201139489 六、發明說明： 【發明所屬之技術領域】 本發明係有關存在負載聚合物之鹼性觸媒下使多官能 環氧樹脂與（甲基）丙烯酸反應而得之部份酯化之環氧樹 脂及其製造方法。 【先前技術】 部份酯化之環氧樹脂爲，可藉由紫外線等之活性能量 線、熱或其雙方之方法聚合，既使無法完全硬化，常溫下 也可發揮機械強度。因此部份酯化之環氧樹脂可有效作爲 加工過程需決定位置之製品之密封劑等原料用。具體上可 作爲液晶面板之密封劑及電氣構件之塗料等之原料用。 特別是液晶面板，部份酯化之環氧樹脂可有效作爲要 求公絲單位之精度之加工過程所使用的密封劑之原料用。 原料含有部份酯化之環氧樹脂之密封劑可將加工時位置不 齊程度限制於最小，形成液晶面板。 但部份酯化之環氧樹脂中會含有大量製造部份酯化之 環氧樹脂時所使用之觸媒殘渣等之不純物，而藉由殘存之 觸媒會緩慢進行硬化，增黏或產生凝膠，故會降低貯藏安 定性。 爲了去除殘存之觸媒曾提案，使用甲醇等有機溶劑洗 淨處理部份酯化之環氧樹脂之方法（專利文獻1 )。 又，爲了提升貯藏安定性曾提案，使殘存於部份酯化 之環氧樹脂中之觸媒氧化不活性化之方法（專利文獻2、3 -5- 201139489 又曾提案，使用強酸性離子交換樹脂處理殘存於部份 酯化之環氧樹脂中之叔膦衍生物所形成之觸媒之方法（專 利文獻4 )。 其他如曾提案，藉由以3級胺作爲觸媒，添加聚合禁 止劑，以提升部份酯化之環氧樹脂之貯藏安定性的方法（ 專利文獻5 )。 [專利文獻1]特開平5-295087號公報 [專利文獻2]特開平5-3203 12號公報 [專利文獻3]特開2002-145984號公報 [專利文獻4]特開平1 1 - 1 2345號公報 [專利文獻5]特開2004-244543號公報 但如專利文獻1，藉由洗淨製造時所使用之觸媒之方 法中’需重覆進行使用溶劑之洗淨處理，既使如此就後述 之電氣特性之觀點仍難得到充分高純度之部份酯化之環氧 樹脂。 又如專利文獻2、3 ’使觸媒氧化而不活性化之方法中 ，不活性化之觸媒會直接殘存於部份酯化之環氧樹脂中， 而無法改善者色之問題及降低電氣特性之問題。 如專利文獻4，使用強酸性離子交換樹脂去除觸媒之 方法中’爲了有效率去除觸媒，需使用二甲基二甘醇等之 補助溶劑’而爲了去除溶劑會有製造成本激增之問題，又 -6 - 201139489 就電氣特性之觀點仍難得到充分高純度之部份酯化之環氧 樹脂。 另如專利文獻5添加聚合禁止劑之方法中，不活性化 之觸媒及聚合禁止劑會直接殘存於部份酯化之環氧樹脂中 ，而無法改善降低電氣特性之問題。 此等先前技術雖可相當程度改善貯藏安定性，且製品 化，但液晶面板用滴液密封劑之領域中，伴隨著近年來液 晶顯示之高畫質化、高性能化，而使上述密封劑所要求之 特性也日漸嚴苛。 【發明內容】 本發明者們爲了提升液晶面板用滴液密封劑所要求之 特性，針對密封劑之主成分的部份酯化之環氧樹脂的電氣 特性專心檢討後發現，較佳爲盡可能不改變部份酯化之環 氧樹脂與原料環氧樹脂之電氣特性，因此需去除殘存於部 份酯化之環氧樹脂中之來自鹼性觸媒的不純物，可達成本 發明。 利用滴液方法之液晶面板之製造方法中，密封劑係以 未硬化狀態接觸液晶後直接進行UV硬化、加熱硬化。因 此部份酯化之環氧樹脂中殘存觸媒殘渣及聚合禁止劑等之 不純物會於硬化過程中，使來自觸媒之不純物等自密封劑 溶出及擴散至液晶面板，而成爲液晶面板之電氣特性惡化 之要因。 液晶面板之驅動周波數目前爲30至120Hz ’最近係開 201139489 發使用2 4 0 Η z之驅動周波數之液晶面板。該類液晶面板爲 電場驅動型之裝置，故自密封劑溶出於液晶面板之不純物 會成爲，可應答直流領域至240Hz之電場應答物質，而大 幅影響液晶面板之特性。 液晶面板之特性變化大致上係分別以電氣特性及顯示 特性之變化表現。液晶面板之電氣特性變化可藉由有關消 耗電力之電壓保持率變化而確認。又電壓保持率與液晶面 板之泄漏電流有關，係藉由溶出於液晶面板之離子物質等 之電荷粒子的存在而改變。 液晶面板之顯示特性變化例如係藉由有關應答速度之 液晶面板之亮度不均表現。液晶面板之亮度不均等爲，與 具有介電各向異性及極限電壓之液晶特有之特性具有關連 而發生之現象，其會受溶出於液晶面板之離子物質等之荷 電粒子與介電體雙極子等的存在影響。 該類液晶面板之電氣特性及顯示特性可藉由，測定介 電特性而評估。部份酯化之環氧樹脂中不純物係以電場應 答物質（介電體物質及荷電粒子）存在，故直流領域至 24 0Hz之範圍內改變周波數等，可改變介電特性（阻抗、 電容及相位角Θ )。 介電特性中阻抗係指，相對於交流信號之電阻，換言 之爲電流之易流性，降低阻抗之結果會增加泄漏電流，而 降低電壓保持率。 介電特性中電容係指靜電容量，換言之爲電氣之易積 存性。電容係依存於電極所挾持之介電物質之空間電荷分 -8- 201139489 極與配向分極，電容數値之變化係指液晶單元之保持容量 之變化，即液晶面板之特性偏差。 介電特性中相位角θ係指電壓與電流之相位差。相位 角自-90°偏移至0°方向時，會發生能暈流失，故相位角Θ改 變時會降低電壓保持率及減緩應答速度。 該類液晶面板之介電特性變化可藉由，測定密封劑之 原料用的部份酯化之環氧樹脂之介電特性（阻抗、電容及 相位角Θ )而預測。 部份酯化之環氧樹脂爲，具有乙烯基、酯鍵、羧基等 之構造，因此會提升極性，故提高測定溫度時會降低阻抗 、提高電容及相位角Θ分歧。故測定對象之部份酯化之環 氧樹脂的介電特性（阻抗、電容及相位角Θ )可藉由，比 較各種測定溫度下原料樹脂及純粹之部份酯化之環氧樹脂 的介電特性確認其變化。相對於基準之原料樹脂及純粹之 部份酯化之環氧樹脂的介電特性，比較對象之部份酯化之 環氧樹脂的介電特性（阻抗、電容及相位角Θ )變化較少 時，可確認爲電氣特性優良之部份酯化之環氧樹脂。 爲了得到電氣特性優良之部份酯化之環氧樹脂，要求 製造純度遠高於先前方法所得之物的部份酯化之環氧樹脂 。爲了實現本發明者們發現，使多官能環氧樹脂與（甲基 )丙烯酸反應製造部份酯化之環氧樹脂之方法中，藉由使 用負載聚合物之鹼性觸媒，反應後過濾或離心分離負載聚 合物之鹼性觸媒去除負載聚合物之鹼性觸媒，可得電氣特 性優良之高純度的部份酯化之環氧樹脂，又無需特別添加 -9 - 201139489 聚合禁止劑也可得優良貯藏安定性，而完成本發明。 [解決課題之方法] 即，本發明如下所述。 [1] 一種部份酯化之環氧樹脂的製造方法，其特徵爲 ’包含存在負載聚合物之鹼性觸媒下，使多官能環氧樹脂 與（甲基）丙烯酸反應之步驟，與去除負載聚合物之鹼性 觸媒，得部份酯化之環氧樹脂之步驟。 [2] 如上述Π ]所記載之部份酯化之環氧樹脂的製造 方法’其中負載聚合物之鹼性觸媒之鹼性觸媒爲，3價有 機磷化合物及/或胺化合物。 [3] 如上述Π]或[2]所記載之部份酯化之環氧樹脂的 製造方法’其中多官能環氧樹脂與（甲基）丙烯酸反應之 步驟中’相對於多官能環氧樹脂之環氧基1當量，係使10 至90當量％之（甲基）丙烯酸反應。 [4] 如上述Π ]至[3]中任何一項所記載之部份酯化之 環氧樹脂的製造方法，其中去除負載聚合物之鹼性觸媒之 步驟中，使用過濾或離心分離。 [5] —種部份酯化之環氧樹脂，其特徵爲，藉由存在 負載聚合物之鹼性觸媒下，使（甲基）丙烯酸與多官能環 氧樹脂反應後，去除負載聚合物之鹼性觸媒而得，其中來 自負載聚合物之鹼性觸媒之鹼性原子含量爲5 Oppm以下。 [6] —種硬化性組成物，其爲含有如上述[5]所記載 之部份酯化之環氧樹脂。 -10- 201139489 [發明之效果] 本發明可提供，藉由以較簡易之物理方法去除負載聚 合物之鹼性觸媒，可得優良電氣特性，又既使未添加聚合 禁止劑也可得優良貯藏安定性之部份酯化之環氧樹脂的製 造方法、部份酯化之環氧樹脂，及使用其之硬化性組成物 [實施發明之最佳形態] 下面將說明本發明較佳之實施形態。 本發明爲，包含存在負載聚合物之鹼性觸媒下，使多 官能環氧樹脂與（甲基）丙烯酸反應之步驟，其次去除負 載聚合物之鹼性觸媒，得部份酯化之環氧樹脂之步驟的， 部份酯化之環氧樹脂之製造方法。 多官能環氧樹脂可爲1分子中具有2個以上環氧基之環 氧樹脂無特殊限定，多官能環氧樹脂如下述化合物》 多官能環氧樹脂如，乙二醇、二乙二醇、三乙二醇、 丙二醇、二丙二醇、三丙二醇等之聚烷二醇類、二羥甲基 丙烷、三羥甲基丙烷、螺甘醇、丙三醇等多價醇類與環氧 氯丙烷反應所得之脂肪族多價縮水甘油醚化合物。 多官能環氧樹脂如，雙酚A、雙酚S、雙酚F、雙酚Ad 等之芳香族二元醇類及此等被乙二醇、丙二醇、烷二醇改 性之二元醇類與環氧氯丙烷反應所得之芳香族多價縮水甘 油醚化合物。 -11 - 201139489 多官能環氧樹脂如，己二酸、衣康酸等之芳香族 酸與環氧氯丙烷反應所得之脂肪族多價縮水甘油酯化 、間苯二甲酸、對苯二甲酸、均苯四酸等之芳香族二 與環氧氯丙烷反應所得之芳香族多價縮水甘油酯化合 又如二胺基二苯基甲烷、苯胺、偏苯二甲基二胺 芳香族胺與環氧氯丙烷反應所得之芳香族多價縮水甘 胺化合物。 多官能環氧樹脂如，海因及其衍生物與環氧氯丙 應所得之海因型多價縮水甘油基化合物。 多官能環氧樹脂如，苯酚或甲酚與甲醛所衍生之 樹脂、酚醛清漆樹脂與環氧氯丙烷反應所得之苯酚、 清漆型多價縮水甘油醚化合物。 (甲基）丙烯酸無特別限定，例如可使用市售之 酸或甲基丙烯酸。 多官能環氧樹脂與（甲基）丙烯酸反應之步驟中 對於多官能環氧樹脂之環氧基1當量被反應之（甲基 烯酸較佳爲10至90當量％，又以20至80當量％爲佳， 爲30至70當量％，特佳爲40至60當量％。 相對於多官能環氧樹脂之環氧基1當量，使上述 內之（甲基）丙烯酸反應時可得，僅使不飽和基反應 次聚合時可得假固定之良好樹脂特性，二次聚合時不 生相.分離等可形成均質聚合物之部份酯化之環氧樹脂 負載聚合物之鹼性觸媒係指，多官能環氧樹脂與 基）丙烯酸反應之步驟中所使用之鹼性觸媒負載於聚 二羧 合物 羧酸 勿。 等之 油基 烷反 苯酚 酚醛 丙烯 ，相 )丙 更佳 範圍 之一 會發 〇 (甲 合物 -12- 201139489 之物。 鹼性觸媒較佳爲3價有機磷化合物及/或胺化合物。鹼 性觸媒之鹼性原子爲磷及/或氮。 3價有機磷化合物如，三乙基膦、三·η-丙基膦、三-n-丁基膦般之烷基膦類及其鹽、三苯基膦、三-m-甲苯基膦 、三-(2,6-二甲氧基苯基）膦等之芳基膦類及其鹽、三苯 基亞磷酸酯、三乙基亞磷酸酯、三（壬基苯基）亞磷酸 酯等之亞磷酸三酯類及其鹽等。3價有機磷化合物之鹽如 ’三苯基膦-乙基溴化物、三苯基膦-丁基溴化物、三苯基 膦·辛基溴化物、三苯基膦-癸基溴化物、三苯基膦-癸基溴 化物、三苯基膦-異丁基溴化物、三苯基膦-丙基氯化物、 三苯基膦-戊基氯化物、三苯基膦-己蕋氯化物等。其中較 佳爲三苯基膦。 胺化合物如，二乙醇胺等之仲胺、三乙醇胺、二甲基 苄基胺、三雙甲基胺基甲基苯酚、三雙乙基胺基甲基苯酚 等之叔胺、I，5,7·三氮雜二環[4.4.0]癸-5 -嫌（TBD) 、7-甲基-1，5,7-三氮雜二環[4.4_0]癸-5-烯（Me-TBD ) > 1,8- 二氮雜二環[5.4.0]十一-7-烯（〇811) 、6-二丁 基胺基-1,8- [5.4.0]十一 -7-烯、1,5-二氮雜二環[4.3.0]壬-5-烯（DBN) 、1,1,3,3-四甲基脈等之強鹼性胺及其鹽。其中較佳爲 1,5,7-三氮雜二環[4.4.0]癸-5-烯（TBD)。胺化合物之鹽 如，氯化苄基三甲基銨、氯化苄基三乙基銨。 負載鹼性觸媒之聚合物無特別限定，可使用以二乙烯 基苯交聯聚苯乙烯之聚合物及以二乙烯基苯交聯丙烯酸樹 -13- 201139489 脂之聚合物等。此等聚合物不溶於多官能環氧樹脂與（甲 基）丙烯酸反應用之溶劑（例如甲基乙基酮、甲基異丁基 酮、甲苯等）、原料及生成物。 負載聚合物之鹼性觸媒爲，鹼性觸媒化學鍵結於不溶 性聚合物，或鹼性觸媒導入單體後，聚合單體，其後藉由 二乙烯基苯等之交聯單體之3次元交聯，可製造不溶於甲 基乙基酮、甲基異丁基酮、甲苯等之溶劑之負載聚合物之 鹼性觸媒。 負載聚合物之鹼性觸媒之具體例如，二苯基膦基聚苯 乙烯、1，5,7-三氮雜二環[4.4.〇]癸·5·烯聚苯乙烯、ν，Ν·( 二異丙基）胺基甲基聚苯乙烯、Ν-(甲基聚苯乙烯）-4_ (甲基胺基）吡啶等。此等之負載聚合物之鹼性觸媒可單 獨或2種以上倂用。 負載聚合物之鹼性觸媒可使用市售之物。市售之負載 聚合物之鹼性觸媒如，PS-PPh3(二苯基膦基聚苯乙稀、 拜歐達公司製）、PS-TBD ( 1，5,7-三氮雜二環[4.4.0]癸-5_ 烯聚苯乙烯、拜歐達公司製）。 負載聚合物之鹼性觸媒之使用比例較佳爲，相對於多 官能環氧樹脂之環氧1當量，負載聚合物之鹼性觸媒之驗 性觸媒爲〇·5至5 _0毫當量，更佳爲1.0至3.0毫當量。負載 聚合物之鹼性觸媒之使用比例就反應率、反應時間及觸媒 成本之觀點較佳爲上述範圍內。 本發明之製造方法中，多官能環氧樹脂與（甲基）丙 烯酸之反應步驟之溫度較佳爲60至120 °C，又以80至120。(： -14- 201139489 爲佳，更佳爲90至1 10t。 存在觸媒下，使多官能環 應時，爲了防止凝膠化需適當 氣相氧之濃度。例如積極將空 會引起觸媒氧化而招致活性降 多官能環氧樹脂與（甲基 反應得部份酯化之環氧樹脂後 硬化，因此較佳於將紫外線遮 多官能環氧樹脂與（甲基）丙 聚合，可於存在相對於環氧樹 進行，但此時於結束反應後需 下進行。回流溶劑如，丙酮、 本發明之製造方法中，多 烯酸反應後爲，去除負載聚合 合物之鹼性觸媒之方法較佳爲 過濾負載聚合物之鹼性角 ΙΟμιη之尼龍網孔NY-1 0HC (拜 聚合物之鹼性觸媒之方法等。 負載離心分離聚合物之鹼 離心分離機之固定分離法，去 本發明之製造方法係藉由 方法去除負載聚合物之鹼性觸 物之鹼性觸媒，可得高純度之 本發明之製造方法因係藉 氧樹脂與（甲基）丙烯酸反 保持反應系內及反應系上之 氣吹入反應系內時需注意， 低。 )丙烯酸之反應爲，藉由該 藉由紫外線等之活性能量線 光之容器內進行反應。又， 烯酸之反應中爲了防止氣相 脂爲良溶劑性之回流溶劑下 去除溶劑，故較佳於無溶劑 甲基乙基酮等。 官能環氧樹脂與（甲基）丙 物之鹼性觸媒。去除負載聚 使用過濾或離心分離。 蜀媒之方法，例如使用開口 豈士 Sefar公司製）濾取負載 性觸媒之方法如，藉由使用 除負載聚合物之鹼性觸媒。 過濾或離心分離般較簡易之 媒，因此幾乎不含負載聚合 部份酯化之環氧樹脂。 由過濾或離心分離等之較簡 -15- 201139489 易之物理方法去除負載聚合物之鹼性觸媒， 了使洗淨用溶劑或觸媒不活性化而使用聚合禁±齊彳$ $ $ 等，可減少製造成本。 本發明之部份酯化之環氧樹脂係由，存在 之鹼性觸媒下，使多官能環氧樹脂與（甲基）丙燃酸反應、 後，去除負載聚合物之鹼性觸媒而得，其中來自負載聚g 物之鹼性觸媒之鹼性原子含Μ爲50ppm以下。 本發明之部份酯化之環氧樹脂中，因來自負載聚合物 之驗性觸媒之驗性原子含量較低爲50ppm以下，故比較先 前之方法所得的部份酯化之環氧樹脂可得較優良之電氣特 性。又，本發明之部份酯化之環氧樹脂中，因來自負載聚 合物之鹼性觸媒之鹼性原子含量較低爲50ppm以下，故反 應過程無需添加聚合禁止劑，既使比較爲了使殘存之觸媒 不活性化而添加聚合禁止劑之部份酯化之環氧樹脂也可得 較優良之貯藏安定性》 部份酯化之環氧樹脂較佳爲不純物較少，因此來自負 載聚合物之鹼性觸媒之鹼性原子含量較佳爲40ppm以下， 又以30ppm以下爲佳，更佳爲20ppm以下，特佳爲lOppm以 下。 來自負載聚合物之鹼性觸媒之鹼性原子之具體例如， 磷或氮等。測定部份酯化之環氧樹脂所含的此等鹼性原子 含量，可推測部份酯化之環氧樹脂中之負載聚合物之鹼性 觸媒殘渣之殘存量。負載聚合物之鹼性觸媒之鹼性原子可 藉由衍生結合等離子發光分析法（ICP/AES )測定。 -16- 201139489 本發明之硬化性組成物爲，含有存在負載聚合物之鹼 性觸媒下，使（甲基）丙烯酸與多官能環氧樹脂後，去除 負載聚合物之鹼性觸媒而得，來自負載聚合物之鹼性觸媒 之鹼性原子含量爲5 Oppm以下之部份酯化之環氧樹脂。 上述硬化組成物可藉由紫外線等之能量線或熱聚合而 得硬化物。 本發明之硬化性組成物因含有，來自負載聚合物之鹼 性觸媒之鹼性觸媒之鹼性原子含量較低爲50Ppm以下，幾 乎不含負載聚合物之鹼性觸媒殘渣及聚合禁止劑之部份酯 化之環氧樹脂’故不會發生起因於觸媒殘渣及聚合禁止劑 之氧化生成物’可得優良之電氣特性及貯藏安定性。因此 本發明之硬化性組成物適用爲，具有電氣特性及污染問題 之液晶面板用滴液密封劑及電氣構件之塗料等。 【實施方式】 下面將舉實施例更詳細說明本發明之具體態樣，但本 發明非限定於此等例。 [實施例1] 準備備有攪拌機、溫度計、回流冷卻管之500ml玻璃 製4口燒瓶，混合雙酚A型環氧樹脂：耶彼庫EXA850CRP [DIC公司製]340g(2.0當量/環氧基）、甲基丙烯酸9〇.4g (1.0虽里）、PS-PPh3(—本基麟基聚苯乙燃，2.0mmol/g )[拜歐達公司製]750mg ( 1.5毫當量/TPP (三苯基膦）觸 -17- 201139489 媒量（g))後’以100°c攪拌反應至酸價爲l.OKOHmg/g以下 。將反應液冷卻至60。(：後，以孔徑ΐ〇μπι之尼龍篩網NY-10HC (瑞士 Sefar公司製）去除觸媒！^ — !^!^，得部份酯化 之環氧樹脂（PR-1 )。所得樹脂之環氧當量爲468g/eq。 又’濕式分解樹脂（PR-1)後，藉由衍生結合等離子發生 分析法（ICP/AES )測定，結果樹脂（pn )中之磷原子 含量爲2ppm以下。 [實施例2] 使用雙酚AD型環氧樹脂·· EPOMIK R1710[普林提公司 製]3 26g ( 2.0當量/環氧基）以外，同實施例丨得部份酯化 之環氧樹脂（PR-2 )。所得樹脂（pr_2 )之環氧當量爲 45 0g/eq。同實施例1進行測定，結果樹脂（PR_2 )中之磷 原子含量爲2ppm以下。 [實施例3] 準備備有搅拌機、溫度計、回流冷卻管之5 00ml玻璃 製4 口燒瓶’混合雙酚a型環氧樹脂：耶彼庫EXA850CRP [DIC 公司製]340g ( 2.0 當 Μ / 環氧基）、PS-PPh3 ( 2.0mmol/g)[拜歐達公司製]750nlg( 1.5毫當量/TPP[三苯 基膦]觸媒量（g)) ，PS-TBD ( 1，5,7-三氮雜二環[4.4.0]癸- 5-烯聚苯乙烯、1.4〇mm〇l/g)[拜歐達公司製]i.〇7g(1.5毫 當量/胺觸媒量（g))後，以1 0 0 °C攪拌的同時，以6小時緩 緩加入丙烯酸76. 〇g ( 1.〇當量）進行反應。結束添加丙烯 -18- 201139489 酸後’以100°c再次攪拌反應至酸價爲l.OKOHmg/g以下。 將反應液冷卻至6(TC後，以孔徑ΙΟμπι之尼龍篩網NY-10HC (瑞士 Sefar公司製）去除觸媒pS_pPh3及 ps_tbD，得部份 酯化之環氧樹脂（PR-3 )。所得樹脂（PR-3 )之環氧當量 爲461g/eq。同實施例〗進行測定，結果樹脂（pR_3 )中之 磷原子含量爲2ppm以下。 [比較例1 ] 準備備有攪拌機、空氣導入管、溫度計、回流冷卻管 之5 00ml玻璃製4 口燒瓶，混合雙酚a型環氧樹脂：耶彼庫 EXA8 50CRP[DIC公司製]340g ( 2.0當量/環氧基）、甲基丙 烯酸90.4g ( 1.0當量）、TPP (三苯基膦）[東京化成公司 製]〇.5g ( 1.9毫當量）、聚合禁止劑之氫醌25mg及p-甲氧 基苯酚100mg後’以l〇〇°C攪拌反應至酸價爲l.〇KOHmg/g 以下。結束反應後將空氣吹入液中，同時以8 0。(：進行2小 時氧化處理，得部份酯化之環氧樹脂（KR- 1 )。所得樹脂 (KR-1 )之環氧當量爲465 g/eq。同實施例1進行測定，結 果樹脂（KR-1)中之磷原子含量爲290pPm。 [比較例2 ] 未添加氣醌25mg、p -甲氧基苯酹100mg以外，同比較 例1進行反應，但反應途中凝膠化。 對實施例1至4及比較例1之部份酯化之環氧樹脂進行 下述加熱安定性試驗及減壓加熱促進試驗。 -19- 201139489 [加i熱安定性試驗] 將各部份酯化之環氧樹脂5〇g放入10〇ml之褐色聚乙烯 容器中，密栓後將容器放置於6 0 °C之烤箱中，經2〇小時、 200小時及500小時後取出，使用E型黏度計（東機產業公 司製 R E 1 0 5 U )以錐形回轉部之回轉速度2 · 5 r P m測定內容 物之黏度。以下述式（1)求取製造後之黏度爲100時之變 化率，結果如表1所示。 黏度變化率=(經過一定期問後之測定黏度/製造後之黏 度）.........⑴ [減壓加熱促進試驗】 將各部份酯化之環氧樹脂50g放入l〇〇ml之褐色聚乙烯 容器中，未密栓下將容器保存於50°C、減壓至lOOPa之真 空烤箱中，經2 0小時、2 0 0小時及5 0 0小時後取出，使用E 型黏度計（東機產業公司製 RE105U )以錐形回轉部之回 轉速度2.5rpm測定黏度。以上述式（1)求取製造後之黏 度爲100時之變化率，結果如表1所示。 -20- 201139489 [表1] 實施例1 實施例2 實施例3 比較例1 部份酯化之環氧樹脂 PR-1 PR·:! PR-3 KR-1 加熱安定性試驗結果 6 0°C/ 2 0小時經過後 1.00 1.00 1.00 1.10 6 0°C/2 0 0小時經過後 1.00 1.00 1.02 1.25 6 0°C/ 5 0 0小時經過後 1.00 1.00 1.05 2.05 減壓加熱促進試驗結果 （100Pa) 5 0°C/ 2 0小時經過後 1.00 1,00 - 1.18 5 0°C/2 0 0小時經過後 1.00 1.01 - 1.39 5 0°C/5 0 0小時經過後 1.04 1.05 凝膠化 如表1所示，實施例1至3之部份酯化之環氧樹脂爲， 60 °C之溫度下既使經過5 00小時黏度也幾乎無變化，又加 熱試驗可確認貯藏安定性優良。 但比較例1之部份酯化之環氧樹脂經過5 00小時後，黏 度變化近乎2倍，會降低加熱安定性。 又，如表1所示，實施例1至3之部份酯化之環氧樹脂 於5 0 °C、1 0 OP a之減壓下既使經過5 0 0小時黏度幾乎未改變 ’又減壓加熱試驗可確認貯藏安定性優良。 但比較例1之部份酯化之環氧樹脂經過5 00小時會凝膠 化。 下面將以下述方法測定實施例1及比較例1之部份酯化 之環氧樹脂的介電特性。 [測定介電特性] 基準用原料爲雙酚A型環氧樹脂：耶彼庫 -21 - 201139489 EXA850CRP[DIC公司製]。使用介電體測定系統1 26096W 型[索拉特公司製]與液體電極SR-C1R (單元容量：2pF， 電極間距離：1mm )[東陽工業公司製]，以FRA法測定原 料樹脂（基準）、實施例1及比較例1之部份酯化之環氧樹 脂的周波數變化爲l.〇xl〇_2Hz至1.0χ106Ηζ時之25°C、50°C 、80°C之介電特性（阻抗、電容、相位角θ )。評估未硬 化狀態之樹脂之介電特性，可使來自樹脂中之不純物的影 響力半定量化。結果如圖1至9所示。又，圖中例如「 1.0E-02」等之記號係指1.0xl(T2。 如圖1至3所示，25 °C下實施例1之部份酯化之環氧樹 脂的介電特性（阻抗、電容及相位角Θ)幾乎同等於基準 之原料樹脂之介電特性，不受部份酯化之環氧樹脂中之不 純物影響，可確認具有優良電氣特性。 又，如圖1至3所示，比較例1之部份酯化之環氧樹脂 的介電特性，相對於原料樹脂之介電特性會發生變化。即 如圖1所示，相對於原料樹脂之阻抗、比較例1之阻抗較低 ，由此可確認比較例1之部份酯化之環氧樹脂會降低電壓 保持率。又，如圖2所示，相對於原料樹脂之電容，比較 例〗之電容會發生變化，由此可確認比較例1之部份酯化之 環氧樹脂的保持容量發生偏差。又，如圖3所示，相對於 原料樹脂之相位角Θ，比較例1之相位角0爲自_90°偏移至0° 方向’由此可確認比較例1之部份酯化之環氧樹脂會發生 能量流失’而使應答速度減緩等。故比較例1之部份酯化 之環氧樹脂的介電特性較低，該較低之介電特性係受比較 -22- 201139489 例1之部份酯化之環氧樹脂中所含的不純物影響。 如圖4至9所示，測定溫度上升至50〇c、“艺時，實施 例1之部份酯化之環氧樹脂的介電特性（阻抗、電容及相 位角Θ )，相對於基準之原料樹脂之介電特性會有若干改 變，但推測其爲受溫度上升時起因於部份酯化之環氧樹脂 中所含的乙烯基、酯構造及羥基等之分子間相互作用影響 。又’如圖4至9所示’比較例1之部份酯化之環氧樹脂的 介電特性會隨著溫度上升，而自原料樹脂之介電特性產生 極大變化，會降低電氣特性。 由圖1至9所示得知，實施例1之部份酯化之環氧樹脂 的介電特性（阻抗、電容及相位角Θ)幾乎與原料樹脂之 介電特性同程度，因幾乎不含不純物，故未受不純物影響 而改變介電特性，確認可爲具有優良電氣特性之部份酯化 之環氧樹脂。 [實施例4] 所使用之觸媒爲PS-PPh3 (二苯基膦基聚苯乙烯， 2.0mmol/g)[拜歐達公司製]500mg ( 1.33毫當量/TPP (三 苯基膦）觸媒量（g))，與TPP (三苯基膦）160mg[關東化 學公司製](0.61毫當量/TPP (三苯基膦）觸媒量（g))以 外，同實施例1得部份酯化之環氧樹脂（PR·4 )。所得樹 脂之環氧當量爲45 8 g/eq。同實施例1進行測定’結果樹脂 (PR-4 )中之磷原子含量爲1 OOppm。 -23- 201139489 [實施例5] 所使用之觸媒爲PS-PPhs (二苯基膦基聚苯乙烯， 2.0mmol/g)[拜歐達公司製]650mg ( 1.73 毫當量 /TPP (= 苯基膦）觸媒量（g)) ’與TPP (三苯基膦）80mg[關東化 學公司製](0.31毫當量/TPP (三苯基膦）觸媒量（g))以 外’同實施例1得部份醋化之環氧樹脂（P R _ 5 )。所得樹 脂之環氧當量爲466g/eq。同實施例1進行測定，結果樹脂 (PR-5)中之磷原子含量爲48ppm。 [實施例6] 所使用之觸媒爲PS-PPh3 (二苯基膦基聚苯乙烯， 2.0mmol/g)[拜歐達公司製]7〇〇mg ( 1.87毫當量/TPP (三 苯基膦）觸媒量（g)) ’與TPP (三苯基膦）40mg[關東化 學公司製](0.15毫當量/TPP (三苯基膦）觸媒量（g))以 外’同實施例1得部份酯化之環氧樹脂（PR_6 )。所得樹 脂之環氧當量爲456g/eq。同實施例1進行測定，結果樹脂 (P R - 6 )中之磷原子含量爲26ppm。 [比較例3 ] 結束反應後未進行8 0 t下2小時氧化處理以外，同比 較例1得部份酯化之環氧樹脂（KR-2 )。所得樹脂（KR-2 )之環氧當量爲465g/eq。將離子交換樹脂（安拜里15DRY (主鏈附苯磺酸之離子交換樹脂），有機公司製）I 5份加 入該樹脂3 00份中，80。〇下攪拌處理3小時。將反應液冷卻 •24- 201139489 至60°C後，以孔徑ΙΟμηι之尼龍篩網NY-10HC (瑞士 Sefar 公司製）去除離子交換樹脂，得部份酯化之環氧樹脂（ KR-3 )。同實施例1進行測定，結果樹脂（KR-2及KR-3 ) 中之磷原子含量各自爲3 0 0ppm、25 0ppm。由此得知，既 使使用強酸性之離子交換樹脂時，所得之部份酯化之環氧 樹脂中含有較多之來自觸媒之不純物（磷原子），確認會 減少降低來自觸媒之不純物的效果。 各自對實施例1之部份酯化之環氧樹脂（PR-1 :磷原 子含量：2Ppm以下）、實施例4之部份酯化之環氧樹脂（ PR-4 :磷原子含量：l〇〇ppm )、實施例5之部份酯化之環 氧樹脂（PR-5:磷原子含量：48ppm)、實施例6之部份醋 化之環氧樹脂（PR-6 :磷原子含量：26ppm)及比較例3之 部份酯化之環氧樹脂（KR-2 :磷原子含量：3 00ppm )， 藉由上述介電特性之測定法測定，測定溫度50 °C下周波數 lOmHz至100Hz之電容、周波數50Hz至ΙΟΚΗζ之相位角。 圖10爲各周波數之各樹脂中所含的磷原子含量與電容之關 係，圖1 1爲各周波數之各樹脂中所含的磷原子含量與相位 角Θ之關係。 如圖1 0所示’部份酯化之環氧樹脂中所含之不純物， 即磷原子含量之變曲點爲50Ppm以下時，確認可明顯減少 電容（保持容量）變化。特別是以周波數200mHz以下之 低周波數測定時’比較高周波數測定時低周波數一方之電 壓變化較緩，因此會明顯表現電容（保持容量）變化。故 如圖1 〇所示’以周波數200mHz以下之低周波數測定時， -25- 201139489 磷原子含S爲5〇ppm以下之部份酯化之環氧樹脂，比較磷 原子含量超過5〇ppm之部份酯化之環氧樹脂會明顯減少電 容（保持容量）變化’確認介電特性無偏差。 如圖1 1所示，磷原子含量之變曲點爲50ppm以下之部 份酯化之環氧樹脂中，自-90°偏移至0°方向之相位角Θ變化 較小，可減少電壓保持率降低及應答速度減緩，確認可具 有優良介電特性。特別是以近年來液晶面板適用之直流領 域（0Hz )至24〇Hz之低周波數領域（例如圖1 1所示， 50Hz至200Hz之領域）測定時，磷原子含量爲50ppm以下 之部份酯化之環氧樹脂，比較磷原子含量超過5 Oppm之部 份酯化之環氧樹脂可明顯減少相位角Θ變化，故不會發生 能量流失，確認具有優良介電特性。 [產業上利用可能性] 藉由本發明之製造方法所得的部份酯化之環氧樹脂可 長期間安定保存，減壓條件下也可具有優良安定性及電氣 特性，可作爲藉由紫外線等之活性能量線、熱中任何一種 聚合之原料用，故適用爲液晶面板之密封劑及電氣構件之 塗料等之原料。 【圖式簡單說明】 圖1爲’原料樹脂及部份酯化之環氧樹脂（實施例1、 比較例1 )之25 °C下測定周波數與阻抗之關係曲線圖。 圖2爲’原料樹脂及部份酯化之環氧樹脂（實施例i、 -26- 201139489 比較例J 1 ) < 25 °c下測定周波數與電容之關係曲線圖。 圖3爲，、， 原料樹脂及部份酯化之環氧樹脂（實施例1、 ^ ^ 1 } t 2s°c下測定周波數與相位角Θ之關係曲線圖。 圖4芦i，1¾ ^料樹脂及部份酯化之環氧樹脂（實施例1、 tt g W 1 ) t 5(rc下測定周波數與阻抗之關係曲線圖。 ® 5胃’原料樹脂及部份酯化之環氧樹脂（實施例1、 tb ^ ^ 1} t5 G °C下測定周波數與電容之關係曲線圖。 ® 6胃’原料樹脂及部份酯化之環氧樹脂（實施例！、 tt € W 1 > t 5(TC下測定周波數與相位角0之關係曲線圖。 ®> 7胃’原料樹脂及部份酯化之環氧樹脂（實施例1、 tt @ Μ Ο之8G°C下測定周波數與阻抗之關係曲線圖。 ® 8胃’原料樹脂及部份酯化之環氧樹脂（實施例！、 比較例1)之8(TC下測定周波數與電容之關係曲線圖。 圖9爲’原料樹脂及部份酯化之環氧樹脂（實施例i、 比較例1 )之8〇。〇下測定周波數與相位角0之關係曲線圖。 圖10爲’各周波數之各樹脂中所含之磷原子含量與電 容之關係曲線圖。 圖11爲’各周波數之各樹脂中所含之磷原子含量與相 位角Θ之關係曲線圖。 -27-201139489 VI. Description of the Invention: [Technical Field] The present invention relates to an epoxy ester obtained by reacting a polyfunctional epoxy resin with (meth)acrylic acid in the presence of a basic catalyst supporting a polymer. Resin and its manufacturing method. [Prior Art] The partially esterified epoxy resin can be polymerized by an active energy ray such as ultraviolet rays, heat, or both, so that it cannot be completely cured, and mechanical strength can be exhibited at normal temperature. Therefore, the partially esterified epoxy resin can be effectively used as a sealing agent for products such as a product whose processing needs to be determined. Specifically, it can be used as a raw material for a sealing agent for a liquid crystal panel and a coating material for an electric component. In particular, a liquid crystal panel, a partially esterified epoxy resin can be effectively used as a raw material for a sealant used in a process requiring precision of a male yarn unit. The sealant containing a partially esterified epoxy resin as a raw material can minimize the degree of misalignment during processing to form a liquid crystal panel. However, the partially esterified epoxy resin may contain a large amount of impurities such as catalyst residues used in the production of the partially esterified epoxy resin, and the residual catalyst may slowly harden, thicken or coagulate. Glue, which will reduce storage stability. In order to remove the residual catalyst, a method of treating a partially esterified epoxy resin is washed with an organic solvent such as methanol (Patent Document 1). Further, in order to improve storage stability, a method of inactivating oxidation of a catalyst remaining in a partially esterified epoxy resin has been proposed (Patent Documents 2, 3-5-201139489 have also proposed the use of strongly acidic ion exchange. A method of treating a catalyst formed by a tertiary phosphine derivative remaining in a partially esterified epoxy resin (Patent Document 4). Others have proposed to add a polymerization inhibitor by using a tertiary amine as a catalyst. A method for improving the storage stability of a partially esterified epoxy resin (Patent Document 5). [Patent Document 5] JP-A-5-295087 [Patent Document 2] JP-A-5-3203 No. 12 [Patent Document 5] Japanese Laid-Open Patent Publication No. 2004-244543. However, as disclosed in Patent Document 1, it is used for cleaning and manufacturing. In the method of the catalyst, it is necessary to repeat the washing treatment using a solvent, and it is difficult to obtain a partially high-purity esterified epoxy resin from the viewpoint of the electrical characteristics described later. Further, as in Patent Document 2, 3 'In the method of oxidizing the catalyst without activation The inactivated catalyst will directly remain in the partially esterified epoxy resin, and will not improve the color problem and reduce the electrical characteristics. For example, Patent Document 4, a method of removing a catalyst using a strongly acidic ion exchange resin In order to remove the catalyst efficiently, it is necessary to use a supplementary solvent such as dimethyl diglycol, and in order to remove the solvent, there is a problem of a sharp increase in manufacturing cost, and -6 - 201139489 is still difficult to obtain a high purity from the viewpoint of electrical characteristics. In the method of adding a polymerization inhibiting agent, the inactivated catalyst and the polymerization inhibiting agent may directly remain in the partially esterified epoxy resin, and cannot be improved. In the field of drip sealants for liquid crystal panels, the liquid crystal display has been improved in image quality and performance in recent years. In order to improve the characteristics required for the drip sealant for liquid crystal panels, the inventors of the present invention have become increasingly demanding. After reviewing the electrical characteristics of the partially esterified epoxy resin of the main component of the sealant, it was found that it is preferable to remove the electrical properties of the partially esterified epoxy resin and the raw material epoxy resin as much as possible, so it is necessary to remove The impurity derived from the alkaline catalyst remaining in the partially esterified epoxy resin can reach the cost of the invention. In the manufacturing method of the liquid crystal panel by the dropping method, the sealant directly contacts the liquid crystal after contacting the liquid crystal in an uncured state. Hardening, heat hardening. Therefore, impurities such as catalyst residues and polymerization inhibitors remaining in the partially esterified epoxy resin will dissolve and diffuse the self-sealant from the catalyst into the liquid crystal panel during the hardening process. It is the cause of the deterioration of the electrical characteristics of the liquid crystal panel. The number of driving cycles of the liquid crystal panel is 30 to 120 Hz. 'Recently opened 201139489 The liquid crystal panel using the driving frequency of 2 4 0 Η z. Such a liquid crystal panel is an electric field driven type device, so that the impurity which is dissolved in the liquid crystal panel from the sealing agent can be an electric field responsive material in the direct current field to 240 Hz, and greatly affects the characteristics of the liquid crystal panel. The change in characteristics of the liquid crystal panel is roughly expressed by changes in electrical characteristics and display characteristics, respectively. The change in the electrical characteristics of the liquid crystal panel can be confirmed by a change in the voltage holding ratio with respect to the power consumption. Further, the voltage holding ratio is related to the leakage current of the liquid crystal panel, and is changed by the presence of charge particles such as ionic substances dissolved in the liquid crystal panel. The change in display characteristics of the liquid crystal panel is expressed, for example, by uneven brightness of the liquid crystal panel regarding the response speed. The brightness unevenness of the liquid crystal panel is related to the characteristic unique to the liquid crystal having dielectric anisotropy and the limit voltage, and is affected by the charged particles and the dielectric dipole of the ionic substance dissolved in the liquid crystal panel. The existence of the influence. The electrical characteristics and display characteristics of such liquid crystal panels can be evaluated by measuring the dielectric properties. The impurities in the partially esterified epoxy resin are present in the electric field responsive material (dielectric material and charged particles), so the number of cycles can be changed in the DC range to 240 Hz, and the dielectric properties (impedance, capacitance, and Phase angle Θ). The impedance in the dielectric property refers to the resistance of the current signal, in other words, the flowability of the current. The result of lowering the impedance increases the leakage current and lowers the voltage holding ratio. In the dielectric property, the capacitance refers to the electrostatic capacity, in other words, the electrical accumulability. The capacitance depends on the space charge of the dielectric substance held by the electrode. -8- 201139489 The pole and the directional polarization change. The change in the capacitance 値 refers to the change in the holding capacity of the liquid crystal cell, that is, the characteristic deviation of the liquid crystal panel. The phase angle θ in the dielectric property refers to the phase difference between voltage and current. When the phase angle shifts from -90° to 0°, halo loss occurs, so the phase angle Θ changes to lower the voltage holding ratio and slow down the response speed. The change in dielectric properties of such liquid crystal panels can be predicted by measuring the dielectric properties (impedance, capacitance, and phase angle Θ) of the partially esterified epoxy resin used as the material for the sealant. The partially esterified epoxy resin has a structure of a vinyl group, an ester bond, a carboxyl group or the like, and thus the polarity is increased. Therefore, when the measurement temperature is increased, the impedance is lowered, and the capacitance and the phase angle are increased. Therefore, the dielectric properties (impedance, capacitance, and phase angle Θ) of the partially esterified epoxy resin of the measurement object can be compared by comparing the dielectric materials of the raw material resin and the purely partially esterified epoxy resin at various measurement temperatures. Characteristics confirm their changes. Comparing the dielectric properties of the reference raw material resin and the purely partially esterified epoxy resin, when the dielectric properties (impedance, capacitance, and phase angle Θ) of the partially esterified epoxy resin of the comparative object are less changed It can be confirmed as a partially esterified epoxy resin having excellent electrical characteristics. In order to obtain a partially esterified epoxy resin having excellent electrical characteristics, it is required to produce a partially esterified epoxy resin having a purity much higher than that obtained by the prior art. In order to achieve the inventors' discovery, in a method of reacting a polyfunctional epoxy resin with (meth)acrylic acid to produce a partially esterified epoxy resin, by using a basic catalyst loaded with a polymer, post-reaction filtration or Centrifugal separation of the polymer-loaded alkaline catalyst to remove the polymer-supported alkaline catalyst, and obtain a high-purity partially esterified epoxy resin with excellent electrical properties without special addition. -9 - 201139489 Polymerization inhibitor The present invention can be accomplished by obtaining excellent storage stability. [Method for Solving the Problem] That is, the present invention is as follows. [1] A method for producing a partially esterified epoxy resin, characterized by the steps of: reacting a polyfunctional epoxy resin with (meth)acrylic acid under an alkaline catalyst containing a supported polymer, and removing The step of loading the polymer's alkaline catalyst to obtain a partially esterified epoxy resin. [2] A method for producing a partially esterified epoxy resin as described above, wherein the basic catalyst for supporting the basic catalyst of the polymer is a trivalent organic phosphorus compound and/or an amine compound. [3] A method for producing a partially esterified epoxy resin as described in the above] or [2], wherein the step of reacting the polyfunctional epoxy resin with the (meth)acrylic acid is relative to the polyfunctional epoxy resin The epoxy group is equivalent to 1 to 90 equivalents of (meth)acrylic acid. [4] The method for producing a partially esterified epoxy resin according to any one of the above items, wherein the step of removing the polymer-supporting alkaline catalyst is carried out by filtration or centrifugation. [5] A partially esterified epoxy resin characterized in that the (meth)acrylic acid is reacted with a polyfunctional epoxy resin to remove the supported polymer by the presence of a basic catalyst supporting the polymer. The basic catalyst is obtained, wherein the basic catalyst derived from the supported polymer has a basic atomic content of 5 Oppm or less. [6] A curable composition comprising an epoxy resin partially esterified as described in the above [5]. -10- 201139489 [Effects of the Invention] The present invention can provide excellent electrical characteristics by removing a basic catalyst supporting a polymer by a simple physical method, and can be excellent even without adding a polymerization inhibiting agent. A method for producing a partially stabilized epoxy resin, a partially esterified epoxy resin, and a hardenable composition using the same. [Best Mode for Carrying Out the Invention] Hereinafter, a preferred embodiment of the present invention will be described. . The present invention relates to a step of reacting a polyfunctional epoxy resin with (meth)acrylic acid under the presence of a basic catalyst supporting a polymer, and secondly removing a basic catalyst supporting a polymer to obtain a partially esterified ring. A method of producing a partially esterified epoxy resin in the step of an oxy resin. The polyfunctional epoxy resin may be an epoxy resin having two or more epoxy groups in one molecule, and the polyfunctional epoxy resin is a compound such as a polyfunctional epoxy resin such as ethylene glycol or diethylene glycol. Polyalkylene glycols such as triethylene glycol, propylene glycol, dipropylene glycol, and tripropylene glycol, and polyvalent alcohols such as dimethylolpropane, trimethylolpropane, spiroglycol, and glycerol are reacted with epichlorohydrin. The resulting aliphatic polyvalent glycidyl ether compound. Polyfunctional epoxy resins such as aromatic diols such as bisphenol A, bisphenol S, bisphenol F, and bisphenol Ad, and such glycols modified by ethylene glycol, propylene glycol, and alkanediol An aromatic polyvalent glycidyl ether compound obtained by reacting with epichlorohydrin. -11 - 201139489 Polyfunctional epoxy resin, such as adipic acid, itaconic acid, etc., aromatic polyvalent glycidyl esterification, isophthalic acid, terephthalic acid, Aromatic polyvalent glycidyl esters obtained by reacting aromatic diene with epichlorohydrin such as pyromellitic acid, such as diaminodiphenylmethane, aniline, dimethylenediamine diamine, and epoxy An aromatic polyvalent glycidylamine compound obtained by reacting chloropropane. A polyfunctional epoxy resin such as hydantoin and its derivatives and a hydantoin-type polyvalent glycidyl compound obtained by epichlorohydrin. A polyfunctional epoxy resin such as a phenol or varnish-derived polyvalent glycidyl ether compound obtained by reacting a resin derived from phenol or cresol with formaldehyde, a novolak resin and epichlorohydrin. The (meth)acrylic acid is not particularly limited, and for example, a commercially available acid or methacrylic acid can be used. The step of reacting the polyfunctional epoxy resin with (meth)acrylic acid is carried out for 1 equivalent of the epoxy group of the polyfunctional epoxy resin (methyloic acid is preferably 10 to 90 equivalent %, and further 20 to 80 equivalents) % is preferably 30 to 70 equivalent %, particularly preferably 40 to 60 equivalent %. Compared with 1 equivalent of the epoxy group of the polyfunctional epoxy resin, the above-mentioned (meth)acrylic acid can be obtained by reaction, and only When the unsaturated group reaction is sub-polymerized, good resin properties of the pseudo-fixation can be obtained, and no phase is formed during the secondary polymerization. A basic catalyst for separating an epoxy resin-supported polymer which is partially esterified, such as a homogeneous polymer, means that the alkaline catalyst used in the step of reacting the polyfunctional epoxy resin with the acrylic acid is supported on the poly Dicarboxylate carboxylic acid. One of the more preferred ranges of oleyl alkaloids, phenol, phenol, propylene, propylene, etc., is a compound of the present invention. The basic catalyst is preferably a trivalent organic phosphorus compound and/or an amine compound. The basic atom of the basic catalyst is phosphorus and/or nitrogen. The trivalent organic phosphorus compound such as triethylphosphine, tri-n-propylphosphine, tri-n-butylphosphine-like alkylphosphine and Arylphosphines such as salts, triphenylphosphine, tris-m-tolylphosphine, tris-(2,6-dimethoxyphenyl)phosphine, and salts thereof, triphenylphosphite, triethyl a phosphite triester such as a phosphite or a tris(nonylphenyl) phosphite, or a salt thereof, etc. A salt of a trivalent organic phosphorus compound such as 'triphenylphosphine-ethyl bromide or triphenylphosphine- Butyl bromide, triphenylphosphine octyl bromide, triphenylphosphine-decyl bromide, triphenylphosphine-decyl bromide, triphenylphosphine-isobutyl bromide, triphenylphosphine -propyl chloride, triphenylphosphine-pentyl chloride, triphenylphosphine-hexane chloride, etc. Among them, triphenylphosphine is preferred. Amine compounds such as secondary amines such as diethanolamine, triethanolamine, Dimethylbenzyl , Three pairs dimethylamino-methylphenol, three pairs of ethyl tertiary amine-methylphenol, I, 5,7 · triazabicyclo [4. 4. 0] 癸-5 - suspected (TBD), 7-methyl-1,5,7-triazabicyclo[4. 4_0]癸-5-ene (Me-TBD) > 1,8-diazabicyclo[5. 4. 0] eleven-7-ene (〇811), 6-dibutylamino-1,8- [5. 4. 0] eleven -7-ene, 1,5-diazabicyclo ring [4. 3. 0] Strongly basic amine such as 壬-5-ene (DBN), 1,1,3,3-tetramethyl ketone and salts thereof. Among them, preferred is 1,5,7-triazabicyclo[4. 4. 0] 癸-5-ene (TBD). The salt of the amine compound is, for example, benzyltrimethylammonium chloride or benzyltriethylammonium chloride. The polymer to which the basic catalyst is supported is not particularly limited, and a polymer of a crosslinked polystyrene of divinylbenzene and a polymer of a crosslinked acrylic acid-triethyl benzene-13-201139489 can be used. These polymers are insoluble in a solvent (e.g., methyl ethyl ketone, methyl isobutyl ketone, toluene, etc.), a raw material, and a product for reacting a polyfunctional epoxy resin with (meth)acrylic acid. The basic catalyst for supporting the polymer is that the basic catalyst is chemically bonded to the insoluble polymer, or the basic catalyst is introduced into the monomer, the monomer is polymerized, and then the crosslinking monomer such as divinylbenzene is used. The 3-dimensional cross-linking can produce a basic catalyst which is insoluble in a solvent which is insoluble in a solvent such as methyl ethyl ketone, methyl isobutyl ketone or toluene. Specific examples of the basic catalyst for supporting the polymer are, for example, diphenylphosphinopolystyrene, 1,5,7-triazabicyclo[4. 4. 〇]癸·5·ene polystyrene, ν, Ν·(diisopropyl)aminomethylpolystyrene, fluorene-(methylpolystyrene)-4_(methylamino)pyridine, and the like. These alkaline polymers of the supported polymer may be used singly or in combination of two or more. Commercially available materials can be used as the basic catalyst for supporting the polymer. Commercially available basic polymers of supported polymers such as PS-PPh3 (diphenylphosphinopolystyrene, manufactured by Bayer), PS-TBD (1,5,7-triazabicyclo[ 4. 4. 0] 癸-5_ ene polystyrene, manufactured by Bayuda Corporation). The proportion of the alkaline catalyst used for supporting the polymer is preferably that the amount of the organic catalyst supporting the polymer is 〇·5 to 5 _0 milliequivalents relative to 1 equivalent of the epoxy of the multifunctional epoxy resin. More preferably 1. 0 to 3. 0 milli equivalents. The ratio of use of the basic catalyst of the supported polymer is preferably within the above range from the viewpoints of the reaction rate, the reaction time, and the catalyst cost. In the production method of the present invention, the temperature of the reaction step of the polyfunctional epoxy resin with (meth)acrylic acid is preferably from 60 to 120 ° C and from 80 to 120. (: -14-201139489 is better, more preferably 90 to 1 10t. In the presence of a catalyst, the polyfunctional ring should be used in time, in order to prevent gelation, the concentration of gas phase oxygen should be appropriate. For example, actively vacating will cause catalyst. Oxidation causes the activity-reducing polyfunctional epoxy resin to be hardened by the epoxy resin which is partially esterified by the methyl group. Therefore, it is preferred to polymerize the ultraviolet-viscous polyfunctional epoxy resin with (meth)propene. It is carried out with respect to the epoxy tree, but at this time, it is required to be carried out after the completion of the reaction. The reflux solvent such as acetone, the production method of the present invention, the polyether acid reaction, the method of removing the basic catalyst of the supported polymer Preferably, the nylon mesh of the supported polymer is filtered, and the nylon mesh NY-1 0HC (the method of the alkaline catalyst of the polymer, etc.), the fixed separation method of the alkali centrifugal centrifuge for loading the centrifugally separated polymer, The manufacturing method of the invention is a method for removing the alkaline catalyst of the basic contact of the polymer supported by the method, and the manufacturing method of the invention having high purity can be obtained by reacting the oxygen-receiving resin with the (meth)acrylic acid in the reaction system. Reaction system It should be noted that the gas is blown into the reaction system, and the reaction of acrylic acid is carried out by the reaction of the active energy line light by ultraviolet rays or the like. The solvent is removed under a solvent refluxing solvent, so it is preferably solvent-free methyl ethyl ketone, etc. The basic catalyst of the functional epoxy resin and the (meth) propyl group is removed by filtration or separated by centrifugation. The method of filtering a load-carrying catalyst, for example, using an open gentleman Sefar company, for example, by using a basic catalyst other than a supported polymer, a relatively simple medium for filtration or centrifugation, and thus has almost no load. The partially esterified epoxy resin is polymerized by a physical method such as filtration or centrifugation, etc. -15-201139489, which removes the alkaline catalyst of the supported polymer and deactivates the solvent or catalyst for washing. The use of polymerization prohibition ± 彳 彳 $ $ $, etc., can reduce the manufacturing cost. Part of the esterified epoxy resin of the present invention, the presence of the basic catalyst, the polyfunctional epoxy resin and (meth) propylene Acid reaction, after The basic catalyst supporting the polymer is obtained, wherein the basic atom derived from the supported poly-glycol has a ruthenium content of 50 ppm or less. In the partially esterified epoxy resin of the present invention, it is derived from a load polymerization. The tester has an inferior atomic content of less than 50 ppm, so that the partially esterified epoxy obtained by the prior method can obtain better electrical properties. Further, the partial esterification of the present invention In the epoxy resin, since the basic atomic content of the basic catalyst derived from the supported polymer is 50 ppm or less, it is not necessary to add a polymerization inhibiting agent in the reaction process, and the polymerization is added in order to inactivate the remaining catalyst. Partially esterified epoxy resin of the inhibiting agent can also obtain better storage stability. Partially esterified epoxy resin is preferably less impurity, so the basic atom derived from the basic catalyst supporting the polymer The content is preferably 40 ppm or less, more preferably 30 ppm or less, still more preferably 20 ppm or less, and particularly preferably 10 ppm or less. Specific examples of the basic atom derived from the basic catalyst supporting the polymer are, for example, phosphorus or nitrogen. The amount of such basic atom contained in the partially esterified epoxy resin is determined, and the residual amount of the alkaline catalyst residue of the supported polymer in the partially esterified epoxy resin can be estimated. The basic atom of the basic catalyst supporting the polymer can be determined by derivatization combined with plasma luminescence analysis (ICP/AES). -16- 201139489 The curable composition of the present invention comprises a basic catalyst containing a supported polymer, and after removing the (meth)acrylic acid and the polyfunctional epoxy resin, removing the basic catalyst supporting the polymer A partially esterified epoxy resin having a basic atomic content of less than 5 Oppm from a basic catalyst supporting a polymer. The hardened composition can be cured by energy rays or thermal polymerization of ultraviolet rays or the like. The curable composition of the present invention contains a basic catalyst derived from a basic catalyst supporting a polymer, and has a basic atomic content of 50 Ppm or less, and contains almost no alkali-supporting catalyst residue and polymerization inhibition. The partially esterified epoxy resin of the agent does not cause excellent electrical properties and storage stability due to oxidation of the catalyst residue and the polymerization inhibiting agent. Therefore, the curable composition of the present invention is preferably used as a drip sealant for a liquid crystal panel and a coating material for an electric member having electrical characteristics and contamination problems. [Embodiment] Hereinafter, specific embodiments of the present invention will be described in more detail by way of examples, but the invention is not limited thereto. [Example 1] A 500-ml glass 4-necked flask equipped with a stirrer, a thermometer, and a reflux cooling tube was prepared, and a bisphenol A type epoxy resin was mixed: yupku EXA850CRP [manufactured by DIC Corporation] 340 g (2. 0 equivalent / epoxy group), 9 methacrylic acid. 4g (1. 0 Although), PS-PPh3 (- Ben-based phenyl-based polystyrene, 2. 0mmol/g ) [made by Baioda Company] 750mg ( 1. 5 meq/TPP (triphenylphosphine) contact -17- 201139489 (g) after the reaction was stirred at 100 ° C until the acid value was 1. OKOHmg/g or less. The reaction solution was cooled to 60. (: After that, the catalyst was removed by a nylon mesh NY-10HC (manufactured by Sefar Co., Ltd.) with a pore size of ΐ〇μπι. ^^ !^!^, and a partially esterified epoxy resin (PR-1) was obtained. The epoxy equivalent is 468 g/eq. After the wet-decomposing resin (PR-1), the phosphorus atom content in the resin (pn) is 2 ppm or less as measured by derivatization-coupled plasma generation analysis (ICP/AES). [Example 2] Using bisphenol AD type epoxy resin··EPOMIK R1710 [manufactured by Principal Company] 3 26g ( 2. In the same manner as the 0 equivalent/epoxy group, a partially esterified epoxy resin (PR-2) was obtained in the same manner. The epoxy equivalent of the obtained resin (pr_2) was 45 0 g/eq. The measurement was carried out in the same manner as in Example 1. As a result, the content of phosphorus atoms in the resin (PR 2 ) was 2 ppm or less. [Example 3] A 500-neck flask made of a blender, a thermometer, and a reflux cooling tube was prepared. A mixed bisphenol a-type epoxy resin: yupku EXA850CRP [manufactured by DIC Corporation] 340 g (2. 0 when Μ / epoxy group), PS-PPh3 ( 2. 0mmol/g) [made by Baioda Company] 750nlg ( 1. 5 meq/TPP [triphenylphosphine] catalyst amount (g)), PS-TBD (1,5,7-triazabicyclo[4. 4. 0] 癸- 5-ene polystyrene, 1. 4〇mm〇l/g)[made by the company]i. 〇7g (1. After 5 milliequivalents/amine catalyst amount (g), the acrylic acid was slowly added at 6 hours while stirring at 100 °C. 〇g ( 1. 〇 equivalent) to carry out the reaction. End of the addition of propylene -18- 201139489 After the acid', the reaction was stirred again at 100 ° C until the acid value was 1. OKOHmg/g or less. After the reaction solution was cooled to 6 (TC, the catalyst pS_pPh3 and ps_tbD were removed by a nylon mesh NY-10HC (manufactured by Sefar Co., Ltd.) having a pore size of ΙΟμπι to obtain a partially esterified epoxy resin (PR-3). The epoxy equivalent of (PR-3) was 461 g/eq. As measured in the same manner as in the Example, the content of the phosphorus atom in the resin (pR_3) was 2 ppm or less. [Comparative Example 1] A mixer, an air introduction tube, and a thermometer were prepared. 5 00 ml glass 4-necked flask with reflux cooling tube, mixed with bisphenol a-type epoxy resin: Yepaku EXA8 50CRP [manufactured by DIC Corporation] 340g ( 2. 0 equivalent / epoxy group), methyl acrylate 90. 4g ( 1. 0 equivalent), TPP (triphenylphosphine) [Tokyo Chemical Co., Ltd.] 〇. 5g ( 1. 9 milliequivalents), 25 mg of hydroquinone of a polymerization inhibitor, and 100 mg of p-methoxyphenol, the reaction was stirred at 1 ° C until the acid value was 1. 〇KOHmg/g or less. After the reaction was completed, air was blown into the liquid while at 80 °. (: A 2-hour oxidation treatment was carried out to obtain a partially esterified epoxy resin (KR-1). The obtained resin (KR-1) had an epoxy equivalent of 465 g/eq. As measured in Example 1, the resin was obtained. The content of the phosphorus atom in KR-1) was 290 pPm. [Comparative Example 2] The reaction was carried out in the same manner as in Comparative Example 1, except that no gas was contained in an amount of 25 mg or p-methoxybenzoquinone (100 mg), but the reaction was gelled. The epoxy resin partially esterified in 1 to 4 and Comparative Example 1 was subjected to the following heating stability test and reduced pressure heating promotion test. -19- 201139489 [Additional heat stability test] Esterification of each part 5 〇g of oxygen resin was placed in a 10 〇ml brown polyethylene container. After tamping, the container was placed in an oven at 60 ° C, and taken out after 2 hr, 200 hr, and 500 hr, using an E-type viscometer ( The machine made by the Toki Sangyo Co., Ltd. RE 1 0 5 U) measures the viscosity of the content at a rotation speed of 2 · 5 r P m of the conical turning portion. The rate of change after the manufacturing viscosity is 100 is obtained by the following formula (1). The results are shown in Table 1. Viscosity change rate = (measured viscosity after a periodic question / viscosity after manufacture). . . . . . . . . (1) [Reduced pressure heating promotion test] 50 g of each part of the esterified epoxy resin was placed in a brown polyethylene container of l〇〇ml, and the container was stored in a vacuum oven at 50 ° C and reduced to 1000 Pa under a non-tight plug. After taking out 20 hours, 200 hours, and 500 hours, an E-type viscometer (RE105U manufactured by Toki Sangyo Co., Ltd.) was used to rotate the speed of the conical turning portion. The viscosity was measured at 5 rpm. The rate of change when the viscosity after the production was 100 was obtained by the above formula (1), and the results are shown in Table 1. -20- 201139489 [Table 1] Example 1 Example 2 Example 3 Comparative Example 1 Partially esterified epoxy resin PR-1 PR::! PR-3 KR-1 Heating stability test result 60 °C / 2 0 hours after the passage 1. 00 1. 00 1. 00 1. 10 6 0 °C/2 0 0 hours after the passage 1. 00 1. 00 1. 02 1. 25 6 0 °C / 5 0 0 hours after the passage 1. 00 1. 00 1. 05 2. 05 Reduced pressure heating test results (100Pa) 5 0 ° C / 2 0 hours after the passage 1. 00 1,00 - 1. 18 5 0 °C/2 0 0 hours after the passage 1. 00 1. 01 - 1. 39 5 0°C/5 0 After 0 hours passed 1. 04 1. 05 Gelation As shown in Table 1, the epoxy resin partially esterified in Examples 1 to 3 is almost unchanged at a temperature of 60 ° C even after 500 hours of viscosity, and the heating test can confirm the storage. Excellent stability. However, after the epoxy resin of the partially esterified epoxy resin of Comparative Example 1 was changed by nearly 2 times after 500 hours, the heating stability was lowered. Further, as shown in Table 1, the partially esterified epoxy resins of Examples 1 to 3 were subjected to a reduced pressure of 50 ° C and 10 0 a, and the viscosity was almost unchanged after 500 hours. The pressure heating test confirmed that the storage stability was excellent. However, the partially esterified epoxy resin of Comparative Example 1 gelled after 500 hours. The dielectric properties of the partially esterified epoxy resins of Example 1 and Comparative Example 1 were measured by the following methods. [Measurement of dielectric properties] The reference material is bisphenol A type epoxy resin: Yeppoku - 21 - 201139489 EXA850CRP [manufactured by DIC Corporation]. Dielectric-body measurement system 1 26096W type [made by Sorat Corporation] and liquid electrode SR-C1R (unit capacity: 2pF, distance between electrodes: 1mm) [manufactured by Toyo Industrial Co., Ltd.], raw material resin (reference) measured by FRA method The change in the number of cycles of the partially esterified epoxy resin of Example 1 and Comparative Example 1 was 1. 〇xl〇_2Hz to 1. Dielectric properties (impedance, capacitance, phase angle θ) at 25°C, 50°C, and 80°C at 0χ106Ηζ. Evaluation of the dielectric properties of the resin in an unhardened state can semi-quantify the influence of impurities from the resin. The results are shown in Figures 1 to 9. Also, for example, "1" in the figure. The mark of 0E-02" refers to 1. 0xl (T2. As shown in Figs. 1 to 3, the dielectric properties (impedance, capacitance, and phase angle Θ) of the partially esterified epoxy resin of Example 1 at 25 ° C are almost equivalent to those of the reference raw material resin. The electrical properties are not affected by the impurities in the partially esterified epoxy resin, and it is confirmed that it has excellent electrical properties. Further, as shown in Figs. 1 to 3, the dielectric of the partially esterified epoxy resin of Comparative Example 1 The characteristics are changed with respect to the dielectric properties of the raw material resin. That is, as shown in Fig. 1, the impedance of the raw material resin and the impedance of Comparative Example 1 are low, whereby the partial esterification ring of Comparative Example 1 can be confirmed. The oxygen resin lowers the voltage holding ratio. Further, as shown in Fig. 2, the capacitance of the comparative example changes with respect to the capacitance of the raw material resin, whereby the retention of the partially esterified epoxy resin of Comparative Example 1 can be confirmed. The capacity is deviated. Further, as shown in Fig. 3, the phase angle 0 of Comparative Example 1 is from _90° to 0° with respect to the phase angle 原料 of the raw material resin, thereby confirming the portion of Comparative Example 1 Esterified epoxy resin will lose energy, and the response speed will be slowed down, etc. The partially esterified epoxy resin has a lower dielectric property, and the lower dielectric property is affected by the impurities contained in the partially esterified epoxy resin of Example -22-201139489. As shown in FIGS. 4 to 9, the dielectric temperature (impedance, capacitance, and phase angle Θ) of the partially esterified epoxy resin of Example 1 was measured at a temperature rise to 50 〇c, and the reference material was used. There are some changes in the dielectric properties of the resin, but it is presumed to be affected by the intermolecular interactions of the vinyl group, the ester structure, and the hydroxyl group contained in the partially esterified epoxy resin when the temperature rises. 4 to 9 show that the dielectric properties of the partially esterified epoxy resin of Comparative Example 1 vary greatly with temperature, and the dielectric properties of the raw material resin greatly change, which lowers electrical characteristics. 9 shows that the dielectric properties (impedance, capacitance, and phase angle Θ) of the partially esterified epoxy resin of Example 1 are almost the same as the dielectric properties of the raw material resin, and since almost no impurities are contained, Changed dielectric properties due to impurities, confirmed to be excellent Partially esterified epoxy resin of gas characteristics. [Example 4] The catalyst used was PS-PPh3 (diphenylphosphinopolystyrene, 2. 0mmol/g) [made by Baioda Co., Ltd.] 500mg ( 1. 33 meq/TPP (triphenylphosphine) catalyst amount (g), and TPP (triphenylphosphine) 160 mg [manufactured by Kanto Chemical Co., Ltd.] (0. A partially esterified epoxy resin (PR·4) was obtained in the same manner as in Example 1 except that 61 meq/TPP (triphenylphosphine) catalyst amount (g). The resulting resin had an epoxy equivalent of 45 8 g/eq. The measurement was carried out in the same manner as in Example 1 and the content of the phosphorus atom in the resin (PR-4) was 1,000 ppm. -23- 201139489 [Example 5] The catalyst used was PS-PPhs (diphenylphosphinopolystyrene, 2. 0mmol/g) [made by Baioda Co., Ltd.] 650mg ( 1. 73 milliequivalent /TPP (= phenylphosphine) catalyst amount (g)) and TPP (triphenylphosphine) 80 mg [made by Kanto Chemical Co., Ltd.] (0. 31 meq/TPP (triphenylphosphine) catalyst amount (g)) A partially acetified epoxy resin (P R _ 5 ) was obtained as in Example 1. The epoxy equivalent of the obtained resin was 466 g/eq. The measurement was carried out in the same manner as in Example 1, and as a result, the content of the phosphorus atom in the resin (PR-5) was 48 ppm. [Example 6] The catalyst used was PS-PPh3 (diphenylphosphinopolystyrene, 2. 0mmol/g) [made by Baioda Co., Ltd.] 7〇〇mg ( 1. 87 meq/TPP (triphenylphosphine) catalyst amount (g)) and TPP (triphenylphosphine) 40 mg [manufactured by Kanto Chemical Co., Ltd.] (0. 15 meq/TPP (triphenylphosphine) catalyst amount (g) except for the epoxy resin (PR_6) partially esterified as in Example 1. The resulting resin had an epoxy equivalent of 456 g/eq. The measurement was carried out in the same manner as in Example 1, and as a result, the phosphorus atom content in the resin (P R - 6 ) was 26 ppm. [Comparative Example 3] A partially esterified epoxy resin (KR-2) was obtained in the same manner as in Example 1 except that the oxidation treatment was not carried out at 80 Torr for 2 hours after completion of the reaction. The epoxy equivalent of the obtained resin (KR-2) was 465 g/eq. Ion exchange resin (Amberley 15DRY (ion chain exchange resin of main chain benzenesulfonic acid), I made 5 parts) was added to 300 parts of the resin, 80. The mixture was stirred for 3 hours under the arm. After cooling the reaction solution from -24 to 201139489 to 60 ° C, the ion exchange resin was removed by a nylon mesh NY-10HC (manufactured by Sefar, Switzerland) having a pore size of ηηηι to obtain a partially esterified epoxy resin (KR-3). The measurement was carried out in the same manner as in Example 1. As a result, the content of phosphorus atoms in the resins (KR-2 and KR-3) was 300 ppm and 25 ppm, respectively. It is thus known that even when a strongly acidic ion exchange resin is used, the partially esterified epoxy resin contains a large amount of impurity (phosphorus atom) derived from the catalyst, which is confirmed to reduce the impurity from the catalyst. Effect. Each of the epoxy resins (PR-1: phosphorus atom content: 2 Ppm or less) which is partially esterified in Example 1, and the partially esterified epoxy resin of Example 4 (PR-4: phosphorus atom content: l〇 〇ppm), partially esterified epoxy resin of Example 5 (PR-5: phosphorus atom content: 48 ppm), partially acetified epoxy resin of Example 6 (PR-6: phosphorus atom content: 26 ppm And a partially esterified epoxy resin of Comparative Example 3 (KR-2: phosphorus atom content: 300 ppm), which was measured by the above-described dielectric property measurement, and measured at a temperature of 50 ° C, a number of cycles of 10 mHz to 100 Hz. Capacitance, cycle number 50Hz to 相位 phase angle. Fig. 10 shows the relationship between the content of phosphorus atoms contained in each resin of each cycle number and the capacitance, and Fig. 11 shows the relationship between the content of phosphorus atoms contained in each resin of each cycle number and the phase angle Θ. As shown in Fig. 10, when the impurity contained in the partially esterified epoxy resin, that is, the point of variation of the phosphorus atom content is 50 Ppm or less, it is confirmed that the capacitance (holding capacity) is significantly reduced. In particular, when the number of low-cycles with a frequency of 200 mHz or less is measured, the voltage change at one of the low-cycle numbers is relatively slow when the number of high-cycles is measured. Therefore, the capacitance (holding capacity) changes significantly. Therefore, as shown in Figure 1 ', when the number of low-cycles below 200mHz is measured, -25- 201139489 Phosphorus atom contains partially esterified epoxy resin with S below 5〇ppm, and the phosphorus atom content is more than 5〇. Partially esterified epoxy at ppm will significantly reduce capacitance (hold capacity) changes to confirm that there is no deviation in dielectric properties. As shown in Fig. 11, in the partially esterified epoxy resin having a phosphorus atomic content of 50 ppm or less, the phase angle Θ from -90° to 0° is small, which can reduce voltage retention. The rate is lowered and the response speed is slowed down, confirming that it has excellent dielectric properties. In particular, in the field of the low-frequency range of the DC field (0 Hz) to 24 Hz (for example, as shown in FIG. 11 and 50 Hz to 200 Hz) suitable for the liquid crystal panel in recent years, a partial ester having a phosphorus atom content of 50 ppm or less is measured. The epoxy resin which is partially esterified with a phosphorus atom content exceeding 5 Oppm can significantly reduce the phase angle Θ change, so energy loss does not occur, and it is confirmed that it has excellent dielectric properties. [Industrial Applicability] The partially esterified epoxy resin obtained by the production method of the present invention can be stably stored for a long period of time, and can have excellent stability and electrical properties under reduced pressure, and can be used as an ultraviolet ray or the like. It is used as a raw material for any of the active energy ray and heat, and is therefore suitable as a raw material for a sealing agent for a liquid crystal panel and a coating for an electric member. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a graph showing the relationship between the number of cycles and impedance at 25 ° C of a raw material resin and a partially esterified epoxy resin (Example 1, Comparative Example 1). Figure 2 is a raw material resin and a partially esterified epoxy resin (Examples i, -26-201139489 Comparative Example J 1 ) < A graph showing the relationship between the number of cycles and the capacitance at 25 °c. Figure 3 is a graph showing the relationship between the number of cycles and the phase angle Θ of the raw material resin and the partially esterified epoxy resin (Example 1, ^ ^ 1 } t 2s °c. Figure 4 reed i, 13⁄4 ^ Resin and partially esterified epoxy resin (Example 1, tt g W 1 ) t 5 (measurement of the relationship between the number of cycles and impedance under rc. ® 5 stomach 'raw resin and partially esterified epoxy Resin (Example 1, tb ^ ^ 1} t5 G °C measured the relationship between the number of cycles and the capacitance. ® 6 stomach 'raw resin and partially esterified epoxy resin (example!, tt € W 1 > t 5 (measurement of the relationship between the number of cycles and phase angle 0 at TC. ®> 7 stomach' raw material resin and partially esterified epoxy resin (Example 1, tt @ Μ Ο 8G °C Measure the relationship between the number of cycles and the impedance. ® 8 stomach 'raw resin and partially esterified epoxy resin (Example!, Comparative Example 1) 8 (measurement of the relationship between the number of cycles and the capacitance under TC. 9 is 8 〇 of the raw material resin and the partially esterified epoxy resin (Example i, Comparative Example 1). The relationship between the number of cycles and the phase angle 0 is measured under the armpit. Graph of the phosphorus atom content and the capacitance of each resin contained in each of the number of cycles in. FIG. 11 is a "phase content and the phosphorus atom of each resin contained in each of the number of cycles in a graph showing the relationship between the angle of Θ. -27-