CN115637013B - Bismaleimide composition, prepreg and copper foil substrate - Google Patents
Bismaleimide composition, prepreg and copper foil substrate Download PDFInfo
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- CN115637013B CN115637013B CN202211348078.3A CN202211348078A CN115637013B CN 115637013 B CN115637013 B CN 115637013B CN 202211348078 A CN202211348078 A CN 202211348078A CN 115637013 B CN115637013 B CN 115637013B
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- bismaleimide
- styrene
- maleic anhydride
- copper foil
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- 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 30
- 229920003192 poly(bis maleimide) Polymers 0.000 title claims abstract description 30
- 239000000203 mixture Substances 0.000 title claims abstract description 23
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 239000011889 copper foil Substances 0.000 title claims abstract description 13
- 239000000758 substrate Substances 0.000 title claims abstract description 12
- 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 28
- 229920000147 Styrene maleic anhydride Polymers 0.000 claims abstract description 28
- 239000003822 epoxy resin Substances 0.000 claims abstract description 23
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 23
- 239000003063 flame retardant Substances 0.000 claims description 14
- 239000011256 inorganic filler Substances 0.000 claims description 13
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 13
- 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 7
- 239000003999 initiator Substances 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 2
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims 1
- 239000000853 adhesive Substances 0.000 claims 1
- 230000001070 adhesive effect Effects 0.000 claims 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 1
- 125000002723 alicyclic group Chemical group 0.000 abstract description 11
- 229920005989 resin Polymers 0.000 abstract description 8
- 239000011347 resin Substances 0.000 abstract description 8
- 230000009477 glass transition Effects 0.000 abstract description 7
- -1 maleimide compound Chemical class 0.000 description 17
- 150000008064 anhydrides Chemical class 0.000 description 10
- 239000000178 monomer Substances 0.000 description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 229910052751 metal Chemical class 0.000 description 8
- 239000002184 metal Chemical class 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 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 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000011342 resin composition Substances 0.000 description 5
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical class CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 4
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 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
- 239000012948 isocyanate Substances 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical class C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 2
- 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
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical class CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 2
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical class C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 2
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical class CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- 239000004114 Ammonium polyphosphate Substances 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229920000388 Polyphosphate Polymers 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- PZBFGYYEXUXCOF-UHFFFAOYSA-N TCEP Chemical compound OC(=O)CCP(CCC(O)=O)CCC(O)=O PZBFGYYEXUXCOF-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 2
- 229920001276 ammonium polyphosphate Polymers 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 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 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 229910001593 boehmite Inorganic materials 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Substances FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 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
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 2
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 description 2
- 239000012933 diacyl peroxide Substances 0.000 description 2
- VONWDASPFIQPDY-UHFFFAOYSA-N dimethyl methylphosphonate Chemical compound COP(C)(=O)OC VONWDASPFIQPDY-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 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 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 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
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 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
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 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
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 2
- MMCOUVMKNAHQOY-UHFFFAOYSA-L oxido carbonate Chemical compound [O-]OC([O-])=O MMCOUVMKNAHQOY-UHFFFAOYSA-L 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- VWSUVZVPDQDVRT-UHFFFAOYSA-N phenylperoxybenzene Chemical compound C=1C=CC=CC=1OOC1=CC=CC=C1 VWSUVZVPDQDVRT-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000001205 polyphosphate Substances 0.000 description 2
- 235000011176 polyphosphates Nutrition 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 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
- 239000000454 talc Substances 0.000 description 2
- 235000012222 talc Nutrition 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 239000011787 zinc oxide 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
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- 238000013473 artificial intelligence Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009529 body temperature measurement Methods 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
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Reinforced Plastic Materials (AREA)
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 low thermal expansion coefficient and high glass transition temperature, and also has low dielectric constant and low dielectric loss, and can be prepared into a semi-cured film or a resin film so as to achieve the purpose of being applied to copper foil substrates and printed circuit boards.
Description
Technical Field
The invention relates to the technology in the 5G field, in particular to a bismaleimide composition, a semi-cured film and a copper foil substrate.
Background
With the increasing demand of people for mobile data, 5G is more and more widely applied 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 time delay, and therefore, the human society is continuously accelerated to enter the 'everything interconnection' era. With the continuous development of 5G and the continuous development of PCB to high precision and high density, the requirements on CCL are continuously improved, and 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 capable of meeting the application characteristics is mainly a BT-type board, however, the high-end printed board applied to 5G is monopoly by Europe and America, and the BT-type high-end printed board used in China is mainly imported. With the continuous development of 5G, breaking through the technical blockade of 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 the dielectric constant of 4.41 is still high for IC package carrier, and the dielectric properties of the substrate are still in room for improvement. Therefore, there is a need for improvements over existing maleimide compounds.
Disclosure of Invention
In view of the above, the present invention aims at overcoming the drawbacks of the prior art, and it is a primary object of the present invention to provide a bismaleimide composition, a semi-cured film and a copper foil substrate, which have a low thermal expansion coefficient and a high glass transition temperature, and also have a low dielectric constant and a low dielectric loss, and which can be manufactured into a semi-cured film or a resin film, thereby achieving the purpose of being applicable to copper foil substrates and printed circuit boards.
In order to achieve the above purpose, the present 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:
R 1 in the general formula 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 the following groups-CH 3, In the reaction system, the styrene-maleic anhydride copolymer introduces a styrene structure with good dielectric property into a crosslinking structure to realize low dielectric constant and dielectric loss, and the bismaleimide resin and the alicyclic epoxy resin are both symmetrical structures, so that the polarity between molecules is low, and the dielectric loss can be reduced after the bismaleimide resin and the alicyclic epoxy resin are compounded.
As a preferred scheme, 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%; styrene-maleic anhydride copolymers with lower anhydride molar masses (typically less than 3%) are less suitable for compounding with epoxy resins.
As a preferred 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 unsuitable 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 percent of anhydride more than about 3 percent can be compounded with epoxy resin to be applied to printed circuit boards, particularly the styrene-maleic anhydride copolymer with 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 4:1,6:1,8:1 and 4:1, and the mixture thereof, such as EF40, EF60 and EF80 of the company Polyscope in the Netherlands, have good thermal reliability, low dielectric property and good printed circuit board processability when being applied to printed circuit boards.
As a preferred embodiment, the weight average molecular weight (Mw) of the styrene-maleic anhydride copolymer is between 10000 and 15000.
As a preferred embodiment, the sum of the equivalents of maleimide groups and the equivalents of anhydride groups: the equivalent weight of the alicyclic epoxy resin is (0.6-1.6): 1, a step of; the styrene-maleic anhydride copolymer is used as the curing agent of the epoxy resin in the printed circuit board, and the equivalent ratio (the styrene-maleic anhydride copolymer anhydride and the phenolic hydroxyl group: the epoxy resin) is in the range of (0.6-1.6): 1, and the optimal ratio is (0.9-1.1): 1.
As a preferable scheme, the flame retardant 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 bisxylyl phosphate, phosphazene, m-benzyl phosphine, melamine polyphosphate, melamine cyanurate, tris-hydroxyethyl isocyanurate, DOPO-HQ, DOPO-NQ, DOPO-PN, DOPO-BPN, and DPO.
As a preferable scheme, the composition 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 auxiliary agent and 0.015-0.045 part of accelerator; the inorganic filler is added mainly to increase the heat conductivity of the resin composition and improve the thermal expansibility and mechanical strength of the resin composition.
As a preferable scheme, 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 spherical, fibrous, plate-like, granular, flake-like or needle-like, and optionally pretreated with a silane coupling agent, and at the same time, the inorganic filler may be a particulate powder having a particle diameter of 100 μm or less, and preferably a particulate powder having a particle diameter of 1nm to 20 μm, and most preferably a nanosized particulate powder having a particle diameter of 1 μm or less; the needle-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, peroxy carbonate, peroxy ester, ketone peroxide, dialkyl peroxide, hydroperoxide and diphenyl peroxide; the accelerator is at least one of boron trifluoride amine compound, ethyl triphenyl phosphonium chloride, 2-methylimidazole, 2-phenyl-1H-imidazole, 2-ethyl-4-methylimidazole, triphenylphosphine, 4-dimethylaminopyridine or metal salt compound, wherein the metal salt compound can be selected from metal salt compounds such as manganese, iron, cobalt, nickel, copper, zinc and the like, or selected from metal catalysts such as zinc octoate, cobalt octoate and the like; the cross-linking 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 prepreg which is prepared from the aforementioned bismaleimide composition.
A copper foil substrate is prepared from the semi-solidified film.
Compared with the prior art, the invention has obvious advantages and beneficial effects, and in particular, the technical scheme can be as follows:
the bismaleimide composition prepared by the formula has lower thermal expansion coefficient and higher glass transition temperature, and also has lower dielectric constant and lower dielectric loss, and can be prepared into a semi-cured film or a resin film, so that the purpose of being applied to a copper foil substrate and a printed circuit board is achieved.
In order to more clearly illustrate the features and effects of the present invention, the present invention will be described in detail 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:
R 1 in the general formula is one of the following groups:
the structural general formula of the alicyclic epoxy resin is as follows:
r 2 in the general formula is-CH 3, In the reaction system, the styrene-maleic anhydride copolymer introduces a styrene structure with good dielectric property into a crosslinking structure to realize low dielectric constant and dielectric loss, and the bismaleimide resin and the alicyclic epoxy resin are both symmetrical structures, so that the polarity between molecules is low, and the dielectric loss can be reduced after the bismaleimide resin and the alicyclic epoxy resin are compounded.
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%; styrene-maleic anhydride copolymers with lower anhydride molar masses (typically less than 3%) are not well suited 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 unsuitable 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 percent of anhydride above about 3 percent can be compounded with epoxy resin to be applied to printed circuit boards, particularly the styrene-maleic anhydride copolymer with the weight average molecular weight of 5000 to 12000, the styrene (S) and the mixture thereof with the molar ratio of Maleic Anhydride (MA) of 4:1,6:1,8:1 and 4:1, such as EF40, EF60 and EF80 of the company Polyscope in the Netherlands, has good thermal reliability, low dielectric property and good printed circuit board processability when being applied to printed circuit boards; thus, the preferred range of weight average molecular weight (Mw) of the styrene-maleic anhydride copolymer of the present invention is between 10000 and 15000; in addition, the sum of the equivalents of maleimide groups and the equivalents of anhydride: the equivalent weight of the alicyclic epoxy resin is (0.6-1.6): 1, a step of; the styrene-maleic anhydride copolymer is used as the curing agent of the epoxy resin in the printed circuit board, and the equivalent ratio (the styrene-maleic anhydride copolymer anhydride and the phenolic hydroxyl group: the epoxy resin) is in the range of (0.6-1.6): 1, and the optimal ratio is (0.9-1.1): 1.
And, further comprising 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 bisxylyl phosphate, phosphazene, m-benzyl phosphine, 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 auxiliary agent and 0.015-0.045 part of accelerator; the inorganic filler is mainly added to increase the heat conductivity of the resin composition and improve the thermal expansibility, mechanical strength and other characteristics of the resin composition; 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 talcum, silicon nitride or calcined kaolin; the inorganic filler may be spherical, fibrous, plate-like, granular, flake-like or needle-like, and optionally pretreated with a silane coupling agent, and at the same time, the inorganic filler may be a particulate powder having a particle diameter of 100 μm or less, and preferably a particulate powder having a particle diameter of 1nm to 20 μm, and most preferably a nanosized particulate powder having a particle diameter of 1 μm or less; the needle-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, peroxy carbonate, peroxy ester, ketone peroxide, dialkyl peroxide, hydroperoxide and diphenyl peroxide; the accelerator is at least one of boron trifluoride amine compound, ethyl triphenyl phosphonium chloride, 2-methylimidazole, 2-phenyl-1H-imidazole, 2-ethyl-4-methylimidazole, triphenylphosphine, 4-dimethylaminopyridine or metal salt compound, wherein the metal salt compound can be selected from metal salt compounds such as manganese, iron, cobalt, nickel, copper, zinc and the like, or selected from metal catalysts such as zinc octoate, cobalt octoate and the like; the cross-linking 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, the preparation process comprises the steps of mixing the raw material components according to the components, uniformly mixing the raw material components in a stirring mode to prepare the bismaleimide composition, immersing the prepared bismaleimide composition into 2116 glass cloth, baking the bismaleimide composition at 170 ℃ for 5 minutes, and drying the bismaleimide composition to prepare 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 steps of taking a 2116 semi-cured film, covering the upper surface and the lower surface of the 2116 semi-cured film with 1oz HTE copper foil, and then placing the film in a vacuum hot press for high-temperature curing, wherein the curing temperature is more than 230 ℃, the curing time is more than 100 minutes, and the high-pressure during curing is 350PSI. This preparation method was used in the subsequent examples.
The raw materials used in the following examples and comparative examples are shown in Table 1.
TABLE 1
The composition ratios of the examples and comparative examples are shown in table 2, for example.
TABLE 2
The performance test was performed on the above examples and comparative examples, and the test results are shown in table 3.
TABLE 3 Table 3
As can be seen from the data of the above examples and comparative examples, 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 semi-cured films and resin films produced therefrom are more suitable for use in IC package carrier boards, and by comparing examples 1 to 6 with example 7, it can be obtained that the styrene-maleic anhydride copolymer having a weight average molecular weight in the range of 5000 to 12000 and a molar ratio of styrene (S) Maleic Anhydride (MA) in the range of 4:1,6:1,8:1 and 4:1 has very good compatibility with cycloaliphatic epoxy resins, and has good thermal reliability and low dielectric properties, and good processability of printed circuit boards when being compounded with cycloaliphatic epoxy resins for use in printed circuit boards.
Test method
Glass transition temperature: the resulting copper-clad plate was subjected to three times of glass transition temperature measurement 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): the dielectric constant of 10GHz was measured by a cavity resonator disturbance method using a test piece (n=3) of the obtained copper-clad laminate from which copper foil was removed, and an average value was obtained 3 times.
Dielectric loss tangent Df from the copper foil-removed test piece (n=3) of the obtained copper-clad laminate, dielectric loss tangent values at 10GHz were measured by the cavity resonator disturbance method, and the average value was obtained 3 times.
Peel strength: the stripping resistance tester is used for taking three samples and testing and averaging the three samples according to the IPC-TM-650-2.4.8 method.
Thermal expansion coefficient is measured by TMA instrument according to TMA test method specified by IPC-TM-650.2.4.24, and the temperature range of 30-120 deg.C is adopted.
Flammability test: flammability test box (UL 94).
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the technical scope of the present invention, so any minor modifications, equivalent changes and modifications made to the above embodiments according to the technical principles of the present invention are still within the scope of the technical solutions of the present invention.
Claims (3)
1. A bismaleimide composition characterized by: the adhesive comprises the following components in parts by weight: 10 parts of BMI2000 bismaleimide, 20 parts of BMI4000 bismaleimide, 15 parts of KR470 epoxy resin, 45 parts of 2021P epoxy resin, 330 parts of EF-60 styrene-maleic anhydride copolymer, 9 parts of PX200 phosphoric acid halogen-free flame retardant, 2.25 parts of DCP initiator, 22.5 parts of TAIC crosslinking assistant, 0.04 parts of 2E4MZ accelerator and 765 parts of SC2050-KC inorganic filler.
2. A prepreg, characterized in that: which is prepared from the bismaleimide composition according to claim 1.
3. The copper foil substrate is characterized in that: which is produced from the prepreg according to claim 2.
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