201205195 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種適合用於形成在基板上形成之阻焊 膜、或形成於搭载有發光二極體晶片之基板上的使光反射 r 之阻劑膜等阻劑膜之感光性組合物，及使用該感光性組合 物之印刷電路板。 【先前技術】 作為用以保護印刷電路板免受高溫之焊錫之保護膜，廣 泛使用阻焊膜。 又，於各種電子機器用途中，於印刷電路板之上面搭載 有發光二極體（以下簡稱為LED(Light Emitting Diode))晶 片°為了亦利用自LED所發出之光中到達上述印刷電路板 之上面侧之光，有時於印刷電路板之上面形成有白色阻焊 膜。於該情形時，不僅可利用自LED晶片之表面直接照射 至與印刷電路板相反侧之光，亦可利用到達印刷電路板之 上面側並經白色阻焊膜反射之反射光。因此，可提高自 LED所產生之光之利用效率。 作為用以形成上述白色阻焊膜之材料之一例，於下述專 ，利文獻1中揭示有以下之阻劑材料：其含有藉由環氧樹脂 與水解性烷氧基矽烷之脫醇反應而獲得之含烷氧基之矽烷 改質環氧樹脂，且進而含有含不飽和基之聚羧酸樹脂、稀 釋劑、光聚合起始劑、及硬化密接性賦予劑。 於下述專利文獻2中，揭示有以下之白色阻焊劑材料： 其含有不具有芳香環之含羧基之樹脂、光聚合起始劑、環 157383.doc 201205195 氧化合物、金紅石型氧化鈦、及稀釋劑。 先前技術文獻 專利文獻 專利文獻1:日本專利特開2007-249148號公報 專利文獻2 :日本專利特開2007-322546號公報 【發明内容】 發明所欲解決之問題 於為在基板上形成阻劑膜而將如專利文獻1〜2所揭示般 之先前之阻劑材料塗佈於基板上或基板上之PET (Polyethylene terephthalate，聚對笨二甲酸乙二酯）膜上之 情形時，有於阻劑材料中含有泡，且該泡不消失而殘留於 硬化之阻劑膜中之情況。即，先前之阻劑材料有消泡性較 低之情況。 進而’於在基板上塗佈先前之阻劑材料之情形時，有阻 劑材料之排斥特性較低而配置於不欲塗佈阻劑材料之區域 之情況。 本發明之目的在於提供一種於塗佈於塗佈對象構件上 時’消泡性及排斥特性優異之感光性組合物，及使用該感 光性組合物之印刷電路板。 解決問題之技術手段 根據本發明，提供一種感光性組合物，其包含具有敌基 之聚合性聚合物、光聚合起始劑、氧化鈦、第1二氧化 石夕、第2二氧化矽、及聚二甲基矽氧烷，上述第1二氧化矽 之-人粒彳空為5 nm以上且1〇〇 nm以下，上述第2二氧化石夕 157383.doc 201205195 之一次粒徑為0.5 μπι以上且10 μιη以下，並且於將煎切速 度為1 rpm時之25 C下之黏度（mPa.s)設為η 1、將剪切速度 為10 rpm時之25°C下之黏度（mPa.s)設為η1〇時，黏度比 (η 1/η 10)為 1.1 以上。 於本發明之感光性組合物之某特定方面，進而含有酴系 抗氧化劑。 於本發明之感光性組合物之其他特定方面，將感光性組 合物100重量％中之上述第！二氧化矽之含量（重量％)設為 c 1、將感光性組合物100重量％中之上述第2二氧化矽之含 量（重量。/。）設為C2時，含量比（C1/C2)為〇」以上且1以下。 本發明之感光性組合物適合用作阻焊劑組合物。本發明 之感光性組合物較佳為阻焊劑組合物。 本發明之印刷電路板包括於表面具有電路之印刷電路板 本體、及於該印刷電路板本體之設置有電路之表面上積層 之阻焊膜，且該阻焊膜係使用根據本發明而構成之感光性 組合物形成。 發明之效果 本發明之感光性組合⑯包含具有缓基之聚合性聚合物、 光聚&起始劑、氧化鈦、一次粒徑為5⑽以上且⑽抛以 下之第1二氧切、—次粒徑為G.5 μηι以上且1G μιη以下之 第2一氧化矽、及聚二甲基矽氧烷，進而感光性組合物中 之上述黏度比⑻/㈣^為！」以上，因此將本發明之感光性 組合物塗佈於塗佈對象構件上時，可提高消泡性，且可使 排斥特性良好。 157383.doc 201205195 【實施方式】 以下對本發明進行詳細說明。 本發明之感光性組合物包含具有羧基之聚合性聚合物 (A)、光聚合起始劑（B)、氧化鈦（c)、第1二氧化矽（D1)、 第2二氧化矽（D2)、及聚二甲基矽氧烷（E)。上述第1二氧化 石夕（D1)之一次粒徑為5 nm以上且1〇〇 nm以下。上述第2二 氧化矽（D2)之一次粒徑為〇5 μιη以上且1〇 以下。於將 本發明之感光性組合物之剪切速度為1 rpin時之25°C下之 黏度（mPa.s)設為ηΐ、將剪切速度為1〇 rpm時之25〇c下之黏 度（mPa.s)設為η10時，本發明之感光性組合物之黏度比 (η1/η10)為 Μ 以上。 藉由採用本發明之感光性組合物中之上述構成，於將感 光性組合物塗佈於基板等塗佈對象構件上時，感光性組合 物之/肖’包〖生I良好。其結果，於藉由本發明之感光性組合 物而形成之阻劑膜等硬化物膜中不易含有泡，且不易產生 空隙。其結果，可提高使用本發明之感光性組合物之印刷 電路板等各種電子零件之可靠性。 進而’藉由採用本發明之感光性組合物中之上述構成， 於將感光性組合物塗佈於基板等塗佈對象構件上時，不易 產生感光性組合物之撥斥《其結果，藉由本發明之感光性 組合物而形成之阻劑膜等硬化物膜不易配置於不欲塗佈之 區域。因此，可提高使用本發明之感光性組合物之印刷電 路板等電子零件之可靠性。 上述黏度比（η1/η1〇)之上限並無特別限定，上述黏度比 157383.doc • 6 - 201205195 (η 1/η 10)較佳為5以下。 以下，對本發明之感光性組合物所含之各成分之詳情加 以說明。 (聚合性聚合物（Α)) 上述聚合性聚合物（Α)具有羧基。具有羧基之聚合性聚 合物（Α)具有聚合性而可聚合。藉由上述聚合性聚合物（α) 具有羧基，感光性組合物之顯影性變良好。作為上述聚合 性聚合物（Α) ’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 月曰」不限定於固體樹脂，亦包括液狀樹脂及寡聚物。 上述聚合性聚合物（Α)較佳為下述含羧基之樹脂 (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之樹脂 (b) 藉由含羧基之（曱基）丙烯酸系共聚合樹脂（bl)、與一 分子中具有環氧乙烧環及乙稀性聚合性不飽和雙鍵之化合 物（b2)之反應而獲得的含幾基之樹脂 (c) 對於一分子中分別含有一個環氧基及聚合性不飽和雙 鍵之化合物與含有聚合性不飽和雙鍵之化合物之共聚物， 使不飽和單羧酸與其反應後，使飽和或不飽和多元酸酐與 所生成之反應物之二級羥基反應而獲得的含羧基之樹脂 (d) 對於使飽和或不飽和多元酸酐與含經基之聚合物反 應後生成之具有羧基之聚合物，使一分子中分別含有一個 %氧基及聚合性不飽和雙鍵之化合物與其反應而獲得的含 157383.doc 201205195 羥基及羧基之樹脂 ⑷使具有芳香環之環氧化合物與飽和多元酸肝或不飽和 多元酸酐反應而獲得之樹脂，或使具有料環之環氧化合 物與含有至少-個不飽和雙鍵之含絲之化合物反應後， 進而使飽和多元_或*飽和多元_反應而獲得之樹脂 感光性組合物100重量％中’ ±述具有羧基之聚合性聚 合物（A)之含量較佳為5重量％以上，更佳為1〇重量％以 上，且較佳為50重量％以下，更佳為4〇重量％以下。若上 述聚合性聚合物⑷之含量為上述下限以上及上述上限以 下’則感光性組合物之硬化性變良好。 (光聚合起始劑（B)) 本發明之感光性組合物含有光聚合起始劑（B)，故可藉 由光之照射使感光性組合物硬化。光聚合起始劑⑺）並無 特別限定。光聚合起始劑（B)可僅使用一種，亦可併用兩 種以上。 作為上述光聚合起始劑（B)，例如可列舉：醯基氧化 膦、ii甲基化三畊、_甲基化呤二唑、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 硫咄口星、苯曱酸酯、吖啶、啡畊、二茂鈦、心胺烷基笨 酮、肟及該等之衍生物。上述光聚合起始劑（B)可僅使用 一種，亦可併用兩種以上。 相對於上述具有羧基之聚合性聚合物（A)1〇〇重量份，上 述光聚合起始劑（B)之含量較佳為〇.!重量份以上，更佳為1 重量伤以上，且較佳為3〇重量份以下，更佳為丨5重量份以 157383.doc 201205195 下。若上述光聚合起始劑（B)之含量為上述下限以上及上 述上限以下，則可進一步提高感光性組合物之感光性。 (氧化鈦（c)) 士本發明之感光性組合物含有氧化鈦，故可形成反射率較 兩之阻劑膜等硬化物肖。本發明之感光性組合物所含有之 氧化鈦（c)並無特別限定。氧化鈦（c)可僅使用一種，亦可 併用兩種以上。 藉由使用氧化鈦（C)，與使用氧化鈦（c)以外之其他無機 填料之情形相比較，可形成反射率更高之阻劑膜。"·、 上述氧化鈦（C)較佳為金紅石型氧化鈦或銳鈦礦型氧化 欽。藉由使用金紅石型氧化鈇，可形成耐熱黃變性更優異 之阻劑膜。上述銳鈦礦型氧化鈦係硬度低於金紅石型氧化 鈦。因此’藉由使用銳鈦礦型氧化鈦，可提高阻劑膜之加 工性。 上述氧化鈦（C)較佳為含有經矽氧化物或聚矽氧化合物 進行了表面處理之金紅石型氧化敛。上述氧化鈦（c)10°0重 量中’上述时氧化物或聚咬氧化合物進行了表面處理 之金紅石型氧化鈥之含量較佳為10重量 重量％以上’且較佳為100重量％以下。 %以上，更佳為30 上述氧化鈦（C)之 總量亦可為上述經矽氧化物或聚矽氧化合物進行了表面處 理之金紅石型氧化鈦。藉由使用上述經石夕氧化物或聚石夕氧 化合物進行了表面處理之金紅石型氧化鈦，可進一步提高 阻劑膜之耐熱黃變性。 作為㈣氧化物或聚石夕氧化合物進行了表面處理之金紅 157383.doc 201205195 石型氧化鈦，例如可列舉：作為金紅石氯化法氧化欽之石 原產業公司製造之商品編ecr_9g、或作為金紅石硫酸法 氧化鈦之石原產業公司製造之商品編號尺_55〇等。 本發明之感光性組合物100重量％中，氧化鈦（c)之含量 較^為3重量％以上，更佳為1〇重量％以上進而較佳心 重量％以上，且較佳為8〇重量％以下，更佳為75重量％以 下，進而較佳為70重量％以下。若氧化鈦（c)之含量為上述 I限以上及上述上限以下，則阻劑膜暴露於高溫下時不易 兴艾進而，可容易地製備具有適於塗佈之黏度的感光性 組合物。 (一氧化梦（D)) 本發明之感光性組合物含有第丨二氧化矽（Dl)及第2二氧 化矽（D2)作為二氧化矽（D)e上述第丨二氧化矽（di)之一次 粒徑為5 nm以上且100 nm以下。上述第2二氧化石夕（D2)之 一次粒徑為0.5 μΐΏ以上且10 μηι以下。上述第1、第2二氧 化矽（Dl)、（D2)均為二氧化矽粒子。上述第丨、第2二氧化 石夕（Dl)、（D2)與下述聚二甲基硬氧炫（£)不同。於本發明之 感光性組合物中，上述第丨、第2二氧化矽（di)、（D2)係與 上述聚二甲基矽氧院（E)分開調配。 上述第1、第2二氧化矽（D1)、（D2)之—次粒徑係藉由使 用雷射繞射法測定粉體粒度而測定之值。 使用具有特定之一次粒徑之上述第1、第2二氧化矽 (Dl)、（D2)兩者較大地有助於感光性組合物之消泡性及排 斥特性之提高。又，藉由使用粒徑相對較小之上述第【二 157383.doc •10· 201205195 氧化石夕（D1) ’容易使上述黏度比（η1/η10)為1·1以上。 本發明之感光性組合物1〇〇重量％中，上述第丨、第2二 氧化石夕（Dl)、（D2)之合計含量較佳為3重量％以上，更佳為 重量/。以上且較佳為5〇重量％以下，更佳為的重量％以 下若上述第卜第2二氧化矽（Dl)、（D2)之合計含量為上 述下限以上及上述上限以下，職光性組合物之消泡性及 排斥特性變得更良好。 將上述感光性組合物1〇〇重量％中之上述第丨二氧化矽 (1)之3里（重量/。）设為c丨、將上述感光性組合物1 重量 /〇中之上述第2_氧化石夕（D2)之含量（重量％)設為c2時，含 里比（C1/C2)較佳為〇」以上，且較佳為丨以下。若上述含量 比（C1/C2)為上述下限以上及上述上限以下 則感光性組 合物之消泡性及排斥特性變得更良好。 (聚一〒基石夕氧院（E)) 本發明之感光性組合物含有聚二曱基矽氧烷（E)，藉此 感光性組合物之消泡性及排斥特性變良好。上述聚二甲基 石夕氧炫（E)並無特別限^。上述聚二甲基石夕氧烧⑻與上述 第1、第2一氧化矽（D1)、⑴2)不同。於本發明之感光性組 δ物中，上述聚二甲基石夕氧烧（Ε)係與上述第1、第2二氧 化矽（Dl)、（D2)分開調配》上述聚二甲基矽氧烷（Ε)可僅使 用一種，亦可併用兩種以上。 本發明之感光性組合物1〇〇重量％中，上述聚二甲基矽 氧烧（Ε)之含量較佳為〇1重量％以上，更佳為〇3重量％以 上，且較佳為5重量％以下，更佳為3重量％以下。若上述 157383.doc 201205195 聚二甲基石夕氧烧（E)之含量為上述下限以上及上述上限以 下則感光性組合物之消泡性及排斥特性變得更良好。 (其他成分） 為了進-步提高硬化性’本發明之感光性組合物較佳為 含有聚合性單體作為與具有缓基之聚合性聚合物㈧不同 之成分。I發明之感光性組合物較佳為含有具有幾基之聚 合性聚合物（A)與聚合性單體兩者。上述聚合性單體具有 聚合性而可聚合。上述聚合性單體並無特別限定。上述聚 合性單體可僅使用一種，亦可併用兩種以上。 作為上述聚合性單體中之聚合性不鮮基，例如可列舉 (处甲基）丙烯酿基及乙烯縣等具有聚合性不飽和雙鍵之官 月b基。其中，較佳為（甲基）丙烯醯基其原因在於可提高 阻劑膜之交聯密度。 上述含聚合性不飽和基之單體較佳為具有（甲基）丙稀酿 基之化合物。作為上述具有（甲基）丙烯醯基之化合物，可 列舉：乙二醇、甲氧基四乙二醇、聚乙二醇或丙二醇等二 醇之二（曱基）丙烯酸酯改質物，或者多元醇、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(曱基)丙 稀酸酯改質物，或者笼祕、岔β = 乂有本酚本酚之環氧乙烷加成物或苯酚 之銥氧丙烷加成物之（甲基）丙烯酸酯改質物，或者甘油二 縮水甘油趟或二經甲基丙院三縮水甘油趟等縮水甘油趟之 (曱基）丙稀酸醋改質物’或者三聚氰胺（甲基）丙烯酸酯。 作為上述多元醇，例如可列舉：己二醇、三羥甲基丙 院、季戍四醇、二季戍四醇及三-經乙基異氰尿酸醋。作 157383.doc 201205195 為上述苯齡之（甲基）丙稀酸醋，例如可列舉苯氧基（甲 丙烯酸酯及雙酚A之二（甲基）丙烯酸酯改質物。 =基）丙料基」係指丙㈣基與甲基丙烯酿基。 (曱基）丙稀酸」係指丙稀酸與曱基丙稀酸。「（曱基）丙稀 酸酯」係指丙烯酸酯與甲基丙烯酸酯。 土 、 於含有上述聚合性單體之情形時，該聚合性單體與上述 具有缓基之聚合性聚合物⑷之合計1〇〇重量％中上 合性單體之含量較佳為5重量％以上，且較佳為⑽重量心 下。若上述聚合性單體之含量為上述下限以上及上述上限 ，則可使感光性組合物充分硬化H阻_ 聯密度變適當，可獲得充分之解析度，且阻劑膜不易黃 變。 為提高阻劑膜之切割加卫性，較佳為感光性組合物含有 具有環狀趟骨架之化合物…藉由使用上述具有環狀驗 骨架之化合物，感光性組合物之硬化性亦變良好。 作為上述具有環狀醚骨架之化合物，例如可列舉：雙酚 S型環氧樹脂、鄰苯二甲酸二縮水甘油醋樹脂、異氰尿酸 三縮水甘油s旨等雜環式環氧樹脂、聯二甲㈣型環氧樹 脂、聯苯酴型環氧樹脂、四縮水甘油基二甲苯齡乙烧樹 脂、雙酴A型環氧樹脂、氫化㈣A型環氧樹脂、雙齡” 樹脂、溴化雙Μ型環氧樹脂、苯紛㈣清漆型環氧樹 脂、Μ祕清漆型環氧樹脂、脂環式環氧樹脂、雙齡Α 之酴搭清漆型環氧樹脂、螯合型環氧樹脂、乙二酸型環氧 樹脂、含胺基之環氧樹脂、橡膠改質環氧樹脂、二環戍二 157383.doc 201205195 稀齡型環氧樹脂、聚石夕氧改質環氧樹脂及ε_己内醋改質環 氧樹知。上述具有環狀醚骨架之化合物可僅使用一種， 可併用兩種以上。 具有環狀趟骨架之化合物係以與叛基之聚合性聚合物 (A)所具有之羧基反應而使感光性組合物硬化之方式發揮 作用。 。相對於聚合性聚合物(A)1〇〇重量份’上述具有環狀醚骨 架之化合物之含量較佳為〇1重量份以上更佳為i重量份 以上，且較佳為50重量份以下，更佳為3〇重量份以下。若 上述具有環狀醚骨架之化合物之含量為上述下限以上及上 述上限以下，則可進一步提高阻劑膜之電氣絕緣性。 為減少暴露於高溫下時阻焊膜黃變之虞，本發明之感光 f生組合物較佳為含有抗氧化劑。上述抗氧化劑較佳為具有 路易斯鹼性部位。自進一步抑制阻劑臈之黃變之觀點而 吕，上述抗氧化劑較佳為選自由酚系抗氧化劑、磷系抗氧 化劑及胺系抗氧化劑所組成之群之至少一種。自進一步抑 制阻劑膜之黃變之觀點而言，上述抗氧化劑較佳為酴系抗 氧化劑。即，本發明之感光性組合物較佳為含有酚系抗氧 化劑。又，於使用酚系抗氧化劑作為上述抗氧化劑之情形 時，與使用酚系抗氧化劑以外之抗氧化劑之情形相比較， 感光性組合物之消泡性及排斥特性兩者變得更良好。 作為上述盼系抗氧化劑之市售品，可列舉：IRgan〇x201205195 VI. Description of the Invention: [Technical Field] The present invention relates to a solder resist film formed on a substrate or formed on a substrate on which a light-emitting diode wafer is mounted. A photosensitive composition of a resist film such as a resist film, and a printed circuit board using the photosensitive composition. [Prior Art] As a protective film for protecting a printed circuit board from high-temperature solder, a solder resist film is widely used. Further, in various electronic device applications, a light-emitting diode (hereinafter abbreviated as an LED (Light Emitting Diode)) wafer is mounted on a printed circuit board. In order to reach the printed circuit board by using light emitted from the LED. The light on the upper side is sometimes formed with a white solder resist film on the printed circuit board. In this case, it is possible to use not only light directly from the surface of the LED chip to the side opposite to the printed circuit board, but also reflected light which reaches the upper side of the printed circuit board and is reflected by the white solder resist film. Therefore, the utilization efficiency of light generated from the LED can be improved. As an example of a material for forming the white solder resist film, the following resist material is disclosed in the following document: it contains a dealcoholization reaction of an epoxy resin and a hydrolyzable alkoxysilane. The obtained alkoxy-containing decane-modified epoxy resin further contains a polycarboxylic acid resin containing an unsaturated group, a diluent, a photopolymerization initiator, and a hardening adhesion imparting agent. Patent Document 2 listed below discloses a white solder resist material containing a carboxyl group-containing resin having no aromatic ring, a photopolymerization initiator, a ring 157383.doc 201205195 oxygen compound, rutile type titanium oxide, and Thinner. CITATION LIST Patent Literature Patent Literature 1: JP-A-2007-249148, JP-A No. 2007-322546, SUMMARY OF THE INVENTION The problem to be solved by the invention is to form a resist film on a substrate. When the previous resist material as disclosed in Patent Documents 1 to 2 is applied to a PET (Polyethylene terephthalate) film on a substrate or a substrate, there is a resist. The material contains bubbles, and the bubbles do not disappear and remain in the hardened resist film. That is, the previous resist material has a low defoaming property. Further, in the case where the previous resist material is applied to the substrate, the repellent property of the resist material is low and is disposed in a region where the resist material is not to be coated. An object of the present invention is to provide a photosensitive composition which is excellent in defoaming property and repellency characteristics when applied to a member to be coated, and a printed wiring board using the photosensitive composition. Solution to Problem According to the present invention, there is provided a photosensitive composition comprising a polymerizable polymer having an enradyl group, a photopolymerization initiator, titanium oxide, first silica dioxide, second cerium oxide, and Polydimethylsiloxane, the first cerium oxide - human granule hollow is 5 nm or more and 1 〇〇 nm or less, and the second SiO 2 157383.doc 201205195 primary particle diameter is 0.5 μπι or more And 10 μηη or less, and the viscosity (mPa.s) at 25 C at a frying speed of 1 rpm is η 1 , and the viscosity at 25 ° C at a shear rate of 10 rpm (mPa.s) When η1〇 is set, the viscosity ratio (η 1/η 10) is 1.1 or more. In a specific aspect of the photosensitive composition of the present invention, a lanthanoid antioxidant is further contained. In other specific aspects of the photosensitive composition of the present invention, the above-mentioned first of 100% by weight of the photosensitive composition! The content (% by weight) of cerium oxide is c1, and the content (weight/%) of the second cerium oxide in 100% by weight of the photosensitive composition is C2, and the content ratio (C1/C2) It is above and above 1. The photosensitive composition of the present invention is suitably used as a solder resist composition. The photosensitive composition of the present invention is preferably a solder resist composition. The printed circuit board of the present invention comprises a printed circuit board body having a circuit on a surface thereof, and a solder resist film laminated on a surface of the printed circuit board body on which the circuit is disposed, and the solder resist film is constructed according to the present invention. The photosensitive composition is formed. Advantageous Effects of Invention The photosensitive composition 16 of the present invention comprises a polymerizable polymer having a slow group, a photopolymerization & initiator, titanium oxide, a primary particle diameter of 5 (10) or more, and (10) a first dioxo prior to the polishing. The second cerium oxide having a particle diameter of G.5 μηι or more and 1 G μηη or less, and polydimethyl methoxyoxane, and the above-mentioned viscosity ratio (8)/(four)^ in the photosensitive composition are! As described above, when the photosensitive composition of the present invention is applied onto a member to be coated, the defoaming property can be improved and the repelling property can be improved. 157383.doc 201205195 [Embodiment] Hereinafter, the present invention will be described in detail. The photosensitive composition of the present invention comprises a polymerizable polymer (A) having a carboxyl group, a photopolymerization initiator (B), titanium oxide (c), first cerium oxide (D1), and second cerium oxide (D2). ), and polydimethyl siloxane (E). The primary particle diameter of the first disulfide (D1) is 5 nm or more and 1 〇〇 nm or less. The primary particle diameter of the second cerium oxide (D2) is 〇5 μmη or more and 1 〇 or less. The viscosity (mPa.s) at 25 ° C when the shear rate of the photosensitive composition of the present invention is 1 rpin is η ΐ , and the viscosity at 25 〇 c when the shear rate is 1 rpm ( When mPa.s) is η10, the viscosity ratio (η1/η10) of the photosensitive composition of the present invention is Μ or more. When the photosensitive composition is applied to a member to be coated such as a substrate by the above-described configuration in the photosensitive composition of the present invention, the photosensitive composition is excellent. As a result, the cured film such as the resist film formed by the photosensitive composition of the present invention is less likely to contain bubbles and is less likely to generate voids. As a result, the reliability of various electronic components such as a printed circuit board using the photosensitive composition of the present invention can be improved. Furthermore, when the photosensitive composition is applied to a member to be coated such as a substrate by the above-described configuration in the photosensitive composition of the present invention, the repulsion of the photosensitive composition is less likely to occur. The cured film such as a resist film formed by the photosensitive composition of the invention is less likely to be disposed in a region where it is not desired to be coated. Therefore, the reliability of electronic components such as printed circuit boards using the photosensitive composition of the present invention can be improved. The upper limit of the viscosity ratio (η1/η1〇) is not particularly limited, and the viscosity ratio 157383.doc • 6 - 201205195 (η 1 / η 10) is preferably 5 or less. Hereinafter, the details of each component contained in the photosensitive composition of the present invention will be described. (Polymerizable polymer (Α)) The above polymerizable polymer (Α) has a carboxyl group. The polymerizable polymer (Α) having a carboxyl group is polymerizable and polymerizable. When the polymerizable polymer (α) has a carboxyl group, the developability of the photosensitive composition is improved. Examples of the polymerizable polymer (Α) include an acrylic resin having a carboxyl group, an epoxy resin having a carboxyl group, and an olefin resin having a carboxyl group. Further, "tree scorpion" is not limited to a solid resin, and includes a liquid resin and an oligomer. The above polymerizable polymer (Α) is preferably the following carboxyl group-containing resin (a) to (e). (a) a carboxyl group-containing resin (b) obtained by copolymerization of an unsaturated carboxylic acid and a compound having a polymerizable unsaturated double bond (b) by a carboxyl group-containing (fluorenyl) acrylic copolymer resin (bl), a group-containing resin (c) obtained by a reaction with a compound (b2) having an epoxy group and an ethylene polymerizable unsaturated double bond in one molecule, each having one epoxy group and polymerized in one molecule a copolymer of a compound having an unsaturated double bond and a compound containing a polymerizable unsaturated double bond, and reacting the unsaturated monocarboxylic acid with a saturated or unsaturated polybasic acid anhydride to react with a secondary hydroxyl group of the resulting reactant The obtained carboxyl group-containing resin (d) is a polymer having a carboxyl group formed by reacting a saturated or unsaturated polybasic acid anhydride with a polymer having a warp group, so that one molecule contains one % of an oxy group and a polymerizable unsaturated double a resin obtained by reacting a compound of a bond with a hydroxy resin and a carboxyl group of 157383.doc 201205195 (4), a resin obtained by reacting an epoxy compound having an aromatic ring with a saturated polybasic acid or an unsaturated polybasic acid anhydride, or A resin photosensitive composition obtained by reacting an epoxy compound having a ring and a silk-containing compound containing at least one unsaturated double bond, and then saturating a polyvalent- or *saturated poly-reaction to obtain a weight of 100% by weight The content of the polymerizable polymer (A) having a carboxyl group is preferably 5% by weight or more, more preferably 1% by weight or more, and is preferably 50% by weight or less, more preferably 4% by weight or less. When the content of the polymerizable polymer (4) is at least the above lower limit and below the upper limit, the curing property of the photosensitive composition is improved. (Photopolymerization initiator (B)) Since the photosensitive composition of the present invention contains the photopolymerization initiator (B), the photosensitive composition can be cured by irradiation of light. The photopolymerization initiator (7)) is not particularly limited. The photopolymerization initiator (B) may be used alone or in combination of two or more. Examples of the photopolymerization initiator (B) include mercaptophosphine oxide, ii methylated tri-till, _methylated oxadiazole, imidazole, benzoin, benzoin alkyl ether, and 蒽醌'benzoxene. Ketones, benzophenones, acetophenones, 9-oxopurine, benzoate, acridine, morphine, ferrocene, pentaalkyl ketone, hydrazine and derivatives thereof. The photopolymerization initiator (B) may be used singly or in combination of two or more. The content of the photopolymerization initiator (B) is preferably 〇.. by weight or more, more preferably 1 part by weight or more, based on 1 part by weight of the polymerizable polymer (A) having a carboxyl group. Preferably, it is 3 parts by weight or less, more preferably 5 parts by weight to 157383.doc 201205195. When the content of the photopolymerization initiator (B) is at least the above lower limit and not more than the above upper limit, the photosensitivity of the photosensitive composition can be further improved. (Titanium oxide (c)) The photosensitive composition of the present invention contains titanium oxide, so that a cured product such as a resist film having a reflectance of two can be formed. The titanium oxide (c) contained in the photosensitive composition of the present invention is not particularly limited. The titanium oxide (c) may be used alone or in combination of two or more. By using titanium oxide (C), a resist film having a higher reflectance can be formed as compared with the case of using an inorganic filler other than titanium oxide (c). "·, the above titanium oxide (C) is preferably rutile-type titanium oxide or anatase-type oxidized. By using rutile-type cerium oxide, a resist film which is more excellent in heat-resistant yellowing can be formed. 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 resist film can be improved. The titanium oxide (C) is preferably a rutile-type oxidizing agent which has been surface-treated with a cerium oxide or a polyfluorene oxide compound. The content of the rutile-type cerium oxide surface-treated with the above-mentioned oxide or polyoxygenate in the above-mentioned titanium oxide (c) of 10 ° 0 is preferably 10% by weight or more and preferably 100% by weight or less. . More preferably, the total amount of the titanium oxide (C) may be rutile-type titanium oxide surface-treated with the above-mentioned cerium oxide or polyoxyxaoxide. The heat-resistant yellowing of the resist film can be further improved by using the above-described rutile-type titanium oxide which has been surface-treated with the shi xi oxide or the polyoxo compound. Gold-red 157383.doc 201205195 As the stone-type titanium oxide, which is surface-treated with (4) an oxide or a polyoxo compound, for example, as a rutile chlorination method, the product ecr_9g manufactured by Ishihara Ishihara Industry Co., Ltd., or as Product number _55〇 manufactured by Ishihara Sangyo Co., Ltd. of rutile sulfuric acid method. In 100% by weight of the photosensitive composition of the present invention, the content of the titanium oxide (c) is 3% by weight or more, more preferably 1% by weight or more, further preferably 7% by weight or more, and preferably 8 Å by weight. % or less is more preferably 75% by weight or less, still more preferably 70% by weight or less. When the content of the titanium oxide (c) is not less than the above-mentioned I limit and not more than the above upper limit, the resist film is less likely to be exposed when exposed to a high temperature, and a photosensitive composition having a viscosity suitable for coating can be easily prepared. (Oxidation Dream (D)) The photosensitive composition of the present invention contains ruthenium dioxide (Dl) and second ruthenium dioxide (D2) as ruthenium dioxide (D)e and the above ruthenium dioxide (di) The primary particle size is 5 nm or more and 100 nm or less. The primary particle diameter of the second dioxide dioxide (D2) is 0.5 μΐΏ or more and 10 μηι or less. The first and second bismuth oxides (D1) and (D2) are all cerium oxide particles. The above-mentioned Dijon and Titanium dioxide (Dl) and (D2) are different from the following polydimethylxanthene (£). In the photosensitive composition of the present invention, the above-mentioned second and second cerium oxide (di) and (D2) are separately formulated from the above-mentioned polydimethyl oxime (E). The primary particle diameter of the first and second cerium oxides (D1) and (D2) is a value measured by measuring the particle size of the powder by a laser diffraction method. The use of both the first and second cerium oxides (D1) and (D2) having a specific primary particle diameter greatly contributes to the improvement of the defoaming property and the repellent property of the photosensitive composition. Further, it is easy to make the viscosity ratio (η1/η10) of 1.1 or more by using the above-mentioned second [157383.doc •10·201205195 oxidized stone (D1)] having a relatively small particle diameter. In the photosensitive composition of the present invention, the total content of the first and second silica dioxides (D1) and (D2) is preferably 3% by weight or more, and more preferably weight/% by weight. In the above, it is preferably 5% by weight or less, more preferably 5% by weight or less. When the total content of the second cerium dioxide (D1) and (D2) is at least the above lower limit and less than the above upper limit, the photo-optic combination The defoaming and repellency properties of the material become better. 3 parts (w/w) of the above-mentioned ruthenium dioxide (1) in 1% by weight of the photosensitive composition is c丨, and the second part of the photosensitive composition 1 by weight/〇 When the content (% by weight) of the oxidized oxide (D2) is c2, the ratio (C1/C2) is preferably 〇 or more, and preferably 丨 or less. When the content ratio (C1/C2) is at least the above lower limit and not more than the above upper limit, the defoaming property and the repellency property of the photosensitive composition are further improved. (Polymerization-based base stone (E)) The photosensitive composition of the present invention contains polydifluorenyl decane (E), whereby the antifoaming property and the repellency property of the photosensitive composition are improved. The above polydimethyl oxalate (E) is not particularly limited. The polydimethyloxazepine (8) is different from the first and second osmium oxide (D1) and (1) 2). In the photosensitive group δ of the present invention, the polydimethyl oxalate (Ε) system is separately formulated from the first and second cerium oxides (D1) and (D2). The oxane may be used singly or in combination of two or more. In the photosensitive composition of the present invention, the content of the polydimethyl oxime oxime is preferably 〇1% by weight or more, more preferably 〇3% by weight or more, and preferably 5% by weight. The weight% or less is more preferably 3% by weight or less. When the content of the above-mentioned 157383.doc 201205195 polydimethyl oxalate (E) is at least the above lower limit and the above upper limit, the defoaming property and the repellency property of the photosensitive composition are further improved. (Other components) In order to further improve the curability, the photosensitive composition of the present invention preferably contains a polymerizable monomer as a component different from the polymerizable polymer (VIII) having a slow group. The photosensitive composition of the invention of the invention preferably contains both a polymer (A) having a plurality of groups and a polymerizable monomer. The above polymerizable monomer is polymerizable and polymerizable. The polymerizable monomer is not particularly limited. The above polymerizable monomers may be used alone or in combination of two or more. The polymerizable non-frying group in the above-mentioned polymerizable monomer may, for example, be a methyl group having a polymerizable unsaturated double bond such as a methyl group or a vinyl group. Among them, the (meth) acrylonitrile group is preferred because the crosslinking density of the resist film can be increased. The above polymerizable unsaturated group-containing monomer is preferably a compound having a (meth) acrylonitrile group. Examples of the compound having a (meth)acryl oxime group include a bis(indenyl) acrylate modified product of a glycol such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol or propylene glycol, or a plurality of compounds. a poly(indenyl) acrylate ester of an oxirane adduct of an alcohol, a polyol, or a propylene oxide adduct of a polyol, or a ring of phenolic phenol a (meth) acrylate modification of an oxyethylene adduct or a oxirane adduct of phenol, or a glycerol diglycidyl or a dimethyl glycerol triglycidyl hydrazide or the like ) Acetone vinegar modified 'or melamine (meth) acrylate. The polyhydric alcohol may, for example, be hexanediol, trimethylolpropane, quaternary tetradecyl alcohol, diquaternol and tris-ethylicocyanuric acid vinegar. 157383.doc 201205195 is the above-mentioned benzene-aged (meth)acrylic acid vinegar, and examples thereof include a phenoxy group (a methacrylic acid ester and a bisphenol A bis(meth) acrylate modified product. "" refers to the propyl (tetra) group and the methacrylic acid. (Mercapto) "acrylic acid" means acrylic acid and mercaptoacrylic acid. "(Indenyl) acrylate" means acrylate and methacrylate. In the case where the above-mentioned polymerizable monomer is contained, the content of the upper monomer of the polymerizable monomer and the polymerizable polymer (4) having the above-mentioned retarding group is preferably 5% by weight. Above, and preferably (10) weight under the heart. When the content of the polymerizable monomer is at least the above lower limit and the above upper limit, the photosensitive composition can be sufficiently cured to have an appropriate H-resistance density, and sufficient resolution can be obtained, and the resist film is not easily yellowed. In order to improve the dicing property of the resist film, it is preferred that the photosensitive composition contains a compound having a cyclic fluorene skeleton. By using the above compound having a cyclic skeleton, the curability of the photosensitive composition is also improved. Examples of the compound having a cyclic ether skeleton include a bisphenol S-type epoxy resin, a phthalic acid diglycidyl vinegar resin, a heterocyclic epoxy resin such as isocyanuric acid triglycidyl s, and the like. A (four) type epoxy resin, biphenyl fluorene type epoxy resin, tetraglycidyl xylene aged ethylbenzene resin, double bismuth A type epoxy resin, hydrogenated (four) A type epoxy resin, double age" resin, brominated biguanide Epoxy resin, benzene (four) varnish type epoxy resin, enamel varnish type epoxy resin, alicyclic epoxy resin, double age Α 酴 lacquer type epoxy resin, chelating epoxy resin, Ethylene Acid type epoxy resin, amine-based epoxy resin, rubber modified epoxy resin, two-ring bismuth 157383.doc 201205195 thin-type epoxy resin, poly-stone oxide modified epoxy resin and ε_ In the vinegar-modified epoxy resin, the above-mentioned compound having a cyclic ether skeleton may be used alone or in combination of two or more. The compound having a cyclic anthracene skeleton is a polymerizable polymer (A) having a cyclic group. The method in which the carboxyl group reacts to harden the photosensitive composition functions. The content of the above compound having a cyclic ether skeleton is preferably 〇1 part by weight or more, more preferably i part by weight or more, and preferably 50 parts by weight or less, based on 1 part by weight of the polymerizable polymer (A). More preferably, it is 3 parts by weight or less. When the content of the compound having a cyclic ether skeleton is at least the above lower limit and not more than the above upper limit, the electrical insulating properties of the resist film can be further improved. Preferably, the photosensitive f-active composition of the present invention contains an antioxidant. The antioxidant preferably has a Lewis basic moiety. From the viewpoint of further inhibiting the yellowing of the resist bismuth, the above antioxidant It is preferably at least one selected from the group consisting of a phenolic antioxidant, a phosphorus antioxidant, and an amine antioxidant. The antioxidant is preferably a lanthanide resistant agent from the viewpoint of further suppressing yellowing of the resist film. The oxidizing agent, that is, the photosensitive composition of the present invention preferably contains a phenolic antioxidant. Further, when a phenolic antioxidant is used as the above antioxidant, phenolic antioxidant is used. Antioxidants other than the case of the agent as compared to both the photosensitive composition of the defoaming and rejection characteristic becomes more favorable as the trypan-based antioxidant of the commercially available product include: IRgan〇x
1010、IRGANOX 1035、IRGANOX 1G76、IRGAN0X 1135、IRGANOX 245、IRGANOX 259、及 IRGANOX •14- I57383.doc ⑧ 201205195 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 Sumili.zer GP(以上均 為住友化學工業公司製造），HOSTANOX 010、 HOSTANOX 016、HOSTANOX 014、及 HOSTANOX 03(以 上均為 Clariant公司製造），Antage ΒΗΤ、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化成公司製造）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-240 ' 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、二氰二醯 157383.doc 15 201205195 胺、二聚氰胺、乙基二胺基-均三，井、24·二胺基-均三 啡、2,4-二胺基·6-曱笨基_均三畊、2,4_二胺基_6_二甲苯 基-均二哨'及四級敍鹽衍生物等。 相對於上述具有羧基之聚合性聚合物（A) 1 〇〇重量份，上 述抗氧化劑之含量較佳為〇.i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 上述抗氧化劑之含量為上述下限以上及上限以下，則可形 成耐熱黃變性更優異之阻劑膜。 本發明之感光性組合物亦可含有溶劑。溶劑之偶極矩較 佳為1 Debye(德拜）以上。藉由使用偶極矩為} Debye以上 之溶劑’可提供適用期優異之感光組合物。 又，本發明之感光性組合物亦可含有著色劑、填充劑、 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 菌片，J、防黴劑、勻化劑、穩定劑、偶合劑、防流掛劑或勞 光體等。 進而，本發明之感光性組合物亦可為包含第1液與第2 而以混合該第i、第2液使用之二液混合型之感光性組 合物。於二液混合型之感光性組合物之情形時，可抑制於 使用則進行聚合或硬化反應。因此，可提高二液各自之適 2期。又，本發明之感光性組合物亦可為僅包含第丨液之 ^液型之感光性組合物。於本發明之感光性組合物中包括 早液型之感光性組合物與二液混合型等多液混合型之感光 性組合物。 157383.doc 201205195 於二液混合型之感光性組合物之情形時，聚合性聚合物 ⑷、光聚合起始劑（B)、氧化鈦（c)、^二氧化石夕⑼）、 第2二氧切（D2)及聚二甲基發氧烧⑻係分別含於上述第i :及上述第2液中之至少一者中…於包含上述聚合性 单體、上述具有環狀㈣架之化合物及上述抗氧化劑之情 形時’上述聚合性單體、上述具有環狀醚骨架之化合物及 上述抗氧化劑係分別含於上述第丨液及上述第2液中之至少 一者中。 將上述第1、第2液混合而成之混合物為感光性組合物， 包含聚合性聚合物⑷、光聚合起始劑⑻、氧化鈦(C)、第 1二氧切则、第2二氧切（D2)及聚二甲基石夕氧烧⑻。 本發明之感光性組合物例如可藉由攪拌混合各調配成分 後’利用三輥混練機均勻混合而製備。 作為用以使感光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、深紫外線燈 uv(uitraviolet，紫外線）Lamp)、高壓水銀燈、低壓水銀 燈、金屬i化物燈及準分子雷射。該等光源係根據感光性 組合物之構成成分之感光波長而適當選擇。光之照射能量 係根據所欲之膜厚或感光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之範圍内。 (LED裝置） 本發明之感光性組合物適合用於形成LEd裝置之阻劑 膜，更適合用於形成阻焊膜。本發明之感光性組合物較佳 157383.doc 201205195 為阻劑組合物，較佳為阻焊劑組合物。 本發明之印刷電路板包括於表面具有電路之印刷電路板 本體、及於該印刷電路板本體之設置有上述電路之表面上 積層的阻焊膜《該阻焊膜係藉由本發明之感光性組合物而 形成。 圖1中，以部分欠缺前視剖面圖示意性地表示具有使用 本發明之一貫施形態之感光性組合物形成之阻焊膜的led 裝置之一例。 於圖1所示之LED裝置1中，於基板2之上面2&積層有藉 由感光性組合物而形成之阻劑膜3。阻劑膜3係圖案膜。因 此，於基板2之上面2a之一部分區域中未形成有阻劑膜3。 於未形成有阻劑膜3之部分之基板2之上面2a設置有電極 4a、4b。基板2較佳為印刷電路板本體。 於阻劑膜3之上面3a積層有LED晶片7。於基板2上隔著 阻劑膜3積層有LED晶片7。於LED晶片7之下面7a之外周 緣’設置有端子8a、8b。藉由焊錫9a、9b，端子8a、8b與 電極4a、4b電性連接。藉由該電性連接，可對led晶片7 供給電力。 以下’藉由列舉本發明之具體之實施例及比較例來明確 本發明。本發明並不限定於以下之實施例。 於實施例及比較例中，使用以下之材料1 )〜丨5)。 1)丙稀酸系聚合物1(具有致基之聚合性聚合物，下述合 成例1中所獲得之丙烯酸聚合物丨） (合成例1) 157383.doc •18· 201205195 …、備皿度。十㉟拌機、滴液漏斗及回流冷凝器之燒瓶 中，放入作為溶劑之乙基卡必醇乙酸賴及作為觸媒之偶 氮雙異丁腈’於氮氣環境下加熱至，用2小時滴加將 甲基丙烯酸與甲基丙歸酸甲酿以3〇:7〇之莫耳比混合之單 體。滴加後’料1小時’將溫度提高至12Gt。其後進行 冷部添加相對於所得樹脂之所有單體單元之總量之莫耳 量的莫耳比成為H)之量的丙烯酸縮水甘域，使用漠化四 丁基敍作為觸媒，於10(rc下加熱30小時，使丙稀酸縮水 甘油sa與缓基進行加成反應。冷卻後，自燒瓶取出，獲得 含有固體成分酸值為60 mg K〇H/g、重量平均分子量為 15000、雙鍵當量為1〇〇〇之含羧基之樹脂5〇重量不揮發 成分）的溶液。以下，將該溶液稱為丙烯酸系聚合物i ^ 2) DPHA(丙烯酸系單體，二季戊四醇六丙烯酸酯，比重 為 1.1) 3) TPO(作為光自由基產生劑之光聚合起始劑，basf Japan公司製造） 4) 828(雙酚A型環氧樹脂’三菱化學公司製造，比重為 1.2) 5) CR-50(氧化鈦’石原產業公司製造，藉由氣化法製造 之金紅石型氧化鈦） 6) R202(二氧化矽，日本Aerosil公司製造，一次粒徑為 14 nm) 7) RX50(二氧化矽，日本Aerosil公司製造，一次粒徑為 40 nm) I57383.doc 19 201205195 8) 5X(二氧切，龍森公司製造，-次粒徑為以㈣ 9) VX-S(二氧化石夕，龍森公司製造一次粒徑為4叫） 10) AA(二氧切，龍森公司製造，—次粒徑為―） U)KF-96(聚二甲基石夕氧燒’信越化學工業公司製造） ⑺KS·川0(複合型聚石夕氧油，聚二甲基石夕魏，信越 化學工業公司製造） Π) IRGAN〇X 1010⑽系抗氧化齊卜Ciba Japan公司製 造） m)IRGAF0S 168(磷系抗氧化劑，Cibajapan&司製造） 15)乙基卡必醇乙酸酯（溶劑，偶極矩為i Debye以上，比 重為1.0) (實施例1) 調配15重量份之合成例1中所獲得之丙烯酸系聚合物i、 5重量伤之DPHA(二季戊四醇六丙稀酸g旨）、2重量份之 TPO(作為光自由基產生劑之光聚合起始劑，BASF Japan公 司製造）、8重量份之828(雙酚A型環氧樹脂，三菱化學公 司製造）、40重量份之CR-50(氧化鈦，石原產業公司製 造）、3重量份之R202(二氧化矽，日本Aerosil公司製造， 一次粒徑為14 nm)，15重量份之VX-S(二氧化矽，龍森公 司製造，一次粒徑為4 μπι)、1重量份之KS-7710(複合型聚 矽氧油，聚二甲基矽氧烷，信越化學工業公司製造）、及 30重量份之乙基卡必醇乙酸酯，利用混合機（練太郎SP-5 00 ’ Thinky公司製造）混合3分鐘後，利用三輥混練機混 合，獲得混合物。其後，使用SP-500將所獲得之混合物消 •20· 157383.doc ⑧ 201205195 泡3分鐘’藉此獲得作為感光性組合物之阻劑材料。 (實施例2〜10及比較例1〜3) 除了如下述表1所示般變更所使用之材料之種類及調配 量以外’與實施例1同樣地獲得阻劑材料。 (評價） (1) 黏度 使用黏度計（東機產業公司製造之r TVE22L」），測定所 獲得之阻劑材料於剪切速度為1 rpni時之25°C下之黏度 ril(mPa.s)、及剪切速度為1〇 rpm時之25t下之黏度 r|10(mPa.s)。 (2) 消泡性 準備於表面貼附有銅箔之100 mmx 100 mm之FR-4基板。 又’手動攪拌所獲得之阻劑材料5 〇次。藉由網版印刷將剛 授拌後之阻劑材料塗佈於上述Fr_4基板之貼附有銅箔之面 上’形成阻劑材料層。其後，於室溫（25°c )下放置1分鐘 後’目測觀察經印刷之1 〇〇 mmx 100 mm之區域之阻劑材料 層中是否存在直徑為0.5 mm以上之泡。根據泡之個數，按 下述基準判疋阻劑材料（感光性組合物）之消泡性。 [消泡性之判定基準] 〇 〇 :確認不到泡 〇.確認到1〜2 0個泡 X :確認到2 1個以上之炮 (3) 排斥特性 於上述（2)消泡性之評價中所使用之FR_4基板之貼附有 157383.doc 2】 201205195 銅箔之面上，貼附作為脫模膜之PET膜。又，手動攪拌所 獲得之阻劑材料50次。藉由網版印刷將剛攪拌後之阻劑材 料印刷至上述FR-4基板上之PET膜上，形成阻劑材料層。 印刷後’於室溫（25t)下放置H、時，目測確認阻劑材料層 對於PET膜表面之排斥之狀態。即，於自印刷區域之邊緣 向外側擴大之情形時，或阻劑材料之液滴自邊緣向外側分 離之情形時，視為產生排斥。關於該排斥之狀態，將自上 述印刷區域之邊緣起直至向外側擴大之阻劑材料層之最外 側邊緣為止之距離、或自上述印刷區域之邊緣起直至位於 外側之阻劑材料液滴為止之距離設為排斥距離。按以下三 等級之基準判定排斥特性。 [排斥特性之判定基準] 00 :排斥距離小於10 mm 0 ·排斥距離為1 〇 mm以上，且小於20 mm x ’排斥距離為20 mm以上 將結果示於下述表丨中。再者，於下述表1中，黏度比 (ηΐ/ηΐ〇)表示剪切速度為i rpm時之25<t下之黏度η1(ιηΡ&·3) 相對於剪切速度為10 rPm時之25。(：下之黏度rilO(mPa.s)的 比°再者’於下述表1中，含量比（C1/C2)表示感光性組合 物1〇〇重量％中之第1二氧化矽之含量（重量％)C1相對於感 光性組合物1 〇〇重量％中之第2二氧化矽之含量（重量％)C2 的比。 157383.doc -22· 2012051951010, IRGANOX 1035, IRGANOX 1G76, IRGAN0X 1135, IRGANOX 245, IRGANOX 259, and IRGANOX • 14- I57383.doc 8 201205195 295 (all of which are manufactured by Ciba Japan), 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 Sumili.zer GP (all manufactured by Sumitomo Chemical Industries, Ltd.), HOSTANOX 010, HOSTANOX 016, HOSTANOX 014, and HOSTANOX 03 (all of which are manufactured by Clariant), Antage ΒΗΤ , 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 Chemical Co., Ltd.). Examples of the phosphorus-based antioxidant include cyclohexylphosphine and triphenylphosphine. As a commercial product of the above-mentioned phosphorus-based antioxidant, Adekastab PEP-4C 'Adekastab PEP-8 ' Adekastab PEP-240 ' 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 of which are 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.). The amine-based antioxidant may, for example, be triethylamine or dicyandiamide 157383.doc 15 201205195 amine, melamine, ethyldiamine-all, well, 24·diamino-mestriphine , 2,4-diamino 6-indole, _ three tillage, 2,4-diamino -6-dimethylphenyl--different whistle' and four-stage salt derivatives. The content of the antioxidant is preferably 〇.i by weight or more, more preferably 5 parts by weight or more, and preferably 30 parts by weight or less based on 1 part by weight of the polymerizable polymer (A) having a carboxyl group. More preferably, it is 15 parts by weight or less. When the content of the antioxidant is not less than the above lower limit and not more than the upper limit, a resist film which is more excellent in heat yellow resistance can be formed. The photosensitive composition of the present invention may also contain a solvent. The dipole moment of the solvent is preferably 1 Debye or more. A photosensitive composition excellent in pot life can be provided by using a solvent having a dipole moment of > Debye or more. Further, the photosensitive composition of the present invention may further contain a coloring agent, a filler, a hardener, a hardening accelerator, a mold release agent, a surface treatment agent, a flame retardant, a viscosity modifier, a dispersant, a dispersion aid, and a surface modification. A granule, a plasticizer, an antibacterial sheet, a J, an antifungal agent, a leveling agent, a stabilizer, a coupling agent, an anti-sagging agent or a mortar. Further, the photosensitive composition of the present invention may be a photosensitive composition comprising a first liquid and a second two-liquid mixing type in which the i-th and second liquids are mixed. In the case of the two-liquid mixing type photosensitive composition, it is possible to suppress polymerization or hardening reaction when it is used. Therefore, it is possible to increase the respective two phases of the two liquids. Further, the photosensitive composition of the present invention may be a photosensitive composition containing only the liquid of the third liquid. The photosensitive composition of the present invention comprises a photosensitive composition of an early liquid type photosensitive composition and a two-liquid mixing type, and the like. 157383.doc 201205195 In the case of a two-liquid mixing type photosensitive composition, a polymerizable polymer (4), a photopolymerization initiator (B), a titanium oxide (c), a sulfur dioxide (9), and a second The oxygen-cut (D2) and the polydimethyl-oxygen (8) are respectively contained in at least one of the above i-: and the second liquid, and include the polymerizable monomer and the compound having the cyclic (four) frame. In the case of the above antioxidant, the polymerizable monomer, the compound having the cyclic ether skeleton, and the antioxidant are contained in at least one of the second liquid and the second liquid, respectively. The mixture obtained by mixing the first and second liquids is a photosensitive composition, and comprises a polymerizable polymer (4), a photopolymerization initiator (8), titanium oxide (C), a first dioxotomy, and a second dioxin. Cut (D2) and polydimethyl-stone (8). The photosensitive composition of the present invention can be produced, for example, by uniformly mixing and mixing the respective components, and then uniformly mixing them by a three-roll kneader. Examples of the light source for curing the photosensitive 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 ultraviolet lamp uv (uitraviolet), a high pressure mercury lamp, a low pressure mercury lamp, a metal i hydride lamp, and an excimer laser. These light sources are appropriately selected depending on the light-sensing wavelength of the constituent components of the photosensitive composition. The irradiation energy of light is appropriately selected depending on the desired film thickness or the constituent components of the photosensitive composition. The irradiation energy of light is generally in the range of 10 to 3000 mJ/cm2. (LED device) The photosensitive composition of the present invention is suitably used for forming a resist film of an LEd device, and is more suitable for forming a solder resist film. The photosensitive composition of the present invention is preferably 157383.doc 201205195 is a resist composition, preferably a solder resist composition. The printed circuit board of the present invention comprises a printed circuit board body having a circuit on a surface thereof, and a solder resist film laminated on a surface of the printed circuit board body on which the circuit is provided. The solder resist film is obtained by the photosensitive combination of the present invention. Formed by matter. In Fig. 1, an example of a led device having a solder resist film formed using the photosensitive composition of the present invention is schematically shown in a partially missing front cross-sectional view. In the LED device 1 shown in Fig. 1, a resist film 3 formed of a photosensitive composition is laminated on the upper surface 2& of the substrate 2. The resist film 3 is a pattern film. Therefore, the resist film 3 is not formed in a partial region of the upper surface 2a of the substrate 2. Electrodes 4a, 4b are provided on the upper surface 2a of the substrate 2 where the resist film 3 is not formed. The substrate 2 is preferably a printed circuit board body. An LED chip 7 is laminated on the upper surface 3a of the resist film 3. The LED wafer 7 is laminated on the substrate 2 via the resist film 3. Terminals 8a, 8b are provided on the outer periphery ' of the lower surface 7a of the LED wafer 7. The terminals 8a, 8b are electrically connected to the electrodes 4a, 4b by solders 9a, 9b. By this electrical connection, power can be supplied to the LED wafer 7. The invention is clarified by the following specific examples and comparative examples of the invention. The invention is not limited to the following examples. In the examples and comparative examples, the following materials 1) to 丨5) were used. 1) Acrylic acid polymer 1 (polymerizable polymer having a radical group, acrylic acid polymer oxime obtained in Synthesis Example 1 below) (Synthesis Example 1) 157383.doc • 18·201205195 ... . In a flask of a gravy mixer, a dropping funnel and a reflux condenser, ethyl carbitol acetic acid as a solvent and azobisisobutyronitrile as a catalyst were placed in a nitrogen atmosphere for 2 hours. A monomer in which methacrylic acid and methyl propyl methacrylate are mixed in a molar ratio of 3 〇:7 Torr is added dropwise. The temperature was increased to 12 Gt after the addition of "1 hour". Thereafter, the cold water is added to the amount of the molar ratio of all the monomer units of the obtained resin to the molar ratio of the molar ratio of H) to the glycidal domain of the acrylic acid, using the desertified tetrabutyl sulphate as a catalyst, at 10 (The heating reaction was carried out for 30 hours under rc, and the glycidyl acrylate was reacted with a slow base. After cooling, it was taken out from the flask to obtain a solid content of 60 mg K/H/g, and a weight average molecular weight of 15,000. A solution having a double bond equivalent of 1 〇〇〇 of a carboxyl group-containing resin and a weight of 5 不 of a nonvolatile component). Hereinafter, this solution is referred to as an acrylic polymer i ^ 2) DPHA (acrylic monomer, dipentaerythritol hexaacrylate, specific gravity 1.1) 3) TPO (photopolymerization initiator as a photoradical generator, basf Made by Japan) 4) 828 (bisphenol A type epoxy resin manufactured by Mitsubishi Chemical Corporation, specific gravity 1.2) 5) CR-50 (titanium oxide 'Ishihara Industry Co., Ltd., rutile type oxidation by gasification method Titanium) 6) R202 (cerium dioxide, manufactured by Aerosil, Japan, primary particle size 14 nm) 7) RX50 (manganese dioxide, manufactured by Aerosil, Japan, primary particle size 40 nm) I57383.doc 19 201205195 8) 5X (Dioxo, manufactured by Longsen Company, - sub-particle size is (4) 9) VX-S (Secondary Oxide, manufactured by Longsen Company, with a particle size of 4) 10) AA (dioxotomy, Longsen Company) Manufactured, the secondary particle size is -) U) KF-96 (polydimethyl sulphur oxide 'made by Shin-Etsu Chemical Co., Ltd.) (7) KS · Chuan 0 (composite poly-stone oxygen oil, polydimethyl Shi Xiwei , manufactured by Shin-Etsu Chemical Co., Ltd.) Π) IRGAN〇X 1010(10) is an anti-oxidation product manufactured by Ciba Japan) m) IRGAF0S 168 (phosphorus system) Oxidizing agent, manufactured by Cibajapan & Division) 15) Ethyl carbitol acetate (solvent, dipole moment of i Debye or more, specific gravity of 1.0) (Example 1) 15 parts by weight of the acrylic acid obtained in Synthesis Example 1 was formulated. Polymer i, 5 weight-damaged DPHA (dipentaerythritol hexa-acrylic acid g), 2 parts by weight of TPO (photopolymerization initiator as photoradical generator, manufactured by BASF Japan Co., Ltd.), 8 parts by weight 828 (bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Corporation), 40 parts by weight of CR-50 (titanium oxide, manufactured by Ishihara Sangyo Co., Ltd.), and 3 parts by weight of R202 (cerium oxide, manufactured by Japan Aerosil Co., Ltd., primary particle) 15 nm), 15 parts by weight of VX-S (cerium dioxide, manufactured by Ronson Corporation, primary particle size 4 μπι), 1 part by weight of KS-7710 (composite polyoxyxene oil, polydimethyl 30% by weight of ethyl carbitol acetate, which was mixed with a mixer (manufactured by Ryotaro SP-5 00 'Thicky Co., Ltd.) for 3 minutes, and then used a three-roller kneading machine. Mix to obtain a mixture. Thereafter, the obtained mixture was bubbled for 3 minutes using SP-500, whereby a resist material as a photosensitive composition was obtained. (Examples 2 to 10 and Comparative Examples 1 to 3) A resist material was obtained in the same manner as in Example 1 except that the type and amount of the materials used were changed as shown in Table 1 below. (Evaluation) (1) Viscosity Using a viscometer (r TVE22L manufactured by Toki Sangyo Co., Ltd.), the viscosity of the obtained resist material at 25 ° C at a shear rate of 1 rpni was measured (mPa.s). And the viscosity r|10 (mPa.s) at 25t at a shear rate of 1 rpm. (2) Defoaming property Prepare a 100 mm x 100 mm FR-4 substrate with a copper foil attached to the surface. Further, the resist material obtained by manual stirring was 5 times. The newly applied resist material is applied to the surface of the Fr_4 substrate to which the copper foil is attached by screen printing to form a resist material layer. Thereafter, after standing at room temperature (25 ° C) for 1 minute, it was visually observed whether or not a bubble having a diameter of 0.5 mm or more was present in the resist material layer in the area of 1 〇〇 mm x 100 mm which was printed. The defoaming property of the resist material (photosensitive composition) was judged based on the number of bubbles. [Criteria for determining the defoaming property] 〇〇: No foaming was confirmed. 1 to 2 bubbles were confirmed. X: 2 or more shots were confirmed. (3) Repulsive characteristics were evaluated in the above (2) defoaming property. Attached to the FR_4 substrate used in the 157383.doc 2] 201205195 The surface of the copper foil is attached with a PET film as a release film. Further, the obtained resist material was manually stirred 50 times. The just-stirred resist material was printed onto the PET film on the FR-4 substrate by screen printing to form a resist material layer. After placing H at room temperature (25 t) after printing, the state of rejection of the resist material layer against the surface of the PET film was visually confirmed. That is, when the edge of the printed region is expanded to the outside, or when the droplet of the resist material is separated from the edge to the outside, it is considered to be repelled. Regarding the state of the repulsion, the distance from the edge of the printing region up to the outermost edge of the resist material layer which is enlarged to the outside, or from the edge of the printing region to the droplet of the resist material located outside The distance is set to the exclusion distance. The rejection characteristics are determined on the basis of the following three grades. [Criteria for determination of repulsion characteristics] 00 : Repulsive distance is less than 10 mm 0 · Repulsive distance is 1 〇 mm or more and less than 20 mm x ” Repulsive distance is 20 mm or more The results are shown in the following table. Further, in Table 1 below, the viscosity ratio (ηΐ/ηΐ〇) indicates that the viscosity η1 (ιηΡ &·3) at 25 lt when the shear rate is i rpm is 10 rPm with respect to the shear rate. 25. (The ratio of the lower viscosity rilO (mPa.s) is further shown in Table 1 below, and the content ratio (C1/C2) indicates the content of the first cerium oxide in 1% by weight of the photosensitive composition. (% by weight) The ratio of C1 to the content (% by weight) of C2 of the second cerium oxide in 1% by weight of the photosensitive composition. 157383.doc -22· 201205195
〔II 1比較例3| »/*» rs 00 ο ΓΛ s〇 (N 0.20 X ο ο 比較例2 VI »〇 CN oo ο g 1 o X 比較例1 VI (N oo ο w-l g 1 0 X 實施例10 in CN 00 ο m 〇 0.20 0 o 0 0 實施例9 <n »—Η ITJ CS oo ο W-) <N r^i 0.20 0 o 0 0 實施例8 »〇 CN oo ο ΓΛ 0.20 0 0 ο 0 實施例7 in «η CN oo ο ο 卜 CN \q o ο ο 實施例6 «ο CS oo ο 一 一 s d o 0 ο 實施例5 w-i ν-> CN oo ο 00 〇 — *〇 0.80 o 0 ο ο 實施例4 ^T) m CN oo ο m — 0.20 o ο ο 實施例3 ^T) (N oo ο ΓΛ Ψ—Λ rn 0.20 0 0 ο 0 實施例2 u-» (N oo ο — κη rs '0.20 o 0 ο 實施例1 ίΝ oo ο 一 0.20 o o ο ο 丙烯酸系聚合物1 DPHA TPO 00 oo CR-50 R202(—次粒徑為14 nm) ! RX50(—次粒徑為40 nm) 5Χ(—次粒徑為1.5 μηι) 乂乂-5(—次粒徑為4#111) (—次粒徑為6 μηι) KF-96 KS-7710 IRGAN0X 1010 IRGAF0S 168 乙基卡必醇乙酸酯 黏度比(η1/η10) 含量比(C1/C2) 判定 判定 丙烯酸系聚合物 丙烯酸系單體 光聚合起始劑 環氧樹脂 氧化欽 二氧化矽 1 聚二甲基矽氧烷 ，酚系抗氧化劑 填系抗氧化劑 溶劑 消泡性 排斥特性 ηβη 評價 157383.doc -23- 201205195 【圖式簡單說明】 圖1係示意性地表示具有使用本發明之一實施形態之感 光性組合物之阻劑膜的LED裝置之一例的部分欠缺前視剖 面圖。 【主要元件符號說明】 1 LED裝置 2 基板 2a ' 3a 上面 3 阻劑膜 4a、 4b 電極 7 LED晶片 7a 下面 8a ' 8b 端子 9a、 9b 焊錫 157383.doc • 24·[II 1 Comparative Example 3| »/*» rs 00 ο ΓΛ s〇(N 0.20 X ο ο Comparative Example 2 VI »〇CN oo ο g 1 o X Comparative Example 1 VI (N oo ο wl g 1 0 X Implementation Example 10 in CN 00 ο m 〇0.20 0 o 0 0 Embodiment 9 <n »-Η ITJ CS oo ο W-) <N r^i 0.20 0 o 0 0 Embodiment 8 »〇CN oo ο ΓΛ 0.20 0 0 ο 0 Embodiment 7 in «η CN oo ο ο 卜 CN \qo ο ο Embodiment 6 «ο CS oo ο 一一sdo 0 ο Example 5 wi ν-> CN oo ο 00 〇 — *〇0.80 o 0 ο ο Example 4 ^T) m CN oo ο m — 0.20 o ο ο Example 3 ^T) (N oo ο ΓΛ Ψ—Λ rn 0.20 0 0 ο 0 Example 2 u-» (N oo ο — κη rs '0.20 o 0 ο Example 1 ίΝ oo ο a 0.20 oo ο ο Acrylic polymer 1 DPHA TPO 00 oo CR-50 R202 (---------- Nm) 5Χ(—the secondary particle size is 1.5 μηι) 乂乂-5 (—the secondary particle size is 4#111) (—the secondary particle size is 6 μηι) KF-96 KS-7710 IRGAN0X 1010 IRGAF0S 168 Kikabi alcohol acetate viscosity ratio (η1/η10) content ratio (C1/C2) determination of acrylic polymer acrylic monomer photopolymerization initiator epoxy resin oxidized cerium oxide 1 polydimethyl oxime Alkane, phenolic antioxidant filling antioxidant solvent defoaming repellency characteristic ηβη evaluation 157383.doc -23- 201205195 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic representation of a photosensitive combination having an embodiment of the present invention. A part of the LED device of the resist film is omitted from the front view. [Main component symbol description] 1 LED device 2 substrate 2a ' 3a upper 3 resist film 4a, 4b electrode 7 LED chip 7a 8a ' 8b terminal 9a, 9b solder 157383.doc • 24·