201116604 六、發明說明： 【發明所屬之技術領域】 本發明爲有關一種能量線硬化型環氧樹脂組成物’特 別是可維持高固定準確度的同時，具有優良之速硬化性’ 而適用於光學構件固定用之能量線硬化型環氧樹脂組成物 【先前技術】 光拾取（light pickup)裝置中’爲將光檢測器固定 於機架時，多使用光硬化型接著劑（專利文獻1、2 )。該 接著劑，多被要求應具有高固定準確度及優良硬化性（速 硬化性）。 固定準確度，係指將光檢測器固定於機架之際，顯示 光檢測器不會由特定位置產生動搖之準確度。固定準確度 越低時，於光拾取裝置之製造時或耐久試驗後，若因光檢 測器由特定位置產生動搖時，將無法進行光檢測。因此， 多要求應具有高固定準確度。 速硬化性係指硬化速度較快，可於更短時間下硬化之 意，即，優良硬化性之意。與以往性質相比較時，近年伴 隨機能提升之要求，對於速硬化性之要求則逐漸提升。 於考慮固定準確度時’光硬化型接著劑中，相較於光 硬化性丙烯酸系樹脂接著劑’以陽離子硬化性環氧樹脂接 著劑爲更佳。此外，陽離子硬化性環氧樹脂接著劑，又以 丙烯酸系樹脂接著劑等不會受到氧所造成之硬化阻礙，且 -5- 201116604 其薄膜硬化性更勝一籌（非專利文獻i)。但是，陽離子 硬化性環氧樹脂，確有硬化速度遲緩等問題。 [先前技術文獻] [專利文獻] [專利文獻1]特開2002-251776號公報 [專利文獻2]特開2007-35238號公報 [非專利文獻] [非專利文獻1]「環氧樹脂手冊」、236頁、昭和 62年12月25日、初版1刷發行 【發明內容】 本發明爲於能量線硬化型環氧樹脂組成物中，可維持 高固定準確度的同時’且可解決硬化速度遲緩之問題點爲 目標。 本發明，爲含有環氧樹脂與具有陽離子硬化性官能基 之矽酸鹽化合物與光酸產生劑之能量線硬化型環氧樹脂組 成物。 關連著固定準確度之低硬化收縮率之性能，其係於調 整位置後之光檢測器使用光硬化型接著劑進行硬化時，不 會產生硬化收縮之觀點爲重點，熱時具有高彈性率之性能 ，則是於熱時之不會基於光檢測器本身之重量，或光檢測 器所附著之FPC (聚醯亞胺電路）之張力也不會動搖之觀 點爲重點，即使熱時其光硬化型接著劑也不會產生軟化而 -6- 201116604 仍顯不其硬度。本發明者們，經過各種硏 得到筒固定準確度下’環氧樹脂組成物： 3 %以下’及熱時（耐久試驗之溫度1 〇 〇 5 OMP a以上者爲必要之條件。 有關速硬化性’本發明者們，經過各 知於滿足近年機能提升之要求下，以往i 5 間必須提升至5〜1 0秒。 本發明即爲提供一種可以維持高固定 並可使樹脂組成物之硬化速度大幅提高之 本發明之能量線硬化型環氧樹脂組成 樹脂與具有陽離子硬化性官能基之砂酸鹽 生劑。 (環氧樹脂） 環氧樹脂，並未有特別限定，例如， 氧樹脂、雙酚F型環氧樹脂、聯苯基型環 氧樹脂、酚-酚醛清漆型環氧樹脂、甲酚-樹脂、氫化雙酚A型環氧樹脂、氫化雙酸 聚丁二烯型環氧樹脂、聚異戊二烯型環氧 氧樹脂、脂肪族系環氧樹脂等。該些樹脂 用，或將二種以上組合使用亦可。 脂環式環氧樹脂，例如，乙烯基g 1,2 -環氧基-4 -乙烯基環己烷（CEL2000) 氧基檸檬酸（CEL3000 ) 、3,4-環氧基 究結果，發現欲 之硬化收縮率以 )下之彈性率以 種硏究結果，得 〜20秒之硬化時 準確度的同時， 發明。 物，爲含有環氧 化合物與光酸產 可爲雙酚A型環 氧樹脂、萘型環 酚醛清漆型環氧 F型環氧樹脂、 樹脂、脂環式環 ’可分別單獨使 曼己烯單氧化物 、1，2 : 8,9二環 環己烯基甲基- 201116604 3 ’，4’-環氧基環己烯羧酸酯（CEL202 1 P ) 、2,2-雙（羥基甲 基丁醇之1，2 -環氧基- 4- (2 -環氧乙基（oxiranyl))環己 酯附加物（EHPE3150) 、3,4-環氧基環己烯基甲基-3，，4，-環氧基環己烯羧酸酯、氫化聯苯基型脂環式環氧樹脂等。 其可分別單獨使用，或將二種以上組合使用亦可。 脂肪族環氧樹脂，例如，乙二醇二縮水甘油醚、二乙 二醇二縮水甘油醚、丙二醇二縮水甘油醚、三丙二醇二縮 水甘油醚、新戊二醇二縮水甘油醚、1，4-丁烷二醇二縮水 甘油醚、1,6-己烷二醇二縮水甘油醚、三羥甲基丙烷三縮 水甘油醚、三羥甲基丙烷二縮水甘油醚、聚乙二醇二縮水 甘油醚等。其可分別單獨使用，或將二種以上組合使用亦 可 ° 環氧樹脂，較佳者爲，雙酚A型環氧樹脂（例如， DIC公司製之EPICLON. 850或EPICLON. 860)、氫化雙酚 A型環氧樹脂（例如，：TER公司製之YX8034 )，特佳者爲 DIC 公司製之 EPICLON. 860。 本發明中，雙酚A型環氧樹脂等酚型環氧樹脂可使用 於精製之成品中。酚型環氧樹脂中，合成中所使用之表氯 醇或，未閉環於環氧基之含鹵素之中間體爲以雜質形式存 在。該些雜質，於陽離子硬化觸媒之存在下，即使照射能 量線下也不會硬化。因此，使用去除該些雜質之酚型環氧 樹脂時，可降低使用能量線進行硬化後之硬化物中之未硬 化成份，且可得到含有低鹵素之能量線硬化型環氧樹脂組 成物。 201116604 酚型環氧樹脂之精製，例如，以蒸餾精製、使用氧化 矽凝膠或氧化鋁等以色層分析儀精製，將以共價鍵所鍵結 之鹵素以氫氧化鈉水溶液等鹼水溶液水解方式精製等。雙 酚A形式之環氧樹脂的蒸餾所得之精製品，例如可由D[C 公司取得EXA-8 50CRP。EXA-8 50CRP與雙酚A反應所得之 高分子量環氧樹脂，例如可由DIC公司取得EXA-8067等‘> 本發明之能量線硬化型環氧樹脂組成物中，鹵素量以 5 00ppm以下時，就電腐蝕（電蝕性）之問題、地球環境 之問題等觀點爲較佳。環氧樹脂於使用EXA-850CRP或 EXA-8 067時，除上述本發明之效果以外，可達成低鹵化 效果。 (具有陽離子硬化性官能基之矽酸鹽化合物） 具有陽離子硬化性官能基之矽酸鹽化合物，只要爲可 經陽離子硬化之矽酸鹽化合物時，並未有特別限定。具有 陽離子硬化性官能基之化合物，例如，縮水甘油基矽酸鹽 、脂環式環氧基矽酸鹽、乙烯基矽酸鹽、環氧丙烷基矽酸 鹽等。 脂環式環氧基矽酸鹽，例如四（3、4 -環氧基環己烯 基甲基）矽酸鹽之縮合物等。其市售品例如X-40-2670 C 信越化學工業（股））等。 環氧丙烷基矽酸鹽’例如四[(3-乙基環氧丙烷-3-基 )甲基）]矽酸鹽之縮合物等。其市售品例如，異構環氧 丙烷〇XT-19l(東亞合成（股））等。 201116604 具有陽離子硬化性官能基之矽酸鹽化合物，較佳爲由 環氧丙烷基矽酸鹽及脂環式環氧基矽酸鹽所形成之群所選 擇之1種以上之矽酸鹽化合物，特別是東亞合成公司製環 氧丙烷基矽酸鹽OXT-191及/或信越化學工業製X-40-2670 (脂環式環氧基矽酸鹽）。 具有陽離子硬化性官能基之矽酸鹽化合物之使用量範 圍，相對於45重量份之環氧樹脂，較佳爲2.5〜10重量份 ，特佳者爲5〜10重量份》相對於45重量份之環氧樹脂， 具有陽離子硬化性官能基之矽酸鹽化合物的使用量過少時 ，所得能量線硬化型環氧樹脂組成物之硬化性提升效果將 不充分，超過10重量份時，對於所得能量線硬化型環氧樹 脂組成物之硬化性提升效果也未有增加作用。 (光酸產生劑） 光酸產生劑，只要經由能量線之照射而可發生路易士 酸或布朗司台德酸之化合物時，則無特別限定，例如，鏑 鹽、碘鑰鹽等。光酸產生劑之使用量範圍，相對於45重量 份之環氧樹脂，較佳爲0.5〜10重量份，更佳爲1〜4重量 份。光酸產生劑可以先溶解或分散於4_丁內酯等溶劑中再 進行添加亦可。 锍鹽例如，三苯基锍六氟磷酸鹽、三苯基锍六氟 銻酸鹽、三苯基鏑四（五氟苯基）硼酸鹽、4,4’-雙[二 苯基二氫硫基]二苯基硫化物雙六氟磷酸鹽、4,4’-雙[二 (冷-羥基乙氧基）苯基二氫硫基]二苯基硫化物雙六氟 -10 - 201116604 銻酸鹽、4，4’-雙[二（/3-羥基乙氧基）苯基二氫硫基] 苯基硫化物雙六氟磷酸鹽、7-[二（p-甲苯甲基）二氫 基]-2-異丙基噻頓酮六氟銻酸鹽、7-[二（p-甲苯甲基 二氫硫基]-2-異丙基噻頓酮四（五氟苯基）硼酸鹽、 苯基羰基-4’-二苯基二氫硫基-二苯基硫化物六氟磷酸 、4- ( p-tert-丁基苯基羰基）-4’-二苯基二氫硫基-二苯 硫化物六氟銻酸鹽、4-(?-^1^-丁基苯基羰基）-4’-二 p-甲苯甲基）二氫硫基-二苯基硫化物四（五氟苯基） 酸鹽、旭電化公司製 SP-170、 SP-172、 SP-150、 SP-152 San-Apro公司製CPI-210S等。蔬鹽中，較佳者爲，旭電 公司製 SP-170、 SP-172或 San-Apro公司製 CPI-210S。該 鹽，可分別單獨使用，或將二種以上組合使用亦可。 碘鎗鹽，例如，二苯基碘鑰四（五氟苯基）硼酸 、二苯基碘鑰六氟磷酸鹽、二苯基碘鑰六氟銻酸鹽 二（4-壬基苯基）碘鑰 六氟磷酸鹽、Rhodia公司 PI2074等。碘鑰鹽中較佳者爲，Rhodia公司製PI2074。 些鹽，可分別單獨使用，或將二種以上組合使用亦可。 (其他添加劑） 本發明之能量線硬化型環氧樹脂組成物，於可達成 發明效果之範圍內，可再含有環氧丙烷化合物（環氧丙 基矽酸鹽除外）'塡料、光增感劑、矽烷偶合劑等其他 加劑。 環氧丙烷化合物，爲基於提高塗佈作業性等之低黏 硫 ) 4- 鹽 基 ( 硼 、 化 些 鹽 製 該 本 烷 添 度 -11 - 201116604 化或低收縮率化之目的所添加者。環氧丙烷化合物，例如 3-乙基-3-羥基甲基環氧丙烷（OXA) 、1，4-雙[{(3-乙 基-3-環氧丙烷基）甲氧基}甲基]苯（XDO) 、3-乙基-3-(苯氧基甲基）環氧丙烷（OXT-211 (POX) ) 、2-乙基 己基環氧丙烷（OXT-212 (EHOX))、苯二甲基雙環氧 丙烷（OXT-121 (XDO))、雙（3-乙基-3-環氧丙烷基甲 基）醚（OXT-221(DOX) ) 、3-乙基-[{ (3-三乙氧基 矽烷基丙氧基）甲基）環氧丙烷、環氧丙烷基倍半矽氧院 、酚-酚醛清漆環氧丙烷等。括弧內爲東亞合成公司貨品 編號。環氧丙烷化合物之添加量，相對於45重量份之環氧 樹脂，較佳爲5〜100重量份，更佳爲1〇〜50重量份。各個 環氧丙烷化合物’可單獨使用亦可，或將二種以上組合使 用亦可。 塡料爲就降低硬化時硬化收縮率之目的而添加者。塡 料例如丙烯酸系塡料、苯乙烯系塡料、丙烯/苯乙烯共聚 系塡料、氟系樹脂塡料' 聚乙烯系塡料、聚丙烯系塡料、 聚矽氧系塡料、氧化矽系塡料、雲母、滑石、玻璃塡料等 。其可分別單獨使用，或將二種以上組合使用亦可。較佳 之塡料爲丙烯/苯乙烯共聚系塡料。塡料之添加量，相對 於45重量份之環氧樹脂，較佳爲5〜1〇〇重量份，更佳爲15 〜6 0重量份。 光增感劑’並未有特別限定，例如可爲，羰基化合物 、有機硫化合物、過硫化物、氧化還原系化合物、偶氮及 —偶氮化合物、鹵化合物、光還原性色素等。光增感劑， -12- 201116604 具體而言例如，苯偶姻甲基醚、苯偶姻異丙基醚、α,α-二甲氧基-α -苯基苯乙酮等苯偶姻衍生物；二苯甲酮、 2，4-二氯二苯甲酮、〇-苯甲醯基苯甲酸甲基、4,4’-雙（二 乙基胺基）二苯甲酮等二苯甲酮衍生物；2,4-二乙基噻頓 酮、2-氯噻頓酮、2-異丙基噻頓酮等噻頓酮衍生物；2-氯 蒽醌、2-甲基蒽醌等蒽醌衍生物；Ν-甲基吖啶酮、Ν-丁基 吖啶酮等吖啶酮衍生物；其他例如α，α -二乙氧基苯乙酮 、苄基、蒹酮、氧葱酮、雙氧鈾化合物等。該些之光增感 劑，可單獨使用，或將二種以上組合使用亦可。較佳之光 增感劑爲2,4-二乙基噻頓酮（日本化藥製DETX-S )。光增 感劑之添加量，相對於45重量份之環氧樹脂爲0.001〜1重 量份，較佳爲〇.〇 05〜0.1重量份。使用光酸產生劑之碘鑰 鹽系ΡΙ2074時，以使用光增感劑DETX-S爲佳，其添加量 ，相對於45重量份之環氧樹脂，較佳爲0.005〜0.1重量份 ，特佳者爲0.01重量份》使用光酸產生劑之鏑鹽系之CPI-21 0S之情形 ，即 使不添 加光增 感劑， 亦可顯 示優良 之硬化 性。 矽烷偶合劑，可配合賦予接著性之目的而添加。矽烷 偶合劑，例如可使用四甲氧基矽烷、四乙氧基矽烷 '四丙 氧基矽烷、四異丙氧基矽烷、四丁氧基矽烷、二甲氧基二 乙氧基矽烷、二甲氧基二異丙氧基矽烷、二乙氧基二異丙 氧基矽烷、二乙氧基二丁氧基矽烷等四烷氧基矽烷類；甲 基三甲氧基矽烷、甲基三乙氧基矽烷、甲基三異丙氧基矽 烷、乙基三乙氧基矽烷、乙基三丁氧基矽烷 '環己基三乙 -13- 201116604 氧基矽烷、苯基三異丙氧基矽烷等三烷氧基矽烷類；二甲 基二甲氧基矽烷、二甲基二乙氧基矽烷、二乙基二乙氧基 矽烷、二乙基二丁氧基矽烷、苯基乙基二乙氧基矽烷等二 烷氧基矽烷類等例示。該些矽烷偶合劑，可單獨或將2種 以上組合使用亦可。矽烷偶合劑之添加量，相對於45重量 份之環氧樹脂，較佳爲0.1〜10重量份，更佳爲0.5〜5重 量份。 (能量線硬化型環氧樹脂組成物之用途） 本發明之能量線硬化型環氧樹脂組成物，可以高固定 準確度迅速地固定於搭載例如，LD (雷射二極體）、光 檢測器（PD : Photo-Detector )、透鏡、稜鏡等光學構件 或透鏡等光學構件之光學模組等，而極適合作爲組裝光學 裝置用之接著劑。光學裝置，例如，亦可使用於專利文獻 1 ' 2或，特開2007-3 1 1 006公報之段落0023所記載之光拾 取裝置中，以偏斜螺絲（Skew-Screw )調整操作器之傾斜 度後之固定使用。又，其他例如，亦可使用於反射體等光 學構件之固定或固定懸吊裝置之纜線等。 【實施方式】 [實施例] 以下，本發明將以實施例進行說明。又，添加量以重 量份表示。 -14· 201116604 [實施例1〜6及比較例1〜2 ] 基於表1所示之添加內容，使光酸產生劑PI2 074或 CPI-210S溶解於4-丁內酯，將其加入EPICLON. 8 50中，攪 拌至透明爲止，製作比較例1及2之能量線硬化型環氧樹脂 組成物。 基於表1所示之添加內容，於比較例1或2之環氧樹脂 組成物中添加OXT- 1 9 1 ’攪拌至均勻爲止’以製作實施例 1〜6之能量線硬化型環氧樹脂組成物。 [表1] 比較例1 實施例1 實施例2 實施例3 比較例2 實施例4 實施例5 實施例6 EPICLON.850 45 45 45 45 45 45 45 45 OXT-191 2.5 5 10 2.5 5 10 PI2074 3 3 3 3 CPI-210S 3 3 3 3 4-丁內酯 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 EPICLON.850 :雙酚A型環氧樹脂（DIC公司製） OXT-191 :異構環氧丙烷（東亞合成公司製） PI2〇74 :确錄鹽系光酸產生劑（Rhodia公司製） CPI-210S :锍系光酸產生劑（San-Apro公司製） 4-丁內酯：溶劑（和光純藥公司製） [試驗例1] 試驗實施例1〜6及比較例1〜2之能量線硬化型環氧樹 脂組成物的硬化性。硬化性爲，分別將能量線硬化型環氧 樹脂組成物塗佈1mm厚度後，以手指接觸方式確認使用濱 松 Photonics公司製 UV照射機以 5〇〇mW/cm2 ( 365nm)、 2 · 5秒鐘、5秒鐘、1 〇秒鐘、1 5秒鐘、2 0秒鐘或3 0秒鐘照射 -15- 201116604 後之硬化狀態。經由手指接觸確認結果，以液狀之情形爲 X，柔軟之硬化物之情形爲△，固化之情形爲〇之方式進 行評估。其結果係如表2所示。 [表2] 比較例 1 實施例 1 實施例 2 實施例 3 比較例 2 實施例 4 實施例 5 實施例 6 500mW/cm2x2.5 秒 X X Δ Δ X X Δ Δ 500mW/cm2x5 秒 X Δ 〇 〇 X Δ 〇 〇 500mW/cm2x 10秒 X 〇 〇 〇 Δ 〇 〇 〇 500mW/cm2xl5 秒 X 〇 〇 〇 Δ 〇 〇 〇 500mW/cm2x20 秒 Δ 〇 〇 0 〇 〇 〇 〇 500m W/cm2x3 0 秒 〇 〇 〇 〇 〇 〇 〇 〇 [實施例7〜1 1及比較例3 ] 基於表3所示之添加內容’製作實施例7〜1 1及比較例 3之能量線硬化型環氧樹脂組成物。 -16- 201116604 [表3] 貨號 實施例7 實施例8 實施例9 實施例10 比較例3 實施例11 EPICLON.860 45 45 45 45 45 45 OXT-211 15 15 15 15 15 15 OXT-121 5 5 5 5 5 5 OXT-191 5 5 10 10 3 PI2074 3 3 3 3 3 DETX-S 0.01 0.01 0.01 0.01 0.01 CPI-210S 3 Art Pari GS-350T 45 45 滑石P-2 20 20 20 20 EPICLON.860 :雙酣A型環氧樹脂（DIC公司製） OXT-211 : 3-乙基-3-(苯氧基甲基）環氧丙院（東亞合成公司製） OXT-121 : 1，4-雙[[(3-乙基-3-環氧丙烷基）甲氧基]甲基]苯（東亞合成公司製） OXT-191 :異構環氧丙烷（東亞合成公司製） ΡΠ074 :砩錄鹽系光酸產生劑（Rhodia公司製） DETX-S : 2,4-二乙基噻頓酮（增感劑：日本化藥公司製） CPI-210S :锍系光酸產生劑（San-Apro公司製）201116604 VI. Description of the Invention: [Technical Field] The present invention relates to an energy ray-curable epoxy resin composition, which is excellent in speed fixation while maintaining high fixation accuracy, and is suitable for optical use. Energy-line-hardening epoxy resin composition for fixing a member [Prior Art] In a light pickup device, a photo-curing adhesive is often used for fixing a photodetector to a frame (Patent Documents 1 and 2) ). The adhesive agent is required to have high fixing accuracy and excellent hardenability (speed hardening property). Fixed accuracy refers to the accuracy with which the photodetector does not shake from a specific location when the photodetector is fixed to the frame. The lower the fixing accuracy, the light detection cannot be performed when the optical detector is shaken by a specific position during the manufacture of the optical pickup device or after the endurance test. Therefore, multiple requirements should have high fixed accuracy. The quick-curing property means that the hardening speed is fast and it can be hardened in a shorter time, that is, it is excellent in hardenability. Compared with the previous nature, in recent years, with the requirement of random increase, the requirement for rapid hardening is gradually improved. In the case where the fixing accuracy is considered, the photocurable adhesive is more preferably a cationically curable epoxy resin binder than the photocurable acrylic resin adhesive. In addition, the cation-curable epoxy resin adhesive is not hindered by the hardening by oxygen, etc., and the film hardening property is superior to that of -5-201116604 (Non-Patent Document i). However, the cationically curable epoxy resin does have problems such as a slow curing rate. [Prior Art Document] [Patent Document 1] JP-A-2002-251776 [Patent Document 2] JP-A-2007-35238 [Non-Patent Document] [Non-Patent Document 1] "Epoxy Resin Manual" 236 pages, December 25, 2003, the first edition of the 1st brush release. [Invention] The present invention is capable of maintaining a high degree of fixation accuracy in an energy ray-curable epoxy resin composition, and can solve the slowing of the hardening speed. The problem is the goal. The present invention is an energy ray-curable epoxy resin composition comprising an epoxy resin and a phthalate compound having a cationically curable functional group and a photoacid generator. The performance of the low-hardening shrinkage ratio of the fixed accuracy is focused on the viewpoint that the photodetector after the adjustment position is hardened by the photo-curing adhesive, and the hardening shrinkage is not caused, and the heat has a high modulus of elasticity. The performance is based on the fact that the heat of the photodetector itself is not based on the weight of the photodetector itself, or the tension of the FPC (polyimine circuit) to which the photodetector is attached is not shaken, even when it is hot, its photohardening The type of adhesive also does not produce softening and -6-201116604 still does not show its hardness. The inventors of the present invention obtained the "epoxy resin composition: 3% or less" and the heat when the cylinder is fixed under various conditions (the temperature of the durability test is 1 〇〇 5 OMP a or more is a necessary condition. The present inventors have known that the i 5 must be raised to 5 to 10 seconds in the past, and it is necessary to maintain a high fixation rate and a hardening rate of the resin composition. The energy ray-curable epoxy resin composition resin of the present invention and the sulphate developer having a cationic hardening functional group are greatly improved. (Epoxy resin) The epoxy resin is not particularly limited, for example, an oxygen resin or a double Phenol F type epoxy resin, biphenyl type epoxy resin, phenol-novolac type epoxy resin, cresol-resin, hydrogenated bisphenol A type epoxy resin, hydrogenated diacid polybutadiene type epoxy resin, A polyisoprene type epoxy resin, an aliphatic epoxy resin, etc. These resins may be used in combination of two or more kinds. The alicyclic epoxy resin, for example, vinyl g 1,2- Epoxy-4-vinylcyclohexane CEL2000) The results of oxycitric acid (CEL3000) and 3,4-epoxy group, and the elastic rate of the desired hardening shrinkage rate were found to be the results of the hardening of ~20 seconds. invention. The product may be a bisphenol A type epoxy resin, a naphthalene type novolac type epoxy F type epoxy resin, a resin, an alicyclic ring, and may be separately used for the mannitol. Oxide, 1,2:8,8-dicyclocyclohexenylmethyl- 201116604 3 ',4'-Epoxycyclohexenecarboxylate (CEL202 1 P ), 2,2-bis(hydroxymethyl) Butanol 1,2-epoxy-4-(2-oxiranyl)cyclohexyl ester addenda (EHPE3150), 3,4-epoxycyclohexenylmethyl-3, 4,-epoxycyclohexene carboxylate, hydrogenated biphenyl alicyclic epoxy resin, etc. These may be used alone or in combination of two or more. Aliphatic epoxy resins, for example, Ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,4-butanediol diglycidyl Ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, trimethylolpropane diglycidyl ether, polyethylene glycol diglycidyl ether, etc. They may be used singly or in combination of two or more. Epoxy resin, preferably bisphenol A type epoxy resin (for example, EPICLON. 850 or EPICLON. 860 by DIC), hydrogenated bisphenol A Epoxy resin (for example, YX8034 manufactured by TER Co., Ltd.), especially EPICLON. 860 manufactured by DIC Corporation. In the present invention, a phenol type epoxy resin such as a bisphenol A type epoxy resin can be used for a refined product. In the phenolic epoxy resin, the epichlorohydrin used in the synthesis or the halogen-containing intermediate which is not ring-closed to the epoxy group exists in the form of impurities. In the presence of the cationic hardening catalyst, It does not harden even under the irradiation energy line. Therefore, when a phenol type epoxy resin which removes these impurities is used, the uncured component in the cured product after hardening using the energy ray can be reduced, and the energy containing low halogen can be obtained. Line-cured epoxy resin composition. 201116604 Purification of phenolic epoxy resin, for example, by distillation, purification by a chromatography analyzer using cerium oxide gel or alumina, and bonding of a halogen bonded by a covalent bond Hydrogen and oxygen An aqueous alkali solution such as a sodium aqueous solution is purified by hydrolysis, etc. A refined product obtained by distillation of an epoxy resin in the form of bisphenol A can be obtained, for example, from D[C Company, EXA-8 50CRP. The high molecular weight of EXA-8 50CRP and bisphenol A is obtained. In the energy ray-curable epoxy resin composition of the present invention, when the amount of halogen is 500 ppm or less, the epoxy resin is a problem of electrocorrosion (electroplating) and the earth. From the viewpoint of environmental problems, etc., when epoxy resin is used in EXA-850CRP or EXA-8 067, in addition to the effects of the present invention described above, a low halogenation effect can be achieved. (Citrate compound having a cationically curable functional group) The phthalate compound having a cationically curable functional group is not particularly limited as long as it is a cation-hardenable phthalate compound. A compound having a cationically curable functional group, for example, glycidyl decanoate, alicyclic epoxy decanoate, vinyl phthalate, propylene oxide ruthenate or the like. An alicyclic epoxy decanoate such as a condensate of tetrakis(3,4-epoxycyclohexenylmethyl) phthalate or the like. Commercial products such as X-40-2670 C Shin-Etsu Chemical Co., Ltd., and the like. A propylene oxide decanoate such as a condensate of tetrakis[(3-ethyl propylene oxide-3-yl)methyl)] decanoate or the like. Commercially available products thereof are, for example, isomeric propylene oxide oxime XT-19l (East Asia Synthetic Co., Ltd.). 201116604 A phthalate compound having a cationically curable functional group, preferably one or more citrate compounds selected from the group consisting of propylene oxide phthalate and alicyclic epoxy silicate. In particular, propylene oxide phthalate OXT-191 manufactured by East Asia Synthesis Co., Ltd. and/or X-40-2670 (alicyclic epoxy ruthenate) manufactured by Shin-Etsu Chemical Co., Ltd. The use amount of the phthalate compound having a cationic hardening functional group is preferably from 2.5 to 10 parts by weight, particularly preferably from 5 to 10 parts by weight, based on 45 parts by weight of the epoxy resin, relative to 45 parts by weight. When the amount of the phthalate compound having a cationically curable functional group is too small, the effect of improving the curability of the obtained energy ray-curable epoxy resin composition is insufficient, and when it exceeds 10 parts by weight, the energy obtained is The hardenability improving effect of the wire-hardened epoxy resin composition also did not increase. (Photoacid generator) The photoacid generator is not particularly limited as long as it can cause a compound of Lewis acid or Bronsted acid via irradiation with an energy ray, and examples thereof include a sulfonium salt and an iodine salt. The photoacid generator is used in an amount of preferably 0.5 to 10 parts by weight, more preferably 1 to 4 parts by weight, based on 45 parts by weight of the epoxy resin. The photoacid generator may be dissolved or dispersed in a solvent such as 4-butyrolactone before being added. Anthracene salts, for example, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrakis(pentafluorophenyl)borate, 4,4'-bis[diphenyldihydrogen sulfide Diphenyl sulfide dihexafluorophosphate, 4,4'-bis[di(col-hydroxyethoxy)phenyldihydrothio]diphenyl sulfide dihexafluoro-10 - 201116604 tannic acid Salt, 4,4'-bis[bis(/3-hydroxyethoxy)phenyldihydrothio]phenyl sulfide bishexafluorophosphate, 7-[bis(p-toluomethyl)dihydro ]-2-isopropylthiophenone hexafluoroantimonate, 7-[bis(p-toluomethyldihydrothio)-2-isopropylthiophenone tetrakis(pentafluorophenyl)borate, Phenylcarbonyl-4'-diphenyldihydrothio-diphenyl sulfide hexafluorophosphate, 4-(p-tert-butylphenylcarbonyl)-4'-diphenyldihydrothio-di Benzene sulfide hexafluoroantimonate, 4-(?-^1^-butylphenylcarbonyl)-4'-di-p-toluomethyl)dihydrothio-diphenyl sulfide tetrakis(pentafluorobenzene) Base acid salt, SP-170, SP-172, SP-150, SP-152 manufactured by Asahi Kasei Co., Ltd., CPI-210S manufactured by San-Apro Co., Ltd., etc. Among the vegetable salts, preferred are SP-170, SP-172 manufactured by Solectron Corporation or CPI-210S manufactured by San-Apro Co., Ltd. These salts may be used alone or in combination of two or more. Iodine salt, for example, diphenyl iodine tetrakis(pentafluorophenyl)borate, diphenyl iodine hexafluorophosphate, diphenyl iodine hexafluoroantimonate bis(4-mercaptophenyl) iodine Key hexafluorophosphate, Rhodia company PI2074 and so on. Preferred among the iodine salts is PI2074 manufactured by Rhodia Corporation. These salts may be used alone or in combination of two or more. (Other Additives) The energy ray-curable epoxy resin composition of the present invention may further contain a propylene oxide compound (excluding epoxy propyl citrate) in the range in which the effects of the invention can be attained. Other additives such as agents and decane coupling agents. The propylene oxide compound is added for the purpose of improving the low viscosity of the coating, such as a low-viscosity sulfur-based 4-basic group (boron, the salt-added -11 - 201116604, or a low shrinkage ratio). A propylene oxide compound such as 3-ethyl-3-hydroxymethyl propylene oxide (OXA), 1,4-bis[{(3-ethyl-3-epoxypropenyl)methoxy}methyl] Benzene (XDO), 3-ethyl-3-(phenoxymethyl) propylene oxide (OXT-211 (POX)), 2-ethylhexyl propylene oxide (OXT-212 (EHOX)), benzene Methyl propylene oxide (OXT-121 (XDO)), bis(3-ethyl-3-epoxypropanemethyl)ether (OXT-221(DOX)), 3-ethyl-[{ (3) -Triethoxydecylpropoxy)methyl) propylene oxide, propylene oxide sesquioxide, phenol novolac propylene oxide, and the like. Within the brackets is the East Asia Synthetic Company's item number. The amount of the propylene oxide compound to be added is preferably 5 to 100 parts by weight, more preferably 1 to 50 parts by weight, based on 45 parts by weight of the epoxy resin. Each of the propylene oxide compounds may be used singly or in combination of two or more. The tanning material is added for the purpose of reducing the hardening shrinkage rate at the time of hardening. For example, acrylic materials, styrene-based materials, propylene/styrene copolymer-based materials, fluororesin materials, polyethylene-based materials, polypropylene-based materials, poly-oxygen-based materials, and cerium oxide System materials, mica, talc, glass materials, etc. They may be used alone or in combination of two or more. A preferred feedstock is a propylene/styrene copolymer tie. The amount of the dip added is preferably 5 to 1 part by weight, more preferably 15 to 60 parts by weight, based on 45 parts by weight of the epoxy resin. The photosensitizer y is not particularly limited, and examples thereof include a carbonyl compound, an organic sulfur compound, a persulfide compound, a redox compound, an azo and an azo compound, a halogen compound, and a photoreductive dye. Photosensitizer, -12- 201116604 Specifically, for example, benzoin methyl ether, benzoin isopropyl ether, α,α-dimethoxy-α-phenylacetophenone, etc. Dibenzophenone, 2,4-dichlorobenzophenone, 〇-benzoyl benzoic acid methyl, 4,4'-bis(diethylamino)benzophenone, etc. Ketone derivatives; thiatonone derivatives such as 2,4-diethylthiophenone, 2-chlorothiophenone, 2-isopropylthione, etc.; 2-chloroindole, 2-methylindole, etc. Anthraquinone derivatives; acridone derivatives such as hydrazine-methylacridone and hydrazine-butylacridone; others such as α,α-diethoxyacetophenone, benzyl, anthrone, and oxysyl ketone , uranium oxide compounds, etc. These light sensitizers may be used singly or in combination of two or more. A preferred light sensitizer is 2,4-diethyl thiodone (DETX-S manufactured by Nippon Kayaku Co., Ltd.). The amount of the photosensitizer added is 0.001 to 1 part by weight, preferably 〇.〇 05 to 0.1 part by weight, based on 45 parts by weight of the epoxy resin. When the iodine salt ΡΙ 2074 of the photoacid generator is used, it is preferable to use the photo sensitizer DETX-S, and the amount thereof is preferably 0.005 to 0.1 parts by weight based on 45 parts by weight of the epoxy resin. In the case of 0.01 parts by weight of the CPI-21 0S using a bismuth salt of a photoacid generator, excellent hardenability can be exhibited without adding a photosensitizer. The decane coupling agent can be added for the purpose of imparting adhesion. As the decane coupling agent, for example, tetramethoxy decane, tetraethoxy decane 'tetrapropoxy decane, tetraisopropoxy decane, tetrabutoxy decane, dimethoxydiethoxy decane, and dimethyl can be used. a tetraalkoxynonane such as oxydiisopropoxydecane, diethoxydiisopropoxydecane or diethoxydibutoxydecane; methyltrimethoxydecane, methyltriethoxy Decane, methyl triisopropoxy decane, ethyl triethoxy decane, ethyl tributoxy decane 'cyclohexyl triethyl-13- 201116604 oxane, phenyl triisopropoxy decane, etc. Oxy decanes; dimethyl dimethoxy decane, dimethyl diethoxy decane, diethyl diethoxy decane, diethyl dibutoxy decane, phenyl ethyl diethoxy decane Examples of the like dialoxy oxanes and the like. These decane coupling agents may be used singly or in combination of two or more kinds. The amount of the decane coupling agent to be added is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, based on 45 parts by weight of the epoxy resin. (Application of the energy ray-curable epoxy resin composition) The energy ray-curable epoxy resin composition of the present invention can be quickly fixed to a mounting, for example, an LD (Laser Diode) or a photodetector with high fixation accuracy. (PD: Photo-Detector), an optical member such as an optical member such as a lens or a cymbal or an optical module such as a lens, and is excellent as an adhesive for assembling an optical device. The optical device can be used, for example, in the optical pickup device described in the patent document 1 ' 2 or the paragraph 0023 of JP-A-2007-3 1 006, and the tilt of the operator is adjusted with a skew screw (Skew-Screw). Fixed use after the degree. Further, for example, a cable for fixing or fixing a suspension device of an optical member such as a reflector or the like may be used. [Embodiment] [Examples] Hereinafter, the present invention will be described by way of examples. Further, the amount added is expressed in parts by weight. -14· 201116604 [Examples 1 to 6 and Comparative Examples 1 to 2] Based on the contents shown in Table 1, the photoacid generator PI2 074 or CPI-210S was dissolved in 4-butyrolactone and added to EPICLON. In 850, the energy ray-curable epoxy resin compositions of Comparative Examples 1 and 2 were produced by stirring until it was transparent. Based on the contents shown in Table 1, the OXT-1 9 1 'stirred until uniform was added to the epoxy resin composition of Comparative Example 1 or 2 to prepare the energy ray-curable epoxy resin of Examples 1 to 6. Things. [Table 1] Comparative Example 1 Example 1 Example 2 Example 3 Comparative Example 2 Example 4 Example 5 Example 6 EPICLON.850 45 45 45 45 45 45 45 45 OXT-191 2.5 5 10 2.5 5 10 PI2074 3 3 3 3 CPI-210S 3 3 3 3 4-butyrolactone 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 EPICLON.850 : bisphenol A type epoxy resin (made by DIC) OXT-191 : isomeric propylene oxide (East Asia Synthetic company) PI2〇74: Confirmed salt photoacid generator (manufactured by Rhodia Co., Ltd.) CPI-210S: Lanthanide photoacid generator (manufactured by San-Apro Co., Ltd.) 4-butyrolactone: Solvent (Wako Pure Chemical Co., Ltd. (Testing Example 1) The curability of the energy ray-curable epoxy resin compositions of Test Examples 1 to 6 and Comparative Examples 1 to 2 was examined. For the hardenability, the energy ray-curable epoxy resin composition was applied to a thickness of 1 mm, and it was confirmed by finger contact using a UV irradiator manufactured by Hamamatsu Photonics Co., Ltd. at 5 〇〇mW/cm 2 (365 nm) for 2 · 5 seconds. , 5 seconds, 1 〇 second, 15 seconds, 20 seconds, or 30 seconds to illuminate the hardened state after -15-201116604. The results were confirmed by finger contact, and the case of liquid was X, the case of softened hardened material was Δ, and the case of solidification was evaluated by means of 〇. The results are shown in Table 2. [Table 2] Comparative Example 1 Example 1 Example 2 Example 3 Comparative Example 2 Example 4 Example 5 Example 6 500 mW/cm2 x 2.5 seconds XX Δ Δ XX Δ Δ 500 mW/cm 2 x 5 seconds X Δ 〇〇X Δ 〇〇500mW/cm2x 10 seconds X 〇〇〇Δ 〇〇〇500mW/cm2xl5 seconds X 〇〇〇Δ 〇〇〇500mW/cm2x20 seconds Δ 〇〇〇〇0 〇〇〇〇500m W/cm2x3 0 seconds 〇〇〇〇〇实施 [Examples 7 to 1 1 and Comparative Example 3] The energy ray-curable epoxy resin compositions of Examples 7 to 1 1 and Comparative Example 3 were produced based on the contents of addition shown in Table 3. -16- 201116604 [Table 3] Item No. Example 7 Example 8 Example 9 Example 10 Comparative Example 3 Example 11 EPICLON.860 45 45 45 45 45 45 OXT-211 15 15 15 15 15 15 OXT-121 5 5 5 5 5 5 OXT-191 5 5 10 10 3 PI2074 3 3 3 3 3 DETX-S 0.01 0.01 0.01 0.01 0.01 CPI-210S 3 Art Pari GS-350T 45 45 Talc P-2 20 20 20 20 EPICLON.860 : Double酣A type epoxy resin (manufactured by DIC Corporation) OXT-211 : 3-ethyl-3-(phenoxymethyl) epoxy propylene compound (manufactured by Toagosei Co., Ltd.) OXT-121 : 1,4-double [[ (3-ethyl-3-epoxypropenyl)methoxy]methyl]benzene (manufactured by Toagosei Co., Ltd.) OXT-191: isomeric propylene oxide (manufactured by Toagosei Co., Ltd.) ΡΠ074: 砩 盐 salt photoacid Producer (manufactured by Rhodia Co., Ltd.) DETX-S : 2,4-diethyl thiatonone (sensitizer: manufactured by Nippon Kayaku Co., Ltd.) CPI-210S: lanthanide photoacid generator (manufactured by San-Apro Co., Ltd.)
ArtParlGS-350T :丙稀/苯乙烯共聚物塡料（根上工業公司製） 滑石P-2 :滑石（日本滑石公司製） [試驗例2] 依試驗1相同方法測試實施例7〜1 1及比較例3之能量 線硬化型環氧樹脂組成物各別之硬化性。其結果係如表4 所示。 -17- 201116604 [表4] 實施例 實施例 實施例 實施例 比較例 實施例 7 8 9 10 3 11 500mW/cm2x2.5 秒 〇 Δ △ Δ X Δ 500mW/cm2x5 秒 〇 〇 〇 〇 Δ 〇 500mW/cm2x 10秒 〇 〇 〇 〇 Δ 〇 500mW/cm2xl 5秒 〇 〇 〇 〇 〇 〇 500mW/cm2x20 秒 〇 〇 〇 〇 〇 〇 [試驗例3] 分別測定實施例7及8與比較例3之能量線硬化型環氧 樹脂組成物之硬化收縮率及彈性率。硬化收縮率爲依 JISK68 3 3記載之CUP法進行測定。彈性率爲使用SII公司製 EXSTAR6 000 ’依平板拉伸法進行測定。其結果係如表5所 示。 [表5] 項目 實施例7 實施例8 比較例3 — 硬化收縮率（0/«) 1.5 1.4 2.1 25°C彈性率（MPa) 3000 4040 4000 10(TC彈性率（MPa) 120 250 295 [實施例12〜14] 基於表6所示之添加內容，製作實施例12〜14之能量 線硬化型環氧樹脂組成物。 -18 - 201116604 [表6] 實施例12 實施例13 實施例14 EPICLON.850 45 45 45 X-40-2670 2.5 5 10 PI2074 3 3 3 4-丁內酯 1.5 1.5 1.5 500m W/cm2x2.5 秒 X Δ Δ 500mW/cm2x5 秒 Δ 〇 〇 500m W/cm2x 10秒 〇 〇 〇 500mW/cm2x 15 秒 〇 〇 〇 X-40-2670 ’·脂環式環氧基矽酸鹽（信越化學工業製) [試驗例4] 依試驗1相同方法測試實施例1 2〜1 4之能量線硬化型 環氧樹脂組成物各別之硬化性。試驗結果係如表6所示。 [實施例1 5〜1 8 ] 基於表7所示之添加內容，製作實施例1 5〜1 8之能量 線硬化型環氧樹脂組成物。 -19- 201116604 [表7]ArtParl GS-350T: propylene/styrene copolymer dip (manufactured by Kasei Kogyo Co., Ltd.) talc P-2: talc (manufactured by Nippon Talc Co., Ltd.) [Test Example 2] Test Examples 7 to 1 1 and compare in the same manner as in Test 1. The energy ray-curable epoxy resin composition of Example 3 has respective hardenability. The results are shown in Table 4. -17- 201116604 [Table 4] EXAMPLES EXAMPLES EXAMPLES Comparative Examples Example 7 8 9 10 3 11 500 mW/cm 2 x 2.5 seconds 〇 Δ Δ X Δ 500 mW/cm 2 x 5 seconds 〇〇〇〇 Δ m 500 mW / Cm2x 10 sec 〇〇〇〇 〇 m 500 mW/cm 2 x l 5 sec 〇〇〇〇〇〇 500 mW/cm 2 x 20 sec [Test Example 3] The energy ray hardening of Examples 7 and 8 and Comparative Example 3 were respectively measured. Hardening shrinkage and modulus of elasticity of the epoxy resin composition. The curing shrinkage ratio was measured in accordance with the CUP method described in JIS K68 3 3 . The modulus of elasticity was measured by the plate stretching method using EXSTAR 6 000 ' manufactured by SII Corporation. The results are shown in Table 5. [Table 5] Item Example 7 Example 8 Comparative Example 3 - Hardening shrinkage ratio (0/«) 1.5 1.4 2.1 25°C elastic modulus (MPa) 3000 4040 4000 10 (TC elastic modulus (MPa) 120 250 295 [Implementation Examples 12 to 14] The energy ray-curable epoxy resin compositions of Examples 12 to 14 were produced based on the contents shown in Table 6. -18 - 201116604 [Table 6] Example 12 Example 13 Example 14 EPICLON. 850 45 45 45 X-40-2670 2.5 5 10 PI2074 3 3 3 4-butyrolactone 1.5 1.5 1.5 500m W/cm2x2.5 seconds X Δ Δ 500mW/cm2x5 seconds Δ 〇〇500m W/cm2x 10 seconds〇〇〇 500 mW/cm2 x 15 sec X-40-2670 '· alicyclic epoxy decanoate (manufactured by Shin-Etsu Chemical Co., Ltd.) [Test Example 4] The energy of Example 1 2 to 1 4 was tested in the same manner as in Test 1. Each of the wire-curable epoxy resin compositions was cured. The test results are shown in Table 6. [Example 1 5 to 1 8] Based on the contents shown in Table 7, Examples 1 to 5 were produced. Energy line hardening epoxy resin composition. -19- 201116604 [Table 7]
實施例15 實施例16 實施例Π 實施例18 EXA-850CRP _ • _ 45 EPICLON.860 • _ 45 - EXA-8067 45 45 _ _ OXT-211 15 15 15 15 OXT-121 5 5 5 5 OXT-191 5 5 5 5 PI2074 3 3 3 3 DETX-S 0.01 . 0.01 0.01 1-651 _ 1 . - Art-Parl 55 55 55 55 GS-350T EXA-850CRP :雙酚A型環氧樹脂（DIC公司製：經由蒸餾之精製品） EXA-8067 :雙酚A型環氧樹脂（DIC公司製：EXA-850CRP與雙酚A之反應物） 1-651 : 2,2-二甲氧基-1,2-二苯基乙烷（汽巴公司製增感劑） [試驗例5] 分別測試實施例1 5及1 6之能量線硬化型環氧樹脂組成 物的LED硬化性。LED硬化性，爲將能量線硬化型環氧樹 脂組成物滴一滴於鋁板上，再使用波長3 6 5nm之LED照射 機以500m W/cm2之照度（照度計濱松Photonics製C60 8 0- 1 3 )照射1 〇秒鐘使其硬化，以手指接觸確認其硬化狀態。 LED硬化性之基準爲，〇：硬化（固體）、「X」印：未 硬化（液狀）。試驗結果係如表8所示。 -20- 201116604 [表8] LED硬化性 實施例15 實施例16 _硬化性 〇 〇 [試驗例6] 使用EN 1 45 8 2燃燒離子層析法分別測定實施例15、u 及1 8之能量線硬化型環氧樹脂組成物的鹵素量。測定結聚 係如表9所示。 [表9] 全鹵素量Example 15 Example 16 Example 实施 Example 18 EXA-850CRP _ • _ 45 EPICLON.860 • _ 45 - EXA-8067 45 45 _ _ OXT-211 15 15 15 15 OXT-121 5 5 5 5 OXT-191 5 5 5 5 PI2074 3 3 3 3 DETX-S 0.01 . 0.01 0.01 1-651 _ 1 . - Art-Parl 55 55 55 55 GS-350T EXA-850CRP : Bisphenol A type epoxy resin (made by DIC company: via Distilled refined product) EXA-8067: bisphenol A epoxy resin (manufactured by DIC Corporation: Reactant of EXA-850CRP and bisphenol A) 1-651 : 2,2-dimethoxy-1,2-di Phenylethane (sensitizer made by Ciba) [Test Example 5] The LED curability of the energy ray-curable epoxy resin compositions of Examples 15 and 16 was tested. LED hardenability, in which an energy ray-curable epoxy resin composition is dropped onto an aluminum plate, and an illuminance of 500 mW/cm 2 is used with an LED illuminator having a wavelength of 365 nm (illuminance meter C60 8 0- 1 3 manufactured by Hamamatsu Photonics) ) It is hardened by irradiation for 1 〇 second, and it is confirmed by finger contact. The standard of LED hardenability is: 硬化: hardened (solid), "X" printed: not hardened (liquid). The test results are shown in Table 8. -20- 201116604 [Table 8] LED hardenability Example 15 Example 16 _ hardenability 试验 [Test Example 6] The energy of Examples 15, u and 18 were respectively measured by using EN 1 45 8 2 combustion ion chromatography. The amount of halogen of the wire-cured epoxy resin composition. The measurement of the aggregation is shown in Table 9. [Table 9] Total halogen amount
實施例15 實施例Π 實施侈 鹵素 氯離子 272〇ρηι 729ppm 340pt 溴離子 ND ND NDExample 15 Example 实施 Implementation of an external halogen chloride ion 272〇ρηι 729ppm 340pt bromide ion ND ND ND
[試驗例7] 分別測定實施例1 5、1 7及1 8之能量線硬化型環氧樹月旨 組成物的深部硬化性。紫外線燈之深部硬化性，爲於内@ 5mm Φ之長度5mm之黑管柱中塡充能量線硬化型環氧樹月旨 組成物，再將紫外線照射機（濱松Photonics公司製LC5 ) 由上方以照度5 00mW/cm2 ( 3 6 5 nm )(照度計：濱松 Photonics製 C6080- 1 3 )進行10秒鐘之紫外線照射，測定 硬化後之能量線硬化型環氧樹脂組成物的長度。以LED所 形成之深部硬化性，爲於內徑之長度5mm之黑管柱 中塡充能量線硬化型環氧樹脂組成物，再將波長3 65nm之 -21 - 201116604 LED照射機由上方以照度500mW/cm2 (照度計：濱松 Photonics製 C608 0- 1 3 )進行1 〇秒鐘之紫外線照射，測定 硬化後之能量線硬化型環氧樹脂組成物的長度。測定結果 係如表10所示。 [表 10] 深部硬化性 實施例15 實施例17 實施例18 深部硬化. 性 紫外線燈 2.2mm 2.7mm 1.5mm LED硬化性 3.9mm - [試驗例8] 分別測定實施例15及17之能量線硬化型環氧樹脂組成 物之各別硬度、硬化收縮率、彈性率。硬度（D )爲依JIS K 7215記載使用硬度計測定。硬化收縮率爲依JISK68 3 3記 載之CUP法爲基準測定。Tan <5與儲存彈性率，爲使用SII 公司製EXSTAR6000，依平板拉伸法測定。 [表 1 1] 實施例15 實施娜7 硬度（D) 樣式D 84 84 硬化收縮率 1.6% 1.5% Tan <5 90°C 90°C 儲存彈性率 25〇C 4270 MPa 3000 MPa 儲存彈性率 100°C 180 MPa 120 MPa 本發明之能量線硬化型環氧樹脂組成物，可以高固定 -22- 201116604 準確度迅速地固定例如搭載有LD、光檢測器、透鏡、稜 鏡等光學構件或透鏡等光學構件之光學模組等，而極適合 作爲光學裝置組裝用之接著劑。 -23-[Test Example 7] The deep hardenability of the energy ray-curable epoxy resin composition of Examples 15, 5, and 18 was measured. The deep-hardening property of the ultraviolet lamp is a composition of the energy-hardening type epoxy resin in the black column of 5 mm in length of 5 mm Φ, and then the ultraviolet irradiation machine (LC5 manufactured by Hamamatsu Photonics Co., Ltd.) is The illuminance of 500 00 mW/cm2 (3 6 5 nm) (illuminance meter: C6080-1 3 manufactured by Hamamatsu Photonics) was irradiated with ultraviolet rays for 10 seconds, and the length of the energy-curing epoxy resin composition after curing was measured. The deep-hardening property formed by the LED is an energy-line-hardened epoxy resin composition in a black column with a length of 5 mm in inner diameter, and then a wavelength of 3 65 nm - 21 - 201116604 LED irradiation machine is illuminated from above. 500 mW/cm2 (illuminance meter: C608 0- 1 3 manufactured by Hamamatsu Photonics) was irradiated with ultraviolet rays for 1 sec second, and the length of the energy-curing epoxy resin composition after hardening was measured. The measurement results are shown in Table 10. [Table 10] Deep hardenability Example 15 Example 17 Example 18 Deep hardening. Ultraviolet light 2.2 mm 2.7 mm 1.5 mm LED hardenability 3.9 mm - [Test Example 8] The energy ray hardening of Examples 15 and 17 was measured, respectively. The hardness, hardening shrinkage, and elastic modulus of the epoxy resin composition. The hardness (D) is measured by a hardness meter according to JIS K 7215. The curing shrinkage ratio was measured based on the CUP method described in JIS K68 3 3 . Tan <5 and storage modulus were measured by the plate stretching method using EXSTAR 6000 manufactured by SII Corporation. [Table 1 1] Example 15 Implementation Na 7 Hardness (D) Pattern D 84 84 Hardening shrinkage rate 1.6% 1.5% Tan < 5 90 ° C 90 ° C Storage elastic modulus 25 〇 C 4270 MPa 3000 MPa Storage modulus 100 °C 180 MPa 120 MPa The energy ray-curable epoxy resin composition of the present invention can be rapidly fixed with high accuracy -22-201116604. For example, an optical member such as an LD, a photodetector, a lens, or a cymbal or a lens is mounted. It is an optical module for optical components, and is extremely suitable as an adhesive for assembling optical devices. -twenty three-