CN115716972A - Halogen-free low dielectric composition, laminate and printed wiring board - Google Patents
Halogen-free low dielectric composition, laminate and printed wiring board Download PDFInfo
- Publication number
- CN115716972A CN115716972A CN202211448827.XA CN202211448827A CN115716972A CN 115716972 A CN115716972 A CN 115716972A CN 202211448827 A CN202211448827 A CN 202211448827A CN 115716972 A CN115716972 A CN 115716972A
- Authority
- CN
- China
- Prior art keywords
- weight
- parts
- halogen
- epoxy resin
- resin
- 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.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 38
- 239000003822 epoxy resin Substances 0.000 claims abstract description 79
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 79
- 229920005989 resin Polymers 0.000 claims abstract description 33
- 239000011347 resin Substances 0.000 claims abstract description 33
- 239000003063 flame retardant Substances 0.000 claims abstract description 30
- 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 23
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000004848 polyfunctional curative Substances 0.000 claims abstract description 17
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims abstract description 7
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 42
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 15
- 229920003986 novolac Polymers 0.000 claims description 14
- -1 phosphate ester Chemical class 0.000 claims description 14
- 239000000758 substrate 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 12
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 12
- 239000011888 foil Substances 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000654 additive Substances 0.000 claims description 10
- 230000000996 additive effect Effects 0.000 claims description 10
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 10
- 239000004744 fabric Substances 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 239000012745 toughening agent Substances 0.000 claims description 8
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-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
- 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
- 239000004305 biphenyl Substances 0.000 claims description 6
- 235000010290 biphenyl Nutrition 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000000454 talc Substances 0.000 claims description 6
- 229910052623 talc Inorganic materials 0.000 claims description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 6
- 229920000388 Polyphosphate Polymers 0.000 claims description 5
- 150000004984 aromatic diamines Chemical group 0.000 claims description 5
- 239000001205 polyphosphate Substances 0.000 claims description 5
- 235000011176 polyphosphates Nutrition 0.000 claims description 5
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 125000003700 epoxy group Chemical group 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 150000002989 phenols Chemical class 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 3
- CQOZJDNCADWEKH-UHFFFAOYSA-N 2-[3,3-bis(2-hydroxyphenyl)propyl]phenol Chemical compound OC1=CC=CC=C1CCC(C=1C(=CC=CC=1)O)C1=CC=CC=C1O CQOZJDNCADWEKH-UHFFFAOYSA-N 0.000 claims description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 claims description 3
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims description 3
- 229910015900 BF3 Inorganic materials 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
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000005062 Polybutadiene Substances 0.000 claims description 3
- 125000002723 alicyclic group Chemical group 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
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 claims description 3
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Substances FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 3
- JAWGVVJVYSANRY-UHFFFAOYSA-N cobalt(3+) Chemical compound [Co+3] JAWGVVJVYSANRY-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 3
- 239000011258 core-shell material Substances 0.000 claims description 3
- 229930003836 cresol Natural products 0.000 claims description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 239000011256 inorganic filler Substances 0.000 claims description 3
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 3
- 239000007788 liquid Substances 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
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- 229920002857 polybutadiene Polymers 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- 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 claims description 2
- 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
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 claims description 2
- 235000021286 stilbenes Nutrition 0.000 claims description 2
- 125000006839 xylylene group Chemical group 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims 1
- 230000009477 glass transition Effects 0.000 abstract description 6
- 125000006157 aromatic diamine group Chemical group 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 14
- 239000011889 copper foil Substances 0.000 description 11
- 239000003365 glass fiber Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229930185605 Bisphenol Natural products 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000011342 resin composition Substances 0.000 description 6
- 238000004513 sizing Methods 0.000 description 6
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 5
- 239000005011 phenolic resin Substances 0.000 description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 238000002485 combustion reaction Methods 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
- 238000004519 manufacturing process Methods 0.000 description 4
- PZBFGYYEXUXCOF-UHFFFAOYSA-N TCEP Chemical compound OC(=O)CCP(CCC(O)=O)CCC(O)=O PZBFGYYEXUXCOF-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000010411 cooking Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 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 description 2
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 2
- 239000004114 Ammonium polyphosphate Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 208000037427 Beta-propeller protein-associated neurodegeneration Diseases 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- 229920009204 Methacrylate-butadiene-styrene Polymers 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 2
- 229920001276 ammonium polyphosphate Polymers 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Natural products O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 201000007614 neurodegeneration with brain iron accumulation 5 Diseases 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 2
- 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
- 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
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- 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 1
- ZRYCRPNCXLQHPN-UHFFFAOYSA-N 3-hydroxy-2-methylbenzaldehyde Chemical compound CC1=C(O)C=CC=C1C=O ZRYCRPNCXLQHPN-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004609 Impact Modifier Substances 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000005130 benzoxazines Chemical class 0.000 description 1
- 230000009172 bursting Effects 0.000 description 1
- WWNGFHNQODFIEX-UHFFFAOYSA-N buta-1,3-diene;methyl 2-methylprop-2-enoate;styrene Chemical compound C=CC=C.COC(=O)C(C)=C.C=CC1=CC=CC=C1 WWNGFHNQODFIEX-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 description 1
- 239000001177 diphosphate Substances 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- ULYZAYCEDJDHCC-UHFFFAOYSA-N isopropyl chloride Chemical compound CC(C)Cl ULYZAYCEDJDHCC-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Abstract
The invention discloses a halogen-free low dielectric composition, a laminated board and a printed circuit board, wherein the halogen-free low dielectric composition comprises: 100 parts by weight of an epoxy resin; (b) A hardener comprising 15 to 25 parts by weight of a flame retardant hardener and 70 to 100 parts by weight of a benzoxazine resin, wherein the benzoxazine resin has an aromatic diamine functional group; (c) 80 to 120 parts by weight of a halogen-free flame retardant; and (d) 80 to 120 parts by weight of an accelerator. The halogen-free low dielectric composition of the present invention can provide a halogen-free epoxy resin composition with specific components and proportions, and has excellent dielectric properties, high glass transition temperature, low thermal expansion coefficient, high heat resistance, good flame retardancy and excellent processability for printed circuit boards.
Description
Technical Field
The present invention relates to a low dielectric composition, a laminate and a printed circuit board, and more particularly to a halogen-free low dielectric composition, a laminate and a printed circuit board.
Background
Printed Circuit Boards (PCBs) are almost an indispensable basic part of all electronic products, such as: information, communication, consumer electronics, automotive, aerospace, military, industrial products, precision instruments, and the like, and the application fields of printed circuit boards are quite extensive.
As the development of electronic product functions becomes more complex, the performance requirements of the printed circuit board become higher and higher. In the printed circuit board technology, the prepared thermosetting resin composition and the reinforcing material are formed into a prepreg in a semi-cured state, and then laminated with the metal foil to form a metal foil laminated board. In order to realize more functions, the number of layers required for the printed circuit board is increased, so that a substrate having a low expansion coefficient and higher heat resistance is urgently needed in the field, and the circuit density of the printed circuit board is also increased, so that a substrate having good machinability is a major development point in the field.
On the other hand, in the prior art, a brominated flame retardant is often added to a resin composition in a printed circuit board to improve the flame retardant effect thereof, so that the flame retardant effect of the printed circuit board reaches the UL94V0 level, and common flame retardants are, for example: tetrabromobisphenol A, tetrabromocyclohexane, hexabromocyclodecane and 2,4, 6-tri (tribromophenoxy) -1,3, 5-triazabenzene, etc., the addition of the flame retardant containing halogen components can prevent the circuit from causing fire due to short circuit, the flame retardant containing halogen components has the advantages of high flame retardant efficiency, small dosage, relatively low cost, etc., however, the flame retardant containing halogen components can release corrosive toxic gases such as hydrogen halide under the conditions of high temperature and open fire, and therefore, the flame retardant containing halogen components can generate great harm to human bodies and natural environment. Under the background of environmental protection and ecological safety, the development of halogen-free printed circuit boards has been accelerated in the art.
Disclosure of Invention
How to improve the defects of the prior art and develop a material with excellent dielectric properties and meeting the requirements of other characteristics of printed circuit boards, such as high glass transition temperature (Tg), low thermal expansion coefficient, high heat resistance and good flame retardancy, and apply the material to the manufacture of high frequency printed circuit boards is a problem that printed circuit board material suppliers are in urgent need of solution at present.
Accordingly, the present invention is directed to a halogen-free low dielectric constant composition, a laminate and a printed circuit board.
The main object of the present invention is to provide a halogen-free low dielectric composition comprising: 100 parts by weight of an epoxy resin; (b) A hardener, which comprises 15 to 25 weight parts of flame retardant hardener and 70 to 100 weight parts of benzoxazine resin, wherein the benzoxazine resin has aromatic diamine functional group; (c) 80 to 120 parts by weight of a halogen-free flame retardant; and (d) 80 to 120 parts by weight of an accelerator.
In a preferred embodiment, the epoxy resin is at least one selected from the group consisting of bisphenol a type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol a novolac type epoxy resins, bisphenol F novolac type epoxy resins, stilbene type epoxy resins, epoxy resins containing a triazine skeleton, epoxy resins containing a fluorene skeleton, triphenol methane type epoxy resins, biphenyl type epoxy resins, xylylene type epoxy resins, biphenyl aralkyl type epoxy resins, naphthalene type epoxy resins, dicyclopentadiene type epoxy resins, alicyclic epoxy resins, diglycidyl ether compounds of polyfunctional phenols and condensed ring aromatics, trifunctional and tetrafunctional epoxy resins having 3 or 4 epoxy groups in the molecule, and phosphorus-containing epoxy resins.
In a preferred embodiment, the flame retardant hardener is at least one selected from the group consisting of DOPO-hydroquinone resin, DOPO-naphthalene diol resin, DOPO-novolac resin, DOPO-bisphenol phenol resin, phenoxyphosphazene compound, phosphate ester, polyphosphate ester, and phosphonate ester and polyphosphonate ester.
In a preferred embodiment, the benzoxazine resin comprises 70 to 85 parts by weight of ODA type benzoxazine and 5 to 15 parts by weight of MDA type benzoxazine.
In a preferred embodiment, the accelerator is selected from the group consisting of boron trifluoride amine complex, 2-ethyl-4-methylimidazole, 2-phenylimidazole, ethyltriphenylphosphonium chloride, triphenylphosphine, cobalt (II) acetylacetonate, 4-dimethylaminopyridine, bromine-terminated liquid butadiene rubber, cobalt (II) bisacetylacetonate, cobalt (III) trisacetylacetonate, triethylamine, tributylamine, and diazabicyclo [2, 2] octane.
In a preferred embodiment, the halogen-free low dielectric composition further comprises an additive, wherein the additive is 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 a preferred embodiment, the halogen-free low dielectric composition further comprises an additive, wherein the additive is a toughening agent, and the toughening agent is a core-shell polymer with a volume average particle size of 0.01 to 1 μm.
In a preferred embodiment, the halogen-free low dielectric constant composition further comprises a solvent, and the solvent is selected from the group consisting of acetone, methyl ethyl ketone, propylene glycol methyl ether acetate, dimethylacetamide and cyclohexanone.
Another object of the present invention is to provide a laminate comprising: a resin substrate, which comprises a plurality of semi-solidified films, wherein each semi-solidified film is made of glass fiber cloth coated with the halogen-free low-dielectric composition; and a metal foil layer disposed on at least one surface of the resin substrate.
Another object of the present invention is to provide a printed circuit board, which includes the above-mentioned laminate.
Therefore, the halogen-free low dielectric composition provided by the invention can provide a halogen-free epoxy resin composition by virtue of specific components and proportions, has excellent dielectric properties, high glass transition temperature, low thermal expansion coefficient, high heat resistance, good flame retardance and excellent PCB processability, and can be applied to the manufacture of printed circuit boards.
The invention is described in detail below with reference to the drawings and specific examples, but the invention is not limited thereto.
Drawings
FIG. 1 is an infrared spectrum of a preferred embodiment of the present invention.
Detailed Description
The invention will be described in detail with reference to the following drawings, which are provided for illustration purposes and the like:
unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. As used in this application, the following terms have the following meanings.
As used herein, terms such as "first," "second," "third," "fourth," and "fifth," describe various elements, components, regions, layers and/or sections, which should not be limited by these terms. These terms may be only used to distinguish one element, component, region, layer or section from another. Terms such as "first," "second," "third," "fourth," and "fifth" used herein do not imply a sequence or order unless clearly indicated by the context.
Unless otherwise stated, the term "or" as used herein means "and/or". The term "comprising" or "comprises" as used herein is intended to mean that it does not exclude the presence or addition of one or more other elements, steps, operations and/or elements; similarly, the terms "comprising," "including," "containing," "including," and "having" are used interchangeably and are not intended to be limiting. "A" means that the grammatical object of the object is one or more than one (i.e., at least one). The singular forms "a", "an", "the" and "the" include plural referents as described herein and in the claims.
The present invention is a halogen-free low dielectric composition comprising: 100 parts by weight of an epoxy resin; (b) A hardener comprising 15 to 25 parts by weight of a flame retardant hardener and 70 to 100 parts by weight of a benzoxazine resin, wherein the benzoxazine resin has an aromatic diamine functional group; (c) 80 to 120 parts by weight of a halogen-free flame retardant; and (d) 80 to 120 parts by weight of an accelerator. The above ratio ranges are based on 100 parts by weight of the epoxy resin.
The "epoxy resins" described herein, for example: at least one selected from the group consisting of bisphenol a-type epoxy resins, bisphenol F-type epoxy resins, bisphenol S-type epoxy resins, phenol novolac-type epoxy resins, cresol novolac-type epoxy resins, bisphenol a novolac-type epoxy resins, bisphenol F novolac-type epoxy resins, stilbene-type epoxy resins, triazine skeleton-containing epoxy resins, fluorene skeleton-containing epoxy resins, triphenol methane-type epoxy resins, biphenyl-type epoxy resins, xylylene-type epoxy resins, biphenyl aralkyl-type epoxy resins, naphthalene-type epoxy resins, dicyclopentadiene-type epoxy resins, alicyclic epoxy resins, diglycidyl ether compounds of polyfunctional phenols and condensed ring aromatics, trifunctional and tetrafunctional epoxy resins having 3 or 4 epoxy groups in the molecule, and phosphorus-containing epoxy resins. In a preferred embodiment, the epoxy resin is a cresol-formaldehyde novolac resin (also referred to herein as CNE epoxy). The epoxy resins herein can raise the glass transition temperature to about 200 ℃.
The "hardener" described herein includes a flame retardant hardener and a benzoxazine resin having an aromatic diamine functional group. In a preferred embodiment, the hardener comprises 15 to 25 parts by weight of a flame retardant hardener such as, but not limited to, a flame retardant hardener such as, but not limited to: 15 parts by weight, 16 parts by weight, 17 parts by weight, 18 parts by weight, 19 parts by weight, 20 parts by weight, 21 parts by weight, 22 parts by weight, 23 parts by weight, 24 parts by weight, 25 parts by weight, or between any two of the foregoing, such as, but not limited to: 70 parts by weight, 75 parts by weight, 80 parts by weight, 85 parts by weight, 90 parts by weight, 95 parts by weight, 100 parts by weight, or a value between any two of the foregoing.
The flame retardant hardener, for example: at least one selected from the group consisting of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) -hydroquinone resin, DOPO-naphthalenediol resin, DOPO-novolac resin, DOPO-bisphenol-novolac resin, phenoxyphosphazene compound, phosphate ester, polyphosphate ester, and phosphonate ester and polyphosphonate ester. In a preferred embodiment, the flame retardant hardening agent can be DOPO compound, DOPO-containing phenolic resin (such as DOPO-HQ, DOPO-PN, DOPO-BPN), DOPO-containing epoxy resin, DOPO-HQ-containing epoxy resin, etc., wherein the DOPO-BPN can be DOPO-BPAN, DOPO-BPFN, DOPO-BPSN, etc. bisphenol phenolic compound. In a preferred embodiment, the flame retardant hardener is bisphenol A phenolic resin containing DOPO functional groups (DOPO-bisphenol A novolac, DOPO-BPAN). The flame-retardant hardening agent is used, so that the effects of flame retardance and hardening can be achieved at the same time.
The "benzoxazine resin" as referred to herein is a thermosetting resin containing nitrogen and having a structure similar to a phenol resin, and the benzoxazine compound is a six-membered heterocyclic compound system composed of an oxygen atom and a nitrogen atom, and is generally a compound prepared by a Mannich (Mannich) reaction of a phenolic compound, a primary amine and a formaldehyde compound, which is subjected to ring-opening polymerization under the action of heat or a catalyst to form a network structure similar to a phenol resin. In a preferred embodiment, the polybenzoxazine compound is a diamine type polybenzoxazine. In a preferred embodiment, the benzoxazine resin comprises 70 to 85 parts by weight of oxydianiline type benzoxazine (ODA type benzoxazine, herein abbreviated as ODA-Bz) and 5 to 15 parts by weight of 4,4 '-diaminodiphenylmethane type benzoxazine (4, 4' -methylenedianiline type benzoxazine, herein abbreviated as MDA-Bz) based on 100 parts by weight of the epoxy resin; the ODA-Bz is exemplified by, but not limited to: 70 parts by weight, 71 parts by weight, 72 parts by weight, 73 parts by weight, 74 parts by weight, 75 parts by weight, 76 parts by weight, 77 parts by weight, 78 parts by weight, 79 parts by weight, 80 parts by weight, 81 parts by weight, 82 parts by weight, 83 parts by weight, 84 parts by weight, 85 parts by weight, or a value between any two of the foregoing; such MDA-Bz is exemplified by, but not limited to: 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight, or any number therebetween. The benzoxazine resin with aromatic diamine functional group is used, has Amine functional group, is easy to react with isocyanate and epoxy group, and can improve heat resistance and reduce dielectric constant (Dk)/dielectric loss (Df).
Halogen-free flame retardants as described herein, for example: may be selected from the group consisting of resorcinol dixylylphosphates (RDXP (e.g., PX-200)), melamine polyphosphate (melamine polyphosphate), tris (2-carboxyethyl) phosphine (tri (2-carboxyethyl) phosphine, TCEP), trimethylphosphate (TMP), tris (isopropylchloride) phosphate, dimethyl-methylphosphate (DMMP), bisphenol diphenyl phosphate (biphenol diphosphate), ammonium polyphosphate (ammonium polyphosphate), hydroquinone-bis- (biphenylphosphate) (hydroquinone bis- (biphenyl phosphate)), bisphenol a-bis- (biphenylphosphate) (biphenol a bis- (biphenyl phosphate)), and Phosphazene compounds (phosphazenes). In a preferred embodiment, the halogen-free flame retardant is a phosphazene flame retardant (e.g., SPB-100), which is an environmentally friendly flame retardant having excellent heat resistance and moisture absorption resistance and suitable for use in the field of electronic materials. In a preferred embodiment, the halogen-free flame retardant comprises 80 to 120 parts by weight, based on 100 parts by weight of the epoxy resin, such as but not limited to: 80 parts by weight, 85 parts by weight, 90 parts by weight, 95 parts by weight, 100 parts by weight, 105 parts by weight, 110 parts by weight, 115 parts by weight, 120 parts by weight, or any two or more of the foregoing values.
An "accelerator" as described herein is an additive that can accelerate performance. In a preferred embodiment, the accelerator is a hardening accelerator. In a preferred embodiment, the accelerator is selected from the group consisting of boron trifluoride amine complex, 2-ethyl-4-methylimidazole (2E 4 MI), 2-methylimidazole, 2-phenylimidazole, ethyltriphenylphosphonium chloride, triphenylphosphine, cobalt (II) acetylacetonate, 4-dimethylaminopyridine, bromine-terminated liquid butadiene rubber, cobalt (II) bisacetylacetonate, cobalt (III) trisacetylacetonate, triethylamine, tributylamine, and diazabicyclo [2, 2] octane. In a preferred embodiment, the accelerator is, for example but not limited to, based on 100 parts by weight of the epoxy resin: 80 parts by weight, 85 parts by weight, 90 parts by weight, 95 parts by weight, 100 parts by weight, 105 parts by weight, 110 parts by weight, 115 parts by weight, 120 parts by weight, or any two of the foregoing values.
In a preferred embodiment, the halogen-free low dielectric composition further comprises: an additive, the additive being 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, zirconia, barium sulfate, magnesium carbonate, barium carbonate, mica, talc, and graphene. In a preferred embodiment, the addition of silicon dioxide improves thermal conductivity, mechanical strength and reduces thermal expansion. In another preferred embodiment, talc is added to reduce drill wear.
In a preferred embodiment, the halogen-free low dielectric composition further comprises: an additive which is a toughening agent which is a core shell polymer having a volume average particle size of 0.01 to 1 μm, such as but not limited to: 0.01 μm, 0.05 μm, 0.10 μm, 0.20 μm, 0.30 μm, 0.40 μm, 0.50 μm, 0.60 μm, 0.70 μm, 0.80 μm, 0.90 μm, 1.0 μm or a value between any two of the foregoing. In a preferred embodiment, the addition of the toughening agent can improve the heat resistance and toughness of the material.
In a preferred embodiment, the halogen-free low dielectric composition further comprises, based on 100 parts by weight of the epoxy resin: 75 to 85 parts by weight of silica; 10 to 20 parts by weight of talc; and 0.5 to 1.5 parts by weight of a toughening agent; such as, but not limited to: 75 parts by weight, 76 parts by weight, 77 parts by weight, 78 parts by weight, 79 parts by weight, 80 parts by weight, 81 parts by weight, 82 parts by weight, 83 parts by weight, 84 parts by weight, 85 parts by weight, or a value between any two of the foregoing; such talc is exemplified by, but not limited to: 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight, 16 parts by weight, 17 parts by weight, 18 parts by weight, 19 parts by weight, 20 parts by weight or a value between any two of the foregoing values; such as, but not limited to: 0.5 parts by weight, 0.6 parts by weight, 0.7 parts by weight, 0.8 parts by weight, 0.9 parts by weight, 1.0 parts by weight, 1.1 parts by weight, 1.2 parts by weight, 1.3 parts by weight, 1.4 parts by weight, 1.5 parts by weight, or any two of the foregoing.
In a preferred embodiment, the halogen-free low dielectric composition further comprises: a solvent selected from the group consisting of acetone, butanone, propylene glycol methyl ether acetate, dimethylacetamide, and cyclohexanone. In a preferred embodiment, the halogen-free low dielectric composition further comprises: 20 to 30 parts by weight of Propylene glycol methyl ether (PM); 45 to 55 parts by weight of Cyclohexanone (Cyclohexanone); and 20 to 30 parts by weight of Methyl Ethyl Ketone (MEK); such propylene glycol methyl ethers are exemplified by, but not limited to: 20 parts by weight, 21 parts by weight, 22 parts by weight, 23 parts by weight, 24 parts by weight, 25 parts by weight, 26 parts by weight, 27 parts by weight, 28 parts by weight, 29 parts by weight, 30 parts by weight, or a value between any two of the foregoing; such cyclohexanone is exemplified by, but not limited to: 45 parts by weight, 46 parts by weight, 47 parts by weight, 48 parts by weight, 49 parts by weight, 50 parts by weight, 51 parts by weight, 52 parts by weight, 53 parts by weight, 54 parts by weight, 55 parts by weight, or a value between any two of the foregoing; such butanone is exemplified by, but not limited to: 20 parts by weight, 21 parts by weight, 22 parts by weight, 23 parts by weight, 24 parts by weight, 25 parts by weight, 26 parts by weight, 27 parts by weight, 28 parts by weight, 29 parts by weight, 30 parts by weight, or any number therebetween.
The invention also provides a laminated board and a printed circuit board. The laminate comprises: a resin substrate, which comprises a plurality of semi-solidified films, wherein each semi-solidified film is made of glass fiber cloth coated with the halogen-free low-dielectric composition; and a metal foil layer disposed on at least one surface of the resin substrate. The printed circuit board comprises a laminate as described above.
Examples
Hereinafter, the present invention will be further described in the detailed description and the embodiments, however, it should be understood that these embodiments are only for helping the easier understanding of the present invention and to clarify aspects of the present invention and the benefits achieved thereby, and not to limit the scope of the present invention.
6 halogen-free low dielectric compositions (examples 1 to 6) were prepared according to the invention followed by the preparation of metal foil laminates using examples 1 to 6. The method for manufacturing a metal foil laminate plate comprises: (a) preparing a resin composition; (c) preparing a prepreg: impregnating or coating a substrate with the resin composition, and drying the substrate to obtain a prepreg (or semi-cured film) in a semi-cured state; and (c) preparing a metal foil laminate: laminating a plurality of the prepregs, laminating a metal foil on the outermost layers of both sides of the prepregs, and then hot-pressing and curing at a high temperature to obtain the metal foil laminated plate.
Specifically, the components and the ratio of the halogen-free low dielectric composition are shown in table 1 below. Then, the semi-cured films prepared in the embodiments 1 to 6 are manufactured in a continuous process, usually by using glass fiber cloth as a substrate, the rolled glass fiber cloth continuously passes through a series of rollers and enters a sizing tank, the tank is filled with the halogen-free low dielectric composition of the present invention, the glass fiber cloth is fully soaked by resin in the sizing tank, then excess resin is scraped off by a metering roller, the mixture enters a sizing furnace and is baked for a certain time, so that the solvent is evaporated and the resin is cured to a certain degree, and the semi-cured films are formed after cooling and rolling. And finally, taking four and two 18-micron copper foils of the semi-cured films in the same batch, laminating the semi-cured films according to the sequence of the copper foils, the four semi-cured films and the copper foils, and pressing the semi-cured films at 220 ℃ for 2 hours under a vacuum condition to form a copper foil laminated plate, wherein the four semi-cured films are cured to form an insulating layer between the two copper foils.
TABLE 1
* The toughening agent is MBS sold by Arkema
Based on methyl methacrylate-butadiene-styrene (MBS) core-cylindrical shell impact modifier (particulate size range: 150-200 nm); the units in the table are parts by weight (based on 100 parts by weight of the epoxy resin).
According to a method similar to that disclosed in examples, three comparative example resin compositions (comparative examples 1 to 3) were prepared, and then metal foil laminate plates were prepared using comparative examples 1 to 3. However, the specific methods of making the examples and comparative examples will generally differ in one or more respects.
Specifically, the components and the proportions of the resin compositions of comparative examples 1 to 3 were as shown in Table 2 below. Then, the semi-cured films of comparative examples 1 to 3 were manufactured in a continuous process, generally using glass fiber cloth as a substrate, the rolled glass fiber cloth continuously passed through a series of rollers into a sizing tank, in which comparative examples 1 to 3 were installed, the glass fiber cloth was sufficiently soaked by resin in the sizing tank, then excess resin was scraped off by a metering roller, and the glass fiber cloth was put into a sizing oven to be baked for a certain period of time to evaporate the solvent and solidify the resin to a certain degree, cooled, and wound up to form the semi-cured films. And finally, taking four and two 18-micron copper foils of the semi-cured films in the same batch, laminating the semi-cured films according to the sequence of the copper foils, the four semi-cured films and the copper foils, and pressing the semi-cured films at 220 ℃ for 2 hours under a vacuum condition to form a copper foil laminated plate, wherein the four semi-cured films are cured to form an insulating layer between the two copper foils.
TABLE 2
* PMA is Propylene glycol methyl ether acetate (Propylene glycol methyl ether acetate); NC-3000 is biphenyl type epoxy resin; the LZ8280 is bisphenol F benzoxazine; the units in the table are parts by weight (based on 100 parts by weight of the epoxy resin).
Characteristic test
Physical properties of the copper clad laminates prepared in examples 1 to 6 and comparative examples 1 to 3 were measured, and the results are recorded in tables 3 and 4.
TABLE 3
TABLE 4
(1) Glass transition temperature (Tg): the measurement was carried out by Differential Scanning Calorimetry (DSC) according to the DSC method defined by IPC-TM-6502.4.25.
(2) Heat resistance (PCT) test of copper foil laminate: the non-copper substrate PCT was subjected to wicking test, and after cooking in a 105KPa pressure cooker at 121 ℃ for 1 hour, the resultant was immersed in a 288 ℃ tin furnace (solderdip), and the presence or absence of delamination of the bursting sheet was observed for 20 seconds.
(3) Water absorption: is the ratio of the weight difference before and after 1 hour of PCT cooking to the weight of the sample before PCT.
(4) Dielectric constant (Dk): the dielectric constant represents the electronic insulation characteristic of the prepared film, and the lower the numerical value, the better the electronic insulation characteristic.
(5) Dielectric loss (Df): the dielectric loss is measured according to IPC-TM-6502.5.5 detection specifications, and represents the capacity 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 is, the better the dielectric loss value is.
(6) Flammability/flame resistance (flaming test, UL 94): according to UL94 vertical burning method, the flame-resistant grade of the plastic material is determined by the spontaneous combustion time, spontaneous combustion speed and falling particle state of the plastic material standard test piece after flame combustion. And HB, V-2, V-1 and V-0 are sequentially arranged according to the grade of flame resistance, and the highest grade is 5V. The UL94 test method refers to the burning of plastic materials 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 then removing the test piece, and measuring the continuous burning time (T1) of the test piece after the removal of the test piece; step two: when the flame of the test piece is extinguished, putting the test piece into the flame for ten seconds, then removing the test piece, and measuring the continuous burning time (T2) of the test piece after the removal; step three: repeating the experiment for a plurality of times and taking the average value; step four: the sum of T1+ T2 is calculated. The UL 94V-0 rating is required to satisfy the UL 94V-0 requirement in that both the average of T1 and the average of T2 in the test piece combustion time T1 should not exceed 10 seconds, and the sum of T1 and T2 should not exceed 50 seconds.
(7) Thermal stratification time (T288): also called "" tin floating result "", this experiment is based on the industry standard IPC-TM-6502.4.24.1, the time required to soak the laminate in a tin furnace at 288 ℃ until the laminate explodes.
(8) Heat resistance: no copper substrate PCT immersion tin test after moisture absorption (pressure cooking at 121 ℃,1 hour later, the temperature of the solder dip 288 ℃,20 seconds to see the existence of the explosion plate, PCT).
FIG. 1 is an infrared spectrum of a preferred embodiment of the present invention.
In summary, the halogen-free low dielectric composition provided by the present invention can provide a halogen-free epoxy resin composition with specific components and ratios, and has excellent dielectric properties, high glass transition temperature, low thermal expansion coefficient, high heat resistance, good flame retardancy and excellent PCB processability, and can be applied to the manufacture of printed circuit boards.
As used herein and not otherwise defined, the terms "substantially" and "about" are used in a descriptive sense and to describe minor variations. When coupled to an event or circumstance, the terminology may include the precise moment the event or circumstance occurs, and the approximation that the event or circumstance occurs to a close approximation. For example, when combined with a numerical value, the term can encompass a range of variation that is less than or equal to ± 10% of the numerical value, such as less than or equal to ± 5%, less than or equal to ± 4%, less than or equal to ± 3%, less than or equal to ± 2%, less than or equal to ± 1%, less than or equal to ± 0.5%, less than or equal to ± 0.1%, or less than or equal to ± 0.05%.
As used herein and not otherwise defined, the terms "substantially" and "approximately" are used for descriptive purposes and descriptive purposes to provide a minimum of variation. When coupled to an event or circumstance, the terminology may include the precise moment the event or circumstance occurs, and the approximation that the event or circumstance occurs to a close approximation. For example, when combined with a numerical value, the term can encompass a range of variation that is less than or equal to ± 10% of the numerical value, such as less than or equal to ± 5%, less than or equal to ± 4%, less than or equal to ± 3%, less than or equal to ± 2%, less than or equal to ± 1%, less than or equal to ± 0.5%, less than or equal to ± 0.1%, or less than or equal to ± 0.05%.
The present invention is capable of other embodiments, and various changes and modifications can be made by one skilled in the art without departing from the spirit and scope of the invention.
Claims (10)
1. A halogen-free low dielectric composition comprising:
(a) 100 parts by weight of an epoxy resin;
(b) A hardener, which comprises 15 to 25 weight parts of flame retardant hardener and 70 to 100 weight parts of benzoxazine resin, wherein the benzoxazine resin has aromatic diamine functional group;
(c) 80 to 120 parts by weight of a halogen-free flame retardant; and
(d) 80 to 120 parts by weight of an accelerator.
2. The halogen-free low dielectric composition of claim 1, wherein the epoxy resin is at least one selected from the group consisting of bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol a novolac type epoxy resin, bisphenol F novolac type epoxy resin, stilbene type epoxy resin, triazine skeleton-containing epoxy resin, fluorene skeleton-containing epoxy resin, triphenol methane type epoxy resin, biphenyl type epoxy resin, xylylene type epoxy resin, biphenyl aralkyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, alicyclic epoxy resin, diglycidyl ether compounds of polyfunctional phenols and condensed ring aromatics, trifunctional and tetrafunctional epoxy resins having 3 or 4 epoxy groups in a molecule, and phosphorous-containing epoxy resins.
3. The halogen-free low dielectric composition of claim 1 wherein the flame retardant hardener is at least one selected from the group consisting of DOPO-hydroquinone resin, DOPO-naphthalene diol resin, DOPO-novolac resin, DOPO-bisphenol phenol formaldehyde resin, phenoxyphosphazene compound, phosphate ester, polyphosphate ester, and phosphonate ester and polyphosphonate ester.
4. The halogen-free low dielectric composition of claim 1 wherein the benzoxazine resin comprises 70 to 85 parts by weight of ODA type benzoxazine and 5 to 15 parts by weight of MDA type benzoxazine.
5. The halogen-free low dielectric composition of claim 1 wherein the accelerator is selected from the group consisting of boron trifluoride amine complex, 2-ethyl-4-methylimidazole, 2-phenylimidazole, ethyltriphenylphosphonium chloride, triphenylphosphine, cobalt (II) acetylacetonate, 4-dimethylaminopyridine, bromine-terminated liquid butadiene rubber, cobalt (II) bisacetylacetonate, cobalt (iii) trisacetylacetonate, triethylamine, tributylamine, and diazabicyclo [2, 2] octane.
6. The halogen-free low dielectric composition of claim 1 further comprising an additive that is 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.
7. The halogen-free low dielectric composition of claim 1 further comprising an additive that is a toughening agent, the toughening agent being a core shell polymer having a volume average particle size of 0.01 to 1 μm.
8. The halogen-free low dielectric composition of claim 1 further comprising a solvent selected from the group consisting of acetone, butanone, propylene glycol methyl ether acetate, dimethylacetamide, and cyclohexanone.
9. A laminate panel, comprising:
a resin substrate comprising a plurality of prepreg sheets, each of the prepreg sheets being made of a glass cloth coated with the halogen-free low dielectric composition 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 |
|---|---|---|---|
| CN202211448827.XA CN115716972A (en) | 2022-11-18 | 2022-11-18 | Halogen-free low dielectric composition, laminate and printed wiring board |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211448827.XA CN115716972A (en) | 2022-11-18 | 2022-11-18 | Halogen-free low dielectric composition, laminate and printed wiring board |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115716972A true CN115716972A (en) | 2023-02-28 |
Family
ID=85255622
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211448827.XA Pending CN115716972A (en) | 2022-11-18 | 2022-11-18 | Halogen-free low dielectric composition, laminate and printed wiring board |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115716972A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103554437A (en) * | 2013-09-04 | 2014-02-05 | 东莞联茂电子科技有限公司 | Halogen-free epoxy resin composition for IC packaging |
| JP2017020011A (en) * | 2016-07-06 | 2017-01-26 | 台光電子材料（昆山）有限公司Ｅｌｉｔｅ Ｅｌｅｃｔｒｏｎｉｃ Ｍａｔｅｒｉａｌ （Ｋｕｎｓｈａｎ） Ｃｏ． Ｌｔｄ | Resin composition, copper-clad laminate and printed circuit sheet using the same |
| CN109233543A (en) * | 2017-05-03 | 2019-01-18 | 中山台光电子材料有限公司 | Resin combination and the article being made from it |
-
2022
- 2022-11-18 CN CN202211448827.XA patent/CN115716972A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103554437A (en) * | 2013-09-04 | 2014-02-05 | 东莞联茂电子科技有限公司 | Halogen-free epoxy resin composition for IC packaging |
| JP2017020011A (en) * | 2016-07-06 | 2017-01-26 | 台光電子材料（昆山）有限公司Ｅｌｉｔｅ Ｅｌｅｃｔｒｏｎｉｃ Ｍａｔｅｒｉａｌ （Ｋｕｎｓｈａｎ） Ｃｏ． Ｌｔｄ | Resin composition, copper-clad laminate and printed circuit sheet using the same |
| CN109233543A (en) * | 2017-05-03 | 2019-01-18 | 中山台光电子材料有限公司 | Resin combination and the article being made from it |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US9288904B2 (en) | Halogen-free resin composition, copper clad laminate using the same, and printed circuit board using the same | |
| US9650512B2 (en) | Halogen-free resin composition, copper clad laminate using the same, and printed circuit board using the same | |
| US9005761B2 (en) | Halogen-free resin composition and its application for copper clad laminate and printed circuit board | |
| KR101897426B1 (en) | Halogen-free resin composition and prepreg and laminated prepared therefrom | |
| 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 | |
| KR101915918B1 (en) | Thermosetting Resin Composition and Prepreg and Laminated board Prepared therefrom | |
| US9394438B2 (en) | Resin composition, copper-clad laminate and printed circuit board for use therewith | |
| US9187635B2 (en) | Halogen-free resin composition, copper clad laminate using the same, and printed circuit board using the same | |
| TWI428242B (en) | Flame retardant prepregs and laminates for printed circuit boards | |
| CN102369227B (en) | Phosphorus-containing phenol novolac resin, hardener comprising the same and epoxy resin composition | |
| US20140004324A1 (en) | Low dielectric resin composition, applicable copper-clad laminate and printed circuit board | |
| 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 | |
| TW201930447A (en) | Halogen-free epoxy resin composition, laminated substrate and printed circuit board thereof | |
| KR101915919B1 (en) | Thermosetting Resin Composition and Prepreg and Laminated board Prepared therefrom | |
| TW202212347A (en) | Phosphorus-containing phenol compound, curable resin composition containing same, and cured object obtained therefrom | |
| CN108148178B (en) | Thermosetting resin composition | |
| JP2017122077A (en) | Phosphazene compound containing cyano group, production method and application | |
| CN109608828B (en) | Thermosetting resin composition, and prepreg, laminated board and metal foil-clad laminated board using same | |
| US9185801B2 (en) | Halogen-free resin composition, copper clad laminate using the same, and printed circuit board using the same | |
| JP7387413B2 (en) | Epoxy resin composition, laminates and printed circuit boards using the same | |
| TWI669329B (en) | Halogen-free thermosetting resin composition and prepreg, laminate, metal foil-clad laminate, and printed circuit board using the same | |
| CN114149657B (en) | Epoxy resin composition with low dielectric loss and high CTI (comparative tracking index) and application thereof | |
| CN115716972A (en) | Halogen-free low dielectric composition, laminate and printed wiring board |
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 |