TWI621664B - Semiconductor device and curable silicone composition for sealing a semiconductor element - Google Patents
Semiconductor device and curable silicone composition for sealing a semiconductor element Download PDFInfo
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- TWI621664B TWI621664B TW103118858A TW103118858A TWI621664B TW I621664 B TWI621664 B TW I621664B TW 103118858 A TW103118858 A TW 103118858A TW 103118858 A TW103118858 A TW 103118858A TW I621664 B TWI621664 B TW I621664B
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- composition
- atoms
- polysiloxane
- organic
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- 239000000203 mixture Substances 0.000 title claims abstract description 67
- 239000004065 semiconductor Substances 0.000 title claims abstract description 63
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 62
- 238000007789 sealing Methods 0.000 title claims abstract description 15
- -1 polysiloxane Polymers 0.000 claims abstract description 91
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 45
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 29
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000006459 hydrosilylation reaction Methods 0.000 claims abstract description 21
- 239000000758 substrate Substances 0.000 claims abstract description 21
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims abstract description 20
- 229920005591 polysilicon Polymers 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 17
- 150000003961 organosilicon compounds Chemical class 0.000 claims abstract description 11
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 125000004434 sulfur atom Chemical group 0.000 claims abstract description 7
- 125000003342 alkenyl group Chemical group 0.000 claims description 23
- 229910052717 sulfur Inorganic materials 0.000 claims description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 4
- 150000003377 silicon compounds Chemical class 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims 1
- 229920000620 organic polymer Polymers 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- 238000012360 testing method Methods 0.000 abstract description 4
- 150000001336 alkenes Chemical class 0.000 abstract 1
- 229910052710 silicon Inorganic materials 0.000 description 20
- 239000000047 product Substances 0.000 description 16
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 15
- 229920005989 resin Polymers 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
- 239000004954 Polyphthalamide Substances 0.000 description 12
- 230000003287 optical effect Effects 0.000 description 12
- 229920006375 polyphtalamide Polymers 0.000 description 12
- 206010040844 Skin exfoliation Diseases 0.000 description 11
- 239000004615 ingredient Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000003566 sealing material Substances 0.000 description 9
- 229920002554 vinyl polymer Polymers 0.000 description 8
- 229910052737 gold Inorganic materials 0.000 description 7
- 239000010931 gold Substances 0.000 description 7
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 125000003545 alkoxy group Chemical group 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910052693 Europium Inorganic materials 0.000 description 4
- 229910004283 SiO 4 Inorganic materials 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000002318 adhesion promoter Substances 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- VMAWODUEPLAHOE-UHFFFAOYSA-N 2,4,6,8-tetrakis(ethenyl)-2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound C=C[Si]1(C)O[Si](C)(C=C)O[Si](C)(C=C)O[Si](C)(C=C)O1 VMAWODUEPLAHOE-UHFFFAOYSA-N 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 description 3
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000011256 inorganic filler Substances 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- 125000000962 organic group Chemical group 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 3
- 229920001843 polymethylhydrosiloxane Polymers 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 125000003944 tolyl group Chemical group 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- QYLFHLNFIHBCPR-UHFFFAOYSA-N 1-ethynylcyclohexan-1-ol Chemical compound C#CC1(O)CCCCC1 QYLFHLNFIHBCPR-UHFFFAOYSA-N 0.000 description 2
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Chemical group CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 150000008064 anhydrides Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- XVSBWQYHSLNOCU-UHFFFAOYSA-N ethenyl(dimethyl)silicon Chemical compound C[Si](C)C=C XVSBWQYHSLNOCU-UHFFFAOYSA-N 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 239000002223 garnet Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000006038 hexenyl group Chemical group 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004344 phenylpropyl group Chemical group 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920000193 polymethacrylate Polymers 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical class C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- WZJUBBHODHNQPW-UHFFFAOYSA-N 2,4,6,8-tetramethyl-1,3,5,7,2$l^{3},4$l^{3},6$l^{3},8$l^{3}-tetraoxatetrasilocane Chemical compound C[Si]1O[Si](C)O[Si](C)O[Si](C)O1 WZJUBBHODHNQPW-UHFFFAOYSA-N 0.000 description 1
- CEBKHWWANWSNTI-UHFFFAOYSA-N 2-methylbut-3-yn-2-ol Chemical compound CC(C)(O)C#C CEBKHWWANWSNTI-UHFFFAOYSA-N 0.000 description 1
- KSLSOBUAIFEGLT-UHFFFAOYSA-N 2-phenylbut-3-yn-2-ol Chemical compound C#CC(O)(C)C1=CC=CC=C1 KSLSOBUAIFEGLT-UHFFFAOYSA-N 0.000 description 1
- IKYAJDOSWUATPI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propane-1-thiol Chemical compound CO[Si](C)(OC)CCCS IKYAJDOSWUATPI-UHFFFAOYSA-N 0.000 description 1
- GRGVQLWQXHFRHO-UHFFFAOYSA-N 3-methylpent-3-en-1-yne Chemical compound CC=C(C)C#C GRGVQLWQXHFRHO-UHFFFAOYSA-N 0.000 description 1
- LITSBNREXIFYBV-UHFFFAOYSA-N 3-oxobutanoic acid platinum Chemical compound [Pt].CC(=O)CC(O)=O.CC(=O)CC(O)=O LITSBNREXIFYBV-UHFFFAOYSA-N 0.000 description 1
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- DAYVBIXMFTUYIG-UHFFFAOYSA-N C(=C)[SiH](N([Si](C)(C)C)C)C=C.[Pt] Chemical compound C(=C)[SiH](N([Si](C)(C)C)C)C=C.[Pt] DAYVBIXMFTUYIG-UHFFFAOYSA-N 0.000 description 1
- RFIAUHDYYXYZQE-UHFFFAOYSA-N C(=C)[Si](N[Si](C)(C)C=C)(C)C.[Pt] Chemical compound C(=C)[Si](N[Si](C)(C)C=C)(C)C.[Pt] RFIAUHDYYXYZQE-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- WYUIWUCVZCRTRH-UHFFFAOYSA-N [[[ethenyl(dimethyl)silyl]amino]-dimethylsilyl]ethene Chemical compound C=C[Si](C)(C)N[Si](C)(C)C=C WYUIWUCVZCRTRH-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- JSAYQGVHWNBMNG-UHFFFAOYSA-N bis(2-methylbut-3-yn-2-yloxy)-prop-1-enylsilane Chemical compound CC=C[SiH](OC(C#C)(C)C)OC(C#C)(C)C JSAYQGVHWNBMNG-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- DDJSWKLBKSLAAZ-UHFFFAOYSA-N cyclotetrasiloxane Chemical compound O1[SiH2]O[SiH2]O[SiH2]O[SiH2]1 DDJSWKLBKSLAAZ-UHFFFAOYSA-N 0.000 description 1
- 125000003493 decenyl group Chemical group [H]C([*])=C([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- GAURFLBIDLSLQU-UHFFFAOYSA-N diethoxy(methyl)silicon Chemical compound CCO[Si](C)OCC GAURFLBIDLSLQU-UHFFFAOYSA-N 0.000 description 1
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 1
- RQCQBDUYEHRNPP-UHFFFAOYSA-N dimethyl-bis(2-methylbut-3-yn-2-yloxy)silane Chemical compound C#CC(C)(C)O[Si](C)(C)OC(C)(C)C#C RQCQBDUYEHRNPP-UHFFFAOYSA-N 0.000 description 1
- 125000005066 dodecenyl group Chemical group C(=CCCCCCCCCCC)* 0.000 description 1
- 210000005069 ears Anatomy 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000006355 external stress Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 description 1
- 125000005187 nonenyl group Chemical group C(=CCCCCCCC)* 0.000 description 1
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 1
- WXIWSQBJNUSTTO-UHFFFAOYSA-N pentane-2,4-dione;platinum Chemical compound [Pt].CC(=O)CC(C)=O.CC(=O)CC(C)=O WXIWSQBJNUSTTO-UHFFFAOYSA-N 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 description 1
- PIZSEPSUZMIOQF-UHFFFAOYSA-N platinum;2,4,6,8-tetrakis(ethenyl)-2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound [Pt].C=C[Si]1(C)O[Si](C)(C=C)O[Si](C)(C=C)O[Si](C)(C=C)O1 PIZSEPSUZMIOQF-UHFFFAOYSA-N 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
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- 238000002310 reflectometry Methods 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 1
- IWZLBIVZPIDURM-UHFFFAOYSA-N trimethoxy(3-prop-1-enoxypropyl)silane Chemical compound CO[Si](OC)(OC)CCCOC=CC IWZLBIVZPIDURM-UHFFFAOYSA-N 0.000 description 1
- NQRACKNXKKOCJY-UHFFFAOYSA-N trimethoxy-[3-(3-trimethoxysilylpropyldisulfanyl)propyl]silane Chemical compound CO[Si](OC)(OC)CCCSSCCC[Si](OC)(OC)OC NQRACKNXKKOCJY-UHFFFAOYSA-N 0.000 description 1
- KOFGNZOFJYBHIN-UHFFFAOYSA-N trimethoxy-[3-(3-trimethoxysilylpropyltrisulfanyl)propyl]silane Chemical compound CO[Si](OC)(OC)CCCSSSCCC[Si](OC)(OC)OC KOFGNZOFJYBHIN-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 125000005065 undecenyl group Chemical group C(=CCCCCCCCCC)* 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
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Abstract
本發明之課題在於提供一種半導體裝置，其係利用聚矽氧硬化物將經鍍金之導線或基板及半導體元件密封而形成，且吸濕回焊試驗後之可靠性優異。 An object of the present invention is to provide a semiconductor device formed by sealing a gold-plated wire or substrate and a semiconductor element with a polysilicon hardened material, and having excellent reliability after a moisture absorption reflow test.
本發明之半導體裝置係一種利用聚矽氧硬化物將經鍍金之導線或基板及半導體元件密封而成者，且上述聚矽氧硬化物為至少包含(A)於一分子中至少具有2個烯基之有機聚矽氧烷、(B)於一分子中至少具有2個鍵結矽原子之氫原子之有機氫化聚矽氧烷、(C)鍵結硫原子且具有鍵結矽原子之水解性基之有機矽化合物、及(D)矽氫化反應用鉑系觸媒之矽氫化反應硬化性聚矽氧組合物之硬化物。 The semiconductor device of the present invention is formed by sealing a gold-plated wire or substrate and a semiconductor element with a polysilicon hardened material, and the polysilicon hardened material contains at least (A) at least 2 alkene in one molecule Based organic polysiloxane, (B) organic hydrogenated polysiloxane having at least 2 hydrogen atoms bonded to silicon atoms in one molecule, (C) bonded sulfur atoms and having the hydrolyzability of bonded silicon atoms The hardened product of the organosilicon compound based on (D) the hydrosilation reaction hardening polysilicone composition of the platinum-based catalyst for hydrosilation reaction.
Description
本發明係關於一種用以密封半導體裝置及該半導體裝置中之半導體元件之硬化性聚矽氧組合物。 The present invention relates to a hardening polysiloxane composition for sealing a semiconductor device and semiconductor elements in the semiconductor device.
關於LED(Light-emitting Diode，發光二極體)等光半導體裝置，為了防止導線或基板之腐蝕，使發光二極體(LED)元件發出之光效率較佳地反射，使用鍍銀之導線或基板，但有銀由於硫化氫等含硫氣體而黑色化之問題。因此，正在研究反射率較銀差，但無含硫氣體所引起之黑色化問題之經鍍金之導線或基板的使用。 For optical semiconductor devices such as LEDs (Light-emitting Diodes), in order to prevent corrosion of wires or substrates, and to better reflect the light emitted by light-emitting diode (LED) elements, silver-plated wires or The substrate has the problem that silver is blackened by sulfur-containing gas such as hydrogen sulfide. Therefore, the use of gold-plated wires or substrates with a reflectivity lower than that of silver but without the blackening problem caused by sulfur-containing gas is being studied.
另一方面，矽氫化反應硬化性聚矽氧組合物藉由加熱而快速地硬化，硬化時不產生副產物，故作為半導體元件之密封劑或接著劑而利用，但矽氫化反應硬化性聚矽氧組合物缺乏接著性，故而，例如於日本專利特開2007-134372號公報中，提出於利用矽氫化反應硬化性聚矽氧組合物將搭載於經鍍金之基板上之半導體元件密封時，事先利用含酸酐基烷氧基矽烷或其部分水解縮合物對上述基板進行處理。 On the other hand, the hydrosilation reaction-curable polysiloxane composition is rapidly cured by heating and does not produce by-products during curing, so it is used as a sealant or adhesive for semiconductor devices, but the hydrosilation reaction-curable polysilicon The oxygen composition lacks adhesion. Therefore, for example, in Japanese Patent Laid-Open No. 2007-134372, it is proposed to seal a semiconductor device mounted on a gold-plated substrate using a hydrosilation-curable polysilicon composition beforehand. The above-mentioned substrate is treated with an anhydride group-containing alkoxysilane or a partially hydrolyzed condensate thereof.
然而，關於根據日本專利特開2007-134372號公報提出之方法，有如下不便：必須事先利用含酸酐基烷氧基矽烷或其部分水解縮合物對經鍍金之基板進行處理。 However, with regard to the method proposed in Japanese Patent Laid-Open No. 2007-134372, there is the following inconvenience: the gold-plated substrate must be processed in advance using an anhydride group-containing alkoxysilane or a partial hydrolysis-condensation product thereof.
此處，於日本專利特開2011-063663號公報中，提出包含具有鍵結矽原子之羥基之支鏈狀有機聚矽氧烷、無機填充劑、縮合觸媒，具有直鏈狀二有機聚矽氧烷殘基之有機聚矽氧烷、及3-巰丙基三甲氧基矽烷等矽烷偶合劑之底填充材料組合物，提出對回焊時之翹曲之行為無影響，耐熱性、耐光性、對金凸塊之接著性優異。然而，該組合物為底填充材料用途，又，由於縮合反應而發生硬化，故而有由於反應，而產生副產物之問題。另一方面，關於矽氫化反應硬化性聚矽氧組合物，3-巰丙基三甲氧基矽烷等鍵結硫原子且具有鍵結矽原子之水解性基之有機矽化合物易於產生硬化阻礙，故而並未研究將上述有機矽化合物用作接著促進劑。 Here, in Japanese Patent Laid-Open No. 2011-063663, a branched-chain organic polysiloxane containing a hydroxyl group having a bonded silicon atom, an inorganic filler, and a condensation catalyst are proposed to have a linear diorganopolysilicon The underfill material composition of siloxane coupling agent of organic polysiloxane and 3-mercaptopropyl trimethoxysilane and other silane coupling agents is proposed to have no effect on the behavior of warpage during reflow, heat resistance and light resistance 3. Excellent adhesion to gold bumps. However, this composition is used as an underfill material and hardens due to a condensation reaction, so there is a problem that by-products are generated due to the reaction. On the other hand, regarding the hydrosilation reaction-curable polysiloxane composition, organosilicon compounds such as 3-mercaptopropyltrimethoxysilane bonded to a sulfur atom and having a hydrolyzable group bonded to a silicon atom are likely to cause hardening inhibition, so No research has been conducted on using the above-mentioned organosilicon compound as an adhesion promoter.
[專利文獻1]日本專利特開2007-134372號公報 [Patent Document 1] Japanese Patent Laid-Open No. 2007-134372
[專利文獻2]日本專利特開2011-063663號公報 [Patent Document 2] Japanese Patent Laid-Open No. 2011-063663
本發明之目的在於提供一種半導體裝置，其係利用聚矽氧硬化物將經鍍金之導線或基板及半導體元件密封而成，且吸濕回焊試驗後之可靠性優異。又，本發明之另一目的在於提供一種硬化性聚矽氧組合物，其用於密封對經鍍金之導線或基板之接著性良好之上述導線或基板及半導體元件。 An object of the present invention is to provide a semiconductor device which is formed by sealing a gold-plated wire or substrate and a semiconductor element with a polysilicon hardened material, and has excellent reliability after a moisture absorption reflow test. In addition, another object of the present invention is to provide a hardenable silicone composition for sealing the above-mentioned wire or substrate and semiconductor device with good adhesion to a gold-plated wire or substrate.
本發明之半導體裝置之特徵在於：其係利用聚矽氧硬化物將經鍍金之導線或基板及半導體元件密封而成者，且上述聚矽氧硬化物為至少包含(A)於一分子中至少具有2個烯基之有機聚矽氧烷、(B)於一分子中至少具有2個鍵結矽原子之氫原子之有機氫化聚矽氧烷{相對於 (A)成分中之烯基1莫耳，本成分中之鍵結矽原子之氫原子成為0.1~10莫耳之量}、(C)鍵結硫原子且具有鍵結矽原子之水解性基之有機矽化合物(相對於本組合物為0.0001~2質量%)、及(D)矽氫化反應用鉑系觸媒(相對於本組合物，鉑原子成為0.01~500質量ppm之量)之矽氫化反應硬化性聚矽氧組合物之硬化物。 The semiconductor device of the present invention is characterized in that it is made of polysilicon hardened material to seal gold-plated wires or substrates and semiconductor elements, and the polysilicon hardened material contains at least (A) in at least one molecule Organic polysiloxane with 2 alkenyl groups, (B) Organic hydrogenated polysiloxane with at least 2 hydrogen atoms bonded to silicon atoms in one molecule (A) 1 mole of alkenyl in the component, the hydrogen atom of the bonded silicon atom in this component becomes an amount of 0.1 to 10 moles), (C) a sulfur atom bonded with a hydrolyzable group bonded to the silicon atom Silicone of the organosilicon compound (0.0001 to 2% by mass relative to the composition), and (D) platinum catalyst for hydrosilation reaction (the amount of platinum atoms to be 0.01 to 500 ppm by mass relative to the composition) Hardened product of hydrogenation-hardenable polysiloxane composition.
關於上述半導體裝置，較佳為聚矽氧硬化物之JIS K 6253所規定之A型硬度計硬度為10~99。 Regarding the above-mentioned semiconductor device, it is preferable that the hardness of the polysilicon hardened product is a type A durometer prescribed in JIS K 6253 of 10 to 99.
又，關於上述半導體裝置，較佳為半導體元件為發光二極體(LED)元件。 In addition, with regard to the above-mentioned semiconductor device, it is preferable that the semiconductor element is a light emitting diode (LED) element.
又，本發明之半導體元件密封用硬化性聚矽氧組合物之特徵在於：其係用於密封半導體裝置中之經鍍金之導線或基板及半導體元件之矽氫化反應硬化性聚矽氧組合物，且其至少包含(A)於一分子中至少具有2個烯基之有機聚矽氧烷、(B)於一分子中至少具有2個鍵結矽原子之氫原子之有機氫化聚矽氧烷{相對於(A)成分中之烯基1莫耳，本成分中之鍵結矽原子之氫原子成為0.1~10莫耳之量}、(C)鍵結硫原子且具有鍵結矽原子之水解性基之有機矽化合物(相對於本組合物為0.0001~2質量%)、及(D)矽氫化反應用鉑系觸媒(相對於本組合物，鉑原子成為0.01~500質量ppm之量)。 Furthermore, the curable polysiloxane composition for sealing a semiconductor element of the present invention is characterized in that it is a hydrosilation reaction-curable polysiloxane composition used for sealing a gold-plated wire or substrate and a semiconductor element in a semiconductor device, And it contains at least (A) an organic polysiloxane having at least 2 alkenyl groups in one molecule, (B) an organic hydrogenated polysiloxane having at least 2 hydrogen atoms bonded to silicon atoms in one molecule { Relative to 1 mole of alkenyl group in (A) component, the hydrogen atom of the bonded silicon atom in this component becomes an amount of 0.1 to 10 moles.) (C) Hydrolysis of the bonded sulfur atom and the bonded silicon atom Organic silicon compound (0.0001 to 2% by mass relative to this composition), and (D) platinum catalyst for hydrosilylation reaction (relative to this composition, platinum atoms are 0.01 to 500 ppm by mass) .
本發明之半導體裝置之特徵在於：吸濕回焊試驗後之可靠性優異。又，本發明之半導體元件密封用硬化性聚矽氧組合物之特徵在於：對經鍍金之導線或基板之接著性良好。 The semiconductor device of the present invention is characterized by excellent reliability after a moisture absorption reflow test. In addition, the curable polysiloxane composition for sealing semiconductor devices of the present invention is characterized by good adhesion to gold-plated wires or substrates.
1‧‧‧聚鄰苯二甲醯胺(PPA)樹脂製殼體 1‧‧‧Polyphthalamide (PPA) resin casing
2‧‧‧經鍍金之導線 2‧‧‧Gold-plated wire
3‧‧‧晶片座 3‧‧‧chip holder
4‧‧‧接著材料 4‧‧‧Next material
5‧‧‧發光二極體(LED)元件 5‧‧‧Light emitting diode (LED) components
6‧‧‧金製接合線 6‧‧‧Gold bonding wire
7‧‧‧包含聚矽氧硬化物之密封材料 7‧‧‧ Sealing material containing polysilicon hardening
圖1係作為本發明之半導體裝置之一例的光半導體裝置(LED)之剖面圖。 1 is a cross-sectional view of an optical semiconductor device (LED) as an example of the semiconductor device of the present invention.
首先，就本發明之半導體裝置詳細地進行說明。 First, the semiconductor device of the present invention will be described in detail.
本發明之半導體裝置為利用聚矽氧硬化物將經鍍金之導線或基板及半導體元件密封而成者。作為該半導體元件，例示有發光二極體(LED)元件、半導體雷射元件、光電二極體元件、光電晶體元件、固體拍攝元件、光電耦合器用發光元件及受光元件，尤佳為發光二極體(LED)元件。 The semiconductor device of the present invention is formed by sealing a gold-plated wire or substrate and a semiconductor element with polysilicon hardened material. Examples of the semiconductor element include a light-emitting diode (LED) element, a semiconductor laser element, a photodiode element, a photoelectric crystal element, a solid-state imaging element, a light-emitting element for a photocoupler, and a light-receiving element, and a light-emitting diode is particularly preferable. Body (LED) components.
藉由圖1詳細地說明本發明之半導體裝置。 The semiconductor device of the present invention will be described in detail with reference to FIG. 1.
圖1為作為半導體裝置之一例之光半導體裝置(LED)之剖面圖。該光半導體裝置(LED)中，發光二極體(LED)元件5藉由接著材料4黏晶於聚鄰苯二甲醯胺(PPA)樹脂製殼體1內之晶片座3上，發光二極體(LED)元件5及經鍍金之導線2藉由金製接合線6而打線結合，發光二極體(LED)元件5、經鍍金之導線2及金製接合線6藉由包含聚矽氧硬化物之密封材料7而密封。 FIG. 1 is a cross-sectional view of an optical semiconductor device (LED) as an example of a semiconductor device. In the optical semiconductor device (LED), the light-emitting diode (LED) element 5 is adhered to the wafer holder 3 in the polyphthalamide (PPA) resin case 1 through the bonding material 4 to emit light. The LED element 5 and the gold-plated wire 2 are wire-bonded by a gold bonding wire 6, the light-emitting diode (LED) element 5, the gold-plated wire 2 and the gold bonding wire 6 are made of polysilicon The sealing material 7 of the oxygen hardened material is sealed.
本發明之半導體裝置中，將經鍍金之導線或基板及半導體元件密封而成之聚矽氧硬化物之特徵在於：其係至少包含如下者之矽氫化反應硬化性聚矽氧組合物之硬化物：(A)於一分子中至少具有2個烯基之有機聚矽氧烷、(B)於一分子中至少具有2個鍵結矽原子之氫原子之有機氫化聚矽氧烷{相對於(A)成分中之烯基1莫耳，本成分中之鍵結矽原子之氫原子成為0.1~10莫耳之量}、(C)鍵結硫原子，且具有鍵結矽原子之水解性基之有機矽化合物(相對於本組合物，為0.0001~2質量%)、及(D)矽氫化反應用鉑系觸媒(相對於本組合物，鉑原子成為0.01~500質量ppm之量)。 In the semiconductor device of the present invention, the polysilicon hardened product sealed by the gold-plated wire or the substrate and the semiconductor element is characterized in that it is a hardened product containing at least the following hydrosilation-reactive hardening polysiloxane composition : (A) Organic polysiloxane with at least 2 alkenyl groups in one molecule, (B) Organic hydrogenated polysiloxane with at least 2 hydrogen atoms bonded to silicon atoms in one molecule A) The alkenyl group in the component is 1 mole, the hydrogen atom of the bonded silicon atom in this component becomes an amount of 0.1 to 10 moles, (C) the bonded sulfur atom, and has a hydrolyzable group bonded to the silicon atom The organosilicon compound (0.0001 to 2% by mass relative to the composition), and (D) the platinum catalyst for hydrosilylation reaction (the amount of platinum atoms to be 0.01 to 500 ppm by mass relative to the composition).
(A)成分為上述組合物之主劑，係於一分子中至少具有2個烯基之有機聚矽氧烷。作為(A)成分中之烯基，例示有：乙烯基、烯丙基、 丁烯基、戊烯基、己烯基、庚烯基、辛烯基、壬烯基、癸烯基、十一碳烯基、十二碳烯基等碳數為2~12個之烯基，較佳為乙烯基。又，作為(A)成分中之烯基以外之鍵結於矽原子之基，例示有：甲基、乙基、丙基、異丙基、丁基、異丁基、第三丁基、戊基、新戊基、己基、環己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基等碳數為1~12個之烷基；苯基、甲苯基、二甲苯基、萘基等碳數為6~20個之芳基；苄基、苯乙基、苯丙基等碳數為7~20個之芳烷基；使該等基之氫原子之一部分或全部經氟原子、氯原子、溴原子等鹵素原子取代之基。再者，於(A)成分中之矽原子中，於無損本發明之目的之範圍內，亦可具有少量羥基或甲氧基、乙氧基等烷氧基。 (A) The component is the main agent of the above composition and is an organic polysiloxane having at least 2 alkenyl groups in one molecule. Examples of the alkenyl group in the component (A) include vinyl, allyl, Butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl and other alkenyl groups with 2 to 12 carbon atoms , Preferably vinyl. In addition, as the group bonded to the silicon atom other than the alkenyl group in the (A) component, there are exemplified methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, pentyl Alkyl, neopentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and other alkyl groups with 1 to 12 carbon atoms; phenyl, tolyl, Aryl groups with 6 to 20 carbons, such as xylyl and naphthyl; aralkyl groups with 7 to 20 carbons, such as benzyl, phenethyl, and phenylpropyl; part of the hydrogen atoms of these groups Or all groups substituted with halogen atoms such as fluorine atom, chlorine atom, bromine atom and the like. In addition, the silicon atoms in the component (A) may have a small amount of alkoxy groups such as hydroxyl groups, methoxy groups, and ethoxy groups within a range that does not impair the object of the present invention.
(A)成分之分子結構並無特別限定，例如，可列舉直鏈狀、具有一部分支鏈之直鏈狀、支鏈狀、環狀、或立體網狀結構。(A)成分可為具有該等分子結構之單獨有機聚矽氧烷，或者亦可為具有該等分子結構之兩種以上之有機聚矽氧烷之混合物。 (A) The molecular structure of the component is not particularly limited, and examples thereof include linear, linear, branched, cyclic, or three-dimensional network structures. (A) The component may be a single organic polysiloxane having such molecular structures, or may be a mixture of two or more organic polysiloxanes having such molecular structures.
關於此種(A)成分，較佳為相對於鍵結矽原子之全部有機基，烯基為0.01~50莫耳%，進而較佳為0.05~40莫耳%，尤佳為0.09~32莫耳%。其原因在於：若(A)成分中之烯基過少，則有無法獲得硬化物之虞，又，若(A)成分中之烯基過多，則有所獲得之硬化物之機械特性變差之虞。又，較佳為(A)成分中之烯基位於有機聚矽氧烷分子之兩末端。再者，(A)成分中之總一價烴基中之烯基之莫耳%例如可藉由傅立葉變換紅外分光光度計(FT-IR)、核磁共振(NMR)、凝膠滲透層析法(GPC)等分析而測定。 With regard to this component (A), it is preferably 0.01 to 50 mol% relative to all organic groups of bonded silicon atoms, further preferably 0.05 to 40 mol%, particularly preferably 0.09 to 32 mol ear%. The reason is that if there are too few alkenyl groups in the (A) component, the hardened product may not be obtained, and if there are too many alkenyl groups in the (A) component, the mechanical properties of the obtained hardened product may deteriorate Yu. In addition, it is preferable that the alkenyl group in the component (A) is located at both ends of the organic polysiloxane molecule. Furthermore, the mole% of the alkenyl group in the total monovalent hydrocarbon group in the component (A) can be determined by Fourier transform infrared spectrophotometer (FT-IR), nuclear magnetic resonance (NMR), gel permeation chromatography ( GPC) and other analysis.
(A)成分係於25℃下為液狀或固體狀之有機聚矽氧烷。於(A)成分於25℃下為液狀之情形時，其25℃下之黏度較佳為在1~1,000,000mPa‧s之範圍內，更佳為在10~1,000,000mPa‧s之範圍內。再者，有機聚矽氧烷之25℃下之黏度例如可藉由按照JIS K7117-1使用B型黏 度計測定而求出。 (A) The component is an organic polysiloxane which is liquid or solid at 25 ° C. When the component (A) is liquid at 25 ° C, the viscosity at 25 ° C is preferably in the range of 1 to 1,000,000 mPa‧s, and more preferably in the range of 10 to 1,000,000 mPa‧s. Furthermore, the viscosity of the organic polysiloxane at 25 ° C. can be used, for example, by using type B viscosity in accordance with JIS K7117-1 The degree is measured and determined.
(B)成分為上述組合物之交聯劑，係於一分子中至少具有2個鍵結矽原子之氫原子之有機氫化聚矽氧烷。作為(B)成分中之氫原子以外之鍵結於矽原子之基，例示有：甲基、乙基、丙基、異丙基、丁基、異丁基、第三丁基、戊基、新戊基、己基、環己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基等碳數為1~12個之烷基；苯基、甲苯基、二甲苯基、萘基等碳數為6~20個之芳基；苄基、苯乙基、苯丙基等碳數為7~20個之芳烷基；使該等基之氫原子之一部分或全部經氟原子、氯原子、溴原子等鹵素原子取代之基。再者，於(B)成分中之矽原子中，於無損本發明之目的之範圍內，亦可具有少量羥基或甲氧基、乙氧基等烷氧基。 (B) The component is a crosslinking agent of the above composition, and is an organic hydrogenated polysiloxane having at least 2 hydrogen atoms bonded to silicon atoms in one molecule. Examples of the group bonded to the silicon atom other than the hydrogen atom in the component (B) include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, pentyl, Neopentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and other alkyl groups with 1 to 12 carbons; phenyl, tolyl, xylene Aryl groups with 6 to 20 carbons, such as radicals and naphthyl; aralkyl groups with 7 to 20 carbons, such as benzyl, phenethyl, and phenylpropyl; part or all of the hydrogen atoms of these radicals A group substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and the like. In addition, the silicon atoms in the component (B) may have a small amount of alkoxy groups such as hydroxyl groups, methoxy groups, and ethoxy groups within a range that does not impair the object of the present invention.
(B)成分之分子結構並無特別限定，例如，可列舉直鏈狀、具有一部分支鏈之直鏈狀、支鏈狀、環狀、或立體網狀結構，較佳可列舉具有一部分支鏈之直鏈狀、支鏈狀、或立體網狀結構。 (B) The molecular structure of the component is not particularly limited, and examples thereof include linear, linear, branched, cyclic, or three-dimensional network structures, and preferably partial chains. The straight chain, branched chain, or three-dimensional network structure.
(B)成分於25℃下為固體狀或液狀。於(B)成分於25℃下為液狀之情形時，其25℃下之黏度較佳為10,000mPa‧s以下，更佳為在0.1~5,000mPa‧s之範圍內，尤佳為在0.5~1,000mPa‧s之範圍內。再者，有機聚矽氧烷之25℃下之黏度例如可藉由按照JIS K7117-1使用B型黏度計測定而求出。 (B) The component is solid or liquid at 25 ° C. When the component (B) is liquid at 25 ° C, the viscosity at 25 ° C is preferably 10,000 mPa‧s or less, more preferably in the range of 0.1 to 5,000 mPa‧s, particularly preferably 0.5 ~ 1,000mPa‧s. In addition, the viscosity at 25 ° C of the organic polysiloxane can be determined by, for example, measurement using a B-type viscometer in accordance with JIS K7117-1.
(B)成分只要可達成本發明之目的，則並不特別限定於特定之有機聚矽氧烷，例如，可列舉：選自由1,1,3,3-四甲基二矽氧烷、1,3,5,7-四甲基環四矽氧烷、三(二甲基氫矽烷氧基)甲基矽烷、三(二甲基氫矽烷氧基)苯基矽烷、1-縮水甘油氧基丙基-1,3,5,7-四甲基環四矽氧烷、1,5-二縮水甘油氧基丙基-1,3,5,7-四甲基環四矽氧烷、1-縮水甘油氧基丙基-5-三甲氧基矽烷基乙基-1,3,5,7-四甲基環四矽氧烷、分子鏈兩封端之三甲基矽烷氧基封阻甲基氫聚矽氧烷、分子鏈兩封端之 三甲基矽烷氧基封阻二甲基矽氧烷-甲基氫矽氧烷共聚物、分子鏈兩封端之二甲基氫矽烷氧基封阻二甲基聚矽氧烷、分子鏈兩封端之二甲基氫矽烷氧基封阻二甲基矽氧烷-甲基氫矽氧烷共聚物、分子鏈兩封端之三甲基矽烷氧基封阻甲基氫矽氧烷-二苯基矽氧烷共聚物、分子鏈兩封端之三甲基矽烷氧基封阻甲基氫矽氧烷-二苯基矽氧烷-二甲基矽氧烷共聚物、包含(CH3)2HSiO1/2單元及SiO4/2單元之共聚物、及包含(CH3)2HSiO1/2單元、SiO4/2單元及(C6H5)SiO3/2單元之共聚物等所組成之群中之1種或2種以上。 (B) The component is not particularly limited to a specific organic polysiloxane as long as it can achieve the purpose of the invention. For example, it can be selected from 1,1,3,3-tetramethyldisilaxane, 1 , 3,5,7-tetramethylcyclotetrasiloxane, tris (dimethylhydrosiloxy) methylsilane, tris (dimethylhydrosiloxy) phenylsilane, 1-glycidoxy Propyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,5-diglycidoxypropyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1 -Glycidoxypropyl-5-trimethoxysilylethyl-1,3,5,7-tetramethylcyclotetrasiloxane, trimethylsiloxyoxy blocking of both ends of the molecular chain Hydrogen-based polysiloxane, molecular chain two-terminated trimethylsiloxy group blocked dimethylsiloxane-methylhydrogen siloxane copolymer, molecular chain two-terminated dimethylhydrosilyloxy group Blocked dimethylpolysiloxane, dimethylhydrosilyloxy with two molecular chain end capping Blocked dimethylsiloxane-methylhydrogen siloxane copolymer, trimethyl with two molecular end capping Siloxyl-blocked methylhydrosiloxane-diphenylsiloxane copolymer, trimethylsiloxy-blocked methyl group with two molecular chain ends Hydrosiloxane-diphenylsiloxane-dimethylsiloxane copolymer, copolymer containing (CH 3 ) 2 HSiO 1/2 units and SiO 4/2 units, and (CH 3 ) 2 HSiO One or more of the group consisting of 1/2 unit, SiO 4/2 unit and (C 6 H 5 ) SiO 3/2 unit copolymer.
關於(B)成分之含量，為相對於(A)成分中之烯基1莫耳，本成分中之鍵結矽原子之氫原子成為0.1~10莫耳之量，較佳為成為0.5~5莫耳之量。其原因在於：若(B)成分之含量為上述範圍之上限以下，則可抑制所獲得之硬化物之機械特性之降低，另一方面，若為上述範圍之下限以上，則所獲得之組合物充分地硬化。再者，(B)成分中之鍵結矽原子之氫原子之量例如可藉由傅立葉變換紅外分光光度計(FT-IR)、核磁共振(NMR)、凝膠滲透層析法(GPC)等分析而測定。 The content of the component (B) is 1 mole of the alkenyl group in the component (A), and the hydrogen atom of the bonded silicon atom in this component is 0.1 to 10 moles, preferably 0.5 to 5. The amount of mole. The reason for this is that if the content of the component (B) is below the upper limit of the above range, the mechanical properties of the obtained hardened product can be prevented from decreasing, while on the other hand, if it is above the lower limit of the above range, the obtained composition Fully hardened. Furthermore, the amount of hydrogen atoms bonded to silicon atoms in the component (B) can be determined by Fourier transform infrared spectrophotometer (FT-IR), nuclear magnetic resonance (NMR), gel permeation chromatography (GPC), etc. Analysis and determination.
(C)成分之有機矽化合物為鍵結硫原子且具有鍵結矽原子之水解性基者，係對上述組合物賦予與經鍍金之導線框架之良好接著性之成分。作為此種(C)成分，例示有：3-巰丙基三甲氧基矽烷、3-巰丙基三乙氧基矽烷、3-巰丙基甲基二甲氧基矽烷、3-巰丙基甲基二乙氧基矽烷等巰基烷基烷氧基矽烷；雙(三甲氧基矽烷基丙基)二硫化物、雙(三甲氧基矽烷基丙基)三硫化物、雙(三甲氧基矽烷基丙基)四硫化物等雙(烷氧基矽烷基烷基)硫化物。 (C) The organosilicon compound of the component is a sulfur atom-bonded and has a silicon atom-bonded hydrolyzable group, and is a component that imparts good adhesion to the above-mentioned composition to the gold-plated lead frame. Examples of such component (C) include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyl Mercaptoalkylalkoxysilanes such as methyldiethoxysilane; bis (trimethoxysilylpropyl) disulfide, bis (trimethoxysilylpropyl) trisulfide, bis (trimethoxysilane Bis (alkoxysilylalkyl) sulfide such as propylpropyl) tetrasulfide.
(C)成分之含量相對於上述組合物為0.0001~2質量%，較佳為成為0.001~1質量%，尤佳為成為0.01~0.2質量%之量。其原因在於：若為上述範圍之下限以上，則對經鍍金之導線或基板之接著性提高，另一方面，若為上述範圍之上限以下，則不產生上述組合物之硬化阻 礙。 (C) The content of the component is 0.0001 to 2% by mass relative to the composition, preferably 0.001 to 1% by mass, and particularly preferably 0.01 to 0.2% by mass. The reason is that if it is more than the lower limit of the above range, the adhesion to the gold-plated wire or substrate is improved, and on the other hand, if it is less than the upper limit of the above range, the curing resistance of the above composition does not occur hinder.
(D)成分為用以促進上述組合物之矽氫化反應之矽氫化反應用鉑系觸媒。作為此種(D)成分，例示有：鉑微粉末、鉑黑、氯鉑酸、氯鉑酸之醇改性物、氯鉑酸與二烯烴之錯合物、鉑-烯烴錯合物、雙(乙醯乙酸)鉑、雙(乙醯丙酮)鉑等鉑-羰基錯合物、氯鉑酸-二乙烯基四甲基二矽氧烷錯合物、氯鉑酸-四乙烯基四甲基環四矽氧烷錯合物等氯鉑酸-烯基矽氧烷錯合物、鉑-二乙烯基四甲基二矽氧烷錯合物、鉑-四乙烯基四甲基環四矽氧烷錯合物等鉑-烯基矽氧烷錯合物、及氯鉑酸與乙炔醇類之錯合物，就矽氫化反應之促進效果較高而言，尤佳為鉑-烯基矽氧烷錯合物。該等矽氫化反應用鉑系觸媒可單獨使用一種，亦可併用兩種以上。 (D) The component is a platinum-based catalyst for hydrosilylation reaction for promoting the hydrosilylation reaction of the above composition. Examples of such component (D) include platinum fine powder, platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, the complex compound of chloroplatinic acid and diene, platinum-olefin complex compound, bis (Acetylacetic acid) platinum, bis (acetylacetone) platinum and other platinum-carbonyl complexes, chloroplatinic acid-divinyltetramethyldisilazane complex, chloroplatinic acid-tetravinyltetramethyl Chloroplatinic acid-alkenyl siloxane complex, platinum-divinyltetramethyldisilazane complex, platinum-tetravinyltetramethylcyclotetrasiloxane For platinum-alkenyl siloxane complexes such as alkane complexes, and complex compounds of chloroplatinic acid and acetylene alcohols, platinum-alkenylsilicone is particularly preferred in terms of the higher effect of the hydrosilation reaction. Alkane complex. These platinum-based catalysts for hydrosilation reaction may be used alone or in combination of two or more.
用於鉑-烯基矽氧烷錯合物之烯基矽氧烷並無特別限定，例如，可列舉：1,3-二乙烯基-1,1,3,3-四甲基二矽氧烷、1,3,5,7-四甲基-1,3,5,7-四乙烯基環四矽氧烷、使該等烯基矽氧烷之甲基之一部分經乙基、苯基等取代之烯基矽氧烷低聚物、及使該等烯基矽氧烷之乙烯基經烯丙基、己烯基等取代之烯基矽氧烷低聚物等。就生成之鉑-烯基矽氧烷錯合物之穩定性良好而言，尤佳為1,3-二乙烯基-1,1,3,3-四甲基二矽氧烷。 The alkenyl siloxane used in the platinum-alkenyl siloxane complex is not particularly limited, for example, 1,3-divinyl-1,1,3,3-tetramethyldisilax Alkane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, part of the methyl group of the alkenylsiloxane via ethyl, phenyl Such as substituted alkenyl siloxane oligomers, and alkenyl siloxane oligomers in which vinyl groups of these alkenyl siloxanes are substituted with allyl, hexenyl, etc. In view of the good stability of the resulting platinum-alkenylsiloxane complex, 1,3-divinyl-1,1,3,3-tetramethyldisilaxane is particularly preferred.
又，為了提高鉑-烯基矽氧烷錯合物之穩定性，較佳為將該等鉑-烯基矽氧烷錯合物溶解於1,3-二乙烯基-1,1,3,3-四甲基二矽氧烷、1,3-二烯丙基-1,1,3,3-四甲基二矽氧烷、1,3-二乙烯基-1,3-二甲基-1,3-二苯基二矽氧烷、1,3-二乙烯基-1,1,3,3-四苯基二矽氧烷、及1,3,5,7-四甲基-1,3,5,7-四乙烯基環四矽氧烷等烯基矽氧烷低聚物或二甲基矽氧烷低聚物等有機矽氧烷低聚物中，尤佳為溶解於烯基矽氧烷低聚物中。 In addition, in order to improve the stability of the platinum-alkenyl siloxane complex, it is preferable to dissolve the platinum-alkenyl siloxane complex in 1,3-divinyl-1,1,3, 3-tetramethyldisilaxane, 1,3-diallyl-1,1,3,3-tetramethyldisilaxane, 1,3-divinyl-1,3-dimethyl -1,3-diphenyldisilaxane, 1,3-divinyl-1,1,3,3-tetraphenyldisilaxane, and 1,3,5,7-tetramethyl- 1,3,5,7-tetravinylcyclotetrasiloxane and other alkenyl siloxane oligomers or dimethyl siloxane oligomers and other organic siloxane oligomers, preferably dissolved in Alkenyl silicone oligomers.
(D)成分之含量為相對於上述組合物，(D)成分中之鉑原子成為 0.01~500質量ppm之量，較佳為成為0.01~100質量ppm之範圍內之量，尤佳為成為0.1~50質量ppm之範圍內之量。其原因在於：若(D)成分之含量為上述範圍之下限以上，則所獲得之組合物充分地硬化，另一方面，若為上述範圍之上限以下，則可抑制所獲得之硬化物之著色。 (D) The content of the component is that the platinum atom in the (D) component becomes The amount of 0.01 to 500 mass ppm is preferably an amount in the range of 0.01 to 100 mass ppm, and particularly preferably an amount in the range of 0.1 to 50 mass ppm. The reason is that if the content of the (D) component is above the lower limit of the above range, the obtained composition is sufficiently hardened, and on the other hand, if it is below the upper limit of the above range, the coloration of the obtained hardened product can be suppressed .
於上述組合物中，亦可含有(E)矽氫化反應抑制劑作為用以延長常溫下之使用壽命，提高保存穩定性之任意成分。作為此種(E)成分，例示有：1-乙炔基環己烷-1-醇、2-甲基-3-丁炔-2-醇、3,5-二甲基-1-己炔-3-醇、及2-苯基-3-丁炔-2-醇等炔醇；3-甲基-3-戊烯-1-炔、及3,5-二甲基-3-己烯-1-炔等烯炔化合物；1,3,5,7-四甲基-1,3,5,7-四乙烯基環四矽氧烷、及1,3,5,7-四甲基-1,3,5,7-四己烯基環四矽氧烷等甲基烯基矽氧烷低聚物；二甲基雙(3-甲基-1-丁炔-3-氧基)矽烷、及甲基乙烯基雙(3-甲基-1-丁炔-3-氧基)矽烷等炔氧基矽烷、以及異氰尿酸三烯丙酯系化合物。 The above composition may also contain (E) a hydrosilation inhibitor as an arbitrary component for extending the service life at normal temperature and improving storage stability. Examples of such component (E) include 1-ethynylcyclohexane-1-ol, 2-methyl-3-butyn-2-ol, 3,5-dimethyl-1-hexyne- 3-alcohol, and 2-phenyl-3-butyn-2-ol and other alkynyl alcohols; 3-methyl-3-pentene-1-yne, and 3,5-dimethyl-3-hexene- Enynes such as 1-alkynes; 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane and 1,3,5,7-tetramethyl- 1,3,5,7-tetrahexenyl cyclotetrasiloxane and other methalkenyl siloxane oligomers; dimethyl bis (3-methyl-1-butyn-3-oxy) silane , And alkynyloxysilane such as methylvinylbis (3-methyl-1-butyn-3-oxy) silane, and triallyl isocyanurate compounds.
(E)成分之含量並無特別限定，係為了上述(A)成分~(D)成分之混合時抑制凝膠化，或抑制硬化之充分之量，進而，係為了可長期保存之充分之量。作為(E)成分之含量，具體而言，相對於上述(A)成分~(D)成分之合計100質量份，較佳為0.0001~5質量份之範圍內，更佳為0.01~3質量份之範圍內。 (E) The content of the component is not particularly limited, and it is a sufficient amount for suppressing gelation or curing when the above components (A) to (D) are mixed, and further, a sufficient amount for long-term storage . The content of the (E) component is specifically, in the range of 0.0001 to 5 parts by mass, more preferably 0.01 to 3 parts by mass, with respect to the total of 100 parts by mass of the components (A) to (D). Within.
又，於上述組合物中，為了進一步提高對硬化中接觸之基材之接著性，亦可含有接著促進劑。作為該接著促進劑，較佳為於一分子中具有1個或2個以上鍵結於矽原子之烷氧基之有機矽化合物。作為該烷氧基，例示有：甲氧基、乙氧基、丙氧基、丁氧基、及甲氧基乙氧基等，尤佳為甲氧基或乙氧基。又，作為鍵結於該有機矽化合物之矽原子的烷氧基以外之基，例示有：烷基、烯基、芳基、芳烷基、及鹵化烷基等經取代或未經取代之一價烴基；3-縮水甘油氧基丙基、及4- 縮水甘油氧基丁基等縮水甘油氧基烷基；2-(3,4-環氧環己基)乙基、及3-(3,4-環氧環己基)丙基等環氧環己基烷基；4-環氧乙烷基丁基、及8-環氧乙烷基辛基等環氧乙烷基烷基等含環氧基一價有機基；3-甲基丙烯醯氧丙基等含丙烯基一價有機基；異氰酸酯基；異氰尿酸酯基；以及氫原子。該有機矽化合物較佳為具有可與本組合物中之脂肪族不飽和烴基或鍵結矽原子之氫原子反應之基，具體而言，較佳為具有鍵結矽原子之脂肪族不飽和烴基或鍵結矽原子之氫原子。 In addition, in the above-mentioned composition, in order to further improve the adhesion to the substrate contacted during curing, an adhesion promoter may be contained. The adhesion promoter is preferably an organosilicon compound having one or more alkoxy groups bonded to silicon atoms in one molecule. Examples of the alkoxy group include methoxy, ethoxy, propoxy, butoxy, and methoxyethoxy groups, and methoxy or ethoxy groups are particularly preferred. In addition, as a group other than the alkoxy group bonded to the silicon atom of the organosilicon compound, there are exemplified one of substituted or unsubstituted ones such as alkyl, alkenyl, aryl, aralkyl, and halogenated alkyl groups. Valent hydrocarbon group; 3-glycidoxypropyl, and 4- Glycidoxyalkyl groups such as glycidoxybutyl; epoxycyclohexylalkyl groups such as 2- (3,4-epoxycyclohexyl) ethyl and 3- (3,4-epoxycyclohexyl) propyl Group; 4-oxiranylbutyl, 8-oxiranyloctyl and other oxiranylalkyl and other epoxy-containing monovalent organic groups; 3-methacryloxypropyl and the like Contains an acryl-based monovalent organic group; isocyanate group; isocyanurate group; and hydrogen atom. The organosilicon compound preferably has a group that can react with the aliphatic unsaturated hydrocarbon group or hydrogen atom bonded to the silicon atom in the composition, and specifically, it is preferably an aliphatic unsaturated hydrocarbon group having bonded silicon atom Or hydrogen atoms bonded to silicon atoms.
接著促進劑之含量並無限定，相對於上述(A)成分~(D)成分之合計100質量份，較佳為0.01~10質量份之範圍內，更佳為0.1~3質量份之範圍內。 Next, the content of the accelerator is not limited, and it is preferably in the range of 0.01 to 10 parts by mass, more preferably in the range of 0.1 to 3 parts by mass with respect to the total of 100 parts by mass of the components (A) to (D). .
又，於上述組合物中可含有螢光體作為其他任意成分。作為該螢光體，例如，可列舉廣泛利用於發光二極體(LED)之包含氧化物系螢光體、氮氧化物系螢光體、氮化物系螢光體、硫化物系螢光體、氧硫化物系螢光體等之黃色、紅色、綠色、藍色發光螢光體。作為氧化物系螢光體，例示有：包含鈰離子之釔、鋁、石榴石系之YAG系綠色~黃色發光螢光體，包含鈰離子之鋱、鋁、石榴石系之TAG系黃色發光螢光體，及包含鈰或銪離子之矽酸鹽系綠色~黃色發光螢光體。作為氮氧化物系螢光體，例示有：包含銪離子之矽、鋁、氧、氮系之賽隆系紅色~綠色發光螢光體。作為氮化物系螢光體，例示有：包含銪離子之鈣、鍶、鋁、矽、氮系之CASN系紅色發光螢光體。作為硫化物系螢光體，例示有：包含銅離子或鋁離子之ZnS系綠色顯色螢光體。作為氧硫化物系螢光體，例示有：包含銪離子之Y2O2S系紅色發光螢光體。該等螢光體可使用1種，或者，亦可使用2種以上之混合物。 In addition, the above-mentioned composition may contain phosphors as other optional components. Examples of the phosphor include oxide-based phosphors, oxynitride-based phosphors, nitride-based phosphors, and sulfide-based phosphors widely used in light-emitting diodes (LEDs). , Oxysulfide-based phosphors, yellow, red, green, blue light-emitting phosphors. Examples of oxide-based phosphors include: YAG-based green to yellow luminescent phosphors containing cerium ions, yttrium, aluminum, and garnet, and TAG-based yellow luminescent phosphors containing cerium ions, yttrium, aluminum, and garnet. The light body and the silicate green-yellow luminescent phosphor containing cerium or europium ions. Examples of the nitrogen oxide-based phosphor include: silicon, aluminum, oxygen, and nitrogen-based sialon-based red-to-green phosphors containing europium ions. Examples of nitride-based phosphors include CASN-based red-emitting phosphors containing calcium, strontium, aluminum, silicon, and nitrogen based on europium ions. Examples of sulfide-based phosphors include ZnS-based green color-forming phosphors containing copper ions or aluminum ions. Examples of oxysulfide-based phosphors include Y 2 O 2 S-based red light-emitting phosphors containing europium ions. One type of these phosphors may be used, or a mixture of two or more types may be used.
該螢光體之含量並無特別限定，於上述組合物中為0.1~70質量%之範圍內，進而較佳為1~20質量%之範圍內。 The content of the phosphor is not particularly limited, and it is in the range of 0.1 to 70% by mass in the above composition, and more preferably in the range of 1 to 20% by mass.
又，於上述組合物中，只要無損本發明之目的，亦可含有選自二氧化矽、玻璃及氧化鋁等之1種或2種以上之無機質填充劑；聚矽氧橡膠粉末；聚矽氧樹脂、及聚甲基丙烯酸酯樹脂等樹脂粉末；選自耐熱劑、染料、顏料、阻燃性賦予劑、界面活性劑、溶劑等之1種或2種以上成分，作為其他任意成分。 In addition, as long as the purpose of the present invention is not impaired, the above composition may contain one or more inorganic fillers selected from silica, glass, alumina, etc .; polysilicone rubber powder; polysilicone Resin powders such as resins and polymethacrylate resins; one or more components selected from heat-resistant agents, dyes, pigments, flame retardancy-imparting agents, surfactants, solvents, etc., as other arbitrary components.
本發明之半導體裝置之製造方法並無特別限定，例如，圖1所示之光半導體裝置(LED)可如下所述製造。 The method of manufacturing the semiconductor device of the present invention is not particularly limited. For example, the optical semiconductor device (LED) shown in FIG. 1 can be manufactured as follows.
藉由接著材料4將發光二極體(LED)元件5黏晶於聚鄰苯二甲醯胺(PPA)樹脂製殼體1內之晶片座3上。其次，將發光二極體(LED)元件5及經鍍金之導線2藉由金製接合線6進行打線結合。其次，將上述組合物注入聚鄰苯二甲醯胺(PPA)樹脂製殼體1內，使其硬化，藉此，利用包含聚矽氧硬化物之密封材料將發光二極體(LED)元件5、經鍍金之導線2及金製接合線6密封。於該製造方法中，作為使上述組合物硬化之方法，可藉由室溫放置或加熱進行硬化，為了使其迅速硬化，較佳為加熱。作為加熱溫度，較佳為在50~200℃之範圍內。 The light-emitting diode (LED) element 5 is bonded to the wafer holder 3 in the housing 1 made of polyphthalamide (PPA) resin by the bonding material 4. Next, the light emitting diode (LED) element 5 and the gold-plated wire 2 are wire-bonded by a gold bonding wire 6. Next, the above composition is injected into the polyphthalamide (PPA) resin case 1 to harden it, whereby the light emitting diode (LED) device is sealed with a sealing material containing polysiloxane hardened material 5. The gold-plated wire 2 and the gold bonding wire 6 are sealed. In this production method, as a method of curing the above composition, curing can be carried out by leaving at room temperature or heating, and in order to rapidly cure it, heating is preferred. The heating temperature is preferably in the range of 50 to 200 ° C.
關於以此方式獲得之半導體裝置，聚矽氧硬化物之JIS K 6253所規定之A型硬度計硬度較佳為10~99，尤佳為15~95。其原因在於：若聚矽氧硬化物之硬度為上述範圍之下限以上，則硬化物之強度變大，可充分地保護半導體元件避免來自外部之應力，另一方面，若為上述範圍之上限以下，則硬化物變得柔軟，可充分地保護半導體元件避免熱衝擊。 Regarding the semiconductor device obtained in this way, the hardness of the type A durometer specified in JIS K 6253 of the polysilicon hardened product is preferably 10 to 99, particularly preferably 15 to 95. The reason is that if the hardness of the polysilicon hardened product is above the lower limit of the above range, the strength of the hardened product becomes greater, which can sufficiently protect the semiconductor device from external stress, on the other hand, if it is below the upper limit of the above range , The hardened product becomes soft and can fully protect the semiconductor element from thermal shock.
其次，詳細地說明本發明之半導體元件密封用硬化性聚矽氧組合物。 Next, the curable polysiloxane composition for sealing a semiconductor element of the present invention will be described in detail.
本發明之半導體元件密封用硬化性聚矽氧組合物之特徵在於：其係用於密封半導體裝置中之經鍍金之導線或基板及半導體元件之矽氫化反應硬化性聚矽氧組合物，且至少包含(A)於一分子中至少具有2 個烯基之有機聚矽氧烷、(B)於一分子中至少具有2個鍵結矽原子之氫原子之有機氫化聚矽氧烷{相對於(A)成分中之烯基1莫耳，本成分中之鍵結矽原子之氫原子成為0.1~10莫耳之量}、(C)鍵結硫原子且具有鍵結矽原子之水解性基之有機矽化合物(相對於本組合物為0.0001~2質量%)、及(D)矽氫化反應用鉑系觸媒(相對於本組合物，鉑原子成為0.01~500質量ppm之量)。 The curable polysiloxane composition for sealing a semiconductor element of the present invention is characterized in that it is a hydrosilation reaction-curable polysiloxane composition used for sealing a gold-plated wire or substrate and a semiconductor element in a semiconductor device, and at least Include (A) in a molecule with at least 2 Alkenyl organic polysiloxane, (B) organic hydrogenated polysiloxane having at least 2 hydrogen atoms bonded to silicon atoms in one molecule {compared to 1 mole of alkenyl in (A) component, The hydrogen atom of the bonded silicon atom in this component becomes an amount of 0.1 to 10 moles), (C) an organosilicon compound bonded to a sulfur atom and having a hydrolyzable group bonded to the silicon atom (relative to this composition: 0.0001 ~ 2% by mass), and (D) platinum catalyst for hydrosilylation reaction (relative to the present composition, the amount of platinum atoms is 0.01 to 500 ppm by mass).
關於上述(A)成分~(D)成分，如上所述。又，於本組合物中，除用以延長常溫下之可使用壽命，提高保存穩定性之(E)矽氫化反應抑制劑以外，亦可含有接著促進劑；螢光體；選自二氧化矽、玻璃、及氧化鋁等之1種或2種以上之無機質填充劑；聚矽氧橡膠粉末；聚矽氧樹脂、及聚甲基丙烯酸酯樹脂等樹脂粉末；選自耐熱劑、染料、顏料、阻燃性賦予劑、界面活性劑、溶劑等之1種或2種以上之成分。關於該等成分及其含量係如上所述。 The components (A) to (D) are as described above. In addition, in this composition, in addition to the (E) hydrosilation reaction inhibitor used to extend the service life at normal temperature and improve storage stability, it may also contain an adhesion promoter; phosphor; selected from silicon dioxide , Glass, and alumina, one or more inorganic fillers; polysiloxane rubber powder; polysiloxane resin, polymethacrylate resin and other resin powder; selected from heat-resistant agents, dyes, pigments, One or more components of flame retardant imparting agent, surfactant, solvent, etc. These components and their contents are as described above.
此種本發明之硬化性聚矽氧組合物為包含上述(A)成分~(D)成分，進而包含上述任意成分者，可設為一液型、或區分為任意成分之二液型。 Such a curable polysiloxane composition of the present invention contains the above-mentioned components (A) to (D), and further contains any of the above-mentioned optional components, and can be set to a one-component type or a two-component type divided into optional components.
使用實施例及比較例詳細地說明本發明之半導體裝置及半導體元件密封用硬化性聚矽氧組合物。再者，化學式中，Me表示甲基，Vi表示乙烯基，Ph表示苯基。 The hardening polysiloxane composition for sealing a semiconductor device and a semiconductor device of the present invention will be described in detail using Examples and Comparative Examples. Furthermore, in the chemical formula, Me represents a methyl group, Vi represents a vinyl group, and Ph represents a phenyl group.
[實施例1~5、比較例1~7] [Examples 1 to 5, Comparative Examples 1 to 7]
將下述成分按照以下之表1所示之組成(質量份)均勻地混合，製備實施例1~5及比較例1~7之硬化性聚矽氧組合物。又，表1中，SiH/Vi表示硬化性聚矽氧組合物中，(B)成分中之鍵結矽原子之氫原子相對於(A)成分中之乙烯基之合計1莫耳之合計莫耳數。 The following components were uniformly mixed according to the composition (parts by mass) shown in Table 1 below to prepare the curable polysiloxane compositions of Examples 1 to 5 and Comparative Examples 1 to 7. In addition, in Table 1, SiH / Vi represents a total of 1 mole of hydrogen atoms bonded to silicon atoms in component (B) relative to the total of vinyl groups in component (A) in the curable polysiloxane composition. Ears.
使用如下成分作為(A)成分。再者，有機聚矽氧烷可藉由公知之 製法獲得。又，黏度為25℃下之值，按照JIS K7117-1使用B型黏度計進行測定。又，乙烯基之含量藉由FT-IR、NMR、GPC等分析進行測定。 The following components are used as (A) components. Furthermore, organic polysiloxanes can be Obtained by the method. In addition, the viscosity is a value at 25 ° C, and is measured using a B-type viscometer in accordance with JIS K7117-1. In addition, the vinyl content is measured by analysis such as FT-IR, NMR, GPC and the like.
(a-1)成分：黏度300mPa‧s，以平均式：Me2ViSiO(Me2SiO)150SiMe2Vi (a-1) Composition: Viscosity 300mPa‧s, with an average formula: Me 2 ViSiO (Me 2 SiO) 150 SiMe 2 Vi
所表示之分子鏈兩封端之二甲基乙烯基矽烷氧基封阻二甲基聚矽氧烷(乙烯基之含量=0.48質量%) The dimethylvinyl silane oxy-blocked dimethyl polysiloxane on both ends of the indicated molecular chain (vinyl content = 0.48% by mass)
(a-2)成分：黏度10,000mPa‧s，以平均式：Me2ViSiO(Me2SiO)500SiMe2Vi (a-2) Composition: viscosity 10,000mPa‧s, with average formula: Me 2 ViSiO (Me 2 SiO) 500 SiMe 2 Vi
所表示之分子鏈兩封端之二甲基乙烯基矽烷氧基封阻二甲基聚矽氧烷(乙烯基之含量=0.15質量%) The dimethylvinyl silane oxy-blocked dimethyl polysiloxane on both ends of the indicated molecular chain (content of vinyl group = 0.15 mass%)
(a-3)成分：黏度1,000mPa‧s，以平均式：Me2ViSiO(MePhSiO)30SiMe2Vi (a-3) Composition: Viscosity 1,000mPa‧s, with the average formula: Me 2 ViSiO (MePhSiO) 30 SiMe 2 Vi
所表示之甲基苯基聚矽氧烷(乙烯基之含量=1.27質量%) The indicated methylphenyl polysiloxane (vinyl content = 1.27% by mass)
(a-4)成分：25℃下為白色固體狀，為甲苯可溶性，以平均單元式：(Me2ViSiO1/2)0.13(Me3SiO1/2)0.45(SiO4/2)0.42(HO1/2)0.01 (a-4) Components: white solid at 25 ° C, soluble in toluene, with an average unit formula: (Me 2 ViSiO 1/2 ) 0.13 (Me 3 SiO 1/2 ) 0.45 (SiO 4/2 ) 0.42 ( HO 1/2 ) 0.01
所表示之於一分子中具有2個以上之乙烯基之有機聚矽氧烷樹脂(乙烯基之含量=3.4質量%) The organic polysiloxane resin with 2 or more vinyl groups in one molecule (vinyl content = 3.4% by mass)
(a-5)成分：25℃下為白色固體狀，為甲苯可溶性，以平均單元式：(Me2ViSiO1/2)0.15(Me3SiO1/2)0.38(SiO4/2)0.47(HO1/2)0.01 (a-5) Ingredients: white solid at 25 ° C, soluble in toluene, with an average unit formula: (Me 2 ViSiO 1/2 ) 0.15 (Me 3 SiO 1/2 ) 0.38 (SiO 4/2 ) 0.47 ( HO 1/2 ) 0.01
所表示之於一分子中具有2個以上之乙烯基之有機聚矽氧烷(乙烯基之含量=4.2質量%) The organic polysiloxane with two or more vinyl groups in one molecule (vinyl content = 4.2% by mass)
(a-6)成分：25℃下為白色固體狀，為甲苯可溶性，以平均單元式： (PhSiO3/2)0.75(Me2ViSiO1/2)0.25 (a-6) Ingredients: white solid at 25 ° C, soluble in toluene, with an average unit formula: (PhSiO 3/2 ) 0.75 (Me 2 ViSiO 1/2 ) 0.25
所表示之於一分子中具有2個以上之乙烯基之有機聚矽氧烷(乙烯基之含量=5.6質量%) The organic polysiloxane with two or more vinyl groups in one molecule (vinyl content = 5.6% by mass)
使用如下成分作為(B)成分。再者，有機氫化聚矽氧烷可藉由公知之製法而獲得。又，黏度為25℃下之值，按照JIS K7117-1使用B型黏度計進行測定。又，鍵結矽原子之氫原子之含量及每個分子之鍵結矽原子之氫原子之個數藉由FT-IR、NMR、GPC等分析進行測定。 The following components are used as component (B). Furthermore, the organic hydrogenated polysiloxane can be obtained by a known method. In addition, the viscosity is a value at 25 ° C, and is measured using a B-type viscometer in accordance with JIS K7117-1. In addition, the content of hydrogen atoms bonded to silicon atoms and the number of hydrogen atoms bonded to silicon atoms per molecule were measured by FT-IR, NMR, GPC and other analyses.
(b-1)成分：以平均式：Me3SiO(MeHSiO)15SiMe3 (b-1) Composition: average formula: Me 3 SiO (MeHSiO) 15 SiMe 3
所表示之黏度5mPa‧s之分子鏈兩封端之三甲基矽烷氧基封阻甲基氫聚矽氧烷(鍵結矽原子之氫原子之含量=1.42質量%) The indicated viscosity of 5mPa‧s molecular chain two-terminated trimethylsiloxy groups block methyl hydrogen polysiloxane (bonded silicon atom hydrogen atom content = 1.42% by mass)
(b-2)成分：以平均式：Me3SiO(MeHSiO)55SiMe3 (b-2) Composition: average formula: Me 3 SiO (MeHSiO) 55 SiMe 3
所表示之黏度20mPa‧s之分子鏈兩封端之三甲基矽烷氧基封阻聚甲基氫矽氧烷(鍵結矽原子之氫原子之含量=1.6質量%) The indicated viscosity of 20mPa‧s molecular chain two-terminated trimethylsilyloxy-blocked polymethylhydrosiloxane (content of hydrogen atoms bonded to silicon atoms = 1.6% by mass)
(b-3)成分：以平均式：HMe2SiO(Ph2SiO)SiMe2H (b-3) Composition: With an average formula: HMe 2 SiO (Ph 2 SiO) SiMe 2 H
所表示之黏度5mPa‧s之分子鏈兩封端之二甲基氫矽烷氧基封阻二苯基聚矽氧烷(鍵結矽原子之氫原子之含量=0.6質量%) The indicated molecular chain with a viscosity of 5 mPa‧s is blocked by two dimethylhydrosiloxyl-blocked diphenylpolysiloxanes (content of hydrogen atoms bonded to silicon atoms = 0.6% by mass)
(b-4)成分：以平均單元式：(PhSiO3/2)0.4(HMe2SiO1/2)0.6 (b-4) Composition: in average unit formula: (PhSiO 3/2 ) 0.4 (HMe 2 SiO 1/2 ) 0.6
所表示之黏度25mPa‧s之於一分子中具有2個以上之鍵結矽原子之氫原子之支鏈狀有機聚矽氧烷(鍵結矽原子之氫原子之含量=0.65質量%) The indicated viscosity is 25 mPa‧s in a molecule of a branched-chain organic polysiloxane having more than two hydrogen atoms bonded to silicon atoms in one molecule (content of hydrogen atoms bonded to silicon atoms = 0.65% by mass)
使用如下成分作為(C)成分。 The following components are used as component (C).
(c-1)成分：3-巰丙基三甲氧基矽烷 (c-1) Ingredient: 3-mercaptopropyl trimethoxysilane
(c-2)成分：雙(3-三乙氧基矽烷基丙基)四硫化物 (c-2) Ingredient: bis (3-triethoxysilylpropyl) tetrasulfide
(c-3)成分：1,3,5-異氰尿酸三縮水甘油酯 (c-3) Ingredient: 1,3,5-isocyanuric acid triglycidyl ester
(c-4)成分：3-甲基丙烯醯氧丙基三甲氧基矽烷 (c-4) Ingredients: 3-methacryloxypropyltrimethoxysilane
(c-5)成分：3-丙烯醯氧丙基三甲氧基矽烷 (c-5) Ingredients: 3-propenyloxypropyltrimethoxysilane
(c-6)成分：3-縮水甘油氧基丙基三甲氧基矽烷 (c-6) Ingredients: 3-glycidoxypropyltrimethoxysilane
(c-7)成分：2-巰基苯并噻唑 (c-7) Ingredient: 2-mercaptobenzothiazole
使用鉑之1,3-二乙烯基四甲基二矽氧烷錯合物之1,3-二乙烯基四甲基二矽氧烷溶液(鉑金屬之含量=約5000質量ppm)作為(D)成分。 Use 1,3-divinyltetramethyldisilazane solution of platinum 1,3-divinyltetramethyldisilazane complex (content of platinum metal = about 5000 mass ppm) as (D )ingredient.
使用1-乙炔基環己烷-1-醇作為(E)成分。 As the (E) component, 1-ethynylcyclohexane-1-ol is used.
[評價及結果] [Evaluation and results]
關於實施例1~5及比較例1~7所獲得之硬化性聚矽氧組合物，將(甲)150℃之凝膠化時間之測定、(乙)聚矽氧硬化物之硬度之測定、(丙)密封材料之初期剝離率之測定、及(丁)密封材料之吸濕回焊後之剝離率之測定結果示於表1。 Regarding the curable polysiloxane compositions obtained in Examples 1 to 5 and Comparative Examples 1 to 7, (A) the measurement of the gelation time at 150 ° C, (B) the measurement of the hardness of the polysiloxane cured product, (C) The initial peeling rate of the sealing material and (D) the peeling rate of the sealing material after moisture absorption and reflow are shown in Table 1.
150℃之凝膠化時間(秒)係使用Alpha Technologies Rheometer MDR 2000P進行測定。 The gelation time (seconds) at 150 ° C was measured using Alpha Technologies Rheometer MDR 2000P.
關於聚矽氧硬化物之硬度，藉由將實施例1~5及比較例1~7所獲得之硬化性聚矽氧組合物於150℃下以1小時、5MPa之壓力進行加壓成形，製作片狀之聚矽氧硬化物，藉由JIS K 6253所規定之A型硬度計測定該硬度。 Regarding the hardness of the polysiloxane cured product, the curable polysiloxane composition obtained in Examples 1 to 5 and Comparative Examples 1 to 7 was press-formed at 150 ° C. for 1 hour under a pressure of 5 MPa to produce The sheet-shaped polysilicon hardened product was measured with an A-type hardness tester specified in JIS K 6253.
[光半導體裝置(LED)之製作] [Fabrication of Optical Semiconductor Device (LED)]
經鍍金之導線自側壁朝著底部阻塞之圓筒狀之聚鄰苯二甲醯胺(PPA)樹脂殼(內徑2.0mm、深度1.0mm)之內底部之中心部外延，於經鍍金之導線之中央部上載置有LED晶片，將各實施例或各比較例之硬化性聚矽氧組合物脫泡，使用分注器注入LED晶片及經鍍金之導線藉由金製接合線電性連接之前驅物之聚鄰苯二甲醯胺(PPA)樹脂殼 內，於加熱烘箱中以100℃加熱30分鐘，繼而以150℃加熱1小時，進行硬化，藉此，製造圖1所示之光半導體裝置(LED)各20個。 The gold-plated wire is extended from the center of the inner bottom of the cylindrical polyphthalamide (PPA) resin shell (inner diameter 2.0mm, depth 1.0mm) blocked from the side wall toward the bottom, on the gold-plated wire Before the LED chip is placed on the central part, the hardening polysiloxane composition of each example or each comparative example is defoamed, and the LED chip and the gold-plated wire are injected into the LED chip and electrically connected by a gold bonding wire using a dispenser Repellent polyphthalamide (PPA) resin shell In the heating oven, heating was performed at 100 ° C. for 30 minutes and then at 150 ° C. for 1 hour to cure, thereby manufacturing 20 optical semiconductor devices (LEDs) each shown in FIG. 1.
[密封材料之初期剝離率] [Initial peeling rate of sealing material]
關於20個上述光半導體裝置(LED)，利用光學顯微鏡觀察經鍍金之導線2與密封材料7間之剝離狀態，將剝離之個數/20個作為剝離率。 Regarding the 20 above-mentioned optical semiconductor devices (LEDs), the peeling state between the gold-plated wire 2 and the sealing material 7 was observed with an optical microscope, and the number of peelings / 20 was taken as the peeling rate.
[吸濕回焊後之剝離率] [Peeling rate after hygroscopic reflow]
使20個上述光半導體裝置(LED)於85℃/85%RH之高溫高濕條件下保持168小時後，於280℃之烘箱內靜置30秒。其後，設為室溫(25℃)，利用光學顯微鏡觀察經鍍金之導線2與密封材料7間之剝離狀態，將剝離之個數/20個作為剝離率。 After the 20 above-mentioned optical semiconductor devices (LEDs) were kept under high temperature and high humidity conditions of 85 ° C / 85% RH for 168 hours, they were allowed to stand in an oven at 280 ° C for 30 seconds. Thereafter, the temperature was set to room temperature (25 ° C.), and the peeling state between the gold-plated wire 2 and the sealing material 7 was observed with an optical microscope, and the number of peelings / 20 was regarded as the peeling rate.
根據表1之結果，表示利用實施例1~5之硬化性聚矽氧組合物之硬化物密封之半導體裝置具有較高之耐剝離性。 According to the results in Table 1, the semiconductor device sealed with the cured product of the curable polysiloxane composition of Examples 1 to 5 has high peel resistance.
本發明之半導體裝置於吸濕回焊試驗後，難以產生與包含經鍍金之導線及聚矽氧硬化物之密封材料之剝離，故而作為可靠性之要求嚴格之光半導體裝置(LED)較佳。 After the moisture absorption reflow test of the semiconductor device of the present invention, it is difficult to cause peeling from the sealing material including the gold-plated wire and the polysilicon hardened material, so it is preferable as an optical semiconductor device (LED) having strict reliability requirements.
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| JP7130316B2 (en) * | 2017-07-05 | 2022-09-05 | モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社 | Curable polyorganosiloxane composition |
| TWI829640B (en) * | 2017-07-10 | 2024-01-21 | 美商陶氏有機矽公司 | Curable silicone composition and optical semiconductor device |
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| JP5545601B2 (en) * | 2011-11-07 | 2014-07-09 | 信越化学工業株式会社 | Phosphor highly-filled wavelength conversion sheet, method for manufacturing light-emitting semiconductor device using the same, and light-emitting semiconductor device |
| JP6087127B2 (en) * | 2012-12-14 | 2017-03-01 | 株式会社カネカ | Thermosetting resin composition with improved fluidity and semiconductor package using the same |
-
2014
- 2014-05-28 KR KR1020157033397A patent/KR20160013872A/en not_active Application Discontinuation
- 2014-05-28 JP JP2015519987A patent/JP6355210B2/en active Active
- 2014-05-28 WO PCT/JP2014/064798 patent/WO2014192969A1/en active Application Filing
- 2014-05-28 CN CN201480029204.6A patent/CN105229783B/en active Active
- 2014-05-29 TW TW103118858A patent/TWI621664B/en active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011009346A (en) * | 2009-06-24 | 2011-01-13 | Shin-Etsu Chemical Co Ltd | Optical semiconductor device |
| JP2013043901A (en) * | 2011-08-22 | 2013-03-04 | Sumitomo Rubber Ind Ltd | Rubber composition for tire and pneumatic tire |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6355210B2 (en) | 2018-07-11 |
| CN105229783A (en) | 2016-01-06 |
| CN105229783B (en) | 2018-06-22 |
| WO2014192969A1 (en) | 2014-12-04 |
| JPWO2014192969A1 (en) | 2017-02-23 |
| TW201502208A (en) | 2015-01-16 |
| KR20160013872A (en) | 2016-02-05 |
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