CN105419348B - A kind of resin combination and prepreg and laminate using it - Google Patents
A kind of resin combination and prepreg and laminate using it Download PDFInfo
- Publication number
- CN105419348B CN105419348B CN201510852434.9A CN201510852434A CN105419348B CN 105419348 B CN105419348 B CN 105419348B CN 201510852434 A CN201510852434 A CN 201510852434A CN 105419348 B CN105419348 B CN 105419348B
- Authority
- CN
- China
- Prior art keywords
- resin
- epoxy resin
- resin combination
- weight
- polyphenylene oxide
- 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.)
- Expired - Fee Related
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- 229920005989 resin Polymers 0.000 title claims abstract description 279
- 239000011347 resin Substances 0.000 title claims abstract description 279
- 239000003822 epoxy resin Substances 0.000 claims abstract description 195
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 195
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 166
- 229920006380 polyphenylene oxide Polymers 0.000 claims abstract description 166
- 230000004048 modification Effects 0.000 claims abstract description 97
- 238000012986 modification Methods 0.000 claims abstract description 97
- 229920000642 polymer Polymers 0.000 claims abstract description 72
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000000203 mixture Substances 0.000 claims description 71
- 239000007787 solid Substances 0.000 claims description 47
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 38
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 34
- 239000011889 copper foil Substances 0.000 claims description 34
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 28
- 239000003063 flame retardant Substances 0.000 claims description 23
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 239000004593 Epoxy Substances 0.000 claims description 17
- 229940106691 bisphenol a Drugs 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 17
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 17
- 150000001412 amines Chemical class 0.000 claims description 16
- 229920003986 novolac Polymers 0.000 claims description 16
- -1 cyclic crown ether Chemical class 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 14
- 239000002585 base Substances 0.000 claims description 13
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 239000004843 novolac epoxy resin Substances 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 10
- 239000000654 additive Substances 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 8
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 claims description 8
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 8
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical class C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 6
- 238000005470 impregnation Methods 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 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
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 5
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- 229920001971 elastomer Polymers 0.000 claims description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 239000012779 reinforcing material Substances 0.000 claims description 5
- 239000011342 resin composition Substances 0.000 claims description 5
- 150000003512 tertiary amines Chemical class 0.000 claims description 5
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 4
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 4
- 125000001118 alkylidene group Chemical group 0.000 claims description 4
- 239000010426 asphalt Substances 0.000 claims description 4
- 125000005605 benzo group Chemical group 0.000 claims description 4
- 239000004842 bisphenol F epoxy resin Substances 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- SQNZJJAZBFDUTD-UHFFFAOYSA-N durene Chemical compound CC1=CC(C)=C(C)C=C1C SQNZJJAZBFDUTD-UHFFFAOYSA-N 0.000 claims description 4
- 239000000806 elastomer Substances 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 150000002460 imidazoles Chemical group 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 claims description 4
- 229920000570 polyether Polymers 0.000 claims description 4
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- 150000003242 quaternary ammonium salts Chemical group 0.000 claims description 4
- 238000007711 solidification Methods 0.000 claims description 4
- 230000008023 solidification Effects 0.000 claims description 4
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 4
- 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
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 239000004305 biphenyl Substances 0.000 claims description 3
- 235000010290 biphenyl Nutrition 0.000 claims description 3
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 150000003222 pyridines Chemical class 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 229920001187 thermosetting polymer Polymers 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 2
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-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
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 229910015900 BF3 Inorganic materials 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229920000858 Cyclodextrin Polymers 0.000 claims description 2
- 239000002841 Lewis acid Substances 0.000 claims description 2
- 239000002879 Lewis base Substances 0.000 claims description 2
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 claims description 2
- AJSHDAOMUKXVDC-UHFFFAOYSA-N butan-1-amine;sulfuric acid Chemical compound CCCC[NH3+].OS([O-])(=O)=O AJSHDAOMUKXVDC-UHFFFAOYSA-N 0.000 claims description 2
- 229920006026 co-polymeric resin Polymers 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 239000002270 dispersing agent Substances 0.000 claims description 2
- JVZRCNQLWOELDU-UHFFFAOYSA-N gamma-Phenylpyridine Natural products C1=CC=CC=C1C1=CC=NC=C1 JVZRCNQLWOELDU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 150000007527 lewis bases Chemical class 0.000 claims description 2
- 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 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- DYFFAVRFJWYYQO-UHFFFAOYSA-N n-methyl-n-phenylaniline Chemical compound C=1C=CC=CC=1N(C)C1=CC=CC=C1 DYFFAVRFJWYYQO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- 239000005011 phenolic resin Substances 0.000 claims description 2
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 2
- 239000012745 toughening agent Substances 0.000 claims description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 2
- 230000017260 vegetative to reproductive phase transition of meristem Effects 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims 2
- 239000002253 acid Substances 0.000 claims 2
- 238000005660 chlorination reaction Methods 0.000 claims 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims 1
- RRTCFFFUTAGOSG-UHFFFAOYSA-N benzene;phenol Chemical compound C1=CC=CC=C1.OC1=CC=CC=C1 RRTCFFFUTAGOSG-UHFFFAOYSA-N 0.000 claims 1
- 150000005130 benzoxazines Chemical class 0.000 claims 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims 1
- 150000001983 dialkylethers Chemical class 0.000 claims 1
- 239000000945 filler Substances 0.000 claims 1
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims 1
- 150000001451 organic peroxides Chemical class 0.000 claims 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- 229910001950 potassium oxide Inorganic materials 0.000 claims 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 claims 1
- CEYYIKYYFSTQRU-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)C CEYYIKYYFSTQRU-UHFFFAOYSA-M 0.000 claims 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-O triphenylphosphanium Chemical compound C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-O 0.000 claims 1
- 239000004744 fabric Substances 0.000 abstract description 21
- 239000003365 glass fiber Substances 0.000 abstract description 18
- 238000002360 preparation method Methods 0.000 description 66
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 32
- 238000003825 pressing Methods 0.000 description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 31
- 239000002904 solvent Substances 0.000 description 28
- 238000006243 chemical reaction Methods 0.000 description 26
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 20
- 238000004519 manufacturing process Methods 0.000 description 17
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 17
- 239000000377 silicon dioxide Substances 0.000 description 15
- 238000007731 hot pressing Methods 0.000 description 14
- 238000011056 performance test Methods 0.000 description 14
- 239000000758 substrate Substances 0.000 description 14
- 125000003700 epoxy group Chemical group 0.000 description 9
- 230000035484 reaction time Effects 0.000 description 9
- 239000008096 xylene Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
- 230000008901 benefit Effects 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011256 inorganic filler Substances 0.000 description 4
- 229910003475 inorganic filler Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- OMIHGPLIXGGMJB-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]hepta-1,3,5-triene Chemical compound C1=CC=C2OC2=C1 OMIHGPLIXGGMJB-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 3
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 3
- 229920001955 polyphenylene ether Polymers 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 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 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 229910001593 boehmite Inorganic materials 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000006193 liquid solution Substances 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-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
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- FBSWPFFKBBRXJB-UHFFFAOYSA-N 3-(4-chlorophenyl)-1h-indole Chemical compound C1=CC(Cl)=CC=C1C1=CNC2=CC=CC=C12 FBSWPFFKBBRXJB-UHFFFAOYSA-N 0.000 description 1
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical compound C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 description 1
- 229960000549 4-dimethylaminophenol Drugs 0.000 description 1
- 229910017083 AlN Inorganic materials 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- IYZKEAIYJSVBRR-UHFFFAOYSA-N C(CCCCCCCCCCCCC)[N+](C)(C)C.[Cl+] Chemical compound C(CCCCCCCCCCCCC)[N+](C)(C)C.[Cl+] IYZKEAIYJSVBRR-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- YJLYANLCNIKXMG-UHFFFAOYSA-N N-Methyldioctylamine Chemical compound CCCCCCCCN(C)CCCCCCCC YJLYANLCNIKXMG-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004727 Noryl Substances 0.000 description 1
- 229920001207 Noryl Polymers 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- IKRMZAOEXULJQX-UHFFFAOYSA-N calcium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Ca+2].O1B([O-])OB2OB([O-])OB1O2 IKRMZAOEXULJQX-UHFFFAOYSA-N 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- NJXBVBPTDHBAID-UHFFFAOYSA-M ethyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 NJXBVBPTDHBAID-UHFFFAOYSA-M 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000002648 laminated material Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000009428 plumbing Methods 0.000 description 1
- 229940068918 polyethylene glycol 400 Drugs 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- 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
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- 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
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/098—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
-
- 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
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/02—Layered products essentially comprising sheet glass, or glass, slag, or like fibres in the form of fibres or filaments
- B32B17/04—Layered products essentially comprising sheet glass, or glass, slag, or like fibres in the form of fibres or filaments bonded with or embedded in a plastic substance
-
- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/04—Layered products comprising a layer of synthetic resin as impregnant, bonding, or embedding substance
-
- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
-
- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/42—Layered products comprising a layer of synthetic resin comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
-
- 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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions 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 C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L87/00—Compositions of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
Abstract
The present invention provides a kind of resin combination and use its prepreg and laminate.The resin combination includes the performed polymer and benzoxazine colophony of epoxy resin modification polyphenylene oxide resin.The present invention is by the way that the performed polymer of epoxy resin modification polyphenylene oxide resin to be used in the resin combination of printed circuit board, the dielectric properties of copper-clad plate can not only be improved, and the glass fiber cloth infiltrating of the resin combination of the performed polymer containing the epoxy resin modification polyphenylene oxide resin is improved, the resin combination made has excellent appearance, heat resistance, dielectric properties and peel strength.
Description
Technical field
The invention belongs to technical field of copper clad laminate, and in particular to a kind of resin combination and prepreg and layer using it
Pressing plate.
Background technique
Polyphenylene oxide resin have excellent water resistance, dimensional stability, flame retardant property and dielectric properties, and by with its
He mixes and obtains the more excellent resin combination of comprehensive performance.To be widely used in various fields as raw material,
For example, pipe accessories (plumbing fixtures), electrical appliance kit, automobile component and coated wire, copper-clad laminate and printing
Circuit etc..
Though the copper-clad laminate based on polyphenylene oxide resin can obtain outstanding dielectric properties, in prior art application, only
Simple physical blending is carried out into uniform glue varnish using polyphenylene oxide resin and other resin combinations, is impregnated in glass fibers
It ties up cloth surface and semi-solid preparation film is made, and then carry out the series of processes such as solidification pressing and copper foil laminated is made.Due to poly-
Phenylene ether resins polarity is lower, poor with the compatibility of other resins in resin combination, carries out influencing the apparent of prepreg；This
Outside, the impregnation of polyphenylene oxide resin and glass fabric is also undesirable, is easy to be gathered into film in glass cloth surface, this also can shadow
The apparent of prepreg is rung, and then is had an adverse effect to the dielectric properties of product.
The patent of Publication No. CN1556830 proposes a kind of method of functionalized polyphenylene ether, i.e., by polyphenylene oxide and bisphenol-A
Type epoxy resin reacts under the action of amines catalyst, obtains the polyphenyl that two end groups are respectively provided with two epoxy groups
Ether/epoxy resin prepolymer, this method improve the application problem of polyphenylene oxide mentioned above to a certain extent, but draw
The bisphenol A type epoxy resin entered, which but produces the dielectric properties of molecular resin, adversely affects-makes its Dk/Df to increase.
Summary of the invention
One of the objects of the present invention is to provide a kind of resin combinations, use epoxy resin modification polyphenylene oxide resin pre-
Aggressiveness and benzoxazine colophony cooperate, and make it have excellent appearance, (Tg that DSC method measures reaches the heat resistance of superelevation
To 180-210 DEG C) and excellent dielectric properties and peel strength.
To achieve the goals above, present invention employs following technical solutions：
A kind of resin combination, the resin combination include the performed polymer and Ben Bing Evil of epoxy resin modification polyphenylene oxide resin
Piperazine resin.
The present invention by the way that polyphenylene oxide resin is modified as the polyphenylene oxide epoxy prepolymer with group, then with benzoxazine
Resin complex reaction, the high heat resistance of low dielectric and benzoxazine colophony in combination with polyphenylene oxide resin, high Tg and fire-retardant
Advantage.Therefore, the resin combination containing epoxy-modified polyphenylene oxide resin performed polymer and benzoxazine is used for printed circuit
In the resin combination of plate, the dielectric properties of copper-clad plate can not only be improved, and improve and contain the epoxy resin modification polyphenylene oxide
The glass fiber cloth infiltrating of the resin combination of the performed polymer of resin, the resin combination made have excellent appearance table
Existing, heat resistance, dielectric properties and peel strength and high Tg.
Preferably, the performed polymer of the epoxy resin modification polyphenylene oxide resin has the structure as shown in formula (I)：
Wherein, X is：
Wherein, R is alkylidene, the singly-bound ,-SO of substituted or unsubstituted C1~C52,-O- ,-CO- ,-SO- or-SC-；
Y is the functional group of functional epoxy resin；
Z1、Z2、Z3、Z4It is identical or different, it independently is hydrogen atom, halogen atom, the alkyl (example below of carbon atom number 8
Such as C1, C2, C3, C4, C5, C6 or C7) or phenyl；
N is the positive integer greater than 1.It should be noted that n indicate high-molecular compound the degree of polymerization, it is above-mentioned various and under
Face enumerate it is various in, n takes identical or different value respectively.
Preferably, in formula (I), X is
Preferably, shown in the polyphenylene oxide resin molecular structure such as formula (II)：
Wherein, X is：
Wherein, R is alkylidene, the singly-bound ,-SO of substituted or unsubstituted C1~C52,-O- ,-CO- ,-SO- or-SC-；
Z1、Z2、Z3、Z4It is identical or different, it independently is hydrogen atom, halogen atom, the alkyl (example below of carbon atom number 8
Such as C1, C2, C3, C4, C5, C6 or C7) or phenyl；
N is the positive integer greater than 1.
Preferably, the X in formula (II) is：
Preferably, the molecular structural formula of the polyphenylene oxide resin such as formula (III) or formula (IV) are shown：
N is the positive integer greater than 1.
Preferably, the functional epoxy resin is isocyanate-modified bisphenol A epoxide resin, isocyanate-modified bis-phenol
F epoxy resin, isocyanate-modified bisphenol-s epoxy resin, phenol novolac epoxy resins, bisphenol-A phenolic epoxy resin, o-cresol
Novolac epoxy resin, trifunctional base epoxy, tetrafunctional base epoxy, bicyclopentadiene epoxy resin, para-aminophenol
Epoxy resin, tricyanic epoxy resin, phosphorous epoxy resin, nitrogen-containing epoxy thermoset, paraxylene epoxy resin, naphthalene type ring oxygen
Resin, benzo croak mutter in type epoxy resin, biphenyl novolac epoxy resin or phenolic group benzene alkyl novolac epoxy resin any one
Or at least two mixture.
Preferably, Y is such as any one in flowering structure in formula (I)：
Wherein, m and n independently is the positive integer greater than 1.
Preferably, the performed polymer of the epoxy resin modification polyphenylene oxide resin is by solid polyphenylene oxide resin and asphalt mixtures modified by epoxy resin
Rouge is reacted as follows and is made：
By 0.005~10 parts by weight of epoxy resin 20-80 parts by weight and catalyst, dissolved under heating and stirring；Again will
Solid 50 parts by weight of polyphenylene oxide resin are dissolved in organic solvent and the polyphenylene oxide resin solution that solid content is 30~70% are made,
Then it is slowly added dropwise in above-mentioned epoxy resin molten mass, in 125~160 DEG C of (such as 125 DEG C, 130 after being added dropwise
DEG C, 135 DEG C, 140 DEG C, 145 DEG C, 150 DEG C or 155 DEG C) under be stirred to react 3.5-12 hours (such as 4 hours, 5 hours, 6 hours,
7 hours, 8 hours, 9 hours, 10 hours or 11 hours), the prepolymer solution of epoxy resin modification polyphenylene oxide resin is made.
In the pre-polymerization production procedure of epoxy resin modification polyphenylene oxide resin, reaction temperature and reaction time are for product
Quality and preparation efficiency there are important influences.When reaction temperature be lower than 125 DEG C, no matter the reaction time how long, epoxy group
Reaction is hardly happened with the hydroxyl of polyphenylene oxide, and reaction temperature then will lead to the pairs such as epoxy autohemagglutination even crosslinking higher than 160 DEG C
Reaction greatly increases, and is unable to get epoxy-modified polyphenylene oxide performed polymer；When reaction temperature is higher than 125 DEG C, if the reaction time
Less than 3.5 hours, then polyphenylene oxide terminal functional group cannot sufficiently connect epoxide functional groups, to influence epoxy-modified polyphenylene oxide tree
Improvement of the rouge in resin combination will lead to side reaction if the reaction time is longer than 12 hours and generate and cause epoxy group
Group's autohemagglutination.
Using the performed polymer of epoxy resin modification polyphenylene oxide resin of the invention preparation method the advantages of be：
Using high boiling solvent as reaction dissolvent, the reaction temperature that pre-polymerization not only can be improved goes on smoothly reaction,
The low volatility of solvent can also provide stable reaction environment.In addition, catalyst used in the present invention can be selectively
Preferential catalysis epoxy is reacted with polyphenylene oxide terminal hydroxy group, is obtained epoxy-modified polyphenylene oxide performed polymer target product, is avoided ring
Overreact caused by the self-polymeric reaction of oxygen resin itself, causes that the molecular weight of product is excessive, crosslinking points are few, and it is solid to reduce resin
Change the intensity of body.The performed polymer of the epoxy resin modification polyphenylene oxide resin of same structure is such as prepared, the preparation method of use is：It will
Melt into liquid polyphenylene oxide resin solution after 100 parts of solid polyphenylene oxide resin, addition polymerization solvent, then by epoxy resin
It 24-35 parts and 0.001-5 parts of imidazoles catalyst, is added in solution, is stirred under 100-120 1-3 hours and is made pre-
Polymeric solution.The organic solvent low boiling point that this method uses, is easy to volatilize under base reaction problem, or cause its reaction temperature
It is unstable.In addition, this method has ignored the self-polymeric reaction of epoxy resin itself, so as to cause overreact, point of product is caused
Son amount is excessive, reduces the intensity of resin solidification body.
Preferably, the catalyst is any in polyethers, cyclic crown ether class, amine, inorganic strong alkali or inorganic acid
It is a kind of or at least two mixture.
Preferably, the polyethers are chain polyethylene glycol (H- (OCH2CH2)n- OH) or/and chain polyethylene glycol dioxane
Base ether (R (OCH2CH2)n- OR) etc..
Preferably, the cyclic crown ether class is any one in 18 hat 6,15 hat 5 or cyclodextrin etc. or at least two
Mixture.
Preferably, the amine be in quaternary ammonium salt, tertiary amine or pyridine compounds any one or at least two it is mixed
Close object.
Preferably, the quaternary ammonium salt be benzyltriethylammoinium chloride (TEBA), tetrabutylammonium bromide, tetrabutylammonium chloride,
4-butyl ammonium hydrogen sulfate (TBAB), tri-n-octyl methyl ammonium chloride, dodecyl trimethyl ammonium chloride or tetradecyltrimethylammonium chlorine
Change in ammonium etc. any one or at least two mixture；
Preferably, the tertiary amine is R3N, wherein R is the branched-chain or straight-chain alkyl below of carbon atom number 18, substitution or does not take
Any one in the phenyl in generation, preferably triethylamine, tri-n-butylamine, dioctylmethylamine or diphenyl methylamine etc. or at least two
Mixture.
Preferably, the pyridine compounds are pyridine, the pyrrole with 8 or less carbon atom branches or linear paraffin substituent group
In pyridine, phenylpyridine or bipyridyl etc. any one or at least two mixture.
Preferably, the bipyridyl is 2,2 '-bipyridyls, 4,4'-Bipyridine, 2,4 '-bipyridyls or 2, in 3 '-bipyridyls
Any one or at least two mixture.
Preferably, the inorganic strong alkali is sodium hydroxide or/and potassium hydroxide.
Preferably, the inorganic acid be in the concentrated sulfuric acid, hydrochloric acid or nitric acid etc. any one or at least two it is mixed
Close object.
Preferably, the temperature being stirred to react is 135-150 DEG C, and the time being stirred to react is 4-8 hours.
Preferably, the organic solvent is n,N-Dimethylformamide, N, N- diethylformamide, cyclohexanone, toluene, two
In toluene, trimethylbenzene or durene any one or at least two mixed solvent.
In the pre-polymerization production procedure of epoxy resin modification polyphenylene oxide resin, raw materials used proportion and catalyst
There are important influences for the quality and preparation efficiency of product for dosage.
In parts by weight, the polyphenylene oxide resin relative to 50 parts by weight, if epoxy resin is less than 20 parts by weight, polyphenylene oxide
Terminal functional group cannot sufficiently connect epoxide functional groups, so that influencing the epoxy group of polyphenylene oxide resin improves efficiency；If asphalt mixtures modified by epoxy resin
Rouge is more than 80 parts by weight, then after the reaction was completed, excessive epoxy resin will affect the formula design of resin combination.Preferably,
The additive amount of epoxy resin is 30~70 parts by weight, preferably 40~60 parts by weight.In addition, if catalyst is less than 0.005 weight
Then reaction rate is slower for part, causes the reaction time elongated, influences reaction efficiency and cost；It can if catalyst is more than 10 parts by weight
Keep reaction rate too fast, side reaction is caused to generate and cause epoxy group autohemagglutination.Preferably, the additive amount of catalyst is 0.005
~5 parts by weight, preferably 0.005~1 parts by weight.
Preferably, the method is：By 50 parts of solid polyphenylene oxide resin, melt into liquid is poly- after adding polymerization solvent
Phenylene ether resins solution, then be added in solution, 30-70 parts of epoxy resin and 0.005~1 part of catalyst at 130~150 DEG C
It is stirred to react 4~8 hours and obtains prepolymer solution.
Preferably, in resin combination, the additive amount of the performed polymer of epoxy resin modification polyphenylene oxide resin is 20-80 weight
Measure part.
Preferably, in resin combination, the content of the benzoxazine colophony is 10-60 parts by weight, such as 15 weight
Part, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight or 55 parts by weight.
Preferably, the benzoxazine colophony is bisphenol A benzoxazine, Bisphenol F benzoxazine, bisphenol S benzoxazine, two
In amine type benzoxazine, phenolphthalein type benzoxazine or dicyclopentadiene-type benzoxazine any one or at least two it is mixed
Close object.
It preferably, also include curing agent in the resin combination, content is 5~50 parts by weight.
Preferably, the curing agent is selected from linear phenolic resin, styrene maleic anhydride copolymer resin, DDS or DDM etc.
In any one or two or more mixtures.
It preferably, also include curing accelerator in the resin combination, content is 0.01~10 parts by weight.
Disclosed herein resin combination, there is weight for the quality of product, preparation efficiency in raw materials used dosage
The influence wanted.Specifically, the performed polymer of the epoxy resin modification polyphenylene oxide resin relative to 50-90 parts by weight, if curing agent
Less than 5 parts by weight, then the epoxide functional groups of the performed polymer end of epoxy resin modification polyphenylene oxide resin are not sufficiently reacted solidification,
So that the Tg (glass transition temperature) of composition is too low；Excessive unreacted crosslinking can be remained if curing agent is more than 50 parts by weight
Agent, so that the performances such as the heat resistance of composition, Tg are bad.
Answer rate slower if curing accelerator is less than 0.01 parts by weight, without obvious catalytic effect；If curing accelerator is super
Crossing 10 parts by weight then keeps reaction rate too fast, influences the preparation process of product and the quality of product.
Preferably, the curing accelerator is selected from imidazoles (imidazole), boron trifluoride amine compound, tonsilon three
Ben Ji Phosphonium (ethyltriphenylphosphoniumchloride), 2-methylimidazole (2-methylimidazole, 2-MI),
2- phenylimidazole (2-phenyl-1H-imidazole, 2PZ), 2-ethyl-4-methylimidazole (2-ethyl-4-
Methylimidazole, 2E4MZ), triphenylphosphine (tri-phenylphosphine, TPP) or 4- dimethylaminopyridine (4-
Dimethylaminopyridine, DMAP) in any one or at least two combined lewis base, or selected from manganese,
In iron, cobalt, nickel, copper or zinc any one or at least two metal salt compound lewis acid, or be selected from organic mistake
Oxide, such as cumyl peroxide (DCP, DicumylPeroxide).
Preferably, resin composition further comprises 5~60 parts by weight (such as 10 parts by weight, 15 parts by weight, 20 weight
Part, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight or 55 parts by weight) without pre-polymerization
The epoxy resin of conjunction.
Preferably, the epoxy resin is isocyanate-modified bisphenol A epoxide resin, isocyanate-modified Bisphenol F epoxy
Resin, isocyanate-modified bisphenol-s epoxy resin, phenol novolac epoxy resins, bisphenol-A phenolic epoxy resin, o-cresol phenolic aldehyde
Epoxy resin, trifunctional base epoxy, tetrafunctional base epoxy, bicyclopentadiene epoxy resin, para-aminophenol epoxy
Resin, tricyanic epoxy resin, phosphorous epoxy resin, nitrogen-containing epoxy thermoset, brominated epoxy resin, paraxylene asphalt mixtures modified by epoxy resin
Rouge, naphthalene type epoxy resin, benzo croak are muttered in type epoxy resin, biphenyl novolac epoxy resin or phenolic group benzene alkyl novolac epoxy resin
Any one or two or more mixtures.
Preferably, inorganic filler is further included in the resin combination, fire retardant, interfacial agent, dispersing agent, is had
In machine silicone elastomer or toughener any one or at least two mixture.
Preferably, the inorganic filler includes silica (molten state or non-melt state and Porous), aluminium oxide, oxidation
Magnesium, magnesium hydroxide, calcium carbonate, aluminium nitride, boron nitride, aluminium hydroxide, aluminum silicon carbide, silicon carbide, sodium carbonate, titanium dioxide, oxygen
Change zinc, zirconium oxide, quartz, diamond dust, class diamond dust, graphite, magnesium carbonate, potassium titanate, ceramic fibre, mica, boehmite
(boehmite, ALOOH), high temperature resistant aluminium hydroxide (ALH), zinc molybdate, ammonium molybdate, zinc borate, calcium phosphate, calcination of talc, cunning
Stone, silicon nitride, section burn kaolin, clay, alkali magnesium sulfate crystal whisker, barium sulfate, magnesium hydroxide crystal whisker, magnesia crystal whisker, oxidation
Calcium pyroborate, carbon nanotube, nanometer grade inorganic particle are any in the powder particle of insulator modification with machine core outer shell
It is a kind of or at least two mixture, and inorganic filler be ball-type or needle must shape, or selectivity is pre- via surfactants
Processing.
In addition, in order to guarantee the good dielectric properties of finished product, the particle powder that inorganic filler is 100 μm of partial size or less,
Preferably 1-20 μm of partial size of particle powder, optimal is 1 μm of partial size down toward nano-sized particles sprills.Needle must shape be inorganic fills out
Fill the powder that object is 50 μm of diameter or less and length is 1-200 μm.
Preferably, the fire retardant is selected from the one or two kinds of of phosphonium flame retardant, nitrogenous flame ratardant or brominated flame-retardant
Above combination.Wherein, common phosphonium flame retardant such as OP-935, SPB-100 or PX-200；Nitrogenous flame ratardant is such as
MelamineCyanurate, brominated flame-retardant such as TBBPA or Tetra-Bromo-bisphenolA, is used equally for the present invention
Technical solution in, and reach good flame retardant effect.
Preferably, known person can be used in the interfacial agent (or siloxanes coupling agent, siloxane), has no especially
It limits, specifically, it is preferable that joining (beta-methoxy using vinyltriethoxysilane, vinyltrimethoxysilane, vinyl
Base-Ethoxysilane), γ-glycidoxypropyltrime,hoxysilane or γ-amine propyl-triethoxysilicane.Wherein divide
Powder is there are commonly the products such as German Bi Ke BYK-103, BYK-901, BYK-161 and BYK-164, and but not limited to this.
Preferably, the elastomer silicone (hybridtypesiliconepowder) is rubber and resin type composite powder
Body, preferably spherical powder.Addition elastomer silicone can increase the heat resistance and impact absorbency of the resin combination.Generally
X-52-7030, KMP-605, KMP-602, KMP-601, KMP-600, KMP- of commercially available elastomer silicone such as SHIN-ETSU HANTOTAI's production
The products such as 590 and KMP-594, but not limited to this.
" comprising " of the present invention, it is intended that it can also include other components, these other components especially except described group
Assign the resin combination different characteristics.In addition to this, " comprising " of the present invention may be replaced by enclosed
" for " or " by ... form ".
For example, the silicon resin composition can also contain various additives, as concrete example, can enumerate antioxidant,
Heat stabilizer, antistatic agent, ultraviolet absorbing agent, pigment, colorant or lubricant etc..These various additives can individually make
With two or more can also being used in mixed way.
The second object of the present invention is to provide a kind of prepreg comprising reinforcing material and by impregnation it is dry after adhere to
Resin combination as described above on reinforcing material.
The reinforcing material is made of natural fiber, organic synthetic fibers, organic fabric or inorfil.
The third object of the present invention is to provide a kind of laminate, the laminate contain at least one it is as described above pre-
Leaching material, by obtaining at least one prepreg heating extrusion forming as described above.
The fourth object of the present invention is to provide a kind of copper-clad laminate, and the copper-clad laminate includes at least one
Overlapping prepreg as described above and cover the prepreg after overlapping one or both sides copper foil.
The fifth object of the present invention is to provide a kind of printed wiring laminate, contain at least one it is as described above
Prepreg.Using circuit board made of above-mentioned laminate, good heat resistance and dielectric properties can be shown, high frequency is conducive to
The signal of wiring board transmits.
Compared with the prior art, the present invention has the advantages that：
The present invention by the way that polyphenylene oxide resin is modified as the polyphenylene oxide epoxy prepolymer with group, then with benzoxazine
Resin complex reaction, the high heat resistance of low dielectric and benzoxazine colophony in combination with polyphenylene oxide resin, high Tg and fire-retardant
Advantage.Therefore, the resin combination containing epoxy-modified polyphenylene oxide resin performed polymer and benzoxazine is used for printed circuit
In the resin combination of plate, the dielectric properties of copper-clad plate can not only be improved, and improve and contain the epoxy resin modification polyphenylene oxide
The glass fiber cloth infiltrating of the resin combination of the performed polymer of resin, the resin combination made have excellent appearance table
Existing, heat resistance, dielectric properties and peel strength and high Tg.
In addition, the method for disclosed synthetic epoxy resin modified polyphenylene ether resin performed polymer, as compared with the past
Synthetic technology effectively inhibits side reaction because of selection different catalysts, solvent, reaction time and reaction temperature etc. ---
The reaction of epoxy resin autohemagglutination can effectively make the molecular weight of performed polymer product reach or approach theoretical value.
Moreover, by being obtained using the preparation method of the pre- aggressiveness of disclosed epoxy resin modification polyphenylene oxide resin
The pre- aggressiveness of the epoxy resin modification polyphenylene oxide resin arrived cooperates, obtained laminated material and copper clad layers with benzoxazine colophony
Pressing plate, with good appearance, the heat resistance (Tg that DSC method measures reaches 180-210 DEG C) of superelevation and excellent
Dielectric properties and peel strength.
In addition, the method for the performed polymer of disclosed epoxy resin modification polyphenylene oxide resin is easy to operate, production
Process is environmentally protective, low in cost, has the feasibility of large-scale production.
To sum up, the Tg of the laminate obtained using resin combination of the invention can reach 180~210 DEG C, peel strength
It can reach 1.51~1.71N/cm, can be tested by PCT (3hr), (288 DEG C) of resistance to immersed solder are greater than 20min, and Dk can reach under 1G
3.75~3.87, Df are 0.005~0.008.
Detailed description of the invention
Fig. 1 is the GPC figure of epoxy resin.
Fig. 2 is the GPC figure of polyphenylene oxide resin.
Fig. 3 is the GPC figure of the performed polymer of epoxy resin modification polyphenylene oxide resin.
Specific embodiment
The technical scheme of the invention is further explained by means of specific implementation.
In the present invention, Fig. 1 is the GPC figure of epoxy resin, and specifying information is as follows：
In the present invention, Fig. 2 is the GPC figure of polyphenylene oxide, and specifying information is as follows：
In the present invention, Fig. 3 is the GPC figure of the performed polymer of epoxy resin modification polyphenylene oxide resin, and specifying information is as follows：
Embodiment one
(1) the prepolymer solution preparation of epoxy resin modification polyphenylene oxide resin：
By 50 parts of bisphenol A type epoxy resin and 0.005 part of pyridine, dissolved under heating and stirring；Again by solid polyphenyl
It 50 parts of ether resin, is dissolved in xylene solvent and the polyphenylene oxide resin solution that solid content is 30~70% is made, be slowly added dropwise
It states in epoxy resin molten mass, is stirred to react at 145 DEG C 6 hours after being added dropwise and obtains epoxy resin modification polyphenylene oxide resin
Prepolymer solution.The GPC of the performed polymer product of epoxy resin, polyphenylene oxide and epoxy resin modification polyphenylene oxide resin schemes difference
.
(2) preparation of the performed polymer composition of epoxy resin modification polyphenylene oxide resin
By the performed polymer of (1) epoxy resin modification polyphenylene oxide resin the step of 60 parts by weight, the phenol novolac of 20 parts by weight
Resin, 40 parts by weight of bisphenol A type benzoxazine colophonies, the 2-MI of 0.1 parts by weight, the molten state silica of 100 parts by weight, 20
The phosphonium flame retardant (PX-200, big eight chemistry of Japan) and the butanone solvent of 30 parts by weight of parts by weight mix, are uniformly dispersed.
(3) preparation of the semi-solid preparation and substrate of resin combination
By the performed polymer composition of above-mentioned epoxy resin modification polyphenylene oxide resin after being impregnated with glass fiber cloth, 170
DEG C 3 minutes production prepregs of baking, prepreg appearance enters shown in table one；Two panels copper foil is coincided in 4 obtained preimpregnation again
Two sides are expected, using vacuum hotpressing machine, in 190 DEG C of temperature, pressure 35kg/cm2, under the conditions of pressing time 90min, pressing and forming,
To obtain a kind of copper foil laminates, performance test is as shown in Table 2.
Embodiment two
(1) the prepolymer solution preparation of epoxy resin modification polyphenylene oxide resin：
By 50 parts of DCPD epoxy resin and 0.005 part of pyridine, dissolved under heating and stirring；Again by solid polyphenylene oxide tree
It 50 parts of rouge, is dissolved in xylene solvent and the polyphenylene oxide resin solution that solid content is 30~70% is made, be slowly added dropwise into above-mentioned ring
It is stirred to react at 145 DEG C 6 hours in oxygen resin melt, after being added dropwise and obtains the pre- of epoxy resin modification polyphenylene oxide resin
Oligomer solution.In the molecular weight determination that the performed polymer of resulting epoxy resin modification polyphenylene oxide resin utilizes GPC, Weight-average molecular
Amount is 6200.
(2) preparation of the performed polymer composition of epoxy resin modification polyphenylene oxide resin
By the performed polymer of step (1) epoxy resin modification polyphenylene oxide resin of 60 parts by weight, the phenol novolac of 20 parts by weight
Resin, 40 parts by weight, two amine type benzoxazine colophony, the 2-MI of 0.1 parts by weight, the molten state silica of 100 parts by weight, 20
The phosphonium flame retardant (PX-200, big eight chemistry of Japan) and the butanone solvent of 30 parts by weight of parts by weight mix, are uniformly dispersed.
(3) preparation of the semi-solid preparation and substrate of resin combination
By the performed polymer composition of above-mentioned epoxy resin modification polyphenylene oxide resin after being impregnated with glass fiber cloth, 170
DEG C 3 minutes production prepregs of baking, prepreg appearance enters shown in table one；Two panels copper foil is coincided in 4 obtained preimpregnation again
Two sides are expected, using vacuum hotpressing machine, in 190 DEG C of temperature, pressure 35kg/cm2, under the conditions of pressing time 90min, pressing and forming,
To obtain a kind of copper foil laminates, performance test is as shown in Table 2.
Embodiment three
(1) the prepolymer solution preparation of epoxy resin modification polyphenylene oxide resin：
By 20 parts of DCPD epoxy resin and 0.005 part of pyridine, dissolved under heating and stirring；Again by solid polyphenylene oxide tree
It 50 parts of rouge, is dissolved in toluene solvant and the polyphenylene oxide resin solution that solid content is 30~70% is made, be slowly added dropwise into above-mentioned epoxy
The pre-polymerization of epoxy resin modification polyphenylene oxide resin is stirred to react 6 hours and obtained in resin melt, after being added dropwise at 145 DEG C
Liquid solution.In the molecular weight determination that the performed polymer of resulting epoxy resin modification polyphenylene oxide resin utilizes GPC, weight average molecular weight
It is 6200.
(2) preparation of the performed polymer composition of epoxy resin modification polyphenylene oxide resin
By the performed polymer of (1) epoxy resin modification polyphenylene oxide resin the step of 60 parts by weight, the phenol novolac of 20 parts by weight
Resin, 40 parts by weight, two amine type benzoxazine colophony, the 2-MI of 0.1 parts by weight, the molten state silica of 100 parts by weight, 20
The phosphonium flame retardant (PX-200, big eight chemistry of Japan) and the butanone solvent of 30 parts by weight of parts by weight mix, are uniformly dispersed.
(3) preparation of the semi-solid preparation and substrate of resin combination
By the performed polymer composition of above-mentioned epoxy resin modification polyphenylene oxide resin after being impregnated with glass fiber cloth, 170
DEG C 3 minutes production prepregs of baking, prepreg appearance enters shown in table one；Two panels copper foil is coincided in 4 obtained preimpregnation again
Two sides are expected, using vacuum hotpressing machine, in 190 DEG C of temperature, pressure 35kg/cm2, under the conditions of pressing time 90min, pressing and forming,
To obtain a kind of copper foil laminates, performance test is as shown in Table 2.
Example IV
(1) the prepolymer solution preparation of epoxy resin modification polyphenylene oxide resin：
By 80 parts of DCPD epoxy resin and 0.005 part of pyridine, dissolved under heating and stirring；Again by solid polyphenylene oxide tree
It 50 parts of rouge, is dissolved in xylene solvent and the polyphenylene oxide resin solution that solid content is 30~70% is made, be slowly added dropwise into above-mentioned ring
It is stirred to react at 145 DEG C 6 hours in oxygen resin melt, after being added dropwise and obtains the pre- of epoxy resin modification polyphenylene oxide resin
Oligomer solution.In the molecular weight determination that the performed polymer of resulting epoxy resin modification polyphenylene oxide resin utilizes GPC, Weight-average molecular
Amount is 6600.
(2) preparation of the performed polymer composition of epoxy resin modification polyphenylene oxide resin
By the performed polymer of (1) epoxy resin modification polyphenylene oxide resin the step of 60 parts by weight, the phenol novolac of 20 parts by weight
Resin, 40 parts by weight, two amine type benzoxazine colophony, the 2-MI of 0.1 parts by weight, the molten state silica of 100 parts by weight, 20
The phosphonium flame retardant (PX-200, big eight chemistry of Japan) and the butanone solvent of 30 parts by weight of parts by weight mix, are uniformly dispersed.
(3) preparation of the semi-solid preparation and substrate of resin combination
By the performed polymer composition of above-mentioned epoxy resin modification polyphenylene oxide resin after being impregnated with glass fiber cloth, 170
DEG C 3 minutes production prepregs of baking, prepreg appearance enters shown in table one；Two panels copper foil is coincided in 4 obtained preimpregnation again
Two sides are expected, using vacuum hotpressing machine, in 190 DEG C of temperature, pressure 35kg/cm2, under the conditions of pressing time 90min, pressing and forming,
To obtain a kind of copper foil laminates, performance test is as shown in Table 2.
Embodiment five
(1) the prepolymer solution preparation of epoxy resin modification polyphenylene oxide resin：
By 50 parts of DCPD epoxy resin and 0.005 part of pyridine, dissolved under heating and stirring；Again by solid polyphenylene oxide tree
It 50 parts of rouge, is dissolved in xylene solvent and the polyphenylene oxide resin solution that solid content is 30~70% is made, be slowly added dropwise into above-mentioned ring
It is stirred to react at 160 DEG C 6 hours in oxygen resin melt, after being added dropwise and obtains the pre- of epoxy resin modification polyphenylene oxide resin
Oligomer solution.
(2) preparation of the performed polymer composition of epoxy resin modification polyphenylene oxide resin
By the performed polymer of (1) epoxy resin modification polyphenylene oxide resin the step of 60 parts by weight, the phenol novolac of 20 parts by weight
Resin, 40 parts by weight, two amine type benzoxazine colophony, the 2-MI of 0.1 parts by weight, the molten state silica of 100 parts by weight, 20
The phosphonium flame retardant (PX-200, big eight chemistry of Japan) and the butanone solvent of 30 parts by weight of parts by weight mix, are uniformly dispersed.Institute
The performed polymer of the epoxy resin modification polyphenylene oxide resin obtained utilizes in the molecular weight determination of GPC, weight average molecular weight 6400.
(3) preparation of the semi-solid preparation and substrate of resin combination
By the performed polymer composition of above-mentioned epoxy resin modification polyphenylene oxide resin after being impregnated with glass fiber cloth, 170
DEG C 3 minutes production prepregs of baking, prepreg appearance enters shown in table one；Two panels copper foil is coincided in 4 obtained preimpregnation again
Two sides are expected, using vacuum hotpressing machine, in 190 DEG C of temperature, pressure 35kg/cm2, under the conditions of pressing time 90min, pressing and forming,
To obtain a kind of copper foil laminates, performance test is as shown in Table 2.
Embodiment six
(1) the prepolymer solution preparation of epoxy resin modification polyphenylene oxide resin：
By 50 parts of DCPD epoxy resin and 0.005 part of pyridine, dissolved under heating and stirring；Again by solid polyphenylene oxide tree
It 50 parts of rouge, is dissolved in xylene solvent and the polyphenylene oxide resin solution that solid content is 30~70% is made, be slowly added dropwise into above-mentioned ring
It is stirred to react at 125 DEG C 6 hours in oxygen resin melt, after being added dropwise and obtains the pre- of epoxy resin modification polyphenylene oxide resin
Oligomer solution.In the molecular weight determination that the performed polymer of resulting epoxy resin modification polyphenylene oxide resin utilizes GPC, Weight-average molecular
Amount is 6150.
(2) preparation of the performed polymer composition of epoxy resin modification polyphenylene oxide resin
By the performed polymer of (1) epoxy resin modification polyphenylene oxide resin the step of 60 parts by weight, the phenol novolac of 20 parts by weight
Resin, 40 parts by weight, two amine type benzoxazine colophony, the 2-MI of 0.1 parts by weight, the molten state silica of 100 parts by weight, 20
The phosphonium flame retardant (PX-200, big eight chemistry of Japan) and the butanone solvent of 30 parts by weight of parts by weight mix, are uniformly dispersed.
(3) preparation of the semi-solid preparation and substrate of resin combination
By the performed polymer composition of above-mentioned epoxy resin modification polyphenylene oxide resin after being impregnated with glass fiber cloth, 170
DEG C 3 minutes production prepregs of baking, prepreg appearance enters shown in table one；Two panels copper foil is coincided in 4 obtained preimpregnation again
Two sides are expected, using vacuum hotpressing machine, in 190 DEG C of temperature, pressure 35kg/cm2, under the conditions of pressing time 90min, pressing and forming,
To obtain a kind of copper foil laminates, performance test is as shown in Table 2.
Embodiment seven
(1) the prepolymer solution preparation of epoxy resin modification polyphenylene oxide resin：
By 50 parts of bisphenol A type epoxy resin and 0.005 part of the concentrated sulfuric acid, dissolved under heating and stirring；It again will be solid poly-
50 parts of phenylene ether resins, be dissolved in xylene solvent be made solid content be 30~70% polyphenylene oxide resin solution, be slowly added dropwise into
It is stirred to react at 145 DEG C 6 hours in above-mentioned epoxy resin molten mass, after being added dropwise and obtains epoxy resin modification polyphenylene oxide tree
Rouge prepolymer solution.In the molecular weight determination that the performed polymer of resulting epoxy resin modification polyphenylene oxide resin utilizes GPC, weight is equal
Molecular weight is 5700.
(2) preparation of the performed polymer composition of epoxy resin modification polyphenylene oxide resin
By the performed polymer of (1) epoxy resin modification polyphenylene oxide resin the step of 60 parts by weight, the phenol novolac of 20 parts by weight
Resin, 40 parts by weight of bisphenol A type benzoxazine colophonies, the 2-MI of 0.1 parts by weight, the molten state silica of 100 parts by weight, 20
The phosphonium flame retardant (PX-200, big eight chemistry of Japan) and the butanone solvent of 30 parts by weight of parts by weight mix, are uniformly dispersed.
(3) preparation of the semi-solid preparation and substrate of resin combination
By the performed polymer composition of above-mentioned epoxy resin modification polyphenylene oxide resin after being impregnated with glass fiber cloth, 170
DEG C 3 minutes production prepregs of baking, prepreg appearance enters shown in table one；Two panels copper foil is coincided in 4 obtained preimpregnation again
Two sides are expected, using vacuum hotpressing machine, in 190 DEG C of temperature, pressure 35kg/cm2, under the conditions of pressing time 90min, pressing and forming,
To obtain a kind of copper foil laminates, performance test is as shown in Table 2.
Embodiment eight
(1) the prepolymer solution preparation of epoxy resin modification polyphenylene oxide resin：
By 50 parts and 0.005 part polyethylene glycol 400 of bisphenol A type epoxy resin, dissolved under heating and stirring；Again by solid-state
50 parts of polyphenylene oxide resin, be dissolved in toluene solvant be made solid content be 30~70% polyphenylene oxide resin solution, be slowly added dropwise
Enter in above-mentioned epoxy resin molten mass, is stirred to react at 145 DEG C 6 hours after being added dropwise and obtains epoxy resin modification polyphenylene oxide
Resin prepolymer liquid solution.In the molecular weight determination that the performed polymer of resulting epoxy resin modification polyphenylene oxide resin utilizes GPC, weight
Average molecular weight is 5600.
(2) preparation of the performed polymer composition of epoxy resin modification polyphenylene oxide resin
Starve the performed polymer of (1) epoxy resin modification polyphenylene oxide resin, 20 parts by weight the step of 60 parts by weight to phenol novolac
Resin, 40 parts by weight of bisphenol A type benzoxazine colophonies, the 2-MI of 0.1 parts by weight, the molten state silica of 100 parts by weight, 20
The phosphonium flame retardant (PX-200, big eight chemistry of Japan) and the butanone solvent of 30 parts by weight of parts by weight mix, are uniformly dispersed.
(3) preparation of the semi-solid preparation and substrate of resin combination
By the performed polymer composition of above-mentioned epoxy resin modification polyphenylene oxide resin after being impregnated with glass fiber cloth, 170
DEG C 3 minutes production prepregs of baking, prepreg appearance enters shown in table one；Two panels copper foil is coincided in 4 obtained preimpregnation again
Two sides are expected, using vacuum hotpressing machine, in 190 DEG C of temperature, pressure 35kg/cm2, under the conditions of pressing time 90min, pressing and forming,
To obtain a kind of copper foil laminates, performance test is as shown in Table 2.
Embodiment nine
(1) the prepolymer solution preparation of epoxy resin modification polyphenylene oxide resin：
By 50 parts of xenyl aralkyl type phenol novolac epoxy resins and 0.005 part of pyridine, dissolved under heating and stirring；
Again by 50 parts of solid polyphenylene oxide resin, it is dissolved in toluene solvant and the polyphenylene oxide resin solution that solid content is 30~70% is made,
It is slowly added dropwise in above-mentioned epoxy resin molten mass, is stirred to react at 145 DEG C 6 hours after being added dropwise and obtains epoxy resin and change
Property polyphenylene oxide resin prepolymer solution.
(2) preparation of the performed polymer composition of epoxy resin modification polyphenylene oxide resin
By the performed polymer of (1) epoxy resin modification polyphenylene oxide resin the step of 60 parts by weight, the phenol novolac of 20 parts by weight
Resin, 40 parts by weight, two amine type benzoxazine colophony, the 2-MI of 0.1 parts by weight, the molten state silica of 100 parts by weight, 20
The phosphonium flame retardant (PX-200, big eight chemistry of Japan) and the butanone solvent of 30 parts by weight of parts by weight mix, are uniformly dispersed.
(3) preparation of the semi-solid preparation and substrate of resin combination
By the performed polymer composition of above-mentioned epoxy resin modification polyphenylene oxide resin after being impregnated with glass fiber cloth, 170
DEG C 3 minutes production prepregs of baking, prepreg appearance enters shown in table one；Two panels copper foil is coincided in 4 obtained preimpregnation again
Two sides are expected, using vacuum hotpressing machine, in 190 DEG C of temperature, pressure 35kg/cm2, under the conditions of pressing time 90min, pressing and forming,
To obtain a kind of copper foil laminates, performance test is as shown in Table 2.
Comparative example one
(1) the prepolymer solution preparation of epoxy resin modification polyphenylene oxide resin：
The PPO solid-state polyphenylene oxide resin of 100 parts by weight is added into butanone solvent, melt into liquid polyphenylene oxide resin is molten
Liquid, then by the bisphenol A type epoxy resin of 24 parts by weight and 2-methylimidazole (2-methylimidazole, the 2- of 0.05 parts by weight
MI), it is added in butanone solution, 1-3 hours is stirred at 120 DEG C and the solution that arrives.Resulting solution body is divided using GPC's
Son measures in fixed, weight average molecular weight 4000.
(2) preparation of the performed polymer composition of epoxy resin modification polyphenylene oxide resin
By the performed polymer of (1) epoxy resin modification polyphenylene oxide resin the step of 60 parts by weight, the phenol novolac of 20 parts by weight
Resin, 40 parts by weight of bisphenol A type benzoxazine colophonies, the 2-MI of 0.1 parts by weight, the molten state silica of 100 parts by weight, 20
The phosphonium flame retardant (PX-200, big eight chemistry of Japan) and the butanone solvent of 30 parts by weight of parts by weight mix, are uniformly dispersed.
(3) preparation of the semi-solid preparation and substrate of resin combination
By the performed polymer composition of above-mentioned epoxy resin modification polyphenylene oxide resin after being impregnated with glass fiber cloth, 170
DEG C 3 minutes production prepregs of baking, prepreg appearance enters shown in table one；Two panels copper foil is coincided in 4 obtained preimpregnation again
Two sides are expected, using vacuum hotpressing machine, in 190 DEG C of temperature, pressure 35kg/cm2, under the conditions of pressing time 90min, pressing and forming,
To obtain a kind of copper foil laminates, performance test is as shown in Table 3.
Comparative example two
(1) the prepolymer solution preparation of epoxy resin modification polyphenylene oxide resin：
By 50 parts of DCPD epoxy resin and 0.005 part of pyridine, dissolved under heating and stirring；Again by solid polyphenylene oxide tree
It 50 parts of rouge, is dissolved in xylene solvent and the polyphenylene oxide resin solution that solid content is 30~70% is made, be slowly added dropwise into above-mentioned ring
It is stirred to react at 100-120 DEG C 6 hours in oxygen resin melt, after being added dropwise and obtains epoxy resin modification polyphenylene oxide resin
Prepolymer solution.In the molecular weight determination that the performed polymer of resulting epoxy resin modification polyphenylene oxide resin utilizes GPC, divide equally again
Son amount is 4000.
(2) preparation of the performed polymer composition of epoxy resin modification polyphenylene oxide resin
By the performed polymer of (1) epoxy resin modification polyphenylene oxide resin the step of 60 parts by weight, the phenol novolac of 20 parts by weight
Resin, 40 parts by weight of bisphenol A type benzoxazine colophonies, the 2-MI of 0.1 parts by weight, the molten state silica of 100 parts by weight, 20
The phosphonium flame retardant (PX-200, big eight chemistry of Japan) and the butanone solvent of 30 parts by weight of parts by weight mix, are uniformly dispersed.
(3) preparation of the semi-solid preparation and substrate of resin combination
By the performed polymer composition of above-mentioned epoxy resin modification polyphenylene oxide resin after being impregnated with glass fiber cloth, 170
DEG C 3 minutes production prepregs of baking, prepreg appearance enters shown in table one；Two panels copper foil is coincided in 4 obtained preimpregnation again
Two sides are expected, using vacuum hotpressing machine, in 190 DEG C of temperature, pressure 35kg/cm2, under the conditions of pressing time 90min, pressing and forming,
To obtain a kind of copper foil laminates, performance test is as shown in Table 3.
Comparative example three
(1) the prepolymer solution preparation of epoxy resin modification polyphenylene oxide resin：
By 50 parts of DCPD epoxy resin and 0.005 part of pyridine, dissolved under heating and stirring；Again by solid polyphenylene oxide tree
It 50 parts of rouge, is dissolved in xylene solvent and the polyphenylene oxide resin solution that solid content is 30~70% is made, be slowly added dropwise into above-mentioned ring
Be stirred to react at 145 DEG C 1-3 hours in oxygen resin melt, after being added dropwise and epoxy resin modification polyphenylene oxide resin it is pre-
Oligomer solution.In the molecular weight determination that the performed polymer of resulting epoxy resin modification polyphenylene oxide resin utilizes GPC, Weight-average molecular
Amount is 4500.
(2) preparation of the performed polymer composition of epoxy resin modification polyphenylene oxide resin
By the performed polymer of (1) epoxy resin modification polyphenylene oxide resin the step of 60 parts by weight, the phenol novolac of 20 parts by weight
Resin, 100 parts by weight, two amine type benzoxazine colophony, the 2-MI of 0.1 parts by weight, the molten state silica of 100 parts by weight, 20
The phosphonium flame retardant (PX-200, big eight chemistry of Japan) and the butanone solvent of 30 parts by weight of parts by weight mix, are uniformly dispersed.
(3) preparation of the semi-solid preparation and substrate of resin combination
By the performed polymer composition of above-mentioned epoxy resin modification polyphenylene oxide resin after being impregnated with glass fiber cloth, 170
DEG C baking 3 minutes production prepreg prepreg appearances enter shown in table one；Two panels copper foil is coincided in 4 obtained prepregs again
Two sides, using vacuum hotpressing machine, in 190 DEG C of temperature, pressure 35kg/cm2, under the conditions of pressing time 90min, pressing and forming, with
A kind of copper foil laminates are obtained, wherein semi-solid preparation film is formed by curing the insulating layer between two copper foils, and performance test is as shown in Table 3.
Comparative example four
(1) preparation of epoxy resin and benzoxazine colophony composition
By the phenol novolacs of 20 parts by weight, 100 parts by weight, two amine type benzoxazine colophony, 0.1 parts by weight 2-MI,
The molten state silica of 100 parts by weight, the phosphonium flame retardant (PX-200, big eight chemistry of Japan) of 20 parts by weight and 30 parts by weight
Butanone solvent mixing, be uniformly dispersed.
(2) preparation of the semi-solid preparation and substrate of resin combination
By above-mentioned epoxy resin and benzoxazine colophony composition through toasting 3 points at 170 DEG C with after the impregnation of glass fiber cloth
Clock makes prepreg, and prepreg appearance enters shown in table one；Two panels copper foil is coincided in 4 obtained prepreg two sides again, is adopted
With vacuum hotpressing machine, in 190 DEG C of temperature, pressure 35kg/cm2, under the conditions of pressing time 90min, pressing and forming, to obtain one kind
Copper foil laminates, wherein semi-solid preparation film is formed by curing the insulating layer between two copper foils, and performance test is as shown in Table 3.
Comparative example five
(1) preparation of epoxy resin, benzoxazine colophony and unmodified polyphenyl ether resin composition
By the unmodified polyphenylene oxide resin of 60 parts by weight, the phenol novolacs of 20 parts by weight, 100 parts by weight, two amine type benzene
Bing oxazine resin, the 2-MI of 0.1 parts by weight, the molten state silica of 100 parts by weight, 20 parts by weight phosphonium flame retardant (PX-
200, Japan it is big eight chemistry) and 30 parts by weight butanone solvent mix, be uniformly dispersed.
(2) preparation of the semi-solid preparation and substrate of resin combination
Epoxy resin, benzoxazine colophony and unmodified polyphenyl ether resin composition with glass fiber cloth after being impregnated with, 170
DEG C 3 minutes production prepregs of baking, prepreg appearance enters shown in table one；Two panels copper foil is coincided in 4 obtained preimpregnation again
Two sides are expected, using vacuum hotpressing machine, in 190 DEG C of temperature, pressure 35kg/cm2, under the conditions of pressing time 90min, pressing and forming,
To obtain a kind of copper foil laminates, wherein semi-solid preparation film is formed by curing the insulating layer between two copper foils, performance test such as three institute of table
Show.
Embodiment one to nine and the resulting prepreg of comparative example one to five are observed into its appearance and recorded as shown in Table 1, knot
Fruit shows that the prepreg appearance of embodiment one to nine is more smooth, and air entrapment amount is less.Outside the prepreg of comparative example one to five
See then very coarse, and surface can form a film when glass is distributed in impregnation, cause impregnation bad, the epoxy official that the display present invention discloses
The modified polyphenylene oxide resin of energy base can effectively improve the wellability of prepreg.
One prepreg appearance of table
The resulting laminate progress characteristic test data of embodiment one to nine are as shown in Table 2, and comparative example one to five is resulting
It is as shown in Table 3 that laminate carries out characteristic test data.Embodiment the result shows that epoxy-modified polyphenylene oxide resin of the invention system
Preparation Method is using different epoxy resin (embodiment one, two and nine), the ratio of different epoxy resin and polyphenylene oxide resin
(embodiment two to four), (embodiment two, five and six) and different catalysts type at 125-160 DEG C of reaction temperature of the present invention
(embodiment one, seven and eight) can obtain ideal epoxy Noryl prepolymer.With do not contain epoxy-modified polyphenylene oxide resin
Resin combination (comparative example four) or resin combination (comparative example five) containing unmodified polyphenylene oxide resin obtained by plate phase
Than, containing disclosed herein epoxy resin modification polyphenylene oxide resin resin combination obtained by plate there is more preferably dielectric
Performance (Dk/Df) and Tg (glass transition temperature), it is preferable electrical property that wherein Dk and Df value is lower, and Tg temperature is more a height of preferably
Tg.
Comparative example one the result shows that using imidazoles as catalyst, 100-120 DEG C of reaction temperature, reaction time 1-3
Hour, polyphenylene ether resin did not played modified effect, extended the reaction time in time to 6 hours (comparative example two), and effect is not yet
Obviously.When temperature is increased to 145 DEG C, the dielectric properties and Tg of the laminate containing the resin prepolymer are significantly changed
It is kind, but since the reaction time is too short, epoxy group reacts insufficient with the hydroxyl of polyphenylene oxide resin, thus gained plate property
Well below the resulting plate of performed polymer (embodiment one to nine) under the conditions of reaction 6 hours at 145 DEG C.In addition, comparative example
One, two and comparative example four, five gained plate properties be not much different, also illustrate and react 1-3 hours at 100-120 DEG C to polyphenyl
Ether resin does not play effective modifying function.
Therefore, the method provided by the invention for preparing epoxy-modified polyphenylene oxide resin, and contain the epoxy-modified polyphenyl
The resulting plate of the resin combination of ether resin and benzoxazine colophony has wide range of applications, and has biggish productive value.
Two example composition laminate characteristic of table
Three comparative example composition layer pressing plate characteristic of table
| Performance | Comparative example one | Comparative example two | Comparative example three | Comparative example four | Comparative example five |
| Tg(DSC)/℃ | 144 | 145 | 159 | 154 | 146 |
| Peel strength (N/mm) | 1.31 | 1.30 | 1.40 | 1.43 | 1.34 |
| PCT(3hr) | Pass | Pass | Pass | Pass | Pass |
| Resistance to immersed solder (288 DEG C)/min | 10 | 10 | 12 | 20 | 15 |
| DK@1G | 4.38 | 4.35 | 4.26 | 4.40 | 4.32 |
| Df@1G | 0.013 | 0.013 | 0.010 | 0.012 | 0.012 |
The Applicant declares that the present invention is explained by the above embodiments method detailed of the invention, but the present invention not office
Be limited to above-mentioned method detailed, that is, do not mean that the invention must rely on the above detailed methods to implement.Technical field
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, selection of concrete mode etc., all of which fall within the scope of protection and disclosure of the present invention.
Claims (39)
1. a kind of resin combination, which includes the performed polymer and benzoxazine of epoxy resin modification polyphenylene oxide resin
Resin；
The performed polymer of the epoxy resin modification polyphenylene oxide resin is by solid polyphenylene oxide resin and epoxy resin according to as follows
Method is reacted and is made：
By 0.005~10 parts by weight of 20~80 parts by weight of epoxy resin and catalyst, dissolved under heating and stirring；Again by solid-state
50 parts by weight of polyphenylene oxide resin, be dissolved in organic solvent be made solid content be 30~70% polyphenylene oxide resin solution, then
It is slowly added dropwise in above-mentioned epoxy resin molten mass, it is small to be stirred to react 3.5~12 at 125~160 DEG C after being added dropwise
When, the prepolymer solution of epoxy resin modification polyphenylene oxide resin is made.
2. resin combination as described in claim 1, which is characterized in that the pre-polymerization of the epoxy resin modification polyphenylene oxide resin
Body has the structure as shown in formula (I)：
Wherein, X is：
Wherein, R is alkylidene, the singly-bound ,-SO of substituted or unsubstituted C1~C52,-O- ,-CO- ,-SO- or-SC-；
Y is the functional group of functional epoxy resin；
Z1、Z2、Z3、Z4It is identical or different, it independently is hydrogen atom, halogen atom, the alkyl or phenyl below of carbon atom number 8；
N is the positive integer greater than 1.
3. resin combination as claimed in claim 2, which is characterized in that in formula (I), X is
4. resin combination as claimed in claim 2, which is characterized in that the polyphenylene oxide resin molecular structure such as formula (II) institute
Show：
Wherein, X is：
Wherein, R is alkylidene, the singly-bound ,-SO of substituted or unsubstituted C1~C52,-O- ,-CO- ,-SO- or-SC-；
Z1、Z2、Z3、Z4It is identical or different, it independently is hydrogen atom, halogen atom, the alkyl or phenyl below of carbon atom number 8；
N is the positive integer greater than 1；
5. resin combination as claimed in claim 4, which is characterized in that the X in formula (II) is：
6. resin combination as claimed in claim 2, which is characterized in that the molecular structural formula of the polyphenylene oxide resin such as formula
(III) or shown in formula (IV)：
N is the positive integer greater than 1.
7. resin combination as claimed in claim 2, which is characterized in that the functional epoxy resin is isocyanate-modified
Bisphenol A epoxide resin, isocyanate-modified bisphenol F epoxy resin, isocyanate-modified bisphenol-s epoxy resin, phenol novolac ring
Oxygen resin, bisphenol-A phenolic epoxy resin, Study On O-cresol Epoxy Resin, trifunctional base epoxy, tetrafunctional base asphalt mixtures modified by epoxy resin
Rouge, para-aminophenol epoxy resin, tricyanic epoxy resin, phosphorous epoxy resin, contains azo-cycle at bicyclopentadiene epoxy resin
Oxygen resin, paraxylene epoxy resin, naphthalene type epoxy resin, benzo croak are muttered type epoxy resin, biphenyl novolac epoxy resin or phenol
In base benzene alkyl novolac epoxy resin any one or at least two mixture.
8. resin combination as claimed in claim 2, which is characterized in that Y is such as any one in flowering structure in formula (I)：
Wherein, m and n independently is the positive integer greater than 1.
9. resin combination as described in claim 1, which is characterized in that the additive amount of the epoxy resin is 30~70 weight
Part.
10. resin combination as claimed in claim 9, which is characterized in that the additive amount of the epoxy resin is 40~60 weights
Measure part.
11. resin combination as described in claim 1, which is characterized in that the additive amount of the catalyst is 0.005~5 weight
Measure part.
12. resin combination as claimed in claim 11, which is characterized in that the additive amount of the catalyst is 0.005~1 weight
Measure part.
13. resin combination as described in claim 1, which is characterized in that the catalyst be polyethers, cyclic crown ether class,
In amine, inorganic strong alkali or inorganic acid any one or at least two mixture.
14. resin combination as claimed in claim 13, which is characterized in that the polyethers be chain polyethylene glycol or/and
Chain dialkylethers.
15. resin combination as claimed in claim 13, which is characterized in that the cyclic crown ether class be 18 hat 6,15 hat 5 or
In cyclodextrin any one or at least two mixture.
16. resin combination as claimed in claim 13, which is characterized in that the amine is quaternary ammonium salt, tertiary amine or pyridine
Close object in any one or at least two mixture.
17. resin combination as claimed in claim 16, which is characterized in that the quaternary ammonium salt be benzyltriethylammoinium chloride,
Tetrabutylammonium bromide, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate, tri-n-octyl methyl ammonium chloride, trimethyl chlorination
In ammonium or tetradecyl trimethyl ammonium chloride any one or at least two mixture.
18. resin combination as claimed in claim 16, which is characterized in that the tertiary amine is R3N, wherein R is carbon atom number 18
Branched-chain or straight-chain alkyl, substitution or the phenyl not replaced below.
19. resin combination as claimed in claim 18, which is characterized in that the tertiary amine is triethylamine, tri-n-butylamine, dioctyl
In methylamine or diphenyl methylamine any one or at least two mixture.
20. resin combination as claimed in claim 16, which is characterized in that the pyridine compounds be pyridine, with 8 with
Any one in the pyridine of lower carbon atom branch or linear paraffin substituent group, phenylpyridine or bipyridyl or at least two
Mixture.
21. resin combination as claimed in claim 20, which is characterized in that the bipyridyl is 2,2 '-bipyridyls, 4,4 '-
In bipyridyl, 2,4 '-bipyridyls or 2,3 '-bipyridyls any one or at least two mixture.
22. resin combination as claimed in claim 13, which is characterized in that the inorganic strong alkali is sodium hydroxide or/and hydrogen
Potassium oxide.
23. resin combination as claimed in claim 13, which is characterized in that the inorganic acid is the concentrated sulfuric acid, hydrochloric acid or nitre
In acid any one or at least two mixture.
24. resin combination as described in claim 1, which is characterized in that the temperature being stirred to react is 130-150 DEG C,
The time being stirred to react is 4-8 hours.
25. resin combination as described in claim 1, which is characterized in that the organic solvent be n,N-Dimethylformamide,
Any one in N, N- diethylformamide, cyclohexanone, toluene, dimethylbenzene, trimethylbenzene or durene or at least two
Mixed solvent.
26. resin combination as described in claim 1, which is characterized in that in resin combination, epoxy resin modification polyphenyl
The additive amount of the performed polymer of ether resin is 20-80 parts by weight.
27. resin combination as described in claim 1, which is characterized in that in resin combination, the benzoxazine colophony
Content be 10-60 parts by weight.
28. resin combination as described in claim 1, which is characterized in that the benzoxazine colophony is bisphenol-A Ben Bing Evil
Piperazine, Bisphenol F benzoxazine, bisphenol S benzoxazine, two amine type benzoxazines, phenolphthalein type benzoxazine or dicyclopentadiene-type benzene
In Bing oxazine any one or at least two mixture.
29. resin combination as described in claim 1, which is characterized in that it also include curing agent in the resin combination,
Content is 5~50 parts by weight.
30. resin combination as claimed in claim 29, which is characterized in that the curing agent is selected from linear phenolic resin, benzene
Any one in thylene maleic acid anhydride copolymer resin, DDS or DDM or two or more mixtures.
31. resin combination as claimed in claim 29, which is characterized in that also promote comprising solidification in the resin combination
Agent, content are 0.01~10 parts by weight.
32. resin combination as claimed in claim 31, which is characterized in that the curing accelerator is selected from imidazoles, borontrifluoride
Boron-amine compound, chlorination Yi base triphenyl phosphonium, 2-methylimidazole, 2- phenylimidazole, 2-ethyl-4-methylimidazole, triphenylphosphine
Or in 4- dimethylaminopyridine any one or at least two combined lewis base, or selected from manganese, iron, cobalt, nickel,
In copper or zinc any one or at least two metal salt compound lewis acid, or be selected from organic peroxide.
33. resin combination as described in claim 1, which is characterized in that the resin composition further comprises 5~60 weight
Part without prepolymerized epoxy resin.
34. resin combination as described in claim 1, which is characterized in that it is described without prepolymerized epoxy resin be isocyanide
Acid esters modified bisphenol A epoxy resin, isocyanate-modified bisphenol F epoxy resin, isocyanate-modified bisphenol-s epoxy resin, benzene
Phenol novolak epoxy, bisphenol-A phenolic epoxy resin, Study On O-cresol Epoxy Resin, trifunctional base epoxy, tetrafunctional base
Epoxy resin, bicyclopentadiene epoxy resin, para-aminophenol epoxy resin, tricyanic epoxy resin, phosphorous epoxy resin,
Nitrogen-containing epoxy thermoset, brominated epoxy resin, paraxylene epoxy resin, naphthalene type epoxy resin, benzo croak mutter type epoxy resin, connection
Any one in phenol formaldehyde epoxy resin or phenolic group benzene alkyl novolac epoxy resin or two or more mixtures.
35. resin combination as described in claim 1, which is characterized in that further included in the resin combination inorganic
Any one in filler, fire retardant, interfacial agent, dispersing agent, elastomer silicone or toughener or at least two
Mixture.
36. a kind of prepreg comprising reinforcing material and by impregnation be attached to after dry on reinforcing material such as claim
Resin combination described in one of 1-35.
37. a kind of laminate, the laminate contains an at least prepreg as claimed in claim 36.
38. a kind of copper-clad laminate, the copper-clad laminate includes the as claimed in claim 36 of at least one overlapping
Prepreg and cover the prepreg after overlapping one or both sides copper foil.
39. a kind of printed wiring laminate contains an at least prepreg as claimed in claim 36.
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| CN201510852434.9A CN105419348B (en) | 2016-01-18 | 2016-01-18 | A kind of resin combination and prepreg and laminate using it |
| PCT/CN2016/082107 WO2017124668A1 (en) | 2016-01-18 | 2016-05-13 | Resin composition, and prepreg and laminated board using same |
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| CN201510852434.9A CN105419348B (en) | 2016-01-18 | 2016-01-18 | A kind of resin combination and prepreg and laminate using it |
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| CN105419348B (en) * | 2016-01-18 | 2018-11-27 | 广东生益科技股份有限公司 | A kind of resin combination and prepreg and laminate using it |
| CN106750260B (en) * | 2016-12-29 | 2019-09-13 | 广东生益科技股份有限公司 | A kind of modified polyphenylene ether resin and its application |
| CN106832778B (en) * | 2017-02-13 | 2019-04-02 | 广州仑利奇合成树脂有限公司 | A kind of halogen-free flameproof epoxy systems and preparation method thereof |
| CN107502261B (en) * | 2017-09-14 | 2020-07-14 | 广州欣凯化工科技有限公司 | High-temperature-resistant anti-freezing resin adhesive for wooden products |
| TW202114490A (en) * | 2019-09-27 | 2021-04-01 | 鼎展電子股份有限公司 | Resistor and capacitor embedded flexible copper foil structure and printed circuit board structure using the same |
| CN113861680B (en) * | 2021-11-04 | 2023-09-22 | 中北大学 | Preparation method of degradable and toughened polybenzoxazine |
| CN114804893B (en) * | 2022-05-17 | 2023-01-03 | 惠州市纵胜电子材料有限公司 | Electronic product shell based on continuous ceramic fibers and preparation method thereof |
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| TW593426B (en) * | 2001-04-25 | 2004-06-21 | Ind Tech Res Inst | Epoxy group-containing curable polyphenylene ether resin, composition made therefrom, and process for preparing the resin |
| KR100595771B1 (en) * | 2001-09-20 | 2006-06-30 | 아사히 가세이 케미칼즈 가부시키가이샤 | Functionalized Polyphenylene Ether |
| US7439310B2 (en) * | 2006-07-06 | 2008-10-21 | Asahi Kasei Chemicals Corporation | Polyphenylene ether modified by reaction with cresol novolac epoxy resin |
| CN102093666B (en) * | 2010-12-23 | 2012-09-26 | 广东生益科技股份有限公司 | Halogen-free resin composite and preparation method of halogen-free copper clad laminate using same |
| CN102516530B (en) * | 2011-12-08 | 2014-03-12 | 中山台光电子材料有限公司 | Epoxy modified polyphenylene ether resin, resin composition and its application |
| CN102850766B (en) * | 2012-09-20 | 2014-07-09 | 苏州生益科技有限公司 | Halogen-free resin composition, prepreg and laminated board made from the same |
| KR101476895B1 (en) * | 2012-12-26 | 2014-12-26 | 주식회사 두산 | Resin compositions and metal foil laminate comprising the resin composition |
| JP6128311B2 (en) * | 2013-02-12 | 2017-05-17 | パナソニックＩｐマネジメント株式会社 | Resin composition, resin varnish, prepreg, metal-clad laminate, and printed wiring board |
| CN105419348B (en) * | 2016-01-18 | 2018-11-27 | 广东生益科技股份有限公司 | A kind of resin combination and prepreg and laminate using it |
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