CN117186617A - Resin composition containing modified cycloolefin copolymer, metal-clad laminate using same and preparation method of metal-clad laminate - Google Patents
Resin composition containing modified cycloolefin copolymer, metal-clad laminate using same and preparation method of metal-clad laminate Download PDFInfo
- Publication number
- CN117186617A CN117186617A CN202311165321.2A CN202311165321A CN117186617A CN 117186617 A CN117186617 A CN 117186617A CN 202311165321 A CN202311165321 A CN 202311165321A CN 117186617 A CN117186617 A CN 117186617A
- Authority
- CN
- China
- Prior art keywords
- cycloolefin copolymer
- resin composition
- modified
- modified cycloolefin
- copolymer
- 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
- 229920001577 copolymer Polymers 0.000 title claims abstract description 73
- 239000011342 resin composition Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 229920005989 resin Polymers 0.000 claims abstract description 63
- 239000011347 resin Substances 0.000 claims abstract description 63
- 229910052751 metal Inorganic materials 0.000 claims abstract description 34
- 239000002184 metal Substances 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 25
- 239000003063 flame retardant Substances 0.000 claims abstract description 22
- 239000003292 glue Substances 0.000 claims abstract description 21
- 239000012745 toughening agent Substances 0.000 claims abstract description 16
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 14
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 claims abstract description 11
- 239000003999 initiator Substances 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 229920013638 modified polyphenyl ether Polymers 0.000 claims abstract description 8
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 8
- 238000011049 filling Methods 0.000 claims abstract description 5
- -1 cyclic olefin Chemical class 0.000 claims description 25
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 16
- 239000011888 foil Substances 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 229920001955 polyphenylene ether Polymers 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 claims description 7
- 239000004711 α-olefin Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 239000004744 fabric Substances 0.000 claims description 6
- 239000000945 filler Substances 0.000 claims description 6
- 239000003365 glass fiber Substances 0.000 claims description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 6
- 229920013636 polyphenyl ether polymer Polymers 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 4
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- ZOUWOGOTHLRRLS-UHFFFAOYSA-N palladium;phosphane Chemical compound P.[Pd] ZOUWOGOTHLRRLS-UHFFFAOYSA-N 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims description 4
- 238000004513 sizing Methods 0.000 claims description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- 239000005062 Polybutadiene Substances 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 3
- 229920002857 polybutadiene Polymers 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 3
- 239000000454 talc Substances 0.000 claims description 3
- 229910052623 talc Inorganic materials 0.000 claims description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- BLCKNMAZFRMCJJ-UHFFFAOYSA-N cyclohexyl cyclohexyloxycarbonyloxy carbonate Chemical compound C1CCCCC1OC(=O)OOC(=O)OC1CCCCC1 BLCKNMAZFRMCJJ-UHFFFAOYSA-N 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N divinylbenzene Substances C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 2
- 150000004692 metal hydroxides Chemical class 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 229920006132 styrene block copolymer Polymers 0.000 claims description 2
- 125000005504 styryl group Chemical group 0.000 claims description 2
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 239000013032 Hydrocarbon resin Substances 0.000 description 16
- 229920006270 hydrocarbon resin Polymers 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 13
- 230000009477 glass transition Effects 0.000 description 13
- 238000012360 testing method Methods 0.000 description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- 239000000758 substrate Substances 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 3
- 239000004713 Cyclic olefin copolymer Substances 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical class C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 description 2
- 125000003636 chemical group Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 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
- 230000003287 optical effect Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229920003192 poly(bis maleimide) Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- 229920006380 polyphenylene oxide Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- DPZNOMCNRMUKPS-UHFFFAOYSA-N resorcinol dimethyl ether Natural products COC1=CC=CC(OC)=C1 DPZNOMCNRMUKPS-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000000930 thermomechanical effect Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- BZQKBFHEWDPQHD-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-[2-(2,3,4,5,6-pentabromophenyl)ethyl]benzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1CCC1=C(Br)C(Br)=C(Br)C(Br)=C1Br BZQKBFHEWDPQHD-UHFFFAOYSA-N 0.000 description 1
- XSHWKULGRFTYIT-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C XSHWKULGRFTYIT-UHFFFAOYSA-N 0.000 description 1
- AXTADRUCVAUCRS-UHFFFAOYSA-N 1-(2-hydroxyethyl)pyrrole-2,5-dione Chemical compound OCCN1C(=O)C=CC1=O AXTADRUCVAUCRS-UHFFFAOYSA-N 0.000 description 1
- 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 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- XIRDTMSOGDWMOX-UHFFFAOYSA-N 3,4,5,6-tetrabromophthalic acid Chemical compound OC(=O)C1=C(Br)C(Br)=C(Br)C(Br)=C1C(O)=O XIRDTMSOGDWMOX-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical class N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 description 1
- 229920002633 Kraton (polymer) Polymers 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-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
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000007973 cyanuric acids Chemical class 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical group BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- DZGCGKFAPXFTNM-UHFFFAOYSA-N ethanol;hydron;chloride Chemical compound Cl.CCO DZGCGKFAPXFTNM-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- CLQUXJZJDVHHMG-UHFFFAOYSA-N nickel;phenol Chemical compound [Ni].OC1=CC=CC=C1.OC1=CC=CC=C1 CLQUXJZJDVHHMG-UHFFFAOYSA-N 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- RERMPCBBVZEPBS-UHFFFAOYSA-N tris(2,6-dimethylphenyl)phosphane Chemical compound CC1=CC=CC(C)=C1P(C=1C(=CC=CC=1C)C)C1=C(C)C=CC=C1C RERMPCBBVZEPBS-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
Abstract
The invention relates to a resin composition containing a modified cycloolefin copolymer, a metal foil-clad laminated plate using the same and a preparation method thereof, wherein the resin composition comprises the following components in parts by weight: 20-40 parts of modified polyphenyl ether resin; 10-30 parts of modified cycloolefin copolymer; 10-25 parts of a cross-linking agent; 5-15 parts of a toughening agent; 15-30 parts of flame retardant; 70-90 parts of filling material; 0.1-0.4 part of initiator; 90-135 parts of organic solvent. Compared with the prior art, the modified cycloolefin copolymer is prepared by introducing polar maleimide groups into the unsaturated cycloolefin copolymer, and can be matched with other unsaturated resins to be used as a component of a thermosetting resin composition to be applied to the preparation of resin composition glue solution and metal foil-clad laminated plates, so that the prepared laminated plates have good dielectric property, peeling strength, heat resistance and mechanical strength.
Description
Technical Field
The invention relates to the technical field of metal foil-clad laminated plates, in particular to a resin composition containing a modified cycloolefin copolymer, a metal foil-clad laminated plate using the same and a preparation method thereof.
Background
Along with the high-speed development of the 5G technology, the development and application of the high-frequency high-speed copper-clad plate also become a great hot spot gradually. At present, the resin with more application in the field of high-frequency and high-speed copper-clad plates mainly comprises modified polyphenylene oxide (PPO) resin, bismaleimide resin (BMI), modified epoxy resin, polyimide resin (PI), polytetrafluoroethylene resin (PTFE), hydrocarbon resin and the like. The hydrocarbon resin has excellent dielectric property due to the low crosslinking density and the nonpolar nature of the molecular structure, and the hydrocarbon resin has the advantages of abundant sources, low cost, easy obtainment and obvious cost compared with other resins. Therefore, the method has wide application prospect in the fields of 5G communication, vehicle millimeter wave radar, internet of things and the like.
However, hydrocarbon resins have problems of insufficient rigidity, low strength, poor heat resistance, low glass transition temperature (Tg), low peel strength and the like due to the flexible and nonpolar carbon chain structure of the hydrocarbon resins, and the use of the hydrocarbon resins is limited. Therefore, it is important to develop hydrocarbon resin substrates having high heat resistance, high peel strength and low thermal expansion coefficient.
Cycloolefin copolymers (COC) are products obtained after polymerization of cyclic olefins with ethylene or α -olefins, have extremely low dielectric properties compared to other resins, have dielectric constants and dielectric losses similar to those of PTFE at high frequencies (10 GHz), and have both flexible aliphatic hydrocarbon segments and rigid cyclic structures. The aliphatic chain segment can keep excellent chemical resistance, water resistance, good mechanical strength, electrical insulation and other characteristics of the cycloolefin copolymer material, and the rigid cyclic structure can endow the cycloolefin copolymer with lower thermal expansion coefficient, higher glass transition temperature (Tg) and good heat resistance.
The cycloolefin copolymer is used as a high-performance hydrocarbon resin material, is mainly applied to the fields of manufacturing optical parts, packaging materials, electronic elements, medical appliances and the like at present, and rarely has research on applying COC to the field of PCB manufacturing due to the excellent optical characteristics, and is mainly because the common COC material has very poor peeling strength and cannot be directly used in a copper-clad plate, and the COC has serious brittleness (low elongation at break) and poor processability, so that the COC is limited to be widely applied to the field of high-frequency high-speed copper-clad plates to a great extent.
Patent CN113121940B discloses a method for forming a modified cyclic olefin copolymer by introducing methacrylate end groups with a certain polarity into the cyclic olefin copolymer, which can crosslink with itself or other unsaturated resins to form a thermosetting material, and can also significantly improve the adhesive property while maintaining the excellent dielectric property of the cyclic olefin copolymer itself. However, the mechanical strength of the copper-clad plate is not studied in the patent, and the methacrylate groups are flexible chain segments, so that the mechanical strength of the forming substrate is affected to a certain extent after the methacrylate groups are introduced, and the application range of the copper-clad plate is limited.
Accordingly, there is a need for a resin composition that can produce a metal foil-clad laminate having good dielectric properties, peel strength, heat resistance, and mechanical strength.
Disclosure of Invention
The present invention has been made in order to solve the above problems, and an object of the present invention is to provide a modified cycloolefin copolymer-containing resin composition, a metal foil-clad laminate using the same, and a method for manufacturing the same, wherein the modified cycloolefin copolymer is manufactured by introducing a polar maleimide group into an unsaturated cycloolefin copolymer, and the maleimide group is a rigid structure, so that the material has high rigidity, the mechanical strength of a resin molded body is well maintained, and secondly, the non-polarity exhibited by a symmetrical structure is good, so that the resin molded body has good dielectric properties. The modified cycloolefin copolymer can be matched with other unsaturated resins, and can be used as a component of a thermosetting resin composition to be applied to preparation of resin composition glue solution and metal foil-clad laminated plates, so that the prepared laminated plates have good dielectric property, peeling strength, heat resistance and mechanical strength.
The aim of the invention is achieved by the following technical scheme:
the first object of the present invention is to provide a modified cycloolefin copolymer-containing resin composition comprising the following components in parts by weight:
further, the modified cycloolefin copolymer has a structure as shown in the formula (I):
in the formula (I), R1 is one or more of aliphatic hydrocarbons containing unsaturated bonds and having 2-10 carbon atoms, and specifically includes-C=C--C＝C-C-、/>-C-C＝C-C-、/>It is noted that R1 includes, but is not limited to, the above structures.
Further, in formula (I), R2 is One or more of them.
Further, in the formula (I), m and n are integers greater than or equal to 1.
Preferably, the modified polyphenyl ether resin is polyphenyl ether resin with double bonds at the end groups, and comprises one or more polyphenyl ether resins modified by unsaturated groups such as allyl, vinyl, styryl or methacrylate groups.
The invention prefers the polyphenyl ether resin with unsaturated group-containing modified terminal, which endows higher reactivity and better increases the reactivity and compatibility with other resins. Specifically, the modified polyphenylene ether resin may be selected from one or a combination of several of styryl-modified polyphenylene ether resin, allyl-modified polyphenylene ether resin, acrylate-modified polyphenylene ether resin and methyl methacrylate-modified polyphenylene ether resin.
Preferably, the crosslinking agent comprises any one or more of a trialkenyl isocyanurate compound, a multifunctional acrylate compound, a multifunctional methacrylate compound, a multifunctional vinyl compound, and a divinylbenzene compound. The addition of the cross-linking agent further improves the cross-linking density of the resin, forms a more stable three-dimensional network structure, and can improve the glass transition temperature, toughness, heat resistance, solvent resistance and other properties of the cured material, so that the prepared metal foil-clad laminated plate has low dielectric constant and dielectric loss.
Preferably, the toughening agent comprises one or more of polybutadiene, styrene-butadiene block copolymer, styrene-butadiene-styrene triblock copolymer, hydrogenated styrene/butadiene/styrene block copolymer, maleic anhydride grafted styrene-butadiene-styrene block copolymer elastomer. The toughening agent adopted by the invention is hydrocarbon resin, so that the dielectric property of the material can be improved to a certain extent, and the use of the toughening agent can also better improve the binding force between the resin and the surface of the copper foil, so that the prepared metal foil-clad laminated plate can obtain good peeling strength.
Preferably, the flame retardant comprises one or a mixture of a plurality of brominated flame retardants, phosphorus flame retardants and nitrogen flame retardants. Specifically, the brominated flame retardant is selected from decabromodiphenyl ether, decabromodiphenyl ethane, brominated styrene or tetrabromophthalic acid amide, and the phosphorus flame retardant is selected from inorganic phosphorus, phosphate, phosphoric acid, hypophosphorous acid, phosphorus oxide, phosphazene, modified phosphazene, 9,10 dihydro 9 oxa 10 phosphaphenanthrene 10 oxide
(DOPO), 10 (2, 5 dihydroxyphenyl) 9,10 dihydro 9 oxa 10 phosphaphenanthrene 10 oxide (DOPO HQ), 10 phenyl 9,10 dihydro 9 oxa 10 phosphaphenanthrene 10 oxide, tris (2, 6 dimethylphenyl) phosphorus, and a nitrogen-based flame retardant selected from triazine compounds, cyanuric acid compounds, isocyanic acid compounds and phenothiazine. Among the above, phosphorus flame retardants and nitrogen flame retardants are preferable, and phosphorus flame retardants are more preferable.
The filler is preferably added to improve the heat resistance and flame retardancy of the resin composition and its cured product, and is not particularly limited. Specific examples of the filler include: spherical, angular silica and other silica fine powders; metal oxides such as aluminum oxide and titanium oxide; metal hydroxides such as aluminum hydroxide and magnesium hydroxide; talc, aluminum borate, barium sulfate, calcium carbonate, and the like; mica. Among the above, silica, mica, and talc are preferable as the filler, and spherical silica is more preferable.
Preferably, the initiator is one or more of dicumyl peroxide, di-tert-butyl peroxide, benzoyl peroxide, tert-butyl peroxybenzoate, dicyclohexyl peroxydicarbonate, cumene hydroperoxide and azobisisobutyronitrile.
Preferably, the organic solvent is any one or more of toluene, butanone, acetone, dimethylformamide, methyl ethyl ketone or propylene glycol methyl ether.
Further, the modified cycloolefin copolymer is prepared by polymerizing cyclic olefin and alpha-olefin and then introducing polar maleimide groups; wherein the catalyst used in the polymerization process of the cyclic olefin and the alpha-olefin is preferably a palladium phosphine sulfonate catalyst, specifically one or more of a bis-o-methoxyphenyl substituted palladium phosphine sulfonate catalyst, a 2- (2, 6-dimethoxybenzene) phenyl and phenyl substituted palladium phosphine sulfonate catalyst, a dicyclohexyl substituted palladium phosphine sulfonate catalyst and a bis-tert-butyl substituted palladium phosphine sulfonate catalyst (such as a palladium phosphine sulfonate nickel phosphine phenol catalyst), preferably, the polymerization reaction temperature of the cyclic olefin and the alpha-olefin is 30-80 ℃, and the polymerization reaction time is 1-3 h.
Preferably, the number average molecular weight of the modified cycloolefin copolymer is preferably 1000 to 12000.
Further preferably, the modified cycloolefin copolymer has a number average molecular weight of 1600 to 5000.
Preferably, among the R1 units and R2 units of the modified cycloolefin copolymer, the R1 unit accounts for 10 to 50% of the total amount of the R1 and R2 units.
Further preferably, among the R1 units and R2 units of the modified cycloolefin copolymer, the R1 unit accounts for 15 to 30% of the total amount of the R1 and R2 units.
A second object of the present invention is to provide a metal foil-clad laminate prepared using the above-mentioned modified cycloolefin copolymer-containing resin composition.
A third object of the present invention is to provide a method for producing the above metal foil-clad laminate, comprising the steps of:
stirring the toughening agent, the modified polyphenyl ether resin, the modified cycloolefin copolymer and the crosslinking agent at a rotating speed of 1000-1500 rpm by using an organic solvent until the resin is completely dissolved;
(ii) adding the flame retardant and the filling material, and uniformly mixing at a rotating speed of 1000-1500 rpm;
(iii) adding the initiator, uniformly mixing at a speed of 1000-1500 rpm, and homogenizing and discharging to obtain resin composition glue solution;
(iv) sizing the glass fiber cloth by the resin composition glue solution through an impregnation process, and placing the glass fiber cloth in an oven to bake for 200-300 seconds at a high temperature of 120-160 ℃ to prepare a prepreg;
and (v) cutting the prepreg, respectively covering the two sides with metal foils, and then pressing at a high temperature of 150-220 ℃ under a vacuum condition to obtain the metal foil-clad laminated board.
Compared with the prior art, the invention has the following advantages:
(1) According to the invention, the modified polyphenyl ether resin and the modified cycloolefin copolymer are used as main resins, and then the partial cross-linking agent is added, so that the cross-linking density of a resin system can reach an ideal state, and a matrix structure with good heat resistance can be obtained after the resin system is cured; the toughening agent adopted by the invention is hydrocarbon resin, so that the dielectric property of the material can be improved to a certain extent, the use of the toughening agent can also better improve the binding force between the resin and the surface of the copper foil, and the substrate can obtain good peel strength.
(2) The modified cycloolefin copolymer prepared by the invention has both flexible aliphatic hydrocarbon chain segments and rigid cyclic structures. The aliphatic chain segment can keep the excellent chemical resistance, water resistance, good mechanical strength, electrical insulation and other characteristics of the cycloolefin copolymer material, and the rigid annular structure can endow the cycloolefin copolymer material with higher glass transition temperature, so that the heat resistance of the material is improved. Compared with the traditional hydrocarbon resin, the modified cycloolefin copolymer has the advantages of maintaining the excellent dielectric property, and simultaneously overcoming the problems of insufficient rigidity, low strength, poor heat resistance, low glass transition temperature, low peeling strength and the like of a cured product of the polyolefin resin due to the flexible and nonpolar carbon chain structure.
(3) The Tg of the metal-clad foil plate prepared by the resin composition glue solution is more than 230 ℃; z-axis CTE < 1.8%; heat resistance: TD is more than or equal to 410 ℃, T288 is more than 120min; electrical properties: the dielectric constant (10 GHZ) is less than or equal to 3.5; dielectric loss (10 GHZ) < 0.0025; in addition, the flame retardant has lower water absorption and good mechanical processing performance, achieves UL94V-0 level, and can completely meet the production requirement of the multilayer board in the field of high-frequency high-speed PCB.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications could be made by those skilled in the art without departing from the inventive concept. These are all within the scope of the present invention.
The conception history of the applicant is as follows:
the modified cycloolefin copolymer is prepared by a method of introducing polar maleimide groups into an unsaturated cycloolefin copolymer, and the properties of the cycloolefin copolymer are not affected basically because the polar maleimide groups account for a small proportion. The end-capped functional group is maleimide group, which is used as a high-performance resin, so that the glass transition temperature, the peeling strength and the heat resistance of the material are improved, the compatibility of the cycloolefin copolymer with other resins is improved, the modified cycloolefin copolymer is used as resin to be applied to resin composition glue solution, and the modified cycloolefin copolymer can be crosslinked with itself or other unsaturated resins to form a thermosetting material, so that the adhesiveness of the modified cycloolefin copolymer with other resins is improved while the high glass transition temperature, the excellent dielectric property and the heat resistance of the cycloolefin copolymer are maintained, and the peeling strength is further obviously improved. The modified cycloolefin copolymer can be matched with other unsaturated resins, and can be used as a component of a thermosetting resin composition to be applied to preparation of resin composition glue solution and metal foil-clad laminated plates, so that the prepared laminated plates have good dielectric property, peeling strength and heat resistance.
In the technical scheme, the characteristics of preparation means, materials, structures or composition ratios and the like which are not explicitly described are regarded as common technical characteristics disclosed in the prior art.
The polyphenyl ether disclosed by the invention is engineering plastic with excellent performance, and has excellent heat resistance, hydrolysis resistance stability, low hygroscopicity, good dimensional stability, flame retardance and excellent adhesion with copper foil, and particularly has excellent dielectric performance in a wider temperature range. Specific examples of the unsaturated group-containing modified polyphenylene ether include methyl methacrylate-modified polyphenylene ether (SA 9000) produced by sabic and styrene-end group-modified polyphenylene ether (OPE-2 st) produced by Mitsubishi gas.
The crosslinking agent disclosed by the invention is a secondary crosslinking agent with more active groups, and can be used for improving the crosslinking density of a resin system well. The crosslinking agent is specifically trimethylolpropane trimethacrylate (TMPTMA) produced by Korean KPX chemical group.
The toughening agent disclosed by the invention can improve the dielectric property of the material to a certain extent, can also better improve the binding force between the resin and the surface of the copper foil, and can obtain good peel strength. The toughening agent is specifically exemplified by hydrogenated styrene-butadiene-styrene block copolymer (P1500) produced by Asahi Karaku chemical Co., ltd.
The metal foil clad laminates referred to herein may have various types of gauge sizes, such as: 36X 48, 36.5X 48.5, 37X 49, 40X 48, 40.5X 48.5, 41X 49, 42X 48, 42.5X 48.5, 43X 49, etc. (unit: inches). But are not limited to these dimensions.
The glass fiber cloth disclosed by the invention can be E-grade, and the specifications can be 101, 104, 106, 1078, 1080, 2113, 2116, 1506 or 7628 and the like. But are not limited to these dimensions.
The metal foil referred to in the invention can be copper, brass, aluminum, nickel, and alloys or composite metal foils of these metals, and metal foils with thickness of 1/3oz, hoz, 1oz, 2oz, 3oz and 4oz can be selected. But are not limited to these dimensions.
In the following examples of the invention, all materials are commercially available.
Examples 1 to 4 and comparative examples 1 to 4
The main raw materials for preparing the resin composition glue solution containing the modified cycloolefin copolymer and the related metal foil clad laminated plate thereof consist of modified polyphenyl ether resin, modified cycloolefin copolymer, a cross-linking agent, a toughening agent, a flame retardant, a filling material, an initiator and an organic solvent.
To compare the effect of the difference between the modified cycloolefin copolymer according to the present invention (hereinafter referred to as polymer (A)) and the general hydrocarbon resin and the difference in the addition amount on the performance of the metal clad laminate prepared, comparative examples and example schemes are designed as follows in Table 1 (in parts by weight):
wherein, the main raw materials and manufacturers are as follows:
SA9000 (Sabic, manufactured by Sade basic industries Co., ltd., methyl methacrylate-modified polyphenylene ether) (modified polyphenylene ether resin).
TMPTMA (trimethylolpropane trimethacrylate) (crosslinker, manufactured by korean KPX chemical group).
P1500: (hydrogenated styrene-butadiene-styrene block copolymer produced by Asahi chemical Co., ltd.) (toughening agent).
B3000 (polybutadiene, manufactured by Nippon Caddy Co., ltd.).
Ricon 100 (styrene-butadiene copolymer, manufactured by Cray Valley company).
Ricon 257 (styrene-butadiene-divinylbenzene terpolymer, manufactured by Cray Valley company).
D1118 (styrene-butadiene-styrene Block copolymer manufactured by Kraton Co., ltd.).
PX-200 (condensed phosphate flame retardant: phosphorus content 12.5%) manufactured by Daba chemical industry Co., ltd.).
SP0045 (manufactured by Jiangsu Lishi New Material technologies Co., ltd., spherical silica, D50 of 3 μm, density of 2.20X10) 3 kg/m 3 ) (filler material).
DCP (dicumyl peroxide) (initiator) manufactured by Ningbo New bridge chemical Co., ltd.
The organic solvents were Toluene (TOL) and Methyl Ethyl Ketone (MEK).
Table 1 specific schemes of examples 1 to 4 and comparative examples 1 to 4 (examples and comparative examples in the present invention are defined based on whether or not a host product (modified cycloolefin resin) is added).
| Raw materials | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Example 1 | Example 2 | Example 3 | Example 4 |
| SA9000 | 35 | 35 | 35 | 35 | 35 | 35 | 35 | 35 |
| Polymer (A) | 10 | 10 | 10 | 30 | ||||
| B3000 | 10 | |||||||
| Ricon 100 | 10 | |||||||
| Ricon 257 | 10 | |||||||
| D1118 | 10 | |||||||
| TMPTMA | 15 | 15 | 15 | 15 | 15 | 15 | 15 | |
| P1500 | 8 | 8 | 8 | 8 | 8 | 8 | 8 | |
| PX-200 | 15 | 15 | 15 | 15 | 15 | 15 | 15 | 15 |
| SP0045 | 80 | 80 | 80 | 80 | 80 | 80 | 80 | 80 |
| DCP | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| TOL | 65 | 65 | 65 | 65 | 65 | 65 | 65 | 65 |
| MEK | 40 | 40 | 40 | 40 | 40 | 40 | 40 | 40 |
The preparation process is as follows:
1. preparation of modified cycloolefin copolymer and resin composition glue:
a. firstly, a glass pressure reactor is dried in vacuum for 1h at the temperature of 90-100 ℃, 60mL of anhydrous toluene and 2.5-3.2 mol of norbornene are added into the reactor under the protection of dry inert gas, and then 8-10 mu mol of palladium phosphine sulfonate nickel phenol catalyst is dissolved in 5mL of dichloromethane and then is added into a polymerization system in a dropwise manner. Under the condition of high-speed stirring, butadiene gas is introduced, the pressure is controlled to be 5-8 bar by continuously supplementing butadiene, the reaction is carried out for 1-2 hours at the temperature of 40-60 ℃, then the pressure reactor is emptied, 200ml of ethanol hydrochloride is added for quenching polymerization reaction, and then the unsaturated cycloolefin copolymer is obtained after washing, filtering, purifying and other operations.
1mol of the reaction product is added into a flask filled with 100mL of anhydrous toluene, 3 to 5mol of acid-binding agent triethylamine is added, then 1.2 to 1.8mol of N-hydroxyethyl maleimide solution is slowly added into the flask in a dropwise manner, the mixture is stirred for 3 to 5 hours at the temperature of 25 to 35 ℃ to react, after the complete reaction, the product is filtered, the acid-binding agent is completely washed off by a solvent, and the modified cycloolefin copolymer (polymer (A)) is obtained after washing, suction filtration and drying.
b. Sequentially adding an organic solvent and a toughening agent according to the formula dosage (see table 1), stirring and dissolving, respectively adding modified polyphenyl ether resin, modified cycloolefin copolymer, different types of hydrocarbon resins and cross-linking agents according to the comparative example and the embodiment scheme, starting a high-speed stirrer, rotating at 1000-1500 rpm (the formula dosage is different in the embodiment 1-4 and the comparative example 1-4, and the other conditions are controlled to be the same), and keeping stirring for about 60-90 minutes until the resin is completely dissolved;
c. adding the filling material and the flame retardant according to the formula dosage after the resin is completely dissolved, and stirring for 20-40 minutes at the rotating speed of 1000-1500 rpm;
d. weighing initiator according to the formula amount, adding the initiator into the glue solution, stirring the glue solution for 20 minutes at a rotating speed of 1000-1500 rpm, homogenizing the glue solution for 5-10 minutes by using a homogenizer, and completing glue mixing.
2. And (3) sizing:
placing the homogenized glue solution in a glue tank, sizing the 2116NE glass fiber cloth by an impregnation process, and placing the glue solution in an oven to bake at a high temperature of 130-160 ℃ for 200-300 s to prepare a prepreg;
3. typesetting and pressing;
cutting the prepreg into 5 pieces with the same size, overlapping the prepreg with the metal foil, and pressing to obtain the metal foil-clad laminated board.
4. Platen parameters:
vacuum degree-0.106 Mpa;
pressure 261-564 psi;
the temperature of the hot plate is 150-220 ℃;
curing time was 200min.
The samples of examples 1-4 and comparative examples 1-4 were tested for various properties as follows:
< glass transition temperature (Tg) >)
The peak temperature of Tan delta was measured as the glass transition temperature (Tg) by a dynamic thermo-mechanical analyzer (DMA: dynamic Mechanical Analysis);
< Peel Strength (PS) >
According to the IPC-TM-650-2.4.8 standard, a universal tensile machine is adopted to test the peel strength of the sample;
< dielectric Property >
The dielectric constant Dk and the dielectric loss tangent Df of the substrate at 10GHz were measured using a network analyzer (N5230A, agilent technologies Co., ltd.);
< test of thermal stress tin immersion time >
Immersing a 50X 50mm double-sided copper sample in a tin furnace at 288 ℃ and recording the time of delamination and foaming on the surface of the sample;
< moisture and heat resistance (PCT) test >
A pressure cooker is adopted to carry out a steaming test on a sample, after the plate is continuously steamed for 120min at 120 ℃ through the pressure cooker (0.105 MPa), the plate is immersed into a tin furnace at 288 ℃ to observe layering foaming time, the sample with layering time less than 5min is evaluated as x, the sample with layering time more than 5min and less than 10min is evaluated as k, and the sample with layering time more than 10min is evaluated as c;
< test of heat resistance at 288 ℃ (T288)
Placing a copper-containing foil substrate with the size of 8mm multiplied by 8mm on a thermo-mechanical analyzer (TMA), heating the copper-containing foil substrate to 288 ℃ from room temperature at a heating rate of 10 ℃/min, maintaining the copper-containing foil substrate at 288 ℃, observing the dimensional change of a sample, and recording the time of post-burst plate generation at 288 ℃;
< flame retardance >
Sample test pieces having dimensions of 130mm by 12.5mm were taken, and 2 combustion tests were performed on each of the 5 test pieces according to the UL94 standard. The flame retardancy was evaluated by the total time of the combustion duration at the time of the combustion test.
< Water absorption Rate >
The measurement was performed according to the IPC-TM-6502.6.2.1 method;
< cleavage temperature (Td) >
Square samples with the dimensions of 6.35mm multiplied by 6.35mm are selected, the lowest weight of the samples is 30mg, the samples are baked for 24 hours at 110+/-2 ℃, and cooled to room temperature in a dryer, a thermogravimetric analyzer (TGA) is adopted, the temperature rise rate of 10 ℃/min is adopted, the temperature rise value of 450 ℃ is adopted, the weight loss percentage of the samples along with the temperature rise is recorded, and the temperature when the weight loss is reported to be 5% is Td;
< bending Strength >
The measurement was performed according to the IPC-TM-650.2.4.4 method, and the test was performed by applying a load to a sample of a prescribed size and shape at room temperature.
The properties of the metal foil-clad laminate thus obtained were measured in the manner described above, and the results are shown in Table 2.
Table 2 test results of various properties of the metal foil-clad laminates prepared in examples 1 to 4 and comparative examples 1 to 4.
As can be seen from comparison of comparative examples 1 to 4 with example 3, the resin composition glue solution obtained by adding the modified cycloolefin copolymer is significantly improved in glass transition temperature, thermal expansion coefficient, peel strength, dielectric properties, heat resistance and flexural strength compared with the common hydrocarbon resin with the same additive amount. The general hydrocarbon resin has the problems of insufficient rigidity, low strength, poor heat resistance, low glass transition temperature (Tg), low peeling strength and the like due to the flexible and nonpolar carbon chain structure of the hydrocarbon resin; the modified cycloolefin copolymer is prepared by the method of introducing polar maleimide groups into the unsaturated cycloolefin copolymer, and the characteristics of the cycloolefin copolymer are not affected basically because the proportion of the polar maleimide groups is small. The end-capped functional group is maleimide group, which is used as a high-performance resin, so that the glass transition temperature, the peeling strength, the heat resistance and the mechanical strength of the material are improved, the compatibility of the cycloolefin copolymer with other resins is improved, the modified cycloolefin copolymer is used as resin to be applied to resin composition glue solution, and the modified cycloolefin copolymer can be crosslinked with itself or other unsaturated resins to form thermosetting materials, so that the adhesiveness of the cycloolefin copolymer with other resins is improved while the high glass transition temperature, the excellent dielectric property and the excellent heat resistance of the cycloolefin copolymer are maintained, and the peeling strength is further obviously improved.
As can be seen from a comparison of example 1 and example 3, when the crosslinking agent is absent in the resin composition, the bonding of the crosslinked network between resins is insufficient due to the low crosslinking density, and thus the metal foil-clad laminate prepared from the dope thereof is deficient in Tg, heat resistance, peel strength, dielectric properties and flexural strength; comparing example 2 with example 3, the resulting metal foil clad laminates exhibited slightly poorer performance, particularly in terms of peel strength and dielectric properties, and only slightly advantageous in terms of Z-axis CTE when the toughening agent was absent from the resin composition. Therefore, according to the specific resin composition provided by the invention, the resin composition system can obtain better resin crosslinking density, and the prepared metal-clad laminated plate has obvious advantages in the aspects of CTE, peeling strength, dielectric property, heat resistance, flame retardance and the like, and basically meets the manufacturing requirements of the copper-clad plate.
It can be seen from examples 3 to 4 that the addition of the modified cycloolefin copolymer can significantly improve Tg of the metal clad laminate, and the CTE is reduced, and the peeling property, dielectric properties and bending strength are also improved to some extent, and the flame retardance, heat resistance and water absorption are good, and the performance improvement effect is more remarkable as the number of parts of the modified cycloolefin copolymer added is increased.
The Tg of the metal-clad foil plate prepared by the resin composition glue solution is more than 230 ℃; z-axis CTE < 1.8%; heat resistance: TD is more than or equal to 410 ℃, T288 is more than 120min; electrical properties: the dielectric constant (10 GHZ) is less than or equal to 3.5; dielectric loss (10 GHZ) < 0.0025; in addition, the flame retardant has lower water absorption and good mechanical processing performance, achieves UL94V-0 level, and can completely meet the production requirement of the multilayer board in the field of high-frequency high-speed PCB.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (10)
1. A modified cycloolefin copolymer-containing resin composition characterized in that the resin composition comprises a resin component;
the resin component comprises a modified cycloolefin copolymer and a thermosetting resin;
the modified cycloolefin copolymer has a structure as shown in the formula (I):
in the formula (I), R1 is one or more aliphatic hydrocarbons containing unsaturated bonds and having 2-10 carbon atoms;
in the formula (I), R2 is One or more of the following;
in the formula (I), m and n are integers greater than or equal to 1;
the thermosetting resin comprises modified polyphenyl ether resin, a cross-linking agent and a toughening agent.
2. The modified cycloolefin copolymer-containing resin composition according to claim 1, wherein the modified cycloolefin copolymer is prepared by polymerizing a cyclic olefin with an α -olefin and then introducing a polar maleimide group;
wherein, the catalyst used in the polymerization process of the cyclic olefin and the alpha-olefin is preferably palladium phosphine sulfonate catalyst;
the temperature of the polymerization reaction of the cyclic olefin and the alpha-olefin is 30-80 ℃, and the time of the polymerization reaction is 1-3 h.
3. The modified cycloolefin copolymer-containing resin composition according to claim 1, characterized in that the modified cycloolefin copolymer has a number average molecular weight of 1000 to 12000;
in the R1 unit and the R2 unit of the modified cycloolefin copolymer, the R1 unit accounts for 10-50% of the total amount of the R1 unit and the R2 unit.
4. The modified cycloolefin copolymer containing resin composition according to claim 1, wherein the modified polyphenylene ether resin is a polyphenylene ether resin having a double bond at a terminal group;
the polyphenyl ether resin with the terminal group containing double bonds comprises one or more polyphenyl ether resins modified by allyl, vinyl, styryl or methacrylate groups.
5. The modified cycloolefin copolymer-containing resin composition according to claim 1, wherein the crosslinking agent includes any one or more of a trialkenyl isocyanurate compound, a polyfunctional acrylate compound, a polyfunctional methacrylate compound, a polyfunctional vinyl compound, and a divinylbenzene compound.
6. The modified cycloolefin copolymer containing resin composition according to claim 1, wherein the toughening agent contains one or more of polybutadiene, a styrene-butadiene block copolymer, a styrene-butadiene-styrene triblock copolymer, a hydrogenated styrene/butadiene/styrene block copolymer, and a maleic anhydride grafted styrene-butadiene-styrene block copolymer.
7. The modified cycloolefin copolymer-containing resin composition according to claim 1, which further comprises a flame retardant, a filler, an initiator and an organic solvent;
the flame retardant comprises one or a combination of a plurality of brominated flame retardants, phosphorus flame retardants and nitrogen flame retardants.
8. The modified cycloolefin copolymer containing resin composition according to claim 7, characterized in that the filler is a combination of one or more of fine silica powder, metal oxide, metal hydroxide, talc, aluminum borate, barium sulfate and calcium carbonate;
the initiator is one or more of dicumyl peroxide, di-tert-butyl peroxide, benzoyl peroxide, tert-butyl peroxybenzoate, dicyclohexyl peroxydicarbonate, cumene hydroperoxide and azobisisobutyronitrile;
the organic solvent is one or more of toluene, butanone, acetone, dimethylformamide or propylene glycol methyl ether.
9. A metal foil-clad laminate using the modified cycloolefin copolymer-containing resin composition according to any one of claims 1 to 8, characterized in that the metal foil-clad laminate is produced using the modified cycloolefin copolymer-containing resin composition.
10. A metal foil-clad laminate using the modified cycloolefin copolymer-containing resin composition according to any one of claims 1 to 8 or the method for producing a metal foil-clad laminate according to claim 9, characterized in that the method for producing comprises the steps of:
stirring the toughening agent, the modified polyphenyl ether resin, the modified cycloolefin copolymer and the crosslinking agent by using an organic solvent until the resin is completely dissolved to obtain a solution A;
(ii) adding a flame retardant and a filling material into the solution A obtained in the step (i) and uniformly mixing to obtain a solution B;
(iii) adding an initiator into the solution B obtained in the step (ii), uniformly mixing, and homogenizing and discharging to obtain a resin composition glue solution;
(iv) sizing the glass fiber cloth by the resin composition glue solution obtained in the step (iii) through an impregnation process, and placing the glass fiber cloth in an oven to bake for 200-300 seconds at a high temperature of 120-160 ℃ to obtain a prepreg;
and (v) cutting the prepreg obtained in the step (iv), respectively covering the two sides with metal foils, and pressing under vacuum conditions to obtain the metal foil-clad laminated board.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311165321.2A CN117186617A (en) | 2023-09-11 | 2023-09-11 | Resin composition containing modified cycloolefin copolymer, metal-clad laminate using same and preparation method of metal-clad laminate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311165321.2A CN117186617A (en) | 2023-09-11 | 2023-09-11 | Resin composition containing modified cycloolefin copolymer, metal-clad laminate using same and preparation method of metal-clad laminate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117186617A true CN117186617A (en) | 2023-12-08 |
Family
ID=88990162
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311165321.2A Pending CN117186617A (en) | 2023-09-11 | 2023-09-11 | Resin composition containing modified cycloolefin copolymer, metal-clad laminate using same and preparation method of metal-clad laminate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117186617A (en) |
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2023
- 2023-09-11 CN CN202311165321.2A patent/CN117186617A/en active Pending
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