TW201235375A - Curable epoxy resin composition - Google Patents

Curable epoxy resin composition Download PDF

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Publication number
TW201235375A
TW201235375A TW101100544A TW101100544A TW201235375A TW 201235375 A TW201235375 A TW 201235375A TW 101100544 A TW101100544 A TW 101100544A TW 101100544 A TW101100544 A TW 101100544A TW 201235375 A TW201235375 A TW 201235375A
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resin composition
epoxy resin
optical semiconductor
compound
group
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TW101100544A
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Chinese (zh)
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Atsuo Tatsumi
Hirose Suzuki
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Daicel Corp
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    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/226—Mixtures of di-epoxy 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
    • C08G59/22—Di-epoxy compounds
    • C08G59/26—Di-epoxy compounds heterocyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • 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
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • 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
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
    • H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
    • H01L2224/321—Disposition
    • H01L2224/32151—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/32221—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/32245—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/4805—Shape
    • H01L2224/4809—Loop shape
    • H01L2224/48091—Arched
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/481—Disposition
    • H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/48245—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
    • H01L2224/48247—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a bond pad of the item
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
    • H01L2224/732—Location after the connecting process
    • H01L2224/73251—Location after the connecting process on different surfaces
    • H01L2224/73265—Layer and wire connectors
    • 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

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  • 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)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
  • Epoxy Resins (AREA)
  • Led Device Packages (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention provides a curable epoxy resin composition. The curable epoxy resin composition can provide cured products which have high transparency, heat resistance, light resistance, crack resistance, and what's more, excellent reflow resistance. The curable epoxy resin composition is characterized by containing alicyclic epoxy compounds (A), monoallyl diglycidyl isocyanurate compounds (B) represented by following formula (1), polycarbonate polyols (C), curing agents (D) and curing catalysts (E). [In the formula, R1 and R2 represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.]

Description

201235375 ， 六、發明說明： 【發明所屬之技術領域] 本發明係關於硬化性環氧樹脂組成物、將該硬化性 環氧樹脂組成物硬化而成之硬化物、包含該硬化性環氧 樹脂組成物而構成之光半導體密封用樹脂組成物、及使 用該光半導體密封精脂組成物將光半導體元件密封而 成之光半導體裝置。 【先前技術】 近年來，光半導體裝置之高輸出化進展，於如此的 光半導體裝置使用之樹脂要求高度㈣熱性及财光性。 例如：於藍色、白色光半導體用之密封材（密封樹脂）， 由光半導體元件發出之光及熱導致之密封樹脂的黃變成 為問題。黃變的密封樹脂，由於會吸收來自於光半導體 元件所發的光，故會使從光半導體裝置輸出之光的光度 隨時間降低。 & 至今為止’高耐熱性之密封樹脂，已知有含有異三 聚氰酸單烯丙基二環氧丙酯與雙酚A型環氧樹脂之組成 物（參照專利文獻1)。但是即使將上述組成物作為高輸出 的藍色、白色光半導體用之密封樹脂，仍會由於光半導 體元件發出的光及熱導致著色進行，使原本應輸出的光 被吸收’其結果會有從光半導體裝置輸出的光的光度降 低的問題。 [先前技術文獻] [專利文獻] [專利文獻1]日本特開2000-344867號公報 201235375 【發明内容】 [發明欲解決之課題] 就：有高度耐熱性及耐光性且不易黃變之密封樹脂 :二”有，環氧環己基甲基(3,4_環氧)環己烧㈣ 曰，％氧％<己基甲基（3,4-環氧）環己燒緩酸醋與ε-己 内酉曰之加成物、1，2,8,9--環惫據捋陡楚曰 ^ , ,，y 一 ％氧檸檬烯荨具脂環骨架之液 & '樹月曰。但是，該等脂環環氧樹脂的硬化物不 : 當施加冷熱循環(反覆加熱與冷卻)此類的 ，、·、衝擊時’會有產生龜裂（裂隙）等問題。 上述光半導體裝置’通常會經歷利用附著焊料而將 “先+導體裝置之電極接合於配線基板的回流步驟。近 年來《作接合材的焊料，逐漸採用高熔點之無船焊料 ’於回流步驟的加熱處理，採用更高溫度⑽：峰部溫 度為240〜260t)e判明於如此的狀況下，於習知的光半 導體裝置目4步驟的加熱處理會造成密封樹脂從光半 導體裝置之導線架剝離，或密封樹脂產生龜裂等劣化的 問題發生。 因此’現狀為就光半導體裝置中的密封樹脂而言， 需求兼具冑耐熱性、耐綠、及耐㈣性，且相流性 也優異的透明密封樹脂。又，本說明書中，「耐回流性 」係心以回流步驟將光半導體裝置進行加熱處理時，密 封樹脂不會發生從導線架剝離或龜裂等的特性。 因此本發明之目的在於提供能提供兼具高透明性、 而ί熱性、耐光性、为而+ χ,ι %. 及耐龜裂性，且耐回流性也優異的硬 化物的硬化性環氧樹脂組成物。 201235375 又’本發明之另一目的在於提供將上述硬化性環氧 樹脂組成物硬化而成之兼具高透明性、耐熱性、耐光性 、及耐龜裂性，且耐回流性亦優異的硬化物。 又，本發明之又另一目的在於提供包含上述硬化性 環氧樹脂組成物而構成之光半導體密封用樹脂組成物， 其可獲得回流步驟之加熱處理導致之劣化或光度隨時間 降低受抑制的光半導體裝置^ 又，本發明之另一目的在於提供回流步驟之加熱處 理導致之劣化或光度隨時間之降低受抑制之光半導體裝 置，其可藉由使用上述光半導體密封用樹脂組成物將光 半導體元件密封而獲得。 [解決課題之手段] 本案發明人等為了解決上述技術課題努力探討，結 果發現.含有脂環環氧化合物、異三聚氰酸單烯丙基二 環氧丙s曰化合物、及聚碳酸酯多元醇當作必要成分，且 進一步含有硬化劑或硬化觸媒之硬化性環氧樹脂組成物 ，可提供兼具高透明性、耐熱性、耐光性、耐龜裂性、 耐回"’l !生之硬化物，以該硬化物將光半導體元件予以密 封而得之光半導體装置，不易發生回流步驟之加熱處理 導致之劣化或光度隨時間降低的情形，乃完成本發明。 亦p本發明提供一種硬化性環氧樹脂組成物，其 包3 .知環j衣氧化合物（A)、與以下式（1)表示之異三聚 氰I單烯丙基一環氧丙酯化合物（B)、與聚碳酸酯多元醇 (C)、與硬化劑（D)或硬化觸媒（E); (1) 201235375 R2201235375, 6. Description of the Invention: [Technical Field of the Invention] The present invention relates to a curable epoxy resin composition, a cured product obtained by hardening the curable epoxy resin composition, and a composition comprising the curable epoxy resin A resin composition for optical semiconductor sealing which is composed of a material, and an optical semiconductor device in which an optical semiconductor element is sealed by using the optical semiconductor sealing resin composition. [Prior Art] In recent years, the high output of optical semiconductor devices has progressed, and the resin used in such an optical semiconductor device requires a high degree of thermal and financial properties. For example, in a sealing material (sealing resin) for blue and white light semiconductors, light emitted from an optical semiconductor element and yellow of a sealing resin caused by heat become a problem. The yellowing sealing resin absorbs light from the optical semiconductor element, so that the luminosity of the light output from the optical semiconductor device decreases with time. & As a sealing resin having high heat resistance, a composition containing a monoallyl diglycidyl isocyanate and a bisphenol A type epoxy resin is known (see Patent Document 1). However, even if the above-mentioned composition is used as a high-output sealing resin for blue and white photo-semiconductors, coloring due to light and heat emitted from the optical-semiconductor element causes the light to be output to be absorbed. The problem of the illuminance of light output by the optical semiconductor device is lowered. [Prior Art] [Patent Document 1] [Patent Document 1] JP-A-2000-344867, JP-A-201235375 [Disclosure] The problem of the invention is to provide a sealing resin which is highly resistant to light and is resistant to yellowing. : 二"有, epoxy cyclohexylmethyl (3,4_epoxy) cyclohexene (four) 曰,% oxygen% < hexylmethyl (3,4-epoxy) cyclohexanone acid vinegar and ε- The adduct of the cockroach, 1,2,8,9--ring 惫 捋 曰 曰 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , 曰 曰The hardened material of the alicyclic epoxy resin does not have problems such as cracking (cracking) when applying such a cold-heat cycle (repetitive heating and cooling), etc. The above-mentioned optical semiconductor device 'will usually The reflow step of bonding the electrodes of the +conductor device to the wiring substrate by the adhesion of the solder is experienced. In recent years, "the solder used as the bonding material, the high-melting-point ship-free solder is gradually used in the heating process of the reflow step, and the higher temperature (10): the peak temperature is 240 to 260 t) is judged under such a condition. The heat treatment in the fourth step of the optical semiconductor device causes a problem that the sealing resin is peeled off from the lead frame of the optical semiconductor device, or the sealing resin is deteriorated such as cracks. Therefore, in the case of the sealing resin in the optical semiconductor device, it is required to have a transparent sealing resin which is excellent in heat resistance, green resistance, and resistance to four (4) and excellent in phase flow property. In addition, in the present invention, when the optical semiconductor device is subjected to a heat treatment by a reflow step, the sealing resin does not have characteristics such as peeling or cracking from the lead frame. Therefore, an object of the present invention is to provide a hardenable epoxy which can provide a cured product which has high transparency, heat resistance, light resistance, and is excellent in reflow resistance and is excellent in reflow resistance. Resin composition. 201235375 Further, another object of the present invention is to provide a hardening which is excellent in transparency, heat resistance, light resistance, and crack resistance, and which is excellent in reflow resistance, obtained by curing the curable epoxy resin composition. Things. Moreover, another object of the present invention is to provide a resin composition for optical semiconductor sealing comprising the above-mentioned curable epoxy resin composition, which can be deteriorated by heat treatment in a reflow step or reduced in luminosity with time. In the optical semiconductor device of the present invention, it is another object of the present invention to provide an optical semiconductor device which is deteriorated by the heat treatment in the reflow step or which has a reduced luminosity with time. The semiconductor element is obtained by sealing. [Means for Solving the Problem] In order to solve the above-mentioned technical problems, the inventors of the present invention have found that an alicyclic epoxy compound, an isomeric cyanuric monoallyl propylene oxide compound, and a polycarbonate are found. Alcohol is an essential component, and further contains a hardening agent or a hardening epoxy resin composition of a curing catalyst, which provides both high transparency, heat resistance, light resistance, crack resistance, and resistance to 'l! The cured product of the raw material, which is obtained by sealing the optical semiconductor element with the cured product, is less likely to be deteriorated by the heat treatment in the reflow step or the luminosity is lowered with time, and the present invention has been completed. Also, the present invention provides a curable epoxy resin composition comprising: a cyclized compound (A), and a different melamine I monoallyl-glycidyl ester represented by the following formula (1) Compound (B), with polycarbonate polyol (C), with hardener (D) or hardening catalyst (E); (1) 201235375 R2

再者，提供如前述硬化性環氧樹脂組成物，其中前 述脂環環氧化合物（A)之脂環環氧基為環氧己烯基。 再者’提供如前述硬化性環氧樹脂組成物，其中前 述脂環環氧化合物（A)為下式（1-1)表示之化合物Further, a curable epoxy resin composition as described above, wherein the alicyclic epoxy group of the alicyclic epoxy compound (A) is hexylene oxide. Further, the above-mentioned curable epoxy resin composition is provided, wherein the alicyclic epoxy compound (A) is a compound represented by the following formula (1-1)

1) 再者，提供如前述硬化性環氧樹脂組成物，更包含 硬化促進劑（F)。 再者，提供如前述硬化性環氧樹脂組成物，更包含 橡膠粒子。 再者，提供如前述硬化性環氧樹脂組成物，更包含 丙烯酸基嵌段共聚物。 又，本發明提供將前述硬化性環氧樹脂組成物予以 硬化而成的硬化物。 又’本發明提供包含前述硬化性環氧樹脂組成物而 構成之光半導體密封用樹脂組成物。 又’本發明提供以前述光半導體密封用樹脂組成物 將光半導體元件予以密封而得之光半導體裝置。 201235375 [發明之效果] 本發明之硬化性ϊ哀氧樹脂組成物由於具上述構成 故藉由使該樹脂組成物硬化’可獲得兼具高耐熱性、耐 光性、透明性、及耐龜裂性，且耐回流性亦為優異之硬 化物。又，使用本發明之硬化性環氧樹脂組成物將光半 導體元件予以密封而得之光半導體裝置，即使於回流步 驟之高溫處理也不易劣化，且光度不易隨時間降低，故 具有優異的品質及耐久性。 【實施方式】 [實施發明之形態] 〈硬化性環氧樹脂組成物&gt; 本發明之硬化性環氧樹脂組成物，其特徵為包含： 脂環環氧化合物（A)、與以了式（1)表示之異三聚氰酸單 嫦丙基二環氧丙酯化合物（B)、與聚碳酸酯多元醇（c)、 與硬化劑（D)或硬化觸媒;1) Further, a curable epoxy resin composition as described above is further provided, and a hardening accelerator (F) is further included. Further, a curable epoxy resin composition as described above is further provided, and rubber particles are further contained. Further, a curable epoxy resin composition as described above is further provided, and an acrylic-based block copolymer is further included. Further, the present invention provides a cured product obtained by curing the curable epoxy resin composition. Further, the present invention provides a resin composition for optical semiconductor sealing comprising the above-mentioned curable epoxy resin composition. Further, the present invention provides an optical semiconductor device obtained by sealing an optical semiconductor element with the resin composition for optical semiconductor sealing. 201235375 [Effects of the Invention] The curable oxime resin composition of the present invention has high heat resistance, light resistance, transparency, and crack resistance by curing the resin composition by the above configuration. And the reflow resistance is also an excellent cured product. Moreover, the optical semiconductor device obtained by sealing the optical semiconductor element using the curable epoxy resin composition of the present invention is not easily deteriorated even in the high temperature treatment in the reflow step, and the luminosity is not easily lowered with time, so that it has excellent quality and Durability. [Embodiment] [Form of the invention] <Curable epoxy resin composition> The curable epoxy resin composition of the present invention is characterized by comprising: an alicyclic epoxy compound (A) and a formula ( 1) an isomeric cyanuric propyl diglycidyl ester compound (B), a polycarbonate polyol (c), a hardener (D) or a hardening catalyst;

[式中’ R1及R2表示氫原子或碳數1〜8之烷基]。本發明之 硬化性環氧樹脂組成物’視需要，也可更含有硬化促進 劑（F) 〇 &lt;脂環環氧化合物（A)&gt; 本發明可使用之脂環環氧化合物（A)，包含⑴具有以 201235375 構成脂環&gt; 4 化合物、二鄰的2個碳原子與氧原子構成之環氧基的 ⑴⑴）壞氧基直接卩單鍵鍵結錢環之化合物。 成之環氧^構成脂環之相鄰的2個碳原子與氧原子構 當中任意：用脂環環氧基)的化合物’可從周知至慣用者 佳。 。其中’脂環環氧基’為環氧己烯基為較 (0具有 成之環氣基 以下式（I)表 以構成脂環之相鄰的2個碳原子與氧原子構 的化合物，尤其從透明性、耐熱性之觀點， 示之脂環環氧樹脂為較佳。[wherein R1 and R2 represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms]. The curable epoxy resin composition of the present invention may further contain a curing accelerator (F) 〇 &lt; alicyclic epoxy compound (A) &gt; alicyclic epoxy compound (A) which can be used in the present invention. And (1) a compound having (1) (1)) a bad oxy group directly bonded to a ring of a ring having an alicyclic &gt; 4 compound and two adjacent carbon atoms and an oxygen atom in 201235375. The epoxy compound which constitutes two adjacent carbon atoms and oxygen atoms adjacent to the alicyclic ring is preferably a compound of the alicyclic epoxy group. . Wherein the 'alicyclic epoxy group' is a cyclohexenyl group which is a compound having a ring gas group of 0 (the following formula (I) is a structure in which two carbon atoms adjacent to the alicyclic ring are bonded to an oxygen atom, especially From the viewpoint of transparency and heat resistance, an alicyclic epoxy resin is preferred.

式（I)中 Φ ’Χ表示單鍵或連結基（具有1個以上原子之2 價之基）。、+， 遗連m基’例如：2價之烴基、幾基、騎鍵 、酉旨鍵、π綠 反®文醋基、醯胺基、及將該等連結多個而得之 基等。 式（1)中之x為單鍵之脂環環氡樹脂’例如下式表示 之化合物。In the formula (I), Φ ' represents a single bond or a linking group (having a base of two or more valences of one or more atoms). And +, the m-group is carried out, for example, a divalent hydrocarbon group, a few groups, a riding bond, a ruthenium bond, a π-green anti-viral vinegar group, a guanamine group, and a plurality of such groups. The alicyclic cyclic oxime resin in which x in the formula (1) is a single bond is, for example, a compound represented by the following formula.

如此的脂環環氧化合物例如也可使用CELLOXIDE 8000(Daicel(股）製）等市售品。 2價之烴基’例如碳數卜1 8之直鍵狀或支鏈狀之伸院 基、2價之脂環烴基等。碳數卜18之直鏈狀或支鏈狀之伸 201235375 -烷基’例如：亞甲基、甲基亞曱基、二甲基亞甲基、伸 乙基、伸丙基、二亞甲基等。2價之脂環烴基，例如：1，2_ 環伸戍基、1，3_環伸戊基、環亞戍基、1&gt;2環伸己基、】 環伸己基、M-環伸己基、環亞己基等2價之環伸燒基 含環亞烷基）等。 連結基X，較佳為含氧原子之連結基，具體而言例如 -CO-、_0-C0-0·、_coo_、_〇_、_c〇NH ;該等基連接多 個而得之基；該等基之i或2個以上與2價之烴基之i或2 個以上連結而得之基等。2價之烴基，例如前述之基。 式（I)表示之脂環環氧化合物之代表例，例如下式 (1-1)〜（1-8)表示之化合物等。例如可使用CELLOXIDE 2021P、CELL〇XIDE2081(Daicel(股）製）等市售品。又， 下式（1-1)〜（1-8)中，卜m表示1〜30之整數。R表示碳數卜8 之伸烷基’例如亞甲基、伸乙基、伸丙基、伸異丙基、 伸丁基、伸異丁基、伸第二丁基、伸戊基、伸己基、伸 庚基、伸辛基等直鏈狀或支鏈狀伸烷基《該等之中，亞 甲基、伸乙基、伸丙基、異伸丙基等碳數1〜3之直鏈狀或 支鏈狀伸烷基較佳。 -10- 201235375As such an alicyclic epoxy compound, for example, a commercially available product such as CELLOXIDE 8000 (manufactured by Daicel Co., Ltd.) can also be used. The divalent hydrocarbon group 'e.e., a straight or branched chain of a carbon number, a divalent alicyclic hydrocarbon group, or the like. Linear or branched extension of carbon number 18 201235375 -alkyl 'e.g.: methylene, methyl sulfenyl, dimethylmethylene, ethyl, propyl, dimethylene Wait. a divalent alicyclic hydrocarbon group, for example, 1,2_cyclodecyl, 1,3_cyclopentyl, cycloalkylene, 1&gt; 2 cyclohexyl, cyclohexyl, M-cyclohexyl, ring A divalent cycloalkyl group such as a hexylene group or a cycloalkylene group or the like. The linking group X is preferably a linking group containing an oxygen atom, specifically, for example, -CO-, _0-C0-0·, _coo_, _〇_, _c〇NH; these groups are bonded to a plurality of groups; i or two or more of these groups are bonded to i or two or more of divalent hydrocarbon groups. A divalent hydrocarbon group such as the aforementioned group. Representative examples of the alicyclic epoxy compound represented by the formula (I) are, for example, compounds represented by the following formulas (1-1) to (1-8). For example, commercially available products such as CELLOXIDE 2021P and CELL® XIDE2081 (manufactured by Daicel Co., Ltd.) can be used. Further, in the following formulae (1-1) to (1-8), m represents an integer of 1 to 30. R represents an alkyl group of a carbon number, such as methylene, ethyl, propyl, isopropyl, butyl, isobutyl, dibutyl, pentyl, hexyl a linear or branched alkyl group such as a heptyl group or a octyl group. Among these, a linear chain having a carbon number of 1 to 3 such as a methylene group, an exoethyl group, a propyl group, and an exo-propyl group A branched or branched alkyl group is preferred. -10- 201235375

(1-5) Ο(1-5) Ο

Ο (1—6)Ο (1-6)

，例如下 (i i)環氧基直接以單鍵鍵結於脂環之化合物 式（II)表示之化合物。For example, a compound represented by the formula (II) wherein the (i i) epoxy group is directly bonded to the alicyclic ring by a single bond.

式（II)中，R’為p價之醇去除p個-OH後之基 表自然數。p價之醇[R’-(OH)p]，例如2,2-雙（羥基 丁醇等多元醇等（碳數1〜15之醇等）。p宜為1~6, ，ρ、η代 甲基）-1-n為1〜30 -11 - 201235375 較佳。P為2以上時’各（）内(圓括弧内)之基的 同也可為不同。上述化合物，具體而言，例如2,2_雙_ 基甲基丁醇之i，2-環氧作環氧乙烧基)環： 成物、EHPE 3150(Daicel(股）製）等。 凡 ° 該等脂環環氧化合物（A)可以單獨使用，或組人2 以上使用。脂環環氧化合物⑷，以上式㈣表示二4In the formula (II), R' is a natural number of the base of the p-valent alcohol after removing p-OH. The p-valent alcohol [R'-(OH)p] is, for example, 2,2-bis (polyol such as hydroxybutanol or the like (alcohol having a carbon number of 1 to 15 or the like). p is preferably 1 to 6, ρ, η. The methyl group-1-n is 1~30 -11 - 201235375 is preferred. When P is 2 or more, the same applies to the base of each (in parentheses). Specific examples of the above compound include, for example, 2,2-bis-methylbutanol i,2-epoxy epoxide-based ring: a compound, EHPE 3150 (manufactured by Daicel Co., Ltd.), and the like.凡 ° These alicyclic epoxy compounds (A) can be used alone or in groups of 2 or more. Alicyclic epoxy compound (4), the above formula (4) represents two 4

環氧環己基甲基（3’4_環氧）環己烧㈣醋、咖 D 2021P尤佳。 脂環環氧化合物（A)之使用量（含量）不肖別限定相 對於脂環環氧化合物（A)與異三聚氰酸單稀丙基二環氧 丙醋化合物（B)之總量（1 00重量％)，為5〇〜9〇重量％較佳， 更佳為60〜90重量％，又更伟兔7Π &amp; θ 里里/0又旯佳為70〜90重量％。脂環環氧化 合物（A)之使用.量低於50重量％時，異三聚氰酸單稀丙基 二環氧丙酯化合物（B)之溶解性不夠，若置於室溫，有時 會容易析出。另一方面，脂環環氧化合物（A)之使用量若 超過90重量。/。’當製作光半導體裝置時有時會容易發 生龜裂。成分（A)、成分（B)、及成分（c)之總量（1〇〇重量 %)中，脂環環氧化合物（A)與異三聚氰酸單烯丙基二環氧 丙醋化合物（B)之含量總和（總量）不特別限定為5〇〜99 重量％較佳。 &lt;異三聚氰酸單烯丙基二環氧丙酯化合物（b)&gt; 本發明可使用之異三聚氰酸單烯丙基二環氧丙醋化 合物（B)，可以用下列通式（1)表示。 -12- (1) 201235375Epoxycyclohexylmethyl (3'4_epoxy) cyclohexane (4) vinegar, coffee D 2021P is especially preferred. The amount (content) of the alicyclic epoxy compound (A) is not limited to the total amount of the alicyclic epoxy compound (A) and the iso-propylene cyanide monoglycidyl acetonate compound (B) ( 100% by weight), preferably 5 〇 to 9 〇 by weight, more preferably 60 to 90% by weight, and more preferably 7 Π & θ 里里/0 is preferably 70 to 90% by weight. When the amount of the alicyclic epoxy compound (A) is less than 50% by weight, the solubility of the monoisopropyl cyanurate compound (B) is insufficient, and if it is left at room temperature, sometimes Will be easy to precipitate. On the other hand, the alicyclic epoxy compound (A) is used in an amount exceeding 90% by weight. /. When cracking an optical semiconductor device, cracks may occur easily. In the total amount (1% by weight) of the component (A), the component (B), and the component (c), the alicyclic epoxy compound (A) and the isomeric cyanuric acid monoallyl propylene glycol vinegar The sum (total amount) of the content of the compound (B) is not particularly limited to 5 〇 to 99% by weight. &lt;Iso-cyanuric acid monoallyl diglycidyl ester compound (b)&gt; The isocyanuric acid monoallyl propylene oxide propylene vinegar compound (B) which can be used in the present invention can be used as follows Expressed by the formula (1). -12- (1) 201235375

惟’式中’ R1及R2表示氫原子或碳數i〜8之烷基。 碳數1〜8之烷基’例如：曱基、乙基、丙基、異兩基 、丁基、異丁基、第二丁基、戊基、己基、庚基、辛基 等直鏈狀或支鏈狀烷基。該等之_，曱基、乙基、内其 、異丙基等碳數1〜3之直鏈狀或支鏈狀烷基為較佳。尤其 R1及R2為氫原子較佳。 異二聚氰酸單烯丙基二環氧丙酯化合物（B)之代表 者例如異二聚亂酸早稀丙基二環氧丙醋、異三聚氛 酸卜稀丙基·3,5_雙（2_曱基環氧丙基）S旨、#三聚氰酸 ι-(2-曱基丙婦基）_3,5_二環氧丙基醋、異三聚氣酸κ(2_ 曱土丙烯基）-3,5·雙（2_甲基環氧丙基）酯等。又，異三聚 fL S夂早烯丙基二環氧丙酯化合物⑻可以單獨使用1 組合使用2種以上。 ^ 異一聚氰酸單烯丙基二環氧丙酯化合物 解於上述脂環《结^ 化合物㈧與異物⑷之範圍任意混合，脂環環氧 之比例不特別P卜仏早稀丙基二環氧丙6旨化合物⑻ 稀丙基二環氧脂環環氧化合物（A):異三聚氰酸單 )較佳。為該範園曰外合物（B)宜為5〇: 5〇〜9〇: 1〇(重量比 固外時，溶解性不容易獲得。 、二鼠峻單埽丙基二環氧丙醋化合物（B)，也可使 -13- 201235375 用添加醇或酸酐等會與環氧基反應之化合物而預先改性 者。 脂環環氧化合物（A)與異三聚氰酸單烯丙基二環氧 丙酯化合物（B)之總量，不特別限定，相對於環氧樹脂（ 具環氧基之化合物）之總量（1〇〇重量％)，為5〇〜1〇〇重量％ 較佳。 &lt;聚碳酸酯多元醇（C)&gt; 聚碳酸酯多元醇（C)，為分子内具有2個以上之羥基 的聚碳酸酯。其中，聚碳酸酯多元醇（C)，較佳為分子内 具有2個末端經基之聚碳酸酯二醇。又，聚碳酸酯多元醇 (C)中的羥基’可為醇性羥基也可為酚性羥基。 聚碳酸酯多元醇（C) ’可以與製造通常之聚碳酸酯多 元醇之方法同樣，利用光氣法或使用如碳酸二曱酯、碳 酸二乙酯之類的碳酸二烷酯或碳酸二苯酯之碳酸酯交換 反應（例如可參照曰本特開昭62-187725號公報、日本特 開平2-175721 5虎公報、日本特開平2-49025號公報、曰本 特開平3-220233號公報、日本特開平3-252420號公報等） 等合成。聚碳酸酯多元醇（C)之碳酸酯鍵由於不易遭熱分 解’故含有聚碳酸酯多元醇之樹脂硬化物即使於高溫高 濕下仍顯示優異的安定性。又，聚碳酸酯多元醇（C)可以 單獨使用1種或組合2種以上使用。 與上述碳酸一烧S旨或碳酸二苯醋一起使用在碳酸酉旨 交換反應的多元醇’例如：1，6 -己烧二醇、乙二醇、二 乙二醇、1,3 -丙二醇、1，4 -丁 二醇、1，3_丁 二醇、2,3 -丁 二醇、1，5 -戊二醇、3·曱基-1，5-戊二醇、L4 -環己烷二曱 -14- 201235375However, in the formula, R1 and R2 represent a hydrogen atom or an alkyl group having a carbon number of i8. Alkyl group having 1 to 8 carbon atoms such as a mercapto group, an ethyl group, a propyl group, a hetero-diyl group, a butyl group, an isobutyl group, a second butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group or the like Or branched alkyl. Preferably, a linear or branched alkyl group having 1 to 3 carbon atoms such as a mercapto group, an ethyl group, an internal group or an isopropyl group is preferred. In particular, R1 and R2 are preferably a hydrogen atom. Representative of the isocyanuric acid monoallyl diglycidyl ester compound (B), for example, heterodimeric acid, early dipropyl propylene glycol propylene glycol, isotrimeric acid isopropyl propylene, 3,5 _双(2_曱-glycidylpropyl)S,#Cyanuric acid ι-(2-mercaptopropyl)_3,5-diepoxypropyl vinegar, isotrimeric gas κ(2_ Aluminium propylene)-3,5.bis(2-methylepoxypropyl) ester. Further, the heterotrimeric fL S夂 early allyl diglycidyl ester compound (8) may be used alone or in combination of two or more. ^ The iso-polycyanate monoallyl diglycidyl ester compound is arbitrarily mixed in the above-mentioned alicyclic ring, and the ratio of the alicyclic epoxy is not particularly P. The epoxy propylene 6 compound (8) is preferably a propylene diepoxy epoxide epoxy compound (A): isocyanuric acid mono). For the Fanyuan 曰 曰 (B) is preferably 5 〇: 5 〇 ~ 9 〇: 1 〇 (when the weight is higher than the solid, the solubility is not easy to obtain. 二, 鼠 峻 埽 monopropyl propylene glycol vinegar The compound (B) can also be previously modified by adding a compound which reacts with an epoxy group, such as an alcohol or an acid anhydride, with the addition of an alcohol or an acid anhydride. The alicyclic epoxy compound (A) and the isomeric cyanuric monoallyl group The total amount of the diglycidyl ester compound (B) is not particularly limited, and is 5 〇 to 1 〇〇% by weight based on the total amount of the epoxy resin (the compound having an epoxy group) (1% by weight). Preferably, the polycarbonate polyol (C) is a polycarbonate having two or more hydroxyl groups in the molecule, wherein the polycarbonate polyol (C) is more preferred. It is preferably a polycarbonate diol having two terminal groups in the molecule. Further, the hydroxyl group in the polycarbonate polyol (C) may be an alcoholic hydroxyl group or a phenolic hydroxyl group. 'Can be used in the same manner as in the production of a conventional polycarbonate polyol, using a phosgene method or using a dialkyl carbonate such as dinonyl carbonate or diethyl carbonate. Carbonate transesterification reaction of diphenyl carbonate (for example, refer to Japanese Patent Publication No. Sho 62-187725, Japanese Patent Application Laid-Open No. Hei 2-157521 Synthetic or the like. The carbonate bond of the polycarbonate polyol (C) is not easily thermally decomposed. Therefore, the resin cured product containing the polycarbonate polyol is high in temperature and high humidity. Further, the polycarbonate polyol (C) may be used singly or in combination of two or more kinds. The above-mentioned carbonic acid-based or biphenyl vinegar is used in the exchange reaction of cesium carbonate. Polyol' such as: 1,6-hexane diol, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 2,3- Butylene glycol, 1,5-pentanediol, 3·mercapto-1,5-pentanediol, L4-cyclohexanedioxin-14- 201235375

伸丁二醇、丙二薛、— 丙二醇、二丙二醇等 醇、1，8-辛烷二醇、 二烯二醇、新戊二醇、Butanediol, propylene disulfide, propylene glycol, dipropylene glycol and other alcohols, 1,8-octanediol, diene glycol, neopentyl glycol,

醇之羥基價，依下式算出。 [數量平均分子量]=56.11&gt;&lt;11/[羥基價]&gt;&lt;1〇〇〇 惟，η代表1分子之聚礙酸g旨多元醇所含之經基數目 ，例如：為聚碳酸酯二醇時，以n = 2計算數量平均分子量 〇 聚碳酸酯多元醇（C)，也可使用piaccel CD205、 CD210、CD220、CD205PL、CD205HL、CD210PL、CD210HL 、CD220PL' CD220HL、CD220EC、CD221T(以上為 Daicel( 股）製）、ETERNACOLL UH-CARB50、UH-CARB100、 UH-CARB300、UH-CARB90(l/3)、UH-CARB90(1/1)、 11!1-0入1^100(以上、宇部興產（股）製）、〇1^11〇1丁6002 、T5 65 2、T4672、T46 92、G3 45 2(以上為旭 匕成 4匕學（股） 製）、Kuraraypolyol ND、MPD(以上為 Kuraray(股）製）等 市售品。 聚碳酸酯多元醇（C)之使用量（含量）不特別限定’相 對於上述成分（A)及成分（B)之合計量（100重量份），1〜50 -15- 201235375 .重量份較佳，更佳為1.5〜30重量份，又更佳為2~2〇重量 伤。聚奴酸酯多元醇（c)之摻合量若超過5〇重量份，硬化 物之T g會降低過度，由於加熱所致之體積變化增大，有 時光半導體裝置會發生燈不亮等不良現象。又，雖然彎 曲強度提高，但是有時透明性會降低。聚碳酸酯多元醇 (C)之摻合量若小於i重量份，耐回流性降低，且有時會 由於回流步驟之加熱處理，造成光半導體裝置中之密封 樹脂從導線架剝離或發生龜裂。 &lt;硬化劑（D)&gt; 硬化劑（D)具有使具環氧基之化合物硬化之作用。本 發明中’硬化劑（D)可使用當作環氧樹脂用硬化劑為周知 或慣用之硬化劑。硬化劑（D)當中以25cc呈液狀之酸酐較 佳，例如：曱基四氫鄰苯二甲酸酐、甲基六氫鄰苯二曱 酸酐、十二烯基琥珀酸酐、甲基内向亞甲基四氫鄰苯二 甲酸針等。又’例如：鄰苯二甲酸酐、四氫鄰笨二曱酸 野、六氫鄰苯二曱酸酐、曱基環己稀二叛酸酐等常溫（ 約2 5 °C )呈固體狀之酸針’可藉由溶於常溫（約2 5 °C )呈液 狀之酸肝而成為液狀的混合物，當作本發明之硬化性環 氧樹脂組成物中的硬化劑（D)使用。又，硬化劑（D)可以 單獨使用1種或組合使用2種以上。 又’本發明中’硬化劑（D)也可使用RikacidMH-70〇( 新曰本理化（股）製）、HN-5500(曰立化成工業（股）製）等市 售品。 硬化劑（D)之含量不特別限定，相對於硬化性環氧樹 脂組成物中所含之具環氧基之化合物全量（1 〇〇重量份） -16- 201235375 ，較佳為50〜200重量份，更佳為1〇〇〜145重量份。更具體 而言，以成為上述硬化性環氧樹脂組成物中含有之所有 具環氧基之化合物中之環氧基每i當量，為〇 5〜15當量之 比例使用較佳。硬化劑（D)之使用量若少於5〇重量份，硬 化不充分，硬化物之強鞅性有降低之傾向，另一方面， 硬化劑（D)之使用量若高於2〇〇重量份，硬化物會著色， 有時色相惡化。 &lt;硬化觸媒（E)&gt; 又，本發明中，硬化觸媒（E)也可使用藉由施以紫外 線照射或加熱處理而產生陽離子物質而使聚合開始之陽 離子觸媒。又，硬化觸媒（E)可以單獨使用i種或組合使 用2種以上。 由於紫外線照射產生陽離子物質之陽離子觸媒，例 如.六氟銻酸鹽、五氟羥基銻酸鹽、六氟磷酸鹽、六氟 砷酸鹽等，使用UVACURE1 590(Daice卜Cytec(股）製）、 CD 1〇1〇、CD-1011、CD-1012(美國 Sartomer 製）、Irgacure 264(Ciba japan(股）製）、CIT_ 1 682(日本曹達（股）製）等市 售品為理想。 藉由施以加熱處理產生陽離子物質之陽離子觸媒， 例如·芳基重氮鹽、芳基鎭鹽、芳基銃鹽、芳烯_離子錯 合物等’較佳為可使用例如pp_33、CP 66、CP 77(adeka( 股）製）、FC-509(3M 製）、UVE1014(G.E.製）、San-Aid SI_60L、San-Aid SI-80L、San-Aid SI-100L、San-Aid SI-110L(三新化學工業（股）製）、cG_24_61(Ciba japan(股 )製）等市售品。再者，鋁或鈦等金屬與乙醯乙酸或二酮 -17- 201235375 類之螯合化合物與三苯基矽醇 并寺石夕醇之化合物、或鋁志 鈦等金屬與乙醯乙酸或二_ 次鋁或 酚類之化合物亦可。 寻 硬化觸媒（Ε)之含I不蛀m 特別限定’相對於硬化性環氧 樹脂組成物中所含之具環氧基之化合物全量(100重量份 )’為0.01〜15重量份較佳，更佳為〇 〇1〜12重量份，又更 佳為0.05〜10重量份，尤佳為〇 ] 住马0 ·1〜10重量份。硬化觸媒（E) 藉由在此範圍内使用，可獲得耐熱性、耐光性、透明性 優異之硬化物。 &lt;硬化促進劑（F)&gt; 本發明之硬化性環氧樹脂組成物也可含有硬化促進 劑（F)。硬化促進劑（F)，係當以硬化劑使具環氧基之化合 物硬化時，具有促進硬化速度之機能之化合物。尤其常 與硬化劑（D)併用《硬化促進劑（F)，可使用周知或慣用 之硬化促進劑’例如：丨，8_二氮雜雙環[5 4 〇]十一烯 -7(DBU)、及其鹽（例如：紛鹽、辛酸鹽、對甲苯續酸鹽 、曱酸鹽、四苯基硼酸鹽）；15-二氮雜雙環[4 3 〇]壬烯 -5(DBN)、及其鹽（例如：鱗鹽、銃鹽、4級鍵鹽、鎮鹽） ;苄基二甲胺、2,4,6-參（二甲胺基曱基）酚、N，N-二曱基 環己胺等3級胺；2-乙基-4-甲基咪唑' 1-氰基乙基-2-乙 基-4 -甲基咪唑等咪唑；磷酸酯、三苯膦等膦類；四苯基 鱗四（對甲苯基）硼酸鹽等鱗化合物；辛酸錫、辛酸辞等 有機金屬鹽；金屬螯合物等。上述硬化促進劑（F)可以單 獨使用或混合使用2種以上。The hydroxyl value of the alcohol is calculated according to the following formula. [Quantum average molecular weight] = 56.11 &lt; 11 / [hydroxyl price] &gt; 1 ,, η represents a molecular weight of one molecule, and the number of radicals contained in the polyol is, for example, a poly For carbonate diols, calculate the number average molecular weight 〇 polycarbonate polyol (C) with n = 2, or use piaccel CD205, CD210, CD220, CD205PL, CD205HL, CD210PL, CD210HL, CD220PL' CD220HL, CD220EC, CD221T ( The above are Daicel (share), ETERNACOLL UH-CARB50, UH-CARB100, UH-CARB300, UH-CARB90 (l/3), UH-CARB90 (1/1), 11!1-0 into 1^100 ( Above, Ube Industries Co., Ltd., 〇1^11〇1丁6002, T5 65 2, T4672, T46 92, G3 45 2 (above is Xu Yucheng 4匕学(股)), Kuraraypolyol ND, MPD (above is Kuraray Co., Ltd.) and other commercial products. The amount (content) of the polycarbonate polyol (C) is not particularly limited to the total amount (100 parts by weight) relative to the above component (A) and component (B), 1 to 50 -15 to 201235375. Preferably, it is preferably 1.5 to 30 parts by weight, and more preferably 2 to 2 inches by weight. When the blending amount of the polysulphonate polyol (c) exceeds 5 parts by weight, the Tg of the cured product may be excessively lowered, and the volume change due to heating may increase, and the optical semiconductor device may be defective in light or the like. phenomenon. Further, although the bending strength is improved, the transparency may be lowered. When the blending amount of the polycarbonate polyol (C) is less than i part by weight, the reflow resistance is lowered, and sometimes the sealing resin in the optical semiconductor device is peeled off or cracked from the lead frame due to the heat treatment in the reflow step. . &lt;Hardener (D)&gt; The hardener (D) has an action of hardening a compound having an epoxy group. In the present invention, the curing agent (D) may be a curing agent known as a curing agent for epoxy resins. Among the hardeners (D), it is preferred to use 25 cc of a liquid anhydride, for example, mercaptotetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecenylsuccinic anhydride, methyl inward armor Base tetrahydrophthalic acid needles, etc. Also, for example, phthalic anhydride, tetrahydro-o-dibenzoic acid field, hexahydrophthalic anhydride, decylcyclohexanic acid anhydride, etc., at a normal temperature (about 25 ° C) as a solid acid needle 'It can be used as a hardener (D) in the curable epoxy resin composition of the present invention by being dissolved in a liquid form of sour liver at room temperature (about 25 ° C). Further, the curing agent (D) may be used alone or in combination of two or more. Further, in the present invention, a commercially available product such as Rikacid MH-70 (manufactured by Shinji Chemicals Co., Ltd.) or HN-5500 (manufactured by Konica Chemicals Co., Ltd.) can be used as the curing agent (D). The content of the hardener (D) is not particularly limited, and is a total amount (1 part by weight) of the epoxy group-containing compound contained in the curable epoxy resin composition of -16 to 201235375, preferably 50 to 200 parts by weight. More preferably, it is from 1 to 145 parts by weight. More specifically, it is preferably used in an amount of from 5 to 15 equivalents per equivalent of the epoxy group in the epoxy group-containing compound contained in the curable epoxy resin composition. When the amount of the hardener (D) used is less than 5 parts by weight, the hardening is insufficient, and the strength of the cured product tends to decrease. On the other hand, the amount of the hardener (D) used is more than 2% by weight. The hardened material will be colored, and sometimes the hue will deteriorate. &lt;Curing Catalyst (E)&gt; Further, in the present invention, the curing catalyst (E) may be a cationic catalyst which starts polymerization by a cationic material by ultraviolet irradiation or heat treatment. Further, the curing catalyst (E) may be used alone or in combination of two or more. A cationic catalyst for generating a cationic substance by ultraviolet irradiation, for example, hexafluoroantimonate, pentafluorohydroxy decanoate, hexafluorophosphate, hexafluoroarsenate or the like, using UVACURE 1 590 (Daice Bu Cytec) Commercial products such as CD 1〇1〇, CD-1011, CD-1012 (manufactured by Sartomer, USA), Irgacure 264 (manufactured by Ciba japan), and CIT_1 682 (made by Japan Soda Co., Ltd.) are preferable. The cationic catalyst which generates a cationic substance by heat treatment, for example, an aryl diazonium salt, an aryl sulfonium salt, an aryl sulfonium salt, an arylene ion complex, etc. is preferably used, for example, pp_33, CP 66, CP 77 (made by Adeka), FC-509 (3M system), UVE1014 (made by GE), San-Aid SI_60L, San-Aid SI-80L, San-Aid SI-100L, San-Aid SI- Commercial products such as 110L (Sanshin Chemical Industry Co., Ltd.) and cG_24_61 (Ciba japan). Further, a metal such as aluminum or titanium and a chelate compound of acetonitrile acetic acid or diketone-17-201235375 and a compound of triphenyl decyl alcohol, or a metal such as aluminum sulphate or acetonitrile or s Sub-aluminum or phenolic compounds are also acceptable. The content of the hardening catalyst (Ε) is not particularly limited. It is preferably 0.01 to 15 parts by weight based on the total amount (100 parts by weight) of the epoxy group-containing compound contained in the curable epoxy resin composition. More preferably, it is 1 to 12 parts by weight, more preferably 0.05 to 10 parts by weight, and particularly preferably 〇] live horse 0 · 1 to 10 parts by weight. When the curing catalyst (E) is used in this range, a cured product excellent in heat resistance, light resistance, and transparency can be obtained. &lt;Curing accelerator (F)&gt; The curable epoxy resin composition of the present invention may contain a curing accelerator (F). The hardening accelerator (F) is a compound which has a function of promoting the curing speed when the epoxy group-containing compound is hardened with a curing agent. In particular, the hardening accelerator (F) is often used in combination with a hardening accelerator (F), and a known or conventional hardening accelerator can be used, for example, hydrazine, 8-diazabicyclo[5 4 fluorene]undecene-7 (DBU). And salts thereof (for example: salt, octanoate, p-toluene, citrate, tetraphenylborate); 15-diazabicyclo[4 3 fluorene]nonene-5 (DBN), and a salt thereof (for example, a scale salt, a phosphonium salt, a 4-stage bond salt, a salt of a salt); a benzyl dimethylamine, a 2,4,6-gin(dimethylaminomercapto)phenol, and an N,N-didecyl group. a tertiary amine such as cyclohexylamine; an imidazole such as 2-ethyl-4-methylimidazolium 1-cyanoethyl-2-ethyl-4-methylimidazole; a phosphine such as a phosphate ester or a triphenylphosphine; a scaly compound of phenyl scale tetrakis(p-tolyl)borate; an organic metal salt such as tin octylate or octanoic acid; a metal chelate compound or the like. These hardening accelerators (F) may be used singly or in combination of two or more.

又，本發明中，硬化促進劑（F)也可使用U-CAT SA -18- 201235375Further, in the present invention, the hardening accelerator (F) can also use U-CAT SA -18- 201235375

U-CAT 410、U-CAT ^ ' 〜J，，ΡΡ-Κ 曰本化學工 TPP-MK(均為北興化學工業（股）製）、ρχ_4Ετ(日本化學 業（股）製）等市售品。U-CAT 410, U-CAT ^ ' ～J,,ΡΡ-Κ 曰本Chemistry TPP-MK (both Beixing Chemical Industry Co., Ltd.), ρχ_4Ετ (Nippon Chemical Industry Co., Ltd.) and other commercial products .

份），為0.05〜5重量份較佳，更佳為〇1〜3重量份，又更佳 為0.2〜3重量份，尤佳為0 25The portion is preferably 0.05 to 5 parts by weight, more preferably 1 to 3 parts by weight, still more preferably 0.2 to 3 parts by weight, particularly preferably 0 25 parts by weight.

另一方面，硬化促進劑（F)之使用量若超過5重量份，有 時硬化物會著色、色相惡化。 &lt;丙烯酸基嵌段共聚物&gt; 本發明之硬化性環氧樹脂組成物，從抑制光半導體 裝置之光度隨時間降低的觀點，更含有丙烯酸基嵌段共 聚物較佳。更詳而言之’本發明之硬化性環氧樹脂組成 物含有丙烯酸基嵌段共聚物時，以該硬化性環氧樹脂组 成物密封之光半導體裝置，即使是高輝度、高輸出，仍 有光度不易降低的傾向。亦即’藉由使用丙烯酸基嵌段 共聚物，將本發明之硬化性環氧樹脂組成物硬化而得之 硬化物，能發揮更高水準的耐熱性、耐光性、及耐龜_ 性。 上述丙烯酸基嵌段共聚物’係含有丙烯酸系單體為 必要單體成分之嵌段共聚物。上述丙烯酸系單體，例如 :丙烯酸曱酯、丙烯酸乙酯、丙烯酸正丁酯、丙歸酸第 三丁醋、丙稀酸2 -乙基己醋、曱基丙稀酸甲醋、甲其丙 -19- 201235375 烯酸乙酯、曱基丙烯酸正丁酯、甲基丙烯酸第三丁酯、 曱基丙烯酸2 -乙基己酯、曱基丙烯酸月桂酯、甲基丙烯 酸硬脂酯等（甲基）丙烯酸烷基酯；丙烯酸環己酯、曱基 丙烯酸環己酯等具有脂環構造之（曱基）丙烯酸酯；甲基 丙烯酸苄酯等具芳香環之（曱基）丙烯酸酯；甲基丙烯酸 2-三氟乙酯等（甲基）丙烯酸之（氟）烷酯；丙烯酸、甲基丙 烯酸、馬來酸、馬來酸酐等分子中具羧基之含羧基之丙 烯酸基單體；丙烯酸2 -羥基乙酯、丙烯酸2 -羥基丙酯、 丙烯酸4-羥基丁酯、曱基丙烯酸2_羥基乙酯、甲基丙缚 酸2 -經基丙酯、甲基丙稀酸4 _羥基丁酯、甘油之單（甲基） 丙稀酸酷等分子中具有羥基之含羥基之丙烯酸基單體； 甲基丙烯酸環氧丙酯、曱基丙烯酸甲基環氧丙酯、甲基 =烯酸3,4-環氧環己基甲醋等分子中具有環氧基之丙烯 酸基單體；丙烯酸烯丙酯、曱基丙烯酸烯丙酯等分子中 具有烯丙基之含烯丙基之丙烯酸基單體；γ-甲基丙烯醯 氧基丙基—曱氧基矽烷、γ曱基丙烯醯氧基丙基三乙氧 等分子中具有水解性⑪基之含耗基之丙稀酸基 單體，2 (2 ·羥基_5’-甲基丙烯醯氧基乙基苯基）-2Η-苯并 三σ坐等具右#_ 、 本开二°坐系紫外線吸收性基之紫外線吸收性 丙烯酸基單體等。 ^ 上述丙婦酸基嵌段共聚物中，也可使用上述丙 稀系單體以外之單體當作單體成分。上述丙烯酸系單 體以外之單艘 . ’例如：笨乙烯、α_甲基苯乙烯等芳香族 乙稀基化合物、丁 _ &amp; 丁一烯、異戊二烯等共軛二烯、乙烯、 丙烯、異丁烯等烯烴等。 -20- 201235375 上述丙烯酸基嵌段共聚物不特別限定，彳 W如：包含2 個聚合物嵌段構成的二嵌段共聚物，或包含3個 眾' 合物嵌 段構成之三嵌段共聚物、包含4個以上之聚八队山 κ 13物嵌段構成 之多嵌段共聚物等。 其中’上述丙烯酸基嵌段共聚物，從耐埶 …、性、耐光 性、及耐龜裂性提高之觀點，宜為玻璃轉移溫产（丁）七 之聚合物嵌段（s)(軟嵌段）、與具有比聚合物嵌段= 之Tg之聚合物嵌段（Η)(硬喪段）交替排列而成之私^ ^ 5««物’更佳為中間為聚合物嵌段（S)’且兩端具聚人物2 段（Η)之H-S-H構造之三嵌段共聚物。又，上述丙:酸2 嵌段共聚物之構成聚合物嵌段（S)之聚合物之Tg不特^ 限定，宜低於30°C。又，構成聚合物嵌段（H)之聚合物之 Tg不特別限定，為30°C以上較佳。上述丙烯酸基嵌段共 聚物具有多數聚合物嵌段（H)時，各聚合物嵌段（⑴可^ 有相同組成也可不同。同樣，上述丙烯酸基嵌段共聚物 即使具有多數聚合物嵌段（S)時’各聚合物嵌段（s)也可具 相同或不同組成。 上述丙烯酸基嵌段共聚物（上述H-S-H構造之三嵌段 共聚物等）中’構成聚合物嵌段（H)之單體成分不特別限 定，例如：均聚物之Tg為30t以上之單體，更詳而言之 ，例如··甲基丙烯酸曱酯、苯乙烯、丙烯醢胺、丙稀腈 等。另一方面，上述丙烯酸基嵌段共聚物中，構成聚合 物嵌段（S)之單體成分不特別限定，例如：均聚物之以低 於3 0 C之單體，更詳言之，例如丙烯酸丁酯或丙烯酸2 _ 乙基己酯等丙烯酸Cno烷酯、丁二烯（丨，4-丁二烯）等。 -21 - 201235375 本發明之硬化性環氧樹脂組成物中，丙烯酸基嵌段 共聚物之較佳具體例，例如：上述聚合物嵌段（s)由以丙 稀酸丁醋（BA)為主之單體構成之聚合物，上述聚合物嵌 段（H)由以甲基丙烯酸甲酯（mma)為主之單體構成之聚 合物、聚曱基丙烯酸甲酯-bl〇ck_聚丙烯酸丁酯-bl〇ck_聚 曱基丙烯酸甲酯三聚物（PMMA-b-PBA-b-PMMA)等。上述 PMMA_b-PBA-b-PMMA，從财熱性、对光性、及耐龜裂 性提高之觀點為較佳。又，上述PMMA-b-PBA-b-PMMA ’可視需要’以提高對於成分（A)及成分（B)之互溶性為 目的，使具有親水性基（例如：羥基、羧基、胺基等）之 單體’例如（曱基）丙烯酸羥基乙酯、（〒基）丙烯酸羥基丙 醋、（曱基）丙烯酸等共聚合於PMMA嵌段及/或PBA嵌段 者。 上述丙烯酸基嵌段共聚物之數量平均分子量不特別 限定，宜為3000〜500000，更佳為10000〜300000，又更佳 為30000〜400000。數量平均分子量若小於3〇〇〇(尤其低於 1 0 000) ’硬化物之強靭性不足，有時耐龜裂性會降低。 另一方面，數量平均分子量若超過5 0 0000，與脂環環氧 化合物（A)之互溶性會降低，有時硬化物之透明性會降低 。上述數量平均分子量例如：可利用凝膠滲透層析法 (GPC法）測定之標準聚苯乙烯換算之分子量計算。 上述丙烯酸基嵌段共聚物，可依照周知或慣用之嵌 段共聚物之製造方法製造。上述丙烯酸基嵌段共聚物之 製造方法中’從容易控制丙稀酸基嵌段共聚物之分子量 、分子量分布及末端構造等之觀點，以活性聚合（活性自 -22- 201235375 由基聚合、活性陰離子聚合、活性陽離子聚合等）為較佳 。上述活性聚合’可依照周知或慣用之方法實施。 又’上述丙稀酸基喪段共聚物，例如也可使用：商 品名「NANOSTRENGTH M52N」、「NANOSTRENGTH M22N」、「NANOSTRENGTH M51」、「NANOSTRENGTH M52」、「NANOSTRENGTH M53」（Arkema(股）製' PMMA-b-PBA-b-PMMA)、商品名「NANOSTRENGTH E21 」、「NANOSTRENGTH E41」（Arkema(股）製、PSt(聚苯 乙烯）-b-PBA-b-PMMA)等市售品。 上述丙烯酸基嵌段共聚物之使用量（含量）不特別限 定，相對於成分（A)及成分（B)之合計量（1〇〇重量份），為 1〜30重量份較佳，更佳為3〜15重量份，又更佳為5〜10重 量份。丙烯酸基嵌段共聚物之使用量若低於1重量份，有 時硬化物之強靭性不足，有時耐熱性、耐光性會降低。 另一方面，丙烯酸基嵌段共聚物之使用量若超過30重量 份，與脂環環氧化合物（A)之互溶性降低，且有時硬化物 之透明性降低。 &lt;橡膠粒子&gt; 本發明之硬化性環氧樹脂組成物也可更含有橡膠粒 子。上述橡膠粒子，例如：粒子狀NBR(丙烯腈-丁二烯橡 膠）、反應性末端羧基NBR(CTBN)、無金屬NBR、粒子狀 SBR(苯乙烯-丁二烯橡膠）等橡膠粒子。上述橡膠粒子， 宜為包含具有橡膠彈性之核部分、與被覆該核部分之至 少1層鞘層構成之多層構造（核鞘構造）之橡膠粒子。上述 橡膠粒子，尤佳為以（曱基）丙烯酸酯當作必要單體成分 -23- 201235375 之聚合物（聚合體）構成，且表面具有羥基及/或羧基（羥基 及羧基任一者或兩者）當作能與脂環環氧樹脂（A)等具環 氧基之化合物反應之官能基之橡膠粒子。上述橡膠粒子 之表面不存在羥基及/或羧基時，會由於冷熱循環等熱衝 擊造成硬化物變得白濁且透明性降低，故為不佳。 上述橡膠粒子中，構成具橡膠彈性之核部分之聚合 物，不特別限定，較佳為以（甲基）丙烯酸甲酯、（甲基） 丙烯酸乙酯、（甲基）丙烯酸丁酯等（曱基）丙烯酸酯當作必 要單體成分。構成上述具橡膠彈性之核部分之聚合物， 除此以外，也可含有例如：苯乙烯、α•曱基苯乙烯等芳 香族乙烯基化合物；丙烯腈、甲基丙烯腈等腈；丁二= 、異戊一烯等共軛二烯；乙烯、丙烯、異丁烯等烯庐’ 當作單體成分。 二f 其中，構成上述具橡膠彈性之核部分之聚合物，就 單體成分而言，含有（甲基）丙烯酸酯，以及選自於芳^ 族乙稀基化合物、_、及共輛二烯構成之群組中旧❹ 種以上之組合較佳。亦即，構成上述核部分之聚合物， 例如（曱基）丙烯酸酯/芳香族乙烯基化合物、（甲基）丙 烯酸6曰/共軛二烯等二元共聚物；（曱基)丙烯酸酯/芳香旅 乙烯基化合物’共軛二烯等三元共聚物等。又構成上： 核部分之聚合物中’也可含有聚二甲基矽氧烷或聚笨基 甲基矽氧烷等聚矽氧或聚胺甲酸酯等。 土 成上述核部分之聚合物’就其他單體成分而言， 也可含有二乙烯基苯、（甲基）丙烯酸烯丙酯、乙二醇二 甲基)丙烯酸酯、馬來酸二烯丙§旨、三聚氰酸三烯丙酯、 -24 - 201235375 鄰苯一甲酸二烯丙酯、丁二醇二丙烯酸酯等1單體（1分子 )中/、有2個以上之反應性官能基之反應***聯單體。 上述橡膠粒子之核部分中，由（曱基）丙烯酸酯/芳香 族乙烯基化合物之二元共聚物（尤其丙烯酸丁酯/苯乙烯） 構成.核邛刀從旎輕易調整橡膠粒子之折射率之觀點為 較佳。 上述橡膠粒子之核部分，可使用通常使用之方法製 造，例如可利用將上述單體以乳化聚合法進行聚合之方 法等製造。乳化聚合法時，可將上述單體全量一次添加 ，也可先聚合上述單體的一部分後，將其餘部分連續或 間歇添加並聚合，再者，也可利用使用種粒之聚合方法 〇 構成上述橡膠粒子之靭層之聚合物，宜為與構成上 述核部分之聚合物為不同種之聚合物。又，如上述，上 述鞘層宜具有羥基及/或羧基當作能與脂環環氧化合物 (A)等具環氧基之化合物反應之官能基。藉此，尤其能使 與脂環環氧化合物（A)之界面的黏著性提高，對於使含有 具該鞘層之橡膠粒子之硬化性環氧樹脂组成物硬化而得 之硬化物’可發揮優異的耐龜裂性。又，也可防止硬化 物之玻璃轉移溫度降低。 構成上述鞘層之聚合物’宜含有（甲基）丙烯酸甲錯 、（甲基）丙烯酸乙酯、（甲基）丙烯酸丁酯等（甲基）丙稀奶 醋當作必要單體成分。例如：上述核部分中，（甲基）丙 烯酸酯使用丙烯酸丁酯時，構成鞘層之聚合物之單體成 分，宜使用丙烯酸丁酯以外之（甲基）丙烯酸酯（例如：（ -25- 201235375 甲基)丙烯酸甲醋、（甲基)丙稀酸乙酿、甲基丙稀酸丁酿 等）。（甲基）丙烯酸S旨以外也可含有的單 苯乙稀…基苯乙稀等芳香族乙稀基化合物、：；猜 、甲基丙埽腈等腈等。上述橡膠粒子中，構成稍層之單 體成刀且將（甲基）丙烯酸酯與上述單體單獨丨種或2種 以上組合較佳，尤其，至少含有芳香族乙烯基化合物時 ，從能輕易調整上述橡膠粒子之折射率之觀點為較佳。 再者，構成上述鞘層之聚合物，就單體成分而言， 為了形成當作能與脂環環氧化合物（A)等具環氧基之化 合物反應之官能基的羥基及/或羧基，宜含有（甲基）丙烯 酸2_羥基乙酯等（甲基）丙烯酸羥基烷酯、或（甲基）丙烯酸 等α，β-不飽和酸、馬來酸酐等α，ρ不飽和酸酐等單體。 上述橡膠粒子中，構成鞘層之聚合物，就單體成分 而s ’且含有（曱基）丙烯酸酯，以及選自於上述單體之1 種或2種以上之组合。亦即，上述鞘層例如為（甲基）丙烯 酸醋/芳香族乙烯基化合物/羥基烷基（甲基）丙烯酸酯、（ 甲基）丙烯酸酯/芳香族乙烯基化合物/α，β_不飽和酸等三 元共聚物等構成之鞘層較佳。 又’構成上述鞘層之聚合物，就其他單體成分而言 ’與核部分同樣，除了上述單體以外，也可含有二乙烯 基苯、（曱基）丙烯酸烯丙酯、乙二醇二（曱基）丙烯酸酯、 馬來酸一烯丙酯、三聚氰酸三稀丙酯、鄰苯二曱酸二埽 兩S旨、丁二醇二丙烯酸酯等1單體〇分子）中具有2個以上 之反應性官能基之反應***聯單體。 上述橡膠粒子（具核鞘構造之橡膠粒子），可藉由將 -26- 201235375 上述核部分以鞘層被覆而得。將上述核部分以勒層被覆 之方法，例如在由上述方法獲得之具橡膠彈性之核部分 之表面，塗佈構成鞘層之共聚物以進行被覆之方法、以 由上述方法獲得之具橡膠彈性之核 以構成勒層之各成分當作枝成分，進行接枝聚^方^ 等。 上述橡膠粒子之平均粒徑不特別限定，i nm，更佳為20〜4〇〇nm。又，上述橡膠粒子之最大粒徑不 特別限定，宜為50〜l〇〇〇nm，更佳為1〇〇〜8〇〇nm。平均粒 徑若大於50〇nm，或最大粒徑大於1〇〇〇nm時橡膠粒子 於硬化物之分散性降低，且有時耐龜裂性降低。另一方 面，平均粒徑若小於l〇nm或最大粒徑小於5〇nm，硬化物 之耐龜裂性提高之效果有時不易獲得。 上述橡膠粒子之折射率不特別限定，宜為14〇〜16〇 ，更佳為1.42〜1.58。又，橡膠粒子之折射率、與將含該 橡膠粒子之硬化性環氧樹脂組成物（本發明之硬化性環 氧樹脂組成物）硬化而獲得之硬化物之折射率之間的差 異，為±0.03以内（_0·03〜〇.03)較佳。上述折射率之差異若 大於±0.03，硬化物之透明性會降低，有時會變得白濁， 光半導體裝置之光度有降低之傾向，有時會喪失光半導 體裝置之機能。 橡膠粒子之折射率，例如：可藉由將橡膠粒子丨§注 入成形模，於2UTC、4MPa進行壓縮成形，獲得厚度lmm 之平板，從獲得之平板切出縱2〇mmx橫6mm之試驗片， 並使用單溴萘當作中間液，於使棱鏡與該試驗片密合之 -27- 201235375 狀態，使用多波長阿貝折射計（商品名「DR_M2」、Atag〇( 股）製）’於2crc、以鈉〇線測定折射率而求取。 本發明之硬化性環氧樹脂組成物之硬化物之折射率 ，例如可從藉由後述光半導體裝置之項目記載之加熱硬 化方法獲得之硬化物，切出縱2〇mm&gt;^f6mmx厚度化爪之 試驗片，並使用單漠萘當作中間液，於使稜鏡與該試驗 片密合之狀態，使用多波長阿貝折射計（商品名「dr_m2 」、AUgo(股）製），測定2〇t、鈉〇線的折射率以求取。 本發明之硬化性環氧樹脂組成物中，上述橡膠粒子 之含$ (摻合量）不特別限定’㈣於硬化性環氧樹脂组 成物中所含之具環氧基之化合物全量（1〇〇重量份），為 〇.5〜30重量份較佳，更佳為丨〜“重量份。橡膠粒子之含 量若少於0.5重量❾，硬化物之耐龜裂性有降低之傾向。 另—方面，橡膠粒子之含量若超過30重量份，硬化物之 耐熱性有降低之傾向。 &lt;添加劑〉 · 本發明之硬化性環氧樹脂組成物中，&amp;了上述以夕 ’在不損及本發明效果之範圍内，也可以使用各種添力 劑。添加劑例如若使用乙二醇、二乙二醇、丙二醇、^ 油等具羥基之化合物’能使反應溫和地進行。此外，^ 不損及黏度或透明性之範_，可使用聚石夕氧系或iu 消泡劑、塗平齊卜γ-環氧丙氧基丙基三甲氧基石夕烷等石 烧偶合劑、界面活性劑、二氧切、氧化料無機填） 劑 H色劑 '抗氧化劑、紫外線吸收劑、離： 吸附體、顏料、螢光體、脫模劑等慣用之添加劑。 -28- 201235375 &lt;硬化物&gt; 藉由使本發明之硬化性環氧樹脂組成物硬化可獲 得^…丨生耐光性、透明性、及耐龜裂性等各物性優異 ，且耐回流性亦為優異之硬化物。硬化時之加熱溫度（ 硬化溫度）不特別限定，宜為45〜200它，更佳為1〇〇〜19〇艺 ，又更佳為io〇〜18(rc ^又，硬化時之加熱時間（硬化時 間）不特別限定，宜為30〜600分鐘’更佳為45〜54〇分鐘， =更佳為60〜48〇分鐘。硬化溫度與硬化時間若低於上述 範圍之下限値時’硬化不充分，反之，若高於上述範圍 之上限値時，樹脂成分有時會分解，均不佳。硬化條件 取失於各種條件，藉由當硬化溫度高時縮短硬化時間， 硬化溫度低時加長硬化時間，可以適當調整。 &lt;光半導體密封用樹脂組成物&gt; 本發明之光半導體密封用樹脂組成物，係包含本發 明之硬化性環氧樹脂組成物而構成。藉由使用本發明之 光半導體密封用樹脂組成物將光半導體元件予以密封， 可以利用耐熱性、耐光性、透明性、及耐龜裂性等各物 ，優異，且耐回流性亦為優異之硬化物將光半導體元件 密封而得到光半導體裝置。 &lt;光半導體裝置&gt; 本發明之光半導體裝置，可藉由以本發明之硬化性 環氧樹脂組成物（光半導體密封用樹脂組成物）將光半導 體兀件予以密封而獲得。光半導體元件之密封，係將以 上述方法製備的硬化性環氧樹脂組成物注入既定成形模 ’並以既定條件進行加熱硬化。藉此，可獲得以硬化性 -29- 201235375 環氧樹脂組成物將光半導 要 儿 导體疋件密封而成的光半導體裝 置。硬化溫度與硬化時間可 卞导篮哀 ^ m ^ m. _ 0 /、上述相同。本發明之光半 導體裝置，不易由於回流 洚TW ± 驟之加熱處理而劣化，且光 度不易時間降低。 一般而言，光半導體验 曰；MM π _L s 置中，如第1圖所示，係以固 日日材105將光半導體元侏μ 等…η 定於導線架。本案發明人 寺’發現輅由將光半導艚奘 裝中的固晶材予以最適化， 也月b 同耐回流性。更詳+ + m β + 吏$ 5之，將光半導體裝置以回流 步驟進仃加熱處理時，視由 a 祝由於畨封樹脂之體積變化所生 之應力，選擇光半導體元件 个會攸導線架剝離之固晶材（ 黏者性•耐久性高之固晶材） 甘S m Μ承為重要。其原因為光丰導 體凡件從導線架剝離時，該半 ^ a ^ , 干導體兀件周邊的密封樹脂 :易發生剝離或龜裂’於回流步驟之加熱處理導致之光 半導體裝置劣化會變得顯著。因此為了提高耐回流性、 防止回流步驟之加熱處理造成光半導體裝置劣化，使用 本發明之硬化性環氧樹脂組成物當作密封樹脂(密封用 樹脂），且使用上述黏著性·耐久性高之固晶材當作固晶 :為有效。上述固晶材’例如於聚醯亞胺樹脂、環氧樹 月曰、聚矽氧樹脂等基礎聚合物令含有導電性粒子等（例如 銀粒子等）而得之固晶材等。如此的固晶#，例如： M2、KER-3100 02、KER-3100(信越化學工業 (股）製）、EH1600-G2(Inabata產業（股）製）、CT2〇〇、CT284 、CT265(京瓷化學（股）製）等。 本發明之硬化性環氧樹脂組成物，不限於上述光半 導體密封用途’也可利用於例如：黏著劑、電氣絕緣材 -30- 201235375 、疊層板、塗膜、印墨、塗 材料、透明基材 '透明片、 透鏡、光學構件、光造形、 電池基板、光導波路、導光 [實施例] 料、填封劑、抗蝕劑、複合 透明薄膜、光學元件、光學 電子紙、觸控面板、太陽能 板、全像記憶體等。 但本發明 以下依據實施例對於本發明更詳細說明 不限於該等實施例。 製造例1 (橡膠粒子之製造） 於配備回流冷卻器之1L聚合容器中，添加離子交換 水500g、*二辛基確*琥拍酸納〇心，於氮氣流下 揽拌一邊升溫至8〇t。於其中一次添加用於形成核部 分所必要之量之約相當於5重量％分量之由丙烯酸丁酉旨 9.5g、苯乙烯2.57g、及二乙烯基苯〇 39§構成之單體混人 物，撥拌20分鐘使乳化後，添加過氧二硫酸卸9 5mg，^ 拌1小時’進行最初的種聚合。接著，添加過氧二硫酸鉀 l8〇.5mg’並攪拌5分鐘。於其中，花費2小時連續添加用 於形成核部分所必要量之其餘（約95重量％分量）之於丙 稀酸丁醋180_5g、苯乙烯48.89g、二乙烯基苯7 ^溶解 二辛基續基號轴酸鈉〇.95g而成的單體混合物，進行第2 次的種聚合’之後進行1小時熟成，獲得核部分。 其次’添加過氧二硫酸鉀60mg，攪拌5分鐘，並於 其中化費30分鐘連續添加於甲基丙烯酸甲酯6〇呂、丙稀酸 1 _5g、及甲基丙烯酸烯丙酯〇.3g中溶解二辛基磺基琥珀酸 鈉0.3g而成之單體混合物，進行種聚合。之後進行1小時 -31- 201235375 熟成，形成被覆核部分之銷層。 其次冷卻至室溫（25。〇，以網眼120μιη的塑膠製網過 濾，獲得含有具核鞘構造之橡膠粒子之乳膠。將獲得之 礼膠於-30。(：冷;東，並以抽吸過滤器進行脫水洗務後，於 60 C進行一日夜送風乾燥，獲得橡膠粒子。獲得之橡膠 粒子之平均粒徑為254nm、最大粒徑為486nm。 ^ 又，橡膠粒子之平均粒徑、最大粒徑，係使用以動 態光散射法為測定原理之「Nan〇tracTM」形式之 粒度分布測定裝置（商品名「υρΑ_Εχΐ5〇」、日機裝（股） 製）測定言式樣，針對獲得之粒度分布曲線，以，累積曲線成 為50%之時點的粒徑累積平均徑當作平均粒徑粒度分 布測定結果之頻率（％)超過〇 〇〇%之時點的最大粒徑當作 最大粒彳二。又，上述試樣，使用將下列製造例2獲得之橡 膠粒子分散環氧化合物丨重量份分散於四氫呋喃2〇重量 份者。 製造例2 (橡膠粒子分散環氧化合物之製造） 將製造例1獲得之橡膠粒子1 0重量份，於氮氣流下升 溫於60。(：之狀態，使用溶解器（diss〇lver)(1〇〇〇rpm、6〇 分鐘）’分散於商品名「Ceii〇xide2021P」（3,4-環氧環己 基甲基（3,4-環氧）環己烷羧酸酯、Daicel(股）製）70重量份 進行真空脫泡，獲得橡膠粒子分散環氧化合物（25 °C之 黏度：624mPa · s)。 又，製造例2獲得之橡膠粒子分散環氧化合物（1〇重 量份之橡膠粒子分散於7〇重量份iCell〇xide2〇21p者）之 -32- 201235375 黏度（於2 5 C之黏度），係使用數位黏度計（商品名「 DVU-EII 型」、Tokimec(股）製）測定。 製造例3 (%氧樹脂之製造.貫施例1〜7、比較例2、3) 將異二聚氰酸單烯丙基二環氧丙酯（商品名「ma_ PGIC」、四國化成工業（股）製）、脂環環氧化合物（商品 名「Cell〇Xide2021i&gt;」、Daicei(股）製）、製造例2獲得之 橡膠粒子分散環氧樹脂、雙酚A型環氧樹脂（商品名「 YD-128」、新日鐵化學（股）製），依表以斤示之摻^配方（ 摻合比例）（單位：重量份）混合，於8〇t攪拌i小時，使異 二聚氰酸單烯丙基二環氧丙酯溶解，其次將聚碳酸酯二 醇（商品名「CD220PL」、Daicel(股）製）依表丄所示之摻合 配方（單位：重量份）混合，於60。(；攪拌i小時，藉此獲得 環氧樹脂（混合物）。又’表i中之「_」，代表未進行該成 分之摻合，表2、表3亦同。 製造例4 (至少含有硬化劑之硬化劑組成物之製造：實施例丨〜？、 比較例1〜3) 將硬化劑（酸Sf)(商品名「Rikacid MH-700」、新 曰本理化（股）製）100重量份、硬化促進劑（商品名r U CAT 18X」、San-apro(股）製）0.5重量份、添加劑（商品名「乙 二醉」、和光純樂工業（股）製）1重量份，使用自公轉式搜 拌裝置（商品名「脫泡練太郎AR-250」 、Thinky(股）樂 均勻混合並脫泡，獲得硬化劑組成物。 實施例1〜7、比較例1〜3 -33- 201235375 (硬化性J衣氧樹脂組成物之製造） 將製k例3獲得之環氧樹脂、製造例4獲得之硬化劑 組成物，使用自公轉式攪拌裝置（商品名「脫泡練太郎 AR-250」、Thinky(股）製）均勾混合並脫泡，以成為表丄 所示摻合比例（單位：重量份），獲得硬化性環氧樹脂組 成物。又，比較例1之情形，環氧樹脂係使用商品名「On the other hand, when the amount of the curing accelerator (F) used exceeds 5 parts by weight, the cured product may be colored and the hue may be deteriorated. &lt;Acrylic-based block copolymer&gt; The curable epoxy resin composition of the present invention preferably contains an acrylic-based block copolymer from the viewpoint of suppressing a decrease in the luminosity of the optical semiconductor device with time. More specifically, when the curable epoxy resin composition of the present invention contains an acryl-based block copolymer, the optical semiconductor device sealed with the curable epoxy resin composition has high luminance and high output. The tendency that the luminosity is not easily lowered. In other words, the cured product obtained by curing the curable epoxy resin composition of the present invention by using an acrylic-based block copolymer can exhibit higher levels of heat resistance, light resistance, and turtle resistance. The above acrylic-based block copolymer ' is a block copolymer containing an acrylic monomer as an essential monomer component. The above acrylic monomer, for example, decyl acrylate, ethyl acrylate, n-butyl acrylate, albino glycerol, 2-ethylhexyl acrylate, thioglycolic acid, acetoacetate -19- 201235375 Ethyl enoate, n-butyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, stearyl methacrylate, etc. An alkyl acrylate; a cyclohexyl acrylate having a alicyclic structure such as cyclohexyl acrylate or cyclohexyl acrylate; an aromatic ring-based (mercapto) acrylate such as benzyl methacrylate; methacrylic acid; a (fluoro)alkyl ester of (meth)acrylic acid such as 2-trifluoroethyl ester; a carboxyl group-containing acrylic monomer having a carboxyl group in a molecule such as acrylic acid, methacrylic acid, maleic acid or maleic anhydride; 2-hydroxyl acrylate Ethyl ester, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-propyl propyl methacrylate, 4-hydroxybutyl methacrylate, glycerin a hydroxy group-containing C having a hydroxyl group in a molecule such as mono (meth) acrylic acid Acid-based monomer; glycidyl methacrylate, methyl epoxidized propyl methacrylate, methyl = olefinic acid 3,4-epoxycyclohexyl acetonitrile, etc. An allyl-containing acrylic group-containing monomer having an allyl group in a molecule such as allyl acrylate or allyl methacrylate; γ-methacryloxypropyl-decyloxydecane, γ-mercaptopropene a hydroxyl group-containing monomer having a hydrolyzable 11 group in a molecule such as methoxypropyltriethoxy or the like, 2 (2·hydroxy-5'-methacryloxyethylphenyl)-2Η - Benzene tri-sigma sitting, etc., having a right-weighted acrylic-based monomer, such as a UV-absorbing group. ^ In the above-mentioned aceto butter group block copolymer, a monomer other than the above-mentioned acryl monomer may be used as a monomer component. A single vessel other than the above-mentioned acrylic monomer. 'For example, an aromatic vinyl compound such as stupid ethylene or α-methylstyrene, a conjugated diene such as butyl methacrylate, isoprene, or ethylene, An olefin such as propylene or isobutylene. -20- 201235375 The above acrylic-based block copolymer is not particularly limited, and 彳W is, for example, a diblock copolymer composed of two polymer blocks, or a triblock copolymer composed of three blocks. A multi-block copolymer composed of four or more poly-Bangshan κ 13 blocks. Among them, the above-mentioned acrylic-based block copolymer is preferably a polymer block (s) of glass transfer and temperature production (butyl) from the viewpoints of improvement in resistance to hydrazine, light resistance, light resistance, and crack resistance (soft embedded) Segment), and a polymer block (Η) having a Tg than the polymer block = (hard segment) is alternately arranged as a private compound block (S) )) and a triblock copolymer of HSH structure with two segments (Η) at both ends. Further, the Tg of the polymer constituting the polymer block (S) of the above-mentioned C:acid 2 block copolymer is not particularly limited, and is preferably less than 30 °C. Further, the Tg of the polymer constituting the polymer block (H) is not particularly limited, and is preferably 30 ° C or higher. When the above acrylic-based block copolymer has a plurality of polymer blocks (H), each of the polymer blocks ((1) may have the same composition or may be different. Similarly, the above-mentioned acrylic-based block copolymer has a plurality of polymer blocks. When (S), the respective polymer blocks (s) may have the same or different compositions. The above-mentioned acrylic-based block copolymer (the above-mentioned HH structure triblock copolymer, etc.) constitutes a polymer block (H) The monomer component is not particularly limited, and examples thereof include a monomer having a Tg of 30 t or more in a homopolymer, and more specifically, for example, decyl methacrylate, styrene, acrylamide, acrylonitrile, and the like. In one aspect, in the above acrylic-based block copolymer, the monomer component constituting the polymer block (S) is not particularly limited, for example, a monomer having a homopolymer of less than 30 C, more specifically, for example, Cno alkyl acrylate such as butyl acrylate or 2-ethylhexyl acrylate, butadiene (丨, 4-butadiene), etc. -21 - 201235375 Acrylic based embedding of the curable epoxy resin composition of the present invention Preferred specific examples of the segment copolymer, for example, the above polymer block s) a polymer composed of a monomer mainly composed of butyl acrylate (BA), the polymer block (H) being a polymer composed of a monomer mainly composed of methyl methacrylate (mma), Polymethyl methacrylate-bl〇ck_polybutyl acrylate-bl〇ck_polymethyl methacrylate terpolymer (PMMA-b-PBA-b-PMMA), etc. The above PMMA_b-PBA-b-PMMA It is preferable from the viewpoints of improvement in finernity, light resistance, and crack resistance. Further, the above PMMA-b-PBA-b-PMMA 'visual need' is to improve the composition of the component (A) and the component (B). For the purpose of mutual solubility, a monomer having a hydrophilic group (for example, a hydroxyl group, a carboxyl group, an amine group, or the like) such as hydroxyethyl (meth) acrylate, hydroxypropyl acrylate (mercapto) acrylate, or the like. The number average molecular weight of the above acrylic-based block copolymer is not particularly limited, and is preferably from 3,000 to 500,000, more preferably from 10,000 to 300,000, still more preferably from 30,000 to 400,000. If the number average molecular weight is less than 3〇〇〇 (especially less than 1 000), the hardness and toughness of the hardened material are insufficient, and sometimes the crack resistance is lowered. On the other hand, if the number average molecular weight exceeds 50,000, the miscibility with the alicyclic epoxy compound (A) may decrease, and the transparency of the cured product may decrease. The above number average molecular weight may be, for example, a gel permeation layer. The calculation of the molecular weight in terms of standard polystyrene measured by the analytical method (GPC method) The above-mentioned acrylic-based block copolymer can be produced according to a known method for producing a block copolymer, or a method for producing the above-mentioned acrylic-based block copolymer. From the viewpoint of easy control of the molecular weight, molecular weight distribution and terminal structure of the acrylic acid-based block copolymer, active polymerization (activity from -22 to 201235375 by radical polymerization, living anionic polymerization, living cationic polymerization, etc.) good. The above living polymerization ' can be carried out in accordance with a known or customary method. Further, the above-mentioned acrylic acid-based fragment copolymer may be used, for example, under the trade names "NANOSTRENGTH M52N", "NANOSTRENGTH M22N", "NANOSTRENGTH M51", "NANOSTRENGTH M52", "NANOSTRENGTH M53" (Arkema system) Commercial products such as PMMA-b-PBA-b-PMMA), trade names "NANOSTRENGTH E21", "NANOSTRENGTH E41" (Arkema, PSt (polystyrene)-b-PBA-b-PMMA). The amount (content) of the acryl-based block copolymer is not particularly limited, and is preferably from 1 to 30 parts by weight, more preferably, based on the total amount of the component (A) and the component (B) (1 part by weight). It is 3 to 15 parts by weight, and more preferably 5 to 10 parts by weight. When the amount of the acrylic-based block copolymer used is less than 1 part by weight, the toughness of the cured product may be insufficient, and heat resistance and light resistance may be lowered. On the other hand, when the amount of the acrylic-based block copolymer used exceeds 30 parts by weight, the miscibility with the alicyclic epoxy compound (A) is lowered, and the transparency of the cured product may be lowered. &lt;Rubber Particles&gt; The curable epoxy resin composition of the present invention may further contain rubber particles. The rubber particles are, for example, rubber particles such as particulate NBR (acrylonitrile-butadiene rubber), reactive terminal carboxyl group NBR (CTBN), metal-free NBR, and particulate SBR (styrene-butadiene rubber). The rubber particles are preferably rubber particles comprising a core portion having rubber elasticity and a multilayer structure (nuclear sheath structure) composed of at least one sheath layer covering the core portion. The rubber particles are preferably composed of a polymer (polymer) having (mercapto) acrylate as an essential monomer component -23-201235375, and having a hydroxyl group and/or a carboxyl group on the surface (either one or both of a hydroxyl group and a carboxyl group). A rubber particle which is a functional group capable of reacting with an epoxy group-containing compound such as an alicyclic epoxy resin (A). When the surface of the rubber particles does not have a hydroxyl group and/or a carboxyl group, the cured product becomes cloudy due to thermal shock such as a heat cycle, and the transparency is lowered, which is not preferable. Among the rubber particles, the polymer constituting the core portion having rubber elasticity is not particularly limited, and is preferably methyl (meth)acrylate, ethyl (meth)acrylate or butyl (meth)acrylate (曱) Acrylate is used as an essential monomer component. The polymer constituting the rubber-elastic core portion may contain, for example, an aromatic vinyl compound such as styrene or α-mercaptostyrene; a nitrile such as acrylonitrile or methacrylonitrile; a conjugated diene such as isoprene; an enethene such as ethylene, propylene or isobutylene is used as a monomer component. And wherein the polymer constituting the rubber-elastic core portion contains a (meth) acrylate as a monomer component, and is selected from the group consisting of an aromatic compound, _, and a total of a diene. It is preferable that the combination of the old ones or more is the group of the constituents. That is, a polymer constituting the above-mentioned core portion, for example, a (meth) acrylate/aromatic vinyl compound, a binary copolymer such as 6 曰/conjugated diene (meth) acrylate; (mercapto) acrylate/ Aromatic brik vinyl compound ternary copolymer such as conjugated diene. Further, the polymer may be contained in the polymer of the core portion, such as polyoxymethylene oxide or polycarbamate such as polydimethylsiloxane or polyphenylmethyloxane. The polymer of the above-mentioned core portion may also contain divinylbenzene, allyl (meth)acrylate, ethylene glycol dimethyl acrylate, and diene maleate in terms of other monomer components. § Purpose, triallyl cyanurate, -24 - 201235375 1,1- phenylene phthalate, butanediol diacrylate, etc. 1 monomer (1 molecule) /, more than 2 reactive functionalities a reactive cross-linking monomer. The core portion of the rubber particles is composed of a binary copolymer of (fluorenyl) acrylate/aromatic vinyl compound (especially butyl acrylate/styrene). The core burr easily adjusts the refractive index of the rubber particles from 旎The point of view is better. The core portion of the rubber particles can be produced by a usual method, and can be produced, for example, by a method of polymerizing the above monomers by an emulsion polymerization method. In the emulsion polymerization method, the above monomers may be added in one portion at a time, or a part of the monomers may be first polymerized, and the remaining portion may be continuously or intermittently added and polymerized. Alternatively, the polymerization method using the seed particles may be used to form the above. The polymer of the tough layer of the rubber particles is preferably a polymer different from the polymer constituting the above-mentioned core portion. Further, as described above, the sheath layer preferably has a hydroxyl group and/or a carboxyl group as a functional group capable of reacting with an epoxy group-containing compound such as an alicyclic epoxy compound (A). Therefore, in particular, the adhesion to the interface with the alicyclic epoxy compound (A) can be improved, and the cured product obtained by curing the curable epoxy resin composition containing the rubber particles having the sheath layer can be excellent. Resistance to cracking. Further, it is also possible to prevent the glass transition temperature of the hardened material from being lowered. The polymer constituting the sheath layer preferably contains (meth)acrylic acid methacrylate such as (meth)acrylic acid ethyl ester or (meth)acrylic acid butyl acrylate as an essential monomer component. For example, in the above-mentioned core portion, when butyl acrylate is used for the (meth) acrylate, the monomer component of the polymer constituting the sheath layer is preferably a (meth) acrylate other than butyl acrylate (for example: (-25- 201235375 methyl methacrylate, (meth) acrylate, methacrylic acid, etc.). An aromatic vinyl compound such as monostyrene, which may be contained in addition to (meth)acrylic acid, or a nitrile such as methacrylonitrile or the like. In the rubber particles, a monomer constituting a slight layer is formed into a knife, and (meth) acrylate is preferably used alone or in combination of two or more kinds, and in particular, when at least an aromatic vinyl compound is contained, The viewpoint of adjusting the refractive index of the above rubber particles is preferred. Further, the polymer constituting the sheath layer is a monomer component for forming a hydroxyl group and/or a carboxyl group which is a functional group reactive with a compound having an epoxy group such as an alicyclic epoxy compound (A). It is preferable to contain a hydroxyalkyl (meth)acrylate such as 2-hydroxyethyl (meth)acrylate, or an α,β-unsaturated acid such as (meth)acrylic acid or an α,ρ unsaturated acid anhydride such as maleic anhydride. . In the rubber particles, the polymer constituting the sheath layer contains s' and contains (mercapto) acrylate, and one or a combination of two or more kinds selected from the above monomers. That is, the sheath layer is, for example, (meth)acrylic acid vinegar/aromatic vinyl compound/hydroxyalkyl (meth) acrylate, (meth) acrylate/aromatic vinyl compound/α, β_unsaturated A sheath layer composed of a terpolymer such as an acid or the like is preferred. Further, the polymer constituting the sheath layer may contain, in addition to the above monomers, divinylbenzene, allyl (meth) acrylate, and ethylene glycol in terms of other monomer components. (Mercapto) acrylate, monoallyl maleate, tri-lapropyl propyl cyanate, diterpene bismuth diacetate, butanediol diacrylate, etc. A reactive crosslinking monomer having two or more reactive functional groups. The rubber particles (rubber particles having a nucleus sheath structure) can be obtained by coating the core portion of -26-201235375 with a sheath. Coating the core portion by a layer coating method, for example, on the surface of the rubber-elastic core portion obtained by the above method, coating the copolymer constituting the sheath layer to perform coating, and obtaining the rubber elasticity obtained by the above method The core is used as a branch component for each component constituting the Le layer, and is grafted and aggregated. The average particle diameter of the above rubber particles is not particularly limited, and i nm is more preferably 20 to 4 Å. Further, the maximum particle diameter of the rubber particles is not particularly limited, but is preferably 50 to 1 nm, more preferably 1 to 8 nm. When the average particle diameter is more than 50 Å, or the maximum particle diameter is more than 1 〇〇〇 nm, the dispersibility of the rubber particles in the cured product is lowered, and the crack resistance is sometimes lowered. On the other hand, if the average particle diameter is less than 10 nm or the maximum particle diameter is less than 5 Å, the effect of improving the crack resistance of the cured product may not be easily obtained. The refractive index of the above rubber particles is not particularly limited, and is preferably 14 〇 16 〇 , more preferably 1.42 〜 1.58. Further, the difference between the refractive index of the rubber particles and the refractive index of the cured product obtained by curing the curable epoxy resin composition containing the rubber particles (the curable epoxy resin composition of the present invention) is ± Within 0.03 (_0·03~〇.03) is preferred. When the difference in refractive index is more than ±0.03, the transparency of the cured product may be lowered, and the film may become cloudy, and the illuminance of the optical semiconductor device may be lowered, and the function of the photo-semiconductor device may be lost. The refractive index of the rubber particles can be, for example, injected into a forming mold by compression molding at 2 UTC and 4 MPa to obtain a flat plate having a thickness of 1 mm, and a test piece having a length of 2 mm and a width of 6 mm can be cut out from the obtained flat plate. Using a monobromonaphthalene as an intermediate liquid, a multi-wavelength Abbe refractometer (trade name "DR_M2", Atag® (manufactured by the company)) was used in the 2crc state in which the prism was brought into close contact with the test piece in the state of -27-201235375. The refractive index is determined by a sodium sputum line. The refractive index of the cured product of the curable epoxy resin composition of the present invention can be, for example, a cured product obtained by a heat curing method described in the item of the optical semiconductor device described later, and cut into a longitudinal thickness of 2 mm> The test piece was used as an intermediate liquid, and a multi-wavelength Abbe refractometer (trade name "dr_m2", manufactured by AUGO) was used to measure the state in which the ruthenium was adhered to the test piece. The refractive index of 〇t and sodium lanthanum is obtained. In the curable epoxy resin composition of the present invention, the rubber particles are contained in an amount of (the amount of blending) which is not particularly limited to (4) the total amount of the epoxy group-containing compound contained in the curable epoxy resin composition (1〇) 〇 parts by weight, preferably from 5 to 30 parts by weight, more preferably from 丨 to "parts by weight. If the content of the rubber particles is less than 0.5% by weight, the crack resistance of the cured product tends to decrease. When the content of the rubber particles exceeds 30 parts by weight, the heat resistance of the cured product tends to decrease. <Additives> The curable epoxy resin composition of the present invention does not impair the above-mentioned Various additives may be used within the scope of the effects of the present invention. For example, if a compound having a hydroxyl group such as ethylene glycol, diethylene glycol, propylene glycol or oil is used, the reaction can be carried out gently. And the viscosity or transparency of the _, can be used polysulfide or iu defoamer, coated with gamma-glycidoxypropyl trimethoxy oxalate and other stone burning coupling agent, surfactant, Dioxo, oxidizing material, inorganic filling) agent H color agent 'antioxidation Chemical agent, ultraviolet absorber, and other conventional additives such as an adsorbent, a pigment, a phosphor, a mold release agent, etc. -28- 201235375 &lt;Cured product&gt; By hardening the curable epoxy resin composition of the present invention It is possible to obtain a cured product which is excellent in various physical properties such as light resistance, transparency, and crack resistance, and which is excellent in reflow resistance. The heating temperature (hardening temperature) at the time of curing is not particularly limited, and is preferably 45~ 200 it, more preferably 1〇〇~19〇艺, and more preferably io〇~18(rc ^ again, the heating time (hardening time) when hardening is not particularly limited, preferably 30~600 minutes' is better 45~54〇 minutes, = more preferably 60~48〇 minutes. If the hardening temperature and the hardening time are lower than the lower limit of the above range, the hardening is insufficient, and if it is higher than the upper limit of the above range, the resin component is When it is decomposed, it is not good. The hardening conditions are lost in various conditions, and the hardening time is shortened when the hardening temperature is high, and the hardening time is lengthened when the hardening temperature is low, and can be appropriately adjusted. &lt;Resin composition for optical semiconductor sealing&gt; Optical semiconductor dense of the present invention The resin composition is composed of the curable epoxy resin composition of the present invention. The optical semiconductor element is sealed by using the resin composition for optical semiconductor sealing of the present invention, and heat resistance, light resistance, and transparency can be utilized. An optical semiconductor device is obtained by sealing an optical semiconductor element with a cured product which is excellent in resistance to cracking and is excellent in reflow resistance. <Optical semiconductor device> The optical semiconductor device of the present invention can be used The photo-semiconductor element is obtained by sealing the curable epoxy resin composition (resin composition for optical semiconductor encapsulation) of the present invention. The sealing of the optical semiconductor element is a curable epoxy resin composition prepared by the above method. The predetermined forming die is injected and heat-hardened under predetermined conditions. Thereby, an optical semiconductor device in which a photo-semiconductor conductor member is sealed with a curable -29-201235375 epoxy resin composition can be obtained. The hardening temperature and the hardening time can be the same as the above-mentioned basket 哀 ^ m ^ m. _ 0 /. The optical semiconductor device of the present invention is less likely to be deteriorated by the heat treatment of the reflow 洚 TW ± , and the luminosity is less likely to be reduced in time. In general, the photo-semiconductor test; MM π _L s is centered, as shown in Fig. 1, the photo-semiconductor element 侏μ, etc. is fixed to the lead frame by the solid-state material 105. The inventor of the case found that the 固 was optimized by the solid crystal material in the semi-conductive splicing of the light, and also had the same resistance to reflow. More details + + m β + 吏$ 5, when the optical semiconductor device is heated by the reflow step, depending on the stress generated by the volume change of the enamel resin, the optical semiconductor component is selected. Stripped solid crystal material (adhesive and high-hardness solid crystal) Gan S m is important. The reason is that when the Guangfeng conductor is peeled off from the lead frame, the sealing resin around the dry conductor element is prone to peeling or cracking. The deterioration of the optical semiconductor device caused by the heat treatment in the reflow step may change. Significantly. Therefore, in order to improve the reflow resistance and prevent deterioration of the optical semiconductor device by the heat treatment in the reflow step, the curable epoxy resin composition of the present invention is used as a sealing resin (resin for sealing), and the above adhesiveness and durability are used. The solid crystal material is used as a solid crystal: it is effective. The above-mentioned solid crystal material is, for example, a solid crystal material obtained by containing a conductive polymer or the like (for example, silver particles or the like) as a base polymer such as a polyimide resin, an epoxy resin or a polysiloxane resin. Such a solid crystal #, for example: M2, KER-3100 02, KER-3100 (Shin-Etsu Chemical Co., Ltd.), EH1600-G2 (Inabata Industries), CT2〇〇, CT284, CT265 (Kyocera Chemical) (share) system, etc. The curable epoxy resin composition of the present invention is not limited to the above-mentioned photo-semiconductor sealing use. It can also be used, for example, for an adhesive, an electrical insulating material -30-201235375, a laminated board, a coating film, an ink, a coating material, and a transparent material. Substrate 'transparent sheet, lens, optical member, optical shape, battery substrate, optical waveguide, light guide [Example] Material, potting agent, resist, composite transparent film, optical element, optical electronic paper, touch panel , solar panels, holographic memory, etc. However, the present invention will be described in more detail below with reference to the embodiments without being limited to the embodiments. Production Example 1 (Production of Rubber Particles) In a 1 L polymerization vessel equipped with a reflux condenser, 500 g of ion-exchanged water and *dioctyl-sodium sulphate were added, and the temperature was raised to 8 Torr under a nitrogen stream. . a monomer mixed with 9.5 g of butyl acrylate, 2.57 g of styrene, and divinyl benzopyrene 39 §, which is equivalent to a 5% by weight component, for the amount necessary for forming a core portion, After mixing for 20 minutes to emulsification, 9 5 mg of peroxodisulfate was added and the mixture was mixed for 1 hour to carry out the initial polymerization. Next, potassium peroxodisulfate 1 8 〇.5 mg' was added and stirred for 5 minutes. Among them, it takes 2 hours to continuously add the remaining amount (about 95% by weight) of the amount necessary for forming the core portion to 180 /5 g of butyl acrylate, 48.89 g of styrene, and dioctyl benzene by dissolving dioctyl benzene. The monomer mixture of the sodium sulphate of 95 g of the base was subjected to the second seed polymerization, and then matured for 1 hour to obtain a core portion. Next, '60 mg of potassium peroxodisulfate was added, stirred for 5 minutes, and continuously added to methyl methacrylate 6 5 Lu, acrylic acid 1 _5 g, and allyl methacrylate 〇. 3 g for 30 minutes. A monomer mixture obtained by dissolving 0.3 g of sodium dioctylsulfosuccinate was subjected to seed polymerization. Thereafter, it is aged for 1 hour -31 - 201235375 to form a pin layer of the core portion. Next, cool to room temperature (25. 〇, filter with a mesh of 120 μιη mesh mesh to obtain a latex containing rubber particles with a nuclear sheath structure. The gum obtained will be obtained at -30. (: cold; east, and pumped After the suction filter was subjected to dehydration washing, it was air-dried overnight at 60 C to obtain rubber particles. The obtained rubber particles had an average particle diameter of 254 nm and a maximum particle diameter of 486 nm. ^ Further, the average particle diameter of the rubber particles was the largest. The particle size is measured by a particle size distribution measuring apparatus (trade name "υρΑ_Εχΐ5〇" or Nikkiso (manufactured by Nikko Co., Ltd.) in the form of "Nan〇tracTM" using the dynamic light scattering method as the measurement principle, and the obtained particle size distribution is obtained. In the curve, the cumulative average diameter of the particle diameter at the point where the cumulative curve becomes 50% is regarded as the maximum particle size at the point where the frequency (%) of the average particle size distribution measurement result exceeds 〇〇〇%. In the above sample, the weight fraction of the rubber particle-dispersed epoxy compound obtained in the following Production Example 2 was dispersed in 2 parts by weight of tetrahydrofuran. Production Example 2 (Rubber particle-dispersed epoxy compound) Manufactured 10 parts by weight of the rubber particles obtained in Production Example 1 and heated to 60 in a nitrogen gas stream. (: In a state of dispersing in a product, using a dissolver (1 rpm, 6 〇 minutes) 70 parts by weight of "Ceii〇xide2021P" (3,4-epoxycyclohexylmethyl (3,4-epoxy)cyclohexanecarboxylate, manufactured by Daicel Co., Ltd.) was vacuum defoamed to obtain rubber particle dispersion. Epoxy compound (viscosity at 25 ° C: 624 mPa · s). Further, the rubber particle-dispersed epoxy compound obtained in Production Example 2 (one part by weight of rubber particles dispersed in 7 parts by weight of iCell〇xide 2 〇 21p) -32- 201235375 Viscosity (viscosity at 2 5 C), measured by a digital viscometer (trade name "DVU-EII type", manufactured by Tokimec Co., Ltd.). Manufacturing Example 3 (Production of % Oxygen Resin) 1 to 7, Comparative Example 2, 3) Isopropyl propylene glycol monomethacrylate (trade name "ma_ PGIC", manufactured by Shikoku Chemicals Co., Ltd.), alicyclic epoxy compound (product) "Cell 〇 Xide 2021i", "Daicei"), rubber particle-dispersed epoxy resin obtained in Production Example 2, bisphenol A type Epoxy resin (trade name "YD-128", Nippon Steel Chemical Co., Ltd.), according to the formula of the mixture of the formula (mixing ratio) (unit: parts by weight), mixing at 8 °t In the hour, the isocyanurate monoallyl diglycidyl ester is dissolved, and then the polycarbonate diol (trade name "CD220PL", Daicel (manufactured by the company)) is blended according to the formula (unit : parts by weight), mixed at 60. (; stirring for 1 hour, thereby obtaining an epoxy resin (mixture). Also, "_" in the table i means that the blending of the component is not carried out, and Table 2 and Table 3 are also with. Production Example 4 (Production of a hardener composition containing at least a curing agent: Example 丨~?, Comparative Examples 1 to 3) A curing agent (acid Sf) (trade name "Rikacid MH-700", Shinji Ryokan ( 100 parts by weight, a hardening accelerator (trade name: r U CAT 18X), manufactured by San-apro Co., Ltd., 0.5 parts by weight, and an additive (trade name "Ethylene", and Wako Pure Chemical Industries Co., Ltd. 1 part by weight, a self-revolving type mixing device (trade name "defoaming ritaro AR-250", and Thinky" was uniformly mixed and defoamed to obtain a hardener composition. Examples 1 to 7, Comparative Examples 1~3 -33-201235375 (Production of Curable J Oxygen Resin Composition) The epoxy resin obtained in Example 3 and the hardener composition obtained in Production Example 4 were used, and a self-revolving stirring device (trade name " Defoaming Ryotaro AR-250" and Thinky Co., Ltd. are all mixed and defoamed to obtain a hardening epoxy resin composition by the blending ratio (unit: parts by weight) shown in Table 。. In the case of Example 1, the epoxy resin is sold under the trade name "

Celloxide2021P」（Daicel(股）製）。 (光半導體裝置之製造） 將上述獲得之硬化性環氧樹脂組成物，澆鑄於第1 圖所示之光半導體之導線架（inGaN元件、3 5mmx2 8mm) 模後’於1 20 c之烘箱（樹脂硬化烘箱）進行5小時加熱獲 得以硬化之樹脂（硬化物）將光半導體元件予以密封之光 半導體裝置。又，第1圖中，1〇〇表示反射件（光反射用樹 脂組成物）、101表示金屬配線、102表示光半導體元件、 103表示接合引線、1 〇4表示透明密封樹脂（硬化物）、丄 表示固晶材。 製造例5 (環氧樹脂之製造：實施例8〜1 4、比較例5、6) 將異三聚氰酸單稀丙基二環氧丙酯（商品名「ma_ DGIC」、四國化成工業（股）製）、脂環環氧化合物（商品 名「Celloxide2021P」、Daicel(股）製）、製造例2獲得之 橡膠粒子分散環氧樹脂、雙盼A型環氧樹脂（商^名「 YD-m 、新日鐵化學（股）製）’依照表2所示之$合配 方（摻合比例）（單位：重量份）混合，於8〇t進行i小時攪 拌，藉此使異三聚氰酸單烯丙基二環氧丙酯溶解，其次 -34- 201235375 將聚碳酸酯二醇（商品名「CD220PL」、Daicel(股）製）依 照表2所不之摻合配方（單位：重量份）混合，於6〇它攪拌^ 小時’藉此獲得環氧樹脂（混合物）。 實施例8〜1 4、比較例4〜6 (硬化.性環氧樹脂組成物之製造） 將製造例5獲得之環氧樹脂、硬化觸媒（商品名「以卜 aid SI-100L」、三新化學工業（股）製），使用自公轉式攪 拌裝置（商品名「脫泡練太郎AR-250」 、Thinky(股）製） 均勻混合並脫泡’使成為表2所示摻合比例（單位：重量 伤）’獲付硬化性ί哀氧樹脂組成物。又，比較例4之情形 ’環氧樹脂使用商品名「〇611〇\丨(^2021?」（〇3461(股） 製）。 (光半導體裝置之製造） 將上述獲得之硬化性環氧樹脂組成物，澆鑄於第1 圖所示之光半導體之導線架（InGaN元件' 3.5mmx2.8mm) 模後’於120 C之烘箱（樹脂硬化烘箱）進行5小時加熱，獲 得以硬化之樹脂（硬化物）將光半導體元件予以密封之光 半導體裝置。 &lt;評價&gt; 針對實施例1〜14及比較例1〜6獲得之光半導體裝置 ’依以下方法實施評價試驗。 [焊料耐熱性試驗] 使實施例1〜14及比較例1〜6獲得之光半導體裝置（各 硬化性環氧樹脂組成物各使用2個），於30°C、70%RH之 條件下靜置16 8小時使吸濕。其次，將上述光半導體裝置 -35- 201235375 放入回流爐（UNI-5016F、日本Antom(股）製），依下列加 熱條件進行加熱。之後’將上述光半導體裝置取出於室 溫壞境下並放冷後，再度放入回流爐，以同條件進行加 熱亦即，於该焊料耐熱性試驗中，對於光半導體裝置 以下列加熱條件施以2次熱履歷。 [加熱條件（光半導體裝置之表面溫度基準）] (1) 預備加熱：於150〜19〇。(：加熱60〜120秒 (2) 預備加熱後之正式加熱：21&lt;rc以上進行6〇〜15〇秒最Celloxide 2021P" (made by Daicel). (Manufacturing of Photo-Semiconductor Device) The curable epoxy resin composition obtained above was cast in a lead frame (inGaN element, 35 mm x 2 8 mm) of the optical semiconductor shown in Fig. 1 in an oven of 1 20 c ( The resin hardening oven was heated for 5 hours to obtain an optical semiconductor device in which the optical semiconductor element was sealed with a cured resin (cured material). In the first drawing, 1 〇〇 indicates a reflector (a resin composition for light reflection), 101 indicates a metal wiring, 102 indicates an optical semiconductor element, 103 indicates a bonding wire, and 1 〇 4 indicates a transparent sealing resin (cured material).丄 denotes a solid crystal material. Production Example 5 (Production of Epoxy Resin: Examples 8 to 14 and Comparative Examples 5 and 6) Isopropyl propylene carbonate (trade name "ma_ DGIC", Shikoku Kasei Industrial Co., Ltd.) (manufactured by the company), an alicyclic epoxy compound (trade name "Celloxide 2021P", manufactured by Daicel Co., Ltd.), a rubber particle-dispersed epoxy resin obtained in Production Example 2, and a double-prepared A-type epoxy resin ("YD" -m, Nippon Steel Chemical Co., Ltd.) 'According to the formula (mixing ratio) shown in Table 2 (unit: part by weight), mix at 8 °t for 1 hour to make heterotrimerization Cyanate monoallyl diglycidyl ester dissolved, followed by -34- 201235375 Polycarbonate diol (trade name "CD220PL", Daicel (manufactured by the company)) according to the blending formula of Table 2 (unit: weight Mix), stir it at 6 ^ for 'hours' to obtain an epoxy resin (mixture). Examples 8 to 14 and Comparative Examples 4 to 6 (Production of a cured epoxy resin composition) The epoxy resin and the curing catalyst obtained in Production Example 5 (trade name "Aid SI-100L", three New Chemical Industry Co., Ltd., using a self-propelled stirring device (trade name "Defoaming Ryotaro AR-250", Thinky Co., Ltd.), uniformly mixing and defoaming, so that the blending ratio shown in Table 2 is obtained ( Unit: Weight injury) 'Accepted hardening oh oxidizing resin composition. In the case of the comparative example 4, the epoxy resin was used as the epoxy resin, and the product name was "〇 611 〇 丨 ^ ^ ^ ^ ^ ^ ^ 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( The composition was cast in a lead frame of an optical semiconductor (InGaN element '3.5 mm x 2.8 mm) shown in Fig. 1 and heated in a 120 C oven (resin hardened oven) for 5 hours to obtain a hardened resin (hardened). An optical semiconductor device in which an optical semiconductor device is sealed. <Evaluation> The optical semiconductor device obtained in Examples 1 to 14 and Comparative Examples 1 to 6 was subjected to an evaluation test by the following method. [Solder heat resistance test] The optical semiconductor devices obtained in Examples 1 to 14 and Comparative Examples 1 to 6 (two for each curable epoxy resin composition) were allowed to stand at 30 ° C and 70% RH for 16 8 hours to absorb moisture. Then, the optical semiconductor device-35-201235375 was placed in a reflow furnace (UNI-5016F, manufactured by Antom, Japan) and heated under the following heating conditions. Then, the above-mentioned optical semiconductor device was taken out at room temperature. And put it cold, put it back again The flow furnace was heated under the same conditions, that is, in the solder heat resistance test, the thermal history was applied twice to the optical semiconductor device under the following heating conditions. [Heating conditions (surface temperature reference of optical semiconductor device)] (1) Preheating: 150~19〇. (: Heating 60~120 seconds (2) Formal heating after preliminary heating: 21 &lt; rc above 6〇~15〇 second

南溫度2 6 0 °C 惟’從預備加熱進行到正式加熱時之升溫速度，控 制最大為3°C /秒。 第2圖顯示以回流爐加熱時，光半導體裝置之表面溫 度折線圖（二次的加熱當中，其中之一的加熱的溫度折線 圖）之一例。 之後’使用數位顯微鏡（VHX_900、Keyence(股）製）觀 察光半導體裝置，觀測到光半導體裝置2個當中有任一個 或兩個於電極表面上發生樹脂剝離時，評為「不良」（耐 回流性不良），於供試驗之2個光半導體裝置均未認為有剝 離時評為「良好」（耐回流性良好）。結果如表i、表2。 [通電試驗] 將實施例1〜14及比較例1〜6獲得之光半導體裝置之 全光束使用全光束測定機測定。 再者，於60°C、90%RH之恆溫槽内測定對於光半導 體裝置流過70mA之電流1〇00小時後之全光束。從下式計 算光度保持率。結果如表1、表2。 -36- 201235375 {光度保持率（％)} = { 1000小時後之全光束（lm)}/{〇小時之全光束（im)} X 100 [熱衝擊試驗] 胃使用熱衝擊試驗機，對於實施例及比較例i〜6 2 Γ之光半導體裝置（各硬化性環氧樹脂組成物各使用2 此、於-40 C加熱15分鐘，接著於120°C加熱15分鐘，以 半個/盾環的熱衝擊，共施加1000個循環。之後，於光 涔的體破置通入2〇mA的電流，進行亮燈確認，計測未亮 ^、光半導體裝置之個數（未亮燈發生數）。結果如表1、 ^所不。 [综合判定] 差)。：料耐熱性試驗之判定為不良時，綜合判定評為x ( 9〇。/。^料耐熱性試驗判定為良好者當中，▲度保持率為 列定評&quot;1且於熱衝擊試驗之未亮燈發生數為〇個者，综合 Ό (非常優異），其餘综合判定評為△(優良）。 -37- 201235375 比較例3 1 1 〇 r—H 不良 T-H 00 〇 X 1比較例2 1 § 1 1 no 1 不良| 〇 X |比較例1 〇 〇 1 1 1 1 110 1 不良| 〇 X |實施例7 〇 1 1 1 no 1 〇 〇 實施例6 〇 〇 1 ο Ο r-H |良好| 〇 〇 實施例5 〇 1 1 Ο r-H r-H &lt; 實施例4 〇 〇 1 1 1 no 1 |良好| 〇 〇 實施例3 〇 1 1 Ο 1—^ τ·^ 〇 〇 |實施例2 〇 1 1 ο »-Η r—Η 〇 〇 實施例1 〇 〇 1-H 1 1 no 1 良好」 〇 〇 CEL2021P MA-DGIC CD220PL YD-128 橡膠粒子 ¥ .tmil 1——J 荽 焊料耐熱性試驗 光度保持率[%] 1 1 夺 學 (N U 澈Μ 1¾ 物·窀 1&lt; 綜合判定 環氧樹脂 [重量份] 崩 蘅 tfti k 硬化性 環氧樹脂 組成物 硬化物 (光半導體 裝置） -8ε- 201235375 【&lt;Ν&lt;】 比較例61 1 1 〇 1不良| 〇〇 〇 X 1比較例5 1 § 1 〇 |不良| CN 00 〇 X 比較例4 100 1 1 1 1 〇 不良| 〇〇 〇 X 1實施例14| 〇 1 1 d (N 〇\ 〇 〇 實施例13 〇 〇 1 〇 c&gt; JttU 〇 〇 實施例12 〇 〇 CN 1 1 vn O &lt;3 實施例11 〇 〇 1 1 iT) o &lt;N 〇\ 〇 〇 實施例10 〇 1 1 O 〇 〇 |實施例9| 〇 00 〇 咖 1 O 良好| CO 〇\ 〇 〇 |實施例8 〇 〇 1 1 o 〇 〇 CEL2021P MA-DGIC CD220PL YD-128 橡膠粒子 San-aid SI-100L 焊料耐熱性試驗 光度保持率[%] r—1 學 CN 輪 M f 命 Z ^ 綜合判定 環氧樹脂 [重量份] 硬化觸媒 [重量份] 環氧樹脂 組成物 硬化物 (光半導體 裝置） -6ε· 201235375 製造例6 (環氧樹脂之製造：實施例15〜18) 將異二聚氣酸单缔丙基二環氧丙醋（商品名「 MA-DGIC」、四國化成工業（股）製）、脂環環氧化合物（ 商品名「Celloxide2021P」、Daicel(股）製）、丙烯酸基嵌 段共聚物（商品名「NANOSTRENGTH M52N」、Arkema( 股）製）’依照表3所示之摻合配方（摻合比例）（單位：重量 份）混合，於8(TC攪拌1小時，使異三聚氰酸單烯丙基二 環氧丙酯（及丙烯酸基嵌段共聚物）溶解，其次將聚碳酸 酯二醇（商品名「CD220PL」、Daicel(股）製）依表3所示摻 合配方（單位：重量份）混合，於60。(：攪拌1小時，藉此獲 得環氧樹脂（混合物）。 實施例1 5 ~ 1 8、比較例7、8 (硬化性環氧樹脂組成物之製造） 將製造例6獲得之環氧樹脂、製造例4獲得之硬化劑 組成物、硬化觸媒（商品名「San_aid SI-100L」、三新 化學工業（股）製）’使用自公轉式攪拌裝置（商品名「脫泡 練太郎AR-250」、Thinky(股）製）均勻混合並脫泡，使成 為表3所示之摻合比例（單位：重量份），獲得硬化性環氧 樹脂組成物。又’比較例7、8之情形，環氧樹脂使用商 品名「Celloxide2021P」（Daicel(股）製）。 (光半導體裝置之製造） 將上述獲得之硬化性環氧樹脂組成物，澆鑄於第1 圖所示之光半導體之導線架（InGaN元件、3.5mmx2.8mm) 模後’於1 20°C之烘箱（樹脂硬化烘箱）進行5小時加熱， -40- 201235375 ' 獲得以硬化之樹脂（硬化物）將光半導體元件予以密封之 光半導體裝置。 &lt;評價&gt; 針對實施例15〜18及比較例7、8獲得之光半導體裝置 ，依以下方法實施通電試驗。 [通電試驗] 使用全光束測定機測定實施例1 5〜1 8及比較例7、8 獲得之光半導體裝置之全光束。再者，測定於溫度8 5 °C 之恆溫槽内對於光半導體裝置流入60mA之電流300小時 後之全光束。由下式計算光度保持率。結果如表3。 {光度保持率（％)} = {3 00小時後之全光束（lm)}/{0小時之全光束（lm)}The south temperature is 260 °C, but the temperature rise from the time of preparatory heating to the main heating is controlled to a maximum of 3 °C / sec. Fig. 2 is a view showing an example of a surface temperature line graph of an optical semiconductor device (a temperature profile of one of heating in the secondary heating) when heated in a reflow furnace. Then, the optical semiconductor device was observed using a digital microscope (VHX_900, manufactured by Keyence), and it was observed that either or both of the optical semiconductor devices were evaluated as "poor" when the resin was peeled off on the surface of the electrode. Poority), when the two optical semiconductor devices to be tested were not considered to be peeled off, they were rated as "good" (good reflow resistance). The results are shown in Tables i and 2. [Electrification test] The total light beams of the optical semiconductor devices obtained in Examples 1 to 14 and Comparative Examples 1 to 6 were measured using a total beam measuring machine. Further, the total light beam after flowing a current of 70 mA for 1 00 hours in the photo-semiconductor device was measured in a thermostat at 60 ° C and 90% RH. The photometric retention rate is calculated from the following formula. The results are shown in Tables 1 and 2. -36- 201235375 {Photostivity (%)} = {Full beam (1000) after 1000 hours} / {Full beam of light (im)} X 100 [Thermal shock test] The stomach uses a thermal shock tester, for EXAMPLES AND COMPARATIVE EXAMPLES i to 6 2 光 Optical semiconductor device (each of the curable epoxy resin compositions was used for 2 minutes, heated at -40 C for 15 minutes, and then heated at 120 ° C for 15 minutes, at half a shield The thermal shock of the ring is applied for a total of 1000 cycles. After that, a current of 2 mA is applied to the body of the diaphragm, and the light is confirmed. The number of the optical semiconductor devices is not brightened. The results are shown in Table 1. ^No. [Comprehensive judgment] Poor). : When the judgment of the heat resistance test is bad, the comprehensive judgment is judged as x (9 〇. / . ) The heat resistance test is judged to be good, the ▲ degree retention rate is listed as "1" and is not in the thermal shock test. The number of lighting occurrences is one, the total is Ό (very good), and the other comprehensive judgments are rated as △ (excellent). -37- 201235375 Comparative Example 3 1 1 〇r-H Bad TH 00 〇X 1 Comparative Example 2 1 § 1 1 no 1 bad | 〇X |Comparative example 1 〇〇1 1 1 1 110 1 bad | 〇X |Example 7 〇1 1 1 no 1 〇〇Example 6 〇〇1 ο Ο rH |Good | 〇〇 Example 5 〇1 1 Ο rH rH &lt;Example 4 〇〇1 1 1 no 1 |Good | 〇〇Example 3 〇1 1 Ο 1—^ τ·^ 〇〇|Example 2 〇1 1 ο » -Η r-Η 〇〇Example 1 〇〇1-H 1 1 no 1 Good" 〇〇CEL2021P MA-DGIC CD220PL YD-128 Rubber particles ¥.tmil 1——J 荽 solder heat resistance test luminosity retention rate [% ] 1 1 夺学(NU Μ 13⁄4 物·窀1&lt; Comprehensive judgment of epoxy resin [parts by weight] collapsed tfti k hardened epoxy tree Composition hardened material (optical semiconductor device) -8ε-201235375 [&lt;Ν&lt;] Comparative Example 61 1 1 〇1 defective | 〇〇〇X 1 Comparative Example 5 1 § 1 〇|bad | CN 00 〇X Comparative Example 4 100 1 1 1 1 〇 | | 〇〇〇 X 1 Example 14| 〇 1 1 d (N 〇 \ 〇〇 Example 13 〇〇 1 〇 c > JttU 〇〇 Example 12 〇〇 CN 1 1 vn O &lt 3 Example 11 〇〇1 1 iT) o &lt;N 〇\ 〇〇 Example 10 〇1 1 O 〇〇|Example 9| 〇00 〇 1 1 O Good|CO 〇\ 〇〇|Example 8 〇〇1 1 o 〇〇CEL2021P MA-DGIC CD220PL YD-128 Rubber Particles San-aid SI-100L Solder Heat Resistance Test Photometric Retention [%] r—1 Learning CN Wheel M f Life Z ^ Comprehensive Determination of Epoxy Resin [ Parts by weight] Hardening catalyst [parts by weight] Epoxy resin composition cured product (optical semiconductor device) -6 ε · 201235375 Production Example 6 (Production of epoxy resin: Examples 15 to 18) Propyl propylene glycol vinegar (trade name "MA-DGIC", manufactured by Shikoku Chemical Industry Co., Ltd.), alicyclic epoxy compound ( Product name "Celloxide 2021P", manufactured by Daicel Co., Ltd., and acrylic-based block copolymer (trade name "NANOSTRENGTH M52N", manufactured by Arkema)" according to the blending formula shown in Table 3 (mixing ratio) (unit : parts by weight), mixed at 8 (TC for 1 hour, dissolving isocyanurate monoallyl diglycidyl ester (and acrylic block copolymer), followed by polycarbonate diol (trade name) "CD220PL" and Daicel (manufactured by Daicel) were mixed according to the blending formula (unit: parts by weight) shown in Table 3, at 60. (: stirring for 1 hour, thereby obtaining an epoxy resin (mixture). Example 1 5 to 18, Comparative Example 7, 8 (Production of Curable Epoxy Resin Composition) The epoxy resin obtained in Production Example 6 was used. The hardener composition and the hardening catalyst (product name "San_aid SI-100L", manufactured by Sanshin Chemical Industry Co., Ltd.) obtained in Production Example 4 are used in a self-revolving stirring device (trade name "Degassing Ryotaro AR-250" "Thinky" was uniformly mixed and defoamed to obtain a blending ratio (unit: parts by weight) shown in Table 3 to obtain a curable epoxy resin composition. Further, in the case of Comparative Examples 7 and 8, For the epoxy resin, the product name "Celloxide 2021P" (manufactured by Daicel Co., Ltd.) was used. (Production of Optical Semiconductor Device) The curable epoxy resin composition obtained above was cast into the lead frame of the optical semiconductor shown in Fig. 1 ( InGaN element, 3.5mm x 2.8mm) After the mold is heated in an oven at 20 ° C (resin hardened oven) for 5 hours, -40- 201235375 ' Obtain light that seals the optical semiconductor component with a hardened resin (hardened) Semiconductor device. &lt;Evaluation&gt; The optical semiconductor devices obtained in Examples 15 to 18 and Comparative Examples 7 and 8 were subjected to an energization test by the following method. [Electrification test] Measurements were carried out using Examples 1 5 to 18 and Comparative Examples 7 and 8 using a full beam measuring machine. The total beam of the optical semiconductor device was measured, and the total beam of the current of 60 mA was applied to the optical semiconductor device for 300 hours in a thermostat at a temperature of 85 ° C. The photoretention ratio was calculated by the following formula. Photoretention retention rate (%)} = {3 00 hours after full beam (lm)} / {0 hour full beam (lm)}

xlOOXlOO

[表3] 實施例15 實施例16 實施例17 實施例18 比較例7 比較例8 硬化性 環氧樹脂 組成物 環氧樹脂 [重量份] CEL2021P 80 80 80 80 100 100 MA-DGIC 20 20 20 20 - - CD220PL 10 10 10 10 - - Μ52Ν - 5 - 5 - - 硬化劑組成物[重量份] 130 130 - - 130 - 硬化觸媒 [重量份] San-aid SI-100L - - 0.5 0.5 參 0.5 硬化物 (光半導體 裝置） 光度保持率[%] 78 87 80 88 74 71 試驗設備 •樹脂硬化烘箱 ESPEC(股）製 GPHH-201 β恆溫槽 ESPEC(股）製小型高溫腔室ST-120B1 -41 - 201235375 •全光束測定機 美國Optronic Laboratories公司製多分光放射測 定系統 OL771 •熱衝擊試驗機[Table 3] Example 15 Example 16 Example 17 Example 18 Comparative Example 7 Comparative Example 8 Curable epoxy resin composition Epoxy resin [parts by weight] CEL2021P 80 80 80 80 100 100 MA-DGIC 20 20 20 20 - - CD220PL 10 10 10 10 - - Μ52Ν - 5 - 5 - - Hardener composition [Parts by weight] 130 130 - - 130 - Hardening catalyst [Parts by weight] San-aid SI-100L - - 0.5 0.5 Reference 0.5 Hardening (Optical semiconductor device) Photometric retention rate [%] 78 87 80 88 74 71 Test equipment • Resin hardening oven ESPEC (stock) GPHH-201 β thermostat ESPEC (stock) small high temperature chamber ST-120B1 -41 - 201235375 • Full beam measuring machine Multi-spectrophotometric system OL771 made by Optronic Laboratories, USA • Thermal shock testing machine

ESPEC(股）製小型冷熱衝擊裝置TSE-11-AESPEC (stock) small thermal shock device TSE-11-A

[產業上之可利用性] 本發明之硬化性環氧樹脂組成物，可理想地使用於 光半導體密封用途。又，本發明之硬化性環氧樹脂組成 物，也可利用於黏著劑、電氣絕緣材、疊層板、塗膜、 印墨、塗料、填封劑、抗蝕劑、複合材料、透明基材、 透明片、透明薄膜、光學元件、光學透鏡、光學構件、 光造形、電子紙、觸控面板 '太陽能電池基板、光導波 路、導光板、全像記憶體等。 【圖式簡單說明】 第1圖顯不以本發明之硬化性環氧樹脂組成物將元 件（光半導體元件）予以密封而得之光半導體裝置之一實 施形態之概略圖。左側之圖（“為立體圖、右侧之圖（b) 為+剖面圖。 第2圖顯示實施例之焊料耐熱性試驗中，光半導體裝 置之表面溫度折線圖（二次加熱當中，其中一次加熱之溫 度折線圖）之一例。 【主要元件符號說明】 100 反射件（光反射用樹脂組成物） 1 〇 1 金屬配線 102 LED元件 -42- 201235375 103 104 105 接合引線 透明密封樹脂 固晶材 -43[Industrial Applicability] The curable epoxy resin composition of the present invention can be preferably used for optical semiconductor sealing applications. Moreover, the curable epoxy resin composition of the present invention can also be used for an adhesive, an electrical insulating material, a laminated board, a coating film, an ink, a coating, a potting agent, a resist, a composite material, a transparent substrate. , transparent sheet, transparent film, optical element, optical lens, optical member, optical shape, electronic paper, touch panel 'solar cell substrate, optical waveguide, light guide plate, holographic memory, and the like. [Brief Description of the Drawings] Fig. 1 is a schematic view showing an embodiment of an optical semiconductor device obtained by sealing a member (optical semiconductor element) with a curable epoxy resin composition of the present invention. The figure on the left side ("the perspective view, the right side view (b) is the + cross-sectional view. The second figure shows the surface temperature line diagram of the optical semiconductor device in the solder heat resistance test of the embodiment (one of the secondary heating, one of the heating) An example of the temperature line diagram. [Description of main component symbols] 100 Reflector (resin composition for light reflection) 1 〇1 Metal wiring 102 LED component-42- 201235375 103 104 105 Bonded lead transparent sealing resin solid crystal material-43

Claims (1)

201235375 - 七、申請專利範圍： 1 · 一種硬化性環氧樹脂組成物，其係包含： 脂環環氧化合物（A)、與以下式（丨）表示之異三聚氰 酸單烯丙基二環氧丙酿化合物（B)'與聚碳酸醋多元醇 (C)、與硬化劑（D)或硬化觸媒（E);201235375 - VII. Patent application scope: 1 · A curable epoxy resin composition comprising: an alicyclic epoxy compound (A) and an isomeric cyanuric acid monoallyl propyl group represented by the following formula (丨) a propylene oxide compound (B)' with a polycarbonate polyol (C), a hardener (D) or a hardening catalyst (E); 2. 如申專利範圍第丨項之硬化性環氧樹脂組成物，其中 該脂環環氧化合物（A)之脂環環氧基為環氧己烯基。 3. 如申請專利範圍第2項之硬化性環氡樹脂組成物，其十 該脂環環氧化合物（A)係下式（1-1)表示之化合物， 4. 如申明專利範圍第1至3項中任一項之硬化性環氧樹脂 組成物’其更包含硬化促進劑（F)。 5. 如申吻專利靶圍第1至4項中任一項之硬化性環氧樹脂 組成物’其更包含橡膠粒子。 6. 如申請專利範圍第丨至5項中任一項之硬化性環氧樹匕 組成物’其更包含丙烯酸基嵌段共聚物。 曰 -44 - 201235375 7. —種硬化物，其係將如申請專利範圍第丨至6項中任一 項之硬化性氧樹脂組成物予以硬化而成。 8. —種光半導體密封用樹脂組成物，其係包含如申請專 利範圍第1至6項中任-項之硬化性環氧樹脂組成物而 構成。 .種光半導體裝置，其係以如申請專利範圍第8項之光 半導體密封用樹脂組成物將光半導體元件予以密封而 獲得。 -45-2. The sclerosing epoxy resin composition according to the ninth aspect of the invention, wherein the alicyclic epoxy group of the alicyclic epoxy compound (A) is hexylene oxide. 3. The epoxidized cyclic oxime resin composition of claim 2, wherein the alicyclic epoxy compound (A) is a compound represented by the following formula (1-1), 4. The curable epoxy resin composition of any one of the three items further comprises a hardening accelerator (F). 5. The curable epoxy resin composition of any one of items 1 to 4 of the patent patent target, which further comprises rubber particles. 6. The sclerosing epoxy resin composition of any one of claims 1-5, which further comprises an acryl-based block copolymer.曰 -44 - 201235375 7. A hardened material obtained by hardening a hardening oxygen resin composition as disclosed in any one of claims No. 6 to 6. A resin composition for sealing a photo-semiconductor comprising the curable epoxy resin composition according to any one of claims 1 to 6. An optical semiconductor device obtained by sealing an optical semiconductor element with a resin composition for optical semiconductor sealing according to item 8 of the patent application. -45-
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KR20140009201A (en) 2014-01-22

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