CN115637013A - Bismaleimide composition, semi-cured film and copper foil substrate - Google Patents
Bismaleimide composition, semi-cured film and copper foil substrate Download PDFInfo
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- CN115637013A CN115637013A CN202211348078.3A CN202211348078A CN115637013A CN 115637013 A CN115637013 A CN 115637013A CN 202211348078 A CN202211348078 A CN 202211348078A CN 115637013 A CN115637013 A CN 115637013A
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- Prior art keywords
- bismaleimide
- styrene
- parts
- maleic anhydride
- monomer
- Prior art date
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Links
- 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 title claims abstract description 36
- 229920003192 poly(bis maleimide) Polymers 0.000 title claims abstract description 36
- 239000000203 mixture Substances 0.000 title claims abstract description 27
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 239000011889 copper foil Substances 0.000 title claims abstract description 11
- 239000000758 substrate Substances 0.000 title claims abstract description 11
- 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 abstract description 30
- 229920000147 Styrene maleic anhydride Polymers 0.000 claims abstract description 30
- 239000003822 epoxy resin Substances 0.000 claims abstract description 23
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 23
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 13
- -1 m-benzylphosphine Chemical compound 0.000 claims description 21
- 239000003063 flame retardant Substances 0.000 claims description 15
- 239000000178 monomer Substances 0.000 claims description 15
- 239000011256 inorganic filler Substances 0.000 claims description 14
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 9
- 150000008064 anhydrides Chemical class 0.000 claims description 9
- 229910052751 metal Chemical class 0.000 claims description 9
- 239000002184 metal Chemical class 0.000 claims description 9
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims description 9
- 238000004132 cross linking Methods 0.000 claims description 8
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical class CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 6
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 239000012948 isocyanate Substances 0.000 claims description 6
- 150000002513 isocyanates Chemical class 0.000 claims description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical class C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 6
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims description 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical class CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 3
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical class C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 claims description 3
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical class CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 3
- 229910015900 BF3 Inorganic materials 0.000 claims description 3
- 229910052582 BN Inorganic materials 0.000 claims description 3
- 229930185605 Bisphenol Natural products 0.000 claims description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 3
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- 229920000388 Polyphosphate Polymers 0.000 claims description 3
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 3
- PZBFGYYEXUXCOF-UHFFFAOYSA-N TCEP Chemical compound OC(=O)CCP(CCC(O)=O)CCC(O)=O PZBFGYYEXUXCOF-UHFFFAOYSA-N 0.000 claims description 3
- BQPNUOYXSVUVMY-UHFFFAOYSA-N [4-[2-(4-diphenoxyphosphoryloxyphenyl)propan-2-yl]phenyl] diphenyl phosphate Chemical compound C=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 BQPNUOYXSVUVMY-UHFFFAOYSA-N 0.000 claims description 3
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 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
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 3
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 3
- GCKAMTHMSCXVIL-UHFFFAOYSA-N bis(2,3-dimethylphenyl) (3-hydroxyphenyl) phosphate Chemical compound P(=O)(OC1=C(C(=CC=C1)C)C)(OC1=C(C(=CC=C1)C)C)OC1=CC(O)=CC=C1 GCKAMTHMSCXVIL-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 229910001593 boehmite Inorganic materials 0.000 claims description 3
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Substances FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 3
- 239000012933 diacyl peroxide Substances 0.000 claims description 3
- VONWDASPFIQPDY-UHFFFAOYSA-N dimethyl methylphosphonate Chemical compound COP(C)(=O)OC VONWDASPFIQPDY-UHFFFAOYSA-N 0.000 claims description 3
- NJXBVBPTDHBAID-UHFFFAOYSA-M ethyl(triphenyl)phosphanium;chloride Chemical class [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 NJXBVBPTDHBAID-UHFFFAOYSA-M 0.000 claims description 3
- WOLATMHLPFJRGC-UHFFFAOYSA-N furan-2,5-dione;styrene Chemical compound O=C1OC(=O)C=C1.C=CC1=CC=CC=C1 WOLATMHLPFJRGC-UHFFFAOYSA-N 0.000 claims description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims description 3
- 239000010445 mica Substances 0.000 claims description 3
- 229910052618 mica group Inorganic materials 0.000 claims description 3
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 claims description 3
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims description 3
- MMCOUVMKNAHQOY-UHFFFAOYSA-L oxido carbonate Chemical compound [O-]OC([O-])=O MMCOUVMKNAHQOY-UHFFFAOYSA-L 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- 150000002978 peroxides Chemical class 0.000 claims description 3
- 125000000864 peroxy group Chemical group O(O*)* 0.000 claims description 3
- VWSUVZVPDQDVRT-UHFFFAOYSA-N phenylperoxybenzene Chemical compound C=1C=CC=CC=1OOC1=CC=CC=C1 VWSUVZVPDQDVRT-UHFFFAOYSA-N 0.000 claims description 3
- 239000001205 polyphosphate Substances 0.000 claims description 3
- 235000011176 polyphosphates Nutrition 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 3
- 239000000454 talc Substances 0.000 claims description 3
- 229910052623 talc Inorganic materials 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 3
- XKCQNWLQCXDVOP-UHFFFAOYSA-N tris(2-chloropropan-2-yl) phosphate Chemical compound CC(C)(Cl)OP(=O)(OC(C)(C)Cl)OC(C)(C)Cl XKCQNWLQCXDVOP-UHFFFAOYSA-N 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims 1
- 230000001070 adhesive effect Effects 0.000 claims 1
- 230000009477 glass transition Effects 0.000 abstract description 7
- 229920005989 resin Polymers 0.000 abstract description 7
- 239000011347 resin Substances 0.000 abstract description 7
- 239000002245 particle Substances 0.000 description 12
- 239000000843 powder Substances 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 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 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 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 4
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- MMEDJBFVJUFIDD-UHFFFAOYSA-N 2-[2-(carboxymethyl)phenyl]acetic acid Chemical compound OC(=O)CC1=CC=CC=C1CC(O)=O MMEDJBFVJUFIDD-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 2
- 150000003923 2,5-pyrrolediones Chemical class 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
- 238000013473 artificial intelligence Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000004643 cyanate ester Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Abstract
The invention discloses a bismaleimide composition, a semi-cured film and a copper foil substrate; the bismaleimide composition comprises 30-90 parts of bismaleimide, 20-60 parts of alicyclic epoxy resin and 55-330 parts of styrene-maleic anhydride copolymer. The bismaleimide composition prepared by the formula has lower thermal expansion coefficient, higher glass transition temperature, lower dielectric constant and lower dielectric loss, can be prepared into semi-cured films or resin films, and further achieves the aim of being applied to copper foil substrates and printed circuit boards.
Description
Technical Field
The invention relates to the technical field of 5G, in particular to a bismaleimide composition, a semi-cured film and a copper foil substrate.
Background
With the increasing demand of people on mobile data, 5G has wider and wider application in the fields of internet of things, artificial intelligence, smart cities and the like due to the characteristics of large transmission data, high transmission rate and low delay, and therefore, the human society is continuously accelerated to enter the 'everything interconnection' era. With the continuous development of 5G, PCB is developed to high precision and high density, the requirements for CCL are continuously improved, and the CCL has the characteristics of low dielectric constant, low dielectric loss, high TG, low thermal expansion coefficient and the like.
At present, the CCL board which can meet the application characteristics is mainly a BT-type board, however, the BT-type high-end printed board applied to 5G is monopolized by Europe and America, and the BT-type high-end printed board used in China is mainly imported. With the continuous development of 5G, the technical blockade for breaking through BT products becomes imperative. Among them, chinese patent CN110997755A discloses a resin composition containing a maleimide compound (a) represented by the following formula (1) and a cyanate ester compound, which has a low thermal expansion coefficient and a high glass transition temperature, but its dielectric constant of 4.41 is still high for an IC package carrier, and there is room for improvement of the dielectric properties of the substrate. Therefore, there is a need for improvement of the existing maleimide compounds.
Disclosure of Invention
In view of the above, the present invention provides a bismaleimide composition, a prepreg and a copper clad laminate, which have a low thermal expansion coefficient, a high glass transition temperature, a low dielectric constant and a low dielectric loss, and can be made into a prepreg or a resin film, thereby achieving the purpose of being applicable to a copper clad laminate and a printed circuit board.
In order to achieve the purpose, the invention adopts the following technical scheme:
a bismaleimide composition comprises 30-90 parts of bismaleimide, 20-60 parts of alicyclic epoxy resin and 55-330 parts of styrene-maleic anhydride copolymer; wherein the general formula of the bismaleimide is as follows:
in the general formula R 1 Is one of the following groups:
the structural general formula of the alicyclic epoxy resin is as follows:
r2 in the general formula is one of-CH of the following groups 3 、
The styrene-maleic anhydride copolymer introduces a styrene structure with good dielectric property into a cross-linking structure in a reaction system to realize low dielectric constant and dielectric loss, and the bismaleimide resin and the alicyclic epoxy resin are both symmetrical structures and have low intermolecular polarity, so that the dielectric loss can be reduced after the bismaleimide resin and the alicyclic epoxy resin are compounded.
As a preferable scheme, the styrene-maleic anhydride copolymer is a styrene-maleic anhydride copolymer with high styrene/maleic anhydride molar ratio, and the percentage of the anhydride molar mass is more than 3%; styrene-maleic anhydride copolymers with lower anhydride molar masses (generally less than 3%) are less suitable for compounding with epoxy resins.
As a preferable embodiment, the weight average molecular weight (Mw) of the styrene-maleic anhydride copolymer is between 9000 and 60000; styrene-maleic anhydride copolymers with too high a molecular weight (Mw generally higher than 60000) have poor compatibility with epoxy resins and are not suitable for printed circuit boards. Experiments prove that the styrene-maleic anhydride copolymer with the weight-average molecular weight of 3000-60000 and the acid anhydride content of more than 3% can be compounded with epoxy resin to be applied to printed circuit boards, in particular, the styrene-maleic anhydride copolymer with the weight-average molecular weight of 5000-12000, the molar ratio of styrene (S) to Maleic Anhydride (MA) of 4.
As a preferable embodiment, the weight average molecular weight (Mw) of the styrene-maleic anhydride copolymer is between 10000 and 15000.
As a preferable embodiment, the sum of the equivalents of the maleimide groups and the equivalents of the acid anhydride is: the equivalent weight of the alicyclic epoxy resin is (0.6-1.6): 1; the styrene-maleic anhydride copolymer is applied to the printed circuit board as a curing agent of the epoxy resin, and the equivalent ratio (styrene-maleic anhydride copolymer anhydride and phenolic hydroxyl group: epoxy resin) is properly in the range of (0.6-1.6): 1, and the optimal ratio is (0.9-1.1): 1.
As a preferable scheme, the halogen-free flame retardant further comprises 3-9 parts of halogen-free flame retardant; the flame retardant is a nitrogen-containing flame retardant or a phosphorus-containing flame retardant, and at least one of the following compounds can be selectively added into the halogen-free flame retardant, but the flame retardant is not limited to the following compounds: bisphenol diphenyl phosphate, ammonium polyphosphate, hydroquinone-bis- (diphenyl phosphate), bisphenol a-bis- (diphenyl phosphate), tris (2-carboxyethyl) phosphine, tris (chloroisopropyl) phosphate, trimethyl phosphate, dimethyl methylphosphonate, resorcinol dixylyl phosphate, phosphazene, m-benzylphosphine, melamine polyphosphate, melamine cyanurate, tris-hydroxyethyl isocyanurate, DOPO-HQ, DOPO-NQ, DOPO-PN, DOPO-BPN, and DPO.
As a preferable scheme, the paint further comprises at least one of the following components, 170-765 parts of inorganic filler, 0.75-2.25 parts of initiator, 7.5-22.5 parts of crosslinking assistant and 0.015-0.045 part of accelerator; the inorganic filler is added mainly to increase the thermal conductivity of the resin composition and to improve the thermal expansibility, mechanical strength, and other properties.
Preferably, the inorganic filler is at least one of silica, alumina, aluminum hydroxide, magnesium oxide, magnesium hydroxide, calcium carbonate, aluminum nitride, boron nitride, aluminum silicon carbide, titanium dioxide, zinc oxide, zirconium oxide, mica, boehmite, calcined talc, silicon nitride, or calcined kaolin; the inorganic filler may be spherical, fibrous, plate-like, granular, plate-like or whisker-like, and may optionally be pretreated with a silane coupling agent, and at the same time, the inorganic filler may be a powder of particles having a particle diameter of 100 μm or less, and preferably a powder of particles having a particle diameter of 1nm to 20 μm, most preferably a powder of nanosized particles having a particle diameter of 1 μm or less; the whisker-like inorganic filler may be a powder having a diameter of 50 μm or less and a length of 1 to 200 μm; the initiator is at least one of diacyl peroxide, peroxy ketal, peroxycarbonate, peroxyester, ketone peroxide, dialkyl peroxide, hydroperoxide and diphenyl peroxide; the accelerant is at least one of boron trifluoride amine complex, ethyl triphenyl phosphonium chloride, 2-methylimidazole, 2-phenyl-1H-imidazole, 2-ethyl-4-methylimidazole, triphenylphosphine, 4-dimethylaminopyridine or metal salt compounds, wherein the metal salt compounds can be metal salt compounds such as manganese, iron, cobalt, nickel, copper, zinc and the like, or metal catalysts such as zinc octoate, cobalt octoate and the like; the crosslinking auxiliary agent is at least one of triallyl isocyanate monomer, triallyl isocyanate monomer prepolymer, butadiene monomer, styrene monomer, pentadiene monomer, norbornene monomer or cyclopentadiene monomer.
A semi-solidified rubber sheet is prepared from the bismaleimide composition.
A copper foil substrate is prepared from the semi-solidified rubber sheet.
Compared with the prior art, the invention has obvious advantages and beneficial effects, and specifically, the technical scheme includes that:
the bismaleimide composition prepared by the formula has lower thermal expansion coefficient, higher glass transition temperature, lower dielectric constant and lower dielectric loss, can be prepared into semi-cured films or resin films, and further achieves the aim of being applied to copper foil substrates and printed circuit boards.
To more clearly illustrate the features and effects of the present invention, the present invention is described in detail below with reference to specific examples.
Detailed Description
The invention discloses a bismaleimide composition, which comprises 30-90 parts of bismaleimide, 20-60 parts of alicyclic epoxy resin and 55-330 parts of styrene-maleic anhydride copolymer; wherein the general formula of the bismaleimide is as follows:
in the general formula R 1 Is one of the following groups:
the structural general formula of the alicyclic epoxy resin is as follows:
r in the general formula 2 Is one of the following groups-CH 3 、
The styreneIn a reaction system, a styrene structure with good dielectric property is introduced into a cross-linking structure by the maleic anhydride copolymer, so that low dielectric constant and dielectric loss are realized, and the bismaleimide resin and the alicyclic epoxy resin are both of symmetrical structures, have low intermolecular polarity, and are favorable for reducing the dielectric loss after being compounded.
The styrene-maleic anhydride copolymer is a styrene-maleic anhydride copolymer with high styrene/maleic anhydride molar ratio, and the percentage of the anhydride molar mass is more than 3%; styrene-maleic anhydride copolymers with lower anhydride molar masses (generally less than 3%) are less suitable for compounding with epoxy resins; and the weight average molecular weight (Mw) of the styrene-maleic anhydride copolymer is between 9000 and 60000; styrene-maleic anhydride copolymers with too high a molecular weight (Mw generally higher than 60000) have poor compatibility with epoxy resins and are not suitable for printed circuit boards. Experiments prove that the styrene-maleic anhydride copolymer with the weight average molecular weight of about 3000 to 60000 and the weight percentage content of anhydride of more than about 3 percent can be compounded with epoxy resin and applied to printed circuit boards, in particular to the weight average molecular weight of 5000 to 12000, the styrene (S) and the styrene-maleic anhydride copolymer with the mole ratio of Maleic Anhydride (MA) of 4; therefore, the preferred range of the weight average molecular weight (Mw) of the styrene-maleic anhydride copolymer of the present invention is between 10000 to 15000; in addition, the sum of the equivalents of maleimide groups and the equivalents of acid anhydride: the equivalent weight of the alicyclic epoxy resin is (0.6-1.6): 1; the styrene-maleic anhydride copolymer is used as a curing agent of epoxy resin in printed circuit boards, and the equivalent ratio (styrene-maleic anhydride copolymer anhydride and phenolic hydroxyl group: epoxy resin) is properly in the range of (0.6-1.6): 1, and the optimal ratio is (0.9-1.1): 1.
And further comprises 3-9 parts of halogen-free flame retardant; the halogen-free flame retardant is a nitrogen-containing flame retardant or a phosphorus-containing flame retardant, and at least one of the following compounds can be selectively added into the halogen-free flame retardant, but the halogen-free flame retardant is not limited to the following compounds: bisphenol diphenyl phosphate, ammonium polyphosphate, hydroquinone-bis- (diphenyl phosphate), bisphenol a-bis- (diphenyl phosphate), tris (2-carboxyethyl) phosphine, tris (chloroisopropyl) phosphate, trimethyl phosphate, dimethyl methylphosphonate, resorcinol dixylyl phosphate, phosphazene, m-benzylphosphine, melamine polyphosphate, melamine cyanurate, tris-hydroxyethyl isocyanurate, DOPO-HQ, DOPO-NQ, DOPO-PN, DOPO-BPN and DPO.
And further comprises at least one of the following components, 170-765 parts of inorganic filler, 0.75-2.25 parts of initiator, 7.5-22.5 parts of crosslinking assistant and 0.015-0.045 part of accelerator; the inorganic filler is added mainly for increasing the thermal conductivity of the resin composition, improving the thermal expansibility, mechanical strength and other characteristics; the inorganic filler is at least one of silicon dioxide, aluminum oxide, aluminum hydroxide, magnesium oxide, magnesium hydroxide, calcium carbonate, aluminum nitride, boron nitride, aluminum silicon carbide, titanium dioxide, zinc oxide, zirconium oxide, mica, boehmite, calcined talc, silicon nitride or calcined kaolin; the inorganic filler may be in a spherical, fibrous, plate-like, granular, plate-like or whisker-like shape, and may optionally be pretreated with a silane coupling agent, and at the same time, the inorganic filler may be a powder of particles having a particle diameter of 100 μm or less, and preferably a powder of particles having a particle diameter of 1nm to 20 μm, and most preferably a powder of nano-sized particles having a particle diameter of 1 μm or less; the whisker-like inorganic filler may be a powder having a diameter of 50 μm or less and a length of 1 to 200 μm; the initiator is at least one of diacyl peroxide, peroxy ketal, peroxycarbonate, peroxy ester, ketone peroxide, dialkyl peroxide, hydroperoxide and diphenyl peroxide; the accelerant is at least one of boron trifluoride amine complex, ethyl triphenyl phosphonium chloride, 2-methylimidazole, 2-phenyl-1H-imidazole, 2-ethyl-4-methylimidazole, triphenylphosphine, 4-dimethylaminopyridine or metal salt compounds, wherein the metal salt compounds can be metal salt compounds such as manganese, iron, cobalt, nickel, copper, zinc and the like, or metal catalysts such as zinc octoate, cobalt octoate and the like; the crosslinking auxiliary agent is at least one of triallyl isocyanate monomer, triallyl isocyanate monomer prepolymer, butadiene monomer, styrene monomer, pentadiene monomer, norbornene monomer or cyclopentadiene monomer.
The invention also discloses a semi-solidified film which is prepared from the bismaleimide composition, and the preparation process comprises the steps of firstly mixing the raw material components according to the components, then uniformly mixing the raw material components in a stirring manner to prepare the bismaleimide composition, then soaking the bismaleimide composition uniformly mixed in 2116 glass cloth, baking the bismaleimide composition for 5 minutes at 170 ℃, and drying the bismaleimide composition to obtain the semi-solidified film.
The invention also discloses a copper foil substrate which is prepared from the semi-cured film; the manufacturing process comprises the following steps of taking a 2116 semi-cured film, covering 1oz HTE copper foils on the upper surface and the lower surface of the 2116 semi-cured film, and then placing the semi-cured film in a vacuum hot press for high-temperature curing at the curing temperature of more than 230 ℃ for more than 100 minutes, wherein the high-pressure during curing is 350PSI. This preparation method was used in the examples that follow.
The raw materials used in the following examples and comparative examples are shown in Table 1.
TABLE 1
The composition ratio of each example to each comparative example is shown in Table 2.
TABLE 2
The above examples and comparative examples were subjected to performance tests, and the test results are shown in table 3.
TABLE 3
From the data of the above examples and comparative examples, it can be seen that the bismaleimide composition of the present invention has a lower thermal expansion coefficient and a higher glass transition temperature, and also has a lower dielectric constant and dielectric loss, and the prepreg and resin film made therefrom are more suitable for application to IC package substrates, and by comparing examples 1-6 with example 7, it can be seen that a styrene-maleic anhydride copolymer having a weight average molecular weight in the range of 5000 to 12000, a molar ratio of styrene (S) to Maleic Anhydride (MA) of 4.
Test method
Glass transition temperature: the obtained copper-clad plate was subjected to three-time measurement of glass transition temperature using an instrumental differential scanning calorimeter (TA DSC 25) according to 2.4.25 in IPC-TM650, and the average value was taken.
Dielectric constant DK (10G): using the test piece (n = 3) of the obtained copper clad laminate from which the copper foil was removed, the dielectric constant at 10GHz was measured by the cavity resonator perturbation method, and the average value was obtained 3 times each.
Dielectric loss tangent Df Using the copper foil-removed test piece (n = 3) of the obtained copper clad laminate, a dielectric loss tangent value of 10GHz was measured by a cavity resonator perturbation method, and an average value was obtained 3 times for each.
Peel strength: the anti-stripping tester takes three samples to test and average according to the IPC-TM-650-2.4.8 method.
The thermal expansion coefficient is measured by using a TMA instrument according to the TMA test method specified by IPC-TM-650.4.24, and the value is in the range of 30-120 ℃.
And (3) testing combustibility: flammability test chamber (UL 94).
The above description is only a preferred embodiment of the present invention, and is not intended to limit the technical scope of the present invention, so that any minor modifications, equivalent changes and modifications made to the above embodiment according to the technical spirit of the present invention are within the technical scope of the present invention.
Claims (10)
1. A bismaleimide composition characterized by: comprises 30-90 parts of bismaleimide, 20-60 parts of alicyclic epoxy resin and 55-330 parts of styrene-maleic anhydride copolymer; wherein the general formula of the bismaleimide is as follows:
in the general formula R 1 Is one of the following groups:
the structural general formula of the alicyclic epoxy resin is as follows:
r in the general formula 2 Is one of the following groups-CH 3 、
2. The bismaleimide composition of claim 1, wherein: the styrene-maleic anhydride copolymer is a styrene-maleic anhydride copolymer with a high styrene/maleic anhydride molar ratio, and the percentage of the anhydride molar mass is more than 3%.
3. The bismaleimide composition of claim 1, wherein: the weight average molecular weight (Mw) of the styrene-maleic anhydride copolymer is between 9000 and 60000.
4. The bismaleimide composition of claim 3, wherein: the weight average molecular weight (Mw) of the styrene-maleic anhydride copolymer is between 10000 and 15000.
5. The bismaleimide composition of claim 1, wherein: sum of the equivalents of maleimide groups and equivalents of anhydride: the equivalent weight of the alicyclic epoxy resin is (0.6-1.6): 1.
6. the bismaleimide composition of claim 1, wherein: further comprises 3-9 parts of halogen-free flame retardant; the halogen-free flame retardant is one or more of bisphenol diphenyl phosphate, ammonium polyphosphate, hydroquinone-bis- (diphenyl phosphate), bisphenol A-bis- (diphenyl phosphate), tris (2-carboxyethyl) phosphine, tris (chloroisopropyl) phosphate, trimethyl phosphate, dimethyl methylphosphonate, resorcinol dixylyl phosphate, phosphazene, m-benzylphosphine, melamine polyphosphate, melamine cyanurate, tris-hydroxyethyl isocyanurate, DOPO-HQ, DOPO-NQ, DOPO-PN, DOPO-BPN or DPO.
7. The bismaleimide composition of any of claims 1 to 6 wherein: the adhesive further comprises at least one of the following components, 170-765 parts of inorganic filler, 0.75-2.25 parts of initiator, 7.5-22.5 parts of crosslinking assistant and 0.015-0.045 part of accelerator.
8. The bismaleimide composition of claim 7, wherein: the inorganic filler is at least one of silicon dioxide, aluminum oxide, aluminum hydroxide, magnesium oxide, magnesium hydroxide, calcium carbonate, aluminum nitride, boron nitride, aluminum silicon carbide, titanium dioxide, zinc oxide, zirconium oxide, mica, boehmite, calcined talc, silicon nitride or calcined kaolin; the initiator is at least one of diacyl peroxide, peroxy ketal, peroxycarbonate, peroxyester, ketone peroxide, dialkyl peroxide, hydroperoxide and diphenyl peroxide; the accelerant is at least one of boron trifluoride amine complex, ethyl triphenyl phosphonium chloride, 2-methylimidazole, 2-phenyl-1H-imidazole, 2-ethyl-4-methylimidazole, triphenylphosphine, 4-dimethylaminopyridine or metal salt compound; the crosslinking assistant is at least one of triallyl isocyanate monomer, triallyl isocyanate monomer prepolymer, butadiene monomer, styrene monomer, pentadiene monomer, norbornene monomer or cyclopentadiene monomer.
9. A semi-cured film characterized in that: prepared from the bismaleimide composition of any of claims 1 to 8.
10. A copper foil substrate characterized in that: which is produced from the prepreg according to claim 9.
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