200844124 九、發明說明： 【發明所屬之技術領域】 - 本發明係關於具備有透明性、耐熱性，特別可利用於 -光學用途的光硬化性樹脂組成物、及使用此光硬化性樹脂 組成物之硬化物。 【先前技術】 以往，作為光硬化性樹脂者已知有丙烯酸系樹脂。但 是’由於丙烯酸系樹脂係利用自由基聚合反應而硬化，因 而將因线中的氧導致阻礙聚合使表面硬化性變差，更有 指出成為原料的丙烯酸單體之皮膚刺激性強、以及與金 或塑膠間的黏合性#聲卩卩^ —i j〇 r玍差夺問碭。此外，已知在硬化時的體積 收縮較大而不利於精密圖案形成等缺失。 、 力一 yj χΜ] .、以 〜用防離子聚合硬化的光硬化性樹脂組居 产开㈣於諸如：不會因空氣導致表面硬化受阻的 等事項，例如在_、塑= 曰：專化。作為陽離子聚合性物質者可例示如: 號A報專所揭示的雙齡a γ 型環氧_、㈣、苯紛粉酸 合物、㈣環氣環己二T/:肪，缩水甘雜 (3 4-崁气芦口甘 f基3，4 一裱氣環己酯、二 皇厂氧衣己基’基)己二酸酯等脂 氧 本專利特開昭5"2831號公報所 ，，弋日 醚、乙烯醚等非含環氧 . 烯基單體、環狀 ^乙別灿㈣）氧的單體或低聚合體 320016 5 200844124 狀有機物質等。 -般m烯㈣化合物單獨聚合的硬化速度雖盘 -丙烯酸同等級的快速，但卻因鏈轉移反應（chain加如 • reaction)而容易發生著色現象，因而頗難適用於光學領域 等要求透明性的領域。且，乙_系化合物相較於透明性 佳的壤氧約匕合物（雙盼A型環氧樹脂、苯紛祕型環氧樹 脂、甲紛祕型環氧樹脂等含芳香族環氧樹脂等），在高溫 下的重量減少較大，頗難適用於要求耐熱性的領域。 再者，環氧樹脂，特別是羧酸—3,4_環氧環己基甲基 :3:4 :環氧環己酯、二(3,4_環氧環己基甲基)己二酸醋等 脂環型環氧樹脂，就硬化速度的觀點，雖比含芳香族環氧 樹脂獲得明顯的改善，但是卻比丙稀酸系樹脂差，近年隨 對生產性提升的要求而要求更加提升硬化性。 —上述狀況下，國際公開W093/02119號公報便有記載： 糟由在乙烯醚系化合物中添加環狀醚系化合物，並施行Μ 硬^的方法’而獲得以乙_系化合物作為主成分的透明 方去。但疋，該硬化物若更進—步加熱時便被著色， ¥八明性明顯降低’因而有頗難適用於要求透明性與耐 熱性的光導波路等光學領域之問題。 專利文獻1:日本專利特公昭52-14278號公報 專利文獻2 ··日本專利特開平5-239402號公報 專利文獻3 ··日本專利特開昭53-32831號公報 專利文獻4 :國際公開w〇93/〇2119號公報 【發明内容】 320016 6 200844124 勢 -(發明所欲解決之課題） 、本叙明人等就構成光硬化性樹脂組成物的成分特性分 討。結果發現，乙稀醚系化合物雖屬反應性優越 '、刀，但是有耐熱性差、硬化收縮大的問題。另一方面， =氧系，合物雖具有能抑制硬化收縮、透明性優越的優 點，但是因為反應性差，所以有硬化速度較慢，且所庐得 ^化物較硬之問題。此外，氧雜環丁院（oxe tane)系化:物 r雖具有能抑制硬化收'缩、柔軟性優越的優點，但是因氧而 阻礙反應’結果有硬化速度變緩慢的問題。 所以，本發明之目的在於提供透明性與耐熱性均優 越’且光硬化速度快速，並能抑制硬化收縮的光硬化性樹 脂組成物及其硬化物。 (解決課題之手段） 本夯明人等為了能達成上述.目的經深入鑽研的結果發 現，藉由使用依-定比例之乙烯醚系化合物與特定之環^ 鍵系化合物，更使用組合特定之光酸產生劑（ph〇t〇_acid generator) ’便可使耐熱性與透明性優越、且光起始劑的 /合解I*生良好，並明顯改善光硬化速度，頗適用於光學用硬 化物製造的光硬化性樹脂組成物，遂而完成本發明。 即’本發明所提供的光硬化性樹脂組成物，係至少含 有下述（A)至（C): (A )乙細縫糸化合物； (Β) έ有環氧基及/或氧雜環丁燒基的環狀 醚系化合物，·及 320016 7 200844124 (C)以陰離子部分為與PFV同等級或更高電荷密度所 構成的陽離子系光酸產生劑 的光硬化性樹脂組成物，其中，上述成分（B)係含有組成物 全體的6至85重量％。構成上述陽離子系光酸產生劑⑹ 的陰離子部位，例如係以PF" BFp或Ml為宜。本 發明的光硬化性樹脂組成物係可使用於例如光導波路或全 像（H〇logram)的製造。本發明的光硬化性樹脂組成物尚且 在使用奈米壓印技術的領域中適用。 本發明尚提供將上述本發明光硬化性樹脂組成物，利 用光照射而硬化獲得的硬化物。上述硬化物可作為例如光 V波路、全像使用。本發明之硬化物最好使用奈米壓 術進行製造。 發明效果 /根據本發明，因為將乙_系化合物與特定環_系 ::物：一定比例混合使用’且組合特定之光酸產生劑來 因而經先照射便快速地硬化為充分的硬度，將可效 …佳地獲得具有充分耐熱性與透明性，且經抑制硬縮 =狀：定性優越的硬化物。因而’可利用在廣範圍的領 或中，4寸別適於作為光學領域的原料利用。 、 【實施方式】 至⑹本發明的光硬化性樹腊組秦 (A) 乙烯醚系化合物； 鱗糸化合 (B) 含有環氧基及/或氧雜 孔滩咏丁烷基的環狀 320016 8 200844124 m 物；及 (C)以陰離子部分為與ppv同等級或更高電荷密度者 -所構成的陽離子系光酸產生劑。 .[(A)乙烯醚系化合物] 本發明的乙烯醚系化合物（Α)只要具有乙稀基之化合 物就可以，而無特別的限制。乙烯醚系化合物⑷係包括： 例如：烷基乙烯醚類、芳香族乙婦醚類、取代乙烯醚類、 /5-取代乙烯關、及分子内具有2以上官能基的多官能基 化合物（一乙稀_類、三乙烯_類等）等。 上述烧基乙稀關可列舉如：含烴基的單宫能或多官 能之乙烯醚化合物及烯丙醚化合物等。單官能乙烯醚化人 物的具體例，可舉例如：正丁基嫌 乂 σ 丞乙烯醚兴丁基乙稀醚、 弟二丁基乙烯醚、正戊基乙稀醚、異戊基乙烯 基乙烯醚、正己基乙烯醚、異己基乙烯醚、第三己 :庚3乙_、環己基甲基乙_、正庚基乙二醚、 兴庚基乙烯醚、第三庚基乙烯醚、辛基乙烯醚、 驗、十烧基乙烯料㈣乙稀軸 基'對甲苯基、對氯苯基…蔡基、心甲； 有芳香族性烴基的芳香族乙烯醚類等等。 、刀內八 二官能化合物可舉例如··聚乙二醇二 & 己烧二乙稀㈠士環己烧二稀丙醚、“乙上醚、U-環 二乙烯醚、辛烷二乙烯醚'U一辛烷二二乙基裱己基 甲基丙烷二乙烯醚、異山梨醇二乙蝉醚:、二羥 稀醚等二乙烯醚類；雙酚-A二乙烯醚、雙酚白烯二乙 ^ —‘乙稀醚等 320016 9 200844124 芳香族二乙烯醚類等。 一 7刀子内含有三官能基以上乙烯醚的化合物可舉例如·· 三^甲基丙燒三乙_、季戊四醇三乙_等三乙料類 (二官能基物季戊四醇四乙烯料四乙烯 物）；二季戍四醇五乙_等五乙_類（五官能基物）I 季戊四醇六乙烯醚等六乙烯醚類（六官能基物）等。 上述取代乙烯醚類的例子可舉例如·· 基乙烯 基乙醚、α—乙基乙烯基乙醚、苯基乙婦基乙驗等。上 述/5-取代乙稀醚類的例子可舉例如：々_甲基乙烯基乙 趟、/5-甲基乙稀基異丙_、m乙稀基正丁鱗、石_ 甲基乙縣異U基乙烯基第三頂等。 作為乙稀醚系化合物的市售品可取自例如：丸盖石油 化學公司製的2-羥乙基乙烯醚咖)、二乙二醇單：烯醚 (DEGV)、2-羥丁基乙稀醚（ΗβνΕ)、三乙二醇二乙烯醚，· isp 公司製RAPI-OJKE系列、[PYR()LR(N_乙烯基_2吻各唆 酉同）V CAPTM(N-乙烯基-2~己内酸胺）等。 [環狀醚系化合物（B” 本發明的環狀醚系化合物（β)係至少含有環氡兵戎^ 雜環丁烷基中之任一化合物’可使用例如:含有環二: 化合物、及含有氧雜環丁烷基的化合物等（以下，分別^稱 為「環氧系化合物」、「氧雜環丁烷系化合物」的情況: =環，m合物⑻係可以在分子内共同含有環氧基 氧雜環丁烧基的化合物’亦可為環氧系化合物與氧= 烧系化合物的混合物。 ”衣 320016 10 200844124 環氧系化合物是可以使用在分子内含右 的液體或固體。環氧系化合物例如包括 卩上環氧基 脂、雙朌A型環氧樹脂、雙盼F型環氧樹月匕脂環式環氧樹 氧樹脂、具有聯苯基骨架的聯苯基型環‘二雙：S型環 環氧樹脂、具有二環戊二稀骨架的二：二含f裏之 脂、盼㈣型環氧樹脂、甲_ 型¥乳樹 烧型環氧樹脂、三苯基甲燒型環氧樹脂 ί = Μ丙酯等。該等環氧系化合物可以單猶 使用、或组合2種以上使用。其中， ^以早獨 度並達硬化的介人从 ^ f為月匕&升硬化速 ，化的化合物，尤以脂環式環氧樹月旨為佳。 環氧系化合物的具體例可裹存丨· 烧）、幾酸-3,4-環氧環己環氧環己 2 η 4广… 甲基—3，4 —環氧環己醋、 Γ錐Γ—辰广己基—5,5-螺—3,4一環氧)環己燒-間二嗜 J::)、4—乙烯基環氧環己烷、雙(3,4-環氧-6—甲基環己 :甲二：，酸醋、羧酸—3, 4_環氧.甲基環己醋、亞甲基 又(:，二魏己院)、二環戊二稀二環氧化物、乙二醇二 ㈣己基甲基㈤' 乙稀雙（3,4—環氧環己院缓酸 酉曰）、環氧六氫酞酸二辛醋、環氧六氫酞酸二乙 u-丁二醇二縮水甘油_ 基己Ιθ 、 _ _ 1，13已一％ —縮水甘油醚、甘 油的·**"、句S 水甘油 2^、二 il«< ® # -r- Α , _ , —匕甲基丙烧的三縮水甘油_、山梨 糖醇的四縮水甘㈣、二季戍四醇的六縮水甘油驗、聚乙 一醇的二縮水甘㈣H醇的二縮水甘油在丙二 醇、甘油等脂肪族多元醇中，加成1種或2種以上環氧烷 320016 11 200844124 t 而獲得的聚⑽多元醇之聚縮水甘油或諸如 鏈二元酸脂肪族高級醇 .曰方族長 苴必々-， 旧^，田越、或紛、甲酚、丁 在該等加成環氧炫而獲得的㈣醇之單增JC .甘油驗；或如：高級脂肪酸的環氧丙酯、環氧：=水 環氧硬脂酸辛酷、環氧硬_丁 =大：油、 乳乙烷、裱氧丙烷、氧化環己烯、氧介 本乙烯、甲基縮水甘油醚、 甘、、由醚、贫U 丁基鈿水甘油醚、烯丙基縮水 η始 甘油_、乙二醇環氧丙基苯基驗、乙- 醇卞基縮水甘油醚、二Γ _ 。— @e 一 一虱丙基四氫吡啶醚、甲基 丙…氧丙酯、醋酸環氧丙酯、曰本專利特門； ，，該專可以單獨使用、或組合2種以上使 =亦可使用將環氧化合物的部分（或全部）氫原子以氣取 氧雜環丁燒系化合物係具有：較環氧基多1個碳數的 3個飽和碳原子、以及i個氧原子所構成之四員環氧= 丁烷基的化合物。特別是具有氧雜環丁烷基，且不具有= 半矽氧烷(SilSe_i〇xane)構造的化合物，因為能控制： 組成物的黏度而容易注入模框中，且能對硬化物賦予黏人 性、耐藥性故適於使用。氧雜環丁烧系化合物只要月处藉2 陽離子系光酸產生劑（C)進行硬化就可以，而無特別的曰限 制’可以使用慣用分子量的具有以往習知分子構造的化合 物。 ° 氧雜環丁烷系化合物的具體例可舉例如：3〜乙基一3一 320016 12 200844124 I基甲基氧雜環丁炫、3-烯丙氧基甲基_3_乙基氧雜環丁 烷、（3一乙基―3 —氧雜環丁烷基甲氧基）甲基苯、4-氟-[卜以一 乙基-3-氧雜環丁烷基甲氧基）曱基]苯、4_曱氧基_[卜（3一 乙基-3-氧雜環丁烷基甲氧基）曱基]苯、3_乙基一 3_(苯氧基 甲基）氧雜環丁烧、異丁氧基甲基（3_乙基-3-氧雜環丁烧^ 甲基）醚、異萡氧基乙基（3-乙基-3-氧雜環丁烷基甲基） 醚、異萡基（3-乙基-3-氧雜環丁烷基甲基）醚、2_乙基己基 (3-乙基-3-氧雜環丁烷基甲基）醚、乙基二乙二醇（3_乙= -3-氧雜環丁烷基甲基）醚、二環戊二烯（3_乙基—3_氧雜ς 丁烷基甲基）醚、二環戊烯氧基乙基（3_乙基_3_氧雜環丁烷 基甲基）醚、二環戊烯基乙基（3-乙基-3-氧雜環丁烷基甲基） 醚、四氫糠基（3-乙基-3-氧雜環丁烷基甲基）醚、四溴苯基 (3乙基3氧雜環丁燒基甲基）醚、[四溴苯氧基乙基（3一 1基二3-氧雜環丁烷基甲基）醚、三溴苯基（3-乙基-3-氧雜 環丁烧基甲基）縫、2-三演苯氧基乙基（3_乙基_3_氧雜環丁 烧基曱棊）醚、2-羥乙基（3一乙基一3_氧雜環丁烷基甲基） 醚、2-羥丙基（3-乙基_3 —氧雜環丁烷基甲基）醚、丁氧基乙 基（3-乙基-3-氧雜環丁烷基甲基）醚、五氯苯基（3_乙基一3_ 氧雜環丁燒基甲基-、五溴苯基（3_乙基_3_氧雜環丁院基 甲基）醚、萡基（3-乙基_3 一氧雜環丁烧基甲基）醚、雙 甲基-3-氧雜環丁烷基甲氧基)甲基]醚、3, 7_雙(3_氧雜環 丁烷基）5-b-壬烷、；[，4_雙[(3_乙基_3_氧雜環丁烷基甲 氧基）甲基]苯、乙二醇雙（3-乙基-3-氧雜環丁烷基甲基） 謎、丁—醇雙（3_乙基_3_氧雜環丁烧基甲基）峻、己 320016 13 200844124 ， (3-乙基-3-氧雜環丁烧基甲基）醚、二環戊烯基雙（3—乙基 - 3-氧雜環丁烷基甲基）醚、三乙二醇雙（3-乙基—3-氧雜環 丁烷基甲基）醚、四乙二醇雙（3-乙基-3-氧雜環丁烷基甲基） -醚、聚乙二醇雙（3-乙基-3-氧雜環丁烷基甲基）醚、E0改 質雙酴A雙（3 -乙基-3-氧雜環丁烧基甲基）_、p〇改質雙 酚A雙（3-乙基-3-氧雜環丁烷基甲基）醚、E〇改質氫化雙 盼A雙（3-乙基-3-氧雜環丁烷基甲基）醚、p〇改質氫化雙 酚A雙（3-乙基-3-氧雜環丁烷基甲基）醚、E〇改質雙酚F 雙（3乙基-3-氧雜％ 丁燒基甲基）鍵、三經甲基丙烧夫（3 一 乙基-3-氧雜環丁烷基甲基）醚、季戊四醇參乙基—3一氧 雜環丁烷基曱基）醚、季戊四醇肆（3—乙基—3 一氧雜環丁烷基 甲基）醚、二季戊四醇陸（3_乙基_3_氧雜環丁烷基甲^ 醚、二季戊四醇伍（3_乙基-3-氧雜環丁烷基甲基）醚、二1 季 戊四醇肆（3_乙基_3_氧雜環丁烷基曱基）醚、己内酯改質二 季戊四醇陸（3_乙基_3_氧雜環丁烷基曱基）醚、二（三羥甲 基)*丙烷肆（3_乙基_3_氧雜環丁烷基曱基）醚、雙氧雜^丁 烧碳酸醋、雙氧雜環丁烧己二酸醋、雙氧雜環丁燒對苯二 甲酸酯、環己烷二羧酸雙氧雜環丁烷酯、3_(3_甲基_ = 才准丁燒基曱氧基）丙基三乙氧基石夕烧、3_(3_乙基—3 6-16804號公報所記載的氧雜環丁烷矽銅等。 丁 ^化^勿可單獨使用、或組合2種以上使用等魏架 氧‘ ％ 丁烷系化合物的市售品可自如：人赤 公司製的3-乙基-3 -（2一乙其甲其、果亞口成（股） 以Q基己虱基曱基）氧雜環丁烷 320016 14 200844124 • (0XT-212)、3-乙基-3-羥基曱基氧雜環丁烷（〇χΤ-1〇1)、 1，4-雙-{[(3-乙基-3-氧雜環丁烷基）甲氧基]曱基}苯 (0ΧΤ-121)及氧雜環丁烷基倍半矽氧烷（〇X-Sq)等。 ’ 本發明中，環狀醚系化合物（B)的含有量係組成物全體 的6至85重量％，最好20至80%重量。若環狀醚系化合物 (B)的含有量未滿6重量％時，即使剛硬化後是呈透明硬化 物，但是之後若更進一步加熱（例如12(rc程度）時，便會 『被著色，導致透明性明顯降低。反之，當含有量超過& k重量％時，當利用陽離子系光酸產生劑（c)的作 時，硬化速度變得非常慢並無法實用。本發明的 樹脂組成物，因為依上述範圍的量使用環狀醚系化合物 (B)，因而可發揮極高的耐熱性。所以，將有利於使用為特 別要求高透明性的領域（尤其是光導波路等光學領域）的材 料。 陽離子系光酸產生劑（C)係由陽離子部位與陰離子部 位構成。本發明特徵之一，係上述陰離子部位為=電荷密 度與PFr同等級或較高的電荷密度所構成。因為本發明的 陽離子系光酸產生劑（C)因係由上述陰離子部位構成，因而 溶解性極良好，可發揮優越的陽離子硬化性’可明顯提升 硬化速度，且可達提供透明性極優越的硬化物效果。、若由 電荷密度較低於PFr的陰離子部位構成時，雖反應性、陽 2子系光酸產生劑（C〉的溶解性將提升，但是因為耐著色性 會降低’因而並不利於要求透明性的領域。此處’本發明 所謂「電荷密度」係採用J.V.Crivelio and j.H w l: 320016 15 200844124 4 .Macromolecules’ 13〇7, Vol.10, 1 997 所記载的定義。 為上述「與pf6-同等級或較高的電荷密度」之陰離子部分 -係可利用含有氟原子的高親核性陰離子，具體例如： • BFr、及 CFsSOr等。 6 作為陰離子部位由PFr構成的陽離子系光酸產生劑（ 之市售品，係可取自如：「Irgacure25〇」（汽巴特殊化二公 司製）、「Uvacurel591」（SCITEC 公司製）等。 “ 構成陽離子系光酸產生劑（C)的陽離子部位，可舉例如 依下述式（1)至（4)所示陽離子部位等。 R!l 一 R21^ 一 R3 Rt — i 一 R21_S 一 “ 印 R4 R5 R5 t ⑴ ⑵ R1 — I — p2 (4) R1 S — R2— S -一 R3[Technical Field] The present invention relates to a photocurable resin composition having transparency and heat resistance, particularly useful for optical use, and a photocurable resin composition using the same Hardened matter. [Prior Art] Conventionally, an acrylic resin has been known as a photocurable resin. However, since the acrylic resin is cured by a radical polymerization reaction, the surface hardenability is deteriorated due to the inhibition of polymerization by oxygen in the wire, and it is pointed out that the acrylic monomer which is a raw material has strong skin irritation and gold. Or the adhesion between the plastics #声卩卩^ — ij〇r玍 玍 砀. Further, it is known that the volume shrinkage at the time of hardening is large, which is disadvantageous for the lack of precision pattern formation or the like. , force yj χΜ], with ~ anti-ionic polymerization hardened photo-curable resin inhabited (four) such as: will not be caused by air-induced surface hardening, such as in _, plastic = 曰: specialization . Examples of the cationically polymerizable substance include, for example, a double-aged a γ-type epoxy _, (4), a benzene powder acid compound, (4) a ring gas ring hexane T/: fat, and a water-reducing sweetness disclosed in No. A newspaper. 3 4-Nanqi Rukou Gan f-based 3,4-helium cyclohexyl ester, Erhuang plant oxygenated hexyl 'dialkyl adipate and other lipooxylates, this patent special open 5 " 2831, 弋Monomers or oligomers other than epoxy, vinyl ether, etc., which do not contain an epoxy group, an ethylenic monomer, a cyclic group, or an oligomer, 320016 5 200844124, an organic substance, and the like. The curing rate of the monomene (tetra) compound alone is faster than that of the disk-acrylic acid, but it is easy to be colored due to the chain transfer reaction (chain addition reaction), so it is difficult to apply transparency in the optical field. field of. Moreover, the B-based compound has an aromatic epoxy resin such as a double-awaiting A-type epoxy resin, a benzene-clear epoxy resin, and a secret-type epoxy resin, compared with a transparent oxygen-based conjugate. Etc.), the weight loss at high temperatures is large, and it is difficult to apply to areas requiring heat resistance. Further, an epoxy resin, particularly a carboxylic acid, 3,4-epoxycyclohexylmethyl: 3:4: epoxycyclohexyl ester, bis(3,4-epoxycyclohexylmethyl) adipate vinegar Epoxy-type epoxy resin, although it has a significant improvement over the aromatic-containing epoxy resin, it is inferior to the acrylic acid-based resin. In recent years, it has been required to improve hardening with the demand for productivity improvement. Sex. - In the above-mentioned case, the publication of the publication No. WO 093/02119 discloses that the method of adding a cyclic ether compound to a vinyl ether compound and performing a method of hydrazine is used to obtain a compound containing a B-based compound as a main component. Go transparent. However, if the cured product is colored more when it is heated in a stepwise manner, it is markedly lowered, and thus it is difficult to apply it to an optical field such as an optical waveguide which requires transparency and heat resistance. [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. 93 〇 119 119 119 016 016 016 016 016 016 016 016 016 016 016 016 016 016 016 016 016 016 016 016 016 016 016 016 016 016 016 016 016 016 016 016 016 016 016 016 016 016 016 016 016 016 016 016. As a result, it was found that although the ethyl ether compound is excellent in reactivity, the knife has a problem of poor heat resistance and large hardening shrinkage. On the other hand, the oxygen-based compound has an advantage of being able to suppress hardening shrinkage and superior transparency. However, since the reactivity is poor, there is a problem that the curing rate is slow and the obtained compound is hard. Further, the oxe tane system has the advantage that it can suppress the hardening and shrinkage, and the flexibility is excellent. However, the reaction is inhibited by oxygen. As a result, the curing rate becomes slow. Therefore, an object of the present invention is to provide a photocurable resin composition which is excellent in both transparency and heat resistance and which has a fast photocuring speed and which can suppress hardening shrinkage and a cured product thereof. (Means for Solving the Problem) In order to achieve the above objectives, Benjamin and others have found that by using a specific ratio of a vinyl ether compound and a specific ring-based compound, it is also possible to use a combination. The photoacid generator (ph〇t〇_acid generator) can make the heat resistance and transparency superior, and the photoinitiator/combination solution I* is good, and the photohardening speed is obviously improved, which is quite suitable for optical use. The photocurable resin composition produced by the cured product is completed by the present invention. That is, the photocurable resin composition provided by the present invention contains at least the following (A) to (C): (A) an ethylidene compound; (Β) an epoxy group and/or an oxetane a halogen-based cyclic ether compound, and 320016 7 200844124 (C) a photocurable resin composition containing a cationic photoacid generator having an anion moiety and a charge density of PFV or higher, wherein Component (B) contains 6 to 85% by weight of the entire composition. The anion site constituting the above-mentioned cationic photoacid generator (6) is preferably PF" BFp or Ml, for example. The photocurable resin composition of the present invention can be used, for example, for the production of optical waveguides or holograms. The photocurable resin composition of the present invention is also applicable to the field of using nanoimprint technology. Further, the present invention provides a cured product obtained by curing the photocurable resin composition of the present invention by light irradiation. The cured product can be used, for example, as a light V-wave path or a full image. The cured product of the present invention is preferably produced by using a nano press. Advantageous Effects of Invention According to the present invention, since a B-based compound is mixed with a specific ring system: a substance in a certain ratio and combined with a specific photoacid generator, it is rapidly hardened to a sufficient hardness by first irradiation. It is effective... It is good to obtain a cured product which has sufficient heat resistance and transparency, and which is suppressed in hardness and shape: qualitatively superior. Therefore, it can be utilized in a wide range of fields, and 4 inches is suitable for use as a raw material in the field of optics. [Embodiment] To (6) the photocurable wax group Qin (A) vinyl ether compound of the present invention; scaly compound (B) ring 320016 containing an epoxy group and/or an oxygen hole beach 8 200844124 m; and (C) a cationic photoacid generator composed of an anion moiety which is of the same class or higher charge density as ppv. [(A) Vinyl ether-based compound] The vinyl ether-based compound (oxime) of the present invention may be a compound having an ethylene group, and is not particularly limited. The vinyl ether compound (4) includes, for example, alkyl vinyl ethers, aromatic ethyl ethers, substituted vinyl ethers, /5-substituted ethylene, and polyfunctional compounds having two or more functional groups in the molecule (1) Ethylene _ class, triethylene _ class, etc.). The above-mentioned alkyl group can be exemplified by a mono- or polyfunctional vinyl ether compound and an allyl ether compound containing a hydrocarbon group. Specific examples of the monofunctional vinyl etherified person include, for example, n-butyl 乂 乂 丞 丞 vinyl ether butyl butyl ether, dibutyl vinyl ether, n-pentyl ethyl ether, isoamyl vinyl ethylene Ether, n-hexyl vinyl ether, isohexyl vinyl ether, third hexanyl: heptane 3 ethyl, cyclohexylmethylethyl _, n-heptyl ethylene diether, decyl vinyl ether, third heptyl vinyl ether, octyl Vinyl ether, test, decalinated vinyl (IV) Ethyl-based p-tolyl, p-chlorophenyl ... Tsai, manicure; aromatic vinyl ethers with aromatic hydrocarbon groups, and the like. In the knife, the octa-functional compound may, for example, be polyethylene glycol di-amp; hexane-diethyl ether (1) singapore di-dipropyl ether, "ethyl ether, U-cyclodivinyl ether, octane diethylene" Ether 'U-octane di-diethylhexylmethyl propane divinyl ether, isosorbide diethyl ether: divinyl ethers such as dihydroxy ether; bisphenol-A divinyl ether, bisphenol leukoene Diethyl 2---Ethyl ether, etc. 320016 9 200844124 Aromatic divinyl ethers, etc. A compound containing a trifunctional or higher vinyl ether in a 7-knife can be exemplified by, for example, trimethyl propyl triacetate and pentaerythritol.乙_等三乙类(difunctional base pentaerythritol tetraethylene tetravinyl); diquaternary quinonetetraol pentylene _ et al pentaerythron (pentafunctional base) I pentaerythritol hexavinyl ether and other hexavinyl ether ( Examples of the above-mentioned substituted vinyl ethers include, for example, vinyl ethyl ether, α-ethyl vinyl ethyl ether, phenylethyl ethyl phthalate, etc. The above 5-substituted vinyl ethers Examples include, for example, 々_methylvinylacetamidine, /5-methylethenyl isopropyl hydrazine, m ethylidene butyl sulphate, and stone _ methyl ethane A sub-U-based vinyl group, the third top, etc. A commercially available product of an ethyl ether-based compound can be taken, for example, from 2-hydroxyethyl vinyl ether (available from Pellet Petrochemical Co., Ltd.), diethylene glycol mono-alkene Ether (DEGV), 2-hydroxybutyl ether ether (ΗβνΕ), triethylene glycol divinyl ether, · RAPI-OJKE series by isp company, [PYR() LR (N_vinyl-2 kiss each Same as) V CAPTM (N-vinyl-2~caprolactam), etc. [Cyclic ether compound (B) The cyclic ether compound (β) of the present invention contains at least a ring 氡 戎 ^ Heterocyclobutane For example, a compound containing a ring: a compound and a compound containing an oxetanyl group can be used (hereinafter, referred to as "epoxy compound" and "oxetane compound", respectively. The case: = ring, m compound (8) is a compound which can contain an epoxy oxetan group in the molecule, and can also be a mixture of an epoxy compound and an oxygen = a fire compound." 200844124 Epoxy compounds are liquids or solids that can be used in the molecule to contain the right. Epoxy compounds include, for example, anthracene epoxy, double A type epoxy resin, double-presence F-type epoxy tree epoxide ring epoxy resin, biphenyl type ring with biphenyl skeleton 'double pair: S-ring epoxy resin, with dicyclopentane Two of the dilute skeletons: two fats containing f, expectant (four) epoxy resin, a type _ milk tree-fired epoxy resin, triphenyl methacrylate type epoxy resin ί = propyl propyl ester, etc. The epoxy compound may be used singly or in combination of two or more kinds. Among them, the compound which is hardened by the early age and the hardening of the compound is a compound of the ruthenium. Epoxy resin is preferred. Specific examples of epoxy compounds can be coated with bismuth·burning, and some acids-3,4-epoxycyclohexyl epoxycyclohexane 2 η 4 wide... methyl-3,4 — Epoxy cyclohexan vinegar, Γ cone Γ 辰 广 己 — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — (3,4-epoxy-6-methylcyclohexyl: methyl two:, acid vinegar, carboxylic acid - 3, 4_epoxy. methylcyclohexanoic acid, methylene again (:, Weiwei) , dicyclopentadienyl diepoxide, ethylene glycol di(tetra)hexylmethyl (5)' ethylene double (3,4-epoxy ring缓 缓 酉曰 酉曰 、 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 _ 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 , glycerol · ** ", sentence S glycerol 2 ^, two il « < ® # -r- Α , _ , — 匕 methyl propyl triglyceride _, sorbitol tetraglycan (four) , quaternary glycerol test of diquaternic quinone alcohol, diglycidyl diglycol of diethylene glycol (tetra) H alcohol, in an aliphatic polyol such as propylene glycol or glycerin, one or more alkylene oxides are added. 320016 11 200844124 t And the obtained poly(10) polyhydric polyglycidol or such as a chain dibasic acid aliphatic higher alcohol. 曰 族 苴 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , Hundred and obtained (4) alcohol alone increase JC. glycerol test; or such as: high-fat fatty acid propyl acrylate, epoxy: = water epoxy stearic acid xinkuo, epoxy hard _ ding = large: oil, milk ethane , propylene oxide, cyclohexene oxide, oxygen-based ethylene, methyl glycidyl ether, glycerol, ether, U butyl hydrated glycerol ether, allyl condensed η glycerol Ethylene glycol phenyl glycidyl inspection, B - Bian alcohol glycidyl ether, di Γ _. — @e 虱 propyl propyl tetrahydropyridine ether, methyl propyl propyl propyl acetate, glycidyl acetate, 曰 专利 专利 ; ; ; ; , , , , , , , , , , , , , , , , , , , , , , , , , The oxetane compound obtained by using a part (or all) of hydrogen atoms of the epoxy compound is composed of three saturated carbon atoms having one carbon number more than the epoxy group, and one oxygen atom. Four member epoxy = butane alkyl compound. In particular, a compound having an oxetanyl group and having no structure of =SilSe_i〇xane can be controlled by: the viscosity of the composition is easily injected into the mold frame, and the adhesion to the hardened material can be imparted. It is suitable for use because of its resistance. The oxetane-based compound may be cured by a two-cationic photoacid generator (C) at a monthly basis, and is not particularly limited. A conventional molecular structure having a conventional molecular structure can be used. Specific examples of the oxetane-based compound include, for example, 3 to ethyl- 3,320,016, 12, 2008,144,124, I-methyl oxetane, 3-allyloxymethyl_3-ethyloxa Cyclobutane, (3-ethyl-3-oxo-butanealkylmethoxy)methylbenzene, 4-fluoro-[b-ethyl-3-oxetanylmethoxy)anthracene Benzene, 4-methoxycarbonyl _[Bu (3-ethyl-3-oxetanylmethoxy)indolyl]benzene, 3-ethyl-1,3-(phenoxymethyl)oxa Cyclobutane, isobutoxymethyl (3_ethyl-3-oxetan) methyl, isomethoxyethyl (3-ethyl-3-oxetanyl) Ether, isodecyl (3-ethyl-3-oxetanylmethyl)ether, 2-ethylhexyl (3-ethyl-3-oxetanylmethyl)ether, Ethylene diethylene glycol (3_B = -3-oxetanylmethyl) ether, dicyclopentadiene (3_ethyl-3-oxaxanthylmethyl) ether, two Cyclopentyloxyethyl (3_ethyl_3_oxetanylmethyl)ether, dicyclopentenylethyl (3-ethyl-3-oxetanylmethyl) Ether, tetrahydroindenyl (3-ethyl-3-oxetanylmethyl) Tetrabromophenyl (3 ethyl 3 oxetanyl methyl) ether, [tetrabromophenoxyethyl (3 - 1 bis 2-oxetanylmethyl) ether, tribromo Phenyl (3-ethyl-3-oxetanylmethyl) sulcate, 2-tris-phenoxyethyl (3-ethyl-3- oxacyclobutane oxime) ether, 2 -Hydroxyethyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxypropyl (3-ethyl-3-cyclobutanemethyl)ether, butoxy Ethyl (3-ethyl-3-oxetanylmethyl)ether, pentachlorophenyl (3-ethyl-3-oxaxenylmethyl), pentabromophenyl (3_B) _3_oxetanyl methyl)ether, fluorenyl (3-ethyl-3-benzoic acid methyl)ether, bismethyl-3-oxetanylmethoxy Methyl]ether, 3,7-bis(3-oxetanyl)5-b-decane, [,4_bis[(3_ethyl_3_oxetanyl) Methoxy)methyl]benzene, ethylene glycol bis(3-ethyl-3-oxetanylmethyl) mystery, butanol bis(3_ethyl_3_oxetanyl) Methyl) Jun, hexane 320016 13 200844124 , (3-ethyl-3-oxetanylmethyl)ether, dicyclopentenyl (3-ethyl-3-oxetanylmethyl)ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, tetraethylene glycol bis (3) -ethyl-3-oxetanylmethyl)-ether, polyethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, E0 modified biguanide A double 3-ethyl-3-oxetanylmethyl)_, p〇 modified bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether, E〇 modified hydrogenation Double-A (3-ethyl-3-oxetanylmethyl)ether, p〇 modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether , E 〇 modified bisphenol F bis (3 ethyl-3-oxa% butyl alkyl) bond, trimethyl propyl ketone (3-ethyl-3-oxetanylmethyl) Ether, pentaerythritol phenylethyl-3-oxetanyl fluorenyl ether, pentaerythritol bismuth (3-ethyl-3-oxetanylmethyl)ether, dipentaerythritol urethane (3-ethyl) _3_oxetanyl methyl ether, dipentaerythritol (3_ethyl-3-oxetanylmethyl)ether, dipentaerythritol quinone (3_ethyl_3_oxocyclohexane) Butyryl decyl ether, caprolactone Modified dipentaerythritol tert (3_ethyl_3_oxetanyl decyl) ether, bis(trimethylol)*propane oxime (3_ethyl_3_oxetanyl fluorenyl) Ether, dioxo-butane-burned carbonated vinegar, dioxane-burned adipic acid vinegar, dioxetane terephthalate, cyclohexanedicarboxylic acid dioxetane, 3_(3_Methyl_= 才 丁 曱 曱 ) ) ) ) ) ) ) 三 氧 氧 、 、 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧. Ding^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ It is a hydroxy oxetane of a ruthenium ketone. The oxetane 320016 14 200844124 • (0XT-212), 3-ethyl-3-hydroxyindenyl oxetane (〇 χΤ-1〇1), 1,4-bis-{[(3-ethyl-3-oxetanyl)methoxy]indolyl}benzene (0ΧΤ-121) and oxetane Sesquiterpene oxide (〇X-Sq) and the like. In the present invention, the content of the cyclic ether compound (B) is from 6 to 85% by weight, preferably from 20 to 80% by weight based on the total of the composition. When the content of the cyclic ether compound (B) is less than 6% by weight, even if it is hardened, it is a transparent cured product, but if it is further heated (for example, at 12 (rc level), it will be colored. The transparency is remarkably lowered. Conversely, when the content exceeds & k% by weight, when the cationic photoacid generator (c) is used, the curing rate becomes very slow and is not practical. The resin composition of the present invention Since the cyclic ether compound (B) is used in an amount within the above range, it is possible to exhibit extremely high heat resistance. Therefore, it is advantageous to use a field in which transparency is particularly required (especially in an optical field such as an optical waveguide). The cationic photoacid generator (C) is composed of a cationic moiety and an anionic moiety. One of the features of the present invention is that the anionic moiety is a charge density equal to or higher than the PFr. Since the cationic photoacid generator (C) is composed of the anion site described above, it has excellent solubility and can exhibit excellent cationic hardenability, which can significantly improve the curing rate. Moreover, it is possible to provide a cured product having excellent transparency. When the charge density is lower than that of the anion site of PFr, the solubility of the reactive, cationic 2 photoacid generator (C> will increase, but Since the coloring resistance is lowered, it is not advantageous for the field of transparency. Here, the so-called "charge density" of the present invention is JVCrivelio and jH wl: 320016 15 200844124 4 .Macromolecules' 13〇7, Vol.10, The definition described in 1 997. The above-mentioned "anionic moiety of the same level or higher charge density as pf6-" can utilize a highly nucleophilic anion containing a fluorine atom, and specific examples thereof include: BFr, CFsSOr, and the like. (6) A commercially available product of a cation-based photoacid generator consisting of PFr ("Irgacure 25" (manufactured by Ciba Specialty Chemicals Co., Ltd.), "Uvacurel 591" (manufactured by SCITEC Co., Ltd.), etc. The cation site of the cationic photoacid generator (C) may, for example, be a cation moiety represented by the following formulas (1) to (4), etc. R!l-R21^-R3 Rt-i-R21_S A "R4" R5 R5 t (1) (2) R1 — I — p2 (4) R1 S — R2 — S — A R3
I R4I R4
⑶ (式中，R1至R6係指相同或互異的苯基或萘基，·只2„與只3,,係 指相同或互異的伸苯基或伸萘基）。 式（1)至（4)中，R至R的苯基或萘基、及R2"盘R3"的 伸苯减伸萘基，亦可其巾—個錢數賴原子被取代基 所取代。此種取代基可舉例如：甲基、乙基、丙基、里丙 基、丁基、異丁基、第三丁基、戊基、己基、庚基、辛基、 壬基夭基+ ^基、十二炫基等直鏈狀或分枝鍵狀& 至Ci2燒基，·甲氧基、己盡其 # 丞乙虱基丙虱基、戊氧基等直鏈狀或 320016 16 200844124 •分枝鍵狀Cl至Cu烷氧基；鹵原子；-〇H基；-C00H基、及 -C00-直鏈狀或分枝鏈狀Cl至Cl2烷酯基等。 . 上述陽離子部位的具體例如依下述式（2-1)、（3-1)、 •及（4-1)所示陽離子部位：(3) (wherein R1 to R6 are the same or mutually different phenyl or naphthyl groups, and only 2 to 3, which means the same or different phenyl or naphthyl). In (4), the phenyl or naphthyl group of R to R, and the benzene-extended naphthyl group of R2"R3" may also be substituted by a substituent of a ruthenium atom. For example, methyl, ethyl, propyl, propyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, decyl fluorenyl + ^, twelve A syllabic group such as a linear or branched bond & to a Ci2 alkyl group, a methoxy group, a hexyl group, a pentyloxy group, etc. or a linear chain or 320016 16 200844124 • a branching key Cl to Cu alkoxy; halogen atom; -〇H group; -C00H group, and -C00-linear or branched chain Cl to Cl2 alkyl ester group, etc. Cation sites of formula (2-1), (3-1), • and (4-1):
((式中，R至R16係指相同或互異，表示選自氫原子、直鏈 狀或分枝鏈狀C!至Cu烷基、直鏈狀或分枝鏈狀Ci至eh 烷氧基、鹵原子、-0H基、—C00H基、—⑶〇一基、及直鏈狀 或分枝鏈狀匕至匕2烷酯基所構成群組中至少丨種的基） 上述R至R的直鏈狀或分枝鏈狀匕至Cu烷基，只要調 配入以上式（2-1)或（3-丨）所示陽離子部位所構成的非離子 性光酸產生劑之光硬化性組成物，便可獲得具有吸收波長 例如300匪以上光（最好波長3〇〇至4〇〇nm光）之性質的極 優越硬化物。此外，以上式（4-υ所示陽離子部位所構成的 320016 17 200844124 陽離子系光酸產生劑，當調配入光硬化性組成物中 士 可與各種基質（乙稀醚系化合物）良好地溶解，可發士 優越的硬化性，且硬化物的著色性等將極優越。X 寸別 本發明的陽離子系光酸產生劑（c)特別以上式（ί)至 (4)[最好式（2-1)至（4-1)]所示陽離子部位、與pF「、BF至 及CF3S〇4_中任一陰離子部位所構成者為佳。 4 ί 陽離子系光酸產生劑（C)的使用量，例如相對於成分（a) 與成为（B)總置1 〇〇重量份，下限是〇· 〇5重量份左右，上 限是20重量份左纟。若未滿0.05重量份時’會有光陽離 子聚合未充分進行、或反應變為過慢的傾向；反之，若超 過20重量份時，會有反應變為過快導致作業性降低、反應 呈不均的情況。最好的下限係〇·!重量份左右，最好的^ 限係10重量份左右。 本發明的光硬化性樹脂組成物，依照使用方法亦可含 有如：光增感劑、樹脂、密接性提升劑、補強劑、軟化劑、 可塑劑、黏度調整劑、溶劑等以往習知的各種添加劑。 上述光增感劑係屬於可更加提升上述陽離子系光酸產 生劑（C)的效率，可更加促進上述光陽離子聚合性化合物的 光陽離子聚合者。此種光增感劑並無特別的限制，例如可 使用··幾化合物、有機硫化合物、過硫化物、氧化還原系 化合物、偶氮化合物、重氮化合物、鹵化合物、光還原性 色素等。光增感劑的具體例如··苯偶姻甲基醚、苯偶姻異 丙醚等苯偶姻衍生物；二苯基酮、2, 4-二氯二苯基酮、鄰 苯甲酿基苯甲酸曱酯、4, 4,-雙（二甲基胺基）二苯基酮等二 18 320016 200844124 苯基酮衍生物；2-氯唭喵而 生物；2-氯惠酉昆、2V夷二 。塞嘲峰塞嘴綱衍 二丁氧基蒽等蒽街生物等t'r衍生物；二丙氧基葱、 亦可併用2種以上。、光增感劑係可單獨使用、 本發明的光硬化性樹脂 以往習知裝置施行授拌、、3入係將上述構成成分使用 光硬化性樹Μ組成物的夢：：：：：：製得到。本發明之 施，所獲得組成物最於^在將光阻隔的狀態下實 之光硬化性樹腊組成物除了可利用為塗料、塗 成开/材料、墨用油墨等油墨、黏合劑、光阻劑、製版材料t 性域4“圍領域中。特別是因為本發明之光硬化 梦月曰組成物可形成具耐熱性且透明性優越的硬化物，因 圣可作為光導波路、全像等光學料使用。本發明之光 =化性樹颜成物尚可適用為㈣壓印（刪。丨_丨n t)技 術所使用的樹脂組成物。 ）技 曝光，，可使用如：水銀燈、氣燈、碳弧燈、金屬齒 二燈、太陽光、電子束、雷射光等照射源。硬化控制係可 精由適當设定曝光時所使用的光強度、溫度、時間等，並 等、擇光更化性組成物的構成成分（硬化控制劑的添加 :、）來貫施。其中，最好採取利用曝光時與曝光後（後烘烤） 本！X明的硬化物係使用上述本發明之光硬化性組 ,、二利用如喷墨法、微影法（Lithography)等慣用方法， 形成所需的影像或形狀之後，再利用曝光便可製得。 320016 19 200844124 身 • 的溫度控制而進行硬化控制之方法。 本發明的光硬化性組成物亦可在經曝光後，再利用例 .如50至2〇〇°C左右的溫度施行熱處理而進行硬化。此種曝 .光後的熱處理對：厚膜硬化、光未照射部分的硬化、以及 充填劑已硬化的樹脂組成物之硬化會有效。 本發明的硬化物係可利用於：塗料、塗敷材料、喷墨 用油墨等油墨、黏合劑、光阻劑、製版材料、光導波路、 全像、成形材料、密封材料等各種用途，就透明性極優越 的觀點而言，將極有效作為光導波路、奈米壓印、或全像 等的光學材料使用。 本發明的透明性係可藉由波長彻i85〇nm之光評估 牙透/。根據本發明，將可獲得上述穿透率例如為以 上（取好801以上，尤卩85%以上為佳）的優越透明性硬化 物。透明性係可利用環狀㈣化合物⑻的種類與 絲產生㈣）的陰離子部位之構造等來進行適 光日之「耐熱性」係指#經利用樹脂組成物的 =:形成硬化物之後’即便再施行熱處理的情況，硬 π越乃I維持透明性的意思。因為本發明硬化物的财熱性 用於經硬化後仍需更進一步加熱， 光照射樹组成物而形成的硬化物:二 置此而所獲得經加“ ：120c-度下，放 之光進P、#玄…、後的硬化物，利用波長400至850nm 仃牙料敎㈣法。㈣本㈣的光魏性樹月旨 320016 20 200844124 ‘組成物，經耐熱試驗後的上述波長範圍之光穿透率將可保 持在84%以上，可形成耐熱性優越的硬化物。所以，對要 、求耐熱性與高度透明性的光學用途，特別是光導波路用途 .將極有用。耐熱性是可藉由適當選擇：環狀醚系化合物（B) 的種類與量、及陽離子系光酸產生劑（〇的陰離子部位之構 造等而進行調整。 稱 丹者 、 尽贫明的光硬化性樹脂組成物係利用光照射便 可極迅速地硬化。因而，可達到提升硬化物生產性的效果C 硬化速度係可藉由例環狀醚系化合物⑻的種類、及陽 離子系光酸產生)的陰離子部位之構造等而適當調整。 A本發明的硬化物特別適用於如光導波路等之光學用 途三光導波路的適用性係可利用周知導波路特性評估進行 判定。此種導波路特性評估並無特別的限制，例如可採用 針對由光硬化性樹脂組成物的硬化物所形成之簡 ^利關知方法進行光㈣敎时法。本發㈣硬化 ==減少（㈣aGk)法的光損失，例如在波長㈣nm f⑽下’最好G.2町，财有優越的光導波路 光導波路係由通稱核芯的高折射率部分、與通稱護面 (c〗ad)的低折射率部分構成之光回路 c 1 ιχιπ try )。本發明的光硬化性樹赌組成物除 it且?生產性地獲得硬化物之^ 1連焊接等作隸度的耐熱性，不㈣硬化後， 就連、爾後仍可保持優越透明性，且能發揮極抑制光損 320016 21 200844124 極有用於光導波路之 失的優越光學特性，就此觀點而言 用途。 在光導波路用途的光硬化性樹脂組成 调整之目的下，將可添加奈〃於折射羊 金屬氧化物包括例如:氧化錯、氧化鈥等乳::二例:: 1至20〇nm左右。此外，在抑制硬化收縮之目 口 = -2,2-二尹基丙醋 乳化雙環己稀及/或破酸 =波路是可❹如先㈣技術、奈米㈣(wherein R to R16 are the same or mutually different, and are selected from a hydrogen atom, a linear or branched chain C! to Cu alkyl group, a linear or branched chain Ci to eh alkoxy group. a halogen atom, an -OH group, a -C00H group, a -(3)-fluorenyl group, and a linear or branched chain-shaped fluorenyl group to a hydrazine 2 alkyl group, at least the group of the above-mentioned groups R to R A linear or branched chain enthalpy to a Cu alkyl group, which is formulated as a photocurable composition of a nonionic photoacid generator composed of a cationic moiety represented by the above formula (2-1) or (3-丨) It is possible to obtain a very superior hardened material having a property of absorbing a wavelength of, for example, 300 Å or more of light (preferably having a wavelength of 3 Å to 4 Å of light). Further, the above formula (320 016 formed by the cation portion shown by 4-υ) 17 200844124 A cationic photoacid generator which is formulated into a photocurable composition and can be dissolved well with various substrates (Ethyl ether compounds), which can be cured with excellent curing properties, and the coloring property of the cured product. It is extremely advantageous. The cationic photoacid generator (c) of the present invention is particularly preferably of the above formulas (ί) to (4) [best formulas (2-1) to (4-1)] The cation moiety shown is preferably composed of any one of pF", BF to and CF3S〇4_. 4 ί The amount of the cationic photoacid generator (C) used, for example, relative to the component (a) (B) is set to 1 part by weight, the lower limit is about 5 parts by weight of 〇·〇, and the upper limit is 20 parts by weight of left 纟. If it is less than 0.05 parts by weight, the photocationic polymerization may not be sufficiently carried out or the reaction may be changed. On the other hand, if it exceeds 20 parts by weight, the reaction may become too fast, resulting in a decrease in workability and uneven reaction. The best lower limit is about !·! parts by weight, the best ^ The photocurable resin composition of the present invention may contain, for example, a photosensitizer, a resin, an adhesion improving agent, a reinforcing agent, a softening agent, a plasticizer, a viscosity adjusting agent, etc. according to the method of use. Various conventional additives such as a solvent, etc. The photo sensitizer belongs to a photocationic polymerization which can further enhance the efficiency of the above-mentioned cationic photoacid generator (C) and further promote the photocationic polymerizable compound. Sensitizer Other restrictions include, for example, a few compounds, an organic sulfur compound, a persulfide compound, a redox compound, an azo compound, a diazo compound, a halogen compound, a photoreducible dye, etc. Specific examples of the photosensitizer include · Benzoin derivatives such as benzoin methyl ether and benzoin isopropyl ether; diphenyl ketone, 2, 4-dichlorodiphenyl ketone, decyl phenyl benzoate, 4, 4 ,-bis(dimethylamino)diphenyl ketone, etc. 2 18 320016 200844124 phenyl ketone derivative; 2-chloroindole and organism; 2-chloro hui 酉 Kun, 2V Yi Er. A t'r derivative such as a dibutyloxy oxime or the like; and a dipropoxy onion may be used in combination of two or more kinds. The photo-sensitizing agent can be used singly, the photocurable resin of the present invention is conventionally applied, and the composition of the photocurable tree stalk is used for the above-mentioned constituent components:::::: get. According to the present invention, the composition obtained is the most suitable photo-curable wax composition in the state of blocking light, except for inks, adhesives, and light which can be used as coating materials, coating materials/inks, inks for inks, and the like. The resisting agent and the plate-making material t-domain 4 are in the field. In particular, the light hardening dream moon 曰 composition of the present invention can form a cured product having heat resistance and excellent transparency, and can be used as a light guide wave, a full image, etc. The optical material used in the present invention can be applied to the resin composition used in the technique of (4) embossing (deleting 丨 丨 丨 nt) technology.), for example, mercury lamp, gas can be used. Light source, carbon arc lamp, metal tooth two lamp, sunlight, electron beam, laser light, etc. The hardening control system can be used to appropriately set the light intensity, temperature, time, etc. used for exposure, etc. The constituent component of the composition for improving the composition (addition of the curing control agent:) is preferably applied. Among them, it is preferable to use the above-described present invention using the cured product at the time of exposure and after exposure (post-baking). Photohardenable group, two use such as inkjet method Conventional methods such as lithography (Lithography), after forming a desired image or shape, can be obtained by exposure. 320016 19 200844124 Method of hardening control by temperature control of the body. Photocurable composition of the present invention After the exposure, the heat treatment may be performed by using a heat treatment at a temperature of about 50 to 2 ° C. The heat treatment after the exposure is: thick film hardening, hardening of the light non-irradiated portion, and The hardening of the hardened resin composition of the filler is effective. The cured product of the present invention can be used for: inks such as paints, coating materials, inks for inkjet, adhesives, photoresists, plate-making materials, optical waveguides, and Various applications, such as an image, a molding material, and a sealing material, are extremely effective as an optical material such as an optical waveguide, a nanoimprint, or a hologram, from the viewpoint of excellent transparency. The transparency of the present invention can be borrowed. It is evaluated by the light having a wavelength of i85 〇 nm. According to the present invention, it is possible to obtain a superior transparency of the above-mentioned transmittance, for example, the above (take 801 or more, especially 85% or more). The transparency can be determined by the structure of the anion site of the type of the cyclic (IV) compound (8) and the anion site of the filament (4), and the "heat resistance" of the light-sensitive day. 'When the heat treatment is performed again, the hard π is the meaning of maintaining transparency. Because the heat of the cured product of the present invention is used for further heating after hardening, the hardened material formed by the light illuminating the tree composition: the second is obtained by adding ": 120c-degree, the light is put into P, #玄..., after the hardened material, using the wavelength of 400 to 850nm 仃 敎 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 320 320 320 320 320 320 320 320 320 320 320 320 320 320 320 320 320 320 320 320 320 320 320 320 320 320 320 320 320 320 320 320 320 320 It can be kept at 84% or more, and it can form a cured product with excellent heat resistance. Therefore, it is extremely useful for optical applications such as heat resistance and high transparency, especially for optical waveguide applications. Heat resistance can be appropriately selected. The type and amount of the cyclic ether compound (B) and the structure of a cationic photoacid generator (an anion site of ruthenium, etc.) are used. Light-curing resin composition is used as light. The irradiation can be hardened very rapidly. Therefore, the effect of improving the productivity of the cured product can be achieved. The C-hardening rate can be achieved by the type of the cyclic ether compound (8) and the anion site of the cationic photoacid. A. The cured product of the present invention is particularly suitable for use in optical applications such as optical waveguides. The applicability of the three-optical waveguide can be determined by the evaluation of the characteristic characteristics of the known waveguide. There is no particular limitation on the evaluation of the characteristics of the waveguide. For example, the light (four) enthalpy method can be used for the method of forming a cured product of a photocurable resin composition. The light loss of the (four) aGk method is, for example, at a wavelength (four) nm f (10). Under the 'best G.2 town, the superior optical waveguide optical path is composed of a high refractive index part of the core, and a low refractive index part of the common surface (c) ad. c 1 ιχιπ try The photocurable tree gambling composition of the present invention can obtain excellent heat resistance even after it is hardened, in addition to it and productively obtaining a cured product. And it can be used to adjust the light-reducing resin composition of the optical waveguide, and it is used for the purpose of adjusting the photo-curable resin composition for optical waveguides. The naphthene may be added to the refracting sheep metal oxide including, for example, oxidized sputum, yttrium oxide, etc.: two cases: about 1 to 20 〇 nm. In addition, in the mouth of inhibiting hardening shrinkage = -2,2-di Yin Ethyl vinegar emulsified bicyclohexyl sulphate and / or broken acid = wave path is as good as first (four) technology, nano (four)
知技術來進行製造。 J y使用光關技術的方法，例如可則在基板上積層著 護面層、核芯層’更施行光阻塗佈後，隔著遮罩施行曝^、 顯影、蝕刻，接著便將光阻劑除去而形成核芯，再依被覆 著該核芯的方式形成上部護面層的方法。另—方面，使用 奈米壓印技術的方法係於可高速且廉價製作nm等級圖案 的技術，因為較光蝕刻技術更能縮短步驟且生產性優越， 因而最好採用此項技術。 更詳細言之，奈米壓印技術係於基材上經塗佈光硬化 f生組成物’按押著具細微圖案的壓印壓模（亦稱鑄模、版等） 之後，再藉由曝光•硬化，而轉印圖案的技術，具體係由 下述步驟構成。 步驟1 :在基材上塗佈光硬化性樹脂組成物，而製作 未硬化被膜 步驟2 :將未硬化被膜（被膜材料）加熱至樹脂組成物 320016 22 200844124 的玻璃轉移溫度（Tg)到軟化點左右，使樹脂變柔軟時，便 按押著具細微圖案的壓印壓模而轉印圖案 步驟3:將經轉印著細微圖案的被膜材料進行冷卻或 光硬化 步驟4 ··拆除壓印壓模，便獲得經壓印的細微構造 本發明的光硬化性樹脂組成物因具有上述構造，因而 與由塑膠、矽等構成的基材間之密接性優越，且利用光施 行硬化速度亦優越，特別適用於奈米壓印技術所使用的樹 脂組成物。此外，本發明之光硬化性樹脂組成物係在利用 光硬化施行細微圖案的轉印前後，就從基材與硬化組成物 的膨脹與收縮較少之觀點㈣，最好使用於奈米 途〇 將本發明的光硬化性m旨纟1成物㈣♦米壓印技術^ 獲得的硬化物，除了上述光導波路之外，例如：在半導骨 :::上全像、精密機械零件及嫌^ ，像纽可區分為表面浮雕全像與體積全像等2種 :、面二子？型係精密地利用光蝕刻或奈米壓印技術製作 =用::立:以_使刚化之物，特 途等。此外，體積全像二=用途、光學元件用 差之物，m 先干擾進订硬化時的折射率 積全像近=雕全像相_途。此外，體 途上倍受特別記憶體，作為全像記憶體的用 320016 23 200844124 r - 全像例如是由將硬化性組成物利用熱或光進行硬化而 獲得的透明硬化物，以透明板夾置的積層體而構成。全像 .係同時照射參照光與記錄光，而對透明板層間的透明硬化 *物記錄目標影像、將數據作成干擾光形式記錄，或者由參 照光的照射而浮現影像、數據的形態來利用，更可由 照相機讀取該等數據，並轉換為資訊等類似二維條碼的形 態來使用。 本發明之光硬化性樹脂組成物的硬化速度較快速（光 ，化性優越）’且此硬化物即使暴露於高溫中仍可避免遭受 著色，可保持優越之透明性，因而最好使用為全像。特別 是當將本發明光硬化性樹脂組成物使用於全像製造時，因 為=要精密的構造體，因而最好添加能抑制硬化收縮的硬 化膨脹性化合物，例如氧化雙環己烯及/或碳酸二 基丙|旨。 貫施例 以下’㈣實施例更詳細說明本發明，惟本發明並不 侷限於該等實施例。 只施例1至7、比較例1至3 一將表1所示種類與量的（A)乙烯醚系化合物、（B)環狀 μ系化合物、及⑹陽離子系光酸產生劑進行混合溶解，而 調製得組成物。 y將厚lmm或200 //111的鐵氟龍（註冊商標）板切取呈樣品 开^狀，在該片上積層著經鐵氟龍（註冊商標）被覆的ρΕτ薄 膜’接著，利用玻璃板上下包夾而形成積層體。將上述所 320016 24 200844124 r •調製得組成物利用注射器注入於樣品形狀的切取部分處， 接著，使用輸送帶式紫外線照射裝置並在下述條件下施行 ，UV照射，依此便形成對應於所使用鐵氟龍（註冊商標）板厚 、度1min或2 0 0 // m的硬化物。所獲得硬化物的凝膠分率、穿 透率、耐熱性，將依照後述方法施行測定、評估。結果如 表1所示。 UV照射裝置：USHI0電機製紫外線照射裝置uvc_ 02516S1AA02 金屬齒素燈 照射條件：160W 輸送帶速度：2m/min 照射次數：1次 320016 25 200844124[表1] rd ^ ?«駟Know the technology to manufacture. J y uses the method of the light-off technique. For example, the protective layer and the core layer may be laminated on the substrate. After the photoresist coating is applied, the mask is exposed, developed, and etched, and then the photoresist is removed. A method of forming an upper core layer by removing the agent to form a core and then covering the core. On the other hand, the method using the nanoimprint technique is a technique for producing a nm-scale pattern at a high speed and at a low cost, and since the photo-etching technique is more capable of shortening steps and superior in productivity, it is preferable to employ this technique. In more detail, the nanoimprint technology is applied to a substrate by applying a photohardenable composition to press a stamped stamper (also known as a mold, plate, etc.) with a fine pattern, and then by exposure. • Hardening, and the technique of transferring a pattern is specifically constituted by the following steps. Step 1: Coating a photocurable resin composition on a substrate to prepare an uncured film Step 2: heating the uncured film (film material) to a glass transition temperature (Tg) to a softening point of the resin composition 320016 22 200844124 When the resin is softened to the left and right, the imprinting stamp having a fine pattern is pressed to transfer the pattern. Step 3: Cooling or photohardening the film material transferred with the fine pattern. Step 4 · Removing the stamping pressure By the mold, the photocurable resin composition of the present invention has the above-described structure, and therefore has excellent adhesion to a substrate made of plastic or tantalum, and is excellent in light curing speed by light. It is especially suitable for the resin composition used in nanoimprint technology. Further, the photocurable resin composition of the present invention is preferably used in a nanometer from the viewpoint of less expansion and contraction of the substrate and the hardened composition before and after the transfer of the fine pattern by photocuring (4). The cured product obtained by the photocurable m of the present invention is a cured product obtained by the above-mentioned optical waveguide, for example, a semi-conductive bone::: a full-image, a precision mechanical part, and a suspected ^, like Newcom can be divided into two types: surface relief full image and volume full image:, face two children? The type is precisely fabricated by photo-etching or nano-imprinting technology. = Use::: To make a rigid object, special way, etc. In addition, the volume is full image 2 = use, the optical component is poor, and m first interferes with the refractive index product at the time of binding hardening. In addition, the body is subjected to special memory, and is used as a holographic memory. 320016 23 200844124 r - The hologram is, for example, a transparent cured product obtained by hardening a curable composition by heat or light, and is sandwiched by a transparent plate. It is composed of a laminate. The hologram is used by simultaneously irradiating the reference light and the recording light, and recording the target image on the transparent hardened layer between the transparent plate layers, recording the data as interference light, or using the reference light to illuminate the image and data. The data can be read by the camera and converted into a form such as information and the like. The photocurable resin composition of the present invention has a faster curing speed (excellent light and chemical properties) and the cured product can be prevented from being colored even when exposed to a high temperature, and can maintain excellent transparency, so that it is preferably used as a whole. image. In particular, when the photocurable resin composition of the present invention is used in holographic production, since a structure to be precise is required, it is preferable to add a hardenable swelling compound capable of suppressing hardening shrinkage, such as oxidized dicyclohexene and/or carbonic acid. Two bases of C. The present invention is described in more detail in the following <RTIgt; (4) Examples, but the invention is not limited to the examples. Only Examples 1 to 7 and Comparative Examples 1 to 3 were prepared by mixing and dissolving (A) a vinyl ether compound, (B) a cyclic μ compound, and (6) a cationic photoacid generator of the type and amount shown in Table 1. And modulate the composition. y The Teflon (registered trademark) plate having a thickness of lmm or 200 //111 is cut into a sample shape, and a Teflon film coated with Teflon (registered trademark) is laminated on the sheet. The laminate is formed by sandwiching. The above-mentioned 320016 24 200844124 r modulating composition is injected into the cut-out portion of the sample shape by a syringe, and then, using a conveyor-type ultraviolet ray irradiation device and performing under the following conditions, UV irradiation is formed corresponding to the use. Teflon (registered trademark) hardened material with a thickness of 1 min or 2 0 0 // m. The gel fraction, the penetration rate, and the heat resistance of the obtained cured product were measured and evaluated in accordance with the method described later. The results are shown in Table 1. UV irradiation device: USHI0 electric mechanism ultraviolet irradiation device uvc_ 02516S1AA02 metal dentate lamp Irradiation condition: 160W Conveyor speed: 2m/min Irradiation times: 1 times 320016 25 200844124[Table 1] rd ^ ?«驷
«φ^Ηί 絮爱»0( V) 【拿Ϊ ¥】嘀裘 100 100 100 100 100 100 100 100 100 100 1,4 -環己烷二甲酵二乙烯醚 (Aldrich公司製5 1, 6-己二酵二乙烯醚 (Aldrich公司製） 羥氡基降萡烷甲酵二乙烯醚 (商品名「ONB-DVEj 、Daicel化學工業公司製） LO Lft S S S s S o ΙΩ Celloxide 2021P: 羧酸-3, 4-環氧環己基甲基- 3’，4’ -環氡環已酯 (Daicel化學工業公司製） Celloxide 8000: 雙（3, 4-環氣環己烷）（Dai cel化學工業公司製） Aronoxetane 0XT-121(東亞合成公司製） m ΙΛ m m in in ΙΛ in in xr> lrgacure250(汽巴特殊化學公司製） P12074(Rhodia 公司製） ist (Μ ΙΛ CO oo CD OO m CD 〇 CO X CNI CD CO % in oo 〇 Ο 00 CO s X CD Ο σ> 03 r»H c» s a> oo 03 ΟΟ 00 OO oo oo 〇 CN1 05 00 % % 卜 〇〇 S o a> 〇 <NI σ> CM σ> CM C» 03 oo CNI 09 «ΝΙ Od CQ 〇 CO a> ο 05 o c» 〇 a> oo oo S O σ> 〇 却 Ξ S S s Od 〇 却 05 οο οο S S % CO oo S S s 〇 CNI Od α> οο % o a> o 凝睿分率（％) 4 0 0 nm 550nm 70 Onm 8 5 0 nm 400am 5 5 0 n m 700nm 850nm 耐熱性 r—ι 次 1___1 r—n 次 i—l 齋 26 320016 200844124 • 實施例8至14、比較例4至6 將表2所示種類與量的（A)乙烯醚系化合物、（B)環狀 、醚系化合物、及（c)陽離子系光酸產生劑進行混合溶解而 . 製得組成物。 將所獲得組成物利用旋塗機在具氧化膜的石夕晶 上’塗佈成厚10/zm之後’利用輸送帶式紫： 施行UV照射。將獲得薄臈硬化物切斷並 攻”、、射衣置 用，依照後述方法施行光損失的測定、’、、、剛定樣品使 所示。 、疋㈣4果如表2 320016 27 200844124 [表2] 比較例 CD 組成[重量份] (Α)乙烯瞇系化合物 100 (6)環狀醚系化合物 CO (C)陽離子系光酸產生剤 Lf^ 評估 CO c=> LO 100 ΙΛ CO o 100 m C<l o 實施例 CO C<l ο 100 m C<1 o CM 〇 100 m CN1 o <=> 100 ΙΛ Cvl o o 100 in oa o OQ o 100 in CNI CD CNI o σ> 100 (NI 〇 (NI o οο 100 LO CO CD C<l o 1，4-環已烷二甲酵二乙烯瞇 (Aldrich公司製） 1,6-己二酵二乙烯鰱 (Aldrich公司製） 羥氡基降萡烷甲酵二乙烯瞇 (商品名「0NB-DVE」、Daicel化學工業公司製） Celloxide 2021P: 羧酸-3, 4-環氧環已基甲基-3’，4’ -環氡環己酯 (Daicel化學工業公司製） Celloxide 8000: 雙（3, 4-環氧環己烷KDaicel化學工業公司製） Aronoxetane 0XT-121(東亞合成公司製） lrgacure250(汽巴特殊化學公司製） PI2〇74(Rhodia 公司製） 初期 加熱後 光損失[dB/cm] 28 320016 200844124 (評估方法） 凝膠分率 、容巧中 例，、比車乂例所得厚200 // m的硬化物，放入MEK 命劑中，測定萃取前的 並依下式進行計算。期4量、與萃取乾燥後的重量’ 量率（心=(卒取乾燥後的重量）/(萃取前的初期重 穿透率、耐熱性 :對依實施例i至7與比較例⑷所得厚-剛硬 Ϊ後的硬化物（初期）、以及對該硬化物在峨施行i小 、寸力，、、、處理而得的硬化物（加熱後），使用日立製作所製分 光 度 °十 U 3綱’測定波長 4GGnm、55Gnm、7_mA 850nm 的^率。該等結果如表1中的「初期穿透率」與「加熱 後牙透率」攔位中所示。再.將加熱後？透率達議以上的 f月況’ #估為「〇」’將當任—波長的穿透率差超過⑽時， 評估為「X」，並記於表i中的「耐熱性」搁位中。另外， 比較例1所得組成物，因為陽離子系光酸產生劑不溶，因 而並未充分地硬化，並無法進行穿透率測定。 光損失（導波路特性） 將實施例8至14與比較例4至6所獲得厚1〇/zm之硬 化物，針對剛硬化後（初期）、及在12(rc施行丨小時加熱 處理後（加熱後）的硬化物，使用波長85〇随之光源利用減' 少法（cut-back法）施行測定。 產業上之可利用性 320016 29 200844124 驀 , 本發明之光硬化性樹脂組成物因 、 性均優越的特性，因而除可適用於日^有透明性與耐熱 :二：墨用油墨、成形材料、密封材料等用途之外= r適用於料波路、奈米壓印、全像等光學領域中。 【圖式簡單說明】 無。 【主要元件符號說明】 f 無0«φ^Ηί 絮爱»0( V) [ΪΪ ¥]嘀裘100 100 100 100 100 100 100 100 100 100 1,4 -cyclohexanedimethyldivinyl ether (Aldirich 5 1, 6- Dihexyl divinyl ether (manufactured by Aldrich Co., Ltd.) Hydroxydecyl decanoyl methyl methacrylate (trade name "ONB-DVEj, manufactured by Daicel Chemical Industry Co., Ltd." LO Lft SSS s S o ΙΩ Celloxide 2021P: Carboxylic acid-3 , 4-epoxycyclohexylmethyl-3',4'-cyclohexanyl ester (manufactured by Daicel Chemical Industry Co., Ltd.) Celloxide 8000: bis (3, 4-cyclohexane) (Dai cel Chemical Industry Co., Ltd. Aronoxetane 0XT-121 (manufactured by Toagosei Co., Ltd.) m ΙΛ mm in in ΙΛ in in xr> lrgacure250 (made by Ciba Specialty Chemicals Co., Ltd.) P12074 (made by Rhodia Co., Ltd.) ist (Μ ΙΛ CO oo CD OO m CD 〇CO X CNI CD CO % in oo 〇Ο 00 CO s X CD Ο σ> 03 r»H c» s a> oo 03 ΟΟ 00 OO oo oo 〇CN1 05 00 % % 卜〇〇 S o a>〇<NIσ> CM σ> CM C» 03 oo CNI 09 «ΝΙ Od CQ 〇CO a> ο 05 Oc» 〇a> oo oo SO σ> 〇 Ξ SS s Od 〇 but 05 οο οο SS % CO oo SS s 〇CNI Od α> οο % o a> o Condensation rate (%) 4 0 0 nm 550nm 70 Onm 8 5 0 nm 400am 5 5 0 nm 700nm 850nm Heat resistance r—ι次 1___1 r—n times i—l Zhai 26 320016 200844124 • Examples 8 to 14 and Comparative Examples 4 to 6 The types shown in Table 2 are The amount of the (A) vinyl ether compound, the (B) cyclic, the ether compound, and the (c) cationic photoacid generator are mixed and dissolved to obtain a composition. The obtained composition was applied to a thickness of 10/zm on a quartz crystal having an oxide film by a spin coater. Using a conveyor belt type violet: UV irradiation was carried out. The thin tantalum cured product was cut and attacked, and the shot was placed, and the light loss was measured according to the method described later, ', and the sample was just set. 疋 (4) 4 fruits are as shown in Table 2 320016 27 200844124 [Table 2] Comparative Example CD Composition [Parts by weight] (Α) Ethylene lanthanide compound 100 (6) Cyclic ether compound CO (C) Cationic photoacid generation 剤Lf^ Evaluation CO c=> LO 100 ΙΛ CO o 100 m C<lo Example CO C<l ο 100 m C<1 o CM 〇100 m CN1 o <=> 100 ΙΛ Cvl oo 100 in oa o OQ o 100 in CNI CD CNI o σ> 100 (NI 〇 (NI o οο 100 LO CO CD C<lo 1,4-cyclohexanedicarboxylic acid divinyl hydrazine (manufactured by Aldrich) 1,6-hexanedivinyl divinyl hydrazine (manufactured by Aldrich) Hydroxydecyl decane Cellulose divinyl fluorene (trade name "0NB-DVE", manufactured by Daicel Chemical Industry Co., Ltd.) Celloxide 2021P: Carboxylic acid-3, 4-epoxycyclohexylmethyl-3',4'-cyclononylcyclohexyl ester ( Daicel Chemical Industry Co., Ltd. Celloxide 8000: bis (3, 4-epoxycyclohexane KDaicel Chemical Industry Co., Ltd.) Ar Onoxetane 0XT-121 (manufactured by Toagosei Co., Ltd.) lrgacure250 (manufactured by Ciba Specialty Chemicals Co., Ltd.) PI2〇74 (manufactured by Rhodia Co., Ltd.) Light loss after initial heating [dB/cm] 28 320016 200844124 (Evaluation method) Gel fraction and volume In the case of the case, the hardened material with a thickness of 200 // m is obtained in the MEK agent, and the pre-extraction is measured and calculated according to the following formula. The amount of the period 4 and the weight after the extraction and drying are measured. (heart = (weight after stroke drying) / (initial heavy transmittance before extraction, heat resistance: thickened-hardened hardened material (initial) obtained in Examples i to 7 and Comparative Example (4), And the cured product obtained after the hardened material is subjected to i small, indentation, and treatment (after heating), using a spectrophotometer manufactured by Hitachi, Ltd., and measuring wavelengths of 4 GGnm, 55 Gnm, and 7 mA 850 nm. Rate. These results are shown in the "Initial Penetration Rate" and "Post Tooth Rate after Heating" in Table 1. Will it be heated? When the penetration rate is higher than the above-mentioned f-month condition ' # 为 〇 ' ' 将 将 — 波长 波长 波长 波长 波长 波长 波长 波长 波长 波长 波长 波长 波长 波长 波长 波长 波长 波长 波长 波长 波长 波长 波长 波长 波长 波长 波长 波长 波长 波长 波长 波长 波长 波长in. Further, in the composition obtained in Comparative Example 1, since the cationic photoacid generator was insoluble, it was not sufficiently cured, and the transmittance measurement could not be performed. Light loss (guide path characteristics) The cured products of the thicknesses of 1 〇/zm obtained in Examples 8 to 14 and Comparative Examples 4 to 6 were obtained after the hardening (initial) and after 12 (r 施 hours of heat treatment ( The cured product after heating is subjected to measurement using a wavelength of 85 〇 and the light source is reduced by a cut-back method. Industrial Applicability 320016 29 200844124 蓦 The photocurable resin composition of the present invention It has excellent properties, so it can be applied to the daily transparency and heat resistance. 2: Ink, ink, molding materials, sealing materials, etc. = r is suitable for optical applications such as material wave, nano-imprint, and hologram. In the field. [Simple description of the diagram] No. [Description of main component symbols] f No 0
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