TWI550022B - Low dielectric resin composition and the use of its copper foil substrate and printed circuit board - Google Patents
Low dielectric resin composition and the use of its copper foil substrate and printed circuit board Download PDFInfo
- Publication number
- TWI550022B TWI550022B TW101137673A TW101137673A TWI550022B TW I550022 B TWI550022 B TW I550022B TW 101137673 A TW101137673 A TW 101137673A TW 101137673 A TW101137673 A TW 101137673A TW I550022 B TWI550022 B TW I550022B
- Authority
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- Taiwan
- Prior art keywords
- resin
- resin composition
- composition according
- oxide
- copper foil
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims description 61
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 40
- 239000011889 copper foil Substances 0.000 title claims description 35
- 239000000758 substrate Substances 0.000 title claims description 30
- 229920005989 resin Polymers 0.000 claims description 75
- 239000011347 resin Substances 0.000 claims description 75
- 239000003822 epoxy resin Substances 0.000 claims description 31
- 229920000647 polyepoxide Polymers 0.000 claims description 31
- 229920001955 polyphenylene ether Polymers 0.000 claims description 28
- -1 tris-hydroxyethyl isocyanurate Chemical compound 0.000 claims description 23
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims description 16
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 15
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 14
- 239000003063 flame retardant Substances 0.000 claims description 13
- 239000011256 inorganic filler Substances 0.000 claims description 12
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 11
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 claims description 10
- 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 description 9
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 9
- 125000001033 ether group Chemical group 0.000 claims description 9
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 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 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- PZBFGYYEXUXCOF-UHFFFAOYSA-N TCEP Chemical compound OC(=O)CCP(CCC(O)=O)CCC(O)=O PZBFGYYEXUXCOF-UHFFFAOYSA-N 0.000 claims description 5
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 5
- 239000000395 magnesium oxide Substances 0.000 claims description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 5
- 239000005011 phenolic resin Substances 0.000 claims description 5
- 239000010452 phosphate Substances 0.000 claims description 5
- 229930185605 Bisphenol Natural products 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
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 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
- 229910003460 diamond Inorganic materials 0.000 claims description 4
- 239000010432 diamond Substances 0.000 claims description 4
- VONWDASPFIQPDY-UHFFFAOYSA-N dimethyl methylphosphonate Chemical compound COP(C)(=O)OC VONWDASPFIQPDY-UHFFFAOYSA-N 0.000 claims description 4
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 4
- 229920001971 elastomer Polymers 0.000 claims description 4
- 239000000347 magnesium hydroxide Substances 0.000 claims description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 4
- 229910052863 mullite Inorganic materials 0.000 claims description 4
- 239000000454 talc Substances 0.000 claims description 4
- 229910052623 talc Inorganic materials 0.000 claims description 4
- 239000012745 toughening agent Substances 0.000 claims description 4
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 4
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 claims description 3
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 3
- 239000004713 Cyclic olefin copolymer Substances 0.000 claims description 3
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- 229920000388 Polyphosphate Polymers 0.000 claims description 3
- 239000007983 Tris buffer Substances 0.000 claims description 3
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 3
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 239000001205 polyphosphate Substances 0.000 claims description 3
- 235000011176 polyphosphates Nutrition 0.000 claims description 3
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 3
- 229910002706 AlOOH Inorganic materials 0.000 claims description 2
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- 229910052582 BN Inorganic materials 0.000 claims description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000005062 Polybutadiene Substances 0.000 claims description 2
- BQPNUOYXSVUVMY-UHFFFAOYSA-N [4-[2-(4-diphenoxyphosphoryloxyphenyl)propan-2-yl]phenyl] diphenyl phosphate Chemical compound C=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 BQPNUOYXSVUVMY-UHFFFAOYSA-N 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- 229910001593 boehmite Inorganic materials 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 239000001506 calcium phosphate Substances 0.000 claims description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 2
- 235000011010 calcium phosphates Nutrition 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical group C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 2
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 claims description 2
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 2
- 239000012212 insulator Substances 0.000 claims description 2
- ULYZAYCEDJDHCC-UHFFFAOYSA-N isopropyl chloride Chemical compound CC(C)Cl ULYZAYCEDJDHCC-UHFFFAOYSA-N 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- NFFIWVVINABMKP-UHFFFAOYSA-N methylidynetantalum Chemical compound [Ta]#C NFFIWVVINABMKP-UHFFFAOYSA-N 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 239000002105 nanoparticle Substances 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000013034 phenoxy resin Substances 0.000 claims description 2
- 229920006287 phenoxy resin Polymers 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 229920006122 polyamide resin Polymers 0.000 claims description 2
- 229920002857 polybutadiene Polymers 0.000 claims description 2
- 229920001225 polyester resin Polymers 0.000 claims description 2
- 239000004645 polyester resin Substances 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 239000009719 polyimide resin Substances 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 229910003468 tantalcarbide Inorganic materials 0.000 claims description 2
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 2
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims 2
- NKMNUSKLXDDOPX-UHFFFAOYSA-N OC1=CC=CC(O)=C1.OC1=CC=CC(O)=C1.OC1=CC=CC(O)=C1 Chemical compound OC1=CC=CC(O)=C1.OC1=CC=CC(O)=C1.OC1=CC=CC(O)=C1 NKMNUSKLXDDOPX-UHFFFAOYSA-N 0.000 claims 1
- CAVCGVPGBKGDTG-UHFFFAOYSA-N alumanylidynemethyl(alumanylidynemethylalumanylidenemethylidene)alumane Chemical compound [Al]#C[Al]=C=[Al]C#[Al] CAVCGVPGBKGDTG-UHFFFAOYSA-N 0.000 claims 1
- 238000001354 calcination Methods 0.000 claims 1
- 239000003431 cross linking reagent Substances 0.000 claims 1
- 239000002270 dispersing agent Substances 0.000 claims 1
- 239000000806 elastomer Substances 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 238000006068 polycondensation reaction Methods 0.000 claims 1
- 229910052715 tantalum Inorganic materials 0.000 claims 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims 1
- 125000005504 styryl group Chemical group 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 10
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 6
- 239000012779 reinforcing material Substances 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Natural products CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 5
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 239000007822 coupling agent Substances 0.000 description 5
- 239000004744 fabric Substances 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 125000005843 halogen group Chemical group 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000004843 novolac epoxy resin Substances 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 4
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 230000008054 signal transmission Effects 0.000 description 4
- 229920001187 thermosetting polymer Polymers 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 239000004848 polyfunctional curative Substances 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 229910000679 solder Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 2
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 2
- IZSHZLKNFQAAKX-UHFFFAOYSA-N 5-cyclopenta-2,4-dien-1-ylcyclopenta-1,3-diene Chemical group C1=CC=CC1C1C=CC=C1 IZSHZLKNFQAAKX-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
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Classifications
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- C08L71/126—Polyphenylene oxides modified by chemical after-treatment
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- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- H—ELECTRICITY
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- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
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- H05K1/024—Dielectric details, e.g. changing the dielectric material around a transmission line
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- 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
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- H05K1/0346—Organic insulating material consisting of one material containing N
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- H—ELECTRICITY
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- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
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- H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
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- 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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
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- H05K2201/012—Flame-retardant; Preventing of inflammation
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- 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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
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- H05K2201/0158—Polyalkene or polyolefin, e.g. polyethylene [PE], polypropylene [PP]
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- 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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
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- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
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Description
本發明係關於一種樹脂組成物,尤指一種應用於銅箔基板及印刷電路板之低介電樹脂組成物。
為因應世界環保潮流及綠色法規,無鹵素(Halogen-free)為當前全球電子產業之環保趨勢,世界各國及相關電子大廠陸續對其電子產品,制定無鹵素電子產品的量產時程表。歐盟之有害物質限用指令(Restriction of Hazardous Substances,RoHS)實施後,包含鉛、鎘、汞、六價鉻、聚溴聯苯與聚溴二苯醚等物質,已不得用於製造電子產品或其零元件。印刷電路板(Printed Circuit Board,PCB)為電子電機產品之基礎,無鹵素以對印刷電路板為首先重點管制物件,國際組織對於印刷電路板之鹵素含量已有嚴格要求,其中國際電工委員會(IEC)61249-2-21規範要求溴、氯化物之含量必須低於900 ppm,且總鹵素含量必須低於1500 ppm;日本電子迴路工業會(JPCA)則規範溴化物與氯化物之含量限制均為900 ppm;而綠色和平組織現階段大力推動的綠化政策,要求所有的製造商完全排除其電子產品中之聚氯乙烯及溴系阻燃劑,以符合兼具無鉛及無鹵素之綠色電子。因此,材料的無鹵化成為目前業者的重點開發項目。
新世代的電子產品趨向輕薄短小,並適合高頻傳輸,因此電路板之配線走向高密度化,電路板的材料選用走向
更嚴謹的需求。高頻電子元件與電路板接合,為了維持傳輸速率及保持傳輸訊號完整性,電路板之基板材料必須兼具較低的介電常數及介電損耗。同時,為了於高溫、高濕度環境下依然維持電子元件正常運作功能,電路板也必須兼具耐熱、難燃及低吸水性的特性。環氧樹脂由於接著性、耐熱性、成形性優異,故廣泛使用於電子零元件及電機機械之覆銅箔積層板或密封材。從防止火災之安全性觀點而言,要求材料具有阻燃性,一般係以無阻燃性之環氧樹脂,配合外加阻燃劑之方式達到阻燃之效果,例如,在環氧樹脂中藉由導入鹵素,尤其是溴,而賦予阻燃性,提高環氧基之反應性。另外,在高溫下經長時間使用後,可能會引起鹵化物之解離,而有微細配線腐蝕之虞。再者使用過後之廢棄電子零元件,在燃燒後會產生鹵化物等有害化合物,對環境亦不友善。為取代上述之鹵化物阻燃劑,有研究使用磷化合物作為阻燃劑,例如添加磷酸酯(中華民國專利公告I238846號)或紅磷(中華民國專利公告322507號)於環氧樹脂組成物中。然而,磷酸酯會因產生水解反應而使酸離析,導致影響其耐遷移性;而紅磷之阻燃性雖高,但在消防法中被指為危險物品,在高溫、潮濕環境下因為會發生微量之膦氣體。
習知之銅箔基板(或稱銅箔積層板)製作之電路板技術中,係利用一環氧基樹脂與硬化劑作為熱固性樹脂組成物原料,將補強材(如玻璃纖維布)與該熱固性樹脂組成加熱結合形成一半固化膠片(prepreg),再將該半固化膠片與上、
下兩片銅箔於高溫高壓下壓合而成。先前技術一般使用環氧基樹脂與具有羥基(-OH)之酚醛(phenol novolac)樹脂硬化劑作為熱固性樹脂組成原料,酚醛樹脂與環氧基樹脂結合會使環氧基開環後形成另一羥基,羥基本身會提高介電常數及介電損耗值,且易與水分結合,增加吸濕性。
中華民國專利公告第I297346號揭露一種使用氰酸酯樹脂、二環戊二烯基環氧樹脂、矽石以及熱塑性樹脂作為熱固性樹脂組成物,此種熱固性樹脂組成物具有低介電常數與低介電損耗等特性。然而此製造方法於製作時必須使用含有鹵素(如溴)成份之阻燃劑,例如四溴環己烷、六溴環癸烷以及2,4,6-三(三溴苯氧基)-1,3,5-三氮雜苯,而這些含有溴成份之阻燃劑於產品製造、使用甚至回收或丟棄時都很容易對環境造成污染。為了提升銅箔基板之耐熱難燃性、低介電損耗、低吸濕性、高交聯密度、高玻璃轉化溫度、高接合性、適當之熱膨脹性,環氧樹脂、硬化劑及補強材的材料選擇成了主要影響因素。
就電氣性質而言,主要需考慮者包括材料的介電常數(dielectric constant)以及介電損耗(又稱損失因數,dissipation factor)。一般而言,由於基板之訊號傳送速度與基板材料之介電常數的平方根成反比,故基板材料的介電常數通常越小越好;另一方面,由於介電損耗越小代表訊號傳遞的損失越少,故介電損耗較小之材料所能提供之傳輸品質也較為良好。
因此,如何開發出具有低介電常數以及低介電損耗之
材料,並將其應用於高頻印刷電路板之製造,乃是現階段印刷電路板材料供應商亟欲解決之問題。
有鑒於上述習知技術之缺憾,發明人有感其未臻於完善,遂竭其心智悉心研究克服,憑其從事該項產業多年之累積經驗,進而研發出一種樹脂組成物,以期達到低介電常數、低介電損耗及高耐熱性之目的。
本發明之主要目的在提供一種樹脂組成物,其藉著包含特定之組成份及比例,以使可達到低介電常數、低介電損耗及高耐熱性;可製作成半固化膠片或樹脂膜,進而達到可應用於銅箔基板及印刷電路板之目的。
為達上述目的,本發明提供一種樹脂組成物,其包含:(A)100重量份之末端苯乙烯基之聚苯醚樹脂;(B)5至75重量份之烯烴共聚物;及(C)1至150重量份之含聚苯醚官能基之氰酸酯樹脂。
上述之組成物的用途,其係用於製造半固化膠片、樹脂膜、銅箔基板及印刷電路板。藉此,本發明之樹脂組成物,其藉著包含特定之組成份及比例,以使可達到低介電常數、低介電損耗及高耐熱性等特性;可製作成半固化膠片或樹脂膜,進而達到可應用於銅箔基板及印刷電路板之目的。
本發明所述之末端苯乙烯基之聚苯醚樹脂,係具有通式(1)之結構:
其中R1、R2、R3、R4、R5、R6及R7可以相同或不同,且是氫原子、鹵素原子、烷基、鹵化烷基或苯基,-(O-X-O)-由通式(2)或通式(3)(其中R8、R9、R10、R14、R15、R16、R17、R22及R23可以相同或不同,且是鹵素原子、含有1-6個碳原子的烷基或苯基,R11、R12、R13、R18、R19、R20及R21可以相同或不同,且是氫原子、鹵素原子、含有1-6個碳原子的烷基或苯基,且A是含有1-20個碳原子及可含有取代基的線性或環狀烴)表示,-(Y-O)-是一種由通式(4)定義的結構的排列或由至少兩種通式(4)定
義的結構的無規則排列(其中R24及R25可以相同或不同,且是鹵素原子、含有1-6個碳原子的烷基或苯基,R26及R27可以相同或不同,且是氫原子、鹵素原子、含有1-6個碳原子的烷基或苯基),Z是含有至少一個碳原子及可包含氧原子、氮原子、硫原子或鹵素原子的有機基團,a及b的每一個是0-300的整數,條件是a或b至少有一不是0,以及c及d的每一個是0或1的整數。
本發明所述之末端苯乙烯基之聚苯醚樹脂,相較於習知之雙官能末端羥基之聚苯醚樹脂,具有較低的介電特性,即具有較低的介電常數及介電損耗。
本發明所述之烯烴共聚物可為甲基苯乙烯共聚物或環型烯烴共聚物(cyclic olefin copolymer),其中環型烯烴共聚物係具有通式(5)之結構:
本發明所述之烯烴共聚物不具有羥基(-OH官能基),因而具有較低的介電特性。
本發明之樹脂組成物,以100重量份之末端苯乙烯基之聚苯醚樹脂為基準,係添加5至75重量份之烯烴共聚物,於此添加範圍內,可使該樹脂組成物降低整體之介電常數及介電損耗,若烯烴共聚物之含量不足5重量份,則達不到電性值要求,若超過75重量份,則耐熱性變差。相
較於習知技術所使用之雙官能末端羥基之聚苯醚樹脂,能與環氧樹脂有效交聯,本發明所述之末端苯乙烯基之聚苯醚樹脂,不易與環氧樹脂交聯反應,導致交聯性差,基板特性不佳。因此,本發明使用烯烴共聚物與末端苯乙烯基之聚苯醚樹脂交聯反應,可有效增加其交聯性,改善基板特性。
一般樹脂中,聚苯醚樹脂通常具有較低的介電特性,而末端苯乙烯基之聚苯醚樹脂相較於一般之聚苯醚樹脂,具有更低的介電常數及介電損耗,可有效達到樹脂組成物具有很低的介電特性,以符合基板之樹脂層之低介電特性需求。於本發明中,添加5至75重量份之烯烴共聚物可再降低介電常數及介電損耗,並提高與末端苯乙烯基之聚苯醚樹脂之交聯性。
本發明所述之含聚苯醚官能基之氰酸酯樹脂,係具有通式(6)之結構。
其中X6係共價鍵、-SO2-、-C(CH3)2-、-CH(CH3)-或-CH2-;Z5至Z12各自獨立係氫或甲基;W為-O-C≡N;n為大於或等於1之整數。
更具體來說,該含聚苯醚官能基之氰酸酯樹脂較佳係選自通式(7)至(10)之至少一者:
其中n為大於或等於1之整數。
相較於習知技術使用之雙酚A型氰酸酯樹脂,本發明所述之含聚苯醚官能基之氰酸酯樹脂,相較於雙酚A型氰酸酯樹脂具有較低的介電常數及介電損耗。
本發明之樹脂組成物,以100重量份之末端苯乙烯基之聚苯醚樹脂為基準,係添加1至150重量份之含聚苯醚官能基之氰酸酯樹脂,於此添加範圍內,可提高與末端苯乙烯基之聚苯醚樹脂及烯烴共聚物之相互交聯性,提高三種樹脂間之鍵結完整性。含聚苯醚官能基之氰酸酯樹脂除了可提高交聯性外,更可增加玻璃轉化溫度及與銅箔之接著力。此外,含聚苯醚官能基之氰酸酯樹脂、烯烴共聚物
及末端苯乙烯基之聚苯醚樹脂三者間,可達到優異的低介電特性。
本發明之樹脂組成物,較佳係再添加苯并噁嗪樹脂,該苯并噁嗪樹脂係包含:雙酚A型苯并噁嗪樹脂、雙酚F型苯并噁嗪樹脂、含二環戊二烯結構之苯并噁嗪樹脂及酚酞型苯并噁嗪樹脂。更具體而言,其較佳係選自下列通式(11)至(13)之至少一者:
其中X1及X2係分別獨立為R或Ar或-SO2-;R係選自-C(CH3)2-、-CH(CH3)-、-CH2-及經取代或未經取代之二環戊二烯基;Ar係選自經取代或未經取代之苯、聯苯、萘、酚醛、雙酚A、雙酚A酚醛、雙酚F及雙酚F酚醛官能基。如Huntsman販賣之商品名LZ-8280,LZ-8290。
本發明之樹脂組成物,以100重量份之末端苯乙烯基之聚苯醚樹脂為基準,係添加5至50重量份之苯并噁嗪樹脂,於此添加範圍內,可使該樹脂組成物降低整體之吸濕率並提高剛性,若苯并噁嗪樹脂之含量不足5重量份,則達不到降低吸濕率及提高剛性要求,若超過50重量份,則基板耐熱性變差。
為提高本發明之樹脂組成物之難燃特性,可進一步添加下列阻燃性化合物。所選用的阻燃性化合物可為磷酸鹽化合物或含氮磷酸鹽化合物,但並不以此為限。更具體來說,阻燃性化合物較佳係包含以下化合物中之至少一種:雙酚聯苯磷酸鹽(bisphenol diphenyl phosphate)、聚磷酸銨(ammonium polyphosphate)、對苯二酚-雙-(聯苯基磷酸鹽)(hydroquinone bis-(diphenyl phosphate))、雙酚A-雙-(聯苯基磷酸鹽)(bisphenol A bis-(diphenylphosphate))、三(2-羧乙基)膦(tri(2-carboxyethyl)phosphine,TCEP)、三(異丙基氯)磷酸鹽、三甲基磷酸鹽(trimethyl phosphate,TMP)、二甲基-甲基磷酸鹽(dimethyl methyl phosphonate,DMMP)、間苯二酚雙二甲苯基磷酸鹽(resorcinol dixylenylphosphate,RDXP(如PX-200))、聚磷酸三聚氰胺
(melamine polyphosphate)、磷氮基化合物、偶磷氮化合物、9,10-二氫-9-氧雜-10-磷菲-10-氧化物(9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide,DOPO)及其衍生物或樹脂、三聚氰胺氰尿酸酯(melamine cyanurate)及三-羥乙基異氰尿酸酯(tri-hydroxy ethyl isocyanurate)等,但並不以此為限。舉例來說,阻燃性化合物可為DOPO化合物、DOPO樹脂(如DOPO-HQ、DOPO-PN、DOPO-BPN)、DOPO鍵結之環氧樹脂等,其中DOPO-BPN可為DOPO-BPAN、DOPO-BPFN、DOPO-BPSN等雙酚酚醛化合物。
本發明之樹脂組成物,尚可進一步添加無機填充物,添加無機填充物之主要作用,在於增加樹脂組成物之熱傳導性、改良其熱膨脹性及機械強度等特性,且無機填充物較佳係均勻分佈於該無鹵樹脂組成物中。
其中,無機填充物可包含二氧化矽(熔融態、非熔融態、多孔質或中空型)、氧化鋁、氫氧化鋁、氧化鎂、氫氧化鎂、碳酸鈣、氮化鋁、氮化硼、碳化鋁矽、碳化矽、碳酸鈉、二氧化鈦、氧化鋅、氧化鋯、石英、鑽石粉、類鑽石粉、石墨、碳酸鎂、鈦酸鉀、陶瓷纖維、雲母、勃姆石(boehmite,AlOOH)、鉬酸鋅、鉬酸銨、硼酸鋅、磷酸鈣、煅燒滑石、滑石、氮化矽、莫萊石、煅燒高嶺土、黏土、鹼式硫酸鎂晶鬚、莫萊石晶鬚、硫酸鋇、氫氧化鎂晶鬚、氧化鎂晶鬚、氧化鈣晶鬚、奈米碳管、奈米級二氧化矽與其相關無機粉體、或具有有機核外層殼為絕緣體修飾之粉
體粒子。且無機填充物可為球型、纖維狀、板狀、粒狀、片狀或針須狀,並可選擇性經由矽烷偶合劑預處理。
無機填充物可為粒徑100μm以下之顆粒粉末,且較佳為粒徑1 nm至20 μm之顆粒粉末,最佳為粒徑1 μm以下之奈米尺寸顆粒粉末;針須狀無機填充物可為直徑50 μm以下且長度1至200 μm之粉末。
本發明之無機填充物的添加量,以100重量份之末端苯乙烯基之聚苯醚樹脂為基準,係添加10至1000重量份之無機填充物。若無機填充物之含量不足10重量份,則無顯著之熱傳導性、改良其熱膨脹性及機械強度等特性改善;若超過1000重量份,則樹脂組成物之填孔流動性變差,與銅箔之接著變差。
以較佳電性值為考慮,本發明之樹脂組成物較佳係使用熔融態二氧化矽、多孔隙二氧化矽、中空二氧化矽、球型二氧化矽等填充物之其中一者或其組合。
本發明之樹脂組成物,尚可進一步添加選自下列群組中之至少一者或其改質物:環氧樹脂、氰酸酯樹脂、苯乙烯馬來酸酐、苯酚樹脂、酚醛樹脂、胺交聯劑、苯氧樹脂、苯乙烯樹脂、聚丁二烯樹脂、聚醯胺樹脂、聚醯亞胺樹脂、聚酯樹脂。
本發明之樹脂組成物,尚可進一步添加環氧樹脂,其可選擇自雙酚A(bisphenol A)環氧樹脂、雙酚F(bisphenol F)環氧樹脂、雙酚S(bisphenol S)環氧樹脂、雙酚AD(bisphenol AD)環氧樹脂、酚醛(phenol novolac)環氧樹脂、雙酚A酚
醛(bisphenol A novolac)環氧樹脂、鄰甲酚(o-cresol novolac)環氧樹脂、三官能基(trifunctional)環氧樹脂、四官能基(tetrafunctional)環氧樹脂、多官能基(multifunctional)環氧樹脂、二環戊二烯環氧樹脂(dicyclopentadiene(DCPD)epoxy resin)、含磷環氧樹脂、含DOPO環氧樹脂、含DOPO-HQ環氧樹脂、對二甲苯環氧樹脂(p-xylene epoxy resin)、萘型(naphthalene)環氧樹脂、苯并哌喃型(benzopyran)環氧樹脂、聯苯酚醛(biphenyl novolac)環氧樹脂、酚基苯烷基酚醛(phenol aralkyl novolac)環氧樹脂或其組合。
本發明之樹脂組成物,較佳係添加二環戊二烯環氧樹脂或萘型環氧樹脂。其中,添加二環戊二烯環氧樹脂可降低樹脂組成之吸濕性;添加萘型環氧樹脂可增加樹脂組成之剛性及耐熱性。
此外,本發明之樹脂組成物尚可選擇性包含介面活性劑(surfactant)、矽烷偶合劑(silane coupling agent)、硬化促進劑(curing accelerator)、增韌劑(toughening agent)或溶劑(solvent)等添加物。添加介面活性劑之主要目的在於改善無機填充物於樹脂組成物中之均勻分散性,避免無機填充物凝聚。添加增韌劑之主要目的在於改善樹脂組成物之韌性。添加硬化促進劑之主要作用在於增加樹脂組成物之反應速率。添加溶劑之主要目的在於改變樹脂組成物之固含量,並調變樹脂組成物之黏度。
所述矽烷偶合劑係可包含矽烷化合物(silane)及矽氧烷化合物(siloxane),依官能基種類又可分為胺基矽烷化合物
(amino silane)、胺基矽氧烷化合物(amino siloxane)、環氧基矽烷化合物(epoxy silane)及環氧基矽氧烷化合物(epoxy siloxane)。
所述硬化促進劑係可包含路易士鹼或路易士酸等催化劑(catalyst)。其中,路易士鹼可包含咪唑(imidazole)、三氟化硼胺複合物、氯化乙基三苯基鏻(ethyltriphenyl phosphonium chloride)、2-甲基咪唑(2-methylimidazole,2MI)、2-苯基咪唑(2-phenyl-1H-imidazole,2PZ)、2-乙基-4-甲基咪唑(2-ethyl-4-methylimidazole,2E4MZ)、三苯基膦(triphenylphosphine,TPP)與4-二甲基胺基吡啶(4-dimethylaminopyridine,DMAP)中之一者或多者。路易士酸係可包含金屬鹽類化合物,如錳、鐵、鈷、鎳、銅、鋅等金屬鹽化合物,如辛酸鋅、辛酸鈷等金屬催化劑。此外,本發明所述之硬化促進劑亦可包含過氧化物(peroxide)、陽離子聚合引發劑、四苯基硼四苯基磷(TPPK)之其一者或其組合。
本發明所述之增韌劑選自:橡膠(rubber)樹脂、聚丁二烯丙烯腈(carboxyl-terminated butadiene acrylonitrile rubber,CTBN)、核殼聚合物(core-shell rubber)等添加物。
本發明所述之溶劑係可包含甲醇、乙醇、乙二醇單甲醚、丙酮、丁酮(甲基乙基酮)、甲基異丁基酮、環己酮、甲苯、二甲苯、甲氧基乙基乙酸酯、乙氧基乙基乙酸酯、丙氧基乙基乙酸酯、乙酸乙酯、二甲基甲醯胺、丙二醇甲基醚等溶劑或其混合溶劑。
為達到低介電常數及低介電損耗的特性,本發明之樹脂組成物必須儘量減少殘存的羥基數。亦即,提高樹脂間之交聯密度。因此,本發明所揭露之樹脂組成物之各組成份間交聯作用,依所揭露之添加比例可促進交聯最佳化,殘留最少樹脂含有未反應官能基。
本發明之又一目的在於揭露一種樹脂膜(film),其具有低介電特性、耐熱性、低吸濕性及不含鹵素等特性,且可應用於積層板和電路板之絕緣層材料。
本發明之樹脂膜係包含前述之樹脂組成物,該樹脂組成物係經由加熱製程而形成半固化態。舉例來說,可將該無鹵樹脂組成物置於聚對苯二甲酸乙二酯(polyethylene terephthalate,PET)膜上並進行加熱以形成樹脂膜。
本發明之再一目的在於揭露一種背膠銅箔(resin coated copper foil,RCC),其包含至少一銅箔及至少一絕緣層。其中,銅箔可進一步包含銅與鋁、鎳、鉑、銀、金等金屬之合金。藉由將本發明所揭露之樹脂膜貼合於至少一片銅箔上,移除所述PET膜,且將樹脂膜及銅箔於高溫高壓下加熱固化,即可形成與銅箔緊密接合之絕緣層。
本發明之再一目的在於揭露一半固化膠片,其具有高機械強度、低介電特性、耐熱性、低吸濕性及不含鹵素等特性。據此,本發明所揭露之半固化膠片可包含一補強材及前述之樹脂組成物,其中該樹脂組成物係附著於該補強材上,並經由高溫加熱形成半固化態。其中,補強材係可為纖維材料、織布及不織布,如玻璃纖維布等,其係可增
加該半固化膠片之機械強度。此外,該補強材可選擇性經由矽烷偶合劑或矽氧烷偶合劑進行預處理,如經矽烷偶合劑預處理之玻璃纖維布。
前述之半固化膠片經由高溫加熱或高溫且高壓下加熱可固化形成固化膠片或是固態絕緣層,其中樹脂組成物若含有溶劑,則該溶劑會於高溫加熱程序中揮發移除。
本發明之又一目的在於揭露一種銅箔基板,其具有高機械強度、低介電特性、耐熱性、低吸濕性及不含鹵素等特性,且特別適用於高速度高頻率訊號傳輸之電路板。據此,本發明提供一種銅箔基板,其包含兩個或兩個以上之銅箔及至少一絕緣層。其中,銅箔可進一步包含銅與鋁、鎳、鉑、銀、金等至少一種金屬之合金;絕緣層係由前述之半固化膠片於高溫高壓下固化而成,如將前述半固化膠片疊合於兩個銅箔之間且於高溫與高壓下進行壓合而成。
本發明所述之銅箔基板至少具有以下優點之一:低介電常數與低介電損耗之特性。該銅箔基板進一步經由製作線路等製程加工後,可形成一電路板,且該電路板與電子元件接合後於高溫、高濕度等嚴苛環境下操作而並不影響其品質。
本發明之再一目的在於揭露一種印刷電路板,其具有高機械強度、低介電特性、耐熱性、低吸濕性及不含鹵素等特性,且適用於高速度高頻率之訊號傳輸。其中,該電路板係包含至少一個前述之銅箔基板,且該電路板係可由習知之製程製作而成。
為進一步揭露本發明,以使本發明所屬技術領域者具有通常知識者可據以實施,以下謹以數個實施例進一步說明本發明。然應注意者,以下實施例僅係用以對本發明做進一步之說明,並非用以限制本發明之實施範圍,且任何本發明所屬技術領域者具有通常知識者在不違背本發明之精神下所得以達成之修飾及變化,均屬於本發明之範圍。
為充分瞭解本發明之目的、特徵及功效,茲藉由下述具體之實施例,對本發明做一詳細說明,說明如後:分別將實施例1至5(E1~E5)及比較例1至2(C1~C2)之樹脂組成物的組成列表於表一。將上述實施例1至5及比較例1至2之樹脂組成物,分批於攪拌槽中混合均勻後置入一含浸槽中,再將玻璃纖維布通過上述含浸槽,使樹脂組成物附著於玻璃纖維布,再進行加熱烘烤成半固化態而得半固化膠片。
將上述分批製得的半固化膠片,取同一批之半固化膠片四張及兩張18 μm銅箔,依銅箔、四片半固化膠片、銅箔之順序進行疊合,再於真空條件下經由220℃壓合2小時形成銅箔基板,其中四片半固化膠片固化形成兩銅箔間之絕緣層。
分別將上述含銅箔基板及銅箔蝕刻後之不含銅基板做物性量測,物性量測專案包含玻璃轉化溫度(Tg)、含銅基板耐熱性(T288)、含銅基板浸錫測試(solder dip 288℃,10
秒,測耐熱回數,S/D)、浸焊測試(solder dip 288℃,測耐熱秒數)、不含銅基板PCT吸濕後浸錫測試(pressure cooking at 121℃,3小時後,測solder dip 288℃,20秒觀看有無爆板,PCT)、銅箔與基板間拉力(peeling strength,half ounce copper foil,P/S)、介電常數(Dk越低越佳)及介電損耗(Df越低越佳)。分別將實施例1至5及比較例1至2之樹脂組成物的量測結果列表於表二。
將實施例1至5與比較例1相比較,比較例1不含末端苯乙烯基之聚苯醚樹脂,導致介電損耗過高,且耐熱性不佳。
將實施例1至5與比較例2相比較,比較例2不含含聚苯醚官能基之氰酸酯樹脂,導致介電常數過高,且耐熱性不佳。
由實施例1至5可以發現,本發明之樹脂組成物包含末端苯乙烯基之聚苯醚樹脂、烯烴共聚物及含聚苯醚官能基之氰酸酯樹脂,具有低介電常數、低介電損耗及高耐熱性的優異特性。
如上所述,本發明完全符合專利三要件:新穎性、進步性和產業上的可利用性。以新穎性和進步性而言,本發明之樹脂組成物,其藉著包含特定之組成份及比例,以使可達到低介電常數、低介電損耗及高耐熱性;可製作成半固化膠片或樹脂膜,進而達到可應用於銅箔基板及印刷電路板之目的;就產業上的可利用性而言,利用本發明所衍生的產品,當可充分滿足目前市場的需求。
本發明在上文中已以較佳實施例揭露,然熟習本項技術者應理解的是,該實施例僅用於描繪本發明,而不應解讀為限制本發明之範圍。應注意的是,舉凡與該實施例等效之變化與置換,均應設為涵蓋于本發明之範疇內。因此,本發明之保護範圍當以下文之申請專利範圍所界定者為準。
Claims (15)
- 一種樹脂組成物,其包含:(A)100重量份之末端苯乙烯基之聚苯醚樹脂;(B)5至75重量份之烯烴共聚物;及(C)1至150重量份之含聚苯醚官能基之氰酸酯樹脂其中該烯烴共聚物為甲基苯乙烯共聚物或環型烯烴共聚物;其中該含聚苯醚官能基之氰酸酯樹脂,係具有通式(6)之結構:
- 如申請專利範圍第1項所述之樹脂組成物,其進一步包含:苯并噁嗪樹脂。
- 如申請專利範圍第2項所述之樹脂組成物,其中,其係包含5至50重量份之苯并噁嗪樹脂。
- 如申請專利範圍第1至3項中任一項所述之樹脂組成物,其進一步包含選自下列群組中之至少一者:環氧樹脂、氰酸酯樹脂、苯酚樹脂、酚醛樹脂、胺交聯劑、苯氧樹脂、 苯乙烯樹脂、聚丁二烯樹脂、聚醯胺樹脂、聚醯亞胺樹脂、聚酯樹脂。
- 如申請專利範圍第1至3項中任一項所述之樹脂組成物,其進一步包含無機填充物,該無機填充物系選自下列群組中之至少一者:二氧化矽、氧化鋁、氫氧化鋁、氧化鎂、氫氧化鎂、碳酸鈣、氮化鋁、氮化硼、碳化鋁矽、碳化矽、碳酸鈉、二氧化鈦、氧化鋅、氧化鋯、石英、鑽石粉、類鑽石粉、石墨、碳酸鎂、鈦酸鉀、陶瓷纖維、雲母、勃姆石(boehmite,AlOOH)、鉬酸鋅、鉬酸銨、硼酸鋅、磷酸鈣、煅燒滑石、滑石、氮化矽、莫萊石、煅燒高嶺土、黏土、鹼式硫酸鎂晶鬚、硫酸鋇、氧化鈣晶鬚、奈米碳管及具有有機核外層殼為絕緣體修飾之粉體粒子。
- 如申請專利範圍第5項所述之樹脂組成物,其中該莫萊石係為莫萊石晶鬚。
- 如申請專利範圍第5項所述之樹脂組成物,其中該氫氧化鎂係為氫氧化鎂晶鬚。
- 如申請專利範圍第5項所述之樹脂組成物,其中該氧化鎂係為氧化鎂晶鬚。
- 如申請專利範圍第5項所述之樹脂組成物,其中該二氧化矽係為奈米級二氧化矽。
- 如申請專利範圍第1至3項中任一項所述之樹脂組成物,其進一步包含選自下列群組中之至少一者:雙酚聯苯磷酸鹽(bisphenol diphenyl phosphate)、聚磷酸銨(ammonium polyphosphate)、對苯二酚-雙-(聯苯基磷酸 鹽)(hydroquinone bis-(diphenyl phosphate))、雙酚A-雙-(聯苯基磷酸鹽)(bisphenol A bis-(diphenylphosphate))、三(2-羧乙基)膦(tri(2-carboxyethyl)phosphine,TCEP)、三(異丙基氯)磷酸鹽、三甲基磷酸鹽(trimethyl phosphate,TMP)、二甲基-甲基磷酸鹽(dimethyl methyl phosphonate,DMMP)、間苯二酚雙二甲苯基磷酸鹽(resorcinol dixylenylphosphate,RDXP(如PX-200))、聚磷酸三聚氰胺(melamine polyphosphate)、偶磷氮化合物、9,10-二氫-9-氧雜-10-磷菲-10-氧化物(9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide,DOPO)及其衍生物或樹脂、三聚氰胺氰尿酸酯(melamine cyanurate)及三-羥乙基異氰尿酸酯(tri-hydroxy ethyl isocyanurate)。
- 如申請專利範圍第1至3項中任一項所述之樹脂組成物,其進一步包含選自下列群組中之至少一者:硬化促進劑、增韌劑、阻燃劑、分散劑、有機矽彈性體及溶劑。
- 一種半固化膠片,其包含如申請專利範圍第1至11項中任一項所述之樹脂組成物。
- 一種樹脂膜,其包含如申請專利範圍第1至11項中任一項所述之樹脂組成物。
- 一種銅箔基板,其包含如申請專利範圍第12項所述之半固化膠片或第13項所述之樹脂膜。
- 一種印刷電路板,其包含如申請專利範圍第14項所述之銅箔基板。
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US20140004324A1 (en) | 2014-01-02 |
CN103509329B (zh) | 2016-01-20 |
CN103509329A (zh) | 2014-01-15 |
TW201400547A (zh) | 2014-01-01 |
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