以下，說明本發明之詳情。 [硬化性組合物] 本發明之硬化性組合物較佳為藉由光之照射進行硬化而使用。本發明之硬化性組合物較佳為用於藉由顯影處理而形成硬化覆膜，更佳為用於藉由顯影處理而形成抗蝕劑膜。本發明之硬化性組合物較佳為顯影型抗蝕劑硬化性組合物。對於本發明之硬化性組合物，為了形成抗蝕劑膜，亦可不進行顯影，本發明之硬化性組合物亦可為非顯影型抗蝕劑硬化性組合物。本發明之硬化性組合物較佳為阻焊劑用硬化性組合物。 本發明之硬化性組合物包含(A)含羧基樹脂、(B)具有3個以上之(甲基)丙烯醯基之第1丙烯酸系單體、(C)下述式(1)所表示之第2丙烯酸系單體、(D)光聚合起始劑、及(E)氧化鈦。 [化2]上述式(1)中，R1及R2分別表示氫原子或甲基，n表示1～6之整數，m表示1～30之整數。 於本發明中，作為與(A)、(D)、(E)成分組合使用之丙烯酸系單體，併用特定之(B)第1丙烯酸系單體及(C)第2丙烯酸系單體。於(C)第2丙烯酸系單體中，2個(甲基)丙烯醯基不經由其他基而直接鍵結於-O-(Cn
H2n
O)m
基。又，於(C)第2丙烯酸系單體中，於2個(甲基)丙烯醯基之間，僅存在-O-(Cn
H2n
O)m
基，不存在其他基。 於本發明中，由於具備上述構成，故而可抑制硬化物暴露於高溫下時之變色，尤其可提高耐熱黃變性。進而，於本發明中，由於具備上述構成，故而可使硬化物不易產生龜裂。 作為與(A)、(B)、(D)、(E)成分組合使用之丙烯酸系單體，使用2個(甲基)丙烯醯基不經由其他基而直接鍵結於-O-(Cn
H2n
O)m
基之第2丙烯酸系單體，藉此與使用2個(甲基)丙烯醯基經由其他基而間接地鍵結於-O-(Cn
H2n
O)m
基之丙烯酸系單體之情形相比，可有效地抑制變色，尤其可有效地提高耐熱黃變性，可有效地抑制龜裂之產生。又，作為與(A)、(B)、(D)、(E)成分組合使用之丙烯酸系單體，使用於2個(甲基)丙烯醯基之間僅存在-O-(Cn
H2n
O)m
基之第2丙烯酸系單體，藉此與使用於2個(甲基)丙烯醯基之間存在-O-(Cn
H2n
O)m
基以外之基之丙烯酸系單體之情形相比，可有效地抑制變色，尤其可有效地提高耐熱黃變性，可有效地抑制龜裂之產生。 進而，於本發明中，由於具備上述構成，故而於在形成硬化物時進行顯影處理之情形時，亦可減少殘渣。 以下，詳細地說明本發明之硬化性組合物中所包含之各成分。 ((A)含羧基樹脂) (A)含羧基樹脂較佳為具有羧基之聚合性聚合物。具有羧基之聚合性聚合物具有聚合性，可進行聚合。(A)含羧基樹脂為具有3個以上之(甲基)丙烯醯基之丙烯酸系單體以外之樹脂，且為式(1)所表示之丙烯酸系單體以外之樹脂。(A)含羧基樹脂可僅使用1種，亦可併用2種以上。 藉由(A)含羧基樹脂具有羧基，硬化性組合物之顯影性變得良好。作為(A)含羧基樹脂，例如可列舉：具有羧基之丙烯酸系樹脂；具有羧基之環氧樹脂；及具有羧基之烯烴樹脂。再者，「樹脂」並不限定於固體樹脂，亦包含液狀樹脂及低聚物。 (A)含羧基樹脂較佳為下述含羧基樹脂(a)～(e)。 (a)藉由不飽和羧酸與具有聚合性不飽和雙鍵之化合物之共聚合而獲得的含羧基樹脂 (b)藉由含羧基(甲基)丙烯酸系共聚合樹脂(b1)與1分子中具有環氧乙烷環及乙烯性聚合性不飽和雙鍵之化合物(b2)之反應而獲得的含羧基樹脂 (c)使1分子中分別具有1個環氧基及聚合性不飽和雙鍵之化合物和具有聚合性不飽和雙鍵之化合物之共聚物與不飽和單羧酸進行反應後，使所生成之反應物之二級羥基與飽和或不飽和多元酸酐進行反應而獲得的含羧基樹脂 (d)使飽和或不飽和多元酸酐與含羥基聚合物進行反應後，使所生成之具有羧基之聚合物與1分子中分別具有1個環氧基及聚合性不飽和雙鍵之化合物進行反應而獲得的含羥基及羧基樹脂 (e)使具有芳香環之環氧化合物與飽和多元酸酐或不飽和多元酸酐進行反應而獲得的樹脂，或者使具有芳香環之環氧化合物與具有至少1個不飽和雙鍵之含羧基化合物進行反應後，進一步與飽和多元酸酐或不飽和多元酸酐進行反應而獲得的樹脂 於上述硬化性組合物之除溶劑以外之總成分100重量%中，(A)含羧基樹脂之含量較佳為3重量%以上，更佳為5重量%以上，且較佳為50重量%以下，更佳為40重量%以下。若(A)含羧基樹脂之含量為上述下限以上及上述上限以下，則硬化性組合物之硬化性、感光性及顯影性變得良好，於顯影後殘渣變得更少。關於硬化性組合物之除溶劑以外之總成分100重量%，於硬化性組合物包含溶劑之情形時，意指硬化性組合物之除溶劑以外之總成分100重量%，於硬化性組合物不包含溶劑之情形時，意指硬化性組合物100重量%。 ((B)具有3個以上之(甲基)丙烯醯基之第1丙烯酸系單體、及(C)式(1)所表示之第2丙烯酸系單體) (B)第1丙烯酸系單體具有3個以上之(甲基)丙烯醯基。(B)第1丙烯酸系單體之(甲基)丙烯醯基之數量可為6以下，亦可為5以下。(B)第1丙烯酸系單體可僅使用1種，亦可併用2種以上。 作為(B)第1丙烯酸系單體，可列舉：多元醇、多元醇之環氧乙烷加成物或多元醇之環氧丙烷加成物之多元(甲基)丙烯酸酯改性物；或苯酚、苯酚之環氧乙烷加成物或苯酚之環氧丙烷加成物之(甲基)丙烯酸酯改性物；或甘油二縮水甘油醚或三羥甲基丙烷三縮水甘油醚等縮水甘油醚之(甲基)丙烯酸酯改性物；或三聚氰胺(甲基)丙烯酸酯等。 作為上述多元醇，例如可列舉：己二醇、三羥甲基丙烷、季戊四醇、二季戊四醇及異氰尿酸三羥基乙酯。作為上述苯酚之(甲基)丙烯酸酯，例如可列舉：苯氧基(甲基)丙烯酸酯及雙酚A之二(甲基)丙烯酸酯改性物。 「(甲基)丙烯醯基」意指丙烯醯基及甲基丙烯醯基。「(甲基)丙烯酸」意指丙烯酸及甲基丙烯酸。「(甲基)丙烯酸酯」意指丙烯酸酯及甲基丙烯酸酯。 (C)第2丙烯酸系單體係由下述式(1)所表示。 [化3]上述式(1)中，R1及R2分別表示氫原子或甲基，n表示1～6之整數，m表示1～30之整數。 就適度地提高顯影性及硬化速度之觀點而言，n較佳為4以下之整數，更佳為3以下之整數，進而較佳為1或2。就適度地提高防龜裂性、顯影性及硬化速度之觀點而言，m較佳為1以上之整數，且較佳為25以下之整數，更佳為20以下之整數，進而較佳為15以下之整數，尤佳為10以下之整數。 (C)第2丙烯酸系單體較佳為伸烷基二醇之二(甲基)丙烯酸酯改性物。 於上述硬化性組合物之除溶劑以外之總成分100重量%中，(B)第1丙烯酸系單體與(C)第2丙烯酸系單體之合計之含量較佳為3重量%以上，更佳為5重量%以上，且較佳為50重量%以下，更佳為40重量%以下。若(B)第1丙烯酸系單體與(C)第2丙烯酸系單體之合計之含量為上述下限以上及上述上限以下，則可進一步抑制硬化物之高溫下之變色，於顯影後殘渣變得更少。 (B)第1丙烯酸系單體之含量相對於(C)第2丙烯酸系單體之含量之比((B)第1丙烯酸系單體之含量/(C)第2丙烯酸系單體之含量)以重量基準計較佳為0.05以上，更佳為1以上，且較佳為20以下，更佳為5以下。若(B)第1丙烯酸系單體之含量變多，則光硬化性變得更良好。若(C)第2丙烯酸系單體之含量變多，則顯影後之殘渣變得更少。 ((D)光聚合起始劑) 上述硬化性組合物由於包含(D)光聚合起始劑，故而可藉由光之照射而使硬化性組合物硬化。(D)光聚合起始劑可僅使用1種，亦可併用2種以上。 作為(D)光聚合起始劑，例如可列舉：醯基氧化膦、鹵甲基化三??、鹵甲基化㗁二唑、咪唑、安息香、安息香烷基醚、蒽醌、苯并蒽酮、二苯甲酮、苯乙酮、9-氧硫??、苯甲酸酯、吖啶、啡??、二茂鈦、α-胺基烷基苯酮、肟及該等之衍生物。 就進一步抑制硬化物之高溫下之變色，使耐光性更高，進一步抑制硬化物之表面之黏膩性之觀點而言，較佳為醯基氧化膦系光聚合起始劑。 於上述硬化性組合物中，相對於(A)含羧基樹脂、(B)第1丙烯酸系單體及(C)第2丙烯酸系單體之合計100重量份，(D)光聚合起始劑之含量較佳為0.1重量份以上，更佳為1重量份以上，且較佳為30重量份以下，更佳為15重量份以下。若(D)光聚合起始劑之含量為上述下限以上及上述上限以下，則硬化性組合物之感光性及硬化性變得更高。 ((E)氧化鈦) 上述硬化性組合物由於包含(E)氧化鈦，故而可形成反射率較高之抗蝕劑膜等之硬化物。藉由使用(E)氧化鈦，與使用(E)氧化鈦以外之其他無機填料之情形相比，可形成反射率較高之硬化物。(E)氧化鈦可僅使用1種，亦可併用2種以上。 (E)氧化鈦較佳為金紅石型氧化鈦或銳鈦礦型氧化鈦，更佳為金紅石型氧化鈦。藉由使用金紅石型氧化鈦，可進一步抑制硬化物之高溫下之變色。上述銳鈦礦型氧化鈦之硬度低於金紅石型氧化鈦。因此，藉由使用銳鈦礦型氧化鈦，硬化物之加工性變得更高。 作為(E)氧化鈦，可列舉硫酸法氧化鈦及氯法氧化鈦等。就進一步抑制硬化物之高溫下之變色之觀點而言，較佳為氯法氧化鈦。氯法氧化鈦係藉由氯法所製造之氧化鈦。 又，就有效地提高(E)氧化鈦及(F)無機填料之分散性之觀點而言，(E)氧化鈦較佳為金紅石型氧化鈦。 (E)氧化鈦較佳為包含作為基於矽氧化物或聚矽氧化合物之表面處理物之金紅石型氧化鈦。於(E)氧化鈦100重量%中，上述作為基於矽氧化物或聚矽氧化合物之表面處理物之金紅石型氧化鈦之含量較佳為10重量%以上，更佳為30重量%以上，且較佳為100重量%以下。(E)氧化鈦之總量可為上述作為基於矽氧化物或聚矽氧化合物之表面處理物之金紅石型氧化鈦。藉由使用上述作為基於矽氧化物或聚矽氧化合物之表面處理物之金紅石型氧化鈦，可進一步抑制硬化物之高溫下之變色。 關於作為基於矽氧化物或聚矽氧化合物之表面處理物之金紅石型氧化鈦，例如可列舉：作為金紅石氯法氧化鈦之石原產業公司製造之編號：CR-90；或作為金紅石硫酸法氧化鈦之石原產業公司製造之編號：R-550等。 (E)氧化鈦之平均粒徑較佳為0.1 μm以上，更佳為0.15 μm以上，且較佳為1 μm以下，更佳為0.5 μm以下。 (E)氧化鈦之平均粒徑係於體積基準粒度分佈曲線中累計值為50%時之粒徑值。該平均粒徑例如可使用雷射光式粒度分佈計進行測定。作為該雷射光式粒度分佈計之市售品，可列舉Beckman Coulter公司製造之「LS 13 320」等。 於上述硬化性組合物之除溶劑以外之成分100重量%中，(E)氧化鈦之含量較佳為3重量%以上，更佳為10重量%以上，進而較佳為15重量%以上，且較佳為80重量%以下，更佳為75重量%以下，進而較佳為70重量%以下。若(E)氧化鈦之含量為上述下限以上及上述上限以下，則可進一步抑制硬化物之高溫下之變色。進而，可容易地製備具有適於塗敷之黏度之硬化性組合物。 ((F)無機填料) 上述硬化性組合物亦可包含(F)與氧化鈦不同之無機填料。(F)無機填料係與氧化鈦不同之無機填料。(F)無機填料可僅使用1種，亦可併用2種以上。 作為(F)無機填料之具體例，可列舉：二氧化矽、氧化鋁、雲母、氧化鈹、鈦酸鉀、鈦酸鋇、鈦酸鍶、鈦酸鈣、氧化鋯、氧化銻、硼酸鋁、氫氧化鋁、氧化鎂、碳酸鈣、碳酸鎂、碳酸鋁、矽酸鈣、矽酸鋁、矽酸鎂、磷酸鈣、硫酸鈣、硫酸鋇、氮化矽、氮化硼、煅燒黏土等黏土、滑石、碳化矽、交聯丙烯酸樹脂之樹脂粒子及聚矽氧粒子等。 就進一步抑制硬化物之高溫下之變色，使硬化物之耐光性更高，進一步抑制硬化物之表面之黏膩性之觀點而言，上述硬化性組合物較佳為包含滑石或二氧化矽，更佳為包含二氧化矽。上述硬化性組合物亦可包含滑石。 (F)無機填料之平均粒徑較佳為0.1 μm以上，更佳為0.2 μm以上，且較佳為10 μm以下，更佳為5 μm以下。 (F)無機填料之平均粒徑係於體積基準粒度分佈曲線中累計值為50%時之粒徑值。該平均粒徑例如可使用雷射光式粒度分佈計進行測定。作為該雷射光式粒度分佈計之市售品，可列舉Beckman Coulter公司製造之「LS 13 320」等。 於上述硬化性組合物100重量%中，(F)無機填料之含量較佳為0.1重量%以上，更佳為1重量%以上，進而較佳為3重量%以上，且較佳為50重量%以下，更佳為30重量%以下，進而較佳為10重量%以下。若(F)無機填料之含量為上述下限以上及上述上限以下，則可進一步抑制硬化物之高溫下之變色，硬化物之耐光性變得更高，可進一步抑制硬化物之表面之黏膩性。 於上述硬化性組合物100重量%中，(E)氧化鈦與(F)無機填料之合計之含量較佳為5重量%以上，更佳為10重量%以上，進而較佳為20重量%以上，且較佳為80重量%以下，更佳為60重量%以下，進而較佳為40重量%以下。若(E)氧化鈦與(F)無機填料之合計之含量為上述下限以上及上述上限以下，則可進一步抑制硬化物之高溫下之變色，硬化物之耐光性變得更高，可進一步抑制硬化物之表面之黏膩性。 於上述硬化性組合物中，(E)氧化鈦之含量相對於(F)無機填料之含量之比((E)氧化鈦之含量/(F)無機填料之含量)以重量基準計較佳為0.1以上，更佳為1以上，且較佳為50以下，更佳為30以下。 ((G)環氧化合物) 以提高硬化物之切割加工性等為目的，上述硬化性組合物較佳為包含(G)環氧化合物。又，藉由使用(G)環氧化合物，硬化性組合物之硬化性亦變得良好。(G)環氧化合物係(A)含羧基樹脂以外之環氧化合物。(G)環氧化合物可僅使用1種，亦可併用2種以上。 作為(G)環氧化合物，例如可列舉：雙酚S型環氧樹脂、鄰苯二甲酸二縮水甘油酯樹脂、異氰尿酸三縮水甘油酯等雜環式環氧樹脂、聯二甲苯酚型環氧樹脂、聯苯酚型環氧樹脂、四縮水甘油基二甲苯醯基乙烷樹脂、雙酚A型環氧樹脂、氫化雙酚A型環氧樹脂、雙酚F型樹脂、溴化雙酚A型環氧樹脂、苯酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、脂環式環氧樹脂、雙酚A之酚醛清漆型環氧樹脂、螯合型環氧樹脂、乙二醛型環氧樹脂、含胺基環氧樹脂、橡膠改性環氧樹脂、二環戊二烯苯酚型環氧樹脂、聚矽氧改性環氧樹脂及ε-己內酯改性環氧樹脂。(G)環氧化合物可僅使用1種，亦可併用2種以上。 (G)環氧化合物較佳為與(A)含羧基樹脂之羧基進行反應而發揮作用，以使硬化性組合物硬化。 就進一步抑制硬化物之高溫下之變色，且使顯影後之殘渣更少之觀點而言，(G)環氧化合物較佳為於25℃下並非為液狀，較佳為於25℃下為固體狀。 (G)環氧化合物於25℃下並非為液狀意指於進行試驗之環氧樹脂結晶化之情形時，將進行試驗之環氧樹脂100 g於80℃之溫度下保持24小時後，於0.5小時之內冷卻至25℃，達到25℃後之經過時間為1小時以內的試驗樣品滿足以下之2個條件中之任一者。 即，(1)於將試驗樣品放入至垂直之試管(採用內徑30毫米、高度120毫米之平底圓筒型之玻璃製者)中直至距試管之底之高度成為55毫米為止，於將試樣之溫度管理為25℃之狀態下藉由攪拌棒攪拌1分鐘後即刻使該試管水平之情形時，直至該試驗樣品之移動面之前端通過距試管之底之距離為60毫米之部分之時間為90秒以上時，設為「於25℃下並非為液狀」。 (2)於25℃之條件下藉由B型黏度計對試驗樣品進行測定之情形時，為3,000,000厘泊以上時，設為「於25℃下並非為液狀」。 (G)環氧化合物於25℃下為固體狀意指滿足上述2個條件(1)及(2)之全部。 於上述硬化性組合物中，相對於(A)含羧基樹脂100重量份，(G)環氧化合物之含量較佳為0.1重量份以上，更佳為1重量份以上，且較佳為50重量份以下，更佳為30重量份以下。若(G)環氧化合物之含量為上述下限以上及上述上限以下，則硬化物之電氣絕緣性變得更高。 ((H)溶劑) 上述硬化性組合物亦可包含(H)溶劑。(H)溶劑可僅使用1種，亦可併用2種以上。 (H)溶劑一般為有機溶劑。作為上述有機溶劑，可列舉：甲基乙基酮、環己酮等酮化合物；甲苯、二甲苯、四甲基苯等芳香族烴化合物；溶纖劑、甲基溶纖劑、丁基溶纖劑、卡必醇、甲基卡必醇、丁基卡必醇、丙二醇單甲醚、二丙二醇單甲醚、二丙二醇二***、三丙二醇單甲醚等二醇醚化合物；乙酸乙酯、乙酸丁酯、乳酸丁酯、乙酸溶纖劑、丁基溶纖劑乙酸酯、卡必醇乙酸酯、丁基卡必醇乙酸酯、丙二醇單甲醚乙酸酯、二乙二醇單***乙酸酯、二丙二醇單甲醚乙酸酯、碳酸丙二酯等酯化合物；辛烷、癸烷等脂肪族烴化合物；石油醚、石腦油等石油系溶劑以及二元酸酯等。上述二元酸酯係被稱為DBE之溶劑。 於上述硬化性組合物100重量%中，(H)溶劑之含量較佳為5重量%以上，更佳為10重量%以上，且較佳為50重量%以下，更佳為30重量%以下。 ((I)抗氧化劑) 就進一步抑制硬化物之高溫下之變色之觀點而言，上述硬化性組合物亦可包含(I)抗氧化劑。(I)抗氧化劑較佳為具有路易士鹼性部位。就進一步抑制硬化物之高溫下之變色之觀點而言，(I)抗氧化劑較佳為酚系抗氧化劑、磷系抗氧化劑或胺系抗氧化劑，更佳為酚系抗氧化劑。 作為上述酚系抗氧化劑之市售品，可列舉：IRGANOX 1010、IRGANOX 1035、IRGANOX 1076、IRGANOX 1135、IRGANOX 245、IRGANOX 259及IRGANOX 295(以上均為Ciba Japan公司製造)；Adekastab AO-30、Adekastab AO-40、Adekastab AO-50、Adekastab AO-60、Adekastab AO-70、Adekastab AO-80、Adekastab AO-90及Adekastab AO-330(以上均為ADEKA公司製造)；Sumilizer GA-80、Sumilizer MDP-S、Sumilizer BBM-S、Sumilizer GM、Sumilizer GS(F)及Sumilizer GP(以上均為住友化學工業公司製造)；HOSTANOX O10、HOSTANOX O16、HOSTANOX O14及HOSTANOX O3(以上均為Clariant公司製造)；Antage BHT、Antage W-300、Antage W-400及Antage W500(以上均為川口化學工業公司製造)；以及SEENOX 224M及SEENOX 326M(以上均為Shipro Kasei公司製造)等。 作為上述磷系抗氧化劑，可列舉：環己基膦及三苯基膦等。作為上述磷系抗氧化劑之市售品，可列舉：Adekastab PEP-4C、Adekastab PEP-8、Adekastab PEP-24G、Adekastab PEP-36、Adekastab HP-10、Adekastab 2112、Adekastab 260、Adekastab 522A、Adekastab 1178、Adekastab 1500、Adekastab C、Adekastab 135A、Adekastab 3010及Adekastab TPP(以上均為ADEKA公司製造)；Sandostab P-EPQ及Hostanox PAR24(以上均為Clariant公司製造)；以及JP-312L、JP-318-0、JPM-308、JPM-313、JPP-613M、JPP-31、JPP-2000PT及JPH-3800 (以上均為城北化學工業公司製造)等。 作為上述胺系抗氧化劑，可列舉：三乙胺、雙氰胺、三聚氰胺、乙基二胺基均三??、2,4-二胺基均三??、2,4-二胺基-6-甲苯基均三??、2,4-二胺基-6-二甲苯基均三??及四級銨鹽衍生物等。 相對於(A)含羧基樹脂100重量份，(I)抗氧化劑之含量較佳為0.1重量份以上，更佳為5重量份以上，且較佳為30重量份以下，更佳為15重量份以下。若(I)抗氧化劑之含量為上述下限以上及上限以下，則進一步抑制硬化物之高溫下之變色。 (其他成分) 上述硬化性組合物亦可包含著色劑、填充劑、消泡劑、硬化劑、硬化促進劑、脫模劑、表面處理劑、阻燃劑、黏度調節劑、分散劑、分散助劑、表面改質劑、塑化劑、抗菌劑、防黴劑、調平劑、穩定劑、偶合劑、防垂流劑或螢光體等。 上述硬化性組合物例如可藉由將各調配成分進行攪拌混合後，藉由三輥研磨機均勻地進行混合而製備。 作為用於使上述硬化性組合物硬化之光源，可列舉發出紫外線或可見光線等活性能量線之照射裝置。作為上述光源，例如可列舉：超高壓水銀燈、Deep UV燈、高壓水銀燈、低壓水銀燈、金屬鹵化物燈及準分子雷射。該等光源係根據硬化性組合物之構成成分之感光波長而適當選擇。光之照射能量係根據所需之厚度或硬化性組合物之構成成分而適當選擇。光之照射能量一般為10～3000 mJ/cm2
之範圍內。 [電子零件及電子零件之製造方法] 本發明之電子零件之製造方法包括：於電子零件本體之表面上塗佈上述硬化性組合物而形成組合物層之步驟；及對上述組合物層照射光而形成硬化覆膜之步驟。於本發明之電子零件之製造方法中，為了形成上述硬化覆膜，可對上述組合物層進行顯影。上述組合物層較佳為抗蝕劑層，上述硬化覆膜較佳為抗蝕劑膜。 於不進行顯影處理之情形時，可於電子零件本體之表面上，部分地且於複數個部位塗佈上述光硬化性組合物。 就防止電子零件本體之熱劣化之觀點而言，為了形成上述硬化覆膜，較佳為不藉由熱硬化劑之作用使上述組合物層熱硬化。就防止電子零件本體之熱劣化之觀點而言，為了形成上述硬化覆膜，較佳為不加熱至150℃以上，更佳為不加熱至100℃以上。 為了形成上述硬化覆膜，較佳為不進行粗化處理。 以下，一面參照圖式，一面說明本發明之具體之電子零件之製造方法。於以下說明之實施形態中，上述組合物層為抗蝕劑層，上述硬化覆膜為抗蝕劑膜。為了形成抗蝕劑膜，使用非顯影型抗蝕劑光硬化性組合物。 圖1(a)～(e)係用以說明使用本發明之一實施形態之硬化性組合物，製造電子零件之方法之一例之剖視圖。 首先，如圖1(a)所示，準備塗佈對象構件11。塗佈對象構件11為電子零件本體。使用基板11A作為塗佈對象構件11，於基板11A之表面上配置複數個電極11B。 其次，如圖1(b)所示，於塗佈對象構件11之表面上塗佈本發明之一實施形態之硬化性組合物(以顯影型抗蝕劑硬化性組合物之形式使用)而形成抗蝕劑層12(組合物層)。於圖1(b)中，於塗佈對象構件11之表面上整體形成抗蝕劑層12。其次，如圖1(c)所示，經由遮罩13，僅對電極11B間上之抗蝕劑層12照射光。其後，如圖1(d)所示，進行顯影，部分地去除位於電極11B上且未照射光之抗蝕劑層12。於部分地去除抗蝕劑層12後，使殘存之抗蝕劑層12熱硬化。其結果為，如圖1(e)所示，獲得於塗佈對象構件11(電子零件本體)之表面上形成有抗蝕劑膜2之電子零件1。 圖2(a)～(c)係用以說明使用本發明之一實施形態之硬化性組合物，製造電子零件之方法之另一例之剖視圖。 如圖2(a)所示，準備塗佈對象構件11。其次，如圖2(b)所示，於塗佈對象構件11之表面上塗佈本發明之第2實施形態之硬化性組合物(以非顯影型抗蝕劑硬化性組合物之形式使用)而形成抗蝕劑層12X(組合物層)。於圖2(b)中，於塗佈對象構件11之表面上，部分地且於複數個部位塗佈上述硬化性組合物，形成複數層抗蝕劑層12X。具體而言，於基板11A之表面上之複數個電極11B之間形成有複數層抗蝕劑層12X。抗蝕劑層12X例如為抗蝕圖案。例如，抗蝕劑層12X係於假定使用顯影型抗蝕劑硬化性組合物時，僅形成於與顯影後殘存而形成之抗蝕劑層部分對應之位置。抗蝕劑層12X未形成於與使用顯影型抗蝕劑硬化性組合物，藉由顯影而去除之抗蝕劑層部分對應之位置。 其次，對抗蝕劑層12X照射光。例如，自抗蝕劑層12X之與塗佈對象構件11側相反之側，對抗蝕劑層12X照射光。其結果為，如圖2(c)所示，抗蝕劑層12X進行光硬化而形成抗蝕劑膜2X(硬化覆膜)。其結果為，獲得於塗佈對象構件11(電子零件本體)之表面上形成有抗蝕劑膜2X之電子零件1X。 硬化性組合物之塗佈方法例如可列舉：藉由點膠機之塗佈方法；藉由網版印刷之塗佈方法；及藉由噴墨裝置之塗佈方法等。就製造效率優異之方面而言，較佳為網版印刷。較佳為將硬化性組合物進行圖案印刷。 再者，使用圖1(a)～(e)及圖2(a)～(c)所說明之具備抗蝕劑膜之電子零件之製造方法為一例，電子零件之製造方法可適當進行變更。 於本發明中，可於塗佈對象構件之表面每塗佈1層光硬化性組合物即照射光而形成硬化物層(抗蝕劑層等)，又，亦可於進行2層以上塗佈後照射光而形成硬化物層。 以下，列舉實施例及比較例，具體地說明本發明。本發明並不僅限定於以下之實施例。 以下，列舉本發明之具體之實施例及比較例，藉此使得本發明明瞭。 於實施例及比較例中，使用以下之材料1)～17)。 1)丙烯酸系聚合物1(含羧基樹脂、下述合成例1中所獲得之丙烯酸系聚合物1) (合成例1) 於具備溫度計、攪拌機、滴液漏斗及回流冷卻器之燒瓶中加入作為溶劑之乙基卡必醇乙酸酯、及作為觸媒之偶氮二異丁腈，於氮氣環境下加熱至80℃，歷時2小時滴加以30：70之莫耳比混合甲基丙烯酸及甲基丙烯酸甲酯而成之單體。滴加後，攪拌1小時，將溫度提高至120℃。其後，進行冷卻。加入相對於所獲得之樹脂之所有單體單元之總量之莫耳量之莫耳比成為10之量的丙烯酸縮水甘油酯，使用溴化四丁基銨作為觸媒，於100℃下加熱30小時，使丙烯酸縮水甘油酯與羧基進行加成反應。冷卻後，自燒瓶中取出，獲得包含固形物成分酸值60 mgKOH/g、重量平均分子量15000、雙鍵當量1000之含羧基樹脂50重量%(不揮發成分)之溶液。以下，將該溶液稱為丙烯酸系聚合物1。 2)DPHA(第1丙烯酸系單體，二季戊四醇六丙烯酸酯，Daicel-Allnex公司製造) 3)TMPTA(第1丙烯酸系單體，三羥甲基丙烷三丙烯酸酯，Daicel-Allnex公司製造) 4)A-200(第2丙烯酸系單體，聚乙二醇二丙烯酸酯，新中村化學工業公司製造) 5)A-400(第2丙烯酸系單體，聚乙二醇二丙烯酸酯，新中村化學工業公司製造) 6)A-600(第2丙烯酸系單體，聚乙二醇二丙烯酸酯，新中村化學工業公司製造) 7)A-1000(第2丙烯酸系單體，聚乙二醇二丙烯酸酯，新中村化學工業公司製造) 8)APG-400(第2丙烯酸系單體，聚丙二醇二丙烯酸酯，新中村化學工業公司製造) 8)A-PTMG-65(第2丙烯酸系單體，聚四亞甲基二醇二丙烯酸酯，新中村化學工業公司製造) 9)BPE-1300N(其他丙烯酸系單體，乙氧基化雙酚A二甲基丙烯酸酯，新中村化學工業公司製造) 10)ABE-300(其他丙烯酸系單體，乙氧基化雙酚A二丙烯酸酯，新中村化學工業公司製造) 11)157S(雙酚A酚醛清漆型環氧樹脂，三菱化學公司製造，於25℃下為固體狀(固體)) 12)jER 828(雙酚A型環氧樹脂，三菱化學公司製造，於25℃下為液狀) 13)TPO(作為光自由基產生劑之光聚合起始劑，BASF Japan公司製造) 14)CR-50(氧化鈦，石原產業公司製造) 15)FH105(滑石，Fuji Talc公司製造) 16)KS-7710(複合物型聚矽氧油、聚二甲基矽氧烷，信越化學工業公司製造) 17)二丙二醇單甲醚(MFDG，溶劑，日本乳化劑公司製造) (實施例1) 調配合成例1中所獲得之丙烯酸系聚合物1 15重量份、DPHA(第1丙烯酸系單體，二季戊四醇六丙烯酸酯，Daicel-Allnex公司製造)5重量份、A-200(第2丙烯酸系單體，聚乙二醇二丙烯酸酯，新中村化學工業公司製造)1重量份、157S(雙酚A酚醛清漆型環氧樹脂，三菱化學公司製造，於25℃下為固體)8重量份、TPO(作為光自由基產生劑之光聚合起始劑，BASF Japan公司製造)2重量份、CR-50(氧化鈦，石原產業公司製造)40重量份、FH105(滑石，Fuji Talc公司製造)10重量份、KS-7710(複合物型聚矽氧油、聚二甲基矽氧烷，信越化學工業公司製造)1重量份及二丙二醇單甲醚(MFDG，溶劑，日本乳化劑公司製造)30重量份，藉由混合機(Thinky公司製造之「練太郎ARE-310」)混合3分鐘後，藉由三輥研磨機進行混合，獲得混合物。其後，使用ARE-310，將所獲得之混合物脫泡3分鐘，藉此獲得作為硬化性組合物之抗蝕劑材料。 (實施例2～15及比較例1～5) 如下述表1、2所示般變更所使用之材料之種類及調配量，除此以外，以與實施例1相同之方式獲得作為硬化性組合物之抗蝕劑材料。 (評價) (1)測定樣品之製作 準備80 mm×90 mm、厚度0.8 mm之FR-4基板。於該基板上，藉由網版印刷法，使用100目之聚酯包邊製版，藉由實心圖案而印刷抗蝕劑材料。印刷後，於80℃之烘箱內乾燥20分鐘，於基板上形成抗蝕劑材料層。其次，經由具有特定之圖案之光罩，使用紫外線照射裝置，以照射能量成為400 mJ/cm2
之方式以100 mW/cm2
之紫外線照度對抗蝕劑材料層照射波長365 nm之紫外線4秒。其後，為了去除未曝光部之抗蝕劑材料層而形成圖案，將抗蝕劑材料層浸漬於碳酸鈉之1重量%水溶液(25℃)中30秒而進行顯影，於基板上形成抗蝕劑膜。其後，於150℃之烘箱內加熱1小時而使抗蝕劑膜後硬化，藉此獲得作為測定樣品之抗蝕劑膜。所獲得之抗蝕劑膜之厚度為20 μm。 (2)耐熱性及耐熱黃變性 將測定樣品放入至加熱烘箱內，於270℃下加熱5分鐘。 使用色彩色差計(柯尼卡美能達公司製造之「CR-400」)，測定進行熱處理之前之評價樣品之L*、a*、b*。又，測定進行熱處理後之評價樣品之L*、a*、b*，根據該等2個測定值求出ΔE*ab。根據進行熱處理後之評價樣品之ΔE*ab，藉由以下之基準判定耐熱性(耐熱變色性)。又，根據熱處理前後之評價樣品之b*之變化量，藉由以下之基準判定耐熱黃變性。 [耐熱性之判定基準] ○：ΔE*ab為0.5以下 △：ΔE*ab超過0.5且為1以下 ×：ΔE*ab超過1 [耐黃變性之判定基準] ○○：b*之變化量為1.0以下 ○：b*超過1.0且為1.5以下 △：b*超過1.5且為2.0以下 ×：b*超過2.0 (3)防龜裂性 將測定樣品放入至加熱烘箱內，於270℃下加熱5分鐘。於在270℃下加熱5分鐘後之測定樣品中，確認到抗蝕劑膜之龜裂之產生狀態。又，將測定樣品放入至加熱烘箱內，於270℃下加熱10分鐘。於在270℃下加熱10分鐘後之測定樣品中，確認到抗蝕劑膜之龜裂之產生狀態。 [防龜裂性之判定基準] ○○：未產生龜裂 ○：產生最大長度未達500 μm之較小之龜裂 △：產生最大長度為500 μm以上且未達1000 μm之龜裂 ×：產生最大長度為1000 μm以上之龜裂 (4)顯影性 去除測定樣品之未曝光部之抗蝕劑殘渣、即抗蝕劑材料層，觀察殘留於形成有圖案之銅表面之抗蝕劑殘渣。自該殘渣，藉由以下之基準判定顯影性。 [顯影性之判定基準] ○○：於銅表面完全未殘留抗蝕劑材料層，清晰可見銅色 ○：於銅表面殘留極少之抗蝕劑材料層，但清晰可見銅色 △：於銅表面殘留較少之抗蝕劑材料層，銅色泛白 ×：於銅表面殘留抗蝕劑材料層，未見銅色 將組成及結果示於下述表1、2。 [表1]
[表2] Hereinafter, the details of the present invention will be described. [Sclerosing Composition] The curable composition of the present invention is preferably used by curing by irradiation with light. The curable composition of the present invention is preferably used for forming a cured film by development treatment, and more preferably for forming a resist film by development treatment. The curable composition of the present invention is preferably a developed resist-curable composition. In the curable composition of the present invention, the resist film may not be developed in order to form a resist film, and the curable composition of the present invention may be a non-developing resist-curable composition. The curable composition of the present invention is preferably a curable composition for a solder resist. The curable composition of the present invention comprises (A) a carboxyl group-containing resin, (B) a first acrylic monomer having three or more (meth)acrylonium groups, and (C) represented by the following formula (1). a second acrylic monomer, (D) a photopolymerization initiator, and (E) titanium oxide. [Chemical 2] In the above formula (1), R1 and R2 each independently represent a hydrogen atom or a methyl group, n represents an integer of 1 to 6, and m represents an integer of 1 to 30. In the present invention, as the acrylic monomer to be used in combination with the components (A), (D) and (E), the specific (B) first acrylic monomer and (C) second acrylic monomer are used in combination. In the (C) second acrylic monomer, two (meth)acrylonyl groups are directly bonded to -O-(C) without passing through other groups. n H 2n O) m base. Further, in the (C) second acrylic monomer, only -O-(C exists between two (meth)acryl fluorenyl groups n H 2n O) m Base, there are no other bases. According to the present invention, since the above configuration is provided, discoloration when the cured product is exposed to a high temperature can be suppressed, and in particular, heat-resistant yellowing can be improved. Further, in the present invention, since the above configuration is provided, it is possible to prevent the cured product from being cracked. As the acrylic monomer used in combination with the components (A), (B), (D), and (E), two (meth)acrylonyl groups are directly bonded to -O-(C) without using other groups. n H 2n O) m The second acrylic monomer is indirectly bonded to -O-(C) via the other groups using two (meth)acrylonium groups. n H 2n O) m Compared with the case of the acrylic monomer, the discoloration can be effectively suppressed, and in particular, the heat-resistant yellowing can be effectively improved, and the occurrence of cracks can be effectively suppressed. Further, as the acrylic monomer used in combination with the components (A), (B), (D), and (E), only -O-(C) is present between two (meth)acryl fluorenyl groups. n H 2n O) m a second acrylic monomer based on the presence of -O-(C) between the two (meth) acrylonitrile groups n H 2n O) m Compared with the case of the acrylic monomer other than the base, the discoloration can be effectively suppressed, and in particular, the heat-resistant yellowing can be effectively improved, and the occurrence of cracks can be effectively suppressed. Further, in the present invention, since the above configuration is provided, the residue can be reduced when the development process is performed when the cured product is formed. Hereinafter, each component contained in the curable composition of the present invention will be described in detail. (A) A carboxyl group-containing resin (A) The carboxyl group-containing resin is preferably a polymerizable polymer having a carboxyl group. The polymerizable polymer having a carboxyl group has polymerizability and can be polymerized. (A) The carboxyl group-containing resin is a resin other than the acrylic monomer having three or more (meth) acrylonitrile groups, and is a resin other than the acrylic monomer represented by the formula (1). (A) The carboxyl group-containing resin may be used alone or in combination of two or more. When the (A) carboxyl group-containing resin has a carboxyl group, the developability of the curable composition becomes good. Examples of the (A) carboxyl group-containing resin include an acrylic resin having a carboxyl group; an epoxy resin having a carboxyl group; and an olefin resin having a carboxyl group. Further, the "resin" is not limited to a solid resin, and includes a liquid resin and an oligomer. The (A) carboxyl group-containing resin is preferably the following carboxyl group-containing resins (a) to (e). (a) a carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid with a compound having a polymerizable unsaturated double bond (b) by a carboxyl group-containing (meth)acrylic copolymer resin (b1) and one molecule The carboxyl group-containing resin (c) obtained by the reaction of the compound (b2) having an oxirane ring and an ethylenically polymerizable unsaturated double bond has one epoxy group and a polymerizable unsaturated double bond in one molecule. a carboxyl group-containing resin obtained by reacting a copolymer of a compound and a compound having a polymerizable unsaturated double bond with an unsaturated monocarboxylic acid, and reacting a secondary hydroxyl group of the resulting reactant with a saturated or unsaturated polybasic acid anhydride (d) reacting a saturated or unsaturated polybasic acid anhydride with a hydroxyl group-containing polymer, and reacting the resulting polymer having a carboxyl group with a compound having one epoxy group and a polymerizable unsaturated double bond in one molecule And the obtained hydroxyl group-containing and carboxyl group-containing resin (e) is a resin obtained by reacting an epoxy compound having an aromatic ring with a saturated polybasic acid anhydride or an unsaturated polybasic acid anhydride, or an epoxy compound having an aromatic ring and having at least one non- saturation After the reaction of the carboxyl group-containing compound of the double bond, the resin obtained by further reacting with a saturated polybasic acid anhydride or an unsaturated polybasic acid anhydride is 100% by weight of the total component other than the solvent of the above curable composition, (A) a carboxyl group-containing resin The content is preferably 3% by weight or more, more preferably 5% by weight or more, and is preferably 50% by weight or less, more preferably 40% by weight or less. When the content of the (A) carboxyl group-containing resin is not less than the above lower limit and not more than the above upper limit, the curable composition, the photosensitivity and the developability of the curable composition are excellent, and the residue is less after development. The 100% by weight of the total component other than the solvent in the curable composition, when the curable composition contains a solvent, means 100% by weight of the total component other than the solvent of the curable composition, and is not in the curable composition. When a solvent is included, it means 100% by weight of the curable composition. (B) a first acrylic monomer having three or more (meth)acryl fluorenyl groups, and (C) a second acrylic monomer represented by the formula (1)) (B) a first acrylic monomer The body has three or more (meth) acrylonitrile groups. (B) The number of (meth)acrylonitrile groups of the first acrylic monomer may be 6 or less, or may be 5 or less. (B) The first acrylic monomer may be used alone or in combination of two or more. Examples of the (B) first acrylic monomer include a polyhydric alcohol (meth) acrylate modified product of a polyol, an ethylene oxide adduct of a polyhydric alcohol, or a propylene oxide adduct of a polyhydric alcohol; a (meth) acrylate modified product of phenol, phenol ethylene oxide adduct or phenol propylene oxide adduct; or glycidol such as glycerol diglycidyl ether or trimethylolpropane triglycidyl ether Ether (meth) acrylate modification; or melamine (meth) acrylate, and the like. Examples of the polyhydric alcohol include hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, and trihydroxyethyl isocyanurate. Examples of the (meth) acrylate of the phenol include a phenoxy (meth) acrylate and a bisphenol A bis (meth) acrylate modified product. "(Meth)acryloyl group" means an acryl group and a methacryl group. "(Meth)acrylic acid" means acrylic acid and methacrylic acid. "(Meth)acrylate" means acrylate and methacrylate. (C) The second acrylic system is represented by the following formula (1). [Chemical 3] In the above formula (1), R1 and R2 each independently represent a hydrogen atom or a methyl group, n represents an integer of 1 to 6, and m represents an integer of 1 to 30. From the viewpoint of appropriately improving the developability and the curing rate, n is preferably an integer of 4 or less, more preferably an integer of 3 or less, still more preferably 1 or 2. m is preferably an integer of 1 or more, and is preferably an integer of 25 or less, more preferably an integer of 20 or less, and further preferably 15 in terms of an appropriate increase in crack resistance, developability, and curing speed. The following integers are particularly preferably integers of 10 or less. (C) The second acrylic monomer is preferably a di(meth)acrylate modified product of an alkylene glycol. In the 100% by weight of the total component other than the solvent of the curable composition, the total content of the (B) first acrylic monomer and the (C) second acrylic monomer is preferably 3% by weight or more. It is preferably 5% by weight or more, and preferably 50% by weight or less, more preferably 40% by weight or less. When the content of the total of the (B) first acrylic monomer and the (C) second acrylic monomer is not less than the above lower limit and not more than the above upper limit, discoloration at a high temperature of the cured product can be further suppressed, and the residue is changed after development. Less. (B) Ratio of the content of the first acrylic monomer to the content of the (C) second acrylic monomer ((B) the content of the first acrylic monomer/(C) the content of the second acrylic monomer The weight ratio is preferably 0.05 or more, more preferably 1 or more, and is preferably 20 or less, more preferably 5 or less. When the content of the (B) first acrylic monomer is increased, the photocurability is further improved. When the content of the (C) second acrylic monomer is increased, the residue after development becomes less. ((D) Photopolymerization Initiator) Since the curable composition contains (D) a photopolymerization initiator, the curable composition can be cured by irradiation of light. (D) The photopolymerization initiator may be used alone or in combination of two or more. Examples of the (D) photopolymerization initiator include mercaptophosphine oxide, halomethylated tris, halomethylated oxadiazole, imidazole, benzoin, benzoin alkyl ether, anthracene, benzofluorene. Ketone, benzophenone, acetophenone, 9-oxo sulfur? , benzoate, acridine, morphine, ferrocene, alpha-aminoalkyl benzophenone, hydrazine and derivatives thereof. From the viewpoint of further suppressing discoloration at a high temperature of the cured product, higher light resistance, and further suppressing the viscosity of the surface of the cured product, a fluorenylphosphine oxide-based photopolymerization initiator is preferred. (D) Photopolymerization initiator in the above curable composition, based on 100 parts by weight of the total of (A) the carboxyl group-containing resin, (B) the first acrylic monomer, and (C) the second acrylic monomer The content is preferably 0.1 part by weight or more, more preferably 1 part by weight or more, and still more preferably 30 parts by weight or less, still more preferably 15 parts by weight or less. When the content of the (D) photopolymerization initiator is not less than the above lower limit and not more than the above upper limit, the photosensitivity and curability of the curable composition are higher. ((E) Titanium Oxide) Since the curable composition contains (E) titanium oxide, a cured product such as a resist film having a high reflectance can be formed. By using (E) titanium oxide, a cured product having a higher reflectance can be formed as compared with the case of using an inorganic filler other than (E) titanium oxide. (E) The titanium oxide may be used alone or in combination of two or more. The (E) titanium oxide is preferably rutile-type titanium oxide or anatase-type titanium oxide, more preferably rutile-type titanium oxide. By using rutile-type titanium oxide, discoloration at high temperatures of the cured product can be further suppressed. The above anatase type titanium oxide has a lower hardness than rutile type titanium oxide. Therefore, by using anatase type titanium oxide, the workability of the cured product becomes higher. Examples of the (E) titanium oxide include sulfuric acid titanium oxide and chlorine titanium oxide. From the viewpoint of further suppressing discoloration at high temperatures of the cured product, titanium chloride is preferred. Titanium chloride is a titanium oxide produced by a chlorine method. Further, from the viewpoint of effectively improving the dispersibility of (E) titanium oxide and (F) inorganic filler, the (E) titanium oxide is preferably rutile-type titanium oxide. The (E) titanium oxide preferably contains rutile-type titanium oxide as a surface treatment material based on cerium oxide or polyoxysiloxane. The content of the rutile-type titanium oxide which is the surface-treated product based on the cerium oxide or the polyfluorene oxide is preferably 10% by weight or more, and more preferably 30% by weight or more, based on 100% by weight of the (E) titanium oxide. It is preferably 100% by weight or less. (E) The total amount of the titanium oxide may be the above-described rutile-type titanium oxide which is a surface-treated material based on a cerium oxide or a polysiloxane. By using the above-described rutile-type titanium oxide which is a surface treatment material based on a cerium oxide or a polyoxygen oxide compound, discoloration at a high temperature of the cured product can be further suppressed. The rutile-type titanium oxide which is a surface-treated material based on a cerium oxide or a polyoxygen oxy-compound is exemplified by the number of CR-90 manufactured by Ishihara Sangyo Co., Ltd. as a rutile chlorinated titanium oxide; or as rutile sulfuric acid. The number of the titanium oxide company Ishihara Industry Co., Ltd. is manufactured by R-550. The average particle diameter of the (E) titanium oxide is preferably 0.1 μm or more, more preferably 0.15 μm or more, and is preferably 1 μm or less, more preferably 0.5 μm or less. (E) The average particle diameter of titanium oxide is a particle diameter value when the cumulative value in the volume-based particle size distribution curve is 50%. The average particle diameter can be measured, for example, using a laser light particle size distribution meter. As a commercial item of this laser light-type particle size distribution meter, "LS13320" by Beckman Coulter company, etc. are mentioned. The content of the (E) titanium oxide in the 100% by weight of the component other than the solvent of the curable composition is preferably 3% by weight or more, more preferably 10% by weight or more, still more preferably 15% by weight or more, and It is preferably 80% by weight or less, more preferably 75% by weight or less, still more preferably 70% by weight or less. When the content of the (E) titanium oxide is not less than the above lower limit and not more than the above upper limit, discoloration at a high temperature of the cured product can be further suppressed. Further, a curable composition having a viscosity suitable for coating can be easily prepared. ((F) Inorganic Filler) The curable composition may further contain (F) an inorganic filler different from titanium oxide. (F) An inorganic filler is an inorganic filler different from titanium oxide. (F) The inorganic filler may be used alone or in combination of two or more. Specific examples of the (F) inorganic filler include cerium oxide, aluminum oxide, mica, cerium oxide, potassium titanate, barium titanate, barium titanate, calcium titanate, zirconia, cerium oxide, aluminum borate, Aluminum hydroxide, magnesium oxide, calcium carbonate, magnesium carbonate, aluminum carbonate, calcium citrate, aluminum citrate, magnesium citrate, calcium phosphate, calcium sulfate, barium sulfate, tantalum nitride, boron nitride, calcined clay, etc. Talc, tantalum carbide, resin particles of crosslinked acrylic resin, and polyfluorene oxide particles. The curable composition preferably contains talc or cerium oxide from the viewpoint of further suppressing discoloration at a high temperature of the cured product, improving the light resistance of the cured product, and further suppressing the viscosity of the surface of the cured product. More preferably, it contains cerium oxide. The above curable composition may also contain talc. The average particle diameter of the inorganic filler (F) is preferably 0.1 μm or more, more preferably 0.2 μm or more, and is preferably 10 μm or less, more preferably 5 μm or less. (F) The average particle diameter of the inorganic filler is a particle diameter value when the cumulative value in the volume-based particle size distribution curve is 50%. The average particle diameter can be measured, for example, using a laser light particle size distribution meter. As a commercial item of this laser light-type particle size distribution meter, "LS13320" by Beckman Coulter company, etc. are mentioned. The content of the (F) inorganic filler in the 100% by weight of the curable composition is preferably 0.1% by weight or more, more preferably 1% by weight or more, still more preferably 3% by weight or more, and preferably 50% by weight. Hereinafter, it is more preferably 30% by weight or less, still more preferably 10% by weight or less. When the content of the (F) inorganic filler is not less than the above lower limit and not more than the above upper limit, discoloration at a high temperature of the cured product can be further suppressed, and the light resistance of the cured product becomes higher, and the surface of the cured product can be further suppressed from being sticky. . The content of the total of the (E) titanium oxide and the (F) inorganic filler in the 100% by weight of the curable composition is preferably 5% by weight or more, more preferably 10% by weight or more, still more preferably 20% by weight or more. It is preferably 80% by weight or less, more preferably 60% by weight or less, still more preferably 40% by weight or less. When the content of the total of the (E) titanium oxide and the (F) inorganic filler is not less than the above lower limit and not more than the above upper limit, the discoloration of the cured product at a high temperature can be further suppressed, and the light resistance of the cured product becomes higher, and the film can be further suppressed. The stickyness of the surface of the cured product. In the above curable composition, the ratio of the content of (E) titanium oxide to the content of (F) inorganic filler ((E) content of titanium oxide / content of (F) inorganic filler) is preferably 0.1 on a weight basis. The above is more preferably 1 or more, and is preferably 50 or less, more preferably 30 or less. ((G) Epoxy Compound) The curable composition preferably contains (G) an epoxy compound for the purpose of improving the cutting workability of the cured product. Further, by using the (G) epoxy compound, the curability of the curable composition is also good. (G) epoxy compound (A) An epoxy compound other than the carboxyl group-containing resin. (E) The epoxy compound may be used alone or in combination of two or more. Examples of the (G) epoxy compound include a bisphenol S type epoxy resin, a diglycidyl phthalate resin, a heterocyclic epoxy resin such as triglycidyl isocyanurate, and a bixylenol type. Epoxy resin, biphenol type epoxy resin, tetraglycidyl xylene decyl ethane resin, bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type resin, brominated bisphenol A type epoxy resin, phenol novolak type epoxy resin, cresol novolac type epoxy resin, alicyclic epoxy resin, bisphenol A novolak type epoxy resin, chelating epoxy resin, ethylene two Aldehyde type epoxy resin, amine-containing epoxy resin, rubber modified epoxy resin, dicyclopentadiene phenol type epoxy resin, polyfluorene modified epoxy resin and ε-caprolactone modified epoxy resin . (E) The epoxy compound may be used alone or in combination of two or more. The (G) epoxy compound preferably reacts with the carboxyl group of the (A) carboxyl group-containing resin to cure the curable composition. The (G) epoxy compound is preferably not liquid at 25 ° C from the viewpoint of further suppressing discoloration at high temperature of the cured product and having less residue after development, and is preferably at 25 ° C. Solid. (G) When the epoxy compound is not liquid at 25 ° C means that the epoxy resin to be tested is crystallized, 100 g of the epoxy resin to be tested is kept at a temperature of 80 ° C for 24 hours, The test sample cooled to 25 ° C in 0.5 hours and the elapsed time of 1 hour after reaching 25 ° C satisfies either of the following two conditions. That is, (1) the test sample is placed in a vertical test tube (using a flat-bottom cylindrical glass mold having an inner diameter of 30 mm and a height of 120 mm) until the height from the bottom of the test tube becomes 55 mm. When the temperature of the sample is controlled at 25 ° C, the tube is leveled by stirring with a stir bar for 1 minute until the front end of the moving surface of the test sample passes through a distance of 60 mm from the bottom of the test tube. When the time is 90 seconds or longer, it is set to "not liquid at 25 ° C". (2) When the test sample is measured by a B-type viscometer under the condition of 25 ° C, when it is 3,000,000 cps or more, it is set to "not liquid at 25 ° C". The fact that the (G) epoxy compound is solid at 25 ° C means that all of the above two conditions (1) and (2) are satisfied. In the above curable composition, the content of the (G) epoxy compound is preferably 0.1 part by weight or more, more preferably 1 part by weight or more, and preferably 50% by weight based on 100 parts by weight of the (A) carboxyl group-containing resin. It is more preferably 30 parts by weight or less. When the content of the (G) epoxy compound is at least the above lower limit and not more than the above upper limit, the electrical insulating properties of the cured product become higher. ((H) Solvent) The curable composition may further contain a (H) solvent. (H) The solvent may be used alone or in combination of two or more. The (H) solvent is generally an organic solvent. Examples of the organic solvent include ketone compounds such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbon compounds such as toluene, xylene, and tetramethylbenzene; cellosolve, methyl cellosolve, and butyl cellosolve. Glycol ether compounds such as carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, tripropylene glycol monomethyl ether; ethyl acetate, butyl acetate , butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate An ester compound such as dipropylene glycol monomethyl ether acetate or propylene carbonate; an aliphatic hydrocarbon compound such as octane or decane; a petroleum solvent such as petroleum ether or naphtha; and a dibasic acid ester. The above dibasic acid ester is referred to as a solvent of DBE. The content of the (H) solvent in 100% by weight of the curable composition is preferably 5% by weight or more, more preferably 10% by weight or more, and is preferably 50% by weight or less, more preferably 30% by weight or less. (I) Antioxidant The above curable composition may further contain (I) an antioxidant in view of further suppressing discoloration at a high temperature of the cured product. (I) The antioxidant preferably has a Lewis basic site. The (I) antioxidant is preferably a phenol-based antioxidant, a phosphorus-based antioxidant or an amine-based antioxidant, and more preferably a phenol-based antioxidant, from the viewpoint of further suppressing discoloration at a high temperature of the cured product. As a commercial item of the phenolic antioxidant, IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, IRGANOX 245, IRGANOX 259, and IRGANOX 295 (all of which are manufactured by Ciba Japan Co., Ltd.); Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-60, Adekastab AO-70, Adekastab AO-80, Adekastab AO-90 and Adekastab AO-330 (all manufactured by ADEKA); Sumilizer GA-80, Sumilizer MDP- S, Sumilizer BBM-S, Sumilizer GM, Sumilizer GS (F) and Sumilizer GP (all manufactured by Sumitomo Chemical Industries); HOSTANOX O10, HOSTANOX O16, HOSTANOX O14 and HOSTANOX O3 (all of which are manufactured by Clariant); Antage BHT, Antage W-300, Antage W-400 and Antage W500 (all of which are manufactured by Kawaguchi Chemical Industry Co., Ltd.); and SEENOX 224M and SEENOX 326M (all of which are manufactured by Shipro Kasei Co., Ltd.). Examples of the phosphorus-based antioxidant include cyclohexylphosphine and triphenylphosphine. Commercial products of the above phosphorus-based antioxidants include Adekastab PEP-4C, Adekastab PEP-8, Adekastab PEP-24G, Adekastab PEP-36, Adekastab HP-10, Adekastab 2112, Adekastab 260, Adekastab 522A, Adekastab 1178. , Adekastab 1500, Adekastab C, Adekastab 135A, Adekastab 3010 and Adekastab TPP (all manufactured by ADEKA); Sandostab P-EPQ and Hostanox PAR24 (all manufactured by Clariant); and JP-312L, JP-318-0 , JPM-308, JPM-313, JPP-613M, JPP-31, JPP-2000PT and JPH-3800 (all of which are manufactured by Chengbei Chemical Industry Co., Ltd.). Examples of the amine-based antioxidant include triethylamine, dicyandiamide, melamine, and ethyldiamine-based, and 2,4-diamine-based, 2,4-diamino- 6-tolyl is a tris?, 2,4-diamino-6-dimethylphenyl sulphate and a quaternary ammonium salt derivative. The content of the (I) antioxidant is preferably 0.1 part by weight or more, more preferably 5 parts by weight or more, and preferably 30 parts by weight or less, more preferably 15 parts by weight, based on 100 parts by weight of the (A) carboxyl group-containing resin. the following. When the content of the (I) antioxidant is not less than the above lower limit and not more than the upper limit, discoloration at a high temperature of the cured product is further suppressed. (Other components) The curable composition may further contain a colorant, a filler, an antifoaming agent, a hardener, a hardening accelerator, a mold release agent, a surface treatment agent, a flame retardant, a viscosity modifier, a dispersant, and a dispersion aid. Agent, surface modifier, plasticizer, antibacterial agent, antifungal agent, leveling agent, stabilizer, coupling agent, anti-sagging agent or phosphor. The curable composition can be prepared, for example, by mixing and mixing the respective components, and then uniformly mixing them by a three-roll mill. Examples of the light source for curing the curable composition include an irradiation device that emits an active energy ray such as ultraviolet rays or visible rays. Examples of the light source include an ultrahigh pressure mercury lamp, a Deep UV lamp, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, and an excimer laser. These light sources are appropriately selected depending on the light-sensing wavelength of the constituent components of the curable composition. The light irradiation energy is appropriately selected depending on the desired thickness or the constituent components of the curable composition. The light irradiation energy is generally 10 to 3000 mJ/cm. 2 Within the scope. [Manufacturing method of electronic component and electronic component] The manufacturing method of the electronic component of the present invention includes the step of applying the curable composition on the surface of the electronic component body to form a composition layer; and irradiating the composition layer with light The step of forming a hardened film. In the method of producing an electronic component of the present invention, in order to form the cured film, the composition layer may be developed. The composition layer is preferably a resist layer, and the cured film is preferably a resist film. When the development process is not performed, the photocurable composition may be applied to the surface of the electronic component body partially and in plural portions. From the viewpoint of preventing thermal deterioration of the electronic component body, in order to form the cured film, it is preferred that the composition layer is not thermally cured by the action of a thermosetting agent. From the viewpoint of preventing thermal deterioration of the electronic component body, in order to form the cured film, it is preferably not heated to 150 ° C or higher, and more preferably not heated to 100 ° C or higher. In order to form the hardened film described above, it is preferred not to carry out the roughening treatment. Hereinafter, a method of manufacturing the specific electronic component of the present invention will be described with reference to the drawings. In the embodiment described below, the composition layer is a resist layer, and the cured film is a resist film. In order to form a resist film, a non-developing resist photocurable composition is used. Fig. 1 (a) to (e) are cross-sectional views for explaining an example of a method of producing an electronic component using the curable composition of one embodiment of the present invention. First, as shown in FIG. 1(a), the coating target member 11 is prepared. The coating target member 11 is an electronic component body. The substrate 11A is used as the coating target member 11, and a plurality of electrodes 11B are disposed on the surface of the substrate 11A. Then, as shown in Fig. 1(b), a curable composition (used in the form of a developed resist-curable composition) of one embodiment of the present invention is applied onto the surface of the coating member 11 to form a surface. Resist layer 12 (composition layer). In FIG. 1(b), a resist layer 12 is integrally formed on the surface of the coating member 11. Next, as shown in FIG. 1(c), only the resist layer 12 between the electrodes 11B is irradiated with light via the mask 13. Thereafter, as shown in FIG. 1(d), development is performed to partially remove the resist layer 12 which is located on the electrode 11B and which is not irradiated with light. After the resist layer 12 is partially removed, the remaining resist layer 12 is thermally hardened. As a result, as shown in FIG. 1(e), the electronic component 1 in which the resist film 2 is formed on the surface of the coating member 11 (electronic component body) is obtained. 2(a) to 2(c) are cross-sectional views for explaining another example of a method of manufacturing an electronic component using the curable composition of one embodiment of the present invention. As shown in FIG. 2(a), the coating target member 11 is prepared. Then, as shown in Fig. 2 (b), the curable composition of the second embodiment of the present invention (used in the form of a non-developing resist-curable composition) is applied to the surface of the coating member 11. A resist layer 12X (composition layer) is formed. In FIG. 2(b), the curable composition is applied to the surface of the coating member 11 partially and in plural portions to form a plurality of resist layers 12X. Specifically, a plurality of resist layers 12X are formed between the plurality of electrodes 11B on the surface of the substrate 11A. The resist layer 12X is, for example, a resist pattern. For example, when the resist type curable composition is used, the resist layer 12X is formed only at a position corresponding to the portion of the resist layer which remains after development. The resist layer 12X is not formed at a position corresponding to the portion of the resist layer which is removed by development using the developed resist-curable composition. Next, the resist layer 12X is irradiated with light. For example, the resist layer 12X is irradiated with light from the side opposite to the side of the coating member 11 of the resist layer 12X. As a result, as shown in FIG. 2(c), the resist layer 12X is photocured to form a resist film 2X (hardened film). As a result, the electronic component 1X in which the resist film 2X is formed on the surface of the coating member 11 (electronic component body) is obtained. Examples of the method for applying the curable composition include a coating method by a dispenser, a coating method by screen printing, a coating method by an inkjet device, and the like. In terms of excellent manufacturing efficiency, screen printing is preferred. Preferably, the curable composition is subjected to pattern printing. Further, a method of manufacturing an electronic component including a resist film described with reference to FIGS. 1(a) to 1(e) and FIGS. 2(a) to 2(c) is taken as an example, and a method of manufacturing an electronic component can be appropriately changed. In the present invention, one layer of the photocurable composition may be applied to the surface of the member to be coated to form a cured layer (such as a resist layer), or two or more layers may be applied. The light is then irradiated to form a hardened layer. Hereinafter, the present invention will be specifically described by way of examples and comparative examples. The invention is not limited to the following examples. Hereinafter, the specific examples and comparative examples of the present invention will be described, and the present invention will be clarified. In the examples and comparative examples, the following materials 1) to 17) were used. 1) Acrylic polymer 1 (carboxyl-containing resin, acrylic polymer 1 obtained in Synthesis Example 1 below) (Synthesis Example 1) was added to a flask equipped with a thermometer, a stirrer, a dropping funnel, and a reflux condenser. Ethyl carbitol acetate as solvent and azobisisobutyronitrile as catalyst, heated to 80 ° C under nitrogen atmosphere, and 30:70 molar ratio of mixed methacrylic acid and A was added over 2 hours. A monomer made of methyl acrylate. After the dropwise addition, the mixture was stirred for 1 hour, and the temperature was raised to 120 °C. Thereafter, cooling is performed. Adding a molar ratio of all the monomer units of the obtained resin to a molar ratio of 10 parts of glycidyl acrylate, using tetrabutylammonium bromide as a catalyst, heating at 100 ° C 30 In an hour, an addition reaction of glycidyl acrylate with a carboxyl group is carried out. After cooling, it was taken out from the flask to obtain a solution containing 50% by weight (nonvolatile content) of a carboxyl group-containing resin having an acid value of 60 mgKOH/g of a solid content, a weight average molecular weight of 15,000, and a double bond equivalent of 1,000. Hereinafter, this solution is referred to as acrylic polymer 1. 2) DPHA (first acrylic monomer, dipentaerythritol hexaacrylate, manufactured by Daicel-Allnex) 3) TMPTA (first acrylic monomer, trimethylolpropane triacrylate, manufactured by Daicel-Allnex) 4 ) A-200 (2nd acrylic monomer, polyethylene glycol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) 5) A-400 (2nd acrylic monomer, polyethylene glycol diacrylate, Xinzhongcun) 6) A-600 (second acrylic monomer, polyethylene glycol diacrylate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) 7) A-1000 (second acrylic monomer, polyethylene glycol Diacrylate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) 8) APG-400 (2nd acrylic monomer, polypropylene glycol diacrylate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) 8) A-PTMG-65 (2nd acrylic single , polytetramethylene glycol diacrylate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) 9) BPE-1300N (other acrylic monomers, ethoxylated bisphenol A dimethacrylate, Xinzhongcun Chemical Industry Co., Ltd.) Manufacturing) 10) ABE-300 (other acrylic monomers, ethoxylated bisphenol A diacrylate, Xinzhongcun Chemical 11) 157S (bisphenol A novolac type epoxy resin, manufactured by Mitsubishi Chemical Corporation, solid at 25 ° C (solid)) 12) jER 828 (bisphenol A type epoxy resin, Mitsubishi Chemical Corporation Manufactured at 25 ° C in liquid form) 13) TPO (photopolymerization initiator as photoradical generator, manufactured by BASF Japan) 14) CR-50 (titanium oxide, manufactured by Ishihara Sangyo Co., Ltd.) 15) FH105 ( Talc, manufactured by Fuji Talc) 16) KS-7710 (composite type polyoxyxide oil, polydimethyl methoxy oxane, manufactured by Shin-Etsu Chemical Co., Ltd.) 17) Dipropylene glycol monomethyl ether (MFDG, solvent, Japanese emulsifier) (manufactured by the company) (Example 1) 15 parts by weight of the acrylic polymer obtained in Synthesis Example 1 and 5 parts by weight of DPHA (first acrylic monomer, dipentaerythritol hexaacrylate, manufactured by Daicel-Allnex Co., Ltd.) A-200 (second acrylic monomer, polyethylene glycol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) 1 part by weight, 157S (bisphenol A novolac type epoxy resin, manufactured by Mitsubishi Chemical Corporation, at 25 ° C Below is a solid) 8 parts by weight, TPO (photopolymerization initiator as photoradical generator, BASF Jap) (manufactured by the company), 2 parts by weight, 40 parts by weight of CR-50 (titanium oxide, manufactured by Ishihara Sangyo Co., Ltd.), 10 parts by weight of FH105 (talc, manufactured by Fuji Talc Co., Ltd.), KS-7710 (composite type polyoxygenated oil, poly Dimethyl decane, manufactured by Shin-Etsu Chemical Co., Ltd.) 1 part by weight and 30 parts by weight of dipropylene glycol monomethyl ether (MFDG, solvent, manufactured by Nippon Emulsifier Co., Ltd.), by a mixer (Kyotaro ARE, manufactured by Thinky Corporation) -310") After mixing for 3 minutes, mixing was carried out by a three-roll mill to obtain a mixture. Thereafter, the obtained mixture was defoamed for 3 minutes using ARE-310, whereby a resist material as a curable composition was obtained. (Examples 2 to 15 and Comparative Examples 1 to 5) A hardening combination was obtained in the same manner as in Example 1 except that the types and the amounts of the materials used were changed as shown in the following Tables 1 and 2. Resist material. (Evaluation) (1) Preparation of measurement sample An FR-4 substrate of 80 mm × 90 mm and a thickness of 0.8 mm was prepared. On the substrate, a resist material was printed by a screen printing method using a 100-mesh polyester edging plate by a solid pattern. After printing, it was dried in an oven at 80 ° C for 20 minutes to form a resist material layer on the substrate. Next, using a UV ray irradiation device with a specific pattern, the irradiation energy becomes 400 mJ/cm. 2 The way is 100 mW/cm 2 The ultraviolet illuminance irradiates the resist material layer with ultraviolet rays having a wavelength of 365 nm for 4 seconds. Thereafter, a pattern was formed in order to remove the resist material layer in the unexposed portion, and the resist material layer was immersed in a 1% by weight aqueous solution (25 ° C) of sodium carbonate for 30 seconds to develop, and a resist was formed on the substrate. Membrane film. Thereafter, the resist film was post-hardened by heating in an oven at 150 ° C for 1 hour, thereby obtaining a resist film as a measurement sample. The thickness of the obtained resist film was 20 μm. (2) Heat resistance and heat-resistant yellowing The measurement sample was placed in a heating oven and heated at 270 ° C for 5 minutes. L*, a*, b* of the evaluation sample before heat treatment were measured using a color difference meter ("CR-400" manufactured by Konica Minolta Co., Ltd.). Further, L*, a*, and b* of the evaluation sample after the heat treatment were measured, and ΔE*ab was obtained from the two measured values. According to the ΔE*ab of the evaluation sample after the heat treatment, heat resistance (heat discoloration resistance) was determined by the following criteria. Further, based on the amount of change in b* of the evaluation sample before and after the heat treatment, heat-resistant yellowing was determined by the following criteria. [Criteria for determination of heat resistance] ○: ΔE*ab is 0.5 or less Δ: ΔE*ab is more than 0.5 and is 1 or less ×: ΔE*ab is more than 1 [Criteria for determination of yellowing resistance] ○○: The amount of change of b* is 1.0 or less ○: b* exceeds 1.0 and is 1.5 or less △: b* exceeds 1.5 and is 2.0 or less ×: b* exceeds 2.0 (3) Anti-crack property The measurement sample is placed in a heating oven and heated at 270 °C. 5 minutes. In the measurement sample after heating at 270 ° C for 5 minutes, the state of occurrence of cracking of the resist film was confirmed. Further, the measurement sample was placed in a heating oven and heated at 270 ° C for 10 minutes. In the measurement sample after heating at 270 ° C for 10 minutes, the state of occurrence of cracking of the resist film was confirmed. [Criteria for Judging Crack Resistance] ○○: No cracks are generated. ○: Small cracks with a maximum length of less than 500 μm are produced. Δ: Cracks with a maximum length of 500 μm or more and less than 1000 μm are produced ×: Cracks having a maximum length of 1000 μm or more were produced. (4) The resist residue of the unexposed portion of the measurement sample, that is, the resist material layer, was removed, and the resist residue remaining on the surface of the patterned copper was observed. From the residue, the developability was judged by the following criteria. [Criteria for the determination of developability] ○○: The resist material layer is not left at all on the copper surface, and the copper color is clearly visible. ○: The resist material layer remains extremely small on the copper surface, but the copper color Δ is clearly visible on the copper surface. The resist material layer remaining less, the copper color was whitened ×: the resist material layer remained on the copper surface, the copper color was not observed, and the results are shown in Tables 1 and 2 below. [Table 1] [Table 2]