TW201540740A - 經聚矽氧改質之環氧樹脂及包含該環氧樹脂之組合物、以及其硬化物 - Google Patents
經聚矽氧改質之環氧樹脂及包含該環氧樹脂之組合物、以及其硬化物 Download PDFInfo
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- TW201540740A TW201540740A TW104110552A TW104110552A TW201540740A TW 201540740 A TW201540740 A TW 201540740A TW 104110552 A TW104110552 A TW 104110552A TW 104110552 A TW104110552 A TW 104110552A TW 201540740 A TW201540740 A TW 201540740A
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- Prior art keywords
- epoxy resin
- group
- following formula
- acid
- anhydride
- Prior art date
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- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 76
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 75
- 239000000203 mixture Substances 0.000 title claims abstract description 38
- 125000000962 organic group Chemical group 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims description 40
- -1 polyoxymethylene Polymers 0.000 claims description 31
- 229920005989 resin Polymers 0.000 claims description 26
- 239000011347 resin Substances 0.000 claims description 26
- 125000004432 carbon atom Chemical group C* 0.000 claims description 24
- 150000008065 acid anhydrides Chemical class 0.000 claims description 23
- 239000000047 product Substances 0.000 claims description 23
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 11
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 10
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 9
- 239000004848 polyfunctional curative Substances 0.000 claims description 9
- 230000001590 oxidative effect Effects 0.000 claims description 8
- 238000007259 addition reaction Methods 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 3
- 229920006324 polyoxymethylene Polymers 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 4
- 150000002430 hydrocarbons Chemical group 0.000 abstract description 19
- 239000004593 Epoxy Substances 0.000 abstract description 10
- 230000035699 permeability Effects 0.000 abstract description 8
- UMRZSTCPUPJPOJ-KNVOCYPGSA-N norbornane Chemical compound C1C[C@H]2CC[C@@H]1C2 UMRZSTCPUPJPOJ-KNVOCYPGSA-N 0.000 abstract 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 36
- 238000006243 chemical reaction Methods 0.000 description 29
- 238000000034 method Methods 0.000 description 27
- 239000002253 acid Substances 0.000 description 19
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 238000005227 gel permeation chromatography Methods 0.000 description 13
- 239000003960 organic solvent Substances 0.000 description 12
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 11
- 239000007789 gas Substances 0.000 description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 150000001336 alkenes Chemical class 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000003963 antioxidant agent Substances 0.000 description 8
- 230000003078 antioxidant effect Effects 0.000 description 8
- 235000006708 antioxidants Nutrition 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 125000003700 epoxy group Chemical group 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000012044 organic layer Substances 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- FWHUTKPMCKSUCV-UHFFFAOYSA-N 1,3-dioxo-3a,4,5,6,7,7a-hexahydro-2-benzofuran-5-carboxylic acid Chemical compound C1C(C(=O)O)CCC2C(=O)OC(=O)C12 FWHUTKPMCKSUCV-UHFFFAOYSA-N 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 238000005481 NMR spectroscopy Methods 0.000 description 7
- 238000006735 epoxidation reaction Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 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 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- OTLDLKLSNZMTTA-UHFFFAOYSA-N octahydro-1h-4,7-methanoindene-1,5-diyldimethanol Chemical compound C1C2C3C(CO)CCC3C1C(CO)C2 OTLDLKLSNZMTTA-UHFFFAOYSA-N 0.000 description 6
- 239000010452 phosphate Substances 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 150000007514 bases Chemical class 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229920005862 polyol Polymers 0.000 description 5
- 150000003077 polyols Chemical class 0.000 description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- RGAHHPQKNPTZEY-UHFFFAOYSA-N 2-ethyl-4-methylhexane-1,1-diol Chemical compound CCC(C)CC(CC)C(O)O RGAHHPQKNPTZEY-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 150000008064 anhydrides Chemical class 0.000 description 4
- 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 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical group CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 4
- 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 4
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 4
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000011342 resin composition Substances 0.000 description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 3
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 235000011054 acetic acid Nutrition 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000007853 buffer solution Substances 0.000 description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 3
- OZEHOHQZIRILDX-UHFFFAOYSA-N ctk1b7797 Chemical compound O=C1OC(=O)C2C1C1(C)CC2CC1 OZEHOHQZIRILDX-UHFFFAOYSA-N 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
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- 229910000403 monosodium phosphate Inorganic materials 0.000 description 3
- 235000019799 monosodium phosphate Nutrition 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
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- 150000004965 peroxy acids Chemical class 0.000 description 3
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- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 3
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- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 2
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 2
- LULAYUGMBFYYEX-UHFFFAOYSA-N 3-chlorobenzoic acid Chemical compound OC(=O)C1=CC=CC(Cl)=C1 LULAYUGMBFYYEX-UHFFFAOYSA-N 0.000 description 2
- 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 2
- LQOPXMZSGSTGMF-UHFFFAOYSA-N 6004-79-1 Chemical compound C1CC2C3C(=O)OC(=O)C3C1C2 LQOPXMZSGSTGMF-UHFFFAOYSA-N 0.000 description 2
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- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
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- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
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- YJFXHWKCPJJECB-UHFFFAOYSA-N anthracene-9,10-dione sulfane Chemical compound S.O=C1c2ccccc2C(=O)c2ccccc12 YJFXHWKCPJJECB-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
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- 238000000354 decomposition reaction Methods 0.000 description 2
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- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
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- 238000005984 hydrogenation reaction Methods 0.000 description 2
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
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Abstract
本發明之目的在於提供一種獲得氣體透過性低且強度優異之硬化物之經聚矽氧改質之環氧樹脂及其組合物、以及使該組合物硬化而獲得之環氧樹脂硬化物。
一種環氧樹脂,其由下述式(1)表示。
□(R1表示碳數1~6之烴基,X表示具有降□烷環氧結構之有機基或碳數1~6之烴基,n表示1~3之整數。於式中複數存在之R1、X分別可相同亦可不同。其中,複數存在之X中之2個以上為具有降□烷環氧結構之有機基)
Description
作為光半導體元件密封用樹脂組合物,多使用如下之組合物,其包含:接著性或機械強度優異之雙酚A型環氧樹脂;無UV(ultraviolet,紫外線)吸收之環氧樹脂,例如氫化雙酚A型環氧樹脂或脂環式環氧樹脂;以及硬化劑及硬化觸媒。然而,伴隨著LED(light emitting diode,發光二極體)元件之亮度及輸出增高,因來自LED元件之光、熱等而引起變色及龜裂之問題。
作為解決該等問題者,已知有獲得無UV吸收且具有可撓性之硬化物的於聚矽氧樹脂中導入環氧基而成之樹脂,例如已知有含有1個以上之縮水甘油基、環氧基環己基等含有環狀醚之基的聚矽氧樹脂(專利文獻1)或環氧基烷氧基矽烷與矽烷醇之反應產物(專利文獻2)、及併用經脂環式環氧改質之聚矽氧樹脂及脂環式環氧樹脂者(專利文獻3)等。然而,由於聚矽氧樹脂與環氧樹脂相比氣體透過性非常高,故而隨著聚矽氧含量增加,變得難以用於必需低氣體透過性之用途。因此,揭示有加成反應型苯基系聚矽氧樹脂組合物作為具有低氣體透過性之樹脂組合物(專利文獻4),但於低氣體透過性、接著性方面仍未充分滿足。
[專利文獻1]日本專利特開2008-45088號公報
[專利文獻2]日本專利特開平7-97433號公報
[專利文獻3]日本專利特開2006-282988號公報
[專利文獻4]日本專利特開2002-265787號公報
本發明係鑒於上述情況而完成者,其目的在於提供一種獲得氣體透過性低且強度優異之硬化物之經聚矽氧改質之環氧樹脂組合物、及使該組合物硬化而獲得之環氧樹脂硬化物。
本發明者等人鑒於如上所述之實際情況,進行努力研究,結果完成本發明。即,本發明係關於下述(1)~(10)。
(1)一種經聚矽氧改質之環氧樹脂,其由下述式(1)表示:
(式中,R1表示碳數1~6之烴基,X表示下述式(2)所表示之有機基或碳數1~6之烴基,n表示1~3之整數;於式中複數存在之R1、X分別可相同亦可不同;其中,複數存在之X中之2個以上為下述式(2)所表示之有機基)
(式中,R2表示碳數2~3之伸烷基,m為整數且表示0~2)。
(2)如(1)之經聚矽氧改質之環氧樹脂,其係下述式(3)所記載之化
合物與下述式(4)所記載之化合物之加成反應產物,
(式中,R1、n分別表示與上述相同之含義,Y表示氫原子或碳數1~6之烴基;於式中複數存在之R1、Y分別可相同亦可不同;其中,複數存在之Y中之2個以上為氫原子)
(式中,m分別表示與上述相同之含義,R3表示單鍵或亞甲基)。
(3)如(1)之經聚矽氧改質之環氧樹脂,其係藉由將下述式(5)之多元烯烴系化合物氧化而獲得,
(式中,R1、n分別表示與上述相同之含義,Z表示下述式(6)所表示之有機基或碳數1~6之烴基;於式中複數存在之R1、Z分別可相同亦可不同;其中,複數存在之Z中之2個以上為下述式(6)所表示之有機基)
[化6]
(式中,R2、m分別表示與上述相同之含義)。
(4)如技術方案1至3中任一項之經聚矽氧改質之環氧樹脂,其中n為2。
(5)一種環氧樹脂組合物,其含有如技術方案1至4中任一項之(A)經聚矽氧改質之環氧樹脂及(B)環氧樹脂硬化劑。
(6)一種環氧樹脂組合物,其含有如技術方案1至4中任一項之(A)經聚矽氧改質之環氧樹脂及(C)環氧樹脂硬化促進劑。
(7)一種環氧樹脂組合物,其特徵在於:如技術方案5之環氧樹脂硬化劑選自胺系硬化劑、酚系硬化劑、酸酐系硬化劑、及多元羧酸樹脂之至少任一種。
(8)一種硬化物,其係使如技術方案5至7中任一項之環氧樹脂組合物硬化而成。
圖1係於實施例1中獲得之經聚矽氧改質之環氧樹脂(A-1)的1H-NMR(Nuclear Magnetic Resonance,核磁共振)圖譜。
圖2係於實施例1中獲得之經聚矽氧改質之環氧樹脂(A-1)的藉由GPC(Gel Permeation Chromatography,凝膠滲透層析術)(B)測定所得之GPC圖。
本發明之經聚矽氧改質之環氧樹脂係下述通式(1)所表示的環狀之經聚矽氧改質之環氧樹脂。
[化7]
式(1)中,R1表示碳數1~6之烴基,X表示下述式(2)所表示之有機基或碳數1~6之烴基,n表示1~3之整數。於式中複數存在之R1、X分別可相同亦可不同。其中,複數存在之X中之2個以上為下述式(2)所表示之有機基。
R1為碳數1~6之烴基,作為具體例,可列舉甲基、乙基、丙基、丁基、戊基、己基、苯基,但就硬化物之耐熱透明性之觀點而言,較佳為甲基、苯基,其中尤佳為甲基。
X為下述式(2)所表示之有機基或碳數1~6之烴基,作為碳數1~6之烴基之具體例,可列舉甲基、乙基、丙基、丁基、戊基、己基、苯基,但就硬化物之耐熱透明性之觀點而言,較佳為甲基、苯基,其中尤佳為甲基。
n為1~3之整數,其中較佳為2。
式(2)中,R2表示碳數2~3之伸烷基,其中,就硬化物之耐熱透明性之觀點而言,較佳為伸乙基、伸丙基。
m為0~2之整數,較佳為1。
本發明之經聚矽氧改質之環氧樹脂可藉由將下述式(3)所表示之環狀氫矽氧烷化合物、與下述式(4)所表示之含有烯基及環氧基之化合物進行加成反應而獲得。
式(3)中,R1、n分別表示與上述相同之含義,Y表示氫原子或碳數1~6之烴基。於式中複數存在之R1、Y分別可相同亦可不同。其中,複數存在之Y中之2個以上為氫原子。
Y為氫原子或碳數1~6之烴基,作為碳數1~6之烴基之具體例,可列舉甲基、乙基、丙基、丁基、戊基、己基、苯基,但就硬化物之耐熱透明性之觀點而言,較佳為甲基、苯基,其中尤佳為甲基。其中,複數存在之Y中之2個以上為氫原子,較佳為3~4個為氫原子。
式(4)中,m分別表示與上述相同之含義,R3表示單鍵或亞甲基,其中較佳為單鍵。
式(4)所表示之化合物可藉由將下述式(7)所表示之化合物進行氧化環氧化而獲得。
式(7)中,m、R3表示與上述相同之含義。
作為氧化環氧化之方法,可列舉藉由過乙酸等過酸進行氧化之方法、藉由過氧化氫水進行氧化之方法、藉由空氣(氧氣)進行氧化之
方法等,但並不限於該等。
作為藉由過酸之環氧化之方法,具體可列舉日本專利特開2006-52187號公報中所記載之方法等。作為可使用之過酸,例如可列舉甲酸、乙酸、丙酸、順丁烯二酸、苯甲酸、間氯苯甲酸、鄰苯二甲酸等有機酸及其等之酸酐。於該等中,就與過氧化氫反應而生成有機過酸之效率、反應溫度、操作之簡便性、經濟性等觀點而言,較佳為使用甲酸、乙酸、鄰苯二甲酸酐,尤其就反應操作之簡便性之觀點而言,更佳為使用甲酸或乙酸。
藉由過氧化氫水之環氧化之方法可適合為各種方法,具體可適合為如於日本專利特開昭59-108793號公報、日本專利特開昭62-234550號公報、日本專利特開平5-213919號公報、日本專利特開平11-349579號公報、日本專利特公平1-33471號公報、日本專利特開2001-17864號公報、日本專利特公平3-57102號公報等中列舉之方法。
除此以外,亦可應用非專利文獻1(James V.Crivello and Ramesh Narayan,Novel Epoxynorbornane Monomers.1.Synthesis and Characterization,Macro molecules 1996,29卷,433~438頁)中所記載之方法。具體而言,可使用過硫酸氫鉀(oxone),將烯基進行環氧化而獲得。
獲得上述式(4)所表示之化合物時之較佳之方法係將作為其前驅物之上述式(7)所表示之化合物、聚酸類及四級銨鹽,於有機溶劑中或於無溶劑下以式(7)所表示之化合物及式(4)所表示之單環氧化合物與過氧化氫水之兩層進行反應。
於氧化環氧化中使用之聚酸類只要為具有聚酸結構之化合物則無特別限制,較佳為包含鎢或鉬之聚酸類,進而較佳為包含鎢之聚酸類,尤佳為鎢酸鹽類。
作為聚酸類中所包含之具體之聚酸及聚酸鹽,可列舉選自鎢酸、12-磷鎢酸、12-硼鎢酸、18-磷鎢酸及12-矽鎢酸等中之鎢系之酸、選自鉬酸及磷鉬酸等中之鉬系之酸、以及其等之鹽等。
作為該等鹽之抗衡陽離子,可列舉銨離子、鹼土金屬離子、鹼金屬離子等。
具體可列舉鈣離子、鎂離子等鹼土金屬離子、鈉、鉀、銫等鹼金屬離子等,但並不限定於該等。作為尤佳之抗衡陽離子,為鈉離子、鉀離子、鈣離子、銨離子。
聚酸類之使用量相對於烯烴系系化合物中之烯基1莫耳(官能基當量),以金屬元素換算(若為tungten acid則為鎢原子之莫耳數,若為鉬酸則為鉬原子之莫耳數)為1.0~40毫莫耳,較佳為2.0~30毫莫耳,進而較佳為2.5~25毫莫耳。
作為四級銨鹽,可較佳地使用總碳數為10以上、較佳為25~100、更佳為25~55之四級銨鹽,尤佳為其烷基鏈全部為脂肪族鏈者。
具體可列舉三癸基甲基銨鹽、二月桂基二甲基銨鹽、三辛基甲基銨鹽、三烷基甲基(烷基為辛基之化合物與烷基為癸基之化合物之混合型)銨鹽、三-十六烷基甲基銨鹽、三甲基十八烷基銨鹽、四戊基銨鹽、十六烷基三甲基銨鹽、苄基三丁基銨鹽、二-十六烷基二甲基銨鹽、三-十六烷基甲基銨鹽、二硬化牛油烷基二甲基銨鹽等,但並不限定於該等。
又,該等鹽之陰離子種使用羧酸根離子。作為羧酸根離子,較佳為乙酸根離子、碳酸根離子、甲酸根離子。又,尤佳為乙酸根離子。
若四級銨鹽之碳數超過100,則有疏水性變得過強而對有機層之溶解性變差之情形。另一方面,若四級銨鹽之碳數未達10,則有親水
性變強而同樣地對有機層之相溶性變差之情形。
於四級銨鹽中一般殘存鹵素。於本發明中,尤其為1質量%以下,更佳為1000ppm以下,進而較佳為700ppm以下。於總鹵素量超過1質量%之情形時,於產物中大量殘存鹵素,故而不佳。
鎢酸類與四級銨之羧酸鹽之使用量較佳為所使用之鎢酸類之價數倍之0.01~0.8倍當量、或1.1~10倍當量。更佳為0.05~0.7倍當量、或1.2~6.0倍當量,進而較佳為0.05~0.5倍當量、或1.3~4.5倍當量。
例如,若為鎢酸則以H2WO4計為2價,故而相對於鎢酸1莫耳,四級銨之羧酸鹽較佳為0.02~1.6莫耳、或2.2~20莫耳之範圍。又,若為磷鎢酸則為3價,故而同樣較佳為0.03~2.4莫耳、或3.3~30莫耳,若為矽鎢酸則為4價,故而較佳為0.04~3.2莫耳、或4.4~40莫耳。
於四級銨之羧酸鹽之量低於鎢酸類之價數倍之1.1倍當量的情形時,會產生環氧化反應難以進行(視情形,反應之進行會變快)、且容易出現副產物之問題。於多於10倍當量之情形時,不僅過剩之四級銨之羧酸鹽之處理較為麻煩,而且存在抑制反應之作用,從而不佳。
將羧酸根離子作為陰離子之四級銨鹽可使用市售品,亦可例如藉由下述等方法而製造:藉由金屬氫氧化物或離子交換樹脂對原料四級銨鹽進行處理,將其轉換為氫氧化四級銨,進而與各種羧酸反應。作為原料四級銨鹽,可列舉四級銨之鹵化物或各種金屬鹽等。又,若存在較佳之氫氧化四級銨,則亦可使用其。
作為緩衝液,可使用任一種,但於本反應中,較佳為使用磷酸鹽水溶液。作為其pH值,較佳為pH值被調整為2~10之間,更佳為pH值為3~9。於pH值未達2之情形時,容易進行環氧基之水解反應、聚合反應。又,於pH值超過10之情形時,會產生反應變得極其慢而反應時間過長之問題。
尤其是於本發明中溶解作為觸媒之鎢酸類時,較佳為以pH值成為2~9之間之方式進行調整。
緩衝液之使用方法例如可列舉如下方法:於作為較佳之緩衝液之磷酸-磷酸鹽水溶液之情形時,對過氧化氫使用0.1~10莫耳%當量之磷酸(或磷酸二氫鈉等磷酸鹽),並藉由鹼性化合物(例如氫氧化鈉、氫氧化鉀、碳酸鈉、碳酸氫鈉、碳酸鉀等)進行pH值調整。此處,較佳為以pH值於添加過氧化氫時成為上述pH值之方式進行添加。又,亦可使用磷酸二氫鈉或磷酸氫二鈉等進行調整。較佳之磷酸鹽之濃度為0.1~60質量%,較佳為5~45質量%。
又,於本反應中,亦可不使用緩衝液,不進行pH值調整,而直接添加磷酸氫二鈉、磷酸二氫鈉、磷酸鈉或三聚磷酸鈉等(或其水合物)磷酸鹽。於步驟簡化之意義方面,尤佳為無pH值調整之繁瑣而直接添加。此情形時之磷酸鹽之使用量相對於過氧化氫而通常為0.1~5莫耳%當量,較佳為0.2~4莫耳%當量,更佳為0.3~3莫耳%當量。此時,若相對於過氧化氫而超過5莫耳%當量則必須進行pH值調整,於未達0.1莫耳%當量之情形時,會產生容易進行所生成之環氧樹脂之水解、或反應變慢等不良情況。
作為本反應中所使用之過氧化氫,就其操作之簡便性而言,較佳為過氧化氫濃度為10~40質量%之濃度之水溶液。於濃度超過40質量%之情形時,操作變難,除此以外,亦容易進行所生成之環氧樹脂之分解反應,故而不佳。
本反應亦可使用有機溶劑。作為進行使用之情形時之有機溶劑之量,相對於作為反應基質之烯烴系化合物1,以質量比計為0.3~10,較佳為0.3~5,更佳為0.5~2.5。於以質量比計超過10之情形時,反應之進行變得極其慢,故而不佳。作為可使用之有機溶劑之具體例,可列舉己烷、環己烷、庚烷等烷烴類、甲苯、二甲苯等芳香族
烴化合物、甲醇、乙醇、異丙醇、丁醇、己醇、環己醇等醇類。又,視情形,亦可使用甲基乙基酮、甲基異丁基酮、環戊酮、環己酮等酮類、二乙醚、四氫呋喃、二烷等醚類、乙酸乙酯、乙酸丁酯、甲酸甲酯等酯合物、乙腈等腈化合物等。
作為具體之反應操作方法,例如於藉由分批式之反應釜進行反應時,添加烯烴系化合物、過氧化氫(水溶液)、聚酸類(觸媒)、緩衝液、四級銨鹽及有機溶劑,並以兩層進行攪拌。對攪拌速度並無特別指定。由於在添加過氧化氫時多數情況下會發熱,故而亦可為於添加各成分後緩緩地添加過氧化氫之方法。
反應溫度雖無特別限定,但較佳為0~90℃,進而較佳為0~75℃,尤佳為15℃~60℃。於反應溫度過高之情形時,容易進行水解反應,若反應溫度較低則反應速度變得極其慢。
又,反應時間雖亦取決於反應溫度、觸媒量等,但就工業生產之觀點而言,長時間之反應會消耗極多之能量,故而不佳。作為較佳之範圍為1~48小時,較佳為3~36小時,進而較佳為4~24小時。
反應結束後,進行過剩之過氧化氫之驟冷處理。驟冷處理較佳為使用鹼性化合物而進行。又,亦較佳為併用還原劑與鹼性化合物。作為較佳之處理方法,可列舉於藉由鹼性化合物將pH值中和調整為6~12後,使用還原劑將殘存之過氧化氫驟冷之方法。於pH值未達6之情形時,還原過剩之過氧化氫時之發熱較大,而有可能產生分解物。
作為還原劑,可列舉亞硫酸鈉、硫代硫酸鈉、肼、草酸、維生素C等。作為還原劑之使用量,相對於過剩量之過氧化氫之莫耳數,通常為0.01~20倍莫耳,更佳為0.05~10倍莫耳,進而較佳為0.05~3倍莫耳。
作為鹼性化合物,可列舉氫氧化鈉、氫氧化鉀、氫氧化鎂、氫氧化鈣等金屬氫氧化物、碳酸鈉、碳酸鉀等金屬碳酸鹽、磷酸鈉、磷
酸氫鈉等磷酸鹽、離子交換樹脂、氧化鋁等鹼性固體。
作為其使用量,若為溶解於水、或有機溶劑(例如甲苯、二甲苯等芳香族烴、甲基異丁基酮、甲基乙基酮等酮類、環己烷、庚烷、辛烷等烴、甲醇、乙醇、異丙醇等醇類等各種溶劑)者,則其使用量相對於過剩量之過氧化氫之莫耳數,通常為0.01~20倍莫耳,更佳為0.05~10倍莫耳,進而較佳為0.05~3倍莫耳。其等可作為水、或上述有機溶劑之溶液添加亦能夠以單一成分添加。
於使用不溶解於水或有機溶劑之固體鹼之情形時,較佳為使用相對於殘存於系統中之過氧化氫之量以質量比計為1~1000倍之量。更佳為10~500倍,進而較佳為10~300倍。於使用不溶解於水或有機溶劑之固體鹼之情形時,亦可於下文記載之水層與有機層分離後進行處理。
於過氧化氫之驟冷後(或進行驟冷前),此時,於有機層與水層未分離、或未使用有機溶劑之情形時,添加上述有機溶劑進行操作,自水層進行反應產物之萃取。此時所使用之有機溶劑相對於原料烯烴系化合物以質量比計為0.5~10倍,較佳為0.5~5倍。於視需要重複進行複數次該操作後,分離有機層,並視需要對該有機層進行水洗而精製。
所獲得之有機層視需要藉由離子交換樹脂或金屬氧化物(尤佳為矽膠或氧化鋁等)、活性碳(其中尤佳為化學活化活性碳)、複合金屬鹽(其中尤佳為鹼性複合金屬鹽)、黏度礦物(其中尤佳為蒙脫石等層狀黏度礦物)等去除雜質,進而進行水洗及過濾等後,將溶劑蒸餾去除,而獲得目標之環氧化合物。視情形亦可進而藉由管柱層析法或蒸餾而精製。
於上述式(7)所表示之化合物之氧化環氧化時,根據反應條件,有混合生成上述式(4)所表示之化合物、與下述式(8)所表示之化合物
之情形。
式(8)中,m、R3表示與上述相同之含義。
於藉由將上述式(3)所表示之化合物與上述式(4)所表示之化合物進行加成反應而獲得本發明之上述式(1)所表示之化合物之情形時,亦可於上述式(4)所表示之化合物中混合上述式(8)所表示之化合物。
於在上述式(4)所表示之化合物中混合有上述式(8)所表示之化合物之情形時,上述式(8)所表示之化合物於混合物中較佳為15質量%以下,更佳為10質量%以下。若包含多於15質量%,則存在硬化物之耐熱透明性較差之可能性。
上述式(3)所表示之化合物與上述式(4)所表示之化合物(於混合之情形時有上述式(8)所表示之化合物)之加成反應可於鉑觸媒存在下,藉由矽氫化反應而製造。
本發明之經聚矽氧改質之環氧樹脂亦可藉由將作為其前驅物之下述式(5)所表示之烯烴系化合物氧化而獲得。
式(5)中,R1、n分別表示與上述相同之含義,Z表示下述式(6)所表示之有機基或碳數1~6之烴基。於式中複數存在之R1、Z分別可相同亦可不同。其中,複數存在之Z中之2個以上為下述式(6)所表示之
有機基。
式(5)中,Z表示下述式(6)所表示之有機基或碳數1~6之烴基,作為碳數1~6之烴基之具體例,可列舉甲基、乙基、丙基、丁基、戊基、己基、苯基,但就硬化物之耐熱透明性之觀點而言,較佳為甲基、苯基,其中尤佳為甲基。
式(6)中,R2、m分別表示與上述相同之含義。
作為氧化之方法,可藉由與上述氧化環氧化方法中所例示者相同之方法而進行。
以此方式獲得之本發明之經聚矽氧改質之環氧樹脂的環氧當量較佳為150~450g/eq.,更佳為160~300g/eq,進而較佳為180~250g/eq。於環氧當量低於150g/eq之情形時,存在其硬化物變得過硬之傾向,於超過450g/eq之情形時,存在硬化物之機械特性變差之傾向而不佳。又,較佳為液狀。
環氧當量可根據JIS K7236記載之方法、或1H-NMR、13C-NMR、29Si-NMR、元素分析等而求出。
本發明之環氧樹脂組合物含有(A)經聚矽氧改質之環氧樹脂、及(B)環氧樹脂硬化劑。
自此處起,對(B)環氧樹脂硬化劑進行說明。
(B)作為環氧樹脂硬化劑,使用具有環氧基及反應性之官能基之硬化劑。例如可列舉胺系硬化劑、酚系硬化劑、酸酐系硬化劑、多元羧酸樹脂,其中較佳為酸酐系硬化劑、多元羧酸樹脂。作為酸酐系硬化劑,可列舉鄰苯二甲酸酐、順丁烯二酸酐、偏苯三甲酸酐、均苯四
甲酸二酐、六氫鄰苯二甲酸酐、3-甲基-六氫鄰苯二甲酸酐、4-甲基-六氫鄰苯二甲酸酐、3-甲基-六氫鄰苯二甲酸酐與4-甲基-六氫鄰苯二甲酸酐之混合物、四氫鄰苯二甲酸酐、耐地酸酐、甲基耐地酸酐、降烷-2,3-二羧酸酐、甲基降烷-2,3-二羧酸酐、2,4-二乙基戊二酸酐等,於該等中,較佳為六氫鄰苯二甲酸酐及其衍生物。
其次,對多元羧酸樹脂進行說明。
多元羧酸樹脂係以如下為特徵之化合物:具有至少2個以上之羧基且將脂肪族烴基或矽氧烷骨架作為主骨架。於本發明中,所謂多元羧酸樹脂,不僅包含具有單一結構之多元羧酸化合物,亦包含取代基之位置不同或取代基不同之複數個化合物之混合體、即多元羧酸組合物,於本發明中,將其等統稱為多元羧酸樹脂。
作為多元羧酸樹脂,尤佳為2~6官能之羧酸,更佳為藉由碳數5以上之2~6官能之多元醇或具有矽氧烷結構之多元醇與酸酐的反應而獲得之化合物。進而較佳為上述酸酐為飽和脂肪族環狀酸酐之聚羧酸。
作為2~6官能之多元醇之醇類,只要為具有醇性羥基之化合物則無特別限定,可列舉乙二醇、丙二醇、1,3-丙二醇、1,2-丁二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、環己烷二甲醇、2,4-二乙基戊二醇、2-乙基-2-丁基-1,3-丙二醇、新戊二醇、三環癸烷二甲醇、降烯二醇等二醇類、甘油、三羥甲基乙烷、三羥甲基丙烷、三羥甲基丁烷、2-羥甲基-1,4-丁二醇等三醇類、季戊四醇、二-三羥甲基丙烷等四醇類、二季戊四醇等六醇類等。
作為尤佳之醇類係碳數為5以上之醇,尤其可列舉1,6-己二醇、1,4-環己烷二甲醇、1,3-環己烷二甲醇、1,2-環己烷二甲醇、2,4-二乙基戊二醇、2-乙基-2-丁基-1,3-丙二醇、新戊二醇、三環癸烷二甲醇、降烯二醇等化合物,其中更佳為2-乙基-2-丁基-1,3-丙二醇、新戊二
醇、2,4-二乙基戊二醇、1,4-環己烷二甲醇、三環癸烷二甲醇、降烯二醇等具有支鏈狀結構或環狀結構之醇類。自賦予較高之照度保持率之觀點而言,尤佳為2,4-二乙基戊二醇、三環癸烷二甲醇。
具有矽氧烷結構之多元醇並無特別限定,可使用例如下述式(9)所表示之聚矽氧油。
式(9)中,A1表示亦可隔著醚鍵之碳總數1~10之伸烷基,A2表示甲基或苯基。又,s為重複數且表示平均值,為1~100。
作為酸酐,尤佳為甲基四氫鄰苯二甲酸酐、甲基耐地酸酐、耐地酸酐、六氫鄰苯二甲酸酐、甲基六氫鄰苯二甲酸酐、丁烷四羧酸酐、二環[2,2,1]庚烷-2,3-二羧酸酐、甲基二環[2,2,1]庚烷-2,3-二羧酸酐、環己烷-1,3,4-三羧酸-3,4-酐等,其中較佳為甲基六氫鄰苯二甲酸酐、環己烷-1,3,4-三羧酸-3,4-酐。此處,為提高硬度,較佳為環己烷-1,3,4-三羧酸-3,4-酐,為提高照度保持率,較佳為甲基六氫鄰苯二甲酸酐。
作為加成反應之條件並無特別指定,作為具體之反應條件之一,使酸酐、多元醇於無觸媒、無溶劑之條件下,於40~150℃下反應並加熱,於反應結束後直接取出。為此種方法。然而,並不限定於本反應條件。
作為以此方式獲得之多元羧酸樹脂,尤佳為下述式(10)所表示之化合物。
[化16]
式(10)中,複數存在之A3表示氫原子、甲基、羧基中之至少一種。A4為源自上述多元醇之碳數2~20之鏈狀、環狀之脂肪族基及/或源自具有矽氧烷結構之多元醇之具有矽氧烷結構的亦可隔著醚鍵之碳總數1~10之伸烷基。t為整數且為2~4。
本發明中之(B)環氧樹脂硬化劑較佳為含有酸酐。作為酸酐,具體可列舉鄰苯二甲酸酐、偏苯三甲酸酐、均苯四甲酸二酐、順丁烯二酸酐、四氫鄰苯二甲酸酐、甲基四氫鄰苯二甲酸酐、甲基耐地酸酐、耐地酸酐、六氫鄰苯二甲酸酐、甲基六氫鄰苯二甲酸酐、丁烷四羧酸酐、二環[2,2,1]庚烷-2,3-二羧酸酐、甲基二環[2,2,1]庚烷-2,3-二羧酸酐、環己烷-1,3,4-三羧酸-3,4-酐等酸酐。
尤佳為甲基四氫鄰苯二甲酸酐、甲基耐地酸酐、耐地酸酐、六氫鄰苯二甲酸酐、甲基六氫鄰苯二甲酸酐、丁烷四羧酸酐、二環[2,2,1]庚烷-2,3-二羧酸酐、甲基二環[2,2,1]庚烷-2,3-二羧酸酐、環己烷-1,3,4-三羧酸-3,4-酐等。
尤佳為下述式(11)所表示之六氫鄰苯二甲酸酐、甲基六氫鄰苯二甲酸酐、環己烷-1,3,4-三羧酸-3,4-酐,其中較佳為甲基六氫鄰苯二甲酸酐、環己烷-1,3,4-三羧酸-3,4-酐。
[化17]
式(11)中,A5表示氫原子、甲基、羧基中之至少一種以上。
較佳為併用多元羧酸樹脂與酸酐,於併用之情形時,其使用比率較佳為下述範圍。
W1/(W1+W2)=0.05~0.70
其中,W1表示多元羧酸樹脂之調配質量份,W2表示酸酐之調配質量份。作為W1/(W1+W2)之範圍,更佳為0.05~0.60,進而較佳為0.10~0.55,尤佳為0.15~0.4。若低於0.05,則於硬化時酸酐之揮發變多之傾向較強,從而不佳。若超過0.70,則變成較高之黏度而變得難以操作。於不含有酸酐(殘存少量之情形除外)之情形時,其形狀成為固體或接近固體之狀態、或者結晶,故而不存在問題。
於併用多元羧酸樹脂與酸酐之情形時,自操作之簡便性之方面而言,亦較佳為於多元羧酸樹脂之製造時在過剩之酸酐中進行製造而製作多元羧酸與酸酐之混合物的方法。
本發明之環氧樹脂組合物中之(B)環氧樹脂硬化劑之調配量為如下量:相對於(A)經聚矽氧改質之環氧樹脂中之環氧基之合計1莫耳,環氧基及具有反應性之官能基(酸酐系硬化劑之情形時為-CO-O-CO-所表示之酸酐基)成為0.3~1.0莫耳,較佳為成為0.4~0.8莫耳。若環氧基及具有反應性之官能基為0.3莫耳以上,則硬化物之耐熱性、透明性提高,故而較理想,若為1.0莫耳以下,則硬化物之機械特性提高,故而較佳。此處,所謂「環氧基及具有反應性之官能基」係胺系硬化劑所具有之胺基、酚系硬化劑所具有之酚性羥基、酸酐系硬化劑
所具有之酸酐基、及多元羧酸樹脂所具有之羧基。
本發明之環氧樹脂組合物含有(A)經聚矽氧改質之環氧樹脂、及(C)環氧樹脂硬化促進劑。
自此處起,對(C)環氧樹脂硬化促進劑進行說明。
(C)作為環氧樹脂硬化促進劑,可列舉O,O-二乙基二硫代磷酸四丁基鏻、四苯基硼酸四苯基鏻等四級鏻鹽、三苯基膦、二苯基膦等有機膦系硬化觸媒、1,8-二氮雙環(5,4,0)十一烯-7、三乙醇胺、二甲苄胺等三級胺系硬化觸媒、1,8-二氮雙環(5,4,0)十一烯-7-酚鹽、1,8-二氮雙環(5,4,0)十一烯-7-辛酸鹽、1,8-二氮雙環(5,4,0)十一烯-7-對甲苯磺酸鹽、1,8-二氮雙環(5,4,0)十一烯-7-甲酸鹽等四級銨鹽、辛酸鋅、萘酸鋅等有機羧酸鹽、雙(乙醯乙酸乙酯)-單乙醯丙酮酸鋁、乙醯乙酸乙酯-二異丙酸鋁等鋁螯合化合物、2-甲基咪唑、2-苯基-4-甲基咪唑等咪唑類、芳香族鋶鹽、芳香族錪鹽、銻系鋶鹽等陽離子熱硬化促進劑、銻系鋶鹽、磷系鋶鹽等陽離子光硬化促進劑等。
(C)環氧樹脂硬化促進劑之調配量相對於(A)成分與(B)成分之合計100質量份而為0.01~3質量份,較佳為0.05~1.5質量份。若環氧樹脂硬化促進劑之調配量少於上述下限值,則有促進環氧樹脂與硬化劑之反應之效果不充分之虞。相反,若環氧樹脂硬化促進劑之調配量多於上述上限值,則有成為硬化時或回焊試驗時之變色之原因之虞。
於本發明之環氧樹脂組合物中,能夠以維持其硬化物之透明性為目的而添加抗氧化劑。作為抗氧化劑,存在亞磷酸化合物、受阻酚系抗氧化劑等,較佳為受阻酚系抗氧化劑。又,作為紫外線吸收劑,較佳為受阻胺系紫外線吸收劑。抗氧化劑之調配量相對於(A)成分100質量份為0.1~0.5質量份,較佳為0.1~0.3質量份。若抗氧化劑之調配量超過上期上限值,則殘存之抗氧化劑會於硬化後之樹脂之表面析出,故而不佳,若未達上述下限值則耐熱性、透明性降低。
除上述各成分以外,亦可視需要並用慣用之添加劑,例如紫外線吸收劑、抗劣化劑、螢光體、熱塑化劑、稀釋劑等。
本發明之環氧樹脂組合物可藉由調配上述各成分及視需要之各種添加劑,並溶解或熔融混合而製造。熔融混合可為公知之方法,例如可將上述成分添加至反應器並以分批式進行熔融混合,又,可將上述各成分投入至捏合機或熱三輥研磨機等混練機而連續地進行熔融混合。(C)環氧樹脂硬化促進劑較佳為預先加熱溶解混合於(B)環氧樹脂硬化劑,並於混合之最終階段與(A)經聚矽氧改質之環氧樹脂成分等分散混合。
以下,藉由合成例、實施例,對本發明進行更詳細之說明。再者,本發明並不限定於該等合成例、實施例。再者,合成例、實施例中之各物性值係藉由以下之方法而測定。此處,份只要無特別說明則表示質量份。
○GC(gas chromatography,氣相層析)分析:製造商:島津製作所
機種:GC2010
管柱:Agilent Technology公司製造 HP-5MS 15m
載氣:氦氣1.0ml/min.
檢測器:FID
分流比:30:1
溫度條件
注入:300℃
管柱:於50℃下保持2分鐘,以10℃/min.升溫至300℃並於300℃下保持20分鐘
檢測器:300℃
○GPC(A):GPC(A)係於下述條件下進行測定。
製造商:Waters
管柱:SHODEX GPC LF-G(保護管柱)、KF-603、KF-602.5、KF-602、KF-601(2根)
流速:0.4ml/min.
管柱溫度:40℃
使用溶劑:THF(四氫呋喃)
檢測器:RI(示差折射率檢測器)
○GPC(B):GPC(B)係於下述條件下進行測定。
製造商:島津製作所
管柱:SHODEX GPC LF-G(保護管柱)、LF-804(3根)
流速:1.0ml/min.
管柱溫度:40℃
使用溶劑:THF(四氫呋喃)
檢測器:RI(示差折射率檢測器)
○NMR:使用日本電子股份有限公司製造之JNM-ECS400,藉由氘氯仿溶劑進行測定。
[合成例1]5-乙烯基-2,3-環氧降烷之合成
向具備攪拌裝置及回流冷卻管之玻璃製燒瓶中,添加5-乙烯基降烯240.4g、乙酸三辛基甲基銨之50質量%二甲苯溶液3.64g(Lion Akzo製造,TOMAA-50)、水40.2g、磷鎢酸n水合物5.8g、鎢酸鈉二水合物4.0g、磷酸二氫鈉二水合物6.4g,一面升溫至50±3℃並攪拌,一面花費50分鐘滴下35質量%過氧化氫水97.2g,並直接於50±3℃下攪拌9小時。
藉由1H-NMR確認反應之進行,結果源自降烯之環內烯基之返
還率為82%。
繼而,於藉由30%氫氧化鈉水溶液使pH值成為9後,添加20%硫代硫酸鈉水溶液36g,攪拌30分鐘並靜置。取出分離為2層之有機層,並藉由減壓蒸餾精製法進行精製,而獲得5-乙烯基-2,3-環氧降烷與5-縮水甘油降烯之混合物140.1g。所獲得之混合物之GC面積比係5-乙烯基-2,3-環氧降烷為95.4%,5-縮水甘油降烯為4.6%。
[實施例1]
向1L之可分離式燒瓶中,添加合成例1中獲得之5-乙烯基-2,3-環氧降烷與5-縮水甘油降烯之混合物(1mol、136.2g)、0.5質量%氯鉑酸甲苯溶液0.18g、甲苯20g並攪拌後,使內溫上升至80℃。其後,花費1小時滴下2,4,6,8-四甲基環四矽氧烷(0.17mol、40.09g),並於110℃下反應4小時。藉由將所獲得之甲苯溶液減壓蒸餾,而獲得以下述化合物(12)為主成分之經聚矽氧改質之環氧樹脂(A-1)。將1H-NMR圖譜示於圖-1,將藉由GPC(B)測定出之GPC圖示於圖-2。
[合成例2]
[用作硬化劑之多元羧酸樹脂與酸酐化合物之混合物之合成]
向具備攪拌機、回流冷卻管、攪拌裝置之燒瓶中,一面實施氮
氣沖洗一面添加三環癸烷二甲醇15g、甲基六氫鄰苯二甲酸酐(新日本理化股份有限公司製造,RIKACID MH,以下稱為酸酐H3)70g、環己烷-1,2,4-三羧酸-1,2-酐(三菱瓦斯化學製造 H-TMAn)15g,於40℃下反應3小時後,於70℃下進行1小時之加熱攪拌。藉由GPC確認三環癸烷二甲醇為1面積%以下,獲得100g多元羧酸樹脂與羧酸酐化合物之混合物(B-1)。所獲得者為無色之液狀樹脂,藉由GPC(A)所得之純度係多元羧酸樹脂(下述式13)為37面積%,環己烷-1,2,4-三羧酸-1,2-酐為11面積%,甲基六氫鄰苯二甲酸酐為52面積%。又,官能基當量為171g/eq.。
以下述表1所示之組成(質量份)製備樹脂組合物。其結果,獲得實施例2、比較例1之環氧樹脂組合物。該等表中之各成分如以下般。又,表中,空欄意指「0」。
(A-2)環氧樹脂:下述式(14)所表示之含有環氧環己烷之聚矽氧樹脂(信越化學工業股份有限公司製造,X-40-2670)
(A-2)環氧樹脂:3,4-環氧環己烷羧酸3',4'-環氧環己基甲酯(Daicel股份有限公司製造,CEL2021P)
(C)硬化促進劑:四級鏻鹽(日本化學工業股份有限公司製造,Hishicolin PX-4MP)
抗氧化劑:季戊四醇四[3-(3',5'-二-第三丁基-4'-羥基苯基)丙酸酯](ADEKA股份有限公司製造,Adekastab AO-60)
藉由以下之方法進行所獲得之組合物及硬化物之特性評價。硬化係將組合物於100℃下加熱1小時,進而於150℃下加熱4小時而進行。將結果示於表1。
(1)黏度
依據JIS K7233,藉由東機產業製造之E型旋轉黏度計於23℃下進行測定。
(2)硬度
依據JIS K6301,對棒狀硬化物進行測定(型號D)。
(3)TMA(thermomechanical analysis,熱機械分析)(Tg(Thermal Gravimetry,熱重量),CTE(Coefficients of thermal expansion,熱膨脹係數))
使用具有5mm×15mm、厚度4mm之試驗片,並使用SII NanoTechnology公司製造之TMA/SS-6100進行測定。
(4)水蒸氣透過率
依據JIS K 7129,測定具有厚度0.5mm之各硬化物之水蒸氣透過率。
根據表1之結果可知,實施例2之組合物之低氣體透過性、強度優異。另一方面,比較例1之組合物雖強度優異,但低氣體透過性較差。
Claims (8)
- 一種經聚矽氧改質之環氧樹脂(A),其由下述式(1)表示:
- 如請求項1之經聚矽氧改質之環氧樹脂,其係下述式(3)所記載之化合物、與下述式(4)所記載之化合物之加成反應產物,
- 如請求項1之經聚矽氧改質之環氧樹脂,其係藉由將下述式(5)之多元烯烴系化合物氧化而獲得,
- 如請求項1至3中任一項之經聚矽氧改質之環氧樹脂,其中n為2。
- 一種環氧樹脂組合物,其含有如請求項1至4中任一項之(A)經聚矽氧改質之環氧樹脂及(B)環氧樹脂硬化劑。
- 一種環氧樹脂組合物,其含有如請求項1至4中任一項之(A)經聚矽氧改質之環氧樹脂及(C)環氧樹脂硬化促進劑。
- 一種環氧樹脂組合物,其特徵在於:如請求項5之環氧樹脂硬化劑選自胺系硬化劑、酚系硬化劑、酸酐系硬化劑、及多元羧酸樹脂之至少任一種。
- 一種硬化物,其係使如請求項5至7中任一項之環氧樹脂組合物硬化而成。
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US5258480A (en) * | 1992-05-18 | 1993-11-02 | General Electric Company | Syntheses of epoxysilicones |
DE4328466C1 (de) | 1993-08-24 | 1995-04-13 | Siemens Ag | Siloxanhaltiges Gießharzsystem |
US6828404B2 (en) * | 2000-10-20 | 2004-12-07 | Rensselaer Polytechnic Institute | Polymerizable siloxanes |
JP4009067B2 (ja) | 2001-03-06 | 2007-11-14 | 信越化学工業株式会社 | 付加硬化型シリコーン樹脂組成物 |
WO2004094435A2 (en) * | 2003-04-16 | 2004-11-04 | Rensselaer Polytechnic Institute | Siloxane monomers and oligomers |
US7019386B2 (en) * | 2004-04-27 | 2006-03-28 | Polyset Company, Inc. | Siloxane epoxy polymers for low-k dielectric applications |
JP2006282988A (ja) | 2005-03-08 | 2006-10-19 | Sanyo Chem Ind Ltd | 光半導体素子封止用エポキシ樹脂組成物 |
JP2006307128A (ja) * | 2005-03-30 | 2006-11-09 | Yokohama Rubber Co Ltd:The | 熱硬化性樹脂組成物ならびにそれを用いた成形用材料およびポッティング材 |
JP2008045088A (ja) | 2006-08-21 | 2008-02-28 | Sekisui Chem Co Ltd | 光半導体用熱硬化性組成物、光半導体素子用封止剤、光半導体素子用ダイボンド材、光半導体素子用アンダーフィル材及び光半導体装置 |
EP2109635B1 (en) * | 2007-11-21 | 2012-11-07 | Momentive Performance Materials Inc. | Organosilicone compositions and methods for preparing them |
JP6047294B2 (ja) * | 2012-03-30 | 2016-12-21 | 株式会社ダイセル | 硬化性エポキシ樹脂組成物 |
-
2015
- 2015-03-25 JP JP2016511579A patent/JP6514685B2/ja active Active
- 2015-03-25 US US15/300,645 patent/US9963542B2/en active Active
- 2015-03-25 WO PCT/JP2015/059119 patent/WO2015151957A1/ja active Application Filing
- 2015-03-25 CN CN201580017513.6A patent/CN106133020A/zh active Pending
- 2015-03-31 TW TW104110552A patent/TW201540740A/zh unknown
Also Published As
Publication number | Publication date |
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WO2015151957A1 (ja) | 2015-10-08 |
JPWO2015151957A1 (ja) | 2017-04-13 |
US9963542B2 (en) | 2018-05-08 |
JP6514685B2 (ja) | 2019-05-15 |
US20170107322A1 (en) | 2017-04-20 |
CN106133020A (zh) | 2016-11-16 |
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