CN116410445A - 环氧树脂组合物以及树脂薄膜 - Google Patents
环氧树脂组合物以及树脂薄膜 Download PDFInfo
- Publication number
- CN116410445A CN116410445A CN202210141269.6A CN202210141269A CN116410445A CN 116410445 A CN116410445 A CN 116410445A CN 202210141269 A CN202210141269 A CN 202210141269A CN 116410445 A CN116410445 A CN 116410445A
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- substituted
- resin composition
- unsubstituted
- monomer
- 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.)
- Pending
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 211
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 211
- 239000000203 mixture Substances 0.000 title claims abstract description 109
- 229920005989 resin Polymers 0.000 title claims abstract description 18
- 239000011347 resin Substances 0.000 title claims abstract description 18
- 239000000178 monomer Substances 0.000 claims abstract description 104
- 239000004848 polyfunctional curative Substances 0.000 claims abstract description 37
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 24
- 125000000732 arylene group Chemical group 0.000 claims abstract description 24
- 239000004593 Epoxy Substances 0.000 claims abstract description 22
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 22
- 239000001257 hydrogen Substances 0.000 claims abstract description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 21
- 125000002993 cycloalkylene group Chemical group 0.000 claims abstract description 16
- 125000002877 alkyl aryl group Chemical group 0.000 claims abstract description 13
- 125000005549 heteroarylene group Chemical group 0.000 claims abstract description 13
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 9
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 239000004842 bisphenol F epoxy resin Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 4
- 150000008064 anhydrides Chemical group 0.000 claims description 4
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 claims description 2
- HDPLHDGYGLENEI-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COCC1CO1 HDPLHDGYGLENEI-UHFFFAOYSA-N 0.000 claims description 2
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 claims description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 2
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 150000002118 epoxides Chemical class 0.000 claims 1
- 125000002947 alkylene group Chemical group 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 description 30
- -1 Ethyl s-triazine Chemical compound 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 12
- 238000005481 NMR spectroscopy Methods 0.000 description 11
- 238000002844 melting Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 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 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000002378 acidificating effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- FIXBBOOKVFTUMJ-UHFFFAOYSA-N 1-(2-aminopropoxy)propan-2-amine Chemical compound CC(N)COCC(C)N FIXBBOOKVFTUMJ-UHFFFAOYSA-N 0.000 description 6
- IAVREABSGIHHMO-UHFFFAOYSA-N 3-hydroxybenzaldehyde Chemical compound OC1=CC=CC(C=O)=C1 IAVREABSGIHHMO-UHFFFAOYSA-N 0.000 description 6
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-WFGJKAKNSA-N acetone d6 Chemical compound [2H]C([2H])([2H])C(=O)C([2H])([2H])[2H] CSCPPACGZOOCGX-WFGJKAKNSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 238000003776 cleavage reaction Methods 0.000 description 6
- 238000005336 cracking Methods 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 229920001451 polypropylene glycol Polymers 0.000 description 6
- 230000003595 spectral effect Effects 0.000 description 6
- 125000004957 naphthylene group Chemical group 0.000 description 5
- 125000000466 oxiranyl group Chemical group 0.000 description 5
- 238000004806 packaging method and process Methods 0.000 description 5
- 230000007017 scission Effects 0.000 description 5
- 229920001187 thermosetting polymer Polymers 0.000 description 5
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- 125000003118 aryl group Chemical group 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
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 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
- 239000007788 liquid Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- 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 4
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 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 3
- 125000000879 imine group Chemical group 0.000 description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- 235000019341 magnesium sulphate Nutrition 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- SOOZEQGBHHIHEF-UHFFFAOYSA-N methyltetrahydrophthalic anhydride Chemical compound C1C=CCC2C(=O)OC(=O)C21C SOOZEQGBHHIHEF-UHFFFAOYSA-N 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 3
- 235000012141 vanillin Nutrition 0.000 description 3
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 2
- PIODUORJBYXSQY-UHFFFAOYSA-N 2-ethylhexanoic acid Chemical compound CCCCC(CC)C(O)=O.CCCCC(CC)C(O)=O PIODUORJBYXSQY-UHFFFAOYSA-N 0.000 description 2
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- OJGMBLNIHDZDGS-UHFFFAOYSA-N N-Ethylaniline Chemical compound CCNC1=CC=CC=C1 OJGMBLNIHDZDGS-UHFFFAOYSA-N 0.000 description 2
- QLBRROYTTDFLDX-UHFFFAOYSA-N [3-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCC(CN)C1 QLBRROYTTDFLDX-UHFFFAOYSA-N 0.000 description 2
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 2
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 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 2
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 2
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 2
- 125000004115 pentoxy group Chemical group [*]OC([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 2
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 125000005730 thiophenylene group Chemical group 0.000 description 2
- RUEBPOOTFCZRBC-UHFFFAOYSA-N (5-methyl-2-phenyl-1h-imidazol-4-yl)methanol Chemical compound OCC1=C(C)NC(C=2C=CC=CC=2)=N1 RUEBPOOTFCZRBC-UHFFFAOYSA-N 0.000 description 1
- DTQZKOBDNLNBCU-UHFFFAOYSA-N 1-methylimidazole Chemical compound CN1C=CN=C1.CN1C=CN=C1 DTQZKOBDNLNBCU-UHFFFAOYSA-N 0.000 description 1
- WOHOXHYMCWWJJH-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1.CC1=NC=CN1 WOHOXHYMCWWJJH-UHFFFAOYSA-N 0.000 description 1
- ZXTHWIZHGLNEPG-UHFFFAOYSA-N 2-phenyl-4,5-dihydro-1,3-oxazole Chemical compound O1CCN=C1C1=CC=CC=C1 ZXTHWIZHGLNEPG-UHFFFAOYSA-N 0.000 description 1
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- GQHTUMJGOHRCHB-UHFFFAOYSA-N DBU Substances C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 125000004653 anthracenylene group Chemical group 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- YMHQVDAATAEZLO-UHFFFAOYSA-N cyclohexane-1,1-diamine Chemical compound NC1(N)CCCCC1 YMHQVDAATAEZLO-UHFFFAOYSA-N 0.000 description 1
- GEQHKFFSPGPGLN-UHFFFAOYSA-N cyclohexane-1,3-diamine Chemical compound NC1CCCC(N)C1 GEQHKFFSPGPGLN-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000005567 fluorenylene group Chemical group 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000004849 latent hardener Substances 0.000 description 1
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000004843 novolac epoxy resin Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 125000005562 phenanthrylene group Chemical group 0.000 description 1
- JYIZNFVTKLARKT-UHFFFAOYSA-N phenol;1,3,5-triazine-2,4,6-triamine Chemical compound OC1=CC=CC=C1.NC1=NC(N)=NC(N)=N1 JYIZNFVTKLARKT-UHFFFAOYSA-N 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 229940037312 stearamide Drugs 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- JABYJIQOLGWMQW-UHFFFAOYSA-N undec-4-ene Chemical compound CCCCCCC=CCCC JABYJIQOLGWMQW-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 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
- C08G59/20—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
- C08G59/28—Di-epoxy compounds containing acyclic nitrogen atoms
-
- 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
- C08G59/50—Amines
- C08G59/5046—Amines heterocyclic
- C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
- C08G59/5073—Amines heterocyclic containing only nitrogen as a heteroatom having two nitrogen atoms in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
- C07D303/20—Ethers with hydroxy compounds containing no oxirane rings
- C07D303/22—Ethers with hydroxy compounds containing no oxirane rings with monohydroxy compounds
- C07D303/23—Oxiranylmethyl ethers of compounds having one hydroxy group bound to a six-membered aromatic ring, the oxiranylmethyl radical not being further substituted, i.e.
-
- 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
- C08G59/24—Di-epoxy compounds carbocyclic
-
- 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
- C08G59/24—Di-epoxy compounds carbocyclic
- C08G59/245—Di-epoxy compounds carbocyclic aromatic
-
- 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
- C08G59/4215—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof cycloaliphatic
-
- 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
- C08G59/50—Amines
- C08G59/5006—Amines aliphatic
- C08G59/502—Polyalkylene polyamines
-
- 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
- C08J5/18—Manufacture of films or sheets
-
- 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
- C08J2363/02—Polyglycidyl ethers of bis-phenols
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Epoxy Resins (AREA)
- Paints Or Removers (AREA)
Abstract
本揭露提供一种环氧树脂组合物及树脂薄膜。所述环氧树脂组合物包含一硬化剂;以及一环氧树脂单体。所述环氧树脂单体具有式(I)所示结构,其中所述A是取代或未取代的C6‑24芳撑基(arylene group)、C3‑16环烷撑基(cycloalkylene group)、C3‑16杂芳撑基(heteroarylene group)、C3‑16的脂环烷撑基(alicyclic alkylene group)、或二价C6‑25烷基芳基(alkylaryl group);X1及X2是独立为Y1及Y2是独立为取代或未取代的C6‑24芳撑基(arylene group),且Y1与Y2不相同;以及,R1是氢、C1‑8烷基、或C1‑8烷氧基,所述硬化剂与所述具有式(I)的环氧树脂单体重量比为1:100至1:1。
Description
技术领域
本揭露关于一种环氧树脂组合物以及树脂薄膜。
背景技术
异方性导电接着剂广泛应用于连结铟锡氧化物(ITO)基板与驱动电路基板(例如软性印刷电路板)上的印刷接点。
由于热固型树脂优异的机械性能、耐化学性、耐热性以及绝缘性,目前主流的异方性导电接着剂都普遍含有热固型树脂。然而,热固型树脂材料固化后无法熔解与溶解,难以重塑、再加工或回收利用,导致利用异方性导电接着剂制备的装置面临拆解不易、残留胶材不易去除等问题。此外,在电子材料领域中,半导体封装逐渐往小型化、薄型化以及形状复杂化等方向发展。因此,随着封装难度的提升,业界对于具有高流动性及低应力的半导体封装材料的需求也日益增加。
发明内容
根据本揭露实施例,本揭露提供一种环氧树脂组合物(例如热固型树脂组合物)。本揭露所述环氧树脂组合物包含一硬化剂;以及一环氧树脂单体。该环氧树脂单体具有式(I)所示结构
,其中A可为取代或未取代的C6-24芳撑基(arylene group)、取代或未取代的C3-16环烷撑基(cycloalkylene group)、取代或取代的C3-16杂芳撑基(heteroarylene group)、取代或未取代的C3-16的脂环烷撑基(alicyclic alkylene group)、或取代或未取代的二价C6-25烷基芳基(alkylaryl group);X1及X2可独立为Y1及Y2可独立为取代或未取代的C6-24芳撑基(arylene group),且Y1与Y2不相同;以及,R1可为氢、C1-8烷基、或C1-8烷氧基。根据本揭露实施例,该硬化剂与该环氧树脂单体的重量比可为1:100至1:1。
根据本揭露实施例,该环氧树脂组合物可更包含一环氧树脂。根据本揭露实施例,该环氧树脂与该具有式(I)所示结构的环氧树脂单体的重量比可为1:100至9:1。
根据本揭露某些实施例,本揭露提供一种树脂薄膜。所述树脂薄膜可包含本揭露所述环氧树脂组合物的固化物。
具体实施方式
以下针对本揭露的环氧树脂组合物以及树脂薄膜作详细说明。应了解的是,以下的叙述提供许多不同的实施例或例子,用以实施本揭露的不同样态。以下所述特定的元件及排列方式仅为简单描述本揭露。当然,这些仅用以举例而非本揭露的限定。本揭露中,用词「约」是指所指定的量可增加或减少一本领域技术人员可认知为一般且合理的大小的量。
本揭露实施例提供一种环氧树脂组合物以及一种树脂薄膜。根据本揭露实施例,树脂薄膜可为该环氧树脂组合物经固化所形成的薄膜。根据本揭露实施例,该环氧树脂组合物包含具有特定结构的环氧树脂单体以及硬化剂。由于本揭露所述环氧树脂单体导入亚胺(imine)基团,使得本揭露所述环氧树脂组合物的固化物可在相对低温(例如80℃或以下)的酸性环境下进行裂解,解决热固型树脂不易裂解的问题。如此一来,当本揭露所述环氧树脂组合物作为封装胶材时,其固化物可在特定条件下轻易被去除,可避免残胶问题,并使利用该环氧树脂组合物进行封装的装置易于被拆解及回收。此外,本揭露所述环氧树脂单体其化学结构仍具有芳香基团,因此利用本揭露所述环氧树脂组合物所得的产品(即包含环氧树脂组合物固化物的产品)除了具有可低温裂解的特性外,亦可具有高耐热性、高耐化性、以及尺寸安定性。再者,藉由环氧树脂单体其不对称性化学结构的设计,使得本揭露所述环氧树脂单体的熔点可大幅降低(解决传统芳香族环氧树脂高熔点的问题),进而使得本揭露所述环氧树脂单体在室温下呈现液态。如此一来,藉由该液态环氧树脂单体的加入,可使得本揭露所述环氧树脂组合物其流动性大幅提升,扩展环氧树脂组合物应用范畴(例如需低温操作的封装系统、或具较高复杂度的封装需求)。根据本揭露实施例,本揭露所述环氧树脂组合物可作为胶材,应用于异方性导电接着剂、底部填充(underfill)胶、或B阶段(b-stageable)贴合膜或液态胶材。
本揭露所述环氧树脂组合物包含一硬化剂,以及一环氧树脂单体。根据本揭露实施例,该硬化剂的添加量并无特别限制,所属技术领域中具有通常知识者可视实际需要加以调整。根据本揭露实施例,该硬化剂与该环氧树脂单体的重量比可为约1:100至1:1,例如约2:100、3:100、5:100、8:100、10:100、15:100、20:100、25:100、30:100、40:100、50:100、60:100、75:100、80:100、或90:100。根据本揭露实施例,本揭露所述环氧树脂单体适合搭配各类型硬化剂使用。该硬化剂种类并无特别限制,所属技术领域中具有通常知识者可视实际需要加以选用。根据本揭露实施例,本揭露所述硬化剂可为酸酐硬化剂、胺硬化剂、酚醛硬化剂、咪唑硬化剂、或上述的组合。举例来说,酸酐硬化剂可为甲基六氢邻苯二甲酸酐(methyl hexahydrophthalic anhydride)、甲基四氢邻苯二甲酸酐(methyltetrahydrophthalic anhydrid,MTHPA)、马来酸酐(maleic anhydride、MA)、苯乙烯-共-马来酸酐(polystyrene-co-maleic anhydride、SMA)、或上述的组合,但不以上述为限。根据本揭露实施例,胺硬化剂可为脂肪胺硬化剂、环状脂肪胺硬化剂、或芳香族胺硬化剂。胺硬化剂可为聚丙二醇双(2-氨基丙基醚)(poly(propylene glycol)bis(2-aminopropyl ether))(例如D-230)、环己二胺、二氨基二苯醚(oxydianiline)、或硬脂酰胺乙氧基化物(stearyl amine ethoxylate、SAA)。根据本揭露实施例,酚醛硬化剂可为苯酚-甲醛酚醛清漆(phenol-formaldehyde novolac、HRJ系列)、或三聚氰胺线型酚醛(melamine phenol novolac)。根据本揭露实施例,该咪唑硬化剂可为1-甲基咪唑(1-methyl imidazole)、2-甲基咪唑(2-methyl imidazole)、2-乙基-4-甲基咪唑(2-ethyl-4-methyl imidiazole)、2-苯基-4-甲基咪唑、2-苯基-4-甲基-5-羟甲基咪唑、2-苯基-4,5-二羟甲基咪唑、2,4-二胺基-6-[2'-甲基咪唑基-(1')]乙基均三嗪、2,4-二胺基-6-(2'-十一烷基咪唑基)乙基均三嗪、2,4-二胺基-6-[2'-乙基-4-甲基咪唑基-(1')]乙基均三嗪、或潜伏型硬化剂(如NOVACURE HXA-3932)等。上述仅为举例,本揭露所使用的酸酐硬化剂、胺硬化剂、酚醛硬化剂、咪唑硬化剂不以此为限。
根据本揭露实施例,本揭露所述环氧树脂单体为具有分子内亚胺基团的不对称环氧树脂单体(即该环氧树脂单体具有不对称的化学结构)。根据本揭露实施例,本揭露所述环氧树脂单体可具有式(I)所示结构
,其中A可为取代或未取代的C6-24芳撑基(arylene group)、取代或未取代的C3-16环烷撑基(cycloalkylene group)、取代或未取代的C3-16杂芳撑基(heteroarylene group)、取代或未取代的C3-16的脂环烷撑基(alicyclic alkylene group)、或取代或未取代的二价C6-25烷基芳基(alkylaryl group);X1及X2可独立为Y1及Y2可独立为取代或未取代的C6-24芳撑基(arylene group);以及,R1可为氢、C1-8烷基、或C1-8烷氧基。值得注意的是,由于本揭露所述环氧树脂单体为不对称环氧树脂单体,因此Y1与Y2需为不相同的基团。根据本揭露实施例,Y1与Y2的组成元素可相同,但其化学结构需不同。
根据本揭露实施例,本揭露所述取代的C6-24芳撑基(arylene group)是指该C6-24芳撑基的至少一者碳上的氢被C1-8烷基、或C1-8烷氧基所取代;本揭露所述取代的C3-16环烷撑基(cycloalkylene group)是指该C3-16环烷撑基的至少一者碳上的氢被C1-8烷基、或C1-8烷氧基所取代;本揭露所述取代的C3-16杂芳撑基(heteroarylene group)是指该C3-16杂芳撑基的至少一者碳上的氢被C1-8烷基、或C1-8烷氧基所取代;本揭露所述取代的C3-16的脂环烷撑基是指该C3-16的脂环烷撑基的至少一者碳上的氢被C1-8烷基、或C1-8烷氧基所取代;以及,本揭露所述取代的二价C6-25烷基芳基(alkylaryl group)是指该二价C6-25烷基芳基的至少一者碳上的氢被C1-8烷基、或C1-8烷氧基所取代。
根据本揭露实施例,A可为取代或未取代苯撑基(phenylene group)、取代或未取代联苯撑基(biphenylene group)、取代或未取代萘撑基(naphthylene group)、取代或未取代噻吩撑基(thienylene group)、取代或未取代吲哚撑基(indolylene)、取代或未取代菲撑基(phenanthrenylene)、取代或未取代茚撑基(indenylene)、取代或未取代蒽撑基(anthracenylene)、或取代或未取代芴撑基(fluorenylene),其中取代的苯撑基(phenylene group)、取代的联苯撑基(biphenylene group)、取代的萘撑基(naphthylenegroup)、取代的噻吩撑基(thienylene group)、取代的吲哚撑基(indolylene)、取代的菲撑基(phenanthrenylene)、取代的茚撑基(indenylene)、取代的蒽撑基(anthracenylene)、或取代的芴撑基(fluorenylene)是指该等基团的至少一者碳上的氢被C1-8烷基所取代或被C1-8烷氧基所取代。
根据本揭露实施例,C1-8烷基可为直链或分支(linear or branched)链的烷基。举例来说,C1-8烷基可为甲基(methyl)、乙基(ethyl)、丙基(propyl)、丁基(butyl)、戊基(pentyl)、己基(hexyl)、庚基(heptyl)、辛基(octyl)、或其异构体(isomer)。根据本揭露实施例,C1-8烷基可为直链或分支(linear or branched)链的烷氧基。举例来说,C1-8烷氧基可为甲氧基(methoxy)、乙氧基(ethoxy)、丙氧基(propoxy)、丁氧基(butoxy)、戊氧基(pentoxy)、己氧基(hexoxy)、庚氧基(heptoxy)、辛氧基(octoxy)或其异构体(isomer)。
根据本揭露实施例,X1可以碳与Y1连接且以氮与A连接,以及X2是以碳与Y2连接且以氮与A连接。此外,根据本揭露实施例,X1可以氮与Y1连接且以碳与A连接,以及X2可以氮与Y2连接且以碳与A连接。
根据本揭露实施例,A可为 其中R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13、R14、R15、R16、R17、R18、R19、R20、R21、R22、R23、R24、R25、R26、R27、R28、及R29可独立为氢、C1-8烷基、或C1-8烷氧基。根据本揭露实施例,R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13、R14、R15、R16、R17、R18、R19、R20、R21、R22、R23、R24、R25、R26、R27、R28、及R29可独立为氢、甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、甲氧基、乙氧基、丙氧基、丁氧基、戊氧基、己氧基、庚氧基、辛氧基或其异构体。
其中R30、R31、R32、R33、R34、及R35可独立为氢、C1-8烷基、或C1-8烷氧基;以及,a、b、c、d、e、以及f可独立为1、2、3、4、或5。根据本揭露实施例,R30、R31、R32、R33、R34、及R35可独立为氢、甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、甲氧基、乙氧基、丙氧基、丁氧基、戊氧基、己氧基、庚氧基、辛氧基或其异构体。
根据本揭露实施例,该环氧树脂单体可为
/> 其中R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13可独立为氢、C1-8烷基、或C1-8烷氧基;以及,Y1及Y2是独立为取代或未取代的C6-24芳撑基(arylene group),且Y1与Y2不相同。
根据本揭露实施例,该环氧树脂单体可为
,其中R1、R14、R15、R16、R17、R18、R19、R20、R21、R22、R23、R24、R25、R26、R27、R28、及R29是独立为氢、C1-8烷基、或C1-8烷氧基;以及,Y1及Y2是独立为取代或未取代的C6-24芳撑基(arylenegroup),且Y1与Y2不相同。
根据本揭露实施例,该环氧树脂单体可为
其中A是取代或未取代的C6-24芳撑基(arylene group)、C3-16环烷撑基(cycloalkylene group)、C3-16杂芳撑基(heteroarylene group)、C3-16的脂环烷撑基(alicyclic alkylene group)、或二价C6-25烷基芳基(alkylaryl group);以及,R1、R30、R31、及R32是独立为氢、C1-8烷基、或C1-8烷氧基。
根据本揭露实施例,该环氧树脂单体的环氧当量重(EEW)为约50克/当量至1500克/当量,例如100克/当量、150克/当量、200克/当量、300克/当量、400克/当量、500克/当量、600克/当量、700克/当量、800克/当量、900克/当量、1000克/当量、1200克/当量、或1400克/当量。根据本揭露实施例,当该环氧树脂单体的环氧当量较高时,本揭露所述环氧树脂组合物的固化物具有较差的酸性环境裂解特性。
根据本揭露实施例,本揭露所述环氧树脂组合物可更包含一环氧树脂,其中该环氧树脂与该环氧树脂单体的重量比为1:100至9:1。当环氧树脂单体的含量过低时,本揭露所述环氧树脂组合物的固化物具有较差的酸性环境裂解特性、且具有较差的流动性。
根据本揭露实施例,该环氧树脂是双酚A环氧树脂、双酚F环氧树脂、双酚S环氧树脂、酚醛环氧树脂、萘基环氧树脂、蒽基环氧树脂、双酚A二缩水甘油醚环氧树脂、乙二醇二缩水甘油醚环氧树脂、丙二醇二缩水甘油醚环氧树脂、或1,4-丁二醇二缩水甘油醚环氧树脂。根据本揭露实施例,该环氧树脂的重量平均分子量可为约200g/mol至2,000,000g/mol,例如8,000g/mol、10,000g/mol、20,000g/mol、50,000g/mol、100,000g/mol、300,000g/mol、500,000g/mol、1,000,000g/mol、1,500,000g/mol、或1,800,000g/mol。本揭露所述环氧树脂的重量平均分子量(Mw)可以凝胶渗透色层分析法(GPC)测得(以聚苯乙烯作为标准品制作检量线)。本实施例使用商品树脂的的重量平均分子量约为<1000或更低。
表1是列举出本揭露实施例所述环氧树脂单体,并显示其化学结构。
表1
根据本揭露实施例,本揭露亦提供一树脂薄膜,其中该树脂薄膜包含本揭露所述环氧树脂组合物的固化物。
为进一步说明本揭露所述环氧树脂单体的制备方法,以下列举说明实施例1、2所述环氧树脂单体的制备流程。
环氧树脂单体的制备
实施例1
将4,4'-亚甲基双(2-乙基)苯胺(4,4'-methylene bis(2-ethylaniline),MOEA)(0.04摩尔)、香草醛(vanillin)(0.04摩尔)、3-羟基苯甲醛(3-hydroxybenzaldehyde,MHB)(0.04摩尔)、对甲苯磺酸(p-toluenesulfonic acid,TsOH)(0.09克)、以及乙醇(ethanol,EtOH)(50毫升)加入一反应瓶中,得到一混合物。接着,将反应瓶在氮气环境下加热至70℃后,搅拌该混合物5小时。接着,将反应瓶降至室温并将所得产物进行浓缩后,得到化合物(1)。上述反应的反应式如下所示:
接着,利用核磁共振光谱分析化合物(1),所得的光谱信息如下:1H NMR(acetone-d6;400MHz)δ:8.48(s,1H,-CH=N-)、8.37(s,1H,-CH=N-)、7.72(s,1H,Ar-H)、7.54(s,1H,Ar-H)、7.28-7.49(m,5H,Ar-H)、7.21~7.03(m,6H,Ar-H)、3.95(s,2H,-CH2-)、3.85(s,3H,-OCH3)、2.75(q,4H,-CH2 CH3-)、1.20(t,6H,-CH2CH3 )。
接着,将化合物(1)(0.04摩尔)、环氧氯丙烷(epichlorohydrin,ECH)(37克)、四丁基溴化铵(tetrabutyl ammonium bromide,TBAB)(1.29克)、加入一反应瓶中,得到一混合物。接着,将反应瓶在氮气环境下加热至80℃后,搅拌该混合物3小时。接着,将反应瓶降至5℃以下,并加入氢氧化钠水溶液(6克)(固含量为40wt%)至该反应瓶中。接着,在5℃以下搅拌5小时将所得产物进行浓缩,并加入乙酸乙酯进行溶解。接着,将所得溶液以去离子水清洗三次。接着以硫酸镁对有机层进行除水并进行浓缩及干燥,得到环氧树脂单体(I)。上述反应的反应式如下:
利用核磁共振光谱分析环氧树脂单体(I),所得的光谱信息如下:1H NMR(acetone-d6;400MHz)δ:8.51(s,1H,-CH=N-)、8.40(s,1H,-CH=N-)、7.75(s,1H,Ar-H)、7.68(s,1H,Ar-H)、7.52(d,1H,Ar-H)、7.47(m,1H,Ar-H)、7.25~6.81(9H,Ar-H)、4.42~2.75(10H,-CH2-;环氧乙烷基团(oxirane)的-CH-及-CH2-)、3.98(s,2H,-CH2-)、3.95(s,6H,-OCH3)、2.75(m,4H,-CH2 CH3-)、1.20(t,6H,-CH2CH3 )。
实施例2
将1,3-环己二甲胺(1,3-bis(aminomethyl)cyclohexane,1,3-BAC)(0.04摩尔)、香草醛(vanillin)(0.04摩尔)、3-羟基苯甲醛(3-hydroxybenzaldehyde,MHB)(0.04摩尔)、对甲苯磺酸(p-toluenesulfonic acid,TsOH)(0.09克)、以及乙醇(ethanol,EtOH)(50毫升)加入一反应瓶中,得到一混合物。接着,将反应瓶在氮气环境下加热至70℃后,搅拌该混合物5小时。接着,将反应瓶降至室温并将所得产物进行浓缩后,得到化合物(2)。上述反应的反应式如下所示:
利用核磁共振光谱分析化合物(2),所得的光谱信息如下:1H NMR(acetone-d6;400MHz)δ:8.21(S,1H,-CH=N-)、8.15(S,1H,-CH=N-)、7.48(s,1H,Ar-H)、7.30(s,1H,Ar-H)、7.25~7.09(m,3H,Ar-H)、6.89~6.79(m,2H,Ar-H)、3.81(s,3H,-OCH3)、3.54~3.36(m,2H,-CH2-)、1.99~1.22(m,6H,-CH2-)、1.0~0.72(m,2H,-CH2-)。
接着,将化合物(2)(0.04摩尔)、环氧氯丙烷(epichlorohydrin,ECH)(37克)、四丁基溴化铵(tetrabutyl ammonium bromide,TBAB)(1.29克)、加入一反应瓶中,得到一混合物。接着,将反应瓶在氮气环境下加热至80℃后,搅拌该混合物3小时。接着,将反应瓶降至5℃以下,并加入氢氧化钠水溶液(6克)(固含量为40wt%)至该反应瓶中。接着,在5℃以下搅拌5小时后,将所得产物进行浓缩,并加入乙酸乙酯进行溶解。接着,将所得溶液以去离子水清洗三次。接着,以硫酸镁对有机层进行除水并进行浓缩及干燥,得到环氧树脂单体(II)。上述反应的反应式如下:
接着,利用核磁共振光谱分析环氧树脂单体(II),所得的光谱信息如下:1H NMR(acetone-d6;400MHz)δ:8.19(m,1H,-CH=N-)、8.14(m,1H,-CH=N-)、7.45(s,1H,Ar-H)、7.30(s,1H,Ar-H)、7.26~7.10(m,3H,Ar-H)、6.93~6.84(m,2H,Ar-H)、4.42~2.75(m,10H,-O-CH2-;环氧乙烷基团(oxirane)的-CH-及-CH2-)、3.81(s,3H,-OCH3)、3.54~3.36(m,4H,-CH2-)、1.99~1.22(m,6H,-CH2-)、1.0~0.72(m,2H,-CH2-)。
比较例1
将4,4'-亚甲基双(2-乙基)苯胺(4,4'-methylene bis(2-ethylaniline),MOEA)(0.04摩尔)、香草醛(vanillin)(0.08摩尔)、对甲苯磺酸(p-toluenesulfonic acid,TsOH)(0.09克)、以及乙醇(ethanol,EtOH)(50毫升)加入一反应瓶中,得到一混合物。接着,将反应瓶在氮气环境下加热至70℃后,搅拌该混合物5小时。接着,将反应瓶降至室温并将所得产物进行浓缩后,得到化合物(3)。上述反应的反应式如下所示:
利用核磁共振光谱分析化合物(3),所得的光谱信息如下:1H NMR(acetone-d6;400MHz)δ:8.47(s,2H,-CH=N-)、7.65(s,2H,Ar-H)、7.43(dd,2H,Ar-H)、7.16(s,2H,Ar-H)、7.10(dd,2H,Ar-H)、7.04(dd,2H,Ar-H)、6.75(dd,2H,Ar-H)、4.42(dd,2H,-CH2-)、3.90(s,6H,-OCH3)、2.75(m,4H,-CH2 CH3)、1.15(t,6H,-CH2CH3 )。
接着,将化合物(3)(0.04摩尔)、环氧氯丙烷(epichlorohydrin,ECH)(37克)、四丁基溴化铵(tetrabutyl ammonium bromide,TBAB)(1.29克)、加入一反应瓶中,得到一混合物。接着,将反应瓶在氮气环境下加热至80℃后,搅拌该混合物3小时。接着,将反应瓶降至5℃以下,并加入氢氧化钠水溶液(6克)(固含量为40wt%)至该反应瓶中。接着,在5℃以下搅拌5小时后,将所得产物完进行浓缩,并加入乙酸乙酯进行溶解。接着,将所得溶液以去离子水清洗三次。接着,以硫酸镁对有机层进行除水并进行浓缩及干燥,得到环氧树脂单体(XI)。上述反应的反应式如下:
接着,利用核磁共振光谱分析环氧树脂单体(XI),所得的光谱信息如下:1H NMR(acetone-d6;400MHz)δ:8.47(s,2H,-CH=N-)、7.70(s,2H,Ar-H)、7.42(dd,2H,Ar-H)、7.15(s,2H,Ar-H)、7.10(dd,2H,Ar-H)、7.05(dd,2H,Ar-H)、6.85(dd,2H,Ar-H)、4.42(dd,2H,-CH2-)、3.90(s,6H,-OCH3)、3.88(dd,2H,-O-CH2-)、3.35(dt,2H,环氧乙烷基团(oxirane)的-CH-)、2.85-2.78(m,4H,环氧乙烷基团(oxirane)的-CH2-)、2.75(m,4H,-CH2 CH3)、1.15(t,6H,-CH2CH3 )。
对实施例1及2所得的环氧树脂单体(I)及环氧树脂单体(II)以及比较例1所得的环氧树脂单体(XI)进行熔点(melting point)及环氧当量(epoxy equivalent)的量测,结果如表2所示。环氧树脂单体的熔点量测是以微示差扫描热卡分析仪(differentialscanning calorimetry,DSC)进行评估;以及,环氧树脂单体的环氧当量是依据ASTM D1652所规定的方式测定。
表2
熔点(℃) | 环氧当量重(克/当量) | |
环氧树脂单体(I) | <25 | 378 |
环氧树脂单体(II) | <25 | 285 |
环氧树脂单体(XI) | 67 | 326 |
由表2可得知,由于环氧树脂单体(XI)为对称型环氧树脂(即其具有对称的化学结构),具有较高的结晶性,因此导致该环氧树脂单体(XI)具有较高的熔点(℃)(在室温下为固态)。此外,本案所述环氧树脂单体(I)及(II)为不对称型环氧树脂(即其具有不对称的化学结构),使得该环氧树脂单体(I)及(II)具有较低的熔点(℃),在室温下呈现液态。
环氧树脂组合物的制备
实施例11
将环氧树脂单体(I)与2-甲基咪唑(2-methyl imidazole,2MI)(作为硬化剂)混合,得到环氧树脂组合物(1)。在此,环氧树脂单体(I)与2-甲基咪唑的当量比为1:1。
实施例12
将环氧树脂单体(I)与聚丙二醇双(2-氨基丙基醚)(poly(propylene glycol)bis(2-aminopropyl ether),分子量为230)(商品编号为D-230)(作为硬化剂)混合,得到环氧树脂组合物(2)。在此,环氧树脂单体(I)与聚丙二醇双(2-氨基丙基醚)的当量比为1:1。
实施例13
将环氧树脂单体(I)、甲基四氢邻苯二甲酸酐(methyltetrahydrophthalicanhydride,MTHPA)(作为硬化剂)、二环[5.4.0]-1,8-二氮-7-壬烯(1,8-diazabicyclo[5.4.0]undec-7-ene,DBU)、以及2-乙基己酸(2-ethylhexanoic acid)混合,得到环氧树脂组合物(3)。在此,环氧树脂单体(I)与甲基四氢基邻苯二甲酸酐的当量比为1:1、二环[5.4.0]-1,8-二氮-7-壬烯的用量为0.25phr、以及2-乙基己酸的用量为0.25phr(以环氧树脂单体(I)为准)。
实施例14
将环氧树脂单体(I)、双酚F环氧树脂(商品编号为EXA-830LVP)、甲基四氢邻苯二甲酸酐(methyltetrahydrophthalic anhydride,MTHPA)(作为硬化剂)、二环[5.4.0]-1,8-二氮-7-壬烯(1,8-diazabicyclo[5.4.0]undec-7-ene,DBU)、以及2-乙基己酸(2-ethylhexanoic acid)混合,得到环氧树脂组合物(4)。在此,环氧树脂单体(I)、双酚F环氧树脂、以及甲基四氢基邻苯二甲酸酐的当量比为1:1:2、二环[5.4.0]-1,8-二氮-7-壬烯的用量为0.5phr、以及2-乙基己酸的用量为0.5phr(以环氧树脂单体(I)为准)。实施例15/>
实施例15依实施例14所述方式进行,除了将环氧树脂单体(I)、双酚F环氧树脂、以及甲基四氢基邻苯二甲酸酐的当量比由1:1:2调整至0.5:1.5:2,得到环氧树脂组合物(5)。
实施例16
实施例16依实施例11所述方式进行,除了将环氧树脂单体(I)与2-甲基咪唑的当量比由1:1调整至10:7,得到环氧树脂组合物(6)。
实施例17
实施例17依实施例12所述方式进行,除了将环氧树脂单体(I)与聚丙二醇双(2-氨基丙基醚)的当量比由1:1调整至10:7,得到环氧树脂组合物(7)。
实施例18
实施例18依实施例13所述方式进行,除了将环氧树脂单体(I)与甲基四氢基邻苯二甲酸酐的当量比由1:1调整至10:7,得到环氧树脂组合物(8)。
实施例19
实施例19依实施例11所述方式进行,除了将环氧树脂单体(I)以环氧树脂单体(II)取代,得到环氧树脂组合物(9)。
实施例20
实施例20依实施例12所述方式进行,除了将环氧树脂单体(I)以环氧树脂单体(II)取代,得到环氧树脂组合物(10)。
实施例21
实施例21依实施例13所述方式进行,除了将环氧树脂单体(I)以环氧树脂单体(II)取代,得到环氧树脂组合物(11)。
实施例22
实施例22依实施例14所述方式进行,除了将环氧树脂单体(I)以环氧树脂单体(II)取代,得到环氧树脂组合物(12)。
实施例23
实施例23依实施例15所述方式进行,除了将环氧树脂单体(I)以环氧树脂单体(II)取代,得到环氧树脂组合物(13)。
比较例2
比较例2依实施例14所述方式进行,除了将环氧树脂单体(I)以环氧树脂单体(XI)取代,得到环氧树脂组合物(14)。
比较例3
比较例3依实施例15所述方式进行,除了将环氧树脂单体(I)以环氧树脂单体(XI)取代,得到环氧树脂组合物(15)。
比较例4
比较例5
比较例6
流动性测试
对实施例12-15所得的环氧树脂组合物(2)-(5)以及比较例2及3所得的环氧树脂组合物(14)-(15)进行流动性的评估,结果如表3所示。在此,以25℃转速10rpm下测得的环氧树脂组合物粘度当作流动性标准。当粘度小于55,000cps,表示环氧树脂组合物具有不错的流动性,并以○表示。当粘度在55,000cps及65,000cps的间时,表示环氧树脂组合物具有尚可的流动性,以△表示;当粘度大于65,000cps时,表示环氧树脂组合物具有差的流动性或不具流动性,以X表示。
表3
由于本揭露所述环氧树脂单体具有不对称的化学结构,本揭露所述环氧树脂单体具有较低的熔点,可在室温下呈现液态。因此,以本揭露所述环氧树脂单体所制备的环氧树脂组合物具有流动性,适合作为封装材料。与环氧树脂组合物(4)相比,从环氧树脂组合物(14)及(15)以环氧树脂单体(XI)(对称型环氧树脂单体)取代环氧树脂单体(I)(不对称型环氧树脂单体),可观察到环氧树脂组合物的流动性明显降低(如表3所示),导致环氧树脂组合物的可加工性降低。环氧树脂组合物的固化物的性质测试
以傅立叶变换红外光谱(fourier-transform infrared spectroscopy,FT-IR)分析实施例11所得的环氧树脂组合物(1)及其固化物,可得知环氧树脂单体(I)其上的环氧乙烷基(oxiranyl)(IR特征峰911cm-1)在环氧树脂单体(I)进行开环交联后消失。
分别取实施例11-13所得的环氧树脂组合物(1)-(3)以及比较例4-6所得的环氧树脂组合物(16)-(18)的固化物进行耐热性评估以及酸裂解测试,结果如表3所示。耐热性评估是取5毫克环氧树脂组合物的固化物,以热重分析仪(thermogravimetric analysis,TGA)在氮气下测量其裂解温度(degraded temperature、Td)(5%重量损失时的温度)。酸裂解测试包含以下步骤:首先,将硫酸与水及四氢呋喃(THF)混合,得到浓度为0.2M的硫酸溶液(水与四氢呋喃的体积比为2:8)。接着,将25毫克环氧树脂组合物的固化物置于5毫升的硫酸溶液中,并在65℃下搅拌。最后,在经过特定时间后,观察固化物是否裂解或溶解于硫酸溶液中。当固化物完全溶解于硫酸溶液中,以◎表示。当固化物完全裂解成碎块并部份溶解于硫酸溶液中,以○表示。当固化物无法裂解或溶解,以X表示。
以傅立叶变换红外光谱(fourier-transform infrared spectroscopy,FT-IR)分析环氧树脂组合物(1)其固化物、以及其经酸裂解测试后的产物,可得知环氧树脂组合物(1)其固化物上的1625cm-1的C=N特征峰在进行酸裂解测试后讯号强度降低,且产生新的1647cm-1特征峰(C=O),这表示本揭露环氧树脂组合物的固化物在酸性环境下其亚胺基团确实会断键,并促进该环氧树脂组合物(1)固化物的裂解。
表4
如表4所示,由本揭露所述环氧树脂组合物(1)-(3)所得的固化物其热裂解温度(Td)皆可大于280℃,表示由本揭露所述环氧树脂组合物所得的固化物仍具有不错的耐热性。与环氧树脂组合物(16)-(18)相比,由于本揭露所述环氧树脂组合物(1)-(3)以环氧树脂单体(I)(不对称型环氧树脂单体)取代传统双酚F环氧树脂(对称型环氧树脂),因此可观察到本揭露所述环氧树脂组合物(1)-(3)其固化物可在65℃的酸性环境下裂解。
分别取实施例14、15、22及23所得的环氧树脂组合物(4)及(5)以及环氧树脂组合物(12)及(13)的固化物进行耐热性评估以及酸裂解测试,结果如表5所示。
表5
如表5所示,由本揭露所述环氧树脂组合物(4)及(5)、以及环氧树脂组合物(12)及(13)所得的固化物其裂解温度(Td)皆可大于300℃,表示由本揭露所述环氧树脂组合物所得的固化物仍具有不错的耐热性。此外,由本揭露所述环氧树脂组合物(4)及(5)、以及环氧树脂组合物(12)及(13)所得的固化物可在65℃的酸性环境下裂解。
分别取实施例16-21所得的环氧树脂组合物(6)-(11)的固化物,进行耐热性评估以及酸裂解测试,结果如表6所示。
表6
如表6所示,由本揭露所述环氧树脂组合物(6)-(11)所得的固化物其裂解温度(Td)皆可大于290℃,表示由本揭露所述环氧树脂组合物所得的固化物仍具有不错的耐热性。此外,由本揭露所述环氧树脂组合物(6)-(11)所得的固化物可在65℃的酸性环境下裂解。
综合上述,本揭露所述环氧树脂组合物的固化物可在相对低温(例如80℃或以下)的酸性环境下进行裂解,解决热固型树脂不易裂解的问题。此外,本揭露所述环氧树脂单体的熔点可大幅降低(例如低于室温),使得本揭露所述环氧树脂组合物其流动性大幅提升。
虽然本揭露已以数个实施例揭露如上,然其并非用以限定本揭露,任何本技术领域中具有通常知识者,在不脱离本揭露的精神和范围内,当可作任意的更动与润饰,因此本揭露的保护范围当视后附的请求项所界定者为准。
Claims (13)
2.如权利要求1所述的环氧树脂组合物,其中X1是以碳与Y1连接且以氮与A连接,以及X2是以碳与Y2连接且以氮与A连接。
3.如权利要求1所述的环氧树脂组合物,其中X1是以氮与Y1连接且以碳与A连接,以及X2是以氮与Y2连接且以碳与A连接。
9.如权利要求1所述的环氧树脂组合物,其中该环氧树脂单体的环氧当量重(EEW)为50克/当量至1500克/当量。
10.如权利要求1所述的环氧树脂组合物,更包含:
环氧树脂,其中该环氧树脂与该具有式(I)所示结构的环氧树脂单体的重量比为1:100至9:1。
11.如权利要求10所述的环氧树脂组合物,其中该环氧树脂是双酚A环氧树脂、双酚F环氧树脂、双酚S环氧树脂、酚醛环氧树脂、萘基环氧树脂、蒽基环氧树脂、双酚A二缩水甘油醚环氧树脂、乙二醇二缩水甘油醚环氧树脂、丙二醇二缩水甘油醚环氧树脂、或1,4-丁二醇二缩水甘油醚环氧树脂。
12.如权利要求1所述的环氧树脂组合物,其中该硬化剂是酸酐硬化剂、胺硬化剂、酚醛硬化剂、咪唑硬化剂、或上述的组合。
13.一种树脂薄膜,包含权利要求1至12任一项所述的环氧树脂组合物的固化物。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
TW110149642A TWI802196B (zh) | 2021-12-30 | 2021-12-30 | 環氧樹脂組合物以及樹脂薄膜 |
TW110149642 | 2021-12-30 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN116410445A true CN116410445A (zh) | 2023-07-11 |
Family
ID=86992387
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210141269.6A Pending CN116410445A (zh) | 2021-12-30 | 2022-02-16 | 环氧树脂组合物以及树脂薄膜 |
Country Status (3)
Country | Link |
---|---|
US (1) | US20230212342A1 (zh) |
CN (1) | CN116410445A (zh) |
TW (1) | TWI802196B (zh) |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104194038B (zh) * | 2014-08-29 | 2017-04-12 | 浙江大学 | 一种环氧树脂组合物及其湿法超声降解方法和应用 |
JP6725787B2 (ja) * | 2016-05-20 | 2020-07-22 | 学校法人東邦大学 | 芳香族ジアミンおよびこれを用いた液晶性エポキシ樹脂熱硬化物 |
-
2021
- 2021-12-30 TW TW110149642A patent/TWI802196B/zh active
-
2022
- 2022-02-16 CN CN202210141269.6A patent/CN116410445A/zh active Pending
- 2022-08-29 US US17/897,288 patent/US20230212342A1/en active Pending
Also Published As
Publication number | Publication date |
---|---|
US20230212342A1 (en) | 2023-07-06 |
TWI802196B (zh) | 2023-05-11 |
TW202325769A (zh) | 2023-07-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN112334513B (zh) | 马来酰亚胺树脂、硬化性树脂组合物及其硬化物 | |
JP5754731B2 (ja) | エポキシ樹脂、エポキシ樹脂の製造方法、及びその使用 | |
EP2915830B1 (en) | Epoxy resin curing agent | |
CN112334512B (zh) | 马来酰亚胺树脂、硬化性树脂组合物及其硬化物 | |
JP6764470B2 (ja) | マレイミド樹脂、硬化性樹脂組成物およびその硬化物 | |
KR20130118319A (ko) | 고분자량 에폭시 수지, 그 고분자량 에폭시 수지를 사용하는 수지 필름, 수지 조성물, 및 경화물 | |
TW201806985A (zh) | 熱硬化性樹脂組成物、預浸體及其硬化物 | |
JP4742625B2 (ja) | 水素化エポキシ樹脂、その製造方法及びエポキシ樹脂組成物 | |
JP6620981B2 (ja) | 熱硬化性成形材料、その製造方法および半導体封止材 | |
TW201529626A (zh) | 環氧樹脂、其製造方法、環氧樹脂組成物及其硬化物 | |
JPH0434565B2 (zh) | ||
TWI802196B (zh) | 環氧樹脂組合物以及樹脂薄膜 | |
JP6863679B2 (ja) | 溶液、その製造方法、エポキシ樹脂組成物及び積層板 | |
KR102099795B1 (ko) | 무수당 알코올 핵을 갖는 화합물 및 이의 제조 방법 | |
WO2006121030A1 (ja) | エポキシ樹脂、その製造方法及びその用途 | |
JP2004359672A (ja) | アニリン系化合物、およびその製造方法 | |
TWI471358B (zh) | A thermosetting resin, a composition thereof, a use thereof, and an epoxy resin composition | |
WO2022004596A1 (ja) | ベンゾオキサジン化合物含有混合物、これを含む硬化性組成物および該硬化性組成物を硬化させてなる硬化物 | |
JP6252978B2 (ja) | エポキシ樹脂硬化剤 | |
JP2010053314A (ja) | 熱硬化性樹脂、熱硬化性組成物、積層フィルム及び積層体 | |
WO2022004593A1 (ja) | ベンゾオキサジン化合物含有混合物の製造方法 | |
JP2023026380A (ja) | エポキシ化合物とエポキシ樹脂及びその硬化物 | |
JP2022013418A (ja) | ベンゾオキサジン化合物含有混合物、これを含む硬化性組成物および該硬化性組成物を硬化させてなる硬化物 | |
JP2023141768A (ja) | エポキシ樹脂、硬化性樹脂組成物、硬化物及び電気・電子材料 | |
JP2014162854A (ja) | 樹脂組成物及び硬化物 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination |