TWI512034B - Curable epoxy resin composition - Google Patents
Curable epoxy resin composition Download PDFInfo
- Publication number
- TWI512034B TWI512034B TW101100545A TW101100545A TWI512034B TW I512034 B TWI512034 B TW I512034B TW 101100545 A TW101100545 A TW 101100545A TW 101100545 A TW101100545 A TW 101100545A TW I512034 B TWI512034 B TW I512034B
- Authority
- TW
- Taiwan
- Prior art keywords
- resin composition
- alicyclic
- epoxy resin
- compound
- optical semiconductor
- Prior art date
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- 239000003822 epoxy resin Substances 0.000 title claims description 88
- 239000000203 mixture Substances 0.000 title claims description 88
- 229920000647 polyepoxide Polymers 0.000 title claims description 88
- 125000002723 alicyclic group Chemical group 0.000 claims description 127
- 230000003287 optical effect Effects 0.000 claims description 84
- 239000004065 semiconductor Substances 0.000 claims description 77
- 150000001875 compounds Chemical class 0.000 claims description 68
- 239000002245 particle Substances 0.000 claims description 56
- 239000004645 polyester resin Substances 0.000 claims description 52
- 229920001225 polyester resin Polymers 0.000 claims description 52
- 229920001971 elastomer Polymers 0.000 claims description 48
- 239000005060 rubber Substances 0.000 claims description 48
- -1 ester compound Chemical class 0.000 claims description 46
- 239000004593 Epoxy Substances 0.000 claims description 40
- 238000007789 sealing Methods 0.000 claims description 33
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 32
- 125000003700 epoxy group Chemical group 0.000 claims description 24
- 125000004432 carbon atom Chemical group C* 0.000 claims description 19
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 17
- 239000004848 polyfunctional curative Substances 0.000 claims description 15
- 239000011342 resin composition Substances 0.000 claims description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 229920000728 polyester Polymers 0.000 claims description 8
- WHNBDXQTMPYBAT-UHFFFAOYSA-N 2-butyloxirane Chemical compound CCCCC1CO1 WHNBDXQTMPYBAT-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 description 47
- 239000000178 monomer Substances 0.000 description 32
- 239000000306 component Substances 0.000 description 30
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 29
- 238000004519 manufacturing process Methods 0.000 description 25
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 24
- 238000002156 mixing Methods 0.000 description 22
- 239000000126 substance Substances 0.000 description 18
- 229920000642 polymer Polymers 0.000 description 16
- 229920005989 resin Polymers 0.000 description 16
- 239000011347 resin Substances 0.000 description 16
- 239000000470 constituent Substances 0.000 description 15
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 150000008065 acid anhydrides Chemical class 0.000 description 9
- 229920002554 vinyl polymer Polymers 0.000 description 9
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 8
- 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 8
- 230000007423 decrease Effects 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 150000002009 diols Chemical class 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 235000013772 propylene glycol Nutrition 0.000 description 5
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229920000459 Nitrile rubber Polymers 0.000 description 4
- 150000008064 anhydrides Chemical class 0.000 description 4
- 150000001993 dienes Chemical class 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 125000005647 linker group Chemical group 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 4
- 125000004430 oxygen atom Chemical group O* 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- FKBMTBAXDISZGN-UHFFFAOYSA-N 5-methyl-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1C(C)CCC2C(=O)OC(=O)C12 FKBMTBAXDISZGN-UHFFFAOYSA-N 0.000 description 3
- YXALYBMHAYZKAP-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl 7-oxabicyclo[4.1.0]heptane-4-carboxylate Chemical compound C1CC2OC2CC1C(=O)OCC1CC2OC2CC1 YXALYBMHAYZKAP-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 125000005410 aryl sulfonium group Chemical group 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000011951 cationic catalyst Substances 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 125000006165 cyclic alkyl group Chemical group 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000011010 flushing procedure Methods 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 150000002825 nitriles Chemical class 0.000 description 3
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 3
- 150000004714 phosphonium salts Chemical class 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- 235000019394 potassium persulphate Nutrition 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 2
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- YWVFNWVZBAWOOY-UHFFFAOYSA-N 4-methylcyclohexane-1,2-dicarboxylic acid Chemical compound CC1CCC(C(O)=O)C(C(O)=O)C1 YWVFNWVZBAWOOY-UHFFFAOYSA-N 0.000 description 2
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 description 2
- OXQXGKNECHBVMO-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptane-4-carboxylic acid Chemical group C1C(C(=O)O)CCC2OC21 OXQXGKNECHBVMO-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- WVKBWQQMWAVNDE-UHFFFAOYSA-N C(O)(O)=O.C(C)(C)C=CC Chemical compound C(O)(O)=O.C(C)(C)C=CC WVKBWQQMWAVNDE-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 239000004641 Diallyl-phthalate Substances 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- RQBBFKINEJYDOB-UHFFFAOYSA-N acetic acid;acetonitrile Chemical compound CC#N.CC(O)=O RQBBFKINEJYDOB-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- PFURGBBHAOXLIO-UHFFFAOYSA-N cyclohexane-1,2-diol Chemical compound OC1CCCCC1O PFURGBBHAOXLIO-UHFFFAOYSA-N 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 125000005594 diketone group Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010556 emulsion polymerization method Methods 0.000 description 2
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229940074404 sodium succinate Drugs 0.000 description 2
- ZDQYSKICYIVCPN-UHFFFAOYSA-L sodium succinate (anhydrous) Chemical compound [Na+].[Na+].[O-]C(=O)CCC([O-])=O ZDQYSKICYIVCPN-UHFFFAOYSA-L 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 229920006027 ternary co-polymer Polymers 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 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
- 238000004383 yellowing Methods 0.000 description 2
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical group NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 1
- TZPCGEVFZZYCIY-UHFFFAOYSA-N 1-octylsulfonyloctane Chemical group CCCCCCCCS(=O)(=O)CCCCCCCC TZPCGEVFZZYCIY-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- MFAWEYJGIGIYFH-UHFFFAOYSA-N 2-[4-(trimethoxymethyl)dodecoxymethyl]oxirane Chemical compound C(C1CO1)OCCCC(C(OC)(OC)OC)CCCCCCCC MFAWEYJGIGIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 description 1
- UIDDPPKZYZTEGS-UHFFFAOYSA-N 3-(2-ethyl-4-methylimidazol-1-yl)propanenitrile Chemical compound CCC1=NC(C)=CN1CCC#N UIDDPPKZYZTEGS-UHFFFAOYSA-N 0.000 description 1
- WVRNUXJQQFPNMN-VAWYXSNFSA-N 3-[(e)-dodec-1-enyl]oxolane-2,5-dione Chemical compound CCCCCCCCCC\C=C\C1CC(=O)OC1=O WVRNUXJQQFPNMN-VAWYXSNFSA-N 0.000 description 1
- YHFGMFYKZBWPRW-UHFFFAOYSA-N 3-methylpentane-1,1-diol Chemical compound CCC(C)CC(O)O YHFGMFYKZBWPRW-UHFFFAOYSA-N 0.000 description 1
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- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/226—Mixtures of di-epoxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/26—Di-epoxy compounds heterocyclic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
-
- 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
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/52—Encapsulations
- H01L33/56—Materials, e.g. epoxy or silicone resin
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
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- General Physics & Mathematics (AREA)
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Description
本發明係關於硬化性環氧樹脂組成物、將該硬化性環氧樹脂組成物硬化而成之硬化物、包含該硬化性環氧樹脂組成物而構成之光半導體密封用樹脂組成物、及使用該光半導體密封用樹脂組成物將光半導體元件予以密封而成之光半導體裝置。The present invention relates to a curable epoxy resin composition, a cured product obtained by curing the curable epoxy resin composition, a resin composition for optical semiconductor sealing comprising the curable epoxy resin composition, and a use thereof. This optical semiconductor sealing resin composition is an optical semiconductor device in which an optical semiconductor element is sealed.
近年來，光半導體裝置之高輸出化已有進展，於光半導體裝置使用之樹脂要求高度的耐熱性及耐光性。例如：於藍色、白色光半導體用之密封材(密封樹脂)，由光半導體元件發出之光及熱導致之密封樹脂的黃變成為問題。黃變的密封樹脂，由於會吸收來自於光半導體元件所發的光，故會使從光半導體裝置輸出之光的光度隨時間降低。In recent years, high output of optical semiconductor devices has progressed, and resins used in optical semiconductor devices require high heat resistance and light resistance. For example, in the sealing material (sealing resin) for blue and white light semiconductors, the light emitted from the optical semiconductor element and the yellow of the sealing resin caused by heat become a problem. The yellowing sealing resin absorbs light emitted from the optical semiconductor element, so that the luminosity of the light output from the optical semiconductor device decreases with time.
至今為止，高耐熱性之密封樹脂，已知有含有異三聚氰酸單烯丙基二環氧丙酯與雙酚A型環氧樹脂之組成物(參照專利文獻1)。但是若將上述硬化物作為高輸出的藍色、白色光半導體用之密封樹脂，會由於光半導體元件發出的光及熱導致著色進行，使原本應輸出的光被吸收，其結果會有從光半導體裝置輸出的光的光度隨時間降低的問題。A composition containing a monoacrylic acid monoallyl diglycidyl ester and a bisphenol A type epoxy resin is known as a sealing resin having high heat resistance (see Patent Document 1). However, when the cured product is used as a sealing resin for a high-output blue and white photo-semiconductor, coloring is caused by light and heat emitted from the optical semiconductor element, and the light to be output is absorbed, and as a result, there is light. The problem that the luminosity of light output by a semiconductor device decreases with time.
專利文獻1 日本特開2000-344867號公報Patent Document 1 Japanese Patent Laid-Open Publication No. 2000-344867
就具有高度耐熱性及耐光性且不易黃變之密封樹脂而言，已知有3,4-環氧環己基甲基(3,4-環氧)環己烷羧酸酯、3,4-環氧環己基甲基(3,4-環氧)環己烷羧酸酯與ε-己內酯之加成物、1,2,8,9-二環氧檸檬烯等具脂環骨架之液狀脂環環氧樹脂。但是，該等脂環環氧樹脂的硬化物不耐各種應力，當施加冷熱循環(反覆加熱與冷卻)此類的熱衝撃時，會有產生龜裂(裂隙)等之問題。3,4-epoxycyclohexylmethyl (3,4-epoxy)cyclohexanecarboxylate, 3,4-, is known as a sealing resin having high heat resistance and light resistance and not easily yellowing. An adduct of epoxycyclohexylmethyl (3,4-epoxy)cyclohexanecarboxylate and ε-caprolactone, and an alicyclic skeleton such as 1,2,8,9-diepoxylimene Epoxy resin. However, the cured products of the alicyclic epoxy resins are not resistant to various stresses, and when hot heat cycles such as heating and cooling (reverse heating and cooling) are applied, cracks (cracks) and the like may occur.
所以，現狀為需要光半導體裝置(尤其是具備高輸出、高輝度之光半導體元件的光半導體裝置)輸出之光隨時間的光度降低受抑制之兼具高度耐熱性、耐光性及耐龜裂性之透明的密封樹脂。Therefore, the current state of the art requires an optical semiconductor device (especially an optical semiconductor device having a high-output, high-intensity optical semiconductor device) to emit light with a reduced luminosity over time, and has high heat resistance, light resistance, and crack resistance. Transparent sealing resin.
因此本發明之目的在於提供能賦予兼具高透明性、耐熱性、耐光性、及耐龜裂性之硬化物之硬化性環氧樹脂組成物。Therefore, an object of the present invention is to provide a curable epoxy resin composition capable of imparting a cured product having high transparency, heat resistance, light resistance, and crack resistance.
又，本發明之另一目的在於提供將上述硬化性環氧樹脂組成物硬化而成之兼具高透明性、耐熱性、耐光性、及耐龜裂性之硬化物。Moreover, another object of the present invention is to provide a cured product which is obtained by curing the curable epoxy resin composition and having high transparency, heat resistance, light resistance, and crack resistance.
又，本發明之另一目的在於提供包含上述硬化性環氧樹脂組成物而構成的光半導體密封用樹脂組成物，能獲得隨時間的光度降低受抑制之光半導體裝置。Moreover, another object of the present invention is to provide an optical semiconductor sealing resin composition comprising the above-mentioned curable epoxy resin composition, and it is possible to obtain an optical semiconductor device in which luminosity reduction with time is suppressed.
又，本發明之另一目的在於提供利用兼具高耐熱性、耐光性、透明性、及耐龜裂性之硬化物予以密封且隨時間之光度降低受抑制之光半導體裝置，其係使用上述光半導體密封用樹脂組成物將光半導體元件予以密封而獲得。Further, another object of the present invention is to provide an optical semiconductor device which is sealed by a cured product having high heat resistance, light resistance, transparency, and crack resistance, and which is suppressed in time due to reduction in luminosity. The resin composition for optical semiconductor sealing is obtained by sealing an optical semiconductor element.
本案發明人為了解決上述課題，努力探討，結果發現：含有脂環環氧化合物、異三聚氰酸單烯丙基二環氧丙酯化合物及脂環聚酯樹脂當作必要成分，且更含有硬化劑及硬化促進劑、或硬化觸媒之硬化性環氧樹脂組成物，可提供兼具優異耐熱性、耐光性、透明性、耐龜裂性之硬化物，以該硬化物密封光半導體元件而得之光半導體裝置，隨時間的光度不易降低，乃完成本發明。In order to solve the above problems, the inventors of the present invention have intensively studied and found that an alicyclic epoxy compound, an isomeric cyanuric acid monoallyl diglycidyl ester compound, and an alicyclic polyester resin are contained as essential components, and more A hardening agent and a curing accelerator or a curing epoxy resin composition for curing a catalyst, which can provide a cured product having excellent heat resistance, light resistance, transparency, and crack resistance, and the optical semiconductor element is sealed with the cured product. In the case of the optical semiconductor device, the luminosity over time is not easily lowered, and the present invention has been completed.
亦即，本發明提供一種硬化性環氧樹脂組成物，其特徵為：包含脂環環氧化合物(A)、與以下式(1)表示之異三聚氰酸單烯丙基二環氧丙酯化合物(B)、與脂環聚酯樹脂(C)、與硬化劑(D)、與硬化促進劑(E)；That is, the present invention provides a curable epoxy resin composition characterized by comprising an alicyclic epoxy compound (A) and an isomeric cyanuric acid monoallyl propylene glycol represented by the following formula (1) Ester compound (B), and alicyclic polyester resin (C), and hardener (D), and hardening accelerator (E);
[式中，R1 及R2 表示氫原子或碳數1~8之烷基]。[wherein, R 1 and R 2 represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms].
又，本發明提供一種硬化性環氧樹脂組成物，其包含：脂環環氧化合物(A)、與以下式(1)表示之異三聚氰酸單烯丙基二環氧丙酯化合物(B)、與脂環聚酯樹脂(C)、與硬化觸媒(F)；Moreover, the present invention provides a curable epoxy resin composition comprising: an alicyclic epoxy compound (A), and a isocyanurate monoallyl diglycidyl compound represented by the following formula (1) ( B), with an alicyclic polyester resin (C), and a hardening catalyst (F);
[式中，R1 及R2 表示氫原子或碳數1~8之烷基]。[wherein, R 1 and R 2 represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms].
再者，提供如前述硬化性環氧樹脂組成物，其中，前述脂環環氧化合物(A)之脂環環氧基為環氧己烯基。Furthermore, the curable epoxy resin composition according to the above aspect, wherein the alicyclic epoxy group of the alicyclic epoxy compound (A) is hexylene oxide.
再者，提供如前述硬化性環氧樹脂組成物，其中，前述脂環環氧化合物(A)以下式(I-1)表示：Furthermore, the above-mentioned curable epoxy resin composition is provided, wherein the alicyclic epoxy compound (A) is represented by the following formula (I-1):
再者，提供如前述硬化性環氧樹脂組成物，其中，脂環聚酯樹脂(C)係於主鏈具有脂環之脂環聚酯。Further, a curable epoxy resin composition as described above is provided, wherein the alicyclic polyester resin (C) is an alicyclic polyester having an alicyclic ring in its main chain.
再者，提供如前述硬化性環氧樹脂組成物，更含有橡膠粒子。Further, a curable epoxy resin composition as described above is further provided, and rubber particles are further contained.
又，本發明提供將前述硬化性環氧樹脂組成物硬化而成的硬化物。Moreover, the present invention provides a cured product obtained by curing the curable epoxy resin composition.
又，本發明提供包含前述硬化性環氧樹脂組成物而構成之光半導體密封用樹脂組成物。Moreover, the present invention provides a resin composition for optical semiconductor sealing comprising the above-mentioned curable epoxy resin composition.
又，本發明提供以前述光半導體密封用樹脂組成物將光半導體元件予以密封而得之光半導體裝置。Moreover, the present invention provides an optical semiconductor device obtained by sealing an optical semiconductor element with the resin composition for optical semiconductor sealing described above.
本發明之硬化性環氧樹脂組成物由於具有上述構成，故藉由使該樹脂組成物硬化可獲得兼具高透明性、耐熱性、耐光性、及耐龜裂性之硬化物。又，使用本發明之硬化性環氧樹脂組成物密封光半導體元件而得之光半導體裝置，光度不易隨時間降低，能發揮優異的品質及耐久性。尤其，本發明之硬化性環氧樹脂組成物，即使當作具備高輸出、高輝度之光半導體元件之光半導體裝置之密封用樹脂使用時，仍能抑制該光半導體裝置的光度隨時間降低。Since the curable epoxy resin composition of the present invention has the above-described configuration, a cured product having high transparency, heat resistance, light resistance, and crack resistance can be obtained by curing the resin composition. Moreover, the optical semiconductor device obtained by sealing the optical semiconductor element using the curable epoxy resin composition of the present invention has a low illuminance with time, and exhibits excellent quality and durability. In particular, when the curable epoxy resin composition of the present invention is used as a sealing resin for an optical semiconductor device having a high-output, high-luminance optical semiconductor device, the luminosity of the optical semiconductor device can be suppressed from decreasing with time.
本發明之硬化性環氧樹脂組成物，包含：脂環環氧化合物(A)、與以下式(1)表示之異三聚氰酸單烯丙基二環氧丙酯化合物(B)與、脂環聚酯樹脂(C)與、硬化劑(D)、與硬化促進劑(E)；The curable epoxy resin composition of the present invention comprises: an alicyclic epoxy compound (A), and a isocyanuric acid monoallyl diglycidyl ester compound (B) represented by the following formula (1); Alicyclic polyester resin (C), hardener (D), and hardening accelerator (E);
[式(1)中，R1 及R2 表示氫原子或碳數1~8之烷基]。In the formula (1), R 1 and R 2 each represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
又，本發明之硬化性環氧樹脂組成物，包含：脂環環氧化合物(A)、與以上式(1)表示之異三聚氰酸單烯丙基二環氧丙酯化合物(B)、與脂環聚酯樹脂(C)、與硬化觸媒(F)。Further, the curable epoxy resin composition of the present invention comprises: an alicyclic epoxy compound (A) and a isocyanuric acid monoallyl diglycidyl ester compound (B) represented by the above formula (1) , with alicyclic polyester resin (C), and hardening catalyst (F).
本發明使用之脂環環氧化合物(A)，包含(i)具有以構成脂環之相鄰的2個碳原子與氧原子構成之環氧基之化合物、及(ii)環氧基直接以單鍵鍵結於脂環之化合物。The alicyclic epoxy compound (A) used in the present invention comprises (i) a compound having an epoxy group constituting two adjacent carbon atoms and an oxygen atom of an alicyclic ring, and (ii) an epoxy group directly A compound that is bonded to an alicyclic ring by a single bond.
(i)具有以構成脂環之相鄰的2個碳原子與氧原子構成之環氧基(脂環環氧基)之化合物，可從公知或慣用者中任意選用。上述脂環環氧基，較佳為環氧己烯基。(i) A compound having an epoxy group (alicyclic epoxy group) constituting two carbon atoms adjacent to an alicyclic ring and an oxygen atom, which may be arbitrarily selected from known or customary. The above alicyclic epoxy group is preferably an epoxyhexene group.
(i)具有以構成脂環之相鄰的2個碳原子與氧原子構成之環氧基之化合物，尤其從透明性、耐熱性之觀點，以下式(I)表示之脂環環氧樹脂(脂環環氧化合物)為理想。(i) a compound having an epoxy group composed of two adjacent carbon atoms and an oxygen atom constituting an alicyclic ring, and an alicyclic epoxy resin represented by the following formula (I), in particular, from the viewpoints of transparency and heat resistance ( An alicyclic epoxy compound is desirable.
式(I)中，X表示單鍵或連結基(具有1個以上之原子的2價基)。上述連結基，例如：2價之烴基、羰基、醚鍵、酯鍵、碳酸酯基、醯胺基、及將該等連結多個而成的基團等。In the formula (I), X represents a single bond or a linking group (a divalent group having one or more atoms). Examples of the linking group include a divalent hydrocarbon group, a carbonyl group, an ether bond, an ester bond, a carbonate group, a guanamine group, and a group obtained by linking a plurality of these groups.
式(I)中之X為單鍵之脂環環氧化合物，例如下式表示之化合物。如此的脂環環氧化合物例如也可使用CELLOXIDE8000(Daicel(股)製)等市售品。The alicyclic epoxy compound in which X in the formula (I) is a single bond, for example, a compound represented by the following formula. As such an alicyclic epoxy compound, for example, a commercially available product such as CELLOXIDE 8000 (manufactured by Daicel Co., Ltd.) can also be used.
上述2價之烴基，例如碳數1~18之直鏈狀或分支鏈狀之伸烷基、2價之脂環烴基等。碳數1~18之直鏈狀或支鏈狀之伸烷基，例如：亞甲基、甲基亞甲基、二甲基亞甲基、伸乙基、伸丙基、三亞甲基等。2價之脂環烴基，例如：1,2-環伸戊基、1,3-環伸戊基、環亞戊基、1,2-環伸己基、1,3-環伸己基、1,4-環伸己基、環亞己基等2價之環伸烷基(含環亞烷基)等。The above-mentioned divalent hydrocarbon group is, for example, a linear or branched alkyl group having 1 to 18 carbon atoms, a divalent alicyclic hydrocarbon group or the like. A linear or branched alkyl group having 1 to 18 carbon atoms, for example, a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylidene group, a propyl group, a trimethylene group or the like. a divalent alicyclic hydrocarbon group, for example, 1,2-cyclopentyl, 1,3-cyclopentyl, cyclopentylene, 1,2-cyclohexyl, 1,3-cyclohexyl, 1, A bivalent cycloalkyl group (including a cycloalkylene group) such as a 4-cyclohexyl group or a cyclohexylene group.
上述連結基X，較佳為含氧原子之連結基，具體而言例如-CO-、-O-CO-O-、-COO-、-O-、-CONH-；該等基連接多個而得之基；該等基之1或2個以上與2價之烴基之1或2個以上連結而得之基等。2價之烴基，例如上述例示者。The linking group X is preferably a linking group containing an oxygen atom, specifically, for example, -CO-, -O-CO-O-, -COO-, -O-, -CONH-; A group obtained by linking one or two or more of the above-mentioned groups to one or more of the divalent hydrocarbon groups. A divalent hydrocarbon group such as the ones exemplified above.
上式(I)表示之脂環環氧化合物之代表例，例如下式(I-1)~(I-8)表示之化合物等。例如可使用CELLOXIDE2021P、CELLOXIDE2081(Daicel(股)製)等市售品。又，下式(I-1)~(I-8)中，l、m表示1~30之整數。R表示碳數1~8之伸烷基，例如亞甲基、伸乙基、伸丙基、伸異丙基、伸丁基、伸異丁基、伸第二丁基、伸戊基、伸己基、伸庚基、伸辛基等直鏈狀或分支鏈狀伸烷基。該等之中，亞甲基、伸乙基、伸丙基、異伸丙基等碳數1~3之直鏈狀或支鏈狀伸烷基較佳。Representative examples of the alicyclic epoxy compound represented by the above formula (I) are, for example, compounds represented by the following formulas (I-1) to (I-8). For example, commercially available products such as CELLOXIDE 2021P and CELLOXIDE 2081 (manufactured by Daicel Co., Ltd.) can be used. Further, in the following formulae (I-1) to (I-8), l and m represent an integer of 1 to 30. R represents an alkylene group having 1 to 8 carbon atoms, such as methylene, ethyl, propyl, isopropyl, butyl, isobutyl, butyl, pentylene, and A linear or branched chain alkyl group such as a hexyl group, a heptyl group or a octyl group. Among these, a linear or branched alkylene group having 1 to 3 carbon atoms such as a methylene group, an ethylidene group, a propyl group or an iso stretched propyl group is preferred.
(ii)環氧基直接以單鍵鍵結於脂環的化合物，例如：下式(II)表示之化合物。(ii) a compound in which an epoxy group is directly bonded to an alicyclic ring by a single bond, for example, a compound represented by the following formula (II).
式(II)中，R'為p價之醇去除p個-OH後之基，p、n代表自然數。p價之醇[R'-(OH)p ]，例如2,2-雙(羥基甲基)-1-丁醇等多元醇等(碳數1~15之醇等)。p宜為1~6，n為1~30較佳。p為2以上時，各( )內(圓括弧內)之基的n可為相同也可為不同。上述化合物，具體而言，例如2,2-雙(羥基甲基)-1-丁醇之1,2-環氧-4-(2-環氧乙基)環己烷加成物、EHPE 3150(Daicel(股)製)等。In the formula (II), R' is a group in which p-valent alcohol removes p-OH, and p and n represent natural numbers. The p-valent alcohol [R'-(OH) p ], for example, a polyhydric alcohol such as 2,2-bis(hydroxymethyl)-1-butanol or the like (an alcohol having 1 to 15 carbon atoms). p is preferably from 1 to 6, and n is preferably from 1 to 30. When p is 2 or more, n of each of the bases (in the parentheses) may be the same or different. The above compound, specifically, for example, 1,2-epoxy-4-(2-epoxyethyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, EHPE 3150 (Daicel (share) system) and so on.
該等脂環環氧化合物(A)可以單獨使用，或組合2種以上使用。脂環環氧化合物(A)，以上式(I-1)表示之3,4-環氧環己基甲基(3,4-環氧)環己烷羧酸酯、CELLOXIDE2021P尤佳。These alicyclic epoxy compounds (A) may be used singly or in combination of two or more. The alicyclic epoxy compound (A) is preferably a 3,4-epoxycyclohexylmethyl (3,4-epoxy)cyclohexanecarboxylate represented by the above formula (I-1), and CELLOXIDE 2021P.
脂環環氧化合物(A)之使用量(含量)不特別限定，相對於脂環環氧化合物(A)與異三聚氰酸單烯丙基二環氧丙酯化合物(B)之總量(100重量%)，為50~90重量%較佳，更佳為60~90重量%，又更佳為70~90重量%。脂環環氧化合物(A)之使用量低於50重量%時，異三聚氰酸單烯丙基二環氧丙酯化合物(B)之溶解性不夠，若置於室溫，有時會容易析出。另一方面，脂環環氧化合物(A)之使用量若超過90重量%，當製作光半導體裝置時，有時會容易發生龜裂。成分(A)、成分(B)、及成分(C)之總量(100重量%)中，脂環環氧化合物(A)與異三聚氰酸單烯丙基二環氧丙酯化合物(B)之含量總和(總量)不特別限定，為70~90重量%較佳。The amount (content) of the alicyclic epoxy compound (A) is not particularly limited, and is relative to the total amount of the alicyclic epoxy compound (A) and the isomeric cyanuric acid monoallyl diglycidyl ester compound (B). (100% by weight), preferably from 50 to 90% by weight, more preferably from 60 to 90% by weight, still more preferably from 70 to 90% by weight. When the amount of the alicyclic epoxy compound (A) used is less than 50% by weight, the solubility of the isocyanurate monoallyl diglycidyl ester compound (B) is insufficient, and if it is left at room temperature, sometimes it may be Easy to precipitate. On the other hand, when the amount of the alicyclic epoxy compound (A) used exceeds 90% by weight, cracks may easily occur when an optical semiconductor device is produced. In the total amount (100% by weight) of the component (A), the component (B), and the component (C), the alicyclic epoxy compound (A) and the isocyanurate monoallyl diglycidyl ester compound ( The sum (total amount) of the content of B) is not particularly limited, and is preferably from 70 to 90% by weight.
本發明使用之異三聚氰酸單烯丙基二環氧丙酯化合物(B)，可以用下列通式(1)表示。The isomeric cyanuric acid monoallyl diglycidyl ester compound (B) used in the present invention can be represented by the following general formula (1).
上式(1)中，R1 及R2 表示氫原子或碳數1~8之烷基。In the above formula (1), R 1 and R 2 each represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
碳數1~8之烷基，例如：甲基、乙基、丙基、異丙基、丁基、異丁基、第二丁基、戊基、己基、庚基、辛基等直鏈狀或支鏈狀烷基。其中，甲基、乙基、丙基、異丙基等碳數1~3之直鏈狀或支鏈狀烷基為較佳。上式(1)中之R1 及R2 為氫原子尤佳。Alkyl groups having 1 to 8 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, heptyl, octyl, etc. Or branched alkyl. Among them, a linear or branched alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, a propyl group or an isopropyl group is preferred. R 1 and R 2 in the above formula (1) are preferably a hydrogen atom.
異三聚氰酸單烯丙基二環氧丙酯化合物(B)之代表例，例如異三聚氰酸單烯丙基二環氧丙酯、異三聚氰酸1-烯丙基-3,5-雙(2-甲基環氧丙基)酯、異三聚氰酸1-(2-甲基丙烯基)-3,5-二環氧丙基酯、異三聚氰酸1-(2-甲基丙烯基)-3,5-雙(2-甲基環氧丙基)酯等。又，異三聚氰酸單烯丙基二環氧丙酯化合物(B)可以單獨使用，或組合2種以上使用。Representative examples of the isomeric cyanuric acid monoallyl diglycidyl ester compound (B), such as isoallyl cyanurethane diglycidyl ester, isomeric cyanuric acid 1-allyl-3 , 5-bis(2-methylepoxypropyl) ester, iso(1,2-methylpropenyl)-3,5-diepoxypropyl ester, isomeric cyanuric acid 1- (2-Methylpropenyl)-3,5-bis(2-methylepoxypropyl) ester or the like. Further, the isocyanuric acid monoallyl diglycidyl ester compound (B) may be used singly or in combination of two or more.
異三聚氰酸單烯丙基二環氧丙酯化合物(B)，可於溶解於上述脂環環氧化合物(A)之範圍任意混合，脂環環氧化合物(A)與異三聚氰酸單烯丙基二環氧丙酯化合物(B)之比例不特別限定，脂環環氧化合物(A)：異三聚氰酸單烯丙基二環氧丙酯化合物(B)宜為50：50~90：10(重量比)較佳。為該範圍外時，異三聚氰酸單烯丙基二環氧丙酯化合物(B)之溶解性不容易獲得。The isocyanuric acid monoallyl diglycidyl ester compound (B) can be optionally mixed in the range of the above alicyclic epoxy compound (A), and the alicyclic epoxy compound (A) and isomeric cyanide The ratio of the acid monoallyl diglycidyl ester compound (B) is not particularly limited, and the alicyclic epoxy compound (A): the isocyanuric acid monoallyl diglycidyl ester compound (B) is preferably 50. : 50 to 90: 10 (weight ratio) is preferred. When it is outside this range, the solubility of the isomeric cyanuric acid monoallyl diglycidyl ester compound (B) is not easily obtained.
異三聚氰酸單烯丙基二環氧丙酯化合物(B)，也可使用添加醇或酸酐等會與環氧基反應之化合物而預先改性者。The isocyanuric acid monoallyl diglycidyl ester compound (B) may be previously modified by adding a compound which reacts with an epoxy group such as an alcohol or an acid anhydride.
脂環環氧化合物(A)與異三聚氰酸單烯丙基二環氧丙酯化合物(B)之總量，相對於環氧樹脂(具環氧基之化合物)之總量(100重量%)不特別限定，從提高耐熱性、耐光性、及耐龜裂性之觀點，為70重量%以上較佳，尤佳為80重量%以上。The total amount of the alicyclic epoxy compound (A) and the isomeric cyanuric acid monoallyl diglycidyl ester compound (B) relative to the total amount of the epoxy resin (the compound having an epoxy group) (100 weight) %) is not particularly limited, and is preferably 70% by weight or more, and particularly preferably 80% by weight or more from the viewpoint of improving heat resistance, light resistance, and crack resistance.
本發明之硬化性環氧樹脂組成物中，脂環聚酯樹脂(C)擔任提高硬化物之耐熱性、耐光性、抑制光半導體裝置之光度降低的任務。上述脂環聚酯樹脂(C)，係具有脂環結構(脂肪族環結構)之聚酯樹脂。尤其，從硬化物之耐熱性、耐光性、耐龜裂性提高之觀點，上述脂環聚酯樹脂(C)較佳為主鏈具有脂環(脂環結構)之脂環聚酯較佳。In the curable epoxy resin composition of the present invention, the alicyclic polyester resin (C) serves to improve the heat resistance and light resistance of the cured product and to suppress the decrease in the luminosity of the optical semiconductor device. The above alicyclic polyester resin (C) is a polyester resin having an alicyclic structure (aliphatic ring structure). In particular, the alicyclic polyester resin (C) is preferably an alicyclic polyester having an alicyclic (alicyclic structure) as a main chain from the viewpoint of improving heat resistance, light resistance, and crack resistance of the cured product.
脂環聚酯樹脂(C)中的脂環結構不特別限定，例如：單環烴結構或橋接環烴結構(例如：二環系烴等)等，尤佳為脂環全由碳-碳單鍵構成之飽和單環烴結構或飽和橋接環烴結構。又，上述脂環聚酯樹脂(C)中的脂環結構，可僅對於來自於二羧酸之構成單元與來自於二醇之構成單元中任一者導入，也可對於兩方同時導入，不特別限定。The alicyclic structure in the alicyclic polyester resin (C) is not particularly limited, and examples thereof include a monocyclic hydrocarbon structure or a bridged cyclic hydrocarbon structure (for example, a bicyclic hydrocarbon), and the like, and particularly preferably an alicyclic carbon-carbon single The bond constitutes a saturated monocyclic hydrocarbon structure or a saturated bridged cyclic hydrocarbon structure. Further, the alicyclic structure in the alicyclic polyester resin (C) may be introduced only for any of the constituent units derived from the dicarboxylic acid and the constituent unit derived from the diol, or may be simultaneously introduced into both of them. Not particularly limited.
脂環聚酯樹脂(C)，具有來自於具脂環結構之單體的構成單元。上述具脂環結構之單體，例如公知或慣用之具有脂環結構之二醇或二羧酸，不特別限定，例如：1,2-環己烷二羧酸、1,3-環己烷二羧酸、1,4-環己烷二羧酸、4-甲基-1,2-環己烷二羧酸、希米克酸、1,4-十氫萘二羧酸、1,5-十氫萘二羧酸、2,6-十氫萘二羧酸、2,7-十氫萘二羧酸等具脂環結構之二羧酸(也包含酸酐等衍生物)等；1,2-環戊二醇、1,3-環戊二醇、1,2-環戊烷二甲醇、1,3-環戊烷二甲醇、雙(羥基甲基)三環[5.2.1.0]癸烷等5員環二醇、1,2-環己烷二醇、1,3-環己烷二醇、1,4-環己烷二醇、1,2-環己烷二甲醇、1,3-環己烷二甲醇、1,4-環己烷二甲醇、2,2-雙-(4-羥基環己基)丙烷等6員環二醇、氫化雙酚A等具有脂環結構之二醇(也含該等之衍生物)等。The alicyclic polyester resin (C) has a constituent unit derived from a monomer having an alicyclic structure. The monomer having an alicyclic structure, for example, a diol or a dicarboxylic acid having an alicyclic structure, which is known or conventionally used, is not particularly limited, and examples thereof include 1,2-cyclohexanedicarboxylic acid and 1,3-cyclohexane. Dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 4-methyl-1,2-cyclohexanedicarboxylic acid, cimic acid, 1,4-decahydronaphthalene dicarboxylic acid, 1,5 a dicarboxylic acid having an alicyclic structure such as decahydronaphthalene dicarboxylic acid, 2,6-decahydronaphthalene dicarboxylic acid or 2,7-decahydronaphthalene dicarboxylic acid (including a derivative such as an acid anhydride), etc.; 2-cyclopentanediol, 1,3-cyclopentanediol, 1,2-cyclopentane dimethanol, 1,3-cyclopentane dimethanol, bis(hydroxymethyl)tricyclo[5.2.1.0]癸5-membered ring diol such as alkane, 1,2-cyclohexane diol, 1,3-cyclohexane diol, 1,4-cyclohexane diol, 1,2-cyclohexanedimethanol, 1, 6-membered cyclic diol such as 3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2-bis-(4-hydroxycyclohexyl)propane, hydrogenated bisphenol A or the like having an alicyclic structure Alcohol (also containing such derivatives) and the like.
脂環聚酯樹脂(C)也可具有來自於不具脂環結構之單體成分的構成單元。上述不具脂環結構之單體成分，例如：對苯二甲酸、間苯二甲酸、鄰苯二甲酸、萘二羧酸等芳香族二羧酸(也包含酸酐等衍生物)；己二酸、癸二酸、壬二酸、琥珀酸、富馬酸、馬來酸等脂肪族二羧酸(也包含酸酐等衍生物)；乙二醇、丙二醇、1,2-丙二醇、1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、新戊二醇、1,5-戊二醇、1,6-己烷二醇、3-甲基戊二醇、二乙二醇、3-甲基-1,5-戊二醇、2-甲基-1,3-丙二醇、2,2-二乙基-1,3-丙二醇、2-丁基-2-乙基-1,3-丙二醇、亞二甲苯二醇、雙酚A之氧乙烯加成物、雙酚A之氧丙烯加成物等二醇(也含該等之衍生物)等。又，於上述不具脂環結構之二羧酸或二醇有適當取代基(例如：烷基、烷氧基、鹵素原子等)鍵結者，也包含在不具脂環結構之單體成分。The alicyclic polyester resin (C) may also have a constituent unit derived from a monomer component having no alicyclic structure. The monomer component having no alicyclic structure, for example, an aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid, phthalic acid or naphthalene dicarboxylic acid (including a derivative such as an acid anhydride); adipic acid, Aliphatic dicarboxylic acids such as azelaic acid, sebacic acid, succinic acid, fumaric acid, maleic acid (including derivatives such as acid anhydrides); ethylene glycol, propylene glycol, 1,2-propanediol, and 1,3-propanediol , 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 3-methylpentanediol, diethylene Alcohol, 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-butyl-2-ethyl- A diol (including such a derivative) such as 1,3-propanediol, dimethylene glycol, an oxyethylene adduct of bisphenol A, or an oxypropylene adduct of bisphenol A. Further, in the above-mentioned dicarboxylic acid or diol having no alicyclic structure, a substituent having a suitable substituent (for example, an alkyl group, an alkoxy group or a halogen atom) is also contained in a monomer component having no alicyclic structure.
具脂環之單體單元相對於構成脂環聚酯樹脂(C)之全部單體單元(全單體成分)(100莫耳%)的比例，不特別限定，較佳為10莫耳%以上(例如：10~80莫耳%)，更佳為25~70莫耳%，又更佳為40~60莫耳%。具脂環之單體單元之比例若少於10莫耳%，硬化物之耐熱性、耐光性、耐龜裂性有時會降低。The ratio of the monomer unit having an alicyclic ring to all the monomer units (all monomer components) (100 mol%) constituting the alicyclic polyester resin (C) is not particularly limited, and is preferably 10 mol% or more. (for example: 10 to 80% by mole), more preferably 25 to 70% by mole, and even more preferably 40 to 60% by mole. When the ratio of the monomer unit having an alicyclic ring is less than 10 mol%, the heat resistance, light resistance, and crack resistance of the cured product may be lowered.
脂環聚酯樹脂(C)，尤佳為含有下式(2)~(4)表示之構成單元當中至少1種以上之脂環聚酯。The alicyclic polyester resin (C) is preferably an alicyclic polyester containing at least one of the constituent units represented by the following formulas (2) to (4).
(式中，R3 表示直鏈狀、支鏈狀、或環狀之碳數2~15之伸烷基。又，R4 ~R7 各自獨立地表示氫原子或直鏈狀或支鏈狀之碳數1~4之烷基，從R4 ~R7 選出的二個也可鍵結並形成環)。(wherein R 3 represents a linear, branched or cyclic alkyl group having 2 to 15 carbon atoms. Further, R 4 to R 7 each independently represent a hydrogen atom or a linear or branched chain. The alkyl group having a carbon number of 1 to 4, and two selected from R 4 to R 7 may be bonded and form a ring).
(式中，R3 表示直鏈狀、支鏈狀、或環狀之碳數2~15之伸烷基。又，R4 ~R7 各自獨立地表示氫原子或直鏈狀或支鏈狀之碳數1~4之烷基，從R4 ~R7 選出的二個也可鍵結成環)。(wherein R 3 represents a linear, branched or cyclic alkyl group having 2 to 15 carbon atoms. Further, R 4 to R 7 each independently represent a hydrogen atom or a linear or branched chain. The alkyl group having a carbon number of 1 to 4, and two selected from R 4 to R 7 may be bonded to form a ring).
(式中，R3 表示直鏈狀、支鏈狀、或環狀之碳數2~15之伸烷基。又，R4 ~R7 各自獨立地表示氫原子或直鏈狀或支鏈狀之碳數1~4之烷基，從R4 ~R7 選出的二個也可鍵結成環)。(wherein R 3 represents a linear, branched or cyclic alkyl group having 2 to 15 carbon atoms. Further, R 4 to R 7 each independently represent a hydrogen atom or a linear or branched chain. The alkyl group having a carbon number of 1 to 4, and two selected from R 4 to R 7 may be bonded to form a ring).
上式(2)~(4)表示之構成單元之較佳具體例，例如：來自於下式(5)表示之4-甲基-1,2-環己烷二羧酸及乙二醇之構成單元。具有該構成單元之脂環聚酯樹脂(C)，可藉由將例如：甲基六氫鄰苯二甲酸酐與乙二醇縮聚而獲得。Preferred specific examples of the constituent units represented by the above formulas (2) to (4) are, for example, 4-methyl-1,2-cyclohexanedicarboxylic acid represented by the following formula (5) and ethylene glycol. Form the unit. The alicyclic polyester resin (C) having such a constituent unit can be obtained by polycondensing, for example, methylhexahydrophthalic anhydride with ethylene glycol.
又，上式(2)~(4)表示之構成單元之其他具體例，例如：來自於下式(6)表示之1,4-環己烷二羧酸及新戊二醇之構成單元。具該構成單元之脂環聚酯樹脂(C)可藉由將例如：1,4-環己烷二羧酸與新戊二醇縮聚而得。Further, another specific example of the constituent unit represented by the above formulas (2) to (4) is, for example, a constituent unit derived from 1,4-cyclohexanedicarboxylic acid and neopentyl glycol represented by the following formula (6). The alicyclic polyester resin (C) having the constituent unit can be obtained by polycondensing, for example, 1,4-cyclohexanedicarboxylic acid with neopentyl glycol.
脂環聚酯樹脂(C)具有上式(2)~(4)表示之構成單元時，該構成單元之含量之合計量(合計含量)不特別限定，相對於脂環聚酯樹脂(C)之全部構成單元(100莫耳%)為20莫耳%以上(例如：20~100莫耳%)較佳，更佳為50~100莫耳%，又更佳為80~100莫耳%。上式(2)~(4)表示之構成單元之含量若少於20莫耳%，有時硬化物之耐熱性、耐光性、耐龜裂性會降低。When the alicyclic polyester resin (C) has a constituent unit represented by the above formulas (2) to (4), the total amount (total content) of the content of the constituent unit is not particularly limited, and is equivalent to the alicyclic polyester resin (C). The total constituent unit (100% by mole) is preferably 20 mol% or more (for example, 20 to 100 mol%), more preferably 50 to 100 mol%, and still more preferably 80 to 100 mol%. When the content of the constituent unit represented by the above formulas (2) to (4) is less than 20 mol%, the heat resistance, light resistance, and crack resistance of the cured product may be lowered.
脂環聚酯樹脂(C)之數量平均分子量不特別限定，較佳為300~100000，更佳為300~30000。脂環聚酯樹脂(C)之數量平均分子量若小於300，硬化物之強靭性不夠，有時耐龜裂性會降低。另一方面，脂環聚酯樹脂(C)之數量平均分子量若超過100000，與硬化劑(D)之互溶性會降低，有時硬化物之透明性會降低。又，脂環聚酯樹脂(C)之數量平均分子量，例如可利用GPC(凝膠滲透層析)法，測定當作標準聚苯乙烯換算之值。The number average molecular weight of the alicyclic polyester resin (C) is not particularly limited, and is preferably from 300 to 100,000, more preferably from 300 to 30,000. When the number average molecular weight of the alicyclic polyester resin (C) is less than 300, the toughness of the cured product is insufficient, and the crack resistance is sometimes lowered. On the other hand, if the number average molecular weight of the alicyclic polyester resin (C) exceeds 100,000, the mutual solubility with the hardener (D) may decrease, and the transparency of the cured product may decrease. Further, the number average molecular weight of the alicyclic polyester resin (C) can be measured, for example, by a GPC (gel permeation chromatography) method in terms of standard polystyrene.
又，脂環聚酯樹脂(C)可以單獨使用1種或組合使用2種以上。Further, the alicyclic polyester resin (C) may be used alone or in combination of two or more.
脂環聚酯樹脂(C)不特別限定，可依照公知或慣用方法製造。更詳言之，例如脂環聚酯樹脂(C)，可藉由以常法將上述二羧酸與二醇縮聚而得，也可將上述二羧酸之衍生物(酸酐、酯、醯鹵化物等)與二醇依常法縮聚而得。The alicyclic polyester resin (C) is not particularly limited and can be produced according to a known or customary method. More specifically, for example, the alicyclic polyester resin (C) can be obtained by polycondensing the above dicarboxylic acid with a diol in a usual manner, or a derivative of the above dicarboxylic acid (anhydride, ester, hydrazine) And the diol is obtained by polycondensation according to the usual method.
本發明之硬化性環氧樹脂組成物中，脂環聚酯樹脂(C)之摻合量(含量)不特別限定，相對於脂環聚酯樹脂(C)與硬化劑(D)之合計量(100重量%)為1~60重量%較佳，更佳為5~30重量%。脂環聚酯樹脂(C)之摻合量若少於1重量%，有時硬化物之耐龜裂性會降低。另一方面，脂環聚酯樹脂(C)之摻合量若超過60重量%，硬化物之透明性或耐熱性有時會降低。In the curable epoxy resin composition of the present invention, the blending amount (content) of the alicyclic polyester resin (C) is not particularly limited, and is equivalent to the total amount of the alicyclic polyester resin (C) and the hardener (D). (100% by weight) is preferably from 1 to 60% by weight, more preferably from 5 to 30% by weight. When the blending amount of the alicyclic polyester resin (C) is less than 1% by weight, the crack resistance of the cured product may be lowered. On the other hand, when the blending amount of the alicyclic polyester resin (C) exceeds 60% by weight, the transparency or heat resistance of the cured product may be lowered.
另一方面，本發明之硬化性環氧樹脂組成物以硬化觸媒(F)當作必要成分時，脂環聚酯樹脂(D)之摻合量(含量)不特別限定，相對於脂環聚酯樹脂(D)與硬化觸媒(F)之合計量(100重量%)為50~99重量%較佳，更佳為65~99重量%。脂環聚酯樹脂(D)之摻合量若少於50重量%，硬化物之耐龜裂性有時會降低。另一方面，脂環聚酯樹脂(D)之摻合量若超過99重量%，硬化物之透明性或耐熱性有時會降低。On the other hand, when the hardening epoxy resin composition of the present invention contains the curing catalyst (F) as an essential component, the blending amount (content) of the alicyclic polyester resin (D) is not particularly limited, and is relative to the alicyclic ring. The total amount (100% by weight) of the polyester resin (D) and the hardening catalyst (F) is preferably from 50 to 99% by weight, more preferably from 65 to 99% by weight. When the blending amount of the alicyclic polyester resin (D) is less than 50% by weight, the crack resistance of the cured product may be lowered. On the other hand, when the blending amount of the alicyclic polyester resin (D) exceeds 99% by weight, the transparency or heat resistance of the cured product may be lowered.
硬化劑(D)具有使具環氧基之化合物硬化的作用。本發明中，硬化劑(D)可使用就環氧樹脂用硬化劑而言為公知或慣用之硬化劑。本發明中，硬化劑(D)又以25℃為液狀之酸酐較佳，例如：甲基四氫鄰苯二甲酸酐、甲基六氫鄰苯二甲酸酐、十二烯基琥珀酸酐、甲基內向亞甲基四氫鄰苯二甲酸酐等。又，例如將鄰苯二甲酸酐、四氫鄰苯二甲酸酐、六氫鄰苯二甲酸酐、甲基環己烯二羧酸酐等常溫(約25℃)為固體狀之酸酐溶於常溫(約25℃)為液狀酸酐而成為液狀混合物，藉此，也可當作本發明之硬化劑(D)使用。本發明之硬化性環氧樹脂組成物中，硬化劑(D)從硬化物之耐熱性、耐光性、耐龜裂性之觀點，為飽和單環烴二羧酸酐(也包含環有烷基等取代基鍵結者)為較佳。又，硬化劑(D)可以單獨使用，或組合2種以上使用。The hardener (D) has a function of hardening a compound having an epoxy group. In the present invention, as the curing agent (D), a curing agent which is known or conventionally used as a curing agent for an epoxy resin can be used. In the present invention, the hardener (D) is preferably an acid anhydride having a liquid state at 25 ° C, for example, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecenylsuccinic anhydride, Methyl inward methylenetetrahydrophthalic anhydride or the like. Further, for example, an acid anhydride having a solid temperature (about 25 ° C) at a normal temperature (about 25 ° C) such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride or methylcyclohexene dicarboxylic anhydride is dissolved in a normal temperature ( About 25 ° C) is a liquid acid anhydride and becomes a liquid mixture, and can also be used as the hardener (D) of the present invention. In the curable epoxy resin composition of the present invention, the curing agent (D) is a saturated monocyclic hydrocarbon dicarboxylic anhydride (including a ring-containing alkyl group, etc.) from the viewpoint of heat resistance, light resistance, and crack resistance of the cured product. Substituent bonders are preferred. Further, the curing agent (D) may be used singly or in combination of two or more.
又，本發明中，硬化劑(D)也可使用Rikacid MH-700(新日本理化(股)製)、HN-5500(日立化成工業(股)製)等市售品。Further, in the present invention, commercially available products such as Rikacid MH-700 (manufactured by Shin Nippon Chemical & Chemical Co., Ltd.) and HN-5500 (manufactured by Hitachi Chemical Co., Ltd.) can be used as the curing agent (D).
硬化劑(D)之使用量(含量)不特別限定，相對於本發明之硬化性環氧樹脂組成物中含有之具環氧基之化合物之全量(100重量份)，為50~200重量份較佳，更佳為100~145重量份。更具體而言，以成為本發明之硬化性環氧樹脂組成物中所含之全部具環氧基之化合物中的環氧基每1當量，0.5~1.5當量之比例使用較佳。硬化劑(D)之使用量若低於50重量份，硬化不充分，硬化物之強韌性有降低之傾向。另一方面，硬化劑(D)之使用量若超過200重量份，硬化物會著色，有時色相會惡化。The amount (content) of the curing agent (D) is not particularly limited, and is 50 to 200 parts by weight based on the total amount (100 parts by weight) of the epoxy group-containing compound contained in the curable epoxy resin composition of the present invention. More preferably, it is preferably 100 to 145 parts by weight. More specifically, the epoxy group in the epoxy group-containing compound contained in the curable epoxy resin composition of the present invention is preferably used in an amount of from 0.5 to 1.5 equivalents per equivalent of the epoxy group. When the amount of the curing agent (D) used is less than 50 parts by weight, the curing is insufficient, and the toughness of the cured product tends to be lowered. On the other hand, when the amount of the curing agent (D) used exceeds 200 parts by weight, the cured product may be colored, and the hue may be deteriorated.
本發明之硬化性環氧樹脂組成物更包含硬化促進劑(E)。硬化促進劑(E)，係於具環氧基化合物利用硬化劑硬化時，具有促進硬化速度之機能之化合物。硬化促進劑(E)，可使用公知或慣用之硬化促進劑，例如：1,8-二氮雜雙環[5.4.0]十一烯-7(DBU)、及其鹽(例如：酚鹽、辛酸鹽、對甲苯磺酸鹽、甲酸鹽、四苯基硼酸鹽)；1,5-二氮雜雙環[4.3.0]壬烯-5(DBN)、及其鹽(例如：鏻鹽、鋶鹽、4級銨鹽、錪鹽)；苄基二甲胺、2,4,6-參(二甲胺基甲基)酚、N,N-二甲基環己胺等3級胺；2-乙基-4-甲基咪唑、1-氰基乙基-2-乙基-4-甲基咪唑等咪唑；磷酸酯、三苯膦等膦類；四苯基鏻四(對甲苯基)硼酸鹽等鏻化合物；辛酸錫、辛酸鋅等有機金屬鹽；金屬螯合物等。該等可以單獨使用，或混合2種以上使用。The curable epoxy resin composition of the present invention further contains a hardening accelerator (E). The hardening accelerator (E) is a compound having a function of promoting the curing speed when the epoxy compound is cured by a curing agent. As the hardening accelerator (E), a known or conventional hardening accelerator such as 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), and a salt thereof (for example, a phenate, Octanoic acid, p-toluenesulfonate, formate, tetraphenyl borate); 1,5-diazabicyclo[4.3.0]nonene-5 (DBN), and salts thereof (eg, phosphonium salts, a phosphonium salt, a 4-grade ammonium salt, a phosphonium salt); a benzylamine, a 2,4,6-glycol (dimethylaminomethyl)phenol, a N-N-dimethylcyclohexylamine or the like; Imidazoles such as 2-ethyl-4-methylimidazole and 1-cyanoethyl-2-ethyl-4-methylimidazole; phosphines such as phosphates and triphenylphosphine; tetraphenylphosphonium tetra(p-tolyl) An antimony compound such as borate; an organic metal salt such as tin octylate or zinc octoate; a metal chelate compound or the like. These may be used alone or in combination of two or more.
又，本發明中，硬化促進劑(E)也可使用U-CAT SA 506、U-CAT SA 102、U-CAT 5003、U-CAT 18X、12XD(開發品)(均為San-apro(股)製)、TPP-K、TPP-MK(均為北興化學工業(股)製)、PX-4ET(日本化學工業(股)製)等市售品。Further, in the present invention, the hardening accelerator (E) may also be U-CAT SA 506, U-CAT SA 102, U-CAT 5003, U-CAT 18X, 12XD (developed product) (both San-apro) )), TPP-K, TPP-MK (both from Beixing Chemical Industry Co., Ltd.) and PX-4ET (manufactured by Nippon Chemical Industry Co., Ltd.).
硬化促進劑(E)之使用量(含量)不特別限定，相對於硬化性環氧樹脂組成物中所含之具環氧基之化合物之全量(100重量份)為0.05~5重量份較佳，更佳為0.1~3重量份，又更佳為0.2~3重量份，尤佳為0.25~2.5重量份。硬化促進劑(E)之使用量若少於0.05重量份，硬化促進效果有時會不夠。另一方面，硬化促進劑(E)之使用量若超過5重量份，硬化物會著色，有時色相會惡化。The amount (content) of the hardening accelerator (E) is not particularly limited, and is preferably 0.05 to 5 parts by weight based on the total amount (100 parts by weight) of the epoxy group-containing compound contained in the curable epoxy resin composition. More preferably, it is 0.1 to 3 parts by weight, more preferably 0.2 to 3 parts by weight, and particularly preferably 0.25 to 2.5 parts by weight. When the amount of the hardening accelerator (E) used is less than 0.05 parts by weight, the hardening promoting effect may be insufficient. On the other hand, when the amount of the curing accelerator (E) used exceeds 5 parts by weight, the cured product may be colored, and the hue may be deteriorated.
本發明之硬化性環氧樹脂組成物中，也可使用硬化觸媒(F)代替上述硬化劑(D)及硬化促進劑(E)。與使用硬化劑(D)及硬化促進劑(E)之情形同樣，藉由使用硬化觸媒(F)，能使具有環氧基之化合物之硬化反應進行並獲得硬化物。上述硬化觸媒(F)不特別限定，可使用藉由實施紫外線照射或加熱處理會產生陽離子物質並開始聚合之陽離子觸媒(陽離子聚合起始劑)。又，硬化觸媒(F)可單獨使用1種或組合使用2種以上。In the curable epoxy resin composition of the present invention, a curing catalyst (F) may be used instead of the curing agent (D) and the curing accelerator (E). As in the case of using the hardener (D) and the hardening accelerator (E), by using the hardening catalyst (F), the hardening reaction of the epoxy group-containing compound can be carried out and a cured product can be obtained. The hardening catalyst (F) is not particularly limited, and a cationic catalyst (cationic polymerization initiator) which generates a cationic substance by polymerization by ultraviolet irradiation or heat treatment and starts polymerization can be used. Further, the curing catalyst (F) may be used alone or in combination of two or more.
由於紫外線照射而產生陽離子物質之陽離子觸媒，例如：六氟銻酸鹽、五氟羥基銻酸鹽、六氟磷酸鹽、六氟砷酸鹽等。UVACURE1590(Daicel‧Cytec(股)製)、CD-1010、CD-1011、CD-1012(美國Sartomer製)、Irgacure 264(Ciba Japan(股)製)、CIT-1682(日本曹達(股)製)等市售品為較佳可使用者。A cationic catalyst which generates a cationic substance due to ultraviolet irradiation, for example, hexafluoroantimonate, pentafluorohydroxy decanoate, hexafluorophosphate, hexafluoroarsenate or the like. UVACURE1590 (made by Daicel‧Cytec), CD-1010, CD-1011, CD-1012 (made by Sartomer, USA), Irgacure 264 (made by Ciba Japan), CIT-1682 (made by Japan Soda Co., Ltd.) Commercial products such as those are preferred.
實施加熱處理會產生陽離子物質之陽離子觸媒，例如：芳基重氮鹽、芳基錪鹽、芳基鋶鹽、芳烯(arene)-離子錯合物等，較佳為可使用例如PP-33、CP-66、CP-77(ADEKA(股)製)、FC-509(3M製)、UVE1014(G.E.製)、San-Aid SI-60L、San-Aid SI-80L、San-Aid SI-100L、San-Aid SI-110L(三新化學工業(股)製)、CG-24-61(Ciba Japan(股)製)等市售品。再者，鋁或鈦等金屬與乙醯乙酸或二酮類之螯合化合物與三苯基矽醇等矽醇之化合物、或鋁或鈦等金屬與乙醯乙酸或二酮類之螯合化合物與雙酚S等酚類之化合物亦可。The heat treatment may produce a cationic catalyst of a cationic substance such as an aryldiazonium salt, an arylsulfonium salt, an arylsulfonium salt, an arene-ion complex, or the like, and preferably, for example, PP- may be used. 33. CP-66, CP-77 (made by ADEKA), FC-509 (made by 3M), UVE1014 (made by GE), San-Aid SI-60L, San-Aid SI-80L, San-Aid SI- Commercial products such as 100L, San-Aid SI-110L (manufactured by Sanshin Chemical Industry Co., Ltd.) and CG-24-61 (manufactured by Ciba Japan Co., Ltd.). Further, a compound of a metal such as aluminum or titanium and a chelating compound of acetonitrile acetic acid or a diketone, a sterol compound such as triphenyl decyl alcohol, or a metal such as aluminum or titanium and a chelating compound of acetonitrile acetic acid or a diketone. A compound such as a phenol such as bisphenol S may also be used.
硬化觸媒(F)之使用量(含量)不特別限定，相對於硬化性環氧樹脂組成物中含有之具環氧基之化合物之全量(100重量份)，為0.01~15重量份較佳，更佳為0.01~12重量份，又更佳為0.05~10重量份，尤佳為0.1~10重量份。藉由於該範圍內使用硬化觸媒(F)，可獲得耐熱性、耐光性、透明性優異之硬化物。The amount (content) of the curing catalyst (F) is not particularly limited, and is preferably 0.01 to 15 parts by weight based on the total amount (100 parts by weight) of the epoxy group-containing compound contained in the curable epoxy resin composition. More preferably, it is 0.01 to 12 parts by weight, more preferably 0.05 to 10 parts by weight, and particularly preferably 0.1 to 10 parts by weight. By using the curing catalyst (F) in this range, a cured product excellent in heat resistance, light resistance, and transparency can be obtained.
本發明之硬化性環氧樹脂組成物也可更含有橡膠粒子。上述橡膠粒子，例如：粒子狀NBR(丙烯腈-丁二烯橡膠)、反應性末端羧基NBR(CTBN)、無金屬NBR、粒子狀SBR(苯乙烯-丁二烯橡膠)等橡膠粒子。上述橡膠粒子，宜為包含具有橡膠彈性之核部分、與被覆該核部分之至少1層鞘層構成之多層構造(核鞘構造)之橡膠粒子為較佳。上述橡膠粒子，尤佳為以(甲基)丙烯酸酯當作必要單體成分之聚合物(聚合體)構成，且表面具有羥基及/或羧基(羥基及羧基任一者或兩者)當作能與脂環環氧樹脂(A)等具環氧基之化合物反應之官能基之橡膠粒子為較佳。上述橡膠粒子之表面不存在羥基及/或羧基時，會由於冷熱循環等熱衝撃造成硬化物變得白濁且透明性降低，故為不佳。The curable epoxy resin composition of the present invention may further contain rubber particles. The rubber particles are, for example, rubber particles such as particulate NBR (acrylonitrile-butadiene rubber), reactive terminal carboxyl group NBR (CTBN), metal-free NBR, and particulate SBR (styrene-butadiene rubber). The rubber particles are preferably rubber particles including a core portion having rubber elasticity and a multilayer structure (nuclear sheath structure) composed of at least one sheath layer covering the core portion. The rubber particles are preferably composed of a polymer (polymer) having (meth) acrylate as an essential monomer component, and having a hydroxyl group and/or a carboxyl group (either one or both of a hydroxyl group and a carboxyl group) on the surface. A rubber particle capable of reacting with a functional group having an epoxy group such as an alicyclic epoxy resin (A) is preferred. When the surface of the rubber particles does not have a hydroxyl group and/or a carboxyl group, the cured product becomes cloudy due to thermal flushing such as a heat cycle, and the transparency is lowered, which is not preferable.
上述橡膠粒子中，構成具橡膠彈性之核部分之聚合物，不特別限定，較佳為以(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯等(甲基)丙烯酸酯當作必要單體成分。構成上述具橡膠彈性之核部分之聚合物，除此以外，也可含有例如：苯乙烯、α-甲基苯乙烯等芳香族乙烯基化合物；丙烯腈、甲基丙烯腈等腈；丁二烯、異戊二烯等共軛二烯；乙烯、丙烯、異丁烯等烯烴等當作單體成分。Among the rubber particles, the polymer constituting the core portion having rubber elasticity is not particularly limited, and is preferably methyl (meth)acrylate, ethyl (meth)acrylate or butyl (meth)acrylate (A) Acrylate is used as an essential monomer component. The polymer constituting the rubber-elastic core portion may contain, for example, an aromatic vinyl compound such as styrene or α-methylstyrene; a nitrile such as acrylonitrile or methacrylonitrile; and butadiene. A conjugated diene such as isoprene; an olefin such as ethylene, propylene or isobutylene is used as a monomer component.
其中，構成上述具橡膠彈性之核部分之聚合物，就單體成分而言，含有(甲基)丙烯酸酯，以及選自於芳香族乙烯基化合物、腈、及共軛二烯構成之群組中1種或2種以上之組合較佳。亦即，構成上述核部分之聚合物，例如：(甲基)丙烯酸酯/芳香族乙烯基化合物、(甲基)丙烯酸酯/共軛二烯等二元共聚合物；(甲基)丙烯酸酯/芳香族乙烯基化合物/共軛二烯等三元共聚合物等。又，構成上述核部分之聚合物中，也可含有聚二甲基矽氧烷或聚苯基甲基矽氧烷等聚矽氧或聚胺甲酸酯等。The polymer constituting the rubber-elastic core portion contains a (meth) acrylate as a monomer component, and a group selected from the group consisting of an aromatic vinyl compound, a nitrile, and a conjugated diene. One type or a combination of two or more types is preferred. That is, a polymer constituting the above-mentioned core portion, for example, a (meth) acrylate/aromatic vinyl compound, a binary copolymer such as a (meth) acrylate/conjugated diene; (meth) acrylate a ternary copolymer such as an aromatic vinyl compound/conjugated diene or the like. Further, the polymer constituting the core portion may contain polyfluorene oxide or polyurethane such as polydimethyl siloxane or polyphenylmethyl siloxane.
構成上述核部分之聚合物，就其他單體成分而言，也可含有二乙烯基苯、(甲基)丙烯酸烯丙酯、乙二醇二(甲基)丙烯酸酯、馬來酸二烯丙酯、三聚氰酸三烯丙酯、鄰苯二甲酸二烯丙酯、丁二醇二丙烯酸酯等1單體(1分子)中具有2個以上之反應性官能基之反應***聯單體。The polymer constituting the above-mentioned core portion may also contain divinylbenzene, allyl (meth)acrylate, ethylene glycol di(meth)acrylate, and dialkyl maleate in terms of other monomer components. a reactive crosslinking monomer having two or more reactive functional groups in one monomer (one molecule) such as ester, triallyl cyanurate, diallyl phthalate or butanediol diacrylate .
上述橡膠粒子之核部分中，由(甲基)丙烯酸酯/芳香族乙烯基化合物之二元共聚合物(尤其丙烯酸丁酯/苯乙烯)構成之核部分，從能輕易調整橡膠粒子之折射率之觀點為較佳。In the core portion of the rubber particles, the core portion composed of the binary copolymer of (meth) acrylate/aromatic vinyl compound (especially butyl acrylate/styrene) can easily adjust the refractive index of the rubber particles. The viewpoint is preferred.
上述橡膠粒子之核部分，可使用通常使用之方法製造，例如可利用將上述單體以乳化聚合法進行聚合之方法等製造。乳化聚合法時，可將上述單體全量一次添加，也可先聚合上述單體的一部分後，將其餘部分連續或間歇添加並聚合，再者，也可利用使用種粒之聚合方法。The core portion of the rubber particles can be produced by a usual method, and can be produced, for example, by a method of polymerizing the above monomers by an emulsion polymerization method. In the emulsion polymerization method, the above monomers may be added in one portion at a time, or a part of the above monomers may be first polymerized, and the remaining portion may be continuously or intermittently added and polymerized. Further, a polymerization method using the seed particles may be used.
構成上述橡膠粒子之鞘層之聚合物，宜為與構成上述核部分之聚合物為不同種之聚合物。又，如上述，上述鞘層宜具有羥基及/或羧基當作能與脂環環氧化合物(A)等具環氧基之化合物反應之官能基。藉此，尤其能使與脂環環氧化合物(A)之界面的黏著性提高，對於使含有具該鞘層之橡膠粒子之硬化性環氧樹脂組成物硬化而得之硬化物，可發揮優異的耐龜裂性。又，也可防止硬化物之玻璃轉移溫度降低。The polymer constituting the sheath layer of the rubber particles is preferably a polymer different from the polymer constituting the core portion. Further, as described above, the sheath layer preferably has a hydroxyl group and/or a carboxyl group as a functional group capable of reacting with an epoxy group-containing compound such as an alicyclic epoxy compound (A). In this way, the adhesion to the interface with the alicyclic epoxy compound (A) can be improved, and the cured product obtained by curing the curable epoxy resin composition containing the rubber particles having the sheath layer can be excellent. Resistance to cracking. Further, it is also possible to prevent the glass transition temperature of the cured product from decreasing.
構成上述鞘層之聚合物，宜含有(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯等(甲基)丙烯酸酯當作必要單體成分。例如：上述核部分中，(甲基)丙烯酸酯使用丙烯酸丁酯時，構成鞘層之聚合物之單體成分，宜使用丙烯酸丁酯以外之(甲基)丙烯酸酯(例如：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、甲基丙烯酸丁酯等)。(甲基)丙烯酸酯以外也可含有的單體成分，例如：苯乙烯、α-甲基苯乙烯等芳香族乙烯基化合物、丙烯腈、甲基丙烯腈等腈等。上述橡膠粒子中，構成鞘層之單體成分，宜將(甲基)丙烯酸酯與上述單體單獨1種或2種以上組合較佳，尤其，至少含有芳香族乙烯基化合物時，從能輕易調整上述橡膠粒子之折射率之觀點為較佳。The polymer constituting the sheath layer preferably contains a (meth) acrylate such as methyl (meth) acrylate, ethyl (meth) acrylate or butyl (meth) acrylate as an essential monomer component. For example, in the above-mentioned core portion, when butyl acrylate is used for the (meth) acrylate, the monomer component of the polymer constituting the sheath layer is preferably a (meth) acrylate other than butyl acrylate (for example, (meth)) Methyl acrylate, ethyl (meth)acrylate, butyl methacrylate, etc.). A monomer component which may be contained in addition to the (meth) acrylate, for example, an aromatic vinyl compound such as styrene or α-methylstyrene, or a nitrile such as acrylonitrile or methacrylonitrile. In the rubber particles, it is preferred to combine the (meth) acrylate with the monomer alone or in combination of two or more kinds, and in particular, when the aromatic vinyl compound is contained at least, it is easy to use. The viewpoint of adjusting the refractive index of the above rubber particles is preferred.
再者，構成上述鞘層之聚合物，就單體成分而言，為了形成當作能與脂環環氧化合物(A)等具環氧基之化合物反應之官能基的羥基及/或羧基，宜含有(甲基)丙烯酸2-羥基乙酯等(甲基)丙烯酸羥基烷酯、或(甲基)丙烯酸等之α,β-不飽和酸、馬來酸酐等之α,β-不飽和酸酐等單體。Further, the polymer constituting the sheath layer is a monomer component for forming a hydroxyl group and/or a carboxyl group which is a functional group capable of reacting with an epoxy group-containing compound such as an alicyclic epoxy compound (A). It is preferable to contain a hydroxyalkyl (meth) acrylate such as 2-hydroxyethyl (meth)acrylate or an α,β-unsaturated acid anhydride such as α,β-unsaturated acid or maleic anhydride such as (meth)acrylic acid. And other monomers.
上述橡膠粒子中，構成鞘層之聚合物，就單體成分而言，宜含有(甲基)丙烯酸酯，以及選自於上述單體之1種或2種以上之組合。亦即，上述鞘層例如為(甲基)丙烯酸酯/芳香族乙烯基/羥基烷基(甲基)丙烯酸酯、(甲基)丙烯酸酯/芳香族乙烯基/α,β-不飽和酸等三元共聚合物等構成之鞘層較佳。In the rubber particles, the polymer constituting the sheath layer preferably contains a (meth) acrylate and a combination of one or a combination of two or more of the above monomers. That is, the sheath layer is, for example, (meth) acrylate/aromatic vinyl/hydroxyalkyl (meth) acrylate, (meth) acrylate/aromatic vinyl/α, β-unsaturated acid, or the like. A sheath composed of a ternary copolymer or the like is preferred.
又，構成上述鞘層之聚合物，就其他單體成分而言，與核部分同樣，除了上述單體以外，也可含有二乙烯基苯、(甲基)丙烯酸烯丙酯、乙二醇二(甲基)丙烯酸酯、馬來酸二烯丙酯、三聚氰酸三烯丙酯、鄰苯二甲酸二烯丙酯、丁二醇二丙烯酸酯等1單體(1分子)中具有2個以上之反應性官能基之反應***聯單體。Further, the polymer constituting the sheath layer may contain, in addition to the above-mentioned monomers, divinylbenzene, allyl (meth)acrylate, and ethylene glycol as the core component. 1 monomer (1 molecule) of (meth) acrylate, diallyl maleate, triallyl cyanurate, diallyl phthalate, butanediol diacrylate, etc. Reactive cross-linking monomers of more than one reactive functional group.
上述橡膠粒子(具核鞘構造之橡膠粒子)，可藉由將上述核部分以鞘層被覆而得。將上述核部分以鞘層被覆之方法，例如在由上述方法獲得之具橡膠彈性之核部分之表面，塗佈構成鞘層之共聚物以進行被覆之方法；以由上述方法獲得之具橡膠彈性之核部分當作幹成分，並以構成鞘層之各成分當作枝成分，進行接枝聚合之方法等。The rubber particles (rubber particles having a nucleus sheath structure) can be obtained by coating the core portion with a sheath. a method in which the core portion is coated with a sheath, for example, a surface of a rubber-elastic core portion obtained by the above method, and a copolymer constituting the sheath layer is coated to carry out coating; and the rubber elastic property obtained by the above method is used. The core portion is used as a dry component, and each component constituting the sheath layer is used as a branch component, and a graft polymerization method or the like is carried out.
上述橡膠粒子之平均粒徑不特別限定，宜為10~500nm，更佳為20~400nm。又，上述橡膠粒子之最大粒徑不特別限定，宜為50~1000nm，更佳為100~800nm。平均粒徑若大於500nm，或最大粒徑大於1000nm時，橡膠粒子於硬化物之分散性降低，且有時耐龜裂性降低。另一方面，平均粒徑若小於10nm或最大粒徑小於50nm，硬化物之耐龜裂性提高之效果有時不易獲得。The average particle diameter of the rubber particles is not particularly limited and is preferably from 10 to 500 nm, more preferably from 20 to 400 nm. Further, the maximum particle diameter of the rubber particles is not particularly limited, but is preferably from 50 to 1,000 nm, more preferably from 100 to 800 nm. When the average particle diameter is more than 500 nm or the maximum particle diameter is more than 1000 nm, the dispersibility of the rubber particles in the cured product is lowered, and the crack resistance is sometimes lowered. On the other hand, when the average particle diameter is less than 10 nm or the maximum particle diameter is less than 50 nm, the effect of improving the crack resistance of the cured product may not be easily obtained.
上述橡膠粒子之折射率不特別限定，宜為1.40~1.60，更佳為1.42~1.58。又，橡膠粒子之折射率、與將含該橡膠粒子之硬化性環氧樹脂組成物(本發明之硬化性環氧樹脂組成物)硬化而獲得之硬化物之折射率之間的差異，為±0.03以內(-0.03~0.03)較佳。上述折射率之差異若大於±0.03，硬化物之透明性會降低，有時會變得白濁，光半導體裝置之光度有降低之傾向，有時會喪失光半導體裝置之機能。The refractive index of the rubber particles is not particularly limited and is preferably from 1.40 to 1.60, more preferably from 1.42 to 1.58. Further, the difference between the refractive index of the rubber particles and the refractive index of the cured product obtained by curing the curable epoxy resin composition containing the rubber particles (the curable epoxy resin composition of the present invention) is ± It is preferably within 0.03 (-0.03 to 0.03). When the difference in refractive index is more than ±0.03, the transparency of the cured product may be lowered, and the opacity may be lowered, and the illuminance of the optical semiconductor device may be lowered, and the function of the optical semiconductor device may be lost.
橡膠粒子之折射率，例如：可藉由將橡膠粒子1g注入成形模，於210℃、4MPa進行壓縮成形，獲得厚度1mm之平板，從獲得之平板切出縱20mm×橫6mm之試驗片，並使用單溴萘當作中間液，於使稜鏡與該試驗片密合之狀態，使用多波長阿貝折射計(商品名「DR-M2」、Atago(股)製)，測定20℃、鈉D線的折射率而求取。The refractive index of the rubber particles can be, for example, injection molded into a molding die at 210 ° C and 4 MPa to obtain a flat plate having a thickness of 1 mm, and a test piece having a length of 20 mm × a width of 6 mm can be cut out from the obtained flat plate. Using a bromine naphthalene as an intermediate liquid, a multi-wavelength Abbe refractometer (trade name "DR-M2", manufactured by Atago Co., Ltd.) was used to measure the enthalpy and the test piece, and 20 ° C and sodium were measured. The refractive index of the D line is obtained.
本發明之硬化性環氧樹脂組成物之硬化物之折射率，例如可從藉由下列光半導體裝置之項目記載之加熱硬化方法獲得之硬化物，切出縱20mm×橫6mm×厚度1mm之試驗片，並使用單溴萘當作中間液，於使稜鏡與該試驗片密合之狀態，使用多波長阿貝折射計(商品名「DR-M2」、Atago(股)製)，測定20℃、鈉D線的折射率以求取。The refractive index of the cured product of the curable epoxy resin composition of the present invention can be, for example, a test obtained by a heat hardening method described in the item of the following optical semiconductor device, and a test of 20 mm in length × 6 mm in width × 1 mm in thickness is cut out. A tablet was used as an intermediate liquid, and a multi-wavelength Abbe refractometer (trade name "DR-M2", manufactured by Atago Co., Ltd.) was used to measure 20 in a state in which ruthenium was adhered to the test piece. The refractive index of °C and sodium D line is obtained.
本發明之硬化性環氧樹脂組成物中，上述橡膠粒子之含量(摻合量)不特別限定，相對於硬化性環氧樹脂組成物中所含之具環氧基之化合物全量(100重量份)，為0.5~30重量份較佳，更佳為1~20重量份。橡膠粒子之含量若少於0.5重量份，硬化物之耐龜裂性有降低之傾向。另一方面，橡膠粒子之含量若超過30重量份，硬化物之耐熱性有降低之傾向。In the curable epoxy resin composition of the present invention, the content (doping amount) of the rubber particles is not particularly limited, and the total amount (100 parts by weight) of the epoxy group-containing compound contained in the curable epoxy resin composition is contained. It is preferably from 0.5 to 30 parts by weight, more preferably from 1 to 20 parts by weight. When the content of the rubber particles is less than 0.5 part by weight, the crack resistance of the cured product tends to decrease. On the other hand, when the content of the rubber particles exceeds 30 parts by weight, the heat resistance of the cured product tends to decrease.
本發明之硬化性環氧樹脂組成物中，除了上述以外，在不損及本發明效果之範圍內，也可以使用各種添加劑。添加劑例如若使用乙二醇、二乙二醇、丙二醇、甘油等具羥基之化合物，能使反應溫和地進行。此外，在不損及黏度或透明性之範圍內，可使用聚矽氧系或氟系消泡劑、塗平劑、γ-環氧丙氧基丙基三甲氧基矽烷等矽烷偶合劑、界面活性劑、二氧化矽、氧化鋁等無機填充劑、難燃劑、著色劑、抗氧化劑、紫外線吸收劑、離子吸附體、顏料、螢光體、脫模劑等慣用之添加劑。In the curable epoxy resin composition of the present invention, various additives may be used in addition to the above, within the range not impairing the effects of the present invention. When the additive is, for example, a compound having a hydroxyl group such as ethylene glycol, diethylene glycol, propylene glycol or glycerin, the reaction can be carried out gently. Further, a polydecane-based or fluorine-based antifoaming agent, a leveling agent, a decane coupling agent such as γ-glycidoxypropyltrimethoxydecane, or an interface may be used insofar as the viscosity or transparency is not impaired. An additive such as an inorganic filler such as an active agent, ceria, or alumina, a flame retardant, a colorant, an antioxidant, an ultraviolet absorber, an ion adsorbent, a pigment, a phosphor, and a release agent.
本發明之硬化性環氧樹脂組成物，只要含有上述脂環環氧化合物(A)、與異三聚氰酸單烯丙基二環氧丙酯化合物(B)、與脂環聚酯樹脂(C)、與硬化劑(D)及硬化促進劑(E)或硬化觸媒(F)即可，製備方法不特別限定。例如：可藉由分別製備含有脂環環氧化合物(A)、異三聚氰酸單烯丙基二環氧丙酯化合物(B)等具環氧基之化合物當作必要成分之α劑、及含有硬化劑(D)及硬化促進劑(E)、或硬化觸媒(F)當作必要成分之β劑，將該α劑與β劑以既定比例攪拌、混合並視需要於真空下脫泡以製備。又，於該情形，脂環聚酯樹脂(C)，可預先當作α劑及/或β劑之構成成分進行混合，也可於混合α劑與β劑時，當作α劑、β劑以外之成分進行摻合。The curable epoxy resin composition of the present invention contains the above-mentioned alicyclic epoxy compound (A), isocyanurate monoallyl diglycidyl ester compound (B), and alicyclic polyester resin ( C), the hardener (D), the hardening accelerator (E) or the curing catalyst (F) may be used, and the preparation method is not particularly limited. For example, an α-agent containing an epoxy group-containing compound such as an alicyclic epoxy compound (A) or a monoallyl propylene glycol epoxide compound (B) as an essential component, And a β agent containing a hardener (D), a hardening accelerator (E), or a hardening catalyst (F) as an essential component, the α agent and the β agent are stirred, mixed, and optionally removed under vacuum in a predetermined ratio. Soak to prepare. Further, in this case, the alicyclic polyester resin (C) may be previously mixed as a constituent component of the alpha agent and/or the beta agent, or may be used as an alpha agent or a beta agent when the alpha agent and the beta agent are mixed. The ingredients other than the ingredients are blended.
製備上述α劑時，攪拌、混合時之溫度不特別限定，較佳為30~150℃，更佳為35~130℃。又，製備上述β劑(由2種以上成分構成時)時，攪拌、混合時之溫度不特別限定，較佳為30~100℃，更佳為35~80℃。攪拌、混合可使用公知之裝置，例如：自轉公轉型混合機、行星混合機、捏合機、溶解器等。In the preparation of the above α agent, the temperature during stirring and mixing is not particularly limited, but is preferably from 30 to 150 ° C, more preferably from 35 to 130 ° C. Further, when the above-mentioned β agent (when two or more components are used) is prepared, the temperature during stirring and mixing is not particularly limited, but is preferably 30 to 100 ° C, and more preferably 35 to 80 ° C. For the stirring and mixing, a known device such as a self-rotating public-transition mixer, a planetary mixer, a kneader, a dissolver, or the like can be used.
尤其，本發明之硬化性環氧樹脂組成物含有硬化劑(D)當作必要成分時，就獲得均質組成物之觀點，較佳為藉由將脂環聚酯樹脂(C)與硬化劑(D)預先混合而獲得該等之混合物(脂環聚酯樹脂(C)與硬化劑(D)之混合物)後，於該混合物摻合硬化促進劑(E)或其他添加劑而製備β劑，然後混合該β劑與α劑以製備。脂環聚酯樹脂(C)與硬化劑(D)混合時之溫度不特別限定，較佳為60~130℃，更佳為90~120℃。混合時間不特別限定，較佳為30~100分鐘，更佳為45~80分鐘。混合不特別限定，宜於氮氣環境下進行。又，混合可使用上述公知之裝置。In particular, when the curable epoxy resin composition of the present invention contains a curing agent (D) as an essential component, a viewpoint of obtaining a homogeneous composition is preferred, by preferably using an alicyclic polyester resin (C) and a hardener ( D) premixing to obtain a mixture of the alicyclic polyester resin (C) and the hardener (D), and then blending the mixture with the hardening accelerator (E) or other additives to prepare the β agent, and then The β agent and the α agent are mixed to prepare. The temperature at which the alicyclic polyester resin (C) and the curing agent (D) are mixed is not particularly limited, and is preferably 60 to 130 ° C, more preferably 90 to 120 ° C. The mixing time is not particularly limited, and is preferably from 30 to 100 minutes, more preferably from 45 to 80 minutes. The mixing is not particularly limited and is preferably carried out under a nitrogen atmosphere. Further, the above-mentioned known device can be used for mixing.
脂環聚酯樹脂(C)與硬化劑(D)混合後，不特別限定，可進一步實施適當的化學處理(例如：氫化或脂環聚酯之末端改性等)等。又，上述脂環聚酯樹脂(C)與硬化劑(D)之混合物中，硬化劑(D)的一部分也可與脂環聚酯樹脂(C)(例如：脂環聚酯之羥基等)反應。The alicyclic polyester resin (C) is not particularly limited as long as it is mixed with the curing agent (D), and may be further subjected to an appropriate chemical treatment (for example, hydrogenation or terminal modification of an alicyclic polyester). Further, in the mixture of the alicyclic polyester resin (C) and the curing agent (D), a part of the curing agent (D) may be combined with the alicyclic polyester resin (C) (for example, a hydroxyl group of an alicyclic polyester, etc.) reaction.
上述脂環聚酯樹脂(C)與硬化劑(D)之混合物，例如也可使用「HN-7200」(日立化成工業(股)製)、「HN-5700」(日立化成工業(股)製)等市售品。For the mixture of the alicyclic polyester resin (C) and the curing agent (D), for example, "HN-7200" (manufactured by Hitachi Chemical Co., Ltd.) and "HN-5700" (Hitachi Chemical Industry Co., Ltd.) can also be used. ) and other commercial products.
藉由使本發明之硬化性環氧樹脂組成物硬化，可獲得透明性、耐熱性、耐光性、及耐龜裂性等各物性優異之硬化物。硬化時之加熱溫度(硬化溫度)不特別限定，宜為45~200℃，更佳為100~190℃，又更佳為100~180℃。又，硬化時之加熱時間(硬化時間)不特別限定，宜為30~600分鐘，更佳為45~540分鐘，又更佳為60~480分鐘。硬化溫度與硬化時間若低於上述範圍之下限值時，硬化不充分，反之，若高於上述範圍之上限值時，樹脂成分有時會分解，均不佳。硬化條件取決於各種條件，藉由當硬化溫度高時縮短硬化時間、硬化溫度低時加長硬化時間等，可以適當調整。By curing the curable epoxy resin composition of the present invention, a cured product excellent in physical properties such as transparency, heat resistance, light resistance, and crack resistance can be obtained. The heating temperature (hardening temperature) at the time of hardening is not particularly limited, and is preferably 45 to 200 ° C, more preferably 100 to 190 ° C, and still more preferably 100 to 180 ° C. Further, the heating time (hardening time) at the time of hardening is not particularly limited, and is preferably 30 to 600 minutes, more preferably 45 to 540 minutes, and still more preferably 60 to 480 minutes. When the curing temperature and the curing time are less than the lower limit of the above range, the curing is insufficient. On the other hand, when the curing temperature is higher than the upper limit of the above range, the resin component may be decomposed and may be poor. The hardening conditions depend on various conditions, and can be appropriately adjusted by shortening the hardening time when the hardening temperature is high, and lengthening the hardening time when the hardening temperature is low.
本發明之光半導體密封用樹脂組成物，係包含本發明之硬化性環氧樹脂組成物而構成。藉由使用本發明之光半導體密封用樹脂組成物，可以利用透明性、耐熱性、耐光性、及耐龜裂性等各物性優異之硬化物將光半導體元件密封，而得到光度不易隨時間降低之光半導體裝置。上述光半導體裝置即使具備高輸出、高輝度之光半導體元件時，光度仍不易隨時間降低。The resin composition for optical semiconductor sealing of the present invention comprises a curable epoxy resin composition of the present invention. By using the resin composition for optical semiconductor sealing of the present invention, it is possible to seal the optical semiconductor element with a cured product excellent in physical properties such as transparency, heat resistance, light resistance, and crack resistance, and it is difficult to reduce the luminosity with time. Optical semiconductor device. When the optical semiconductor device described above has a high-output, high-luminance optical semiconductor element, the illuminance does not easily decrease with time.
本發明之光半導體裝置，可藉由以本發明之硬化性環氧樹脂組成物(光半導體密封用樹脂組成物)將光半導體元件予以密封而獲得。光半導體元件之密封，係將以上述方法製備的硬化性環氧樹脂組成物注入既定成形模，並以既定條件進行加熱硬化。藉此，可獲得以硬化性環氧樹脂組成物將光半導體元件密封而成的光半導體裝置。硬化溫度與硬化時間可與上述相同。The optical semiconductor device of the present invention can be obtained by sealing the optical semiconductor element with the curable epoxy resin composition (resin composition for optical semiconductor sealing) of the present invention. In the sealing of the optical semiconductor element, the curable epoxy resin composition prepared by the above method is injected into a predetermined forming mold and heat-hardened under predetermined conditions. Thereby, an optical semiconductor device in which an optical semiconductor element is sealed with a curable epoxy resin composition can be obtained. The hardening temperature and the hardening time may be the same as described above.
本發明之硬化性環氧樹脂組成物，不限於上述光半導體(光半導體元件)之密封用途，也可利用於例如：黏著劑、電絕緣材、疊層板、塗覆、印墨、塗料、填封劑、抗蝕劑、複合材料、透明基材、透明片、透明薄膜、光學元件、光學透鏡、光學構件、光造形、電子紙、觸控面板、太陽能電池基板、光導波路、導光板、全像記憶體等。The curable epoxy resin composition of the present invention is not limited to the sealing use of the above-mentioned optical semiconductor (optical semiconductor element), and can be used, for example, for an adhesive, an electrical insulating material, a laminated plate, a coating, an ink, a coating, or the like. Sealing agent, resist, composite material, transparent substrate, transparent sheet, transparent film, optical element, optical lens, optical member, optical shape, electronic paper, touch panel, solar cell substrate, optical waveguide, light guide plate, Full image memory, etc.
以下依據實施例更詳細說明本發明，但本發明不限於該等實施例。The invention will be described in more detail below on the basis of examples, but the invention is not limited to the examples.
於配備回流冷卻器之1L聚合容器中，添加離子交換水500g、及二辛基磺基琥珀酸鈉0.68g，於氮氣流下攪拌的同時，升溫至80℃。於其中，一次添加用於形成核部分所必要之量之約相當於5重量%分量之由丙烯酸丁酯9.5g、苯乙烯2.57g、及二乙烯基苯0.39g構成之單體混合物，攪拌20分鐘使乳化後，添加過氧基二硫酸鉀9.5mg，攪拌1小時，進行起初的種聚合。接著，添加過氧基二硫酸鉀180.5mg，並攪拌5分鐘。於其中，花費2小時連續添加用於形成核部分所必要量之其餘(約95重量%分量)之於丙烯酸丁酯180.5g、苯乙烯48.89g、二乙烯基苯7.33g溶解二辛基磺基琥珀酸鈉0.95g而成的單體混合物，進行第2次的種聚合，之後進行1小時熟成，獲得核部分。Into a 1 L polymerization vessel equipped with a reflux condenser, 500 g of ion-exchanged water and 0.68 g of sodium dioctylsulfosuccinate were added, and the mixture was heated to 80 ° C while stirring under a nitrogen stream. a monomer mixture consisting of 9.5 g of butyl acrylate, 2.57 g of styrene, and 0.39 g of divinylbenzene in an amount equivalent to about 5% by weight of the amount necessary for forming the core portion, and stirring 20 After emulsification for a minute, 9.5 mg of potassium peroxydisulfate was added, and the mixture was stirred for 1 hour to carry out initial seed polymerization. Next, 180.5 mg of potassium peroxydisulfate was added and stirred for 5 minutes. Among them, it took 2 hours to continuously add the remaining amount (about 95% by weight) of the amount necessary for forming the core portion to 180.5 g of butyl acrylate, 48.89 g of styrene, 7.33 g of divinylbenzene to dissolve dioctylsulfonyl group. A monomer mixture of 0.95 g of sodium succinate was subjected to the second seed polymerization, followed by aging for 1 hour to obtain a core portion.
其次，添加過氧基二硫酸鉀60mg，攪拌5分鐘，並於其中花費30分鐘連續添加於甲基丙烯酸甲酯60g、丙烯酸1.5g、及甲基丙烯酸烯丙酯0.3g中溶解二辛基磺基琥珀酸鈉0.3g而成之單體混合物，進行種聚合。之後進行1小時熟成，形成被覆核部分之鞘層。Next, 60 mg of potassium peroxydisulfate was added, stirred for 5 minutes, and it was added thereto for 30 minutes to continuously add dioctylsulfonate to 60 g of methyl methacrylate, 1.5 g of acrylic acid, and 0.3 g of allyl methacrylate. A monomer mixture of 0.3 g of sodium succinate was used for seed polymerization. Thereafter, the mixture was aged for 1 hour to form a sheath layer covering the core portion.
其次冷卻至室溫(25℃)，以網眼120μm的塑膠製網過濾，獲得含有具核鞘構造之橡膠粒子之乳膠。將獲得之乳膠於-30℃冷凍，並以抽吸過濾器進行脫水洗滌後，於60℃進行一日夜送風乾燥，獲得橡膠粒子。獲得之橡膠粒子之平均粒徑為254nm、最大粒徑為486nm。Subsequently, the mixture was cooled to room temperature (25 ° C), and filtered through a plastic mesh having a mesh size of 120 μm to obtain a latex containing rubber particles having a core-sheath structure. The obtained latex was frozen at -30 ° C, dehydrated and washed with a suction filter, and then air-dried at 60 ° C for one day and night to obtain rubber particles. The obtained rubber particles had an average particle diameter of 254 nm and a maximum particle diameter of 486 nm.
又，橡膠粒子之平均粒徑、最大粒徑，係使用以動態光散射法為測定原理之「NanotracTM 」形式之Nanotrac粒度分布測定裝置(商品名「UPA-EX150」、日機裝(股)製)測定試樣，針對獲得之粒度分布曲線，以累積曲線成為50%之時點的粒徑累積平均徑當作平均粒徑、粒度分布測定結果之頻度(%)超過0.00%之時點的最大粒徑當作最大粒徑。又，上述試樣，使用將下列製造例2獲得之橡膠粒子分散環氧化合物1重量份分散於四氫呋喃20重量份者。Further, the average particle diameter of the rubber particles, maximum particle diameter, based dynamic light scattering method using Nanotrac particle size is in the form of "Nanotrac (TM)" principle of distribution measuring apparatus (trade name "UPA-EX150", Nikkiso (shares) For the obtained particle size distribution curve, the cumulative average diameter of the particle diameter at the point where the cumulative curve becomes 50% is taken as the average particle diameter, and the frequency (%) of the particle size distribution measurement result is more than 0.00%. The diameter is taken as the maximum particle size. In the sample, one part by weight of the rubber particle-dispersed epoxy compound obtained in the following Production Example 2 was dispersed in 20 parts by weight of tetrahydrofuran.
將製造例1獲得之橡膠粒子10重量份，於氮氣流下、升溫於60℃之狀態，使用溶解器(1000rpm、60分鐘)，分散於商品名「Celloxide2021P」(3,4-環氧環己基甲基(3,4-環氧)環己烷羧酸酯、Daicel(股)製)70重量份，進行真空脫泡，獲得橡膠粒子分散環氧化合物(25℃之黏度：624mPa‧s)。10 parts by weight of the rubber particles obtained in Production Example 1 were heated to 60 ° C under a nitrogen stream, and dispersed in a product name "Celloxide 2021P" (3,4-epoxycyclohexyl) using a dissolver (1000 rpm, 60 minutes). 70 parts by weight of a base (3,4-epoxy)cyclohexanecarboxylate and a Daicel (manufactured by Daicel) was vacuum-deaerated to obtain a rubber particle-dispersed epoxy compound (viscosity at 25 ° C: 624 mPa ‧ s).
又，製造例2獲得之橡膠粒子分散環氧化合物(10重量份之橡膠粒子分散於70重量份之Celloxide2021P者)之黏度(於25℃之黏度)，係使用數位黏度計(商品名「DVU-EII型」、Tokimec(股)製)測定。Further, the viscosity (the viscosity at 25 ° C) of the rubber particle-dispersed epoxy compound (10 parts by weight of the rubber particles dispersed in 70 parts by weight of Celloxide 2021P) obtained in Production Example 2 was measured by a digital viscometer (trade name "DVU- EII type", Tokimec (manufactured by the company).
將異三聚氰酸單烯丙基二環氧丙酯(商品名「MA-DGIC」、四國化成工業(股)製)、脂環環氧化合物(商品名「Celloxide2021P」、Daicel(股)製)、製造例2獲得之橡膠粒子分散環氧樹脂、雙酚A型環氧樹脂(商品名「YD-128」、新日鐵化學(股)製)，依表1所示之摻合配方(摻合比例)(單位：重量份)混合，於80℃攪拌1小時，使異三聚氰酸單烯丙基二環氧丙酯溶解，獲得環氧樹脂(混合物)(相當於上述α劑)。又，表1中之「-」，代表未進行該成分之摻合，表2亦同。Isopropyl propylene carbonate (trade name "MA-DGIC", manufactured by Shikoku Chemicals Co., Ltd.), alicyclic epoxy compound (trade name "Celloxide 2021P", Daicel (share)) , the rubber particle-dispersed epoxy resin obtained in Production Example 2, and the bisphenol A-type epoxy resin (trade name "YD-128", manufactured by Nippon Steel Chemical Co., Ltd.), and the blending formula shown in Table 1 (mixing ratio) (unit: parts by weight), mixing, stirring at 80 ° C for 1 hour, dissolving isocyanurate monoallyl diglycidyl ester to obtain an epoxy resin (mixture) (corresponding to the above α agent ). Further, "-" in Table 1 indicates that the blending of the components was not carried out, and Table 2 is also the same.
(至少含有硬化劑之硬化劑組成物(以下稱為「K劑」)之製造：實施例1~6、比較例1~3)(Manufacture of at least a hardener composition containing a curing agent (hereinafter referred to as "K agent"): Examples 1 to 6 and Comparative Examples 1 to 3)
將硬化劑(酸酐)(商品名「Rikacid MH-700」、新日本理化(股)製)、硬化劑(酸酐)與脂環聚酯樹脂之混合物(商品名「HN-7200」、商品名「HN-5700」，皆日立化成工業(股)製)、硬化促進劑(商品名「U-CAT 18X」、San-apro(股)製)、添加劑(商品名「乙二醇」、和光純藥工業(股)製)，依照表1所示之摻合配方(單位：重量份)，使用自公轉式攪拌裝置(商品名「脫泡練太郎AR-250」、Thinky(股)製)均勻混合並脫泡，獲得K劑(相當於上述β劑)。A mixture of a curing agent (anhydride) (trade name "Rikacid MH-700", manufactured by Nippon Chemical and Chemical Co., Ltd.), a curing agent (anhydride), and an alicyclic polyester resin (trade name "HN-7200", trade name" HN-5700", all manufactured by Hitachi Chemical Co., Ltd.), hardening accelerator (trade name "U-CAT 18X", San-apro (share)), additives (trade name "ethylene glycol", and korea Industrial (stock) system, according to the blending formula shown in Table 1 (unit: parts by weight), using a self-revolving stirring device (trade name "defoaming Rantaro AR-250", Thinky (stock) system) evenly mixed And defoaming, K agent (corresponding to the above β agent) is obtained.
將製造例3獲得之環氧樹脂、製造例4獲得之K劑，使用自公轉式攪拌裝置(商品名「脫泡練太郎AR-250」、Thinky(股)製)均勻混合並脫泡，以成為表1所示摻合比例(單位：重量份)，獲得硬化性環氧樹脂組成物。又，比較例1之情形，環氧樹脂係使用商品名「Celloxide2021P」(Daicel(股)製)。The epoxy resin obtained in the production example 3 and the K agent obtained in the production example 4 were uniformly mixed and defoamed using a self-rotating stirring device (trade name "defoaming Ryotaro AR-250", manufactured by Thinky Co., Ltd.) to The blending ratio (unit: parts by weight) shown in Table 1 was obtained to obtain a curable epoxy resin composition. Further, in the case of Comparative Example 1, the epoxy resin was used under the trade name "Celloxide 2021P" (manufactured by Daicel Co., Ltd.).
將上述獲得之硬化性環氧樹脂組成物，澆鑄於第1圖所示之光半導體之導線架(InGaN元件、3.5mm×2.8mm)模後，於120℃之烘箱(樹脂硬化烘箱)進行5小時加熱，獲得以硬化之樹脂(硬化物)將光半導體元件予以密封之光半導體裝置。又，第1圖中，100表示反射件(光反射用樹脂組成物)、101表示金屬配線、102表示光半導體元件、103表示接合引線、104表示透明密封樹脂(硬化物)。The curable epoxy resin composition obtained above was cast into a lead frame (InGaN element, 3.5 mm × 2.8 mm) of the optical semiconductor shown in Fig. 1, and then dried in an oven (resin-hardened oven) at 120 °C. After heating in an hour, an optical semiconductor device in which an optical semiconductor element is sealed with a hardened resin (hardened material) is obtained. In the first drawing, 100 denotes a reflector (a resin composition for light reflection), 101 denotes a metal wiring, 102 denotes an optical semiconductor element, 103 denotes a bonding wire, and 104 denotes a transparent sealing resin (cured material).
將異三聚氰酸單烯丙基二環氧丙酯(商品名「MA-DGIC」、四國化成工業(股)製)、脂環環氧化合物(商品名「Celloxide2021P」、Daicel(股)製)、製造例2獲得之橡膠粒子分散環氧樹脂、雙酚A型環氧樹脂(商品名「YD-128」、新日鐵化學(股)製)，依照表2所示之摻合配方(摻合比例)(單位：重量份)混合，於80℃進行1小時攪拌，藉此使異三聚氰酸單烯丙基二環氧丙酯溶解，獲得環氧樹脂(混合物)(相當於上述α劑)。Isopropyl propylene carbonate (trade name "MA-DGIC", manufactured by Shikoku Chemicals Co., Ltd.), alicyclic epoxy compound (trade name "Celloxide 2021P", Daicel (share)) , the rubber particle-dispersed epoxy resin obtained in Production Example 2, and the bisphenol A-type epoxy resin (trade name "YD-128", manufactured by Nippon Steel Chemical Co., Ltd.), according to the blending formula shown in Table 2. (mixing ratio) (unit: parts by weight), and stirring at 80 ° C for 1 hour, thereby dissolving isoallyl cyanuric propylene glycol acrylate to obtain an epoxy resin (mixture) (equivalent to The above α agent).
於具備攪拌機、溫度計、及回流冷卻器之反應容器中，添加1,4-環己烷二羧酸(東京化成工業(股)製)172重量份、新戊二醇(東京化成工業(股)製)208重量份、四丁基鈦酸酯(和光純藥工業(股)製)0.1重量份，加熱至160℃，再花費4小時從160℃升溫至250℃。其次，花費1小時減壓至5mmHg，再減壓至0.3mmHg以下後於250℃使反應1小時，獲得脂環聚酯樹脂。172 parts by weight of 1,4-cyclohexanedicarboxylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and neopentyl glycol (Tokyo Chemical Industry Co., Ltd.) were added to a reaction vessel equipped with a stirrer, a thermometer, and a reflux condenser. 208 parts by weight of 0.1 parts by weight of tetrabutyl titanate (manufactured by Wako Pure Chemical Industries, Ltd.), heated to 160 ° C, and further heated from 160 ° C to 250 ° C for 4 hours. Next, the pressure was reduced to 5 mmHg for 1 hour, and the pressure was reduced to 0.3 mmHg or less, and the reaction was allowed to proceed at 250 ° C for 1 hour to obtain an alicyclic polyester resin.
將製造例5獲得之環氧樹脂、製造例6獲得之脂環聚酯樹脂、硬化觸媒(商品名「San-aid SI-100L」、三新化學工業(股)製)，使用自公轉式攪拌裝置(商品名「脫泡練太郎AR-250」、Thinky(股)製)均勻混合並脫泡，使成為表2所示摻合比例(單位：重量份)，獲得硬化性環氧樹脂組成物。又，比較例4之情形，環氧樹脂使用商品名「Celloxide2021P」(Daicel(股)製)。The epoxy resin obtained in Production Example 5, the alicyclic polyester resin obtained in Production Example 6, and the curing catalyst (trade name "San-aid SI-100L", manufactured by Sanshin Chemical Industry Co., Ltd.) were used in the self-revolving type. The stirring device (trade name "Defoaming Ryotaro AR-250", manufactured by Thinky Co., Ltd.) was uniformly mixed and defoamed to obtain the blending ratio (unit: parts by weight) shown in Table 2, and a curable epoxy resin composition was obtained. Things. Further, in the case of Comparative Example 4, the epoxy resin was used under the trade name "Celloxide 2021P" (manufactured by Daicel Co., Ltd.).
將上述獲得之硬化性環氧樹脂組成物，澆鑄於第1圖所示之光半導體之導線架(InGaN元件、3.5mm×2.8mm)模後，於120℃之烘箱(樹脂硬化烘箱)進行5小時加熱，獲得以硬化之樹脂(硬化物)將光半導體元件予以密封之光半導體裝置。The curable epoxy resin composition obtained above was cast into a lead frame (InGaN element, 3.5 mm × 2.8 mm) of the optical semiconductor shown in Fig. 1, and then dried in an oven (resin-hardened oven) at 120 °C. After heating in an hour, an optical semiconductor device in which an optical semiconductor element is sealed with a hardened resin (hardened material) is obtained.
針對實施例及比較例獲得之光半導體裝置，依以下方法實施評價試驗。For the optical semiconductor devices obtained in the examples and the comparative examples, evaluation tests were carried out in the following manner.
實施例及比較例獲得之光半導體裝置之全光束，使用全光束測定機測定。再者，測定於85℃之恆溫槽內對光半導體裝置流過60mA之電流100小時後之全光束。由下式計算光度保持率。結果示於表1、表2。The total light beams of the optical semiconductor devices obtained in the examples and the comparative examples were measured using a full beam measuring machine. Further, a total beam of a current of 60 mA was applied to the optical semiconductor device for 100 hours in a thermostat at 85 ° C. The photometric retention rate is calculated by the following formula. The results are shown in Tables 1 and 2.
{光度保持率(%)}{Photometric retention rate (%)}
={100小時後之全光束(lm)}/{0小時之全光束(lm)}×100={100 hours after full beam (lm)}/{0 hour full beam (lm)}×100
將實施例及比較例獲得之光半導體裝置(各硬化性環氧樹脂組成物使用2個)暴露於-40℃之氣體環境下30分鐘，接著，於100℃之氣體環境下暴露30分鐘當作1個循環的熱衝撃，使用熱衝撃試驗機給予200個循環。之後，使用數位顯微鏡(VHX-900、KEYENCE(股)製)觀察光半導體裝置之密封樹脂(硬化性環氧樹脂組成物之硬化物)產生的龜裂的長度，並計測2個光半導體裝置中具有長度為90μm以上之龜裂之光半導體裝置之個數。結果示於表1、表2。The optical semiconductor device obtained in the examples and the comparative examples (two for each curable epoxy resin composition) was exposed to a gas atmosphere at -40 ° C for 30 minutes, and then exposed to a gas atmosphere at 100 ° C for 30 minutes. One cycle of hot flushing was given for 200 cycles using a hot stamping tester. After that, the length of the crack generated by the sealing resin (cured material of the curable epoxy resin composition) of the optical semiconductor device was observed with a digital microscope (VHX-900, manufactured by KEYENCE Co., Ltd.), and measured in two optical semiconductor devices. The number of optical semiconductor devices having cracks having a length of 90 μm or more. The results are shown in Tables 1 and 2.
於通電試驗的光度保持率為90%以上，且熱衝撃試驗中產生長度90μm以上之龜裂之光半導體裝置個數為0個者，於綜合判定評為○(良好)。除此以外於綜合判定評為×(不良)。結果示於表1、表2。The photo-sustaining rate of the electric current test was 90% or more, and the number of cracked optical semiconductor devices having a length of 90 μm or more in the thermal punching test was zero, and was evaluated as ○ (good) in the overall judgment. In addition to this, it was rated as × (bad) in the comprehensive judgment. The results are shown in Tables 1 and 2.
又，實施例及比較例使用之成分如下。Moreover, the components used in the examples and comparative examples are as follows.
CEL2021P(CELLOXIDE2021P)：3,4-環氧環己基甲基(3,4-環氧)環己烷羧酸酯、Daicel(股)製CEL2021P (CELLOXIDE 2021P): 3,4-epoxycyclohexylmethyl (3,4-epoxy)cyclohexanecarboxylate, manufactured by Daicel
MA-DGIC：異三聚氰酸單烯丙基二環氧丙酯、四國化成工業(股)製MA-DGIC: Isopropyl propylene glycol monoisopropyl epoxide, Siguo Chemical Industry Co., Ltd.
YD-128：雙酚A型環氧樹脂、新日鐵化學(股)製YD-128: bisphenol A epoxy resin, Nippon Steel Chemical Co., Ltd.
MH-700(Rikacid MH-700)：4-甲基六氫鄰苯二甲酸酐/六氫鄰苯二甲酸酐=70/30、新日本理化(股)製MH-700 (Rikacid MH-700): 4-methylhexahydrophthalic anhydride/hexahydrophthalic anhydride=70/30, New Japan Physical and Chemical Co., Ltd.
HN-7200：4-甲基六氫鄰苯二甲酸酐與脂環聚酯之混合物、日立化成工業(股)製HN-7200: a mixture of 4-methylhexahydrophthalic anhydride and an alicyclic polyester, manufactured by Hitachi Chemical Co., Ltd.
HN-5700(舊稱「DHZ-01」)：4-甲基六氫鄰苯二甲酸酐/3-甲基六氫鄰苯二甲酸酐=70/30與脂環聚酯之混合物、日立化成工業(股)製HN-5700 (formerly known as "DHZ-01"): 4-methylhexahydrophthalic anhydride/3-methylhexahydrophthalic anhydride=70/30 mixture with alicyclic polyester, Hitachi Chemical Industrial (share) system
U-CAT 18X：硬化促進劑、SAN-APRO(股)製U-CAT 18X: Hardening accelerator, SAN-APRO (share) system
乙二醇：和光純藥工業(股)製Ethylene glycol: Wako Pure Chemical Industries Co., Ltd.
SAN-AID SI-100L：芳基鋶鹽、三新化學工業(股)製SAN-AID SI-100L: aryl sulfonium salt, Sanxin Chemical Industry Co., Ltd.
試驗設備Test equipment
‧樹脂硬化烘箱‧Resin hardening oven
ESPEC(股)製 GPHH-201ESPEC (share) system GPHH-201
‧恆溫槽‧Thermostat
ESPEC(股)製 小型高溫腔室 ST-120B1ESPEC (stock) system small high temperature chamber ST-120B1
。全光束測定機. Full beam measuring machine
美國Optronic Laboratories公司製 多重分光放射測定系統 OL771Multi-spectral radiometry system manufactured by Optronic Laboratories, USA OL771
。熱衝撃試驗機. Hot punching test machine
ESPEC(股)製 小型冷熱衝撃裝置 TSE-11-AESPEC (stock) system small hot and cold flushing device TSE-11-A
本發明之硬化性環氧樹脂組成物，可理想地使用於光半導體元件之密封用途。又，本發明之硬化性環氧樹脂組成物，也可利用於黏著劑、電絕緣材、疊層板、塗覆、印墨、塗料、填封劑、抗蝕劑、複合材料、透明基材、透明片、透明薄膜、光學元件、光學透鏡、光學構件、光造形、電子紙、觸控面板、太陽能電池基板、光導波路、導光板、全像記憶體等。The curable epoxy resin composition of the present invention can be preferably used for sealing applications of optical semiconductor elements. Moreover, the curable epoxy resin composition of the present invention can also be used for an adhesive, an electrical insulating material, a laminated board, a coating, an ink, a coating, a potting agent, a resist, a composite material, a transparent substrate. , transparent sheet, transparent film, optical element, optical lens, optical member, optical shape, electronic paper, touch panel, solar cell substrate, optical waveguide, light guide plate, holographic memory, and the like.
100．．．反射件(光反射用樹脂組成物)100. . . Reflector (resin composition for light reflection)
101．．．金屬配線101. . . Metal wiring
102．．．LED元件102. . . LED component
103．．．接合導線103. . . Bonding wire
104．．．透明密封樹脂104. . . Transparent sealing resin
第1圖顯示以本發明之硬化性環氧樹脂組成物將元件(光半導體元件)密封而得之光半導體裝置之一實施形態之概略圖。左側之圖(a)為立體圖，右側之圖(b)為剖面圖。Fig. 1 is a schematic view showing an embodiment of an optical semiconductor device obtained by sealing an element (optical semiconductor element) with a curable epoxy resin composition of the present invention. The left side view (a) is a perspective view, and the right side view (b) is a cross-sectional view.
Claims (9)
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| JP6082746B2 (en) * | 2012-09-07 | 2017-02-15 | 株式会社ダイセル | Curable epoxy resin composition, cured product thereof, and optical semiconductor device |
| JP6185703B2 (en) * | 2012-10-19 | 2017-08-23 | 株式会社ダイセル | Curable epoxy resin composition, cured product thereof, and optical semiconductor device |
| JP6059538B2 (en) * | 2013-01-09 | 2017-01-11 | 株式会社ダイセル | Curable epoxy resin composition |
| WO2014109317A1 (en) * | 2013-01-09 | 2014-07-17 | 株式会社ダイセル | Curable epoxy resin composition |
| JP2017125212A (en) * | 2017-04-10 | 2017-07-20 | 株式会社ダイセル | Curable epoxy resin composition and cured article and optical semiconductor device |
| CN111918899B (en) | 2018-03-28 | 2023-05-16 | 日本板硝子株式会社 | Cured product of resin composition, laminate, and resin composition |
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| JP2002003582A (en) * | 2000-04-17 | 2002-01-09 | Mitsubishi Electric Corp | Liquid thermosetting resin composition and method of fabricating insulating coil using the same |
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| JP2003277591A (en) * | 2002-03-26 | 2003-10-02 | Sumitomo Bakelite Co Ltd | Epoxy resin composition, prepreg and laminate |
| WO2007061037A1 (en) * | 2005-11-25 | 2007-05-31 | Hitachi Chemical Co., Ltd. | Liquid resin composition for electronic component and electronic component device |
| JP5638812B2 (en) * | 2010-02-01 | 2014-12-10 | 株式会社ダイセル | Curable epoxy resin composition |
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| JP2002003582A (en) * | 2000-04-17 | 2002-01-09 | Mitsubishi Electric Corp | Liquid thermosetting resin composition and method of fabricating insulating coil using the same |
| JP2004131553A (en) * | 2002-10-09 | 2004-04-30 | Yokohama Tlo Co Ltd | Epoxy resin composition |
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