CN109504087B - Resin composition, and prepreg and laminated board prepared from same - Google Patents
Resin composition, and prepreg and laminated board prepared from same Download PDFInfo
- Publication number
- CN109504087B CN109504087B CN201811435227.3A CN201811435227A CN109504087B CN 109504087 B CN109504087 B CN 109504087B CN 201811435227 A CN201811435227 A CN 201811435227A CN 109504087 B CN109504087 B CN 109504087B
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- Prior art keywords
- resin
- parts
- epoxy resin
- resin composition
- compound
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims abstract description 44
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical class O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 claims abstract description 82
- -1 allyl compound Chemical class 0.000 claims abstract description 82
- 229920005989 resin Polymers 0.000 claims abstract description 61
- 239000011347 resin Substances 0.000 claims abstract description 61
- 239000003822 epoxy resin Substances 0.000 claims abstract description 60
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 60
- 229920003192 poly(bis maleimide) Polymers 0.000 claims abstract description 36
- 239000007787 solid Substances 0.000 claims abstract description 31
- 239000002904 solvent Substances 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 238000011049 filling Methods 0.000 claims abstract description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims description 30
- 239000011574 phosphorus Substances 0.000 claims description 30
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 18
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 17
- 239000005011 phenolic resin Substances 0.000 claims description 17
- 239000004843 novolac epoxy resin Substances 0.000 claims description 16
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 239000011256 inorganic filler Substances 0.000 claims description 12
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 11
- 125000002947 alkylene group Chemical group 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 11
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 10
- 229920001568 phenolic resin Polymers 0.000 claims description 10
- 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 claims description 9
- 229920001971 elastomer Polymers 0.000 claims description 9
- 239000000806 elastomer Substances 0.000 claims description 9
- 239000000945 filler Substances 0.000 claims description 9
- 239000011888 foil Substances 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 7
- 239000012779 reinforcing material Substances 0.000 claims description 7
- 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 6
- 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 6
- 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 description 6
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 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
- 229920002857 polybutadiene Polymers 0.000 claims description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 6
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 239000004305 biphenyl Substances 0.000 claims description 5
- 235000010290 biphenyl Nutrition 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000003365 glass fiber Substances 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 239000005062 Polybutadiene Substances 0.000 claims description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 4
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 4
- 125000001624 naphthyl group Chemical group 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 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
- 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
- 239000004695 Polyether sulfone Substances 0.000 claims description 3
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 3
- 125000002723 alicyclic group Chemical group 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- 239000004842 bisphenol F epoxy resin Substances 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 229930003836 cresol Natural products 0.000 claims description 3
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 3
- 239000012948 isocyanate Substances 0.000 claims description 3
- 150000002513 isocyanates Chemical class 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 239000013034 phenoxy resin Substances 0.000 claims description 3
- 229920006287 phenoxy resin Polymers 0.000 claims description 3
- 150000004714 phosphonium salts Chemical class 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
- 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
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 229910052582 BN Inorganic materials 0.000 claims description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 229920000265 Polyparaphenylene Polymers 0.000 claims description 2
- 229920000147 Styrene maleic anhydride Polymers 0.000 claims description 2
- 150000008065 acid anhydrides Chemical class 0.000 claims description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 150000001412 amines Chemical group 0.000 claims description 2
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 2
- 229910002113 barium titanate Inorganic materials 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 239000000378 calcium silicate Substances 0.000 claims description 2
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 2
- 229910002026 crystalline silica Inorganic materials 0.000 claims description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 claims description 2
- 239000005350 fused silica glass Substances 0.000 claims description 2
- 239000004845 glycidylamine epoxy resin Substances 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 125000002524 organometallic group Chemical group 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920000768 polyamine Polymers 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 claims description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 2
- 229920001909 styrene-acrylic polymer Polymers 0.000 claims description 2
- 150000003440 styrenes Chemical class 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- 239000004568 cement Substances 0.000 claims 2
- 239000007788 liquid Substances 0.000 claims 2
- QIRNGVVZBINFMX-UHFFFAOYSA-N 2-allylphenol Chemical compound OC1=CC=CC=C1CC=C QIRNGVVZBINFMX-UHFFFAOYSA-N 0.000 claims 1
- CVSYQJLKYFKETF-UHFFFAOYSA-N C1(=CC=CC2=CC=CC=C12)O.C1(=CC=CC=C1)O.C1(=CC=CC=C1)C1=CC=CC=C1 Chemical compound C1(=CC=CC2=CC=CC=C12)O.C1(=CC=CC=C1)O.C1(=CC=CC=C1)C1=CC=CC=C1 CVSYQJLKYFKETF-UHFFFAOYSA-N 0.000 claims 1
- 238000007731 hot pressing Methods 0.000 claims 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims 1
- 150000002989 phenols Chemical class 0.000 claims 1
- 239000003063 flame retardant Substances 0.000 abstract description 27
- 239000000463 material Substances 0.000 abstract description 13
- 230000014759 maintenance of location Effects 0.000 abstract description 11
- 239000000758 substrate Substances 0.000 abstract description 9
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 abstract description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 39
- 238000003756 stirring Methods 0.000 description 22
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 20
- 239000000047 product Substances 0.000 description 20
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- 239000004744 fabric Substances 0.000 description 11
- 239000003921 oil Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000003292 glue Substances 0.000 description 8
- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical group C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000006872 improvement Effects 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000013067 intermediate product Substances 0.000 description 3
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical class CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 230000035882 stress Effects 0.000 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 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 239000000654 additive Substances 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
- 239000007822 coupling agent Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 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 description 1
- 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 description 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- VVJKKWFAADXIJK-UHFFFAOYSA-N allylamine Natural products NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 150000005130 benzoxazines Chemical group 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000000314 lubricant Substances 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
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 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 description 1
- 150000002897 organic nitrogen compounds Chemical class 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000005156 substituted alkylene group Chemical group 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 230000035900 sweating Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
-
- 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
-
- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- 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
-
- 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/06—Interconnection of layers permitting easy separation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The invention discloses a resin composition, which comprises the following components in percentage by weight of solid: modified bismaleimide prepolymer: 100 parts of (A); epoxy resin: 5-30 parts; curing agent: 0-20 parts of a solvent; filling: 0-150 parts; curing accelerator: 0.001-5 parts; the modified bismaleimide prepolymer is prepared by at least prepolymerizing bismaleimide resin and an allyl compound. Compared with the prior art, the resin composition disclosed by the invention has excellent peel strength, halogen-free flame retardance, high heat resistance, high-temperature modulus retention rate, excellent toughness, thermal expansion coefficient and high modulus retention rate, especially meets the halogen-free flame retardant UL94V-0, and has excellent high-temperature modulus retention rate and low thermal expansion coefficient, so that the resin composition is well suitable for high-performance circuit materials such as HDI high-multilayer substrates.
Description
Technical Field
The invention relates to the technical field of electronic materials, in particular to a high-heat-resistance resin composition and a prepreg and a laminated board prepared from the high-heat-resistance resin composition.
Background
In recent years, with the continuous development of mobile internet technology, the multi-functionalization, portability, and lightness and thinness are continuously the targets sought for electronic products, which means that more components are loaded on electronic products, more printed circuits adopt High Density Interconnect (HDI) technology, and the thickness of the whole printed circuit board is thinner, so that a higher requirement is put on a substrate-copper clad plate for manufacturing the printed circuit board, and the copper clad plate is required to have performance similar to a package substrate, i.e., a package material of the type rising in the industry is required to have high heat resistance, high glass transition temperature, excellent adhesion, good processability, and more importantly, the plate has better modulus retention rate at high temperature.
The bismaleimide resin as a high-performance resin material has excellent heat resistance and higher high-temperature modulus retention rate, but is poor in solubility, can only be dissolved in some high-boiling-point solvents such as N, N-dimethylformamide, N-methylpyrrolidone and the like, and is harsh in process conditions, and meanwhile, a cured bismaleimide resin is high in crosslinking density and high in brittleness, and other service performances are seriously affected. Therefore, in the prior art, aromatic diamine or diallyl compound is generally adopted for modification, and the modified bismaleimide resin has good processability and excellent performance, but the intrinsic flame retardance can not reach UL94V-0 grade no matter the maleimide resin is modified by the diamine or the diallyl compound, and a halogen-free flame retardant is required to be added to meet the requirement of European Union instruction.
Halogen-free flame retardation of laminates for printed circuits is generally achieved by adding a resin containing flame retardant elements such as nitrogen, phosphorus, and silicon and an inorganic filler (e.g., an inorganic compound containing crystal water such as aluminum hydroxide and magnesium hydroxide) to a resin matrix. Compared with the flame retardant containing phosphorus resin, the flame retardant containing silicon and nitrogen resin or inorganic filler has the problem of low flame retardant efficiency, and cannot meet the requirement of UL 94V-0. Therefore, the phosphorus-containing resin is dominant as a main flame retardant in the current halogen-free substrate material. These phosphorus-containing flame retardants are mainly reactive resins and additive flame retardants such as phosphorus-containing epoxy resins, phosphazene compounds, phosphoric esters or phosphorus-containing phenolic resins, and the like. After the components are introduced, the flame retardance of the board can be improved, but the flame retardant resin taking the epoxy resin or the phenolic resin as the matrix greatly reduces the heat resistance, the glass transition temperature, the high-temperature lower mold quantity retention rate and the like of a modified bismaleimide resin system, and is difficult to meet the application requirements of the modified bismaleimide resin system in high-performance fields such as high-density interconnection or integrated circuit packaging/class packaging.
Therefore, in order to obtain a halogen-free flame-retardant high-performance bismaleimide resin, a scheme of adding a phosphorus-containing flame retardant to a bismaleimide resin system is disclosed in the prior art.
For example, patent CN102276837A discloses a technical scheme of adding a phosphorus-containing compound (phosphazene) to a bismaleimide resin system, although a cured product which does not contain halogen and has good flame retardant performance can be obtained, these flame retardants do not form a good cross-linked network structure with the bismaleimide resin system, and under the high-temperature curing condition (often higher than 200 ℃) of the bismaleimide resin, the phosphazene compound which does not participate in the reaction emerges on the surface of the substrate in a manner similar to "sweating", which not only affects the heat resistance of the board, but also affects the bonding force between the board and the copper foil.
For example, patent CN103665864 discloses allyl modified bismaleimide resin, and organic phosphorus flame retardant or organic nitrogen compound is added to the glue solution, in this technical scheme, although the problem of solubility of bismaleimide resin can be solved, and halogen-free high flame retardant sheet can be obtained, but the addition of flame retardant component affects heat resistance, humidity resistance and water absorption of the final cured product, so it is difficult to obtain high performance sheet with excellent overall performance.
For example, JP2012153896 discloses a technical scheme of adding phosphorus-containing epoxy resin into a bismaleimide resin system, which can also meet the halogen-free flame retardant requirement, but the glass transition temperature, heat resistance and modulus retention rate at high temperature of the resin are greatly reduced due to the presence of the epoxy resin.
In view of the above, there is a need to develop a high-performance substrate material for printed circuit boards suitable for the field of class carrier boards, package carrier boards and high-density interconnection technologies, and the laminated board or copper-clad board prepared by using the material has excellent halogen-free flame retardancy, high heat resistance, low thermal expansion coefficient and high modulus retention rate at high temperature.
Disclosure of Invention
The invention aims to provide a resin composition for solving the technical problems, and a prepreg and a laminated board prepared by using the resin composition, wherein the resin composition simultaneously has excellent peel strength, halogen-free flame retardance, high heat resistance, high-temperature modulus retention rate, excellent toughness, thermal expansion coefficient and high modulus retention rate, particularly meets the halogen-free flame retardance UL94V-0, and simultaneously has excellent high-temperature modulus retention rate and low thermal expansion coefficient, so that the resin composition is well suitable for high-performance circuit materials such as HDI high-density multi-layer substrates.
Wherein the resin composition comprises the following components in percentage by weight of solid:
modified bismaleimide prepolymer: 100 parts of (A);
epoxy resin: 5-30 parts;
curing agent: 0-20 parts of a solvent;
filling: 0-150 parts;
curing accelerator: 0.001-5 parts;
the modified bismaleimide prepolymer is prepared by at least prepolymerizing bismaleimide resin and an allyl compound, wherein the allyl compound contains a phosphorus-containing allyl compound represented by the following structural formula (1) or structural formula (2):
wherein R is1Is a linear alkylene or substituted alkylene of C1-C10 or an aromatic group of C6-C20.
As a further improvement of the invention, the weight ratio of the bismaleimide resin to the allyl compound is 100: 10-100.
As a further improvement of the present invention, the bismaleimide resin has the following structural formula:
wherein, R group is selected from at least one of the following structural formulas:
in a further improvement of the present invention, the allyl compound further contains a phosphorus-free allyl compound selected from one or a mixture of two or more of diallyl bisphenol a, diallyl bisphenol S, allyl phenoxy resin, allyl phenolic resin, and diallyl diphenyl ether, and the content of the phosphorus-free allyl compound is 10 to 90 parts by mass based on 100 parts by mass of the total allyl compound.
As a further improvement of the present invention, the epoxy resin is one or a mixture of any more of bisphenol a epoxy resin, bisphenol F epoxy resin, phosphorus-containing epoxy resin, nitrogen-containing 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, polyphenylene oxide-modified epoxy resin, alicyclic epoxy resin, glycidylamine epoxy resin, and glycidylester epoxy resin.
In a further improvement of the present invention, the curing agent is an amine compound, an amide compound, an acid anhydride compound, or a phenol compound.
As a further improvement of the present invention, the filler is an inorganic filler or an organic filler, and the inorganic filler is 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 selected from one or a mixture of at least any two of polytetrafluoroethylene powder, polyphenylene sulfide powder or polyether sulfone powder.
Correspondingly, the invention also provides a prepreg, which is prepared by adding a solvent into the resin composition to dissolve the resin composition to prepare a glue solution, dipping the reinforcing material into the glue solution, and heating and drying the dipped reinforcing material.
Correspondingly, the invention also provides a laminated board, wherein the double surfaces of at least one prepreg are covered with release films, and the laminated board can be obtained by hot press forming.
Correspondingly, the invention also provides a laminated plate, wherein the laminated plate can be obtained by coating metal foil on one side or two sides of at least one prepreg and performing hot press forming.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
(1) according to the invention, the allyl compound containing the DOPO or DPPO structure is used as the bismaleimide resin modifier, on the basis of not affecting the performance of the bismaleimide resin, the phosphorus-containing group is well introduced into the crosslinking network structure of the bismaleimide resin, so that the nitrogen element and the phosphorus element in one crosslinking network structure are cooperatively flame-retardant, the phosphorus content required by the flame retardance of the cured product to reach UL94V-0 can be reduced, other flame retardants are not required to be added, and the cured product with excellent halogen-free flame retardance, high heat resistance, high adhesion, excellent toughness and thermal expansion coefficient is obtained;
(2) when the straight-chain alkyl is arranged at the middle position of DOPO or DPPO in the allyl compound structure, the crosslinking density of the whole bismaleimide polymer crosslinking network structure can be adjusted, the brittleness of the bismaleimide resin is effectively reduced, the generation of stress in the curing reaction process is relieved, the thermal expansion coefficient of the plate is reduced, and meanwhile, the excellent high-temperature modulus is kept.
(3) When the modified bismaleimide prepolymer is prepared, the phosphorus-free allyl compound is properly added, so that the preparation process of the prepolymer can be effectively controlled, the allyl compound plays a role in polymerization inhibition in the addition reaction of maleimide and allyl, the solubility of the bismaleimide resin is improved, the overall polymerization reaction rate can be well controlled, and a final cured product with more excellent comprehensive performance is obtained.
(4) The allyl compound containing the DOPO or DPPO structure reacts with bismaleimide, and-NH-active hydrogen in the structure reacts with epoxy groups, so that a final cured product with high heat resistance, low thermal expansion coefficient and high modulus can be obtained under the condition of adding a small amount of epoxy resin, and the allyl compound has excellent adhesion, and meets the requirements of high-performance printed circuit boards such as HDI multilayer substrates and ultrathin packaging substrates.
Detailed Description
The present invention will be described in detail below with reference to specific embodiments. These embodiments are not intended to limit the present invention, and structural, methodological, or functional changes made by those skilled in the art according to these embodiments are included in the scope of the present invention. Variations in reaction conditions, amounts of reactants or starting materials, which may be made by one of ordinary skill in the art in light of these examples, are within the scope of the invention.
In a specific embodiment of the present invention, a flame retardant resin prepolymer, specifically a modified bismaleimide prepolymer, is prepared by at least pre-polymerizing bismaleimide resin and an allyl compound, wherein the allyl compound contains a phosphorus-containing allyl compound represented by structural formula (1) or structural formula (2):
wherein R1 is C1-C10 straight chain alkylene or substituted alkylene or C6-C20 aromatic group;
the weight ratio of the bismaleimide resin to the allylic compound is 100:10-100, preferably 100:20-60, and specifically may be 100:10, 100:15, 100:20, 100:25, 100:30, 100:35, 100:40, 100:45, 100:50, 100:55, 100:60, 100:65, 100:70, 100:75, 100:80, 100:85, 100:90, 100:95, or 100: 100.
Further, in the above allyl compound structural formulas (1) and (2), R1 isWhen R1 is a linear alkylene group, and is arranged at the middle position containing DOPO or DPPO at two sides, the linear alkylene group of C2-C6 can adjust the crosslinking density of the whole bismaleimide polymer crosslinking network structure, effectively reduce the brittleness of the bismaleimide resin and relieve the generation of stress in the curing reaction process. But when R is1When the chain length of the linear alkylene group is too long, the linear long chain is easily broken under high temperature conditions, which affects the heat resistance of the cured product, and when R is too long1When the chain length of the linear alkylene group is too short, the above-described effect is difficult to obtain.
In the above allyl compound structural formulas (1) and (2), the aromatic group in R1 is
Among them, preferred is
Straight chain alkylene is
Or substituted alkylene groups thereof, among which preferred is
Further, the bismaleimide resin has the following structural formula:
wherein, R group is selected from at least one of the following structural formulas:
the allyl compound further contains a phosphorus-free allyl compound, preferably, the phosphorus-free allyl compound is one or a mixture of two or more selected from diallyl bisphenol a, diallyl bisphenol S, allyl phenoxy resin, allyl phenolic resin, and diallyl diphenyl ether, and the content of the phosphorus-free allyl compound is 10 to 90 parts, preferably 30 to 50 parts, more preferably 30 parts, 31 parts, 32 parts, 33 parts, 34 parts, 35 parts, 36 parts, 37 parts, 38 parts, 39 parts, 40 parts, 41 parts, 42 parts, 43 parts, 44 parts, 45 parts, 46 parts, 47 parts, 48 parts, 49 parts, and 50 parts, based on 100 parts by mass of the total allyl compound.
When the prepolymer is prepared, the phosphorus-free allyl compound is properly added, so that the preparation process of the prepolymer can be effectively controlled, the phosphorus-free allyl compound plays a role in polymerization slowing in the addition reaction of maleimide groups and allyl groups, the solubility of the bismaleimide resin is improved, but when the content is higher, the reaction of the phosphorus-containing allyl groups and the maleimide groups is influenced, and DOPO or DPPO cannot be well introduced into a bismaleimide system.
The invention also provides a resin composition, which comprises the following components in percentage by weight of solid:
the above flame retardant type resin prepolymer, i.e., modified bismaleimide prepolymer: 100 parts of (A);
epoxy resin: 5-30 parts;
curing agent: 0-20 parts of a solvent;
filling: 0-150 parts;
curing accelerator: 0.001-5 parts.
Further, the epoxy resin is one or a mixture of any more of bisphenol a epoxy resin, bisphenol F epoxy resin, phosphorus-containing epoxy resin, nitrogen-containing 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 type epoxy resin, naphthalene ring type epoxy resin, dicyclopentadiene type epoxy resin, isocyanate type epoxy resin, aralkyl novolac epoxy resin, polyphenylene oxide modified epoxy resin, alicyclic epoxy resin, glycidylamine type epoxy resin, and glycidyl ester type epoxy resin. Bisphenol A epoxy resin, bisphenol A novolac epoxy resin, biphenyl type epoxy resin, naphthalene ring type epoxy resin or dicyclopentadiene type epoxy resin is preferable in the present invention.
Further, the curing agent is an amine-based compound, an amide-based compound, dicyandiamide, an acid anhydride-based compound, a benzoxazine resin or a phenol-based compound, and the content thereof is preferably 1 to 10 parts by weight based on 100 parts by weight of the modified bismaleimide prepolymer.
Specifically, the amine compound may be diaminodiphenylmethane, diaminodiphenylsulfone, diethylenetriamine, dicarboxyphthalimide, imidazole, or the like; the amide compound may be a low molecular weight polyamide; the acid anhydride compound may be phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, maleic anhydride, hydrogenated phthalic anhydride, nadic anhydride, etc., and preferably styrene-maleic anhydride; the phenol compound may be bisphenol a phenol resin, phenol resin, naphthol phenol resin, biphenol naphthol resin, dicyclopentadiene phenol addition resin, phenol aralkyl resin, naphthol aralkyl resin, or the like.
The curing agent of the invention is preferably a diaminodiphenyl sulfone or a biphenyl phenol type phenolic resin or a benzoxazine resin. When the curing agent is diamino diphenyl sulfone, the components of the resin composition and the contents of the components are as follows:
modified bismaleimide prepolymer: 100 parts of (A);
epoxy resin: 5-30 parts;
diamino diphenyl sulfone: 0 to 10 portions of
Filling: 20-150 parts;
curing accelerator: 0.001-2 parts.
When the curing agent is biphenyl phenol type phenolic resin, the components of the resin composition and the contents of the components are as follows:
modified bismaleimide prepolymer: 100 parts of (A);
epoxy resin: 5-30 parts;
phenol type phenol resin: 0 to 20 portions of
Filling: 20-150 parts;
curing accelerator: 0.001-2 parts.
When the curing agent is benzoxazine resin, the components of the resin composition and the contents of the components are as follows:
modified bismaleimide prepolymer: 100 parts of (A);
epoxy resin: 5-30 parts;
benzoxazine resin: 0 to 20 portions of
Filling: 20-150 parts;
curing accelerator: 0.001-2 parts.
Further, the filler is selected from 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 salt, metal hydrate or inorganic phosphorus, preferably any one or a mixture of at least any two 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 or glass fiber powder; the organic filler is one or a mixture of at least any two of polytetrafluoroethylene powder, polyphenylene sulfide powder and polyether sulfone powder.
In the present invention, the filler is preferably an inorganic filler, more preferably a surface-treated inorganic filler, and most preferably a surface-treated silica. The surface treating agent for carrying out surface treatment on the inorganic filler is selected from any one or a mixture of at least two of a silane coupling agent, an organic silicon oligomer or a titanate coupling agent, the particle size median value of the filler is 0.2-20 mu m, preferably the particle size median value of the filler is 0.5-5 mu m, and the filler located in the particle size section has good dispersibility and good processability.
More preferably, the surface treatment agent is used in an amount of 0.1 to 5.0%, preferably 0.5 to 3.0%, and further preferably 0.75 to 2.0%, based on 100% by mass of the inorganic filler.
Further, the curing accelerator is selected from dimethylaminopyridine, imidazole, organometallic salts, triphenylphosphine and phosphonium salts thereof, and the like. The curing accelerator may be added according to the actual condition, and is selected from dimethylaminopyridine, tertiary amine and salts thereof, imidazole, organic metal salts, triphenylphosphine and phosphonium salts thereof, etc., and the content thereof is preferably 0.01 to 2.0 parts based on 100 parts of the flame-retardant resin prepolymer.
The resin composition of the present invention further comprises an elastomer, wherein the elastomer is a low modulus component, and is selected from at least one of polybutadienes, styrenes, polyurethanes, polyesters, polyamines, acrylates or silicones, preferably a low modulus component containing a reactive group, the reactive group may be an epoxy group, a hydroxyl group, an amino group, an acid anhydride group, a carboxyl group or a vinyl group, and is more preferably selected from epoxy-modified polybutadiene, acid anhydride-modified polybutadiene, a styrene-butadiene copolymer, a styrene-propylene copolymer or a styrene-acrylic copolymer, and the content of the elastomer is preferably 5 to 20 parts based on 100 parts of the flame retardant resin prepolymer.
When the low-modulus elastomer is properly added to the flame-retardant resin composition, the generation of stress can be reduced in the curing reaction process, the thermal expansion coefficient of the plate can be effectively improved, and meanwhile, the brittleness of the bismaleimide resin can be further improved.
Further, an antioxidant, a heat stabilizer, an antistatic agent, an ultraviolet absorber, a pigment, a colorant, a lubricant, or the like may be added to the resin composition according to the actual circumstances. These various additives may be used alone or in combination of two or more.
The invention also provides a prepreg prepared by adopting the resin composition, which comprises the following preparation steps:
dissolving the flame-retardant resin composition by using a solvent, uniformly stirring and curing the mixture until the solid content is 60-75 percent to prepare a resin composition glue solution;
and (3) soaking the reinforcing material in the resin composition glue solution, and then baking the soaked reinforcing material at the temperature of 50-170 ℃ for 1-10min to dry to obtain the prepreg.
Among them, the reinforcing material is natural fiber, organic synthetic fiber, organic fabric or inorganic fabric, and the inorganic fabric is particularly preferably glass fiber cloth, and the glass fiber cloth is preferably open fiber cloth or flat cloth. In addition, in order to improve the interfacial bonding between the resin and the glass cloth, the glass cloth generally needs to be chemically treated, mainly by a coupling agent such as epoxy silane, amino silane, etc.
The solvent is selected from one or the 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 invention also provides a laminated board prepared by adopting the prepreg, which comprises the following preparation steps:
and covering a release film on the double surfaces of at least one prepreg, and performing hot press forming to obtain the laminated board, wherein the number of the prepregs can be determined according to the thickness of the required laminated board, and one or more prepregs can be used. The release film can be a PET film or a release aluminum foil.
The invention also provides another laminated board prepared by adopting the prepreg, which comprises the following preparation steps:
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 number of prepregs may be determined according to the thickness of the laminate desired, and one or more prepregs may be used. The metal foil may be a copper foil or an aluminum foil, and the thickness thereof is not particularly limited.
The pressing condition of the laminated board is that the laminated board is pressed for 2-4 hours under the pressure of 0.2-2 MPa and the temperature of 180-250 ℃.
The prepreg, the laminated board and the metal foil laminated board are all used for preparing circuit boards.
In order to better illustrate the present invention, the following specific examples are provided to further describe the present invention, and the following specific synthetic examples of the preparation of the flame retardant bismaleimide prepolymer are as follows:
synthesis example 1
Adding 100 parts of solvent N, N-dimethylformamide into a 500mL three-neck flask, putting 4, 4' -diphenylmethane bismaleimide, DOPO-containing allyl compound A-1 (linear chain type) and diallyl bisphenol A into the three-neck flask in sequence according to the mass part of 100:80:20, continuously stirring under the condition of an oil bath at 110 ℃, starting timing after the solid in the flask is completely dissolved, and continuously stirring for 1hr, and distilling the obtained product to obtain a modified bismaleimide prepolymer 1 with the solid content of 75%.
Synthesis example II
Adding 100 parts of solvent N, N-dimethylformamide into a 500mL three-neck flask, putting 4, 4' -diphenylmethane bismaleimide, DOPO-containing allyl compound A-2 (aromatic type) and diallyl bisphenol A into the three-neck flask in sequence according to the mass part of 100:60:20, continuously stirring under the condition of an oil bath at 110 ℃, starting timing after the solid in the flask is completely dissolved, and continuously stirring for 1hr, and distilling the obtained product to obtain a modified bismaleimide prepolymer 2 with the solid content of 75%.
Synthesis example three
Adding 100 parts of solvent N, N-dimethylformamide into a 500mL three-neck flask, putting 4, 4' -diphenylmethane bismaleimide, allyl compound A-3 (linear chain type) containing DPPO group and diallyl diphenyl ether into the three-neck flask in sequence according to the mass ratio of 100:40:30, continuously stirring under the condition of an oil bath at 110 ℃, starting timing after the solid in the flask is completely dissolved, and continuously stirring for 1hr, and distilling the obtained product to obtain the modified bismaleimide prepolymer 3 with the solid content of 75%.
Synthesis example four
Adding 100 parts of solvent N, N-dimethylformamide into a 500mL three-neck flask, putting 4, 4' -diphenylmethane bismaleimide, allyl compound A-4 (aromatic type) containing DPPO group and diallyl bisphenol A into the three-neck flask in sequence according to the mass part of 100:30:50, continuously stirring under the condition of an oil bath at 110 ℃, starting timing after the solid in the flask is completely dissolved, and continuously stirring for 1hr, and distilling the obtained product to obtain a modified bismaleimide prepolymer 4 with the solid content of 75%.
Synthesis example five (different content ratio compared with Synthesis example 1)
Adding 100 parts of solvent N, N-dimethylformamide into a 500mL three-neck flask, putting 4, 4' -diphenylmethane bismaleimide, DOPO-containing allyl compound A-1 (linear chain type) and diallyl diphenyl ether into the three-neck flask in sequence according to the mass part of 100:20:40, continuously stirring under the condition of an oil bath at 110 ℃, starting timing after the solid in the flask is completely dissolved, and continuously stirring for 1hr, and distilling the obtained product to obtain the modified bismaleimide prepolymer 5 with the solid content of 75%.
Synthesis example six
Adding 100 parts of solvent N, N-dimethylformamide into a 500mL three-neck flask, putting 4, 4' -diphenylmethane bismaleimide, DOPO-containing allyl compound A-1 (linear chain type) and diallyl bisphenol A into the three-neck flask in sequence according to the mass part of 100:30:70, continuously stirring under the condition of an oil bath at 110 ℃, starting timing after the solid in the flask is completely dissolved, and continuously stirring for 1hr, and distilling the obtained product to obtain a modified bismaleimide prepolymer 6 with the solid content of 75%.
Synthesis example seven
Adding 100 parts of solvent N, N-dimethylformamide into a 500mL three-neck flask, putting 4, 4' -diphenylmethane bismaleimide, DOPO-containing allyl compound A-1 (linear chain type) and diallyl diphenyl ether into the three-neck flask in sequence according to the mass part of 100:10:40, continuously stirring under the condition of an oil bath at 110 ℃, starting 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 7 with the solid content of 75%.
Synthesis example eight (prepolymerization of bismaleimide with phosphorus-containing allyl Compound)
Adding 100 parts of solvent N, N-dimethylformamide into a 500mL three-neck flask, sequentially adding 4, 4' -diphenylmethane bismaleimide and allyl compound A-1 (linear chain type) containing DOPO groups into the three-neck flask according to the mass part of 100:50, continuously stirring under the condition of an oil bath at 110 ℃, timing when the solid in the flask is completely dissolved, continuously stirring for 1hr, and distilling the obtained product to obtain a modified bismaleimide resin prepolymer 8 with the solid content of 75%.
Comparative Synthesis example No. (Bima + allyl Compound copolymerization)
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 when the solid in the flask is completely dissolved, continuously stirring for 1hr, and distilling the obtained product to obtain the modified bismaleimide prepolymer 9 with the solid content of 75%.
Comparative Synthesis example ten (bismaleimide + allyl + phosphorus-containing Compound copolymerization)
Adding 100 parts of solvent N, N-dimethylformamide into a 500mL three-neck flask, putting 4, 4' -diphenylmethane bismaleimide, diallyl bisphenol A and a phosphorus compound (DOPO) into the three-neck flask in sequence according to the mass part of 100:60:10, continuously stirring under the condition of an oil bath at 110 ℃, timing when the solid in the flask is completely dissolved, continuously stirring for 0.2hr, and distilling the obtained product to obtain the modified bismaleimide prepolymer 10 with the solid content of 75%.
Comparative Synthesis example eleven (bismaleimide + allyl Compound + phosphorus-containing epoxy resin copolymerization)
Adding 100 parts of solvent N, N-dimethylformamide into a 500mL three-neck flask, putting 4, 4' -diphenylmethane bismaleimide, an allyl compound and phosphorus-containing epoxy resin into the three-neck flask in sequence according to the mass part of 100:50:30, stirring and reacting for 2 hours under the condition of 110 ℃ oil bath, distilling the obtained product to obtain a solid substance, and preparing the modified bismaleimide prepolymer 11 with the solid content of 75% by using an organic solvent.
Preparing a prepreg: the components and the mixture ratio in the following table 1 and table 2 are adopted to prepare glue solution with 62 percent of solid content, the glue solution is soaked by glass fiber cloth, and the prepreg is prepared by drying in a 160 ℃ oven for 5 min.
Preparing a copper-clad laminate: and (3) superposing the 8 semi-solidified materials with the burrs cut off, attaching 35-micron copper foils to the upper part and the lower part of the semi-solidified materials, and placing the semi-solidified materials in a vacuum hot press for pressing to obtain the copper-clad plate. The specific pressing process is pressing for 4 hours under the pressure of 1.5Mpa and the temperature of 220 ℃.
The properties of the copper-clad laminate obtained are shown in tables 1 and 2:
table 1 shows specific examples of the present invention
Table 2 comparative examples of the invention
*1: the glue reacts too fast, GT is short, and the plate substrate has serious dry flower defects;
*2: the copper of the plate is removed, and precipitates are formed on the surface of the plate
The preparation method of the allyl compounds A-1 to A-4 comprises the following steps:
the first step is as follows: 1mol of allylamine compound is taken and evenly mixed with a proper amount of organic solvent, 0.5mol of terephthalaldehyde is dripped into a reaction bottle at the temperature of 50-100 ℃, and the reaction is carried out for 1-5 hours under the protection of nitrogen;
the second step is that: after the reaction is finished, cooling the reaction mixture, performing suction filtration to obtain a crude product, dissolving the crude product in deionized water, heating, cooling and recrystallizing by the same method, repeating for 2-5 times, and finally drying in a vacuum drying oven at 60-90 ℃ for 24 hours to obtain an intermediate product;
step three: taking 0.5mol of intermediate product and 1mol of DOPO, adding a proper amount of organic solvent, gradually heating to completely dissolve the intermediate product and the DOPO, reacting for 5-7 hours at 90-120 ℃ under the protection of nitrogen, cooling to room temperature after the reaction is finished, dissolving and heating by deionized water, cooling and recrystallizing by the same method, repeating for 2-5 times, and finally drying for 24 hours at 60-90 ℃ in a vacuum drying oven to obtain the allyl compound.
In the above process different aldehyde compounds and phosphorus compounds are selected to obtain allyl compounds of the following structure:
allyl Compound A-1: structural formula (1), R1Is composed of
Allyl Compound A-2: structural formula (1), R1Is composed of
Allyl Compound A-3: structural formula (2), R1Is composed of
Allyl Compound A-4: structural formula (2), R1Is composed of
Allyl Compound A-5: structural formula (1), R1Is composed of
4, 4' -diphenylmethane bismaleimide: xian Shuangma new materials, Inc.;
unmodified bismaleimide: 4, 4' -diphenylmethane bismaleimide and new material of Xian bismaleimide;
4, 4' -diphenylmethane bismaleimide: xian Shuangma new materials, Inc.;
biphenyl type epoxy resin: NC3000H, japan chemicals;
phenol type phenol resin: KAYAHARD GPH-103, Japan chemical;
phosphorus-containing phenolic resin: LC950, SHIN-A;
phosphorus-containing epoxy resin: KEG-H5138, Kolon;
phosphazene: SPB100, tsukamur chemical;
filling: silicon dioxide, surface treatment is carried out on the silicon dioxide by using a silane coupling agent, the average grain diameter is 1.0 mu m, and Jiangsu birry;
curing accelerator: 2-methylimidazole, formed in four countries;
phosphorus-containing epoxy resin: KEG-H5138, Kolon;
phosphazene compound: SPB100, Otsuka chemistry;
elastomer: KMP-605, Beacon Chemicals.
The performance evaluation method comprises the following steps:
(1) glass transition temperature (DMA): measuring Tg with DMA at a temperature rise rate of 10 deg.C/min and a frequency of 10Hz,
temperature range: 30-320 ℃.
(2) 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.
(3) Flame retardancy: UL94 vertical burning (UL 94V), according to ASTM (D63-77) method test.
(4) Peel strength resistance: the peel strength of the metal cap was tested according to the "post thermal stress" experimental conditions in the IPC-TM-650 method.
(5) Coefficient of thermal expansion (X/Y-CTE): 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 direction is the transverse direction (X) and the longitudinal direction (Y) of the glass cloth surface, and the unit is X/Yppm/DEG C.
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-listed detailed description is only a specific description of a possible embodiment of the present invention, and they are not intended to limit the scope of the present invention, and equivalent embodiments or modifications made without departing from the technical spirit of the present invention should be included in the scope of the present invention.
Claims (21)
1. A resin composition characterized by comprising, by solid weight:
modified bismaleimide prepolymer: 100 parts of (A);
epoxy resin: 5-30 parts;
curing agent: 0-20 parts of a solvent;
filling: 0-150 parts;
curing accelerator: 0.001-5 parts;
the modified bismaleimide prepolymer is prepared by at least prepolymerizing bismaleimide resin and an allyl compound, wherein the allyl compound contains a phosphorus-containing allyl compound represented by the following structural formula (1) or structural formula (2):
wherein R is1Is a linear alkylene or substituted alkylene of C1-C10 or an aromatic group of C6-C20.
2. The resin composition of claim 1, wherein the weight ratio of the bismaleimide resin to the allylic compound is 100:10 to 100: 100.
3. The resin composition of claim 1, wherein the bismaleimide resin has the following structural formula:
wherein, R group is selected from at least one of the following structural formulas:
(a)
(b)
(c)
(d)
(e)
(f)
(g)
(h)
(i)
4. the resin composition according to claim 1, wherein the allyl compound further contains a phosphorus-free allyl compound selected from one or a mixture of two or more of diallyl bisphenol A, diallyl bisphenol S, allyl phenoxy resin, allyl phenol resin, and diallyl diphenyl ether, and the content of the phosphorus-free allyl compound is 10 to 90 parts by mass based on 100 parts by mass of the total allyl compound.
5. The resin composition according to claim 1, wherein the epoxy resin is one or a mixture of any of bisphenol A epoxy resin, bisphenol F epoxy resin, phosphorous epoxy resin, nitrogen-containing 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, polyphenylene ether-modified epoxy resin, alicyclic epoxy resin, glycidylamine epoxy resin, and glycidylester epoxy resin.
6. The resin composition according to claim 1, wherein the curing agent is an amine-based compound, an amide-based compound, an acid anhydride-based compound, a benzoxazine resin, or a phenol-based compound.
7. The resin composition according to claim 6, wherein the amine compound is diaminodiphenylmethane, diaminodiphenylsulfone, diethylenetriamine, dicyandiamide, biscarboxyphthalimide, or imidazole; the amide compound is a low-molecular polyamide; the acid anhydride compound is styrene-maleic anhydride; the phenolic compound is bisphenol A phenolic resin, phenol phenolic resin, naphthol phenolic resin, biphenyl phenol naphthol resin, dicyclopentadiene phenol addition resin, phenol aralkyl resin, naphthol aralkyl resin.
8. The resin composition according to claim 7, comprising, based on solid weight:
modified bismaleimide prepolymer: 100 parts of (A);
epoxy resin: 5-30 parts;
diamino diphenyl sulfone: 0 to 10 portions of
Filling: 20-150 parts;
curing accelerator: 0.001-2 parts.
9. The resin composition according to claim 7, comprising, based on solid weight:
modified bismaleimide prepolymer: 100 parts of (A);
epoxy resin: 5-30 parts;
phenol type phenol resin: 0 to 20 portions of
Filling: 20-150 parts;
curing accelerator: 0.001-2 parts.
10. The resin composition according to claim 6, comprising, based on solid weight:
modified bismaleimide prepolymer: 100 parts of (A);
epoxy resin: 5-30 parts;
benzoxazine resin: 0-20 parts of a solvent;
filling: 20-150 parts;
curing accelerator: 0.001-2 parts.
11. The resin composition according to claim 1, wherein the filler is an inorganic filler or an organic filler, and the inorganic filler is one or a mixture of at least any two of non-metal oxide, metal nitride, non-metal nitride, inorganic salt, metal hydrate, and inorganic phosphorus; the organic filler is selected from one or a mixture of at least any two of polytetrafluoroethylene powder, polyphenylene sulfide powder or polyether sulfone powder.
12. The resin composition according to claim 1, wherein the filler is any one or a mixture of at least two 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, or glass fiber powder.
13. The resin composition according to claim 1, wherein the filler is surface-treated silica.
14. The resin composition according to claim 1, wherein the curing accelerator is at least one selected from the group consisting of dimethylaminopyridine, imidazole, organometallic salts, triphenylphosphine, and phosphonium salts thereof.
15. The resin composition according to claim 1, further comprising an elastomer.
16. The resin composition according to claim 15, wherein the elastomer is at least one selected from the group consisting of polybutadienes, styrenes, polyurethanes, polyesters, polyamines, acrylates and silicones.
17. The resin composition of claim 15, wherein the elastomer is an epoxy-modified polybutadiene, an anhydride-modified polybutadiene, a styrene butadiene copolymer, a styrene propylene copolymer, or a styrene acrylic copolymer.
18. The resin composition according to claim 15, wherein the elastomer is contained in an amount of 5 to 20 parts by weight based on 100 parts by weight of the modified bismaleimide prepolymer.
19. A prepreg obtained by dissolving a resin composition according to any one of claims 1 to 18 in a solvent to prepare a liquid cement, impregnating a reinforcing material in the liquid cement, and heating and drying the impregnated reinforcing material.
20. A laminate obtained by coating at least one prepreg according to claim 19 on both sides with a release film and hot press forming.
21. A laminate which is obtained by coating at least one prepreg according to claim 19 on one or both sides with a metal foil and hot-pressing.
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| CN114316115B (en) | 2021-12-31 | 2023-12-26 | 广东盈骅新材料科技有限公司 | Allyl flame-retardant prepolymer, resin composition, composite resin, prepreg and laminated board |
| CN114536923B (en) * | 2022-03-30 | 2024-04-26 | 常州中英科技股份有限公司 | Fluorine-containing resin-based high-heat-conductivity high-frequency copper-clad plate with high dielectric constant |
| CN116004006B (en) * | 2022-12-27 | 2024-12-13 | 苏州生益科技有限公司 | Resin composition and use of the same |
| CN116004008A (en) * | 2022-12-31 | 2023-04-25 | 苏州生益科技有限公司 | Resin composition and its application |
| CN116875053B (en) * | 2023-07-31 | 2025-05-16 | 常熟生益科技有限公司 | Resin composition and application thereof |
| CN116987386A (en) * | 2023-08-01 | 2023-11-03 | 苏州生益科技有限公司 | Resin compositions and their applications |
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| US20030003305A1 (en) * | 2001-03-27 | 2003-01-02 | International Business Machines Corporation | Halogen free triazines, bismaleimide/epoxy polymers, prepregs made therefrom for circuit boards and resin coated articles, and use |
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| JP5023877B2 (en) * | 2006-12-05 | 2012-09-12 | 日立化成工業株式会社 | Flame retardant resin compound, thermosetting resin composition using the same, prepreg and laminate |
| CN101652026B (en) * | 2009-08-31 | 2011-03-30 | 苏州生益科技有限公司 | Preparation method of copper clad plate |
| CN102199351B (en) * | 2011-04-08 | 2012-12-05 | 苏州生益科技有限公司 | Thermosetting resin composition, prepreg and laminated board |
| CN102838864B (en) * | 2012-09-20 | 2014-07-30 | 苏州生益科技有限公司 | Resin composition and prepreg and laminate manufactured by using same |
| CN103980708B (en) * | 2014-05-28 | 2017-01-11 | 苏州生益科技有限公司 | Halogen-free flame-retardant thermosetting resin composition of integrated circuit, prepreg and laminate |
| CN104447869B (en) * | 2014-10-27 | 2019-03-01 | 复旦大学 | It is a kind of containing DOPO and the asymmetric bismaleimide of molecular structure, preparation method and in the application prepared in compound resin |
| CN106240132A (en) * | 2016-07-27 | 2016-12-21 | 重庆德凯实业股份有限公司 | A kind of manufacture method of halogen-free flameproof High Tg CCL |
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| EP0376444A2 (en) * | 1988-12-27 | 1990-07-04 | Ford Motor Company Limited | A thermosetting organic composition |
| US20030003305A1 (en) * | 2001-03-27 | 2003-01-02 | International Business Machines Corporation | Halogen free triazines, bismaleimide/epoxy polymers, prepregs made therefrom for circuit boards and resin coated articles, and use |
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