JP5516035B2 - Epoxy resin molding material, substrate for mounting optical semiconductor element, manufacturing method thereof, and optical semiconductor device - Google Patents
Epoxy resin molding material, substrate for mounting optical semiconductor element, manufacturing method thereof, and optical semiconductor device Download PDFInfo
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- JP5516035B2 JP5516035B2 JP2010105524A JP2010105524A JP5516035B2 JP 5516035 B2 JP5516035 B2 JP 5516035B2 JP 2010105524 A JP2010105524 A JP 2010105524A JP 2010105524 A JP2010105524 A JP 2010105524A JP 5516035 B2 JP5516035 B2 JP 5516035B2
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- Prior art keywords
- optical semiconductor
- epoxy resin
- semiconductor element
- molding material
- curing agent
- Prior art date
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- 239000004065 semiconductor Substances 0.000 title claims description 94
- 230000003287 optical effect Effects 0.000 title claims description 93
- 239000003822 epoxy resin Substances 0.000 title claims description 69
- 229920000647 polyepoxide Polymers 0.000 title claims description 69
- 239000000758 substrate Substances 0.000 title claims description 40
- 239000012778 molding material Substances 0.000 title claims description 23
- 238000004519 manufacturing process Methods 0.000 title claims description 21
- 239000011342 resin composition Substances 0.000 claims description 89
- 229920001187 thermosetting polymer Polymers 0.000 claims description 85
- 239000003795 chemical substances by application Substances 0.000 claims description 70
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 54
- 229920005989 resin Polymers 0.000 claims description 42
- 239000011347 resin Substances 0.000 claims description 42
- 150000008065 acid anhydrides Chemical class 0.000 claims description 20
- 239000012463 white pigment Substances 0.000 claims description 19
- 239000000126 substance Substances 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 11
- 238000007789 sealing Methods 0.000 claims description 11
- 125000004018 acid anhydride group Chemical group 0.000 claims description 10
- 238000013329 compounding Methods 0.000 claims description 9
- 125000003700 epoxy group Chemical group 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910000410 antimony oxide Inorganic materials 0.000 claims description 5
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 5
- 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 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 description 21
- 238000000465 moulding Methods 0.000 description 21
- 238000001721 transfer moulding Methods 0.000 description 19
- -1 aromatic dicarboxylic acids Chemical class 0.000 description 18
- 238000000034 method Methods 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 16
- 238000002156 mixing Methods 0.000 description 15
- 239000000463 material Substances 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 12
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 12
- 239000011256 inorganic filler Substances 0.000 description 12
- 229910003475 inorganic filler Inorganic materials 0.000 description 12
- 238000005259 measurement Methods 0.000 description 12
- 239000002253 acid Substances 0.000 description 11
- 238000004898 kneading Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 229930195734 saturated hydrocarbon Natural products 0.000 description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 10
- 238000011109 contamination Methods 0.000 description 9
- 230000007423 decrease Effects 0.000 description 9
- 239000000178 monomer Substances 0.000 description 9
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 8
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 8
- 238000009833 condensation Methods 0.000 description 7
- 230000005494 condensation Effects 0.000 description 7
- 238000006482 condensation reaction Methods 0.000 description 7
- 125000005843 halogen group Chemical group 0.000 description 7
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 7
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000018044 dehydration Effects 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 6
- 238000007747 plating Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 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 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 239000007822 coupling agent Substances 0.000 description 5
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 125000002723 alicyclic group Chemical group 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 description 4
- 239000004914 cyclooctane Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002790 naphthalenes Chemical class 0.000 description 4
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- 125000000962 organic group Chemical group 0.000 description 4
- 238000006068 polycondensation reaction Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 4
- 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 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000001579 optical reflectometry Methods 0.000 description 3
- 150000002903 organophosphorus compounds Chemical class 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 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 2
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 2
- PAVNZLVXYJDFNR-UHFFFAOYSA-N 3,3-dimethyloxane-2,6-dione Chemical compound CC1(C)CCC(=O)OC1=O PAVNZLVXYJDFNR-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 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 2
- LTPBRCUWZOMYOC-UHFFFAOYSA-N Beryllium oxide Chemical compound O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-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
- 239000004793 Polystyrene Substances 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 241000209149 Zea Species 0.000 description 2
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 2
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-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
- 239000006227 byproduct Substances 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 125000003262 carboxylic acid ester group Chemical group [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 235000005822 corn Nutrition 0.000 description 2
- 150000007973 cyanuric acids Chemical class 0.000 description 2
- XBZSBBLNHFMTEB-UHFFFAOYSA-N cyclohexane-1,3-dicarboxylic acid Chemical compound OC(=O)C1CCCC(C(O)=O)C1 XBZSBBLNHFMTEB-UHFFFAOYSA-N 0.000 description 2
- PPQREHKVAOVYBT-UHFFFAOYSA-H dialuminum;tricarbonate Chemical compound [Al+3].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O PPQREHKVAOVYBT-UHFFFAOYSA-H 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 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 2
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 2
- 150000002763 monocarboxylic acids Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 239000003973 paint Substances 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
- 229920000768 polyamine Polymers 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 150000003504 terephthalic acids Chemical class 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 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
- 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 1
- MWIQWRCANQOMBX-UHFFFAOYSA-N 2,2-diethylpentanedioic acid Chemical compound CCC(CC)(C(O)=O)CCC(O)=O MWIQWRCANQOMBX-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
- IUVCFHHAEHNCFT-INIZCTEOSA-N 2-[(1s)-1-[4-amino-3-(3-fluoro-4-propan-2-yloxyphenyl)pyrazolo[3,4-d]pyrimidin-1-yl]ethyl]-6-fluoro-3-(3-fluorophenyl)chromen-4-one Chemical group C1=C(F)C(OC(C)C)=CC=C1C(C1=C(N)N=CN=C11)=NN1[C@@H](C)C1=C(C=2C=C(F)C=CC=2)C(=O)C2=CC(F)=CC=C2O1 IUVCFHHAEHNCFT-INIZCTEOSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- ODGCZQFTJDEYNI-UHFFFAOYSA-N 2-methylcyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1(C)C=CCCC1C(O)=O ODGCZQFTJDEYNI-UHFFFAOYSA-N 0.000 description 1
- UVYLEXYRTBDZNM-UHFFFAOYSA-N 4,4-diethyloxane-2,6-dione Chemical compound CCC1(CC)CC(=O)OC(=O)C1 UVYLEXYRTBDZNM-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000004844 aliphatic epoxy resin Substances 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 229940118662 aluminum carbonate Drugs 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- NIDNOXCRFUCAKQ-UHFFFAOYSA-N bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2C(O)=O NIDNOXCRFUCAKQ-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 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
- 239000012024 dehydrating agents Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000012772 electrical insulation material Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- RQAGEUFKLGHJPA-UHFFFAOYSA-N prop-2-enoylsilicon Chemical compound [Si]C(=O)C=C RQAGEUFKLGHJPA-UHFFFAOYSA-N 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical class OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- JIYNFFGKZCOPKN-UHFFFAOYSA-N sbb061129 Chemical compound O=C1OC(=O)C2C1C1C=C(C)C2C1 JIYNFFGKZCOPKN-UHFFFAOYSA-N 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-N sodium;hydron;carbonate Chemical compound [Na+].OC(O)=O UIIMBOGNXHQVGW-UHFFFAOYSA-N 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000000000 tetracarboxylic acids Chemical class 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
- 238000003856 thermoforming Methods 0.000 description 1
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical class OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- H01L2224/16245—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 metallic
-
- 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
- H01L2224/32245—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 metallic
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/4805—Shape
- H01L2224/4809—Loop shape
- H01L2224/48091—Arched
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/481—Disposition
- H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/48245—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
- H01L2224/48247—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a bond pad of the item
-
- 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
Description
本発明は、熱硬化性樹脂組成物、エポキシ樹脂成形材料、光半導体素子搭載用基板及びその製造方法、並びに光半導体装置に関する。 The present invention relates to a thermosetting resin composition, an epoxy resin molding material, a substrate for mounting an optical semiconductor element, a manufacturing method thereof, and an optical semiconductor device.
ＬＥＤ（Ｌｉｇｈｔ Ｅｍｉｔｔｉｎｇ Ｄｉｏｄｅ：発光ダイオード）等の光半導体素子と蛍光体とを組み合わせた光半導体装置は、エネルギー効率が高く、寿命が長いことから、屋外用ディスプレイ、携帯液晶バックライト、車載用途に使用され、その需要が拡大しつつある。これに伴いＬＥＤデバイスの高輝度化が進んでおり、素子の発熱量増大によるジャンクション温度の上昇や、直接的な光エネルギーの増大による光半導体装置の劣化を防ぐことが求められている。 An optical semiconductor device combining an optical semiconductor element such as an LED (Light Emitting Diode) and a phosphor is high in energy efficiency and has a long life, so it is used for outdoor displays, portable liquid crystal backlights, and in-vehicle applications. The demand is expanding. As a result, the brightness of LED devices is increasing, and it is required to prevent an increase in junction temperature due to an increase in the amount of heat generated by the element and deterioration of the optical semiconductor device due to a direct increase in light energy.
特許文献１には、エポキシ樹脂と酸無水物等の硬化剤とからなる熱硬化性樹脂組成物を用いた光半導体素子搭載用基板が開示されている。 Patent Document 1 discloses an optical semiconductor element mounting substrate using a thermosetting resin composition comprising an epoxy resin and a curing agent such as an acid anhydride.
一般に、酸無水物はエポキシ樹脂の硬化剤として用いられ、また、ジアミンとの反応によりポリイミド化合物を得るための原料として用いられる。酸無水物は、安価で、透明性、電気絶縁性、耐薬品性、耐湿性及び接着性に優れており、電気絶縁材料、半導体装置材料、光半導体封止材料、接着材料、塗料材料等の様々な用途で用いられている。また、酸無水物の一種として、多価カルボン酸の重縮合によって形成されるポリカルボン酸無水物があり、例えば、ポリアゼライン酸、ポリセバシン酸等の脂肪族ジカルボン酸の分子間脱水縮合反応によって得られるポリカルボン酸無水物が市販されている。 In general, an acid anhydride is used as a curing agent for an epoxy resin, and is also used as a raw material for obtaining a polyimide compound by reaction with a diamine. Acid anhydrides are inexpensive and have excellent transparency, electrical insulation, chemical resistance, moisture resistance, and adhesion, and include electrical insulation materials, semiconductor device materials, optical semiconductor sealing materials, adhesive materials, paint materials, etc. It is used for various purposes. Also, as one kind of acid anhydride, there is a polycarboxylic acid anhydride formed by polycondensation of polyvalent carboxylic acid, and it can be obtained, for example, by intermolecular dehydration condensation reaction of aliphatic dicarboxylic acid such as polyazeline acid and polysebacic acid. Polycarboxylic acid anhydrides are commercially available.
ところで、酸無水物のその他用途として、特許文献２では、脂肪族及び芳香族ジカルボン酸を分子間で縮合して得られる、平均分子量が２００００を超える高分子量のポリカルボン酸無水物（多価カルボン酸縮合体）の使用が生体医学用途において提案されている。 Incidentally, as other uses of acid anhydrides, Patent Document 2 discloses a polycarboxylic acid anhydride (polyvalent carboxylic acid) having a high average molecular weight exceeding 20000, obtained by condensing aliphatic and aromatic dicarboxylic acids between molecules. The use of acid condensates has been proposed for biomedical applications.
しかしながら、エポキシ樹脂等の熱硬化性樹脂の硬化剤として実用化されている酸無水物系硬化剤は、ポリアミン、フェノールノボラック及びイミダゾール系硬化剤ほど種類が豊富ではない。上述のポリカルボン酸無水物は、エポキシ樹脂用の硬化剤として分子設計されたものではなく、その用途は限られている。 However, there are not as many types of acid anhydride curing agents that are put into practical use as curing agents for thermosetting resins such as epoxy resins, as are polyamines, phenol novolacs, and imidazole curing agents. The above-mentioned polycarboxylic acid anhydrides are not molecularly designed as curing agents for epoxy resins, and their uses are limited.
また、酸無水物系硬化剤には、耐紫外線特性、耐熱着色性及び各種光学特性に優れた光学材料への適用にむけて脂環式構造を導入することが試みられている。しかし、従来の脂環式酸無水物は、一般的に融点が４０℃未満と低く、用途に制限があった。一方、ジアミンと組み合わせてポリイミド樹脂を形成するために従来用いられている芳香族又は直鎖状若しくは環状脂肪族のテトラカルボン酸無水物の多くは、その融点が１５０℃以上であり、ポリイミド樹脂の原料以外への適用は困難であった。 In addition, an attempt has been made to introduce an alicyclic structure into an acid anhydride-based curing agent for application to an optical material excellent in ultraviolet resistance, heat resistance and various optical characteristics. However, conventional alicyclic acid anhydrides generally have a low melting point of less than 40 ° C. and have limited applications. On the other hand, most of aromatic or linear or cycloaliphatic tetracarboxylic acid anhydrides conventionally used for forming a polyimide resin in combination with a diamine have a melting point of 150 ° C. or higher. Application to materials other than raw materials has been difficult.
また、従来の熱硬化性樹脂組成物は、トランスファー成形によって光半導体搭載用基板を製造しようとした場合、成形時に成形金型の上型と下型との隙間に樹脂組成物が染み出し、樹脂よごれが発生しやすい傾向がある。加熱成形時に樹脂よごれが発生すると、光半導体素子搭載領域となる基板の開口部（凹部）に樹脂よごれが張り出し、光半導体素子を搭載する際の障害になる。また、開口部に光半導体素子を搭載できたとしても、樹脂汚れは、光半導体素子と金属配線とをボンディングワイヤなどによって電気的に接続する際の接続不良等の障害を引き起こすことがある。そのため、基板の開口部に樹脂汚れが存在する場合には、光半導体素子搭載用基板の製造プロセスに樹脂よごれの除去工程が追加される。このような除去工程は、作業性を低下させ、製造時間のロスとなり製造コストの増加に繋がり易いため、樹脂汚れを低減することが望まれている。 In addition, when a conventional thermosetting resin composition is intended to produce a substrate for mounting an optical semiconductor by transfer molding, the resin composition oozes into the gap between the upper mold and the lower mold of the molding die during molding. There is a tendency for dirt to occur. If resin contamination occurs during thermoforming, the resin contamination protrudes into the opening (concave portion) of the substrate, which is the optical semiconductor element mounting region, and becomes an obstacle when mounting the optical semiconductor element. Further, even if the optical semiconductor element can be mounted in the opening, the resin stain may cause a failure such as a connection failure when the optical semiconductor element and the metal wiring are electrically connected by a bonding wire or the like. For this reason, in the case where there is resin contamination in the opening of the substrate, a resin dirt removing step is added to the manufacturing process of the optical semiconductor element mounting substrate. Since such a removal process reduces workability, loss of manufacturing time, and easily increases manufacturing cost, it is desired to reduce resin contamination.
本発明は、上記事情に鑑みてなされたものであり、成形時における樹脂汚れの発生を低減し成形性に十分に優れる熱硬化性樹脂組成物及びエポキシ樹脂成形材料、これを用いた光半導体素子搭載用基板及びその製造方法、並びに光半導体装置を提供することを目的とする。 The present invention has been made in view of the above circumstances, and is a thermosetting resin composition and an epoxy resin molding material that are sufficiently excellent in moldability by reducing the occurrence of resin stains during molding, and an optical semiconductor element using the same It is an object to provide a mounting substrate, a manufacturing method thereof, and an optical semiconductor device.
本発明は、（Ａ）エポキシ樹脂及び（Ｂ）硬化剤を含有する熱硬化性樹脂組成物であって、（Ｂ）硬化剤が、下記一般式（１）で表される成分を有する多価カルボン酸縮合体を含む熱硬化性樹脂組成物を提供する。式（１）中、Ｒｘは、２価の有機基を示し、同一分子中の複数のＲｘは同一でも異なっていてもよく、Ｒｙは、１価の有機基を示し、同一分子中の２個のＲｙは同一でも異なっていてもよく、ｎ１は１以上の整数を示す。
上記成分を含む多価カルボン酸縮合体を含有する（Ｂ）硬化剤は、例えば、トランスファー成形用材料として用いられたときに、流動性、成形性、作業性、保存安定性及び配合設計の自由度の観点から求められる適度な融点や粘度を容易に達成することが可能である。よって、上述の構成を備える本発明の熱硬化性樹脂組成物は、成形時における樹脂汚れの発生を低減し成形性に十分に優れるものとなる。 The (B) curing agent containing the polyvalent carboxylic acid condensate containing the above components, for example, when used as a transfer molding material, fluidity, moldability, workability, storage stability and freedom of compounding design. It is possible to easily achieve an appropriate melting point and viscosity required from the viewpoint of degree. Therefore, the thermosetting resin composition of the present invention having the above-described configuration is sufficiently excellent in moldability by reducing the occurrence of resin stains during molding.
上記Ｒｘは、脂肪族炭化水素環を有し該脂肪族炭化水素環がハロゲン原子又は直鎖状若しくは分岐状の炭化水素基で置換されていてもよい２価の基であり、上記Ｒｙは、酸無水物基又はカルボン酸エステル基で置換されていてもよい１価の炭化水素基であることが好ましい。 R x is a divalent group which has an aliphatic hydrocarbon ring and the aliphatic hydrocarbon ring may be substituted with a halogen atom or a linear or branched hydrocarbon group, and the R y Is preferably a monovalent hydrocarbon group which may be substituted with an acid anhydride group or a carboxylic acid ester group.
また、上記Ｒｘは、下記一般式（１０）で表される２価の基であることが好ましい。式（１０）中、ｍは０〜４の整数を示し、Ｒｚはハロゲン原子又は直鎖状若しくは分岐状の炭素数１〜４の炭化水素基を示し、ｍが２〜４であるとき複数のＲｚは同一でも異なっていてもよく、互いに連結して環を形成していてもよい。
上記Ｒｙは、下記化学式（２０）で表される１価の基、又は、シクロブタン、シクロペンタン、シクロヘキサン、シクロへプタン、シクロオクタン、ノルボルネン、ジシクロペンタジエン、アダマンタン、水素化ナフタレン及び水素化ビフェニルから選ばれる環式脂肪族炭化水素から水素原子を除くことにより誘導される１価の基であることが好ましい。
熱硬化性樹脂組成物の着色を抑制する観点から、上記一般式（１）で表される成分は、下記一般式（１ａ）で表される成分を含むことが好ましい。式（１ａ）中、ｍは０〜４の整数を示し、Ｒｚはハロゲン原子又は直鎖状若しくは分岐状の炭素数１〜４の炭化水素基を示し、ｍが２〜４であるとき複数のＲｚは同一でも異なっていてもよく、互いに連結して環を形成していてもよく、ｎ１は１以上の整数を示す。
上記多価カルボン酸縮合体の数平均分子量は、好ましくは２００〜２００００である。 The number average molecular weight of the polyvalent carboxylic acid condensate is preferably 200 to 20000.
ＩＣＩコーンプレート型粘度計によって測定される多価カルボン酸縮合体の粘度は、１５０℃で１０〜３００００ｍＰａ・ｓであることが好ましい。 The viscosity of the polyvalent carboxylic acid condensate measured with an ICI cone plate viscometer is preferably 10 to 30000 mPa · s at 150 ° C.
本発明の熱硬化性樹脂組成物において、（Ｂ）硬化剤の配合量は、（Ａ）エポキシ樹脂１００質量部に対して１０〜１５０質量部であることが好ましい。 In the thermosetting resin composition of the present invention, the blending amount of the (B) curing agent is preferably 10 to 150 parts by mass with respect to 100 parts by mass of the (A) epoxy resin.
本発明の熱硬化性樹脂組成物では、（Ｂ）硬化剤が、多価カルボン酸が分子内で閉環縮合してなる酸無水物を更に含むことができる。また、（Ｂ）硬化剤が、下記化学式（３）で表される多価カルボン酸縮合体を更に含むことができる。この場合、（Ａ）エポキシ樹脂中に含まれるエポキシ基と、エポキシ基と反応可能な（Ｂ）硬化剤中の酸無水物基との当量比が、１：０．３〜１：１．２であることが好ましい。これにより、本発明の熱硬化性樹脂組成物の成形時における樹脂汚れをより一層低減することができる。
硬化後、可視光から近紫外光領域における光反射率を高くできることから、本発明の熱硬化性樹脂組成物は、（Ｄ）白色顔料を更に含有することが好ましい Since the light reflectance in the visible light to near ultraviolet light region can be increased after curing, the thermosetting resin composition of the present invention preferably further contains (D) a white pigment.
（Ｄ）白色顔料は、アルミナ、酸化マグネシウム、酸化アンチモン、酸化チタン、酸化ジルコニウム及び無機中空粒子からなる群より選ばれる少なくとも１種の無機物を含むことが好ましい。 (D) The white pigment preferably contains at least one inorganic substance selected from the group consisting of alumina, magnesium oxide, antimony oxide, titanium oxide, zirconium oxide and inorganic hollow particles.
熱硬化性樹脂組成物中における分散性を向上する観点から、（Ｄ）白色顔料の中心粒径は、０．１〜５０μｍであることが好ましい。 From the viewpoint of improving dispersibility in the thermosetting resin composition, it is preferable that the center particle diameter of the (D) white pigment is 0.1 to 50 μm.
（Ｄ）白色顔料の配合量は、熱硬化性樹脂組成物全体に対して１０〜８５体積％であると、本発明の熱硬化性樹脂組成物は、より成形性に優れるものとなる。 (D) When the compounding quantity of a white pigment is 10-85 volume% with respect to the whole thermosetting resin composition, the thermosetting resin composition of this invention will become more excellent in a moldability.
また、本発明は、（Ａ）エポキシ樹脂及び（Ｂ）硬化剤を含有する熱硬化性樹脂組成物であって、ＩＣＩコーンプレート型粘度計によって測定される（Ｂ）硬化剤の粘度が、１５０℃で１．０〜１０００ｍＰａ・ｓである熱硬化性樹脂組成物を提供する。 The present invention also relates to a thermosetting resin composition containing (A) an epoxy resin and (B) a curing agent, wherein the viscosity of (B) the curing agent measured by an ICI cone plate viscometer is 150. A thermosetting resin composition having a temperature of 1.0 to 1000 mPa · s at a temperature is provided.
さらに、本発明は、（Ａ）エポキシ樹脂及び（Ｂ）硬化剤を含有するエポキシ樹脂成形材料であって、（Ｂ）硬化剤が多価カルボン酸縮合体を含むエポキシ樹脂成形材料を提供する。 Furthermore, the present invention provides an epoxy resin molding material containing (A) an epoxy resin and (B) a curing agent, wherein (B) the curing agent contains a polyvalent carboxylic acid condensate.
本発明はまた、底面及び壁面から構成される凹部を有し、凹部の底面が光半導体素子搭載部であり、凹部の壁面の少なくとも一部が本発明の熱硬化性樹脂組成物又はエポキシ樹脂成形材料の硬化物からなる光半導体素子搭載用基板を提供する。 The present invention also has a recess composed of a bottom surface and a wall surface, the bottom surface of the recess is an optical semiconductor element mounting portion, and at least a part of the wall surface of the recess is the thermosetting resin composition or epoxy resin molding of the present invention. Provided is an optical semiconductor element mounting substrate made of a cured material.
本発明はさらに、底面及び壁面から構成される凹部を有する光半導体素子搭載用基板の製造方法であって、凹部の壁面の少なくとも一部を、本発明の熱硬化性樹脂組成物又はエポキシ樹脂成形材料を用いて形成する工程を備える光半導体素子搭載用基板の製造方法を提供する。 The present invention further relates to a method for manufacturing a substrate for mounting an optical semiconductor element having a recess composed of a bottom surface and a wall surface, wherein at least part of the wall surface of the recess is molded with the thermosetting resin composition or epoxy resin molding of the present invention. Provided is a method for manufacturing a substrate for mounting an optical semiconductor element comprising a step of forming using a material.
本発明は、底面及び壁面から構成される凹部を有する光半導体素子搭載用基板と、光半導体素子搭載用基板の凹部内に設けられた光半導体素子と、凹部を充填して光半導体素子を封止する封止樹脂部とを備え、凹部の壁面の少なくとも一部が本発明の熱硬化性樹脂組成物又はエポキシ樹脂成形材料の硬化物からなる光半導体装置を提供する。 The present invention includes a substrate for mounting an optical semiconductor element having a recess composed of a bottom surface and a wall surface, an optical semiconductor element provided in the recess of the substrate for mounting an optical semiconductor element, and sealing the optical semiconductor element by filling the recess. There is provided an optical semiconductor device including a sealing resin portion to be stopped, and at least a part of the wall surface of the recess is made of a cured product of the thermosetting resin composition or the epoxy resin molding material of the present invention.
本発明によれば、成形時における樹脂汚れの発生を低減し成形性に十分に優れる熱硬化性樹脂組成物、エポキシ樹脂成形材料、これを用いた光半導体素子搭載用基板及びその製造方法、並びに光半導体装置を提供することができる。 According to the present invention, a thermosetting resin composition, an epoxy resin molding material, a substrate for mounting an optical semiconductor element using the same, and a method for producing the same, which reduce the occurrence of resin stains during molding and are sufficiently excellent in moldability, and An optical semiconductor device can be provided.
以下、必要に応じて図面を参照しつつ、本発明の好適な実施形態について詳細に説明する。なお、図面中、同一要素には同一符号を付すこととし、重複する説明は省略する。また、上下左右等の位置関係は、特に断らない限り、図面に示す位置関係に基づくものとする。更に、図面の寸法比率は図示の比率に限られるものではない。また、本明細書における「（メタ）アクリレート」とは、「アクリレート」又はそれに対応する「メタクリレート」を意味する。 Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as necessary. In the drawings, the same elements are denoted by the same reference numerals, and redundant description is omitted. Further, the positional relationship such as up, down, left and right is based on the positional relationship shown in the drawings unless otherwise specified. Further, the dimensional ratios in the drawings are not limited to the illustrated ratios. In addition, “(meth) acrylate” in the present specification means “acrylate” or “methacrylate” corresponding thereto.
［熱硬化性樹脂組成物］
本発明の一実施形態に係る熱硬化性樹脂組成物は、（Ａ）エポキシ樹脂及び（Ｂ）硬化剤を含有するものであり、（Ｂ）硬化剤が、上記一般式（１）で表される成分を有する多価カルボン酸縮合体を含むものである。
[Thermosetting resin composition]
The thermosetting resin composition according to an embodiment of the present invention contains (A) an epoxy resin and (B) a curing agent, and (B) the curing agent is represented by the general formula (1). And a polyvalent carboxylic acid condensate having the following components.
また、本発明の別の実施形態に係る熱硬化性樹脂組成物は、（Ａ）エポキシ樹脂及び（Ｂ）硬化剤を含有する熱硬化性樹脂組成物であって、ＩＣＩコーンプレート型粘度計によって測定される（Ｂ）硬化剤の粘度が、１５０℃で１．０〜１０００ｍＰａ・ｓである。 Moreover, the thermosetting resin composition which concerns on another embodiment of this invention is a thermosetting resin composition containing (A) epoxy resin and (B) hardening | curing agent, Comprising: By ICI cone plate type viscometer The viscosity of the (B) curing agent to be measured is 1.0 to 1000 mPa · s at 150 ° C.
＜（Ａ）エポキシ樹脂＞
（Ａ）エポキシ樹脂としては、電子部品封止用エポキシ樹脂成形材料で一般に使用されているものを用いることができる。エポキシ樹脂として、例えば、フェノールノボラック型エポキシ樹脂及びオルソクレゾールノボラック型エポキシ樹脂等のフェノール類とアルデヒド類のノボラック樹脂をエポキシ化したもの、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳ及びアルキル置換ビスフェノール等のジグリシジルエーテル、ジアミノジフェニルメタン及びイソシアヌル酸等のポリアミンとエピクロルヒドリンとの反応により得られるグリシジルアミン型エポキシ樹脂、オレフィン結合を過酢酸等の過酸で酸化して得られる線状脂肪族エポキシ樹脂、並びに脂環族エポキシ樹脂が挙げられる。これらは、１種を単独で又は２種以上を組み合わせて用いることができる。
<(A) Epoxy resin>
(A) As an epoxy resin, what is generally used with the epoxy resin molding material for electronic component sealing can be used. Examples of epoxy resins include epoxidized phenol and aldehyde novolak resins such as phenol novolac type epoxy resin and orthocresol novolak type epoxy resin, diglycidyl such as bisphenol A, bisphenol F, bisphenol S and alkyl-substituted bisphenol. Glycidylamine type epoxy resin obtained by reaction of polyamine such as ether, diaminodiphenylmethane and isocyanuric acid with epichlorohydrin, linear aliphatic epoxy resin obtained by oxidizing olefin bond with peracid such as peracetic acid, and alicyclic An epoxy resin is mentioned. These can be used alone or in combination of two or more.
これらのうち、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、ジグリシジルイソシアヌレート、トリグリシジルイソシアヌレート、及び、１，２−シクロヘキサンジカルボン酸、１，３−シクロヘキサンジカルボン酸又は１，４−シクロヘキサンジカルボン酸から誘導されるジカルボン酸ジグリシジルエステルが、比較的着色が少ないことから好ましい。同様の理由から、フタル酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、メチルテトラヒドロフタル酸、ナジック酸及びメチルナジック酸等のジカルボン酸のジグリシジルエステルも好適である。芳香環が水素化された脂環式構造を有する核水素化トリメリット酸、核水素化ピロメリット酸等のグリシジルエステルも挙げられる。シラン化合物を有機溶媒、有機塩基及び水の存在下に加熱して、加水分解・縮合させることにより製造される、エポキシ基を有するポリオルガノシロキサンも挙げられる。また、（Ａ）成分として、グリシジル（メタ）アクリレート単量体と、これと重合可能な単量体との共重合体である、下記式（７）で示されるエポキシ樹脂を用いることもできる。 Among these, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, diglycidyl isocyanurate, triglycidyl isocyanurate, and 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid or A dicarboxylic acid diglycidyl ester derived from 1,4-cyclohexanedicarboxylic acid is preferable because of relatively little coloring. For the same reason, diglycidyl esters of dicarboxylic acids such as phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methyltetrahydrophthalic acid, nadic acid and methylnadic acid are also suitable. Examples thereof include glycidyl esters such as nuclear hydrogenated trimellitic acid and nuclear hydrogenated pyromellitic acid having an alicyclic structure in which an aromatic ring is hydrogenated. Polyorganosiloxane having an epoxy group produced by heating and hydrolyzing and condensing a silane compound in the presence of an organic solvent, an organic base and water is also included. Further, as the component (A), an epoxy resin represented by the following formula (7), which is a copolymer of a glycidyl (meth) acrylate monomer and a polymerizable monomer, can also be used.
式（７）中、Ｒ１はグリシジル基を示し、Ｒ２は水素原子又はメチル基を示し、Ｒ３は水素原子又は炭素数１〜６の飽和若しくは不飽和の１価の炭化水素基を示し、Ｒ４は１価の飽和炭化水素基を示す。ａ及びｂは正の整数を示す。 In Formula (7), R 1 represents a glycidyl group, R 2 represents a hydrogen atom or a methyl group, R 3 represents a hydrogen atom or a saturated or unsaturated monovalent hydrocarbon group having 1 to 6 carbon atoms. , R 4 represents a monovalent saturated hydrocarbon group. a and b represent a positive integer.
硬化物の着色を抑制するために、エポキシ樹脂は、シクロブタン、シクロペンタン、シクロヘキサン、シクロへプタン、シクロオクタン、ノルボルネン、ジシクロペンタジエン、アダマンタン、水素化ナフタレン及び水素化ビフェニルから選ばれる環式脂肪族炭化水素から水素原子を除くことにより誘導される脂肪族炭化水素基を有する脂環式エポキシ樹脂であることも好ましい。上記環式脂肪族炭化水素は、ハロゲン原子又は直鎖状若しくは分岐状の炭化水素基で置換されていてもよい。 In order to suppress coloration of the cured product, the epoxy resin is a cycloaliphatic selected from cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, norbornene, dicyclopentadiene, adamantane, hydrogenated naphthalene, and hydrogenated biphenyl. An alicyclic epoxy resin having an aliphatic hydrocarbon group derived by removing a hydrogen atom from a hydrocarbon is also preferred. The cycloaliphatic hydrocarbon may be substituted with a halogen atom or a linear or branched hydrocarbon group.
＜（Ｂ）硬化剤＞
本実施形態に係る硬化剤は、多価カルボン酸縮合体を含むものであればよく、ＩＣＩコーンプレート型粘度計によって測定される（Ｂ）硬化剤の粘度が、１５０℃で１．０〜１０００ｍＰａ・ｓであることが好ましく、１０〜２００ｍＰａ・ｓであることがより好ましい。（Ｂ）硬化剤の粘度が、係る特定範囲内にあることにより、例えば、多価カルボン酸縮合体を配合した熱硬化性樹脂組成物をトランスファー成形に用いたときに、バリ発生が抑制されるなど、良好な成形性が得られる。硬化剤の粘度を調整する方法としては、多価カルボン酸縮合体の平均分子量を制御することなどにより多価カルボン酸縮合体の粘度を調整する方法や、多価カルボン酸縮合体と、併用可能な硬化剤との配合比を調整する方法が挙げられる。
<(B) Curing agent>
The hardening | curing agent which concerns on this embodiment should just contain a polyhydric carboxylic acid condensate, and the viscosity of the (B) hardening | curing agent measured with an ICI cone plate type viscometer is 1.0-1000 mPa at 150 degreeC. -It is preferable that it is s, and it is more preferable that it is 10-200 mPa * s. (B) When the viscosity of the curing agent is within the specific range, for example, when a thermosetting resin composition containing a polyvalent carboxylic acid condensate is used for transfer molding, the occurrence of burrs is suppressed. Good moldability can be obtained. As a method of adjusting the viscosity of the curing agent, a method of adjusting the viscosity of the polyvalent carboxylic acid condensate by controlling the average molecular weight of the polyvalent carboxylic acid condensate, or a combination with the polyvalent carboxylic acid condensate can be used. The method of adjusting the compounding ratio with a hardener is mentioned.
（Ｂ）硬化剤の粘度を調整するのに望ましい多価カルボン酸縮合体の粘度は、１５０℃で１０〜３００００ｍＰａ・ｓであることが好ましく、１０〜１００００ｍＰａ・ｓであることがより好ましい。上記温度範囲における多価カルボン酸縮合体の粘度が１０ｍＰａ・ｓ未満では、トランスファー成形時の樹脂汚れの発生を抑える効果が低くなる傾向にあり、３００００ｍＰａ・ｓを超えると、トランスファー成形時の金型内で熱硬化性樹脂組成物の流動性が低下する傾向にある。多価カルボン酸縮合体の粘度は、例えばＲｅｓｅａｃｈ Ｅｑｕｉｐｍｅｎｔ（Ｌｏｎｄｏｎ）ＬＴＤ．製のＩＣＩコーンプレート型粘度計を用いて測定することができる。 (B) The viscosity of the polyvalent carboxylic acid condensate desirable for adjusting the viscosity of the curing agent is preferably 10 to 30000 mPa · s at 150 ° C., more preferably 10 to 10000 mPa · s. When the viscosity of the polyvalent carboxylic acid condensate in the above temperature range is less than 10 mPa · s, the effect of suppressing the occurrence of resin stains at the time of transfer molding tends to be low, and when it exceeds 30000 mPa · s, the mold at the time of transfer molding The fluidity of the thermosetting resin composition tends to decrease. The viscosity of the polyvalent carboxylic acid condensate can be measured, for example, by Research Equipment (London) LTD. It can be measured using a manufactured ICI cone plate viscometer.
本明細書において「多価カルボン酸縮合体」とは、２以上のカルボキシル基を有する多価カルボン酸の１種又は２種以上が分子間で縮合して形成される重合体を意味する。より詳細には、多価カルボン酸縮合体は、２以上のカルボキル基を有する２分子以上のモノマーの分子間で、それぞれが有するカルボキシ基が脱水縮合することにより酸無水物基（酸無水物結合）を生成し、生成した酸無水物基によって各モノマー単位が鎖状又は環状に連結されている重合体である。一方、「多価カルボン酸のカルボキシル基を分子内で脱水縮合させて得ることのできる酸無水物化合物」とは、２以上のカルボキシル基を有する多価カルボン酸のカルボキシル基が分子内で脱水縮合して酸無水物基を生成し、生成した酸無水物基を含む環状構造が形成されている酸無水物化合物を意味する。 In the present specification, the “polycarboxylic acid condensate” means a polymer formed by condensation of one or more polycarboxylic acids having two or more carboxyl groups between molecules. More specifically, the polyvalent carboxylic acid condensate has an acid anhydride group (an acid anhydride bond) formed by dehydration condensation between carboxy groups of two or more monomers having two or more carboxy groups. ) And each monomer unit is linked in a chain or cyclic manner by the generated acid anhydride group. On the other hand, “an acid anhydride compound that can be obtained by dehydrating and condensing a carboxyl group of a polyvalent carboxylic acid in a molecule” means that a carboxyl group of a polyvalent carboxylic acid having two or more carboxyl groups is dehydrated and condensed in the molecule. It means an acid anhydride compound in which an acid anhydride group is generated and a cyclic structure including the generated acid anhydride group is formed.
本実施形態に係る多価カルボン酸縮合体は、通常、重合度の異なる複数の成分から構成され、繰り返し単位及び末端基の構成が異なる複数の成分を含み得る。本実施形態に係る多価カルボン酸縮合体は、下記一般式（１）で表される成分を主成分として含むことが好ましい。式（１）中、Ｒｘは２価の有機基を示し、Ｒｙは１価の有機基を示す。好ましくは、式（１）の成分の割合は多価カルボン酸縮合体全量を基準として６０質量％以上である。 The polyvalent carboxylic acid condensate according to the present embodiment is usually composed of a plurality of components having different degrees of polymerization, and may include a plurality of components having different constitutions of repeating units and terminal groups. The polyvalent carboxylic acid condensate according to the present embodiment preferably includes a component represented by the following general formula (1) as a main component. In formula (1), R x represents a divalent organic group, and R y represents a monovalent organic group. Preferably, the proportion of the component of formula (1) is 60% by mass or more based on the total amount of the polyvalent carboxylic acid condensate.
式（１）中のＲｘは飽和炭化水素環を有する２価の飽和炭化水素基であることが好ましい。Ｒｘが飽和炭化水素環を有する飽和炭化水素基であることにより、当該多価カルボン酸縮合体はエポキシ樹脂の透明な硬化物を形成させることが可能である。同一分子中の複数のＲｘは同一でも異なっていてもよい。Ｒｘの飽和炭化水素環はハロゲン原子又は直鎖状若しくは分岐状の炭化水素基で置換されていてもよい。飽和炭化水素環を置換する炭化水素基は好ましくは飽和炭化水素基である。飽和炭化水素環は単環でもよいし、２以上の環から構成される縮合環、ポリシクロ環、スピロ環又は環集合であってもよい。Ｒｘの炭素数は好ましくは３〜１５である。 R x in formula (1) is preferably a divalent saturated hydrocarbon group having a saturated hydrocarbon ring. When R x is a saturated hydrocarbon group having a saturated hydrocarbon ring, the polyvalent carboxylic acid condensate can form a transparent cured product of an epoxy resin. A plurality of R x in the same molecule may be the same or different. The saturated hydrocarbon ring of R x may be substituted with a halogen atom or a linear or branched hydrocarbon group. The hydrocarbon group that substitutes the saturated hydrocarbon ring is preferably a saturated hydrocarbon group. The saturated hydrocarbon ring may be a single ring or a condensed ring, a polycyclo ring, a spiro ring or a ring assembly composed of two or more rings. R x preferably has 3 to 15 carbon atoms.
Ｒｘは一般式（１）で表される成分（重合体）を得るために用いられるモノマーとしての多価カルボン酸からカルボキシル基を除いて誘導される基である。モノマーとしての多価カルボン酸は、重縮合の反応温度よりも高い沸点を有することが好ましい。 R x is a group derived by removing a carboxyl group from a polyvalent carboxylic acid as a monomer used to obtain the component (polymer) represented by the general formula (1). The polyvalent carboxylic acid as a monomer preferably has a boiling point higher than the reaction temperature of polycondensation.
より具体的には、Ｒｘはシクロブタン、シクロペンタン、シクロヘキサン、シクロへプタン、シクロオクタン、ノルボルネン、ジシクロペンタジエン、アダマンタン、水素化ナフタレン及び水素化ビフェニルから選ばれる環式脂肪族炭化水素から水素原子を除くことにより誘導される２価の基であることが好ましい。Ｒｘがこれらの基であることにより、透明で熱による着色の少ない硬化物が得られるという効果がより一層顕著に奏される。これら環式飽和炭化水素は、ハロゲン原子又は直鎖状若しくは分岐状の炭化水素基（好ましくは飽和炭化水素基）で置換されていてもよい。 More specifically, R x is a hydrogen atom from a cyclic aliphatic hydrocarbon selected from cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, norbornene, dicyclopentadiene, adamantane, hydrogenated naphthalene and hydrogenated biphenyl. It is preferably a divalent group derived by removing. When R x is these groups, the effect of obtaining a cured product that is transparent and less colored by heat is more remarkably exhibited. These cyclic saturated hydrocarbons may be substituted with a halogen atom or a linear or branched hydrocarbon group (preferably a saturated hydrocarbon group).
特に、Ｒｘは１，２−シクロヘキサンジカルボン酸、１，３−シクロヘキサンジカルボン酸、１，４−シクロヘキサンジカルボン酸又はこれらの誘導体からカルボキシル基を除いて誘導される基であることが好ましい。すなわち、Ｒｘは下記一般式（１０）で表される２価の基であることが好ましい。式（１０）中、ｍは０〜４の整数を示す。Ｒｚはハロゲン原子又は直鎖状若しくは分岐状の炭素数１〜４の炭化水素基を示す。ｍが２〜４であるとき、複数のＲｚは同一でも異なっていてもよく、互いに連結して環を形成していてもよい。 In particular, R x is preferably a group derived by removing a carboxyl group from 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid or derivatives thereof. That is, R x is preferably a divalent group represented by the following general formula (10). In formula (10), m represents an integer of 0 to 4. R z represents a halogen atom or a linear or branched hydrocarbon group having 1 to 4 carbon atoms. When m is 2 to 4, a plurality of R z may be the same or different, and may be connected to each other to form a ring.
式（１）中の末端基であるＲｙは酸無水物基又はカルボン酸エステル基で置換されていてもよい１価の炭化水素基を示す。２個のＲｙは同一でも異なっていてもよい。Ｒｙは、直鎖状、分岐状若しくは環状の炭素数２〜１５の脂肪族若しくは芳香族モノカルボン酸（安息香酸等）からカルボキシル基を除くことにより誘導される１価の基であってもよい。 R y as a terminal group in the formula (1) represents a monovalent hydrocarbon group which may be substituted with an acid anhydride group or a carboxylic acid ester group. Two R y may be the same or different. R y may be a monovalent group derived by removing a carboxyl group from a linear, branched, or cyclic C 2-15 aliphatic or aromatic monocarboxylic acid (benzoic acid or the like). Good.
Ｒｙは、好ましくは、下記化学式（２０）で表される１価の基、又は、シクロブタン、シクロペンタン、シクロヘキサン、シクロへプタン、シクロオクタン、ノルボルネン、ジシクロペンタジエン、アダマンタン、水素化ナフタレン及び水素化ビフェニルから選ばれる環式脂肪族炭化水素から水素原子を除くことにより誘導される１価の基である。Ｒｙがこれらの基であることにより、熱による着色の少ない硬化物が得られるという効果がより一層顕著に奏される。また、Ｒｙがこれらの基であると、多価カルボン酸縮合体中のカルボン酸残基の濃度が低減すると共に、分子量の分散を抑えることができる。 R y is preferably a monovalent group represented by the following chemical formula (20), or cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, norbornene, dicyclopentadiene, adamantane, hydrogenated naphthalene and hydrogen It is a monovalent group derived by removing a hydrogen atom from a cycloaliphatic hydrocarbon selected from conjugated biphenyl. By Ry being these groups, the effect of obtaining a cured product with less coloring due to heat is more remarkably exhibited. Further, when R y is such a group, the concentration of the carboxylic acid residue in the polyvalent carboxylic acid condensate can be reduced, and dispersion of the molecular weight can be suppressed.
Ｒｘが上記一般式（１０）で表される２価の基であり、同時に、Ｒｙが上記化学式（２０）で表される１価の基であってもよい。すなわち、本実施形態に係る多価カルボン酸縮合体は、一般式（１）で表される成分として、下記一般式（１ａ）で表される成分を含んでいてもよい。 R x may be a divalent group represented by the general formula (10), and at the same time, R y may be a monovalent group represented by the chemical formula (20). That is, the polyvalent carboxylic acid condensate according to the present embodiment may include a component represented by the following general formula (1a) as the component represented by the general formula (1).
式（１）及び（１ａ）のｎ１は１以上の整数を示し、好ましくは１〜２００の整数である。 N1 of Formula (1) and (1a) shows an integer greater than or equal to 1 , Preferably it is an integer of 1-200.
多価カルボン酸縮合体の数平均分子量Ｍｎは、２００〜２００００であることが好ましく、３００〜２００００であることがより好ましく、３００〜１００００であることが更に好ましい。Ｍｎが２００未満では、粘度が低くなりすぎて熱硬化性樹脂組成物のトランスファー成形時の樹脂汚れの発生を抑制し難くなる傾向があり、２００００を超えると、エポキシ樹脂との相溶性が低下する傾向や、熱硬化性樹脂組成物のトランスファー成形時の流動性が低下する傾向がある。 The number average molecular weight Mn of the polyvalent carboxylic acid condensate is preferably 200 to 20000, more preferably 300 to 20000, and still more preferably 300 to 10,000. If Mn is less than 200, the viscosity tends to be too low to make it difficult to suppress the occurrence of resin stains during transfer molding of the thermosetting resin composition, and if it exceeds 20000, the compatibility with the epoxy resin decreases. There is a tendency that the fluidity at the time of transfer molding of the thermosetting resin composition tends to decrease.
本発明で用いられる数平均分子量Ｍｎは、ゲルパーミエーションクロマトグラフィー法（ＧＰＣ）により標準ポリスチレンによる検量線を用いて下記条件で測定することで得られる。
（ＧＰＣ条件）
ポンプ：Ｌ−６２００型（株式会社日立製作所製、商品名）
カラム：ＴＳＫｇｅｌ―Ｇ５０００ＨＸＬ及びＴＳＫｇｅｌ−Ｇ２０００ＨＸＬ（東ソー株式会社製、商品名）
検出器：Ｌ−３３００ＲＩ型（株式会社日立製作所製、商品名）
溶離液：テトラヒドロフラン
測定温度：３０℃
流量：１．０ｍＬ／分
The number average molecular weight Mn used in the present invention can be obtained by measuring under the following conditions using a standard polystyrene calibration curve by gel permeation chromatography (GPC).
(GPC conditions)
Pump: L-6200 type (manufactured by Hitachi, Ltd., trade name)
Column: TSKgel-G5000HXL and TSKgel-G2000HXL (trade name, manufactured by Tosoh Corporation)
Detector: L-3300RI type (manufactured by Hitachi, Ltd., trade name)
Eluent: Tetrahydrofuran Measurement temperature: 30 ° C
Flow rate: 1.0 mL / min
本実施形態に係る多価カルボン酸縮合体は、多価カルボン酸及び必要に応じて用いられるモノカルボン酸を含む反応液中で脱水縮合させることにより、得られる。例えば、下記一般式（５）で表される多価カルボン酸及び下記一般式（６）で表されるモノカルボン酸を含む反応液中で、それぞれが有するカルボキシル基を分子間で脱水縮合させる工程を備える方法によって得ることができる。 The polyvalent carboxylic acid condensate according to this embodiment can be obtained by dehydration condensation in a reaction solution containing a polyvalent carboxylic acid and a monocarboxylic acid used as necessary. For example, in a reaction solution containing a polyvalent carboxylic acid represented by the following general formula (5) and a monocarboxylic acid represented by the following general formula (6), the respective carboxyl groups possessed by dehydration condensation between molecules Can be obtained by a method comprising:
脱水縮合の反応液は、例えば、多価カルボン酸及びモノカルボン酸と、これらを溶解する無水酢酸又は無水プロピオン酸、塩化アセチル、脂肪族酸塩化物及び有機塩基（トリメチルアミン等）から選ばれる脱水剤とを含有する。例えば、反応液を５〜６０分にわたって窒素雰囲気下で還流した後、反応液の温度を１８０℃まで上昇させて窒素気流下の開放系で、生成する酢酸及び水を留去することにより重縮合を進行させる。揮発成分の発生が認められなくなった時点で、反応容器内を減圧しながら１８０℃の温度で３時間にわたって、より好ましくは８時間にわたって溶融状態で重縮合を進行させる。生成した多価カルボン酸縮合体を、無水酢酸等の非プロトン性溶媒を用いた再結晶や再沈殿法によって精製してもよい。なお、脱水縮合反応において、目的のＩＣＩコーンプレート粘度、数平均分子量、軟化点が得られるように適宜反応条件を変えることができ、ここに示した反応条件に限られるものではない。 The dehydrating condensation reaction liquid is, for example, a polyhydric carboxylic acid and a monocarboxylic acid, and a dehydrating agent selected from acetic anhydride or propionic anhydride, acetyl chloride, an aliphatic acid chloride, and an organic base (such as trimethylamine) that dissolve them. Containing. For example, after the reaction solution is refluxed in a nitrogen atmosphere for 5 to 60 minutes, the temperature of the reaction solution is increased to 180 ° C., and polycondensation is performed by distilling off the generated acetic acid and water in an open system under a nitrogen stream. To advance. When generation of volatile components is no longer observed, polycondensation proceeds in a molten state at a temperature of 180 ° C. for 3 hours, more preferably for 8 hours while reducing the pressure in the reaction vessel. The produced polyvalent carboxylic acid condensate may be purified by recrystallization or reprecipitation using an aprotic solvent such as acetic anhydride. In the dehydration condensation reaction, the reaction conditions can be appropriately changed so as to obtain the desired ICI corn plate viscosity, number average molecular weight, and softening point, and the reaction conditions are not limited to those shown here.
係る方法によって得られる多価カルボン酸縮合体は、式（６）のモノカルボン酸の２分子との縮合物、式（５）の多価カルボン酸と式（６）のモノカルボン酸との縮合物、多価カルボン酸及びモノカルボン酸の未反応物、並びに、無水酢酸及び無水プロピオン酸等の反応試薬と多価カルボン酸又はモノカルボン酸とが縮合反応して生成する酸無水物のような副生成物を含んでいる場合がある。これら副生成物は、精製によって除いてもよく、また、混合物のまま硬化剤として用いることもできる。 The polycarboxylic acid condensate obtained by such a method is a condensate of two molecules of monocarboxylic acid of formula (6), condensation of polycarboxylic acid of formula (5) and monocarboxylic acid of formula (6) , Unreacted products of polycarboxylic acids and monocarboxylic acids, and acid anhydrides formed by condensation reaction of reaction reagents such as acetic anhydride and propionic anhydride with polycarboxylic acids or monocarboxylic acids May contain by-products. These by-products may be removed by purification, or may be used as a curing agent in a mixture.
本発明で用いられる多価カルボン酸縮合体は、縮合反応前の多価カルボン酸とモノカルボン酸の仕込み組成比で生成物のＩＣＩコーンプレート粘度、数平均分子量及び軟化点を目的に応じて調整することができる。多価カルボン酸の比率が多くなるほど、ＩＣＩコーンプレート粘度、数平均分子量、軟化点が増加する傾向にある。但し、縮合反応の条件によっては必ずしも上記のような傾向を示すわけではなく、脱水縮合反応の条件である反応温度、減圧度、反応時間の要素も加味する必要がある。 The polyvalent carboxylic acid condensate used in the present invention is prepared by adjusting the ICI corn plate viscosity, number average molecular weight and softening point of the product according to the charged composition ratio of the polyvalent carboxylic acid and the monocarboxylic acid before the condensation reaction. can do. As the ratio of polyvalent carboxylic acid increases, the ICI cone plate viscosity, number average molecular weight, and softening point tend to increase. However, depending on the conditions of the condensation reaction, the above-mentioned tendency is not necessarily exhibited, and it is necessary to take into account the reaction temperature, the degree of pressure reduction, and the reaction time, which are the conditions for the dehydration condensation reaction.
多価カルボン酸縮合体の軟化点は、２０〜２００℃であることが好ましく、２０〜１３０℃であることがより好ましく、３０〜９０℃であることが更に好ましい。これにより、多価カルボン酸縮合体を含む樹脂組成物中に２本ロールミル等を用いて無機フィラーを分散させる場合に、良好な分散性及び作業性が得られる。無機フィラーの分散性に優れることは、トランスファー成形用の熱硬化性樹脂組成物等において特に重要である。また、ロールミルを用いて熱硬化性樹脂組成物を製造する際の混練性の観点から、多価カルボン酸縮合体の軟化点が３０〜８０℃であることが好ましく、３０〜５０℃であることがより好ましい。軟化点が２０℃未満では熱硬化性樹脂組成物の製造時においてハンドリング性、混練性及び分散性が低下し、トランスファー成形時の樹脂汚れの発生を効果的に抑える難くなる傾向がある。軟化点が２００℃を超えると、トランスファー成形によって１００〜２００℃に加熱した場合に樹脂組成物中に硬化剤が溶け残る可能性があり、均一な成形体が得られ難くなる傾向がある。多価カルボン酸縮合体の軟化点は、主鎖の構造の選択と数平均分子量の調整で所望の範囲にすることができる。一般に、モノマーとして調査の二価カルボン酸を用いると軟化点を低くすることができ、また、極性の高い構造を導入すると軟化点を高くすることができる。また、一般に、数平均分子量を大きくすれば軟化点を低下させることができる。 The softening point of the polyvalent carboxylic acid condensate is preferably 20 to 200 ° C, more preferably 20 to 130 ° C, and still more preferably 30 to 90 ° C. Thereby, when disperse | distributing an inorganic filler using a 2 roll mill etc. in the resin composition containing a polyhydric carboxylic acid condensate, favorable dispersibility and workability | operativity are obtained. The excellent dispersibility of the inorganic filler is particularly important in a thermosetting resin composition for transfer molding. Moreover, it is preferable that the softening point of a polyhydric carboxylic acid condensate is 30-80 degreeC from a viewpoint of the kneadability at the time of manufacturing a thermosetting resin composition using a roll mill, and it is 30-50 degreeC. Is more preferable. When the softening point is less than 20 ° C., the handling property, kneading property and dispersibility are lowered during the production of the thermosetting resin composition, and it is difficult to effectively suppress the occurrence of resin stains during transfer molding. When the softening point exceeds 200 ° C., the curing agent may remain undissolved in the resin composition when heated to 100 to 200 ° C. by transfer molding, and it tends to be difficult to obtain a uniform molded body. The softening point of the polyvalent carboxylic acid condensate can be set to a desired range by selecting the structure of the main chain and adjusting the number average molecular weight. Generally, the softening point can be lowered by using the divalent carboxylic acid investigated as a monomer, and the softening point can be increased by introducing a highly polar structure. In general, the softening point can be lowered by increasing the number average molecular weight.
本実施形態の硬化性樹脂組成物において、多価カルボン酸縮合体の含有量は、（Ｂ）硬化剤全体を基準として、１０〜１００質量％であることが好ましく、２０〜７０質量％であることがより好ましく、２０〜５０質量％であることが更に好ましい。 In the curable resin composition of the present embodiment, the content of the polyvalent carboxylic acid condensate is preferably 10 to 100% by mass, based on the entire (B) curing agent, and is 20 to 70% by mass. It is more preferable, and it is still more preferable that it is 20-50 mass%.
なお、（Ｂ）硬化剤は、多価カルボン酸が分子内で閉環縮合してなる酸無水物を更に含んでいてもよい。この場合、（Ａ）エポキシ樹脂中に含まれるエポキシ基と、エポキシ基と反応可能な（Ｂ）硬化剤中の酸無水物基との当量比が、１：０．３〜１：１．２であることが好ましい。これにより、本発明の熱硬化性樹脂組成物の成形時における樹脂汚れをより一層低減することができる。 In addition, (B) hardening | curing agent may further contain the acid anhydride formed by polycyclic carboxylic acid ring-closing condensation in a molecule | numerator. In this case, the equivalent ratio of (A) the epoxy group contained in the epoxy resin and the acid anhydride group in the (B) curing agent capable of reacting with the epoxy group is 1: 0.3 to 1: 1.2. It is preferable that Thereby, the resin stain | pollution | contamination at the time of shaping | molding of the thermosetting resin composition of this invention can be reduced further.
本実施形態の熱硬化性樹脂組成物において、（Ｂ）硬化剤として、上記多価カルボン酸縮合体と共に、電子部品封止用エポキシ樹脂成形材料で一般に使用されている硬化剤を併用することができる。このような硬化剤としては、エポキシ樹脂と反応するものであれば、特に限定されないが、無色又は淡黄色であることが好ましい。このような硬化剤として、例えば、酸無水物系硬化剤、イソシアヌル酸誘導体系硬化剤、フェノール系硬化剤が挙げられる。酸無水物系硬化剤としては、例えば、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、テトラヒドロ無水フタル酸、無水メチルナジック酸、無水ナジック酸、無水グルタル酸、無水ジメチルグルタル酸、無水ジエチルグルタル酸、無水コハク酸、メチルヘキサヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸が挙げられる。イソシアヌル酸誘導体としては、１，３，５−トリス（１−カルボキシメチル）イソシアヌレート、１，３，５−トリス（２−カルボキシエチル）イソシアヌレート、１，３，５−トリス（３−カルボキシプロピル）イソシアヌレート、１，３−ビス（２−カルボキシエチル）イソシアヌレートが挙げられる。これらの硬化剤の中では、無水フタル酸、無水トリメリット酸、ヘキサヒドロ無水フタル酸、テトラヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、無水グルタル酸、無水ジメチルグルタル酸、無水ジエチルグルタル酸又は１，３，５−トリス（３−カルボキシプロピル）イソシアヌレートを用いることが好ましい。また、上記硬化剤は、１種を単独で又は２種以上を組み合わせてもよい。これらの併用可能な硬化剤を含む場合、多価カルボン酸縮合体との配合比率を変えることによって、（Ｂ）硬化剤の全体としての粘度を調整することができ、好ましい。 In the thermosetting resin composition of the present embodiment, (B) a curing agent generally used in an epoxy resin molding material for electronic component sealing may be used in combination with the polyvalent carboxylic acid condensate as the curing agent. it can. Such a curing agent is not particularly limited as long as it reacts with the epoxy resin, but is preferably colorless or light yellow. Examples of such a curing agent include an acid anhydride curing agent, an isocyanuric acid derivative curing agent, and a phenol curing agent. Examples of the acid anhydride curing agent include phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, glutaric anhydride. Examples include acid, dimethyl glutaric anhydride, diethyl glutaric anhydride, succinic anhydride, methyl hexahydrophthalic anhydride, and methyl tetrahydrophthalic anhydride. Isocyanuric acid derivatives include 1,3,5-tris (1-carboxymethyl) isocyanurate, 1,3,5-tris (2-carboxyethyl) isocyanurate, 1,3,5-tris (3-carboxypropyl) ) Isocyanurate, 1,3-bis (2-carboxyethyl) isocyanurate. Among these curing agents, phthalic anhydride, trimellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, glutaric anhydride, dimethylglutaric anhydride, anhydrous It is preferable to use diethyl glutaric acid or 1,3,5-tris (3-carboxypropyl) isocyanurate. Moreover, the said hardening | curing agent may be used individually by 1 type or in combination of 2 or more types. When these curing agents that can be used in combination are included, the viscosity of the (B) curing agent as a whole can be adjusted by changing the blending ratio with the polyvalent carboxylic acid condensate, which is preferable.
上述の併用可能な硬化剤は、分子量が１００〜４００であることが好ましい。また、無水トリメリット酸、無水ピロメリット酸等の芳香環を有する酸無水物よりも、芳香環の不飽和結合のすべてを水素化した無水物が好ましい。酸無水物系硬化剤として、ポリイミド樹脂の原料として一般的に使用される酸無水物を用いてもよい。 The above-described curing agent that can be used in combination preferably has a molecular weight of 100 to 400. In addition, an anhydride obtained by hydrogenating all unsaturated bonds of an aromatic ring is preferable to an acid anhydride having an aromatic ring such as trimellitic anhydride or pyromellitic anhydride. As the acid anhydride curing agent, an acid anhydride generally used as a raw material for the polyimide resin may be used.
本発明の熱硬化性樹脂組成物において、（Ｂ）硬化剤の配合量は、（Ａ）エポキシ樹脂１００質量部に対して、１〜１５０質量部であることが好ましく、樹脂汚れを抑制するという観点から、５０〜１２０質量部であることがより好ましい。 In the thermosetting resin composition of the present invention, the blending amount of the (B) curing agent is preferably 1 to 150 parts by mass with respect to 100 parts by mass of the (A) epoxy resin, and suppresses resin stains. From a viewpoint, it is more preferable that it is 50-120 mass parts.
また、（Ｂ）硬化剤は、（Ａ）エポキシ樹脂中のエポキシ基１当量に対して、当該エポキシ基との反応可能な（Ｂ）硬化剤中の活性基（酸無水物基又は水酸基）が０．５〜０．９当量となるように配合することが好ましく、０．７〜０．８当量となることがより好ましい。上記活性基が０．５当量未満では、熱硬化性樹脂組成物の硬化速度が遅くなると共に、得られる硬化体のガラス転移温度が低くなり、充分な弾性率が得られ難くなる傾向がある。一方、上記活性基が０．９当量を超えると、硬化後の強度が低下する傾向がある。 Further, (B) the curing agent has an active group (an acid anhydride group or a hydroxyl group) in (B) the curing agent capable of reacting with the epoxy group with respect to 1 equivalent of the epoxy group in (A) the epoxy resin. It is preferable to mix | blend so that it may become 0.5-0.9 equivalent, and it is more preferable that it will be 0.7-0.8 equivalent. If the said active group is less than 0.5 equivalent, while the cure rate of a thermosetting resin composition will become slow, the glass transition temperature of the hardened | cured material obtained will become low, and there exists a tendency for sufficient elasticity modulus to become difficult to be obtained. On the other hand, when the active group exceeds 0.9 equivalent, the strength after curing tends to decrease.
＜（Ｃ）硬化促進剤＞
本発明の熱硬化性樹脂組成物には必要に応じて（Ｃ）硬化促進剤（硬化触媒）を配合することができる。（Ｃ）硬化促進剤としては、（Ａ）及び（Ｂ）成分間の硬化反応を促進させるような触媒機能を有するものであれば、特に限定されることなく用いることができる。硬化促進剤としては、例えば、アミン化合物、イミダゾール化合物、有機リン化合物、アルカリ金属化合物、アルカリ土類金属化合物、第４級アンモニウム塩が挙げられる。これらの硬化促進剤の中でも、アミン化合物、イミダゾール化合物又は有機リン化合物を用いることが好ましい。アミン化合物としては、例えば、１，８−ジアザ−ビシクロ（５，４，０）ウンデセン−７、トリエチレンジアミン、トリ−２，４，６−ジメチルアミノメチルフェノールが挙げられる。また、イミダゾール化合物として、例えば、２−エチル−４−メチルイミダゾールが挙げられる。更に、有機リン化合物としては、例えば、トリフェニルホスフィン、テトラフェニルホスホニウムテトラフェニルボレート、テトラ−ｎ−ブチルホスホニウム−ｏ，ｏ−ジエチルホスホロジチオエート、テトラ−ｎ−ブチルホスホニウム−テトラフルオロボレート、テトラ−ｎ−ブチルホスホニウム−テトラフェニルボレートが挙げられる。これらの硬化促進剤は、１種を単独で又は２種以上を組み合わせて使用してもよい。
<(C) Curing accelerator>
If necessary, the thermosetting resin composition of the present invention can be blended with (C) a curing accelerator (curing catalyst). (C) As a hardening accelerator, if it has a catalyst function which accelerates | stimulates hardening reaction between (A) and (B) component, it can use without being specifically limited. Examples of the curing accelerator include amine compounds, imidazole compounds, organic phosphorus compounds, alkali metal compounds, alkaline earth metal compounds, and quaternary ammonium salts. Among these curing accelerators, it is preferable to use an amine compound, an imidazole compound, or an organic phosphorus compound. Examples of the amine compound include 1,8-diaza-bicyclo (5,4,0) undecene-7, triethylenediamine, and tri-2,4,6-dimethylaminomethylphenol. Examples of the imidazole compound include 2-ethyl-4-methylimidazole. Furthermore, examples of the organic phosphorus compound include triphenylphosphine, tetraphenylphosphonium tetraphenylborate, tetra-n-butylphosphonium-o, o-diethylphosphorodithioate, tetra-n-butylphosphonium-tetrafluoroborate, tetra -N-butylphosphonium-tetraphenylborate. These curing accelerators may be used alone or in combination of two or more.
上記（Ｃ）硬化促進剤の配合量は、（Ａ）エポキシ樹脂１００質量部に対して、０．０１〜８質量部であることが好ましく、０．１〜３質量部であることがより好ましい。硬化促進剤の含有量が、０．０１質量部未満では、十分な硬化促進効果を得られない場合があり、８質量部を超えると、得られる成形体に変色が見られる場合がある。 The blending amount of the (C) curing accelerator is preferably 0.01 to 8 parts by mass and more preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the (A) epoxy resin. . If the content of the curing accelerator is less than 0.01 parts by mass, a sufficient curing acceleration effect may not be obtained, and if it exceeds 8 parts by mass, discoloration may be seen in the resulting molded article.
＜（Ｄ）白色顔料＞
光半導体装置等に利用可能な白色の成形樹脂として用いる場合には、本発明の熱硬化性樹脂組成物に更に（Ｄ）白色顔料を含むことが好ましい。（Ｄ）白色顔料としては、公知のものを使用することができ、特に限定されない。白色顔料として、例えば、アルミナ、酸化マグネシウム、酸化アンチモン、酸化チタン、酸化ジルコニウム及び無機中空粒子が挙げられる。これらは１種を単独で又は２種以上併用することができる。無機中空粒子としては、例えば、珪酸ソーダガラス、アルミ珪酸ガラス、硼珪酸ソーダガラス、シラス（白砂）が挙げられる。白色顔料の粒径は、中心粒径が０．１〜５０μｍであることが好ましい。この中心粒径が０．１μｍ未満であると粒子が凝集しやすく分散性が低下する傾向があり、５０μｍを超えると熱硬化性樹脂組成物からなる硬化物の反射特性が十分に得られ難くなる。
<(D) White pigment>
When used as a white molding resin that can be used in an optical semiconductor device or the like, it is preferable that the thermosetting resin composition of the present invention further contains (D) a white pigment. (D) As a white pigment, a well-known thing can be used and it does not specifically limit. Examples of the white pigment include alumina, magnesium oxide, antimony oxide, titanium oxide, zirconium oxide, and inorganic hollow particles. These can be used alone or in combination of two or more. Examples of the inorganic hollow particles include sodium silicate glass, aluminum silicate glass, borosilicate soda glass, and shirasu (white sand). The white pigment preferably has a center particle size of 0.1 to 50 μm. If the center particle size is less than 0.1 μm, the particles tend to aggregate and the dispersibility tends to decrease, and if it exceeds 50 μm, it is difficult to sufficiently obtain the reflection characteristics of the cured product made of the thermosetting resin composition. .
（Ｄ）白色顔料の配合量は、特に限定されないが、熱硬化性樹脂組成物全体に対して、１０〜８５体積％であることが好ましく、２０〜７５体積％であることがより好ましい。この配合量が１０体積％未満であると硬化後の熱硬化性樹脂組成物の光反射特性が十分に得られ難い傾向があり、８５体積％を超えると熱硬化性樹脂組成物の成形性が低下する傾向がある。 (D) Although the compounding quantity of a white pigment is not specifically limited, It is preferable that it is 10-85 volume% with respect to the whole thermosetting resin composition, and it is more preferable that it is 20-75 volume%. If the blending amount is less than 10% by volume, the light-reflecting properties of the cured thermosetting resin composition tend not to be sufficiently obtained, and if it exceeds 85% by volume, the moldability of the thermosetting resin composition tends to be low. There is a tendency to decrease.
また、熱硬化性樹脂組成物が（Ｄ）白色顔料と共に後述する無機充填剤を含有する場合、（Ｄ）白色顔料と無機充填材との合計配合量が、熱硬化性樹脂組成物全体に対して、１０〜８５体積％であると、熱硬化性樹脂組成物の成形性をより一層向上することができる。 Moreover, when a thermosetting resin composition contains the inorganic filler mentioned later with (D) white pigment, the total compounding quantity of (D) white pigment and an inorganic filler is with respect to the whole thermosetting resin composition. And the moldability of a thermosetting resin composition can be further improved as it is 10 to 85 volume%.
＜その他の成分＞
（無機充填材）
熱硬化性樹脂組成物は成形性を調整するために、無機充填材を含むことが好ましい。なお、無機充填剤として、上記白色顔料と同様のものを用いてもよい。無機充填材として、例えば、シリカ、酸化アンチモン、酸化チタン、水酸化アルミニウム、水酸化マグネシウム、硫酸バリウム、炭酸マグネシウム、炭酸バリウム、アルミナ、マイカ、ベリリア、チタン酸バリウム、チタン酸カリウム、チタン酸ストロンチウム、チタン酸カルシウム、炭酸アルミニウム、ケイ酸アルミニウム、炭酸カルシウム、ケイ酸カルシウム、ケイ酸マグネシウム、窒化ケイ素、窒化ホウ素、焼成クレー等のクレー、タルク、ホウ酸アルミニウム、ホウ酸アルミニウム、炭化ケイ素が挙げられる。熱伝導性、光反射特性、成形性及び難燃性の点から、無機充填剤は、シリカ、アルミナ、酸化マグネシウム、酸化アンチモン、酸化チタン、酸化ジルコニウム、水酸化アルミニウム、水酸化マグネシウムからなる群から選ばれる２種以上の混合物であることが好ましい。無機充填材の平均粒径は、白色顔料とのパッキング性を向上させる観点から、１〜１００μｍであることが好ましく、１〜４０μｍであることがより好ましい。本実施形態の熱硬化性樹脂組成物における無機充填剤の配合量は、（Ａ）成分及び（Ｂ）成分の合計量１００質量部に対して、１〜１０００質量部であることが好ましく、１〜８００質量部であることがより好ましい。
<Other ingredients>
(Inorganic filler)
The thermosetting resin composition preferably contains an inorganic filler in order to adjust moldability. In addition, you may use the thing similar to the said white pigment as an inorganic filler. Examples of inorganic fillers include silica, antimony oxide, titanium oxide, aluminum hydroxide, magnesium hydroxide, barium sulfate, magnesium carbonate, barium carbonate, alumina, mica, beryllia, barium titanate, potassium titanate, strontium titanate, Examples include calcium titanate, aluminum carbonate, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, clay such as calcined clay, talc, aluminum borate, aluminum borate, and silicon carbide. From the viewpoint of thermal conductivity, light reflection characteristics, moldability and flame retardancy, the inorganic filler is selected from the group consisting of silica, alumina, magnesium oxide, antimony oxide, titanium oxide, zirconium oxide, aluminum hydroxide, and magnesium hydroxide. A mixture of two or more selected is preferable. The average particle diameter of the inorganic filler is preferably 1 to 100 μm, more preferably 1 to 40 μm, from the viewpoint of improving packing properties with the white pigment. It is preferable that the compounding quantity of the inorganic filler in the thermosetting resin composition of this embodiment is 1-1000 mass parts with respect to 100 mass parts of total amounts of (A) component and (B) component. More preferably, it is -800 mass parts.
（カップリング剤）
熱硬化性樹脂組成物には、熱硬化性樹脂成分である（Ａ）〜（Ｃ）成分と、（Ｄ）白色顔料及び必要に応じて添加される無機充填材との接着性を向上させる観点からカップリング剤を添加することが好ましい。カップリング剤としては、特に限定されないが、例えば、シランカップリング剤及びチタネート系カップリング剤が挙げられる。シランカップリング剤としては、一般にエポキシシラン系、アミノシラン系、カチオニックシラン系、ビニルシラン系、アクリルシラン系、メルカプトシラン系及びこれらの複合系が挙げられ、任意の添加量で用いることができる。なお、カップリング剤の配合量は、熱硬化性樹脂組成物全体に対して５質量％以下であることが好ましい。
(Coupling agent)
In the thermosetting resin composition, the viewpoint of improving the adhesiveness between the components (A) to (C), which are thermosetting resin components, and (D) the white pigment and the inorganic filler added as necessary. It is preferable to add a coupling agent. Although it does not specifically limit as a coupling agent, For example, a silane coupling agent and a titanate coupling agent are mentioned. Examples of the silane coupling agent generally include epoxy silane, amino silane, cationic silane, vinyl silane, acryl silane, mercapto silane, and composites thereof, and can be used in any amount. In addition, it is preferable that the compounding quantity of a coupling agent is 5 mass% or less with respect to the whole thermosetting resin composition.
また、本実施形態の樹熱硬化性脂組成物には、必要に応じて、酸化防止剤、離型剤、イオン捕捉剤等の添加剤を添加してもよい。 Moreover, you may add additives, such as antioxidant, a mold release agent, and an ion capture agent, to the tree thermosetting fat composition of this embodiment as needed.
［熱硬化性樹脂組成物の作製方法］
本実施形態の熱硬化性樹脂組成物は、上記した各種成分を均一に分散混合することで得ることができ、その手段や条件等は特に限定されない。熱硬化性樹脂組成物を作製する一般的な方法として、各成分を押出機、ニーダー、ロール、エクストルーダー等によって混練した後、混練物を冷却し、粉砕する方法を挙げることができる。各成分を混練する際には、分散性を向上する観点から、溶融状態で行うことが好ましい。混練の条件は、各成分の種類や配合量により適宜決定すればよく、例えば、１５〜１００℃で５〜４０分間混練することが好ましく、２０〜１００℃で１０〜３０分間混練することがより好ましい。混練温度が１５℃未満であると、各成分を混練させ難くなり、分散性も低下する傾向にあり、１００℃を超えると、樹脂組成物の高分子量化が進行し、樹脂組成物が硬化してしまう可能性がある。また、混練時間が５分未満であると、トランスファー成形時に樹脂バリが発生してしまう可能性がある。混練時間が４０分を超えると、樹脂組成物の高分子量化が進行し、樹脂組成物が硬化してしまう可能性がある。
[Method for producing thermosetting resin composition]
The thermosetting resin composition of the present embodiment can be obtained by uniformly dispersing and mixing the various components described above, and the means and conditions thereof are not particularly limited. As a general method for producing a thermosetting resin composition, there can be mentioned a method in which each component is kneaded with an extruder, a kneader, a roll, an extruder, etc., and then the kneaded product is cooled and pulverized. When kneading each component, it is preferable to carry out in a molten state from the viewpoint of improving dispersibility. The kneading conditions may be appropriately determined depending on the type and blending amount of each component. For example, kneading is preferably performed at 15 to 100 ° C. for 5 to 40 minutes, more preferably kneading at 20 to 100 ° C. for 10 to 30 minutes. preferable. When the kneading temperature is less than 15 ° C., it becomes difficult to knead each component and the dispersibility also tends to decrease. When the kneading temperature exceeds 100 ° C., the resin composition increases in molecular weight, and the resin composition is cured. There is a possibility that. If the kneading time is less than 5 minutes, resin burrs may be generated during transfer molding. If the kneading time exceeds 40 minutes, the resin composition may be increased in molecular weight and the resin composition may be cured.
本発明の熱硬化性樹脂組成物は、（Ａ）エポキシ樹脂及び（Ｂ）硬化剤を予め混合する予備混合工程を経た後に、他の成分を加えて、ロールミルや押出機により混練することによって製造することもできる。例えば、（Ａ）エポキシ樹脂及び（Ｂ）硬化剤の少なくとも一方が、０〜３５℃で液状である場合、又は、１００〜２００℃で１０ｍＰａ・ｓ未満の低粘度である場合には、予備混合工程を行うことが好ましい。このような（Ａ）エポキシ樹脂及び（Ｂ）硬化剤を用いて予備混合を行うことで得られる熱硬化性樹脂組成物は、貯蔵安定性が向上し、トランスファー成形時の成形性により優れるものとなる。 The thermosetting resin composition of the present invention is produced by passing through a premixing step in which (A) an epoxy resin and (B) a curing agent are mixed in advance, and then adding other components and kneading with a roll mill or an extruder. You can also For example, when at least one of (A) epoxy resin and (B) curing agent is liquid at 0 to 35 ° C., or has a low viscosity of less than 10 mPa · s at 100 to 200 ° C., premixing It is preferable to perform a process. The thermosetting resin composition obtained by premixing using such (A) epoxy resin and (B) curing agent has improved storage stability and is more excellent in moldability during transfer molding. Become.
上記予備混合工程における予備混合物の粘度は、１００〜１５０℃で１０〜１００００ｍＰａ・ｓであることが好ましく、１００℃での粘度が１０〜１００００ｍＰａ・ｓであることがより好ましい。該粘度が１０ｍＰａ・ｓ未満ではトランスファー成形時にバリが発生しやすくなり、１００００ｍＰａ・ｓを超えると成形時の流動性が低下し、金型に熱硬化性樹脂組成物を流し込み難くなり、成形性が低下する傾向がある。 The viscosity of the preliminary mixture in the preliminary mixing step is preferably 10 to 10,000 mPa · s at 100 to 150 ° C., and more preferably 10 to 10,000 mPa · s at 100 ° C. If the viscosity is less than 10 mPa · s, burrs are likely to occur during transfer molding, and if it exceeds 10,000 mPa · s, the fluidity during molding decreases, making it difficult to pour the thermosetting resin composition into the mold, and the moldability is reduced. There is a tendency to decrease.
上記予備混合工程において、析出物が発生することにより粘度の増加を防ぐ観点から、（Ａ）エポキシ樹脂及び（Ｂ）硬化剤の硬化反応物であるゲル等が析出して析出物による予備混合物に白濁が生じないように混合条件を調製することが好ましい。「析出物による白濁」とは、電磁波の可視光領域における散乱があることを示す。より具体的には光のレイリー散乱、ミー散乱、回折散乱現象を生じるような、散乱中心を有する微粒子が存在しないことを示す。 In the pre-mixing step, from the viewpoint of preventing increase in viscosity due to the generation of precipitates, (A) the epoxy resin and (B) the curing reaction product of the curing agent, etc. are deposited into a pre-mixed mixture of precipitates. It is preferable to adjust the mixing conditions so that white turbidity does not occur. “White turbidity due to precipitates” indicates that there is scattering of electromagnetic waves in the visible light region. More specifically, it indicates that there is no fine particle having a scattering center that causes Rayleigh scattering, Mie scattering, and diffraction scattering phenomenon of light.
予備混合工程において、具体的には、（Ａ）エポキシ１００質量部及び（Ｂ）硬化剤１２０質量部を耐熱ガラス製の容器に秤量し、この混合容器をシリコーンオイルや水等の流体を媒体としたヒーターを用いて、３５〜１８０℃で加熱する方法を用いることができる。加熱方法としては上記の方法に限定されるものではなく、熱電対、電磁波照射等を用いることができ、さらに溶解を促進するために超音波を照射してもよい。 Specifically, in the preliminary mixing step, 100 parts by mass of (A) epoxy and 120 parts by mass of (B) curing agent are weighed in a heat-resistant glass container, and the mixing container is made of a fluid such as silicone oil or water as a medium. The method of heating at 35-180 degreeC can be used using the heater which was made. The heating method is not limited to the above method, and a thermocouple, electromagnetic wave irradiation, or the like can be used, and ultrasonic waves may be irradiated to promote dissolution.
また、予備混合工程において、（Ａ）エポキシ樹脂及び（Ｂ）硬化剤は、熱硬化性樹脂組成物に配合する（Ａ）エポキシ樹脂及び（Ｂ）硬化剤の一部を予備混合することが可能である。具体的には、（Ａ）エポキシ樹脂１００質量部に対し、（Ｂ）硬化剤１２０質量部含む熱硬化性樹脂組成物を製造する場合、まず、（Ａ）エポキシ樹脂５０質量部及び（Ｂ）硬化剤１２０質量部を耐熱ガラス製の容器に秤量し、この混合容器をシリコーンオイルや水などの流体を媒体としたヒーターを用いて３５〜１８０℃で加熱することで予備混合物を得る。そして、得られた予備混合物と、残りの（Ａ）エポキシ樹脂５０質量部、（Ｃ）硬化促進剤及びその他の成分とをロール混練などにより混合し熱硬化性樹脂組成物を製造してもよい。 In the premixing step, (A) epoxy resin and (B) curing agent can be premixed with (A) epoxy resin and (B) a part of curing agent to be blended in the thermosetting resin composition. It is. Specifically, when producing a thermosetting resin composition containing 120 parts by mass of (B) curing agent with respect to 100 parts by mass of (A) epoxy resin, first, 50 parts by mass of (A) epoxy resin and (B) 120 parts by mass of the curing agent is weighed in a container made of heat-resistant glass, and this mixing container is heated at 35 to 180 ° C. using a heater using a fluid such as silicone oil or water as a medium to obtain a preliminary mixture. And the obtained preliminary mixture, the remaining (A) 50 parts by mass of the epoxy resin, (C) the curing accelerator and other components may be mixed by roll kneading to produce a thermosetting resin composition. .
本実施形態の熱硬化性樹脂組成物は、室温付近（１５〜３０℃）において、加圧成形しタブレットを作製可能であり、熱硬化後の、波長３５０〜８００ｎｍにおける光反射率が８０％以上であることが好ましい。上記加圧成形は、例えば、室温において、５〜５０ＭＰａ、１〜５秒間程度の条件で行うことができる。上記光反射率が８０％未満では、光半導体装置の輝度向上に充分寄与できない傾向があり、より好ましい光反射率は９０％以上である。 The thermosetting resin composition of the present embodiment can be pressure-molded to produce a tablet near room temperature (15 to 30 ° C.), and the light reflectance at a wavelength of 350 to 800 nm after thermosetting is 80% or more. It is preferable that The pressure molding can be performed, for example, at room temperature under conditions of 5 to 50 MPa and 1 to 5 seconds. If the light reflectance is less than 80%, there is a tendency that it cannot sufficiently contribute to the improvement of the luminance of the optical semiconductor device, and a more preferable light reflectance is 90% or more.
本発明の熱硬化性樹脂組成物は、成形温度１００℃〜２００℃、成形圧力５〜２０ＭＰａ、成形時間６０〜１８０秒の条件でトランスファー成形した時のバリの長さが５ｍｍ以下となることが好ましい。バリの長さが５ｍｍを超えると、光半導体素子搭載用基板を作製する際、光半導体素子搭載領域となる開口部（凹部）に樹脂汚れが発生し、光半導体素子を搭載する際の障害となる可能性があり、また、光半導体素子と金属配線とを電気的に接続する際の障害になる可能性がある。半導体装置製造時の作業性の観点から、上記バリ長さは、３ｍｍ以下であることがより好ましく、１ｍｍ以下であることが更に好ましい。 The thermosetting resin composition of the present invention may have a burr length of 5 mm or less when transfer molded under conditions of a molding temperature of 100 ° C. to 200 ° C., a molding pressure of 5 to 20 MPa, and a molding time of 60 to 180 seconds. preferable. If the length of the burr exceeds 5 mm, when manufacturing the optical semiconductor element mounting substrate, resin contamination occurs in the opening (recessed portion) that becomes the optical semiconductor element mounting region, and this is an obstacle to mounting the optical semiconductor element. In addition, there is a possibility that it becomes an obstacle when electrically connecting the optical semiconductor element and the metal wiring. From the viewpoint of workability at the time of manufacturing a semiconductor device, the burr length is more preferably 3 mm or less, and further preferably 1 mm or less.
本実施形態の熱硬化性樹脂組成物は、高い透明性及び耐熱性を必要とする電気絶縁材料、光半導体封止材料、接着材料、塗料材料並びにトランスファー成形用エポキシ樹脂成形材料など様々な用途において有用である。 The thermosetting resin composition of the present embodiment is used in various applications such as electrical insulating materials, optical semiconductor sealing materials, adhesive materials, paint materials, and epoxy resin molding materials for transfer molding that require high transparency and heat resistance. Useful.
［エポキシ樹脂成形材料］
本発明のエポキシ樹脂成形材料は、上記（Ａ）エポキシ樹脂及び上記（Ｂ）硬化剤を含有するエポキシ樹脂成形材料であって、（Ｂ）硬化剤が上述の多価カルボン酸縮合体を含むものである。
[Epoxy resin molding materials]
The epoxy resin molding material of the present invention is an epoxy resin molding material containing the above (A) epoxy resin and the above (B) curing agent, and (B) the curing agent contains the polyvalent carboxylic acid condensate described above. .
［光半導体素子搭載用基板］
本発明の半導体素子搭載用基板は、底面及び壁面から構成される凹部を有し、凹部の底面が光半導体素子搭載部であり、凹部の壁面の少なくとも一部が本発明の熱硬化性樹脂組成物の硬化物からなるものである。図１は、本発明の光半導体素子搭載用基板の一実施形態を示す斜視図である。光半導体素子搭載用基板１１０は、Ｎｉ／Ａｇめっき１０４が形成された金属配線１０５と、リフレクター１０３とを備え、Ｎｉ／Ａｇめっき１０４が形成された金属配線１０５とリフレクター１０３とから形成された凹部２００を有している。すなわち、凹部２００の底面はＮｉ／Ａｇめっき１０４が形成された金属配線１０５から構成され、凹部２００の壁面はリフレクター１０３から構成されるものであり、リフレクター１０３は、上記本発明の熱硬化性樹脂組成物の硬化物からなる成形体である。
[Optical semiconductor device mounting substrate]
The substrate for mounting a semiconductor element of the present invention has a recess composed of a bottom surface and a wall surface, the bottom surface of the recess is an optical semiconductor element mounting portion, and at least a part of the wall surface of the recess is the thermosetting resin composition of the present invention. It consists of a cured product. FIG. 1 is a perspective view showing an embodiment of a substrate for mounting an optical semiconductor element of the present invention. The optical semiconductor element mounting substrate 110 includes a metal wiring 105 on which the Ni / Ag plating 104 is formed and a reflector 103, and a recess formed from the metal wiring 105 on which the Ni / Ag plating 104 is formed and the reflector 103. 200. That is, the bottom surface of the concave portion 200 is composed of the metal wiring 105 on which the Ni / Ag plating 104 is formed, and the wall surface of the concave portion 200 is composed of the reflector 103. The reflector 103 is the thermosetting resin of the present invention. It is a molded article made of a cured product of the composition.
本発明の光半導体素子搭載用基板の製造方法は特に限定されないが、例えば、本発明の熱硬化性樹脂組成物を用いたトランスファー成形により製造することができる。図２は、本発明の光半導体素子搭載用基板を製造する工程の一実施形態を示す概略図である。光半導体素子搭載用基板は、例えば、金属箔から打ち抜きやエッチング等の公知の方法により金属配線１０５を形成し、電気めっきによりＮｉ／Ａｇめっき１０４を施す工程（図２（ａ））、次いで、該金属配線１０５を所定形状の金型１５１に配置し、金型１５１の樹脂注入口１５０から本発明の熱硬化性樹脂組成物を注入し、所定の条件でトランスファー成形する工程（図２（ｂ））、そして、金型１５１を外す工程（図２（ｃ））を経て製造することができる。このようにして、光半導体素子搭載用基板には、熱硬化性樹脂組成物の硬化物からなるリフレクター１０３に周囲を囲まれてなる光半導体素子搭載領域（凹部）２００が形成される。なお、上記トランスファー成形の条件としては、金型温度１７０〜２００℃、成形圧力０．５〜２０ＭＰａで６０〜１２０秒間、アフターキュア温度１２０℃〜１８０℃で１〜３時間が好ましい。 Although the manufacturing method of the optical semiconductor element mounting substrate of this invention is not specifically limited, For example, it can manufacture by transfer molding using the thermosetting resin composition of this invention. FIG. 2 is a schematic view showing an embodiment of a process for producing an optical semiconductor element mounting substrate of the present invention. The optical semiconductor element mounting substrate is formed by, for example, forming a metal wiring 105 from a metal foil by a known method such as punching or etching, and applying Ni / Ag plating 104 by electroplating (FIG. 2A), A step of placing the metal wiring 105 in a mold 151 having a predetermined shape, injecting the thermosetting resin composition of the present invention from the resin injection port 150 of the mold 151, and performing transfer molding under a predetermined condition (FIG. 2B). )) And a step of removing the mold 151 (FIG. 2C). In this manner, the optical semiconductor element mounting region (recessed portion) 200 is formed on the optical semiconductor element mounting substrate. The optical semiconductor element mounting region (concave portion) 200 is surrounded by the reflector 103 made of a cured product of the thermosetting resin composition. The transfer molding is preferably performed at a mold temperature of 170 to 200 ° C., a molding pressure of 0.5 to 20 MPa for 60 to 120 seconds, and an after cure temperature of 120 to 180 ° C. for 1 to 3 hours.
［光半導体装置］
本発明の光半導体装置は、上記光半導体素子搭載用基板と、光半導体素子搭載用基板の凹部内に設けられた光半導体素子と、凹部を充填して光半導体素子を封止する封止樹脂部とを備えるものである。
[Optical semiconductor device]
An optical semiconductor device of the present invention includes the optical semiconductor element mounting substrate, an optical semiconductor element provided in a recess of the optical semiconductor element mounting substrate, and a sealing resin that fills the recess and seals the optical semiconductor element. Part.
図３は、本発明の光半導体素子搭載用基板１１０に光半導体素子１００を搭載した状態の一実施形態を示す斜視図である。図３に示すように、光半導体素子１００は、光半導体素子搭載用基板１１０の光半導体素子搭載領域（凹部）２００の所定位置に搭載され、金属配線１０５とボンディングワイヤ１０２により電気的に接続される。図４及び５は、本発明の光半導体装置の一実施形態を示す模式断面図である。図４及び５に示すように、光半導体装置は、光半導体素子搭載用基板１１０と、光半導体素子搭載用基板１１０の凹部２００内の所定位置に設けられた光半導体素子１００と、凹部２００を充填して光半導体素子を封止する蛍光体１０６を含む透明封止樹脂１０１からなる封止樹脂部とを備えており、光半導体素子１００とＮｉ／Ａｇめっき１０４が形成された金属配線１０５とがボンディングワイヤ１０２又ははんだバンプ１０７により電気的に接続されている。 FIG. 3 is a perspective view showing an embodiment in which the optical semiconductor element 100 is mounted on the optical semiconductor element mounting substrate 110 of the present invention. As shown in FIG. 3, the optical semiconductor element 100 is mounted at a predetermined position in the optical semiconductor element mounting region (concave portion) 200 of the optical semiconductor element mounting substrate 110 and is electrically connected by the metal wiring 105 and the bonding wire 102. The 4 and 5 are schematic cross-sectional views showing an embodiment of the optical semiconductor device of the present invention. As shown in FIGS. 4 and 5, the optical semiconductor device includes an optical semiconductor element mounting substrate 110, an optical semiconductor element 100 provided at a predetermined position in the concave portion 200 of the optical semiconductor element mounting substrate 110, and the concave portion 200. A sealing resin portion made of a transparent sealing resin 101 including a phosphor 106 that fills and seals the optical semiconductor element, and the optical semiconductor element 100 and the metal wiring 105 on which the Ni / Ag plating 104 is formed; Are electrically connected by bonding wires 102 or solder bumps 107.
図６もまた、本発明の光半導体装置の一実施形態を示す模式断面図である。図６に示す光半導体装置では、リフレクター３０３が形成されたリード３０４上の所定位置にダイボンド材３０６を介してＬＥＤ素子３００が配置され、ＬＥＤ素子３００とリード３０４とがボンディングワイヤ３０１により電気的に接続され、蛍光体３０５を含む透明封止樹脂３０２によりＬＥＤ体素子３００が封止されている。 FIG. 6 is also a schematic cross-sectional view showing an embodiment of the optical semiconductor device of the present invention. In the optical semiconductor device shown in FIG. 6, the LED element 300 is disposed via a die bonding material 306 at a predetermined position on the lead 304 on which the reflector 303 is formed, and the LED element 300 and the lead 304 are electrically connected by the bonding wire 301. The LED body element 300 is sealed with a transparent sealing resin 302 that is connected and includes a phosphor 305.
以上、本発明の好適な実施形態について説明したが、本発明はこれに制限されるものではない。 As mentioned above, although preferred embodiment of this invention was described, this invention is not restrict | limited to this.
以下に、本発明を実施例に基づいて具体的に説明するが、本発明はこれに限定されるものではない。 Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited thereto.
＜多価カルボン酸縮合体の作製＞
下記の合成例Ａ１、Ａ２及びＡ３にそれぞれ示した繰り返し単位用モノマーと両末端用のモノマーとを、無水酢酸中で５〜６０分にわたって窒素雰囲気下で還流した後、温度を１８０℃まで上昇させ、窒素気流下、開放系で反応によって生成した酢酸及び水を留去した。揮発成分が認められなくなったところで、反応容器内を減圧しながら１８０℃の温度で１〜１５時間にわたって溶融縮合し、多価カルボン酸縮合体を得た。
（合成例Ａ１）
繰り返し単位：水素化テレフタル酸（東京化成社製）；１２５ｇ
両末端：水素化−１，２−無水トリメリット酸（三菱ガス化学社製）；１２６ｇ
（合成例Ａ２）
繰り返し単位：水素化テレフタル酸（東京化成社製）；２１８ｇ
両末端：水素化無水トリメリット酸（三菱ガス化学社製）；８６ｇ
（合成例Ａ３）
繰り返し単位：なし
両末端：水素化−１，２−無水トリメリット酸（三菱ガス化学社製）；１００ｇ
<Preparation of polyvalent carboxylic acid condensate>
The monomer for repeating unit and the monomer for both ends shown in Synthesis Examples A1, A2 and A3 below were refluxed in acetic anhydride for 5 to 60 minutes in a nitrogen atmosphere, and then the temperature was raised to 180 ° C. Acetic acid and water produced by the reaction in an open system were distilled off under a nitrogen stream. When no volatile components were observed, the reaction vessel was melt-condensed at a temperature of 180 ° C. for 1 to 15 hours while reducing the pressure in the reaction vessel to obtain a polyvalent carboxylic acid condensate.
(Synthesis Example A1)
Repeating unit: Hydrogenated terephthalic acid (manufactured by Tokyo Chemical Industry); 125 g
Both ends: Hydrogenated-1,2-trimellitic anhydride (manufactured by Mitsubishi Gas Chemical Company); 126 g
(Synthesis Example A2)
Repeating unit: hydrogenated terephthalic acid (manufactured by Tokyo Chemical Industry); 218 g
Both ends: hydrogenated trimellitic anhydride (manufactured by Mitsubishi Gas Chemical Company); 86 g
(Synthesis Example A3)
Repeating unit: None Both ends: Hydrogenated-1,2-trimellitic anhydride (Mitsubishi Gas Chemical Co., Ltd.); 100 g
＜多価カルボン酸縮合体の特性評価＞
合成例Ａ１、Ａ２及びＡ３の多価カルボン酸縮合体の数平均分子量、粘度、軟化点及び外観を評価した。その結果を表１に示す。
<Characteristic evaluation of polyvalent carboxylic acid condensate>
The number average molecular weight, viscosity, softening point and appearance of the polyvalent carboxylic acid condensates of Synthesis Examples A1 , A2 and A3 were evaluated. The results are shown in Table 1.
数平均分子量Ｍｎは、下記条件のゲルパーミエーションクロマトグラフィー法（ＧＰＣ）により標準ポリスチレンによる検量線を用いて測定した。
・装置：ポンプ（株式会社日立製作所製、商品名：Ｌ−６２００型）、カラム（東ソー株式会社製、商品名：ＴＳＫｇｅｌ―Ｇ５０００ＨＸＬ、ＴＳＫｇｅｌ−Ｇ２０００ＨＸＬ）、検出器（株式会社日立製作所製、商品名：Ｌ−３３００ＲＩ型）
・溶離液：テトラヒドロフラン、流量１．０ｍＬ／分
・測定温度：３０℃
The number average molecular weight Mn was measured using a standard polystyrene calibration curve by gel permeation chromatography (GPC) under the following conditions.
Apparatus: Pump (manufactured by Hitachi, Ltd., trade name: L-6200 type), column (manufactured by Tosoh Corporation, trade name: TSKgel-G5000HXL, TSKgel-G2000HXL), detector (trade name, manufactured by Hitachi, Ltd.) : L-3300RI type)
・ Eluent: Tetrahydrofuran, flow rate 1.0 mL / min ・ Measurement temperature: 30 ° C.
粘度測定は、Ｒｅｓｅａｃｈ Ｅｑｕｉｐｍｅｎｔ（Ｌｏｎｄｏｎ）ＬＴＤ．製のＩＣＩコーンプレート型粘度計を用いて行った。なお、表２及び３には樹脂組成物に含まれる硬化剤成分をすべて混合した際の１５０℃における粘度を示した。 Viscosity measurements were taken from Research Equipment (London) LTD. This was carried out using an ICI cone plate viscometer made by the manufacturer. Tables 2 and 3 show the viscosities at 150 ° C. when all the curing agent components contained in the resin composition are mixed.
軟化点は、ＪＩＳ Ｋ ２２０７準拠の環球式軟化点試験法を用いて測定した。外観については目視で判断した。 The softening point was measured using a ring and ball softening point test method in accordance with JIS K 2207. The appearance was judged visually.
上記合成例で得られた多価カルボン酸縮合体は、軟化点及び粘度ともに熱硬化性樹脂組成物を製造するには非常に扱い易い性状となり、硬化剤として熱硬化性樹脂組成物に好適に用いることができる。 The polyvalent carboxylic acid condensate obtained in the above synthesis example is very easy to handle for producing a thermosetting resin composition in terms of both softening point and viscosity, and is suitable as a curing agent for a thermosetting resin composition. Can be used.
＜熱硬化性樹脂組成物の作製＞
（実施例１〜４、６〜９、１１、１３及び１４、参考例５、１０及び１２、比較例１〜３）
表２に示した配合比（質量部）に従い、（Ａ）エポキシ樹脂、（Ｂ）硬化剤を予備混合した後、残りの成分を加え、ミキサーを用いて十分混合した後、ミキシングロールにより所定条件で溶融混練し、冷却、粉砕を行い、実施例１〜４、６〜９、１１、１３及び１４、参考例５、１０及び１２及び比較例１〜３の熱硬化性樹脂組成物を作製した。
<Preparation of thermosetting resin composition>
(Examples 1-4, 6-9, 11, 13, and 14, Reference Examples 5, 10, and 12 , Comparative Examples 1-3)
According to the blending ratio (parts by mass) shown in Table 2, after premixing (A) epoxy resin and (B) curing agent, the remaining components are added and mixed thoroughly using a mixer, and then mixed with a predetermined condition by a mixing roll. The mixture was melt kneaded, cooled, and pulverized to produce thermosetting resin compositions of Examples 1 to 4, 6 to 9, 11, 13, and 14, Reference Examples 5, 10, and 12, and Comparative Examples 1 to 3 . .
＜熱硬化性樹脂組成物の評価＞
得られた熱硬化性樹脂組成物を成形金型温度１８０℃、成形圧力６．９ＭＰａ、キュア時間９０秒の条件でトランスファー成形し、下記の評価を行った。評価結果を表２及び３に示す。
<Evaluation of thermosetting resin composition>
The obtained thermosetting resin composition was transfer molded under the conditions of a molding die temperature of 180 ° C., a molding pressure of 6.9 MPa, and a curing time of 90 seconds, and the following evaluation was performed. The evaluation results are shown in Tables 2 and 3.
（光反射性試験）
得られた熱硬化性樹脂組成物を上述の条件でトランスファー成形した後、１５０℃で２時間ポストキュアして、厚み１．０ｍｍのテストピースを作製した。積分球型分光光度計Ｖ−７５０型（日本分光株式会社製、商品名）を用いて、波長４００ｎｍにおける上記テストピースの初期光学反射率（光反射率）を測定した。そして、下記の評価基準により光反射特性を評価した。
Ａ：光波長４００ｎｍにおいて光反射率８０％以上
Ｂ：光波長４００ｎｍにおいて光反射率７０％以上、８０％未満
Ｃ：光波長４００ｎｍにおいて光反射率７０％未満
(Light reflectivity test)
The obtained thermosetting resin composition was transfer molded under the above conditions, and then post-cured at 150 ° C. for 2 hours to prepare a test piece having a thickness of 1.0 mm. The initial optical reflectivity (light reflectivity) of the test piece at a wavelength of 400 nm was measured using an integrating sphere spectrophotometer V-750 type (trade name, manufactured by JASCO Corporation). The light reflection characteristics were evaluated according to the following evaluation criteria.
A: Light reflectance of 80% or more at a light wavelength of 400 nm B: Light reflectance of 70% or more and less than 80% at a light wavelength of 400 nm C: Light reflectance of less than 70% at a light wavelength of 400 nm
（トランスファー成形性）
（スパイラルフロー）
ＥＭＭＩ−１−６６の規格に準じたスパイラルフロー測定用金型を用いて、熱硬化性樹脂組成物を上記条件でトランスファー成形し、そのときの流動距離（ｃｍ）を求めた。
(Transfer formability)
(Spiral flow)
The thermosetting resin composition was transfer molded under the above conditions using a spiral flow measurement mold according to the standard of EMMI-1-66, and the flow distance (cm) at that time was determined.
（バリ長さ）
得られた熱硬化性樹脂組成物を、ポットを用いて、バリ測定用金型（図７を参照）に流し込み、次いで硬化させることによって熱硬化性樹脂組成物を成形した。なお、成形時の金型温度は１８０℃、成形圧力は６．９ＭＰａ、樹脂の流し込み時間（トランスファー時間）は１０秒であり、硬化温度は１８０℃、硬化時間は９０秒とした。成形後、バリ測定用金型の上型を外し、成形時に金型の上型と下型との隙間を流れて生じたバリの長さの最大値を、ノギスを使用して測定した。
(Burr length)
The obtained thermosetting resin composition was poured into a mold for burr measurement (see FIG. 7) using a pot, and then cured to form a thermosetting resin composition. The mold temperature during molding was 180 ° C., the molding pressure was 6.9 MPa, the resin pouring time (transfer time) was 10 seconds, the curing temperature was 180 ° C., and the curing time was 90 seconds. After molding, the upper mold of the mold for measuring burrs was removed, and the maximum value of the length of burrs generated by flowing through the gap between the upper mold and the lower mold of the mold was measured using calipers.
図７は、バリ長さの測定時に使用するバリ測定用金型の構造及びバリを模式的に示した図であり、（ａ）は側面断面図、（ｂ）は平面図である。図７に示したように、バリ測定用金型は、一対の上型４００と下型４０１とから構成され、上型４００は樹脂注入口４０２を有する。また、下型４０１は、樹脂注入口４０２に対向するキャビティ４０３と、キャビティ４０３から金型外周部に向かって伸びる６本のスリット４０４、４０５、４０６、４０７、４０８及び４０９を有する。バリは、図７に示したように、熱硬化性樹脂組成物がキャビティ４０３の外延から各スリットに沿って流れ込み硬化した部分（樹脂バリ）４１０を意味する。ここで、本発明で規定する「バリの長さ」とは、図７に示すバリ測定用金型を用いトランスファー成形を行った際の、金型中心のキャビティ４０３から、金型の上型４００と下型４０１との合わせ目の隙間にはみ出した硬化物（樹脂バリ４１０）の放射方向の最大長さをノギスで測定した値である。また、バリ測定用金型の寸法は、上型４００及び下型４０１の外形が（１４０ｍｍ）×（１４０ｍｍ）、樹脂注入口の径が上部７ｍｍ、下部４ｍｍ、キャビティの径が３０ｍｍ、キャビティの深さが４ｍｍであり、６本のスリット４０４から４０９の深さは、順に７５、５０、３０、２０、１０及び２μｍである。 FIGS. 7A and 7B are diagrams schematically showing the structure and burrs of a burr measuring mold used when measuring the burr length, where FIG. 7A is a side sectional view and FIG. 7B is a plan view. As shown in FIG. 7, the burr measurement mold is composed of a pair of an upper mold 400 and a lower mold 401, and the upper mold 400 has a resin injection port 402. The lower mold 401 has a cavity 403 facing the resin injection port 402 and six slits 404, 405, 406, 407, 408, and 409 extending from the cavity 403 toward the outer periphery of the mold. As shown in FIG. 7, the burr means a portion (resin burr) 410 in which the thermosetting resin composition flows from the outer extension of the cavity 403 along each slit and is cured. Here, the “burr length” defined in the present invention refers to the upper mold 400 of the mold from the cavity 403 at the center of the mold when transfer molding is performed using the mold for burr measurement shown in FIG. This is a value obtained by measuring the maximum radial length of the cured product (resin burr 410) that protrudes into the gap between the seam and the lower mold 401 with a caliper. The dimensions of the mold for burr measurement are as follows: the outer shape of the upper die 400 and the lower die 401 is (140 mm) × (140 mm), the diameter of the resin injection port is 7 mm at the top, 4 mm at the bottom, the diameter of the cavity is 30 mm, and the depth of the cavity The depth of the six slits 404 to 409 is 75, 50, 30, 20, 10, and 2 μm in this order.
表２及び３中、＊１〜９は以下の通りである。
＊１：トリスグリシジルイソシアヌレート（エポキシ当量１００、日産化学社製、商品名：ＴＥＰＩＣ−Ｓ）
＊２：３，４−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（ダイセル化学社製、商品名：セロキサイド２０２１Ｐ）
＊３：ヘキサヒドロ無水フタル酸（和光純薬工業社製）
＊４：水素化−１，２−無水トリメリット酸（三菱ガス化学社製）
＊５：テトラ−ｎ−ブチルホスホニウム−ｏ，ｏ−ジエチルホスホロジチエート（日本化学工業社製、商品名：ＰＸ−４ＥＴ）
＊６：トリメトキシエポキシシラン（東レダウコーニング社製、商品名：Ａ−１８７）
＊７：溶融シリカ（電気化学工業社製、商品名：ＦＢ−３０１）
＊８：中空粒子（住友３Ｍ社製、商品名：Ｓ６０−ＨＳ）
＊９：アルミナ（アドマテックス社製、商品名：ＡＯ−２５Ｒ）
In Tables 2 and 3, * 1 to 9 are as follows.
* 1: Trisglycidyl isocyanurate (epoxy equivalent 100, manufactured by Nissan Chemical Co., Ltd., trade name: TEPIC-S)
* 2: 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate (manufactured by Daicel Chemical Industries, trade name: Celoxide 2021P)
* 3: Hexahydrophthalic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.)
* 4: Hydrogenated 1,2-trimellitic anhydride (Mitsubishi Gas Chemical Co., Ltd.)
* 5: Tetra-n-butylphosphonium-o, o-diethyl phosphorodithioate (manufactured by Nippon Chemical Industry Co., Ltd., trade name: PX-4ET)
* 6: Trimethoxyepoxysilane (manufactured by Toray Dow Corning, trade name: A-187)
* 7: Fused silica (trade name: FB-301, manufactured by Denki Kagaku Kogyo Co., Ltd.)
* 8: Hollow particles (manufactured by Sumitomo 3M, trade name: S60-HS)
* 9: Alumina (manufactured by Admatechs, trade name: AO-25R)
表２に示したように、本発明の熱硬化性樹脂組成物は、光反射特性に優れ、バリを低減、すなわち、樹脂汚れを十分に低減することが可能である。 As shown in Table 2, the thermosetting resin composition of the present invention is excellent in light reflection characteristics and can reduce burrs, that is, sufficiently reduce resin contamination.
本発明の熱硬化性樹脂組成物を用いてトランスファー成形することにより、光半導体素子搭載領域の樹脂汚れが十分に低減した光半導体素子搭載用基板を作製することができる。これにより、光半導体素子搭載領域の開口部に光半導体素子を搭載でき、光半導体素子と金属配線とをボンディングワイヤなど公知の方法により電気的に接続することが可能になる。また、本発明によれば、光半導体素子搭載用基板の製造工程においてバリを除去する工程が不要となりコストや製造時間など生産性の面で非常に有利となる。 By carrying out transfer molding using the thermosetting resin composition of the present invention, a substrate for mounting an optical semiconductor element in which resin contamination in the optical semiconductor element mounting region is sufficiently reduced can be produced. Thus, the optical semiconductor element can be mounted in the opening of the optical semiconductor element mounting region, and the optical semiconductor element and the metal wiring can be electrically connected by a known method such as a bonding wire. In addition, according to the present invention, a step of removing burrs is not required in the manufacturing process of the optical semiconductor element mounting substrate, which is very advantageous in terms of productivity such as cost and manufacturing time.
１００…光半導体素子、１０１…透明封止樹脂、１０２…ボンディングワイヤ、１０３…熱硬化性樹脂組成物の硬化物（リフレクター）、１０４…Ｎｉ／Ａｇめっき、１０５…金属配線、１０６…蛍光体、１０７…はんだバンプ、１１０…光半導体素子搭載用基板、２００…光半導体素子搭載領域、１５０…樹脂注入口、１５１…金型、３００…ＬＥＤ素子、３０１…ボンディングワイヤ、３０２…透明封止樹脂、３０３…リフレクター、３０４…リード、３０５…蛍光体、３０６…ダイボンド材、４００…バリ測定用金型（上型）、４０１…バリ測定用金型（下型）、４０２…樹脂注入口、４０３…キャビティ、４０４…スリット（７５μｍ）、４０５…スリット（５０μｍ）、４０６…スリット（３０μｍ）、４０７…スリット（２０μｍ）、４０８…スリット（１０μｍ）、４０９…スリット（２μｍ）、４１０…樹脂バリ。
DESCRIPTION OF SYMBOLS 100 ... Optical semiconductor element, 101 ... Transparent sealing resin, 102 ... Bonding wire, 103 ... Hardened | cured material (reflector) of a thermosetting resin composition, 104 ... Ni / Ag plating, 105 ... Metal wiring, 106 ... Phosphor, DESCRIPTION OF SYMBOLS 107 ... Solder bump, 110 ... Optical semiconductor element mounting substrate, 200 ... Optical semiconductor element mounting area, 150 ... Resin injection port, 151 ... Mold, 300 ... LED element, 301 ... Bonding wire, 302 ... Transparent sealing resin, 303: reflector, 304 ... lead, 305 ... phosphor, 306 ... die bond material, 400 ... mold for burr measurement (upper mold), 401 ... mold for burr measurement (lower mold), 402 ... resin injection port, 403 ... Cavity, 404 ... slit (75 μm), 405 ... slit (50 μm), 406 ... slit (30 μm), 407 ... slit (20 μm) , 408 ... slit (10 [mu] m), 409 ... slit (2 [mu] m), 410 ... resin burrs.
Claims (9)
前記凹部の底面が光半導体素子搭載部であり、前記凹部の壁面の少なくとも一部が、請求項１〜６のいずれか一項に記載のエポキシ樹脂成形材料の硬化物からなる、光半導体素子搭載用基板。 Having a recess composed of a bottom surface and a wall surface;
The bottom surface of the recess is the photosemiconductor element mounting portion, at least a part of the wall surface of the concave portion, a cured product of the epoxy resin molding material according to any one of claims 1 to 6, an optical semiconductor element mounting Substrate.
前記凹部の壁面の少なくとも一部を、請求項１〜６のいずれか一項に記載のエポキシ樹脂成形材料を用いて形成する工程を備える、光半導体素子搭載用基板の製造方法。 A method of manufacturing a substrate for mounting an optical semiconductor element having a recess composed of a bottom surface and a wall surface,
At least a portion, comprising the step of forming by using an epoxy resin molding material according to any one of claims 1 to 6, the manufacturing method of the optical semiconductor element mounting board of the wall of the recess.
前記光半導体素子搭載用基板の凹部内に設けられた光半導体素子と、
前記凹部を充填して前記光半導体素子を封止する封止樹脂部と、
を備え、
前記凹部の壁面の少なくとも一部が、請求項１〜６のいずれか一項に記載のエポキシ樹脂成形材料の硬化物からなる、光半導体装置。 An optical semiconductor element mounting substrate having a recess composed of a bottom surface and a wall surface;
An optical semiconductor element provided in a recess of the optical semiconductor element mounting substrate;
A sealing resin portion that fills the recess and seals the optical semiconductor element;
With
At least part of the wall of the recess, a cured product of the epoxy resin molding material according to any one of claims 1 to 6, the optical semiconductor device.
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| JP2010105524A JP5516035B2 (en) | 2008-01-09 | 2010-04-30 | Epoxy resin molding material, substrate for mounting optical semiconductor element, manufacturing method thereof, and optical semiconductor device |
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| JP2008248711 | 2008-09-26 | ||
| JP2010105524A JP5516035B2 (en) | 2008-01-09 | 2010-04-30 | Epoxy resin molding material, substrate for mounting optical semiconductor element, manufacturing method thereof, and optical semiconductor device |
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| JP2010105524A Active JP5516035B2 (en) | 2008-01-09 | 2010-04-30 | Epoxy resin molding material, substrate for mounting optical semiconductor element, manufacturing method thereof, and optical semiconductor device |
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| CN109996855A (en) * | 2016-12-22 | 2019-07-09 | 日产化学株式会社 | Heat-storing material |
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| KR20150140868A (en) | 2008-01-09 | 2015-12-16 | 히타치가세이가부시끼가이샤 | Thermosetting resin composition, epoxy resin molding material, and polyvalent carboxylic acid condensate |
| US8637593B2 (en) | 2008-01-09 | 2014-01-28 | Hitachi Chemical Company, Ltd. | Thermosetting resin composition, epoxy resin molding material, and polyvalent carboxylic acid condensate |
| JP4666075B2 (en) * | 2008-01-11 | 2011-04-06 | 日立化成工業株式会社 | Polyvalent carboxylic acid condensate, and curing agent for epoxy resin, epoxy resin composition, polyamide resin and polyester resin using the same |
| JP5640319B2 (en) * | 2008-03-11 | 2014-12-17 | 日立化成株式会社 | Curing agent for thermosetting resin, thermosetting resin composition, cured product, and semiconductor device |
| JP5401905B2 (en) * | 2008-04-25 | 2014-01-29 | 日立化成株式会社 | Thermosetting resin composition |
| JP5936804B2 (en) * | 2009-12-14 | 2016-06-22 | 日立化成株式会社 | Thermosetting resin composition, substrate for mounting optical semiconductor element, manufacturing method thereof, and optical semiconductor device |
| EP2725060A4 (en) * | 2011-06-27 | 2015-04-15 | Daicel Corp | Curable resin composition for reflection of light, and optical semiconductor device |
| JP6107559B2 (en) * | 2012-11-09 | 2017-04-05 | 豊田合成株式会社 | Light emitting device |
| JP2014141584A (en) * | 2013-01-24 | 2014-08-07 | Toyama Prefecture | Thermosetting resin composition |
| JP6220133B2 (en) * | 2013-02-26 | 2017-10-25 | 京セラ株式会社 | Optical semiconductor case molding resin composition and optical semiconductor case |
| EP2987818B1 (en) | 2013-04-19 | 2018-04-18 | New Japan Chemical Co., Ltd. | Novel polycarboxylic acid anhydride and use thereof |
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| JP2010242095A (en) | 2010-10-28 |
| JP2010100798A (en) | 2010-05-06 |
| JP5516165B2 (en) | 2014-06-11 |
| JP4586925B2 (en) | 2010-11-24 |
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