TWI450913B - Thermosetting resin composition and application board and circuit board - Google Patents
Thermosetting resin composition and application board and circuit board Download PDFInfo
- Publication number
- TWI450913B TWI450913B TW100140395A TW100140395A TWI450913B TW I450913 B TWI450913 B TW I450913B TW 100140395 A TW100140395 A TW 100140395A TW 100140395 A TW100140395 A TW 100140395A TW I450913 B TWI450913 B TW I450913B
- Authority
- TW
- Taiwan
- Prior art keywords
- resin
- epoxy resin
- bisphenol
- composition
- benzoxazine
- Prior art date
Links
- 239000011342 resin composition Substances 0.000 title claims description 39
- 229920001187 thermosetting polymer Polymers 0.000 title claims description 10
- 229920005989 resin Polymers 0.000 claims description 75
- 239000011347 resin Substances 0.000 claims description 75
- 239000003822 epoxy resin Substances 0.000 claims description 46
- 229920000647 polyepoxide Polymers 0.000 claims description 46
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 claims description 38
- 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 28
- 239000003063 flame retardant Substances 0.000 claims description 27
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 26
- 239000011256 inorganic filler Substances 0.000 claims description 19
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 19
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 15
- 229910052698 phosphorus Inorganic materials 0.000 claims description 14
- 239000011574 phosphorus Substances 0.000 claims description 14
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 11
- 239000005011 phenolic resin Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 9
- 229910001593 boehmite Inorganic materials 0.000 claims description 8
- 229920001971 elastomer Polymers 0.000 claims description 8
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical group C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 6
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 6
- 239000003431 cross linking reagent Substances 0.000 claims description 6
- 239000000806 elastomer Substances 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- 125000000524 functional group Chemical group 0.000 claims description 5
- 239000004843 novolac epoxy resin Substances 0.000 claims description 5
- 239000012745 toughening agent Substances 0.000 claims description 5
- 229930185605 Bisphenol Natural products 0.000 claims description 4
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims description 4
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 4
- 229920001955 polyphenylene ether Polymers 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229920002857 polybutadiene Polymers 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 2
- KYNSBQPICQTCGU-UHFFFAOYSA-N Benzopyrane Chemical compound C1=CC=C2C=CCOC2=C1 KYNSBQPICQTCGU-UHFFFAOYSA-N 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 150000008065 acid anhydrides Chemical class 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 239000004842 bisphenol F epoxy resin Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 150000002466 imines Chemical class 0.000 claims description 2
- 239000012948 isocyanate Substances 0.000 claims description 2
- 150000002513 isocyanates Chemical class 0.000 claims description 2
- 229920006122 polyamide resin Polymers 0.000 claims description 2
- 229920001225 polyester resin Polymers 0.000 claims description 2
- 239000004645 polyester resin Substances 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 239000009719 polyimide resin Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 45
- 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 25
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 18
- 239000000758 substrate Substances 0.000 description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 14
- 229920003986 novolac Polymers 0.000 description 13
- 229940106691 bisphenol a Drugs 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 239000000843 powder Substances 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 235000010290 biphenyl Nutrition 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000004305 biphenyl Substances 0.000 description 9
- 229910000420 cerium oxide Inorganic materials 0.000 description 9
- 239000011889 copper foil Substances 0.000 description 9
- 239000004615 ingredient Substances 0.000 description 9
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 9
- 125000005577 anthracene group Chemical group 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 125000001624 naphthyl group Chemical group 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- -1 phosphorus compound Chemical class 0.000 description 7
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 6
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 239000004744 fabric Substances 0.000 description 5
- 239000003365 glass fiber Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000012779 reinforcing material Substances 0.000 description 5
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 239000007822 coupling agent Substances 0.000 description 4
- 239000005350 fused silica glass Substances 0.000 description 4
- 150000004820 halides Chemical class 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000008054 signal transmission Effects 0.000 description 4
- 239000000126 substance Substances 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
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 150000002923 oximes Chemical class 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- QQOWHRYOXYEMTL-UHFFFAOYSA-N triazin-4-amine Chemical compound N=C1C=CN=NN1 QQOWHRYOXYEMTL-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- MFAWEYJGIGIYFH-UHFFFAOYSA-N 2-[4-(trimethoxymethyl)dodecoxymethyl]oxirane Chemical compound C(C1CO1)OCCCC(C(OC)(OC)OC)CCCCCCCC MFAWEYJGIGIYFH-UHFFFAOYSA-N 0.000 description 1
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- QMAQLCVJIYANPZ-UHFFFAOYSA-N 2-propoxyethyl acetate Chemical compound CCCOCCOC(C)=O QMAQLCVJIYANPZ-UHFFFAOYSA-N 0.000 description 1
- LBIHNTAFJVHBLJ-UHFFFAOYSA-N 3-(triethoxymethyl)undec-1-ene Chemical compound C(=C)C(C(OCC)(OCC)OCC)CCCCCCCC LBIHNTAFJVHBLJ-UHFFFAOYSA-N 0.000 description 1
- SXPGQGNWEWPWQZ-UHFFFAOYSA-N 4-(triethoxymethyl)dodecan-1-amine Chemical compound NCCCC(C(OCC)(OCC)OCC)CCCCCCCC SXPGQGNWEWPWQZ-UHFFFAOYSA-N 0.000 description 1
- 229960000549 4-dimethylaminophenol Drugs 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- JZHKIUBMQMDQRG-UHFFFAOYSA-N C(=C)C(C(OC)(OC)OC)CCCCCCCC Chemical compound C(=C)C(C(OC)(OC)OC)CCCCCCCC JZHKIUBMQMDQRG-UHFFFAOYSA-N 0.000 description 1
- UTBRISLBLJQSMK-UHFFFAOYSA-N COC(COCC)CCCCCCCC Chemical compound COC(COCC)CCCCCCCC UTBRISLBLJQSMK-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- ZWOQODLNWUDJFT-UHFFFAOYSA-N aluminum lanthanum Chemical compound [Al].[La] ZWOQODLNWUDJFT-UHFFFAOYSA-N 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- BCZWPKDRLPGFFZ-UHFFFAOYSA-N azanylidynecerium Chemical compound [Ce]#N BCZWPKDRLPGFFZ-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 150000004074 biphenyls Chemical class 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Substances FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- HUYMNZHBCIXTGV-UHFFFAOYSA-N cyclopenta-1,3-diene;3,4-dihydro-2h-1,2-benzoxazine Chemical compound C1C=CC=C1.C1C=CC=C1.C1=CC=C2ONCCC2=C1 HUYMNZHBCIXTGV-UHFFFAOYSA-N 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 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 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- NJXBVBPTDHBAID-UHFFFAOYSA-M ethyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 NJXBVBPTDHBAID-UHFFFAOYSA-M 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- NFFIWVVINABMKP-UHFFFAOYSA-N methylidynetantalum Chemical compound [Ta]#C NFFIWVVINABMKP-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910003468 tantalcarbide Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 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 description 1
- 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 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A30/00—Adapting or protecting infrastructure or their operation
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Reinforced Plastic Materials (AREA)
Description
本發明係關於一種苯并噁嗪樹脂,尤指一種應用於積層板及電路板之苯并噁嗪樹脂。
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組件。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對象,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(dielectric constant,Dk)及介電損耗(又稱損失因子,dissipation factor,Df)。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組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。
然而,近來之電子產品,傾向於輕量化、小型化、電路微細化,在如此之要求下,比重大的鹵化物在輕量化的觀點上並不理想。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組件,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308566號及第460537號,揭示一種包含二氫氧氮萘環樹脂之熱固性樹脂組成物,該二氫氧氮萘環樹脂係如雙酚A苯并噁嗪樹脂(Bisphenol-A Benzoxazine,BPA-BZ)或雙酚F苯并噁嗪樹脂(Bisphenol-F Benzoxazine,BPF-BZ),其可改善組成物之硬化性,且不犧牲機械性質。中華民國專利公開第201114853號,揭示一種二環戊二烯-二氫苯并噁嗪樹脂(Dicyclopenta-diene-Dihydrobenzoxazine,DCPD-BZ),由於該苯并噁嗪樹脂之飽和環狀結構,運用在熱固性樹脂組成物中,可有效降低熱膨脹係數、降低基板的介電常數與介電損耗。
就電氣性質而言,主要需考量者包括材料的介電常數以及介電損耗。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。
有鑑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,進而研發出一種苯并噁嗪樹脂,以期達到低介電常數、低介電損耗、高剛性及高耐熱性之目的。
本發明之主要目的在提供一種苯并噁嗪樹脂,其藉著包含萘環、聯苯或蒽環結構,應用於熱固性樹脂組中可達到低介電常數、低介電損耗、高剛性及高耐熱性,可製作成半固化膠片或樹脂膜,進而達到可應用於積層板及電路板之目的。
為達上述目的,本發明提供一種苯并噁嗪樹脂,其係選自下列化合物之其中一者:
其中,n及m為任意正整數,Y代表氫基、脂肪族官能基或芳香族官能基。
本發明所述之含萘環、聯苯或蒽環結構之苯并噁嗪樹脂,具有苯并噁嗪之官能基,其可與酚類或胺類等其它交聯劑(cross-linking agent)反應鍵結,且其分別具有萘環、聯苯或蒽環結構,可提供該樹脂高剛性及高耐熱性。本發明所述之含萘環、聯苯、蒽環結構之苯并噁嗪樹脂,可應用於樹脂產業,如一般常見之環氧樹脂應用產業,作為接著劑、金屬箔基板之絕緣層材料或半固化膠片等。
本發明所述之含萘環結構之苯并噁嗪樹脂,係由含萘環之酚醛樹脂(naphthalene type phenol novolac),與苯胺及甲醛等三種原料所合成,其合成方法係使用先前技術中普遍使用之方法。同理,含聯苯結構之苯并噁嗪樹脂及含蒽環結構之苯并噁嗪樹脂,係分別為含聯苯之酚醛樹脂(biphenyl type phenol novolac)及含蒽環之酚醛樹脂(anthracene type phenol novolac),與苯胺及甲醛等三種原料所合成。
本發明之另一目的係提供一種熱固性樹脂組成物,其包含:(1)上述之苯并噁嗪樹脂;以及(2)交聯劑。該樹脂組成物係具有高耐熱性及高剛性。
所述之交聯劑係選自下列群組之至少一者:苯酚樹脂、胺樹脂、酚醛樹脂、酸酐樹脂、苯乙烯樹脂、丁二烯樹脂、聚醯胺樹脂、聚醯亞胺樹脂、聚酯樹脂、聚醚樹脂、聚苯醚樹脂、氰酸酯樹脂、異氰酸酯樹脂、馬來醯亞胺樹脂、雙酚A苯並噁嗪樹脂、雙酚F苯並噁嗪樹脂、溴化樹脂、含磷樹脂及含氮樹脂。該交聯劑之作用在於與本發明所述之含萘環、聯苯或蒽環結構之苯并噁嗪樹脂鍵結,完成交聯反應。
上述之組成物,其進一步包含環氧樹脂及硬化促進劑。
所述之環氧樹脂係選自下列群組之至少一者: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、雙酚F酚醛(bisphenol F 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 epoxy resin)、含磷環氧樹脂、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)環氧樹脂及酚基苯烷基酚醛(phenol aralkyl novolac)環氧樹脂。
所述之硬化促進劑係選自下列群組之至少一者:路易士鹼及路易士酸。其中路易士鹼可包括咪唑、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,2PI)、2-乙基-4-甲基咪唑(2-ethyl-4-methylimidazole,2E4MI)、三苯基膦(triphenylphosphine,TPP)、4-二甲基胺基吡啶(4-dimethylaminopyridine,DMAP)等。路易士酸則可包括錳、鐵、鈷、鎳、銅及鋅之金屬鹽化合物。添加硬化促進劑之主要目的,在於增加所述樹脂組成物之反應速率。
上述之組成物,其進一步包含選自下列群組中之至少一者:無機填充物、界面活性劑、增韌劑、阻燃劑、有機矽彈性體及溶劑。
所述無機填充物並無特別限制,習知用於積層板之無機填充物均可,例如:二氧化矽(熔融態或非熔融態與多孔質)、氧化鋁、氧化鎂、氫氧化鎂、碳酸鈣、氮化鋁、氮化硼、氫氧化鋁、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)、氫氧化鋁(Aluminium Trihydrate,ATH,Al(OH)3)、鉬酸鋅、鉬酸銨、硼酸鋅、磷酸鈣、煅燒滑石、滑石、氮化矽、莫萊石、段燒高嶺土、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、片狀或針鬚狀,並可選擇性經由界面活性劑預處理。
無機填充物可為粒徑100 μm以下之顆粒粉末,且較佳為粒徑1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;針鬚狀無機填充物可為直徑50 μm以下且長度1至200 μm之粉末。添加無機填充物之主要目的,在於增加所述樹脂組成物之熱傳導性,改良熱膨脹性及機械強度,且提高剛性,較佳係使無機填充物均勻分佈於該樹脂組成物中。
所述界面活性劑,或稱矽氧烷偶合劑(Siloxane)可使用公知者,並無特別限定,具體而言,係選自乙烯基三乙氧基矽烷、乙烯基三甲氧基矽烷、乙烯基參(β-甲氧基-乙氧基矽烷)、γ-環氧丙氧基丙基三甲氧基矽烷、γ-胺丙基三乙氧基矽烷,其中分散劑可為BYK-103、BYK-901、BYK-161或BYK-164等。添加界面活性劑之主要目的,在於改善無機填充物於所述樹脂組成物中之均勻分散性。
所述增韌劑選自:橡膠樹脂、聚丁二烯、核殼聚合物等添加物。添加增韌劑之主要目的,在於改善樹脂組成物之韌性。
所述阻燃劑選自:含磷阻燃劑、含氮阻燃劑(如Melamine Cyanurate)、含溴阻燃劑(TBBPA,Tetra-Bromo-Bisphenol A)之其一者或其組合,其中,含磷耐燃劑可為磷酸鹽類含磷耐燃劑或DOPO類含磷耐燃劑,前者與樹脂並無交聯性,且可為例如Exolit OP 935(可購自Clariant公司)、SPB-100(可購自大塚化學)、PX-200(可購自大八化學);後者與樹脂具有交聯性,且可為例如由DOPO或其衍生物所取代之雙酚酚醛樹脂(Bisphenol novolac,BPN)或酚醛樹脂(Phenol novolac,PN),如DOPO-雙酚A酚醛樹脂(DOPO-bisphenol-A novolac,DOPO-BPAN)或DOPO-酚醛樹脂(DOPO-phenol novolac,DOPO-PN),但不以此為限。
所述有機矽彈性體(Hybrid type silicone powder)一般為橡膠及樹脂型複合粉體,較佳為球狀粉體,添加有機矽彈性體可增加本發明之熱固性樹脂組成的耐熱性且衝擊吸收性。該有機矽彈性體並無特別限制,習知用於積層板之有機矽彈性體均可,例如:信越生產之X-52-7030、KMP-605、KMP-602、KMP-601、KMP-600、KMP-590及KMP-594等產品。
所述溶劑係包含甲醇、乙醇、乙二醇單甲醚、丙酮、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。添加溶劑之主要目的,在於改變所述樹脂組成物之固含量,並調變該樹脂組成物之黏度。
本發明之再一目的係提供一種無鹵無磷樹脂組成物,其包含:(1)萘型環氧樹脂;(2)上述之苯并噁嗪樹脂;(3)硬化促進劑;以及選擇性添加(4)氫氧化鋁及勃姆石中之一者或其組合。
本發明所述之無鹵無磷樹脂組成物,係使用氫氧化鋁或勃姆石作為阻燃劑,有效改善先前技術使用鹵素阻燃劑(如溴化阻燃劑)於燃燒時會釋放戴奧辛(Dioxin)等有害物,及使用含磷阻燃劑會造成較差的化學阻抗性。本發明使用氫氧化鋁及勃姆石作為阻燃劑之原理,為利用高溫時氫氧化鋁及勃姆石會釋放出結晶水以阻止火焰繼續燃燒。此外,使用萘型環氧樹脂(特別是四官能萘型環氧樹脂),及本發明所述之含萘環、聯苯或蒽環結構之苯并噁嗪樹脂,因具有萘環、聯苯或蒽環等高耐熱耐燃結構,搭配氫氧化鋁及勃姆石使用,可有效達到UL-94規範之V-0耐燃功效。
上述之組成物,其進一步包含選自下列群組中之至少一者:無機填充物、界面活性劑、增韌劑、阻燃劑、有機矽彈性體及溶劑。
本發明之再一目的係提供一種半固化膠片,其具有低介電常數、低介電損耗、高剛性、高耐熱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無鹵樹脂組成物,其中該無鹵樹脂組成物係以含浸等方式附著於該補強材上,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,其中無鹵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。
本發明之再一目的係提供一種積層板,其具有低介電常數、低介電損耗、高剛性、高耐熱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,本發明提供一種積層板,其包含兩個或兩個以上之金屬箔及至少一絕緣層。其中,金屬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。該積層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。
本發明之再一目的係提供一種電路板,其包含上述之積層板,具有低介電常數、低介電損耗、高剛性、高耐熱性及不含鹵素等特性,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積層板,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2至5之樹脂組成物列表於表一,比較例1至4之樹脂組成物列表於表三。
實施例1(E1)
一種樹脂組成物,包括以下成份:
(A)100重量份之式一所示苯并噁嗪樹脂;
(B)20重量份之酚醛樹脂(Phenol novolac)。
實施例2(E2)
一種樹脂組成物,包括以下成份:
(A)100重量份之二環戊二烯環氧樹脂(HP-7200);
(B)75重量份之式三所示苯并噁嗪樹脂;
(C)10重量份之胺基三嗪酚醛樹脂(Amino triazine novolac,ATN);
(D)30重量份之DOPO-BPAN樹脂阻燃劑;
(E)80重量份之二氧化矽(Silica)無機填充物;
(F)0.3重量份之2E4MI觸媒;
(G)20重量份之甲基乙基酮(MEK)。
實施例3(E3)
一種樹脂組成物,包括以下成份:
(A)50重量份之二環戊二烯環氧樹脂(HP-7200);
(B)50重量份之雙酚A環氧樹脂(BE-188E);
(C)40重量份之雙酚A苯并噁嗪樹脂(BPA-BZ);
(D)35重量份之式三所示苯并噁嗪樹脂;
(E)25重量份之苯乙烯馬來酸酐樹脂(Styrene-maleic anhydride,SMA);
(F)30重量份之磷腈化合物(SPB-100)阻燃劑;
(G)70重量份之熔融態二氧化矽(Fused silica)無機填充物;
(H)0.35重量份之2E4MI觸媒;
(I)20重量份之甲基乙基酮(MEK)。
實施例4(E4)
一種樹脂組成物,包括以下成份:
(A)100重量份之雙酚A氰酸酯樹脂(BA-230S);
(B)40重量份之式五所示苯并噁嗪樹脂;
(C)30重量份之聚苯醚樹脂(PPO);
(D)10重量份之萘型酚樹脂(EXB-9500);
(E)50重量份之熔融態二氧化矽(Fused silica)無機填充物;
(F)25重量份之含磷阻燃劑(PX-200);
(G)0.01重量份之辛酸鋅觸媒(Zn);
(H)20重量份之甲基乙基酮(MEK)。
實施例5(E5)
一種無鹵無磷樹脂組成物,包括以下成份:
(A)100重量份之四官能萘型環氧樹脂(HP-4700);
(B)40重量份之式一所示苯并噁嗪樹脂;
(C)20重量份之萘型酚樹脂(EXB-9500);
(D)0.3重量份之2E4MI觸媒;
(E)50重量份之勃姆石(Boehmite)無機填充物;
(F)20重量份之甲基乙基酮(MEK)。
比較例1(C1)
一種樹脂組成物,包括以下成份:
(A)100重量份之二環戊二烯環氧樹脂(HP-7200);
(B)75重量份之雙酚A苯并噁嗪樹脂(BPA-BZ);
(C)10重量份之胺基三嗪酚醛樹脂(Amino triazine novolac,ATN);
(D)30重量份之DOPO-BPAN樹脂阻燃劑;
(E)80重量份之二氧化矽(Silica)無機填充物;
(F)0.3重量份之2E4MI觸媒;
(G)20重量份之甲基乙基酮。
比較例2(C2)
一種樹脂組成物,包括以下成份:
(A)50重量份之二環戊二烯環氧樹脂(HP-7200);
(B)50重量份之雙酚A環氧樹脂(BE-188E);
(C)75重量份之雙酚A苯并噁嗪樹脂(BPA-BZ);
(D)25重量份之苯乙烯馬來酸酐樹脂(Styrene-maleic anhydride,SMA);
(E)30重量份之磷腈化合物(SPB-100)阻燃劑;
(F)70重量份之熔融態二氧化矽(Fused silica)無機填充物;
(G)0.35重量份之2E4MI觸媒;
(H)20重量份之甲基乙基酮。
比較例3(C3)
一種樹脂組成物,包括以下成份:
(A)100重量份之雙酚A氰酸酯樹脂(BA-230S);
(B)40重量份之雙酚A苯并噁嗪樹脂(BPA-BZ);
(C)30重量份之聚苯醚樹脂(PPO);
(D)10重量份之萘型酚樹脂(EXB-9500);
(E)50重量份之熔融態二氧化矽(Fused silica)無機填充物;
(F)25重量份之含磷阻燃劑(PX-200);
(G)0.01重量份之辛酸鋅觸媒(Zn);
(H)20重量份之甲基乙基酮(MEK)。
比較例4(C4)
一種樹脂組成物,包括以下成份:
(A)100重量份之四官能萘型環氧樹脂(HP-4700);
(B)40重量份之雙酚A苯并噁嗪樹脂(BPA-BZ);
(C)20重量份之萘型酚樹脂(EXB-9500);
(D)0.3重量份之2E4MI觸媒;
(E)50重量份之二氧化矽(Silica)無機填充物;
(F)20重量份之甲基乙基酮(MEK)。
將上述實施例2至5及比較例1至4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190℃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,物性量測項目包含玻璃轉化溫度(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)、介電常數(Dk越低越佳)、介電損耗(Df越低越佳)、耐燃性(flaming test,UL94,其中等級優劣排列為V-0>V-1>V-2)。
其中實施例2至5之樹脂組成物製作之基板物性量測結果列表於表二中,比較例1至4之樹脂組成物製作之基板物性量測結果列表於表四中。由表二及表四,綜合比較實施例2至5及比較例1至4可發現,依本發明所揭露之苯并噁嗪樹脂,相較於習知技術所使用之雙酚A苯并噁嗪樹脂,能提升基板耐熱性(Tg、T288、S/D)。此外,實施例5之樹脂組成物不含阻燃劑,亦可達到UL94 V-0耐燃標準,對照比較例4只有較差的V-2耐燃性。
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,本發明藉著於樹脂組成物中包含特定之苯并噁嗪樹脂,以使可達到低介電常數、低介電損耗、高剛性及高耐熱性;可製作成半固化膠片或樹脂膜,進而達到可應用於積層板及電路板之目的;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,均應設為涵蓋於本發明之範疇內。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 (10)
- 一種苯并噁嗪樹脂,其係選自下列化合物之其中一者:
- 一種熱固性樹脂組成物,其包含:(1)如申請專利範圍第1項所述之苯并噁嗪樹脂;以及(2)交聯劑。
- 如申請專利範圍第2項所述之組成物,其中該交聯劑係選自下列群組之至少一者:苯酚樹脂、酚醛樹脂、酸酐樹脂、 苯乙烯樹脂、丁二烯樹脂、聚醯胺樹脂、聚醯亞胺樹脂、聚酯樹脂、聚醚樹脂、聚苯醚樹脂、氰酸酯樹脂、異氰酸酯樹脂、馬來醯亞胺樹脂、雙酚A苯並噁嗪樹脂、雙酚F苯並噁嗪樹脂、溴化樹脂及含磷樹脂。
- 如申請專利範圍第2項所述之組成物,其進一步包含環氧樹脂及硬化促進劑。
- 如申請專利範圍第4項所述之組成物,其中該環氧樹脂係選自下列群組之至少一者:雙酚A環氧樹脂、雙酚F環氧樹脂、雙酚S環氧樹脂、雙酚AD環氧樹脂、雙酚A酚醛環氧樹脂、雙酚F酚醛環氧樹脂、鄰甲酚環氧樹脂、三官能基環氧樹脂、四官能基環氧樹脂、二環戊二烯環氧樹脂、含磷環氧樹脂、對二甲苯環氧樹脂、萘型環氧樹脂、苯并哌喃型環氧樹脂、聯苯酚醛環氧樹脂及酚基苯烷基酚醛環氧樹脂。
- 一種無鹵無磷樹脂組成物,其包含:(1)萘型環氧樹脂;(2)如申請專利範圍第1項所述之苯并噁嗪樹脂;(3)硬化促進劑;以及選擇性添加(4)氫氧化鋁及勃姆石中之一者或其組合。
- 如申請專利範圍第2或6項所述之組成物,其進一步包含選自下列群組中之至少一者:無機填充物、界面活性劑、增韌劑、阻燃劑、有機矽彈性體及溶劑。
- 一種半固化膠片,其係包含如申請專利範圍第2至7項中任一項所述之組成物。
- 一種積層板,其係包含如申請專利範圍第8項所述之半固 化膠片。
- 一種電路板,其包含如申請專利範圍第9項所述之積層板。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
TW100140395A TWI450913B (zh) | 2011-11-04 | 2011-11-04 | Thermosetting resin composition and application board and circuit board |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
TW100140395A TWI450913B (zh) | 2011-11-04 | 2011-11-04 | Thermosetting resin composition and application board and circuit board |
Publications (2)
Publication Number | Publication Date |
---|---|
TW201319113A TW201319113A (zh) | 2013-05-16 |
TWI450913B true TWI450913B (zh) | 2014-09-01 |
Family
ID=48872343
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW100140395A TWI450913B (zh) | 2011-11-04 | 2011-11-04 | Thermosetting resin composition and application board and circuit board |
Country Status (1)
Country | Link |
---|---|
TW (1) | TWI450913B (zh) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111164127A (zh) * | 2017-10-20 | 2020-05-15 | 日本化药株式会社 | 硬化性树脂组合物、清漆、预浸体、硬化物、及积层板或覆铜积层板 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6620905B1 (en) * | 2002-02-23 | 2003-09-16 | National Starch And Chemical Investment Holding Corporation | Curable compositions containing benzoxazine |
EP1647576A1 (en) * | 2005-04-01 | 2006-04-19 | Huntsman Advanced Materials (Switzerland) GmbH | Composition comprising benzoxazine and epoxy resin |
CN101817925A (zh) * | 2010-04-15 | 2010-09-01 | 华烁科技股份有限公司 | 存储稳定性高的二氨型苯并噁嗪树脂的制造方法 |
CN101830862A (zh) * | 2010-04-15 | 2010-09-15 | 华烁科技股份有限公司 | 一种高耐热、高阻燃、低成本的酚醛型苯并噁嗪树脂的制备方法 |
-
2011
- 2011-11-04 TW TW100140395A patent/TWI450913B/zh not_active IP Right Cessation
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6620905B1 (en) * | 2002-02-23 | 2003-09-16 | National Starch And Chemical Investment Holding Corporation | Curable compositions containing benzoxazine |
EP1647576A1 (en) * | 2005-04-01 | 2006-04-19 | Huntsman Advanced Materials (Switzerland) GmbH | Composition comprising benzoxazine and epoxy resin |
CN101817925A (zh) * | 2010-04-15 | 2010-09-01 | 华烁科技股份有限公司 | 存储稳定性高的二氨型苯并噁嗪树脂的制造方法 |
CN101830862A (zh) * | 2010-04-15 | 2010-09-15 | 华烁科技股份有限公司 | 一种高耐热、高阻燃、低成本的酚醛型苯并噁嗪树脂的制备方法 |
Also Published As
Publication number | Publication date |
---|---|
TW201319113A (zh) | 2013-05-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
TWI460225B (zh) | Halogen-free resin composition and the use of its copper foil substrate and printed circuit board | |
TWI476244B (zh) | Halogen-free resin composition | |
TWI550022B (zh) | Low dielectric resin composition and the use of its copper foil substrate and printed circuit board | |
TWI486393B (zh) | Halogen-free resin composition and copper foil substrate and printed circuit board to which the same applies | |
TWI491671B (zh) | Low dielectric halogen-free resin compositions and circuit boards for which they are used | |
CN103131131B (zh) | 无卤素树脂组合物及其应用的铜箔基板及印刷电路板 | |
TWI588202B (zh) | Low dielectric resin composition and copper foil substrate and printed circuit board using the same | |
TWI481659B (zh) | Halogen-free resin composition and its application of copper foil substrate and printed circuit board | |
US9005761B2 (en) | Halogen-free resin composition and its application for copper clad laminate and printed circuit board | |
CN103013110B (zh) | 无卤素树脂组成物及应用其的铜箔基板及印刷电路板 | |
TWI646142B (zh) | Resin composition and copper foil substrate and printed circuit board using same | |
TWI478981B (zh) | Halogen-free resin composition and its application | |
TWI466891B (zh) | A vinylated phosphazene compound, a resin composition comprising the same, and a circuit board to which the resin composition is used | |
JP2020117607A (ja) | エポキシ樹脂組成物及びその硬化物 | |
CN103131007B (zh) | 热固性树脂组合物及应用其的积层板及电路板 | |
TWI421297B (zh) | Halogen-free resin composition and its application of copper foil substrate and printed circuit board | |
TWI452064B (zh) | Resin composition and its application | |
TW201425446A (zh) | 無鹵素樹脂組成物及應用其之銅箔基板及印刷電路板 | |
CN101845200A (zh) | 无卤热固性树脂组合物及由其制得的预浸料和层压板 | |
TWI435909B (zh) | Epoxy resin composition and the application of its low dielectric constant insulation material | |
TWI450913B (zh) | Thermosetting resin composition and application board and circuit board | |
TWI429344B (zh) | Halogen-free resin composition and its application of copper foil substrate and printed circuit board | |
CN102234363B (zh) | 无卤素难燃树脂组合物 | |
TWI477527B (zh) | Halogen-free flame retardant resin composition |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
MM4A | Annulment or lapse of patent due to non-payment of fees |