TWI637405B - 低介電樹脂組合物及應用其的膠片及電路板 - Google Patents
低介電樹脂組合物及應用其的膠片及電路板 Download PDFInfo
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- TWI637405B TWI637405B TW106108432A TW106108432A TWI637405B TW I637405 B TWI637405 B TW I637405B TW 106108432 A TW106108432 A TW 106108432A TW 106108432 A TW106108432 A TW 106108432A TW I637405 B TWI637405 B TW I637405B
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- Prior art keywords
- low dielectric
- resin composition
- dielectric resin
- resin
- anhydride
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims abstract description 97
- 229920005989 resin Polymers 0.000 claims abstract description 70
- 239000011347 resin Substances 0.000 claims abstract description 70
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 29
- 239000003822 epoxy resin Substances 0.000 claims abstract description 20
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 20
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 13
- 239000010410 layer Substances 0.000 claims description 24
- -1 ethylene-butylene-styrene Chemical class 0.000 claims description 18
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 14
- 150000002148 esters Chemical class 0.000 claims description 13
- 229920001955 polyphenylene ether Polymers 0.000 claims description 13
- NADYEWVQIJRXJM-UHFFFAOYSA-N 1,3-bis(oxiran-2-ylmethyl)-5-prop-2-enyl-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC=C)C(=O)N1CC1CO1 NADYEWVQIJRXJM-UHFFFAOYSA-N 0.000 claims description 11
- 239000012790 adhesive layer Substances 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 10
- 150000001993 dienes Chemical class 0.000 claims description 8
- IRDLUHRVLVEUHA-UHFFFAOYSA-N diethyl dithiophosphate Chemical compound CCOP(S)(=S)OCC IRDLUHRVLVEUHA-UHFFFAOYSA-N 0.000 claims description 8
- 239000003292 glue Substances 0.000 claims description 8
- 229920002943 EPDM rubber Polymers 0.000 claims description 6
- 239000005062 Polybutadiene Substances 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 229920002857 polybutadiene Polymers 0.000 claims description 6
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 4
- 125000003700 epoxy group Chemical group 0.000 claims description 4
- 150000003512 tertiary amines Chemical class 0.000 claims description 4
- DWECLTSJFWPZCT-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinan-2-one Chemical compound C1N(CC2OC2)CN(CC2OC2)C(=O)N1CC1CO1 DWECLTSJFWPZCT-UHFFFAOYSA-N 0.000 claims description 3
- 229920006132 styrene block copolymer Polymers 0.000 claims description 3
- XFHNJLUAFSZQRV-UHFFFAOYSA-N 1-(oxiran-2-ylmethyl)-3,5-bis(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC=C)C(=O)N(CC=C)C(=O)N1CC1OC1 XFHNJLUAFSZQRV-UHFFFAOYSA-N 0.000 claims description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 2
- 239000004713 Cyclic olefin copolymer Substances 0.000 claims description 2
- 239000007983 Tris buffer Substances 0.000 claims description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 2
- 150000003003 phosphines Chemical class 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 claims description 2
- IBWGNZVCJVLSHB-UHFFFAOYSA-M tetrabutylphosphanium;chloride Chemical compound [Cl-].CCCC[P+](CCCC)(CCCC)CCCC IBWGNZVCJVLSHB-UHFFFAOYSA-M 0.000 claims description 2
- LIXPXSXEKKHIRR-UHFFFAOYSA-M tetraethylphosphanium;bromide Chemical compound [Br-].CC[P+](CC)(CC)CC LIXPXSXEKKHIRR-UHFFFAOYSA-M 0.000 claims description 2
- ZOMVKCHODRHQEV-UHFFFAOYSA-M tetraethylphosphanium;hydroxide Chemical compound [OH-].CC[P+](CC)(CC)CC ZOMVKCHODRHQEV-UHFFFAOYSA-M 0.000 claims description 2
- RYVBINGWVJJDPU-UHFFFAOYSA-M tributyl(hexadecyl)phosphanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[P+](CCCC)(CCCC)CCCC RYVBINGWVJJDPU-UHFFFAOYSA-M 0.000 claims description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims 2
- KEXQTSAIHPVLAD-UHFFFAOYSA-N 4,5,6,7-tetrabutyl-2H-benzotriazole Chemical class C(CCC)C1=C(C(=C(C2=C1NN=N2)CCCC)CCCC)CCCC KEXQTSAIHPVLAD-UHFFFAOYSA-N 0.000 claims 1
- RDVLKFWQJDSWBB-UHFFFAOYSA-N Cl.OP(O)=O Chemical class Cl.OP(O)=O RDVLKFWQJDSWBB-UHFFFAOYSA-N 0.000 claims 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims 1
- 229910019142 PO4 Inorganic materials 0.000 claims 1
- TUDUDQJRUPFUMA-UHFFFAOYSA-M ethyl(trioctyl)phosphanium;bromide Chemical compound [Br-].CCCCCCCC[P+](CC)(CCCCCCCC)CCCCCCCC TUDUDQJRUPFUMA-UHFFFAOYSA-M 0.000 claims 1
- 235000019256 formaldehyde Nutrition 0.000 claims 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 claims 1
- 239000003431 cross linking reagent Substances 0.000 abstract description 30
- 229920001721 polyimide Polymers 0.000 abstract description 5
- 239000009719 polyimide resin Substances 0.000 abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 42
- 230000000052 comparative effect Effects 0.000 description 19
- 239000010408 film Substances 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 11
- KRDXTHSSNCTAGY-UHFFFAOYSA-N 2-cyclohexylpyrrolidine Chemical compound C1CCNC1C1CCCCC1 KRDXTHSSNCTAGY-UHFFFAOYSA-N 0.000 description 10
- 229920002554 vinyl polymer Polymers 0.000 description 10
- 239000011889 copper foil Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 6
- 230000008054 signal transmission Effects 0.000 description 6
- 229920001748 polybutylene Polymers 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 150000001451 organic peroxides Chemical group 0.000 description 4
- 150000002978 peroxides Chemical class 0.000 description 4
- 229910000679 solder Inorganic materials 0.000 description 4
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- DBNJSZYFWVVQBO-UHFFFAOYSA-N SOOS Chemical compound SOOS DBNJSZYFWVVQBO-UHFFFAOYSA-N 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 238000005476 soldering Methods 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229920000106 Liquid crystal polymer Polymers 0.000 description 2
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- SJPFBRJHYRBAGV-UHFFFAOYSA-N n-[[3-[[bis(oxiran-2-ylmethyl)amino]methyl]phenyl]methyl]-1-(oxiran-2-yl)-n-(oxiran-2-ylmethyl)methanamine Chemical compound C1OC1CN(CC=1C=C(CN(CC2OC2)CC2OC2)C=CC=1)CC1CO1 SJPFBRJHYRBAGV-UHFFFAOYSA-N 0.000 description 2
- MMCOUVMKNAHQOY-UHFFFAOYSA-L oxido carbonate Chemical compound [O-]OC([O-])=O MMCOUVMKNAHQOY-UHFFFAOYSA-L 0.000 description 2
- 238000007719 peel strength test Methods 0.000 description 2
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 1
- OXYKVVLTXXXVRT-UHFFFAOYSA-N (4-chlorobenzoyl) 4-chlorobenzenecarboperoxoate Chemical compound C1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1 OXYKVVLTXXXVRT-UHFFFAOYSA-N 0.000 description 1
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 1
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 1
- WVGXBYVKFQJQGN-UHFFFAOYSA-N 1-tert-butylperoxy-2-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC=C1OOC(C)(C)C WVGXBYVKFQJQGN-UHFFFAOYSA-N 0.000 description 1
- 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 1
- DPGYCJUCJYUHTM-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-yloxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)CC(C)(C)C DPGYCJUCJYUHTM-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- YAQDPWONDFRAHF-UHFFFAOYSA-N 2-methyl-2-(2-methylpentan-2-ylperoxy)pentane Chemical compound CCCC(C)(C)OOC(C)(C)CCC YAQDPWONDFRAHF-UHFFFAOYSA-N 0.000 description 1
- KFJDQPJLANOOOB-UHFFFAOYSA-N 2h-benzotriazole-4-carboxylic acid Chemical compound OC(=O)C1=CC=CC2=NNN=C12 KFJDQPJLANOOOB-UHFFFAOYSA-N 0.000 description 1
- PBVAJRFEEOIAGW-UHFFFAOYSA-N 3-[bis(2-carboxyethyl)phosphanyl]propanoic acid;hydrochloride Chemical compound Cl.OC(=O)CCP(CCC(O)=O)CCC(O)=O PBVAJRFEEOIAGW-UHFFFAOYSA-N 0.000 description 1
- YPIFGDQKSSMYHQ-UHFFFAOYSA-M 7,7-dimethyloctanoate Chemical compound CC(C)(C)CCCCCC([O-])=O YPIFGDQKSSMYHQ-UHFFFAOYSA-M 0.000 description 1
- DURWVQDYQSIGKC-UHFFFAOYSA-N 8-methyl-1-(8-methylnonylperoxy)nonane Chemical compound C(CCCCCCC(C)C)OOCCCCCCCC(C)C DURWVQDYQSIGKC-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- YOWJRQZLZDBONJ-UHFFFAOYSA-N P.OP(O)=O Chemical compound P.OP(O)=O YOWJRQZLZDBONJ-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GMJZOMKCRBNEED-UHFFFAOYSA-N [(5-benzhydrylperoxy-2,5-dimethylhexan-2-yl)peroxy-phenylmethyl]benzene Chemical compound CC(C)(CCC(C)(OOC(C1=CC=CC=C1)C1=CC=CC=C1)C)OOC(C1=CC=CC=C1)C1=CC=CC=C1 GMJZOMKCRBNEED-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000013039 cover film Substances 0.000 description 1
- WRKRMDNAUJERQT-UHFFFAOYSA-N cumene hydroxyperoxide Chemical compound OOOO.CC(C)C1=CC=CC=C1 WRKRMDNAUJERQT-UHFFFAOYSA-N 0.000 description 1
- BLCKNMAZFRMCJJ-UHFFFAOYSA-N cyclohexyl cyclohexyloxycarbonyloxy carbonate Chemical compound C1CCCCC1OC(=O)OOC(=O)OC1CCCCC1 BLCKNMAZFRMCJJ-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- QUPCNWFFTANZPX-UHFFFAOYSA-N hydrogen peroxide;1-methyl-4-propan-2-ylcyclohexane Chemical compound OO.CC(C)C1CCC(C)CC1 QUPCNWFFTANZPX-UHFFFAOYSA-N 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000010365 information processing Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- IBIRZFNPWYRWOG-UHFFFAOYSA-N phosphane;phosphoric acid Chemical compound P.OP(O)(O)=O IBIRZFNPWYRWOG-UHFFFAOYSA-N 0.000 description 1
- REJGOFYVRVIODZ-UHFFFAOYSA-N phosphanium;chloride Chemical compound P.Cl REJGOFYVRVIODZ-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 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
- FFIUNPRXUCRYFU-UHFFFAOYSA-N tert-butyl pentaneperoxoate Chemical compound CCCCC(=O)OOC(C)(C)C FFIUNPRXUCRYFU-UHFFFAOYSA-N 0.000 description 1
- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- ABJGUZZWSKMTEI-UHFFFAOYSA-M tributyl(dodecyl)phosphanium;bromide Chemical compound [Br-].CCCCCCCCCCCC[P+](CCCC)(CCCC)CCCC ABJGUZZWSKMTEI-UHFFFAOYSA-M 0.000 description 1
- GGJHLMANZFSVPZ-UHFFFAOYSA-M tributyl(prop-2-enyl)phosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CC=C GGJHLMANZFSVPZ-UHFFFAOYSA-M 0.000 description 1
- ILMHHPQBPCVAKL-UHFFFAOYSA-N tridecylphosphanium;bromide Chemical compound [Br-].CCCCCCCCCCCCC[PH3+] ILMHHPQBPCVAKL-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/246—Intercrosslinking of at least two polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/006—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to block copolymers containing at least one sequence of polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
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Abstract
一種低介電樹脂組合物,其包括含酸酐的低介電樹脂、環氧樹脂、硬質交聯劑、軟質交聯劑及促進劑,該含酸酐的低介電樹脂選自馬來酸酐接枝改質樹脂及含酸酐的聚醯亞胺樹脂中的一種或兩種,其中,該含酸酐的聚醯亞胺樹脂的介電常數小於3。另,本發明還提供一種應用所述低介電樹脂組合物的膠片,一種應用所述低介電樹脂組合物製得的電路板。
Description
本發明涉及一種低介電樹脂組合物、應用該低介電樹脂組合物的膠片及電路板。
在大資料時代,電子產品的資訊處理不斷向著信號傳輸高頻化和高速數位化的方向發展。若要保證電子產品在高頻信號傳輸的條件下同時具有良好的信號傳輸品質,需要電路板的導電銅箔中的傳輸線與其所連接的電子元件之間處於阻抗匹配狀態,避免造成信號反射、散射、衰減及延遲等現象。電路板中與導電線路相接觸的膠層的材料的介電常數是影響高頻傳輸阻抗匹配的其中一種因素。為了實現高頻信號傳輸阻抗匹配,膠層通常需要選擇介電常數較低的材料。
而傳統的電路板所使用的膠層中樹脂組合物含有極性官能團,造成介電常數及介電損失偏大。例如,環氧樹脂中環氧基因開環後形成有羥基,而導致介電常數高達3.4以上,介電損失高達0.02以上;聚醯亞胺因含有聚醯亞胺基,導致介電常數高達3.2以上,介電損失高達0.007以上;液晶高分子雖介電常數小於3.0,介電損失小於0.002,但是,由液晶高分子製成的膠片無法滿足電路板製程中高溫壓合的要求,且液晶高分子的價格昂貴。為改善上述習知材料的介電常數及介電損失,需要選擇較低極性的樹脂材料。然而,一般的低極性
材料無法與極性分子相混合,而用於製作膠片的樹脂組合物製作過程需要將低極性樹脂與極性溶劑或極性添加劑等混合。
有鑑於此,有必要提供一種新的低介電樹脂組合物,以解決上述問題。
另,還有必要提供一種應用所述低介電樹脂組合物的膠片。
另,還有必要提供一種應用所述低介電樹脂組合物製得的電路板。
一種低介電樹脂組合物,其包括含酸酐的低介電樹脂、環氧樹脂、硬質交聯劑、軟質交聯劑及促進劑,所述含酸酐的低介電樹脂選自馬來酸酐接枝改質樹脂及含酸酐的聚醯亞胺樹脂中的一種或兩種,其中,該含酸酐的聚醯亞胺樹脂的介電常數小於3。
一種應用所述低介電樹脂組合物的膠片,其包括樹脂層及結合於該樹脂層至少一表面的離型膜,該樹脂層的材質為所述低介電樹脂組合物。
一種應用所述低介電樹脂組合物製得的電路板,其包括電路基板及結合於該電路基板至少一表面的膠層,該膠層由所述低介電樹脂組合物經烘烤後製得。
本發明的低介電樹脂組合物採用含酸酐的低介電樹脂,該含酸酐的低介電樹脂相較於不含酸酐的低介電樹脂可以更好的溶解於有機溶劑中,且含酸酐的低介電樹脂相較於不含酸酐的低介電樹脂與其它有機組分的相容性更好,有助於獲得介電常數更低、性能更好的低介電樹脂組合物,從而使由該低介電樹脂組合物製得的電路板的膠層具有較低的介電常數,進而使該電路板具有高頻化和高速數位化的信號傳輸性能。
100‧‧‧膠片
10‧‧‧離型膜
20‧‧‧樹脂層
200‧‧‧電路板
201‧‧‧電路基板
202‧‧‧膠層
圖1是本發明一較佳實施例的膠片的截面示意圖。
圖2是本發明一較佳實施例的電路板的截面示意圖。
本發明較佳實施方式提供一種低介電樹脂組合物,其主要用於電路板的基材、膠層或覆蓋膜中。該低介電樹脂組合物包括含酸酐的低介電樹脂、環氧樹脂、硬質交聯劑、軟質交聯劑及促進劑。
所述低介電樹脂組合物中,該含酸酐的低介電樹脂的含量範圍為100重量份,該環氧樹脂的含量範圍為5~30重量份,該硬質交聯劑的含量為5~50重量份,該軟質交聯劑的含量為5~50重量份,該促進劑的含量範圍為0.1~5重量份。
所述低介電樹脂組合物的介電常數Dk小於2.4,介電損失Df小於0.004。
所述含酸酐的低介電樹脂包括但不限於馬來酸酐接枝改質樹脂及含酸酐的聚醯亞胺樹脂中的一種或兩種。其中,該馬來酸酐接枝改質樹脂包括但不限於馬來酸酐接枝苯乙烯-乙烯-丁烯-苯乙烯嵌段共聚物(SEBS-g-MA)、馬來酸酐接枝環烯烴共聚物(COC-g-MA)、及馬來酸酐接枝三元乙丙橡膠(EPDM-g-MA)中的一種或幾種。所述含酸酐的聚醯亞胺樹脂的介電常數Dk小於3。該含酸酐的低介電樹脂相較於不含酸酐的低介電樹脂可以更好的溶解於有機溶劑中,且含酸酐的低介電樹脂相較於不含酸酐的低介電樹脂與其它有機組分的相容性更好,有助於獲得介電常數更低、性能更好的低介電樹脂組合物。
所述馬來酸酐接枝苯乙烯-乙烯-丁烯-苯乙烯嵌段共聚物(SEBS-g-MA)的結構式如下:
其中,w、x、y、z均為大於0的自然數。
所述馬來酸酐接枝環烯烴共聚物(COC-g-MA)的結構式如下:
其中,X、Y均為大於0的自然數。
所述馬來酸酐接枝三元乙丙橡膠(EPDM-g-MA)的結構式如下:
其中p、q均為大於0的自然數。
所述環氧樹脂為特殊環氧樹脂,該特殊環氧樹脂為含有兩個以上環氧基團的環氧樹脂或含有乙烯基的環氧樹脂。所述環氧樹脂包括但不限於1,3-雙(環氧乙烷基甲基)-5-(2-丙烯基)-1,3,5-三嗪-2,4,6(1H,3H,5H)-三酮、1-環氧乙烷基甲基-3,5-二-2-丙烯基-1,3,5-三嗪-2,4,6(1H,3H,5H)-三酮、1,3,5-三縮水甘油-S-三嗪三酮、N,N,N',N'-四(環氧乙烷基甲基)-1,3-苯二甲胺、及2,2',2",2'''-[1,2-聯二亞甲基四(4,1-亞苯基亞甲氧)]四環氧乙烷中的一種或幾種。
其中,1,3-雙(環氧乙烷基甲基)-5-(2-丙烯基)-1,3,5-三嗪-2,4,6(1H,3H,5H)-三酮的結構式為:
1-環氧乙烷基甲基-3,5-二-2-丙烯基-1,3,5-三嗪-2,4,6(1H,3H,5H)-三酮的結構式為:
1,3,5-三縮水甘油-S-三嗪三酮的結構式為:
N,N,N',N'-四(環氧乙烷基甲基)-1,3-苯二甲胺的結構式為:
2,2',2",2'''-[1,2-聯二亞甲基四(4,1-亞苯基亞甲氧)]四環氧乙烷的結構式為:
所述硬質交聯劑可以為未端含乙烯基與活性酯的聚苯醚樹脂。該未端含乙烯基與活性酯的聚苯醚樹脂的分子量的範圍為1500~2500g/mol。該硬質交聯劑可以調整所述低介電樹脂組合物所形成的膠層的硬度。
所述軟質交聯劑可以為馬來酸化液態聚丁二烯。該馬來酸化液態聚丁二烯的分子量的範圍為2000~8000g/mol,其結構式為:
其中,x1、y1、z1均為大於0的自然數。該軟質交聯劑可以調整所述低介電樹脂組合物所形成的膠層的柔軟度。
所述環氧樹脂中的環氧基可以與含酸酐的低介電樹脂中的酸酐、硬質交聯劑中的活性酯基、軟質交聯劑中的酸酐發生交聯反應,從而將含酸酐的低介電樹脂、硬質交聯劑及軟質交聯劑串聯起來,得到耐熱性較高且交聯密度較高的低介電樹脂組合物。
所述促進劑為環氧與酸酐反應促進劑。該環氧與酸酐反應促進劑包括但不限於三級胺類促進劑及有機膦衍生物中的一種或兩種。
所述三級胺類促進劑包括但不限於N,N-二甲基苄胺、N,N-二甲基苯胺及三乙胺中的一種或幾種。
所述有機膦衍生物包括但不限於丙烯基三丁基鏻溴化物(Allyltri-n-butylphosphonium bromide,C15H32P.Br)、溴化三丁基(十二烷基)磷(Dodecyltributylphosphonium bromide,C24H52BrP)、乙基三正辛基溴化膦(ltrioctylphosphonium bromide,C26H56BrP)、十六烷基三丁基溴化鏻(Tributylhexadecylphosphonium bromide,C28H60BrP)、碘化三丁基甲基膦(Methyltributylphosphonium iodide,C13H30IP)、四乙基溴化膦(Tetraethylphosphonium Bromide,C8H20BrP)、四乙基氫氧化膦溶液(Tetraethylphosphonium hydroxide,C8H21OP)、四丁基溴化膦(Tetrabutylphosphonium bromide,C16H36BrP)、四丁基氯化膦(Tetra-n-butylphosphonium chloride,C16H36ClP)、四丁基O,O-二乙基二硫代磷酸膦(Tetra-n-butylphosphonium O,O-Diethylphosphorodithioate,C20H46O2P2S2)、
四丁基苯並三唑鹽(Tetra-n-butylphosphonium Benzotriazolate,C22H40N3P)、三(2-甲醯乙基)膦鹽酸鹽(Tris(2-carboxyethyl)phosphinehydrochloride,C9H16ClO6P)。
所述低介電樹脂組合物還包括熱起始劑。所述低介電樹脂組合物中,該熱起始劑的含量範圍為0.1~5重量份。
所述熱起始劑為利用示差掃描熱卡計DSC所測定的發熱峰在100~200℃範圍內的有機過氧化物。該有機過氧化物選自二醯基過氧化物、過氧基縮酮、過氧化碳酸酯、過氧酯、酮過氧化物、二烷基過氧化物及氫過氧化物中的一種或幾種。其中,該二醯基過氧化物包括但不限於異壬醯基過氧化物、癸醯基過氧化物、月桂醯基過氧化物、對氯苯甲醯基過氧化物及二(3,5,5-三甲基己醯基)過氧化物中的一種或幾種。該過氧基縮酮包括但不限於2,2-二(4,4-二-(二-第三丁基過氧基)環己基)丙烷。該過氧化碳酸酯包括但不限於二-3-甲氧基丁基過氧二碳酸酯及二環己基過氧二碳酸酯中的一種或兩種。該過氧酯包括但不限於第三丁基過氧苯甲酸酯、第三丁基過氧乙酸酯、第三丁基過氧-2-乙基己酸酯、第三丁基過氧異丁酸酯、第三丁基過氧戊酸酯、第三丁基二過氧己二酸酯、異丙苯基過氧新癸酸酯、第三丁基過氧苯甲酸酯、1,1,3,3-四甲基過氧基-2-乙基己酸酯及2,5-二甲基-2,5-二(苯甲醯基過氧基)己烷中的一種或幾種。該酮過氧化物包括但不限於甲基乙基酮過氧化物及環己酮過氧化物中的一種或兩種。該二烷基過氧化物包括但不限於二-第三丁基過氧化物、二異丙苯基過氧化物、第三丁基異丙苯基過氧化物、1,1-二(第三己基過氧基)-3,3,5-三甲基環己烷、二-第三己基過氧化物及二(2-第三丁基過氧基異丙基)苯中的一種或幾種。該氫過氧化物包括但不限於異丙苯羥基過氧化物、第三丁基過氧化氫及對-薄荷烷過氧化氫中的一種或幾種。在加熱時,該熱起始劑會分解產生自由基,該自由基與乙烯基作用進行起始反應。
優選的,所述有機過氧化物選自過氧酯及二烷基過氧化物中的一種或兩種。更優選的,所述有機過氧化物選自第三丁基過氧基苯甲酸酯、1,1,3,3-四甲基丁基過氧基-2-乙基己酸酯及二(2-第三丁基過氧基異丙基)苯中的一種或幾種。
可以理解的,所述低介電樹脂組合物還可以包括習知應用於低介電樹脂組合物的潤滑劑、填充物、阻燃劑及離子捕捉劑等。
所述低介電樹脂組合物還包括溶劑。所述低介電樹脂組合物中,該溶劑的加入量可根據需要進行變更,只要使所述含酸酐的低介電樹脂、環氧樹脂、硬質交聯劑、軟質交聯劑、促進劑及熱起始劑等能夠完全溶解便可。該溶劑可以為習知應用於樹脂組合物的甲苯等。
所述低介電樹脂組合物的製備方法可以為:將含酸酐的低介電樹脂、環氧樹脂、硬質交聯劑、軟質交聯劑、促進劑及熱起始劑等按照預定比例加入至反應瓶中,向反應瓶中加入適量的溶劑,混合攪拌,使含酸酐的低介電樹脂、環氧樹脂、硬質交聯劑、軟質交聯劑、促進劑及熱起始劑溶解於溶劑中,即製得所述低介電樹脂組合物。
請參閱圖1,本發明還提供一種由上述低介電樹脂組合物製得的膠片100,該膠片100包括樹脂層20及結合於該樹脂層20至少一表面的離型膜10。該樹脂層20藉由將所述低介電樹脂組合物塗敷在離型膜10的表面後形成。
請參閱圖2,本發明還提供一種由上述膠片100製得的電路板200,其包括電路基板201及結合於該電路基板201至少一表面的膠層202。該膠層202藉由將所述膠片100的樹脂層20貼合於電路基板201的表面,移除離型膜10,再經烘烤製得。因所述低介電樹脂組合物具有較低的介電常數、介電損失、較高的交聯密度及較高的耐熱性,故由其製作的電路板200的膠層202也具有較低的介電常數、介電損失、較高的交聯密度及較高的耐熱性,因此,在後續的習
知的電路板的焊錫製程中,該膠層202中的化學交聯的網路結構不會失效,可適應電路板的耐熱性需求。
下面藉由實施例來對本發明進行具體說明。
實施例1
於1000ml反應瓶中依序加入100g COC-g-MA、20g未端含乙烯基與活性酯的聚苯醚樹脂(沙特基礎工業公司(SABIC),型號:SA9000)、15g馬來酸化液態聚丁二烯(克雷威利化工有限公司(Cray valley Ricon),型號:130MA13)、5g 1,3-雙(環氧乙烷基甲基)-5-(2-丙烯基)-1,3,5-三嗪-2,4,6(1H,3H,5H)-三酮、1g第三丁基異丙苯基過氧化物、1g四丁基O,O-二乙基二硫代磷酸膦、568g甲苯,攪拌溶解即配置得到低介電樹脂組合物。
實施例2
於1000ml反應瓶中依序加入100g EPDM-g-MA、20g未端含乙烯基與活性酯的聚苯醚樹脂(沙特基礎工業公司(SABIC),型號:SA9000)、15g馬來酸化液態聚丁二烯(克雷威利化工有限公司(Cray valley Ricon),型號:130MA13)、5g 1,3-雙(環氧乙烷基甲基)-5-(2-丙烯基)-1,3,5-三嗪-2,4,6(1H,3H,5H)-三酮、1g第三丁基異丙苯基過氧化物、1g四丁基O,O-二乙基二硫代磷酸膦、568g甲苯,攪拌溶解即配置得到低介電樹脂組合物。
實施例3
於1000ml反應瓶中依序加入100g含酸酐的聚醯亞胺樹脂、20g未端含乙烯基與活性酯的聚苯醚樹脂(沙特基礎工業公司(SABIC),型號:SA9000)、15g馬來酸化液態聚丁二烯(克雷威利化工有限公司(Cray valley Ricon),型號:130MA13)、5g 1,3-雙(環氧乙烷基甲基)-5-(2-丙烯基)-1,3,5-三嗪-2,4,6(1H,3H,5H)-三酮、1g第三丁基異丙苯基過氧化物、1g四丁基O,O-二乙基二硫代磷酸膦、568g甲苯,攪拌溶解即配置得到低介電樹脂組合物。
實施例4
於1000ml反應瓶中依序加入100g SEBS-g-MA、20g未端含乙烯基與活性酯的聚苯醚樹脂(沙特基礎工業公司(SABIC),型號:SA9000)、15g馬來酸化液態聚丁二烯(克雷威利化工有限公司(Cray valley Ricon),型號:130MA13)、5g 1,3-雙(環氧乙烷基甲基)-5-(2-丙烯基)-1,3,5-三嗪-2,4,6(1H,3H,5H)-三酮、1g第三丁基異丙苯基過氧化物、1g四丁基O,O-二乙基二硫代磷酸膦、568g甲苯,攪拌溶解即配置得到低介電樹脂組合物。
實施例5
於1000ml反應瓶中依序加入100g SEBS-g-MA、30g未端含乙烯基與活性酯的聚苯醚樹脂(沙特基礎工業公司(SABIC),型號:SA9000)、15g馬來酸化液態聚丁二烯(克雷威利化工有限公司(Cray valley Ricon),型號:130MA13)、5g 1,3-雙(環氧乙烷基甲基)-5-(2-丙烯基)-1,3,5-三嗪-2,4,6(1H,3H,5H)-三酮、1g第三丁基異丙苯基過氧化物、1g四丁基O,O-二乙基二硫代磷酸膦、608g甲苯,攪拌溶解即配置得到低介電樹脂組合物。
實施例6
於1000ml反應瓶中依序加入100g SEBS-g-MA、20g未端含乙烯基與活性酯的聚苯醚樹脂(沙特基礎工業公司(SABIC),型號:SA9000)、30g馬來酸化液態聚丁二烯(克雷威利化工有限公司(Cray valley Ricon),型號:130MA13)、5g 1,3-雙(環氧乙烷基甲基)-5-(2-丙烯基)-l,3,51三嗪-2,4,6(1H,3H,5H)-三酮、1g第三丁基異丙苯基過氧化物、1g四丁基O,O-二乙基二硫代磷酸膦、628g甲苯,攪拌溶解即配置得到低介電樹脂組合物。
比較例1
於1000ml反應瓶中依序加入100g COC-g-MA、400g甲苯,攪拌溶解即配置得到樹脂組合物。
比較例2
於1000ml反應瓶中依序加入100g EPDM-g-MA、400g甲苯,攪拌溶解即配置得到樹脂組合物。
比較例3
於1000ml反應瓶中依序加100g含酸酐的聚醯亞胺樹脂、400g甲苯,攪拌溶解即配置得到樹脂組合物。
比較例4
於1000ml反應瓶中依序加入100g SEBS-g-MA、400g甲苯,攪拌溶解即配置得到樹脂組合物。
比較例5
於1000ml反應瓶中依序加入100g三元乙丙橡膠(EPDM)、20g未端含乙烯基與活性酯的聚苯醚樹脂(沙特基礎工業公司(SABIC),型號:SA9000)、15g馬來酸化液態聚丁二烯(克雷威利化工有限公司(Cray valley Ricon),型號:130MA13)、5g 1,3-雙(環氧乙烷基甲基)-5-(2-丙烯基)-1,3,5-三嗪-2,4,6(1H,3H,5H)-三酮、1g第三丁基異丙苯基過氧化物、1g四丁基O,O-二乙基二硫代磷酸膦、568g甲苯,攪拌溶解即配置得到樹脂組合物。
比較例6
於1000ml反應瓶中依序加入100g SEBS-g-MA、60g未端含乙烯基與活性酯的聚苯醚樹脂(沙特基礎工業公司(SABIC),型號:SA9000)、15g馬來酸化液態聚丁二烯(克雷威利化工有限公司(Cray valley Ricon),型號:130MA13)、5g 1,3-雙(環氧乙烷基甲基)-5-(2-丙烯基)-1,3,5-三嗪-2,4,6(1H,3H,5H)-三酮、1g第三丁基異丙苯基過氧化物、1g四丁基O,O-二乙基二硫代磷酸膦、728g甲苯,攪拌溶解即配置得到樹脂組合物。
比較例7
於1000ml反應瓶中依序加入100g SEBS-g-MA、20g未端含乙烯基與活性酯的聚苯醚樹脂(沙特基礎工業公司(SABIC),型號:SA9000)、60g馬來酸化液態聚丁二烯(克雷威利化工有限公司(Cray valley Ricon),型號:130MA13)、5g 1,3-雙(環氧乙烷基甲基)-5-(2-丙烯基)-1,3,5-三嗪-2,4,6(1H,3H,5H)-三酮、1g第三丁基異丙苯基過氧化物、1g四丁基O,O-二乙基二硫代磷酸膦、748g甲苯,攪拌溶解即配置得到樹脂組合物。
對實施例1~6所製備的低介電樹脂組合物以及比較例1~7所製備的樹脂組合物的介電常數Dk和介電損失Df分別進行測試。然後,使用銅箔和聚醯亞胺(Polyimide,PI)薄膜製備包括銅箔和覆蓋層的電路基板,使用實施例1~6所製備的低介電樹脂組合物以及對比例1~7所製備的樹脂組合物分別製備膠片,利用該膠片製備電路板的結合於電路基板的表面的膠層,然後對該具有膠層的電路板進行銅剝離強度測試、PI剝離強度測試、漂錫耐熱性測試及彈性模量測試,檢測結果請參照表一的性能檢測資料。其中,若漂錫耐熱性測試條件大於等於260℃ 10sec(秒)時,錫不脫落,則漂錫耐熱性測試結果為“通過”,表明電路板達到耐熱性的需求。
由表一可以看出:本發明實施例1~6中的低介電樹脂組合物的介電常數Dk及介電損失Df較低,與比較例1~4中的樹脂組合物的介電常數Dk及較低的介電損失Df大致相等;本案實施例1、4的低介電樹脂組合物所製得的電路板的銅箔剝離強度以及PI剝離強度均高於比較例1~4中的樹脂組合物所製得的電路板的銅箔剝離強度以及PI剝離強度;實施例2、5的低介電樹脂組合物所製得的電路板的銅箔剝離強度高於比較例1~4中的樹脂組合物所製得的電路板的銅箔剝離強度,且其實施例2、5的低介電樹脂組合物所製得的電路板的PI剝離強度與比較例1~4中的樹脂組合物所製得的電路板的PI剝離強度接近;實施例3、6的低介電樹脂組合物所製得的電路板的PI剝離強度高於比較例1~4中的樹脂組合物所製得的電路板的PI剝離強度,且其實施例3、6的低介電樹脂組合物所製得的電路板的銅箔剝離強度與比較例1~4中的樹脂組合物所製得的電路板的銅箔剝離強度接近;實施例1~6的低介電樹脂組合物所製得的電路板的漂錫耐熱性明顯高於比較例1~4的樹脂組合物所製得的電路板的漂錫耐熱性。比較例5的樹脂組合物因EPDM與其他物料無法相容,導致液態樹脂組合物溶液分層,無法測得相關性能。比較例6的樹脂組合物所製得的膠層脆裂,無法測得相關性能。比較例7的樹脂組合物所製得的膠層表面自粘,無法測得相關性能。綜上可知,本發明的低介電樹脂組合物在具有較低的介電常數及介電損失的同時,還具有較高的銅箔玻璃強度、PI剝離強度及漂錫耐熱性。
此外,由實施例4與實施例5對比可知,在低介電樹脂組合物中硬質交聯劑含量較高時,由該低介電樹脂組合物製得的電路板的彈性模量較大,即電路板的硬度較大。由實施例4與實施例6對比可知,在低介電樹脂組合物中軟質交聯劑含量較高時,由該低介電樹脂組合物製得的電路板的彈性模量較小,即電路板的硬度較小。因此,可以藉由調整低介電樹脂組合物中所添加的硬質
交聯劑與軟質交聯劑的含量,來調整由該低介電樹脂組合物所製得的電路板軟硬。
本發明的低介電樹脂組合物的介電常數Dk低於2.4,介電損失Df低於0.004,從而使由該低介電樹脂組合物製得的電路板的膠層具有較低的介電常數,進而使該電路板具有高頻化和高速數位化的信號傳輸性能。此外,所述低介電樹脂組合物採用含酸酐的低介電樹脂,該含酸酐的低介電樹脂相較於不含酸酐的低介電樹脂可以更好的溶解於有機溶劑中,且含酸酐的低介電樹脂相較於不含酸酐的低介電樹脂與其它有機組分的相容性更好,有助於獲得介電常數更低、性能更好的低介電樹脂組合物。此外,環氧樹脂中的環氧基可以與含酸酐的低介電樹脂中的酸酐、硬質交聯劑中的活性酯基、軟質交聯劑中的酸酐發生交聯反應,從而將含酸酐的低介電樹脂、硬質交聯劑及軟質交聯劑串聯起來,得到耐熱性較高且交聯密度較高的低介電樹脂組合物,可以使由該低介電樹脂組合物製得的電路板的膠層具有較好的耐熱性,可適應電路板的耐熱性需求。
另外,對於本領域的普通技術人員來說,可以根據本發明的技術構思做出其它各種相應的改變與變形,而所有這些改變與變形都應屬於本發明申請專利範圍的保護範圍。
Claims (7)
- 一種低介電樹脂組合物,其包括含酸酐的低介電樹脂、環氧樹脂及促進劑,其改良在於,所述含酸酐的低介電樹脂選自馬來酸酐接枝改質樹脂及含酸酐的聚醯亞胺樹脂中的一種或兩種,其中,該含酸酐的聚醯亞胺樹脂的介電常數小於3,所述馬來酸酐接枝改質樹脂包括馬來酸酐接枝苯乙烯-乙烯-丁烯-苯乙烯嵌段共聚物、馬來酸酐接枝環烯烴共聚物及馬來酸酐接枝三元乙丙橡膠中的一種或幾種,所述低介電樹脂組合物還包括未端含乙烯基與活性酯的聚苯醚樹脂及馬來酸化液態聚丁二烯,所述環氧樹脂為含有兩個以上環氧基團的環氧樹脂或含有乙烯基的環氧樹脂,所述低介電樹脂組合物中,含酸酐的低介電樹脂的含量範圍為100重量份,該環氧樹脂的含量範圍為5~30重量份,所述未端含乙烯基與活性酯的聚苯醚樹脂的含量為5~50重量份,所述馬來酸化液態聚丁二烯的含量為5~50重量份,該促進劑的含量範圍為0.1~5重量份。
- 如申請專利範圍第1項所述的低介電樹脂組合物,其中,所述低介電樹脂組合物的介電常數小於2.4,介電損失小於0.004。
- 如申請專利範圍第1項所述的低介電樹脂組合物,其中,所述環氧樹脂包括1,3-雙(環氧乙烷基甲基)-5-(2-丙烯基)-1,3,5-三嗪-2,4,6(1H,3H,5H)-三酮、1-環氧乙烷基甲基-3,5-二-2-丙烯基-1,3,5-三嗪-2,4,6(1H,3H,5H)-三酮、1,3,5-三縮水甘油-S-三嗪三酮、N,N,N',N'-四(環氧乙烷基甲基)-1,3-苯二甲胺、及2,2',2",2'''-[1,2-聯二亞甲基四(4,1-亞苯基亞甲氧)]四環氧乙烷中的一種或幾種。
- 如申請專利範圍第1項所述的低介電樹脂組合物,其中,所述促進劑包括三級胺類促進劑及有機膦衍生物中的一種或兩種,該三級胺類促進劑包括N,N-二甲基苄胺、N,N-二甲基苯胺及三乙胺中的一種或幾種,該有機膦衍生物包括丙烯基三丁基鏻溴化物、溴化三丁基(十二烷基)磷、乙基三正辛基溴化膦、十六烷基三丁基溴化鏻、碘化三丁基甲基膦、四乙基溴化膦、四乙基氫氧化膦 溶液、四丁基溴化膦、四丁基氯化膦、四丁基O,O-二乙基二硫代磷酸膦、四丁基苯並三唑鹽及三(2-甲醯乙基)膦鹽酸鹽中的一種或幾種。
- 如申請專利範圍第1項所述的低介電樹脂組合物,其中,所述低介電樹脂組合物還包括熱起始劑,所述低介電樹脂組合物中,該熱起始劑的含量範圍為0.1~5重量份。
- 一種膠片,其包括樹脂層及結合於該樹脂層至少一表面的離型膜,其改良在於,該樹脂層的材質為申請專利範圍第1至5項任意一項所述的低介電樹脂組合物。
- 一種電路板,其包括電路基板及結合於該電路基板至少一表面的膠層,其改良在於,該膠層由申請專利範圍第1至5項任意一項所述的低介電樹脂組合物經烘烤後製得。
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| US15/871,141 US10894882B2 (en) | 2017-03-15 | 2018-01-15 | Low dielectric resin composition, film and circuit board using the same |
| JP2018045308A JP6822995B2 (ja) | 2017-03-15 | 2018-03-13 | 低誘電率樹脂組成物及びこれを応用したフィルム及び回路基板 |
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