JP7328240B2 - epoxy resin composition - Google Patents
epoxy resin composition Download PDFInfo
- Publication number
- JP7328240B2 JP7328240B2 JP2020548205A JP2020548205A JP7328240B2 JP 7328240 B2 JP7328240 B2 JP 7328240B2 JP 2020548205 A JP2020548205 A JP 2020548205A JP 2020548205 A JP2020548205 A JP 2020548205A JP 7328240 B2 JP7328240 B2 JP 7328240B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- epoxy resin
- resin composition
- anion
- hydrogen atom
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000003822 epoxy resin Substances 0.000 title claims description 80
- 229920000647 polyepoxide Polymers 0.000 title claims description 80
- 239000000203 mixture Substances 0.000 title claims description 36
- -1 ester compound Chemical class 0.000 claims description 64
- 150000004693 imidazolium salts Chemical class 0.000 claims description 19
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 18
- 150000001450 anions Chemical class 0.000 claims description 17
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 14
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 11
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 claims description 10
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 8
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 8
- 239000004065 semiconductor Substances 0.000 claims description 6
- 239000003566 sealing material Substances 0.000 claims description 5
- 125000004185 ester group Chemical group 0.000 claims description 4
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 4
- 125000003368 amide group Chemical group 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000001033 ether group Chemical group 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 description 15
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 14
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 8
- 229910052801 chlorine Inorganic materials 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical group CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 4
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- HXMUPILCYSJMLQ-UHFFFAOYSA-M 1-ethyl-3-methylimidazol-3-ium;4-methylbenzenesulfonate Chemical compound CC[N+]=1C=CN(C)C=1.CC1=CC=C(S([O-])(=O)=O)C=C1 HXMUPILCYSJMLQ-UHFFFAOYSA-M 0.000 description 3
- KXTSPQCZQYDUGX-UHFFFAOYSA-N 1h-imidazol-1-ium;phthalate Chemical compound [NH2+]1C=CN=C1.[NH2+]1C=CN=C1.[O-]C(=O)C1=CC=CC=C1C([O-])=O KXTSPQCZQYDUGX-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 238000004891 communication Methods 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 2
- BUZMJVBOGDBMGI-UHFFFAOYSA-N 1-phenylpropylbenzene Chemical compound C=1C=CC=CC=1C(CC)C1=CC=CC=C1 BUZMJVBOGDBMGI-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 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 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000004203 carnauba wax Substances 0.000 description 2
- 235000013869 carnauba wax Nutrition 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 2
- 239000008393 encapsulating agent Substances 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000013538 functional additive Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000012552 review Methods 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- HXCQZBAIXOFBAR-KSBRXOFISA-L (z)-but-2-enedioate;1-ethyl-3-methylimidazol-3-ium Chemical compound CCN1C=C[N+](C)=C1.CCN1C=C[N+](C)=C1.[O-]C(=O)\C=C/C([O-])=O HXCQZBAIXOFBAR-KSBRXOFISA-L 0.000 description 1
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 description 1
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- BMQZYMYBQZGEEY-UHFFFAOYSA-M 1-ethyl-3-methylimidazolium chloride Chemical compound [Cl-].CCN1C=C[N+](C)=C1 BMQZYMYBQZGEEY-UHFFFAOYSA-M 0.000 description 1
- VJPVMNOPCPAQLC-UHFFFAOYSA-M 2-carboxyphenolate 1-ethyl-3-methylimidazol-3-ium Chemical compound CCn1cc[n+](C)c1.Oc1ccccc1C([O-])=O VJPVMNOPCPAQLC-UHFFFAOYSA-M 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 description 1
- LVNLBBGBASVLLI-UHFFFAOYSA-N 3-triethoxysilylpropylurea Chemical compound CCO[Si](OCC)(OCC)CCCNC(N)=O LVNLBBGBASVLLI-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- ROXSFAJHEZHIBS-UHFFFAOYSA-M C(C)OC([O-])=O.C[N+]1=CN(C=C1)CC Chemical compound C(C)OC([O-])=O.C[N+]1=CN(C=C1)CC ROXSFAJHEZHIBS-UHFFFAOYSA-M 0.000 description 1
- YBQKMDQQQBZUBS-UHFFFAOYSA-L CC[N+]1=CN(C)C=C1.CC[N+]1=CN(C)C=C1.[O-]C(=O)CCC([O-])=O Chemical compound CC[N+]1=CN(C)C=C1.CC[N+]1=CN(C)C=C1.[O-]C(=O)CCC([O-])=O YBQKMDQQQBZUBS-UHFFFAOYSA-L 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 125000005910 alkyl carbonate group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 239000004643 cyanate ester Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G59/40—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 curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
-
- 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
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Description
本発明は、エポキシ樹脂組成物に関する。さらに詳しくは、プリント配線板や半導体封止材料などの電子部品用のエポキシ樹脂系封止剤の製造に適したエポキシ樹脂組成物に関する。 The present invention relates to epoxy resin compositions. More particularly, it relates to an epoxy resin composition suitable for producing epoxy resin-based encapsulants for electronic parts such as printed wiring boards and semiconductor encapsulants.
エポキシ樹脂は、その優れた接着性、絶縁性、耐熱性からプリント配線板や半導体封止材料として用いられてきた。しかしこのエポキシ樹脂も近年の高周波通信、例えば１ＧＨｚ以上での高周波通信でのエネルギー損失を抑制するために低誘電正接化か望まれている。この低誘電正接化ニーズにこたえるため、従来エポキシ樹脂の硬化物に使用されていたフェノール樹脂の代わりに活性エステル化合物を用いた方法が開示されている（例えば、特許文献１）。こうすることで、エポキシ樹脂と活性エステルの反応であるので、水酸基が原理上、生成しないため、低誘電正接化を実現できた。 Epoxy resins have been used as printed wiring boards and semiconductor sealing materials because of their excellent adhesiveness, insulation and heat resistance. However, this epoxy resin is also desired to have a low dielectric loss tangent in order to suppress energy loss in recent high-frequency communication, for example, high-frequency communication at 1 GHz or higher. In order to meet the need for low dielectric loss tangent, a method has been disclosed in which an active ester compound is used instead of the phenolic resin conventionally used in cured epoxy resins (for example, Patent Document 1). By doing so, since the reaction between the epoxy resin and the active ester does not generate hydroxyl groups in principle, a low dielectric loss tangent can be achieved.
しかしながら、活性エステル化合物とエポキシ樹脂との反応は非常に遅く、より有効な硬化促進剤の開発が急務である。一般的に最も有効とされている硬化促進剤は、４－ジメチルアミノピリジンであるが、この化合物は求核性が非常に強いために、硬化促進剤として働く半面、エポキシ樹脂中の塩素原子に結合した炭素原子に求核してしまうため、エポキシ樹脂中の共有結合で結合している塩素原子が脱離し、樹脂中に遊離塩素を生成してしまう。この遊離塩素が、電子部品用のデバイスの信頼性を悪化させるという観点で問題があった。 However, the reaction between the active ester compound and the epoxy resin is very slow, and there is an urgent need to develop a more effective curing accelerator. Generally, the most effective curing accelerator is 4-dimethylaminopyridine, but because this compound has a very strong nucleophilicity, it works as a curing accelerator, but on the other hand, it does not react to the chlorine atoms in the epoxy resin. Since it becomes nucleophilic to the bonded carbon atom, the chlorine atom that is covalently bonded in the epoxy resin is eliminated, and free chlorine is generated in the resin. There is a problem in that this free chlorine deteriorates the reliability of devices for electronic parts.
そこで、活性エステル化合物とエポキシ樹脂との反応において硬化促進剤として優れ、なおかつ遊離塩素を生成しない硬化促進剤を用いたエポキシ樹脂組成物を提供することを目的とする。 Therefore, an object of the present invention is to provide an epoxy resin composition using a curing accelerator which is excellent as a curing accelerator in the reaction between an active ester compound and an epoxy resin and which does not generate free chlorine.
本発明者らは、上記の目的を達成するべく検討を行った結果、本発明に到達した。
すなわち、本発明は、エポキシ樹脂（Ａ）、活性エステル化合物（Ｂ）、および硬化促進剤（Ｃ）を含有するエポキシ樹脂組成物であって、硬化促進剤（Ｃ）が一般式（１）で示されるイミダゾリウムカチオン（Ｄ）と、アニオン（Ｅ）からなるイミダゾリウム塩（Ｓ）を含むことを特徴とするエポキシ樹脂組成物である。The present inventors arrived at the present invention as a result of conducting studies to achieve the above object.
That is, the present invention is an epoxy resin composition containing an epoxy resin (A), an active ester compound (B), and a curing accelerator (C), wherein the curing accelerator (C) is represented by general formula (1) It is an epoxy resin composition characterized by containing an imidazolium salt (S) consisting of an imidazolium cation (D) and an anion (E) shown.
［式（１）中、Ｒ１は、水素原子、メチル基、エチル基、プロピル基又はブチル基を表し、Ｒ２及びＲ３は、同一または異なって、メチル基、エチル基、プロピル基又はブチル基を表し、Ｒ４及びＲ５は、同一または異なって、水素原子、メチル基又はエチル基を表す。］ [In the formula (1), R1 represents a hydrogen atom, a methyl group, an ethyl group, a propyl group or a butyl group; R2 and R3 are the same or different and represent a methyl group, an ethyl group, a propyl group or a butyl group; , R4 and R5 are the same or different and represent a hydrogen atom, a methyl group or an ethyl group. ]
本発明のエポキシ樹脂組成物は、活性エステル化合物とエポキシ樹脂との反応において硬化促進剤として優れ、なおかつ遊離塩素を生成しないという効果を奏する。 INDUSTRIAL APPLICABILITY The epoxy resin composition of the present invention exhibits the effect of being excellent as a curing accelerator in the reaction between an active ester compound and an epoxy resin and not generating free chlorine.
以下、本発明のエポキシ樹脂組成物について説明する。
本発明のエポキシ樹脂組成物は、エポキシ樹脂（Ａ）、活性エステル化合物（Ｂ）、および硬化促進剤（Ｃ）を含有するエポキシ樹脂組成物であって、硬化促進剤（Ｃ）が一般式（１）で示されるイミダゾリウムカチオン（Ｄ）とアニオン（Ｅ）からなるイミダゾリウム塩（Ｓ）を含む。The epoxy resin composition of the present invention is described below.
The epoxy resin composition of the present invention is an epoxy resin composition containing an epoxy resin (A), an active ester compound (B), and a curing accelerator (C), wherein the curing accelerator (C) has the general formula ( 1) contains an imidazolium salt (S) consisting of an imidazolium cation (D) and an anion (E).
エポキシ樹脂（Ａ）は、１分子内にエポキシ基を２個以上有する、オリゴマー、ポリマー全般であり、その分子量、分子構造は特に限定するものではないが、例えば、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ハイドロキノン型エポキシ樹脂、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビフェニル型エポキシ樹脂、スチルベン型エポキシ樹脂、トリフェノールメタン型エポキシ樹脂、アルキル変性トリフェノールメタン型エポキシ樹脂、トリアジン核含有エポキシ樹脂、ジシクロペンタジエン変性フェノール型エポキシ樹脂、フェニレン及び／又はビフェニレン骨格を有するフェノールアラルキル型エポキシ樹脂、ナフトール型エポキシ樹脂、ナフタレン型エポキシ樹脂、フェニレン及び／又はビフェニレン骨格を有するナフトールアラルキル型エポキシ樹脂等が挙げられ、これらは単独でも混合して用いても差し支えない。 Epoxy resin (A) is generally oligomers and polymers having two or more epoxy groups in one molecule, and its molecular weight and molecular structure are not particularly limited, but examples thereof include phenol novolak type epoxy resins and cresol novolacs. type epoxy resin, hydroquinone type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, stilbene type epoxy resin, triphenolmethane type epoxy resin, alkyl-modified triphenolmethane type epoxy resin, triazine nucleus-containing resin Epoxy resins, dicyclopentadiene-modified phenol-type epoxy resins, phenol aralkyl-type epoxy resins having a phenylene and/or biphenylene skeleton, naphthol-type epoxy resins, naphthalene-type epoxy resins, naphthol-aralkyl-type epoxy resins having a phenylene and/or biphenylene skeleton, etc. These may be used singly or in combination.
エポキシ樹脂（Ａ）の例としては、ＤＩＣ株式会社製の：ＨＰ－４０３２、ＨＰ－４７００、ＨＰ－７２００、ＨＰ－８２０、ＨＰ－４７７０、ＨＰ－５０００、ＥＸＡ－８５０、ＥＸＡ－８３０、ＥＸＡ－１５１４、ＥＸＡ－４８５０シリーズ；日本化薬株式会社製の：ＥＰＰＮ－２０１Ｌ、ＢＲＥＮ－１０５、ＥＰＰＮ－５０２Ｈ、ＥＯＣＮ－１０２０、ＮＣ－２０００－Ｌ、ＸＤ－１０００、ＮＣ－７０００Ｌ、ＮＣ－７３００Ｌ、ＥＰＰＮ－５０１Ｈ、ＮＣ－３０００；三菱ケミカル株式会社製の：ＸＹ－４０００などが挙げられる。 Examples of the epoxy resin (A) include those manufactured by DIC Corporation: HP-4032, HP-4700, HP-7200, HP-820, HP-4770, HP-5000, EXA-850, EXA-830, EXA- 1514, EXA-4850 series; manufactured by Nippon Kayaku Co., Ltd.: EPPN-201L, BREN-105, EPPN-502H, EOCN-1020, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN -501H, NC-3000; XY-4000 manufactured by Mitsubishi Chemical Corporation.
活性エステル化合物（Ｂ）とは、フェノール性水酸基をエステル化して得られるエステル化合物であり、分子中に２個以上のエステル基をもつことが好ましく、エポキシ樹脂を硬化させることができるものであれば、とくに制限なく使用できる。
好ましい活性エステル化合物（Ｂ）は、多価カルボン酸とフェノール性水酸基を有する化合物とエステル化する、又は多価フェノールとカルボン酸とエステル化することで得られる。
多価カルボン酸とは、２つ以上のカルボキシル基を有するカルボン酸であり、アジピン酸、セバシン酸などの脂肪族カルボン酸や、芳香族化合物の水素原子を２つ以上のカルボキシル基で置換したカルボン酸等が挙げられる。多価フェノールとは、２つ以上のフェノール性水酸基を有する化合物であり、芳香族化合物の水素原子を２つ以上の水酸基で置換したもの等が挙げられる。The active ester compound (B) is an ester compound obtained by esterifying a phenolic hydroxyl group, and preferably has two or more ester groups in the molecule, as long as it can cure the epoxy resin. can be used without any restrictions.
A preferred active ester compound (B) is obtained by esterifying a polyhydric carboxylic acid and a compound having a phenolic hydroxyl group, or by esterifying a polyhydric phenol and a carboxylic acid.
A polyvalent carboxylic acid is a carboxylic acid having two or more carboxyl groups, and includes aliphatic carboxylic acids such as adipic acid and sebacic acid, and carboxylic acids obtained by substituting hydrogen atoms of aromatic compounds with two or more carboxyl groups. acids and the like. A polyhydric phenol is a compound having two or more phenolic hydroxyl groups, and examples thereof include aromatic compounds in which hydrogen atoms are substituted with two or more hydroxyl groups.
好ましい活性エステル化合物（Ｂ）の具体例としては、ベンゼン、ナフタレン、ビフェニル、ジフェニルプロパン、ジフェニルメタン、ジフェニルエーテル、ジフェニルスルホン等の芳香環の水素原子の２つ以上をカルボキシル基で置換したものから選ばれる芳香族カルボン酸と、ベンゼン、ナフタレン、ビフェニル、ジフェニルプロパン、ジフェニルメタン、ジフェニルエーテル、ジフェニルスルホン等の芳香環の水素原子の１つを水酸基で置換したフェノール類とが縮合反応によって得られる芳香族エステルが挙げられる。 Specific examples of the preferred active ester compound (B) include aromatics selected from benzene, naphthalene, biphenyl, diphenylpropane, diphenylmethane, diphenylether, diphenylsulfone, etc., in which two or more hydrogen atoms of the aromatic ring are substituted with carboxyl groups. aromatic esters obtained by the condensation reaction of phenols in which one hydrogen atom of the aromatic ring is substituted with a hydroxyl group, such as benzene, naphthalene, biphenyl, diphenylpropane, diphenylmethane, diphenylether, and diphenylsulfone. .
活性エステル化合物（Ｂ）の配合量は、硬化性及び低誘電正接化の観点から、エポキシ樹脂（Ａ）のエポキシ基等量と活性エステル化合物（Ｂ）のエステル基等量のモル比が、０．６～１．４であることが好ましい。 From the viewpoint of curability and low dielectric loss tangent, the amount of the active ester compound (B) is such that the molar ratio of the epoxy group equivalent of the epoxy resin (A) to the ester group equivalent of the active ester compound (B) is 0. .6 to 1.4 is preferred.
硬化促進剤（Ｃ）は、一般式（１）で示されるイミダゾリウムカチオン（Ｄ）と、アニオン（Ｅ）からなるイミダゾリウム塩（Ｓ）を含む。 The curing accelerator (C) contains an imidazolium salt (S) consisting of an imidazolium cation (D) represented by the general formula (1) and an anion (E).
イミダゾリウムカチオン（Ｄ）は、一般式（１）であらわされ、式（１）中、Ｒ１は、水素原子、メチル基、エチル基、プロピル基又はブチル基を表し、Ｒ２及びＲ３は、同一または異なって、メチル基、エチル基、プロピル基又はブチル基を表し、Ｒ４及びＲ５は、同一または異なって、水素原子、メチル基又はエチル基を表す。 The imidazolium cation (D) is represented by the general formula (1), wherein R1 represents a hydrogen atom, a methyl group, an ethyl group, a propyl group or a butyl group, and R2 and R3 are the same or Differently, they represent a methyl group, an ethyl group, a propyl group or a butyl group, and R4 and R5 are the same or different and represent a hydrogen atom, a methyl group or an ethyl group.
イミダゾリウムカチオン（Ｄ）は、エポキシ樹脂組成物の硬化性の観点から、Ｒ１が水素原子のものが特に好ましい。さらにＲ４、Ｒ５は、水素原子が好ましい。 From the viewpoint of curability of the epoxy resin composition, the imidazolium cation (D) is particularly preferably one in which R1 is a hydrogen atom. Furthermore, R4 and R5 are preferably hydrogen atoms.
イミダゾリウムカチオン（Ｄ）の具体例としては、１－エチル－３－メチルイミダゾリウムカチオン、１－プロピル－３－メチルイミダゾリウムカチオン、１－ブチル－３－メチルイミダゾリウムカチオン、１－ブチル－２，３－ジメチルイミダゾリウムカチオン、１，３－ジメチルイミダゾリウムカチオン、１，３－ジエチルイミダゾリウムカチオン、１，２，３－トリメチルイミダゾリウムカチオン、１，２，３，４－テトラメチルイミダゾリウムカチオン、１，３，４－トリメチル－２－エチルイミダゾリウムカチオン、１，３－ジメチル－２，４－ジエチルイミダゾリウムカチオン、１，２－ジメチル－３，４－ジエチルイミダゾリウムカチオン、１－メチル－２，３，４－トリエチルイミダゾリウムカチオン、１，２，３，４－テトラエチルイミダゾリウムカチオン、１，３－ジメチル－２－エチルイミダゾリウムカチオン、１－エチル－２，３－ジメチルイミダゾリウムカチオン、及び１，２，３－トリエチルイミダゾリウムカチオン等が挙げられる。 Specific examples of the imidazolium cation (D) include 1-ethyl-3-methylimidazolium cation, 1-propyl-3-methylimidazolium cation, 1-butyl-3-methylimidazolium cation, 1-butyl-2 ,3-dimethylimidazolium cation, 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, 1,2,3-trimethylimidazolium cation, 1,2,3,4-tetramethylimidazolium cation , 1,3,4-trimethyl-2-ethylimidazolium cation, 1,3-dimethyl-2,4-diethylimidazolium cation, 1,2-dimethyl-3,4-diethylimidazolium cation, 1-methyl- 2,3,4-triethylimidazolium cation, 1,2,3,4-tetraethylimidazolium cation, 1,3-dimethyl-2-ethylimidazolium cation, 1-ethyl-2,3-dimethylimidazolium cation, and 1,2,3-triethylimidazolium cation.
イミダゾリウムカチオン（Ｄ）の製造は、例えば、四級化アミンカチオンのアルキル炭酸塩を使用する反応、および四級化アミンカチオンの水酸化物を使用する反応等により得られる。 The imidazolium cation (D) can be produced, for example, by a reaction using an alkyl carbonate of a quaternary amine cation, a reaction using a hydroxide of a quaternary amine cation, and the like.
アニオン（Ｅ）としては、カルボキシラートアニオン（Ｅ１）、ボレートアニオン、スルホネートアニオンが挙げられる。
カルボキシラートアニオン（Ｅ１）の具体例としては、オクチル酸、フタル酸、イソフタル酸、安息香酸、コハク酸、マレイン酸などからのアニオンが挙げられる。
ボレートアニオンの具体例としては、テトラフェニルボレートなどが挙げられる。
スルホネートアニオンの具体例としては、ｐ－トルエンスルホン酸、メタンスルホン酸などからのアニオンが挙げられる。
これらの中で、カルボキシラートアニオン（Ｅ１）が、硬化性の観点で好ましく、下記一般式（２）で示さる特定のカルボキシラートアニオン（Ｅ２）が、同様の観点でさらに好ましい。Anions (E) include carboxylate anions (E1), borate anions and sulfonate anions.
Specific examples of carboxylate anions (E1) include anions from octylic acid, phthalic acid, isophthalic acid, benzoic acid, succinic acid, maleic acid, and the like.
Specific examples of borate anions include tetraphenylborate.
Specific examples of sulfonate anions include anions from p-toluenesulfonic acid, methanesulfonic acid, and the like.
Among these, the carboxylate anion (E1) is preferable from the viewpoint of curability, and the specific carboxylate anion (E2) represented by the following general formula (2) is more preferable from the same viewpoint.
一般式（２）中、Ｙは、カルボキシル基、水酸基、チオール基、アミド基からなる群より選ばれる基を表わす。Ｒ６、Ｒ７はそれぞれ、水酸基、アミノ基、ニトロ基、カルボキシル基、エーテル基を有してもよい炭素数１～１０の炭化水素基、又は水素原子を示し、Ｒ６、Ｒ７が相互に結合し環を形成しても良い。 In general formula (2), Y represents a group selected from the group consisting of a carboxyl group, a hydroxyl group, a thiol group and an amide group. R6 and R7 each represent a hydrocarbon group having 1 to 10 carbon atoms which may have a hydroxyl group, an amino group, a nitro group, a carboxyl group, an ether group, or a hydrogen atom; may be formed.
式（２）のアニオン（Ｅ２）のＹは、カルボキシル基、水酸基、チオール基、アミド基からなる群より選ばれるが、これにより、式（２）中のカルボキシラートアニオンと官能基Ｙとの２つの官能基が、エポキシ樹脂（Ａ）と活性エステル化合物（Ｂ）の反応を促進させることができるため好ましい。 Y of the anion (E2) of formula (2) is selected from the group consisting of a carboxyl group, a hydroxyl group, a thiol group and an amide group. Two functional groups are preferred because they can promote the reaction between the epoxy resin (A) and the active ester compound (B).
上記の反応機構で反応を促進することができるため、官能基Ｙとしては、カルボキシル基、水酸基、チオール基がより好ましく、さらにカルボキシル基、水酸基が最も好ましい。 The functional group Y is more preferably a carboxyl group, a hydroxyl group, or a thiol group, and most preferably a carboxyl group or a hydroxyl group, because the reaction can be promoted by the above reaction mechanism.
式（２）のアニオン（Ｅ２）のＲ６、Ｒ７は、それぞれ、水酸基、アミノ基、ニトロ基、カルボキシル基、エーテル基を有してもよい炭素数１～１０の炭化水素基、又は水素原子を示し、Ｒ６、Ｒ７が相互に結合し環を形成しても良い。好ましくは、Ｒ６、Ｒ７が相互に結合し環を形成していることで、その環がベンゼン環であることがさらに好ましい。 R6 and R7 of the anion (E2) of formula (2) are each a hydroxyl group, an amino group, a nitro group, a carboxyl group, a hydrocarbon group having 1 to 10 carbon atoms which may have an ether group, or a hydrogen atom. and R6 and R7 may combine to form a ring. Preferably, R6 and R7 are bonded together to form a ring, and the ring is more preferably a benzene ring.
アニオン（Ｅ２）の中で、エポキシ樹脂（Ａ）のエポキシ基と活性エステル化合物（Ｂ）のエステル基の相互作用の強さの観点から、フタル酸、サリチル酸からのアニオンが特に好ましい。 Among the anions (E2), anions from phthalic acid and salicylic acid are particularly preferred from the viewpoint of the strength of interaction between the epoxy group of the epoxy resin (A) and the ester group of the active ester compound (B).
イミダゾリウム塩（Ｓ）の合成方法としては、例えば、前記のイミダゾリウムを有するカチオン（Ｄ）とアニオン（Ｅ）となりうるカルボン酸を一定な比率で反応させる方法が挙げられる。 A method for synthesizing the imidazolium salt (S) includes, for example, a method of reacting a cation (D) having the imidazolium and a carboxylic acid that can be an anion (E) at a constant ratio.
本発明のエポキシ樹脂組成物は、これを硬化することにより、最終的に硬化エポキシ樹脂が得られる。硬化促進剤（Ｃ）の配合量はエポキシ樹脂（Ａ）と活性エステル化合物（Ｂ）の反応性に応じて調整されるが、エポキシ樹脂（Ａ）１００重量部に対して通常１～２５重量部、好ましくは２～２０重量部である。最適な配合量は、要求される硬化特性などに合わせて設定すればよい。 By curing the epoxy resin composition of the present invention, a cured epoxy resin is finally obtained. The amount of the curing accelerator (C) is adjusted according to the reactivity of the epoxy resin (A) and the active ester compound (B), but usually 1 to 25 parts by weight per 100 parts by weight of the epoxy resin (A). , preferably 2 to 20 parts by weight. The optimum compounding amount may be set according to the required curing properties.
本発明のエポキシ樹脂組成物は、さらにシリカ、アルミナなどの無機充填材（Ｈ）を含むことが好ましい。本発明のエポキシ樹脂組成物を電子部品の封止などに用いる場合、得られる半導体装置の耐半田性向上などを目的として、エポキシ樹脂組成物中に配合されるものであり、その種類については、特に制限はなく、一般に封止材料に用いられているものを使用することができる。 The epoxy resin composition of the present invention preferably further contains an inorganic filler (H) such as silica and alumina. When the epoxy resin composition of the present invention is used for encapsulation of electronic parts, etc., it is blended in the epoxy resin composition for the purpose of improving the solder resistance of the resulting semiconductor device. There is no particular limitation, and those commonly used for sealing materials can be used.
本発明のエポキシ樹脂組成物は、さらに他の機能性ある化合物（機能性添加剤）を含むことが好ましい。 The epoxy resin composition of the present invention preferably further contains other functional compounds (functional additives).
機能性添加剤には、例えば、３－グリシジルオキシプロピルトリメトキシシラン、３－メルカプトプロピルトリメトキシシラン、Ｎ－フェニル－３－アミノプロピルトリメトキシシラン、３－ウレイドプロピルトリエトキシシラン及びフェニルトリメトキシシラン、等のアルコキシシラン類やチタネートエステル類及びアルミナートエステル類に代表されるカップリング剤；カーボンブラック等の着色剤；臭素化エポキシ樹脂、酸化アンチモン、水酸化アルミニウム、水酸化マグネシウム、酸化亜鉛及びリン系化合物等の難燃剤；シリコーンオイル及びシリコーンゴム等の低応力成分；カルナバワックス等の天然ワックス、ポリエチレンワックス等の合成ワックス；ステアリン酸やステアリン酸亜鉛等の高級脂肪酸、該高級脂肪酸の金属塩類及びパラフィン等の離型剤；マグネシウム、アルミニウム、チタン及びビスマス系等のイオンキャッチャー、ビスマス酸化防止剤等の各種添加剤；ベンゾオキサジン、シアネートエステル、ビスマレイミドのような耐熱性ＵＰさせる変性化合物が挙げられる。 Functional additives include, for example, 3-glycidyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane and phenyltrimethoxysilane. Coupling agents represented by alkoxysilanes such as , titanate esters and aluminate esters; colorants such as carbon black; brominated epoxy resins, antimony oxide, aluminum hydroxide, magnesium hydroxide, zinc oxide and phosphorus low stress components such as silicone oil and silicone rubber; natural waxes such as carnauba wax, synthetic waxes such as polyethylene wax; higher fatty acids such as stearic acid and zinc stearate, metal salts of the higher fatty acids and Release agents such as paraffin; ion catchers such as magnesium, aluminum, titanium, and bismuth; various additives such as bismuth antioxidants; modified compounds such as benzoxazine, cyanate ester, and bismaleimide that improve heat resistance. .
他の機能性ある化合物は、「総説エポキシ樹脂第一巻」、「総説エポキシ樹脂第一巻」、エポキシ樹脂技術協会、２００３；エクトロニクス実装学会誌、１４、２０４、２０１１；ｊｏｕｒｎａｌ ｏｆ Ａｐｐｌｉｅｄ Ｐｏｌｙｍｅｒ Ｓｃｉｅｎｃｅ，１０９，２０２３－２０２８，２００８；Ｐｏｌｙｍｅｒ Ｐｒｅｐｒｉｎｔｓ，Ｊａｐａｎ，６０，１Ｋ１９，２０１１；ネックワークポリマー，３３，１３０，２０１２；Ｐｏｌｙｍ．Ｉｎｔ．５４，１１０３－１１０９，２００５；Ｊｏｕｒｎａｌ ｏｆ Ａｐｐｌｉｅｄ Ｐｏｌｙｍｅｒ Ｓｃｉｅｎｃｅ，９２，２３７５－２３８６，２００４；ネックワークポリマー，２９，１７５，２００８；高分子論文集，６５，５６２，２００８；高分子論文集，６６（６），２１７，２００９などに記載されている。 Other functional compounds are described in "Review Epoxy Resin Vol. 1", "Review Epoxy Resin Vol. 1", Epoxy Resin Technology Association, 2003; Electronics Mounting Society Journal, 14, 204, 2011; journal of Applied Polymer Science , 109, 2023-2028, 2008; Polymer Preprints, Japan, 60, 1K19, 2011; Neckwork Polymer, 33, 130, 2012; Polym. Int. 54, 1103-1109, 2005; Journal of Applied Polymer Science, 92, 2375-2386, 2004; Neckwork Polymer, 29, 175, 2008; 6), 217, 2009.
本発明のエポキシ樹脂組成物は、上記成分及び、必要に応じて、その他の添加剤等を、ミキサーを用いて常温で均一混合し、さらにロール、ニーダー、コニーダー及び二軸押出機等の混練機を用いて、加熱混練した後、冷却、粉砕することによって得ることができる。また、上記で得たエポキシ樹脂組成物は、紛体である場合、使用にあたっての作業性を向上させるために、プレス等により加圧タブレット化して使用することもできる。 The epoxy resin composition of the present invention is prepared by uniformly mixing the above-mentioned components and, if necessary, other additives, etc., using a mixer at room temperature, followed by kneading machines such as rolls, kneaders, co-kneaders and twin-screw extruders. It can be obtained by heating and kneading using, cooling and pulverizing. In addition, when the epoxy resin composition obtained above is in the form of powder, in order to improve workability in use, it can be used after being pressurized into tablets by a press or the like.
本発明のエポキシ樹脂組成物の用い方としては、例えば、プリント配線基板や半導体素子等の各種の電子部品を封止し、具体例に半導体装置を製造する場合、トランスファーモールド、コンプレッションモールド及びインジェクションモールド等の従来からの成形方法により、硬化成形すればよい。 Examples of how the epoxy resin composition of the present invention is used include, for example, when sealing various electronic components such as printed wiring boards and semiconductor elements and manufacturing semiconductor devices, transfer molding, compression molding and injection molding are used. Curing molding may be performed by a conventional molding method such as.
以下、実施例及び比較例により本発明をさらに説明するが、本発明はこれらに限定されるものではない。以下、特に定めない限り、％は重量％、部は重量部を示す。 EXAMPLES The present invention will be further described below with reference to Examples and Comparative Examples, but the present invention is not limited to these. Hereinafter, unless otherwise specified, % means % by weight, and part means part by weight.
＜イミダゾリウム塩（Ｓ－１）の製造方法＞
攪拌式のオートクレーブに、炭酸ジエチル（東京化成工業株式会社社製）１４１部および溶媒のエタノール５００部を仕込み、この中に１－メチルイミダゾール（東京化成工業株式会社社製）８２部を仕込み、反応温度１３５℃にて８０時間反応させた。これにより、１－エチル－３－メチルイミダゾリウムのエチル炭酸塩（Ｓ－１－１）のエタノール溶液を得た。滴下ロート、および還流管を備え付けたガラス製丸底３つ口フラスコに、フタル酸（東京化成工業株式会社社製）１６６部を徐々に投入し、その後、エバポレータで溶剤を除去することで、１－エチル－３－メチルイミダゾリウム・フタル酸塩（Ｓ－１）を得られた。<Method for producing imidazolium salt (S-1)>
A stirring autoclave was charged with 141 parts of diethyl carbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 500 parts of ethanol as a solvent, and 82 parts of 1-methylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) was charged therein to react. The reaction was carried out at a temperature of 135°C for 80 hours. As a result, an ethanol solution of 1-ethyl-3-methylimidazolium ethyl carbonate (S-1-1) was obtained. 166 parts of phthalic acid (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was gradually added to a glass round-bottomed three-necked flask equipped with a dropping funnel and a reflux tube, and then the solvent was removed with an evaporator. -ethyl-3-methylimidazolium phthalate (S-1) was obtained.
＜イミダゾリウム塩（Ｓ－２）の製造方法＞
イミダゾリウム塩（Ｓ－１）の製造方法の１－メチルイミダゾールの代わりに、１，２ジメチルイミダゾール（東京化成工業株式会社社製）９６部を用いることで、１－エチル－２，３－メチルイミダゾリウム・フタル酸塩（Ｓ－２）を得られた。<Method for producing imidazolium salt (S-2)>
By using 96 parts of 1,2 dimethylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of 1-methylimidazole in the method for producing imidazolium salt (S-1), 1-ethyl-2,3-methyl An imidazolium phthalate (S-2) was obtained.
＜イミダゾリウム塩（Ｓ－３）の製造方法＞
イミダゾリウム塩（Ｓ－１）の製造方法のフタル酸の代わりに、マレイン酸（東京化成工業株式会社社製）１１６部を用いることで、１－エチル－３－メチルイミダゾリウム・マレイン酸塩（Ｓ－３）を得られた。<Method for producing imidazolium salt (S-3)>
Instead of phthalic acid in the method for producing imidazolium salt (S-1), 1-ethyl-3-methylimidazolium maleate ( S-3) was obtained.
＜イミダゾリウム塩（Ｓ－４）の製造方法＞
イミダゾリウム塩（Ｓ－１）の製造方法のフタル酸の代わりに、サリチル酸（東京化成工業株式会社社製）１３８部を用いることで、１－エチル－３－メチルイミダゾリウム・サリチル酸塩（Ｓ－４）を得られた。<Method for producing imidazolium salt (S-4)>
Instead of phthalic acid in the method for producing imidazolium salt (S-1), 1-ethyl-3-methylimidazolium salicylate (S- 4) was obtained.
＜イミダゾリウム塩（Ｓ－５）の製造方法＞
イミダゾリウム塩（Ｓ－１）の製造方法のフタル酸の代わりに、コハク酸（東京化成工業株式会社社製）１１８部を用いることで、１－エチル－３－メチルイミダゾリウム・コハク酸塩（Ｓ－５）を得られた。<Method for producing imidazolium salt (S-5)>
Instead of phthalic acid in the method for producing imidazolium salt (S-1), 1-ethyl-3-methylimidazolium succinate ( S-5) was obtained.
＜イミダゾリウム塩（Ｓ－６）の製造方法＞
イミダゾリウム塩（Ｓ－１）の製造方法のフタル酸の代わりに、ｐ－トルエンスルホン酸（東京化成工業株式会社社製）１７２部を用いることで、１－エチル－３－メチルイミダゾリウム・ｐ－トルエンスルホン酸塩（Ｓ－６）を得られた。<Method for producing imidazolium salt (S-6)>
Instead of phthalic acid in the method for producing imidazolium salt (S-1), 1-ethyl-3-methylimidazolium p -toluenesulfonate (S-6) was obtained.
＜イミダゾリウム塩（Ｓ－７）の製造方法＞
１－エチル－３－メチルイミダゾリウム・クロライド（東京化成工業株式会社社製）１４６部をメタノール５００部に溶かした溶液を、テトラフェニルボレート・ナトリウム（東京化成工業株式会社社製）３４２部をメタノール１０００部に溶かした溶液中に撹拌しながら、滴下することで沈殿物を生成させた。その沈殿物を取り出し、減圧乾燥機で溶剤を除去することで、１－エチル－３－メチルイミダゾリウム・テトラフェニルボレート（Ｓ－７）を得られた。<Method for producing imidazolium salt (S-7)>
A solution of 146 parts of 1-ethyl-3-methylimidazolium chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 500 parts of methanol, sodium tetraphenylborate (manufactured by Tokyo Chemical Industry Co., Ltd.) 342 parts of methanol A precipitate was generated by adding dropwise to a solution dissolved in 1000 parts while stirring. The precipitate was taken out and the solvent was removed with a vacuum dryer to obtain 1-ethyl-3-methylimidazolium tetraphenylborate (S-7).
＜活性エステル化合物（Ｂ－１）の製造方法＞
滴下ロート、および還流管を備え付けたガラス製丸底３つ口フラスコに、イソフタル酸（東京化成工業株式会社社製）３３部と、１―ナフトール（東京化成工業株式会社社製）５８部、および無水酢酸（東京化成工業株式会社社製）４９部を入れ、窒素雰囲気化で１４５℃５時間反応させることで、１―ナフトールのアセチル化を行った。さらに、２００～２５０℃で反応することで、脱酢酸しながら、１―ナフトールのエステル化反応を行った。得られた生成物をメタノールで十分洗浄し、５０℃で減圧乾燥することで１―ナフトールと、イソフタル酸の活性エステル化合物（Ｂ－１）が得られた。<Method for producing active ester compound (B-1)>
A dropping funnel and a glass round-bottom three-necked flask equipped with a reflux tube are charged with 33 parts of isophthalic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 58 parts of 1-naphthol (manufactured by Tokyo Chemical Industry Co., Ltd.), and 1-Naphthol was acetylated by adding 49 parts of acetic anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and reacting at 145° C. for 5 hours in a nitrogen atmosphere. Further, the esterification reaction of 1-naphthol was carried out while deacetic acid was reacted at 200 to 250°C. The resulting product was thoroughly washed with methanol and dried under reduced pressure at 50° C. to obtain 1-naphthol and an active ester compound (B-1) of isophthalic acid.
実施例１
エポキシ樹脂：日本化薬（株）製、商品名ＮＣ３０００（軟化点５８℃、エポキシ当量２７３）１００部；活性エステル化合物（Ｂ－１）６５部；イミダゾリウム塩（Ｓ－１）をエポキシ樹脂硬化促進剤として７部；１重量％のシランカップリング剤で処理した溶融シリカ粉末１０００部、カルナバワックス１．５部およびカーボンブラック１部を均一に粉砕混合後、 １００℃の熱ロールを用いて１０分間溶融混練し、冷却後粉砕してエポキシ樹脂組成物（封止材）を得た。得られたエポキシ樹脂組成物を、以下の方法で評価した。結果を表１に示す。Example 1
Epoxy resin: Nippon Kayaku Co., Ltd., trade name NC3000 (softening point 58 ° C., epoxy equivalent 273) 100 parts; active ester compound (B-1) 65 parts; imidazolium salt (S-1) epoxy resin curing 7 parts as an accelerator; 1000 parts of fused silica powder treated with 1% by weight of silane coupling agent, 1.5 parts of carnauba wax and 1 part of carbon black were uniformly pulverized and mixed, then 10 using a hot roll at 100°C. The mixture was melt-kneaded for 1 minute, cooled and pulverized to obtain an epoxy resin composition (sealing material). The obtained epoxy resin composition was evaluated by the following methods. Table 1 shows the results.
＜性能評価＞
＜ゲルタイム＞
キュラストメーター７型（株式会社エー・アンド・デイ製、商品名）を使用して、温度１７５℃、樹脂用ダイスＰ－２００および振幅角度±１／４°の条件で、それぞれの上記エポキシ樹脂組成物について硬化トルクを測定し、硬化トルクの立ち上がる点をゲルタイム（単位は秒）とした。<Performance evaluation>
<Gel Time>
Using a Curastometer Model 7 (manufactured by A&D Co., Ltd., trade name), under the conditions of a temperature of 175 ° C., a resin die P-200 and an amplitude angle of ± 1/4 °, each of the above epoxy resins The curing torque was measured for the composition, and the gel time (in seconds) was defined as the point at which the curing torque rises.
＜硬化性（硬化トルク）＞
上記のキュラストメーターでの測定で、測定開始から３００秒後の硬化トルクの値（単位はｋｇｆ・ｃｍ）を硬化性（脱型時の強度および硬度）の指標とした。<Curability (curing torque)>
In the measurement with the above curastometer, the value of curing torque (unit: kgf·cm) 300 seconds after the start of measurement was used as an index of curability (strength and hardness at demolding).
＜遊離塩素イオンの測定＞
上記エポキシ樹脂組成物の内、エポキシ樹脂と活性エステル化合物（Ｂ－１）とエポキシ樹脂硬化促進剤のみを１０分間、１３０℃で溶融混練し、１７５℃で３０分硬化させた組成物１０部を超純水１００部と一緒にオートクレーブ中で１３０℃、２０時間加熱した後の液を、イオンクロマトグラフを用いて塩素含量を測定した。<Measurement of free chlorine ions>
Of the above epoxy resin composition, only the epoxy resin, active ester compound (B-1), and epoxy resin curing accelerator were melt-kneaded for 10 minutes at 130°C and cured at 175°C for 30 minutes. After heating with 100 parts of ultrapure water in an autoclave at 130° C. for 20 hours, the chlorine content of the liquid was measured using ion chromatography.
実施例２～７、比較例１
表２のように、硬化促進剤を変えて、実施例１と同様にしてエポキシ樹脂組成物（封止材）を得て、実施例１と同様にして評価した。結果を表１に示す。なお、比較例の硬化促進剤には、４－ジメチルアミノピリジンを用いた。Examples 2 to 7, Comparative Example 1
As shown in Table 2, an epoxy resin composition (sealant) was obtained in the same manner as in Example 1 by changing the curing accelerator, and evaluated in the same manner as in Example 1. Table 1 shows the results. 4-dimethylaminopyridine was used as the curing accelerator in Comparative Examples.
表１から明らかなように、本発明の実施例１～７のエポキシ樹脂組成物（封止材）は、硬化性は比較例と比べてそれ以上もしくは同等レベルであり、遊離塩素イオンが極めて少なく電子部品用デバイスに用いた時に信頼性が高くなり、最適であることが分かる。 As is clear from Table 1, the epoxy resin compositions (sealing materials) of Examples 1 to 7 of the present invention have curability higher than or equal to that of Comparative Examples, and free chlorine ions are extremely low. It can be seen that the reliability is high when used in devices for electronic parts, and that it is optimal.
本発明のエポキシ樹脂組成物は、電子部品用のデバイスにおいて、高周波通信でのエネルギー損失を抑制でき、またデバイスの信頼性を高めることができるため、プリント配線板や半導体などの電子部品用のエポキシ樹脂系封止剤の製造に好適である。
INDUSTRIAL APPLICABILITY The epoxy resin composition of the present invention can suppress energy loss in high-frequency communication and improve device reliability in devices for electronic parts. Suitable for the production of resin-based sealants.
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| JP2014097930A (en) * | 2012-11-13 | 2014-05-29 | San Apro Kk | Heat base generator |
| JP5915610B2 (en) * | 2013-09-18 | 2016-05-11 | 味の素株式会社 | Resin composition |
| JP6648425B2 (en) * | 2015-06-22 | 2020-02-14 | 味の素株式会社 | Resin composition |
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| JP2011184679A (en) | 2010-02-15 | 2011-09-22 | Hitachi Chem Co Ltd | Insulating resin, wiring board and method for manufacturing wiring board |
| WO2012136273A1 (en) | 2011-04-08 | 2012-10-11 | Basf Se | Hyperbranched polymers for modifying the toughness of anionically cured epoxy resin systems |
| CN102964778A (en) | 2012-12-06 | 2013-03-13 | 西北师范大学 | Preparation method of ionic liquid-epoxy resin composite material |
| JP2015209492A (en) | 2014-04-25 | 2015-11-24 | 旭化成イーマテリアルズ株式会社 | Liquid curing agent, curable resin composition, fine chemical, and composition |
| CN107090294A (en) | 2017-06-01 | 2017-08-25 | 滨州学院 | A kind of room temperature curing epoxy expansive soil modifier and its preparation and application |
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