparative Examples was spin-coated on the glass substrate, and then prebaked at 90 ° C for 125 seconds using a hot plate. After the pre-baked substrate was cooled at room temperature, the distance from the quartz glass mask was set to 150 mm, and an exposure machine (UX-1100SM; manufactured by Ushio Co., Ltd.) was used at 60 mJ/cm.2
The amount of exposure (365 nm reference) is used to illuminate the light. At this time, the reticle is a reticle formed on the same plane by the next pattern. A square-shaped opening (hole pattern) having a square pattern of 30 mm, and a water-based developer containing 0.12% of nonionic surfactant and 0.04% of potassium hydroxide after light irradiation, and the coating film After immersing at 25 ° C for 60 seconds, the solution was developed, washed with water, and then baked in an oven at 90 ° C for 1 hour. The pattern thus obtained was evaluated for physical properties as follows, and the results are shown in Table 2 below. (1) Hole width: The average value of the bottom X direction and the Y direction measured at the time of formation of the hole pattern. In the foregoing implementation, pattern formation was performed using a 30 mm square pattern. (2) CD‒Bias (key dimension deviation value): the value of the actual pattern size minus the applicable mask size. The closer the actual pattern size is to the applicable mask size, the pattern formation performance can be judged. The better. At this time, it is judged that the composition having a value close to 0 is a more excellent composition. (3) Residue after development: When the hole pattern is formed, it is confirmed by a microscope whether or not it remains on the surface of the unexposed portion after the development stage (it is preferable if it is not produced). (4) Heat-resistant residual film ratio: The cured product after development of the pattern formation was further heated at 90 ° C for 1 hour, and further heated at 230 ° C for 30 minutes to observe the degree of film shrinkage caused by additional heating. A material having excellent hardening properties under low-temperature curing conditions is considered to have a small film shrinkage during additional heating, and a high heat-resistant residual film ratio after additional heating can be judged to be more excellent in low-temperature hardening performance. (5) Chemical resistance evaluation: the film will be immersed in HNO by heating at 90 ° C for 1 hour and hardening stage.3
The aqueous solution of HCl was treated for 45 minutes/6 minutes. Thereafter, the adhesion was confirmed by a method of adhering the tape to the surface cut by the cutter and peeling it off according to the ASTM D‒3359‒08 standard test conditions. After the chemical treatment, in the Cutting/Tape test, the degree of peeling of the coating film is defined as 0B to 5B according to the standard test method, and it is judged that 5B is the one having the best performance (5B: peeling 0%, 4B: peeling is smaller than 5%, 3B: 5 or more to less than 15%, 2B: 15 or more to less than 35%, 1B: 35 to 65%, and 0 to 65%. (6) Transmittance: The cured product after development after the formation of the pattern was heated at 90 ° C for 1 hour, and after final hardening, the transmittance of the coating film portion was measured.
With reference to the above-mentioned Table 2, the photosensitive resin composition of the present invention can be confirmed to have excellent pattern formation characteristics, chemical resistance, heat resistance and the like in a pattern produced under low-temperature curing conditions. Specifically, in Comparative Example 1 using only the first resin and Comparative Example 4 in which the second resin of the present invention was not used, the present characteristics of the pore pattern were remarkably low, and the development residue was produced only in Comparative Example 2 using the second resin. The heat-resistant residual film ratio is less than 70%, so that the low-temperature hardening property is poor. Further, in Comparative Example 3 in which no thiol compound was used and Comparative Example 5 in which a bifunctional thiol was used, it was found that the reliability was remarkably lowered.