CN112080102A - Resin composition, prepreg, insulating film, metal-clad laminate, and printed wiring board provided with same - Google Patents
Resin composition, prepreg, insulating film, metal-clad laminate, and printed wiring board provided with same Download PDFInfo
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- CN112080102A CN112080102A CN201910511365.3A CN201910511365A CN112080102A CN 112080102 A CN112080102 A CN 112080102A CN 201910511365 A CN201910511365 A CN 201910511365A CN 112080102 A CN112080102 A CN 112080102A
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- Prior art keywords
- resin
- parts
- resin composition
- epoxy resin
- weight
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims abstract description 81
- -1 ester compound Chemical class 0.000 claims abstract description 86
- 229920005989 resin Polymers 0.000 claims abstract description 80
- 239000011347 resin Substances 0.000 claims abstract description 80
- 239000003822 epoxy resin Substances 0.000 claims abstract description 72
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 72
- 229910052751 metal Inorganic materials 0.000 claims abstract description 29
- 239000002184 metal Substances 0.000 claims abstract description 29
- 150000002148 esters Chemical class 0.000 claims abstract description 22
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims abstract description 19
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 claims abstract description 11
- 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 38
- 239000003063 flame retardant Substances 0.000 claims description 38
- 239000004643 cyanate ester Substances 0.000 claims description 32
- 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 claims description 26
- 229910052739 hydrogen Inorganic materials 0.000 claims description 25
- 239000001257 hydrogen Substances 0.000 claims description 25
- 125000003118 aryl group Chemical group 0.000 claims description 23
- 239000003999 initiator Substances 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 22
- 229920003192 poly(bis maleimide) Polymers 0.000 claims description 22
- 239000005011 phenolic resin Substances 0.000 claims description 19
- 125000001624 naphthyl group Chemical group 0.000 claims description 18
- 150000002431 hydrogen Chemical class 0.000 claims description 17
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 16
- 239000011574 phosphorus Substances 0.000 claims description 16
- 229910052698 phosphorus Inorganic materials 0.000 claims description 16
- 239000000945 filler Substances 0.000 claims description 15
- 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 claims description 14
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 14
- 239000004843 novolac epoxy resin Substances 0.000 claims description 14
- 239000011888 foil Substances 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 239000012779 reinforcing material Substances 0.000 claims description 10
- 239000012752 auxiliary agent Substances 0.000 claims description 9
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 9
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 239000007822 coupling agent Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 239000004305 biphenyl Substances 0.000 claims description 7
- 235000010290 biphenyl Nutrition 0.000 claims description 7
- 239000011256 inorganic filler Substances 0.000 claims description 7
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 7
- 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 claims description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 6
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 6
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 6
- IZSHZLKNFQAAKX-UHFFFAOYSA-N 5-cyclopenta-2,4-dien-1-ylcyclopenta-1,3-diene Chemical group C1=CC=CC1C1C=CC=C1 IZSHZLKNFQAAKX-UHFFFAOYSA-N 0.000 claims description 6
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 6
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 150000004767 nitrides Chemical class 0.000 claims description 6
- 229910052755 nonmetal Inorganic materials 0.000 claims description 6
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 6
- 239000012766 organic filler Substances 0.000 claims description 6
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 6
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims description 5
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 claims description 5
- RIAHASMJDOMQER-UHFFFAOYSA-N 5-ethyl-2-methyl-1h-imidazole Chemical compound CCC1=CN=C(C)N1 RIAHASMJDOMQER-UHFFFAOYSA-N 0.000 claims description 5
- 239000002270 dispersing agent Substances 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 4
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 4
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 claims description 4
- 239000012796 inorganic flame retardant Substances 0.000 claims description 4
- KNDQHSIWLOJIGP-UMRXKNAASA-N (3ar,4s,7r,7as)-rel-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione Chemical compound O=C1OC(=O)[C@@H]2[C@H]1[C@]1([H])C=C[C@@]2([H])C1 KNDQHSIWLOJIGP-UMRXKNAASA-N 0.000 claims description 3
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims description 3
- KGSFMPRFQVLGTJ-UHFFFAOYSA-N 1,1,2-triphenylethylbenzene Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 KGSFMPRFQVLGTJ-UHFFFAOYSA-N 0.000 claims description 3
- KHVOZEHHEARTGS-UHFFFAOYSA-N 1,3-dioxoisoindole-4,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C2C(=O)NC(=O)C2=C1C(O)=O KHVOZEHHEARTGS-UHFFFAOYSA-N 0.000 claims description 3
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- SFRDXVJWXWOTEW-UHFFFAOYSA-N 2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)CO SFRDXVJWXWOTEW-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims description 3
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 claims description 3
- PBEHQFUSQJKBAS-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol;phenol Chemical compound OC1=CC=CC=C1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 PBEHQFUSQJKBAS-UHFFFAOYSA-N 0.000 claims description 3
- PVFQHGDIOXNKIC-UHFFFAOYSA-N 4-[2-[3-[2-(4-hydroxyphenyl)propan-2-yl]phenyl]propan-2-yl]phenol Chemical compound C=1C=CC(C(C)(C)C=2C=CC(O)=CC=2)=CC=1C(C)(C)C1=CC=C(O)C=C1 PVFQHGDIOXNKIC-UHFFFAOYSA-N 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 3
- 239000004695 Polyether sulfone Substances 0.000 claims description 3
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 3
- 229920000147 Styrene maleic anhydride Polymers 0.000 claims description 3
- 150000008065 acid anhydrides Chemical class 0.000 claims description 3
- 125000002723 alicyclic group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 3
- 239000004842 bisphenol F epoxy resin Substances 0.000 claims description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 3
- 229930003836 cresol Natural products 0.000 claims description 3
- BLCKNMAZFRMCJJ-UHFFFAOYSA-N cyclohexyl cyclohexyloxycarbonyloxy carbonate Chemical compound C1CCCCC1OC(=O)OOC(=O)OC1CCCCC1 BLCKNMAZFRMCJJ-UHFFFAOYSA-N 0.000 claims description 3
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 3
- 239000004845 glycidylamine epoxy resin Substances 0.000 claims description 3
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims description 3
- 239000012948 isocyanate Substances 0.000 claims description 3
- 150000002513 isocyanates Chemical class 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- VSWALKINGSNVAR-UHFFFAOYSA-N naphthalen-1-ol;phenol Chemical compound OC1=CC=CC=C1.C1=CC=C2C(O)=CC=CC2=C1 VSWALKINGSNVAR-UHFFFAOYSA-N 0.000 claims description 3
- 150000002989 phenols Chemical class 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 229920006393 polyether sulfone Polymers 0.000 claims description 3
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 3
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 3
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 claims description 3
- JRQJLSWAMYZFGP-UHFFFAOYSA-N 1,1'-biphenyl;phenol Chemical compound OC1=CC=CC=C1.C1=CC=CC=C1C1=CC=CC=C1 JRQJLSWAMYZFGP-UHFFFAOYSA-N 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- ADJMNWKZSCQHPS-UHFFFAOYSA-L zinc;6-methylheptanoate Chemical compound [Zn+2].CC(C)CCCCC([O-])=O.CC(C)CCCCC([O-])=O ADJMNWKZSCQHPS-UHFFFAOYSA-L 0.000 claims description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 abstract description 19
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 8
- 125000004185 ester group Chemical group 0.000 abstract description 6
- 238000004132 cross linking Methods 0.000 abstract description 5
- 239000011203 carbon fibre reinforced carbon Substances 0.000 abstract description 4
- 238000010526 radical polymerization reaction Methods 0.000 abstract description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 abstract description 4
- 229920002554 vinyl polymer Polymers 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 description 12
- 239000004744 fabric Substances 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000003292 glue Substances 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 230000006872 improvement Effects 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- JESXATFQYMPTNL-UHFFFAOYSA-N 2-ethenylphenol Chemical compound OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 7
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000003825 pressing Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 229920001187 thermosetting polymer Polymers 0.000 description 6
- 239000006087 Silane Coupling Agent Substances 0.000 description 5
- 239000000975 dye Substances 0.000 description 5
- 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 5
- 238000010438 heat treatment Methods 0.000 description 5
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N benzene-dicarboxylic acid Natural products OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 229920001568 phenolic resin Polymers 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-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
- 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
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 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
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
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- 239000011248 coating agent Substances 0.000 description 2
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- 238000011156 evaluation Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000007850 fluorescent dye Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
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- 230000008569 process Effects 0.000 description 2
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- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-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
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-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
- FWLHAQYOFMQTHQ-UHFFFAOYSA-N 2-N-[8-[[8-(4-aminoanilino)-10-phenylphenazin-10-ium-2-yl]amino]-10-phenylphenazin-10-ium-2-yl]-8-N,10-diphenylphenazin-10-ium-2,8-diamine hydroxy-oxido-dioxochromium Chemical compound O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.Nc1ccc(Nc2ccc3nc4ccc(Nc5ccc6nc7ccc(Nc8ccc9nc%10ccc(Nc%11ccccc%11)cc%10[n+](-c%10ccccc%10)c9c8)cc7[n+](-c7ccccc7)c6c5)cc4[n+](-c4ccccc4)c3c2)cc1 FWLHAQYOFMQTHQ-UHFFFAOYSA-N 0.000 description 1
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 description 1
- YNGIFMKMDRDNBQ-UHFFFAOYSA-N 3-ethenylphenol Chemical compound OC1=CC=CC(C=C)=C1 YNGIFMKMDRDNBQ-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 1
- QRFTXHFUNIFHST-UHFFFAOYSA-N 4,5,6,7-tetrabromoisoindole-1,3-dione Chemical compound BrC1=C(Br)C(Br)=C2C(=O)NC(=O)C2=C1Br QRFTXHFUNIFHST-UHFFFAOYSA-N 0.000 description 1
- WOCGGVRGNIEDSZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical compound C=1C=C(O)C(CC=C)=CC=1C(C)(C)C1=CC=C(O)C(CC=C)=C1 WOCGGVRGNIEDSZ-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
- 229910052582 BN Inorganic materials 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- YBUPZEKLPLIZNR-UHFFFAOYSA-N C.C(C)C=1C=CC=C(C1N1C(C=CC1=O)=O)C.C(C)C=1C=CC=C(C1N1C(C=CC1=O)=O)C Chemical compound C.C(C)C=1C=CC=C(C1N1C(C=CC1=O)=O)C.C(C)C=1C=CC=C(C1N1C(C=CC1=O)=O)C YBUPZEKLPLIZNR-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910000684 Cobalt-chrome Inorganic materials 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000004480 active ingredient Substances 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
- 125000003277 amino group Chemical group 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 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
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000010952 cobalt-chrome Substances 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
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate group Chemical group [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 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
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000005516 engineering process Methods 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
- 239000012467 final product Substances 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical group O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 1
- 150000003949 imides Chemical group 0.000 description 1
- 238000010030 laminating Methods 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
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 150000003071 polychlorinated biphenyls Chemical class 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 125000002755 pyrazolinyl group Chemical group 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000008054 signal transmission Effects 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
- 238000002791 soaking Methods 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 1
- 230000008646 thermal stress 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
Classifications
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/092—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising epoxy resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2479/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The invention provides an active ester compound, a resin composition, a prepreg, an insulating film, a metal foil-clad laminate and a printed wiring board with the active ester compound and the resin composition. The active ester compound is an active ester compound containing two reactive groups, wherein the active ester group does not generate hydroxyl with stronger polarity when reacting with epoxy resin, so that the low dielectric constant and low dielectric loss are obtained after reaction, simultaneously, the terminal carbon-carbon double bond and maleimide group generate free radical polymerization reaction, the dielectric constant and dielectric loss of a cured product are further reduced, the toughness problem of the maleimide resin is well improved, the crosslinking density of the cured product is improved through the reaction of the active ester and the epoxy resin and the reaction of the maleimide group and vinyl, and finally, the cured product which simultaneously meets the requirements of high heat resistance, high modulus, low dielectric constant, low dielectric loss, low CTE and low warpage is obtained.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a resin composition with high heat resistance, high modulus, low dielectric constant, low dielectric loss and low warpage, a prepreg, an insulating film, a metal foil-clad laminated board and a printed circuit board with the resin composition.
Background
With the upgrading of technologies, new requirements are put on PCBs in the consumer electronics markets such as automobile markets and smart phones, and after the 5G commercial market appears in 2018, the requirements on the dielectric property of PCB base materials are further stepped, and the high-frequency high-speed copper-clad plate is one of indispensable electronic base materials in the 5G era. In short, the PCB substrate material needs to have a low dielectric constant and dielectric loss tangent to reduce the delay, distortion and loss of signals during high-speed transmission and the interference between signals. Accordingly, it is desirable to provide a thermosetting resin composition which can exhibit a sufficiently low dielectric constant and a sufficiently low dielectric loss tangent in a signal transmission process of high speed and high frequency, in a printed circuit board material produced using the thermosetting resin composition.
In the prior art, materials prepared from thermosetting resin compositions taking epoxy resin and curing agent thereof as essential components have the advantages of good heat resistance, insulativity, processability, low cost and the like, so the thermosetting resin compositions are widely applied to electronic materials such as semiconductors, printed circuit boards and the like. The curing agent commonly used for epoxy resins includes polyamine, acid anhydride, phenolic resin, etc. Curing agents containing active hydrogen in their molecular structure, such as amines and phenolic resins, have a large number of hydroxyl groups in the cured epoxy resin, which results in an increase in the water absorption of the cured product and a decrease in the wet heat resistance and dielectric properties. To solve the above problems occurring when the conventional curing agents cure epoxy resins, active esters have been found to be a promising curing agent for epoxy resins. The active ester can react with the epoxy resin under a mild condition; meanwhile, the epoxy resin cured by the active ester does not contain hydroxyl and replaces ester group, and an epoxy resin cured product with excellent moisture and heat resistance and dielectric property can be obtained. Japanese patent laid-open Nos. JP2002012650A, JP2003082063A, JP2004155990A, JP2009235165A and JP2012246367A disclose active ester resins which are used as curing agents for epoxy resins to suitably reduce the dielectric constant and dielectric loss of cured epoxy resins, and generally the dielectric constant is 2.8 to 3.3 and the dielectric loss is 0.002 to 0.005. However, in the case of producing a high-performance substrate for high frequency and high speed, in order to improve heat resistance, thermal expansion coefficient or flame retardancy, other components such as bismaleimide resin, benzoxazine resin or phosphorus-containing flame retardant are added to the resin composition, and thus the dielectric constant of the finally obtained substrate material still fails to satisfy the requirements of the high-frequency and high-speed substrate.
On the other hand, among the existing resin materials for manufacturing printed circuit boards, bismaleimide is one of the excellent resins, and is a thermosetting resin containing an imide structure, and the high crosslinking density after curing makes the resin have high glass transition temperature, excellent thermal stability and higher rigidity, and is one of the first materials for manufacturing thin substrates at present. However, the cured bismaleimide resin has a great brittleness, and the improvement of the warpage of the sheet material is insufficient, so that the application of the bismaleimide resin to high-performance sheet materials such as thin package substrates is limited.
In view of the above, it is desirable to provide a novel resin composition, and a prepreg, an insulating film, a metal-clad laminate, and a printed wiring board having the same to solve the above problems.
Disclosure of Invention
An object of the present invention is to provide a resin composition having high heat resistance, high modulus, low dielectric constant, low dielectric loss, low CTE and low warpage, and a prepreg, an insulating film, a metal-clad laminate, and a printed wiring board prepared using the same.
In order to achieve the purpose, the invention adopts the following technical scheme:
a resin composition comprising, by weight:
(A) epoxy resin: 5-80 parts;
(B) maleimide resin: 1-100 parts;
(C) curing agent: 1-100 parts;
the curing agent at least comprises an active ester compound shown as a structural formula (1)
Structural formula (1)
Wherein R is1Represents hydrogen or C1-C5 alkyl, m is an integer from 1 to 10, A is one of the following groups:
wherein R is10、R11、R12、R13Are respectively selected from hydrogen, alkyl of C1-C5, or aryl or aralkyl of C6-C10.
Further, A in the active ester compound shown in the structural formula (1) contains dicyclopentadienyl, tricyclopentadienyl or naphthyl;
and/or said R1 is hydrogen, methyl, ethyl, propyl, tert-butyl or pentyl;
and/or, said R10、R11、R12、R13Each independently selected from hydrogen, methyl, ethyl, propyl, tert-butyl, pentyl, phenyl, biphenyl or naphthyl;
further, R1 is hydrogen, m is 1, a is biscyclopentadienyl;
or, R1 is hydrogen, m is 1, and A is naphthyl.
Further, the mass percentage content of the active ester compound shown as the structural formula (1) in the curing agent is 1-100%, and preferably 5-50%;
or the curing agent also contains at least one of cyanate ester, amine compound, amide compound, anhydride compound, phenol compound and active ester compound different from the structural formula (1);
preferably, the cyanate ester is selected from bisphenol a type cyanate ester, bisphenol E type cyanate ester, novalac type cyanate ester, phenolic type cyanate ester, bisphenol F type cyanate ester, bisphenol M type cyanate ester, or bisphenol S type cyanate ester;
preferably, the amine-based compound is selected from diaminodiphenylmethane, diaminodiphenylsulfone, diethylenetriamine, dicarboxyphthalimide or imidazole;
preferably, the amide-based compound is selected from dicyandiamide or a low-molecular polyamide;
preferably, the acid anhydride-based compound is selected from phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, maleic anhydride, hydrogenated phthalic anhydride, nadic anhydride, or styrene-maleic anhydride;
preferably, the phenolic compound is selected from bisphenol a phenol resin, phenol resin, naphthol phenol resin, biphenyl phenol type naphthol resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin, naphthol aralkyl resin or trimethylolmethane resin;
preferably, the active ester compound different from formula (1) is selected from compounds represented by formula (7):
structural formula (7)
Wherein, X is phenyl or naphthyl; j is 0 or 1; k is 0 or 1; n represents a repeating unit and is 0.25 to 1.25.
Further, the resin composition includes, by weight: (A) epoxy resin: 5-80 parts;
(B) maleimide resin: 1-100 parts;
(C) an active ester according to structural formula (1): 1-60 parts;
(D) cyanate ester: 0.5-40 parts.
Further, the epoxy resin is selected from one or more of bisphenol a epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol E epoxy resin, phosphorus epoxy resin, nitrogen epoxy resin, o-cresol novolac epoxy resin, bisphenol a novolac epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, triphenylmethane epoxy resin, tetraphenylethane epoxy resin, biphenyl epoxy resin, naphthalene ring epoxy resin, dicyclopentadiene epoxy resin, isocyanate epoxy resin, aralkyl novolac epoxy resin, alicyclic epoxy resin, glycidylamine epoxy resin, glycidylether epoxy resin, and glycidylester epoxy resin;
and/or the maleimide resin is selected from bismaleimide resin, polymaleimide resin or maleimide resin modified prepolymer;
preferably, the bismaleimide resin is an aromatic type bismaleimide or an aliphatic type bismaleimide resin;
preferably, the polymaleimide resin contains at least 3 maleimide groups in the molecular structure, and further, the polymaleimide resin is shown in the following structure:
wherein n is1Is an integer of 2 to 10, R5Is hydrogen or methyl;
the modified prepolymer of the maleimide resin is allyl modified maleimide resin prepolymer or amino modified maleimide resin prepolymer.
Further, the resin composition further includes a filler,
preferably, the filler is an organic filler or an inorganic filler; further, the inorganic filler is selected from one or a mixture of at least any two of non-metal oxide, metal nitride, non-metal nitride, inorganic hydrate, inorganic salt, metal hydrate and inorganic phosphorus; the organic filler is selected from at least one of polytetrafluoroethylene powder, polyphenylene sulfide and polyether sulfone powder;
preferably, the resin composition further includes 0 to 200 parts by weight, preferably 10 to 100 parts by weight, more preferably 30 to 70 parts by weight of a filler, based on 100 parts by weight of the resin composition;
and/or, the resin composition further comprises a curing accelerator;
preferably, the curing accelerator is at least one selected from the group consisting of 4-dimethylaminopyridine, 2-methylimidazole, 2-methyl-4-ethylimidazole, 2-phenylimidazole, and zinc isooctanoate,
preferably, the curing accelerator is contained in an amount of 0.001 to 5 parts by weight, preferably 0.01 to 1 part by weight, based on 100 parts by weight of the resin composition;
and/or, the resin composition further comprises an initiator;
preferably, the initiator is selected from azo-type initiators, peroxy-type initiators or redox-type initiators;
further, the initiator is selected from one or more of the following initiators: dicumyl peroxide, di-tert-butyl peroxide, tert-butyl peroxybenzoate, dicyclohexyl peroxydicarbonate, cumene hydroperoxide, and azobisisobutyronitrile;
preferably, the initiator is contained in an amount of 0.001 to 6 parts by weight, based on 100 parts by weight of the resin composition;
and/or, the resin composition further comprises a flame retardant;
preferably, the flame retardant is selected from at least one of a bromine-based flame retardant, a phosphorus-based flame retardant, a nitrogen-based flame retardant, an organosilicon flame retardant, an organic metal salt flame retardant or an inorganic flame retardant;
preferably, the content of the flame retardant is 1 to 80 parts by weight, preferably 5 to 50 parts by weight, based on 100 parts by weight of the resin composition;
and/or, the resin composition further comprises other auxiliary agents;
preferably, the other auxiliary agents comprise at least one of a coupling agent, a dispersing agent and a dye;
preferably, the content of the other auxiliary agent is 0 to 5 parts by weight based on 100 parts by weight of the resin composition.
A prepreg comprises a reinforcing material and a resin composition attached to the surface of the reinforcing material, wherein the resin composition is the resin composition.
An insulation film comprising a carrier film and a resin composition applied to a surface of the carrier film, wherein the resin composition is the resin composition described in any one of the above.
A metal foil-clad laminate comprises at least one prepreg as described above and a metal foil formed on at least one side of the prepreg.
A printed wiring board comprising at least one prepreg as described above, or at least one insulating film as described above.
Has the advantages that: the active ester compound is an active ester compound containing two reactive groups, wherein the active ester group does not generate hydroxyl with stronger polarity when reacting with epoxy resin, so that the low dielectric constant and low dielectric loss are obtained after the reaction, simultaneously, the terminal carbon-carbon double bond and maleimide group generate free radical polymerization reaction, the dielectric constant and the dielectric loss of a cured product are further reduced, simultaneously, the toughness problem of the maleimide resin is well improved, the crosslinking density of the cured product is improved through the reaction of the active ester and the epoxy resin and the reaction of the maleimide group and vinyl group, and finally, the cured product which simultaneously meets the requirements of high heat resistance, high modulus, low dielectric constant, low dielectric loss, low CTE and low warpage is obtained.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
While the following is a detailed description of the embodiments of the present invention, it should be noted that those skilled in the art can make various modifications and improvements without departing from the principle of the embodiments of the present invention, and such modifications and improvements are considered to be within the scope of the embodiments of the present invention.
The term "comprising" or "containing" in the present specification means that other components capable of imparting different characteristics to the resin composition may be contained in addition to the components.
"based on 100 parts by weight of the resin composition" in the present specification means that the total amount of components excluding the flame retardant, the filler, the catalyst, the auxiliary and the initiator is 100 parts by weight.
In order to achieve the purpose, the invention adopts the following technical scheme:
an active ester compound represented by the structural formula (1):
structural formula (1)
Wherein R is1Represents hydrogen or C1-C5 alkyl, m is an integer from 1 to 10, A is one of the following groups:
wherein R is10、R11、R12、R13Are respectively selected from hydrogen, alkyl of C1-C5, or aryl or aralkyl of C6-C10.
The active ester compound shown as the structural formula (1) can be used as an epoxy resin curing agent, and can specifically form a resin composition together with at least epoxy resin and maleimide resin. The active ester compound is an active ester compound containing two reactive groups, wherein the active ester group does not generate hydroxyl with stronger polarity when reacting with epoxy resin, so that the low dielectric constant and low dielectric loss are obtained after reaction, simultaneously, the terminal carbon-carbon double bond and maleimide group generate free radical polymerization reaction, the dielectric constant and dielectric loss of a cured product are further reduced, the toughness problem of the maleimide resin is well improved, the crosslinking density of the cured product is improved through the reaction of the active ester and the epoxy resin and the reaction of the maleimide group and vinyl, and finally, the cured product which simultaneously meets the requirements of high heat resistance, high modulus, low dielectric constant, low dielectric loss, low CTE and low warpage is obtained.
Preferably, said R is1May be hydrogen, methyl, ethyl, propyl, tert-butyl or pentyl, more preferably, said R1May be hydrogen or methyl.
Preferably, said R is10、R11、R12、R13Each independently selected from hydrogen, methyl, ethyl, propyl, tert-butyl or pentyl, or phenyl, biphenyl or naphthyl, more preferably hydrogen, methyl or phenyl, more preferably said R10、R11、R12、R13Each independently hydrogen, methyl or phenyl.
Preferably, a in the active ester compound represented by the structural formula (1) contains dicyclopentadienyl, tricyclopentadienyl or naphthyl.
For example, in said R1When the compound is hydrogen, m is 1, and A is dicyclopentadienyl, the active ester compound shown in the structural formula (1) is dicyclopentadiene active ester, and the structural formula is shown as follows:
for example, in said R1When the compound is hydrogen, m is 1, and A is naphthyl, the active ester compound shown in the structural formula (1) is naphthalene active ester, and the structural formula is shown as follows:
more preferably, the active ester compound is a dicyclopentadienyl-containing active ester represented by the structural formula (2).
The preparation method of the active ester compound shown as the structural formula (1) in the invention comprises the following steps: the aromatic phenolic resin, the aromatic dicarboxylic acid or the aromatic dicarboxylic acid halide compound and the vinyl phenol are reacted to obtain the aromatic phenolic resin, and the reaction molar ratio is as follows:
aromatic phenol resin: aromatic dicarboxylic acid or aromatic dicarboxylic acid halide compound 0.5-0.98;
aromatic phenol resin: 0.5-9.5 parts of vinylphenol;
the aromatic dicarboxylic acid halide compound is aromatic dicarboxylic acid chloride, aromatic dicarboxylic acid bromide or aromatic dicarboxylic acid fluoride, and preferably terephthalic acid dichloride.
The vinylphenol is p-vinylphenol, m-vinylphenol or o-vinylphenol, preferably p-vinylphenol.
The following is an example of the preparation of dicyclopentadiene active ester, the reaction mechanism of which is shown below:
alternatively, the active ester compound represented by the formula (1) in the present invention can also be prepared by the following method:
firstly, reacting aromatic phenol resin and aromatic dicarboxylic acid, and then adding p-vinylphenol to continuously react to obtain the active ester compound, wherein the following reaction mechanism is shown as follows by taking the preparation of dicyclopentadiene active ester as an example:
the first step is as follows:
the second step is that:
firstly, reacting aromatic phenol resin and aromatic diformyl chloride, and then adding p-vinylphenol to continuously react to obtain the active ester compound, wherein the following reaction mechanism is shown as follows by taking the preparation of dicyclopentadiene active ester as an example:
the first step is as follows:
the second step is that:
the aromatic dicarboxylic acid chloride can be replaced by other aromatic dicarboxylic acid halide compounds, and the reaction mechanism is the same as above, and is not described in detail herein.
Of course, the method is not limited thereto, and other methods can be used to prepare the active ester compound shown in formula (1), that is, all methods capable of preparing the active ester compound shown in formula (1) are within the scope of the present invention.
A resin composition comprising, by weight:
(A) epoxy resin: 5-80 parts;
(B) maleimide resin: 1-100 parts;
(C) curing agent: 1-100 parts;
the curing agent at least comprises an active ester compound shown as a structural formula (1).
As will be appreciated by those skilled in the art: "by weight" means calculated as the weight of active ingredient, or solids content, e.g., a solution of the resin, where weight refers to the solids content of the resin.
As a further improvement of the invention, the active ester content shown in the structural formula (1) can be adjusted according to the performance requirements of different degrees. The content of the active ester compound shown as the structural formula (1) in the curing agent is 1-100% (mass percentage). More preferably 5-50%; e.g. 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, (all inclusive), 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99% or 100%, and specific points between the foregoing, to the extent that space is limited and the invention is not intended to be exhaustive of the specific points included in the stated ranges, for brevity.
As a further preferred aspect of the present invention, the thermosetting resin composition comprises, by weight:
(A) epoxy resin: 20-60 parts;
(B) maleimide resin: 20-80 parts;
(C) curing agent: 1-100 parts;
the curing agent contains an active ester compound shown in a structural formula (1), and the specific structure and the category of the active ester compound are as described above.
As a further improvement of the present invention, the epoxy resin is selected from one or more of bisphenol a epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol E epoxy resin, phosphorus epoxy resin, nitrogen epoxy resin, o-cresol epoxy resin, bisphenol a novolac epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, triphenylmethane epoxy resin, tetraphenylethane epoxy resin, biphenyl epoxy resin, naphthalene ring epoxy resin, dicyclopentadiene epoxy resin, isocyanate epoxy resin, aralkyl novolac epoxy resin, alicyclic epoxy resin, glycidylamine epoxy resin, glycidylether epoxy resin, and glycidylether epoxy resin.
More preferably, the epoxy resin may be a naphthalene ring type epoxy resin having a structural formula shown in formula (4), a biphenyl type epoxy resin having a structural formula shown in formula (5), or a dicyclopentadiene type epoxy resin having a structural formula shown in formula (6):
wherein p is an integer of 1 to 10;
wherein n is an integer of 1 to 10;
wherein m is an integer of 1 to 10.
As a further improvement of the present invention, the maleimide resin is a bismaleimide resin or a polymaleimide resin or a modified prepolymer thereof. The bismaleimide resin is aromatic bismaleimide or aliphatic bismaleimide resin.
Preferably, the aromatic bismaleimide resin is represented by the following structural formula:
wherein R is1Selected from:
R2and R3Same or different, are respectively selected from H and H3C-or C2H5-。
In a further improvement of the present invention, the aromatic bismaleimide resin is preferably one or a mixture of more than one of 4,4 ' -diphenylmethane bismaleimide, 4 ' -diphenyl ether bismaleimide, 4 ' -diphenyl sulfone bismaleimide and bis (3-ethyl-5-methyl-4-maleimidobenzene) methane. The aromatic bismaleimide resin may be BMI-4000, BMI-2300, BMI-1000, BMI-5100, etc. obtained by curdling Japan, or BMI-70 obtained by curdling Japan.
Preferably, the aliphatic bismaleimide resin is at least one of the following structures:
wherein n is an integer of 1 to 10.
The polymaleimide resin at least contains 3 maleimide groups in a molecular structure, and is shown in the following structure:
wherein n is1Is an integer of 2 to 10, R5Is hydrogen or methyl.
The modified prepolymer of the maleimide resin is allyl modified maleimide resin prepolymer or amino modified maleimide resin prepolymer.
In a further improvement of the present invention, the curing agent further contains at least one of a cyanate ester, an amine compound, an amide compound, an acid anhydride compound, a phenol compound, and an active ester compound different from the formula (1). The content is 0 to 99 parts by weight, preferably 5 to 60 parts by weight, for example, 0 part by weight, 5 parts by weight, 10 parts by weight, 25 parts by weight, 35 parts by weight, 60 parts by weight, 70 parts by weight, 85 parts by weight, 99 parts by weight, and specific points between the above values, which are limited by space and in the interest of brevity, the present invention is not exhaustive and the range of the specific points included is not limited.
Specifically, the cyanate ester may be bisphenol a type cyanate ester, bisphenol E type cyanate ester, novalac type cyanate ester, phenol type cyanate ester, bisphenol F type cyanate ester, bisphenol M type cyanate ester, or bisphenol S type cyanate ester; the amine compound may be diaminodiphenylmethane, diaminodiphenylsulfone, diethylenetriamine, dicarboxyphthalimide, imidazole, etc., and diaminodiphenylmethane and diaminodiphenylsulfone are preferable; the amide compound may be dicyandiamide, low molecular polyamide, or the like, and is preferably dicyandiamide; the acid anhydride compound may be phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, maleic anhydride, hydrogenated phthalic anhydride, nadic anhydride, or the like, and is preferably styrene-maleic anhydride; the phenolic compound may be bisphenol a phenol resin, phenol resin, naphthol phenol resin, biphenol naphthol resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin, naphthol aralkyl resin, trimethylolmethane resin, or the like; the active ester compound different from the structural formula (1) may be selected from compounds represented by the structural formula (7):
wherein, X is phenyl or naphthyl; j is 0 or 1; k is 0 or 1; n represents a repeating unit and is 0.25 to 1.25.
Of course, it is understood that the active ester compound other than the active ester compound of formula (1) may be selected.
As a further preferred of the present invention, the resin composition comprises, by weight:
(A) epoxy resin: 5-80 parts;
(B) maleimide resin: 1-100 parts;
(C) an active ester according to structural formula (1): 1-60 parts;
(D) cyanate ester: 0.5 to 40 portions of
When (2) a cyanate ester is added to the resin composition, the following reaction occurs in the resin composition: reacting cyanate ester group with maleimide group; reacting cyanate group with epoxy group; the epoxy group reacts with the active ester group; fourthly, free radical polymerization reaction of maleimide group and carbon-carbon double bond in the active ester; therefore, the mutual reaction among the components can improve the crosslinking density of the cured product, the advantages and the disadvantages of the performances generated by the reactions are mutually complemented, and finally the final cured product with higher Tg, high modulus, high toughness, low dielectric constant, low dielectric loss, low CTE and high rigidity is obtained.
As a further improvement of the present invention, the resin composition further comprises a filler in an amount of 0 to 200 parts by weight based on 100 parts by weight of the resin composition, and it is understood that the resin composition may or may not contain the filler.
Preferably, the filler content is 10 to 100 parts by weight, more preferably 30 to 70 parts by weight, such as 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, 150 parts by weight, 160 parts by weight, 170 parts by weight, 180 parts by weight, 190 parts by weight or 200 parts by weight; and the particular points between the above numerical values, are not intended to be exhaustive or to be in a concise sense and the invention is not intended to be exhaustive of the particular points included in the range.
Specifically, the filler is an organic filler or an inorganic filler, wherein the inorganic filler is selected from one or a mixture of at least any two of non-metal oxide, metal nitride, non-metal nitride, inorganic hydrate, inorganic salt, metal hydrate or inorganic phosphorus; the organic filler is at least one selected from polytetrafluoroethylene powder, polyphenylene sulfide and polyether sulfone powder.
More preferably, the inorganic filler is at least one selected from the group consisting of fused silica, crystalline silica, spherical silica, hollow silica, aluminum hydroxide, alumina, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, mica, and glass fiber powder.
Preferably, the filler is silica, more preferably, surface-treated spherical silica.
Preferably, the filler has a median particle size of 1 to 15 μm, such as 1 μm, 2 μm, 5 μm, 8 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm or 15 μm, and specific values therebetween are not intended to be exhaustive, and for brevity, the invention is not intended to be limited to the specific values included in the ranges.
More preferably, the median value of the particle size of the filler is 1-10 μm.
Specifically, the surface treatment agent is a silane coupling agent, such as an epoxy silane coupling agent or an aminosilane coupling agent.
In the present invention, the resin composition further includes a curing accelerator.
Preferably, the curing accelerator is selected from at least one of 4-dimethylaminopyridine, 2-methylimidazole, 2-methyl-4-ethylimidazole, 2-phenylimidazole, and zinc isooctoate, for example: a mixture of 4-dimethylaminopyridine and 2-methylimidazole, a mixture of 2-methylimidazole and 2-methyl-4-ethylimidazole, a mixture of 2-phenylimidazole and zinc isooctoate, and a mixture of 2-methylimidazole, 2-methyl-4-ethylimidazole and 2-phenylimidazole, although not limited thereto.
The curing accelerator is contained in an amount of 0.001 to 5 parts by weight, for example, 0.001 part by weight, 0.01 part by weight, 1 part by weight, 2.5 parts by weight, 5 parts by weight, and specific points between the above-mentioned values, based on 100 parts by weight of the resin composition, are limited to space and in the interest of brevity, and the present invention is not exhaustive of the specific points included in the range.
More preferably, the curing accelerator is contained in an amount of 0.01 to 1 part by weight.
The resin composition may further include an initiator according to reactivity between resin components; the initiator is 0.001 to 6 parts by weight based on 100 parts by weight of the resin composition; the initiator can be selected from azo initiators, peroxy initiators and redox initiators, and preferably one or more of the following initiators: dicumyl peroxide, di-tert-butyl peroxide, tert-butyl peroxybenzoate, dicyclohexyl peroxydicarbonate, cumene hydroperoxide and azobisisobutyronitrile.
According to the present invention, the resin composition further comprises a flame retardant to improve the flame retardancy of a finally formed cured product, which can be understood as a prepreg, an insulating film, a metal foil-clad laminate, a printed wiring board, and the like.
Further, the content of the flame retardant is 1 to 80 parts by weight, for example, 1 part by weight, 5 parts by weight, 10 parts by weight, 20 parts by weight, 50 parts by weight, 70 parts by weight, 80 parts by weight, and specific points between the above values, which are limited by space and in the interest of brevity, the present invention is not exhaustive and does not list the specific points included in the range.
Preferably, the content of the flame retardant is 5 to 50 parts by weight.
Specifically, the flame retardant may be a bromine-based flame retardant, a phosphorus-based flame retardant, a nitrogen-based flame retardant, an organosilicon flame retardant, an organic metal salt flame retardant, an inorganic flame retardant, or the like. Wherein the bromine flame retardant can be decabromodiphenyl ether, decabromodiphenyl ethane, brominated styrene or tetrabromophthalimide. The phosphorus-containing flame retardant may be an inorganic phosphorus, a phosphate compound, a phosphonic acid compound, a phosphinic acid compound, a phosphine oxide compound, an organic phosphorus-containing compound such as 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2, 5-dihydroxyphenyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-phenyl-9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, tris (2, 6-dimethylphenyl) phosphine, phosphazene, or the like. The nitrogen-based flame retardant may be a triazine compound, a cyanuric acid compound, an isocyanic acid compound, phenothiazine, or the like. The organic silicon flame retardant can be organic silicon oil, organic silicon rubber, organic silicon resin and the like. The organometallic flame retardant may be ferrocene, acetylacetone metal complexes, organometallic carbonyl compounds, and the like. The inorganic flame retardant may be aluminum hydroxide, magnesium hydroxide, aluminum oxide, barium oxide, or the like.
Of course, the kind of the flame retardant is not limited thereto, it being understood that the flame retardant to be added may be selected according to the specific application field of the laminate, e.g. the application field requiring halogen, preferably a non-halogen flame retardant, such as a phosphorus or nitrogen containing flame retardant, more preferably phosphazene, DOPO or DOPO-HQ.
Preferably, when the phosphorus-containing flame retardant is selected, nitrogen and phosphorus are formed to be used for realizing synergistic flame retardance with nitrogen elements of the active ester compound in the curing agent, so that the flame retardant efficiency is improved.
According to different requirements of the final product, the resin composition further comprises other auxiliary agents, and preferably, the other auxiliary agents are 0-5 parts by weight based on 100 parts by weight of the resin composition.
The other auxiliary agents comprise a coupling agent, a dispersing agent and a dye. The coupling agent is a silane coupling agent, such as an epoxy silane coupling agent or an aminosilane coupling agent; the dispersant is amino silane compound having amino group and having hydrolytic group or hydroxyl group such as gamma-aminopropyltriethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane, epoxy silane compound having epoxy group and having hydrolytic group or hydroxyl group such as 3-acryloxypropyltrimethoxysilane, vinyl silane compound having vinyl group and having hydrolytic group or hydroxyl group such as gamma-methacryloxypropyltrimethoxysilane, and cationic silane coupling agent, and the dispersant can be Disperbyk-110, 111, 118, 180, 161, 2009, BYK-W996, W9010, W903 (all product names) manufactured by BYK; the dye is fluorescent dye and black dye, wherein the fluorescent dye is pyrazoline and the like, and the black dye is carbon black (liquid or powder), pyridine complex, azo complex, aniline black, black talcum powder, cobalt chromium metal oxide, azine, phthalocyanine and the like.
The preparation method of the resin composition is a conventional technical means in the field, and specifically comprises the following steps: taking a container, putting solid components in the container, adding a liquid organic solvent, stirring until the solid components are completely dissolved, adding liquid resin, a filler and a curing accelerator, continuously stirring uniformly, and finally adjusting the solid content of the liquid to 50-80% by using the solvent to prepare a glue solution, wherein the solid content is calculated by weight.
The organic solvent and the solvent used in the present invention are not particularly limited. For example, the organic solvent may be selected from one or a combination of any of acetone, butanone, toluene, methyl isobutyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, ethylene glycol methyl ether, propylene glycol methyl ether, benzene, toluene and cyclohexane.
The amount of the solvent to be added is selected by a person skilled in the art according to his own experience, as long as the viscosity of the resulting glue solution is such that it is suitable for use.
In order to achieve the above object, the present invention further provides a prepreg, which includes a reinforcing material, and the above resin composition attached to a surface of the reinforcing material.
The reinforcing material is natural fiber, organic synthetic fiber, organic fabric or inorganic fabric, and the inorganic fabric is preferably glass fiber cloth, and the glass fiber cloth is preferably open fiber cloth or flat cloth.
In addition, when the reinforcing material is a glass cloth, the glass cloth generally needs to be chemically treated to improve the interface between the resin composition and the glass cloth. The main method of the chemical treatment is a coupling agent treatment. The coupling agent used is preferably an epoxy silane, an aminosilane or the like to provide good water resistance and heat resistance.
The preparation method of the prepreg comprises the following steps: and (3) soaking the reinforcing material in the resin composition glue solution, then baking the soaked reinforcing material for 1-10min at the temperature of 50-170 ℃, and drying to obtain the prepreg.
In order to achieve the above object, the present invention further provides an insulation film comprising a carrier film and the above resin composition coated on the surface of the carrier film.
The preparation method of the insulating film comprises the following steps: and adding the resin composition into a solvent, dissolving to prepare a glue solution, coating the glue solution on a carrier film, heating and drying the carrier film coated with the glue solution, and forming an insulating resin layer by using the glue solution to obtain the insulating film.
The solvent is selected from one or more of acetone, butanone, toluene, methyl isobutyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, ethylene glycol methyl ether and propylene glycol methyl ether.
The carrier film may be a polyethylene terephthalate (PET) film, a release film, a copper foil, an aluminum foil, or the like, and is preferably a PET film.
The above-mentioned heating and drying conditions are baking at 50-170 deg.C for 1-10min, but not limited thereto.
Further, the side of the insulating resin layer facing away from the carrier film is covered with a protective film to protect the insulating resin layer.
Specifically, the material of the protective film is the same as that of the carrier film, but of course, the material is not limited thereto.
In order to achieve the above object, the present invention further provides a metal-clad laminate including at least one prepreg as described above and a metal foil formed on at least one side of the prepreg.
The metal foil-clad laminate is formed by bonding one or two prepregs by heating and pressing to form a laminate, and then bonding a metal foil on one side or both sides of the laminate by heating and pressing.
The preparation steps of the metal foil-clad laminate are as follows: and covering a metal foil on one or two sides of one prepreg, or covering a metal foil on one or two sides of at least 2 prepregs after laminating, and performing hot press forming to obtain the metal foil laminated board.
The pressing conditions of the metal foil and the laminated board are that the metal foil and the laminated board are pressed for 2-4 hours under the pressure of 0.2-2 MPa and the temperature of 180-250 ℃.
Specifically, the number of prepregs may be determined according to the thickness of a desired laminate, and one or more prepregs may be used.
The metal foil can be copper foil or aluminum foil, and the material is not limited; the thickness of the metal foil is also not particularly limited, and may be, for example, 5 μm, 8 μm, 12 μm, 18 μm, 35 μm or 70 μm.
In order to achieve the above object, the present invention further provides a printed wiring board, which includes at least one prepreg as described above, or at least one insulating film as described above.
The following examples are provided to further illustrate embodiments of the present invention. It is to be understood that the embodiments of the present invention are not limited to the following specific examples. The present invention can be modified as appropriate without changing the scope of the claims.
Synthesis example 1: synthesis of Dicyclopentadienyl active ester Compounds
Taking dicyclopentadiene phenol resin and benzene dicarboxylic acid, stirring and dissolving the dicyclopentadiene phenol resin and the benzene dicarboxylic acid uniformly in a toluene solvent, introducing nitrogen at the same time at the temperature of 60 ℃, adding a tetrabutylammonium bromide catalyst, then slowly dropping a 20% sodium hydroxide aqueous solution, reacting for 4 hours, then adding p-vinylphenol, continuing to react for 1 hour, washing for a plurality of times after the reaction is finished, and drying for 3 hours under the vacuum condition of 80 ℃ to obtain the dicyclopentadiene active ester compound marked as active ester A.
Synthesis example 2: synthesis of naphthyl active ester Compound
Taking naphthol resin and benzenedicarboxylic acid, stirring and dissolving the naphthol resin and the benzenedicarboxylic acid uniformly in a toluene solvent, introducing nitrogen at the same time at the temperature of 60 ℃, adding a tetrabutylammonium bromide catalyst, slowly dropping a 20% sodium hydroxide aqueous solution, reacting for 4 hours, adding p-vinylphenol, continuing to react for 1 hour, washing for a plurality of times after the reaction is finished, and drying for 3 hours under the vacuum condition of 80 ℃ to obtain the naphthyl active ester compound, which is marked as active ester B.
The components and contents of the resin compositions of examples 1 to 7 and comparative examples 1 to 2 are shown in the following table 1:
TABLE 1
The detailed specification of the components is as follows:
TABLE 2
The preparation method of the allyl modified bismaleimide prepolymer comprises the following steps: adding 100 parts of solvent N, N-dimethylformamide into a 500mL three-neck flask, sequentially adding 4, 4' -diphenylmethane bismaleimide and diallyl bisphenol A into the three-neck flask according to the mass part of 100:60, continuously stirring under the condition of an oil bath at 110 ℃, timing after the solid in the flask is completely dissolved, continuously stirring for 1hr, and distilling the obtained product to obtain a modified bismaleimide prepolymer with the solid content of 75%.
Example (b):
according to the component content in the table 1, the components and a proper amount of butanone solvent are stirred and mixed uniformly to obtain a glue solution with the solid content of 65 weight percent.
The glue solution is soaked and coated on E glass fiber cloth (7628), and is dried in an oven at 160 ℃ for 5min to prepare a prepreg.
And coating the glue solution on a PET carrier, and drying in a 160 ℃ oven for 5min to obtain the insulating film.
Preparation of performance evaluation sample laminates:
and (3) placing 18-micron metal copper foils on the upper prepreg and the lower prepreg respectively, and placing the prepregs in a vacuum hot press for pressing to obtain the laminated board a. The specific pressing process is pressing for 2 hours under the pressure of 1.5Mpa and the temperature of 220 ℃.
The performance evaluation method comprises the following steps:
(1) glass transition temperature Tg (. degree. C.): according to differential scanning calorimetry, the measurement was carried out by the DSC method specified by IPC-TM-6502.4.25.
(2) Dielectric constant: the dielectric constant at 1GHz was measured with the laminate a by the IPC-TM-6502.5.5.9 plate method.
(3) Dielectric loss tangent: the dielectric loss factor at 1GHz was measured with laminate a using the plate method according to IPC-TM-6502.5.5.9.
(4) E' modulus: the modulus values at 50 ℃ and 260 ℃ were determined in GPa at a heating rate of 10 ℃/min and a frequency of 10Hz, determined by DMA.
(5) Coefficient of thermal expansion (X/Y) direction: adopting a TA instrument TMA to measure, wherein the temperature rise rate is 10 ℃/min from 30-350 ℃, and the linear expansion coefficient in the surface direction of 50-130 ℃ is measured, and the measurement directions are the transverse direction (X) and the longitudinal direction (Y) of the glass cloth surface, and the unit is X/Y ppm/DEG C.
(6) Peel strength: the peel strength of the metal cap was tested according to the "post thermal stress" experimental conditions in the IPC-TM-650 method.
The laminate properties obtained are shown in table 3.
TABLE 3
As can be seen from the above examples, the examples of the active ester of the present invention can obtain lower dielectric constant and low dielectric loss, and simultaneously have excellent Tg value, high temperature modulus and modulus retention rate, and low thermal expansion coefficient. In particular, example 1 had much lower values of dielectric constant and dielectric loss than comparative example 1 (prior art active ester), while the heat resistance and modulus values were also significantly improved.
It should be understood that although the present description refers to embodiments, not every embodiment contains only a single technical solution, and such description is for clarity only, and those skilled in the art should make the description as a whole, and the technical solutions in the embodiments can also be combined appropriately to form other embodiments understood by those skilled in the art.
The above list of details is only for the concrete description of the feasible embodiments of the present application, they are not intended to limit the scope of the present application, and all equivalent embodiments or modifications that do not depart from the technical spirit of the present application are intended to be included within the scope of the present application.
Claims (10)
1. A resin composition characterized by comprising, by weight:
(A) epoxy resin: 5-80 parts;
(B) maleimide resin: 1-100 parts;
(C) curing agent: 1-100 parts;
the curing agent at least comprises an active ester compound shown as a structural formula (1)
Structural formula (1)
Wherein R is1Represents hydrogen or C1-C5 alkyl, m is an integer from 1 to 10, A is one of the following groups:
wherein R is10、R11、R12、R13Are respectively selected from hydrogen, alkyl of C1-C5, or aryl or aralkyl of C6-C10.
2. The resin composition of claim 1, wherein: a in the active ester compound shown in the structural formula (1) contains dicyclopentadienyl, tricyclopentadienyl or naphthyl;
and/or said R1 is hydrogen, methyl, ethyl, propyl, tert-butyl or pentyl;
and/or, said R10、R11、R12、R13Each independently selected from hydrogen, methyl, ethyl, propyl, tert-butyl, pentyl, phenyl, biphenyl or naphthyl;
further, R1 is hydrogen, m is 1, a is biscyclopentadienyl;
or, R1 is hydrogen, m is 1, and A is naphthyl.
3. The resin composition of claim 1, wherein:
the mass percentage content of the active ester compound shown as the structural formula (1) in the curing agent is 1-100%, preferably 5-50%;
or the curing agent also contains at least one of cyanate ester, amine compound, amide compound, anhydride compound, phenol compound and active ester compound different from the structural formula (1);
preferably, the cyanate ester is selected from bisphenol a type cyanate ester, bisphenol E type cyanate ester, novalac type cyanate ester, phenolic type cyanate ester, bisphenol F type cyanate ester, bisphenol M type cyanate ester, or bisphenol S type cyanate ester;
preferably, the amine-based compound is selected from diaminodiphenylmethane, diaminodiphenylsulfone, diethylenetriamine, dicarboxyphthalimide or imidazole;
preferably, the amide-based compound is selected from dicyandiamide or a low-molecular polyamide;
preferably, the acid anhydride-based compound is selected from phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, maleic anhydride, hydrogenated phthalic anhydride, nadic anhydride, or styrene-maleic anhydride;
preferably, the phenolic compound is selected from bisphenol a phenol resin, phenol resin, naphthol phenol resin, biphenyl phenol type naphthol resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin, naphthol aralkyl resin or trimethylolmethane resin;
preferably, the active ester compound different from formula (1) is selected from compounds represented by formula (7):
structural formula (7)
Wherein, X is phenyl or naphthyl; j is 0 or 1; k is 0 or 1; n represents a repeating unit and is 0.25 to 1.25.
4. The resin composition of claim 1, wherein: the resin composition comprises, by weight: (A) epoxy resin: 5-80 parts;
(B) maleimide resin: 1-100 parts;
(C) an active ester according to structural formula (1): 1-60 parts;
(D) cyanate ester: 0.5-40 parts.
5. The resin composition of claim 1, wherein:
the epoxy resin is selected from one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol E epoxy resin, phosphorus epoxy resin, nitrogen epoxy resin, o-cresol novolac epoxy resin, bisphenol A novolac epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, triphenylmethane epoxy resin, tetraphenylethane epoxy resin, biphenyl epoxy resin, naphthalene ring epoxy resin, dicyclopentadiene epoxy resin, isocyanate epoxy resin, aralkyl novolac epoxy resin, alicyclic epoxy resin, glycidylamine epoxy resin, glycidylether epoxy resin and glycidylester epoxy resin;
and/or the maleimide resin is selected from bismaleimide resin, polymaleimide resin or maleimide resin modified prepolymer;
preferably, the bismaleimide resin is an aromatic type bismaleimide or an aliphatic type bismaleimide resin;
preferably, the polymaleimide resin contains at least 3 maleimide groups in the molecular structure, and further, the polymaleimide resin is shown in the following structure:
wherein n is1Is an integer of 2 to 10, R5Is hydrogen or methyl;
the modified prepolymer of the maleimide resin is allyl modified maleimide resin prepolymer or amino modified maleimide resin prepolymer.
6. The resin composition according to claim 1,
the resin composition further comprises a filler,
preferably, the filler is an organic filler or an inorganic filler; further, the inorganic filler is selected from one or a mixture of at least any two of non-metal oxide, metal nitride, non-metal nitride, inorganic hydrate, inorganic salt, metal hydrate and inorganic phosphorus; the organic filler is selected from at least one of polytetrafluoroethylene powder, polyphenylene sulfide and polyether sulfone powder;
preferably, the resin composition further includes 0 to 200 parts by weight, preferably 10 to 100 parts by weight, more preferably 30 to 70 parts by weight of a filler, based on 100 parts by weight of the resin composition;
and/or, the resin composition further comprises a curing accelerator;
preferably, the curing accelerator is at least one selected from the group consisting of 4-dimethylaminopyridine, 2-methylimidazole, 2-methyl-4-ethylimidazole, 2-phenylimidazole, and zinc isooctanoate,
preferably, the curing accelerator is contained in an amount of 0.001 to 5 parts by weight, preferably 0.01 to 1 part by weight, based on 100 parts by weight of the resin composition;
and/or, the resin composition further comprises an initiator;
preferably, the initiator is selected from azo-type initiators, peroxy-type initiators or redox-type initiators;
further, the initiator is selected from one or more of the following initiators: dicumyl peroxide, di-tert-butyl peroxide, tert-butyl peroxybenzoate, dicyclohexyl peroxydicarbonate, cumene hydroperoxide, and azobisisobutyronitrile;
preferably, the initiator is contained in an amount of 0.001 to 6 parts by weight, based on 100 parts by weight of the resin composition;
and/or, the resin composition further comprises a flame retardant;
preferably, the flame retardant is selected from at least one of a bromine-based flame retardant, a phosphorus-based flame retardant, a nitrogen-based flame retardant, an organosilicon flame retardant, an organic metal salt flame retardant or an inorganic flame retardant;
preferably, the content of the flame retardant is 1 to 80 parts by weight, preferably 5 to 50 parts by weight, based on 100 parts by weight of the resin composition;
and/or, the resin composition further comprises other auxiliary agents;
preferably, the other auxiliary agents comprise at least one of a coupling agent, a dispersing agent and a dye;
preferably, the content of the other auxiliary agent is 0 to 5 parts by weight based on 100 parts by weight of the resin composition.
7. A prepreg characterized in that: the prepreg comprises a reinforcing material and a resin composition attached to the surface of the reinforcing material, wherein the resin composition is the resin composition in any one of claims 1 to 6.
8. An insulating film characterized in that: the insulation film comprises a carrier film and a resin composition coated on the surface of the carrier film, wherein the resin composition is the resin composition as claimed in any one of claims 1 to 6.
9. A metal-clad laminate characterized by: the metal-foil-clad laminate includes at least one prepreg according to claim 7, and a metal foil formed on at least one side of the prepreg.
10. A printed wiring board characterized in that: the printed wiring board comprises at least one prepreg according to claim 7, or at least one insulating film according to claim 8.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| WO2018235425A1 (en) * | 2017-06-21 | 2018-12-27 | Dic株式会社 | Active ester resin and composition and hardened substance using same |
-
2019
- 2019-06-13 CN CN201910511365.3A patent/CN112080102A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103342895A (en) * | 2013-07-29 | 2013-10-09 | 苏州生益科技有限公司 | Thermosetting resin composition as well as prepreg and laminated board manufactured by using same |
| WO2018235425A1 (en) * | 2017-06-21 | 2018-12-27 | Dic株式会社 | Active ester resin and composition and hardened substance using same |
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Application publication date: 20201215 |