JP6133004B2 - Thermosetting resin composition for light reflection, substrate for mounting optical semiconductor element, method for manufacturing the same, and optical semiconductor device - Google Patents
Thermosetting resin composition for light reflection, substrate for mounting optical semiconductor element, method for manufacturing the same, and optical semiconductor device Download PDFInfo
- Publication number
- JP6133004B2 JP6133004B2 JP2009084900A JP2009084900A JP6133004B2 JP 6133004 B2 JP6133004 B2 JP 6133004B2 JP 2009084900 A JP2009084900 A JP 2009084900A JP 2009084900 A JP2009084900 A JP 2009084900A JP 6133004 B2 JP6133004 B2 JP 6133004B2
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- JP
- Japan
- Prior art keywords
- optical semiconductor
- light
- thermosetting resin
- semiconductor element
- resin composition
- Prior art date
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- 239000004065 semiconductor Substances 0.000 title claims description 129
- 230000003287 optical effect Effects 0.000 title claims description 128
- 229920001187 thermosetting polymer Polymers 0.000 title claims description 106
- 239000011342 resin composition Substances 0.000 title claims description 91
- 239000000758 substrate Substances 0.000 title claims description 65
- 238000000034 method Methods 0.000 title claims description 37
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- 229920005989 resin Polymers 0.000 claims description 62
- 239000011347 resin Substances 0.000 claims description 62
- 239000002245 particle Substances 0.000 claims description 29
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 26
- 229920000647 polyepoxide Polymers 0.000 claims description 26
- 239000003822 epoxy resin Substances 0.000 claims description 25
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 24
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 20
- 238000007789 sealing Methods 0.000 claims description 14
- 238000000465 moulding Methods 0.000 claims description 12
- 238000001721 transfer moulding Methods 0.000 claims description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- 241000282376 Panthera tigris Species 0.000 claims 1
- 239000000463 material Substances 0.000 description 27
- 239000003795 chemical substances by application Substances 0.000 description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 18
- 239000010410 layer Substances 0.000 description 18
- 239000000047 product Substances 0.000 description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 14
- -1 bulk Substances 0.000 description 13
- 239000000126 substance Substances 0.000 description 12
- 239000011889 copper foil Substances 0.000 description 11
- 239000002585 base Substances 0.000 description 10
- 238000004898 kneading Methods 0.000 description 10
- 238000002156 mixing Methods 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 8
- 239000004020 conductor Substances 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 238000013329 compounding Methods 0.000 description 6
- 239000007822 coupling agent Substances 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 238000007747 plating Methods 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000012463 white pigment Substances 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 150000008065 acid anhydrides Chemical class 0.000 description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical group C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 239000011256 inorganic filler Substances 0.000 description 5
- 229910003475 inorganic filler Inorganic materials 0.000 description 5
- 239000011800 void material Substances 0.000 description 5
- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical group C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 4
- 239000012778 molding material Substances 0.000 description 4
- 238000001579 optical reflectometry Methods 0.000 description 4
- 238000012360 testing method Methods 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
- 239000004925 Acrylic resin Substances 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 3
- 239000012790 adhesive layer Substances 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000007766 curtain coating Methods 0.000 description 3
- 238000007607 die coating method Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000005350 fused silica glass Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 150000002903 organophosphorus compounds Chemical class 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 239000005368 silicate glass Substances 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 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
- PAVNZLVXYJDFNR-UHFFFAOYSA-N 3,3-dimethyloxane-2,6-dione Chemical compound CC1(C)CCC(=O)OC1=O PAVNZLVXYJDFNR-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical group C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-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
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-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
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 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
- 230000008901 benefit Effects 0.000 description 2
- 239000005388 borosilicate glass Substances 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
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000013078 crystal Substances 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
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 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 2
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 239000007788 liquid Substances 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
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
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- 150000004706 metal oxides Chemical class 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-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
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
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- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-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
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- 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
- 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 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- MWIQWRCANQOMBX-UHFFFAOYSA-N 2,2-diethylpentanedioic acid Chemical compound CCC(CC)(C(O)=O)CCC(O)=O MWIQWRCANQOMBX-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
- 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
- UVYLEXYRTBDZNM-UHFFFAOYSA-N 4,4-diethyloxane-2,6-dione Chemical compound CCC1(CC)CC(=O)OC(=O)C1 UVYLEXYRTBDZNM-UHFFFAOYSA-N 0.000 description 1
- OECTYKWYRCHAKR-UHFFFAOYSA-N 4-vinylcyclohexene dioxide Chemical compound C1OC1C1CC2OC2CC1 OECTYKWYRCHAKR-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- RBHIUNHSNSQJNG-UHFFFAOYSA-N 6-methyl-3-(2-methyloxiran-2-yl)-7-oxabicyclo[4.1.0]heptane Chemical compound C1CC2(C)OC2CC1C1(C)CO1 RBHIUNHSNSQJNG-UHFFFAOYSA-N 0.000 description 1
- YXALYBMHAYZKAP-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl 7-oxabicyclo[4.1.0]heptane-4-carboxylate Chemical compound C1CC2OC2CC1C(=O)OCC1CC2OC2CC1 YXALYBMHAYZKAP-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
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- 150000001339 alkali metal compounds Chemical class 0.000 description 1
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- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 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
- DJUWPHRCMMMSCV-UHFFFAOYSA-N bis(7-oxabicyclo[4.1.0]heptan-4-ylmethyl) hexanedioate Chemical compound C1CC2OC2CC1COC(=O)CCCCC(=O)OCC1CC2OC2CC1 DJUWPHRCMMMSCV-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
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- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
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- 239000002131 composite material Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
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- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- XBZSBBLNHFMTEB-UHFFFAOYSA-N cyclohexane-1,3-dicarboxylic acid Chemical compound OC(=O)C1CCCC(C(O)=O)C1 XBZSBBLNHFMTEB-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
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- 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
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- 238000007429 general method Methods 0.000 description 1
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- 125000003055 glycidyl group Chemical group C(C1CO1)* 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
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Images
Classifications
-
- 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
- H01L2224/26—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
-
- 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
- H01L2224/4805—Shape
- H01L2224/4809—Loop shape
- H01L2224/48091—Arched
-
- 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
-
- 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
- H01L2224/732—Location after the connecting process
- H01L2224/73251—Location after the connecting process on different surfaces
- H01L2224/73265—Layer and wire connectors
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
- Led Device Packages (AREA)
Description
本発明は、光反射用熱硬化性樹脂組成物、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 for light reflection, a substrate for mounting an optical semiconductor element, a method for manufacturing the same, and an optical semiconductor device.
ＬＥＤ（Ｌｉｇｈｔ Ｅｍｉｔｔｉｎｇ Ｄｉｏｄｅ：発光ダイオード）等の光半導体素子と蛍光体とを組み合わせた光半導体装置は、エネルギー効率が高く、寿命が長いことから、屋外用ディスプレイ、携帯液晶バックライト、車載用途に使用され、その需要が拡大しつつある。これに伴いＬＥＤデバイスの高輝度化が進んでおり、素子の発熱量増大によるジャンクション温度の上昇や、直接的な光エネルギーの増大による光半導体装置の劣化を防ぐことが求められている。 An optical semiconductor device combining an optical semiconductor element such as an LED (Light Emitting Diode) and a phosphor is high in energy efficiency and has a long life, so it is used for outdoor displays, portable liquid crystal backlights, and in-vehicle applications. The demand is expanding. As a result, the brightness of LED devices is increasing, and it is required to prevent an increase in junction temperature due to an increase in the amount of heat generated by the element and deterioration of the optical semiconductor device due to a direct increase in light energy.
特許文献１には、可視光から近紫外光領域において高い反射率を有する光反射用熱硬化性樹脂組成物を用いた光半導体素子搭載用基板が開示されている。また、特許文献２には、白色度を長く維持できる成形用樹脂組成物が開示されている。 Patent Document 1 discloses a substrate for mounting an optical semiconductor element using a light-reflective thermosetting resin composition having a high reflectance in the visible light to near ultraviolet light region. Patent Document 2 discloses a molding resin composition that can maintain whiteness for a long time.
しかし、従来の光反射用熱硬化性樹脂組成物を用いた光半導体素子搭載用基板では、光半導体素子の外周を取り囲むように備えられた光反射用熱硬化性樹脂組成物の硬化物からなる壁面、又は該硬化物によって電極間が充填された基板底部を、光半導体素子からの発光が一部透過して漏れ光が発生することがある。その結果、光半導体装置の上面へ放射されるべき光が損失して、光取出し効率を低下させる傾向にある。 However, the conventional substrate for mounting an optical semiconductor element using the thermosetting resin composition for reflecting light is made of a cured product of the thermosetting resin composition for reflecting light provided so as to surround the outer periphery of the optical semiconductor element. The light emitted from the optical semiconductor element may partially transmit through the wall surface or the bottom of the substrate filled with the cured product between the electrodes, and leakage light may be generated. As a result, light to be emitted to the upper surface of the optical semiconductor device is lost, and the light extraction efficiency tends to be reduced.
従来の光反射用熱硬化性樹脂組成物を用いた光半導体素子搭載用基板は、これを小型化する場合、光半導体素子の外周を取り囲むように備えられた光反射用熱硬化性樹脂組成物の硬化物からなる壁面、又は同樹脂組成物の硬化物によって電極間が充填された基板底部を薄厚化し対応している。しかしながら、小型の光半導体装置により高出力の素子を搭載することが可能となり、その結果、壁面や底部の薄厚化に伴い光半導体素子からの発光が一部透過する漏れ光が発生し易くなる。そして、光漏れが発生すると光半導体装置の上面へ放射されるべき光が損失して、光半導体装置としての光取出し効率を低下させてしまう。また、従来の白色度を長く維持できる成形用樹脂組成物において、光漏れを抑制するために白色顔料の添加量を多くすると、樹脂組成物の成形性が低下してしまい、光半導体素子搭載用基板を製造することが難しい傾向にある。 A conventional substrate for mounting an optical semiconductor element using a thermosetting resin composition for light reflection is a thermosetting resin composition for light reflection that is provided so as to surround the outer periphery of the optical semiconductor element when the substrate is miniaturized. The wall surface made of the cured product or the bottom of the substrate filled with the cured product of the resin composition is made thinner. However, it is possible to mount a high-power element by a small optical semiconductor device, and as a result, leakage light that partially transmits light emitted from the optical semiconductor element is easily generated as the wall surface and the bottom are made thinner. When light leakage occurs, light to be emitted to the upper surface of the optical semiconductor device is lost, and the light extraction efficiency as the optical semiconductor device is reduced. In addition, in a conventional molding resin composition capable of maintaining a long whiteness, if the amount of white pigment added is increased in order to suppress light leakage, the moldability of the resin composition decreases, and the optical semiconductor element mounting It tends to be difficult to manufacture a substrate.
そこで、本発明は、光半導体素子搭載用基板における光漏れを十分に低減できる硬化物を形成可能な光反射用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を提供することを目的とする。 Accordingly, the present invention relates to a light-reflective thermosetting resin composition capable of forming a cured product capable of sufficiently reducing light leakage in an optical semiconductor element mounting substrate, an optical semiconductor element mounting substrate using the same, and a method for manufacturing the same. An object is to provide an optical semiconductor device.
本発明者らは、光反射用熱硬化性樹脂組成物の光漏れを発生させる要因について鋭意検討を重ねた結果、光反射用熱硬化性樹脂組成物中に含有される熱硬化性樹脂よりも屈折率が大きい無機酸化物を所定量含有させることで光漏れを低減できることを見出し、本発明を完成するに至った。 As a result of intensive studies on the factors causing light leakage of the light-reflective thermosetting resin composition, the present inventors have found that the light-reflective thermosetting resin composition contains more than the thermosetting resin contained in the light-reflective thermosetting resin composition. The inventors have found that light leakage can be reduced by containing a predetermined amount of an inorganic oxide having a large refractive index, and have completed the present invention.
本発明は、エポキシ樹脂を含む熱硬化性樹脂と、屈折率１．６〜３．０の無機酸化物とを含有し、無機酸化物の配合量が、熱硬化性樹脂１００質量部に対して７０〜４００質量部である光反射用熱硬化性樹脂組成物を提供する。 This invention contains the thermosetting resin containing an epoxy resin, and the inorganic oxide of refractive index 1.6-3.0, and the compounding quantity of an inorganic oxide is with respect to 100 mass parts of thermosetting resins. The thermosetting resin composition for light reflection which is 70-400 mass parts is provided.
上記無機酸化物は、酸化チタン、酸化亜鉛、酸化アルミニウム、酸化マグネシウム、酸化ジルコニウム、酸化アンチモン、水酸化アルミニウム及び水酸化マグネシウムからなる群より選ばれる少なくとも１種の無機酸化物を含むことが好ましい。 The inorganic oxide preferably contains at least one inorganic oxide selected from the group consisting of titanium oxide, zinc oxide, aluminum oxide, magnesium oxide, zirconium oxide, antimony oxide, aluminum hydroxide, and magnesium hydroxide.
光反射性熱硬化性樹脂組成物中における分散性を向上する観点から、無機酸化物の中心粒径は０．１〜２０μｍであることが好ましい。また、無機酸化物の配合量が、熱硬化性樹脂１００質量部に対して１３０〜４００質量部であると、トランスファー成形性に優れるものとなる。 From the viewpoint of improving dispersibility in the light-reflective thermosetting resin composition, the center particle size of the inorganic oxide is preferably 0.1 to 20 μm. Moreover, it becomes what is excellent in transfer moldability that the compounding quantity of an inorganic oxide is 130-400 mass parts with respect to 100 mass parts of thermosetting resins.
本発明の光反射用熱硬化性樹脂組成物は、空隙部の屈折率が１．０〜１．１である中空粒子を更に含有することが好ましい。 The light-reflective thermosetting resin composition of the present invention preferably further contains hollow particles having a void portion having a refractive index of 1.0 to 1.1.
上記中空粒子の外殻は、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、架橋スチレン系樹脂及び架橋アクリル系樹脂からなる群より選ばれる少なくとも１種の材質を含むことが好ましい。 The outer shell of the hollow particles preferably contains at least one material selected from the group consisting of sodium silicate glass, aluminum silicate glass, borosilicate soda glass, a crosslinked styrene resin, and a crosslinked acrylic resin.
光反射性の観点から、中空粒子の中心粒径は０．１〜５０μｍであることが好ましい。また、中空粒子の配合量は、熱硬化性樹脂１００質量部に対して２０〜８５質量部であると、トランスファー成形性に優れるものとなる。 From the viewpoint of light reflectivity, the center particle diameter of the hollow particles is preferably 0.1 to 50 μm. Moreover, the compounding quantity of a hollow particle will be excellent in transfer moldability in it being 20-85 mass parts with respect to 100 mass parts of thermosetting resins.
本発明の光反射用熱硬化性樹脂組成物は、硬化後の波長８００〜４６０ｎｍにおける光反射率が９０％以上であることが好ましい。 The light reflecting thermosetting resin composition of the present invention preferably has a light reflectance of 90% or more at a wavelength of 800 to 460 nm after curing.
本発明は、底面及び壁面から構成される凹部を有し、凹部の底面が光半導体素子搭載部であり、凹部の壁面の少なくとも一部が本発明の光反射用熱硬化性樹脂組成物の硬化物からなる光半導体素子搭載用基板を提供する。 The present invention has a recess composed of a bottom surface and a wall surface, the bottom surface of the recess is an optical semiconductor element mounting portion, and at least a part of the wall surface of the recess is cured of the thermosetting resin composition for light reflection of the present invention. Provided is an optical semiconductor element mounting substrate made of a material.
本発明はまた、底面及び壁面から構成される凹部を有する光半導体素子搭載用基板の製造方法であって、凹部の壁面の少なくとも一部を本発明の光反射用熱硬化性樹脂組成物を用いたトランスファー成形により形成する工程を備える光半導体素子搭載用基板の製造方法を提供する。 The present invention is also a method for manufacturing a substrate for mounting an optical semiconductor element having a recess composed of a bottom surface and a wall surface, wherein the thermosetting resin composition for light reflection of the present invention is used for at least a part of the wall surface of the recess. The manufacturing method of the board | substrate for optical-semiconductor element mounting provided with the process formed by transfer molding which was performed.
本発明はさらに、底面及び壁面から構成される凹部を有する光半導体素子搭載用基板と、光半導体素子搭載用基板の凹部内に設けられた光半導体素子と、凹部を充填して光半導体素子を封止する封止樹脂部とを備え、凹部の壁面の少なくとも一部が、本発明の光反射用熱硬化性樹脂組成物の硬化物からなる光半導体装置を提供する。 The present invention further includes an optical semiconductor element mounting substrate having a recess composed of a bottom surface and a wall surface, an optical semiconductor element provided in the recess of the optical semiconductor element mounting substrate, and an optical semiconductor element filled with the recess. There is provided an optical semiconductor device including a sealing resin portion to be sealed, and at least a part of the wall surface of the recess is made of a cured product of the thermosetting resin composition for light reflection of the present invention.
本発明によれば、光半導体素子搭載用基板における光漏れを十分に低減できる硬化物を形成可能な光反射用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を提供することを目的とする。 ADVANTAGE OF THE INVENTION According to this invention, the thermosetting resin composition for light reflection which can form the hardened | cured material which can fully reduce the light leak in the optical semiconductor element mounting substrate, the optical semiconductor element mounting substrate using the same, and its manufacturing method An object is to provide an optical semiconductor device.
以下、必要に応じて図面を参照しつつ、本発明の好適な実施形態について詳細に説明する。なお、図面中、同一要素には同一符号を付すこととし、重複する説明は省略する。また、上下左右等の位置関係は、特に断らない限り、図面に示す位置関係に基づくものとする。更に、図面の寸法比率は図示の比率に限られるものではない。また、本明細書における「（メタ）アクリレート」とは、「アクリレート」及びそれに対応する「メタクリレート」を意味する。 Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as necessary. In the drawings, the same elements are denoted by the same reference numerals, and redundant description is omitted. Further, the positional relationship such as up, down, left and right is based on the positional relationship shown in the drawings unless otherwise specified. Further, the dimensional ratios in the drawings are not limited to the illustrated ratios. In addition, “(meth) acrylate” in the present specification means “acrylate” and “methacrylate” corresponding thereto.
（屈折率の測定方法）
本実施形態に係る屈折率は、温度２５℃におけるｄ線（５８７．５６２ｎｍ、Ｈｅ）の光に対する値を示すものである。屈折率は、臨界角法、プリズムカップリング法、ベッケ法、ｖブロック法等の原理に従い、種々の屈折計を用いて測定することができる。測定装置としては、分光計、アッベ屈折計、プルリッヒ屈折計、エリプソメーターが挙げられる。屈折率の測定方法は、測定対象物の性状（固体、液体等）に合わせて選択することができる。また、測定対象物が固体である場合には、その形状が薄膜、バルク又は粉体により屈折率の測定方法を選択することができる。例えば、測定対象物が固体の場合、測定対象物を公知の方法で薄膜化してアッベ屈折計又はエリプソメーターを用いて測定することができる。無機酸化物等の白色顔料の屈折率は、白色顔料を構成する成分の形状（バルクや薄膜）における測定値を適用してもよい。白色顔料が粉体である場合には、ベッケ法が用いられる。本明細書において、熱硬化性樹脂の屈折率は、Ｖブロック法（測定装置：ＫＰＲ、カルニュー光学製）により、白色顔料の屈折率は、ベッケ法（標準溶液と比較する方法）により測定したものである。なお、中空粒子については、空気や不活性ガスによって空隙部が満たされているため、空隙部の屈折率として、空気又は不活性ガスの屈折率に相当する「１．０〜１．１」の数値を適用することができる。
(Measurement method of refractive index)
The refractive index according to the present embodiment indicates a value for light of d-line (587.562 nm, He) at a temperature of 25 ° C. The refractive index can be measured using various refractometers according to principles such as a critical angle method, a prism coupling method, a Becke method, and a v-block method. Examples of the measuring apparatus include a spectrometer, an Abbe refractometer, a Pullrich refractometer, and an ellipsometer. The method of measuring the refractive index can be selected according to the properties (solid, liquid, etc.) of the measurement object. When the measurement object is a solid, the refractive index measurement method can be selected depending on the shape of the thin film, bulk, or powder. For example, when the measurement object is a solid, the measurement object can be thinned by a known method and measured using an Abbe refractometer or an ellipsometer. As the refractive index of a white pigment such as an inorganic oxide, a measured value in the shape (bulk or thin film) of a component constituting the white pigment may be applied. When the white pigment is powder, the Becke method is used. In the present specification, the refractive index of the thermosetting resin is measured by the V block method (measurement apparatus: KPR, manufactured by Kalnew Optical), and the refractive index of the white pigment is measured by the Becke method (method compared with the standard solution). It is. In addition, about the hollow particle, since the void portion is filled with air or inert gas, the refractive index of the void portion is “1.0 to 1.1” corresponding to the refractive index of air or inert gas. Numerical values can be applied.
［光反射用熱硬化性樹脂組成物］
本発明の光反射用熱硬化性樹脂組成物は、エポキシ樹脂を含む熱硬化性樹脂と、屈折率１．６〜３．０の無機酸化物とを含有し、無機酸化物の配合量が、熱硬化性樹脂１００質量部に対して７０〜４００質量部である。
[Thermosetting resin composition for light reflection]
The thermosetting resin composition for light reflection of the present invention contains a thermosetting resin containing an epoxy resin and an inorganic oxide having a refractive index of 1.6 to 3.0, and the blending amount of the inorganic oxide is It is 70-400 mass parts with respect to 100 mass parts of thermosetting resins.
＜屈折率１．６〜３．０の無機酸化物＞
本発明に係る無機酸化物の屈折率は、１．６〜３．０であり、１．８〜３．０であることが好ましく、２．０〜３．０であることがより好ましい。屈折率が１．６〜３．０の範囲にある無機酸化物としては、屈折率２．５〜２．７の酸化チタン、屈折率１．９〜２．０の酸化亜鉛、屈折率１．６〜１．８の酸化アルミニウム、屈折率１．７の酸化マグネシウム、屈折率２．４の酸化ジルコニウム、屈折率１．６の水酸化アルミニウム、屈折率１．６の水酸化マグネシウムが挙げられる。これらの中でも、無機酸化物として屈折率のより高い酸化チタンを含むことが好ましい。また、無機酸化物は、光反射用熱硬化性樹脂組成物中に含有される熱硬化性樹脂の屈折率よりも大きい屈折率を有することが求められるため、用いられる熱硬化性樹脂を構成する成分との組合せで適宜選択することができる。ここで、本明細書における屈折率は、波長５４０ｎｍの光で測定した値である。
<Inorganic oxide having a refractive index of 1.6 to 3.0>
The refractive index of the inorganic oxide according to the present invention is 1.6 to 3.0, preferably 1.8 to 3.0, and more preferably 2.0 to 3.0. Examples of the inorganic oxide having a refractive index in the range of 1.6 to 3.0 include titanium oxide having a refractive index of 2.5 to 2.7, zinc oxide having a refractive index of 1.9 to 2.0, and a refractive index of 1. Examples thereof include aluminum oxide having 6 to 1.8, magnesium oxide having a refractive index of 1.7, zirconium oxide having a refractive index of 2.4, aluminum hydroxide having a refractive index of 1.6, and magnesium hydroxide having a refractive index of 1.6. Among these, it is preferable to include titanium oxide having a higher refractive index as an inorganic oxide. Further, since the inorganic oxide is required to have a refractive index larger than the refractive index of the thermosetting resin contained in the light reflecting thermosetting resin composition, it constitutes the thermosetting resin used. It can select suitably with the combination with a component. Here, the refractive index in this specification is a value measured with light having a wavelength of 540 nm.
上記酸化チタンは、酸化チタン（ＴｉＯ２）としての含有量が８０〜９７重量％に調整された微小粒子系の酸化チタンをベースに、特定の表面処理剤で表面処理されたものである。酸化チタンの表面処理剤としては、例えば、シリカ、アルミナ、ジルコニア等の金属酸化物；シランカップリング剤、チタンカップリング剤、有機酸、ポリオール、シリコーン等の有機物が挙げられる。シリカ、アルミナ及びジルコニアから選ばれた少なくとも一種、又はシリカ、アルミナ、ジルコニア及び有機物から選ばれた少なくとも一種で表面処理された酸化チタンが好ましい。熱硬化性樹脂との密着性を向上させる観点から、エポキシシラン等のシランカップリング剤を用いてさらに表面を有機処理してもよい。酸化チタンの結晶型としては、屈折率２．７のルチル型、屈折率２．５のアナターゼ型及び屈折率２．６のブルッカイト型がある。酸化チタンの結晶型は特に限定されないが、屈折率及び光吸収特性の観点からルチル型が好ましい。 The titanium oxide is surface-treated with a specific surface treatment agent based on fine particle titanium oxide whose content as titanium oxide (TiO 2 ) is adjusted to 80 to 97% by weight. Examples of the surface treatment agent for titanium oxide include metal oxides such as silica, alumina, and zirconia; and organic substances such as silane coupling agents, titanium coupling agents, organic acids, polyols, and silicones. Titanium oxide surface-treated with at least one selected from silica, alumina and zirconia, or at least one selected from silica, alumina, zirconia and organic substances is preferred. From the viewpoint of improving the adhesion with the thermosetting resin, the surface may be further organically treated using a silane coupling agent such as epoxysilane. As a crystal type of titanium oxide, there are a rutile type having a refractive index of 2.7, an anatase type having a refractive index of 2.5, and a brookite type having a refractive index of 2.6. The crystal type of titanium oxide is not particularly limited, but the rutile type is preferable from the viewpoint of refractive index and light absorption characteristics.
酸化チタンは、市販品を入手して使用することができる。ルチル型酸化チタンとして、例えば、堺化学工業社製の商品名：Ｄ−９１８、ＦＴＲ−７００、石原産業社製の商品名：タイペークＣＲ−５０、ＣＲ−５０−２、ＣＲ−６０、ＣＲ−６０−２、ＣＲ−６３、ＣＲ−８０、ＣＲ−９０、ＣＲ−９０−２、ＣＲ−９３、ＣＲ−９５、ＣＲ−９７、テイカ社製の商品名：ＪＲ−４０３、ＪＲ−８０５、ＪＲ−８０６、ＪＲ−７０１、ＪＲ−８００、冨士チタン工業社製の商品名：ＴＲ−６００、ＴＲ−７００、ＴＲ−７５０、ＴＲ−８４０、ＴＲ−９００が挙げられる。ここで、酸化チタンは、原料となる天然物を、公知の硫酸法又は塩酸法で製造して得られる。硫酸法又は塩酸法のそれぞれから得られる酸化チタンは、屈折率が同等であるにもかかわらず、製造時に処理液から混入する元素の違いにより、酸化チタンの色、すなわち反射スペクトル特性が異なるものが得られる。通常、塩酸法から得られる酸化チタンは波長４６０〜８００ｎｍの光反射率が高く、硫酸法から得られる酸化チタンは波長４６０〜８００ｎｍの光反射率が前者に劣る。特に本発明の光半導体装置に光反射用熱硬化性樹脂組成物を使用する際、光反射用熱硬化性樹脂組成物に含まれる酸化チタンは波長４６０〜８００ｎｍの光反射率が高い塩酸法で製造されるものを用いることが好ましい。 Titanium oxide can be used by obtaining a commercial product. Examples of the rutile titanium oxide include trade names manufactured by Sakai Chemical Industry Co., Ltd .: D-918, FTR-700, trade names manufactured by Ishihara Sangyo Co., Ltd .: Taipei CR-50, CR-50-2, CR-60, CR- 60-2, CR-63, CR-80, CR-90, CR-90-2, CR-93, CR-95, CR-97, trade names manufactured by Teica: JR-403, JR-805, JR -806, JR-701, JR-800, trade names manufactured by Fuji Titanium Industry Co., Ltd .: TR-600, TR-700, TR-750, TR-840, TR-900. Here, titanium oxide is obtained by producing a natural product as a raw material by a known sulfuric acid method or hydrochloric acid method. Titanium oxide obtained from each of the sulfuric acid method and hydrochloric acid method has different refractive index, but the color of titanium oxide, that is, the reflection spectrum characteristics, is different due to the difference in the elements mixed from the treatment liquid during production. can get. Usually, titanium oxide obtained from the hydrochloric acid method has a high light reflectance at a wavelength of 460 to 800 nm, and titanium oxide obtained from a sulfuric acid method has a light reflectance at a wavelength of 460 to 800 nm inferior to the former. In particular, when the light-reflective thermosetting resin composition is used in the optical semiconductor device of the present invention, titanium oxide contained in the light-reflective thermosetting resin composition is a hydrochloric acid method having a high light reflectance at a wavelength of 460 to 800 nm. It is preferable to use what is manufactured.
無機酸化物の中心粒径は、光反射用熱硬化性樹脂組成物中における分散性の観点から、０．１〜２０μｍであることが好ましく、０．１〜１０μｍであることがより好ましく、０．１〜５μｍであることが更に好ましい。無機酸化物の中心粒子径を上記の範囲内とすることにより、表面反射率の高い成形品を与える光反射用熱硬化性樹脂組成物を得ることができる。 The central particle diameter of the inorganic oxide is preferably 0.1 to 20 μm, more preferably 0.1 to 10 μm, from the viewpoint of dispersibility in the light-reflective thermosetting resin composition. More preferably, it is 1-5 micrometers. By setting the center particle diameter of the inorganic oxide within the above range, it is possible to obtain a light-reflective thermosetting resin composition that gives a molded product having a high surface reflectance.
無機酸化物の配合量は、熱硬化性樹脂１００質量部に対して７０〜４００質量部であり、９０〜４００質量部であることが好ましく、１３０〜４００質量部であることがより好ましく、１３０〜３８０質量部であることが更に好ましい。また、光反射用熱硬化性樹脂組成物をトランスファー成形用として使用する場合には、熱硬化性樹脂１００質量部に対して、７０〜４００質量部であることが好ましく、基板コーティング用として使用する場合には、１３０〜４００質量部であることが好ましい。無機酸化物の配合量が７０質量部未満では、光反射用熱硬化性樹脂組成物から形成される硬化物の光漏れ特性が十分に得られ難い傾向があり、４００質量部を超えると光反射用熱硬化性樹脂組成物の成型性が低下する傾向がある。 The compounding amount of the inorganic oxide is 70 to 400 parts by mass with respect to 100 parts by mass of the thermosetting resin, preferably 90 to 400 parts by mass, more preferably 130 to 400 parts by mass, and 130 More preferably, it is -380 mass parts. Moreover, when using the thermosetting resin composition for light reflections for transfer molding, it is preferable that it is 70-400 mass parts with respect to 100 mass parts of thermosetting resins, and it uses it for board | substrate coating. In the case, it is preferably 130 to 400 parts by mass. If the blending amount of the inorganic oxide is less than 70 parts by mass, the light leakage property of the cured product formed from the thermosetting resin composition for light reflection tends to be insufficient, and if it exceeds 400 parts by mass, the light reflection is There exists a tendency for the moldability of the thermosetting resin composition for water to fall.
＜熱硬化性樹脂＞
（エポキシ樹脂）
エポキシ樹脂としては、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を用いることができる。エポキシ樹脂として、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等のフェノール類とアルデヒド類のノボラック樹脂をエポキシ化したもの、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及びイソシアヌル酸等のポリアミンとエピクロルヒドリンと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、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、並びに脂環族エポキシ樹脂が挙げられる。これらは、１種を単独で又は２種以上を組み合わせて用いることができる。
<Thermosetting resin>
(Epoxy resin)
As an epoxy resin, what is generally used with the epoxy resin molding material for electronic component sealing can be used. Epoxy resins include, for example, epoxidized phenol and aldehyde novolak resins such as phenol novolac type epoxy resin and orthocresol novolak type epoxy resin, diglycidyl such as bisphenol A, bisphenol F, bisphenol S and alkyl substituted bisphenol Glycidylamine type epoxy resin obtained by reaction of polyamine such as ether, diaminodiphenylmethane and isocyanuric acid with epichlorohydrin, linear aliphatic epoxy resin obtained by oxidizing olefin bond with peracid such as peracetic acid, and alicyclic An epoxy resin is mentioned. These can be used alone or in combination of two or more.
これらのうち、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、及び、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又は１，４−シクロヘキサン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、比較的着色が少ないことから好ましい。同様の理由から、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等のジカルボン酸のジグリシジルエステルも好適である。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、核水素化ピロメリット酸等のグリシジルエステルも挙げられる。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製造される、エポキシ基を有するポリオルガノシロキサンも挙げられる。 Among these, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, diglycidyl isocyanurate, triglycidyl isocyanurate, and 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid or A dicarboxylic acid diglycidyl ester derived from 1,4-cyclohexanedicarboxylic acid is preferable because of relatively little coloring. For the same reason, diglycidyl esters of dicarboxylic acids such as phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methyltetrahydrophthalic acid, nadic acid and methylnadic acid are also suitable. Examples thereof include glycidyl esters such as nuclear hydrogenated trimellitic acid and nuclear hydrogenated pyromellitic acid having an alicyclic structure in which an aromatic ring is hydrogenated. Polyorganosiloxane having an epoxy group produced by heating and hydrolyzing and condensing a silane compound in the presence of an organic solvent, an organic base and water is also included.
エポキシ樹脂として、その入手方法に制限はなく市販品を使用することもできる。例えば、３，４−エポキシシクロヘキシルメチル−３’，４’−エポキシシクロヘキサンカルボキシレートとして、セロキサイド２０２１、セロキサイド２０２１Ａ、セロキサイド２０２１Ｐ（以上、ダイセル化学工業社製、商品名）、ＥＲＬ４２２１、ＥＲＬ４２２１Ｄ、ＥＲＬ４２２１Ｅ（以上、ダウケミカル日本社製、商品名）を入手できる。また、ビス（３，４−エポキシシクロヘキシルメチル）アジペートとして、ＥＲＬ４２９９（ダウケミカル日本社製、商品名）、ＥＸＡ７０１５（大日本インキ化学工業社製、商品名）を入手できる。更に、１−エポキシエチル−３，４−エポキシシクロヘキサン又はリモネンジエポキシドとして、エピコートＹＸ８０００、エピコートＹＸ８０３４、エピコートＹＬ７１７０（以上、ジャパンエポキシレジン社製、商品名）、セロキサイド２０８１、セロキサイド３０００、エポリードＧＴ３０１、エポリードＧＴ４０１、ＥＨＰＥ３１５０（以上、ダイセル化学工業社製）を、トリスグリシジルイソシアヌレートであるＴＥＰＩＣ（日産化学製、商品名）を入手可能である。 There is no restriction | limiting in the acquisition method as an epoxy resin, and a commercial item can also be used. For example, as 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, Celoxide 2021, Celoxide 2021A, Celoxide 2021P (above, Daicel Chemical Industries, trade name), ERL 4221, ERL 4221D, ERL 4221E (above Available from Dow Chemical Japan Co., Ltd.). Further, as bis (3,4-epoxycyclohexylmethyl) adipate, ERL4299 (manufactured by Dow Chemical Japan, trade name) and EXA7015 (manufactured by Dainippon Ink & Chemicals, trade name) can be obtained. Further, as 1-epoxyethyl-3,4-epoxycyclohexane or limonene diepoxide, Epicoat YX8000, Epicoat YX8034, Epicoat YL7170 (above, trade name, manufactured by Japan Epoxy Resin Co., Ltd.), Celoxide 2081, Celoxide 3000, Epolide GT301, Epolide GTPIC, EHPE3150 (manufactured by Daicel Chemical Industries, Ltd.), and TEPIC (trade name, manufactured by Nissan Chemical Co., Ltd.) which is trisglycidyl isocyanurate are available.
（硬化剤）
本発明の光反射用熱硬化性樹脂組成物は、硬化剤を含むことが好ましい。硬化剤としては、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硬化剤を用いることができる。このような硬化剤としては、エポキシ樹脂と反応するものであれば、特に限定されないが、着色の少ないものが好ましく、無色又は淡黄色であることがより好ましい。
(Curing agent)
The light reflecting thermosetting resin composition of the present invention preferably contains a curing agent. As a hardening | curing agent, the hardening | curing agent generally used with the epoxy resin molding material for electronic component sealing can be used. Such a curing agent is not particularly limited as long as it reacts with an epoxy resin, but is preferably less colored, and more preferably colorless or light yellow.
このような硬化剤として、例えば、酸無水物系硬化剤、イソシアヌル酸誘導体系硬化剤、フェノール系硬化剤が挙げられる。酸無水物系硬化剤としては、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、メチルテトラヒドロ無水フタル酸が挙げられる。イソシアヌル酸誘導体としては、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、１，３−ビス（２−カルボキシエチル）イソシアヌレートが挙げられる。これらの硬化剤の中では、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又は１，３，５−トリス（３−カルボキシプロピル）イソシアヌレートを用いることが好ましい。上記硬化剤は、１種を単独で又は２種以上を組み合わせてもよい。 Examples of such a curing agent include an acid anhydride curing agent, an isocyanuric acid derivative curing agent, and a phenol curing agent. Examples of the acid anhydride curing agent include phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, glutaric anhydride. Examples include acid, dimethyl glutaric anhydride, diethyl glutaric anhydride, succinic anhydride, methyl hexahydrophthalic anhydride, and methyl tetrahydrophthalic anhydride. Isocyanuric acid derivatives include 1,3,5-tris (1-carboxymethyl) isocyanurate, 1,3,5-tris (2-carboxyethyl) isocyanurate, 1,3,5-tris (3-carboxypropyl) ) Isocyanurate, 1,3-bis (2-carboxyethyl) isocyanurate. Among these curing agents, phthalic anhydride, trimellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, glutaric anhydride, dimethylglutaric anhydride, anhydrous It is preferable to use diethyl glutaric acid or 1,3,5-tris (3-carboxypropyl) isocyanurate. The above curing agents may be used alone or in combination of two or more.
上述の硬化剤は、分子量が１００〜４００であることが好ましい。また、無水トリメリット酸、無水ピロメリット酸等の芳香環を有する酸無水物よりも、芳香環の不飽和結合のすべてを水素化した無水物が好ましい。酸無水物系硬化剤として、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用いてもよい。 The above-mentioned curing agent preferably has a molecular weight of 100 to 400. In addition, an anhydride obtained by hydrogenating all unsaturated bonds of an aromatic ring is preferable to an acid anhydride having an aromatic ring such as trimellitic anhydride or pyromellitic anhydride. As the acid anhydride curing agent, an acid anhydride generally used as a raw material for the polyimide resin may be used.
本発明の光反射用熱硬化性樹脂組成物において、硬化剤の配合量は、エポキシ樹脂１００質量部に対して、１〜１５０質量部であることが好ましく、５０〜１２０質量部であることがより好ましい。 In the thermosetting resin composition for light reflection of the present invention, the blending amount of the curing agent is preferably 1 to 150 parts by mass, and preferably 50 to 120 parts by mass with respect to 100 parts by mass of the epoxy resin. More preferred.
また、硬化剤は、エポキシ樹脂中のエポキシ基１当量に対して、当該エポキシ基との反応可能な硬化剤中の活性基（酸無水物基又は水酸基）が０．５〜０．９当量となるように配合することが好ましく、０．７〜０．８当量となることがより好ましい。上記活性基が０．５当量未満では、熱硬化性樹脂組成物の硬化速度が遅くなると共に、得られる硬化体のガラス転移温度が低くなり、充分な弾性率が得られ難くなる傾向がある。一方、上記活性基が０．９当量を超えると、硬化後の強度が低下する傾向がある。 The curing agent has 0.5 to 0.9 equivalent of an active group (an acid anhydride group or a hydroxyl group) in the curing agent capable of reacting with the epoxy group with respect to 1 equivalent of the epoxy group in the epoxy resin. It is preferable to mix | blend so that it may become 0.7-0.8 equivalent. If the said active group is less than 0.5 equivalent, while the cure rate of a thermosetting resin composition will become slow, the glass transition temperature of the hardened | cured material obtained will become low, and there exists a tendency for sufficient elasticity modulus to become difficult to be obtained. On the other hand, when the active group exceeds 0.9 equivalent, the strength after curing tends to decrease.
（硬化促進剤）
本発明の光反射用熱硬化性樹脂組成物は、硬化反応を促進するために、硬化促進剤を含むことが好ましい。硬化促進剤としては、例えば、アミン化合物、イミダゾール化合物、有機リン化合物、アルカリ金属化合物、アルカリ土類金属化合物、第４級アンモニウム塩が挙げられる。これらの硬化促進剤の中でも、アミン化合物、イミダゾール化合物又は有機リン化合物を用いることが好ましい。アミン化合物としては、例えば、１，８−ジアザ−ビシクロ（５，４，０）ウンデセン−７、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が挙げられる。また、イミダゾール化合物として、例えば、２−エチル−４−メチルイミダゾールが挙げられる。更に、有機リン化合物としては、例えば、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−ブチルホスホニウム−ｏ，ｏ−ジエチルホスホロジチオエート、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が挙げられる。これらの硬化促進剤は、１種を単独で又は２種以上を組み合わせて使用してもよい。
(Curing accelerator)
The light-reflective thermosetting resin composition of the present invention preferably contains a curing accelerator in order to accelerate the curing reaction. Examples of the curing accelerator include amine compounds, imidazole compounds, organic phosphorus compounds, alkali metal compounds, alkaline earth metal compounds, and quaternary ammonium salts. Among these curing accelerators, it is preferable to use an amine compound, an imidazole compound, or an organic phosphorus compound. Examples of the amine compound include 1,8-diaza-bicyclo (5,4,0) undecene-7, triethylenediamine, and tri-2,4,6-dimethylaminomethylphenol. Examples of the imidazole compound include 2-ethyl-4-methylimidazole. Furthermore, examples of the organic phosphorus compound include triphenylphosphine, tetraphenylphosphonium tetraphenylborate, tetra-n-butylphosphonium-o, o-diethylphosphorodithioate, tetra-n-butylphosphonium-tetrafluoroborate, tetra -N-butylphosphonium-tetraphenylborate. These curing accelerators may be used alone or in combination of two or more.
上記硬化促進剤の配合量は、エポキシ樹脂１００質量部に対して、０．０１〜８質量部であることが好ましく、０．１〜３質量部であることがより好ましい。硬化促進剤の配合量が、０．０１質量部未満では、十分な硬化促進効果を得られない場合があり、８質量部を超えると、得られる硬化物に変色が見られる場合がある。 The blending amount of the curing accelerator is preferably 0.01 to 8 parts by mass and more preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the epoxy resin. When the blending amount of the curing accelerator is less than 0.01 parts by mass, a sufficient curing acceleration effect may not be obtained, and when it exceeds 8 parts by mass, discoloration may be seen in the obtained cured product.
エポキシ樹脂、並びに必要に応じて配合される硬化剤及び硬化促進剤を含む熱硬化性樹脂の屈折率は、通常１．３〜１．６であり、１．４〜１．５であることが好ましい。 The refractive index of the thermosetting resin containing an epoxy resin and a curing agent and a curing accelerator blended as necessary is usually 1.3 to 1.6 and 1.4 to 1.5. preferable.
＜空隙部の屈折率が１．０〜１．１である中空粒子＞
本実施形態において、光反射用熱硬化性樹脂組成物は、屈折率１．６〜３．０の無機酸化物と共に、空隙部の屈折率が１．０〜１．１である中空粒子を含有することができる。これにより、光漏れをより効果的に抑制できる光反射用熱硬化性樹脂組成物を得ることができる。
<Hollow particles having a refractive index of voids of 1.0 to 1.1>
In the present embodiment, the thermosetting resin composition for light reflection contains hollow particles having a refractive index of 1.0 to 1.1 in the void together with an inorganic oxide having a refractive index of 1.6 to 3.0. can do. Thereby, the thermosetting resin composition for light reflection which can suppress light leakage more effectively can be obtained.
中空粒子の空隙部は、真空であってもよく、屈折率１．０〜１．１の媒質で満たされていてもよい。中空粒子は、中空粒子外殻を透過した光が中空粒子内部で反射されるため、空隙部の屈折率は熱硬化性樹脂の屈折率よりも屈折率が低い媒質で満たされていることがより好ましい。このような媒質としては、通常、空気が好ましいが、窒素やアルゴン等の不活性ガスであってもよく、これらの混合気体であってもよい。 The voids of the hollow particles may be in a vacuum or may be filled with a medium having a refractive index of 1.0 to 1.1. In the hollow particles, since the light transmitted through the outer shell of the hollow particles is reflected inside the hollow particles, the refractive index of the void is more preferably filled with a medium having a lower refractive index than that of the thermosetting resin. preferable. As such a medium, air is usually preferable, but it may be an inert gas such as nitrogen or argon, or a mixed gas thereof.
中空粒子は、熱処理や樹脂組成物調製工程で中空粒子が破壊され、空隙部が無くなると光漏れ特性が失われるので、その外殻が耐熱性及び耐圧強度が高い材質から形成されることが好ましい。このような材質としては、無機化合物では、無機ガラス、シリカ、アルミナ等の金属酸化物、炭酸カルシウム、炭酸バリウム、珪酸カルシウム、炭酸ニッケル等の金属塩を好適に用いることができ、具体的には、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が挙げられる。有機化合物では、ポリスチレン系樹脂、ポリ（メタ）アクリレート系樹脂及びこれらの架橋体を好適に用いることができる。中空粒子の外殻は、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、架橋スチレン系樹脂、架橋アクリル系樹脂からなる群より選ばれる少なくとも１種の材質から構成されることが好ましい。 The hollow particles are preferably formed of a material having high heat resistance and pressure strength because the hollow particles are destroyed in the heat treatment and the resin composition preparation process, and the light leakage characteristics are lost when the voids disappear. . As such a material, as an inorganic compound, a metal oxide such as inorganic glass, silica, and alumina, and a metal salt such as calcium carbonate, barium carbonate, calcium silicate, and nickel carbonate can be suitably used. , Sodium silicate glass, aluminum silicate glass, and sodium borosilicate glass. As the organic compound, a polystyrene resin, a poly (meth) acrylate resin, and a crosslinked product thereof can be suitably used. The outer shell of the hollow particles is preferably composed of at least one material selected from the group consisting of sodium silicate glass, aluminum silicate glass, sodium borosilicate glass, crosslinked styrene resin, and crosslinked acrylic resin.
中空粒子の中心粒径は、０．１〜５０μｍであることが好ましく、０．１〜３０μｍであることがより好ましい。中空粒子の中心粒径が０．１μｍ未満では光反射用熱硬化性樹脂組成物を調製する際に中空粒子の分散が不均一になることがあり、５０μｍを超えると形成される硬化物の厚みが厚くなり、硬化物の反射率が低下する傾向がある。 The center particle diameter of the hollow particles is preferably 0.1 to 50 μm, and more preferably 0.1 to 30 μm. If the center particle diameter of the hollow particles is less than 0.1 μm, the dispersion of the hollow particles may be non-uniform when preparing the thermosetting resin composition for light reflection, and if it exceeds 50 μm, the thickness of the cured product formed Tends to be thick and the reflectivity of the cured product tends to decrease.
中空粒子の配合量は、熱硬化性樹脂１００質量部に対して、２０〜８５質量部であることが好ましい。光反射用熱硬化性樹脂組成物をトランスファー成形用として使用する場合には、熱硬化性樹脂１００質量部に対して、２０〜８５質量部であることがより好ましく、基板コーティング用として使用する場合には、２０〜５０質量部であることがより好ましい。 It is preferable that the compounding quantity of a hollow particle is 20-85 mass parts with respect to 100 mass parts of thermosetting resins. When the light-reflective thermosetting resin composition is used for transfer molding, it is more preferably 20 to 85 parts by mass with respect to 100 parts by mass of the thermosetting resin, and the substrate is used for substrate coating. Is more preferably 20 to 50 parts by mass.
＜その他の成分＞
本発明の光反射用熱硬化性樹脂組成物は、成形性を向上させる観点から、無機充填材を更に含んでいてもよい。また、これらを添加する際は、熱硬化性樹脂成分との密着性を向上させる観点から、カップリング剤を添加することができる。
<Other ingredients>
The light-reflective thermosetting resin composition of the present invention may further contain an inorganic filler from the viewpoint of improving moldability. Moreover, when adding these, a coupling agent can be added from a viewpoint of improving adhesiveness with a thermosetting resin component.
（無機充填材）
無機充填材としては、例えば、シリカ、硫酸バリウム、炭酸マグネシウム、炭酸バリウムが挙げられる。成型性の点から、無機充填剤は、シリカが好ましい。また、無機充填材の中心粒径は、白色顔料とのパッキング性を向上させる観点から、１〜１００μｍであることが好ましい。
(Inorganic filler)
Examples of the inorganic filler include silica, barium sulfate, magnesium carbonate, and barium carbonate. From the viewpoint of moldability, the inorganic filler is preferably silica. Moreover, it is preferable that the center particle diameter of an inorganic filler is 1-100 micrometers from a viewpoint of improving packing property with a white pigment.
（カップリング剤）
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が挙げられる。シランカップリング剤としては、一般にエポキシシラン系、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複合系が挙げられ、任意の添加量で用いることができる。なお、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％以下であることが好ましい。
(Coupling agent)
Although it does not specifically limit as a coupling agent, For example, a silane coupling agent and a titanate coupling agent are mentioned. Examples of the silane coupling agent generally include epoxy silane, amino silane, cationic silane, vinyl silane, acryl silane, mercapto silane, and composites thereof, and can be used in any amount. In addition, it is preferable that the compounding quantity of a coupling agent is 5 mass% or less with respect to the whole thermosetting resin composition.
また、本発明の光反射用熱硬化性樹脂組成物には、必要に応じて、酸化防止剤、離型剤、イオン捕捉剤等の添加剤を添加してもよい。 Moreover, you may add additives, such as antioxidant, a mold release agent, and an ion capture agent, to the thermosetting resin composition for light reflections of this invention as needed.
［光反射用熱硬化性樹脂組成物の作製方法］
本実施形態の光反射用熱硬化性樹脂組成物は、上述した各種成分を均一に分散混合することで得ることができ、その手段や条件等は特に限定されない。光反射用熱硬化性樹脂組成物を作製する一般的な方法として、各成分をニーダー、ロール、エクストルーダー、らいかい機、自転と公転を組み合わせた遊星式混合機等によって混練する方法を挙げることができる。各成分を混練する際には、分散性を向上する観点から、溶融状態で行うことが好ましい。
[Method for producing thermosetting resin composition for light reflection]
The light-reflective thermosetting resin composition of the present embodiment can be obtained by uniformly dispersing and mixing the various components described above, and means and conditions thereof are not particularly limited. As a general method for producing a thermosetting resin composition for light reflection, a method of kneading each component with a kneader, a roll, an extruder, a raking machine, a planetary mixer that combines rotation and revolution, etc. Can do. When kneading each component, it is preferable to carry out in a molten state from the viewpoint of improving dispersibility.
混練の条件は、各成分の種類や配合量により適宜決定すればよく、例えば、１５〜１００℃で５〜４０分間混練することが好ましく、２０〜１００℃で１０〜３０分間混練することがより好ましい。混練温度が１５℃未満であると、各成分を混練させ難くなり、分散性も低下する傾向にあり、１００℃を超えると、熱硬化性樹脂の高分子量化が進行し、混練時に熱硬化性樹脂が硬化してしまう可能性がある。また、混練時間が５分未満であると、十分な分散効果が得られない可能性がある。混練時間が４０分を超えると、熱硬化性樹脂の高分子量化が進行し、熱硬化性樹脂が硬化してしまう可能性がある。 The kneading conditions may be appropriately determined depending on the type and blending amount of each component. For example, kneading is preferably performed at 15 to 100 ° C. for 5 to 40 minutes, and kneading at 20 to 100 ° C. for 10 to 30 minutes is more preferable. preferable. When the kneading temperature is less than 15 ° C., it becomes difficult to knead each component and the dispersibility tends to decrease. When the kneading temperature exceeds 100 ° C., the high molecular weight of the thermosetting resin proceeds, and thermosetting during kneading. The resin may be cured. Further, if the kneading time is less than 5 minutes, a sufficient dispersion effect may not be obtained. If the kneading time exceeds 40 minutes, the thermosetting resin may increase in molecular weight, and the thermosetting resin may be cured.
本実施形態の光反射用熱硬化性樹脂組成物は、熱硬化後の、波長４６０〜８００ｎｍにおける光反射率が９０％以上であることが好ましい。上記光反射率が９０％未満では、光半導体装置の輝度向上に充分寄与できない傾向があり、より好ましい光反射率は９５％以上である。 The light reflecting thermosetting resin composition of the present embodiment preferably has a light reflectance of 90% or more at a wavelength of 460 to 800 nm after thermosetting. If the light reflectance is less than 90%, there is a tendency that it cannot sufficiently contribute to the improvement of the luminance of the optical semiconductor device, and a more preferable light reflectance is 95% or more.
本実施形態の光反射用熱硬化性樹脂組成物は、高い光反射性及び耐熱性を必要とする光半導体素子実装用基板材料、電気絶縁材料、光半導体封止材料、接着材料、塗料材料並びにトランスファー成型用エポキシ樹脂成形材料など様々な用途において有用である。以下トランスファー成型用エポキシ樹脂成形材料として使用する際の例を述べる。 The light-reflective thermosetting resin composition of this embodiment includes a substrate material for mounting an optical semiconductor element that requires high light reflectivity and heat resistance, an electrical insulating material, an optical semiconductor sealing material, an adhesive material, a paint material, and It is useful in various applications such as an epoxy resin molding material for transfer molding. An example when used as an epoxy resin molding material for transfer molding will be described below.
本発明の光反射用熱硬化性樹脂組成物は、トランスファー成形時の成形温度が１８０℃で、９０秒間の条件で成形したときに、成形直後３０秒以内のショアＤ硬度、即ち、熱時硬度が８０〜９５であることが好ましい。熱時硬度が８０未満であると、成形体の硬化が阻害されており、金型から成形物を離型する際に成形物がなき別れるなど破壊されてしまう可能性がある。このような成形体の破壊が発生すると光半導体素子搭載用基板を製造する歩留りが低下し、光半導体装置を作製できなくなる。 The thermosetting resin composition for light reflection of the present invention has a Shore D hardness within 30 seconds immediately after molding, that is, a hardness during heating, when the molding temperature at the time of transfer molding is 180 ° C. and the conditions are 90 seconds. Is preferably 80 to 95. When the hot hardness is less than 80, curing of the molded product is hindered, and when the molded product is released from the mold, the molded product may be broken or broken. When such a molded body breaks down, the yield for manufacturing the substrate for mounting an optical semiconductor element decreases, and the optical semiconductor device cannot be manufactured.
本発明の光反射用熱硬化性樹脂組成物は、成形温度１８０℃、成形圧力６．９ＭＰａ、成形時間６０〜１２０秒の条件でトランスファー成形した時のバリの長さが５ｍｍ以下となることが好ましい。バリの長さが５ｍｍを超えると、光半導体素子搭載用基板を作製する際、光半導体素子搭載領域となる開口部（凹部）に樹脂汚れが発生し、光半導体素子を搭載する際の障害となる可能性があり、また、光半導体素子と金属配線とを電気的に接続する際の障害になる可能性がある。半導体装置製造時の作業性の観点から、上記バリ長さは、３ｍｍ以下であることがより好ましく、１ｍｍ以下であることがさらに好ましい。 The light-reflective thermosetting resin composition of the present invention may have a burr length of 5 mm or less when transfer molded under conditions of a molding temperature of 180 ° C., a molding pressure of 6.9 MPa, and a molding time of 60 to 120 seconds. preferable. If the length of the burr exceeds 5 mm, when manufacturing the optical semiconductor element mounting substrate, resin contamination occurs in the opening (recessed portion) that becomes the optical semiconductor element mounting region, and this is an obstacle to mounting the optical semiconductor element. In addition, there is a possibility that it becomes an obstacle when electrically connecting the optical semiconductor element and the metal wiring. From the viewpoint of workability at the time of manufacturing a semiconductor device, the burr length is more preferably 3 mm or less, and further preferably 1 mm or less.
また、本発明の光反射用熱硬化性樹脂組成物は、基板コーティング用として使用することもできる。この際の光反射用熱硬化性樹脂組成物の基板への塗布方法は、印刷、ダイコート、カーテンコート、スプレーコート等の塗布方法を用いることができる。 Moreover, the thermosetting resin composition for light reflection of the present invention can also be used for substrate coating. In this case, as a method of applying the light-reflective thermosetting resin composition to the substrate, a coating method such as printing, die coating, curtain coating, or spray coating can be used.
［光半導体素子搭載用基板］
本発明の光半導体素子搭載用基板は、底面及び壁面から構成される凹部を有し、凹部の底面が光半導体素子搭載部（光半導体素子搭載領域）であり、凹部の壁面、すなわち凹部の内周側面の少なくとも一部が本発明の光反射用熱硬化性樹脂組成物の硬化物からなるものである。図１は、本発明の光半導体素子搭載用基板の一実施形態を示す斜視図である。光半導体素子搭載用基板１１０は、Ｎｉ／Ａｇめっき１０４が形成された金属配線１０５（第１の接続端子および第２の接続端子）と、金属配線１０５（第１の接続端子および第２の接続端子）間に設けられた絶縁性樹脂成形体１０３’と、リフレクター１０３とを備え、Ｎｉ／Ａｇめっき１０４が形成された金属配線１０５及び樹脂成形体１０３’とリフレクター１０３とから形成された凹部２００を有している。この凹部２００の底面は、Ｎｉ／Ａｇめっき１０４が形成された金属配線１０５及び絶縁性樹脂成形体１０３’から構成され、凹部２００の壁面はリフレクター１０３から構成されるものである。そして、リフレクター１０３及び絶縁性樹脂成形体１０３’が、上記本発明の光反射用熱硬化性樹脂組成物の硬化物からなる成形体である。
[Optical semiconductor device mounting substrate]
The substrate for mounting an optical semiconductor element according to the present invention has a recess composed of a bottom surface and a wall surface, and the bottom surface of the recess is an optical semiconductor element mounting portion (optical semiconductor element mounting region). At least a part of the peripheral side surface is made of a cured product of the thermosetting resin composition for light reflection of the present invention. FIG. 1 is a perspective view showing an embodiment of a substrate for mounting an optical semiconductor element of the present invention. The substrate for mounting an
本発明の光半導体素子搭載用基板の製造方法は特に限定されないが、例えば、本発明の光反射用熱硬化性樹脂組成物を用いたトランスファー成形により製造することができる。図２は、本発明の光半導体素子搭載用基板を製造する工程の一実施形態を示す概略図である。光半導体素子搭載用基板は、例えば、金属箔から打ち抜きやエッチング等の公知の方法により金属配線１０５を形成し、電気めっきによりＮｉ／Ａｇめっき１０４を施す工程（図２（ａ））、次いで、該金属配線１０５を所定形状の金型１５１に配置し、金型１５１の樹脂注入口１５０から本発明の光反射用熱硬化性樹脂組成物を注入し、所定の条件でトランスファー成形する工程（図２（ｂ））、そして、金型１５１を外す工程（図２（ｃ））を経て製造することができる。このようにして、光半導体素子搭載用基板には、光反射用熱硬化性樹脂組成物の硬化物からなるリフレクター１０３に周囲を囲まれてなる光半導体素子搭載領域（凹部）２００が形成される。また、凹部の底面は、第１の接続端子となる金属配線１０５及び第２の接続端子となる金属配線１０５と、これらの間に設けられ光反射用熱硬化性樹脂組成物の硬化物からなる絶縁性樹脂成形体１０３’とから構成される。なお、上記トランスファー成形の条件としては、金型温度１７０〜２００℃、成形圧力０．５〜２０ＭＰａで６０〜１２０秒間、アフターキュア温度１２０℃〜１８０℃で１〜３時間が好ましい。
Although the manufacturing method of the board | substrate for optical semiconductor element mounting of this invention is not specifically limited, For example, it can manufacture by transfer molding using the thermosetting resin composition for light reflections of this invention. FIG. 2 is a schematic view showing an embodiment of a process for producing an optical semiconductor element mounting substrate of the present invention. The optical semiconductor element mounting substrate is formed by, for example, forming a
［光半導体装置］
本発明の光半導体装置は、上記光半導体素子搭載用基板と、光半導体素子搭載用基板の凹部内に設けられた光半導体素子と、凹部を充填して光半導体素子を封止する封止樹脂部とを備えるものである。
[Optical semiconductor device]
An optical semiconductor device of the present invention includes the optical semiconductor element mounting substrate, an optical semiconductor element provided in a recess of the optical semiconductor element mounting substrate, and a sealing resin that fills the recess and seals the optical semiconductor element. Part.
図３は、本発明の光半導体素子搭載用基板１１０に光半導体素子１００を搭載した状態の一実施形態を示す斜視図である。図３に示すように、光半導体素子１００は、光半導体素子搭載用基板１１０の光半導体素子搭載領域（凹部）２００の所定位置に搭載され、金属配線１０５とボンディングワイヤ１０２により電気的に接続される。図４及び５は、本発明の光半導体装置の一実施形態を示す模式断面図である。図４及び５に示すように、光半導体装置は、光半導体素子搭載用基板１１０と、光半導体素子搭載用基板１１０の凹部２００内の所定位置に設けられた光半導体素子１００と、凹部２００を充填して光半導体素子を封止する蛍光体１０６を含む透明封止樹脂１０１からなる封止樹脂部とを備えており、光半導体素子１００とＮｉ／Ａｇめっき１０４が形成された金属配線１０５とがボンディングワイヤ１０２又ははんだバンプ１０７により電気的に接続されている。
FIG. 3 is a perspective view showing an embodiment in which the
図６もまた、本発明の光半導体装置の一実施形態を示す模式断面図である。図６に示す光半導体装置では、リフレクター３０３が形成されたリード３０４上の所定位置にダイボンド材３０６を介してＬＥＤ素子３００が配置され、ＬＥＤ素子３００とリード３０４とがボンディングワイヤ３０１により電気的に接続され、蛍光体３０５を含む透明封止樹脂３０２によりＬＥＤ素子３００が封止されている。
FIG. 6 is also a schematic cross-sectional view showing an embodiment of the optical semiconductor device of the present invention. In the optical semiconductor device shown in FIG. 6, the
以上、本発明の好適な実施形態について説明したが、本発明はこれに制限されるものではない。例えば、本発明の光反射用熱硬化性樹脂組成物は光反射コート剤として用いることができる。この実施形態として、銅張積層板、光半導体素子搭載用基板及び光半導体素子について説明する。 As mentioned above, although preferred embodiment of this invention was described, this invention is not restrict | limited to this. For example, the thermosetting resin composition for light reflection of the present invention can be used as a light reflection coating agent. As this embodiment, a copper-clad laminate, an optical semiconductor element mounting substrate, and an optical semiconductor element will be described.
本発明に係る銅張積層板は、上述した本発明の光反射用熱硬化性樹脂組成物を用いて形成された光反射樹脂層と、該光反射樹脂層上に積層された銅箔と、を備えるものである。 The copper-clad laminate according to the present invention is a light-reflecting resin layer formed using the above-described thermosetting resin composition for light reflection of the present invention, a copper foil laminated on the light-reflecting resin layer, Is provided.
図７は、本発明に係る銅張積層板の好適な一実施形態を示す模式断面図である。図７に示すように、銅張積層板４００は、基材４０１と、該基材４０１上に積層された光反射樹脂層４０２と、該光反射樹脂層４０２上に積層された銅箔４０３と、を備えている。ここで、光反射樹脂層４０２は、上述した本発明の光反射用熱硬化性樹脂組成物を用いて形成されている。
FIG. 7 is a schematic cross-sectional view showing a preferred embodiment of a copper clad laminate according to the present invention. As shown in FIG. 7, a copper clad
基材４０１としては、銅張積層板に用いられる基材を特に制限なく用いることができるが、例えば、エポキシ樹脂積層板等の樹脂積層板、光半導体搭載用基板などが挙げられる。
As the
銅張積層板４００は、例えば、本発明の樹脂組成物を基材４０１表面に塗布し、銅箔４０３を重ね、加熱加圧硬化して上記樹脂組成物からなる光反射層４０２を形成することにより作製することができる。
The copper clad
本発明の樹脂組成物の基板４０１への塗布方法としては、例えば、印刷法、ダイコート法、カーテンコート法、スプレーコート法、ロールコート法等の塗布方法を用いることができる。このとき、本発明の光反射用熱硬化性樹脂組成物には、塗布が容易となるように溶媒を含有させることができる。なお、溶媒を用いる場合、上述した各成分の配合割合で樹脂組成物全量を基準としたものについては、溶媒を除いたものを全量として設定することが好ましい。
As a method for applying the resin composition of the present invention to the
加熱加圧の条件としては、特に限定されないが、例えば、１３０〜１８０℃、０．５〜４ＭＰａ、３０〜６００分間の条件で加熱加圧を行うことが好ましい。 The heating and pressing conditions are not particularly limited. For example, it is preferable to perform heating and pressing under conditions of 130 to 180 ° C., 0.5 to 4 MPa, and 30 to 600 minutes.
上記本発明に係る銅張積層板を使用し、ＬＥＤ実装用等の光学部材用のプリント配線板を作製することができる。なお、図７に示した銅張積層板４００は、基材４０１の片面に光反射樹脂層４０２及び銅箔４０３を積層したものであるが、本発明に係る銅張積層板は、基材４０１の両面に光反射層４０２及び銅箔４０３をそれぞれ積層したものであってもよい。また、図７に示した銅張積層板４００は、基材４０１上に光反射層４０２及び銅箔４０３を積層したものであるが、本発明に係る銅張積層板は、基材４０１を用いることなく、光反射樹脂層４０２及び銅箔４０３のみで構成されていてもよい。この場合、光反射樹脂層４０２が基材としての役割をはたすこととなる。この場合、例えば、ガラスクロス等に本発明の樹脂組成物を含浸させ、硬化させたものを光反射樹脂層４０２とすることができる。
Using the copper-clad laminate according to the present invention, a printed wiring board for an optical member such as for LED mounting can be produced. 7 is obtained by laminating a light reflecting
図８は、本発明に係る銅張積層板を用いて作製された光半導体装置の一例を示す模式断面図である。図８に示すように、光半導体装置５００は、光半導体素子４１０と、該光半導体素子４１０が封止されるように設けられた透明な封止樹脂４０４とを備える表面実装型の発光ダイオードである。光半導体装置５００において、半導体素子４１０は、接着層４０８を介して銅箔４０３に接着されており、ワイヤー４０９により銅箔４０３と電気的に接続されている。
FIG. 8 is a schematic cross-sectional view showing an example of an optical semiconductor device manufactured using the copper-clad laminate according to the present invention. As shown in FIG. 8, the
更に、本発明に係る光半導体素子搭載用基板の他の実施形態として、上述した本発明の光反射用熱硬化性樹脂組成物を用いて、基材上の複数の導体部材（接続端子）間に形成された光反射層を備える光半導体素子搭載用基板が挙げられる。また、本発明に係る光半導体装置の他の実施形態は、上記の光半導体素子搭載用基板に光半導体素子を搭載してなるものである。 Furthermore, as another embodiment of the substrate for mounting an optical semiconductor element according to the present invention, using the above-described thermosetting resin composition for light reflection of the present invention, a plurality of conductor members (connection terminals) on the base material are used. An optical semiconductor element mounting substrate provided with the light reflecting layer formed in the above. In another embodiment of the optical semiconductor device according to the present invention, the optical semiconductor element is mounted on the optical semiconductor element mounting substrate.
図９は、本発明に係る光半導体装置の好適な一実施形態を示す模式断面図である。図９に示すように、光半導体装置６００は、基材６０１と、該該基材６０１の表面に形成された複数の導体部材６０２と、複数の導体部材（接続端子）６０２間に形成された、上記本発明の光反射用熱硬化性樹脂組成物からなる光反射層６０３と、を備える光半導体素子搭載用基板に、光半導体素子６１０が搭載され、該光半導体素子６１０が封止されるように透明な封止樹脂６０４が設けられた、表面実装型の発光ダイオードである。光半導体装置６００において、光半導体素子６１０は、接着層６０８を介して導体部材６０２に接着されており、ワイヤー６０９により導体部材６０２と電気的に接続されている。
FIG. 9 is a schematic cross-sectional view showing a preferred embodiment of the optical semiconductor device according to the present invention. As shown in FIG. 9, the
基材６０１としては、光半導体素子搭載用基板に用いられる基材を特に制限なく用いることができるが、例えば、エポキシ樹脂積層板等の樹脂積層板などが挙げられる。
As the
導体部材６０２は、接続端子として機能するものであり、例えば、銅箔をフォトエッチングする方法等、公知の方法により形成することができる。
The
光半導体素子搭載用基板は、本発明の光反射用熱硬化性樹脂組成物を基材６０１上の複数の導体部材６０２間に塗布し、加熱硬化して上記光反射用熱硬化性樹脂組成物からなる光反射層６０３を形成することにより作製することができる。
For the substrate for mounting an optical semiconductor element, the thermosetting resin composition for light reflection of the present invention is applied between the plurality of
本発明の光反射用熱硬化性樹脂組成物の基板６０１への塗布方法としては、例えば、印刷法、ダイコート法、カーテンコート法、スプレーコート法、ロールコート法等の塗布方法を用いることができる。このとき、本発明の光反射用熱硬化性樹脂組成物には、塗布が容易となるように溶媒を含有させることができる。なお、溶媒を用いる場合、上述した各成分の配合割合で樹脂組成物全量を基準としたものについては、溶媒を除いたものを全量として設定することが好ましい。
As a method for applying the light-reflective thermosetting resin composition of the present invention to the
光反射用熱硬化性樹脂組成物の塗膜を加熱硬化する際の加熱条件としては、特に限定されないが、例えば、１３０〜１８０℃、３０〜６００分間の条件で加熱を行うことが好ましい。 Although it does not specifically limit as heating conditions at the time of heat-hardening the coating film of the thermosetting resin composition for light reflections, For example, it is preferable to heat on 130-180 degreeC and the conditions for 30 to 600 minutes.
以下に、本発明を実施例に基づいて具体的に説明するが、本発明はこれに限定されるものではない。 Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited thereto.
＜光反射用熱硬化性樹脂組成物の作製＞
（実施例１〜１１、比較例１〜６）
表１及び２に示した配合比（質量部）に従い、各成分を配合し、ミキサーによって十分混練した後、ミキシングロールにより４０℃で１５分溶融混練し、冷却、粉砕を行い、実施例及び比較例の光反射用熱硬化性樹脂組成物を作製した。
<Preparation of thermosetting resin composition for light reflection>
(Examples 1-11, Comparative Examples 1-6)
In accordance with the blending ratio (parts by mass) shown in Tables 1 and 2, each component was blended and sufficiently kneaded with a mixer, then melt-kneaded with a mixing roll at 40 ° C. for 15 minutes, cooled and pulverized. The thermosetting resin composition for light reflection of an example was produced.
＜光反射用熱硬化性樹脂組成物の評価＞
得られた熱硬化性樹脂組成物を１８０℃のホットプレート上で加圧成形し、１５０℃で２時間ポストキュアして、厚み０．１ｍｍ±０．０５ｍｍのテストピースを作製し、下記の評価を行った。評価結果を表１及び２に示す。
<Evaluation of thermosetting resin composition for light reflection>
The obtained thermosetting resin composition was pressure-molded on a 180 ° C. hot plate, post-cured at 150 ° C. for 2 hours, and a test piece having a thickness of 0.1 mm ± 0.05 mm was prepared. Went. The evaluation results are shown in Tables 1 and 2.
（光反射率の測定）
積分球型分光光度計Ｖ−７５０型（日本分光株式会社製、商品名）を用いて、波長４６０ｎｍにおける上記テストピースの初期光学反射率（光反射率）を測定した。
(Measurement of light reflectance)
The initial optical reflectivity (light reflectivity) of the test piece at a wavelength of 460 nm was measured using an integrating sphere spectrophotometer V-750 type (trade name, manufactured by JASCO Corporation).
（漏れ光測定）
波長４６０ｎｍに波長ピークを有する発光素子を搭載し、これを取り囲むように反射枠が備えられた表面実装型光半導体装置を光源として用い、表面実装型光半導体装置に対向するようにＣＣＤカメラを設置し、発光素子からの配光分布を撮影して輝度が最も高い領域を数値化した。この状態で、表面実装型光半導体装置に１００ｍＡの電流を流した際の輝度は、２５００００ｃｄ／ｍ２であり、これを光源の輝度とした。
(Leakage light measurement)
A light-emitting element having a wavelength peak at a wavelength of 460 nm is mounted, and a surface mount type optical semiconductor device provided with a reflection frame so as to surround it is used as a light source, and a CCD camera is installed so as to face the surface mount type optical semiconductor device Then, the distribution of light distribution from the light emitting elements was photographed and the region with the highest luminance was digitized. In this state, the luminance when a current of 100 mA was passed through the surface-mounted optical semiconductor device was 250,000 cd / m 2 , which was used as the luminance of the light source.
表面実装型光半導体装置とＣＣＤカメラとを遮る位置に発光素子からの距離が１ｍｍとなるように上記テストピースを設置し、１００ｍＡの電流を流した際の光源からの光がテストピースを透過してくる光の配光分布を撮影し輝度が最も高い領域を数値化し漏れ光の値とし、漏れ光低減率の対光源比を評価した。 The test piece is placed at a position where the surface mount type optical semiconductor device and the CCD camera are blocked so that the distance from the light emitting element is 1 mm, and light from the light source when a current of 100 mA is passed through the test piece. The distribution of the incoming light was photographed, and the area with the highest luminance was digitized to obtain the leakage light value, and the ratio of the leakage light reduction ratio to the light source was evaluated.
表１及び２中、＊１〜１１は以下の通りである。
＊１：トリス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：ＴＥＰＩＣ−Ｓ）
＊２：メチルヘキサヒドロ無水フタル酸（日立化成工業社製）
＊３：ヘキサヒドロ無水フタル酸（和光純薬工業社製）
＊４：テトラ−ｎ−ブチルホスホニウム−ｏ，ｏ−ジエチルホスホロジチオエート（日本化学工業社製、商品名：ＰＸ−４ＥＴ）
＊５：トリメトキシエポキシシラン（東レダウコーニング社製、商品名：Ａ−１８７）
＊６：溶融シリカ（電気化学工業社製、商品名：ＦＢ−９５０）
＊７：溶融シリカ（電気化学工業社製、商品名：ＦＢ−３０１）
＊８：溶融シリカ（アドマテックス社製、商品名：ＳＯ−２５Ｒ）
＊９：酸化チタン（堺化学工業社製、商品名：ＦＴＲ−７００）
＊１０：酸化亜鉛（堺化学工業社製、商品名：ＳＴＲ−１００Ｃ−ＬＰ）
＊１１：中空粒子（住友３Ｍ社製、商品名：Ｓ６０−ＨＳ）
In Tables 1 and 2, * 1 to 11 are as follows.
* 1: Trisglycidyl isocyanurate (epoxy equivalent 100, manufactured by Nissan Chemical Co., Ltd., trade name: TEPIC-S)
* 2: Methylhexahydrophthalic anhydride (manufactured by Hitachi Chemical Co., Ltd.)
* 3: Hexahydrophthalic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.)
* 4: Tetra-n-butylphosphonium-o, o-diethyl phosphorodithioate (made by Nippon Chemical Industry Co., Ltd., trade name: PX-4ET)
* 5: Trimethoxyepoxysilane (manufactured by Toray Dow Corning, trade name: A-187)
* 6: Fused silica (manufactured by Denki Kagaku Kogyo, trade name: FB-950)
* 7: Fused silica (trade name: FB-301, manufactured by Denki Kagaku Kogyo Co., Ltd.)
* 8: Fused silica (manufactured by Admatechs, trade name: SO-25R)
* 9: Titanium oxide (manufactured by Sakai Chemical Industry Co., Ltd., trade name: FTR-700)
* 10: Zinc oxide (manufactured by Sakai Chemical Industry Co., Ltd., trade name: STR-100C-LP)
* 11: Hollow particles (manufactured by Sumitomo 3M, trade name: S60-HS)
表１及び表２に示したように、実施例１〜１１で得られた光反射用熱硬化性樹脂組成物は、いずれも０．１ｍｍの薄い厚みの場合であっても、光反射率が高く、光漏れが少ない。これに対して、比較例１〜６で得られた光反射用熱硬化性樹脂組成物は、光漏れが著しい。特に中空粒子だけを使用した比較例６では、十分な光漏れ抑制効果が得られないことが確認された。また、酸化チタンと中空粒子とを組み合わせた実施例３では、実施例５に比べ光漏れ抑制効果がより高いことが確認された。 As shown in Tables 1 and 2, the light-reflective thermosetting resin compositions obtained in Examples 1 to 11 had a light reflectance even when the thickness was 0.1 mm. High and less light leakage. On the other hand, the light-reflective thermosetting resin compositions obtained in Comparative Examples 1 to 6 have significant light leakage. In particular, in Comparative Example 6 using only hollow particles, it was confirmed that a sufficient light leakage suppression effect could not be obtained. Moreover, in Example 3 which combined the titanium oxide and the hollow particle, it was confirmed that the light leakage suppression effect is higher than Example 5.
本発明によれば、光漏れを十分に低減できる硬化物を形成可能な光反射用熱硬化性樹脂組成物を用いることで、光取り出し効率を向上させ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を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the board | substrate for optical semiconductor element mounting which improved light extraction efficiency by using the thermosetting resin composition for light reflection which can form the hardened | cured material which can fully reduce light leakage, and its manufacturing method In addition, an optical semiconductor device can be provided.
１００…光半導体素子、１０１…透明封止樹脂、１０２…ボンディングワイヤ、１０３…光反射用熱硬化性樹脂組成物の硬化物（リフレクター）、１０３’…光反射用熱硬化性樹脂組成物の硬化物（絶縁性樹脂成形体）、１０４…Ｎｉ／Ａｇめっき、１０５…金属配線、１０６…蛍光体、１０７…はんだバンプ、１１０…光半導体素子搭載用基板、１５０…樹脂注入口、１５１…金型、２００…光半導体素子搭載領域、３００…ＬＥＤ素子、３０１…ワイヤボンド、３０２…透明封止樹脂、３０３…リフレクター、３０４…リード、３０５…蛍光体、３０６…ダイボンド材、４００…銅張積層板、４０１…基材、４０２…光反射樹脂層、４０３…銅箔、４０４…封止樹脂、４０８…接着層、４０９…ワイヤー、４１０…光半導体素子、５００，６００…光半導体装置、６０１…基材、６０２…導体部材、６０３…光反射樹脂層、６０４…封止樹脂、６０８…接着層、６０９…ワイヤー、６１０…光半導体素子。
DESCRIPTION OF
Claims (5)
前記無機酸化物は、酸化チタン又は酸化亜鉛であり、かつ、前記無機酸化物の中心粒径が０．１〜２０μｍであり、
前記無機酸化物の配合量が、前記熱硬化性樹脂１００質量部に対して、１３０〜４００質量部である、トランスファー成形に用いられる光反射用熱硬化性樹脂組成物。 Containing a thermosetting resin including an epoxy resin and an inorganic oxide having a refractive index of 1.8 to 3.0,
The inorganic oxide is titanium oxide or zinc oxide, and the inorganic oxide has a central particle size of 0.1 to 20 μm,
The amount of the inorganic oxide, with respect to the thermosetting resin 100 parts by weight and 130 to 400 parts by weight, tigers down Sufa light reflecting thermosetting resin composition used for molding.
前記凹部の底面が光半導体素子搭載部であり、前記凹部の壁面の少なくとも一部が請求項１又は２に記載の光反射用熱硬化性樹脂組成物の硬化物からなる、光半導体素子搭載用基板。 Having a recess composed of a bottom and a wall;
The bottom surface of the concave portion is an optical semiconductor element mounting portion, and at least a part of the wall surface of the concave portion is made of a cured product of the light-reflecting thermosetting resin composition according to claim 1 or 2 . substrate.
前記凹部の壁面の少なくとも一部を、請求項１又は２に記載の光反射用熱硬化性樹脂組成物を用いたトランスファー成形により形成する工程を備える、光半導体素子搭載用基板の製造方法。 A method for manufacturing a substrate for mounting an optical semiconductor element having a recess composed of a bottom and a wall,
The manufacturing method of the board | substrate for optical semiconductor element mounting provided with the process of forming at least one part of the wall surface of the said recessed part by the transfer molding using the thermosetting resin composition for light reflections of Claim 1 or 2 .
前記光半導体素子搭載用基板の凹部内に設けられた光半導体素子と、
前記凹部を充填して前記光半導体素子を封止する封止樹脂部と、
を備え、
前記凹部の壁面の少なくとも一部が、請求項１又は２に記載の光反射用熱硬化性樹脂組成物の硬化物からなる、光半導体装置。 An optical semiconductor element mounting substrate having a recess composed of a bottom surface and a wall surface;
An optical semiconductor element provided in a recess of the optical semiconductor element mounting substrate;
A sealing resin portion that fills the recess and seals the optical semiconductor element;
With
An optical semiconductor device, wherein at least a part of the wall surface of the recess is made of a cured product of the thermosetting resin composition for light reflection according to claim 1 or 2 .
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