JP2007314740A - Epoxy resin composition, its cured product and photosemiconductor device - Google Patents
Epoxy resin composition, its cured product and photosemiconductor device Download PDFInfo
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- JP2007314740A JP2007314740A JP2006171305A JP2006171305A JP2007314740A JP 2007314740 A JP2007314740 A JP 2007314740A JP 2006171305 A JP2006171305 A JP 2006171305A JP 2006171305 A JP2006171305 A JP 2006171305A JP 2007314740 A JP2007314740 A JP 2007314740A
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- epoxy resin
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 63
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 63
- 239000000203 mixture Substances 0.000 title claims abstract description 34
- 239000000412 dendrimer Substances 0.000 claims abstract description 15
- 229920000736 dendritic polymer Polymers 0.000 claims abstract description 15
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims abstract description 10
- 239000004065 semiconductor Substances 0.000 claims description 11
- 230000003287 optical effect Effects 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 238000001723 curing Methods 0.000 description 10
- 125000002723 alicyclic group Chemical group 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 7
- 238000004040 coloring Methods 0.000 description 5
- 239000003566 sealing material Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 150000008065 acid anhydrides Chemical class 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 3
- 125000004018 acid anhydride group Chemical group 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- FKBMTBAXDISZGN-BOJSHJERSA-N (3ar,7as)-5-methyl-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1C(C)CC[C@@H]2C(=O)OC(=O)[C@H]12 FKBMTBAXDISZGN-BOJSHJERSA-N 0.000 description 2
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- FKBMTBAXDISZGN-UHFFFAOYSA-N 5-methyl-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1C(C)CCC2C(=O)OC(=O)C12 FKBMTBAXDISZGN-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 150000002118 epoxides Chemical group 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000013007 heat curing Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-UHFFFAOYSA-N 0.000 description 2
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- ICJOOQVYYVIPAG-UHFFFAOYSA-N 1-phenylbutane-1,3-dione;zinc Chemical compound [Zn].CC(=O)CC(=O)C1=CC=CC=C1 ICJOOQVYYVIPAG-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- UITKHKNFVCYWNG-UHFFFAOYSA-N 4-(3,4-dicarboxybenzoyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 UITKHKNFVCYWNG-UHFFFAOYSA-N 0.000 description 1
- OECTYKWYRCHAKR-UHFFFAOYSA-N 4-vinylcyclohexene dioxide Chemical compound C1OC1C1CC2OC2CC1 OECTYKWYRCHAKR-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical class C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- VBQRUYIOTHNGOP-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinine 6-oxide Chemical compound C1=CC=C2P(=O)OC3=CC=CC=C3C2=C1 VBQRUYIOTHNGOP-UHFFFAOYSA-N 0.000 description 1
- UBGVHKXCHHMPRK-UHFFFAOYSA-N benzotriazol-2-ide;tetrabutylphosphanium Chemical compound C1=CC=CC2=N[N-]N=C21.CCCC[P+](CCCC)(CCCC)CCCC UBGVHKXCHHMPRK-UHFFFAOYSA-N 0.000 description 1
- DJUWPHRCMMMSCV-UHFFFAOYSA-N bis(7-oxabicyclo[4.1.0]heptan-4-ylmethyl) hexanedioate Chemical compound C1CC2OC2CC1COC(=O)CCCCC(=O)OCC1CC2OC2CC1 DJUWPHRCMMMSCV-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- DLIJPAHLBJIQHE-UHFFFAOYSA-N butylphosphane Chemical compound CCCCP DLIJPAHLBJIQHE-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000012772 electrical insulation material Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- -1 glycidyl ester Chemical class 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- WATYAKBWIQTPDE-UHFFFAOYSA-N pentane-2,4-dione;zinc Chemical compound [Zn].CC(=O)CC(C)=O WATYAKBWIQTPDE-UHFFFAOYSA-N 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000004382 potting Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- JBCJMTUHAXHILC-UHFFFAOYSA-N zinc;octanoic acid Chemical compound [Zn+2].CCCCCCCC(O)=O JBCJMTUHAXHILC-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
- Led Device Packages (AREA)
Abstract
Description
本発明は、エポキシ樹脂組成物、その硬化物及び光半導体装置に関する。さらに詳しくは、着色が少なく、耐クラック性及び透明性に優れる硬化物を与えるエポキシ樹脂組成物、その硬化物及び光半導体装置に関する。 The present invention relates to an epoxy resin composition, a cured product thereof, and an optical semiconductor device. More specifically, the present invention relates to an epoxy resin composition that gives a cured product with little coloring and excellent crack resistance and transparency, the cured product, and an optical semiconductor device.
一般に、酸無水物とエポキシ樹脂から得られるエポキシ樹脂硬化物は、安価で、透明性、電気絶縁性、耐薬品性、耐湿性、接着性等に優れており、電気絶縁材料、半導体材料、接着材料、塗料材料等、様々な用途で用いられている。代表的な使用例の一つとして、発光ダイオード(Light−emitting diode:以下LEDと略す)の発光素子を保護するための封止材を挙げることができるが、近年になって短波長の光を発する光源と蛍光体とを組み合わせた白色LEDが普及するにつれ、封止材の劣化が問題視されるようになってきた。 Generally, epoxy resin cured products obtained from acid anhydrides and epoxy resins are inexpensive and have excellent transparency, electrical insulation, chemical resistance, moisture resistance, adhesiveness, etc., electrical insulation materials, semiconductor materials, adhesives It is used in various applications such as materials and paint materials. As a typical use example, a sealing material for protecting a light-emitting element of a light-emitting diode (hereinafter abbreviated as an LED) can be given. As white LEDs that combine a light source that emits light and a phosphor have become widespread, degradation of sealing materials has become a problem.
すなわち、白色LEDの場合、より高エネルギーの光源を用いるため、従来の赤色や緑色のLEDに比べて封止材が劣化して着色しやすく、LEDの寿命が短くなってしまうという問題が発生する。また、発光素子の改良によって小型化及び大電流化が進むにつれ、LEDを長時間点灯させた場合に発生する熱も大きくなり、これによっても同様に封止材の劣化が引き起こされる。 That is, in the case of a white LED, since a higher energy light source is used, there is a problem that the sealing material is degraded and easily colored as compared with a conventional red or green LED, and the life of the LED is shortened. . In addition, as the size of the light emitting element is improved and the current is increased, the heat generated when the LED is lit for a long time is increased, which also causes deterioration of the sealing material.
このような光や熱による劣化を抑制することは、エポキシ樹脂のさらなる普及において重要な課題となっている。これを解決する方法として、光や熱により劣化しやすい芳香族エポキシ樹脂に代わって脂環式エポキシ樹脂を用いたエポキシ樹脂組成物の提案がなされている(例えば、特許文献1、2及び3参照)。 Suppressing such deterioration due to light and heat is an important issue in the further spread of epoxy resins. As a method for solving this problem, there has been proposed an epoxy resin composition using an alicyclic epoxy resin in place of an aromatic epoxy resin that is easily deteriorated by light or heat (see, for example, Patent Documents 1, 2, and 3). ).
一方で、こういった脂環式エポキシ樹脂を用いたエポキシ樹脂組成物は、得られる硬化物が強靭性に乏しく、温度等の条件変化によってクラックを生じやすいという欠点があった。これを解決するためにエポキシ樹脂組成物から得られる硬化物を強靭化する方法としては、種々の高分子からなる改質剤を用いる手法が知られており、例えばエポキシ樹脂組成物にポリエステル樹脂を添加することにより硬化物の透明性を損なわずに強靭性を向上させる方法が提案されている(例えば、特許文献4参照)。 On the other hand, an epoxy resin composition using such an alicyclic epoxy resin has a drawback that the obtained cured product has poor toughness and is liable to crack due to changes in conditions such as temperature. In order to solve this, as a method for toughening a cured product obtained from an epoxy resin composition, a technique using a modifier composed of various polymers is known. For example, a polyester resin is added to an epoxy resin composition. There has been proposed a method for improving toughness without impairing the transparency of a cured product by addition (see, for example, Patent Document 4).
しかし、一般にポリエステル樹脂は縮合時に色が付きやすいため、上記特許文献4に記載された発明では、その実施例に示されるように硬化物が黄色から褐色に著しく着色してしまう。そのため、例えば上記LED封止材のように無色透明であることが要求される用途においては実用上問題があった。
本発明は、上記の問題を鑑みてなされたものであり、着色が少なく、耐クラック性及び透明性に優れる硬化物を与えるエポキシ樹脂組成物、その硬化物及び光半導体装置を提供するものである。 The present invention has been made in view of the above problems, and provides an epoxy resin composition that gives a cured product that is less colored and has excellent crack resistance and transparency, a cured product thereof, and an optical semiconductor device. .
本発明者らは、上記の課題を解決するため鋭意検討した結果、エポキシ樹脂及び多価カルボン酸無水物に対し、改質剤として樹枝状高分子を添加混合することにより、着色が少なく、耐クラック性及び透明性に優れる硬化物を与えるエポキシ樹脂組成物が容易に得られることを見出し、本発明を完成させるに至った。 As a result of intensive studies to solve the above-mentioned problems, the inventors have added and mixed a dendritic polymer as a modifier to the epoxy resin and the polyvalent carboxylic acid anhydride, thereby reducing coloring and resistance. It has been found that an epoxy resin composition giving a cured product having excellent cracking properties and transparency can be easily obtained, and the present invention has been completed.
本発明は、以下に関する。
(1)エポキシ樹脂、多価カルボン酸無水物及び樹枝状高分子を含むエポキシ樹脂組成物。
(2)多価カルボン酸無水物が、下記一般式(1)で表される化合物である項(1)記載のエポキシ樹脂組成物。
The present invention relates to the following.
(1) An epoxy resin composition comprising an epoxy resin, a polyvalent carboxylic acid anhydride and a dendritic polymer.
(2) The epoxy resin composition according to item (1), wherein the polyvalent carboxylic acid anhydride is a compound represented by the following general formula (1).
(式中、R1〜R4は、それぞれ独立に、水素原子又は直鎖若しくは分岐状の炭素数1〜4のアルキル基を表し、R1〜R4から選ばれる二つが結合して環を形成してもよい。)
(Wherein R 1 to R 4 each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, and two selected from R 1 to R 4 are bonded to form a ring. It may be formed.)
(3)樹枝状高分子が、ポリエステルである項(1)又は項(2)記載のエポキシ樹脂組成物。
(4)樹枝状高分子が、エポキシ樹脂100重量部に対して1〜60重量部含まれる項(1)〜(3)のいずれかに記載のエポキシ樹脂組成物。
(5)項(1)〜(4)のいずれかに記載のエポキシ樹脂組成物を硬化させてなる硬化物。
(6)項(5)記載の硬化物で光半導体素子が封止されてなる光半導体装置。
(3) The epoxy resin composition according to item (1) or item (2), wherein the dendritic polymer is polyester.
(4) The epoxy resin composition according to any one of items (1) to (3), wherein the dendritic polymer is contained in an amount of 1 to 60 parts by weight with respect to 100 parts by weight of the epoxy resin.
(5) A cured product obtained by curing the epoxy resin composition according to any one of items (1) to (4).
(6) An optical semiconductor device in which an optical semiconductor element is sealed with a cured product according to item (5).
本発明によれば、着色が少なく、耐クラック性及び透明性に優れる硬化物を与えるエポキシ樹脂組成物、その硬化物及び光半導体装置を容易に得ることができる ADVANTAGE OF THE INVENTION According to this invention, the epoxy resin composition which gives the hardened | cured material which has little coloring, and is excellent in crack resistance and transparency, its hardened | cured material, and an optical semiconductor device can be obtained easily.
以下、本発明を詳細に説明する。
本発明に用いる多価カルボン酸無水物は特に制限は無く、例えば無水コハク酸、無水マレイン酸、無水フタル酸、テトラヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、メチルエンドメチレンテトラヒドロ無水フタル酸、無水イタコン酸、ピロメリット酸無水物、ベンゾフェノンテトラカルボン酸無水物等が挙げられる。これらは二種類以上併用してもよい。
Hereinafter, the present invention will be described in detail.
The polycarboxylic acid anhydride used in the present invention is not particularly limited. For example, succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, itaconic anhydride Examples include acid, pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, and the like. Two or more of these may be used in combination.
本発明により得られる硬化物が、着色が少なく、耐クラック性及び透明性に優れるという効果をより顕著に発揮させるためには、多価カルボン酸無水物が上記一般式(1)で表される化合物であることが好ましい。 In order for the cured product obtained by the present invention to exhibit the effects of less coloring and excellent crack resistance and transparency, the polyvalent carboxylic acid anhydride is represented by the general formula (1). A compound is preferred.
このような化合物としては、例えばヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、メチルエンドメチレンヘキサヒドロ無水フタル酸等が挙げられる。これらは二種類以上併用してもよい。 Examples of such compounds include hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylendomethylenehexahydrophthalic anhydride, and the like. Two or more of these may be used in combination.
多価カルボン酸無水物の使用量は、エポキシ樹脂中のエポキシ基1当量に対して酸無水物基が0.8〜1当量になるよう配合することが好ましく、0.9〜1当量になるよう配合することがより好ましい。酸無水物基が0.8当量未満であると、硬化が不十分となり、硬化物の機械的特性が著しく低下するおそれがある。また、酸無水物基が1当量を超える場合にも、同様に硬化物の機械的特性が低下するおそれがある。 The amount of polyvalent carboxylic acid anhydride used is preferably such that the acid anhydride group is 0.8-1 equivalent to 1 equivalent of epoxy group in the epoxy resin, and is 0.9-1 equivalent. It is more preferable to blend so that. If the acid anhydride group is less than 0.8 equivalent, curing may be insufficient, and the mechanical properties of the cured product may be significantly reduced. Also, when the acid anhydride group exceeds 1 equivalent, the mechanical properties of the cured product may be similarly reduced.
本発明に用いる樹枝状高分子には特に制限は無いが、本発明により得られる硬化物の特徴である、着色が少なく、耐クラック性及び透明性に優れるという効果をより顕著に発揮させるためには、ポリエステルであることが好ましい。また、少なくとも1個の反応性エポキシド基又はヒドロキシル基を有する核に1〜50世代、好ましくは1〜10世代の少なくとも1個のジヒドロキシモノカルボン酸が付加されたポリエステルであることがより好ましい The dendritic polymer used in the present invention is not particularly limited, but in order to exhibit the effects of the cured product obtained by the present invention, which is less colored and excellent in crack resistance and transparency, more remarkably. Is preferably polyester. Further, it is more preferable that the polyester has 1 to 50 generations, preferably 1 to 10 generations of at least one dihydroxymonocarboxylic acid added to a nucleus having at least one reactive epoxide group or hydroxyl group.
好ましい核としては、ネオペンチルグリコール、トリメチロールプロパン、ペンタエリスリトール、2−ブチル−2−エチル−1,3−プロパンジオール等のアルコール類、モノカルボン酸のグリシジルエステル、モノアルコールのグリシジルエーテル等のエポキシド類などが挙げられる。 Preferred nuclei include alcohols such as neopentyl glycol, trimethylolpropane, pentaerythritol, 2-butyl-2-ethyl-1,3-propanediol, epoxides such as glycidyl esters of monocarboxylic acids, glycidyl ethers of monoalcohols, etc. And the like.
ジヒドロキシモノカルボン酸としては2,2−ビス(ヒドロキシメチル)プロピオン酸、2,2−ビス(ヒドロキシメチル)ブタン酸などが挙げられる。本発明に用いる樹枝状高分子の製造方法には特に制限は無く、公知の方法を適用することができる。 Examples of the dihydroxy monocarboxylic acid include 2,2-bis (hydroxymethyl) propionic acid and 2,2-bis (hydroxymethyl) butanoic acid. There is no restriction | limiting in particular in the manufacturing method of the dendritic polymer used for this invention, A well-known method is applicable.
本発明において、樹枝状高分子は、エポキシ樹脂100重量部に対して1〜60重量部含まれることが好ましく、30〜50重量部含まれることがより好ましい。樹枝状高分子の含有量が1重量部未満であると、得られる硬化物の強靭性が十分でなく、耐クラック性が低下するおそれがある。また、樹枝状高分子の含有量が60重量部を超えると、得られる硬化物のガラス転移温度が著しく低下するおそれがあり、実用上好ましくない。 In this invention, it is preferable that 1-60 weight part is contained with respect to 100 weight part of epoxy resins, and it is more preferable that dendritic polymer is contained 30-50 weight part. When the content of the dendritic polymer is less than 1 part by weight, the toughness of the obtained cured product is not sufficient, and the crack resistance may be lowered. On the other hand, if the content of the dendritic polymer exceeds 60 parts by weight, the glass transition temperature of the resulting cured product may be remarkably lowered, which is not preferable for practical use.
本発明に用いるエポキシ樹脂は特に制限は無いが、耐光性及び耐熱性の面から脂環式エポキシ樹脂が好ましい。脂環式エポキシ樹脂は、1分子中に脂環式骨格及び2個以上のエポキシ基を有するものであり、例えば3’,4’−エポキシシクロヘキシルメチル−3,4−エポキシシクロヘキサンカルボキシレート、ビス(3,4−エポキシシクロヘキシルメチル)アジペート、ビニルシクロヘキセンジオキサイド、水素添加ビスフェノールAジグリシジルエーテル等が挙げられる。これらは二種類以上併用してもよい。 Although there is no restriction | limiting in particular in the epoxy resin used for this invention, An alicyclic epoxy resin is preferable from the surface of light resistance and heat resistance. The alicyclic epoxy resin has an alicyclic skeleton and two or more epoxy groups in one molecule. For example, 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis ( 3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene dioxide, hydrogenated bisphenol A diglycidyl ether, and the like. Two or more of these may be used in combination.
また、目的に応じて脂環式エポキシ樹脂以外のエポキシ樹脂も用いることができる。このようなエポキシ樹脂としては、例えばビスフェノールA、ビスフェノールS等のビスフェノール類とエピクロロヒドリンとの反応により得られるビスフェノール型エポキシ樹脂、フェノールノボラックとエピクロロヒドリンとの反応により得られるフェノールノボラック型エポキシ樹脂、多価カルボン酸とエピクロロヒドリンとの反応により得られるグリシジルエステル型エポキシ樹脂などが挙げられる。これらは二種類以上併用してもよい。 Further, an epoxy resin other than the alicyclic epoxy resin can also be used depending on the purpose. Examples of such epoxy resins include bisphenol type epoxy resins obtained by reaction of bisphenols such as bisphenol A and bisphenol S with epichlorohydrin, and phenol novolak types obtained by reaction of phenol novolac and epichlorohydrin. Examples thereof include an epoxy resin, a glycidyl ester type epoxy resin obtained by a reaction between a polyvalent carboxylic acid and epichlorohydrin. Two or more of these may be used in combination.
これらの脂環式エポキシ樹脂以外のエポキシ樹脂の使用量は、脂環式エポキシ樹脂100重量部に対して0〜80重量部とするのが好ましく、0〜20重量部とするのがより好ましい。脂環式エポキシ樹脂以外のエポキシ樹脂の使用量が80重量部を超えると硬化物の耐光性及び耐熱性が低下するおそれがある。 The amount of the epoxy resin other than these alicyclic epoxy resins is preferably 0 to 80 parts by weight, more preferably 0 to 20 parts by weight with respect to 100 parts by weight of the alicyclic epoxy resin. When the usage-amount of epoxy resins other than an alicyclic epoxy resin exceeds 80 weight part, there exists a possibility that the light resistance and heat resistance of hardened | cured material may fall.
本発明においては、エポキシ樹脂、多価カルボン酸無水物及び樹枝状高分子を混合することにより目的とするエポキシ樹脂組成物を得ることができるが、その製造方法には特に制限は無く、公知の方法を適用することができる。 In the present invention, the target epoxy resin composition can be obtained by mixing an epoxy resin, a polyvalent carboxylic acid anhydride and a dendritic polymer, but the production method is not particularly limited, and is publicly known. The method can be applied.
本発明におけるエポキシ樹脂組成物は、目的に応じて硬化促進剤を適宜添加することができる。硬化促進剤としては、例えば2−エチル−4−メチルイミダゾール、1−メチルイミダゾール等のイミダゾール類、ベンジルジメチルアミン、N,N−ジメチルアニリン等の三級アミン、テトラメチルアンモニウムクロライド、ベンジルトリエチルアンモニウムクロライド等の四級アンモニウム塩、テトラ−n−ブチルホスホニウム o,o−ジエチルホスホロジチオネート、テトラブチルホスホニウム ベンゾトリアゾラート等のホスホニウム塩、オクチル酸亜鉛、ステアリン酸亜鉛等の金属塩、アセチルアセトン亜鉛、ベンゾイルアセトン亜鉛等の金属錯体などが挙げられる。 In the epoxy resin composition of the present invention, a curing accelerator can be appropriately added depending on the purpose. Examples of the curing accelerator include imidazoles such as 2-ethyl-4-methylimidazole and 1-methylimidazole, tertiary amines such as benzyldimethylamine and N, N-dimethylaniline, tetramethylammonium chloride, and benzyltriethylammonium chloride. Quaternary ammonium salts such as tetra-n-butylphosphonium o, o-diethyl phosphorodithionate, phosphonium salts such as tetrabutylphosphonium benzotriazolate, metal salts such as zinc octylate and zinc stearate, zinc acetylacetone, Examples thereof include metal complexes such as benzoylacetone zinc.
硬化促進剤のエポキシ樹脂組成物中の配合量は、0.01〜8重量%とするのが好ましく、0.1〜5重量%とするのがより好ましい。硬化促進剤の配合量が0.01重量%未満であると、十分な効果が得られないおそれがある。また、硬化促進剤の配合量が8重量%を超えると、得られる硬化物が着色したり耐熱性が低下したりするおそれがある。 The blending amount of the curing accelerator in the epoxy resin composition is preferably 0.01 to 8% by weight, and more preferably 0.1 to 5% by weight. If the blending amount of the curing accelerator is less than 0.01% by weight, a sufficient effect may not be obtained. Moreover, when the compounding quantity of a hardening accelerator exceeds 8 weight%, there exists a possibility that the hardened | cured material obtained may be colored or heat resistance may fall.
本発明におけるエポキシ樹脂組成物には、得られる硬化物の特性を損ねない範囲で各種添加剤を目的に応じてさらに添加することができる。添加剤としては、可撓化剤、熱安定剤、紫外線吸収剤、難燃剤、帯電防止剤、消泡剤、チキソトロピー性付与剤、離型剤等が挙げられる。更に、例えば、硬化物の耐光性及び耐熱性をさらに向上させるための酸化防止剤、硬化における重合反応を制御するための連鎖移動剤、硬化物の機械的物性、接着性、取扱い性を改良するための充填剤、可塑剤、低応力化剤、カップリング剤、染料、光散乱剤などが挙げられる。 Various additives can be further added to the epoxy resin composition according to the present invention depending on the purpose within a range that does not impair the properties of the resulting cured product. Examples of the additive include a flexibilizer, a heat stabilizer, an ultraviolet absorber, a flame retardant, an antistatic agent, an antifoaming agent, a thixotropic agent, and a release agent. Furthermore, for example, an antioxidant for further improving the light resistance and heat resistance of the cured product, a chain transfer agent for controlling the polymerization reaction during curing, and improving the mechanical properties, adhesiveness, and handleability of the cured product. Fillers, plasticizers, stress reducing agents, coupling agents, dyes, light scattering agents and the like.
本発明におけるエポキシ樹脂組成物を加熱硬化させることにより、着色が少なく、耐クラック性及び透明性に優れる硬化物を得ることができる。硬化物の製造方法には特に制限は無く、公知の方法を適用することができる。加熱硬化の温度及び時間は特に限定されないが、90〜180℃、1〜12時間が好ましい。エポキシ樹脂組成物を塗布、ポッティング、含浸等の方法により、LED発光素子等の表面上に設け、加熱硬化することにより、LED発光素子等を封止することができる。 By curing the epoxy resin composition in the present invention with heat, a cured product with little coloration and excellent crack resistance and transparency can be obtained. There is no restriction | limiting in particular in the manufacturing method of hardened | cured material, A well-known method is applicable. Although the temperature and time of heat-curing are not specifically limited, 90-180 degreeC and 1-12 hours are preferable. The LED light-emitting element or the like can be sealed by providing the epoxy resin composition on the surface of the LED light-emitting element or the like by a method such as coating, potting, or impregnation, followed by heat curing.
本発明の光半導体装置は、LED発光素子、フォトダイオード素子等の光半導体素子が上記硬化物で封止されたものであり、着色が少なく、耐クラック性及び透明性に優れ、さらに耐光性及び耐熱性にも優れるものである。 The optical semiconductor device of the present invention is an optical semiconductor element such as an LED light emitting element or a photodiode element sealed with the above cured product, has little coloring, is excellent in crack resistance and transparency, and further has light resistance and It also has excellent heat resistance.
以下、実施例により本発明をさらに具体的に説明する。本発明はこれらの実施例により制限されるものではない。
(実施例1)
トリメチロールプロパンを核とし、2,2−ビス(ヒドロキシメチル)プロピオン酸を付加させて得られる樹枝状高分子(BOLTORN P−500:Perstorp社製)40重量部に対して、エポキシ樹脂として3’,4’−エポキシシクロヘキシルメチル−3,4−エポキシシクロヘキサンカルボキシレート(セロキサイド2021P:ダイセル化学工業株式会社製/エポキシ当量138(g/eq))100重量部、硬化促進剤としてテトラ−n−ブチルホスホニウム o,o−ジエチルホスホロジチオネート(ヒシコーリンPX−4ET:日本化学工業株式会社製)1重量部、安定剤として9,10−ジヒドロ−9−ホスファ−10−オキサフェナンスレン−9−オキシド(HCA:三光化学株式会社製)1重量部を加え、80℃に加熱して攪拌し、均一に溶解させた。
Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is not limited by these examples.
Example 1
3 'as an epoxy resin with respect to 40 parts by weight of a dendritic polymer (BOLTORN P-500: manufactured by Perstorp) obtained by adding 2,2-bis (hydroxymethyl) propionic acid with trimethylolpropane as a core , 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (Celoxide 2021P: manufactured by Daicel Chemical Industries, Ltd./epoxy equivalent 138 (g / eq)), tetra-n-butylphosphonium as a curing accelerator 1 part by weight of o, o-diethyl phosphorodithionate (Hishicolin PX-4ET: manufactured by Nippon Chemical Industry Co., Ltd.), 9,10-dihydro-9-phospha-10-oxaphenanthrene-9-oxide (as a stabilizer) HCA: manufactured by Sanko Chemical Co., Ltd.) The mixture was heated and stirred to dissolve uniformly.
さらに、多価カルボン酸無水物として4−メチルヘキサヒドロ無水フタル酸(HN−7000:日立化成工業株式会社製/酸無水物当量168(g/eq))116重量部を80℃に加熱して攪拌しながら加え、均一になるまで溶解させてエポキシ樹脂組成物(I)を得た。 Furthermore, 116 parts by weight of 4-methylhexahydrophthalic anhydride (HN-7000: manufactured by Hitachi Chemical Co., Ltd./acid anhydride equivalent 168 (g / eq)) as polyvalent carboxylic acid anhydride was heated to 80 ° C. The resultant was added with stirring and dissolved until uniform to obtain an epoxy resin composition (I).
次に、エポキシ樹脂組成物(I)を減圧下で十分に脱泡させてから、金属製のクリップを中央に置いた金属製シャーレに静かに注入し、120℃で1時間加熱した後にさらに150℃で4時間加熱して硬化物(I)を得た。 Next, after sufficiently degassing the epoxy resin composition (I) under reduced pressure, the metal clip was gently poured into a metal petri dish placed at the center, heated at 120 ° C. for 1 hour, and then further 150 Heated at 4 ° C. for 4 hours to obtain a cured product (I).
(比較例1)
3’,4’−エポキシシクロヘキシルメチル−3,4−エポキシシクロヘキサンカルボキシレート(セロキサイド2021P:ダイセル化学工業株式会社製/エポキシ当量138(g/eq))100重量部、硬化促進剤としてテトラ−n−ブチルホスホニウム o,o−ジエチルホスホロジチオネート(ヒシコーリンPX−4ET:日本化学工業株式会社製)1重量部、安定剤として9,10−ジヒドロ−9−ホスファ−10−オキサフェナンスレン−9−オキシド(HCA:三光化学株式会社製)1重量部を加え、80℃に加熱して攪拌し、均一に溶解させた。
(Comparative Example 1)
100 parts by weight of 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (Celoxide 2021P: manufactured by Daicel Chemical Industries, Ltd./epoxy equivalent 138 (g / eq)), tetra-n- as a curing accelerator 1 part by weight of butylphosphonium o, o-diethyl phosphorodithionate (Hishicolin PX-4ET: manufactured by Nippon Chemical Industry Co., Ltd.), 9,10-dihydro-9-phospha-10-oxaphenanthrene-9- as a stabilizer 1 part by weight of oxide (HCA: manufactured by Sanko Chemical Co., Ltd.) was added, heated to 80 ° C., stirred and dissolved uniformly.
さらに、4−メチルヘキサヒドロ無水フタル酸(HN−7000:日立化成工業株式会社製/酸無水物当量168(g/eq))116重量部を80℃に加熱して攪拌しながら加え、均一になるまで溶解させてエポキシ樹脂組成物(II)を得た。
以下、実施例1と同様にして硬化物(II)を得た。
Furthermore, 116 parts by weight of 4-methylhexahydrophthalic anhydride (HN-7000: manufactured by Hitachi Chemical Co., Ltd./acid anhydride equivalent 168 (g / eq)) was heated to 80 ° C. and added with stirring. It was made to melt | dissolve until it became epoxy resin composition (II).
Thereafter, a cured product (II) was obtained in the same manner as in Example 1.
実施例1及び比較例1で得た硬化物(I)、(II)の外観及びクラックを評価し、その結果を表1に示した。表1における特性評価の方法は以下の通りである。
・外観:目視により判定した。
・クラック:硬化物を−30℃で20時間放置した後、室温(25℃)で10時間放置し、クラック発生の有無を目視で確認した。
○:クラック無し
×:クラック有り
The appearance and cracks of the cured products (I) and (II) obtained in Example 1 and Comparative Example 1 were evaluated, and the results are shown in Table 1. The characteristic evaluation method in Table 1 is as follows.
Appearance: Judged by visual inspection.
-Crack: The cured product was allowed to stand at -30 ° C for 20 hours and then allowed to stand at room temperature (25 ° C) for 10 hours, and the presence or absence of cracks was visually confirmed.
○: No crack
×: Crack present
表1に示したように、実施例1で得られた硬化物は、クラックも無く、無色透明であることが判った。それに対し比較例1の硬化物は、クラックが発生し、黄色に着色していた。本発明により、着色が少なく、耐クラック性及び透明性に優れる硬化物を与えるエポキシ樹脂組成物及びその硬化物を得ることができた。
As shown in Table 1, it was found that the cured product obtained in Example 1 was colorless and transparent without cracks. In contrast, the cured product of Comparative Example 1 was cracked and colored yellow. According to the present invention, it was possible to obtain an epoxy resin composition and a cured product thereof that give a cured product with little coloration and excellent crack resistance and transparency.
Claims (6)
(式中、R1〜R4は、それぞれ独立に、水素原子又は直鎖若しくは分岐状の炭素数1〜4のアルキル基を表し、R1〜R4から選ばれる二つが結合して環を形成してもよい。) The epoxy resin composition according to claim 1, wherein the polyvalent carboxylic acid anhydride is a compound represented by the following general formula (1).
(Wherein R 1 to R 4 each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, and two selected from R 1 to R 4 are bonded to form a ring. It may be formed.)
An optical semiconductor device comprising an optical semiconductor element sealed with the cured product according to claim 5.
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JP2009102510A (en) * | 2007-10-23 | 2009-05-14 | Hitachi Chem Co Ltd | Epoxy resin curing agent, epoxy resin composition, cured product thereof, and photosemiconductor device |
WO2010013638A1 (en) * | 2008-07-29 | 2010-02-04 | 日立化成工業株式会社 | Epoxy resin curing agent, epoxy resin composition, hardened material thereof, and optical semiconductor device |
JP2010278411A (en) * | 2009-04-28 | 2010-12-09 | Hitachi Chem Co Ltd | White coating agent, substrate for mounting optical semiconductor element using the same, and optical semiconductor device |
WO2013035542A1 (en) * | 2011-09-06 | 2013-03-14 | 株式会社ダイセル | Resin composition for sealing optical semiconductor, and optical semiconductor device using same |
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JP2009102510A (en) * | 2007-10-23 | 2009-05-14 | Hitachi Chem Co Ltd | Epoxy resin curing agent, epoxy resin composition, cured product thereof, and photosemiconductor device |
CN104693419A (en) * | 2008-07-29 | 2015-06-10 | 日立化成工业株式会社 | Epoxy resin curing agent, epoxy resin composition, hardened material thereof, and optical semiconductor device |
KR20110055481A (en) * | 2008-07-29 | 2011-05-25 | 히다치 가세고교 가부시끼가이샤 | Epoxy resin curing agent, epoxy resin composition, hardened material thereof, and optical semiconductor device |
TWI464192B (en) * | 2008-07-29 | 2014-12-11 | Hitachi Chemical Co Ltd | An epoxy resin hardener, an epoxy resin composition, a cured product thereof, and an optical semiconductor device |
WO2010013638A1 (en) * | 2008-07-29 | 2010-02-04 | 日立化成工業株式会社 | Epoxy resin curing agent, epoxy resin composition, hardened material thereof, and optical semiconductor device |
KR101636587B1 (en) * | 2008-07-29 | 2016-07-05 | 히타치가세이가부시끼가이샤 | Epoxy resin curing agent, epoxy resin composition, hardened material thereof, and optical semiconductor device |
JP2010278411A (en) * | 2009-04-28 | 2010-12-09 | Hitachi Chem Co Ltd | White coating agent, substrate for mounting optical semiconductor element using the same, and optical semiconductor device |
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WO2017126568A1 (en) * | 2016-01-20 | 2017-07-27 | 新日本理化株式会社 | Epoxy resin composition |
CN108473665A (en) * | 2016-01-20 | 2018-08-31 | 新日本理化株式会社 | Composition epoxy resin |
JPWO2017126568A1 (en) * | 2016-01-20 | 2018-11-15 | 新日本理化株式会社 | Epoxy resin composition |
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