CN117002106A - Metal foil laminate, printed circuit board and method for manufacturing the same - Google Patents
Metal foil laminate, printed circuit board and method for manufacturing the same Download PDFInfo
- Publication number
- CN117002106A CN117002106A CN202210475667.1A CN202210475667A CN117002106A CN 117002106 A CN117002106 A CN 117002106A CN 202210475667 A CN202210475667 A CN 202210475667A CN 117002106 A CN117002106 A CN 117002106A
- Authority
- CN
- China
- Prior art keywords
- diisocyanate
- metal foil
- maleic anhydride
- compound
- styrene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011888 foil Substances 0.000 title claims abstract description 53
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 53
- 239000002184 metal Substances 0.000 title claims abstract description 53
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 title claims description 15
- -1 styrene maleic anhydride compound Chemical class 0.000 claims abstract description 81
- 229920000147 Styrene maleic anhydride Polymers 0.000 claims abstract description 78
- 150000001875 compounds Chemical class 0.000 claims abstract description 44
- 239000011342 resin composition Substances 0.000 claims abstract description 28
- 229920000098 polyolefin Polymers 0.000 claims abstract description 23
- 239000000758 substrate Substances 0.000 claims abstract description 19
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 17
- 239000004642 Polyimide Substances 0.000 claims abstract description 10
- 229920001721 polyimide Polymers 0.000 claims abstract description 10
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 7
- 230000004048 modification Effects 0.000 claims abstract description 7
- 238000012986 modification Methods 0.000 claims abstract description 7
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 38
- 238000010438 heat treatment Methods 0.000 claims description 33
- 229920005989 resin Polymers 0.000 claims description 24
- 239000011347 resin Substances 0.000 claims description 24
- 238000001816 cooling Methods 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 16
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 15
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 14
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 13
- 229920001187 thermosetting polymer Polymers 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 12
- 229920005996 polystyrene-poly(ethylene-butylene)-polystyrene Polymers 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000007731 hot pressing Methods 0.000 claims description 9
- PAUHLEIGHAUFAK-UHFFFAOYSA-N 1-isocyanato-1-[(1-isocyanatocyclohexyl)methyl]cyclohexane Chemical compound C1CCCCC1(N=C=O)CC1(N=C=O)CCCCC1 PAUHLEIGHAUFAK-UHFFFAOYSA-N 0.000 claims description 8
- 239000004743 Polypropylene Substances 0.000 claims description 8
- 229920001155 polypropylene Polymers 0.000 claims description 8
- 239000004698 Polyethylene Substances 0.000 claims description 7
- 229920000573 polyethylene Polymers 0.000 claims description 7
- 239000004634 thermosetting polymer Substances 0.000 claims description 7
- 239000003822 epoxy resin Substances 0.000 claims description 6
- 239000000945 filler Substances 0.000 claims description 6
- 229920000647 polyepoxide Polymers 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical class CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 6
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical class O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 claims 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 claims description 4
- GFNDFCFPJQPVQL-UHFFFAOYSA-N 1,12-diisocyanatododecane Chemical compound O=C=NCCCCCCCCCCCCN=C=O GFNDFCFPJQPVQL-UHFFFAOYSA-N 0.000 claims description 3
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical class O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 claims description 3
- MTZUIIAIAKMWLI-UHFFFAOYSA-N 1,2-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC=C1N=C=O MTZUIIAIAKMWLI-UHFFFAOYSA-N 0.000 claims description 3
- ZGDSDWSIFQBAJS-UHFFFAOYSA-N 1,2-diisocyanatopropane Chemical compound O=C=NC(C)CN=C=O ZGDSDWSIFQBAJS-UHFFFAOYSA-N 0.000 claims description 3
- UFXYYTWJETZVHG-UHFFFAOYSA-N 1,3-diisocyanatobutane Chemical compound O=C=NC(C)CCN=C=O UFXYYTWJETZVHG-UHFFFAOYSA-N 0.000 claims description 3
- IKYNWXNXXHWHLL-UHFFFAOYSA-N 1,3-diisocyanatopropane Chemical compound O=C=NCCCN=C=O IKYNWXNXXHWHLL-UHFFFAOYSA-N 0.000 claims description 3
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 claims description 3
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 claims description 3
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 claims description 3
- DFPJRUKWEPYFJT-UHFFFAOYSA-N 1,5-diisocyanatopentane Chemical compound O=C=NCCCCCN=C=O DFPJRUKWEPYFJT-UHFFFAOYSA-N 0.000 claims description 3
- ABWDWYZSKJSXRD-UHFFFAOYSA-N N=C=O.N=C=O.C1CC=CC1 Chemical compound N=C=O.N=C=O.C1CC=CC1 ABWDWYZSKJSXRD-UHFFFAOYSA-N 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000002657 fibrous material Substances 0.000 claims description 3
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 claims description 3
- 239000004305 biphenyl Substances 0.000 claims description 2
- 229920002521 macromolecule Polymers 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 48
- WOLATMHLPFJRGC-UHFFFAOYSA-N furan-2,5-dione;styrene Chemical class O=C1OC(=O)C=C1.C=CC1=CC=CC=C1 WOLATMHLPFJRGC-UHFFFAOYSA-N 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 13
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 13
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 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 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 7
- 238000004090 dissolution Methods 0.000 description 7
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 6
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 239000011889 copper foil Substances 0.000 description 6
- 239000011258 core-shell material Substances 0.000 description 6
- 229920001971 elastomer Polymers 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229920003192 poly(bis maleimide) Polymers 0.000 description 6
- 239000005060 rubber Substances 0.000 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 description 5
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 239000012948 isocyanate Substances 0.000 description 5
- 239000012745 toughening agent Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 230000000051 modifying effect Effects 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 229940126062 Compound A Drugs 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000004643 cyanate ester Substances 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000012779 reinforcing material Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-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
- 239000005062 Polybutadiene Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 238000007385 chemical modification Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- JNGZXGGOCLZBFB-IVCQMTBJSA-N compound E Chemical compound N([C@@H](C)C(=O)N[C@@H]1C(N(C)C2=CC=CC=C2C(C=2C=CC=CC=2)=N1)=O)C(=O)CC1=CC(F)=CC(F)=C1 JNGZXGGOCLZBFB-IVCQMTBJSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920004934 Dacron® Polymers 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
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 241000863480 Vinca Species 0.000 description 1
- 238000007718 adhesive strength test Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 1
- VIRZZYBEAHUHST-UHFFFAOYSA-N bicyclo[4.2.0]octa-1,3,5-triene Chemical compound C1CC=2C1=CC=CC2.C2CC=1C2=CC=CC1 VIRZZYBEAHUHST-UHFFFAOYSA-N 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- BXOUVIIITJXIKB-UHFFFAOYSA-N ethene;styrene Chemical group C=C.C=CC1=CC=CC=C1 BXOUVIIITJXIKB-UHFFFAOYSA-N 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L35/06—Copolymers with vinyl aromatic monomers
-
- 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
-
- 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
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
-
- 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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
-
- 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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
-
- 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
- H05K1/036—Multilayers with layers of different types
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Laminated Bodies (AREA)
Abstract
The application provides a metal foil laminated plate, a printed circuit board and a manufacturing method thereof. The metal foil laminate comprises: a substrate coated with a toughened resin composition; a metal foil; wherein the resin composition comprises a toughening modification compound which comprises a styrene maleic anhydride compound, an anhydride grafted olefin polymer and a diisocyanate compound; wherein, in the toughened and modified compound, the diisocyanate forms polyimide bonds with the styrene maleic anhydride compound and the olefin polymer grafted by the anhydride respectively. The application has high toughness and excellent mechanical property, thus having wide application range in the fields of electronics, aerospace and the like.
Description
Technical Field
The present application relates to a metal foil laminate, a printed circuit board and a method for manufacturing the same, and more particularly, to a metal foil laminate, a printed circuit board and a method for manufacturing the same with olefin polymer toughening modified styrene maleic anhydride.
Background
Styrene maleic anhydride (styrene maleic anhydride, SMA) is a copolymer polymerized from styrene monomer and maleic anhydride monomer. The styrene maleic anhydride polymer is characterized by excellent electrical properties, high heat resistance and high dimensional stability, and is widely used in industry and commerce.
However, styrene maleic anhydride polymers also have some disadvantages, such as: after curing and crosslinking, the polymer is hard and brittle, so that the mechanical property is poor, and when the polymer is applied to a Copper Clad Laminate (CCL), the substrate can crack and generate white lines when the substrate is drilled on a Printed Circuit Board (PCB) due to the hard and brittle characteristic after crosslinking, thereby causing short circuit failure. In order to improve the poor processing, rubber or toughening agent is added additionally to improve the toughness so as to improve the hole cracks and white lines, and if the improving effect is not good, a large amount of the toughening agent is needed to be added to achieve the improving effect, however, the physical property or the dielectric property of the polymer may be influenced by the large amount of the toughening agent.
Disclosure of Invention
In view of this, how to improve the properties of styrene maleic anhydride polymer, which makes it applicable to metal foil laminate and printed circuit board with high toughness and excellent mechanical properties, is one of the problems to be solved by the present application.
The main object of the present application is to provide a metal foil laminate comprising: a substrate coated with a toughened resin composition; a metal foil; wherein the resin composition comprises a toughening modification compound which comprises a styrene maleic anhydride compound, an anhydride grafted olefin polymer and a diisocyanate compound; wherein, in the toughened and modified compound, the diisocyanate forms polyimide bonds with the styrene maleic anhydride compound and the olefin polymer grafted by the anhydride respectively.
In a preferred embodiment, the resin composition further comprises a thermosetting polymer.
In a preferred embodiment, the anhydride grafted olefin polymer comprises: styrene-ethylene/butylene-styrene copolymer grafted maleic anhydride, polypropylene grafted maleic anhydride or polyethylene grafted maleic anhydride.
In a preferred embodiment, the diisocyanate is selected from the group consisting of trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1, 2-propylene diisocyanate, 1, 3-butylene diisocyanate, dodecamethylene diisocyanate, 2, 4-trimethylhexamethylene diisocyanate, etc., 1, 3-cyclopentene diisocyanate, 1, 3-cyclohexane diisocyanate, 1, 4-cyclohexane diisocyanate, methylene dicyclohexyl diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated toluene diisocyanate, hydrogenated tetramethylxylylene diisocyanate, phenylene diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, 2 '-diphenylmethane diisocyanate, 4' -toluidine diisocyanate, 4 '-diphenyl ether diisocyanate, 4' -diphenylmethane diisocyanate, 1, 5-naphthalene diisocyanate and xylylene diisocyanate.
In a preferred embodiment, the substrate is a fibrous material.
In a preferred embodiment, the metal foil laminate comprises two layers of the metal foil, with a plurality of layers of the substrate laminated therebetween.
Another object of the present application is to provide a printed circuit board comprising the metal foil laminate as described above.
Another object of the present application is to provide a method for producing the metal foil laminate described above, comprising: (a) preparing a toughened and modified compound: adding a styrene maleic anhydride compound and a solvent, heating to dissolve the styrene maleic anhydride compound and the solvent, adding an olefin polymer grafted by the maleic anhydride, heating to dissolve the olefin polymer, adding a diisocyanate compound, heating and gradually heating the synthetic solution to 120-150 ℃, reacting for 0.5-2 hours, stopping heating and cooling to room temperature; (b) preparing a resin composition: adding thermosetting resin into the toughened and modified compound solution, stirring and dissolving; (c) preparing a prepreg: impregnating or coating a substrate with the resin composition, and drying the substrate to obtain a semi-cured prepreg; (d) preparing a metal foil laminate: the prepreg was laminated with a metal foil laminated on each of the outermost layers on both sides thereof, followed by high-temperature hot-press curing to obtain a metal foil laminated plate.
In a preferred embodiment, step (b) further comprises adding a material selected from the group consisting of polybenzoxazine compounds, epoxy resins, toughening resins, solvents, fillers, and combinations thereof.
In a preferred embodiment, the hot-pressing conditions of step (d) are elevated to 200 ℃ to 220 ℃ at an elevated rate of 3.0 ℃/min, and hot-pressing for 180 minutes at the temperature at a pressure of 8 kg/cm at initial pressure and 15 kg/cm at full pressure.
Therefore, the metal foil laminated plate and the printed circuit board provided by the application comprise a toughening modification compound which toughens and modifies a styrene maleic anhydride compound by using an olefin polymer, and a diisocyanate compound and the diisocyanate compound form a polyimide bond, so that the mechanical property and the electrical property of the substrate can be effectively improved, and the metal foil laminated plate and the printed circuit board provided by the application have good mechanical property and electrical property and low water absorption rate. The application has high toughness and excellent mechanical properties, and therefore, compared with the prior art, the application is more suitable for the application in the field of electronic motors.
Drawings
The details of one or more embodiments of the subject matter described in this specification are set forth in the accompanying drawings and the description below. Other features, aspects, and advantages of the subject matter of the present description will become apparent from the description, the drawings, and the claims, wherein:
FIG. 1 is a schematic representation of a reaction scheme according to a preferred embodiment of the present application.
Wherein, the reference numerals:
100 toughened and modified compound
110 styrene maleic anhydride Compound
120 styrene-ethylene/butene-styrene copolymer grafted maleic anhydride
130 isophorone diisocyanate
Detailed Description
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. As used in the present application, the following terms have the following meanings.
As used herein, terms such as "first," "second," "third," "fourth," and "fifth," etc., describe various elements, components, regions, layers and/or sections that are not limited by these terms. These terms are only used to distinguish one element, component, region, layer or section from another. Unless the context clearly indicates otherwise, terms such as "first", "second", "third", "fourth" and "fifth" as used herein do not imply a sequence or order.
The term "or" as used herein means "and/or" unless otherwise indicated. The terms "comprises" or "comprising" when used herein are intended to exclude the presence of, or the addition to, one or more other elements, steps, operations, and/or components; similarly, the terms "include", "contain", "include", "have" and "have" as used herein are interchangeable and are not limiting. "a" or "an" means that the grammatical object of the article is one or more (i.e., at least one). As used herein and in the claims, the singular forms "a", "an", and "the" include plural referents.
The present application is a metal foil laminate and a printed circuit board comprising the same. The metal foil laminate comprises: a substrate coated with a toughened resin composition; a metal foil; wherein the resin composition comprises a toughening modification compound which comprises a styrene maleic anhydride compound, an anhydride grafted olefin polymer and a diisocyanate compound; wherein, in the toughened and modified compound, the diisocyanate forms polyimide bonds with the styrene maleic anhydride compound and the olefin polymer grafted by the anhydride respectively.
The term "styrene maleic anhydride compound" as used herein includes copolymers (styrene maleic anhydride, SMA) polymerized from styrene monomers and maleic anhydride monomers. In a preferred embodiment, the styrene maleic anhydride compound has a ratio of styrene to maleic anhydride of 3:1 to 6:1, such as but not limited to: 3:1 to 6:1, 3:1 to 5:1, 3:1 to 4:1, 4:1 to 6:1, 5:1 to 6:1, or between any two of the foregoing ratios. In a more preferred embodiment, the styrene maleic anhydride compound has a ratio of styrene to maleic anhydride of 3:1, 4:1, 5:1 or 6:1.
The anhydride grafted olefin-based polymeric polymers described herein have excellent electrical properties, and good impact resistance; preferably, the olefin polymer is grafted with maleic anhydride, has good compatibility with base material resin and achieves the modifying effect. In a preferred embodiment, the anhydride grafted olefin polymer is such as, but not limited to: styrene-ethylene/butylene-styrene copolymer grafted maleic anhydride (SEBS-g-MA), polypropylene grafted maleic anhydride (PP (Poly Propylene) -g-MA) or polyethylene grafted maleic anhydride (PE (Poly Ethylene) -g-MA).
In the diisocyanate compound, the diisocyanate group forms a polyimide bond with the anhydride of the styrene maleic anhydride compound and the anhydride of the olefin polymer grafted by the anhydride, so as to achieve chemical modification. The cyanate ester compound can increase the reactive functional groups in the resin structure, thereby improving the crosslinking density of the epoxy cured product and improving the heat resistance. For example, the cyanate ester compound may be a polyfunctional aliphatic isocyanate compound, a polyfunctional alicyclic isocyanate, a polyfunctional aromatic isocyanate compound, for example: trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1, 2-propylene diisocyanate, 1, 3-butylene diisocyanate, dodecamethylene diisocyanate, 2, 4-trimethylhexamethylene diisocyanate and the like, 1, 3-cyclopentene diisocyanate, 1, 3-cyclohexane diisocyanate, 1, 4-cyclohexane diisocyanate, methylene dicyclohexyl diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate hydrogenated xylylene diisocyanate, hydrogenated toluene diisocyanate, hydrogenated tetramethylxylylene diisocyanate, phenylene diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, 2 '-diphenylmethane diisocyanate, 4' -toluidine diisocyanate, 4 '-diphenyl ether diisocyanate, 4' -diphenyl diisocyanate, 1, 5-naphthalene diisocyanate, xylylene diisocyanate, and the like. In a preferred embodiment, the diisocyanate compound comprises: isophorone diisocyanate (IPDI), methylene dicyclohexyl diisocyanate (Methylene dicyclohexyldiisocyanate or hydrogenated MDI, HMDI), or hexamethylene diisocyanate (Hexamethylene diisocyanate, HDI)).
In a preferred embodiment, the toughened and modified compound of the present application is a composition comprising a styrene maleic anhydride compound (IPDI/SEBS-g-MA/SMA) toughened by grafting maleic anhydride with an isophorone diisocyanate modified styrene-ethylene/butylene-styrene copolymer, a methylene dicyclohexyl diisocyanate modified styrene-ethylene/butylene-styrene copolymer grafted maleic anhydride toughened styrene maleic anhydride compound (HMDI/SEBS-g-MA/SMA), a hexamethylene diisocyanate modified styrene-ethylene/butylene-styrene copolymer grafted maleic anhydride toughened styrene maleic anhydride compound (HDI/SEBS-g-MA/SMA), an isophorone diisocyanate modified polypropylene grafted maleic anhydride toughened styrene maleic anhydride compound (IPDI/PP-g-MA/SMA), a methylene dicyclohexyl diisocyanate modified polypropylene grafted maleic anhydride toughened styrene maleic anhydride compound (HMDI/PP-g-MA/SMA), a hexamethylene diisocyanate grafted maleic anhydride toughened styrene maleic anhydride compound (HDI/PP-g-MA), a hexamethylene diisocyanate grafted maleic anhydride toughened styrene maleic anhydride compound (HDI/MA-MA/SMA), an isocyanate grafted maleic anhydride toughened styrene maleic anhydride compound (IPDI/PP-g-MA/SMA), the group consisting of a styrene maleic anhydride compound toughened by grafting maleic anhydride to methylene dicyclohexyl diisocyanate modified polyethylene (HMDI/PE-g-MA/SMA) and a styrene maleic anhydride compound toughened by grafting maleic anhydride to hexamethylene diisocyanate modified polyethylene (HDI/PE-g-MA/SMA).
In a preferred embodiment, the resin composition comprises (A) a toughening modifier compound; (B) a thermosetting polymer; and/or (C) a toughening resin. In a preferred embodiment, in the toughened resin composition of the present application, (a) the toughened modifying compound: (B) thermosetting polymer: the composition ratio of the (C) toughening resin is 15 to 30:20 to 35:0.1 to 5. For example: (A) The toughening modification compound accounts for 15 to 30 percent of the whole resin composition, such as: 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30% or between any two of the foregoing; (B) Thermosetting polymers are 20% to 35% of the total resin composition, such as: 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35% or between any two of the foregoing; (C) The toughening resin is 0.1% to 5% of the total resin composition, such as: 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% or between any two of the foregoing values.
In a preferred embodiment, the toughening resin of the present application is a core shell polymer and/or polybutadiene resin. Core-shell polymers such as core-shell rubbers (core shell rebber, CSR). Such as polybutadiene homopolymer or butadiene-styrene copolymer.
The thermosetting polymer of the application may also be bismaleimide trimethamidePolymers, cyanate ester polymers, benzocyclobutene (benzocyclobutene) polymers, or phenolic resins (phenolic). In a preferred embodiment, the thermosetting polymer of the present application is a Bismaleimide (BMI) resin having carbonyl groups, a nitrogen-containing epoxy resin, and is cured by unsaturation of the end groups during processing without generating volatile materials during curing, which facilitates processing into composite materials.
In a preferred embodiment, the substrate is a fibrous material, such as: glass fiber cloth. In a preferred embodiment, the metal foil laminate comprises two layers of the metal foil, a plurality of layers of the substrate being laminated therebetween, the plurality of layers being, for example: two, three, four, five, six, seven, eight, nine, ten or more than ten layers.
The toughened resin composition of the present application may further comprise: a filler, a polybenzoxazine compound and/or a solvent.
In a preferred embodiment, the filler is an inorganic filler, such as: selected from the group consisting of silica, alumina, aluminum hydroxide, magnesium oxide, magnesium hydroxide, calcium carbonate, aluminum nitride, boron nitride, aluminum silicon carbide, titanium dioxide, zinc oxide, zirconium oxide, barium sulfate, magnesium carbonate, barium carbonate, mica, talc, and graphene.
In a preferred embodiment, the polybenzoxazine compound is a bisphenol type polybenzoxazine or a diamine type polybenzoxazine. In a more preferred embodiment, the polybenzoxazine compound is at least one selected from the group consisting of bisphenol A type benzoxazine (BPA-BZ), bisphenol F type benzoxazine (BPF-BZ), bisphenol S type benzoxazine (BPS-BZ), diaminodiphenyl methane type benzoxazine (DDM-BZ), diaminodiphenyl ether type benzoxazine (ODA-BZ) and polyimide type benzoxazine (polybenzoxazine with polyimide).
In a preferred embodiment, the solvent is selected from the group consisting of toluene, gamma-butyrolactone, methyl ethyl ketone, cyclohexanone, methyl ethyl ketone, acetone, xylene, methyl isobutyl ketone, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, and combinations thereof.
Further, the method for manufacturing a metal foil laminate of the present application comprises: (a) preparing a toughened and modified compound: adding a styrene maleic anhydride compound and a solvent, heating to dissolve the styrene maleic anhydride compound and the solvent, adding an olefin polymer grafted by the maleic anhydride, heating to dissolve the olefin polymer, adding a diisocyanate compound, heating and gradually heating the synthetic solution to 120-150 ℃, reacting for 0.5-2 hours, stopping heating and cooling to room temperature; (b) preparing a resin composition: adding thermosetting resin into the toughened and modified compound solution, stirring and dissolving; (c) preparing a prepreg: impregnating or coating a substrate with the resin composition, and drying the substrate to obtain a semi-cured prepreg; (d) preparing a metal foil laminate: the prepreg was laminated with a metal foil laminated on each of the outermost layers on both sides thereof, followed by high-temperature hot-press curing to obtain a metal foil laminated plate.
In a preferred embodiment, step (a) is to add a styrene maleic anhydride compound and a solvent to a reaction flask, heat to about 50 to 80 ℃ and stir well; the reaction is warmed to 50 to 80 ℃, such as but not limited to: 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃ or any two values between the two. In a preferred embodiment, step (a) is to gradually (e.g., within 20 minutes) add an anhydride grafted olefin polymer to the solution under stirring, and then raise the temperature to 80 to 100 ℃ to dissolve the polymer completely, thereby forming a synthetic solution; the reaction is raised to 80 to 100 ℃, such as but not limited to: 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃ or any two values between the two values. In a preferred embodiment, step (a) is to add diisocyanate compound, heat and gradually raise the temperature of the synthesized solution to 120 to 150 ℃ and react for 0.5 to 2 hours; the reaction is raised to 120 to 150 ℃, such as but not limited to: 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃ or any two values between the two values; the reaction time is 0.5 to 2 hours, such as but not limited to: 0.5 hours, 1 hour, 1.5 hours, 2 hours or between the two time points.
In a preferred embodiment, step (b) further comprises adding a material selected from the group consisting of polybenzoxazine compounds, epoxy resins, toughening resins, solvents, fillers, and combinations thereof.
In a preferred embodiment, the hot pressing conditions of step (d) are elevated to a temperature of 200 ℃ to 220 ℃ at a rate of about 3.0 ℃/min and hot pressing at that temperature for about 180 minutes at a pressure of about 8 kg/cm at initial pressure and about 15 kg/cm at full pressure.
The application not only forms the chemical modification of polyimide bond by the reaction of isocyanate and anhydride, but also achieves the effect of toughening and improving by the modification of olefin polymer and styrene maleic anhydride compound, so that the application has high toughness and excellent mechanical property.
Examples
The present application will be further described in terms of detailed description and embodiments, however, it should be understood that these embodiments are merely used to facilitate easier understanding of the present application and to clarify aspects of the present application and the benefits achieved thereby, and are not intended to limit the scope of the present application.
Example 1
7 toughened and modified compounds (example compounds A-G) were prepared according to the present application. Metal foil laminates were then prepared using the example compounds a-G.
Examples Compound A
Referring to the exemplary reaction scheme of fig. 1, m, n, X, Y in fig. 1 is the same or different positive integer. 200 g of styrene maleic anhydride compound 110 (styrene/maleic anhydride ratio: 3/1) and 600 g of toluene were charged into a 3 liter four-port separable reaction flask equipped with a heating device, thermometer, stirrer, cooling tube, heated to about 60℃and stirred uniformly to dissolve completely. With stirring, 5 g of styrene-ethylene/butylene-styrene copolymer grafted maleic anhydride 120 were gradually added to the toluene solution over 20 minutes, at which time the temperature of the synthesis solution was raised to 90℃to allow complete dissolution. Next, about 5 g of isophorone diisocyanate 130 was added, the synthetic solution was heated and gradually warmed to about 130℃and reacted for 1 hour. And then stopping heating and cooling to room temperature to obtain the compound A of the embodiment, namely the toughened and modified compound 100.
Examples compound B
200 g of a styrene maleic anhydride compound (styrene/maleic anhydride ratio: 3/1) and 600 g of toluene were added to a 3 liter four-port separable reaction flask equipped with a heating device, a thermometer, a stirrer, and a cooling tube, heated to about 60℃and stirred uniformly to be completely dissolved. With stirring, 5 g of polypropylene-grafted maleic anhydride were gradually added to the toluene solution over 20 minutes, at which time the temperature of the synthesis solution was raised to 90℃to allow complete dissolution. Next, about 5 g of isophorone diisocyanate was added, the synthesis solution was heated and gradually warmed to about 130℃and reacted for 1 hour. And then stopping heating and cooling to room temperature to obtain the compound B of the example.
Examples compound C
200 g of a styrene maleic anhydride compound (styrene/maleic anhydride ratio: 3/1) and 600 g of toluene were added to a 3 liter four-port separable reaction flask equipped with a heating device, a thermometer, a stirrer, and a cooling tube, heated to about 60℃and stirred uniformly to be completely dissolved. With stirring, 5 g of polyethylene-grafted maleic anhydride were gradually added to the toluene solution over 20 minutes, at which time the temperature of the synthesis solution was raised to 90℃to allow complete dissolution. Next, about 5 g of isophorone diisocyanate was added, the synthesis solution was heated and gradually warmed to about 130℃and reacted for 1 hour. And then stopping heating and cooling to room temperature to obtain the compound C of the example.
Examples compound D
200 g of a styrene maleic anhydride compound (styrene/maleic anhydride ratio: 4/1) and 600 g of toluene were added to a 3 liter four-port separable reaction flask equipped with a heating device, a thermometer, a stirrer, and a cooling tube, heated to about 60℃and stirred uniformly to be completely dissolved. While stirring, 5 g of styrene-ethylene/butylene-styrene copolymer grafted maleic anhydride were gradually added to the toluene solution over 20 minutes, at which time the temperature of the synthesis solution was raised to 90℃to allow complete dissolution. Next, about 5 g of isophorone diisocyanate was added, the synthesis solution was heated and gradually warmed to about 130℃and reacted for 1 hour. And then stopping heating and cooling to room temperature to obtain the compound D of the example.
Examples Compound E
200 g of a styrene maleic anhydride compound (styrene/maleic anhydride ratio: 6/1) and 600 g of toluene were added to a 3 liter four-port separable reaction flask equipped with a heating device, a thermometer, a stirrer, and a cooling tube, heated to about 60℃and stirred uniformly to be completely dissolved. With stirring, 5 g of styrene-ethylene/butylene-styrene copolymer grafted maleic anhydride were gradually added to the toluene solution over 20 minutes, at which time the temperature of the synthesis solution was raised to 90℃to allow complete dissolution. Next, about 5 g of isophorone diisocyanate was added, the synthesis solution was heated and gradually warmed to about 130℃and reacted for 1 hour. And then stopping heating and cooling to room temperature to obtain the compound E of the example.
Examples compound F
200 g of a styrene maleic anhydride compound (styrene/maleic anhydride ratio: 3/1) and 600 g of toluene were added to a 3 liter four-port separable reaction flask equipped with a heating device, a thermometer, a stirrer, and a cooling tube, heated to about 60℃and stirred uniformly to be completely dissolved. With stirring, 5 g of styrene-ethylene/butylene-styrene copolymer grafted maleic anhydride were gradually added to the toluene solution over 20 minutes, at which time the temperature of the synthesis solution was raised to 90℃to allow complete dissolution. Next, about 5 g of methylene dicyclohexyl diisocyanate was added, the synthesis solution was heated and gradually warmed to about 130℃and reacted for 1 hour. And then stopping heating and cooling to room temperature to obtain the compound F of the example.
Examples Compound G
200 g of a styrene maleic anhydride compound (styrene/maleic anhydride ratio: 3/1) and 600 g of toluene were added to a 3 liter four-port separable reaction flask equipped with a heating device, a thermometer, a stirrer, and a cooling tube, heated to about 60℃and stirred uniformly to be completely dissolved. With stirring, 5 g of styrene-ethylene/butylene-styrene copolymer grafted maleic anhydride were gradually added to the toluene solution over 20 minutes, at which time the temperature of the synthesis solution was raised to 90℃to allow complete dissolution. Next, about 5 g of hexamethylene diisocyanate was added, the synthesis solution was heated and gradually warmed to about 130℃and reacted for 1 hour. And then stopping heating and cooling to room temperature to obtain the compound G of the example.
Material
Styrene maleic anhydride compounds having a styrene/maleic anhydride ratio of 3/1, 4/1 and 6/1 are produced by Polyscope; styrene-ethylene/butylene-styrene copolymer grafted maleic anhydride was produced by taiwan Li Changrong company; polypropylene grafted maleic anhydride is produced by ExxonMobil chemical company, exxelor, product model Exxelor TM PO1015; the polyethylene grafted maleic anhydride is produced by Exxelor chemical industry company, product model Exxelor TM PE1040。
Table 1 below shows the preparation ingredients and contents of the compounds A to G of the examples.
TABLE 1
Remarks: SMA (3/1) in the table represents a styrene maleic anhydride compound having a styrene/maleic anhydride ratio of 3/1; SMA (4/1) represents a styrene maleic anhydride compound having a styrene/maleic anhydride ratio of 4/1; SMA (6/1) represents a styrene maleic anhydride compound having a styrene/maleic anhydride ratio of 6/1.
Example 2
The following provides a non-limiting method of preparing the toughened and modified compounds of the present application into metal foil laminate. Ten non-limiting example laminates (example laminates 1-10) and six comparative example laminates (comparative example laminates 1-6) were prepared with example compounds according to a method similar to the method disclosed below. However, the specific methods of preparing the example laminate plates 1 to 10 and the comparative example laminate plates 1 to 6 will generally differ in one or more respects from the methods disclosed below.
Example laminate 1
Preparation of a resin composition: the solution of the compound A of the above example was taken at 30 g, 10 g of bisphenol A type polybenzoxazine (BPA-Benzoxazine, BPA-BZ), 5 g of thermosetting resin (BMI), 25 g of epoxy resin (brominated epoxy), 1 g of toughening resin (Ricon 100) and 40 g of solvent (butanone, MEK) were added, and the mixture was uniformly mixed by a homogenizing mixer to dissolve the respective components. After the resin was completely dissolved, 30 g of silica was added thereto, and the mixture was uniformly mixed with a homogenizing mixer and dispersed in a solvent to prepare a varnish-like resin composition.
Preparing a prepreg: the reinforcing material Glass fiber cloth (base material E-Glass) is impregnated or coated with the varnish liquid resin composition, and the impregnated or coated base material is dried at 80 ℃ for 3 minutes and 180 ℃ for 7 minutes to obtain a prepreg in a semi-cured state (B-stage).
Preparing a metal foil laminated plate: four prepregs were laminated, and 0.5oz of metal foil (copper foil) was laminated on each of the outermost layers on both sides thereof, followed by hot press curing at high temperature. The hot pressing conditions are as follows: the temperature is raised to 200 ℃ to 220 ℃ at a heating rate of 3.0 ℃/min, and the copper foil laminated plate is prepared by hot pressing for 180 minutes at a pressure of 15 kg/square centimeter (8 kg/square centimeter at initial pressure) at the temperature.
Examples laminate panels 2-10
The example laminate sheets 2-10 were prepared according to a method similar to that of example laminate sheet 1, however, example laminate sheets 2-10 may differ in one or more respects, with the specific differences shown in table 2 below.
Table 2 shows the preparation compositions and contents of the laminate sheets 1 to 10 of examples, and the results of measuring the physical properties such as the adhesion strength, the thermal expansion coefficient in the Z-axis direction of the thermal expansion coefficient, the heat resistance, the dielectric properties and the drilled hole white streak.
TABLE 2
Remarks: SMA (3/1) in the table represents a styrene maleic anhydride compound having a styrene/maleic anhydride ratio of 3/1; SMA (4/1) represents a styrene maleic anhydride compound having a styrene/maleic anhydride ratio of 4/1; SMA (6/1) represents a styrene maleic anhydride compound having a styrene/maleic anhydride ratio of 6/1. CSR is core-shell rubber body. Ricon 100 is a butadiene-styrene copolymer. EG represents E-Glass. The units of addition of each component in the table are grams.
Comparative example laminate 1
Preparation of a resin composition: 7.5 g of styrene maleic anhydride (styrene/maleic anhydride ratio 3/1) which was not toughened and modified was dissolved in 22.5 g of toluene, 10 g of BPA-BZ, 5 g of thermosetting resin (BMI), 25 g of epoxy resin (brominated epoxy), 2.5 g of toughening resin (Ricon 100) and 40 g of solvent (butanone, MEK) were added and mixed uniformly by a homogenizing mixer to dissolve the components. After the resin was completely dissolved, 30 g of silica was added thereto, and the mixture was uniformly mixed with a homogenizing mixer and dispersed in a solvent to prepare a varnish-like resin composition.
Preparing a prepreg: the reinforcing material Glass fiber cloth (base material E-Glass) is impregnated or coated with the varnish liquid resin composition, and the impregnated or coated base material is dried at 80 ℃ for 3 minutes and 180 ℃ for 7 minutes to obtain a prepreg in a semi-cured state (B-stage).
Preparing a metal foil laminated plate: four prepregs were laminated, and 0.5oz of copper foil was laminated on each of the outermost layers on both sides, followed by hot press curing at high temperature. The hot pressing conditions are as follows: heating to 200 ℃ to 220 ℃ at a heating rate of 3.0 ℃/min, and hot-pressing at the temperature for 180 minutes at a pressure of 15 kg/square centimeter (8 kg/square centimeter at initial pressure). To obtain a copper foil laminate.
Comparative example laminate 2-6
Comparative example laminate sheets 2-6 were prepared in a similar manner to comparative example laminate sheet 1, however comparative example laminate sheets 2-6 may differ in one or more respects, the specific differences being disclosed in Table 3 below.
Table 3 shows the preparation components and contents of the laminate sheets 1 to 6 of the comparative examples, and the results of measuring the adhesion strength, thermal expansion coefficient in the Z-axis direction, heat resistance and other physical properties, dielectric properties and drilled hole white streak test.
TABLE 3 Table 3
Remarks: SMA (3/1) in the table represents a styrene maleic anhydride compound having a styrene/maleic anhydride ratio of 3/1; SMA (4/1) represents a styrene maleic anhydride compound having a styrene/maleic anhydride ratio of 4/1; SMA (6/1) represents a styrene maleic anhydride compound having a styrene/maleic anhydride ratio of 6/1. CSR is core-shell rubber body. Ricon 100 is a butadiene-styrene copolymer. EG represents E-Glass. The units of addition of each component in the table are grams.
Material
BPA-BZ is produced by Yuanhong corporation; filler SiO 2 Is a 10um cut produced by the company silviceae; thermosetting resins BMI are produced by Dacron and Chemie; brominated epoxy resins are produced by vinca resin company; the reinforcing material is E-Glass cloth 2116 produced by Taibo Glass company; the toughening resin is Ricon 100 manufactured by CSR, polyscope company manufactured by Kaneka company; the copper foil was H1.5 OZ from Nanya.
Characterization test
Drilling white lines: 100 mechanical holes are drilled on a sample by using a mechanical drill, the inner diameter of each hole is 0.3mm, the number of white lines and Kong Lie holes of the drilled holes are observed, and the white lines and hole cracks influence the hole filling effect of the resin so as to cause the explosion plate phenomenon.
CTE test: according to IPC-TM-650.2.4.24.5 specifications, the coefficient of thermal expansion (coefficient of thermal exapansion, CTE) change rate (total Z-CTE) in the Z-axis direction of a thermal expansion Coefficient (CTE) of a sample to be measured at a temperature lower than the glass transition temperature (Tg) is measured using a thermo-mechanical analyzer (thermal mechanical analyzer, TMA). Z-CTE is measured in% at a temperature in the range of 50 ℃ to 260 ℃.
And (3) adhesive strength test: the adhesion strength is the adhesion of the metal foil to the laminated prepreg, and in this test, the adhesion is expressed by the amount of force required by tearing a copper foil of 1/8 inch width vertically from the panel. Tear strength is in pounds force per inch (lbf/in).
Heat resistance test: immersing the dried metal foil laminate in a solder bath at 288 ℃ for 100 seconds, repeating the process 3 times, showing excellent heat resistance, and recording as "" O ""; when the appearance had a bubbling bulge, it was recorded as "×" indicating that the heat resistance was poor.
From the above results, it is understood that, compared with the laminate sheets 1 to 6 of the comparative examples which contain styrene maleic anhydride which has not been toughened and modified, the crosslinked laminate sheets 1 to 10 of the examples have the characteristics that they are not excellent in mechanical properties and cannot be improved even if a large amount of toughening agent or rubber is externally added, the laminate sheets 1 to 10 of the examples contain the toughened and modified compound, exhibit good mechanical properties and electrical properties, have a low water absorption, and can also reduce the amount of externally added toughening agent or rubber. Therefore, the application is more suitable for being applied to the wide fields of composite materials, electronic circuit materials and the like.
In summary, the present application provides a metal foil laminate, a printed circuit board and a method for manufacturing the same, wherein the metal foil laminate comprises an olefin polymer for toughening and modifying a styrene maleic anhydride compound, and a diisocyanate compound and the diisocyanate compound form a polyimide bond, so that the metal foil laminate has good mechanical properties and electrical properties, and low water absorption. Therefore, compared with the characteristics of hard and brittle after the styrene maleic anhydride polymer is crosslinked and poor mechanical properties in the prior art, the application is more suitable for the application in the field of electronic motors.
The terms "substantially" and "about" are used herein and are not otherwise defined as describing or claiming small variations. When combined with an event or circumstance, the term can include the exact whereabouts of the event or circumstance and the whereabouts of the event or circumstance to a close approximation. For example, when combined with a numerical value, the term can include a variation of less than or equal to + -10%, such as less than or equal to + -5%, less than or equal to + -4%, less than or equal to + -3%, less than or equal to + -2%, less than or equal to + -1%, less than or equal to + -0.5%, less than or equal to + -0.1%, or less than or equal to + -0.05% of the numerical value.
The foregoing has outlined the components of several embodiments so that those skilled in the art may better understand the concepts of the embodiments of the application. It will be appreciated by those skilled in the art that the embodiments of the application may be used as a basis for designing or modifying other processes and structures for carrying out the same purposes and/or achieving the same advantages of the embodiments introduced herein. Those skilled in the art to which the application pertains will also appreciate that such equivalent constructions do not depart from the spirit and scope of the application and that they may make various changes, substitutions and other selections herein without departing from the spirit and scope of the application. Accordingly, the scope of the application is defined by the appended claims.
Claims (10)
1. A metal foil laminate, comprising:
a substrate coated with a toughened resin composition; and
A metal foil;
wherein the resin composition comprises a toughening modification compound which comprises a styrene maleic anhydride compound, an anhydride grafted olefin polymer and a diisocyanate compound; wherein, in the toughened and modified compound, the diisocyanate forms polyimide bonds with the styrene maleic anhydride compound and the olefin polymer grafted by the anhydride respectively.
2. The metal foil laminate of claim 1 wherein the resin composition further comprises a thermosetting polymer.
3. The metal foil laminate of claim 1 wherein the anhydride grafted olefinic polymeric macromolecule comprises: styrene-ethylene/butylene-styrene copolymer grafted maleic anhydride, polypropylene grafted maleic anhydride or polyethylene grafted maleic anhydride.
4. The metal foil laminate of claim 1, wherein the diisocyanate is selected from the group consisting of trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1, 2-propylene diisocyanate, 1, 3-butylene diisocyanate, dodecamethylene diisocyanate, 2, 4-trimethylhexamethylene diisocyanate, etc., 1, 3-cyclopentene diisocyanate, 1, 3-cyclohexane diisocyanate, 1, 4-cyclohexane diisocyanate, methylene dicyclohexyl diisocyanate, isophorone diisocyanate hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated toluene diisocyanate, hydrogenated tetramethylxylylene diisocyanate, phenylene diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, 2 '-diphenylmethane diisocyanate, 4' -toluidine diisocyanate, 4 '-diphenyl ether diisocyanate, 4' -diphenyl diisocyanate, 1, 5-naphthalene diisocyanate and xylylene diisocyanate.
5. The metal foil laminate of claim 1 wherein the substrate is a fibrous material.
6. The metal foil laminate of claim 1, wherein the metal foil laminate comprises two layers of the metal foil, the two layers of metal foil sandwiching the substrate.
7. A printed circuit board comprising the metal foil laminate of any one of claims 1 to 6.
8. A method of manufacturing the metal foil laminate according to any one of claims 1 to 6, comprising:
(a) Preparing a toughened and modified compound: adding a styrene maleic anhydride compound and a solvent, heating to dissolve the styrene maleic anhydride compound and the solvent, adding an olefin polymer grafted by the maleic anhydride, heating to dissolve the olefin polymer, adding a diisocyanate compound, heating and gradually heating the synthetic solution to 120-150 ℃, reacting for 0.5-2 hours, stopping heating and cooling to room temperature;
(b) Preparation of a resin composition: adding thermosetting resin into the toughened and modified compound solution, stirring and dissolving;
(c) Preparing a prepreg: impregnating or coating a substrate with the resin composition, and drying the substrate to obtain a semi-cured prepreg; and
(d) Preparing a metal foil laminated plate: the prepreg was laminated with a metal foil laminated on each of the outermost layers on both sides thereof, followed by high-temperature hot-press curing to obtain a metal foil laminated plate.
9. The method of claim 8, wherein step (b) further comprises adding a material selected from the group consisting of polybenzoxazine compounds, epoxy resins, toughening resins, solvents, fillers, and combinations thereof.
10. The manufacturing method according to claim 8, wherein the hot pressing condition of step (d) is to heat up to 200 ℃ to 220 ℃ at a heating rate of 3.0 ℃/min, and to heat press at the temperature for 180 minutes at a pressure of 8 kg/cm at initial pressure and 15 kg/cm at full pressure.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210475667.1A CN117002106A (en) | 2022-04-29 | 2022-04-29 | Metal foil laminate, printed circuit board and method for manufacturing the same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210475667.1A CN117002106A (en) | 2022-04-29 | 2022-04-29 | Metal foil laminate, printed circuit board and method for manufacturing the same |
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| CN117002106A true CN117002106A (en) | 2023-11-07 |
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| CN202210475667.1A Pending CN117002106A (en) | 2022-04-29 | 2022-04-29 | Metal foil laminate, printed circuit board and method for manufacturing the same |
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