CN118271535A - Resin composition, prepreg and copper-clad laminate manufactured by using resin composition - Google Patents
Resin composition, prepreg and copper-clad laminate manufactured by using resin composition Download PDFInfo
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- CN118271535A CN118271535A CN202410523327.0A CN202410523327A CN118271535A CN 118271535 A CN118271535 A CN 118271535A CN 202410523327 A CN202410523327 A CN 202410523327A CN 118271535 A CN118271535 A CN 118271535A
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- Prior art keywords
- resin composition
- bis
- parts
- weight
- vinylphenyl
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims abstract description 65
- -1 vinyl benzyl groups Chemical group 0.000 claims abstract description 67
- 229920005989 resin Polymers 0.000 claims abstract description 54
- 239000011347 resin Substances 0.000 claims abstract description 54
- 150000001875 compounds Chemical class 0.000 claims abstract description 36
- 229920001955 polyphenylene ether Polymers 0.000 claims abstract description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 12
- 229920013636 polyphenyl ether polymer Polymers 0.000 claims abstract description 3
- 239000003063 flame retardant Substances 0.000 claims description 25
- 239000000758 substrate Substances 0.000 claims description 21
- 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 claims description 17
- FAPKAHJYPAALBJ-UHFFFAOYSA-N 1-ethenyl-2-[1-(2-ethenylphenyl)ethyl]benzene Chemical compound C=1C=CC=C(C=C)C=1C(C)C1=CC=CC=C1C=C FAPKAHJYPAALBJ-UHFFFAOYSA-N 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000654 additive Substances 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 239000011256 inorganic filler Substances 0.000 claims description 9
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 239000003431 cross linking reagent Substances 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 8
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 239000000945 filler Substances 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 4
- 239000012766 organic filler Substances 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 229920001187 thermosetting polymer Polymers 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000011888 foil Substances 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 claims description 2
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 claims description 2
- WVAFEFUPWRPQSY-UHFFFAOYSA-N 1,2,3-tris(ethenyl)benzene Chemical compound C=CC1=CC=CC(C=C)=C1C=C WVAFEFUPWRPQSY-UHFFFAOYSA-N 0.000 claims description 2
- KTRQRAQRHBLCSQ-UHFFFAOYSA-N 1,2,4-tris(ethenyl)cyclohexane Chemical compound C=CC1CCC(C=C)C(C=C)C1 KTRQRAQRHBLCSQ-UHFFFAOYSA-N 0.000 claims description 2
- CCNDOQHYOIISTA-UHFFFAOYSA-N 1,2-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1C(C)(C)OOC(C)(C)C CCNDOQHYOIISTA-UHFFFAOYSA-N 0.000 claims description 2
- QLLUAUADIMPKIH-UHFFFAOYSA-N 1,2-bis(ethenyl)naphthalene Chemical compound C1=CC=CC2=C(C=C)C(C=C)=CC=C21 QLLUAUADIMPKIH-UHFFFAOYSA-N 0.000 claims description 2
- YUAYXCGERFHZJE-UHFFFAOYSA-N 1-(1-phenylprop-2-enoxy)prop-2-enylbenzene Chemical compound C=1C=CC=CC=1C(C=C)OC(C=C)C1=CC=CC=C1 YUAYXCGERFHZJE-UHFFFAOYSA-N 0.000 claims description 2
- ODBCKCWTWALFKM-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhex-3-yne Chemical compound CC(C)(C)OOC(C)(C)C#CC(C)(C)OOC(C)(C)C ODBCKCWTWALFKM-UHFFFAOYSA-N 0.000 claims description 2
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 claims description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- RIQSLGAADRJNSG-UHFFFAOYSA-N 2-ethylhexoxycarbonyloxyperoxy 2-ethylhexyl carbonate Chemical compound CCCCC(CC)COC(=O)OOOOC(=O)OCC(CC)CCCC RIQSLGAADRJNSG-UHFFFAOYSA-N 0.000 claims description 2
- FRWYFWZENXDZMU-UHFFFAOYSA-N 2-iodoquinoline Chemical compound C1=CC=CC2=NC(I)=CC=C21 FRWYFWZENXDZMU-UHFFFAOYSA-N 0.000 claims description 2
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 claims description 2
- 229910052582 BN Inorganic materials 0.000 claims description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 2
- 239000004695 Polyether sulfone Substances 0.000 claims description 2
- 239000004697 Polyetherimide Substances 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 2
- JUIBLDFFVYKUAC-UHFFFAOYSA-N [5-(2-ethylhexanoylperoxy)-2,5-dimethylhexan-2-yl] 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)CCC(C)(C)OOC(=O)C(CC)CCCC JUIBLDFFVYKUAC-UHFFFAOYSA-N 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 239000003963 antioxidant agent Substances 0.000 claims description 2
- 239000002216 antistatic agent Substances 0.000 claims description 2
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 2
- 229910002113 barium titanate Inorganic materials 0.000 claims description 2
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 239000000378 calcium silicate Substances 0.000 claims description 2
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- 229910052570 clay Inorganic materials 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 2
- 229910002026 crystalline silica Inorganic materials 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 2
- 239000005350 fused silica glass Substances 0.000 claims description 2
- 239000012760 heat stabilizer Substances 0.000 claims description 2
- 150000002430 hydrocarbons Chemical group 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 239000004611 light stabiliser Substances 0.000 claims description 2
- 239000000314 lubricant Substances 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 239000003607 modifier Substances 0.000 claims description 2
- 239000006082 mold release agent Substances 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 125000000864 peroxy group Chemical group O(O*)* 0.000 claims description 2
- 239000004014 plasticizer Substances 0.000 claims description 2
- 229920006393 polyether sulfone Polymers 0.000 claims description 2
- 229920001601 polyetherimide Polymers 0.000 claims description 2
- 229920006380 polyphenylene oxide Polymers 0.000 claims description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 239000012745 toughening agent Substances 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- IYSVFZBXZVPIFA-UHFFFAOYSA-N 1-ethenyl-4-(4-ethenylphenyl)benzene Chemical group C1=CC(C=C)=CC=C1C1=CC=C(C=C)C=C1 IYSVFZBXZVPIFA-UHFFFAOYSA-N 0.000 claims 1
- 239000000839 emulsion Substances 0.000 claims 1
- 229940070710 valerate Drugs 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 13
- 238000010521 absorption reaction Methods 0.000 abstract description 9
- 230000009477 glass transition Effects 0.000 abstract description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 29
- 150000002500 ions Chemical class 0.000 description 16
- 238000000034 method Methods 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- 238000004255 ion exchange chromatography Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000011889 copper foil Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 238000003475 lamination Methods 0.000 description 6
- 239000006087 Silane Coupling Agent Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000004744 fabric Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000013032 Hydrocarbon resin Substances 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 229920006270 hydrocarbon resin Polymers 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- DYIZJUDNMOIZQO-UHFFFAOYSA-N 4,5,6,7-tetrabromo-2-[2-(4,5,6,7-tetrabromo-1,3-dioxoisoindol-2-yl)ethyl]isoindole-1,3-dione Chemical compound O=C1C(C(=C(Br)C(Br)=C2Br)Br)=C2C(=O)N1CCN1C(=O)C2=C(Br)C(Br)=C(Br)C(Br)=C2C1=O DYIZJUDNMOIZQO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000004745 nonwoven fabric Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 239000002759 woven fabric Substances 0.000 description 3
- BPNJDDYBNRHHQT-UHFFFAOYSA-N 1-ethenyl-4-(1-phenylbut-3-en-2-yl)benzene Chemical compound C=CC1=CC=C(C=C1)C(CC2=CC=CC=C2)C=C BPNJDDYBNRHHQT-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 2
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- MYOQALXKVOJACM-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy pentaneperoxoate Chemical compound CCCCC(=O)OOOC(C)(C)C MYOQALXKVOJACM-UHFFFAOYSA-N 0.000 description 1
- BZQKBFHEWDPQHD-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-[2-(2,3,4,5,6-pentabromophenyl)ethyl]benzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1CCC1=C(Br)C(Br)=C(Br)C(Br)=C1Br BZQKBFHEWDPQHD-UHFFFAOYSA-N 0.000 description 1
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- IAAMWBRTUSKTFF-UHFFFAOYSA-N 1-ethenyl-3-(1-phenylbut-3-en-2-yl)benzene Chemical compound C=CC1=CC(=CC=C1)C(CC2=CC=CC=C2)C=C IAAMWBRTUSKTFF-UHFFFAOYSA-N 0.000 description 1
- BEAJSLIPFWZETL-UHFFFAOYSA-N 1-ethenyl-4-[1-(4-ethenylphenyl)ethyl]benzene Chemical compound C=1C=C(C=C)C=CC=1C(C)C1=CC=C(C=C)C=C1 BEAJSLIPFWZETL-UHFFFAOYSA-N 0.000 description 1
- WVGXBYVKFQJQGN-UHFFFAOYSA-N 1-tert-butylperoxy-2-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC=C1OOC(C)(C)C WVGXBYVKFQJQGN-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- KMRIWYPVRWEWRG-UHFFFAOYSA-N 2-(6-oxobenzo[c][2,1]benzoxaphosphinin-6-yl)benzene-1,4-diol Chemical compound OC1=CC=C(O)C(P2(=O)C3=CC=CC=C3C3=CC=CC=C3O2)=C1 KMRIWYPVRWEWRG-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- GXIPHHIBYMWSMN-UHFFFAOYSA-N 6-phenylbenzo[c][2,1]benzoxaphosphinine 6-oxide Chemical compound O1C2=CC=CC=C2C2=CC=CC=C2P1(=O)C1=CC=CC=C1 GXIPHHIBYMWSMN-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229920000271 Kevlar® Polymers 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- VMCRDONCOBHEHW-UHFFFAOYSA-N [2,6-bis(2,6-dimethylphenyl)phenyl]phosphane Chemical compound CC1=CC=CC(C)=C1C1=CC=CC(C=2C(=CC=CC=2C)C)=C1P VMCRDONCOBHEHW-UHFFFAOYSA-N 0.000 description 1
- MWGMEGAYPPQWFG-UHFFFAOYSA-N [SiH4].OC(=O)C=C Chemical compound [SiH4].OC(=O)C=C MWGMEGAYPPQWFG-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- AZDCYKCDXXPQIK-UHFFFAOYSA-N ethenoxymethylbenzene Chemical compound C=COCC1=CC=CC=C1 AZDCYKCDXXPQIK-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 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 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 239000004761 kevlar Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 230000006855 networking Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- RERMPCBBVZEPBS-UHFFFAOYSA-N tris(2,6-dimethylphenyl)phosphane Chemical compound CC1=CC=CC(C)=C1P(C=1C(=CC=CC=1C)C)C1=C(C)C=CC=C1C RERMPCBBVZEPBS-UHFFFAOYSA-N 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention provides a resin composition, and a prepreg and a copper-clad laminate manufactured by using the same, wherein the resin composition comprises the following components: (A) The end group is polyphenyl ether resin containing vinyl benzyl groups; (B) And a bis (vinylphenyl) compound wherein the sum of the chloride ion amount of the polyphenylene ether resin having a vinylbenzyl group as the terminal group and the bis (vinylphenyl) compound represented by the formula (I) is 700ppm or less. The resin composition has good dielectric properties, and maintains its high glass transition temperature, low water absorption and wet heat resistance.
Description
Technical Field
The invention belongs to the technical field of laminated boards, and relates to a resin composition, and a prepreg and a copper-clad laminated board manufactured by using the resin composition.
Background
In recent years, with the development of high performance, high functionality, and networking of computers and information communication apparatuses, operation signals tend to be high-frequency in order to transmit and process large-capacity information at high speed, and thus, there is a demand for materials for circuit substrates, particularly those using broadband electronic apparatuses such as mobile communication devices.
Epoxy resins excellent in adhesion characteristics are widely used as materials for printed circuit boards. However, epoxy resin circuit boards generally have a high dielectric constant and a high dielectric loss tangent (dielectric constant Dk is greater than 4, and dielectric loss tangent Df is about 0.02), and thus have insufficient high-frequency characteristics, and are not suitable for the requirements of high-frequency signals. Therefore, it is necessary to develop a resin excellent in dielectric characteristics, that is, a resin having a low dielectric constant and low dielectric loss tangent. Thermosetting polyphenylene ether resins, bismaleimide resins, vinylbenzyl ether resins, hydrocarbon resins, etc. that have excellent dielectric properties have been studied by those skilled in the art for a long time; as is well known, the curable and crosslinked hydrocarbon resin (polyolefin resin) has a low dielectric loss tangent Df (comparable to polytetrafluoroethylene resin) and good fluidity, and attracts a great deal of intensive research on the curable and crosslinked hydrocarbon resin (polyolefin resin) by a large number of technicians, but the curable and crosslinked hydrocarbon resin cannot meet the process manufacturing requirements of high-multilayer printed wiring boards due to insufficient heat resistance, and needs to be matched with other resins with good heat resistance.
Chinese patent application CN1745142a discloses the use of a polyphenylene ether resin containing vinyl phenyl and m-vinyl phenyl at the end groups as a main resin, the use of trialkenyl isocyanurate as a crosslinking curing agent, optionally adding inorganic filler and flame retardant to obtain a polyphenylene ether resin composition, and then impregnating NE-type glass fiber fabric to obtain prepregs and laminates having excellent dielectric properties and higher glass transition temperatures, but the patent application does not investigate the effect of the chloride ion amount of polyphenylene ether used on various properties.
Chinese patent application CN 111116814A discloses that using a modified polyphenylene ether resin and a prepolymer obtained by prepolymerizing with a bis (vinylphenyl) compound as a main resin, adding an inorganic filler and a flame retardant as necessary to obtain a polyphenylene ether resin composition, and then impregnating L-glass fiber cloth to obtain prepregs and laminates having excellent dielectric properties and a higher glass transition temperature, but because of the problem of controlling in the production process of the bis (vinylphenyl) compound, chloride ion residues are easily caused to affect the properties of the sheet. And the patent application does not investigate the influence of the chloride ion amounts of polyphenylene ether and bis (vinylphenyl) compounds used therein on various properties.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a resin composition, and a prepreg and a copper clad laminate manufactured by using the resin composition, wherein the resin composition has good dielectric property, and keeps high glass transition temperature, low water absorption and wet heat resistance.
To achieve the purpose, the invention adopts the following technical scheme:
In one aspect, the present invention provides a resin composition comprising the following components:
(A) The end group is polyphenyl ether resin containing vinyl benzyl groups;
(B) Bis (vinylphenyl) compounds of formula (I),
Wherein R is any one of structures shown in formulas (II) to (IV):
Wherein n 1 represents an integer from 0 to 30 (e.g., 0, 1, 3, 5, 8, 10, 15, 18, 20, 25, 28, or 30), n 2 represents an integer from 0 to 6 (e.g., 0, 1, 2,3,4,5, or 6), and n 3、n4、n5、n6 and n 7 each independently represent an integer from 1 to 6 (e.g., 1, 2,3,4,5, or 6);
The sum of the chloride ion amount of the polyphenylene ether resin having a terminal group containing a vinylbenzyl group and the bis (vinylphenyl) compound represented by the formula (I) is 700ppm or less.
Since the polyphenylene ether resin containing a vinylbenzyl group and the bis (vinylphenyl) compound in the resin composition of the present invention and the sum of the chloride ion amounts of the polyphenylene ether resin and the bis (vinylphenyl) compound is controlled to 700ppm or less, the resin composition can have good dielectric properties and maintain its high glass transition temperature, low water absorption and wet heat resistance.
In the present invention, the sum of the chloride ion amounts of the polyphenylene ether resin having a vinylbenzyl group as the terminal group and the bis (vinylphenyl) compound represented by the formula (I) is not particularly limited as long as it is 700ppm or less, and for example, the sum of the chloride ion amounts of the both may be 700ppm, 600ppm, 500ppm, 300ppm, 100ppm, 80ppm, 60ppm, 50ppm, 40ppm, 30ppm, 20ppm, 10ppm, etc., preferably 500ppm or less, more preferably 300ppm or less. The smaller the amount of the above Cl ions, the more preferable the amount of the above Cl ions, but since the polyphenylene ether resin having a vinylbenzyl group and the bis (vinylphenyl) compound are inevitably mixed in some extent at the time of production, there is a fear that the cost increases in order to reduce the amount of the above Cl ions. Therefore, from the viewpoint of cost, the amount of Cl ions in the resin composition is preferably 5ppm or more. More preferably 10ppm or more, still more preferably 20ppm or more, and still more preferably 30ppm or more. The Cl ion content is herein tested using method 2.3.41 (ion chromatography) in IPC-TM-650.
Specifically, the dielectric loss Df of the bis (vinylphenyl) compound in the resin composition is superior to that of a polyphenylene ether resin having a vinylbenzyl group at the end, and the sensitivity of the amount of Cl ions to the dielectric loss Df of the resin composition of the present invention is somewhat higher than that of a polyphenylene ether resin having only a vinylbenzyl group, and thus, special attention is required to the Cl ion amount of the bis (vinylphenyl) compound.
In the present invention, the amount of chloride ions of the polyphenylene ether resin having a vinylbenzyl group and the bis (vinylphenyl) compound represented by the formula (I) refers to the residual amount of chloride ions in the product obtained as a result of the preparation process of the polyphenylene ether resin having a vinylbenzyl group and the bis (vinylphenyl) compound represented by the formula (I).
Preferably, the structure of the polyphenylene ether resin having a terminal group of the component (A) which is a vinyl benzyl group is represented by the following formula (5):
In formula (5), a and b are integers of 1 to 30 (e.g., 1, 3, 5, 8, 10, 15, 20, 25, 30, etc.), and Z is a structure defined by formula (6):
- (-O-Y-) -in formula (5) is a structure defined by formula (7):
In the formula (7), R 4 and R 6 are the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 8 or less carbon atoms or a phenyl group, and R 5 and R 7 are the same or different and are a halogen atom, an alkyl group having 8 or less carbon atoms or a phenyl group;
- (-O-X-O-) in formula (5) is a structure defined by formula (8):
In the formula (8), R 8、R9、R10、R11、R12、R13、R14 and R 15 are the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group having 8 or less carbon atoms or a phenyl group, and B is an alkylene group having 20 or less carbon atoms,
N is 0 or 1; r 16 is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms (for example, 1, 2, 3, 5, 7, 9 or 10, etc.).
Preferably, the bis (vinylphenyl) compound represented by formula (I) is selected from the group consisting of bis (vinylphenyl) ethane, bis (vinylphenyl) dimethylene benzene, bis (vinylphenyl) dimethylene ether, bis (vinylphenyl) diethyleneglycol benzene; bis (vinylphenyl) compounds are preferred. More preferably, the bis (vinylphenyl) compound is bis (vinylphenyl) ethane (BVPE).
Preferably, the bis (vinylphenyl) ethane is selected from any one of the compounds of the structures of the following formula (9), formula (10) or formula (11):
In the present invention, the bis (vinylphenyl) ethane may be selected from any one or more of isomers of p, p-divinyl-1, 2-diphenylethane (p, p-BVPE), m, p-divinyl-1, 2-diphenylethane (m, p-BVPE), and m, m-divinyl-1, 2-diphenylethane (m, m-BVPE). Wherein p represents para and m represents meta.
Preferably, the bis (vinylphenyl) compound is 5 to 95 parts by weight (e.g., 5 parts by weight, 8 parts by weight, 25 parts by weight, 35 parts by weight, 45 parts by weight, 50 parts by weight, 60 parts by weight, 70 parts by weight, 80 parts by weight, 90 parts by weight, or 95 parts by weight) based on 100 parts by weight of the total amount of the resin components in the resin composition, and the polyphenylene ether resin having a terminal group containing a vinylbenzyl group is 5 to 95 parts by weight (e.g., 5 parts by weight, 8 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 35 parts by weight, 45 parts by weight, 50 parts by weight, 60 parts by weight, 70 parts by weight, 80 parts by weight, 90 parts by weight, or 95 parts by weight).
In the present invention, the resin composition may contain a crosslinking agent which reacts with the compound to cure the compound, in addition to the above two resins; preferably, the crosslinking agent is a compound containing a styrene reactive group, and may be any one or a combination of at least two of a polyfunctional vinyl aromatic copolymer, divinylbenzene, divinylnaphthalene, t-butylstyrene, bis (vinylbenzyl) ether, trivinylbenzene, trivinylbiphenyl, 1,2, 4-trivinylcyclohexane, and the like, but is not limited thereto.
In the present invention, the crosslinking agent is used in an amount of 1 to 90 parts by weight, for example, 1 part by weight, 3 parts by weight, 5 parts by weight, 8 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight, 60 parts by weight, 70 parts by weight, 80 parts by weight, or 90 parts by weight, based on 100 parts by weight of the total amount of the resin components in the resin composition.
In the resin composition according to the present invention, an initiator may be further included, preferably, the initiator is selected from one or a combination of at least two of dicumyl peroxide, t-butyl peroxybenzoate, 2, 5-bis (2-ethylhexanoylperoxy) -2, 5-dimethylhexane, di- (t-butylperoxyisopropyl) benzene, peroxy (2, 4-dichlorobenzoyl), 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane, peroxy-2-ethylhexyl carbonate, 2, 5-dimethyl-2, 5-bis (t-butylperoxy) -3-hexyne, 4-bis (t-butylperoxy) pentanoate, 1-bis (t-butylperoxy) -3, 5-trimethylcyclohexane, 3,5, 7-pentamethyl-1, 2, 4-trioxepane, di-t-butylperoxide or t-butylperoxycumene.
Preferably, the initiator is used in an amount of 0 to 3 parts by weight, for example, 0.1 part by weight, 0.5 part by weight, 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight or 3 parts by weight, based on 100 parts by weight of the total amount of the resin components in the resin composition.
In the present invention, the resin composition further comprises a filler comprising an organic filler and/or an inorganic filler.
Preferably, the inorganic filler is selected from one or a combination of at least two of crystalline silica, fused silica, spherical silica, hollow silica, glass frit, aluminum nitride, boron nitride, silicon carbide, silicon aluminum carbide, aluminum hydroxide, magnesium hydroxide, titanium dioxide, strontium titanate, barium titanate, zinc oxide, zirconium oxide, aluminum oxide, beryllium oxide, magnesium oxide, barium sulfate, talc, clay, calcium silicate, calcium carbonate, or mica.
Preferably, the organic filler is selected from one or a combination of at least two of polytetrafluoroethylene powder, polyphenylene sulfide, polyetherimide, polyphenylene oxide or polyethersulfone powder.
The shape and particle size of the inorganic filler are not limited, but the particle size of the inorganic filler used in the present invention is usually 0.01 to 50. Mu.m, for example, 0.01 to 20. Mu.m, 0.05. Mu.m, 0.08. Mu.m, 0.1. Mu.m, 0.2. Mu.m, 0.5. Mu.m, 1. Mu.m, 3. Mu.m, 5. Mu.m, 8. Mu.m, 10. Mu.m, 15. Mu.m, 20. Mu.m, 25. Mu.m, 30. Mu.m, 35. Mu.m, 40. Mu.m, 45. Mu.m, 50. Mu.m, etc., preferably 0.01 to 20. Mu.m, more preferably 0.01 to 10. Mu.m, and the inorganic filler having such particle size range is more easily dispersed in the resin liquid.
The amount of the filler to be used in the resin composition is not particularly limited, and is preferably 5 to 400 parts by weight, for example, 5 to 10 parts by weight, 20 parts by weight, 30 parts by weight, 40 parts by weight, 50 parts by weight, 60 parts by weight, 70 parts by weight, 80 parts by weight, 90 parts by weight, 100 parts by weight, 110 parts by weight, 120 parts by weight, 130 parts by weight, 140 parts by weight or 150 parts by weight, 200 parts by weight, 250 parts by weight, 300 parts by weight, 350 parts by weight or 400 parts by weight, more preferably 5 to 200 parts by weight, and further preferably 5 to 150 parts by weight based on 100 parts by weight of the total amount of the resin components in the resin composition.
Preferably, the resin composition of the present invention further includes a flame retardant, which may be a bromine-containing flame retardant or a halogen-free flame retardant.
The inclusion of a flame retardant in the resin composition of the present invention is determined by the need for flame retardancy, so that the resin cured product has flame retardant properties, which meet the requirements of UL 94V-0. The flame retardant to be added as needed is not particularly limited, and is preferably one which does not affect the dielectric properties.
Preferably, the bromine-containing flame retardant is one or a combination of at least two of decabromodiphenyl ether, decabromodiphenyl ethane, ethylene bis-tetrabromophthalimide or brominated polycarbonate. Alternative commercial brominated flame retardants are BT-93, BT-93W, satex-8010 or HP-3010, but are not limited to the above.
Preferably, the halogen-free flame retardant is one or a combination of at least two of a phosphorus-containing halogen-free flame retardant, a nitrogen-containing halogen-free flame retardant and a silicon-containing halogen-free flame retardant.
Preferably, the halogen-free flame retardant is one or a combination of at least two of tris (2, 6-dimethylphenyl) phosphine, 10- (2, 5-dihydroxyphenyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2, 6-bis (2, 6-dimethylphenyl) phosphinobenzene or 10-phenyl-9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, phenoxyphosphane cyanide, phosphate or polyphosphate.
Alternative commercial halogen-free flame retardants are SP-100, PX-200, PX-202, OP-930, OP-935, JH-100, XP-7866, etc., but are not limited to the above.
In the present invention, the amount of the flame retardant is not particularly limited depending on the requirement that the cured product reaches the UL 94V-0 level. The flame retardant is used in an amount of 5 to 80 parts by weight, for example, 5 parts by weight, 8 parts by weight, 10 parts by weight, 20 parts by weight, 30 parts by weight, 40 parts by weight, 50 parts by weight, 60 parts by weight, 70 parts by weight or 80 parts by weight, preferably 10 to 60 parts by weight, more preferably 15 to 40 parts by weight, based on 100 parts by weight of the total amount of the resin components in the resin composition, in view of not sacrificing the heat resistance, dielectric properties, hygroscopicity of the cured product. When the addition amount of the flame retardant is insufficient, a good flame retardant effect cannot be achieved; when the flame retardant is added in an amount of more than 80 parts, there is a risk that the heat resistance of the system is lowered and the water absorption is increased, and the dielectric properties of the system are deteriorated.
Preferably, the resin composition further comprises other additives introduced to solve some problems, the other additives being one or a combination of at least two of antioxidants, heat stabilizers, light stabilizers, plasticizers, lubricants, flow modifiers, anti-drip agents, anti-blocking agents, antistatic agents, flow promoters, processing aids, substrate adhesives, mold release agents, toughening agents, low shrinkage additives, or stress relief additives.
In the thermosetting resin composition of the present invention, the amount of the other additive is not particularly limited, and is preferably 0.1 to 10 parts by weight, for example, 0.1 to 0.5 part by weight, 0.8 part by weight, 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, or 10 parts by weight, more preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the total amount of the resin components in the resin composition.
In another aspect, the present invention provides a method for preparing the resin composition as described above, which can be prepared by compounding, stirring, and mixing the polyphenylene ether, the bis (vinylphenyl) compound, the crosslinking agent, the initiator, the filler, the flame retardant, and various other additives by a known method.
In another aspect, the present invention provides a resin dope obtained by dissolving or dispersing the resin composition as described above in a solvent.
The solvent in the present invention is not particularly limited, and specific examples thereof include alcohols such as methanol, ethanol and butanol, ethers such as ethyl cellosolve, butyl cellosolve, ethylene glycol-methyl ether, carbitol and butyl carbitol, ketones such as acetone, butanone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene and mesitylene, esters such as ethoxyethyl acetate and ethyl acetate, and nitrogen-containing solvents such as N, N-dimethylformamide, N-dimethylacetamide and N-methyl-2-pyrrolidone. The solvent may be used alone or in combination of two or more, and is preferably an aromatic hydrocarbon solvent such as toluene, xylene, mesitylene, or a ketone solvent such as acetone, butanone, methyl ethyl ketone, methyl isobutyl ketone, or cyclohexanone. The amount of the solvent to be used may be selected by one skilled in the art according to his own experience, so that the resulting resin dope may have a viscosity suitable for use.
In the process of dissolving or dispersing the resin composition in the solvent as described above, an emulsifier may be added. The powder filler and the like can be uniformly dispersed in the glue solution by dispersing the emulsifier.
In another aspect, the present invention provides a prepreg comprising a substrate and the thermosetting resin composition as described above attached to the substrate after impregnation drying.
The prepreg according to the present invention may be also called a prepreg, and may be obtained by impregnating a substrate with the above-mentioned resin dope, then heating and drying the substrate to remove the organic solvent and partially curing the resin composition in the substrate. The substrate may also be referred to as a reinforcing material in the present invention.
Preferably, the substrate is a woven or nonwoven fabric made of organic, carbon or inorganic fibers.
Preferably, the organic fibers comprise aramid fibers, such as Kevlar fibers from dupont.
The inorganic fiber-made woven or nonwoven fabric is not particularly limited, and preferably, the inorganic fiber-made woven or nonwoven fabric contains 50 to 99.9% (e.g., 50%, 55%, 58%, 60%, 65%, 70%, 75%, 80%, 85%, 88%, 90%, 95%, or 99%) by weight of SiO 2, 0 to 30% (e.g., 0%, 5%, 10%, 15%, 20%, 25%, or 30%) by weight of CaO, 0 to 20% (e.g., 0%, 5%, 10%, 15%, or 20%) by weight of Al 2O3, 0 to 25% (e.g., 0%, 5%, 10%, 15%, 20%, or 25%) by weight of B 2O3, and 0 to 5% (e.g., 0%, 0.5%, 1%, 2%, 3%, 4%, or 5%) by weight of MgO in the composition. Preferably, the substrate (reinforcing material) is preferably a woven fibre cloth, optionally E-Glass, T-Glass, NE-Glass, L2-Glass, NER-Glass, Q-Glass, particularly preferably NE-Glass. The thickness of the substrate to be used is not particularly limited either.
The resin content used to impregnate the above-mentioned substrate is preferably such that 30 mass% or more, for example, 30 mass%, 35 mass%, 40 mass%, 50 mass%, 60 mass%, 70 mass% or more of the resin content in the semi-curing is attained. Since the dielectric constant of the substrate tends to be higher than that of the resin composition, the content of the resin composition component in the prepreg is preferably the above content in order to reduce the dielectric constant of the laminate made from these prepregs.
Preferably, the above-mentioned prepreg is dried at a temperature of 80 to 200 ℃, for example 80 ℃, 90 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃,150 ℃, 170 ℃, 190 ℃, 200 ℃, or the like; the drying time is 1-30 min, such as 1min, 5min, 8min, 13min, 17min, 21min, 24min, 28min or 30 min.
In another aspect, the present invention provides a laminate comprising at least one prepreg as described above.
In another aspect, the present invention provides a metal foil-clad laminate comprising one or at least two laminated prepregs as described above, and a metal foil on one or both sides of the laminated prepregs.
Preferably, the metal foil is copper foil. Preferably, the copper foil is an electrodeposited or calendered copper foil having a surface roughness of less than 5 microns, such as less than 4 microns, less than 3 microns, less than 2 microns, less than 1 micron, less than 0.8 microns, less than 0.5 microns, and the like. The signal loss of the laminated board material in the high-frequency high-speed printed circuit board can be improved and increased.
Meanwhile, in order to improve the adhesive force of one side of the copper foil prepreg, it is further preferable that the copper foil is chemically treated with a silane coupling agent, wherein the silane coupling agent is one or a mixture of at least two of an aminosilane coupling agent, an epoxy silane coupling agent, a vinyl silane coupling agent, or an acrylate silane coupling agent.
In another aspect, the present invention provides a high frequency high speed circuit substrate comprising one or at least two superimposed prepregs as described above.
Specifically, the high-speed circuit substrate is prepared by the following steps:
And overlapping at least one prepreg, placing copper foils on the upper side and the lower side of the overlapped prepreg, and performing lamination forming to obtain the laminated prepreg. The overlapping preferably employs an automatic stacking operation, thereby making the process operation easier.
The lamination is preferably vacuum lamination, which can be achieved by a vacuum laminator. The laminating time is 70-120 min, such as 70min, 75min, 80min, 85min, 90min, 95min, 100min, 105min, 110min, 115min or 120 min; the lamination temperature is 180-220 ℃, such as 180 ℃, 185 ℃, 190 ℃, 195 ℃, 200 ℃, 205 ℃, 210 ℃, 215 ℃ or 220 ℃; the lamination pressure is 20 to 60kg/cm 2, such as 20kg/cm2、25kg/cm2、30kg/cm2、35kg/cm2、40kg/cm2、45kg/cm2、50kg/cm2、55kg/cm2、58kg/cm2 or 60kg/cm 2, etc.
Compared with the prior art, the invention has the following beneficial effects:
the resin composition has good dielectric property, keeps the advantages of high glass transition temperature, low water absorption, wet heat resistance and the like, and the circuit substrate obtained by the resin composition has good dielectric property, and keeps the advantages of high glass transition temperature, low water absorption and wet heat resistance.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Commercially available end groups are polyphenylene ethers containing vinylbenzyl groups: OPE-2ST 2200 (Mitsubishi gas) was tested for Cl ion content of 930ppm using method 2.3.41 (ion chromatography) in IPC-TM-650.
Preparation example 1
Commercial OPE-2ST 2200 was placed in a vessel, 50% toluene was added and stirred to dissolve, and the mass ratio of methanol to water was 80:20 was washed 1 time and dried at 80℃under reduced pressure for 3 hours. Cl ion content was measured using method 2.3.41 (ion chromatography) in IPC-TM-650 and resulted in 773ppm, product name OPE-2ST 2200-1.
Preparation example 2
As with the preparation of preparation 1, but the number of washes was increased from 1 to 3, the Cl ion content was also measured using method 2.3.41 (ion chromatography) in IPC-TM-650, resulting in 421ppm, product name OPE-2ST 2200-2.
Preparation example 3
As in the preparation of preparation 1, but the number of washes was increased from 1 to 5, the Cl ion content was also measured using method 2.3.41 (ion chromatography) in IPC-TM-650, resulting in 63ppm, product name OPE-2ST 2200-3.
Commercial bis (p-vinylphenyl) ethane BVPE (New Stark) was tested for Cl ion content at 998ppm using method 2.3.41 (ion chromatography) in IPC-TM-650.
Preparation example 4
The commercial BVPE (Xingshun new material) is placed in a container, 75% of the BVPE is added to be stirred and dissolved, then water with the same mass as toluene is added to be stirred for 1-2 hours, and the mixture is stood for layering, and the upper layer solution is taken. The previous washing process is repeated for 5 times, the washed upper layer solution is distilled, toluene is removed, and the residual solution is led into toluene and methanol to be separated out. Cl ion content was measured using method 2.3.41 (ion chromatography) in IPC-TM-650 and the result was 67ppm, product name BVPE-1.
Preparation example 5
The commercial BVPE (Xingshun new material) is placed in a container, 75% of the BVPE is added to be stirred and dissolved, then water with the same mass as toluene is added to be stirred for 1-2 hours, and the mixture is stood for layering, and the upper layer solution is taken. The previous washing process is repeated for 2 times, the washed upper layer solution is distilled, toluene is removed, and the residual solution is led into toluene and methanol to be separated out. Cl ion content was measured using method 2.3.41 (ion chromatography) in IPC-TM-650 and the result was 235ppm, product name BVPE-2.
Table 1 shows the raw materials used in the examples and comparative examples.
TABLE 1
Example 1
70.0 Parts by weight of a self-made bifunctional vinylbenzyl-modified polyphenylene ether OPE-2ST 2200-2 and 30.0 parts by weight of a bis (vinylphenyl) compound BVPE-1 (Cl content: 67 ppm) were dissolved in a toluene solvent to obtain a resin dope. The resin glue solution was infiltrated with NE-fiberglass cloth (Nittobo, model 2116 NE), passed through a nip shaft and dried in an oven, and toluene solvent was removed to prepare 2116 prepreg. 6 prepregs of 2116 are placed together in an overlapping manner, copper foil with the thickness of 1OZ is matched on the upper surface and the lower surface, the prepreg is subjected to vacuum lamination and solidification in a press for 120min, the solidification pressure is 50kg/cm 2, the solidification temperature is 210 ℃, and the high-speed circuit substrate with the thickness of 0.76mm is manufactured.
Examples 2 to 9 and comparative examples 1 to 5 were prepared as in example 1, and the amounts of the respective components are shown in tables 2 to 4.
TABLE 2
TABLE 3 Table 3
TABLE 4 Table 4
The test method of the above characteristics is as follows:
1) Glass transition temperature (Tg): the Tg of the laminates was determined according to dynamic thermomechanical analysis (DMA) and the DMA method specified in IPC-TM-6502.4.24.4.
2) Water absorption rate: the sample was dried at 105-110 ℃ for 1h, taken out and placed at room temperature and weighed for m 1, after immersing the sample in 23 ℃/24h, the sample was taken out from the water, the surface water was removed by wiping with a dry cloth and then weighed for m 2, and the% water absorption= (m 2-m1)/m1 x 100) was calculated.
3) Dielectric constant Dk and dielectric dissipation factor Df: the test frequency was 10GHz according to the separation medium column cavity SPDR (Split Post Dielectric Resonator) method.
Physical property analysis:
From the results shown in tables 2 to 4, it can be seen that: the present invention can provide a resin composition having low dielectric characteristics, high Tg and low water absorption. It can be seen from example 3 compared with example 1 that the addition of the initiator deteriorates the dielectric properties of the resin composition.
In contrast, comparative example 1 using a resin compound having a large amount of Cl ions had a lower dielectric loss than example 1, comparative example 2 had a lower dielectric loss than example 5, and comparative example 3 had a lower dielectric loss than example 6. In addition, if the bis (vinylphenyl) compound is replaced with another crosslinking agent, the Cl ion amount of the whole system is in the range of 700ppm or less, but the heat resistance and dielectric loss are deteriorated.
The applicant states that the present invention is described by way of the above examples as well as the resin composition of the present invention and the prepreg and copper clad laminate manufactured using the same, but the present invention is not limited to the above examples, i.e., it does not mean that the present invention must be practiced by relying on the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (10)
1. A resin composition, characterized in that the resin composition comprises the following components:
(A) The end group is polyphenyl ether resin containing vinyl benzyl groups;
(B) A bis (vinylphenyl) compound represented by formula (I);
wherein R is any one of structures shown in formulas (II) to (IV):
Wherein n 1 represents an integer of 0 to 30, n 2 represents an integer of 0 to 6, and n 3、n4、n5、n6 and n 7 each independently represent an integer of 1 to 6;
The sum of the chloride ion amount of the polyphenylene ether resin having a terminal group containing a vinylbenzyl group and the bis (vinylphenyl) compound represented by the formula (I) is 700ppm or less.
2. The resin composition according to claim 1, wherein the sum of the chloride ion amount of the polyphenylene ether resin having a vinylbenzyl group as the terminal group and the bis (vinylphenyl) compound represented by the formula (I) is 500ppm or less, more preferably 300ppm or less.
3. The resin composition according to claim 1 or 2, wherein the terminal group of the component (a) is a polyphenylene ether resin having a vinylbenzyl group, the structure of which is represented by the following formula (5):
In the formula (5), a and b are integers of 1 to 30, and Z is a structure defined by the formula (6):
- (-O-Y-) -in formula (5) is a structure defined by formula (7):
In the formula (7), R 4 and R 6 are the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 8 or less carbon atoms or a phenyl group, and R 5 and R 7 are the same or different and are a halogen atom, an alkyl group having 8 or less carbon atoms or a phenyl group;
- (-O-X-O-) in formula (5) is a structure defined by formula (8):
In the formula (8), R 8、R9、R10、R11、R12、R13、R14 and R 15 are the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group having 8 or less carbon atoms or a phenyl group, and B is an alkylene group having 20 or less carbon atoms,
-O-、N is 0 or 1; r 16 is hydrogen atom or hydrocarbon group with 1-10 carbon atoms;
Preferably, the bis (vinylphenyl) compound represented by formula (I) is selected from the group consisting of bis (vinylphenyl) ethane, bis (vinylphenyl) dimethylene benzene, bis (vinylphenyl) dimethylene ether, bis (vinylphenyl) diethyleneglycol benzene; preferably bis (vinylphenyl) compounds;
Preferably, the bis (vinylphenyl) compound is bis (vinylphenyl) ethane;
preferably, the bis (vinylphenyl) ethane is selected from any one of the compounds of the structures of the following formula (9), formula (10) or formula (11):
4. A resin composition according to any one of claims 1 to 3, wherein the polyphenylene ether resin is 5 to 95 parts by weight and the bis (vinyl phenyl) compound is 5 to 95 parts by weight based on 100 parts by weight of the total amount of resin components in the resin composition.
5. The resin composition according to any one of claims 1 to 4, wherein the resin composition further comprises a crosslinking agent;
Preferably, the crosslinking agent is a compound containing a styrene-reactive group, and may be any one or a combination of at least two of a polyfunctional vinyl aromatic copolymer, divinylbenzene, divinylbiphenyl, divinylnaphthalene, t-butylstyrene, bis (vinylbenzyl) ether, trivinylbenzene, trivinylbiphenyl, 1,2, 4-trivinylcyclohexane, and the like;
the crosslinking agent is used in an amount of 1 to 90 parts by weight based on 100 parts by weight of the total amount of the resin components in the resin composition;
Preferably, the resin composition further comprises an initiator, preferably, the initiator is selected from one or a combination of at least two of dicumyl peroxide, t-butyl peroxybenzoate, 2, 5-bis (2-ethylhexanoylperoxy) -2, 5-dimethylhexane, di- (t-butylperoxyisopropyl) benzene, peroxy (2, 4-dichlorobenzoyl), 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane, peroxy-2-ethylhexyl carbonate, 2, 5-dimethyl-2, 5-bis (t-butylperoxy) -3-hexyne, 4-bis (t-butylperoxy) butyl valerate, 1-bis (t-butylperoxy) -3, 5-trimethylcyclohexane, 3,5, 7-pentamethyl-1, 2, 4-trioxepane, di-t-butyl peroxide or t-butylperoxyisopropyl;
Preferably, the initiator is used in an amount of 0 to 3 parts by weight based on 100 parts by weight of the total amount of the resin components in the resin composition;
Preferably, the resin composition further comprises a filler comprising an organic filler and/or an inorganic filler;
Preferably, the inorganic filler is selected from one or a combination of at least two of crystalline silica, fused silica, spherical silica, hollow silica, glass frit, aluminum nitride, boron nitride, silicon carbide, silicon aluminum carbide, aluminum hydroxide, magnesium hydroxide, titanium dioxide, strontium titanate, barium titanate, zinc oxide, zirconium oxide, aluminum oxide, beryllium oxide, magnesium oxide, barium sulfate, talc, clay, calcium silicate, calcium carbonate, or mica;
Preferably, the organic filler is selected from one or a combination of at least two of polytetrafluoroethylene powder, polyphenylene sulfide, polyetherimide, polyphenylene oxide or polyethersulfone powder;
Preferably, the filler is used in an amount of 5 to 400 parts by weight based on 100 parts by weight of the total amount of the resin components in the resin composition;
preferably, the resin composition further includes a flame retardant, which may be a bromine-containing flame retardant or a halogen-free flame retardant;
Preferably, the flame retardant is used in an amount of 5 to 80 parts by weight based on 100 parts by weight of the total amount of the resin components in the resin composition;
Preferably, the resin composition further comprises other additives, which are one or a combination of at least two of antioxidants, heat stabilizers, light stabilizers, plasticizers, lubricants, flow modifiers, drip retardants, antiblocking agents, antistatic agents, flow promoters, processing aids, substrate adhesives, mold release agents, toughening agents, low shrinkage additives, or stress relief additives;
Preferably, the other additives are used in an amount of preferably 0.1 to 10 parts by weight based on 100 parts by weight of the total amount of the resin components in the resin composition.
6. A resin emulsion obtained by dissolving or dispersing the resin composition according to any one of claims 1 to 5 in a solvent.
7. A prepreg comprising a substrate and the thermosetting resin composition according to any one of claims 1 to 5 attached to the substrate after impregnation drying.
8. A laminate comprising at least one prepreg according to claim 7.
9. A metal foil-clad laminate comprising one or at least two laminated prepregs according to claim 7 and a metal foil on one or both sides of the laminated prepregs.
10. A high frequency, high speed circuit substrate comprising one or at least two superimposed prepregs according to claim 7.
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN118271535A true CN118271535A (en) | 2024-07-02 |
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