JP6096090B2 - Thermosetting resin composition, optical semiconductor element mounting substrate using the same, method for producing the same, and optical semiconductor device - Google Patents
Thermosetting resin composition, optical semiconductor element mounting substrate using the same, method for producing the same, and optical semiconductor device Download PDFInfo
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- JP6096090B2 JP6096090B2 JP2013198253A JP2013198253A JP6096090B2 JP 6096090 B2 JP6096090 B2 JP 6096090B2 JP 2013198253 A JP2013198253 A JP 2013198253A JP 2013198253 A JP2013198253 A JP 2013198253A JP 6096090 B2 JP6096090 B2 JP 6096090B2
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- Prior art keywords
- optical semiconductor
- resin composition
- thermosetting resin
- semiconductor element
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- 239000011342 resin composition Substances 0.000 title claims description 87
- 229920001187 thermosetting polymer Polymers 0.000 title claims description 86
- 239000004065 semiconductor Substances 0.000 title claims description 72
- 230000003287 optical effect Effects 0.000 title claims description 68
- 239000000758 substrate Substances 0.000 title claims description 27
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 229920005989 resin Polymers 0.000 claims description 40
- 239000011347 resin Substances 0.000 claims description 40
- -1 tetrafluoroborate Chemical compound 0.000 claims description 38
- 239000003822 epoxy resin Substances 0.000 claims description 37
- 229920000647 polyepoxide Polymers 0.000 claims description 37
- 239000003054 catalyst Substances 0.000 claims description 34
- 239000003795 chemical substances by application Substances 0.000 claims description 34
- 238000004898 kneading Methods 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 20
- 239000012463 white pigment Substances 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 14
- 230000002093 peripheral effect Effects 0.000 claims description 11
- 238000007789 sealing Methods 0.000 claims description 10
- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical group CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000001721 transfer moulding Methods 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 8
- 125000003700 epoxy group Chemical group 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 229910000410 antimony oxide Inorganic materials 0.000 claims description 5
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 5
- 125000004018 acid anhydride group Chemical group 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 3
- 150000001642 boronic acid derivatives Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 description 23
- 229910052751 metal Inorganic materials 0.000 description 21
- 239000002184 metal Substances 0.000 description 21
- 238000002844 melting Methods 0.000 description 16
- 230000008018 melting Effects 0.000 description 16
- 239000002994 raw material Substances 0.000 description 16
- 125000001424 substituent group Chemical group 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 15
- 239000011256 inorganic filler Substances 0.000 description 14
- 229910003475 inorganic filler Inorganic materials 0.000 description 14
- 238000002156 mixing Methods 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 125000003118 aryl group Chemical group 0.000 description 9
- 150000002736 metal compounds Chemical class 0.000 description 9
- 238000000465 moulding Methods 0.000 description 9
- 239000007822 coupling agent Substances 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical class OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 6
- 238000007747 plating Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000007983 Tris buffer Substances 0.000 description 5
- 150000008065 acid anhydrides Chemical class 0.000 description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical group CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 125000003710 aryl alkyl group Chemical group 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 239000013522 chelant Chemical group 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 150000002460 imidazoles Chemical class 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 150000004010 onium ions Chemical class 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 150000004714 phosphonium salts Chemical class 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 125000005415 substituted alkoxy group Chemical group 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- 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 3
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 3
- 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 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical class CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000004843 novolac epoxy resin Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 2
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 2
- UVYLEXYRTBDZNM-UHFFFAOYSA-N 4,4-diethyloxane-2,6-dione Chemical compound CCC1(CC)CC(=O)OC(=O)C1 UVYLEXYRTBDZNM-UHFFFAOYSA-N 0.000 description 2
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- MMNYLVQQZFXFBS-UHFFFAOYSA-N carboxy trifluoromethanesulfonate Chemical compound OC(=O)OS(=O)(=O)C(F)(F)F MMNYLVQQZFXFBS-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 150000007973 cyanuric acids Chemical class 0.000 description 2
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 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 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 229910052752 metalloid Inorganic materials 0.000 description 2
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 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
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-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
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- ODGCZQFTJDEYNI-UHFFFAOYSA-N 2-methylcyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1(C)C=CCCC1C(O)=O ODGCZQFTJDEYNI-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
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- IJHKMDHEGBKCLG-UHFFFAOYSA-N CC1(CC(=O)OC(C1)=O)C.C1(CCCC(=O)O1)=O Chemical compound CC1(CC(=O)OC(C1)=O)C.C1(CCCC(=O)O1)=O IJHKMDHEGBKCLG-UHFFFAOYSA-N 0.000 description 1
- KKUKTXOBAWVSHC-UHFFFAOYSA-N Dimethylphosphate Chemical compound COP(O)(=O)OC KKUKTXOBAWVSHC-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 101000832669 Rattus norvegicus Probable alcohol sulfotransferase Proteins 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- PXMYOKGECYPCMO-UHFFFAOYSA-J [F-].[F-].[F-].[F-].C(C)[P+](CCCCCCCCCCCC)(CC)CC.C(C)[P+](CC)(CC)CCCCCCCCCCCC.C(C)[P+](CC)(CC)CCCCCCCCCCCC.C(C)[P+](CC)(CC)CCCCCCCCCCCC Chemical compound [F-].[F-].[F-].[F-].C(C)[P+](CCCCCCCCCCCC)(CC)CC.C(C)[P+](CC)(CC)CCCCCCCCCCCC.C(C)[P+](CC)(CC)CCCCCCCCCCCC.C(C)[P+](CC)(CC)CCCCCCCCCCCC PXMYOKGECYPCMO-UHFFFAOYSA-J 0.000 description 1
- JGRKMXAWRZAUMG-UHFFFAOYSA-J [F-].[F-].[F-].[F-].C(CC)[P+](CCCCCCCCCCCC)(CCC)CCC.C(CC)[P+](CCC)(CCC)CCCCCCCCCCCC.C(CC)[P+](CCC)(CCC)CCCCCCCCCCCC.C(CC)[P+](CCC)(CCC)CCCCCCCCCCCC Chemical compound [F-].[F-].[F-].[F-].C(CC)[P+](CCCCCCCCCCCC)(CCC)CCC.C(CC)[P+](CCC)(CCC)CCCCCCCCCCCC.C(CC)[P+](CCC)(CCC)CCCCCCCCCCCC.C(CC)[P+](CCC)(CCC)CCCCCCCCCCCC JGRKMXAWRZAUMG-UHFFFAOYSA-J 0.000 description 1
- WSDYKLXDCSSLME-UHFFFAOYSA-J [F-].[F-].[F-].[F-].C(CC)[P+](CCCCCCCCCCCCCCCC)(CCC)CCC.C(CC)[P+](CCC)(CCC)CCCCCCCCCCCCCCCC.C(CC)[P+](CCC)(CCC)CCCCCCCCCCCCCCCC.C(CC)[P+](CCC)(CCC)CCCCCCCCCCCCCCCC Chemical compound [F-].[F-].[F-].[F-].C(CC)[P+](CCCCCCCCCCCCCCCC)(CCC)CCC.C(CC)[P+](CCC)(CCC)CCCCCCCCCCCCCCCC.C(CC)[P+](CCC)(CCC)CCCCCCCCCCCCCCCC.C(CC)[P+](CCC)(CCC)CCCCCCCCCCCCCCCC WSDYKLXDCSSLME-UHFFFAOYSA-J 0.000 description 1
- JAAACXYTSIBDAP-UHFFFAOYSA-J [F-].[F-].[F-].[F-].C(CCC)[P+](CCCCCCCC)(CCCC)CCCC.C(CCC)[P+](CCCC)(CCCC)CCCCCCCC.C(CCC)[P+](CCCC)(CCCC)CCCCCCCC.C(CCC)[P+](CCCC)(CCCC)CCCCCCCC Chemical compound [F-].[F-].[F-].[F-].C(CCC)[P+](CCCCCCCC)(CCCC)CCCC.C(CCC)[P+](CCCC)(CCCC)CCCCCCCC.C(CCC)[P+](CCCC)(CCCC)CCCCCCCC.C(CCC)[P+](CCCC)(CCCC)CCCCCCCC JAAACXYTSIBDAP-UHFFFAOYSA-J 0.000 description 1
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Images
Classifications
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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
- H01L2224/10—Bump connectors; Manufacturing methods related thereto
- H01L2224/15—Structure, shape, material or disposition of the bump connectors after the connecting process
- H01L2224/16—Structure, shape, material or disposition of the bump connectors after the connecting process of an individual bump connector
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/10—Bump connectors; Manufacturing methods related thereto
- H01L2224/15—Structure, shape, material or disposition of the bump connectors after the connecting process
- H01L2224/16—Structure, shape, material or disposition of the bump connectors after the connecting process of an individual bump connector
- H01L2224/161—Disposition
- H01L2224/16151—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/16221—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/16245—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
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- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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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
- H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
- H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
- H01L2224/321—Disposition
- H01L2224/32151—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/32221—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/32245—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
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- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/481—Disposition
- H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/48245—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
- H01L2224/48247—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a bond pad of the item
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
- H01L24/73—Means for bonding being of different types provided for in two or more of groups H01L24/10, H01L24/18, H01L24/26, H01L24/34, H01L24/42, H01L24/50, H01L24/63, H01L24/71
Description
本発明は、光反射部材を形成するために用いられる熱硬化性樹脂組成物、これを用いた光半導体素子搭載用基板及びその製造方法並びに光半導体装置に関する。 The present invention relates to a thermosetting resin composition used for forming a light reflecting member, an optical semiconductor element mounting substrate using the same, a method for manufacturing the same, and an optical semiconductor device.
一般に、光半導体装置は、ＬＥＤ（Ｌｉｇｈｔ Ｅｍｉｔｔｉｎｇ Ｄｉｏｄｅ：発光ダイオード）などの光半導体素子と蛍光体を組み合わせて構成される。光半導体装置は高エネルギー効率、長寿命などの利点を有することから、近年、屋外用ディスプレイ、携帯液晶バックライト、車載用途などにおいてその需要が拡大している。 In general, an optical semiconductor device is configured by combining an optical semiconductor element such as an LED (Light Emitting Diode) and a phosphor. Since the optical semiconductor device has advantages such as high energy efficiency and long life, the demand for the display for outdoor use, portable liquid crystal backlight, in-vehicle use and the like has been increasing in recent years.
光半導体素子搭載用基板を構成する光反射部材は、硬化後の光反射特性に優れた熱硬化性樹脂組成物によって形成することができる。光反射部材は、光反射とともに、電極間の絶縁維持、支持体等の機能を兼ね備える場合が多い。 The light reflecting member constituting the substrate for mounting an optical semiconductor element can be formed of a thermosetting resin composition having excellent light reflection characteristics after curing. In many cases, the light reflecting member has the functions of maintaining the insulation between the electrodes and supporting the light as well as reflecting the light.
ところで、光半導体装置の用途拡大に対応して高輝度化が進むのに伴って、ＬＥＤの発熱量増大によるジャンクション温度の上昇又は直接的な光エネルギーの増大に起因する材料の熱劣化及び光劣化の問題が顕在化する傾向にある。 By the way, with the progress of high brightness in response to the expansion of the use of optical semiconductor devices, thermal degradation and light degradation of materials due to an increase in junction temperature due to an increase in the amount of heat generated by LEDs or a direct increase in light energy. This problem tends to become apparent.
そこで、例えば特許文献１には、エポキシ樹脂及び硬化剤を含有し、耐熱試験後の光反射特性に優れる熱硬化性樹脂組成物及びこれを用いた光半導体素子搭載用基板が開示されている。 Thus, for example, Patent Document 1 discloses a thermosetting resin composition containing an epoxy resin and a curing agent and having excellent light reflection characteristics after a heat resistance test, and an optical semiconductor element mounting substrate using the same.
しかしながら、光反射部材を形成するために用いられる従来の熱硬化性樹脂組成物は、ある程度高温の加熱をともなう溶融混錬によって得ることが困難であった。具体的には、溶融混練の際に熱硬化反応の進行により混錬物が流動性を失って、固まった混錬物の清掃作業、混練設備の破損などが起こりやすいという問題があり、効率的な製造と品質や特性の安定した熱硬化樹脂組成物を製造することが困難であった。そのため、例えば固体原料を溶融することなく低温で混錬する方法によって熱硬化性樹脂組成物を製造する必要があり、このことが生産効率向上の妨げとなる場合があった。 However, it has been difficult to obtain the conventional thermosetting resin composition used for forming the light reflecting member by melt kneading accompanied by heating at a certain high temperature. Specifically, there is a problem that the kneaded material loses its fluidity due to the progress of the thermosetting reaction during melt kneading, and there is a problem that the kneaded kneaded material is easily cleaned and the kneading equipment is easily damaged. It was difficult to produce a thermosetting resin composition with stable production and quality and characteristics. Therefore, for example, it is necessary to produce a thermosetting resin composition by a method of kneading at a low temperature without melting a solid raw material, which may hinder improvement in production efficiency.
本発明は係る事情に鑑みてなされたものであり、その主な目的は、硬化後の可視光から近紫外光の反射率が高く、光反射用部材を形成するための熱硬化性樹脂組成物において、より優れた生産性で製造されることを可能にすることにある。 The present invention has been made in view of such circumstances, and its main purpose is a thermosetting resin composition for forming a light reflecting member having high reflectivity from visible light to near ultraviolet light after curing. Therefore, it is possible to manufacture with higher productivity.
本発明は、（Ａ）エポキシ樹脂、（Ｂ）硬化剤及び（Ｃ）硬化触媒を含有する熱硬化性樹脂組成物に関する。本発明に係る熱硬化性樹脂組成物は、エポキシ樹脂、硬化剤及び硬化触媒を含む混合物を３０℃〜１５０℃で溶融混練する工程を備える方法によって得ることのできる混錬物である。本発明に係る熱硬化性樹脂組成物の硬化後の波長８００ｎｍ〜３５０ｎｍにおける光反射率（光拡散反射率）は７０％以上である。本発明に係る熱硬化性樹脂組成物は光反射部材を形成するために用いられる。 The present invention relates to a thermosetting resin composition containing (A) an epoxy resin, (B) a curing agent, and (C) a curing catalyst. The thermosetting resin composition according to the present invention is a kneaded material that can be obtained by a method including a step of melt-kneading a mixture containing an epoxy resin, a curing agent, and a curing catalyst at 30 ° C. to 150 ° C. The light reflectance (light diffuse reflectance) at a wavelength of 800 nm to 350 nm after curing of the thermosetting resin composition according to the present invention is 70% or more. The thermosetting resin composition according to the present invention is used for forming a light reflecting member.
上記本発明に係る熱硬化性樹脂は、光反射部材を形成するために用いられる従来の熱硬化性樹脂組成物と比較して、より優れた生産性で製造されることが可能である。 Compared with the conventional thermosetting resin composition used in order to form the light reflection member, the thermosetting resin according to the present invention can be manufactured with higher productivity.
本発明に係る熱硬化性樹脂組成物は、１２０℃におけるゲルタイムが２０００秒〜２０００００秒、かつ１８０℃におけるゲルタイムが１０秒〜２０００秒であることが好ましい。これにより、溶融混錬の際に流動性を失うことがより確実に防止されるとともに、より優れた成形性、特にトランスファー成形性が得られる。 The thermosetting resin composition according to the present invention preferably has a gel time at 120 ° C. of 2000 seconds to 200000 seconds and a gel time of 180 ° C. of 10 seconds to 2000 seconds. As a result, loss of fluidity during melting and kneading can be prevented more reliably, and more excellent moldability, particularly transfer moldability can be obtained.
硬化触媒は、好ましくは、２５℃〜２５０℃において固体の塩である。より具体的には、硬化触媒は、下記一般式（１）で表されるオニウム塩を含むことが好ましい。 The curing catalyst is preferably a solid salt at 25 ° C to 250 ° C. More specifically, the curing catalyst preferably contains an onium salt represented by the following general formula (1).
式（１）中、Ｘ＋は、脂肪族４級ホスホニウムイオン、芳香族４級ホスホニウムイオン、１，８−ジアザ−ビシクロ（５，４，０）ウンデカン−７−エンのオニウムイオン及びイミダゾール誘導体のオニウムイオンから選ばれるカチオンを示し、Ｙ−は、テトラフルオロホウ酸イオン、テトラフェニルホウ酸イオン、ヘキサフルオロリン酸イオン、ビストリフルオロメチルスルホニルイミド酸イオン、トリス（トリフルオロメチルスルホニル）炭素酸イオン、トリフルオロメタンスルホン酸イオン、ハロゲン化酢酸イオン、カルボン酸イオン及びハロゲンイオンから選ばれるアニオンを示す。 In the formula (1), X + represents an aliphatic quaternary phosphonium ion, an aromatic quaternary phosphonium ion, an onium ion of 1,8-diaza-bicyclo (5,4,0) undecan-7-ene, and an imidazole derivative. Represents a cation selected from onium ions, Y − represents a tetrafluoroborate ion, a tetraphenylborate ion, a hexafluorophosphate ion, a bistrifluoromethylsulfonylimido ion, a tris (trifluoromethylsulfonyl) carbonate ion, An anion selected from trifluoromethanesulfonate ion, halogenated acetate ion, carboxylate ion and halogen ion is shown.
上記オニウム塩は、下記一般式（２）で表されるホスホニウム塩であることが特に好ましい。これにより、溶融混錬時の安定性が更に向上するとともに、より優れた成形性が得られる。 The onium salt is particularly preferably a phosphonium salt represented by the following general formula (2). Thereby, stability at the time of melt kneading is further improved, and more excellent moldability can be obtained.
式（２）中、Ｒ１、Ｒ２、Ｒ３及びＲ４はそれぞれ独立にアリール基、アラルキル基又は炭素原子数１〜１８の直鎖状若しくは分岐状のアルキル基を示し、アリール基及びアラルキル基はヒドロキシ基又はアルコキシ基で置換されていてもよい。 In formula (2), R 1 , R 2 , R 3 and R 4 each independently represents an aryl group, an aralkyl group or a linear or branched alkyl group having 1 to 18 carbon atoms, and the aryl group and aralkyl The group may be substituted with a hydroxy group or an alkoxy group.
硬化触媒の含有率は、エポキシ樹脂及び硬化剤の合計量に対して０．００１質量％〜５質量％であることが好ましい。 It is preferable that the content rate of a curing catalyst is 0.001 mass%-5 mass% with respect to the total amount of an epoxy resin and a hardening | curing agent.
本発明に係る熱硬化性樹脂組成物は、（Ｄ）金属アルコキサイド、金属キレート及び金属アシレートからなる群より選ばれる少なくとも１種の金属化合物を更に含有していてもよい。この金属化合物は、好ましくは、下記一般式（３）又は（４）で表される化合物である。 The thermosetting resin composition according to the present invention may further contain (D) at least one metal compound selected from the group consisting of metal alkoxides, metal chelates and metal acylates. This metal compound is preferably a compound represented by the following general formula (3) or (4).
式（３）中、Ｍは亜鉛、チタン、アルミニウム、バリウム、ホウ素、ケイ素及びジルコニウムから選ばれる金属又は半金属元素を示し、Ｒｘは、置換基を有していてもよい炭素数２〜５０のアシレート基、置換基を有していてもよい炭素数２〜５０のアルコキシ基、又はキレート基を示し、ｍはＭの結合価数を示し、同一分子中の複数のＲｘは同一でも異なっていてもよい。 In the formula (3), M represents a metal or metalloid element selected from zinc, titanium, aluminum, barium, boron, silicon and zirconium, and R x has 2 to 50 carbon atoms which may have a substituent. An acylate group, an optionally substituted alkoxy group having 2 to 50 carbon atoms, or a chelate group, m represents a valence number of M, and a plurality of R x in the same molecule are the same or different. It may be.
式（４）中、ｎは正の整数を示し、Ｒ５は、水素原子、置換基を有していてもよいメチル基、置換基を有していてもよいエチル基、置換基を有していてもよいプロピル基、置換基を有していてもよいイソプロピル基、置換基を有していてもよいフェニル基又は置換基を有していてもよいグリシドキシプロピル基を示し、Ｒ６、Ｒ７及びＲ８はそれぞれ独立に水素原子、置換基を有していてもよいアルコキシ基、メチル基、エチル基、プロピル基、イソプロピル基、フェニル基、グリシドキシプロピル基、３−アミノプロピル基、アミノフェニル基、アミノフェノキシプロピル基、キレート基、又はアシレート基を示し、同一分子中の複数のＲ７及びＲ８は同一でも異なっていてもよい。 In the formula (4), n represents a positive integer, and R 5 has a hydrogen atom, a methyl group which may have a substituent, an ethyl group which may have a substituent, or a substituent. A propyl group which may have a substituent, an isopropyl group which may have a substituent, a phenyl group which may have a substituent or a glycidoxypropyl group which may have a substituent, R 6 R 7 and R 8 are each independently a hydrogen atom, an optionally substituted alkoxy group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a phenyl group, a glycidoxypropyl group, or 3-aminopropyl. A group, an aminophenyl group, an aminophenoxypropyl group, a chelate group, or an acylate group, and a plurality of R 7 and R 8 in the same molecule may be the same or different.
これら金属化合物の含有率は、エポキシ樹脂及び硬化剤の合計量に対して０．００１質量％〜５質量％であることが好ましい。 It is preferable that the content rate of these metal compounds is 0.001 mass%-5 mass% with respect to the total amount of an epoxy resin and a hardening | curing agent.
エポキシ樹脂が２以上のエポキシ基を有する化合物であり、硬化剤が酸無水物基を有する化合物であってもよい。 The epoxy resin may be a compound having two or more epoxy groups, and the curing agent may be a compound having an acid anhydride group.
本発明に係る熱硬化性樹脂組成物は、（Ｅ）アルミナ、酸化マグネシウム、酸化アンチモン、酸化チタン、酸化ジルコニウム及び無機中空粒子からなる群から選ばれる少なくとも１種の白色顔料を更に含有することが好ましい。これにより、硬化後の光反射特性を更に優れたものとすることができる。これら白色顔料の中心粒径は好ましくは０．１μｍ〜５０μｍである。また、白色顔料の含有率は、当該熱硬化性樹脂組成物全体に対して１０体積％〜８５体積％であることが好ましい。 The thermosetting resin composition according to the present invention may further contain (E) at least one white pigment selected from the group consisting of alumina, magnesium oxide, antimony oxide, titanium oxide, zirconium oxide, and inorganic hollow particles. preferable. Thereby, the light reflection characteristics after curing can be further improved. The center particle diameter of these white pigments is preferably 0.1 μm to 50 μm. Moreover, it is preferable that the content rate of a white pigment is 10 volume%-85 volume% with respect to the said thermosetting resin composition whole.
別の側面において、本発明は、底面及び内周側面から構成される凹部を有するとともに、該内周側面を形成する樹脂成形品を有し、該底面が光半導体素子搭載領域である光半導体素子搭載用基板に関する。本発明に係る光半導体素子搭載用基板において、前記樹脂成形品は、上記本発明に係る熱硬化性樹脂組成物から形成することのできるものである。 In another aspect, the present invention provides an optical semiconductor element having a recess formed of a bottom surface and an inner peripheral side surface, and having a resin molded product forming the inner peripheral side surface, wherein the bottom surface is an optical semiconductor element mounting region The present invention relates to a mounting board. In the optical semiconductor element mounting substrate according to the present invention, the resin molded product can be formed from the thermosetting resin composition according to the present invention.
更に別の側面において、本発明は、底面及び内周側面から構成される凹部を有するとともに、該内周側面を形成する樹脂成形品を有し、該底面が光半導体素子搭載領域である光半導体素子搭載用基板の製造方法に関する。本発明に係る製造方法は、上記本発明に係る熱硬化性樹脂組成物をトランスファー成形することにより前記樹脂成形品を形成する工程を備える。 In yet another aspect, the present invention provides an optical semiconductor having a recess formed of a bottom surface and an inner peripheral side surface, a resin molded product forming the inner peripheral side surface, and the bottom surface being an optical semiconductor element mounting region The present invention relates to a method for manufacturing an element mounting substrate. The manufacturing method according to the present invention includes a step of forming the resin molded product by transfer molding the thermosetting resin composition according to the present invention.
更に別の側面において、本発明は光半導体装置に関する。本発明に係る光半導体装置は、上記本発明に係る光半導体素子搭載用基板と、当該光半導体素子搭載用基板の光半導体素子搭載領域に搭載された光半導体素子と、光半導体素子を当該光半導体素子搭載用基板の凹部内で覆う封止樹脂層と、を備える。 In still another aspect, the present invention relates to an optical semiconductor device. An optical semiconductor device according to the present invention includes an optical semiconductor element mounting substrate according to the present invention, an optical semiconductor element mounted in an optical semiconductor element mounting region of the optical semiconductor element mounting substrate, and the optical semiconductor element in the optical semiconductor device. And a sealing resin layer covering the concave portion of the semiconductor element mounting substrate.
本発明によれば、硬化後の可視光から近紫外光の反射率が高く、優れた生産性で製造されることが可能な、光反射部材用の熱硬化性樹脂組成物が提供される。例えば、固まった樹脂の清掃作業、混練設備の破損などに起因する製造効率の低下を防ぐことができる。本発明の熱硬化性樹脂組成物及びこれから得られる光半導体素子搭載用基板は、品質や特性の安定性の点でも優れる。 According to the present invention, there is provided a thermosetting resin composition for a light reflecting member, which has a high reflectance from visible light to near ultraviolet light after curing and can be produced with excellent productivity. For example, it is possible to prevent a decrease in manufacturing efficiency due to a cleaning operation of a hardened resin, breakage of a kneading facility, or the like. The thermosetting resin composition of the present invention and the substrate for mounting an optical semiconductor element obtained therefrom are excellent in terms of quality and stability of characteristics.
また、本発明に係る熱硬化性樹脂組成物は、優れた成形性も有する。従来、光反射材用の熱硬化性樹脂組成物をトランスファー成形する際、金型内に注入された樹脂組成物の溶融粘度が上昇して、所定の形状を得るために必要な樹脂流動距離が著しく不足してしまう場合があり、熱硬化性樹脂組成物の混練時の時間や温度条件を厳密に管理しないと実用に供することができないという問題があった。係る問題を克服する上でも、本発明の熱硬化性樹脂組成物は有利である。 Moreover, the thermosetting resin composition according to the present invention also has excellent moldability. Conventionally, when a thermosetting resin composition for a light reflecting material is transfer molded, the melt viscosity of the resin composition injected into the mold is increased, and the resin flow distance necessary to obtain a predetermined shape is increased. There is a case where it is extremely insufficient, and there is a problem that it cannot be put into practical use unless the time and temperature conditions during kneading of the thermosetting resin composition are strictly controlled. The thermosetting resin composition of the present invention is advantageous also in overcoming such problems.
以下、本発明の好適な実施形態について詳細に説明する。ただし、本発明は以下の実施形態に限定されるものではない。 Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.
本実施形態に係る熱硬化性樹脂組成物は、エポキシ樹脂、硬化剤及び硬化触媒を含有し、硬化後の可視光から近紫外光の波長領域における反射率が高く、光反射部材を形成するために用いられる。この熱硬化性樹脂組成物は、これらの混合物を、その流動性を維持しながら３０℃〜１５０℃で連続的に溶融混練する工程を備える方法によって得ることのできる混錬物である。硬化反応を実質的に進行させることなく混合物を溶融混錬することが好ましい。 The thermosetting resin composition according to the present embodiment contains an epoxy resin, a curing agent, and a curing catalyst, and has a high reflectance in the wavelength region from visible light to near ultraviolet light after curing, and forms a light reflecting member. Used for. This thermosetting resin composition is a kneaded material that can be obtained by a method comprising a step of continuously melting and kneading these mixtures at 30 ° C. to 150 ° C. while maintaining their fluidity. It is preferable to melt and knead the mixture without substantially proceeding with the curing reaction.
熱硬化性樹脂組成物の１２０℃におけるゲルタイムは２０００秒〜１０００００秒であることが好ましい。この程度のゲルタイムを有する熱硬化性樹脂組成物であれば、通常、混合物の流動性を維持しながら３０℃〜１５０℃での溶融混錬により得ることが可能である。 The gel time at 120 ° C. of the thermosetting resin composition is preferably 2000 seconds to 100,000 seconds. A thermosetting resin composition having such a gel time can usually be obtained by melt kneading at 30 ° C. to 150 ° C. while maintaining the fluidity of the mixture.
また、熱硬化性樹脂組成物の１８０℃におけるゲルタイムは１０秒〜２０００秒であることが好ましい。これにより、トランスファー成形等の方法により、熱硬化性樹脂組成物の硬化物である樹脂成形品を良好な成形性で形成することができる。 Moreover, it is preferable that the gel time in 180 degreeC of a thermosetting resin composition is 10 second-2000 second. Thereby, the resin molded product which is a hardened | cured material of a thermosetting resin composition can be formed with favorable moldability by methods, such as transfer molding.
これらゲルタイムは、例えば、ＪＳＲ型キュラストメータを用いる方法、又は、攪拌棒で混ぜながら熱硬化性樹脂組成物をホットプレート上で所定の温度に加熱し、樹脂組成物が流動性を失うまで時間をゲルタイムとして測定する方法によって測定することができる。後述の実施例では後者を選択した。 These gel times can be determined by, for example, a method using a JSR type curast meter, or heating the thermosetting resin composition to a predetermined temperature on a hot plate while mixing with a stir bar, and the resin composition loses fluidity. It can measure by the method of measuring as gel time. In the examples described later, the latter was selected.
本実施形態に係る熱硬化性樹脂組成物は、優れた貯蔵安定性を有する。貯蔵安定性とは、例えば熱硬化性樹脂組成物を製造した後、−５℃以上１０℃以下の環境下に所定時間保管されたときに、スパイラルフローの初期値からの変動が小さいことであると言い換えることができる。スパイラルフローはトランスファー成形時の流動性を評価する指標として用いることができる。 The thermosetting resin composition according to this embodiment has excellent storage stability. Storage stability is, for example, that when a thermosetting resin composition is produced and then stored for a predetermined time in an environment of −5 ° C. or more and 10 ° C. or less, the fluctuation from the initial value of the spiral flow is small. In other words. Spiral flow can be used as an index for evaluating fluidity during transfer molding.
スパイラルフローの初期値に対する保持率は、好ましくは３０％以上、より好ましくは５０％以上、更に好ましくは７０％以上である。例えば、熱硬化性樹脂組成物を溶融混錬によって製造した後、７２０時間、１０℃以下の環境下で７２０時間に保管したときに、スパイラルフローの初期値（製造直後の値）に対する保持率が５０％未満であると、光半導体素子搭載用基板の凹部を形成するための金型中に、溶融粘度の上昇によって熱硬化性樹脂組成物が流入できなくなり、光半導体素子搭載用基板の製造が困難となる傾向がある。スパイラルフローの保持率が初期値に対して７０％を超えると、製造後の長期保管がより容易になるため、特に粘度上昇にともなう樹脂組成物の廃棄によるロスが低減でき、実用上優れている。 The retention rate with respect to the initial value of the spiral flow is preferably 30% or more, more preferably 50% or more, and further preferably 70% or more. For example, after the thermosetting resin composition is manufactured by melt kneading, when it is stored for 720 hours in an environment of 10 ° C. or lower for 720 hours, the retention rate relative to the initial value of spiral flow (the value immediately after manufacture) is If it is less than 50%, the thermosetting resin composition cannot flow into the mold for forming the concave portion of the substrate for mounting an optical semiconductor element due to an increase in melt viscosity. It tends to be difficult. When the retention rate of the spiral flow exceeds 70% with respect to the initial value, long-term storage after production becomes easier, and in particular, loss due to disposal of the resin composition accompanying an increase in viscosity can be reduced, which is excellent in practical use. .
熱硬化性樹脂組成物のスパイラルフローは、特に制限はないが、成形温度１００℃〜２００℃、成形圧力０．５〜２０ＭＰａ、６０〜１２０秒の条件で５０ｃｍ以上であることが好ましく、８０ｃｍ以上であることがより好ましく、１００ｃｍ以上であることがさらに好ましくい。スパイラルフローが５０ｃｍ未満であると、光半導体素子搭載用基板の凹部を形成するための金型中に、溶融粘度の上昇によって熱硬化性樹脂組成物が流入できなくなり、光半導体素子搭載用基板の製造が困難となる傾向がある。スパイラルフローが１００ｃｍを超えると、成形用金型の設計における自由度が高く、一度の成形で複数個の光半導体素子搭載用基板の製造することが容易になり、特に優れた生産性が得られる。 The spiral flow of the thermosetting resin composition is not particularly limited, but is preferably 50 cm or more and 80 cm or more under conditions of a molding temperature of 100 ° C. to 200 ° C., a molding pressure of 0.5 to 20 MPa, and 60 to 120 seconds. It is more preferable that it is 100 cm or more. When the spiral flow is less than 50 cm, the thermosetting resin composition cannot flow into the mold for forming the recesses of the substrate for mounting an optical semiconductor element due to an increase in melt viscosity. Manufacturing tends to be difficult. When the spiral flow exceeds 100 cm, the degree of freedom in designing the molding die is high, and it becomes easy to manufacture a plurality of substrates for mounting an optical semiconductor element by one molding, and particularly excellent productivity can be obtained. .
熱硬化性樹脂組成物を構成するエポキシ樹脂及び硬化剤として、それぞれ複数種類用いることができる。 A plurality of types can be used as the epoxy resin and the curing agent constituting the thermosetting resin composition.
エポキシ樹脂は、電子部品封止用エポキシ樹脂成形材料において一般に使用されている、２以上のエポキシ基を有するものであってもよい。例えば、フェノールノボラック型エポキシ樹脂及びオルソクレゾールノボラック型エポキシ樹脂をはじめとする、フェノール類とアルデヒド類とから形成されるノボラック樹脂をエポキシ化したノボラック型エポキシ樹脂、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳ及びアルキル置換ビスフェノール等のジグリシジルエーテル、ジアミノジフェニルメタン、イソシアヌル酸等のポリアミンとエピクロルヒドリンの反応により得られるグリシジルアミン型エポキシ樹脂、並びに、オレフィン結合を過酢酸等の過酸で酸化して得られる線状脂肪族エポキシ樹脂及び脂環族エポキシ樹脂から１種又は複数種のエポキシ樹脂が選択される。 The epoxy resin may have two or more epoxy groups that are generally used in an epoxy resin molding material for sealing electronic parts. For example, novolac epoxy resins obtained by epoxidizing novolac resins formed from phenols and aldehydes, such as phenol novolac epoxy resins and orthocresol novolac epoxy resins, bisphenol A, bisphenol F, bisphenol S and alkyl Diglycidyl ethers such as substituted bisphenols, diaminodiphenylmethane, isocyanuric acid and other polyamines obtained by the reaction of epichlorohydrin and glycidylamine type epoxy resins, and linear aliphatics obtained by oxidizing olefinic bonds with peracids such as peracetic acid One or more epoxy resins are selected from the epoxy resin and the alicyclic epoxy resin.
これらのうち比較的着色の少ないものが好ましい。具体的には、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、ジグリシジルイソシアヌレート、トリグリシジルイソシアヌレート、並びに、１，２−シクロヘキサンジカルボン酸、１，３−シクロヘキサンジカルボン酸及び１，４−シクロヘキサンジカルボン酸から選ばれるジカルボン酸から誘導されるジカルボン酸ジグリシジルエステルが好ましい。同様の観点から、フタル酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、メチルテトラヒドロフタル酸、ナジック酸及びメチルナジック酸から選ばれるジカルボン酸のジグリシジルエステル、並びに、芳香環が水素化された脂環式構造を有する核水素化トリメリット酸又は核水素化ピロメリット酸のグリシジルエステルも好ましい。 Of these, those with relatively little coloring are preferred. Specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, diglycidyl isocyanurate, triglycidyl isocyanurate, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid And a dicarboxylic acid diglycidyl ester derived from a dicarboxylic acid selected from 1,4-cyclohexanedicarboxylic acid. From the same viewpoint, diglycidyl ester of dicarboxylic acid selected from phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methyltetrahydrophthalic acid, nadic acid and methylnadic acid, and alicyclic hydrogenated aromatic ring Also preferred is a glycidyl ester of nuclear hydrogenated trimellitic acid or nuclear hydrogenated pyromellitic acid having a structure.
また、シラン化合物を有機溶媒、有機塩基及び水の存在下に加熱して、加水分解縮合させることにより得られる、主鎖としてのシリコーン骨格とエポキシ基とを有するポリオルガノシロキサンも好ましい。 A polyorganosiloxane having a silicone skeleton and an epoxy group as a main chain obtained by heating and hydrolyzing and condensing a silane compound in the presence of an organic solvent, an organic base and water is also preferred.
硬化剤は、電子部品封止用エポキシ樹脂成形材料で一般に使用されているものであってよく、エポキシ樹脂と反応して硬化物を形成可能なものであれば、特に制限なく用いることができるが、比較的着色のない硬化剤が好ましい。例えば、酸無水物系硬化剤、イソシアヌル酸誘導体、及びフェノール系硬化剤が好適である。 The curing agent may be one that is generally used in an epoxy resin molding material for sealing electronic parts, and can be used without particular limitation as long as it can react with the epoxy resin to form a cured product. A curing agent that is relatively uncolored is preferred. For example, an acid anhydride curing agent, an isocyanuric acid derivative, and a phenol curing agent are suitable.
酸無水物系硬化剤としては、酸無水物基を有する化合物が用いられる。酸無水物系硬化剤は、例えば、無水フタル酸、無水マレイン酸、無水トリメリット酸、無水ピロメリット酸、ヘキサヒドロ無水フタル酸、テトラヒドロ無水フタル酸、無水メチルナジック酸、無水ナジック酸、無水グルタル酸、無水ジメチルグルタル酸、無水ジエチルグルタル酸、無水コハク酸、メチルヘキサヒドロ無水フタル酸及びメチルテトラヒドロ無水フタル酸から選ばれる。これらは単独で用いても２種類以上併用してもよい。 As the acid anhydride curing agent, a compound having an acid anhydride group is used. Acid anhydride curing agents include, for example, phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, glutaric anhydride Dimethyl glutaric anhydride, diethyl glutaric anhydride, succinic anhydride, methyl hexahydrophthalic anhydride and methyl tetrahydrophthalic anhydride. These may be used alone or in combination of two or more.
イソシアヌル酸誘導体は、例えば、１，３，５−トリス（１−カルボキシメチル）イソシアヌレート、１，３，５−トリス（２−カルボキシエチル）イソシアヌレート、１，３，５−トリス（３−カルボキシプロピル）イソシアヌレート及び１，３−ビス（２−カルボキシエチル）イソシアヌレートから選ばれる。これらは単独で用いても２種類以上併用してもよい。 Isocyanuric acid derivatives include, for example, 1,3,5-tris (1-carboxymethyl) isocyanurate, 1,3,5-tris (2-carboxyethyl) isocyanurate, 1,3,5-tris (3-carboxyl). Propyl) isocyanurate and 1,3-bis (2-carboxyethyl) isocyanurate. These may be used alone or in combination of two or more.
これらのなかでも、硬化剤は、無水フタル酸、無水トリメリット酸、ヘキサヒドロ無水フタル酸、テトラヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、無水グルタル酸、無水ジメチルグルタル酸、無水ジエチルグルタル酸及び１，３，５−トリス（３−カルボキシプロピル）イソシアヌレートからなる群より選ばれる１種以上であることが特に好ましい。 Among these, the curing agent is phthalic anhydride, trimellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, glutaric anhydride, dimethylglutaric anhydride, Particularly preferred is one or more selected from the group consisting of diethyl glutaric anhydride and 1,3,5-tris (3-carboxypropyl) isocyanurate.
硬化剤の分子量は１００〜４００程度が好ましい。また、無色又は淡黄色の硬化剤が好ましい。 The molecular weight of the curing agent is preferably about 100 to 400. A colorless or light yellow curing agent is preferred.
硬化剤は、ポリイミド樹脂の原料として一般的に使用される酸無水物を含んでもよい。例えば、無水トリメリット酸及び無水ピロメリット酸のような、芳香環を有する酸無水物の芳香環の不飽和結合のすべてを水素化させた水素化無水トリメリット酸及び水素化無水ピロメリット酸も硬化剤として好適である。 A hardening | curing agent may also contain the acid anhydride generally used as a raw material of a polyimide resin. For example, hydrogenated trimellitic anhydride and hydrogenated pyromellitic anhydride in which all unsaturated bonds of the aromatic ring of an acid anhydride having an aromatic ring such as trimellitic anhydride and pyromellitic anhydride are hydrogenated Suitable as a curing agent.
熱硬化性樹脂組成物において、エポキシ樹脂中のエポキシ基１当量に対して、当該エポキシ基と反応する硬化剤中の活性基（例えば酸無水物基又は水酸基）の比率が０．５〜０．９当量であることが好ましく、０．７〜０．８当量であることがより好ましい。活性基が０．５当量未満であると、熱硬化性樹脂組成物（エポキシ樹脂組成物）の硬化速度が小さくなる傾向がある。また、得られる硬化体のガラス転移温度が低くなったり、充分な弾性率が得られなくなったりする場合もある。一方、上記活性基の比率が０．９当量を超えると硬化後の樹脂成形品の強度が低下する傾向がある。 In the thermosetting resin composition, the ratio of the active group (for example, acid anhydride group or hydroxyl group) in the curing agent that reacts with the epoxy group to 0.5 equivalent to 1 equivalent of the epoxy group in the epoxy resin. It is preferably 9 equivalents, and more preferably 0.7 to 0.8 equivalents. When the active group is less than 0.5 equivalent, the curing rate of the thermosetting resin composition (epoxy resin composition) tends to be small. Moreover, the glass transition temperature of the hardened | cured material obtained may become low, or sufficient elasticity may not be obtained. On the other hand, when the ratio of the active group exceeds 0.9 equivalent, the strength of the resin molded product after curing tends to decrease.
硬化触媒は、好ましくは、２５℃〜２５０℃において固体（好ましくは塩）である。言い換えると、硬化触媒は２５℃〜２５０℃の融点を有することが好ましい。硬化触媒が混練装置内で固体であると、エポキシ樹脂と硬化剤の反応効率が低下するため、混練装置内での増粘又は硬化を特に効果的に防ぐことができる。硬化触媒の融点が２５℃未満であると、溶融混練の際に硬化触媒がエポキシ樹脂や硬化剤と相溶し、反応効率が向上して混練装置内での熱硬化性樹脂組成物の増粘又は硬化を招きやすくなる傾向がある。硬化触媒の融点が２５０℃を超えると、熱硬化性樹脂組成物をトランスファー成形により成形するときに、硬化時間が長くなる傾向がある。硬化時間が長くなると、光半導体素子搭載用基板の製造工程が長時間化してしまう場合がある。同様の観点から、硬化触媒はより好ましくは５０℃〜２５０℃、更に好ましくは８０℃〜２３０℃の温度域で固体である。言い換えると、硬化触媒の融点はより好ましくは５０℃〜２５０℃、更に好ましくは８０℃〜２３０℃である。 The curing catalyst is preferably a solid (preferably a salt) at 25 ° C to 250 ° C. In other words, the curing catalyst preferably has a melting point of 25 ° C to 250 ° C. When the curing catalyst is solid in the kneading apparatus, the reaction efficiency between the epoxy resin and the curing agent is reduced, and thus thickening or curing in the kneading apparatus can be particularly effectively prevented. When the melting point of the curing catalyst is less than 25 ° C., the curing catalyst is compatible with the epoxy resin and the curing agent during melt-kneading, the reaction efficiency is improved, and the viscosity of the thermosetting resin composition in the kneading apparatus is increased. Or, it tends to cause curing. When the melting point of the curing catalyst exceeds 250 ° C., the curing time tends to be long when the thermosetting resin composition is molded by transfer molding. If the curing time becomes long, the manufacturing process of the substrate for mounting an optical semiconductor element may take a long time. From the same viewpoint, the curing catalyst is more preferably a solid in a temperature range of 50 ° C to 250 ° C, and more preferably 80 ° C to 230 ° C. In other words, the melting point of the curing catalyst is more preferably 50 ° C to 250 ° C, still more preferably 80 ° C to 230 ° C.
硬化触媒は、下記一般式（１）で表されるオニウム塩を含むことが好ましい。 The curing catalyst preferably contains an onium salt represented by the following general formula (1).
式（１）中、Ｘ＋は、脂肪族４級ホスホニウムイオン、芳香族４級ホスホニウムイオン、１，８−ジアザ−ビシクロ（５，４，０）ウンデカン−７−エンのオニウムイオン及びイミダゾール誘導体のオニウムイオンから選ばれるカチオンを示し、Ｙ−は、テトラフルオロホウ酸イオン、テトラフェニルホウ酸イオン、ヘキサフルオロリン酸イオン、ビストリフルオロメチルスルホニルイミド酸イオン、トリス（トリフルオロメチルスルホニル）炭素酸イオン、トリフルオロメタンスルホン酸イオン、ハロゲン化酢酸イオン、カルボン酸イオン及びハロゲンイオンから選ばれるアニオンを示す。 In the formula (1), X + represents an aliphatic quaternary phosphonium ion, an aromatic quaternary phosphonium ion, an onium ion of 1,8-diaza-bicyclo (5,4,0) undecan-7-ene, and an imidazole derivative. Represents a cation selected from onium ions, Y − represents a tetrafluoroborate ion, a tetraphenylborate ion, a hexafluorophosphate ion, a bistrifluoromethylsulfonylimido ion, a tris (trifluoromethylsulfonyl) carbonate ion, An anion selected from trifluoromethanesulfonate ion, halogenated acetate ion, carboxylate ion and halogen ion is shown.
上記オニウム塩は、下記一般式（２）で表されるホスホニウム塩であることが特に好ましい。 The onium salt is particularly preferably a phosphonium salt represented by the following general formula (2).
式（２）中、Ｒ１、Ｒ２、Ｒ３及びＲ４はそれぞれ独立にアリール基、アラルキル基又は炭素原子数１〜１８の直鎖状若しくは分岐状のアルキル基を示し、アリール基及びアラルキル基はヒドロキシ基又はアルコキシ基で置換されていてもよい。 In formula (2), R 1 , R 2 , R 3 and R 4 each independently represents an aryl group, an aralkyl group or a linear or branched alkyl group having 1 to 18 carbon atoms, and the aryl group and aralkyl The group may be substituted with a hydroxy group or an alkoxy group.
硬化触媒の含有率は、エポキシ樹脂及び硬化剤の合計量に対して０．００１質量％〜５質量％であることが好ましい。 It is preferable that the content rate of a curing catalyst is 0.001 mass%-5 mass% with respect to the total amount of an epoxy resin and a hardening | curing agent.
以上挙げた化合物の中でも、硬化触媒は、テトラエチルホスホニウム４フッ化ホウ素、テトラｎ−ブチルホスホニウム４フッ化ホウ素、トリメチルｎ−ドデシルホスホニウム４フッ化ホウ素、トリメチルｎ−ヘキサデシルホスホニウム４フッ化ホウ素、トリエチルｎ−ヘキサデシルホスホニウム４フッ化ホウ素、トリエチルｎ−ドデシルホスホニウム４フッ化ホウ素、トリブチルｎ−オクチルホスホニウム４フッ化ホウ素、トリブチルｎ−デシルホスホニウム４フッ化ホウ素、トリブチルｎ−ドデシルホスホニウム４フッ化ホウ素、トリブチルｎ−ヘキサデシルホスホニウム４フッ化ホウ素、トリフェニルｎ−ブチルホスホニウム４フッ化ホウ素、トリフェニルｎ−ドデシルホスホニウム４フッ化ホウ素、トリフェニルｎ−ヘキサデシルホスホニウム４フッ化ホウ素、テトラｎ−オクチルホスホニウム４フッ化ホウ素、トリオクチルｎ−ドデシルホスホニウム４フッ化ホウ素、トリオクチルｎ−ヘキサデシルホスホニウム４フッ化ホウ素、トリプロピルｎ−ドデシルホスホニウム４ フッ化ホウ素、トリプロピルｎ−ヘキサデシルホスホニウム４フッ化ホウ素、トリス（ヒドロキシプロピル）ｎ−オクチルホスホニウム４フッ化ホウ素、トリス（ヒドロキシプロピル）ｎ−ドデシルホスホニウム４フッ化ホウ素、トリス（ヒドロキシプロピル）ｎ−テトラデシルホスホニウム４フッ化ホウ素及びトリス（ヒドロキシプロピル）ｎ−ヘキサデシルホスホニウム４フッ化ホウ素からなる群より選ばれる少なくとも１種のホスホニウム塩を含むことが好ましい。さらにこれらの中でも、硬化後の着色性が少なく、さらに貯蔵安定性にも優れる点から、テトラ−ｎ−ブチルホスホニウムテトラフルオロボレート及びテトラ−ｎ−ブチルホスホニウムテトラフェニルボレートが好ましい。 Among the compounds listed above, the curing catalysts are tetraethylphosphonium tetrafluoroboron, tetra n-butylphosphonium tetrafluoride, trimethyl n-dodecylphosphonium tetrafluoride, trimethyl n-hexadecylphosphonium tetrafluoride, triethyl. n-hexadecylphosphonium tetrafluoride, triethyl n-dodecylphosphonium tetrafluoride, tributyl n-octylphosphonium tetrafluoride, tributyl n-decylphosphonium tetrafluoride, tributyl n-dodecylphosphonium tetrafluoride, Tributyl n-hexadecylphosphonium tetrafluoride, triphenyl n-butylphosphonium tetrafluoride, triphenyl n-dodecylphosphonium tetrafluoride, triphenyl n-hexadecylphos Nitrogen tetrafluoride, Tetra n-octylphosphonium tetrafluoride, Trioctyl n-dodecylphosphonium tetrafluoride, Trioctyl n-hexadecylphosphonium tetrafluoride, Tripropyl n-dodecylphosphonium tetrafluoride, Tripropyl n-hexadecylphosphonium tetrafluoride, tris (hydroxypropyl) n-octylphosphonium tetrafluoride, tris (hydroxypropyl) n-dodecylphosphonium tetrafluoride, tris (hydroxypropyl) n-tetradecylphosphonium tetrafluoride It is preferable to contain at least one phosphonium salt selected from the group consisting of boron fluoride and tris (hydroxypropyl) n-hexadecylphosphonium tetrafluoride. Further, among these, tetra-n-butylphosphonium tetrafluoroborate and tetra-n-butylphosphonium tetraphenylborate are preferable from the viewpoint of little colorability after curing and excellent storage stability.
硬化触媒は上記のようなオニウム塩を含むことが好ましいが、その場合にこれら以外のエポキシ樹脂用硬化触媒を更に含んでいてもよい。その他の硬化触媒としては、例えば、１，８−ジアザ−ビシクロ（５，４，０）ウンデカン−７−エン、トリエチレンジアミン、トリ−２，４，６−ジメチルアミノメチルフェノール等の３級アミン類、２−エチル−４メチルイミダゾール、２−メチルイミダゾール等のイミダゾール類、トリフェニルホスフィン、テトラフェニルホスホニウムテトラフェニルボレート、テトラ−ｎ−ブチルホスウム−ｏ，ｏ−ジエチルホスホロジチオエート等の４級ホスホニウム塩、４級アンモニウム塩、有機金属塩類及びこれらの誘導体が挙げられる。これらは単独で使用してもよく又は併用してもよい。これらの硬化促進剤の中では、３級アミン類及びイミダゾール類が好ましい。 The curing catalyst preferably contains an onium salt as described above, but in that case, it may further contain an epoxy resin curing catalyst other than these. Examples of other curing catalysts include tertiary amines such as 1,8-diaza-bicyclo (5,4,0) undecan-7-ene, triethylenediamine, tri-2,4,6-dimethylaminomethylphenol. , Quaternary phosphonium salts such as 2-phenyl-4-methylimidazole, imidazoles such as 2-methylimidazole, triphenylphosphine, tetraphenylphosphonium tetraphenylborate, tetra-n-butylphosphine-o, o-diethylphosphorodithioate Quaternary ammonium salts, organometallic salts, and derivatives thereof may be mentioned. These may be used alone or in combination. Among these curing accelerators, tertiary amines and imidazoles are preferable.
熱硬化性樹脂組成物における硬化触媒の含有率は、エポキシ樹脂及び硬化剤の合計量に対して０．００１質量％〜５質量％であることが好ましい。硬化触媒の含有率が０．００１質量％未満であると、硬化促進効果が小さくなる傾向があり、５質量％を超えると、得られる樹脂成形体に変色が見られる場合がある。同様の観点から、硬化触媒の含有率は０．０１〜３．０質量％であることがより好ましい。 It is preferable that the content rate of the curing catalyst in a thermosetting resin composition is 0.001 mass%-5 mass% with respect to the total amount of an epoxy resin and a hardening | curing agent. When the content of the curing catalyst is less than 0.001% by mass, the curing accelerating effect tends to be small. From the same viewpoint, the content of the curing catalyst is more preferably 0.01 to 3.0% by mass.
熱硬化性樹脂組成物は、金属アルコキサイド、金属キレート及び金属アシレートからなる群より選ばれる少なくとも１種の金属化合物を更に含有することが好ましい。これら金属化合物によって硬化触媒を活性化させることができる。この金属化合物は、好ましくは、下記一般式（３）又は（４）で表される化合物である。 The thermosetting resin composition preferably further contains at least one metal compound selected from the group consisting of metal alkoxides, metal chelates, and metal acylates. The curing catalyst can be activated by these metal compounds. This metal compound is preferably a compound represented by the following general formula (3) or (4).
式（３）中、Ｍは亜鉛、チタン、アルミニウム、バリウム、ホウ素、ケイ素及びジルコニウムから選ばれる金属又は半金属元素を示し、Ｒｘは、置換基を有していてもよい炭素数２〜５０のアシレート基、置換基を有していてもよい炭素数２〜５０のアルコキシ基、又はキレート基を示し、ｍはＭの結合価数を示し、同一分子中の複数のＲｘは同一でも異なっていてもよい。 In the formula (3), M represents a metal or metalloid element selected from zinc, titanium, aluminum, barium, boron, silicon and zirconium, and R x has 2 to 50 carbon atoms which may have a substituent. An acylate group, an optionally substituted alkoxy group having 2 to 50 carbon atoms, or a chelate group, m represents a valence number of M, and a plurality of R x in the same molecule are the same or different. It may be.
式（４）中、ｎは正の整数を示し、Ｒ５は、水素原子、置換基を有していてもよいメチル基、置換基を有していてもよいエチル基、置換基を有していてもよいプロピル基、置換基を有していてもよいイソプロピル基、置換基を有していてもよいフェニル基又は置換基を有していてもよいグリシドキシプロピル基を示し、Ｒ６、Ｒ７及びＲ８はそれぞれ独立に水素原子、置換基を有していてもよいアルコキシ基、メチル基、エチル基、プロピル基、イソプロピル基、フェニル基、グリシドキシプロピル基、３−アミノプロピル基、アミノフェニル基、アミノフェノキシプロピル基、キレート基、又はアシレート基を示し、同一分子中の複数のＲ７及びＲ８は同一でも異なっていてもよい。 In the formula (4), n represents a positive integer, and R 5 has a hydrogen atom, a methyl group which may have a substituent, an ethyl group which may have a substituent, or a substituent. A propyl group which may have a substituent, an isopropyl group which may have a substituent, a phenyl group which may have a substituent or a glycidoxypropyl group which may have a substituent, R 6 R 7 and R 8 are each independently a hydrogen atom, an optionally substituted alkoxy group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a phenyl group, a glycidoxypropyl group, or 3-aminopropyl. A group, an aminophenyl group, an aminophenoxypropyl group, a chelate group, or an acylate group, and a plurality of R 7 and R 8 in the same molecule may be the same or different.
これら金属化合物の含有率は、エポキシ樹脂及び硬化剤の合計量に対して０．００１質量％〜５質量％であることが好ましい。金属化合物の含有率が０．００１質量％未満であると、硬化促進効果が小さくなる傾向があり、５．０質量％を超えると硬化阻害が起きる場合や、トランスファー成形時の金型からの離型性が低下する場合がある。同様の観点から、金属化合物の含有率は０．００１質量％〜３．０質量％であることがより好ましい。 It is preferable that the content rate of these metal compounds is 0.001 mass%-5 mass% with respect to the total amount of an epoxy resin and a hardening | curing agent. When the content of the metal compound is less than 0.001% by mass, the effect of promoting the curing tends to be small. When the content exceeds 5.0% by mass, the inhibition of curing occurs, or the mold is separated from the mold during transfer molding. The moldability may be reduced. From the same viewpoint, the content of the metal compound is more preferably 0.001% by mass to 3.0% by mass.
熱硬化性樹脂組成物は、高い反射率を達成するために、白色顔料を含有することが好ましい。白色顔料は、公知のものを特に制限なく使用することができる。白色顔料は、例えば、アルミナ、酸化マグネシウム、酸化アンチモン、酸化チタン及び酸化ジルコニウムからなる群より選ばれる少なくとも１種である。白色顔料は無機中空粒子であってもよい。
無機中空粒子は、例えば、珪酸ソーダガラス、アルミ珪酸ガラス、硼珪酸ソーダガラス又はシラスを含む。白色顔料の中心粒径は０．１〜５０μｍの範囲にあることが好ましい。この中心粒径が０．１μｍ未満であると粒子が凝集しやすいために分散性が低下する傾向があり、５０μｍを超えると硬化物の反射特性が低下する可能性がある。
The thermosetting resin composition preferably contains a white pigment in order to achieve high reflectance. A well-known thing can be especially used for a white pigment without a restriction | limiting. The white pigment is at least one selected from the group consisting of alumina, magnesium oxide, antimony oxide, titanium oxide, and zirconium oxide, for example. The white pigment may be inorganic hollow particles.
The inorganic hollow particles include, for example, sodium silicate glass, aluminum silicate glass, borosilicate soda glass, or shirasu. The center particle diameter of the white pigment is preferably in the range of 0.1 to 50 μm. When the center particle size is less than 0.1 μm, the particles tend to aggregate, so that the dispersibility tends to be lowered. When the center particle size exceeds 50 μm, the reflection property of the cured product may be lowered.
熱硬化性樹脂組成物は、白色顔料以外の無機充填材を更に含有していてもよい。無機充填剤の配合によって成形性を調整することができる。無機充填材は、特に限定されないが、例えば、シリカ、酸化アンチモン、酸化チタン、水酸化アルミニウム、水酸化マグネシウム、硫酸バリウム、炭酸マグネシウム及び炭酸バリウムからなる群から選ばれる少なくとも１種である。熱伝導性、光反射特性、成型性及び難燃性の点からは、シリカ、アルミナ、酸化マグネシウム、酸化アンチモン、酸化チタン、酸化ジルコニウム、水酸化アルミニウム及び水酸化マグネシウムから選ばれる２種類以上の組み合わせが好ましい。 The thermosetting resin composition may further contain an inorganic filler other than the white pigment. The moldability can be adjusted by blending the inorganic filler. The inorganic filler is not particularly limited, but is at least one selected from the group consisting of silica, antimony oxide, titanium oxide, aluminum hydroxide, magnesium hydroxide, barium sulfate, magnesium carbonate, and barium carbonate. Two or more combinations selected from silica, alumina, magnesium oxide, antimony oxide, titanium oxide, zirconium oxide, aluminum hydroxide, and magnesium hydroxide from the viewpoints of thermal conductivity, light reflection characteristics, moldability, and flame retardancy Is preferred.
無機充填材の中心粒径は、特に限定されないが、白色顔料とのパッキングが効率良くなるように１〜１００μｍの範囲にあることが好ましい。 The center particle diameter of the inorganic filler is not particularly limited, but is preferably in the range of 1 to 100 μm so that packing with the white pigment is efficient.
樹脂材料と白色顔料及び無機充填剤との濡れ性向上のために、カップリング剤の利用が有効である。白色顔料及び無機充填剤を予めカップリング剤で処理しておくことが好ましい。 In order to improve the wettability between the resin material, the white pigment and the inorganic filler, it is effective to use a coupling agent. It is preferable to treat the white pigment and the inorganic filler with a coupling agent in advance.
白色顔料及びこれ以外の無機充填材の合計量は、熱硬化性樹脂組成物全体に対して、１０体積％〜８５体積％の範囲にあることが好ましい、この量が１０体積％未満であると硬化物の光反射特性が低下する傾向があり、８５体積％を超えると樹脂組成物の成型性が低下する傾向がある。樹脂組成物の成形性が低下すると基板の作製が困難となる。 The total amount of the white pigment and the other inorganic filler is preferably in the range of 10% by volume to 85% by volume with respect to the entire thermosetting resin composition, and this amount is less than 10% by volume. There exists a tendency for the light reflection characteristic of hardened | cured material to fall, and when it exceeds 85 volume%, there exists a tendency for the moldability of a resin composition to fall. If the moldability of the resin composition is lowered, it becomes difficult to produce a substrate.
熱硬化性樹脂組成物は、エポキシ樹脂及び硬化剤と無機充填材及び白色顔料との接着性を向上させる観点から、カップリング剤を含有することが好ましい。カップリング剤としては、特に限定されないが、例えば、シランカップリング剤及びチタネート系カップリング剤等がある。シランカップリング剤としては、エポキシシラン系、アミノシラン系、カチオニックシラン系、ビニルシラン系、アクリルシラン系、メルカプトシラン系及びこれらの組み合わせがある。任意の付着量で多々用いられる。カップリング剤の量、種類及び処理条件は特に限定されない。カップリング剤の配合量は熱硬化性樹脂組成物全体に対して５質量％以下が好ましい。 It is preferable that a thermosetting resin composition contains a coupling agent from a viewpoint of improving the adhesiveness of an epoxy resin and a hardening | curing agent, an inorganic filler, and a white pigment. Although it does not specifically limit as a coupling agent, For example, there exist a silane coupling agent, a titanate coupling agent, etc. Examples of the silane coupling agent include epoxy silane, amino silane, cationic silane, vinyl silane, acrylic silane, mercapto silane, and combinations thereof. Often used in any amount of deposit. The amount, type and processing conditions of the coupling agent are not particularly limited. As for the compounding quantity of a coupling agent, 5 mass% or less is preferable with respect to the whole thermosetting resin composition.
熱硬化性樹脂組成物は、必要に応じて、酸化防止剤、離型剤及びイオン捕捉剤等の添加剤を含有してもよい。 The thermosetting resin composition may contain additives such as an antioxidant, a release agent, and an ion scavenger as necessary.
熱硬化前の熱硬化性樹脂組成物は、加圧成形により室温（１５〜３０℃）においてタブレットを形成可能であることが好ましい。加圧成形は、例えば、室温（２５℃）において、５〜５０ＭＰａ、１〜５秒程度の条件下で成形を行うことができればよい。 It is preferable that the thermosetting resin composition before thermosetting can form a tablet at room temperature (15-30 degreeC) by pressure molding. For example, the pressure molding may be performed at room temperature (25 ° C.) under conditions of 5 to 50 MPa and about 1 to 5 seconds.
熱硬化性樹脂組成物の熱硬化によって形成される硬化物の光反射率は、波長３５０ｎｍ〜８００ｎｍにおいて好ましくは７０％以上、より好ましくは８０％以上、さらに好ましくは９０％以上である。この光反射率が７０％未満であると、光反射部材による光半導体装置の輝度向上の効果が低下する傾向がある。 The light reflectance of the cured product formed by thermosetting the thermosetting resin composition is preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more at a wavelength of 350 nm to 800 nm. If the light reflectance is less than 70%, the effect of improving the luminance of the optical semiconductor device by the light reflecting member tends to be reduced.
本実施形態に係る熱硬化性樹脂組成物は、上記各成分の混合物を溶融混錬し、混錬物を冷却及び粉砕する方法によって製造することができる。溶融混錬の手段や条件等は特に限定されない。加熱、溶融、混合及び分散を工程を行なうことが可能な混錬装置が用いることができる。混錬装置は、例えば押出機、ニーダー、ロール及びエクストルーダーから選ばれる。この混錬装置に原材料を一定量供給しながら、混合物を混錬装置内で連続的に溶融混練する。 The thermosetting resin composition according to the present embodiment can be produced by a method in which the mixture of the above components is melt-kneaded and the kneaded product is cooled and pulverized. Melt kneading means and conditions are not particularly limited. A kneading apparatus capable of performing heating, melting, mixing, and dispersing processes can be used. The kneading apparatus is selected from, for example, an extruder, a kneader, a roll, and an extruder. The mixture is continuously melt-kneaded in the kneading apparatus while supplying a certain amount of raw materials to the kneading apparatus.
溶融混練工程では、エポキシ樹脂、硬化剤及び硬化触媒を主として含む熱硬化樹脂成分を熱エネルギーによって融解し、熱硬化反応が実質的に進行しないように温度条件を管理しながら混合物が混錬される。溶融混練の条件は、成分の種類や配合量により適宜決定すればよく、特に制限はない。溶融混錬の条件は、第１に各種原材料の分散性向上、第２に加熱、溶融した樹脂成分と無機充填剤との濡れ性向上及び第３に硬化反応の制御に留意して設定される。 In the melt-kneading process, a thermosetting resin component mainly containing an epoxy resin, a curing agent and a curing catalyst is melted by heat energy, and the mixture is kneaded while controlling the temperature conditions so that the thermosetting reaction does not substantially proceed. . The conditions for melt-kneading may be appropriately determined depending on the type and blending amount of the components, and are not particularly limited. The conditions for melt-kneading are set in consideration of firstly dispersibility improvement of various raw materials, secondly improvement of wettability between heated and melted resin components and inorganic filler, and thirdly control of curing reaction. .
溶融混錬の温度及び時間は、好ましくは３０℃〜１５０℃で２〜４０分間、より好ましくは６０℃〜１４０℃で２〜２０分間である。 The melt kneading temperature and time are preferably 30 ° C. to 150 ° C. for 2 to 40 minutes, more preferably 60 ° C. to 140 ° C. for 2 to 20 minutes.
溶融混練の温度が３０℃未満であると、各成分を溶融混練させることが困難であり、分散性も低下する傾向にあり、１５０℃を超えると、樹脂組成物の高分子量化が進行し、樹脂組成物が装置内で硬化してしまう可能性がある。 When the temperature of the melt kneading is less than 30 ° C., it is difficult to melt and knead each component, and the dispersibility tends to decrease. When the temperature exceeds 150 ° C., the resin composition increases in molecular weight, There is a possibility that the resin composition is cured in the apparatus.
また、溶融混練の時間が２分未満であると、トランスファー成形時に樹脂バリが発生しやすくなる傾向がある。樹脂バリが発生すると、光半導体素子搭載領域の開口部に樹脂汚れが発生し、光半導体素子を搭載する際の障害になったり、光半導体素子と金属配線とをボンディングワイヤなど公知の方法により電気的に接続する際の障害になったりする可能性がある。一方、混練時間の時間が４０分を超えると、樹脂組成物の高分子化が装置内で進行する可能性がある。 Further, if the melt kneading time is less than 2 minutes, resin burrs tend to be easily generated during transfer molding. When resin burrs occur, resin contamination occurs in the opening of the optical semiconductor element mounting region, which may be an obstacle when mounting the optical semiconductor element, or the optical semiconductor element and the metal wiring may be electrically connected by a known method such as a bonding wire. May be a hindrance to connection. On the other hand, when the kneading time exceeds 40 minutes, the resin composition may be polymerized in the apparatus.
原材料として用いられるエポキシ樹脂、硬化剤及び硬化触媒等の原材料は、粉末状であることが好ましい。この場合、必要に応じて、溶融混錬の前に粉末状の各原材料を予備混合（乾式混合）して混合粉を得てもよい。粉末状の各原材料を、混合機能の高い混合機、例えば、高速羽攪拌混合機、ヘンシェルミキサ、レディゲミキサを使用して混合することが分散性向上に有効である。混合機は、高分散性を得られるものであればよく、これらに制限されるものではない。 The raw materials such as epoxy resin, curing agent and curing catalyst used as the raw material are preferably in the form of powder. In this case, if necessary, the powdered raw materials may be premixed (dry-mixed) before melt-kneading to obtain a mixed powder. It is effective for improving the dispersibility to mix powdery raw materials using a mixer having a high mixing function, for example, a high-speed blade stirring mixer, a Henschel mixer, and a Redige mixer. The mixer is not limited to these as long as high dispersibility can be obtained.
粉末状の原材料を用いる場合、それらの粒度を細かくすることにより、高い分散性で各原材料が混合された混合物を容易に得ることができる。場合によっては、予め微粉砕をして原材料の粒度を小さくしてもよい。 When powdery raw materials are used, a mixture in which the raw materials are mixed with high dispersibility can be easily obtained by reducing the particle size of the raw materials. In some cases, the raw material may be finely pulverized to reduce the particle size of the raw material.
混合の際、加熱により樹脂材料（エポキシ樹脂、硬化剤及び硬化触媒等）を溶融状態としながらこれらを無機充填剤と強力に混合することにより、樹脂材料と無機充填剤との良好な濡れ性を得ることができる。例えば、樹脂材料を軟化点付近まで加熱された樹脂材料を無機充填剤と混合し、圧縮、摩擦、剪断力等を与えて充填剤表面に樹脂材料がコーティングされた状態とするのがよい。各種原材料を配合し混合した後、加熱機構の付属した高速羽攪拌混合機や、ヘンシェルミキサ、レディゲミキサに混合物を投入して混合状態としながら、材料温度を樹脂材料の軟化点付近に加熱してやれば、混練と同程度の材料の均一分散と無機充填剤との濡れを得ることが可能である。 At the time of mixing, the resin material (epoxy resin, curing agent, curing catalyst, etc.) is in a molten state by heating, and these are strongly mixed with the inorganic filler, thereby providing good wettability between the resin material and the inorganic filler. Can be obtained. For example, the resin material heated to the vicinity of the softening point may be mixed with an inorganic filler, and compression, friction, shearing force, etc. may be applied so that the surface of the filler is coated with the resin material. After mixing and mixing various raw materials, if the material temperature is heated to the vicinity of the softening point of the resin material while putting the mixture into a high-speed feather agitator with a heating mechanism, a Henschel mixer, a Redige mixer and mixing, It is possible to obtain uniform dispersion of the material and wettability with the inorganic filler as much as kneading.
この際、予め硬化触媒を分離しておくことにより、加熱されたときの硬化反応を抑制し、長時間の混合を行ったときの過反応によるゲル化を防止することができる。 At this time, by separating the curing catalyst in advance, the curing reaction when heated can be suppressed, and gelation due to overreaction when mixing for a long time can be prevented.
粉末状の原材料の加熱方法として、高周波加熱方法を採用することにより、粉末状の原材料の内部も同時に均一に素早く加熱することができるようになる。 By adopting a high-frequency heating method as a method for heating the powdery raw material, the inside of the powdery raw material can be simultaneously and quickly heated.
予備混合後の混合物を、高周波加熱装置を利用して加熱してもよい。この場合は、より濡れ性を向上させるために、高周波加熱処理後の混合物に対して機械的に圧縮力等を与えることが望ましい。具体的には圧縮ロールを使用するが、同様な効果を得ることができるものであれば、他の機械設備を使用しても差し支えない。 The mixture after the preliminary mixing may be heated using a high-frequency heating device. In this case, in order to further improve the wettability, it is desirable to mechanically apply a compressive force or the like to the mixture after the high-frequency heat treatment. Specifically, a compression roll is used, but other mechanical equipment may be used as long as the same effect can be obtained.
予め硬化触媒が混合されている場合、特に硬化反応の進行の抑制に留意が必要である。このため、混合加熱後の製品特性を満足した状態で混合物を取り出したならば、直ちに、冷却を行い混合物の温度を下げて硬化反応の進行を防止することが重要である。混合物の温度を下げる方法としては、冷却ロールを用いる方法がある。 When a curing catalyst is mixed in advance, it is particularly necessary to pay attention to the suppression of the progress of the curing reaction. For this reason, if the mixture is taken out in a state where the product characteristics after mixing and heating are satisfied, it is important to immediately cool and reduce the temperature of the mixture to prevent the progress of the curing reaction. As a method for lowering the temperature of the mixture, there is a method using a cooling roll.
エポキシ樹脂の硬化反応の制御は、前述の混合加熱時の材料温度と加熱時間及び硬化促進剤の種類と使用量の組み合わせに大きく影響される。各種の熱硬化性光反射用樹脂組成物により組成が異なり、さらに要求される流動性、成形性等も変わるため一概に論ずることはできないが、諸特性を満足するように混合物加熱時の材料温度と時間を調整してやればよい。 The control of the curing reaction of the epoxy resin is greatly influenced by the combination of the material temperature and the heating time at the time of mixing and heating described above, and the type and amount of curing accelerator used. The composition varies depending on the various thermosetting resin compositions for light reflection, and the fluidity and moldability required also vary, so it cannot be discussed in general, but the material temperature when heating the mixture to satisfy various characteristics And adjust the time.
図１は光半導体装置の一実施形態を示す斜視図であり、図２は図１のＩＩ−ＩＩ線に沿う断面図である。図１、２に示す光半導体装置１は、底面Ｓ１及び内周側面Ｓ２から構成される凹部１１を有する光半導体素子搭載用基板１０と、光半導体素子搭載領域である底面Ｓ１に搭載された光半導体素子２０と、光半導体素子２０を凹部１１内で覆う封止樹脂層３０とから主として構成される。
FIG. 1 is a perspective view showing an embodiment of an optical semiconductor device, and FIG. 2 is a sectional view taken along line II-II in FIG. The optical semiconductor device 1 shown in FIGS. 1 and 2 includes an optical semiconductor
光半導体素子搭載用基板１０は、板状の金属配線１２と、金属配線１２上に設けられたＮｉ／Ａｇめっき１３及びリフレクター１５を有する。Ｎｉ／Ａｇめっき１３は底面Ｓ１を構成している。リフレクター１５は、底面Ｓ１（Ｎｉ／Ａｇめっき１３）が露出する開口を形成する内周側面Ｓ２を有する。リフレクター１５は、上述の実施形態に係る熱硬化性樹脂組成物を成形して形成される樹脂成形品である。
The optical semiconductor
光半導体素子２０は、ボンディングワイヤ２１を介して金属配線１２及びＮｉ／Ａｇめっき１３と電気的に接続されている。金属配線１２は、光半導体素子２０の底部に接している部分とボンディングワイヤ２１が接続されている部分とに分割されている。これら二つの部分の間には絶縁層１６が介在している。絶縁層１６は、上述の実施形態に係る熱硬化性樹脂組成物によって形成されていてもよい。
The
封止樹脂層３０は、透明樹脂層３１と、透明樹脂層３１内に分散した波長変換手段である蛍光体３２とを含む。封止樹脂層３０は、蛍光体を含有する公知の透明封止樹脂組成物を用いて形成することができる。
The sealing
光半導体装置１は、例えば、上述の実施形態に係る光反射用熱硬化性樹脂組成物をトランスファー成形により成形して金属配線１２上にリフレクター１５としての樹脂成形品を形成する工程と、金属配線１２上に電気めっきによりＮｉ／Ａｇめっき１３を形成する工程と、光半導体素子２０を半導体搭載領域（底面Ｓ１）に搭載する工程と、封止樹脂層３０を形成する工程とを備える方法によって製造することができる。トランスファー成形の後、形成された樹脂成形品をアフターキュアすることなく、光半導体素子２０の搭載等を行うことができる。
The optical semiconductor device 1 includes, for example, a step of forming a light-curing thermosetting resin composition according to the above-described embodiment by transfer molding to form a resin molded product as the
金属配線１２は、例えば、金属箔からの打ち抜き及びエッチング等の公知の方法により形成することができる。金属配線１２を所定形状の金型に配置し、金型の樹脂注入口から熱硬化性樹脂組成物を注入し、これを好ましくは金型温度１７０〜２００℃、成形圧力０．５〜２０ＭＰａで６０〜１２０秒の条件で熱硬化させた後、金型を外す方法により、リフレクター１５として樹脂成形品が得ることができる。
The
本発明に係る光半導体素子搭載用基板及び光半導体素子は、上記実施形態に限定されるものではなく、その趣旨を逸脱しない範囲で適宜変形が可能である。例えば、図３の断面図に示されるように、光半導体素子２０がはんだバンプ２２を介して金属配線１２及びＮｉ／Ａｇめっき１３と電気的に接続されていてもよい。また、図４に示されるように、金属配線を用いるのに代えて、リード４０を用いてもよい。図４に示す実施形態に係る光半導体装置１においては、光半導体素子（ＬＥＤ素子）２０がダイボンド材４２によって半導体素子搭載用基板１０に接着されている。光半導体素子搭載用基板は２以上の凹部を有していてもよい。
The substrate for mounting an optical semiconductor element and the optical semiconductor element according to the present invention are not limited to the above-described embodiments, and can be appropriately modified without departing from the gist thereof. For example, as shown in the sectional view of FIG. 3, the
以下、実施例を挙げて本発明についてさらに具体的に説明する。ただし、本発明はこれら実施例に限定されるものではない。 Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.
熱硬化性樹脂組成物の作製
（実施例１〜８、参考例１〜８）
表１及び表２に示す配合表に従って各材料を配合し、高速羽攪拌機（カワタ社製、ＳＭＰ−２）を用い回転数３０００ｍｉｎ−１で１０分間乾式混合した。得られた混合物を、２軸混練押出機（栗本鉄工所社製、ＫＥＸ−５０）を用い、機内最低温度５０℃、機内最高温度１３０℃の条件で溶融混練した。いずれの混合物も、装置内で硬化することなく流動性を維持した状態で溶融混錬することができた。得られた混練物（光反射部材用熱硬化性樹脂組成物）について以下の評価を行った。なお、表中の各成分の配合量の単位は、重量部であり、空欄は配合なしを意味する。
Preparation of thermosetting resin composition (Examples 1-8, Reference Examples 1-8)
Each material was blended according to the blending table shown in Table 1 and Table 2, and dry-mixed for 10 minutes at a rotational speed of 3000 min −1 using a high-speed blade stirrer (SMP-2, manufactured by Kawata). The obtained mixture was melt-kneaded using a twin-screw kneading extruder (manufactured by Kurimoto Iron Works Co., Ltd., KEX-50) under conditions of an in-machine minimum temperature of 50 ° C and an in-machine maximum temperature of 130 ° C. All the mixtures could be melt-kneaded while maintaining fluidity without curing in the apparatus. The following evaluation was performed about the obtained kneaded material (thermosetting resin composition for light reflection members). In addition, the unit of the compounding quantity of each component in a table | surface is a weight part, and the blank means no compounding.
熱硬化性樹脂組成物の評価
（光反射性試験）
各熱硬化性樹脂組成物を、成形型温度１８０℃、成型圧力６．９ＭＰａ、キュア時間９０秒の条件でトランスファー成型し、その後１５０℃で２時間ポストキュアすることにより、厚み１．０ｍｍのテストピースとしての樹脂成形品を作製した。このテストピースの波長４００ｎｍにおける光反射率を、積分球型分光光度計、Ｖ−７５０型（日本分光株式会社製）を用いて測定した。そして、下記の評価基準に基づいて光反射特性を評価した。評価結果を表１及び表２に示す。
光反射率の評価基準
Ａ：光波長４００ｎｍにおいて光反射率８０％以上
Ｂ：光波長４００ｎｍにおいて光反射率７０％以上８０％未満
Ｃ：光波長４００ｎｍにおいて光反射率７０％未満
Evaluation of thermosetting resin composition (light reflectivity test)
Each thermosetting resin composition was transfer-molded under conditions of a mold temperature of 180 ° C., a molding pressure of 6.9 MPa, and a curing time of 90 seconds, and then post-cured at 150 ° C. for 2 hours to obtain a test with a thickness of 1.0 mm. A resin molded product as a piece was produced. The light reflectance at a wavelength of 400 nm of this test piece was measured using an integrating sphere spectrophotometer, V-750 type (manufactured by JASCO Corporation). And the light reflection characteristic was evaluated based on the following evaluation criteria. The evaluation results are shown in Tables 1 and 2.
Evaluation criteria A of light reflectance: A light reflectance of 80% or more at a light wavelength of 400 nm B: Light reflectance of 70% or more and less than 80% at a light wavelength of 400 nm C: Light reflectance of less than 70% at a light wavelength of 400 nm
（ゲルタイム）
１２０℃又は１８０℃に設定したホットプレート上で加熱しながら、熱硬化性樹脂組成物１ｇをステンレス製スパチュラで攪拌し、熱硬化反応が進行して攪拌不可能となるまでに流動性が失われるまでの時間をゲルタイムとして測定した。評価結果を表１及び表２に示す。
(Geltime)
While heating on a hot plate set at 120 ° C. or 180 ° C., 1 g of the thermosetting resin composition is stirred with a stainless steel spatula and fluidity is lost until the thermosetting reaction proceeds and stirring becomes impossible. The time until was measured as gel time. The evaluation results are shown in Tables 1 and 2.
（スパイラルフロー）
ＥＭＭＩ−１−６６の規格に準じたスパイラルフロー測定用金型を用いて、熱硬化性樹脂組成物を上記条件で成形し、そのときの流動距離（ｃｍ）を求めた。求めた結果を表１及び表２に示す。
(Spiral flow)
The thermosetting resin composition was molded under the above conditions using a spiral flow measurement mold in accordance with the standard of EMMI-1-66, and the flow distance (cm) at that time was determined. The obtained results are shown in Tables 1 and 2.
（Ａ）エポキシ樹脂
１：トリグリシジルイソシアヌレート（エポキシ当量１００、日産化学社製、商品名ＴＥＰＩＳ−Ｓ）
（Ｂ）硬化剤
２：ヘキサヒドロ無水フタル酸（和光純薬社製）
（Ｃ）硬化触媒
３：テトラ−ｎ−ブチルホスホニウムテトラフルオロボレート（日本化学工業社製、商品名ＰＸ−４ＦＢ 融点１００℃）
４：テトラ−ｎ−ブチルホスホニウムテトラフェニルボレート（日本化学工業社製、商品名ＰＸ−４ＰＢ 融点２３０℃）
５：テトラフェニルホスホニウムテトラフェニルボレート（東京化成工業社製）
６：１，８−ジアザ−ビシクロ（５，４，０）ウンデセンテトラフェニルボレート（サンアプロ社製、商品名Ｕ−ＣＡＴ ５００２、融点１３０℃）
７：テトラ−ｎ−ブチルホスホニウム−０，０−ジエチルホスホロジチエート（日本化学工業社製、商品名ＰＸ−４ＥＴ、融点２５℃以下）
８：テトラ−ｎ−ブチルホスホニウムジメチルホスフェート（日本化学工業社製、商品名ＰＸ−４ＭＤ、融点２５℃以下）
９：テトラ−ｎ−ブチルホスホニウムアセテート、融点２５℃以下）
１０：テトラ−ｎ−ブチルホスホニウムオクチレート、融点２５℃以下）
１１：トリフェニルホスフィン（東京化成工業社製、融点５０℃）
（カップリング剤）
１２：γ−グリシジドキシトリメトキシシラン（東レダウコーニング社製、商品名Ａ−１８７）
（無機充填剤）
１３：溶融シリカ（電気化学工業社製、商品名ＦＢ−３０１）
（白色顔料）
１４：中空粒子（住友３Ｍ社製、商品名Ｓ６０−ＨＳ）
１５：アルミナ（アドマテックス社製、商品名ＡＯ−２５Ｒ）
(A) Epoxy resin 1: triglycidyl isocyanurate (epoxy equivalent 100, manufactured by Nissan Chemical Co., Ltd., trade name TEPS-S)
(B) Hardener 2: Hexahydrophthalic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.)
(C) Curing catalyst 3: Tetra-n-butylphosphonium tetrafluoroborate (manufactured by Nippon Chemical Industry Co., Ltd., trade name: PX-4FB, melting point: 100 ° C.)
4: Tetra-n-butylphosphonium tetraphenylborate (manufactured by Nippon Chemical Industry Co., Ltd., trade name: PX-4PB, melting point: 230 ° C.)
5: Tetraphenylphosphonium tetraphenylborate (manufactured by Tokyo Chemical Industry Co., Ltd.)
6: 1,8-diaza-bicyclo (5,4,0) undecenetetraphenylborate (manufactured by San Apro, trade name U-CAT 5002, melting point 130 ° C.)
7: Tetra-n-butylphosphonium-0,0-diethyl phosphorodithioate (manufactured by Nippon Chemical Industry Co., Ltd., trade name: PX-4ET, melting point: 25 ° C. or less)
8: Tetra-n-butylphosphonium dimethyl phosphate (manufactured by Nippon Chemical Industry Co., Ltd., trade name: PX-4MD, melting point: 25 ° C. or lower)
9: Tetra-n-butylphosphonium acetate, melting point 25 ° C. or less)
10: Tetra-n-butylphosphonium octylate, melting point 25 ° C. or less)
11: Triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd., melting point 50 ° C.)
(Coupling agent)
12: γ-glycididoxytrimethoxysilane (manufactured by Toray Dow Corning, trade name A-187)
(Inorganic filler)
13: Fused silica (trade name FB-301, manufactured by Denki Kagaku Kogyo Co., Ltd.)
(White pigment)
14: Hollow particles (manufactured by Sumitomo 3M, trade name S60-HS)
15: Alumina (manufactured by Admatechs, trade name AO-25R)
実施例の熱硬化性樹脂組成物は、最高温度１３０℃の溶融混錬中によって得ることが可能であり、また、その硬化物の光反射特性が十分に優れていた。さらに、実施例の熱硬化性樹脂組成物は、適度なスパイラルフローを維持していることから、トランスファー成形時の流動性にも優れることは明らかである。 The thermosetting resin compositions of the examples could be obtained by melt kneading at a maximum temperature of 130 ° C., and the light reflection characteristics of the cured products were sufficiently excellent. Furthermore, since the thermosetting resin compositions of the examples maintain an appropriate spiral flow, it is clear that the fluidity during transfer molding is also excellent.
さらに、表１及び表２に示すように、実施例の熱硬化性樹脂組成物は、光反射特性に優れていることが明らかである。 Furthermore, as shown in Table 1 and Table 2, it is clear that the thermosetting resin compositions of the examples are excellent in light reflection characteristics.
１…光半導体装置、１０…光半導体素子搭載用基板、１１…凹部、１２…金属配線、１５…リフレクター、１６…絶縁層、２０…光半導体素子、２１…ボンディングワイヤ、２２…はんだバンプ、３０…封止樹脂層、３１…透明樹脂層、３２…蛍光体、４０…リード、４２…ダイボンド材、Ｓ１…底面（光半導体素子搭載領域）、Ｓ２…内周側面。
DESCRIPTION OF SYMBOLS 1 ... Optical semiconductor device, 10 ... Substrate for optical semiconductor element mounting, 11 ... Recess, 12 ... Metal wiring, 15 ... Reflector, 16 ... Insulating layer, 20 ... Optical semiconductor element, 21 ... Bonding wire, 22 ... Solder bump, 30 DESCRIPTION OF SYMBOLS ... Sealing resin layer, 31 ... Transparent resin layer, 32 ... Phosphor, 40 ... Lead, 42 ... Die-bonding material, S1 ... Bottom surface (optical semiconductor element mounting area), S2 ... Inner peripheral side surface.
Claims (9)
前記硬化触媒が、テトラ−ｎ−ブチルホスホニウムテトラフルオロボレート、テトラ−ｎ−ブチルホスホニウムテトラフェニルボレート、テトラフェニルホスホニウムテトラフェニルボレート及び１，８−ジアザ−ビシクロ（５，４，０）ウンデセンテトラフェニルボレートからなる群より選ばれる少なくとも１種を含み、
前記エポキシ樹脂、前記硬化剤及び前記硬化触媒を含む混合物を３０℃〜１５０℃で溶融混練する工程を備える方法によって得ることのできる混錬物であり、
光反射部材を形成するために用いられる、熱硬化性樹脂組成物。 (A) epoxy resin, (B) curing agent, (C) curing catalyst, and (E) at least one selected from the group consisting of alumina, magnesium oxide, antimony oxide, titanium oxide, zirconium oxide, and inorganic hollow particles. A thermosetting resin composition containing a white pigment,
The curing catalyst is tetra-n-butylphosphonium tetrafluoroborate, tetra-n-butylphosphonium tetraphenylborate, tetraphenylphosphonium tetraphenylborate and 1,8-diaza-bicyclo (5,4,0) undecenetetraphenyl. Including at least one selected from the group consisting of borates,
A kneaded product obtainable by a method comprising a step of melt-kneading a mixture containing the epoxy resin, the curing agent and the curing catalyst at 30 ° C. to 150 ° C .;
A thermosetting resin composition used for forming a light reflecting member.
前記樹脂成形品が、請求項１〜６のいずれか一項に記載の熱硬化性樹脂組成物から形成することのできるものである、光半導体素子搭載用基板。 It has a recess composed of a bottom surface and an inner peripheral side surface, and has a resin molded product forming the inner peripheral side surface, and the bottom surface is an optical semiconductor element mounting substrate, which is an optical semiconductor element mounting region,
A substrate for mounting an optical semiconductor element, wherein the resin molded product can be formed from the thermosetting resin composition according to any one of claims 1 to 6 .
請求項１〜６のいずれか一項に記載の熱硬化性樹脂組成物をトランスファー成形することにより前記樹脂成形品を形成する工程を備える、製造方法。 A method of manufacturing a substrate for mounting an optical semiconductor element having a recess formed of a bottom surface and an inner peripheral side surface, and having a resin molded product forming the inner peripheral side surface, wherein the bottom surface is an optical semiconductor element mounting region. ,
A manufacturing method provided with the process of forming the said resin molded product by carrying out transfer molding of the thermosetting resin composition as described in any one of Claims 1-6 .
当該光半導体素子搭載用基板の光半導体素子搭載領域に搭載された光半導体素子と、
前記光半導体素子を当該光半導体素子搭載用基板の凹部内で覆う封止樹脂層と、
を備える光半導体装置。 The substrate for mounting an optical semiconductor element according to claim 7 ,
An optical semiconductor element mounted on the optical semiconductor element mounting region of the optical semiconductor element mounting substrate;
A sealing resin layer that covers the optical semiconductor element within the recess of the optical semiconductor element mounting substrate;
An optical semiconductor device comprising:
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| WO2014199728A1 (en) * | 2013-06-13 | 2014-12-18 | 日東電工株式会社 | Epoxy resin composition for optical semiconductor reflectors, thermosetting resin composition for optical semiconductor devices, lead frame for optical semiconductor devices obtained using said thermosetting resin composition for optical semiconductor devices, sealed optical semiconductor element, and optical semiconductor device |
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