WO2014065143A1 - 熱硬化性樹脂組成物 - Google Patents
熱硬化性樹脂組成物 Download PDFInfo
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- WO2014065143A1 WO2014065143A1 PCT/JP2013/077848 JP2013077848W WO2014065143A1 WO 2014065143 A1 WO2014065143 A1 WO 2014065143A1 JP 2013077848 W JP2013077848 W JP 2013077848W WO 2014065143 A1 WO2014065143 A1 WO 2014065143A1
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- Prior art keywords
- thermosetting resin
- formula
- resin composition
- group
- compound
- Prior art date
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- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 106
- 239000011342 resin composition Substances 0.000 title claims abstract description 78
- 150000001875 compounds Chemical class 0.000 claims abstract description 64
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 58
- 229920005989 resin Polymers 0.000 claims abstract description 47
- 239000011347 resin Substances 0.000 claims abstract description 47
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 34
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 10
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 8
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 64
- 239000000047 product Substances 0.000 claims description 47
- 239000000203 mixture Substances 0.000 claims description 41
- 239000000377 silicon dioxide Substances 0.000 claims description 30
- 230000003287 optical effect Effects 0.000 claims description 25
- 239000004065 semiconductor Substances 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 21
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
- -1 organosiloxane compound Chemical class 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 15
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 15
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000013329 compounding Methods 0.000 claims description 6
- 239000000565 sealant Substances 0.000 claims description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- 230000008878 coupling Effects 0.000 claims description 2
- 238000010168 coupling process Methods 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- 238000012360 testing method Methods 0.000 description 31
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 22
- 239000000463 material Substances 0.000 description 20
- 238000000034 method Methods 0.000 description 20
- 238000001723 curing Methods 0.000 description 18
- 229920006375 polyphtalamide Polymers 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 230000006750 UV protection Effects 0.000 description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 11
- 229920002050 silicone resin Polymers 0.000 description 11
- 238000002834 transmittance Methods 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 9
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 8
- 229920005601 base polymer Polymers 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 238000007789 sealing Methods 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 238000004383 yellowing Methods 0.000 description 7
- 239000004954 Polyphthalamide Substances 0.000 description 6
- 230000004888 barrier function Effects 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 5
- 229920006128 poly(nonamethylene terephthalamide) Polymers 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- VMAWODUEPLAHOE-UHFFFAOYSA-N 2,4,6,8-tetrakis(ethenyl)-2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound C=C[Si]1(C)O[Si](C)(C=C)O[Si](C)(C=C)O[Si](C)(C=C)O1 VMAWODUEPLAHOE-UHFFFAOYSA-N 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000008393 encapsulating agent Substances 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 229910021485 fumed silica Inorganic materials 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 3
- QYLFHLNFIHBCPR-UHFFFAOYSA-N 1-ethynylcyclohexan-1-ol Chemical compound C#CC1(O)CCCCC1 QYLFHLNFIHBCPR-UHFFFAOYSA-N 0.000 description 2
- 229910002012 Aerosil® Inorganic materials 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 150000002903 organophosphorus compounds Chemical class 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- 150000003606 tin compounds Chemical class 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- LUWOGHUBWAZEQL-UHFFFAOYSA-N 2-(oxiran-2-ylmethoxymethyl)oxirane trimethoxysilane Chemical compound C(C1CO1)OCC1CO1.CO[SiH](OC)OC LUWOGHUBWAZEQL-UHFFFAOYSA-N 0.000 description 1
- NECRQCBKTGZNMH-UHFFFAOYSA-N 3,5-dimethylhex-1-yn-3-ol Chemical compound CC(C)CC(C)(O)C#C NECRQCBKTGZNMH-UHFFFAOYSA-N 0.000 description 1
- 102100027123 55 kDa erythrocyte membrane protein Human genes 0.000 description 1
- 239000004956 Amodel Substances 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 108050007394 Kinesin-like protein KIF20B Proteins 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 101000709029 Toxoplasma gondii Rhomboid-like protease 5 Proteins 0.000 description 1
- FCCRGBVYSYHQRQ-UHFFFAOYSA-N [ethenyl(dimethyl)silyl]oxy-dimethylsilicon Chemical compound C[Si](C)O[Si](C)(C)C=C FCCRGBVYSYHQRQ-UHFFFAOYSA-N 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- YKIOKAURTKXMSB-UHFFFAOYSA-N adams's catalyst Chemical compound O=[Pt]=O YKIOKAURTKXMSB-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000007718 adhesive strength test Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 1
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 description 1
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011067 equilibration Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- ZMKOJNOAFRBHTG-UHFFFAOYSA-N ethenyl(ethenylsilyloxy)silane Chemical compound C=C[SiH2]O[SiH2]C=C ZMKOJNOAFRBHTG-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 1
- POPVULPQMGGUMJ-UHFFFAOYSA-N octasilsesquioxane cage Chemical compound O1[SiH](O[SiH](O2)O[SiH](O3)O4)O[SiH]4O[SiH]4O[SiH]1O[SiH]2O[SiH]3O4 POPVULPQMGGUMJ-UHFFFAOYSA-N 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229910003446 platinum oxide Inorganic materials 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 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
- 238000012795 verification Methods 0.000 description 1
Classifications
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
-
- 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
-
- 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
-
- 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
-
- 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
- C08G77/045—Polysiloxanes containing less than 25 silicon atoms
-
- 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
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5435—Silicon-containing compounds containing oxygen containing oxygen in a ring
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
Definitions
- the present invention is a thermosetting resin composition
- a thermosetting resin composition comprising a thermosetting resin composed of silsesquioxane and organopolysiloxane having both heat resistance and a high refractive index, wherein the thermosetting resin composition is cured.
- a cured product an optical semiconductor composition containing the thermosetting resin composition, and an optical semiconductor element including the optical semiconductor composition.
- White LEDs have been used for lighting and other purposes, but heat generation of the LED package has become a problem as the output increases.
- a silicone resin has been used as a sealing material for white LEDs instead of an epoxy resin.
- Silicone resins used for LEDs are roughly classified into two types, phenyl silicone resins and methyl silicone resins.
- phenyl silicone resin has a high refractive index and good light extraction efficiency. Furthermore, since it has a high gas barrier property and good adhesion to the package, it has excellent reliability such as moisture absorption reflow resistance or heat cycle resistance. However, the heat-resistant yellowing is superior to the epoxy resin, and is not sufficient to cope with the large output of the LED.
- Methyl silicone resin is very excellent in heat-resistant yellowing, but the light extraction efficiency of the LED is not good because of its low refractive index.
- the methyl silicone resin is mainly composed of dimethyl silicone, the gas barrier property is low, the adhesion with the package is inferior, and there is a problem that the methyl silicone resin is easily peeled off during moisture absorption reflow. When peeling occurs, the luminance of light generated from the LED is lowered, which is not preferable.
- the commonly used phenyl silicone resin is not only severely deteriorated in luminance due to yellowing but also cracks due to resin deterioration.
- the dimethyl silicone resin has little luminance degradation due to yellowing, the resin progresses in the high temperature region, cracks are generated and the luminance deteriorates, and it may not be applicable to the high power LED application.
- thermosetting resin composition having all the balance such as anti-moisture reflow or anti-heat cycle, which can cope with an increase in the output of the white LED, and has both a high refractive index and heat resistance. It was anxious.
- a cage-type silsesquioxane material excellent in heat resistance and UV resistance has attracted attention, and an LED encapsulant using the material has been reported.
- Patent Document 1 discloses an LED encapsulant made of a thermosetting resin composition comprising a thermosetting resin in which a SiH group is introduced into a cage-type octasilsesquioxane and an organopolysiloxane having an alkenyl group. .
- Patent Document 2 discloses a thermosetting resin composition using an incomplete cage type silsesquioxane called a so-called double decker type.
- the silsesquioxane is a compound obtained by hydrolytic condensation of phenyltrimethoxysilane. Since the position of the Si-Ph group is not random but the structure is controlled, the heat resistance and light resistance are improved while maintaining a high refractive index. Excellent.
- Patent Document 2 discloses a thermosetting containing a SiH group and a vinyl group obtained by reacting a silanol group part of silsesquioxane having an incomplete cage structure with a SiH group-modified compound and an organopolysiloxane having an alkenyl group. A functional resin is disclosed. And what hardened this thermosetting resin has high heat resistance in spite of being high refractive index, and also has good adhesiveness with the polyphthalamide resin base material or silver base material which is the package material of LED. It is shown.
- Patent Document 1 only describes the heat resistance at 200 ° C. of the thermosetting resin composition, and it is used for LED sealants such as adhesion to a substrate, heat cycle resistance, moisture absorption reflow resistance, and the like. There is no description of required properties. Further, since the composition is basically composed of units of -Me 2 Si-O, the refractive index is not high. Moreover, although the property of this composition is solid at normal temperature and can be applied to sealing of LED by a molding method, it cannot be applied to sealing of LED of a dispenser method.
- thermosetting resin containing a SiH group and a vinyl group obtained from the reaction of a double-decker silsesquioxane having four SiH groups described in Patent Document 2 and an organopolysiloxane having two vinyl groups was used.
- the cured product has a problem that the adhesion performance is deteriorated when the double-decker silsesquioxane content is small.
- the present invention is a thermosetting resin composition having both heat resistance and UV resistance, high refractive index and gas barrier property, low hardness, high adhesion, and excellent moisture absorption reflow resistance and heat cycle resistance.
- a thermosetting resin composition having excellent reliability as an LED encapsulant is provided.
- thermosetting resin containing a SiH group and an alkenyl group obtained from a reaction between a silsesquioxane having a SiH group and an organopolysiloxane having two alkenyl groups, and a straight chain having a SiH group only at one end.
- a chain-like organopolysiloxane compound, a coupling agent having an epoxy group as an additive, and a Pt catalyst in a thermosetting resin composition sacrificing high refractive index, heat resistance, and even adhesion performance.
- thermosetting resin composition containing the following (A) to (D).
- D a Pt catalyst
- thermosetting resin composition according to item 1 or 2 which contains an organosiloxane compound (E) having two or more alkenyl groups as required. 4). 4. The thermosetting resin composition according to any one of items 1 to 3, wherein the thermosetting resin (A) is a compound represented by the following formula (1).
- each X is independently A group represented by the following formula (XI), formula (X-II) or formula (X-III), and per molecule of the compound represented by formula (1) [the compound is represented by formula (XI ), A group represented by formula (X-II), and a group represented by formula (X-III) are different from each other in the case of a mixture of the compounds represented by formula (
- the number of groups represented by XI) is a
- the number of groups represented by formula (X-II) is b
- the number of groups represented by formula (X-III) is c
- R 1 is each independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl and cyclohexyl
- m is 1 to 100.
- R 2 and R 3 are each independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl, cyclohexyl and phenyl, and r is —OSi (R 3 ) 2 —. Where r is an average value satisfying 2-20.
- R 4 and R 5 are each independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl, cyclohexyl and phenyl, and s is —OSi (R 5 ) 2 —. S is an average value satisfying 2 to 20. 5. 5.
- the thermosetting according to any one of items 1 to 4, wherein the linear organopolysiloxane compound (B) having a SiH group only at one end is a compound represented by the following formula (2): Resin composition.
- R 6 and R 7 are each independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl and cyclohexyl, m ′ is the number of repeating —OSi (R 7 ) 2 — An average value satisfying 20. 6). 6.
- R 8 and R 9 are each independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl, cyclohexyl and phenyl, and n is —OSi (R 9 ) 2 —.
- the compounding ratio of the thermosetting resin (A) is 70 to 95% by mass
- the compounding ratio of the organopolysiloxane compound (B) is 2 to 20% by mass
- the silane coupling 7.
- thermosetting resin composition according to any one of items 3 to 7, which contains the organosiloxane compound (E) in a proportion of 1 to 10% by mass as necessary. 9.
- a cured product obtained by curing the thermosetting resin composition according to any one of 1 to 9 above.
- An optical semiconductor composition comprising the thermosetting resin composition according to any one of items 1 to 9. 12 12.
- An optical semiconductor element comprising the optical semiconductor composition according to item 11 as a sealing agent.
- the cured product obtained by curing the thermosetting resin composition of the present invention has a high refractive index and high heat resistance, and can maintain the advantage of excellent adhesion, while also reducing the hardness of the cured product. it can. Therefore, the cured product sealed with the thermosetting resin composition of the present invention is excellent in stress relaxation ability, and the optical semiconductor device prepared using the thermosetting resin composition can be used for heat cycle resistance test and the like.
- the optical semiconductor device can withstand strict reliability tests. Furthermore, the optical semiconductor device is low in hardness but low in surface tack, can be diced, and has excellent moldability.
- thermosetting resin composition of the present invention has a silsesquioxane skeleton as a main component, the cured product is excellent in heat resistance and UV resistance. Furthermore, it exhibits excellent adhesion to housing base materials such as polyphthalamide resin, silver or ceramics, and can withstand strict reliability tests such as moisture reflow or heat cycle tests.
- thermosetting resin composition of the present invention is that an organopolysiloxane compound having a SiH group only at one end of the present invention is an incomplete cage silsesquioxane having a SiH group and an alkenyl group as main components.
- the alkenyl group of the thermosetting resin By reacting with the alkenyl group of the thermosetting resin, the crosslink density can be suppressed, resulting in a low hardness capable of stress relaxation, and an organopolysiloxane compound having a SiH group at one end This is considered to be due to the fact that only one end of the organopolysiloxane is bonded, the degree of freedom is high, and the physical properties of the cured resin itself are not changed.
- thermosetting resin composition of the present invention is characterized by containing the following (A) to (D).
- D Pt catalyst
- Thermosetting resin (A) which is a reaction product of silsesquioxane having SiH groups and organopolysiloxane having two alkenyl groups, and containing SiH groups and alkenyl groups, This is a reaction product of silsesquioxane having SiH group and organopolysiloxane having two alkenyl groups.
- silsesquioxanes having a SiH group examples include double-decker silsesquioxanes and cage-type silsesquioxanes having a T8 structure.
- the cage silsesquioxane having a T8 structure has eight functional groups, whereas the double-decker silsesquioxane used in the present invention has only four functional groups. Easy to control the structure.
- the double-decker silsesquioxane preferably used in the present invention is incompletely condensed, has a relatively high degree of molecular freedom, and is excellent in flexibility. . From such a viewpoint, double-decker silsesquioxane is preferable.
- thermosetting resin (A) examples include a compound represented by the following formula (1).
- Xs are each independently a group represented by the following formula (XI), formula (X-II) or formula (X-III).
- R 1 is each independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl and cyclohexyl, and m is 1 to 100. Among these, m is preferably 1.
- R 2 and R 3 are each independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl, cyclohexyl and phenyl, preferably methyl.
- r is the number of repetitions of —OSi (R 3 ) 2 —, and r is an average value satisfying 2 to 20. r is more preferably 2 to 10.
- R 1 is the same as R 1 in Formula (1).
- R 4 and R 5 are each independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl, cyclohexyl and phenyl, and s is —OSi (R 5 ) 2 —.
- S is an average value satisfying 2 to 20.
- s is preferably from 2 to 10, and more preferably from 2 to 4.
- the compound is represented by the group represented by the formula (XI), the group represented by the formula (X-II), and the formula (X-III)
- the number of groups represented by the formula (XI) of the compound 1 molecule average is a
- the number of groups represented by the formula (X-II) is b
- c + is the number of groups represented by formula (X-III)
- a + 2b + c 4, 0 ⁇ a ⁇ 3, 0 ⁇ b ⁇ 1, and 0 ⁇ c ⁇ 3 .
- the above compound represented by the general formula (1) has a> c, and on average, the number of SiH groups is larger than that of vinyl groups, and can be defined as a so-called SiH group type thermosetting resin. From the viewpoint of conspicuous excellent characteristics when a cured product is used, a is preferably from 1.0 to 3.0, and more preferably from 1.3 to 2.5.
- A, b, and c in the compound represented by the general formula (1) can be adjusted by the inventor's discretion, for example, in accordance with the production method described in International Publication No. 2011/145638. Can be adjusted.
- the thermosetting resin composition of the present invention preferably contains 70 to 95% by mass, and preferably 80 to 90% by mass of the thermosetting resin (A) based on the total amount of the thermosetting resin composition. More preferred.
- the characteristics possessed by the double-decker silsesquioxane that is, the characteristics such as heat resistance, UV resistance, and high refractive index are maintained. It is possible.
- cured material can be D45 or less by making the mixture ratio of a thermosetting resin (A) into 95 mass% or less.
- R 6 and R 7 are each independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl and cyclohexyl, and in particular, a methyl group having 1 carbon atom, A butyl group having a number of 4 is preferred.
- m ′ is the number of repetitions of —OSi (R 7 ) 2 —.
- m ′ is an average value satisfying 4 to 20, and preferably an average value satisfying 4 to 15. Further, an average value satisfying 5 to 10 is preferable.
- the organopolysiloxane compound (B) can be produced by a known and usual method. For example, it can be synthesized by the method described in Japanese Unexamined Patent Publication No. 2000-273178 or Japanese Unexamined Patent Publication No. 2001-055546.
- the organopolysiloxane compound (B) is used to reduce the hardness. That is, by reacting with the alkenyl group of the thermosetting resin (A) to lower the overall crosslink density, an increase in hardness can be suppressed and a reduction in hardness can be achieved.
- the content of the organopolysiloxane compound (B) in the thermosetting resin composition of the present invention is such that the refractive index of the cured product obtained by curing the thermosetting resin composition is 1.5 or more. An amount is preferred. Moreover, since hardness will not fall if there is too little, it is preferable that it is content that the hardness of hardened
- the number average molecular weight of the organopolysiloxane compound (B) is preferably 148 to 2000, and more preferably 400 to 1000. If the number average molecular weight of the organopolysiloxane compound (B) is 400 or less, the volatility becomes high and there is a risk of dispersal at the stage of blending and curing the cured composition, so a number average molecular weight of 400 or more is more preferable.
- the number average molecular weight of the organopolysiloxane compound (B) is set to 2000 or less, a reaction product of silsesquioxane having SiH group and organopolysiloxane having two alkenyl groups, It is possible to maintain compatibility with a thermosetting resin containing an alkenyl group, maintain the transparency of the cured product, and maintain adhesion performance.
- the blending ratio of the organopolysiloxane compound (B) is preferably 5 to 20% by mass, more preferably 5 to 15% by mass in the total thermosetting resin composition of the present invention.
- the blending ratio of the organopolysiloxane compound (B) is preferably 5 to 20% by mass, more preferably 5 to 15% by mass in the total thermosetting resin composition of the present invention.
- (C) Coupling agent having an epoxy group examples include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and 3-glycidoxypropyltrimethoxysilane. , 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane and 3-glycidoxypropylmethyldiethoxysilane. Among these, 3-glycidoxypropyltrimethoxysilane is more preferable.
- the blending ratio of the silane coupling agent (C) is preferably 0.1 to 5.0% by mass and preferably 0.2 to 2% by mass in the total thermosetting resin composition of the present invention. More preferred. More preferably, the content is 0.25% by mass to 1.0% by mass.
- Pt catalyst (D) is a catalyst containing platinum, and the platinum may not be oxidized or may be oxidized. Examples of oxidized platinum include platinum oxide. Examples of the partially oxidized platinum include an Adams catalyst.
- Examples of the Pt catalyst include a Karstedt catalyst, a Spear catalyst, and hexachloroplatinic acid. These are generally well known catalysts. Among these, a non-oxidized type Karsted catalyst is preferable.
- the blending ratio of the Pt catalyst (D) in the total thermosetting resin composition of the present invention is preferably an amount sufficient to advance the curing of the curable resin composition of the present invention, specifically, 0.01 ppm to 10 ppm is preferable, and 0.1 ppm to 1 ppm is more preferable.
- Curing can be advanced by setting the blending ratio of the Pt catalyst (D) to 0.01 ppm or more. By setting the blending ratio of the Pt catalyst (D) to 0.1 ppm or more, the curing can be rapidly advanced. Moreover, the heat resistance of hardened
- thermosetting resin composition of the present invention may contain (E) an organosiloxane compound having two or more alkenyl groups as required.
- organosiloxane compound (E) having two or more alkenyl groups include compounds represented by the following general formula.
- R 8 and R 9 are each independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl, cyclohexyl and phenyl, and n is —OSi (R 9 ) 2 —. The average value satisfying 1 to 50.
- the organopolysiloxane compound (E) is a component for adjusting the viscosity of the cured composition of the present invention and assisting the cured product with strength or flexibility.
- R 8 and R 9 are all alkyl having 1 to 4 carbon atoms, methyl having 1 carbon atoms is preferably used, and is represented by the following general formula (4).
- n ′ is an average value satisfying 1 to 20.
- n 'exceeds 20 the compatibility with the cured composition of the present invention is deteriorated, which is not preferable.
- 5 or more is preferable, and 10 or less is preferable from the viewpoint of a gas barrier. From the viewpoint of flexibility and gas barrier, 5 to 8 is particularly preferable.
- x is an average value satisfying 1 to 50, preferably 1 to 20.
- y + z is an average value satisfying 1 to 50, and a value satisfying y / (y + z) ⁇ 0.5 is preferable from the viewpoint of refractive index and gas barrier.
- y + z is preferably 10 or more.
- organosiloxane compounds (E) having two or more alkenyl groups may be used in combination as desired by the inventor.
- the organosiloxane compound (E) can be produced by a known and commonly used method. Specifically, for example, the organosiloxane compound represented by the formula (4) is subjected to an equilibration reaction between tetramethylvinyldisiloxane and octamethylcyclotetrasiloxane in the presence of a solid acid catalyst such as activated clay, and then filtered. Can be produced by removing the solid acid catalyst by a low boiling point under a vacuum condition of about 0.13 kPa and a temperature of 100 to 120 ° C.
- the organosiloxane compound represented by the formula (5) or the formula (6) can be produced by a known and commonly used method.
- the organosiloxane compound represented by Formula (5) or Formula (6) is industrially available from GELEST.
- the blending ratio of the organosiloxane compound (E) is preferably 10% by mass or less in the total thermosetting resin composition of the present invention. It is preferable to adjust the blending ratio of the organosiloxane compound (E) to 10% by mass or less because the heat resistance is improved and the resin strength is increased.
- thermosetting resin composition of the present invention may further contain the following components.
- Curing retarder known ones used in addition-type curable compositions with hydrosilylation catalysts can be used. Specific examples include compounds containing two or more alkenyl groups, compounds containing aliphatic unsaturated bonds, organophosphorus compounds, tin compounds, and organic peroxides. These may be used alone or in combination of two or more.
- Examples of the compound containing two or more alkenyl groups include disiloxanes containing both vinyl groups, trisiloxanes, and vinyl group-containing cyclic siloxanes such as 1,3,5,7-tetravinyltetramethylcyclotetrasiloxane. Can be mentioned.
- Examples of the compound containing an aliphatic unsaturated bond include 3-methyl-1-dodecin-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 1-ethynyl-1-cyclohexanol and the like. Mention may be made of propargyl alcohols, ene-yne compounds, maleic esters such as maleic anhydride and dimethyl maleate.
- organophosphorus compounds examples include triorganophosphine, diorganophosphine, organophosphone, and triorganophosphite.
- tin compounds include stannous halide dihydrate and stannous carboxylate.
- organic peroxide include di-t-butyl peroxide, dicumyl peroxide, benzoyl peroxide, and t-butyl perbenzoate.
- 1,3-divinyldisiloxane 1,3,5,7-tetravinyltetramethylcyclotetrasiloxane or 1-ethynyl-1-cyclohexanol is preferred.
- thermosetting resin composition of the present invention By blending a curing retarder with the thermosetting resin composition of the present invention, an increase in viscosity at room temperature can be suppressed and a pot life can be earned.
- the content of the curing retarder in the thermosetting resin composition of the present invention is preferably 0.001 to 0.1% by mass, and more preferably 0.01 to 0.05% by mass.
- thermosetting resin composition of the present invention ii) Phosphor A phosphor is dispersed in the thermosetting resin composition of the present invention to have a light emitting function and can be used as a composition for LED.
- the phosphor content in the thermosetting resin composition of the present invention is preferably 1 to 90% by mass, and more preferably 2 to 50% by mass.
- the concentration distribution of the phosphor in the composition may be uniform or different.
- the type of phosphor to be used, the presence / absence of the phosphor concentration distribution, and the conditions for the distribution may be determined according to the use environment, application, and purpose of the LED.
- silica Silica may be added to the thermosetting resin composition of the present invention for the purpose of improving the resin strength or preventing the precipitation of the phosphor.
- the ratio of silica in the thermosetting resin composition of the present invention is preferably 1 to 10% by weight ratio with respect to the total amount of the thermosetting resin composition.
- Silica may be a finely divided natural silica (natural silica), or may be industrially synthesized silica (synthetic silica). Since natural silica is a crystal, it has a crystal axis. For this reason, although the optical characteristic derived from a crystal
- Synthetic silica includes wet synthetic silica and dry synthetic silica, but the use is not particularly limited in the present invention.
- synthetic silica may have water of crystallization regardless of the production method, and if this water of crystallization may affect the thermosetting resin composition or cured product, LED element, etc., the number of water of crystallization It is preferable to select in consideration of the above.
- Synthetic silica is amorphous rather than crystal, so there is no crystal axis, and optical characteristics derived from crystal cannot be expected. However, in addition to controlling the particle distribution, it is possible to take advantage of the feature that the particle diameter can be made extremely small.
- fumed silica has a nano-order particle size and excellent particle dispersibility. Furthermore, when compared with the same weight, the smaller the particle diameter, the larger the total surface area, so that the light reflection direction becomes more diversified, so that it can be used more preferably.
- silica has a large surface area and is a hydrophilic material (hydrophilic silica) due to the effect of silanol present on the surface, but can also be made into hydrophobic silica by chemical modification.
- hydrophilic silica hydrophilic silica
- Which type of silica is used is selected depending on the purpose, but in the present invention, it is preferable to use hydrophilic silica in experimental verification.
- thermosetting resin composition of the present invention is not particularly limited.
- a mixer such as a homodisper, a homomixer, a universal mixer, a planetarium mixer, a kneader, a triple roll or a bead mill
- examples include a method of mixing the above-described curing accelerator, silicone resin, and, if necessary, each predetermined amount of the thermosetting agent, antioxidant, and the like under heating.
- thermosetting resin composition of this invention or its hardened
- light such as a die bonding material for connecting to sealing agent, a housing material, a lead electrode, or a heat sink, a light emitting diode
- a light emitting element of a semiconductor element is flip-chip mounted, it can be used as an underfill material or a passivation film on the light emitting element.
- the optical semiconductor device which can take out the light by the light emission from an optical semiconductor element efficiently can be manufactured, it can use suitably as a sealing agent, an underfill material, or a die-bonding material.
- the temperature is preferably 60 to 200 ° C., more preferably 80 to 160 ° C.
- the time is preferably 1 hour to 24 hours, more preferably 2 hours to 5 hours.
- the hardness of the cured product obtained by curing the thermosetting resin composition of the present invention is preferably 45 or less in D hardness and 30 or more in A hardness.
- the refractive index is preferably a high refractive index of 1.5 or more. When the refractive index is 1.5 or more, the cured product is excellent in LED light extraction efficiency.
- the method for sealing the light emitting element with the composition for optical semiconductors of the present invention is not particularly limited.
- the composition for optical semiconductor of the present invention is previously injected into a mold mold, and the light emitting elements are fixed thereto.
- Examples include a method of curing after immersing a lead frame or the like, and a method of injecting and curing the composition for optical semiconductors of the present invention into a mold in which a light emitting element is inserted.
- Examples of the method for injecting the composition for optical semiconductor of the present invention include injection by a dispenser, transfer molding, and injection molding. Further, as other sealing methods, for example, the optical semiconductor composition of the present invention is dropped onto a light emitting device, stencil printing, screen printing, a method of applying and curing through a mask, and a light emitting device on the bottom. A method of injecting the composition for optical semiconductor of the present invention into a cup or the like with a dispenser or the like and curing it.
- An optical semiconductor element containing the composition for optical semiconductor elements of the present invention as a sealant is also one aspect of the present invention.
- Thermosetting resin comprising a silsesquioxane having a SiH group and an organopolysiloxane having two alkenyl groups, which is a component (A) of the present invention.
- Silsesquioxane derivative base polymer 1 and silsesquioxane derivative base polymer 2 produced by the method disclosed in International Publication No. 2011/145638 as thermosetting resins containing SiH group and alkenyl group was used.
- the number average molecular weight of the polymer synthesized in the present invention was measured as follows. Using a high-performance liquid chromatograph system CO-2065plus manufactured by JASCO Corporation, 20 ⁇ L of a THF solution having a sample concentration of 1 mass% was used as an analysis sample. Column: Shodex KF804L [manufactured by Showa Denko KK] (two in series Connection), column temperature: 40 ° C., detector: RI, eluent: THF, eluent flow rate: 1.0 mL per minute, measured by GPC method, and determined by polystyrene conversion.
- (B) Linear organopolysiloxane compound having a SiH group only at one end
- the number average molecular weight manufactured by JNC Corporation A 900 or 500 single-ended SiH silicone was used.
- a SiH silicone having a number average molecular weight of 500 at both ends was used as a comparative compound for the component (B).
- organopolysiloxane having SiH groups at only one end and having number average molecular weights of 900 and 500 those produced by referring to the method described in Japanese Patent Application Laid-Open No. 2000-273178 were used.
- the both-end SiH silicone having a number average molecular weight of 500 was prepared by referring to the method described in Japanese Patent Application Laid-Open No. 2003-252995.
- SiH silicone at both ends with a number average molecular weight of 500 As a comparative component of the component (B) of the present invention, a both-end SiH silicone having a number average molecular weight of 500 represented by the following formula was used.
- Silane coupling agent having epoxy group Glycidyl ether trimethoxysilane registered trade name Silaace S510 (manufactured by JNC Corporation) was used as the silane coupling agent which is the component (C) of the present invention.
- Pt catalyst As the Pt catalyst which is the component (D) of the present invention, a Karsted catalyst trade name Pt-VTS 3 wt% xylene solution (manufactured by Umicore) was used.
- thermosetting resin composition ⁇ Preparation of thermosetting resin composition>
- the compound synthesized in the above example or a mixture of polyorganosiloxane was placed in a screw tube.
- the screw tube was set in a rotating / revolving mixer ["Awatori Nertaro (registered trademark) ARE-250" manufactured by Sinky Co., Ltd.] and mixed and degassed.
- Humicore's Calsted catalyst (trade name Pt-vtx: xylene solution with 3% Pt concentration) cure retarder: MVS-H (trade name, 1,3,5,7-tetravinyl-1,3,5, 7-tetramethylcyclotetrasiloxane (manufactured by JNC Corporation) diluted 10 times so that the Pt concentration becomes a predetermined amount, mixed and defoamed again with a rotation / revolution mixer, and thermosetting resin Compositions a to e and comparative compositions f to h and j were obtained.
- Table 1 shows the blending amount (g) of each thermosetting resin composition.
- thermosetting resin in which silica was nano-dispersed using a three-roll mill was prepared according to the blending ratio shown in Table 3 of silsesquioxane derivative base polymer 1, one-end SiH silicone having a molecular weight of 900, S510, and silica.
- thermosetting resin compositions As1 to as3 which are thermosetting resin compositions. It was.
- Table 3 shows the blending amount (g) of each thermosetting resin composition.
- silica is as follows.
- Silica I Fumed silica Hydrophilic type Average primary particle size 7nm
- Product name Aerosil # 300 Made by Nippon Aerosil Co., Ltd.
- Silica II Fumed silica Hydrophilic type average primary particle size 12nm
- thermosetting resin composition is sandwiched between 2 sheets of glass with a Naflon SP packing (4 mm diameter) manufactured by Nichias Co., Ltd. Then, it was cured by heating at 150 ° C. for 4 hours in order, and the glass was peeled off to obtain cured products a to e having a smooth surface of 4 mm and comparative cured products f to h and j.
- ⁇ Viscosity> The viscosity of the cured product was measured using a TV-22 viscometer cone plate type manufactured by Toki Sangyo Co., Ltd. at a constant temperature bath temperature of 25 ° C.
- a cured product having a thickness of 4 mm was prepared, and the light transmittance at a wavelength of 400 nm was measured with an ultraviolet-visible spectrophotometer UV-1650 manufactured by Shimadzu Corporation.
- the heat resistance test was performed and evaluated by the following method.
- a cured product having a thickness of 4 mm was prepared, and the light transmittance at a wavelength of 400 nm was measured with an ultraviolet-visible spectrophotometer UV-1650 manufactured by Shimadzu Corporation to obtain an initial transmittance.
- the cured product was placed in an oven at 180 ° C. [constant temperature dryer: DX302 manufactured by Yamato Scientific Co., Ltd.] and heat-treated for a certain time (1000 hours in Table 2).
- the light transmittance of the cured product after the heat resistance test was measured with an ultraviolet-visible spectrophotometer. From the transmittance at a wavelength of 400 nm, the retention at this wavelength (transmittance after heat treatment for a certain time / initial transmittance at each wavelength ⁇ 100 ) was calculated and evaluated.
- the transmittance retention at 400 nm after a heat resistance test at 180 ° C. of 1000 hours was 85% or more, “Yes”, when it was 75% or more, ⁇ , and when it was 75% or less, ⁇ .
- UV transmittance UV light was irradiated on a cured product having a thickness of 4 mm using a Deep UV Lamp manufactured by Ushio Co., Ltd. through a 365 nm band pass filter at an irradiation intensity of 550 to 600 mW / cm 2 .
- the retention rate of 400 nm after irradiation for 2000 hours was 99% or more, it was evaluated as ⁇ , when 97% or more, ⁇ , and when 97 or less, ⁇ .
- ⁇ Adhesive strength test PPA> The test was conducted according to JIS K6850 (1999).
- the test piece was a thermosetting resin between a polyphthalamide resin [Amodel (trade name) A-4122NLWH905 manufactured by Solvay Advanced Polymers Co., Ltd.] adjusted as a substrate according to JIS K6850 (1999).
- the composition was sandwiched and heat cured at 80 ° C. for 1 hour and then at 150 ° C. for 1 hour.
- the adhesion test was measured using a 5 kN load cell with a tensile / compression tester [Autograph AGS-500B manufactured by Shimadzu Corporation].
- ⁇ Adhesion strength test PA9T> The test was conducted according to JIS K6850 (1999).
- the test piece has a thermosetting resin composition sandwiched between polyphthalamide resin [Kuraray Co., Ltd. Genesta (trade name) PA9T] adjusted in accordance with JIS K6850 (1999) as a base material. This was prepared by heating and curing at 80 ° C. for 1 hour and then at 150 ° C. for 1 hour.
- the adhesion test was measured using a 5 kN load cell with a tensile / compression tester [Autograph AGS-500B manufactured by Shimadzu Corporation].
- thermosetting resin composition was injected into 16 PPA resin packages [Model No. 5050 D / G manufactured by Enomoto Co., Ltd.] whose power source was silver-plated with a dispenser (Model No. MPP-1 manufactured by Musashi Co., Ltd.). Thereafter, it was cured by heating at 80 ° C. for 1 hour and 150 ° C. for 4 hours.
- PPA resin packages were absorbed in an environmental tester (model number SH-241 manufactured by Espec Corp.) under moisture absorption conditions of a relative temperature of 30 ° C., a humidity of 60%, and 192 hours, and then a simulated reflow machine [Malcom ( Reflow was performed twice under a temperature condition (260 ° C.) in accordance with JEDEC standards using a model No. SRS-1C] manufactured by Co., Ltd. The number of peeled pieces and the number of cracks generated in 16 pieces are shown.
- thermosetting resin composition After injecting a thermosetting resin composition into 16 PPA resin packages [Model No. 5050 D / G made by Enomoto Co., Ltd.] for power LED having a silver-plated bottom, using a dispenser (model No. MPP1 made by Musashi Co., Ltd.) Heat curing was performed under the conditions of 80 ° C. for 1 hour and 150 ° C. for 4 hours. These PPA resin packages were reflowed once with a simulated reflow machine [model SRS-1C manufactured by Malcolm Co., Ltd.] under temperature conditions (260 ° C.) according to JEDEC standards.
- the cured products a to e using the compositions a to e of the present invention have a hardness in the hardness range of D45 or less to A30, a refractive index of 1.5 or more, and further heat-resistant yellowing, It was found that it was excellent in UV resistance, had good adhesion to a polyphthalamide resin (PPA, PA9T), and was excellent in moisture absorption reflow and heat cycle resistance.
- PPA polyphthalamide resin
- PA9T polyphthalamide resin
- the comparative cured product f using the comparative composition f that does not use an organopolysiloxane compound having a SiH group only at one end had high adhesion but was too hard and did not have heat cycle resistance. Moreover, the hardness of the comparative cured product g using the comparative composition g was reduced only to D45. Moreover, the heat resistance deteriorated.
- the comparative cured product h using the comparative composition h had a hardness of 66 and a low hardness of 66, but both heat resistance and UV resistance were deteriorated, and adhesion was also deteriorated.
- Comparative cured product j using comparative composition j had a D hardness of 30 and was excellent in heat resistance, UV resistance and adhesion, but was inferior in moisture absorption reflow resistance and heat cycle resistance.
- the composition of the present invention in which silica is dispersed is also in the hardness range of D45 or less to A30, the refractive index is 1.5 or more, and further excellent in heat yellowing resistance and UV resistance.
- the adhesiveness with the polyphthalamide resin (PPA, PA9T) was also good, and further excellent in moisture absorption reflow and heat cycle resistance.
- this composition is a nano-dispersed silica, which can prevent the precipitation of the phosphor, efficiently extract light, and contribute to reducing the color variation.
- thermosetting resin composition of the present invention has high heat resistance and high UV resistance, has high adhesion to a substrate and is excellent in toughness, it gives a cured product excellent in moisture absorption reflow resistance and heat cycle resistance. In particular, it is very useful as a sealant for optical semiconductor elements such as high power LEDs.
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Abstract
Description
1.以下の(A)~(D)を含有する熱硬化性樹脂組成物。
(A)SiH基を有するシルセスキオキサンとアルケニル基を2個有するオルガノポリシロキサンとの反応物であって、SiH基とアルケニル基とを含む熱硬化性樹脂
(B)片末端にのみSiH基を有する直鎖状のオルガノポリシロキサン化合物
(C)エポキシ基を有するシランカップリング剤
(D)Pt触媒
2.前記シルセスキオキサンがダブルデッカー型シルセスキオキサンである前項1に記載の熱硬化性樹脂組成物。
3.必要に応じて(E)アルケニル基を2個以上有するオルガノシロキサン化合物を含む前項1または2に記載の熱硬化性樹脂組成物。
4.前記熱硬化性樹脂(A)が、下記式(1)で示される化合物であることを特徴とする前項1~3のいずれか1に記載の熱硬化性樹脂組成物。
下記式(X-I)、式(X-II)または式(X-III)で表される基であり、式(1)で表される化合物1分子あたり[該化合物が式(X-I)で表される基と式(X-II)で表される基と式(X-III)で表される基の割合が異なる化合物の混合物である場合は該化合物1分子平均]の式(X-I)で表される基の数をa、式(X-II)で表される基の数をb、式(X-III)で表される基の数をcとした場合に、a+2b+c=4であり、0<a≦3であり、0≦b≦1であり、0<c≦3である。
R1はそれぞれ独立して、炭素数1~4のアルキル、シクロペンチル及びシクロヘキシルから選択される基であり、mは1~100である。
5.前記片末端にのみSiH基を有する直鎖状のオルガノポリシロキサン化合物(B)が下記式(2)で示される化合物であることを特徴とする前項1~4のいずれか1に記載の熱硬化性樹脂組成物。
6.前記アルケニル基を2個以上有するオルガノポリシロキサン化合物(E)が下記式(3)で示される化合物であることを特徴とする前項3~5のいずれか1に記載の熱硬化性樹脂組成物。
7.熱硬化性樹脂組成物全量基準で、前記熱硬化性樹脂(A)の配合割合が70~95質量%、前記オルガノポリシロキサン化合物(B)の配合割合が2~20質量%、前記シランカップリング剤(C)の配合割合が0.1~5.0質量%である前項1~6のいずれか1に記載の熱硬化性樹脂組成物。
8.必要に応じて前記オルガノシロキサン化合物(E)を1~10質量%の割合で含有する前項3~7のいずれか1に記載の熱硬化性樹脂組成物。
9.さらにシリカ及び蛍光体の少なくとも一方を含有する前項1~8のいずれか1に記載の熱硬化性樹脂組成物。
10.前項1~9のいずれか1に記載の熱硬化性樹脂組成物を硬化させて得られる硬化物。
11.前項1~9のいずれか1に記載の熱硬化性樹脂組成物を含有する光半導体用組成物。
12.前項11に記載の光半導体用組成物を封止剤として含む光半導体素子。
(A)SiH基を有するシルセスキオキサンとアルケニル基を2個有するオルガノポリシロキサンとの反応物であって、SiH基とアルケニル基とを含む熱硬化性樹脂
(B)片末端にのみSiH基を有する直鎖状のオルガノポリシロキサン化合物
(C)エポキシ基を有するシランカップリング剤
(D)Pt触媒
以下、各成分について説明する。
熱硬化性樹脂(A)は、SiH基を有するシルセスキオキサンとアルケニル基を2個有するオルガノポリシロキサンとの反応物である。
片末端にのみSiH基を有する直鎖状のオルガノポリシロキサン化合物(B)としては、下記式(2)で表わされる化合物が挙げられる。
エポキシ基を有するシランカップリング剤(C)としては、例えば、2-(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、3-グリシドキシプロピルトリメトキシシラン、3-グリシドキシプロピルメチルジメトキシシラン、3-グリシドキシプロピルトリエトキシシランおよび3-グリシドキシプロピルメチルジエトキシシランが挙げられる。これらの中でも3-グリシドキシプロピルトリメトキシシランがより好ましい。
Pt触媒(D)は、白金を含む触媒であり、該白金は酸化されていなくてもよいし、酸化されていてもよい。酸化された白金としては、例えば、酸化白金が挙げられる。部分的に酸化された白金としては、例えば、アダムス触媒が挙げられる。
本発明の熱硬化性樹脂組成物は、必要に応じて(E)アルケニル基を2個以上有するオルガノシロキサン化合物を含んでもよい。アルケニル基を2個以上有するオルガノシロキサン化合物(E)としては、下記一般式で示される化合物が挙げられる。
i)硬化遅延材
硬化遅延材としては、ヒドロシリル化触媒による付加型硬化性組成物で用いられている公知のものが使用できる。具体的には、例えば、アルケニル基を2個以上含む化合物、脂肪族不飽和結合を含有する化合物、有機リン化合物、スズ系化合物および有機過酸化物が挙げられる。これらを単独使用、または2種以上併用してもよい。
本発明の熱硬化性樹脂組成物に蛍光体を分散させることで発光機能を有し、LED用の組成物として用いることができる。本発明の熱硬化性樹脂組成物における蛍光体の含有量は、1~90質量%であることが好ましく、2~50質量%であることがより好ましい。
本発明の熱硬化性樹脂組成物には、樹脂強度を向上させる目的や、蛍光体の沈降を防止する目的で、シリカを添加してもよい。本発明の熱硬化性樹脂組成物におけるシリカの割合は、熱硬化性樹脂組成物全量に対する重量比で1~10%であることが好ましい。
限定されない。
本発明の(A)成分である、SiH基とアルケニル基とを含む熱硬化性樹脂として、国際公開第2011/145638号に開示されている方法で製造した、下記シルセスキオキサン誘導体ベースポリマー1およびシルセスキオキサン誘導体ベースポリマー2を用いた。
前記式(1)において、a[式(X-I)]=2.34、2b[式(X-II)]=0、c[式(X-III)]=1.66である、下記化学式で表される化合物をシルセスキオキサン誘導体ベースポリマー1とした。
前記式(1)において、a[式(X-I)]=2.37、2b[式(X-II)]=0.48、c[式(X-III)]=1.14である、下記化学式で表される化合物をシルセスキオキサン誘導体ベースポリマー2とした。
本発明で合成したポリマーの数平均分子量は、次のように測定した。日本分光(株)製の高速液体クロマトグラフシステムCO-2065plusを使用し、試料濃度1質量%のTHF溶液20μLを分析サンプルとして、カラム:Shodex KF804L[昭和電工(株)製](直列に2本接続)、カラム温度:40℃、検出器:RI、溶離液:THF、および溶離液流速:1.0mL毎分でGPC法により測定し、ポリスチレン換算することにより求めた。
本発明の(B)成分である、片末端にのみSiH基を有するオルガノポリシロキサンとして、JNC株式会社製の数平均分子量が900または500の片末端SiHシリコーンを用いた。また、(B)成分の比較化合物として、数平均分子量500の両末端SiHシリコーンを用いた。
前記式(2)において、R6=ブチル、R7=メチル、m=11である、下記化学式により表される化合物を数平均分子量が900の片末端SiHシリコーンとした。
前記式(2)において、R6=ブチル、R7=メチル、m=5である、下記化学式で表される化合物を数平均分子量が500の片末端SiHシリコーンとした。
本発明の(B)成分の比較成分として、下記式で表される数平均分子量500の両末端SiHシリコーンを用いた。
本発明の(C)成分であるシランカップリング剤として、グリシジルエーテルトリメトキシシラン:登録商標名サイラエースS510(JNC株式会社製)を用いた。
本発明の(D)成分であるPt触媒は、カルステッド触媒 商標名Pt-VTS 3wt%キシレン溶液(ユミコア社製)を用いた。
本発明の(E)成分であるアルケニル基を2個以上有するオルガノポリシロキサン化合物は、前記式(3)において、R8=メチル、R9=メチル、n=8である、下記化学式で表される化合物を数平均分子量が700の両末端ビニルシリコーンとした。
スクリュー管に上記実施例で合成した化合物、またはポリオルガノシロキサンの混合物を入れた。スクリュー管を自転・公転ミキサー[株式会社シンキー製「あわとり練太郎(登録商標)」ARE-250]にセットし、混合・脱泡を行った。
上記熱硬化性樹脂組成物に、フィラーとしてシリカを分散させ、組成物cs1およびcs2を得た。表3にフィラー含有組成物の配合量(g)を示す。
シリカI:ヒュームドシリカ 親水性タイプ 平均1次粒経 7nm 商品名:アエロジル#300 日本アエロジル株式会社製
シリカII:ヒュームドシリカ 親水性タイプ平均1次粒経 12nm 商品名:レオロシールQS102 トクヤマ株式会社製
上記熱硬化性樹脂組成物を、ガラス2枚にニチアス(株)製ナフロンSPパッキン(4mm径)をスペーサーとして挟み、この中に熱硬化性樹脂組成物を流し込み、減圧脱泡後、80℃にて1時間、その後150℃にて4時間の順に加熱することにより硬化させ、ガラスをはがして4mm厚の表面が平滑な硬化物a~e並びに比較硬化物f~hおよびjを得た。
硬化物の粘度は、東機産業(株)製のTV-22形粘度計コーンプレートタイプを使用し、恒温槽温度25℃にて測定した。
厚さ4mmの硬化物を作製し、島津製作所(株)製紫外可視分光光度計 UV-1650にて波長400nmにおける光の透過率を測定した。
耐熱試験は、以下の方法にて実施、評価した。厚さ4mmの硬化物を作製し、島津製作所(株)製紫外可視分光光度計 UV-1650にて波長400nmにおける光の透過率を測定し、初期透過率とした。硬化物を180℃のオーブン[定温乾燥機:ヤマト科学(株)製DX302]に入れ、一定時間(表2では1000時間)加熱処理した。
耐UV透過率は、4mm厚の硬化物に、ウシオ株式会社製のDeep UV Lampを用い、365nmのバンドパスフィルターを通して、550~600mW/cm2の照射強度にてUV照射した。2000時間照射後における400nmの保持率99%以上であれば〇、97%以上であれば△、97以下であれば×とした。
試験片は硬化物をバンドソーにて切断し、JIS K7142(2008年)に従って試験片を作製した。この試験片を用いて、アッベ屈折計[(株)アタゴ製NAR-2T]によりナトリウムランプのD線(586nm)を用いて屈折率を測定した。中間液はヨウ化メチレンを用いた。
JIS K6253(2006年)の規定に準じて、D硬度を西東京精密(株)製デュロメータWR-105Dにより、A硬度を西東京精密(株)製デュロメータWR-104Aにより測定した。
サンプル表面を指で触れて硬化物表面のタック性を確認した。タック性がなく指がサンプル表面で滑る場合を「〇」とし、ややグリップ感がある場合を「△」、べたつきを感じる場合を「×」とした。
JIS K6850(1999年)に従って試験を行った。試験片は、基材としてポリフタルアミド樹脂[ソルベイアドバンスドポリマーズ(株)製アモデル(商品名)A-4122NLWH905]をJIS K6850(1999年)に従って寸法を調整して作製したものの間に熱硬化性樹脂組成物を挟み、80℃にて1時間、その後150℃にて1時間で加熱硬化させて作製した。接着試験は引張圧縮試験機[(株)島津製作所製オートグラフAGS-500B]により5kNのロードセルを用いて測定した。
前記接着強さ試験 PPAにおいてせん断接着強さを測定した際の試験体の破断面について、凝集破壊の場合は凝集、界面剥離の場合は、界面とした。なお、凝集破壊とは、基材と組成物の硬化物が界面剥離せずに硬化物自体が破断したことを指し、基材との密着性があることを意味する。凝集破壊と界面剥離が混在しているものは、凝集/界面とした。
JIS K6850(1999年)に従って試験を行った。試験片は、基材としてポリフタルアミド樹脂[クラレ(株)製ジェネスタ(商品名)PA9T]をJIS K6850(1999年)に従って寸法を調整して作製したものの間に熱硬化性樹脂組成物を挟み、80℃にて1時間、その後150℃にて1時間で加熱硬化させて作製した。接着試験は引張圧縮試験機[(株)島津製作所製オートグラフAGS-500B]により5kNのロードセルを用いて測定した。
前記接着強さ試験 PA9Tにおいてせん断接着強さを測定した際の試験体の破断面について、凝集破壊の場合は凝集、界面剥離の場合は、界面とした。なお、凝集破壊とは、基材と組成物の硬化物が界面剥離せずに硬化物自体が破断したことを指し、基材との密着性があることを意味する。凝集破壊と界面剥離が混在しているものは、凝集/界面とした。
JIS Z0208に従って試験を行った。試験片は、厚さ0.9mmの硬化物を作成し、水分吸収材として塩化カルシウムを敷き詰めた直径70mmのカップに前記硬化物をのせて固定し、40℃、湿度90RHの条件で24時間毎に重量増加分を計測した。なお有効面積は28.26cm2である。水蒸気透湿度は以下に式で求めた。
水蒸気透過率(g/m2/24h)=240×{(透湿性試験後の試験体総重量(g))-(透湿性試験前の試験体総重量(g))}×/28.26
底辺部が銀メッキされたパワーLED用のPPA樹脂パッケージ[エノモト(株)製 型番5050 D/G]16個に熱硬化性樹脂組成物をディスペンサー(武蔵株式会社製 型番MPP-1)で注入した後、80℃1時間150℃4時間で加熱硬化させた。これらのPPA樹脂パッケージを、環境試験機(エスペック社製 型番SH-241)内にて、相対温度30℃、湿度60%、192時間の吸湿条件にて吸湿させた後、模擬リフロー機[マルコム(株)製 型番SRS-1C]にてJEDEC規格に準じた温度条件(260℃)にてリフローを2回通した。16個中の剥離個数、クラック発生個数を示した。
底辺部が銀メッキされたパワーLED用のPPA樹脂パッケージ[エノモト(株)製 型番5050 D/G]16個に熱硬化性樹脂組成物をディスペンサー(武蔵株式会社製 型番MPP1)で注入した後、80℃1時間150℃4時間の条件で加熱硬化させた。これらのPPA樹脂パッケージを、模擬リフロー機[マルコム(株)製 型番SRS-1C]にてJEDEC規格に準じた温度条件(260℃)にてリフローを1回通した。この後、冷熱衝撃装置[エスペック(株)製 型番TSE-11]のテストエリアに入れ、-40℃で30分間さらし、105℃で30分間さらすことを1サイクルとして、500サイクル繰り返すことにより実施した。なお、両さらし温度の間の移動時間は2分間で実施した。剥離、クラックの発生を顕微鏡にて観察した。15個中の不良率を示す。
Claims (12)
- 以下の(A)~(D)を含有する熱硬化性樹脂組成物。
(A)SiH基を有するシルセスキオキサンとアルケニル基を2個有するオルガノポリシロキサンとの反応物であって、SiH基とアルケニル基とを含む熱硬化性樹脂
(B)片末端にのみSiH基を有する直鎖状のオルガノポリシロキサン化合物
(C)エポキシ基を有するシランカップリング剤
(D)Pt触媒 - 前記シルセスキオキサンがダブルデッカー型シルセスキオキサンである請求項1に記載の熱硬化性樹脂組成物。
- 必要に応じて(E)アルケニル基を2個以上有するオルガノシロキサン化合物を含む請求項1または2に記載の熱硬化性樹脂組成物。
- 前記熱硬化性樹脂(A)が、下記式(1)で示される化合物であることを特徴とする請求項1~3のいずれか1項に記載の熱硬化性樹脂組成物。
式(1)において、Xはそれぞれ独立して、
下記式(X-I)、式(X-II)または式(X-III)で表される基であり、式(1)で表される化合物1分子あたり[該化合物が式(X-I)で表される基と式(X-II)で表される基と式(X-III)で表される基の割合が異なる化合物の混合物である場合は該化合物1分子平均]の式(X-I)で表される基の数をa、式(X-II)で表される基の数をb、式(X-III)で表される基の数をcとした場合に、
a+2b+c=4であり、0<a≦3であり、0≦b≦1であり、0<c≦3である。
R1はそれぞれ独立して、炭素数1~4のアルキル、シクロペンチル及びシクロヘキシルから選択される基であり、mは1~100である。
式(X-II)において、R2、R3はそれぞれ独立して、炭素数1~4のアルキル、シクロペンチル、シクロヘキシルおよびフェニルから選択される基であり、rは-OSi(R3)2-の繰り返しの数であり、rは、2~20を満たす平均値である。
式(X-III)において、R4及びR5はそれぞれ独立して、炭素数1~4のアルキル、シクロペンチル、シクロヘキシルおよびフェニルから選択される基であり、sは-OSi(R5)2-の繰り返しの数であり、sは、2~20を満たす平均値である。 - 熱硬化性樹脂組成物全量基準で、前記熱硬化性樹脂(A)の配合割合が70~95質量%、前記オルガノポリシロキサン化合物(B)の配合割合が2~20質量%、前記シランカップリング剤(C)の配合割合が0.1~5.0質量%である請求項1~6のいずれか1項に記載の熱硬化性樹脂組成物。
- 必要に応じて前記オルガノシロキサン化合物(E)を1~10質量%の割合で含有する請求項3~7のいずれか1項に記載の熱硬化性樹脂組成物。
- さらにシリカ及び蛍光体の少なくとも一方を含有する請求項1~8のいずれか1項に記載の熱硬化性樹脂組成物。
- 請求項1~9のいずれか1項に記載の熱硬化性樹脂組成物を硬化させて得られる硬化物。
- 請求項1~9のいずれか1項に記載の熱硬化性樹脂組成物を含有する光半導体用組成物。
- 請求項11に記載の光半導体用組成物を封止剤として含む光半導体素子。
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Publication number | Priority date | Publication date | Assignee | Title |
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US20140225420A1 (en) * | 2010-03-25 | 2014-08-14 | Brandt Weibezahn | Methods and Devices for Monitoring and Changing Air Pressure in a Rotating Wheel |
JP2016069485A (ja) * | 2014-09-29 | 2016-05-09 | Jnc株式会社 | 熱硬化性樹脂組成物 |
KR20180096570A (ko) | 2015-12-24 | 2018-08-29 | 제이엔씨 주식회사 | 열경화성 수지 조성물 |
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US11317507B2 (en) * | 2018-03-09 | 2022-04-26 | Arisawa Mfg. Co., Ltd. | Laminate and method for manufacturing the same |
CN108641085A (zh) * | 2018-05-16 | 2018-10-12 | 西南科技大学 | 苯并环丁烯官能化双夹板型倍半硅氧烷及其制备方法和其复合树脂的制备方法 |
TW202122496A (zh) | 2019-12-11 | 2021-06-16 | 美商陶氏全球科技公司 | 快速矽氫化固化組合物 |
Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06234922A (ja) * | 1993-02-09 | 1994-08-23 | Shin Etsu Chem Co Ltd | 低弾性率シリコーンゲル組成物及びそのゲル状硬化物 |
JP2000273178A (ja) | 1999-03-19 | 2000-10-03 | Chisso Corp | クロロメチルフェニル基含有ジオルガノポリシロキサンおよびその製造方法 |
JP2001055446A (ja) | 1999-08-18 | 2001-02-27 | Chisso Corp | ポリオルガノシロキサンおよびその製造方法 |
JP2003252995A (ja) | 2001-12-27 | 2003-09-10 | Chisso Corp | ポリオルガノシロキサンの製造方法および該ポリオルガノシロキサンを含有する液状シリコーンゴム |
JP2007031619A (ja) * | 2005-07-28 | 2007-02-08 | Nagase Chemtex Corp | 光素子封止用樹脂組成物 |
JP2007224102A (ja) * | 2006-02-22 | 2007-09-06 | Shin Etsu Chem Co Ltd | 熱伝導性シリコーン組成物、熱伝導性シリコーン成形体及びその製造方法 |
WO2008133138A1 (ja) * | 2007-04-17 | 2008-11-06 | Kaneka Corporation | 多面体構造ポリシロキサン変性体および該変性体を用いた組成物 |
JP2010095616A (ja) * | 2008-10-16 | 2010-04-30 | Kaneka Corp | ポリシロキサン系組成物およびそれから得られる硬化物 |
JP2011190372A (ja) * | 2010-03-15 | 2011-09-29 | Shin-Etsu Chemical Co Ltd | 発光ダイオード用付加硬化型シリコーン樹脂組成物 |
WO2011145638A1 (ja) | 2010-05-18 | 2011-11-24 | Jnc株式会社 | 新規有機ケイ素化合物、該有機ケイ素化合物を含む熱硬化性樹脂組成物、硬化樹脂および光半導体用封止材料 |
JP2012012556A (ja) * | 2010-07-05 | 2012-01-19 | Kaneka Corp | オルガノポリシロキサン系組成物を用いた光学デバイス。 |
JP2012102167A (ja) | 2010-11-05 | 2012-05-31 | Nitto Denko Corp | シリコーン樹脂、封止材料および光半導体装置 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101774306B1 (ko) | 2010-05-28 | 2017-09-04 | 가부시키가이샤 가네카 | 폴리실록산계 조성물, 경화물, 및, 광학 디바이스 |
-
2013
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- 2013-10-11 JP JP2014543233A patent/JP6599614B2/ja active Active
- 2013-10-11 KR KR1020157010373A patent/KR102172115B1/ko active IP Right Grant
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- 2013-10-11 EP EP13849766.4A patent/EP2910606B1/en active Active
- 2013-10-11 CN CN201380054770.8A patent/CN104736640B/zh active Active
- 2013-10-22 TW TW102138138A patent/TWI589624B/zh not_active IP Right Cessation
Patent Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06234922A (ja) * | 1993-02-09 | 1994-08-23 | Shin Etsu Chem Co Ltd | 低弾性率シリコーンゲル組成物及びそのゲル状硬化物 |
JP2000273178A (ja) | 1999-03-19 | 2000-10-03 | Chisso Corp | クロロメチルフェニル基含有ジオルガノポリシロキサンおよびその製造方法 |
JP2001055446A (ja) | 1999-08-18 | 2001-02-27 | Chisso Corp | ポリオルガノシロキサンおよびその製造方法 |
JP2003252995A (ja) | 2001-12-27 | 2003-09-10 | Chisso Corp | ポリオルガノシロキサンの製造方法および該ポリオルガノシロキサンを含有する液状シリコーンゴム |
JP2007031619A (ja) * | 2005-07-28 | 2007-02-08 | Nagase Chemtex Corp | 光素子封止用樹脂組成物 |
JP2007224102A (ja) * | 2006-02-22 | 2007-09-06 | Shin Etsu Chem Co Ltd | 熱伝導性シリコーン組成物、熱伝導性シリコーン成形体及びその製造方法 |
WO2008133138A1 (ja) * | 2007-04-17 | 2008-11-06 | Kaneka Corporation | 多面体構造ポリシロキサン変性体および該変性体を用いた組成物 |
JP2010095616A (ja) * | 2008-10-16 | 2010-04-30 | Kaneka Corp | ポリシロキサン系組成物およびそれから得られる硬化物 |
JP2011190372A (ja) * | 2010-03-15 | 2011-09-29 | Shin-Etsu Chemical Co Ltd | 発光ダイオード用付加硬化型シリコーン樹脂組成物 |
WO2011145638A1 (ja) | 2010-05-18 | 2011-11-24 | Jnc株式会社 | 新規有機ケイ素化合物、該有機ケイ素化合物を含む熱硬化性樹脂組成物、硬化樹脂および光半導体用封止材料 |
JP2012012556A (ja) * | 2010-07-05 | 2012-01-19 | Kaneka Corp | オルガノポリシロキサン系組成物を用いた光学デバイス。 |
JP2012102167A (ja) | 2010-11-05 | 2012-05-31 | Nitto Denko Corp | シリコーン樹脂、封止材料および光半導体装置 |
Non-Patent Citations (1)
Title |
---|
See also references of EP2910606A4 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20140225420A1 (en) * | 2010-03-25 | 2014-08-14 | Brandt Weibezahn | Methods and Devices for Monitoring and Changing Air Pressure in a Rotating Wheel |
JP2016069485A (ja) * | 2014-09-29 | 2016-05-09 | Jnc株式会社 | 熱硬化性樹脂組成物 |
KR20180096570A (ko) | 2015-12-24 | 2018-08-29 | 제이엔씨 주식회사 | 열경화성 수지 조성물 |
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US9512273B2 (en) | 2016-12-06 |
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