TW201137044A - Curable resin composition and cured article thereof - Google Patents

Curable resin composition and cured article thereof Download PDF

Info

Publication number
TW201137044A
TW201137044A TW100106828A TW100106828A TW201137044A TW 201137044 A TW201137044 A TW 201137044A TW 100106828 A TW100106828 A TW 100106828A TW 100106828 A TW100106828 A TW 100106828A TW 201137044 A TW201137044 A TW 201137044A
Authority
TW
Taiwan
Prior art keywords
group
resin composition
epoxy resin
acid
curable resin
Prior art date
Application number
TW100106828A
Other languages
Chinese (zh)
Other versions
TWI538959B (en
Inventor
Yoshihiro Kawada
Masanori Oda
Chie Sasaki
Naofusa Miyagawa
Masataka Nakanishi
Original Assignee
Nippon Kayaku Kk
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Kayaku Kk filed Critical Nippon Kayaku Kk
Publication of TW201137044A publication Critical patent/TW201137044A/en
Application granted granted Critical
Publication of TWI538959B publication Critical patent/TWI538959B/en

Links

Classifications

    • 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
    • H01L23/296—Organo-silicon compounds
    • 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
    • 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
    • C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
    • C08G59/306—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing silicon
    • 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
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4215—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof cycloaliphatic
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • 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
    • 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
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/52—Encapsulations
    • H01L33/56—Materials, e.g. epoxy or silicone resin

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Epoxy Resins (AREA)
  • Silicon Polymers (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
  • Led Device Packages (AREA)

Abstract

Disclosed is a curable resin composition which provides a cured article that satisfies physical properties required for use in an electrical or electronic material, particularly as a semiconductor sealant. Specifically disclosed is a curable resin composition which provides a cured article that has excellent curability, adhesiveness, light resistance, heat resistance, and gas impermeability, and when being used as an LED sealant, generates little resin stress to a chip and does not cause deterioration of illuminance. The curable resin composition comprises (A) an epoxycyclohexyl group-containing organopolysiloxane, (B) an alicyclic epoxy resin, and (C) an acid anhydride, wherein the amount of the alicyclic epoxy resin (B) is from 1.5 to 40% by weight of the total amount of the epoxycyclohexyl group-containing organopolysiloxane (A) and the alicyclic epoxy resin (B).

Description

201137044 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種適合於電氣電子材料用途，尤其適 合於光半導體用途之硬化性樹脂組成物及其硬化物。 【先前技術】 先前以來，作為LED製品等光半導體元件之密封材 料’就性能與經濟性之平衡之觀點而言，—直採用環氧樹 脂組成物H，廣泛使用以耐熱性、透明性、機械特性 ，平衡優異之雙酚A型環氧樹脂為代表的環氧丙基醚型環 氧樹脂組成物。 但是，發展LED製品之發光波長之短波長化（於主要 進行藍色發光之LED製品中表示__以下之情形）之姓 果指出：因短波長之光之影響，上述密封材料於led晶片 上著色，最終導致LED製品之照明度下降。 因此，以3，，4，-環氧環己基甲酸从環氧環己基甲酉旨 late)為代表之脂環族環氧樹脂盘且 a ^ θ /…、有方香環之環氧丙基醚 1娘氧樹脂組成物相比，於透明性方 ,,, 处生方面更優異，因此將其 作為LED密封材料而積極研究（專利文獻1、2 )。 又，近年來之LED製品祜扣山士 明+ 裂口°被才曰出有以下問題：因為對照 明或TV之背光等進行更高高亮度 發 化LED點允時伴隨大量 發熱，因此即便為使用該脂環 ^ . 展軋树脂之樹脂組成物， '、會於LED晶片上產生著色，最 下 一 取、作為led製品其照明度 ，且就耐久性方面而言，亦遺留 缉有問碭（專利文獻3 )。 201137044 [專利文獻1]曰本特開平9—213997號 [專利文獻2]日本專利361 8238號 [專利文獻3]日本特再2〇〇5_ 1〇〇445號 [專利文獻4]日本特開2〇〇6_ 225515號 [專利文獻5]日本特開2〇〇7_ 324256號 [專利文獻6]日本特開2〇〇〇_ 174347號 【發明内容】 就上述環氧樹脂之耐久性之問題而言， 二已：究：以如聚，夕氧樹脂或㈣改質環氧樹脂等為 代表之導入有矽氧烷骨架（具體 /、巧ύ1〜0鍵之哥 架）之環氧樹脂用作密封材料。 已知-般導入有矽氧烷骨架之環氧樹脂與不導 貌骨架之環氧樹脂相比，對於熱與光更穩定。 用於⑽製品之密封材料時，就LED晶 = 而+ w > 丄 < 考色之觀點 而5，可谓導入有石夕氧烧骨架之環氧樹脂之耐久性比不壤 入矽氧烷骨架之環氧樹脂更優異。 導 但是，由於導入有該石夕氧烧骨架之樹脂類 氧樹脂㈣，硬化物之硬度並不充分，因此存在如下等缺 點：用於配線之金線因振動而斷裂，又， 、 不足而容易剝落（專利文獻4)。 &之接者性 為了解決此種問題’於專利文獻4中，進 試：併用交聯密度高（於所有石夕原子中以超過40莫耳:;之 •氧—原子)之有機聚二二 长氧樹月日與脂環族環氧樹脂。 201137044 仁疋右為專利文獻4中所記載之組成 問題：因有機聚石夕氧之交聯密度 "下述 含量多，故雖接著性優里，作硬化版 “展氧樹脂之 f ru一硬化物變得過硬 _密封時晶片容易受到應力可知由此會=: 過程中之照明度劇烈劣化之問題。 站売 J 一方面’ 一般而〗使用聚石夕氧樹脂或聚石夕氧改質 %氧樹脂t LEDk透氣性性欠佳。因此，當使 氧樹脂或聚石夕氧改質環氧樹脂作為LED密封材料時，雖妙 於LED晶片上之著色不會成為問題，但產 ： 成構件之劣化、著色之問題。尤其，當於生活環境： 時，各種化合物懸浮，此種化合物渗入内部而成為產生不 良情況之起因。例如當用於照明用途年， 仔在如下之課題： 因^境中之氣體等穿透㈣之密封材料，而使锻敷於作為 LED封裝體内之構成構件之金屬導線架上之銀成分（為了 提鬲反射率而實施過鍍銀）變色或黑化，最終使作為 製品之性能下降（專利文獻5、6 )。 為了解決該耐透氣性性之問題，於專利文獻5、6中使 用包覆耐透氣性性之㈣劑、藉由無機材料包覆金屬部等 方法，但存在如下問題：不僅步驟增加，生產性變差，而 且因包覆部與密封劑之間之折射率差而導致光之取出效 變差。 … 本發明係鑒於上述先前技術而完成之發明，其目的在 於提供一種可提供滿足作為電氣電子材料用途，尤其光半 導體密封材料所要求之各種物性之硬化物的硬化性樹脂組 201137044 成物’具體而言’其目的在於提供—種可提供硬化性、接 者性、耐光性、耐熱性及对透氣性性優異，並且用作⑽ 密封材料時對於晶片之樹脂應力較少，不產生照明度劣化 之硬化物的硬化性樹脂組成物。 本發明人等為達成上述目的而反覆潛 完成了下述所示之本發明。 °果 ⑴-種硬化性樹脂組成物，係含有含環氧環己基之 有機聚碎氧（A )、脂環族環氧樹脂（B )及酸gf ( c )，且 脂環族環氧樹脂⑻於含環氧環己基之有機聚石夕氧（A) 與脂環族環氧樹脂⑻之總量中所佔之量為h %。 里里 種硬化性樹脂組成物，係含有含環氧環己基之 有機聚妙氧（A)、脂環族環氧樹脂（B)及酸針（〇，且 脂《環氧樹脂⑻於含環氧環己基之有機聚石夕氧（A) '、月曰％族環氧樹脂（B )之總量中所佔之量為2〜重量％。 (3 )如上述（1 )或（2 )之硬化性樹脂組成物，其中， 脂=環氧樹脂⑻於含環氧環己基之有機聚石夕氧：A) %族環氧樹脂⑻之總量中所佔之含量為咖（含環 氧：己基之有機聚矽氧（A)之重量平均分子量）+(含環 氧衷己基之有機聚矽氧（A)之環氧當量）重量❶/〇以下。 )如上述（1 )至（3 )中任-項之硬化性樹脂組成 進一步含有多元羧酸（D)。 (5 )如上述（4 )之硬化性樹脂組成物，其中，上述 缓S义（D )係、藉由碳數為5以上之2〜6官能之多元醇 201137044 與飽和脂肪族環狀酸酐之反 久應所獲得的化合物。 (6)如上述（1)至（5)中# 中任一項之硬化性樹脂組成 物’其中，上述含環葡援；3甘 且古q 衣氧衣己基之有機聚石夕氧（A)之結構中 具有苯基。 ()^ ^述（1 ) i ( 6 )巾任—項之硬化性樹脂組成 ” t ’上述含環氧環己基之有機聚矽氧…係具有由 二甲基取代、二苯基取代或該等之混合物所構成之鏈狀聚 石夕氧部位，以及具有環氧環己基之三維縮合物部位（倍半 石夕氧烧（SilSeSqui(3xane)部位）的嵌段型之化合物。 (、8) -種硬化物，係上述⑴至⑺中任一項之硬 化性樹脂組成物經硬化而成。 (9) 一種光半導體密封用硬化性樹脂組成物係由上 述（1 )至（7 )申任一項之硬化性樹脂組成物構成。 (1〇) —種光半導體裝置，係利用如上述（9)之光半 導體密封用硬化性樹脂組成物進行硬化及密封而得。 本發明之硬化性樹脂組成物作為電氣電子材料用途， 尤其是有用為光半導體密封材料，可提供硬化性、接著性、 耐光性、耐熱性及耐透氣性性優異，並且用作led密封材 料時對於晶片之樹脂應力較少，不產生照明度劣化之硬化 物。 【實施方式】 以下，對本發明之硬化性樹脂組成物加以記載。 本發明之硬化性樹脂組成物包括含環氧環己基之有機 聚矽氧（A )、脂環族環氧樹脂（B )及酸酐（C )。 7 201137044 含環氧環己基之有機聚矽氧（A)係至少其分 %氧％己基之環氧樹脂，一般可藉由將含有環氧環甚 二烷氧基矽烷用於原料之溶膠—凝膠反應來合成。具 言，可列舉日本特開_4—25_號公報、日本特開、· _=4:號r、w°2°°4/G72i5G號公報'日本特開屬 _ = _6/("399()號公報' 日本特開觸6 一 1 〇4248號公報、卿勒/ 13·號公報、日本特開顧 —1〇849號公報、日本㈣編—公報、w咖5 /100445號公報、日本特開細—17464〇號公報等中所記 =具有三維擴展之網眼狀之結構的倍半石夕氧垸型有機聚 本發明中之有機聚石夕氧之結構並無特別限定，就相溶 2面而t ’其結構中具有芳香族基之有機聚石夕氧相溶性 車父佳。 2，由於就通常之單純之三維網眼結構之矽氧烷化合 物而5。所獲得的硬化物變得過硬，因此較理想的是設定 為緩和硬度之結構。於本發明中’尤加為設定《^分子中 具有聚碎氧鍵段與藉^溶膠-凝膠反應所獲得之上述倍半 =燒結構之嵌段結構體（以下，稱為嵌段㈣氧院化合 物（幻））。即，散段型石夕氧烧化合物（ai)係」分子中 :有鏈狀聚矽氧部位與由倍半矽氧烷結構所構成之三維縮 δ物部位之嵌段結構體。 非如通常之嵌段共聚物 ’而是成為以三維地擴 嵌段型矽氧烷化合物（A1 )並 般於直鏈上具有重複單位之化合物 201137044 展之網眼狀之結構即倍半石夕氧貌結構部位為核，鍵狀 矽氧部位延伸，而與.下一個倍半矽 Λ 拔 4· u « 乳坑、、口構部位鍵結之結 結構於對本發明之硬化性組成物之硬化物賦予硬度 /、柔軟性之平衡的意義而言有效。 嵌段型矽氧烷化合物（Α Π你丨4 π , … …）例如可如下述般將由通式 ⑴所表示之Μ基料化合物（a)與由通式⑺ :之聚石夕氧油⑴作為原料來製造，亦可視需要使用通式 ()所表不之烧氧基钱化合物（e)作為原料。嵌段” 氧烧化合物（A1)之鏈狀聚石夕氧部位係由聚石夕氧油⑴形 成：三維之網眼狀倍半矽氧烷部位係由烷氧基矽烷⑷" 及視需要為烧氧基石夕烧（c))形成。 以下，對各原料進行詳細說明。 烷氧基矽烷化合物（a)係由下述式（1)表示 xsi(〇R2)3 r n 通式（1)中之χ若為具有環氧環己基之有機基，則並 無特別限制。例如可列舉：点—(3,4_環氧環己基)乙基' r - (3,4一環氧環己基)丙基、冷—(3,4_環氧環己基)丙 基 '万一（3,4一環氡環己基）丁基等經具有環氧基之環己基 取代之碳數為1〜5的院基。該等之中，較佳為經具有環氧 基之環己基取代之碳數為丨〜3之烷基，特佳為沒—（3,4一 環氧環己基）乙基。 通式（1 )中’存在複數個之I彼此可相同’亦可不同， 表不碳數為1〜10之直鏈狀、之鏈狀或環狀之烷基。例如 可列舉：甲基、乙基、正丙基、異丙基、正丁基、異丁基、 201137044 第丁基正戊基'正己基、環戊基'環己基等。就相溶 性、反應性等反應條件之觀點而言，該等r2較佳為甲基或 乙基，特佳為甲基。 烷氧基矽烷（a )較佳之具體例可列舉：y? - (3,4 -環 氧環己基)乙基二甲氧基矽烷 '石—(3,4_環氧環己基)乙基 -乙氧基碎烧等’特佳為沒_ (3,4 —環氧環己基）乙基三甲 氧基矽烷。該等烷氧基矽烷化合物⑴可單獨使用，亦可 使用2種以上’亦可與後述之烷氧基矽烷⑴併用。 聚夕氧油（b )係下述之鏈狀聚矽氧油，即：具有下述 弋（）所示之構的末端具有矽醇基（silan〇l gr〇up)之鏈狀 聚矽氧油： HO—一~-Si-"Ο—)—η 丁丨 / Η ⑵ 通式（2)中，多個存在之I彼此可相同亦可不同，表 示碳數為1〜10之烷基、碳數為6〜14之芳基、碳 〜10之稀基。又，通式（2)中，m表示重複數。” 碳數為1〜10之烷基可列舉碳數為丨〜1〇之直鏈狀、 支鍵狀或環狀之烷基，例如可列舉：甲基、乙基、正丙美 異丙基、正丁基、異丁基、第二丁基、第三丁基正戊美、 異戊基'戊基、正己基、環戊基'環己基、辛基、2—乙基 己基、壬基、癸基等。該等之中，若考慮耐光性，則較佳 201137044 為甲基、乙基、環己基、正丙基。 奴數為 6〜14之关其办丨丄—η 之方基例如可列舉：苯基、鄰甲苯基、 間甲苯基、冑甲苯基、二甲苯基等。 碳數為2〜10之稀基可列舉：乙稀基、卜甲基乙稀基、 烯丙基、丙稀基、丁稀基、戊稀基、己稀基㈣基等。 就耐光性'耐熱性之觀點而言，R3較佳為甲基、苯基、 環己基、正丙基’特佳為曱基、苯基。再者，於本發明中， 就相浴性方面而言’特佳為至少取代基之一部分具有苯基 者。 通式（2)之化合物之m以平均值計表示3〜2〇〇，較佳 為3〜1〇〇,更佳為3〜5〇。若瓜小於3，則硬化物變得過硬， 低彈性模數特性下降。若m超過2〇〇,則存在硬化物之機械 特性惡化的傾向而不佳。 〜聚矽氧油（b)之重量平均分子量（Mw)較佳為3〇〇 * 18,000 (凝膠滲透層析儀（GPC)測定值）之範圍者。該 等之中，若考慮低溫下之彈性模數，則分子量較佳為3〇〇 1 〇’〇〇0者，若進而考慮組成物化時之相溶性，則更佳為 3〇0〜5’000者，特佳為500〜3，000者。於重量平均分子量 於300之情形時，則可能特性鏈段之鏈狀聚矽氧部分之 生難以顯現出’而有損作為嵌段型之特性，若 1 8，0 0 〇，目丨丨g 士 只J具有強烈之層分離結構，當用於光學材料時穿透 變 ， ’而變得難以使用。於本發明中，可算出使用GpC '下述條件下所測定之聚苯乙烯換算之重量平均分子量 (MW)作為聚矽氧油（b)之分子量。 11 201137044 GPC之各種條件 製造者：島津製作所 管柱：保護管柱（Guard Column) SHODEX GPC LF—G LF- 804 ( 3 根） 流速：1.0 ml / min.201137044 VI. Description of the Invention: [Technical Field] The present invention relates to a curable resin composition suitable for use in an electric and electronic material, particularly suitable for use in an optical semiconductor, and a cured product thereof. [Prior Art] As a sealing material for optical semiconductor elements such as LED products, in terms of balance between performance and economy, the epoxy resin composition H is used directly, and heat resistance, transparency, and mechanical use are widely used. A epoxidized propyl ether type epoxy resin composition represented by a bisphenol A type epoxy resin excellent in balance. However, the development of the short-wavelength of the wavelength of the light-emitting wavelength of the LED product (in the case of the LED product which mainly performs blue light emission) indicates that the above-mentioned sealing material is on the led wafer due to the influence of light of a short wavelength. Coloring eventually leads to a decrease in the illumination of LED products. Therefore, an alicyclic epoxy resin disk represented by 3,4,4-epoxycyclohexylcarboxylic acid from epoxycyclohexylcarbazide and a ^ θ /..., a glyceryl ether 1 having a square scented ring Since the matte resin composition is superior in transparency and hygiene, it has been actively studied as an LED sealing material (Patent Documents 1 and 2). In addition, in recent years, LED products have been smashed with the following problems: because of the higher brightness and brightness of the backlights of the lighting or TV, it is accompanied by a large amount of heat, so even if it is used The alicyclic ring. The resin composition of the rolled resin, 'will produce coloration on the LED wafer, the bottom is taken as the illumination of the led product, and in terms of durability, there is also a question left ( Patent Document 3). [Patent Document 1] Japanese Patent Laid-Open No. Hei 9-213997 [Patent Document 2] Japanese Patent No. 361 8238 [Patent Document 3] Japanese Patent No. 2〇〇5_1〇〇445 [Patent Document 4] Japanese Patent Laid-Open No. 2 [Patent Document 5] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. , two have: research: as a representative of such as poly, oxime resin or (four) modified epoxy resin, etc. introduced into the oxime skeleton (specific /, ύ ύ 1~0 key of the brother frame) epoxy resin used as a seal material. It is known that an epoxy resin having a naphthene skeleton introduced is more stable to heat and light than an epoxy resin having a non-lead skeleton. When used for the sealing material of the product (10), as far as the LED crystal = and + w > 丄 < from the point of view of the color, it can be said that the durability of the epoxy resin introduced into the skeleton of the oxylate is lower than that of the oxime The epoxy resin of the skeleton is more excellent. However, since the hardness of the cured product is not sufficient due to the introduction of the resin-based oxygen resin (four) of the oxylate skeleton, the gold wire used for wiring is broken by vibration, and is insufficient. Peeling (Patent Document 4). In order to solve such a problem, in the patent document 4, a test is conducted: an organic polydimer having a high crosslink density (more than 40 moles in all the stone atoms: oxygen atoms) Dihydrogen tree tree day with cycloaliphatic epoxy resin. 201137044 仁疋右 is a composition problem described in Patent Document 4: Because of the cross-linking density of organic poly-stones, the following contents are high, so the adhesion is excellent, and the hardened version of the oxy-resin is hardened. The material becomes too hard _The wafer is susceptible to stress when sealed. It is known that the illuminance in the process is severely degraded. Station 売J On the one hand, 'Generally, the use of polysulfide or polysulfide Oxygen resin t LEDk has poor gas permeability. Therefore, when oxygen resin or polyoxo-modified epoxy resin is used as the LED sealing material, although the coloring on the LED wafer is not a problem, it is produced: The problem of deterioration and coloration. In particular, when in the living environment: various compounds are suspended, such compounds penetrate into the interior and become a cause of undesirable conditions. For example, when used for lighting purposes, the following topics are considered: The gas in the middle penetrates the sealing material of (4), and discolors or blackens the silver component (silver plated for the purpose of improving the reflectance) which is forged on the metal lead frame which is a constituent member of the LED package body, In the end, the performance of the product is lowered (Patent Documents 5 and 6). In order to solve the problem of the gas permeation resistance, Patent Documents 5 and 6 use a coating agent which is resistant to gas permeability (IV) and is coated with an inorganic material. The method is the same, but there is a problem that not only the steps are increased, the productivity is deteriorated, but also the light extraction effect is deteriorated due to the difference in refractive index between the coating portion and the sealant. The present invention is in view of the above prior art. The invention has been made in an effort to provide a curable resin group which can provide a cured product which satisfies various physical properties required for electrical and electronic materials, in particular, an optical semiconductor sealing material, and is intended to provide a specific type. It is a curable resin composition which is excellent in hardenability, heat resistance, heat resistance, and gas permeability, and is used as a (10) sealing material, which has less stress on a wafer and does not cause deterioration of illuminance. The inventors of the present invention have completed the present invention described below in order to achieve the above object. The fruit (1)-curable resin composition contains There are organic poly-crushed oxygen (A), alicyclic epoxy resin (B) and acid gf (c) containing epoxy cyclohexyl group, and the alicyclic epoxy resin (8) is on the organic poly-stone containing epoxycyclohexyl group. The amount of oxygen (A) and the total amount of the alicyclic epoxy resin (8) is h%. The sturdy resin composition contains an organic cyclooxygen (A) and a fat containing an epoxycyclohexyl group. Ring-group epoxy resin (B) and acid needle (〇, and grease "epoxy resin (8) in epoxy cyclohexyl-containing organic polyoxo (A) ', moon 曰% epoxy resin (B) total (3) The curable resin composition according to (1) or (2) above, wherein the fat = epoxy resin (8) is on the organic polystone containing epoxycyclohexyl group Oxygen: A) The content of the total amount of the epoxy resin (8) is the coffee (the weight average molecular weight of the organic polyfluorene (A) containing epoxy: hexyl group) + (the organic polyfluorene containing epoxy group) The epoxy equivalent of oxygen (A) is less than ❶/〇. The curable resin composition according to any one of the above (1) to (3) further contains a polyvalent carboxylic acid (D). (5) The curable resin composition according to the above (4), wherein the above-mentioned retarded (D)-based polyether alcohol 201137044 having a carbon number of 5 or more and a saturated aliphatic cyclic anhydride The compound obtained should be obtained for a long time. (6) The curable resin composition of any one of the above-mentioned (1) to (5), wherein the above-mentioned organic polycime (A) containing a ring of chlorhexidine; The structure has a phenyl group. ()) (1) i (6) towel--the hardening resin composition of the item "t' The above-mentioned epoxycyclohexyl-containing organopolyoxo... has a dimethyl substitution, a diphenyl substitution or the a chain-shaped polyoxo-oxygen moiety composed of a mixture of the same, and a block-type compound having a three-dimensional condensate portion of an epoxycyclohexyl group (Sil SeSqui (3xane) portion) (8) A hardened resin composition obtained by curing the curable resin composition according to any one of the above (1) to (7). (9) A curable resin composition for optical semiconductor sealing is claimed by the above (1) to (7) (1) An optical semiconductor device obtained by curing and sealing the curable resin composition for optical semiconductor sealing according to the above (9). The curable resin of the present invention. The composition is useful as an electrical and electronic material, and is particularly useful as an optical semiconductor sealing material, and is excellent in hardenability, adhesion, light resistance, heat resistance, and gas permeability resistance, and is used as a resin for a lead sealing material. Less, no illumination [Embodiment] The curable resin composition of the present invention is described below. The curable resin composition of the present invention comprises an organocyclohexyloxy group (A) or an alicyclic epoxy group containing an epoxycyclohexyl group. Resin (B) and anhydride (C). 7 201137044 Epoxy cyclohexyl-containing organopolyfluorene (A) is an epoxy resin containing at least % oxygen % hexyl group, generally by containing an epoxy ring dioxane Oxy decane is used for the sol-gel reaction of a raw material to synthesize it. In other words, Japanese Patent Publication No. _4-25_, Japanese Special Opening, _=4: No. r, w°2°°4/ G72i5G Bulletin 'Japan Special Ownership _ = _6/("399() Bulletin' Japan Special Openance 6-1 〇4248 Bulletin, Qingle / 13· Bulletin, Japan Special Open Gu - 1〇 849公报 中 日本 日本 日本 日本 17 17 17 17 17 17 17 17 17 = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = The structure of the organic polyoxo oxygen in the invention is not particularly limited, and is an organic polystone having two sides and having an aromatic group in its structure. In the case of a typical three-dimensional network structure of a oxane compound, the hardened material obtained is too hard, and therefore it is preferable to set the structure to moderate the hardness. In the present invention, 'Ulga is a block structure in which the above-mentioned half-half-sinter-fired structure having a poly-heavy-oxygen bond segment and a sol-gel reaction is obtained (hereinafter, referred to as a block (four) oxygen plant) Compound (phantom). That is, in the molecular form of the scattered-type oxoxane compound (ai): a block of a chain-like polyoxo moiety and a three-dimensional condensate fraction composed of a sesquiterpene structure The structure is not a normal block copolymer, but is a mesh-like structure which is a three-dimensionally expanded block type siloxane compound (A1) and has a repeating unit in the linear chain. The oxidized structure of the semi-stone nucleus is a nucleus, and the bond-like 矽 oxygen portion is extended, and the next sesquiterpene is extracted from the nucleus pit and the mouth structure is bonded to the sclerosing composition of the present invention. The hardened material gives the meaning of the balance of hardness and softness. Effective. The block type siloxane compound (Α 丨 4 π , ...) can be, for example, a ruthenium base compound (a) represented by the formula (1) and a polyoxanthine oil (1) represented by the formula (7) As a raw material, it is also possible to use the alkoxy money compound (e) represented by the formula () as a raw material. The chain-shaped polyoxo-oxygen moiety of the oxy-sinter compound (A1) is formed from polyoxanol (1): the three-dimensional network of sesquioxaxane is composed of alkoxy decane (4) " The alkoxy decane compound (a) is represented by the following formula (1): xsi(〇R2)3 rn In the formula (1), the alkoxy decane compound (a) is described in detail. Further, if it is an organic group having an epoxycyclohexyl group, it is not particularly limited, and examples thereof include: -(3,4-epoxycyclohexyl)ethyl'r-(3,4-epoxycyclohexyl). a propyl, cold-(3,4-epoxycyclohexyl)propyl valence (3,4-cyclohexylcyclohexyl) butyl group substituted with an epoxy group-containing cyclohexyl group having a carbon number of 1 to 5 Among these, an alkyl group having a carbon number of 丨 〜 3 substituted by a cyclohexyl group having an epoxy group is preferred, and a bis-(3,4-epoxycyclohexyl)ethyl group is particularly preferred. (1) The plural 'I may be the same as each other' may be different, and the alkyl group having a linear number, a chain or a cyclic alkyl group having a carbon number of 1 to 10 is not mentioned. For example, a methyl group or an ethyl group may be mentioned. , n-propyl, isopropyl, n-butyl, Isobutyl, 201137044 butyl n-pentyl 'n-hexyl, cyclopentyl 'cyclohexyl, etc.. From the viewpoint of reaction conditions such as compatibility and reactivity, the r2 is preferably a methyl group or an ethyl group. Preferably, a specific example of the alkoxydecane (a) is y?-(3,4-epoxycyclohexyl)ethyldimethoxydecane' stone-(3,4-epoxy ring) Ethyl-ethoxy pulverization, etc., particularly preferably _(3,4-epoxycyclohexyl)ethyltrimethoxydecane. These alkoxydecane compounds (1) may be used singly or in 2 The above-mentioned 'can also be used together with the alkoxy decane (1) mentioned later. The polyoxo-oxygen oil (b) is a chain polyoxyl oil which has the structure of the following 弋(), and has a sterol. Chain (silan〇l gr〇up) chain polyoxygenated oil: HO—one ~-Si-"Ο—)—η丁丨/Η (2) In the general formula (2), a plurality of existing I The same or different, it means an alkyl group having a carbon number of 1 to 10, an aryl group having a carbon number of 6 to 14, and a rare group of carbon ～10. Further, in the formula (2), m represents a repeating number. The alkyl group of 1 to 10 may be exemplified by a carbon number of 丨~1〇. The chain-like, branched-chain or cyclic alkyl group may, for example, be a methyl group, an ethyl group, a n-propyl isopropyl group, a n-butyl group, an isobutyl group, a second butyl group or a third butyl group. , isoamyl 'pentyl, n-hexyl, cyclopentyl 'cyclohexyl, octyl, 2-ethylhexyl, decyl, decyl and the like. Among these, in consideration of light resistance, 201137044 is preferably a methyl group, an ethyl group, a cyclohexyl group or a n-propyl group. The number of slaves is 6 to 14, and examples thereof include a phenyl group, an o-tolyl group, an m-tolyl group, an anthracenyl group, and a xylyl group. Examples of the dilute group having a carbon number of 2 to 10 include an ethylene group, a methyl ethyl group, an allyl group, an acryl group, a butyl group, a pentyl group, a hexyl group, and the like. From the viewpoint of light resistance 'heat resistance, R3 is preferably a methyl group, a phenyl group, a cyclohexyl group or a n-propyl group. Particularly preferably a fluorenyl group or a phenyl group. Further, in the present invention, it is particularly preferable that at least one of the substituents has a phenyl group in terms of phase bathing property. The m of the compound of the formula (2) represents, on average, 3 to 2 Torr, preferably 3 to 1 Torr, more preferably 3 to 5 Å. If the melon is less than 3, the cured product becomes too hard and the low elastic modulus property is lowered. If m exceeds 2 Å, the mechanical properties of the cured product tend to be deteriorated. The weight average molecular weight (Mw) of the polyoxyxane oil (b) is preferably in the range of 3 〇〇 * 18,000 (measured by gel permeation chromatography (GPC)). Among these, in consideration of the elastic modulus at a low temperature, the molecular weight is preferably 3〇〇1 〇'〇〇0, and further considering the compatibility at the time of composition structuring, it is more preferably 3〇0 to 5'. 000, especially good for 500 to 3,000. When the weight average molecular weight is 300, it is possible that the chain-like polyoxygen moiety of the characteristic segment is difficult to develop and is detrimental to the characteristics of the block type, if it is 1,800 〇, the target is only J has a strong layer separation structure that becomes penetrating when used in optical materials, and becomes difficult to use. In the present invention, the weight average molecular weight (MW) in terms of polystyrene measured under the following conditions using GpC' can be calculated as the molecular weight of the polyoxyxanic oil (b). 11 201137044 Various conditions of GPC Manufacturer: Shimadzu Manufacturing Column: Guard Column SHODEX GPC LF-G LF- 804 (3) Flow rate: 1.0 ml / min.

管柱溫度：40°C 使用溶劑：THE (四氫呋喃） 檢測器：RI (示差折射檢測器） 聚矽氧油（b)之動黏度較佳為10〜200cSt之範圍之動 黏度，更佳為30〜90cSt之動黏度。當小於10cSt時，存在 嵌段型矽氧烷化合物（A1 )之黏度變得過低，不適合作為 光半導體密封劑之情形，又，當大於200cSt時，存在嵌段 型矽氧烷化合物（A1 )之黏度上升，對作業性產生危害之 傾向而不佳。 聚矽氧油（b )較佳之具體例可列舉以下之製品名。例 如可列舉：Dow Corning Toray Silicone 公司製造之 PRX413、BY16- 873，信越化學工業公司製造之X- 21 -5841、KF — 9701，Momentive 公司製造之 XC96 — 723 ' TSR160、YR3370、YF3800、XF3905、YF3057、YF3807、 YF3802、YF3897、YF3804、XF3905，Gelest 公司製造之 DMS-S12、DMS-S14、DMS-S15、DMS-S21'DMS — S27、DMS- S31、DMS- S32、DMS— S33、DMS- S35 ' DMS- S42、DMS- S45、DMS- S51、PDS- 0332、PDS--1615、PDS - 9931等。上述之中，就分子量、動黏度之觀 12 201137044 點而言’較佳為 PRX413、BY16- 873、X— 21 — 5841、KF ~ 9701、XC96- 723、YF3800、YF3804、DMS- S12、DMS -S14、DMS- S15、DMS — S21，PDS- 1615。該等之中， 為了具備聚矽氧部位之柔軟性之特徵，就分子量之觀點而 言’特佳為 X— 21 — 5841、XC96— 723、YF3800、YF3804、 DMS — 514、PDS— 1615。該等聚矽氧油（b)可單獨使用， 亦可併用2種以上。 其次’對燒氧基碎烧（c )進行詳細描述。烧氧基石夕烧 (c)具有下述式（3)之結構。 R4Si(OR5)3 ( 3) 通式（3)中，I表示曱基、苯基或環氧丙基基。 通式（3 )中，多個存在之Rs彼此可相同亦可不同，表 示碳數為1〜10之直鏈狀、支鏈狀或環狀之烷基。例如可 列舉.甲基、乙基、正丙基、異丙基、正丁基、異丁基、 第三丁基、正戊基、正己基、環戊基、環己基等。就相溶 性、反應性等反應條件之觀點而言，該等R$較佳為甲基或 乙基。 烷氧基矽烷（c )較佳之具體例可列舉：曱基三曱氧基 矽烷、苯基三曱氧基矽烷、曱基三乙氧基矽烷、笨基三乙 氧基矽烷等。上述之中，較佳為曱基三甲氧基矽烷、苯基 三曱氧基矽烷。 於本發明中，為了調節嵌段型矽氧烷化合物（八丨）之 为子畺、形成組成物時之相溶性或硬化物之耐熱性、耐光 性、低透濕性、低透氣性等，烷氧基矽烷（c)可與烷氧基 13 201137044 矽烷（a)併用。 當使用烷氧基矽烷（c)時，較佳 ⑴之合計莫耳之中，一= 莫耳％之範圍使用，更佳為5〜5〇 六卞。特佳為1〇〜40 莫耳％。若大於7 0莫耳％，目丨丨締儿此 ^ 旲耳則硬化物之交聯密度下降，機 械強度下降，故不佳。 执 烷氧基矽烷.(〇、聚矽氧油⑴、烷氧基矽烷⑷ 之反應比率’㈣為相對於❹氧油（b)切醇基㈣⑽ _州當量，將貌氧基石夕烧（a)(以及視需要而使用之烧 氧基矽烷（c))中之烷氧基作為當量值，於1 5〜_，較 佳為2〜200，特佳為2〜1〇〇之間進行反應。 若當量值超過200 ,則使用嵌段型矽氧烷化合物（ai ) 之硬化物變得過硬，目標之低彈性模數特性下降。 以下，對嵌段型矽氧院化合物（A1)之較佳製造方法 進行具體說明。 嵌段型矽氧烷化合物（A1)之製造方法，較佳為經過 由以下（1) 、（ ii )所示之製造步驟。 製造步驟（i):進行矽醇末端聚矽氧油（1))與具有烷 氧基之烷氧基矽烷（a)(以及視需要而添加之烷氧基矽烷 (c))之脫醇縮合之步驟 製造步驟（ii ):添加水而進行烷氧基矽烷（a )(以 及視需要而添加之烷氧基矽烷（c))之烷氧基彼此之水解 縮合的步驟 只要經由各步驟，則製造步驟（i)、（ u )能夠以任何 14 201137044 順序進行反應。 較佳之製造方法，具體可 〈製造方法（一）> u下三種製造方法。 首先，製造步驟⑴為如 基之聚石夕氧油⑴與具有燒氧基/·藉由末端具有石夕醇 (a) <石夕化合物即院氧基矽烷 〔丑）（以及視需要而添加之烷氧 及應從取诊® 基夕烷（〇)之脫醇縮合Column temperature: 40 ° C Solvent: THE (tetrahydrofuran) Detector: RI (differential refraction detector) The viscosity of the polyoxygenated oil (b) is preferably a dynamic viscosity in the range of 10 to 200 cSt, more preferably 30 ~90cSt dynamic viscosity. When it is less than 10 cSt, the viscosity of the block type siloxane compound (A1) becomes too low, which is not suitable as a photo-semiconductor sealant, and when it is more than 200 cSt, the block type siloxane compound (A1) exists. The viscosity rises and the tendency to harm the workability is not good. Preferred examples of the polyoxygenated oil (b) include the following product names. For example, PRX413, BY16-873 manufactured by Dow Corning Toray Silicone Co., Ltd., X-215-1841, KF-9701 manufactured by Shin-Etsu Chemical Co., Ltd., XC96-723' manufactured by Momentive Corporation, TSR160, YR3370, YF3800, XF3905, YF3057 , YF3807, YF3802, YF3897, YF3804, XF3905, DMS-S12, DMS-S14, DMS-S15, DMS-S21'DMS - S27, DMS-S31, DMS-S32, DMS-S33, DMS-S35 manufactured by Gelest 'DMS-S42, DMS-S45, DMS-S51, PDS- 0332, PDS--1615, PDS-9031, etc. Among the above, in terms of molecular weight and dynamic viscosity 12 201137044 points, 'preferably PRX413, BY16-873, X-21-5841, KF ~ 9701, XC96-723, YF3800, YF3804, DMS-S12, DMS - S14, DMS-S15, DMS - S21, PDS-1615. Among these, in order to provide the flexibility of the polyoxymethylene moiety, it is particularly preferable that X-21-19841, XC96-723, YF3800, YF3804, DMS-514, and PDS-1615 are used in terms of molecular weight. These polyoxygenated oils (b) may be used singly or in combination of two or more. Next, the alkoxy calcination (c) is described in detail. The oxy-stone is calcined (c) has the structure of the following formula (3). R4Si(OR5)3 (3) In the formula (3), I represents a mercapto group, a phenyl group or a glycidyl group. In the general formula (3), a plurality of Rs present may be the same or different, and represent a linear, branched or cyclic alkyl group having a carbon number of 1 to 10. For example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, cyclopentyl, cyclohexyl and the like can be mentioned. The R$ is preferably a methyl group or an ethyl group from the viewpoints of reaction conditions such as compatibility and reactivity. Specific examples of the alkoxydecane (c) include decyltrimethoxy decane, phenyltrimethoxy decane, decyltriethoxydecane, and phenyltriethoxydecane. Among the above, mercaptotrimethoxydecane and phenyltrimethoxydecane are preferred. In the present invention, in order to adjust the solubility of the block type siloxane compound (artichoke) to the oxime, the compatibility of the composition, the heat resistance of the cured product, the light resistance, the low moisture permeability, the low gas permeability, and the like, The alkoxydecane (c) can be used in combination with the alkoxy 13 201137044 decane (a). When alkoxydecane (c) is used, it is preferably used in the range of one mole % of the total moles of (1), more preferably 5 to 5 inches. Very good for 1〇~40%. If it is more than 70% by mole, the crosslink density of the hardened material is lowered and the mechanical strength is lowered, so it is not good. Alkoxy oxane. (反应, polyoxyxane (1), alkoxy decane (4) reaction ratio '(d) is relative to the oxirane oil (b) sterol group (four) (10) _ state equivalent, will look at the oxygen stone (a) The alkoxy group in (and optionally the alkoxydecane (c)) used as an equivalent value is carried out between 15 and _, preferably 2 to 200, particularly preferably 2 to 1 Torr. When the equivalent value exceeds 200, the cured product using the block type siloxane compound (ai) becomes too hard, and the low elastic modulus characteristic of the target is lowered. Hereinafter, the block type oxime compound (A1) A preferred method for producing the block type siloxane compound (A1) is preferably a production step shown by the following (1) and (ii). Manufacturing step (i): 矽Step (ii) of the step of dealcoholating condensation of an alcohol-terminated polyoxyxanic oil (1)) with an alkoxy alkane (a) having an alkoxy group (and optionally alkoxydecane (c)): The step of hydrolyzing and condensing the alkoxy groups of the alkoxydecane (a) (and the alkoxydecane (c) optionally added) by adding water is only required via Step, the manufacturing step (i), (u) the reaction can be performed in any order 14201137044. A preferred manufacturing method is specifically the following three manufacturing methods: [manufacturing method (1) > First, the manufacturing step (1) is as the base of the polysulfuric acid (1) with an alkoxy group / by the end having a linalool (a) < shixi compound, oxy oxane [ugly] (and optionally Alkylation added and dealcoholization condensation from the diarrhea® ketone (〇)

反應將聚矽氧油末端進行烷氧AThe reaction will carry out the alkoxy A at the end of the polyoxygenated oil.

^ Κ巻*石夕燒改質.，難it卜痛错· P 氧基矽烷改質體Cd)。 糟此獲仔说 繼而，製造步驟（ii)為如下 凡人』 戈下步驟：於具有烷氧基之矽 化合物即烷氧基矽烷（a)(以 視需要而添加之烧氧基石夕 院（〇)、及製造步驟⑴中所獲得之聚石夕氧油之院氧基 矽烷改質體⑷中添加水來進行烷氧基彼此之水解縮合反 應0 &lt;製造方法（二）&gt; 首先，製造步驟（ii)為如下步驟：藉由進行烷氧基矽 烷（a)(以及視需要而添加之烷氧基矽烷（c))之因添加 水而進行之烷氧基彼此的水解縮合反應，獲得分子内具有 烷氧基之倍半矽氧烷（e)。 繼而，製造步驟（i)為如下步驟：藉由聚矽氧油（b) 與倍半石夕氧烧（e )之反應，而使殘留於倍半矽氧烧結構之 烷氧基與矽醇基進行脫醇縮合反應。 &lt;製造方法（三）&gt; 首先，製造步驟（i)係藉由末端具有矽醇基之聚矽氧 油（b )與烷氧基石夕烷（a )(以及視需要而添加之烷氧基矽 15 201137044 烷（C))之脫醇縮合反應，而對聚矽氧油末端加以烷氧基 矽烷改質，藉此形成烷氧基矽烷改質體（d)，然後於系統 内添加水’接著製造步驟（ii)係以單一容器(onepot)進行 殘存之烷氧基矽烷（a)(以及烷氧基矽烷（c))、及烷氧 基石夕烧改質體（d)之烧氧基彼此之水解縮合反應，藉此製 造嵌段型石夕氧院化合物（A1 )。 於本發明中，就縮短製造步驟之觀點而言，較佳為使 用逐次於單一容器中反應之上述製造方法（三）。 以下’更具體地描述製造方法（三）。 於以單一谷器進行反應之情形時，若按照與上述製造 方法（三）相反之順序進行反應，亦即於製造步驟（丨丨）後 進行製造步驟（1)，則製造步驟（ii)所形成之具有烷氧基 之倍半石夕氧院寡聚物與聚矽氧油（b)不相溶，於下一製造 步驟（i)中不會進行脫醇縮合聚合，因而聚矽氧油殘留之 :能性較高。另一方面’若使用如製造方法（三）般於製 造步驟（1 )後以單一容器進行製造步驟（Η )之方法，則聚 矽氧油（b)與烷氧基矽烷（a)或烷氧基矽烷（c)之相溶 性相對較高，0此可避免如上述之不相溶而不進行反應之 =題。進而，由於對料基未反應之低分子貌氧基石夕院大 存在，因此就反應性之觀點而言亦較佳。當以單一容器 進行反應時，首先於製造步驟⑴中，進行聚石夕氧油（b) 與烷氧基矽烷（a)(以及視需要添加之烷氧基矽烷（c)) 之脫醇縮合，使聚矽氧油之末端進行烷氧基矽烷基改質， 而獲得烷氧基矽烷改質體（d)。在製造步驟（i)中由於未 201137044 添加水，因此不會產生烷氧基彼此之水解縮合，當相對於 矽醇基1當量，使用3當量以上之烷氧基進行反應時，認 為烧氧基石夕烧改質體（d )係以由如下述式（4 )所示之結 構存在。^ Κ巻 * Shi Xi burn modified. It is difficult to change the pain · P oxydecane modified body Cd). The latter is said to be followed by the manufacturing step (ii) as follows: Steps: alkoxydecane (a), an alkoxy group-containing compound (added to the alumite as needed) And the addition of water to the oxydecane modified body (4) of the polyoxime oil obtained in the production step (1) to carry out a hydrolysis condensation reaction of the alkoxy groups with each other. 0 &lt;Production Method (2)&gt; First, manufacture Step (ii) is a step of obtaining a hydrolysis condensation reaction of alkoxy groups by adding water with alkoxydecane (a) (and alkoxydecane (c) added as needed) a sesquioxane (e) having an alkoxy group in the molecule. Then, the production step (i) is a step of reacting a polyoxyxanic oil (b) with a sesquiterpoxide (e), and The alkoxy group remaining in the sesquiterpoxy-oxygen structure is subjected to a dealcoholization condensation reaction with a decyl alcohol group. <Production Method (3)&gt; First, the production step (i) is carried out by a fluorenyl group having a thiol group at the terminal. Oxygen oil (b) with alkoxy oxetane (a) (and alkoxy hydrazine 15 as desired) C)) a dealcoholization condensation reaction, wherein the polyoxyxanthene oil is modified with an alkoxydecane, thereby forming an alkoxydecane modified body (d), and then adding water to the system'. Next, a manufacturing step (ii) Hydrolysis and condensation reaction of the alkoxydecane (a) (and alkoxydecane (c)) remaining in a single container (one) with the alkoxy group of the alkoxylate modified body (d) Thus, a block type oxalate compound (A1) is produced. In the present invention, from the viewpoint of shortening the production steps, it is preferred to use the above-described production method (3) which is successively reacted in a single vessel. More specifically, the production method (3) is described. When the reaction is carried out in a single trough, the reaction is carried out in the reverse order of the above production method (3), that is, after the production step (丨丨). 1), the sesquioxane oligomer having an alkoxy group formed in the production step (ii) is incompatible with the polyoxyxane oil (b), and will not be carried out in the next production step (i) De-alcohol condensation polymerization, thus the residual polyoxygenated oil: higher energy. Another If the method of the production step (Η) is carried out in a single vessel after the production step (1) as in the production method (3), the polyoxyxane oil (b) and the alkoxydecane (a) or alkoxy group are used. The compatibility of decane (c) is relatively high, and this avoids the problem of incompatibility as described above without performing the reaction. Further, since the low-molecular spectroscopy which is unreacted to the substrate is present, It is also preferable from the viewpoint of reactivity. When the reaction is carried out in a single vessel, first, in the production step (1), the polyoxosulfuric acid (b) and the alkoxydecane (a) (and the alkoxy group added as needed) The dealcoholization condensation of the decane (c)) causes the alkoxy decyl group to be modified with an alkoxy decyl group to obtain an alkoxy decane modified body (d). In the production step (i), since water is not added in 201137044, hydrolysis and condensation of alkoxy groups are not caused, and when a reaction is carried out using 3 equivalents or more of alkoxy groups with respect to 1 equivalent of the sterol group, it is considered to be an alkoxylate. The kiln modified body (d) is present in a structure represented by the following formula (4).

(式（4)中，R2、R3、m表示與上述相同之含義，R6 表示上述X及/或R4)。 於製造步驟（0中，若相對於矽醇基丨當量，使烷氧 基以少於1.0當量之量反應，則於製造步驟（丨）結束時不 存在烷氧基’因此無法進入至製造步驟（Η)，又，若使烷 氧基於1.0〜1.5當量之間進行反應，則烷氧基矽烷（a )(以 及視需要而添加之烷氧基矽烷（c))中之2個以上之烷氧 基會與聚矽氧油（b)之矽醇基反應，造成製造步驟（i)結 束時過度成為高分子而產生.凝膠化。因此，必需相對於矽 醇基1當量’使烧氧基以多於丨_5 #量進行反應^就控制反 應之觀點而言，較佳為2.0當量以上。 於製造步驟（i)結束後，進行第2段反應（製造步驟 (ii)),即直接添加水來進行烷氧基彼此之水解縮合。 於製造步驟（ii)中，產生下述所示之（j)〜（HI) 之反應。(In the formula (4), R2, R3, and m have the same meanings as described above, and R6 represents the above X and/or R4). In the production step (0, if the alkoxy group is reacted in an amount of less than 1.0 equivalent relative to the oxime oxime equivalent, no alkoxy group is present at the end of the production step (丨), and thus it is impossible to proceed to the production step. (Η), in addition, when the alkoxy group is reacted between 1.0 and 1.5 equivalents, two or more of the alkoxydecane (a) (and optionally the alkoxydecane (c)) may be added. The oxy group reacts with the sterol group of the polyoxyxane oil (b), causing excessive formation of a polymer at the end of the production step (i) to cause gelation. Therefore, it is necessary to make oxygen for 1 equivalent with respect to the sterol group. The reaction is carried out in an amount of more than 丨_5 #, and is preferably 2.0 equivalents or more from the viewpoint of controlling the reaction. After the completion of the production step (i), the second-stage reaction (manufacturing step (ii)) is carried out, that is, Water is directly added to carry out hydrolysis condensation of the alkoxy groups. In the production step (ii), the reactions (j) to (HI) shown below are produced.

17 201137044 添加之烧氧基矽烷（c))之烷氧基彼此之縮合反應。 (II )製造步驟（i )中所獲得之烷氧基矽烷改質體（d) 與烧氧基矽烷（a)(以及視需要而添加之烷氧基矽烷（c)) 之烧氧基彼此之縮合反應。 (ΠΙ )製造步驟（丨）中所獲得之烷氧基矽烷改質體（d) 與（I)中所生成之烷氧基矽烷（a)(以及視需要而添加之 院氧基碎貌（c ))之部分縮合物之烷氧基彼此的縮合反應。 於製造步驟（ii )中’上述反應係複合地產生，倍半石夕 氧烷結構部位之形成、及進而與來自聚矽氧油之鏈狀聚矽 氧部位之縮合係同時進行。 欲段型石夕氧烷化合物（A1)之製造亦可於無觸媒下進 行，但若無觸媒，則反應進行較緩慢，就縮短反應時間之 觀點而σ ’較佳為於觸媒存在下進行。可使用之觸媒，只 要為顯示酸性或鹼性之化合物，則可使用。酸性觸媒之例 可列舉：鹽酸、硫酸、硝酸等無機酸或甲酸、乙酸、草酸 等有機酸。又，鹼性觸媒之例可使用：如氫氧化鈉、氫氧 化鉀、氫氧化鋰、氫氧化鉋之鹼金屬氫氧化物，如碳酸鈉、 碳酸鉀、碳酸氫鈉、碳酸氫鉀之鹼金屬碳酸鹽等無機鹼， 氣一乙私一伸乙二胺（Diethylene triamine)、正丁基胺、 二甲基胺乙醇、三乙醇胺、日甲基氫氧化銨等有機鹼。該 等之中，尤其就容易自產物去除觸媒之觀點而言，較佳為 無機驗，特佳為氫氧化納、氫氧化鉀。觸媒之添加量相對 於反應系統中之烷氧基矽烷（a)(以及視需要而添加之烷 氧基石夕烧（〇 )之合計44，通常為Q•謝〜7 5重量％， 18 201137044 較佳為0.01〜5重量％。17 201137044 The alkoxy groups of the added alkoxydecane (c)) are condensed with each other. (II) alkoxydecane modified body (d) obtained in the step (i) and an alkoxy group of the alkoxydecane (a) (and optionally alkoxydecane (c)) The condensation reaction. (ΠΙ) the alkoxydecane modified body (d) obtained in the production step (丨) and the alkoxydecane (a) formed in (I) (and the addition of the hospitaloxy group as needed ( c)) The condensation reaction of the alkoxy groups of the partial condensates with each other. In the production step (ii), the above reaction is produced in a composite manner, and the formation of the sesquiterpene structural site and further the condensation with the chain-like polyoxo oxygen moiety from the polyoxygenated oil are carried out simultaneously. The preparation of the segment-type oxalate compound (A1) can also be carried out without a catalyst, but if the catalyst is not used, the reaction proceeds slowly, and the reaction time is shortened, and σ' is preferably present in the catalyst. Go on. The catalyst that can be used can be used as long as it exhibits an acidic or basic compound. Examples of the acidic catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid, and organic acids such as formic acid, acetic acid, and oxalic acid. Further, examples of the alkaline catalyst can be used: alkali hydroxide such as sodium hydroxide, potassium hydroxide, lithium hydroxide or hydroxide, such as sodium carbonate, potassium carbonate, sodium hydrogencarbonate or potassium hydrogencarbonate. An inorganic base such as a metal carbonate, an organic base such as Diethylene triamine, n-butylamine, dimethylamine ethanol, triethanolamine or N-methylammonium hydroxide. Among these, in particular, from the viewpoint of easily removing the catalyst from the product, it is preferably an inorganic test, and particularly preferably sodium hydroxide or potassium hydroxide. The amount of catalyst added is 44 relative to the alkoxy decane (a) in the reaction system (and the alkoxy sulphate (〇) added as needed, usually Q•谢~7 5 wt%, 18 201137044 It is preferably 0.01 to 5% by weight.

之縮合單獨進行， -狀態下使用。其中，較佳為以使觸媒預 醇、丙醇、丁醇等醇類中之狀態下添加。 作為使用水等之水溶液進行添加，係使 (以及視需要而添加之烷氧基矽烷（C)) 由此所生成之倍半石夕氧烧寡聚物與聚石夕 氧油（b )不相溶而有可能產生白濁。 令I “又型矽氧烷化合物（A1 )之製造可於無溶劑或者溶 W中進仃又，亦可於製造步驟之中途追加溶劑。使用溶 劑時之溶劑’若為溶解烧氧基㈣（a)、院氧基㈣（c)、 Λ氧油（b )、烧氧基矽烧改質體（d )之溶劑，則並無 特别限制。此種溶劑例如可例示：二曱基曱醯胺、二曱基 乙醯胺、四氫呋喃之類的非質子性極性溶劑，甲基乙基酮、 曱基異丁基酮、 乳酸乙g旨、丁酉 嗣、環戊酮之類之酮類，乙酸乙酯、乙酸丁酯、 丁 異丙g旨等g旨類，甲醇、乙醇、丙醇、丁醇 之類之醇類，己烷、環己烷、甲苯、二曱苯之類之烴等。 於本發明中，就控制反應之觀點而言，較佳為於醇類中之 反應，更佳為甲醇、乙醇。溶劑之使用量若為反應順利進 打之範圍，則並無特別限制，但相對於烷氧基矽烷（a)(以 及視需要而添加之烷氧基矽烷（c ))、聚矽氧油（b )之化 合物之合計重量1〇〇份，通常使用〇〜9〇〇重量份左右。反 應溫度雖然亦取決於觸媒量，但通常為2〇〜l6〇〇c，較佳為 40〜140°C，特佳為50〜15〇〇C。又，反應時間通常於各製 19 201137044 造步驟中分別為1〜40小時’較佳為5〜3〇小時。 反應結束後，視需要藉由淬冷（quenching)、及/或水洗 來去除觸媒。當進行水洗時，較佳為根據所使用之溶劑之 種類而添加可與水分離之溶劑。較佳之溶劑例如可例示： 甲基乙基_、曱基異丁基酮、環戊酮之類的酮類，乙酸乙 酯、乙酸丁酯、乳酸乙酯、丁酸異丙酯等酯類，己烷、環 己院、甲笨、二甲苯之類之烴等。 本反應可僅藉由水洗來進行觸媒之去除，但由於在酸 性、驗性條件之任一條件下進行反應，故而較佳為於藉由 中和反應進行淬冷後進行水洗、或者使用吸附劑吸附觸媒 後藉由過渡而去除吸附劑。 若為顯示酸性或驗性之化合物，則可用於中和反應。 顯示酸性之化合物之例可列舉：鹽酸、硫酸、硝酸等無機 酸或曱酸、乙酸、草酸等有機酸。又，顯示鹼性之化合物 之例可使用·氫氧化鈉、氫氧化鉀、氫氧化鋰、氫氧化鉋 之類的鹼金屬氫氧化物，碳酸鈉、碳酸鉀、碳酸氫鈉、碳 酸氫斜之類的鹼金屬碳酸鹽，磷酸、磷酸二氫鈉、磷酸氫 二納、構酸三鈉、聚磷酸、三聚磷酸鈉之類的磷酸鹽類等 無機鹼，氨、三乙胺、二伸乙三胺、正丁基胺、二甲基胺 乙醇、三乙醇胺、四甲基氩氧化銨等有機鹼。該等之中， 就容易自產物中去除之觀點而言，特佳為無機鹼或無機 酸’進而較佳為更容易將pH調整為中性附近之磷酸鹽類等。 吸附劑可例示：活性白土、活性碳、沸石、無機.有 機系之合成吸附劑、離子交換樹脂等，具體例可列舉下述 20 201137044 製品。 活性白土例如可列舉：東新化成公司製造之活性白土 SA35、SA1、T、R- 15、E、Nikkanite G- 36、G- 153、G — 168，水澤化學工業（Mizusawa Industrial Chemicals)公 司製作之Galleon Earth、Mizuka Ace等。活性碳例如可列 舉：Ajinomoto Fine — Techno 公司製造之 CL—Η、Y — 10S、 Y— 10SF，Futamura Chemical 公司製造之 S、Υ、FC、DP、 SA1000、K、A、KA、M、CW130BR、CW130AR、GM130A 等。沸石例如可列舉：Union Showa公司製造之Molecular Sieve3A、4A、5A、13X等。合成吸附劑例如可列舉：協和 化學公司製造之 Kyoward 100、200、300、400、500、600、 700、1000、2000，或者 Rohm&amp;Hass 公司製造之 Amberlystl5JWET、15DRY、16WET、31 WET、A2卜 Amberlite IRA400JC1、IRA403BLCU、IRA404JC卜或者 Dow Chemical 公司製造之 Dowex66、HCR— S、HCR— W2、MAC— 3 等》 將吸附劑添加至反應液中，進行攪拌、加熱等處理， 吸附觸媒後，過濾吸附劑，進而對殘渣進行水洗，藉此可 去除觸媒、吸附劑。 於反應結束後或淬冷後，可藉由水洗、過濾以外之慣 用分離純化方法進行純化。純化方法例如可列舉：管柱層 析法、減壓濃縮、蒸餾、萃取等。該等純化方法可單獨進 行，亦可組合複數種來進行。 當使用與水混合之溶劑作為反應溶劑來進行反應時， 較佳為於淬冷後藉由蒸餾或減壓濃縮而將與水混合之反應 21 201137044 溶劑自系統中去除之後’使用可與水分離之溶劑進行水洗。 水洗後藉由減壓濃縮等而去除溶劑，藉此可獲得嵌段 型矽氧烷化合物（A 1 )。 以上述方式所獲得之嵌段型矽氧烷化合物（A1 )之外 觀通常為無色透明且於251具有流動性之液狀。又，其分 子量係以GPC測定之重量平均分子量較佳為8〇〇〜 2〇,〇〇〇,更佳為 1，000〜10,000,特佳為 15〇()〜6,〇〇()。當 重量平均分子量小於8〇〇時，存在耐熱性下降之可能性， 當重量平均分子量大於20,000時，黏度上升而對作業性產 生危害。再者，分子量可根據烷氧基矽烷(以及視需 要而添加之烷氧基矽烷（c))與聚矽氧油之當量比、 聚矽氧油（b )之分子量、反應時之水之添加量、反應時間、 反應溫度而進行調整。 重量平均分子量係利用GPC (凝膠滲透層析儀）於下 述條件下所測定之聚苯乙烯換算之重量平均分子量（m w )。 GPC之各種條件 製造者：島津製作所 管柱：保護管柱 SHODEXGPCLF—GLF— 804 ( 3 根） 流速：1 .〇ml/min. 管柱溫度：40。匚 使用溶劑：THE (四氫呋喃） 檢測器：RI (示差折射檢測器） 又，忒嵌段型矽氧烷化合物（A1 )之環氧當量（以ns K— 7236中所記載之方法測定）較佳為3〇〇〜i^oog/叫， 22 201137044 更佳為400〜l，200g/eq·。當環氧當量小於3〇〇g//eq時， 存在其硬化物變得較硬，彈性模數變得過高之傾向，當環 氧當量大於l，600g/eq.時，存在硬化物之機械特性惡化之 傾向而不佳。 嵌段型矽氧烷化合物（AI)之黏度（E型黏度計，於 25 °C測定）較佳為50〜2〇,〇〇〇mPa . s，更佳為5〇〇〜 10,000mPa · s，特佳為8〇〇〜5 〇〇〇mPa · s。當黏度小於 OmPa s時’存在黏度過低而不適合光半導體密封材料用 途之可能性’當黏度大於2〇,〇〇〇mPa· s時，存在黏度過高 而作業性欠佳之情形。 嵌段型石夕氧烧化合物（A1)中源自倍半石夕氧烧之3個 氧鍵結㈣原子相對於所切原子之比例較佳I 8〜％莫 耳％更佳為8〜25莫耳％。若源自倍半石夕氧院之3個氧鍵 結的石夕原子相對於所切原子之比例小於8莫耳％，則存在 表現出鏈狀聚Μ部位之特徵，硬化物變得過軟之傾向。 二’若超過3〇莫耳％，則表現出倍半矽氧烷結構部位之特 徵’硬化物變得過硬。若 硬化㈣付過硬，則咖密封時 對於阳片之樹脂應力變Α，因此容易產生咖 戶在之石夕原子之比例可藉由嵌段型彻化合彩 HNMR、”Si NMR、元素分析等而求出。 又，本發明中之含環氧環己基之有 段型矽氧烷化合物“…… ’氧C A)及療 加 ()較理想的是其結構令包含茉其典 架。當將笨基骨牟邋入 本土月 土月木v入至嵌段型矽氧烷化合物（Αι)中時， 23 201137044 只要聚矽氧油（b)、烷氧基矽烷（a)(以及視需要而添加 之烷氧基矽烷（C))之至少任一者中包含該苯基骨架即可。 因結構中具有苯基骨架，硬化物之強度或折射率得到提 昇。因折射率得到提昇，於用作光半導體密封材料時，光 取出效率得到提昇。又，苯基骨架亦具有填埋分子間之空 間’防止氣體之穿透之效果。 當包含苯基作為含環氧環己基之有機聚矽氧之取代基 夺於3環氧環己基之有機聚石夕氧中，較佳為於已進行重 算時苯基成4卜45重量％之範圍，特佳為成為2〜川 重量/〇之範圍。其原因在於：若超過45重量％，則黏度變 高，又，由於官能基當量變得過大，因此耐熱性欠佳。 本發明之硬化性樹脂組成物含有脂環族環氧樹脂 (B)。脂環族環氧樹脂（B)係為了對硬化物賦予強勃性 而導入。 脂環族環氧樹脂⑻較佳為骨架中具有環氧環己烧結 冓b σ物，特佳為藉由具有環己烯結構之化合物之氧化 反應而獲得之環氧樹脂。 該等環氧樹脂可列舉：將可藉由以下反應製造之化合 物氧化而得者：環己烯叛酸與醇類之自旨化反應、或環己稀 甲1醇與m酸類之醋化反應（Tetrahedron νο136 Ρ 2409 (198〇)，Tetrahedron Letter P.4475 ( 1980)等中所記載之 方法）、或者環己烯醛之季先科反應（τ— “action ) 。八本特開2003 — 170059號公報、日本特開2〇〇4— 262871 〜報等中所5己載之方法），進而環己烯羧酸酯之酯交換 24 201137044 反應（日本特開麵-052187號公報等中所記載之方法）。 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 ^ ， 丙二酵、1,2 — 丁二醇、 1，4一 丁二醇、1，5—戊二醇、16— ^ 匕一醇、環己燒二甲醇、 2,4 一二乙基戊二醇、2—乙基—2〜 ,._ ^ ^ J巷一 1，3 —丙二醇、新 戊二醇、三環癸烷二甲醇、降莰煸_ T人碲一醇等二醇類，丙三醇、 三羥甲基乙烷、三羥曱基丙烧、 —暴丁院、2 —經甲基 -Μ-丁二醇等三醇類，新戊四醇、二—三㈣基丙烧等 四醇類等。又’羧酸類可列舉：草酸、順丁烯二酸、反丁 稀一酸、鄰苯二甲酸、問笑-田缺 間本一甲酸、己二酸、環己烷二羧 酸等’但並不限定於此。 進而，可列舉藉由環己稀經衍生物與醇體之縮酸反應 所產生之縮醛化合物。 該等環氧樹脂之具體例，可列舉：ERL_ 422i、uvr_ 5 ERL 4299 (全部為商品名，均為D〇w Chemical製 造），celloxide2021P、Ep〇lead gt4〇i、騰E3i5〇、 EHPE3150CE (全部為商品名，均為⑽以匕學工業製造） 及一 ％戊一烯一 ί衣氧化物等，但並不限定於該等（參考文 獻：環氧樹脂總論基礎篇ΙΡ76— 85 )。 該等可單獨使用，亦可併肖2種以上。於本發明中， 就提昇耐透氣性性之觀點而言’具有環氧環己烧結構之化 合物亦較佳。 月曰衣私％氧树脂（Β)之環氧當量（藉由jis κ_ 中所5己載之方法測定）較佳為100〜500g/eq·，更佳為100 25 201137044 〜300g/ eq.。 脂環族環氧樹脂（B)之分子量較佳為2〇〇〜ι〇〇〇, 佳為200〜600。 本發明之硬化性樹脂組成物可摻合成脂環族環氧齡 ⑻於含環氧環己基之有機聚石夕氧（A)與脂環族環氧^ 脂⑻之總量中料之量達到2Q〜4G重量％，亦可推合 成達到1.5〜40重量％。若脂環族環氧樹脂（b)之含量: 過40重量％，則所獲得之硬化物變得過硬，於作為咖 密封材料時容易產生裂痕，或者晶片被過度地施加應力， 二明度容易劣化。另一方面’若脂環族環氧樹脂⑻之含 :未達Μ重量％，則所獲得之硬化物較脆，線膨脹係數較 又’接者性較差，作為光半導體密封材料之適性欠佳。 月曰環族環氧樹脂（Β)之含量 為1 8〜2〇會I。/ I更佳為U〜2〇重量％，特佳 ，當增加脂環族環氧樹脂之含量時， *性二t 現到所獲得之硬化物之硬度與柔 聚石夕W 出效率主要取決於含環氧環己基之有機 A)(較佳為嵌段型矽氧烷化合The condensation is carried out separately, in the - state. Among them, it is preferably added in a state of an alcohol such as a catalyst prealcohol, propanol or butanol. The addition of the aqueous solution of water or the like is carried out (and the alkoxydecane (C) to be added as needed). The sesquiterpene oxygenated oligomer and the polysulfuric acid (b) are not formed thereby. It is soluble and may be cloudy. Let "I-type oxoane compound (A1) be produced without solvent or W, or add solvent in the middle of the manufacturing process. Solvent when using solvent 'if dissolved alkoxy (4) The solvent of a), the oxy group (4) (c), the oxime oil (b), and the alkoxylated oxime (d) is not particularly limited. For example, the solvent is exemplified by diterpenoid hydrazine. Aprotic polar solvent such as amine, dimercaptoacetamide or tetrahydrofuran, methyl ethyl ketone, decyl isobutyl ketone, lactic acid, ketones such as butyl hydrazine and cyclopentanone, acetic acid Ethyl ester, butyl acetate, butyl isopropion, etc., alcohols such as methanol, ethanol, propanol, butanol, hydrocarbons such as hexane, cyclohexane, toluene, and diphenylbenzene. In the present invention, from the viewpoint of controlling the reaction, it is preferably a reaction in an alcohol, more preferably methanol or ethanol. The amount of the solvent used is not particularly limited as long as the reaction proceeds smoothly. a combination of alkoxydecane (a) (and alkoxydecane (c) added as needed) and a compound of polyoxyxane (b) The weight is 1 part, usually about 〇〇~9〇〇 parts by weight. Although the reaction temperature depends on the amount of the catalyst, it is usually 2〇~l6〇〇c, preferably 40~140°C, especially preferably 50~15〇〇C. Further, the reaction time is usually 1 to 40 hours, preferably 5 to 3 hours, in each of the steps 19 201137044. After the reaction is completed, quenching is required as needed. And/or washing with water to remove the catalyst. When washing with water, it is preferred to add a solvent which can be separated from water depending on the kind of the solvent to be used. Preferred solvents are, for example, methyl ethyl group, decyl isobutylene. Ketones such as ketone and cyclopentanone, esters such as ethyl acetate, butyl acetate, ethyl lactate, and isopropyl butyrate; hydrocarbons such as hexane, cyclohexyl, methyl, xylene, etc. The reaction may be carried out by washing only with water. However, since the reaction is carried out under any of acidic conditions and conditions, it is preferably subjected to quenching by a neutralization reaction, followed by water washing or use. After the adsorbent adsorbs the catalyst, the adsorbent is removed by the transition. Examples of the compound which can be used for the neutralization reaction include inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid, and organic acids such as citric acid, acetic acid, and oxalic acid, and examples of compounds exhibiting basicity can be used. Alkali metal hydroxide such as sodium hydroxide, potassium hydroxide, lithium hydroxide or hydroxide, alkali metal carbonate such as sodium carbonate, potassium carbonate, sodium hydrogencarbonate or hydrogencarbonate, phosphoric acid, dihydrogen phosphate Inorganic bases such as sodium, dibasic hydrogen phosphate, trisodium citrate, polyphosphoric acid, and sodium tripolyphosphate, ammonia, triethylamine, diethylenetriamine, n-butylamine, dimethylamine An organic base such as ethanol, triethanolamine or tetramethylammonium arsenide. Among these, from the viewpoint of easy removal from the product, it is particularly preferable to use an inorganic base or an inorganic acid, and it is more preferable to adjust the pH to Phosphates in the vicinity of neutral. The adsorbent can be exemplified by activated clay, activated carbon, zeolite, inorganic, organic synthetic adsorbent, ion exchange resin, and the like. Specific examples thereof include the following 20 201137044 products. Examples of the activated clay include activated clay SA35, SA1, T, R-15, E, Nikkanite G-36, G-153, G-168 manufactured by Dongshin Chemical Co., Ltd., manufactured by Mizusawa Industrial Chemicals Co., Ltd. Galleon Earth, Mizuka Ace, etc. Examples of the activated carbon include: CL-Η, Y-10S, Y-10SF manufactured by Ajinomoto Fine-Techno Co., Ltd., S, Υ, FC, DP, SA1000, K, A, KA, M, CW130BR manufactured by Futamura Chemical Co., Ltd. CW130AR, GM130A, etc. Examples of the zeolite include Molecular Sieve 3A, 4A, 5A, and 13X manufactured by Union Showa. Examples of the synthetic adsorbent include Kyoward 100, 200, 300, 400, 500, 600, 700, 1000, 2000 manufactured by Kyowa Chemical Co., Ltd., or Amberlystl 5 JWET, 15 DRY, 16 WET, 31 WET, A2 Amberlite manufactured by Rohm &amp; IRA400JC1, IRA403BLCU, IRA404JC or Dowex66, HCR-S, HCR-W2, MAC-3, etc. manufactured by Dow Chemical Co., Ltd. Add the adsorbent to the reaction solution, stir, heat, etc., after adsorption, filter adsorption The agent is further washed with water to remove the catalyst and the adsorbent. After completion of the reaction or after quenching, purification can be carried out by a conventional separation and purification method other than water washing and filtration. The purification method may, for example, be a column chromatography method, concentration under reduced pressure, distillation, extraction or the like. These purification methods may be carried out singly or in combination of plural kinds. When the reaction is carried out using a solvent mixed with water as a reaction solvent, it is preferred to carry out the reaction with water after distillation or concentration under reduced pressure after quenching. 21 201137044 After the solvent is removed from the system, the use can be separated from water. The solvent is washed with water. After washing with water, the solvent is removed by concentration under reduced pressure or the like, whereby a block type siloxane compound (A1) can be obtained. The block type siloxane compound (A1) obtained in the above manner is usually in the form of a liquid which is colorless and transparent and has fluidity at 251. Further, the molecular weight of the molecular weight measured by GPC is preferably 8 Å to 2 Å, 〇〇〇, more preferably 1,000 to 10,000, and particularly preferably 15 Å to 6 Å. When the weight average molecular weight is less than 8 Å, there is a possibility that heat resistance is lowered. When the weight average molecular weight is more than 20,000, the viscosity is increased to cause workability. Further, the molecular weight may be based on the equivalent ratio of the alkoxydecane (and the alkoxydecane (c) added as needed) to the polyoxyxanic acid, the molecular weight of the polyoxyxanic oil (b), and the addition of water during the reaction. The amount, reaction time, and reaction temperature were adjusted. The weight average molecular weight is a polystyrene-equivalent weight average molecular weight (m w ) measured by GPC (gel permeation chromatography) under the following conditions. Various conditions of GPC Manufacturer: Shimadzu Manufacturing Column: Protection column SHODEXGPCLF-GLF- 804 (3) Flow rate: 1. 〇ml/min. Column temperature: 40.匚 Solvent: THE (tetrahydrofuran) detector: RI (differential refraction detector) Further, the epoxy equivalent of the oxime block type siloxane compound (A1) (measured by the method described in ns K-7236) is preferred. For 3〇〇~i^oog/call, 22 201137044 is better for 400~l, 200g/eq·. When the epoxy equivalent is less than 3 〇〇g//eq, there is a tendency that the cured product becomes hard and the elastic modulus becomes too high, and when the epoxy equivalent is more than 1,600 g/eq., there is a cured product. The tendency to deteriorate mechanical properties is not good. The viscosity of the block type siloxane compound (AI) (E-type viscosity meter, measured at 25 ° C) is preferably 50 to 2 Torr, 〇〇〇mPa.s, more preferably 5 〇〇 to 10,000 mPa · s , especially good for 8〇〇~5 〇〇〇mPa · s. When the viscosity is less than OmPa s, there is a possibility that the viscosity is too low and it is not suitable for the use of the optical semiconductor sealing material. When the viscosity is more than 2 〇, 〇〇〇mPa·s, there is a case where the viscosity is too high and the workability is poor. The ratio of the three oxygen bonds (four) atoms to the atoms to be cut in the block type oxalate compound (A1) is preferably from 8 to 5% by mole. Moer%. If the ratio of the three oxygen-bonded ceremonial atoms derived from the sesquitertes is less than 8 mol%, there is a characteristic of exhibiting a chain-like polyfluorene site, and the hardened material becomes too soft. The tendency. If the amount exceeds 3 〇 mol%, it exhibits the characteristic of the structural structure of the sesquiterpene oxide. The cured product becomes too hard. If the hardening (4) is too hard, the stress on the resin of the positive film becomes squeaky when the coffee is sealed, so that the ratio of the atoms of the cherished atoms in the coffee can be easily generated by the block type, the HNMR, the Si NMR, the elemental analysis, and the like. Further, the epoxidized cyclohexyl group-containing segmented siloxane compound "...' oxy-CA) and therapeutic () are preferably structurally arranged to contain jasmine. When the stupid base bone is poured into the local moon-moon moon v into the block type oxane compound (Αι), 23 201137044 as long as the polyoxygenated oil (b), alkoxy decane (a) (and The phenyl skeleton may be contained in at least one of the alkoxydecane (C) to be added. Due to the phenyl skeleton in the structure, the strength or refractive index of the cured product is increased. As the refractive index is improved, the light extraction efficiency is improved when used as an optical semiconductor sealing material. Further, the phenyl skeleton also has the effect of preventing the penetration of gas by filling the space between the molecules. When the substituent comprising a phenyl group as an epoxy group having an epoxycyclohexyl group is taken up in an organopolycarboyl group of 3 epoxycyclohexyl groups, it is preferred that the phenyl group is 4 to 45% by weight when the recalculation has been carried out. The range is particularly good for the range of 2~chuan weight/〇. The reason for this is that if it exceeds 45% by weight, the viscosity becomes high, and since the functional group equivalent becomes excessively large, heat resistance is unsatisfactory. The curable resin composition of the present invention contains an alicyclic epoxy resin (B). The alicyclic epoxy resin (B) is introduced in order to impart strong sturdiness to the cured product. The alicyclic epoxy resin (8) preferably has an epoxy ring-sintered 冓b σ substance in the skeleton, and particularly preferably an epoxy resin obtained by an oxidation reaction of a compound having a cyclohexene structure. The epoxy resin may be exemplified by oxidation of a compound which can be produced by the following reaction: a self-reacting reaction of cyclohexene retinoic acid with an alcohol, or a vinegarization reaction of cyclohexylmethyl alcohol and m acid (Tetrahedron νο136 Ρ 2409 (198〇), Tetrahedron Letter P.4475 (1980), etc.), or the cyclohexaaldehyde quaternary reaction (τ-“action). 八本特开2003-170059号Japanese Patent Application Laid-Open No. Hei No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 052,187, and the like. The alcohol is not particularly limited as long as it is a compound having an alcoholic base group, and examples thereof include ethylene glycol, propylene glycol, 1 ^, propylene glycol, 1,2-butanediol, and 1,4-butadiene. Alcohol, 1,5-pentanediol, 16-thyl alcohol, cyclohexane dimethanol, 2,4 diethyl pentanediol, 2-ethyl-2~, ._ ^ ^ J Lane-1 , 3 - propylene glycol, neopentyl glycol, tricyclodecane dimethanol, hydrazine _ T-sterol and other glycols, glycerol, trimethylol , trioxin-propyl propyl ketone, - tyrosin, 2 - triols such as methyl- Μ-butanediol, tetraols such as neopentyl alcohol, di-tris(tetra)-propylpropene, etc. Examples of the acid include oxalic acid, maleic acid, anti-butyric acid, phthalic acid, gimmick-field, monocarboxylic acid, adipic acid, cyclohexanedicarboxylic acid, etc., but are not limited thereto. Further, an acetal compound produced by a reaction of a cyclohexane-diluted derivative with an alcoholic acid is exemplified. Specific examples of the epoxy resin include ERL_422i and uvr_5 ERL 4299 (all Trade name, all manufactured by D〇w Chemical), celloxide2021P, Ep〇lead gt4〇i, Teng E3i5〇, EHPE3150CE (all are trade names, all (10) manufactured by Yixue Industry) and one% pentylene Oxide, etc., but not limited to these (Reference: Epoxy Resin General Basics ΙΡ76-85). These may be used alone or in combination of two or more. In the present invention, the air resistance is improved. From the viewpoint of sexuality, a compound having an epoxy ring-hexane structure is also preferred. The oxygen equivalent (measured by the method of 5 in jis κ_) is preferably 100 to 500 g/eq·, more preferably 100 25 201137044 to 300 g/eq. The molecular weight of the alicyclic epoxy resin (B) is higher. Preferably, it is 2〇〇~ι〇〇〇, preferably 200~600. The curable resin composition of the present invention can be blended into an alicyclic epoxy age (8) in an epoxy-containing cyclohexyl-containing organic polyoxo (A). The amount of the material in the total amount of the alicyclic epoxy resin (8) is from 2 to 4% by weight, and can also be converted to 1.5 to 40% by weight. If the content of the alicyclic epoxy resin (b) is more than 40% by weight, the obtained cured product becomes too hard, cracks are likely to occur as a coffee seal material, or the wafer is excessively stressed, and the second brightness is easily deteriorated. . On the other hand, if the content of the alicyclic epoxy resin (8) is less than 5% by weight, the hardened material obtained is brittle, the coefficient of linear expansion is less, and the suitability of the optical semiconductor sealing material is poor. . The content of the lunar ring epoxy resin (Β) is 1 8~2〇I. /I is more preferably U~2〇% by weight, especially good. When the content of the alicyclic epoxy resin is increased, the hardness of the hardened material obtained by the second two is determined mainly by the hardness of the hardened material and the efficiency of the softening. In the case of an epoxy-containing cyclohexyl group, organic A) (preferably a block type oxoxane compound)

Si:之分散性™己基之有機聚&quot;(A I ‘耐f:、耐光性、光取出效率等之觀點而言係有效； 何枓，但其較脆，且線埶膨腊w^ 令双之 為了使其以^ 因此，於本發明中， 於環氧化：物％性而導入有脂環族環氧樹脂⑻。通常， 氣化合物彼此之反應令’於使作為主成分之環氧樹脂 26 201137044 理想地反應時，係由彼此之環氧當量來決定量比’但 明人發現到於決定該量比時，除環氧當量 聚矽氧（A ) Φ所人士 J〒應有機 與柔軟性之平衡、^氧/^分純，藉此可獲得硬度 傅先取出效率優異之硬化物。 氧基含環氧環己基之有機❹氧（A)之環 曰：〔 係、指含環氧環己基之有機聚矽氧（A)之重 置平均分子量除以含費 ^心里 3㈣環己基之有機聚矽氧（A)之環氧 &quot;(各有4當量之環氧基之樹脂量 所得之值，藉此可估叶含产蔚里 g/eq.)) 1分子十所人右D衣氧衣己基之有機聚石夕氧（A)之 知可將該每基氧的:均量4發明人藉由實驗而獲 樹脂⑻之“ # 4基準來決定脂環族環氧 人严胃„ 量，具體而言，脂環族環氧樹脂（B)於 ::ί:已基之有機聚石夕氧⑷與脂環族環氧樹脂⑻ 氧了:二之量子(重量%)與該含環氧環己基之有㈣ 環族環氧樹脂(:)= = = ;即，發現到藉由將脂 己=機聚，氧(A)之重量平均分子量)+(含環： =基之有機聚石夕氧（A)之環氧當量）重量％( 源自鍵狀聚錢部位之柔軟性不受到損害， 族Ϊ氧ΐ ί之平衡更優異之硬化物，進而發現到當脂環 衣氧樹月曰（B)之含晉 時，·s /())滿足上述式（比例ρ ) —脂渾濁之產生，絲出效率變得良好。 環氧Γ己=推合比率含有脂環族環氧樹脂(B)，於含 己基之有機聚石夕氧“）-酸肝…或任意 27 201137044 =加之多元幾酸（D))之硬化之間，可置人脂環 树脂（B) ~酸裒氣 ” ）（及/或多元羧酸⑼）之交聛 右系統中具有超過所需之脂環族環氧樹脂⑻，則僅:; 族環氧樹脂⑻—酸肝(c)(及/或多元幾酸(二環 硬化系佔據於硬化物中，因此存在損害源自鏈狀聚石夕氣^ 位之柔軟性，且變成較脆且較弱之硬化物之可能性。又 於硬化物中’僅上述脂環族環氧樹脂⑻—酸酐（c)(， /或多元叛酸⑻)之硬化系對於其他部分之相溶性較低及 因此成為樹脂渾濁之原0 ’且存在進而導致絲出 降之可能性。 卜 藉由以上述比例摻合脂環族環氧樹脂（B),可獲得有 效地表現出源自鏈狀聚石夕氧部位之柔軟性，硬度與柔：性 之平衡更優異，且提高了光取出效率之硬化物。 根據上述式，每i分子之環氧基量越多，脂環族環氧 樹脂（B)之導入量越多。另-方面，每1分子之環氧基量 越少’脂環族環氧樹脂（B)之導入量越少。 根據上述式所算出之比例p較理想的是4〇以下（即， 脂環族環氧樹脂（B )之最大含量為4〇重量％以下）。但是， :例P係上述1.5〜40重量％之範圍内之量。較佳為脂環族 環氧樹脂（B )為1.5〜2〇重量％ ,且比例p為4〇以下。 本發明之硬化性樹脂組成物含有酸酐（c)作為硬化 劑。酸酐（C )因透明性優異且為液狀，故作業.性亦優異。 酸酐具體可列舉：鄰苯二曱酸酐、苯偏三酸酐、焦蜜 石酸二酐、順丁烯二酸酐、四氫鄰苯二曱酸酐、曱基四氫 28 201137044 鄰苯二甲酸酐、甲基耐地酸酐、耐地酸酐、六氫鄰笨二甲 酸酐、甲基六氫鄰苯二甲酸酐、丁烷四甲酸酐、雙環[Hi ] 庚烷一 2,3 —二曱酸酐、甲基雙環[2JJ]庚烷—2,3 —二甲酸 酐、環己烷~ 1，2,4 —三曱酸_ι，2—酐等酸酐。 酸軒特佳為：甲基四氫鄰苯二曱酸酐、曱基耐地酸野 (methylnadic anhydride)、耐地酸酐（nadic anhydride)、六氫 鄰苯二曱酸酐、甲基六氫鄰苯二曱酸酐、丁烷四曱酸酐、 雙環[2,2，1]庚烷一2,3—二曱酸酐、甲基雙環[2,2，1；1庚烷— 2’3 —二甲酸酐、環己烷一1,2,4 一三甲酸一1,2 —酐。 上述酸酐之中，更佳為由下述式（5)Si: Dispersibility TM hexyl-based organic poly&quot; (AI's resistance to f:, lightfastness, light extraction efficiency, etc.; is effective, but it is brittle, and the wire is swollen w^ Therefore, in the present invention, an alicyclic epoxy resin (8) is introduced in an epoxidation ratio. Usually, the gas compounds react with each other to cause the epoxy resin 26 as a main component. 201137044 When the reaction is ideally determined, the ratio is determined by the epoxy equivalent of each other. However, when it is found that the ratio is determined, the epoxy equivalent of polyoxyl (A) Φ should be organic and soft. The balance, ^ oxygen / ^ pure, by which the hardness of the first extraction efficiency is excellent. The oxygen-containing cyclohexyl group of organic oxime (A) ring: [system, refers to the epoxy ring The reset average molecular weight of the hexyl-organic polyfluorene (A) is divided by the amount of the epoxy resin of the organic polyfluorene (A) containing 3 (tetra)cyclohexyl groups (amount of resin having 4 equivalents of epoxy groups each) Value, by which it can be estimated that the leaves contain virgin g/eq.)) 1 molecule of ten people right D oxime hexyl group organic poly-stone (A) It is known that the average amount of oxygen per unit of oxygen is obtained by the inventors from the "# 4 basis of the resin (8) to determine the amount of the alicyclic epoxy group, specifically, the alicyclic epoxy resin ( B) in:: ί: Organic-based polysulfide (4) and alicyclic epoxy resin (8) Oxygen: two quantum (% by weight) and the epoxy-containing cyclohexyl (4) cycloalloy ( :) = = = ; that is, the weight average molecular weight of oxygen (A) + (including the epoxy equivalent of the organic polyphosphorus (A) of the ring: = group) is found by the polymerization of the fat. % (from the softness of the bond-shaped money-storing part is not damaged, the balance of the family's Ϊ ΐ ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί /()) satisfies the above formula (proportion ρ) - the generation of fat turbidity, and the silking efficiency becomes good. Epoxy oxime = push ratio containing alicyclic epoxy resin (B), hardening of hexyl-containing organic polyoxo-oxygen ")-acid liver ... or any 27 201137044 = plus polybasic acid (D) Between the alicyclic resin (B) ~ acid oxime" (and / or polycarboxylic acid (9)) in the right system has more than the desired alicyclic epoxy resin (8), then only: Epoxy resin (8) - acid liver (c) (and / or polybasic acid (bicyclic hardening system occupies in the hardened material, so there is damage from the softness of the chain polystone, and becomes brittle and The possibility of a weaker hardened material. In the hardened material, only the hardening of the above-mentioned alicyclic epoxy resin (8)-anhydride (c) (or polybasic acid (8)) is less compatible with other parts. Therefore, it becomes the original turbidity of the resin 0' and there is a possibility of causing the silk to fall and fall. By blending the alicyclic epoxy resin (B) in the above ratio, it is possible to effectively exhibit the origin of the chain-like polylithic eve. The softness of the oxygen site, the hardness and the softness: the balance of the properties is superior, and the cured product of the light extraction efficiency is improved. According to the above formula, each i molecule The more the amount of epoxy groups, the more the amount of introduction of the alicyclic epoxy resin (B). In other respects, the smaller the amount of epoxy groups per molecule, the amount of introduction of the alicyclic epoxy resin (B) The ratio p calculated according to the above formula is preferably 4 Å or less (that is, the maximum content of the alicyclic epoxy resin (B) is 4 〇 or less by weight). However, Example P is the above 1.5~ The amount in the range of 40% by weight, preferably the alicyclic epoxy resin (B) is 1.5 to 2% by weight, and the ratio p is 4 Å or less. The curable resin composition of the present invention contains an acid anhydride (c) The acid anhydride (C) is excellent in transparency and liquid, so it is also excellent in workability. Specific examples of the acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, and cis-butene. Diacid anhydride, tetrahydrophthalic anhydride, mercapto tetrahydrogen 28 201137044 phthalic anhydride, methyl acid anhydride, ceric anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride Butane tetracarboxylic anhydride, bicyclo[Hi]heptane-2,3-diphthalic anhydride, methylbicyclo[2JJ]heptane-2,3-dicarboxylic anhydride, cyclohexane ~ 1,2,4 - tridecanoic acid _ι, 2-anhydride and other anhydrides. Acid Xuanjia is: methyl tetrahydrophthalic anhydride, methylnadic anhydride, acid anhydride ( Nadic anhydride), hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butane tetraphthalic anhydride, bicyclo[2,2,1]heptane-2,3-diphthalic anhydride, methyl bicyclic [2,2,1; 1 heptane-2'3-dicarboxylic anhydride, cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride. Among the above acid anhydrides, more preferably (5)

(式中，Q表示氫原子、甲基、羧基之至少一種）所表 示之六氫鄰苯二甲酸酐、曱基六氫鄰苯二曱酸酐、環己烷 —1，2,4~三甲酸—1，2一酐，其中，較佳為甲基六氫鄰苯二 甲酸酐、環己烷一1，2,4 一三甲酸一 1,2 —酐。 本發明之硬化性樹脂組成物中之酸酐（C )之使用量相 對於所有環氧樹脂之環氧基1當量，較佳為0.7〜1.2當量。 當相對於環氧基1當量未達0.7當量時，或者超過1.2當量 時’气存在硬化變得不完全，無法獲得良好之硬化物性之 可此性。當與後述之多元羧酸等硬化劑併用時，較理想的 29 201137044 是將所使用之硬化劑之總量設定為上述範圍。 於本發明中，酸酐（c)較理想的是與作為其他硬化劑 之多元羧酸（D)併用，併用時之含量較理想的是以與後述 之多元羧酸（D )之比例來決定’較佳為下述式之範圍。 Wl/ (W1 + W2) =0_05 〜0.70 (其中’ W1表示多元羧酸（D)之摻合重量份，W2 表示酸酐（C)之摻合重量份）。 於上述中，Wl/( W1 + W2)之範圍更佳為〇.05〜〇 6〇， 進而更佳為〇.1〇〜0.55，特佳為0.15〜〇_4。若小於〇〇5， 則硬化時酸酐（C)之揮發變多之傾向較強而不佳。若超過 〇·70 ’則成為高黏度，而難以操作。 酸酐之混合物。 虽併用酸酐（c)與多元羧酸（D)時，就操作之簡便 陡方面而§，如下之方法亦較佳，即當製造多元羧酸（〇 ) 時於過剩之酸酐（C)中製造，從而製作多元羧酸（D)與 本發明中所使用之多元鲮酸（D)較理想的是具有至少 2個以上之羧基， 並將脂肪族烴基作為主骨架之化合物(wherein, Q represents at least one of a hydrogen atom, a methyl group and a carboxyl group), hexahydrophthalic anhydride, mercaptohexahydrophthalic anhydride, cyclohexane-1,2,4-tricarboxylic acid The 1,2-monoanhydride, wherein methylhexahydrophthalic anhydride, cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride is preferred. The acid anhydride (C) used in the curable resin composition of the present invention is preferably used in an amount of from 0.7 to 1.2 equivalents per equivalent of the epoxy group of the epoxy resin. When the amount is less than 0.7 equivalents per equivalent of the epoxy group, or when it exceeds 1.2 equivalents, the hardening of the gas becomes incomplete, and good cured physical properties cannot be obtained. When it is used in combination with a curing agent such as a polyvalent carboxylic acid to be described later, it is preferable that 29 201137044 is used to set the total amount of the curing agent to be used in the above range. In the present invention, the acid anhydride (c) is preferably used in combination with a polyvalent carboxylic acid (D) which is another curing agent, and the content thereof is preferably determined in proportion to a ratio of a polycarboxylic acid (D) to be described later. It is preferably in the range of the following formula. Wl / (W1 + W2) = 0_05 to 0.70 (wherein "W1 represents a blended parts by weight of the polycarboxylic acid (D), and W2 represents a blended by weight of the acid anhydride (C)). In the above, the range of Wl/(W1 + W2) is more preferably 〇.05~〇6〇, and further preferably 〇.1〇~0.55, particularly preferably 0.15~〇_4. If it is less than 〇〇5, the tendency of the acid anhydride (C) to volatilize during hardening becomes stronger and lower. If it exceeds 〇·70 ′, it becomes highly viscous and difficult to handle. a mixture of anhydrides. When the acid anhydride (c) and the polycarboxylic acid (D) are used in combination, the operation is simple and steep, and the following method is also preferable, that is, in the production of the polybasic carboxylic acid (〇) in the excess acid anhydride (C). The polycarboxylic acid (D) and the polybasic acid (D) used in the present invention are preferably compounds having at least two or more carboxyl groups and having an aliphatic hydrocarbon group as a main skeleton.

等總稱為多元羧酸。The total is called polycarboxylic acid.

6官能之羧酸，更佳為藉 元醇與酸酐之反應所獲得 备飽和脂肪族環狀酸酐即 30 201137044 聚缓酸。 2〜6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、丨，3 _丙二醇、 :::丁二醇、Μ- 丁二醇、1’5—戍二醇、丨，6—已二醇、 匕烷二曱醇、2,4—二乙基戊二醇、2_乙基丁其— 内二醇、新戊二醇、三環癸烷二曱醇、降莰烯二：、 :醇改質矽油等二醇類，丙三醇、三羥曱基乙⑮、三 土丙烷、三羥甲基丁烷、2 —羥 — 類，新Λ ^ ^ Μ— 丁二醇等三醇 研戍四醇、二—三羥曱基丙烷 等六醇類等。 醉頬-新戊四醇 特佳之多元醇係碳數為5以上之醇，特佳 ，環己炫二甲醇、…環己炫二二，已二 二广、2,4-二乙基戊二醇、2—乙基—2—丁武—&amp;己坑 一醇、新戊二醇、=環癸浐__ 土 一1，3 —丙 質矽油尊“醇、降获烯二醇、甲醇改 '由專，其中更佳為2—乙基一 2— 丁装 T醇改 新戊二醇、24——6 Λ ^ 土 ι，3'-丙二醇、 〜甲醇、降莰烯二醢、田瞒 甲醇、二環 結構或環狀社構二、。改質矽油等具有支鏈鏈狀 狀π構、矽氧烷結構之多元醇。 狀 此處，具體而言，甲醇改質 所示之化合物： h由較佳為下述式（4Α) R? R? r7A 6-functional carboxylic acid, more preferably a reaction of a glycol with an acid anhydride, is obtained by preparing a saturated aliphatic cyclic anhydride, 30 201137044. The 2 to 6-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, hydrazine, 3-propylene glycol, ::: butanediol, and hydrazine-butanediol. 1'5-decanediol, hydrazine, 6-hexane diol, decane decyl alcohol, 2,4-diethylpentanediol, 2-ethylbutyrolactone, neopentyl glycol, neopentyl glycol, three Cyclohexane dinonanol, norbornene II:, alcohol modified oxime oil and other glycols, glycerol, trishydroxylethane 15, tris-propane, trimethylol butane, 2-hydroxy- , New Λ ^ ^ Μ - butanediol and other triols such as tetraol, di-trihydroxyhydrazine propane and other hexaols. Drunken-Pentaerythritol is a good polyol with a carbon number of 5 or more, especially good, cyclohexyl dimethanol, ... cyclohexanthene, two, two, two, 2,4-diethylpentane Alcohol, 2-ethyl-2, butyl-&amp; hexanol, neopentyl glycol, = ring 癸浐__ 土-1,3 - propyl hydrazine oil "alcohol, olefin diol, methanol Change 'from the special, which is better 2 - ethyl 2 - butyl T alcohol modified neopentyl glycol, 24 - 6 Λ ^ soil ι, 3 '- propylene glycol, ~ methanol, decylene diterpenoids, 瞒Methanol, bicyclic structure or cyclic structure II. Polyol having a branched chain π-structure and a decane structure, such as modified eucalyptus oil. Here, specifically, a compound represented by methanol modification: h is preferably of the following formula (4Α) R? R? r7

r7 I Si〜Re〜_〇H (4 A) 31 201137044 (式（4A )中，R8表示碳總數為ii 〇之伸烷基’尺 表示甲基或笨基’ P以平均值計表示1〜1〇〇)。 於式（4A )中，Rs之具體例可列舉：亞曱基伸乙基、 伸丙基、伸異丙基、伸丁基、伸異丁基、伸戊基、伸異戍 基、伸己基、伸庚基、伸辛基等伸院基，乙氧基伸乙基、 丙氧基伸乙基、丙氧基伸丙基、乙氧基伸丙基等。特佳者 為丙氧基伸乙基、乙氧基伸丙基。 其次，R?表示甲基或苯基，可為同種或異種中之任一 種。 於式（4A)中，p以平均值計為i'wo,較佳為2〜8〇, 更佳為5〜30。 酸酐特佳為：甲基四氫鄰苯二曱酸酐、甲基耐地酸酐、 耐地酸針 '六氫鄰苯二甲酸針、甲基六氫鄰苯二甲酸針、 丁烧四幾kgf、雙環[2,2，1]庚炫—2,3~二叛g請、甲基雙 環[2,2，ij庚院-2,3 —二甲酸奸、環己m4_三曱酸— ’酐等其中較佳為甲基六氫鄰笨二甲酸酐、環己烷— i，2,4—三曱酸一1，2 -酐。 加成反應之條件並無特別指定，具體之反應條件之一 為如下方法：使酸Sf、多元醇於無觸媒、無溶劑之條件下， 且於40〜15代反應並進行加熱，反應結束後直接取出。但 並不限定於本反應條件。 .以上述方式所獲得之多缓酸，特佳為由下述式（6)表 示之化合物： 32 (6) 201137044 pR7 I Si~Re~_〇H (4 A) 31 201137044 (In the formula (4A), R8 represents that the total number of carbons is ii 伸, and the alkyl group' represents a methyl group or a stupid base. P is expressed by the average value 1~ 1〇〇). In the formula (4A), specific examples of Rs include an anthracene group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a decyl group, and a hexyl group. Shen Gengji, Shen Xinji, etc., ethoxylated ethyl, propoxyethyl, propoxypropyl, ethoxypropyl and the like. Particularly preferred are propoxy ethyl and ethoxy propionyl. Next, R? represents a methyl group or a phenyl group, and may be either of the same species or a heterogeneous species. In the formula (4A), p is i'wo, preferably 2 to 8 Å, more preferably 5 to 30, in terms of an average value. The acid anhydride is particularly preferably: methyl tetrahydrophthalic anhydride, methyl acid anhydride, lysine needle hexahydrophthalic acid needle, methyl hexahydrophthalic acid needle, diced four or more kgf, Double ring [2, 2, 1] Geng Xuan - 2, 3 ~ two rebellious g, methyl bicyclo [2, 2, ij Gengyuan-2, 3 - dicarboxylic acid, cycloheximide m4_ tridecanoic acid - 'anhydride Among them, methylhexahydrophthalic anhydride and cyclohexane-i,2,4-tridecanoic acid-1,2-anhydride are preferred. The conditions of the addition reaction are not specifically specified. One of the specific reaction conditions is as follows: the acid Sf and the polyol are reacted in a solvent-free, solvent-free condition, and reacted in 40 to 15 generations, and the reaction is completed. Take it out directly. However, it is not limited to the reaction conditions. The polyacid which is obtained in the above manner is particularly preferably a compound represented by the following formula (6): 32 (6) 201137044 p

之脂肪族基）m較佳為1〜7，特佳為2〜6 由於作為硬化劑成分之多元羧酸（D )之結晶性較高， 因此長期保存後可能會引起含環氧環己基之有機聚矽氧 (A)之黏度上升，但於本發明之硬化性樹脂組成物中，因 將脂環族環氧樹脂（B)作為必需成分，故可抑制黏度上升。 其原因在於脂環族環氧樹脂（B)可使多元羧酸溶解並使其 相洛於有機聚矽氧結構中，又，藉此可提高作為硬化劑之 多凡羧酸對於硬化性組成物之導入量。又，藉由將多元羧 馱用作硬化劑，具有進一步提昇硬化物之耐透氣性性之效 果0 本發明之硬化性樹脂組成物較佳為含有鋅鹽及/或辞 錯合物（Ε )作為硬化促進劑。 辞鹽及/或辞錯合物（Ε)係以鋅離子為中心元素之鹽 及/或錯合物，較佳為具有磷酸酯或磷酸作為相對離子及 /或配位子。又，特佳為：上述鋅鹽，以及磷酸、碳數為1 〜30之烧基之填酸醋（單烧基酿體、二烧基醋體、三烧基 酿體、或該等之混合物）之鋅鹽及/或鋅錯合物。於上述 33 201137044 中，烷基可列舉：甲I、里系甘 J + I異丙基、丁基、2_乙基己基、辛 基、異癸基、異硬酯基、癸基 '十六基等。 於本發明中，特佳為碳數為3〜）5之烧基之麟酸醋， 該醋體可為混合物’亦可為單體，較佳為其主成分為磷酸 單烷基酯體。 特佳為：單烷基酯體於所含有之磷酸酯中以單烷基 醋體、二烷基醋體、三垸基醋體之莫耳比（以氣相層析法 之純度代替。但是，由於必需進行三曱基石夕基化，因此靈 敏度會出現差異）計，於已進行三甲基石夕基化處理階段， 單烷基酯體之存在量為5〇面積％以上。 進而，使所獲彳于之磷酸酯與例如碳酸鋅、氫氧化鋅等 反應，藉此可獲得本發明中所使用之鋅鹽及/或辞錯合物 (專利文獻EP699708號公報）。 此種磷酸醋之鋅鹽及/或鋅錯合物之詳細情況，磷原 子與鋅原子之比率（P/Zn)較佳為丨2〜2 3,更佳為ι 3 〜2.0。特佳為1.4〜1.9。即，於特佳之形態中，較佳為相 對於鋅離子1莫耳，磷酸酯（或源自磷酸酯之磷酸）成為 2.0莫耳以下，且具有幾個分子因離子鍵（或配位鍵）而相 關聯之結構，而非單純之離子結構者。此種鋅鹽及/或鋅 錯合物亦可藉由例如日本特表2〇〇3 — 5丨495號公報中所記 載之方法而獲得。 又，上述鋅鹽及/或鋅錯合物（E )亦可使用羧酸鋅（較 佳為2 —乙基己酸鋅、硬脂酸鋅、二十二酸鋅，肉豆蔻酸鋅 等碳數為3〜20之烷基甲酸鋅）。 34 201137044 :本發明之硬化性樹脂組成物中，鋅鹽及/或鋅錯a 物（）之含量相對於含環氧環己基之有機聚 ： 脂環族環氧樹脂（B)之總量， 與 合物⑻為〇.〇1〜8重量。/汁鋅鹽及，或鋅錯 8重里/〇,更佳為0.05〜5重量％，進而 更佳為0·1〜4重詈％。7 . ^ /又，特佳為〇. 1〜2重量％ 〇 字本卷月之硬化性樹脂組成物用於光學材料龙 用於光半導體密封劑時，較佳為含有作為光穩定劑之受;且 胺化合物、作為抗氧化劑之嶙系化合物作為特佳之成分。 上述胺化合物例如可 卒.丁烧四曱酸四 (1，2,2,6,6—五甲基—4…辰。定基）醋、1，2,3,4- 丁烧四甲酸四 (’ ’ ’ 曱基4—哌啶基）酯、！，2,3,4- 丁烷四甲酸與 1，2,2,6,6—五甲其 e Λ 穴 土 4 0辰。定醇及3,9—雙（2—羥基一ι，ι—二 Τ 基乙基）—248in~ a- ’，mo~四氧雜螺[5,5]十一烷之混合酯化 物、癸二酸雙（2,2 6 6 —四田甘 ，’ 四曱基一 4 —哌啶基）癸二酸酯、碳 酸雙（1-十一烷氧基—29&lt;乙 ^ 2,2,6,6~四甲基哌啶一 4—基）酯、甲 基丙稀酸2,2,6,6 —四甲真 τ丞—4一哌啶酯、癸二酸雙（2,2 ό ό —四甲基—4~°辰咬基）酉旨、癸二酸雙（1，2,2，Μ—五甲基—’4 -派咬基)醋、4—苯甲醯氧基—2,2，M一四甲基錢、卜 [2— [3一 (3,5 —二—篦=Τ 甘 弟二丁基一4一羥基苯基）丙醯氧基]乙 基]—4— [3—(35—-贫 _ 一—弟三丁基一4 —羥基苯基）丙醯氧基] 2’2’Μ四甲基η底咬、甲基丙稀酸五曱基—4 0底定基S曰、[[3,5一雙〇，卜二甲基乙基）—4一經基苯基] 曱基]丁基丙二酸 又五曱基一4一哌啶基）醋、癸 一酸雙（2,2,6,6~~四甲其 Μ T i — 1(辛氧基）一4—哌啶基）酯、1，1 — 35 201137044 二甲基乙基氫過氧化物（l，l-dimethylethylhydroperoxide)與 辛烷之反應產物、N，N，，N，，，N，，，~四一（4,6 —雙一（丁基—（N ''甲基一2,2,6,6 —四曱基0底咬一4 —基）胺基）一三〇井— 基）~~4,7 — 二氮雜癸烧一 1，1〇— 二胺、二丁胺· ι，3,5 —三口 井· N，N’一雙（2,2,6,6—四甲基一4 -哌啶基一1，6-六亞曱 基二胺與N — (2,2,6,6 —四曱基—4 一哌啶基）丁基胺之縮聚 物、聚[[6—(1，1，3,3 —四曱基丁基）胺基-1，3,5—三α井一2,4 一基][(2,2,6,6—四曱基一4 —旅。定基）亞胺基]六亞曱基 [(2,2,6,6 —四曱基一4一哌啶基）亞胺基;]]、琥珀酸二曱酯與 4〜經基一2,2,6,6—四曱基一1 —哌啶乙醇之聚合物、2,2,4,4 〜四曱基一20—（冷一十二烷氧基羰基）乙基_7_氧雜— 〇 —氮雜一螺[5,1，11，2]二十一烧—21—酮、冷一丙胺 馱’Ν, — (2,2,6,6 —四曱基一哌啶基）一十二烷基酯/十四 烷基酯、Ν—乙醯基一 3—十二烷基—丨一（2，2,6,6—四曱基~ 4〜哌啶基）吡咯啶—2,5_二酮、2,2,4,4一四曱基—7_氧雜 5 一 氮雜一螺[5,1，11，2]二十一烧一21—酮、2,2,4,4 四曱基一21 -氧雜一 3,20 -二氮雜雙環一 [5，1，11，2]—二 十烷~2〇 —丙酸十二烷基酯/十四酯、丙二酸、[(4 一曱 ^基苯基亞甲基]一雙（1，2,2,6,6—五曱基一 4 —哌啶基） ^ 2,2,6,6 —四甲基—4 —哌啶醇之高級脂肪酸酯、1&gt;3—苯 一甲醯胺（l，3-benzenedicarboxamide)、N，N，-雙（2,2,6,6-四 甲基〜4一哌啶基）等受阻胺系化合物等。 上述光穩定劑即胺化合物，可使用以下所示之市售品。 】如可列舉.汽巴精化（Ciba Specialty Chemicals )製 36 201137044 造之 TINUVIN765、TINUVIN770DF、TINUVIN144、 TINUVIN123 、 TINUVIN622LD 、 TINUVIN152 、 CHIMASSORB944，Adeka 製造之 LA- 52、LA— 57、LA-62 、 LA- 63P 、 LA— 77Y 、 LA— 81 、 LA— 82 、 LA- 87 等。 於本發明之硬化性樹脂組成物中，光穩定劑之使用量 相對於含環氧環己基之有機聚矽氧（A )與脂環族環氧樹脂 (B )之總量，以重量比計為0.005〜5重量％，更佳為0.01 〜4重量％，0.1〜2重量％。 上述磷系化合物並無特別限定，例如可列舉：1，1，3 — 三（2—曱基一4 一雙十三烷基亞磷酸酯一 5—第三丁基苯基） 丁 烧 (1,1,3-tris(2-methyl-4-ditridecylphosphito-5-t-butylphenyl)butane)、二硬酯基新戊四醇上亞磷酸酯、雙（2,4 一二一第三丁基苯基）新戊四醇二亞磷酸酯、雙（2,6_二一 第三丁基一4 一甲基苯基）新戊四醇二亞磷酸酯、苯基雙酚A 新戊四醇二亞磷酸酯、二環己基新戊四醇二亞磷酸酯、亞 磷酸三（二乙基苯基）酯、亞磷酸三（二一異丙基苯基）酯、亞 磷酸三（二一正丁基苯基）醋、亞磷酸三（2,4—二一第三丁基 苯基）酿、亞磷酸三（2,6—二一第三丁基苯基）酯、亞磷酸三 (2,6—二一第三丁基苯基）酯、2,2|—亞曱基雙（4,6-二一第 三丁基苯基）（2,4_二一第三丁基苯基）亞磷酸酯、2,2，_亞甲 基雙（4,6—二一第三丁基苯基）（2_第三丁基一 4 —甲基苯基） 亞磷酸酯、2,2'—亞曱基雙（4 一曱基一 6 —第三丁基苯基）（2 一第三丁基一4 一曱基苯基）亞磷酸酯、2,2,一亞乙基雙（4 — 甲基一6 —第三丁基苯基）（2 —第三丁基一4 —曱基苯基）亞 37 201137044 磷酸酯、四（2,4-二一第三丁基苯基）一4,4，一伸聯苯基二亞 膦 酸 酯 （tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylenephosphonite)、四（2,4 —二一第三丁 基苯基）一 4,3'—伸聯苯基二亞膦酸酯、四（2,4一二一第三丁基苯基）一 3，3'—伸聯苯基二亞膦酸酯、四（2,6—二一第三丁基苯基）一 4,4'一伸聯苯基二亞膦酸酯、四（2,6—二一第三丁基苯基）一 4,3'—伸聯苯基二亞膦酸酯、四（2,6—二一第三丁基苯基）一 3,3^ —伸聯苯基二亞膦酸酯、雙（2,4一二一第三丁基苯基）一 4 一苯基一苯基亞膦酸酯、雙（2,4一二一第三丁基苯基）一3 —苯基一苯基亞膦酸酯、雙（2,6 —二一正丁基苯基）_3 —苯 基一苯基亞膦酸酯、雙（2,6—二一第三丁基苯基）一 4一苯基 一苯基亞膦酸g旨、雙（2,6—二一第三丁基苯基）一3 —苯基一 苯基亞膦酸S旨、四（2,4—二一第三丁基一5_曱基苯基）一 4,4'—伸聯苯基二亞膦酸酯、磷酸三丁酯、磷酸三甲酯、磷 酸三甲苯醋（tricresyl phosphate)、構酸三苯醋、填酸三氣苯 酯、峨酸三乙酯、攝酸曱盼基二苯酯（diphenyl cresyl phosphate)、峨酸單鄰聯苯基二苯基酯 （diphenyl monoorthoxenyl phosphate )、填酸三丁氧基乙酯、填酸二 丁酯、磷酸二辛酯、磷酸二異丙酯等。 上述磷系化合物亦可使用市售品。 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、Adekastab 260、 Adekastab 522A、Adekastab 1178 、Adekastab 1500、 38 201137044The aliphatic group) m is preferably from 1 to 7, particularly preferably from 2 to 6. Since the polycarboxylic acid (D) as a hardener component has high crystallinity, it may cause epoxycyclohexyl group after long-term storage. In the curable resin composition of the present invention, since the alicyclic epoxy resin (B) is an essential component, the viscosity can be suppressed from increasing. The reason for this is that the alicyclic epoxy resin (B) dissolves the polycarboxylic acid and causes it to be in the organic polyoxo structure, thereby increasing the amount of the carboxylic acid as a hardener for the hardenable composition. The amount of import. Further, by using a polycarboxylate as a curing agent, it has an effect of further improving the gas permeability resistance of the cured product. The curable resin composition of the present invention preferably contains a zinc salt and/or a rhodium complex (Ε). As a hardening accelerator. The salt and/or the complex (Ε) is a salt and/or a complex of zinc ions as a central element, and preferably has a phosphate or phosphoric acid as a relative ion and/or a ligand. Further, particularly preferred are: the above-mentioned zinc salt, and phosphoric acid, a sulphuric acid-filled vinegar having a carbon number of 1 to 30 (single-burning broth, di-burning vinegar, tri-burning broth, or a mixture thereof) a zinc salt and/or a zinc complex. In the above-mentioned 33 201137044, the alkyl group may be exemplified by: A, linyl J + I isopropyl, butyl, 2-ethylhexyl, octyl, isodecyl, isostearyl, fluorenyl '16 Base. In the present invention, it is particularly preferred to use a calcined linoleic acid having a carbon number of 3 to 5, which may be a mixture, or a monomer, preferably having a main component of a monoalkyl phosphate. Particularly preferred is that the monoalkyl ester body is substituted by the purity of the monoalkyl vinegar, the dialkyl vinegar, and the triterpene vinegar in the phosphate ester contained therein (by gas chromatography). Since the sensitivity of the triterpene base metallization is necessary, the amount of the monoalkyl ester body is 5 Å or more in the stage of the trimethyl schistification treatment. Further, the obtained phosphate ester is reacted with, for example, zinc carbonate, zinc hydroxide or the like to obtain a zinc salt and/or a speech-compounding compound used in the present invention (Patent Document EP699708). The details of the zinc salt and/or zinc complex of the phosphoric acid vinegar, the ratio of the phosphorus atom to the zinc atom (P/Zn) is preferably 丨2 to 2 3, more preferably ι 3 to 2.0. Very good for 1.4 to 1.9. That is, in a particularly preferred form, it is preferred that the phosphate (or phosphoric acid-derived phosphoric acid) is 2.0 mol or less and has several molecules due to ionic bonds (or coordinate bonds) with respect to 1 mol of zinc ions. And the associated structure, not the simple ion structure. Such a zinc salt and/or a zinc complex can also be obtained by a method described in, for example, Japanese Patent Publication No. 23-5-495. Further, as the zinc salt and/or the zinc complex (E), zinc carboxylate (preferably zinc 2-ethylhexanoate, zinc stearate, zinc behenate, zinc myristate or the like may be used. The number is 3 to 20% zinc formate). 34 201137044: The content of the zinc salt and/or the zinc complex () in the curable resin composition of the present invention relative to the total amount of the organopoly:cycloaliphatic epoxy resin (B) containing an epoxycyclohexyl group, The compound (8) is 〇.〇1~8 by weight. / juice zinc salt and, or zinc wrong 8 weights / 〇, more preferably 0.05 to 5% by weight, and even more preferably 0. 1 to 4% by weight. 7 . ^ / again, particularly preferably 〇. 1 to 2% by weight 〇 本 卷 之 之 之 之 之 光学 光学 光学 光学 硬化 硬化 硬化 硬化 硬化 硬化 硬化 硬化 硬化 硬化 硬化 硬化 硬化 硬化 硬化 硬化 硬化 硬化 硬化 硬化 硬化 硬化 硬化 硬化 硬化 硬化 硬化And an amine compound and an oxime compound which is an antioxidant are excellent components. The above-mentioned amine compound can be, for example, tetrabutyl succinic acid tetrakis(1,2,2,6,6-pentamethyl- 4 butyl hydrazine), 1,2,3,4-butane tetracarboxylic acid tetra ( ' ' 'Mercapto-4-piperidinyl) ester,! , 2,3,4-butane tetracarboxylic acid and 1,2,2,6,6-pentamethine e Λ acupoints soil 4 0 Chen. Alcohol and 3,9-bis(2-hydroxyl,1,2-diylethyl)-248in~ a- ', a mixed ester of mo~tetraoxaspiro[5,5]undecane, hydrazine Diacid di(2,2 6 6 -tetradagan, 'tetradecyl- 4 -piperidinyl) sebacate, bis(1-undecyloxy-29&lt;2^2,2,6 , 6~Tetramethylpiperidine-4-yl)ester, methyl acrylate 2,2,6,6-tetramethyltradoxime-4 piperidinyl ester, azelaic acid bis(2,2 ό ό —Tetramethyl—4~°chen bite base”, bismuth (1,2,2, Μ-pentamethyl-'4-tele-based) vinegar, 4-benzylidene-oxyl-2 , 2, M-tetramethyl money, Bu [2 - [3, (3,5 - di- 篦 = 甘 Gandi dibutyl 4-hydroxyphenyl) propyl oxime] ethyl] - 4 - [3-(35--lean_-di-tert-butyl-4-hydroxyphenyl)propenyloxy] 2'2'Μtetramethyl η bottom bite, methacrylic acid pentadecyl- 4 0 Bottom group S曰, [[3,5-bi-indole, bis-dimethylethyl)- 4-monophenyl)mercapto]butylmalonic acid and pentylene-tetra- 4-piperidinyl) vinegar, hydrazine Monosodium bis(2,2,6,6~~tetramethylpyrazine T i —1(octyloxy)-4-piperidinyl) ester 1,1 — 35 201137044 Reaction product of dimethylethylhydroperoxide (1,1-dimethylethylhydroperoxide) with octane, N,N,,N,,,N,,,~4 (4,6 - double one (butyl - (N ''methyl - 2, 2, 6, 6 - tetradecyl 0 bottom base 4 - base) amine) a three wells - base) ~ ~ 4, 7 - two Azaindole-1,1〇-diamine, dibutylamine·ι,3,5—three wells · N,N'-double (2,2,6,6-tetramethyl-4-piperidinyl a polycondensate of 1,6-hexamethylenediamine and N-(2,2,6,6-tetradecyl-4-piperidinyl)butylamine, poly[[6—(1,1, 3,3 -tetradecylbutyl)amino-1,3,5-three alpha well- 2,4-yl][(2,2,6,6-tetradecyl- 4 - british. Amino]hexamethylene[(2,2,6,6-tetradecyl-4-tetrahydropyridinyl)imine;]], dinonyl succinate and 4~ vial 2, 2, 6 , 6-tetradecyl-1 - piperidine ethanol polymer, 2,2,4,4~tetradecyl-20-(cold-dodecyloxycarbonyl)ethyl_7_oxa-indole- Aza-snail [5,1,11,2] twenty-one burnt-21-ketone, cold-propylamine 驮'Ν, — (2,2,6,6-tetradecyl- Pyridyl)-dodecylester/tetradecylester, fluorenyl-ethenyl-3-dodecyl-indole-(2,2,6,6-tetradecyl~4~piperidyl) Pyrrolidine-2,5-dione, 2,2,4,4-tetradecyl-7-oxa-5-aza-spiro[5,1,11,2] 21-one-one-one ketone, 2,2,4,4 tetradecyl-21-oxa-3,20-diazabicyclo-[5,1,11,2]-eicosane~2〇-dodecyl propionate/ Tetradecyl ester, malonic acid, [(4 曱 phenylphenylmethylene]-double (1,2,2,6,6-pentamethyl- 4-piperidinyl) ^ 2,2,6 , 6-tetramethyl-4-piperidol higher fatty acid ester, 1&gt;3-benzenedicarboxamide, N,N,-bis (2,2,6,6- A hindered amine compound such as tetramethyl to 4-piperidinyl). As the amine compound which is a light stabilizer, the following commercially available products can be used. 】 Illustrated by Ciba Specialty Chemicals 36 201137044 made of TINUVIN765, TINUVIN770DF, TINUVIN144, TINUVIN123, TINUVIN622LD, TINUVIN152, CHIMASSORB944, Adeka LA-52, LA-57, LA-62, LA- 63P, LA-77Y, LA-81, LA-82, LA-87, etc. In the curable resin composition of the present invention, the light stabilizer is used in an amount by weight relative to the total amount of the epoxycyclohexyl group-containing organopolyfluorene (A) and the alicyclic epoxy resin (B). It is 0.005 to 5% by weight, more preferably 0.01 to 4% by weight, and 0.1 to 2% by weight. The phosphorus-based compound is not particularly limited, and examples thereof include 1,1,3 - tris(2-indenyl-4-tetradecylphosphite-5-t-butylphenyl)-butylate (1) , 1,3-tris(2-methyl-4-ditridecylphosphito-5-t-butylphenyl)butane), distearyl neopentyl alcohol phosphite, bis (2,4 1-2 dibutyl benzene) Pentaerythritol diphosphite, bis(2,6-di-dibutylbutyl-4-methylphenyl)neopentitol diphosphite, phenylbisphenol A pentaerythritol II Phosphite, dicyclohexyl neopentyl alcohol diphosphite, tris(diethylphenyl) phosphite, tris(diisopropylphenyl) phosphite, tris(di-n-butyl) Phenyl) vinegar, tris(2,4-di-butyt-butylphenyl) phosphite, tris(2,6-di-p-butylphenyl) phosphite, tris(phosphinic acid) 6-Di-tert-butylphenyl)ester, 2,2|-fluorenylene bis(4,6-di-di-t-butylphenyl) (2,4-di-tert-butylphenyl) Phosphite, 2,2,-methylenebis(4,6-di-dibutylphenyl) (2-tert-butyl-4-methylbenzene) Phosphite, 2,2'-fluorenylene bis(4-indenyl-6-t-butylphenyl) (2-tributyl-4-indanylphenyl) phosphite, 2, 2, monoethylene bis(4-methyl-6-t-butylphenyl) (2-t-butyl-4-indolylphenyl) ya 37 201137044 phosphate, tetra (2,4-di a tetrabutyl phenyl)-4,4-di-tert-butylphenyl-4,4'-biphenylenephosphonite, four (2,4 - Di-tert-butylphenyl)- 4,3'-extended biphenyl diphosphinate, tetrakis(2,41-2 dibutylphenyl)-3,3'-extended biphenyl Diphosphonite, tetrakis(2,6-di-di-t-butylphenyl)- 4,4'-extended biphenyl diphosphinate, tetrakis(2,6-di-tert-butylphenyl) a 4,3'-extended biphenyl diphosphinate, tetrakis(2,6-di-t-butylphenyl)- 3,3^-biphenyldiphosphinate, bis ( 2,41-2 dibutylphenyl)-4-phenylphenylphosphonate, bis(2,4,2-di-t-butylphenyl)-3-phenyl-phenylene Phosphonate, double (2,6 - Mono-n-butylphenyl)-3-phenylphenylphosphonate, bis(2,6-di-di-t-butylphenyl)-tetraphenyl-phenylphosphinic acid 2,6-di-tert-butylphenyl)-3-phenyl-phenylphosphinic acid S, tetrakis(2,4-di-tert-butyl-5-nonylphenyl)-4 4'-Extended biphenyl diphosphinate, tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl vinegar, triethyl phenyl ester, triethyl citrate , diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxylate, dibutyl acid, dioctyl phosphate Ester, diisopropyl phosphate, and the like. Commercially available products can also be used as the phosphorus compound. For example, Adekastab PEP-4C manufactured by Adeka, Adekastab PEP-8, Adekastab PEP-24G, Adekastab PEP-3, Adekastab HP-10, Adekastab 2112, Adekastab 260, Adekastab 522A, Adekastab 1178, Adekastab 1500, 38 201137044

HkastabC、Adekastabl35A、Adekastab3GiGAdekastab 於本發明之硬化性樹脂組成物中，碟系化合物之使用 量=於含環氧環己基之有機料氧（A)與 脂二之總量’以重量比計為。.005〜5重量%，更佳為。： 〜4重罝％，（^丨〜〗重量％。 本發明之硬化性樹脂组成物較佳為包含含環氧環 氧(A)及脂環族環氧樹脂⑻作為環氧樹二 包含酸野㈤及多元㈣（D)作為硬化劑…本發明 =性：:？成物較佳為包含含環氧環己基之有 月曰氧樹脂（B)作為環氧樹脂，包含酸酐 夕兀羧酸（D )作為硬化劑，包含鋅 合物⑻作為添加劑。進而 八戈辞錯 較佳為包含受阻胺系光穩定劑生樹脂組成物 加劑。 ^、3有磷之杬氧化劑作為添 該等亦可與下述所示之盆 添加劑併用。 為氧樹脂、硬化劑、各種 環氧樹脂成分，及可與含環氧環己基之有 及:環族環氧樹脂(Β)併用之其他環氧樹脂，可列舉:J 除二^ %氧樹脂、雙紛Α型環氧樹脂、聯苯型環氧樹脂、 :可芳 ，了歹J舉.雙齡Α、雙紛S、硫代二齡、第雙酚、 、 4,4 —聯笨酚、2,2，—聯苯 ' 苯]—Μ、二醇、對苯-紛、門:5’5—四甲基卜聯 本一酚間求二酚、萘二酚、三—（4 39 201137044 —羥基苯基）甲烷、1，1，2,2—四（4 一羥基苯基）乙烷、酚類（苯 齡、經烧基取代苯齡、蔡齡、經烧基取代蔡齡、二經基苯、 二羥基萘等）與甲醛、乙醛、苯甲醛'對羥基苯甲醛、鄰 羥基苯甲醛、對羥基苯乙酮、鄰羥基苯乙酮、二環戊二烯、 糠路、4,4’一雙（氯甲基）一 ι，ι’_聯苯、4,4，一雙（甲氧基甲基） —1，1’一聯苯、1，4一雙（氣甲基）苯、丨，4—雙（甲氧基甲基）苯 等之縮聚物及該等之改質物，四溴雙酚A等函化雙酚類， 自醇類衍生出之環氧丙基醚化物，環氧丙基胺系環氧樹 脂、環氧丙基酯系環氧樹脂等固體或液狀環氧樹脂，但並 不限定於該等。該等可單獨使用，亦可併用2種以上。 當併用含環氧環己基之有機聚矽氧（A )及脂環族環氧 樹脂（B)與其他環氧樹脂作為環氧樹脂成分時，含環氧環 己基之有機聚矽氧（A )及脂環族環氧樹脂（B )之總重量 於所有環氧樹脂中所佔之比例較佳為6〇重量％以上特佳 為70重量％以上。 硬化劑成分，可與酸酐（C)或多元鼓酸（D)併用之 硬化劑例如可列舉：胺系化合物、酸針系化合物、醯胺系 化合物、⑮系化合物、羧酸系化合物等。可使用之硬化劑 之具體例可列舉：胺類或聚醯胺化合物（二胺基二苯基曱 烷 '二伸乙三胺、三伸乙四胺、二胺基二苯基砜、異佛_ 酮二胺、二氰二胺、由次亞麻油酸之二聚物與乙二胺所合 成之聚醯胺樹脂等）、酸針與聚碎氧系之醇類之反應物（鄰 苯一曱S夂fif笨偏二酸酐、焦蜜石酸二酐、順丁烯二酸酐、 四氫鄰苯二曱酸酐、曱基四氫鄰笨二曱酸酐、曱基耐地酸 40 201137044 酐、耐地酸酐、六氫鄰苯二甲酸酐、曱基六氫鄰苯二甲酸 酐、丁烷四羧酸酐、雙環[2,2，1]庚烷—2,3—二羧酸酐、甲 基雙環[2,2，1]庚烧一2,3 —二缓酸酐、環己烧_ι，2,4 —三缓 酸一1，2 —酐等酸酐與曱醇改質聚矽氧等聚矽氧系醇類之反 應物等）' 多元酚類（雙酚A、雙酚F、雙酚s、第雙酚、 萜二紛、4,4'~聯笨酌·、2,2’一聯苯酶、3,3’，5,5,一四甲基一 [1，1 ·—聯苯]一 4,4'—二醇、對苯二盼、間苯二齡、蔡二酴、 二一（4 一經基苯基）甲烷、i，l，2,2 —四（4 —羥基苯基）乙烷、 紛類（苯盼、經烷基取代苯酚、萘酚、經烷基取代萘酚、 一起基笨、二經基萘等）與甲酸：、乙酸、苯甲路、對經基 苯曱酿、鄰羥基苯甲醛、對羥基笨乙酮、鄰羥基苯乙酮、 二環戊二烯、糠醛、4,4，一雙（氯甲基）—u，—聯苯、4,4ι_ 雙（曱氧基曱基）一1，1，一聯苯、1,4 —雙（氣甲基）苯、丨，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 函化雙酚類’萜烯與酚類之縮合物）、以及其他（味唑、 三氟化硼一胺錯合物、胍衍生物等）等，但並不限定於該 等。該等可單獨使用，亦可併用2種以上。 虽除酸酐（C )或多元羧酸（D )以外併用其他硬化劑 作為硬化劑成分時，酸酐（C )與多元羧酸（D )之總重量 於所有硬化劑中所佔之比例較佳為3〇重量％以上，特佳為 40重量％以上。 於本發明之硬化性樹脂組成物中，將上述含環氧環己 =之有機聚矽氧（A )及上述脂環族環氧樹脂（B )作為必 兩成刀之環氧樹脂成分、與將上述酸軒（c )作為必需成分 41 201137044 之硬化劑成分之摻合比率較佳為以相對於環氧八 環氧基1當量，硬化劑成分成為〇 7〜12 ♦ 曰刀之 〜1.1 〇當量的比例使用硬化劑。 特佳為0·75 當相對於環氧基1當量’硬化劑成分未達〇 7 者超過1.2當量時，均存在硬化變得Μ全，無^良= 之硬化物性之可能性。 叉^民好 於本發明之硬化性樹脂組成物中，較佳為進而 化觸媒。當硬化性組成物中含有上述鋅鹽及，或辞錯入物 U)時’上述鋅鹽及/或鋅錯合物（Ε)本身顯示出作為 硬化觸媒之作用，因此亦可不另外添加硬化觸媒，但亦可 併用其他硬化觸媒。 可使用之硬化促進劑可列舉：2—曱基咪唑、2—苯基 咪唑、2—十一基咪唑、2一十七基咪唑、2—苯基—4— ^ 基咪唑、1—节基一2一苯基咪唑、1一节基一2—甲基咪唑、 1—氰乙基一2—甲基咪唑、1~氰乙基—2 一苯基咪唑、i — 氰乙基—2 —十一基咪唑、2,4~~二胺基一6(2，一曱基咪唑（1，）) 乙基均一 d井、2,4 _ 一胺基一6(2'--—基味°坐（1'))乙基 -均二口井、2，4 —二胺基一6(2’一乙基一 4—曱基咪唑（1，））乙 基一均二〇井、2,4 一二胺基~ 6(2'—甲基咪唑（1，)）乙基—均 二0井·異二聚氛酸加成物、2·-甲基味哇異三聚氰酸之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 —二羥曱基咪唑、2 —苯基一4 —羥甲基一5 —曱基咪唑、1 _氰乙基一2 —苯基一3,5 —二氰基乙氧基曱基咪唑之各種 °米嗤類，及該等咪唑類與鄰苯二曱酸、間苯二曱酸、對苯 42 201137044 一曱酸、苯偏三酸、焦蜜石酸、萘二叛酸、順丁稀二酸、 草酸等多元羧酸之鹽類，二氰二胺等醯胺類，丨，8一二氮雜 又衣（5.4.0)十婦—7専一氮雜化合物及該等之四苯基棚酸 酯、笨酚酚醛清漆等之鹽類，與上述多元緩酸類或次磷酸 類之鹽類’溴化四丁基銨、溴化十六基三甲基銨、溴化三 辛基曱基銨等銨鹽，三苯基膦、三（曱苯曱醯基）膦、四苯基 漠化鱗、四苯基鱗四苯基硼酸酯等膦類或鱗化合物，2,4,6 —二胺基曱基苯酚等酚類，胺加合物，辛酸錫等金屬化合 物等’以及將該等硬化促進劑微膠囊化而成之微膠囊型硬 化促進劑等。使用該等硬化促進劑中之哪一個係根據例如 透明性、硬化速度、作業條件等對所獲得之透明樹脂組成 物所要求之特性而適宜選擇。硬化促進劑係相對於硬化性 組成物中所含有之環氧樹脂成，分100重量份，通常於〇.〇〇 1 〜15重量份之範圍内使用。 本發明之硬化性樹脂組成物亦可添加如以下所列舉之 各種添加劑、助劑。 於本發明之硬化性樹脂組成物中，亦可包含含有磷之 化合物作為難燃性賦予成分。含有磷之化合物可為反應型 之化合物’亦可為添加塑之化合物。含有填之化合物之具 體例可列舉：磷酸三曱酯、磷酸三乙酯、磷酸三曱苯酯 (tricresyl phosphate)、填酸三（二曱苯）酉旨（trixylylenyl phosphate)、填酸曱苯二苯 S旨（cresyl diphenyl phosphate)、 磷酸曱苯基一2,6 —二（苯二甲基）酯（cresyl-2,6-dixylylenyl phosphate)、1，3 —伸苯基雙（（二（苯二甲基）磷酸酯）、1，4 -伸 43 201137044 苯基雙（二（苯二甲基）磷酸酯）、4,4·一聯苯基（二（苯二甲基） 雄酸酯）（4,4'-biphenyl(dixylylenyl phosphate)等麟酸酯類； 9,10 —二氫一 9 -氧雜一10 —磷雜菲一 10 —氧化物 (9,10-dihydro-9-oxa_ 1 〇-phosphaphenanthrene 10-oxide)、 10(2,5 —二羥基苯基）一10H—9 —氧雜一10 -磷雜菲—10-氧化物等膦（phosphane)類；使環氧樹脂與上述膦類之活性 氫反應而獲得之含有磷之環氧化合物、紅磷等，較佳為構 酸酯類、膦類或含有磷之環氧化合物，特佳為1，3 —伸苯基 雙（二（苯二甲基）磷酸酯）、1，4 —伸笨基雙（二（苯二曱基）磷酸 酯）、4,4'—聯苯基（二（苯二曱基）鱗酸酯）或含有麟之環氧化 合物。含有磷之化合物之含量較佳為含有磷之化合物/硬 化性組成物中所含有之環氧樹脂=〇丨〜〇 6 (重量比）。若 未達〇· 1，則難燃性不充分，若超過0.6 ’則有可能會對硬 化物之吸濕性、介電特性帶來不良影響。 進而，於本發明之硬化性樹脂組成物中，視需要亦可 摻合黏合劑樹脂。黏合劑樹脂可列舉：丁醛系樹脂、縮醛 系樹脂、丙烯酸系樹脂、環氧―尼龍系樹脂、NBR_酚系樹 脂' 環氧一 NBR系樹脂、聚醯胺系樹脂、聚醢亞胺系樹脂、 聚矽氧系樹脂等，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 硬化性樹脂組成物中所含有之環氧樹月旨成分與硬化劑成分 重量份，通常視需要而使用0 05〜50重量份，較佳為 〇·〇5〜20重量份。 於本發明之硬化性樹脂組成物中，可視需要添加無機 44 201137044 7充劑。無機填充劑可列舉：結晶二氧切、熔融二氧化 石乳化銘、錯英石、碳㈣、碳切、氮化石夕、 鎂橄欖石、塊滑石、尖晶石、二氧化欽、 /月 之b體或將該等球形化而成之顆粒等，但並不限定 於該等。該等填充材可單獨使用，亦可使帛2種以上。該 等無機填充材之含量係使用於本發明之硬化性樹脂組成物 中佔〇〜95重量％之量。進而，可於本發明之硬化性樹脂組 成物中添加㈣偶合劑、硬脂酸、棕櫚酸、硬脂酸辞、硬 脂酸舞等脫模劑、顏料等各種摻合劑、各種熱硬化性樹脂。 於將本發明之硬化性樹脂組成物用於光學材料，尤其 用於光半導體密封劑時’可藉由使用上述所使用之無機填 充材之粒徑，為奈米等級之填充材料，以於不阻礙透明性 之下增強機械強度等。奈米等級之標準，就透明性之觀點 而言，平均粒徑為50〇nm以下，特佳為使用平均粒徑為 200nm以下之填充材。HkastabC, Adekastabl 35A, Adekastab3GiGAdekastab In the curable resin composition of the present invention, the amount of the dish compound used is = by weight of the total amount of oxygen (A) and the fat of the organic material containing epoxycyclohexyl group. .005~5 wt%, more preferably. : 〜4重罝%, (^丨~〗% by weight. The curable resin composition of the present invention preferably comprises an epoxy-containing epoxy (A) and an alicyclic epoxy resin (8) as an epoxy resin. Wild (5) and multi-component (4) (D) as a hardener. The present invention is preferably an anthracene-containing oxidized resin containing an epoxycyclohexyl group (B) as an epoxy resin, comprising an acid anhydride (D) as a hardener, comprising a zinc compound (8) as an additive. Further, it is preferable to include a hindered amine-based light stabilizer raw resin composition additive. ^, 3 phosphorus-containing oxidizing agent is added as such It can be used in combination with the potting additives shown below. It is an oxygen resin, a hardener, various epoxy resin components, and other epoxy resins which can be combined with an epoxy-containing cyclohexyl group: a cycloolefin epoxy resin. , can be listed as: J addition of 2% oxygen resin, double bismuth type epoxy resin, biphenyl type epoxy resin, : can be Fang, 歹J lift. Double age Α, double S S, thio 2nd age, the first Bisphenol, 4,4-biphenol, 2,2,-biphenyl 'benzene】-indole, diol, p-benzene-distribution, 5:5-tetramethyl-di- phenol Diphenol, naphthalenediol, tris-(4 39 201137044-hydroxyphenyl)methane, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, phenols (benzene age, burnt-substituted benzene) Age, Cai Ling, burnt-based replacement of Cai Ling, dipyridylbenzene, dihydroxynaphthalene, etc.) with formaldehyde, acetaldehyde, benzaldehyde 'p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxybenzene Ethyl ketone, dicyclopentadiene, hydrazine, 4,4'-double (chloromethyl)- ι, ι'_biphenyl, 4,4, bis(methoxymethyl)-1,1' a polycondensate of monophenyl, 1,4-bis(gasmethyl)benzene, anthracene, 4-bis(methoxymethyl)benzene, and the like, and a modified bisphenol such as tetrabromobisphenol A a solid or liquid epoxy resin such as a glycopropyl etherate derived from an alcohol, a glycidylamine epoxy resin or a glycidyl ester epoxy resin, but is not limited thereto. These may be used singly or in combination of two or more. When an epoxy group containing an epoxycyclohexyl group (A) and an alicyclic epoxy resin (B) and other epoxy resins are used as an epoxy resin component, Epoxycyclohexyl The ratio of the total weight of the organopolyfluorene (A) and the alicyclic epoxy resin (B) to all the epoxy resins is preferably 6% by weight or more, particularly preferably 70% by weight or more. Examples of the curing agent which can be used in combination with the acid anhydride (C) or the polybasic acid (D) include an amine compound, an acid needle compound, a guanamine compound, a 15 compound, a carboxylic acid compound, etc. A hardener which can be used. Specific examples thereof include amines or polyamine compounds (diaminodiphenyl decane' diethylenetriamine, triethylenetetramine, diaminodiphenyl sulfone, isophorone ketone diamine, a reaction product of dicyandiamide, a polyamidene resin synthesized from a dimer linoleic acid dimer and ethylenediamine, an acid needle and a poly(hydrogenated alcohol) alcohol (o-benzoquinone S夂fif stupid) Meta-anhydride, pyromellitic dianhydride, maleic anhydride, tetrahydrophthalic anhydride, mercapto tetrahydro-o-phthalic anhydride, mercapto-resistant acid 40 201137044 anhydride, acid anhydride, hexahydrogen Phthalic anhydride, mercapto hexahydrophthalic anhydride, butane tetracarboxylic anhydride, bicyclo[2,2,1]heptane-2,3-dicarboxylic anhydride, Bis-ring [2,2,1] Geng-single 2,3-di-slow-acid anhydride, cyclohexanol_ι, 2,4-three-salt acid-1,2-anhydride and other anhydrides and sterol-modified polyoxyl Polyoxo alcohols, etc.) 'Polyphenols (bisphenol A, bisphenol F, bisphenol s, bisphenol, bismuth, 4, 4'~ 笨 酌,, 2, 2' A biphenylase, 3,3',5,5,tetramethyl-[1,1--biphenyl]- 4,4'-diol, p-phenylene, m-phenylene, Cai Erqi , di-(4-monophenylene)methane, i,l,2,2-tetrakis(4-hydroxyphenyl)ethane, heterogeneous (benzene, alkyl substituted phenol, naphthol, alkyl substituted Naphthol, agglomerated, dipyridyl, etc.) with formic acid: acetic acid, benzoyl, p-benzoquinone, o-hydroxybenzaldehyde, p-hydroxyethylidene, o-hydroxyacetophenone, dicyclopentan Diene, furfural, 4,4, bis(chloromethyl)-u,-biphenyl, 4,4ι_bis(decyloxyfluorenyl)-1,1,biphenyl, 1,4-bis (gas a polycondensate of methyl)benzene, anthracene, 4-bis(decyloxymethyl)benzene, etc., and such modified substances, functionalized bisphenols such as tetrabromobisphenol A, terpene and phenols Condensate), and others (taste oxazole, a boron trifluoride-amine complexes, and guanidine derivatives) and the like, but is not limited to this and the like. These may be used alone or in combination of two or more. When the other hardener is used as the hardener component in addition to the acid anhydride (C) or the polycarboxylic acid (D), the ratio of the total weight of the acid anhydride (C) to the polycarboxylic acid (D) to all the hardeners is preferably 3〇% by weight or more, particularly preferably 40% by weight or more. In the curable resin composition of the present invention, the above-mentioned epoxy group-containing organic polyfluorene oxide (A) and the above alicyclic epoxy resin (B) are used as an epoxy resin component of a must-have knife and The blending ratio of the above-mentioned acid (c) as an essential component 41 201137044 is preferably 1 equivalent to the epoxy epoxide group, and the hardener component is 〇7 to 12 ♦ 曰 之 〜 1.1 〇 A hardener is used in the equivalent ratio. It is particularly preferable that when the amount of the hardener component is less than 1.2 equivalents per 1 equivalent of the epoxy group, the hardening becomes complete and there is no possibility of hardening physical properties. For the curable resin composition of the present invention, it is preferred to further convert the catalyst. When the hardening composition contains the above-mentioned zinc salt and or the erroneous substance U), the above-mentioned zinc salt and/or zinc complex (Ε) itself exhibits a function as a curing catalyst, and therefore may not be additionally hardened. Catalyst, but other hardening catalysts can also be used in combination. The hardening accelerator which can be used may, for example, be 2-nonylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2,7-cysyl imidazole, 2-phenyl-4-methylimidazole, 1-phenylene group 2- phenylimidazole, 1 benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, i-cyanoethyl-2 Eleven imidazole, 2,4~~diamino- 6 (2, monodecyl imidazole (1,)) ethyl uniform d well, 2,4 _monoamine- 6 (2'---basic taste °Sit (1')) Ethyl-homogeneous well, 2,4-diamine- 6 (2'-ethyl-tetra- 4-mercaptoimidazole (1,)) ethyl-one bismuth well, 2 , 4 - diamino~ 6 (2'-methylimidazolium (1,)) ethyl - homodioxane, heterodimeric acid adduct, 2·-methyl miso isocyanuric acid 2: 3 adduct, 2-phenylimidazole isocyanurate adduct, 2-phenyl-3,5-dihydroxydecylimidazole, 2-phenyl-4-hydroxymethyl-5-oxime Various rice oximes of imidazole, 1-cyanoethyl-2-phenyl- 3,5-dicyanoethoxy decyl imidazole, and these imidazoles with phthalic acid and m-benzoquinone Acid, p-benzene 42 201137044 A salt of a polycarboxylic acid such as citric acid, trimellitic acid, pyromic acid, naphthalene diphenolic acid, cis-butyl diacid, oxalic acid, guanamine such as dicyandiamide, hydrazine, arsenic Miscellaneous clothing (5.4.0) Ten women - 7 専 a nitrogen compound and the salts of such tetraphenyl phthalate, phenol novolac varnish, and the above salts of polybasic acid or hypophosphite Ammonium salts such as tetrabutylammonium bromide, hexadecyltrimethylammonium bromide, trioctyldecylammonium bromide, triphenylphosphine, tris(phenylphenylphosphonium)phosphine, tetraphenyl desertification scale a phosphine or a scaly compound such as tetraphenylphosphonium tetraphenylborate, a phenol such as 2,4,6-diaminononylphenol, an amine adduct, a metal compound such as tin octylate, etc. A microcapsule type hardening accelerator obtained by microencapsulation of a hardening accelerator. Which of these hardening accelerators is used is suitably selected depending on characteristics required for the obtained transparent resin composition, for example, transparency, curing speed, working conditions and the like. The curing accelerator is used in an amount of 100 parts by weight based on the epoxy resin contained in the curable composition, and is usually used in an amount of from 1 to 15 parts by weight. The curable resin composition of the present invention may also contain various additives and auxiliary agents as listed below. The curable resin composition of the present invention may further contain a compound containing phosphorus as a flame retardancy imparting component. The phosphorus-containing compound may be a reactive compound or may be a plasticized compound. Specific examples of the compound to be filled include tridecyl phosphate, triethyl phosphate, tricrasyl phosphate, trixylylenyl phosphate, and phthalic acid Cresyl diphenyl phosphate, cresyl-2,6-dixylylenyl phosphate, 1,3-phenylene bis((di(benzene) Dimethyl)phosphate), 1,4 -Extension 43 201137044 Phenylbis(bis(phenyldimethyl)phosphate), 4,4·-biphenyl (bis(phenylenediyl) androstate) (4,4'-biphenyl (dixylylenyl phosphate) and other lincosates; 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (9,10-dihydro-9-oxa_ 1 Phosphate of 〇-phosphaphenanthrene 10-oxide), 10(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphonium-10-oxide; A phosphorus-containing epoxy compound, red phosphorus or the like obtained by reacting active hydrogen of a phosphine, preferably an acid ester, a phosphine or an epoxy compound containing phosphorus, particularly preferably a 1,3 -phenylene group (bis(phenyldimethyl)phosphate), 1,4-extended bis(bis(phenylenediyl)phosphate), 4,4'-biphenyl (bis(phenylenedifluoryl) squarate Ester) or an epoxy compound containing lin. The content of the phosphorus-containing compound is preferably an epoxy resin containing a phosphorus compound/curable composition: 〇丨~〇6 (weight ratio). -1, the flame retardancy is insufficient, and if it exceeds 0.6', the hygroscopicity and dielectric properties of the cured product may be adversely affected. Further, in the curable resin composition of the present invention, if necessary, The binder resin may be blended, and the binder resin may, for example, be butyraldehyde resin, acetal resin, acrylic resin, epoxy-nylon resin, NBR_phenol resin, epoxy-NBR resin, polyamine The resin, the polyimide resin, the polyoxymethylene resin, and the like are not limited thereto. The blending amount of the binder resin is preferably such that the flame retardancy and heat resistance of the cured product are not impaired. The weight fraction of the epoxy resin component and the hardener component contained in the curable resin composition Usually, it is used in an amount of from 0.05 to 50 parts by weight, preferably from 5 to 20 parts by weight. In the curable resin composition of the present invention, inorganic 44 201137044 7 filler may be added as needed. The inorganic filler may be used. Listed: crystalline dioxotomy, fused silica emulsified imprint, smectite, carbon (four), carbon cut, nitrite, forsterite, talc, spinel, dioxate, / month b body or These spheroidized particles and the like are not limited thereto. These fillers may be used singly or in combination of two or more. The content of the inorganic filler is 5% to 95% by weight based on the curable resin composition of the present invention. Further, in the curable resin composition of the present invention, (iv) a coupling agent such as a coupling agent, stearic acid, palmitic acid, stearic acid or stearic acid, a blending agent such as a pigment, and various other thermosetting resins may be added. . When the curable resin composition of the present invention is used for an optical material, particularly when used in a photo-semiconductor encapsulant, 'the particle size of the inorganic filler used above can be used as a nano-grade filler material, so as not to It hinders transparency and enhances mechanical strength and the like. The standard of the nanometer grade is an average particle diameter of 50 Å or less from the viewpoint of transparency, and particularly preferably a filler having an average particle diameter of 200 nm or less.

於將本發明之硬化性樹脂組成物用於光學材料，尤其 用於光半導體密封劑時’視需要可添加螢光體。螢光體例 如係具有如下作用者’即：吸收自藍色LED元件所發出之 藍色光之一部分’並發出經波長轉換之黃色光，藉此形成 白色光。使螢光體預先分散於硬化性樹脂組成物中，然後 密封光半導體。螢光體並無特別限制，可使用先前公知之 螢光體’例如可例示：稀土類元素之鋁酸鹽、硫代鎵酸 (thiogallic acid)鹽、原石夕酸鹽。更具體而言，可列舉：YAG 螢光體、TAG螢光體、原矽酸鹽螢光體，硫代鎵酸鹽榮光 45 201137044 體，硫化物螢光體等螢光體，且可例示ΥΑ1〇3 : Ce、 Y3Al5〇12 : Ce、Y4Al2〇9 : Ce、Y202s : Eu、Sr5(P〇4)3Cl :When the curable resin composition of the present invention is used for an optical material, particularly when used in an optical semiconductor encapsulant, a phosphor may be added as needed. The phosphor is, for example, a member that absorbs a portion of the blue light emitted from the blue LED element and emits wavelength-converted yellow light, thereby forming white light. The phosphor is previously dispersed in the curable resin composition, and then the photo-semiconductor is sealed. The phosphor is not particularly limited, and a conventionally known phosphor can be used, for example, an aluminate of a rare earth element, a thiogallic acid salt, or a protothenate. More specifically, a YAG phosphor, a TAG phosphor, a protoporate phosphor, a thiogallate glory 45 201137044 body, a sulfide phosphor or the like can be cited, and ΥΑ 1 can be exemplified. 〇3 : Ce, Y3Al5〇12 : Ce, Y4Al2〇9 : Ce, Y202s : Eu, Sr5(P〇4)3Cl :

Eu、（SrEu)O · AhO3等。上述螢光體之粒徑係使用該領域 中公知之粒徑’平均粒徑為1〜250 μ m，特佳為2〜50 /z m。 當使用該等螢光體時’其添加量相對於含環氧環己基之有 機聚矽氧（A)等有機成分1〇〇重量份為1〜80重量份，較 佳為5〜60重量份。 當將本發明之硬化性樹脂組成物用於光學材料，尤其 用於光半導體密封劑時，為了防止各種螢光體於硬化時沈 版’可添加以二氧化石夕微粉末（亦稱為Aerosil或Aerosol) 為代表之觸變性賦予劑。此種二氧化矽微粉末，例如可列 舉：Aerosil 50、Aerosil 90、Aerosil 130、Aerosil 200、Aerosil 300、Aerosil 380、Aerosil 0X50、Aerosil TT600、Aerosil R972 ^ Aerosil R974 &gt; Aerosil R202 ^ Aerosil R812 &gt; Aerosil R812S、Aerosil R805、RY200、RX200 (日本 Aer〇sil 公司 製造）等。 本發明之硬化性樹脂組成物可含有酚系化合物作為抗 氧化劑。 酚系化合物並無特別限定 三丁基_4_甲基苯酴、正十八 一 4一經基苯基）丙酸醋、四[亞 例如可列舉：2,6—二一第 —3 — (3,5 ~~ 二一第三丁基Eu, (SrEu)O · AhO3, etc. The particle size of the above-mentioned phosphor is 1 to 250 μm, particularly preferably 2 to 50 /z m, which is known in the art. When the phosphors are used, the amount thereof is 1 to 80 parts by weight, preferably 5 to 60 parts by weight, per part by weight based on 1 part by weight of the organic component of the organopolyfluorene (A) containing epoxycyclohexyl group. . When the curable resin composition of the present invention is used for an optical material, particularly for a photo-semiconductor encapsulant, in order to prevent various phosphors from sinking at the time of hardening, it is possible to add a silica dioxide powder (also known as Aerosil). Or Aerosol) is a representative thixotropy imparting agent. Such a cerium oxide micropowder may, for example, be: Aerosil 50, Aerosil 90, Aerosil 130, Aerosil 200, Aerosil 300, Aerosil 380, Aerosil 0X50, Aerosil TT600, Aerosil R972 ^ Aerosil R974 &gt; Aerosil R202 ^ Aerosil R812 &gt; Aerosil R812S, Aerosil R805, RY200, RX200 (manufactured by Aer〇sil, Japan). The curable resin composition of the present invention may contain a phenolic compound as an antioxidant. The phenolic compound is not particularly limited to tributyl-4-methylbenzoquinone, n-octadecyl-4-phenylphenylpropionic acid vinegar, and the fourth is exemplified by 2,6-two-first- 3 ( 3,5 ~~ two one third butyl

第三丁基一 6 — 基一4 一經基苯基）丙酸酯]甲院、2，4~~二 第三丁基一4 甲基苯酚、1，6 —已二醇—雙--[3~(3,5 經基节基） —經基苯基）丙酸酯]、三（3,5 —二一第三丁義—4 46 201137044 一異氰尿酸酯、1，3,5 —三甲基一2,4,6 —三（3,5 —二一第三丁 基一4 —羥基苄基）苯、新戊四醇—四[3 — (3,5—二一第三丁 基—4 —羥基苯基）丙酸酯]、3,9 —雙一 [2 — [3 — (3 —第三丁 基—4 —羥基一5 —曱基苯基）一丙醯氧基]—1,1—二甲基乙 基]—2,4,8，10 -四氧雜螺[5,5]十一烷、三乙二醇一雙[3—（3 —第三丁基—5 —甲基一4 —羥基苯基）丙酸酯]、2,2，一亞丁 基雙（4,6 —二一第三丁基苯酚）、4,4·_亞丁基雙（3-甲基一6 一第三丁基苯酚）、2,2, 一亞甲基雙（4—甲基一6 —第三丁基 苯酚）、2,2'_亞甲基雙（4一乙基一 6 —第三丁基苯酚）、2 — 第三丁基一 6 — (3—第三丁基一2_羥基一5 —甲基苄基）一 4 —甲基苯酌·丙稀酸S旨、2— [1 — (2_經基一3，5— 一第三戊基 苯基）乙基]—4,6—二一第三戊基苯基丙烯酸酯、4,4’一硫代 雙（3 —甲基一 6 —第三丁基苯酚）、4,4·-亞丁基雙（3-曱基 —6 —第三丁基苯酚）、2 —第三丁基一4—曱基苯酚、2,4一 二一第三丁基苯酚、2,4 —二一第三戊基苯酚、4,4· —硫代雙 (3—曱基一6—第三丁基苯酚）、4,4·—亞丁基雙（3—甲基一 6 _第三丁基苯酚）、雙一[3,3—雙_(4’一羥基一3·—第三丁基 苯基）一丁酸]—二醇酯、2,4 —二一第三丁基苯酚、2,4 —二 一第三戊基苯酚、2—[1一（2—羥基一 3,5—二一第三戊基苯 基）乙基]一4,6 —二一第三戊基苯基丙烯酸酯、雙一[3,3 —雙 一（4，一羥基一3,一第三丁基苯基）一丁酸]一二醇酯等。 上述酚系化合物亦可使用市售品。 例如可列舉：汽巴精化製造之IRGANOX1010、 IRGANOX1035 、 IRGANOX1076 、 IRGANOX1 135 、 47 201137044 IRGANOX245 、 IRGANOX259 、 IRGAN6X295 、 IRGANOX3114、. IRGANOX1098、IRGANOX1520L，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— 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。 此外，可使用市售的添加劑作為樹脂之防著色劑。例 如可列舉：汽巴精化製造之TINUVIN328、TINUVIN234、 TINUVIN326、TINUVIN120 ' TINUVIN477、TINUVIN479、 CHIMASSORB2020FDL，CHIMASSORB119FL 等。 當添加上述酚系化合物時，其摻合量並無特別限定， 可以於本發明之硬化性樹脂組成物中佔0.005〜5.0重量％ 之量來添加。 本發明之硬化性樹脂組成物係藉由均勻地混合各成分 而獲得。本發明之硬化性樹脂組成物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》例如視需要使用 擠出機、捏合機、輥、行星式混合機等將環氧樹脂成分、 硬化劑成分、鋅鹽及/或鋅錯合物充分地混合直至均勻， 而獲得硬化性樹脂組成物，當所獲得之本發明之硬化性樹 脂組成物為液狀時，藉由封裝（potting)或澆鑄（casting)，將 該組成物含浸於基材，或者使硬化性樹脂組成物流入模具 中澆鑄成型，並藉由加熱使其硬化。又，當所獲得之本發 48 201137044 明之硬化性樹脂組成物為因辦吐 X初馮固體時，於熔融後進行 型、或者使用轉注成型機望 _ 轉成 科风生機專進行成型 其硬化❶再者，任音忐八* s 曰田加熱而使 思成刀之硬化促進劑、胺化合物、今右 填之化合物、齡系化人私 有 -σ物、黏合劑樹脂，無機填充材等σ 要於上述混合步驟中添加.日人β ^ ^ ΟΛ 0 鄉中添加、處合即可。硬化溫度、時間Α 80〜200〇C、2〜1 Ο ,ι、吐 丈 丁间局 夺。硬化方法，可於高溫下瞬 化性樹脂組成物硬化，作較 更硬 為逐步地升溫來進行硬化反 *’、 - 5，於80〜150°c之間進行初始硬化，於1〇〇t 〜2〇〇°C之間進行後硬化。硬化之階段，較佳為分成2〜8 個階段進行升溫，更佳為2〜4個階段。 又，使本發明之硬化性樹脂組成物溶解於甲苯、二甲 苯、丙酮、甲基乙基酮、甲基異丁基銅、二甲基甲酿胺、 一曱基乙醯胺、N—甲基吡咯啶酮等溶劑中而製成硬化性樹 脂組成物清漆，㈣硬化性㈣組成物清漆含浸於玻璃纖 維、碳纖維、聚酯纖維、聚醯胺纖維、氧化铭纖維、紙等 基材中並進行加熱乾燥而獲得預浸體，將該預浸體熱壓成 形，藉此可製成本發明之硬化性樹脂組成物之硬化物。此 時之溶劑係使用於本發明之硬化性樹脂組成物與該溶劑之 混合物令通常佔10〜70重量％，較佳為佔15〜7〇重量％的 置。又，亦可於液狀組成物之狀態下，藉由RTM方式獲得 含有碳纖維之環氧樹脂硬化物。 又，亦可將本發明之硬化性樹脂組成物用作膜型密封 用組成物。當獲得此種膜型樹脂組成物時，於剝離膜上塗 佈上述/胃漆並在加熱下去除溶劑，然後進行B階段化，藉 49 201137044 此可將本發明之硬化性樹脂組成物形成為片狀之接著劑。 該片材狀接著劑可用作多層基板等中之層間絕緣層、光半 導體之整體膜密封。 其次’對將本發明之硬化性樹脂組成物用作光半導體 之密封材料或晶粒結著材料的情形進行詳細說明。 當本發明之硬化性樹脂組成物用作高亮度白色㈣等 光半導體之密封材料'或者晶粒結著材料時，藉由充分地 混合環氧樹脂、硬化劑、偶合劑、抗氧化劑、光穩定劑等 添加物來製備環氧樹脂組成物’並將其用作密封材料、或 者用於晶粒結著材料與密封材料兩者。混合方法，使用捏 合機、三親機、萬能混合機、行星式混合機、均質混合機、 均質分散機、珠磨機等，於常溫或加溫而混合。 高亮度白色LED等光半導體元件一般係將積層於藍寶 石、尖晶石、SiC、Si、Zn〇等之基板上之以^、㈣、Tert-butyl-6-yl- 4-mono-phenyl)propionate] A, 2,4~~di-tert-butyl-4-methylphenol, 1,6-hexanediol-bis-[ 3~(3,5 via a benzyl group)-p-phenyl)propionate], three (3,5-two-third-buty- 4 46 201137044 an isocyanurate, 1,3,5 —trimethyl- 2,4,6-tris(3,5-di-di-tert-butyl 4- 4-hydroxybenzyl)benzene, neopentyl alcohol-four [3 — (3,5-two one third Butyl-4-hydroxyphenyl)propionate], 3,9-bis-[2 - [3 - (3 - tert-butyl-4-hydroxy-1-nonylphenyl)-propenyloxy ]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, triethylene glycol-double [3-(3-t-butyl) —5 —Methyl 4-hydroxyphenyl)propionate], 2,2, monobutylenebis(4,6-di-p-butylphenol), 4,4·-butylenebis(3- Methyl-6-t-butylphenol), 2,2, monomethylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis(4-ethyl a 6-tert-butylphenol), 2 - a third butyl group 6 - (3 - third butyl a 2-hydroxy-5-methylbenzyl)- 4-methylbenzene-propionic acid S, 2-[1 - (2_------ 3, 5----- Base]—4,6—two, a third amyl phenyl acrylate, 4,4′-thiobis(3-methyl-6-t-butylphenol), 4,4·-butylene bis ( 3-mercapto-6-t-butylphenol), 2-t-butyl-4-nonylphenol, 2,41-2 dibutylphenol, 2,4-di-p-tert-butylphenol , 4,4·-thiobis(3-indenyl-6-tert-butylphenol), 4,4·-butylidenebis(3-methyl-6-t-butylphenol), double-[ 3,3-bis-(4'-hydroxy-3--t-butylphenyl)-butyric acid]-glycol ester, 2,4-di-tert-butylphenol, 2,4-two-one Tripentylphenol, 2-[1 -(2-hydroxy-3,5-di-p-triphenyl)ethyl]- 4,6-di-p-tert-butylphenyl acrylate, double-[ 3,3 - di-(4, monohydroxy-3, monobutylphenyl)-butyric acid]-glycol ester, etc. Commercially available products of the above phenolic compound are also exemplified. Manufacturing I RGANOX1010, IRGANOX1035, IRGANOX1076, IRGANOX1 135, 47 201137044 IRGANOX245, IRGANOX259, IRGAN6X295, IRGANOX3114, IRGANOX1098, IRGANOX1520L, Adekastab AO-20 manufactured by Adeka, 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) manufactured by Sumitomo Chemical Industries , Sumilizer GP, etc. Further, a commercially available additive can be used as a coloring inhibitor for the resin. For example, TINUVIN328, TINUVIN234, TINUVIN326, TINUVIN120 'TINUVIN477, TINUVIN479, CHIMASSORB2020FDL, CHIMASSORB119FL, etc. manufactured by Ciba Specialty Chemicals. When the phenolic compound is added, the amount of the phenolic compound to be added is not particularly limited, and may be added in an amount of 0.005 to 5.0% by weight based on the curable resin composition of the present invention. The curable resin composition of the present invention is obtained by uniformly mixing the components. The curable resin composition of the present invention can be easily formed into a cured product by the same method as previously known. For example, an epoxy resin, a kneader, a roll, a planetary mixer or the like is used as needed. The component, the hardener component, the zinc salt, and/or the zinc complex are sufficiently mixed until uniform to obtain a curable resin composition, and when the obtained curable resin composition of the present invention is in a liquid state, by encapsulation ( Potting or casting, impregnating the composition with the substrate, or flowing the curable resin composition into a mold for casting, and hardening it by heating. Further, when the obtained curable resin composition of the present invention is in the form of a molten solid, it is subjected to a type after melting, or a transfer molding machine is used, and it is molded into a hardened concrete. In addition, Ren Yin 忐 * * 曰 加热 加热 加热 加热 加热 加热 加热 加热 加热 加热 加热 加热 加热 加热 加热 加热 加热 加热 加热 加热 加热 加热 加热 加热 加热 加热 加热 加热 加热 加热 加热 加热 加热 加热 加热 加热 加热 加热 加热 加热 加热 加热 加热 加热 加热 加热It is added in the above mixing step. The Japanese β ^ ^ ΟΛ 0 is added to the township and can be combined. Hardening temperature, time Α 80~200〇C, 2~1 Ο, ι, 吐, 丁 局 。. The hardening method can harden the transient resin composition at a high temperature, and harder to gradually heat up to harden the anti-*, -5, and initially harden between 80 and 150 ° C, at 1 〇〇t Post-hardening between ~2〇〇°C. In the hardening stage, it is preferably divided into 2 to 8 stages for temperature rise, more preferably 2 to 4 stages. Further, the curable resin composition of the present invention is dissolved in toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl copper, dimethyl ketoamine, monomethyl acetamide, N-A A curable resin composition varnish is formed in a solvent such as pyrrolidone, and (4) a curable (iv) composition varnish is impregnated into a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, oxidized fiber, or paper. The prepreg is obtained by heating and drying, and the prepreg is hot-pressed to obtain a cured product of the curable resin composition of the present invention. The solvent at this time is usually used in an amount of 10 to 70% by weight, preferably 15 to 7 % by weight, based on the mixture of the curable resin composition of the present invention and the solvent. Further, an epoxy resin-containing cured product containing carbon fibers can be obtained by the RTM method in the state of a liquid composition. Further, the curable resin composition of the present invention can also be used as a film-type sealing composition. When such a film-type resin composition is obtained, the above-mentioned/gastric lacquer is applied onto the release film, and the solvent is removed under heating, and then B-staged, and the curable resin composition of the present invention can be formed as 49 201137044. A sheet-like adhesive. The sheet-like adhesive can be used as an integral film seal of an interlayer insulating layer or a photoconductor in a multilayer substrate or the like. Next, the case where the curable resin composition of the present invention is used as a sealing material or a crystal grain-forming material of a photo-semiconductor will be described in detail. When the curable resin composition of the present invention is used as a sealing material for a high-brightness white (tetra) white semiconductor or a grain-bonding material, by sufficiently mixing an epoxy resin, a hardener, a coupling agent, an antioxidant, and light stabilization Additives such as an agent to prepare an epoxy resin composition' and use it as a sealing material, or for both a grain bonding material and a sealing material. The mixing method is carried out by using a kneader, a three-parent machine, a universal mixer, a planetary mixer, a homomixer, a homogenizer, a bead mill, or the like, and mixing at room temperature or heating. Optical semiconductor components such as high-brightness white LEDs are generally laminated on substrates of sapphire, spinel, SiC, Si, Zn, etc., (4),

GaA1As、GaAsP、A1Ga、Inp、⑽、_、ain、㈣心等 之半導體晶片，使用接著劑（晶粒結著材料）接著於導線 架或散熱板、封裝體（paekage)而形成。亦存在為了使電流 流通而連接有金線等線之類型。為了使上述半導體晶片免 受熱或濕氣之影響，且發揮透鏡功能之作用，而以環氧樹 脂等密封材料密封該半導體晶片。本發明之硬化性樹脂組 成物可用作該密封㈣m結著n就步驟方面而 言’較佳為將本發明之硬化性樹脂組成物用於晶粒結著材 料與密封材料兩者。 使用本發明之硬化性樹脂組成物將半導體晶片接著於 50 201137044 基板上之方法，可藉由分注器、封裝、網版印刷來塗佈本 發明之硬化性樹脂組成物後’載置半導體晶片並進行加熱 硬化，而使半導體晶片接著。加熱可使用熱風循環式、紅 外線、兩頻波等方法。 加熱條件較佳為例如於8〇〜23〇它下加熱i分鐘〜Μ 小時左右。為了減少加熱硬化時所產生之内部應力，例如 可於80〜120 C下使其預硬化3〇分鐘〜5小時後，於 〜180 C、30分鐘〜1〇小時之條件下使其進行後硬化。 密封材料之成形方式，可使用如下方式等：於***有 如上述般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4匕來進行成形之注入方 &lt; ;預先將密封材 料主入至模具上’使固定於基板上之半導體晶片浸潰於其 中並進行加熱硬化後，自模具脫模之壓縮成形方式。 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 '高頻波等方法。 加熱條件較佳為例如8〇〜23〇〇c、i分鐘〜24小時左 右。為了減少加熱硬化時所產生之内部應力，例如可於 〜120°C下使其預硬化3〇分鐘〜5小時後，於i2〇〜i8〇t、 3〇分鐘〜1〇小時之條件下使其進行後硬化。 進而本發明之硬化性樹脂組成物可用於使用環氧樹 脂等硬化性樹脂之一般之用*，例如除接著劑、塗料、塗 佈劑、成形材料（包含片材、膜、FRp等）、絕緣材料（包 含印刷基板、電線包覆等）、㈣材料以外，可列舉密封 材料、基板用之氰酸酿樹脂組成物，或者作為抗蝕劑用硬 51 201137044 化劑之於丙烯酸醋系樹脂等其他樹脂等中之添加劑等。 接著劑，除土木用、建築用、汽車用、—般事務用、 醫療用之接著劑以夕卜可列舉電子材料用之接著劑 之中，電子材料用之接著劑，可列舉 望户麻^ J幻举.增層（buUd-up)基板 專夕層基板之層間接著劑、晶粒接著劑、底膠等半導體用 接耆劑，BGA增強用底膠、各向異性導電臈（A⑺、各 向異性導電性膠（ACP)等構裝用接著劑等。 密封劑’可列舉：電容器、電晶體、二極體、發光二 極體、IC、LSI等用之封裝、浸潰、轉注成形密封劑，^ LSI 類之 COB、COF、TAB 犛田·&gt; u + 專用之封裝密封劑，倒裝晶片（fHpA semiconductor wafer of GaA1As, GaAsP, A1Ga, Inp, (10), _, ain, or (tetra) core is formed using an adhesive (grain bonding material) followed by a lead frame, a heat dissipation plate, or a package. There is also a type in which a gold wire or the like is connected in order to make a current flow. In order to protect the semiconductor wafer from heat or moisture and function as a lens, the semiconductor wafer is sealed with a sealing material such as epoxy resin. The curable resin composition of the present invention can be used as the seal (4), and in the case of the step, it is preferable to use the curable resin composition of the present invention for both the grain-forming material and the sealing material. The method of attaching a semiconductor wafer to a substrate of 50 201137044 using the curable resin composition of the present invention, and coating the semiconductor wafer with the curable resin composition of the present invention by dispenser, package, screen printing And heat hardening to make the semiconductor wafer follow. For heating, a hot air circulation type, an infrared line, a two-frequency wave, or the like can be used. The heating condition is preferably, for example, about 8 Torr to 23 Torr, and it is heated for about 1 minute to about Μ hours. In order to reduce the internal stress generated during heat curing, for example, it can be pre-cured at 80 to 120 C for 3 minutes to 5 hours, and then post-hardened at ~180 C for 30 minutes to 1 hour. . In the molding method of the sealing material, the injection material may be injected into the mold frame in which the substrate of the semiconductor wafer is fixed as described above, and the injection is performed by heating the hard surface to form the molding. Mainly introduced into the mold to form a compression molding method in which the semiconductor wafer fixed on the substrate is immersed therein and heat-hardened, and then released from the mold. Examples of the injection method include a dispenser, transfer molding, and injection molding. For heating, a hot air circulation type or an infrared "high frequency wave" method can be used. The heating conditions are preferably, for example, 8 〇 to 23 〇〇 c, i minutes to 24 hours or so. In order to reduce the internal stress generated during heat curing, for example, it can be pre-cured at ~120 ° C for 3 〇 minutes to 5 hours, and then i2 〇 ~ i8 〇 t, 3 〇 minutes ~ 1 〇 hours. It is post-hardened. Further, the curable resin composition of the present invention can be used for general use of a curable resin such as an epoxy resin, for example, an adhesive, a coating material, a coating agent, a molding material (including a sheet, a film, an FRp, etc.), and insulation. Examples of the material (including a printed circuit board, a wire coating, and the like) and (4) materials include a sealing material, a cyanic acid resin composition for a substrate, or a resist 51 for a resist, such as an acrylic vinegar resin. Additives in resins and the like. The adhesive agent, in addition to the adhesive for civil engineering, construction, automotive, general use, and medical use, may be listed as an adhesive for electronic materials, and an adhesive for electronic materials, J magical lifting. Buu-up substrate interlayer adhesive, interlayer adhesive, primer for semiconductor, etc., BGA reinforcing primer, anisotropic conductive crucible (A(7), each An adhesive or the like for the assembly of an anisotropic conductive paste (ACP) or the like. Examples of the sealant include a package, a dipping, and a transfer molding seal for a capacitor, a transistor, a diode, a light emitting diode, an IC, and an LSI. Agent, ^ LSI type COB, COF, TAB 牦田·&gt; u + special package sealant, flip chip (fHp

ChlP)等用之底膠’ QFP、驗、csp等IC封裝體類構裝時 之密封劑（包含加強用底膠）等。 本發明所獲得之硬化物可用於以光學零件材料為代表 之各種用it。所謂光學用材料’ 一般表示用於使可見光、 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、SMD型等LED用密封材料以 外’可列舉如下所述者：液晶顯示器領域中之基板材料、 導光板、稜鏡片、偏光板 '相位差板、視野角補償膜、接 著劑' 偏光片保護膜等液晶用膜等液晶顯示裝置周邊材 料。又’下-代平板顯不器所期待之彩色PDP之密封材料、 抗反射膜、光學補償膜、外殼材料、冑面玻璃之保護膜、 前面玻璃替代材料、接著劑，又，LED顯示裝置中所使用 之LED之模具材,料、LED之密封材料、冑面玻璃之保護膜、 前面玻璃替代材料、接著劑，又，電漿定址液晶（pALc) 52 201137044ChlP) and other primers used as sealing agents (including reinforcing primers) for IC package construction such as QFP, inspection, and csp. The cured product obtained by the present invention can be used for various applications represented by optical component materials. The material "optical material" generally means a material for use in light, such as visible light, infrared rays, ultraviolet rays, X-rays, and laser light. More specifically, in addition to the sealing material for LEDs such as a lamp type and an SMD type, a substrate material, a light guide plate, a cymbal sheet, a polarizing plate, a phase difference plate, and a viewing angle compensation film in the field of liquid crystal display can be cited. And a material surrounding the liquid crystal display device such as a film for liquid crystal such as a polarizer protective film. The sealing material of the color PDP, the anti-reflection film, the optical compensation film, the outer casing material, the protective film of the face glass, the front glass substitute material, the adhesive agent, and the LED display device are also desired in the next-generation flat panel display device. The mold material of the LED used, the sealing material of the LED, the protective film of the face glass, the front glass substitute material, the adhesive, and the plasma addressed liquid crystal (pALc) 52 201137044

顯示器令之基板材料、導光板、稜鏡片、偏向板、相位差 板、視野角補償膜、接著劑、偏光片保護膜，又，有機 (電致發光）顯示器中之前面玻璃之保護膜、前面玻璃替 代材料、接著劑，又，場發射顯示器（FED)中之各種膜基 板、前面玻璃之保護膜、前面玻璃代替材料、接著劑。在 光記錄領域中，為VD (光碟）、CD/ CD — R〇M、CD _ R /RW、DVD-R/DVD-RAM、MO/MD、pD (相變化光 碟）、光學卡用之光碟基板材料、光學取像鏡頭（pickup lens)、保護膜、密封材料、接著劑等。 於光學機器領域中，為靜物攝影機之透鏡用材料、觀 景器稜鏡（finder prism)、目標稜鏡（Urget扣⑽）、觀景器蓋 cover)、光接收感測器部。又，攝影機之攝影透鏡、 觀景器° X ’投影電視之投射透鏡、保護膜、密封材料、 接著劑專。光感測機器之透鏡用材料、密封材料、接著劑、 膜等。於光零件領域中，為光通信系統中之光開關周邊之 纖維材料、透鏡、波導管、元件之密封材料、接著劑等。 光連接器周邊之光纖維材料、套圈（ferrule)'密封材料、接 者劑專。光被動零件、光電路零件中之透鏡、波導管、㈣ 之密封材料、CCD之密封材料、接 ^ r ^ 接者d專。光電子積體電 路（OEIC)周邊之基板材料、纖 ^ *付针疋件之密封材料、 接考劑4。於光纖維領域中，為 衣哪顯不态用照明•弁導 管等工.業用途之感測器類、顯示 ^ - ffl a - ^ ^ 铩識類等，又，通信基 礎建汉用及豕庭内之數位機器連 ㉟雷技mm 士 4 運接用之先纖。於半導體積 體電路周邊材枓中，為LSI、超 1材枓用之顯微蝕刻術用 53 201137044 :抗蝕劑材料。於汽車·運輸機領域中，A :汽車用之燈 二射器軸承5隻圏、齒輪部分、耐钱塗層、開關部分、 刖照:登、引擎内零件、電氣零件、各種内外裝&amp;、驅動引 擎^車'由罐、&amp;車用防鏽鋼板、内側板（interior panel) ' 内裝材料、保護·自束用線組、燃料管、汽車燈、玻璃替 代°° 又’鐵道車輛用之複層玻璃。又，飛機之構造材料 之勒H賦予劑 '引擎周邊構件保護•捆束用線組、耐钮 塗層。於建築領域中，為内裝·加工用材料、電覆蓋層、 片材玻璃中間膜、玻璃替代品、太陽電池周邊材料。於 農業用中’為建築物（hGuse)被覆用膜。下—代之光•電子 功能有機材料’為有機弘元件周邊材料、有機光折射元件、 光-光轉換元件之光學放大元件、光運算元件、有機太陽 電池周邊之基板材料、光纖材料、元件之密封材料、接 劑等。 [實施例] 以下，藉由合成例、實施例更詳細地說明本發明。再 者’本發明並不限定於該等合成例、實施例。力以下之人 成例、實施例中，「份」表示重量份，「％」表示重量％: 再者，實施例中之各物性值係藉由以下之方法測定。 (η分子量：藉由凝膠滲透層析儀（GPC)，算出下 述條件下所測定之聚苯乙烯換算之重量平均分子量。 GPC之各種條件 製造者：島津製作所 管柱：保護管柱 SH0DEXGPCLF—GLF— 804 ( 3 根） 54 201137044 流速：l.Oml/min.The substrate material, the light guide plate, the cymbal sheet, the deflecting plate, the phase difference plate, the viewing angle compensation film, the adhesive, the polarizer protective film, and the protective film of the front glass in the organic (electroluminescence) display, the front side Glass substitute materials, adhesives, and various film substrates in field emission displays (FEDs), protective films for front glass, front glass replacement materials, and adhesives. In the field of optical recording, VD (disc), CD/CD-R〇M, CD_R/RW, DVD-R/DVD-RAM, MO/MD, pD (phase change disc), optical disc Substrate material, optical pickup lens, protective film, sealing material, adhesive, and the like. In the field of optical equipment, it is a lens material for a still camera, a finder prism, a target U (Urget buckle (10)), a viewfinder cover cover, and a light receiving sensor unit. In addition, the camera lens, the viewfinder, the projection lens of the X′′ projection TV, the protective film, the sealing material, and the adhesive agent. A material for a lens of a light sensing machine, a sealing material, an adhesive, a film, or the like. In the field of optical components, it is a fiber material, a lens, a waveguide, a sealing material for an element, an adhesive, and the like around the optical switch in an optical communication system. Optical fiber material around the optical connector, ferrule 'sealing material, connector special. Light passive parts, lenses in optical circuit parts, waveguides, (4) sealing materials, CCD sealing materials, and connectors. A substrate material around the photoelectron integrated circuit (OEIC), a sealing material for the needle assembly, and a test agent 4. In the field of optical fiber, it is used for lighting, such as lighting, 弁 catheters, etc., for the use of sensors, display ^ - ffl a - ^ ^ 铩 类, etc., and communication infrastructure for Han and 豕The digital machine in the court is equipped with 35 Raytech mm 4 for the first fiber. Among the peripheral materials of the semiconductor integrated circuit, it is used for micro-etching of LSI and super-materials. 53 201137044: Resist material. In the field of automobiles and transport aircraft, A: automotive lamp dipole bearing 5 cymbals, gear parts, money-resistant coating, switch parts, illuminating: boarding, engine parts, electrical parts, various interior and exterior &amp; Drive engine ^car' is replaced by tank, &amp; car rust-proof steel plate, interior panel (interior panel), interior material, protection, self-bundling line group, fuel pipe, car lamp, glass instead of ° Laminated glass. In addition, the construction material of the aircraft, the H-granting agent, the engine peripheral member protection, the bundle for binding, and the button coating. In the field of construction, it is a material for interior and processing, an electric cover, an intermediate film for sheet glass, a substitute for glass, and a material for solar cells. In agriculture, it is a film for building (hGuse) coating. The next-generation light-electronic functional organic material is an organic material peripheral material, an organic light-refracting element, an optical amplifying element of a light-to-light conversion element, an optical arithmetic element, a substrate material around an organic solar cell, an optical fiber material, and an element. Sealing materials, joints, etc. [Examples] Hereinafter, the present invention will be described in more detail by way of Synthesis Examples and Examples. Further, the present invention is not limited to the above-described synthesis examples and examples. In the examples and examples, "parts" means parts by weight, and "%" means % by weight: Further, each physical property value in the examples is measured by the following method. (η Molecular weight: The weight average molecular weight in terms of polystyrene measured under the following conditions was calculated by a gel permeation chromatography (GPC). Various conditions of GPC Manufacturer: Shimadzu Corporation column: protection column SH0DEXGPCLF - GLF— 804 (3) 54 201137044 Flow rate: l.Oml/min.

管柱溫度：40°C 使用溶劑：THE (四氫呋喃） 檢測器：RI (示差折射檢測器） (2) 環氧當直.藉由 JIS K ~~ 7 ? ^ λ * ή* /236中所記载之方法測 定。 (3) 黏度：使用東機產業股份有限公司製造之ε型黏 度計（TV — 20)於25°C下測定。 (合成例1 ) 製造步驟（1)係將/3 — (3，4環氧環己基）乙基三甲氧基 矽烷285份、重量平均分子量為19〇〇 (Gpc測定值）之矽 醇基末端曱基苯基聚矽氧油475份（矽醇基當量為95〇，且 作為使用GPC所測定之重量平均分子量之一半而算出）、 0.5%氫氧化鉀（KOH)甲醇溶液4〇份裝入至反應容器中， 將浴溫設定為751並升溫。升溫後，於回流下反應8小時。 製造步驟（ii )係追加甲醇655份後，歷時6〇分鐘滴 加50〇/〇蒸餾水甲醇溶液123份，並於回流下以乃它反應8 小時。反應結束後，利用5%磷酸二氫鈉水溶液中和後，於 8〇 C下將約90%之甲醇蒸餾回收。繼而，添加曱基異丁基 酮（MIBK) 750份，並重複進行3次水洗^對於所獲得之 有機相，於減壓下且於1〇〇。(3下去除溶劑，藉此獲得含環氧 環己基之有機聚矽氧（S _丨）62〇份。所獲得之化合物（s —1)之環氧當量為605g/eq·，重量平均分子量為212〇, 外觀為無色透明之液狀樹脂。又，比例p之值為3 5，源自 55 201137044 倍半石夕氧院之3個氧鍵結之矽原子相對於所有矽原子之比 例約為1 8莫耳％。 (合成例2 ) 製造步驟（i)係將/3 一（3,4環氧環己基）乙基三甲氧基 矽烷375份、重量平均分子量為i9〇〇 ( GPc測定值）之矽 醇基末知甲基苯基聚矽氧油475份（矽醇基當量為95〇，且 作為使用GPC所測定之重量平均分子量之一半而算出）、 0.5%氫氧化鉀（K0H)甲醇溶液4〇份裝入至反應容器中， 將/谷溫设定為75°C並升溫。升溫後，於回流下反應8小時。 製造步驟（ii)係追加甲醇655份後，歷時6〇分鐘滴 加5 0 /〇蒸餾水曱醇溶液丨44份，並於回流下以乃艺反應8 小時。反應結束後，利用5%磷酸二氩鈉水溶液中和後，於 80 C下將約90%之甲醇蒸餾回收。繼而，添加甲基異丁基 酮（MIBK ) 75G份，並重複進行3次水洗。對於所獲得之 有機相於減壓下且於1 〇〇 C下去除溶劑，藉此獲得含環氧 環己基之有機聚矽氧（s_ 2 ) 647份。所獲得之化合物（s —2)之環氧當量為541g/eq，重量平均分子量為η㈧， 外觀為無色透明之液狀樹脂。又，比例p之值為39，源自 倍半矽氧烷之3個氧鍵結之矽原子相對於所有矽原子之比 例約為20莫耳％。 (合成例3) 製造步驟（i)係將石—（3,4環氧環己基）乙基三甲氧基 矽烷263份、重量平均分子量為19〇〇 (Gpc測定值）之矽 醇基末端甲基苯基聚矽氧油475份（矽醇基當量為95〇，且 56 201137044 作為使用GPC所測定之重量平均分子量之一半而算出）、 〇_5%氫氧化鉀（K〇H)曱醇溶液4〇份裝入至反應容器中， 將浴'皿又疋為75 C並升溫。升溫後，於回流下反應8小時。 製造步驟（.ii)係追加曱醇655份後，歷時6〇分鐘滴 加50/〇蒸餾水甲醇溶液115份，並於回流下以乃。c反應8 小時。反應結束後，利用5%磷酸二氫鈉水溶液中和後，於 8〇°C下將約90%之甲醇蒸餾回收。繼而，添加曱基異丁基 _ ( MIBK) 75G份’並重複進行3次水洗。對於所獲得之 有機相，於減壓下且於i 〇〇它下去除溶劑，藉此獲得含環氧 %己基之有機聚矽氧（S _ 3 ) 6〇5份。所獲得之化合物（S —3)之環氧當量為636g/eq，重量平均分子量為μ⑽， 外觀為無色透明之液狀樹脂。又，比例ρ之值為3 3，源自 倍半矽氧烷之3個氧鍵結之矽原子相對於所有矽原子之比 例約為17莫耳％。 (合成例4) 製造步驟（i)係將/3—(3,4環氧環己基）乙基三曱氧基 錢106份、重量平均分子量為1700 (GPC敎值）之石夕 醇基末端曱基苯基聚矽氧油234份（矽醇基當量為，且 作為使用GPC所測定之重量平均分子量之一半而算出）、 〇篇氫氧化鉀（KOH)曱醇溶液18份（K〇H份數為〇〇9 伤）裝入至反應容器巾’將浴溫設定為饥並升溫。升溫 後，於回流下反應8小時。 恤 製造步驟（ii)係追加甲醇3〇5份後，歷時6〇分鐘滴 加5〇%蒸鶴水甲醇溶液8“份，並於回流下以7代反應8 57 201137044 小時。反應結束後，利用5%磷酸二氫鈉水溶液中和後，於 80 °C下進行甲醇之蒸餾回收。繼而，添加 、 I Φ开j暴綱 (MJBK) 38〇份，並4複進行3次水洗n對於有機 相，於減壓下且於10(TC下去除溶劑，藉此獲得含環氧環己 基之有機聚矽氧（S—4) 300份。所獲得之化合物4) 之環氧當量為729g/eq.，重量平均分子量為22〇〇，外觀為 無色透明之液狀樹脂。又，比例p之值為3〇,源自倍半矽 氧烷之3個氧鍵結之矽原子相對於所有矽原子之比例約為 1 5莫耳％。 _ (合成例5) 製造步驟（i )係將/? — (3,4環氧環己基）乙基三甲氧基 矽烷39.4份、重量平均分子量為19〇〇 (Gpc測定值）之矽 醇基末端甲基苯基聚矽氧油137份（矽醇基當量為95〇，且 作為使用GPC所測定之重量平均分子量之一半而算出）、 0‘5%氫氧化鉀（KOH)甲醇溶液10份裝入至反應容器中， 將浴溫設定為75°C並升溫《升溫後，於回流下反應1〇小時。 製造步驟（Π)係追加曱醇14〇份後，歷時6〇分鐘滴 加50%蒸德水甲醇溶液17.3份，並於回流下以75t反應8 小時。反應結束後’利用5%磷酸二氫鈉水溶液中和後，於 80 C下將約90%之曱醇蒸館回收。繼而，添加曱基異丁基 酮（MIBK) 200份’並重複進行3次水洗。對於所獲得之 有機相’於減壓下且於l〇(TC下去除溶劑，藉此獲得含環氧 環己基之有機聚石夕氧（S — 5 ) 1 5 2份。所獲得之化合物（S —5)之環氧當量為i〇40g/eq·，重量平均分子量為2290, 58 201137044 又，比例 22，源 -狀狀树钿。又，比例ρ之值為22，源自 個氧鍵結之矽原子相對於所有矽原子之比 外觀為無色透明之液狀樹脂。 倍半矽氧烷之3個氢Μ眭夕 例約為10莫耳％。 (合成例6 (硬化劑組成物（Η —丨）之製備）） 於具備攪拌機、回流冷卻管、攪拌裝置之燒瓶中，一 面實施氮氣沖洗一面添加三環癸烷二甲醇2〇份（〇χΕΑ製 造TCD- AlcholDM)、曱基六氫鄰苯二曱酸酐（新曰本理 化製造，RIKACID MH，以下稱為酸酐CDA—丨）1〇〇份， 於40°C下反應3小時後，於7(rc下進行！小時加熱攪拌（藉 由GPC確認三環癸烷二曱醇之消失（i面積％以下）），藉 此獲得含有多元羧酸與酸酐之硬化劑組成物（Η _ i ) 12〇 份。所獲得之無色之液狀樹脂由GPC所測得之純度係多元 羧酸（下述式（F))為55面積％’甲基六氫鄰苯二曱酸針 為45面積％。又，官能基當量為2〇lg/ eq.。 式（F)Column temperature: 40 ° C Solvent: THE (tetrahydrofuran) Detector: RI (differential refraction detector) (2) Epoxy straight. By JIS K ~~ 7 ? ^ λ * ή * /236 Method of measurement. (3) Viscosity: Measured at 25 ° C using an ε-type viscometer (TV-20) manufactured by Toki Sangyo Co., Ltd. (Synthesis Example 1) The production step (1) is a decyl group terminal of 285 parts of /3 - (3,4 epoxycyclohexyl)ethyltrimethoxydecane and having a weight average molecular weight of 19 Å (measured by Gpc). 475 parts of mercaptophenyl polyoxyxane (calculated as a decyl group equivalent of 95 Å and calculated as one half of the weight average molecular weight measured by GPC), and loaded with 0.5% potassium hydroxide (KOH) methanol solution Into the reaction vessel, the bath temperature was set to 751 and the temperature was raised. After the temperature was raised, the reaction was carried out under reflux for 8 hours. In the production step (ii), after adding 655 parts of methanol, 123 parts of a 50 〇/〇 distilled water methanol solution was added dropwise over 6 minutes, and it was reacted under reflux for 8 hours. After completion of the reaction, after neutralizing with a 5% aqueous solution of sodium dihydrogen phosphate, about 90% of methanol was distilled and recovered at 8 ° C. Then, 750 parts of mercaptoisobutyl ketone (MIBK) was added, and water washing was repeated 3 times for the obtained organic phase under reduced pressure at 1 Torr. (3) The solvent was removed, whereby 62 parts of an organocyclooxy group (S 丨 ) containing an epoxycyclohexyl group was obtained. The obtained compound (s-1) had an epoxy equivalent of 605 g/eq·, and a weight average molecular weight. It is 212 〇, the appearance is a colorless and transparent liquid resin. Moreover, the ratio of the ratio of p is 3 5, which is derived from the ratio of the three oxygen-bonded ruthenium atoms to the 矽 atoms of 55 201137044. It is 1 8 mol%. (Synthesis Example 2) The production step (i) is 375 parts of /3 (3,4 epoxycyclohexyl)ethyltrimethoxydecane, and the weight average molecular weight is i9 〇〇 (Measurement by GPc) ) 矽 基 475 475 475 475 475 475 475 475 475 475 475 475 475 475 475 475 475 475 475 475 475 475 475 475 475 475 475 475 475 475 475 475 475 475 475 475 475 475 475 475 475 475 475 475 475 475 475 475 4 parts of a methanol solution was placed in a reaction vessel, and the temperature was set to 75 ° C and the temperature was raised. After the temperature was raised, the reaction was carried out for 8 hours under reflux. The production step (ii) was followed by adding 655 parts of methanol to a period of 6 Add 45 parts of 50 〇 distilled water sterol solution to 〇 minute, and react for 8 hours under reflux. After the reaction is over, use After neutralizing the 5% aqueous sodium dihydrogen phosphate solution, about 90% of the methanol was distilled and recovered at 80 C. Then, 75 parts of methyl isobutyl ketone (MIBK) was added, and the water washing was repeated three times. The organic phase was subjected to removal of the solvent under reduced pressure at 1 ° C to obtain 647 parts of an organocyclohexyloxy group (s 2 ) containing an epoxycyclohexyl group. The epoxy equivalent of the obtained compound (s-2) was 541 g / eq, weight average molecular weight η (eight), the appearance of a colorless transparent liquid resin. In addition, the ratio of p is 39, the three oxygen-bonded ruthenium atoms derived from sesquiterpene oxide relative to all ruthenium atoms The ratio is about 20 mol%. (Synthesis Example 3) The production step (i) is 263 parts of stone-(3,4 epoxycyclohexyl)ethyltrimethoxydecane, and the weight average molecular weight is 19 Å (Gpc measurement) ) 475 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 4 parts of potassium (K〇H) sterol solution was charged into the reaction vessel, and the bath was again boiled to 75 C and warmed up. Thereafter, the reaction was carried out for 8 hours under reflux. The production step (.ii) was carried out by adding 655 parts of decyl alcohol, and 115 parts of 50/〇 distilled water methanol solution was added dropwise thereto over 6 minutes, and reacted under reflux for 8 hours. After completion of the reaction, after neutralizing with a 5% aqueous solution of sodium dihydrogen phosphate, about 90% of methanol was distilled and recovered at 8 ° C. Then, fluorenyl isobutyl _ (MIBK) 75 G parts was added and repeated 3 The water was washed once. For the obtained organic phase, the solvent was removed under reduced pressure and under i ,, thereby obtaining 5 parts of an organopolyxyloxy group (S _ 3 ) 6 环氧 containing epoxy hexyl groups. The obtained compound (S-3) had an epoxy equivalent of 636 g/eq, a weight average molecular weight of μ (10), and a colorless transparent liquid resin. Further, the value of the ratio ρ is 3 3 , and the ratio of the three oxygen-bonded germanium atoms derived from the sesquioxane is about 17 mol% with respect to all the germanium atoms. (Synthesis Example 4) The production step (i) was carried out by using 106 parts of /3-(3,4 epoxycyclohexyl)ethyltrimethoxyethanol and having a weight average molecular weight of 1,700 (GPC enthalpy). 234 parts of mercaptophenyl polyoxyl oil (calculated as decyl group equivalent and calculated as one-half of the weight average molecular weight measured by GPC), and 18 parts of potassium hydroxide (KOH) decyl alcohol solution (K〇H) The number of servings is 〇〇9 wound) loaded into the reaction container towel 'Set the bath temperature to hunger and heat up. After the temperature was raised, the reaction was carried out under reflux for 8 hours. After the step (ii) of adding 3 to 5 parts of methanol, 8 parts of 5 parts of steamed methanol solution of methanol was added dropwise over 6 minutes, and 7 generations of reaction was carried out under reflux for 8 57, 2011,370,44 hours. After the reaction was completed, use After neutralizing 5% aqueous solution of sodium dihydrogen phosphate, the methanol was recovered by distillation at 80 ° C. Then, I Φ opened J (MJBK) 38 〇, and 4 times washed 3 times for the organic phase The solvent was removed under reduced pressure at 10 (TC, thereby obtaining 300 parts of an organocyclooxy group (S-4) containing an epoxycyclohexyl group. The obtained compound 4) had an epoxy equivalent of 729 g/eq. The weight average molecular weight is 22 〇〇, and the appearance is a colorless and transparent liquid resin. Further, the ratio of the ratio p is 3 〇, and the three oxygen-bonded ruthenium atoms derived from sesquioxanes are relative to all ruthenium atoms. The ratio is about 15 mol%. _ (Synthesis Example 5) The production step (i) is 39.4 parts of (3,4 epoxycyclohexyl)ethyltrimethoxydecane, and the weight average molecular weight is 19〇〇. (Gpc measured value) 137 parts of sterol-terminated methylphenyl polyoxyl oil (the sterol group equivalent is 95 Å, and the weight is determined by using GPC) 10 parts of the average molecular weight was calculated), 10 parts of 0'5% potassium hydroxide (KOH) methanol solution was placed in the reaction vessel, and the bath temperature was set to 75 ° C and the temperature was raised. After the temperature was raised, the reaction was carried out under reflux for 1 hour. After the production step (Π) is to add 14 parts of decyl alcohol, 17.3 parts of 50% steamed water methanol solution is added dropwise over 6 minutes, and reacted at 75t for 8 hours under reflux. After the reaction is finished, 'utilize 5% phosphoric acid II. After neutralization of the aqueous sodium hydrogen solution, about 90% of the sterol was vaporized and recovered at 80 C. Then, 200 parts of thiol isobutyl ketone (MIBK) was added and the water washing was repeated three times. 'Under the reduced pressure and removing the solvent under TC, thereby obtaining an epoxy-cyclohexyl-containing organopolyoxan (S-5) 152 parts. The obtained compound (S-5) ring The oxygen equivalent is i〇40g/eq·, the weight average molecular weight is 2290, 58 201137044, and the ratio is 22, the source-like tree 钿. In addition, the ratio ρ is 22, and the 矽 atom derived from the oxygen bond is relative to The ratio of all germanium atoms is a colorless and transparent liquid resin. The three hydrogen halides of sesquiterpene are about 10 mole%. (Synthesis Example 6 (Preparation of a hardener composition ()-丨))) In a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, a tricyclic decane dimethanol was added while being purged with nitrogen. Manufactured TCD-AlcholDM), mercapto hexahydrophthalic anhydride (manufactured by Shinjuku Physicochemicals, RIKACID MH, hereinafter referred to as anhydride CDA-丨), and reacted at 40 ° C for 3 hours, at 7 (Circle under rc! hour heating and stirring (confirmation of the disappearance of tricyclodecane decyl alcohol by GPC (i area% or less)), thereby obtaining a hardener composition (Η _ i ) containing a polyvalent carboxylic acid and an acid anhydride 12 Backup. The colorless liquid resin obtained was a polybasic carboxylic acid (the following formula (F)) having a purity of 55 area% and a methylhexahydrophthalic acid needle of 45 area% as measured by GPC. Further, the functional group equivalent was 2 〇 lg / eq. Formula (F)

(合成例7 (硬化劑組成物（Η — 2 )之製備）） 於具備攪拌機、回流冷卻管、攪拌裝置之燒瓶中，一 面實施氮氣沖洗一面添加2,4 —二乙基戊二醇20份（Kyowa(Synthesis Example 7 (Preparation of hardener composition (Η-2))) In a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, 20 parts of 2,4-diethylpentanediol was added while performing nitrogen purge. (Kyowa

Hakko Chemical 製造 Kyowa DiolPD—9)、酸昕（cda — / 201137044 1 ) 100份，於40 C下反應3小時後，於7〇〇c下進行1小時 加熱祝拌（藉由G P C而確s忍到2，4 —二乙基戊二醇之消失（1 面積％以下）），藉此獲得含有多元羧酸與酸酐之硬化劑組 成物（Η — 2 ) 120份。所獲得無色之液狀樹脂由GPC所測 得之純度係多元羧酸（下述式（G))為50面積％，酸酐（CDA —1)為50面積％。又，官能基當量為2〇lg/eq。 式（G )Hakko Chemical manufactures Kyowa DiolPD—9) and acid bismuth (cda — / 201137044 1 ) 100 parts, reacts at 40 C for 3 hours, and then heats for 1 hour at 7 °c (by GPC) The disappearance of 2,4-diethylpentanediol (1 area% or less), thereby obtaining 120 parts of a hardener composition (Η-2) containing a polyvalent carboxylic acid and an acid anhydride. The colorless liquid resin obtained by GPC was a polycarboxylic acid (the following formula (G)) having a purity of 50% by area and an acid anhydride (CDA-1) of 50% by area. Further, the functional group equivalent was 2 〇 lg / eq. Formula (G)

合成例中所獲得之環氧樹脂（S — 1 ) ( s — 2 ) ( S — 3 )、 脂環族環氧樹脂CAE— 1 (日本化藥製造SEJ— 〇1R ( 3,4 —環氧環己基甲基一3’，4’ 一環氧環己基羧酸酯係使用 合成例6中所獲得之硬化劑組成物（H —丨酸酐與多元羧酸 之混合物）、用作為硬化促進劑之四級鱗鹽（c _丨日本化 學工業製造HISHICOLIN PX4MP )以下述表1所示之摻合 比（重量份）進行摻合，並進行2〇分鐘消泡，藉此獲得實 施例1、2及比較例1〜3之硬化性樹脂組成物。 使用所獲彳于之硬化性樹脂組成物，按以下所示之要領 進行硬度測定、熱耐久性試驗、以及與銀之接著試驗。將 結果彙總並示於表卜再者，硬化條件係於u〇t： χ2小時之 預硬化後’進行1401 χ5小時之硬化。 (硬度（蕭氏D)) 60 201137044 依據JIS K6253進行蕭氏D硬度之測定。 (耐熱特性試驗（DMA測定）） 將實施例及比較例中所獲得之硬化性樹脂組成物實施 2〇分鐘真空消泡後，於寬7mm，長5cm ’厚度約8〇(^m 之試驗片用模具中慢慢地澆鑄成型，其後利用聚醯亞胺膜 自上方覆蓋。於上述條件下使該澆鑄成型物硬化而獲得動 態黏彈性用試驗片。使用該等試驗片，於下述所示之條件 下實施動態黏彈性試驗（DMA測定）。 •測定條件 動態黏彈性測定器：TA-instruments製造，DMA一 298〇 測定溫度範圍：~ 3 0。(：〜2 8 0。(： 升溫速度：2。(： /分 試驗片尺寸：使用切成5mmx5〇mm者（厚度約為8〇〇 β m) 〇 •分析條件Epoxy resin (S-1) (s-2) (S-3) obtained in the synthesis example, alicyclic epoxy resin CAE-1 (Japan Chemical Manufacturing SEJ-〇1R (3,4-epoxy) The cyclohexylmethyl-3',4'-epoxycyclohexylcarboxylate is a hardener composition obtained by the synthesis of Example 6 (a mixture of H-phthalic anhydride and a polycarboxylic acid), and used as a hardening accelerator. The quaternary scale salt (c _ 丨 HISHICOLIN PX4MP manufactured by Nippon Chemical Industry Co., Ltd.) was blended at a blending ratio (parts by weight) shown in Table 1 below, and defoamed for 2 minutes, thereby obtaining Examples 1 and 2 and The curable resin composition of Comparative Examples 1 to 3 was subjected to hardness measurement, thermal durability test, and subsequent test with silver using the obtained curable resin composition, and the results were summarized. Further, the hardening conditions are based on u〇t: 预 2 hours of pre-hardening 'hardening for 1401 χ 5 hours. (Hardness (Shore D)) 60 201137044 The D hardness was measured according to JIS K6253. (heat resistance characteristic test (DMA measurement)) obtained in the examples and comparative examples The curable resin composition was vacuum-defoamed for 2 minutes, and then slowly cast in a mold having a width of 7 mm and a length of 5 cm and a thickness of about 8 Å (^m), and then using a polyimide film from above. The test piece was cured under the above conditions to obtain a test piece for dynamic viscoelasticity. Using these test pieces, a dynamic viscoelasticity test (DMA measurement) was carried out under the conditions shown below. Elastic measuring device: manufactured by TA-instruments, DMA 298 〇 measuring temperature range: ~ 3 0. (: ~ 2 8 0. (: heating rate: 2. (: / min. test piece size: use cut into 5mmx5〇mm (thickness is about 8 〇〇β m) 〇•Analysis conditions

Tg .將DMA測定中之Tan_ 5之峰值點作為 (銀接著性試驗（拉伸剪切試驗）） 以使接著面積成為25mmxlGmm之方式，將實施例及比 較例中所獲侍之硬化性樹脂組成物均勻地塗佈（塗佈重量 ^ 一為（UH2〜〇.〇15§)於實施過鐘銀之25職亀似厚度 2mm之SUS基材之將 目上万將相冋之基材貼合於該塗 佈面上並利用大型夾呈因宗垃基品 時U疋接者面，然後進行特定之硬化 時間而使其熱硬化，蕤 猎此製成拉伸剪切用樣品。使用該等 …於下述所示之條件實施拉伸剪切試驗。 201137044 *測定條件Tg. The peak point of Tan_5 in the DMA measurement was taken as (silver adhesion test (tensile shear test)) so that the bonding area became 25 mm x 1 Gmm, and the curable resin obtained in the examples and the comparative examples was composed. Uniform coating (coating weight ^ one (UH2 ~ 〇. 〇 15 §) in the implementation of the 25 silver SUS 厚度 厚度 钟 钟 钟 实施 实施 实施 实施 SUS SUS SUS SUS SUS SUS SUS SUS SUS SUS SUS SUS SUS SUS SUS On the coated surface, a large-sized clip is used to form a U-joined surface, and then a specific hardening time is used to thermally harden it. ...the tensile shear test was carried out under the conditions shown below. 201137044 *Measurement conditions

Tensilon : Orientec 製造 RTA— 500 測定模式：拉伸 移動速度：3mm/分 •分析條件 拉伸剪切強度係取斷裂最大值，並轉換成平均接著面 積。 [表1] 比較例1 實施例1 比較例2 實施例2 比較例3 S-1 100 90 S-2 100 S-3 95 100 CAE-1 10 5 Η—1 26.2 35.7 29.6 29.3 25.1 C-l 0.5 0.5 0.5 0.5 0.5 硬度（蕭氏cn 58 70 69 58 52 Tg (DMA) 57 81 79 57 50 接著強度（MPa) 8.1 15.5 10.9 12.5 9.7 於表1中，若對比較例1與實施例丨、及實施例2與比 較例3進行比較，貝可確認藉由於15〜4〇重量％，較佳為 比例P (重量％)之範圍内含有脂環族環氧樹脂，不僅硬度 ⑻得到提昇，而且耐熱特性Tg、及接著強度亦大幅度 地提昇。 比較例2係為了獲得具有與實施例丨相同之硬度 硬化物而4成者’若比較兩者，雖然耐熱特性^ 62 201137044 二提高至相同程度，但實施心之接著強度遠高於比較例 又由比較例1與實施例2之比較評價亦可判斷該結果。 β即，可知：藉由於$40重量％，較佳為比例ρ (重 里/。）之範圍内添加脂環族環氧樹脂，，顯現藉由聚矽氧烷 結構所無法達成之程度之接著強度。 合成例中所獲得之環氧樹脂（n)、脂環族環氧樹 脂（⑽―1) ’係使用合成例中所獲得之硬化劑組成物（Η -1)、用作為硬化促進劑之磷酸酯辞錯合物（c_2幻叫 Wustdes公司製&amp; xc—92⑹、用作為光穩定劑之受阻 月女（L- 1汽巴精化製造TINUVIN 77〇df)、抗氧化劑（〇 1 Adeka製造Adekastab260 )，以下述表2所示之摻合 比（重量份）進行掺合，並進行2〇分鐘消泡，藉此獲得實 施例3及比較例4之硬化性樹脂組成物。 使用所獲得之硬化性樹脂組成物，按以下所示之要領 進行硬化性樹脂組成物之穩定性與硬化物之硬度之評價。 將結果彙總並示於表2。再者，硬化條件係於i 1〇它χ2小時 之預硬化後’進行140°cx5小時之硬化。 (穩定性試驗） 於剛摻合之後與6小時後分別測定25°C下之黏度（E 型旋轉式黏度計），以該黏度之上升程度來評價穩定性。 (硬度（蕭氏D)) 依據JIS K6253進行蕭氏d硬度之測定。 [表2] 63 201137044 實施例3 比較例4 S-1 90 100 CAE-1 10 H-1 35.7 26.2 C-2 0.5 0.5 L-1 0.2 0.2 0-1 0.2 0.2 初始之黏度（mPa) 2611 3226 6小時後之黏度上升率 —33% 39% 硬度（D) 70 59 根據本結果可知，於製成為一液時，6小時後之黏度其 黏度上升率低於初始黏度，，且為穩定性更高之組成物。 合成例中所獲得之環氧樹脂（S — 4 ) ( S - 5 )、脂環 族環氧樹脂（CAE — 1 )，係使用合成例6中所獲得之硬化 劑組成物（Η— 1 )、合成例7中所獲得之硬化劑組成物（H ~ 2 )、用作為硬化促進劑之磷酸酯鋅錯合物（c _ 2 )、用 作為光穩定劑之受阻胺（L— υ 、抗氧化劑（0—丨），以 下述表3所示之摻合比（重量份）進行掺合’並進行2〇分 釦消泡，藉此獲得實施例4〜ό、比較例5之硬化性樹脂組 成物。進而，使所獲得之硬化性樹脂組成物按以下之要領 硬化，並進行穿透率與耐光性之評價。 (穿透率試驗） 於以成為30mmx20mmx高度imm之方式利用耐熱膠帶 製成壩（dam)之玻璃基板上，慢慢地將實施例及比較例之硬 化性樹脂組成物進行澆鑄成型。將該澆鑄成型物進行11〇 C x3小時之預硬化後，進行15〇充X丨小時之硬化，從而獲 64 201137044 得厚度為lmm之穿透率用試驗片。比較46〇nm下之各個硬 化物之穿透率。 (UV耐久性穿透率試驗） 於真空下將實施例及比較例之硬化性樹脂組成物進行 2〇分鐘消泡後，於底面直徑為5cm，高度為2cm之鋁杯慢 慢地濟鑄成型《在與上述穿透率試驗相同之硬化條件下， 將該澆鑄成型物放入烘箱中使其硬化，獲得厚度為2mm之 穿透性用試驗片《使用該等試驗片，藉由分光光度計測定 紫外線照射前後之穿透率（測定波長：375nm、4〇〇nm、 465nm ) ’並算出其變化率。紫外線照射條件如下。Tensilon : Orientec Manufacture RTA— 500 Measurement mode: Stretching Movement speed: 3 mm/min • Analysis conditions The tensile shear strength is taken as the maximum value of the fracture and converted into the average joint area. [Table 1] Comparative Example 1 Example 1 Comparative Example 2 Example 2 Comparative Example 3 S-1 100 90 S-2 100 S-3 95 100 CAE-1 10 5 Η-1 1 26.2 35.7 29.6 29.3 25.1 Cl 0.5 0.5 0.5 0.5 0.5 Hardness (Shore cn 58 70 69 58 52 Tg (DMA) 57 81 79 57 50 Next strength (MPa) 8.1 15.5 10.9 12.5 9.7 In Table 1, for Comparative Example 1 and Example 丨, and Example 2 In comparison with Comparative Example 3, it was confirmed that the alicyclic epoxy resin was contained in the range of 15 to 4% by weight, preferably in the ratio of P (% by weight), not only the hardness (8) was improved, but also the heat resistance Tg, Then, the strength was also greatly improved. In Comparative Example 2, in order to obtain a cured product having the same hardness as that of Example 4, if the two were compared, although the heat resistance characteristics were improved to the same degree, the implementation of the heart was achieved. The subsequent strength is much higher than that of the comparative example, and the result can be judged by comparison and comparison between Comparative Example 1 and Example 2. Since β is, it is known that it is preferably within a range of ratio ρ (recurring/.) by $40% by weight. Adding an alicyclic epoxy resin The strength of the bond which cannot be achieved by the structure. The epoxy resin (n) and the alicyclic epoxy resin ((10)-1) obtained in the synthesis example use the hardener composition obtained in the synthesis example (Η - 1), a phosphate compound as a hardening accelerator (c_2 phantom Wustes Co., Ltd. &amp; xc-92 (6), used as a light stabilizer for the obstructed moon female (L-1 car Ciba refined manufacturing TINUVIN 77〇df ), an antioxidant (Adekastab 260 manufactured by Adeka), blended at a blending ratio (parts by weight) shown in Table 2 below, and defoamed for 2 minutes, thereby obtaining hardening of Example 3 and Comparative Example 4. The resin composition obtained was subjected to evaluation of the stability of the curable resin composition and the hardness of the cured product using the obtained curable resin composition. The results are summarized and shown in Table 2. The hardening conditions were based on i 1 〇 after 2 hours of pre-hardening 'hardening at 140 ° c x 5 hours. (Stability test) The viscosity at 25 ° C was measured after 6 hours after the blending (E-rotation) Viscosity meter), the stability is evaluated by the degree of increase in viscosity (Hardness (Shore D)) Measurement of Shore d hardness according to JIS K6253 [Table 2] 63 201137044 Example 3 Comparative Example 4 S-1 90 100 CAE-1 10 H-1 35.7 26.2 C-2 0.5 0.5 L-1 0.2 0.2 0-1 0.2 0.2 Initial viscosity (mPa) 2611 3226 Viscosity increase rate after 6 hours—33% 39% Hardness (D) 70 59 According to the results, when it is made into one liquid, The viscosity after 6 hours has a viscosity increase rate lower than the initial viscosity, and is a composition with higher stability. The epoxy resin (S-4) (S-5) and the alicyclic epoxy resin (CAE-1) obtained in the synthesis example were the hardener compositions obtained in Synthesis Example 6 (Η-1). The hardener composition (H ~ 2 ) obtained in Synthesis Example 7, the zinc phosphate complex (c _ 2 ) used as a hardening accelerator, and the hindered amine (L- 、, anti-resistant) used as a light stabilizer The oxidizing agent (0-丨) was blended with the blending ratio (parts by weight) shown in Table 3 below and subjected to 2 〇 defoaming, whereby the curable resins of Examples 4 to ό and Comparative Example 5 were obtained. Further, the obtained curable resin composition was hardened in the following manner, and the transmittance and light resistance were evaluated. (Permeability test) It was made of heat-resistant tape in a manner of being 30 mm x 20 mm x height imm. The curable resin composition of the examples and the comparative examples was cast-molded slowly on the glass substrate of the dam. The cast molded product was pre-cured at 11 〇C x 3 hours, and then subjected to 15 Torr. Hardening of the hour, thus obtaining a test piece with a penetration rate of lmm of thickness of 2011. The transmittance of each cured product at 46 〇 nm was compared. (UV Durability Transmittance Test) The curable resin composition of the examples and the comparative examples was defoamed under vacuum for 2 minutes, and the diameter at the bottom surface was 5cm, 2cm high aluminum cup is slowly cast. "Under the same hardening conditions as the above penetration test, the cast molded product is placed in an oven to be hardened to obtain a penetration of 2 mm. Test piece "The penetration rate (measurement wavelength: 375 nm, 4 〇〇 nm, 465 nm)" before and after ultraviolet irradiation was measured by a spectrophotometer using these test pieces, and the rate of change was calculated. The ultraviolet irradiation conditions were as follows.

务、外線照射機·· EYE Super UV Tester SUV — Wl 1 溫度：60°C 照射能量：50〜60mW / cm2 照射時間：100小時 [表3] 實施例4 實施例5 比較例5 p實施例6 S-4 90 80 100 S-5 95 CAE-1 10 20 5 H-1 24.6 27.0 22.6 H-2 16.5 C-2 0.5 0.5 0.5 0.5 L-1 0.2 0.2 0.2 0.2 0~ 1 0.2 0.2 0.2 0.2 穿透率（46011111) 92.4 92.3 92.4 91.9 耐光試驗（穿透率保持率） 98.3% 98.7% 98.9% 99.1% 65 201137044 根據本結果’可確認到：本發明之硬化性樹脂組成物 係即使加入了脂環族環氧樹脂，亦具有與未混合脂環族環 氧樹脂者相同程度之耐光特性，且光學特性優異之並不逊 色之硬化性樹脂組成物。 合成例中所獲得之環氧樹脂（S ~ 4 )、脂環族環氧樹 脂（CAE— 1)，係使用合成例6中所獲得之硬化劑組成物 (Η — 1 )、用作為硬化促進劑之磷酸酯鋅錯合物（c _ 2 )、 用作為光穩定劑之受阻胺（L _ 1 )、抗氧化劑（〇 _ 1 ), 以下述表4所示之摻合比（重量份）進行摻合，並進行2〇 分鐘消泡，藉此獲得實施例7、8之硬化性樹脂組成物。 (LED點亮試驗） 使用所獲得之硬化性樹脂組成物，將其填充至注射器 並利用精密喷出裝置，澆鑄至搭載有中心發光波為465nm 之晶片之外徑5mm見方、及外徑3mm見方的表面構裝型 LED封裝體。將該澆鑄成型物投入至加熱爐，於}2〇它下進 行1小時之硬化處理，進而於15 0 °C下進行3小時之硬化處 理而製成LED封裝體。點亮試驗係進行規定電流即30mA 之一倍之60mA下之點亮試驗（加速試驗）。於下述中表示 詳細之條件。測定項目，使用積分球測定點燈前後200小 時之照明度，並算出試驗用LED之照明度之保持率。又， 本試驗係於多濕高溫之驅動環境下進行。 •點·燈詳細條件 發光波長：465nm 驅動方式：恆定電流方式，60mA (發光元件之規定電 66 201137044 流為30mA ) 驅動環境：85°C、85% [表4] 實施例7 實施例8 S-4 90 90 CAE-1 10 10 H-1 24.6 24.6 C-2 0.3 0.3 L-1 0.2 0.2 0-1 0.2 0.2 LED晶片 3mm見方 5mm見方 200h後之照明度保掊垄 105% 109% 400h後之照明度保掊峯 98% 83% 根據以上結果’可確認本發明之硬化性樹脂組成物於 高溫高濕且流通過剩之電流之加速試驗中亦顯現較高之照 明度保持率’作為LED，具有較高之特性。 合成例中所獲得之環氧樹脂（s — 4 )、脂環族環氧樹 脂（CAE— 1 ) ’係使用硬化劑組成物（H_ i )、酸酐（cda 1)、用作為硬化促進劑之四級鱗鹽（C— 1)、用作為光 穩定劑之受阻胺（L-2汽巴精化製造TINUVIN 144)， 抗氧化劑（Ο ~~ 2 Adeka製造Adekastab AO60 )及添加劑（〇 〜3 Adeka製造Adekastab3010 )，以下述表5所示之摻合 比（重量份）進行摻合，並進行2〇分鐘消泡，藉此獲得實 施例9〜11 ’比較例6、7之硬化性樹脂組成物。 (腐敍氣體穿透性試驗） 67 201137044 使用所獲得之硬化性樹脂組成物，將其填充至注射器 中並利用精密喷出裝置，澆鑄至搭載有中心發光波為465nm 之晶片之外徑5mm見方的表面構裝型LED封裝體。將該澆 鑄成型物投入至加熱爐中，於120°C下進行1小時之硬化處 理’進而於1 50 C下進行3小時之硬化處理而製成LED封 裝體。於下述條件下將LED封裝體放置於腐蝕性氣體中， 觀察内部密封之經鍍銀之導線架部之顏色的變化。將結果 示於表5。 •測定條件 腐蝕氣體：硫化銨20%水溶液（當硫成分與銀進行反 應時變黑） 接觸方法：於廣口玻璃瓶中，使硫化銨水溶液之容器 與上述LED封裝體混合存在，於蓋上廣口玻璃瓶而於密閉 狀況下，使所揮發之硫化銨氣體與LED封裝體接觸。 •分析條件 腐蝕之判定：觀察LED封裝體内部之導線架變黑（稱 為黑化…夺間，該變色時間越長，判斷為对腐蝕氣體性 越優異。觀察係於10分鐘後、2小時後、“、時後取出來 進行確認’評㈣將無變色者記作Q，將茶色〜褐色者記 作X ’將完全黑化者記作xx。 68 201137044 [表5]EYE Super UV Tester SUV — Wl 1 Temperature: 60° C. Irradiation energy: 50 to 60 mW / cm 2 Irradiation time: 100 hours [Table 3] Example 4 Example 5 Comparative Example 5 p Example 6 S-4 90 80 100 S-5 95 CAE-1 10 20 5 H-1 24.6 27.0 22.6 H-2 16.5 C-2 0.5 0.5 0.5 0.5 L-1 0.2 0.2 0.2 0.2 0~ 1 0.2 0.2 0.2 0.2 Permeability (46011111) 92.4 92.3 92.4 91.9 Light resistance test (permeability retention rate) 98.3% 98.7% 98.9% 99.1% 65 201137044 According to the results, it can be confirmed that the curable resin composition of the present invention has an alicyclic ring even though it is added. The oxyresin also has a light-resistant resin composition which is light-resistant to the same extent as the alicyclic epoxy resin, and which is excellent in optical properties. The epoxy resin (S ~ 4 ) and the alicyclic epoxy resin (CAE-1) obtained in the synthesis example were used as the hardening accelerator by using the hardener composition (Η-1) obtained in Synthesis Example 6. The zinc phosphate complex (c _ 2 ), the hindered amine (L _ 1 ) used as a light stabilizer, and the antioxidant (〇 _ 1 ), the blending ratio (parts by weight) shown in Table 4 below The blending was carried out, and defoaming was carried out for 2 minutes, whereby the curable resin compositions of Examples 7 and 8 were obtained. (LED lighting test) Using the obtained curable resin composition, it was filled in a syringe and cast into a wafer having a central light-emitting wave of 465 nm and an outer diameter of 5 mm square and a diameter of 3 mm square by a precision discharge device. Surface mount type LED package. This cast molded product was placed in a heating furnace, hardened for 1 hour under the conditions of 2 Torr, and further subjected to a hardening treatment at 150 ° C for 3 hours to prepare an LED package. The lighting test is a lighting test (acceleration test) at 60 mA which is one of 30 mA of a predetermined current. The detailed conditions are shown below. For the measurement item, the illuminance of 200 hours before and after lighting was measured using an integrating sphere, and the illuminance retention rate of the test LED was calculated. Moreover, the test was carried out in a humidified and high-temperature driving environment. • Point lamp detailed condition Illumination wavelength: 465nm Drive method: Constant current mode, 60mA (Specified power for light-emitting elements 66 201137044 Flow is 30mA) Drive environment: 85°C, 85% [Table 4] Example 7 Example 8 S -4 90 90 CAE-1 10 10 H-1 24.6 24.6 C-2 0.3 0.3 L-1 0.2 0.2 0-1 0.2 0.2 LED wafer 3mm square 5mm square after 200h illumination degree protection ridge 105% 109% 400h According to the above results, it can be confirmed that the curable resin composition of the present invention exhibits a high illuminance retention rate in an accelerated test of high-temperature and high-humidity and a current flowing through the remaining current as an LED. Higher characteristics. The epoxy resin (s-4) and the alicyclic epoxy resin (CAE-1) obtained in the synthesis example use a hardener composition (H_i), an acid anhydride (cda 1), and are used as a hardening accelerator. Grade IV scale salt (C-1), hindered amine used as light stabilizer (Luncoal refined by L-2 Ciba), antioxidant (Adekastab AO60 manufactured by Adeka) and additives (〇~3 Adeka) Adekastab 3010) was produced, blended at a blending ratio (parts by weight) shown in Table 5 below, and defoamed for 2 minutes, thereby obtaining the curable resin compositions of Examples 9 to 11 'Comparative Examples 6 and 7. . (Corruption Gas Penetration Test) 67 201137044 The obtained curable resin composition was filled in a syringe and cast into a 5 mm square outer diameter of a wafer having a central illuminating wave of 465 nm by a precision ejection device. Surface mount type LED package. This cast molded product was placed in a heating furnace, and subjected to a hardening treatment at 120 ° C for 1 hour, and further hardened at 1 50 C for 3 hours to obtain an LED 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 of the inner seal was observed. The results are shown in Table 5. • Determination of the conditional corrosive gas: Ammonium sulfide 20% aqueous solution (blackening when the sulfur component reacts with silver) Contact method: In a wide-mouth glass bottle, the container of the aqueous ammonium sulfide solution is mixed with the above LED package, and placed on the lid The wide-mouthed glass bottle is in a sealed state, and the vulcanized ammonium sulfide gas is brought into contact with the LED package. • Analysis of Conditional Corrosion: Observe that the lead frame inside the LED package becomes black (referred to as blackening, and the longer the discoloration time, the more excellent the corrosion gas property is. The observation is after 10 minutes, 2 hours. After, ", and then take it out to confirm" (4), the person who has no discoloration is referred to as Q, the person who is brown to brown is referred to as X', and the person who is completely blackened is denoted as xx. 68 201137044 [Table 5]

實施例9 實施例10 實施例11 比較例6 比較例7 S-4 90 80 80 100 100 CAE—1 10 20 20 H-l 30.7 33.7 28,2 CDA-1 28.2 23.6 C-l 0.3 0.3 0.3 0.3 0.3 L—2 0.2 0.2 0.2 0.2 0.2 0-2 0.2 0.2 0.2 0.2 0.2 0-3 0.2 0.2 0.2 0.2 0.2 導線架之 變色時間 10分鐘 〇 〇 〇 〇 〇 2小時 〇 〇 〇 〇 X 6小時 〇 〇 ~~δ~ X XX 根據上述結果，可明確到：實施例之硬化性樹脂組成 物與比較例之硬化性樹脂組成物（含有聚矽氧烷化合物與 酸酐）相比，導線架之鍍銀不變色，可判明長期之耐腐蝕 氣體性優異。Example 9 Example 10 Example 11 Comparative Example 6 Comparative Example 7 S-4 90 80 80 100 100 CAE-1 10 20 20 Hl 30.7 33.7 28, 2 CDA-1 28.2 23.6 Cl 0.3 0.3 0.3 0.3 0.3 L-2 0.2 0.2 0.2 0.2 0-2 0.2 0.2 0.2 0.2 0.2 0-3 0.2 0.2 0.2 0.2 0.2 Discoloration time of lead frame 10 minutes 〇〇〇〇〇 2 hours 〇〇〇〇 X 6 hours 〇〇 ~~ δ~ X XX As a result of the above, it is clear that the curable resin composition of the example and the curable resin composition of the comparative example (containing the polyoxyalkylene compound and the acid anhydride) do not discolor the silver plating of the lead frame, and it is possible to recognize the long-term resistance. Excellent in corrosion gas.

合成例A 於具備授拌機、回流冷卻管、攪拌裝置之燒瓶中，一 面實施氮氣沖洗一面將兩末端甲醇改質聚矽氧（χ22 — 160AS信越化學工業股份有限公司製造，式（4八）中心為 甲基且心為丙氧基伸乙基之化合物）5〇〇份、rikacid (4—曱基六氫鄰苯二曱酸酐，新日本理化製造）份投 入至反應容器中，然後於8crc下反應4小時。藉此獲得無 色透明液體之多元羧酸（H— 4) 668份。Synthesis Example A In a flask equipped with a blender, a reflux cooling tube, and a stirring device, the both ends of the methanol were modified by polynitrogen gas while being purged with nitrogen (χ22-160AS Shin-Etsu Chemical Co., Ltd., formula (48) 5 parts of a compound with a methyl group and a core of propoxyethyl group), rikacid (4-mercaptohexahydrophthalic anhydride, manufactured by Nippon Chemical Co., Ltd.) is put into a reaction vessel, and then under 8crc Reaction for 4 hours. Thus, 668 parts of a polycarboxylic acid (H-4) of a colorless transparent liquid was obtained.

貪施例A — F ’比較例A、B 69 201137044 合成例中所獲得之環氧樹脂（S — 2 )、脂環族環氧樹 脂（C AE — 1 )，係使用合成例A中所獲得之多元羧萨（Η -4) ’並使用2 -乙基己酸鋅（Hope Chemical股份有限八 司製造以下稱為C—3)、受阻胺（LA一 81 Adeka製造: 以下稱為L — 3 )、麟化合物（Adeka260，以下稱為〇 — 4 ) 以下述表6所示之摻合比（重量份）進行摻合，並進行2〇 分鐘消泡’藉此獲得本發明或比較用之硬化性樹脂組成物。 使用所獲得之硬化性樹脂組成物，按以下所示之要領 進行各種試驗。將結果橐總並示於表6。 (1 )回流焊測試 將所獲得之硬化性樹脂組成物實施20分鐘真空消泡 後’將其填充於注射器並使用精密喷出裝置’以開口部成 為平面之方式洗鑄至搭载有具有· 465 nm之發光波長之發光 元件的表面構裝型LED。於進行120°C χ3小時之預硬化後， 進行1 50°C χ2小時之硬化’然後將表面構裝型[ED密封。 將所獲得之試驗用LED進行30。(：、70%x72Hr之吸濕後， 使用咼溫觀察裝置（SMT Scope SK— 5000山陽精工股份有 限公司製造）’確認於以下之回流焊條件下之試驗用LED 自反射器（聚酿胺製）的剝離。於η 3下進行測試，並以 (NG數）/ (測試數）進行評價。 條件係以2°C /秒自25t升溫至15(TC，其後，於I50 C下保持2分鐘，進而以2。(： /秒升溫至260°C，將溫度保 持1 0秒後，以1 3 °C /秒冷卻至室溫。 (2 )熱循環測試 70 201137044 /…、循衣4驗係與（丨）同樣地進行摻合、澆鑄成型、硬 化後於冷熱衝擊試驗中，將升溫及降溫所需要之時間設 定為二鐘而重複進行5〇次一 4〇。。15分鐘〜贿XU分 鐘之循環’並以目視觀察試驗用LED有無產生裂痕。於η =5進行測試，並以（肋數）/(測試數）表示評價結果。 [表6] 摻合 組成 S—2 ~ΓΑΡ-·1 實施例A 100 實施例B 100 實施例C 100 實施例D 100 實施例E 100 實施例F 100 比較例A ΐπο 比較例Β 100 Η—4 1U.U 118.2 5.0 100.9 5.0 100.9 2.5 92.3 2.5 92.3 2.0 90 6 0.5 〇&lt; λ 0.0 0^3 7 1一 J L-3 0.9 0.2 1.6— 0.2 卜0.8 0.2 1.9 0.2 卜0.8 0.2 0.8 Λ -&gt; 0.7 0,7 評價 0—4 回流焊測試 0.2 0/3 0.2 0/3~~ 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 熱循環測試 0/5 0/5 0/3 0/5 0/3 0/5-1 0/3 0/5 0/3 0/5 3/3 3/5 3/3 5/5 根據以上結果，可知本發明之硬化性樹脂組成物與比 較例相比，具有較高之強韌性，由熱循環所產生之裂痕較 少，可解決由回流焊所引起之自反射器之剝離等課題。 合成例Β 於具備攪拌機、回流冷卻管、攪拌裝置、迪恩—斯達 克（Dean — Stark)管之燒瓶中，一面實施氮氣沖洗一面添 加曱苯150份' 2,4-二乙基戊二醇（Ky〇wa Chemical 製造 Kyowa Diol PD9 ) 80 份、3 —環己稀緩酸】26 份、對甲苯磺酸2份’然後於加熱回流下—面去除水一面 進行10小時反應。反應結束後，利用1〇%碳酸氫鈉水溶液 50份進行2次水洗’進而利用水50份將所獲得之有機層進 行2次水洗後，利用旋轉蒸發器將有機溶劑進行濃縮，藉 71 201137044 此獲得本發明之二烯化合物（D —丨）187份。可確認到：該 二烯化合物（D — 1 )之形狀為液狀’由氣相層析法所測得 之純度為96%，利用凝膠滲透層析儀之分析之結果為純度 &gt; 98%。Grease Example A - F 'Comparative Example A, B 69 201137044 The epoxy resin (S - 2 ) and the alicyclic epoxy resin (C AE - 1 ) obtained in the synthesis example were obtained in Synthesis Example A. Polycarboxyxa (Η -4) ' and use zinc 2-ethylhexanoate (made by Hope Chemical Co., Ltd., hereinafter referred to as C-3), hindered amine (manufactured by LA-81 Adeka: hereinafter referred to as L-3 ), a compound (Adeka 260, hereinafter referred to as 〇-4) is blended at a blending ratio (parts by weight) shown in the following Table 6, and defoamed for 2 minutes to thereby obtain the hardening of the present invention or comparative use. Resin composition. Using the obtained curable resin composition, various tests were carried out in the manner shown below. The results are summarized and shown in Table 6. (1) Reflow soldering test After the vacuum curable resin composition obtained was subjected to vacuum defoaming for 20 minutes, it was filled in a syringe, and the opening was flattened to the surface by using a precision discharge device. A surface mount type LED of a light-emitting element having an emission wavelength of nm. After pre-hardening at 120 ° C for 3 hours, hardening was carried out at 150 ° C for 2 hours' and then the surface was mounted [ED sealed. The test LED obtained was subjected to 30. (: After the moisture absorption of 70% x 72Hr, the test LED self-reflector was confirmed under the following reflow conditions using a temperature observation device (SMT Scope SK-5000 manufactured by Sanyo Seiko Co., Ltd.) Peeling. The test was carried out under η 3 and evaluated by (NG number) / (test number). The condition was raised from 25 t to 15 (TC) at 2 ° C / sec, and thereafter maintained at 2 ° C under 2 ° C. In minutes, further increase the temperature to 260 ° C by 2 (: / sec, keep the temperature for 10 sec, and then cool to room temperature at 13 ° C / sec. (2) Thermal cycle test 70 201137044 /..., 衣衣4 In the same manner as in (丨), after blending, casting, and hardening, in the thermal shock test, the time required for heating and cooling is set to two times and repeated five times to four times. 15 minutes ~ bribe XU minute cycle ' and visually observe whether the test LED has cracks. Test at η = 5, and the evaluation results are expressed by (number of ribs) / (test number). [Table 6] Blending composition S-2~ -1 Example A 100 Example B 100 Example C 100 Example D 100 Example E 100 Example F 100 Comparative Example A Ϊ́πο Comparative example Η100 Η—4 1U.U 118.2 5.0 100.9 5.0 100.9 2.5 92.3 2.5 92.3 2.0 90 6 0.5 〇&lt; λ 0.0 0^3 7 1 a J L-3 0.9 0.2 1.6- 0.2 Bu 0.8 0.2 1.9 0.2 Bu 0.8 0.2 0.8 Λ -&gt; 0.7 0,7 Evaluation 0—4 Reflow soldering test 0.2 0/3 0.2 0/3~~ 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Thermal cycle test 0/5 0/5 0/3 0/ 5 0/3 0/5-1 0/3 0/5 0/3 0/5 3/3 3/5 3/3 5/5 From the above results, it is understood that the curable resin composition of the present invention is compared with the comparative example. Compared with the high toughness, there are fewer cracks caused by thermal cycling, which can solve the problem of peeling from the reflector caused by reflow soldering. Synthetic example 具备 With agitator, reflux cooling tube, stirring device, Di In a flask of Dean-Stark tube, 150 parts of '2,4-diethylpentanediol (Kyowa Diol PD9 manufactured by Ky〇wa Chemical) was added to the flask with nitrogen gas on the one hand, 80 parts, 3 - cycloheximide acid] 26 parts, 2 parts of p-toluenesulfonic acid, and then reacted under heating and reflux for 10 hours. After the reaction, 50 parts of 1% by weight aqueous sodium hydrogencarbonate solution was used. After the water washing was performed twice, the obtained organic layer was washed twice with water, and then the organic solvent was concentrated by a rotary evaporator, and 71 parts of the diene compound (D-丨) of the present invention was obtained by 71 201137044. . It was confirmed that the shape of the diene compound (D-1) was liquid, and the purity measured by gas chromatography was 96%, and the result of analysis by gel permeation chromatography was purity &gt; 98. %.

合成例C 於具備攪拌機、回流冷卻管、攪拌裝置之燒瓶中，— 面實施氮氣沖洗一面添加水15份、12 —鶴磷酸0.95份、填 酸氩二鈉0.78份、乙酸二硬化牛脂烷基二曱基録2 7份 (Lion Akzo 製造 50% 己烷溶液，Arquad 2HT acetate )， 生成鎢酸系觸媒後，添加甲苯120份、二烯化合物d- i 94 份，進而再次進行攪拌，藉此製成乳液狀態之溶液。將該 溶液升溫至50°C，一面激烈地攪拌一面添加35%過氧化氫 水55份，然後直接於5〇r下攪拌13小時。藉由確認 反應之進行。結果反應結束後之基質之轉換&gt;99%，原料波 峰消失。 繼而矛J用1 /〇苛性鈉水溶液中和後，添加2〇〇乂硫代硫 酸鈉水溶液25份並進行3〇分鐘攪拌，然後靜置。取出分Synthesis Example C In a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, 15 parts of water, 0.95 parts of 12-heopic acid phosphate, 0.78 parts of argon acid disodium, and a hardened tallow alkyl acetate were added while performing nitrogen purge. 2 parts of 曱基录 (Lion Akzo produces 50% hexane solution, Arquad 2HT acetate), and after forming a tungstic acid-based catalyst, 120 parts of toluene and 94 parts of the diene compound d-i are added, and the mixture is further stirred. A solution in the form of an emulsion. The solution was heated to 50 ° C, and 55 parts of 35% hydrogen peroxide water was added thereto while stirring vigorously, followed by stirring at 5 Torr for 13 hours. By confirming the progress of the reaction. As a result, the conversion of the substrate after the completion of the reaction was &gt;99%, and the peak of the raw material disappeared. Then, the spear J was neutralized with a 1 / 〇 aqueous caustic soda solution, and 25 parts of an aqueous solution of sodium thiosulfate was added thereto, stirred for 3 minutes, and then allowed to stand. Take out points

成層之有機層，於其中添加活性碳（NORIT製造CAP SUPER) 2〇份、蒙脫$广 . (Kmrnmne 工業製造 Kuiiipia F ) 20份，於室溫下糌挑 + 3小時後進行過濾。利用水1〇〇份將 所獲得之濾液進行3女 ^ ^ '人水洗，自所獲得之有機層中蒸餾去 除有機浴劑，藉此獲得 月曰環族環氧樹脂（CA£— 2 ) 90份。 %氧當量為216g/eq. βThe organic layer was layered, and activated carbon (manufactured by NORIT CAP SUPER), 2 parts, and montmorillonite (Kmrnmne industrial Kuiiipia F) were added thereto, and the mixture was filtered at room temperature for 3 hours and then filtered. The obtained filtrate was subjected to water washing by 3 parts of water, and the organic bath was distilled off from the obtained organic layer, thereby obtaining a lunar ring epoxy resin (CA£-2) 90. Share. % oxygen equivalent is 216g/eq. β

合成例D 72 201137044 於具備攪拌機、回流冷卻管、攪拌裝置、迪恩—斯達 克管之燒瓶中，一面實施氮氣沖洗一面添加甲苯1〇〇份、3 —%、己烯一 1 —羧酸i26份、三環十五烷二甲醇98份、對 曱苯磺酸3份，然後於回流條件下一面使用迪恩一斯達克 管進行脫水，一面進行15小時反應。反應結束後，添加三 聚磷酸鈉5份，並於10〇t下攪拌！小時。冷卻至室溫後， 添加甲基異丁基酮3〇〇份，並利用水3〇〇份進行3次水洗， 於所獲得之有機層添加矽膠1〇〇份、活性碳丨份，於室溫 下攪拌2小時後進行過濾。自所獲得之濾液中去除溶劑等， 藉此獲得二烯化合物D — 2 1 90份。Synthesis Example D 72 201137044 In a flask equipped with a stirrer, a reflux cooling tube, a stirring device, and a Dean-Stark tube, 1 part of toluene, 3 -%, hexene-1 -carboxylic acid was added while performing nitrogen purge. I26 parts, 98 parts of tricyclopentadecane dimethanol, and 3 parts of p-toluenesulfonic acid were then subjected to dehydration using a Dean-Stark tube under reflux for 15 hours. After the reaction was completed, 5 parts of sodium tripolyphosphate was added and stirred at 10 Torr. hour. After cooling to room temperature, 3 parts of methyl isobutyl ketone was added, and 3 times of water was washed with 3 parts of water, and 1 part of phthalocyanine and activated carbon mash were added to the obtained organic layer. After stirring for 2 hours at room temperature, filtration was carried out. The solvent or the like is removed from the obtained filtrate, whereby a diene compound D - 2 1 90 parts is obtained.

合成例E 於具備攪拌機、回流冷卻管、攪拌裝置之燒瓶中 面實施氮氣沖洗-面添加水12份、1 2 —鶴魏Q 3 8份、構 酸〇·56份、碳酸納，將PH調整為4.7。進而添加氣化三辛 基甲基銨0.6伤（東京化成製造），生成鶴酸系觸媒後，添 加甲笨50份、二婦化合物D_241份進而再次進行授掉， 藉此製成乳液狀態之溶液。將該溶液升溫至贼，一面激 烈地授拌-面添加3G%過氧化氫水24 8份，然後直接於％ C下授拌1 5 j時。繼而，添加i %苛性鋼水溶液Μ份、 硫代硫酸鈉水溶液1 〇份廿、隹— 伤並進仃1小時攪拌，然後靜置。取 出分離成2層之有機厚， 日進而於所獲得之水層添加30份之 甲苯，然後萃取水層中之右她 _ ^ ^ w Υ之有機物。進而重複上述步驟2次， 並混合所獲得之有機層。 具中添加活性碳（NORIT製造 CAP SUPER) 20 份、蒙脫 · 象脱石（Kunlmine工業製造Kunipia 73 201137044 F) 20份，於室溫下攪拌3小時後進行過濾。利用水1〇〇份 將所獲得之濾液進行3次水洗’自所獲得之有機'層蒸铜去 除有機溶劑，藉此獲得脂環族環氧樹脂（CAE—3) 4〇份。 環氧當量為233g/eq. °Synthesis Example E A nitrogen purge was applied to a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, and 12 parts of water, 12 parts of Heiwei Q 3 parts, 56 parts of lanthanum acid, and sodium carbonate were added to adjust the pH. Is 4.7. Furthermore, gasification of trioctylmethylammonium 0.6 was added (manufactured by Tokyo Chemical Industry Co., Ltd.), and after the formation of a tartaric acid-based catalyst, 50 parts of a scorpion and a D-241 part of a disaccharide compound were added and then transferred again, thereby preparing an emulsion state. Solution. The solution was warmed to a thief, and 24 parts of 3G% hydrogen peroxide water was vigorously added to the dough-side, and then directly mixed at 5 C for 1 5 j. Then, an aqueous solution of i% caustic steel was added, and an aqueous solution of sodium thiosulfate was added, and the mixture was shaken for 1 hour, and then allowed to stand. The organic layer separated into two layers was taken out, and 30 parts of toluene was added to the obtained aqueous layer, and then the organic matter of the right _ ^ ^ w 中 in the aqueous layer was extracted. The above procedure was repeated twice, and the obtained organic layer was mixed. 20 parts of activated carbon (CAP SUPER manufactured by NORIT), 20 parts of montmorillonite (Kunpmine Industries, Kunipia 73 201137044 F) were added, and the mixture was stirred at room temperature for 3 hours and then filtered. The obtained filtrate was washed three times with water to remove the organic solvent from the obtained organic 'layer evaporated copper, thereby obtaining 4 parts of an alicyclic epoxy resin (CAE-3). The epoxy equivalent is 233g/eq. °

實施例G — K 較例C — D 使用脂環族環氧樹脂（CAE — 1 )，合成例c、e中所 獲得之脂環族環氧樹脂（CAE — 2) (CAE — 3)，同樣於入 成例5中所獲得之環氧樹脂（S — 5 )’以下述表7所亍之 摻合比（重量份）進行摻合’並進行20分鐘消泡，藉此獲 得實施例及比較例之環氧樹脂組成物。藉由目視判斷所獲 得之環氧樹脂組成物之渾濁’並進行評價。再者，環氧樹 脂（S — 5)之環氧當量為l〇40g/ eq.，重量平均分子量為 2290，比例P之值為22。 [表7] 來老例1 1實施例G 實施例Η 實施例I 比較例C 參考例2 -~~ 脂環族 環氧樹脂 脂環族環氧樹脂/環氧樹脂（重量比） 環氧樹脂 0/100 5/95 15/85 30/70 50/50 100/0 CAE-1 透明 透明 透明 有渾濁 有渾濁 透明 S-5 參考例3 實施例J比較例D參考例4 脂環族 環氧樹脂 脂環族環氧樹脂/環氧樹脂（重量比） 環氧樹脂 0/100 20/80 70/30 100/0 CAE-2 透明 透明 有渾濁 透明 S — 5 參考例5丨實施例Κ 比較例E 參考例6 脂環族 環氧樹脂 脂環族'環氧樹脂/¾ 1氧樹脂（重量比） 環氧樹脂 0/100 20/80 70/30 100/0 CAE-3 h透明 透明 有渾濁 透明 S-5 74 201137044 根據上述結果’藉由將脂環殡環氧樹脂（B)之摻合量 (重量％)設定為！·5〜40重量％，進而基於含環氧環己基 之有機聚石夕氧⑷之分散性而以滿足比例ρ之方式導入， 亦可抑制樹脂渾濁。 、參…、特疋之形態對本發明進行了詳細說明但對於本 領域從業人員而言，可明確可於不脫離本發明之精神與範 圍進行各種變更及修正。 再者’本申請案係基於2〇1〇年3月2日所提出申請之 Si利申請案（曰本特願2°1〇-〇45927 )，引用其所有内 用又’此處所引用之所有參照係作為整體而編入。 【圖式簡單說明】 無 【主要元件符號說明】 無 75Example G - K Comparative Example C - D Using an alicyclic epoxy resin (CAE-1), the alicyclic epoxy resin (CAE-2) (CAE-3) obtained in Synthesis Examples c and e, The epoxy resin (S-5) obtained in Example 5 was blended with the blending ratio (parts by weight) shown in Table 7 below and defoamed for 20 minutes, thereby obtaining examples and comparisons. An epoxy resin composition. The turbidity of the obtained epoxy resin composition was judged by visual observation and evaluated. Further, the epoxy resin (S-5) had an epoxy equivalent of 10 〇 40 g / eq., a weight average molecular weight of 2290, and a ratio of P of 22. [Table 7] Old Example 1 1 Example G Example 实施 Example I Comparative Example C Reference Example 2 -~~ alicyclic epoxy resin alicyclic epoxy resin/epoxy resin (weight ratio) epoxy resin 0/100 5/95 15/85 30/70 50/50 100/0 CAE-1 Transparent transparent transparent turbid and turbid transparent S-5 Reference Example 3 Comparative Example D Reference Example 4 Cycloaliphatic epoxy resin Alicyclic epoxy resin/epoxy resin (weight ratio) Epoxy resin 0/100 20/80 70/30 100/0 CAE-2 Transparent transparent turbid transparent S — 5 Reference Example 5 Example Κ Comparative Example E Reference Example 6 Cycloaliphatic epoxy resin alicyclic 'epoxy resin/3⁄4 1 oxy resin (weight ratio) Epoxy resin 0/100 20/80 70/30 100/0 CAE-3 h transparent transparent turbid transparent S -5 74 201137044 According to the above results 'by setting the blending amount (% by weight) of the alicyclic oxime epoxy resin (B) to! 5 to 40% by weight, and further based on the dispersibility of the organopolycarboyloxy group (4) containing an epoxycyclohexyl group to introduce the ratio ρ, the resin turbidity can also be suppressed. The present invention has been described in detail with reference to the embodiments of the invention, and various modifications and changes can be made without departing from the spirit and scope of the invention. Furthermore, 'this application is based on the Si Li application filed by the application on March 2, 2002 (曰本特愿2°1〇-〇45927), citing all its internal uses and 'here quoted here All reference frames are incorporated as a whole. [Simple description of the diagram] None [Key component symbol description] None 75

Claims (1)

201137044 七、申請專利範圍： 1，一種硬化性樹脂組成物，係含有含環氧環己基之有機 聚矽氧（A )、脂環族環氧樹脂（B )及酸酐（C )， 且脂環族環氧樹脂（B )於含環氧環己基之有機聚矽氧 (A)與脂環族環氧樹脂（B ) 之總量中所佔之量為1.5〜40 重量％。 2· 一種硬化性樹脂組成物，係含有含環氧環己基之有機 聚石夕氧（A )、脂環族環氧樹脂（B )及酸酐（C )， 且脂環族環氧樹脂（B )於含環氧環己基之有機聚矽氧 (A)與脂環族環氧樹脂（B)之總量中所佔之量為2〜40 重量d/p 3. 如申晴專利範圍第1 2 3或2項之硬化性樹脂組成物，其 中月曰環族環氧樹脂（B )於含環氧環己基之有機聚矽氧（A ) 月a %族％氧樹脂（B )之總量中所佔之含量如下： 76 1 〇x (含環氧環己基之有機聚矽氧（A )之重量平均分 2 子量）+(含環氧環己基之有機聚矽氧（A)之環氧當量）重 3 量％以下。 201137044 具有苯基。 、7.如中請專利範圍第項中任—項之硬化性樹脂組 成物’其中，該含環氧環己基之有機聚石夕氧（A)係下 化合物： 具有由二甲基取代、二苯基取代或該等之混合物所構 成之鏈狀聚石夕氧部位，以及有環氧環己基之三維縮 位（倍半石夕氧烧（SilSeSqUi〇xane)部位）㈣段型化合物 8. 一種硬化物，係巾請專利範圍第項中任一項。之 硬化性樹脂組成物經硬化而成。 9·-種光半導體密封用硬化性樹脂紙成物，係由 利範圍第1至7項中任一項之硬化性槲 性樹脂組成物構成。 1〇.一種光半導體裝置’係利用申請專利範圍第9項之 先.導體密封用硬化性樹脂組成物進行硬化及密封而得、 八、圖式： (無） 77201137044 VII. Patent application scope: 1. A curable resin composition containing an organic polyfluorene oxide (A) containing an epoxycyclohexyl group, an alicyclic epoxy resin (B) and an acid anhydride (C), and an alicyclic ring. The epoxy resin (B) is present in an amount of from 1.5 to 40% by weight based on the total of the epoxycyclohexyl group-containing organopolyfluorene (A) and the alicyclic epoxy resin (B). 2. A curable resin composition comprising an organocyclohexyloxy group (A) containing an epoxycyclohexyl group, an alicyclic epoxy resin (B), and an acid anhydride (C), and an alicyclic epoxy resin (B) The amount of the organopolyfluorene (A) and the alicyclic epoxy resin (B) containing the epoxycyclohexyl group is 2 to 40 weight d/p. 3. 2 or 2 of the curable resin composition, wherein the total amount of the epoxy resin (B) in the epoxy group containing the epoxy cyclohexyl group (A) month a % group% oxygen resin (B) The content of the content is as follows: 76 1 〇x (the weight of the organic polyfluorene (A) containing epoxy cyclohexyl group is 2 parts by weight) + (the ring of organopolyfluorene (A) containing epoxycyclohexyl) The oxygen equivalent weight is less than 3% by weight. 201137044 has a phenyl group. 7. The sclerosing resin composition of any one of the above-mentioned patent scopes, wherein the epoxycyclohexyl-containing organic polyoxo (A) compound has: substituted by dimethyl, a phenyl substitution or a mixture of such a mixture, and a three-dimensional adenation of an epoxycyclohexyl group (SilSeSqUi〇xane site) (four) segment type compound 8. For hardened materials, please refer to any of the scope of patents. The curable resin composition is cured. A curable resin paper product for sealing a photo-semiconductor, which is composed of a curable inert resin composition according to any one of items 1 to 7. 1. An optical semiconductor device is obtained by curing and sealing a curable resin composition for conductor sealing according to the ninth application of the patent application. 8. Pattern: (None) 77
TW100106828A 2010-03-02 2011-03-02 Hardened resin composition and hardened product thereof TWI538959B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2010045927 2010-03-02

Publications (2)

Publication Number Publication Date
TW201137044A true TW201137044A (en) 2011-11-01
TWI538959B TWI538959B (en) 2016-06-21

Family

ID=44542235

Family Applications (1)

Application Number Title Priority Date Filing Date
TW100106828A TWI538959B (en) 2010-03-02 2011-03-02 Hardened resin composition and hardened product thereof

Country Status (5)

Country Link
JP (1) JP5878862B2 (en)
KR (1) KR20130036184A (en)
CN (1) CN102791760A (en)
TW (1) TWI538959B (en)
WO (1) WO2011108588A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI656151B (en) * 2016-12-28 2019-04-11 日商三菱瓦斯化學股份有限公司 Prepreg, laminated board, metal foil laminated board, printed circuit board, and multilayer printed circuit board

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5626856B2 (en) * 2010-06-11 2014-11-19 日本化薬株式会社 Curable resin composition and cured product thereof
JP5680928B2 (en) * 2010-10-04 2015-03-04 新日鉄住金化学株式会社 Epoxy silicone resin-containing curable resin composition
JP5472924B2 (en) * 2010-10-21 2014-04-16 日本化薬株式会社 Curable resin composition and cured product thereof
JP5891617B2 (en) * 2011-05-17 2016-03-23 三菱化学株式会社 Thermosetting resin composition, semiconductor device member, and semiconductor device using the same
JP6031739B2 (en) * 2011-09-08 2016-11-24 三菱化学株式会社 Thermosetting resin composition, semiconductor device member, and semiconductor device using the same
WO2013035740A1 (en) * 2011-09-09 2013-03-14 日本化薬株式会社 Curable resin composition for sealing optical semiconductor element and cured product thereof
JP6150415B2 (en) * 2011-09-27 2017-06-21 日本化薬株式会社 Curable resin composition and cured product thereof
KR101905834B1 (en) * 2012-05-31 2018-10-08 엘지이노텍 주식회사 Epoxy resin composition and light emitting apparatus
JP2014056924A (en) * 2012-09-12 2014-03-27 Hitachi Chemical Co Ltd Semiconductor device manufacturing method and thermosetting resin composition used therefor, and semiconductor device obtained by those
JP6162557B2 (en) * 2012-09-21 2017-07-12 日本化薬株式会社 Transparent adhesive material
JP5967654B2 (en) * 2012-11-28 2016-08-10 日本化薬株式会社 Resin composition and cured product thereof (2)
US9326350B2 (en) 2013-02-07 2016-04-26 Everlight Electronics Co., Ltd. Light-emitting device with multi-color temperature and multi-loop configuration
KR102007194B1 (en) 2013-02-14 2019-08-05 엘지이노텍 주식회사 Epoxy resin composite and light emitting apparatus using the same
WO2015056723A1 (en) * 2013-10-16 2015-04-23 日本化薬株式会社 Curable resin composition and cured product thereof
WO2016052212A1 (en) * 2014-10-02 2016-04-07 株式会社ダイセル Curable composition for nanoimprinting
JP2016164254A (en) * 2015-02-10 2016-09-08 株式会社ダイセル Curable epoxy resin composition for optical material

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4205368B2 (en) * 2002-06-11 2009-01-07 株式会社Ａｄｅｋａ Curable composition for optical materials
JP4651935B2 (en) * 2003-12-10 2011-03-16 東レ・ダウコーニング株式会社 Active energy ray-curable organopolysiloxane resin composition, light transmission member, and method for producing light transmission member
JP4629367B2 (en) * 2004-05-31 2011-02-09 東レ・ダウコーニング株式会社 Active energy ray-curable organopolysiloxane resin composition, optical transmission member and method for producing the same
WO2006003990A1 (en) * 2004-07-02 2006-01-12 Nippon Kayaku Kabushiki Kaisha Photosensitive resin composition for optical waveguide and optical waveguide composed of cured product thereof
JP2006225515A (en) * 2005-02-17 2006-08-31 Jsr Corp Optical semiconductor element, sealing material therefor and sealing composition
WO2007135909A1 (en) * 2006-05-18 2007-11-29 Nippon Kayaku Kabushiki Kaisha Thermosetting resin composition and cured product thereof
JP5179839B2 (en) * 2007-11-08 2013-04-10 株式会社ダイセル Epoxy resin composition and cured product thereof
WO2010026714A1 (en) * 2008-09-03 2010-03-11 日本化薬株式会社 Siloxane compound, curable resin composition, cured object obtained therefrom, and photosemiconductor element
KR101692450B1 (en) * 2009-06-22 2017-01-03 니폰 가야꾸 가부시끼가이샤 Polyvalent carboxylic acid, composition thereof, curable resin composition, cured product, and method for manufacturing a polyvalent carboxylic acid

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI656151B (en) * 2016-12-28 2019-04-11 日商三菱瓦斯化學股份有限公司 Prepreg, laminated board, metal foil laminated board, printed circuit board, and multilayer printed circuit board

Also Published As

Publication number Publication date
KR20130036184A (en) 2013-04-11
WO2011108588A1 (en) 2011-09-09
JP5878862B2 (en) 2016-03-08
JPWO2011108588A1 (en) 2013-06-27
TWI538959B (en) 2016-06-21
CN102791760A (en) 2012-11-21

Similar Documents

Publication Publication Date Title
TW201137044A (en) Curable resin composition and cured article thereof
JP6669653B2 (en) Polyvalent carboxylic acid, polyvalent carboxylic acid composition containing the same, epoxy resin composition, thermosetting resin composition, cured product thereof, and optical semiconductor device
TWI488890B (en) A polycarboxylic acid composition and a method for producing the same, and a hardening resin composition comprising the polycarboxylic acid composition
JP5730852B2 (en) Method for producing organopolysiloxane, organopolysiloxane obtained by the production method, and composition containing the organopolysiloxane
TWI504628B (en) Hardened resin composition and hardened product thereof
TWI512016B (en) Polycarboxylic acid resin and its composition
TWI494376B (en) A hardened resin composition for light semiconductors and a hardened product thereof
TWI485202B (en) Hardened resin composition and hardened product thereof
TWI564318B (en) Epoxy resin composition
JP2012087249A (en) Curable resin composition and cured product thereof
TW201038549A (en) Diolefin compound, epoxy resin and composition thereof
JP5832601B2 (en) Curable resin composition and cured product thereof
JP6767816B2 (en) Polycarboxylic acid and polyvalent carboxylic acid composition containing it, epoxy resin composition, cured products thereof, and optical semiconductor device
JP6478808B2 (en) Polyvalent carboxylic acid, polyvalent carboxylic acid composition containing the same, and epoxy resin composition

Legal Events

Date Code Title Description
MM4A Annulment or lapse of patent due to non-payment of fees