JP2023158145A - epoxy resin composition - Google Patents
epoxy resin composition Download PDFInfo
- Publication number
- JP2023158145A JP2023158145A JP2023145263A JP2023145263A JP2023158145A JP 2023158145 A JP2023158145 A JP 2023158145A JP 2023145263 A JP2023145263 A JP 2023145263A JP 2023145263 A JP2023145263 A JP 2023145263A JP 2023158145 A JP2023158145 A JP 2023158145A
- Authority
- JP
- Japan
- Prior art keywords
- group
- carbon atoms
- epoxy resin
- formula
- resin composition
- 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 56
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 56
- 239000000203 mixture Substances 0.000 title claims abstract description 47
- 150000001875 compounds Chemical class 0.000 claims abstract description 47
- 239000004417 polycarbonate Substances 0.000 claims abstract description 28
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 28
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 13
- -1 adamantane-2-ylidene group Chemical group 0.000 claims description 60
- 125000004432 carbon atom Chemical group C* 0.000 claims description 46
- 125000003545 alkoxy group Chemical group 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 125000002947 alkylene group Chemical group 0.000 claims description 11
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 11
- 125000001118 alkylidene group Chemical group 0.000 claims description 10
- 125000002993 cycloalkylene group Chemical group 0.000 claims description 8
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 7
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 claims description 6
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 claims description 3
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 125000004434 sulfur atom Chemical group 0.000 claims description 3
- 230000000694 effects Effects 0.000 description 25
- 238000001723 curing Methods 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 19
- 239000003795 chemical substances by application Substances 0.000 description 18
- 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 16
- 238000005809 transesterification reaction Methods 0.000 description 16
- 238000000034 method Methods 0.000 description 15
- 239000003054 catalyst Substances 0.000 description 10
- 229920003986 novolac Polymers 0.000 description 10
- 125000001424 substituent group Chemical group 0.000 description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 9
- PXKLMJQFEQBVLD-UHFFFAOYSA-N Bisphenol F Natural products C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 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 7
- 238000002156 mixing Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 5
- 230000001771 impaired effect Effects 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- BHWMWBACMSEDTE-UHFFFAOYSA-N 4-[1-(4-hydroxyphenyl)cyclododecyl]phenol Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCCCCCCCC1 BHWMWBACMSEDTE-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- 150000001339 alkali metal compounds Chemical class 0.000 description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 239000011256 inorganic filler Substances 0.000 description 4
- 229910003475 inorganic filler Inorganic materials 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- 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 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 3
- 229910000024 caesium carbonate Inorganic materials 0.000 description 3
- 125000005587 carbonate group Chemical group 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 229930003836 cresol Natural products 0.000 description 3
- 238000006735 epoxidation reaction Methods 0.000 description 3
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 150000003018 phosphorus compounds Chemical class 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- LTPBRCUWZOMYOC-UHFFFAOYSA-N Beryllium oxide Chemical compound O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000012695 Interfacial polymerization Methods 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 2
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 239000002516 radical scavenger Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 229910052845 zircon Inorganic materials 0.000 description 2
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 2
- GCLVVFYKIZYIIL-UHFFFAOYSA-N (2-butylphenyl)-diphenylborane Chemical compound CCCCC1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1 GCLVVFYKIZYIIL-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 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
- QVLAWKAXOMEXPM-UHFFFAOYSA-N 1,1,1,2-tetrachloroethane Chemical compound ClCC(Cl)(Cl)Cl QVLAWKAXOMEXPM-UHFFFAOYSA-N 0.000 description 1
- OWEYKIWAZBBXJK-UHFFFAOYSA-N 1,1-Dichloro-2,2-bis(4-hydroxyphenyl)ethylene Chemical compound C1=CC(O)=CC=C1C(=C(Cl)Cl)C1=CC=C(O)C=C1 OWEYKIWAZBBXJK-UHFFFAOYSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- AHBGXHAWSHTPOM-UHFFFAOYSA-N 1,3,2$l^{4},4$l^{4}-dioxadistibetane 2,4-dioxide Chemical compound O=[Sb]O[Sb](=O)=O AHBGXHAWSHTPOM-UHFFFAOYSA-N 0.000 description 1
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 1
- 125000005655 1,3-cyclohexylene group Chemical group [H]C1([H])C([H])([H])C([H])([*:1])C([H])([H])C([H])([*:2])C1([H])[H] 0.000 description 1
- 125000005838 1,3-cyclopentylene group Chemical group [H]C1([H])C([H])([H])C([H])([*:2])C([H])([H])C1([H])[*:1] 0.000 description 1
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 description 1
- 125000004955 1,4-cyclohexylene group Chemical group [H]C1([H])C([H])([H])C([H])([*:1])C([H])([H])C([H])([H])C1([H])[*:2] 0.000 description 1
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- MQCPOLNSJCWPGT-UHFFFAOYSA-N 2,2'-Bisphenol F Chemical compound OC1=CC=CC=C1CC1=CC=CC=C1O MQCPOLNSJCWPGT-UHFFFAOYSA-N 0.000 description 1
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- YMTYZTXUZLQUSF-UHFFFAOYSA-N 3,3'-Dimethylbisphenol A Chemical compound C1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=CC=2)=C1 YMTYZTXUZLQUSF-UHFFFAOYSA-N 0.000 description 1
- UIDDPPKZYZTEGS-UHFFFAOYSA-N 3-(2-ethyl-4-methylimidazol-1-yl)propanenitrile Chemical compound CCC1=NC(C)=CN1CCC#N UIDDPPKZYZTEGS-UHFFFAOYSA-N 0.000 description 1
- BVYPJEBKDLFIDL-UHFFFAOYSA-N 3-(2-phenylimidazol-1-yl)propanenitrile Chemical compound N#CCCN1C=CN=C1C1=CC=CC=C1 BVYPJEBKDLFIDL-UHFFFAOYSA-N 0.000 description 1
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 description 1
- UMPGNGRIGSEMTC-UHFFFAOYSA-N 4-[1-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexyl]phenol Chemical compound C1C(C)CC(C)(C)CC1(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 UMPGNGRIGSEMTC-UHFFFAOYSA-N 0.000 description 1
- GYLZMVYMSPSPDA-UHFFFAOYSA-N 4-[1-(4-hydroxyphenyl)-3-methylcyclohexyl]phenol Chemical compound C1C(C)CCCC1(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 GYLZMVYMSPSPDA-UHFFFAOYSA-N 0.000 description 1
- NUDSREQIJYWLRA-UHFFFAOYSA-N 4-[9-(4-hydroxy-3-methylphenyl)fluoren-9-yl]-2-methylphenol Chemical compound C1=C(O)C(C)=CC(C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=C(C)C(O)=CC=2)=C1 NUDSREQIJYWLRA-UHFFFAOYSA-N 0.000 description 1
- NUKYPUAOHBNCPY-UHFFFAOYSA-N 4-aminopyridine Chemical compound NC1=CC=NC=C1 NUKYPUAOHBNCPY-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- 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 1
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004110 Zinc silicate Substances 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- UUQQGGWZVKUCBD-UHFFFAOYSA-N [4-(hydroxymethyl)-2-phenyl-1h-imidazol-5-yl]methanol Chemical compound N1C(CO)=C(CO)N=C1C1=CC=CC=C1 UUQQGGWZVKUCBD-UHFFFAOYSA-N 0.000 description 1
- 230000035508 accumulation Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- XFSBVAOIAHNAPC-WSORPINJSA-N acetylbenzoylaconine Chemical compound O([C@H]1[C@]2(O)C[C@H]3C45[C@@H]6[C@@H]([C@@]([C@H]31)(OC(C)=O)[C@@H](O)[C@@H]2OC)[C@H](OC)C4[C@]([C@@H](C[C@H]5OC)O)(COC)CN6CC)C(=O)C1=CC=CC=C1 XFSBVAOIAHNAPC-WSORPINJSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000001343 alkyl silanes Chemical class 0.000 description 1
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-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
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000005010 aminoquinolines Chemical class 0.000 description 1
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 229910000411 antimony tetroxide Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 1
- 125000000649 benzylidene group Chemical group [H]C(=[*])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- PDYNXWPJDVOHDW-UHFFFAOYSA-N bis(3-methylphenyl) carbonate Chemical compound CC1=CC=CC(OC(=O)OC=2C=C(C)C=CC=2)=C1 PDYNXWPJDVOHDW-UHFFFAOYSA-N 0.000 description 1
- PACOTQGTEZMTOT-UHFFFAOYSA-N bis(ethenyl) carbonate Chemical compound C=COC(=O)OC=C PACOTQGTEZMTOT-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 150000007973 cyanuric acids Chemical class 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- ANHGITKPRSIRHT-UHFFFAOYSA-N cyclohexyl phenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1CCCCC1 ANHGITKPRSIRHT-UHFFFAOYSA-N 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- FYIBPWZEZWVDQB-UHFFFAOYSA-N dicyclohexyl carbonate Chemical compound C1CCCCC1OC(=O)OC1CCCCC1 FYIBPWZEZWVDQB-UHFFFAOYSA-N 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- YCNSGSUGQPDYTK-UHFFFAOYSA-N ethyl phenyl carbonate Chemical compound CCOC(=O)OC1=CC=CC=C1 YCNSGSUGQPDYTK-UHFFFAOYSA-N 0.000 description 1
- 229960004979 fampridine Drugs 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910052839 forsterite Inorganic materials 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000002440 hydroxy compounds Chemical class 0.000 description 1
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000002648 laminated material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910052744 lithium 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
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- XTBFPVLHGVYOQH-UHFFFAOYSA-N methyl phenyl carbonate Chemical compound COC(=O)OC1=CC=CC=C1 XTBFPVLHGVYOQH-UHFFFAOYSA-N 0.000 description 1
- NQMRYBIKMRVZLB-UHFFFAOYSA-N methylamine hydrochloride Chemical compound [Cl-].[NH3+]C NQMRYBIKMRVZLB-UHFFFAOYSA-N 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- WLFOHIVICZSIKG-UHFFFAOYSA-N n,n-dimethyl-1h-imidazol-2-amine Chemical compound CN(C)C1=NC=CN1 WLFOHIVICZSIKG-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical class [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001639 phenylmethylene group Chemical group [H]C(=*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 150000004714 phosphonium salts Chemical group 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- IYMSIPPWHNIMGE-UHFFFAOYSA-N silylurea Chemical compound NC(=O)N[SiH3] IYMSIPPWHNIMGE-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 description 1
- KCTAHLRCZMOTKM-UHFFFAOYSA-N tripropylphosphane Chemical compound CCCP(CCC)CCC KCTAHLRCZMOTKM-UHFFFAOYSA-N 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- XSMMCTCMFDWXIX-UHFFFAOYSA-N zinc silicate Chemical compound [Zn+2].[O-][Si]([O-])=O XSMMCTCMFDWXIX-UHFFFAOYSA-N 0.000 description 1
- 235000019352 zinc silicate Nutrition 0.000 description 1
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
- 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
-
- 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
- C08G59/32—Epoxy compounds containing three or more epoxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
本発明は、耐熱性及び誘電特性に優れるエポキシ樹脂組成物に関する。 The present invention relates to an epoxy resin composition that has excellent heat resistance and dielectric properties.
エポキシ樹脂は、硬化剤で硬化させることにより、機械的性質、密着性、耐水性、耐薬品性、耐熱性、電気絶縁性などに優れた硬化物となるために、接着剤、塗料、積層板、成形材料、注型材料などの幅広い分野に利用されている。
例えば、特許文献１、２には、ビスフェノールＡ型のポリカーボネートオリゴマーを硬化剤として使用することにより、可撓性、柔軟性、耐熱性に優れ、機械特性が向上したエポキシ樹脂発泡体が得られることが具体的に開示されているが、その耐熱性等の性能は、近年求められるレベルからみて、十分といえるものではなかった。
When epoxy resin is cured with a curing agent, it becomes a cured product with excellent mechanical properties, adhesion, water resistance, chemical resistance, heat resistance, electrical insulation, etc., so it is used in adhesives, paints, and laminates. It is used in a wide range of fields such as , molding materials, and casting materials.
For example, Patent Documents 1 and 2 disclose that by using a bisphenol A type polycarbonate oligomer as a curing agent, an epoxy resin foam with excellent flexibility, softness, heat resistance, and improved mechanical properties can be obtained. has been specifically disclosed, but its performance such as heat resistance has not been sufficient in view of the level required in recent years.
本発明は、上述した事情を背景としてなされたものであって、耐熱性のみならず誘電特性にも優れるエポキシ樹脂組成物を提供することを目的とする。 The present invention was made against the background of the above-mentioned circumstances, and an object of the present invention is to provide an epoxy resin composition that is excellent not only in heat resistance but also in dielectric properties.
本発明者らは、上述の課題解決のために鋭意検討した結果、下記式（１）及び／又は式（２）及び／又は式（３）で表され、重量平均分子量（Ｍｗ）が５００以上１０，０００以下の範囲であることを特徴とするポリカーボネートオリゴマーを硬化剤として、１分子中に２個以上のエポキシ基を有するポリエポキシ化合物と組み合わせてエポキシ樹脂組成物とすることにより、耐熱性のみならず誘電特性をも向上し得ることを見出し、本発明を完成した。 As a result of intensive studies aimed at solving the above-mentioned problems, the present inventors found that the compound is represented by the following formula (1) and/or formula (2) and/or formula (3) and has a weight average molecular weight (Mw) of 500 or more. 10,000 or less as a curing agent and a polyepoxy compound having two or more epoxy groups in one molecule to form an epoxy resin composition. The present invention was completed based on the discovery that the dielectric properties could also be improved.
本発明は以下の通りである。
１．（Ａ）下記式（１）及び／又は式（２）及び／又は式（３）で表され、重量平均分子量（Ｍｗ）が５００以上１０，０００以下の範囲であることを特徴とするポリカーボネートオリゴマーと、（Ｂ）１分子中に２個以上のエポキシ基を有するポリエポキシ化合物を含有することを特徴とするエポキシ樹脂組成物。
２．１．記載のエポキシ樹脂組成物を硬化してなる硬化物。
The invention is as follows.
1. (A) A polycarbonate oligomer represented by the following formula (1) and/or formula (2) and/or formula (3) and characterized by having a weight average molecular weight (Mw) in the range of 500 or more and 10,000 or less and (B) an epoxy resin composition containing a polyepoxy compound having two or more epoxy groups in one molecule.
2.1. A cured product obtained by curing the epoxy resin composition described above.
本発明によるエポキシ樹脂組成物は、式（１）及び／又は式（２）及び／又は式（３）で表され、特定の重量平均分子量を有するポリカーボネートオリゴマーを硬化剤として含有することにより、誘電特性が向上し工業的に有利な効果を発揮する。
また、本発明によるエポキシ樹脂組成物を硬化することにより得られた硬化物は、ガラス転移温度が高く耐熱性に優れているため、耐熱性が要求される工業用材料として好適である。
The epoxy resin composition according to the present invention is represented by formula (1) and/or formula (2) and/or formula (3) and contains a polycarbonate oligomer having a specific weight average molecular weight as a curing agent, thereby producing a dielectric material. Improved properties and industrially advantageous effects.
Further, the cured product obtained by curing the epoxy resin composition according to the present invention has a high glass transition temperature and excellent heat resistance, and is therefore suitable as an industrial material that requires heat resistance.
以下、本発明のエポキシ樹脂組成物について詳細に説明する。
＜本発明の成分（Ａ）について＞
本発明における成分（Ａ）のポリカーボネートオリゴマーは、重量平均分子量（Ｍｗ）が５００以上１０，０００以下の範囲である、下記式（１）及び／又は式（２）及び／又は式（３）で表される化合物である。
<About component (A) of the present invention>
The polycarbonate oligomer of component (A) in the present invention has a weight average molecular weight (Mw) of 500 or more and 10,000 or less and is represented by the following formula (1) and/or formula (2) and/or formula (3). The compound represented by
上記式（１）～（３）において、Ｒ１、Ｒ２、Ｒ３及びＲ４のいずれかが、炭素原子数１～８のアルキル基である場合、アルキル基としては、好ましくは炭素原子数１～６の直鎖状、分岐鎖状のアルキル基であり、具体的には、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、イソブチル基等が挙げられる。このようなアルキル基には、本発明の効果を損なわない範囲で例えばフェニル基、炭素原子数１～４のアルコキシ基等の置換基を有していてもよい。
上記式（１）～（３）において、Ｒ１、Ｒ２、Ｒ３及びＲ４のいずれかが、炭素原子数５～１２のシクロアルキル基である場合、シクロアルキル基としては、好ましくは炭素原子数５～７のシクロアルキル基であり、具体的には、例えば、シクロヘキシル基、シクロペンチル基、シクロへプチル基等が挙げられる。このようなシクロアルキル基には、本発明の効果を損なわない範囲で、例えば、直鎖又は分岐鎖状の炭素原子数１～４のアルキル基、炭素原子数１～４のアルコキシ基、フェニル基等の置換基を有していてもよい。
また、上記式（１）～（３）において、Ｒ１、Ｒ２、Ｒ３及びＲ４のいずれかが、炭素原子数１～８のアルコキシ基である場合、アルコキシ基としては、好ましくは炭素原子数１～４の直鎖状、分岐鎖状のアルコキシ基であり、具体的には、例えば、メトキシ基、エトキシ基等が挙げられる。このようなアルコキシ基には本願の効果を損なわない範囲で、例えば、フェニル基、炭素原子数１～４のアルコキシ基等の置換基を有していてもよい。
さらに、上記式（１）～（３）において、Ｒ１、Ｒ２、Ｒ３及びＲ４のいずれかが、炭素原子数６～１２の芳香族炭化水素基である場合、芳香族炭化水素基としては、具体的には、例えば、フェニル基、ナフチル基等が挙げられる。このような芳香族炭化水素基には、本発明の効果を損なわない範囲で、例えば、炭素原子数１～４のアルキル基及び／又は、炭素原子数１～４のアルコキシ基が１～３程度置換していてもよい。
In the above formulas (1) to (3), when any one of R 1 , R 2 , R 3 and R 4 is an alkyl group having 1 to 8 carbon atoms, the alkyl group preferably has a carbon number of It is a linear or branched alkyl group having 1 to 6 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an isobutyl group, and the like. Such an alkyl group may have a substituent such as a phenyl group or an alkoxy group having 1 to 4 carbon atoms, as long as the effects of the present invention are not impaired.
In the above formulas (1) to (3), when any of R 1 , R 2 , R 3 and R 4 is a cycloalkyl group having 5 to 12 carbon atoms, the cycloalkyl group is preferably a carbon It is a cycloalkyl group having 5 to 7 atoms, and specific examples thereof include a cyclohexyl group, a cyclopentyl group, a cycloheptyl group, and the like. Such cycloalkyl groups include, for example, linear or branched alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, and phenyl groups, as long as the effects of the present invention are not impaired. It may have substituents such as.
In addition, in the above formulas (1) to (3), when any one of R 1 , R 2 , R 3 and R 4 is an alkoxy group having 1 to 8 carbon atoms, the alkoxy group is preferably a carbon It is a linear or branched alkoxy group having 1 to 4 atoms, and specific examples thereof include a methoxy group and an ethoxy group. Such an alkoxy group may have a substituent, such as a phenyl group or an alkoxy group having 1 to 4 carbon atoms, within a range that does not impair the effects of the present application.
Furthermore, in the above formulas (1) to (3), when any of R 1 , R 2 , R 3 and R 4 is an aromatic hydrocarbon group having 6 to 12 carbon atoms, the aromatic hydrocarbon group Specific examples thereof include phenyl group, naphthyl group, and the like. Such an aromatic hydrocarbon group may contain, for example, about 1 to 3 alkyl groups having 1 to 4 carbon atoms and/or alkoxy groups having 1 to 4 carbon atoms, as long as the effects of the present invention are not impaired. May be replaced.
上記式（１）～（３）において、Ｘが炭素原子数１～１５のアルキレン基である場合、アルキレン基としては、好ましくは直鎖状又は分岐鎖状の炭素原子数１～８のアルキレン基であり、より好ましくは直鎖状又は分岐鎖状の炭素原子数１～４のアルキレン基であり、具体的には、例えば、メチレン基、エチレン基、プロピレン基、ブチレン基等が挙げられる。このようなアルキレン基には、本発明の効果を損なわない範囲で、例えば芳香族炭化水素基、アルコキシ基等の置換基を有していてもよく、フェニルメチレン基、ジフェニルメチレン基などが例示できる。
上記式（１）～（３）において、Ｘが炭素原子数５～１５のシクロアルキレン基である場合、シクロアルキレン基としては、好ましくは炭素原子数５～７のシクロアルキレン基であり、具体的には、例えば、１，３－シクロペンチレン基、１，４－シクロヘキシレン基、１，３－シクロヘキシレン基等が挙げられる。このようなシクロアルキレン基には、本発明の効果を損なわない範囲で、例えば、炭素原子数１～４のアルキル基が１～３程度置換していてもよい。
上記式（１）～（３）において、Ｘが炭素原子数２～１５のアルキリデン基である場合、好ましいアルキリデン基としては、直鎖状又は分岐鎖状の炭素原子数２～１５のアルキリデン基であり、具体的には、例えば、エチリデン基、プロパン－１－イリデン基、イソプロピリデン基、ブタン－１－イリデン基、ブタン－２－イリデン基、２－メチルプロパン－１－イリデン基、ペンタン－２－イリデン基、３－メチルブタン－１－イリデン基、ヘキサン－２－イリデン基、ヘプタン－４－イリデン基、２－エチルヘキサン－１－イリデン基、ノナン－２－イリデン基等が挙げられる。このようなアルキリデン基には本発明の効果を損なわない範囲で、例えば、芳香族炭化水素基、アルコキシ基等の置換基を有していてもよい。
上記式（１）～（３）において、Ｘが炭素原子数５～１５のシクロアルキリデン基である場合、シクロアルキリデン基としては具体的には、例えば、シクロペンチリデン基、シクロヘキシリデン基、シクロヘプチリデン基、シクロドデシリデン基等が挙げられる。このようなシクロアルキリデン基には、本発明の効果を損なわない範囲で、例えば、芳香族炭化水素基、アルキル基、アルコキシ基等の置換基を有していてもよく、具体的には、炭素原子数１～４のアルキル基が１～３程度置換していてもよい。その具体例としては、３－メチルシクロヘキサン－１－イリデン基、３，３，５－トリメチルシクロヘキサン－１－イリデン基等が挙げられる。また、このようなシクロアルキリデン基には、本発明の効果を損なわない範囲で、例えば、芳香族炭化水素基が縮合していてもよい。その具体例としては、フルオレン－９－イリデン基等が挙げられる。
上記式（１）～（３）において、Ｘがフェニレン基である場合、フェニレン基としては具体的には、例えば、１，４－フェニレン基、１，３－フェニレン基等が挙げられる。このようなフェニレン基には、本発明の効果を損なわない範囲で、例えば、芳香族炭化水素基、アルキル基、アルコキシ基等の置換基を有していてもよい。
In the above formulas (1) to (3), when X is an alkylene group having 1 to 15 carbon atoms, the alkylene group is preferably a linear or branched alkylene group having 1 to 8 carbon atoms. More preferably, it is a linear or branched alkylene group having 1 to 4 carbon atoms, and specific examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group, and the like. Such an alkylene group may have a substituent such as an aromatic hydrocarbon group or an alkoxy group within a range that does not impair the effects of the present invention, and examples thereof include a phenylmethylene group and a diphenylmethylene group. .
In the above formulas (1) to (3), when X is a cycloalkylene group having 5 to 15 carbon atoms, the cycloalkylene group is preferably a cycloalkylene group having 5 to 7 carbon atoms, and specifically Examples of the group include 1,3-cyclopentylene group, 1,4-cyclohexylene group, and 1,3-cyclohexylene group. Such a cycloalkylene group may be substituted with, for example, about 1 to 3 alkyl groups having 1 to 4 carbon atoms, as long as the effects of the present invention are not impaired.
In the above formulas (1) to (3), when X is an alkylidene group having 2 to 15 carbon atoms, the preferable alkylidene group is a linear or branched alkylidene group having 2 to 15 carbon atoms. Yes, specifically, for example, ethylidene group, propan-1-ylidene group, isopropylidene group, butane-1-ylidene group, butan-2-ylidene group, 2-methylpropan-1-ylidene group, pentane-2 -ylidene group, 3-methylbutane-1-ylidene group, hexane-2-ylidene group, heptane-4-ylidene group, 2-ethylhexane-1-ylidene group, nonane-2-ylidene group, and the like. Such an alkylidene group may have a substituent such as an aromatic hydrocarbon group or an alkoxy group within a range that does not impair the effects of the present invention.
In the above formulas (1) to (3), when X is a cycloalkylidene group having 5 to 15 carbon atoms, specific examples of the cycloalkylidene group include cyclopentylidene group, cyclohexylidene group, cyclohexylidene group, Examples include heptylidene group and cyclododecylidene group. Such a cycloalkylidene group may have a substituent such as an aromatic hydrocarbon group, an alkyl group, or an alkoxy group within a range that does not impair the effects of the present invention. Approximately 1 to 3 alkyl groups having 1 to 4 atoms may be substituted. Specific examples thereof include 3-methylcyclohexane-1-ylidene group and 3,3,5-trimethylcyclohexane-1-ylidene group. Furthermore, such a cycloalkylidene group may be condensed with, for example, an aromatic hydrocarbon group within a range that does not impair the effects of the present invention. Specific examples thereof include fluorene-9-ylidene group and the like.
In the above formulas (1) to (3), when X is a phenylene group, specific examples of the phenylene group include a 1,4-phenylene group and a 1,3-phenylene group. Such a phenylene group may have a substituent, such as an aromatic hydrocarbon group, an alkyl group, or an alkoxy group, within a range that does not impair the effects of the present invention.
上記式（１）～（３）における、Ｘの好ましい態様として、単結合、置換基を有していてもよい炭素原子数１～４のアルキレン基、置換基を有していてもよい炭素原子数１～４のアルキリデン基、置換基を有していてもよい炭素原子数５～１５のシクロアルキリデン基が挙げられる。
中でも、Ｘのより好ましい態様として、単結合、メチレン基、エチレン基、エチリデン基、プロピリデン基、イソプロピリデン基、ブチリデン基、フェニルメチリデン基、１－フェニルエタン－１－イリデン基、シクロペンチリデン基、シクロヘキシリデン基、シクロヘプチリデン基、シクロドデシリデン基、４－メチルシクロヘキサン－１－イリデン基、３，３，５－トリメチルシクロヘキサン－１－イリデン基、フルオレン－９－イリデン基が挙げられる。
In the above formulas (1) to (3), preferred embodiments of X include a single bond, an alkylene group having 1 to 4 carbon atoms which may have a substituent, and a carbon atom which may have a substituent. Examples include an alkylidene group having 1 to 4 carbon atoms and a cycloalkylidene group having 5 to 15 carbon atoms which may have a substituent.
Among them, more preferable embodiments of X include a single bond, a methylene group, an ethylene group, an ethylidene group, a propylidene group, an isopropylidene group, a butylidene group, a phenylmethylidene group, a 1-phenylethane-1-ylidene group, and a cyclopentylidene group. , cyclohexylidene group, cycloheptylidene group, cyclododecylidene group, 4-methylcyclohexane-1-ylidene group, 3,3,5-trimethylcyclohexane-1-ylidene group, fluorene-9-ylidene group. It will be done.
式（１）及び／又は式（２）及び／又は式（３）で表されるポリカーボネートオリゴマーは、従来公知の任意の製造方法により製造されるものを使用できる。具体的には、例えば、界面重合法、溶融エステル交換法、ピリジン法、環状カーボネート化合物の開環重合法、プレポリマーの固相エステル交換法等を挙げることができる。中でも、界面重合法、溶融エステル交換法、プレポリマーの固相エステル交換法を用いることが産業上有利である。これらの中でも、ホスゲンを使用しない溶融エステル交換法や、溶融エステル交換法によるプレポリマーの固相エステル交換法が、特に好ましい。
上記の製造方法は、下記式（４）で表されるジヒドロキシ化合物と炭酸エステル形成剤とを使用して行われる。
The above manufacturing method is carried out using a dihydroxy compound represented by the following formula (4) and a carbonate ester forming agent.
＜式（４）で表されるジヒドロキシ化合物について＞
式（４）で表されるジヒドロキシ化合物としては、具体的には、例えば、２,２－ビス（４－ヒドロキシ－３－メチルフェニル）プロパン、１，１－ビス（４－ヒドロキシフェニル）－１－フェニルエタン、１，１－ビス（４－ヒドロキシフェニル）－３，３，５－トリメチルシクロヘキサン、４，４’－ジヒドロキシビフェニル等のジヒドロキシビフェニル化合物類、９，９－ビス（４－ヒドロキシ－３－メチルフェニル）フルオレン、１,１－ビス（４－ヒドロキシフェニル）エタン、１,１－ビス（４－ヒドロキシフェニル）メタン又は１,１－ビス（ヒドロキシフェニル）メタンの異性体混合物、１,１－ビス（４－ヒドロキシフェニル）シクロドデカン、１，１－ビス（４－ヒドロキシフェニル）－３－メチルシクロヘキサンなどが挙げられる。
重合反応に際し、式（４）で表されるジヒドロキシ化合物は単独でも、２種以上を任意の割合で混合して用いても良い。また、式（４）で表されるジヒドロキシ化合物以外のジヒドロキシ化合物を使用する場合には、全芳香族ジヒドロキシ化合物中、式（４）で表されるジヒドロキシ化合物以外のヒドロキシ化合物共重合原料の割合は、０～９０モル％の範囲、好ましくは０～８５モル％の範囲、より好ましくは０～８０モル％の範囲である。
本発明における式（１）及び／又は式（２）及び／又は式（３）で表されるポリカーボネートオリゴマーの重量平均分子量は、５００以上１０，０００以下の範囲であり、好ましくは６００以上９，０００以下の範囲、より好ましくは８００以上８，５００以下の範囲、更に好ましくは１，０００以上８，０００以下の範囲である。
<About the dihydroxy compound represented by formula (4)>
Specifically, the dihydroxy compound represented by formula (4) includes, for example, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)-1 -Dihydroxybiphenyl compounds such as phenylethane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4'-dihydroxybiphenyl, 9,9-bis(4-hydroxy-3 - methylphenyl)fluorene, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)methane or isomer mixture of 1,1-bis(hydroxyphenyl)methane, 1,1 -bis(4-hydroxyphenyl)cyclododecane, 1,1-bis(4-hydroxyphenyl)-3-methylcyclohexane, and the like.
In the polymerization reaction, the dihydroxy compound represented by formula (4) may be used alone or in a mixture of two or more in any proportion. In addition, when using a dihydroxy compound other than the dihydroxy compound represented by formula (4), the proportion of the hydroxy compound copolymerization raw material other than the dihydroxy compound represented by formula (4) in the wholly aromatic dihydroxy compound is , in the range of 0 to 90 mol%, preferably in the range of 0 to 85 mol%, more preferably in the range of 0 to 80 mol%.
The weight average molecular weight of the polycarbonate oligomer represented by formula (1) and/or formula (2) and/or formula (3) in the present invention is in the range of 500 to 10,000, preferably 600 to 9,000. 000 or less, more preferably 800 or more and 8,500 or less, still more preferably 1,000 or more and 8,000 or less.
＜炭酸エステル形成剤について＞
式（４）で表されるジヒドロキシ化合物と反応させる炭酸エステル形成剤としては、具体的には、例えば、ジフェニルカーボネート、ジトリルカーボネート、ビス（ｍ－クレジル）カーボネート等の炭酸ジアリール、ジメチルカーボネート、ジエチルカーボネート、ジシクロヘキシルカーボネート等の炭酸ジアルキル、メチルフェニルカーボネート、エチルフェニルカーボネート、シクロヘキシルフェニルカーボネート等の炭酸アルキルアリール又はジビニルカーボネート、ジイソプロペニルカーボネート、ジプロペニルカーボネート等の炭酸ジアルケニル等や炭酸が挙げられる。さらに、ホスゲン等のジハロゲン化カルボニル化合物等やトリホスゲンも挙げられる。これらの中で、炭酸ジアリールが好ましく、ジフェニルカーボネートが特に好ましい。
<About carbonate ester forming agent>
Specific examples of the carbonate ester forming agent to be reacted with the dihydroxy compound represented by formula (4) include diaryl carbonates such as diphenyl carbonate, ditolyl carbonate, and bis(m-cresyl) carbonate, dimethyl carbonate, and diethyl carbonate. carbonate, dialkyl carbonate such as dicyclohexyl carbonate, alkylaryl carbonate such as methylphenyl carbonate, ethylphenyl carbonate, cyclohexylphenyl carbonate, dialkenyl carbonate such as divinyl carbonate, diisopropenyl carbonate, dipropenyl carbonate, etc., and carbonic acid. Further examples include dihalogenated carbonyl compounds such as phosgene, and triphosgene. Among these, diaryl carbonate is preferred, and diphenyl carbonate is particularly preferred.
＜溶融エステル交換法について＞
式（１）及び／又は式（２）及び／又は式（３）で表されるポリカーボネートオリゴマーで表されるポリカーボネートオリゴマーの製造方法として、溶融エステル交換法について説明する。
溶融エステル交換反応の方法としては、式（４）で表されるジヒドロキシ化合物と、炭酸エステル形成剤としてジフェニルカーボネートを使用する場合には、触媒の存在下、常圧又は減圧の不活性ガス雰囲気で加熱しながら撹拌し、生成するフェノールを留出させて行われる。通常、式（４）で表されるジヒドロキシ化合物と炭酸エステル形成剤の混合比率や、エステル交換反応時の減圧度を調整して、所望の分子量及び末端水酸基量を調整した、式（１）及び／又は式（２）及び／又は式（３）で表されるポリカーボネートオリゴマーを得ることができる。
式（１）及び／又は式（２）及び／又は式（３）で表されるポリカーボネートオリゴマーを得るために、式（４）で表されるジヒドロキシ化合物と炭酸エステル形成剤との混合比率は、式（４）で表されるジヒドロキシ化合物１モルに対して、炭酸エステル形成剤を通常０．２～５モル倍、好ましくは０．３～３．３モル倍、更に好ましくは０．４～２．５モル倍用いる。
溶融エステル交換反応に際し、反応速度を高めるため、必要に応じてエステル交換触媒が用いられる。エステル交換触媒としては、特に制限はなく、例えば、リチウム、ナトリウム、セシウムの水酸化物、炭酸塩、炭酸水素化合物等の無機アルカリ金属化合物、アルコラート、有機カルボン酸塩等の有機アルカリ金属化合物等のアルカリ金属化合物；ベリリウム、マグネシウム等の水酸化物、炭酸塩等の無機アルカリ土類金属化合物、アルコラート、有機カルボン酸塩等の有機アルカリ土類金属化合物等のアルカリ土類金属化合物；テトラメチルホウ素、テトラエチルホウ素、ブチルトリフェニルホウ素等のナトリウム塩、カルシウム塩、マグネシウム塩等の塩基性ホウ素化合物；トリエチルホスフィン、トリ－ｎ－プロピルホスフィン等の３価のリン化合物、又は、これらの化合物から誘導される４級ホスホニウム塩等の塩基性リン化合物；テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラブチルアンモニウムヒドロキシド等の塩基性アンモニウム化合物；４－アミノピリジン、２－ジメチルアミノイミダゾール、アミノキノリン等アミン系化合物等の公知のエステル交換触媒を用いることができる。中でも、アルカリ金属化合物が好ましく、特に炭酸セシウム、水酸化セシウム等のセシウム化合物が好ましい。
触媒の使用量は、触媒残留物による生成オリゴマーの品質上の問題が生じない範囲で用いられ、触媒の種類により好適な添加量が異なるので一概には言えないが、概略、例えば、式（Ｂ）で表されるジヒドロキシ化合物１モルに対して通常０．０５～１００μモル、好ましくは０．０８～５０μモル、より好ましくは０．１～２０μモル、さらに好ましくは０．１～５μモルである。触媒はそのままで添加してもよいし、溶媒に溶解して添加してもよく、溶媒としては、例えば水、フェノール等の反応に影響しないものが好ましい。
溶融エステル交換反応の反応条件は、温度は通常１２０～３６０℃の範囲、好ましくは１５０～２８０℃の範囲、より好ましくは１８０～２６０℃の範囲である。反応温度が低すぎるとエステル交換反応が進行せず、反応温度が高いと分解反応等の副反応が進行するので好ましくない。反応は好ましくは減圧下でおこなわれる。反応圧力は、反応温度において原料である炭酸エステル形成剤が系外に留出せず、フェノール等の副生物が留出できる圧力であることが好ましい。このような反応条件において、反応は通常０．５～１０時間程度で完結する。
<About melt transesterification method>
A melt transesterification method will be described as a method for producing a polycarbonate oligomer represented by formula (1) and/or formula (2) and/or formula (3).
As a method for melt transesterification, when using a dihydroxy compound represented by formula (4) and diphenyl carbonate as a carbonate ester forming agent, it is carried out in the presence of a catalyst in an inert gas atmosphere at normal pressure or reduced pressure. This is done by stirring while heating and distilling off the produced phenol. Usually, the formula (1) and A polycarbonate oligomer represented by formula (2) and/or formula (3) can be obtained.
In order to obtain the polycarbonate oligomer represented by formula (1) and/or formula (2) and/or formula (3), the mixing ratio of the dihydroxy compound represented by formula (4) and the carbonate ester forming agent is as follows: The amount of the carbonate ester forming agent is usually 0.2 to 5 moles, preferably 0.3 to 3.3 moles, and more preferably 0.4 to 2 moles per mole of the dihydroxy compound represented by formula (4). Use .5 mole times.
During the melt transesterification reaction, a transesterification catalyst is used as necessary to increase the reaction rate. There are no particular restrictions on the transesterification catalyst, and examples include inorganic alkali metal compounds such as hydroxides, carbonates, and hydrogen carbonates of lithium, sodium, and cesium, and organic alkali metal compounds such as alcoholates and organic carboxylates. Alkali metal compounds; inorganic alkaline earth metal compounds such as hydroxides and carbonates such as beryllium and magnesium; alkaline earth metal compounds such as organic alkaline earth metal compounds such as alcoholates and organic carboxylates; tetramethylboron; Basic boron compounds such as sodium salts, calcium salts, and magnesium salts such as tetraethylboron and butyltriphenylboron; trivalent phosphorus compounds such as triethylphosphine and tri-n-propylphosphine, or derivatives from these compounds Basic phosphorus compounds such as quaternary phosphonium salts; Basic ammonium compounds such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrabutylammonium hydroxide; Amine-based compounds such as 4-aminopyridine, 2-dimethylaminoimidazole, and aminoquinoline Known transesterification catalysts such as compounds can be used. Among these, alkali metal compounds are preferred, and cesium compounds such as cesium carbonate and cesium hydroxide are particularly preferred.
The amount of catalyst to be used is within a range that does not cause quality problems of the produced oligomers due to catalyst residue, and since the suitable addition amount differs depending on the type of catalyst, it cannot be stated unconditionally, but roughly speaking, for example, formula (B ) is usually 0.05 to 100 μmol, preferably 0.08 to 50 μmol, more preferably 0.1 to 20 μmol, and even more preferably 0.1 to 5 μmol per mole of the dihydroxy compound represented by . The catalyst may be added as it is, or may be added after being dissolved in a solvent. Preferably, the solvent is one that does not affect the reaction, such as water or phenol.
The reaction conditions for the melt transesterification reaction are such that the temperature is usually in the range of 120 to 360°C, preferably in the range of 150 to 280°C, more preferably in the range of 180 to 260°C. If the reaction temperature is too low, the transesterification reaction will not proceed, and if the reaction temperature is too high, side reactions such as decomposition reactions will proceed, which is not preferable. The reaction is preferably carried out under reduced pressure. The reaction pressure is preferably such that the carbonate ester forming agent, which is a raw material, does not distill out of the system at the reaction temperature, and by-products such as phenol can distill out. Under such reaction conditions, the reaction is usually completed in about 0.5 to 10 hours.
＜本発明の成分（Ｂ）について＞
本発明のエポキシ樹脂組成物に含まれる成分（Ｂ）は、１分子中に２個以上のエポキシ基を有するポリエポキシ化合物である。所謂プレポリマー（中間生成物）と呼称されるものであり、１分子中に２個以上のエポキシ基を有するとともに比較的低分子量を有するものである。そして、本発明のエポキシ樹脂組成物は、後述する硬化（重合）させることにより、硬化物であるエポキシ樹脂硬化物を得ることができる。
本発明のエポキシ樹脂組成物に含まれる成分（Ｂ）として、好ましい化学構造は下記式（５）により表されるポリエポキシ化合物である。
上記式（５）における、Ｙの好ましい態様として、炭素原子数１～５のアルキリデン基、炭素原子数１～５のアルキレン基が挙げられ、具体的には、メチレン基、エチリデン基、イソプロピリデン基、プロパン－１－イリデン基、ブタン－２－イリデン基、ブタン－１－イリデン基、３－メチルブタン－２－イリデン基、２－メチルペンタン－４－イリデン基等が挙げられる。
上記式（５）で表されるポリエポキシ化合物としては、例えば、ポリエポキシ化合物の化学構造に対応するポリヒドロキシ化合物と、エピクロルヒドリン等のエピハロヒドリンとの反応により得られる化合物が挙げられる。上記式（５）で表されるポリエポキシ化合物の原料であるポリヒドロキシ化合物の具体例としては、２，２－ビス（４－ヒドロキシフェニル）プロパン（ビスフェノールＡ）、２，２－ビス（４－ヒドロキシフェニル）エタン（ビスフェノールＥ）、２，２－ビス（４－ヒドロキシフェニル）メタン（ビスフェノールＦ）、４，４’－ジヒドロキシビフェニルが挙げられる。
式（５）により表されるポリエポキシ化合物以外のポリエポキシ化合物の原料であるポリヒドロキシ化合物の具体例としては、フェノールノボラック樹脂、クレゾールノボラック樹脂、ビフェニルノボラック樹脂等が挙げられる。
本発明における成分（Ｂ）ポリエポキシ化合物の具体例としては、例えば、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、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、キシレンノボラック型エポキシ樹脂、トリグリシジルイソシアヌレート、脂環式エポキシ樹脂、ジシクロペンタジエンノボラック型エポキシ樹脂、ビフェニルノボラック型エポキシ樹脂のほか、公知のエポキシ樹脂、例えば、特開平０１－９８６１３号公報等に記載された下記式で表わされるエポキシ樹脂等が挙げられる。なお、下記式中のａは、各々独立して１以上の整数を表し、ｂは各々１以下の正数を表す。
Component (B) contained in the epoxy resin composition of the present invention is a polyepoxy compound having two or more epoxy groups in one molecule. It is a so-called prepolymer (intermediate product), and has two or more epoxy groups in one molecule and a relatively low molecular weight. The epoxy resin composition of the present invention can be cured (polymerized) to obtain a cured epoxy resin product as described below.
A preferred chemical structure of component (B) contained in the epoxy resin composition of the present invention is a polyepoxy compound represented by the following formula (5).
Preferred embodiments of Y in the above formula (5) include an alkylidene group having 1 to 5 carbon atoms and an alkylene group having 1 to 5 carbon atoms, specifically, a methylene group, an ethylidene group, an isopropylidene group. , propan-1-ylidene group, butane-2-ylidene group, butane-1-ylidene group, 3-methylbutan-2-ylidene group, 2-methylpentan-4-ylidene group, and the like.
Examples of the polyepoxy compound represented by the above formula (5) include compounds obtained by reacting a polyhydroxy compound corresponding to the chemical structure of the polyepoxy compound with an epihalohydrin such as epichlorohydrin. Specific examples of polyhydroxy compounds that are raw materials for the polyepoxy compound represented by formula (5) above include 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 2,2-bis(4- Examples include hydroxyphenyl)ethane (bisphenol E), 2,2-bis(4-hydroxyphenyl)methane (bisphenol F), and 4,4'-dihydroxybiphenyl.
Specific examples of polyhydroxy compounds that are raw materials for polyepoxy compounds other than the polyepoxy compound represented by formula (5) include phenol novolac resins, cresol novolak resins, biphenyl novolak resins, and the like.
Specific examples of the component (B) polyepoxy compound in the present invention include bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, xylene novolac type epoxy resin. In addition to epoxy resins, triglycidyl isocyanurate, alicyclic epoxy resins, dicyclopentadiene novolac type epoxy resins, biphenyl novolac type epoxy resins, known epoxy resins, such as the following described in JP-A No. 01-98613, etc. Examples include epoxy resins represented by the following formulas. In addition, a in the following formula each independently represents an integer of 1 or more, and b each represents a positive number of 1 or less.
本発明の成分（Ｂ）ポリエポキシ化合物を得る方法は、特に限定されるものではないが、例えば、１）ポリヒドロキシ化合物のエポキシ化反応は、原料となるポリヒドロキシ化合物をエピハロヒドリンに溶解し、テトラメチルアンモニウムクロライドやトリメチルベンジルアンモニウムクロライド等の第４級アンモニウム塩などを触媒として反応させた後、アルカリ金属水酸化物等塩基性化合物をそのままで、及び／又は水溶液として添加してさらに反応させることにより得る方法や、２）原料ポリヒドロキシ化合物をエピクロルヒドリン等のエピハロヒドリンに溶解しメタノールやエタノール等の極性溶媒を添加し、水酸化ナトリウム、水酸化カリウムなどのアルカリ金属水酸化物の固体を添加し、又は添加しながら反応させる方法、また、３）アルカリ金属水酸化物の水溶液を使用し、アルカリ金属水酸化物を逐次的に添加すると共に反応系内から減圧下、又は常圧下、連続的に水及びエピハロヒドリンを留出させ、これを分液し、水は除去しエピハロヒドリンは反応系内に連続的に戻す方法、４）原料ポリヒドロキシ化合物と、例えばアリルクロリド、アリルブロミド等のハロゲン化ビニル化合物を溶媒中で塩基の存在下に反応させ、次いで、反応終了後、そのままｍ－クロロ過安息香酸等の炭素－炭素二重結合をエポキシ基に酸化可能な酸化剤を作用させるか、又は、例えば反応液と水を混合し、反応生成物を取り出した後、該反応生成物に前記酸化剤を作用させるかした後、例えば、必要に応じて残存する酸化剤を分解処理し、次いで濃縮処理することにより、ジエポキシ化合物を得る方法等が知られている。本発明における１分子中に２個以上のエポキシ基を有するポリエポキシ化合物を得るには、これら何れの方法でもよいし、これ以外の方法によるものでもよい。
本発明のポリエポキシ化合物を製造するに際して、エポキシ化反応の進行とともに、二量体、三量体、四量体等のオリゴマーが少量副生するが、本発明においては、用いるポリエポキシ化合物がオリゴマーを少量含んでいてもよい。また、本発明に用いるポリエポキシ化合物は、エポキシ化反応時、エポキシ基の形成が未完了のままの加水分解性塩素を有する末端基を含む化合物等を少量含んでいてもよい。
The method for obtaining the polyepoxy compound (B) of the present invention is not particularly limited, but for example, 1) the epoxidation reaction of the polyhydroxy compound is performed by dissolving the raw material polyhydroxy compound in epihalohydrin, By reacting with a quaternary ammonium salt such as methylammonium chloride or trimethylbenzylammonium chloride as a catalyst, and then adding a basic compound such as an alkali metal hydroxide as it is or as an aqueous solution and further reacting. 2) Dissolving the raw material polyhydroxy compound in epihalohydrin such as epichlorohydrin, adding a polar solvent such as methanol or ethanol, and adding a solid alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, or 3) Using an aqueous solution of alkali metal hydroxide, the alkali metal hydroxide is added sequentially and water and water are added continuously from within the reaction system under reduced pressure or normal pressure. A method in which epihalohydrin is distilled out, separated into liquids, water is removed, and epihalohydrin is continuously returned to the reaction system; 4) A method in which a raw material polyhydroxy compound and a halogenated vinyl compound such as allyl chloride or allyl bromide are mixed in a solvent. After the reaction is complete, an oxidizing agent capable of oxidizing the carbon-carbon double bond to the epoxy group, such as m-chloroperbenzoic acid, is directly applied to the epoxy group, or, for example, the reaction solution is and water, and after taking out the reaction product, after allowing the oxidizing agent to act on the reaction product, for example, if necessary, the remaining oxidizing agent is decomposed, and then the reaction product is concentrated. , a method for obtaining a diepoxy compound, etc. are known. In order to obtain the polyepoxy compound having two or more epoxy groups in one molecule in the present invention, any of these methods or other methods may be used.
When producing the polyepoxy compound of the present invention, a small amount of oligomers such as dimers, trimers, and tetramers are produced as by-products as the epoxidation reaction progresses, but in the present invention, the polyepoxy compound used is an oligomer. May contain small amounts of. Further, the polyepoxy compound used in the present invention may contain a small amount of a compound containing a terminal group having hydrolyzable chlorine in which the formation of an epoxy group remains incomplete during the epoxidation reaction.
＜任意の成分＞
本発明のエポキシ樹脂組成物には、前記の成分（Ａ）と成分（Ｂ）の他にも、本発明の効果を著しく損なわない範囲で、任意の成分を含有させることが可能である。任意の成分としては、例えば硬化促進剤、カップリング剤、難燃剤、無機充填材、樹脂、触媒、レベリング剤、消泡剤、イオン捕捉剤、応力緩和剤、染料、着色剤等が挙げられる。これらの任意の成分は、１種が単独で含まれてもよく、２種以上が任意の比率および組み合わせで含まれていてもよい。
硬化促進剤としては、本発明の効果を著しく損なわない限り任意のものを用いることができるが、例えば、三級アミン化合物、２－メチルイミダゾール、２－エチル－４－メチルイミダゾール、２－フェニルイミダゾール、１－シアノエチル－２－フェニルイミダゾール、１－シアノエチル－２－エチル－４－メチルイミダゾール、２－フェニル－４，５－ジヒドロキシメチルイミダゾール、２－フェニル－４－メチル－５－ヒドロキシメチルイミダゾール等のイミダゾール類、有機スルフィン類、リン化合物、テトラフェニルボロン塩およびこれらの誘導体等が挙げられる。
カップリング剤としては、本発明の効果を著しく損なわない限り任意のものを用いることができるが、例えば、エポキシシラン、アミノシラン、ウレイドシラン、ビニルシラン、アルキルシラン、有機チタネート、アルミニウムアルキレート等が挙げられる。
難燃剤としても、本発明の効果を著しく損なわない限り任意のものを用いることができるが、例えば、赤燐、燐酸、燐酸エステル、メラミン、メラミン誘導体、トリアジン環を有する化合物、シアヌル酸誘導体、イソシアヌル酸誘導体の窒素含有化合物、シクロホスファゼン等の燐窒素含有化合物、酸化亜鉛、酸化鉄、酸化モリブデン、フェロセン等の金属化合物、三酸化アンチモン、四酸化アンチモン、五酸化アンチモン等の酸化アンチモン、ブロム化エポキシ樹脂等が挙げられる。
無機充填材としても、本発明の効果を著しく損なわない限り任意のものを用いることができるが、例えば、溶融シリカ、結晶シリカ、アルミナ、ジルコン、珪酸カルシウム、炭酸カルシウム、チタン酸カリウム、炭化珪素、窒化アルミ、窒化ホウ素、ベリリア、ジルコン、フォステライト、ステアライト、スピレル、ムライト、チタニア等の粉体、また、これらを球形化したビーズ、ガラス繊維等が挙げられる。無機充填材を含有させることにより、得られるエポキシ樹脂組成物を用いたエポキシ樹脂硬化物の吸湿性、熱伝導性および接着性の向上、熱膨張係数の低減を図ることができる。
また、無機充填材としても、本発明の効果を著しく損なわない限り任意のものを用いることができるが、例えば、水酸化アルミニウム、水酸化マグネシウム、珪酸亜鉛、モリブデン酸亜鉛等を含有させることができる。これらを含有させることにより、難燃効果の向上を図ることができる。
イオン捕捉剤としても、本発明の効果を著しく損なわない限り任意のものを用いることができるが、例えば、ハイドロタルサイト類、マグネシウム、アルミニウム、チタン、ジルコニウム、ビスマス等の元素の含水酸化物等が挙げられる。イオン捕捉剤を含有させることにより、得られるエポキシ樹脂組成物を用いた電子機器の耐湿性、高温放置特性（耐熱性）を向上させることができる。
応力緩和剤としても、本発明の効果を著しく損なわない限り任意のものを用いることができるが、例えばシリコーンゴム粉末等が挙げられる。さらに、着色剤としても、本発明の効果を著しく損なわない限り任意のものを用いることができるが、例えばカーボンブラック等が挙げられる。
<Optional ingredients>
In addition to the component (A) and component (B) described above, the epoxy resin composition of the present invention can contain any other component as long as the effects of the present invention are not significantly impaired. Examples of optional components include curing accelerators, coupling agents, flame retardants, inorganic fillers, resins, catalysts, leveling agents, antifoaming agents, ion scavengers, stress relievers, dyes, colorants, and the like. One type of these optional components may be contained alone, or two or more types may be contained in any ratio and combination.
Any curing accelerator can be used as long as it does not significantly impair the effects of the present invention, and examples thereof include tertiary amine compounds, 2-methylimidazole, 2-ethyl-4-methylimidazole, and 2-phenylimidazole. , 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, etc. Examples include imidazoles, organic sulfins, phosphorus compounds, tetraphenylboron salts, and derivatives thereof.
Any coupling agent can be used as long as it does not significantly impair the effects of the present invention, and examples thereof include epoxysilane, aminosilane, ureidosilane, vinylsilane, alkylsilane, organic titanate, aluminum alkylate, etc. .
Any flame retardant can be used as long as it does not significantly impair the effects of the present invention, but examples include red phosphorus, phosphoric acid, phosphoric esters, melamine, melamine derivatives, compounds having a triazine ring, cyanuric acid derivatives, isocyanuric acid, etc. Nitrogen-containing compounds such as acid derivatives, phosphorous nitrogen-containing compounds such as cyclophosphazene, metal compounds such as zinc oxide, iron oxide, molybdenum oxide, and ferrocene, antimony oxides such as antimony trioxide, antimony tetroxide, and antimony pentoxide, and brominated epoxy. Examples include resin.
Any inorganic filler can be used as long as it does not significantly impair the effects of the present invention, but examples include fused silica, crystalline silica, alumina, zircon, calcium silicate, calcium carbonate, potassium titanate, silicon carbide, Powders of aluminum nitride, boron nitride, beryllia, zircon, forsterite, stearite, spirel, mullite, titania, etc., as well as beads made of these into spheres, glass fibers, etc., can be mentioned. By containing an inorganic filler, it is possible to improve the hygroscopicity, thermal conductivity, and adhesiveness of the cured epoxy resin product using the obtained epoxy resin composition, and to reduce the coefficient of thermal expansion.
Further, any inorganic filler can be used as long as it does not significantly impair the effects of the present invention, and for example, aluminum hydroxide, magnesium hydroxide, zinc silicate, zinc molybdate, etc. can be included. . By containing these, the flame retardant effect can be improved.
Any ion scavenger can be used as long as it does not significantly impair the effects of the present invention, but examples include hydrotalcites, hydrous oxides of elements such as magnesium, aluminum, titanium, zirconium, and bismuth. Can be mentioned. By containing an ion scavenger, the moisture resistance and high temperature storage characteristics (heat resistance) of electronic devices using the resulting epoxy resin composition can be improved.
Any stress relaxation agent may be used as long as it does not significantly impair the effects of the present invention, and examples thereof include silicone rubber powder. Furthermore, any coloring agent may be used as long as it does not significantly impair the effects of the present invention, and examples thereof include carbon black.
本発明のエポキシ樹脂組成物は、成分（Ａ）ポリカーボネートオリゴマーを硬化剤として含有するものであるが、本発明の効果を損なわない範囲で公知のエポキシ硬化剤を併用することもできる。公知のエポキシ硬化剤としては、例えば、フェノールノボラック樹脂、クレゾールノボラック樹脂、ビスフェノールＡ 、ビスフェノールＦ等のフェノール類、メチルテトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、無水ピロメリット酸等の酸無水物類、ジアミノジフェニルメタン、ジアミノジフェニルスルホン、ジシアンジアミド等のアミン類が挙げられる。成分（Ａ）ポリカーボネートオリゴマーは、使用する全ての硬化剤の総量に対して１重量％以上配合することが好ましく、３重量％以上配合することがより好ましく、５重量％以上配合することが特に好ましい。成分（Ａ）ポリカーボネートオリゴマーの配合量が少ないと、得られる硬化物の物性改良効果が小さくなり好ましくない。そのため、全ての硬化剤における成分（Ａ）ポリカーボネートオリゴマーの配合量比は、好ましくは７０重量％以上であり、より好ましくは８０重量％以上であり、さらに好ましくは９０重量％であり、特に好ましくは９５重量％である。 Although the epoxy resin composition of the present invention contains component (A) polycarbonate oligomer as a curing agent, a known epoxy curing agent may be used in combination without impairing the effects of the present invention. Known epoxy curing agents include, for example, phenol novolac resins, cresol novolac resins, phenols such as bisphenol A and bisphenol F, acid anhydrides such as methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, and pyromellitic anhydride; Examples include amines such as diaminodiphenylmethane, diaminodiphenylsulfone, and dicyandiamide. Component (A) polycarbonate oligomer is preferably blended in an amount of 1% by weight or more, more preferably 3% by weight or more, and particularly preferably 5% by weight or more based on the total amount of all curing agents used. . If the amount of the polycarbonate oligomer (component (A)) is small, the effect of improving the physical properties of the resulting cured product will be undesirable. Therefore, the blending ratio of component (A) polycarbonate oligomer in all curing agents is preferably 70% by weight or more, more preferably 80% by weight or more, still more preferably 90% by weight, and particularly preferably It is 95% by weight.
＜成分（Ａ）と成分（Ｂ）との混合比率について＞
本発明のエポキシ樹脂組成物は、成分（Ａ）の水酸基、炭酸エステル基と成分（Ｂ）のエポキシ基との反応により硬化する。成分（Ａ）と成分（Ｂ）との混合比率は、化学当量の観点からは、成分（Ａ）の水酸基及び炭酸エステル基の合計モル数に対する成分（Ｂ）エポキシ基のモル数の比、すなわち、「（成分（Ｂ）エポキシ基のモル数）／（成分（Ａ）の水酸基及び炭酸エステル基の合計モル数）」が、通常０．５～１０の範囲、好ましくは０．９～５の範囲、より好ましくは０．９５～１．０５の範囲、特に好ましくは１で調整するとよい。
<About the mixing ratio of component (A) and component (B)>
The epoxy resin composition of the present invention is cured by the reaction between the hydroxyl group or carbonate group of component (A) and the epoxy group of component (B). From the viewpoint of chemical equivalent, the mixing ratio of component (A) and component (B) is the ratio of the number of moles of the epoxy group of component (B) to the total number of moles of the hydroxyl group and carbonate group of component (A), i.e. , "(number of moles of epoxy group in component (B))/(total number of moles of hydroxyl group and carbonate group in component (A))" is usually in the range of 0.5 to 10, preferably 0.9 to 5. It may be adjusted within a range, more preferably within a range of 0.95 to 1.05, particularly preferably within a range of 1.
＜成分（Ａ）と成分（Ｂ）との混合について＞
本発明のエポキシ樹脂組成物は、成分（Ａ）と成分（Ｂ）のほか、必要に応じた任意成分を含有するものであり、硬化させる前に均一に混合する必要がある。本発明の成分（Ａ）のポリカーボネートオリゴマーが固体である場合には、特に、均一に混合していることを確認した後に、硬化させる必要がある。これらを混合する方法および装置は、これらの成分を均一に分散混合でき、本発明の効果を著しく損なわない限り特に制限されない。ただし、通常は、これらの成分を所定量秤量して同一の系に存在させた後、例えば、ボールミル、二本ロールミル、三本ロールミル、真空雷潰機、ポットミル、ハイブリッドミキサー等を用いて分散混合を行えばよい。
<About mixing component (A) and component (B)>
The epoxy resin composition of the present invention contains, in addition to component (A) and component (B), optional components as required, and must be uniformly mixed before curing. When the polycarbonate oligomer of component (A) of the present invention is solid, it is necessary to cure it, especially after confirming that it is uniformly mixed. The method and device for mixing these components are not particularly limited as long as these components can be uniformly dispersed and mixed and do not significantly impair the effects of the present invention. However, usually, after weighing a predetermined amount of these components and making them exist in the same system, they are dispersed and mixed using, for example, a ball mill, two-roll mill, three-roll mill, vacuum crusher, pot mill, hybrid mixer, etc. All you have to do is
＜硬化方法について＞
本発明のエポキシ樹脂組成物を硬化させる方法としては、従来公知のエポキシ樹脂の硬化方法を用いることができ、例えば、エポキシ樹脂組成物を加熱及び／又は光照射して硬化させる方法により行うことができる。
エポキシ樹脂組成物を加熱する場合の加熱温度及び加熱時間は特に限定されるものではなく、エポキシ樹脂組成物の配合に応じて適宜決定することが好ましい。エポキシ樹脂組成物を加熱する際、段階的に昇温しながら加熱することも好ましい。具体的には、本発明の成分（Ａ）ポリカーボネートオリゴマーと成分（Ｂ）ポリエポキシ化合物を、通常６０～１８０℃で１～１０時間加熱溶融（最適には１５０℃、６時間）しながら均一に混合して、硬化促進剤等の任意成分を添加・混合してエポキシ樹脂組成物を調製する。次いで、得られたエポキシ樹脂組成物を、加圧下、１００～２００℃で０．１～６０分間プレ成形硬化（最適には６ＭＰａ、１８０℃、３０分間）させ、さらに硬化性能の向上を図るために、７０～２００℃の温度で０．１～１０時間の範囲で後硬化（最適には１８０℃、４時間）を行う。また、エポキシ樹脂組成物の粘性が低い場合には、プレ成形硬化前に増粘を目的として、５０～１５０℃（最適には１５０℃）の加熱により重合させても良い。
<About the curing method>
As a method for curing the epoxy resin composition of the present invention, conventionally known epoxy resin curing methods can be used. For example, the epoxy resin composition may be cured by heating and/or light irradiation. can.
The heating temperature and heating time when heating the epoxy resin composition are not particularly limited, and are preferably appropriately determined depending on the formulation of the epoxy resin composition. When heating the epoxy resin composition, it is also preferable to heat the epoxy resin composition while increasing the temperature in stages. Specifically, component (A) polycarbonate oligomer and component (B) polyepoxy compound of the present invention are uniformly melted by heating at usually 60 to 180°C for 1 to 10 hours (optimally 150°C for 6 hours). After mixing, optional components such as a curing accelerator are added and mixed to prepare an epoxy resin composition. Next, the obtained epoxy resin composition was pre-molded and cured under pressure at 100 to 200 °C for 0.1 to 60 minutes (optimally 6 MPa, 180 °C, 30 minutes) to further improve the curing performance. Then, post-curing is carried out at a temperature of 70 to 200°C for 0.1 to 10 hours (optimally 180°C for 4 hours). Furthermore, when the epoxy resin composition has a low viscosity, it may be polymerized by heating at 50 to 150°C (optimally 150°C) for the purpose of thickening the composition before pre-molding and curing.
＜エポキシ樹脂組成物の用途について＞
本発明のエポキシ樹脂組成物は、式（１）及び／又は式（２）及び／又は式（３）で表され、特定の重量平均分子量を有するポリカーボネートオリゴマーを含有することにより、耐熱性のみならず誘電特性が向上し、工業的に有利な効果を発揮する。
本発明のエポキシ樹脂組成物は、半導体封止材、電気絶縁材料、銅張り積層板用樹脂、レジスト、電子部品の封止用樹脂、液晶のカラーフィルター用樹脂、塗料、各種コーティング剤、接着剤、ビルドアップ積層板材料、ＦＲＰとして有用である。
<About the uses of epoxy resin compositions>
The epoxy resin composition of the present invention is represented by formula (1) and/or formula (2) and/or formula (3) and contains polycarbonate oligomers having a specific weight average molecular weight. First, the dielectric properties are improved and industrially advantageous effects are exhibited.
The epoxy resin composition of the present invention is applicable to semiconductor encapsulating materials, electrical insulating materials, resins for copper-clad laminates, resists, resins for encapsulating electronic components, resins for color filters of liquid crystals, paints, various coating agents, and adhesives. It is useful as a build-up laminate material, FRP.
以下、本発明を実施例により具体的に説明するが、本発明はこれら実施例に限定されるものではない。
なお、以下の例における重量平均分子量（Ｍｗ）はゲル浸透クロマトグラフィーにより測定した。その分析方法は以下のとおりである。
＜分析方法＞
１．ゲル浸透クロマトグラフィー測定
装置：東ソー株式会社製 HLC-8320GPC
流量：0.35ml/min、移動相：テトラヒドロフラン、打ち込み量：10μl
カラム：TSKgel guardcolumn SuperMP(HZ)-N, TSKgel SuperMultiporeHZ-
N×3本
検出器：RI
解析方法：ポリスチレン換算の相対分子量とする。
ポリスチレン標品：東ソー株式会社製 A-500,A-2500,A-5000,F-1,F-2,F-4
２．末端ヒドロキシル濃度の測定
１Ｈ－ＮＭＲを用い、TCE（1,1,1,2-テトラクロロエタン）を内部標準として、ビスフェノールＡ、ビスフェノールＣを標品に用いTCEとの重量比の検量線を作成した。この検量線からフェノール末端重量を求める方法で定量した。
装置：ＢＲＵＫＥＲ社製 AscendTM 400
測定条件：室温、積算回数120回
３．動的粘弾性測定
測定装置：EXSTAR DMS6100（日立ハイテクサイエンス社製）
４．比誘電率・誘電正接
測定装置：PNA-LネットワークアナライザN5230A（アジレント・テクノロジ
ー社製）
空洞共振器 1GHz用 CP431（関東電子応用開発社製）
EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples.
In addition, the weight average molecular weight (Mw) in the following examples was measured by gel permeation chromatography. The analysis method is as follows.
<Analysis method>
1. Gel permeation chromatography measurement equipment: Tosoh Corporation HLC-8320GPC
Flow rate: 0.35ml/min, mobile phase: tetrahydrofuran, injection amount: 10μl
Column: TSKgel guardcolumn SuperMP(HZ)-N, TSKgel SuperMultiporeHZ-
N×3 detector: RI
Analysis method: Relative molecular weight in terms of polystyrene.
Polystyrene standard: Tosoh Corporation A-500, A-2500, A-5000, F-1, F-2, F-4
2. Measuring terminal hydroxyl concentration
Using 1 H-NMR, a calibration curve of the weight ratio with TCE was created using TCE (1,1,1,2-tetrachloroethane) as an internal standard and bisphenol A and bisphenol C as standards. Quantification was performed by determining the weight of the phenol end from this calibration curve.
Equipment: BRUKER AscendTM 400
Measurement conditions: room temperature, 120 accumulations 3. Dynamic viscoelasticity measurement Measuring device: EXSTAR DMS6100 (manufactured by Hitachi High-Tech Science)
4. Relative permittivity/dissipation factor Measuring device: PNA-L network analyzer N5230A (Agilent Technologies)
-manufactured by)
Cavity resonator for 1GHz CP431 (manufactured by Kanto Denshi Applied Development Co., Ltd.)
＜参考例１＞１，１－ビス（４－ヒドロキシフェニル）シクロドデカンのポリカーボネートオリゴマーの合成
温度計、撹拌機、冷却器を備えた４つ口フラスコに１，１－ビス（４－ヒドロキシフェニル）シクロドデカン４７７ｇ（１．４モル）、ジフェニルカーボネート２０３ｇ（１．０モル）を仕込み、反応容器を窒素置換した後、９０℃で０．１％炭酸セシウム水溶液０．１ｇを加えた。２００℃まで昇温した後、減圧操作を行い、１３．３ｋＰａで４時間、１．３ｋＰａで1時間、２３０℃に昇温し０．３ｋＰａで１時間、２４０℃に昇温し０．３ｋＰａで２時間、生成したフェノールを留出させながら反応し、少なくとも上記化学構造式の何れか１種以上で表される１,１－ビス（４－ヒドロキシフェニル）シクロドデカンのポリカーボネートオリゴマー４７０ｇを得た。得られたポリカーボネートオリゴマーの重量平均分子量は２４２３（ゲル浸透クロマトグラフィー）、末端ヒドロキシル濃度は１．６２ｍｍｏｌ／ｇであった。
<Reference Example 1> Synthesis of polycarbonate oligomer of 1,1-bis(4-hydroxyphenyl)cyclododecane
477 g (1.4 mol) of 1,1-bis(4-hydroxyphenyl)cyclododecane and 203 g (1.0 mol) of diphenyl carbonate were charged into a four-necked flask equipped with a thermometer, stirrer, and condenser, and the reaction was started. After purging the container with nitrogen, 0.1 g of a 0.1% cesium carbonate aqueous solution was added at 90°C. After raising the temperature to 200°C, perform a pressure reduction operation, raise the temperature to 13.3kPa for 4 hours, 1.3kPa for 1 hour, raise the temperature to 230°C and raise the temperature to 0.3kPa for 1 hour, raise the temperature to 240°C and lower the pressure to 0.3kPa. The reaction was carried out for 2 hours while distilling off the produced phenol to obtain 470 g of a polycarbonate oligomer of 1,1-bis(4-hydroxyphenyl)cyclododecane represented by at least one of the above chemical structural formulas. The weight average molecular weight of the obtained polycarbonate oligomer was 2423 (gel permeation chromatography), and the terminal hydroxyl concentration was 1.62 mmol/g.
＜実施例１＞「参考例１」のポリカーボネートオリゴマーを用いたエポキシ樹脂組成物
エポキシ当量が１８４～１９４のビスフェノールＡ型エポキシ樹脂（製造元：三菱化学株式会社）１００ｇと参考例１で得たポリカーボネートオリゴマー１４９ｇを計り取り、プラネタリーミキサーを用いて約１５０℃で約６時間、加熱混合を行った。室温まで冷却した後、この混合物５０ｇを分け取り、１１０℃の二本ロールミルへ投入した。ここにトリフェニルホスフィン０．４ｇを添加し、３分間混練を行った。この混合物を１００mm×１００mmの押込み型にチャージし、圧縮成形機にて、１８０℃×３０分×６ＭＰａの条件でプレスした。成形した板を１８０℃熱風循環式オーブンで４時間、後硬化させた。作成した硬化板を切削加工し、物性測定を行った。
硬化板をJISK7171に準拠し、動的粘弾性測定をした結果、ガラス転移温度（Ｔｇ）は１７５℃であった。また、ASTM D 250を参考に、比誘電率、誘電正接を測定した結果、比誘電率は２．６８、誘電正接は０．０１３２であった。
<Example 1> Epoxy resin composition using the polycarbonate oligomer of "Reference Example 1" 100 g of bisphenol A epoxy resin (manufacturer: Mitsubishi Chemical Corporation) with an epoxy equivalent of 184 to 194 and the polycarbonate oligomer obtained in Reference Example 1 149 g was weighed out and heated and mixed at about 150° C. for about 6 hours using a planetary mixer. After cooling to room temperature, 50 g of this mixture was taken out and placed in a two-roll mill at 110°C. 0.4 g of triphenylphosphine was added thereto and kneaded for 3 minutes. This mixture was charged into a 100 mm x 100 mm push die and pressed using a compression molding machine under conditions of 180° C. x 30 minutes x 6 MPa. The formed plate was post-cured for 4 hours in a hot air circulation oven at 180°C. The prepared hardened plate was cut and its physical properties were measured.
The cured plate was subjected to dynamic viscoelasticity measurement according to JISK7171, and as a result, the glass transition temperature (Tg) was 175°C. Further, as a result of measuring the dielectric constant and dielectric loss tangent with reference to ASTM D 250, the dielectric constant was 2.68 and the dielectric loss tangent was 0.0132.
＜参考例２＞ビスフェノールＡのポリカーボネートオリゴマーの合成
温度計、撹拌機、冷却器を備えた４つ口フラスコに２，２－ビス（４－ヒドロキシフェニル）プロパン４２５．４ｇ（１．９モル）、ジフェニルカーボネート２８０ｇ（１．３モル）を仕込み、反応容器を窒素置換した後、９０℃で０．２％炭酸セシウム水溶液０．５７ｇを加えた。２１０℃まで昇温した後、減圧度を０．６ｋＰａに調整し、８時間、生成したフェノールを留出させながら反応し、目的とするポリカーボネートオリゴマー５１０ｇを得た。得られたポリカーボネートオリゴマーの重量平均分子量は２２１０（ゲル浸透クロマトグラフィー）、末端ヒドロキシル濃度は１．３０ｍｍｏｌ／ｇであった。
<Reference Example 2> Synthesis of polycarbonate oligomer of bisphenol A In a four-necked flask equipped with a thermometer, stirrer, and condenser, 425.4 g (1.9 mol) of 2,2-bis(4-hydroxyphenyl)propane, After charging 280 g (1.3 mol) of diphenyl carbonate and purging the reaction vessel with nitrogen, 0.57 g of a 0.2% aqueous cesium carbonate solution was added at 90°C. After raising the temperature to 210° C., the degree of vacuum was adjusted to 0.6 kPa, and reaction was carried out for 8 hours while distilling the produced phenol to obtain 510 g of the desired polycarbonate oligomer. The weight average molecular weight of the obtained polycarbonate oligomer was 2210 (gel permeation chromatography), and the terminal hydroxyl concentration was 1.30 mmol/g.
＜比較例１＞「参考例２」のポリカーボネートオリゴマーを用いたエポキシ樹脂組成物
エポキシ当量が１８４～１９４のビスフェノールＡ型エポキシ樹脂（製造元：三菱化学株式会社）１００ｇと参考例２で得たポリカーボネートオリゴマー１１４ｇを計り取り、プラネタリーミキサーを用いて約１５０℃で約６時間、加熱混合を行った。室温まで冷却した後、この混合物５０ｇを分け取り、１１０℃の二本ロールミルへ投入した。ここにトリフェニルホスフィン０．４ｇを添加し、３分間混練を行った。この混合物を１３０℃の熱風循環式オーブンへ入れて２５分間保持し、増粘させた。この混合物を１００mm×１００mmの押込み型にチャージし、圧縮成形機にて、１８０℃×３０分×６ＭＰａの条件でプレスした。成形した板を１８０℃熱風循環式オーブンで４時間、後硬化させた。作成した硬化板を切削加工し、物性測定を行った。
硬化板をJISK7171に準拠し、動的粘弾性測定をした結果、ガラス転移温度（Ｔｇ）は１２２℃であった。また、ASTM D 250を参考に、比誘電率、誘電正接を測定した結果、比誘電率は２．８２、誘電正接は０．０１５０であった。
<Comparative Example 1> Epoxy resin composition using the polycarbonate oligomer of "Reference Example 2" 100 g of bisphenol A epoxy resin (manufacturer: Mitsubishi Chemical Corporation) with an epoxy equivalent of 184 to 194 and the polycarbonate oligomer obtained in Reference Example 2 114 g was weighed out and heated and mixed at about 150° C. for about 6 hours using a planetary mixer. After cooling to room temperature, 50 g of this mixture was taken out and placed in a two-roll mill at 110°C. 0.4 g of triphenylphosphine was added thereto and kneaded for 3 minutes. The mixture was placed in a hot air circulation oven at 130°C and held for 25 minutes to thicken it. This mixture was charged into a 100 mm x 100 mm push die and pressed using a compression molding machine under conditions of 180° C. x 30 minutes x 6 MPa. The formed plate was post-cured for 4 hours in a hot air circulation oven at 180°C. The prepared hardened plate was cut and its physical properties were measured.
The cured plate was subjected to dynamic viscoelasticity measurement according to JISK7171, and as a result, the glass transition temperature (Tg) was 122°C. Further, as a result of measuring the dielectric constant and dielectric loss tangent with reference to ASTM D 250, the dielectric constant was 2.82 and the dielectric loss tangent was 0.0150.
実施例１と比較例１の結果より、本発明のエポキシ樹脂組成物は、従来公知のエポキシ樹脂組成物に比べて、ガラス転移温度が大きく向上し、耐熱性に優れるのみならず、誘電特性に優れた硬化物を生成することが確認された。 From the results of Example 1 and Comparative Example 1, the epoxy resin composition of the present invention has a significantly improved glass transition temperature and excellent heat resistance as well as improved dielectric properties compared to conventionally known epoxy resin compositions. It was confirmed that an excellent cured product was produced.
Claims (2)
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018193020 | 2018-10-12 | ||
| JP2018193020 | 2018-10-12 | ||
| JP2018247436 | 2018-12-28 | ||
| JP2018247436 | 2018-12-28 | ||
| JP2020550529A JP7355304B2 (en) | 2018-10-12 | 2019-10-03 | epoxy resin composition |
| PCT/JP2019/039054 WO2020075611A1 (en) | 2018-10-12 | 2019-10-03 | Epoxy resin composition |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2020550529A Division JP7355304B2 (en) | 2018-10-12 | 2019-10-03 | epoxy resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2023158145A true JP2023158145A (en) | 2023-10-26 |
Family
ID=70164885
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2020550529A Active JP7355304B2 (en) | 2018-10-12 | 2019-10-03 | epoxy resin composition |
| JP2023145263A Pending JP2023158145A (en) | 2018-10-12 | 2023-09-07 | epoxy resin composition |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2020550529A Active JP7355304B2 (en) | 2018-10-12 | 2019-10-03 | epoxy resin composition |
Country Status (5)
| Country | Link |
|---|---|
| JP (2) | JP7355304B2 (en) |
| KR (1) | KR20210075982A (en) |
| CN (1) | CN112752781B (en) |
| TW (1) | TWI809208B (en) |
| WO (1) | WO2020075611A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117957264A (en) * | 2021-09-24 | 2024-04-30 | 三菱化学株式会社 | Resin composition, cured product, resin sheet, insulating layer, electric/electronic component, printed wiring board, and curing agent for epoxy resin |
| WO2024026679A1 (en) * | 2022-08-02 | 2024-02-08 | 上纬创新育成股份有限公司 | Carbonate ester-containing epoxy resin, preparation method therefor, epoxy cured product prepared therefrom, and method for degrading epoxy cured product |
| JP2024083262A (en) * | 2022-12-09 | 2024-06-20 | 上緯創新育成股▲ふん▼有限公司 | Polycarbonate oligomer, its production method, curable composition, epoxy cured product produced therefrom, and method for decomposing epoxy cured product with amine |
| WO2024119458A1 (en) * | 2022-12-09 | 2024-06-13 | 上纬创新育成股份有限公司 | Polycarbonate oligomer and preparation method therefor, curable composition, epoxy cured product, and method for degrading epoxy cured product by means of aminolysis |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0781025B2 (en) | 1987-10-15 | 1995-08-30 | 三井石油化学工業株式会社 | Method for producing epoxy foam |
| US4943619A (en) * | 1988-12-19 | 1990-07-24 | The University Of Connecticut | Polycarbonate-epoxy polymer |
| JPH0416337A (en) | 1990-05-10 | 1992-01-21 | Mitsui Petrochem Ind Ltd | Epoxy resin foamable sheet, foamed cured body and composite material |
| TW222660B (en) * | 1992-02-25 | 1994-04-21 | Gen Electric | |
| JPH05262969A (en) * | 1992-03-19 | 1993-10-12 | Nippon G Ii Plast Kk | Polycarbonate-based resin composition for optical use |
| JP2003342461A (en) | 2002-05-27 | 2003-12-03 | Toray Ind Inc | Resin composition for storage medium substrate, storage medium substrate comprising the same, and storage medium |
| JP2007009187A (en) | 2005-05-31 | 2007-01-18 | Toray Ind Inc | Transparent resin molded body and eyeglass lens comprising the same |
| WO2009040921A1 (en) * | 2007-09-27 | 2009-04-02 | Panasonic Electric Works Co., Ltd. | Epoxy resin composition and, produced therewith, prepreg and metal clad laminate |
| JP2013018240A (en) | 2011-07-13 | 2013-01-31 | Mitsubishi Chemicals Corp | Method of manufacturing polycarbonate resin molding |
| JP2013159639A (en) | 2012-02-01 | 2013-08-19 | Toyo Ink Sc Holdings Co Ltd | Thermosetting resin composition containing carboxy group-containing modified urethane ester resin |
| JP6212420B2 (en) * | 2014-03-25 | 2017-10-11 | 富士フイルム株式会社 | Composition, Underfill Laminate, Laminate, Semiconductor Device Manufacturing Method, and Semiconductor Device |
-
2019
- 2019-10-03 KR KR1020217009209A patent/KR20210075982A/en active Search and Examination
- 2019-10-03 CN CN201980062849.2A patent/CN112752781B/en active Active
- 2019-10-03 WO PCT/JP2019/039054 patent/WO2020075611A1/en active Application Filing
- 2019-10-03 JP JP2020550529A patent/JP7355304B2/en active Active
- 2019-10-08 TW TW108136396A patent/TWI809208B/en active
-
2023
- 2023-09-07 JP JP2023145263A patent/JP2023158145A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| TWI809208B (en) | 2023-07-21 |
| CN112752781A (en) | 2021-05-04 |
| CN112752781B (en) | 2023-08-15 |
| WO2020075611A1 (en) | 2020-04-16 |
| JP7355304B2 (en) | 2023-10-03 |
| TW202024175A (en) | 2020-07-01 |
| KR20210075982A (en) | 2021-06-23 |
| JPWO2020075611A1 (en) | 2021-09-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP7355304B2 (en) | epoxy resin composition | |
| KR101524485B1 (en) | Modified epoxy resin, epoxy resin compositions and cured articles | |
| JP5166610B2 (en) | Epoxy resin, production method thereof, epoxy resin composition and cured product using the same | |
| JP4259536B2 (en) | Method for producing phenol resin and method for producing epoxy resin | |
| JP2007231083A (en) | Epoxy resin composition, cured product thereof, new epoxy resin, new phenol resin, and semiconductor sealing material | |
| KR101896963B1 (en) | Epoxy resin compound and radiant heat circuit board using the same | |
| JP5664817B2 (en) | Phenolic hydroxyl group-containing compound, phenol resin, curable composition, cured product thereof, semiconductor sealing material, and printed wiring board | |
| KR20100008771A (en) | Crystalline modified epoxy resin, epoxy resin composition and crystalline cured product | |
| WO2014073557A1 (en) | Phenolic-hydroxyl-containing resin, epoxy resin, curable resin composition, substance obtained by curing same, and semiconductor sealant | |
| KR101966212B1 (en) | Epoxy resin compound and radiant heat circuit board using the same | |
| KR100724996B1 (en) | Epoxy resins, process for production thereof, epoxy resin compositions and cured articles | |
| JP4237600B2 (en) | Epoxy resin composition for semiconductor encapsulation and semiconductor device using the same | |
| JP2013010903A (en) | Epoxy resin, curing resin composition, cured product thereof, semiconductor sealing material, and printed wiring board | |
| JP2012046465A (en) | Phenolic resin, epoxy resin, method for producing them, epoxy resin composition, and cured product | |
| WO2021201046A1 (en) | Polyhydric hydroxy resin, epoxy resin, method for producing same, epoxy resin composition using same and cured product | |
| JP2010184963A (en) | Epoxy resin composition and cured product of the same, epoxy resin and method for producing the same, sealing material for semiconductor, and semiconductor device | |
| JP5679248B1 (en) | Epoxy compound, epoxy resin, curable composition, cured product thereof, semiconductor sealing material, and printed wiring board | |
| JP2013119608A (en) | Epoxy resin, epoxy resin composition and cured product thereof | |
| JP5040404B2 (en) | Epoxy resin composition for sealing material, cured product thereof and semiconductor device | |
| JP6241186B2 (en) | Phenol resin, epoxy resin, production method thereof, curable composition, cured product thereof, semiconductor sealing material, and printed wiring board | |
| JPH111546A (en) | Epoxy resin composition and electronic component | |
| JP6066158B2 (en) | Epoxy resin, curable resin composition, cured product thereof, semiconductor sealing material, and semiconductor device | |
| JP2012197366A (en) | Epoxy resin composition and molding | |
| JP2004339277A (en) | Phenol resin, curing agent for epoxy resin, and epoxy resin composition | |
| JP6288493B2 (en) | Phenol resin, epoxy resin, production method thereof, curable composition, cured product thereof, semiconductor sealing material, and printed wiring board |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20230915 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20230915 |