TW201527408A - Epoxy resin composition for optical semiconductor device, lead frame for optical semiconductor device and obtained using same, sealed semiconductor element, and optical semiconductor device - Google Patents
Epoxy resin composition for optical semiconductor device, lead frame for optical semiconductor device and obtained using same, sealed semiconductor element, and optical semiconductor device Download PDFInfo
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- TW201527408A TW201527408A TW103139903A TW103139903A TW201527408A TW 201527408 A TW201527408 A TW 201527408A TW 103139903 A TW103139903 A TW 103139903A TW 103139903 A TW103139903 A TW 103139903A TW 201527408 A TW201527408 A TW 201527408A
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- Prior art keywords
- optical semiconductor
- semiconductor device
- epoxy resin
- reflector
- resin composition
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 164
- 230000003287 optical effect Effects 0.000 title claims abstract description 152
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 94
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 94
- 239000000203 mixture Substances 0.000 title claims abstract description 68
- 239000007788 liquid Substances 0.000 claims abstract description 30
- 239000011256 inorganic filler Substances 0.000 claims abstract description 16
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 6
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 35
- 239000004848 polyfunctional curative Substances 0.000 claims description 26
- -1 3,4-epoxycyclohexyl Chemical group 0.000 claims description 22
- 229920005989 resin Polymers 0.000 claims description 19
- 239000011347 resin Substances 0.000 claims description 19
- 238000007789 sealing Methods 0.000 claims description 18
- 238000001721 transfer moulding Methods 0.000 claims description 11
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 4
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical group C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 4
- 238000001746 injection moulding Methods 0.000 claims description 4
- 229920006324 polyoxymethylene Polymers 0.000 claims description 4
- JSGRIFNBTXDZQU-UHFFFAOYSA-N C1(=CC=CC=C1)C(C(OC)(OC)OC)CCCCCCCC Chemical compound C1(=CC=CC=C1)C(C(OC)(OC)OC)CCCCCCCC JSGRIFNBTXDZQU-UHFFFAOYSA-N 0.000 claims description 3
- MFAWEYJGIGIYFH-UHFFFAOYSA-N 2-[4-(trimethoxymethyl)dodecoxymethyl]oxirane Chemical compound C(C1CO1)OCCCC(C(OC)(OC)OC)CCCCCCCC MFAWEYJGIGIYFH-UHFFFAOYSA-N 0.000 claims description 2
- JZHKIUBMQMDQRG-UHFFFAOYSA-N C(=C)C(C(OC)(OC)OC)CCCCCCCC Chemical compound C(=C)C(C(OC)(OC)OC)CCCCCCCC JZHKIUBMQMDQRG-UHFFFAOYSA-N 0.000 claims description 2
- DBJFSFSBHGPDPG-UHFFFAOYSA-N C(C(=C)C)(=O)OCCCC(C(OC)(OC)OC)CCCCCCCC Chemical compound C(C(=C)C)(=O)OCCCC(C(OC)(OC)OC)CCCCCCCC DBJFSFSBHGPDPG-UHFFFAOYSA-N 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 34
- 229910052751 metal Inorganic materials 0.000 abstract description 30
- 239000002184 metal Substances 0.000 abstract description 30
- 230000007774 longterm Effects 0.000 abstract description 17
- 230000009477 glass transition Effects 0.000 abstract description 15
- 239000000463 material Substances 0.000 abstract description 12
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract 1
- 229910000077 silane Inorganic materials 0.000 abstract 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 40
- 239000007787 solid Substances 0.000 description 19
- 239000000843 powder Substances 0.000 description 13
- 239000002245 particle Substances 0.000 description 11
- 238000002156 mixing Methods 0.000 description 10
- 150000008065 acid anhydrides Chemical class 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000012948 isocyanate Substances 0.000 description 8
- 150000002513 isocyanates Chemical class 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- 229910000420 cerium oxide Inorganic materials 0.000 description 7
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 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 6
- 239000013078 crystal Substances 0.000 description 6
- 239000003063 flame retardant Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 6
- 239000012463 white pigment Substances 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 5
- 239000011342 resin composition Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 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 4
- 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 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 239000002518 antifoaming agent Substances 0.000 description 3
- 150000007973 cyanuric acids Chemical class 0.000 description 3
- LSDYBCGXPCFFNM-UHFFFAOYSA-M dimethyl phosphate;tributyl(methyl)phosphanium Chemical compound COP([O-])(=O)OC.CCCC[P+](C)(CCCC)CCCC LSDYBCGXPCFFNM-UHFFFAOYSA-M 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- QXBYUPMEYVDXIQ-UHFFFAOYSA-N 4-methyl-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound CC1CCCC2C(=O)OC(=O)C12 QXBYUPMEYVDXIQ-UHFFFAOYSA-N 0.000 description 2
- LWMIDUUVMLBKQF-UHFFFAOYSA-N 4-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound CC1CC=CC2C(=O)OC(=O)C12 LWMIDUUVMLBKQF-UHFFFAOYSA-N 0.000 description 2
- JDBDDNFATWXGQZ-UHFFFAOYSA-N 5-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1=CC(C)CC2C(=O)OC(=O)C12 JDBDDNFATWXGQZ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 2
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920002098 polyfluorene Polymers 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- 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 2
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 description 1
- KNDQHSIWLOJIGP-UMRXKNAASA-N (3ar,4s,7r,7as)-rel-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione Chemical compound O=C1OC(=O)[C@@H]2[C@H]1[C@]1([H])C=C[C@@]2([H])C1 KNDQHSIWLOJIGP-UMRXKNAASA-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
- KMOUUZVZFBCRAM-UHFFFAOYSA-N 1,2,3,6-tetrahydrophthalic anhydride Chemical compound C1C=CCC2C(=O)OC(=O)C21 KMOUUZVZFBCRAM-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- WCPFORYMJHCRRY-UHFFFAOYSA-N 2-(isocyanatomethyl)oxirane Chemical compound O=C=NCC1CO1 WCPFORYMJHCRRY-UHFFFAOYSA-N 0.000 description 1
- 125000000143 2-carboxyethyl group Chemical group [H]OC(=O)C([H])([H])C([H])([H])* 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- WMQAQMYIZDJCDJ-UHFFFAOYSA-N 2-methyloxolane-2-carboxylic acid Chemical compound OC(=O)C1(C)CCCO1 WMQAQMYIZDJCDJ-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
- PAVNZLVXYJDFNR-UHFFFAOYSA-N 3,3-dimethyloxane-2,6-dione Chemical compound CC1(C)CCC(=O)OC1=O PAVNZLVXYJDFNR-UHFFFAOYSA-N 0.000 description 1
- BXZUCNLJIRDUBO-UHFFFAOYSA-N 3-but-1-enoxypropyl(trimethoxy)silane Chemical compound CCC=COCCC[Si](OC)(OC)OC BXZUCNLJIRDUBO-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- CUBBKYGTXMYJGQ-UHFFFAOYSA-N CC1CC(OC1)C(=O)OC(=O)C2CC(CO2)C Chemical compound CC1CC(OC1)C(=O)OC(=O)C2CC(CO2)C CUBBKYGTXMYJGQ-UHFFFAOYSA-N 0.000 description 1
- LPJCTRAHZHFCIG-UHFFFAOYSA-N COC(C(OC)(OC)OC)(CCCCCCCC)CCC.CCC=C Chemical compound COC(C(OC)(OC)OC)(CCCCCCCC)CCC.CCC=C LPJCTRAHZHFCIG-UHFFFAOYSA-N 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000004844 aliphatic epoxy resin Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- NIDNOXCRFUCAKQ-UHFFFAOYSA-N bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2C(O)=O NIDNOXCRFUCAKQ-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical class C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 239000003398 denaturant Substances 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 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
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 1
- 229940091173 hydantoin Drugs 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- YTVNOVQHSGMMOV-UHFFFAOYSA-N naphthalenetetracarboxylic dianhydride Chemical compound C1=CC(C(=O)OC2=O)=C3C2=CC=C2C(=O)OC(=O)C1=C32 YTVNOVQHSGMMOV-UHFFFAOYSA-N 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000001579 optical reflectometry Methods 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- JIYNFFGKZCOPKN-UHFFFAOYSA-N sbb061129 Chemical compound O=C1OC(=O)C2C1C1C=C(C)C2C1 JIYNFFGKZCOPKN-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 description 1
- UJJLJRQIPMGXEZ-UHFFFAOYSA-N tetrahydro-2-furoic acid Chemical compound OC(=O)C1CCCO1 UJJLJRQIPMGXEZ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 1
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical class OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 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
- 239000013638 trimer Substances 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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- H—ELECTRICITY
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- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/52—Encapsulations
- H01L33/56—Materials, e.g. epoxy or silicone resin
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- 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
- C08G59/245—Di-epoxy compounds carbocyclic aromatic
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- C—CHEMISTRY; METALLURGY
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
- C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- 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
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- 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
- H01L33/62—Arrangements for conducting electric current to or from the semiconductor body, e.g. lead-frames, wire-bonds or solder balls
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K2003/2244—Oxides; Hydroxides of metals of zirconium
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- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
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- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
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- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/481—Disposition
- H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/48245—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
- H01L2224/48247—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a bond pad of the item
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- H—ELECTRICITY
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- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/481—Disposition
- H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
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- H01L2224/48257—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a die pad of the item
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- H01L2924/11—Device type
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- 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
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Abstract
Description
本發明係有關於一種成為反射器(反射部)之形成材料的光半導體裝置用環氧樹脂組成物及使用其製得之光半導體裝置用引線框、密封型光半導體元件以及光半導體裝置，前述反射器可使例如從光半導體元件發出之光反射。 The present invention relates to an epoxy resin composition for an optical semiconductor device which is a material for forming a reflector (reflecting portion), and a lead frame for a photo-semiconductor device, a sealed optical semiconductor device, and an optical semiconductor device which are obtained by using the same. The reflector can reflect, for example, light emitted from the optical semiconductor component.
習知，搭載光半導體元件而成的光半導體裝置係例如圖1所示採取下述構成：於第1板部1及第2板部2所構成之金屬引線框上搭載光半導體元件3，並形成有樹脂材料所構成之光反射用反射器4，該光反射用反射器4係形成為包圍上述光半導體元件3周圍且更填滿第1板部1與第2板部2之間。而且，使用因應需求含有螢光體的聚矽氧樹脂等透明樹脂，將已搭載於凹部5之光半導體元件3予以樹脂密封而形成有密封樹脂層6，該凹部5係形成為上述金屬引線框與反射器4之內周面。在圖1中，7、8係將金屬引線框與光半導體元件3予以電連接之接合線，可因應需求設置。 In the optical semiconductor device in which the optical semiconductor device is mounted, for example, as shown in FIG. 1, the optical semiconductor device 3 is mounted on the metal lead frame formed by the first plate portion 1 and the second plate portion 2, and A light reflecting reflector 4 composed of a resin material is formed, and the light reflecting reflector 4 is formed to surround the periphery of the optical semiconductor element 3 and further fill the space between the first plate portion 1 and the second plate portion 2. In addition, the optical resin element 3 mounted on the concave portion 5 is resin-sealed by using a transparent resin such as a polyoxyn resin containing a phosphor, and the sealing resin layer 6 is formed. The concave portion 5 is formed as the metal lead frame. With the inner circumference of the reflector 4. In Fig. 1, 7, 8 are bonding wires for electrically connecting the metal lead frame and the optical semiconductor element 3, and can be set as needed.
在此種光半導體裝置中，近年多使用以環氧樹脂等為代表的熱硬化性樹脂，藉由例如轉注成形等來成形製造上述反射器4。而且，自習知係於上述熱硬化性樹脂中摻混氧化鈦作為白色顏料，以使從上述光半導體元件3發出之光反射(參照專利文獻1)。 In such an optical semiconductor device, a thermosetting resin typified by an epoxy resin or the like is used in many years, and the reflector 4 is molded by, for example, transfer molding. In addition, it is known that the titanium oxide is blended as a white pigment in the thermosetting resin to reflect light emitted from the optical semiconductor element 3 (see Patent Document 1).
專利文獻1：日本專利特開2011-258845號公報 Patent Document 1: Japanese Patent Laid-Open No. 2011-258845
然而，如上述使用氧化鈦作為白色顏料來形成反射器時，就初始光反射率來說可毫無問題地實現高度光反射率，但使用一段時間後有其光反射率降低之問題。如此一來，在長期發揮高度光反射率、即長期耐光性之方面依舊不夠充分，因而有進一步提升此長期耐光性的強烈需求。此外，若考慮到其用途，除上述耐光性之提升外，連帶關於硬化物之玻璃轉移溫度(Tg)亦需要較高，但現況是尚未獲得充分滿足需求的成品。 However, when titanium oxide is used as the white pigment to form the reflector as described above, the high light reflectance can be realized without any problem in terms of the initial light reflectance, but there is a problem that the light reflectance is lowered after a certain period of use. As a result, the long-term high light reflectance, that is, the long-term light resistance, is still insufficient, and there is a strong demand for further improvement of the long-term light resistance. In addition, in consideration of the use thereof, in addition to the above-mentioned improvement in light resistance, the glass transition temperature (Tg) associated with the cured product is also required to be high, but the current situation is that the finished product which has not sufficiently satisfied the demand has not yet been obtained.
本發明乃有鑑於上述情況而起，其目的在於提供一種不僅具有高度的初始光反射率且具有優異的長期耐光性、並可獲得高玻璃轉移溫度的硬化物之光半導體裝置用環氧樹脂組成物，及使用其製得之光半導體裝置用引線框、密封型光半導體元件以及光半導體裝置。 The present invention has been made in view of the above circumstances, and an object thereof is to provide an epoxy resin composition for an optical semiconductor device which has not only a high initial light reflectance but also excellent long-term light resistance and a high glass transition temperature. And a lead frame for a photo-semiconductor device, a hermetic optical semiconductor device, and an optical semiconductor device.
為了達成上述目的，本發明第1主旨為一種光半導體裝置用環氧樹脂組成物，該光半導體裝置用環氧樹脂組成物含有下述(A)~(E)，下述(C)及(E)之合計含量為環氧樹脂組成物整體之70~90體積%，且相對於下述(C)，下述(D)之含量為0.1~8重量%；(A)環氧樹脂；(B)以液狀硬化劑作為主成分之硬化劑；(C)氧化鋯；(D)矽烷系化合物；(E)無機質充填劑。 In order to achieve the above object, a first aspect of the present invention provides an epoxy resin composition for an optical semiconductor device comprising the following (A) to (E), the following (C) and The total content of E) is 70 to 90% by volume of the entire epoxy resin composition, and the content of the following (D) is 0.1 to 8% by weight with respect to the following (C); (A) epoxy resin; B) a hardener having a liquid hardener as a main component; (C) zirconium oxide; (D) a decane compound; (E) an inorganic filler.
而且，本發明第2主旨為一種光半導體裝置用引線框，該光半導體裝置用引線框係用以僅於厚度方向之一面上搭載光半導體元件的板狀光半導體裝置用引線框，其具備多數個彼此隔有間隙配置的板部且於上述間隙形成反射器而成，該反射器係使用上述第1主旨之光半導體裝置用環氧樹脂組成物充填至上述間隙並使其硬化而成。又，本發明第3主旨為一種光半導體裝置用引線框，該光半導體裝置用引線框係具備光半導體元件搭載區並形成反射器而成的立體狀光半導體裝置用引線框，且該反射器呈以其本身之至少一部分包圍元件搭載區周圍的狀態；上述反射器係使用上述第1主旨之光半導體裝置用環氧樹脂組成物形成而成。 Further, the second aspect of the present invention is a lead frame for an optical semiconductor device, wherein the lead frame for the optical semiconductor device is used for a lead frame for a plate-shaped optical semiconductor device in which an optical semiconductor element is mounted on only one surface in a thickness direction, and a lead frame is provided The reflector is formed by a plate portion which is disposed with a gap therebetween, and a reflector is formed in the gap. The reflector is filled and hardened by using the epoxy resin composition for an optical semiconductor device according to the first aspect. According to a third aspect of the present invention, in a lead frame for an optical semiconductor device, a lead frame for a three-dimensional optical semiconductor device in which a photo-semiconductor mounting region is provided and a reflector is formed, and the reflector is provided The reflector is surrounded by at least a part of the component mounting region, and the reflector is formed using the epoxy resin composition for an optical semiconductor device according to the first aspect.
此外，本發明第4主旨為一種光半導體裝置，該 光半導體裝置係使於其一面上具有用以搭載光半導體元件之元件搭載區的板部彼此隔有間隙配置，且於上述元件搭載區之預定位置上搭載光半導體元件而成者；於上述間隙形成反射器而成，且該反射器係使用上述第1主旨之光半導體裝置用環氧樹脂組成物充填至上述間隙並使其硬化而成。又，本發明第5主旨為一種光半導體裝置，該光半導體裝置係於光半導體裝置用引線框之預定位置上搭載光半導體元件而成者，該光半導體裝置用引線框係具備光半導體元件搭載區並形成反射器而成，且該反射器呈以其本身之至少一部分包圍元件搭載區周圍的狀態；上述反射器係使用上述第1主旨之光半導體裝置用環氧樹脂組成物形成而成。 Further, a fourth object of the present invention is an optical semiconductor device, In the optical semiconductor device, a plate portion having an element mounting region on which an optical semiconductor element is mounted is provided with a gap therebetween, and an optical semiconductor element is mounted on a predetermined position of the element mounting region; The reflector is formed by using the epoxy resin composition for an optical semiconductor device according to the first aspect described above, and filling the gap with the epoxy resin. According to a fifth aspect of the invention, there is provided an optical semiconductor device in which an optical semiconductor device is mounted on a predetermined position of a lead frame for an optical semiconductor device, and the lead frame of the optical semiconductor device is provided with an optical semiconductor device. The reflector is formed in a state in which the reflector surrounds the periphery of the element mounting region by at least a part thereof, and the reflector is formed using the epoxy resin composition for an optical semiconductor device according to the first aspect.
而且，本發明第6主旨為一種密封型光半導體元件，該密封型光半導體元件於背面形成多數連接用電極而成之光半導體元件之側面，形成由上述第1主旨之光半導體裝置用環氧樹脂組成物所構成的反射器，並以密封層被覆上述光半導體元件上部之發光面或受光面而構成。又，本發明第7主旨為一種光半導體裝置，該光半導體裝置係使上述第6主旨之密封型光半導體元件藉由其連接用電極搭載於配線電路基板之預定位置而成者。 According to a sixth aspect of the present invention, there is provided a sealed optical semiconductor device comprising: a side surface of an optical semiconductor device in which a plurality of connection electrodes are formed on a back surface, and an epoxy for an optical semiconductor device according to the first aspect is formed. A reflector composed of a resin composition is formed by covering a light-emitting surface or a light-receiving surface of the upper portion of the optical semiconductor element with a sealing layer. According to a seventh aspect of the invention, the optical semiconductor device of the sixth aspect of the invention is characterized in that the sealed optical semiconductor device of the sixth aspect is mounted on a predetermined position of the printed circuit board by the connection electrode.
本發明人等為了獲得一種初始光反射率高之外長期耐光性亦佳且具有高玻璃轉移溫度之光半導體裝置用環氧樹脂組成物，不斷重複進行精闢研討。在其研究過程中，本發明人等想起白色顏料不用習知一直使用的氧化鈦 而是利用其他白色顏料來改善長期耐光性，於是進行種種檢討的結果，著眼於使用氧化鋯來作為白色顏料，進而獲得下述見解：由於氧化鋯在作為材料上硬度高於顏料級的氧化鈦，所以若在摻混高充填量之二氧化矽等無機質充填劑的樹脂組成物中運用氧化鋯來取代顏料級的氧化鈦，在製作樹脂材料時，會因為直接與樹脂組成物接觸之金屬製裝置的摩耗而使獲得的樹脂組成物變黑，亦即會發生初始光反射率變低之問題。爰此，本發明人等為了解決此問題而進一步重複進行研討的結果發現：將上述氧化鋯連同作為硬化劑之液狀硬化劑一起使用，並將含有無機質充填劑及上述氧化鋯之充填劑整體設定為特定比率，且按特定比率使用矽烷系化合物，如此便可獲得一種可成為反射器之形成材料的環氧樹脂組成物，而該反射器可實現高度的初始光反射率同時長期耐光性優異且具備高玻璃轉移溫度。 The inventors of the present invention have repeatedly conducted intensive studies in order to obtain an epoxy resin composition for an optical semiconductor device which has a high initial light reflectance and a long-term light resistance and a high glass transition temperature. In the course of its research, the inventors of the present invention have thought of the white pigment without the conventionally used titanium oxide. Instead of using other white pigments to improve the long-term light resistance, the results of various reviews focused on the use of zirconia as a white pigment, and the following insights were obtained: since zirconia has a hardness higher than that of the pigment grade as a material. Therefore, if a zirconia is used in place of a pigment-grade titanium oxide in a resin composition of an inorganic filler such as a high-filling amount of cerium oxide, when a resin material is produced, it is made of a metal which is in direct contact with the resin composition. The wear of the device causes the obtained resin composition to become black, that is, the problem that the initial light reflectance becomes low. As a result of further investigations in order to solve this problem, the present inventors have found that the zirconia is used together with a liquid hardener as a curing agent, and the filler containing the inorganic filler and the zirconia as a whole is used. By setting a specific ratio and using a decane compound at a specific ratio, an epoxy resin composition which can be used as a material for forming a reflector can be obtained, and the reflector can achieve a high initial light reflectance and excellent long-term light resistance. And has a high glass transition temperature.
如上述，本發明係一種光半導體裝置用環氧樹脂組成物，其含有前述環氧樹脂(A)、以液狀硬化劑作為主成分之硬化劑(B)、氧化鋯(C)、矽烷系化合物(D)及無機質充填劑(E)，且將上述(C)及(E)之合計含量及上述(D)之含量設定為特定量。因此，可成為不僅初始光反射率高且具備優異的長期耐光性、亦具有高玻璃轉移溫度的組成物。因此，就使用上述光半導體裝置用環氧樹脂組成物形成反射器而成的光半導體裝置而言，可獲得可靠性高的光半導體裝置。 As described above, the present invention relates to an epoxy resin composition for an optical semiconductor device comprising the epoxy resin (A), a hardener (B) containing a liquid hardener as a main component, zirconium oxide (C), and a decane system. The compound (D) and the inorganic filler (E) are set to a specific amount by the total content of the above (C) and (E) and the content of the above (D). Therefore, it is possible to have a composition having high initial light reflectance, excellent long-term light resistance, and high glass transition temperature. Therefore, an optical semiconductor device in which a reflector is formed using the epoxy resin composition for an optical semiconductor device described above can provide a highly reliable optical semiconductor device.
而且，上述矽烷系化合物(D)若為特定的矽烷系 化合物，便可具備更優異的初始光反射率及長期耐光性、以及更高的玻璃轉移溫度。 Further, the above decane-based compound (D) is a specific decane system. The compound has better initial light reflectance and long-term light resistance, as well as higher glass transition temperature.
1‧‧‧第1板部 1‧‧‧1st Board
2‧‧‧第2板部 2‧‧‧2nd Board
3‧‧‧光半導體元件 3‧‧‧Optical semiconductor components
4、11、15‧‧‧反射器 4, 11, 15‧‧ ‧ reflector
5‧‧‧凹部 5‧‧‧ recess
6‧‧‧密封樹脂層 6‧‧‧ sealing resin layer
7、8、12‧‧‧接合線 7, 8, 12‧‧ ‧ bonding wire
10‧‧‧金屬引線框 10‧‧‧Metal lead frame
11‧‧‧光反射用反射器 11‧‧‧Light reflection reflector
15‧‧‧光反射用反射器 15‧‧‧Light reflection reflector
16‧‧‧密封層 16‧‧‧ Sealing layer
17‧‧‧連接用電極 17‧‧‧Connecting electrode
圖1係示意顯示光半導體裝置之構成的截面圖。 Fig. 1 is a cross-sectional view schematically showing the configuration of an optical semiconductor device.
圖2係示意顯示光半導體裝置之其他構成的俯視圖。 Fig. 2 is a plan view schematically showing another configuration of the optical semiconductor device.
圖3係上述示意顯示光半導體裝置之其他構成的俯視圖之X-X’箭頭截面圖。 Fig. 3 is a cross-sectional view taken along the line X-X' of the plan view showing another configuration of the optical semiconductor device.
圖4係示意顯示密封型光半導體元件之構成的截面圖。 Fig. 4 is a cross-sectional view schematically showing the configuration of a sealed type optical semiconductor element.
以下記載之構成要件的說明僅為本發明實施態樣之一例(代表例)，且不受該等內容限定。 The description of the constituent elements described below is only an example (representative example) of the embodiment of the present invention, and is not limited by the contents.
以下，針對本發明予以詳細說明。 Hereinafter, the present invention will be described in detail.
本發明之光半導體裝置用環氧樹脂組成物(以下亦稱「環氧樹脂組成物」)例如先前所述係可在如圖1所示光半導體裝置或如後述圖2及圖3所示光半導體裝置、以及如圖4所示密封型光半導體元件中，作為反射器4、11、15形成材料使用者，可使用環氧樹脂(A成分)、以液狀硬化劑作為主成分之硬化劑(B成分)、氧化鋯(C成分)、矽烷系化合物(D成分)及無機質充填劑(E成分)而製得，通常係以液狀、或粉末狀、又或將其粉末製錠成錠狀來供給作為反射器4、11、15之形成材料。而，在本發明中，上述「作為主成分」之主旨為包含僅以主成分構成之情況。 The epoxy resin composition for an optical semiconductor device of the present invention (hereinafter also referred to as "epoxy resin composition") can be, for example, the optical semiconductor device shown in Fig. 1 or the light shown in Fig. 2 and Fig. 3 which will be described later. In the semiconductor device and the sealed optical semiconductor device shown in FIG. 4, as a material for forming the reflectors 4, 11, and 15, an epoxy resin (component A) and a hardener having a liquid hardener as a main component can be used. (B component), zirconia (component C), decane-based compound (component D), and inorganic filler (component E), usually obtained in the form of a liquid or a powder, or a powder thereof. The material for forming the reflectors 4, 11, 15 is supplied. In the present invention, the above-mentioned "as a main component" is intended to include a case where only a main component is included.
〈A：環氧樹脂〉 <A: Epoxy resin>
以上述環氧樹脂(A成分)來說，可舉如：雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、苯酚酚醛型環氧樹脂或甲酚酚醛型環氧樹脂等酚醛型環氧樹脂、三聚異氰酸單環氧丙酯、三聚異氰酸二環氧丙酯、三聚異氰酸三環氧丙酯、海因環氧樹脂等含氮環環氧樹脂、加氫雙酚A型環氧樹脂、加氫雙酚F型環氧樹脂、脂肪族系環氧樹脂、聚矽氧改質環氧樹脂、縮水甘油醚型環氧樹脂、烷基取代雙酚等藉由二縮水甘油醚、二胺基二苯甲烷及異三聚氰酸等多胺與環氧氯丙烷之反應而獲得的縮水甘油胺型環氧樹脂；及以過乙酸等過酸將烯烴鍵進行酸化而獲得之線狀脂肪族及脂環式環氧樹脂、低吸水率硬化物型之主流的聯苯型環氧樹脂、二環環型環氧樹脂、萘型環氧樹脂等。該等可單獨使用亦可將2種以上合併使用。該等環氧樹脂中，從透明性及耐變色性優異的觀點看來，又宜單獨使用或合併使用脂環式環氧樹脂或三聚異氰酸三環氧丙酯等具有異三聚氰醯環結構者。從同樣理由來看，酞酸、四氫酞酸、六氫酞酸、甲基四氫酞酸、納迪克酸、甲基納迪克酸等二羧酸之二縮水甘油酯亦佳。又可舉如芳香環具有經氫化之脂環式結構的核氫化偏苯三甲酸、核氫化焦蜜石酸等縮水甘油酯等。 The epoxy resin (component A) may, for example, be a bisphenol A epoxy resin, a bisphenol F epoxy resin, a bisphenol S epoxy resin, a phenol novolak epoxy resin or a cresol novolac. Phenolic epoxy resin such as epoxy resin, monoglycidyl isocyanate, diglycidyl isocyanate, triglycidyl isocyanate, hydantoin, etc. Nitrogen-containing epoxy resin, hydrogenated bisphenol A epoxy resin, hydrogenated bisphenol F epoxy resin, aliphatic epoxy resin, polyoxymethylene modified epoxy resin, glycidyl ether epoxy resin a glycidylamine type epoxy resin obtained by reacting a polyamine such as diglycidyl ether, diaminodiphenylmethane or iso-cyanuric acid with epichlorohydrin, such as an alkyl-substituted bisphenol; A biphenyl type epoxy resin, a bicyclic ring type epoxy resin, a naphthalene type which is a linear aliphatic and alicyclic epoxy resin obtained by acidifying an olefin bond, such as acetic acid, and a low water absorption hardening type. Epoxy resin, etc. These may be used alone or in combination of two or more. Among these epoxy resins, from the viewpoint of excellent transparency and discoloration resistance, it is also preferred to use alicyclic epoxy resin or trisuccinyl isocyanate with isomeric cyanide alone or in combination.醯 ring structure. For the same reason, diglycidyl esters of dicarboxylic acids such as capric acid, tetrahydrofurfuric acid, hexahydrononanoic acid, methyltetrahydrofurfuric acid, nadic acid, and methyl nadic acid are also preferred. Further, examples thereof include a nuclear hydrogenated trimellitic acid having a hydrogenated alicyclic structure, a glycidyl ester such as nuclear hydrogenated pyrophoric acid, and the like.
以上述環氧樹脂(A成分)而言，常溫下可為固體亦可為液狀，一般來說，使用之環氧樹脂的平均環氧當量為90~1000者為佳，又，為固體時，從處置性之便利性的觀點看來則以軟化點為50~160℃者為佳。即，其理由在於 環氧當量一旦過小，環氧樹脂組成物硬化物就有可能變脆。又，環氧當量一旦過大，便有環氧樹脂組成物硬化物之玻璃轉移溫度(Tg)變低的傾向。 The epoxy resin (component A) may be solid or liquid at normal temperature. Generally, the epoxy resin used has an average epoxy equivalent of 90 to 1000, and is solid. From the viewpoint of convenience of handling, it is preferred that the softening point is 50 to 160 °C. That is, the reason is Once the epoxy equivalent is too small, the cured epoxy resin composition may become brittle. Further, when the epoxy equivalent is too large, the glass transition temperature (Tg) of the cured epoxy resin composition tends to be low.
〈B：硬化劑〉 <B: Hardener>
在本發明中，硬化劑(B成分)係以液狀硬化劑作為主成分者，如先前所述包含硬化劑成分僅由液狀硬化劑構成之情況。具體上，液狀硬化劑在硬化劑整體佔40重量%以上為佳，特別理想則是硬化劑成分僅以液狀硬化劑構成。而，上述液狀硬化劑係表示在室溫(25℃)下呈現液狀之硬化劑。而且，例如從耐熱性及耐光性之觀點看來，此種液狀硬化劑可舉如呈液狀之酸酐系硬化劑等。 In the present invention, the curing agent (component B) is a liquid curing agent as a main component, and as described above, the curing agent component is composed only of a liquid curing agent. Specifically, the liquid curing agent is preferably 40% by weight or more based on the entire curing agent, and it is particularly preferred that the curing agent component is composed only of a liquid curing agent. Further, the above liquid hardener means a liquid hardener which exhibits a liquid state at room temperature (25 ° C). Further, for example, from the viewpoint of heat resistance and light resistance, such a liquid hardener may, for example, be a liquid acid anhydride-based hardener.
就上述呈液狀之酸酐系硬化劑來說，可舉如3-甲基六氫酞酸酐(液狀)、4-甲基六氫酞酸酐(液狀)、3-甲基四氫酞酸酐(液狀)、4-甲基四氫酞酸酐(液狀)、甲基納迪克酸酐(液狀)、環己烷-1,2,4-三羧酸-1,2-酐(液狀)等。該等可單獨使用亦可將2種以上合併使用。又，作為飽和脂肪鏈骨架、不飽和脂肪鏈骨架或聚矽氧骨架之末端基乃至於側鏈而具有該等酸酐之寡聚物，亦可單獨使用或合併2種以上使用及與上述酸酐合併使用。該等呈液狀之酸酐系硬化劑中，又宜使用3-甲基六氫酞酸酐、4-甲基六氫酞酸酐、3-甲基四氫酞酸酐、4-甲基四氫酞酸酐、以及於該等中混合有呈固體之六氫酞酸酐者。 The above-mentioned liquid acid anhydride-based hardener may, for example, be 3-methylhexahydrophthalic anhydride (liquid), 4-methylhexahydrophthalic anhydride (liquid), 3-methyltetrahydrophthalic anhydride (liquid), 4-methyltetrahydrophthalic anhydride (liquid), methyl nadic anhydride (liquid), cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride (liquid) )Wait. These may be used alone or in combination of two or more. Further, an oligomer having such an acid anhydride as a terminal group of a saturated aliphatic chain skeleton, an unsaturated aliphatic chain skeleton or a polyfluorene skeleton, or a side chain may be used singly or in combination of two or more kinds thereof and combined with the above acid anhydride. use. Among these liquid anhydride-based hardeners, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, and 4-methyltetrahydrofurfuric anhydride are preferably used. And in which the solid hexahydrophthalic anhydride is mixed.
而且，連同上述呈液狀之液狀硬化劑一起，可在不阻礙本發明效果之範圍內，適當地單獨或合併使用2種以 上呈固體之酸酐系硬化劑，例如六氫酞酸酐(固體)、酞酸酐(固體)、馬來酸酐(固體)、琥珀酸酐(固體)、偏苯三甲酸酐(固體)、納迪克酸酐(固體)、焦蜜石酸酐(固體)、萘-1,4,5,8-四羧酸二酐(固體)及其核氫化物、四氫酞酸酐(固體)、二甲基戊二酸酐(固體)、戊二酸酐(固體)等。而，上述酸酐系硬化劑中之固體係表示在室溫(25℃)下呈現固體之態樣。 Further, together with the liquid-like liquid hardener described above, two kinds may be appropriately used singly or in combination, without departing from the effects of the present invention. An acid anhydride hardener such as hexahydrophthalic anhydride (solid), phthalic anhydride (solid), maleic anhydride (solid), succinic anhydride (solid), trimellitic anhydride (solid), nadic anhydride (solid) ), pyrogallite (solid), naphthalene-1,4,5,8-tetracarboxylic dianhydride (solid) and its nuclear hydride, tetrahydrophthalic anhydride (solid), dimethyl glutaric anhydride (solid) ), glutaric anhydride (solid), and the like. On the other hand, the solid in the acid anhydride-based hardener means a solid state at room temperature (25 ° C).
此外，可連同上述呈液狀之酸酐系硬化劑一起，在不阻礙本發明效果之範圍內使用上述酸酐之水解生成物的羧酸或異三聚氰酸衍生物系硬化劑等。 In addition, a carboxylic acid or a isocyanuric acid derivative-based curing agent or the like which is a hydrolysis product of the above-mentioned acid anhydride can be used in the range which does not inhibit the effects of the present invention, together with the above-mentioned liquid acid anhydride-based curing agent.
又，就上述異三聚氰酸衍生物系硬化劑而言，可舉如1,3,5-參(1-羧甲基)三聚異氰酸酯、1,3,5-參(2-羧乙基)三聚異氰酸酯、1,3,5-參(3-羧丙基)三聚異氰酸酯、1,3-雙(2-羧乙基)三聚異氰酸酯等。該等可單獨使用亦可將2種以上合併使用。此外，作為異三聚氰酸衍生物系硬化劑以無色或淡黃色的硬化劑為佳。 Further, the above-mentioned isocyanuric acid derivative-based curing agent may, for example, be 1,3,5-gin(1-carboxymethyl)trimeric isocyanate or 1,3,5-gin (2-carboxyethyl) A trimeric isocyanate, a 1,3,5-gin (3-carboxypropyl) trimer isocyanate, a 1,3-bis(2-carboxyethyl)trimeric isocyanate or the like. These may be used alone or in combination of two or more. Further, as the hardening agent for the isocyanuric acid derivative, a colorless or yellowish hardener is preferred.
在此，上述A成分與上述B成分之摻混比率宜設定為相對於A成分中之環氧基1當量，B成分中可與環氧基發生反應之活性基(酸酐基或羧基)為0.4~1.4當量，較理想為0.6~1.2當量。即，其理由在於活性基一旦過少，便有環氧樹脂組成物之硬化速度減慢，同時其硬化物之玻璃轉移溫度(Tg)減低的傾向，而活性基一旦過多則有耐濕性降低的傾向。 Here, the blending ratio of the component A and the component B is preferably set to 1 equivalent to the epoxy group in the component A, and the reactive group (anhydride group or carboxyl group) which can react with the epoxy group in the component B is 0.4. ~1.4 equivalents, more preferably 0.6 to 1.2 equivalents. That is, the reason is that when the amount of the active group is too small, the curing rate of the epoxy resin composition is slowed down, and the glass transition temperature (Tg) of the cured product tends to decrease, and when the active group is excessive, the moisture resistance is lowered. tendency.
又，因應其目的及用途，可在不阻礙本發明效果之範圍內單獨或合併使用2種以上上述硬化劑以外的其他 環氧樹脂系硬化劑，例如苯酚系硬化劑、胺系硬化劑及以醇將上述酸酐系硬化劑予以部分酯化者等的硬化劑。而，即便在使用該等硬化劑的情況下，其摻混比率依照上述A成分與B成分之摻混比率(當量比)即可。 Further, in addition to the purpose and the use thereof, it is possible to use two or more kinds of the above-mentioned hardeners alone or in combination within a range that does not impair the effects of the present invention. The epoxy resin-based curing agent is, for example, a phenol-based curing agent, an amine-based curing agent, and a curing agent such as a partial esterification of the above-described acid anhydride-based curing agent with an alcohol. Further, even in the case of using such a curing agent, the blending ratio may be in accordance with the blending ratio (equivalent ratio) of the component A and the component B described above.
〈C：氧化鋯(ZrO2)〉 <C: Zirconia (ZrO 2 )>
可與上述A成分及B成分一起使用的氧化鋯(C成分)在本發明中係作為白色顏料使用。上述氧化鋯中有單斜晶、正方晶、立方晶等多種結晶系，其中從成本等觀點看來，又宜使用單斜晶之氧化鋯。就上述氧化鋯從流動性等觀點來看，宜使用平均粒徑為0.01~50μm者，較理想為0.1~30μm，特別理想為0.1~20μm。而，上述平均粒徑例如可使用雷射繞射散射式粒度分布計來測定。 Zirconium oxide (component C) which can be used together with the above component A and component B is used as a white pigment in the present invention. Among the above zirconia, there are various crystal systems such as monoclinic crystal, tetragonal crystal, and cubic crystal. Among them, monoclinic zirconia is preferably used from the viewpoint of cost and the like. The zirconia is preferably used in an amount of from 0.01 to 50 μm, more preferably from 0.1 to 30 μm, particularly preferably from 0.1 to 20 μm, from the viewpoint of fluidity and the like. Further, the above average particle diameter can be measured, for example, by using a laser diffraction scattering type particle size distribution meter.
相對於環氧樹脂組成物整體，上述氧化鋯(C成分)之含有比率理想為3~50體積%，較理想為5~30體積%。即，其理由在於C成分之含有比率一旦過少，便有難以獲得充分的光反射性，尤其是難以獲得優異的初始光反射率的傾向。C成分之含有比率一旦過多，便可能藉由顯著的增黏而在捏合等環氧樹脂組成物的製作上發生困難。 The content ratio of the zirconia (component C) is preferably from 3 to 50% by volume, and more preferably from 5 to 30% by volume, based on the entire epoxy resin composition. In other words, the reason is that when the content ratio of the component C is too small, it is difficult to obtain sufficient light reflectivity, and in particular, it is difficult to obtain an excellent initial light reflectance. When the content ratio of the component C is too large, it may cause difficulty in the production of an epoxy resin composition such as kneading by remarkably increasing the viscosity.
〈D：矽烷系化合物〉 <D: decane compound>
就上述矽烷系化合物(D成分)來說，可舉如各種矽烷系化合物，例如下述通式(1)所示之矽烷系化合物。 The decane-based compound (component D) may, for example, be a decane-based compound represented by the following formula (1).
(X)n(R)3-nSi(R’)…(1) (X) n (R) 3-n Si(R')...(1)
[式(1)中，X為CH3O-或C2H5O-，R為CH3-或C2H5-，R’為-CmH2m+1、-CH=CH2、-C6H5或-R”Y[m為1~12之正數，R” 為-CH2-、-CH2CH2-或-CH2CH2CH2-，Y為縮水甘油醚基、3,4-環氧環己基、-OOC(CH3)C=CH2、-NH2或-NHCH2CH2NH2]，n為1、2或3]。 [In the formula (1), X is CH 3 O- or C 2 H 5 O-, R is CH 3 - or C 2 H 5 -, and R' is -C m H 2m+1 , -CH=CH 2 , -C 6 H 5 or -R"Y[m is a positive number from 1 to 12, R" is -CH 2 -, -CH 2 CH 2 - or -CH 2 CH 2 CH 2 -, Y is a glycidyl ether group, 3,4-epoxycyclohexyl, -OOC(CH 3 )C=CH 2 , -NH 2 or -NHCH 2 CH 2 NH 2 ], n is 1, 2 or 3].
具體上，可使用3-環氧丙氧基丙基三甲氧矽烷、3-甲基丙烯醯氧基丙基三甲氧矽烷等矽烷耦合劑或苯基三甲氧矽烷、乙烯基三甲氧矽烷等矽烷等。該等可單獨使用或可將2種以上合併使用。其中，從玻璃轉移溫度之降低抑制效果等觀點看來，又宜使用苯基三甲氧矽烷。 Specifically, a decane coupling agent such as 3-glycidoxypropyltrimethoxysilane or 3-methylpropenyloxypropyltrimethoxysilane or a decane such as phenyltrimethoxysilane or vinyltrimethoxysilane can be used. . These may be used alone or in combination of two or more. Among them, phenyltrimethoxydecane is preferably used from the viewpoint of suppressing the effect of lowering the glass transition temperature.
相對於上述氧化鋯(C成分)，上述矽烷系化合物(D成分)之含有比率必須在0.1~8重量%。較理想為0.2~7重量%，特別理想為0.2~6重量%。即，D成分之含有比率一旦過少，便無法獲得優異的初始光反射率；一旦過多則玻璃轉移溫度之降低會變很顯著。 The content ratio of the above decane-based compound (component D) must be 0.1 to 8% by weight based on the zirconia (component C). It is preferably 0.2 to 7% by weight, particularly preferably 0.2 to 6% by weight. That is, once the content ratio of the component D is too small, an excellent initial light reflectance cannot be obtained; and if it is too large, the glass transition temperature is lowered significantly.
〈E：無機質充填劑〉 <E: Inorganic Filler>
可與上述A~D成分一起使用的無機質充填劑(E成分)可舉如石英玻璃粉末、滑石、熔融二氧化矽粉末或結晶性二氧化矽粉末等二氧化矽粉末、氧化鋁粉末、氮化鋁粉末、氮化矽粉末等。其中，從線膨脹係數之減低等觀點看來，又宜使用熔融二氧化矽粉末，尤其從高充填性及高流動性的觀點看來，則宜使用熔融球狀二氧化矽粉末。而，無機質充填劑(E成分)中有將上述氧化鋯(C成分)除外。有關上述無機質充填劑(E成分)之粒徑及其分布，宜以可使藉由轉注成形等成形環氧樹脂組成物時的溢料等減低至最低的方式，來考量與上述氧化鋯(C成分)之粒徑及其分布的組合。 具體上，無機質充填劑(E成分)之平均粒徑在5~100μm為佳，特別理想在10~80μm。而，上述平均粒徑與前述同樣地例如可使用雷射繞射散射式粒度分布計來進行測定。 The inorganic filler (component E) which can be used together with the above components A to D can be, for example, quartz glass powder, talc, molten cerium oxide powder or crystalline cerium oxide powder, such as cerium oxide powder, alumina powder, or nitriding. Aluminum powder, tantalum nitride powder, and the like. Among them, from the viewpoint of the reduction of the coefficient of linear expansion, it is preferable to use a molten cerium oxide powder, and in particular, from the viewpoint of high filling property and high fluidity, it is preferable to use a molten spherical cerium oxide powder. Further, in the inorganic filler (component E), the above-mentioned zirconia (component C) is excluded. The particle size and the distribution of the above-mentioned inorganic filler (component E) are preferably considered to be the same as the above-mentioned zirconia (C) in such a manner that the flash or the like when the epoxy resin composition is formed by transfer molding or the like is minimized. The composition of the particle size and its distribution. Specifically, the inorganic filler (E component) preferably has an average particle diameter of 5 to 100 μm, particularly preferably 10 to 80 μm. Further, the above average particle diameter can be measured by, for example, a laser diffraction scattering type particle size distribution meter as described above.
而且，在上述無機質充填劑(E成分)之含有比率中，宜設定成上述氧化鋯(C成分)與無機質充填劑(E成分)之合計含有比率為環氧樹脂組成物整體之70~90體積%。較理想為75~85體積%。上述合計含有比率一旦過少，有產生成形時發生翹曲等問題的傾向。又，合計含有比率一旦過多，有捏合摻混成分時對捏合機賦予龐大負荷而無法進行捏合的傾向，結果有難以製作成形材料之環氧樹脂組成物的傾向。 Further, in the content ratio of the inorganic filler (component E), it is preferable to set the total content ratio of the zirconia (C component) and the inorganic filler (E component) to 70 to 90 by volume of the entire epoxy resin composition. %. It is preferably 75 to 85% by volume. When the total content ratio is too small, there is a tendency that warpage or the like occurs during molding. In addition, when the total content ratio is too large, when the kneaded blending component is kneaded, a large load is applied to the kneader, and kneading tends not to occur, and as a result, it is difficult to produce an epoxy resin composition of a molding material.
此外，從初始光反射率的觀點看來，上述氧化鋯(C成分)與無機質充填劑(E成分)之混合比率以體積比計為(C成分)/(E成分)=0.028~1.0為佳，特別理想為0.033~0.50。即，C成分與E成分之混合比率一旦落在上述範圍以外，如體積比過小，有環氧樹脂組成物之初始光反射率降低的傾向，體積比過大則有環氧樹脂組成物之熔融黏度上升而難以捏合的傾向。 Further, from the viewpoint of the initial light reflectance, the mixing ratio of the above zirconia (C component) to the inorganic filler (E component) is preferably (C component) / (E component) = 0.028 to 1.0 by volume ratio. Especially ideal is 0.033~0.50. That is, when the mixing ratio of the C component and the E component falls outside the above range, if the volume ratio is too small, the initial light reflectance of the epoxy resin composition tends to decrease, and when the volume ratio is too large, the melt viscosity of the epoxy resin composition is obtained. The tendency to rise and it is difficult to pinch.
〈其他添加劑〉 <Other Additives>
而且，於本發明之環氧樹脂組成物中，除上述A~E成分以外可因應需求摻混硬化促進劑、脫模劑。更可適宜摻混變性劑(可塑劑)、抗氧化劑、阻燃劑、消泡劑、調平劑、紫外線吸收劑等各種添加劑。 Further, in the epoxy resin composition of the present invention, in addition to the above components A to E, a curing accelerator and a releasing agent may be blended as needed. Further, various additives such as a denaturant (plasticizer), an antioxidant, a flame retardant, an antifoaming agent, a leveling agent, and an ultraviolet absorber can be suitably blended.
就上述硬化促進劑而言，可舉如1,8-二偶氮雙環 [5.4.0]十一烯-7、三伸乙二胺、三-2,4,6-二甲基胺基甲基苯酚、N,N-二甲基苄胺、N,N-二甲基胺基苯、N,N-二甲基胺基環己烷等3級胺類；2-乙基-4-甲咪唑、2-甲咪唑等咪唑類；三苯膦、四氟硼酸四苯基鏻、四苯基硼酸四苯基鏻、四正丁基溴化鏻、四苯基溴化鏻、二甲基磷酸甲基三丁基鏻、四苯基鏻-o,o-二乙基二硫代磷酸鹽、四正丁基鏻-o,o-二乙基二硫代磷酸鹽等磷化合物；三伸乙基二銨．辛基羧酸鹽等4級銨鹽、有機金屬鹽類及該等之衍生物等。該等可單獨使用或可將2種以上合併使用。該等硬化促進劑中，以使用3級胺類、咪唑類、磷化合物為佳。其中，為了獲得著色度少、透明且強韌的硬化物，又以使用磷化合物尤佳。 As the hardening accelerator, there may be mentioned 1,8-diazobicyclo ring. [5.4.0] undecene-7, triamethylenediamine, tris-2,4,6-dimethylaminomethylphenol, N,N-dimethylbenzylamine, N,N-dimethyl 3-aminoamines such as arylaminobenzene, N,N-dimethylaminocyclohexane; imidazoles such as 2-ethyl-4-methylimidazole and 2-methylimidazole; triphenylphosphine and tetraphenyltetrafluoroborate Base, tetraphenylphosphonium tetraphenylborate, tetra-n-butylphosphonium bromide, tetraphenylphosphonium bromide, methyltributylphosphonium dimethyl phosphate, tetraphenylphosphonium-o,o-diethyl Phosphorus compound such as dithiophosphate, tetra-n-butylphosphonium-o, o-diethyldithiophosphate; tri-ethylammonium. a 4-grade ammonium salt such as an octyl carboxylate, an organic metal salt, or the like. These may be used alone or in combination of two or more. Among these hardening accelerators, a tertiary amine, an imidazole or a phosphorus compound is preferably used. Among them, in order to obtain a cured product having a small degree of coloration, transparency, and toughness, it is particularly preferable to use a phosphorus compound.
相對於上述環氧樹脂(A成分)，上述硬化促進劑之含量設定為0.001~8.0重量%為佳，較理想為0.01~3.0重量%。即，其理由在於硬化促進劑之含量一旦過少，可能會無法獲得充分的硬化促進效果；又，硬化促進劑之含量一旦過多，有於獲得之硬化物發生變色的傾向。 The content of the curing accelerator is preferably 0.001 to 8.0% by weight, more preferably 0.01 to 3.0% by weight, based on the epoxy resin (component A). That is, the reason is that once the content of the hardening accelerator is too small, a sufficient hardening promoting effect may not be obtained, and if the content of the hardening accelerator is too large, the obtained cured product tends to be discolored.
以上述脫模劑來說，可使用各種脫模劑，其中又宜使用具有醚鍵之脫模劑，舉例如具備下述通式(2)所示結構式的脫模劑。 In the above-mentioned release agent, various release agents can be used. Among them, a release agent having an ether bond is preferably used, and for example, a release agent having a structural formula represented by the following formula (2) is used.
CH3．(CH3)k．CH2O(CHRm．CHRn．O)x．H…(2) CH 3 . (CH 3 )k. CH 2 O(CHRm.CHRn.O)x. H...(2)
[式(2)中，Rm、Rn為氫原子或一價烷基，兩者可彼此相同或互異。又，k為1~100之正數，x為1~100之正數。] [In the formula (2), Rm and Rn are a hydrogen atom or a monovalent alkyl group, and the two may be the same or different from each other. Also, k is a positive number from 1 to 100, and x is a positive number from 1 to 100. ]
上述式(2)中，Rm、Rn為氫原子或一價烷基，理 想係k為10~50之正數且x為3~30之正數。較理想係Rm及Rn為氫原子，k為28~48之正數且x為5~20之正數。即，其理由在於重複次數k之值若過小，脫模性會降低，又重複次數x之值過小則分散性降低，因而有無法獲得穩定的強度及脫模性的傾向。另一方面，重複次數k之值一旦過大，熔點便會增高，因而有捏合困難而在環氧樹脂組成物之製造步驟中發生困難的傾向，重複次數x之值若過大則有脫模性降低的傾向。 In the above formula (2), Rm and Rn are a hydrogen atom or a monovalent alkyl group. I want to make k a positive number of 10~50 and x is a positive number of 3~30. Preferably, Rm and Rn are hydrogen atoms, k is a positive number from 28 to 48, and x is a positive number from 5 to 20. In other words, the reason is that if the value of the number of repetitions k is too small, the mold release property is lowered, and when the value of the number of repetitions x is too small, the dispersibility is lowered, and thus there is a tendency that stable strength and mold release property cannot be obtained. On the other hand, when the value of the number of repetitions k is too large, the melting point is increased, and thus the kneading is difficult, and the epoxy resin composition tends to be difficult to be produced. If the value of the number of repetitions x is too large, the mold release property is lowered. Propensity.
上述脫模劑之含量以設定為環氧樹脂組成物體整體中佔0.001~3重量%之範圍為佳，設定為0.01~1重量%之範圍較佳。即，其理由在於脫模劑含量過少或過多，有招致硬化物之強度不足而引發脫模性降低的傾向。 The content of the above-mentioned release agent is preferably in the range of 0.001 to 3% by weight based on the total amount of the epoxy resin composition, and is preferably in the range of 0.01 to 1% by weight. That is, the reason is that the content of the releasing agent is too small or too large, and there is a tendency that the strength of the cured product is insufficient and the mold release property is lowered.
以上述變性劑(可塑劑)來說，可舉如聚矽氧類、醇類等。 The above-mentioned denaturing agent (plasticizer) may, for example, be a polyoxane or an alcohol.
就上述抗氧化劑而言，可舉如苯酚系化合物、胺系化合物、有機硫系化合物、膦系化合物等。 The antioxidant may, for example, be a phenol compound, an amine compound, an organic sulfur compound or a phosphine compound.
就上述阻燃劑而言，可舉如氫氧化鎂等金屬氫氧化物、溴系阻燃劑、氮系阻燃劑、磷系阻燃劑等，此外亦可使用三氧化銻等阻燃助劑。 The flame retardant may, for example, be a metal hydroxide such as magnesium hydroxide, a bromine-based flame retardant, a nitrogen-based flame retardant or a phosphorus-based flame retardant, or may be a flame retardant such as antimony trioxide. Agent.
就上述消泡劑來說，可舉如聚矽氧系等習知公知之脫泡劑。 The antifoaming agent may, for example, be a conventionally known defoaming agent such as polyfluorene.
〈環氧樹脂組成物〉 <Epoxy Resin Composition>
本發明之環氧樹脂組成物例如可以下述方法製造。即，將上述A~E成分、還有硬化促進劑及脫模劑、以及可 因應需求使用之各種添加劑予以適宜摻混後，使用捏合機等進行熔融混合，接著將之冷卻固化並進行粉碎，即可製造粉末狀的環氧樹脂組成物。 The epoxy resin composition of the present invention can be produced, for example, by the following method. That is, the above A to E components, as well as a hardening accelerator and a release agent, and The powdery epoxy resin composition can be produced by appropriately blending various additives to be used in a desired manner, followed by melt-mixing using a kneader or the like, followed by cooling and solidifying and pulverizing.
而且，例如藉由將上述所得環氧樹脂組成物予以轉注成形或射出成形而獲得的硬化物來說，在波長450~800nm下，其光反射率在80%以上為佳，較理想在90%以上。而，上限通常為100%。具體上，上述硬化物在波長450nm下之光反射率為85~98%為佳。上述光反射率例如可以下述方法來進行。即，在預定的硬化條件下，例如於175℃×2分鐘成形後進行175℃×3小時的後續硬化來製作厚1mm之環氧樹脂組成物的硬化物，在室溫(25±10℃)下藉由使用分光光度計(例如、日本分光公司製分光光度計V-670)來測定上述範圍內之波長下的上述硬化物之光反射率。 Further, for example, the cured product obtained by transferring or injection-molding the obtained epoxy resin composition has a light reflectance of 80% or more at a wavelength of 450 to 800 nm, preferably 90%. the above. However, the upper limit is usually 100%. Specifically, it is preferable that the cured product has a light reflectance of 85 to 98% at a wavelength of 450 nm. The above light reflectance can be performed, for example, by the following method. That is, under predetermined curing conditions, for example, after 175 ° C × 2 minutes, it is subjected to subsequent hardening at 175 ° C for 3 hours to prepare a cured product of an epoxy resin composition having a thickness of 1 mm at room temperature (25 ± 10 ° C). The light reflectance of the cured product at a wavelength within the above range is measured by using a spectrophotometer (for example, a spectrophotometer V-670 manufactured by JASCO Corporation).
〈光半導體裝置〉 <Optical semiconductor device>
使用本發明之環氧樹脂組成物形成的光半導體裝置例如可以下述方法製造。即，將金屬引線框設置於轉注成形機之模具內，並使用上述環氧樹脂組成物藉由轉注成形來形成反射器。如此一來，便可製作以包圍光半導體元件搭載區周圍的方式形成環狀反射器而成的光半導體裝置用金屬引線框。接著，將光半導體元件搭載於上述反射器內部之金屬引線框上的光半導體元件搭載區，使用接合線將光半導體元件及金屬引線框予以電連接。然後使用聚矽氧樹脂等將含有上述光半導體元件之反射器的內側區域進行樹脂密封而形成密封樹脂層。以上述方法可製作例如圖1所示 之立體狀(杯型)的光半導體裝置。該光半導體裝置如前述係採取下述構成：於第1板部1及第2板部2所構成之金屬引線框的第2板部2上搭載有光半導體元件3，並以包圍上述光半導體元件3周圍的方式形成有本發明之環氧樹脂組成物所構成的光反射用反射器4。而且，於以上述金屬引線框與反射器4之內周面形成的凹部5形成有密封樹脂層6，該密封樹脂層6係用以密封光半導體元件3且具有透明性。於該密封樹脂層6中因應需求含有螢光體。圖1中，7、8係用以將金屬引線框及光半導體元件3予以電連接的接合線。 The optical semiconductor device formed using the epoxy resin composition of the present invention can be produced, for example, by the following method. That is, the metal lead frame is placed in a mold of a transfer molding machine, and a reflector is formed by transfer molding using the above epoxy resin composition. In this way, a metal lead frame for an optical semiconductor device in which an annular reflector is formed to surround the periphery of the mounting region of the optical semiconductor element can be produced. Next, the optical semiconductor element is mounted on the optical semiconductor element mounting region on the metal lead frame inside the reflector, and the optical semiconductor element and the metal lead frame are electrically connected by using a bonding wire. Then, the inner region of the reflector including the above-described optical semiconductor element is resin-sealed using a polyoxyxylene resin or the like to form a sealing resin layer. In the above method, for example, as shown in FIG. 1, A three-dimensional (cup type) optical semiconductor device. In the above-described optical semiconductor device, the optical semiconductor element 3 is mounted on the second plate portion 2 of the metal lead frame formed by the first plate portion 1 and the second plate portion 2, and surrounds the optical semiconductor. A light reflection reflector 4 composed of the epoxy resin composition of the present invention is formed around the element 3. Further, a sealing resin layer 6 for sealing the optical semiconductor element 3 and having transparency is formed in the concave portion 5 formed on the inner circumferential surface of the metal lead frame and the reflector 4. A phosphor is contained in the sealing resin layer 6 as needed. In Fig. 1, 7, 8 are bonding wires for electrically connecting the metal lead frame and the optical semiconductor element 3.
而，在本發明中亦可使用各種基板來替代上述圖1之金屬引線框。就上述各種基板來說，可舉如有機基板、無機基板、可撓印刷基板等。又，亦可藉由射出成形來替代上述轉注成形，以形成反射器。 However, various substrates may be used in the present invention instead of the metal lead frame of FIG. 1 described above. Examples of the various substrates described above include an organic substrate, an inorganic substrate, and a flexible printed substrate. Alternatively, the above-described transfer molding may be replaced by injection molding to form a reflector.
又，就與上述構成有所不同的光半導體裝置來說，可舉如使用板狀的光半導體裝置用引線框，例如圖2及圖3(圖2之X-X’箭頭截面圖)中所示之光半導體裝置。即，該光半導體裝置係採用下述構成：於彼此設有間隔配置之金屬引線框10厚度方向之一面的預定位置上分別搭載光半導體元件3，並於上述金屬引線框10間之間隙形成有本發明之環氧樹脂組成物所構成的光反射用反射器11。又，如圖3所示，於金屬引線框10之間隙多處形成有反射器11，該反射器11係充填本發明之環氧樹脂組成物並使其硬化而形成。而，在圖2及圖3中，12係用以將上述光半導體元件3及金屬引線框10予以電連接之接合線。此種光半導體裝置係將上 述金屬引線框10設置於轉注成形機之模具內，並藉由轉注成形將環氧樹脂組成物充填於凹部且使其硬化而分別形成反射器11，該凹部係形成於設有間隔配置之金屬引線框10之間隙及金屬引線框10中與光半導體元件3搭載面為相反之面。接著，將光半導體元件3搭載於上述金屬引線框10之預定位置的光半導體元件搭載區後，使用接合線12將光半導體元件3及金屬引線框10予以電連接。以上述方法即可製作圖2及圖3所示之光半導體裝置。 In addition, as for the optical semiconductor device which is different from the above-described configuration, a lead frame for a plate-shaped optical semiconductor device can be used, for example, in FIGS. 2 and 3 (X-X' arrow cross-sectional view of FIG. 2). A light semiconductor device. In other words, the optical semiconductor device has a configuration in which the optical semiconductor element 3 is mounted at a predetermined position on one surface in the thickness direction of the metal lead frame 10 which is disposed at intervals, and is formed in a gap between the metal lead frames 10 The light reflection reflector 11 composed of the epoxy resin composition of the present invention. Further, as shown in FIG. 3, a reflector 11 is formed at a plurality of places in the gap of the metal lead frame 10, and the reflector 11 is formed by filling and hardening the epoxy resin composition of the present invention. In FIGS. 2 and 3, reference numeral 12 denotes a bonding wire for electrically connecting the optical semiconductor element 3 and the metal lead frame 10. Such an optical semiconductor device will be on The metal lead frame 10 is disposed in a mold of a transfer molding machine, and is filled with a resin composition by a transfer molding to be hardened to form a reflector 11 which is formed in a metal provided with a space. The gap between the lead frame 10 and the metal lead frame 10 are opposite to the surface on which the optical semiconductor element 3 is mounted. Next, the optical semiconductor element 3 is mounted on the optical semiconductor element mounting region at a predetermined position of the metal lead frame 10, and then the optical semiconductor element 3 and the metal lead frame 10 are electrically connected by the bonding wires 12. The optical semiconductor device shown in Figs. 2 and 3 can be produced by the above method.
〈密封型光半導體元件〉 <Sealed Optical Semiconductor Element>
此外，於圖4顯示將本發明之環氧樹脂組成物作為反射器形成材料使用的密封型光半導體元件。即，該密封型光半導體元件係採取下述構成：於光半導體元件3之側面全部形成有本發明之環氧樹脂組成物所構成之光反射用反射器15，並進一步以密封層16被覆上述光半導體元件3之上部(發光面或受光面)。圖中，17為連接用電極(凸塊)。又，上述密封層16可由環氧樹脂及聚矽氧樹脂、或玻璃及陶瓷等無機材料所形成，且於上述密封層16中可含有螢光體亦可未摻混螢光體。 Further, a sealed optical semiconductor element in which the epoxy resin composition of the present invention is used as a reflector forming material is shown in FIG. In other words, the sealed optical-semiconductor element has a configuration in which the light-reflecting reflector 15 composed of the epoxy resin composition of the present invention is formed on all sides of the optical-semiconductor element 3, and the sealing layer 16 is further coated with the sealing layer 16 described above. The upper portion (light emitting surface or light receiving surface) of the optical semiconductor element 3. In the figure, 17 is an electrode for connection (bump). Further, the sealing layer 16 may be formed of an epoxy resin, a polyoxymethylene resin, or an inorganic material such as glass or ceramic, and the sealing layer 16 may or may not contain a phosphor.
此種密封型光半導體元件例如可以下述方法製造。即，於切割膠帶等黏著面上，在已將設置於與其發光面為相反面之連接用電極(凸塊)17埋入上述膠帶面之狀態下，設置一定間隔來配置倒裝晶片型光半導體(發光)元件3(例如藍色LED晶片等)。接著，利用壓縮成形機、轉注成形機或射出成形機，使用本發明之環氧樹脂組成物包埋上 述光半導體元件3之側面全部以及發光面。然後藉由乾燥機等進行後續加熱，藉此使上述環氧樹脂組成物之熱硬化反應完成，而於光半導體元件3之側面全部形成本發明之環氧樹脂組成物所構成的光反射用反射器15。接著，將形成於發光面上的反射器15研磨除去，使發光面顯露，並於該顯露之發光面上，在以屏障材包圍周圍的狀態下澆注聚矽氧樹脂等密封材，或將片狀之密封材黏貼於發光面而形成密封層16。接下來，使用刀片切割機將光半導體元件3間之中央線彼此切割而使其單片化成一個個的元件。然後，將切割膠帶擴張拉伸使黏著性減低，以使切割膠帶上形成有反射器15的密封型光半導體元件3彼此完全分離而單片化，藉此可製造圖4所示之密封型光半導體元件3。 Such a sealed optical semiconductor element can be produced, for example, by the following method. In other words, in a state in which the connection electrode (bump) 17 provided on the opposite side of the light-emitting surface is buried in the tape surface, the flip-chip type optical semiconductor is placed at a predetermined interval. (Light-emitting) element 3 (for example, a blue LED wafer or the like). Next, the epoxy resin composition of the present invention is embedded by a compression molding machine, a transfer molding machine, or an injection molding machine. All of the side faces of the optical semiconductor element 3 and the light-emitting surface are described. Then, by subsequent heating by a dryer or the like, the thermosetting reaction of the epoxy resin composition is completed, and the light reflection reflection formed by the epoxy resin composition of the present invention is formed on all sides of the optical semiconductor element 3. Device 15. Next, the reflector 15 formed on the light-emitting surface is polished and removed to expose the light-emitting surface, and a sealing material such as polyoxymethylene resin is poured onto the exposed light-emitting surface while surrounding the barrier material, or the sheet is molded. The sealing material is adhered to the light emitting surface to form the sealing layer 16. Next, the center line between the optical semiconductor elements 3 is cut from each other using a blade cutter to be singulated into individual elements. Then, the dicing tape is stretched and stretched to reduce the adhesiveness, so that the sealed optical semiconductor elements 3 on which the reflector 15 is formed on the dicing tape are completely separated from each other and singulated, whereby the sealed light shown in Fig. 4 can be manufactured. Semiconductor element 3.
就使用以此方法製得之密封型光半導體元件3之構成的光半導體裝置來說，可舉具備下述構成的光半導體裝置為例：於配線電路基板之形成有電路的預定位置上，藉由上述光半導體元件3之連接用電極17進行搭載而形成。 An optical semiconductor device having a configuration in which the sealed optical semiconductor device 3 is obtained by the above-described method is exemplified by an optical semiconductor device having a configuration in which a predetermined position of a circuit board on which a circuit is formed is used. It is formed by mounting the connection electrode 17 of the optical semiconductor element 3 described above.
接下來，針對實施例與比較例合併加以說明。惟，本發明不受該等實施例限定。 Next, a description will be given of a combination of an embodiment and a comparative example. However, the invention is not limited by the examples.
首先，在環氧樹脂組成物之製作前，先準備下述所示各成分。 First, each component shown below was prepared before the preparation of the epoxy resin composition.
[環氧樹脂] [Epoxy resin]
三聚異氰酸三環氧丙酯(環氧當量100) Tripolyglycidyl isocyanate (epoxy equivalent 100)
[硬化劑b1] [hardener b1]
4-甲基六氫酞酸酐(x)與六氫酞酸酐(y)之混合物(液體；混合重量比x/y=70/30)(新日本理化公司製，RIKACID MH-700) a mixture of 4-methylhexahydrophthalic anhydride (x) and hexahydrophthalic anhydride (y) (liquid; mixing weight ratio x/y = 70/30) (RIKACID MH-700, manufactured by Nippon Chemical and Chemical Co., Ltd.)
[硬化劑b2] [hardener b2]
1,2,3,6-四氫酞酸酐(固體)(新日本理化公司製，RIKACID TH-PA) 1,2,3,6-tetrahydrophthalic anhydride (solid) (manufactured by Nippon Chemical and Chemical Co., Ltd., RIKACID TH-PA)
[氧化鋯c1] [Zirconium oxide c1]
第一稀元素化學工業公司製，SG氧化鋯、單斜晶、折射率2.1、平均粒徑4.3μm First rare element chemical industry company, SG zirconia, monoclinic crystal, refractive index 2.1, average particle size 4.3μm
[氧化鋯c2] [zirconia c2]
第一稀元素化學工業公司製，UEP氧化鋯、單斜晶、折射率2.1、平均粒徑0.5μm First rare element chemical industry company, UEP zirconia, monoclinic crystal, refractive index 2.1, average particle size 0.5μm
[氧化鈦] [titanium oxide]
堺化學工業公司製，FTR-700、金紅石型、單一粒徑0.2μm Made by 堺Chemical Industries, Inc., FTR-700, rutile, single particle size 0.2μm
[矽烷系化合物d1] [decane compound d1]
3-環氧丙氧基丙基三甲氧矽烷(信越化學工業公司製，KBM-403) 3-glycidoxypropyltrimethoxy decane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403)
[矽烷系化合物d2] [decane compound d2]
3-甲基丙烯醯氧基丙基三甲氧矽烷(信越化學工業公司製，KBM-503) 3-Methyl propylene methoxy propyl trimethoxy decane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-503)
[矽烷系化合物d3] [decane compound d3]
苯基三甲氧矽烷(信越化學工業公司製，KBM-103) Phenyltrimethoxy decane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-103)
[矽烷系化合物d4] [decane compound d4]
乙烯基三甲氧矽烷(東麗．道康寧公司製，SZ6300) Vinyl trimethoxy decane (made by Toray Dow Corning, SZ6300)
[無機質充填劑] [Inorganic Filler]
熔融球狀二氧化矽粉末(平均粒徑20μm) Melted spherical cerium oxide powder (average particle size 20 μm)
[硬化促進劑] [hardening accelerator]
二甲基磷酸甲基三丁基鏻(日本化學工業公司製、HISHICOLIN PX-4MP) Methyltributylphosphonium dimethyl phosphate (manufactured by Nippon Chemical Industry Co., Ltd., HISHICOLIN PX-4MP)
[內部脫模劑] [internal release agent]
C(碳數)>14、乙氧化醇/乙烯均聚物(丸菱油化工業公司製、UNT-750) C (carbon number)>14, ethoxylated alcohol/ethylene homopolymer (manufactured by Maruishi Oil Chemical Industry Co., Ltd., UNT-750)
[實施例1~8、比較例1~5] [Examples 1 to 8 and Comparative Examples 1 to 5]
將後述表1~表2所示之各成分以同表所示比率加以摻混，以捏合機進行熔融捏合(溫度100~130℃)並於熟成後，冷卻至室溫(25℃)並進行粉碎而製出目的之粉末狀的環氧樹脂組成物。 Each component shown in Tables 1 to 2 described later was blended at a ratio shown in the same table, and melt-kneaded (temperature: 100 to 130 ° C) in a kneader, and after aging, it was cooled to room temperature (25 ° C) and carried out. The powdery epoxy resin composition of the object is produced by pulverization.
使用以上述方法所製得之實施例及比較例的環氧樹脂組成物，依照下述方法進行各種特定評估[初始光反射率、長期耐光性、玻璃轉移溫度]之測定。其結果合併顯示於後述表1~表2。 Using the epoxy resin compositions of the examples and the comparative examples obtained by the above methods, various specific evaluations [initial light reflectance, long-term light resistance, and glass transition temperature] were measured in accordance with the following methods. The results are combined and shown in Tables 1 to 2 described later.
[初始光反射率] [Initial light reflectance]
使用上述各環氧樹脂組成物，在預定的硬化條件(條件：175℃×2分鐘之成形+175℃×3小時硬化)下製作厚1mm之試驗片，並使用該試驗片(硬化物)測定室溫(25℃)下的光反射率。而，作為測定裝置係使用日本分光公司製之分光光度計V-670，在室溫(25℃)下測定波長450nm下的光反射 率。 Using each of the above epoxy resin compositions, a test piece having a thickness of 1 mm was prepared under predetermined curing conditions (condition: 175 ° C × 2 minutes of molding + 175 ° C × 3 hours of hardening), and the test piece (cured product) was used for measurement. Light reflectance at room temperature (25 ° C). Further, as a measuring device, a spectrophotometer V-670 manufactured by JASCO Corporation was used, and light reflection at a wavelength of 450 nm was measured at room temperature (25 ° C). rate.
[長期耐光性] [Long-term light resistance]
使用以與上述同樣的方式所製作之各試驗片，在室溫(25℃)下測定波長600nm下的光反射率。其後，在以110℃之熱板加熱其試驗片之狀態下，透過g線(436nm)帶通濾波器照射強度1W/cm2之高壓水銀燈之光15分鐘後，以與上述同樣的方式測定波長600nm下的光反射率(加速試驗)。然後算出上述加速試驗前後之光反射率的降低度(光照射後之光反射率-光照射前之光反射率)。而，於測定係與上述同樣地使用日本分光公司製之分光光度計V-670。 The light reflectance at a wavelength of 600 nm was measured at room temperature (25 ° C) using each test piece prepared in the same manner as above. Thereafter, the test piece was heated by a hot plate at 110 ° C, and the light of a high-pressure mercury lamp having a strength of 1 W/cm 2 was irradiated through a g-line (436 nm) band pass filter for 15 minutes, and then measured in the same manner as above. Light reflectance at a wavelength of 600 nm (acceleration test). Then, the degree of decrease in the light reflectance before and after the above-described acceleration test (light reflectance after light irradiation - light reflectance before light irradiation) was calculated. Further, in the measurement system, a spectrophotometer V-670 manufactured by JASCO Corporation was used in the same manner as described above.
[玻璃轉移溫度] [glass transition temperature]
使用上述各環氧樹脂組成物，在預定的硬化條件(條件：175℃×2分鐘之成形+175℃×3小時硬化)下製作長20mm之角柱狀試驗片，並以熱機械分析裝置[島津製作所公司製、TMA-50]進行測定。 Using each of the above epoxy resin compositions, a columnar test piece having a length of 20 mm was produced under predetermined curing conditions (condition: 175 ° C × 2 minutes of formation + 175 ° C × 3 hours of hardening), and a thermomechanical analysis apparatus [Shimadzu The company's company, TMA-50, was used for the measurement.
[表1]
[表2]
從上述結果可知，以液狀硬化劑作為主成分且摻 混氧化鋯及特定量之矽烷系化合物而成的實施例成品不僅獲得高的初始光反射率，且關於長期耐光性亦獲得優異的結果。而且，具有高玻璃轉移溫度。 From the above results, it is known that a liquid hardener is used as a main component and is doped. The finished article obtained by mixing zirconia and a specific amount of a decane-based compound not only obtained high initial light reflectance, but also obtained excellent results with respect to long-term light resistance. Moreover, it has a high glass transition temperature.
相對於此，未使用矽烷系化合物之比較例1成品的結果則為初始光反射率很差。又，使用過多矽烷系化合物的比較例2成品於初始光反射率及長期耐光性方面雖獲得與實施例略同等程度之評估結果，但玻璃轉移溫度極低。而且，使用固體硬化劑之比較例3成品的結果為初始光反射率及長期耐光性很差。此外，使用氧化鈦作為白色顏料的比較例4及5成品於初始光反射率方面雖獲得與實施例略同等程度之評估結果，但兩者的長期耐光性都很差，其中又以使用固體硬化劑之比較例5成品玻璃轉移溫度較低。 On the other hand, as a result of the finished product of Comparative Example 1 in which no decane-based compound was used, the initial light reflectance was poor. Further, in the comparative example 2 using an excessive amount of the decane-based compound, the results of the evaluation of the initial light reflectance and the long-term light resistance were slightly the same as those of the examples, but the glass transition temperature was extremely low. Further, as a result of the finished product of Comparative Example 3 using a solid hardener, the initial light reflectance and the long-term light resistance were poor. Further, Comparative Examples 4 and 5 using titanium oxide as a white pigment obtained the same evaluation results as the examples in terms of initial light reflectance, but the long-term light resistance of both was poor, and solid hardening was used. Comparative Example 5 of the agent The transfer temperature of the finished glass was low.
[光半導體(發光)裝置之製作] [Production of Optical Semiconductor (Light Emitting) Device]
接下來，使用將上述實施例成品之粉末製錠而成之錠狀的環氧樹脂組成物來製造圖1所示構成的光半導體(發光)裝置。即，將由銅(鍍銀)製之第1板部1及第2板部2所構成的金屬引線框設置於轉注成形機之模具內，使用上述環氧樹脂組成物進行轉注成形(條件：175℃×2分鐘之成形+175℃×3小時硬化)而如圖1所示於金屬引線框之預定位置上形成有反射器4。接下來搭載光半導體(發光)元件(大小：0.5mm×0.5mm)3，將該光半導體元件3及上述金屬引線框以接合線7、8進行電連接而製造出具備反射器4、金屬引線框及光半導體元件3之組件。 Next, an optical semiconductor (light-emitting) device having the structure shown in Fig. 1 was produced by using an ingot-shaped epoxy resin composition obtained by ingoting the powder of the finished product of the above embodiment. In other words, the metal lead frame made of the first plate portion 1 and the second plate portion 2 made of copper (silver plating) is placed in a mold of a transfer molding machine, and the epoxy resin composition is used for transfer molding (condition: 175) The formation of °C × 2 minutes + 175 ° C × 3 hours hardening) and the reflector 4 is formed at a predetermined position of the metal lead frame as shown in FIG. Next, an optical semiconductor (light-emitting) element (size: 0.5 mm × 0.5 mm) 3 is mounted, and the optical semiconductor element 3 and the metal lead frame are electrically connected by bonding wires 7 and 8, thereby manufacturing a reflector 4 and a metal lead. The frame and the components of the optical semiconductor component 3.
接著將聚矽氧樹脂(信越聚矽氧公司製、 KER-2500)充填至由上述金屬引線框及反射器4之內周面所形成的凹部5，將上述光半導體元件3進行樹脂密封(成形條件：150℃×4小時)而形成透明的密封樹脂層6，並依各反射器以切割進行單片化而製作出圖1所示之光半導體(發光)裝置。所得光半導體(發光)裝置具備高初始光反射率以及長期耐光性優異的反射器4，可製出具備高可靠性的良好成品。 Next, the polyoxyn resin (manufactured by Shin-Etsu Chemical Co., Ltd., KER-2500) is filled in the recessed portion 5 formed by the inner peripheral surface of the metal lead frame and the reflector 4, and the optical semiconductor element 3 is resin-sealed (forming conditions: 150 ° C × 4 hours) to form a transparent sealing resin. The layer 6 was diced by dicing according to each reflector to fabricate the optical semiconductor (light-emitting) device shown in Fig. 1. The obtained photo-semiconductor (light-emitting) device includes the reflector 4 having high initial light reflectance and long-term light resistance, and can produce a good finished product having high reliability.
又，作為前述圖2及圖3所示光半導體裝置、及圖4所示密封型光半導體元件中的反射器11、15形成材料係使用將上述實施例品之粉末予以製錠而成之錠狀環氧樹脂組成物，依照前述製造方法製出圖2及圖3所示光半導體裝置及圖4所示密封型光半導體元件。所得光半導體裝置與上述同樣地可製出具備高可靠性的良好成品。另一方面，藉由上述密封型光半導體元件之連接用電極，將上述所得密封型光半導體元件搭載於形成有配線電路基板之電路的預定位置上來製作光半導體裝置。所得光半導體裝置與上述同樣地可製出具備高可靠性的良好成品。 Further, as the material for forming the reflectors 11 and 15 in the optical semiconductor device shown in Figs. 2 and 3 and the sealed optical semiconductor device shown in Fig. 4, an ingot obtained by molding the powder of the above-mentioned example product is used. In the epoxy resin composition, the optical semiconductor device shown in Figs. 2 and 3 and the sealed optical semiconductor device shown in Fig. 4 were produced in accordance with the above-described manufacturing method. The obtained optical semiconductor device can produce a good finished product having high reliability in the same manner as described above. On the other hand, the obtained sealing type optical semiconductor element is mounted on a predetermined position of a circuit on which the printed circuit board is formed by the connection electrode of the sealed optical semiconductor element, thereby fabricating an optical semiconductor device. The obtained optical semiconductor device can produce a good finished product having high reliability in the same manner as described above.
上述實施例中雖顯示了本發明之具體形態，但上述實施例僅為例示，非作限定解釋者。對於熟知此項技藝之人士為明顯可知之各種變形均設想在本發明範圍內。 The embodiments of the present invention have been described in the above embodiments, but the above embodiments are merely illustrative and not intended to be limiting. Various modifications that are apparent to those skilled in the art are contemplated as being within the scope of the invention.
本發明之光半導體裝置用環氧樹脂組成物可有效作為反射器之形成材料使用，該反射器係用以使從內藏於光半導體裝置之光半導體元件發出之光反射。 The epoxy resin composition for an optical semiconductor device of the present invention can be effectively used as a material for forming a reflector for reflecting light emitted from an optical semiconductor element built in an optical semiconductor device.
1‧‧‧第1板部 1‧‧‧1st Board
2‧‧‧第2板部 2‧‧‧2nd Board
3‧‧‧光半導體元件 3‧‧‧Optical semiconductor components
4‧‧‧反射器 4‧‧‧ reflector
5‧‧‧凹部 5‧‧‧ recess
6‧‧‧密封樹脂層 6‧‧‧ sealing resin layer
7、8‧‧‧接合線 7,8‧‧‧bonding line
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| TWI758594B (en) * | 2018-03-28 | 2022-03-21 | 日商東麗工程股份有限公司 | Transfer substrate, mounting method using the same, and manufacturing method of image display device |
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| JP7567317B2 (en) | 2020-09-24 | 2024-10-16 | 株式会社レゾナック | Light-reflecting thermosetting resin composition, optical semiconductor element mounting substrate, and optical semiconductor device |
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| JP4873963B2 (en) * | 2006-02-27 | 2012-02-08 | 京セラ株式会社 | LIGHT EMITTING DEVICE AND LIGHTING DEVICE USING THE SAME |
| KR100911168B1 (en) * | 2007-12-31 | 2009-08-06 | 제일모직주식회사 | Epoxy resin composition for encapsulating semiconductor device?and semiconductor device using the?same |
| JP2010189553A (en) * | 2009-02-18 | 2010-09-02 | Hitachi Chem Co Ltd | Thermosetting resin composition for light reflection, substrate for mounting optical semiconductor element, manufacturing method thereof, and optical semiconductor apparatus |
| JP5721969B2 (en) | 2010-06-11 | 2015-05-20 | 日東電工株式会社 | Epoxy resin composition for reflector of optical semiconductor device, lead frame for optical semiconductor device obtained using the same, and optical semiconductor device |
| JP5745319B2 (en) * | 2011-04-14 | 2015-07-08 | 日東電工株式会社 | Fluorescent reflection sheet and method for manufacturing light emitting diode device |
| JP5764423B2 (en) * | 2011-08-02 | 2015-08-19 | 日東電工株式会社 | Epoxy resin composition for optical semiconductor device, lead frame for optical semiconductor device or substrate for optical semiconductor device obtained by using the same, and optical semiconductor device |
| JP2013110199A (en) * | 2011-11-18 | 2013-06-06 | Citizen Electronics Co Ltd | Led light-emitting device |
| JP5865038B2 (en) * | 2011-11-30 | 2016-02-17 | 日東電工株式会社 | ELECTRODE CONNECTION BOARD, ITS MANUFACTURING METHOD, AND LIGHT EMITTING DIODE DEVICE |
| JP5970835B2 (en) * | 2012-02-02 | 2016-08-17 | 大日本印刷株式会社 | Lead frame member, lead frame member with resin, and semiconductor device |
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