TW201211093A - Curable resin composition and cured product thereof - Google Patents

Curable resin composition and cured product thereof Download PDF

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Publication number
TW201211093A
TW201211093A TW100118218A TW100118218A TW201211093A TW 201211093 A TW201211093 A TW 201211093A TW 100118218 A TW100118218 A TW 100118218A TW 100118218 A TW100118218 A TW 100118218A TW 201211093 A TW201211093 A TW 201211093A
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Taiwan
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resin composition
curable resin
acid
epoxy resin
hardening
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TW100118218A
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Chinese (zh)
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TWI492958B (en
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Masataka Nakanishi
Chie Sasaki
Hideyuki Ota
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Nippon Kayaku Kk
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/095—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00 with a principal constituent of the material being a combination of two or more materials provided in the groups H01L2924/013 - H01L2924/0715
    • H01L2924/097—Glass-ceramics, e.g. devitrified glass
    • H01L2924/09701—Low temperature co-fired ceramic [LTCC]

Abstract

Disclosed is a curable resin composition which can be favorably used as an optical material, has excellent storage stability and curing stability, and provides a cured product having excellent durability against light and heat and excellent gas permeability resistance. The curable resin composition comprises an epoxy resin having an epoxycyclohexane structure and an alcohol having a tricyclodecane structure as essential components.

Description

201211093 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種具有特定結構之硬化性樹脂組成 物，且關於一種適合於電氣電子材料用途，尤其是光半導 體用途之該硬化性樹脂組成物及硬化物。 【先前技術】 環氧樹脂藉由以各種硬化劑硬化，而成為通常機械性 質耐水性、耐化學品性、耐熱性、電氣性質等優異之硬 化物，用於接著劑、塗料、積層板、成形材料、濟鑄材料、 抗蝕劑等廣泛領域。 另外，於光電子學相關領域，伴隨近年來之高度資訊 化。’為順利地傳輸及處理魔大之資訊，而正在開發產生光 訊號之技術代替先前之藉由電氣配線之訊號傳輸。其中， 於光波導、藍色LED及光半導體等光學零件之領域期待 開發出透明性優異之樹脂。 尤其於需要光學特性之領域，例如LED冑品等領域 中’多使用環氧樹脂之酸野硬化物。作為自先前以來用於 此種LED製品等光半導體元件之密封材料的環氧樹脂，廣 泛使用耐熱性、透明性、機械特性之平衡優異之㈣A型 環氧樹脂所代表之縮水甘油醚型環氧樹脂組成物。 然而，LED製品之發光波長之短波長化（主要為彻⑽ 以下之藍色發光）發展之結果指Α，由於短波長之光之影 響，上述密封材料於LED晶片上著色，最終作為led製品 而照度降低。 201211093 因此，由於3,4一環氧環己基曱基_ 3，，4，一環氧環己基 甲酸酯所代表之脂環式環氡樹脂，與具有芳香環之縮水甘 油醚型環氡樹脂組成物相比較，於透明性方面優異，故作 為LED密封材料而積極研究。（專利文獻1、2) 然而，近年來之LED製品面向照明或τν之背光等， 高亮度化進一步發展，LED點亮時伴隨大量發熱。因此， 使用如上所述之脂環式環氧樹脂之樹脂組成物亦於[ED晶 片上產生著色，最終觀測到作為LED製品而照度下降之情 形因此，期待開發出提高耐久性之樹脂組成物。 專利文獻1 :曰本特開平9_ 213997號公報 專利文獻2 :日本專利3618238號公報 專利文獻3 :日本特開2〇〇8_ 285591號公報 專利文獻4 :國際公開第2〇〇5/1〇〇445號 【發明内容】 般之月曰％式％^氧樹脂的硬化物之硬度與脆度成為 題。這與用作先前之LED之密封材料之情形時亦相同， 其LED密封材料由於其光之出射變得重要，故與一般之 封材料相比，無法大量混入盔 機填料#，無法進行機械$ 度之、強。因此，容易產生龜裂等，對成為該密封材料: 樹月曰結構要求向度之韌性。為了進行改善，對三羥… ^等醇之添加等進行了研究（專利文獻3)，該等醇之添加 =例如當與酸㈣之硬化時，自室溫起進行醇與酸針之 反應，故對於料穩定性具有較大之缺點 定性變得非常差。 人无化物之穩 4 201211093 =外’由於LED存在上述環氧樹脂 正研究將聚矽氧樹脂或聚矽氧改 久f生之問題， 入有嫩骨架（具體而言為具有質：氧"旨等所代表之導 脂用作密封材料。（專利文獻4) 鍵之月架）之樹 對孰氧院骨架之樹脂與環氧樹脂相比， #白於應用於LED製品之密封材料之 广寺，自led晶片上之著色之觀點而言，可以說與 樹脂：比耐久性更優異。然而’料入切 架 脂類與環氧樹脂料，耐透氣性[因此，於使用聚：： 樹脂或聚#氧改質環氧樹脂作為LED密封材料之情 雖然㈣晶片上之著色不成為問題，但存在以下課題.、使 鍍敷於金屬引線架（即LED封裝體内之構成構件）上之銀 成分（為提高反射率而實施了鍍銀），變色或黑化最' 為LED製品之性能降低。 因此在市場上，與該先前之脂環式環氧樹脂相比，更 謀求-種對光或熱之耐久性高、亦滿足耐透氣性之環氧樹 脂組成物材料作為光學材料。 本發明係鑒於上述先前技術之問題而形成者，其目的 在於提供一種硬化性樹脂組成物，其可適宜用作光學材 料，提供具有優異之儲存穩定性與硬化穩定性，並且對光 或熱之耐久性或耐透氣性優異之硬化物。 本發明人等鑒於如上所述之實際情況，進行深入研 究’結果完成本發明。 即，本發明係關於： 201211093 (1 ) 一種硬化性樹脂組成物，其含有具有環氧環己烷 結構之環氧樹脂、具有三環癸烷結構之醇； (2 )如前項（丨）之硬化性樹脂組成物，其中，具有 環氧環己烧結構之環氧樹脂為脂環式環氧樹脂； (3 )如前項（丨）之硬化性樹脂組成物，其中，具有 環氧環己统結構之環氧樹脂為具有環氧環己烷結構及矽氧 烷結構的環氧樹脂； (4 ) 一種硬化性樹脂組成物，其含有前項（1 )至（3 ) 中任一項之硬化性樹脂組成物與硬化劑及/或硬化促進 劑； (5 )如前項（4 )之硬化性樹脂組成物，其中，硬化 劑為酸酐； (6 ) 一種硬化物，其係將前項（4 )、（ 5 )中任一項之 硬化性樹脂組成物硬化而獲得； (7)種光半導體裝置，其含有前項（4)、（5)中任 一項之硬化性樹脂組成物。 本發明之硬化性樹脂組成物由於儲存穩定性或硬化物 之穩定性優異，另外對光、熱之財著色性或耐透氣性亦優 異，故作為光學材料，尤其是光半導體用（led製品等） 之接著材料、密封材料而極其有用。尤其藉由使環氧樹脂 成為骨架中含有環氧環己烷結構及矽氧烷結構之構成，可 形成耐氣體性更優異之硬化物。 另外，本發明之硬化性樹脂組成物不僅耐透濕性、耐 吸濕性、接著性均優異，並且尤其於製成以酸酐為硬化劑 201211093 之熱硬化性樹脂組成物之情形時，亦具有抑制硬化時之揮 發之效果。 【實施方式】 以下’對本發明之硬化性樹脂組成物進行說明。 本發明之環氧樹脂係使用具有環氧環己烷結構之環氧 樹脂。 本發明中具有環氧環己烷結構之環氧樹脂可列舉脂環 式％氧樹脂、具有環氧環己烷結構及矽氧烷結構之環氧 脂。 ' 作為脂環式環氧樹脂，只要為具有兩個以上環氧環己 烷結構之化合物，且其結構中具有脂環結構者則並無特 別限定。 ~ 具體而言可列舉：將可藉由「環己烯羧酸與醇類之酯 化反應」或者「環己烯曱醇與羧酸類之酯化反應（Tetrahedr〇n ν〇1·36 p.2409 (1980)、Tetrahedron Letter p.4475 (1980)等中 。己載之方法）」、進而「環己烯羧酸酯之酯交換反應（日本 特開2006— 052187號公報等中記載之方法）」而製造之化 合物氧化而成者等。 作為醇類’只要為具有醇性經基之化合物，則並無特 別限定，可列舉：乙二醇、丙二醇、1>3_丙二醇、U2—丁 一醇、丨，4 — 丁二醇、i，5 —戊二醇、1，6 —己二醇、環己烷二 甲醇、2，4~二乙基戊二醇、2—乙基一2_ 丁基一1,3 —丙二 醇、新戊二醇、三環癸烷二甲醇、降莰烯二醇等二醇類； 甘油、二羥甲基乙烷、三羥甲基丙烷、三羥曱基丁烷、2 — 201211093 羥甲基一1 4 ~~ τ ，丁一醇等三醇類；新戊四醇、=經甲Α 丙烷等四醇類等。另休“， 砰—-羥甲基 ^ 卜，作為羧酸類，可列舉：草酸、馬 來酸、昌馬酸、鄰I _ y, —甲酉夂、間本二甲酸、己二酸、環己 烧二甲酸等’但並不限定於此。 r之’可列舉藉由環己烯醛衍生物與醇之縮醛反應而 仵之縮齡化合物。作 ^ ^ g 應方法，只要應用一般之縮醛化 反應即可’例如p應- 面、隹… 有.使用甲苯、二甲苯等溶液，- 面進仃共沸脫水一面進行 -_ . 丁反應之方法（美國專利第2945008 … 於濃鹽酸中溶解多元醇後，-面慢慢添加路類 :用之方法（日本特開昭48 一 9_號公報）；將 將右拖、./ ^之方法（美國專利第3〇92640號說明書）； ^劑用於反應介f之方法（日本特開平卜215州 ::報”使用固體酸觸媒之方法（曰本特開2〇。7 _ 23。992 ’么）#。自結構之穩定性而言，較佳為環狀縮醛結構。 :外’可列舉將乙稀基環己烯或檸檬烯、二環戊二烯、 :冬二烯、甲基二環戊二烯、二環己烯、辛二烯等脂環 式多疋烯烴氧化而成者等。 作為該等環氧樹脂之具體例，可列舉：erl_ 422i、erl 二4299(全部為商品名’均為D〇w 製朴_“ ^、ΕηΡΕ315()、ΕΗΡΕ31實E (全部為商品名均為 W學工業製造）及二環戍二稀二環氧化物等，但並不 限疋於該等（參考文獻：總論環氧樹月旨基礎編旧〜⑴。 該等可單獨使用，亦可併用2種以上。 作為具有環氧環己院結構及石夕氧院結構之環氧樹脂， 8 201211093 只要為具有環氧環己烧結構之有機聚石夕氧院則並無特別 限定，本發明中尤其可列舉：藉由「將具有環氧環己基之 烧氧基石夕燒用於原料之溶膠—凝膠反應」而獲得之環 脂。 、 具體而言，可列舉以下公報中記載之具有三維伸展之 網眼狀結構的倍半矽氧烷（silsesqui〇xane)型之有機聚矽 氧烷：日本特開2004- 256609號公報、日本特開2〇〇4 — 346M4號公報、國際公開第2〇〇4/〇7215〇號、日本特開 2006- 8747號公報、國際公開第2〇〇6/〇〇399〇號、日本特 開2006- 104248號公報、國際公開第2〇〇7/ 1359〇9號、 曰本特開2004— 10849號公報、日本特開2〇〇4_ 359933號 公報、國際公開第2005/ i 00445號、日本特開2〇〇8 —丨7464〇 號公報等。 對有機聚矽氧烷之結構雖無特別限定，但由於單純之 三維網眼結構之矽氧烷化合物過硬，故期待緩和硬度之結 構。 本發明中尤佳為：1分子中具有聚矽氧鏈段、與藉由溶 膠一凝膠反應而獲得之上述倍半矽氧烷結構的嵌段結構 體作為此種化合物之製造法，可列舉如國際公開第2 〇 1 〇 /026714號中記載之製造方法及結構。 作為具有二環癸院結構之醇，可列舉三環癸烷二甲 醇、曱基二環癸烷二甲醇、五環十五烷二曱醇等。作為此 種化合物，彳列舉將環戊二#或甲&環戍二稀之聚合物（例 如一環戊二烯、甲基二環戊二烯、三環戊二烯等）之烯烴 9 201211093 部分進行氫甲酿化後，藉由還原而製成醇之方法。 本發明之硬化性樹脂組成物係藉由將「上述具有環 2己燒結構之環氧樹脂、與具有三環癸烧結構之醇」以特 疋之比例均勻混合而獲得。 作為均勻混合之方法，例如可使用「將該等於〇〜100 °c之範圍内一面攪拌一面均句熔融混合之方法或使用有 機命劑加以今解，使其均句後蒸館去除溶劑，獲得本發明 之硬化性樹脂組成物」之方法。 作為該等摻合量，相對於具有環氧環己烧結構之環氧 樹脂’具有三環癸院結構之醇為i 5〜4q重量％，較佳為2 30重1%，尤佳為2·25〜25重量％。過量之醇有引起硬 化不良之問題之可能性’因而欠佳，若過少則難以發揮效 果。 本發明之硬化性樹脂組成物不僅提高勃性、透明性' 时透氣性、耐透濕性、耐吸濕性、接著性，尤其於製成以 酸酐作為硬化劑之熱硬化性樹脂組成物之 硬化時之揮發之效果’化合物向環财之釋放亦:= 制，亦有助於作業者之安全性。尤其於僅使用少量樹脂之 表面構裝f LED、薄膜之塗佈材料或膜等用途中較顯著， 有助於解決「酸酐揮發、硬化劑與環氧之平衡破壞、產生 硬化不良、無法獲得真正之硬化物、著色嚴重」等問題。 另外，本發明之硬化性組成物於硬化時著色亦較少。 本發明之硬化性樹脂組成物中’可單獨使用作為必需 成分之具有環氧環己烷結構之環氧樹脂，亦可將上述具有 201211093 環氧環己烷結構之環氧樹脂與其他環氧樹脂併用而使用。 於併用之情形時，上述環氧樹脂於全部環氧樹脂中所占之 比例較佳為70重量％以上，尤佳為80量量％。 士作為本發明之硬化性樹脂組成物中可使用之其他環氧 樹脂，可列舉酚醛清漆型環氧樹脂、雙酚A型環氧樹脂、 聯本型環氧樹脂、三苯曱烷型環氧樹脂、苯酚芳烷基型環 氧樹脂等。具體而言，可列舉：雙酚A、雙酚S、硫代二紛、 苐雙酚、祐二酚、4,4，一聯苯酚、2,2，一聯苯酚、3,3,，5,5,〜 四甲基一[U—聯苯酚]一 4,4·_二醇、對苯二酚、間苯二 酚、萘二酚、三—（4 一羥苯基）甲烷、1，1，2,2 —四（4—羥笨 基）乙烷；酚類（苯酚、經烷基取代的苯酚、萘酚、經烷基 取代的萘酚、二羥基苯、二羥基萘等）與甲醛、乙醛、苯 甲醛、對羥基苯曱醛、鄰羥基苯甲醛、對羥基苯乙酮、鄰 細基苯乙酮、二環戊二烯、糠醛、4,4，一雙（氣甲基 ~聯苯、4,4'一雙（曱氧基甲基）一1，1，一聯苯、1，4一雙（氣甲 基）苯、丨，4 —雙（曱氧基曱基）苯等之縮聚物及該等之改質 物，四溴雙酚A等齒化雙酚類；由醇類衍生之縮水甘油醚 化物、脂環式環氧樹脂、縮水甘油胺系環氧樹脂、縮水甘 油S旨系環氧樹脂等固體或液狀環氧樹脂，但並不限定於該 等。 、° 本發明之硬化性樹脂組成物可含有硬化劑及/或硬化 促進劑（硬化觸媒）。 以下’對藉由硬化劑之熱硬化（硬化性樹脂組成物A )、 藉由酸性硬化促進劑之陽離子硬化（硬化性樹脂組成物B) 201211093 進行說明。 藉由硬化劑之熱硬化（硬化性樹脂組成物A) 作為本發明之硬化性樹脂組成物A所含有之硬化劑， 例如可列舉胺系化合物、酸酐系化合物、酿胺系化合物、 酚系化合物、羧酸系化合物等。作為可使用之硬化劑之具 體例，可列舉：二胺基二笨甲院、二伸乙三胺、三伸乙四 胺、二胺基二苯基砜、異佛酮二胺、二氰基二醯胺、由次 亞麻油酸之二聚物與乙二胺合成之聚醯胺樹脂、鄰苯二甲 酸酐、1，2,4—苯三曱酸酐、焦蜜石酸酐、馬來酸酐、四氫 鄰苯二甲酸酐、曱基四氫鄰苯二曱酸酐、曱基耐地酸酐 (methyl nadic anhydride )、对地酸酐 '六氮鄰苯二甲酸肝 、 甲基六氫鄰笨二曱酸酐、丁烧四甲酸酐、二環[2,2，丨]庚院— 2,3 —二曱酸酐、甲基二環[2,2，1]庚烷一2,3 —二曱酸酐、環 己烷一1，2,4 —三甲酸—ι，2 —酐、雙酚A、雙酚F、雙酚s、 第雙酚 '萜二酚、4,4,一聯苯酚、2,2，一聯苯酚、3,3',5,5，一 四甲基一[1，Γ —聯苯]一 4,4, 一二醇、對苯二酚、間苯二酚、 萘二盼、三一（4一羥苯基）甲烷、—四（4 -羥苯基）乙 烧；盼類（笨酚、經烷基取代的苯酚、萘酚、經烷基取代 的萘酴、二羥基苯、二羥基萘等）與甲醛、乙醛、苯甲醛、 對經基苯甲醛、鄰羥基苯甲醛、對羥基苯乙酮、鄰羥基苯 乙酮、二環戊二烯、糠醛、4,4，_雙（氣甲基）一1，1，一聯苯、 4，t —雙（曱氧基曱基）一 M，—聯苯、丨，4 一雙（氣甲基）苯、1，4 —雙（曱氧基甲基）苯等之縮聚物及該等之改質物；四溴雙酚 A等画化雙酚類、咪唑、三氟硼烧—胺錯合物、脈衍生物、 12 201211093 祐烯與酚類之縮合物等，但並不限定於該等。該等可單獨 使用，亦可使用2種以上。 本發明中’尤佳為上述酸肝或羧酸樹脂所代表之具有 酸酐結構及/或羧酸結構之化合物。 作為具有酸酐結構之化合物’較佳為甲基四氫鄰苯二 曱酸酐、甲基耐地酸酐、耐地酸酐、六氫鄰苯二曱酸野、 曱基六氫鄰苯二曱酸酐、丁烷四甲酸酐、二产 己烷-1，2,4-三甲酸—1’2—酐等，尤佳為曱基六氫鄰笨二 甲酸酐、環己烷一1，2,4一三曱酸—i，2__奸。 作為具有叛酸結構之化合物（以下稱為聚叛酸），尤佳 為2〜4官能之聚羧酸，進而較佳為藉由使2〜4官能之多 元醇與酸酐進行加成反應而獲得之聚缓酸。 作為2〜4官能之多元醇，只要為具有醇性羥基之化合 物’則並無特別限定，可列舉：乙二醇、丙二醇、…丙 二醇、U2- 丁二醇、M- 丁二醇、以—戊二醇、ι>6—己 二醇、環己烷二甲醇、2,4 —二乙基戊二醇、2—乙基—2 — 丁基-i，3—丙二醇、新戊二醇、三環癸燒二甲醇、降获歸 一甘油、三經甲基乙院、三經甲基丙烧、三 ”基丁院小經甲基一 丁二醇等三醇類；新戍四 醇、一一二經甲基丙院等四醇類等。 尤佳之2〜4官能之多元醇為環己烷二甲醇、24_二乙 基戊二醇、2-乙基—2- 丁基叫，3_丙二醇、新戊二：、 二環癸燒H降_二醇等支鍵狀或環狀之醇類。 13 201211093 作為製造聚叛酸時之酸酐，較佳為：甲基四氯鄰苯二 甲酸酐：甲基耐地酸酐、耐地酸酐、六氫鄰苯二甲酸酐、 甲基六氫鄰苯二甲酸針、丁按四田祕 J况四甲酸酐、二環[2,2，1]庚烷一 2,3-二甲酸肝、甲基二環庚烷—2,3—二甲酸針環 己烷一1，2,4 —三甲酸一 1，2~酐等。 加成反應之條件並未特別指定，具體之反應條件之一 為如y方法：將酸針及多元醇於無觸媒、無溶劑之條件下， 於40°C〜15(TC -面加熱-面進行反應，反應結束後直接取 出。但並不限定於本反應條件。 酸酐、聚羧酸可分別單獨使用或者使用2種以上。於 此情形時，酸酐與聚羧酸之比率以其重量比計為9〇/ 1〇〜 20/80’ 尤佳為 80/20〜30/70。 本發明之硬化性樹脂組成物中，相對於環氧樹脂之環 氧基1當量，硬化劑之使用量以官能基當量計較佳為〇5〜 1.5當量。進而較佳為〇·7〜L1當量，尤佳為〇;〜〗〇當量。 於相對於環氧基1當量而未達〇5當量之情形、或者超出 1 ·5當量之情形時，均有硬化不完全而無法獲得良好之硬化 物性之虞。 本發明之硬化性樹脂組成物Α中，亦可將硬化促進劑 (硬化觸媒）與硬化劑併用。作為可使用之硬化促進劑之 具體例，可列舉：2 —甲基咪唑' 2 —苯基咪唑、2 —十一烷 基咪唑、2 —十七烷基咪唑、2 一苯基_ 4 _甲基咪唑、i — 苄基一2—苯基咪唑、丨―苄基_2_甲基咪唑、丨―氰乙基 —2 —曱基咪唑、1—氰乙基—2_苯基咪唑、氰乙基—2 201211093 —十一烷基咪唑、2,4~~二胺基—6_ (2,一甲基咪唑乙基 -均三畊、2,4 —二胺基—6 — (2，一十一烷基咪唑（1·))乙基— 均三of、2,4一二胺基一6 — (2，一乙基，4—甲基咪唑（1'))乙 基一均二崎、2，4 —二胺基一6(2’ 一甲基咪唑_ (1，））乙基一均 三姘一異三聚氰酸加成物、2_甲基咪唑異三聚氰酸之2: 3 加成物、2—苯基咪唑異三聚氰酸加成物、2一苯基一 3,5_ 一羥甲基咪唑、2 —苯基—4 —羥曱基—5—甲基咪唑、1 — 氰乙基一 2—苯基一3，5 —二氰基乙氧基甲基咪唑之各種咪 唑類；及該等咪唑類與鄰苯二甲酸、間苯二甲酸 曱酸、1，2,4 —笨二甲酸、焦蜜石酸、萘二甲酸、馬來酸、 草酸等多元羧酸之鹽寧；二氰二胺等醯胺類；丨，8一二吖雙 裱（5,4’0)十 7 —烯等二吖化合物及該等之四苯基硼酸 鹽；苯盼盼醛清漆等之鹽類；與上述多元羧酸類、或次膦 駿（phosphinicacid)類之鹽類；溴化四丁基銨、溴化鯨蠟 基三曱基銨、溴化三辛基甲基銨等銨鹽；三苯膦、三（甲苯 甲醯基)膦、溴化四苯基鱗、四苯基鱗四苯基硼酸鹽等膦類 或鐫化合物·’ 2,4,6-三胺基曱基苯紛等㈣·，胺加合物、 辛酸亞錫等金屬化合㈣，及將該等硬化促進劑製成微膠 囊之微膠囊型硬化促進料。使用該等硬化促進劑中哪一 種’係根據例如透明性、硬化速度或作業條件之類對所得 之透明樹脂組成物所要求之特性而適當選擇。硬化促進劑 相對於環氧樹脂1〇〇重量份’通常以〇 〇〇1〜15重量份之範 圍使用。 中亦可含有含磷化合物201211093 VI. Description of the Invention: [Technical Field] The present invention relates to a curable resin composition having a specific structure, and to a curable resin composition suitable for use in electrical and electronic materials, particularly in optical semiconductor applications And hardened matter. [Prior Art] The epoxy resin is cured by various hardeners and is a cured product excellent in mechanical properties such as water resistance, chemical resistance, heat resistance, electrical properties, etc., and is used for an adhesive, a coating, a laminate, and a molding. Materials, casting materials, resists and other fields. In addition, in the field of optoelectronics, it has been highly informative in recent years. In order to successfully transmit and process the information of Magic, the technology for generating optical signals is being developed to replace the previous transmission of signals by electrical wiring. Among them, in the field of optical components such as optical waveguides, blue LEDs, and optical semiconductors, it is expected to develop resins having excellent transparency. Especially in the field where optical characteristics are required, for example, in the field of LED products, etc., an acid-based hardened material of an epoxy resin is often used. As an epoxy resin used for a sealing material for such an optical semiconductor element such as an LED product, a heat-resistant, transparent, and mechanical property balance is widely used. (IV) A glycidyl ether type epoxy represented by an A-type epoxy resin Resin composition. However, the short-wavelength of the wavelength of the LED product (mainly the blue luminescence below (10)) indicates that the sealing material is colored on the LED wafer due to the influence of short-wavelength light, and finally as a LED product. The illuminance is reduced. 201211093 Therefore, the alicyclic cyclic oxime resin represented by 3,4-epoxycyclohexyl decyl _ 3,4, an epoxycyclohexyl methacrylate, and the glycidyl ether type cyclic oxime resin having an aromatic ring Since the composition is excellent in transparency, it is actively studied as an LED sealing material. (Patent Documents 1 and 2) However, in recent years, LED products have been exposed to illumination or a backlight of τν, and the luminance has been further developed, and a large amount of heat is generated when the LED is turned on. Therefore, the resin composition using the alicyclic epoxy resin as described above is also colored on the [ED wafer, and finally the illuminance is lowered as an LED product. Therefore, it has been desired to develop a resin composition which improves durability. CITATION LIST Patent Document 2: Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. 445 [Summary of the Invention] The hardness and brittleness of the cured product of the 5% of the oxygen resin are the same as the problem. This is also the same as the case of the sealing material used as the previous LED. Since the LED sealing material becomes important due to the light emission thereof, it is impossible to mix the helmet filler # in a large amount compared with the general sealing material, and the mechanical $ cannot be performed. Strong and strong. Therefore, cracks and the like are likely to occur, and the toughness is required for the sealing material: the structure of the tree. In order to improve, the addition of an alcohol such as trishydroxyl] has been studied (Patent Document 3), and the addition of such alcohols = for example, when curing with an acid (4), the reaction of an alcohol with an acid needle is carried out from room temperature, The material has a large disadvantage and the properties become very poor. The stability of human-free compound 4 201211093 = external 'Because of the presence of LED in the above epoxy resin is studying the problem of changing the polyoxynoxy resin or polyfluorene oxide for a long time, into the tender skeleton (specifically, quality: oxygen " The conductive grease represented by the purpose of the purpose is used as a sealing material. (Patent Document 4) The tree of the key frame of the moon is compared with the epoxy resin of the epoxy resin skeleton, and the white is widely used for the sealing material of the LED product. The temple, from the viewpoint of coloring on the led wafer, can be said to be superior to the resin: durability. However, it is resistant to gas permeability [is therefore used in the use of poly:: resin or poly-oxygen modified epoxy resin as the LED sealing material. (4) The color on the wafer does not become a problem. However, there are the following problems: silver components plated on a metal lead frame (ie, a component in an LED package) (silver plating is performed to improve reflectance), and discoloration or blackening is the most Performance is reduced. Therefore, on the market, an epoxy resin composition material having high durability against light or heat and satisfying gas permeation resistance is more desirable as an optical material than the conventional alicyclic epoxy resin. The present invention has been made in view of the problems of the prior art described above, and an object thereof is to provide a curable resin composition which can be suitably used as an optical material to provide excellent storage stability and hardening stability, and to light or heat. A cured product excellent in durability or gas permeability. The present inventors have conducted intensive studies in view of the actual situation as described above to complete the present invention. That is, the present invention relates to: 201211093 (1) A curable resin composition containing an epoxy resin having an epoxycyclohexane structure and an alcohol having a tricyclodecane structure; (2) as in the above item (丨) a curable resin composition, wherein the epoxy resin having an epoxy ring-fired structure is an alicyclic epoxy resin; (3) a curable resin composition according to the above item (丨), wherein the epoxy ring has an epoxy ring The epoxy resin of the structure is an epoxy resin having an epoxycyclohexane structure and a decane structure; (4) A curable resin composition containing the curability of any one of the above items (1) to (3) a resin composition and a hardener and/or a hardening accelerator; (5) The curable resin composition according to the above item (4), wherein the hardener is an acid anhydride; (6) a cured product which is the former item (4), (5) The curable resin composition of any one of the above items (4), (5), wherein the curable resin composition of any one of the above items (4) and (5) is obtained. The curable resin composition of the present invention is excellent in storage stability and stability of a cured product, and is excellent in coloring property against light and heat, and gas permeation resistance. Therefore, it is used as an optical material, particularly for a light semiconductor (led product, etc.) ) It is extremely useful for materials and sealing materials. In particular, by forming the epoxy resin into a structure containing an epoxycyclohexane structure and a siloxane structure in the skeleton, a cured product having more excellent gas resistance can be formed. In addition, the curable resin composition of the present invention is excellent not only in moisture permeability resistance, moisture absorption resistance, and adhesion, but also in the case of forming a thermosetting resin composition having an acid anhydride as a curing agent 201211093. The effect of volatilization during hardening. [Embodiment] Hereinafter, the curable resin composition of the present invention will be described. The epoxy resin of the present invention is an epoxy resin having an epoxycyclohexane structure. The epoxy resin having an epoxycyclohexane structure in the present invention may, for example, be an alicyclic type oxy-resin or an epoxy resin having an epoxycyclohexane structure and a decane structure. The alicyclic epoxy resin is not particularly limited as long as it has a compound having two or more epoxycyclohexane structures and has an alicyclic structure in its structure. ~ Specifically, it can be exemplified by the esterification reaction of cyclohexene carboxylic acid with an alcohol or the esterification reaction of cyclohexene sterol with a carboxylic acid (Tetrahedr〇n ν〇1·36 p. 2409 (1980), Tetrahedron Letter p. 4475 (1980), etc., and the method of "the method of loading"), and further, "the transesterification reaction of a cyclohexene carboxylate (method described in JP-A-2006-052187, etc.) The compound produced is oxidized and the like. The alcohol is not particularly limited as long as it is a compound having an alcoholic trans group, and examples thereof include ethylene glycol, propylene glycol, 1> 3-propylene glycol, U2-butanol, anthracene, 4-butanediol, and i. , 5-pentanediol, 1,6-hexanediol, cyclohexanedimethanol, 2,4-diethylpentanediol, 2-ethyl-2-butyl-1,3-1,3-propanediol, neopentyl a glycol such as an alcohol, a tricyclodecane dimethanol or a decenediol; glycerin, dimethylolethane, trimethylolpropane, trishydroxybutane, 2 — 201211093 hydroxymethyl-l 4 ~~ τ, triols such as butanol; neopentyl alcohol, = tetraol such as formazan propane. Also, ", 砰-hydroxymethyl group", as the carboxylic acid, may be exemplified by: oxalic acid, maleic acid, cyanic acid, o-I y, - formazan, m-dicarboxylic acid, adipic acid, ring The calcined dicarboxylic acid or the like is not limited thereto. The term "r" can be exemplified by the reaction of a cyclohexenal derivative with an acetal of an alcohol, and the method is as follows. The acetalization reaction can be carried out, for example, p--face, 隹... using a solution such as toluene or xylene, and performing azeotropic dehydration on the surface. - _. Ding reaction method (US Patent No. 2945008... Concentrated hydrochloric acid After dissolving the polyol, the surface is added slowly: the method used (Japanese Unexamined Model No. 48-9); the method of dragging the right, ./^ (U.S. Patent No. 3,926,540) ^ Agent for the reaction of f method (Japan Special Kaiping 215 State:: newspaper) using solid acid catalyst method (曰本特开2〇.7 _ 23.992 '么) #. Self-structural stability In terms of nature, a cyclic acetal structure is preferred. The external one may include ethylene cyclohexene or limonene, dicyclopentadiene, : winter diene, Oxidized polycyclic olefins such as dicyclopentadiene, dicyclohexene, and octadiene are oxidized, etc. Specific examples of such epoxy resins include erl_422i and erl 2299 (all The product name 'is D〇w _ _ _, ^ ΡΕ ΡΕ ΡΕ ( ( ( ( 实 实 实 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( In the above (Reference: General Epoxy Tree Foundation) ~~1). These may be used alone or in combination of two or more. As an epoxy compound having an epoxy ring structure and a stone structure Resin, 8 201211093 is not particularly limited as long as it is an organic polyoxo compound having an epoxy ring-fired structure, and in particular, in the present invention, "the use of an alkoxylate having an epoxycyclohexyl group is used for The cycloaliphatic-type organic polyfluorene having a three-dimensionally stretched network structure as described in the following publication is exemplified by the sol-gel reaction of the raw material. Oxytomane: JP-A-2004-256609, Japan Special 2〇〇4 — 346M4, International Publication No. 2〇〇4/〇7215〇, Japanese Patent Laid-Open No. 2006-8749, International Publication No. 2〇〇6/〇〇399〇, Japanese Patent Laid-Open No. 2006-104248, International Japanese Laid-Open Patent Publication No. 2/1359/9, 曰本特开2004-10849, Japanese Patent Laid-Open No. Hei. No. 4-359933, International Publication No. 2005/i 00445, and Japanese Special Publication No. 2-8丨7464〇, etc. The structure of the organopolyoxane is not particularly limited, but since the simple three-dimensional network structure of the siloxane compound is too hard, it is expected to relax the structure of the hardness. In the present invention, a block structure having a polyfluorene oxide segment and a sesquiterpene oxide structure obtained by a sol-gel reaction in one molecule is particularly preferable as a method for producing such a compound. A manufacturing method and structure as described in International Publication No. 2/026714. Examples of the alcohol having a bicyclic brothel structure include tricyclodecane dimethyl alcohol, decyl dicyclodecane dimethanol, pentacyclopentadecanediol, and the like. As such a compound, 彳 exemplifies an olefin of a cyclopentane # or a methyl epoxide (for example, a cyclopentadiene, a methyl dicyclopentadiene, a tricyclopentadiene, etc.) 9 201211093 part A method of producing an alcohol by reduction after hydrogenation. The curable resin composition of the present invention is obtained by uniformly mixing "the above-mentioned epoxy resin having a ring-shaped structure having a ring structure and an alcohol having a tricyclic sinter structure" at a specific ratio. As a method of uniformly mixing, for example, a method of melt-mixing one side of a range equal to 〇~100 °c or using an organic life agent can be used to remove the solvent. A method of the curable resin composition of the present invention. As the blending amount, the alcohol having a three-ring brothel structure with respect to the epoxy resin having an epoxycyclohexene structure is i 5 to 4% by weight, preferably 2 to 30 by 1%, and particularly preferably 2 · 25 to 25% by weight. Excess alcohol has the possibility of causing a problem of poor hardening. Therefore, it is not preferable, and if it is too small, it is difficult to exert an effect. The curable resin composition of the present invention not only improves the air permeability, the transparency, the moisture permeability, the moisture absorption resistance, the adhesion resistance, but also the hardening of the thermosetting resin composition which is made of an acid anhydride as a curing agent. The effect of the volatilization of the time 'the release of the compound to the ring is also:= system, which also contributes to the safety of the operator. In particular, it is particularly useful in applications such as surface coating f LED, film coating material or film using only a small amount of resin, which helps to solve the problem of "acid anhydride volatilization, balance failure of hardener and epoxy, poor hardening, and inability to obtain real Problems such as hardened materials and serious coloration. Further, the curable composition of the present invention is less colored when cured. In the curable resin composition of the present invention, an epoxy resin having an epoxycyclohexane structure as an essential component may be used alone, and the above epoxy resin having an epoxycyclohexane structure of 201211093 may be used together with other epoxy resins. Use it together. In the case of use in combination, the proportion of the above epoxy resin in the total epoxy resin is preferably 70% by weight or more, and particularly preferably 80% by volume. Other epoxy resins which can be used in the curable resin composition of the present invention include novolac type epoxy resin, bisphenol A type epoxy resin, conjugated epoxy resin, and triphenyl decene type epoxy. Resin, phenol aralkyl type epoxy resin, and the like. Specific examples thereof include bisphenol A, bisphenol S, thiodisulfonium, bisphenol, diphenol, 4,4, monophenol, 2,2, monophenol, 3, 3, and 5, 5,~ tetramethyl-[U-biphenol]- 4,4·-diol, hydroquinone, resorcinol, naphthalenediol, tris-(4-hydroxyphenyl)methane, 1,1 , 2,2-tetrakis(4-hydroxyphenyl)ethane; phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde , acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-fine acetophenone, dicyclopentadiene, furfural, 4,4, a pair (gas methyl group ~ Biphenyl, 4,4'-bis(decyloxymethyl)-1,1,biphenyl, 1,4-bis(gasmethyl)benzene, anthracene, 4-bis(decyloxyfluorenyl)benzene Polycondensate and the like, such as brominated bisphenols such as tetrabromobisphenol A; glycidyl ether compounds derived from alcohols, alicyclic epoxy resins, glycidylamine epoxy resins, glycidol S is a solid or liquid epoxy resin such as an epoxy resin, but is not limited thereto. The curable resin composition of the present invention may contain a curing agent and/or a curing accelerator (curing catalyst). The following 'thermal hardening by a curing agent (curable resin composition A), by acid hardening) Catalytic curing of the accelerator (curable resin composition B) 201211093. The heat curing by the curing agent (curable resin composition A) is a curing agent contained in the curable resin composition A of the present invention, for example, Examples of the amine-based compound, the acid anhydride-based compound, the amine-based compound, the phenol-based compound, and the carboxylic acid-based compound. Specific examples of the hardener that can be used include diamine-based bismuth and diethylenetriamine. , succinylamine, diaminodiphenyl sulfone, isophorone diamine, dicyanodiamine, polyamine resin synthesized from dilinoleic acid dimer and ethylenediamine, o-benzene Dicarboxylic anhydride, trimellitic anhydride, pyrogallic anhydride, maleic anhydride, tetrahydrophthalic anhydride, mercaptotetrahydrophthalic anhydride, mercaptoic acid anhydride (methyl nadic) Anhydride), phthalic anhydride, hexanitrophthalic acid Liver, methyl hexahydro phthalic anhydride, butyl succinic anhydride, bicyclo [2, 2, 丨] Gengyuan - 2,3-diphthalic anhydride, methyl bicyclo [2, 2, 1] g Alkane-2,3-dicarboxylic anhydride, cyclohexane-1,2,4-tricarboxylic acid-ι,2-anhydride, bisphenol A, bisphenol F, bisphenol s, bisphenol 'nonylphenol, 4 , 4, monophenol, 2, 2, monophenol, 3,3', 5,5, tetramethyl-[1, fluorene-biphenyl]-4,4, monodiol, hydroquinone , resorcinol, naphthacene, tris(4-hydroxyphenyl)methane, tetrakis(4-hydroxyphenyl)ethene; expectant (phenol, alkyl substituted phenol, naphthol, Alkyl-substituted naphthoquinone, dihydroxybenzene, dihydroxynaphthalene, etc.) with formaldehyde, acetaldehyde, benzaldehyde, p-benzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, bicyclo Pentadiene, furfural, 4,4,_bis (gas methyl)-1,1,biphenyl, 4,t-bis(decyloxy)-M,-biphenyl, anthracene, 4 pairs a polycondensate of (gas methyl)benzene, 1,4-bis(decyloxymethyl)benzene, and the like; and a modified bisphenol, tetrabromobisphenol A or the like Trifluoroborane burn - amine complexes, derivatives vein, 12201211093 Woo alkylene condensates of phenols and the like, but is not limited to such. These may be used alone or in combination of two or more. In the present invention, a compound having an acid anhydride structure and/or a carboxylic acid structure represented by the above-mentioned acid liver or carboxylic acid resin is particularly preferred. The compound having an acid anhydride structure is preferably methyltetrahydrophthalic anhydride, methylic acid anhydride, ceric acid anhydride, hexahydrophthalic acid wild, mercaptohexahydrophthalic anhydride, or Alkane tetracarboxylic anhydride, hexane-1,2,4-tricarboxylic acid-1'2-anhydride, etc., especially preferably mercaptohexahydrophthalic anhydride, cyclohexane-1,2,4-13 Tannic acid - i, 2__ rape. The compound having a tickitic structure (hereinafter referred to as polyglycolic acid) is preferably a 2 to 4 functional polycarboxylic acid, and more preferably obtained by subjecting a 2 to 4 functional polyol to an acid anhydride addition reaction. The polyacid is slow. The 2~4-functional polyol is not particularly limited as long as it is a compound having an alcoholic hydroxyl group, and examples thereof include ethylene glycol, propylene glycol, ... propylene glycol, U2-butanediol, M-butanediol, and Pentanediol, ι>6-hexanediol, cyclohexanedimethanol, 2,4-diethylpentanediol, 2-ethyl-2-butyl-i, 3-propanediol, neopentyl glycol, Tricycloanthrene, di-methanol, reduced glycerol, tri-methyl ketone, tri-methyl propyl ketone, triterpenoid trimethyl butyl butyl glycol and other triols; neodymidine, One or two tetraethers such as methyl propyl acetate, etc. The preferred 2~4 functional polyols are cyclohexanedimethanol, 24_diethylpentanediol, 2-ethyl-2-butyl , 3_ propylene glycol, neopentyl:: bicyclic oxime H-lowering diol or other branched or cyclic alcohols. 13 201211093 As an acid anhydride for the production of polyphenolic acid, preferably: methyl tetrachloro Phthalic anhydride: methylic acid anhydride, ceric acid anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic acid needle, Ding according to the four conditions, tetracarboxylic anhydride, bicyclo [2, 2 , 1] heptane-2,3-dicarboxylic acid liver Methyl dicycloheptane-2,3-dicarboxylic acid cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride, etc. The conditions of the addition reaction are not specified, and one of the specific reaction conditions For the y method: the acid needle and the polyol are reacted at 40 ° C to 15 (TC - surface heating - surface under conditions of no catalyst or solvent), and the reaction is directly taken out after the reaction is completed. However, it is not limited to this. The acid anhydride and the polycarboxylic acid may be used singly or in combination of two or more kinds. In this case, the ratio of the acid anhydride to the polycarboxylic acid is 9 〇 / 1 〇 to 20 / 80 Å by weight ratio, particularly preferably 80. In the curable resin composition of the present invention, the curing agent is preferably used in an amount of from 〇5 to 1.5 equivalents based on 1 equivalent of the epoxy group of the epoxy resin. It is 〇·7~L1 equivalent, especially preferably 〇;~〗 〇 。. In the case of less than 5 equivalents relative to 1 equivalent of epoxy group, or more than 1.5 equivalents, there is incomplete hardening. However, it is not possible to obtain a good hardening property. In the curable resin composition of the present invention, a hardening accelerator (hard) may also be obtained. The catalyst is used in combination with a hardener. Specific examples of the hardening accelerator that can be used include 2-methylimidazole ' 2 -phenylimidazole, 2 -undecylimidazole, and 2 -heptadecylimidazole. 2-Phenyl-4 _methylimidazole, i-benzyl-2-phenylimidazole, hydrazine-benzyl-2-methylimidazole, hydrazine-cyanoethyl-2-mercaptoimidazole, 1-cyanoethyl —2—Phenyl imidazole, cyanoethyl-2 2 201211093 — undecylimidazole, 2,4~~diamino—6 — (2, monomethylimidazolium-average three-pill, 2,4-diamine —-6 — (2, undecylimidazolium (1·)) ethyl—same tri-, 2,4-diamino- 6-(2,1-ethyl, 4-methylimidazole (1' )) ethyl-one homo-bis-sodium, 2,4-diamino- 6 (2'-methylimidazole _ (1,)) ethyl-all-trimethylene-iso-cyanuric acid adduct, 2_A 2:3 adduct of 2-imidazolyl isocyanuric acid, 2-phenylimidazole isocyanuric acid addition product, 2-phenyl-3,5-monomethylolimidazole, 2-phenyl-4-yl- Various imidazoles of hydroxymethyl 5-methylimidazole, 1-cyanoethyl-2-phenyl- 3,5-dicyanoethoxymethylimidazole And the salts of these imidazoles with polycarboxylic acids such as phthalic acid, isophthalic acid, phthalic acid, pyromic acid, naphthalene dicarboxylic acid, maleic acid, oxalic acid, etc. a guanamine such as dicyandiamide; a ruthenium compound such as ruthenium, ruthenium bismuth (5,4'0), or a tetraphenylborate; and phenylpanoran varnish; a salt; a salt of the above polycarboxylic acid or a phosphinic acid; an ammonium salt such as tetrabutylammonium bromide, cetyltrimethylammonium bromide or trioctylmethylammonium bromide; Phosphine or antimony compound such as triphenylphosphine, tris(tolylmethyl)phosphine, tetraphenylphosphonium bromide or tetraphenylphosphinium tetraphenylborate·' 2,4,6-triaminodecylbenzene (4), a metal compound such as an amine adduct or stannous octoate (4), and a microcapsule-type hardening accelerator which is a microcapsule of the hardening accelerator. Which of these hardening accelerators is used is appropriately selected depending on the properties required for the obtained transparent resin composition, such as transparency, curing rate, or working conditions. The hardening accelerator is usually used in an amount of from 1 to 15 parts by weight based on 1 part by weight of the epoxy resin. May also contain phosphorus compounds

本發明之硬化性樹脂組成物A 15 201211093 作為難燃性賦予成分。作為含填化合物，可為反應型者’ 亦可為添加型者。作為含磷化合物之具體例，玎列舉：磷 酸二曱酯、填酸三乙酯、碟酸三甲苯酯、璘酸二（一甲笨） 酯、磷酸曱苯基二苯酯、磷酸甲苯基—2,6—二（二曱苯）酯、 1，3 ~伸苯基雙（磷酸二（二曱苯）醋）、I〆一伸苯基雙（填酸二 (二曱笨）酯）、4,4, ~聯苯基（填酸二（二甲苯）δ旨）等磷酸酯 類；9,10 —二氫一 9 -氧雜-1〇_磷雜菲一 10—氧化物、 1〇(2’5—二羥苯基）—1〇^—9一氧雜—1〇—磷雜菲一1〇—氧 化物等膦類；使環氧樹脂與上述膦類之活性氫反應所得之 含碟環氧化合物、紅磷等，較佳為磷酸酯類、膦類或含磷 環氡化合物，尤佳為1，3_伸苯基雙（磷酸二（二甲苯）酯）、 1’4 —伸苯基雙（磷酸二（二曱苯）酯）、4,4，_聯苯基（磷酸二 (二甲苯）S旨）或含磷環氧化合物。含磷化合物之含量較佳為 含磷化合物/全部環氧樹脂=〇」〜〇 6 (重量比）。若未達 〇· 1 ’則有難燃性不充分之擔憂，若超出〇 6，則有對硬化物 之吸濕性、介電特性造成不良影響之擔憂。 進而，本發明之硬化性樹脂組成物Α中亦可視需要而 摻合黏合劑樹脂。作為黏合劑樹脂，舉： 縮㈣脂:丙稀酸系樹脂 '環氧_尼龍系樹脂：-齡 系樹月日、環氧-NBR系樹脂、聚酿胺系樹脂、聚酿亞胺系 樹月曰、聚⑦氧系樹脂等’但並不限定於該等。黏合劑樹脂 之摻合量較佳為不損及硬化物之難燃性、耐熱性之範圍， 相對於樹脂成分100重量份，通常為〇 〇5〜5〇重量份，較 佳為視需要使用〇.〇5〜20重量份。 201211093 本發明之硬化性樹脂組成物A中，可視需要添加無機 填充劑。作為無機填充劑，可列舉：結晶二氧化矽、炼融 二氧化矽 '氧化鋁、鍅英石、矽酸鈣、碳酸鈣、碳化矽、 氮化矽、氮化硼、氧化錯、鎂橄欖石、塊滑石、尖晶石、 二氧化欽、滑石等粉體或將該等球形化而成之顆粒等但 並不限定於該等。該等可單獨使用，亦可使用2種以上。 該等無機填充劑之含量係使用在本發明之硬化性樹脂組成 物中占0 9 5重量％之量。進而，本發明之硬化性樹脂組成 物A中可添加：矽烷偶合劑、硬脂酸、棕櫚酸、硬脂酸鋅、 硬脂酸鈣等脫模劑；顏料等各種摻合劑；羧酸鋅（2 —乙基 己酸辞硬月g酸鋅、二十二酸辞、肉豆缝酸辞）或鱗酸酿 鋅（鱗酸辛㈣、鱗酸硬脂㈣等）等鋅化合物；各種熱 硬化性樹脂。 於將本發明之硬化性樹脂組成物A肖於光學材料、尤 其是光半導體密封劑之情形時，上述使用之無機填充材料 之粒徑可藉由使用奈米級水準之填充材料，在不妨礙透明 性的情形下補充機械強度等。自透明性之觀點而言，作為 奈米級水準之標準較佳為使用平均粒徑為500 run以下、尤 佳為平均粒徑為200 nm以下之填充材料。 ;將本發明〜硬化性樹脂組成⑯A肖於光學材料、尤 其是光半導體密封劑之情形時，可視需要添加螢光體。榮 "系”有如下作用者.例如藉由吸收由藍色[ED元件發 _色光之'^刀，發出經波長轉換之黃色光，而形成 白色光。將螢光體減分散於硬化性樹脂組成物中後密封 17 201211093 光半導體。作為螢光體，並無特別限制，可使用先前公知 之螢光體，例如可列舉稀土類元素之鋁酸鹽、硫代沒食子 酸鹽、原矽酸鹽等《更具體而言，可列舉：YAG螢光體、 TAG螢光體、原矽酸鹽螢光體、硫代五倍子酸鹽螢光體、 硫化物螢光體等螢光體，可例示：YA103:Ce、Y3Al5012:Ce、 Y4Al2〇9:Ce、Y2〇2S:Eu、Sr5(P〇4)3Cl:Eu、（SrEu)0.Al203 等。 作為該螢光體之粒徑，係使用該領域中公知之粒徑，但作 為平均粒徑’較佳為1〜250 /zm，尤佳為2〜50 //m。於 使用該等螢光體之情形時，相對於該樹脂成分丨〇〇重量份， 其添加量為1〜80重量份，較佳為5〜60重量份。 於將本發明之硬化性樹脂組成物A用於光學材料、尤 其是光半導體密封劑之情形時，為防止各種螢光體之硬化 時沈澱，可添加以二氧化矽微粉末（亦稱為Aer〇sil或 Aerosol)為代表之觸變性賦予劑。作為此種二氧化矽微粉 末’例如可列舉：Aerosil 50、Aer〇sil 9〇、八⑽川13〇、The curable resin composition A 15 201211093 of the present invention is a flame retardancy imparting component. As the filler-containing compound, it may be a reactive type or may be an additive type. Specific examples of the phosphorus-containing compound include bismuth diphosphate, triethyl sulphate, tricresyl oleate, bis(monomethyl) decanoate, phenyl diphenyl phosphate, and toluyl phosphate. 2,6-di(diphenylene) benzoate, 1,3~phenylene bis(di(diphenylene) vinegar), I phenylene bis(di(diphenyl) ester), 4 , 4, ~biphenyl (filled with di(xylene) δ) and other phosphates; 9,10-dihydro-9-oxa-1〇_phosphaphenanthrene-10-oxide, 1〇 ( a phosphine such as 2'5-dihydroxyphenyl)-1 〇^-9-oxa- 1 〇-phosphaphenanthrene- 1 〇-oxide; the epoxy resin is reacted with the active hydrogen of the above phosphine The dish epoxy compound, red phosphorus, etc., preferably a phosphate ester, a phosphine or a phosphorus-containing cyclic ruthenium compound, particularly preferably 1,3_phenylphenyl bis(xylylene phosphate), 1'4 — Phenyl bis(di(diphenylene) phosphate), 4,4,-biphenyl (di(xylene)S) or a phosphorus-containing epoxy compound. The content of the phosphorus-containing compound is preferably a phosphorus-containing compound/all epoxy resin = 〇" to 〇 6 (weight ratio). If it is less than 〇·1', there is a concern that the flame retardancy is insufficient. If it exceeds 〇6, there is a concern that the hygroscopicity and dielectric properties of the cured product are adversely affected. Further, in the curable resin composition of the present invention, a binder resin may be blended as needed. As the binder resin, the following are: condensed (tetra) fat: acrylic acid resin 'epoxy _ nylon resin: - aging tree, day, epoxy-NBR resin, polyamine resin, poly urethane tree Moonworm, poly 7-oxygen resin, etc. 'but are not limited to these. The blending amount of the binder resin is preferably in a range that does not impair the flame retardancy and heat resistance of the cured product, and is usually 〇〇5 to 5 parts by weight based on 100 parts by weight of the resin component, preferably used as needed. 〇.〇 5~20 parts by weight. 201211093 In the curable resin composition A of the present invention, an inorganic filler may be added as needed. Examples of the inorganic filler include crystalline cerium oxide, sulphurized cerium oxide 'alumina, bismuth, calcium silicate, calcium carbonate, cerium carbide, cerium nitride, boron nitride, oxidized oxalate, forsterite. The powder such as talc, spinel, dioxins, talc, or the like, or the like, is not limited thereto. These may be used alone or in combination of two or more. The content of the inorganic filler is used in an amount of 9.55% by weight in the curable resin composition of the present invention. Further, the curable resin composition A of the present invention may contain a mold release agent such as a decane coupling agent, stearic acid, palmitic acid, zinc stearate or calcium stearate; various admixtures such as a pigment; and zinc carboxylate ( 2 -ethylhexanoic acid, hard acid, g-zinc, twenty-six acid, and soy-sealed acid) or zinc-based compounds such as zinc sulphate (succinic acid (tetra), citric acid stearic acid (tetra), etc.; various thermosetting properties Resin. When the curable resin composition A of the present invention is used in the case of an optical material, particularly a photo-semiconductor encapsulant, the particle size of the inorganic filler used above can be prevented by using a nano-level filler. In the case of transparency, mechanical strength and the like are supplemented. From the viewpoint of transparency, it is preferable to use a filler having an average particle diameter of 500 run or less, and particularly preferably an average particle diameter of 200 nm or less, as a standard for the nano level. When the composition of the present invention to the curable resin 16A is used in the case of an optical material, particularly an optical semiconductor encapsulant, a phosphor may be added as needed. Rong "system has the following effects. For example, by absorbing the wavelength-converted yellow light by the blue [ED device _ color light'^ knife, white light is formed. The phosphor is less dispersed in the hardenability. Post-sealing of the resin composition 17 201211093 Optical semiconductor. The phosphor is not particularly limited, and a conventionally known phosphor can be used, and examples thereof include an aluminate of a rare earth element, a thiogallate, and an original. More specifically, a phosphor such as a YAG phosphor, a TAG phosphor, an orthosilicate phosphor, a thiopentate phosphor, or a sulfide phosphor may be mentioned. YA103: Ce, Y3Al5012: Ce, Y4Al2〇9: Ce, Y2〇2S: Eu, Sr5(P〇4)3Cl:Eu, (SrEu)0.Al203, etc. As the particle diameter of the phosphor, The particle diameter known in the art is used, but the average particle diameter ' is preferably from 1 to 250 /zm, particularly preferably from 2 to 50 //m. In the case of using the phosphor, relative to the resin component The amount by weight of the bismuth is 1 to 80 parts by weight, preferably 5 to 60 parts by weight. The curable resin composition A of the present invention is used for In the case of a material, in particular, a photo-semiconductor encapsulant, a thixotropy-imparting agent typified by cerium oxide micropowder (also referred to as Aer〇sil or Aerosol) may be added in order to prevent precipitation of various phosphors upon hardening. Examples of such a cerium oxide micropowder include Aerosil 50, Aer〇sil 9〇, and 八(10)川13〇.

Aerosil 20〇.Aerosil 30〇.Aerosil 38〇.Aerosil OXSO^Aerosil TT600 ^ Aerosil R972 ^ Aerosil R974 ^ Aerosil R202 ^ Aerosil R812 ' Aerosil R812S > Aerosil R805、RY2〇〇、rx200 (日 本Aerosil公司製造）等〇 於將本發明之硬化性樹脂組成物A心光學㈣、％ 其是光半導體密封劑之情形時，4防止著色，可含有作為 光穩定劑之胺化合物、或者作Α 乍為抗氧化材料之磷系化合物 或盼系化合物。 四（1，2,2,6,6 ~ 五曱 作為上述胺化合物，例如可列舉 18 201211093 基一4 一派咬基）_1，2,3,4 — 丁院四甲酸醋、四（2,2,6,6 —四曱 基—4 —派咬基尸1，2,3,4 — 丁院四曱酸酉旨、ι，2,3,4 — 丁烧四 曱酸與1，2,2,6,6—五甲基—4—哌啶醇及3,9一雙（2一羥基 -1，1 —二甲基乙基）一2,4,8，1〇 —四氧雜螺[5,5]十一烷之混 合醋化物、癸二酸雙（2,2，6,6 —四甲基一4 一略唆基）癸二酸 酯、碳酸雙（1 一十一烷氡基一2,2,6,6 —四甲基哌啶一4 —基） 醋、曱基丙稀酸2，2,6，6 —四曱基—4 —娘咬基醋、癸二酸雙 (2，2,6,6 —四甲基一 4 —哌啶基）醋、癸二酸雙0,2,2,6,6 -五 甲基一4 —哌啶基）酯、4 —笨甲醯氧基—2,2,6,6—四曱基哌 啶、1 — [2 — [3—（3，5—二一三級丁基_ 4_羥苯基）丙醯氧基] 乙基]一 4 — [3 —（3,5 —二一三級丁基_4_羥苯基）丙醯氧基] 一 2,2,6,6—四甲基哌啶、甲基丙烯酸^2,6,6 -五曱基一4 —哌啶基酯、雙（1，2,2,6,6—五曱基一4_哌啶基）[[3,5—雙 (1，1一二曱基乙基）一 4—羥苯基]甲基]丁基丙二酸酯、癸二 酸雙（2,2,6,6 —四曱基一1(辛氧基）一4 —派咬基）酯、1，1 一二 甲基乙基氫過氧化物與辛烷之反應生成物、Ν,Ν'，Ν"，Ν"·-θ 一（4,6 —雙一（丁基一（Ν —曱基一 2,2,6,6 —四曱基0底咬一4 _基）胺基）—三〇井一2—基）一4,7—二氣癸烧一1，10—二 胺、二丁基胺一1，3,5 —三砷一Ν，Ν· —雙（2,2,6,6 -四曱基一4 —哌啶基）一1，6—己二胺與Ν —（2,2,6,6 —四曱基一4一哌啶 基）丁基胺之聚縮合物、聚[[6—(1，1，3,3_四曱基丁基）胺基 —1，3,5 —三崎一:2,4 —二基][(2,2,6,6 -四曱基一4 — 口底咬基） 亞胺基]六亞甲基[(2,2,6,6 —四曱基一4一 〇底咬基）亞胺 基]]、琥珀酸二曱酯與4一羥基一2,2,6,6_四甲基一 1 —裱啶 201211093 乙醇之聚合物、2,2,4,4 一四甲基一20—(/5 —月桂氧基羰基） 乙基一7 —氧雜一3,20 —二氮二螺環[5,1^2]二十—烷_ 21 -酮、；9 -丙胺醆N，一（2,2,6,6 —四甲基一4一哌啶基十 二烷基酯/十四烷基酯、N—乙醯基一 3 —十二烷基一 1_ (2,2,6,6 —四甲基—4 —。底咬基）》比略咬一 2,5 —二酮、2,2,4,4 —四甲基一7 —氧雜—3,20 —二氮二螺環[5，]^ i，]]二十一烷 —21— 酮、2,2,4,4~ 四甲基—21—氧雜一3,20 —二氮二環— [5’1，11，2] —二十—烷_2〇 一丙酸十二烷基酯//十四烷基 醋、丙二酸[(4 —曱氧基笨基）—亞曱基]—雙（1，2,2,6,6—五 甲基一 4 —哌啶基）酯、2,2,6,6 一四甲基一4 一哌啶醇之高級 脂肪酸酯、1,3—笨二羧基醯胺一N，N，—雙（2,2,6,6—四甲基 —4 —哌啶基）等受阻胺系、辛苯酮等二苯曱酮系化合物、2 — (2H—苯并三唑 — 2_基）—4_(1，1，3,3_四曱基丁基）苯 酚、2—（2—羥基—5_曱笨基）苯并三唑、2_[2_羥基—3 —(3,4’5’6 —四氫鄰苯二甲醯亞胺—甲基）—5 一曱基笨基] 苯并三唑、2—（3—三級丁基_2一羥基_5_曱基笨基5 一氣苯并三唑、2—(2—羥基一3,5—二一三級戊苯基）笨并 三°坐、曱基—3~(3—(2H-苯并三吐—2—基）—5_三級丁 基:4—__經苯基）丙酸醋與聚乙二醇之反應生成物、2-(2H 本并一唑一基）—6—十二烷基—4_甲基苯酚等苯并 -坐系化。物、2’4 -二-三級丁基苯基—3,5—二—三級丁 基—4—經基苯旨等苯甲酸㈣、2— (4,6_二苯基— 1，3，5 —二崎一2— A、 r r / 基）—5—[(己基）氧基]苯酚等三姘系化合 物4，尤佳為受阻胺系化合物。 20 201211093 作為上述光穩定材料之胺化合物可使用如下所示之市 售品。 作為市售之胺系化合物，並無特別限定，例如可列舉：Aerosil 20〇.Aerosil 30〇.Aerosil 38〇.Aerosil OXSO^Aerosil TT600 ^ Aerosil R972 ^ Aerosil R974 ^ Aerosil R202 ^ Aerosil R812 ' Aerosil R812S > Aerosil R805, RY2〇〇, rx200 (made by Japan Aerosil) etc. When the curable resin composition of the present invention A is optical (4) and % is a photo-semiconductor encapsulant, 4 prevents coloration, and may contain an amine compound as a light stabilizer or phosphorus as an anti-oxidation material. A compound or a desired compound. Four (1, 2, 2, 6, 6 ~ quinone as the above-mentioned amine compound, for example, 18 201211093 base- 4 one bite base) _1, 2, 3, 4 - Dingyuan tetracarboxylic acid vinegar, four (2, 2 ,6,6 —四曱基—4 — 派基基, 1,2,3,4 — 丁院四曱酸酉, ι,2,3,4 — 丁烧四曱酸和1,2,2 6,6-pentamethyl-4-piperidol and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,1〇-tetraoxaspiro[ Mixed vinegar of 5,5]undecane, bis(2,2,6,6-tetramethyl- 4 fluorenyl) sebacate, bis(1-11-decyl) a 2,2,6,6-tetramethylpiperidine-4-yl) vinegar, mercaptopropionic acid 2,2,6,6-tetradecyl- 4 - Ninja vinegar, azelaic acid bis ( 2,2,6,6-tetramethyl-4-piperidinyl)acetic acid, azelaic acid bis 0,2,2,6,6-pentamethyl-4-piperidinyl), 4醯oxy-2,2,6,6-tetradecylpiperidine, 1 — [2 — [3—(3,5-di-tri-butyl-4-hydroxyphenyl)propenyloxy] a group of 4,4-(3,5,5-di-tert-butyl-4-ylhydroxyphenyl)propanoxy]-2,2,6,6-tetramethylpiperidine ^2,6,6-pentamethyl- 4-piperidinyl methacrylate, bis(1,2,2,6,6-pentamethyl- 4-piperidinyl)[[3,5-double (1,1,2-diylethyl)-4-hydroxyphenyl]methyl]butylmalonate, azelaic acid bis(2,2,6,6-tetradecyl-1 (octyloxy) ) a 4-bite base ester, 1,1-dimethylol hydroperoxide and octane reaction product, Ν, Ν ', Ν ", Ν " · θ a (4,6 - Double one (butyl-(anthracene-fluorenyl- 2,2,6,6-tetradecyl-based base biting a 4-base) amine group) - Sanchajing-2 base) a 4,7-two gas Strontium-1,10-diamine, dibutylamine-1,3,5-tris-arsenic, bis-bis(2,2,6,6-tetradecyl-4-piperidyl) Polycondensation of 1,6-hexanediamine with hydrazine-(2,2,6,6-tetradecyl-4-piperidinyl)butylamine, poly[[6—(1,1,3,3) _ tetradecyl butyl)amino group - 1,3,5 - sakisaki: 2,4 -diyl][(2,2,6,6-tetradecyl- 4 - oleole) imine group ] hexamethylene [(2,2,6,6-tetradecyl- 4 〇 咬 base) imine]], dinonyl succinate and 4-hydroxy- 2,2,6,6_ Tetramethyl- 1 - Acridine 201211093 polymer of ethanol, 2,2,4,4-tetramethyl- 20-(/5-lauric oxycarbonyl) ethyl-7-oxa- 3,20-diaza dispiro[5, 1^2]tetradecane- 21-keto, 9-propylamine oxime N, mono(2,2,6,6-tetramethyl- 4 piperidinyl dodecyl ester/tetradecyl ester N-Ethylamino-3-dodecyl-1_(2,2,6,6-tetramethyl-4). Bottom bite base) is slightly biting a 2,5-dione, 2,2,4,4-tetramethyl-7-oxa-3,20-diaza dispiro[5,]^ i,] Twenty-alkane- 21-ketone, 2,2,4,4~tetramethyl-21-oxa-3,20-diazabicyclo-[5'1,11,2]-tetradecane 〇 十二 十二 十二 十二 十二 / / / / 十四 十四 十四 十四 十四 十四 十四 十四 十四 十四 十四 十四 十四 十四 十四 十四 十四 十四 十四 十四 十四 十四 十四 十四 十四 十四 十四 十四 十二 十二 十二 十二 十二 十二 十二Pentamethyl-4-piperidinyl ester, higher fatty acid ester of 2,2,6,6-tetramethyl-tetra-piperidinol, 1,3-phenyldicarboxyguanamine-N,N,- A benzophenone-based compound such as a bis(2,2,6,6-tetramethyl-4-piperidinyl) group such as a hindered amine or a benzophenone, or a 2-(2H-benzotriazol-2-yl group) —4—(1,1,3,3_tetradecylbutyl)phenol, 2-(2-hydroxy-5-indolyl)benzotriazole, 2_[2_hydroxy-3—(3,4' 5'6-tetrahydrophthalic acid imine-methyl)-5 fluorenyl benzotriazole, 2-(3-triphenyl)-2-hydroxy-5_indolyl 5 gas benzotriazole, 2-(2-hydroxy-3,5-di-p-pentylphenyl) stupid and three-degree sitting, sulfhydryl- 3~(3—(2H- And three spit - 2 - base) - 5_ tertiary butyl: 4- _ _ phenyl) propionic acid vinegar and polyethylene glycol reaction product, 2- (2H benzo- azole-based) - 6 - Benzo-sedation of dodecyl-4-ylphenol, 2'4-di-tert-butylphenyl-3,5-di-tert-butyl-4-yl-benzene Triterpenoids such as benzoic acid (tetra), 2-(4,6-diphenyl-1,3,5-disaki-2-A, rr/yl)-5-[(hexyl)oxy]phenol 4. A commercially available product as shown below is used as the amine compound of the above-mentioned light-stable material. The commercially available amine-based compound is not particularly limited, and examples thereof include, for example,

Ciba Specialty Chemicals 製造之 TINUVIN 765、TINUVIN 770DF、TINUV][N 144、TINUVI.N 123，TINUVIN 622LD、 TINUVIN 152、CHIMASSORB 944; Adeka 製造之 LA—52、 LA - 57、LA_ 62、LA - 63P、LA - 77Y、LA - 81、LA - 82、 LA — 87 等。 作為上述礙系化合物，並無特別限定，例如可列舉： 1,1,3 —三（2—曱基一4 —二一十三烷基亞磷酸酯一5 —三級 丁基苯基）丁烧、二硬脂基基新戊四醇二亞填酸酯、雙（2，4 一二一三級丁基苯基）新戊四醇二亞磷酸酯、雙（2，6 —二一 三級丁基一 4 —甲基苯基）新戊四醇二亞雄酸酯、苯基雙酚a 新戊四醇二亞填酸酯、二環己基新戊四醇二亞攝酸酯、三（二 乙基苯基）亞構酸酯、三（二一異丙基苯基）亞填酸酯、三（二 —正丁基苯基）亞磷酸酯、三（2,4 一二一三級丁基苯基）亞磷 酸酯、三（2，6 —二一三級丁基苯基）亞鱗酸酯、三（2，6 —二一 三級丁基苯基）亞磷酸酯、2,2，一亞甲基雙（4,6 —二一三級丁 基苯基）(2,4 —二一三級丁基苯基）亞鱗酸醋、2,2'—亞甲基雙 (4,6 —二一三級丁基苯基）（2_三級丁基一 4 —甲基苯基）亞 磷酸酯、2,2’ 一亞甲基雙（4_甲基一6 —三級丁基苯基）（2 — 三級丁基一4 —甲基苯基）亞磷酸酯、2,2，一亞乙基雙（4 —甲 基一 6 —三級丁基苯基）（2_三級丁基一4 —甲基苯基）亞鱗 酸酯、四（2，4 —二一三級丁基苯基）一 4,4' 一聯伸苯基二亞膦 21 201211093 酸酯、四（2,4 —二一三級丁基苯基）一4,3'—聯伸苯基二亞膦 酸酯、四（2,4一二一三級丁基苯基）一 3,3'—聯伸苯基二亞膦 酸酯、四（2,6_二一三級丁基苯基）一4,4’一聯伸苯基二亞膦 酸酯、四（2,6_二一三級丁基苯基）一 4,3，_聯伸苯基二亞膦 酸酯、四（2,6_二一三級丁.基苯基）一3，3’一聯伸苯基二亞膦 酸醋、雙（2,4 一 ——二級丁基笨基）一4 一苯基一苯基亞鱗酸 酯、雙（2,4 —二一三級丁基苯基）一 3—苯基一苯基亞膦酸 酯、雙（2，6—二一正丁基苯基）一3 —苯基一苯基亞膦酸酯、 雙（2,6 —二一三級丁基苯基）一 4一苯基一苯基亞膦酸酯、雙 (2,6 —二一三級丁基苯基）一 3—苯基一苯基亞膦酸酯、四 (2,4_二一三級丁基一5—甲基苯基）—4,4，一聯伸苯基二亞 膦酸酯、磷酸三丁酯、磷酸三曱酯、磷酸三甲苯酯、磷酸 二本酯、碟酸二氯苯酯、磷酸三乙酯、破酸二苯基甲苯酯、 磷酸二苯基單鄰聯苯基酯、磷酸三丁氧基乙酯、磷酸二丁 酯、碗酸二辛酯、碟酸二異丙醋等。 上述璃系化合物亦可使用市售品。作為市售之磷系化 合物，並無特別限定，例如可列舉：Adeka製造之Adekastab PEP - 4C、Adekastab PEP — 8、Adekastab PEP - 24G、 Adekastab PEP- 36、Adekastab HP- 10、Adekastab 2112、TINUVIN 765, TINUVIN 770DF, TINUV] manufactured by Ciba Specialty Chemicals [N 144, TINUVI.N 123, TINUVIN 622LD, TINUVIN 152, CHIMASSORB 944; LA-52, LA-57, LA_62, LA-63P, LA manufactured by Adeka - 77Y, LA-81, LA-82, LA-87, etc. The above-mentioned hindrance compound is not particularly limited, and examples thereof include 1,1,3-tris(2-mercapto-4-phenodialkylphosphite-5-tributylphenyl) Calcined, distearyl neopentyl alcohol di-salt, bis (2,4 213 butyl phenyl) pentaerythritol diphosphite, double (2,6 - two one three Butyl 4- 4-methylphenyl) pentaerythritol di-m-androstate, phenyl bisphenol a pentaerythritol di-perylate, dicyclohexyl neopentyl alcohol di-p-ate, three (Diethylphenyl) phthalate, tris(diisopropylphenyl) sublamate, tris(di-n-butylphenyl) phosphite, three (2,4 one two one three Butyl phenyl) phosphite, tris(2,6-di-tris-butylphenyl) sulphate, tris(2,6-di-tris-butylphenyl) phosphite, 2 , 2, monomethylene bis(4,6-di-tert-butylphenyl) (2,4-di-tert-butylphenyl) squaraine, 2,2'-methylene double (4,6-di-tert-butyl butylphenyl) (2-tris-butyl-4-methylphenyl) phosphite, 2,2'-a Bis(4-methyl-6-tertiary butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2, monoethylene bis(4-methyl a 6-tertiary butylphenyl) (2-tris-butyl-4-methylphenyl) squarate, tetras(2,4-di-tert-butylphenyl)-4,4' A phenyldiphosphine 21 201211093 acid ester, tetrakis(2,4-di-tert-butylphenyl)-4,3'-co-phenyldiphosphinate, four (2,4 Di-tertiary butyl phenyl)- 3,3'-co-phenylphenyl diphosphinate, tetrakis(2,6-di-triphenyl)- 4,4'-linked phenyl Diphosphonite, tetrakis(2,6-di-tert-butylphenyl)-4,3,_linked phenyldiphosphinate, tetrakis(2,6-di-tert-butyl) Phenyl)-3,3'-linked phenyldiphosphinic acid vinegar, bis(2,4-di-butyl butyl)- 4-phenyl-phenyl squarate, double (2 , 4—di-tert-butyl butylphenyl)-3-phenyl-phenylphosphinate, bis(2,6-di-n-butylphenyl)-3-phenylphenylphosphinic acid Ester, bis (2,6-di-tertiary butyl) )) 4-phenylphenyl phenyl phosphonate, bis(2,6-di-tris-butylphenyl)-3-phenyl-phenylphosphinate, tetra (2,4_2) a tertiary butyl 5-methylphenyl)-4,4, a monophenylene diphosphinate, tributyl phosphate, tridecyl phosphate, tricresyl phosphate, di-ester phosphate, dish Dichlorophenyl acid ester, triethyl phosphate, diphenyl toluene acid ester, diphenyl mono-o-phenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl benzoate, dish Acid diisopropyl vinegar and the like. Commercially available products can also be used as the above-mentioned glass-based compound. The commercially available phosphorus-based compound is not particularly limited, and examples thereof include Adekastab PEP-4C manufactured by Adeka, Adekastab PEP-8, Adekastab PEP-24G, Adekastab PEP-36, Adekastab HP-10, Adekastab 2112,

Adekastab 260 > Adekastab 522 A ^ Adekastab 11 78 > Adekastab 1500 ^ Adekastab C . Adekastab 135A ^ Adekastab 3010 > Adekastab TPP ° 作為龄化合物’並無特別限定，例如可列舉：2,6 三級丁基―4—甲基苯酚、正十八烷基-3-(3,5-二 22 201211093 級丁基一 4一經苯基）丙酸醋、四[亞曱基一3—(3,5 —二一三 級丁基一 4 —羥笨基）丙酸酯]甲烷、2,4 —二一三級丁基一6 —曱基本齡、1，6'—己二醇_雙一 [3 — (3,5 —二一三級丁基一 4_羥笨基）丙酸酯]、三（3,5_二一三級丁基一 4_羥基苄基） 一異三聚氰酸酯、1，3,5 —三甲基一 2,4,6 —三（3,5—二一三級 丁基一 4 —羥基苄基）苯、新戊四醇基一四一[3 —（3,5 —二一 三級丁基一 4一羥苯基）丙酸酯]、3,9 —雙一[2— [3 —（3 —三 級丁基一4 —羥基一5—甲基苯基）一丙醯氧基]_ 1,1—二曱 基乙基]一2,4,8，10 —四氧雜螺[5,5]十一烷、三乙二醇一雙[3 —(3—三級丁基一 5 —曱基一4 —羥基苯基）丙酸酯]、2,2·— 亞丁基雙（4,6—二一三級丁基苯酚）、4,4’一亞丁基雙（3—曱 基一 6 —三級丁基苯酚）、2,2’一亞曱基雙（4 —曱基一 6 —三級 丁基苯酚）、2,2，--亞甲基雙（4—乙基一 6 —三級丁基苯酚）、 2—三級丁基一 6 — (3—三級丁基一 2 —經基一 5 —曱基苄基） —4 —甲基苯酚丙烯酸酯、2— [1 — (2—羥基一3，5 —二一三 級戊基苯基）乙基]—4,6 —二一三級戊基苯基丙烯酸酯、4,4' _硫代雙（3 —甲基一6—三級丁基苯酚）、4，f 一亞丁基雙（3 一曱基一 6 —三級丁基苯酚）、2—三級丁基一4 一甲基苯酚、 2，4一二一三級丁基苯盼、2,4 —二一三級戊基苯盼、4，4' 一 硫代雙（3 —甲基一6 —三級丁基笨盼）、4,4'—亞丁基雙（3 — 甲基一6 —三級丁基苯酚）、雙—[3，3 一雙—（4·—羥基一 3·— 三級丁基苯基）一 丁酸]—二醇酯、2,4 一二—三級丁基笨 酚、2,4 —二一三級戊基苯酚、2_ Π — (2_羥基~3,5—二一 三級戊基苯基）乙基]一 4,6 —二一三級戊基苯基丙烯酸酯、 23 201211093 雙一 [3,3 —雙一（4·一羥基_ 3·—三級丁基苯基）_ 丁酸]—二 醇酯等。 上述酚系化合物亦可使用市售品。作為市售之酚系化 合物，並無特別限定，例如可列舉：Ciba Specialty Chemicals 製造之 IRGANOX 1010、IRGANOX 1035、IRGANOX 1076、 IRGANOX 1135、IRGANOX 245、IRGANOX 259、IRGANOX 295、IRGANOX 3114、IRGANOX 1098、IRGANOX 1520L ; Adeka 製造之 Adekastab AO — 20、Adekastab AO — 30、 Adekastab AO— 40 ' Adekastab AO— 50 ' Adekastab AO — 60、Adekastab AO— 70、Adekastab AO— 80、Adekastab AO 一 90、Adekastab AO- 330 ;住友化學工業製造之 Sumilizer GA- 80、Sumilizer MDP- S、Sumilizer BBM- S、Sumilizer GM、Sumilizer GS ( F)、Sumilizer GP 等。 另外，作為樹脂之抗著色劑，亦可使用市售之添加材 料。例如可列舉：Ciba Specialty Chemicals 製造之 TINUVIN 328、TINUVIN 234、TINUVIN 326、TINUVIN 120、TINUVIN 477'TINUVIN 479> CHIMASSORB 2020FDL' CHIMASSORB 119FL 等。 較佳為含有上述磷系化合物、胺化合物、酚系化合物 中之至少1種以上，其摻合量，並無特別限定，相對於該 硬化性樹脂組成物，為0.005〜5.0重量％之範圍。 本發明之硬化性樹脂組成物A係藉由將上述各成分均 勻混合而獲得。本發明之硬化性樹脂組成物A可藉由與先 前已知之方法相同之方法而容易地製成其硬化物。例如將 24 201211093 環氧樹脂、具有三環癸烷結構之醇、硬化劑以及視需要之 硬化促進劑、含磷化合物、黏合劑樹脂、無機填充材料及 摻合劑，視需要使用擠出機、捏合機、輥機等充分混合至 均勻而獲得硬化性樹脂組成物，將該硬化性樹脂組成物熔 融後，使用澆鑄或轉注成形機等進行成形，進而於8〇〜2〇〇 °C加熱2〜10小時，藉此可獲得本發明之硬化物。 另外，將本發明之硬化性樹脂組成物A溶解於甲苯、 二甲苯、丙酮、曱基乙基酮、曱基異丁基酮、二甲基甲醯 胺、二甲基乙醯胺、N—曱基吡咯啶酮等溶劑中，製成硬化 性樹脂組成物清漆’使其含浸於玻璃纖維、碳纖維、聚酯 纖維、聚醯胺纖維、氧化鋁纖維、紙等基材中，並加熱乾 燥，將所得之預浸體進行熱壓成形，藉此可製成本發明之 硬化性樹脂組成物A之硬化物。此時之溶劑使用量，在本 發明之硬化性樹脂組成物A與該溶劑之混合物中通常占ι〇 70重量。/〇、較佳為1 $〜70重量％。另外，亦可以液狀組 成物之狀態，以RTM方式獲得含有碳纖維之環氧樹脂硬化 另外’亦可使用本發明之硬化性樹脂組成物A作為膜 型組成物之改質劑。具體而言，可用於提高B階段中之可 撓特性等之情形。此種膜型樹脂組成物係藉由將本發明之 硬化性樹脂組成物A製成上述硬化性樹脂組成物清漆而塗 佈於剝離膜上，於加熱下去除溶劑後，進行B階段化，而 獲知為片狀之接著劑。該片狀接著劑可用作多層基板等中 之層間絕緣層。 25 201211093 其次，對將本發明之硬化性樹脂組成物A用作光半導 體之密封材料或固晶材料之情形進行詳細說明。 於將本發明之硬化性樹脂組成物A料高亮度 led等光半導體之密封材料或固晶材料之情形時，藉 環氧樹脂、含有多元㈣等之硬化劑、偶合材料、抗氧化 :以及光穩定劑等添加物充分混合而製備環氧樹脂組成 物，用於密封材料、或者固晶材料與密封材料之兩者。作 為混合方法’係使用捏合機、三輥機、萬能混合機、行星 式混合機、均質混合機、句相分散機、珠磨機等而進行常 溫或加溫混合。 节 向亮度白色LED等光半導體元件通常係使用接著劑 (固晶材料），使積層於藍寶石、尖晶石、等 基板上之 GaAs、GaP、GaAlAs、GaAsp、八心、bp、GW、 mN'AIWN等半導體晶片接著於引線架、散熱板或 封裝體上而成。亦有為了流通電流而連接有金㈣導線之 類型。為了保護該半導體晶片不受熱或濕氣之影響，且發 揮透鏡功能之作用，而以環氧樹脂等密封材料進行密封。 本發明之硬化性樹脂組成物A可用作該密封材料或固晶材 料為了步驟之方便，較佳為將本發明之硬化性樹脂組成 物A用於固晶材料與密封材料之兩者。 作為使用本發明之硬化性樹脂組成物A將半導體晶片 接著於基板上之方法’可藉由分注器、灌注（pGtting)、網 板印刷而塗佈本發明之硬化性樹脂組成物A後，載置半導 體晶片而進行加熱硬化，使半導體晶片接著。加熱可使用 26 201211093 =環式、、紅外線、高頻等方法。加熱條件較佳為例如 時產生〜23GC進行1分鐘〜24小時左右。為降低加熱硬化 之内部應力’例如可於8〇〜12(TC進行3〇分鐘〜5 小時預備硬化後，於120〜靴、30分鐘〜10小時之條件 下進行後硬化。 件 作為密封材料之成形方式，可使用以下方式：向插入 有如上所述固定有半導體晶片之基板之模框内注入密封材 料後進行加熱硬化而成形之注人方式；預先向模具上注入 密封材料’於其中浸潰固定於基板上之半導體晶片而進行 加熱硬化後，自模具中脫模之壓縮成形方式等。作為注入 方法可列舉分注器、轉注成形、射出成形等。加熱可使 用熱風循環式、紅外線、高頻等方法。 加熱條件較佳為例如於8〇〜23〇〇c進行1分鐘〜24小 時左右。為降低加熱硬化時產生之内部應力，例如可於80 〜120 c下進行30分鐘〜5小時預備硬化後於 C、3 0分鐘〜丨〇小時之條件下進行後硬化。 硬化性樹脂組成物B(藉由酸性硬化促進劑（硬化觸媒） 之陽離子硬化） 使用酸性硬化促進劑而硬化之本發明之硬化性樹脂組 成物B含有光聚合起始劑或熱聚合起始劑作為酸性硬化促 進劑。進而亦可含有稀釋劑、聚合性單體、聚合性寡聚物、 聚合起始助劑、光敏劑等各種公知之化合物、材料等。另 外亦可根據期望含有無機填充材料、著色顏料、紫外線 吸收劑、抗氧化劑、穩定劑等各種公知之添加劑。 27 201211093 作為酸性硬化促進劑，較佳為陽離子聚合起始劑’尤 佳為光陽離子聚合起始劑。作為陽離子聚合起始劑，可列 舉含有錤鹽、錡鹽、重氮鹽等鏽鹽者，該等可單獨使用或 使用2種以上。 活性能量線陽離子聚合起始劑之例為：金屬氟硼錯鹽 及三氟化硼錯合物（美國專利第3379653號說明書）、雙（全 氟烷基磺醯基）曱烷金屬鹽（美國專利第3586616號說明 書）、芳基重氮化合物（美國專利第37〇8296號說明書）、 Via族元素之芳香族鑌鹽（美國專利第4〇584〇〇號說明書）、 Va族元素之^香族鏘鹽（美國專利第4〇69〇55號說明書）、 Ilia〜Va族元素之二羰基螯合物（美國專利第4〇68〇91號說 明書）、硫代吡喃鏽鹽（美國專利第4139655號說明書）、 MF6 —陰離子形式之VIb族元素（美國專利第4161478號說 明書·Μ係選自磷、銻及砷）、芳基銃錯鹽（美國專利第 4231951號說明書）' 芳香族鎭錯鹽及芳香族疏錯鹽（美國 專利第4256828號說明書）、及雙μ—(二苯基銃基）苯基]硫 化物 雙 /、氟* 金屬鹽（Journa 丨 of Polymer Science.Adekastab 260 > Adekastab 522 A ^ Adekastab 11 78 > Adekastab 1500 ^ Adekastab C . Adekastab 135A ^ Adekastab 3010 > Adekastab TPP ° The compound of the age is not particularly limited, for example, 2,6 tertiary butyl - 4-methylphenol, n-octadecyl-3-(3,5-di 22 201211093 butyl-4-isophenyl) propionic acid vinegar, four [arsinylene-3-(3,5-two) Tertiary butyl 4-hydroxyphenyl) propionate] methane, 2,4-di-tert-butyl butyl- 6-indole basic age, 1,6'-hexanediol_double one [3 - (3 , 5 - 2 - 13 butyl - 4 - hydroxyphenyl) propionate], tris (3,5 - di-tri-butyl 4- 4-hydroxybenzyl) monoisocyanurate, 1, 3,5-trimethyl- 2,4,6-tris (3,5-di-tris-butyl-4-hydroxy-hydroxybenzyl)benzene, neopentyl alcohol 1-4 [3 - (3,5 —2,3-tert-butyl-4-hydroxyphenyl)propionate], 3,9—bi-[2—[3—(3—tris-butyl-4-hydroxy-5-methylphenyl) Monopropoxy]- 1,1-didecylethyl]- 2,4,8,10-tetraoxaspiro[5,5]undecane, triethylene glycol-double [3 — (3-three-tert-butyl-5-fluorenyl-4-hydroxyphenyl)propionate], 2,2·-butylenebis(4,6-di-tris-butylphenol), 4,4' Monobutylene bis(3-indenyl-6-tert-butylphenol), 2,2'-indenylene bis(4-indenyl-6-tert-butylphenol), 2,2,-- Methyl bis(4-ethyl-6-tertiary butyl phenol), 2-tris-butyl-6-(3-tertiary butyl-2-trans-yl-5-fluorenylbenzyl)-4 Methyl phenol acrylate, 2-[1 - (2-hydroxy-3,5-di-p-pentylphenyl)ethyl]-4,6-di-p-pentyl phenyl acrylate, 4, 4' _ thiobis (3-methyl-6-tert-butylphenol), 4, f-butylidene bis(3-indenyl-6-tert-butylphenol), 2- to 3-butyl 4 monomethylphenol, 2,4,23,3 butyl benzene, 2,4 - 2,3 pentyl benzene, 4,4' thio bis (3-methyl -6 - 3) Butyl phenyl), 4,4'-butylidene bis(3-methyl-6-tertiary butyl phenol), bis-[3,3-double-(4.-hydroxy-3?-? base Butyl]butyric acid]-diol ester, 2,4 di-tertiary butyl phenol, 2,4-di-p-pentyl phenol, 2 Π — (2_hydroxy~3,5-two Tertiary pentylphenyl)ethyl]- 4,6-di-p-pentyl pentyl phenyl acrylate, 23 201211093 bis-[3,3-bis-(4.-hydroxy- 3 -3-butyl) Phenyl)-butyric acid]-glycol ester and the like. Commercially available products can also be used as the phenolic compound. The commercially available phenolic compound is not particularly limited, and examples thereof include IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, IRGANOX 245, IRGANOX 259, IRGANOX 295, IRGANOX 3114, IRGANOX 1098, IRGANOX manufactured by Ciba Specialty Chemicals. 1520L; Adeka made Adekastab AO-20, Adekastab AO-30, Adekastab AO-40 'Adekastab AO-50' Adekastab AO-60, Adekastab AO-70, Adekastab AO-80, Adekastab AO-90, Adekastab AO-330; Sumilizer GA-80, Sumilizer MDP-S, Sumilizer BBM-S, Sumilizer GM, Sumilizer GS (F), Sumilizer GP, etc. manufactured by Sumitomo Chemical Industries. Further, as the anti-coloring agent for the resin, commercially available additive materials can also be used. For example, TINUVIN 328, TINUVIN 234, TINUVIN 326, TINUVIN 120, TINUVIN 477 'TINUVIN 479> manufactured by Ciba Specialty Chemicals, CHIMASSORB 2020 FDL' CHIMASSORB 119FL, and the like can be cited. It is preferable that at least one of the above-mentioned phosphorus compound, the amine compound, and the phenol compound is contained, and the amount thereof is not particularly limited, and is in the range of 0.005 to 5.0% by weight based on the curable resin composition. The curable resin composition A of the present invention is obtained by uniformly mixing the above components. The curable resin composition A of the present invention can be easily produced into a cured product by the same method as the previously known method. For example, 24 201211093 epoxy resin, alcohol having a tricyclodecane structure, a hardener, and optionally a hardening accelerator, a phosphorus-containing compound, a binder resin, an inorganic filler, and a blending agent, if necessary, using an extruder, kneading The machine, the roller, and the like are sufficiently mixed to obtain a curable resin composition, and the curable resin composition is melted, and then molded by a casting or a transfer molding machine, and further heated at 8 Torr to 2 ° C. After 10 hours, the cured product of the present invention can be obtained. Further, the curable resin composition A of the present invention is dissolved in toluene, xylene, acetone, mercaptoethyl ketone, decyl isobutyl ketone, dimethylformamide, dimethylacetamide, N- In a solvent such as decyl pyrrolidone, a curable resin composition varnish is formed to be impregnated into a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, or paper, and dried by heating. The obtained prepreg is subjected to hot press forming, whereby a cured product of the curable resin composition A of the present invention can be obtained. The amount of the solvent used at this time is usually 70% by weight in the mixture of the curable resin composition A of the present invention and the solvent. /〇, preferably 1 $ to 70% by weight. Further, in the state of the liquid composition, the epoxy resin containing carbon fibers may be obtained by RTM method. Further, the curable resin composition A of the present invention may be used as a modifier of the film type composition. Specifically, it can be used to improve the flexibility characteristics and the like in the B stage. The film-type resin composition is applied to the release film by forming the curable resin composition A of the present invention into the above-mentioned curable resin composition varnish, and the solvent is removed by heating, and then B-staged. Known as a tablet-like adhesive. The sheet-like adhesive can be used as an interlayer insulating layer in a multilayer substrate or the like. 25 201211093 Next, a case where the curable resin composition A of the present invention is used as a sealing material or a solid crystal material of a photo-semiconductor will be described in detail. When the curable resin composition of the present invention is made of a high-brightness LED or the like, or a solid crystal material, a hardener, a coupling material, an antioxidant, and light are used. An additive such as a stabilizer is sufficiently mixed to prepare an epoxy resin composition for a sealing material, or both a solid crystal material and a sealing material. As the mixing method, a kneader, a three-roller, a universal mixer, a planetary mixer, a homomixer, a sentence phase disperser, a bead mill or the like is used for room temperature or warm mixing. An optical semiconductor element such as a brightness-illuminated white LED is usually made of an adhesive (solid crystal material), and is laminated on GaAs, GaP, GaAlAs, GaAsp, Baxin, bp, GW, mN' on a substrate such as sapphire, spinel, or the like. A semiconductor wafer such as AIWN is formed on a lead frame, a heat sink or a package. There are also types of gold (four) wires that are connected for current flow. In order to protect the semiconductor wafer from heat or moisture, and to function as a lens, it is sealed with a sealing material such as an epoxy resin. The curable resin composition A of the present invention can be used as the sealing material or the solid crystal material. For the convenience of the step, the curable resin composition A of the present invention is preferably used for both the solid crystal material and the sealing material. After the method of adhering the semiconductor wafer to the substrate using the curable resin composition A of the present invention, the curable resin composition A of the present invention can be applied by a dispenser, pGtting, or screen printing. The semiconductor wafer is placed and heat-hardened to follow the semiconductor wafer. Heating can be used 26 201211093 = ring, infrared, high frequency and other methods. The heating conditions are preferably, for example, ～23 GC for 1 minute to 24 hours. In order to reduce the internal stress of heat hardening, for example, it can be post-hardened under conditions of 120 靴 to 5 hours to 10 hours after TC 〇 〇 〇 〇 〇 〇 〇 〇 〇 、 、 、 。 。 。 。 。 。 。 。 。 。 。 In the molding method, a method of injecting a sealing material into a mold frame in which a substrate on which a semiconductor wafer is fixed as described above is inserted and then heat-hardening is formed, and a sealing material is injected into the mold in advance to impregnate the mold. A semiconductor wafer to be mounted on a substrate and heat-hardened, and then subjected to a compression molding method such as demolding from a mold. Examples of the injection method include a dispenser, transfer molding, injection molding, etc. Heating can be performed by using a hot air circulation type, an infrared ray, or a high temperature. The heating condition is preferably, for example, about 8 to 23 〇〇c for about 1 minute to 24 hours. To reduce the internal stress generated during heat curing, for example, it can be carried out at 80 to 120 c for 30 minutes to 5 hours. After pre-hardening, post-hardening is carried out under conditions of C, 30 minutes to 丨〇 hours. Curable resin composition B (by acid hardening accelerator (hardening touch) Cation hardening) The curable resin composition B of the present invention which is cured by using an acidic curing accelerator contains a photopolymerization initiator or a thermal polymerization initiator as an acid hardening accelerator. Further, it may contain a diluent or a polymerization sheet. Various known compounds, materials, and the like, such as a bulk, a polymerizable oligomer, a polymerization initiator, and a photosensitizer, and various inorganic fillers, coloring pigments, ultraviolet absorbers, antioxidants, stabilizers, and the like are known as desired. 27 201211093 As the acid hardening accelerator, a cationic polymerization initiator is preferred, and a photocationic polymerization initiator is preferred. Examples of the cationic polymerization initiator include a phosphonium salt, a phosphonium salt, a diazonium salt, and the like. For the rust salt, these may be used alone or in combination of two or more. Examples of the active energy cation polymerization initiator are: metal fluoroboron salt and boron trifluoride complex (U.S. Patent No. 3,375, 653), double (Perfluoroalkylsulfonyl) decane metal salt (US Patent No. 3586616), aryl diazonium compound (US Patent No. 37〇8296) The specification), the aromatic sulfonium salt of the Via group element (the specification of the US Patent No. 4 584 〇〇), the fragrant salt of the Va group element (the specification of the US Patent No. 4〇69〇55), the Ilia~Va family Elemental dicarbonyl chelates (U.S. Patent No. 4,68,91), thiopyranium rust (U.S. Patent No. 4,139, 655), MF6 - anionic form of Group VIb (US Patent No. 4,161,478) · lanthanide is selected from the group consisting of phosphorus, antimony and arsenic), aryl sulfonium salt (U.S. Patent No. 4,231,951), 'aromatic erroneous salt and aromatic error-causing salt (US Patent No. 4256828), and double μ- (diphenylindenyl)phenyl]sulfide bis, fluorine* metal salt (Journa 丨of Polymer Science.

Polymer Chemistry，第 2 卷，第 1789 項（1984 年））。除此 以外’亦可使用鐵化合物之混合配位體金屬鹽及矽烧醇— 紹錯合物。 另外’作為具體例’可列舉：「Adeka Optomer SP150」、 「Adeka Optomer SP170」（均為旭電化工業公司製造）、 「UVE — 1014」（General Electronics 公司製造）、「CD — 1012」（Sartomer 公司製造）、「rp — 2074」（Rhodia 公司製 28 201211093 造）等。 相對於環氧樹脂成分1 〇〇重量份，該陽離子聚合起始 劑之使用量較佳為0·01〜50重量份，更佳為0.1〜10重量 份0 進而’可同時使用該等光陽離子聚合起始劑與公知之 聚合起始助劑及光敏劑之丨種或2種以上。作為聚合起始 助劑之例，例如可列舉以下光自由基聚合起始劑：安息香、 一笨甲醯、安息香甲醚、安息香異丙醚、苯乙酮、2,2—二 甲氧基—2 —苯基苯乙酮、i，l一二氯苯乙酮、1一羥基環己 基笨基酮、2-甲基—1 一（4—甲基硫代苯基）一2—口末啉醇丙 惊 s 1 —酮、N，N —二甲基胺基苯乙酮、2一甲基蒽醌、2 — 心酿 2 —二級丁基蒽蛾、1 一氣蒽酿、2 —戊基蒽g昆、 異丙基嗟噸酮（2 - isopropylthioxanthone )、2,4 -二甲 基噻噸詷、2,4_二乙基噻噸酮、2,4_二異丙基噻噸酮、苯 乙鲷二曱基縮酮、二苯甲酮、4_甲基二苯甲酮、4,4，—二 氣二苯甲酮、4,4，一雙二乙基胺基二苯曱酮、米其勒酮等。 相對於可進行光自由基聚合之成分100重量份，光自由基 A 5起始劑等聚合起始助劑之使用量為0.01〜30重量份， 較佳為0.1〜1〇重量份。 作為光敏劑之具體例，可列舉：蒽、2 一異丙基噻噸嗣、 ’4〜二甲基噻噸酮、2,4 —二乙基噻噸酮、2,4 —二異丙基噻 =_!、吖啶橙、吖啶黃、膦R、苯并黃素（benz〇flavine)、 :磺素T ( Setoflavin T)、茈、N，N —二曱基胺基苯甲酸乙 知、N，N—二甲基胺基苯甲酸異戊酯、三乙醇胺、三乙胺等 29 201211093 。相對於全環氧樹脂成分1 0 0重量份，光敏劑之使用量為 〇.〇1〜30重量份，較佳為〇.丨〜1〇重量份。 進而，本發明之硬化性樹脂組成物B中，可視需要添 加無機填充劑或矽烷偶合材料、脫模劑、顏料等各種摻合 劑’各種熱硬化性樹脂》具體例係如上所述。 本發明之硬化性樹脂組成物B係藉由將各成分均勻混 合而獲得。另外’亦可溶解於聚乙二醇單乙醚或環己酮、 r — 丁内酯等有機溶劑中而變得均勻後，藉由乾燥來去除 溶劑而使用。此時之溶劑使用量，在本發明之硬化性樹脂 組成物B與該溶劑之混合物中占丨〇〜7〇重量％、較佳為丄$ 〜70重量％。本發明之硬化性樹脂組成物B可藉由紫外線 照射而硬化，該紫外線照射量由於根據硬化性樹脂組成物 之摻合而有所不同，故根據各硬化條件而決定。只要為硬 化性樹脂組成物會硬化之照射量即可，只要滿足硬化物之 接著強度良好之硬化條件即可。該硬化時，由於光必需穿 透至細微部分，故於構成硬化性樹脂組成物B之環氧樹脂 中要求透明性高者。另外，該等環氧樹脂系之光硬化中， 僅藉由光照射難以完全硬化，於要求耐熱性之用途中必需 藉由在光照射後進行加熱而使反應硬化完全結束。 於光照射後進行加熱之情形時，可於通常之硬化性樹 脂組成物B之硬化溫度域進行。例如於常溫〜丨5〇ι下較佳 為30分鐘〜7天之範圍。雖因為硬化性樹脂組成物B之摻 合而改變’但越是特別高之溫度域，則越對光照射後之硬 化促進有效’ H由短時間之熱處理即有效。另外，越為低 201211093 溫，則越| jj p. 水长時間之熱處理。藉由此種熱後硬化，亦表 現出老化處理之效果。 另外，使該等硬化性樹脂組成物B硬化而獲得之硬化 多’亦可根據用途而採用各種形狀’並無特別限定， 例士可製成膜狀、片狀、塊狀等形狀。成形之方法根據應 用之部位、★番| ： 攝件而有所不同，例如可應用鑄造法、澆鑄法、 祠板P刷法、旋轉塗佈法、喷霧法、轉印&、分注器方式 等成形方法’但並不限定於該等。成形模型可使用研磨玻 璃、硬質不鏽鋼研磨板、聚碳酸醋板、聚對苯二甲酸乙二 酯板、聚甲基丙烯酸甲酯板等。$外’為提高與成形膜型 之脫模性’可應用聚對笨二甲酸乙二酯膜、聚碳酸酯膜、 聚氣乙烯膜1乙烯膜、聚四氟乙烯膜、聚丙烯膜、聚醯 亞胺膜等。 例如於用於陽離子硬化性之抗蝕劑時，首先將溶解於 聚乙二醇單乙醚或環己酮或者r — 丁内酯等有機溶劑中之 本發明之光陽離子型硬化性樹脂組成物B，利用網板印刷、 旋轉塗佈法等方法，以5〜16〇M m之膜厚塗佈於覆銅積層 板或陶瓷基板或者玻璃基板等基板上，形成塗膜。然後， 將該塗膜於60〜1 lot預備乾燥後，通過描繪有所期望之圖 案之負片而照射紫外線（例如低壓水銀燈、高壓水銀燈、 超高壓水銀燈、氤燈、雷射光等）’繼而於7〇〜l2〇〇c進行 曝光後烘烤處理。其後以聚乙二醇單乙醚等溶劑將未曝光 部分溶解去除（顯影）後，進而若有需要，則藉由紫外線 之照射及/或加熱（例如於100〜200°c進行0.5〜3小時） 31 201211093 進仃充分之硬化，獲得硬化物。如此亦可獲得印刷配線板。 將本發明之硬化性樹脂組成物Α及硬化性樹脂組成物 Β硬化而得之硬化物，可用於以光學零件材料為代表之各種 用途。所謂光學用材料，一般係指用於「使可見光、紅外 線、紫外線、X射線、雷射等光通過該材料中之用途」之材 料。更具體而言，除燈型或SMD型等LED用密封材料以外， 可列舉如下者。液晶顯不器領域中之基板材料、導光板、 棱鏡片、偏光板、相位差板、視角修正膜、接著劑、偏光 子保漠膜#液_晶用膜等液晶顯示裝置周邊材判^另外，作 為下一代平板顯示器而被期待之彩色pDp之密封材料、防 反射膜丨學修正膜、外殼材料、前面玻璃之保護膜、前 面玻璃代替材料、接著劑，另外，使用於led顯示裝置之 LED之模具材料、LED之密封材料、前面玻璃之保護膜、 引面玻璃代替材料' 接著劑，另夕卜，電漿定址液晶（PALC ) 顯示器中之基板材料、冑光板、稜鏡片、偏轉板、相位差Polymer Chemistry, Vol. 2, No. 1789 (1984)). In addition to this, a mixed ligand metal salt of an iron compound and a samarium alcohol-salt complex can also be used. In addition, 'as a specific example', "Adeka Optomer SP150", "Adeka Optomer SP170" (all manufactured by Asahi Denki Kogyo Co., Ltd.), "UVE-1014" (manufactured by General Electronics), "CD-1012" (Sartomer Corporation) Manufacturing), "rp-2074" (made by Rhodia Corporation 28 201211093). The cationic polymerization initiator is preferably used in an amount of from 0.01 to 50 parts by weight, more preferably from 0.1 to 10 parts by weight, based on 1 part by weight of the epoxy resin component. Further, the photocations can be used simultaneously. Two or more kinds of polymerization initiators and known polymerization initiators and photosensitizers. As examples of the polymerization initiation assistant, for example, the following photoradical polymerization initiators: benzoin, benzoin, benzoin methyl ether, benzoin isopropyl ether, acetophenone, 2,2-dimethoxy- 2-phenylacetophenone, i,l-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1 mono(4-methylthiophenyl)-2-endoline Alcohol propyl s 1 - ketone, N, N - dimethylamino acetophenone, 2 - methyl hydrazine, 2 - heart-boiled 2 - secondary butyl quinone moth, 1 gas brewing, 2-pentyl蒽g Kun, isopropylthioxanthone, 2,4-dimethylthioxanthene, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, Phenylethyl hydrazide ketal, benzophenone, 4-methylbenzophenone, 4,4, dibenzophenone, 4,4, mono-diethylaminodibenzophenone , Michelin and the like. The polymerization starting assistant such as a photoradical A 5 initiator is used in an amount of 0.01 to 30 parts by weight, preferably 0.1 to 1 part by weight, based on 100 parts by weight of the component capable of photoradical polymerization. Specific examples of the photosensitizer include hydrazine, 2-isopropylthioxanthene, '4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-diisopropyl Thio=_!, acridine orange, acridine yellow, phosphine R, benzyl flavine, setoflavin T, hydrazine, N,N-didecylaminobenzoic acid , N,N-dimethylaminobenzoic acid isoamyl ester, triethanolamine, triethylamine, etc. 29 201211093. The photosensitizer is used in an amount of from 1 to 30 parts by weight, preferably from 〇.丨 to 1 part by weight, based on 100 parts by weight of the total epoxy resin component. Further, in the curable resin composition B of the present invention, various additives such as an inorganic filler, a decane coupling material, a release agent, and a pigment may be added as needed. Specific examples of the various thermosetting resins are as described above. The curable resin composition B of the present invention is obtained by uniformly mixing the components. Further, it may be dissolved in an organic solvent such as polyethylene glycol monoethyl ether or cyclohexanone or r-butyrolactone to make it uniform, and then used to remove the solvent by drying. The amount of the solvent used at this time is ～7% by weight, preferably 丄$ to 70% by weight, based on the mixture of the curable resin composition B of the present invention and the solvent. The curable resin composition B of the present invention can be cured by irradiation with ultraviolet rays, and the amount of ultraviolet irradiation varies depending on the blending of the curable resin composition, and is therefore determined depending on the respective curing conditions. The amount of irradiation in which the hard resin composition is hardened may be used as long as it satisfies the curing condition in which the subsequent strength of the cured product is good. At the time of the hardening, since the light must penetrate into the fine portion, the epoxy resin constituting the curable resin composition B is required to have high transparency. Further, in the photohardening of the epoxy resin type, it is difficult to completely cure only by light irradiation, and in applications requiring heat resistance, it is necessary to completely complete the reaction hardening by heating after light irradiation. When heating is performed after light irradiation, it can be carried out in the hardening temperature range of the usual curable resin composition B. For example, it is preferably in the range of 30 minutes to 7 days at room temperature ~ 丨 5 〇ι. Although it is changed by the blending of the curable resin composition B, the more the temperature range is particularly high, the more effective it is to harden the light after irradiation, and it is effective by heat treatment for a short period of time. In addition, the lower the temperature of 201211093, the more | jj p. The heat treatment of water for a long time. By this post-heat hardening, the effect of the aging treatment is also exhibited. In addition, the hardening resin composition B is hardened and hardened, and various shapes are used depending on the application. The shape is not particularly limited, and the shape can be formed into a film shape, a sheet shape, a block shape or the like. The method of forming varies depending on the location of the application, the film, and the like. For example, casting method, casting method, slab P brush method, spin coating method, spray method, transfer & The forming method such as the method is 'but is not limited to these. The forming model may be a ground glass, a hard stainless steel plate, a polycarbonate plate, a polyethylene terephthalate plate, a polymethyl methacrylate plate or the like. $External 'to improve the release property from the formed film type' can be applied to polyethylene terephthalate film, polycarbonate film, polyethylene film 1 vinyl film, polytetrafluoroethylene film, polypropylene film, poly醯 imine film and the like. For example, in the case of a cationically curable resist, the photocationic curable resin composition B of the present invention which is first dissolved in an organic solvent such as polyethylene glycol monoethyl ether or cyclohexanone or r-butyrolactone The film thickness is applied to a copper clad laminate, a ceramic substrate or a glass substrate by a method such as screen printing or spin coating, and a film thickness of 5 to 16 〇M m is applied to form a coating film. Then, the coating film is pre-dried in 60 to 1 lot, and then irradiated with ultraviolet rays (for example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, a laser beam, etc.) by drawing a negative film having a desired pattern, and then 7 〇~l2〇〇c is subjected to post-exposure baking treatment. Thereafter, the unexposed portion is dissolved and removed (developed) with a solvent such as polyethylene glycol monoethyl ether, and further, if necessary, irradiated with ultraviolet rays and/or heated (for example, at 100 to 200 ° C for 0.5 to 3 hours). 31 201211093 Advance hardening and obtain hardened material. Thus, a printed wiring board can also be obtained. The cured product obtained by curing the curable resin composition Α and the curable resin composition of the present invention can be used for various applications such as optical component materials. The material for optics generally refers to a material used for "the use of visible light, infrared rays, ultraviolet rays, X-rays, and laser light through the material." More specifically, in addition to the sealing material for LEDs such as a lamp type or an SMD type, the following may be mentioned. A liquid crystal display device such as a substrate material, a light guide plate, a prism sheet, a polarizing plate, a phase difference plate, a viewing angle correction film, an adhesive, a polarizing film, and a film for liquid crystal display in the field of liquid crystal display A color pDp sealing material, an antireflection film drop correction film, a case material, a front glass protective film, a front glass substitute material, an adhesive, and an LED used for a LED display device, which are expected as a next-generation flat panel display. The mold material, the LED sealing material, the front glass protective film, the lead glass instead of the material 'the next agent, in addition, the substrate material in the plasma-addressed liquid crystal (PALC) display, the calender plate, the cymbal plate, the deflector plate, Phase difference

板視角L正膜、接著劑、偏光子保護膜，另外’有機EL (EleCtr〇-lUmineseenee)顯示器中之前面玻璃之保護膜、 刖面玻璃代替材料、接著劑，另外場發射顯示器（)令 之各種膜基板、前面玻璃之保護膜、前面玻璃代替材料、 接著劑。光記錄領域中之VD(Vide〇Disk)、cD/cD_ ROM' CD—r /RW、DVD— R/DVD- RAM、MO/MD、 PD (相變磁碟）、朵與 九千卡用之磁碟基板材料、讀取透鏡、保 濩膜、密封材料、接著劑等。 光學機器領域中’靜物攝影機之透鏡用材料、取景器 32 201211093 棱鏡、目標稜 A, 機之攝影#感測器^卜，攝像 謹腹、你兄取景器。另外，投影電視之投射透鏡、保 京封奸封材料、接著劑等。光感測機器之透鏡用材料、 密封材料、垃金Μ n 之光劑H光零件領域巾，光通信系統中 料、接著劑光波導、元件之密封材 光連接器周邊之光纖材料、套圈、密封材 LED之=、等。光被動零件、光電路零件中，透鏡、波導、 '、封材料、CCD之密封材料、接 體電路（〇Elc)甚 寸疋电于積 材料、接著劍望 基板材料、纖維材料、元件之密封 管等， 。先纖領域中，裝飾顯示器用照明、導光 基礎建設用感測器類’顯示、標識類等，以及通信 體電路周邊材：中内L之二：機器連接用之光纖。半導體積 -4, #1, u 超1^SI材料用之顯微蝕刻術用之 抗触劑材料。汽車、 永❹h 域中’汽車用之反射燈、軸 承濩圏、齒輪部分、耐蝕 内零件、雷痛U I開關。P分、前照燈、引擎 士車用防鐘- 纟種内外裝品、驅動引擎、煞車油罐、 ::::鏽2、内飾板、内裝材料、保護及捆束用線束、 燃料軟管、汽車燈、铋接 s .. 代替品。另外，鐵道車輛用之雙 層玻璃。另外，飛機之結構 構件、保護及捆束用線束㈣賦予劑、引擎周邊 耐蝕塗層。建築領域中，内裝 太陽電池周邊材Π二材、玻璃中間膜、玻璃代替品、 之光、電子功能有機材料 、料下代 .^ ^ .仇也 為有機EE凡件周邊材料、有機 折件、料光—光轉換裝置之光放大元件、光運算 33 201211093 疋件、有機太陽電池周邊之基板材料、纖維材料、元件之 密封材料、接著劑等。 作為密封劑，可列舉：電容器、電晶體、二極體、發 光二極體、IC、LSI等用之灌注(potting)、浸潰（__)、 轉移模具㈣、、LSI類之C〇B、⑺F、TAB等用之灌注 (P〇t^ng)密封、倒裝晶片等用之底部填充劑、q卯、bga、 等1C封裝類構裝時之密封（增強用底部填充劑）等。 作為光學用材料之其他用途，可列舉使用硬化性樹脂 二成物A及硬化性樹脂組成物B之一般用*，例如除了接 者劑、塗料、塗佈劑、成形材料（包括片材、膜、FRP等）、 ，緣村料（包括印刷基板、電線包覆等）、密封劑以外，尚 可列舉基板用之氰酸醋樹脂組成物、或作為抗㈣】用硬化 劑之丙烯酸酷系樹脂等向其他樹脂等中之添加 接著劑，除了土木用、建築用、汽車用、一般事務用= 療用之接著劑以外，尚可列舉電子材料用之接著劑。該等 中，作為電子材料用之接著劑，可列舉：增層（buiid_y 基板等多層基板之層間接著劑、固晶冑、底部填充劑等半 導體用接著劑、BGA增強用底部填充劑、異向性導電性膜 (ACF)、異向性導電性導電f (Acp)等構裝用接著劑等: 實施例 之說明，以 ’本發明並 、欠藉由實施例，對本發明進行更具體 下，八要無特別說明，則份係指重量份。再者 不限定於該等實施例。 7236進行測 另外，本發明中，環氧當量係根據JIS κ — 34 201211093 定，黏度係於饥使用E型錢計進行測定。另外，氣相 層析法（以下料GC)中之分析條件㈣分離柱f使用 HP5-MS(0.25mmI.D.x15m ’膜厚 〇 2^m)，將管枉供 箱溫度設定為初始溫度10(rc，以每分鐘15。〇之速度升溫， 並於30(TC保持25分鐘。另夕卜，將氦作為載體氣體。進而， 凝膠滲透層析法（以下稱為GPC)之測定中為如下所述。 KF- 803L ' KF- 802.5 管柱為Shodex SYSTEM-21管柱 (x2根）、KF- 802 )，連結溶析液為四氫吱嚼流速為Η /min’管柱溫度為40〇C，另夕卜，檢測係以以進行校準 曲線係使用Shodex製造之標準聚笨乙稀。 合成例1 向具備攪拌機、回流冷卻管、攪拌裝置之燒瓶中，一 面實施氮氣沖洗，-面加人水1G份、12_鎢錢2 〇份、 嫣酸納3.0份、填酸氮二納3.2份、乙酸三辛基甲基敍2 9 份（Lion Akzo製造，50重量％二曱笨溶液，t〇maa _ 5〇 )、 甲苯m份、3-環己稀甲基=3一環己稀叛酸醋22〇份，將 該溶液升溫至48°C，一面劇烈攪拌一面用3〇分鐘添加35 重量％過氧化氫水220份，直接於48艺攪拌14小時。 反應結束後’以20重量％氫氧化鈉水溶液中和後，添 加飽和硫代硫酸鈉水溶液45份進行3〇分鐘之攪拌，靜置。 取出分離為2層之有機層，肖其中添加活性碳（A— Fine - Techno 製造 ’ CP2 )20 份、蒙脫石（Kunimine industries 製造’ Kunipia F) 20份，於室溫下料3小時後，過據。 對所獲得之濾液以水100份進行3次水洗，自所獲得之有 35 201211093 機層中蒸餾去除甲苯，藉此獲得 I >显下 J | 氧樹脂（EP— 1 ) 222份》所獲得 ‘，，、热色之液狀環 130 g/eq，黏度為205 mPa.s ( 25°c ) 衣氧當量為 合成例2 叼汉應谷 你刊艰匕基）乙基r甲 基石夕院1〇6份、重量平均分子量1700 (g τ” 烧醇末端甲基苯基聚石夕氧油234份（妙燒醇當 ）之$ 使用GPC測得之重量平均分子量之1/2而算出）、〇’ = 氧化鉀（KOH) f醇溶液18份’將浴溫設定為抑，.：: 升溫。升溫後，於回流下反應8小時。 <、 繼而，追加甲醇305份後1 60分鐘滴下蒸館水之甲 醇溶液（濃度50重量％) 86.4份，於回流下以75〇c反應8 小時。反應結束後，以5%磷酸二氫鈉水溶液中和後，於 °C蒸德回收甲醇之約90%。添加甲基異丁基酮38〇份以 2〇〇份之水反覆進行3次水洗。然後對有機相使用旋轉蒸發 器，於減壓下、1 〇(TC下去除溶劑，藉此獲得具有矽氧烷結 構之環氧樹脂（EP — 2 ) 300份。所獲得之化合物之環氧當 量為729 g/eq ’黏度為^90 mPa.s ( 25°C )，重量平均分 子量為2200 ’外觀為無色透明。 合成例3 向具備攪拌機、回流冷卻管、攪拌裝置、迪安一斯塔 克（Dean — Stark )管之燒瓶中’一面實施氮氣沖洗，一面 添加1，4一環己烷二曱酸二甲酯（岩谷瓦斯製造，DMCD — p) 14〇份、環己烯一4 —曱醇314份、四丁氧鈦（tetrabutoxy 36 201211093 titanium) 0.07份，一面去除反應生成之甲醇，一面進行i2〇 °c下1小時、i5〇°c下i小時、17(rc下}小時、19(rc下12 小時之反應。以氣相層析法（GC )進行反應後，冷卻至5〇 。(：。 冷卻結束後，添加347份之甲苯並使其均勻後，以1〇 重量％氫氧化鈉水溶液80份對反應溶液清洗3次，進而以 水100伤/次反覆水洗至廢水成為中性為止，使用旋轉蒸 發器於加熱減壓下蒸餾去除甲苯與未反應之3—環己烯—i -甲醇，藉此獲得以雙（3_環己職甲基）=1，4—環己院二 甲酸為主要成分之在常溫下為液狀之化合物（D—1) 240 份。 合成例4 向具備攪拌機、回流冷卻管、攪拌裝置之燒瓶中，一 面進仃虱氣沖洗，-面添加水15份、12-鎢磷酸〇_95份、 鱗&氣—鈉G·78份、乙酸三辛基錄t 5G%二甲苯溶液2.7 伤甲苯1 80份 合成例3中所獲得之化合物（D - 1 ) 11 8 广將該冷液升溫至6〇°c，一面劇烈攪拌，一面以i小時 ^ ^ 35質里％過氧化氫水70份，直接於601下搜拌13小 時。以氣相層析法確認反應之進行，結果為原料波峰消失。 。繼而以1重量％氫氧化鈉水溶液中和後，添加20重量 、”代硫奴鈉水溶液25份進行3〇分鐘之攪拌，靜置。取出 ^離為2層 <有機|，向其中添加活性碳（Aji_〇t〇Fine sh hn〇 製造 ’ CP1 ) 20 份、膨潤土（ Hojun 製造，Bengel )2〇伤，於室溫下攪拌i小時後，過濾。對所獲得之濾 37 201211093 液以水⑽份進行3次水洗’自所獲得之有機層中蒸德去 除曱苯，藉此獲得在常溫下為液狀之環氧樹脂（Ep_3) 119 份。所獲得之環氧樹脂之環氧當量為217 g/eq，黏度為 7520 mPa*s ( 25°C ) ° 實施例1、2、比較例1、2 將作為實施例之合成例1中所獲得之環氧樹脂（Ep — 1 )、二環癸烷二曱醇（AL — 1 )、作為比較例之三羥曱基丙 烷（AL— 2 )，以如下表丨所記載之摻合量均勻混合，獲得 實施例用之硬化性樹脂組成物（F — 1) (F—2)與比較例用 之硬化性樹脂組成物（F — 3 ) ( F — 4 )。 [表1] 實施例1 賫施例2 比較例1 比較例2 組成 硬化性樹脂組成物 F-1 F-2 F-3 F-4 環氧樹脂 EP-1 5.0 5.0 5.0 5.0 醇 AL-1 0.5 0.2 AL-2 0.5 0.2 實施例3、4、5、比較例3、4、5 對於所獲得之硬化性樹脂組成物（F — 1 ) ( F — 2 ) ( F — 3 ) ( F — 4 )及環氧樹脂（EP — 1 )，以如下表2所記載之摻 合量摻合酸性硬化促進劑（陽離子聚合起始劑）（三新化學 工業製造，San - Aid SI - 60，以下稱為c i )，獲得硬化 性樹脂組成物。 進而’對所獲得之化合物評價保存穩定性、硬化性。 結果同樣示於表2。 38 201211093 (評價方法） •保存穩定性： 將硬化性樹脂組成物於室溫下保管24小時之時之保管 穩疋性。若於24小時内發生凝膠化，則記為χ，若保持液 狀，則記為〇。 ”、 •硬化性： 於80〇C硬化1小時之時之硬化性。將硬化者記為〇， 將未硬化者（具有流動性者或半固體狀態者）記為χ。 [表2] 硬化性樹脂組成物 實施例 3 F—1 實施例 4 r? 1 實施例 5 比較例 3 比較例 4 比較例 5 組成 環氧樹脂 ΕΡ--1 5.0 r — 1 5.0 F—2 5.0 F-3 5.0 5.0 5 0 .醇 AL1 0.5 0.5 0.2 AL—2 0.5 0.2 廊冰森1 C — 1 0,05 — ---J 0.10 0.05 0.05 0.05 0 05 汁價 結果 保弁穩 硬化 定性 LJ. 〇 〇 〇 X 〇 〇 14 〇 〇 〇 〇 X 〇 根據以上結果，若為三羥甲基丙烷等醇，加入硬化性 良好之範圍内之量，則保存穩定性差，若要求保存穩定性， 則硬化性變差（比較例3、4)。另夕卜若不加入醇，則可確 保硬化性、保存穩定性（比較例5)。 實施例6、7、比較例6、7 對於所獲得之硬化性樹脂組成物（F — 1 )及環氧樹脂 (ΕΡ 1 )，以如下表3所記載之摻合量摻合酸性硬化促進 劑（C — 1 )，獲得硬化性樹脂組成物。 39 201211093 進而’對所獲得之化合物評價透濕度。結果同樣示於 表3。 (評價方法） •透濕度 濕度條件：60°C、90%、24小時 硬化條件：80。(：、1小時 [表3] 實施例6 比較例6 實施例7 比較例7 硬化性樹脂組成物 F-1 一 F-1 — 組成 環氧樹脂 EP-1 5.0 5.0 5.0 5.0 醇 AL-1 0.5 0.5 硬化促谁#丨 C-1 0.05 0.05 0.10 0.10 评價結果1 透濕唐 87 150 55 120 根據以上結果可知，本發明之硬化性樹脂組成物對於 对透濕性有效。 實施例8、比較例8 對於所獲得之硬化性樹脂組成物（F — 1 )及環氧樹脂 (EP— 1)，以如下表4之摻合量摻合酸性硬化促進劑（c_ i )’獲得硬化性樹脂組成物。 進而，對所獲得之化合物評價接著剪切強度。結果同 樣系於表4。 (評價方法） •接著剪切強度 硬化條件：8 0 °C、1小時 1 吸濕試驗條件：60。(：、90%、63小時 201211093 [表4] 實施例8 比較例8 硬化性樹脂組▲物 F一 1 — 組成 環氧樹脂 EP-1 5.0 5.0 醇 AL-1 0.5 硬化促進劑 C-1 0.10 0.10 評價結果 接著剪切強度 MPa 43.5 29.5 吸濕試驗後之接著剪切強度 MPa 11.3 8.6 根據以上結果可知，本發明之硬化性樹脂組成物流不 僅接著性優異，而且具有較高之对濕性。 實施例9、】0、比較例9、10 以與實施例1相同之方式，製作實施例用之硬化性樹 脂組或物（F — 1 )、（ F — 5 )、比較例用之硬化性樹脂組成物 (F—3)、（f_6)。組成示於表5。 對所獲得之硬化性樹脂組成物，使用作為硬化劑之曱 基六氫鄰苯二甲酸酐（新曰本理化製造，rjKACID MH，以 下稱為Η— 1 )、作為硬化促進劑之四級鱗鹽（日本化學工業 製造，Hishicolin PX4MP，以下稱為C 一 2 ),以如下表5記 載之摻合量摻合，分別獲得硬化性樹脂組成物。 進而’對所獲得之化合物評價保存穩定性。結果同樣 示於表5。 (評價方法） •儲存穩定性： 以初始之黏度與4小時後之黏度來比較在室溫下放置4 小時之時之黏度上升。 201211093 黏度上升越劇烈，可判斷保存穩定性越差β [表5] 實施例9 比較例9 實施例10 比較例10 硬化性樹脂組成物 F— 1 F-3 F-5 F-6 組成 環氧樹脂 EP-1 5.0 5.0 5.0 5.0 醇 AL-1 0.5 1.0 AL-2 0.5 1.0 硬化劑 H-1 6.5 6.5 6.5 6.5 /6 t化促進劑 C —2 0.02 0.02 0.02 0.02 評價 結果 初始之黏度（mPa.s) 384 420 1623 1587 4小時後之黏度（mpa.s) 584 2368 3528 82432 根據以上結果可知，使用本發明之硬化性樹脂組成物 之硬化性樹脂組成物的保管穩定性優異。 實施例11、12、比較例11 對於實施例用之硬化性樹脂組成物（F 一 1 ) ( f — 5 )、 作為比較例用之環氧樹脂（ΕΡ _ 1 )，使用酸酐（η — 1 )作 為硬化劑，且使用十六烷基三甲基氫氧化銨（東京化成工 業（股）製造，25%甲醇溶液，以下稱為c — 3 )作為硬化 促進劑，以下述表6所示之摻合比（重量份）摻合，進行 20分鐘消泡，獲得硬化性樹脂組成物。 使用所獲得之硬化性樹脂組成物，以如下所示之要領 進行揮發試驗，將結果一併示於表6。另外，硬化條件為 12〇°c χ2小時之預備硬化後1 50°C x5小時》 (揮發試驗） 對實施例及比較例中所獲得之硬化性樹脂組成物實施 真工消泡20分鐘後’以成為30 mmx20 mmx高度1 mm之 42 201211093 方式緩緩地澆鑄於以耐熱帶製成障壁之玻璃基板上。正確 測定所澆鑄之樹脂之重量後，使該澆鑄物以上述條件進行 硬化。 測定如此獲得之硬化物之重量，確認硬化時之重量減 少。（實施例、比較例之硬化係以相同之烘箱進行同樣之硬 化） [表6] 實施例11 實施例12 比較例11 硬4 S性樹脂組成物 F-1 F-5 _ 組成 環乾樹脂 EP-1 5.0 5.0 5.0 醇 AL-1 0.5 1.0 硬化劑 H-1 6.5 6.5 6.5 硬化 促進劑 C-3 0.02 0,02 0.02 評價結果 揮發試驗（: ¥發量） 5.2% 4.9% 13.0% 若將實施例U、12與比較例U加以比較，可知本發明 之硬化性樹脂组成物之揮發量少。本發明之硬化性樹脂組 成物具有抑制硬化時之揮發之效果。 實施例13、14、比較例12 使用合成例2中所獲得之有機聚矽氧烷化合物（EP _ 2 ) 作為環氧樹脂H 7所記載之組成製作硬化性樹脂組成 物（7 H F 8 )。使用酸針（H ~ 1 )作為硬化劑，使用 硬化促進㉚（C ~ 2 )作為硬化促進劑，以下述表7中所示 之摻口比（重量份）進行摻合，進行2g分鐘消泡。獲得本 發明或比較用之硬化性樹脂組成物。 (腐蝕氣體穿透性試驗） 43 201211093 使用所獲得之硬化性樹脂組成物，填充至注射器中， 使用精密噴出裝置，澆鑄成搭載有中心發光波465 nm 曰曰 片的外徑5 mm見方之表面構裝型LED封裝體（内徑4.4 mm，外壁高度1.25 mm )。將該澆鑄物投入加熱爐中，進行 12〇 C、1小時，進而15〇〇c、3小時之硬化處理而製作 封裝體。以下述條件將LED封裝體放置於腐蝕性氣體中， 觀察密封内部之鍍銀引線架部之顏色的變化。結果示於表 7 〇 測定條件 腐触氣體：硫化銨20%水溶液（硫成分與銀反應後變 成黑色） 接觸方法.於廣口玻璃瓶中，使硫化敍水溶液之容器 與上述LED封裝體混合存在’蓋上廣口玻璃瓶之蓋子，於 也、閉情況下使所揮發之硫化銨氣體與LED封裝體接觸。 腐蝕之判定：觀察LED封裝體内部之引線架變成黑色 (稱為黑化）之時間，其變色時間越長，則判斷耐腐蝕氣 體性越優異。 觀察10分鐘後、3 0分鐘後、1小時後取出並確認’評 價係將無變色者記為〇，將開始變色者記為△，將茶色〜 褐色者記為x，將完全黑化者記為X X。 201211093 [表7]Plate viewing angle L positive film, adhesive, polarizer protective film, and other 'organic EL (EleCtr〇-lUmineseenee) display in front of the glass protective film, face glass replacement material, adhesive, and field emission display () Various film substrates, a protective film for the front glass, a front glass substitute material, and a subsequent agent. VD (Vide〇Disk), cD/cD_ROM' CD-r / RW, DVD-R/DVD-RAM, MO/MD, PD (phase-change disk), flower and nine thousand cards in the field of optical recording Disk substrate material, reading lens, film, sealing material, adhesive, etc. In the field of optical machines, the material for the lens of the still-life camera, the viewfinder 32 201211093 Prism, the target edge A, the camera of the machine #传感器^^, the camera, the belly, your brother viewfinder. In addition, projection lenses for projection televisions, security seals, adhesives, and the like. Lens material for light sensing machine, sealing material, light agent H light parts field towel, optical communication system material, adhesive optical waveguide, component sealing material, optical fiber material around the optical connector, ferrule , sealing material LED =, and so on. In light passive parts and optical circuit parts, lenses, waveguides, ', sealing materials, CCD sealing materials, and connecting circuits (〇Elc) are evenly sealed, and then sealed with the substrate material, fiber material, and components. Tube, etc. In the field of pre-fibre, lighting for decorative displays, sensors for light-conducting infrastructure, display, identification, etc., and communication circuit peripheral materials: two in the middle: the fiber for machine connection. Semiconductor product -4, #1, u Anti-contact agent material for microetching of 1^SI materials. Automobiles, permanent ❹h domain's reflectors for automobiles, bearings, gears, corrosion-resistant internal parts, Thunder U I switches. P-point, headlights, anti-clock for engine and car - 内 kinds of interior and exterior products, drive engine, brake oil tank, :::: rust 2, interior trim, interior materials, harness for protection and bundling, fuel Hose, car light, splicing s.. Replacement. In addition, double-layer glass for railway vehicles. In addition, the structural components of the aircraft, the wiring harness for protection and bundling (4), and the corrosion-resistant coating around the engine. In the field of construction, the interior of the solar cell is made of two materials, a glass intermediate film, a glass substitute, a light, an electronic functional organic material, and a material for the next generation. ^ ^. Qiu is also an organic EE peripheral material, organic folding parts Light-amplifying element, optical operation 33, 2012-11093 基板 、, substrate material around the organic solar cell, fiber material, sealing material for components, adhesive, etc. Examples of the sealing agent include potting, impregnation (__), transfer mold (four), capacitor C, B, etc. for capacitors, transistors, diodes, light-emitting diodes, ICs, and LSIs. (7) Insulation (P〇t^ng) for F, TAB, etc., underfill, flip-chip, etc., underfill, q卯, bga, etc. 1C package type seal (enhanced underfill). Other uses of the material for optics include the use of the curable resin dimer A and the curable resin composition B, for example, in addition to a carrier, a coating, a coating agent, a molding material (including a sheet, a film). , FRP, etc., and other materials, such as a printed material (including a printed circuit board, a wire coating, etc.) and a sealant, may be exemplified by a cyanate resin composition for a substrate or an acrylic resin which is used as a hardener for the anti-(4) In addition to an adhesive for use in other resins and the like, in addition to an adhesive for civil engineering, construction, automotive, general affairs, and therapeutic use, an adhesive for electronic materials is also exemplified. In the above, examples of the adhesive for the electronic material include an interlayer adhesive for a multilayer substrate such as a buiid_y substrate, a semiconductor adhesive such as a die bond, an underfill, a BGA reinforcing underfill, and an anisotropic. Conductive film (ACF), an anisotropic conductive conductive f (Acp), etc., and the like: In the description of the embodiments, the present invention is further exemplified by the present invention. Unless otherwise specified, the parts are parts by weight. Further, it is not limited to the examples. 7236. In addition, in the present invention, the epoxy equivalent is determined according to JIS κ - 34 201211093, and the viscosity is used for hunger. The meter is used for the measurement. In addition, the analysis conditions in the gas chromatography (hereinafter referred to as GC) (4) separation column f using HP5-MS (0.25 mm I.D.x15m 'film thickness 〇 2 ^ m), the tube is supplied The temperature of the tank was set to an initial temperature of 10 (rc, which was raised at a rate of 15 每 per minute, and was maintained at 30 (TC for 25 minutes. In addition, 氦 was used as a carrier gas. Further, gel permeation chromatography (hereinafter referred to as The measurement for GPC) is as follows: KF- 803L ' KF- 802.5 pipe column Shodex SYSTEM-21 column (x2 root), KF- 802), linked to the solution is tetrahydro hydrazine, the flow rate is Η / min 'column temperature is 40 〇 C, in addition, the detection system is used to carry out the calibration curve A standard polystyrene manufactured by Shodex was used. Synthesis Example 1 A nitrogen purge was applied to a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, and 1 G of water was added to the surface, and 12 g of tungsten was added. 3.0 parts of sodium sulphate, 3.2 parts of diazonahydride, 23 parts of trioctylmethyl acetate (manufactured by Lion Akzo, 50% by weight of diterpene solution, t〇maa _ 5〇), toluene m, 3- Cyclohexamethylene methyl group = 3 ring of stearyl vinegar 22 parts, the solution was heated to 48 ° C, and while stirring vigorously, 220 parts of 35 wt% hydrogen peroxide water was added for 3 minutes, directly stirring at 48 art. 14 hours. After the completion of the reaction, the mixture was neutralized with a 20% by weight aqueous sodium hydroxide solution, and then 45 parts of a saturated aqueous sodium thiosulfate solution was added thereto, and the mixture was stirred for 3 minutes, and allowed to stand. The organic layer separated into 2 layers was taken out and added thereto. Activated carbon (A-Fine - Techno made 'CP2) 20 parts, montmorillonite (manufactured by Kunimine industries' Kunipia F) 20 parts, after 3 hours at room temperature, passed the data. The obtained filtrate was washed three times with 100 parts of water, and toluene was distilled off from the obtained layer of 35 201211093, thereby obtaining I. >Showing J | Oxygen Resin (EP-1) 222 parts obtained, ',, hot color liquid ring 130 g / eq, viscosity 205 mPa.s (25 ° c) clothing oxygen equivalent is a synthesis example 2 叼汉应谷你刊难匕) Ethyl r methyl Shi Xiyuan 1 〇 6 parts, weight average molecular weight 1700 (g τ) saponin end methyl phenyl polyoxanol 234 parts When) is calculated as 1/2 of the weight average molecular weight measured by GPC), 〇' = 18 parts of potassium oxide (KOH) f-alcohol solution', the bath temperature is set to swell, and the temperature is raised. After the temperature was raised, the reaction was carried out under reflux for 8 hours. <> Then, after adding 305 parts of methanol, 86.4 parts of a methanol solution (concentration: 50% by weight) of steamed water was dropped for 1 60 minutes, and reacted at 75 ° C for 8 hours under reflux. After completion of the reaction, the mixture was neutralized with a 5% aqueous solution of sodium dihydrogen phosphate, and about 90% of methanol was recovered by distillation at °C. 38 parts of methyl isobutyl ketone was added and washed twice with 2 parts of water. Then, the organic phase was subjected to a rotary evaporator under reduced pressure at 1 Torr (TC to remove the solvent, thereby obtaining 300 parts of an epoxy resin (EP-2) having a decane structure. The epoxy equivalent of the obtained compound. It is 729 g/eq 'viscosity is ^90 mPa.s (25 ° C), and the weight average molecular weight is 2200'. The appearance is colorless and transparent. Synthesis Example 3 With mixer, reflux cooling tube, stirring device, Dean-Stark (Dean — Stark) The flask was filled with nitrogen gas while adding dimethyl 1,4-cyclohexanedicarboxylate (manufactured by Iwatani Gas, DMCD-p) 14 parts, cyclohexene-4-nonanol 314 parts, tetrabutoxy 36 (tetrabutoxy 36 201211093 titanium) 0.07 parts, while removing the methanol formed by the reaction, while performing i2 ° ° ° 1 hour, i5 ° ° ° i hour, 17 (rc = hour), 19 ( The reaction was carried out for 12 hours under rc. After the reaction was carried out by gas chromatography (GC), it was cooled to 5 Torr. (: After cooling, 347 parts of toluene was added and homogenized, and then oxidized by 1% by weight. 80 parts of sodium solution was washed 3 times for the reaction solution, and then 100 times of water/repetition Washing until the wastewater becomes neutral, distilling off toluene and unreacted 3-cyclohexene-i-methanol by heating under reduced pressure using a rotary evaporator, thereby obtaining bis(3_cyclohexylmethyl)=1 , 4 parts of a compound (D-1) which is a liquid component at room temperature as a main component of 4-cyclohexan dicarboxylic acid. Synthesis Example 4 In a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, helium gas was introduced into one side. Rinse, add 15 parts of water, -95 parts of 12-tungstophosphonium phosphate, scaly & gas-sodium G·78 parts, trioctyl acetate t 5G% xylene solution 2.7 wound toluene 1 80 parts in synthesis example 3 The obtained compound (D - 1 ) 11 8 widely heated the cold liquid to 6 ° ° C, while stirring vigorously, one side of i ^ ^ ^ 35 mass % hydrogen peroxide water 70 parts, directly mixed under 601 13 hours. The progress of the reaction was confirmed by gas chromatography. As a result, the peak of the starting material disappeared. Then, after neutralizing with a 1% by weight aqueous sodium hydroxide solution, 20 parts by weight of 25 parts of sodium thiosulfate aqueous solution was added for 3 minutes. Stir and let stand. Take out 2 layers of <organic|, add activated carbon to it (Aji_〇t〇Fine sh hn 20 parts of 'CP1', bentonite (made by Hojun, Bengel) 2 bruises, stirred at room temperature for 1 hour, and then filtered. The obtained filter 37 201211093 was washed with water (10) portions 3 times. In the organic layer, benzene is removed by steaming, thereby obtaining 119 parts of epoxy resin (Ep_3) which is liquid at normal temperature. The obtained epoxy resin has an epoxy equivalent of 217 g/eq and a viscosity of 7520 mPa*. s (25 ° C) ° Examples 1 and 2, Comparative Examples 1 and 2 Epoxy resin (Ep-1) obtained in Synthesis Example 1 of the Example, dicyclodecanedioxanol (AL-1) As a comparative example, trishydroxypropylpropane (AL-2) was uniformly mixed in the blending amounts described in the following Table to obtain a curable resin composition (F-1) (F-2) for the examples. The curable resin composition (F-3) (F-4) used in the comparative example. [Table 1] Example 1 Example 2 Comparative Example 1 Comparative Example 2 Composition of curable resin composition F-1 F-2 F-3 F-4 Epoxy resin EP-1 5.0 5.0 5.0 5.0 Alcohol AL-1 0.5 0.2 AL-2 0.5 0.2 Examples 3, 4, 5, Comparative Examples 3, 4, 5 For the obtained curable resin composition (F-1) (F-2) (F-3) (F-4) And an epoxy resin (EP-1), which is blended with an acid hardening accelerator (cationic polymerization initiator) in the blending amount as shown in the following Table 2 (manufactured by Sanshin Chemical Industry, San-Aid SI-60, hereinafter referred to as Ci), a curable resin composition is obtained. Further, the obtained compound was evaluated for storage stability and hardenability. The results are also shown in Table 2. 38 201211093 (Evaluation method) • Storage stability: The storage of the curable resin composition at room temperature for 24 hours is stable. If gelation occurs within 24 hours, it is marked as χ, and if it remains in liquid form, it is marked as 〇. ", Hardenability: Hardenability at 80 ° C for 1 hour. The hardened person is referred to as 〇, and the unhardened person (having a fluid or semi-solid state) is referred to as χ. [Table 2] Hardening Resin Composition Example 3 F-1 Example 4 r? 1 Example 5 Comparative Example 3 Comparative Example 4 Comparative Example 5 Composition Epoxy Resin -1--1 5.0 r — 1 5.0 F-2 5.0 F-3 5.0 5.0 50 0. Alcohol AL1 0.5 0.5 0.2 AL—2 0.5 0.2 Lang Bingsen 1 C — 1 0,05 — ---J 0.10 0.05 0.05 0.05 0 05 Juice price results in stable and hardening qualitative LJ. 〇〇〇X 〇〇 14 〇〇〇〇X 〇 According to the above results, when an alcohol such as trimethylolpropane is added in an amount having a good hardenability, the storage stability is poor, and if storage stability is required, the hardenability is deteriorated (Comparative Example) 3, 4) Further, if alcohol is not added, curability and storage stability can be ensured (Comparative Example 5). Examples 6 and 7, Comparative Examples 6 and 7 The obtained curable resin composition (F) — 1 ) and epoxy resin (ΕΡ 1 ), blended with an acid hardening accelerator (C) in the blending amount shown in Table 3 below. — 1 ), a curable resin composition was obtained. 39 201211093 Further, 'the obtained compound was evaluated for moisture permeability. The results are also shown in Table 3. (Evaluation method) • Moisture and humidity conditions: 60 ° C, 90%, 24 hours Hardening conditions: 80. (:, 1 hour [Table 3] Example 6 Comparative Example 6 Example 7 Comparative Example 7 Curable resin composition F-1 - F-1 - Composition Epoxy Resin EP-1 5.0 5.0 5.0 5.0 Alcohol AL-1 0.5 0.5 hardening which #丨C-1 0.05 0.05 0.10 0.10 Evaluation result 1 permeable to wet 87 150 55 120 According to the above results, the curable resin composition of the present invention is effective for moisture permeability. Example 8 and Comparative Example 8 The obtained curable resin composition (F-1) and epoxy resin (EP-1) were obtained by blending an acidic hardening accelerator (c_i) with the blending amount of Table 4 below. The curable resin composition. Further, the obtained compound was evaluated for the subsequent shear strength. The results are also shown in Table 4. (Evaluation method) • Subsequent shear strength hardening conditions: 80 ° C, 1 hour 1 moisture absorption test condition : 60. (:, 90%, 63 hours 201211093 [Table 4] Example 8 Comparative Example 8 Curable resin group ▲F-1 - Composition Epoxy resin EP-1 5.0 5.0 Alcohol AL-1 0.5 Hardening accelerator C-1 0.10 0.10 Evaluation results Subsequent shear strength MPa 43.5 29.5 After moisture absorption test Then, the shear strength MPa is 11.3. 8.6 From the above results, it is understood that the curable resin composition stream of the present invention is excellent not only in adhesion but also in high wettability. Example 9, 0, and Comparative Examples 9 and 10 The curable resin groups or materials (F-1) and (F-5) used in the examples and the curability of the comparative examples were produced in the same manner as in Example 1. Resin composition (F-3), (f_6). The composition is shown in Table 5. For the curable resin composition obtained, sulfhydryl hexahydrophthalic anhydride (manufactured by Shinjuku Physicochemical Co., Ltd., rjKACID MH, hereinafter referred to as Η-1) as a curing agent, and a four-stage scale as a hardening accelerator are used. Salt (manufactured by Nippon Chemical Industry, Hishicolin PX4MP, hereinafter referred to as C-2) was blended in the blending amounts described in Table 5 below to obtain a curable resin composition. Further, the obtained compound was evaluated for storage stability. The results are also shown in Table 5. (Evaluation method) • Storage stability: The viscosity at the time of leaving at room temperature for 4 hours was compared with the initial viscosity and the viscosity after 4 hours. 201211093 The more the viscosity rises, the worse the storage stability is judged β [Table 5] Example 9 Comparative Example 9 Example 10 Comparative Example 10 Curable resin composition F-1 F-3 F-5 F-6 Composition epoxy Resin EP-1 5.0 5.0 5.0 5.0 Alcohol AL-1 0.5 1.0 AL-2 0.5 1.0 Hardener H-1 6.5 6.5 6.5 6.5 /6 t Promoter C —2 0.02 0.02 0.02 0.02 Evaluation result Initial viscosity (mPa.s) 384 420 1623 1587 Viscosity after 4 hours (mpa.s) 584 2368 3528 82432 According to the above results, the curable resin composition using the curable resin composition of the present invention is excellent in storage stability. Examples 11, 12, and Comparative Example 11 For the curable resin composition (F-1) (f-5) used in the examples, the epoxy resin (ΕΡ_1) used as a comparative example, an acid anhydride (η-1) was used. As a hardener, and using cetyltrimethylammonium hydroxide (manufactured by Tokyo Chemical Industry Co., Ltd., 25% methanol solution, hereinafter referred to as c-3) as a hardening accelerator, as shown in Table 6 below. The blending ratio (parts by weight) was blended, and defoaming was carried out for 20 minutes to obtain a curable resin composition. Using the obtained curable resin composition, a volatilization test was carried out in the following manner, and the results are shown together in Table 6. Further, the curing conditions were 12 ° C for 2 hours after the preliminary hardening of 12 ° C χ 2 hours (volatilization test) After performing the practical defoaming for 20 minutes on the curable resin composition obtained in the examples and the comparative examples' It is slowly cast on a glass substrate made of a heat-resistant tape with a barrier of 30 mm x 20 mm x 1 mm in height 42 201211093. After the weight of the cast resin is accurately measured, the cast material is cured under the above conditions. The weight of the hardened material thus obtained was measured, and it was confirmed that the weight at the time of hardening was reduced. (The hardening of the examples and the comparative examples was the same hardening in the same oven) [Table 6] Example 11 Example 12 Comparative Example 11 Hard 4 S resin composition F-1 F-5 _ Composition of cycloid resin EP -1 5.0 5.0 5.0 Alcohol AL-1 0.5 1.0 Hardener H-1 6.5 6.5 6.5 Hardening accelerator C-3 0.02 0,02 0.02 Evaluation results Volatilization test (: ¥ hair) 5.2% 4.9% 13.0% If the example When U and 12 were compared with Comparative Example U, it was found that the amount of volatilization of the curable resin composition of the present invention was small. The curable resin composition of the present invention has an effect of suppressing volatilization at the time of curing. Examples 13 and 14 and Comparative Example 12 An organopolysiloxane compound (EP _ 2 ) obtained in Synthesis Example 2 was used as a composition described in the epoxy resin H 7 to prepare a curable resin composition (7 H F 8 ). Using acid needle (H ~ 1 ) as a hardener, using hardening promotion 30 (C ~ 2) as a hardening accelerator, blending with the blend ratio (parts by weight) shown in Table 7 below, and performing 2 g minutes of defoaming . The curable resin composition of the present invention or comparative use is obtained. (Corrosion gas permeability test) 43 201211093 The obtained curable resin composition was filled in a syringe, and cast into a surface of an outer diameter of 5 mm square with a central light-emitting wave of 465 nm using a precision discharge device. The packaged LED package (4.4 mm inner diameter and 1.25 mm outer wall height). The cast product was placed in a heating furnace, and subjected to hardening treatment at 12 ° C for 1 hour, and further at 15 ° C for 3 hours to prepare a package. The LED package was placed in a corrosive gas under the following conditions, and the change in color of the silver-plated lead frame portion inside the seal was observed. The results are shown in Table 7. 〇 Measurement conditions: Corrosion gas: Ammonium sulfide 20% aqueous solution (the sulfur component turns black after reacting with silver). Contact method. In a wide-mouth glass bottle, the container of the sulfurized aqueous solution is mixed with the above LED package. 'Cap the lid of the wide-mouthed glass bottle, and in the case of closing, the vulcanized ammonium sulfide gas is brought into contact with the LED package. Corrosion determination: When the lead frame inside the LED package became black (referred to as blackening), the longer the discoloration time was, the more excellent the corrosion resistance was judged. After 10 minutes, 30 minutes, and 1 hour after the observation, it was taken out and confirmed that the evaluation was marked as 〇, the person who started discoloration was denoted by △, the person who turned brown to brown was denoted by x, and the person who completely blackened was recorded as For XX. 201211093 [Table 7]

t實施例13 實施例14 比較例12 硬化性樹脂組成物 F—7 F-8 組成 環氧樹脂 EP-2 14.6 14.6 14.6 醇 AL-1 0.7 0.3 硬化劑 H-1 3.4 3.4 3 4 硬化促進劑 C—2 0.06 0.06 0.06 評價結果 腐蝕氣體穿透性試驗 10分鐘 〇 〇 〇 30分鐘 〇 〇 △ 1小時 〇 〇 X 根據上述結果瞭解到，本發明之硬化性樹脂組成物與 比較例之硬化性樹脂組成物相比，引線架之鍍銀不變色， 且耐腐蝕氣體性優異》 實施例1 5、16 使用合成例1、4中所獲得之環氧樹脂（Ep 一 1 ) ( Ep 一 3 )’以表8所記載之組成製作硬化性樹脂組成物（ρ 一 9 ) (F - 10)。將作為硬化劑之酸酐（H— i )、n# —環己烧三 甲酸一1，2—酐（三菱瓦斯化學製造，η—ΤΜΑη，以下稱為 Η— 2 )’使用硬化促進劑（C — 2 )作為硬化促進劑，以下述 表8所示之摻合比（重量份）進行摻合，進行2 〇分鐘消泡， 獲得本發明之硬化性樹脂組成物。 (穿透率試驗） 對所獲得之硬化性樹脂組成物實施真空消泡2〇分鐘 後’以成為3 0 mm X 2 0 mm X高度1 mm之方式緩緩地洗鎮於 以财熱帶製成障壁之玻璃基板上。使該澆鑄物於12(rc χ3 小時之預備硬化後以150t><l小時進行硬化，獲得厚度i 45 201211093 mm之穿透率用試驗片。測定4〇〇 nm下之各硬化物之穿透 率〇 (LED點亮試驗） 將所獲得之硬化性樹脂組成物填充於注射器中，使用 精密喷出裝置’澆鑄成搭載有中心發光波465 nm之晶片的 外徑5 mm見方之表面安裝型LED封裝體（内徑4 4爪爪， 外壁高度1·25 mm)。將該澆鑄物投入加熱爐中，進行12〇 °C、1小時，進而i 5〇〇c、3小時之硬化處理而製作led封 裝體。安裝LED後，以下述條件點亮LED並測定照度，梦 果示於表8。 點亮詳細條件 發光波長：465 nm 驅動方式：定電流方式、60 mA (發光元件額定電流為 30 mA ) 驅動環境：85°C、85% 驅動時間：200小時 評價：200小時點亮後之照度保持率 [表8] 貫施例 15 16 環肩 ^樹脂組成物 F-9 F-10 組成 環氧樹脂（EP— 1) 4.0 5.0 環氧樹脂（EP—3) 6.0 5.0 醇（AL-1) 1.4 1.4 硬化劑 酸酐（Η—1) 6.8 7.2 酸酐（Η—2) 1.2 1.2 硬化促進劑 硬化促進劑（C —2) 0.02 0.02 400nm下之穿透率（〇/0) 89.2 90.5 LED點亮試驗照度保持率（〇/0) 91.2 89.7 46 201211093 根據以上妹果·^主 Γ ^ ^ 、° 知，本發明之硬化性樹脂組成物係對 「儲存穩定性或廍π从 學㈣^ 之穩定性優#，並且對光或熱之光 学特性亦優異，i隹& 上+ ，耐腐蝕氣體性等特性亦優異之光學 材料」有用之化人私 _ , 成八/|χ ·σ 。另外，自儲存穩定性或硬化時揮發 方面可明瞭，製成硬化性樹脂組成物時之特性中 ’、具有優異之特性。進、^ ^ 延肉月瞭耐透濕性、耐吸濕性、接 者性亦優異。 詳細說明，但本 圍而進行各種變 雖已參照特定之態樣對本發明進行了 業者可明瞭，可不脫離本發明之精神與範 更及修正。 =者’本中請案係基於2G1()年5月25日提出申請之 利申請案（特願2010— 118877 )，藉由引用而援引其 卜本文中引用之所有參照均作為整體而併入。 【圖式簡單說明】 無 【主要元件符號說明】 無t Example 13 Example 14 Comparative Example 12 Curable resin composition F-7 F-8 Composition Epoxy Resin EP-2 14.6 14.6 14.6 Alcohol AL-1 0.7 0.3 Hardener H-1 3.4 3.4 3 4 Hardening Accelerator C —2 0.06 0.06 0.06 Evaluation result Corrosion gas permeability test 10 minutes 〇〇〇 30 minutes 〇〇 Δ 1 hour 〇〇 X According to the above results, it is understood that the curable resin composition of the present invention and the curable resin of the comparative example are composed. Compared with the material, the silver plating of the lead frame does not change color, and the corrosion resistance is excellent. Example 1 5, 16 The epoxy resin (Ep-1) (Ep-3) obtained in Synthesis Examples 1 and 4 was used. The composition described in Table 8 was used to prepare a curable resin composition (ρ - 9 ) (F - 10). Using an acid anhydride (H—i) as a hardener, n#—cyclohexane tricarboxylic acid-1,2-anhydride (manufactured by Mitsubishi Gas Chemical, η—ΤΜΑη, hereinafter referred to as “Η-2”), using a hardening accelerator (C) 2) As a curing accelerator, the blending ratio (parts by weight) shown in the following Table 8 was blended, and defoaming was carried out for 2 minutes to obtain a curable resin composition of the present invention. (Permeability test) Vacuum defoaming of the obtained curable resin composition was carried out for 2 minutes, and then slowly washed in a manner of 30 mm X 2 0 mm X height 1 mm. On the glass substrate of the barrier. The cast material was hardened at 150 t < l hours after preliminary hardening for 12 hours (rc χ 3 hours) to obtain a test piece for a transmittance of thickness i 45 201211093 mm. The wear of each hardened material at 4 〇〇 nm was measured. Permeability 〇 (LED lighting test) The obtained curable resin composition was filled in a syringe, and was cast into a surface mount type having an outer diameter of 5 mm square, which was mounted on a wafer having a central light-emitting wave of 465 nm using a precision discharge device. LED package (inner diameter 4 4 claws, outer wall height 1·25 mm). The cast material was placed in a heating furnace and subjected to hardening treatment at 12 ° C for 1 hour and then for 5 hours and 3 hours. After the LED is mounted, the LED is illuminated under the following conditions and the illuminance is measured. The dream is shown in Table 8. Lighting detailed conditions Illumination wavelength: 465 nm Driving method: constant current mode, 60 mA (lighting element rated current is 30 mA ) Driving environment: 85 ° C, 85% Driving time: 200 hours Evaluation: illuminance retention after 200 hours of lighting [Table 8] Example 15 16 Ring shoulder ^Resin composition F-9 F-10 Composition Epoxy Resin (EP-1) 4.0 5.0 Epoxy Resin (EP-3) 6.0 5 .0 Alcohol (AL-1) 1.4 1.4 Hardener anhydride (Η-1) 6.8 7.2 Anhydride (Η-2) 1.2 1.2 Hardening accelerator hardening accelerator (C-2) 0.02 0.02 400nm penetration rate (〇/ 0) 89.2 90.5 LED lighting test illuminance retention rate (〇/0) 91.2 89.7 46 201211093 According to the above-mentioned sisters, ^ main Γ ^ ^, °, the curable resin composition of the present invention is "storage stability or 廍π 从学(四)^ The stability is excellent #, and the optical properties of light or heat are also excellent, i隹&+, and corrosion-resistant gas properties are also excellent optical materials. /|χ · σ. In addition, it is clear from the viewpoint of storage stability or volatilization during hardening, and has excellent characteristics in the properties of the curable resin composition. It has excellent moisture permeability. Further, the moisture absorption resistance and the splicing property are also excellent. The detailed description of the present invention has been made in view of the specific aspects, and the invention can be modified without departing from the spirit and scope of the present invention. 'This case is based on the application for the application on May 25 of 2G1() (Application No. 2010-118877), by reference to invoke all of which is incorporated by reference herein BU are incorporated as a whole. [Drawings briefly described the major elements None None REFERENCE SIGNS

Claims (1)

201211093 七、申請專利範圍： 1. 一種硬化性樹脂組成物，其含有具有環氧環己烷結構 之環氧樹脂、具有三環癸烷結構之醇。 2. 如申請專利範圍第1項之硬化性樹脂組成物，其中， 具有環氧環己烷結構之環氧樹脂為脂環式環氧樹脂。 3 ·如申請專利範圍第1項之硬化性樹脂組成物，其中， 具有環氧環己烷結構之環氧樹脂為具有環氧環己烷結構及 碎氧燒結構的環氧樹脂。 4 · 一種硬化性樹脂組成物，其含有申請專利範圍第1至 3項中任一項之硬化性樹脂組成物與硬化劑及/或硬化促 進劑。 5. 如申請專利範圍第4項之硬化性樹脂組成物，其中， 硬化劑為酸酐。 6. —種硬化物，其係將申請專利範圍第4或5項之硬化 性樹脂組成物硬化而獲得。 7. —種光半導體裝置，其含有申請專利範圍第4或5項 之硬化性樹脂組成物。 48201211093 VII. Patent application scope: 1. A curable resin composition containing an epoxy resin having an epoxycyclohexane structure and an alcohol having a tricyclodecane structure. 2. The curable resin composition according to claim 1, wherein the epoxy resin having an epoxycyclohexane structure is an alicyclic epoxy resin. 3. The curable resin composition according to claim 1, wherein the epoxy resin having an epoxycyclohexane structure is an epoxy resin having an epoxycyclohexane structure and a oxy-oxygen structure. A curable resin composition comprising the curable resin composition according to any one of claims 1 to 3, and a hardener and/or a hardening accelerator. 5. The curable resin composition of claim 4, wherein the hardener is an acid anhydride. A cured product obtained by hardening a curable resin composition of claim 4 or 5. 7. An optical semiconductor device comprising the curable resin composition of claim 4 or 5. 48
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