JP2009173789A - Silicone composition for photosemiconductor encapsulation, and photosemiconductor device using it - Google Patents
Silicone composition for photosemiconductor encapsulation, and photosemiconductor device using it Download PDFInfo
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- JP2009173789A JP2009173789A JP2008014786A JP2008014786A JP2009173789A JP 2009173789 A JP2009173789 A JP 2009173789A JP 2008014786 A JP2008014786 A JP 2008014786A JP 2008014786 A JP2008014786 A JP 2008014786A JP 2009173789 A JP2009173789 A JP 2009173789A
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- 239000000203 mixture Substances 0.000 title claims abstract description 59
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 38
- 238000005538 encapsulation Methods 0.000 title claims abstract description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 29
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 24
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 14
- 230000035699 permeability Effects 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 125000005375 organosiloxane group Chemical group 0.000 claims abstract description 6
- 230000003197 catalytic effect Effects 0.000 claims abstract description 3
- 239000004065 semiconductor Substances 0.000 claims description 61
- 230000003287 optical effect Effects 0.000 claims description 57
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 34
- 229910052710 silicon Inorganic materials 0.000 claims description 23
- 238000007789 sealing Methods 0.000 claims description 22
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 18
- 229910004283 SiO 4 Inorganic materials 0.000 claims description 17
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 238000005260 corrosion Methods 0.000 abstract description 12
- 230000007797 corrosion Effects 0.000 abstract description 12
- 239000004615 ingredient Substances 0.000 abstract description 3
- 239000002562 thickening agent Substances 0.000 abstract 1
- 238000001723 curing Methods 0.000 description 16
- 239000000047 product Substances 0.000 description 16
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- 125000000217 alkyl group Chemical group 0.000 description 6
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- -1 3-chloropropyl group Chemical group 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 230000015572 biosynthetic process Effects 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
- 239000000919 ceramic Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 125000004093 cyano group Chemical group *C#N 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 229920002050 silicone resin Polymers 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 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 3
- 238000001914 filtration Methods 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 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 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 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 3
- 125000000962 organic group Chemical group 0.000 description 3
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000004382 potting Methods 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 125000005999 2-bromoethyl group Chemical group 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 125000000068 chlorophenyl group Chemical group 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- YLJJAVFOBDSYAN-UHFFFAOYSA-N dichloro-ethenyl-methylsilane Chemical compound C[Si](Cl)(Cl)C=C YLJJAVFOBDSYAN-UHFFFAOYSA-N 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 2
- 125000001207 fluorophenyl group Chemical group 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 239000002683 reaction inhibitor Substances 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 125000005372 silanol group Chemical group 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- MZWXWSVCNSPBLH-UHFFFAOYSA-N 3-(3-aminopropyl-methoxy-methylsilyl)oxypropan-1-amine Chemical compound NCCC[Si](C)(OC)OCCCN MZWXWSVCNSPBLH-UHFFFAOYSA-N 0.000 description 1
- ZDZYGYFHTPFREM-UHFFFAOYSA-N 3-[3-aminopropyl(dimethoxy)silyl]oxypropan-1-amine Chemical compound NCCC[Si](OC)(OC)OCCCN ZDZYGYFHTPFREM-UHFFFAOYSA-N 0.000 description 1
- QYXVDGZUXHFXTO-UHFFFAOYSA-L 3-oxobutanoate;platinum(2+) Chemical compound [Pt+2].CC(=O)CC([O-])=O.CC(=O)CC([O-])=O QYXVDGZUXHFXTO-UHFFFAOYSA-L 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-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
- 229920001875 Ebonite Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- 241000233855 Orchidaceae Species 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 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
- 238000007259 addition reaction Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003302 alkenyloxy group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 125000005998 bromoethyl group Chemical group 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- UNJPQTDTZAKTFK-UHFFFAOYSA-K cerium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ce+3] UNJPQTDTZAKTFK-UHFFFAOYSA-K 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010227 cup method (microbiological evaluation) Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- 239000011151 fibre-reinforced plastic Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000005054 phenyltrichlorosilane Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- ORVMIVQULIKXCP-UHFFFAOYSA-N trichloro(phenyl)silane Chemical compound Cl[Si](Cl)(Cl)C1=CC=CC=C1 ORVMIVQULIKXCP-UHFFFAOYSA-N 0.000 description 1
- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-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
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/4805—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
Abstract
Description
本発明は、例えばＬＥＤ（発光ダイオード）などの光半導体素子を封止する光半導体封止用シリコーン組成物及びそれを用いた光半導体装置に関する。 The present invention relates to an optical semiconductor encapsulating silicone composition for encapsulating an optical semiconductor element such as an LED (light emitting diode), and an optical semiconductor device using the same.
光半導体装置として知られるＬＥＤランプは、光半導体素子として発光ダイオード（ＬＥＤ）を有し、支持基材にダイボンドされたＬＥＤを透明な樹脂からなる封止剤で封止した構成である。このＬＥＤを封止する封止剤としては、従来からエポキシ樹脂ベースの組成物が汎用されていた。 An LED lamp known as an optical semiconductor device has a light emitting diode (LED) as an optical semiconductor element, and has a configuration in which an LED die-bonded to a supporting substrate is sealed with a sealing agent made of a transparent resin. As a sealant for sealing this LED, an epoxy resin-based composition has been widely used.
しかし、エポキシ樹脂ベースの封止剤では、近年の半導体パッケージの小型化やＬＥＤの高輝度化にともなう発熱量の増大や光の短波長化によってクラッキングや黄変が発生しやすく、信頼性の低下を招いていた。 However, epoxy resin-based sealants are prone to cracking and yellowing due to increased heat generation and shorter wavelength of light due to recent miniaturization of semiconductor packages and higher brightness of LEDs, resulting in lower reliability. Was invited.
そこで、優れた耐熱性を有する点から、封止剤としてシリコーン組成物が使用されている。特に、付加反応硬化型のシリコーン組成物は、加熱により短時間で硬化するため生産性がよく、ＬＥＤの封止剤として適している（例えば特許文献１参照）。 Then, the silicone composition is used as a sealing agent from the point which has the outstanding heat resistance. In particular, an addition reaction curable silicone composition cures in a short time by heating, and thus has high productivity and is suitable as an LED sealant (see, for example, Patent Document 1).
しかしながら、シリコーン組成物は、一般に気体透過性に優れるため、外部環境からの影響を受けやすい。ＬＥＤランプが大気中の硫黄化合物や排気ガスなどに曝されると、硫黄化合物などがシリコーン組成物の硬化物を透過して、該硬化物で封止された支持基材上の金属電極、特にＡｇ電極を経時的に腐食して黒変させる。
本発明の目的は、このような課題に対処するためになされたもので、金属電極の腐食を防止することが可能な光半導体封止用シリコーン組成物およびそれを用いた高信頼性の光半導体装置を提供することにある。 SUMMARY OF THE INVENTION An object of the present invention is to cope with such problems, and is a silicone composition for sealing an optical semiconductor capable of preventing corrosion of a metal electrode, and a highly reliable optical semiconductor using the same. To provide an apparatus.
本発明者らは、上記目的を達成するために鋭意検討した結果、ベースポリマーの（Ａ）成分について、アルケニル基を含有し、ＳｉＯ４／２単位を少なくとも１０％含む三次元網目状のポリオルガノシロキサンを（Ａ）成分全体の５重量％以上配合し、硬化後の透湿度を１００ｇ／ｍ２・２４時間以下とすることによって、光半導体素子を実装する支持基材に配置された金属電極、特にＡｇ電極の腐食を防止可能な光半導体封止用シリコーン組成物およびそれを用いた高信頼性の光半導体装置が得られることを見出し、本発明をなすに至った。 As a result of intensive studies to achieve the above object, the inventors of the present invention have found that the component (A) of the base polymer contains an alkenyl group and contains at least 10% of SiO 4/2 units in a three-dimensional network polyorgano. A metal electrode disposed on a support substrate on which an optical semiconductor element is mounted by blending 5% by weight or more of siloxane with the total component (A) and having a moisture permeability after curing of 100 g / m 2 · 24 hours or less, In particular, it has been found that a silicone composition for sealing an optical semiconductor capable of preventing corrosion of an Ag electrode and a highly reliable optical semiconductor device using the same are obtained, and the present invention has been made.
すなわち、本発明の光半導体封止用シリコーン組成物は、
（Ａ）下記（Ａ１）を含むアルケニル基含有ポリオルガノシロキサン １００重量部（但し、（Ａ１）の配合量が（Ａ）成分全体の５重量％以上となる量）
（Ａ１）１分子中にケイ素原子に結合したアルケニル基を平均１個以上有し、ＳｉＯ４／２単位を１０％以上含むポリオルガノシロキサン、
（Ｂ）２５℃における粘度が１０００ｍＰａ・ｓ以下であり、１分子中にケイ素原子に結合した水素原子を２個以上有するポリオルガノシロキサンまたはオルガノシロキサンオリゴマー 前記（Ａ）成分のケイ素原子に結合したアルケニル基１モルに対して、ケイ素原子に結合した水素原子が０．３〜４．０モルとなる量、
（Ｃ）接着性付与剤 ０．１〜２０重量部、
および
（Ｄ）白金系触媒 触媒量
を含有し、硬化後の透湿度が１００ｇ／ｍ２・２４時間以下であることを特徴とする。
That is, the silicone composition for sealing an optical semiconductor of the present invention is
(A) 100 parts by weight of an alkenyl group-containing polyorganosiloxane containing the following (A1) (however, the amount of (A1) is 5% by weight or more of the total component (A))
(A1) a polyorganosiloxane having an average of one or more alkenyl groups bonded to silicon atoms in one molecule and containing 10% or more of SiO 4/2 units,
(B) Polyorganosiloxane or organosiloxane oligomer having a viscosity at 25 ° C. of 1000 mPa · s or less and having two or more hydrogen atoms bonded to a silicon atom in one molecule. Alkenyl bonded to a silicon atom of the component (A) The amount of hydrogen atoms bonded to silicon atoms from 0.3 to 4.0 moles per mole of group,
(C) 0.1-20 parts by weight of an adhesion-imparting agent,
And (D) a platinum-based catalyst, characterized in that it contains a catalytic amount and has a moisture permeability of 100 g / m 2 · 24 hours or less after curing.
また、本発明の光半導体装置は、光半導体封止用シリコーン組成物の硬化物により、光半導体素子が封止されてなることを特徴とする。 Further, the optical semiconductor device of the present invention is characterized in that the optical semiconductor element is sealed with a cured product of the silicone composition for sealing an optical semiconductor.
上記構成により、金属電極の腐食を防止することが可能な光半導体封止用シリコーン組成物及びそれを用いた光半導体装置を提供することができる。 By the said structure, the silicone composition for optical semiconductor sealing which can prevent corrosion of a metal electrode, and an optical semiconductor device using the same can be provided.
以下、本発明の光半導体封止用シリコーン組成物について詳細に説明する。 Hereinafter, the silicone composition for sealing an optical semiconductor of the present invention will be described in detail.
［（Ａ）成分］
（Ａ）成分は、本発明の特徴を付与する成分である。すなわち、ＬＥＤランプが過酷な外部環境に曝されて、例えば大気中の硫黄化合物がＬＥＤランプの封止剤（本組成物の硬化物）を透過した場合に、この封止剤で封止された金属電極、特にＡｇ電極の腐食を効果的に抑制する成分である。
[(A) component]
(A) A component is a component which provides the characteristics of this invention. That is, when the LED lamp is exposed to a harsh external environment, for example, when sulfur compounds in the air permeate the LED lamp sealant (cured product of the present composition), the LED lamp is sealed with this sealant. It is a component that effectively suppresses corrosion of metal electrodes, particularly Ag electrodes.
（Ａ）成分は、（Ａ１）１分子中にケイ素原子に結合したアルケニル基を平均１個以上有し、ＳｉＯ４／２単位を有する三次元網目状のポリオルガノシロキサンを含む。（Ａ１）は、硬化後の透湿度を１００ｇ／ｍ２・２４時間以下に調整しやすくする上で、さらにケイ素原子に結合したフェニル基を有することが好ましい。（Ａ１）におけるフェニル基の含有量は、好ましくは、ケイ素原子に結合した全有機基中の１５〜７０モル％であり、より好ましくは３０〜７０モル％である。 The component (A) includes (A1) a three-dimensional network-like polyorganosiloxane having an average of one or more alkenyl groups bonded to silicon atoms in one molecule and having SiO 4/2 units. (A1) preferably further has a phenyl group bonded to a silicon atom in order to easily adjust the moisture permeability after curing to 100 g / m 2 · 24 hours or less. The content of the phenyl group in (A1) is preferably 15 to 70 mol%, more preferably 30 to 70 mol% in the total organic groups bonded to the silicon atom.
（Ａ１）は、平均単位式：
（Ｒ１ ３ＳｉＯ１／２）ａ（Ｒ１ ２ＳｉＯ２／２）ｂ（Ｒ１ＳｉＯ３／２）ｃ（ＳｉＯ４／２）ｄ
で表される。
(A1) is the average unit formula:
(R 1 3 SiO 1/2 ) a (R 1 2 SiO 2/2 ) b (R 1 SiO 3/2 ) c (SiO 4/2 ) d
It is represented by
式中、Ｒ１は、置換もしくは非置換の１価炭化水素基であり、アルケニル基を必ず含む。
Ｒ１としては、例えばメチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、tert−ブチル基、ヘキシル基、シクロヘキシル基、オクチル基のようなアルキル基；ビニル基、アリル基、ブテニル基、ペテニル基、ヘキセニル基のようなアルケニル基；フェニル基、トリル基のようなアリール基；ベンジル基、フェニルエチル基のようなアラルキル基；ならびにこれらの基の水素原子の少なくとも一部がフッ素、塩素、臭素などのハロゲン原子やシアノ基で置換された基、例えばクロロメチル基、２−ブロモエチル基、３−クロロプロピル基、クロロフェニル基、フルオロフェニル基、シアノエチル基等のハロゲン置換アルキル基、シアノ置換アルキル基、ハロゲン置換アリール基等が挙げられ、好ましくはアルキル基、アルケニル基、アリール基であり、より好ましくはメチル基、ビニル基、フェニル基である。
In the formula, R 1 is a substituted or unsubstituted monovalent hydrocarbon group and always includes an alkenyl group.
R 1 is, for example, an alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, hexyl, cyclohexyl, octyl; vinyl, allyl, butenyl An alkenyl group such as a group, a petenyl group or a hexenyl group; an aryl group such as a phenyl group or a tolyl group; an aralkyl group such as a benzyl group or a phenylethyl group; and at least a part of the hydrogen atoms of these groups are fluorine, Groups substituted with halogen atoms such as chlorine and bromine and cyano groups, such as halogen-substituted alkyl groups such as chloromethyl group, 2-bromoethyl group, 3-chloropropyl group, chlorophenyl group, fluorophenyl group, cyanoethyl group, cyano substitution Examples include an alkyl group and a halogen-substituted aryl group, preferably an alkyl group Alkenyl group, an aryl group, more preferably a methyl group, a vinyl group, a phenyl group.
また、ａは正数であり、ｂは０又は正数であり、ｃは０又は正数であり、ｄは正数であり、０＜ａ／（ｃ＋ｄ）＜０．４であり、０≦ｂ／（ｃ＋ｄ）＜０．１であり、０．１≦ｄ／（ａ＋ｂ＋ｃ＋ｄ）＜０．４、好ましくは０．２＜ｄ／（ａ＋ｂ＋ｃ＋ｄ）＜０．４となる数である。 A is a positive number, b is 0 or a positive number, c is 0 or a positive number, d is a positive number, 0 <a / (c + d) <0.4, and 0 ≦ b / (c + d) <0.1, and 0.1 ≦ d / (a + b + c + d) <0.4, preferably 0.2 <d / (a + b + c + d) <0.4.
アルケニル基の結合位置は、制限されず、Ｒ１ ３ＳｉＯ１／２単位のＳｉ原子に結合しても、Ｒ１ ２ＳｉＯ２／２単位のＳｉ素原子に結合しても、Ｒ１ＳｉＯ３／２単位のＳｉ原子に結合してもよい。フェニル基の結合位置についても、同様である。
Bonding position of the alkenyl group is not limited, be bonded to Si atoms of the R 1 3 SiO 1/2 units, it is attached to the Si atom of the R 1 2 SiO 2/2 units,
（Ａ１）としては、例えば、下記のようなポリオルガノシロキサンが挙げられる。
［（Ｃ６Ｈ５）（ＣＨ３）２ＳｉＯ１／２］ｓ［（ＣＨ２＝ＣＨ）（ＣＨ３）２ＳｉＯ１／２］ｔ（ＳｉＯ４／２）ｋ
［（ＣＨ３）３ＳｉＯ１／２］ｕ［（Ｃ６Ｈ５）２ＳｉＯ２／２］ｌ［（ＣＨ２＝ＣＨ）ＣＨ３ＳｉＯ２／２］ｍ（ＳｉＯ４／２）ｋ
［（ＣＨ２＝ＣＨ）（ＣＨ３）２ＳｉＯ１／２］ｔ［（ＣＨ３）３ＳｉＯ１／２］ｕ［（Ｃ６Ｈ５）２ＳｉＯ２／２］ｌ［（ＣＨ２＝ＣＨ）ＣＨ３ＳｉＯ２／２］ｍ（ＳｉＯ４／２）ｋ
［（ＣＨ２＝ＣＨ）（ＣＨ３）２ＳｉＯ１／２］ｔ［（Ｃ６Ｈ５）２ＳｉＯ２／２］ｌ（ＳｉＯ４／２）ｋ
［（ＣＨ２＝ＣＨ）（ＣＨ３）２ＳｉＯ１／２］ｔ［（ＣＨ３）２ＳｉＯ２／２］ｎ［（Ｃ６Ｈ５）ＳｉＯ３／２］ｈ（ＳｉＯ４／２）ｋ
［（ＣＨ３）３ＳｉＯ１／２］ｕ［（ＣＨ２＝ＣＨ）ＣＨ３ＳｉＯ２／２］ｍ［（ＣＨ２＝ＣＨ）ＳｉＯ３／２］ｉ［（Ｃ６Ｈ５）ＳｉＯ３／２］ｈ（ＳｉＯ４／２）ｋ
［（ＣＨ２＝ＣＨ）（ＣＨ３）２ＳｉＯ１／２］ｔ［（ＣＨ３）３ＳｉＯ１／２］ｕ［（Ｃ６Ｈ５）２ＳｉＯ２／２］ｌ［（ＣＨ２＝ＣＨ）ＳｉＯ３／２］ｉ（ＳｉＯ４／２）ｋ
［（ＣＨ３）３ＳｉＯ１／２］ｕ［（ＣＨ２＝ＣＨ）（ＣＨ３）２ＳｉＯ１／２］ｔ［（Ｃ６Ｈ５）ＳｉＯ３／２］ｈ（ＳｉＯ４／２）ｋ
［（ＣＨ３）３ＳｉＯ１／２］ｕ［（ＣＨ２＝ＣＨ）（ＣＨ３）２ＳｉＯ１／２］ｔ［（Ｃ６Ｈ５）ＳｉＯ３／２］ｈ［（ＣＨ２＝ＣＨ）ＳｉＯ３／２］ｉ（ＳｉＯ４／２）ｋ
［（ＣＨ２＝ＣＨ）（ＣＨ３）２ＳｉＯ１／２］ｔ［（Ｃ６Ｈ５）ＳｉＯ３／２］ｈ（ＳｉＯ４／２）ｋ
Examples of (A1) include the following polyorganosiloxanes.
[(C 6 H 5 ) (CH 3 ) 2 SiO 1/2 ] s [(CH 2 ═CH) (CH 3 ) 2 SiO 1/2 ] t (SiO 4/2 ) k
[(CH 3 ) 3 SiO 1/2 ] u [(C 6 H 5 ) 2 SiO 2/2 ] l [(CH 2 ═CH) CH 3 SiO 2/2 ] m (SiO 4/2 ) k
[(CH 2 = CH) (CH 3 ) 2 SiO 1/2 ] t [(CH 3 ) 3 SiO 1/2 ] u [(C 6 H 5 ) 2 SiO 2/2 ] l [(CH 2 = CH ) CH 3 SiO 2/2 ] m (SiO 4/2 ) k
[(CH 2 = CH) ( CH 3) 2
[(CH 2 ═CH) (CH 3 ) 2 SiO 1/2 ] t [(CH 3 ) 2 SiO 2/2 ] n [(C 6 H 5 ) SiO 3/2 ] h (SiO 4/2 ) k
[(CH 3 ) 3 SiO 1/2 ] u [(CH 2 = CH) CH 3 SiO 2/2 ] m [(CH 2 = CH) SiO 3/2 ] i [(C 6 H 5 ) SiO 3 / 2 ] h (SiO 4/2 ) k
[(CH 2 = CH) (CH 3 ) 2 SiO 1/2 ] t [(CH 3 ) 3 SiO 1/2 ] u [(C 6 H 5 ) 2 SiO 2/2 ] l [(CH 2 = CH ) SiO 3/2 ] i (SiO 4/2 ) k
[(CH 3 ) 3 SiO 1/2 ] u [(CH 2 ═CH) (CH 3 ) 2 SiO 1/2 ] t [(C 6 H 5 ) SiO 3/2 ] h (SiO 4/2 ) k
[(CH 3 ) 3 SiO 1/2 ] u [(CH 2 = CH) (CH 3 ) 2 SiO 1/2 ] t [(C 6 H 5 ) SiO 3/2 ] h [(CH 2 = CH) SiO 3/2 ] i (SiO 4/2 ) k
[(CH 2 = CH) ( CH 3) 2
式中、ｓは０又は正数であり、ｔは０又は正数であり、ｕは０又は正数であり、ｌは０又は正数であり、ｍは０又は正数であり、ｎは０又は正数であり、ｈは０又は正数であり、ｉは０又は正数であり、ｊは０又は正数であり、ｋは正数である。ｓ＋ｔ＋ｕ＝ａであり、ｌ＋ｍ＋ｎ＝ｂであり、ｈ＋ｉ＋ｊ＝ｃであり、ｋ＝ｄである。ａ、ｂ、ｃ、ｄは、前記規定のとおりである。 Where s is 0 or a positive number, t is 0 or a positive number, u is 0 or a positive number, l is 0 or a positive number, m is 0 or a positive number, and n is 0 or a positive number, h is 0 or a positive number, i is 0 or a positive number, j is 0 or a positive number, and k is a positive number. s + t + u = a, l + m + n = b, h + i + j = c, and k = d. a, b, c, and d are as defined above.
このような（Ａ１）の屈折率は、好ましくは、１．４５〜１．５７であり、より好ましくは１．５０〜１．５７である。なお、屈折率は、周知の屈折率計（例えば、アタゴ社製、Ｎｏ．２５６３８）を用いて測定することができる。 The refractive index of such (A1) is preferably 1.45 to 1.57, more preferably 1.50 to 1.57. The refractive index can be measured using a known refractometer (for example, No. 25638 manufactured by Atago Co., Ltd.).
（Ａ１）の製造方法としては、周知の方法を用いればよく、例えば、各単位源となる化合物を上述した割合で組み合わせた後、酸、アルカリの存在下で共加水分解する方法等が挙げられる。一般に、加水分解工程を経て製造された（Ａ１）のようなシリコーンレジンは、末端官能基としてシラノール基（Ｓｉ−ＯＨ）を含有している場合があるため、必要に応じて、このシラノール基を例えば、１，１，３，３−テトラメチルジビニルジシラザンのようなシラノール基反応性ケイ素化合物で処理してもよい。これによって、良好な硬化性が得られる。 As a production method of (A1), a well-known method may be used. For example, a method of co-hydrolyzing in the presence of an acid or an alkali after combining the compounds serving as unit sources in the above-described proportions may be mentioned. . In general, a silicone resin such as (A1) produced through a hydrolysis step may contain a silanol group (Si-OH) as a terminal functional group. For example, it may be treated with a silanol group reactive silicon compound such as 1,1,3,3-tetramethyldivinyldisilazane. Thereby, good curability is obtained.
上記（Ａ１）に加えて、（Ａ）成分には、さらに、（Ａ２）１分子中にケイ素原子に結合したアルケニル基を平均１個以上有する直鎖状のポリオルガノシロキサンを含有してもよい。このアルケニル基は、分子鎖末端のケイ素原子に結合していても、分子鎖途中のケイ素原子に結合していても、両者に結合していてもよいが、組成物の硬化速度、硬化物の物性の点から、少なくとも分子鎖末端のケイ素原子、特に、分子鎖両末端のケイ素原子に結合していることが好ましい。 In addition to the above (A1), the component (A) may further contain (A2) a linear polyorganosiloxane having an average of one or more alkenyl groups bonded to silicon atoms in one molecule. . The alkenyl group may be bonded to the silicon atom at the end of the molecular chain, or may be bonded to the silicon atom in the middle of the molecular chain, or may be bonded to both. From the viewpoint of physical properties, it is preferable that it is bonded to at least a silicon atom at the molecular chain terminal, in particular, a silicon atom at both molecular chain terminals.
（Ａ２）のアルケニル基以外のケイ素原子に結合した有機基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、tert−ブチル基、ヘキシル基、シクロヘキシル基、オクチル基のようなアルキル基；フェニル基、トリル基のようなアリール基；ベンジル基、フェニルエチル基のようなアラルキル基；ならびにこれらの基の水素原子の少なくとも一部がフッ素、塩素、臭素などのハロゲン原子やシアノ基で置換された基、例えばクロロメチル基、２−ブロモエチル基、３−クロロプロピル基、クロロフェニル基、フルオロフェニル基、シアノエチル基等のハロゲン置換アルキル基、シアノ置換アルキル基、ハロゲン置換アリール基等が挙げられ、好ましくはアルキル基、アリール基であり、より好ましくはメチル基、フェニル基である。フェニル基を含むことで、硬化後の透湿度を１００ｇ／ｍ２・２４時間以下に調整しやすくすることができる。フェニル基の含有量は、ケイ素原子に結合した全有機基中の１５〜７０モル％、好ましくは３０〜７０モル％である。フェニル基の結合位置は、特に制限されず、分子鎖末端のケイ素原子に結合していても、分子鎖途中のケイ素原子に結合していてもよい。 Examples of the organic group bonded to a silicon atom other than the alkenyl group in (A2) include, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a hexyl group, a cyclohexyl group, and an octyl group. An alkyl group such as a group; an aryl group such as a phenyl group and a tolyl group; an aralkyl group such as a benzyl group and a phenylethyl group; and at least a part of hydrogen atoms of these groups are halogens such as fluorine, chlorine and bromine Groups substituted with atoms or cyano groups, for example, halogen-substituted alkyl groups such as chloromethyl group, 2-bromoethyl group, 3-chloropropyl group, chlorophenyl group, fluorophenyl group, cyanoethyl group, cyano-substituted alkyl group, halogen-substituted aryl Group, etc., preferably an alkyl group or an aryl group, more preferably Or a methyl group or a phenyl group. By including a phenyl group, the moisture permeability after curing can be easily adjusted to 100 g / m 2 · 24 hours or less. Content of a phenyl group is 15-70 mol% in all the organic groups couple | bonded with the silicon atom, Preferably it is 30-70 mol%. The bonding position of the phenyl group is not particularly limited, and may be bonded to a silicon atom at the end of the molecular chain or may be bonded to a silicon atom in the middle of the molecular chain.
このような（Ａ２）の屈折率は、（Ａ１）と同様に、１．４５〜１．５７であることが好ましく、より好ましくは１．５０〜１．５７である。 The refractive index of (A2) is preferably 1.45 to 1.57, more preferably 1.50 to 1.57, as in (A1).
（Ａ２）としては、例えば、下記のようなポリオルガノシロキサンが挙げられる。
式中、Ｖｉはビニル基である。ｐ、ｑは、ｐ＋ｑが１０〜１００、好ましくは２０〜７０である。なお、ｐおよびｑは、（Ａ２）の一般式での組成、数値を示しているにすぎず、分子レベルを制限するものではない。 In the formula, Vi is a vinyl group. In p and q, p + q is 10 to 100, preferably 20 to 70. In addition, p and q are only the composition and numerical value in the general formula of (A2), and do not limit the molecular level.
（Ａ２）の２５℃における粘度は、１〜１００,０００ｍＰａ・ｓであり、好ましくは１００〜１００００ｍＰａ・ｓである。１ｍＰａ・ｓ未満であると、硬化後の物性が低下し易くなる。一方、１００，０００ｍＰａ・ｓを超えると、組成物の流動性が低下して作業性が悪化し易くなる。 The viscosity of (A2) at 25 ° C. is 1 to 100,000 mPa · s, preferably 100 to 10000 mPa · s. If it is less than 1 mPa · s, the physical properties after curing are likely to be lowered. On the other hand, when it exceeds 100,000 mPa · s, the fluidity of the composition is lowered and the workability is liable to deteriorate.
（Ａ１）と（Ａ２）の配合割合は、（Ａ１）の配合量が（Ａ）成分全体（１００重量部）の５重量％以上、好ましくは５〜７０重量％となる量割合である。（Ａ１）の配合量が（Ａ）成分全体の５重量％未満であると、金属電極の腐食防止の効果が十分に得られない。 The blending ratio of (A1) and (A2) is such that the blending amount of (A1) is 5% by weight or more, preferably 5 to 70% by weight of the entire component (A) (100 parts by weight). When the blending amount of (A1) is less than 5% by weight of the entire component (A), the effect of preventing corrosion of the metal electrode cannot be sufficiently obtained.
［（Ｂ）成分］
（Ｂ）成分は架橋剤であり、１分子中にケイ素原子に結合した水素原子（Ｓｉ−Ｈ基）を２個以上、好ましくは３個以上有するポリオルガノシロキサン、もしくはオルガノシロキサンオリゴマーである。１分子中のケイ素原子数は３〜４００、好ましくは、４〜３００であり、シロキサンオリゴマーの場合には、ケイ素原子数が２〜５０、好ましくは４〜２０である。
[Component (B)]
Component (B) is a cross-linking agent, and is a polyorganosiloxane or an organosiloxane oligomer having 2 or more, preferably 3 or more hydrogen atoms bonded to silicon atoms in one molecule. The number of silicon atoms in one molecule is 3 to 400, preferably 4 to 300. In the case of a siloxane oligomer, the number of silicon atoms is 2 to 50, preferably 4 to 20.
（Ｂ）成分としては、平均組成式：
Ｒ７ ｘＨｙＳｉＯ［４−（ｘ＋ｙ）］／２
で示されるものが用いられる。
As the component (B), an average composition formula:
R 7 x H y SiO [4- (x + y)] / 2
What is shown by is used.
式中、Ｒ７は、脂肪族不飽和炭化水素基を除く、置換または非置換の１価炭化水素基である。Ｒ７としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、tert−ブチル基、ヘキシル基、シクロヘキシル基、オクチル基のようなアルキル基；フェニル基、トリル基のようなアリール基；ベンジル基、フェニルエチル基のようなアラルキル基；およびこれらの基の水素原子の一部または全部がフッ素、塩素、臭素などのハロゲン原子やシアノ基で置換されているもの、例えばクロロメチル基、ブロモエチル基、トリフルオロプロピル基、シアノエチル基などの炭素数１〜１２の１価炭化水素基が挙げられ、なかでも、合成のし易さ、コストの点から、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基等の炭素数１〜４のアルキル基が好ましく、メチル基がより好ましい。 In the formula, R 7 is a substituted or unsubstituted monovalent hydrocarbon group excluding an aliphatic unsaturated hydrocarbon group. R 7 includes, for example, an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a hexyl group, a cyclohexyl group, and an octyl group; Aryl groups such as; aralkyl groups such as benzyl and phenylethyl groups; and those in which some or all of the hydrogen atoms in these groups are substituted with halogen atoms such as fluorine, chlorine, bromine or cyano groups, Examples thereof include monovalent hydrocarbon groups having 1 to 12 carbon atoms such as chloromethyl group, bromoethyl group, trifluoropropyl group, and cyanoethyl group. Among them, from the viewpoint of ease of synthesis and cost, methyl group, ethyl group C1-C4 alkyl groups such as propyl group, isopropyl group, butyl group and isobutyl group are preferred, and methyl group is more preferred. .
ｘ、ｙは、それぞれ正数であり、０．８≦ｘ≦２．２、０．００２≦ｙ≦１、０．８＜ｘ＋ｙ＜３を満足する正数であり、好ましくは、１≦ｘ≦２．２、０．０１≦ｙ≦１、１．８≦ｘ＋ｙ≦２．５を満足する正数である。 x and y are positive numbers, respectively, and are positive numbers satisfying 0.8 ≦ x ≦ 2.2, 0.002 ≦ y ≦ 1, and 0.8 <x + y <3, preferably 1 ≦ x It is a positive number that satisfies ≦ 2.2, 0.01 ≦ y ≦ 1, and 1.8 ≦ x + y ≦ 2.5.
水素原子は、分子鎖末端のケイ素原子に結合していても、分子鎖途中のケイ素原子に結合していても、両者に結合していてもよい。 The hydrogen atom may be bonded to the silicon atom at the end of the molecular chain, may be bonded to the silicon atom in the middle of the molecular chain, or may be bonded to both.
（Ｂ）成分の分子構造としては、直鎖状、分岐鎖状、環状または三次元網目状のいずれでもよいが、Ｒ７ ２ＨＳｉＯ１／２単位（Ｒ７は前記規定のとおり）とＳｉＯ４／２単位とを含有する三次元網目状であることが好ましい。 The molecular structure of the component (B) may be linear, branched, cyclic, or three-dimensional network, but R 7 2 HSiO 1/2 unit (R 7 is as defined above) and SiO 4 It is preferably a three-dimensional network containing / 2 units.
（Ｂ）成分の２５℃における粘度は、１０００ｍＰａ・ｓ以下、好ましくは１〜５００ｍＰａ・ｓである。 (B) The viscosity in 25 degreeC of a component is 1000 mPa * s or less, Preferably it is 1-500 mPa * s.
（Ｂ）成分の配合量は、（Ａ）成分のケイ素原子に結合したアルケニル基（（Ａ１）のケイ素原子に結合したアルケニル基と（Ａ２）のケイ素原子に結合したアルケニル基との合計）１モルに対して、ケイ素原子に結合した水素原子が０．３〜４．０モルとなる量、好ましくは０．５〜２．０モルとなる量である。０．３モル未満であると、十分な架橋が得られない。一方、４．０モルを越えると、未反応のＳｉ−Ｈ基が残存し、硬化後の物性が経時変化しやすい。 The blending amount of the component (B) is the alkenyl group bonded to the silicon atom of the component (A) (the sum of the alkenyl group bonded to the silicon atom of (A1) and the alkenyl group bonded to the silicon atom of (A2)) 1 The amount of hydrogen atoms bonded to silicon atoms is 0.3 to 4.0 moles, preferably 0.5 to 2.0 moles relative to moles. If the amount is less than 0.3 mol, sufficient crosslinking cannot be obtained. On the other hand, if it exceeds 4.0 mol, unreacted Si-H groups remain, and the physical properties after curing are likely to change with time.
［（Ｃ）成分］
（Ｃ）成分は、組成物に接着性を付与する成分であり、公知のものを使用できる。
[Component (C)]
(C) component is a component which provides adhesiveness to a composition, and can use a well-known thing.
（Ｃ）成分は、オルガノシラン、またはケイ素原子数２〜５０個、好ましくは４〜２０個のオルガノシロキサンオリゴマーを用いることができる。（Ｃ）成分は、ケイ素原子に結合したアルコキシ基及び／又はアルケニルオキシ基を有し、かつ、Ｓｉ−Ｈ基、アルケニル基、アクリル基、メタクリル基、エポキシ基、メルカプト基、エステル基、無水カルボキシ基、アミノ基及びアミド基から選ばれる少なくとも１個の反応性官能基を有することが好ましい。 As the component (C), organosilane or an organosiloxane oligomer having 2 to 50, preferably 4 to 20, silicon atoms can be used. The component (C) has an alkoxy group and / or an alkenyloxy group bonded to a silicon atom, and has a Si-H group, an alkenyl group, an acrylic group, a methacryl group, an epoxy group, a mercapto group, an ester group, and an anhydrous carboxy group. It preferably has at least one reactive functional group selected from a group, an amino group and an amide group.
（Ｃ）成分としては、例えば、γ−グリシドキシプロピルトリメトキシシラン、β−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン等のエポキシ官能性基含有アルコキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリ（メトキシエトキシ）シラン等のアルケニル基含有アルコキシシラン、γ−アミノプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、Ｎ−β（アミノエチル）−γ−アミノプロピルトリメトキシシラン、Ｎ−β（アミノエチル）−γ−アミノプロピルメチルジメトキシシラン、Ｎ−フェニル−γ−アミノプロピルトリメトキシシラン等のアミノ基含有アルコキシシラン、γ−メタクリロキシプロピルトリメトキシシラン、γ−アクリロキシプロピルトリメトキシシラン等のアクリル基又はメタクリル基含有アルコキシシラン、メルカプトプロピルトリメトキシシラン等のメルカプト基含有アルコキシシランなどのアルコキシシランが挙げられる。また、オルガノシロキサンオリゴマーとしては、下記のような化合物が挙げられる。
（Ｃ）成分は、１種単独または２種以上を併用してもよく、これらの反応生成物であってもよい。 As the component (C), one type may be used alone, or two or more types may be used in combination, and these reaction products may be used.
（Ｃ）成分の配合量は、（Ａ）成分１００重量部に対して０．１〜２０重量部、好ましくは１〜１０重量部である。配合量が０．１重量部未満では、十分な接着性が得られない。一方、２０重量部を越えると、コストの点で不経済である。 (C) The compounding quantity of component is 0.1-20 weight part with respect to 100 weight part of (A) component, Preferably it is 1-10 weight part. When the blending amount is less than 0.1 parts by weight, sufficient adhesiveness cannot be obtained. On the other hand, exceeding 20 parts by weight is uneconomical in terms of cost.
［（Ｄ）成分］
（Ｄ）成分の白金系触媒は、組成物の硬化を促進させる成分である。
[(D) component]
The platinum-based catalyst of component (D) is a component that promotes curing of the composition.
（Ｄ）成分としては、ヒドロシリル化反応に用いられる触媒として周知の白金系触媒を使用することができ、例えば白金黒、塩化第二白金、塩化白金酸、塩化白金酸と一価アルコールとの反応物、塩化白金酸とオレフィン類やビニルシロキサンとの錯体、白金ビスアセトアセテートなどが挙げられる。 As the component (D), a well-known platinum-based catalyst can be used as a catalyst used in the hydrosilylation reaction. For example, platinum black, platinum chloride, chloroplatinic acid, chloroplatinic acid and a monohydric alcohol are reacted. Products, complexes of chloroplatinic acid with olefins and vinyl siloxane, platinum bisacetoacetate and the like.
（Ｄ）成分の配合量は、硬化に必要な量であればよく、所望の硬化速度などに応じて適宜調整することができる。通常、組成物の合計重量に対して、白金元素に換算して０．５〜３００ｐｐｍ、好ましくは、硬化物の透明性、コストの点から、１〜２０ｐｐｍである。 (D) The compounding quantity of a component should just be a quantity required for hardening, and can be suitably adjusted according to a desired hardening rate. Usually, it is 0.5 to 300 ppm in terms of platinum element with respect to the total weight of the composition, preferably 1 to 20 ppm from the viewpoint of transparency of the cured product and cost.
［その他任意成分］
本発明の光半導体封止用シリコーン組成物は、上記（Ａ）〜（Ｄ）の各成分を基本成分とし、これらに必要に応じて、反応抑制剤、補強性あるいは非補強性の微粉末充填剤、染料、顔料、難燃性付与剤、耐熱性向上剤、耐酸化劣化剤、波長調整剤、溶剤等を、硬化後の透明性に影響を与えない範囲で、かつ本発明の目的を損なわない範囲で添加してもよい。
[Other optional ingredients]
The silicone composition for sealing an optical semiconductor of the present invention comprises the above components (A) to (D) as basic components, and a reaction inhibitor, reinforcing or non-reinforcing fine powder filling as necessary. Agents, dyes, pigments, flame retardants, heat resistance improvers, oxidation degradation agents, wavelength adjusting agents, solvents, etc., as long as they do not affect the transparency after curing, and the object of the present invention is impaired. You may add in the range which is not.
本発明の光半導体封止用シリコーン組成物の製造方法としては、各成分の添加順序は特に限定されるものではなく、（Ａ）〜（Ｄ）の基本成分と上述した任意成分を周知の混練機で混練する方法等が挙げられる。また、２液に分けて保存し、使用時にこの２液を混合して用いてもよく、この場合には、（Ａ）成分の一部と（Ｄ）成分を混合したものを（I）液とし、残りの（Ａ）成分、（Ｂ）成分、（Ｃ）成分及びその他任意成分（例えば反応抑制剤など）を混合したものを（II）液とし、（I）液と（II）液を混合することもできる。混練機としては、必要に応じて加熱手段及び冷却手段を備えた例えばプラネタリーミキサー、３本ロール、ニーダー、品川ミキサー等が挙げられ、単独またはこれらを組み合わせて使用することができる。 As a manufacturing method of the silicone composition for optical semiconductor sealing of this invention, the addition order of each component is not specifically limited, The basic component of (A)-(D) and the arbitrary component mentioned above are known kneading | mixing. Examples thereof include a kneading method using a machine. In addition, the two liquids may be stored separately and used at the time of use. In this case, a mixture of a part of the component (A) and the component (D) is used as the liquid (I). The mixture of the remaining component (A), component (B), component (C) and other optional components (such as a reaction inhibitor) is the liquid (II), and the liquid (I) and liquid (II) It can also be mixed. Examples of the kneader include a planetary mixer, a three-roller, a kneader, and a Shinagawa mixer, which are provided with a heating unit and a cooling unit, if necessary, and these can be used alone or in combination.
光半導体封止用シリコーン組成物は液状であり、２５℃における粘度は１〜１００Ｐａ・ｓであることが好ましい。粘度が１００Ｐａ・ｓを超えると、例えばＬＥＤにポッティングする際にディスペンサーの目詰まりを生じやすい。一方、１Ｐａ・ｓ未満であると、ポッティングする際に液ダレを起しやすい。 The silicone composition for encapsulating an optical semiconductor is liquid and preferably has a viscosity at 25 ° C. of 1 to 100 Pa · s. When the viscosity exceeds 100 Pa · s, for example, when potting an LED, the dispenser is likely to be clogged. On the other hand, if it is less than 1 Pa · s, dripping tends to occur when potting.
光半導体封止用シリコーン組成物の硬化方法は、特に限定されず、室温もしくは５０〜２００℃で加熱により硬化が進行するが、迅速に硬化させるためには加熱することが好ましい。加熱する場合、加熱時間は、加熱温度に応じて適宜調整することができる。硬化物は、透明な硬質のゴム状もしくは可撓性を有するレジン状である。 The curing method of the silicone composition for encapsulating an optical semiconductor is not particularly limited, and curing proceeds by heating at room temperature or 50 to 200 ° C. However, it is preferable to heat in order to cure quickly. In the case of heating, the heating time can be appropriately adjusted according to the heating temperature. The cured product is a transparent hard rubber or flexible resin.
硬化後の透湿度は、１００ｇ／ｍ２・２４時間以下、好ましくは７０ｇ／ｍ２・２４時間以下である。透湿度は、ＪＩＳ Ｚ ０２０８（４０℃、相対湿度９０％、カップ法）に準拠して得られる値である。透湿度が１００ｇ／ｍ２・２４時間を越えると、ＬＥＤランプが大気中の硫黄化合物や排気ガスなどに曝された場合に、硫黄化合物などが本組成物の硬化物を透過しやすくなり、該硬化物で封止された支持基材上の金属電極、特にＡｇ電極が腐食される場合がある。 The moisture permeability after curing is 100 g / m 2 · 24 hours or less, preferably 70 g / m 2 · 24 hours or less. The moisture permeability is a value obtained according to JIS Z 0208 (40 ° C., relative humidity 90%, cup method). When the moisture permeability exceeds 100 g / m 2 · 24 hours, when the LED lamp is exposed to sulfur compounds or exhaust gas in the atmosphere, the sulfur compounds and the like easily pass through the cured product of the composition, In some cases, a metal electrode, particularly an Ag electrode, on a supporting substrate sealed with a cured product is corroded.
硬化後の線膨張係数は、１０〜２９０×１０−６／℃であり、好ましくは１０〜２５０×１０−６／℃である。一般に、ＬＥＤを実装する支持基材として、機械的強度に優れる点からポリフタルアミド樹脂やセラミックスなどが多用されているが、これらの材料から構成される支持基材と、従来のシリコーン組成物の硬化物との間では線膨張係数の違いから、剥離を生じやすい。本組成物は硬化後、上記線膨張係数の範囲を有しており、これは支持基材の構成材料（例えばポリフタルアミド樹脂、液晶ポリマー、セラミックスなど）の線膨張係数に近い値である。これによって、支持基材と硬化物との間に発生する残存応力の影響を緩和することができ、長期にわたり優れた接着性を有することができる。 The linear expansion coefficient after curing is 10 to 290 × 10 −6 / ° C., preferably 10 to 250 × 10 −6 / ° C. In general, polyphthalamide resins and ceramics are frequently used as support substrates for mounting LEDs from the viewpoint of excellent mechanical strength. However, support substrates composed of these materials and conventional silicone compositions Peeling is likely to occur between cured products due to the difference in linear expansion coefficient. The composition has a range of the linear expansion coefficient after curing, which is a value close to the linear expansion coefficient of the constituent material of the support base (for example, polyphthalamide resin, liquid crystal polymer, ceramics, etc.). Thereby, the influence of the residual stress generated between the supporting substrate and the cured product can be relaxed, and excellent adhesiveness can be obtained over a long period of time.
次に、本発明の光半導体装置について図面を参照して説明する。図１は、本発明に係る光半導体装置の一例を示す断面図であり、ＬＥＤランプを示している。 Next, the optical semiconductor device of the present invention will be described with reference to the drawings. FIG. 1 is a cross-sectional view showing an example of an optical semiconductor device according to the present invention, and shows an LED lamp.
光半導体装置１は、光半導体素子（ＬＥＤ）２と、ポリフタルアミド樹脂から構成された支持基材３と、Ａｇメッキされたリード電極５と、光半導体封止用シリコーン組成物の硬化物４と、を備えている。光半導体素子（ＬＥＤ）２は、光半導体封止用シリコーン組成物の硬化物４で封止されている。
The
この光半導体装置１は、例えば以下のようにして作製される。
For example, the
まず、Ａｇメッキされたリード電極５を有し、ポリフタルアミド樹脂から構成された支持基材３に光半導体素子（ＬＥＤ）２をダイボンドし、光半導体素子２とリード電極５とをボンディングワイヤで接続する。
First, an optical semiconductor element (LED) 2 is die-bonded to a
次に、光半導体素子２に上述した光半導体封止用シリコーン組成物をポッティングした後、例えば１５０℃で１時間加熱して硬化させ、硬化物４を形成する。
Next, after potting the above-described silicone composition for encapsulating an optical semiconductor on the
このようにして得られる光半導体装置１は、光半導体封止用シリコーン組成物の硬化物４で光半導体素子２が封止されているため、装置１が過酷な外部環境に曝されて、大気中の硫黄化合物などが硬化物４内に透過するような場合にも、Ａｇメッキされたリード電極５の腐食を抑制することができ、信頼性に優れている。
In the
なお、上記実施形態では、光半導体素子２の一例としてＬＥＤを用いて説明したが、これ以外に、例えばフォトトランジスタ、フォトダイオード、ＣＣＤ、太陽電池モジュール、ＥＰＲＯＭ、フォトカプラなどに適用することもできる。
In the above-described embodiment, the LED is described as an example of the
また、支持基材３の構成材料の一例として、ポリフタルアミド樹脂を用いて説明したが、これ以外に、各種繊維強化プラスチック、セラミックス等を用いることもできる。
Moreover, although demonstrated using polyphthalamide resin as an example of the constituent material of the
本発明を実施例により詳細に説明するが、本発明は実施例に限定されるものではない。実施例及び比較例中、粘度は２５℃において測定した値であり、屈折率は屈折率計（アタゴ社製、Ｎｏ．２５６３８）を用いて２５℃において測定した値である。また、実施例および比較例で得られた光半導体封止用シリコーン組成物は、以下のようにして評価し、結果を表１に示した。 The present invention will be described in detail with reference to examples, but the present invention is not limited to the examples. In Examples and Comparative Examples, the viscosity is a value measured at 25 ° C., and the refractive index is a value measured at 25 ° C. using a refractometer (manufactured by Atago Co., No. 25638). Moreover, the silicone composition for optical semiconductor sealing obtained by the Example and the comparative example was evaluated as follows, and the result was shown in Table 1.
［透湿度］
光半導体封止用シリコーン組成物を１５０℃で１時間加熱してテストピースを作製した。このテストピースを用いて、ＪＩＳ Ｚ ０２０８（温度４０℃、相対湿度９０％）に準拠して測定した。
[Moisture permeability]
The silicone composition for sealing an optical semiconductor was heated at 150 ° C. for 1 hour to prepare a test piece. It measured based on JISZ0208 (temperature 40 degreeC, relative humidity 90%) using this test piece.
［腐食性試験］
光半導体封止用シリコーン組成物を銀メッキ板に０．１ｍｍ厚で塗布し、１５０℃で１時間放置して硬化させてテストピースを作製した。このテストピースを硫黄結晶０．１ｇとともに１００ｃｃガラス瓶に入れ密閉して７０℃で放置し、所定時間ごとに（１日後、３日後）シリコーンゴムを剥がして、銀メッキ板の腐食の程度を目視で観察した。腐食なし（変色なし）を○とし、多少の腐食（薄い変色）を△とし、黒変を×とした。
[Corrosion test]
A silicone composition for encapsulating an optical semiconductor was applied to a silver-plated plate with a thickness of 0.1 mm, and allowed to stand at 150 ° C. for 1 hour to be cured to prepare a test piece. This test piece was placed in a 100 cc glass bottle together with 0.1 g of sulfur crystals, sealed and allowed to stand at 70 ° C., and the silicone rubber was peeled off every predetermined time (1 day and 3 days later) to visually check the degree of corrosion of the silver-plated plate. Observed. No corrosion (no discoloration) was marked with ◯, some corrosion (light discoloration) was marked with △, and black discoloration was marked with x.
［線膨張係数］
光半導体封止用シリコーン組成物を１５０℃で１時間加熱して６ｍｍ×６ｍｍ×６ｍｍのテストピースを作製した。このテストピースを用いて、ＴＭＡ（熱機械的分析）により２５〜１５０℃の範囲で測定した。
[Linear expansion coefficient]
The silicone composition for sealing an optical semiconductor was heated at 150 ° C. for 1 hour to prepare a test piece of 6 mm × 6 mm × 6 mm. Using this test piece, measurement was performed in the range of 25 to 150 ° C. by TMA (thermomechanical analysis).
［（Ａ１−１）シリコーンレジンの合成例］
［（Ｃ６Ｈ５）ＳｉＯ３／２］５２［（ＣＨ２＝ＣＨ）ＳｉＯ３／２］１１［（ＣＨ３）２ＳｉＯ］３７で表されるポリオルガノシロキサンの５０％トルエン溶液７０重量部と、（Ａ１−２）の５０％キシレン溶液３０重量部を混合し、水酸化セリウム１０００ｐｐｍとともに５時間加熱還流させた。中和剤としてエチレンクロロヒドリンを添加し、１１５℃で２時間中和処理を行った。冷却後、助剤ろ過を行い、（Ａ１−１）の溶液を得た。
[Synthesis Example of (A1-1) Silicone Resin]
[(C 6 H 5 ) SiO 3/2 ] 52 [(CH 2 ═CH) SiO 3/2 ] 11 [(CH 3 ) 2 SiO] 70 parts by weight of a 50% toluene solution of a polyorganosiloxane represented by 37 And 30 parts by weight of a 50% xylene solution of (A1-2) were mixed and heated to reflux with 1000 ppm of cerium hydroxide for 5 hours. Ethylene chlorohydrin was added as a neutralizing agent and neutralized at 115 ° C. for 2 hours. After cooling, auxiliary filtration was performed to obtain a solution of (A1-1).
［（Ａ１−２）シリコーンレジンの合成例］
テトラエトキシシラン１１６０重量部、メチルビニルジクロロシラン１００重量部、トリメチルクロロシラン１００重量部、キシレン１００重量部を混合し、水を用いて加水分解を行った。８０℃以下で１時間の撹拌後、分液しキシレン溶液を得た。さらにキシレン２００重量部と水酸化カリウムを２００ｐｐｍとなるように加え、２時間加熱還流を行った。中和剤としてリン酸を用いて、８０℃で１時間撹拌した。冷却後、助剤ろ過を行い、（Ａ１−２）のキシレン溶液を得た。
[Synthesis Example of (A1-2) Silicone Resin]
1160 parts by weight of tetraethoxysilane, 100 parts by weight of methylvinyldichlorosilane, 100 parts by weight of trimethylchlorosilane and 100 parts by weight of xylene were mixed and hydrolyzed using water. After stirring for 1 hour at 80 ° C. or lower, liquid separation was performed to obtain a xylene solution. Further, 200 parts by weight of xylene and potassium hydroxide were added so as to be 200 ppm, and the mixture was refluxed for 2 hours. The mixture was stirred at 80 ° C. for 1 hour using phosphoric acid as a neutralizing agent. After cooling, auxiliary filtration was performed to obtain a xylene solution of (A1-2).
［（Ａ１−３）シリコーンレジンの合成例］
フェニルトリクロロシラン７０重量部、ジフェニルジクロロシラン１３７重量部、メチルビニルジクロロシラン１７重量部、ジメチルジクロロシラン１．３重量部、キシレン１５０重量部を混合し、水を用いて加水分解を行った。８０℃で２時間の撹拌後、分液しキシレン溶液を得た。水酸化カリウムを２００ｐｐｍとなるように加え、２時間加熱還流を行った。中和剤としてリン酸を用いて、８０℃で１時間撹拌した。冷却後、助剤ろ過を行い、（Ａ１−３）のキシレン溶液を得た。なお、（Ａ１−１）、（Ａ１−２）、（Ａ１−３）の各溶液使用に際しては、（Ａ２−１）または（Ａ２−２）と混合後、溶剤成分を減圧加熱除去し使用した。
[Synthesis Example of (A1-3) Silicone Resin]
70 parts by weight of phenyltrichlorosilane, 137 parts by weight of diphenyldichlorosilane, 17 parts by weight of methylvinyldichlorosilane, 1.3 parts by weight of dimethyldichlorosilane, and 150 parts by weight of xylene were mixed and hydrolyzed using water. After stirring at 80 ° C. for 2 hours, liquid separation was performed to obtain a xylene solution. Potassium hydroxide was added so that it might become 200 ppm, and it heated and refluxed for 2 hours. The mixture was stirred at 80 ° C. for 1 hour using phosphoric acid as a neutralizing agent. After cooling, auxiliary filtration was performed to obtain a xylene solution of (A1-3). In addition, when using each solution of (A1-1), (A1-2), and (A1-3), after mixing with (A2-1) or (A2-2), the solvent component was removed by heating under reduced pressure. .
［実施例１］
（Ａ１−１）式：
（ＳｉＯ２）２１．５［（Ｃ６Ｈ５）ＳｉＯ３／２］５３［（ＣＨ２＝ＣＨ）ＳｉＯ３／２］７［（ＣＨ２＝ＣＨ）ＣＨ３ＳｉＯ］３［（ＣＨ３）３ＳｉＯ１／２］１５．５
で表されるポリオルガノシロキサン８重量部、（Ａ２−１）粘度が４０００ｍＰａ・ｓであり、式：
［（ＣＨ２＝ＣＨ）（ＣＨ３）２ＳｉＯ１／２］［（Ｃ６Ｈ５）２ＳｉＯ］１５［（ＣＨ３）２ＳｉＯ］２０［（ＣＨ２＝ＣＨ）（ＣＨ３）２ＳｉＯ１／２］
で表され、両末端にビニル基を含有したポリオルガノシロキサン９２重量部、（Ｂ）粘度が２０ｍＰａ・ｓであり、式：
（ＳｉＯ２）４［Ｈ（ＣＨ３）２ＳｉＯ１／２］８
で表されるポリオルガノハイドロジェンシロキサン５．５重量部、（Ｃ）接着性付与剤として、ＣＨ２＝Ｃ（ＣＨ３）ＣＯＯ（ＣＨ２）３Ｓｉ（ＯＣＨ３）３と［（ＣＨ３）ＨＳｉＯ］３［（ＣＨ３）２ＳｉＯ］との反応生成物１．５重量部、（Ｄ）ビニルダイマー白金錯体０．０３重量部（白金量として５ｐｐｍ）をプラネタリーミキサーで混練して、光半導体封止用シリコーン組成物を得た。この組成物の特性を測定し、結果を表１に示した。
[Example 1]
(A1-1) Formula:
(SiO 2 ) 21.5 [(C 6 H 5 ) SiO 3/2 ] 53 [(CH 2 ═CH) SiO 3/2 ] 7 [(CH 2 ═CH) CH 3 SiO] 3 [(CH 3 ) 3 SiO 1/2 ] 15.5
8 parts by weight of a polyorganosiloxane represented by the formula (A2-1), the viscosity is 4000 mPa · s, and the formula:
[(CH 2 = CH) ( CH 3) 2
92 parts by weight of polyorganosiloxane containing vinyl groups at both ends, (B) the viscosity is 20 mPa · s, and the formula:
(SiO 2 ) 4 [H (CH 3 ) 2 SiO 1/2 ] 8
5.5 parts by weight of a polyorganohydrogensiloxane represented by formula (C) As an adhesion-imparting agent, CH 2 ═C (CH 3 ) COO (CH 2 ) 3 Si (OCH 3 ) 3 and [(CH 3 ) HSiO] 3 [(CH 3 ) 2 SiO] reaction product 1.5 parts by weight, (D) vinyl dimer platinum complex 0.03 parts by weight (
［比較例１］
（Ａ１−３）式：
［（Ｃ６Ｈ５）ＳｉＯ３／２］３３［（Ｃ６Ｈ５）２ＳｉＯ］５４［（ＣＨ２＝ＣＨ）ＣＨ３ＳｉＯ］１２［（ＣＨ３）２ＳｉＯ］
で表されるポリオルガノシロキサン４０重量部、（Ａ２−１）粘度が４０００ｍＰａ・ｓであり、式：
［（ＣＨ２＝ＣＨ）（ＣＨ３）２ＳｉＯ１／２］［（Ｃ６Ｈ５）２ＳｉＯ］１５［（ＣＨ３）２ＳｉＯ］２０［（ＣＨ２＝ＣＨ）（ＣＨ３）２ＳｉＯ１／２］
で表され、両末端にビニル基を含有したポリオルガノシロキサン６０重量部、（Ｂ）粘度が２０ｍＰａ・ｓであり、式：
（ＳｉＯ２）４［Ｈ（ＣＨ３）２ＳｉＯ１／２］８
で表されるポリオルガノハイドロジェンシロキサン９．５重量部、（Ｃ）接着性付与剤として、ＣＨ２＝Ｃ（ＣＨ３）ＣＯＯ（ＣＨ２）３Ｓｉ（ＯＣＨ３）３と［（ＣＨ３）ＨＳｉＯ］３［（ＣＨ３）２ＳｉＯ］との反応生成物１．５重量部、（Ｄ）ビニルダイマー白金錯体０．０３重量部（白金量として５ｐｐｍ）をプラネタリーミキサーで混練して、光半導体封止用シリコーン組成物を得た。この組成物の特性を測定し、結果を表１に示した。
[Comparative Example 1]
(A1-3) Formula:
[(C 6 H 5 ) SiO 3/2 ] 33 [(C 6 H 5 ) 2 SiO] 54 [(CH 2 ═CH) CH 3 SiO] 12 [(CH 3 ) 2 SiO]
40 parts by weight of the polyorganosiloxane represented by formula (A2-1) has a viscosity of 4000 mPa · s, and the formula:
[(CH 2 = CH) ( CH 3) 2
60 parts by weight of a polyorganosiloxane containing vinyl groups at both ends, (B) the viscosity is 20 mPa · s, and the formula:
(SiO 2 ) 4 [H (CH 3 ) 2 SiO 1/2 ] 8
9.5 parts by weight of a polyorganohydrogensiloxane represented by the formula (C) As an adhesion-imparting agent, CH 2 ═C (CH 3 ) COO (CH 2 ) 3 Si (OCH 3 ) 3 and [(CH 3 ) HSiO] 3 [(CH 3 ) 2 SiO] reaction product 1.5 parts by weight, (D) vinyl dimer platinum complex 0.03 part by weight (
［比較例２］
（Ａ２−１）粘度が４０００ｍＰａ・ｓであり、式：
［（ＣＨ２＝ＣＨ）（ＣＨ３）２ＳｉＯ１／２］［（Ｃ６Ｈ５）２ＳｉＯ］１５［（ＣＨ３）２ＳｉＯ］２０［（ＣＨ２＝ＣＨ）（ＣＨ３）２ＳｉＯ１／２］
で表されるポリオルガノシロキサン１００重量部、（Ｂ）粘度が２０ｍＰａ・ｓであり、式：
（ＳｉＯ２）４［Ｈ（ＣＨ３）２ＳｉＯ１／２］８
で表されるポリオルガノハイドロジェンシロキサン６．５重量部、（Ｃ）接着性付与剤として、ＣＨ２＝Ｃ（ＣＨ３）ＣＯＯ（ＣＨ２）３Ｓｉ（ＯＣＨ３）３と［（ＣＨ３）ＨＳｉＯ］３［（ＣＨ３）２ＳｉＯ］との反応生成物１．５重量部、（Ｄ）ビニルダイマー白金錯体０．０３重量部（白金量として５ｐｐｍ）をプラネタリーミキサーで混練して、光半導体封止用シリコーン組成物を得た。この組成物の特性を測定し、結果を表１に示した。
[Comparative Example 2]
(A2-1) The viscosity is 4000 mPa · s, and the formula:
[(CH 2 = CH) ( CH 3) 2
100 parts by weight of the polyorganosiloxane represented by the formula (B), the viscosity is 20 mPa · s, and the formula:
(SiO 2 ) 4 [H (CH 3 ) 2 SiO 1/2 ] 8
6.5 parts by weight of a polyorganohydrogensiloxane represented by the formula (C) As an adhesion-imparting agent, CH 2 ═C (CH 3 ) COO (CH 2 ) 3 Si (OCH 3 ) 3 and [(CH 3 ) HSiO] 3 [(CH 3 ) 2 SiO] reaction product 1.5 parts by weight, (D) vinyl dimer platinum complex 0.03 parts by weight (
［比較例３］
（Ａ１−２）式：
（ＳｉＯ２）５６［（ＣＨ２＝ＣＨ）ＣＨ３ＳｉＯ］７［（ＣＨ３）３ＳｉＯ１／２］３７
で表されるポリオルガノシロキサン１０重量部、（Ａ２−２）粘度３０００ｍＰａ・ｓ、式：
［（ＣＨ２＝ＣＨ）（ＣＨ３）２ＳｉＯ１／２］［（ＣＨ３）２ＳｉＯ］５００［（ＣＨ２＝ＣＨ）（ＣＨ３）２ＳｉＯ１／２］
で表され、両末端にビニル基を含有したポリオルガノシロキサン９０重量部、（Ｂ）粘度が２０ｍＰａ・ｓであり、式：
（ＳｉＯ２）４［Ｈ（ＣＨ３）２ＳｉＯ１／２］８
で表されるポリオルガノハイドロジェンシロキサン３重量部、（Ｃ）接着性付与剤として、ＣＨ２＝Ｃ（ＣＨ３）ＣＯＯ（ＣＨ２）３Ｓｉ（ＯＣＨ３）３と［（ＣＨ３）ＨＳｉＯ］３［（ＣＨ３）２ＳｉＯ］との反応生成物１．５重量部、（Ｄ）ビニルダイマー白金錯体０．０３重量部（白金量として５ｐｐｍ）をプラネタリーミキサーで混練して、光半導体封止用シリコーン組成物を得た。この組成物の特性を測定し、結果を表１に示した。
[Comparative Example 3]
(A1-2) Formula:
(SiO 2 ) 56 [(CH 2 ═CH) CH 3 SiO] 7 [(CH 3 ) 3 SiO 1/2 ] 37
10 parts by weight of polyorganosiloxane represented by the formula: (A2-2) viscosity 3000 mPa · s, formula:
[(CH 2 = CH) (CH 3 ) 2 SiO 1/2 ] [(CH 3 ) 2 SiO] 500 [(CH 2 = CH) (CH 3 ) 2 SiO 1/2 ]
90 parts by weight of a polyorganosiloxane containing vinyl groups at both ends, (B) the viscosity is 20 mPa · s, and the formula:
(SiO 2 ) 4 [H (CH 3 ) 2 SiO 1/2 ] 8
3 parts by weight of a polyorganohydrogensiloxane represented by formula (C) As an adhesion-imparting agent, CH 2 ═C (CH 3 ) COO (CH 2 ) 3 Si (OCH 3 ) 3 and [(CH 3 ) HSiO] 3 1.5 parts by weight of the reaction product with [(CH 3 ) 2 SiO] and 0.03 parts by weight of (D) vinyl dimer platinum complex (5 ppm as platinum amount) were kneaded with a planetary mixer, A silicone composition for stopping was obtained. The properties of this composition were measured and the results are shown in Table 1.
表１から明らかなように、（Ａ１−１）ビニル基とフェニル基を有し、ＳｉＯ２単位を１０％以上有する三次元網目状のポリオルガノシロキサンを（Ａ）成分全体の８重量％配合し、残りを（Ａ２−１）フェニル基を有し、両末端にビニル基を含有したポリオルガノシロキサンを配合した実施例１は、硬化後の透湿度が１００ｇ／ｍ２・２４時間以下である。これにより、Ａｇメッキ板を使用した腐食性試験では、実施例は１日経過後で変色がなく、３日経過しても変色（腐食）抑制の効果がある。 As is clear from Table 1, (A1-1) 3% polyorganosiloxane having a vinyl group and a phenyl group and having a SiO 2 unit of 10% or more is blended in an amount of 8% by weight of the total component (A). In Example 1, in which the remainder is (A2-1) having a phenyl group and a polyorganosiloxane containing vinyl groups at both ends is blended, the moisture permeability after curing is 100 g / m 2 · 24 hours or less. Thereby, in the corrosivity test using an Ag plating plate, the examples have no discoloration after 1 day, and have the effect of suppressing discoloration (corrosion) even after 3 days.
また、硬化後の線膨張係数は、１０〜２９０×１０−６／℃であり、ＬＥＤのような光半導体素子を実装する支持基材の構成材料（例えばポリフタルアミド樹脂、セラミックスなど）の線膨張係数に近い値にすることができる。これにより、支持基材と本組成物の硬化物との間に発生する残存応力の影響を緩和することができ、長期にわたり優れた接着性を有することができる。 Further, the linear expansion coefficient after curing is 10 to 290 × 10 −6 / ° C., and the line of the constituent material (for example, polyphthalamide resin, ceramics, etc.) of the supporting substrate on which the optical semiconductor element such as LED is mounted. The value can be close to the expansion coefficient. Thereby, the influence of the residual stress which generate | occur | produces between a support base material and the hardened | cured material of this composition can be relieved, and it can have the adhesiveness outstanding over the long term.
１…光半導体装置、２…光半導体素子（ＬＥＤ）、３…支持基材、４…光半導体封止用組成物の硬化物、５…リード電極（Ａｇメッキ）、６…ボンディングワイヤ。
DESCRIPTION OF
Claims (8)
（Ａ１）１分子中にケイ素原子に結合したアルケニル基を平均１個以上有し、ＳｉＯ４／２単位を１０％以上含むポリオルガノシロキサン、
（Ｂ）２５℃における粘度が１０００ｍＰａ・ｓ以下であり、１分子中にケイ素原子に結合した水素原子を２個以上有するポリオルガノシロキサンまたはオルガノシロキサンオリゴマー 前記（Ａ）成分のケイ素原子に結合したアルケニル基１モルに対して、ケイ素原子に結合した水素原子が０．３〜４．０モルとなる量、
（Ｃ）接着性付与剤 ０．１〜２０重量部、
および
（Ｄ）白金系触媒 触媒量
を含有し、硬化後の透湿度が１００ｇ／ｍ２・２４時間以下であることを特徴とする光半導体封止用シリコーン組成物。 (A) 100 parts by weight of an alkenyl group-containing polyorganosiloxane containing the following (A1) (however, the amount of (A1) is 5% by weight or more of the total component (A))
(A1) a polyorganosiloxane having an average of one or more alkenyl groups bonded to silicon atoms in one molecule and containing 10% or more of SiO 4/2 units,
(B) Polyorganosiloxane or organosiloxane oligomer having a viscosity at 25 ° C. of 1000 mPa · s or less and having two or more hydrogen atoms bonded to a silicon atom in one molecule. Alkenyl bonded to a silicon atom of the component (A) The amount of hydrogen atoms bonded to silicon atoms from 0.3 to 4.0 moles per mole of group,
(C) 0.1-20 parts by weight of an adhesion-imparting agent,
And (D) a platinum-based catalyst. A silicone composition for encapsulating an optical semiconductor, comprising a catalytic amount and having a moisture permeability after curing of 100 g / m 2 · 24 hours or less.
（Ｒ１ ３ＳｉＯ１／２）ａ（Ｒ１ ２ＳｉＯ２／２）ｂ（Ｒ１ＳｉＯ３／２）ｃ（ＳｉＯ４／２）ｄ
（式中、Ｒ１はビニル基、フェニル基又はメチル基であり、ａは正数であり、ｂは０又は正数であり、ｃは０又は正数であり、ｄは正数であり、０＜ａ／（ｃ＋ｄ）＜０．４であり、０≦ｂ／（ｃ＋ｄ）＜０．１であり、０．１≦ｄ／（ａ＋ｂ＋ｃ＋ｄ）＜０．４となる数である。）で表されることを特徴とする請求項１または２に記載の光半導体封止用シリコーン組成物。 Said (A1) is an average unit formula:
(R 1 3 SiO 1/2 ) a (R 1 2 SiO 2/2 ) b (R 1 SiO 3/2 ) c (SiO 4/2 ) d
(Wherein R 1 is a vinyl group, a phenyl group or a methyl group, a is a positive number, b is 0 or a positive number, c is 0 or a positive number, d is a positive number, 0 <a / (c + d) <0.4, 0 ≦ b / (c + d) <0.1, and 0.1 ≦ d / (a + b + c + d) <0.4. The silicone composition for optical semiconductor sealing of Claim 1 or 2 characterized by the above-mentioned.
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