CN114806078A - Low-expansion-coefficient halogen-free resin composition, laminated plate and printed circuit board - Google Patents
Low-expansion-coefficient halogen-free resin composition, laminated plate and printed circuit board Download PDFInfo
- Publication number
- CN114806078A CN114806078A CN202110060714.1A CN202110060714A CN114806078A CN 114806078 A CN114806078 A CN 114806078A CN 202110060714 A CN202110060714 A CN 202110060714A CN 114806078 A CN114806078 A CN 114806078A
- Authority
- CN
- China
- Prior art keywords
- halogen
- weight
- resin composition
- parts
- expansion coefficient
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 36
- 239000004848 polyfunctional curative Substances 0.000 claims abstract description 28
- 239000003822 epoxy resin Substances 0.000 claims abstract description 25
- 239000003063 flame retardant Substances 0.000 claims abstract description 25
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 25
- 229920005989 resin Polymers 0.000 claims abstract description 25
- 239000011347 resin Substances 0.000 claims abstract description 25
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 18
- 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 abstract description 13
- 239000004643 cyanate ester Substances 0.000 claims abstract description 13
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229920003192 poly(bis maleimide) Polymers 0.000 claims abstract description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 8
- 239000011574 phosphorus Substances 0.000 claims abstract description 8
- 229930185605 Bisphenol Natural products 0.000 claims abstract 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 abstract 9
- 239000000758 substrate Substances 0.000 claims description 20
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 15
- 239000004744 fabric Substances 0.000 claims description 15
- 239000003365 glass fiber Substances 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- -1 phosphazene compound Chemical class 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 12
- 150000002431 hydrogen Chemical class 0.000 claims description 10
- 150000002978 peroxides Chemical class 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 8
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 8
- 239000011256 inorganic filler Substances 0.000 claims description 8
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 8
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 8
- 229920006395 saturated elastomer Polymers 0.000 claims description 7
- 125000006732 (C1-C15) alkyl group Chemical group 0.000 claims description 6
- AAOADXIHXYIOMT-UHFFFAOYSA-N 1,1'-biphenyl;phosphoric acid Chemical compound OP(O)(O)=O.C1=CC=CC=C1C1=CC=CC=C1 AAOADXIHXYIOMT-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 6
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 6
- 125000004122 cyclic group Chemical group 0.000 claims description 6
- VOOLKNUJNPZAHE-UHFFFAOYSA-N formaldehyde;2-methylphenol Chemical compound O=C.CC1=CC=CC=C1O VOOLKNUJNPZAHE-UHFFFAOYSA-N 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 5
- 239000011888 foil Substances 0.000 claims description 5
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims description 4
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- 229920000388 Polyphosphate Polymers 0.000 claims description 4
- PZBFGYYEXUXCOF-UHFFFAOYSA-N TCEP Chemical compound OC(=O)CCP(CCC(O)=O)CCC(O)=O PZBFGYYEXUXCOF-UHFFFAOYSA-N 0.000 claims description 4
- AHZMUXQJTGRNHT-UHFFFAOYSA-N [4-[2-(4-cyanatophenyl)propan-2-yl]phenyl] cyanate Chemical compound C=1C=C(OC#N)C=CC=1C(C)(C)C1=CC=C(OC#N)C=C1 AHZMUXQJTGRNHT-UHFFFAOYSA-N 0.000 claims description 4
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 4
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 4
- 239000001205 polyphosphate Substances 0.000 claims description 4
- 235000011176 polyphosphates Nutrition 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- IKFPAKYBSYICFK-UHFFFAOYSA-N 1-[4-(4-propylphenoxy)phenyl]pyrrole-2,5-dione Chemical compound C1=CC(CCC)=CC=C1OC1=CC=C(N2C(C=CC2=O)=O)C=C1 IKFPAKYBSYICFK-UHFFFAOYSA-N 0.000 claims description 3
- NHWYMYDMYCNUKI-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)-3,5-diethylphenyl]methyl]-2,6-diethylphenyl]pyrrole-2,5-dione Chemical compound C=1C(CC)=C(N2C(C=CC2=O)=O)C(CC)=CC=1CC(C=C1CC)=CC(CC)=C1N1C(=O)C=CC1=O NHWYMYDMYCNUKI-UHFFFAOYSA-N 0.000 claims description 3
- RUORVEVRVBXRIO-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)-3,5-dimethylphenyl]methyl]-2,6-dimethylphenyl]pyrrole-2,5-dione Chemical compound C=1C(C)=C(N2C(C=CC2=O)=O)C(C)=CC=1CC(C=C1C)=CC(C)=C1N1C(=O)C=CC1=O RUORVEVRVBXRIO-UHFFFAOYSA-N 0.000 claims description 3
- YNSSPVZNXLACMW-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)-3-ethyl-5-methylphenyl]methyl]-2-ethyl-6-methylphenyl]pyrrole-2,5-dione Chemical compound C=1C(C)=C(N2C(C=CC2=O)=O)C(CC)=CC=1CC(C=C1CC)=CC(C)=C1N1C(=O)C=CC1=O YNSSPVZNXLACMW-UHFFFAOYSA-N 0.000 claims description 3
- 229910052582 BN Inorganic materials 0.000 claims description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 239000007983 Tris buffer Substances 0.000 claims description 3
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 3
- 125000000392 cycloalkenyl group Chemical group 0.000 claims description 3
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- ULYZAYCEDJDHCC-UHFFFAOYSA-N isopropyl chloride Chemical compound CC(C)Cl ULYZAYCEDJDHCC-UHFFFAOYSA-N 0.000 claims description 3
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 3
- 239000001095 magnesium carbonate Substances 0.000 claims description 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- 239000010445 mica Substances 0.000 claims description 3
- 229910052618 mica group Inorganic materials 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- 239000000454 talc Substances 0.000 claims description 3
- 229910052623 talc Inorganic materials 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 3
- QPPQHRDVPBTVEV-UHFFFAOYSA-N isopropyl dihydrogen phosphate Chemical compound CC(C)OP(O)(O)=O QPPQHRDVPBTVEV-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 17
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 abstract description 4
- 239000004843 novolac epoxy resin Substances 0.000 abstract description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 31
- 239000011889 copper foil Substances 0.000 description 23
- 238000012360 testing method Methods 0.000 description 23
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- 229910052802 copper Inorganic materials 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 229910052718 tin Inorganic materials 0.000 description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010292 electrical insulation Methods 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 238000010030 laminating Methods 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- RVPBHEHFYATJIP-UHFFFAOYSA-N P1OC=CC2=C1C=CC=C2 Chemical compound P1OC=CC2=C1C=CC=C2 RVPBHEHFYATJIP-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- JUPWRUDTZGBNEX-UHFFFAOYSA-N cobalt;pentane-2,4-dione Chemical compound [Co].CC(=O)CC(C)=O.CC(=O)CC(C)=O.CC(=O)CC(C)=O JUPWRUDTZGBNEX-UHFFFAOYSA-N 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 2
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 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 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000007790 scraping Methods 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 2
- RUEBPOOTFCZRBC-UHFFFAOYSA-N (5-methyl-2-phenyl-1h-imidazol-4-yl)methanol Chemical compound OCC1=C(C)NC(C=2C=CC=CC=2)=N1 RUEBPOOTFCZRBC-UHFFFAOYSA-N 0.000 description 1
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 description 1
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 1
- 125000006736 (C6-C20) aryl group Chemical group 0.000 description 1
- GRPTWLLWXYXFLX-UHFFFAOYSA-N 1,1,2,2,3,3-hexabromocyclodecane Chemical compound BrC1(Br)CCCCCCCC(Br)(Br)C1(Br)Br GRPTWLLWXYXFLX-UHFFFAOYSA-N 0.000 description 1
- OMIVCRYZSXDGAB-UHFFFAOYSA-N 1,4-butanediyl Chemical group [CH2]CC[CH2] OMIVCRYZSXDGAB-UHFFFAOYSA-N 0.000 description 1
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 1
- 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 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- 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 1
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 description 1
- QBFHSEQNGHSFLZ-UHFFFAOYSA-N 2,4,6-tris(2,3,4-tribromophenoxy)-1,3,5-triazine Chemical compound BrC1=C(Br)C(Br)=CC=C1OC1=NC(OC=2C(=C(Br)C(Br)=CC=2)Br)=NC(OC=2C(=C(Br)C(Br)=CC=2)Br)=N1 QBFHSEQNGHSFLZ-UHFFFAOYSA-N 0.000 description 1
- KRDXTHSSNCTAGY-UHFFFAOYSA-N 2-cyclohexylpyrrolidine Chemical compound C1CCNC1C1CCCCC1 KRDXTHSSNCTAGY-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- 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
- UIDDPPKZYZTEGS-UHFFFAOYSA-N 3-(2-ethyl-4-methylimidazol-1-yl)propanenitrile Chemical compound CCC1=NC(C)=CN1CCC#N UIDDPPKZYZTEGS-UHFFFAOYSA-N 0.000 description 1
- 208000037427 Beta-propeller protein-associated neurodegeneration Diseases 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 241000863480 Vinca Species 0.000 description 1
- DDNCQMVWWZOMLN-IRLDBZIGSA-N Vinpocetine Chemical compound C1=CC=C2C(CCN3CCC4)=C5[C@@H]3[C@]4(CC)C=C(C(=O)OCC)N5C2=C1 DDNCQMVWWZOMLN-IRLDBZIGSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- UUQQGGWZVKUCBD-UHFFFAOYSA-N [4-(hydroxymethyl)-2-phenyl-1h-imidazol-5-yl]methanol Chemical compound N1C(CO)=C(CO)N=C1C1=CC=CC=C1 UUQQGGWZVKUCBD-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- GCKAMTHMSCXVIL-UHFFFAOYSA-N bis(2,3-dimethylphenyl) (3-hydroxyphenyl) phosphate Chemical compound P(=O)(OC1=C(C(=CC=C1)C)C)(OC1=C(C(=CC=C1)C)C)OC1=CC(O)=CC=C1 GCKAMTHMSCXVIL-UHFFFAOYSA-N 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 150000001868 cobalt Chemical class 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
- FCEOGYWNOSBEPV-FDGPNNRMSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FCEOGYWNOSBEPV-FDGPNNRMSA-N 0.000 description 1
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- ZKXWKVVCCTZOLD-FDGPNNRMSA-N copper;(z)-4-hydroxypent-3-en-2-one Chemical compound [Cu].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O ZKXWKVVCCTZOLD-FDGPNNRMSA-N 0.000 description 1
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000005007 epoxy-phenolic resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 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 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- AQBLLJNPHDIAPN-LNTINUHCSA-K iron(3+);(z)-4-oxopent-2-en-2-olate Chemical compound [Fe+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O AQBLLJNPHDIAPN-LNTINUHCSA-K 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- ZQZQURFYFJBOCE-FDGPNNRMSA-L manganese(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Mn+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O ZQZQURFYFJBOCE-FDGPNNRMSA-L 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000006178 methyl benzyl group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical class CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 201000007614 neurodegeneration with brain iron accumulation 5 Diseases 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 description 1
- JFOJYGMDZRCSPA-UHFFFAOYSA-J octadecanoate;tin(4+) Chemical compound [Sn+4].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O JFOJYGMDZRCSPA-UHFFFAOYSA-J 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- NRNFFDZCBYOZJY-UHFFFAOYSA-N p-quinodimethane Chemical group C=C1C=CC(=C)C=C1 NRNFFDZCBYOZJY-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- PRCNQQRRDGMPKS-UHFFFAOYSA-N pentane-2,4-dione;zinc Chemical compound [Zn].CC(=O)CC(C)=O.CC(=O)CC(C)=O PRCNQQRRDGMPKS-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 229960000744 vinpocetine Drugs 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/036—Multilayers with layers of different types
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/02—Coating on the layer surface on fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/101—Glass fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/558—Impact strength, toughness
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2479/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/16—Solid spheres
- C08K7/18—Solid spheres inorganic
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The application discloses a halogen-free resin composition with low expansion coefficient, a laminated plate and a printed circuit board. The halogen-free resin composition comprises: (a)30 to 40 parts by weight of an o-cresol novolac epoxy resin, (b)50 to 70 parts by weight of a bismaleimide resin, (c)75 to 105 parts by weight of a cyanate ester hardener, (d)30 to 45 parts by weight of a bisphenol a-type DOPO hardener, (e)10 to 20 parts by weight of a non-DOPO phosphorus-containing flame retardant, and (f)2 to 12 parts by weight of a DOPO flame retardant. The halogen-free resin composition can provide an epoxy resin composition with low expansion coefficient, low dielectric loss and high rigidity through specific components and proportions, and provides better toughness and heat resistance.
Description
Technical Field
The present invention relates to a resin composition, and a laminate and a printed circuit board using the same, and more particularly, to a halogen-free resin composition with low expansion coefficient, low dielectric loss and high rigidity, a laminate and a printed circuit board.
Background
Under the continuous heat in the communication electronics market, high-frequency and high-speed transmission has become a necessary option, and the circuit board for carrying components, power supply and signal transmission has become a key in the development of the field, while the prior art printed circuit board made of epoxy resin and phenolic resin material has not been able to satisfy the advanced application of high frequency.
In the printed circuit board technology, a thermosetting resin composition mainly comprising epoxy resin and a hardener is heated and combined with a reinforcing material (such as glass fiber cloth) to form a prepreg (preprg), and then the prepreg is laminated with an upper copper foil and a lower copper foil at high temperature and high pressure to form a copper foil laminated plate (or called a copper foil substrate). The general thermosetting resin composition uses phenolic novolac resin hardener having hydroxyl (-OH) group, which can open the ring of epoxy group to form hydroxyl group after combining with epoxy resin, and the hydroxyl group can increase the dielectric constant and dielectric loss value, and is easy to react with H 2 O bonds, resulting in increased hygroscopicity.
The prior art epoxy resin composition uses fire retardant (especially bromine fire retardant) containing halogen component, such as tetrabromocyclohexane, hexabromocyclodecane and 2,4, 6-tri (tribromophenoxy) -1,3, 5-triazabenzene, etc., the fire retardant containing halogen component has the advantages of good fire resistance and less addition, however, halogen product is easy to pollute environment when being manufactured and used, even being recycled or discarded, besides, halogen-containing electronic equipment waste can generate corrosive, toxic gas and smoke when being burned, and carcinogenic substances such as dioxin, dibenzofuran, etc. can be detected in the products after being burned. Therefore, halogen-free flame-retardant printed circuit boards have become the focus of development in the art.
In addition to the development of halogen-free flame retardant printed circuit boards, the characteristics of copper foil substrates such as heat resistance, flame retardancy, low dielectric loss, low moisture absorption, high crosslinking density, high glass transition temperature, high adhesion, and proper thermal expansion are important issues for the development and manufacture of printed circuit boards, and therefore, the selection of materials for epoxy resin, hardener, and reinforcing material is a major factor.
Disclosure of Invention
The present application provides a halogen-free resin composition with low expansion coefficient, low dielectric loss and high rigidity, a laminate and a printed circuit board, which are directed to overcome the disadvantages of the prior art.
In order to solve the above technical problems, one of the technical solutions adopted in the present application is to provide a halogen-free resin composition with low expansion coefficient, low dielectric loss and high rigidity, which comprises:
(a)30 to 40 parts by weight of an o-cresol formaldehyde epoxy resin;
(b)50 to 70 parts by weight of a bismaleimide resin;
(c)75 to 105 parts by weight of a cyanate ester hardener;
(d)30 to 45 parts by weight of bisphenol a DOPO hardener;
(e)10 to 20 parts by weight of a non-DOPO phosphorus-containing flame retardant; and
(f)2 to 12 parts by weight of a DOPO flame retardant;
wherein the DOPO flame retardant is selected from the group consisting of the following chemical formulas (I) and (II):
wherein R is 1 Is C (R) 4 ) 2 ；R 2 And R 3 Each of which isIndependently hydrogen, C1-C15 alkyl, C6-C12 aryl, C7-C15 aralkyl, or C7-C15 alkaryl; or R 2 And R 3 Can form a saturated or unsaturated cyclic ring substituted or unsubstituted with C1-C6 alkyl; each R 4 Independently hydrogen, C1-C6 alkyl, C6-C12 aryl, or C3-C12 cycloalkyl; and each m is independently selected from a positive integer from 1 to 4;
wherein A is a direct bond, C6-C12 aryl, C3-C12 cycloalkyl, or C3-C12 cycloalkenyl, and the cycloalkyl or cycloalkenyl can be optionally substituted with C1-C6 alkyl;
wherein R is 1 、R 2 、R 3 And R 4 Independently hydrogen, C1-C15 alkyl, C6-C12 aryl, C7-C15 aralkyl, or C7-C15 alkaryl; or R 1 And R 2 Or R 3 And R 4 Can form a saturated or unsaturated cyclic ring substituted or unsubstituted with C1-C6 alkyl; each m is independently selected from a positive integer of 1 to 4, each R 5 And R 6 Independently hydrogen or C1-C6 alkyl; each n is independently selected from a positive integer from 0 to 5.
Further, the bismaleimide is selected from the group consisting of bis (4-maleimidophenyl) methane, 2-bis (4- (4-maleimidophenoxy) -phenyl) propane, bis (3, 5-dimethyl-4-maleimidophenyl) methane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane and bis (3, 5-diethyl-4-maleimidophenyl) methane.
Still further, the cyanate ester hardener includes 45 to 55 parts by weight of a phenolic cyanate ester hardener and 30 to 50 parts by weight of a bisphenol a cyanate ester hardener.
Still further, the bisphenol a DOPO hardener has the following structure:
still further, the non-DOPO flame retardant is selected from the group consisting of resorcinol bisxylylphosphate, melamine polyphosphate, tris (2-carboxyethyl) phosphine, trimethylphosphate, tris (isopropylchloride) phosphate, dimethyl-methyl phosphate, bisphenol biphenyl phosphate, ammonium polyphosphate, hydroquinone-bis- (biphenyl phosphate), bisphenol a-bis- (biphenyl phosphate), and phosphazene compound.
Further, the low expansion coefficient halogen-free resin composition further comprises: a hardening accelerator selected from the group consisting of phosphorus-based hardening accelerators, amine-based hardening accelerators, imidazole-based hardening accelerators, guanidine-based hardening accelerators, metal-based hardening accelerators and peroxide-based hardening accelerators.
Still further, the hardening accelerator includes: 1 part by weight of a metal-based curing accelerator, 1 part by weight of 2-ethyl-4-methylimidazole, and 1 part by weight of a peroxide-based curing accelerator.
Further, the low expansion coefficient halogen-free resin composition further comprises: an inorganic filler selected from the group consisting of silica, alumina, aluminum hydroxide, magnesium oxide, magnesium hydroxide, calcium carbonate, aluminum nitride, boron nitride, aluminum silicon carbide, titanium dioxide, zinc oxide, zirconium oxide, barium sulfate, magnesium carbonate, barium carbonate, mica, talc, and graphene.
In order to solve the above technical problem, another technical solution adopted by the present application is to provide a laminate, including: the resin substrate comprises a plurality of semi-solidified films, and each semi-solidified film is prepared by coating glass fiber cloth with the halogen-free resin composition with low expansion coefficient, low dielectric loss and high rigidity; and a metal foil layer disposed on at least one surface of the resin substrate.
In order to solve the above technical problem, another technical solution adopted by the present application is to provide a printed circuit board, which includes a laminate as in the present application.
The halogen-free resin composition with the low expansion coefficient, the laminated plate and the printed circuit board have the advantages that the halogen-free resin composition with the low expansion coefficient, the laminated plate and the printed circuit board can be provided through specific components and proportions, meanwhile, the toughness and the heat resistance of the plate are improved, and the cost is reduced. Moreover, the composition can be made into a semi-cured film or a resin film, so as to achieve the purpose of being applied to a copper foil substrate and a printed circuit board, and the product derived from the composition can be utilized to fully meet the requirements of the current market in terms of industrial applicability.
For a better understanding of the nature and technical content of the present application, reference should be made to the following detailed description of the present application, which is provided for purposes of illustration and description only and is not intended to be limiting.
Detailed Description
The following description is provided by way of specific examples to describe embodiments of the halogen-free resin composition with low expansion coefficient, laminates and printed circuit boards disclosed herein, and those skilled in the art can understand the advantages and effects of the present disclosure from the disclosure of the present disclosure. The present application is capable of other and different embodiments and its several details are capable of modifications and variations in various respects, all without departing from the present application. The following embodiments will further explain the related art of the present application in detail, but the disclosure is not intended to limit the scope of the present application. In addition, the term "or" as used herein should be taken to include any one or combination of more of the associated listed items as the case may be.
The term "alkyl" as used herein includes saturated monovalent hydrocarbon radicals having straight or branched chain moieties. Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, pentyl, and hexyl.
The term "alkenyl" as used herein includes alkyl moieties having at least one carbon-carbon double bond, wherein alkyl is as defined above. Examples of alkenyl groups include, but are not limited to, ethenyl and propenyl.
The term "aryl" as used herein includes organic groups derived from aromatic hydrocarbons by removal of one hydrogen, such as phenyl, naphthyl, indenyl, and fluorenyl. "aryl" encompasses fused ring groups in which at least one ring is aromatic.
The term "aralkyl" as used herein is an "aryl-alkyl-" group. Non-limiting examples of aralkyl groups are benzyl (C6H5CH2-) and methylbenzyl (CH3C6H4CH 2-).
The term "alkaryl" as used herein is an "alkyl-aryl-" group. Non-limiting examples of alkaryl groups are methylphenyl-, dimethylphenyl-, ethylphenyl-, propylphenyl-, isopropylphenyl-, butylphenyl-, isobutylphenyl-, and tert-butylphenyl-.
As used herein, the term "cycloalkyl" includes non-aromatic saturated cyclic alkyl moieties, wherein alkyl is as defined above. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl.
Unless otherwise indicated, all of the above hydrocarbon-derived groups can have from about 1 to about 20 carbon atoms (e.g., C1-C20 alkyl, C6-C20 aryl, C7-C20 alkaryl, C7-C20 aralkyl) or from 1 to about 12 carbon atoms (e.g., C1-C12 alkyl, C6-C12 aryl, C7-C12 alkaryl, C7-C12 aralkyl), or from 1 to about 8 carbon atoms, or from 1 to about 6 carbon atoms.
The present application provides a halogen-free resin composition with low expansion coefficient, low dielectric loss and high rigidity, a laminate and a printed circuit board, which are directed to overcome the disadvantages of the prior art.
In order to solve the above technical problems, one of the technical solutions adopted in the present application is to provide a halogen-free resin composition with low expansion coefficient, low dielectric loss and high rigidity, which comprises:
(a)30 to 40 parts by weight of an o-cresol formaldehyde epoxy resin;
(b)50 to 70 parts by weight of a bismaleimide resin;
(c)75 to 105 parts by weight of a cyanate ester hardener;
(d)30 to 45 parts by weight of bisphenol a DOPO hardener;
(e)10 to 20 parts by weight of a non-DOPO phosphorus-containing flame retardant; and
(f)2 to 12 parts by weight of a DOPO flame retardant.
The molecular structure of the o-cresol formaldehyde epoxy resin is that an epoxy group is connected on each benzene ring, compared with bisphenol A epoxy resin in the prior art, the epoxy value of the o-cresol formaldehyde epoxy resin is up to more than 0.5eq/100g, 2.5 times of cross-linking points can be provided when the resin is cured, a three-dimensional structure with high cross-linking density is easily formed, and the o-cresol formaldehyde epoxy resin has better thermal stability, mechanical strength, electrical insulation performance, water resistance, chemical resistance and higher glass transition temperature (Tg), is applied to electronic components, and can still maintain good electrical insulation performance in high-temperature and humid environments. Preferably, the o-cresol novolac epoxy resin may be commercially available NPCN-701, NPCN-702, NPCN-703 or NPCN-704 (all trade names) manufactured by Nanasia plastics industries, Ltd; CNE202 manufactured by vinpocetine artificial resin factory; n-665, N-670, N-673, N-680, N-690 and N-695 manufactured by Dainippon ink chemical industries, Ltd; YDCN-701, YDCN-702, YDCN-703, YDCN-704, YDCN-701P, YDCN-702P, YDCN-703P, YDCN-704-P, YDCN-701S, YDCN-702S, YDCN-703S manufactured by eastern chemical Co.Ltd of Japan; SQCN700-1, SQCN700-2, SQCN700-3, SQCN700-4, SQCN700-4.5, SQCN702, SQCN703, SQCN700-1, SQCN704L, SQCN704ML, SQCN707, SQCN704H manufactured by Shandong Shengquan chemical industry.
The bismaleimide resin of the present application is not particularly limited, and is mainly a compound having two maleimide groups in the molecule, and a prepolymer of a bismaleimide compound or a prepolymer of a bismaleimide compound and an amine compound may be used. Preferably, the bismaleimide is selected from the group consisting of bis (4-maleimidophenyl) methane, 2-bis (4- (4-maleimidophenoxy) -phenyl) propane, bis (3, 5-dimethyl-4-maleimidophenyl) methane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane and bis (3, 5-diethyl-4-maleimidophenyl) methane.
The hardener of the present application can increase the reactive functionality in the resin structure, increasing the glass transition temperature. 45 to 55 parts by weight of a phenolic cyanate ester hardener, 30 to 50 parts by weight of a bisphenol a cyanate ester hardener, and 30 to 45 parts by weight of a bisphenol a DOPO hardener. The phenolic cyanate hardener has the heat resistance and the flame retardance of phenolic resin and the dielectric property of cyanate. Preferably, the phenolic cyanate ester hardener comprises commercially available Yangzhou StartType CE-05CS, the bisphenol A cyanate ester hardener comprises commercially available Lonza model ULL-950S, and the bisphenol A DOPO type hardener comprises commercially available Olin model XQ-83006.
Bisphenol a DOPO type hardeners, for example, may have the following structure:
non-DOPO phosphorus containing flame retardants, as defined herein, means that they do not contain 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) derivatives. In detail, the P-O-C bond in the DOPO structure is easily hydrolyzed into P-OH, which increases the Dielectric Constant and Dielectric loss of the material, so that the non-DOPO flame retardant can avoid increasing Dk and DF of the material, wherein Dk is the Dielectric Constant (ε r) and DF is the Dielectric loss.
In more detail, the non-DOPO flame retardant is selected from resorcinol dixylylphosphates (RDXP (e.g. PX-200)), melamine polyphosphates (melamine polyphosphates), tris (2-carboxyethyl) phosphine (TCEP), trimethy lphosphates (TMP), tris (isopropylchloride) phosphates, dimethyl methyl phosphate (DMMP), bisphenol diphenyl phosphate (biphenol diphenyl phosphate), ammonium polyphosphate (ammonium polyphosphate), hydroquinone-bis- (biphenylphosphate) (hydroquinone bis- (biphenylphosphate)), bisphenol A-bis- (biphenylphosphate) (biphenol A bis- (biphenylphosphate)), and Phosphazene compounds (commercially available products such as SPB-100, SPH-100, SPV-100). Preferably, 20 to 30 parts by weight of resorcinol dixylylphosphate is used in combination with 5 to 15 parts by weight of the phosphazene compound (e.g., SPB-100). Preferably, the non-DOPO flame retardant of the present application is resorcinol dixylyl phosphate (e.g., PX-200) in an amount of 10 to 20 parts by weight, which provides excellent halogen-free flame retardant effect.
In another aspect, the DOPO flame retardant of the present application is selected from the group consisting of the following formulas (I) and (II):
wherein R is 1 Is C (R) 4 ) 2 ；R 2 And R 3 Each independently hydrogen, C1-C15 alkyl, C6-C12 aryl, C7-C15 aralkyl, or C7-C15 alkaryl; or R 2 And R 3 Can form a saturated or unsaturated cyclic ring substituted or unsubstituted with C1-C6 alkyl; each R 4 Independently hydrogen, C1-C6 alkyl, C6-C12 aryl, or C3-C12 cycloalkyl; and each m is independently selected from a positive integer from 1 to 4;
wherein A is a direct bond, C6-C12 aryl, C3-C12 cycloalkyl, or C3-C12 cycloalkenyl, and the cycloalkyl or cycloalkenyl can be optionally substituted with C1-C6 alkyl;
wherein R is 1 、R 2 、R 3 And R 4 Independently hydrogen, C1-C15 alkyl, C6-C12 aryl, C7-C15 aralkyl, or C7-C15 alkaryl; or R 1 And R 2 Or R 3 And R 4 Can form a saturated or unsaturated cyclic ring substituted or unsubstituted with C1-C6 alkyl; each m is independently selected from a positive integer of 1 to 4, each R 5 And R 6 Independently hydrogen or C1-C6 alkyl; each n is independently selected from a positive integer from 0 to 5.
Specifically, the DOPO flame retardant may be selected from the group consisting of 6H-ibenz [ c, e ] [1,2] oxaphosphinobenzene, 6,6'- (1, 2-ethanediyl) bis-, 6,6' -dioxide, 6H-dibenzene [ c, e ] [1,2] oxaphosphinobenzene, 6,6'- (1, 4-butanediyl) bis-, 6,6' -dioxide, or 6H-dibenzene [ c, e ] [1,2] oxaphosphinobenzene, 6,6'- (p-xylylene) bis-, 6,6' -dioxide.
In addition, the resin composition of the present application further comprises: the curing accelerator which can cause the cyanate ester to undergo a ring-opening reaction is selected from the group consisting of phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, metal-based curing accelerators and peroxide-based curing accelerators. Preferably, the metal-based curing accelerator is mixed with the peroxide-based curing accelerator.
More specifically, examples of the metallic hardening accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organic metal complex include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, organic zinc complexes such as zinc (II) acetylacetonate, organic iron complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate. Preferably, the metal-based hardening accelerator is cobalt (III) acetylacetonate (Co (acac) 3).
Examples of the peroxide-based curing accelerator include cyclohexanone peroxide, tert-butyl peroxybenzoate, methyl ethyl ketone peroxide, dicumyl peroxide, tert-butyl cumyl peroxide, di-tert-butyl peroxide, dicumyl peroxide, cumyl hydroperoxide, and tert-butyl hydroperoxide. Preferably, the peroxide-based hardening accelerator is dicumyl peroxide (DCP) commercially available from Arkema.
The imidazole-based hardening accelerator may be selected from the group consisting of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4, 5-dihydroxymethylimidazole and 2-phenyl-4-methyl-5-hydroxymethylimidazole.
More preferably, the hardening accelerator of the present application may be 1 part by weight of a metal-based hardening accelerator, 1 part by weight of 2-ethyl-4-methylimidazole and 1 part by weight of a peroxide-based hardening accelerator based on 100 parts by weight of the epoxy resin.
In addition, the resin composition of the present application further comprises: the inorganic filler can increase the thermal conductivity of the halogen-free low-dielectric epoxy resin composition and improve the thermal expansion and mechanical strength of the halogen-free low-dielectric epoxy resin composition, and preferably, the inorganic filler is uniformly distributed in the halogen-free low-dielectric epoxy resin composition. Preferably, the inorganic filler may be previously surface-treated with a silane coupling agent. Preferably, the inorganic filler may be spherical, flaky, granular, columnar, plate-like, needle-like or irregular. Preferably, the inorganic filler is selected from the group consisting of silica (e.g., fused, non-fused, porous or hollow silica), alumina, aluminum hydroxide, magnesium oxide, magnesium hydroxide, calcium carbonate, aluminum nitride, boron nitride, aluminum silicon carbide, titanium dioxide, zinc oxide, zirconium oxide, barium sulfate, magnesium carbonate, barium carbonate, mica, talc, and graphene. Preferably, the inorganic filler may be added in an amount of 200 to 200 parts by weight based on 100 parts by weight of the epoxy resin. Preferably, NQ-1035I, available from Nomoray, is used to effectively increase thermal conductivity, mechanical strength, and reduce thermal expansion.
In addition, the halogen-free low dielectric constant epoxy resin composition further comprises a suitable amount of solvent, such as ketones, esters, ethers, alcohols, and the like, and more specifically, the solvent is selected from the group consisting of acetone, methyl ethyl ketone, propylene glycol methyl ether acetate, dimethylacetamide, and cyclohexanone. For example, the solvent may be selected from a combination of 60 to 70 parts by weight of Methyl Ethyl Ketone (MEK) and 70 to 80 parts by weight of Cyclohexanone (cyclohexone), or other solvents, and the like.
In order to solve the above technical problem, another technical solution adopted by the present application is to provide a laminate, including: the resin substrate comprises a plurality of semi-solidified films, and each semi-solidified film is prepared by coating glass fiber cloth with the halogen-free resin composition with low expansion coefficient, low dielectric loss and high rigidity; and a metal foil layer disposed on at least one surface of the resin substrate.
This application still provides another technical scheme is a laminated board, and it includes: (a) the resin substrate comprises a plurality of semi-solidified films, and each semi-solidified film is prepared by coating a glass fiber cloth with the halogen-free low-dielectric epoxy resin composition; and (b) a metal foil layer disposed on at least one surface of the resin substrate, or the metal foil layer may be disposed on the resin substrate up and down as required.
In addition, the present application further provides another technical solution, which is a printed circuit board including the laminate of the present application.
The following examples and comparative examples are conducted on the halogen-free epoxy resin composition of the present application to illustrate the best laminate properties achieved by the specific composition ratio formulation of the present application.
Examples
The following examples E1-E4 were prepared in a continuous process using the halogen-free low dielectric epoxy resin composition of the present application to produce prepreg. Usually, a glass fiber cloth is used as a substrate. The rolled glass fiber cloth continuously passes through a series of rollers and enters a sizing groove, and the groove is filled with the halogen-free low-dielectric epoxy resin composition. Fully soaking glass fiber cloth in resin in a glue feeding groove, scraping redundant resin through a metering roller, baking the glass fiber cloth in a glue feeding furnace for a certain time to evaporate a solvent and solidify the resin to a certain degree, cooling and rolling the glass fiber cloth to form a semi-solidified film, taking four semi-solidified films and two 18 mu m copper foils of the same batch of semi-solidified films, laminating the semi-solidified films according to the sequence of the copper foils, the four semi-solidified films and the copper foils, and laminating the semi-solidified films at 220 ℃ for 2 hours under a vacuum condition to form a copper foil substrate, wherein the four semi-solidified films form an insulating layer between the two copper foils.
TABLE 1
Cresol novolac epoxy: CNE-202 cresol novolac epoxy resin manufactured by Vinca rayon.
Bismleimides: KI-70 manufactured by KI.
Cyanate ester (PN type): CE-05CS, manufactured by Yangzhou Tianqi corporation.
BPAN-DOPO: XQ-83006, manufactured by Olin corporation.
Cyanate ester (BPA type): ULL-9505, manufactured by Lonza.
Comparative example
Prepreg was manufactured in a continuous process according to the components and proportions of comparative examples C1 to C7 of table 2 below. Usually, a glass fiber cloth is used as a substrate. The rolled glass fiber cloth continuously passes through a series of rollers and enters a sizing groove, and the groove is filled with the halogen-free low-dielectric epoxy resin composition. Fully soaking glass fiber cloth in resin in a glue feeding groove, scraping redundant resin through a metering roller, baking the glass fiber cloth in a glue feeding furnace for a certain time to evaporate a solvent and solidify the resin to a certain degree, cooling and rolling the glass fiber cloth to form a semi-solidified film, taking four semi-solidified films and two 18 mu m copper foils of the same batch of semi-solidified films, laminating the semi-solidified films according to the sequence of the copper foils, the four semi-solidified films and the copper foils, and laminating the semi-solidified films at 220 ℃ for 2 hours under a vacuum condition to form a copper foil substrate, wherein the four semi-solidified films form an insulating layer between the two copper foils.
TABLE 2
HP-7200: DCPD (dicyclopentadiene type) type epoxy resins.
NC-3000: biphenyl type epoxy resin from chemical company of Japan.
Maleic anhydride modified polyimide resin of formula 1-3 and flame retardants of formula I-III: see, patent number TWI632190 and application number TW 109106662.
Physical Property test
Physical properties of the copper clad laminates of examples E1 to E4 and comparative examples C1 to C7 were measured, and the test results were recorded in table 3:
glass transition temperature (Tg): according to Differential Scanning Calorimetry (DSC), the measurement was carried out according to the DSC method specified by IPC-TM-6502.4.25.
Heat resistance of copper foil laminate (T288): also known as the "tin floating result", the heat resistance test was conducted by immersing the copper clad laminate in a tin furnace at 288 ℃ for the time required for board explosion according to the industry standard IPC-TM-6502.4.24.1.
And (3) carrying out wicking test on the copper foil-containing laminated plate after moisture absorption: the prepreg containing copper foil layer was used for heat resistance (T288) test and the copper clad laminate was immersed in a tin furnace at 288 ℃ for the time required for board burst according to industry standard IPC-TM-6502.4.24.1.
Heat resistance (S/D) test of copper foil laminate: copper-containing substrates were tested for wicking (solder dip 288 ℃,10 seconds, heat cycle resistance).
Heat resistance (PCT) test of copper foil laminate: no copper substrate PCT immersion tin test after moisture absorption (pressure cooking at 121 ℃,1 hour later, the solder dip 288 ℃, 20 seconds to see the existence of explosion plate).
Tension (P/S) between copper foil and substrate: the determination was made according to the IPC-TM-6502.4.1 test specification.
Dielectric constant (Dk): the dielectric constant represents the electrical insulation property of the film produced, and lower values represent better electrical insulation properties, as determined by IPC-TM-6502.5.5 test specifications.
Dielectric loss (Df): dielectric loss, measured according to IPC-TM-6502.5.5 test specifications, indicates the ability of a substance to absorb microwaves of a certain frequency at a certain temperature, and generally, in the specifications of communication products, the lower the dielectric loss value, the better.
Flame resistance (flaming test, UL 94): the flame resistance rating of the plastic material is determined according to the UL94 vertical combustion method by the spontaneous combustion time, spontaneous combustion speed and falling particle state of the standard test piece of the plastic material after flame combustion. And HB, V-2, V-1 and V-0 are sequentially ranked according to the grade of flame resistance, and the highest grade is 5V. Whereas the UL94 test method refers to the burning of plastic material in a vertical manner on a flame. Every ten seconds is taken as a test period, and the steps are as follows: the method comprises the following steps: placing the test piece in the flame for ten seconds and removing the test piece, and measuring the burning time of the test piece after the removal (T1); step two: when the flame of the test piece is extinguished, the test piece is put into the flame for ten seconds and then removed, and the continuous burning time of the test piece after the removal is measured (T2); step three: repeating the experiment for a plurality of times and taking the average value; step four: the total of T1+ T2 was calculated. The UL 94V-0 rating is required to satisfy the UL 94V-0 requirement that neither the average of T1 nor the average of T2 should exceed 10 seconds, and the sum of T1 and T2 should not exceed 50 seconds.
Coefficient of Thermal Expansion (CTE) in the X/Y axis: the determination was made according to the IPC-TM-650-2.4.24 test specification.
Z-axis Coefficient of Thermal Expansion (CTE) (50-260 ℃): the determination was made according to the IPC-TM-650-2.4.24.1 test specification.
Modulus (X/Y) was measured according to the IPC-TM-6502.4.24.4 test protocol.
TABLE 3
Advantageous effects of the embodiments
The halogen-free resin composition with the low expansion coefficient, the laminated plate and the printed circuit board have the advantages that the halogen-free resin composition with the low expansion coefficient, the laminated plate and the printed circuit board can be provided through specific components and proportions, meanwhile, the toughness and the heat resistance of the plate are improved, and the cost is reduced. Moreover, the composition can be made into a semi-cured film or a resin film, so as to achieve the purpose of being applied to a copper foil substrate and a printed circuit board, and the product derived from the composition can be utilized to fully meet the requirements of the current market in terms of industrial applicability.
Furthermore, the copper clad laminate prepared by the halogen-free resin composition with low expansion coefficient, low dielectric loss and high rigidity provided by the application has lower expansion coefficient, and compared with the prior art, the CTE of an X/Y axis is lower than 10 ppm/DEG C, the CTE of a Z axis (50-260 ℃) is lower than 1%, and the dielectric loss (Df) of 0.008 at 10GHz is lower, so that the copper clad laminate provides more excellent glass transition temperature (Tg), has better rigidity in sheet toughness, and obviously has better heat-resisting effect compared with the prior art.
The disclosure is intended to cover alternatives, modifications and equivalents, which may be included within the spirit and scope of the disclosure as defined by the appended claims.
Claims (10)
1. The halogen-free resin composition with low expansion coefficient, the laminate and the printed circuit board are characterized by comprising the following components in percentage by weight:
(a)30 to 40 parts by weight of an o-cresol formaldehyde epoxy resin;
(b)50 to 70 parts by weight of a bismaleimide resin;
(c)75 to 105 parts by weight of a cyanate ester hardener;
(d)30 to 45 parts by weight of bisphenol a DOPO hardener;
(e)10 to 20 parts by weight of a non-DOPO phosphorus-containing flame retardant; and
(f)2 to 12 parts by weight of a DOPO flame retardant;
wherein the DOPO flame retardant is selected from the group consisting of the following chemical formulas (I) and (II):
wherein R is 1 Is C (R) 4 ) 2 ；R 2 And R 3 Each independently hydrogen, C1-C15 alkyl, C6-C12 aryl, C7-C15 aralkyl, or C7-C15 alkaryl; or R 2 And R 3 Can form a saturated or unsaturated cyclic ring substituted or unsubstituted with C1-C6 alkyl; each R 4 Independently hydrogen, C1-C6 alkyl, C6-C12 aryl, or C3-C12 cycloalkyl; and each m is independently selected from a positive integer from 1 to 4;
wherein A is a direct bond, C6-C12 aryl, C3-C12 cycloalkyl, or C3-C12 cycloalkenyl, and the cycloalkyl or cycloalkenyl can be optionally substituted with C1-C6 alkyl;
wherein R is 1 、R 2 、R 3 And R 4 Independently hydrogen, C1-C15 alkyl, C6-C12 aryl, C7-C15 aralkyl, or C7-C15 alkaryl; or R 1 And R 2 Or R 3 And R 4 Can form a saturated or unsaturated cyclic ring substituted or unsubstituted with C1-C6 alkyl; each m is independently selected from a positive integer of 1 to 4, each R 5 And R 6 Independently hydrogen or C1-C6 alkyl; each n is independently selected from a positive integer from 0 to 5.
2. The low expansion factor halogen-free resin composition of claim 1 wherein the bismaleimide is selected from the group consisting of bis (4-maleimidophenyl) methane, 2-bis (4- (4-maleimidophenoxy) -phenyl) propane, bis (3, 5-dimethyl-4-maleimidophenyl) methane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane and bis (3, 5-diethyl-4-maleimidophenyl) methane.
3. The halogen-free resin composition with low expansion coefficient of claim 1, wherein the cyanate ester hardener comprises 45 to 55 weight parts of phenolic cyanate ester hardener and 30 to 50 weight parts of bisphenol A cyanate ester hardener.
4. The halogen-free resin composition with low expansion coefficient as claimed in claim 1, wherein the bisphenol A DOPO hardener has the following structure:
5. the halogen-free resin composition with low expansion coefficient of claim 1, wherein the non-DOPO flame retardant is selected from the group consisting of resorcinol bisxylylphosphate, melamine polyphosphate, tris (2-carboxyethyl) phosphine, trimethylphosphate, tris (isopropylchloride) phosphate, dimethyl-methyl phosphate, bisphenol biphenyl phosphate, ammonium polyphosphate, hydroquinone-bis- (biphenyl phosphate), bisphenol A-bis- (biphenyl phosphate) and phosphazene compound.
6. The low expansion coefficient halogen-free resin composition of claim 1, wherein the low expansion coefficient halogen-free resin composition further comprises: a hardening accelerator selected from the group consisting of phosphorus-based hardening accelerators, amine-based hardening accelerators, imidazole-based hardening accelerators, guanidine-based hardening accelerators, metal-based hardening accelerators and peroxide-based hardening accelerators.
7. The halogen-free resin composition with low expansion coefficient of claim 6, wherein the hardening accelerator comprises: 1 part by weight of a metal-based curing accelerator, 1 part by weight of 2-ethyl-4-methylimidazole, and 1 part by weight of a peroxide-based curing accelerator.
8. The low expansion coefficient halogen-free resin composition of claim 1, wherein the low expansion coefficient halogen-free resin composition further comprises: an inorganic filler selected from the group consisting of silica, alumina, aluminum hydroxide, magnesium oxide, magnesium hydroxide, calcium carbonate, aluminum nitride, boron nitride, aluminum silicon carbide, titanium dioxide, zinc oxide, zirconium oxide, barium sulfate, magnesium carbonate, barium carbonate, mica, talc, and graphene.
9. A laminate panel, comprising:
a resin substrate comprising a plurality of prepreg sheets, wherein each prepreg sheet is made of a glass fiber cloth coated with the halogen-free resin composition with low expansion coefficient according to claim 1; and
and the metal foil layer is arranged on at least one surface of the resin substrate.
10. A printed circuit board comprising the laminate of claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110060714.1A CN114806078B (en) | 2021-01-18 | 2021-01-18 | Low expansion coefficient halogen-free resin composition, laminated board and printed circuit board |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110060714.1A CN114806078B (en) | 2021-01-18 | 2021-01-18 | Low expansion coefficient halogen-free resin composition, laminated board and printed circuit board |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114806078A true CN114806078A (en) | 2022-07-29 |
| CN114806078B CN114806078B (en) | 2023-12-05 |
Family
ID=82523582
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110060714.1A Active CN114806078B (en) | 2021-01-18 | 2021-01-18 | Low expansion coefficient halogen-free resin composition, laminated board and printed circuit board |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114806078B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20190202168A1 (en) * | 2018-01-02 | 2019-07-04 | Iteq Corporation | Laminated substrate |
| CN110028758A (en) * | 2018-01-12 | 2019-07-19 | 联茂(无锡)电子科技有限公司 | Halogen-free epoxy resin composition, laminated plates and printed circuit board |
-
2021
- 2021-01-18 CN CN202110060714.1A patent/CN114806078B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20190202168A1 (en) * | 2018-01-02 | 2019-07-04 | Iteq Corporation | Laminated substrate |
| TW201930447A (en) * | 2018-01-02 | 2019-08-01 | 聯茂電子股份有限公司 | Halogen-free epoxy resin composition, laminated substrate and printed circuit board thereof |
| CN110028758A (en) * | 2018-01-12 | 2019-07-19 | 联茂(无锡)电子科技有限公司 | Halogen-free epoxy resin composition, laminated plates and printed circuit board |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114806078B (en) | 2023-12-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US9399712B2 (en) | Vinylbenzyl-etherified-DOPO compound resin composition and preparation and application thereof | |
| US9422412B2 (en) | Halogen-free resin composition and copper clad laminate and printed circuit board using same | |
| US9279051B2 (en) | Halogen-free resin composition, and copper clad laminate and printed circuit board using same | |
| JP6420479B2 (en) | Thermosetting resin composition, and prepreg and laminate produced using the same | |
| US9867287B2 (en) | Low dielectric resin composition with phosphorus-containing flame retardant and preparation method and application thereof | |
| TWI675063B (en) | Halogen-free epoxy resin composition, laminated substrate and printed circuit board thereof | |
| US8404764B1 (en) | Resin composition and prepreg, laminate and circuit board thereof | |
| CN110885428B (en) | Halogen-free thermosetting resin composition, prepreg using same, laminated board and printed circuit board | |
| CN111205595A (en) | Halogen-free low dielectric composition, laminate and printed wiring board | |
| CN109851997A (en) | A kind of compositions of thermosetting resin and prepreg, laminate and metal-clad laminate using it | |
| WO2021256351A1 (en) | Phosphorus-containing phenol compound, curable resin composition containing same, and cured object obtained therefrom | |
| CN108148178B (en) | Thermosetting resin composition | |
| CN114806167A (en) | Low-expansion-coefficient halogen-free resin composition, laminated plate and printed circuit board | |
| TWI669329B (en) | Halogen-free thermosetting resin composition and prepreg, laminate, metal foil-clad laminate, and printed circuit board using the same | |
| CN114573946B (en) | Halogen-free low dielectric epoxy resin composition, laminated board and printed circuit board | |
| CN114806078B (en) | Low expansion coefficient halogen-free resin composition, laminated board and printed circuit board | |
| TWI765504B (en) | LOW EXPANSION COEFFICIENT, LOW Df, HIGH RIGIDITY, HALOGEN-FREE RESIN COMPOSITION, LAMINATES AND PRINTED CIRCUIT BOARDS | |
| TWI779446B (en) | LOW EXPANSION COEFFICIENT, LOW Df, HIGH RIGIDITY, HALOGEN-FREE RESIN COMPOSITION, LAMINATES AND PRINTED CIRCUIT BOARDS | |
| JP2016153497A (en) | Epoxy resin composition, prepreg using the epoxy resin composition, resin film with supporter, metal foil-clad laminate sheet and multilayer printed board | |
| CN111138809B (en) | Halogen-free resin composition | |
| TWI724806B (en) | Halogen-free low-dielectric composition, laminated substrate and printed circuit board therof | |
| TWI740729B (en) | Halogen-free low-dielectric epoxy resin composition, laminated board and printed circuit board | |
| JP2002363259A (en) | Flame-retardant resin composition | |
| JP2012111828A (en) | High-heat-resistant epoxy resin composition, prepreg, metal-clad laminate, and printed wiring board | |
| TW202313647A (en) | Halogen-free low-dielectric composition, laminated substrate and printed circuit board therof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |