WO2014073621A1 - Epoxy resin composition, cured product of same, and light emitting diode - Google Patents
Epoxy resin composition, cured product of same, and light emitting diode Download PDFInfo
- Publication number
- WO2014073621A1 WO2014073621A1 PCT/JP2013/080163 JP2013080163W WO2014073621A1 WO 2014073621 A1 WO2014073621 A1 WO 2014073621A1 JP 2013080163 W JP2013080163 W JP 2013080163W WO 2014073621 A1 WO2014073621 A1 WO 2014073621A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- epoxy resin
- resin composition
- acid anhydride
- mass
- acid
- Prior art date
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 293
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 293
- 239000000203 mixture Substances 0.000 title claims abstract description 132
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 71
- 150000001875 compounds Chemical class 0.000 claims abstract description 69
- -1 glycidyl ester Chemical class 0.000 claims abstract description 48
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 30
- 125000000524 functional group Chemical group 0.000 claims abstract description 26
- FWHUTKPMCKSUCV-UHFFFAOYSA-N 1,3-dioxo-3a,4,5,6,7,7a-hexahydro-2-benzofuran-5-carboxylic acid Chemical compound C1C(C(=O)O)CCC2C(=O)OC(=O)C12 FWHUTKPMCKSUCV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000004018 acid anhydride group Chemical group 0.000 claims abstract description 10
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims description 20
- 239000003963 antioxidant agent Substances 0.000 claims description 17
- 230000003078 antioxidant effect Effects 0.000 claims description 14
- 238000013329 compounding Methods 0.000 claims description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 6
- XFUOBHWPTSIEOV-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) cyclohexane-1,2-dicarboxylate Chemical compound C1CCCC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 XFUOBHWPTSIEOV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 5
- KTPIWUHKYIJBCR-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) cyclohex-4-ene-1,2-dicarboxylate Chemical compound C1C=CCC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 KTPIWUHKYIJBCR-UHFFFAOYSA-N 0.000 claims description 4
- KBWLNCUTNDKMPN-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) hexanedioate Chemical compound C1OC1COC(=O)CCCCC(=O)OCC1CO1 KBWLNCUTNDKMPN-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 abstract description 15
- 238000001723 curing Methods 0.000 description 41
- 238000004040 coloring Methods 0.000 description 18
- 238000010438 heat treatment Methods 0.000 description 12
- 239000003566 sealing material Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000002834 transmittance Methods 0.000 description 6
- 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 5
- 239000004593 Epoxy Substances 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 5
- 230000008719 thickening Effects 0.000 description 5
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 3
- 239000012212 insulator Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 3
- 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 2
- FAVZTHXOOBZCOB-UHFFFAOYSA-N 2,6-Bis(1,1-dimethylethyl)-4-methyl phenol Natural products CC(C)CC1=CC(C)=CC(CC(C)C)=C1O FAVZTHXOOBZCOB-UHFFFAOYSA-N 0.000 description 2
- 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 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- WTEPWWCRWNCUNA-UHFFFAOYSA-M benzyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 WTEPWWCRWNCUNA-UHFFFAOYSA-M 0.000 description 2
- 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 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 150000003842 bromide salts Chemical class 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 150000002903 organophosphorus compounds Chemical class 0.000 description 2
- 125000005496 phosphonium group Chemical group 0.000 description 2
- 150000004714 phosphonium salts Chemical group 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000004382 potting Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 description 2
- BRKFQVAOMSWFDU-UHFFFAOYSA-M tetraphenylphosphanium;bromide Chemical compound [Br-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BRKFQVAOMSWFDU-UHFFFAOYSA-M 0.000 description 2
- 125000005591 trimellitate group Chemical group 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- ZWVMLYRJXORSEP-LURJTMIESA-N (2s)-hexane-1,2,6-triol Chemical compound OCCCC[C@H](O)CO ZWVMLYRJXORSEP-LURJTMIESA-N 0.000 description 1
- FBHPRUXJQNWTEW-UHFFFAOYSA-N 1-benzyl-2-methylimidazole Chemical compound CC1=NC=CN1CC1=CC=CC=C1 FBHPRUXJQNWTEW-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-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
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 1
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 1
- CUFXMPWHOWYNSO-UHFFFAOYSA-N 2-[(4-methylphenoxy)methyl]oxirane Chemical compound C1=CC(C)=CC=C1OCC1OC1 CUFXMPWHOWYNSO-UHFFFAOYSA-N 0.000 description 1
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 description 1
- PMNLUUOXGOOLSP-UHFFFAOYSA-N 2-mercaptopropanoic acid Chemical class CC(S)C(O)=O PMNLUUOXGOOLSP-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- UIDDPPKZYZTEGS-UHFFFAOYSA-N 3-(2-ethyl-4-methylimidazol-1-yl)propanenitrile Chemical compound CCC1=NC(C)=CN1CCC#N UIDDPPKZYZTEGS-UHFFFAOYSA-N 0.000 description 1
- WVRNUXJQQFPNMN-VAWYXSNFSA-N 3-[(e)-dodec-1-enyl]oxolane-2,5-dione Chemical compound CCCCCCCCCC\C=C\C1CC(=O)OC1=O WVRNUXJQQFPNMN-VAWYXSNFSA-N 0.000 description 1
- RDNPPYMJRALIIH-UHFFFAOYSA-N 3-methylcyclohex-3-ene-1,1,2,2-tetracarboxylic acid Chemical compound CC1=CCCC(C(O)=O)(C(O)=O)C1(C(O)=O)C(O)=O RDNPPYMJRALIIH-UHFFFAOYSA-N 0.000 description 1
- VNGLVZLEUDIDQH-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol;2-methyloxirane Chemical compound CC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 VNGLVZLEUDIDQH-UHFFFAOYSA-N 0.000 description 1
- WPSWDCBWMRJJED-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol;oxirane Chemical compound C1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 WPSWDCBWMRJJED-UHFFFAOYSA-N 0.000 description 1
- OECTYKWYRCHAKR-UHFFFAOYSA-N 4-vinylcyclohexene dioxide Chemical compound C1OC1C1CC2OC2CC1 OECTYKWYRCHAKR-UHFFFAOYSA-N 0.000 description 1
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 239000007848 Bronsted acid Chemical class 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 239000004609 Impact Modifier Substances 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 1
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 1
- 229920002732 Polyanhydride Polymers 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- CGRTZESQZZGAAU-UHFFFAOYSA-N [2-[3-[1-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]-2-methylpropan-2-yl]-2,4,8,10-tetraoxaspiro[5.5]undecan-9-yl]-2-methylpropyl] 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCC(C)(C)C2OCC3(CO2)COC(OC3)C(C)(C)COC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 CGRTZESQZZGAAU-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 1
- ZDGWGNDTQZGISB-UHFFFAOYSA-N acetic acid;perchloric acid Chemical compound CC(O)=O.OCl(=O)(=O)=O ZDGWGNDTQZGISB-UHFFFAOYSA-N 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- JNDMLEXHDPKVFC-UHFFFAOYSA-N aluminum;oxygen(2-);yttrium(3+) Chemical compound [O-2].[O-2].[O-2].[Al+3].[Y+3] JNDMLEXHDPKVFC-UHFFFAOYSA-N 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- JRPRCOLKIYRSNH-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,2-dicarboxylate Chemical compound C=1C=CC=C(C(=O)OCC2OC2)C=1C(=O)OCC1CO1 JRPRCOLKIYRSNH-UHFFFAOYSA-N 0.000 description 1
- NEPKLUNSRVEBIX-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,4-dicarboxylate Chemical compound C=1C=C(C(=O)OCC2OC2)C=CC=1C(=O)OCC1CO1 NEPKLUNSRVEBIX-UHFFFAOYSA-N 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- USJRLGNYCQWLPF-UHFFFAOYSA-N chlorophosphane Chemical compound ClP USJRLGNYCQWLPF-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
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- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
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- 238000009730 filament winding 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
- 235000011187 glycerol Nutrition 0.000 description 1
- 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 1
- FLBJFXNAEMSXGL-UHFFFAOYSA-N het anhydride Chemical compound O=C1OC(=O)C2C1C1(Cl)C(Cl)=C(Cl)C2(Cl)C1(Cl)Cl FLBJFXNAEMSXGL-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
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- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000005040 ion trap Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- MDCWDBMBZLORER-UHFFFAOYSA-N triphenyl borate Chemical compound C=1C=CC=CC=1OB(OC=1C=CC=CC=1)OC1=CC=CC=C1 MDCWDBMBZLORER-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/52—Encapsulations
- H01L33/56—Materials, e.g. epoxy or silicone resin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/226—Mixtures of di-epoxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4215—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof cycloaliphatic
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
Definitions
- the epoxy resin composition of the present invention has the following effects (1) to (3).
- (1) The workability is good because the viscosity after blending is low and the viscosity increase factor at room temperature within the daytime working time is low.
- (2) Curability is good without adding a curing accelerator.
- (3) The obtained cured product is colorless and transparent, excellent in crack resistance, and has very little coloring even under long-time light irradiation and heating at 150 ° C. for 1000 hours.
- the epoxy resin composition of the present invention has the effects as described above, for example, sealing materials for photoelectric conversion elements such as blue LEDs and white LEDs, coating materials, paints, adhesives, and various moldings. Products, insulating members, decorative materials, etc., which are suitably used for applications that require more heat-resistant coloring.
- the content of H-TMAn can be appropriately selected in the range of 30 to 90% by mass according to the use and required performance of the epoxy resin composition.
- the content of H-TMAn in the acid anhydride (A) is preferably 40% by mass or more, and more preferably 50% by mass or more. More preferably, it is more preferably 60% by mass or more.
- the upper limit of the content of H-TMAn in the acid anhydride (A) is preferably 85% by mass or less and more preferably 80% by mass or less from the viewpoint of the viscosity of the epoxy resin composition.
- the epoxy resin (B) may be composed only of an alicyclic epoxy resin compound and a glycidyl ester type epoxy resin compound, or may further contain another epoxy resin compound.
- the total content of the alicyclic epoxy resin compound and the glycidyl ester type epoxy resin compound in the epoxy resin (B) is preferably 70% by mass or more, more preferably 80% by mass or more, and further preferably 90% by mass or more.
- the upper limit of the total content of the alicyclic epoxy resin compound and the glycidyl ester type epoxy resin compound in the epoxy resin (B) is not particularly limited, but is, for example, 100% by mass.
- the content of the alicyclic epoxy resin compound is 30 to 90% by mass, preferably 40 to 85% by mass, and more preferably 50 to 80% by mass.
- the more the content of the alicyclic epoxy resin compound, the higher the color resistance of the cured product of the epoxy resin composition, and the content of the alicyclic epoxy resin compound is the lower limit value.
- the cured product of the epoxy resin composition is further excellent in heat-resistant colorability.
- the cured product of the epoxy resin composition becomes flexible and can suppress the occurrence of cracks against heat shock, The heat resistance coloring property is further improved.
- the glycidyl ester type epoxy resin compound in the epoxy resin (B) can increase the flexibility of the cured product of the epoxy resin composition and suppress the occurrence of cracks due to heat shock.
- the content of the glycidyl ester type epoxy resin compound is preferably 10 to 60% by mass, more preferably 15 to 50% by mass, and further preferably 20 to 40% by mass. preferable.
- the cured product of the epoxy resin composition is further excellent in crack resistance.
- cured material of an epoxy resin composition is further excellent in heat-resistant coloring.
- the content of the alicyclic epoxy resin compound or the glycidyl ester type epoxy resin compound in the epoxy resin (B) in the epoxy resin composition or its cured product is determined by nuclear magnetic resonance (NMR) or gas chromatography. It can be measured by component analysis by chromatography (GC).
- the content of the other epoxy resin compound is preferably 30% by mass or less, more preferably 20% by mass or less, and further preferably 10% by mass or less.
- the lower limit of the content of the other epoxy resin compound is not particularly limited, and is, for example, 0% by mass.
- Other epoxy resin compounds can be used alone or in admixture of two or more within the above content range.
- the nuclear hydrogenated epoxy resin is more preferably used because it improves the colorless transparency of the cured product of the epoxy resin composition.
- the acid anhydride (A) is cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride (H-TMAn)
- the number of functional groups of the acid anhydride group in one molecule is 1, Since the number of functional groups of the carboxyl group is 1, the equivalent of the acid anhydride is 2.
- the epoxy resin (B) is 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate, the number of functional groups of the epoxy group is 2 in one molecule, so the equivalent of the epoxy resin is 2.
- the equivalent of the epoxy resin is 2.
- the functional group number X of the acid anhydride group contained in the acid anhydride (A) is (number of functional groups of the acid anhydride group of each acid anhydride compound) ⁇ (the acid anhydride group).
- the number of functional groups Y of the carboxyl group contained in the acid anhydride (A) is (the number of functional groups of the carboxyl group of each acid anhydride compound) ⁇ (the acid anhydride compound). Of the molar fraction).
- the number of functional groups Z of the epoxy group contained in the epoxy resin (B) is (the number of functional groups of the epoxy group of each epoxy resin compound) ⁇ (mol content of the epoxy resin compound). Rate) total amount.
- the blending equivalent ratio of the acid anhydride represented by the above formula (1) and the epoxy resin is in the range of 0.4 to 0.7, and 0.4 to 0.6. Is preferable, and a range of 0.4 to 0.5 is more preferable.
- the heat-resistant coloring property of the cured product is improved.
- the blending equivalent ratio is less than or equal to the above upper limit value, the remaining unreacted acid anhydride is suppressed, and the heat resistant colorability of the cured product is improved.
- the total content of the acid anhydride (A) and the epoxy resin (B) is preferably 70 to 100% by mass, and more preferably 80 to 100% by mass. Preferably, it is 90 to 100% by mass.
- the epoxy resin (B) has a blending amount of the acid anhydride (A) and the epoxy resin (B) within the range of the blending equivalent ratio of the acid anhydride and the epoxy resin.
- the viscosity of the epoxy resin composition exceeds 5 Pa ⁇ s, or the above-mentioned viscosity increase ratio exceeds 3 times.
- the use of a high-viscosity epoxy resin composition and the workability of the epoxy resin composition are further deteriorated due to a further increase in viscosity of the epoxy resin composition during daytime working hours.
- the viscosity increase ratio is more preferably 2 times or less in view of workability.
- the epoxy resin composition of this embodiment is An acid anhydride (A) and an epoxy resin (B) are contained, (A) 30 to 90% by mass of cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride is contained in the acid anhydride (A), (B) 30 to 90% by mass of an alicyclic epoxy resin compound is contained in the epoxy resin (B), and a glycidyl ester type epoxy resin compound is contained, (C) By setting the compounding equivalent ratio of the acid anhydride represented by the following formula (1) and the epoxy resin in the range of 0.4 to 0.7, the following effects (1) to (3) are obtained. .
- the epoxy resin composition having the effects (1) to (3) is suitable as a sealing material for photoelectric conversion elements such as blue LEDs and white LEDs.
- n-octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate
- 2,6-bis (1,1-dimethylethyl) -4-methylphenol (BHT) 2,6-bis (1,1-dimethylethyl) -4-methylphenol
- the content of the antioxidant is preferably 0.1 to 5% by mass, more preferably 0.1 to 4% by mass, and 0.1 to 3%. More preferably, it is mass%.
- the epoxy resin composition of the present embodiment absorbs at least a part of light emitted from a light emitting element having a main emission peak wavelength of 550 nm or less when used as a material for sealing a light emitting element of a white LED. It is preferable to include a fluorescent material capable of emitting fluorescence. Such a fluorescent material can emit various colors when combined with a light emitting diode (LED). For example, when a yellow phosphor and a blue LED are combined, white light can be emitted.
- LED light emitting diode
- the content of the fluorescent material is preferably 0.01 to 30% by mass, more preferably 0.01 to 20% by mass, and 0.1 to 10% by mass. % Is more preferable.
- phosphorus-based curing accelerators are preferred.
- Specific examples of the phosphorus curing accelerator are not particularly limited.
- organophosphorus compounds such as triphenylphosphine and triphenyl phosphite, tetraphenylphosphonium bromide, tetra-n-butylphosphonium bromide, and benzyltriphenyl.
- Quaternary phosphonium salts such as phosphonium chloride and benzyltriphenylphosphonium bromide can be mentioned.
- Use of such a phosphorus-based curing accelerator is more preferable because a cured product having excellent heat-resistant colorability can be obtained.
- curing accelerators can be used alone or in admixture of two or more.
- an aliphatic polyol such as ethylene glycol and propylene glycol
- an aliphatic or aromatic carboxylic acid compound such as a phenol compound, a polyalkylene glycol, etc.
- the epoxy resin composition of this embodiment is divided and stored in two or more components, for example, a component containing an acid anhydride (A) and a component containing an epoxy resin (B), and these are prepared before curing. May be. Moreover, you may preserve
- the curing method of the above-described epoxy resin composition is not particularly limited, and for example, a curing method using a conventionally known curing apparatus such as a closed curing furnace or a tunnel furnace capable of continuous curing can be employed.
- the heating method in the case of the said hardening is not specifically limited, For example, conventionally well-known methods, such as hot air circulation, infrared heating, high frequency heating, are employable.
- the curing temperature and curing time are preferably in the range of 30 to 10 hours at 80 to 250 ° C. When it is desired to reduce the internal stress of the cured product, it is preferable to pre-cure under conditions of 80 to 120 ° C. and 0.5 to 5 hours, and then post-cure under conditions of 120 to 180 ° C. and 0.1 to 5 hours. .
- curing is preferably performed under conditions of 150 to 250 ° C. and 30 seconds to 30 minutes.
- the above-mentioned cured epoxy resin is colorless and transparent, has crack resistance, and has little coloration under long-time heating.
- it is suitable as a sealing material for light-emitting diodes, particularly blue LED and white LED sealing materials. Can be used.
- the epoxy resin composition of the present embodiment is not limited to the above-mentioned applications.
- other light emitting elements such as LEDs and semiconductor lasers, photoconductive elements, photodiodes, solar cells, phototransistors, photothyristors, etc.
- Insulating and sealing materials for photoelectric conversion elements typified by optical coupling elements such as light receiving elements, photocouplers, photointerrupters, adhesives such as liquid crystals, resins for optical modeling, and surface coating agents such as plastics, glass, and metals It can also be used for applications that require transparency, such as decorative materials.
- the epoxy resin composition of the present embodiment can be applied to insulating seals and molded products having a thickness of 2 mm or more by a conventionally known method such as potting, casting, filament winding, and lamination.
- a mold transformer current transformer (CT), zero-layer current transformer (ZCT), instrument transformer (PT), stationary instrument transformer (ZPT)
- Gas switch parts insulation spacers, support insulators, operating rods, sealed terminals, bushings, insulation columns, etc.
- solid insulation switch parts insulation spacers, support insulators, operating rods, sealed terminals, bushings, insulation columns, etc.
- solid insulation switch parts overhead distribution line automation equipment parts (rotary insulators, voltage detection elements, general capacitors, etc.), underground Distribution line equipment parts (molded transformers, power transformers, etc.), power capacitors, resin insulators, heavy electrical insulation insulating seals such as linear motor car coils, impregnating varnishes for various rotating equipment coils (generators, It can also be used for motors).
- the epoxy resin composition of the present embodiment can also be used for, for example, various FRP molded products, various coating materials, adhesives, decorative materials, and the like as applications that do not necessarily require laminates or insulation.
- Viscosity of Epoxy Resin Composition The viscosity of the epoxy resin composition was measured using a dynamic viscoelasticity measuring device (ARES manufactured by TA Instruments Inc.) with a 25 mm ⁇ aluminum plate and a distance between plates of 0.05 mm, furnace Measurement was performed at an internal temperature of 30 ° C.
- the viscosity increase ratio of the epoxy resin composition was such that the epoxy resin composition was allowed to elapse for 7 hours at room temperature (15 to 27 ° C.) in a glass screw bottle with a lid with respect to the viscosity immediately after the preparation of the epoxy resin composition. It was set as the ratio of the viscosity of the subsequent epoxy resin composition.
- the obtained cured product was heated at 150 ° C. for 1000 hours.
- the light transmittance was measured with a spectrophotometer (Spectrophotometer UV-3100 manufactured by Shimadzu Corporation), and from the surface reflectance calculated from the refractive index measured separately.
- the light transmittance at 400 nm corresponding to 1 mm thickness was determined.
- the maintenance factor of the light transmittance by heat processing was calculated
- the light transmittance was measured with a spectrophotometer (Spectrophotometer UV-3100 manufactured by Shimadzu Corporation), and from the surface reflectance calculated from the refractive index measured separately. The light transmittance at 400 nm corresponding to 1 mm thickness was determined. And the maintenance factor of the light transmittance by UV irradiation was calculated
- this light-emitting diode was heated in a reflow furnace (XNB-738PC (C) manufactured by Furukawa Electric Co., Ltd.) for a maximum of 260 ° C. and a heat history of 40 seconds at a temperature range of 230 to 260 ° C. Was applied three times.
- the above operation was performed 10 samples for each cured product, and the crack resistance was evaluated as follows from the occurrence of peeling and cracks in the cured product of the light-emitting diode after thermal history.
- Epoxy resin (B) (2-1) Alicyclic epoxy resin compound / 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate [Daicel Co., Ltd., CEL2021P]
- Antioxidants / hindered phenol antioxidants AO-50 [manufactured by ADEKA Corporation, hereinafter also referred to as “AO-50”. ] • Hindered phenol antioxidant: 2,6-bis (1,1-dimethylethyl) -4-methylphenol [manufactured by Kanto Chemical Co., Ltd., hereinafter also referred to as “BHT”. ]
- Example 1 H-TMAn [Mitsubishi Gas Chemical Co., Ltd.] 79.0 parts by mass, mixture of hexahydrophthalic anhydride and methylhexahydrophthalic anhydride [MH700G made by Shin Nippon Rika Co., Ltd.] 21.0 parts by mass, alicyclic Epoxy resin compound [3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate: CEL2021P, manufactured by Daicel Corporation] 172 parts by mass, hexahydrophthalic acid diglycidyl ester which is a glycidyl ester type epoxy resin compound [ SR-HHPA from Sakamoto Yakuhin Kogyo Co., Ltd., 73.9 parts by mass, 2.8 parts by mass of hindered phenol antioxidant AO-50 (manufactured by ADEKA Co., Ltd.), and Sunapro, a bromide salt of quaternary phosphon
- Examples 2 to 16 and Comparative Examples 1 to 9 An epoxy resin composition was obtained in the same manner as in Example 1 except that the types and ratios of the raw material components were changed as shown in Tables 1 to 3. Measurement of physical properties and evaluation of the obtained epoxy resin composition and cured product thereof were performed by the above-described methods. The results are shown in Tables 1 to 3.
- the acid anhydride (A) and the epoxy resin (B) are contained, and the acid anhydride (A) contains 30 to 90% by mass of cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride.
- the epoxy resin (B) contains 30 to 90% by mass of the alicyclic epoxy resin compound, the glycidyl ester type epoxy resin compound, and the compounding equivalent ratio of the acid anhydride and the epoxy resin is 0.4 to 0.4%.
- An epoxy resin composition in the range of 0.7 has a low viscosity after preparation, a low rate of thickening at room temperature, excellent workability, and a cured product can be obtained without adding a curing accelerator. It was found that the curability was good. Further, it was found that the cured product was colorless and transparent, excellent in crack resistance, and little colored under prolonged light irradiation and heating at 150 ° C. for 1000 hours.
- the content of H-TMAn in the acid anhydride (A) is controlled to 30 to 90% by mass
- the content of the alicyclic epoxy resin compound in the epoxy resin (B) is controlled to 30 to 90% by mass
- the content of the glycidyl ester type epoxy resin compound in the epoxy resin (B) is controlled to 10 to 60% by mass and setting the compounding equivalent ratio of the acid anhydride and the epoxy resin to 0.4 to 0.7
- heat resistance is improved. It has been found that a cured product can be obtained that is more excellent in colorability and UV color resistance, better in workability of the epoxy resin composition, and more excellent in crack resistance.
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Abstract
Description
(1)調合後の粘度が低く、室温放置における増粘倍率が低くて、作業性に優れること。
(2)硬化促進剤を添加しなくても硬化性が良好であること。
(3)得られる硬化物が無色透明で、耐クラック性に優れ、長時間の光照射および150℃1000時間での加熱下での着色が少ないこと。 An object of the present invention is to provide an epoxy resin composition having the following characteristics (1) to (3) and suitable as a sealing material for photoelectric conversion elements such as blue LEDs and white LEDs, and a cured product thereof. There is.
(1) The viscosity after preparation is low, the viscosity increase ratio at room temperature is low, and the workability is excellent.
(2) Curability is good without adding a curing accelerator.
(3) The obtained cured product is colorless and transparent, excellent in crack resistance, and has little coloration under prolonged light irradiation and heating at 150 ° C. for 1000 hours.
1. 酸無水物(A)およびエポキシ樹脂(B)を含有し、
(a)酸無水物(A)がシクロヘキサン-1,2,4-トリカルボン酸-1,2-無水物を30~90質量%含有し、
(b)エポキシ樹脂(B)が脂環式エポキシ樹脂化合物を30~90質量%含有し、グリシジルエステル型エポキシ樹脂化合物を含有し、
(c)下記の式(1)で表わされる酸無水物とエポキシ樹脂との配合当量比が0.4~0.7の範囲である、エポキシ樹脂組成物。
酸無水物とエポキシ樹脂との配合当量比=(X+Y)/Z (1)
X:酸無水物(A)中に含まれる酸無水物基の官能基数
Y:酸無水物(A)中に含まれるカルボキシル基の官能基数
Z:エポキシ樹脂(B)中に含まれるエポキシ基の官能基数
2. エポキシ樹脂(B)におけるグリシジルエステル型エポキシ樹脂化合物の含有量が10~60質量%である、上記1のエポキシ樹脂組成物。
3. グリシジルエステル型エポキシ樹脂化合物が、アジピン酸ジグリシジルエステル、長鎖二塩基酸ジグリシジルエステル、テトラヒドロフタル酸ジグリシジルエステルおよびヘキサヒドロフタル酸ジグリシジルエステルからなる群より選ばれる少なくとも1つである、上記1または2のエポキシ樹脂組成物。
4. 脂環式エポキシ樹脂化合物が、3,4-エポキシシクロヘキセニルメチル-3’,4’-エポキシシクロヘキセンカルボキシレートである、上記1~3のいずれかのエポキシ樹脂組成物。
5. さらに、ヒンダードフェノール系酸化防止剤を0.1~5質量%含有する、上記1~4のいずれかのエポキシ樹脂組成物。
6. さらに、リン系硬化促進剤を0.01~5質量%含有する、上記1~5のいずれかのエポキシ樹脂組成物。
7. さらに、主発光ピーク波長が550nm以下である発光素子から発光される光の少なくとも一部を吸収して蛍光を発光することが可能な蛍光物質を含有する、上記1~6のいずれかのエポキシ樹脂組成物。
8. 上記1~7のいずれかのエポキシ樹脂組成物を硬化して得られるエポキシ樹脂硬化物。
9. 上記8のエポキシ樹脂硬化物で発光素子が封止されている発光ダイオード。 That is, this invention provides the following epoxy resin compositions, its hardened | cured material, and a light emitting diode.
1. Containing an acid anhydride (A) and an epoxy resin (B),
(A) The acid anhydride (A) contains 30 to 90% by mass of cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride,
(B) The epoxy resin (B) contains 30 to 90% by mass of the alicyclic epoxy resin compound, and contains the glycidyl ester type epoxy resin compound,
(C) An epoxy resin composition having a compounding equivalent ratio of an acid anhydride represented by the following formula (1) and an epoxy resin in the range of 0.4 to 0.7.
Compounding equivalent ratio of acid anhydride and epoxy resin = (X + Y) / Z (1)
X: Number of functional groups of acid anhydride group contained in acid anhydride (A) Y: Number of functional groups of carboxyl group contained in acid anhydride (A) Z: Number of functional groups of epoxy group contained in epoxy resin (B) Number of functional groups The epoxy resin composition according to 1 above, wherein the content of the glycidyl ester type epoxy resin compound in the epoxy resin (B) is 10 to 60% by mass.
3. The glycidyl ester type epoxy resin compound is at least one selected from the group consisting of adipic acid diglycidyl ester, long-chain dibasic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester and hexahydrophthalic acid diglycidyl ester, 1 or 2 epoxy resin composition.
4). 4. The epoxy resin composition according to any one of 1 to 3 above, wherein the alicyclic epoxy resin compound is 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate.
5. The epoxy resin composition according to any one of 1 to 4 above, further comprising 0.1 to 5% by mass of a hindered phenol antioxidant.
6). The epoxy resin composition according to any one of 1 to 5, further comprising 0.01 to 5% by mass of a phosphorus curing accelerator.
7). The epoxy resin according to any one of the above 1 to 6, further comprising a fluorescent material capable of emitting fluorescence by absorbing at least part of light emitted from the light emitting element having a main emission peak wavelength of 550 nm or less. Composition.
8). 8. A cured epoxy resin obtained by curing the epoxy resin composition according to any one of 1 to 7 above.
9. A light emitting diode in which a light emitting element is sealed with the cured epoxy resin according to 8 above.
(1)調合後の粘度が低く、日中作業時間内での室温放置における増粘倍率が低いので、作業性が良好である。
(2)硬化促進剤を添加しなくても硬化性が良好である。
(3)得られる硬化物が無色透明で、耐クラック性に優れ、長時間の光照射および150℃1000時間の加熱下でも着色が極めて少ない。 The epoxy resin composition of the present invention has the following effects (1) to (3).
(1) The workability is good because the viscosity after blending is low and the viscosity increase factor at room temperature within the daytime working time is low.
(2) Curability is good without adding a curing accelerator.
(3) The obtained cured product is colorless and transparent, excellent in crack resistance, and has very little coloring even under long-time light irradiation and heating at 150 ° C. for 1000 hours.
本実施形態のエポキシ樹脂組成物は、特定組成の酸無水物(A)とエポキシ樹脂(B)とを含有する。 ≪Epoxy resin composition≫
The epoxy resin composition of this embodiment contains the acid anhydride (A) and epoxy resin (B) of a specific composition.
本実施形態のエポキシ樹脂組成物に用いる酸無水物(A)は、シクロヘキサン-1,2,4-トリカルボン酸-1,2-無水物を30~90質量%含有する。酸無水物(A)がシクロヘキサン-1,2,4-トリカルボン酸-1,2-無水物を30~90質量%含有すると、得られるエポキシ樹脂組成物の硬化物は、耐クラック性に優れる。 <Acid anhydride (A)>
The acid anhydride (A) used in the epoxy resin composition of the present embodiment contains 30 to 90% by mass of cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride. When the acid anhydride (A) contains 30 to 90% by mass of cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride, the cured product of the resulting epoxy resin composition is excellent in crack resistance.
本実施形態のエポキシ樹脂組成物で使用するエポキシ樹脂(B)は、脂環式エポキシ樹脂化合物を30~90質量%含有し、グリシジルエステル型エポキシ樹脂化合物を含有する。エポキシ樹脂(B)が脂環式エポキシ樹脂化合物を30~90質量%含有すると、エポキシ樹脂組成物の硬化物は、耐熱着色性に優れる。一方、エポキシ樹脂(B)がグリシジルエステル型エポキシ樹脂化合物を含有すると、エポキシ樹脂組成物の硬化物は、柔軟性が高まり、ヒートショックによるクラック発生などを抑制することができる。 <Epoxy resin (B)>
The epoxy resin (B) used in the epoxy resin composition of the present embodiment contains 30 to 90% by mass of an alicyclic epoxy resin compound and a glycidyl ester type epoxy resin compound. When the epoxy resin (B) contains 30 to 90% by mass of the alicyclic epoxy resin compound, the cured product of the epoxy resin composition is excellent in heat resistant colorability. On the other hand, when the epoxy resin (B) contains a glycidyl ester type epoxy resin compound, the cured product of the epoxy resin composition has increased flexibility and can suppress the occurrence of cracks due to heat shock.
本実施形態のエポキシ樹脂組成物において、酸無水物(A)とエポキシ樹脂(B)との配合量は、下記の式(1)で表わされる酸無水物とエポキシ樹脂との配合当量比が0.4~0.7の範囲となる量である。 <Blending amount of acid anhydride (A) and epoxy resin (B)>
In the epoxy resin composition of the present embodiment, the blending amount of the acid anhydride (A) and the epoxy resin (B) is such that the blending equivalent ratio of the acid anhydride and the epoxy resin represented by the following formula (1) is 0. The amount is in the range of 4 to 0.7.
X:酸無水物(A)中に含まれる酸無水物基の官能基数
Y:酸無水物(A)中に含まれるカルボキシル基の官能基数
Z:エポキシ樹脂(B)中に含まれるエポキシ基の官能基数 Compounding equivalent ratio of acid anhydride and epoxy resin = (X + Y) / Z (1)
X: Number of functional groups of acid anhydride group contained in acid anhydride (A) Y: Number of functional groups of carboxyl group contained in acid anhydride (A) Z: Number of functional groups of epoxy group contained in epoxy resin (B) Number of functional groups
酸無水物(A)およびエポキシ樹脂(B)を含有させ、
(a)酸無水物(A)中にシクロヘキサン-1,2,4-トリカルボン酸-1,2-無水物を30~90質量%含有させ、
(b)エポキシ樹脂(B)中に脂環式エポキシ樹脂化合物を30~90質量%含有させ、グリシジルエステル型エポキシ樹脂化合物を含有させ、
(c)下記の式(1)で表わされる酸無水物とエポキシ樹脂との配合当量比を0.4~0.7の範囲とすることにより、下記(1)~(3)の効果を奏する。 The epoxy resin composition of this embodiment is
An acid anhydride (A) and an epoxy resin (B) are contained,
(A) 30 to 90% by mass of cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride is contained in the acid anhydride (A),
(B) 30 to 90% by mass of an alicyclic epoxy resin compound is contained in the epoxy resin (B), and a glycidyl ester type epoxy resin compound is contained,
(C) By setting the compounding equivalent ratio of the acid anhydride represented by the following formula (1) and the epoxy resin in the range of 0.4 to 0.7, the following effects (1) to (3) are obtained. .
(2)得られるエポキシ樹脂組成物の硬化物は、無色透明で、耐クラック性があり、長時間の光照射および150℃1000時間の加熱下でも着色が極めて少ない。
(3)硬化促進剤を添加しなくても硬化性が良好である。また、特定の硬化促進剤を使用することで、エポキシ樹脂組成物の増粘速度は上昇するものの、さらに加熱による着色が少なく、耐熱着色性に優れる硬化物が得られる。 (1) The resulting epoxy resin composition has a low viscosity after preparation, and is excellent in workability since it has a low viscosity increase rate at room temperature within daytime working hours.
(2) The cured product of the resulting epoxy resin composition is colorless and transparent, has crack resistance, and has very little coloring even under prolonged light irradiation and heating at 150 ° C. for 1000 hours.
(3) The curability is good without adding a curing accelerator. Moreover, although the viscosity increase rate of an epoxy resin composition rises by using a specific hardening accelerator, there is little coloring by heating and the hardened | cured material which is excellent in heat-resistant coloring property is obtained.
本実施形態のエポキシ樹脂組成物は、高い耐熱着色性が求められる場合には、酸化防止剤を含有させることが好ましい。酸化防止剤としては、特に限定されないが、例えば、ヒンダードフェノール系酸化防止剤、イオウ系酸化防止剤(メルカプトプロピオン酸誘導体など)、リン系酸化防止剤(HCAなど)などが挙げられる。特にヒンダードフェノール系酸化防止剤が有効である。ヒンダードフェノール系酸化防止剤の具体例としては、特に限定されないが、例えば、n-オクタデシル3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオネート、トリエチレングリコールビス[3-(3-tert-ブチル-4-ヒドロキシ-5-メチルフェニル)プロピオネート]、3,9-ビス{2-[3-(3-tert-ブチル-4-ヒドロキシ-5-メチルフェニル)プロピオニルオキシ]-1,1-ジメチルエチル}-2,4,8,10-テトラオキサスピロ[5.5]ウンデカン、2,6-ビス(1,1-ジメチルエチル)-4-メチルフェノール(BHT)が挙げられる。 <Antioxidant>
The epoxy resin composition of the present embodiment preferably contains an antioxidant when high heat resistance colorability is required. Although it does not specifically limit as antioxidant, For example, hindered phenolic antioxidant, sulfur type antioxidant (mercaptopropionic acid derivative etc.), phosphorus antioxidant (HCA etc.), etc. are mentioned. In particular, hindered phenol antioxidants are effective. Specific examples of the hindered phenol antioxidant are not particularly limited. For example, n-octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, triethylene glycol bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy]- 1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5.5] undecane, 2,6-bis (1,1-dimethylethyl) -4-methylphenol (BHT) .
本実施形態のエポキシ樹脂組成物は、白色LEDの発光素子を封止する材料に用いる場合には、主発光ピーク波長が550nm以下である発光素子から発光される光の少なくとも一部を吸収して蛍光を発光することが可能な蛍光物質を含むことが好ましい。このような蛍光物質は、発光ダイオード(LED)と組み合わせると、様々な色を発光することができる。例えば、黄色蛍光体と青色LEDとを組み合わせると、白色を発光することができる。 <Fluorescent substance>
The epoxy resin composition of the present embodiment absorbs at least a part of light emitted from a light emitting element having a main emission peak wavelength of 550 nm or less when used as a material for sealing a light emitting element of a white LED. It is preferable to include a fluorescent material capable of emitting fluorescence. Such a fluorescent material can emit various colors when combined with a light emitting diode (LED). For example, when a yellow phosphor and a blue LED are combined, white light can be emitted.
本実施形態のエポキシ樹脂組成物は、硬化促進剤を使用しなくても硬化するためコスト面でのメリットがあるが、硬化促進剤を添加することにより、さらにエポキシ樹脂組成物の硬化物の耐熱着色性を改善することができる。より耐熱着色性が要求されるLED等の光電変換素子の封止材料では、耐熱着色性の要求水準に応じて硬化促進剤を適宜使用できる。 <Curing accelerator>
The epoxy resin composition of this embodiment has a merit in cost because it cures without using a curing accelerator, but by adding a curing accelerator, the heat resistance of the cured product of the epoxy resin composition is further increased. Colorability can be improved. In a sealing material for a photoelectric conversion element such as an LED that requires more heat resistant colorability, a curing accelerator can be appropriately used according to the required level of heat resistant colorability.
本実施形態のエポキシ樹脂組成物には、必要に応じて、エチレングリコール、プロピレングリコール等脂肪族ポリオール、脂肪族または芳香族カルボン酸化合物、フェノール化合物等の炭酸ガス発生防止剤、ポリアルキレングリコール等の可撓性付与剤、可塑剤、滑剤、シラン系等のカップリング剤、無機充填剤の表面処理剤、難燃剤、着色剤、帯電防止剤、レベリング剤、イオントラップ剤、摺動性改良剤、各種ゴム、有機ポリマービーズ等の耐衝撃性改良剤、揺変性付与剤、界面活性剤、表面張力低下剤、消泡剤、沈降防止剤、光拡散剤、紫外線吸収剤、離型剤、導電性充填剤、粘度調整用低粘度溶剤等の添加剤を、得られるエポキシ樹脂組成物およびその硬化物の特性を損なわない範囲で含有させることができる。 <Other additives>
In the epoxy resin composition of the present embodiment, if necessary, an aliphatic polyol such as ethylene glycol and propylene glycol, an aliphatic or aromatic carboxylic acid compound, a carbon dioxide gas generation inhibitor such as a phenol compound, a polyalkylene glycol, etc. Flexibility imparting agent, plasticizer, lubricant, silane-based coupling agent, inorganic filler surface treatment agent, flame retardant, colorant, antistatic agent, leveling agent, ion trap agent, slidability improver, Various rubbers, impact modifiers such as organic polymer beads, thixotropic agents, surfactants, surface tension reducing agents, antifoaming agents, anti-settling agents, light diffusing agents, ultraviolet absorbers, mold release agents, conductivity Additives such as a filler and a low-viscosity solvent for viscosity adjustment can be contained within a range that does not impair the properties of the resulting epoxy resin composition and its cured product.
本実施形態のエポキシ樹脂組成物は、2つ以上の成分、例えば酸無水物(A)を含む成分とエポキシ樹脂(B)を含む成分に分けて保存しておき、硬化前にこれらを調合してもよい。また、各成分を配合したエポキシ樹脂組成物として保存し、そのまま硬化に供してもよい。各成分を配合したエポキシ樹脂組成物として保存する場合には、低温(通常-40~15℃)で保存することが好ましい。 <How to save>
The epoxy resin composition of this embodiment is divided and stored in two or more components, for example, a component containing an acid anhydride (A) and a component containing an epoxy resin (B), and these are prepared before curing. May be. Moreover, you may preserve | save as an epoxy resin composition which mix | blended each component, and you may use for hardening as it is. When storing as an epoxy resin composition containing each component, it is preferably stored at a low temperature (usually −40 to 15 ° C.).
本実施形態のエポキシ樹脂硬化物は、上述のエポキシ樹脂組成物を硬化して得られる。 ≪Hardened epoxy resin≫
The cured epoxy resin of this embodiment is obtained by curing the above-described epoxy resin composition.
本実施形態の発光ダイオードは、上述のエポキシ樹脂硬化物で発光素子が封止されている発光ダイオードである。 ≪Light emitting diode≫
The light emitting diode of this embodiment is a light emitting diode in which the light emitting element is sealed with the above-described cured epoxy resin.
本実施形態のエポキシ樹脂組成物は、前記用途に限定されるものではなく、例えば、その他のLED、半導体レーザー等の発光素子、光導電素子、フォトダイオード、太陽電池、フォトトランジスタ、フォトサイリスタ等の受光素子、フォトカプラー、フォトインタラプター等の光結合素子で代表される光電変換素子の絶縁封止材料、液晶等の接着剤、光造形用の樹脂、更にプラスティック、ガラス、金属等の表面コーティング剤、装飾材料等の透明性を要求される用途にも用いることができる。 ≪Other uses≫
The epoxy resin composition of the present embodiment is not limited to the above-mentioned applications. For example, other light emitting elements such as LEDs and semiconductor lasers, photoconductive elements, photodiodes, solar cells, phototransistors, photothyristors, etc. Insulating and sealing materials for photoelectric conversion elements typified by optical coupling elements such as light receiving elements, photocouplers, photointerrupters, adhesives such as liquid crystals, resins for optical modeling, and surface coating agents such as plastics, glass, and metals It can also be used for applications that require transparency, such as decorative materials.
エポキシ樹脂組成物の粘度は、動的粘弾性測定装置(ティー・エイ・インスツルメント社製 ARES)を用い、25mmΦアルミプレートでプレート間距離0.05mm、炉内温度30℃にて測定した。 (1) Viscosity of Epoxy Resin Composition The viscosity of the epoxy resin composition was measured using a dynamic viscoelasticity measuring device (ARES manufactured by TA Instruments Inc.) with a 25 mmφ aluminum plate and a distance between plates of 0.05 mm, furnace Measurement was performed at an internal temperature of 30 ° C.
○:調合直後の粘度が5Pa・s以下のエポキシ樹脂組成物。
×:調合直後の粘度が5Pa・sを超えるエポキシ樹脂組成物。 [Viscosity evaluation immediately after compounding]
○: An epoxy resin composition having a viscosity immediately after blending of 5 Pa · s or less.
X: An epoxy resin composition having a viscosity immediately after preparation exceeding 5 Pa · s.
○:増粘倍率が2倍を超え3倍以下のエポキシ樹脂組成物。
×:増粘倍率が3倍を超えるエポキシ樹脂組成物。 A: An epoxy resin composition having a viscosity increase ratio of 2 times or less.
○: An epoxy resin composition having a thickening ratio of more than 2 times and 3 times or less.
X: An epoxy resin composition having a thickening ratio exceeding 3 times.
所定量の試料(エポキシ樹脂組成物)をビーカー内で攪拌機にて混合し、エポキシ樹脂組成物中の溶存不活性ガスを真空にて脱気した。その後、エポキシ樹脂組成物を50mm角深さ3mmのシリコーン型に注型し、熱風乾燥機内にて100℃3時間の前硬化の後、150℃2時間の後硬化を行ない、硬化物を得た。 (2) Heat-resistant coloring property test A predetermined amount of the sample (epoxy resin composition) was mixed in a beaker with a stirrer, and the dissolved inert gas in the epoxy resin composition was degassed in vacuum. Thereafter, the epoxy resin composition was poured into a silicone mold having a 50 mm square and a depth of 3 mm, precured in a hot air dryer at 100 ° C. for 3 hours, and then postcured at 150 ° C. for 2 hours to obtain a cured product. .
耐熱着色性試験と同様にして得られた硬化物を、大日本プラスチックス株式会社製 アイ・スーパー・UVテスター SUV-W11の試験炉内に設置し、55℃/50RH%の条件下、波長範囲295~450nm(360~380nmに最高強度ピークを有する)の光を照射面光強度68mW/cm2にて120時間UV照射した。 (3) UV coloring resistance test (light resistance test)
The cured product obtained in the same manner as in the heat-resistant coloring property test was placed in a test furnace of Dainippon Plastics Co., Ltd. Eye Super UV Tester SUV-W11, and the wavelength range was 55 ° C / 50RH%. UV irradiation with light of 295 to 450 nm (having the highest intensity peak at 360 to 380 nm) was performed at an irradiation surface light intensity of 68 mW / cm 2 for 120 hours.
所定量の試料(エポキシ樹脂組成物)をビーカー内で攪拌機にて混合し、エポキシ樹脂組成物中の溶存イナートガスを真空にて脱気した。その後、エポキシ樹脂組成物を表面実装型発光ダイオードに流し込み、熱風乾燥機内にて100℃3時間の前硬化を行い、次いで150℃2時間の後硬化を行い、硬化物を得た。さらに、該硬化物で封止した発光ダイオードを得た。 (4) Crack resistance test A predetermined amount of the sample (epoxy resin composition) was mixed in a beaker with a stirrer, and dissolved inert gas in the epoxy resin composition was degassed in vacuum. Thereafter, the epoxy resin composition was poured into a surface-mounted light emitting diode, precured at 100 ° C. for 3 hours in a hot air dryer, and then postcured at 150 ° C. for 2 hours to obtain a cured product. Further, a light emitting diode sealed with the cured product was obtained.
○:剥離またはクラックの発生が0サンプルの硬化物
△:剥離またはクラックの発生が1サンプルの硬化物
×:剥離またはクラックの発生が2サンプル以上の硬化物 [Evaluation of crack resistance]
○: Hardened product of 0 samples with no peeling or cracking Δ: Hardened material with 1 sample of peeling or cracking ×: Hardened material with 2 or more samples of peeling or cracking
・シクロヘキサン-1,2,4-トリカルボン酸-1,2-無水物〔三菱ガス化学(株)製、以下「H-TMAn」とも記す。〕
・ヘキサヒドロ無水フタル酸およびメチルヘキサヒドロ無水フタル酸の混合物〔新日本理化(株)製、MH700G、以下「無水フタル酸混合物」とも記す。〕
・メチルヘキサヒドロ無水フタル酸〔新日本理化(株)製、MH、以下「MeHHPA」とも記す。〕 (1) Acid anhydride (A)
Cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride [Mitsubishi Gas Chemical Co., Ltd., hereinafter also referred to as “H-TMAn”. ]
A mixture of hexahydrophthalic anhydride and methylhexahydrophthalic anhydride [manufactured by Shin Nippon Rika Co., Ltd., MH700G, hereinafter also referred to as “phthalic anhydride mixture”. ]
・ Methylhexahydrophthalic anhydride [manufactured by Shin Nippon Rika Co., Ltd., MH, hereinafter also referred to as “MeHHPA”. ]
(2-1)脂環式エポキシ樹脂化合物
・3,4-エポキシシクロヘキセニルメチル-3’,4’-エポキシシクロヘキセンカルボキシレート〔株式会社ダイセル製、CEL2021P〕 (2) Epoxy resin (B)
(2-1) Alicyclic epoxy resin compound / 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate [Daicel Co., Ltd., CEL2021P]
・ヘキサヒドロフタル酸ジグリシジルエステル〔阪本薬品工業(株)製、SR-HHPA〕 (2-2) Glycidyl ester type epoxy resin compound / hexahydrophthalic acid diglycidyl ester (SR-HHPA manufactured by Sakamoto Pharmaceutical Co., Ltd.)
・ヘキサン-1,6-ジグリシジルエーテル〔阪本薬品工業(株)製、SR-16H〕 (2-3) Linear epoxy resin compound / hexane-1,6-diglycidyl ether [manufactured by Sakamoto Pharmaceutical Co., Ltd., SR-16H]
・ヒンダードフェノール系酸化防止剤:AO-50〔株式会社ADEKA製、以下「AO-50」とも記す。〕
・ヒンダードフェノール系酸化防止剤:2,6-ビス(1,1-ジメチルエチル)-4-メチルフェノール〔関東化学株式会社製、以下「BHT」とも記す。〕 (3) Antioxidants / hindered phenol antioxidants: AO-50 [manufactured by ADEKA Corporation, hereinafter also referred to as “AO-50”. ]
• Hindered phenol antioxidant: 2,6-bis (1,1-dimethylethyl) -4-methylphenol [manufactured by Kanto Chemical Co., Ltd., hereinafter also referred to as “BHT”. ]
・第四級ホスホニウムのブロマイド塩〔サンアプロ社製、以下「U-CAT5003」とも記す。〕 (4) Curing accelerator / Bromide salt of quaternary phosphonium [manufactured by San Apro, hereinafter referred to as “U-CAT5003”. ]
・セリウムをドープしたイットリウムアルミニウム酸化物〔Y3Al5O12:Ce、黄色蛍光体。〕 (5) Yttrium aluminum oxide doped with fluorescent substance / cerium [Y 3 Al 5 O 12 : Ce, yellow phosphor. ]
H-TMAn〔三菱ガス化学(株)製〕79.0質量部、ヘキサヒドロ無水フタル酸およびメチルヘキサヒドロ無水フタル酸の混合物〔新日本理化(株)製 MH700G〕21.0質量部、脂環式エポキシ樹脂化合物〔3,4-エポキシシクロヘキセニルメチル-3’,4’-エポキシシクロヘキセンカルボキシレート:株式会社ダイセル製 CEL2021P〕172質量部、グリシジルエステル型エポキシ樹脂化合物であるヘキサヒドロフタル酸ジグリシジルエステル〔阪本薬品工業(株)製SR-HHPA〕73.9質量部、ヒンダードフェノール系酸化防止剤AO-50(株式会社ADEKA製)2.8質量部、および第四級ホスホニウムのブロマイド塩であるサンアプロ社製「U-CAT5003」0.80質量部を混合し、エポキシ樹脂組成物を得た。得られたエポキシ樹脂組成物およびその硬化物の物性測定およびその評価を、前記の方法により行った。結果を第1表に示す。 [Example 1]
H-TMAn [Mitsubishi Gas Chemical Co., Ltd.] 79.0 parts by mass, mixture of hexahydrophthalic anhydride and methylhexahydrophthalic anhydride [MH700G made by Shin Nippon Rika Co., Ltd.] 21.0 parts by mass, alicyclic Epoxy resin compound [3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate: CEL2021P, manufactured by Daicel Corporation] 172 parts by mass, hexahydrophthalic acid diglycidyl ester which is a glycidyl ester type epoxy resin compound [ SR-HHPA from Sakamoto Yakuhin Kogyo Co., Ltd., 73.9 parts by mass, 2.8 parts by mass of hindered phenol antioxidant AO-50 (manufactured by ADEKA Co., Ltd.), and Sunapro, a bromide salt of quaternary phosphonium "U-CAT5003" 0.80 parts by mass, mixed with epoxy A resin composition was obtained. Measurement of physical properties and evaluation of the obtained epoxy resin composition and cured product thereof were performed by the above-described methods. The results are shown in Table 1.
原料成分の種類および割合を表1~3に示すとおりに変更した以外は実施例1と同様にしてエポキシ樹脂組成物を得た。得られたエポキシ樹脂組成物およびその硬化物の物性測定およびその評価を、前記の方法により行った。結果を表1~3に示す。 [Examples 2 to 16 and Comparative Examples 1 to 9]
An epoxy resin composition was obtained in the same manner as in Example 1 except that the types and ratios of the raw material components were changed as shown in Tables 1 to 3. Measurement of physical properties and evaluation of the obtained epoxy resin composition and cured product thereof were performed by the above-described methods. The results are shown in Tables 1 to 3.
Claims (9)
- 酸無水物(A)およびエポキシ樹脂(B)を含有し、
(a)酸無水物(A)がシクロヘキサン-1,2,4-トリカルボン酸-1,2-無水物を30~90質量%含有し、
(b)エポキシ樹脂(B)が脂環式エポキシ樹脂化合物を30~90質量%含有し、グリシジルエステル型エポキシ樹脂化合物を含有し、
(c)下記の式(1)で表わされる酸無水物とエポキシ樹脂との配合当量比が0.4~0.7の範囲である、エポキシ樹脂組成物。
酸無水物とエポキシ樹脂との配合当量比=(X+Y)/Z (1)
X:酸無水物(A)中に含まれる酸無水物基の官能基数
Y:酸無水物(A)中に含まれるカルボキシル基の官能基数
Z:エポキシ樹脂(B)中に含まれるエポキシ基の官能基数 Containing an acid anhydride (A) and an epoxy resin (B),
(A) The acid anhydride (A) contains 30 to 90% by mass of cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride,
(B) The epoxy resin (B) contains 30 to 90% by mass of the alicyclic epoxy resin compound, and contains the glycidyl ester type epoxy resin compound,
(C) An epoxy resin composition having a compounding equivalent ratio of an acid anhydride represented by the following formula (1) and an epoxy resin in the range of 0.4 to 0.7.
Compounding equivalent ratio of acid anhydride and epoxy resin = (X + Y) / Z (1)
X: Number of functional groups of acid anhydride group contained in acid anhydride (A) Y: Number of functional groups of carboxyl group contained in acid anhydride (A) Z: Number of functional groups of epoxy group contained in epoxy resin (B) Number of functional groups - エポキシ樹脂(B)におけるグリシジルエステル型エポキシ樹脂化合物の含有量が10~60質量%である、請求項1に記載のエポキシ樹脂組成物。 The epoxy resin composition according to claim 1, wherein the content of the glycidyl ester type epoxy resin compound in the epoxy resin (B) is 10 to 60% by mass.
- グリシジルエステル型エポキシ樹脂化合物が、アジピン酸ジグリシジルエステル、長鎖二塩基酸ジグリシジルエステル、テトラヒドロフタル酸ジグリシジルエステルおよびヘキサヒドロフタル酸ジグリシジルエステルからなる群より選ばれる少なくとも1つである、請求項1または2に記載のエポキシ樹脂組成物。 The glycidyl ester type epoxy resin compound is at least one selected from the group consisting of adipic acid diglycidyl ester, long-chain dibasic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester and hexahydrophthalic acid diglycidyl ester, Item 3. The epoxy resin composition according to Item 1 or 2.
- 脂環式エポキシ樹脂化合物が、3,4-エポキシシクロヘキセニルメチル-3’,4’-エポキシシクロヘキセンカルボキシレートである、請求項1~3のいずれか一項に記載のエポキシ樹脂組成物。 The epoxy resin composition according to any one of claims 1 to 3, wherein the alicyclic epoxy resin compound is 3,4-epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexenecarboxylate.
- さらに、ヒンダードフェノール系酸化防止剤を0.1~5質量%含有する、請求項1~4のいずれか一項に記載のエポキシ樹脂組成物。 The epoxy resin composition according to any one of claims 1 to 4, further comprising 0.1 to 5% by mass of a hindered phenol-based antioxidant.
- さらに、リン系硬化促進剤を0.01~5質量%含有する、請求項1~5のいずれか一項に記載のエポキシ樹脂組成物。 The epoxy resin composition according to any one of claims 1 to 5, further comprising 0.01 to 5% by mass of a phosphorus curing accelerator.
- さらに、主発光ピーク波長が550nm以下である発光素子から発光される光の少なくとも一部を吸収して蛍光を発光することが可能な蛍光物質を含有する、請求項1~6のいずれか一項に記載のエポキシ樹脂組成物。 The fluorescent material according to any one of claims 1 to 6, further comprising a fluorescent material capable of emitting fluorescence by absorbing at least a part of light emitted from the light emitting element having a main emission peak wavelength of 550 nm or less. The epoxy resin composition described in 1.
- 請求項1~7のいずれか一項に記載のエポキシ樹脂組成物を硬化して得られるエポキシ樹脂硬化物。 A cured epoxy resin obtained by curing the epoxy resin composition according to any one of claims 1 to 7.
- 請求項8に記載のエポキシ樹脂硬化物で発光素子が封止されている発光ダイオード。 A light-emitting diode in which the light-emitting element is sealed with the cured epoxy resin according to claim 8.
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CN112750766A (en) * | 2020-12-14 | 2021-05-04 | 山东融创电子科技有限公司 | Preparation process of long-life diode |
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