CN103509329A - 低介电树脂组成物及应用其的铜箔基板及印刷电路板 - Google Patents
低介电树脂组成物及应用其的铜箔基板及印刷电路板 Download PDFInfo
- Publication number
- CN103509329A CN103509329A CN201210217552.9A CN201210217552A CN103509329A CN 103509329 A CN103509329 A CN 103509329A CN 201210217552 A CN201210217552 A CN 201210217552A CN 103509329 A CN103509329 A CN 103509329A
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- Prior art keywords
- resin
- resin combination
- circuit board
- combination
- copper foil
- Prior art date
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000011889 copper foil Substances 0.000 title abstract description 24
- 239000000805 composite resin Substances 0.000 title abstract 4
- 239000002131 composite material Substances 0.000 title 1
- 229920005989 resin Polymers 0.000 claims abstract description 131
- 239000011347 resin Substances 0.000 claims abstract description 131
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 31
- 229920006380 polyphenylene oxide Polymers 0.000 claims abstract description 31
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims abstract description 17
- 125000005504 styryl group Chemical group 0.000 claims abstract description 17
- 239000004643 cyanate ester Substances 0.000 claims abstract description 14
- 239000003822 epoxy resin Substances 0.000 claims description 37
- 229920000647 polyepoxide Polymers 0.000 claims description 37
- -1 phosphoric acid salt Chemical class 0.000 claims description 33
- 229910052802 copper Inorganic materials 0.000 claims description 23
- 239000010949 copper Substances 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000003063 flame retardant Substances 0.000 claims description 16
- 239000011256 inorganic filler Substances 0.000 claims description 14
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 13
- 125000000524 functional group Chemical group 0.000 claims description 13
- 238000000465 moulding Methods 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
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 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
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 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
- 229910000147 aluminium phosphate Inorganic materials 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
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
- 229910003460 diamond Inorganic materials 0.000 claims description 4
- 239000010432 diamond Substances 0.000 claims description 4
- 239000000428 dust Substances 0.000 claims description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 4
- 239000000347 magnesium hydroxide Substances 0.000 claims description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 4
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 229960001866 silicon dioxide Drugs 0.000 claims description 4
- 239000000454 talc Substances 0.000 claims description 4
- 235000012222 talc Nutrition 0.000 claims description 4
- 229910052623 talc Inorganic materials 0.000 claims description 4
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 3
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 3
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 3
- 229910001593 boehmite Inorganic materials 0.000 claims description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 3
- 229920003987 resole Polymers 0.000 claims description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 2
- 229910017083 AlN Inorganic materials 0.000 claims description 2
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 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
- IUBPJIAHYCFKGA-UHFFFAOYSA-N C=1(C(=CC=CC1)C)C.C=1(C(=CC=CC1)C)C.C1(O)=CC(O)=CC=C1 Chemical group C=1(C(=CC=CC1)C)C.C=1(C(=CC=CC1)C)C.C1(O)=CC(O)=CC=C1 IUBPJIAHYCFKGA-UHFFFAOYSA-N 0.000 claims description 2
- 239000004971 Cross linker Substances 0.000 claims description 2
- GHXDFIBBCNLVSG-UHFFFAOYSA-N P(=O)(O)(O)O.C1(=CC=CC=C1)C1=CC=CC=C1.C1(=CC=CC=C1)O.C1(=CC=CC=C1)O Chemical compound P(=O)(O)(O)O.C1(=CC=CC=C1)C1=CC=CC=C1.C1(=CC=CC=C1)O.C1(=CC=CC=C1)O GHXDFIBBCNLVSG-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 239000005062 Polybutadiene Substances 0.000 claims description 2
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-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
- 229910021502 aluminium hydroxide Inorganic materials 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
- 238000001354 calcination Methods 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
- 239000000919 ceramic Substances 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- 229920001577 copolymer Polymers 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
- 239000000835 fiber Substances 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- ULYZAYCEDJDHCC-UHFFFAOYSA-N isopropyl chloride Chemical compound CC(C)Cl ULYZAYCEDJDHCC-UHFFFAOYSA-N 0.000 claims description 2
- QPPQHRDVPBTVEV-UHFFFAOYSA-N isopropyl dihydrogen phosphate Chemical compound CC(C)OP(O)(O)=O QPPQHRDVPBTVEV-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
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 235000014380 magnesium carbonate Nutrition 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
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- 229960001708 magnesium carbonate Drugs 0.000 claims description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-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
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 229920001568 phenolic resin Polymers 0.000 claims description 2
- 239000005011 phenolic resin Substances 0.000 claims description 2
- 239000013034 phenoxy resin Substances 0.000 claims description 2
- 229920006287 phenoxy resin Polymers 0.000 claims description 2
- 235000021317 phosphate Nutrition 0.000 claims description 2
- 150000003016 phosphoric acids Chemical class 0.000 claims description 2
- 229920006122 polyamide resin Polymers 0.000 claims description 2
- 229920002857 polybutadiene Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 239000009719 polyimide resin Substances 0.000 claims description 2
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000004575 stone Substances 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
- XOYXELNNPALJIE-UHFFFAOYSA-N trimethylazanium phosphate Chemical compound C[NH+](C)C.C[NH+](C)C.C[NH+](C)C.[O-]P([O-])([O-])=O XOYXELNNPALJIE-UHFFFAOYSA-N 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
- 239000006185 dispersion Substances 0.000 claims 1
- 229920002379 silicone rubber Polymers 0.000 claims 1
- 125000001033 ether group Chemical group 0.000 abstract 1
- 229920013636 polyphenyl ether polymer Polymers 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 description 14
- 150000002367 halogens Chemical class 0.000 description 14
- 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 10
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 10
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 9
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- 125000005843 halogen group Chemical group 0.000 description 7
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- 238000004519 manufacturing process Methods 0.000 description 7
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000006087 Silane Coupling Agent Substances 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
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- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 5
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- 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 group 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 4
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 4
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- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- 229940106691 bisphenol a Drugs 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
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- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 4
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- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
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- 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
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- 239000002879 Lewis base Substances 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
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Classifications
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- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
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- C08L71/123—Polyphenylene oxides not modified by chemical after-treatment
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- B32B3/10—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L71/12—Polyphenylene oxides
- 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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- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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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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- 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
- H05K2201/01—Dielectrics
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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]
-
- 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
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0203—Fillers and particles
- H05K2201/0206—Materials
- H05K2201/0209—Inorganic, non-metallic particles
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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Abstract
本发明提供一种树脂组成物,其包含:(A)100重量份的未端苯乙烯基的聚苯醚树脂;(B)5至75重量份的烯烃共聚物;及(C)1至150重量份的含聚苯醚官能团的氰酸酯树脂。本发明通过包含特定的组成份及比例,以使可达到低介电常数、低介电损耗及高耐热性的特性;可制作成半固化胶片或树脂膜,进而达到可应用于铜箔基板及印刷电路板的目的。
Description
技术领域
本发明涉及一种树脂组成物,尤指一种应用于铜箔基板及印刷电路板的低介电树脂组成物。
背景技术
为符合世界环保潮流及绿色法规,无卤素(Halogen-free)为当前全球电子产业的环保趋势,世界各国及相关电子大厂陆续对其电子产品,制定无卤素电子产品的量产时程表。欧盟的有害物质限用指令(Restriction of HazardousSubstances,RoHS)实施后,包含铅、镉、汞、六价铬、聚溴联苯与聚溴二苯醚等物质,已不得用于制造电子产品或其零组件。印刷电路板(Printed CircuitBoard,PCB)为电子电机产品的基础,无卤素以对印刷电路板为首先重点管制对象,国际组织对于印刷电路板的卤素含量已有严格要求,其中国际电工委员会(IEC)61249-2-21规范要求溴、氯化物的含量必须低于900ppm,且总卤素含量必须低于1500ppm;日本电子回路工业会(JPCA)则规范溴化物与氯化物的含量限制均为900ppm;而绿色和平组织现阶段大力推动的绿化政策,要求所有的制造商完全排除其电子产品中的聚氯乙烯及溴系阻燃剂,以符合兼具无铅及无卤素的绿色电子。因此,材料的无卤化成为目前从业者的重点开发项目。
新世代的电子产品趋向轻薄短小,并适合高频传输,因此电路板的配线走向高密度化,电路板的材料选用走向更严谨的需求。高频电子组件与电路板接合,为了维持传输速率及保持传输讯号完整性,电路板的基板材料必须兼具较低的介电常数及介电损耗。同时,为了于高温、高湿度环境下依然维持电子组件正常运作功能,电路板也必须兼具耐热、难燃及低吸水性的特性。环氧树脂由于接着性、耐热性、成形性优异,故广泛使用于电子零组件及电机机械的覆铜箔积层板或密封材。从防止火灾的安全性观点而言,要求材料具有阻燃性,一般以无阻燃性的环氧树脂,配合外加阻燃剂的方式达到阻燃的效果,例如,在环氧树脂中通过导入卤素,尤其是溴,而赋予阻燃性,提高环氧基的反应性。另外,在高温下经长时间使用后,可能会引起卤化物的解离,而有微细配线腐蚀的危险。再者使用过后的废弃电子零组件,在燃烧后会产生卤化物等有害化合物,对环境亦不友善。为取代上述的卤化物阻燃剂,有研究使用磷化合物作为阻燃剂,例如添加磷酸酯(台湾专利公告I238846号)或红磷(台湾专利公告322507号)于环氧树脂组成物中。然而,磷酸酯会因产生水解反应而使酸离析,导致影响其耐迁移性;而红磷的阻燃性虽高,但在消防法中被指为危险物品,在高温、潮湿环境下因为会发生微量的膦气体。
熟知的铜箔基板(或称铜箔积层板)制作电路板技术中,是利用环氧基树脂与硬化剂作为热固性树脂组成物原料,将补强材(如玻璃纤维布)与该热固性树脂组成加热结合形成半固化胶片(prepreg),再将该半固化胶片与上、下两片铜箔于高温高压下压合而成。现有技术一般使用环氧基树脂与具有羟基(-OH)的酚醛(phenol novolac)树脂硬化剂作为热固性树脂组成原料,酚醛树脂与环氧基树脂结合会使环氧基开环后形成另一羟基,羟基本身会提高介电常数及介电损耗值,且易与水分结合,增加吸湿性。
先前专利公告第I297346号公开了一种使用氰酸酯树脂、二环戊二烯基环氧树脂、硅石以及热塑性树脂作为热固性树脂组成物,此种热固性树脂组成物具有低介电常数与低介电损耗等特性。然而此制造方法于制作时必须使用含有卤素(如溴)成份的阻燃剂,例如四溴环己烷、六溴环癸烷以及2,4,6-三(三溴苯氧基)-1,3,5-三氮杂苯,而这些含有溴成份的阻燃剂在产品制造、使用甚至回收或丢弃时都很容易对环境造成污染。为了提升铜箔基板的耐热难燃性、低介电损耗、低吸湿性、高交联密度、高玻璃转化温度、高接合性、适当的热膨胀性,环氧树脂、硬化剂及补强材的材料选择成了主要影响因素。
就电气性质而言,主要需考虑者包括材料的介电常数(dielectric constant)以及介电损耗(又称损失因子,dissipation factor)。一般而言,由于基板的讯号传送速度与基板材料的介电常数的平方根成反比,故基板材料的介电常数通常越小越好;另一方面,由于介电损耗越小代表讯号传递的损失越少,故介电损耗较小的材料所能提供的传输质量也较为良好。
因此,如何开发出具有低介电常数以及低介电损耗的材料,并将其应用于高频印刷电路板的制造,乃是现阶段印刷电路板材料供货商亟欲解决的问题。
发明内容
鉴于上述现有技术的缺憾,发明人有感其未臻于完善,遂竭其心智悉心研究克服,凭其从事该项产业多年的累积经验,进而研发出一种树脂组成物,以期达到低介电常数、低介电损耗及高耐热性的目的。
本发明的主要目的在提供一种树脂组成物,其借着包含特定的组成份及比例,以使可达到低介电常数、低介电损耗及高耐热性;可制作成半固化胶片或树脂膜,进而达到可应用于铜箔基板及印刷电路板的目的。
为达上述目的,本发明提供一种树脂组成物,其包含:(A)100重量份的未端苯乙烯基的聚苯醚树脂;(B)5至75重量份的烯烃共聚物;及(C)1至150重量份的含聚苯醚官能基的氰酸酯树脂。
上述的组成物的用途,其用于制造半固化胶片、树脂膜、铜箔基板及印刷电路板。因此,本发明的树脂组成物,其通过包含特定的组成份及比例,以使可达到低介电常数、低介电损耗及高耐热性等特性;可制作成半固化胶片或树脂膜,进而达到可应用于铜箔基板及印刷电路板的目的。
本发明所述的未端苯乙烯基的聚苯醚树脂,具有通式(1)的结构:
其中R1、R2、R3、R4、R5、R6及R7可以相同或不同,且是氢原子、卤素原子、烷基、卤化烷基或苯基,-(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,且是卤素原子、含有1-6个碳原子的烷基或苯基,R11、R12、R13、R18、R19、R20及R21可以相同或不同,且是氢原子、卤素原子、含有1-6个碳原子的烷基或苯基,且A是含有1-20个碳原子及可含有取代基的线性或环状烃)表示,-(Y-O)-是一种由通式(4)定义的结构的排列或由至少两种通式(4)定义的结构的无规则排列(其中R24及R25可以相同或不同,且是卤素原子、含有1-6个碳原子的烷基或苯基,R26及R27可以相同或不同,且是氢原子、卤素原子、含有1-6个碳原子的烷基或苯基),Z是含有至少一个碳原子及可包含氧原子、氮原子、硫原子或卤素原子的有机基团,a及b的每一个是0-300的整数,条件是a或b至少有一不是0,以及c及d的每一个是0或1的整数。
本发明所述的未端苯乙烯基的聚苯醚树脂,相较于现有的双官能未端羟基的聚苯醚树脂,具有较低的介电特性,即具有较低的介电常数及介电损耗。
本发明所述的烯烃共聚物可为甲基苯乙烯共聚物或环型烯烃共聚物(cyclic olefin copolymer),其中环型烯烃共聚物具有通式(5)的结构:
本发明所述的烯烃共聚物不具有羟基(-OH官能基),因而具有较低的介电特性。
本发明的树脂组成物,以100重量份的未端苯乙烯基的聚苯醚树脂为基准,添加5至75重量份的烯烃共聚物,在此添加范围内,可使该树脂组成物降低整体的介电常数及介电损耗,若烯烃共聚物的含量不足5重量份,则达不到电性值要求,若超过75重量份,则耐热性变差。相较于现有技术所使用的双官能未端羟基的聚苯醚树脂,能与环氧树脂有效交联,本发明所述的未端苯乙烯基的聚苯醚树脂,不易与环氧树脂交联反应,导致交联性差,基板特性不佳。因此,本发明使用烯烃共聚物与未端苯乙烯基的聚苯醚树脂交联反应,可有效增加其交联性,改善基板特性。
一般树脂中,聚苯醚树脂通常具有较低的介电特性,而未端苯乙烯基的聚苯醚树脂相较于一般的聚苯醚树脂,具有更低的介电常数及介电损耗,可有效达到树脂组成物具有很低的介电特性,以符合基板的树脂层的低介电特性需求。于本发明中,添加5至75重量份的烯烃共聚物可再降低介电常数及介电损耗,并提高与未端苯乙烯基的聚苯醚树脂的交联性。
本发明所述的含聚苯醚官能基的氰酸酯树脂,具有通式(6)的结构。
其中X6是共价键、-SO2-、-C(CH3)2-、-CH(CH3)-或-CH2-;Z5至Z12各自独立为氢或甲基;W为-O-C≡N;n为大于或等于1的整数。
更具体来说,该含聚苯醚官能基的氰酸酯树脂较佳为选自通式(7)至(10)的至少一种:
其中n为大于或等于1的整数。
相较于现有技术使用的双酚A型氰酸酯树脂,本发明所述的含聚苯醚官能基的氰酸酯树脂,相较于双酚A型氰酸酯树脂具有较低的介电常数及介电损耗。
本发明的树脂组成物,以100重量份的未端苯乙烯基的聚苯醚树脂为基准,添加1至150重量份的含聚苯醚官能基的氰酸酯树脂,在此添加范围内,可提高与未端苯乙烯基的聚苯醚树脂及烯烃共聚物的相互交联性,提高三种树脂间的键结完整性。含聚苯醚官能基的氰酸酯树脂除了可提高交联性外,更可增加玻璃转化温度及与铜箔的接着力。此外,含聚苯醚官能基的氰酸酯树脂、烯烃共聚物及未端苯乙烯基的聚苯醚树脂三者间,可达到优异的低介电特性。
本发明的树脂组成物,较佳是再添加苯并恶嗪树脂,该苯并恶嗪树脂包含:双酚A型苯并恶嗪树脂、双酚F型苯并恶嗪树脂、含二环戊二烯结构的苯并恶嗪树脂及酚酞型苯并恶嗪树脂。更具体而言,其较佳选自下列通式(11)至(13)的至少一种:
其中X1及X2分别独立为R或Ar或-SO2-;R为选自-C(CH3)2-、-CH(CH3)-、-CH2-及经取代或未经取代的二环戊二烯基;Ar为选自经取代或未经取代的苯、联苯、萘、酚醛、双酚A、双酚A酚醛、双酚F及双酚F酚醛官能基。如Huntsman贩卖的商品名LZ-8280,LZ-8290。
本发明的树脂组成物,以100重量份的未端苯乙烯基的聚苯醚树脂为基准,添加5至50重量份的苯并恶嗪树脂,在此添加范围内,可使该树脂组成物降低整体的吸湿率并提高刚性,若苯并恶嗪树脂的含量不足5重量份,则达不到降低吸湿率及提高刚性要求,若超过50重量份,则基板耐热性变差。
为提高本发明的树脂组成物的难燃特性,可进一步添加下列阻燃性化合物。所选用的阻燃性化合物可为磷酸盐化合物或含氮磷酸盐化合物,但并不以此为限。更具体来说,阻燃性化合物较佳为包含以下化合物中的至少一种:双酚联苯磷酸盐(bisphenol diphenyl phosphate)、聚磷酸铵(ammoniumpolyphosphate)、对苯二酚-双-(联苯基磷酸盐)(hydroquinone bis-(diphenylphosphate))、双酚A-双-(联苯基磷酸盐)(bisphenol A bis-(diphenylphosphate))、三(2-羧乙基)膦(tri(2-carboxyethyl)phosphine,TCEP)、三(异丙基氯)磷酸盐、三甲基磷酸盐(trimethyl phosphate,TMP)、二甲基-甲基磷酸盐(dimethyl methylphosphonate,DMMP)、间苯二酚双二甲苯基磷酸盐(resorcinoldixylenylphosphate,RDXP(如PX-200))、聚磷酸三聚氰胺(melaminepolyphosphate)、磷氮基化合物、偶磷氮化合物、9,10-二氢-9-氧杂-10-磷菲-10-氧化物(9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide,DOPO)及其衍生物或树脂、三聚氰胺氰尿酸酯(melamine cyanurate)及三-羟乙基异氰尿酸酯(tri-hydroxy ethyl isocyanurate)等,但并不以此为限。举例来说,阻燃性化合物可为DOPO化合物、DOPO树脂(如DOPO-HQ、DOPO-PN、DOPO-BPN)、DOPO键结的环氧树脂等,其中DOPO-BPN可为DOPO-BPAN、DOPO-BPFN、DOPO-BP SN等双酚酚醛化合物。
本发明的树脂组成物,还可进一步添加无机填充物,添加无机填充物的主要作用,在于增加树脂组成物的热传导性、改良其热膨胀性及机械强度等特性,且无机填充物较佳均匀分布于该无卤树脂组成物中。
其中,无机填充物可包含二氧化硅(熔融态、非熔融态、多孔质或中空型)、氧化铝、氢氧化铝、氧化镁、氢氧化镁、碳酸钙、氮化铝、氮化硼、碳化铝硅、碳化硅、碳酸钠、二氧化钛、氧化锌、氧化锆、石英、钻石粉、类钻石粉、石墨、碳酸镁、钛酸钾、陶瓷纤维、云母、勃姆石(boehmite,AlOOH)、钼酸锌、钼酸铵、硼酸锌、磷酸钙、煅烧滑石、滑石、氮化硅、莫莱石、段烧高岭土、黏土、碱式硫酸镁晶须、莫莱石晶须、硫酸钡、氢氧化镁晶须、氧化镁晶须、氧化钙晶须、纳米碳管、纳米级二氧化硅与其相关无机粉体、或具有有机核外层壳为绝缘体修饰的粉体粒子。且无机填充物可为球型、纤维状、板状、粒状、片状或针须状,并可选择性由硅烷偶合剂预处理。
无机填充物可为粒径100μm以下的颗粒粉末,且较佳为粒径1nm至20μm的颗粒粉末,最佳为粒径1μm以下的纳米尺寸颗粒粉末;针须状无机填充物可为直径50μm以下且长度1至200μm的粉末。
本发明的无机填充物的添加量,以100重量份的未端苯乙烯基的聚苯醚树脂为基准,添加10至1000重量份的无机填充物。若无机填充物的含量不足10重量份,则无显著的热传导性、改良其热膨胀性及机械强度等特性改善;若超过1000重量份,则树脂组成物的填孔流动性变差,与铜箔的接着变差。
以较佳电性值为考虑,本发明的树脂组成物较佳使用熔融态二氧化硅、多孔隙二氧化硅、中空二氧化硅、球型二氧化硅等填充物的其中一种或其组合。
本发明的树脂组成物,还可进一步添加选自下列群组中的至少一者或其改质物:环氧树脂、氰酸酯树脂、苯乙烯马来酸酐、苯酚树脂、酚醛树脂、胺交联剂、苯氧树脂、苯乙烯树脂、聚丁二烯树脂、聚酰胺树脂、聚酰亚胺树脂、聚酯树脂。
本发明的树脂组成物,还可进一步添加环氧树脂,其可选择自双酚A(bisphenol A)环氧树脂、双酚F(bisphenol F)环氧树脂、双酚S(bisphenol S)环氧树脂、双酚AD(bisphenol AD)环氧树脂、酚醛(phenol novolac)环氧树脂、双酚A酚醛(bisphenol A novolac)环氧树脂、邻甲酚(o-cresol novolac)环氧树脂、三官能团(trifunctional)环氧树脂、四官能团(tetrafunctional)环氧树脂、多官能团(multifunctional)环氧树脂、二环戊二烯环氧树脂(dicyclopentadiene(DCPD)epoxy resin)、含磷环氧树脂、含DOPO环氧树脂、含DOPO-HQ环氧树脂、对二甲苯环氧树脂(p-xylene epoxy resin)、萘型(naphthalene)环氧树脂、苯并哌喃型(benzopyran)环氧树脂、联苯酚醛(biphenyl novolac)环氧树脂、酚基苯烷基酚醛(phenol aralkyl novolac)环氧树脂或其组合。
本发明的树脂组成物,较佳为添加二环戊二烯环氧树脂或萘型环氧树脂。其中,添加二环戊二烯环氧树脂可降低树脂组成的吸湿性;添加萘型环氧树脂可增加树脂组成的刚性及耐热性。
此外,本发明的树脂组成物还可选择性包含界面活性剂(surfactant)、硅烷偶合剂(silane coupling agent)、硬化促进剂(curing accelerator)、增韧剂(toughening agent)或溶剂(solvent)等添加物。添加界面活性剂的主要目的在于改善无机填充物于树脂组成物中的均匀分散性,避免无机填充物凝聚。添加增韧剂的主要目的在于改善树脂组成物的韧性。添加硬化促进剂的主要作用在于增加树脂组成物的反应速率。添加溶剂的主要目的在于改变树脂组成物的固含量,并调变树脂组成物的黏度。
所述硅烷偶合剂可包含硅烷化合物(silane)及硅氧烷化合物(siloxane),依官能基种类又可分为胺基硅烷化合物(amino silane)、胺基硅氧烷化合物(aminosiloxane)、环氧基硅烷化合物(epoxy silane)及环氧基硅氧烷化合物(epoxysiloxane)。
所述硬化促进剂可包含路易斯碱或路易斯酸等催化剂(catalyst)。其中,路易斯碱可包含咪唑(imidazole)、三氟化硼胺复合物、氯化乙基三苯基磷(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)与4-二甲基胺基吡啶(4-dimethylaminopyridine,DMAP)中的一种或多种。路易斯酸为可包含金属盐类化合物,如锰、铁、钴、镍、铜、锌等金属盐化合物,如辛酸锌、辛酸钴等金属催化剂。此外,本发明所述的硬化促进剂亦可包含过氧化物(peroxide)、阳离子聚合引发剂、四苯基硼四苯基磷(TPPK)的其一者或其组合。
本发明所述的增韧剂选自:橡胶(rubber)树脂、聚丁二烯丙烯腈(carboxyl-terminated butadiene acrylonitrile rubber,CTBN)、核壳聚合物(core-shell rubber)等添加物。
本发明所述的溶剂可包含甲醇、乙醇、乙二醇单甲醚、丙酮、丁酮(甲基乙基酮)、甲基异丁基酮、环己酮、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、二甲基甲酰胺、丙二醇甲基醚等溶剂或其混合溶剂。
为达到低介电常数及低介电损耗的特性,本发明的树脂组成物必须尽量减少残存的羟基数。亦即,提高树脂间的交联密度。因此,本发明所公开的树脂组成物的各组成份间交联作用,依所揭露的添加比例可促进交联最佳化,残留最少树脂含有未反应官能基。
本发明的又一目的在于揭露一种树脂膜(film),其具有低介电特性、耐热性、低吸湿性及不含卤素等特性,且可应用于积层板和电路板的绝缘层材料。
本发明的树脂膜包含前述的树脂组成物,该树脂组成物经由加热制程而形成半固化态。举例来说,可将该无卤树脂组成物置于聚对苯二甲酸乙二酯(polyethylene terephthalate,PET)膜上并进行加热以形成树脂膜。
本发明的再一目的在于公开一种背胶铜箔(resin coated copper foil,RCC),其包含至少一铜箔及至少一绝缘层。其中,铜箔可进一步包含铜与铝、镍、铂、银、金等金属的合金。通过将本发明所公开的树脂膜贴合于至少一片铜箔上,移除所述PET膜,且将树脂膜及铜箔于高温高压下加热固化,即可形成与铜箔紧密接合的绝缘层。
本发明的再一目的在于公开半固化胶片,其具有高机械强度、低介电特性、耐热性、低吸湿性及不含卤素等特性。据此,本发明所公开的半固化胶片可包含补强材及前述的树脂组成物,其中该树脂组成物附着于该补强材上,并经由高温加热形成半固化态。其中,补强材可为纤维材料、织布及不织布,如玻璃纤维布等,其可增加该半固化胶片的机械强度。此外,该补强材可选择性经由硅烷偶合剂或硅氧烷偶合剂进行预处理,如经硅烷偶合剂预处理的玻璃纤维布。
前述的半固化胶片经由高温加热或高温且高压下加热可固化形成固化胶片或是固态绝缘层,其中树脂组成物若含有溶剂,则该溶剂会于高温加热程序中挥发移除。
本发明的又一目的在于公开一种铜箔基板,其具有高机械强度、低介电特性、耐热性、低吸湿性及不含卤素等特性,且特别适用于高速度高频率讯号传输的电路板。据此,本发明提供一种铜箔基板,其包含两个或两个以上的铜箔及至少绝缘层。其中,铜箔可进一步包含铜与铝、镍、铂、银、金等至少一种金属的合金;绝缘层由前述的半固化胶片于高温高压下固化而成,如将前述半固化胶片迭合于两个铜箔的间且于高温与高压下进行压合而成。
本发明所述的铜箔基板至少具有以下优点之一:低介电常数与低介电损耗的特性。该铜箔基板进一步经由制作线路等制程加工后,可形成一电路板,且该电路板与电子组件接合后于高温、高湿度等严苛环境下操作而并不影响其质量。
本发明的再一目的在于公开一种印刷电路板,其具有高机械强度、低介电特性、耐热性、低吸湿性及不含卤素等特性,且适用于高速度高频率的讯号传输。其中,该电路板包含至少一个前述的铜箔基板,且该电路板可由现有的制程制作而成。
为进一步公开本发明,以使本发明所属技术领域人员具有通常知识者可据以实施,以下谨以数个实施例进一步说明本发明。然应注意,以下实施例仅用以对本发明做进一步的说明,并非用以限制本发明的实施范围,且任何本发明所属技术领域者具有通常知识者在不违背本发明的精神下所得以达成的修饰及变化,均属于本发明的保护范围。
具体实施方式
为充分了解本发明的目的、特征及功效,现通过下述具体的实施例,对本发明做一详细说明,说明如后:
分别将实施例1至5(E1~E5)及比较例1至2(C1~C2)的树脂组成物的组成列表于表一。将上述实施例1至5及比较例1至2的树脂组成物,分批于搅拌槽中混合均匀后置入含浸槽中,再将玻璃纤维布通过上述含浸槽,使树脂组成物附着于玻璃纤维布,再进行加热烘烤成半固化态而得半固化胶片。
将上述分批制得的半固化胶片,取同一批的半固化胶片四张及两张18μm铜箔,依铜箔、四片半固化胶片、铜箔的顺序进行迭合,再于真空条件下经由220℃压合2小时形成铜箔基板,其中四片半固化胶片固化形成两铜箔间的绝缘层。
分别将上述含铜箔基板及铜箔蚀刻后的不含铜基板做物性量测,物性量测项目包含玻璃转化温度(Tg)、含铜基板耐热性(T288)、含铜基板浸锡测试(solderdip 288℃,10秒,测耐热回数,S/D)、浸焊测试(solder dip 288℃,测耐热秒数)、不含铜基板PCT吸湿后浸锡测试(pressure cooking at 121℃,3小时后,测solder dip 288℃,20秒观看有无爆板,PCT)、铜箔与基板间拉力(peelingstrength,halfounce copper foil,P/S)、介电常数(Dk越低越佳)、介电损耗(Df越低越佳)。分别将实施例1至5及比较例1至2的树脂组成物的量测结果列表于表二。
表一
表二
将实施例1至5与比较例1相比较,比较例1不含未端苯乙烯基的聚苯醚树脂,导致介电损耗过高,且耐热性不佳。
将实施例1至5与比较例2相比较,比较例2不含含聚苯醚官能基的氰酸酯树脂,导致介电常数过高,且耐热性不佳。
由实施例1至5可以发现,本发明的树脂组成物包含未端苯乙烯基的聚苯醚树脂、烯烃共聚物及含聚苯醚官能基的氰酸酯树脂,具有低介电常数、低介电损耗及高耐热性的优异特性。
如上所述,本发明完全符合专利三要件:新颖性、创造性和产业上的可利用性。以新颖性和创造性而言,本发明的树脂组成物,其通过包含特定的组成份及比例,以使可达到低介电常数、低介电损耗及高耐热性;可制作成半固化胶片或树脂膜,进而达到可应用于铜箔基板及印刷电路板的目的;就产业上的可利用性而言,利用本发明所衍生的产品,当可充分满足目前市场的需求。
本发明在上文中已以较佳实施例公开,然本领域技术人员应理解的是,该实施例仅用于描绘本发明,而不应解读为限制本发明的范围。应注意的是,举凡与该实施例等效的变化与置换,均应设为涵盖于本发明的权利要求范围内。因此,本发明的保护范围当以下文的权利要求所界定为准。
Claims (12)
1.一种树脂组成物,其包含:
(A)100重量份的未端苯乙烯基的聚苯醚树脂;
(B)5至75重量份的烯烃共聚物;及
(C)1至150重量份的含聚苯醚官能团的氰酸酯树脂。
2.如权利要求1所述的树脂组成物,其中该烯烃共聚物为甲基苯乙烯共聚物或环型烯烃共聚物。
3.如权利要求1所述的树脂组成物,其进一步包含:苯并恶嗪树脂。
4.如权利要求3所述的树脂组成物,其中,包含5至50重量份的苯并恶嗪树脂。
5.如权利要求1至3中任一项所述的树脂组成物,其进一步包含选自下列树脂组中的至少一种:环氧树脂、氰酸酯树脂、苯酚树脂、酚醛树脂、胺交联剂、苯氧树脂、苯并恶嗪树脂、苯乙烯树脂、聚丁二烯树脂、聚酰胺树脂、聚酰亚胺树脂、聚酯树脂。
6.如权利要求1至3中任一项所述的树脂组成物,其进一步包含无机填充物,该无机填充物选自下列物质组中的至少一种:二氧化硅、氧化铝、氢氧化铝、氧化镁、氢氧化镁、碳酸钙、氮化铝、氮化硼、碳化铝硅、碳化硅、碳酸钠、二氧化钛、氧化锌、氧化锆、石英、钻石粉、类钻石粉、石墨、碳酸镁、钛酸钾、陶瓷纤维、云母、勃姆石、钼酸锌、钼酸铵、硼酸锌、磷酸钙、煅烧滑石、滑石、氮化硅、莫莱石、段烧高岭土、黏土、碱式硫酸镁晶须、莫莱石晶须、硫酸钡、氢氧化镁晶须、氧化镁晶须、氧化钙晶须、纳米碳管、纳米级二氧化硅与其相关无机粉体及具有有机核外层壳为绝缘体修饰的粉体粒子。
7.如权利要求1至3中任一项所述的树脂组成物,其进一步包含选自下列物质组中的至少一种:双酚联苯磷酸盐、聚磷酸铵、对苯二酚-双-(联苯基磷酸盐)、双酚A-双-(联苯基磷酸盐)、三(2-羧乙基)膦、三(异丙基氯)磷酸盐、三甲基磷酸盐、二甲基-甲基磷酸盐、间苯二酚双二甲苯基磷酸盐、聚磷酸三聚氰胺、偶磷氮化合物、9,10-二氢-9-氧杂-10-磷菲-10-氧化物及其衍生物或树脂、三聚氰胺氰尿酸酯及三-羟乙基异氰尿酸酯。
8.如权利要求1至3中任一项所述的树脂组成物,其进一步包含选自下列物质组中的至少一种:硬化促进剂、增韧剂、阻燃剂、分散剂、有机硅弹性体及溶剂。
9.一种半固化胶片,其包含如权利要求1至8中任一项所述的树脂组成物。
10.一种树脂膜,其包含如权利要求1至8中任一项所述的树脂组成物。
11.一种铜箔基板,其包含如权利要求9所述的半固化胶片或权利要求9所述的树脂膜。
12.一种印刷电路板,其包含如权利要求11所述的铜箔基板。
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TWI550022B (zh) | 2016-09-21 |
CN103509329B (zh) | 2016-01-20 |
US20140004324A1 (en) | 2014-01-02 |
TW201400547A (zh) | 2014-01-01 |
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