JP6003763B2 - Thermosetting resin composition, light reflective anisotropic conductive adhesive, and light emitting device - Google Patents
Thermosetting resin composition, light reflective anisotropic conductive adhesive, and light emitting device Download PDFInfo
- Publication number
- JP6003763B2 JP6003763B2 JP2013068302A JP2013068302A JP6003763B2 JP 6003763 B2 JP6003763 B2 JP 6003763B2 JP 2013068302 A JP2013068302 A JP 2013068302A JP 2013068302 A JP2013068302 A JP 2013068302A JP 6003763 B2 JP6003763 B2 JP 6003763B2
- Authority
- JP
- Japan
- Prior art keywords
- light
- particles
- group
- reflective
- anisotropic conductive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000853 adhesive Substances 0.000 title claims description 100
- 230000001070 adhesive effect Effects 0.000 title claims description 100
- 229920001187 thermosetting polymer Polymers 0.000 title claims description 52
- 239000011342 resin composition Substances 0.000 title claims description 50
- 239000002245 particle Substances 0.000 claims description 141
- -1 siloxane compound Chemical class 0.000 claims description 48
- 229920005989 resin Polymers 0.000 claims description 40
- 239000011347 resin Substances 0.000 claims description 40
- 125000003700 epoxy group Chemical group 0.000 claims description 39
- 239000003795 chemical substances by application Substances 0.000 claims description 30
- 239000010954 inorganic particle Substances 0.000 claims description 24
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 18
- 239000003822 epoxy resin Substances 0.000 claims description 17
- 229920000647 polyepoxide Polymers 0.000 claims description 17
- 239000002923 metal particle Substances 0.000 claims description 15
- 239000007771 core particle Substances 0.000 claims description 13
- 239000007769 metal material Substances 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 11
- 150000008065 acid anhydrides Chemical group 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 125000001424 substituent group Chemical group 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 9
- 125000000962 organic group Chemical group 0.000 claims description 9
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 9
- 239000011787 zinc oxide Substances 0.000 claims description 8
- 229910052582 BN Inorganic materials 0.000 claims description 7
- 125000002947 alkylene group Chemical group 0.000 claims description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 6
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 6
- 125000005647 linker group Chemical group 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 239000004332 silver Substances 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 claims description 3
- 150000002460 imidazoles Chemical class 0.000 claims 2
- 239000004593 Epoxy Substances 0.000 description 27
- 150000001875 compounds Chemical class 0.000 description 20
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 18
- 239000000047 product Substances 0.000 description 18
- 238000012360 testing method Methods 0.000 description 18
- 239000000758 substrate Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 14
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 12
- 238000005259 measurement Methods 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 239000010931 gold Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 229910052737 gold Inorganic materials 0.000 description 9
- 238000006459 hydrosilylation reaction Methods 0.000 description 9
- 238000002845 discoloration Methods 0.000 description 8
- 229920005992 thermoplastic resin Polymers 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 7
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 7
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].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.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 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 7
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910000077 silane Inorganic materials 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 230000004907 flux Effects 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 125000002723 alicyclic group Chemical group 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 125000000623 heterocyclic group Chemical group 0.000 description 4
- 238000001579 optical reflectometry Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000007500 overflow downdraw method Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 2
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 2
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 125000000732 arylene group Chemical group 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 238000001782 photodegradation Methods 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000002310 reflectometry Methods 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- NIDNOXCRFUCAKQ-UMRXKNAASA-N (1s,2r,3s,4r)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1[C@H]2C=C[C@@H]1[C@H](C(=O)O)[C@@H]2C(O)=O NIDNOXCRFUCAKQ-UMRXKNAASA-N 0.000 description 1
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 description 1
- KNDQHSIWLOJIGP-UMRXKNAASA-N (3ar,4s,7r,7as)-rel-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione Chemical compound O=C1OC(=O)[C@@H]2[C@H]1[C@]1([H])C=C[C@@]2([H])C1 KNDQHSIWLOJIGP-UMRXKNAASA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- 125000002030 1,2-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([*:2])C([H])=C1[H] 0.000 description 1
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 description 1
- GVPODVKBTHCGFU-UHFFFAOYSA-N 2,4,6-tribromoaniline Chemical compound NC1=C(Br)C=C(Br)C=C1Br GVPODVKBTHCGFU-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- LJBWJFWNFUKAGS-UHFFFAOYSA-N 2-[bis(2-hydroxyphenyl)methyl]phenol Chemical compound OC1=CC=CC=C1C(C=1C(=CC=CC=1)O)C1=CC=CC=C1O LJBWJFWNFUKAGS-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- ALKYHXVLJMQRLQ-UHFFFAOYSA-N 3-Hydroxy-2-naphthoate Chemical compound C1=CC=C2C=C(O)C(C(=O)O)=CC2=C1 ALKYHXVLJMQRLQ-UHFFFAOYSA-N 0.000 description 1
- IBFJDBNISOJRCW-UHFFFAOYSA-N 3-methylphthalic acid Chemical compound CC1=CC=CC(C(O)=O)=C1C(O)=O IBFJDBNISOJRCW-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- ODJUOZPKKHIEOZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3,5-dimethylphenyl)propan-2-yl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=C(C)C=2)=C1 ODJUOZPKKHIEOZ-UHFFFAOYSA-N 0.000 description 1
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 1
- QXBYUPMEYVDXIQ-UHFFFAOYSA-N 4-methyl-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound CC1CCCC2C(=O)OC(=O)C12 QXBYUPMEYVDXIQ-UHFFFAOYSA-N 0.000 description 1
- XRBNDLYHPCVYGC-UHFFFAOYSA-N 4-phenylbenzene-1,2,3-triol Chemical group OC1=C(O)C(O)=CC=C1C1=CC=CC=C1 XRBNDLYHPCVYGC-UHFFFAOYSA-N 0.000 description 1
- 125000006043 5-hexenyl group Chemical group 0.000 description 1
- XBWHBPMCIGBGTA-UHFFFAOYSA-N 5-methyl-2-oxaspiro[3.5]non-5-ene-1,3-dione Chemical compound CC1=CCCCC11C(=O)OC1=O XBWHBPMCIGBGTA-UHFFFAOYSA-N 0.000 description 1
- FKBMTBAXDISZGN-UHFFFAOYSA-N 5-methyl-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1C(C)CCC2C(=O)OC(=O)C12 FKBMTBAXDISZGN-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 description 1
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 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
- 229930185605 Bisphenol Natural products 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229960004050 aminobenzoic acid Drugs 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- IVVOCRBADNIWDM-UHFFFAOYSA-N bicyclo[2.2.1]heptane-2,3-dicarboxylic acid Chemical compound C1CC2C(C(O)=O)C(C(=O)O)C1C2 IVVOCRBADNIWDM-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- OZEHOHQZIRILDX-UHFFFAOYSA-N ctk1b7797 Chemical compound O=C1OC(=O)C2C1C1(C)CC2CC1 OZEHOHQZIRILDX-UHFFFAOYSA-N 0.000 description 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- YMHQVDAATAEZLO-UHFFFAOYSA-N cyclohexane-1,1-diamine Chemical compound NC1(N)CCCCC1 YMHQVDAATAEZLO-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229920006332 epoxy adhesive Polymers 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RCNRJBWHLARWRP-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane;platinum Chemical compound [Pt].C=C[Si](C)(C)O[Si](C)(C)C=C RCNRJBWHLARWRP-UHFFFAOYSA-N 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 235000011187 glycerol Nutrition 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
- VBZWSGALLODQNC-UHFFFAOYSA-N hexafluoroacetone Chemical compound FC(F)(F)C(=O)C(F)(F)F VBZWSGALLODQNC-UHFFFAOYSA-N 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
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000003999 initiator Substances 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
- 239000007788 liquid Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- ZXQPRTUUOOOZAS-UHFFFAOYSA-N oxiran-2-yl(oxiran-2-ylmethoxy)methanamine Chemical compound C1OC1C(N)OCC1CO1 ZXQPRTUUOOOZAS-UHFFFAOYSA-N 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- PMOIAJVKYNVHQE-UHFFFAOYSA-N phosphanium;bromide Chemical group [PH4+].[Br-] PMOIAJVKYNVHQE-UHFFFAOYSA-N 0.000 description 1
- 150000004714 phosphonium salts Chemical group 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
- H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L24/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
- H01L24/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
- C08G59/306—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing silicon
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3254—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen
- C08G59/3281—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen containing silicon
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
- C09J9/02—Electrically-conducting adhesives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/124—Intrinsically conductive polymers
- H01B1/128—Intrinsically conductive polymers comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes
-
- 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
- H01L33/58—Optical field-shaping elements
- H01L33/60—Reflective elements
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/10—Bump connectors; Manufacturing methods related thereto
- H01L2224/15—Structure, shape, material or disposition of the bump connectors after the connecting process
- H01L2224/16—Structure, shape, material or disposition of the bump connectors after the connecting process of an individual bump connector
- H01L2224/161—Disposition
- H01L2224/16151—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/16221—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/16225—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
- H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
- H01L2224/29001—Core members of the layer connector
- H01L2224/29099—Material
- H01L2224/29198—Material with a principal constituent of the material being a combination of two or more materials in the form of a matrix with a filler, i.e. being a hybrid material, e.g. segmented structures, foams
- H01L2224/29298—Fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
- H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
- H01L2224/321—Disposition
- H01L2224/32151—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/32221—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/32225—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
- H01L2224/45—Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
- H01L2224/45001—Core members of the connector
- H01L2224/45099—Material
- H01L2224/451—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof
- H01L2224/45138—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
- H01L2224/45144—Gold (Au) as principal constituent
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/4805—Shape
- H01L2224/4809—Loop shape
- H01L2224/48091—Arched
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/481—Disposition
- H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/48225—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
- H01L2224/48227—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation connecting the wire to a bond pad of the item
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
- H01L2224/732—Location after the connecting process
- H01L2224/73201—Location after the connecting process on the same surface
- H01L2224/73203—Bump and layer connectors
- H01L2224/73204—Bump and layer connectors the bump connector being embedded into the layer connector
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
- H01L2224/732—Location after the connecting process
- H01L2224/73251—Location after the connecting process on different surfaces
- H01L2224/73265—Layer and wire connectors
-
- 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
- H01L2924/06—Polymers
- H01L2924/078—Adhesive characteristics other than chemical
- H01L2924/07802—Adhesive characteristics other than chemical not being an ohmic electrical conductor
-
- 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
- H01L2924/10—Details of semiconductor or other solid state devices to be connected
- H01L2924/11—Device type
- H01L2924/12—Passive devices, e.g. 2 terminal devices
- H01L2924/1204—Optical Diode
- H01L2924/12041—LED
-
- 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
- H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
- H01L2924/181—Encapsulation
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Led Device Packages (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Epoxy Resins (AREA)
Description
本発明は、熱硬化性樹脂組成物、当該熱硬化型エポキシ系接着剤を利用した光反射性異方性導電接着剤、その接着剤を用いて発光素子を配線板に実装してなる発光装置に関する。 The present invention relates to a thermosetting resin composition, a light-reflective anisotropic conductive adhesive using the thermosetting epoxy adhesive, and a light-emitting device in which a light-emitting element is mounted on a wiring board using the adhesive. About.
従来、発光ダイオード（ＬＥＤ）素子の実装に用いた異方性導電ペーストや異方性導電フィルム等の異方性導電接着剤の絶縁性接着成分の熱や光による変色に伴ってＬＥＤ素子の発光効率（光取り出し効率）が低下することを防止するために、ＬＥＤ封止用樹脂として上市されている、耐熱性、耐光性に優れた２液硬化型メチルシリコーン樹脂や２液硬化型フェニルシリコーン樹脂（非特許文献１）を、異方性導電ペーストや異方性導電フィルム中の絶縁性接着成分に採用することが試みられている。 Conventionally, light emission of LED elements accompanying discoloration of insulating adhesive components of anisotropic conductive adhesives such as anisotropic conductive pastes and anisotropic conductive films used for mounting of light emitting diode (LED) elements due to heat or light discoloration Two-component curable methylsilicone resin and two-component curable phenylsilicone resin that are marketed as LED sealing resins to prevent the efficiency (light extraction efficiency) from decreasing. It has been attempted to employ (Non-Patent Document 1) as an insulating adhesive component in an anisotropic conductive paste or anisotropic conductive film.
また、異方性導電接着剤の絶縁性接着成分の変色防止という観点とは別に、ＬＥＤ素子を構造的に改良することによりその発光効率を改善しようとすることも行われている。たとえば、阻止の発光ダイオード（ＬＥＤ）素子を使用した旧タイプの発光装置の構造は、図５に示すように、基板３１上にダイボンド接着剤３２でＬＥＤ素子３３を接合し、その上面のｐ電極３４とｎ電極３５とを、基板３１の接続端子３６に金ワイヤ３７でワイヤボンディングし、ＬＥＤ素子３３全体を透明モールド樹脂３８で封止したものとなっているが、図５の発光装置の場合、ＬＥＤ素子３３が発する光のうち、上面側に出射する４００〜５００ｎｍの波長の光を金ワイヤが吸収し、また、下面側に出射した光の一部がダイボンド接着剤３２により吸収されてしまい、ＬＥＤ素子３３の発光効率が低下するという問題があるところ、図６に示すように、ＬＥＤ素子３３をフリップチップ実装することが提案されている（特許文献１）。
Further, apart from the viewpoint of preventing discoloration of the insulating adhesive component of the anisotropic conductive adhesive, attempts have been made to improve the luminous efficiency by structurally improving the LED element. For example, in the structure of an old type light emitting device using a blocking light emitting diode (LED) element, an
このフリップチップ実装技術においては、ｐ電極３４とｎ電極３５とにバンプ３９がそれぞれ形成されており、更に、ＬＥＤ素子３３のバンプ形成面には、ｐ電極３４とｎ電極３５と絶縁されるように光反射層４０が設けられている。そして、ＬＥＤ素子３３と基板３１とは、異方性導電ペースト４１や異方性導電フィルム（図示せず）を用い、それらを硬化させて接続固定される。このため、図６の発光装置においては、ＬＥＤ素子３３の上方への出射した光は金ワイヤで吸収されず、下方へ出射した光の殆どは光反射層４０で反射して上方に出射するので、発光効率（光取り出し効率）が低下しない。
In this flip chip mounting technology,
しかしながら、非特許文献１に記載されているような２液硬化型メチルシリコーン樹脂や２液硬化型フェニルシリコーン樹脂を異方性導電接着剤の絶縁性接着成分に採用した場合、熱や光により絶縁性接着成分の変色は抑制できるものの、実装基板に対するＬＥＤ素子の剥離強度（ダイシェア強度）が実用に適さないレベルとなってしまうという問題があった。
However, when a two-component curable methylsilicone resin or a two-component curable phenylsilicone resin as described in Non-Patent
また、特許文献１の技術ではＬＥＤ素子３３に光反射層４０を、ｐ電極３４とｎ電極３５と絶縁するように金属蒸着法などにより設けなければならず、製造上、コストアップが避けられないという問題があり、他方、光反射層４０を設けない場合には、硬化した異方性導電ペーストや異方性導電フィルム中の金、ニッケルあるいは銅で被覆された導電粒子の表面は茶色乃至は暗茶色を呈し、また、導電粒子を分散させているエポキシ樹脂バインダー自体も、その硬化のために常用されるイミダゾール系潜在性硬化剤のために茶色を呈しており、発光素子が発した光の発光効率（光取り出し効率）を向上させることが困難であるという問題がある。
Further, in the technique of
本発明の第１の目的は、以上の従来の技術の問題点を解決することであり、発光ダイオード（ＬＥＤ）素子等の発光素子を配線板に異方性導電接着剤を用いてフリップチップ実装して発光装置を製造する際に、熱や光により変色しにくい上に実用上十分なダイシェア強度を示す異方性導電接着剤に適した絶縁性接着成分としての熱硬化性樹脂組成物を提供することであり、更に、第２の目的は、製造コストの増大を招くような光反射層をＬＥＤ素子に設けなくても発光効率を改善できる光反射性異方性導電接着剤を提供することであり、更に、そのような光反射性異方性導電接着剤を使用して発光素子を配線板にフリップチップ実装してなる発光装置を提供することである。 SUMMARY OF THE INVENTION A first object of the present invention is to solve the above-mentioned problems of the prior art, and to mount a light emitting element such as a light emitting diode (LED) element on a wiring board using an anisotropic conductive adhesive. Provides a thermosetting resin composition as an insulating adhesive component suitable for anisotropic conductive adhesives that are resistant to discoloration by heat and light and exhibit practically sufficient die shear strength when manufacturing light emitting devices Furthermore, the second object is to provide a light-reflective anisotropic conductive adhesive that can improve the light emission efficiency without providing a light-reflective layer on the LED element that causes an increase in manufacturing cost. Furthermore, it is to provide a light emitting device in which a light emitting element is flip-chip mounted on a wiring board using such a light reflective anisotropic conductive adhesive.
本発明者らは、第１の目的に関し、異方性導電接着剤の絶縁性接着成分として、特定の構造を有するエポキシ基含有シロキサン化合物、より具体的にはテトラキス（ジグリシジルイソシアヌリル変性シロキシ）シランを使用することにより、熱や光により異方性導電接着剤が変色してしまうことを防止でき、しかも実用上十分なダイシェア強度を示すことを見出した。また、本発明者らは、第２の目的に関し、異方性導電接着剤そのものに光反射機能を持たせれば、発光効率を低下させないようにできるとの仮定の下、異方性導電接着剤に、光反射性絶縁粒子を配合することにより、発光素子の発光効率を低下させないようにできることを見出した。そして、これらの知見に基づき本発明を完成させるに至った。 With regard to the first object, the present inventors have disclosed an epoxy group-containing siloxane compound having a specific structure as an insulating adhesive component of an anisotropic conductive adhesive, more specifically tetrakis (diglycidyl isocyanuryl-modified siloxy). It was found that the use of silane can prevent the anisotropic conductive adhesive from being discolored by heat or light, and exhibits practically sufficient die shear strength. In addition, regarding the second object, the inventors of the present invention have assumed that the anisotropic conductive adhesive itself has a light reflecting function, so that the luminous efficiency can be prevented from being lowered. Furthermore, it has been found that the light-emitting efficiency of the light-emitting element can be prevented from being lowered by blending light-reflective insulating particles. And based on these knowledge, it came to complete this invention.
即ち、本発明は、第１の目的を達成すべく、式（１）で表されるエポキシ基含有シロキサン化合物と、エポキシ樹脂用硬化剤とを含有することを特徴とする熱硬化性樹脂組成物を提供する。 That is, this invention contains the epoxy group containing siloxane compound represented by Formula (1), and the hardening | curing agent for epoxy resins, in order to achieve the 1st objective, The thermosetting resin composition characterized by the above-mentioned. I will provide a.
式（１）中、置換基Ｒは独立的にアルキル基又はフェニル基である。連結基Ａは、独立的に２価の炭化水素基である。置換基Ｒ１及びＲ２は、独立的にエポキシ基含有有機基、アルキル基又はアリール基であるが、Ｒ１及びＲ２の少なくとも一方がエポキシ基含有有機基である。 In the formula (1), the substituent R is independently an alkyl group or a phenyl group. The linking group A is independently a divalent hydrocarbon group. The substituents R1 and R2 are independently an epoxy group-containing organic group, an alkyl group, or an aryl group, and at least one of R1 and R2 is an epoxy group-containing organic group.
また、本発明は、第２の目的を達成すべく、発光素子を配線板に異方性導電接続するために使用する光反射性異方性導電接着剤であって、式（１）で表されるエポキシ基含有シロキサン化合物と、エポキシ樹脂用硬化剤とを含有する本発明の熱硬化性樹脂組成物、導電粒子及び光反射性絶縁粒子を含有することを特徴とする光反射性異方性導電接着剤を提供する。 The present invention also provides a light-reflective anisotropic conductive adhesive used for anisotropic conductive connection of a light emitting element to a wiring board in order to achieve the second object, represented by the formula (1). A light-reflective anisotropy comprising the thermosetting resin composition of the present invention, the conductive particles, and the light-reflective insulating particles, comprising the epoxy group-containing siloxane compound and the epoxy resin curing agent A conductive adhesive is provided.
また、本発明は、この光反射性異方性導電接着剤の特に好ましい態様として、導電粒子が、金属材料により被覆されているコア粒子と、その表面に酸化チタン粒子、窒化ホウ素粒子、酸化亜鉛粒子又は酸化アルミニウム粒子から選択された少なくとも一種の無機粒子から形成された光反射層とからなる光反射性導電粒子である光反射性異方性導電接着剤を提供する。 Further, in the present invention, as a particularly preferred embodiment of the light-reflective anisotropic conductive adhesive, core particles in which conductive particles are coated with a metal material, titanium oxide particles, boron nitride particles, and zinc oxide on the surface thereof are used. Provided is a light-reflective anisotropic conductive adhesive which is a light-reflective conductive particle comprising a light-reflecting layer formed from at least one kind of inorganic particles selected from particles or aluminum oxide particles.
また、本発明は、上述の光反射性異方性導電接着剤を介して、発光素子をフリップチップ方式で配線板に実装されてなる発光装置を提供する。 The present invention also provides a light-emitting device in which a light-emitting element is mounted on a wiring board by a flip-chip method through the above-described light-reflective anisotropic conductive adhesive.
発光素子を配線板に異方性導電接続するために使用する異方性導電接着剤のバインダーとして有用な本発明の熱硬化性樹脂組成物は、エポキシ樹脂用硬化剤で硬化する式（１）で表されるエポキシ基含有シロキサン化合物を含有する。このシロキサン化合物は、その中心のケイ素原子に対して４つのシリレンオキシ基が結合しており、しかもそれぞれのシリレンオキシ基の末端に、エポキシ基含有有機基で置換されたイソシアヌリルアルキル基が結合した構造を有している。このため、熱や光により異方性導電接着剤が変色してしまうことを防止でき、しかも実用上十分なダイシェア強度を実現することができる。また、この熱硬化性樹脂組成物は、異方性導電接着剤だけでなく、絶縁性接着剤や導電接着剤のバインダーとしても有用である。 The thermosetting resin composition of the present invention useful as a binder for an anisotropic conductive adhesive used for anisotropic conductive connection of a light emitting element to a wiring board is a formula (1) that cures with a curing agent for epoxy resin. The epoxy group containing siloxane compound represented by these is contained. In this siloxane compound, four silyleneoxy groups are bonded to the center silicon atom, and an isocyanurylalkyl group substituted with an epoxy group-containing organic group is bonded to the terminal of each silyleneoxy group. It has the structure. For this reason, it can prevent that an anisotropic conductive adhesive discolors with a heat | fever or light, and also can implement | achieve practically sufficient die shear strength. Moreover, this thermosetting resin composition is useful not only as an anisotropic conductive adhesive but also as a binder for an insulating adhesive or a conductive adhesive.
また、本発明の光反射性異方性導電接着剤は、熱硬化性樹脂組成物の効果に加え、光反射性絶縁粒子を含有しているから、光を反射することができる。特に、光反射性絶縁粒子が、酸化チタン、窒化ホウ素、酸化亜鉛及び酸化アルミニウムからなる群より選択される少なくとも一種の無機粒子、又は鱗片状もしくは球状金属粒子の表面を絶縁性樹脂で被覆した樹脂被覆金属粒子である場合には、粒子自体がほぼ白色であるため、可視光に対する反射特性の波長依存性が小さく、従って、発光効率を向上させることができ、しかも発光素子の発光色をそのままの色で反射させることができる。 Moreover, since the light-reflective anisotropic conductive adhesive of this invention contains the light-reflective insulating particle in addition to the effect of a thermosetting resin composition, it can reflect light. In particular, the light-reflective insulating particles are at least one inorganic particle selected from the group consisting of titanium oxide, boron nitride, zinc oxide and aluminum oxide, or a resin in which the surface of scaly or spherical metal particles is coated with an insulating resin. In the case of coated metal particles, since the particles themselves are almost white, the wavelength dependency of the reflection characteristic with respect to visible light is small, so that the light emission efficiency can be improved and the light emission color of the light emitting element remains unchanged. Can be reflected by color.
また、更に、導電粒子として、金属材料で被覆されているコア粒子と、その表面に酸化チタン粒子、窒化ホウ素粒子、酸化亜鉛粒子又は酸化アルミニウム粒子から形成された白色〜灰色の光反射層とから構成されている光反射性導電粒子を使用した場合、この光反射性導電粒子自体が白色〜灰色を呈しているため、可視光に対する反射特性の波長依存性が小さく、従って、発光効率を更に向上させることができ、しかも発光素子の発光色をそのままの色で反射させることができる。 Further, as conductive particles, core particles coated with a metal material, and a white to gray light reflecting layer formed on the surface thereof from titanium oxide particles, boron nitride particles, zinc oxide particles or aluminum oxide particles. When the configured light-reflective conductive particles are used, the light-reflective conductive particles themselves exhibit a white to gray color, so that the wavelength dependency of the reflection characteristic with respect to visible light is small, and thus the luminous efficiency is further improved. In addition, the emission color of the light emitting element can be reflected as it is.
本発明の熱硬化性樹脂組成物は、式（１）で表されるエポキシ基含有シロキサン化合物と、エポキシ樹脂用硬化剤とを含有する。この熱硬化性樹脂組成物は、発光素子を配線板に異方性導電接続するために使用する光反射性異方性導電接着剤のバインダーとして有用なものである。 The thermosetting resin composition of this invention contains the epoxy group containing siloxane compound represented by Formula (1), and the hardening | curing agent for epoxy resins. This thermosetting resin composition is useful as a binder for a light-reflective anisotropic conductive adhesive used for anisotropic conductive connection of a light emitting element to a wiring board.
＜熱硬化性樹脂組成物＞
前述したとおり、本発明の熱硬化性樹脂組成物は、式（１）で表されるエポキシ基含有シロキサン化合物と、エポキシ樹脂用硬化剤とを含有する。式（１）で表されるエポキシ基含有シロキサン化合物を含有することにより、熱や光により異方性導電接着剤が変色してしまうことを防止でき、しかも実用上十分なダイシェア強度を実現することができる。
<Thermosetting resin composition>
As described above, the thermosetting resin composition of the present invention contains an epoxy group-containing siloxane compound represented by formula (1) and a curing agent for epoxy resin. By containing the epoxy group-containing siloxane compound represented by the formula (1), it is possible to prevent the anisotropic conductive adhesive from being discolored by heat or light, and to achieve practically sufficient die shear strength. Can do.
＜置換基Ｒ＞
式（１）中、Ｒは独立的にアルキル基又はフェニル基である。変色し難さの点からアルキル基が好ましい。アルキル基としては、基材への接着性の点から炭素数１〜６のアルキル基、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、へプチル基、イソへプチル基、ヘキシル基が好ましく、中でも、炭素数１〜３の低級アルキル基、例えば、メチル基、エチル基、プロピル基、イソプロピル基が好ましい。特に、熱光耐黄変性の点からメチル基が好ましい。
<Substituent R>
In formula (1), R is an alkyl group or a phenyl group independently. From the viewpoint of difficulty in discoloration, an alkyl group is preferable. As the alkyl group, an alkyl group having 1 to 6 carbon atoms from the viewpoint of adhesion to a substrate, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert- A butyl group, a heptyl group, an isoheptyl group, and a hexyl group are preferable, and among them, a lower alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, a propyl group, and an isopropyl group are preferable. In particular, a methyl group is preferable from the viewpoint of heat-resistant yellowing resistance.
＜連結基Ａ＞
Ａは、独立的に２価の炭化水素基、例えば、炭素数２以上のアルキレン基、アリーレン基、アラルキレン基であるが、変色し難さの点から炭素数２以上のアルキレン基が好ましい。
<Linking group A>
A is independently a divalent hydrocarbon group, for example, an alkylene group having 2 or more carbon atoms, an arylene group, or an aralkylene group, and an alkylene group having 2 or more carbon atoms is preferable from the viewpoint of difficulty in discoloration.
炭素数２以上のアルキレン基としては、例えば、炭素数６までのアルキレン基が好ましく、具体的には、ジメチレン基、トリメチレン基、テトラメチレン基、ペンタメチレン基、ヘキサメチレン基が挙げられる。これらのアルキレン基には、メチル基等のアルキル基が結合してもよい。 As an alkylene group having 2 or more carbon atoms, for example, an alkylene group having up to 6 carbon atoms is preferable, and specific examples include a dimethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group. An alkyl group such as a methyl group may be bonded to these alkylene groups.
アリーレン基としては、例えば、１，４−フェニレン基、１，３−フェニレン基、１，２−フェニレン基、１，４−ナフタレン基、１，５−ナフタレン基が挙げられる。好ましくは、１，４−フェニレン基である。 Examples of the arylene group include a 1,4-phenylene group, a 1,3-phenylene group, a 1,2-phenylene group, a 1,4-naphthalene group, and a 1,5-naphthalene group. A 1,4-phenylene group is preferable.
アラルキレン基としては、例えば、フェニルジメチレン基、フェニルトリメチレン基が挙げられる。 Examples of the aralkylene group include a phenyl dimethylene group and a phenyl trimethylene group.
＜置換基Ｒ１、Ｒ２＞
置換基Ｒ１、Ｒ２は、独立的にエポキシ基含有有機基、アルキル基又はアリール基であるが、Ｒ１及びＲ２の少なくとも一方、好ましくは双方がエポキシ基含有有機基である。
<Substituents R1, R2>
The substituents R1 and R2 are independently an epoxy group-containing organic group, an alkyl group, or an aryl group, but at least one of R1 and R2, preferably both, is an epoxy group-containing organic group.
エポキシ基含有有機基としては、例えば、グリシジル基、１，２−エポキシ−５−ヘキセニル基、２，６−ジメチル−２，３−エポキシ−７−オクテニル基、１，２−エポキシ−９−デセニル基が挙げられる。中でも、基材との接着性の点からグリシジル基が好ましい。 Examples of the epoxy group-containing organic group include glycidyl group, 1,2-epoxy-5-hexenyl group, 2,6-dimethyl-2,3-epoxy-7-octenyl group, 1,2-epoxy-9-decenyl. Groups. Among these, a glycidyl group is preferable from the viewpoint of adhesiveness with a substrate.
従って、式（１）で表されるエポキシ基含有シロキサン化合物の好ましい態様は、置換基Ｒが炭素数１〜３の低級アルキル基であり、連結基Ａが炭素数２〜６のアルキレン基であり、置換基Ｒ１、Ｒ２が共にエポキシ基含有有機基である態様である。 Accordingly, in a preferred embodiment of the epoxy group-containing siloxane compound represented by the formula (1), the substituent R is a lower alkyl group having 1 to 3 carbon atoms, and the linking group A is an alkylene group having 2 to 6 carbon atoms. The substituents R1 and R2 are both epoxy group-containing organic groups.
式（１）で表されるエポキシ基含有シロキサン化合物の特に好ましい態様は、以下の式（１ａ）で表される化合物である。 A particularly preferred embodiment of the epoxy group-containing siloxane compound represented by the formula (1) is a compound represented by the following formula (1a).
式（１）乃至（１ａ）で表されるエポキシ基含有シロキサン化合物の熱硬化性樹脂組成物中の含有量は、少なすぎると接着機能が低下する傾向があり、多すぎると未硬化エポキシ成分が多くなるので、好ましくは４５〜６５質量％、より好ましくは５０〜６０質量％である。 When the content of the epoxy group-containing siloxane compound represented by the formulas (1) to (1a) in the thermosetting resin composition is too small, the adhesive function tends to be lowered. Since it increases, Preferably it is 45-65 mass%, More preferably, it is 50-60 mass%.
また、式（１）で表されるエポキシ基含有シロキサン化合物は、以下の反応式（いわゆるハイドロシリレーション反応）に示すように、式（ａ）のテトラキス（ハイドロジェンシリレンオキシシランと、式（ｂ）のイソシアヌレートとを均一に混合した後、カールステッド（Ｋａｒｓｔｅｄｔ）触媒（１，３−ジビニル−１，１，３，３−テトラメチルジシロキサン白金（０）錯体溶液）の存在下で室温〜１５０℃に加熱することにより製造することができる。反応混合物からは、常法（濃縮処理・カラム処理等）により式（１）の化合物を単離することができる。 In addition, the epoxy group-containing siloxane compound represented by the formula (1), as shown in the following reaction formula (so-called hydrosilylation reaction), tetrakis (hydrogensilyleneoxysilane) of the formula (a) and the formula (b ) Isocyanurate, and then in the presence of a Karlstedt catalyst (1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum (0) complex solution) at room temperature to The compound of the formula (1) can be isolated from the reaction mixture by a conventional method (concentration treatment, column treatment, etc.).
化学反応式において、Ｒ、Ａ、Ｒ１及びＲ２は、式（１）において説明したとおりである。Ａ′は、連結基Ａに対応した末端アルケニル基である。例えば、Ａがジメチレン基である場合にはビニル基であり、トリメチレン基である場合にアリル基であり、ヘキサメチレン基である場合には、５−ヘキセニル基である。 In the chemical reaction formula, R, A, R1 and R2 are as described in formula (1). A ′ is a terminal alkenyl group corresponding to the linking group A. For example, when A is a dimethylene group, it is a vinyl group, when it is a trimethylene group, it is an allyl group, and when it is a hexamethylene group, it is a 5-hexenyl group.
式（１）のエポキシ基含有シロキサン化合物の特に好ましい態様である式（１ａ）の化合物も、以下の反応式に従って、式（ａ′）のテトラキス（ハイドロジェンジメチルシロキシ）シランと、式（ｂ′）の１−アリル−３，５−ジグリシジルイソシアヌレートとをハイドロシリレーション反応させることにより製造することができる。 The compound of formula (1a), which is a particularly preferred embodiment of the epoxy group-containing siloxane compound of formula (1), is also represented by the following formula: tetrakis (hydrogendimethylsiloxy) silane of formula (a ′) and formula (b ′ ) Of 1-allyl-3,5-diglycidyl isocyanurate.
本発明の熱硬化性樹脂組成物は、式（１）のエポキシ基含有シロキサン化合物の他に、発明の効果を損なわない範囲で、複素環系エポキシ化合物や脂環式エポキシ化合物や水素添加エポキシ化合物などを含有することができる。 In addition to the epoxy group-containing siloxane compound of the formula (1), the thermosetting resin composition of the present invention is a heterocyclic epoxy compound, an alicyclic epoxy compound, or a hydrogenated epoxy compound as long as the effects of the invention are not impaired. Etc. can be contained.
複素環系エポキシ化合物としては、トリアジン環を有するエポキシ化合物、例えば１，３，５−トリス（２，３−エポキシプロピル）−１，３，５−トリアジン−２，４，６−（１Ｈ，３Ｈ，５Ｈ）−トリオン（換言すれば、トリグリシジルイソシヌレート）を挙げることができる。 As the heterocyclic epoxy compound, an epoxy compound having a triazine ring, for example, 1,3,5-tris (2,3-epoxypropyl) -1,3,5-triazine-2,4,6- (1H, 3H) , 5H) -trione (in other words, triglycidyl isocyanurate).
脂環式エポキシ化合物としては、分子内に２つ以上のエポキシ基を有するものが好ましく挙げられる。これらは液状であっても、固体状であってもよい。具体的には、グリシジルヘキサヒドロビスフェノールＡ、３，４−エポキシシクロヘキセニルメチル−３′，４′−エポキシシクロヘキセンカルボキシレート等を挙げることができる。中でも、硬化物にＬＥＤ素子の実装等に適した光透過性を確保でき、速硬化性にも優れている点から、グリシジルヘキサヒドロビスフェノールＡ、３，４−エポキシシクロヘキセニルメチル−３′，４′−エポキシシクロヘキセンカルボキシレートを好ましく使用することができる。 Preferred examples of the alicyclic epoxy compound include those having two or more epoxy groups in the molecule. These may be liquid or solid. Specific examples include glycidyl hexahydrobisphenol A, 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate, and the like. Among them, glycidyl hexahydrobisphenol A, 3,4-epoxycyclohexenylmethyl-3 ′, 4 is preferable because it can ensure light transmission suitable for mounting LED elements on the cured product and is excellent in rapid curing. '-Epoxycyclohexene carboxylate can be preferably used.
水素添加エポキシ化合物としては、前述の複素環系エポキシ化合物や脂環式エポキシ化合物の水素添加物や、その他公知の水素添加エポキシ樹脂を使用することできる。 As the hydrogenated epoxy compound, hydrogenated products of the above-described heterocyclic epoxy compounds and alicyclic epoxy compounds, and other known hydrogenated epoxy resins can be used.
これらの脂環式エポキシ化合物や複素環系エポキシ化合物や水素添加エポキシ化合物は、式（１）のエポキシ基含有シロキサン化合物に対し、単独で併用してもよいが、２種以上を併用してもよい。また、これらのエポキシ化合物に加えて本発明の効果を損なわない限り、他のエポキシ化合物を併用してもよい。例えば、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳ、テトラメチルビスフェノールＡ、ジアリールビスフェノールＡ、ハイドロキノン、カテコール、レゾルシン、クレゾール、テトラブロモビスフェノールＡ、トリヒドロキシビフェニル、ベンゾフェノン、ビスレゾルシノール、ビスフェノールヘキサフルオロアセトン、テトラメチルビスフェノールＡ、テトラメチルビスフェノールＦ、トリス（ヒドロキシフェニル）メタン、ビキシレノール、フェノールノボラック、クレゾールノボラックなどの多価フェノールとエピクロルヒドリンとを反応させて得られるグリシジルエーテル； グリセリン、ネオペンチルグリコール、エチレングリコール、プロピレングリコール、チレングリコール、ヘキシレングリコール、ポリエチレングリコール、ポリプロピレングリコールなどの脂肪族多価アルコールとエピクロルヒドリンとを反応させて得られるポリグリシジルエーテル； ｐ−オキシ安息香酸、β−オキシナフトエ酸のようなヒドロキシカルボン酸とエピクロルヒドリンとを反応させて得られるグリシジルエーテルエステル； フタル酸、メチルフタル酸、イソフタル酸、テレフタル酸、テトラハイドロフタル酸、エンドメチレンテトラハイドロフタル酸、エンドメチレンヘキサハイドロフタル酸、トリメリット酸、重合脂肪酸のようなポリカルボン酸から得られるポリグリシジルエステル； アミノフェノール、アミノアルキルフェノールから得られるグリシジルアミノグリシジルエーテル； アミノ安息香酸から得られるグリシジルアミノグリシジルエステル； アニリン、トルイジン、トリブロムアニリン、キシリレンジアミン、ジアミノシクロヘキサン、ビスアミノメチルシクロヘキサン、４，４′−ジアミノジフェニルメタン、４，４′−ジアミノジフェニルスルホンなどから得られるグリシジルアミン； エポキシ化ポリオレフィン等の公知のエポキシ樹脂類が挙げられる。 These alicyclic epoxy compounds, heterocyclic epoxy compounds and hydrogenated epoxy compounds may be used alone or in combination of two or more with respect to the epoxy group-containing siloxane compound of formula (1). Good. In addition to these epoxy compounds, other epoxy compounds may be used in combination as long as the effects of the present invention are not impaired. For example, bisphenol A, bisphenol F, bisphenol S, tetramethylbisphenol A, diarylbisphenol A, hydroquinone, catechol, resorcin, cresol, tetrabromobisphenol A, trihydroxybiphenyl, benzophenone, bisresorcinol, bisphenol hexafluoroacetone, tetramethylbisphenol G, glycidyl ether obtained by reacting polychlorophenol such as A, tetramethylbisphenol F, tris (hydroxyphenyl) methane, bixylenol, phenol novolak, cresol novolak and epichlorohydrin; glycerin, neopentyl glycol, ethylene glycol, propylene glycol , Tylene glycol, hexylene glycol, polyethylene Polyglycidyl ether obtained by reacting aliphatic polyhydric alcohols such as polyglycol and polypropylene glycol with epichlorohydrin; obtained by reacting hydroxycarboxylic acid such as p-oxybenzoic acid and β-oxynaphthoic acid with epichlorohydrin Glycidyl ether esters obtained from phthalic acid, methylphthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, endomethylenetetrahydrophthalic acid, endomethylenehexahydrophthalic acid, trimellitic acid, polycarboxylic acids such as polymerized fatty acids Polyglycidyl ester obtained; glycidyl aminoglycidyl ether obtained from aminophenol and aminoalkylphenol; glycidyl aminoglycidyl ester obtained from aminobenzoic acid; Glycidylamine obtained from niline, toluidine, tribromoaniline, xylylenediamine, diaminocyclohexane, bisaminomethylcyclohexane, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, etc .; known epoxidized polyolefin, etc. Examples include epoxy resins.
エポキシ樹脂用硬化剤としては、公知のエポキシ樹脂用硬化剤を使用することができる。例えば、アミン系硬化剤、ポリアミド系硬化剤、酸無水物系硬化剤、イミダゾール系硬化剤、ポリメルカプタン系硬化剤、ポリスルフィド系硬化剤、三フッ化ホウ素−アミン錯体系硬化剤、ジシアンジアミド、有機酸ヒドラジッド等の中から選択して使用することができる。中でも、光透過性、耐熱性等の観点から酸無水物系硬化剤を好ましく使用することができる。 As the curing agent for epoxy resin, a known curing agent for epoxy resin can be used. For example, amine curing agent, polyamide curing agent, acid anhydride curing agent, imidazole curing agent, polymercaptan curing agent, polysulfide curing agent, boron trifluoride-amine complex curing agent, dicyandiamide, organic acid It can be selected from among hydrazides and the like. Among these, acid anhydride curing agents can be preferably used from the viewpoints of light transmittance, heat resistance, and the like.
酸無水物系硬化剤としては、無水コハク酸、無水フタル酸、無水マレイン酸、無水トリメリット酸、無水ピロメリット酸、ヘキサヒドロ無水フタル酸、３−メチル−ヘキサヒドロ無水フタル酸、４−メチル−ヘキサヒドロ無水フタル酸、あるいは４−メチル−ヘキサヒドロ無水フタル酸とヘキサヒドロ無水フタル酸との混合物、テトラヒドロ無水フタル酸、メチル-テトラヒドロ無水フタル酸、無水ナジック酸、無水メチルナジック酸、ノルボルナン−２，３−ジカルボン酸無水物、メチルノルボルナン−２，３−ジカルボン酸無水物、メチルシクロヘキセンジカルボン酸無水物等を挙げることができる。 Examples of acid anhydride curing agents include succinic anhydride, phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, 3-methyl-hexahydrophthalic anhydride, 4-methyl-hexahydro. Phthalic anhydride, or a mixture of 4-methyl-hexahydrophthalic anhydride and hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl-tetrahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, norbornane-2,3-dicarboxylic acid An acid anhydride, methylnorbornane-2,3-dicarboxylic acid anhydride, methylcyclohexene dicarboxylic acid anhydride, etc. can be mentioned.
酸無水物系硬化剤等のエポキシ樹脂用硬化剤の熱硬化性樹脂組成物中の配合量は、式（１）で表されるエポキシ基含有シロキサン化合物１００質量部に対して、少なすぎると未硬化エポキシ成分が多くなり、多すぎると余剰の硬化剤の影響で被着体材料の腐食が促進される傾向があるので、好ましくは、５０〜１２０質量部、より好ましくは６０〜１００質量部である。 If the amount of the epoxy resin curing agent such as an acid anhydride curing agent in the thermosetting resin composition is too small relative to 100 parts by mass of the epoxy group-containing siloxane compound represented by the formula (1), Since the amount of the cured epoxy component is increased and the amount of the cured epoxy component is too large, corrosion of the adherend material tends to be promoted due to the influence of the excess curing agent, and therefore, preferably 50 to 120 parts by mass, more preferably 60 to 100 parts by mass. is there.
本発明の熱硬化性樹脂組成物は、硬化反応を円滑に、かつ短時間で完了させるために、公知の硬化促進剤を含有することができる。好ましい硬化促進剤としては、第四級ホスホニウム塩系硬化促進剤やイミダゾール系硬化促進剤が挙げられる。具体的には、第四級ホスホニウムのブロマイド塩（「Ｕ−ＣＡＴ５００３」（商標）、サンアプロ社製）、２−エチル−４−メチルイミダゾール等を挙げることができる。特に、酸無水物系硬化剤用の硬化促進剤としては、イミダゾール系硬化促進剤を好ましく使用することができる。この場合、イミダゾール系硬化促進剤の添加量は、少なすぎると硬化が不十分となる傾向があり、多すぎると熱・光に対する変色が大きくなる傾向があるので、酸無水物系硬化剤１００質量部に対し、イミダゾール系硬化促進剤を好ましくは０．２０〜２．００質量部、より好ましくは０．６０〜１．００質量部である。
The thermosetting resin composition of the present invention can contain a known curing accelerator in order to complete the curing reaction smoothly and in a short time. Preferred curing accelerators include quaternary phosphonium salt-based curing accelerators and imidazole-based curing accelerators. Specific examples include quaternary phosphonium bromide salts ("U-CAT5003" (trademark), manufactured by San Apro), 2-ethyl-4-methylimidazole, and the like. In particular, as a curing accelerator for an acid anhydride curing agent, an imidazole curing accelerator can be preferably used. In this case, if the amount of the imidazole curing accelerator added is too small, curing tends to be insufficient, and if too large, discoloration with respect to heat and light tends to increase, so an acid
以上説明した本発明の熱硬化性樹脂組成物は、発光素子の実装のための光反射性異方性導電接着剤の絶縁性接着成分であるバインダーとして使用する場合には、なるべく無色透明であることが好ましい。光反射性異方性導電接着剤中の光反射性導電粒子の光反射効率を低下させず、しかも入射光の光色を代えずに反射させるためである。ここで、無色透明とは、光反射性異方性導電接着剤の硬化物が、波長３８０〜７８０ｎｍの可視光に対して光路長１ｍｍの光透過率（ＪＩＳ Ｋ７１０５）が８０％以上、好ましくは９０％以上となることを意味する。 The thermosetting resin composition of the present invention described above is as colorless and transparent as possible when used as a binder that is an insulating adhesive component of a light-reflective anisotropic conductive adhesive for mounting a light-emitting element. It is preferable. This is because the light-reflecting conductive particles in the light-reflective anisotropic conductive adhesive are reflected without lowering the light reflection efficiency and without changing the light color of the incident light. Here, colorless and transparent means that the cured product of the light-reflective anisotropic conductive adhesive has a light transmittance (JIS K7105) of 80% or more with respect to visible light having a wavelength of 380 to 780 nm, preferably 80% or more. It means 90% or more.
本発明の熱硬化性樹脂組成物は、式（１）のエポキシ基含有シロキサン化合物とエポキシ用硬化剤と、必要に応じて配合される他の成分とを、公知の手法で混合することにより製造することができる。 The thermosetting resin composition of the present invention is produced by mixing the epoxy group-containing siloxane compound of formula (1), the curing agent for epoxy, and other components blended as necessary by a known method. can do.
次に、発光素子を配線板に異方性導電接続するために使用する本発明の光反射性異方性導電接着剤について説明する。この光反射性異方性導電接着剤は、熱硬化性樹脂組成物、導電粒子及び光反射性絶縁粒子を含有し、熱硬化性樹脂組成物が、式（１）で表されるエポキシ基含有シロキサン化合物と、エポキシ樹脂用硬化剤とを含有する本発明の熱硬化性樹脂組成物であることを特徴とするものである。 Next, the light-reflective anisotropic conductive adhesive of the present invention used for anisotropic conductive connection of the light emitting element to the wiring board will be described. This light-reflective anisotropic conductive adhesive contains a thermosetting resin composition, conductive particles and light-reflective insulating particles, and the thermosetting resin composition contains an epoxy group represented by the formula (1). The thermosetting resin composition of the present invention contains a siloxane compound and an epoxy resin curing agent.
＜光反射性絶縁粒子＞
本発明の光反射性異方性導電接着剤が含有する光反射性絶縁粒子は、異方性導電接着剤に入射した光を外部に反射するためのものである。
<Light reflective insulating particles>
The light-reflective insulating particles contained in the light-reflective anisotropic conductive adhesive of the present invention are for reflecting light incident on the anisotropic conductive adhesive to the outside.
なお、光反射性を有する粒子には、金属粒子、金属粒子を樹脂被覆した粒子、自然光の下で灰色から白色である金属酸化物、金属窒素化物、金属硫化物等の無機粒子、樹脂コア粒子を無機粒子で被覆した粒子、粒子の材質によらず、その表面に凹凸がある粒子が含まれる。しかし、これらの粒子の中で、本発明で使用できる光反射性絶縁粒子には、絶縁性を示すことが求められている関係上、絶縁被覆されていない金属粒子は含まれない。また、金属酸化物粒子のうち、ＩＴＯのように導電性を有するものは使用できない。また、光反射性且つ絶縁性を示す無機粒子であっても、ＳｉＯ２のように、その屈折率が使用する熱硬化性樹脂組成物の屈折率よりも低いものは使用できない。 The light-reflective particles include metal particles, particles coated with metal particles, inorganic particles such as metal oxides, metal nitrides, and metal sulfides that are gray to white under natural light, resin core particles The particle | grains which coat | covered with the inorganic particle and the particle | grains with the unevenness | corrugation on the surface are contained irrespective of the material of particle | grains. However, among these particles, the light-reflective insulating particles that can be used in the present invention do not include metal particles that are not covered with insulation because they are required to exhibit insulating properties. Moreover, among metal oxide particles, those having conductivity such as ITO cannot be used. Even inorganic particles showing light reflectivity and insulation, as SiO 2, low can not be used than the refractive index of the thermosetting resin composition whose refractive index is used.
このような光反射性絶縁粒子の好ましい具体例としては、酸化チタン（ＴｉＯ２）、窒化ホウ素（ＢＮ）、酸化亜鉛（ＺｎＯ）及び酸化アルミニウム（Ａｌ２Ｏ３）からなる群より選択される少なくとも一種の無機粒子が挙げられる。中でも、高屈折率の点からＴｉＯ２を使用することが好ましい。 Preferable specific examples of such light-reflective insulating particles include at least selected from the group consisting of titanium oxide (TiO 2 ), boron nitride (BN), zinc oxide (ZnO), and aluminum oxide (Al 2 O 3 ). A kind of inorganic particles can be mentioned. Among these, it is preferable to use TiO 2 from the viewpoint of a high refractive index.
光反射性絶縁粒子の形状としては、球状、鱗片状、不定形条、針状等でもよいが、反射効率を考慮すると、球状、鱗片状が好ましい。また、その大きさとしては、球状である場合、小さすぎると反射率が低くなり、大きすぎると異方性導電粒子による接続を阻害する傾向があるので、好ましくは０．０２〜２０μｍ、より好ましくは０．２〜１μｍであり、鱗片状である場合には、長径が好ましくは０．１〜１００μｍ、より好ましくは１〜５０μｍ、短径が好ましくは０．０１〜１０μｍ、より好ましくは０．１〜５μｍ、厚さが好ましくは０．０１〜１０μｍ、より好ましくは０．１〜５μｍである。 The shape of the light-reflective insulating particles may be spherical, scaly, indeterminate, needle-like, etc., but considering the reflection efficiency, spherical and scaly are preferable. In addition, when the size is spherical, if it is too small, the reflectance is low, and if it is too large, there is a tendency to inhibit connection by anisotropic conductive particles, so it is preferably 0.02 to 20 μm, more preferably Is 0.2 to 1 μm, and in the case of scaly, the major axis is preferably 0.1 to 100 μm, more preferably 1 to 50 μm, and the minor axis is preferably 0.01 to 10 μm, more preferably 0.00. The thickness is preferably 1 to 5 μm, and the thickness is preferably 0.01 to 10 μm, more preferably 0.1 to 5 μm.
無機粒子からなる光反射性絶縁粒子は、その屈折率（ＪＩＳ Ｋ７１４２）が、好ましくは熱硬化性樹脂組成物の硬化物の屈折率（ＪＩＳ Ｋ７１４２）よりも大きいこと、より好ましくは少なくとも０．０２程度大きいことが好ましい。これは、屈折率差が小さいとそれらの界面での反射効率が低下するからである。 The light-reflective insulating particles made of inorganic particles have a refractive index (JIS K7142) that is preferably larger than the refractive index (JIS K7142) of the cured product of the thermosetting resin composition, more preferably at least 0.02. It is preferable that the degree is large. This is because when the difference in refractive index is small, the reflection efficiency at the interface between them decreases.
光反射性絶縁粒子としては、以上説明した無機粒子を使用してもよいが、鱗片状又は球状金属粒子の表面を透明な絶縁性樹脂で被覆した樹脂被覆金属粒子を使用してもよい。金属粒子としては、ニッケル、銀、アルミニウム等を挙げることができる。粒子の形状としては、無定型、球状、鱗片状、針状等を挙げることができるが、中でも、光拡散効果の点から球状、全反射効果の点から鱗片状の形状が好ましい。特に、光の反射率の点から鱗片状銀粒子又は球状銀粒子である。 As the light-reflective insulating particles, the inorganic particles described above may be used, but resin-coated metal particles obtained by coating the surface of scale-like or spherical metal particles with a transparent insulating resin may be used. Examples of the metal particles include nickel, silver, and aluminum. Examples of the shape of the particles include an amorphous shape, a spherical shape, a scaly shape, and a needle shape. Among these, a spherical shape is preferable from the viewpoint of the light diffusion effect, and a scaly shape is preferable from the viewpoint of the total reflection effect. In particular, in terms of light reflectivity, they are scaly silver particles or spherical silver particles.
光反射性絶縁粒子としての樹脂被覆金属粒子の大きさは、形状によっても異なるが、一般に大きすぎると、異方性導電粒子による接続を阻害するおそれがあり、小さすぎると光を反射しにくくなるので、好ましくは球状の場合には粒径０．１〜３０μｍ、より好ましくは０．２〜１０μｍであり、鱗片状の場合には、長径が好ましくは０．１〜１００μｍ、より好ましくは１〜５０μｍで厚みが好ましくは０．０１〜１０μｍ、より好ましくは０．１〜５μｍである。ここで、光反射性絶縁粒子の大きさは、絶縁被覆されている場合には、その絶縁被覆も含めた大きさである。 The size of the resin-coated metal particles as the light-reflective insulating particles varies depending on the shape, but in general, if it is too large, there is a possibility that the connection by anisotropic conductive particles may be hindered, and if it is too small, it is difficult to reflect light. Therefore, in the case of a spherical shape, the particle diameter is preferably 0.1 to 30 μm, more preferably 0.2 to 10 μm. In the case of a scale shape, the major axis is preferably 0.1 to 100 μm, more preferably 1 to 1 μm. The thickness at 50 μm is preferably 0.01 to 10 μm, more preferably 0.1 to 5 μm. Here, the size of the light-reflective insulating particles is the size including the insulating coating when the insulating coating is applied.
このような樹脂被覆金属粒子における当該樹脂としては、種々の絶縁性樹脂を使用することができる。機械的強度や透明性等の点からアクリル系樹脂の硬化物を好ましく利用することができる。好ましくは、ベンゾイルパーオキサイド等の有機過酸化物などのラジカル開始剤の存在下で、メタクリル酸メチルとメタクリル酸２−ヒドロキシエチルとをラジカル共重合させた樹脂を挙げることができる。この場合、２，４−トリレンジイソシアネート等のイソシアネート系架橋剤で架橋されていることがより好ましい。また、金属粒子としては、予めシランカップリング剤でγ−グリシドキシ基やビニル基等を金属表面に導入しておくことが好ましい。 Various insulating resins can be used as the resin in such resin-coated metal particles. From the standpoint of mechanical strength and transparency, a cured product of acrylic resin can be preferably used. Preferable examples include resins obtained by radical copolymerization of methyl methacrylate and 2-hydroxyethyl methacrylate in the presence of a radical initiator such as an organic peroxide such as benzoyl peroxide. In this case, it is more preferable that it is crosslinked with an isocyanate-based crosslinking agent such as 2,4-tolylene diisocyanate. Moreover, as a metal particle, it is preferable to introduce | transduce (gamma) -glycidoxy group, a vinyl group, etc. to the metal surface previously with a silane coupling agent.
このような樹脂被覆金属粒子は、例えば、トルエンなどの溶媒中に金属粒子とシランカップリング剤とを投入し、室温で約１時間攪拌した後、ラジカルモノマーとラジカル重合開始剤と、必要に応じて架橋剤とを投入し、ラジカル重合開始温度に加温しながら撹拌することにより製造することができる。 For example, such resin-coated metal particles are prepared by adding metal particles and a silane coupling agent in a solvent such as toluene and stirring the mixture at room temperature for about 1 hour, and then, if necessary, a radical monomer and a radical polymerization initiator. Then, a crosslinking agent is added, and the mixture is stirred by heating to the radical polymerization starting temperature.
以上説明した光反射性絶縁粒子の、光反射性異方性導電接着剤中の配合量は、少なすぎると十分な光反射を実現することができず、また多すぎると併用している導電粒子に基づく接続が阻害されるので、光反射性異方性導電接着剤中に光反射性絶縁粒子を好ましくは１〜５０体積％、より好ましくは５〜２５体積％である。 If the amount of the light-reflective insulating particles described above in the light-reflective anisotropic conductive adhesive is too small, sufficient light reflection cannot be realized, and if it is too large, the conductive particles used in combination. Therefore, the light-reflective insulating particles in the light-reflective anisotropic conductive adhesive are preferably 1 to 50% by volume, more preferably 5 to 25% by volume.
＜導電粒子＞
本発明の光反射性異方性導電接着剤を構成する導電粒子としては、異方性導電接続用の従来の導電粒子において用いられている金属の粒子を利用することができる。例えば、金、ニッケル、銅、銀、半田、パラジウム、アルミニウム、それらの合金、それらの多層化物（例えば、ニッケルメッキ／金フラッシュメッキ物）等を挙げることができる。中でも、金、ニッケル、銅は、導電粒子を茶色としてしまうことから、本発明の効果を他の金属材料よりも享受することができる。
<Conductive particles>
As the conductive particles constituting the light-reflective anisotropic conductive adhesive of the present invention, metal particles used in conventional conductive particles for anisotropic conductive connection can be used. Examples thereof include gold, nickel, copper, silver, solder, palladium, aluminum, alloys thereof, multilayered products thereof (for example, nickel plating / gold flash plating products), and the like. Above all, gold, nickel, and copper turn the conductive particles brown, so that the effects of the present invention can be enjoyed over other metal materials.
また、導電粒子として、樹脂粒子を金属材料で被覆した金属被覆樹脂粒子を使用することができる。このような樹脂粒子としては、スチレン系樹脂粒子、ベンゾグアナミン樹脂粒子、ナイロン樹脂粒子などが挙げられる。樹脂粒子を金属材料で被覆する方法としても従来公知の方法を採用することができ、無電解メッキ法、電解メッキ法等を利用することができる。また、被覆する金属材料の層厚は、良好な接続信頼性を確保するに足る厚さであり、樹脂粒子の粒径や金属の種類にもよるが、通常、０．１〜３μｍである。 Further, as the conductive particles, metal-coated resin particles obtained by coating resin particles with a metal material can be used. Examples of such resin particles include styrene resin particles, benzoguanamine resin particles, and nylon resin particles. As a method of coating the resin particles with a metal material, a conventionally known method can be employed, and an electroless plating method, an electrolytic plating method, or the like can be used. The layer thickness of the metal material to be coated is sufficient to ensure good connection reliability, and is usually 0.1 to 3 μm although it depends on the particle size of the resin particles and the type of metal.
また、樹脂粒子の粒径は、小さすぎると導通不良が生じ、大きすぎるとパターン間ショートが生じる傾向があるので、好ましくは１〜２０μｍ、より好ましくは３〜１０μｍ、特に好ましくは３〜５μｍである。この場合、コア粒子１の形状としては球形が好ましいが、フレーク状、ラクビーボール状であってもよい。
In addition, if the particle size of the resin particles is too small, poor conduction occurs, and if it is too large, there is a tendency for short between patterns to occur. Therefore, it is preferably 1 to 20 μm, more preferably 3 to 10 μm, particularly preferably 3 to 5 μm. is there. In this case, the shape of the
好ましい金属被覆樹脂粒子は球状形状であり、その粒径は大きすぎると接続信頼性の低下となるので、好ましくは１〜２０μｍ、より好ましくは３〜１０μｍである。 Preferable metal-coated resin particles have a spherical shape, and if the particle size is too large, the connection reliability is lowered, so that it is preferably 1 to 20 μm, more preferably 3 to 10 μm.
特に、本発明においては、上述したような導電粒子に対し光反射性を付与し、光反射性導電粒子とすることが好ましい。図１Ａ、図１Ｂは、このような光反射性導電粒子１０、２０の断面図である。まず、図１Ａの光反射性導電粒子から説明する。
In particular, in the present invention, it is preferable to impart light reflectivity to the conductive particles as described above to obtain light reflective conductive particles. 1A and 1B are sectional views of such light-reflective
光反射性導電粒子１０は、金属材料で被覆されているコア粒子１と、その表面に酸化チタン（ＴｉＯ２）粒子、窒化ホウ素（ＢＮ）粒子、酸化亜鉛（ＺｎＯ）粒子又は酸化アルミニウム（Ａｌ２Ｏ３）粒子から選択された少なくとも一種の無機粒子２から形成された光反射層３とから構成される。酸化チタン粒子、窒化ホウ素粒子、酸化亜鉛粒子又は酸化アルミニウム粒子は、太陽光の下では白色を呈する無機粒子である。従って、それらから形成された光反射層３は白色〜灰色を呈する。白色〜灰色を呈しているということは、可視光に対する反射特性の波長依存性が小さく、且つ可視光を反射しやすいことを意味する。
The light-reflective
なお、酸化チタン粒子、窒化ホウ素粒子、酸化亜鉛粒子又は酸化アルミニウム粒子のうち、硬化した光反射性異方性導電接着剤の熱硬化性樹脂組成物の硬化物の光劣化が懸念される場合には、光劣化に対して触媒性がなく、屈折率も高い酸化亜鉛粒子を好ましく使用することができる。 Of the titanium oxide particles, boron nitride particles, zinc oxide particles, or aluminum oxide particles, when there is a concern about photodegradation of the cured product of the thermosetting resin composition of the cured light-reflective anisotropic conductive adhesive. Can be preferably used zinc oxide particles which are not catalytic to photodegradation and have a high refractive index.
コア粒子１は、異方性導電接続に共されるものであるので、その表面が金属材料で構成されている。ここで、表面が金属材料で被覆されている態様としては、前述したように、コア粒子１そのものが金属材料である態様、もしくは樹脂粒子の表面が金属材料で被覆された態様が挙げられる。
Since the
無機粒子２から形成された光反射層３の層厚は、コア粒子１の粒径との相対的大きさの観点からみると、コア粒子１の粒径に対し、小さすぎると反射率の低下が著しくなり、大きすぎると導通不良が生ずるので、好ましくは０．５〜５０％、より好ましくは１〜２５％である。
From the viewpoint of the relative size with respect to the particle size of the
また、光反射性導電粒子１０において、光反射層３を構成する無機粒子２の粒径は、小さすぎると光反射現象が生じ難くなり、大きすぎると光反射層の形成が困難となる傾向があるので、好ましくは０．０２〜４μｍ、より好ましくは０．１〜１μｍ、特に好ましくは０．２〜０．５μｍである。この場合、光反射させる光の波長の観点からみると、無機粒子２の粒径は、反射させるべき光（即ち、発光素子が発する光）が透過してしまわないように、その光の波長の５０％以上であることが好ましい。この場合、無機粒子２の形状としては無定型、球状、鱗片状、針状等を挙げることができるが、中でも、光拡散効果の点から球状、全反射効果の点から鱗片状の形状が好ましい。
Further, in the light-reflective
図１Ａの光反射性導電粒子１０は、大小の粉末同士を物理的に衝突させることにより大粒径粒子の表面に小粒径粒子からなる膜を形成させる公知の成膜技術（いわゆるメカノフュージョン法）により製造することができる。この場合、無機粒子２は、コア粒子１の表面の金属材料に食い込むように固定され、他方、無機粒子同士が融着固定されにくいから、無機粒子のモノレイヤーが光反射層３を構成する。従って、図１Ａの場合、光反射層３の層厚は、無機粒子２の粒径と同等乃至はわずかに薄くなると考えられる。
The light-reflective
次に、図１Ｂの光反射性導電粒子２０について説明する。この光反射性導電粒子２０においては、光反射層３が接着剤として機能する熱可塑性樹脂４を含有し、この熱可塑性樹脂４により無機粒子２同士も固定され、無機粒子２が多層化（例えば２層あるいは３層に多層化）している点で、図１Ａの光反射性導電粒子１０と相違する。このような熱可塑性樹脂４を含有することにより、光反射層３の機械的強度が向上し、無機粒子の剥落などが生じにくくなる。
Next, the light reflective
熱可塑性樹脂４としては、環境低負荷を意図してハロゲンフリーの熱可塑性樹脂を好ましく使用することができ、例えば、ポリエチレン、ポリプロピレン等のポリオレフィンやポリスチレン、アクリル樹脂等を好ましく使用することができる。 As the thermoplastic resin 4, a halogen-free thermoplastic resin can be preferably used for the purpose of low environmental load. For example, polyolefins such as polyethylene and polypropylene, polystyrene, acrylic resins, and the like can be preferably used.
このような光反射性導電粒子２０も、メカノフュージョン法により製造することができる。メカノフュージョン法に適用する熱可塑性樹脂４の粒子径は、小さすぎると接着機能が低下し、大きすぎるとコア粒子に付着しにくくなるので、好ましくは０．０２〜４μｍ、より好ましくは０．１〜１μｍである。また、このような熱可塑性樹脂４の配合量は、少なすぎると接着機能が低下し、多すぎると粒子の凝集体が形成されるので、無機粒子２の１００質量部に対し、好ましくは０．２〜５００質量部、より好ましくは４〜２５質量部である。
Such light-reflective
本発明の光反射性異方性導電接着剤中の光反射性導電粒子等の導電粒子の配合量は、少なすぎると導通不良が生じる傾向があり、多すぎるとパターン間ショートが生ずる傾向があるので、熱硬化性樹脂組成物１００質量部に対し、光反射性導電粒子等の導電粒子の配合量は、好ましくは１〜１００質量部、より好ましくは１０〜５０質量部である。 If the blending amount of the conductive particles such as the light-reflective conductive particles in the light-reflective anisotropic conductive adhesive of the present invention is too small, conduction failure tends to occur, and if it is too large, there is a tendency to cause a short circuit between patterns. Therefore, the blending amount of conductive particles such as light-reflective conductive particles is preferably 1 to 100 parts by mass, more preferably 10 to 50 parts by mass with respect to 100 parts by mass of the thermosetting resin composition.
＜光反射性異方性導電接着剤の製造＞
本発明の光反射性異方性導電接着剤は、以上説明した光反射性絶縁粒子と導電粒子と熱硬化性樹脂組成物とを、常法に従って均一に混合することにより製造することができる。また、光反射性異方性導電フィルムとする場合には、それらをトルエン等の溶媒とともに分散混合し、剥離処理したＰＥＴフィルムに所期の厚さとなるように塗布し、約８０℃程度の温度で乾燥すればよい。
<Production of light-reflective anisotropic conductive adhesive>
The light-reflective anisotropic conductive adhesive of the present invention can be produced by uniformly mixing the light-reflective insulating particles, the conductive particles, and the thermosetting resin composition described above according to a conventional method. In the case of light-reflective anisotropic conductive films, they are dispersed and mixed together with a solvent such as toluene, and applied to a peeled PET film so as to have a desired thickness, and a temperature of about 80 ° C. Just dry.
＜光反射性異方性導電接着剤の反射特性＞
本発明の光反射性異方性導電接着剤の反射特性は、発光素子の発光効率を向上させるために、光反射性異方性導電接着剤の硬化物の波長４５０ｎｍの光に対する反射率（ＪＩＳ Ｋ７１０５）が、少なくとも３０％であること望ましい。このような反射率とするためには、使用する光反射性導電粒子の反射特性や配合量、熱硬化性樹脂組成物の配合組成などを適宜調整すればよい。通常、反射特性の良好な光反射性導電粒子の配合量を増量すれば、反射率も増大する傾向がある。
<Reflection characteristics of light-reflective anisotropic conductive adhesive>
The reflection characteristic of the light-reflective anisotropic conductive adhesive of the present invention is such that the reflectance of the cured light-reflective anisotropic conductive adhesive to light having a wavelength of 450 nm (JIS) is improved in order to improve the light emission efficiency of the light-emitting element. Preferably, K7105) is at least 30%. In order to obtain such a reflectance, the reflection characteristics and blending amount of the light-reflective conductive particles to be used, the blending composition of the thermosetting resin composition, and the like may be appropriately adjusted. Usually, if the amount of the light-reflective conductive particles having good reflection characteristics is increased, the reflectance tends to increase.
また、光反射性異方性導電接着剤の反射特性は屈折率という観点から評価することもできる。即ち、その硬化物の屈折率が、導電粒子と光反射性絶縁粒子とを除いた熱硬化性樹脂組成物の硬化物の屈折率よりも大きいと、光反射性絶縁電粒子とそれを取り巻く熱硬化性樹脂組成物の硬化物との界面での光反射量が増大するからである。具体的には、光反射性粒子の屈折率（ＪＩＳ Ｋ７１４２）から、熱硬化性樹脂組成物の硬化物の屈折率（ＪＩＳ Ｋ７１４２）を差し引いた差が、好ましくは０．０２以上、より好ましくは０．２以上であることが望まれる。なお、通常、エポキシ樹脂を主体とする熱硬化性樹脂組成物の屈折率は約１．５である。 Further, the reflection characteristics of the light-reflective anisotropic conductive adhesive can be evaluated from the viewpoint of refractive index. That is, when the refractive index of the cured product is larger than the refractive index of the cured product of the thermosetting resin composition excluding the conductive particles and the light-reflective insulating particles, the light-reflective insulating particles and the heat surrounding them are obtained. This is because the amount of light reflection at the interface between the curable resin composition and the cured product increases. Specifically, the difference obtained by subtracting the refractive index of the cured product of the thermosetting resin composition (JIS K7142) from the refractive index of the light reflective particles (JIS K7142) is preferably 0.02 or more, more preferably It is desired to be 0.2 or more. In general, the refractive index of a thermosetting resin composition mainly composed of an epoxy resin is about 1.5.
＜発光装置＞
次に、本発明の発光装置について図２を参照しながら説明する。発光装置２００は、基板２１上の接続端子２２と、発光素子としてＬＥＤ素子２３のｎ電極２４とｐ電極２５とのそれぞれに形成された接続用のバンプ２６との間に、前述の本発明の光反射性異方性導電接着剤を塗布し、基板２１とＬＥＤ素子２３とがフリップチップ実装されている発光装置である。ここで、光反射性異方性導電接着剤の硬化物１００は、光反射性絶縁粒子１０が熱硬化性樹脂組成物の硬化物１１中に分散してなるものである。なお、必要に応じて、ＬＥＤ素子２３の全体を覆うように透明モールド樹脂で封止してもよい。また、ＬＥＤ素子２３に従来と同様に光反射層を設けてもよい。
<Light emitting device>
Next, the light emitting device of the present invention will be described with reference to FIG. The light-emitting device 200 includes the
このように構成されている発光装置２００においては、ＬＥＤ素子２３は発した光のうち、基板２１側に向かって発した光は、光反射性異方性導電接着剤の硬化物１００中の光反射性絶縁粒子１０で反射し、ＬＥＤ素子２３の上面から出射する。従って、発光効率の低下を防止することができる。
In the light emitting device 200 configured as described above, among the light emitted from the LED element 23, the light emitted toward the
本発明の発光装置２００における光反射性異方性導電接着剤以外の構成（ＬＥＤ素子２３、バンプ２６、基板２１、接続端子２２等）は、従来の発光装置の構成と同様とすることができる。また、本発明の発光装置２００は、本発明の光反射性異方性導電接着剤を使用すること以外は、従来の異方性導電接続技術を利用して製造することができる。なお、発光素子としては、ＬＥＤ素子の他、本発明の効果を損なわない範囲で公知の発光素子を適用することができる。
Configurations other than the light-reflective anisotropic conductive adhesive (the LED element 23, the
参考例（式（１ａ）のエポキシ基含有シロキサン化合物の製造）
窒素気流中、還流冷却管と磁気撹拌子とを備えた１００ｍｌ三口フラスコに、２８．３７ｇ（１００．８８ｍｍｏｌ）の１−アリル−３，５−ジグリシジルイソシアヌレート（ＭＡＤＧＩＣ、四国化成工業（株））と、６．６３ｇ（２０．１７ｍｍｏｌ）のテトラキス（ハイドロジェンジメチルシロキシ）シラン（ＳＩＴ７２７８．０、Ｇｅｌｅｓｔ Ｉｎｃ．）］とを投入し、混合物を８０℃で均一に溶融するまで撹拌した。続いて、この溶融混合物に２％Ｋａｒｓｔｅｄｔ触媒溶液（キシレン溶液）３０．２μＬを添加し、撹拌しながら１４０℃になるまで加熱し、溶融混合物の温度が１４０℃に到達してから、その温度を９時間保持して、１−アリル−３，５−ジグリシジルイソシアヌレートとテトラキス（ハイドロジェンジメチルシロキシ）シランとを反応させた。
Reference Example (Production of Epoxy Group-Containing Siloxane Compound of Formula (1a))
In a 100 ml three-necked flask equipped with a reflux condenser and a magnetic stirring bar in a nitrogen stream, 28.37 g (100.88 mmol) of 1-allyl-3,5-diglycidyl isocyanurate (MADGIC, Shikoku Chemical Industry Co., Ltd.) ) And 6.63 g (20.17 mmol) of tetrakis (hydrogendimethylsiloxy) silane (SIT7278.0, Gelest Inc.)] were added and the mixture was stirred at 80 ° C. until uniformly melted. Subsequently, 30.2 μL of a 2% Karstedt catalyst solution (xylene solution) is added to the molten mixture, and the mixture is heated to 140 ° C. with stirring. After the temperature of the molten mixture reaches 140 ° C., the temperature is adjusted. Holding for 9 hours, 1-allyl-3,5-diglycidyl isocyanurate and tetrakis (hydrogendimethylsiloxy) silane were reacted.
反応終了後、反応混合物を冷却し、未反応モノマーを減圧下（１５０℃/０．１ｋＰａ）で留去し、式（１ａ）のエポキシ基含有シロキサン化合物を得た。 After completion of the reaction, the reaction mixture was cooled, and unreacted monomers were distilled off under reduced pressure (150 ° C./0.1 kPa) to obtain an epoxy group-containing siloxane compound of the formula (1a).
＜ヒドロシリル化反応の進行程度評価＞
ヒドロシリル化反応の進行具合を確認するために、以下に説明するようにＦＴ−ＩＲ測定と１ＨＮＭＲ測定とを行った。
<Evaluation of progress of hydrosilylation reaction>
In order to confirm the progress of the hydrosilylation reaction, FT-IR measurement and 1 HNMR measurement were performed as described below.
（ＦＴ−ＩＲ測定）
ヒドロシリル化反応物の減圧蒸留残渣、並びに原料の１−アリル−３，５−ジグリシジルイソシアヌレート（ＭＡＤＧＩＣ）とテトラキス（ハイドロジェンジメチルシロキシ）シラン（ＳＩＴ７２７８．０）について、それぞれＦＴ−ＩＲ測定（測定装置：フーリエ変換赤外分光光度計 ＦＴ−ＩＲ−４６０ＰＬＵＳ、日本分光（株）製）を行い、得られた結果を図３に示した。原料のテトラキス（ハイドロジェンジメチルシロキシ）シラン（ＳＩＴ７２７８．０）については、Ｓｉ−Ｈ基特有のスペクトルとして、２１４０ｃｍ−１付近の伸縮ピーク、９００ｃｍ−１付近の変角振動ピークが検出された。また、１６９０ｃｍ−１及び１４６０ｃｍ−１付近には、イソシアヌレート由来のシャープなカルボニル基伸縮ピークが検出された。反応物の減圧蒸留残渣については、Ｓｉ−Ｈ基に特有な２１４０ｃｍ−１付近と９００ｃｍ−１付近のピークは検出されず、一方、イソシアヌレートに由来する１６９０ｃｍ−１及び１４６０ｃｍ−１付近のピークが検出された。
(FT-IR measurement)
FT-IR measurement (measurement) for the hydrosilylation reaction residue under reduced pressure and the raw materials 1-allyl-3,5-diglycidyl isocyanurate (MADGIC) and tetrakis (hydrogendimethylsiloxy) silane (SIT7278.0) Apparatus: Fourier transform infrared spectrophotometer FT-IR-460PLUS, manufactured by JASCO Corporation), and the obtained results are shown in FIG. The starting material, tetrakis (hydrogen dimethylsiloxy) silane (SIT7278.0), as Si-H group-specific spectral, stretching peak around 2140 cm -1, is bending vibration peak near 900 cm -1 were detected. In addition, sharp carbonyl group stretching peaks derived from isocyanurate were detected in the vicinity of 1690 cm −1 and 1460 cm −1 . The vacuum distillation residue of the reaction product, the peak in the vicinity of and around 900 cm -1 characteristic 2140 cm -1 in the Si-H groups detected, whereas, the peak near 1690 cm -1 and 1460 cm -1 derived from isocyanurate was detected.
これらのことから、式（１ａ）のエポキシ基含有シロキサン化合物が生成していることが確認できた。即ち、ハイドロシリレーション（ハイドロシリル化反応）が完結していることが確認できた。 From these things, it has confirmed that the epoxy-group containing siloxane compound of Formula (1a) was producing | generating. That is, it was confirmed that hydrosilylation (hydrosilylation reaction) was completed.
（１Ｈ-ＮＭＲ測定）
ヒドロシリル化反応物の減圧蒸留残渣について、１Ｈ-ＮＭＲ測定（測定装置：ＭＥＲＣＵＲＹ３００、ＶＡＲＩＡＮ製）を行い、得られた結果を図４に示した。ケミカルシフトが０ｐｐｍ付近には、シリコーン由来のＳｉ−Ｍｅ基に対応するシグナルが観測された。また、ケミカルシフトが４．１２〜２．６６ｐｐｍには、グリシジルイソシアヌレート由来のシグナルが多数確認された。他方、アリル基のα，β位炭素隣接プロトンにみられる特有のシグナルとＳｉ−Ｈ基のシグナル（両者とも、ケミカルシフト６．００〜５．００ｐｐｍ）とは、共に確認されなかった。
(1 H-NMR measurement)
The 1 H-NMR measurement (measuring device: MERCURY300, manufactured by VARIAN) was performed on the vacuum distillation residue of the hydrosilylation reaction product, and the obtained result is shown in FIG. When the chemical shift was around 0 ppm, a signal corresponding to the Si-Me group derived from silicone was observed. Moreover, many signals derived from glycidyl isocyanurate were confirmed at a chemical shift of 4.12 to 2.66 ppm. On the other hand, neither a peculiar signal seen in the α and β carbon adjacent protons of the allyl group nor a Si—H group signal (both chemical shifts of 6.00 to 5.00 ppm) were confirmed.
これらのことからも、式（１ａ）のエポキシ基含有シロキサン化合物が生成していることが確認できた。即ち、ハイドロシリレーション（ハイドロシリル化反応）が完結していることが確認できた。なお、ＭＡＤＧＩＣの投入量をコントロールすることにより、部分的にＳｉ−Ｈ基が残存する化合物を意図的に製造できることが期待される。 Also from these things, it has confirmed that the epoxy-group containing siloxane compound of Formula (1a) was producing | generating. That is, it was confirmed that hydrosilylation (hydrosilylation reaction) was completed. Note that it is expected that a compound in which Si-H groups partially remain can be intentionally produced by controlling the amount of MADGIC input.
実施例１
得られたエポキシ基含有シロキサン化合物を用い、表１に示す配合組成の成分を均一に混合することにより絶縁性接着剤として本発明の熱硬化性樹脂組成物を調製した。なお、実施例１においては、エポキシ基／酸無水物の官能基数の比が１／１．１となるように、エポキシ化合物と酸無水物系硬化剤とを配合した。
Example 1
The thermosetting resin composition of the present invention was prepared as an insulating adhesive by uniformly mixing the components of the composition shown in Table 1 using the obtained epoxy group-containing siloxane compound. In Example 1, an epoxy compound and an acid anhydride curing agent were blended so that the ratio of the number of functional groups of epoxy group / acid anhydride was 1 / 1.1.
比較例１〜３
また、比較例１の絶縁性接着剤としての熱硬化性樹脂組成物は、エポキシ化合物として、式（１ａ）のエポキシ基含有シロキサン化合物に代えて１，３，５−トリグリシジルイソシアネートを使用した例であり、比較例２の絶縁性接着剤としての熱硬化性樹脂組成物は、２液硬化型ジメチルシリコーン樹脂（ＩＶＳ４７４２、モメンティブマテリアル社）であり、比較例３の絶縁性接着剤としての熱硬化性樹脂組成物は、２液硬化型フェニルシリコーン樹脂（ＳＣＲ−１０１２、信越化学工業（株））である。
Comparative Examples 1-3
Moreover, the thermosetting resin composition as an insulating adhesive of Comparative Example 1 is an example in which 1,3,5-triglycidyl isocyanate is used as an epoxy compound in place of the epoxy group-containing siloxane compound of the formula (1a). The thermosetting resin composition as the insulating adhesive of Comparative Example 2 is a two-component curable dimethyl silicone resin (IVS4742, Momentive Materials), and the thermosetting as the insulating adhesive of Comparative Example 3 The conductive resin composition is a two-component curable phenyl silicone resin (SCR-1012, Shin-Etsu Chemical Co., Ltd.).
＜評価＞
得られた絶縁性接着剤としての熱硬化性樹脂組成物について、ダイシェア強度試験、耐熱試験と耐熱光試験とを行った。得られた結果を表２に示す。
<Evaluation>
The thermosetting resin composition as the obtained insulating adhesive was subjected to a die shear strength test, a heat resistance test, and a heat resistance light test. The obtained results are shown in Table 2.
＜ダイシェア強度試験＞
金バンプ（高１０μｍ、径８０μｍ、ピッチ１９０μｍ）が形成された１０μｍ厚の銀ベタ電極を有するＬＥＤ用ガラスエポキシ基板（特注品、関西電子工業（株）））に、径が４ｍｍとなるように絶縁性接着剤を塗布し、そこへ０．３ｍｍ角のフリップチップ型ＬＥＤ素子（ＧＭ３５Ｒ４６０Ｇ、昭和電工（株））を載せ、フリップチップ型ＬＥＤ素子が表側となるようにガラスエポキシ基板を８０℃に保持されたホットプレートに置き、２分間加熱してＬＥＤ素子をＬＥＤ用ガラスエポキシ基板に仮固定した。このＬＥＤ素子が仮固定されたＬＥＤ用ガラスエポキシ基板を熱圧着装置に適用し、ＬＥＤ素子に８０ｇｆ／ｃｈｉｐの圧力を印加しながら２３０℃で１５秒間熱圧着処理を行うことにより、ＬＥＤ用ガラスエポキシ基板にＬＥＤ素子が実装されたＬＥＤ装置を作成した。実施例１又は比較例１の絶縁性接着剤を使用して作成したＬＥＤ装置の場合、熱圧着処理後に更に２６０℃、２０秒のリフロー処理を行った。
<Die shear strength test>
A glass epoxy substrate for LED (special order product, Kansai Electronics Co., Ltd.) having a silver solid electrode with a thickness of 10 μm on which gold bumps (high 10 μm, diameter 80 μm, pitch 190 μm) are formed so that the diameter is 4 mm. Apply an insulating adhesive and place a 0.3 mm square flip chip type LED element (GM35R460G, Showa Denko KK) on the glass epoxy substrate at 80 ° C. so that the flip chip type LED element is on the front side. The LED element was placed on a held hot plate and heated for 2 minutes to temporarily fix the LED element on the glass epoxy substrate for LED. The glass epoxy substrate for LED, to which this LED element is temporarily fixed, is applied to a thermocompression bonding apparatus and subjected to thermocompression bonding at 230 ° C. for 15 seconds while applying a pressure of 80 gf / chip to the LED element. An LED device having LED elements mounted on a substrate was created. In the case of the LED device produced using the insulating adhesive of Example 1 or Comparative Example 1, a reflow treatment at 260 ° C. for 20 seconds was further performed after the thermocompression treatment.
このようにして作成したＬＥＤ装置について、ダイシェア強度(ｇｆ／ｃｈｉｐ)を測定した。実用上、ダイシェア強度は少なくとも２００ｇｆ／ｃｈｉｐ、好ましくは２５０ｇｆ／ｃｈｉｐ以上であることが望まれる。 The die shear strength (gf / chip) of the LED device thus produced was measured. In practice, the die shear strength is desired to be at least 200 gf / chip, preferably 250 gf / chip or more.
＜耐熱試験＞
１ｍｍ高さのスペーサが四隅に配置された２枚のアルミニウム平板（長１００ｍｍ×幅５０．０ｍｍ×厚０．５０ｍｍ）で絶縁性接着剤を挟み、実施例１及び比較例１の絶縁性接着剤については、まず１２０℃で３０分加熱し、続いて１４０℃で１時間加熱することにより硬化樹脂シートサンプルを作成した。また、比較例２及び３の絶縁性接着剤については、まず８０℃で１時間加熱し、続いて１５０℃で２時間加熱することにより硬化樹脂シートサンプルを作成した。
<Heat resistance test>
The insulating adhesives of Example 1 and Comparative Example 1 are sandwiched between two aluminum flat plates (
得られた硬化樹脂シートサンプルを、１５０℃に設定されたオーブン内に１０００時間放置し、放置前後の分光特性（Ｌ＊、ａ＊、ｂ＊）を、分光測色計（ＣＭ−３６００ｄ、コニカミノルタオプティクス（株））を用いて測定し、得られた測定値から色差（ΔＥ）を算出した。実用上、ΔＥは３５以下であることが望まれる。 The obtained cured resin sheet sample is allowed to stand in an oven set at 150 ° C. for 1000 hours, and spectral characteristics (L * , a * , b * ) before and after being left are measured with a spectrocolorimeter (CM-3600d, Konica). Minolta Optics Co., Ltd.), and the color difference (ΔE) was calculated from the measured values. In practice, ΔE is desirably 35 or less.
＜耐熱光試験＞
耐熱試験に供した硬化樹脂シートサンプルと同様の硬化樹脂シートサンプルを作成し、それを、温度１２０℃で光強度１６ｍＷ／ｃｍ２に設定された熱光試験機（スーパーウインミニ、ダイプラウィンテス（株）；メタルハライドランプ使用）内に１０００時間放置し、得られた硬化樹脂シートを、１５０℃に設定されたオーブン内に１０００時間放置し、放置前後の分光特性（Ｌ＊、ａ＊、ｂ＊）を、分光測色計（ＣＭ−３６００ｄ、コニカミノルタオプティクス（株））を用いて測定し、得られた測定値から色差（ΔＥ）を算出した。実用上、ΔＥは２０以下であることが望まれる。
<Heat-resistant light test>
A cured resin sheet sample similar to the cured resin sheet sample subjected to the heat resistance test was prepared, and the cured resin sheet sample was prepared at a temperature of 120 ° C. with a light intensity of 16 mW / cm 2 (super win mini, die pla wintes ( ); Used in a metal halide lamp) for 1000 hours, and the resulting cured resin sheet is left in an oven set at 150 ° C. for 1000 hours to obtain spectral characteristics before and after being left (L * , a * , b *). ) Was measured using a spectrocolorimeter (CM-3600d, Konica Minolta Optics, Inc.), and the color difference (ΔE) was calculated from the obtained measurement values. Practically, ΔE is desired to be 20 or less.
表２から解るように、実施例１のエポキシ基含有シロキサン化合物を硬化成分として用いた硬化樹脂シートサンプルは、ダイシェア強度、耐熱試験及び耐熱光試験の結果がいずれも実用上好ましいものであったが、比較例１の場合には、熱硬化性エポキシ樹脂組成物を使用しているため、ダイシェア強度については好ましい結果が得られたが、式（１ａ）のエポキシ含有シロキサン化合物を使用していないため、耐熱試験に関し、満足できる結果が得られなかった。 As can be seen from Table 2, the cured resin sheet sample using the epoxy group-containing siloxane compound of Example 1 as a curing component was practically preferable in terms of die shear strength, heat resistance test and heat resistance light test. In the case of Comparative Example 1, since a thermosetting epoxy resin composition was used, a favorable result was obtained for the die shear strength, but the epoxy-containing siloxane compound of the formula (1a) was not used. Satisfactory results were not obtained for the heat resistance test.
なお、比較例２及び３については、式（１ａ）のエポキシ基含有シロキサン化合物のみならず、熱硬化性エポキシ樹脂組成物を使用していないため、ダイシェア強度が著しく低く、耐熱試験、耐熱光試験をするまでもないものであった。 In Comparative Examples 2 and 3, not only the epoxy group-containing siloxane compound of the formula (1a) but also the thermosetting epoxy resin composition is not used, so the die shear strength is remarkably low, and the heat resistance test and heat resistance light test. It was not necessary to do.
実施例２
絶縁性接着剤として実施例１の熱硬化性樹脂組成物１００質量部に対し、光反射性絶縁粒子（平均粒径０．５μｍの二酸化チタン酸粉末（ＫＲ−３８０、チタン工業（株））２４．０質量部と、導電粒子（平均粒径５μｍの金被覆樹脂導電粒子（平均粒径４．６μｍの球状アクリル樹脂粒子に０．２μｍ厚の無電解金メッキを施した粒子（ライト２０ＧＮＢ４、日本化学工業（株））５．００質量部とを均一に混合することにより実施例２の光反射性異方性導電接着剤を調製した。
Example 2
For 100 parts by mass of the thermosetting resin composition of Example 1 as an insulating adhesive, light-reflective insulating particles (titanium dioxide powder having an average particle size of 0.5 μm (KR-380, Titanium Industry Co., Ltd.)) 24 0.0 parts by mass and conductive particles (gold-coated resin conductive particles having an average particle size of 5 μm (particles obtained by electroless gold plating of 0.2 μm thickness on spherical acrylic resin particles having an average particle size of 4.6 μm) (Light 20GNB4, Nippon Chemical The light-reflective anisotropic conductive adhesive of Example 2 was prepared by uniformly mixing 5.00 parts by mass with Kogyo Co., Ltd.).
比較例４
光反射性絶縁粒子を使用しない以外は、実施例４と同様の操作を繰り返すことにより異方性導電接着剤を調製した。
Comparative Example 4
An anisotropic conductive adhesive was prepared by repeating the same operation as in Example 4 except that the light-reflective insulating particles were not used.
（評価）
得られた光反射性異方性導電接着剤の光反射率評価試験、ＬＥＤ実装サンプルにおける全光束量評価試験を以下に説明するように測定した。
(Evaluation)
The light reflectivity evaluation test of the obtained light-reflective anisotropic conductive adhesive and the total light flux evaluation test in the LED mounting sample were measured as described below.
（光反射率評価試験）
得られた実施例２及び比較例４の異方性導電接着剤を、セラミック製の白色板に乾燥厚で１００μｍとなるように塗布し、２００℃で１分間加熱し、硬化させた。この硬化物について、分光光度計（Ｕ３３００、日立製作所（株））を用いて、波長４５０ｎｍの光に対する反射率（ＪＩＳ Ｋ７１５０）を測定した。反射率は、実用上３０％以上であるところ、実施例２の光反射性異方性導電接着剤は３０％を超える反射率を示したのに対し、比較例４の異方性導電接着剤は３０％を超える反射率を示さなかった。
(Light reflectance evaluation test)
The obtained anisotropic conductive adhesives of Example 2 and Comparative Example 4 were applied to a ceramic white plate so as to have a dry thickness of 100 μm, and heated at 200 ° C. for 1 minute to be cured. About this hardened | cured material, the reflectance (JIS K7150) with respect to the light of wavelength 450nm was measured using the spectrophotometer (U3300, Hitachi Ltd.). The reflectance is 30% or more practically, whereas the light-reflective anisotropic conductive adhesive of Example 2 showed a reflectance exceeding 30%, whereas the anisotropic conductive adhesive of Comparative Example 4 Did not show a reflectivity greater than 30%.
（ＬＥＤ実装サンプルにおける全光束量評価試験）
１００μｍピッチの銅配線にＮｉ／Ａｕ（５．０μｍ厚／０．３μｍ厚）メッキ処理した配線を有するガラスエポキシ基板に、バンプボンダー（ＦＢ７００、カイジョー（株））を用いて１５μｍ高の金バンプを形成した。この金バンプ付きエポキシ基板に、実施例２の光反射性異方性導電接着剤又は比較例４の異方性導電接着剤を用いて、青色ＬＥＤ（Ｖｆ＝３．２（Ｉｆ＝２０ｍＡ））を２００℃、６０秒、１Ｋｇ／チップという条件でフィリップチップ実装し、テスト用ＬＥＤモジュールを得た。
(Evaluation test of total luminous flux in LED mounting sample)
Using a bump bonder (FB700, Kaijo Co., Ltd.) on a glass epoxy board having a Ni / Au (5.0 μm thickness / 0.3 μm thickness) plated wiring on a 100 μm pitch copper wiring, a gold bump of 15 μm height is formed. Formed. By using the light-reflective anisotropic conductive adhesive of Example 2 or the anisotropic conductive adhesive of Comparative Example 4 on this epoxy substrate with gold bumps, a blue LED (Vf = 3.2 (If = 20 mA)) Was mounted on a lip chip under the conditions of 200 ° C., 60 seconds, and 1 kg / chip to obtain a test LED module.
得られたテスト用ＬＥＤモジュールについて、全光束測定システム（積分全球）（ＬＥ−２１００、大塚電子株式会社）を用いて全光束量を測定した（測定条件 Ｉｆ＝２０ｍＡ（定電流制御））。全光束量、実用上３００ｍｌｍ以上であることが望まれるところ、実施例２の光反射性異方性導電接着剤は３００ｍｌｍを超える反射率を示したのに対し、比較例４の異方性導電接着剤は３００ｍｌｍを超える反射率を示さなかった。 About the obtained LED module for a test, the total luminous flux amount was measured using the total luminous flux measurement system (integral sphere) (LE-2100, Otsuka Electronics Co., Ltd.) (measurement condition If = 20 mA (constant current control)). Where the total luminous flux is desired to be practically 300 mlm or more, the light-reflective anisotropic conductive adhesive of Example 2 showed a reflectance exceeding 300 mlm, whereas the anisotropic conductive of Comparative Example 4 The adhesive did not show reflectivity above 300 mlm.
本発明の熱硬化性樹脂組成物並びにそれを絶縁性接着成分として含有する光反射性異方性導電接着剤は、発光ダイオード（ＬＥＤ）素子等の発光素子を配線板に異方性導電接着剤を用いてフリップチップ実装して発光装置を製造する際に、製造コストの増大を招くような光反射層を発光素子に設けなくても、発光効率を低下させないようにすることができる。しかも、ダイシェア強度も高く維持でき、耐熱性、耐熱光性にも優れている。よって、本発明の熱硬化性樹脂組成物及び光反射性異方性導電接着剤は、ＬＥＤ素子をフリップチップ実装する際に有用である。 The thermosetting resin composition of the present invention and the light-reflective anisotropic conductive adhesive containing the same as an insulating adhesive component include an anisotropic conductive adhesive for a light-emitting element such as a light-emitting diode (LED) element on a wiring board. When a light-emitting device is manufactured by flip-chip mounting using a light-emitting element, the light-emitting efficiency can be prevented from being lowered even if a light-reflective layer that causes an increase in manufacturing cost is not provided in the light-emitting element. In addition, the die shear strength can be maintained high, and the heat resistance and heat resistance are excellent. Therefore, the thermosetting resin composition and the light-reflective anisotropic conductive adhesive of the present invention are useful when LED chips are flip-chip mounted.
１ コア粒子
２ 無機粒子
３ 光反射層
４ 熱可塑性樹脂
１０、２０ 光反射性導電粒子
１１ 熱硬化性樹脂組成物の硬化物
２１ 基板
２２ 接続端子
２３ ＬＥＤ素子
２４ ｎ電極
２５ ｐ電極
２６ バンプ
１００ 光反射性異方性導電接着剤の硬化物
２００ 発光装置
DESCRIPTION OF
Claims (15)
（式（１）中、置換基Ｒは炭素数１〜３の低級アルキル基であり、連結基Ａは炭素数２〜６のアルキレン基であり、置換基Ｒ１及びＲ２は、独立的にエポキシ基含有有機基、アルキル基又はアリール基であるが、Ｒ１及びＲ２が共にエポキシ基含有有機基である。）
で表されるエポキシ基含有シロキサン化合物と、エポキシ樹脂用硬化剤とを含有することを特徴とする熱硬化性樹脂組成物。 Formula (1)
(In the formula (1), the substituent R is a lower alkyl group having 1 to 3 carbon atoms, the linking group A is an alkylene group having 2 to 6 carbon atoms, and the substituents R1 and R2 are independently epoxy groups. (It is a contained organic group, an alkyl group or an aryl group, but R1 and R2 are both epoxy group-containing organic groups .)
The thermosetting resin composition characterized by containing the epoxy group containing siloxane compound represented by these, and the hardening | curing agent for epoxy resins.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013068302A JP6003763B2 (en) | 2012-10-30 | 2013-03-28 | Thermosetting resin composition, light reflective anisotropic conductive adhesive, and light emitting device |
| TW102139433A TWI636097B (en) | 2012-10-30 | 2013-10-30 | Thermosetting resin composition, light-reflective anisotropic conductive adhesive, and light-emitting device |
| CN201380056560.2A CN104736591A (en) | 2012-10-30 | 2013-10-30 | Thermosetting resin composition, light-reflective anisotropic electroconductive adhesive, and light-emitting device |
| PCT/JP2013/079468 WO2014069546A1 (en) | 2012-10-30 | 2013-10-30 | Thermosetting resin composition, light-reflective anisotropic electroconductive adhesive, and light-emitting device |
| KR1020157005900A KR102139124B1 (en) | 2012-10-30 | 2013-10-30 | Thermosetting resin composition, light-reflective anisotropic electroconductive adhesive, and light-emitting device |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012238489 | 2012-10-30 | ||
| JP2012238489 | 2012-10-30 | ||
| JP2013068302A JP6003763B2 (en) | 2012-10-30 | 2013-03-28 | Thermosetting resin composition, light reflective anisotropic conductive adhesive, and light emitting device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2014111708A JP2014111708A (en) | 2014-06-19 |
| JP6003763B2 true JP6003763B2 (en) | 2016-10-05 |
Family
ID=50627446
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2013068302A Active JP6003763B2 (en) | 2012-10-30 | 2013-03-28 | Thermosetting resin composition, light reflective anisotropic conductive adhesive, and light emitting device |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP6003763B2 (en) |
| KR (1) | KR102139124B1 (en) |
| CN (1) | CN104736591A (en) |
| TW (1) | TWI636097B (en) |
| WO (1) | WO2014069546A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10658554B2 (en) * | 2014-06-19 | 2020-05-19 | Inkron Oy | LED lamp with siloxane particle material |
| TWI556478B (en) | 2014-06-30 | 2016-11-01 | 億光電子工業股份有限公司 | Light emitting diode device |
| JP6721325B2 (en) * | 2015-12-14 | 2020-07-15 | デクセリアルズ株式会社 | Thermosetting adhesive sheet and method for manufacturing semiconductor device |
| JP6623121B2 (en) * | 2016-06-08 | 2019-12-18 | デクセリアルズ株式会社 | Photo-curable resin composition, image display device, and manufacturing method thereof |
| CN109651425B (en) * | 2017-10-12 | 2021-02-26 | 弗洛里光电材料（苏州）有限公司 | Isocyanate compound containing multiple silicon-hydrogen bonds and application thereof |
| KR102167662B1 (en) * | 2017-11-28 | 2020-10-19 | 주식회사 엘지화학 | Visibility improvement film for display panel and display device comprising the same |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11168235A (en) | 1997-12-05 | 1999-06-22 | Toyoda Gosei Co Ltd | Light emitting diode |
| TWI433875B (en) * | 2008-01-28 | 2014-04-11 | Shinetsu Chemical Co | Diglygidylisocyanurylmodified organopolysiloxane and composition including the organopolysiloxane |
| JP5353629B2 (en) * | 2008-11-14 | 2013-11-27 | 信越化学工業株式会社 | Thermosetting resin composition |
| JP5305452B2 (en) | 2009-06-12 | 2013-10-02 | 信越化学工業株式会社 | Resin composition for optical semiconductor element sealing |
| JP5617210B2 (en) * | 2009-09-14 | 2014-11-05 | デクセリアルズ株式会社 | Light-reflective anisotropic conductive adhesive and light-emitting device |
| JP2011173951A (en) * | 2010-02-23 | 2011-09-08 | Dic Corp | Epoxy resin composition, cured product thereof, resin composition for sealing optical semiconductor, and optical semiconductor device |
| JP2012057006A (en) | 2010-09-07 | 2012-03-22 | Shin-Etsu Chemical Co Ltd | Epoxy resin composition, method of manufacturing the same, and semiconductor device using the same |
| JP5523376B2 (en) * | 2011-03-03 | 2014-06-18 | 新日鉄住金化学株式会社 | Epoxy silicone resin and curable resin composition using the same |
| KR101995599B1 (en) | 2011-03-16 | 2019-07-02 | 데쿠세리아루즈 가부시키가이샤 | Light-reflecting anisotropically conductive adhesive and light emitting device |
| JP6052006B2 (en) * | 2012-10-30 | 2016-12-27 | デクセリアルズ株式会社 | Novel epoxy group-containing siloxane compounds |
-
2013
- 2013-03-28 JP JP2013068302A patent/JP6003763B2/en active Active
- 2013-10-30 WO PCT/JP2013/079468 patent/WO2014069546A1/en active Application Filing
- 2013-10-30 CN CN201380056560.2A patent/CN104736591A/en active Pending
- 2013-10-30 KR KR1020157005900A patent/KR102139124B1/en active IP Right Grant
- 2013-10-30 TW TW102139433A patent/TWI636097B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| TWI636097B (en) | 2018-09-21 |
| WO2014069546A1 (en) | 2014-05-08 |
| CN104736591A (en) | 2015-06-24 |
| JP2014111708A (en) | 2014-06-19 |
| KR102139124B1 (en) | 2020-07-29 |
| TW201430067A (en) | 2014-08-01 |
| KR20150081247A (en) | 2015-07-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5958107B2 (en) | Light-reflective anisotropic conductive adhesive and light-emitting device | |
| JP5888023B2 (en) | Light-reflective anisotropic conductive adhesive and light-emitting device | |
| JP5617210B2 (en) | Light-reflective anisotropic conductive adhesive and light-emitting device | |
| JP5914987B2 (en) | Light-reflective anisotropic conductive paste and light-emitting device | |
| JP5609716B2 (en) | Light-reflective anisotropic conductive adhesive and light-emitting device | |
| JP6003763B2 (en) | Thermosetting resin composition, light reflective anisotropic conductive adhesive, and light emitting device | |
| JP2011222875A (en) | Light-reflective, anisotropic and conductive adhesive, and light-emitting device | |
| WO2014013984A1 (en) | Light-reflective anisotropic electro-conductive adhesive agent, and light-emitting device | |
| JP6115457B2 (en) | Process for producing glycidyl isocyanuryl-modified polysiloxane | |
| JP6384046B2 (en) | Light-reflective anisotropic conductive adhesive and light-emitting device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20151113 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20160607 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20160715 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20160809 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20160822 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6003763 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |