TW201217421A - Production method for curing articles and curing articles - Google Patents

Production method for curing articles and curing articles Download PDF

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Publication number
TW201217421A
TW201217421A TW100135136A TW100135136A TW201217421A TW 201217421 A TW201217421 A TW 201217421A TW 100135136 A TW100135136 A TW 100135136A TW 100135136 A TW100135136 A TW 100135136A TW 201217421 A TW201217421 A TW 201217421A
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Taiwan
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group
hardening
curing
curable
epoxy resin
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TW100135136A
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Chinese (zh)
Inventor
Hiroyuki Hirakawa
Atsuo Tatsumi
Atsushi Sato
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Daicel Chem
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates 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
    • C08G59/18Macromolecules 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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00Details of semiconductor or other solid state devices
    • H01L23/28Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293Organic, e.g. plastic
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates 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
    • C08G59/18Macromolecules 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
    • C08G59/20Macromolecules 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
    • C08G59/22Di-epoxy compounds
    • C08G59/24Di-epoxy compounds carbocyclic
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00Details of semiconductor or other solid state devices
    • H01L23/28Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00Details of semiconductor or other solid state devices
    • H01L23/28Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001Technical content checked by a classifier
    • H01L2924/0002Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

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

Abstract

The present invention provides a production method characterizing by comprising alicyclic epoxy compounds (A), curing agent (B) and curing accelerant (C) which are used as curable components. Comparing to total content of curable components, the content of the alicyclic epoxy compounds (A) is curable epoxy compositions over 60 wt% which cure under the curing conditions of 95 DEG C to 135 DEG C through over 4.5 hours. Based on the production method, to form a curing article having excellent transparency, excellent photo resistance, for example, while using as sealing materials of photo-semiconductor device, excellent crack resistance in thermal cycling test by optimizing temperature and time.

Description

201217421 六、發明說明: 【發明所屬之技術領域】 本發明係有關硬化物之製造方法及硬化物,含有該 硬化物的封閉材料、以及含有該封閉材料的光半導體^ 置。 、 【先前技術】 在使用於光半導體裝置的樹脂,特別是光半導體之 封閉材中’被要求高透光率、光度保持率以及在熱循戸 試驗中的優異耐龜裂性。雖然先前根據脂環式環氧: 脂,可實現高透光率、光度保持率,但在熱循環試驗中, 有易產生龜裂的問題。$ 了解決該問題,採取了使 化觸媒將硬化溫度分幾個階段進行階段性硬化的方法’201217421 SUMMARY OF THE INVENTION [Technical Field] The present invention relates to a method for producing a cured product and a cured product, a sealing material containing the cured product, and an optical semiconductor comprising the sealing material. [Prior Art] In the resin used for the optical semiconductor device, particularly in the sealing material of the optical semiconductor, high light transmittance, luminosity retention, and excellent crack resistance in the heat cycle test are required. Although high transmittance and luminosity retention can be achieved according to the alicyclic epoxy: grease, there is a problem that cracks are liable to occur in the heat cycle test. To solve this problem, a method has been adopted in which the catalyst is used to harden the hardening temperature in several stages.

或在脂環式環氧樹脂中混合具有芳香族環的㈣A 環氧樹脂等的方法。但是’前者之方法作業性差,I法 獲得充分的耐龜裂性,後者之方法有起因於芳香族環而 使光度保持率降低的缺點。 、 在專利文獻1中,¥恭古 4ώ Δ A. 物,該組成物含有硬化觸:有成物硬化的硬化 之包含34環負=不僅含有:作為環氧樹脂 ^碲土甲基·3,4 ·環氧基環己烯羧 U曰的月曰環式環氧樹脂;及包含2,2_雙 之1,2-環氧基_4·(2-環氧乙浐美 環氧樹脂兩者,而且相斟私基)衣己烷加成物的脂環式 n1 4 對於上述透光性封閉材料全質量 “’使J述式(A)或(B)所示化合物之至少一:全:: •01質® %至1質量%而成: U(TC、1小時後,在i * 忒硬化物於 裂性不良。 C、1小時之條件硬化,耐龜 * 4 - 201217421Or a method of mixing an aromatic ring-containing (tetra) A epoxy resin or the like in an alicyclic epoxy resin. However, the former method is inferior in workability, and the I method obtains sufficient crack resistance, and the latter method has a disadvantage of reducing the luminosity retention rate due to the aromatic ring. In Patent Document 1, ¥Kango 4ώ Δ A., which contains a hardening touch: contains a hardened hardened 34 ring negative = not only contains: as epoxy resin methyl bromide methyl 3, 4 · Epoxy cyclohexene carboxy fluorene Epoxy fluorene epoxy resin; and 2,2-bis, 1,2-epoxy _4 · (2-epoxy acetonitrile epoxy resin two And the alicyclic n1 4 of the hexyl hexane adduct is at least one of the compounds of the above-mentioned translucent sealing material "to make the formula (A) or (B): :: • 01 quality ® % to 1% by mass: U (TC, after 1 hour, in i * 忒 hardened material in poor cracking. C, 1 hour hardening, resistant to turtles * 4 - 201217421

Cn H2n+1 NCn H2n+1 N

/•(G2H4〇)—H 、(C2H4W厂H .· (a) x+y表示1至ίο之 (式中,n表示12至18之整數 整數) ΟηΗίιπΊ/•(G2H4〇)—H , (C2H4W Factory H .· (a) x+y means 1 to ίο (where n is an integer from 12 to 18) ΟηΗίιπΊ

0—(ΟΗ2ΟΗ20)ϋ-Η • Φ) (式中,η表示8或9、m表示2至15之整數) ’其使用酸 之雙酚A二 在專利文獻2中’記載有一種環氣樹脂 酐系硬化劑與硬化促進劑,將作為環氧樹脂 環氧丙醚予以熱硬化。在專利文獻2十,記載有欲減低 硬化物之内部應力時,較佳為於80〇c至13(rc左右以 0.5小時至5小時左右之條件進行前硬化後,於u〇c>c至 1 8 0 C左右、以0 · 1小時至1 5小時左右之條件進行後硬 化’而在實施例中’雖有藉由於12 0 °C、1小時之前硬化 後,於1 50。(:、3小時之後硬化而製成的硬化物,但在此 種條件下,所得硬化物的耐龜裂性差《又,上述環氧樹 脂為5mm厚之情形時,於150°c、5曰熱處理後之黃色 指數(yellow index)增加15.2,而可觀察到熱變黃。 先前技術文獻 專利文獻 專利文獻1 日本專利第4366934號公報 專利文獻2 日本特開2008-179733號公報 -5- 201217421 【發明内容】 發明欲解決課題 發月之目的係提供一種硬化物的硬化方法,該硬 化物的透明性、紛土 _ 月性耐光性(光度保持性等)優異、且在熱循 環試驗中耐龜裂柯I U .. 聚性優異’例如適合作為光半導 封閉材料等。 & κ 本發明之其他目的係提供一種以該硬化方法硬化的 硬化物’其透明性、耐光性優異、且在熱循環試驗中耐 龜裂性優異者。 本發明之其他目的係提供一種含有該硬化物的 封閉材料、及光半導體裝置,其透明性、耐光性優異, 且在熱循環試驗中耐龜裂性優異。 解決課題之手段 本發明人等為了解決上述課題,經戮力研討,結果 首先發現一種硬化性樹脂組成物,其含有;相對於硬化 性成分全量而言,60重量%以上之脂環式環氧化合物; 酸酐等之硬化劑•,及硬化促進劑,將該硬化性組成物以 特定之硬化方法硬化時,可獲得透明性、耐光性優異, 且在熱循環試驗中耐龜裂性優異的硬化物、封閉材料、 以及光半導體裝置,於是完成本發明。 亦即,本發明係提供一種硬化物之製造方法,其特 徵為含有脂環式環氧化合物(A)、硬化劑(B)、及硬化促 進劑(C)作為硬化性成分,將相對於硬化性成分全量而 言’該脂環式環氧化合物(A)之含量為60重量%以上之硬 化性環氧樹脂組成物,在溫度95°C以上135。(:以下、且 4.5小時以上的硬化條件下硬化之製造方法。 -6- 201217421 又,本發明提供一種以上述硬化物之製造方法所 造的硬化物。 又’本發明提供一種含上述硬化物的封閉材料。 再者,本發明提供一種含上述封閉材料的半導體 置。 χ 發明效果 根據本發明之硬化物的製造方法,藉由在硬化條件 中使溫度、時間最適化,而可獲得透明性優異,例如使 用作為光半導體裝置之封閉材料時之耐光性優異、在熱 循環試驗中耐龜裂性優異的硬化物、封閉材料、以及半 導體裝置。 【實施方式】 <硬化物之製造方法> 本發明之硬化物的製造方法,其特徵為硬化性環氧 樹脂組成物含有脂環式環氧化合物(Α)、硬化劑(Β)、及 硬化促進劑(c)作為硬化性成分,將相對於硬化性成分全 量而S,5玄脂環式環氧化合物(Α)之含量為60重量%以上 之硬化性壞氧樹脂組成物,在溫度95<>c以上! 35t以 下、且4.5小時以上之硬化條件下硬化。 <硬化條件> 本發明.之硬化物的製造方法,係將上述硬化性環氧 樹脂組成物在溫| 95t以上135tW、且4 5小時以 上之硬化條件下硬化。在本說明書中,可將硬化性環氧 樹脂組成物例如放入預定的鑄模中,或不放入,而藉由 於預定溫度下載置預^時間而進行硬化。硬化亦可不設 201217421 定時間間隔(interval)而在預定時間連續進行,亦可於中 途設定時間間隔,在設定時間間隔的情形時,硬化時間 係指在時間間隔前後以預定溫度處理的硬化時間的總合 計時間。 硬化溫度為95。(:以上l35t以下,較佳為1〇〇。〇以 上小於13G°C,更佳為IGGt以上12G°C以下·>硬化溫度 只要是在上述溫度範圍内即可,可為固定,亦可為數種 不同的溫度。上述時間間隔係指溫度低於95它的時間, 亦可為室溫附近(例如25t左右卜在該時間間隔中,將 硬化性環氧樹脂組成物自鑄模移除,亦可將自該鑄模移 除的硬化性環氧樹脂組成物再以上述硬化溫度硬化。硬 化溫度可為固$ ’亦可在溫度饥以上13代以下之範 圍變動其中,較佳為不論有無時間間隔,硬化溫度均 為固定。 硬化時間為4.5小時以上(例如4 5小時以上24小時 以下),較佳A 5小時以上2〇小時以下,更佳為5小時 以上16小時以下。時間間隔亦可設定為30分鐘以上(例 如3〇分鐘以上至30日)。時間間隔方面,較佳為30分 鐘至1〇曰’更佳為30分鐘至3曰。設定時間間隔時, 例:可將硬化性環氧樹脂組成物放入預定的鑄模内,以 預定/皿度硬化1小時至2小時,接著將硬化性環氧樹脂 :成物放冷至室溫附近後,自鑄模内取出,接著以剩餘 間以預定溫度硬化。本發明硬化物的製造方法,藉由 2化性環氧樹脂組成物以上述硬化條件硬化,可獲得 在,、,、循環試驗中耐龜裂性優異的硬化物。 201217421 〈硬化性環氧樹脂組成物> 在本發明之硬化物的製造方法中所使用的硬化性環 氧樹脂組成物含有脂環式環氧化合物(A)、硬化劑(B)及 硬化促進劑(c)作為硬化性成分,相對於硬化性成分全量 而吕,該脂環式環氧化合物(A)之含量為6〇重量%以上。 〈脂環式環氧化合物(A)> 本發明所使用的脂環式環氧化合物(A)方面,只要是 為具有脂肪族環的化合物則無特別限定,但較佳為⑴具 有環氧基之化合物,該環氧基係包含構成脂環之鄰接的 2個碳原子與氧原子、及⑴)在脂環中使環氧基以直接單 鍵鍵結的化合物。 (1)具有環氧基之化合物,其中該環氧基係包含構成 月a環之鄰接的二個碳原子與氧原子,可由周知慣用之物 中任意選擇使用。脂環環氧基方面,較佳為環氧環己烷 基。 (1)具有環氧基的化合物,其中該環氧基係包含構成 脂環之鄰接的二個碳原子與氧原子,在具有環氧基之化 合物方面,特別是就透明性、耐熱性之觀點,以下述式 (1)所示脂環式環氧樹脂為理想。0—(ΟΗ2ΟΗ20)ϋ-Η • Φ) (wherein η represents 8 or 9, m represents an integer of 2 to 15) 'The acid bisphenol A 2 is described in Patent Document 2, and a ring gas resin is described. The anhydride-based curing agent and the curing accelerator are thermally cured as epoxy epoxy propylene ether. In Patent Document 20, it is described that, in order to reduce the internal stress of the cured product, it is preferably from 80 〇c to 13 (about rc for about 0.5 to 5 hours, and then pre-hardened, and then u〇c>c to After 1 8 0 C, post-hardening is carried out under conditions of about 0.1 hour to about 15 hours, and in the examples, although it is cured by 120 ° C and 1 hour before, it is at 50 ° (:, a cured product obtained by hardening after 3 hours, but under such conditions, the obtained cured product has poor crack resistance. Further, when the epoxy resin is 5 mm thick, it is heat treated at 150 ° C and 5 Torr. The yellow index is increased by 15.2, and the heat is yellowed. The prior art is disclosed in the patent document. Patent Document 1 Japanese Patent No. 4366934 Patent Document 2 Japanese Patent Laid-Open Publication No. 2008-179733-5-201217421 The object of the invention is to provide a method for hardening a cured product, which is excellent in transparency, gradual light resistance (photometric retention, etc.), and is resistant to cracking in a heat cycle test. .. excellent in aggregation', for example, suitable as A semi-conductive sealing material, etc. & κ Another object of the present invention is to provide a cured product which is cured by the curing method, which is excellent in transparency and light resistance, and excellent in crack resistance in a heat cycle test. In order to solve the above problems, the present inventors have provided a sealing material containing the cured product and an optical semiconductor device which are excellent in transparency and light resistance, and are excellent in crack resistance in a heat cycle test. As a result, it was found that a curable resin composition containing 60% by weight or more of an alicyclic epoxy compound, a curing agent such as an acid anhydride, and a hardening promotion are found in the curable resin composition. When the curable composition is cured by a specific curing method, it is possible to obtain a cured product, a sealing material, and an optical semiconductor device which are excellent in transparency and light resistance, and which are excellent in crack resistance in a heat cycle test, and are completed. The present invention provides a method for producing a cured product, which comprises an alicyclic epoxy compound (A), The curing agent (B) and the curing accelerator (C) are curable components, and the content of the alicyclic epoxy compound (A) is 60% by weight or more based on the total amount of the curable component. The resin composition is produced at a temperature of 95° C. or more and 135. (:: a method of curing under the curing conditions of 4.5 hours or more. -6-201217421 Further, the present invention provides a hardening by the method for producing the cured product described above. Further, the present invention provides a sealing material comprising the above-mentioned cured product. Further, the present invention provides a semiconductor device comprising the above-mentioned sealing material. 发明 Effect of the invention According to the method for producing a cured product of the present invention, in a hardening condition When the temperature and time are optimized, it is excellent in transparency, for example, when it is used as a sealing material for an optical semiconductor device, it is excellent in light resistance, and is excellent in crack resistance in a heat cycle test, a sealing material, and a semiconductor device. [Embodiment] The method for producing a cured product according to the present invention is characterized in that the curable epoxy resin composition contains an alicyclic epoxy compound (Α), a curing agent (Β), and The curing accelerator (c) is a curable component, and the curable ortho-oxygen resin composition having a content of S,5 ortho-alicyclic epoxy compound (Α) is 60% by weight or more based on the total amount of the curable component, at a temperature. 95<>c or more! It hardens under 35t and hardening conditions of 4.5 hours or more. <Curing Condition; The method for producing a cured product according to the present invention is characterized in that the curable epoxy resin composition is cured under a curing condition of a temperature of from 95 t to 135 tW and for more than 45 hours. In the present specification, the curable epoxy resin composition may be placed, for example, in a predetermined mold, or may be placed, and hardened by a predetermined temperature downloading time. Hardening may be performed continuously at a predetermined time without setting the 201217421 interval, or may be set in the middle of the time interval. In the case of setting the time interval, the hardening time refers to the hardening time treated at a predetermined temperature before and after the time interval. Total total time. The hardening temperature is 95. (: l35t or less, preferably 1〇〇. 〇 or more is less than 13G °C, more preferably IGGt or more and 12G °C or less. · The curing temperature may be within the above temperature range, and may be fixed or may be There are several different temperatures. The above time interval means that the temperature is lower than 95. It can also be near room temperature (for example, about 25t). In this time interval, the hardening epoxy resin composition is removed from the mold. The curable epoxy resin composition removed from the mold may be hardened at the above-mentioned hardening temperature. The hardening temperature may be solid or may vary within a range of temperature below 13 generations, preferably with or without a time interval. The curing temperature is fixed. The curing time is 4.5 hours or more (for example, 45 hours or more and 24 hours or less), preferably A 5 hours or more and 2 hours or less, more preferably 5 hours or more and 16 hours or less. The time interval can also be set. It is 30 minutes or more (for example, 3 minutes or more to 30 days). In terms of time interval, it is preferably 30 minutes to 1 inch', more preferably 30 minutes to 3 inches. When setting the time interval, for example, a hardenable ring can be used. Oxygen resin group The product is placed in a predetermined mold and hardened at a predetermined/dish level for 1 hour to 2 hours, and then the hardened epoxy resin is cooled to room temperature, taken out from the mold, and then the remaining portion is predetermined. The method for producing a cured product of the present invention is obtained by curing the cured epoxy resin composition under the above-mentioned curing conditions, thereby obtaining a cured product excellent in crack resistance in a cycle test. Epoxy resin composition> The curable epoxy resin composition used in the method for producing a cured product of the present invention contains an alicyclic epoxy compound (A), a curing agent (B), and a curing accelerator (c). The content of the alicyclic epoxy compound (A) is 6% by weight or more based on the total amount of the curable component. The alicyclic epoxy compound (A) > The alicyclic epoxy compound (A) is not particularly limited as long as it is a compound having an aliphatic ring, but is preferably a compound having an epoxy group, and the epoxy group includes a contiguous 2 which constitutes an alicyclic ring. Carbon atoms and oxygen atoms, And (1) a compound in which an epoxy group is directly bonded by a single bond in an alicyclic ring. (1) A compound having an epoxy group, wherein the epoxy group contains two carbon atoms and oxygen constituting the adjacent a-ring of the month a. The atom may be optionally selected from the conventionally used ones. The alicyclic epoxy group is preferably an epoxycyclohexane group. (1) A compound having an epoxy group, wherein the epoxy group comprises an alicyclic ring. The two adjacent carbon atoms and the oxygen atom are preferably an alicyclic epoxy resin represented by the following formula (1) from the viewpoint of transparency and heat resistance in the case of a compound having an epoxy group.

可例舉單鍵、2元烴基、羰基、醚鍵、酯鍵、碳酸 酯基、醯胺基、及該等經複數個連結的基等。 201217421 2元烴基方面’可例舉碳數1至1 8之直鏈狀或分支 鏈狀之伸烷基、2元脂環式烴基等。碳數1至μ之直鏈 狀或分支鏈狀之伸烧基方面,可例舉亞曱基、曱基亞甲 基一甲基亞甲基、伸乙基、伸丙基(pr0pyiene)、三亞 甲基(trimethylene)等。2元脂環式烴基方面,可例舉丨,2_ 環戊烯、1,3-環戊烯、環亞戊基、1>2_伸環己基、153_伸 環己基、1,4-伸環己基、環亞己基等之2元環伸烷基(含 環亞烷基)等。 連結基X方面’較佳為含有氧原子的連結基,具體 言之,可例舉-CO-、-〇-CO_〇_、_CO〇· ' ·〇_、_c〇NH ; 該等之基為經複數個連結之基;該等之基的丨或2個以 上與2元烴基之1或2個以上連結的基等。2元烴基方 面’可例舉前述基。 式(1)所示脂環式環氧化合物所代表的例子方面,可 例舉下述式(1 -1)至(1 _ 8)所示化合物等。可使用例如A single bond, a divalent hydrocarbon group, a carbonyl group, an ether bond, an ester bond, a carbonate group, a decylamino group, and the like, and a plurality of linked groups may be mentioned. The 201217421 divalent hydrocarbon group' may, for example, be a linear or branched alkyl group having a carbon number of 1 to 18, a 2-membered alicyclic hydrocarbon group or the like. The straight chain or branched chain stretching group having a carbon number of 1 to μ may, for example, be an anthracenylene group, a fluorenylmethylidene group, a methyl group, an ethyl group, a propyl group (pr0pyiene), or a Sanya group. Trimethylene and the like. The 2-membered alicyclic hydrocarbon group may, for example, be 丨, 2_cyclopentene, 1,3-cyclopentene, cyclopentylene, 1> 2_cyclohexylene, 153_cyclohexylene, 1,4-stretch A 2-membered cycloalkyl group (including a cycloalkylene group) such as a cyclohexyl group or a cyclohexylene group. The linking group X is preferably a linking group containing an oxygen atom, and specifically, -CO-, -〇-CO_〇_, _CO〇·'·〇_, _c〇NH; It is a group of a plurality of linked groups; or a group of two or more of these groups or a group of two or more hydrocarbon groups having two or more hydrocarbon groups. The above-mentioned group can be exemplified as the 2-membered hydrocarbon group. Examples of the alicyclic epoxy compound represented by the formula (1) include compounds represented by the following formulas (1 to 1) to (1 to 8). Can be used, for example

Celloside 2021P、Celloside 2081(Daicel 化學工業-公司製) 等之市售品。此外,下述式中,表示1至3〇之整 數。R為碳數1至8之伸烷基,可例舉亞曱基、伸乙基、 伸丙基、異伸丙基、伸丁基、異伸丁基、二級伸丁基、 伸戊基、伸己基、伸庚基、伸辛基等之直鏈狀或分支鏈 狀伸烷基。該等中,較佳為亞甲基、伸乙基、伸丙基、 異伸丙基等之碳數1至3之直鏈狀或分支鏈狀伸烷基。 201217421Commercial products such as Celloside 2021P and Celloside 2081 (Daicel Chemical Industry Co., Ltd.). Further, in the following formula, an integer of 1 to 3 表示 is shown. R is an alkylene group having 1 to 8 carbon atoms, and may, for example, be an anthracenylene group, an exoethyl group, a propyl group, an exo-propyl group, a butyl group, an isobutylene group, a secondary butyl group, or a pentyl group. A linear or branched chain alkyl group such as a hexyl group, a heptyl group, and a octyl group. Among these, a linear or branched alkyl group having 1 to 3 carbon atoms such as a methylene group, an exoethyl group, a propyl group or an exo-propyl group is preferable. 201217421

(ii)脂環中使環氧基以直接單鍵鍵結的化合物方 面,可例舉下述式(II)所示化合物。(ii) The compound of the following formula (II) is exemplified as the compound in which the epoxy group is directly bonded to the epoxy group in the alicyclic ring.

式(II)中,RI係自p價醇去除p個-OH之基;ρ、η 表示自然數。ρ價之醇[R'-(OH)p]方面,可例舉2,2-雙(羥 甲基)-1-丁醇等之多元醇等(碳數1至15之醇等)°ρ較佳 為1至6,η較佳為1至30。ρ為2以上之情形,各自之 -11- 201217421 ()内之基中@ η可為相同或相$。上述化合物方面,具 體。之可例舉2,2-雙(經甲基)小丁醇之環氧基 -4-(2-環氧乙烧基(〇xiranyl ))環己烷加成物、 3150(Daicel化學工業公司製)等。 脂環式環氧化合物(A)方面,可將上述例示之化合物 單獨使用或組合二種以上使用,較佳可使用例如In the formula (II), the RI system removes p-OH groups from the p-valent alcohol; ρ and η represent natural numbers. In the case of the ρ-valent alcohol [R'-(OH)p], a polyol such as 2,2-bis(hydroxymethyl)-1-butanol or the like (an alcohol having 1 to 15 carbon atoms, etc.) °ρ can be exemplified. It is preferably from 1 to 6, and η is preferably from 1 to 30. In the case where ρ is 2 or more, @ η in the base of each of -11- 201217421 () may be the same or phase $. In terms of the above compounds, it is specific. An example of 2,2-bis(methyl)butanol-based epoxy-4-(2-oxiranyl)cyclohexane adduct, 3150 (Daicel Chemical Industry Co., Ltd.) System) and so on. In the case of the alicyclic epoxy compound (A), the above-exemplified compounds may be used singly or in combination of two or more. It is preferred to use, for example,

Celloside 2021P、Celloside 208 1、EHPE 3150(Daicel 化 學工業製)等之市售品。 相對於硬化性環氧樹脂組成物所含有的硬化性成分 全量而言,脂環式環氧化合物(A)之含量為6〇重量%以上 (例如60至1 00重量%)。硬化性成分係指以熱或放射線 硬化的硬化性化合物。相對於硬化性成分全量而言,脂 環式環氧化合物(A)之含量較佳為設定在7〇重量%(7〇至 100重里/〇) ’更佳為重量0/〇以上(8〇至1 重量%) 〇 此外,若使用2種以上脂環式環氧化合物(A)時,上述含 量為其合計之含量。藉由將脂環式環氧化合物(A)之含量 設定在上述範圍内,於使硬化性環氧樹脂組成物硬化 時,可獲得透光率及光度保持率優異的硬化物。 本發明之硬化物的製造方法所使用的硬化性環氧樹 脂組成物中’硬化性成分的合計含量例如為3〇至9〇重 量/。,較佳為40至80重量%,更佳為4〇至7〇重量0/〇。 藉由將硬化性環氧樹脂組成物中硬化性成分之含量設定 在上述範圍内,可獲得硬化性優異的樹脂組成物。 -12- 201217421 &lt;脂環式環氧化合物(A)以外之硬化性成分〉 β本發明所使用的硬化性環氧樹脂組成物亦可含有脂 環式環氧化合物⑷以外的環氧化合物。脂環式環氧化合 物(Α)以外的環氧化合物方面,可使用在環氡六氫酞酸二 辛酯、環氧六氫酞酸雙(2·乙基己基)酯、Μ•丁二醇二環 氧丙醚、1,6-己二醇二環氧丙醚、甘油之三環氧丙醚、 三羥甲基丙烷之三環氧丙醚、山梨醇之四環氧丙醚'二 新戊四醇之六環氡丙醚、聚乙二醇之二環氧丙醚、聚丙 一醇之二環氧丙醚、丙二醇、甘油等之脂肪族多元醇中 加成一種或二種以上氧化烯而得的聚醚聚醇之聚環氧丙 醚;脂肪族長鏈二元酸脂肪族高級醇之單環氧丙醚或苯 齡、甲酌·、丁基笨酴、又在該等中加成氧化烯而得的聚 喊醇之單環氧丙醚;高級脂肪酸之環氧丙酯、環氧化大 豆油、環氧硬脂酸辛酯、環氧硬脂酸丁酯、環氧化亞麻 仁油、環氧化丁二烯、環氧乙烷、環氧丙烷、氧化苯乙 烯、甲基環氧丙醚、丁基環氧丙醚、烯丙基環氧丙喊、 苯基環氧丙醚、乙二醇環氧丙基苯醚、乙二醇节基環氧 丙喊、二乙一醇環氧丙基四氫0底喃醚、環氧丙基甲基丙 烯酸酯、乙酸環氧丙酯等、或該等環氧化合物之氫原子 一部分或全部以I取代之物。 又,除了上述以外’亦可使用内部具有環氧基的寡 聚物形式的放射線硬化性樹脂。可例舉例如環氧化聚丁 二烯(製品名:Epolead ΡΒ3600、ΡΒ4700,Daicel 化學工 業股份有限公司)、環氧化苯乙烯丁二烯短嵌段共聚物 (teleblock cop〇lymer)(製品名 Epofriend AT501,Daicel -13- 201217421 化學工業股份有限公司)等。又,有酚醛清漆型環氧樹 脂,例如將苯酚、甲酚、齒化苯酚及烷笨酚等之苯酚類 與甲醛在酸性觸媒下反應所得酚醛清漆類與環氧氯丙烷 及/或曱基環氧氣丙烷反應所得之物(製品名: EOCN-103、EOCN-104S ' EOCN-1020、EOCN-1027、 EPPN-201、BREN-S,日本化藥股份有限公司;製品名: DEN-431、DEN-439,道氏化學公司及製品名:N-73、 VH-4150 ’大曰本油墨化學工業股份有限公司)等。又, 有使雙酚A、雙酚F、雙酚S及四溴雙酚a等之雙盼類 與環氧氣丙烧反應所得的雙盼型環氧樹脂、或使雙紛A 之二環氧丙醚與前述雙酚類之縮合物與環氧氯丙烷反應 所得的雙盼型環氧樹脂(製品名:epik〇te 1〇〇4、epikote 1002 ’油化Shell股份有限公司;製品名:DER_33〇、 DER-337’道氏化學公司)等。 脂環式環氧化合物(A)以外的環氧化合物方面,可單 獨使用上述例示之化合物或組合二種以上使用。脂環式 環氧化合物(A)以外的環氧化合物方面,較佳為使用具有 雙酚A型環氧樹脂等之芳香族環的環氧化合物。亦可不 使用脂環式環氧化合物(A)以外的環氧化合物。 &lt;硬化劑(B)&gt; 本發明之硬化物之制;止古π At m , &lt; H k方法所使用的硬化性環氧樹 月Η組成物含有硬化齋丨f 、 r* JL· 劑(B)。硬化劑(B)具有使具環氧基的 化合物硬化的作用。太路bB 士 本發明中的硬化劑(B)方面,可使用 周知慣用之硬化劑作為援_m尤 马裒氧樹知用硬化劑。本發明中 硬化劑(B ),其中較# a 0 ^τ 佳為25 C下且液狀的酸酐,可例舉甲 -14- 201217421 基四氫酞酸酐、甲基六氫酞酸酐、十二碳烯琥珀酸酐、 甲基橋聯亞甲基(methyl endo-methylene)四氫欧酸針 等。又,例如敌酸酐、四氫献酸肝、六氫酖酸酐、曱基 環己烯二羧酸酐等之常溫(25。〇下為固體狀的酸酐,藉由 溶解於常溫(25。(〕)下為液狀的酸酐中’成為液狀混合物, 而可使用作為本發明中的硬化劑(B)。又,本發明中,可 使用Rikacid MH-700(新曰本理ί化製)、HN-5500(日立化 成製)等之市售品作為硬化劑(B)。 硬化劑(B)可使用一種,亦可以任意之比率混合二種 以上使用。其使用量方面,例如相對於硬化性環氧樹脂 組成物中含有之具有環氧基的化合物之總量丨〇〇重量份 而5 ’為50至150重量份’較佳為1〇〇至145重量份, 更具體言之’上述硬化性環氧樹脂組成物中含有之全部 的具有%氡基的化合物中的每丨當量環氧基,較佳為使 用0.5至1.5當量的比率。硬化劑(B)之使用量若低於5〇 重量份,則效果不充分,硬化物之強韌性有降低的傾向, 方面’硬化劑(B)之使用量若超過150重量份,則硬化 物有著色而色調惡化的情形。此外,若使用二種以上的 硬化劑(B)時,上述使用量為其合計的使用量。 本發明中’因硬化性環氧樹脂組成物中含有之全部 的具有壞氧基的化合物中的每丨當量環氧基,較佳為使 用〇.5至1.5當量硬化劑(B)的比率,故硬化時的反應點 夕,又,吾人認為因使硬化性環氧樹脂組成物在溫度95t: 、13 5 ◦以下的低溫下硬化’故可平穩且平均地進行硬 可製k在熱猶環試驗中耐龜裂性優異的硬化物。 201217421 〈硬化促進劑(c)&gt; 本發明硬化物之製造方法所使用的硬化性環氧樹脂 組成物含有硬化促進劑(C)。硬化促進劑(c)係在以硬化 劑硬化具有環氧基的化合物時,具有促進硬化速度功能 的化合物。亦可含於本發明硬化性環氧樹脂組成物中的 硬化促進劑(C) ’可使用周知慣用的硬化促進劑,可例舉 例如1,8-二氮雜雙環[5.4.0]十一稀_7(DBU)及其鹽(例如 苯盼鹽、辛酸鹽、對曱苯磺酸鹽、甲酸鹽、四苯基硼酸 鹽),1,5-二氮雜雙環[4.3.0]壬稀-5(DBN)及其鹽(例如鱗 鹽、鍍鹽、四級銨鹽、碘鑌鹽);苄基二曱胺、2,4,6-參(二 曱胺基甲基)苯酚、N,N-二甲基環己胺等之三級胺;2·乙 基-4-甲基咪唑、1-氰乙基·2_乙基_4_曱基咪唑等之咪唑; 磷酸8日、二笨膦等之膦類;四苯鱗四(對甲苯基)蝴酸鹽 等之鎮化合物;辛酸錫、辛酸鋅等之有機金屬鹽;金屬 螯合物等。該等可單獨使用或混合二種以上使用。 又’本發明中,可使用U-CAT SA506、U-CAT SA 102、U-CAT 5003、U-CAT 18X、12XD(開發品)(均為 San-apro公司製)、ΤΡΡ·Κ、TPP-MK(均為北興化學工業 製)、PX-4ET(日本化學工業製)等之市售品作為硬化促進 劑(C) 〇 硬化促進劑(C)可使用一種或以任意比率混合二種 以上使用亦無妨。其使用量方面,例如相對於硬化性環 氧樹脂組成物中含有之具有環氧基的化合物之總量ι〇〇 重量份而a ,為0.05至5重量份,較佳為〇.1至3重量 份,特佳為0.2至3重量份,最佳為0.25至2 5重量份 -16- 201217421 左右。硬化促進劑(C)之使用量若低於0.05重量份,有 硬化促進效果不充分的情形’ 一方面,硬化促進劑(〇 之使用量若超過5重量份時,則有硬化物著色而色調惡 化的情形。此外’使用二種以上硬化促進劑(c)的情形 時,上述使用量為其合計的使用量。 &lt;無機充填劑&gt; 本發明.硬化物之製造方法所使用的硬化性環氧樹脂 組成物亦可進一步含有無機充填劑。無機充填劑並無特 別限定’但可使用一種以上的二氧化矽、氧化鋁、雲母、 合成雲母、滑石、氧化弼、碳酸辦、氧化錯、氧化鈦、 鈦酸鋇、高嶺土( kaolin )、皂土、矽藻冬、氮化硼、氮 化鋁、碳化矽、氧化鋅、氧化鈽(IV)、氧化鉋、氧化鎂、 玻璃珠、玻璃纖維、石墨、氫氧化鈣、氫氧化鎂、氫氧 化鋁、纖維素等◊又,無機充填劑可例舉奈米二氧化矽、 奈米二氧化鈦、奈米氧化鍅、碳奈米管等。 該等無機充填劑可以例如國際公開第96/3 1572號記 載之燄火水解法、燄火熱分解法、電漿法等周知的方法 製造。適當的無機充填劑方面,可使用經穩定化的膠體 狀無機微粒之奈米分散溶膠類等,市售品方面,有 BAYER公司製之二氧化石夕溶膠、Goldschmidt公司製之 Sn02溶膠類、MERCK公司製之Ti02溶膠類、Nissan Chemicals 公司製之 Si02、Zr02、Al2〇3 及 Sb203 溶膠或 DEGUSSA公司製之Aerosil分散物類等之市售品可取 得。 -17- 201217421 無機充填劑可藉由表面改質使該等的黏度行為變 化。微粒的表面改質可使用周知的表面改質劑進行。此 種表面改質劑方面,可使用例如與存在於無機充填劑表 面的S能基可進行共價鍵或錯合物形成(complex formation)等相互作用的化合物、或與聚合物基質可相互 作用的化合物。此種表面改質劑可使用例如分子内具有 羧基、(一級、二級、三級)胺基四級銨基、羰基、環 氧丙基乙烯基、(甲i)丙烯醯氧基、魏基等之官能基 的化合物等。此種表面改質劑通常在標準溫度及壓力條 件下為液體’其係由分子内碳數為例# 15以下,較佳為 10以下,特佳為8以下之低分子有機化合物所構成。該 低分子有機化合物之分子量為例如5〇〇以下較佳為 以下’特佳為200以下。 適當的表面改質劑可你丨整$赌 J例举甲酸、乙酸、丙酸、丁酸、 戍酸、己酸、丙稀酸、 甲基丙烯酸、巴豆酸、檸檬酸、 己一酸、號ίό酸、戊二酿、苜滅 曼草酸、順丁烯二酸及反丁烯 一酸等之竣數1至12之始4« &amp;和或不飽和單及聚羧酸類(較 佳為單羧酸類)及該等之酯 曰頸(較佳為甲基丙烯酸甲酯等 之C!至C4烷酯類);醯胺類 败頸,乙醯基丙_、2,4-己二酮、 3,5-庚二酮、乙醯乙酸及 1王h烷乙醯乙酸類等之β-二羰基化合物等。又雖I牿 a Λ ^ …、特別限义,但可將周知慣用的 矽烷偶合劑作為表面改質劑使用。 無機充填劑之粒徑通常為Λ η, 鉍从* 吊马〇·〇1ηιη至200μιη左右, 較佳為O.lnm至ΐ〇〇μιη,转杜 何住马0.1nm至50μηι左右。 -18- 201217421 若硬化性成分之合計含量為丨00重量份,無機充填 劑之含量較佳為1至2000重量份,再佳為10至重 量份。又,相對於硬化性環氧樹脂組成物之全量而言, 無機充填劑之含量為例如5至95wt%,較佳為10至 90wt%。此外,在使用二種以上的無機充填劑時,上述 含量為其合計的含量。 &lt;橡膠微粒&gt; 本發明使用的硬化性環氧樹脂組成物中亦可含有橡 膠微粒。橡膠微粒可例舉粒狀NBR(丙烯腈-丁二烯橡 膠).、反應性末端叛基NBR(CTBN)'無金屬nbr、粒狀 苯乙烯·丁二稀橡膠)等。橡膠微粒具有包含具橡膠 彈性的芯部分、與被覆該芯部分之至少—層的外殼層的 多層結構(芯-外殼結構),作Α π + 作為可在表面與脂環式環氧樹 脂反應的官能基,具有羥基及/或羧基,且平均粒徑為 iOnm至5〇〇nm,最大粒徑為5〇nmi義⑽的橡膠微 粒,其巾亦可具有該橡膠微粒之折射率與該硬化性環氧 樹脂組成物之硬化物之折射率葚 耵+差為±0.02以内的橡膠微 粒。橡膠微粒可使用一種或以 A作恩比年混合二種以上使 用亦無妨。相對於硬化性成分 取刀之合计100重量份而言, 橡膠微粒之含量為例如〇.5 I 30重量份,較佳為1至2〇 重量份’再佳為!至10重 1伤調配量若低於0.5重量 份時,耐龜裂性有降低的傾向, 右超出30重量份,則耐 熱性及透明性有降低的傾向 π此外,使用二種以上的橡 膠微粒時,上述含量為其合計的含量。 -19- 201217421 &lt;添加劑&gt; 在無損於本發明之效果範圍内,本發明中此等硬化 性環氧樹脂組成物,除了上述以外,可使用各種添加劑。 添加劑若使用例如乙二醇、二乙二醇、丙二醇、甘油等 之具有羥基的化合物,則可使反應緩慢進行。此外,在 無損於黏度或透明性的範圍内’亦可使用聚矽氧系或敦 系消泡劑、調平劑、γ_環氧丙氧基丙基三甲氧基矽燒等 之碎烧偶合劑、界面活性劑、難燃劑、著色劑、抗氧化 劑、紫外線吸收劑、離子吸附體、顏料、螢光體、脫模 劑等之慣用添加劑。 本發明硬化物之製造方法所使用的硬化性環氧樹脂 組成物’可藉由將上述各成分均勻混合而獲得。若要獲 得上述硬化性環氧樹脂組成物,就得使用自轉-公轉型搜 拌脫/包裝置、均化器、行星式(planetary)混合器、三輥 磨、珠磨等一般所知的混合用機器,將各成分進行攪拌、 溶解、混合、分散等,以盡可能變得均勻為理想。 〈硬化物&gt; 本發月藉由以上述硬化條件使上述硬化性環氧樹脂 組成物硬化,而可獲得透明性、耐光性(光度保持性等) 優異、且在熱循環試驗中耐龜裂性等諸物性均為優異的 硬化物。 ' &lt;封閉材料&gt; 、本發明之封閉材料,係藉由將上述硬化性環氧樹 組成物作為封閉劑使用,並以上述硬化條件使之硬化 而使透明性、耐光性(光度保持性等)優異,且在熱循 試驗中耐龜裂性等之諸物性均為優異。 -20- 201217421 &lt;光半導體裝置&gt; 本發明之光半導體裝置可藉由以上述硬化性環氧樹 脂組成物封閉光半導體元件,並以上述硬化條件使之硬 化而獲得。光半導體元件之封閉係將以前述方法所調製 的硬化性環氧樹脂組成物注入預定的成形鑄模内,以上 述硬化條件加熱硬化而進行。本發明光半導體裝置的透 明性、耐光性(光度保持性等)優異、且在熱循環試驗中 耐龜裂性等之諸物性均為優異。 根據本發明硬化物的製造方法,可獲得透明性、耐 光性(光度保持性等)優異,且在熱循環試驗中耐龜裂性 等之諸物性均為優異的光半導體封閉材料、黏結材料、 電絕緣材料、積層板、塗膜、油墨、塗料、封膠(seaUnt)、 光阻、複合材料、透明基材、透明薄片、透明薄膜 '光 學兀件、光學透鏡、光學構件、雷射微影術 lithography)、電子紙、觸控面板、太陽電池基板光波 導(optical waveguide)、導光板、全像記憶體(h〇i〇graphic memory)等 ° 實施例 以下根據實施例更詳細說明本發明,但本發明並不 限定於該等實施例。 製造例1 (環氧樹脂A劑) 藉由依照表1所示調配處方(單位:重量份),將2,2_ 雙(羥曱基)-1-丁醇之1,2-環氧基_4·(2_環氧乙烷基)環己 烷加成物(Daicel化學工業公司製ΕΗρΕ315〇)與3 4環氧 -21 - 201217421 基環己基甲基-3',4’-環氧基環己烷羧酸酯(DaUei化學工 業公司製Celloside 2021P)或者雙酚a型環氧樹脂(新曰 鐵化學公司製Y D -12 8)加以混合,並於§ 〇。匚、攪摔1小 時’而使2,2-雙(羥曱基)-1-丁醇之ι,2-環氧基_4_(2_環氧 乙烷基)環己烷加成物溶解’獲得環氧樹脂(混合物)。 製造例2 (硬化劑、硬化促進劑及添加劑、可撓性提供劑之混合 物,在以下稱為B劑) 作為B劑,係使用自轉-公轉型攪拌裝置(脫泡攪拌 機(Thinky Mixer) AR-250 Thinky 公司製),將硬化劑(新 日本理化公司製Rikacid MH-700 ; 4-甲基六氫酞酸酐/六 氫酞酸酐=70/30) : 100重量份、硬化促進劑(San apr〇公 司製1 8X). 0.5重量份、添加劑(和光純藥工業公司製乙 —醇).1重董份、可撓性提供劑(新日本理化製Rikaeid HF-08) . 3重量份,予以均勻混合、脫泡並獲得B劑。 實施例1至7、比較例1至7 ,將以製造例1所得的環氧樹脂A劑與以製造例2所 '寻的B劑,依照表1所示的調配處方(單位:重量份), =用自轉-公轉型攪拌裝置(脫泡攪拌機 司製)’將各成分均勻混合、脫泡,獲得硬化性環氧樹 脂組成物。 硬化條件(j) 將以實施例1、3所得的樹脂組成物注入鑄模中(形 俨-燈形狀’大々、:0 3),插入經封裝藍色之發光二極 件的引導框架(lead frame )後,以烤爐(Espec公司 -22- 201217421 製GPHH-20 1) ’於1 00°C下加熱硬化1 5小時,獲得以樹 脂封閉元件的光半導體裝置。 硬化條件(2) 將以貫施例2、4至7所得的樹脂組成物注入鑄模(形 狀.燈形狀’大小.03)中,插入經封裝藍色之發光二 極體元件的引導框架後,以烤爐(Espec公司製GPHH-201) 於120°C下加熱硬化7小時,獲得以樹脂封閉元件的光半 導體裝置。 硬化條件(3) 將以比較例1、4所得的樹脂組成物注入鱗模(形狀: 燈形狀’大小;0 3)中’插入經封裝藍色之發光二極體 元件的引導框架後,以烤爐(Espec公司製GPHH-201), 於120°C下加熱硬化4小時,獲得以樹脂封閉元件的光半 導體裝置。 硬化條件(4) 藉由將比較例2、5至7獲得的樹脂組成物注入鑄模 (形狀:燈形狀,大小:03)中,插入經封裝藍色之發光 二極體元件的引導框架後,以烤爐(Espec公司製 GPHH-201),於i〇(TC下加熱硬化2小時後,於丨⑻它下 加熱硬化3小時,獲得以硬化的樹脂封閉元件的光半導 體裝置。 硬化條件(5) 藉由將比較例3獲得的樹脂組成物注入鑄模(形狀: 燈形狀,大小:φ 3)中,插入經封裝藍色發光二極體元 件的引導框架後,以烤爐(ESpec公司製GPHH 2〇1)於 -23- 201217421 1 50°C下加熱硬化7小時,獲得以硬化的樹脂封閉元件的 光半導體裝置》 透光率 將以實施例及比較例之調配處方所致硬化前硬化性 環氧樹脂組成物於預定的鑄模中鑄製,以上述硬化條件 熱硬化,並製作厚度3mm的板。使用分光光度計(島津 製作所公司製分光光度計UV-2450)測定450nm之透光 率。結果如表1所示。 光度保持率 使用全光束測定機(美國〇ptr〇nic Laboratories公司 製多重分光放射測定系統〇L77丨),測定由實施例及比 較例所得之光半導體裝置的全光束。進一步在23t:、 60 /eRH之恆溫恆濕槽内,於3〇〇小時測定在光半導體 襞置中流經l〇0mA的電流後之全光束。由次式計算光度 保持率。結果如表1所示β {光度保持率(%)}叫300小時後全光束小時 之全光束(Im)}xl〇〇 耐龜裂性試驗Commercial products such as Celloside 2021P, Celloside 208 1, and EHPE 3150 (made by Daicel Chemical Industry Co., Ltd.). The content of the alicyclic epoxy compound (A) is 6% by weight or more (e.g., 60 to 100% by weight) based on the total amount of the curable component contained in the curable epoxy resin composition. The curable component means a curable compound which is hardened by heat or radiation. The content of the alicyclic epoxy compound (A) is preferably set to 7% by weight (7 Torr to 100% by weight/min) relative to the total amount of the curable component. More preferably, the weight is 0/〇 or more (8 〇). In the case of using two or more kinds of alicyclic epoxy compounds (A), the above contents are the total contents. By setting the content of the alicyclic epoxy compound (A) within the above range, when the curable epoxy resin composition is cured, a cured product excellent in light transmittance and photometric retention can be obtained. The total content of the curable components in the curable epoxy resin composition used in the method for producing a cured product of the present invention is, for example, 3 Torr to 9 Torr. Preferably, it is 40 to 80% by weight, more preferably 4 to 7 inches by weight / Torr. By setting the content of the curable component in the curable epoxy resin composition within the above range, a resin composition having excellent curability can be obtained. -12-201217421 &lt;Current component other than the alicyclic epoxy compound (A)> The curable epoxy resin composition used in the present invention may contain an epoxy compound other than the alicyclic epoxy compound (4). As the epoxy compound other than the alicyclic epoxy compound (fluorene), it can be used in dioctyl octane hexahydrophthalate, bis(2·ethylhexyl) epoxide hexahydrophthalate, and butyl bromide. Diglycidyl ether, 1,6-hexanediol diglycidyl ether, triglycidyl ether of glycerol, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol Adding one or more alkylene oxides to an aliphatic polyol such as pentacyclopropanol of pentaerythritol, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, propylene glycol or glycerin The polyglycidyl ether of the polyether polyol; the monoglycidyl ether of the aliphatic long-chain dibasic acid aliphatic higher alcohol or the benzene age, the butyl group, the butyl alum, and the addition in the same Polypropylene glycol monoglycidyl ether derived from alkylene oxide; glycidyl ester of higher fatty acid, epoxidized soybean oil, octyl epoxy stearate, butyl epoxy stearate, epoxidized linseed oil, ring Oxidized butadiene, ethylene oxide, propylene oxide, styrene oxide, methyl epoxidized ether, butyl epoxidized ether, allyl propylene propylene, phenyl epoxidized ether, Ethylene glycol epoxidized propyl ether, ethylene glycol, propylene, propylene, ethylene glycol, propyl propyl methacrylate, glycidyl methacrylate, glycidyl acetate, etc. Or a part or all of the hydrogen atom of the epoxy compound is substituted with I. Further, in addition to the above, a radiation curable resin having an epoxy group-containing oligomer in its interior may be used. For example, epoxidized polybutadiene (product name: Epolead ΡΒ 3600, ΡΒ 4700, Daicel Chemical Industry Co., Ltd.), epoxidized styrene butadiene short block copolymer (teleblock cop〇lymer) (product name Epofriend AT501) , Daicel -13- 201217421 Chemical Industry Co., Ltd.) and so on. Further, there is a novolac type epoxy resin, for example, a novolak obtained by reacting a phenol such as phenol, cresol, a toothed phenol or an alkaloid with formaldehyde under an acidic catalyst, and an epichlorohydrin and/or a mercapto group. The product obtained by the reaction of epoxidized gas (product name: EOCN-103, EOCN-104S 'EOCN-1020, EOCN-1027, EPPN-201, BREN-S, Nippon Kayaku Co., Ltd.; product name: DEN-431, DEN -439, Dow Chemical Company and product name: N-73, VH-4150 'Otsuka Ink Chemical Industry Co., Ltd.), etc. Further, there is a double-prospective epoxy resin obtained by reacting a bisphenol A, a bisphenol F, a bisphenol S, a tetrabromobisphenol a or the like with an epoxy gas, or a double epoxy resin. A double-prospective epoxy resin obtained by reacting a condensate of a propyl ether with the above bisphenol and epichlorohydrin (product name: epik〇te 1〇〇4, epikote 1002 'oiled Shell Co., Ltd.; product name: DER_33 〇, DER-337 'Dow Chemical Company', etc. The epoxy compound other than the alicyclic epoxy compound (A) may be used singly or in combination of two or more kinds as exemplified above. In the case of the epoxy compound other than the alicyclic epoxy compound (A), an epoxy compound having an aromatic ring such as a bisphenol A epoxy resin is preferably used. Epoxy compounds other than the alicyclic epoxy compound (A) may not be used. &lt;hardener (B)&gt; The process of the cured product of the present invention; the curable epoxy resin composition of the π At m , &lt; H k method contains hardened 丨 丨 f, r* JL· Agent (B). The hardener (B) has an effect of hardening the epoxy group-containing compound. In the case of the hardener (B) in the present invention, a known curing agent can be used as a curing agent for the ym. In the present invention, the hardener (B), wherein # a 0 ^τ is preferably a 25 C liquid and acid anhydride, may be exemplified by A-14-201217421-based tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, and twelve Carbene succinic anhydride, methyl endo-methylene tetrahydro acid needle, and the like. Further, for example, an anion anhydride such as a hydrocarbon anhydride, a tetrahydrogenated liver, a hexahydrophthalic anhydride or a nonylcyclohexene dicarboxylic anhydride (25. a solid anhydride in the form of a solid is dissolved in a normal temperature (25.). In the case of a liquid acid anhydride, it is used as a liquid mixture, and can be used as the curing agent (B) in the present invention. Further, in the present invention, Rikacid MH-700 (manufactured by Shintobu Chemical Co., Ltd.), HN can be used. Commercial product such as -5500 (Hitachi Chemical Co., Ltd.) is used as a curing agent (B). The curing agent (B) may be used alone or in combination of two or more kinds in any ratio. The amount of use thereof is, for example, relative to a hardenable ring. The total amount of the epoxy group-containing compound contained in the oxyresin composition is 丨〇〇 by weight and 5' is 50 to 150 parts by weight, preferably from 1 to 145 parts by weight, more specifically, the above-mentioned sclerosing property. It is preferable to use a ratio of 0.5 to 1.5 equivalents per one equivalent of the epoxy group in the compound having a % mercapto group contained in the epoxy resin composition. The amount of the hardener (B) used is less than 5 〇 by weight. The effect is not sufficient, and the toughness of the hardened material tends to decrease, and the aspect When the amount of the curing agent (B) is more than 150 parts by weight, the cured product may be colored and the color tone may be deteriorated. When two or more kinds of curing agents (B) are used, the above-mentioned amount used is the total amount used. In the present invention, it is preferable to use a ratio of 〇.5 to 1.5 equivalents of the hardener (B) per one equivalent of the epoxy group in the compound having a bad oxy group contained in the curable epoxy resin composition. Therefore, in the case of the reaction at the time of hardening, it is considered that the hardenable epoxy resin composition is hardened at a low temperature of 95t:, 13 5 ◦ or less, so that it can be smoothly and evenly produced in the heat. In the test, the cured product is excellent in crack resistance. 201217421 <Curing accelerator (c)> The curable epoxy resin composition used in the method for producing a cured product of the present invention contains a curing accelerator (C). c) a compound having a function of promoting a curing rate when a compound having an epoxy group is hardened with a curing agent. The hardening accelerator (C) which may be contained in the curable epoxy resin composition of the present invention may be used conventionally. Hardening The agent may, for example, be 1,8-diazabicyclo[5.4.0]undec-7 (DBU) and a salt thereof (for example, benzene salt, octanoate, p-toluenesulfonate, formate, Tetraphenylborate), 1,5-diazabicyclo[4.3.0]indole-5 (DBN) and its salts (eg, scale salts, plated salts, quaternary ammonium salts, iodonium salts); benzyl a tertiary amine such as diamine, 2,4,6-glycol(diamylaminomethyl)phenol or N,N-dimethylcyclohexylamine; 2·ethyl-4-methylimidazole, 1- An imidazole such as cyanoethyl·2_ethyl_4_mercaptoimidazole; a phosphine such as phosphoric acid 8 or diphenylphosphine; a benzoic acid tetraphenylphosphonate; An organic metal salt such as zinc octoate; a metal chelate compound or the like. These may be used alone or in combination of two or more. Further, in the present invention, U-CAT SA506, U-CAT SA 102, U-CAT 5003, U-CAT 18X, and 12XD (developed products) (all manufactured by San-apro Co., Ltd.), ΤΡΡ·Κ, TPP- can be used. Commercial products such as MK (both manufactured by Kitachem Chemical Industries Co., Ltd.) and PX-4ET (manufactured by Nippon Chemical Industry Co., Ltd.) are used as curing accelerators (C). The cerium hardening accelerator (C) can be used alone or in combination of two or more kinds at any ratio. It doesn't matter. The amount of use thereof is, for example, 0.05 to 5 parts by weight, preferably 〇.1 to 3, relative to the total amount of the compound having an epoxy group contained in the curable epoxy resin composition, and a part by weight. The parts by weight are particularly preferably from 0.2 to 3 parts by weight, most preferably from 0.25 to 25 parts by weight, from 16 to 201217421. When the amount of use of the curing accelerator (C) is less than 0.05 part by weight, the curing acceleration effect may be insufficient. On the one hand, when the amount of the curing agent is more than 5 parts by weight, the cured product is colored and the color tone is changed. In the case of using two or more kinds of the hardening accelerators (c), the above-mentioned amount used is the total amount used. <Inorganic filler> The curable property used in the method for producing a cured product The epoxy resin composition may further contain an inorganic filler. The inorganic filler is not particularly limited 'but more than one type of cerium oxide, aluminum oxide, mica, synthetic mica, talc, cerium oxide, carbonic acid, oxidized, Titanium oxide, barium titanate, kaolin, bentonite, diatomaceous earth, boron nitride, aluminum nitride, tantalum carbide, zinc oxide, cerium oxide (IV), oxidized planer, magnesia, glass beads, glass fiber And graphite, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, cellulose, etc., and the inorganic filler may, for example, be nano cerium oxide, nano titanium dioxide, nano cerium oxide, carbon nanotube or the like. The inorganic filler may be produced by a known method such as a pyrotechnic hydrolysis method, a pyrotechnic pyrolysis method, or a plasma method described in International Publication No. 96/3 1572. For the suitable inorganic filler, a stabilized colloidal inorganic substance may be used. In the case of commercially available products, there are commercially available products such as silica dioxide sol produced by BAYER, Sn02 sol manufactured by Goldschmidt, Ti02 sol manufactured by MERCK, and Si02 and Zr02 manufactured by Nissan Chemicals. Commercial products such as Al2〇3 and Sb203 sol or Aerosil dispersions manufactured by DEGUSSA can be obtained. -17- 201217421 Inorganic fillers can be modified by surface modification to change the viscosity behavior of the particles. It is carried out using a well-known surface modifier. For such a surface modifier, for example, a compound which can interact with a complex structure such as a covalent bond or a complex group existing on the surface of the inorganic filler can be used. Or a compound that can interact with a polymer matrix. Such a surface modifier can be used, for example, having a carboxyl group, a (primary, secondary, tertiary) amine in the molecule. a compound of a quaternary ammonium group, a carbonyl group, a epoxypropylvinyl group, a (i) acryloxy group, a functional group such as a thio group, etc. Such a surface modifier is usually a liquid under standard temperature and pressure conditions. The molecular weight of the low molecular organic compound is preferably 5 or less, preferably 10 or less, and particularly preferably 10 or less. The molecular weight of the low molecular organic compound is, for example, 5 Å or less, preferably the following. It is especially good for 200. Appropriate surface modifiers can be used to formulate formic acid, acetic acid, propionic acid, butyric acid, citric acid, caproic acid, acrylic acid, methacrylic acid, crotonic acid, citric acid.己, 己 ό 、, 戊 酿 苜, 苜 曼 曼 曼 顺 顺 顺 顺 顺 曼 曼 曼 1 1 1 « « « « « « « « « « « « « « « « « « Acids (preferably monocarboxylic acids) and such ester necks (preferably C! to C4 alkyl esters such as methyl methacrylate); guanamines, acetaminophen _, 2, A β-dicarbonyl compound such as 4-hexanedione, 3,5-heptanedione, acetamidineacetic acid or 1 king alkaneacetic acid. Further, although I 牿 a Λ ^ ..., a specific limitation, a well-known decane coupling agent can be used as a surface modifier. The particle diameter of the inorganic filler is usually Λη, and 铋 is from about 吊 〇 〇 〇 η η η η 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 。 。 。 。 。 。 。 。 。 。 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 -18- 201217421 If the total content of the hardening component is 丨 00 parts by weight, the content of the inorganic filler is preferably from 1 to 2000 parts by weight, more preferably from 10 parts by weight. Further, the content of the inorganic filler is, for example, 5 to 95% by weight, preferably 10 to 90% by weight based on the total amount of the curable epoxy resin composition. Further, when two or more kinds of inorganic fillers are used, the above contents are the total contents. &lt;Rubber Particles&gt; The curable epoxy resin composition used in the present invention may further contain rubber particles. The rubber fine particles may, for example, be a granular NBR (acrylonitrile-butadiene rubber), a reactive terminal mercapto NBR (CTBN) 'metal-free nbr, a granular styrene-butadiene rubber). The rubber particles have a multilayer structure (core-shell structure) comprising a rubber-elastic core portion and an outer shell layer covering at least a layer of the core portion, as π π + as a surface reactive with the alicyclic epoxy resin a rubber particle having a hydroxyl group and/or a carboxyl group and having an average particle diameter of iOnm to 5 〇〇 nm and a maximum particle diameter of 5 〇 nmi (10), and the towel may have a refractive index of the rubber particle and the sclerosing property The rubber particles of the cured product of the epoxy resin composition have a refractive index 葚耵 + difference of ± 0.02 or less. It is also possible to use one type of rubber fine particles or two or more kinds of mixed with A. The content of the rubber fine particles is, for example, 〇.5 I 30 parts by weight, preferably 1 to 2 parts by weight, based on 100 parts by weight of the total of the curable component knives. When the amount is less than 0.5 part by weight, the crack resistance tends to be lowered, and when it is more than 30 parts by weight, the heat resistance and the transparency tend to be lowered. Further, two or more kinds of rubber particles are used. In the case, the above content is the total content. -19-201217421 &lt;Additives&gt; In addition to the above, various additives may be used in the curable epoxy resin composition of the present invention within the range of the effects of the present invention. When a compound having a hydroxyl group such as ethylene glycol, diethylene glycol, propylene glycol or glycerin is used as the additive, the reaction can be progressed slowly. In addition, in the range of no loss of viscosity or transparency, it is also possible to use a polysiloxane or a defoamer, a leveling agent, a gamma-glycidoxypropyltrimethoxysulfonium, etc. Conventional additives such as a mixture, a surfactant, a flame retardant, a colorant, an antioxidant, an ultraviolet absorber, an ion adsorbent, a pigment, a phosphor, a release agent, and the like. The curable epoxy resin composition used in the method for producing a cured product of the present invention can be obtained by uniformly mixing the above components. In order to obtain the above-mentioned hardenable epoxy resin composition, it is necessary to use a general-known mixing such as a spin-transformer mixing/packing device, a homogenizer, a planetary mixer, a three-roll mill, and a bead mill. It is desirable to use a machine to stir, dissolve, mix, disperse, etc. the components as much as possible. <Cured product> The cured curable epoxy resin composition is cured by the above-mentioned curing conditions, and is excellent in transparency, light resistance (photosusceptibility, etc.), and is resistant to cracking in a heat cycle test. All physical properties such as sex are excellent hardened materials. 'Blocking material> The sealing material of the present invention is obtained by using the curable epoxy resin composition as a blocking agent and curing it under the above-mentioned curing conditions to impart transparency and light resistance (photos retention). It is excellent, and it is excellent in the physical properties such as crack resistance in the heat cycle test. -20-201217421 &lt;Optical semiconductor device&gt; The optical semiconductor device of the present invention can be obtained by blocking the optical semiconductor element with the curable epoxy resin composition and hardening it under the above-described curing conditions. The sealing of the optical semiconductor element is carried out by injecting a curable epoxy resin composition prepared by the above method into a predetermined molding die, and heating and hardening the above-described curing conditions. The optical semiconductor device of the present invention is excellent in transparency, light resistance (photosusceptibility, etc.), and excellent in physical properties such as crack resistance in a heat cycle test. According to the method for producing a cured product of the present invention, it is possible to obtain an optical semiconductor sealing material and a bonding material which are excellent in transparency, light resistance (photosustainability, etc.), and excellent in physical properties such as crack resistance in a heat cycle test. Electrical insulating materials, laminates, coatings, inks, coatings, sealants (seaUnt), photoresists, composites, transparent substrates, transparent sheets, transparent films, optical components, optical lenses, optical components, laser lithography Lithography, electronic paper, touch panel, solar cell substrate optical waveguide, light guide plate, holographic memory, etc. Embodiments Hereinafter, the present invention will be described in more detail based on embodiments. However, the invention is not limited to the embodiments. Production Example 1 (Epoxy Resin A) By formulating the formulation (unit: parts by weight) according to Table 1, 2,2-bis(hydroxyindenyl)-1-butanol 1,2-epoxy group 4·(2-Ethylene oxide)cyclohexane adduct (ΕΗρΕ315〇 manufactured by Daicel Chemical Industry Co., Ltd.) and 3 4 epoxy-21 - 201217421 Cyclohexylmethyl-3',4'-epoxy group A cyclohexane carboxylate (Celloside 2021P manufactured by DaUei Chemical Co., Ltd.) or a bisphenol a-type epoxy resin (YD-12 8 manufactured by Nippon Steel Chemical Co., Ltd.) was mixed and found in § 〇. Dissolve 2,2-bis(hydroxyindenyl)-1-butanol, i,2-epoxy-4-(2-oxiranyl)cyclohexane adduct by hydrazine and stirring for 1 hour 'Get epoxy resin (mixture). Production Example 2 (a mixture of a hardener, a hardening accelerator and an additive, and a flexible providing agent, hereinafter referred to as a B agent) As a B agent, a spinning-common mixing device (Thinky Mixer) AR- is used. 250 Thinky Company), hardener (Rikacid MH-700, manufactured by Nippon Chemical and Chemical Co., Ltd.; 4-methylhexahydrophthalic anhydride/hexahydrophthalic anhydride = 70/30): 100 parts by weight, hardening accelerator (San apr〇 Company made 1 8X). 0.5 parts by weight, additive (B-King, manufactured by Wako Pure Chemical Industries, Ltd.). 1 heavy Dong, flexible supply (Rikaeid HF-08, manufactured by Nippon Chemical Co., Ltd.). 3 parts by weight, uniform Mix, defoam and obtain B agent. In Examples 1 to 7 and Comparative Examples 1 to 7, the epoxy resin A obtained in Production Example 1 and the B agent obtained in Production Example 2 were formulated according to Table 1 (unit: parts by weight). , = The mixture was uniformly mixed and defoamed by a rotation-common transformation stirring device (manufactured by a defoaming mixer) to obtain a curable epoxy resin composition. Hardening condition (j) The resin composition obtained in Examples 1 and 3 was injected into a mold (shape-light shape '大々, : 0 3), and a guide frame (lead) of the packaged blue light-emitting diode was inserted. After the frame was heated and hardened at 100 ° C for 15 hours in an oven (Espec Inc.-22-201217421 GPHH-20 1), an optical semiconductor device with a resin sealing member was obtained. Hardening Condition (2) The resin composition obtained in each of Examples 2, 4 to 7 was injected into a mold (shape, lamp shape 'size. 03), and inserted into a guide frame of the packaged blue light-emitting diode element. The film was heat-hardened at 120 ° C for 7 hours in an oven (GPHH-201, manufactured by Espec Co., Ltd.) to obtain an optical semiconductor device with a resin sealing member. Hardening condition (3) The resin composition obtained in Comparative Examples 1 and 4 was injected into a scale mold (shape: lamp shape 'size; 0 3), and 'inserted into the guide frame of the packaged blue light-emitting diode element, An oven (GPHH-201 manufactured by Espec Co., Ltd.) was heat-hardened at 120 ° C for 4 hours to obtain an optical semiconductor device with a resin sealing member. Hardening condition (4) After injecting the resin composition obtained in Comparative Examples 2, 5 to 7, into a mold (shape: lamp shape, size: 03), after inserting the guide frame of the packaged blue light-emitting diode element, An oven (GPHH-201 manufactured by Espec Co., Ltd.) was heat-hardened for 2 hours at TC, and then heat-hardened under a crucible (8) for 3 hours to obtain an optical semiconductor device with a cured resin sealing member. The resin composition obtained in Comparative Example 3 was injected into a mold (shape: lamp shape, size: φ 3), and inserted into a guide frame of the packaged blue light-emitting diode element, and then baked in an oven (GPHH manufactured by ESpec Co., Ltd.) 2〇1) -23-201217421 1 heat hardening at 50 ° C for 7 hours to obtain an optical semiconductor device with a cured resin sealing member." Light transmittance will be hardened before hardening by the formulation of the examples and comparative examples. The epoxy resin composition was cast in a predetermined mold, and heat-hardened under the above-mentioned hardening conditions to prepare a plate having a thickness of 3 mm. The light transmittance at 450 nm was measured using a spectrophotometer (Spectrophotometer UV-2450 manufactured by Shimadzu Corporation). The results are shown in Table 1. The luminosity retention rate was measured using a full beam measuring machine (Multiple Spectroradiometric System 〇L77丨, manufactured by Ptr〇nic Laboratories, Inc., USA), and the total light beams of the optical semiconductor devices obtained in the examples and the comparative examples were measured. Further at 23t: In a constant temperature and humidity chamber of 60 /eRH, the total beam after flowing a current of 10 mA in the photo-semiconductor device was measured at 3 hr. The photo-retention ratio was calculated by the following formula. The results are shown in Table 1. Retention rate (%)} is called full beam (Im)}xl〇〇 crack resistance test after 300 hours

在由實施例及比較例所P 刼“ μ 所侍的光半導體裝置中,使用 …、衝擊试驗機(小型冷熱衝擊 制、教置TSE-11-AEspec公司 製)’將-4(TC · 15分鐘及12(Γ ν 榭墼,冷紅&amp; C · 15分鐘作為一循環的熱 衝擊’進行400循環的試驗。 (VHX 900 v 其後,使用數位微觀測器 (VHX-900 Keyence 公司製), 光丰遙俨担罢由 )觀察龜裂之長度’在5個 九牛導體裝置中,計測發生的 物的光半導體裝置個數。级 &quot;又有90μπι以上之 ,果如表1所示。 -24- 201217421 比較例 l 1 S ο ο ι 1 1 Ο I § 00 沄 1 ο •—4 ο 1 1 1 Ο 1 s 00 On 寸 - Ο 1 ο ο 1 1 1 ο 1 On 00 v〇 On «ο 1 Ο i·^ 1 ο ο Τ-Η 1 1 Ο 1 1 § in On u-&gt; C^i 〇 I 1 ο ο 1 1 1 1 Ο σ\ Os yn &lt;N 〇 I 1 ο ο 1 1 1 ο 1 s; 00 Os — 1 1 ο ο ^&quot;4 1 1 0 1 &lt; § ON ON 寸 1 Ο ο *—ί ο 1 ο 1 I 1 On 00 ON 00 〇 v〇 Ο 1 ο ο 1 Ο 1 1 1 S ON o : 1 ο ο 1 Ο 1 1 1 On 00 VO On o 實施作. 寸 ο 1 ο ο 1 Ο t 1 1 〇\ 00 S; o , Ο 1 ο ο 0 1 1 1 1 Ό Os o (N ο r*H 1 t ο Ο 1 Ο 1 1 1 00 ON o Ο 1 1 ο »*Μ Ο ο 1 1 1 1 5: 00 On o I CEL2021P ΕΗΡΕ3150 YD-128 1 Α劑 Β劑 ① 100°Cx5h ② 12〇x7h ③ 120t&gt;4h ④ 10CT〇2h、14(r〇3h 1 ⑤ 150t:x7h | 透光率(%) I 光度保持率(%) 犁單 1 t »· m 調配 硬化條 件 -lnc\l_ 201217421 產業上可 根據 度、時間 為光半導: 循壤試驗, 【圖式簡 無。 【主要元 無。 利用性 本發明之製造方法,藉由在硬 最適化,而可形成透明噃優異, 蜜裝置之封閉材料之情形的耐光 卜耐龜裂性優異的硬化物。 單說明】 件符號說明】 性優異、在熱 -26-In the optical semiconductor devices of the examples and the comparative examples, the optical semiconductor device was used, and the impact tester (small thermal shock system, manufactured by TSE-11-AEspec Co., Ltd.) was used - 4 (TC · A test of 400 cycles was carried out for 15 minutes and 12 (Γ ν 榭墼, cold red &amp; C · 15 minutes as a thermal shock of a cycle). (VHX 900 v Thereafter, using a digital microobserver (VHX-900 Keyence) )), see the length of the crack' in the five nine-nine conductors, the number of optical semiconductor devices that measure the occurrence of the material. The level &quot; has more than 90μπι, as shown in Table 1. -24- 201217421 Comparative Example l 1 S ο ο ι 1 1 Ο I § 00 沄1 ο • -4 ο 1 1 1 Ο 1 s 00 On Inch - Ο 1 ο ο 1 1 1 ο 1 On 00 v〇 On «ο 1 Ο i·^ 1 ο ο Τ-Η 1 1 Ο 1 1 § in On u-&gt; C^i 〇I 1 ο ο 1 1 1 1 Ο σ\ Os yn &lt;N 〇I 1 ο ο 1 1 1 ο 1 s; 00 Os — 1 1 ο ο ^&quot;4 1 1 0 1 &lt; § ON ON inch 1 Ο ο *—ί ο 1 ο 1 I 1 On 00 ON 00 〇v〇Ο 1 ο ο 1 Ο 1 1 1 S ON o : 1 ο ο 1 Ο 1 1 1 On 00 VO On o Implementation. Inch ο 1 ο ο 1 Ο t 1 1 〇 00 00 S; o , Ο 1 ο ο 0 1 1 1 1 Ό Os o (N ο r*H 1 t ο Ο 1 Ο 1 1 1 00 ON o Ο 1 1 ο »*Μ Ο ο 1 1 1 1 5: 00 On o I CEL2021P ΕΗΡΕ3150 YD-128 1 Tincture tincture 1 100°Cx5h 2 12〇x7h 3 120t&gt;4h 4 10CT〇2h , 14 (r〇3h 1 5 150t: x7h | light transmittance (%) I luminosity retention rate (%) plow single 1 t »· m blending hardening conditions -lnc\l_ 201217421 industry can be based on degree, time is light half Guide: According to the soil test, [The figure is simple. [The main element is not. The use of the manufacturing method of the present invention, by the hardening of the hardening, can form a transparent enamel, the sealing material of the honey device is resistant to light and resistance A hardened material with excellent cracking properties. Single explanation] Description of the symbols] Excellent, hot -26-

Claims (1)

201217421 七、申請專利範圍: 1. 一種硬化物之製造方法,其牲 丹特徵為包含脂環式環氧化 合物(A)、硬化劑(B)、及硬化促進劑(c)作為硬化性成 分,相對於硬化性成分全量而言,將該脂環式環氧化 合物(A)之含量為60重量%以上之硬化性環氧樹脂組成 物,在溫度95°C以上135Ό以下、且4.5小時以上之硬 化條件下硬化之方法。 2. —種硬化物,其係以如申請專利範圍第丨項之製造方 法所製造。 .3·—種封閉材料,其含有如申請專利範圍第2項之硬化 物。 4.—種光半導體裝置,其含有如申請專利範圍第3項之 封閉材料β -27- 201217421 四、指定代表圖: (一) 本案指定代表圖為:無。 (二) 本代表圖之元件符號簡單說明: 無0 五、本案若有化學式時,請揭示最能顯示發明特徵的化學式:201217421 VII. Patent application scope: 1. A method for producing a cured product, which is characterized in that it comprises an alicyclic epoxy compound (A), a hardener (B), and a hardening accelerator (c) as a hardening component. The curable epoxy resin composition having a content of the alicyclic epoxy compound (A) of 60% by weight or more, based on the total amount of the curable component, is at a temperature of 95 ° C or more and 135 ° or less and 4.5 hours or more. A method of hardening under hardening conditions. 2. A cured product produced by the method of manufacture of the scope of the patent application. .3. A closure material comprising a hardener as in item 2 of the scope of the patent application. 4. An optical semiconductor device comprising a sealing material as claimed in item 3 of the patent scope β -27- 201217421 IV. Designation of representative drawings: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: None 0. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention:
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WO2014196515A1 (en) * 2013-06-03 2014-12-11 株式会社ダイセル Curable epoxy resin composition
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3283606B2 (en) * 1993-02-17 2002-05-20 日本化薬株式会社 Organopolysiloxane and epoxy resin composition containing the same
JP3623530B2 (en) * 1994-04-18 2005-02-23 日東電工株式会社 Optical semiconductor device
JP2003026763A (en) * 2001-07-13 2003-01-29 New Japan Chem Co Ltd Epoxy resin composition
JP2007016063A (en) * 2005-07-05 2007-01-25 San Apro Kk Epoxy resin composition for sealing semiconductor
JP4398500B2 (en) * 2007-04-06 2010-01-13 株式会社日本触媒 Resin composition and optical member
JP5154340B2 (en) * 2008-08-27 2013-02-27 株式会社ダイセル Resin composition for optical semiconductor encapsulation
JP5606752B2 (en) * 2010-02-25 2014-10-15 株式会社ダイセル Resin composition for optical semiconductor sealing and optical semiconductor device using the same

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TWI700331B (en) * 2018-01-11 2020-08-01 南韓商Lg化學股份有限公司 Epoxy resin composition for molding semiconductor, molding film and semiconductor package using the same
US11702520B2 (en) 2018-01-11 2023-07-18 Lg Chem, Ltd. Epoxy resin composition for molding semiconductor, molding film and semiconductor package using the same

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