JP2006049533A - Resin sealing light emitting diode device and sealing method - Google Patents
Resin sealing light emitting diode device and sealing method Download PDFInfo
- Publication number
- JP2006049533A JP2006049533A JP2004227410A JP2004227410A JP2006049533A JP 2006049533 A JP2006049533 A JP 2006049533A JP 2004227410 A JP2004227410 A JP 2004227410A JP 2004227410 A JP2004227410 A JP 2004227410A JP 2006049533 A JP2006049533 A JP 2006049533A
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- JP
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- Prior art keywords
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- emitting diode
- composition
- light
- silicone
- Prior art date
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- Pending
Links
- 238000007789 sealing Methods 0.000 title claims description 33
- 238000000034 method Methods 0.000 title claims description 17
- 229920005989 resin Polymers 0.000 title abstract description 12
- 239000011347 resin Substances 0.000 title abstract description 12
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 74
- 239000000203 mixture Substances 0.000 claims abstract description 67
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 42
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 40
- 229920002050 silicone resin Polymers 0.000 claims abstract description 24
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 238000006459 hydrosilylation reaction Methods 0.000 claims abstract description 13
- 229920006136 organohydrogenpolysiloxane Polymers 0.000 claims abstract description 5
- 230000003197 catalytic effect Effects 0.000 claims abstract description 4
- -1 Polysiloxane Polymers 0.000 claims description 21
- 238000001723 curing Methods 0.000 claims description 14
- 125000000962 organic group Chemical group 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 7
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 6
- 229910004283 SiO 4 Inorganic materials 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 3
- 238000013006 addition curing Methods 0.000 claims description 2
- 239000011342 resin composition Substances 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- 238000005266 casting Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 4
- 230000001737 promoting effect Effects 0.000 abstract description 3
- 239000002210 silicon-based material Substances 0.000 abstract 1
- 229910052710 silicon Inorganic materials 0.000 description 25
- 150000002430 hydrocarbons Chemical group 0.000 description 23
- 239000010410 layer Substances 0.000 description 20
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 16
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 11
- 125000003118 aryl group Chemical group 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 8
- 229910052697 platinum Inorganic materials 0.000 description 8
- 238000007259 addition reaction Methods 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 239000003822 epoxy resin Substances 0.000 description 6
- 229920000647 polyepoxide Polymers 0.000 description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 230000035939 shock Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000806 elastomer Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000008393 encapsulating agent Substances 0.000 description 3
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000003566 sealing material Substances 0.000 description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000013007 heat curing Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000005375 organosiloxane group Chemical group 0.000 description 2
- 150000003058 platinum compounds Chemical class 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000010125 resin casting Methods 0.000 description 2
- 239000007779 soft material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000006039 1-hexenyl group Chemical group 0.000 description 1
- 125000005999 2-bromoethyl group Chemical group 0.000 description 1
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 description 1
- 125000004648 C2-C8 alkenyl group Chemical group 0.000 description 1
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RGVOWOYASHMOCQ-UHFFFAOYSA-N [Pt].C1CCC=CC=CC1 Chemical compound [Pt].C1CCC=CC=CC1 RGVOWOYASHMOCQ-UHFFFAOYSA-N 0.000 description 1
- PXAJQJMDEXJWFB-UHFFFAOYSA-N acetone oxime Chemical group CC(C)=NO PXAJQJMDEXJWFB-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000003302 alkenyloxy group Chemical group 0.000 description 1
- 229940045985 antineoplastic platinum compound Drugs 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 125000000068 chlorophenyl group Chemical group 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000392 cycloalkenyl group Chemical group 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 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 1
- YAJIVAPCZRKADM-UHFFFAOYSA-L cycloocta-1,3-diene;platinum(2+);dichloride Chemical compound Cl[Pt]Cl.C1CCC=CC=CC1 YAJIVAPCZRKADM-UHFFFAOYSA-L 0.000 description 1
- UBDOHRFXPUJBOY-UHFFFAOYSA-L cyclopenta-1,3-diene;dichloroplatinum Chemical compound Cl[Pt]Cl.C1C=CC=C1 UBDOHRFXPUJBOY-UHFFFAOYSA-L 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 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 1
- 230000007547 defect Effects 0.000 description 1
- AJSWTYBRTBDKJF-UHFFFAOYSA-L dichloroplatinum;2-(3-pyridin-2-ylpropyl)pyridine Chemical compound Cl[Pt]Cl.C=1C=CC=NC=1CCCC1=CC=CC=N1 AJSWTYBRTBDKJF-UHFFFAOYSA-L 0.000 description 1
- 125000004212 difluorophenyl group Chemical group 0.000 description 1
- 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 1
- 238000005516 engineering process Methods 0.000 description 1
- RCNRJBWHLARWRP-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane;platinum Chemical class [Pt].C=C[Si](C)(C)O[Si](C)(C)C=C RCNRJBWHLARWRP-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 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 1
- 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 1
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000006178 methyl benzyl group Chemical group 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical group CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 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 1
- 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 1
- 125000005447 octyloxy 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])O* 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 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 1
- 125000004344 phenylpropyl group Chemical group 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- FBCMODDAYVHEHB-UHFFFAOYSA-N platinum;triphenylphosphane Chemical compound [Pt].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 FBCMODDAYVHEHB-UHFFFAOYSA-N 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001843 polymethylhydrosiloxane Polymers 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- 238000010187 selection method Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/52—Encapsulations
- H01L33/56—Materials, e.g. epoxy or silicone resin
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Led Device Packages (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、発光ダイオードチップ、リードフレーム及びこれらを接続するボンデイングワイヤーからなる発光ダイオード素子（以下ＬＥＤ素子という）をシリコーンで封止した発光ダイオード装置及びその封止方法、特に、青色〜紫外光を発するＬＥＤ素子からなる発光ダイオード装置及びそのＬＥＤ素子封止方法に関する。 The present invention relates to a light emitting diode device in which a light emitting diode element (hereinafter referred to as an LED element) composed of a light emitting diode chip, a lead frame, and a bonding wire connecting them is sealed with silicone, and a sealing method thereof, in particular, blue to ultraviolet light. The present invention relates to a light-emitting diode device including LED elements that emit light and a method for sealing the LED elements.
ＬＥＤ素子は透明の樹脂で封止して発光装置として用いられるが、封止用の透明樹脂としてエポキシ樹脂が一般的に用いられてきた。エポキシ樹脂は、透明性に優れ、十分な強度、剛性を有していることが理由であるが、近年その需要拡大が期待されている青色〜紫外光を発するＬＥＤ素子の封止、あるいは、蛍光体を混合した樹脂で青色〜紫外光を発するＬＥＤ素子を封止する白色発光装置については、シリコーン樹脂が注目されている。これは、エポキシ樹脂は、ＬＥＤ素子の高輝度、短波長化に対応した十分な耐熱性、耐光性を有していないことによる。すなわち、エポキシ系樹脂封止体にチップからの紫外線等が照射されると、有機高分子の繋ぎ目が切断され、各種の光学的特性及び化学的特性が劣化することによって、発光ダイオードチップの周囲からエポキシ樹脂が次第に黄変し、着色現象が発生して発光装置の寿命が限定されるという欠点を有しているためである。これに対して、シリコーン樹脂は、透明性に優れ、紫外線による劣化が著しく少ない点で特に青色〜紫外光を発するＬＥＤ素子の封止用として期待されているのである。 An LED element is sealed with a transparent resin and used as a light emitting device, and an epoxy resin has generally been used as a transparent resin for sealing. The epoxy resin is excellent in transparency, and has sufficient strength and rigidity. However, in recent years, the demand for blue-ultraviolet light emitting LED elements, which are expected to increase in demand, or fluorescent light is expected. Silicone resins have attracted attention for white light emitting devices that seal LED elements emitting blue to ultraviolet light with a resin mixed with a body. This is because the epoxy resin does not have sufficient heat resistance and light resistance corresponding to the high brightness and short wavelength of the LED element. That is, when the epoxy resin encapsulant is irradiated with ultraviolet rays or the like from the chip, the joints of the organic polymer are cut, and various optical and chemical characteristics are deteriorated. This is because the epoxy resin is gradually yellowed to cause a coloring phenomenon and thus has a disadvantage that the lifetime of the light emitting device is limited. On the other hand, silicone resins are expected to be used for sealing LED elements that emit blue to ultraviolet light, in that they are excellent in transparency and are significantly less deteriorated by ultraviolet rays.
例えば、特許文献１では、化合物半導体上の水酸基と反応し得るアルコキシ基を含有し、付加反応によりシリコーン樹脂を生成するシロキサン化合物をＬＥＤ素子の封止用樹脂として用いることが提案されており、この場合にはオルガノシロキサン骨格を有する高分子化合物が用いられている。しかしながら、硬質のシリコーン樹脂を用いる場合には耐光性は改善されるものの、一般にシリコーン樹脂は膨張率が大きく、ＬＥＤ素子に急激な温度変化がある場合にＬＥＤ素子を構成する金属部分とシリコーンとの膨張の差によって発生する歪が大きくなるという問題がある。ＬＥＤ素子はエネルギーが高く通電時は高温となるもので、ＯＮ−ＯＦＦにより急激な温度変化が発生しやすいものであって、繰り返しの温度変化による歪によって、クラックなどが発生しやすいという問題を有する。 For example, Patent Document 1 proposes to use a siloxane compound containing an alkoxy group capable of reacting with a hydroxyl group on a compound semiconductor and generating a silicone resin by an addition reaction as a sealing resin for an LED element. In some cases, a polymer compound having an organosiloxane skeleton is used. However, although the light resistance is improved when a hard silicone resin is used, the silicone resin generally has a large expansion coefficient, and when the LED element undergoes a rapid temperature change, the metal portion constituting the LED element and the silicone There is a problem that the strain generated by the difference in expansion increases. LED elements are high in energy and become hot when energized, and are subject to rapid temperature changes due to ON-OFF, and have the problem that cracks and the like are likely to occur due to distortion due to repeated temperature changes. .
ＬＥＤ素子の封止にエラストマーまたはゲル状のシリコーンを用いる例も知られている。例えば、特許文献２では、蛍光体を分散させた液状のシリコーンが封止に用いられており、加熱硬化後にゲル状となるシリコーンとゴム状のシリコーンとを比較し、ゴム状のものがＬＥＤ素子の保護の点で好ましいとされている。弾性のあるシリコーンエラストマーをＬＥＤ素子の封止に用いる場合には、外部からの機械的な力によって変形しやすいものであり、変形によってはＬＥＤ素子のボンデイングワイヤーが切断するという問題も発生し、さらに、エラストマー自体の機械的強度も十分なレベルとは言いがたい。 An example of using elastomer or gel silicone for sealing an LED element is also known. For example, in Patent Document 2, a liquid silicone in which a phosphor is dispersed is used for sealing. Silicone that becomes gel after heat-curing is compared with rubber-like silicone. It is preferable in terms of protection. When an elastic silicone elastomer is used for sealing an LED element, it is easily deformed by an external mechanical force. Depending on the deformation, there is a problem that the bonding wire of the LED element is cut. It is difficult to say that the mechanical strength of the elastomer itself is sufficient.
一方、ＬＥＤ素子の封止方法として単一の硬質樹脂またはエラストマーのような単一の軟質材料で封止するのに代えて、ＬＥＤ素子の表面を軟質の材料で覆い、更に硬質樹脂で封止する２層構造の提案もされている。例えば、特許文献３では、内層にエラストマーとも呼べるようなゴム弾性を有するシリコーンを用い、外層にエポキシ樹脂を用いることが提案されている。特許文献４では、ＬＥＤ素子表面をまずゲル状またはエラストマー状のシリコーンで被覆し、更にこれを硬質のシリコーン樹脂で封止することが提案されている。 On the other hand, instead of sealing with a single hard resin or a single soft material such as an elastomer as a sealing method of the LED element, the surface of the LED element is covered with a soft material and further sealed with a hard resin. A two-layer structure has also been proposed. For example, Patent Document 3 proposes using silicone having rubber elasticity, which can be called an elastomer, for the inner layer and using an epoxy resin for the outer layer. Patent Document 4 proposes that the surface of the LED element is first coated with gel-like or elastomer-like silicone and then sealed with a hard silicone resin.
この２層構造によって得られる発光ダイオード装置は、いずれかのみで封止した場合の欠点が改良されたものではあるが、使用する内層の軟質シリコーンが有する膨張率が金属と大きく異なるという問題はなくなっているわけではない。内層とする軟質のシリコーン自体の線膨張は大きいものであるために、ＬＥＤ素子に急激な温度変化がある場合にリードフレームと樹脂の膨張の差によって発生するＬＥＤ素子金属部分とこれに接するシリコーン部分とに発生する歪がなくなったわけではなく、急激な温度変化の繰り返しによる界面の剥離などの問題は依然として残っていたのである。 The light-emitting diode device obtained by this two-layer structure has improved defects when sealed with either one, but there is no problem that the expansion coefficient of the soft silicone of the inner layer used is significantly different from that of metal. I don't mean. Since the linear expansion of the soft silicone itself as the inner layer is large, the LED element metal part generated by the difference in expansion between the lead frame and the resin and the silicone part in contact with the LED element when there is a rapid temperature change in the LED element However, the problem of the peeling of the interface due to repeated rapid temperature changes still remained.
このようにシリコーンを用いたＬＥＤ素子の封止として、内層に軟質のシリコーン、外層に硬質のシリコーンとする２層構造を採用することで、単一のシリコーン組成物による封止の問題点を解決する方向が見出されているが、未だ十分なものではなく、特に内層に用いるに最適なシリコーン組成物が求められていたのである。更に最適な軟質シリコーン内層に対して最適な組合わせとなる外層の硬質シリコーン層に用いる組成物が求められていたのである。 In this way, the problem of sealing with a single silicone composition is solved by adopting a two-layer structure that uses soft silicone for the inner layer and hard silicone for the outer layer for sealing LED elements using silicone. However, it has not been sufficient yet, and there has been a demand for a silicone composition particularly suitable for use in the inner layer. Further, there has been a demand for a composition used for an outer hard silicone layer which is an optimal combination with an optimal soft silicone inner layer.
本発明は、内層に軟質のシリコーン、外層に硬質のシリコーンとする２層構造のＬＥＤ素子封止、特に、青色〜紫外光を発するＬＥＤ素子の封止及び白色の発光装置とするための封止における従来技術の問題点に鑑み、シリコーン系材料の透明性、耐光性・耐熱性を保持しながら、急激な温度変化に伴う歪によって発生するクラックが格段に改良され、強度と硬度とのバランスに優れる封止材料組成物とそれによって封止された発光ダイオードを提供することを課題とする。 The present invention relates to a two-layer LED element sealing in which soft silicone is used for the inner layer and hard silicone is used for the outer layer, in particular, sealing of LED elements emitting blue to ultraviolet light and sealing for making a white light emitting device. In view of the problems of conventional technology in Japan, cracks caused by strain accompanying rapid temperature changes have been remarkably improved while maintaining the transparency, light resistance and heat resistance of silicone materials. It is an object of the present invention to provide an excellent encapsulating material composition and a light emitting diode encapsulated thereby.
本発明者等は、前記課題を解決するため、鋭意検討を重ねた結果、特定組成の軟質の付加硬化型シリコーンと特定の付加硬化型シリコーンレジンとを組合わせてＬＥＤを封止することにより、急激な温度変化によるクラックの発生が著しく少なく、シリコーン封止が本来有する光透過率、屈折率、耐光性、耐熱性や、硬くかつ割れ難く、成形時の収縮も少ないといった特徴を損なわない封止発光ダイオード装置を提供できることを見いだし、本発明をなすに至った。 As a result of intensive studies to solve the above problems, the present inventors sealed a LED by combining a soft addition-curable silicone having a specific composition and a specific addition-curable silicone resin. Cracking due to sudden temperature changes is extremely low, sealing without impairing characteristics such as light transmittance, refractive index, light resistance, heat resistance inherent to silicone sealing, hard and hard to crack, and little shrinkage during molding It has been found that a light emitting diode device can be provided, and the present invention has been made.
すなわち、本発明は、
（１）発光ダイオード素子表面が、軟質の付加硬化型シリコーンで被覆され、更に樹脂状の付加硬化型シリコーンレジンで封止された発光ダイオード装置において、軟質の付加硬化型シリコーンが（Ａ）〜（Ｃ）からなる組成物の硬化物であり、硬化後の硬さがタイプＥデュロメータで５以上７５以下であることを特徴とする発光ダイオード装置。
（Ａ）一分子あたり少なくとも平均１．８個のケイ素原子に結合したアルケニル基を有し、２５℃、せん断速度０．９ｓ−１における粘度が１０ｍＰａ・ｓ以上１０，０００ｍＰａ・ｓ以下であるオルガノポリシロキサン、
（Ｂ）一分子あたり少なくとも平均４個のケイ素原子に結合した水素原子を有し、２５℃、せん断速度０．９ｓ−１における粘度が１０ｍＰａ・ｓ以上１０，０００ｍＰａ・ｓ以下であるオルガノ水素ポリシロキサン（ただし、（Ａ）成分のアルケニル基の１個に対して０．９〜２個のケイ素原子に結合した水素原子となるような量）、
（Ｃ）組成物の硬化を促進する触媒量のヒドロシリル化触媒
That is, the present invention
(1) In a light-emitting diode device in which the surface of a light-emitting diode element is coated with a soft addition-curable silicone and further sealed with a resin-like addition-curable silicone resin, the soft addition-curable silicone is (A) to ( A light-emitting diode device, which is a cured product of the composition comprising C) and has a hardness after curing of 5 to 75 with a Type E durometer.
(A) Organo having an alkenyl group bonded to at least 1.8 silicon atoms on average per molecule and having a viscosity at 25 ° C. and a shear rate of 0.9 s −1 of 10 mPa · s to 10,000 mPa · s Polysiloxane,
(B) an organohydrogenpolysiloxane having hydrogen atoms bonded to an average of 4 silicon atoms per molecule and having a viscosity at 25 ° C. and a shear rate of 0.9 s −1 of 10 mPa · s to 10,000 mPa · s Siloxane (provided that hydrogen atoms bonded to 0.9 to 2 silicon atoms with respect to one alkenyl group of component (A)),
(C) A catalytic amount of hydrosilylation catalyst that promotes curing of the composition
（２）（Ａ）は、そのケイ素原子に結合したアルケニル基が、一分子あたり平均約２個であり、分子の末端に位置するオルガノポリシロキサンである請求項１記載の発光ダイオード装置。
（３）付加硬化型シリコーンレジンが、（ａ）平均組成式が（Ｒ３ＳｉＯ１／２）Ｍ・（Ｒ２ＳｉＯ２／２）Ｄ・（ＲＳｉＯ３／２）Ｔ・（ＳｉＯ４／２）Ｑ（但し、Ｒは、各々同一でも異なっていてもよい有機基、水酸基または水素原子から選択され、Ｍ、Ｄ、Ｔ、Ｑは０以上１未満の数であり、かつＭ＋Ｄ＋Ｔ＋Ｑ＝１、Ｑ＋Ｔ＞０である）で表されるオルガノポリシロキサンであって、Ｒとして多重結合を有する炭化水素基および水素原子を含むオルガノポリシロキサン、またはＲとして多重結合を有する炭化水素基およびまたは水素原子を含むオルガノポリシロキサン混合物、（ｂ）有効量のヒドロシリル化触媒からなる組成物の硬化物である（１）または（２）の発光ダイオード装置。
(2) The light-emitting diode device according to claim 1, wherein (A) is an organopolysiloxane having an average of about two alkenyl groups bonded to silicon atoms per molecule and located at the end of the molecule.
(3) Addition-curing silicone resin, (a) The average composition formula is (R 3 SiO 1/2 ) M · (R 2 SiO 2/2 ) D · (RSiO 3/2 ) T · (SiO 4/2 Q (provided that each R is selected from the same or different organic group, hydroxyl group or hydrogen atom, M, D, T, Q is a number from 0 to less than 1, and M + D + T + Q = 1, Q + T >, And R includes a hydrocarbon group having a multiple bond and a hydrogen atom, or R includes a hydrocarbon group and / or a hydrogen atom having a multiple bond. The light-emitting diode device according to (1) or (2), which is a cured product of a composition comprising an organopolysiloxane mixture and (b) an effective amount of a hydrosilylation catalyst.
（４）（Ａ）〜（Ｃ）からなる硬化して軟質となるシリコーンの液状組成物に発光ダイオード素子を浸漬して塗布後に、該軟質となる組成物を硬化または未硬化の状態で、シリコーンレジン組成物により注型成型する（１）〜（３）の発光ダイオード素子の封止方法。 (4) After immersing and applying the light emitting diode element in a liquid silicone composition which is cured and softened comprising (A) to (C), the softened composition is cured or uncured in a silicone state. (1)-(3) light emitting diode element sealing method cast-molded with a resin composition.
本発明による発光ダイオード装置は、急激な温度変化によるクラックの発生が著しく少なく、その封止部で光の透過部分の透過率が高く、耐光性、耐熱性に優れ、硬くかつ割れ難く、成形時の収縮も少ないもので工業的な有用性に優れるものである。 The light emitting diode device according to the present invention is remarkably less likely to generate cracks due to rapid temperature changes, has a high light transmittance at the sealed portion, is excellent in light resistance and heat resistance, is hard and difficult to crack, and is molded. It is excellent in industrial usefulness because it has less shrinkage.
本発明について、具体的に説明する。
本発明の（Ａ）成分は、硬化して軟質となる内層のシリコーンにおける主要成分であって、ケイ素原子に結合したアルケニル基を１分子中に少なくとも平均１．８個有し、ケイ素原子に結合した他の有機基が炭素−炭素二重結合あるいは炭素−炭素三重結合を含まない置換もしくは非置換の炭素数１以上２０以下の１価の炭化水素基であり、２５℃、せん断速度０．９ｓ−１における粘度が１０ｍＰａ・ｓ以上１０，０００ｍＰａ・ｓ以下のアルケニル基含有オルガノポリシロキサンである。
The present invention will be specifically described.
The component (A) of the present invention is a main component in the silicone of the inner layer that is cured to be soft and has an average of at least 1.8 alkenyl groups bonded to silicon atoms in one molecule and bonded to silicon atoms. The other organic group is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms and containing no carbon-carbon double bond or carbon-carbon triple bond, and has a shear rate of 0.9 s at 25 ° C. -1 is an alkenyl group-containing organopolysiloxane having a viscosity of 10 mPa · s to 10,000 mPa · s.
（Ａ）成分のアルケニル基としては、例えば、ビニル基、アリル基、１−ブテニル基、１−ヘキセニル基などの炭素原子数２〜８のアルケニル基を例示することができ、好ましくはビニル基、アリル基であり、特に好ましくはビニル基である。これらのアルケニル基は、後記（Ｂ）成分と反応して網目構造を形成し、分子中に少なくとも１．８個以上、好ましくは１．６個以上１０個以下存在していることが必要である。かかるアルケニル基は、分子鎖の末端のケイ素原子に結合していてもよいし、分子鎖の途中のケイ素原子に結合していてもよい。硬化反応速度及び特性の点から、アルケニル基が分子中に平均２個であり分子鎖末端のケイ素原子のみに結合したアルケニル基オルガノポリシロキサンが好ましい。 (A) As an alkenyl group of a component, C2-C8 alkenyl groups, such as a vinyl group, an allyl group, 1-butenyl group, 1-hexenyl group, can be illustrated, Preferably a vinyl group, An allyl group, particularly preferably a vinyl group. These alkenyl groups react with the component (B) described later to form a network structure, and are required to be present in the molecule at least 1.8 or more, preferably 1.6 or more and 10 or less. . Such an alkenyl group 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. From the viewpoint of curing reaction rate and characteristics, an alkenyl group organopolysiloxane having an average of two alkenyl groups in the molecule and bonded only to the silicon atom at the end of the molecular chain is preferred.
（Ａ）成分のケイ素原子に結合したアルケニル基以外の他の有機基は、好ましくは炭素数１〜１２の炭素−炭素二重結合あるいは炭素−炭素三重結合を含まない置換もしくは非置換の１価の炭化水素基であり、具体的にはメチル基、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、ｔ−ブチル基、ペンチル基、ネオペンチル基、ヘキシル基、２−エチルヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ドデシル基などのアルキル基；シクロペンチル基、シクロヘキシル基、シクロヘプチル基などのシクロアルキル基；フェニル基、トリル基、キシリル基、ビフェニル基、ナフチル基などのアリール基；ベンジル基、フェニルエチル基、フェニルプロピル基、メチルベンジル基などのアラルキル基；これらの炭化水素基中の水素原子の一部または全部がハロゲン原子、シアノ基などによって置換されたクロロメチル基、２−ブロモエチル基、３，３，３−トリフルオロプロピル基、３−クロロプロピル基、クロロフェニル基、ジブロモフェニル基、テトラクロロフェニル基、ジフルオロフェニル基、β−シアノエチル基、γ−シアノプロピル基、β−シアノプロピル基などの置換炭化水素基などが挙げられる。特に好ましい有機基はメチル基、フェニル基である。一般にシリコーンの屈折率は、そのシロキサン骨格に結合した有機基の種類によって異なり、メチル基に比較してフェニル基などの芳香族基が結合したシリコーンは屈折率が高くなる。従って、本発明の発光ダイオード装置においてはこれを封止する外層の樹脂状のシリコーン層が芳香族基を多く含むものである場合は、これに応じて内層の軟質シリコーン層の屈折率も同等のレベルとするためにフェニル基の比率を高めることがより好ましい。 The organic group other than the alkenyl group bonded to the silicon atom of the component (A) is preferably a substituted or unsubstituted monovalent group containing no carbon-carbon double bond or carbon-carbon triple bond having 1 to 12 carbon atoms. Specifically, a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, neopentyl group, hexyl group, 2-ethylhexyl group, heptyl group Alkyl groups such as octyl group, nonyl group, decyl group and dodecyl group; cycloalkyl groups such as cyclopentyl group, cyclohexyl group and cycloheptyl group; aryl groups such as phenyl group, tolyl group, xylyl group, biphenyl group and naphthyl group Aralkyl groups such as benzyl group, phenylethyl group, phenylpropyl group, methylbenzyl group; Chloromethyl group, 2-bromoethyl group, 3,3,3-trifluoropropyl group, 3-chloropropyl group, chlorophenyl group in which some or all of the hydrogen atoms in the hydrogen group are substituted by halogen atoms, cyano groups, etc. And substituted hydrocarbon groups such as a dibromophenyl group, a tetrachlorophenyl group, a difluorophenyl group, a β-cyanoethyl group, a γ-cyanopropyl group, and a β-cyanopropyl group. Particularly preferred organic groups are a methyl group and a phenyl group. In general, the refractive index of silicone varies depending on the type of organic group bonded to the siloxane skeleton, and the refractive index of silicone bonded with an aromatic group such as a phenyl group is higher than that of a methyl group. Accordingly, in the light-emitting diode device of the present invention, when the outer resin-like silicone layer that seals it contains a large amount of aromatic groups, the refractive index of the inner soft silicone layer is set to the same level accordingly. Therefore, it is more preferable to increase the ratio of the phenyl group.
（Ａ）成分のアルケニル基含有オルガノポリシロキサンは、直鎖状でも分岐状でもよく、また、これらの混合物であってもよい。ポリシロキサン骨格における分岐はこれ自体で架橋と同様な働きをするものであり、内層のシリコーンが硬化後に本発明の範囲内の硬度を有するものである限り、この分岐は３官能シロキサン（Ｔ構造）または４官能シロキサン（Ｑ構造）であってもよい。本発明の硬化して軟質のシリコーンとなる組成物は、ＬＥＤ素子を被覆するという工程での作業性から適当な流動性を備えていることが必要である。この様な見地から、（Ａ）成分の粘度は、２５℃、せん断速度０．９ｓ−１において１０ｍＰａ・ｓ以上１０，０００ｍＰａ・ｓ以下の範囲にあることが望ましく、より好ましくは１００ｍＰａ・ｓ以上５，０００ｍＰａ・ｓ以下、特に好ましいのは２００ｍＰａ・ｓ以上３，０００ｍＰａ・ｓ以下の範囲である。このアルケニル基含有オルガノポリシロキサンは当業者にとって公知の方法によって製造される。 The alkenyl group-containing organopolysiloxane (A) may be linear or branched, or a mixture thereof. The branch in the polysiloxane skeleton itself acts like a crosslink, and this branch is a trifunctional siloxane (T structure) as long as the silicone of the inner layer has a hardness within the scope of the present invention after curing. Or tetrafunctional siloxane (Q structure) may be sufficient. The composition to be cured and soft silicone of the present invention needs to have appropriate fluidity from the viewpoint of workability in the process of coating the LED element. From such a viewpoint, the viscosity of the component (A) is desirably in the range of 10 mPa · s to 10,000 mPa · s at 25 ° C. and a shear rate of 0.9 s −1 , more preferably 100 mPa · s or more. 5,000 mPa · s or less, particularly preferably in the range of 200 mPa · s to 3,000 mPa · s. This alkenyl group-containing organopolysiloxane is produced by methods known to those skilled in the art.
本発明の（Ｂ）成分は、（Ａ）成分の架橋剤となるものであって、ケイ素原子に結合した水素原子を少なくとも平均４個、好ましくは３〜３０個有するオルガノ水素ポリシロキサンである。ケイ素原子に結合する水素以外の他の有機基は、炭素−炭素二重結合あるいは炭素−炭素三重結合を含まない置換もしくは非置換の炭素数１以上２０以下の１価炭化水素基であって、２５℃、せん断速度０．９ｓ−１における粘度が１０ｍＰａ・ｓ以上１０，０００ｍＰａ・ｓ以下である。 Component (B) of the present invention is an organohydrogenpolysiloxane that serves as a crosslinking agent for component (A) and has an average of at least 4, preferably 3 to 30, hydrogen atoms bonded to silicon atoms. The organic group other than hydrogen bonded to the silicon atom is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, which does not contain a carbon-carbon double bond or carbon-carbon triple bond, The viscosity at 25 ° C. and a shear rate of 0.9 s −1 is 10 mPa · s or more and 10,000 mPa · s or less.
（Ｂ）成分における水素原子以外の他の有機基は、（Ａ）成分において他の有機基として例示したものと同様であり、好ましくはメチル基、フェニル基である。封止材料の屈折率の観点から（Ａ）成分のメチル基とフェニル基との選択について前述したのと同様にしてフェニル基を含むことがより好ましい。 The organic group other than the hydrogen atom in the component (B) is the same as that exemplified as the other organic group in the component (A), and is preferably a methyl group or a phenyl group. From the viewpoint of the refractive index of the sealing material, it is more preferable that the phenyl group is contained in the same manner as described above for the selection of the methyl group and the phenyl group of the component (A).
（Ｂ）成分の架橋剤は、直鎖状でも分岐状でもよく、また、これらの混合物であってもよい。このオルガノ水素ポリシロキサンは当業者にとって公知の方法によって製造される。また、（Ａ）成分においてその粘度が制限されると同様に、適当な流動性を備えていることが必要であり、（Ｂ）成分の粘度は、２５℃、せん断速度０．９ｓ−１において１０ｍＰａ・ｓ以上１０，０００ｍＰａ・ｓ以下の範囲にあることが望ましく、より好ましくは５０ｍＰａ・ｓ以上５，０００ｍＰａ・ｓ以下、特に好ましいのは１００ｍＰａ・ｓ以上２，０００ｍＰａ・ｓ以下の範囲である。 The crosslinking agent as component (B) may be linear or branched, or a mixture thereof. This organohydrogenpolysiloxane is prepared by methods known to those skilled in the art. Moreover, it is necessary that the component (A) has an appropriate fluidity as well as the viscosity of the component (A) is limited. The viscosity of the component (B) is 25 ° C. and a shear rate of 0.9 s −1 . Desirably, it is in the range of 10 mPa · s to 10,000 mPa · s, more preferably 50 mPa · s to 5,000 mPa · s, and particularly preferably in the range of 100 mPa · s to 2,000 mPa · s. .
本発明の（Ｂ）成分の配合量は、（Ａ）成分を架橋して必要な硬度を有するものとするために、（Ａ）成分のアルケニル基の１個に対して０．９〜２個のケイ素原子に結合した水素原子となるような量で使用され、（Ａ）成分１００重量部に対して通常５重量部以上８０重量部以下である。 The blending amount of the component (B) of the present invention is 0.9 to 2 with respect to one alkenyl group of the component (A) in order to crosslink the component (A) and have the necessary hardness. It is used in such an amount that it becomes a hydrogen atom bonded to a silicon atom, and is usually 5 parts by weight or more and 80 parts by weight or less with respect to 100 parts by weight of component (A).
本発明の（Ｃ）成分は、炭素−炭素多重結合とケイ素原子に結合した水素原子との付加反応を促進するための金属及びその化合物からなるヒドロシリル化触媒であって、通常使用されるものである。このような金属としては、例えば、白金、ロジウム、パラジウム、ルテニウム、及びイリジウムであって、有利には白金を使用することができる。金属は場合により微粒子状の担持材料（例えば、活性炭、酸化アルミニウム、酸化ケイ素）に固定する。ヒドロシリル化触媒としては、白金及び白金化合物を使用することが好ましい。白金化合物としては、白金ハロゲン化物（例えば、ＰｔＣｌ４、Ｈ２ＰｔＣｌ４・６Ｈ２Ｏ、Ｎａ２ＰｔＣｌ４・４Ｈ２Ｏ）、白金−オレフィン錯体、白金−アルコール錯体、白金−アルコラート錯体、白金−エーテル錯体、白金−アルデヒド錯体、白金−ケトン錯体、白金−ビニルシロキサン錯体（例えば、白金−１，３−ジビニル−１，１，３，３−テトラメチルジシロキサン錯体、ビス−（γ−ピコリン）−白金ジクロライド、トリメチレンジピリジン−白金ジクロライド、ジシクロペンタジエン−白金ジクロライド、シクロオクタジエン−白金ジクロライド、シクロペンタジエン−白金ジクロライド）、ビス（アルキニル）ビス（トリフェニルホスフィン）白金錯体、ビス（アルキニル）（シクロオクタジエン）白金錯体などが挙げられる。また、ヒドロシリル化触媒はマイクロカプセル化した形で使用することもできる。この場合触媒を含有し、かつオルガノポリシロキサン中に不溶の微粒子固体は、例えば、樹脂（例えば、ポリエステル樹脂またはシリコーン樹脂）である。また、ヒドロシリル化触媒は包接化合物の形で、例えば、シクロデキストリン内で使用することも可能である。ヒドロシリル化触媒の添加量は触媒量であり、白金触媒を使用する場合、（Ａ）と（Ｂ）とからなる組成物中の白金金属として０．１〜５００ｐｐｍ、特に１〜２００ｐｐｍの範囲が好ましい。 The component (C) of the present invention is a hydrosilylation catalyst comprising a metal and a compound thereof for promoting an addition reaction between a carbon-carbon multiple bond and a hydrogen atom bonded to a silicon atom, and is usually used. is there. Examples of such metals include platinum, rhodium, palladium, ruthenium, and iridium, and platinum can be used advantageously. The metal is optionally fixed to a particulate support material (for example, activated carbon, aluminum oxide, silicon oxide). As the hydrosilylation catalyst, it is preferable to use platinum and a platinum compound. Platinum compounds include platinum halides (eg, PtCl 4 , H 2 PtCl 4 .6H 2 O, Na 2 PtCl 4 .4H 2 O), platinum-olefin complexes, platinum-alcohol complexes, platinum-alcolate complexes, platinum- Ether complexes, platinum-aldehyde complexes, platinum-ketone complexes, platinum-vinylsiloxane complexes (eg, platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complexes, bis- (γ-picoline)) -Platinum dichloride, trimethylenedipyridine-platinum dichloride, dicyclopentadiene-platinum dichloride, cyclooctadiene-platinum dichloride, cyclopentadiene-platinum dichloride), bis (alkynyl) bis (triphenylphosphine) platinum complex, bis (alkynyl) (Cyclooctadiene) platinum complex And the like. The hydrosilylation catalyst can also be used in a microencapsulated form. In this case, the particulate solid containing the catalyst and insoluble in the organopolysiloxane is, for example, a resin (for example, a polyester resin or a silicone resin). The hydrosilylation catalyst can also be used in the form of an inclusion compound, for example, in a cyclodextrin. The addition amount of the hydrosilylation catalyst is a catalytic amount, and when a platinum catalyst is used, the platinum metal in the composition comprising (A) and (B) is preferably 0.1 to 500 ppm, particularly preferably 1 to 200 ppm. .
本発明の（Ａ）〜（Ｃ）からなる組成物は、硬化後の硬さが、ＪＩＳ Ｋ６２５３に規定するデュロメータ硬さ試験方法に従い、タイプＥデュロメータを用い、試験片の厚さ約１０ｍｍにて測定したときに５以上７５以下であることを必要とし、好ましくは５以上６０以下である。５以下では柔らかすぎてシリコーンレジンによる封止工程で変形が大きくなり、７５以上では軟質層として十分な応力吸収効果を発揮できない。この硬度は、用いる（Ａ）成分の重合度と架橋点となるアルケニル基および分岐構造、更に（Ｂ）成分の水素原子量および重合度を調整することにより達成される。 In the composition comprising (A) to (C) of the present invention, the hardness after curing is in accordance with the durometer hardness test method specified in JIS K6253, using a type E durometer, with a test piece thickness of about 10 mm. It needs to be 5 or more and 75 or less when measured, and preferably 5 or more and 60 or less. If it is 5 or less, it is too soft, and the deformation becomes large in the sealing process with a silicone resin. If it is 75 or more, a sufficient stress absorbing effect as a soft layer cannot be exhibited. This hardness is achieved by adjusting the degree of polymerization of the component (A) to be used, the alkenyl group and the branched structure serving as a crosslinking point, and the amount of hydrogen atoms and the degree of polymerization of the component (B).
本発明の発光ダイオード装置は、ＬＥＤ素子を（Ａ）〜（Ｃ）からなる組成物で被覆し、更に、硬化して樹脂状となる付加硬化型シリコーンレジンで封止してなるものであり、この付加硬化型シリコーンレジンは、（ａ）平均組成式が（Ｒ３ＳｉＯ１／２）Ｍ・（Ｒ２ＳｉＯ２／２）Ｄ・（ＲＳｉＯ３／２）Ｔ・（ＳｉＯ４／２）Ｑ（但し、Ｒは、各々同一でも異なっていてもよい有機基、水酸基または水素原子から選択され、Ｍ、Ｄ、Ｔ、Ｑは０以上１未満の数であり、かつＭ＋Ｄ＋Ｔ＋Ｑ＝１、Ｑ＋Ｔ＞０である）で表され、Ｒとして多重結合を有する炭化水素基および水素原子を含むオルガノポリシロキサン、またはＲとして多重結合を有する炭化水素基およびまたは水素原子を含むオルガノポリシロキサン混合物と（ｂ）有効量の付加反応用触媒とからなる組成物である。（ａ）成分は混合物中の平均組成として、Ｔユニット（ＲＳｉＯ３／２）、Ｑユニット（ＳｉＯ４／２）の分岐構造を有するものであり、架橋等の反応により更に高度の三次元網目構造を取ることのできるポリマーである。その為、すべての平均組成式においてはＱ＋Ｔ＞０である。 The light-emitting diode device of the present invention is obtained by coating an LED element with a composition comprising (A) to (C), and further sealing with an addition-curable silicone resin that is cured into a resinous state, This addition-curable silicone resin has (a) an average composition formula of (R 3 SiO 1/2 ) M · (R 2 SiO 2/2 ) D · (RSiO 3/2 ) T · (SiO 4/2 ) Q (Wherein R is selected from the same or different organic groups, hydroxyl groups or hydrogen atoms, M, D, T and Q are a number from 0 to less than 1, and M + D + T + Q = 1, Q + T> 0 Or an organopolysiloxane mixture containing a hydrocarbon group and a hydrogen atom having multiple bonds as R, or an organopolysiloxane mixture containing a hydrocarbon group and / or a hydrogen atom having multiple bonds as R; A composition comprising an effective amount of an addition reaction catalyst. The component (a) has a branched structure of T unit (RSiO 3/2 ) and Q unit (SiO 4/2 ) as an average composition in the mixture, and has a more advanced three-dimensional network structure by a reaction such as crosslinking. It is a polymer that can be removed. Therefore, in all average composition formulas, Q + T> 0.
このようなポリオルガノシロキサンは、シリコーンレジンとも呼ばれるものであって、硬化前の組成物は固体であっても液体であっても良いが、液体であることが本発明の目的とするＬＥＤ封止の成型の容易さからより好ましい。（ａ）成分のポリオルガノシロキサンは当業者には公知の方法によって製造されるものでよく、例えば、オルガノシラン類およびまたはオルガノシロキサン類の加水分解等の反応によって得られる。 Such a polyorganosiloxane is also called a silicone resin, and the composition before curing may be a solid or a liquid. It is more preferable because of the ease of molding. The polyorganosiloxane as component (a) may be produced by a method known to those skilled in the art, and is obtained, for example, by a reaction such as hydrolysis of organosilanes and / or organosiloxanes.
（ａ）成分におけるＲは、それぞれ単独で同一でまたは異なってよい。式は平均組成式であるので、これらの選択の方法は、同一構造ユニット、例えば（Ｒ２ＳｉＯ２／２）Ｄ構造ユニットの中でＲとして同時に異なるもの、例えばメチル基とフェニル基と水素原子の３種類の基を同時に選択することを妨げるものでない。また、各ユニットをつなぐ為の構造が各ユニット構造と異なる形態を取っていてもよい。 R in the component (a) may be the same or different each independently. Since the formula is an average composition formula, these selection methods are different in the same structural unit, for example, (R 2 SiO 2/2 ) D structural unit, as R at the same time, for example, methyl group, phenyl group and hydrogen atom. It does not preclude the simultaneous selection of these three types of groups. Moreover, the structure for connecting each unit may take the form different from each unit structure.
Ｒの例を挙げれば、直鎖状または分岐状の炭素数１〜２０のアルキル基又はアルケニル基及びそのハロゲン置換体、アセチレン基またはアセチレン基を含む炭化水素基、炭素数５〜２５のシクロアルキル基又はシクロアルケニル基及びそのハロゲン置換体、炭素数６〜２５のアラルキル基又はアリール基及びそのハロゲン置換体であり、これら炭化水素基の具体例としては、前記の（Ａ）成分でアルケニル基またはその他の有機基として例示したものをあげることができる。多重結合を有するＲとは炭素−炭素二重結合および炭素−炭素三重結合を含む炭化水素基を意味し、アルケニル基やアセチレン基であって、多重結合を有する炭化水素基として最も好ましいのはビニル基である。 Examples of R include a linear or branched alkyl group or alkenyl group having 1 to 20 carbon atoms and a halogen-substituted product thereof, an acetylene group or a hydrocarbon group containing an acetylene group, and a cycloalkyl group having 5 to 25 carbon atoms. Group or cycloalkenyl group and its halogen substituent, aralkyl group having 6 to 25 carbon atoms or aryl group and its halogen substituent, and specific examples of these hydrocarbon groups include alkenyl group or What was illustrated as another organic group can be mention | raise | lifted. R having a multiple bond means a hydrocarbon group containing a carbon-carbon double bond and a carbon-carbon triple bond, and is an alkenyl group or an acetylene group, and is most preferably a hydrocarbon group having a multiple bond. It is a group.
Ｒは、更に、水素原子、水酸基、アルコキシ基、アシルオキシ基、ケトキシメート基、アルケニルオキシ基、酸無水物基、カルボニル基、糖類、シアノ基、オキサゾリン基、イソシアナート基、等およびまたはこれらの基の炭化水素置換体より選択することができる。これらの具体例をあげれば、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、ブトキシ基、イソブトキシ基、ターシャリーブトキシ基、ヘキシロキシ基、イソヘキシロキシ基、２−ヘキシロキシ基、オクチロキシ基、イソオクチロキシ基、２−オクチロキシ基、アセトキシ基、ジメチルケトオキシム基、メチルエチルケトオキシム基、グリシジル基、エチレングリコキシ基、ジエチレングリコキシ基、ポリエチレングリコキシ基、プロピレングリコキシ基、ジプロピレングリコキシ基、ポリプロピレングリコキシ基、メトキシエチレングリコキシ基、エトキシエチレングリコキシ基、メトキシジエチレングリコキシ基、エトキシジエチレングリコキシ基、メトキシプロピレングリコキシ基、メトキシジプロピレングリコキシ基、エトキシジプロピレングリコキシ基、等である。これら例示されるものの中でも、メチル基、エチル基、プロピル基、フェニル基、ビニル基、水素原子が特に好ましい。 R is further a hydrogen atom, a hydroxyl group, an alkoxy group, an acyloxy group, a ketoximate group, an alkenyloxy group, an acid anhydride group, a carbonyl group, a saccharide, a cyano group, an oxazoline group, an isocyanate group, and the like, and / or It can be selected from hydrocarbon substitutes. Specific examples thereof include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, tertiary butoxy group, hexyloxy group, isohexyloxy group, 2-hexyloxy group, octyloxy group, isooctyloxy group, 2 -Octyloxy, acetoxy, dimethylketoxime, methylethylketoxime, glycidyl, ethyleneglycoxy, diethyleneglycoxy, polyethyleneglycoxy, propyleneglycoxy, dipropyleneglycoxy, polypropyleneglycoxy, methoxy Ethyleneglycoxy group, ethoxyethyleneglycoxy group, methoxydiethyleneglycoxy group, ethoxydiethyleneglycoxy group, methoxypropyleneglycoxy group, methoxydipropyleneglycoxy group, Toki Siji propylene glycoxy group, and the like. Of these, a methyl group, an ethyl group, a propyl group, a phenyl group, a vinyl group, and a hydrogen atom are particularly preferable.
（ａ）成分にはいくつかの組合わせが可能であり、例えば、（イ）多重結合を有しケイ素原子に結合した炭化水素基とケイ素原子に結合した水素原子の双方を一分子中に含むオルガノポリシロキサンまたはこれらの混合物でもよく、（ロ）一分子中に多重結合を有しケイ素原子に結合した炭化水素基を含みケイ素原子に結合した水素原子を含まないオルガノポリシロキサンと、一分子中にケイ素原子に結合した水素原子を含むが多重結合を有する炭化水素基を含まないオルガノポリシロキサンとの混合物、（ハ）更には（イ）のオルガノポリシロキサン（多重結合を有しケイ素原子に結合した炭化水素基とケイ素原子に結合した水素原子の双方を一分子中に含む）と一分子中に多重結合を有しケイ素原子に結合した炭化水素基を含みケイ素原子に結合した水素原子を含まないオルガノポリシロキサン及びまたは一分子中にケイ素原子に結合した水素原子を含むが多重結合を有する炭化水素基を含まないオルガノポリシロキサンとの混合物であってもよい。すなわち、（ａ）成分が混合物である場合であっても、混合物としてケイ素原子に結合した多重結合を有する炭化水素基と水素原子の双方が混合物のいずれかに存在し、混合物として硬化して樹脂状となる量のＴユニット及びまたはＱユニットを含んでいればよい。 The component (a) can be combined in several combinations, for example, (a) a hydrocarbon group having multiple bonds and a hydrogen atom bonded to a silicon atom and a hydrogen atom bonded to a silicon atom are contained in one molecule. It may be an organopolysiloxane or a mixture thereof, and (b) an organopolysiloxane having multiple bonds in one molecule and containing a hydrocarbon group bonded to a silicon atom and not containing a hydrogen atom bonded to a silicon atom; A mixture with an organopolysiloxane containing a hydrogen atom bonded to a silicon atom but not containing a hydrocarbon group having multiple bonds, (c) and (a) an organopolysiloxane (having multiple bonds and bonding to a silicon atom) A hydrocarbon group and a hydrogen atom bonded to a silicon atom in one molecule) and a silicon atom containing a hydrocarbon group having multiple bonds in one molecule and bonded to a silicon atom. Including hydrogen atoms bonded to silicon atoms in the organopolysiloxane and or in one molecule containing no hydrogen atom bonded to be a mixture of an organopolysiloxane containing no hydrocarbon group with a multiple bond. That is, even when the component (a) is a mixture, both hydrocarbon groups having multiple bonds bonded to silicon atoms and hydrogen atoms are present in the mixture as a mixture, and the resin is cured as a mixture. It is only necessary to include a quantity of T units and / or Q units.
（ａ）成分のポリシロキサンにおいて、必ず含まれるケイ素原子に結合した多重結合を有する炭化水素基およびケイ素原子に結合した水素原子は、選択された２つまたは１つのユニットに存在することが好ましい。本発明において、ケイ素原子に結合した炭化水素基およびケイ素原子に結合した水素原子の存在位置は、最も好ましくは（Ｒ２ＳｉＯ２／２）構造ユニットである。 In the polysiloxane of component (a), it is preferable that the hydrocarbon group having a multiple bond bonded to a silicon atom and the hydrogen atom bonded to the silicon atom are present in the selected two or one unit. In the present invention, the position of the hydrocarbon group bonded to the silicon atom and the hydrogen atom bonded to the silicon atom are most preferably (R 2 SiO 2/2 ) structural unit.
本発明の（ａ）成分であるポリオルガノシロキサンは、ＬＥＤ素子の封止材料として耐熱性、耐光性、屈折率の点から、前記平均組成式におけるＲとして芳香族基を持つことが好ましい。芳香族基の例としてはアラルキル基及びアリール基があげられるが、最も好ましいのはフェニル基である。芳香族基の量は、全ユニットのＲに対して５〜９０ｍｏｌ％が好ましく、より好ましくは１０〜６０ｍｏｌ％である。芳香族基の量が少ないと耐熱性、耐光性、屈折率の改良効果が得られず、また量が多すぎると経済的に不利になる。芳香族基は（ＳｉＯ４／２）構造ユニットを除くどのユニットに導入することもできるが、（Ｒ２ＳｉＯ２／２）構造ユニット、（ＲＳｉＯ３／２）構造ユニットに導入することが好ましく、最も好ましいのは（ＲＳｉＯ３／２）構造ユニットへの導入である。 The polyorganosiloxane which is the component (a) of the present invention preferably has an aromatic group as R in the average composition formula from the viewpoint of heat resistance, light resistance, and refractive index as a sealing material for LED elements. Examples of the aromatic group include an aralkyl group and an aryl group, and a phenyl group is most preferable. The amount of the aromatic group is preferably 5 to 90 mol%, more preferably 10 to 60 mol% with respect to R of all units. If the amount of the aromatic group is small, the effect of improving heat resistance, light resistance and refractive index cannot be obtained, and if the amount is too large, it is economically disadvantageous. The aromatic group can be introduced into any unit except the (SiO 4/2 ) structural unit, but is preferably introduced into the (R 2 SiO 2/2 ) structural unit and the (RSiO 3/2 ) structural unit, Most preferred is the introduction into the (RSiO 3/2 ) structural unit.
また、本発明の（ａ）成分について、水素原子と直接結合するケイ素原子は全ケイ素原子の１〜４０ｍｏｌ％であることがより好ましく、さらに好ましくは３〜３０ｍｏｌ％、最も好ましくは５〜２０ｍｏｌ％である。この量が多いと硬度は上がるがもろくなる傾向にあり、またこの量が少ないと硬度が上がらなくなるので上記範囲に入っていることがより好ましい。また、本発明の（ａ）成分が多重結合を有しケイ素原子に結合した炭化水素基とケイ素原子に結合した水素原子の双方を分子中に含む場合には、水素原子と直接結合するケイ素原子は全ケイ素原子の１〜４０ｍｏｌ％であることがより好ましく、さらに好ましくは３〜３０ｍｏｌ％、最も好ましくは５〜２０ｍｏｌ％である。４０ｍｏｌ％以上では、得られる硬化物の硬度は上がるがもろくなる傾向にあり、またこの量が１ｍｏｌ％以下では十分な硬度の硬化物が得られなくなる。 In the component (a) of the present invention, the silicon atom directly bonded to the hydrogen atom is more preferably 1 to 40 mol%, further preferably 3 to 30 mol%, most preferably 5 to 20 mol% of all silicon atoms. It is. If this amount is large, the hardness tends to increase but it tends to be brittle. If this amount is small, the hardness does not increase, so it is more preferable that the amount falls within the above range. In addition, when the component (a) of the present invention contains both a hydrocarbon group having multiple bonds and a hydrogen atom bonded to a silicon atom and a hydrogen atom bonded to the silicon atom, a silicon atom directly bonded to the hydrogen atom Is more preferably 1 to 40 mol% of all silicon atoms, still more preferably 3 to 30 mol%, and most preferably 5 to 20 mol%. When the amount is 40 mol% or more, the hardness of the obtained cured product tends to increase but becomes brittle, and when the amount is 1 mol% or less, a cured product having sufficient hardness cannot be obtained.
Ｍ、Ｄ、Ｔ、Ｑは各々のユニットの割合を示す数で０以上１未満である。好ましくは、Ｍが０〜０．６、Ｄが０．１〜０．８、Ｔが０．１〜０．７、Ｑが０〜０．３であり、さらに好ましくは、Ｍが０．１〜０．４、Ｄが０．１〜０．６、Ｔが０．３〜０．６、Ｑが０である。Ｔ＋Ｑは０．９〜０．３の範囲が好ましく、より好ましくは０．８〜０．５である。 M, D, T, and Q are numbers indicating the ratio of each unit and are 0 or more and less than 1. Preferably, M is 0 to 0.6, D is 0.1 to 0.8, T is 0.1 to 0.7, Q is 0 to 0.3, and more preferably, M is 0.1. -0.4, D is 0.1-0.6, T is 0.3-0.6, and Q is 0. T + Q is preferably in the range of 0.9 to 0.3, more preferably 0.8 to 0.5.
さらに分岐度を表す（２Ｄ＋３Ｔ＋４Ｑ）／（Ｄ＋Ｔ＋Ｑ）の値が、３．０＞（２Ｄ＋３Ｔ＋４Ｑ）／（Ｄ＋Ｔ＋Ｑ）＞２．０であることが好ましく、より好ましくは、２．８＞（２Ｄ＋３Ｔ＋４Ｑ）／（Ｄ＋Ｔ＋Ｑ）＞２．２であり、さらに好ましくは、２．８＞（２Ｄ＋３Ｔ＋４Ｑ）／（Ｄ＋Ｔ＋Ｑ）＞２．５である。 Further, the value of (2D + 3T + 4Q) / (D + T + Q) representing the degree of branching is preferably 3.0> (2D + 3T + 4Q) / (D + T + Q)> 2.0, more preferably 2.8> (2D + 3T + 4Q) / ( D + T + Q)> 2.2, and more preferably 2.8> (2D + 3T + 4Q) / (D + T + Q)> 2.5.
本発明の樹脂状の付加硬化型シリコーンレジンにおける（ｂ）成分であるヒドロシリル化触媒には、前記（Ｃ）成分として例示したと同様なものを用いることができ、水素原子が結合したケイ素原子と多重結合を有する炭化水素との付加反応を促進する為の触媒として通常使用されるものである。この付加反応用触媒は有効量（即ち、いわゆる触媒量）で用いられ、金属換算で通常（ａ）成分に対し１〜１０００ｐｐｍ、好ましくは２〜５００ｐｐｍである。 As the hydrosilylation catalyst as the component (b) in the resinous addition-curable silicone resin of the present invention, the same catalyst as exemplified as the component (C) can be used, and a silicon atom bonded with a hydrogen atom and It is usually used as a catalyst for promoting an addition reaction with a hydrocarbon having multiple bonds. This catalyst for addition reaction is used in an effective amount (that is, so-called catalyst amount), and is usually 1 to 1000 ppm, preferably 2 to 500 ppm relative to component (a) in terms of metal.
本発明の（ａ）及び（ｂ）からなる封止組成物は、付加反応による架橋硬化後に、樹脂状であることが必要である。本発明において樹脂状とは、ＪＩＳ Ｋ６２５３に規定するデュロメータ硬さ試験方法に従い、タイプＤデュロメータを用い、試験片の厚さ６ｍｍにて測定したときに、３０〜９０、より好ましくは、４０〜９０の硬さを示すことである。このような硬度範囲の硬化物は、用いる（ａ）成分の分岐度を表す（２Ｄ＋３Ｔ＋４Ｑ）／（Ｄ＋Ｔ＋Ｑ）を特定範囲とすることにより達成される。 The sealing composition comprising (a) and (b) of the present invention needs to be resinous after cross-linking and curing by addition reaction. In the present invention, the resinous state is 30 to 90, more preferably 40 to 90, when measured at a thickness of 6 mm using a type D durometer in accordance with a durometer hardness test method defined in JIS K6253. Is to show the hardness. A cured product having such a hardness range is achieved by setting (2D + 3T + 4Q) / (D + T + Q) representing the degree of branching of the component (a) to be used in a specific range.
本発明におけるＬＥＤ素子の例を挙げれば、従来のＧａＰ、ＧａＡｓ、ＧａＮベースの赤・緑・黄色発光ＬＥＤ素子と近年開発が進んでいる高輝度、短波長のＬＥＤ素子等を挙げることができる。本発明の組成物は従来型のＬＥＤ素子の封止にも用いることはできるが、特に効果を発揮するのは、近年開発が進んでいる高輝度、短波長のものであり、さらに言えば、高輝度青色、白色用、青〜近紫外のＬＥＤ素子であって、発光のピーク波長が４９０〜３５０ｎｍとなるＬＥＤ素子である。これらのＬＥＤ素子に使用される封止材料は、青〜紫外の波長に対する耐光性が特に必要になる他、ＬＥＤ素子の発光輝度が高く、より高いエネルギーの光に曝されることになる為、特に耐光性及び耐熱性が必要とされる。現在、広く用いられているエポキシ系の封止剤を用いる場合に比較して、本発明の封止剤組成物は耐光性及び耐熱性に優れることにより、発光ダイオード装置の寿命を格段に向上させることができる。これら高輝度青色、白色用、青〜近紫外のＬＥＤ素子を例示すれば、ＡｌＧａＩｎＮの黄色、ＩｎＧａＮの青色、緑色さらにはＩｎＧａＮと蛍光体を組み合わせた白色発光ダイオード装置等を挙げることができる。 Examples of LED elements in the present invention include conventional GaP, GaAs, and GaN-based red / green / yellow light emitting LED elements and high-luminance, short-wavelength LED elements that have been developed recently. The composition of the present invention can also be used for sealing conventional LED elements, but it is particularly high-brightness, short-wavelength, which has been developed in recent years. It is a high-luminance blue, white LED, blue to near-ultraviolet LED element having an emission peak wavelength of 490 to 350 nm. The sealing material used for these LED elements is particularly required to have light resistance to blue to ultraviolet wavelengths, and the LED element has a high emission luminance, so that it will be exposed to higher energy light, In particular, light resistance and heat resistance are required. Compared with the case where an epoxy-based encapsulant that is currently widely used is used, the encapsulant composition of the present invention is excellent in light resistance and heat resistance, thereby significantly improving the life of the light-emitting diode device. be able to. Examples of these high-luminance blue and white LED elements for blue to near-ultraviolet include AlGaInN yellow, InGaN blue, green, and a white light emitting diode device combining InGaN and a phosphor.
封止した発光ダイオード装置の具体例を挙げれば砲弾型、大型パッケージ形、面実装形、等を挙げることができる。これらの形状については、例えば、株式会社 工業調査会 発行の「フラットパネルディスプレイ大辞典」２００１年１２月２５日発行８９７〜９０６ページに記載されている。 Specific examples of the sealed light emitting diode device include a shell type, a large package type, and a surface mount type. These shapes are described, for example, in “Flat Panel Display Dictionary” issued on December 25, 2001, pages 897 to 906, published by Industrial Research Council, Inc.
本発明の（Ａ）〜（Ｃ）からなる硬化して軟質のシリコーンとなる組成物を用いてＬＥＤ素子を被覆する方法は、特に限定されず、例えば、ＬＥＤ素子全体を液状の組成物に浸漬する方法、ＬＥＤ素子に対して液状組成物を滴下する方法などが用いられるが、素子表面を比較的均一に被覆する上では浸漬する方法が好適に用いられる。被覆厚みに特に限定はないが、通常０．０１〜２ｍｍ程度の厚みで被覆する。液状組成物を被覆した後、被覆した組成物を硬化してまたは硬化することなくそのまま次の封止工程に用いることができるが、組成物を硬化してから封止工程に移すことが好ましい。組成物の硬化は、硬化に適する温度にした炉を通過させることにより容易に行うことができる。硬化の温度は、通常５０〜１８０℃で、硬化の時間は１〜１２０分程度である。 The method of coating the LED element with the composition that is cured and becomes soft silicone comprising (A) to (C) of the present invention is not particularly limited, and for example, the entire LED element is immersed in a liquid composition. For example, a method of dripping the liquid composition onto the LED element is used, and a method of dipping is preferably used to coat the surface of the element relatively uniformly. Although there is no particular limitation on the coating thickness, it is usually coated with a thickness of about 0.01 to 2 mm. After coating the liquid composition, the coated composition can be used as it is in the next sealing step without being cured or cured, but it is preferable to transfer the composition to the sealing step after curing. The composition can be easily cured by passing it through a furnace at a temperature suitable for curing. The curing temperature is usually 50 to 180 ° C., and the curing time is about 1 to 120 minutes.
硬化して軟質となるシリコーンで被覆後に、ＬＥＤ素子は更に（ａ）及び（ｂ）からなる硬化して樹脂状となる組成物を用いて封止される。封止の方法は、特に限定されないが、例えば、樹脂製の凹型に本発明のシリコーン組成物を注入しさらに素子を漬け、温度を上げ固化させる方法、トランスファー成型法等により作製される。樹脂型のみならず従来のエポキシを使用した封止剤では使用できなかった金属製の金型を使用できることも、本発明のシリコーンレジンによる封止の長所である。 After being coated with the softened and soft silicone, the LED element is further sealed with a cured and resinous composition comprising (a) and (b). The sealing method is not particularly limited. For example, the sealing is made by a method of injecting the silicone composition of the present invention into a resin-made concave mold, dipping the element, raising the temperature and solidifying, a transfer molding method, or the like. It is also an advantage of sealing with the silicone resin of the present invention that not only a resin mold but also a metal mold that could not be used with a sealing agent using a conventional epoxy can be used.
また、本発明の組成物においてはその効果を損なうことのない範囲内で種々の添加物を添加することができる。例えば、硬化性、ポットライフを与えるための付加反応用反応制御剤や硬度・粘度を調節するための反応性又は非反応性の直鎖状又は環状の低分子ポリオルガノポリシロキサン等、白色発光用のＹＡＧ等の蛍光発光剤、また、微粒子状シリカ、酸化チタン等の無機充填剤や顔料、有機充填剤、難燃剤、耐熱剤、酸化防止剤等を配合してもよい。 Moreover, in the composition of this invention, various additives can be added in the range which does not impair the effect. For example, for white light emission, such as a reaction control agent for addition reaction for imparting curability and pot life, and a reactive or non-reactive linear or cyclic low-molecular polyorganopolysiloxane for adjusting hardness and viscosity. Fluorescent light-emitting agents such as YAG, inorganic fillers such as particulate silica and titanium oxide, pigments, organic fillers, flame retardants, heat-resistant agents, antioxidants, and the like may be blended.
以下に本発明の詳細な実施例を示すが、本発明はこれによって限定されるものではない。
本発明の実施例には以下のシリコーン組成物を用いた。
（Ａ−１）両末端がジメチルビニルシリル基で封鎖された、２５℃で９００ｍＰａ・ｓの粘度を有するジメチルポリシロキサン。
（Ｂ−１）両末端がトリメチルシリル基で封鎖され、２５℃で３００ｍＰａ・ｓの粘度を有し、主鎖中に１４個のメチルハイドロジェンシロキサン単位を含有する、メチル水素ポリシロキサン。
（Ｃ、ｂ）塩化白金酸から誘導されたビニル基含有シロキサン白金錯体。（ヒドロシリル化触媒）
（ａ）平均組成が（Ｍｅ３ＳｉＯ１／２）０．１７・（ＭｅＨＳｉＯ２／２）０．２０・（ＭｅＶｉＳｉＯ２／２）０．２５（ＰｈＳｉＯ３／２）０．３８である、２５℃で９００ｍＰａ・ｓの粘度を有するオルガノポリシロキサン。ここで、Ｍｅはメチル基、Ｖｉはビニル基、Ｐｈはフェニル基を示す。
Although the detailed Example of this invention is shown below, this invention is not limited by this.
In the examples of the present invention, the following silicone compositions were used.
(A-1) Dimethylpolysiloxane having both ends blocked with dimethylvinylsilyl groups and having a viscosity of 900 mPa · s at 25 ° C.
(B-1) A methylhydrogen polysiloxane having both ends blocked with trimethylsilyl groups, having a viscosity of 300 mPa · s at 25 ° C., and containing 14 methylhydrogensiloxane units in the main chain.
(C, b) A vinyl group-containing siloxane platinum complex derived from chloroplatinic acid. (Hydrosilylation catalyst)
(A) The average composition is (Me 3 SiO 1/2 ) 0.17 · (MeHSiO 2/2 ) 0.20 · (MeViSiO 2/2 ) 0.25 (PhSiO 3/2 ) 0.38 , 25 Organopolysiloxane having a viscosity of 900 mPa · s at ° C. Here, Me represents a methyl group, Vi represents a vinyl group, and Ph represents a phenyl group.
硬度はデュロメータを用い、厚さ１０ｍｍまたは６ｍｍのシート状硬化物で測定した。また、割れ難さの試験として熱衝撃試験を実施した。熱衝撃試験は（株）エスペック製、小型冷熱衝撃装置（ＴＳＥ−１１−Ａ）を用いマイナス４０℃と１１０℃の各温度で３０分間保持の条件でサイクル試験を実施した。マイナス４０℃から１１０℃、１１０℃からマイナス４０℃には、３分以内で到達する。 The hardness was measured with a sheet-like cured product having a thickness of 10 mm or 6 mm using a durometer. Moreover, the thermal shock test was implemented as a test of a cracking difficulty. The thermal shock test was carried out using a small thermal shock apparatus (TSE-11-A) manufactured by Espec Co., Ltd. under the conditions of holding at minus 40 ° C. and 110 ° C. for 30 minutes. Minus 40 ° C to 110 ° C and 110 ° C to minus 40 ° C are reached within 3 minutes.
［実施例１］
（Ａ−１）のジメチルポリシロキサン９０重量部と、（Ｂ−１）のメチル水素ポリシロキサン１０重量部、及び（Ｃ）の白金錯体０．０５部を計量し均一になるまで混合した。この混合液をアスピレーターで減圧脱泡した。この付加硬化型シリコーン混合物の粘度は７００ｍＰａ・ｓであった。次いで銀メッキした金属製リードフレーム（５ｍｍ砲弾型用）を混合液中に２分間浸漬させた後、リードフレームを取り出し、３分間保持することにより余分な付加硬化型シリコーン混合物を取り除いた後、１００℃で１５分間加熱硬化した。得られた軟質の付加硬化型シリコーンで被覆されたリードフレームをマイクロスコープで観察した結果、ほぼ５０〜２００ミクロンの厚みで被覆されていた。また、この付加硬化混合物を１００℃で１５分間加熱硬化した厚さ１０ｍｍのシートの硬度は、タイプＥデュロメータで５０であった。次いで（ａ）のオルガノポリシロキサン１００重量部と（ｂ）の白金錯体０．０２重量部を計量し均一になるまで混合した。この混合液をアスピレーターで減圧脱泡した付加型シリコーンレジン混合物の粘度は８００ｍＰａ・ｓであった。得られた付加型シリコーンレジン混合物を樹脂製キャスティングケース（５ｍｍ砲弾型）に注入し、更に先に得られたすでに軟質の付加型シリコーンで被覆されたリードフレームを挿入し、１５０℃で３時間加熱硬化した。この付加型シリコーンレジン混合物を別途１５０℃で３時間加熱硬化した厚さ６ｍｍのシートの硬度は、透明であり、タイプＤデュロメータによる硬度は６０であった。得られた二層構造の封止部を有する発光ダイオード装置を熱衝撃試験機で３００サイクル評価したところ、クラックは全く見られなかった。
[Example 1]
90 parts by weight of dimethylpolysiloxane (A-1), 10 parts by weight of methylhydrogenpolysiloxane (B-1), and 0.05 part of platinum complex (C) were weighed and mixed until uniform. This mixed solution was degassed under reduced pressure with an aspirator. The viscosity of this addition-curable silicone mixture was 700 mPa · s. Next, a silver-plated metal lead frame (for a 5 mm shell type) was immersed in the mixed solution for 2 minutes, and then the lead frame was taken out and held for 3 minutes to remove excess addition-curable silicone mixture, and then 100 Heat cured at 15 ° C. for 15 minutes. The obtained lead frame covered with the soft addition-curable silicone was observed with a microscope, and as a result, it was coated with a thickness of about 50 to 200 microns. Further, the hardness of a sheet having a thickness of 10 mm obtained by heating and curing the addition-cured mixture at 100 ° C. for 15 minutes was 50 with a type E durometer. Next, 100 parts by weight of the organopolysiloxane (a) and 0.02 part by weight of the platinum complex (b) were weighed and mixed until uniform. The viscosity of the addition-type silicone resin mixture obtained by degassing this mixed solution with an aspirator was 800 mPa · s. The obtained addition type silicone resin mixture was poured into a resin casting case (5 mm shell type), and the lead frame already coated with the soft addition type silicone previously obtained was inserted, and heated at 150 ° C. for 3 hours. Cured. The sheet of 6 mm thickness obtained by separately heat-curing this addition-type silicone resin mixture at 150 ° C. for 3 hours was transparent, and the hardness by a type D durometer was 60. When the obtained light-emitting diode device having a two-layered sealing portion was evaluated with a thermal shock tester for 300 cycles, no cracks were observed.
［比較例１］
実施例１と同様に、（ａ）のオルガノポリシロキサン１００重量部とヒドロシリル化触媒（ｂ）０．０２重量部を計量し均一になるまで混合した。この混合液を減圧脱泡した後の粘度は８００ｍＰａ・ｓであった。得られたシリコーンレジン混合物を樹脂製キャスティングケース（５ｍｍ砲弾型）に注入し、軟質のシリコーンで被覆されていない銀メッキした金属製リードフレームを挿入後１５０℃で３時間加熱硬化した。得られた単層の封止部を有する発光ダイオード装置を熱衝撃試験機で、１０サイクル評価したところ、全てのサンプルにクラックが見られた。
[Comparative Example 1]
In the same manner as in Example 1, 100 parts by weight of the organopolysiloxane (a) and 0.02 part by weight of the hydrosilylation catalyst (b) were weighed and mixed until uniform. The viscosity of the mixture after degassing under reduced pressure was 800 mPa · s. The obtained silicone resin mixture was poured into a resin casting case (5 mm shell type), and a silver-plated metal lead frame not covered with soft silicone was inserted and cured by heating at 150 ° C. for 3 hours. When the obtained light emitting diode device having a single-layer sealing portion was evaluated for 10 cycles with a thermal shock tester, cracks were found in all the samples.
本発明の発光ダイオード装置は、特に、青色〜紫外光を発するＬＥＤ素子からなる発光ダイオード装置は、急激な温度変化によっても封止部にクラックが発生し難く、封止部は、シリコーン系材料の透明性、耐光性・耐熱性を保持しながら、強度と硬度とのバランスに優れ有用である。 The light-emitting diode device according to the present invention, in particular, a light-emitting diode device composed of LED elements that emit blue to ultraviolet light is less likely to crack in the sealed portion even with a sudden temperature change. While maintaining transparency, light resistance, and heat resistance, it has an excellent balance between strength and hardness and is useful.
Claims (4)
（Ａ）一分子あたり少なくとも平均１．８個のケイ素原子に結合したアルケニル基を有し、２５℃、せん断速度０．９ｓ−１における粘度が１０ｍＰａ・ｓ以上１０，０００ｍＰａ・ｓ以下であるオルガノポリシロキサン、
（Ｂ）一分子あたり少なくとも平均４個のケイ素原子に結合した水素原子を有し、２５℃、せん断速度０．９ｓ−１における粘度が１０ｍＰａ・ｓ以上１０，０００ｍＰａ・ｓ以下であるオルガノ水素ポリシロキサン（ただし、（Ａ）成分のアルケニル基の１個に対して０．９〜２個のケイ素原子に結合した水素原子となるような量）、
（Ｃ）組成物の硬化を促進する触媒量のヒドロシリル化触媒 In the light-emitting diode device in which the surface of the light-emitting diode element is coated with a soft addition-curable silicone and further sealed with a resinous addition-curable silicone resin, the soft addition-curable silicone is changed from (A) to (C). A light-emitting diode device, which is a cured product of the composition having a hardness after curing of 5 to 75 in a type E durometer.
(A) Organo having an alkenyl group bonded to at least 1.8 silicon atoms on average per molecule and having a viscosity at 25 ° C. and a shear rate of 0.9 s −1 of 10 mPa · s to 10,000 mPa · s Polysiloxane,
(B) an organohydrogenpolysiloxane having hydrogen atoms bonded to an average of 4 silicon atoms per molecule and having a viscosity at 25 ° C. and a shear rate of 0.9 s −1 of 10 mPa · s to 10,000 mPa · s Siloxane (provided that hydrogen atoms bonded to 0.9 to 2 silicon atoms with respect to one alkenyl group of component (A)),
(C) A catalytic amount of hydrosilylation catalyst that promotes curing of the composition
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| JP2004227410A JP2006049533A (en) | 2004-08-04 | 2004-08-04 | Resin sealing light emitting diode device and sealing method |
| CN2005800266201A CN101432894B (en) | 2004-08-04 | 2005-07-28 | Resin-encapsulated light emitting diode and method for encapsulating light emitting diode |
| PCT/EP2005/008247 WO2006013066A2 (en) | 2004-08-04 | 2005-07-28 | Resin-encapsulated light emitting diode and method for encapsulating light emitting diode |
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| JP2008010591A (en) * | 2006-06-28 | 2008-01-17 | Nichia Chem Ind Ltd | Light emitting device, manufacturing method thereof, package, and substrate for mounting light emitting element |
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| JP2009537992A (en) * | 2006-05-17 | 2009-10-29 | スリーエム イノベイティブ プロパティズ カンパニー | Method of making a light emitting device having a multilayer silicon-containing encapsulant |
| JP2010529645A (en) * | 2007-06-01 | 2010-08-26 | ワッカー ケミー アクチエンゲゼルシャフト | Silicon molded member having a light emitter |
| JP2010530738A (en) * | 2007-06-01 | 2010-09-16 | ワッカー ケミー アクチエンゲゼルシャフト | Photoreactor |
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| JPH03116857A (en) * | 1989-09-29 | 1991-05-17 | Mitsui Petrochem Ind Ltd | Light emitting or photodetective device |
| JP2001085748A (en) * | 1999-09-14 | 2001-03-30 | Matsushita Electric Works Ltd | Light-emitting device |
| DE10238799A1 (en) * | 2002-08-23 | 2004-03-11 | Siemens Ag | Organic light emitting diode (OLED) and / or display, sealing process and use thereof |
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| JP2004231824A (en) * | 2003-01-31 | 2004-08-19 | Wacker Asahikasei Silicone Co Ltd | Organopolysiloxane composition and cured product thereof |
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| CN101432894A (en) | 2009-05-13 |
| WO2006013066A3 (en) | 2008-12-11 |
| WO2006013066A2 (en) | 2006-02-09 |
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